WO2005085402A1 - Composition d’huile pour machine frigorifique - Google Patents

Composition d’huile pour machine frigorifique Download PDF

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Publication number
WO2005085402A1
WO2005085402A1 PCT/JP2005/003510 JP2005003510W WO2005085402A1 WO 2005085402 A1 WO2005085402 A1 WO 2005085402A1 JP 2005003510 W JP2005003510 W JP 2005003510W WO 2005085402 A1 WO2005085402 A1 WO 2005085402A1
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Prior art keywords
acid
group
branched
linear
ester
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PCT/JP2005/003510
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English (en)
Japanese (ja)
Inventor
Kazuo Tagawa
Katsuya Takigawa
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Nippon Oil Corporation
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Filing date
Publication date
Priority claimed from JP2004061240A external-priority patent/JP4493373B2/ja
Priority claimed from JP2004100513A external-priority patent/JP4520764B2/ja
Application filed by Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to CN2005800070412A priority Critical patent/CN1930276B/zh
Priority to US10/591,499 priority patent/US20070257229A1/en
Publication of WO2005085402A1 publication Critical patent/WO2005085402A1/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
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/021—Hydroxy compounds having hydroxy groups bound to acyclic or cycloaliphatic carbon atoms
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/042—Epoxides
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
    • C10M2207/126—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids monocarboxylic
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/24—Epoxidised acids; Ester derivatives thereof
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/281—Esters of (cyclo)aliphatic monocarboxylic acids
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • 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
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/283—Esters of polyhydroxy compounds
    • C10M2207/2835—Esters of polyhydroxy compounds used as base material
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/047—Thioderivatives not containing metallic elements
    • 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
    • C10N2020/101—Containing Hydrofluorocarbons
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • 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
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/66—Hydrolytic stability
    • 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 refrigerator oil composition.
  • Patent Document 1 Japanese Patent Publication No. Hei 3—505602
  • Patent Document 2 JP-A-3-128992
  • Patent Document 3 JP-A-3-200895
  • the present invention has been made in view of the above-mentioned problems of the related art, and achieves a high level of both lubricity and stability for refrigeration and air-conditioning equipment using HFC refrigerant or the like. Refrigeration that can operate refrigeration and air conditioning equipment stably for a long period of time.
  • An object is to provide a machine oil composition.
  • the present invention includes a polyol ester as a base oil, a phosphorothioate, a phosphorus-based additive other than the phosphorothionate, and a glycidyl ester type epoxy compound.
  • the present invention provides a refrigerating machine oil composition characterized in that:
  • a phosphorus-based additive other than phosphorothionate is simply referred to as "phosphorous-based additive" in some cases, and phosphorothionate is not included in the phosphorus-based additive.
  • a polyol ester is used as a base oil, a phosphorothioate and a phosphorus-based additive are combined, and these are added together with a glycidyl ester-type epoxy compound, whereby lubricity and stability are improved. Since both properties are sufficiently enhanced, it is possible to operate the refrigeration / air-conditioning equipment stably for a long period of time even when used with an HFC refrigerant.
  • the effect of improving the wear resistance and stability of the refrigerating machine oil composition of the present invention can be very useful because it can contribute to prolonging the service period of the refrigeration and air conditioning equipment.
  • the long-term reliability of the refrigeration / air-conditioning device can be improved without improving the hardware such as the sliding material inside the compressor.
  • the effect of improving abrasion resistance and stability according to the present invention is a synergistic effect of a phosphorothioate, a phosphorus-based additive, and a glycidyl ester type epoxy conjugate in a refrigerator oil composition containing a polyol ester as a base oil. This is due to action and can only be obtained by making these essential components.
  • the refrigerating machine oil composition to which the refrigerating machine oil composition of the present invention is applied is not particularly limited. However, when the refrigerating machine oil composition of the present invention is used as a refrigerating machine oil composition for a packaged air conditioner, the refrigerating machine oil composition is used. Is a mixed base oil of a tetraester of pentaerythritol and a fatty acid and a diester of neopentyl dallycol and a fatty acid, a phosphorothioate, a phosphorus-based additive other than the phosphorothionate, and a glycidyl ester-based epoxy conjugate. It is preferable to contain The term “package air conditioner” in the present invention means that the rated cooling power consumption exceeds 3 kW and the outdoor unit and the indoor unit are connected. If the length of the pipe (pipe length) is 10m or more, use it.
  • Air conditioners to which refrigerating machine oil is applied are generally classified into a room air conditioner for home use and a package conditioner represented by a large air conditioner for business use for building air conditioning. These air conditioners have structural differences that go beyond the differences in output. For example, in the case of a room air conditioner, the length of the pipe connecting the outdoor unit and the indoor unit is short (about 5 m), whereas in the case of a knock air conditioner, the outdoor unit and the indoor unit are connected. The maximum length of the pipe is several tens of meters. Therefore, in the case of the packaged air conditioner used, since the piping is long, the amount of air and moisture mixed into the refrigeration cycle including the piping at the time of application may increase the deterioration factor of the refrigerating machine oil. There is concern.
  • the refrigerating machine oil used for the air conditioner can discharge the compressor power also into the refrigerating cycle
  • the refrigerating machine oil has a characteristic of circulating through the refrigerating cycle and returning to the compressor again (hereinafter referred to as oil returnability). Is required.
  • oil returnability a characteristic of circulating through the refrigerating cycle and returning to the compressor again
  • the refrigerating machine oil composition for a packaged air conditioner of the present invention uses, as a base oil, a mixed ester of a tetraester of pentaerythritol with a fatty acid and a mixed ester of a diester of neopentyldaricol with a fatty acid.
  • the base oil contains phosphorothioate, a phosphorus-based additive other than the phosphorothionate, and a glycidyl ester-based epoxy compound to provide stability to air and moisture, compatibility with HFC refrigerants, etc. All of the oil return and lubricity can be improved in a well-balanced manner.
  • the refrigerating machine oil composition for a packaged air conditioner of the present invention it is possible to prevent the deterioration of the refrigerating machine oil thread and components due to the incorporation of air and moisture, to ensure sufficient oil return, prevent abrasion, and improve energy efficiency. Improvement can be achieved, and the package air conditioner can be operated stably for a long period of time.
  • both lubricity and stability can be achieved at a high level, and the refrigeration / air-conditioning apparatus can be stably operated for a long period of time. It becomes possible to provide a possible refrigerator oil composition.
  • the refrigerator oil composition of the present invention contains (A) a polyol ester as a base oil.
  • a polyol ester an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 6 to 20 carbon atoms is preferably used.
  • diol examples include ethylene glycol, 1,3 propanediol, propylene glycol, 1,4 butanediol, 1,2 butanediol, 2-methyl-1,3 propanediol, 1 , 5 pentanediol, neopentyl glycol, 1,6 xanthione, 2-ethyl-2, methyl-1,3 propanediol, 1,7 ptandionone, 2-methyl-2-propyl1,3 propanediole , 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-decanediol, 1,12-dodecanediol, etc.
  • Examples of the polyol having 3 to 20 hydroxyl groups include trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), tory (trimethylolpropane), and pentaerythritol.
  • polyols include neopentyl glycol, trimethylolone ethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, and di (pentaerythritol).
  • hindered alcohols such as tree (pentaerythritol).
  • the fatty acid used in the polyol ester is not particularly limited in the number of carbon atoms, but usually one having 1 to 24 carbon atoms is used.
  • fatty acids having 1 to 24 carbon atoms those having 3 or more carbon atoms are preferable for lubricating point force, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are more preferable.
  • Those having several tens or more are particularly preferred. From the viewpoint of compatibility with the refrigerant, those having 18 or less carbon atoms are preferred, those having 12 or less carbon atoms are more preferred, and those having 9 or less carbon atoms are more preferred.
  • the fatty acids to be used may be linear fatty acids or branched fatty acids! /, Or may be misaligned! /, But linear fatty acids are preferred because of their lubricity. Branched fatty acids are preferred from the viewpoint of hydrolysis stability. Furthermore, the powerful fatty acids can be either saturated or unsaturated fatty acids.
  • Examples of the fatty acid include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, and hexadecane Acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc., and these fatty acids are linear fatty acids and branched fatty acids.
  • a fatty acid (neo acid) which is an ⁇ -carbon nuclear-grade carbon atom may be used.
  • valeric acid ⁇ -pentanoic acid
  • caproic acid ⁇ -xanoic acid
  • enanthic acid ⁇ -heptanoic acid
  • prillic acid ⁇ -octanoic acid
  • pelargonic acid ⁇ -nonanoic acid
  • Prulinic acid ⁇ -decanoic acid
  • oleic acid cis-9-year-old cutadecenoic acid
  • isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3, 5, 5-trimethylhexanoic acid is preferably used.
  • the (A) polyol ester according to the present invention is a partial ester in which some of the hydroxyl groups of the polyol are left unesterified and have a V, as long as they have two or more ester groups. It may be a complete ester in which all the hydroxyl groups are esterified, or a mixture of a partial ester and a complete ester, but a complete ester is preferred!
  • the combination of the above-mentioned alcohol and fatty acid is not particularly limited, but lubricity, hydrolytic stability, compatibility with HFC refrigerant, and the like. It is preferable to select a combination of an alcohol and a fatty acid constituting the polyol ester (A) according to the properties required for the above.
  • the fatty acid composition of (A) the polyol ester is 20 mol% or more of linear fatty acid (80 mol% or less of branched fatty acid).
  • the fatty acid composition of (A) the polyol ester is 20 mol% or more of linear fatty acid (80 mol% or less of branched fatty acid).
  • Preferred linear fatty acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, and heptadecaic acid. Acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid and the like.
  • the alcohol constituting (A) the polyol ester hindered alcohol is preferred, and among them, pentaerythritol is particularly preferred! /.
  • the fatty acid composition of the (A) polyol ester is preferably 20 mol% or less of linear fatty acids (80 mol% or more of branched fatty acids). More than 10 mol% of chain fatty acids (90 mol% or less of branched fatty acids) It is particularly preferred that the preferred linear fatty acid is 5 mol% or more (branched fatty acid 95 mol% or less), and it is particularly preferred that all the preferred fatty acids are branched fatty acids.
  • Preferred branched fatty acids are, for example, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 2-methyloctanoic acid , 3,5,5-trimethylhexanoic acid and the like.
  • 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are more preferred, and it is particularly preferable that both 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are essential components. preferable.
  • the alcohol constituting the (A) polyol ester hindered alcohol is preferred, and pentaerythritol is particularly preferred.
  • a mixed fatty acid of pentanoic acid and Z or heptanoic acid and 3,5,5-trimethylhexanoic acid it is preferable to use these three types of mixed fats.
  • U especially preferred to use an acid.
  • the mixing ratio (molar ratio) of the three fatty acids is appropriately selected, but the ratio of pentanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and still more preferably the total amount of the mixed fatty acids. 10-50%.
  • the ratio of heptanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and further preferably 10 to 50%.
  • the ratio of 3,5,5-trimethylhexanoic acid is preferably 10% or more and less than 70%, preferably 20% to 60%, more preferably 30 to 50%.
