WO2013125528A1 - 冷凍機油組成物及びその製造方法、冷凍機用作動流体組成物 - Google Patents
冷凍機油組成物及びその製造方法、冷凍機用作動流体組成物 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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- 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
- C09K5/042—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising compounds containing carbon and hydrogen only
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- C09K5/00—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
- C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
- C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
- C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
- C10M129/68—Esters
- C10M129/74—Esters of polyhydroxy compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
- C10M135/20—Thiols; Sulfides; Polysulfides
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- 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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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/11—Ethers
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
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- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
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- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/24—Only one single fluoro component present
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- 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
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- 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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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- 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
- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/083—Dibenzyl sulfide
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
- C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
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- 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
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- 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
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- 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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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/01—Physico-chemical properties
- C10N2020/071—Branched chain compounds
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- 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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- 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
- C10N2020/103—Containing Hydrocarbons
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- 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
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- 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, a method for producing the same, and a working fluid composition for a refrigerator.
- R410A which is a mixed refrigerant of 1/1 (mass ratio) of ethane (R125), is widely used.
- Some refrigerating machine oils used with the above HFC refrigerants contain various additives in order to improve lubricity.
- antiwear additives that improve lubricity include oil agents such as alcohols, esters, and long chain fatty acids, antiwear agents such as phosphate esters and metal dithiophosphates, and organic sulfur. Extreme pressure agents such as compounds and organic halogen compounds are known.
- oil agents such as alcohols, esters, and long chain fatty acids
- antiwear agents such as phosphate esters and metal dithiophosphates
- organic sulfur Extreme pressure agents such as compounds and organic halogen compounds are known.
- triphenylphosphine among alcohol-based and ester-based oily agents and phosphate esters is used. Fate and tricresyl phosphate are used.
- Patent Document 1 discloses a refrigerating machine lubricating oil in which a phosphorus-based additive and a specific epoxy compound are added together.
- Patent Document 2 discloses an HFC refrigerant in which triphenyl phosphate and tri (alkylphenyl) phosphate are added in combination.
- Patent Document 3 discloses a compressor lubricating oil for use in which tricresyl phosphate and an epoxy or carbodiimide made of glycidyl ether are added for use in an HFC refrigerant.
- HFC refrigerant has an ozone depletion potential (ODP) of zero
- GWP global warming potential
- low GWP refrigerants such as hydrofluoroolefins (HFO) such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (R32) are used as alternative refrigerants for the above HFC refrigerants.
- HFO hydrofluoroolefins
- R32 difluoromethane
- HFO-1234yf hydrofluoroolefins
- R32 difluoromethane
- hydrocarbon refrigerants such as isobutane (R600a) and propane (R290) have a GWP as low as 20 or less and suitable physical properties, so they are flammable but have already been put into practical use for refrigerators. .
- R32 or a mixed refrigerant containing R32 has a high pressure during use and a high discharge temperature in the compressor, so that the oil film of the refrigerating machine oil in which the refrigerant is melted becomes thin, and severe lubrication conditions occur. .
- the friction coefficient can be kept low when the load condition is relatively mild such as in the mixed lubrication region.
- load conditions become severe, the effect of wear resistance is lost.
- triphenyl phosphate and tricresyl phosphate have a certain degree of wear resistance, they are insufficient in wear resistance in the presence of a low GWP refrigerant having severe lubricating conditions.
- the present invention has been made in view of the problems of the prior art, and is a refrigerating machine oil composition for a compatible refrigerant that has a large wear resistance effect even under severe lubrication conditions such as in the presence of a low GWP refrigerant and is excellent in long-term reliability. It is an object of the present invention to provide a product, a method for producing the product, and a working fluid composition for a refrigerator.
- the present invention provides a tetraester of pentaerythritol and one selected from fatty acids having 5 to 18 carbon atoms, and one selected from dipentaerythritol and fatty acids having 5 to 18 carbon atoms.
- a refrigerating machine oil composition having a kinematic viscosity at 40 ° C. of 3 to 500 mm 2 / s.
- the constituent fatty acid of the ester additive is one selected from fatty acids having 5 to 18 carbon atoms as described above. That is, the constituent fatty acid of the ester additive needs to have a single composition.
- the base oil which is an ester other than the ester additive includes all esters other than the ester additive.
- the constituent fatty acid is selected from fatty acids having 5 to 18 carbon atoms.
- Esters can be used as base oils.
- the constituent alcohol of the ester which is the base oil is pentaerythritol and / or dipentaerythritol and the constituent fatty acid is a mixed fatty acid containing a fatty acid having 5 to 18 carbon atoms
- pentaerythritol and carbon are synthesized during the synthesis of the base oil.
- a tetraester and / or dipentaerythritol selected from a fatty acid having 5 to 18 fatty acids and a hexaester selected from a fatty acid having 5 to 18 carbons may be formed.
- the wear resistance effect according to the present invention is exhibited for the first time by blending the ester additive into a base oil that is an ester other than the ester additive, and is an unexpected remarkable effect. It can be said.
- the ester additive is preferably at least one selected from pentaerythritol tetra (2-ethylhexanoate) and dipentaerythritol hexa (hexanoate).
- the kinematic viscosity at 40 ° C. of the refrigerating machine oil composition is preferably 3 to 300 mm 2 / s.
- the base oil is preferably a polyol ester.
- the base oil is preferably a polyol ester obtained from pentaerythritol, a mixed acid of carboxylic acid having 4 to 7 carbon atoms and 3,5,5-trimethylhexanoic acid.
- the base oil is preferably a polyol ester obtained from pentaerythritol, branched butanoic acid and 3,5,5-trimethylhexanoic acid and having a kinematic viscosity at 40 ° C. of 30 to 110 mm 2 / s.
- the blending amount of the ester additive is preferably 2 to 7% by mass based on the total amount of the refrigerating machine oil composition.
- the refrigerating machine oil composition of the present invention preferably further contains 0.1 to 5% by mass of a phosphate ester and / or 0.01 to 2% by mass of a sulfide compound based on the total amount of the refrigerating machine oil composition. .
- the phosphate ester is preferably at least one selected from triphenyl phosphate, tricresyl phosphate, and alkylphenyl phosphate having an alkyl group having 3 to 4 carbon atoms.
- the sulfide compound is preferably a thiobisphenol compound.
- the present invention also provides at least one tetraester selected from pentaerythritol and one fatty acid selected from fatty acids having 5 to 18 carbon atoms, and at least one hexaester selected from dipentaerythritol and one fatty acid selected from fatty acids having 5 to 18 carbon atoms.
- a method for producing a refrigerating machine oil composition which is 2 to 20% by mass as a reference, and wherein the refrigerating machine oil composition has a kinematic viscosity at 40 ° C. of 3 to 500 mm 2 / s.
- the present invention also includes the above refrigerating machine oil composition of the present invention, a refrigerant containing at least one selected from hydrofluorocarbons, hydrofluoroolefins and hydrocarbons and having a global warming potential (GWP) of 700 or less,
- GWP global warming potential
- the refrigerant preferably contains difluoromethane (R32).
