WO2023157867A1 - 冷凍機油組成物及び冷凍機用混合組成物 - Google Patents

冷凍機油組成物及び冷凍機用混合組成物 Download PDF

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Publication number
WO2023157867A1
WO2023157867A1 PCT/JP2023/005182 JP2023005182W WO2023157867A1 WO 2023157867 A1 WO2023157867 A1 WO 2023157867A1 JP 2023005182 W JP2023005182 W JP 2023005182W WO 2023157867 A1 WO2023157867 A1 WO 2023157867A1
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Prior art keywords
oil composition
refrigerating machine
mass
modified silicone
compound
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2023/005182
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English (en)
French (fr)
Japanese (ja)
Inventor
知也 松本
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Publication date
Application filed by Idemitsu Kosan Co Ltd filed Critical Idemitsu Kosan Co Ltd
Priority to US18/726,444 priority Critical patent/US12577448B2/en
Priority to KR1020247026489A priority patent/KR20240150433A/ko
Priority to EP23756392.9A priority patent/EP4481021A4/en
Priority to CN202380021463.3A priority patent/CN118679236A/zh
Priority to JP2024501399A priority patent/JPWO2023157867A1/ja
Publication of WO2023157867A1 publication Critical patent/WO2023157867A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • 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
    • C10M129/16—Ethers
    • C10M129/18—Epoxides
    • 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
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C10M129/66—Epoxidised acids or esters
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M155/00—Lubricating compositions characterised by the additive being a macromolecular compound containing atoms of elements not provided for in groups C10M143/00 - C10M153/00
    • C10M155/02—Monomer containing silicon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
    • C10M169/04—Mixtures of base-materials and additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • 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
    • C09K2205/11—Ethers
    • C09K2205/114—Cyclic ethers
    • 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
    • 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
    • C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/04—Well-defined cycloaliphatic 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
    • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
    • C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/041—Triaryl phosphates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/041—Siloxanes with specific structure containing aliphatic substituents
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/046—Siloxanes with specific structure containing silicon-oxygen-carbon bonds
    • 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
    • C10M2229/00—Organic macromolecular compounds containing atoms of elements not provided for in groups C10M2205/00, C10M2209/00, C10M2213/00, C10M2217/00, C10M2221/00 or C10M2225/00 as ingredients in lubricant compositions
    • C10M2229/04—Siloxanes with specific structure
    • C10M2229/047—Siloxanes with specific structure containing alkylene oxide groups
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/01—Physico-chemical properties
    • C10N2020/02—Viscosity; Viscosity index
    • 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
    • C10N2020/04—Molecular weight; Molecular weight distribution
    • 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
    • C10N2030/04—Detergent property or dispersant property
    • 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
    • C10N2030/08—Resistance to extreme temperature
    • C—CHEMISTRY; METALLURGY
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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
    • C10N2030/10—Inhibition of oxidation, e.g. anti-oxidants
    • C—CHEMISTRY; METALLURGY
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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
    • C10N2030/20—Colour, e.g. dyes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention relates to a refrigerator oil composition and a mixture composition for refrigerators.
  • the term "refrigerating machine mixed composition” refers to a composition obtained by mixing a "refrigerating machine oil composition” and a “refrigerant”.
  • a refrigerator such as a compression refrigerator, generally includes at least a compressor, a condenser, an expansion mechanism (e.g., an expansion valve, etc.), and an evaporator, and a mixed composition for a refrigerator circulates in a closed system. have a structure.
  • Hydrochlorofluorocarbons which have been widely used in the past, have been replaced by fluorocarbon compounds, which have a low environmental load, as refrigerants used in refrigerators such as compression refrigerators.
  • fluorocarbon compounds include saturated fluorocarbon compounds (Hydro- Fluoro-Carbon; hereinafter also referred to as "HFC") is being used.
  • 1,3,3,3-tetrafluoropropene (R1234ze), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,2,3,3, which have low global warming potential (GWP)
  • HFO unsaturated fluorocarbon compounds
  • -tetrafluoropropene (R1234ye)
  • HFOs unsaturated fluorocarbon compounds
  • GWP global warming potential
  • HFCs saturated fluorocarbon compounds
  • their thermal stability at high temperatures is It has the disadvantage of being inferior to Therefore, when the content of the unsaturated fluorocarbon compound (HFO) in the refrigerant increases, there is a problem that the acid value of the refrigerating machine oil composition tends to increase.
  • refrigerators have become more compact and have higher performance, and their operating conditions have become more severe than before. Therefore, refrigerator oil compositions are required to have higher quality than ever before. For example, while the amount of refrigerating machine oil composition used in the equipment is decreasing as the refrigerating machine becomes more compact, the frictional heat in the sliding parts of the compressor due to the harsher operating conditions causes localized high temperatures. It is easy to occur in some places. When the mixed composition for a refrigerator is exposed to such a portion, the acid value of the refrigerator oil composition tends to increase.
  • the present invention has been made in view of such a demand, and effectively increases the acid value even when the content of the unsaturated fluorohydrocarbon compound (HFO) in the refrigerant is increased. It is an object of the present invention to provide a refrigerating machine oil composition capable of suppressing the refrigerating machine oil composition and a mixed composition for a refrigerating machine containing the refrigerating machine oil composition.
  • HFO unsaturated fluorohydrocarbon compound
  • Requirement ( ⁇ ) At least one divalent group represented by the following formula (2) is present in the molecule. • Requirement ( ⁇ ): It has at least one ester group in the molecule.
  • General formula (1) below CxFyHz ( 1 ) [In the general formula (1), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and has one or more carbon-carbon unsaturated bonds in the molecule. ] and the refrigerating machine oil composition according to [1] above.
  • a method for producing a refrigerator oil composition comprising the step of mixing Requirement ( ⁇ ): At least one divalent group represented by the following formula (2) is present in the molecule. • Requirement ( ⁇ ): It has at least one ester group in the molecule.
  • a refrigerating machine oil composition that can effectively suppress an increase in acid value even when the content of an unsaturated fluorocarbon compound (HFO) in the refrigerant is increased, and the refrigerating machine oil composition It becomes possible to provide a mixed composition for a refrigerator containing the machine oil composition.
  • HFO unsaturated fluorocarbon compound
  • the refrigerating machine oil composition of the present embodiment has the following general formula (1) CxFyHz ( 1 ) [In the general formula (1), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and has one or more carbon-carbon unsaturated bonds in the molecule.
  • the refrigerator oil composition of the present embodiment comprises a base oil (A) containing polyvinyl ethers, a modified silicone compound (B), and an epoxy compound (C) that satisfies the following requirements ( ⁇ ) and ( ⁇ ): contains.
  • the present inventors have found that one of the factors that facilitates an increase in the acid value of the refrigerating machine oil composition when the content of the unsaturated fluorocarbon compound (HFO) in the refrigerant increases is the unsaturated fluorocarbon compound in a high-temperature environment.
  • the fluorine content is generated by decomposition of a hydrocarbon compound (HFO)
  • various investigations have been carried out.
  • the refrigerating machine oil composition having the above configuration suppresses an increase in the fluorine concentration in the refrigerating machine oil composition due to the fluorine content generated by the decomposition of the unsaturated fluorocarbon compound (HFO) in a high-temperature environment.
  • an increase in the acid value of a refrigerating machine oil composition can be suppressed.