  • pentaerythritol is particularly preferable among the above-mentioned hindered alcohols.
  • the pour point of the (A) polyol ester used in the present invention is not particularly limited !, but from the viewpoint of low temperature performance, preferably 20 ° C or lower, more preferably 25 ° C or lower, still more preferably. Is below 30 ° C.
  • the acid value of the polyol ester (A) is not particularly limited !, but from the viewpoint of stability, it is preferably 0.1 mgKOHZg or less, more preferably 0.05 mgKOHZg or less, and still more preferably 0 mgKOHZg or less. It is less than 03mgKOHZg.
  • the kinematic viscosity of the polyol ester (A) is not particularly limited !, but from the viewpoint of stirring resistance, the kinematic viscosity at 40 ° C is preferably 200 mm 2 Zs or less, more preferably 100 m 2 Zs or less. m 2 Zs or less, more preferably 80 mm 2 Zs or less.
  • the kinematic viscosity at 40 ° C. is preferably 3 mm 2 Zs or more, more preferably 5 mm 2 Zs or more, and still more preferably 10 mm 2 Zs or more, from the viewpoint of lubricity.
  • the viscosity index of the polyol ester (A) is not particularly limited, but is preferably 80 or more, more preferably 90 or more, from the viewpoint of low-temperature stirring resistance.
  • the content of the polyol ester (A) in the refrigerating machine oil composition of the present invention is not particularly limited, but from the viewpoint of the effects on various properties such as lubricity, stability, and compatibility, the total composition is referred to. Is preferably 70% by mass or more, more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.
  • (A-1) a tetraester of pentaerythritol and a fatty acid (hereinafter sometimes referred to as “ester (A- 1) ”) and (A-2) a mixed ester of diester of neopentyldaricol and a fatty acid (hereinafter sometimes referred to as" ester (A-2) ”) as a base oil.
  • ester (A-1) a tetraester of pentaerythritol and a fatty acid
  • (A-2) a mixed ester of diester of neopentyldaricol and a fatty acid
  • ester (A-2) a mixed ester of diester of neopentyldaricol and a fatty acid
  • the number of carbon atoms of the fatty acid constituting the ester (A-1) is not limited, but usually one having 1 to 24 carbon atoms is used. From the viewpoint of lubricity, the fatty acid preferably has 3 or more, more preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. Regarding the refrigerant compatibility, the carbon number of the fatty acid is preferably 18 or less, more preferably 12 or less, still more preferably 9 or less.
  • the fatty acid constituting the ester (A-1) may be a linear fatty acid or a branched fatty acid, which may be less than or equal to a linear fatty acid.
  • a linear fatty acid is preferred from the viewpoint of lubricity.
  • a branched fatty acid is preferred from the viewpoint of hydrolysis stability.
  • the fatty acid may be either a saturated fatty acid or an unsaturated fatty acid.
  • Specific examples of the fatty acid constituting the ester (A-1) include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, and tetradecane.
  • fatty acids may be either linear fatty acids or branched fatty acids, and furthermore, fatty acids whose ⁇ carbon atom is a quaternary carbon atom Acid).
  • valeric acid ⁇ -pentanoic acid
  • cabronic acid ⁇ -xanoic acid
  • enanthic acid ⁇ -heptanoic acid
  • caprylic acid ⁇ -octanoic acid
  • ⁇ ⁇ -largonic acid ⁇ -nonanoic acid
  • Power prulinic acid ⁇ -decanoic acid
  • oleic acid cis-9-octadecenoic acid
  • isopentanoic acid (3-methylbutanoic acid)
  • 2-methylhexanoic acid 2-ethylpentanoic acid
  • 2-ethylhexanoic acid 2-ethylhexanoic acid
  • 3,5,5-trimethylhexanoic acid are preferably used.
  • the ester (A-1) may be a partial ester in which some of the four hydroxyl groups of pentaerythritol remain without being esterified, and all the hydroxyl groups may be esterified. It may be an ester, or a mixture of a partial ester and a complete ester, but preferably a complete ester.
  • the fatty acid constituting the ester (A-1) may be one kind of the above-mentioned fatty acids alone or a combination of two or more kinds thereof. It is preferable to select the fatty acid constituting the pentaerythritol ester according to the required properties such as compatibility with the refrigerant.
  • the fatty acid composition of the ester (A-1) is 20 mol% or more of linear fatty acids (80 mol% of branched fatty acids). Below) (more preferably 25 mol% or more (branched fatty acid 75 mol% or less), more preferably 30 mol% or more (branched fatty acid 70 mol% or less). Is more preferred.
  • Preferred linear fatty acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and Examples include cutadecanoic acid, nonadecanoic acid, icosanoic acid, and oleic acid.
  • the fatty acid composition of the ester (A-1) is preferably 20 mol% or less of linear fatty acids (80 mol% or more of branched fatty acids). More preferably 10 mol% or less of linear fatty acids (90 mol% or more of branched fatty acids), more preferably 5 mol% or less of linear fatty acids (95 mol% or more of branched fatty acids). It is particularly preferred that all fatty acids are branched fatty acids.
  • Preferred branched fatty acids include, for example, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 2-methyl Octanoic acid, 3,5,5-trimethylhexanoic acid and the like can be mentioned. Among them, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are more preferred. Both 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are essential components. But especially preferred.
  • the mixing ratio (molar ratio) of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is preferably 10: 90-90: 10, more preferably 20: 80-80: 20, and furthermore, Preferably it is 30: 70-70: 30.
  • a mixed fatty acid of pentanoic acid and Z or heptanoic acid and 3,5,5-trimethylhexanoic acid it is preferable to use a mixed fatty acid of pentanoic acid and Z or heptanoic acid and 3,5,5-trimethylhexanoic acid. It is particularly preferred to use three types of mixed fatty acids.
  • the mixing ratio (molar ratio) of the three types of fatty acids is appropriately selected, and the ratio of pentanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and still more preferably 10 to 60% based on the total amount of the mixed fatty acids. — 50%.
  • the ratio of heptanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and further preferably 10 to 50%.
  • the ester ( ⁇ -1) In order to achieve a high level of balance between lubricity, hydrolyzability, and compatibility with HFC refrigerants, etc., the ester ( ⁇ -1) must be
  • the fatty acid composition is preferably straight-chain fatty acids of 20 mol% or less (branched fatty acids of 80 mol% or more), more preferably straight-chain fatty acids of 10 mol% or less (branched fatty acids of 90 mol% or more). It is particularly preferred that all fatty acids, which are more preferably 5 mol% or less of chain fatty acids (95 mol% or more of branched fatty acids), are branched fatty acids.
  • V-branched fatty acids include the branched fatty acids exemplified in the description when importance is placed on the hydrolytic stability, and include 2-ethylhexanoic acid and 3,5,5-trimethylhexane. It is particularly preferred that both acids are essential components.
  • the mixing ratio (molar ratio) of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is preferably 10: 90-90: 10, more preferably 20: 80-80: 20, and Preferably it is 30: 70-70: 30.
  • the number of carbon atoms of the fatty acid constituting the ester (A-2) is not particularly limited. Those having 1 to 24 carbon atoms are used. From the viewpoint of lubricity, the fatty acid preferably has 3 or more, more preferably 4 or more, more preferably 5 or more, and still more preferably 6 or more. As for the refrigerant compatibility, the carbon number of the fatty acid is preferably 18 or less, more preferably 12 or less, still more preferably 9 or less.
  • the fatty acid constituting the ester (A-2) may be a linear fatty acid or a branched fatty acid!
  • the branched chain fatty acid is also preferable in terms of the hydrolysis stability.
  • the powerful fatty acids may be the difference between saturated fatty acids and unsaturated fatty acids!
  • fatty acid constituting the ester (A-2) include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, and tetradecane. Acids, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc., and these fatty acids may be either linear fatty acids or branched fatty acids.
  • Fatty acids (neo acids) in which the ⁇ carbon atom is a quaternary carbon atom may be used.
  • valeric acid ⁇ -pentanoic acid
  • hydroproic acid ⁇ -hexanoic acid
  • enanthic acid ⁇ -heptanoic acid
  • power prillic acid ⁇ -octanoic acid
  • pelargonic acid ⁇ -nonanoic acid
  • Force-puric acid ⁇ -decanoic acid
  • oleic acid ds-9-year-old cactadecenoic acid
  • isopentanoic acid (3-methylbutanoic acid)
  • 2-methylhexanoic acid 2-ethylpentanoic acid
  • 2-ethyl Hexanoic acid 2-ethyl Hexanoic acid and 3,5,5-trimethylhexanoic acid
  • the ester (A-2) may be a complete ester obtained by esterifying all the hydroxyl groups, even if one of the two hydroxyl groups of neopentyl glycol is a partial ester remaining without being esterified. It may be an ester, or even a mixture of a partial ester and a complete ester !, but it is preferably a complete ester! /.
  • the combination with the above-mentioned fatty acid is not particularly limited, but it depends on the required properties such as lubricity, hydrolytic stability, and compatibility with the HFC refrigerant. Therefore, it is preferable to select the fatty acids that make up neopentyldaricol ester.
  • the fatty acid composition of the stele (A-2) is preferably at least 20 mol% of linear fatty acids (up to 80 mol% of branched fatty acids), preferably at least 25 mol% of linear fatty acids (up to 75 mol% of branched fatty acids) It is even more preferable that the linear fatty acid is more preferably 30 mol% or more (branched fatty acid 70 mol% or less).
  • Preferred linear fatty acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, pendecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, and Examples include cutadecanoic acid, nonadecanoic acid, icosanoic acid, and oleic acid.
  • the fatty acid composition of the ester (A-2) is preferably 40 mol% or less of linear fatty acids (60 mol% or more of branched fatty acids).
  • Straight-chain fatty acids 30 mol% or less are more preferable.
  • Straight-chain fatty acids 20 mol% or less are more preferable. More preferably, it is 10 mol% or less (branched fatty acid 90 mol% or more). All the fatty acids are particularly preferably branched fatty acids.
  • Preferred branched fatty acids include, for example, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, and 2-methylotatan Acid, 3,5,5-trimethylhexanoic acid and the like.
  • 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are more preferred.
  • Both 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are essential components. Is particularly preferred.
  • the mixing ratio (molar ratio) of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid is preferably 10: 90-90: 10, more preferably 20: 80-80: 20, furthermore Preferably it is 30: 70-70: 30.
  • a mixed fatty acid of pentanoic acid and Z or heptanoic acid and 3,5,5-trimethylhexanoic acid it is preferable to use a mixed fatty acid of pentanoic acid and Z or heptanoic acid and 3,5,5-trimethylhexanoic acid. It is particularly preferred to use three types of mixed fatty acids.
  • the mixing ratio (molar ratio) of the three types of fatty acids is appropriately selected, and the ratio of pentanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and still more preferably 10 to 60% based on the total amount of the mixed fatty acids. — 50%.
  • the ratio of heptanoic acid is preferably 1 to 60%, more preferably 5 to 55%, and further preferably 10 to 50%.
