WO2016056392A1 - 冷凍機油及び冷凍機用作動流体組成物 - Google Patents
冷凍機油及び冷凍機用作動流体組成物 Download PDFInfo
- Publication number
- WO2016056392A1 WO2016056392A1 PCT/JP2015/076946 JP2015076946W WO2016056392A1 WO 2016056392 A1 WO2016056392 A1 WO 2016056392A1 JP 2015076946 W JP2015076946 W JP 2015076946W WO 2016056392 A1 WO2016056392 A1 WO 2016056392A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- mass
- oil
- refrigerant
- refrigerating machine
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/40—Esters containing free hydroxy or carboxyl groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/02—Materials undergoing a change of physical state when used
- C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
-
- C—CHEMISTRY; METALLURGY
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
-
- 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
-
- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/122—Halogenated hydrocarbons
-
- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/10—Components
- C09K2205/12—Hydrocarbons
- C09K2205/126—Unsaturated fluorinated hydrocarbons
-
- 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
- C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
- C09K2205/22—All components of a mixture being fluoro compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/02—Hydroxy compounds
- C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
- C10M2207/026—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings with tertiary alkyl groups
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
- C10M2223/041—Triaryl phosphates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- 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
- C10N2020/069—Linear chain compounds
-
- 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
- C10N2020/071—Branched chain compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
-
- 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
- C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
-
- 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
- C10N2030/70—Soluble oils
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to refrigerating machine oil, working fluid composition for refrigerating machines, application of the composition to refrigerating machine oil or working fluid composition for refrigerating machine, and production of refrigerating machine oil or working fluid composition for refrigerating machine. For application.
- CFC chlorofluorocarbon
- HCFC hydrochlorofluorocarbon
- HFC-134a fluoroethane
- HFC-125 pentafluoroethane
- HFC refrigerants for example, R134a, which is standardly used as a refrigerant for car air conditioners, has a zero global warming potential (GWP) although its ozone depletion potential (ODP) is zero, it is subject to regulation in Europe. It has become. Therefore, hydrofluoroolefins (HFO) such as 1,3,3,3-tetrafluoropropene (HFO-1234ze) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), difluoromethane (HFC- Low GWP refrigerants such as 32) are attracting attention. Further, for example, Patent Document 1 discloses a mixed refrigerant including an HFC refrigerant and an HFO refrigerant.
- HFO hydrofluoroolefins
- refrigerating machine oil containing hydrocarbon oil such as mineral oil or alkylbenzene has been preferably used.
- refrigerating machine oil has a phase with a refrigerant depending on the type of refrigerant that coexists.
- Refrigerating machine oil needs to be developed for each refrigerant to exhibit unpredictable behavior such as solubility, lubricity, melt viscosity with refrigerant, thermal and chemical stability.
- the present invention relates to a refrigerating machine oil excellent in compatibility with a refrigerant containing a predetermined amount of difluoromethane, pentafluoroethane, 2,3,3,3-tetrafluoropropene, and 1,1,1,2-tetrafluoroethane.
- Another object of the present invention is to provide a working fluid composition for a refrigerator containing the refrigerator oil.
- the present invention contains at least one oxygen-containing oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less as a base oil, and 15% by mass or more of difluoromethane, 15% by mass based on the total amount of refrigerant.
- Refrigerating machine oil used together with the above pentafluoroethane, 15 mass% or more of 2,3,3,3-tetrafluoropropene, and a refrigerant containing 15 mass% or more of 1,1,1,2-tetrafluoroethane I will provide a.
- the refrigerating machine oil preferably contains an ester of a fatty acid and a polyhydric alcohol in which the ratio of the fatty acid having 4 to 20 carbon atoms is 20 to 100 mol% as the oxygen-containing oil.
- the present invention also relates to the above refrigerating machine oil and 15% by mass or more of difluoromethane, 15% by mass or more of pentafluoroethane, and 15% by mass or more of 2,3,3,3-tetrafluoropropene based on the total amount of refrigerant. And a refrigerant containing 15% by mass or more of 1,1,1,2-tetrafluoroethane, and a working fluid composition for a refrigerator.
- the present invention is an application of the composition to a refrigerating machine oil or a working fluid composition for a refrigerating machine, wherein the composition is an oxygenated oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less. Containing at least one base oil, the refrigerating machine oil is 15% by mass or more of difluoromethane, 15% by mass or more of pentafluoroethane, 15% by mass or more of 2,3,3,3-tetra, based on the total amount of refrigerant.
- the working fluid composition for a refrigerator is 15% by mass or more based on the total amount of refrigerant oil and refrigerant.
- difluoromethane 15% by weight or more of pentafluoroethane, 15% by weight or more of 2,3,3,3-tetrafluoropropene, and 15% by weight or more of 1,1,1,2-tetrafluoroethane Containing a medium, to provide applications.
- the present invention is an application of the composition for producing a refrigerating machine oil or a working fluid composition for a refrigerating machine, wherein the composition contains a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less. Containing at least one oxygen oil as a base oil, the refrigerating machine oil is 15% by mass or more of difluoromethane, 15% by mass or more of pentafluoroethane, 15% by mass or more of 2,3,3, based on the total amount of refrigerant.
- the working fluid composition for a refrigerator has a refrigerant oil and a refrigerant total amount of 15 % By weight of difluoromethane, 15% by weight or more of pentafluoroethane, 15% by weight or more of 2,3,3,3-tetrafluoropropene, and 15% by weight or more of 1,1,1,2-tetrafluoroethane Containing a refrigerant containing, provides applications.
- compatibility with a refrigerant containing a predetermined amount of difluoromethane, pentafluoroethane, 2,3,3,3-tetrafluoropropene, and 1,1,1,2-tetrafluoroethane is excellent.
- a refrigerating machine oil and a working fluid composition for a refrigerating machine containing the refrigerating machine oil can be provided.
- the refrigerating machine oil according to the present embodiment contains at least one oxygen-containing oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less as a base oil, and 15% by mass or more of difluoro based on the total amount of refrigerant.
- the working fluid composition for a refrigerator includes a refrigerator oil containing at least one oxygenated oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less as a base oil, and a refrigerant. 15% by weight or more difluoromethane, 15% by weight or more pentafluoroethane, 15% by weight or more 2,3,3,3-tetrafluoropropene, and 15% by weight or more 1,1,1, And a refrigerant containing 2-tetrafluoroethane.
- the working fluid composition for a refrigerator according to the present embodiment includes the refrigerating machine oil according to the present embodiment, 15% by mass or more of difluoromethane, 15% by mass or more of pentafluoroethane, 15% by mass based on the total amount of the refrigerant. % Of 2,3,3,3-tetrafluoropropene and a refrigerant containing 15% by weight of 1,1,1,2-tetrafluoroethane.
- the base oil according to the present embodiment is at least one oxygen-containing oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less.
- the carbon / oxygen molar ratio of the oxygen-containing oil is preferably 3.2 or more and 5.0 or less, more preferably 4.0 or more and 5.0 or less, from the viewpoint of compatibility with the refrigerant and stability. .
- the carbon / oxygen molar ratio may be 2.5 or more and 5.0 or less, 3.2 or more and 5.8 or less, or 4.0 or more and 5.8 or less.
- the carbon / oxygen molar ratio is preferably 2.5 or more, more preferably 3.2 or more, still more preferably 4.0 or more, and preferably 5.8 or less, more preferably 5.0 or less.
- the carbon / oxygen molar ratio can be quantitatively analyzed by a general elemental analysis method.
- Examples of the method for analyzing carbon include a method of analyzing by a thermal conductivity method or a gas chromatography method after conversion to carbon dioxide by combustion.