  • the refrigerating machine oil composition of the present embodiment having the above configuration suppresses an increase in the acid value of the refrigerating machine oil composition by at least one of the following actions (i) and (ii). It is speculated that (i) The action of inhibiting the decomposition of unsaturated fluorocarbon compounds (HFO) in a high-temperature environment.
  • HFO unsaturated fluorocarbon compounds
  • base oil (A) modified silicone compound (B)” and “epoxy compound (C)" are respectively referred to as “component (A)", “component (B)” and Also referred to as “component (C)".
  • the refrigerating machine oil composition of the present embodiment may be composed only of the component (A), the component (B), and the component (C), but the component ( Components other than A), component (B), and component (C) may be contained.
  • the total content of component (A), component (B), and component (C) is preferably 80% by mass or more, more preferably, based on the total amount of the refrigerator oil composition. 85% by mass or more, more preferably 90% by mass or more.
  • the refrigerator oil composition of this embodiment contains a base oil (A).
  • the content of the base oil (A) is preferably 85.5% based on the total amount of the refrigerating machine oil composition, from the viewpoint of the long-term stability required as a refrigerating machine oil composition. It is 0% by mass or more, more preferably 90.0% by mass or more, and still more preferably 92.0% by mass or more.
  • the viewpoint of making it easier to secure the contents of the component (B) and the component (C) in the refrigerating machine oil composition and to make it easier to secure the contents of additives other than the component (B) and the component (C).
  • it is preferably 99.0% by mass or less, more preferably 98.5% by mass or less, and even more preferably 98.0% by mass or less.
  • the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 85.0% by mass to 99.0% by mass, more preferably 90.0% by mass to 98.5% by mass, and still more preferably 92.0% by mass to 98.0% by mass. .
  • the refrigerator oil composition of the present embodiment contains polyvinyl ethers (hereinafter also referred to as “PVE”) as the base oil (A). PVE will be described in detail below.
  • PVE Polyvinyl ethers
  • PVE is a polymer having one or more structural units derived from vinyl ether, and PVE that is used as a base oil in refrigerator oil compositions can be used without particular limitation.
  • PVE may be used individually by 1 type, and may be used in combination of 2 or more type.
  • PVE is preferably a polymer having one or more structural units derived from vinyl ether and having an alkyl group having 1 to 4 carbon atoms in a side chain, from the viewpoint of compatibility with refrigerants.
  • the PVE is preferably a polymer (A-2) having one or more structural units represented by the following general formula (A-2).
  • R 1a , R 2a and R 3a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms.
  • R 4a represents a divalent hydrocarbon group having 2 to 10 carbon atoms.
  • R 5a represents a hydrocarbon group having 1 to 10 carbon atoms.
  • r is the number of repeating units of OR 4a and is usually 0 to 10, preferably 0 to 5, more preferably 0 to 3, still more preferably 0;
  • the plurality of OR 4a may be the same or different from each other.
  • hydrocarbon groups having 1 to 8 carbon atoms represented by R 1a , R 2a and R 3a include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, Alkyl groups such as various heptyl groups and various octyl groups; cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, and various dimethylcyclohexyl groups; phenyl groups, various methylphenyl groups, and various ethylphenyl groups , aryl groups such as various dimethylphenyl groups; arylalkyl groups such as benzyl groups, various phenylethyl groups, and various methylbenzyl groups; and the like.
  • variable means “linear, branched, or cyclic” hydrocarbon groups. , isobutyl group, tert-butyl group, and cyclobutyl group”.
  • positional isomers such as ortho-, meta-, and para-isomers are included, and the same applies hereinafter.
  • the number of carbon atoms in the hydrocarbon group represented by R 1a , R 2a and R 3a is preferably 1-6, more preferably 1-3.
  • R 1a , R 2a and R 3a are each independently preferably a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, still more preferably a hydrogen atom.
  • Examples of the divalent hydrocarbon group having 2 to 10 carbon atoms represented by R 4a include ethylene group, 1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, Divalent aliphatic groups such as various heptylene groups, various octylene groups, various nonylene groups, and various decylene groups; divalent alicyclic groups such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, and propylcyclohexane; various phenylene groups , various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, and various naphthylene groups; divalent alkylaromatic groups having a monovalent binding site; divalent alkylaromatic groups having a binding site in the alkyl group portion of polyalkylaromatic hydrocarbons such as x
  • the number of carbon atoms in the hydrocarbon group represented by R 4a is preferably 2-6, more preferably 2-4.
  • R 4a is preferably a divalent aliphatic group having 2 to 10 carbon atoms, more preferably a divalent aliphatic group having 2 to 4 carbon atoms.
  • Hydrocarbon groups having 1 to 10 carbon atoms represented by R 5a include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups.
  • Alkyl groups such as groups, various nonyl groups, various decyl groups; Cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, and various dimethylcyclohexyl groups; Aryl groups such as phenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups; benzyl groups, various phenylethyl groups, various methylbenzyl groups, various arylalkyl groups such as a phenylpropyl group and various phenylbutyl groups; and the like.
  • Cycloalkyl groups such as cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl
  • the hydrocarbon group represented by R 5a preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms.
  • R 5a is preferably an alkyl group having 1 to 6 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, from the viewpoint of further improving compatibility with the refrigerant.
  • the number of units (degree of polymerization) of the structural unit represented by the general formula (A-2) is appropriately selected according to the kinematic viscosity required for the base oil (A).
  • the polymer having a structural unit represented by the general formula (A-2) may be a homopolymer having only one type of the structural unit, or a copolymer having two or more types of the structural unit. may be When the polymer is a copolymer, the form of copolymerization is not particularly limited, and may be block copolymer, random copolymer or graft copolymer.
  • the polymer (A-2) preferably has a structural unit (a2) in which R5a is an ethyl group.
  • the content of the structural unit (a2) is preferably 70 based on the total amount (100 mol%) of the structural units other than the terminal structural units of the polymer (A-2), from the viewpoint of further improving the refrigerant solubility.
  • mol % or more and 100 mol % or less more preferably 80 mol % or more and 100 mol % or less, still more preferably 90 mol % or more and 100 mol % or less.
  • a monovalent group derived from a saturated hydrocarbon, ether, alcohol, ketone, amide, nitrile or the like may be introduced into the terminal portion of the polymer (A-2).
  • the polymer (A-2) preferably has a group represented by the following general formula (A-2-i) at one end.
  • R 6a , R 7a and R 8a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.
  • a hydrogen group is preferred, and a hydrogen atom or an alkyl group having 1 to 3 carbon atoms is more preferred.
  • hydrocarbon group having 1 to 8 carbon atoms represented by R 6a , R 7a and R 8a the number of carbon atoms represented by R 1a , R 2a and R 3a in the above general formula (A-2)
  • Examples of the hydrocarbon groups of 1 to 8 are the same as those listed above.
  • R 9a represents a divalent hydrocarbon group having 2 to 10 carbon atoms, preferably a divalent hydrocarbon group having 2 to 6 carbon atoms, and 2 to 4 carbon atoms. is more preferred.
  • r1 is the number of repeating units of OR 9a and is usually 0 to 10, preferably 0 to 5, more preferably 0 to 3, still more preferably 0 is.
  • the plurality of OR 9a may be the same or different from each other.
  • the divalent hydrocarbon group having 2 to 10 carbon atoms represented by R 9a the divalent hydrocarbon group having 2 to 10 carbon atoms represented by R 4a in the above general formula (A-2) Same as listed.
  • R 10a represents a hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrocarbon group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms.
