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
  • 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
  • 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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
• • 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
  • C10M105/18—Ethers, e.g. 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
  • 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
• • 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
  • C10M107/30—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M107/32—Condensation polymers of aldehydes or ketones; Polyesters; Polyethers
  • C10M107/34—Polyoxyalkylenes
• • 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
  • 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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
• • 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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
  • C10M137/04—Phosphate esters
• • 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
  • C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
  • C10M137/12—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond
  • C10M137/14—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having a phosphorus-to-carbon bond containing sulfur
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
  • C10M169/04—Mixtures of base-materials and additives
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
  • C10M2207/0406—Ethers; Acetals; Ortho-esters; Ortho-carbonates 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
  • 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
  • C10M2207/2805—Esters 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
  • 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
  • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
  • C10M2207/28—Esters
  • C10M2207/30—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids
  • C10M2207/301—Complex esters, i.e. compounds containing at leasst three esterified carboxyl groups and derived from the combination of at least three different types of the following five types of compounds: monohydroxyl compounds, polyhydroxy xompounds, monocarboxylic acids, polycarboxylic acids or hydroxy carboxylic acids 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
  • 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/101—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof
  • C10M2209/1013—Condensation polymers of aldehydes or ketones and phenols, e.g. Also polyoxyalkylene ether derivatives thereof 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
  • C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
  • C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
  • C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
  • C10M2209/1085—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
• • 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
  • C10N2020/09—Characteristics associated with water
  • C10N2020/097—Refrigerants
  • C10N2020/101—Containing Hydrofluorocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
  • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • 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.
• Refrigerators such as refrigerators, car air conditioners, room air conditioners, and vending machines are equipped with a compressor for circulating the refrigerant in the refrigeration cycle.
• the compressor is filled with refrigerating machine oil for lubricating the sliding member.
• Refrigerating machine oil is required to have characteristics such as wear resistance and stability.
• Refrigerating machine oil generally contains a lubricating base oil and additives selected according to the required characteristics as described above.
• an additive antioxidant for improving wear resistance
• a normal phosphate ester, an acidic phosphate ester, or the like has been used (for example, Patent Documents 1 and 2).
• an object of the present invention is to provide a refrigerating machine oil having excellent wear resistance.
• the present invention provides a refrigerating machine oil containing a lubricating base oil and a compound represented by the following formula (A).
• R a and R b each independently represent a monovalent hydrocarbon group
• R c represents a divalent hydrocarbon group
• X represents a polar group
• Z a and Z b each independently represent An oxygen atom or a sulfur atom is represented.
• the refrigerating machine oil preferably contains at least one oxygen-containing oil selected from the group consisting of esters and ethers as a lubricating oil base oil.
• the refrigerating machine oil preferably further contains an epoxy compound.
• the refrigerating machine oil is preferably selected from the group consisting of 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 as epoxy compounds. Contains at least one selected.
• the refrigerating machine oil preferably contains at least one selected from the group consisting of a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, and an alicyclic epoxy compound as an epoxy compound.
• the polar group represented by X in the formula (A) preferably has an oxygen atom.
• the refrigerating machine oil which concerns on one Embodiment contains lubricating base oil and the compound represented by a following formula (A).
• R a and R b each independently represent a monovalent hydrocarbon group
• R c represents a divalent hydrocarbon group
• X represents a polar group
• Z a and Z b each independently represent An oxygen atom or a sulfur atom is represented.
• hydrocarbon oil As the lubricating base oil, hydrocarbon oil, oxygen-containing oil, or the like can be used.
• hydrocarbon oil include mineral oil-based hydrocarbon oil and synthetic hydrocarbon oil.
• oxygen-containing oil include esters, ethers, carbonates, ketones, silicones, and polysiloxanes.
• Mineral oil-based hydrocarbon oils are obtained by removing solvent oil from solvent oil fractions obtained by atmospheric distillation and vacuum distillation of paraffinic and naphthenic crude oil, solvent refining, hydrorefining, hydrocracking, solvent dewatering. It can be obtained by purification by a method such as wax, hydrodewaxing, clay treatment, or sulfuric acid washing. These purification methods may be used individually by 1 type, and may be used in combination of 2 or more type.
• Synthetic hydrocarbon oils include alkylbenzene, alkylnaphthalene, poly ⁇ -olefin (PAO), polybutene, ethylene- ⁇ -olefin copolymer, and the like.
• alkylbenzene the following alkylbenzene (A) and / or alkylbenzene (B) can be used.
• alkyl group having 1 to 19 carbon atoms that the alkylbenzene (A) has include, for example, a methyl group, an ethyl group, a propyl group (including all isomers, the same applies hereinafter), a butyl group, a pentyl group, and a hexyl group.
• alkyl groups may be linear or branched, and are preferably branched from the viewpoint of stability, viscosity characteristics and the like.
• the alkyl group is a branched alkyl group derived from an oligomer of an olefin such as propylene, butene and isobutylene, particularly from the viewpoint of availability.