- As a method for analyzing oxygen a carbon reduction method in which the oxygen is converted into carbon monoxide by carbon and then quantitatively analyzed is generally used, and the Shutze-Schaucher method has been widely put into practical use.
- oxygen-containing oil examples include esters, polyvinyl ethers, polyalkylene glycols, carbonates, ketones, polyphenyl ethers, silicones, polysiloxanes, perfluoroethers, and the like. Esters, polyvinyl ethers or polyalkylene glycols are preferable, and esters are more preferable. preferable.
- esters include aromatic esters, dibasic acid esters, polyol esters, complex esters, carbonate esters, and mixtures thereof, and polyol esters are preferred.
- aromatic ester examples include 1 to 6 valent, preferably 1 to 4 valent, more preferably 1 to 3 valent aromatic carboxylic acid, and an aliphatic alcohol having 1 to 18 carbon atoms, preferably 1 to 12 carbon atoms. Esters are used.
- Specific examples of the monovalent to hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof.
- aliphatic alcohol having 1 to 18 carbon atoms include methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and penta. Examples include decanol, hexadecanol, heptadecanol, octadecanol, and mixtures thereof. These aliphatic alcohols having 1 to 18 carbon atoms may be linear or branched.
- the divalent or higher valent aromatic carboxylic acid may be a simple ester composed of an alcohol composed of one kind of aliphatic alcohol, or a complex ester composed of an alcohol composed of two or more kinds of aliphatic alcohol. May be.
- Dibasic acid esters include dibasic acids having 5 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, Preferred are esters with monohydric alcohols having 1 to 15 carbon atoms having a linear or branched alkyl group such as heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, and the like, and mixtures thereof. Used.
- Polyol ester is an ester synthesized from polyhydric alcohol and fatty acid.
- a saturated fatty acid is preferably used as the fatty acid.
- the number of carbon atoms of the fatty acid is preferably 4 to 20, more preferably 4 to 18, still more preferably 4 to 9, and particularly preferably 5 to 9.
- the number of carbon atoms of the fatty acid may be 5 to 20, or 5 to 18. 4 or more, or 5 or more may be sufficient as the carbon number of a fatty acid, and 20 or less, 18 or less, or 9 or less may be sufficient as it.
- the polyol ester may be a partial ester in which some of the hydroxyl groups of the polyhydric alcohol are not esterified and remain as hydroxyl groups, or may be a complete ester in which all of the hydroxyl groups are esterified. It may be a mixture of an ester and a complete ester.
- the hydroxyl value of the polyol ester is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, still more preferably 3 mgKOH / g or less.
- the proportion of fatty acids having 4 to 20 carbon atoms is preferably 20 to 100 mol%, more preferably 50 to 100 mol%, and 70 to 100 mol%. Is more preferable, and 90 to 100 mol% is particularly preferable.
- fatty acid having 4 to 20 carbon atoms include butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, and pentadecanoic acid. Hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid and icosanoic acid. These fatty acids having 4 to 20 carbon atoms may be linear or branched.
- fatty acids having a branch at the ⁇ -position and / or ⁇ -position are preferred, and 2-methylpropanoic acid, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethylhexadecanoic acid and the like are more preferable, among which 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid are more preferable. preferable.
- the fatty acid may contain a fatty acid other than a fatty acid having 4 to 20 carbon atoms.
- fatty acids other than fatty acids having 4 to 20 carbon atoms include, for example, fatty acids having 21 to 24 carbon atoms.
- Specific examples include linear or branched henicoic acid, linear or branched docosanoic acid, Examples thereof include linear or branched tricosanoic acid and linear or branched tetracosanoic acid.
- a polyhydric alcohol having 2 to 6 hydroxyl groups is preferably used as the polyhydric alcohol constituting the polyol ester.
- the number of carbon atoms of the polyhydric alcohol is preferably 4 to 12, and more preferably 5 to 10.
- hindered alcohols such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, dipentaerythritol are preferable. .
- Pentaerythritol or a mixed ester of pentaerythritol and dipentaerythritol) is more preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.
- the complex ester is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol.
- fatty acid, dibasic acid, monohydric alcohol, and polyol those exemplified in the description of the dibasic acid ester and polyol ester can be used.
- Carbonic acid ester is a compound having a carbonate structure represented by the following formula (A) in the molecule.
- the carbonate ester may have one or more carbonate ester structures in one molecule.
- the above-mentioned aliphatic alcohols and polyols can be used, and polyglycols and those obtained by adding polyglycols to polyols can also be used.
- the carbonate ester may be composed of carbonic acid and a fatty acid and / or dibasic acid.
- carbonate esters having a structure represented by the following general formula (A-1) are preferable.
- X 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group or the following general formula (A-2): Y 2- (OA 3 ) e- (A-2)
- Y 2 represents a hydrogen atom, an alkyl group or a cycloalkyl group
- a 3 represents an alkylene group having 2 to 4 carbon atoms
- e represents an integer of 1 to 50
- a 1 and A 2 may be the same or different and each represents an alkylene group having 2 to 4 carbon atoms
- Y 1 represents a hydrogen atom, an alkyl group or a cycloalkyl group
- Represents a residue of a compound having 3 to 20 hydroxyl groups, a represents an integer of 1 to 20, b represents an integer of 0 to 19 and a + b 3 to 20, c represents an integer of 0 to 50, and d represents an integer of 1 to Each represents an integer of 50]
- X 1 represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a group represented by the general formula (A-2).
- the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 24, preferably 1 to 18, and more preferably 1 to 12.
- the alkyl group may be linear or branched.
- alkyl group having 1 to 24 carbon atoms include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, straight Chain or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or Branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched Heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl
- cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- examples of the alkylene group having 2 to 4 carbon atoms represented by A 3 include an ethylene group, a propylene group, a trimethylene group, a butylene group, a tetramethylene group, a 1-methyltrimethylene group, Examples include 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group and the like.
- Y 2 in the general formula (A-2) represents a hydrogen atom, an alkyl group, or a cycloalkylalkyl group.
- the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 24, preferably 1 to 18, and more preferably 1 to 12.
- the alkyl group may be linear or branched. Specific examples of the alkyl group having 1 to 24 carbon atoms include the groups listed in the description relating to X 1 .
- cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- Y 2 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or
- X 1 is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group represented by the general formula (A-2).
- Specific examples of the compound having 3 to 20 hydroxyl groups with B as a residue include the aforementioned polyols.
- a 1 and A 2 may be the same or different and each represents an alkylene group having 2 to 4 carbon atoms.
- ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene Examples include groups.
- Y 1 is a hydrogen atom, an alkyl group or a cycloalkylalkyl group.
- the number of carbon atoms of the alkyl group is not particularly limited, but is usually 1 to 24, preferably 1 to 18, and more preferably 1 to 12.
- the alkyl group may be linear or branched. Specific examples of the alkyl group having 1 to 24 carbon atoms include the groups listed in the description relating to X 1 .
- cycloalkyl group examples include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.
- Y 1 is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or
- c, d and e represent the degree of polymerization of the polyoxyalkylene moiety. These polyoxyalkylene moieties may be the same or different in the molecule.
- the polymerization mode of the oxyalkylene group is not particularly limited, and may be random copolymerization or block copolymerization.
- Polyvinyl ether has a structural unit represented by the following general formula (1).
- R 1 , R 2 and R 3 may be the same or different from each other and each represents a hydrogen atom or a hydrocarbon group, and R 4 represents a divalent hydrocarbon group or a divalent ether-bonded oxygen-containing carbon atom.
- R 5 represents a hydrocarbon group
- m represents an integer of 0 or more.
- the plurality of R 4 may be the same as or different from each other.