  • R 10a is preferably an alkyl group having 1 to 6 carbon atoms when r1 in the general formula (A-2-i) is 0, and when r1 is 1 or more, carbon Alkyl groups of numbers 1 to 4 are preferred.
  • the hydrocarbon group having 1 to 10 carbon atoms represented by R 10a is the same as those listed as the hydrocarbon group having 1 to 10 carbon atoms represented by R 5a in the general formula (A-2). is mentioned.
  • the other terminal portion is the general formula (A-2- i), a group represented by the following general formula (A-2-ii), a group represented by the following general formula (A-2-iii), and a group having an olefinically unsaturated bond Either is preferred.
  • R 6a , R 7a , R 8a , R 9a , R 10a and r1 are defined in general formula (A-2-i) above. is the same as In formula (A-2-ii), R 11a , R 12a and r2 are the same as defined for R 9a , R 10a and r1 in general formula (A-2-i) above.
  • the content of PVE in the base oil (A) is preferably 50 mass based on the total amount of the base oil (A). % to 100% by mass, more preferably 60% to 100% by mass, still more preferably 70% to 100% by mass, even more preferably 80% to 100% by mass, still more preferably 90% to 100% by mass %, and more preferably 100% by mass.
  • the base oil (A) may further contain other base oils within a range that does not impair the effects of the present invention.
  • Other base oils include one or more selected from the group consisting of mineral oils and synthetic oils not falling under the aforementioned PVE.
  • Mineral oils include, for example, atmospheric residual oils obtained by atmospheric distillation of crude oils such as paraffinic crude oils, intermediate crude oils, and naphthenic crude oils; distillates obtained by vacuum distillation of these atmospheric residual oils oil; mineral oil obtained by subjecting the distillate to one or more refining treatments such as solvent deasphalting, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, and hydrorefining;
  • mineral oil may be used individually by 1 type, and may be used in combination of 2 or more types.
  • Synthetic oils that do not fall under the aforementioned PVE include, for example, polyalkylene glycols, poly(oxy)alkylene glycols or copolymers of their monoethers and polyvinyl ethers, polyol esters, polyesters, polycarbonates, ⁇ - Hydrogenated olefin oligomers, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, oils produced by isomerizing GTL WAX (gas-to-liquid wax) produced by the Fischer-Tropsch process, etc. .
  • the base oil (A) contains a synthetic oil that does not correspond to the aforementioned PVE
  • the synthetic oil may be used alone or in combination of two or more.
  • the content of mineral oil is small from the viewpoint of the solubility of the component (B) and the component (C).
  • the mineral oil content is preferably 10% by mass or less, more preferably 5% by mass or less, even more preferably 1% by mass or less, and even more preferably 0.1% by mass or less, based on the total amount of the base oil (A). It should contain no more than 1% by mass, more preferably no mineral oil.
  • the content of synthetic oil that does not correspond to PVE is small from the viewpoint of easily improving the effects of the present invention.
  • the content of the synthetic oil not applicable to PVE is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 1% by mass or less, based on the total amount of the base oil (A). More preferably, it contains no more than 0.1% by mass, and even more preferably, it does not contain synthetic oil that does not correspond to PVE.
  • the 100° C. kinematic viscosity of the base oil (A) is preferably 3 mm 2 /s or more, more preferably 4 mm 2 /s or more, still more preferably 5 mm 2 / s, from the viewpoint of improving lubricating performance (load-bearing performance) and sealing performance. s or more. From the viewpoint of improving compatibility with the refrigerant, it is preferably 50 mm 2 /s or less, more preferably 40 mm 2 /s or less, and even more preferably 30 mm 2 /s or less. The upper and lower limits of these numerical ranges can be combined arbitrarily.
  • the 100° C. kinematic viscosity of base oil (A) is a value measured according to JIS K2283:2000.
  • the hydroxyl value of the base oil (A) is preferably 30 mgKOH/g or less, more preferably 25 mgKOH/g or less, still more preferably 20 mgKOH/g or less, still more preferably from the viewpoint of improving the thermal stability of the refrigerating machine oil composition. It is 15 mgKOH/g or less, more preferably 10 mgKOH/g or less, still more preferably 5 mgKOH/g or less. Moreover, the hydroxyl value of the base oil (A) is usually 0.1 mgKOH/g or more. As used herein, the hydroxyl value of base oil (A) is a value measured by a neutralization titration method in accordance with JIS K0070:1992.
  • the number average molecular weight (Mn) of the base oil (A) is preferably 300 or more, more preferably 400 or more, still more preferably 500 or more, from the viewpoint of improving lubricating performance (load-bearing performance) and sealing performance. From the viewpoint of improving compatibility with the refrigerant, it is preferably 10,000 or less, more preferably 7,000 or less, and even more preferably 5,000 or less. The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 300 to 10,000, more preferably 400 to 7,000, still more preferably 500 to 5,000. As used herein, the number average molecular weight (Mn) of the base oil (A) is a value measured by the method described in Examples below.
  • the refrigerator oil composition of the present embodiment contains a modified silicone compound (B).
  • the modified silicone compound (B) is used in combination with the epoxy compound (C) to effectively suppress the elution of fluorine content into the refrigerator oil composition due to the decomposition of the unsaturated fluorocarbon compound (HFO). It is possible to effectively suppress an increase in the acid value of the refrigerating machine oil composition. If the refrigerator oil composition does not contain the modified silicone compound (B), the increase in acid value of the refrigerator oil composition cannot be sufficiently suppressed.
  • the content of the modified silicone compound (B) is preferably 0.05% by mass based on the total amount of the refrigerating machine oil composition from the viewpoint of making it easier to improve the effects of the present invention. above, more preferably 0.08% by mass or more, still more preferably 0.10% by mass or more, even more preferably 0.30% by mass or more, still more preferably 0.60% by mass or more, and still more preferably 0.90% by mass % by mass or more.
  • the upper limit of the content of the modified silicone compound (B) is not particularly limited, it is preferably 5.0% by mass or less, more preferably 4.0% by mass or less, from the viewpoint of obtaining an effect commensurate with the amount added.
  • the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, preferably 0.05% by mass to 5.0% by mass, more preferably 0.08% by mass to 4.0% by mass, still more preferably 0.10% by mass to 3.0% by mass, more More preferably 0.30 mass % to 3.0 mass %, still more preferably 0.60 mass % to 3.0 mass %, and still more preferably 0.90 mass % to 3.0 mass %.
  • the modified silicone compound (B) can be used without any particular limitation as long as it is a silicone compound in which at least one of the side chain and the terminal of the polysiloxane skeleton in the unmodified silicone compound is modified.
  • the unmodified silicone compound is a silicone in which all of the side chains and terminals of the polysiloxane skeleton are composed of alkyl groups, and no functional groups other than the alkyl groups have been introduced into the side chains and terminals of the polysiloxane skeleton. is a compound.
  • Preferred examples of the unmodified silicone compound include compounds represented by the following general formula (b1-1).
  • R b1 and R b2 are each independently an alkyl group having 1 to 10 carbon atoms.
  • nb is an integer of 1 or more.
  • the number of carbon atoms in the alkyl group that can be selected as R b1 and R b2 is preferably 1-6, more preferably 1-3, still more preferably 1-2, and most preferably 1.
  • Rb1 is referred to as the side chain alkyl group of the polysiloxane skeleton
  • Rb2 is referred to as the terminal alkyl group of the polysiloxane skeleton.