  • the ratio of hexanoic acid 5- trimethyl preferably 10- 70%, good Mashiku ⁇ or 20- 60 0/0, more preferably ⁇ or a 30- 50 0/0.
  • the ester (A-2) The fatty acid composition is preferably 40 mol% or less of linear fatty acids (60 mol% or more of branched fatty acids), more preferably 30 mol% or less of linear fatty acids (90 mol% or more of branched fatty acids).
  • the fatty acid is 20 mol% or less of linear fatty acids (80 mol% or more of branched fatty acids) .More preferably, it is 10 mol% or less of linear fatty acids (90 mol% or more of branched fatty acids). Particularly preferred are branched fatty acids. Preferred examples of the branched fatty acid include the branched fatty acids exemplified in the description when importance is placed on the hydrolytic stability, and include 2-ethylhexanoic acid and 3,5,5-trimethylhexyl. Particularly preferred is 2-ethylhexanoic acid, which is more preferably sanic acid.
  • the content of the ester (A-2) is preferably 80% by mass or less (the ester (A-1) is 20% by mass or more). It is even more preferable that the content of the ester (A-1) is 60% by mass or less (the ester (A-1) is 40% by mass or more). Above) is even more preferred.
  • the kinematic viscosity of the mixed base oil of the ester (A-1) and the ester (A-2) is not particularly limited, but the kinematic viscosity at 40 ° C is considered from the viewpoint of oil return in long piping. Is preferably 60 mm 2 Zs or less, more preferably 50 mm 2 Zs or less, still more preferably 46 mm 2 Zs or less, and particularly preferably 40 mm 2 Zs or less. On the other hand, from the viewpoint of wear resistance, the kinematic viscosity at 40 ° C.
  • the pour point of the mixed base oil of the ester (A-1) and the ester (A-2) is not particularly limited, but is preferably ⁇ 20 ° C. or lower, more preferably — The temperature is 25 ° C or lower, and more preferably -30 ° C or lower.
  • the acid value of the mixed base oil is not particularly limited, but is preferably 0.10 mgKOHZg or less, more preferably 0.05 mgKO HZg or less.
  • the refrigerating machine oil composition of the present invention contains a mixed base oil of ester (A-1) and ester (A-2), the refrigerating machine oil composition contains ester (A-1), (A-- A polyol ester other than 2) may be further contained.
  • esters other than the esters (A-1) and (A-2) trimethylolethane, trimethylolpropane, trimethylolbutane, di (trimethylolpropane), Esters of hindered alcohols such as tri- (trimethylolpropane), di (pentaerythritol) and tory (pentaerythritol) are more preferred, and esters of trimethylolethane, trimethylolpropane and trimethylolbutane are even more preferred! /.
  • Preferable polyol esters other than the esters (A-1) and (A-2) include, for example, valeric acid, caproic acid, enanthic acid, force prillic acid, pelargonic acid, force pric acid, oleic acid, Isopentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid
  • At least one fatty acid selected from the group consisting of trimethylolethane and trimethylolethane examples include at least one alcohol selected from methylolpropane and trimethylolbutane, and diesters, triesters, tetraesters, and mixtures thereof obtained from lime.
  • the polyol ester is composed of two or more kinds of fatty acids because the low-temperature characteristics of the refrigerating machine oil composition and the compatibility with the refrigerant tend to be improved.
  • the polyol ester composed of two or more fatty acids includes a mixture of two or more esters of a polyol and one fatty acid, and an ester of a polyol and two or more mixed fatty acids. .
  • the refrigerating machine oil composition of the present invention may contain (A) an ester oil other than the polyol ester (such as an aromatic ester, a dibasic acid ester, a complex ester, or a carbonate ester) as long as the excellent properties are not impaired. May be contained as a base oil. Sarapiko, other than ester oil Oxygen-containing synthetic oils (polybutyl ether, ketone, polyphenol ether, silicone, polysiloxane, perfluoroether, etc.), mineral oils, and hydrocarbon-based synthetic oils (olefin polymer, naphthalene conjugate, alkylbenzene, etc.) ) May be further contained.
  • an ester oil other than the polyol ester such as an aromatic ester, a dibasic acid ester, a complex ester, or a carbonate ester
  • Oxygen-containing synthetic oils polybutyl ether, ketone, polyphenol ether, silicone, polysiloxane, perflu
  • an aromatic carboxylic acid having a valency of 116, preferably 114, and more preferably 113, and an aliphatic carboxylic acid having a carbon number of 11 to 18, preferably 11 to 12 are used.
  • Esters with alcohol and the like can be mentioned.
  • Specific examples of the hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof.
  • the aliphatic alcohol having 118 carbon atoms may be a linear or branched one.
  • aromatic ester obtained by using the aromatic compound and the aliphatic alcohol include dibutyl phthalate, di (2-ethylhexyl) phthalate, diphenol phthalate, Didecyl phthalate, didodecyl phthalate, ditridecyl phthalate, triptyl trimellitate, tri (2-ethylhexyl) trimellitate, trinole trimellitate, tridecyl trimellitate, tridodecyl trimellitate, trimellitate And tritridecyl acid.
  • an aromatic carboxylic acid having a valency of 2 or more when an aromatic carboxylic acid having a valency of 2 or more is used, a simple ester composed of one kind of aliphatic alcohol may be used, or a complex ester composed of two or more kinds of aliphatic alcohols may be used. It may be a synthetic ester.
  • Examples of the dibasic acid ester include daltaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,2-cyclohexanedicarboxylic acid, and 4-cyclohexene-1,2-dicarboxylic acid
  • Esters with a monohydric alcohol having 11 to 15 carbon atoms and mixtures thereof are preferably used, and more specifically, ditridecyl glutarate, di 2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di 2 —Ethylhexyl sebacate, diester of 1,2-cyclohexanedicarboxylic acid with a 419 monovalent alcohol, 4-cyclohexene 1,2-dicarboxylic acid with a 419 monovalent alcohol And diesters and mixtures thereof.
  • the carbonate is a compound having a carbonate bond represented by the following formula (1) in the molecule.
  • the number of carbonate bond represented by the above formula (1) may be one per molecule, or two or more.
  • the alcohol constituting the carbonate ester the dibasic acid ester and the monohydric alcohol and polyol exemplified in the description of the (A) polyol ester, and the polyglycol added to the polyglycol and the polyol are used. Things can be used. Further, a compound obtained from carbonic acid and a fatty acid and Z or a dibasic acid may be used.
  • an ester other than (A) the polyol ester When using an ester other than (A) the polyol ester, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
  • esters other than the above-mentioned (A) polyol ester dibasic acid esters and carbonate esters are preferred because of their excellent compatibility with the refrigerant.
  • alicyclic dicarboxylic acid esters such as 1,2-cyclohexanedicarboxylic acid and 4-cyclohexene-1,2-dicarboxylic acid are compatible with the refrigerant. It is more preferable from the viewpoint of thermal stability and thermal stability.
  • dibasic acid ester preferably used in the present invention include at least one monohydric alcohol selected from the group consisting of butanol, pentanol, hexanol, heptanol, octanol and nonanol. At least one member selected from the group consisting of 1,1,2-cyclohexanedicarboxylic acid and 4-cyclohexene 1,2-dicarboxylic acid And dibasic acid esters obtained from basic acids, and mixtures thereof.
  • the dibasic acid ester used in the present invention since the low-temperature characteristics of the refrigerating machine oil composition and the compatibility with the refrigerant tend to be improved, the monohydric alcohol constituting the dibasic acid ester cannot be used. It is preferable to use two or more types.
  • the dibasic acid ester composed of two or more monohydric alcohols is a mixture of two or more esters of a dibasic acid and one alcohol and a mixed alcohol of two or more dibasic acids and two or more alcohols. It contains the ester of the above.
  • X 1 is preferably a hydrogen atom, an alkyl group, a cycloalkyl group or a compound having a structure represented by the following general formula (3).
  • Y 2 represents a hydrogen atom, an alkyl group or a cycloalkyl group
  • a 3 represents an alkylene group having 24 carbon atoms
  • e represents an integer of 150
  • a 1 and A 2 may be the same or different and each represents an alkylene group having 2 to 4 carbon atoms;
  • Y 1 represents a hydrogen atom, an alkyl group or a cycloalkyl group;
  • D represents an integer of 1 to 50.
  • X 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or a group represented by the above formula (3).
  • the number of carbon atoms of the alkyl group referred to herein is not particularly limited, but is usually 124, preferably 118, and more preferably 112.
  • the alkyl group may be straight-chain or branched.
  • alkyl group having 1 to 24 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, and a linear chain.
  • a branched pentyl group a straight or branched hexyl group, a straight or branched heptyl group, a straight or branched octyl group, a straight or branched nor group, a straight or branched decyl group, Straight-chain or branched undecyl group, straight-chain or branched dodecyl group, straight-chain or branched tridecyl group, Chain or branched tetradecyl, straight or branched pentadecyl, straight or branched hexadecyl, straight or branched heptadecyl, straight or branched octadecyl, straight or branched nonadecyl, A straight-chain or branched icosyl group, a straight-chain or branched helicosyl group, a straight-chain or branched docosyl group, a straight-chain or branched tricosyl
  • cycloalkyl group examples include a cyclopentyl group and a cyclohexyl group.
  • examples of the alkylene group having 2 to 4 carbon atoms represented by A 3 include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, a 1-methyltrimethylene group. Group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group and the like.
  • Y 2 in the above formula (2) represents a hydrogen atom, an alkyl group or a cycloalkylalkyl group.
  • the number of carbon atoms in the alkyl group referred to herein is not particularly limited, but is usually 124, preferably 118, and more preferably 112.
  • the alkyl group may be linear or branched.
  • the alkyl group of 1 one 24 carbon atoms include alkyl groups shown examples in the description of the X 1.
  • cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • a hydrogen atom or an alkyl group having 11 to 12 carbon atoms is preferable, and a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, -Butyl group, iso-butynole group, sec-butynole group, tert-butynole group, n-pentynole group, iso-pentynole group, neo-pentynole group, n-hexynole group, iso-hexynole group, n- Heptinole, iso-heptinole, n-octyl, iso-octyl, n-nor, iso-nonyl, n-decyl, iso-decyl, n-decyl, More preferably, it is any one of an iso-de
  • the group represented by X 1 is preferably a hydrogen atom, an alkyl group having 11 to 12 carbon atoms, a hydrogen atom preferably a group represented by the above general formula (3), methyl Group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl Nore, n-pentinole, iso-pentinole, neo-pentinole, n-hexinole, iso-hexyl, n-heptyl, iso-heptyl, n-hexyl, iso- Octyl, n-nonyl, iso-nonyl, n-decyl, iso-decyl, n-indecyl, iso-indecyl, n-dodecyl, iso-dodecyl or the general formula (3
  • Specific examples of the compound having B as a residue and having 3 to 20 hydroxyl groups include the aforementioned polyols.
  • a 1 and A 2 may be the same or different and each represent an alkylene group having 2 to 4 carbon atoms.
  • the alkylene group include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, a 1-methyltrimethylene group, a 2-methyltrimethylene group, a 1,1-dimethylethylene group, , 2-dimethylethylene group and the like.