- the number of carbon atoms of the hydrocarbon group represented by R 1 , R 2 and R 3 in the general formula (1) is preferably 1 to 8, more preferably 2 to 7, and still more preferably 3 to 6. Further, at least one of R 1 , R 2 and R 3 in the general formula (1) is preferably a hydrogen atom, and more preferably all are hydrogen atoms.
- the carbon number of the divalent hydrocarbon group and ether-bonded oxygen-containing hydrocarbon group represented by R 4 in the general formula (1) is preferably 1 to 10, more preferably 2 to 8, and still more preferably 3 to 6. is there.
- the divalent ether bond oxygen-containing hydrocarbon group represented by R 4 in the general formula (1) may be, for example, a hydrocarbon group having oxygen in the side chain forming an ether bond.
- R 5 in the general formula (1) is preferably a hydrocarbon group having 1 to 20 carbon atoms.
- the hydrocarbon group include an alkyl group, a cycloalkyl group, a phenyl group, an aryl group, and an arylalkyl group. Among these, an alkyl group is preferable, and an alkyl group having 1 to 5 carbon atoms is more preferable.
- M in the general formula (1) is preferably 0 to 20, more preferably 1 to 18, and still more preferably 2 to 16.
- the average value of m in all structural units constituting the polyvinyl ether is preferably 0-10.
- the polyvinyl ether may be a homopolymer composed of one type selected from the structural unit represented by the general formula (1), or two or more types selected from the structural unit represented by the general formula (1).
- the copolymer comprised by the structural unit represented by General formula (1), and another structural unit may be sufficient.
- the lubricity, insulating properties, hygroscopicity, and the like can be further improved while satisfying compatibility with the refrigerant of the refrigerating machine oil.
- the various characteristics of the refrigerating machine oil can be made desired by appropriately selecting the kind of raw material monomer, the kind of initiator, the ratio of structural units in the copolymer, and the like.
- the copolymer may be either a block copolymer or a random copolymer.
- the copolymer includes the structural unit (1-1) represented by the general formula (1) and R 5 is an alkyl group having 1 to 3 carbon atoms, and the general And a structural unit (1-2) which is an alkyl group represented by the formula (1) and wherein R 5 is an alkyl group having 3 to 20, preferably 3 to 10, and more preferably 3 to 8 carbon atoms.
- R 5 is an alkyl group having 3 to 20, preferably 3 to 10, and more preferably 3 to 8 carbon atoms.
- the molar ratio of the structural unit (1-1) to the structural unit (1-2) is 5: It is preferably 95 to 95: 5, more preferably 20:80 to 90:10, and still more preferably 70:30 to 90:10.
- the molar ratio is within the above range, the compatibility with the refrigerant can be further improved, and the hygroscopicity tends to be lowered.
- the polyvinyl ether may be composed only of the structural unit represented by the general formula (1), but is a copolymer further including a structural unit represented by the following general formula (2). Also good.
- the copolymer may be a block copolymer or a random copolymer.
- R 6 to R 9 may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]
- Polyvinyl ether is a polymerization of a vinyl ether monomer corresponding to general formula (1), or a hydrocarbon monomer having a vinyl ether monomer corresponding to general formula (1) and an olefinic double bond corresponding to general formula (2) And can be produced by copolymerization.
- a vinyl ether monomer corresponding to the structural unit represented by the general formula (1) a monomer represented by the following general formula (3) is preferable.
- R 1, R 2, R 3, R 4, R 5 and m is, R 1, R 2, R 3, R 4, R 5 and the same definition as m, respectively in the general formula (1) Show the contents. ]
- the polyvinyl ether preferably has the following terminal structure (A) or (B).
- R 11 , R 21 and R 31 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 41 is a divalent divalent hydrocarbon having 1 to 10 carbon atoms.
- m is 2 or more, the plurality of R 41 may be the same as or different from each other.
- R 61 , R 71 , R 81 and R 91 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. ]
- R 12 , R 22 and R 32 may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R 42 is a divalent divalent hydrocarbon having 1 to 10 carbon atoms.
- R 42 represents a hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group
- R 52 represents a hydrocarbon group having 1 to 20 carbon atoms
- m represents the same definition as m in formula (1).
- the plurality of R 41 may be the same or different.
- R 62 , R 72 , R 82 and R 92 may be the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
- R 13 , R 23 and R 33 may be the same or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms. ]
- polyvinyl ether compounds the following polyvinyl ethers (a), (b), (c), (d) and (e) are particularly suitable as the main component (base oil) of the refrigerating machine oil.
- A One end is represented by the general formula (4) or (5), and the other end has a structure represented by the general formula (6) or (7), and R in the general formula (1) 1 , R 2 and R 3 are all hydrogen atoms, m is an integer of 0 to 4, R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R 5 is a hydrocarbon group having 1 to 20 carbon atoms.
- R 1 , R 2 and R 3 in the general formula (1) are all hydrogen atoms, m is an integer of 0 to 4, R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, R 5 Polyvinyl ether in which is a hydrocarbon group having 1 to 20 carbon atoms.
- R 1 , R 2 and R 3 in the general formula (1) are all hydrogen atoms, m is an integer of 0 to 4, R 4 is a divalent hydrocarbon group having 2 to 4 carbon atoms, R 5 Polyvinyl ether in which is a hydrocarbon group having 1 to 20 carbon atoms.
- R 5 in the general formula (1) is a hydrocarbon group having 1 to 3 carbon atoms; Polyvinyl ether having a structural unit in which R 5 is a hydrocarbon group having 3 to 20 carbon atoms.
- the polyvinyl ether is preferably a polyvinyl ether having a low degree of unsaturation derived from an unsaturated group or the like.
- the degree of unsaturation of polyvinyl ether is preferably 0.04 meq / g or less, more preferably 0.03 meq / g or less, and still more preferably 0.02 meq / g or less.
- the peroxide value of polyvinyl ether is preferably 10.0 meq / kg or less, more preferably 5.0 meq / kg or less, and even more preferably 1.0 meq / kg.
- the carbonyl value of polyvinyl ether is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and still more preferably 20 ppm by weight or less.
- the hydroxyl value of polyvinyl ether is preferably 10 mgKOH / g or less, more preferably 5 mgKOH / g or less, and still more preferably 3 mgKOH / g or less.
- the degree of unsaturation, the peroxide value, and the carbonyl value are values measured by a standard oil analysis test method established by the Japan Oil Chemists' Society.
- the degree of unsaturation in the present invention refers to reacting a sample with a Wis solution (ICl-acetic acid solution) and leaving it in the dark, then reducing excess ICl to iodine and titrating the iodine with sodium thiosulfate. Then, the iodine value is calculated, and the iodine value is a value (meq / g) converted into a vinyl equivalent.
- the peroxide value in the present invention refers to a value (meq / kg) obtained by adding potassium iodide to a sample, titrating the resulting free iodine with sodium thiosulfate, and converting this free iodine to the number of milliequivalents per 1 kg of the sample.
- the carbonyl value in the present invention refers to a calibration value obtained by reacting 2,4-dinitrophenylhydrazine on a sample to produce a chromogenic quinoid ion, and measuring the absorbance at 480 nm of this sample in advance using cinnamaldehyde as a standard substance. The value (weight ppm) converted into the amount of carbonyl based on the line.
- the hydroxyl value in the present invention means a hydroxyl value measured according to JIS K0070: 1992.
- Polyalkylene glycol may have various chemical structures, but polyethylene glycol, polypropylene glycol, polybutylene glycol and the like are exemplified as basic compounds.
- the unit structure of polyalkylene glycol is oxyethylene, oxypropylene, or oxybutylene.
- Polyalkylene glycols having these unit structures can be obtained by ring-opening polymerization using monomers ethylene oxide, propylene oxide, and butylene oxide as raw materials.
- Examples of the polyalkylene glycol include a compound represented by the following general formula (9).