  • the above-mentioned "at least one site of the side chain and terminal of the polysiloxane skeleton is modified” means the alkyl group of the side chain of the polysiloxane skeleton in the unmodified silicone compound (general formula (b1-1 ) and at least one of the terminal alkyl group (R b2 in the general formula (b1-1)) is substituted with a functional group other than the alkyl group.
  • Side chain-modified modified silicones include, for example, monoamine-modified silicones, diamine-modified silicones, special amino-modified silicones, epoxy-modified silicones, alicyclic epoxy-modified silicones, carbinol-modified silicones, mercapto-modified silicones, carboxyl-modified silicones, hydro Jen-modified silicone, amino-polyether-modified silicone, epoxy-polyether-modified silicone, epoxy-aralkyl-modified silicone, polyether-modified silicone, aralkyl-modified silicone, fluoroalkyl-modified silicone, long-chain alkyl-modified silicone, higher fatty acid ester-modified silicone, Examples include higher fatty acid amide-modified silicones, polyether/long-chain alkyl/aralkyl-modified silicones, long-chain alkyl/aralkyl-modified silicones, and phenyl-modified silicones. These may be used individually by 1 type, and may be used in combination of 2 or more type
  • Terminal-modified modified silicones include, for example, amino-modified silicones, epoxy-modified silicones, alicyclic epoxy-modified silicones, carbinol-modified silicones, methacryl-modified silicones, polyether-modified silicones, mercapto-modified silicones, carboxyl-modified silicones, and phenol-modified silicones.
  • Both end-modified modified silicones such as silicone, silanol-modified silicone, acrylic-modified silicone, and carboxylic acid anhydride-modified silicone; epoxy-modified silicone, carbinol-modified silicone, diol-modified silicone, methacrylic-modified silicone, and carboxyl-modified silicone; Modified silicones with one end modified type can be mentioned.
  • side chain end-modified modified silicone examples include side chain amino-modified/both-ends methoxy-modified silicone, side-chain epoxy-modified/both-ends epoxy-modified silicone, and the like.
  • the modified silicone compound (B) contains a side chain-modified silicone (B1) in which at least the side chains of the polysiloxane skeleton are modified. is preferred.
  • the content of the side chain-modified silicone (B1) in the modified silicone compound (B) is preferably from 50% by mass to 50% by mass, based on the total amount of the modified silicone compound (B), from the viewpoint of making it easier to improve the effects of the present invention.
  • the side chain-modified silicone (B1) includes a side chain-modified silicone (B1a) having one or more epoxy groups in the side chain and one or more polyethers in the side chain. It preferably contains one or more selected from side chain-modified silicones (B1b) having a group.
  • the side chain-modified silicone having one or more epoxy groups in the side chain (B1a) includes side chain-modified epoxy-modified silicone, side-chain-modified alicyclic epoxy-modified silicone, and side-chain-modified epoxy polyether. Modified silicone, side chain modified type epoxy/aralkyl modified silicone; side chain terminal modified type side chain epoxy modified/both terminal epoxy modified silicone, and the like.
  • a commercially available product may be used as the side chain-modified silicone (B1a) having one or more epoxy groups in the side chain.
  • Commercial products of side chain modified epoxy-modified silicone include X-22-343, KF-101, KF-1001 and X-22-2000 manufactured by Shin-Etsu Chemical Co., Ltd.; SF8411 Fluid manufactured by Dow Toray Industries, Inc. , SF8413 Fluid, and the like.
  • Commercial products of side chain-modified alicyclic epoxy-modified silicone include X-22-2046 and KF-102 manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-839 Fluid and L-9300 manufactured by Dow Toray Industries, Inc. is mentioned.
  • side chain-modified epoxy/polyether-modified silicone Commercial products of side chain-modified epoxy/polyether-modified silicone include X-22-4741 and KF-1002 manufactured by Shin-Etsu Chemical Co., Ltd.; BY16-876 and FZ-3736 Fluid manufactured by Dow Toray Industries, Inc. is mentioned.
  • Commercially available products of the side chain-modified epoxy-aralkyl-modified silicone include KF-1005 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • Examples of commercially available products of side chain terminal modified type side chain epoxy modified/both terminal epoxy modified silicone include X-22-9002 manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • the side chain-modified silicone (B1a) having one or more epoxy groups in the side chain is a side chain-modified epoxy-modified silicone and a side chain-modified alicyclic epoxy. It is preferably one or more selected from the group consisting of modified silicones.
  • the side chain-modified silicone (B1a) having one or more epoxy groups in the side chain may be used singly or in combination of two or more.
  • the side chain-modified silicone having one or more polyether groups in the side chain (B1b) includes side chain-modified polyether-modified silicone, side chain-modified amino/polyether-modified silicone, and side chain-modified polyether.
  • side chain-modified silicone examples include long-chain alkyl/aralkyl-modified silicones.
  • a silicone compound having both an epoxy group and a polyether group in a side chain such as a side chain-modified epoxy/polyether-modified silicone, is a side chain having one or more epoxy groups in the side chain. It shall be classified as chain-modified silicone (B1a).
  • a commercially available product may be used as the side chain-modified silicone (B1b) having one or more polyether groups in the side chain.
  • Commercially available side chain-modified polyether-modified silicones include KF-351A, KF-352A, KF-353, KF-354L, KF-355A, KF-615A, KF-945 manufactured by Shin-Etsu Chemical Co., Ltd. KF-640, KF-642, KF-643, KF-644, KF-6020, KF-6204, X-22-4515, KF-6011, KF-6012, KF-6015, KF-6015, Dow Toray FZ-2110 manufactured by Co., Ltd. and the like can be mentioned.
  • side chain-modified amino/polyether-modified silicone examples include X-22-3939A manufactured by Shin-Etsu Chemical Co., Ltd., and the like.
  • X-22-2516 manufactured by Shin-Etsu Chemical Co., Ltd. and the like are examples of commercially available products of side chain-modified polyether/long-chain alkyl/aralkyl-modified silicone.
  • the side chain-modified silicone (B1b) having one or more polyether groups in the side chain is preferably a side chain-modified polyether-modified silicone from the viewpoint of availability and effectiveness.
  • the side chain-modified silicone (B1b) having one or more polyether groups in the side chain may be used singly or in combination of two or more.
  • the content of one or more types is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, and still more preferably 70% by mass to 100% by mass, based on the total amount of the side chain-modified silicone (B1). %, even more preferably 80% to 100% by weight, still more preferably 90% to 100% by weight, and even more preferably 95% to 100% by weight.
  • the refrigerator oil composition of this embodiment contains an epoxy compound (C) that satisfies the following requirements ( ⁇ ) and ( ⁇ ).
  • ( ⁇ ) has at least one divalent group represented by the following formula (2) in the molecule;
  • ( ⁇ ) has at least one ester group in the molecule;
  • the epoxy compound (C) is used in combination with the modified silicone compound (B) to effectively suppress the elution of fluorine content into the refrigerator oil composition due to the decomposition of the unsaturated fluorocarbon compound (HFO). It is possible to effectively suppress an increase in the acid value of the refrigerating machine oil composition. If the refrigerator oil composition does not contain the epoxy compound (C), the increase in acid value of the refrigerator oil composition cannot be sufficiently suppressed.
  • the epoxy compound (C) has a molecular weight of 300 or more, the reactivity of the epoxy group can be moderately suppressed, the decomposition of the unsaturated fluorohydrocarbon compound can be suppressed, and the base oil can be It is preferable because the solubility of is improved, it is more preferably 320 or more, and still more preferably 350 or more.