  • Y 1 represents a hydrogen atom, an alkyl group or a cycloalkyl group.
  • the number of carbon atoms in the alkyl group is not particularly limited, but is usually 124, preferably 118, and more preferably 112.
  • the alkyl group may be linear or branched.
  • the alkyl group having a carbon number of 1 one 24 and specific examples thereof include Al kill groups exemplified in the description of X 1.
  • cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • the group represented by Y 1 is preferably a hydrogen atom or a hydrogen atom which is preferably an alkyl group having 11 to 12 carbon atoms, a methyl group, an ethyl group, an n-propyl group, an iso- Propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentynole, neo-pentynole, n-hexynole, iso-hexynole , N-heptinol group, iso-heptyl group, n-octyl group, iso-octyl group, n-nor group, iso-nor group, n-decyl group, iso-decyl group, n-dendecyl More preferably, it is any one of a group, an iso-indecyl group,
  • c, d and e represent the degree of polymerization of the polyoxyalkylene chain.
  • the polyoxyalkylene chains in the molecule may be the same or different.
  • the carbonate represented by the above formula (2) has a plurality of different polyoxyalkylene chains
  • the polymerization form of the oxyalkylene group is not particularly limited, and may be random copolymerization or block copolymerization.
  • a polyalkylene glycol polyol ether is produced by adding an alkylene oxide to a polyol compound, and this is mixed with a chromate formate. React at 0-30 ° C in the presence of alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal alkoxides such as sodium methoxide and sodium ethoxide, or alkalis such as metal sodium. This is obtained.
  • alkali metal hydroxides such as sodium hydroxide and potassium hydroxide
  • alkali metal alkoxides such as sodium methoxide and sodium ethoxide
  • alkalis such as metal sodium
  • a polyalkylene glycol polyol ether may be provided with a source of carbonic acid such as polyester carbonate or phosgene by an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an alkali metal hydroxide such as sodium methoxide or sodium ethoxide. It is obtained by reacting at 80-150 ° C in the presence of an alkali such as metal alkoxide or sodium metal. Thereafter, free hydroxyl groups are etherified as required.
  • a source of carbonic acid such as polyester carbonate or phosgene
  • an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide
  • an alkali metal hydroxide such as sodium methoxide or sodium ethoxide
  • the product obtained from the above-mentioned raw materials may be purified to remove by-products and unreacted products! / A small amount of by-products and unreacted products may be removed from the lubricating oil of the present invention. As long as excellent performance is not impaired, there is no problem even if present.
  • a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
  • the molecular weight of the carbonate ester used in the present invention is not particularly limited, but the number average molecular weight is preferably from 200 to 4,000 to improve the hermeticity of the compressor. More preferably, there is.
  • the kinematic viscosity of the carbonate ester used in the present invention at 100 ° C. is preferably 2-150 mm 2 / s, more preferably 4-100 mm 2 / s.
  • the mineral oil for example, a lubricating oil fraction obtained by subjecting a paraffin-based crude oil, an intermediate-based crude oil or a naphthenic-based crude oil to atmospheric distillation and reduced-pressure distillation can be subjected to solvent removal, solvent removal, and the like.
  • Paraffinic mineral oil or naphthenic mineral oil obtained by appropriately combining one or more purification means of extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment Is mentioned.
  • highly refined mineral oil (hereinafter, referred to as "highly refined mineral oil”) from the viewpoint of better thermal stability.
  • highly refined mineral oil A paraffinic, intermediate or naphthenic crude oil or a crude oil obtained by vacuum distillation of a residual oil obtained by distillation under normal pressure. Refined oil; deeply dewaxed oil obtained by further deep dewaxing after refining; hydrogenated oil obtained by hydrogenation treatment, and the like.
  • the refining method in the above-mentioned refining step is not particularly limited.
  • (a) hydrogenation treatment, (b) dewaxing treatment (solvent dewaxing or water Dewaxing), (c) solvent extraction, (d) alkali washing or sulfuric acid washing, and (e) clay treatment either alone or in combination of two or more in an appropriate order.
  • Method It is also effective to repeat any one of the processes (a) to (e) in a plurality of stages.
  • a method of hydrotreating a distillate or a method of performing an alkali washing or a sulfuric acid washing treatment after the hydrogenation;
  • a method of hydrotreating the distillate Dewaxing method;
  • Hydrogenation treatment after distillate is subjected to solvent extraction;
  • Distillation oil is subjected to two-stage or three-stage hydrogenation treatment, followed by alkali washing Or a method of washing with sulfuric acid;
  • V a method of performing the above-mentioned treatment (i)-(iv), followed by a dewaxing treatment again to obtain a deeply-dewaxed oil.
  • naphthenic mineral oils and mineral oils obtained by deep dewaxing treatment are preferable, such as low-temperature fluidity and no wax precipitation at low temperatures.
  • This deep dewaxing treatment is usually performed by a solvent dewaxing method under severe conditions, such as a catalytic dewaxing method using a zeolite catalyst.
  • the non-aromatic unsaturated component (unsaturation degree) of the highly refined mineral oil is preferably 10% by mass or less, more preferably 5% by mass or less, still more preferably 1% by mass or less, particularly preferably 0.1% by mass or less. If the non-aromatic unsaturated content exceeds 10% by mass, sludge will be generated and become chewy, and as a result, expansion mechanisms such as cabilli which constitute the refrigerant circulation system will tend to be clogged.
  • Examples of the olefin polymer include those obtained by polymerizing an olefin having 2 to 12 carbon atoms, and those obtained by subjecting a compound obtained by the polymerization to a hydrogenation treatment.
  • Examples of the olefin polymer include polybutene, polyisobutene, and 5 carbon atoms.
  • Preferred are oligomers of 12 ⁇ -olefins (poly atolefin), ethylene propylene copolymers, and hydrogenated ones of these.
  • the method for producing the olefin polymer is not particularly limited, and can be produced by various known methods.
  • poly- ⁇ -olefin is prepared by using ⁇ -olefin produced from ethylene as a raw material and subjecting it to a known polymerization method such as a Ziegler catalyst method, a radical polymerization method, a salt aluminum method, or a boron fluoride method.
  • a known polymerization method such as a Ziegler catalyst method, a radical polymerization method, a salt aluminum method, or a boron fluoride method.
  • the naphthalene conjugate is not particularly limited as long as it has a naphthalene skeleton. From the viewpoint of excellent compatibility with a power refrigerant, it has 114 alkyl groups having 11 to 10 carbon atoms, and Alkyl groups having a total carbon number of 1 to 10 preferably have 1 to 8 carbon atoms of 1 to 3 alkyl groups, and alkyl groups having a total carbon number of 3 to 8 are more preferable. I like it.
  • alkyl group having 11 to 10 carbon atoms that the naphthalene conjugate has include a methyl group, an ethyl group, an ⁇ -propyl group, an isopropyl group, a linear or branched butyl group.
  • a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
  • the method for producing the naphthalene compound is not particularly limited, and can be produced by various known methods. Examples of this include halogenated compounds of hydrocarbons having 11 to 10 carbon atoms, olefins having 2 to 10 carbon atoms or styrenes having 8 to 10 carbon atoms, sulfuric acid, phosphoric acid, keitandastenoic acid, hydrofluoric acid, etc.
  • the alkylbenzene is not particularly limited, but has excellent compatibility with the refrigerant, has 114 alkyl groups having 1 to 40 carbon atoms, and has a total carbon number of 1 to 40 of the alkyl groups. More preferred are those having 114 alkyl groups each having 1 to 30 carbon atoms and having a total carbon number of 3 to 30 alkyl groups.
  • alkyl group having 1 to 40 carbon atoms in the alkylbenzene include methyl Group, ethyl group, n-propyl group, isopropyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear Linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or branched A straight chain or branched dodecyl group, a straight chain or branched tridecyl group, a straight or branched tetradecyl group, a straight or branched pentadecyl group, Linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched non
  • the above-mentioned alkyl groups may be linear, branched, or displaced! /, However, in view of compatibility with organic materials used in the refrigerant circulation system, linear alkyl groups may be used. Group is preferred. On the other hand, branched alkyl groups are preferred in terms of refrigerant compatibility, thermal stability, lubricity, etc. In particular, in view of availability, branched alkyl groups derived from oligomers of olefins such as propylene, butene, and isobutylene Alkyl groups are more preferred.
  • alkylbenzene When alkylbenzene is used, a compound having a single structure may be used alone, or two or more compounds having different structures may be used in combination.
  • the method for producing the above-mentioned alkylbenzene is arbitrary, and is not limited at all.
  • the alkylbenzene can be produced by the following synthesis method.
  • the aromatic compound as a raw material specifically, benzene, toluene, xylene, ethylbenzene, methylethylbenzene, getylbenzene, a mixture thereof and the like are used.
  • linear or branched C6-40 carbon olefins obtained by polymerization of lower monoolefins (preferably propylene) such as ethylene, propylene, butene, and isobutylene; waxes, heavy oils, petroleum oils Distillate, linear or branched carbon having 6 to 40 carbon atoms obtained by thermal decomposition of polyethylene, polypropylene, etc .; petroleum fractionation power of kerosene, gas oil, etc. also separates n-paraffins and uses it as a catalyst.
  • a straight-chain olefin having 9 to 40 carbon atoms obtained by olefin formation, a mixture thereof and the like can be used.
  • a Friedel-Crafts type catalyst such as aluminum chloride and zinc chloride, sulfuric acid, phosphoric acid, kytungstic acid, hydrogen fluoride
  • a conventionally known alkylation catalyst such as an acid catalyst such as an acid and activated clay can be used.
  • Examples of the polyvinyl ether used in the present invention include a polyvinyl ether-based compound having a structural unit represented by the following general formula (4).
  • R 1 -R 3 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms, and R 4 is a divalent carbon atom having 1-10 carbon atoms. It represents a hydrocarbon group or a divalent, ether bond oxygen-containing hydrocarbon group with carbon number 2-2 0, R 5 represents a hydrocarbon group of 1 one 20 carbon atoms, s is the number of the average value Ca ⁇ -10 R 1 —R 5 may be the same or different for each structural unit, and when the structural unit represented by the general formula (4) has a plurality of R 4 O, R 40 may be the same or different. ]
  • a block copolymer or a random copolymer having a structural unit represented by the above general formula (4) and a structural unit represented by the following general formula (5) is converted into a polyvinyl ether system.
  • Compounds can also be used.
  • R 6 -R 9 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 120 carbon atoms, and R 6 -R 9 may be the same or different for each structural unit. May be. ]
  • R 1 to R 3 each represent a hydrogen atom or a hydrocarbon group having 118 carbon atoms (preferably a hydrocarbon group having 114 carbon atoms), and they are the same or different. You can do it.
  • Specific examples of strong hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, and various pentyl groups.
  • Alkyl groups such as various hexyl groups, various heptyl groups, various octyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups Groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, etc .; aryl groups such as benzyl group, various phenylethyl groups, various methylbenzyl groups, etc.
  • R 22 to R 24 a prime atom is preferable.