• the number of alkyl groups in the alkylbenzene (A) is 1 to 4, and preferably 1 or 2 (ie, monoalkylbenzene, dialkylbenzene, or a mixture thereof) from the viewpoint of stability and availability. is there.
• the alkylbenzene (A) may contain only an alkylbenzene having a single structure, has 1 to 4 alkyl groups having 1 to 19 carbon atoms, and has a total carbon number of 9 to 19 alkyl groups. If it is the alkylbenzene which satisfy
• alkyl group having 1 to 40 carbon atoms that the alkylbenzene (B) has include a methyl group, an ethyl group, a propyl group (including all isomers, the same applies hereinafter), a butyl group, a pentyl group, and a hexyl group.
• alkyl groups may be linear or branched, and are preferably branched from the viewpoint of stability, viscosity characteristics and the like.
• the alkyl group is a branched alkyl group derived from an oligomer of an olefin such as propylene, butene and isobutylene, particularly from the viewpoint of availability.
• the alkyl group is preferably a linear or branched alkyl derived from a linear alkylating agent such as a linear paraffin, a linear ⁇ -olefin, or a halide thereof from the viewpoint of a higher flash point. Group, more preferably a branched alkyl group.
• the number of alkyl groups in the alkylbenzene (B) is 1 to 4, and preferably 1 or 2 (that is, monoalkylbenzene, dialkylbenzene, or a mixture thereof) from the viewpoint of stability and availability. is there.
• the alkylbenzene (B) may contain only an alkylbenzene having a single structure, has 1 to 4 alkyl groups having 1 to 40 carbon atoms, and has a total carbon number of 20 to 40 alkyl groups. If it is the alkylbenzene which satisfy
• Poly ⁇ -olefin is a compound obtained, for example, by polymerizing several molecules of a straight chain olefin having 6 to 18 carbon atoms having a double bond only at one end and then hydrogenating the polymer.
• the poly ⁇ -olefin may be, for example, isoparaffin having a molecular weight distribution centered on a trimer or tetramer of ⁇ -decene having 10 carbon atoms or ⁇ -dodecene having 12 carbon atoms.
• esters include aromatic esters, dibasic acid esters, polyol esters, complex esters, carbonate esters, and mixtures thereof.
• the ester is preferably a polyol ester or a complex ester.
• Polyol ester is an ester of 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 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%, still more preferably 70 to 100 mol%, particularly preferably 90. ⁇ 100 mol%.
• 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 may be linear or branched.
• the fatty acid is preferably a fatty acid having a branch at the ⁇ -position and / or ⁇ -position, and more preferably 2-methylpropanoic acid, 2-methylbutanoic acid, 2-methylpentanoic acid, 2-methylhexanoic acid, 2-ethyl It is selected from pentanoic acid, 2-methylheptanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexadecanoic acid, more preferably 2-ethylhexanoic acid and 3,5,5- Selected from trimethylhexanoic acid.
• the fatty acid may contain a fatty acid other than a fatty acid having 4 to 20 carbon atoms.
• the fatty acid other than the fatty acid having 4 to 20 carbon atoms may be, for example, a fatty acid having 21 to 24 carbon atoms.
• the fatty acid having 21 to 24 carbon atoms may be henicoic acid, docosanoic acid, tricosanoic acid, tetracosanoic acid or the like, and may be linear or branched.
• the polyhydric alcohol constituting the polyol ester a polyhydric alcohol having 2 to 6 hydroxyl groups is preferably used.
• the carbon number of the polyhydric alcohol is preferably 4 to 12, more preferably 5 to 10.
• the polyhydric alcohol is preferably hindered such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, dipentaerythritol.
• pentaerythritol More preferred is pentaerythritol, dipentaerythritol, or a mixed alcohol of pentaerythritol and dipentaerythritol, since it is an alcohol and is particularly excellent in compatibility with the refrigerant and hydrolysis stability.
• the complex ester is an ester synthesized by the following method (a) or (b), for example.
• Method of esterifying with monohydric alcohol (b) Adjusting the molar ratio between the polyhydric alcohol and the polybasic acid to synthesize an ester intermediate in which a part of the hydroxyl groups of the polyhydric alcohol remain unesterified, Next, a method of esterifying the remaining hydroxyl group with a monovalent fatty acid
• the complex ester obtained by the method (b) is slightly inferior in stability to the complex ester obtained by the method (a) because a relatively strong acid is generated when hydrolyzed during use as a refrigerating machine oil. There is a tendency. Therefore, the complex ester is preferably a complex ester obtained by the method (a) having higher stability.
• the complex ester is preferably at least one selected from polyhydric alcohols having 2 to 4 hydroxyl groups, at least one selected from polybasic acids having 6 to 12 carbon atoms, and 4 to 18 carbon atoms.
• polyhydric alcohol having 2 to 4 hydroxyl groups examples include neopentyl glycol, trimethylol propane, pentaerythritol and the like.