  • the molecular weight of the epoxy compound (C) is preferably 2,000 or less, more preferably 1,500 or less, from the viewpoint of solubility in refrigerator oil and sludge formation after stability evaluation. It is more preferably 1,000 or less.
  • the content of the epoxy compound (C) is preferably 0.05% by mass or more, based on the total amount of the refrigerating machine oil composition, from the viewpoint of making it easier to improve the effects of the present invention. , more preferably 0.07% by mass or more, and still more preferably 0.08% by mass or more.
  • the upper limit of the content of the epoxy compound (C) is not particularly limited. Preferably, it is 3.0% by mass or less. The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, it is preferably 0.05% by mass to 5.0% by mass, more preferably 0.07% by mass to 4.0% by mass, and still more preferably 0.08% by mass to 3.0% by mass. .
  • the epoxy compound (C) one or more selected from the group consisting of those satisfying the above two requirements ( ⁇ ) and ( ⁇ ) can be used without particular limitation.
  • the epoxy compound (C) includes an epoxidized fatty acid ester (C1), an epoxidized vegetable oil (C2), and an epoxidized alicyclic carboxylic acid ester (C3).
  • the content of one or more selected from the group consisting of epoxidized fatty acid ester (C1), epoxidized vegetable oil (C2), and epoxidized alicyclic carboxylic acid ester (C3) in the epoxy compound (C) is Based on the total amount of the epoxy compound (C), preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, still more preferably 70% by mass to 100% by mass, still more preferably 80% by mass to 100% by weight, more preferably 90% to 100% by weight, more preferably 95% to 100% by weight.
  • the epoxidized fatty acid ester (C1), the epoxidized vegetable oil (C2), and the epoxidized alicyclic carboxylic acid ester (C3) are described below.
  • the epoxidized fatty acid ester (C1) is an ester of a fatty acid having 8 to 30 carbon atoms (preferably 12 to 20 carbon atoms) and an alcohol having 1 to 10 carbon atoms, phenol, or an alkylphenol having 7 to 14 carbon atoms.
  • An epoxidized one can be exemplified.
  • epoxidized fatty acid ester (C1) one represented by the following general formula (c1) is preferably used from the viewpoint of effectively suppressing an increase in the acid value of the refrigerator oil composition.
  • R c1 is a hydrocarbon group having 4 to 20 carbon atoms
  • R c2 is a hydrocarbon group having 1 to 10 carbon atoms
  • p is an integer of 1 to 3
  • n is an integer of 0 to 12
  • m is an integer of 1 to 3.
  • the multiple structures in [] may be the same or different.
  • the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, and the like.
  • Cycloalkyl groups such as alkyl groups; cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups; phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups aryl groups such as groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups; aryl groups such as benzyl groups, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups; Alkyl group; In the epoxidized fatty acid ester represented by (c1) above, R c1 is an alkyl group having 5 to 12 carbon atoms, R c2 is an al
  • epoxidized fatty acid esters (C1) include butyl esters, hexyl esters, 2-ethylhexyl esters, benzyl esters, cyclohexyl esters, and methoxyethyl esters of linoleic acid, oleic acid, palmitic acid, linolenic acid, or stearic acid. , octyl ester, phenyl ester, or epoxidized butyl phenyl ester.
  • epoxidized fatty acid ester (C1) Commercially available products of the epoxidized fatty acid ester (C1) include Sanso Cizer E-6000 manufactured by Shin Nippon Rika Co., Ltd., Chemicizer T-5000 manufactured by Sanwa Gosei Kagaku Co., Ltd., and the like.
  • the epoxidized fatty acid ester (C1) may be used alone or in combination of two or more.
  • epoxidized vegetable oil (C2) examples include epoxidized vegetable oils such as soybean oil, linseed oil, rice bran oil and cottonseed oil.
  • epoxidized vegetable oil (C2) those having a group represented by the following general formula (c2) are preferably used from the viewpoint of making it easier to improve the effects of the present invention.
  • a glycerin ester having one or more groups represented by (c2) is preferable, and a triglyceride having one or more groups represented by the following general formula (c2) is more preferable, and a group represented by the following general formula (c2) Triglycerides having two or more are more preferred.
  • R c1 is a hydrocarbon group having 4 to 20 carbon atoms
  • p is an integer of 1 to 3
  • n is an integer of 0 to 12
  • m is an integer of 1 to 3.
  • R c1 is an alkyl group having 4 to 12 carbon atoms
  • p is 1
  • n is an integer of 1 to 10
  • m is 1 or 2. things are preferred.
  • C2 Commercial products of epoxidized vegetable oil (C2) include Sanso Cizer E-2000H manufactured by Shin Nippon Rika Co., Ltd., Chemicizer SE-80 manufactured by Sanwa Gosei Chemical Co., Ltd., Chemicizer SE-100, Chemicizer T-3000N, and Chemicizer LE. -3000, Chemisizer T-2000, NOF Corporation Newsizer 510R, ADEKA Corporation Adekasizer O-180A, and the like.
  • the epoxidized vegetable oil (C2) may be used alone or in combination of two or more.
  • the epoxidized alicyclic carboxylic acid ester (C3) is an ester of an alicyclic carboxylic acid having 5 to 12 ring carbon atoms and an alcohol or phenol having 1 to 8 carbon atoms, or an alkylphenol having 7 to 14 carbon atoms.
  • An epoxidized one can be exemplified, and the alicyclic carboxylic acid may be a monocarboxylic acid or a dicarboxylic acid.
  • epoxidized alicyclic carboxylic acid ester (C3) one represented by the following general formula (c3) is preferably used from the viewpoint of effectively suppressing an increase in the acid value of the refrigerator oil composition.
  • R c3 and R c4 are each independently a hydrocarbon group having 4 to 20 carbon atoms.
  • Specific examples of the above hydrocarbon group include those having the corresponding number of carbon atoms than those listed as the hydrocarbon group in formula (c1).
  • those in which R c3 and R c4 are each independently an alkyl group having 6 to 12 carbon atoms are preferred.
  • epoxidized alicyclic carboxylic acid ester examples include epoxidized alicyclic dicarboxylic acid esters, more specifically di-2-ethylhexyl 4,5-epoxycyclohexane-1,2-dicarboxylate. mentioned.
  • Commercially available products of the epoxidized alicyclic carboxylic acid ester include Sanso Cizer E-PS manufactured by Shin Nippon Rika Co., Ltd., and the like.
  • the epoxidized alicyclic carboxylic acid ester (C3) may be used alone or in combination of two or more.
  • the epoxy compound (C) contains one or more selected from the group consisting of epoxidized fatty acid ester (C1) and epoxidized vegetable oil (C2). is more preferred, and it is even more preferred to contain an epoxidized fatty acid ester (C1).
  • the content ratio [(B)/(C)] of the modified silicone compound (B) and the epoxy compound (C) is The mass ratio is preferably 0.10 or more, more preferably 0.15 or more, still more preferably 0.20 or more, still more preferably 0.50 or more, still more preferably 1.0 or more, and still more preferably 5.5. 0 or more, and more preferably 8.0 or more. Also, it is preferably 20 or less, more preferably 18 or less, still more preferably 16 or less. The upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, preferably 0.10 to 20, more preferably 0.15 to 18, still more preferably 0.20 to 16, still more preferably 0.50 to 16, still more preferably 1.0 to 16 , more preferably 5.0-16, even more preferably 8.0-16.
  • the refrigerator oil composition of the present embodiment may further contain an antioxidant (D).
  • the antioxidant (D) preferably includes one or more selected from the group consisting of phenol antioxidants and amine antioxidants.
