WO2017122786A1 - 冷凍機油、及び冷凍機用組成物 - Google Patents
冷凍機油、及び冷凍機用組成物 Download PDFInfo
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- WO2017122786A1 WO2017122786A1 PCT/JP2017/001042 JP2017001042W WO2017122786A1 WO 2017122786 A1 WO2017122786 A1 WO 2017122786A1 JP 2017001042 W JP2017001042 W JP 2017001042W WO 2017122786 A1 WO2017122786 A1 WO 2017122786A1
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- machine oil
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- 0 *C(*)(c1ccccc1)OP(Oc1ccccc1)(Oc1cccc(C(*)(*)OP(Oc2ccccc2)(Oc2ccccc2)=O)c1)=O Chemical compound *C(*)(c1ccccc1)OP(Oc1ccccc1)(Oc1cccc(C(*)(*)OP(Oc2ccccc2)(Oc2ccccc2)=O)c1)=O 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
- C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
- C10M105/32—Esters
- C10M105/38—Esters of polyhydroxy compounds
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- 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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
- C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
- C10M133/38—Heterocyclic nitrogen compounds
- C10M133/44—Five-membered ring containing nitrogen and carbon only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M137/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus
- C10M137/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing phosphorus having no phosphorus-to-carbon bond
- C10M137/04—Phosphate esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- 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
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/04—Ethers; Acetals; Ortho-esters; Ortho-carbonates
- C10M2207/042—Epoxides
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- C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
- C10M2207/28—Esters
- C10M2207/283—Esters of polyhydroxy compounds
- C10M2207/2835—Esters of polyhydroxy compounds used as base material
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/02—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/04—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical
- C10M2209/043—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol or ester thereof; bound to an aldehyde, ketonic, ether, ketal or acetal radical used as base material
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- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2209/00—Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
- C10M2215/22—Heterocyclic nitrogen compounds
- C10M2215/223—Five-membered rings containing nitrogen and carbon only
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
- C10M2223/04—Phosphate esters
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
- C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
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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
- 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
- C10M2229/02—Unspecified siloxanes; Silicones
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/101—Containing Hydrofluorocarbons
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- 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
- C10N2020/103—Containing Hydrocarbons
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- 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
- C10N2020/105—Containing Ammonia
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- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
- C10N2020/09—Characteristics associated with water
- C10N2020/097—Refrigerants
- C10N2020/106—Containing Carbon dioxide
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
- C10N2030/02—Pour-point; Viscosity index
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- 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
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- 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 refrigerating machine oil and a composition for a refrigerating machine using the refrigerating machine oil.
- the refrigerator has a structure in which a mixture of refrigerant and refrigerator oil (hereinafter also referred to as “composition for refrigerator”) circulates in a closed system, and the refrigerator oil has compatibility with the refrigerant, Stability and lubrication performance are required.
- composition for refrigerator a mixture of refrigerant and refrigerator oil
- many refrigerating machine oils containing an oxygen-containing organic compound such as a vinyl ether compound as a main component are used (for example, see Patent Document 1).
- hydrofluorocarbon HFC
- hydrochlorofluorocarbon HCFC
- saturated hydrofluorocarbons saturated HFCs
- R32 difluoroethane
- R410A mixture of difluoroethane and pentafluoroethane
- TCP tricresyl phosphate
- Patent Document 2 It is known to add a phosphoric acid ester compound having one (see, for example, Patent Document 2). It is also known that wear resistance is improved by using a phosphate ester compound having one phosphorus atom such as tricresyl phosphate (TCP) in combination with a benzotriazole-based compound in a lubricating oil composition. (See Patent Documents 3 and 4).
- TCP tricresyl phosphate
- JP-A-6-128578 Japanese Patent Laid-Open No. 10-130683 JP-A-8-259980 Japanese Patent Laid-Open No. 7-126680
- the present invention has been made in view of the above problems, and when using a refrigerating machine oil containing an oxygen-containing organic compound as a base oil, it is an object to reduce the friction coefficient while improving wear resistance.
- the present invention provides the following refrigerating machine oil, a composition for a refrigerating machine, and a method for producing refrigerating machine oil.
- Refrigerating machine oil containing a base oil containing an oxygen-containing organic compound, a polyphosphate ester compound, and a benzotriazole compound (2) A refrigerating machine composition comprising a refrigerant and the refrigerating machine oil described in (1) above.
- a method for producing refrigerating machine oil wherein a refrigerating machine oil is obtained by blending at least a polyphosphate ester compound and a benzotriazole compound with a base oil containing an oxygen-containing organic compound.
- a refrigerating machine oil capable of reducing the coefficient of friction while improving wear resistance is provided by including a specific phosphorus compound and a benzotriazole compound in the base oil.
- the refrigerating machine oil according to one embodiment of the present invention includes a base oil, a polyphosphate ester compound, and a benzotriazole compound.
- a base oil a polyphosphate ester compound
- a benzotriazole compound a benzotriazole compound
- the base oil in this embodiment contains an oxygen-containing organic compound.
- oxygen-containing organic compounds include synthetic oils containing an ether group, ketone group, ester group, carbonate group, etc. in the molecule, and hetero atoms (sulfur atom, fluorine atom, chlorine atom, silicon atom, nitrogen atom) together with these groups. And synthetic oils containing atoms). More specifically, polyvinyl ethers (PVE), polyoxyalkylene glycols (PAG), poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether (ECP), and polyol esters (POE) ).
- An oxygen-containing organic compound may be used individually by 1 type, and may use 2 or more types together.
- PVE polyvinyl ethers
- PEG polyoxyalkylene glycols
- PVE polyvinyl ethers
- PVE is a polyphosphate ester compound in which R 9 is a group represented by the following general formula (1) and R 9 is represented by the general formula (2).
- R 9 is a group represented by the following general formula (1)
- R 9 is represented by the general formula (2).
- the oxygen-containing organic compound is a main component of the refrigerating machine oil, and the oxygen-containing organic compound is preferably contained in an amount of 70 to 99.98% by mass with respect to the total amount of the refrigerating machine oil, and 90 to 99.5% by mass. %, More preferably 93.0 to 99.3% by mass.
- Polyvinyl ethers (PVE) are polymers having a structural unit derived from vinyl ether, and specific examples include polyvinyl compounds having a structural unit represented by the following general formula (A-1).
- R 1a , R 2a and R 3a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other.
- the hydrocarbon group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, and various hexyl groups.
- R 1a , R 2a and R 3a are more preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms, more preferably a hydrogen atom.
- r represents the number of repetitions, and the average value is a number in the range of 0 to 10, with 0 being preferred.
- R 4a represents a divalent hydrocarbon group having 2 to 10 carbon atoms.
- the divalent hydrocarbon group having 2 to 10 carbon atoms include an ethylene group, a phenylethylene group, 1, 2-propylene group, 2-phenyl-1,2-propylene group, 1,3-propylene group, various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups
- a divalent aliphatic hydrocarbon group such as cyclohexane, methylcyclohexane, ethylcyclohexane, dimethylcyclohexane, propylcyclohexane, and other alicyclic hydrocarbon groups having two bonding sites; various phenylene groups; Divalent aromatic carbonization such as various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various naphthylenes,
- alkyl aromatic hydrocarbon groups having a bonding site in the base portion Of these, an aliphatic hydrocarbon group having 2 to 4 carbon atoms is more preferred.
- the plurality of R 4a O may be the same or different.
- R 5a in the general formula (A-1) represents a hydrocarbon group having 1 to 10 carbon atoms.
- the hydrocarbon group include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group.
- Alkyl groups such as n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups and various decyl groups; cyclopentyl group, Cyclohexyl groups, various methyl cyclohexyl groups, various ethyl cyclohexyl groups, various propyl cyclohexyl groups, various dimethyl cyclohexyl groups and other cycloalkyl groups; phenyl groups, various methyl phenyl groups, various ethyl phenyl groups, various dimethyl phenyl groups, various propyl phenyl groups , Various trimethylphenyl groups, various butylphenyl groups, various naphths An aryl group such as a til group; an arylalkyl group such as
- R 1a , R 2a and R 3a are all hydrogen atoms, r is 0, and R 5a is an ethyl group.
- a polymer or copolymer containing 50 to 100 mol% of structural units and 0 to 50 mol% of structural units in which R 5a is an alkyl group having 3 or 4 carbon atoms is preferred.
- the proportion of structural units in which R 5a is an ethyl group is 70 to 100 mol%, and the proportion of structural units in which R 5a is an alkyl group having 3 or 4 carbon atoms is more preferably 0 to 30 mol%.
- the former is 80 to 95% and the latter is 5 to 20 mol%.
- the alkyl group having 3 or 4 carbon atoms of R 5a n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group can be used. Is preferred.