  • R 4 in the general formula (4) represents a divalent hydrocarbon group having 1 to 10 (preferably 2 to 10) carbon atoms or a divalent ether bond having 2 to 20 carbon atoms containing oxygen. Represents a hydrocarbon group.
  • divalent hydrocarbon group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a phenylethylene group, a 1,2-propylene group, a 2-phenyl-1,2-propylene group, Divalent aliphatic hydrocarbon groups such as 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various otaylene groups, various nonylene groups, and various decylene groups
  • An alicyclic hydrocarbon group having two binding sites on an alicyclic hydrocarbon such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and provylcyclohexane; various phenylene groups; , Various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups, and other divalent aromatic hydro
  • divalent ether-linked oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include a methoxymethylene group, a methoxyethylene group, a methoxymethylethylene group, a 1,1 bismethoxymethylethylene group, , 2-bismethoxymethylethylene group, ethoxymethylethylene group, (2-methoxyethoxy) methylethylene group, (1-methyl-2-methoxy) methylethylene group, and the like.
  • s in the general formula (15) represents a repeating number of R 19 0, the average value is 0 10, preferably a number 0 5 ranges. When the R 19 0 there is more than one in the same configuration units, 0 plurality of R 19 may be the same or different.
  • R 5 in the general formula (4) is the number 1 one 20 carbons, preferably a hydrocarbon group of 1 one 10, as the force Cal hydrocarbon group include a methyl group, Ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various hydroxyl groups, Alkyl groups such as various decyl groups; cycloalkyl groups such as cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups; -Methyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylcyclohexy
  • the molar ratio of carbon and oxygen is preferably in the range of 4.2-7.0. preferable. If the molar ratio is less than 4.2, the hygroscopicity becomes excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to decrease.
  • R 6 to R 9 may be the same or different and each represent a hydrogen atom or a hydrocarbon group having 120 carbon atoms.
  • the hydrocarbon group having 1 one 20 carbon atoms include the hydrocarbon groups exemplified in the description of R 5 in the general formula (4).
  • R 6 —R 9 may be the same or different for each structural unit.
  • the molar ratio of carbon and oxygen is preferably in the range of 4.2-7.0. If the molar ratio is less than 4.2, the hygroscopicity tends to be excessively high, and if it exceeds 7.0, the compatibility with the refrigerant tends to decrease.
  • a homopolymer in which only the structural unit represented by the general formula (4) also has a force the structural unit represented by the general formula (4), and the homopolymer represented by the general formula (5) And a block copolymer or a random copolymer composed of the constituent units to be used.
  • These homopolymers and copolymers must be produced by polymerization of the corresponding vinyl ether monomer and copolymerization of the corresponding hydrocarbon monomer having a olefinic double bond with the corresponding vinyl ether monomer. Can be.
  • the polybutyl ether used in the present invention includes:
  • One of the terminal structures is represented by the following general formula (6) or (7), and the other has a structure represented by the following general formula (8) or (9); and
  • R 1C> — R 12 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms, and R 13 is a divalent group having 1-10 carbon atoms.
  • R 13 is a divalent group having 1-10 carbon atoms.
  • R 14 is a C 1 to C 20 hydrocarbon group.
  • Represents a hydrogen radical, t represents the number of the average value of 0 10, when the terminal structure represented by the general formula (6) has a plurality of R 13 0, in each of a plurality of R 13 0 are the same They can be different.
  • R 13 — R ie may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 120 carbon atoms.
  • R 19 — R 21 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 18 carbon atoms
  • R 22 is a divalent carbon atom having 11 to 10 carbon atoms.
  • R 23 represents a hydrocarbon group having 120 carbon atoms
  • t represents a number having an average value of 0 to 10.
  • the terminal structure represented by the general formula (8) has a plurality of R 2 3 ⁇ 4, the plurality of R 2 ⁇ ⁇ ⁇ ⁇ may be the same or different.
  • R 24 — R may be the same or different and each represents a hydrogen atom or a carbon number. Represents one to twenty hydrocarbon groups. ]
  • R 28 to R 3 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 118 carbon atoms. ]
  • One of the terminals has a structure represented by the general formula (6) or (7) and the other has a structure represented by the general formula (8) or (9), and R 1 in the general formula (4) — R 3 is a hydrogen atom, s is a number from 0 to 4, R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 5 is a carbon atom having 1 to 20 carbon atoms. Being a hydrogen group;
  • R 1 to R 3 are all hydrogen atoms, s is a number from 0 to 4, and R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms.
  • R 5 is a hydrocarbon group having 120 carbon atoms;
  • R 1 — R 3 in the general formula (4) is All are hydrogen atoms, s is a number from 0 to 4, R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 5 is a hydrocarbon group having 1 to 20 carbon atoms thing;
  • R 1 to R 3 are all hydrogen atoms, s is a number from 0 to 4, and R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms. And R 5 is a hydrocarbon group having 120 carbon atoms.
  • the present invention has a structural unit represented by the above general formula (4), one of its terminals is represented by the general formula (6), and the other is represented by the following general formula (11)
  • Polyvinyl ether compounds having the structure shown can also be used. [Formula 8]
  • R dl — represents a hydrogen atom or a hydrocarbon group having 18 carbon atoms which may be the same or different, and R 34 and R 36 may be the same or different.
  • R 34 and R 36 may be the same or different.
  • R 35 and R 37 may be the same or different
  • each represents a hydrocarbon group having 110 carbon atoms
  • u and V are the same or different.
  • the terminal structure represented by the general formula (22) has a plurality of R 34 0 or R 36 0, more R 34 0 or R 360 may be the same or different.
  • a structural unit represented by the following general formula (12) or (13) is also obtained, the weight average molecular weight is 300 to 5,000, and one of the terminals is represented by the following general formula (14) or
  • a polyvinyl ether-based compound consisting of a homopolymer or copolymer of an alkyl vinyl ether having the structure represented by (15) can also be used.
  • R 3 ° represents a hydrocarbon group having 118 carbon atoms.
  • R 39 represents a hydrocarbon group having 118 carbon atoms.
  • R 4C> represents an alkyl group having 13 to 13 carbon atoms
  • R 41 represents a hydrocarbon group having 118 carbon atoms.
  • R 42 represents a hydrocarbon group having 118 carbon atoms.
  • one or more of the other base oils can be used in combination with the esters (A-1) and (A-2) to form a base for a refrigerating machine oil for a package air conditioner.
  • the material alkyl benzene, ester oils other than the esters (A-1) and (A-2), and polyvinyl ethers are preferably used.
  • the content of these other base oils is not particularly limited.
  • the content of the base oil is 50% based on the total amount of the composition. It is preferably at most 30% by mass, more preferably at most 30% by mass, even more preferably at most 10% by mass, and most preferably contains no other base oil.
  • the content of the base oil other than (A) the polyol ester is preferably 30% by mass or less, based on the total amount of the composition, from the viewpoint of affecting various properties such as lubricity, stability, and compatibility. It is more preferably at most 20% by mass, further preferably at most 10% by mass, particularly preferably at most 5% by mass. Most preferably, the refrigerating machine oil composition of the present invention contains no base oil other than (A) the polyol ester.
  • the refrigerator oil composition of the present invention contains a mixed base oil of ester (A-1) and ester (A-2), the content of the base oil other than the mixed base oil is oil. From the viewpoint of the balance of various properties such as reversion, lubricity and stability, it is preferably 50% by mass or less, more preferably 30% by mass or less 10% by mass, based on the total amount of the composition. Most preferably, the base oil contains no base oil other than the mixed base oil of the ester (A-1) and the ester (A-2). [0125] (phosphorothionate)
  • the refrigerator oil composition of the present invention contains (B) a phosphorothionate.
  • a phosphorothionate As the phosphorothionate (B), a compound represented by the following general formula (16) is preferably used.
  • R 43 , R 44 and R 45 may be the same or different and each represent a hydrocarbon group having 124 carbon atoms.
  • Specific examples of the hydrocarbon group having 1 to 24 carbon atoms represented by R 43 to R 45 include an alkyl group, a cycloalkyl group, an alkenyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, Arylalkyl groups and the like.
  • alkyl group examples include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, a pendecyl group, a dodecyl group, and a tridecyl group.
  • alkyl groups such as tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group and octadecyl group (these alkyl groups may be linear or branched).
  • Examples of the cycloalkyl group include cycloalkyl groups having 5 to 7 carbon atoms such as a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
  • Examples of the alkylcycloalkyl group include a methylcyclopentyl group, a dimethylcyclopentyl group, a methylethylcyclopentyl group, a getylcyclopentyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, and a methylethylcyclohexyl group.
  • Alkylcycloalkyl groups having 6 to 11 carbon atoms such as cycloalkyl groups of alkyl groups), such as hexyl groups, acetylcyclohexyl groups, methylcycloheptyl groups, dimethylcycloheptyl groups, methylethylcycloheptyl groups, and getylcycloheptyl groups.
  • alkenyl group examples include a butenyl group, a pentenyl group, a hexyl group, a heptenyl group, an otathenyl group, a nonenyl group, a decenyl group, a decenyl group, Dodecenyl group, tri Alkenyl groups such as decenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecyl group, octadecyl group, etc. (These alkenyl groups may be linear or branched and the position of the double bond may be different. Is optional).
  • Examples of the aryl group include aryl groups such as a phenyl group and a naphthyl group.
  • Examples of the alkylaryl group include a tolyl group, a xylyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a pentylphenyl group, a hexylphenyl group, and a heptylphenyl group.
  • C7-C18 alkylaryl groups such as octylphenol, norphenol, decylphenol, undecylphenol, dodecylphenyl, etc. However, the position of substitution on the aryl group is also arbitrary).
  • arylalkyl group examples include a benzyl group, a phenyl group, a phenyl group, a phenyl group, a phenylpentyl group, and a phenylhexyl group.
  • Aryl alkyl groups (these alkyl groups may be linear or branched).
  • the hydrocarbon group having 1 to 24 carbon atoms represented by R 43 to R 45 is preferably an alkyl group, an aryl group, or an alkyl group having 4 to 18 carbon atoms, which is preferably an alkyl aryl group.
  • Alkyl aryl and phenyl groups of numbers 7 to 24 are more preferred!
  • phosphorothionate represented by the general formula (16) include tributylphosphorothionate, tripentylphosphorothionate, trihexylphosphorothionate, and triheptylphosphorothionate.
  • Trioctylphosphorothionate Trioctylphosphorothionate, trinonylphosphorothionate, tridecylphosphorothionate, tridandecylphosphorothionate, tridodecylphosphorothionate, tritridecylphosphorothionate, tritetradecylphosphoronate Thionate, tripentadecylphosphorothionate, trihexadecylphosphorothionate, triheptadecylphosphorothionate, trioctadecylphosphorothionate, trioleylphosphorothionate, triphenylphosphorothionate Tricresylphosphorothionate, trixylphosphorothionate, cresyldiphenylphosphorothionate, xylendiphenylphosphorothionate, tris (n-propylpyrufurel) phosphorothionate, tris ( Isopropylphenyl
  • the content of the phosphorothionate (B) in the refrigerator oil composition of the present invention is preferably 0.01 to 5% by mass or less based on the total amount of the composition.