• the polyhydric alcohol having 2 to 4 hydroxyl groups is preferably neopentyl glycol and trimethylol from the viewpoint of securing a suitable viscosity when a complex ester is used as a base oil and obtaining good low temperature characteristics. From the viewpoint of being selected from propane and capable of widely adjusting the viscosity, neopentyl glycol is more preferable.
• the polyhydric alcohol constituting the complex ester is preferably a dihydric alcohol having 2 to 10 carbon atoms other than neopentyl glycol in addition to the polyhydric alcohol having 2 to 4 hydroxyl groups.
• the dihydric alcohol having 2 to 10 carbon atoms other than neopentyl glycol include ethylene glycol, propanediol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, and 3-methyl-1,5. -Pentanediol, 2,2-diethyl-1,3-pentanediol and the like.
• the dihydric alcohol is preferably butanediol from the viewpoint of excellent lubricating base oil characteristics.
• butanediol examples include 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, and the like.
• the butanediol is preferably selected from 1,3-butanediol and 1,4-butanediol from the viewpoint of obtaining good characteristics.
• the amount of the dihydric alcohol having 2 to 10 carbon atoms other than neopentyl glycol is preferably 1.2 mol or less, more preferably 0.8 mol, based on 1 mol of the polyhydric alcohol having 2 to 4 hydroxyl groups. It is less than mol, more preferably less than 0.4 mol.
• polybasic acid having 6 to 12 carbon atoms examples include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, trimellitic acid and the like.
• the polybasic acid is preferably selected from adipic acid and sebacic acid, more preferably adipic acid, from the viewpoint of excellent balance of characteristics of the synthesized ester and easy availability.
• the amount of the polybasic acid having 6 to 12 carbon atoms is preferably 0.4 mol to 4 mol, more preferably 0.5 mol to 3 mol per mol of the polyhydric alcohol having 2 to 4 hydroxyl groups. Mol, more preferably 0.6 mol to 2.5 mol.
• Examples of the monohydric alcohol having 4 to 18 carbon atoms include aliphatic alcohols such as butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, dodecanol, and oleyl alcohol. These monohydric alcohols may be linear or branched.
• the monohydric alcohol having 4 to 18 carbon atoms is preferably a monohydric alcohol having 6 to 10 carbon atoms, and more preferably a monohydric alcohol having 8 to 10 carbon atoms from the viewpoint of balance of characteristics.
• the monohydric alcohol is more preferably selected from 2-ethylhexanol and 3,5,5-trimethylhexanol from the viewpoint of improving the low temperature characteristics of the synthesized complex ester.
• Examples of the monovalent fatty acid having 2 to 12 carbon atoms include ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid and the like. These monovalent fatty acids may be linear or branched.
• the monovalent fatty acid having 2 to 12 carbon atoms is preferably a monovalent fatty acid having 8 to 10 carbon atoms, and among these, 2-ethylhexanoic acid, 3,5,5-trimethyl are more preferable from the viewpoint of low temperature characteristics. Hexanoic acid.
• ethers include polyvinyl ether, polyalkylene glycol, polyphenyl ether, perfluoroether, and mixtures thereof.
• the ether is preferably selected from polyvinyl ether and polyalkylene glycol, more preferably polyvinyl ether.
• Polyvinyl ether has a structural unit represented by the following 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
• R 4 is a divalent hydrocarbon group or a divalent ether bond.
• 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 is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 8 or less, more preferably 7 Hereinafter, it is more preferably 6 or less.
• R 1, at least one of R 2 and R 3 is a hydrogen atom, more preferably all of R 1, R 2 and R 3 are hydrogen atoms.
• the carbon number of the divalent hydrocarbon group represented by R 4 and the ether-bonded oxygen-containing hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and preferably 10 or less. More preferably, it is 8 or less, More preferably, it is 6 or less.
• the divalent ether bond oxygen-containing hydrocarbon group represented by R 4 may be, for example, a hydrocarbon group having oxygen in the side chain to form an ether bond.
• R 5 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.
• the hydrocarbon group is preferably an alkyl group, more preferably an alkyl group having 1 to 5 carbon atoms.
• M is preferably 0 or more, more preferably 1 or more, still more preferably 2 or more, and is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less.
• the average value of m in all structural units constituting the polyvinyl ether is preferably 0 to 10.
• the polyvinyl ether may be a homopolymer composed of one type selected from the structural unit represented by the formula (1), or composed of two or more types selected from the structural unit represented by the formula (1).
• the copolymer may be a copolymer composed of the structural unit represented by the formula (1) and another structural unit.
• 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 a structural unit (1-1) represented by the above formula (1) and R 5 is an alkyl group having 1 to 3 carbon atoms, and the above formula ( And a structural unit (1-2) in which R 5 is an alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 8 carbon atoms.
• R 5 is an alkyl group having 3 to 20, preferably 3 to 10, more preferably 3 to 8 carbon atoms.
• the molar ratio of the structural unit (1-1) to the structural unit (1-2) is preferably 5:95 to 95: 5, more preferably 20:80 to 90:10, and still more preferably 70:30 to 90:10.
