WO2014142313A1 - 冷凍機油組成物及び冷凍機システム - Google Patents
冷凍機油組成物及び冷凍機システム Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
- C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
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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
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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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
- 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
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
- C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/107—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106
- C10M2209/1075—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of two or more specified different alkylene oxides covered by groups C10M2209/104 - C10M2209/106 used as base material
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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
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
- C10M2209/1085—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
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- 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
- C10N2020/01—Physico-chemical properties
- C10N2020/02—Viscosity; Viscosity index
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- 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
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- 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
- C10N2020/106—Containing Carbon dioxide
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- 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
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B9/00—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point
- F25B9/002—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant
- F25B9/008—Compression machines, plants or systems, in which the refrigerant is air or other gas of low boiling point characterised by the refrigerant the refrigerant being carbon dioxide
Definitions
- the present invention relates to a refrigerating machine oil composition, and more particularly to a refrigerating machine oil composition and a refrigerating machine system that are used in a refrigerating machine system that uses a refrigerant that has a low global warming potential and that can be used particularly in current car air conditioner systems. .
- chlorofluorocarbon CFC
- hydrochlorofluorocarbon HCFC
- HFC hydrofluorocarbon
- hydrofluorocarbons include 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane, 1,1,1-trifluoroethane (hereinafter referred to as R134a, R32, R125, and R143a, respectively).
- R134a has been mainly used in car air conditioner systems.
- this HFC is also concerned about the influence of global warming.
- GWP global warming potential
- unsaturated fluorinated hydrocarbon compounds see, for example, Patent Document 1
- fluorinated ether compounds see, for example, Patent Document 2
- fluoride fluoride
- a refrigerant having a specific polar structure in the molecule such as an alcohol compound and a fluorinated ketone compound has been proposed.
- trans-1,3,3,3-tetrafluoropropene (R1234ze), carbon dioxide, R32, A composition comprising a third component selected from 1,1-difluoroethane (R152a), fluoroethane (R161), R134a, propylene, propane and mixtures thereof (see, for example, Patent Document 3) has been found.
- the present invention is a refrigeration using a refrigerant composed of a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound and CO 2 , which is a refrigerant that has a low global warming potential and can be used particularly in car air conditioners.
- a refrigerating machine oil composition that can be used for a refrigerating machine system, has excellent compatibility with the refrigerant and has excellent stability, such as excellent stability, and a refrigerating machine system using the same. It is for the purpose.
- the present inventors have used a refrigerant comprising a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound and CO 2 as a refrigerant, It has been found that the purpose can be achieved by using a base oil composed of a specific oxygen-containing compound having specific properties as machine oil.
- the present invention has been completed based on such findings.
- a refrigerating machine oil composition used for a refrigerant comprising a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound and CO 2 , comprising polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) A group consisting of alkylene glycol or a copolymer of its monoether and polyvinyl ether and at least one selected from polyol esters, having a kinematic viscosity at 100 ° C.
- a refrigerating machine oil composition containing oil (2) The refrigerating machine oil composition according to (1), wherein the base oil has a kinematic viscosity at 100 ° C. of 5 mm 2 / s to 30 mm 2 / s and a water content in the composition of 700 ppm or less,
- the polyoxyalkylene glycol is represented by the general formula (I) R 1 -[(OR 2 ) m-OR 3 ] n (I) (Wherein R 1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R 2 Is an alkylene group having 2 to 4 carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 to 6, and m is an average value of m ⁇ n Wherein the refrigerating machine oil composition according to the above (1) or (2), (4) The polyvinyl ether is represented by the general formula (II)
- R 4 , R 5 and R 6 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R 7 has 2 carbon atoms.
- divalent hydrocarbon group of ⁇ 10 represents a number of hydrocarbon radicals
- p is the average value of 0 to 10 1 to 10 carbon atoms, of a plurality if R 7 O is plural R 7 O may be the same or different.
- a copolymer of the poly (oxy) alkylene glycol or its monoether and polyvinyl ether is represented by the general formula (VIII) or (IX)
- R 29 , R 30 and R 31 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R 33 has 2 to 4 carbon atoms.
- a divalent hydrocarbon group, R 34 is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group which may have a substituent having 1 to 20 carbon atoms, or a group having 2 to 20 carbon atoms
- R 32 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 32 , R 33 , and R 34 are the same or different when there are a plurality of them.
- .v is a number in the range of the average value thereof 1-50, when R 33 O is plural, the plurality of R 33 O may optionally be the same or different .
- k 1 ⁇ 50 and u are numbers from 0 to 50, and k and u can be either block or random if there are multiple X and y each represent a number of 1 to 50, and when there are a plurality of x and y, each of them may be block or random, and X and Y are each a hydrogen atom, a hydroxyl group, or a carbon number of 1 to 20 Represents a hydrocarbon group.
- the base oil is blended with at least one selected from an antioxidant, an extreme pressure agent, an acid scavenger, an oxygen scavenger, a copper deactivator, a rust inhibitor, and an antifoaming agent, (1) to the refrigerating machine oil composition according to any one of (6), (8)
- GWP global warming potential
- the refrigerant is a mixture of trans-1,3,3,3-tetrafluoropropene (R1234ze), 1,1,1,2-tetrafluoroethane (R134a) and CO 2
- a refrigerator system in which the moisture content in the refrigerator system is 500 ppm by mass or less, and (12) a car air conditioner, GHP, air conditioner, refrigerator, vending machine, showcase, water heater or floor heating
- a refrigerant comprising a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound, and CO 2 , which is a refrigerant that has a low global warming potential and can be used particularly for a car air conditioner or the like, is used.
- a refrigerating machine oil composition that satisfies various performances of refrigerating machine oil, such as having excellent compatibility with the refrigerant and excellent stability, and a refrigerating machine system using the same are provided. can do.
- the refrigerating machine oil composition of the present invention is a refrigerating machine oil composition used for a refrigerant comprising a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound, and CO 2 , comprising polyoxyalkylene glycols, polyvinyl ether A poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether, and a polyol ester, and a kinematic viscosity at 100 ° C. of 2 mm 2 / s to 50 mm 2 / s, Contains a base oil having a hydroxyl value of 5 mgKOH / g or less.
- Refrigerant refrigerator using the refrigerator oil composition of the present invention consists of a mixture of an unsaturated fluorinated hydrocarbon compound and a saturated fluorinated hydrocarbon compound CO 2.
- the unsaturated fluorinated hydrocarbon compound constituting the mixture used as a refrigerant is preferably, for example, a linear or branched chain olefin having 2 to 6 carbon atoms, or a 4 to 6 carbon atoms. Mention may be made of fluorinated cyclic olefins.
- ethylene having 1 to 3 fluorine atoms introduced propene having 1 to 5 fluorine atoms introduced, butenes having 1 to 7 fluorine atoms introduced, 1 to 9 Pentenes introduced with fluorine atoms, hexenes introduced with 1 to 11 fluorine atoms, cyclobutene introduced with 1 to 5 fluorine atoms, cyclopentene introduced with 1 to 7 fluorine atoms, 1 And cyclohexene introduced with up to 9 fluorine atoms.
- propene fluoride is preferable, and from the viewpoint of environmental performance such as GWP, for example, various isomers of pentafluoropropene, 3,3,3-trifluoropropene, and 1, 3,3,3-tetrafluoropropene (R1234ze) and the like are preferable.
- this unsaturated fluorinated hydrocarbon compound may be used alone or in combination of two or more. Since the unsaturated fluorinated hydrocarbon compound is a refrigerant having a low GWP, it is usually 45% by mass or more, preferably 45% by mass or more and 96% by mass or less, based on the total amount of the refrigerant from the viewpoint of environmental performance, stability and the like. Preferably it is 75 to 96 mass%, More preferably, it is 79 to 96 mass%, Most preferably, it is 82 to 90 mass%.
- saturated fluorinated hydrocarbon compounds The saturated fluorinated hydrocarbon compound constituting the mixture used as the refrigerant is preferably an alkane fluoride having 2 to 4 carbon atoms, particularly fluoroethane (R161), difluoromethane (R32), or ethane fluoride.
- R134a also referred to as HFC134a
- saturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more.
- the blending amount of the saturated fluorinated hydrocarbon compound is usually 2% by mass or more and 50% by mass or less, preferably 2% by mass or more and 40% by mass or less based on the total amount of refrigerant from the viewpoint of environmental performance and stability such as GWP. Or less, more preferably 2% by mass or more and 30% by mass or less, further preferably 2% by mass or more and 20% by mass or less, still more preferably 2% by mass or more and 15% by mass or less, and particularly preferably 6% by mass or more and 15% by mass or less. It is.