- the refrigerating machine oil composition of the present invention can maintain a low coefficient of friction as well as wear resistance even under severe lubrication load conditions in the presence of a low GWP refrigerant, and exhibits a special effect that it can be used stably over a long period of time. .
- the refrigerating machine oil composition according to the first embodiment of the present invention is a tetraester of pentaerythritol and one selected from fatty acids having 5 to 18 carbon atoms, and 1 selected from dipentaerythritol and fatty acids having 5 to 18 carbon atoms. It contains at least one ester additive selected from hexaesters with seeds and a base oil that is an ester other than the ester additive.
- the content of the ester additive is 2 to 20% by mass based on the total amount of the refrigerator oil composition, and the kinematic viscosity at 40 ° C. of the refrigerator oil composition is 3 to 500 mm 2 / s.
- the constituent alcohol of the ester additive is pentaerythritol and / or dipentaerythritol. When any alcohol is used, the ester additive is a complete ester. In addition, this constituent alcohol may contain impurities inevitably included in a normal manufacturing process.
- the constituent fatty acid of the ester additive is one selected from fatty acids having 5 to 18 carbon atoms and needs to have a single composition.
- the constituent fatty acids in one molecule may have a single composition.
- pentaerythritol tetraester and dipentaerythritol hexaester are used in combination, the constituent fatty acids of each complete ester are the same or different from each other. May be.
- this constituent fatty acid may contain impurities that are inevitably included in the normal production process.
- the fatty acid having 5 to 18 carbon atoms may be either a saturated fatty acid or an unsaturated fatty acid, and may be either a linear fatty acid or a branched fatty acid.
- fatty acid specifically, Linear or branched pentanoic acid, linear or branched hexanoic acid, linear or branched heptanoic acid, linear or branched octanoic acid, linear or branched nonanoic acid, Linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or branched tetradecanoic acid, Saturated fatty acids such as linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid; Linear
- the number of carbon atoms of the constituent fatty acid of the ester additive is 5 to 18, preferably 5 to 12, and more preferably 6 to 9.
- the number of carbon atoms of the constituent fatty acid is less than 5, the effect of improving the wear resistance is insufficient, and when it exceeds 18, the solubility in the base oil at a low temperature is lowered.
- the ester additive can be obtained by a dehydration condensation reaction of pentaerythritol and / or dipentaerythritol and one selected from fatty acids having 5 to 18 carbon atoms.
- the acid value of the ester additive is preferably 0.1 mgKOH / g or less, and the hydroxyl value is 10 mgKOH / g or less. It is preferable that
- the content of the ester additive is 2 to 20% by mass, preferably 2 to 15% by mass, more preferably 2 to 7% by mass based on the total amount of the refrigerating machine oil composition. Even if the blending amount of the ester additive is less than 2% by mass or exceeds 20% by mass, the effect of improving the wear resistance is insufficient.
- the said compounding quantity can be suitably selected according to the kind of base oil, kinematic viscosity, etc. within this range.
- the base oil in the first embodiment is an ester other than the ester additive.
- the ester can be obtained by dehydration condensation reaction of alcohol and fatty acid.
- diesters of dibasic acids and monohydric alcohols polyols (particularly neopentyl).
- Polyol and a fatty acid ester of a fatty acid, or a complex ester of a polyol, a polybasic acid and a monohydric alcohol (or fatty acid) can be mentioned as a suitable base oil component.
- polyol esters having excellent stability are preferred.
- an ester synthesized from pentaerythritol, a carboxylic acid having 4 to 7 carbon atoms, and 3,5,5-trimethylhexanoic acid has a large lubricity improving effect due to the blending of the ester additive.
- a polyol ester in which the carboxylic acid having 4 to 7 carbon atoms is branched butanoic acid is more preferable.
- the kinematic viscosity at 40 ° C. of the polyol ester of pentaerythritol, branched butanoic acid and 3,5,5-trimethylhexanoic acid is preferably 30 to 110 mm 2 / s.
- the base oil according to this embodiment is an ester of a polyhydric alcohol and a fatty acid, and the molar ratio of the fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms in the fatty acid is 15:85 to 90:10, and the fatty acid having 4 to 6 carbon atoms contains 2-methylpropanoic acid, and the fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms in the total amount of fatty acids constituting the ester.
- An ester (hereinafter referred to as “polyhydric alcohol fatty acid ester (A)”) having a total ratio of 20 mol% or more can be preferably used.
- the polyhydric alcohol fatty acid ester (A) includes a complete ester in which all the hydroxyl groups of the polyhydric alcohol are esterified, a partial ester in which some of the hydroxyl groups of the polyhydric alcohol remain without being esterified, and a complete ester.
- a mixture of an ester and a partial ester is included, but the hydroxyl value of the polyhydric alcohol fatty acid ester (A) is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and most preferably 3 mgKOH / g or less.
- the molar ratio of the fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms is 15:85 to 90:10, preferably 15 : 85 to 85:15, more preferably 20:80 to 80:20, still more preferably 25:75 to 75:25, and most preferably 30:70 to 70:30. Further, the total ratio of the fatty acid having 4 to 6 carbon atoms and the fatty acid having 7 to 9 carbon atoms having a branch to the total amount of the fatty acid constituting the polyhydric alcohol fatty acid ester (A) is 20 mol% or more.
- the ratio of the fatty acid is a value based on the total amount of fatty acids constituting the polyhydric alcohol fatty acid ester (A) contained in the refrigerating machine oil.
- fatty acids having 4 to 6 carbon atoms include butanoic acid, 2-methylpropanoic acid, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, and 2-methylpentane.
- examples include acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, hexanoic acid and the like.
- those having a branch in the alkyl skeleton such as 2-methylpropanoic acid are preferable.
- branched fatty acids having 7 to 9 carbon atoms include 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, and 2,2-dimethylpentanoic acid.
- the molar ratio of the fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms is 15:85 to 90:10, and has 4 to 6 carbon atoms.
- a fatty acid other than the fatty acid having 4 to 6 carbon atoms and the branched fatty acid having 7 to 9 carbon atoms may be contained as a constituent acid component.
- fatty acids other than fatty acids having 4 to 6 carbon atoms and branched fatty acids having 7 to 9 carbon atoms include fatty acids having 2 to 3 carbon atoms such as acetic acid and propionic acid; heptanoic acid, octanoic acid and nonane C7-9 linear fatty acids such as acids; decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, oleic acid, etc.
- Examples thereof include fatty acids having 10 to 20 carbon atoms.
- the total ratio of the fatty acid having 4 to 6 and the branched fatty acid having 7 to 9 carbon atoms needs to be 20 mol% or more, preferably 25 mol% or more, and preferably 30 mol% or more. More preferably, it is more preferably 80 mol% or more. When this ratio is 20 mol% or more, the compatibility with the refrigerant (particularly the difluoromethane refrigerant) is sufficient.
- polyhydric alcohol fatty acid esters (A) those in which the acid constituents consist only of 2-methylpropanoic acid and 3,5,5-trimethylhexanoic acid ensure that the necessary viscosity is ensured and that the refrigerant (particularly difluoromethane refrigerant) It is particularly preferable in terms of compatibility with compatibility.