• 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 above formula (1), but may be a copolymer further having a structural unit represented by the following formula (2). .
• the copolymer may be a block copolymer or a random copolymer.
• R 6 to R 9 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. ]
• the polyvinyl ether is represented by the polymerization of a vinyl ether monomer corresponding to the structural unit represented by the formula (1), or the vinyl ether monomer corresponding to the structural unit represented by the formula (1) and the formula (2). It can be produced by copolymerization with a hydrocarbon monomer having an olefinic double bond corresponding to the structural unit.
• a monomer represented by the following formula (3) is suitable. Wherein, 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 and m, respectively formula (1) Indicates. ]
• 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 has 1 to 10 carbon atoms.
• R 61 , R 71 , R 81 and R 91 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 12 , R 22 and R 32 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, and R 42 has 1 to 10 carbon atoms.
• 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. ]
• polyvinyl ethers the following polyvinyl ethers (a), (b), (c), (d) and (e) are particularly suitable as the base oil.
• one end is represented by formula (4) or (5) and the other end is represented by formula (6) or (7), and R 1 and R in formula (1)
• B It has only the structural unit represented by Formula (1), Comprising: One terminal is represented by Formula (4), and the other terminal has a structure represented by Formula (6).
• R 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 1 carbon atom.
• Polyvinyl ether which is ⁇ 20 hydrocarbon groups.
• One end is represented by formula (4) or (5) and the other end is represented by formula (8), and R 1 , R 2 and R 3 in 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, and R 5 is a hydrocarbon group having 1 to 20 carbon atoms.
• (D) It has only the structural unit represented by Formula (1), and has one end represented by Formula (5) and the other end represented by Formula (8).
• R 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
• R 5 is 1 carbon atom.
• Polyvinyl ether which is ⁇ 20 hydrocarbon groups.
• the weight average molecular weight of polyvinyl ether is preferably 500 or more, more preferably 600 or more, preferably 3000 or less, more preferably 2000 or less, and further preferably 1500 or less.
• the weight average molecular weight of polyvinyl ether is 500 or more, the lubricity in the presence of a refrigerant is excellent.
• the weight average molecular weight is 3000 or less, the composition range showing compatibility with the refrigerant under a low temperature condition is widened, and poor lubrication of the refrigerant compressor and inhibition of heat exchange in the evaporator can be suppressed.
• the number average molecular weight of the polyvinyl ether is preferably 500 or more, more preferably 600 or more, preferably 3000 or less, more preferably 2000 or less, and further preferably 1500 or less.
• the number average molecular weight of polyvinyl ether is 500 or more, the lubricity in the presence of a refrigerant is excellent.
• the number average molecular weight is 3000 or less, the composition range showing compatibility with the refrigerant under a low temperature condition is widened, and poor lubrication of the refrigerant compressor and inhibition of heat exchange in the evaporator can be suppressed.
• the weight average molecular weight and number average molecular weight of polyvinyl ether mean the weight average molecular weight and the number average molecular weight (polystyrene (standard sample) conversion value) obtained by GPC analysis, respectively.
• a weight average molecular weight and a number average molecular weight can be measured as follows, for example.
• 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 still more preferably 1.0 meq / kg or less.
• 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. That is, the degree of unsaturation in the present invention is determined by 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 content with sodium thiosulfate. The iodine value is calculated, and the iodine value is converted to a vinyl equivalent (meq / g).
• the peroxide value in the present invention is 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 is a calibration curve obtained by allowing 2,4-dinitrophenylhydrazine to act on a sample to produce a chromoid quinoid ion, measuring the absorbance of this sample at 480 nm, and using cinnamaldehyde as a standard substance in advance.
• the hydroxyl value in the present invention means a hydroxyl value measured according to JIS K0070: 1992.
• polyalkylene glycol examples include polyethylene glycol, polypropylene glycol and polybutylene glycol.
• Polyalkylene glycol has oxyethylene, oxypropylene, oxybutylene or the like as a structural unit.
• Polyalkylene glycols having these structural units 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 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.
• At least one of R ⁇ and R ⁇ is preferably an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group, from the viewpoint of excellent compatibility.
• both R ⁇ and R ⁇ are preferably alkyl groups, more preferably alkyl groups having 1 to 4 carbon atoms, and still more preferably methyl groups.
• both R ⁇ and R ⁇ are preferably hydrogen atoms.
• R ⁇ represents an alkylene group having 2 to 4 carbon atoms, and specific examples of such 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.
• Oxyalkylene group represented by (OR ⁇ ) f may consist of one oxyalkylene group, or may be composed of two or more oxyalkylene groups.
• the polyalkylene glycol represented by the formula (9) is preferably a copolymer having an oxyethylene group (EO) and an oxypropylene group (PO) from the viewpoint of excellent compatibility with the refrigerant and viscosity-temperature characteristics. It is a coalescence.
• the ratio of oxyethylene groups to the total of oxyethylene groups and oxypropylene groups (EO / (PO + EO)) is preferably 0.1 to 0.8. More preferably, it is 0.3 to 0.6.