  • Phenolic antioxidants include 2,6-di-tert-butyl-p-cresol (DBPC), 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis(4-methyl -6-tert-butylphenol) and the like.
  • Amine-based antioxidants include phenyl- ⁇ -naphthylamine, N,N'-diphenyl-p-phenylenediamine, and the like.
  • the content of the antioxidant (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, based on the total amount of the refrigerating machine oil composition. Preferably, it is 0.1% by mass or more. Also, it is preferably 5% by mass or less, more preferably 3% by mass or less, and still more preferably 1% by mass or less. The upper and lower limits of these numerical ranges can be combined arbitrarily.
  • the antioxidant (D) may be used alone or in combination of two or more.
  • the content ratio of the modified silicone compound (B) and the antioxidant (D) is [(B)/(D)] is preferably 0.10 or more, more preferably 0.20 or more, and still more preferably 0.30 or more in mass ratio. Also, it is preferably 10.0 or less, more preferably 5.0 or less, and still more preferably 4.0 or less.
  • the content ratio of the epoxy compound (C) and the antioxidant (D) [ (C)/(D)] is preferably 0.10 or more, more preferably 0.20 or more, and still more preferably 0.30 or more in mass ratio. Also, it is preferably 10.0 or less, more preferably 5.0 or less, still more preferably 4.0 or less, and even more preferably 2.0 or less.
  • the refrigerator oil composition of the present embodiment may further contain a glycidyl ether compound (E).
  • a glycidyl ether compound (E) an aliphatic mono- or polyhydric alcohol having usually 3 to 30 carbon atoms, preferably 4 to 24 carbon atoms, more preferably 6 to 16 carbon atoms, or an aromatic compound containing one or more hydroxyl groups. and glycidyl ethers derived from The aliphatic mono- or polyhydric alcohol may be linear, branched or cyclic, and may be saturated or unsaturated, but saturated aliphatic mono-alcohol is preferred.
  • all hydroxyl groups are preferably glycidyl-etherified from the viewpoint of the stability of the refrigerating machine oil composition.
  • Glycidyl ether compounds include, for example, phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether and the like.
  • Alcohol-derived glycidyl ethers ie, alkyl glycidyl ethers having 6 to 16 carbon atoms in the alkyl group are more preferred.
  • glycidyl ethers examples include 2-ethylhexyl glycidyl ether, isononyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether and the like, with 2-ethylhexyl glycidyl ether being most preferred.
  • an alkyl glycidyl ether such as 2-ethylhexyl glycidyl ether, an increase in the acid value of the refrigerating machine oil composition can be appropriately prevented, and oxidation stability at high temperatures can be easily improved.
  • the content of the glycidyl ether compound (E) is preferably 0.10 to 10.00% by mass based on the total amount of the refrigerator oil composition.
  • the content of the glycidyl ether compound (E) is more preferably 0.4% by mass or more, and still more preferably 0.5% by mass or more.
  • Glycidyl ether compounds (E) may be used alone or in combination of two or more.
  • composition of the present embodiment contains a glycidyl ether compound (E)
  • content ratio of the modified silicone compound (B) and the glycidyl ether compound (E) is The mass ratio [(B)/(E)] is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.04 or more. Also, it is preferably 5.0 or less, more preferably 2.0 or less, and still more preferably 1.0 or less.
  • the content ratio of the epoxy compound (C) and the glycidyl ether compound (E) [ (C)/(E)] is preferably 0.01 or more, more preferably 0.03 or more, and still more preferably 0.04 or more in mass ratio. Also, it is preferably 5.0 or less, more preferably 2.0 or less, and still more preferably 1.0 or less.
  • the refrigerating machine oil composition of the present embodiment may further contain a stabilizer (F).
  • Stabilizers (F) include aliphatic unsaturated compounds, terpenes having double bonds, and the like.
  • the unsaturated aliphatic compound is preferably an unsaturated hydrocarbon, and specific examples thereof include olefins; polyenes such as dienes and trienes.
  • olefin ⁇ -olefins such as 1-tetradecene, 1-hexadecene, and 1-octadecene are preferable from the viewpoint of reactivity with oxygen.
  • vitamin A ((2E,4E,6E,8E)-3,7-dimethyl-9, represented by the molecular formula C 20 H 30 O
  • Unsaturated aliphatic alcohols with conjugated double bonds such as -(2,6,6-trimethylcyclohex-1-yl)non-2,4,6,8-tetraen-1-ol) are preferred.
  • the terpene having a double bond is preferably a terpene hydrocarbon having a double bond, and from the viewpoint of reactivity with oxygen, ⁇ -pinene, ⁇ -pinene, ⁇ -farnesene (C 15 H 24 : 3, 7,11-trimethyldodeca-1,3,6,10-tetraene) and ⁇ -farnesene (C 15 H 24 : 7,11-dimethyl-3-methylidendodeca-1,6,10-triene) are more preferred.
  • the content of the stabilizer (F) is preferably 0.10% by mass or more, more preferably 0.20% by mass or more, and still more preferably 0.30% by mass or more, based on the total amount of the refrigerating machine oil composition. . Also, it is preferably 8.0% by mass or less, more preferably 5.0% by mass or less, and still more preferably 3.0% by mass or less.
  • the upper and lower limits of these numerical ranges can be combined arbitrarily. Specifically, more preferably 0.10% by mass to 8.0% by mass, still more preferably 0.20% by mass to 5.0% by mass, still more preferably 0.30% by mass to 3.0% by mass is.
  • the stabilizer (F) may be used alone or in combination of two or more.
  • composition of the present embodiment contains the stabilizer (F)
  • content ratio of the modified silicone compound (B) and the stabilizer (F) is The mass ratio [(B)/(F)] is preferably 0.01 or more, more preferably 0.04 or more, and still more preferably 0.06 or more. Also, it is preferably 5.0 or less, more preferably 3.0 or less, and still more preferably 1.0 or less.
  • the content ratio of the epoxy compound (C) and the stabilizer (F) [ (C)/(F)] is preferably 0.01 or more, more preferably 0.04 or more, and still more preferably 0.06 or more in mass ratio. Also, it is preferably 5.0 or less, more preferably 3.0 or less, and still more preferably 1.0 or less.
  • the refrigerator oil composition of the present embodiment contains other Additives (hereinafter also referred to as “other additives”) may be contained.
  • Other additives include, for example, extreme pressure agents and antifoaming agents.
  • the refrigerator oil composition of the present embodiment may consist only of the base oil (A), the modified silicone compound (B), and the epoxy compound (C), but the base oil (A), the modified silicone In addition to the compound (B) and the epoxy compound (C), it is further selected from the group consisting of an antioxidant (D), a glycidyl ether compound (E), a stabilizer (F), an extreme pressure agent, and an antifoaming agent.
  • an antioxidant D
  • E glycidyl ether compound
  • F stabilizer
  • an extreme pressure agent and an antifoaming agent.
  • an antifoaming agent may contain one or more of
  • extreme pressure agent As the extreme pressure agent, a phosphorus-based extreme-pressure agent, a metal salt of carboxylic acid, and a sulfur-based extreme-pressure agent are preferable.
  • Phosphorus-based extreme pressure agents include, for example, phosphates, acid phosphates, phosphites, acid phosphites, and amine salts thereof.
  • tricresyl phosphate (TCP) trithiophenyl phosphate
  • tri(nonylphenyl) phosphite dioleyl hydrogen phosphite
  • 2-ethylhexyldiphenyl phosphite from the viewpoint of improving extreme pressure properties and friction properties.