- the polyvinyl ether compound has a structural unit represented by the general formula (A-1), and the number of repetitions may be appropriately selected according to the desired kinematic viscosity.
- the said polyvinyl ether type compound can be manufactured by superposition
- the vinyl ether monomers that can be used here are those represented by the following general formula (A-2).
- R 1a , R 2a , R 3a , R 4a and R 5a and r are the same as described above.
- the vinyl ether monomers include various monomers corresponding to the above-mentioned polyvinyl ether compounds.
- 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 represented by the general formula (A-1) by a known method. Good.
- the polyvinyl ether compound those having the following terminal structures (1) to (4) are preferable.
- One end of which is represented by the following general formula (A-1-i) and the other end is represented by the following general formula (A-1-ii) (Wherein R 6a , R 7a and R 8a each independently represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same as or different from each other.
- R 9a represents carbon A divalent hydrocarbon group having 2 to 10 carbon atoms
- R 10a is a hydrocarbon group having 1 to 10 carbon atoms
- r1 is an average value of 0 to 10
- a plurality of R 9a O may be the same or different.
- R 11a , R 12a and R 13a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same as or different from each other, and R 14a represents carbon A divalent hydrocarbon group of 2 to 10, R 15a represents a hydrocarbon group of 1 to 10 carbon atoms, r2 represents a number having an average value of 0 to 10, and when there are a plurality of R 14a O, a plurality of R 14a O may be the same or different.
- R 16a , R 17a and R 18a each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same as or different from each other.
- R 19a and R 21a independently represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different from each other, and
- R 20a and R 22a each independently represents a carbon atom having 1 to 10 carbon atoms.
- the polyvinyl ether-based mixture may be a mixture of two or more selected from those having the terminal structures (1) to (4). Preferred examples of such a mixture include a mixture of the above (1) and (4), and a mixture of (2) and (3). It is preferable to select a polymerization degree, a terminal structure, etc. so that a polyvinyl ether type compound may become the viscosity range of the preferable base oil mentioned later. Moreover, a polyvinyl ether type compound may be used individually by 1 type, and may be used in combination of 2 or more type.
- polyvinyl compounds having the structural unit represented by the general formula (A-1) particularly one terminal is represented by the general formula (A-1-i) and the remaining terminal is represented by the general formula (A-1).
- Those represented by A-1-ii) are preferred.
- R 6a , R 7a , R 8a , R 11a , R 12a and R 13a are hydrogen atoms, and any of r1 and r2 More preferably, R 10a and R 15a are each an alkyl group having 1 to 4 carbon atoms.
- PAG Polyoxyalkylene glycols
- the monovalent hydrocarbon group having 1 to 10 carbon atoms in each of R 1b and R 3b may be linear, branched, or cyclic.
- the hydrocarbon group is preferably an alkyl group, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, Various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups and the like can be mentioned.
- the monovalent hydrocarbon group has good compatibility with the refrigerant when the number of carbon atoms is 10 or less.
- the carbon number of the monovalent hydrocarbon group is more preferably 1 to 4.
- the hydrocarbon group portion of the acyl group having 2 to 10 carbon atoms in each of R 1b and R 3b may be linear, branched or cyclic.
- the hydrocarbon group portion of the acyl group is preferably an alkyl group, and specific examples thereof include those having 1 to 9 carbon atoms among the alkyl groups that can be selected as R 1b and R 3b described above.
- a preferred acyl group has 2 to 4 carbon atoms.
- R 1b and R 3b are both hydrocarbon groups or acyl groups, R 1b and R 3b may be the same or different from each other.
- n is 2 or more, a plurality of R 3b in one molecule may be the same or different.
- R 1b is a hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites
- the hydrocarbon group may be a chain or a cyclic one.
- the hydrocarbon group having two bonding sites is preferably an aliphatic hydrocarbon group, for example, ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group. Examples thereof include a len group and a cyclohexylene group.
- hydrocarbon groups examples include residues obtained by removing hydroxyl groups from bisphenols such as biphenol, bisphenol F, and bisphenol A.
- the hydrocarbon group having 3 to 6 binding sites is preferably an aliphatic hydrocarbon group, for example, trimethylolpropane, glycerin, pentaerythritol, sorbitol, 1,2,3-trihydroxycyclohexane, 1,3,3, Examples thereof include a residue obtained by removing a hydroxyl group from a polyhydric alcohol such as 5-trihydroxycyclohexane.
- coolant becomes favorable because carbon number of this aliphatic hydrocarbon group shall be 10 or less.
- the aliphatic hydrocarbon group preferably has 2 to 6 carbon atoms.
- the oxygen-containing hydrocarbon group having 1 to 10 carbon atoms in each of R 1b and R 3b includes a chain aliphatic group having an ether bond, a cyclic aliphatic group (for example, a tetrahydrofurfuryl group), and the like. Can be mentioned. At least one of R 1b and R 3b is preferably an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms.
- R 2b in the general formula (B-1) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.
- the oxyalkylene groups in one molecule may be the same, or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferable. More preferably, it contains 50 mol% or more of oxypropylene units.
- n is an integer of 1 to 6, and is determined according to the number of R 1b binding sites.
- n is 1, and when R 1b is an aliphatic hydrocarbon group having 2, 3, 4, 5, and 6 binding sites, n is 2, 3 respectively. , 4, 5 and 6.
- m is a number with an average value of m ⁇ n of 6 to 80. When the average value is 80 or less, the compatibility is improved.
- N is preferably an integer of 1 to 3, more preferably 1.
- the average value of m ⁇ n is preferably set as appropriate so as to be within a preferable viscosity range of the base oil described later.
- the polyoxyalkylene glycols represented by the general formula (B-1) include polyoxyalkylene glycols having a hydroxyl group at the terminal, and the content of the hydroxyl group is 50 mol with respect to all terminal groups. %, It can be used preferably even if it is contained.
- the copolymer of poly (oxy) alkylene glycol or its monoether and polyvinyl ether that can be used as the base oil in the refrigerating machine oil of this embodiment is represented by the following general formula (C-1).
- copolymers represented by general formula (C-2) hereinafter referred to as polyvinyl ether copolymer I and polyvinyl ether copolymer II), respectively.
- Poly (oxy) alkylene glycol refers to both polyalkylene glycol and polyoxyalkylene glycol.
- R 1c , R 2c and R 3c each independently represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different from each other, and R 5c is A divalent hydrocarbon group having 2 to 4 carbon atoms, R 6c is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic hydrocarbon group having 1 to 20 carbon atoms, or 2 to 20 carbon atoms An acyl group or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms, R 4c represents a hydrocarbon group having 1 to 10 carbon atoms, and when there are a plurality of R 1c to R 6c , they may be the same or different. Good.
- the hydrocarbon group having 1 to 8 carbon atoms of R 1c to R 3c is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec- Alkyl groups such as butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups; cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, etc.
- a cycloalkyl group an aryl group such as various dimethylphenyl groups; and an arylalkyl group such as a benzyl group, various phenylethyl groups, and various methylbenzyl groups.
- a hydrogen atom is especially preferable as each of these R1c , R2c, and R3c.
- examples of the divalent hydrocarbon group having 2 to 4 carbon atoms represented by R 5c include divalent alkylene groups such as a methylene group, an ethylene group, various propylene groups, and various butylene groups.
- v represents the number of repeating R 5c O, and the average value thereof is 1 to 50, preferably 1 to 20, more preferably 1 to 10, and particularly preferably 1 to 5. The number of ranges.
- R 5c O there is a plurality the plurality of R 5c O may be the same or different.
- v may be the same for each structural unit, or may be different.
- W represents a number of 1 to 50, preferably 1 to 10, more preferably 1 to 2, particularly preferably 1, u represents 0 to 50, preferably 2 to 25, more preferably 5 to 15, When there are a plurality of w and u, each of them may be block or random.
- R 6c in formula (C-1) preferably represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms.
- Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and various pentyl groups.
- acyl group having 2 to 10 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, piperoyl group, benzoyl group, and toluoyl group.
- oxygen-containing hydrocarbon group having 2 to 50 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxypropyl group, ethoxy
- Preferable examples include propyl group, (2-methoxyethoxy) propyl group, (1-methyl-2-methoxy) propyl group and the like.
- the hydrocarbon group having 1 to 10 carbon atoms represented by R 4c is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, Alkyl groups such as isobutyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups; cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups Groups, cycloalkyl groups such as various dimethylcyclohexyl groups; phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butyl
- Aryl group; benzyl group, various phenylethyl groups, An arylalkyl group such as various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups is shown.
- R 1c to R 5c and v are the same as described above.
- R 4c and R 5c may be the same or different when there are a plurality of R 4c and R 5c .
- x and y each represent a number from 1 to 50, and when there are a plurality of x and y, each may be a block or random.