• EO / (PO + EO) is preferably 0 to 0.5, more preferably 0 to 0.2, and even more preferably 0 (ie, propylene oxide homopolymer). It is.
• 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 average value of the product of f and g (f ⁇ g) is preferably 6 to 80 from the viewpoint of satisfying the required performance as a refrigerating machine oil in a well-balanced manner.
• the weight average molecular weight of the polyalkylene glycol is preferably 500 or more, more preferably 600 or more, preferably 3000 or less, more preferably 2000 or less, and further preferably 1500 or less.
• the weight average molecular weight of the polyalkylene glycol is 500 or more, the lubricity in the presence of a refrigerant is excellent.
• the weight average molecular weight is 3000 or less, the composition range showing compatibility with the refrigerant under a low temperature condition is widened, and poor lubrication of the refrigerant compressor and inhibition of heat exchange in the evaporator can be suppressed.
• the number average molecular weight of the polyalkylene glycol is preferably 500 or more, more preferably 600 or more, preferably 3000 or less, more preferably 2000 or less, and further preferably 1500 or less.
• the number average molecular weight of the polyalkylene glycol is 500 or more, the lubricity in the presence of a refrigerant is excellent.
• the number average molecular weight is 3000 or less, the composition range showing compatibility with the refrigerant under a low temperature condition is widened, and poor lubrication of the refrigerant compressor and inhibition of heat exchange in the evaporator can be suppressed.
• the weight average molecular weight and the number average molecular weight of the polyalkylene glycol mean the weight average molecular weight and the number average molecular weight (in terms of polypropylene glycol (standard sample)) obtained by GPC analysis, respectively.
• a weight average molecular weight and a number average molecular weight can be measured as follows, for example.
• the hydroxyl value of the polyalkylene glycol 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). For example, an alcohol (R ⁇ OH; R ⁇ formula (9) R alpha and represent the same definition in) etherified or esterified into by addition polymerization of one or more predetermined alkylene oxide, further terminal hydroxyl groups By doing this, the polyalkylene glycol represented by 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. In view of the above, a block copolymer is preferable, and a random copolymer is preferable from the viewpoint of excellent low-temperature fluidity.
• the degree of unsaturation of the polyalkylene glycol is preferably 0.04 meq / g or less, more preferably 0.03 meq / g or less, still more 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 still more preferably 1.0 meq / kg or less.
• the carbonyl value 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 lubricating base oil is preferably at least one selected from oxygenated oils, more preferably at least one selected from esters and ethers.
• Kinematic viscosity at 40 ° C. of the lubricating base oil is preferably 3 mm 2 / s or more, more preferably 4 mm 2 / s or more, may be even more preferably at 5 mm 2 / s or more.
• Kinematic viscosity at 40 ° C. of the lubricating base oil is preferably 1000 mm 2 / s or less, more preferably 500 mm 2 / s or less, more preferably may be at 400 mm 2 / s or less.
• the kinematic viscosity at 100 ° C. of the lubricating base oil may be preferably 1 mm 2 / s or more, more preferably 2 mm 2 / s or more.
• the kinematic viscosity at 100 ° C. of the lubricating base oil may be preferably 100 mm 2 / s or less, more preferably 50 mm 2 / s or less.
• the kinematic viscosity in the present invention means a kinematic viscosity measured according to JIS K2283: 2000.
• the content of the lubricating base oil may be 50% by mass or more, 60% by mass or more, 70% by mass or more, 80% by mass or more, or 90% by mass or more based on the total amount of the refrigerating machine oil.
• the compound represented by the formula (A) is preferably a compound represented by any one of the following formulas (A-1) to (A-3). Wherein (A-1) ⁇ (A -3), R a, R b, R c and X are R a, R b in the formula (A), respectively R c and X synonymous.
• the monovalent hydrocarbon group represented by R a and R b may have 2 to 18, 2 to 16, 2 to 14, 2 to 12, 2 to 10, or 2 to 8 carbon atoms.
• the monovalent hydrocarbon group may be a linear or branched alkyl group.
• the divalent hydrocarbon group represented by R c may have 1 to 4, 1 to 3, 1 to 2, or 1 carbon atoms.
• the divalent hydrocarbon group may be a linear or branched alkylene group.
• the polar group represented by X may have an oxygen atom.
• the polar group includes, for example, —OH group, —COOH group, —COOR group, —CONHNH 2 group, —CONH 2 group, —NR 2 group, —CN group, —CH (COOH) CH 2 COOH group, —CH It may be either a (COOR) CH 2 COOH group or a group represented by the following formulas (x-1) to (x-4).
• the polar group represented by X is preferably an —OH group, —COOH group, —COOR group, —CH (COOH) CH 2 COOH group, or —CH (COOR) CH 2 COOH group.
• R in the —COOR group, —NR 2 group, and —CH (COOR) CH 2 COOH group may be a monovalent hydrocarbon group or a linear or branched alkyl group.
• the monovalent hydrocarbon group and alkyl group may have 1 to 12, 1 to 8, or 1 to 2.