  • the abrasion resistance and stability (particularly, heat-oxidation stability) of the refrigerating machine oil composition can be further improved. More specifically, from the viewpoint that a high level of abrasion resistance can be obtained, the added amount of phosphorothionate is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. It is.
  • a wear reduction effect commensurate with the content cannot be obtained, and on the contrary, it may cause a decrease in stability or the occurrence of corrosive wear.
  • the refrigerator oil composition of the present invention further contains (C) a phosphorus-based additive (a phosphorus-based additive other than the above-mentioned phosphorothionate).
  • a phosphorus-based additive includes at least one phosphorus compound selected from the group consisting of phosphate esters, acidic phosphate esters, amine salts of acidic phosphate esters, chlorinated phosphate esters, and phosphite ester power. Is preferred.
  • These phosphorus conjugates are esters of phosphoric acid or phosphorous acid with alkynol or polyether-type alcohol or derivatives thereof.
  • Examples of the phosphoric acid ester include tributyl phosphate, tripentyl phosphate, trihexynolephosphate, triheptinolephosphate, trioctinolephosphate, trino-norrephosphate, tridecylphosphate, tridecylphosphate, and tridodecyl.
  • Phosphate tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleinolephosphate, trife-norephosphate, tricresinolephosphate, trixie Leninolephosphate, cresyl diphe-norephosphate, xyle-lediphe-norephosphate, and the like;
  • Examples of the acidic phosphoric acid ester include monobutyl acid phosphate and monopentyl acid. Phosphate, monohexinorea acid phosphate, monoheptinorea acid phosphate, monooctyl acid phosphate, mono-nole acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, Monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl Ruacid phosphate, diheptyl acid phosphate, dioctyl acid phosphate Ethate, dinoy
  • Examples of the amine salt of the acidic phosphoric acid ester include the acidic phosphoric acid ester methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine. Salts with amines such as min, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine and the like;
  • chlorinated phosphoric acid ester examples include Tris' dichloro propyl phosphate, Tris' chloroethynole phosphate, Tris' chloro phenol phosphate, polyoxyanoleylene'bis [di (chloroanolequinole)] Phosphates and the like;
  • Examples of the phosphite include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, octyl phosphite, dinol phosphite, didecyl phosphite, didecyl phosphite, and diphenyl phosphite.
  • the content of the phosphorus-based additive (C) in the refrigerator oil composition of the present invention is preferably 0.01 to 5% by mass or less based on the total amount of the composition.
  • the amount of the phosphorus-based additive is preferably 0.01% by mass or more, and more preferably 0.1% by mass or more, from the viewpoint that a high level of abrasion resistance is obtained.
  • the content is further increased, a wear reduction effect commensurate with the content cannot be obtained, and instead it may cause a decrease in stability or the occurrence of corrosive wear.
  • the content is 5% by mass or less, preferably 4% by mass or less, more preferably 3% by mass or less.
  • the refrigerating machine oil composition of the present invention further contains (D) a glycidyl ester type epoxy conjugate in addition to (B) the phosphorothionate and (C) the phosphorus-based additive.
  • the balance between wear resistance and stability and the effect achieved by the present invention are due to the synergistic action of these three components.
  • the glycidyl ester type epoxy resin conjugate used in the present invention is more epoxidized for refrigeration oil than other epoxy compounds such as glycidinoleatene compound epoxy compound and cyclohexenedioxide. When used as an additive, it is distinguished in terms of the effect of inhibiting metal catalyst corrosion and improving lubricity.
  • Preferable examples of the (D) glycidyl ester type epoxy conjugate include a compound represented by the following general formula (2).
  • R 4b represents a hydrocarbon group having 118 carbon atoms.
  • a hydrocarbon group include an alkyl group having 11 to 18 carbon atoms, an alkyl group having 2 to 18 carbon atoms, a cycloalkyl group having 5 to 7 carbon atoms, an alkylcycloalkyl group having 6 to 18 carbon atoms, 6-10 carbon atoms A reel group, an alkylaryl group having 7 to 18 carbon atoms, an arylalkyl group having 7 to 18 carbon atoms, and the like.
  • an alkyl group having 5 to 15 carbon atoms an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkyl phenyl group having an alkyl group having 14 to 14 carbon atoms are preferable.
  • glycidyl ester type epoxy compounds preferred! / ⁇ are specifically, for example, glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, glycidyl tert-butyl benzoate, glycidyl acrylate And glycidyl methacrylate.
  • the content of (D) the glycidyl ester type epoxy resin conjugate in the refrigerator oil composition of the present invention is preferably 0.01 to 5% by mass or less based on the total amount of the composition.
  • the amount of the (D) glycidyl ester type epoxy compound to be added is preferably 0.01% by mass or more, more preferably 0.1% by mass or more. % By mass or more.
  • the content of (D) the glycidyl ester type epoxy resin conjugate is preferably 3% by mass or less, more preferably 2% by mass or less. % By mass or less.
  • the refrigerator oil composition of the present invention comprises (A) a polyol ester as a base oil, (B) a phosphorothioate, (C) a phosphorus-based additive, and (D) a glycidyl ester. It contains a type epoxy as an essential component, and includes (E) an oil agent, (F) benzotriazole and Z or a derivative thereof, (G) an epoxy conjugate other than the glycidyl ester type epoxy conjugate, and Other additives may be further contained.
  • the oil agent includes an ester oil agent, a monohydric alcohol oil agent, a carboxylic acid oil agent, an ether oil agent and the like.
  • the ester oily agent is obtained by reacting an alcohol with a carboxylic acid.
  • the alcohol may be a monohydric alcohol or a polyhydric alcohol.
  • the carboxylic acid may be a monobasic acid or a polybasic acid.
  • the monohydric alcohol constituting the ester oily agent one having usually 124, preferably 111, and more preferably 118 carbon atoms is used, and as such alcohol, a linear alcohol is used. However, it may be branched or saturated or unsaturated.
  • alcohol having 124 carbon atoms include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, and linear Linear or branched hexanol, linear or branched octanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Linear or branched dodecanol, linear or branched tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched Branched hexadecanol, linear or branched heptadecanol, linear or branched otadadenol, linear or branched nonadenicol, linear or branched iconol Examples include sanol, linear or branched henicosanol, linear or branched branche
  • the polyhydric alcohol constituting the ester oily agent one having usually 2 to 10 valency, preferably 2 to 6 valency is used.
  • Specific examples of the 2-10 polyhydric alcohol include, for example, ethylene glycol, diethylene glycol, polyethylene glycol (3-15 mer of ethylene glycol), propylene glycol, dipropylene glycol, and polypropylene glycol (propylene glycol 3).
  • dihydric alcohols such as 1,2 pentanediol, 1,3 pentanediol, 1,4 pentanediol, 1,5 pentanediol, and neopentyl glycol; glycerin, polyglycerin (glycerin dimer to octamer, for example, diglycerin , Triglycerin, tetraglycerin, etc.), trimethy Alkane (trimethylolethane, trimethylolpropane, trimethylolbutane, etc.) and their dimer-octamer, pentaerythritol and their dimer-tetramer, 1,2,
  • Still more preferred are ethylene glycol, propylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitan, and mixtures thereof.
  • neopentyldaricol, trimethylolethane, trimethylolpropane, pentaerythritol, and mixtures thereof are preferable because higher acid resistance can be obtained.
  • the alcohol constituting the ester oily agent may be a monohydric alcohol or a polyhydric alcohol as described above. From the viewpoint of preventing precipitation at low temperatures, monohydric alcohols are preferred.
  • a fatty acid having 2 to 24 carbon atoms is usually used, and the fatty acid may be linear or branched, and may be saturated or unsaturated. It may be unsaturated or unsaturated.
  • the polybasic acid examples include a dibasic acid and trimellitic acid, and are preferably a dibasic acid from the viewpoint of preventing precipitation under a refrigerant atmosphere and at a low temperature.
  • the dibasic acid may be either a chain dibasic acid or a cyclic dibasic acid. In the case of a linear dibasic acid, it may be linear or branched, and may be saturated or unsaturated.
  • As the chain dibasic acid a chain dibasic acid having 2 to 16 carbon atoms is preferred. Specific examples include ethanenic acid, propane diacid, linear or branched butane diacid, and linear dibasic acid.
  • Linear or branched pentanedioic acid linear or branched hexanedioic acid, linear or branched heptanedioic acid, linear or branched octanedioic acid, linear or branched Nonanninic acid, linear or branched decandioic acid, linear or branched pendecanedioic acid, linear or Branched dodecane diacid, linear or branched tridecandioic acid, linear or branched tetradecandioic acid, linear or branched heptadecandioic acid, linear or branched hexadecane Diacid, linear or branched hexenedioic acid, linear or branched heptenedioic acid, linear or branched otatenedioic acid, linear or branched nonennilic acid, linear Linear or branched decenedioic acid, linear or branched dode
  • cyclic dibasic acid examples include 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, and aromatic dicarboxylic acid.
  • a chain dibasic acid is preferred from the viewpoint of stability.
  • the acid constituting the ester oil agent may be a monobasic acid or a polybasic acid as described above. However, from the viewpoint that the effect of improving the wear resistance and the frictional characteristics is more excellent, the acid is preferably used. Base acids are preferred.
  • the combination of the alcohol and the acid in the ester oil agent is arbitrary and not particularly limited, and examples thereof include esters obtained by the following combination (i)-(vii).
  • the (ii) one (vii) ester oily agent may be a complete ester in which all of the hydroxyl group of the polyhydric alcohol or the carboxyl group of the polybasic acid are esterified. Part may be a partial ester remaining as a hydroxyl group or a carboxyl group,
  • a point force having less influence on the anti-precipitation property under a refrigerant atmosphere and at a low temperature is preferably a perfect ester, and a partial ester is preferable from the viewpoint of an effect of improving frictional characteristics.
  • esters of (i) are preferred.
  • Esters of (i) are more preferred. These esters have extremely high effects of improving abrasion resistance and friction characteristics, and have little effect on the anti-precipitation property and the heat and acid stability under a refrigerant atmosphere and at a low temperature.
  • the carbon number of the monobasic acid is determined from the viewpoints of further improving abrasion resistance and friction characteristics, and from the viewpoint of heat and acid stability. It is preferably 10 or more, more preferably 12 or more, and still more preferably 14 or more.
  • the number of carbon atoms of the monobasic acid is preferably 28 or less, more preferably 26 or less, and still more preferably 24 or less from the viewpoint of preventing precipitation under a cooling atmosphere and at a low temperature.
  • esters include methyl stearate, butyl stearate, methyl palmitate, isopropyl palmitate, and the like.
  • the dibasic acid is preferably in the form of a chain!
  • esters include diisodecyl adipate, diisonol adipate, diisobutyl adipate and the like.
  • ester oil agents at least one selected from an ester of a monohydric alcohol and a monobasic acid and an ester of a linear dibasic acid and a monohydric alcohol is preferable.