- CO 2 refrigerant The mixture used as the refrigerant of the refrigerator using the refrigerator oil composition of the present invention has a low global warming potential and blends CO 2 as a refrigerant suitable for environmental protection. Since CO 2 as a refrigerant usually requires high pressure, its use amount is generally limited in a refrigeration system such as a car air conditioner, and in consideration of compatibility with a refrigerator oil composition, etc. Is usually 12% by mass or less of CO 2 in the refrigerant, preferably 1% by mass or more and 10% by mass or less, more preferably 2% by mass or more and 7% by mass or less of CO 2. .
- the refrigerant of the refrigerator using the refrigerator oil composition of the present invention comprises a mixture of the unsaturated fluorinated hydrocarbon compound, the saturated fluorinated hydrocarbon compound, and the CO 2 .
- Refrigerant in the present invention environmental performance, in terms of stability and the like, preferably, a R1234ze (also referred to as HFO1234ze), and CO 2, (also referred to as HFC134a) R134a, the refrigerant selected from R32, R152a, R161, etc.
- the refrigerant in the present invention is 79% by mass to 96% by mass R1234ze (HFO1234ze), 2% by mass to 7% by mass CO 2 , and 2% by mass to 15% by mass R134a (HFC134a). It is preferable to consist of a mixture of
- refrigerant in the present invention other refrigerants can be used in combination with the refrigerant composed of the mixture as long as the effects of the present invention are not impaired.
- a refrigerant specifically, any of the refrigerants described in JP2011-256361A can be used, and for example, propylene, propane, and the like can be used.
- the refrigerant in the present invention has a GWP of 1300 or less, preferably 1000 or less, more preferably 800 or less, 500 or less, 400 or less, 300 or less or 200 or less, particularly 150 or 100 or less, and even 50 or less GWP. It is preferable to have.
- the refrigerating machine oil composition of the present invention is a lubricating oil composition for a refrigerating machine system using the above-described refrigerant, and includes, as a base oil, polyoxyalkylene glycols (PAG), polyvinyl ethers (PVE), poly (oxy) ) Consisting of at least one selected from alkylene glycol or a copolymer of its monoether and polyvinyl ether (ECP) and polyol esters (POE), having a kinematic viscosity at 100 ° C. of 2 mm 2 / s to 50 mm 2 / s, Contains a base oil having a hydroxyl value of 5 mgKOH / g or less.
- PAG polyoxyalkylene glycols
- PVE polyvinyl ethers
- PEO poly (oxy) ) Consisting of at least one selected from alkylene glycol or a copolymer of its monoether and polyvinyl ether (ECP
- Base oil Polyoxyalkylene glycols (PAG)
- PAG Polyoxyalkylene glycols
- Examples of the polyoxyalkylene glycols that can be used as the base oil in the refrigerating machine oil composition of the present invention include, for example, the general formula (I) R 1 -[(OR 2 ) m -OR 3 ] n (I) (Wherein R 1 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R 2 Is an alkylene group having 2 to 4 carbon atoms, R 3 is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms (R 1 and R 3 may be a heterocyclic ring), n Represents an integer of 1 to 6, and m represents a number with an average value of m
- the alkyl group represented by R 1 and R 3 may be linear, branched or cyclic.
- Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. When the number of carbon atoms in the alkyl group exceeds 10, compatibility with the refrigerant may be reduced, and rough separation may occur.
- the alkyl group preferably has 1 to 6 carbon atoms.
- the alkyl group part of the acyl group represented by R 1 or R 3 may be linear, branched or cyclic. Specific examples of the alkyl group part of the acyl group include the alkyl group described above. The various groups having 1 to 9 carbon atoms, which are given as specific examples of the group, can be similarly exemplified. When the acyl group has more than 10 carbon atoms, the compatibility with the refrigerant is lowered, and phase separation may occur. A preferred acyl group has 2 to 6 carbon atoms. When R 1 and R 3 are both alkyl groups or acyl groups, R 1 and R 3 may be the same or different from each other.
- a plurality of R 3 in one molecule may be the same or different.
- R 1 is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites
- the aliphatic hydrocarbon group may be a chain or a cyclic one. Also good.
- the aliphatic hydrocarbon group having two bonding sites include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group.
- Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, 1,3,5-trihydroxycyclohexane, and the like.
- excluded the hydroxyl group from the polyhydric alcohol of this can be mentioned.
- compatibility with the refrigerant may be reduced, and phase separation may occur.
- a preferred carbon number is 2-6.
- R 1 and R 3 may be a heterocyclic ring, and the heterocyclic hetero atom is oxygen and / or sulfur.
- the heterocycle contains oxygen or sulfur.
- the heterocycle may be saturated or unsaturated.
- R 1 and R 3 may be saturated cyclic ether or saturated cyclic thioether. Such cyclic compounds may or may not be substituted.
- the heterocycle may be linked via its substituent or one unspecified substituent, in which case the substituent is, for example, —CH 2 —, —C 2 It may be a hydrocarbon linkage which is H 4 — or —C 3 H 6 —.
- R 1 and R 3 may include a C 4 -C 6 heterocyclic moiety connected directly or via a hydrocarbon linkage.
- the heterocyclic moiety may be a furan or thiophene ring.
- the heterocyclic moiety may alternatively be a furfuryl, or a furfuryl derivative such as tetrahydrofurfuryl, and may be connected directly or via a hydrocarbon linkage.
- Examples of original compounds from which R 1 and R 3 are derived include tetrahydrofuran, methyltetrahydrofuran, tetrahydrothiophene, or methyltetrahydrothiophene substituents.
- R 1 and R 3 are 2-hydroxymethyl-are those derivable from tetrahydrofuran, such as those wherein R 1 and R 3 is bonded through has been and oxygen derived from methyl tetrahydrofuran, what its inducible Can be considered to have groups according to the above definition.
- R 2 in the general formula (I) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- the oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.
- n is an integer of 1 to 6, and is determined according to the number of R 1 binding sites.
- n is 1, and when R 1 is an aliphatic hydrocarbon group having 2, 3, 4, 5, and 6 binding sites, n is 2, 3 respectively. , 4, 5 and 6.
- m is a number with an average value of m ⁇ n of 6 to 80, and if the average value of m ⁇ n deviates from the above range, the object of the present invention cannot be sufficiently achieved.
- the polyoxyalkylene glycol represented by the general formula (I) includes a polyoxyalkylene glycol having a hydroxyl group at the terminal, and the content of the hydroxyl group is 50 mol% or less with respect to all terminal groups. If it is the ratio which becomes, even if it contains, it can be used conveniently. If the hydroxyl group content exceeds 50 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable.
- Such polyoxyalkylene glycols include the following structural formulas:
- polyoxypropylene glycol monobutyl ether represented by the following formula is preferred.
- polyoxyalkylene glycols represented by the general formula (I) any of those described in detail in JP-A-2-305893 can be used. In this invention, these polyoxyalkylene glycols may be used individually by 1 type, and may be used in combination of 2 or more type.
- polyvinyl ethers (PVE) In the refrigerating machine oil composition of the present invention, the polyvinyl ethers that can be used as the base oil include those represented by the general formula (II)
- the main component is a polyvinyl ether compound having a structural unit represented by:
- R 4 , R 5 and R 6 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different.
- the hydrocarbon group is specifically 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.
- R 4 , R 5 and R 6 are particularly preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.
- R 7 in the general formula (II) represents a divalent hydrocarbon group having 2 to 10 carbon atoms.
- the divalent hydrocarbon group having 2 to 10 carbon atoms specifically refers to Ethylene group, phenylethylene group, 1,2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylenes Groups, divalent aliphatic groups such as various nonylene groups and various decylene groups; alicyclic groups having two bonding sites on cycloaliphatic hydrocarbons such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, propylcyclohexane, etc.
- Divalent aromatic hydrocarbons such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylenes, etc.
- alkyl aromatic groups having a binding site in the alkyl group portion Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred.
- a plurality of R 7 Os may be the same or different.
- p represents the number of repetitions, and the average value is a number in the range of 0 to 10, preferably 0 to 5.
- R 8 in the general formula (II) represents a hydrocarbon group having 1 to 10 carbon atoms, which is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n Alkyl groups such as -butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups; cyclopentyl group, cyclohexyl group , Various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various cycloalkyl groups such as dimethylcyclohexyl groups; phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphen
- a hydrocarbon group having 8 or less carbon atoms is preferable.
- p is 0, an alkyl group having 1 to 6 carbon atoms is particularly preferable, and when p is 1 or more, an alkyl group having 1 to 4 carbon atoms is particularly preferable.
- the polyvinyl ether compound in the present invention has a structural unit represented by the above general formula (II), and the number of repetitions thereof (that is, the degree of polymerization) may be appropriately selected according to the desired kinematic viscosity. Usually, it is 2 mm 2 / s or more and 50 mm 2 / s or less (100 ° C.), preferably 5 mm 2 / s or more and 30 mm 2 / s or less (100 ° C.).
- the polyvinyl ether compound in the present invention can be produced by polymerization of a corresponding vinyl ether monomer.