- the polyhydric alcohol fatty acid ester (A) according to the present embodiment may be a mixture of two or more esters having different molecular structures. In such a case, each molecule does not necessarily satisfy the above conditions. However, the above-mentioned conditions should be satisfied as a whole fatty acid constituting the pentaerythritol fatty acid ester contained in the refrigerating machine oil.
- the polyhydric alcohol fatty acid ester (A) essentially comprises a fatty acid having 4 to 6 carbon atoms and a branched fatty acid having 7 to 9 carbon atoms as an acid component constituting the ester, and other fatty acids as necessary.
- the polyhydric alcohol fatty acid ester (A) may have only two types of fatty acids as acid components, or may have three or more types of fatty acids having different structures as acid components.
- the polyhydric alcohol fatty acid ester preferably contains only a fatty acid in which the carbon atom adjacent to the carbonyl carbon ( ⁇ -position carbon atom) is not a quaternary carbon as an acid component.
- the lubricity in the presence of the difluoromethane refrigerant tends to be insufficient.
- polyhydric alcohol constituting the polyhydric alcohol fatty acid ester (A)
- polyhydric alcohols having 2 to 6 hydroxyl groups are preferably used.
- dihydric alcohol 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, , 12-dodecanediol and the like.
- trihydric or higher alcohols include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- ( Pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (glycerin dimer to trimer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol Polysaccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, and partial etherified products thereof It is.
- neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di-ethylene are more excellent in hydrolytic stability.
- esters of hindered alcohols such as-(pentaerythritol), tri- (pentaerythritol), neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, esters of di- (pentaerythritol) Is more preferred, neopentyl glycol, trimethylolpropane, pentaerythritol, di- (pentaerythritol) is more preferred, compatibility with the refrigerant and hydrolysis Since particularly excellent qualitative, pentaerythritol, di - (pentaerythritol) or pentaerythritol and di - mixed esters of (pentaerythritol) is most preferred.
- hindered alcohols such as-(pentaerythritol), tri- (pentaerythritol), ne
- the constituent fatty acid of the polyhydric alcohol fatty acid ester (A) include the following.
- the acid component which comprises a polyhydric alcohol fatty acid ester (A).
- the content of the polyhydric alcohol fatty acid ester (A) is 50% by mass or more based on the total amount of the refrigerating machine oil, preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 75% by mass or more.
- the refrigerating machine oil composition according to the present embodiment may contain a polyhydric alcohol fatty acid ester (A) and another ester as a base oil, and further contain additives other than the ester additive described later. Although it may be contained, if the polyhydric alcohol fatty acid ester (A) is less than 50% by mass, the required viscosity and the compatibility cannot be achieved at a high level.
- the refrigerating machine oil composition according to the present embodiment contains a polyhydric alcohol fatty acid ester (A) as a base oil
- a polyhydric alcohol fatty acid ester (A) as a base oil
- the polyhydric alcohol fatty acid ester (A) is contained alone (ie, the polyhydric alcohol fatty acid ester (A) is contained).
- an ester other than the polyhydric alcohol fatty acid ester (A) is further contained as a base oil to such an extent that the excellent performance is not impaired. May be.
- the base oil other than the polyhydric alcohol fatty acid ester (A) include an ester additive and a polyol ester other than the polyhydric alcohol fatty acid ester (A), a complex ester, and an alicyclic dicarboxylic acid ester.
- polyol esters other than the polyhydric alcohol fatty acid ester (A) include esters of polyhydric alcohols such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, pentaerythritol, dipentaerythritol and fatty acids. Particularly preferred are esters of neopentyl glycol and fatty acids, esters of pentaerythritol and fatty acids, and esters of dipentaerythritol and fatty acids.
- the neopentyl glycol ester is preferably an ester of neopentyl glycol and a fatty acid having 5 to 9 carbon atoms.
- neopentyl glycol esters include neopentyl glycol di 3,5,5-trimethyl hexanate, neopentyl glycol di 2-ethyl hexanate, neopentyl glycol di 2-methyl hexanate, Neopentyl glycol di-2-ethylpentanoate, neopentyl glycol and 2-methylhexanoic acid 2-ethylpentanoic acid ester, neopentyl glycol and 3-methylhexanoic acid-5-methylhexanoic acid ester, neopentyl glycol Esters of 2-methylhexanoic acid, 2-ethylhexanoic acid, neopentyl glycol and 3,5-dimethylhexanoic
- the pentaerythritol ester is preferably an ester of pentaerythritol and two or more mixed fatty acids selected from fatty acids having 5 to 9 carbon atoms.
- specific examples of such pentaerythritol esters include pentaerythritol, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, and 2-ethylpentanoic acid.
- esters with two or more fatty acids selected from 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid are examples of such pentaerythritol esters.
- the dipentaerythritol ester is preferably an ester of dipentaerythritol and two or more mixed fatty acids selected from fatty acids having 5 to 9 carbon atoms.
- specific examples of such dipentaerythritol esters include dipentaerythritol, pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethyl Examples thereof include esters with two or more fatty acids selected from pentanoic acid, 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid.
- the content of the oxygen-containing synthetic oil other than the polyhydric alcohol fatty acid ester (A) is not limited as long as it does not impair the excellent lubricity and compatibility of the refrigerating machine oil according to the embodiment. On the basis, it is preferably less than 50% by mass, more preferably 45% by mass or less, further preferably 40% by mass or less, still more preferably 35% by mass or less, and 30% by mass.
- esters other than polyol esters as base oil If the case is preferably less than 50 wt% total amount of the refrigerating machine oil basis, more preferably at most 40 mass%, more preferably not more than 30 wt%.
- ester additive and a polyhydric alcohol fatty acid ester (A) When there are too many compounding quantities of polyol esters other than a pentaerythritol fatty acid ester, and other esters, the effect by use of an ester additive and a polyhydric alcohol fatty acid ester (A) will become difficult to be acquired.
- the polyol ester other than the polyhydric alcohol fatty acid ester (A) may be a partial ester in which some of the hydroxyl groups of the polyhydric alcohol are not esterified and remain as hydroxyl groups, and all the hydroxyl groups are esterified. It may be a complete ester or a mixture of a partial ester and a complete ester, but the hydroxyl value is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, most preferably 3 mgKOH / g or less. Preferably there is.
- the refrigerating machine oil which concerns on this embodiment contains polyol esters other than a polyhydric-alcohol fatty acid ester (A), even if it contains what consists of 1 type of the polyol ester of a single structure as this polyol ester. It may also contain a mixture of two or more polyol esters having different structures.
- the polyol ester other than the polyhydric alcohol fatty acid ester (A) is an ester of one fatty acid and one polyhydric alcohol as long as it has a different structure from the ester additive and the polyhydric alcohol fatty acid ester.
- the refrigerating machine oil composition according to the present embodiment may further contain various additives described later.
- the refrigerating machine oil composition according to the present embodiment can further contain a phosphate ester.
- the phosphate ester itself has a function as an antiwear additive, but when the above ester additive and phosphate ester are used in combination, the wear resistance of the refrigerating machine oil composition can be drastically improved.