- X c and Y c each independently represent a hydrogen atom, a hydroxyl group, or a hydrocarbon group having 1 to 20 carbon atoms.
- repeating numbers u, w, x, and y in the general formulas (C-1) and (C-2) are appropriately selected so as to have a desired viscosity described later.
- group copolymers I and II what is necessary is just a method by which it is obtained, and there is no restriction
- the vinyl ether copolymer I represented by the general formula (C-1) has one terminal represented by the following general formula (C-3) or (C-4), and the remaining terminal
- the polyvinyl ether copolymer I having the structure represented by the general formula (C-5) or (C-6) can be obtained.
- R 1c to R 6c and v are the same as described above.
- R 1c to R 6c and v are the same as described above.
- polyol ester that can be used as the base oil in the refrigerating machine oil
- an ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 1 to 24 carbon atoms is preferably used.
- diol examples include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5- Pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, etc.
- polyol examples include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), and tri- (pentaerythritol).
- Glycerin polyglycerin (glycerin 2 to 20-mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol and other polyhydric alcohols, xylose, arabinose, Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gen Anosu, saccharides such as Merenjitosu, and their partially etherified products and methyl glucosides (glycosides) and the like.
- neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri Hindered alcohols such as-(pentaerythritol) are preferred.
- the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used.
- those having 3 or more carbon atoms are preferable, those having 4 or more carbon atoms are more preferable, and those having 5 or more carbon atoms are even more preferable from the viewpoint of lubricity.
- a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is still more preferable.
- any of a linear fatty acid and a branched fatty acid may be sufficient, a linear fatty acid is preferable from the point of lubricity, and a branched fatty acid is preferable from the point of hydrolysis stability. Furthermore, either a saturated fatty acid or an unsaturated fatty acid may be used.
- fatty acids include isobutyric acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid , Linear or branched ones such as nonadecanoic acid, icosanoic acid and oleic acid, or so-called neoacids in which the ⁇ carbon atom is quaternary.
- the polyol ester may be a partial ester remaining without all the hydroxyl groups of the polyol being esterified, or may be a complete ester in which all the hydroxyl groups are esterified, or a partial ester and a complete ester. A complete ester is preferable.
- neopentyl glycol trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol
- esters of hindered alcohols such as di- (pentaerythritol) and tri- (pentaerythritol)
- esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol The ester of pentaerythritol is most preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.
- preferred polyol esters include neopentyl glycol and isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid and 2-ethylpentane.
- the ester with two or more fatty acids may be a mixture of two or more of one kind of fatty acid and a polyol.
- Two or more kinds of mixed fatty acid and an ester of a polyol, in particular, an ester of a mixed fatty acid and a polyol Excellent low temperature characteristics and compatibility with refrigerants.
- the oxygen-containing organic compound contained in the refrigerating machine oil preferably has a kinematic viscosity at 100 ° C. of 1 to 30 mm 2 / s.
- the kinematic viscosity is 1 mm 2 / s or more, good lubrication performance is exhibited and the sealing performance is improved.
- it is 30 mm ⁇ 2 > / s or less, it is excellent in compatibility with a refrigerant
- the 100 ° C. kinematic viscosity of the oxygen-containing organic compound is more preferably 2 to 20 mm 2 / s, and further preferably 3 to 15 mm 2 / s.
- the base oil may consist of only the oxygen-containing organic compound, but in addition to the oxygen-containing organic compound, mineral oil, synthetic oil other than the oxygen-containing organic compound, or these may be used as long as the object of the present invention is not impaired. Both of them may be contained.
- the base oil other than the oxygen-containing organic compound is preferably less than 10% by mass, more preferably less than 5% by mass, and more preferably less than 1% by mass with respect to the total amount of refrigerating machine oil. preferable.
- the base oil other than the oxygen-containing organic compound has a kinematic viscosity at 100 ° C. of preferably 1 to 30 mm 2 / s, more preferably 2 to 20 mm 2 / s, and further preferably 3 to 15 mm 2 / s. s.
- the polyphosphate ester compound contained in the refrigerating machine oil of this embodiment is a phosphate ester compound having at least two phosphate skeletons in one molecule.
- the polyphosphate ester compound is specifically a compound represented by the following general formula (1).
- n represents an integer of 1 to 10
- R 1 to R 8 each independently represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms
- R 9 represents a carbon number of 2 Represents a divalent hydrocarbon group of ⁇ 20.
- the refrigerating machine oil of the present embodiment contains the above-mentioned polyphosphate ester compound and a benzotriazole compound described later, thereby reducing the coefficient of friction in the sliding portion of the refrigerator and improving the wear resistance. It becomes possible.
- a polyphosphate ester type compound may be used individually by 1 type, and may use 2 or more types together.
- the alkyl group in R 1 to R 8 may be linear, branched or cyclic, and may be a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, or various pentyl groups.
- R 1 to R 8 are preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, more preferably a hydrogen atom or a methyl group, and most preferably a hydrogen atom.
- R 9 in the general formula (1) is preferably an alkylene group, an arylene group, or a hydrocarbon group composed of an arylene group and an alkylene group, and preferably includes an arylene group.
- the alkylene group is, for example, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, an undecylene group, A dodecylene group, a tetradecylene group, a hexadecylene group, an octadecylene group, an icosalen group, etc.
- the alkylene group may be a cyclic alkylene group such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a cycloheptylene group, a cyclooctylene group, a dicyclopentylene group, or a tricyclopentylene group. Good.
- the arylene group may be either substituted or unsubstituted, and specific examples include a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenyl group,
- the arylene group is preferably unsubstituted. Of these, a phenylene group is preferred.
- R 9 is composed of an arylene group and an alkylene group
- the arylene group is the same as described above, and examples of the alkylene group include a linear, branched, or cyclic alkylene group having 1 to 14 carbon atoms.
- a methylene group or the same as described above can be used.
- n is preferably 1 to 8
- n may be a single substance composed of a specific kind, or n may be a mixture composed of two or more kinds.
- n is more preferably 1 to 3, and n is particularly preferably 1.
- R 9 are preferably groups represented by the following general formulas (2) to (4), more preferably groups represented by the general formula (2) or (3), The group represented by the general formula (2) is more preferable.
- general formula (2) may be any of ortho form, meta form and para form, meta form is preferred.
- preferable polyphosphate ester compounds include compounds represented by the following general formulas (5) and (6). In these, the compound shown by the following general formula (5) is more preferable.
- n represents an integer of 1 to 10, preferably 1 to 8, and more preferably 1 to 5.
- the polyphosphate ester compound represented by the general formula (5) exhibits the effect of improving the wear resistance and reducing the friction coefficient when the base oil contains PVE as the oxygen-containing organic compound. When n is 1 to 3, particularly when n is 1, the effect is easily exhibited.
- the content of the polyphosphate ester compound is preferably 0.01 to 5.0% by mass with respect to the total amount of the refrigerating machine oil.
- the content of the polyphosphate ester compound is 0.5 to 5. 0% by mass is more preferable, 1.0 to 5.0% by mass is further preferable, and 1.0 to 3.0% by mass is particularly preferable.
- benzotriazole compounds examples include benzotriazole and benzotriazole derivatives.
- the benzotriazole is specifically 1,2,3-benzotriazole represented by the general formula (7).
- guide_body of benzotriazole the alkyl benzotriazole represented by the following general formula (8), the aminoalkyl benzotriazole represented by General formula (9), etc. are mentioned.
- R 11 represents a linear or branched alkyl group having 1 to 4 carbon atoms, and a represents an integer of 1 to 3. When there are a plurality of R 11 s , they may be the same or different. Specific examples of R 11 include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and the like. R 11 preferably represents a methyl group or an ethyl group, and a is preferably 1 or 2, and more preferably 1.
- R 12 is a linear or branched alkyl group having 1 to 4 carbon atoms
- b is an integer of 0 to 3
- R 13 is a methylene group or ethylene group
- R 14 and R 15 each independently represents a hydrogen atom or a linear or branched alkyl group having 1 to 18 carbon atoms.
- R 14 and R 15 may be the same as or different from each other.
- alkyl group for R 12 examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group.
- alkyl group of R 14 and R 15 examples include, for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various pentyl groups, Hexyl group, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups And the like.
- R 12 preferably represents a methyl group or an ethyl group
- R 14 and R 15 preferably represent a linear or branched alkyl group having 1 to 12 carbon atoms
- b
- R 12 is a methyl group
- b is 0 or 1
- R 13 is a methylene group or an ethylene group
- R 14 and R 15 are linear or branched.
- a branched alkyl group having 1 to 12 carbon atoms such as dialkylaminoalkylbenzotriazole, dialkylaminoalkyltolyltriazole, or a mixture thereof is preferred, and among them, those in which R 14 and R 15 each have 4 to 12 carbon atoms are further included.