- the vinyl ether monomers that can be used here are represented by the general formula (III)
- the vinyl ether monomers include various monomers corresponding to the above polyvinyl ether compounds, such as vinyl methyl ether; vinyl ethyl ether; vinyl n-propyl ether; vinyl isopropyl ether; vinyl n-butyl ether; Vinyl-sec-butyl ether; vinyl-tert-butyl ether; vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-methoxyethyl ether; vinyl-2-ethoxyethyl ether; Vinyl-2-methoxy-propyl ether; vinyl-3,6-dioxaheptyl ether; vinyl-3,6,9-trioxadecyl ether; vinyl-1,4-dimethyl-3 6-dioxaheptyl ether; vinyl-1,4,7-trimethyl-3,6,
- the terminal of the polyvinyl ether compound having the structural unit represented by the general formula (II) used in the refrigerating machine oil composition of the present invention can be converted into a desired structure by a known method.
- the group to be converted include saturated hydrocarbons, ethers, alcohols, ketones, amides, and nitriles.
- the polyvinyl ether compound used for the base oil in the refrigerating machine oil composition of the present invention those having the following terminal structure are suitable. That is, (1) One terminal is represented by the general formula (IV)
- R 9 , R 10 and R 11 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R 12 represents a carbon number divalent hydrocarbon group having 2 ⁇ 10, R 13 represents the number of hydrocarbon group, q has an average value of 0 to 10 1 to 10 carbon atoms, of a plurality if R 12 O is more R 12 O may be the same or different. And the remaining ends are represented by the general formula (V)
- R 14 , R 15 and R 16 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R 17 represents A divalent hydrocarbon group of 2 to 10, R 18 is a hydrocarbon group having 1 to 10 carbon atoms, r represents an average value of 0 to 10, and when there are a plurality of R 17 O, a plurality of R 17 17 O may be the same or different.
- One terminal is represented by the general formula (IV) and the other terminal is the general formula (VI).
- R 19 , R 20 and R 21 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different
- R 22 and R 24 Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different
- R 23 and R 25 each represent a hydrocarbon group having 1 to 10 carbon atoms. They may be the same or different, and s and t each represent an average value of 0 to 10, and they may be the same or different, and it is more R 22 O if there are R 22 O may be the same or different and a plurality of R 24 in the case where there are multiple R 24 O May be the same or different.
- R 26 , R 27 and R 28 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different.
- the polyvinyl ether-based mixture may be a mixture of two or more selected from those having the terminal structures (1) to (4). Preferred examples of such a mixture include a mixture of the above (1) and (4), and a mixture of (2) and (3).
- the kinematic viscosity of the refrigerating machine oil composition before mixing with the refrigerant is 2 mm 2 / s or more and 50 mm 2 / s or less at 100 ° C., so that a polyvinyl ether compound in this viscosity range is generated. It is preferable to select the raw material, initiator and reaction conditions.
- the number average molecular weight of this polymer is usually 500 or more, preferably 600 or more and 3000 or less.
- this polyvinyl ether type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- Poly (oxy) alkylene glycol refers to both polyalkylene glycol and polyoxyalkylene glycol.
- the copolymer of poly (oxy) alkylene glycol or its monoether and polyvinyl ether that can be used as the base oil in the refrigerating machine oil composition of the present invention includes general formula (VIII) and general formula (IX).
- R 29 , R 30 and R 31 each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R 33 represents 2 carbon atoms.
- R 34 is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group optionally having a substituent having 1 to 20 carbon atoms, 2 carbon atoms ⁇ 20 acyl group or oxygen containing hydrocarbon group having 2 to 50 carbon atoms
- R 32 represents a hydrocarbon group having 1 to 10 carbon atoms
- R 32 , R 33 and R 34 are respectively It may be the same or different.
- the hydrocarbon group having 1 to 8 carbon atoms represented by each of R 29 to R 31 specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group.
- examples of the divalent hydrocarbon group having 2 to 4 carbon atoms represented by R 33 include divalent alkylene groups such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and various butylene groups.
- v represents the number of repeating R 33 O, and the average value thereof is in the range of 1 to 50, preferably 1 to 20, more preferably 1 to 10, particularly preferably 1 to 5. Is a number.
- plural R 33 O may be the same or different.
- K is 1 to 50, preferably 1 to 10, more preferably 1 to 2, particularly preferably 1, u is a number from 0 to 50, preferably 2 to 25, more preferably 5 to 15, If there are a plurality of k and u, each of them may be block or random.
- R 34 in the general formula (VIII) preferably represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms.
- Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and various pentyl groups.
- acyl group having 2 to 10 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, piperoyl group, benzoyl group, and toluoyl group.
- oxygen-containing hydrocarbon group having 2 to 50 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxypropyl group, ethoxy
- Preferable examples include propyl group, (2-methoxyethoxy) propyl group, (1-methyl-2-methoxy) propyl group and the like.
- the hydrocarbon group having 1 to 10 carbon atoms represented by R 32 is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, or an isobutyl group.
- Alkyl groups such as various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups; cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, Cycloalkyl groups such as various dimethylcyclohexyl groups; aryl groups such as phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups Benzyl group, various phenylethyl groups, various groups A benzylyl group, various phenylpropyl groups, arylphenyl groups of various phenylbutyl groups and the like are
- the polyvinyl ether copolymer I having the structural unit represented by the general formula (VIII) into a copolymer, it is possible to improve lubricity, insulation, hygroscopicity, etc. while satisfying compatibility. There is an effect that can be done.
- the performance of the oil can be adjusted to the target level. Therefore, there is an effect that an oil agent can be freely obtained in accordance with requirements such as lubricity and compatibility that differ depending on the type of compressor, the material of the lubrication part, the refrigerating capacity, the type of refrigerant, and the like in the refrigeration system or the air conditioning system.
- R 29 to R 32 , R 33 and v are the same as described above.
- R 33 and R 32 may be the same or different when there are a plurality of them.
- x and y each represent a number from 1 to 50, and when there are a plurality of x and y, each may be a block or random.
- X and Y each independently represent a hydrogen atom, a hydroxyl group or 1 to 20 hydrocarbon groups.
- the method for producing the polyvinyl ether copolymers I and II is not particularly limited as long as it is a method by which it can be obtained.
- paragraphs [0059] to [0074] of JP-A-2008-115266. Can be produced by the method described in 1. above.
- this poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether may be used singly or in combination of two or more.
- polyol esters (POE) In the refrigerating machine oil composition of the present invention, as a polyol ester that can be used as a base oil, an ester of a diol or a polyol having about 3 to 20 hydroxyl groups and a fatty acid having about 1 to 24 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-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc. Can be mentioned.
- polyol examples include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), and tri- (pentaerythritol).
- Glycerin polyglycerin (glycerin 2 to 20-mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol and other polyhydric alcohols, xylose, arabinose, Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gel Chianosu, saccharides such as Merenjitosu, and their partially etherified products and methyl glucosides (glycosides) and the like.
- neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri Hindered alcohols such as-(pentaerythritol) are preferred.
- the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used.
- those having 3 or more carbon atoms are preferable, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are even more preferable, and those having 10 or more carbon atoms are more preferable.
- coolant a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is still more preferable.
- any of a linear fatty acid and a branched fatty acid may be sufficient, a linear fatty acid is preferable from the point of lubricity, and a branched fatty acid is preferable from the point of hydrolysis stability. Furthermore, either saturated fatty acid or unsaturated fatty acid may be used.
- fatty acid examples include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid , Linear or branched ones such as icosanoic acid and oleic acid, or so-called neoacids in which the ⁇ carbon atom is quaternary.
- valeric acid n-pentanoic acid
- caproic acid n-hexanoic acid
- enanthic acid n-heptanoic acid
- caprylic acid n-octanoic acid
- pelargonic acid n-nonanoic acid
- Capric acid n-decanoic acid
- oleic acid cis-9-octadecenoic acid
- isopentanoic acid 3-methylbutanoic acid
- 2-methylhexanoic acid 2-ethylpentanoic acid
- 2-ethylhexanoic acid 2,3,5-trimethylhexanoic acid and the like are preferable.
- the polyol ester may be a partial ester remaining without all the hydroxyl groups of the polyol being esterified, or may be a complete ester in which all the hydroxyl groups are esterified, or a partial ester and a complete ester. A complete ester is preferable.
- neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol
- esters of hindered alcohols such as di- (pentaerythritol) and tri- (pentaerythritol)
- esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol The ester of pentaerythritol is most preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.
- preferred polyol esters include neopentyl glycol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2 -Diester of one or more fatty acids selected from ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; trimethylolethane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, caprin Tritates with one or more fatty acids selected from acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid Esters: trimethylolpropane and valeric acid, caproic acid,
- ester with two or more fatty acids may be a mixture of two or more esters of one type of fatty acid and polyol.