- R ⁇ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a residue of a compound having 2 to 8 hydroxyl groups
- R ⁇ represents carbon
- R 2 represents an alkylene group having 2 to 4
- R ⁇ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms
- f represents an integer of 1 to 80
- g represents 1 to Represents an integer of 8.
- the alkyl group represented by R ⁇ and R ⁇ may be linear, branched, or cyclic.
- the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6. When the number of carbon atoms in the alkyl group exceeds 10, the compatibility with the refrigerant tends to decrease.
- the alkyl group part of the acyl group represented by R ⁇ and R ⁇ may be linear, branched or cyclic.
- the carbon number of the acyl group is preferably 2 to 10, more preferably 2 to 6. If the number of carbon atoms in the acyl group exceeds 10, the compatibility with the refrigerant may be reduced and phase separation may occur.
- the groups represented by R ⁇ and R ⁇ are both alkyl groups or are both acyl groups
- the groups represented by R ⁇ and R ⁇ may be the same or different.
- g is 2 or more, a plurality of groups represented by R ⁇ and R ⁇ in the same molecule may be the same or different.
- the compound When the group represented by R ⁇ is a residue of a compound having 2 to 8 hydroxyl groups, the compound may be linear or cyclic.
- R ⁇ and R ⁇ are preferably an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms), particularly methyl.
- the group is preferable from the viewpoint of compatibility with the refrigerant.
- both R ⁇ and R ⁇ are preferably alkyl groups (more preferably alkyl groups having 1 to 4 carbon atoms), and both are more preferably methyl groups.
- R ⁇ or R ⁇ is an alkyl group (more preferably an alkyl group having 1 to 4 carbon atoms), and the other is a hydrogen atom, and one is methyl It is more preferable that the other is a hydrogen atom. From the viewpoint of lubricity and sludge solubility, both R ⁇ and R ⁇ are preferably hydrogen atoms.
- R ⁇ in the general formula (9) represents an alkylene group having 2 to 4 carbon atoms.
- an alkylene group include an ethylene group, a propylene group, and a butylene group.
- examples of the oxyalkylene group of the repeating unit represented by OR ⁇ include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- the oxyalkylene group in the same molecule may be composed of one kind of oxyalkylene group or may be composed of two or more kinds of oxyalkylene groups.
- a copolymer containing an oxyethylene group (EO) and an oxypropylene group (PO) from the viewpoint of compatibility with a refrigerant and viscosity-temperature characteristics.
- the ratio of the oxyethylene group to the total of the oxyethylene group and the oxypropylene group (EO / (PO + EO)) is 0.1 to 0.00 from the viewpoint of baking load and viscosity-temperature characteristics. It is preferably in the range of 8, more preferably in the range of 0.3 to 0.6.
- the value of EO / (PO + EO) is preferably in the range of 0 to 0.5, more preferably in the range of 0 to 0.2, and 0 (ie, propylene Most preferred is an oxide homopolymer).
- f represents the number of repetitions (polymerization degree) of the oxyalkylene group OR ⁇ and is an integer of 1 to 80.
- g is an integer of 1 to 8.
- R ⁇ is an alkyl group or an acyl group
- g is 1.
- R ⁇ is a residue of a compound having 2 to 8 hydroxyl groups
- g is the number of hydroxyl groups that the compound has.
- the product of f and g (f ⁇ g) is not particularly limited, but in order to satisfy the required performance as a refrigerating machine oil in a well-balanced manner, the average value of f ⁇ g is preferably 6 to 80.
- the number average molecular weight of the polyalkylene glycol represented by the general formula (9) is preferably 500 to 3000, more preferably 600 to 2000, more preferably 600 to 1500, and n is the number average molecular weight of the polyalkylene glycol. It is preferable that the number satisfies the above conditions. When the number average molecular weight of the polyalkylene glycol is too low, the lubricity in the presence of the refrigerant is insufficient. On the other hand, when the number average molecular weight is too high, the composition range showing compatibility with the refrigerant under low temperature conditions is narrowed, and the refrigerant compressor is poorly lubricated and heat exchange in the evaporator is liable to occur.
- the hydroxyl value of the polyalkylene glycol is not particularly limited, but is preferably 100 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 30 mgKOH / g or less, and most preferably 10 mgKOH / g or less.
- Polyalkylene glycol can be synthesized using a known method ("alkylene oxide polymer", Mitsuta Shibata et al., Kaibundo, issued on November 20, 1990).
- alkylene oxide polymer Mitsuta Shibata et al., Kaibundo, issued on November 20, 1990.
- an alcohol R ⁇ OH; R ⁇ is the formula representing the (9) R alpha same definition in) the by addition polymerization of one or more predetermined alkylene oxide, etherified or further terminal hydroxyl group
- esterification the polyalkylene glycol represented by the general formula (9) is obtained.
- the resulting polyalkylene glycol may be either a random copolymer or a block copolymer, but tends to be more excellent in oxidation stability and lubricity. Therefore, a block copolymer is preferable, and a random copolymer is preferable because it tends to be more excellent in low-temperature fluidity.
- the kinematic viscosity of polyalkylene glycol at 100 ° C. is preferably 5 to 20 mm 2 / s, preferably 6 to 18 mm 2 / s, more preferably 7 to 16 mm 2 / s, and still more preferably 8 to 15 mm 2 / s. Most preferably, it is 10 to 15 mm 2 / s.
- the kinematic viscosity at 100 ° C. is less than the lower limit, the lubricity in the presence of the refrigerant becomes insufficient.
- the kinematic viscosity at 40 ° C. of the polyalkylene glycol is preferably 10 to 200 mm 2 / s, more preferably 20 to 150 mm 2 / s at 40 ° C. If the kinematic viscosity at 40 ° C. is less than 10 mm 2 / s, the lubricity and the sealing performance of the compressor tend to be reduced. If the kinematic viscosity exceeds 200 mm 2 / s, it is compatible with the refrigerant under low temperature conditions.
- the composition range showing the above becomes narrow, and the lubrication failure of the refrigerant compressor and the heat exchange in the evaporator tend to be hindered.
- the pour point of the polyalkylene glycol represented by the general formula (9) is preferably ⁇ 10 ° C. or less, more preferably ⁇ 20 to ⁇ 50 ° C.
- the refrigerating machine oil tends to solidify in the refrigerant circulation system at low temperatures.
- an alkylene oxide such as propylene oxide may cause a side reaction to form an unsaturated group such as an aryl group in the molecule.
- an unsaturated group such as an aryl group in the molecule.
- the thermal stability of the polyalkylene glycol itself is reduced, a polymer is produced and sludge is produced, or the antioxidant property (antioxidant property) is lowered. Therefore, a phenomenon such as generation of peroxide is likely to occur.
- a peroxide when a peroxide is generated, it decomposes to generate a compound having a carbonyl group, and the compound having a carbonyl group generates sludge, which easily causes capillary clogging.
- the polyalkylene glycol according to this embodiment is preferably a polyalkylene glycol having a low degree of unsaturation derived from an unsaturated group or the like.
- the degree of unsaturation of the polyalkylene glycol is preferably 0.04 meq / g or less, more preferably 0.03 meq / g or less, and most preferably 0.02 meq / g or less.
- the peroxide value is preferably 10.0 meq / kg or less, more preferably 5.0 meq / kg or less, and most preferably 1.0 meq / kg.
- the carbonyl value is preferably 100 ppm by weight or less, more preferably 50 ppm by weight or less, and most preferably 20 ppm by weight or less.
- the reaction temperature when reacting propylene oxide is preferably 120 ° C. or lower (more preferably 110 ° C. or lower). If an alkaline catalyst is used in the production, the use of an inorganic adsorbent such as activated carbon, activated clay, bentonite, dolomite, aluminosilicate, etc. to remove this may reduce the degree of unsaturation. it can.