- a benzotriazole type compound may be used individually by 1 type, and may use 2 or more types together. Specific examples of preferred benzotriazole compounds include 1,2,3-benzotriazole, methylbenzotriazole, 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole, and the like.
- the content of the benzotriazole-based compound is preferably 0.01% by mass or more based on the total amount of the refrigerating machine oil.
- the friction coefficient can be reduced while improving the wear resistance by using the polyphosphate ester compound in combination with the content of 0.01% by mass or more.
- the content of the benzotriazole-based compound is more preferably 0.01 to 1.00% by mass, and further preferably 0.02 to 1.00% by mass. .
- the refrigerating machine oil includes, in addition to the polyphosphate ester compound and the benzotriazole compound, an antioxidant, an acid scavenger, an antifoaming agent, an extreme pressure agent, an oil agent, an oxygen scavenger, You may contain any 1 type (s) or 2 or more types of various additives, such as a metal deactivator and a rust preventive agent. That is, the refrigerating machine oil may be composed of a base oil, the polyphosphate ester compound, and the benzotriazole compound, or the base oil, the polyphosphate ester compound, and the benzotriazole compound. Or an additive other than these.
- the base oil may contain mineral oil and synthetic oil other than the oxygen-containing organic compound in addition to the oxygen-containing organic compound, but is preferably composed of the oxygen-containing organic compound.
- the additives other than the polyphosphate ester compound and the benzotriazole compound are preferably contained in an amount of 15% by mass or less, more preferably 0 to 5% by mass, based on the total amount of the refrigerating machine oil.
- Antioxidants include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6-tert Phenyl-based antioxidants such as phenyl- ⁇ -naphthylamine and N, N′-di-phenyl-p-phenylenediamine are preferred, and phenolic antioxidants are preferred.
- the content of the antioxidant is usually 0.01 to 5% by mass, preferably 0.05 to 3% by mass, based on the total amount of the refrigerating machine oil, from the viewpoints of effects and economy.
- the acid scavenger examples include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
- epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ -olefin oxide, and epoxidized soybean oil.
- phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, and ⁇ -olefin oxide are preferable in terms of compatibility.
- the alkyl group of the alkyl glycidyl ether and the alkylene group of the alkylene glycol glycidyl ether may have a branch, and usually have 3 to 30, preferably 4 to 24, and particularly preferably 6 to 16 carbon atoms. is there.
- the ⁇ -olefin oxide generally has a total carbon number of 4 to 50, preferably 4 to 24, particularly 6 to 16.
- one type of acid scavenger may be used, or two or more types may be used in combination.
- the content thereof is usually 0.005 to 5% by mass, preferably 0.05 to 3% by mass, based on the total amount of the refrigerating machine oil, from the viewpoints of effects and suppression of sludge generation.
- the stability of refrigerating machine oil can be improved by containing an acid scavenger.
- an antifoamer a silicone type antifoamer, a fluorinated silicone type antifoamer, etc. can be mentioned, for example.
- the content of the antifoaming agent is usually 0.005 to 2% by mass, preferably 0.01 to 1% by mass, based on the total amount of refrigerating machine oil.
- extreme pressure agents include phosphorous extreme pressure agents such as phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, and amine salts thereof. These phosphorus-based extreme pressure agents have one phosphorus atom in the molecule, and include tricresyl phosphate, trithiophenyl phosphate, tri (nonylphenyl) phosphite, dioleyl hydrogen phosphite, 2-ethylhexyl. Examples thereof include diphenyl phosphite.
- the metal salt of carboxylic acid is mentioned.
- the metal salt of the carboxylic acid here is preferably a carboxylic acid having 3 to 60 carbon atoms, more preferably a metal salt of a fatty acid having 3 to 30 carbon atoms, particularly 12 to 30 carbon atoms.
- the dimer acid and trimer acid of the said fatty acid, and the metal salt of C3-C30 dicarboxylic acid can be mentioned.
- metal salts of fatty acids having 12 to 30 carbon atoms and dicarboxylic acids having 3 to 30 carbon atoms are particularly preferred.
- an alkali metal or an alkaline earth metal is preferable, and an alkali metal is particularly optimal.
- extreme pressure agents other than the above include sulfur-based extreme pressure agents such as sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, and dialkylthiodipropionates. be able to.
- the content of the extreme pressure agent is usually 0.001 to 5% by mass, particularly preferably 0.005 to 3% by mass, based on the total amount of refrigerating machine oil, from the viewpoint of lubricity and stability.
- One of these extreme pressure agents may be used alone, or two or more thereof may be used in combination.
- oily agents include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid, lauryl Aliphatic saturated and unsaturated monoalcohols such as alcohol, oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide and oleic acid amide, glycerin And partial esters of polyhydric alcohols such as sorbitol and aliphatic saturated or unsaturated monocarboxylic acids. These may be used individually by 1 type and may be used in combination of 2 or more type. The content thereof is usually selected in the range of 0.01 to 10% by mass, preferably 0.1 to 5% by mass with respect to the total amount of the refrig
- oxygen scavenger examples include 4,4′-thiobis (3-methyl-6-tert-butylphenol), diphenyl sulfide, dioctyl diphenyl sulfide, dialkyl diphenylene sulfide, benzothiophene, dibenzothiophene, phenothiazine, benzothiapyran, thiapyran, thianthrene, Examples thereof include sulfur-containing aromatic compounds such as dibenzothiapyran and diphenylene disulfide, aliphatic unsaturated compounds such as various olefins, dienes and trienes, and terpenes having a double bond.
- Examples of the metal deactivator include N- [N, N′-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl] triazole.
- Examples of the rust preventive include metal sulfonates, aliphatic amines, organic phosphites, organic phosphates, organic sulfonates, organic phosphates, alkenyl succinates, polyhydric alcohol esters, and the like. be able to.
- the refrigerating machine oil according to the present embodiment can further contain other known various additives as long as the object of the present invention is not impaired.
- the refrigerating machine oil according to the present embodiment is used in a refrigerant environment, and specifically is used in a refrigerating machine after being mixed with a refrigerant. That is, in this embodiment, it uses for a refrigerator with the form of the composition for refrigerators containing refrigerator oil and a refrigerant
- the amount of refrigerant and refrigerator oil used is preferably in the range of 99/1 to 10/90, more preferably 95/5 to 30/70, by mass ratio of refrigerant / refrigerant oil. When this mass ratio is within the above range, the refrigerating capacity and lubricity in the refrigerator can be made appropriate.
- the refrigerant to be used include one or two or more kinds selected from fluorinated hydrocarbons, natural refrigerants such as carbon dioxide, hydrocarbons, and ammonia.
- fluorinated hydrocarbon examples include a saturated fluorinated hydrocarbon compound (saturated HFC) and an unsaturated fluorinated hydrocarbon compound (HFO).
- saturated fluorinated hydrocarbon compound is usually an alkane fluoride having 1 to 4 carbon atoms, preferably an alkane fluoride having 1 to 3 carbon atoms, and an alkane having 1 to 2 carbon atoms (methane or ethane). Fluoride is more preferred.
- Specific 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-penta Fluoroethane (R125) can be mentioned, among which difluoromethane and 1,1,1,2,2-pentafluoroethane are preferable.
- These saturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more.
- 2 mixed refrigerants in which two or more kinds of saturated fluorinated hydrocarbon compounds having 1 to 3 carbon atoms are mixed, or 2 kinds of saturated fluorinated hydrocarbon compounds having 1 to 2 carbon atoms are used.
- species or more is mentioned.
- Specific examples of the mixed refrigerant include a mixture of R32 and R125 (R410A), a mixture of R125, R143a and R134a (R404A), a mixture of R32, R125 and R134a (R407A, R407C, R407E, etc.), and a mixture of R125 and R143a ( R507A) and the like.
- unsaturated fluorinated hydrocarbon compounds include those having a carbon-carbon double bond, such as linear or branched chain olefins having 2 to 6 carbon atoms and fluorinated products of cyclic olefins having 4 to 6 carbon atoms. Can be mentioned.
- ethylene introduced with 1 to 3 fluorine atoms
- propene introduced with 1 to 5 fluorine atoms
- butene introduced with 1 to 7 fluorine atoms
- 1 to 9 Penten introduced with fluorine atoms
- hexene introduced with 1 to 11 fluorine atoms
- cyclobutene introduced with 1 to 5 fluorine atoms
- cyclopentene introduced with 1 to 7 fluorine atoms
- 1 to 9 cyclohexene introduced with one fluorine atom.
- propene fluoride is preferable, propene having 3 to 5 fluorine atoms introduced is more preferable, and propene having 4 fluorine atoms introduced is most preferable.
- 1,3,3,3-tetrafluoropropene (HFO1234ze) and 2,3,3,3-tetrafluoropropene (HFO1234yf) are preferable compounds.