  • Examples of the monohydric alcohol oily agent include the monohydric alcohols exemplified in the description of the ester oily agent.
  • the total carbon number of the monohydric alcoholic agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more, from the viewpoint of improving the friction and wear characteristics. Further, if the total carbon number is too large, precipitation may easily occur in a refrigerant atmosphere. Therefore, the total carbon number is preferably 20 or less, more preferably 18 or less, and most preferably 16 or less.
  • the carboxylic acid oil agent may be a monobasic acid or a polybasic acid.
  • Such carboxylic acids examples thereof include the monobasic acids and polybasic acids exemplified in the description of the ester oil agent. Of these, monobasic acids are preferred from the viewpoint of improving the friction characteristics and wear characteristics.
  • the total carbon number of the carboxylic acid oil agent is preferably 6 or more, more preferably 8 or more, and most preferably 10 or more, from the viewpoint of improving the friction characteristics and wear characteristics. If the total carbon number of the carboxylic acid oil agent is too large, precipitation may easily occur in a refrigerant atmosphere.Therefore, the total carbon number is preferably 20 or less, more preferably 18 or less, and most preferably 16 or less. preferable.
  • ether oil agent examples include etherified products of tri- to hexa-valent aliphatic polyhydric alcohols, and di- or tri-molecular condensates of 3- to hexa-valent aliphatic poly-alcohols. No.
  • the etherified product of a trivalent hexahydric aliphatic polyhydric alcohol is, for example, represented by the following general formula (18)
  • R 47 -R 71 may be the same or different and each is a hydrogen atom or a linear or branched alkyl group, aryl group, aralkyl group, and R a O) having 118 carbon atoms.
  • a glycol ether residue represented by R b (R a is an alkylene group having 2 to 6 carbon atoms, R b is an alkyl group having 1 to 20 carbon atoms, an aryl group, an aralkyl group, and n is an integer of 1 to 10) Indicates a group. ]
  • 3- to 6-valent aliphatic polyhydric alcohol examples include glycerin, trimethylolpronon, erythritol, pentaerythritol, arabitol, sorbitol, mannitol, and the like.
  • R 47 to R 71 in the above general formulas (18) to (23) represent methyl, ethyl, n-propyl, isopropyl, various butyl, various pentyl, various hexyl, various Heptyl group, various octyl groups, various nonyl groups, various decyl groups, various pentadecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups , A phenyl group and a benzyl group.
  • the etherified product also includes a partially etherified product in which a part of R 47 to R 71 is a hydrogen atom.
  • the bimolecular condensate or trimolecular condensate of the tri- or hexahydric aliphatic polyhydric alcohol may be the same or different from the compounds represented by the above general formulas (18) to (23). of And condensates.
  • a bimolecular condensate of an alcohol represented by the general formula (18) and an etherified product of a trimolecular condensate are represented by the general formulas (24) and (25), respectively.
  • ethers of bimolecular condensates and trimolecular condensates of alcohols represented by the general formula (21) are represented by general formulas (26) and (27), respectively.
  • bimolecular and trimolecular condensates of tri- to hexahydric aliphatic polyhydric alcohols include diglycerin, ditrimethylolpropane, dipentaerythritol, disorbitol, triglycerin, tritrimethylolpropane, and tripentane. Erythritol, trisorbitol, etc. Is mentioned.
  • ether oil agents represented by the general formulas (18) to (23) include trihexyl ether of glycerin, dimethyloctyl triether of glycerin, and di (methyloxyisopropylene) dodecyl triether of glycerin.
  • an ester is used in the refrigerator oil composition of the present invention.
  • an oil agent a monohydric alcohol oil agent, a carboxylic acid oil agent and an ether oil agent may be used alone or in combination of two or more.
  • an ester oil agent and an ether oil agent are preferable from the viewpoint of achieving a high level of friction characteristics, wear characteristics, anti-precipitation properties and stability in a well-balanced manner.
  • Ester oil agents and ether oil agents have better anti-sedimentation properties than monohydric alcohol oil agents, which can only achieve a high level of abrasion resistance and friction properties. Excellent stability.
  • the content of the oily agent (E) is arbitrary, but is preferably 0.01% by mass or more, more preferably 0.01% by mass or more, based on the total amount of the composition, from the viewpoint of excellent abrasion resistance and the effect of improving friction characteristics. is 0.
  • the content is preferably 10% by mass, based on the total amount of the composition, from the viewpoint of excellent anti-precipitation properties in a refrigerant atmosphere and at a low temperature, and excellent heat and acid stability of the refrigerating machine oil composition. Or less, more preferably 7.5% by mass or less, even more preferably 5% by mass or less.
  • the ratio of the total content of (B) the phosphorothionate, (C) the phosphorus-based additive, and (D) the glycidyl ester type epoxy additive to the content of (E) the oily agent is as follows: From the viewpoint that the abrasion resistance and friction characteristics can be further improved, the weight ratio is preferably 1:10 to 10: 1, more preferably 1: 5 to 5: 1, and still more preferably 1: 3-1. : 1
  • the refrigerator oil composition of the present invention preferably further contains (F) benzotriazole and Z or a derivative thereof.
  • (F) benzotriazole and Z or a derivative thereof By incorporating (F) benzotriazole and Z or a derivative thereof, the effect of improving wear resistance and friction characteristics can be further enhanced.
  • Benzotriazole is a compound represented by the following formula (28). [Formula 25]
  • benzotriazole derivative examples include, for example, an alkylbenzotriazole represented by the following general formula (29) and an (alkyl) aminoalkylbenzotriazole represented by the following general formula (30).
  • R 72 represents a linear or branched alkyl group having 14 to 14 carbon atoms, preferably a methyl group or an ethyl group
  • X represents 113, preferably 1 or 2 Indicates the number of Examples of R 72 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • Preferable examples include methyl benzotriazole (tolyltriazole), dimethylbenzotriazole, ethylbenzotriazole, ethylmethylbenzotriazole, getylbenzotriazole, and mixtures thereof.
  • R 73 represents a linear or branched alkyl group having 14 to 14 carbon atoms, preferably a methyl group or an ethyl group
  • R 74 represents a methylene group or an ethylene group.
  • R 75 and R 76 may be the same or different and each may be a hydrogen atom or a linear or branched alkyl group having 118 carbon atoms, preferably a linear or branched alkyl group having 11 12 carbon atoms.
  • y is a number of 0-3, preferably 0 or 1.
  • R73 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
  • R 75 and R 76 for example, separately, a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a linear or Branched pentyl, straight or branched hexyl, straight or branched heptyl, straight or branched octyl, straight or branched nor, straight or branched Branched decyl group, straight or branched pentadecyl group, straight or branched dodecyl group, straight or branched tridecyl group, straight or branched tetradecyl group, straight or branched pentadecyl group And alkyl groups such as linear or branched hexadecyl groups, linear or branched heptadecyl groups,
  • R 73 is a methyl group, y is 0 or 1, since R is particularly excellent in antioxidant properties.
  • dialkylaminoalkylbenzotriazoles examples include dimethylaminomethylbenzotriazole, getylaminomethylbenzotriazole, di (linear or branched) propylaminomethylbenzotriazole, and di (direct Chain or branched) butylaminomethylbenzotriazole, di (linear or branched) pentylaminomethylbenzotriazole, di (linear or branched) hexylaminomethylbenzotriazole, di (linear) Or branched) heptylaminomethylbenzotriazole, di (linear or branched) octylaminomethylbenzotriazole, di (linear or branched) nor-aminoaminobenzotriazole, di (linear) Or branched) decylaminomethylbenzotriazole, di (linear or branched) pentadecylaminomethylbenzotriazole, di Straight or branched)
  • the content of (F) benzotriazole and Z or a derivative thereof in the refrigerator oil composition of the present invention is optional. Based on the total amount of the power composition, it is preferably 0.001% by mass or more, more preferably 0.005% by mass or more. It is. If less than 0.001% by mass, benzotria There is a possibility that the effect of improving the abrasion resistance and the frictional properties due to the inclusion of sol and Z or its derivative may be insufficient. Further, the content of (F) benzotriazole and Z or a derivative thereof is preferably 1.0% by mass or less, more preferably 0.5% by mass or less, based on the total amount of the composition. If the content exceeds 1.0% by mass, the effect of improving the wear resistance and the frictional properties corresponding to the content may not be obtained, which may be economically disadvantageous.
  • the refrigerating machine oil composition of the present invention may further contain the following epoxy compounds (G-1) to (G-7) in addition to the (D) glycidyl ester type epoxy resin conjugate.
  • (G-1) The epoxy compound shown in (G-7) may be used alone or in combination of two or more.
  • phenylglycidyl ether type epoxy compound examples include phenyldaricidyl ether and alkylphenylglycidyl ether.
  • the alkylphenol glycidyl ether as used herein includes those having 113 alkyl groups having 113 carbon atoms, among which those having one alkyl group having 410 carbon atoms, for example, n-butylphenyl- Luglycidyl ether, i-butylphenol glycidyl ether, sec-butylphenylglycidyl ether, tertbutylbutylglycidylether, pentylphenolglycidylether, hexylphenolglycidylether, heptylphenolglycidylether, octylphenolglycidyl Ether, norphenyldaricidyl ether, decylphenol glycidyl ether and the like
  • (G-2) alkyl glycidyl ether type epoxy compound specifically, Luglycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether
  • Tridecyl glycidyl ether Tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylol propane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether Sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.
  • (G-3) aryloxy silane compound examples include 1,2-epoxystyrene and alkyl 1,2-epoxystyrene.
  • (G-4) alkyloxysilane compound examples include 1,2 epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxydecane, 1,2-epoxidedodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1, Examples thereof include 2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, and 1,2-epoxyicosane.
  • alicyclic epoxyy conjugates include 1,2-epoxycyclohexane, 1,2 epoxycyclopentane, 3,4 epoxycyclohexynolemethinolee 3,4-epoxycycline Rate, bis (3,4-epoxycyclohexylmethyl) adipate, exo 2,3 epoxynorbornane, bis (3,4 epoxy 6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] Hept-3yl) spiro (1,3- Dioxane 5,3,1- [7] oxabicyclo [4.1.0] heptane, 4- (1,1-methylepoxyethyl) -1,2 epoxy 2-methylcyclohexane, 4-epoxyethyl-1,2-eppo Xycyclohexane can be exemplified.
  • (G-6) epoxidized fatty acid monoesters include esters of epoxidized fatty acids having 12 to 20 carbon atoms with alcohols or phenols having 118 carbon atoms, alkylphenols, and the like. Can be exemplified. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenol and butylphenol esters of epoxystearic acid are preferably used.
  • Specific examples of the (G-7) epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
  • epoxidized conjugates the glycidyl ether-type epoxidized conjugate, alicyclic epoxy conjugated epoxide, and epoxide conjugated, since the thermal and hydrolytic stability can be further improved.
  • Alicyclic epoxy conjugates which are preferred for fatty acid monoesters, are more preferred.
  • the amount of the epoxidized conjugate is not particularly limited, but the total content of other epoxidized conjugates is based on the total amount of the composition. preferably 0. 1- 5.0 wt 0/0, more preferably 0. 2-2. 0% by weight.