  • tricresyl phosphate TCP
  • metal salts of carboxylic acids include metal salts of carboxylic acids having 3 to 60 (preferably 3 to 30) carbon atoms. Among these, one or more selected from metal salts of fatty acids having 12 to 30 carbon atoms and metal salts of dicarboxylic acids having 3 to 30 carbon atoms are preferred. Moreover, as the metal constituting the metal salt, alkali metals and alkaline earth metals are preferable, and alkali metals are more preferable.
  • sulfur-based extreme pressure agents include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, and dialkylthiodipropionates.
  • antifoaming agent examples include silicone antifoaming agents such as silicone oils and fluorinated silicone oils.
  • the silicone compound used as the antifoaming agent is an unmodified silicone compound that is not classified as the modified silicone compound (B).
  • the method for producing the above refrigerator oil composition is not particularly limited.
  • the method for producing the refrigerating machine oil composition of the present embodiment is represented by the following general formula (1) CxFyHz ( 1 ) [In the general formula (1), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and has one or more carbon-carbon unsaturated bonds in the molecule.
  • Requirement ( ⁇ ) It has at least one ester group in the molecule.
  • the method for mixing the above components is not particularly limited, but for example, a method comprising the step of blending the base oil (A) with the modified silicone compound (B) and the epoxy compound (C) can be mentioned.
  • the antioxidant (D), the glycidyl ether compound (E), the stabilizer (F), and other additives are respectively obtained by adding the modified silicone compound (B) and the epoxy compound (C) to the base oil (A). It may be blended with the base oil (A) at the same time as blending, or may be blended separately. In addition, each component may be blended after adding a diluent oil or the like to form a solution (dispersion). After blending each component, it is preferable to stir and uniformly disperse the components by a known method.
  • the acid value of the refrigerating machine oil composition after the thermal stability test described in the examples below is preferably less than 0.17 mgKOH/g, more preferably 0.16 mgKOH/g or less, and still more preferably 0.14 mgKOH/g or less. , more preferably 0.12 mg KOH/g or less, still more preferably 0.10 mg KOH/g or less, and still more preferably 0.09 mg KOH/g or less.
  • the amount of fluorine in the refrigerating machine oil composition after the thermal stability test described in the examples described later is preferably less than 19 mass ppm, more preferably 15 mass ppm or less, still more preferably based on the total amount of the refrigerating machine oil composition. It is 12 mass ppm or less, more preferably 10 mass ppm or less, still more preferably 9 mass ppm or less.
  • the above refrigerator oil composition is mixed with a refrigerant and used as a mixture composition for refrigerators. That is, the mixed composition for a refrigerator contains the above-described refrigerator oil composition and a refrigerant.
  • the refrigerant will be described below.
  • the refrigerant used in the present embodiment has the following general formula (1) CxFyHz ( 1 ) [In the general formula (1), x is an integer of 2 to 6, y is an integer of 1 to 11, and z is an integer of 1 to 11, and has one or more carbon-carbon unsaturated bonds in the molecule. ] is a refrigerant containing one or more unsaturated fluorohydrocarbon compounds selected from the compounds represented by
  • the above general formula (1) represents the kind and number of elements in the molecule, and specifically represents an unsaturated fluorohydrocarbon compound having 2 to 6 carbon atoms (C).
  • Unsaturated fluorohydrocarbon compounds having 2 to 6 carbon atoms have physical and chemical properties such as boiling point, freezing point and latent heat of vaporization required as refrigerants.
  • the bonding form of x carbon atoms represented by C x includes unsaturated bonds such as carbon-carbon single bonds and carbon-carbon double bonds.
  • the carbon-carbon unsaturated bond is preferably a carbon-carbon double bond from the viewpoint of stability, and the unsaturated fluorocarbon compound has an unsaturated bond such as a carbon-carbon double bond in the molecule.
  • Preferred examples of the unsaturated fluorohydrocarbon compound include fluorides of linear or branched chain olefins having 2 to 6 carbon atoms and cyclic olefins having 4 to 6 carbon atoms. Specifically, ethylene fluoride into which 1 to 3 fluorine atoms have been introduced, propene fluoride into which 1 to 5 fluorine atoms have been introduced, and butene into which 1 to 7 fluorine atoms have been introduced.
  • Fluorides pentene fluorides introduced with 1 to 9 fluorine atoms, hexene fluorides introduced with 1 to 11 fluorine atoms, and cyclobutene fluorides introduced with 1 to 5 fluorine atoms , cyclopentene fluorides into which 1 to 7 fluorine atoms have been introduced, and cyclohexene fluorides into which 1 to 9 fluorine atoms have been introduced.
  • propene fluorides are preferred, and propene having 3 to 5 fluorine atoms introduced is more preferred.
  • 1,3,3,3-tetrafluoropropene (R1234ze), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,2,3,3-tetrafluoropropene (R1234ye) One or more selected from are preferable, and 2,3,3,3-tetrafluoropropene (R1234yf) is more preferable.
  • the above unsaturated hydrofluorocarbon compounds may be used singly or in combination of two or more.
  • 1,3,3,3-tetrafluoropropene (R1234ze), 2,3,3,3-tetrafluoropropene (R1234yf), and 1,2,3,3-tetrafluoropropene (R1234ye); You may use only 1 type independently.
  • the refrigerant may be a mixed refrigerant containing, if necessary, other compounds in addition to the unsaturated fluorocarbon compound represented by the general formula (1).
  • a saturated fluorocarbon compound preferably an alkane fluoride having 1 to 4 carbon atoms, more preferably an alkane fluoride having 1 to 3 carbon atoms, more preferably an alkane having 1 or 2 carbon atoms (methane or ethane ).
  • the methane or ethane fluorides include trifluoromethane (R23), difluoromethane (R32), 1,1-difluoroethane (R152a), 1,1,1-trifluoroethane (R143a), 1,1,2- Trifluoroethane (R143), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2,2-tetrafluoroethane (R134), 1,1,1,2,2-pentafluoroethane (R125), etc.
  • difluoromethane and 1,1,1,2,2-pentafluoroethane are preferred.
  • These saturated fluorocarbon compounds may be used singly or in combination of two or more.
  • the refrigerant may contain a natural refrigerant.
  • natural refrigerants include hydrocarbon refrigerants (HC), carbon dioxide (CO 2 , carbon dioxide gas), ammonia, and the like. These natural refrigerants may be used singly or in combination of two or more.
  • the hydrocarbon refrigerant is preferably a hydrocarbon having 1 or more and 8 or less carbon atoms, more preferably a hydrocarbon having 1 or more and 5 or less carbon atoms, and still more preferably a hydrocarbon having 3 or more and 5 or less carbon atoms. When the number of carbon atoms is 8 or less, the boiling point of the refrigerant does not become too high, which is preferable as a refrigerant.
  • the hydrocarbon refrigerants include methane, ethane, ethylene, propane (R290), cyclopropane, propylene, n-butane, isobutane (R600a), 2-methylbutane, n-pentane, isopentane, cyclopentaneisobutane, and normal hexane.
  • methane ethane
  • ethylene propane (R290)
  • cyclopropane propylene
  • n-butane isobutane (R600a)
  • 2-methylbutane n-pentane
  • isopentane cyclopentaneisobutane
  • normal hexane normal hexane.
  • One or more selected from the group consisting of may be mentioned, and one of these may be used alone, or two or more may be used in combination.