- These unsaturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more, or may be used in combination with a refrigerant other than the unsaturated fluorinated hydrocarbon compound. .
- a mixed refrigerant of a saturated fluorinated hydrocarbon compound and an unsaturated fluorinated hydrocarbon compound can be given as an example of a case where the refrigerant is used in combination with a refrigerant other than the unsaturated fluorinated hydrocarbon compound.
- Specific examples of the mixed refrigerant include a mixed refrigerant of R-32, HFO1234ze, and R152a (AC5, the mixing ratio is 13.23: 76.20: 9.96).
- Natural refrigerants include carbon dioxide (carbon dioxide), hydrocarbons such as propane, n-butane, isobutane, 2-methylbutane, n-pentane, cyclopentane, isobutane, and normal butane, and ammonia. 1 type may be used independently, 2 or more types may be used in combination, and it may combine with refrigerants other than a natural system refrigerant.
- a mixed refrigerant with a saturated fluorinated hydrocarbon compound, an unsaturated fluorinated hydrocarbon compound, or both of these can be mentioned.
- Specific examples of the mixed refrigerant include a mixed refrigerant of carbon dioxide, HFO1234ze, and R134a (AC6, blending ratio is 5.15: 79.02: 15.41).
- fluorinated hydrocarbons are preferable, and saturated fluorinated hydrocarbon compounds are more preferable.
- the refrigerant may be a mixture of a saturated fluorinated hydrocarbon compound and another refrigerant, but is preferably composed of only a saturated fluorinated hydrocarbon compound.
- R32, R125, and R410A which is a mixture thereof are more preferable.
- the refrigerant preferably contains R32.
- the ratio of R32 in the whole refrigerant is preferably 50% by mass or more, more preferably 70% by mass or more, and 100% by mass, that is, R32 alone, based on the total amount of refrigerant.
- the refrigerant is most preferable.
- the refrigerating machine oil or the refrigerating machine composition according to the present embodiment is used by filling the inside of the refrigerating machine.
- the refrigerator is a compressor, a condenser, an expansion mechanism (such as an expansion valve) and an evaporator, or a refrigeration cycle having a configuration in which a compressor, a condenser, an expansion mechanism, a dryer and an evaporator are essential.
- the refrigerating machine oil is used for lubricating a sliding portion provided in, for example, a compressor.
- the sliding part of the refrigerator is preferably between metal and metal, and examples of the metal of the sliding part include iron and steel materials.
- the refrigerating machine oil of the present embodiment can reduce the friction coefficient while improving the wear resistance between iron and steel materials.
- the refrigerating machine oil and the refrigerating machine composition more specifically include various refrigerators such as a car air conditioner, a gas heat pump (GHP), an air conditioner, a refrigerator, a vending machine, a showcase, a water heater, and a floor heater. It can be used in systems, hot water supply systems, and heating systems.
- the properties of the base oil, the characteristics of the refrigerator oil and the composition for the refrigerator were determined according to the following procedure.
- the base oil and additives are as follows.
- PAG Polyoxypropylene glycol (100 ° C.
- ECP Polypropylene glycol (PPG) / polyethyl vinyl ether (PEV) copolymer (PPG / PEV molar ratio 5/5, 100 ° C.
- PPG / PEV molar ratio 5/5 100 ° C.
- POE pentaerythritol octanoic acid (C8 acid) nonanoic acid (C9 acid) ester (C8 acid / C9 acid molar ratio 1 / 1.1, 100 ° C.
- Polyphosphate ester compound 1 Compound in which n is a mixture of 1 to 3 in the above general formula (5)
- Polyphosphate ester compound 2 Compound in which n is a mixture of 1 to 8 in the above general formula (5)
- Polyphosphate ester compound 3 Compound represented by the above general formula (6)
- Polyphosphate ester compound 4 Compound represented by the above general formula (1), wherein R 1 , R 3 , R 5 , R 7 is a hydrogen atom, R 2 , R 4 , R 6 and R 8 are alkyl groups having 1 to 20 carbon atoms, R 9 is a divalent hydrocarbon group having 2 to 20 carbon atoms, and n is 1 to 8 A compound that is a mixture.
- Benzotriazole compound 1 1,2,3-benzotriazole benzotriazole compound 2: methylbenzotriazole benzotriazole compound 3: 1- [N, N-bis (2-ethylhexyl) aminomethyl] methylbenzotriazole antioxidant Agent: 2,6-di-tert-butyl-4-methylphenol (DBPC) Acid scavenger: 2-ethylhexyl glycidyl ether antifoaming agent: silicone-based antifoaming agent