- the kinematic viscosity at 100 ° C. of the base oil in the refrigerator oil composition of the present invention is 2 mm 2 / s or more and 50 mm 2 / s or less. If the kinematic viscosity is 2 mm 2 / s or more, good lubrication performance (load resistance) is exhibited and the sealing property is good, and if it is 50 mm 2 / s or less, the compatibility between the refrigerant and the refrigerating machine oil is improved. Excellent and energy saving. From the above viewpoint, the kinematic viscosity at 100 ° C.
- the kinematic viscosity at 100 ° C. of the base oil in the present invention can be measured using a glass capillary viscometer according to JIS K2283-1983.
- the hydroxyl value of the base oil in the refrigerator oil composition of the present invention is 5 mgKOH / g or less.
- the hydroxyl value of the base oil is preferably 4 mgKOH / g or less, more preferably 3 mgKOH / g or less, still more preferably 2 mgKOH / g or less, and particularly preferably 1.5 mgKOH / g or less.
- the hydroxyl value of the base oil in the present invention can be measured by a neutralization titration method according to JIS K0070.
- the number average molecular weight of the base oil is preferably 500 or more, more preferably 600 or more and 3000 or less, and further preferably 700 or more and 2500 or less.
- the flash point of the base oil is preferably 150 ° C. or higher. If the number average molecular weight of the base oil is 500 or more, desired performance as a refrigerating machine oil can be exhibited, and the flash point of the base oil can be 150 ° C. or more.
- the base oil in the refrigerating machine oil composition of the present invention has the above properties, it is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass with the base oil composed of the oxygen-containing compound.
- % Containing other base oil can be used at a ratio of% or less.
- base oils that can be used in combination with the oxygen-containing compounds include other polyesters, polycarbonates, hydrides of ⁇ -olefin oligomers, mineral oils, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, and the like. be able to.
- the refrigerating machine oil composition of the present invention has at least one selected from among antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust preventives, oiliness agents, antifoaming agents, and the like. Seed additives can be included.
- the extreme pressure agent include phosphorus extreme pressure agents such as phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, and amine salts thereof.
- tricresyl phosphate trithiophenyl phosphate, tri (nonylphenyl) phosphite, dioleyl hydrogen phosphite, 2-ethylhexyl diphenyl phosphite in terms of extreme pressure and friction characteristics Etc. are particularly preferred.
- the metal salt of carboxylic acid is mentioned.
- the metal salt of the carboxylic acid here is preferably a carboxylic acid having 3 to 60 carbon atoms, more preferably a metal salt of a fatty acid having 3 to 30 carbon atoms, particularly 12 to 30 carbon atoms.
- the dimer acid and trimer acid of the said fatty acid, and the metal salt of C3-C30 dicarboxylic acid can be mentioned.
- metal salts of fatty acids having 12 to 30 carbon atoms and dicarboxylic acids having 3 to 30 carbon atoms are particularly preferred.
- an alkali metal or an alkaline earth metal is preferable, and an alkali metal is particularly optimal.
- extreme pressure agents other than the above include sulfur-based extreme pressure agents such as sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, and dialkylthiodipropionates. be able to.
- the blending amount of the extreme pressure agent is usually 0.001% by mass or more and 5% by mass or less, particularly preferably 0.005% by mass or more and 3% by mass or less based on the total amount of the composition from the viewpoint of lubricity and stability.
- One of these extreme pressure agents may be used alone, or two or more thereof may be used in combination.
- antioxidants examples include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6- It is preferable to add a phenolic antioxidant such as tert-butylphenol) or an amine antioxidant such as phenyl- ⁇ -naphthylamine or N, N′-di-phenyl-p-phenylenediamine.
- the antioxidant is blended in the composition in an amount of usually 0.01% by mass or more and 5% by mass or less, preferably 0.05% by mass or more and 3% by mass or less.
- the acid scavenger examples include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
- epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
- phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, and ⁇ -olefin oxide are preferable in terms of compatibility.
- the alkyl group of the alkyl glycidyl ether and the alkylene group of the alkylene glycol glycidyl ether may have a branch and usually have 3 to 30, preferably 4 to 24, particularly 6 to 16 carbon atoms.
- the ⁇ -olefin oxide generally has a total carbon number of 4 to 50, preferably 4 to 24, particularly 6 to 16.
- one type of acid scavenger may be used, or two or more types may be used in combination.
- the compounding quantity is 0.005 mass% or more and 5 mass% or less normally with respect to a composition from the point of an effect and suppression of sludge generation, Especially 0.05 mass% or more and 3 mass% or less are preferable.
- the stability of the refrigerating machine oil composition can be improved by blending this acid scavenger.
- the combined use of the extreme pressure agent and the antioxidant exhibits the effect of further improving the stability.
- the oxygen scavenger include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
- the copper deactivator include N- [N, N′-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl] triazole.
- rust preventive examples include metal sulfonates, aliphatic amines, organic phosphites, organic phosphates, organic sulfonates, organic phosphates, alkenyl succinates, polyhydric alcohol esters, and the like. be able to.
- oily agent examples include aliphatic fatty acid saturated (and unsaturated) monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, and hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid.
- Aliphatic saturated (and unsaturated) monoalcohols such as lauryl alcohol and oleyl alcohol, aliphatic saturated (and unsaturated) monoamines such as stearylamine and oleylamine, aliphatic saturated (and unsaturated) such as lauric acid amide and oleic acid amide Saturated) monocarboxylic acid amide, glycerin, sorbitol and other polyhydric alcohols and aliphatic saturated (or unsaturated) monocarboxylic acid partial esters.
- the antifoaming agent include silicone oil and fluorinated silicone oil.
- the refrigerating machine oil composition of the present invention may further contain other known various additives as long as the object of the present invention is not impaired.
- the refrigerating machine oil composition of the present invention is used in combination with a refrigerant comprising a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound, and CO 2.
- the water content in the composition is preferably 700 ppm by mass or less, more preferably 500 ppm by mass or less, further preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. , 100 mass ppm or less is most preferable. If the water content in the refrigerating machine oil composition is within the above range, the composition is preferably excellent in stability.
- the refrigerating machine oil composition of the present invention is applied to a refrigerating machine system using a refrigerant composed of a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound, and CO 2 .
- the amount of the refrigerant and various refrigerator oil compositions used is 99/1 to 10/90 in terms of mass ratio of the refrigerant / refrigerator oil composition, Further, it is preferably in the range of 95/5 to 30/70.
- the refrigerating machine oil composition of the present invention can be used in various refrigerating machines, but can be preferably applied particularly to a compression refrigeration cycle of a compression refrigerating machine.
- the refrigerating machine oil composition of the present invention is used for various refrigerator / heater systems such as a car air conditioner, an electric car air conditioner, a gas heat pump (GHP), an air conditioner, a refrigerator, a vending machine, a showcase, a hot water heater, and a floor heater.
- the water content in a system shall be 500 mass ppm or less.
- the moisture content is preferably 300 mass ppm or less, more preferably 200 mass ppm or less, and even more preferably 100 mass ppm or less.
- the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
- the properties of the base oil and various characteristics of the refrigerator oil composition were determined according to the following procedure. ⁇ Properties of base oil> (1) Kinematic viscosity (40 ° C, 100 ° C) It was measured using a glass capillary viscometer according to JIS K2283-1983. (2) Hydroxyl value It measured by the neutralization titration method according to JISK0070. (3) Acid value The acid value was measured by an indicator photometric titration method (see Appendix 1 in the JIS standard on the left) according to JIS K2501.
- the water content in the refrigerating machine oil composition was measured by Karl Fischer titration according to JIS K 2275.
- the water content in the refrigerator system was measured by Karl Fischer titration in accordance with JIS K 2275 after extracting the refrigerator oil composition from the system.
- shield tube test a glass tube was filled with oil / refrigerant 4 mL / 1 g, and a metal catalyst of iron (Fe), copper (Cu), and aluminum (Al), sealed, and sealed at a temperature of 175 ° C. After maintaining for days, the oil appearance and Fe catalyst appearance were visually observed, and the acid value was measured.
- the moisture mixed shield tube test was performed in the same manner as described above by adding a predetermined moisture content to the oil with a microsyringe and changing the moisture content in the range of 50 to 2000 mass ppm as shown in Table 2. A tube test was performed.
- Base oil A1 Polypropylene glycol dimethyl ether, 40 ° C. kinematic viscosity; 42.8 mm 2 / s, 100 ° C. kinematic viscosity; 9.52 mm 2 / s, hydroxyl value (OHV); 0.9 mgKOH / g
- A2 Polypropylene glycol dimethyl ether, 40 ° C. kinematic viscosity; 43.5 mm 2 / s, 100 ° C.