- Preferred phosphoric acid esters include triphenyl phosphate (TPP), tricresyl phosphate (TCP), and alkyl phenyl phosphate (APP) having an alkyl group having 3 to 4 carbon atoms. Furthermore, as APP, a mixture of one (mono-type), two (di-type) and three (tri-type) alkylphenyl groups can be used, and the mixing ratio is not particularly limited. .
- the blending amount of the phosphate ester is preferably 0.1 to 3% by mass, more preferably 0.2 to 2%, based on the total amount of the refrigerating machine oil composition, from the viewpoint of further effect of improving wear resistance and stability. % By mass.
- the refrigerating machine oil composition according to the present embodiment can further contain a sulfide compound.
- the sulfide compound itself has a function as an antiwear additive.
- the wear resistance of the refrigerating machine oil composition can be dramatically improved.
- sulfide compound a monosulfide compound is preferable.
- sulfur compounds having high activity such as disulfide compounds deteriorate the stability of refrigeration oil and change the quality of copper used in refrigeration equipment.
- the sulfide compound is particularly preferably a thiobisphenol compound that is antioxidant, that is, has a radical scavenging ability and is also a stabilizer.
- the blending amount of the sulfide compound is preferably 0.05 to 2% by mass, more preferably 0.1 to 1% by mass, based on the total amount of the refrigerating machine oil composition.
- the compounding amount of the sulfide compound is less than 0.05% by mass, it tends to be difficult to obtain a further effect of improving the wear resistance by the compounding of the sulfide compound.
- the compounding amount exceeds 2% by mass, the corrosion depends on the use atmosphere. May cause wear.
- a phosphate ester and a sulfide compound may be used in combination.
- the refrigerator oil composition according to the present embodiment is an antioxidant, a friction modifier, an antiwear agent, an extreme pressure agent, and the like conventionally used in lubricating oils, as long as the object of the present invention is not impaired.
- Additives such as rust preventives, metal deactivators, and antifoaming agents can be included to further improve performance.
- di-tert di-tert.
- friction modifiers include aliphatic amines, aliphatic amides, aliphatic imides, alcohols, esters, acidic phosphate amine salts, phenolic compounds such as butyl-p-cresol, and amine compounds such as alkyldiphenylamine, Metal deactivators such as phosphite amine salts, zinc dialkyldithiophosphates as antiwear agents, sulfurized olefins and sulfurized fats as extreme pressure agents, alkenyl succinic acid esters or partial esters as rust inhibitors Examples thereof include benzotriazole, and examples of the antifoaming agent include silicone compounds and polyester compounds.
- the kinematic viscosity at 40 ° C. of the refrigerating machine oil composition according to this embodiment is 3 to 500 mm 2 / s, preferably 3 to 300 mm 2 / s, and more preferably 5 to 150 mm 2 / s.
- the viscosity index of the refrigerator oil composition is preferably 10 or more.
- the kinematic viscosity and the viscosity index at 40 ° C. referred to in the present invention mean values measured in accordance with JIS K2283.
- the pour point of the refrigerating machine oil composition is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
- the flash point of the refrigerator oil composition is preferably 120 ° C or higher, more preferably 200 ° C or higher.
- the pour point is JIS K2269 “Pour point of crude oil and petroleum products and cloud point test method of petroleum products”, and the flash point is JIS K2265 “Crude oil and petroleum products-flash point test method”. It can be measured according to the method.
- the acid value of the refrigerating machine oil composition is not particularly limited, but is preferably 0.1 mg KOH / g in order to prevent corrosion of the metal used in the refrigerating machine or piping and to prevent deterioration of the refrigerating machine oil itself.
- the acid value as used in the field of this invention means the acid value measured based on JISK2501 "Petroleum products and lubricating oil-neutralization test method".
- the water content of the refrigerating machine oil composition is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less.
- the moisture content is required to be low from the viewpoint of stability of the refrigerator oil and electrical insulation.
- the ester additive is added to a base oil that is an ester other than the ester additive, and the blending amount of the ester additive is 2 to 20 based on the total amount of the refrigerating machine oil composition. It can be obtained by blending such that the kinematic viscosity at 40 ° C. of the obtained refrigerator oil composition is 3 to 500 mm 2 / s by mass%.
- the refrigerating machine oil composition contains components other than the ester additive and base oil (the above-mentioned phosphate ester, sulfide compound, etc.), the blending of these components into the base oil is the same as the ester additive. Alternatively, it may be before or after blending the ester additive.
- the refrigerant used together with the refrigerating machine oil composition according to the present embodiment is not particularly limited, but a refrigerant that is compatible with the refrigerating machine oil composition, that is, a refrigerant that is compatible at room temperature without being separated into two layers is preferable.
- the refrigerating machine oil composition according to the present embodiment includes a low GWP refrigerant such as hydrofluoroolefin (HFO) such as 2,3,3,3-tetrafluoropropene (HFO-1234yf) and difluoromethane (R32), or
- HFO hydrofluoroolefin
- R600a isobutane
- propane propane
- the working fluid composition for a refrigerator according to the second embodiment of the present invention contains the refrigerator oil composition according to the first embodiment, and at least one selected from hydrofluorocarbons, hydrofluoroolefins, and hydrocarbons, And a refrigerant having a global warming potential (GWP) of 700 or less.
- GWP global warming potential
- HFCs hydrofluorocarbons having a GWP of 700 or less
- mixed refrigerants such as R410A
- R32 or R32 which is a high-pressure hydrofluorocarbon (HFC) having a low boiling point
- HFC refrigerants are characterized by a high boiling point and high pressure, and when used, the discharge temperature of the compressor becomes high, so that the oil film becomes thin and severe lubrication conditions occur. For this reason, wear resistance is insufficient when conventional refrigerator oil is used.
- HFC refrigerant even when the above HFC refrigerant is used, excellent wear resistance can be realized.
- HFO hydrofluoroolefins
- HFO-1234yf 2,3,3,3-tetrafluoropropene
- HFO-1234ze 1,3,3,3-tetrafluoropropene
- HFO-1225ye 1,2,3,3,3-pentafluoropropene
- examples of the hydrocarbon refrigerant having a GWP of 700 or less include saturated hydrocarbons having 3 to 6 carbon atoms, particularly isobutane (R600a) and propane (R290).
- R600a isobutane
- R290 propane
- the viscosity of the refrigerating machine oil is lowered, resulting in severe lubrication conditions. For this reason, wear resistance is insufficient when conventional refrigerator oil is used.
- excellent wear resistance can be realized even when the above hydrocarbon refrigerant is used.
- Example 1 to 12 Comparative Examples 1 to 12
- refrigerating machine oil compositions having the compositions shown in Tables 1 to 3 were prepared using the base oils and additives shown below, respectively.
- A Ester base oil
- A-1 POE-1: ester of 2-erythritol, 2-methylpropanoic acid and 3,5,5-trimethylhexanoic acid in a mixed ratio of 7: 3 by mass (40 ° C. Kinematic viscosity: 34.4 mm 2 / s, viscosity index: 77)
- A-2) POE-2: ester of pentaerythritol and 2-methylpropanoic acid and 2-ethylhexanoic acid in a mixed ratio of 3: 7 by mass ratio (kinematic viscosity at 40 ° C .: 36.7 mm 2 / s Viscosity index: 78)
- C Other additives (C-1) tricresyl phosphate (TCP) (C-2) Triphenyl phosphate (TPP) (C-3) Tridecyl phosphate (TDP) (C-4) Dibenzyl sulfide (C-5) Didodecyl sulfide (C-6) 4,4′-thiobis (3-methyl-6-tert.butylphenol)
- Lubricity test In the lubricity test, a high-pressure atmosphere friction tester (rotating sliding method of rotating vane material and fixed disk material) manufactured by Shinko Engineering Co., Ltd., which can create a refrigerant atmosphere similar to that of an actual compressor, was used.