• the compound represented by the formula (A) may be a compound represented by the following formula (A-4).
• R d and R e each independently represent a linear or branched alkyl group having 2 to 8 carbon atoms
• X a represents an —OH group, —COOH group, or —COOR ′ group
• R ′ represents a carbon number of 1 Represents a linear or branched alkyl group of ⁇ 8).
• the content of the compound represented by the formula (A) may be 0.005% by mass or more, 0.01% by mass or more, or 0.02% by mass or more based on the total amount of the refrigerating machine oil, and 0.1% by mass. Hereinafter, it may be 0.2% by mass or less or 1% by mass or less.
• the content of the compound represented by the formula (A) is 0.005 to 0.1% by mass, 0.005 to 0.2% by mass, 0.005 to 1% by mass, and 0.005% by mass based on the total amount of the refrigerating machine oil. 01 to 0.1% by mass, 0.01 to 0.2% by mass, 0.01 to 1% by mass, 0.02 to 0.1% by mass, 0.02 to 0.2% by mass, or 0.02 to It may be 1% by weight.
• the refrigerating machine oil may further contain an epoxy compound.
• the epoxy compound 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 are used individually by 1 type or in combination of 2 or more types.
• the glycidyl ether type epoxy compound may be, for example, an aryl glycidyl ether type epoxy compound or an alkyl glycidyl ether type epoxy compound represented by the following formula (B-1).
• R f represents an aryl group having 6 to 18 carbon atoms or an alkyl group having 5 to 18 carbon atoms.
• the glycidyl ether type epoxy compound represented by the formula (B-1) is preferably 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
• the glycidyl ether type epoxy compound may be a compound other than the epoxy compound represented by the formula (B-1), specifically, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetra It may be glycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, or the like.
• the glycidyl ester type epoxy compound may be, for example, a compound represented by the following formula (B-2).
• R g represents an aryl group having 6 to 18 carbon atoms, an alkyl group having 5 to 18 carbon atoms, or an alkenyl group having 5 to 18 carbon atoms.
• the glycidyl ester type epoxy compound represented by the formula (B-2) is preferably glycidyl benzoate, glycidyl neodecanoate, glycidyl-2,2-dimethyloctanoate, glycidyl acrylate, or glycidyl methacrylate.
• the alicyclic epoxy compound is a compound represented by the following formula (B-3) having a partial structure in which the carbon atoms constituting the epoxy group directly constitute an alicyclic ring.
• Examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3 ′, 4′-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, bis (3,4-epoxy (Cyclohexylmethyl) 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, It may be 4-epoxyethyl-1,2-epoxycyclohexane.
• allyloxirane compounds examples include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene, and the like.
• 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, 1,2-epoxyoctadecane, 1,2-epoxynonadecane, and 1,2-epoxyicosane.
• epoxidized fatty acid monoesters examples include esters of epoxidized fatty acids having 12 to 20 carbon atoms with alcohols having 1 to 8 carbon atoms, phenol or alkylphenol.
• the epoxidized fatty acid monoester is preferably a butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl or butylphenyl ester of epoxystearate.
• Examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.
• the refrigerating machine oil contains both the compound represented by the formula (A) and the epoxy compound
• the refrigerating machine oil has only abrasion resistance as compared with, for example, a conventional refrigerating machine oil containing an acidic phosphate ester and an epoxy compound. It also has excellent stability.
• the epoxy compound is preferably at least one selected from a glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, and an alicyclic epoxy compound, more preferably, from the viewpoint of both wear resistance and stability. It is at least one selected from glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds.
• the content of the epoxy compound is preferably 0.1% by mass or more, more preferably 0.15% by mass or more, and further preferably 0.2% by mass or more, based on the total amount of refrigerating machine oil, from the viewpoint of improving stability. is there.
• the content of the epoxy compound is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, still more preferably 2.0% by mass or less, based on the total amount of refrigerating machine oil, from the viewpoint of improving lubricity. is there.
• Refrigerating machine oil may further contain other additives.
• other additives include acid scavengers other than epoxy compounds, antioxidants, extreme pressure agents, oiliness agents, antifoaming agents, metal deactivators, and compounds other than compounds represented by formula (A).
• the content of these additives may be 10% by mass or less or 5% by mass or less based on the total amount of refrigerating machine oil.
• the refrigerating machine oil preferably further contains at least one of an antioxidant and an antiwear agent other than the compound represented by the formula (A) among the other additives described above.
• Antioxidants are 2,6-di-tert. It may be a phenol-based antioxidant such as butyl-p-cresol or bisphenol A, or an amine-based antioxidant such as alkylphenyl ⁇ -naphthylamine or dialkyldiphenylamine.
• Antiwear agents other than the compound represented by the formula (A) include phosphoric acid esters, acidic phosphoric acid esters, thiophosphoric acid esters, amine salts of acidic phosphoric acid esters, chlorinated phosphoric acid esters, phosphorous acid esters and the like. It may be a system wear inhibitor.