- kinematic viscosity 9.34 mm 2 / s, hydroxyl value (OHV); 3.5 mgKOH / g A3: Polyoxypropylene / polyoxyethylene copolymer dimethyl ether, (PO / EO molar ratio is 7: 3), 40 ° C. kinematic viscosity; 43.1 mm 2 / s, 100 ° C. kinematic viscosity; 10.3 mm 2 / s , Hydroxyl value (OHV); 1.2 mgKOH / g A4: Polyethyl vinyl ether, 40 ° C. kinematic viscosity; 68.5 mm 2 / s, 100 ° C. kinematic viscosity; 8.39 mm 2 / s, hydroxyl value (OHV); 1.1 mgKOH / g
- kinematic viscosity 68.5 mm 2 / s, 100 ° C. kinematic viscosity; 8.32 mm 2 / s, hydroxyl value (OHV); 3.2 mgKOH / g A7: Polypropylene glycol dimethyl ether, 40 ° C. kinematic viscosity; 44.56 mm 2 / s, 100 ° C.
- kinematic viscosity 70.3 mm 2 / s, 100 ° C.
- kinematic viscosity 8.27 mm 2 / s, hydroxyl value (OHV): 8.6 mg KOH / g
- A9 Polypropylene glycol dimethyl ether, 40 ° C. kinematic viscosity: 148.3 mm 2 / s, 100 ° C. kinematic viscosity; 27.34 mm 2 / s, hydroxyl value (OHV): 2.7 mg KOH / g
- A10 Polypropylene glycol dimethyl ether, 40 ° C. kinematic viscosity; 370.6 mm 2 / s, 100 ° C. kinematic viscosity; 53.8 mm 2 / s, hydroxyl value (OHV); 3.9 mgKOH / g
- Additive B1 (acid scavenger): C14 ⁇ -olefin oxide
- B2 antioxidant
- DBPC 2,6-di-t-butyl-4-methylphenol
- B3 extreme pressure agent
- TCP tricresyl phosphate
- Examples 1 to 11 and Comparative Examples 1 to 3 Refrigerating machine oil compositions having the compositions shown in Table 1 were prepared, and the compatibility of the refrigerating machine oil composition with the AC6A refrigerant and the stability of the refrigerating machine oil composition were evaluated using an AC6A refrigerant. The results are shown in Table 1. In addition, the compounding quantity of each component is shown by the mass%.
- the refrigerating machine oil compositions (Examples 1 to 11) of the present invention have a two-layer separation temperature exceeding 30 ° C. or 50 ° C. for all of the various refrigerating machine oils, and in the shield tube test. Excellent stability.
- Comparative Example 1 separated from the refrigerant at room temperature, and Comparative Examples 2 and 3 had a two-layer separation temperature exceeding 50 ° C., but the shield tube test had poor stability.
- Examples 12 to 15 and Comparative Examples 4 and 5 Refrigerating machine oil compositions having the compositions shown in Table 2 were prepared, and the water content of each refrigerating machine oil composition was changed as shown in Table 2 to evaluate the stability of the refrigerating machine oil composition. The results are shown in Table 2.
- the refrigeration oil composition of the present invention is excellent in stability as a result of the shield tube test in Examples 12 to 15 having a water content of 500 ppm or less.
- the shield tube test resulted in extremely poor stability.
- the lubricating oil composition for a refrigerator of the present invention has a low global warming potential, and is composed of a mixture of an unsaturated fluorinated hydrocarbon compound, a saturated fluorinated hydrocarbon compound, and CO 2 that can be used particularly for a car air conditioner. It is suitably used for a refrigerator system using a refrigerant.
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Abstract
Description
従って、冷凍機システムにおいては、地球温暖化係数(GWP)が低い等環境保護に適した冷媒とともに、当該冷媒に対する優れた相溶性を有し、しかも安定性に優れた冷凍機油組成物が求められていた。
(1)不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒に用いる冷凍機油組成物であって、ポリオキシアルキレングリコール類、ポリビニルエーテル類、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体、及びポリオールエステル類から選ばれる少なくとも一種からなり、100℃における動粘度が2~50mm2/s、水酸基価が5mgKOH/g以下である基油を含有する冷凍機油組成物、
(2)基油の100℃における動粘度が5mm2/s以上30mm2/s以下であり、組成物中の水分含有量が700ppm以下である、前記(1)に記載の冷凍機油組成物、
R1-[(OR2)m-OR3]n ・・・(I)
(式中、R1は水素原子、炭素数1~10のアルキル基、炭素数2~10のアシル基又は結合部2~6個を有する炭素数1~10の脂肪族炭化水素基、R2は炭素数2~4のアルキレン基、R3は水素原子、炭素数1~10のアルキル基又は炭素数2~10のアシル基、nは1~6の整数、mはm×nの平均値が6~80となる数を示す。)で表される、前記(1)又は(2)に記載の冷凍機油組成物、
(4)前記ポリビニルエーテル類が、一般式(II)
で表される、前記(1)又は(2)に記載の冷凍機油組成物、
(5)前記ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体が、一般式(VIII)又は(IX)
で表される、前記(1)又は(2)に記載の冷凍機油組成物、
(7)前記基油に、酸化防止剤、極圧剤、酸捕捉剤、酸素捕捉剤、銅不活性化剤、防錆剤、及び消泡剤から選ばれる少なくとも一種を配合してなる、前記(1)~(6)のいずれかに記載の冷凍機油組成物、
(8)前記冷媒の地球温暖化係数(GWP)が150以下である、前記(1)~(7)のいずれかに記載の冷凍機油組成物、
(10)組成物の水分含有量が300質量ppm以下である、前記(1)~(9)のいずれかに記載の冷凍機油組成物、
(11)前記(1)~(10)のいずれかに記載の冷凍機油組成物、及び不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒を用いた冷凍機システムであり、該冷凍機システム内の水分含有量が500質量ppm以下である冷凍機システム、及び
(12)カーエアコン、GHP、空調、冷蔵庫、自動販売機、ショーケース、給湯器又は床暖房に用いられる、前記(11)記載の冷凍機システム、
を提供するものである。
本発明の冷凍機油組成物は、不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒に用いる冷凍機油組成物であって、ポリオキシアルキレングリコール類、ポリビニルエーテル類、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体、及びポリオールエステル類から選ばれる少なくとも一種からなり、100℃における動粘度が2mm2/s以上50mm2/s以下、水酸基価が5mgKOH/g以下である基油を含有する。