- the basic test conditions were oil amount: 600 ml, test temperature: 110 ° C., rotation speed: 500 rpm, load load: 100 kgf, test time: 1 hour, SKH-51 as the vane material, and FC250 as the disk material. .
- the test was conducted under the following four test conditions depending on the type of refrigerant. Lubricity test- (1): R32 was used as the refrigerant, and the pressure in the test container was 3.1 MPa.
- Lubricity test- (2) HFO-1234yf (abbreviated as yf in the table) was used as the refrigerant, and the pressure in the test container was 1.6 MPa.
- Lubricity test-(3): R410A (R32 / R125 1/1 by mass ratio) was used as the refrigerant, and the pressure in the test container was 3.1 MPa.
- the results shown in Table 1 show that the wear amount in Examples 1 to 4 is significantly reduced compared with Comparative Examples 1 to 4, and the effect of wear resistance is great. Also, from the results shown in Tables 2 and 3, in Examples 5 to 12, the combination of the additives (B-1), (B-2) and (C-1) to (C-6) It can be seen that the response to the effect of improving the wear resistance of the additive is greatly improved. Further, from the comparison between Example 5 and Comparative Examples 5, 7, and 8, whether the amount of the ester additive according to the present invention is too small or too large, the response for amplifying the additive effect is reduced. I understand.
- the refrigeration oil composition of the present invention is a refrigeration oil excellent in long-term reliability that can maintain the effect of wear resistance even under severe lubrication conditions, it has a compressor, a condenser, a squeezing device, an evaporator, etc.
- Refrigeration and air conditioning systems with high cooling efficiency that circulate refrigerant between them especially in systems with compressors such as rotary type, swing type, scroll type, etc., and can be suitably used for room air conditioners, packaged air conditioners, refrigerators, cars It can be used in fields such as air conditioners and industrial refrigerators.
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Abstract
Description
本発明の第1実施形態に係る冷凍機油組成物は、ペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのテトラエステル及びジペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのヘキサエステルから選ばれる少なくとも1種のエステル添加剤と、前記エステル添加剤以外のエステルである基油を含有してなる。かかる冷凍機油組成物において、エステル添加剤の含有量は冷凍機油組成物全量を基準として2~20質量%であり、冷凍機油組成物の40℃における動粘度が3~500mm2/sである。
直鎖状又は分岐状のペンタン酸、直鎖状又は分岐状のヘキサン酸、直鎖状又は分岐状のヘプタン酸、直鎖状又は分岐状のオクタン酸、直鎖状又は分岐状のノナン酸、直鎖状又は分岐状のデカン酸、直鎖状又は分岐状のウンデカン酸、直鎖状又は分岐状のドデカン酸、直鎖状又は分岐状のトリデカン酸、直鎖状又は分岐状のテトラデカン酸、直鎖状又は分岐状のペンタデカン酸、直鎖状又は分岐状のヘキサデカン酸、直鎖状又は分岐状のヘプタデカン酸、直鎖状又は分岐状のオクタデカン酸等の飽和脂肪酸;
直鎖状又は分岐状のペンテン酸、直鎖状又は分岐状のヘキセン酸、直鎖状又は分岐状のヘプテン酸、直鎖状又は分岐状のオクテン酸、直鎖状又は分岐状のノネン酸、直鎖状又は分岐状のデセン酸、直鎖状又は分岐状のウンデセン酸、直鎖状又は分岐状のドデセン酸、直鎖状又は分岐状のトリデセン酸、直鎖状又は分岐状のテトラデセン酸、直鎖状又は分岐状のペンタデセン酸、直鎖状又は分岐状のヘキサデセン酸、直鎖状又は分岐状のヘプタデセン酸、直鎖状又は分岐状のオクタデセン酸等の不飽和脂肪酸等が挙げられる。
(i)ブタン酸、2-メチルプロパン酸、ペンタン酸、2-メチルブタン酸、3-メチルブタン酸、2,2-ジメチルプロパン酸、2-メチルペンタン酸、3-メチルペンタン酸、4-メチルペンタン酸、2,2-ジメチルブタン酸、2,3-ジメチルブタン酸、3,3-ジメチルブタン酸およびヘキサン酸から選ばれる1~13種と、2-メチルヘキサン酸、3-メチルヘキサン酸、4-メチルヘキサン酸、5-メチルヘキサン酸、2,2-ジメチルペンタン酸、2,3-ジメチルペンタン酸、2,4-ジメチルペンタン酸、3,3-ジメチルペンタン酸、3,4-ジメチルペンタン酸、4,4-ジメチルペンタン酸、2-エチルペンタン酸、3-エチルペンタン酸および2-エチル-3-メチルブタン酸から選ばれる1~13種との組合せ;
(ii)ブタン酸、2-メチルプロパン酸、ペンタン酸、2-メチルブタン酸、3-メチルブタン酸、2,2-ジメチルプロパン酸、2-メチルペンタン酸、3-メチルペンタン酸、4-メチルペンタン酸、2,2-ジメチルブタン酸、2,3-ジメチルブタン酸、3,3-ジメチルブタン酸およびヘキサン酸から選ばれる1~13種と、2-メチルヘプタン酸、3-メチルヘプタン酸、4-メチルヘプタン酸、5-メチルヘプタン酸、6-メチルヘプタン酸、2,2-ジメチルヘキサン酸、3,3-ジメチルヘキサン酸、4,4-ジメチルヘキサン酸、5,5-ジメチルヘキサン酸、2,3-ジメチルヘキサン酸、2,4-ジメチルヘキサン酸、2,5-ジメチルヘキサン酸、3,4-ジメチルヘキサン酸、3,5-ジメチルヘキサン酸、4,5-ジメチルヘキサン酸、2,2,3-トリメチルペンタン酸、2,3,3-トリメチルペンタン酸、2,4,4-トリメチルペンタン酸、3,4,4-トリメチルペンタン酸、2-エチルヘキサン酸、3-エチルヘキサン酸、2-プロピルペンタン酸、2-メチル-2-エチルペンタン酸、2-メチル-3-エチルペンタン酸および3-メチル-3-エチルペンタン酸から選ばれる1~25種との組合せ;