  • the refrigerant contains the unsaturated fluorocarbon compound represented by the above general formula (1).
  • the content of the unsaturated fluorohydrocarbon compound represented by the general formula (1) is preferably 50% by mass to 100% by mass, more preferably 60% by mass to 100% by mass, based on the total amount of the refrigerant.
  • the refrigerating machine oil composition of the present embodiment is excellent in the effect of suppressing an increase in acid value even with a refrigerant containing a large amount of unsaturated fluorocarbon compounds.
  • the amount of the refrigerant and the refrigerant oil composition used is preferably 1 in terms of the mass ratio of the refrigerant oil composition to the refrigerant [(refrigerant oil composition)/(refrigerant)]. /99 to 90/10, more preferably 5/95 to 70/30.
  • the mass ratio of the refrigerating machine oil composition to the refrigerant is within the above range, lubricity and suitable refrigerating capacity in the refrigerating machine can be obtained.
  • the refrigerating machine oil composition and the mixed composition for refrigerating machines described above are preferably used in, for example, air conditioners, refrigerators, vending machines, showcases, refrigerating systems, hot water supply systems, or heating systems.
  • air conditioners include car air conditioners such as open type car air conditioners and electric car air conditioners; gas heat pump (GHP) air conditioners; and the like.
  • An aspect of the present invention provides the following [1] to [14].
  • x is an integer of 2 to 6
  • y is an integer of 1 to 11
  • z is an integer of 1 to 11, and has one or more carbon-carbon unsaturated bonds in the molecule.
  • Requirement ( ⁇ ) At least one divalent group represented by the following formula (2) is present in the molecule. • Requirement ( ⁇ ): It has at least one ester group in the molecule.
  • the side chain-modified silicone (B1) comprises a side chain-modified silicone (B1a) having one or more epoxy groups in the side chain and a side chain-modified silicone (B2a) having one or more polyether groups in the side chain.
  • the refrigerating machine oil composition according to any one of [1] to [9].
  • a method for producing a refrigerator oil composition comprising the step of mixing Requirement ( ⁇ ): At least one divalent group represented by the following formula (2) is present in the molecule. • Requirement ( ⁇ ): It has at least one ester group in the molecule.
  • GPC uses two columns "TSKgel SuperMultiporeHZ-M” manufactured by Tosoh Corporation that are sequentially connected, tetrahydrofuran as an eluent, and a refractive index detector (RI detector) as a detector.
  • RI detector refractive index detector
  • Mn number average molecular weight
  • ⁇ Modified silicone compound (B)> ⁇ “Epoxy-modified silicone”: KF-101 (manufactured by Shin-Etsu Chemical Co., Ltd.) ⁇ “Alicyclic epoxy-modified silicone”: KF-102 (manufactured by Shin-Etsu Chemical Co., Ltd.) ⁇ "Polyether-modified silicone”: KF-945 (manufactured by Shin-Etsu Chemical Co., Ltd.), HLB value 4 Epoxy-modified silicones and alicyclic epoxy-modified silicones are modified silicones corresponding to side chain-modified silicones (B1a) having one or more epoxy groups in side chains. Polyether-modified silicone is modified silicone corresponding to side chain-modified silicone (B1b) having one or more polyether groups in the side chain.
  • Epoxy compound (C)> ⁇ “Epoxy compound 1”: epoxidized soybean oil represented by the following formula, molecular weight: 933, Sanso Cizer E-2000H (manufactured by Shin Nippon Rika Co., Ltd.) The epoxidized soybean oil represented by the above formula is an epoxy compound corresponding to the epoxidized vegetable oil (C2).
  • the epoxidized soybean oil represented by the above formula is an epoxy compound corresponding to the epoxidized vegetable oil (C2).
  • Epoxy compound 3 epoxidized fatty acid ester represented by the following formula, molecular weight: 411, Sanso Cizer E-6000 (manufactured by New Japan Chemical Co., Ltd.)
  • the epoxidized fatty acid ester represented by the above formula is an epoxy compound corresponding to the epoxidized fatty acid ester (C1).
  • ⁇ “Epoxy compound 4” epoxidized fatty acid ester (C 17 H 33 OCOOC 8 H 17 ), molecular weight: 411, Chemicizer T-5000 (manufactured by Sanwa Gosei Kagaku Co., Ltd.)
  • Epoxy compound 4 is an epoxy compound corresponding to the epoxidized fatty acid ester (C1).
  • Refrigerating machine oil compositions having the compositions shown in Tables 1 to 3 were prepared by mixing the respective components described above, and the thermal stability tests described below were conducted.
  • the numerical unit of the composition in Tables 1 to 3 is "% by mass”.
  • the content of modified silicone compound (B) in Tables 1 to 3 means the content in terms of solid content.
  • ⁇ Thermal stability test> It was performed in accordance with Annex C of JIS K2211:2009. Specifically, in an autoclave tube having an internal volume of 200 mL, a mixed composition for a refrigerator (water content of 500 mass ppm, air content of 25 mL) obtained by mixing 30 g of the refrigerator oil composition of Examples and Comparative Examples and 30 g of R1234yf , and a metal catalyst consisting of iron, copper, and aluminum. Next, after evacuating, the tube was sealed and held at a temperature of 175 ° C. for 14 days. ) was visually observed.
  • a mixed composition for a refrigerator water content of 500 mass ppm, air content of 25 mL
  • the oil appearance was evaluated by ASTM color, and oil appearance judged to be 0.5 or less (L0.5) was judged to be good, and larger than 0.5 (L1.0, L1. 5 etc.) was judged to be poor in oil appearance.
  • the acid value of the refrigerating machine oil composition and the amount of fluorine in the refrigerating machine oil composition were evaluated by the methods described below.
  • the amount of fluorine in the refrigerating machine oil composition is determined by separating the refrigerant from the mixed composition for refrigerating machines after the autoclave test, and measuring fluorine ions ( F ⁇ ) was detected and measured.
  • Tables 1 and 2 show the following.
  • the refrigerating machine oil compositions of Examples I-1 to I-12 are excellent in the effect of suppressing the increase in acid value of the refrigerating machine oil composition after the thermal stability test, and the fluorine content in the refrigerating machine oil composition after the test is also small. I understand.
  • the refrigerator oil compositions of Comparative Examples I-1 to I-9 had an insufficient effect of suppressing the increase in acid value of the refrigerator oil composition after the thermal stability test, and the refrigerator oil composition after the test It can be seen that the amount of fluorine in the material is also large.
  • Table 3 shows the following.
  • the refrigerating machine oil compositions of Examples II-1 to II-8 are excellent in the effect of suppressing the increase in acid value of the refrigerating machine oil composition after the thermal stability test, and the fluorine content in the refrigerating machine oil composition after the test is also small. I understand.
  • the refrigerating machine oil compositions of Comparative Examples II-1 to II-7 had an insufficient effect of suppressing the increase in acid value of the refrigerating machine oil composition after the thermal stability test. It can be seen that the amount of fluorine in the material is also large.
  • the refrigerating machine oil composition containing the modified silicone compound (B) and the epoxy compound (C) is excellent in the effect of suppressing the increase in acid value of the refrigerating machine oil composition after the thermal stability test. It can be seen that the amount of fluorine in the refrigerator oil composition is also small.

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US20250084295A1 (en) 2025-03-13
JPWO2023157867A1 (https=) 2023-08-24
US12577448B2 (en) 2026-03-17
EP4481021A4 (en) 2026-02-18
CN118679236A (zh) 2024-09-20

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