- an inorganic adsorbent such as activated carbon, activated clay, bentonite, dolomite, aluminosilicate, etc.
- the polyalkylene glycol needs to have a carbon / oxygen molar ratio within a predetermined range.
- a polymer having the molar ratio within the above range can be produced. can do.
- the base oil may further contain, for example, a hydrocarbon oil such as mineral oil, olefin polymer, naphthalene compound, and alkylbenzene in addition to the oxygen-containing oil.
- a hydrocarbon oil such as mineral oil, olefin polymer, naphthalene compound, and alkylbenzene
- the content of the oxygen-containing oil is preferably 5% by mass or more, more preferably 30% by mass or more, and still more preferably 95% by mass or more based on the total amount of the base oil.
- the refrigerating machine oil may further contain various additives as necessary.
- additives include acid scavengers, antioxidants, extreme pressure agents, oiliness agents, antifoaming agents, metal deactivators, antiwear agents, viscosity index improvers, pour point depressants, cleaning dispersants, frictions. Examples thereof include a regulator and a rust inhibitor.
- the content of the additive is preferably 5% by mass or less, and more preferably 2% by mass or less, based on the total amount of refrigerating machine oil.
- the refrigerating machine oil preferably further contains an acid scavenger from the viewpoint of further improving the thermal and chemical stability.
- the acid scavenger include epoxy compounds and carbodiimide compounds.
- the epoxy compound is not particularly limited, and examples thereof include glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, oxirane compounds, alkyl oxirane compounds, alicyclic epoxy compounds, epoxidized fatty acid monoesters, and epoxidized vegetable oils. These epoxy compounds can be used individually by 1 type or in combination of 2 or more types.
- Examples of glycidyl ether type epoxy compounds include n-butylphenyl glycidyl ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether Octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl glycidyl ether, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-eth
- glycidyl ester type epoxy compound examples include glycidyl benzoate, glycidyl neodecanoate, glycidyl-2,2-dimethyloctanoate, glycidyl acrylate, and glycidyl methacrylate.
- the alicyclic epoxy compound is a compound having a partial structure represented by the following general formula (10), in which carbon atoms constituting the epoxy group directly constitute an alicyclic ring.
- Examples of the alicyclic epoxy compounds include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxycyclohexyl).
- Methyl) adipate exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3-yl)- Spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methylcyclohexane, 4 -Epoxyethyl-1,2-epoxycyclohexane.
- allyloxirane compound examples include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.
- alkyloxirane compounds examples include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1, 2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1, Examples include 2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, and 1,2-epoxyicosane.
- Examples of the epoxidized fatty acid monoester include esters of an epoxidized fatty acid having 12 to 20 carbon atoms and an alcohol having 1 to 8 carbon atoms, phenol, or alkylphenol.
- esters of an epoxidized fatty acid having 12 to 20 carbon atoms and an alcohol having 1 to 8 carbon atoms, phenol, or alkylphenol are preferably used.
- butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.
- Examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.
- the carbodiimide compound is not particularly limited, and for example, dialkylcarbodiimide, diphenylcarbodiimide, and bis (alkylphenyl) carbodiimide can be used.
- dialkyl carbodiimide examples include diisopropyl carbodiimide and dicyclohexyl carbodiimide.
- bis (alkylphenyl) carbodiimide examples include ditolylcarbodiimide, bis (isopropylphenyl) carbodiimide, bis (diisopropylphenyl) carbodiimide, bis (triisopropylphenyl) carbodiimide, bis (butylphenyl) carbodiimide, bis (dibutylphenyl) carbodiimide, bis (Nonylphenyl) carbodiimide and the like can be mentioned.
- the refrigerating machine oil preferably further contains an antiwear agent among the above-mentioned additives.
- Suitable antiwear agents include, for example, phosphate esters, thiophosphate esters, sulfide compounds, and zinc dialkyldithiophosphates.
- phosphate esters triphenyl phosphate (TPP) and tricresyl phosphate (TCP) are preferable.
- TPP triphenyl phosphate
- TCP tricresyl phosphate
- thiophosphates triphenyl phosphorothioate
- sulfide compounds monosulfide compounds are preferable from the viewpoints of ensuring the stability of the refrigerating machine oil and suppressing the deterioration of copper frequently used in the refrigeration equipment.
- the refrigerating machine oil preferably further contains an antioxidant among the above-mentioned additives.
- Antioxidants include di-tert. Examples thereof include phenol compounds such as butyl-p-cresol and amine compounds such as alkyldiphenylamine.
- the refrigerating machine oil preferably contains 0.02 to 0.5% by mass of a phenolic compound as an antioxidant based on the total amount of the refrigerating machine oil.
- the refrigerating machine oil preferably further contains a friction modifier, an extreme pressure agent, a rust inhibitor, a metal deactivator, and an antifoaming agent among the above-mentioned additives.
- the friction modifier include aliphatic amines, aliphatic amides, aliphatic imides, alcohols, esters, phosphate ester amine salts, phosphite ester amine salts, and the like.
- extreme pressure agents include sulfurized olefins and sulfurized fats and oils.
- the rust preventive agent include esters or partial esters of alkenyl succinic acid.
- the metal deactivator include benzotriazole and benzotriazole derivatives.
- antifoaming agents include silicone compounds and polyester compounds.
- the content of the base oil in the refrigerating machine oil is 80% by mass or more based on the total amount of refrigerating machine oil in order to be excellent in characteristics required for refrigerating machine oil such as lubricity, compatibility, thermal / chemical stability, and electrical insulation. It is preferable that it is 90 mass% or more, and it is still more preferable that it is 95 mass% or more.
- the kinematic viscosity of the refrigerating machine oil at 40 ° C. may be preferably 3 to 1000 mm 2 / s, more preferably 4 to 500 mm 2 / s, and most preferably 5 to 400 mm 2 / s.
- the kinematic viscosity at 40 ° C. of the refrigerating machine oil is preferably 3 mm 2 / s or more, more preferably 4 mm 2 / s or more, still more preferably 5 mm 2 / s or more, preferably 1000 mm 2 / s or less, more preferably May be 500 mm 2 / s or less, more preferably 400 mm 2 / s or less.
- the kinematic viscosity of the refrigerating machine oil at 100 ° C. may be preferably 1 to 100 mm 2 / s, more preferably 2 to 50 mm 2 / s.
- the kinematic viscosity at 100 ° C. of the refrigerating machine oil may be preferably 1 mm 2 / s or more, more preferably 2 mm 2 / s or more, preferably 100 mm 2 / s or less, more preferably 50 mm 2 / s or less. Good.
- the volume resistivity of the refrigerating machine oil is not particularly limited, but is preferably 1.0 ⁇ 10 9 ⁇ ⁇ m or more, more preferably 1.0 ⁇ 10 10 ⁇ ⁇ m or more, and most preferably 1.0 ⁇ 10 11 ⁇ . -It may be m or more. In particular, when it is used for a hermetic refrigerator, high electrical insulation tends to be required.
- the volume resistivity in this invention means the value in 25 degreeC measured based on JISC2101: 1999 "electrical insulation oil test method".
- the water content of the refrigerating machine oil is not particularly limited, but may be preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less, based on the total amount of refrigerating machine oil.
- the moisture content is required to be small from the viewpoint of the influence on the thermal / chemical stability and electrical insulation of the refrigerator oil.
- the acid value of the refrigerating machine oil is not particularly limited, but is preferable in order to prevent corrosion of the metal used in the refrigerating machine or piping and to prevent decomposition of the ester when the refrigerating machine oil contains an ester. May be 1.0 mg KOH / g or less, more preferably 0.1 mg KOH / g or less.