(iii)ブタン酸、2-メチルプロパン酸、ペンタン酸、2-メチルブタン酸、3-メチルブタン酸、2,2-ジメチルプロパン酸、2-メチルペンタン酸、3-メチルペンタン酸、4-メチルペンタン酸、2,2-ジメチルブタン酸、2,3-ジメチルブタン酸、3,3-ジメチルブタン酸およびヘキサン酸から選ばれる1~13種と、2-メチルオクタン酸、3-メチルオクタン酸、4-メチルオクタン酸、5-メチルオクタン酸、6-メチルオクタン酸、7-メチルオクタン酸、8-メチルオクタン酸、2,2-ジメチルヘプタン酸、3,3-ジメチルヘプタン酸、4,4-ジメチルヘプタン酸、5,5-ジメチルヘプタン酸、6,6-ジメチルヘプタン酸、2,3-ジメチルヘプタン酸、2,4-ジメチルヘプタン酸、2,5-ジメチルヘプタン酸、2,6-ジメチルヘプタン酸、3,4-ジメチルヘプタン酸、3,5-ジメチルヘプタン酸、3,6-ジメチルヘプタン酸、4,5-ジメチルヘプタン酸、4,6-ジメチルヘプタン酸、2-エチルヘプタン酸、3-エチルヘプタン酸、4-エチルヘプタン酸、5-エチルヘプタン酸、2-プロピルヘキサン酸、3-プロピルヘキサン酸、2-ブチルペンタン酸、2,2,3-トリメチルヘキサン酸、2,2,4-トリメチルヘキサン酸、2,2,5-トリメチルヘキサン酸、2,3,3-トリメチルヘキサン酸、2,3,4-トリメチルヘキサン酸、2,3,5-トリメチルヘキサン酸、3,3,4-トリメチルヘキサン酸、3,3,5-トリメチルヘキサン酸、3,5,5-トリメチルヘキサン酸、4,4,5-トリメチルヘキサン酸、4,5,5-トリメチルヘキサン酸、2,2,3,3-テトラメチルペンタン酸、2,2,3,4-テトラメチルペンタン酸、2,2,4,4-テトラメチルペンタン酸、2,3,4,4-テトラメチルペンタン酸、3,3,4,4-テトラメチルペンタン酸、2,2-ジエチルペンタン酸、2,3-ジエチルペンタン酸、3,3-ジエチルペンタン酸、2-エチル-2,3,3-トリメチル酪酸、3-エチル-2,2,3-トリメチル酪酸および2,2-ジイソプロピルプロピオン酸から選ばれる1~50種との組合せ。
(i)2-メチルプロパン酸と、2-メチルヘキサン酸、3-メチルヘキサン酸、4-メチルヘキサン酸、5-メチルヘキサン酸、2,2-ジメチルペンタン酸、2,3-ジメチルペンタン酸、2,4-ジメチルペンタン酸、3,3-ジメチルペンタン酸、3,4-ジメチルペンタン酸、4,4-ジメチルペンタン酸、2-エチルペンタン酸、3-エチルペンタン酸および2-エチル-3-メチルブタン酸から選ばれる1~13種との組合せ;
(ii)2-メチルプロパン酸と、2-メチルヘプタン酸、3-メチルヘプタン酸、4-メチルヘプタン酸、5-メチルヘプタン酸、6-メチルヘプタン酸、2,2-ジメチルヘキサン酸、3,3-ジメチルヘキサン酸、4,4-ジメチルヘキサン酸、5,5-ジメチルヘキサン酸、2,3-ジメチルヘキサン酸、2,4-ジメチルヘキサン酸、2,5-ジメチルヘキサン酸、3,4-ジメチルヘキサン酸、3,5-ジメチルヘキサン酸、4,5-ジメチルヘキサン酸、2,2,3-トリメチルペンタン酸、2,3,3-トリメチルペンタン酸、2,4,4-トリメチルペンタン酸、3,4,4-トリメチルペンタン酸、2-エチルヘキサン酸、3-エチルヘキサン酸、2-プロピルペンタン酸、2-メチル-2-エチルペンタン酸、2-メチル-3-エチルペンタン酸および3-メチル-3-エチルペンタン酸から選ばれる1~25種との組合せ;
(iii)2-メチルプロパン酸と、2-メチルオクタン酸、3-メチルオクタン酸、4-メチルオクタン酸、5-メチルオクタン酸、6-メチルオクタン酸、7-メチルオクタン酸、8-メチルオクタン酸、2,2-ジメチルヘプタン酸、3,3-ジメチルヘプタン酸、4,4-ジメチルヘプタン酸、5,5-ジメチルヘプタン酸、6,6-ジメチルヘプタン酸、2,3-ジメチルヘプタン酸、2,4-ジメチルヘプタン酸、2,5-ジメチルヘプタン酸、2,6-ジメチルヘプタン酸、3,4-ジメチルヘプタン酸、3,5-ジメチルヘプタン酸、3,6-ジメチルヘプタン酸、4,5-ジメチルヘプタン酸、4,6-ジメチルヘプタン酸、2-エチルヘプタン酸、3-エチルヘプタン酸、4-エチルヘプタン酸、5-エチルヘプタン酸、2-プロピルヘキサン酸、3-プロピルヘキサン酸、2-ブチルペンタン酸、2,2,3-トリメチルヘキサン酸、2,2,4-トリメチルヘキサン酸、2,2,5-トリメチルヘキサン酸、2,3,3-トリメチルヘキサン酸、2,3,4-トリメチルヘキサン酸、2,3,5-トリメチルヘキサン酸、3,3,4-トリメチルヘキサン酸、3,3,5-トリメチルヘキサン酸、3,5,5-トリメチルヘキサン酸、4,4,5-トリメチルヘキサン酸、4,5,5-トリメチルヘキサン酸、2,2,3,3-テトラメチルペンタン酸、2,2,3,4-テトラメチルペンタン酸、2,2,4,4-テトラメチルペンタン酸、2,3,4,4-テトラメチルペンタン酸、3,3,4,4-テトラメチルペンタン酸、2,2-ジエチルペンタン酸、2,3-ジエチルペンタン酸、3,3-ジエチルペンタン酸、2-エチル-2,3,3-トリメチル酪酸、3-エチル-2,2,3-トリメチル酪酸および2,2-ジイソプロピルプロピオン酸から選ばれる1~50種との組合せ。
本発明の第2実施形態に係る冷凍機用作動流体組成物は、上記第1実施形態に係る冷凍機油組成物と、ハイドロフルオロカーボン、ハイドロフルオロオレフィン及び炭化水素から選ばれる少なくとも1種を含有し、地球温暖化係数(GWP)が700以下である冷媒と、を含有する。なお、本実施形態における冷凍機油組成物は上記第1実施形態の場合と同様であるため、ここでは重複する説明を省略する。
実施例1~12及び比較例1~12においては、それぞれ以下に示す基油及び添加剤を用いて、表1~3に示す組成を有する冷凍機油組成物を調製した。
(A-1)POE-1:ペンタエリスリトールと、2-メチルプロパン酸と3、5,5-トリメチルヘキサン酸が質量比で7:3の混合酸とのエステル(40℃における動粘度:34.4mm2/s、粘度指数:77)
(A-2)POE-2:ペンタエリスリトールと、2-メチルプロパン酸と2-エチルヘキサン酸が質量比で3:7の混合酸とのエステル(40℃における動粘度:36.7mm2/s、粘度指数:78)
(A-3)POE-3:ジペンタエリスリトールと、n―ブタン酸と3、5、5-トリメチルヘキサン酸が質量比で7:3の混合酸とのエステル(40℃における動粘度:65.1mm2/s、粘度指数:90)
(A-4)POE-4:ペンタエリスリトールと、n-ペンタン酸、n-ヘプタン酸と3、5、5-トリメチルヘキサン酸が質量比で4:4:2である混合酸とのエステル(40℃における動粘度:28.5mm2/s、粘度指数:133)
(A-5)POE-5:トリメチロールプロパンと、オレイン酸のエステル(40℃における動粘度:48.3mm2/s、粘度指数:176)
(B-1)PE2EH:ペンタエリスリトールテトラ(2-エチルヘキサノエート)(ペンタエリスリトールと2-エチルヘキサン酸のテトラエステル、酸価:0.01mgKOH/g、水酸基価:1mgKOH/g)
(B-2)DPEH:ジペンタエリスリトールヘキサ(ヘキサノエート)(ジペンタエリスリトールとn-ヘキサン酸とのヘキサエステル、酸価:0.01mgKOH/g、水酸基価:1mgKOH/g)
(C-1)トリクレジルフォスフェート(TCP)
(C-2)トリフェニルフォスフェート(TPP)
(C-3)トリデシルフォスフェート(TDP)
(C-4)ジベンジルスルフィド
(C-5)ジドデシルスルフィド
(C-6)4,4’-チオビス(3-メチル-6-tert.ブチルフェノール)
潤滑性試験においては、実コンプレッサと類似の冷媒雰囲気にできる、神鋼造機(株)製の高圧雰囲気摩擦試験機(回転ベーン材と固定ディスク材との回転しゅう動方式)を用いた。基本の試験条件は、油量:600ml、試験温度:110℃、回転数:500rpm、負荷荷重:100kgf、試験時間:1時間で、ベーン材としてはSKH-51、ディスク材としてはFC250を用いた。
試験は、冷媒の種類に応じて次の4種の試験条件で行った。
潤滑性試験-(1):冷媒にR32を使用し、試験容器内圧力は3.1MPaとした。
潤滑性試験-(2):冷媒にHFO-1234yf(表ではyfと略す)を使用し、試験容器内圧力は1.6MPaとした。