• 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, may be even more preferably at 5 mm 2 / s or more.
• Kinematic viscosity at 40 ° C. of the refrigerating machine oil is preferably 500 mm 2 / s or less, more preferably 400 mm 2 / s or less, more preferably may be less 300 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.
• Kinematic viscosity at 100 ° C. of the refrigerating machine oil is preferably 100 mm 2 / s or less, more preferably be not more than 50 mm 2 / s.
• the pour point of the refrigerating machine oil may be preferably ⁇ 10 ° C. or lower, more preferably ⁇ 20 ° C. or lower.
• the pour point in the present invention means a pour point measured according to JIS K2269-1987.
• the volume resistivity of the refrigerating machine oil is preferably 1.0 ⁇ 10 9 ⁇ ⁇ m or more, more preferably 1.0 ⁇ 10 10 ⁇ ⁇ m or more, and further preferably 1.0 ⁇ 10 11 ⁇ ⁇ m or more. It's okay.
• the volume resistivity in the present invention means a volume resistivity at 25 ° C. measured according to JIS C2101: 1999.
• the water content of the refrigerating machine oil is preferably 200 ppm or less, more preferably 100 ppm or less, and even more preferably 50 ppm or less, based on the total amount of the refrigerating machine oil.
• the acid value of the refrigerating machine oil is preferably 1.0 mgKOH / g or less, more preferably 0.1 mgKOH / g or less.
• the acid value in the present invention means an acid value measured according to JIS K2501: 2003.
• the ash content of the refrigerating machine oil is preferably 100 ppm or less, more preferably 50 ppm or less.
• the ash content in the present invention means an ash content measured according to JIS K2272: 1998.
• Refrigerator oil according to the present embodiment is used together with a refrigerant.
• the refrigerant include saturated fluorinated hydrocarbon refrigerants, unsaturated fluorinated hydrocarbon refrigerants, hydrocarbon refrigerants, fluorinated ether refrigerants such as perfluoroethers, bis (trifluoromethyl) sulfide refrigerant, and trifluoroiodomethane.
• refrigerants natural refrigerants such as ammonia and carbon dioxide, and mixed refrigerants containing one or more of these refrigerants.
• the saturated fluorinated hydrocarbon refrigerant is preferably a saturated fluorinated hydrocarbon having 1 to 3 carbon atoms, more preferably 1 to 2 carbon atoms.
• the saturated fluorinated hydrocarbon refrigerant is appropriately selected from the above depending on the application and required performance.
• R32 alone; R23 alone; R134a alone; R125 alone; R134a / R32 60 to 80% by mass / 40
• R20 / R125 40-70 wt% / 60-30 wt% mixture
• R125 / R143a 40-60 wt% / 60-40 wt% mixture
• R134a / R32 / R125 60 Mixture of wt% / 30 wt% / 10 wt%
• R134a / R32 / R125 40-70 wt% / 15-35 wt% / 5-40 wt% mixture
• R125 / R134a / R143a 35-55 wt%
• a preferred example is a mixture of 1 to 15% by mass / 40 to 60% by mass.
• the unsaturated fluorinated hydrocarbon (HFO) refrigerant is preferably an unsaturated fluorinated hydrocarbon having 2 to 3 carbon atoms, more preferably fluoropropene, and still more preferably fluoropropene having 3 to 5 fluorine atoms.
• the unsaturated fluorinated hydrocarbon refrigerant is preferably 1,2,3,3,3-pentafluoropropene (HFO-1225ye), 1,3,3,3-tetrafluoropropene (HFO-1234ze), 2, Any of 3,3,3-tetrafluoropropene (HFO-1234yf), 1,2,3,3-tetrafluoropropene (HFO-1234ye), and 3,3,3-trifluoropropene (HFO-1243zf) One or a mixture of two or more.
• the unsaturated fluorinated hydrocarbon refrigerant is preferably one or more selected from HFO-1225ye, HFO-1234ze and HFO-1234yf from the viewpoint of the physical properties of the refrigerant.
• the unsaturated fluorinated hydrocarbon refrigerant may be fluoroethylene, preferably 1,1,2,3-trifluoroethylene (HFO-1123).
• the unsaturated fluorinated hydrocarbon refrigerant may be 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) and cis-1-chloro-2,3,3,3-tetra It may be any of fluoropropene (HCFO-1224yd (Z)), trans-1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd (E)) and mixtures thereof.
• the hydrocarbon refrigerant is preferably a hydrocarbon having 1 to 5 carbon atoms, more preferably a hydrocarbon having 2 to 4 carbon atoms.
• specific examples of the hydrocarbon include methane, ethylene, ethane, propylene, propane (R290), cyclopropane, normal butane, isobutane, cyclobutane, methylcyclopropane, 2-methylbutane, normal pentane, or two or more of these. Of the mixture.
• hydrocarbon refrigerants that are gaseous at 25 ° C. and 1 atm are preferably used, and propane, normal butane, isobutane, 2-methylbutane, or a mixture thereof is more preferably used.