本発明の冷凍機油組成物を用いる冷凍機の冷媒は、不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる。
(不飽和フッ化炭化水素化合物)
本発明において、冷媒として用いられる混合物を構成する不飽和フッ化炭化水素化合物としては、好ましくは、例えば、炭素数2~6の直鎖状又は分岐状の鎖状オレフィンや炭素数4~6の環状オレフィンのフッ素化物を挙げることができる。
これらの不飽和フッ化炭化水素化合物の中では、プロペンのフッ化物が好ましく、GWP等の環境性能の観点から、例えばペンタフルオロプロペンの各種異性体、3,3,3-トリフルオロプロペン及び1,3,3,3-テトラフルオロプロペン(R1234ze)等が好適である。
上記不飽和フッ化炭化水素化合物はGWPの低い冷媒であるから、環境性能、安定性等の観点から冷媒全量に基づき、通常、45質量%以上、好ましくは45質量%以上96質量%以下、より好ましくは75質量%以上96質量%以下、さらに好ましくは79質量%以上96質量%以下、特に好ましくは82質量%以上90質量%以下で配合される。
冷媒として用いられる混合物を構成する飽和フッ化炭化水素化合物としては、炭素数2~4のアルカンのフッ化物が好ましく、特に、フルオロエタン(R161)、ジフルオロメタン(R32)、エタンのフッ化物である1,1-ジフルオロエタン(R152a)、1,1,1-トリフルオロエタン、1,1,2-トリフルオロエタン、1,1,1,2-テトラフルオロエタン(R134a)、1,1,2,2-テトラフルオロエタン、1,1,1,2,2-ペンタフルオロエタンが用いられ、特に、R134a(HFC134aともいう)が安定性や飽和蒸気圧特性の観点から好適である。これらの飽和フッ化炭化水素化合物は、1種を単独で用いてもよく、2種以上組み合わせて用いてもよい。
また、当該飽和フッ化炭化水素化合物の配合量は、GWP等の環境性能や安定性の観点から、冷媒全量に基づき、通常2質量%以上50質量%以下、好ましくは2質量%以上40質量%以下、より好ましくは2質量%以上30質量%以下、さらに好ましくは2質量%以上20質量%以下、よりさらに好ましくは2質量%以上15質量%以下、特に好ましくは6質量%以上15質量%以下である。
本発明の冷凍機油組成物を用いる冷凍機の冷媒として用いられる混合物には、地球温暖化係数が低く、環境保護に適した冷媒としてCO2を配合する。冷媒としてのCO2は、通常、高圧を必要とするため、一般にカーエアコンなどの冷凍システムではその使用量は制限され、また、冷凍機油組成物との相溶性等を考慮して、本発明においては、冷媒中、通常、冷媒全量につき12質量%以下のCO2が配合され、好ましくは1質量%以上10質量%以下、より好ましくは2質量%以上7質量%以下のCO2が配合される。
本発明の冷凍機油組成物を用いる冷凍機の冷媒は、前記不飽和フッ化炭化水素化合物と前記飽和フッ化炭化水素化合物と前記CO2との混合物からなる。
本発明における冷媒は、環境性能、安定性等の観点から、好ましくは、R1234ze(HFO1234zeともいう)と、CO2と、R134a(HFC134aともいう)、R32、R152a、R161等から選ばれる冷媒との混合物からなり、より好ましくは、R1234ze(HFO1234ze)とCO2とR134a(HFC134a)との混合物からなる。さらに好ましくは、本発明における冷媒は、79質量%以上96質量%以下のR1234ze(HFO1234ze)、2質量%以上7質量%以下のCO2、及び2質量%以上15質量%以下のR134a(HFC134a)の混合物からなることが好ましい。
本発明における冷媒は1300以下、好ましくは1000以下、さらに好ましくは800以下、500以下、400以下、300以下または200以下のGWPを有し、特に150以下または100以下、さらには50以下のGWPを有することが好ましい。
本発明の冷凍機油組成物は、前述の冷媒を用いる冷凍機システム用の潤滑油組成物であって、基油として、ポリオキシアルキレングリコール類(PAG)、ポリビニルエーテル類(PVE)、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体(ECP)及びポリオールエステル類(POE)から選ばれる少なくとも一種からなり、100℃における動粘度が2mm2/s以上50mm2/s以下、水酸基価が5mgKOH/g以下である基油を含有する。
(ポリオキシアルキレングリコール類(PAG))
本発明の冷凍機油組成物において、基油として用いることのできるポリオキシアルキレングリコール類としては、例えば一般式(I)
R1-[(OR2)m-OR3]n ・・・ (I)
(式中、R1は水素原子、炭素数1~10のアルキル基、炭素数2~10のアシル基又は結合部2~6個を有する炭素数1~10の脂肪族炭化水素基、R2は炭素数2~4のアルキレン基、R3は水素原子、炭素数1~10のアルキル基又は炭素数2~10のアシル基(R1及びR3は複素環であってもよい)、nは1~6の整数、mはm×nの平均値が6~80となる数を示す。)
で表される化合物が挙げられる。
また、R1、R3で表されるアシル基のアルキル基部分は直鎖状、分岐鎖状、環状のいずれであってもよく、該アシル基のアルキル基部分の具体例としては、上記アルキル基の具体例として挙げた炭素数1~9の種々の基を同様に挙げることができる。該アシル基の炭素数が10を超えると冷媒との相溶性が低下し、相分離を生じる場合がある。好ましいアシル基の炭素数は2~6である。
R1及びR3が、いずれもアルキル基又はアシル基である場合には、R1とR3は同一であってもよいし、たがいに異なっていてもよい。
R1が結合部位2~6個を有する炭素数1~10の脂肪族炭化水素基である場合、この脂肪族炭化水素基は鎖状のものであってもよいし、環状のものであってもよい。結合部位2個を有する脂肪族炭化水素基としては、例えばエチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、シクロペンチレン基、シクロヘキシレン基などが挙げられる。また、結合部位3~6個を有する脂肪族炭化水素基としては、例えばトリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール、1,2,3-トリヒドロキシシクロヘキサン、1,3,5-トリヒドロキシシクロヘキサンなどの多価アルコールから水酸基を除いた残基を挙げることができる。
この脂肪族炭化水素基の炭素数が10を超えると冷媒との相溶性が低下し、相分離が生じる場合がある。好ましい炭素数は2~6である。
例えば、その複素環部分は、フランまたはチオフェン環であってもよい。複素環部分は、代わりに、フルフリル、またはテトラヒドロフルフリルのようなフルフリル誘導体であってもよく、直接または炭化水素リンケージを介して接続されてもよい。R1及びR3が誘導されるもとの化合物の例には、テトラヒドロフラン、メチルテトラヒドロフラン、テトラヒドロチオフェン、またはメチルテトラヒドロチオフェン置換基が含まれる。R1及びR3の好ましい例は、2-ヒドロキシメチルテトラヒドロフランから誘導可能なものであり、R1及びR3がメチルテトラヒドロフランから誘導されて且つ酸素を介して結合するものなど、その誘導可能なものは上記の定義に従う基を有するとみなすことができるものである。
前記一般式(I)中のnは1~6の整数で、R1の結合部位の数に応じて定められる。例えばR1がアルキル基やアシル基の場合、nは1であり、R1が結合部位2,3,4,5及び6個を有する脂肪族炭化水素基である場合、nはそれぞれ2,3,4,5及び6となる。また、mはm×nの平均値が6~80となる数であり、m×nの平均値が前記範囲を逸脱すると本発明の目的は十分に達せられない。
このようなポリオキシアルキレングリコール類としては、下記構造式
で表されるポリオキシプロピレングリコールジメチルエーテル、下記構造式
で表されるポリオキシエチレンポリオキシプロピレングリコールジメチルエーテル、及び下記構造式
で表されるポリオキシプロピレングリコールモノブチルエーテル、さらにはポリオキシプロピレングリコールジアセテートなどが、経済性及び効果の点で好適である。
なお、上記一般式(I)で表されるポリオキシアルキレングリコール類については、特開平2-305893号公報に詳細に記載されたものをいずれも使用することができる。
本発明においては、このポリオキシアルキレングリコール類は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の冷凍機油組成物において、基油として用いることのできるポリビニルエーテル類としては、一般式(II)
上記一般式(II)におけるR4,R5及びR6はそれぞれ水素原子又は炭素数1~8の炭化水素基を示し、それらはたがいに同一であっても異なっていてもよい。ここで炭化水素基とは、具体的にはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基などのアルキル基;シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種ジメチルシクロヘキシル基などのシクロアルキル基;フェニル基、各種メチルフェニル基、各種エチルフェニル基、各種ジメチルフェニル基などのアリール基;ベンジル基、各種フェニルエチル基、各種メチルベンジル基などのアリールアルキル基を示す。なお、これらのR4、R5、R6としては水素原子あるいは炭素数3以下の炭化水素基が特に好ましい。
なお、一般式(II)におけるpは繰り返し数を示し、その平均値が0~10、好ましくは0~5の範囲の数である。