潤滑性試験-(3):冷媒にR410A(質量比でR32/R125=1/1)を使用し、試験容器内圧力は3.1MPa とした。
潤滑性試験-(4):n-ヘキサン(表ではn-C6と略す)を冷凍機油組成物に対して容積比で20%配合して試験した(R290等の炭化水素冷媒の代替として使用)。圧力は常圧より若干高くなった程度であった。
なお、耐摩耗性の評価は、ディスク材の摩耗量が極めて少ないことから、ベーン材の摩耗量によって行った。得られた結果を表1~3に示す。
含有水分量を100ppmに調整した試料油90gをオートクレーブに秤取し、触媒(鉄、銅、アルミの線、いずれも外径1.6mm×50mm)と各々の冷媒(R32、HFO-1234yf、R410A、n-ヘキサンを使用)10gを封入した後、175℃に加熱し、100時間後の試料油の外観と酸価を測定した(JIS C2101)。得られた結果を表1~3に示す。
なお、安定性試験前の試料油(新油)の酸価は、すべて0.01mgKOH/gであった。
また、表2、3に示した結果から、実施例5~12においては、添加剤(B-1)、(B-2)と(C-1)~(C-6)との併用により、添加剤の耐摩耗向上効果のレスポンスが大幅に向上していることがわかる。また、実施例5と比較例5、7、8との比較から、本発明に係るエステル添加剤の配合量が少なすぎても、多すぎても、その添加効果を増幅させるレスポンスが低下することがわかる。
Claims (13)
- ペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのテトラエステル及びジペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのヘキサエステルから選ばれる少なくとも1種のエステル添加剤と、前記エステル添加剤以外のエステルである基油を含有し、
前記エステル添加剤の含有量が冷凍機油組成物全量を基準として2~20質量%であり、
冷凍機油組成物の40℃における動粘度が3~500mm2/sである、冷凍機油組成物。 - 前記エステル添加剤が、ペンタエリスリトールテトラ(2-エチルヘキサノエート)及びジペンタエリスリトールヘキサ(ヘキサノエート)から選ばれる少なくとも1種である、請求項1に記載の冷凍機油組成物。
- 40℃における動粘度が3~300mm2/sである、請求項1又は2に記載の冷凍機油組成物。
- 前記基油がポリオールエステルである、請求項1~3のいずれか一項に記載の冷凍機油組成物。
- 前記基油がペンタエリスリトールと炭素数4~7のカルボン酸及び3,5,5-トリメチルヘキサン酸の混合酸とから得られるポリオールエステルである、請求項1~4のいずれか一項に記載の冷凍機油組成物。
- 前記基油が、ペンタエリスリトールと分岐のブタン酸及び3,5,5-トリメチルヘキサン酸とから得られる、40℃における動粘度が30~110mm2/sのポリオールエステルである、請求項1~5のいずれか一項に記載の冷凍機油組成物。
- 前記エステル添加剤の配合量が前記冷凍機油組成物全量を基準として2~7質量%である、請求項1~6のいずれか一項に記載の冷凍機油組成物。
- 前記冷凍機油組成物全量を基準として0.1~5質量%のリン酸エステル及び/又は0.01~2質量%のスルフィド化合物をさらに含有する、請求項1~7のいずれか一項に記載の冷凍機油組成物。
- 前記リン酸エステルがトリフェニルフォスフェート、トリクレジルフォスフェート及び炭素数3~4のアルキル基を有するアルキルフェニルフォスフェートから選ばれる少なくとも1種である、請求項8に記載の冷凍機油組成物。
- 前記スルフィド化合物がチオビスフェノール化合物である、請求項8又は9に記載の冷凍機油組成物。
- ペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのテトラエステル及びジペンタエリスリトールと炭素数5~18の脂肪酸から選ばれる1種とのヘキサエステルから選ばれる少なくとも1種のエステル添加剤を、前記エステル添加剤以外のエステルである基油に配合して冷凍機油組成物を得る工程を備え、
前記エステル添加剤の配合量が前記冷凍機油組成物全量を基準として2~20質量%であり、
前記冷凍機油組成物の40℃における動粘度が3~500mm2/sである、冷凍機油組成物の製造方法。 - 請求項1~11のいずれか一項に記載の冷凍機油組成物と、
ハイドロフルオロカーボン、ハイドロフルオロオレフィン及び炭化水素から選ばれる少なくとも1種を含有し、地球温暖化係数が700以下である冷媒と、
を含有する冷凍機用作動流体組成物。 - 前記冷媒はジフルオロメタン(R32)を含有する、請求項12の冷凍機用作動流体組成物。
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KR (1) | KR101897456B1 (ja) |
CN (1) | CN104114683B (ja) |
IN (1) | IN2014DN06608A (ja) |
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Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05171174A (ja) | 1991-04-30 | 1993-07-09 | Tonen Corp | 潤滑油組成物 |
JPH08503975A (ja) * | 1992-06-03 | 1996-04-30 | ヘンケル・コーポレイション | 冷媒の熱媒液用ポリオールエステル潤滑剤 |
JPH08157847A (ja) | 1994-12-08 | 1996-06-18 | Japan Energy Corp | Hfcフロン圧縮機用潤滑油組成物、hfcフロン圧縮機の潤滑性向上方法及び同潤滑油組成物を含有する作動流体組成物 |
JPH09189453A (ja) | 1995-11-09 | 1997-07-22 | Sanyo Electric Co Ltd | 冷凍装置 |
JP2001226690A (ja) * | 2000-02-18 | 2001-08-21 | Japan Energy Corp | 冷凍装置用潤滑油組成物及び冷凍装置 |
JP2002356694A (ja) * | 2001-05-29 | 2002-12-13 | Nof Corp | 冷凍機潤滑油組成物および冷凍機作動流体用組成物 |
JP2005325151A (ja) * | 2004-05-12 | 2005-11-24 | Japan Energy Corp | 冷凍機用潤滑油組成物 |
JP2012031239A (ja) * | 2010-07-29 | 2012-02-16 | Hitachi Appliances Inc | 冷凍空調用圧縮機及び冷凍空調装置 |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2137263C (en) | 1992-06-03 | 2003-10-14 | Nicholas E. Schnur | Polyol ester lubricants for refrigerating compressors operating at high temperature |
EP0612835B1 (en) * | 1993-02-19 | 1999-08-25 | Idemitsu Kosan Company Limited | Refrigerating machine oil composition |
US6008169A (en) * | 1996-04-17 | 1999-12-28 | Idemitsu Kosan Co., Ltd. | Refrigerator oil composition comprising saturated hydroxy fatty acids and derivatives thereof |
JP4079469B2 (ja) * | 1996-06-25 | 2008-04-23 | 出光興産株式会社 | 冷凍機油組成物 |
TW546371B (en) * | 1998-12-11 | 2003-08-11 | Idemitsu Kosan Co | Refrigerator oil composition, and method of using the composition for lubrication |