- the acid value in the present invention means an acid value measured according to JIS K2501: 2003 “Petroleum products and lubricants—neutralization number test method”.
- the ash content of the refrigerating machine oil is not particularly limited, but may be preferably 100 ppm or less, more preferably 50 ppm or less in order to increase the thermal / chemical stability of the refrigerating machine oil according to this embodiment and suppress the generation of sludge and the like.
- the ash content in the present invention means an ash value measured according to JIS K2272: 1998 “Crude oil and petroleum products—Ash and sulfate ash test methods”.
- the pour point of the refrigerating machine oil is preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower, and further preferably ⁇ 30 ° C. or lower.
- the pour point in the present invention means a pour point measured according to JIS K2269.
- a composition containing at least one oxygen-containing oil as a base oil and further containing the various additives described above is used as a component of the refrigerating machine oil used together with the refrigerant according to the present embodiment, or It is suitably used as a constituent of a working fluid composition for a refrigerator that contains the refrigerant according to the present embodiment.
- the oxygen-containing oil having a carbon / oxygen molar ratio of 2.5 or more and 5.8 or less, and the various additives described above are used in the refrigerating machine oil or the refrigerating machine oil used in the present embodiment together with the refrigerant according to the present embodiment. It is used suitably for manufacture of the working fluid composition for refrigerators containing the said refrigerant
- the refrigerating machine oil according to this embodiment is used together with the refrigerant according to this embodiment.
- the working fluid composition for refrigerators according to the present embodiment contains the refrigerant according to the present embodiment.
- the content of each refrigerant in tetrafluoroethane (HFC-134a) may be 15% by mass or more and 20% by mass or more based on the total amount of the refrigerant.
- the content of each of these refrigerants may be 35% by mass or less, or 30% by mass or less.
- the content of each of these refrigerants may be the same or different.
- the refrigerant according to the present embodiment includes difluoromethane (HFC-32), pentafluoroethane (HFC-125), 2,3,3,3-tetrafluoropropene (HFO-1234yf), and 1,1,1,2 -In addition to tetrafluoroethane (HFC-134a), it may further contain other known refrigerants such as other saturated fluorinated hydrocarbon refrigerants and other unsaturated fluorinated hydrocarbon refrigerants.
- HFC-134 1,1,2,2-tetrafluoroethane
- HFC-152a 1,1-difluoroethane
- fluoroethane HFC-161
- HFC-227ea 1,1,1,2,3,3-heptafluoropropane
- HFC-236ea 1,1,1,3,3 , 3-hexafluoropropane
- HFC-236fa 1,1,1,3,3-pentafluoropropane
- HFC-245fa 1,1,1,3,3-pentafluorobutane
- HFO-1225ye 1,2,3,3,3-pentafluoropropene
- HFO-1234ze 1,3,3,3-tetrafluoropropene
- Examples include 2,3,3-tetrafluoropropene (HFO-1234ye) and 3,3,3-trifluoropropene (HFO-1243zf).
- the content of the refrigerating machine oil in the working fluid composition for a refrigerating machine is not particularly limited, but may preferably be 1 to 500 parts by mass, more preferably 2 to 400 parts by mass with respect to 100 parts by mass of the refrigerant.
- the working fluid composition for a refrigerator according to the present embodiment is preferably used for a room air conditioner having a reciprocating or rotating hermetic compressor, a refrigerator, or an open or hermetic car air conditioner.
- the working fluid composition for refrigerating machine and the refrigerating machine oil according to the present embodiment are preferably used for a dehumidifier, a water heater, a freezer, a freezer / refrigerated warehouse, a vending machine, a showcase, a cooling device for a chemical plant, and the like.
- the working fluid composition for refrigerating machine and the refrigerating machine oil according to this embodiment are also preferably used for those having a centrifugal compressor.
- Base oil 10 Polymer of ethyl vinyl ether (Mw: 890)
- Test oils 1 to 14 having the compositions shown in Tables 3 to 5 were prepared using the base oils 1 to 10 and the following additives.
- Additive 1 Glycidyl neodecanoate additive 2: 2-ethylhexyl glycidyl ether additive 3: tricresyl phosphate additive 4: 2,6-di-tert. -Butyl-p-cresol
- Refrigerants R448A and R449A used in the stability test and the refrigerant compatibility test described later are refrigerants having the following compositions (content is based on the total amount of refrigerant).
- R448A HFC-32 (26 mass%), HFC-125 (26 mass%), HFO-1234yf (20 mass%), HFC-134a (21 mass%), HFO-1234ze (E) (7 mass%)
- R449A HFC-32 (24.3 mass%), HFC-125 (24.7 mass%), HFO-1234yf (25.3 mass%), HFC-134a (25.7 mass%)
- the stability test was performed according to JIS K2211: 2009 (autoclave test). Specifically, 80 g of test oil whose water content was adjusted to 100 ppm was weighed into an autoclave, and the catalyst (iron, copper, and aluminum wires, each having an outer diameter of 1.6 mm ⁇ length of 50 mm), and R448A After enclosing 20 g of (refrigerant), it was heated to 140 ° C., and the acid value (JIS C2101: 1999) of the sample oil after 160 hours was measured.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Emergency Medicine (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
Abstract
Description
Y2-(OA3)e- (A-2)
(上記式(A-2)中、Y2は水素原子、アルキル基又はシクロアルキル基を示し、A3は炭素数2~4のアルキレン基を示し、eは1~50の整数を示す)で表される基を示し、A1及びA2は同一でも異なっていてもよく、それぞれ炭素数2~4のアルキレン基を示し、Y1は水素原子、アルキル基又はシクロアルキル基を示し、Bは水酸基3~20個を有する化合物の残基を示し、aは1~20、bは0~19でかつa+b=3~20となる整数を示し、cは0~50の整数、dは1~50の整数をそれぞれ示す]