で表されるものである。このビニルエーテル系モノマーとしては、上記ポリビニルエーテル系化合物に対応する各種のものがあるが、例えばビニルメチルエーテル;ビニルエチルエーテル;ビニル-n-プロピルエーテル;ビニル-イソプロピルエーテル;ビニル-n-ブチルエーテル;ビニル-イソブチルエーテル;ビニル-sec-ブチルエーテル;ビニル-tert-ブチルエーテル;ビニル-n-ペンチルエーテル;ビニル-n-ヘキシルエーテル;ビニル-2-メトキシエチルエーテル;ビニル-2-エトキシエチルエーテル;ビニル-2-メトキシ-1-メチルエチルエーテル;ビニル-2-メトキシ-プロピルエーテル;ビニル-3,6-ジオキサヘプチルエーテル;ビニル-3,6,9-トリオキサデシルエーテル;ビニル-1,4-ジメチル-3,6-ジオキサヘプチルエーテル;ビニル-1,4,7-トリメチル-3,6,9-トリオキサデシルエーテル;ビニル-2,6-ジオキサ-4-ヘプチルエーテル;ビニル-2,6,9-トリオキサ-4-デシルエーテル;1-メトキシプロペン;1-エトキシプロペン;1-n-プロポキシプロペン;1-イソプロポキシプロペン;1-n-ブトキシプロペン;1-イソブトキシプロペン;1-sec-ブトキシプロペン;1-tert-ブトキシプロペン;2-メトキシプロペン;2-エトキシプロペン;2-n-プロポキシプロペン;2-イソプロポキシプロペン;2-n-ブトキシプロペン;2-イソブトキシプロペン;2-sec-ブトキシプロペン;2-tert-ブトキシプロペン;1-メトキシ-1-ブテン;1-エトキシ-1-ブテン;1-n-プロポキシ-1-ブテン;1-イソプロポキシ-1-ブテン;1-n-ブトキシ-1-ブテン;1-イソブトキシ-1-ブテン;1-sec-ブトキシ-1-ブテン;1-tert-ブトキシ-1-ブテン;2-メトキシ-1-ブテン;2-エトキシ-1-ブテン;2-n-プロポキシ-1-ブテン;2-イソプロポキシ-1-ブテン;2-n-ブトキシ-1-ブテン;2-イソブトキシ-1-ブテン;2-sec-ブトキシ-1-ブテン;2-tert-ブトキシ-1-ブテン;2-メトキシ-2-ブテン;2-エトキシ-2-ブテン;2-n-プロポキシ-2-ブテン;2-イソプロポキシ-2-ブテン;2-n-ブトキシ-2-ブテン;2-イソブトキシ-2-ブテン;2-sec-ブトキシ-2-ブテン;2-tert-ブトキシ-2-ブテン等が挙げられる。これらのビニルエーテル系モノマーは公知の方法により製造することができる。
本発明の冷凍機油組成物における基油に用いられるポリビニルエーテル系化合物としては、次の末端構造を有するものが好適である。
すなわち、
(1)その一つの末端が、一般式(IV)
で表され、かつ残りの末端が一般式(V)
で表される構造を有するもの、
(2)その一つの末端が上記一般式(IV)で表され、かつ残りの末端が一般式(VI)
で表される構造を有するもの、
(3)その一つの末端が前記一般式(IV)で表され、かつ残りの末端がオレフィン性不飽和結合を有するもの、
(4)その一つの末端が前記一般式(IV)で表され、かつ残りの末端が一般式(VII)
で表される構造のものである。
該ポリビニルエーテル系混合物は、前記(1)~(4)の末端構造を有するものの中から選ばれた二種以上の混合物であってもよい。このような混合物としては、例えば前記(1)のものと(4)のものとの混合物、及び前記(2)のものと(3)のものとの混合物を好ましく挙げることができる。
本発明においては、このポリビニルエーテル系化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
ポリ(オキシ)アルキレングリコールとは、ポリアルキレングリコール及びポリオキシアルキレングリコールの両方を指す。
本発明の冷凍機油組成物において、基油として用いることのできるポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体としては、一般式(VIII)及び一般式(IX)
上記一般式(VIII)におけるR29、R30及びR31はそれぞれ水素原子又は炭素数1~8の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、R33は炭素数2~4の二価の炭化水素基、R34は炭素数1~20の脂肪族もしくは脂環式炭化水素基、炭素数1~20の置換基を有してもよい芳香族基、炭素数2~20のアシル基又は炭素数2~50の酸素含有炭化水素基、R32は炭素数1~10の炭化水素基を示し、R32、R33、R34はそれらが複数ある場合にはそれぞれ同一でも異なっていてもよい。
なお、一般式(VIII)におけるvは、R33Oの繰り返し数を示し、その平均値が1~50、好ましくは1~20、さらに好ましくは1~10、特に好ましくは1~5の範囲の数である。R33Oが複数ある場合には、複数のR33Oは同一でも異なっていてもよい。
また、kは1~50、好ましくは1~10、さらに好ましくは1~2、特に好ましくは1、uは0~50、好ましくは2~25、さらに好ましくは5~15、の数を示し、kおよびuはそれらが複数ある場合にはそれぞれブロックでもランダムでもよい。
この炭素数1~10のアルキル基とは、具体的にはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種プロピルシクロヘキシル基、各種ジメチルシクロヘキシル基などを示す。
また、炭素数2~10のアシル基としては、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピパロイル基、ベンゾイル基、トルオイル基などを挙げることができる。
さらに、炭素数2~50の酸素含有炭化水素基の具体例としては、メトキシメチル基、メトキシエチル基、メトキシプロピル基、1,1-ビスメトキシプロピル基、1,2-ビスメトキシプロピル基、エトキシプロピル基、(2-メトキシエトキシ)プロピル基、(1-メチル-2-メトキシ)プロピル基などを好ましく挙げることができる。
なお、R29~R31、R34、R33及びv並びにR29~R32は、それぞれ構成単位毎に同一であっても異なっていてもよい。
本発明においては、このポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
本発明の冷凍機油組成物において、基油として用いることのできるポリオールエステル類としては、ジオールあるいは水酸基を3~20個程度有するポリオールと、炭素数1~24程度の脂肪酸とのエステルが好ましく用いられる。ここで、ジオールとしては、例えばエチレングリコール、1,3-プロパンジオール、プロピレングリコール、1,4-ブタンジオール、1,2-ブタンジオール、2-メチル-1,3-プロパンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、2-エチル-2-メチル-1,3-プロパンジオール、1,7-ヘプタンジオール、2-メチル-2-プロピル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,11-ウンデカンジオール、1,12-ドデカンジオールなどが挙げられる。
また、直鎖状脂肪酸、分岐状脂肪酸の何れであっても良く、潤滑性の点からは直鎖状脂肪酸が好ましく、加水分解安定性の点からは分岐状脂肪酸が好ましい。更に、飽和脂肪酸、不飽和脂肪酸の何れであっても良い。
なお、ポリオールエステルとしては、ポリオールの全ての水酸基がエステル化されずに残った部分エステルであっても良く、全ての水酸基がエステル化された完全エステルであっても良く、また部分エステルと完全エステルの混合物であっても良いが、完全エステルであることが好ましい。
本発明の冷凍機油組成物における基油の100℃の動粘度は、2mm2/s以上50mm2/s以下である。該動粘度が2mm2/s以上であれば良好な潤滑性能(耐荷重性)が発揮されると共に、シール性もよく、また50mm2/s以下であれば冷媒と冷凍機油との相溶性に優れ、省エネルギー性も良好である。上記観点から、基油の100℃の動粘度は、好ましくは3mm2/s以上40mm2/s以下、さらに好ましくは5mm2/s以上30mm2/s以下である。
本発明における基油の100℃における動粘度は、JIS K2283-1983に準じ、ガラス製毛管式粘度計を用いて測定することができる。
本発明における基油の水酸基価は、JIS K0070に準じ、中和滴定法により測定することができる。
当該含酸素化合物と併用できる基油としては、例えば他のポリエステル類、ポリカーボネート類、α-オレフィンオリゴマーの水素化物、さらには鉱油、脂環式炭化水素化合物、アルキル化芳香族炭化水素化合物などを挙げることができる。
本発明の冷凍機油組成物には、酸化防止剤、極圧剤、酸捕捉剤、酸素捕捉剤、銅不活性化剤、防錆剤、油性剤、消泡剤などの中から選ばれる少なくとも1種の添加剤を含有させることができる。
前記極圧剤としては、リン酸エステル、酸性リン酸エステル、亜リン酸エステル、酸性亜リン酸エステル及びこれらのアミン塩などのリン系極圧剤を挙げることができる。
これらのリン系極圧剤の中で、極圧性、摩擦特性などの点からトリクレジルホスフェート、トリチオフェニルホスフェート、トリ(ノニルフェニル)ホスファイト、ジオレイルハイドロゲンホスファイト、2-エチルヘキシルジフェニルホスファイトなどが特に好ましい。
一方、金属塩を構成する金属としてはアルカリ金属又はアルカリ土類金属が好ましく、特に、アルカリ金属が最適である。
さらに、上記以外の極圧剤として、例えば、硫化油脂、硫化脂肪酸、硫化エステル、硫化オレフィン、ジヒドロカルビルポリサルファイド、チオカーバメート類、チオテルペン類、ジアルキルチオジプロピオネート類などの硫黄系極圧剤を挙げることができる。
上記極圧剤の配合量は、潤滑性及び安定性の点から、組成物全量に基づき、通常0.001質量%以上5質量%以下、特に0.005質量%以上3質量%以下が好ましい。
前記の極圧剤は1種を単独で用いてもよく、2種以上を組合わせて用いてもよい。
このアルキルグリシジルエーテルのアルキル基、及びアルキレングリコールグリシジルエーテルのアルキレン基は、分岐を有していてもよく、炭素数は通常3~30、好ましくは4~24、特に6~16のものである。また、α-オレフィンオキシドは全炭素数が一般に4~50、好ましくは4~24、特に6~16のものを使用する。本発明においては、上記酸捕捉剤は1種を用いてもよく、2種以上を組み合わせて用いてもよい。また、その配合量は、効果及びスラッジ発生の抑制の点から、組成物に対して、通常0.005質量%以上5質量%以下、特に0.05質量%以上3質量%以下が好ましい。
酸素捕捉剤としては、例えばフェニルグリシジルエーテル、アルキルグリシジルエーテル、アルキレングリコールグリシジルエーテル、シクロヘキセンオキシド、α-オレフィンオキシド、エポキシ化大豆油などのエポキシ化合物等を挙げることができる。
銅不活性化剤としては、例えばN-[N,N’-ジアルキル(炭素数3~12のアルキル基)アミノメチル]トリアゾール等を挙げることができる。
防錆剤としては、例えば金属スルホネート、脂肪族アミン類、有機亜リン酸エステル、有機リン酸エステル、有機スルフォン酸金属塩、有機リン酸金属塩、アルケニルコハク酸エステル、多価アルコールエステル等を挙げることができる。