DE60130083T2 (de) * | 2000-10-16 | 2008-05-15 | Nof Corp. | Herstellung von Estern für die Verwendung als Basisschmieröl |
JP4772504B2 (ja) * | 2003-08-01 | 2011-09-14 | Jx日鉱日石エネルギー株式会社 | 冷凍機油組成物 |
US7959824B2 (en) * | 2003-08-01 | 2011-06-14 | Nippon Oil Corporation | Refrigerating machine oil composition |
JP5139665B2 (ja) * | 2006-11-02 | 2013-02-06 | 出光興産株式会社 | 冷凍機用潤滑油組成物 |
JP5572284B2 (ja) * | 2007-02-27 | 2014-08-13 | Jx日鉱日石エネルギー株式会社 | 冷凍機油および冷凍機用作動流体組成物 |
JP2009074018A (ja) * | 2007-02-27 | 2009-04-09 | Nippon Oil Corp | 冷凍機油および冷凍機用作動流体組成物 |
JP5612250B2 (ja) * | 2008-03-07 | 2014-10-22 | 出光興産株式会社 | 冷凍機用潤滑油組成物 |
JP5407157B2 (ja) * | 2008-03-18 | 2014-02-05 | ダイキン工業株式会社 | 冷凍装置 |
-
2012
- 2012-02-22 JP JP2012036442A patent/JP5689428B2/ja active Active
-
2013
- 2013-02-19 US US14/379,363 patent/US9234155B2/en active Active
- 2013-02-19 WO PCT/JP2013/054013 patent/WO2013125528A1/ja active Application Filing
- 2013-02-19 CN CN201380010063.9A patent/CN104114683B/zh active Active
- 2013-02-19 IN IN6608DEN2014 patent/IN2014DN06608A/en unknown
- 2013-02-19 EP EP13752191.0A patent/EP2818537B1/en active Active
- 2013-02-19 KR KR1020147021417A patent/KR101897456B1/ko active IP Right Grant
- 2013-02-22 TW TW102106298A patent/TWI582226B/zh active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05171174A (ja) | 1991-04-30 | 1993-07-09 | Tonen Corp | 潤滑油組成物 |
JPH08503975A (ja) * | 1992-06-03 | 1996-04-30 | ヘンケル・コーポレイション | 冷媒の熱媒液用ポリオールエステル潤滑剤 |
JPH08157847A (ja) | 1994-12-08 | 1996-06-18 | Japan Energy Corp | Hfcフロン圧縮機用潤滑油組成物、hfcフロン圧縮機の潤滑性向上方法及び同潤滑油組成物を含有する作動流体組成物 |
JPH09189453A (ja) | 1995-11-09 | 1997-07-22 | Sanyo Electric Co Ltd | 冷凍装置 |
JP2001226690A (ja) * | 2000-02-18 | 2001-08-21 | Japan Energy Corp | 冷凍装置用潤滑油組成物及び冷凍装置 |
JP2002356694A (ja) * | 2001-05-29 | 2002-12-13 | Nof Corp | 冷凍機潤滑油組成物および冷凍機作動流体用組成物 |
JP2005325151A (ja) * | 2004-05-12 | 2005-11-24 | Japan Energy Corp | 冷凍機用潤滑油組成物 |
JP2012031239A (ja) * | 2010-07-29 | 2012-02-16 | Hitachi Appliances Inc | 冷凍空調用圧縮機及び冷凍空調装置 |
Non-Patent Citations (1)
Title |
---|
See also references of EP2818537A4 |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014132676A1 (ja) * | 2013-02-26 | 2014-09-04 | Jx日鉱日石エネルギー株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
EP2963098A4 (en) * | 2013-02-26 | 2016-03-23 | Jx Nippon Oil & Energy Corp | COOLING MACHINE OIL AND WORKING FLUID COMPOSITION FOR REFRIGERATOR |
US9944881B2 (en) | 2013-02-26 | 2018-04-17 | Jxtg Nippon Oil & Energy Corporation | Refrigerating machine oil, and working fluid composition for refrigerating machines |
US10626344B2 (en) | 2013-02-26 | 2020-04-21 | Jxtg Nippon Oil & Energy Corporation | Refrigerating machine oil, and working fluid composition for refrigerating machines |
CN106471107A (zh) * | 2014-05-30 | 2017-03-01 | Kh新化株式会社 | 冷冻机油组合物及使用该组合物的冷冻机用工作流体组合物 |
US10266788B2 (en) | 2014-05-30 | 2019-04-23 | Kh Neochem Co., Ltd. | Refrigerating-machine oil composition and working fluid composition including same for refrigerating machine |
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Publication number | Publication date |
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CN104114683B (zh) | 2016-01-06 |
KR20140125773A (ko) | 2014-10-29 |
EP2818537A4 (en) | 2015-04-15 |
JP2013170255A (ja) | 2013-09-02 |
EP2818537A1 (en) | 2014-12-31 |
IN2014DN06608A (ja) | 2015-06-26 |
US20150028252A1 (en) | 2015-01-29 |
JP5689428B2 (ja) | 2015-03-25 |
KR101897456B1 (ko) | 2018-09-12 |
CN104114683A (zh) | 2014-10-22 |
US9234155B2 (en) | 2016-01-12 |
TWI582226B (zh) | 2017-05-11 |
EP2818537B1 (en) | 2020-01-22 |
TW201343902A (zh) | 2013-11-01 |
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