(a)一方の末端が一般式(4)又は(5)で表され、かつ他方の末端が一般式(6)又は(7)で表される構造を有し、一般式(1)におけるR1、R2及びR3がいずれも水素原子、mが0~4の整数、R4が炭素数2~4の二価の炭化水素基、R5が炭素数1~20の炭化水素基であるポリビニルエーテル。
(b)一般式(1)で表される構造単位のみを有するものであって、一方の末端が一般式(4)で表され、かつ他方の末端が一般式(6)で表される構造を有し、一般式(1)におけるR1、R2及びR3がいずれも水素原子、mが0~4の整数、R4が炭素数2~4の二価の炭化水素基、R5が炭素数1~20の炭化水素基であるポリビニルエーテル。
(c)一方の末端が一般式(4)又は(5)で表され、かつ他方の末端が一般式(8)で表される構造を有し、一般式(1)におけるR1、R2及びR3がいずれも水素原子、mが0~4の整数、R4が炭素数2~4の二価の炭化水素基、R5が炭素数1~20の炭化水素基であるポリビニルエーテル。
(d)一般式(1)で表される構造単位のみを有するものであって、一方の末端が一般式(5)で表され、かつ他方の末端が一般式(8)で表される構造を有し、一般式(1)におけるR1、R2及びR3がいずれも水素原子、mが0~4の整数、R4が炭素数2~4の二価の炭化水素基、R5が炭素数1~20の炭化水素基であるポリビニルエーテル。
(e)上記(a),(b),(c)及び(d)のいずれかであって、一般式(1)におけるR5が炭素数1~3の炭化水素基である構造単位と該R5が炭素数3~20の炭化水素基である構造単位とを有するポリビニルエーテル。
Rα-[(ORβ)f-ORγ]g (9)
[式(1)中、Rα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2~8個の水酸基を有する化合物の残基を表し、Rβは炭素数2~4のアルキレン基を表し、Rγは水素原子、炭素数1~10のアルキル基又は炭素数2~10のアシル基を表し、fは1~80の整数を表し、gは1~8の整数を表す。]
iC4:2-メチルプロパン酸
nC5:n-ペンタン酸
iC8:2-エチルヘキサン酸
iC9:3,5,5-トリメチルヘキサン酸
nC10:n-デカン酸
iC18:2-エチルヘキサデカン酸
nC22:ドコサン酸
PET:ペンタエリスリトール
基油10:エチルビニルエーテルの重合体(Mw:890)
添加剤1:グリシジルネオデカノエート
添加剤2:2-エチルヘキシルグリシジルエーテル
添加剤3:トリクレジルホスフェート
添加剤4:2,6-ジ-tert.-ブチル-p-クレゾール
R448A:HFC-32(26質量%)、HFC-125(26質量%)、HFO-1234yf(20質量%)、HFC-134a(21質量%)、HFO-1234ze(E)(7質量%)
R449A:HFC-32(24.3質量%)、HFC-125(24.7質量%)、HFO-1234yf(25.3質量%)、HFC-134a(25.7質量%)
安定性試験は、JIS K2211:2009(オートクレーブテスト)に準拠して行った。具体的には、含有水分量を100ppmに調整した供試油80g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×長さ50mm)、及び、R448A(冷媒)20gを封入した後、140℃に加熱し、160時間後の供試油の酸価(JIS C2101:1999)を測定した。
JIS K2211:2009「冷凍機油」の「冷媒との相溶性試験方法」に準拠して、R448A又はR449A(冷媒)10gに対して供試油を10g配合し、冷媒と冷凍機油とが0℃において相互に溶解しているかを観察した。
Claims (5)
- 炭素/酸素モル比が2.5以上5.8以下である含酸素油の少なくとも1種を基油として含有し、
冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒と共に用いられる、冷凍機油。 - 前記含酸素油として、炭素数4~20の脂肪酸の割合が20~100モル%である脂肪酸と多価アルコールとのエステルを含有する、請求項1に記載の冷凍機油。
- 請求項1又は2に記載の冷凍機油と、
冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒と、
を含有する、冷凍機用作動流体組成物。 - 組成物の冷凍機油又は冷凍機用作動流体組成物への応用であって、
前記組成物は、炭素/酸素モル比が2.5以上5.8以下である含酸素油の少なくとも1種を基油として含有し、
前記冷凍機油は、冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒と共に用いられ、
前記冷凍機用作動流体組成物は、前記冷凍機油と、冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒とを含有する、応用。 - 組成物の冷凍機油又は冷凍機用作動流体組成物の製造のための応用であって、
前記組成物は、炭素/酸素モル比が2.5以上5.8以下である含酸素油の少なくとも1種を基油として含有し、
前記冷凍機油は、冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒と共に用いられ、
前記冷凍機用作動流体組成物は、前記冷凍機油と、冷媒全量基準で、15質量%以上のジフルオロメタン、15質量%以上のペンタフルオロエタン、15質量%以上の2,3,3,3-テトラフルオロプロペン、及び15質量%以上の1,1,1,2-テトラフルオロエタンを含有する冷媒とを含有する、応用。
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2016552884A JPWO2016056392A1 (ja) | 2014-10-09 | 2015-09-24 | 冷凍機油及び冷凍機用作動流体組成物 |
KR1020237005875A KR102605776B1 (ko) | 2014-10-09 | 2015-09-24 | 냉동기유 및 냉동기용 작동 유체 조성물 |
CN201580054263.3A CN106795446A (zh) | 2014-10-09 | 2015-09-24 | 冷冻机油和冷冻机用工作流体组合物 |
KR1020177012175A KR102504399B1 (ko) | 2014-10-09 | 2015-09-24 | 냉동기유 및 냉동기용 작동 유체 조성물 |
US15/516,150 US10023823B2 (en) | 2014-10-09 | 2015-09-24 | Refrigerator oil and working fluid composition for refrigerator |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2014207798 | 2014-10-09 | ||
JP2014-207798 | 2014-10-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2016056392A1 true WO2016056392A1 (ja) | 2016-04-14 |
Family
ID=55653010
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2015/076946 WO2016056392A1 (ja) | 2014-10-09 | 2015-09-24 | 冷凍機油及び冷凍機用作動流体組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US10023823B2 (ja) |
JP (3) | JPWO2016056392A1 (ja) |
KR (2) | KR102605776B1 (ja) |
CN (1) | CN106795446A (ja) |
TW (1) | TWI576424B (ja) |
WO (1) | WO2016056392A1 (ja) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018190354A1 (ja) * | 2017-04-12 | 2018-10-18 | 出光興産株式会社 | 冷凍機油、及び冷凍機用組成物 |
JP2020180618A (ja) * | 2020-07-21 | 2020-11-05 | 東芝キヤリア株式会社 | 密閉型圧縮機および冷凍サイクル装置 |
US11384271B2 (en) * | 2018-04-02 | 2022-07-12 | Eneos Corporation | Refrigerator, refrigerator oil, working fluid composition for refrigerator |
WO2023157867A1 (ja) * | 2022-02-15 | 2023-08-24 | 出光興産株式会社 | 冷凍機油組成物及び冷凍機用混合組成物 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6937108B2 (ja) * | 2016-11-04 | 2021-09-22 | 日立ジョンソンコントロールズ空調株式会社 | 電動圧縮機及び冷凍空調装置 |
CN110343509B (zh) * | 2018-04-02 | 2021-09-14 | 江西天宇化工有限公司 | 一种不可燃且能降低温室效应的混合制冷剂及其应用 |
WO2019208722A1 (ja) * | 2018-04-25 | 2019-10-31 | ダイキン工業株式会社 | 冷媒を含有する組成物、その用途、それを利用する冷凍方法及びそれを有する冷凍機 |
CN111944489B (zh) * | 2020-07-21 | 2021-10-29 | 浙江衢化氟化学有限公司 | 一种含有氟代烃的组合物及其制备方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012509390A (ja) * | 2008-11-19 | 2012-04-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | テトラフルオロプロペン組成物およびその使用 |
JP2012526182A (ja) * | 2009-05-08 | 2012-10-25 | ハネウェル・インターナショナル・インコーポレーテッド | 熱伝達組成物および熱伝達方法 |
JP2013529703A (ja) * | 2010-06-22 | 2013-07-22 | アーケマ・インコーポレイテッド | ヒドロフルオロカーボンとヒドロフルオロオレフィンの熱伝達組成物 |
WO2013147048A1 (ja) * | 2012-03-29 | 2013-10-03 | Jx日鉱日石エネルギー株式会社 | 冷凍機用作動流体組成物 |
Family Cites Families (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP3173684B2 (ja) * | 1992-06-04 | 2001-06-04 | 出光興産株式会社 | 圧縮型冷凍機用潤滑油 |
JP4112645B2 (ja) * | 1996-02-05 | 2008-07-02 | 出光興産株式会社 | 圧縮型冷凍機用潤滑油 |
JP3501258B2 (ja) * | 1996-11-18 | 2004-03-02 | 出光興産株式会社 | 冷凍装置及び冷媒圧縮機 |
JPH10159734A (ja) * | 1996-11-28 | 1998-06-16 | Sanyo Electric Co Ltd | 冷凍装置 |
JP5154120B2 (ja) | 2007-03-27 | 2013-02-27 | Jx日鉱日石エネルギー株式会社 | ランキンサイクル発電のタービン用潤滑油及び作動流体組成物 |
JP5435859B2 (ja) * | 2007-11-26 | 2014-03-05 | 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 |
JP5297138B2 (ja) | 2008-10-08 | 2013-09-25 | Jx日鉱日石エネルギー株式会社 | ランキンサイクル発電のタービン用潤滑油及び作動流体組成物 |
US20100122545A1 (en) | 2008-11-19 | 2010-05-20 | E. I. Du Pont De Nemours And Company | Tetrafluoropropene compositions and uses thereof |