• the refrigerant used together with the refrigerating machine oil may be a mixed refrigerant including one or more selected from the above-mentioned refrigerants, for example, one selected from unsaturated hydrocarbon (HFO) refrigerants or A refrigerant mixture of two or more refrigerants and one or two or more refrigerants selected from saturated fluorinated hydrocarbon (HFC) refrigerants, or a refrigerant selected from hydrocarbon refrigerants and natural refrigerants, or It may be a mixed refrigerant obtained by further mixing two or more kinds of refrigerants.
• HFO unsaturated hydrocarbon
• HFC saturated fluorinated hydrocarbon
• the refrigerant is, for example, one or more HFO refrigerants selected from HFO-1225ye, HFO-1234ze, HFO-1234yf, HFO-1123, HCFO-1224yd, and the like, and R32, R134a, R125. , R152a, R227ea, R236fa, etc., or a mixed refrigerant with one or more HFC refrigerants, or a mixed refrigerant obtained by further mixing a hydrocarbon refrigerant such as R290, R600a, or a natural refrigerant such as R744 with the mixed refrigerant. It may be.
• such a mixed refrigerant is R444A, R445A, R446A, R447A, R447B, R448A, R449A, R449C, R452B, R454B, R454C, R455A, R456A, R457A, R458A, R459A, R459B, R459A, R459B, , R513A and the like, but is not limited thereto.
• Refrigerator oil according to the present embodiment is usually present in the state of a working fluid composition for a refrigerator mixed with a refrigerant in a refrigerator. That is, the working fluid composition for a refrigerator according to the present embodiment contains the above-described refrigerator oil and the above-described refrigerant.
• the content of the refrigerating machine oil in the working fluid composition for a refrigerating machine is preferably 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 refrigerating machine oil and the working fluid composition for the refrigerating machine according to the present embodiment include an air conditioner having a reciprocating or rotating hermetic compressor, a refrigerator, an open type or a sealed car air conditioner, a dehumidifier, a water heater, and a freezer. It is suitably used for refrigerators such as refrigerators, refrigerators, vending machines, showcases, chemical plants, refrigerators having a centrifugal compressor, and the like.
• refrigeration oils having the compositions shown in Tables 1 to 3 were prepared using the following base oils and additives.
• Base oil 1 Polyol ester of pentaerythritol and 2-methylpropanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid (mass ratio: 35/65) (kinematic viscosity at 40 ° C .: 67 .2 mm 2 / s, viscosity index: 84)
• Base oil 2 To an ester intermediate obtained by reacting neopentyl glycol (1 mol) and 1,4-butanediol (0.3 mol) with adipic acid (2.4 mol), 2-ethylhexanol (2.4 mol) Mol)), and a complex ester obtained by removing the remaining unreacted product by distillation (kinematic viscosity at 40 ° C .: 68.2 mm 2
• Base oil 3 polyethyl vinyl ether (number average molecular weight: 1900, kinematic viscosity at 40 ° C .: 71.0 mm 2 / s, kinematic viscosity at 100 ° C .: 8.6 mm 2 / s, viscosity index: 89)
• Base oil 4 Polyol ester of pentaerythritol and 2-ethylhexanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid (mass ratio: 50/50) (kinematic viscosity at 40 ° C .: 68 mm) 2 / s)
• Base oil 5 3,5,5-trimethylhexanol as an ester intermediate obtained by reacting neopentyl glycol (1 mol) and 1,4-butanediol (0.3 mol) with adipic acid (2.4 mol) (2.4 mol) was further reacted, and the complex ester obtained by removing
• Base oil 6 Polyol ester of dipentaerythritol and 2-ethylhexanoic acid / 3,5,5-trimethylhexanoic acid mixed fatty acid (mass ratio: 50/50) (kinematic viscosity at 40 ° C .: 220 mm 2 / s)
• Base oil 7 Polyol ester of pentaerythritol and a mixed fatty acid (mass ratio: 25/75) of pentanoic acid / 3,5,5-trimethylhexanoic acid (kinematic viscosity at 40 ° C .: 68 mm 2 / s)
• Base oil 8 Polypropylene glycol dimethyl ether (number average molecular weight (Mn): 1000, 40 ° C.
• A1 Compound represented by the following formula (A-1-1)
• A2 Compound represented by the following formula (A-1-2)
• A3 Compound represented by the following formula (A-1-3)
• a1 tricresyl phosphate a2: di (n-octyl) acid phosphate
• B1 glycidyl neodecanoate
• B2 2-ethylhexyl glycidyl ether
• the abrasion resistance test was performed by a high-speed four-ball test. Using SUJ-2 as a hard sphere, the test was conducted under the conditions of a test oil amount of 20 mL, a test temperature of 80 ° C., a rotation speed of 1200 rpm, a load load of 294 N, and a test time of 30 minutes. For the evaluation of wear resistance, the average value of the wear scar diameter (mm) of the fixed sphere was used.
• Example 8 the refrigerating machine oils of Examples 10 to 16 were prepared using the following base oils in place of the base oil 1.

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