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Abstract
Description
このような飽和HFC冷媒との相溶性や、耐摩耗性、耐焼付性等の潤滑性能を改善する技術として、含酸素有機化合物からなる基油に、トリクレジルホスフェート(TCP)等のリン原子を1つ有するリン酸エステル化合物を添加することが知られている(例えば、特許文献2参照)。
また、トリクレジルホスフェート(TCP)等のリン原子を1つ有するリン酸エステル化合物を、潤滑油組成物においてベンゾトリアゾール系化合物と併用することで、耐摩耗性が向上することも知られている(特許文献3、4参照)。
しかしながら、特許文献2~4に示すように、TCP等のリン原子を1つ有するリン酸エステル化合物、又はTCP等に加えベンゾトリアゾール系化合物を配合したとしても、潤滑油組成物は、冷凍機の摺動部分において、耐摩耗性を良好にしつつ摩擦係数を十分に低くすることが難しい。
(1)含酸素有機化合物を含む基油と、多リン酸エステル系化合物と、ベンゾトリアゾール系化合物とを含む冷凍機油。
(2)冷媒と、上記(1)に記載される冷凍機油とを含む冷凍機用組成物。
(3)含酸素有機化合物を含む基油に、多リン酸エステル系化合物と、ベンゾトリアゾール系化合物とを少なくとも配合して冷凍機油を得る、冷凍機油の製造方法。
本発明の一実施形態に係る冷凍機油は、基油と、多リン酸エステル系化合物と、ベンゾトリアゾール系化合物とを含む。以下、冷凍機油に含有される各成分について詳細に説明する。
本実施形態における基油は、含酸素有機化合物を含むものである。含酸素有機化合物としては、分子中にエーテル基、ケトン基、エステル基、カーボネート基などを含有する合成油、さらにはこれらの基とともにヘテロ原子(硫黄原子、フッ素原子、塩素原子、珪素原子、窒素原子など)を含有する合成油が挙げられる。より具体的には、ポリビニルエーテル類(PVE)、ポリオキシアルキレングリコール類(PAG)、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体(ECP)、及びポリオールエステル類(POE)が挙げられる。含酸素有機化合物は、1種単独で使用してもよいし、2種以上を併用してもよい。
これらの中では、ポリビニルエーテル類(PVE)及びポリオキシアルキレングリコール類(PAG)から選ばれる1種以上が好ましく、中でも、ポリビニルエーテル類(PVE)から選ばれる1種以上がより好ましい。なお、PVEは、特に、後述する一般式(1)で表され、かつR9が一般式(2)で表される基である多リン酸エステル化合物や、一般式(5)で示される多リン酸エステル化合物に対して使用される場合に、摩擦係数、耐摩耗性を良好にしやすくなる。
含酸素有機化合物は、冷凍機油の主成分となるものであり、含酸素有機化合物は、冷凍機油全量に対して、70~99.98質量%含有されることが好ましく、90~99.5質量%含有されることがより好ましく、93.0~99.3質量%含有されることが更に好ましい。
<ポリビニルエーテル類(PVE)>
ポリビニルエーテル類(PVE)は、ビニルエーテル由来の構成単位を有する重合体であり、具体的には、下記一般式(A-1)で表される構成単位を有するポリビニル系化合物が挙げられる。
R1a、R2a及びR3aは水素原子あるいは炭素数3以下のアルキル基がより好ましく、いずれも水素原子であることがさらに好ましい。なお、一般式(A-1)におけるrは、繰り返し数を示し、その平均値が0~10の範囲の数であるが、0が好ましい。
また、前記R5aの炭素数3もしくは4のアルキル基としては、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基が使用できるが、特にイソブチル基が好ましい。
中でも、ポリビニルエーテル系化合物としては、次の(1)~(4)の末端構造を有するものが好適である。
(1)その1つの末端が下記一般式(A-1-i)で表され、残りの末端が下記一般式(A-1-ii)で表されるもの
(式中、R6a,R7a及びR8aは、それぞれ独立に水素原子又は炭素数1~8の炭化水素基を示し、それらは互いに同一であっても異なっていてもよい。R9aは炭素数2~10の二価の炭化水素基、R10aは炭素数1~10の炭化水素基、r1はその平均値が0~10の数を示し、R9aOが複数ある場合には複数のR9aOは同一であっても異なっていてもよい。)
(式中、R16a、R17a及びR18aは、それぞれ独立に水素原子又は炭素数1~8の炭化水素基を示し、それらは互いに同一であっても異なっていてもよい。R19a及びR21aはそれぞれ独立に炭素数2~10の二価の炭化水素基を示し、それらは互いに同一であっても異なっていてもよく、R20a及びR22aはそれぞれ独立に炭素数1~10の炭化水素基を示し、それらは互いに同一であっても異なっていてもよく、r3及びr4はそれぞれその平均値が0~10の数を示し、それらは互いに同一であっても異なっていてもよく、また複数のR19aOがある場合には複数のR19aOは同一であっても異なっていてもよいし、複数のR21aOがある場合には複数のR21aOは同一であっても異なっていてもよい。)
(4)その一つの末端が上記一般式(A-1-i)で表され、かつ残りの末端が一般式(A-1-iv)で表されるもの
(式中、R23a,R24a及びR25aは、それぞれ水素原子又は炭素数1~8の炭化水素基を示し、それらは互いに同一であっても異なっていてもよい。)
ポリビニルエーテル系化合物は、後述する好ましい基油の粘度範囲となるように、重合度、末端構造等を選定することが好ましい。また、ポリビニルエーテル系化合物は、1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
中でも、式(A-1-i)及び式(A-1-ii)において、R6a,R7a、R8a、R11a,R12a及びR13aが水素原子であるとともに、r1及びr2のいずれもが0であり、R10a,R15aが炭素数1~4のアルキル基であることがより好ましい。
ポリオキシアルキレングリコール類(PAG)としては、下記一般式(B-1)で表される化合物が挙げられる。なお、基油中にPAGが含まれる場合、当該PAGは、単独で又は2種以上を併用してもよい。
R1b-[(OR2b)m-OR3b]n (B-1)
(式中、R1bは水素原子、炭素数1~10の1価の炭化水素基、炭素数2~10のアシル基、結合部2~6個を有する炭素数1~10の炭化水素基又は炭素数1~10の酸素含有炭化水素基、R2bは炭素数2~4のアルキレン基、R3bは水素原子、炭素数1~10の炭化水素基又は炭素数2~10のアシル基又は炭素数1~10の酸素含有炭化水素基、nは1~6の整数、mはm×nの平均値が6~80となる数を示す。)
また、R1b及びR3bの各々における炭素数2~10のアシル基が有する炭化水素基部分は、直鎖状、分岐鎖状、環状のいずれであってもよい。該アシル基の炭化水素基部分は、アルキル基が好ましく、その具体例としては、上述のR1b及びR3bとして選択し得るアルキル基のうち炭素数1~9のものが挙げられる。該アシル基の炭素数が10以下とすることで冷媒との相溶性が良好となる。好ましいアシル基の炭素数は2~4である。
R1b及びR3bが、いずれも炭化水素基又はアシル基である場合には、R1bとR3bは同一であってもよいし、互いに異なっていてもよい。
R1bが結合部位2~6個を有する炭素数1~10の炭化水素基である場合、この炭化水素基は鎖状のものであってもよいし、環状のものであってもよい。結合部位2個を有する炭化水素基としては、脂肪族炭化水素基が好ましく、例えばエチレン基、プロピレン基、ブチレン基、ペンチレン基、ヘキシレン基、ヘプチレン基、オクチレン基、ノニレン基、デシレン基、シクロペンチレン基、シクロヘキシレン基などが挙げられる。その他の炭化水素基としては、ビフェノール、ビスフェノールF、ビスフェノールAなどのビスフェノール類から水酸基を除いた残基を挙げることができる。また、結合部位3~6個を有する炭化水素基としては、脂肪族炭化水素基が好ましく、例えばトリメチロールプロパン、グリセリン、ペンタエリスリトール、ソルビトール、1,2,3-トリヒドロキシシクロヘキサン、1,3,5-トリヒドロキシシクロヘキサンなどの多価アルコールから水酸基を除いた残基を挙げることができる。
この脂肪族炭化水素基の炭素数が10以下とすることで冷媒との相溶性が良好となる。この脂肪族炭化水素基の好ましい炭素数は2~6である。
上記R1b及びR3bの少なくとも一つはアルキル基、特に炭素数1~4のアルキル基であることが好ましい。
前記一般式(B-1)中のnは1~6の整数で、R1bの結合部位の数に応じて定められる。例えばR1bがアルキル基やアシル基の場合、nは1であり、R1bが結合部位2,3,4,5及び6個を有する脂肪族炭化水素基である場合、nはそれぞれ2,3,4,5及び6となる。また、mはm×nの平均値が6~80となる数である。該平均値は80以下となることで相溶性が良好になる。また、nは、好ましくは1~3の整数、より好ましくは1である。ただし、m×nの平均値は、後述する好ましい基油の粘度範囲となるように、適宜設定されることが好ましい。
前記一般式(B-1)で表されるポリオキシアルキレングリコール類は、末端に水酸基を有するポリオキシアルキレングリコールを包含するものであり、該水酸基の含有量が全末端基に対して、50モル%以下になるような割合であれば、含有していても好適に使用することができる。
本実施形態の冷凍機油において、基油として用いることのできる、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体としては、以下の一般式(C-1)で表される共重合体、及び一般式(C-2)で表される共重合体(以下、それぞれをポリビニルエーテル系共重合体I及びポリビニルエーテル系共重合体IIと称する。)が挙げられる。なお、ポリ(オキシ)アルキレングリコールとは、ポリアルキレングリコール及びポリオキシアルキレングリコールの両方を指す。