前記消泡剤としては、例えば、シリコーン油やフッ素化シリコーン油などを挙げることができる。
本発明の冷凍機油組成物には、さらに本発明の目的を阻害しない範囲で、他の公知の各種添加剤を配合することができる。
本発明の冷凍機油組成物は、不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒を用いた冷凍機システムに適用される。
本発明の冷凍機油組成物を使用する冷凍機システムにおける潤滑方法において、前記冷媒と各種冷凍機油組成物の使用量については、冷媒/冷凍機油組成物の質量比で99/1~10/90、更に95/5~30/70の範囲にあることが好ましい。冷媒の量が上記範囲よりも少ない場合は冷凍能力の低下が見られ、また上記範囲よりも多い場合は潤滑性能が低下し好ましくない。本発明の冷凍機油組成物は、種々の冷凍機に使用可能であるが、特に、圧縮型冷凍機の圧縮式冷凍サイクルに好ましく適用できる。
本発明においては、前記冷凍機システムに用いる場合、システム内の水分含有量は500質量ppm以下とする。該システム内の水分含有量が500質量ppmを超えると、冷凍機油組成物の安定性が悪くなるため、システム内を構成する部材の腐食や銅メッキの発生原因となる。当該水分含有量は、300質量ppm以下であることが好ましく、200質量ppm以下であることがより好ましく、100質量ppm以下であることがさらに好ましい。
なお、基油の性状及び冷凍機油組成物の諸特性は、以下に示す要領に従って求めた。
<基油の性状>
(1)動粘度(40℃、100℃)
JIS K2283-1983に準じ、ガラス製毛管式粘度計を用いて測定した。
(2)水酸基価
JIS K0070に準じ、中和滴定法により測定した。
(3)酸価
JIS K2501に準じ、指示薬光度滴定法(左記JIS規格における付属書1参照)により測定した。
(4)水分含有量
冷凍機油組成物中の水分含有量は、JIS K 2275に準じ、カールフィッシャー式滴定法により測定した。また、冷凍機システム内の水分含有量は、システム内から冷凍機油組成物を抜き取り、同じくJIS K 2275に準じてカールフィッシャー式滴定法により測定した。
(5)二層分離温度
二層分離温度測定管(内容積10mL)に油/冷媒(0.3g/2.7g)を充填し、恒温槽に保持した。恒温槽の温度を室温(25℃)より、温度を1℃/minの割合で上げ、二層分離温度を測定した。
(6)安定性(シールドチューブ試験、水分混合シールドチューブ試験)
シールドチューブ試験は、ガラス管に、油/冷媒4mL/1g、及び鉄(Fe)、銅(Cu)、アルミニウム(Al)の金属触媒を充填して封管し、温度175℃の条件にて30日間保持後、油外観、Fe触媒外観を目視観察すると共に、酸価を測定して行った。
また、水分混合シールドチューブ試験は、油にマイクロシリンジで所定の水分量を添加することで、水分含有量を50~2000質量ppmの範囲で、表2に示すように変えて上記と同様にシールドチューブ試験を行った。
(1)基油
A1:ポリプロピレングリコールジメチルエーテル、40℃動粘度;42.8mm2/s、100℃動粘度;9.52mm2/s、水酸基価(OHV);0.9mgKOH/g
A2:ポリプロピレングリコールジメチルエーテル、40℃動粘度;43.5mm2/s、100℃動粘度;9.34mm2/s、水酸基価(OHV);3.5mgKOH/g
A3:ポリオキシプロピレン/ポリオキシエチレン共重合体ジメチルエーテル、(PO/EOのモル比は7:3)、40℃動粘度;43.1mm2/s、100℃動粘度;10.3mm2/s、水酸基価(OHV);1.2mgKOH/g
A4:ポリエチルビニルエーテル、40℃動粘度;68.5mm2/s、100℃動粘度;8.39mm2/s、水酸基価(OHV);1.1mgKOH/g
A6:ペンタエリスリトールと2-エチルへキサン酸及び3,5,5-トリメチルヘキサン酸(2-エチルへキサン酸/3,5,5-トリメチルヘキサン酸=1/1(モル比))とのエステル、40℃動粘度;68.5mm2/s、100℃動粘度;8.32mm2/s、水酸基価(OHV);3.2mgKOH/g
A7:ポリプロピレングリコールジメチルエーテル、40℃動粘度;44.56mm2/s、100℃動粘度;9.13mm2/s、水酸基価(OHV);6.7mgKOH/g
A8:ペンタエリスリトールと2-エチルへキサン酸及び3,5,5-トリメチルヘキサン酸(2-エチルへキサン酸/3,5,5-トリメチルヘキサン酸=1/1(モル比))とのエステル、40℃動粘度;70.3mm2/s、100℃動粘度;8.27mm2/s、水酸基価(OHV);8.6mgKOH/g
A9:ポリプロピレングリコールジメチルエーテル、40℃動粘度;148.3mm2/s、100℃動粘度;27.34mm2/s、水酸基価(OHV);2.7mgKOH/g
A10:ポリプロピレングリコールジメチルエーテル、40℃動粘度;370.6mm2/s、100℃動粘度;53.8mm2/s、水酸基価(OHV);3.9mgKOH/g
B1(酸捕捉剤):C14α-オレフィンオキシド
B2(酸化防止剤):2,6-ジ-t-ブチル-4-メチルフェノール(DBPC)
B3(極圧剤):トリクレジルホスフェート(TCP)
(3)また、使用した冷媒は、AC6A[R1234ze(HFO1234ze)/R134a(HFC134a)/ CO2=83.73/10.56/5.71(質量比)混合冷媒、GWP;147]であった。
表1に示す組成の冷凍機油組成物を調製し、AC6A冷媒を用いて、冷凍機油組成物とAC6A冷媒との相溶性及び冷凍機油組成物の安定性を評価した。その結果を表1に示す。なお、各成分の配合量は質量%で示す。
表2に示す組成の冷凍機油組成物を調製し、各々の冷凍機油組成物の水分量を表2に示すように変化させ、冷凍機油組成物の安定性を評価した。その結果を表2に示す。
Claims (12)
- 不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒に用いる冷凍機油組成物であって、
ポリオキシアルキレングリコール類、ポリビニルエーテル類、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体、及びポリオールエステル類から選ばれる少なくとも一種からなり、100℃における動粘度が2mm2/s以上50mm2/s以下、水酸基価が5mgKOH/g以下である基油を含有する冷凍機油組成物。 - 基油の100℃における動粘度が5mm2/s以上30mm2/s以下であり、組成物中の水分含有量が700質量ppm以下である、請求項1に記載の冷凍機油組成物。
- 前記ポリオキシアルキレングリコール類が、一般式(I)
R1-[(OR2)m-OR3]n ・・・(I)
(式中、R1は水素原子、炭素数1~10のアルキル基、炭素数2~10のアシル基又は結合部2~6個を有する炭素数1~10の脂肪族炭化水素基、R2は炭素数2~4のアルキレン基、R3は水素原子、炭素数1~10のアルキル基又は炭素数2~10のアシル基、nは1~6の整数、mはm×nの平均値が6~80となる数を示す。)で表される、請求項1又は2に記載の冷凍機油組成物。 - 前記ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体が、一般式(VIII)又は(IX)
で表される、請求項1又は2に記載の冷凍機油組成物。 - 前記ポリオールエステル類が、ジオールあるいは水酸基を3~20個有するポリオールと、炭素数1~24の脂肪酸とのエステルである、請求項1又は2に記載の冷凍機油組成物。
- 前記基油に、酸化防止剤、極圧剤、酸捕捉剤、酸素捕捉剤、銅不活性化剤、防錆剤、油性剤及び消泡剤から選ばれる少なくとも一種を配合してなる、請求項1~6のいずれかに記載の冷凍機油組成物。
- 前記冷媒の地球温暖化係数(GWP)が150以下である、請求項1~7のいずれかに記載の冷凍機油組成物。
- 前記冷媒が、トランス-1,3,3,3-テトラフルオロプロペン(R1234ze)と1,1,1,2-テトラフルオロエタン(R134a)とCO2との混合物である、請求項1~8のいずれかに記載の冷凍機油組成物。
- 組成物中の水分含有量が300質量ppm以下である、請求項1~9のいずれかに記載の冷凍機油組成物。
- 請求項1~10のいずれかに記載の冷凍機油組成物、及び不飽和フッ化炭化水素化合物と飽和フッ化炭化水素化合物とCO2との混合物からなる冷媒を用いた冷凍機システムであり、該冷凍機システム内の水分含有量が500質量ppm以下である冷凍機システム。
- カーエアコン、ガスヒートポンプ、空調、冷蔵庫、自動販売機、ショーケース、給湯機又は床暖房に用いられる、請求項11記載の冷凍機システム。
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WO2017103987A1 (ja) * | 2015-12-15 | 2017-06-22 | 三菱電機株式会社 | 除湿機 |
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Also Published As
Publication number | Publication date |
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EP2975102A1 (en) | 2016-01-20 |
CN105121611A (zh) | 2015-12-02 |
TW201443224A (zh) | 2014-11-16 |
MX2015012206A (es) | 2016-04-15 |
BR112015023171A2 (pt) | 2017-07-18 |
US9976106B2 (en) | 2018-05-22 |
JP6010492B2 (ja) | 2016-10-19 |
US20160040094A1 (en) | 2016-02-11 |
EP2975102B1 (en) | 2023-05-31 |
KR20150129744A (ko) | 2015-11-20 |
JP2014177607A (ja) | 2014-09-25 |
EP2975102A4 (en) | 2017-01-04 |
KR102117822B1 (ko) | 2020-06-02 |
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