  • a known refrigerator oil additive for example, phenol-based antioxidant such as di-tert-butyl-p-cresol, bisphenol A, etc.
  • Agents phenyl ⁇ naphthylamine, ⁇ , page (2-naphthyl) ⁇ amine-based antioxidants such as phenylene diamine, antiwear agents such as ditin dithiophosphate, extreme pressure of chlorinated paraffins, sulfur compounds, etc.
  • Additives such as oiling agents such as fatty acids, fatty acids, etc., defoamers such as silicones, viscosity index improvers, pour point depressants, detergents and dispersants, alone or in combination of two or more. It is possible.
  • the total amount of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of the composition.
  • the volume resistivity of the refrigerator oil composition of the present invention is not particularly limited, it is 1.0 ⁇ 10 9 ⁇ ⁇ ⁇ It is preferably at least m. In particular, when used in hermetic refrigerators, high electrical insulation tends to be required.
  • the volume resistivity means a value [ ⁇ 'cm] at 25 ° C measured in accordance with JIS C 2101 “Test method for electrical insulating oil”.
  • the water content of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerator oil composition. it can.
  • it is required to have a low water content from the viewpoint of the thermal stability of the oil and its influence on the electrical insulation.
  • the total acid value of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 0.1 mgKOH / g or less in order to prevent corrosion of metal used in the refrigerator or piping. , More preferably 0.05 mgKOHZg or less.
  • the total acid value means a value [mgKOHZg] measured in accordance with JIS K 2501 “Petroleum products and lubricating oil-neutralization value test method”.
  • the ash content of the refrigerator oil composition of the present invention is not particularly limited. However, it is preferable that the ash content of the refrigerator oil composition of the present invention be improved in order to enhance the thermal stability of hydrolysis and suppress the generation of sludge and the like. It can be less than 100 ppm, more preferably less than 50 ppm.
  • the ash means a value [ppm] measured according to JIS K 2272 “Test method for ash and sulfated ash of crude oil and petroleum products”.
  • the refrigerants used in the refrigerator using the refrigerator oil composition of the present invention include HFC refrigerants, fluorinated ether-based refrigerants such as perfluoroethers, non-fluorine-containing ether-based refrigerants such as dimethyl ether, and carbon dioxide, ammonia, and carbon dioxide.
  • Power as a natural refrigerant such as hydrogen may be used alone or as a mixture of two or more.
  • HFC refrigerants include hydrated fluorocarbons having 113, preferably 112 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HF C-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HF C — 134), 1, 1, 1, 2,—tetrafluoroethane (HFC—134a), 1, 1, 1—trifluoroethane (HFC—143a), 1,1 difluorene (HFC—152a) HFC, etc., or these And mixtures of two or more of these. These refrigerants are appropriately selected depending on the application and required performance.
  • HFC-32 alone; HFC-23 alone; HFC-134a alone; HFC-125 alone; HFC-l 34a / HFC-32 60- 80 mass 0 /.
  • Examples of natural refrigerants include carbon dioxide, ammonia, and hydrocarbons.
  • a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant.
  • it is an alkane, cycloalkane, alkene or a mixture thereof having 115, preferably 114 carbon atoms.
  • Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, and a mixture of two or more thereof.
  • propane, butane, isobutane or a mixture thereof is preferred.
  • the refrigerating machine oil composition of the present invention usually exists in a refrigerating machine in the form of a refrigerating machine fluid composition mixed with the above-described refrigerant.
  • the mixing ratio of the refrigerating machine oil to the refrigerant in the fluid composition is not particularly limited, but the refrigerating machine oil is preferably 11 to 500 parts by weight, more preferably 2 to 400 parts by weight, based on 100 parts by weight of the refrigerant.
  • the refrigerating machine oil composition of the present invention sufficiently satisfies all required properties such as lubricity, refrigerant compatibility, low-temperature fluidity, and stability in a well-balanced manner. It can be suitably used for refrigeration equipment having a closed type or a closed type compressor or a heat pump. In particular, when used in a refrigerator using an aluminum-based member, it is possible to achieve both a high level of both the anti-wear property and the thermal stability of the aluminum-based member.
  • the refrigerating machine oil composition of the present invention contains a mixed base oil of an ester (A-1) and an ester (A-2), it is used for a knockage air conditioner.
  • the refrigerating machine oil composition of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, a centrifugal type and the like.
  • a refrigerant circulation system in which the refrigerating machine oil composition of the present invention can be suitably used, typically, a refrigerant compressor, a condenser, an expansion mechanism, and an evaporator flow in this order, respectively.
  • a refrigerant compressor typically, a condenser, an expansion mechanism, and an evaporator flow in this order, respectively.
  • An example is shown in which they are connected via a passage and, if necessary, are provided with a dryer in the passage.
  • a motor that also has a rotor and a stator force in a closed container for storing refrigerating machine oil, a rotating shaft fitted to the rotor, and a motor connected via the rotating shaft are connected to the motor.
  • a high-pressure container-type compressor in which a high-pressure refrigerant gas discharged from the compressor stays in a closed container, and a rotor and a stator in a closed container that stores refrigerating machine oil.
  • the motor, the rotating shaft fitted to the rotor, and the compressor section connected to the motor via the rotating shaft are housed, and the high-pressure refrigerant gas discharged from the compressor section is moved out of the sealed container. Examples thereof include a low-pressure container type compressor that is directly discharged.
  • Examples of the insulating film that is a material of an electric insulation system for a motor include a crystalline plastic film having a glass transition point of 50 ° C or higher, specifically, for example, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether Ketone, polyethylene naphthalate, polyamide imide, polyimide group at least one selected
  • the insulating film which has a low glass transition temperature and a high glass transition temperature on the film! ⁇
  • a composite film coated with a resin layer is preferably used because it is less likely to cause deterioration in tensile strength characteristics and electrical insulation characteristics.
  • the magnet wire used for the motor part as the magnet wire used for the motor part,
  • Enamel coating with a glass transition temperature of 120 ° C or more such as a single layer of polyester, polyesterimide, polyamide and polyamideimide, or a composite coating of a layer having a low glass transition temperature on the lower layer and a layer having a high glass transition temperature on the upper layer.
  • Those having a coating are preferably used.
  • the composite-coated enameled wire include a polyester imide in a lower layer and a polyamide imide in an upper layer (AIZEI), and a polyester imide in a lower layer and a polyamide imide in an upper layer (AIZPE).
  • Examples of the desiccant to be filled in the drier include keic acid and aluminum acid having a pore diameter of 3.3 angstroms or less and a carbon dioxide absorption capacity at a carbon dioxide gas partial pressure of 250 mmHg at 25 ° C of 1.0% or less.
  • a synthetic zeolite composed of an alkali metal complex salt is preferably used. Specific examples include XH-9, XH-10, XH-11, XH-600 and the like manufactured by Union Showa Co., Ltd.
  • Example 1-16 and Comparative Example 1-14 refrigerating machine oil compositions having the compositions shown in Table 16 were prepared using the base oils and the additives described below, respectively.
  • Base oil 1 tetraester of pentaerythritol with an equimolar mixture of 2-ethylhexanoic acid and 3,5,5 trimethylhexanoic acid (branched fatty acid 100%) (kinematic viscosity at 40 ° C: 68. (5mm 2 Zs, pour point: 25 ° C, separation temperature with R410A 10 ° C)
  • Additive 8 diisodecyl adipate
  • Additive 10 Lauric acid.
  • the sliding part of the FALEX tester (ASTM D2714) was installed in a pressure-resistant container, a coolant was introduced into the container, and the FALEX test was performed under the following conditions.
  • Test material steel ring, steel block
  • Test start temperature 80 ° C
  • Refrigerant atmosphere pressure 500kPa o
  • the wear resistance was evaluated by determining the amount of wear as a decrease in the weight change of the block before and after the test.
  • the frictional force was measured every second, and the frictional characteristics were evaluated by the average friction coefficient obtained by dividing the obtained frictional force by the load. Table 16 shows the results.
  • Additive 1 0.5 1-1 0.5 0.5
  • Additive 2 1-1 0.5 1-1 0.5
  • Additive 3 1-1 0.5 0.5-1
  • Composition Additive 4 1-11-11-1 [% by mass]
  • Additive 5 1-11-11-1
  • A1 Tetraester of pentaerythritol and equimolar mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (kinematic viscosity at 40 ° C: 68.5 mm s, pour point: -25 ° C)
  • A2 Tetraester of neopentyl glycol and 2-ethylhexanoic acid (kinematic viscosity at 40 ° C: 7.8 mmVs, pour point: 40 ° C or less)
  • ester of pentaerythritol and normal pentanoic acid (kinematic viscosity at 40 ° C 15 mm s, pour point: 40 ° C or less)
  • X2 Diester of neopentyl glycol and oleic acid (kinematic viscosity at 40 ° C: 24 mm s, pour point: 40 ° C or less)
  • G2 Ferul glycidyl ether.
  • a FALEX test (ASTM D2670) was performed under the following conditions while blowing a refrigerant into the refrigerator oil composition. The amount of wear of the blocks and pins at this time was determined as the amount of weight reduction. The results obtained are shown in Tables 7-9.
  • Refrigerant blowing amount lOLZh
  • Refrigerant R407C.
  • the sliding part of the FALEX tester (ASTM D2714) was installed in a pressure-resistant container, a coolant was introduced into the container, and the FALEX test was performed under the following conditions.
  • the friction characteristics were evaluated by the average friction coefficient.
  • the average friction coefficient was calculated by measuring the friction force every second during the test time and dividing the obtained friction force by the load. The results obtained are shown in Tables 7-9.
  • Test material steel ring, steel block
  • Test start temperature 80 ° C
  • An air conditioner for home use (Mitsubishi Electric, model number: PLZ-RP40A, rated cooling capacity: 3.6 kW) is equipped with an open window, the height difference between the indoor unit and the outdoor unit is set to 20 m, and oil is returned.
  • the outdoor unit was arranged above the indoor unit so that the difference in gender was remarkable.
  • Each refrigerating machine oil composition was introduced into the compressor of the air conditioner, and first, the oil level in a stationary state was measured. Next, the operation of the air conditioner was started, and the time required for the oil level to return to the original level (recovery time) was measured.
  • the results obtained are shown in Tables 7-9. In the table, recovery Time is short! It means that it has excellent oil return properties.

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Abstract

Une composition d’huile pour machine frigorifique qui comprend un ester polyol comme huile de base, un phosphorothionate, un additif de composé de phosphore autre que les phosphorothionates et un ester glycidylique de type composé époxy. Un appareil frigorifique/de climatisation utilisant un réfrigérant d’hydrofluorocarbone, etc., la composition de l’huile pour machine frigorifique pouvant combiner des propriétés lubrifiantes et un degré de stabilité élevé. L’appareil frigorifique/de climatisation peut donc fonctionner de façon stable pendant longtemps.
PCT/JP2005/003510 2004-03-04 2005-03-02 Composition d’huile pour machine frigorifique WO2005085402A1 (fr)

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