US8889031B2 (en) * | 2010-11-30 | 2014-11-18 | Jx Nippon Oil & Energy Corporation | Working fluid composition for refrigerator machine and refrigerating machine oil |
JP2013009488A (ja) | 2011-06-23 | 2013-01-10 | Toyota Motor Corp | 電力復旧システム |
US9169427B2 (en) | 2011-07-13 | 2015-10-27 | Honeywell International Inc. | Low GWP heat transfer compositions containing difluoromethane, a fluorinated ethane and 1,3,3,3-tetrafluoropropene |
US10273394B2 (en) * | 2011-10-26 | 2019-04-30 | Jx Nippon Oil & Energy Corporation | Refrigerating machine working fluid composition and refrigerant oil |
PL2814896T3 (pl) * | 2012-02-13 | 2019-03-29 | The Chemours Company Fc, Llc | Mieszanki chłodnicze zawierające tetrafluoropropen, difluorometan, pentafluoroetan i tetrafluoroetan oraz ich zastosowania |
JP5689428B2 (ja) | 2012-02-22 | 2015-03-25 | Jx日鉱日石エネルギー株式会社 | 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 |
JP5871688B2 (ja) * | 2012-03-29 | 2016-03-01 | Jx日鉱日石エネルギー株式会社 | 冷凍機用作動流体組成物 |
JP5882860B2 (ja) * | 2012-08-30 | 2016-03-09 | Jx日鉱日石エネルギー株式会社 | 潤滑油組成物 |
KR102124305B1 (ko) * | 2012-09-28 | 2020-06-18 | 이데미쓰 고산 가부시키가이샤 | 압축형 냉동기용 윤활유 |
WO2014112417A1 (ja) * | 2013-01-17 | 2014-07-24 | 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 |
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 |
JP6262035B2 (ja) * | 2014-03-14 | 2018-01-17 | Jxtg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 |
JP2015209441A (ja) * | 2014-04-23 | 2015-11-24 | 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 |
JP6681828B2 (ja) * | 2014-05-22 | 2020-04-15 | Jxtg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 |
JP2016098256A (ja) * | 2014-11-18 | 2016-05-30 | Jx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 |
-
2015
- 2015-09-24 US US15/516,150 patent/US10023823B2/en active Active
- 2015-09-24 CN CN201580054263.3A patent/CN106795446A/zh active Pending
- 2015-09-24 JP JP2016552884A patent/JPWO2016056392A1/ja active Pending
- 2015-09-24 KR KR1020237005875A patent/KR102605776B1/ko active IP Right Grant
- 2015-09-24 WO PCT/JP2015/076946 patent/WO2016056392A1/ja active Application Filing
- 2015-09-24 KR KR1020177012175A patent/KR102504399B1/ko active Application Filing
- 2015-10-05 TW TW104132727A patent/TWI576424B/zh active
-
2019
- 2019-06-03 JP JP2019103804A patent/JP6846462B2/ja active Active
-
2021
- 2021-03-01 JP JP2021031556A patent/JP7065222B2/ja active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012509390A (ja) * | 2008-11-19 | 2012-04-19 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | テトラフルオロプロペン組成物およびその使用 |
JP2012526182A (ja) * | 2009-05-08 | 2012-10-25 | ハネウェル・インターナショナル・インコーポレーテッド | 熱伝達組成物および熱伝達方法 |
JP2013529703A (ja) * | 2010-06-22 | 2013-07-22 | アーケマ・インコーポレイテッド | ヒドロフルオロカーボンとヒドロフルオロオレフィンの熱伝達組成物 |
WO2013147048A1 (ja) * | 2012-03-29 | 2013-10-03 | Jx日鉱日石エネルギー株式会社 | 冷凍機用作動流体組成物 |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2018190354A1 (ja) * | 2017-04-12 | 2018-10-18 | 出光興産株式会社 | 冷凍機油、及び冷凍機用組成物 |
JP2018177953A (ja) * | 2017-04-12 | 2018-11-15 | 出光興産株式会社 | 冷凍機油、及び冷凍機用組成物 |
KR20190134648A (ko) * | 2017-04-12 | 2019-12-04 | 이데미쓰 고산 가부시키가이샤 | 냉동기유, 및 냉동기용 조성물 |
EP3611243A4 (en) * | 2017-04-12 | 2020-12-30 | Idemitsu Kosan Co., Ltd. | COOLING OIL AND COMPOSITION FOR REFRIGERATING UNITS |
JP2021121680A (ja) * | 2017-04-12 | 2021-08-26 | 出光興産株式会社 | 冷凍機油、及び冷凍機用組成物 |
JP7095940B2 (ja) | 2017-04-12 | 2022-07-05 | 出光興産株式会社 | 冷凍機油、及び冷凍機用組成物 |
US11518922B2 (en) | 2017-04-12 | 2022-12-06 | Idemitsu Kosan Co., Ltd. | Refrigerator oil and composition for refrigerators |
KR102587463B1 (ko) * | 2017-04-12 | 2023-10-10 | 이데미쓰 고산 가부시키가이샤 | 냉동기유, 및 냉동기용 조성물 |
US11384271B2 (en) * | 2018-04-02 | 2022-07-12 | Eneos Corporation | Refrigerator, refrigerator oil, working fluid composition for refrigerator |
JP2020180618A (ja) * | 2020-07-21 | 2020-11-05 | 東芝キヤリア株式会社 | 密閉型圧縮機および冷凍サイクル装置 |
WO2023157867A1 (ja) * | 2022-02-15 | 2023-08-24 | 出光興産株式会社 | 冷凍機油組成物及び冷凍機用混合組成物 |
Also Published As
Publication number | Publication date |
---|---|
TWI576424B (zh) | 2017-04-01 |
US10023823B2 (en) | 2018-07-17 |
US20170327759A1 (en) | 2017-11-16 |
KR102504399B1 (ko) | 2023-03-02 |
JP6846462B2 (ja) | 2021-03-24 |
KR20230030036A (ko) | 2023-03-03 |
JP7065222B2 (ja) | 2022-05-11 |
KR102605776B1 (ko) | 2023-11-30 |
JP2019163486A (ja) | 2019-09-26 |
JP2021088722A (ja) | 2021-06-10 |
TW201614058A (en) | 2016-04-16 |
JPWO2016056392A1 (ja) | 2017-07-20 |
KR20170063940A (ko) | 2017-06-08 |
CN106795446A (zh) | 2017-05-31 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6262035B2 (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
JP7065222B2 (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
WO2013146683A1 (ja) | 冷凍機用作動流体組成物 | |
WO2015163072A1 (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
WO2013147048A1 (ja) | 冷凍機用作動流体組成物 | |
JP6964586B2 (ja) | 冷凍機油 | |
JP6705834B2 (ja) | 冷凍機油 | |
JP6914908B2 (ja) | 冷凍機油 | |
JP6685277B2 (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
JP6641346B2 (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
JP2019210484A (ja) | 冷凍機油及び冷凍機用作動流体組成物 | |
WO2020158518A1 (ja) | 冷凍機油及び冷凍機油の製造方法 | |
WO2020045452A1 (ja) | 冷凍機油 | |
CN118126756A (zh) | 冷冻机油和冷冻机用工作流体组合物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 15849709 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2016552884 Country of ref document: JP Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 15516150 Country of ref document: US |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
ENP | Entry into the national phase |
Ref document number: 20177012175 Country of ref document: KR Kind code of ref document: A |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 15849709 Country of ref document: EP Kind code of ref document: A1 |