ここでR1c~R3cのうちの炭素数1~8の炭化水素基とは、具体的にはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基などのアルキル基;シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種ジメチルシクロヘキシル基などのシクロアルキル基;各種ジメチルフェニル基などのアリール基;ベンジル基、各種フェニルエチル基、各種メチルベンジル基などのアリールアルキル基を示す。なお、これらのR1c,R2c及びR3cの各々としては、特に水素原子が好ましい。
なお、一般式(C-1)におけるvは、R5cOの繰り返し数を示し、その平均値が1~50、好ましくは1~20、さらに好ましくは1~10、特に好ましくは1~5の範囲の数である。R5cOが複数ある場合には、複数のR5cOは同一でも異なっていてもよい。vは構成単位毎に同じであってもよいし、異なっていてもよい。
また、wは1~50、好ましくは1~10、さらに好ましくは1~2、特に好ましくは1、uは0~50、好ましくは2~25、さらに好ましくは5~15、の数を示し、wおよびuはそれらが複数ある場合にはそれぞれブロックでもランダムでもよい。
この炭素数1~10のアルキル基とは、具体的にはメチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、シクロペンチル基、シクロヘキシル基、各種メチルシクロヘキシル基、各種エチルシクロヘキシル基、各種プロピルシクロヘキシル基、各種ジメチルシクロヘキシル基などを示す。
また、炭素数2~10のアシル基としては、アセチル基、プロピオニル基、ブチリル基、イソブチリル基、バレリル基、イソバレリル基、ピパロイル基、ベンゾイル基、トルオイル基などを挙げることができる。
さらに、炭素数2~50の酸素含有炭化水素基の具体例としては、メトキシメチル基、メトキシエチル基、メトキシプロピル基、1,1-ビスメトキシプロピル基、1,2-ビスメトキシプロピル基、エトキシプロピル基、(2-メトキシエトキシ)プロピル基、(1-メチル-2-メトキシ)プロピル基などを好ましく挙げることができる。
前記一般式(C-1)で表される構成単位を有するポリビニルエーテル系共重合体Iは共重合体にすることにより、相溶性を満足しつつ潤滑性、絶縁性、吸湿性等を向上させることができる。
なお、一般式(C-1)、(C-2)における繰り返し数u、w、x、yは、後述する所望の粘度となるように適宜選択されることが好ましい。また、ポリビニルエーテル系共重合体I、IIの製造方法については、それが得られる方法であればよく、特に制限はない。
(上記(C-3)、(C-4)において、R1c~R6c及びvは前記と同じである。)
(上記(C-5)、(C-6)において、R1c~R6c及びvは前記と同じである。)
冷凍機油において、基油として用いることのできるポリオールエステル類としては、ジオールあるいは水酸基を3~20個有するポリオールと、炭素数1~24の脂肪酸とのエステルが好ましく用いられる。ここで、ジオールとしては、例えばエチレングリコール、1,3-プロパンジオール、プロピレングリコール、1,4-ブタンジオール、1,2-ブタンジオール、2-メチル-1,3-プロパンジオール、1,5-ペンタンジオール、ネオペンチルグリコール、1,6-ヘキサンジオール、2-エチル-2-メチル-1,3-プロパンジオール、1,7-ヘプタンジオール、2-メチル-2-プロピル-1,3-プロパンジオール、2,2-ジエチル-1,3-プロパンジオール、1,8-オクタンジオール、1,9-ノナンジオール、1,10-デカンジオール、1,11-ウンデカンジオール、1,12-ドデカンジオールなどが挙げられる。ポリオールとしては、例えば、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ-(トリメチロールプロパン)、トリ-(トリメチロールプロパン)、ペンタエリスリトール、ジ-(ペンタエリスリトール)、トリ-(ペンタエリスリトール)、グリセリン、ポリグリセリン(グリセリンの2~20量体)、1,3,5-ペンタントリオール、ソルビトール、ソルビタン、ソルビトールグリセリン縮合物、アドニトール、アラビトール、キシリトール、マンニトールなどの多価アルコール、キシロース、アラビノース、リボース、ラムノース、グルコース、フルクトース、ガラクトース、マンノース、ソルボース、セロビオース、マルトース、イソマルトース、トレハロース、シュクロース、ラフィノース、ゲンチアノース、メレンジトースなどの糖類、並びにこれらの部分エーテル化物、及びメチルグルコシド(配糖体)などが挙げられる。これらの中でもポリオールとしては、ネオペンチルグリコール、トリメチロールエタン、トリメチロールプロパン、トリメチロールブタン、ジ-(トリメチロールプロパン)、トリ-(トリメチロールプロパン)、ペンタエリスリトール、ジ-(ペンタエリスリトール)、トリ-(ペンタエリスリトール)などのヒンダードアルコールが好ましい。
また、直鎖状脂肪酸、分岐状脂肪酸の何れであってもよく、潤滑性の点からは直鎖状脂肪酸が好ましく、加水分解安定性の点からは分岐状脂肪酸が好ましい。更に、飽和脂肪酸、不飽和脂肪酸のいずれであってもよい。
なお、ポリオールエステルとしては、ポリオールの全ての水酸基がエステル化されずに残った部分エステルであってもよく、全ての水酸基がエステル化された完全エステルであってもよく、また部分エステルと完全エステルの混合物であってもよいが、完全エステルであることが好ましい。
なお、基油は、上記含酸素有機化合物のみからなるものでもよいが、本発明の目的を阻害しない限り、含酸素有機化合物に加えて、鉱油、上記含酸素有機化合物以外の合成油、又はこれらの両方を含有していてもよい。なお、上記含酸素有機化合物以外の基油は、冷凍機油全量に対して、10質量%未満であることが好ましく、5質量%未満であることがより好ましく、1質量%未満であることがさらに好ましい。含酸素有機化合物以外の基油も含酸素有機化合物と同様に、100℃動粘度が、好ましくは1~30mm2/s、より好ましくは2~20mm2/s、さらに好ましくは3~15mm2/sである。
本実施形態の冷凍機油に含有される多リン酸エステル系化合物は、一分子中に少なくとも2つのリン酸骨格を有するリン酸エステル化合物である。多リン酸エステル系化合物は、具体的には以下の一般式(1)で表される化合物である。
(ただし、式(1)において、nは1~10の整数を表し、R1~R8は、それぞれ独立に水素原子又は炭素数1~20のアルキル基を表し、R9は、炭素数2~20の二価の炭化水素基を表す。)
本実施形態の冷凍機油は、上記の多リン酸エステル系化合物及び後述するベンゾトリアゾール系化合物を含有することで、冷凍機の摺動部分における摩擦係数を低減させ、かつ耐摩耗性を良好にすることが可能になる。
なお、多リン酸エステル系化合物は、1種単独で使用してもよいし、2種以上を併用してもよい。
R1~R8は、水素原子又は炭素数1~4のアルキル基が好ましく、水素原子又はメチル基がより好ましく、水素原子であることが最も好ましい。
さらに、R9がアリーレン基とアルキレン基からなる場合、アリーレン基は上記と同じであるとともに、アルキレン基としては、直鎖状、分岐鎖状、又は環状の炭素数1~14のアルキレン基が挙げられ、例えば、メチレン基や上記したものと同様のものが使用できる。また、直鎖状又は分岐鎖状の炭素数1~5のアルキレン基であることが好ましく、具体的にはメチレン基、1,1-エチレン、1,2-エチレン等の各種エチレン基、1,3-プロピレン、1,2-プロピレン、2,2-プロピレン等の各種プロピレン基、各種ブチレン基、各種ペンチレン基が挙げられ、これらの中では2,2-プロピレン基(-C(CH3)2-)がより好ましい。
また、一般式(1)において、nは、1~8が好ましく、nが特定の一種からなる単体であってもよいし、nが特定の二種以上からなる混合物であってもよい。nは1~3であることがより好ましく、中でもnは1が特に好ましい。nを小さくすることにより、分子量が小さくなるため、基油に対する溶解度を高めやすくなり、さらには、摩擦係数を低減させやすくなる。
式(5)において、nは1~10の整数を表し、好ましくは1~8、より好ましくは1~5である。なお、一般式(5)に示される多リン酸エステル系化合物は、基油が上記含酸素有機化合物としてPVEを含む場合に、耐摩耗性を良好にし、かつ摩擦係数を低減させる効果を発揮しやすく、nが1~3である場合、特にnが1である場合に、その効果を発揮しやすい。
また、冷凍機油の安定性及び耐摩耗性を考慮しつつ、摺動部における摩擦係数を効果的に低減させるためには、上記多リン酸エステル系化合物の含有量は、0.5~5.0質量%がより好ましく、1.0~5.0質量%がさらに好ましく、1.0~3.0質量%が特に好ましい。
冷凍機油に含有されるベンゾトリアゾール系化合物は、ベンゾトリアゾール、及びベンゾトリアゾール誘導体が挙げられる。
ベンゾトリアゾールは、具体的には、一般式(7)で表される1,2,3-ベンゾトリアゾールである。また、ベンゾトリアゾールの誘導体としては、以下の一般式(8)で表されるアルキルベンゾトリアゾール、一般式(9)で表されるアミノアルキルベンゾトリアゾール等が挙げられる。
R11は、好ましくはメチル基又はエチル基を示し、aは好ましくは1又は2であり、より好ましくは1である。
R12のアルキル基としては、例えば、メチル基、エチル基、n-プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基等が挙げられる。また、R14 及びR15のアルキル基としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、n-ブチル基、イソブチル基、sec-ブチル基、tert-ブチル基、各種ペンチル基、各種ヘキシル基、各種ヘプチル基、各種オクチル基、各種ノニル基、各種デシル基、各種ウンデシル基、各種ドデシル基、各種トリデシル基、各種テトラデシル基、各種ペンタデシル基、各種ヘキサデシル基、各種ヘプタデシル基、各種オクタデシル基等のアルキル基が挙げられる。
R12は好ましくはメチル基又はエチル基を示し、R14及びR15は好ましくは直鎖状又は分枝状の炭素数1~12のアルキル基、bは好ましくは0又は1の数を示す。
なお、ベンゾトリアゾール系化合物は、1種単独で使用してもよいし、2種以上を併用してもよい。
また、ベンゾトリアゾール系化合物の好ましい具体例としては、1,2,3-ベンゾトリアゾール、メチルベンゾトリアゾール、1-[N,N-ビス(2-エチルヘキシル)アミノメチル]メチルベンゾトリアゾール等が挙げられる。
本実施形態に係る冷凍機油は、上記多リン酸エステル系化合物、ベンゾトリアゾール系化合物以外にも、さらに、酸化防止剤、酸捕捉剤、消泡剤、極圧剤、油性剤、酸素捕捉剤、金属不活性化剤、及び防錆剤等の各種添加剤のいずれか1種又は2種以上を含有してもよい。すなわち、冷凍機油は、基油と、上記多リン酸エステル系化合物と、上記ベンゾトリアゾール系化合物とからなるものでもよいし、基油と、上記多リン酸エステル系化合物と、ベンゾトリアゾール系化合物と、これら以外の添加剤とからなるものでもよい。この際、基油は、上記したように、含酸素有機化合物に加え、鉱油、上記含酸素有機化合物以外の合成油を含んでもよいが、含酸素有機化合物からなることが好ましい。
また、上記各種添加剤としては、上記した中では、酸化防止剤、酸捕捉剤、及び消泡剤のいずれか1種又は2種以上を含有することが好ましい。上記多リン酸エステル系化合物及びベンゾトリアゾール系化合物以外の添加剤は、冷凍機油全量に対して、好ましくは15質量%以下、より好ましくは0~5質量%含有される。
酸化防止剤としては、2,6-ジ-tert-ブチル-4-メチルフェノール、2,6-ジ-tert-ブチル-4-エチルフェノール、2,2’-メチレンビス(4-メチル-6-tert-ブチルフェノール)等のフェノール系、フェニル-α-ナフチルアミン、N,N’-ジ-フェニル-p-フェニレンジアミン等のアミン系の酸化防止剤が挙げられるが、フェノール系の酸化防止剤が好ましい。酸化防止剤の含有量は、効果及び経済性などの点から、冷凍機油全量に対して、通常0.01~5質量%、好ましくは0.05~3質量%である。
このアルキルグリシジルエーテルのアルキル基、及びアルキレングリコールグリシジルエーテルのアルキレン基は、分岐を有していてもよく、炭素数は通常3~30、好ましくは4~24、特に好ましくは6~16のものである。また、α-オレフィンオキシドは全炭素数が一般に4~50、好ましくは4~24、特に6~16のものを使用する。本実施形態においては、上記酸捕捉剤は1種を用いてもよく、2種以上を組み合わせて用いてもよい。また、その含有量は、効果及びスラッジ発生の抑制の点から、冷凍機油全量に対して、通常0.005~5質量%、好ましくは0.05~3質量%である。
本実施形態においては、酸捕捉剤を含有させることにより、冷凍機油の安定性を向上させることができる。
また、消泡剤としては、例えば、シリコーン系消泡剤やフッ素化シリコーン系消泡剤などを挙げることができる。消泡剤の含有量は、冷凍機油全量に対して、通常0.005~2質量%、好ましくは0.01~1質量%である。
これらのリン系極圧剤は、その分子中にリン原子を1つ有するものであり、トリクレジルホスフェート、トリチオフェニルホスフェート、トリ(ノニルフェニル)ホスファイト、ジオレイルハイドロゲンホスファイト、2-エチルヘキシルジフェニルホスファイトなどが挙げられる。
一方、金属塩を構成する金属としてはアルカリ金属又はアルカリ土類金属が好ましく、特に、アルカリ金属が最適である。
さらに、上記以外の極圧剤として、例えば、硫化油脂、硫化脂肪酸、硫化エステル、硫化オレフィン、ジヒドロカルビルポリサルファイド、チオカーバメート類、チオテルペン類、ジアルキルチオジプロピオネート類などの硫黄系極圧剤を挙げることができる。
上記極圧剤の含有量は、潤滑性及び安定性の点から、冷凍機油全量に対して、通常0.001~5質量%、特に0.005~3質量%が好ましい。
これら極圧剤は1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。
これらは1種を単独で用いてもよく、2種以上を組み合わせて用いてもよい。また、その含有量は、冷凍機油全量に対して、通常0.01~10質量%、好ましくは0.1~5質量%の範囲で選定される。
金属不活性化剤としては、例えばN-[N,N’-ジアルキル(炭素数3~12のアルキル基)アミノメチル]トリアゾール等を挙げることができる。
防錆剤としては、例えば金属スルホネート、脂肪族アミン類、有機亜リン酸エステル、有機リン酸エステル、有機スルフォン酸金属塩、有機リン酸金属塩、アルケニルコハク酸エステル、多価アルコールエステル等を挙げることができる。
本実施形態に係る冷凍機油には、さらに本発明の目的を阻害しない範囲で、他の公知の各種添加剤を含有させることができる。
本実施形態に係る冷凍機油は、冷媒環境下で使用されるものであり、具体的には冷媒と混合されて冷凍機で使用されるものである。すなわち、本実施形態では、冷凍機油と冷媒とを含有する冷凍機用組成物の形態で冷凍機に使用される。冷凍機用組成物において、冷媒と冷凍機油の使用量については、冷媒/冷凍機油の質量比で99/1~10/90、更に95/5~30/70の範囲にあることが好ましい。この質量比を上記範囲内とすると、冷凍機における冷凍能力、及び潤滑性を適切にできる。
使用される冷媒としては、フッ化炭化水素や、自然系冷媒である二酸化炭素、炭化水素、及びアンモニアの中から選択される1種又は2種以上が挙げられる。
フッ化炭化水素としては、飽和フッ化炭化水素化合物(飽和HFC)や不飽和フッ化炭化水素化合物(HFO)が挙げられる。
飽和フッ化炭化水素化合物としては、通常、炭素数1~4のアルカンのフッ化物であり、炭素数1~3のアルカンのフッ化物が好ましく、炭素数1~2のアルカン(メタン又はエタン)のフッ化物がより好ましい。具体的なメタン又はエタンのフッ化物としては、トリフルオロメタン(R23)、ジフルオロメタン(R32)、1,1-ジフルオロエタン(R152a)、1,1,1-トリフルオロエタン(R143a)、1,1,2-トリフルオロエタン(R143)、1,1,1,2-テトラフルオロエタン(R134a)、1,1,2,2-テトラフルオロエタン(R134)、1,1,1,2,2-ペンタフルオロエタン(R125)が挙げられ、これらの中ではジフルオロメタン、1,1,1,2,2-ペンタフルオロエタンが好ましい。
これらの飽和フッ化炭化水素化合物は、1種を単独で用いてよく、2種以上組み合わせて用いてもよい。ここで、2種以上組み合わせて用いる場合の例として、炭素数1~3の飽和フッ化炭化水素化合物を2種以上混合した混合冷媒や、炭素数1~2の飽和フッ化炭化水素化合物を2種以上混合した混合冷媒が挙げられる。
具体的な混合冷媒としては、R32とR125の混合物(R410A)、R125とR143aとR134aの混合物(R404A)、R32とR125とR134aの混合物(R407A、R407C、R407E等)、R125とR143aの混合物(R507A)等が挙げられる。
より具体的には、1~3個のフッ素原子が導入されたエチレン、1~5個のフッ素原子が導入されたプロペン、1~7個のフッ素原子が導入されたブテン、1~9個のフッ素原子が導入されたペンテン、1~11個のフッ素原子が導入されたヘキセン、1~5個のフッ素原子が導入されたシクロブテン、1~7個のフッ素原子が導入されたシクロペンテン、1~9個のフッ素原子が導入されたシクロヘキセンなどが挙げられる。
これらの不飽和フッ化炭化水素化合物の中では、プロペンのフッ化物が好ましく、フッ素原子が3~5個導入されたプロペンがより好ましく、フッ素原子が4個導入されたプロペンが最も好ましい。具体的には、1,3,3,3-テトラフルオロプロペン(HFO1234ze)、2,3,3,3-テトラフルオロプロペン(HFO1234yf)が好ましい化合物として挙げられる。
これらの不飽和フッ化炭化水素化合物は、1種を単独で用いてよく、2種以上を組み合わせて用いてもよいし、不飽和フッ化炭化水素化合物以外の冷媒と組み合わせて使用してもよい。ここで、不飽和フッ化炭化水素化合物以外の冷媒と組み合わせて用いる場合の例として、飽和フッ化炭化水素化合物と不飽和フッ化炭化水素化合物の混合冷媒が挙げられる。具体的な混合冷媒としては、R-32とHFO1234zeとR152aの混合冷媒(AC5、混合比は13.23:76.20:9.96)等が挙げられる。
自然系冷媒としては、二酸化炭素(炭酸ガス)や、プロパン、n-ブタン、イソブタン、2-メチルブタン、n-ペンタン、シクロペンタン、イソブタン、ノルマルブタン等の炭化水素や、アンモニアが挙げられ、これらの1種を単独で用いても、2種以上を組み合わせて用いてもよいし、自然系冷媒以外の冷媒と組み合わせてもよい。ここで、自然系冷媒以外の冷媒と組み合わせて用いる場合の例としては、飽和フッ化炭化水素化合物、不飽和フッ化炭化水素化合物、又はこれら両方との混合冷媒が挙げられる。具体的な混合冷媒としては、二酸化炭素とHFO1234zeとR134aの混合冷媒(AC6、配合比は5.15:79.02:15.41)等が挙げられる。
本実施形態に係る冷凍機油又は冷凍機用組成物は、冷凍機内部に充填して使用されるものである。ここで、冷凍機とは、圧縮機、凝縮器、膨張機構(膨張弁など)及び蒸発器、あるいは圧縮機、凝縮器、膨張機構、乾燥器及び蒸発器を必須とする構成からなる冷凍サイクルを有する。冷凍機油は、例えば圧縮機等に設けられる摺動部分を潤滑するために使用されるものである。
なお、冷凍機の摺動部分は、金属-金属間であることが好ましく、摺動部分の金属としては、鉄、鋼材が挙げられる。本実施形態の冷凍機油は、鉄ないし鋼材間の耐摩耗性を向上させつつ、摩擦係数を低下させることが可能である。
また、上記冷凍機油及び冷凍機用組成物は、より具体的には、例えばカーエアコン、ガスヒートポンプ(GHP)、空調、冷蔵庫、自動販売機、ショーケース、給湯機、床暖房などの各種冷凍機システム、給湯システム、及び暖房システムに用いることができる。
本発明の一実施形態に係る冷凍機油の製造方法は、上記した含酸素有機化合物を含む基油に、少なくとも上記多リン酸エステル系化合物及びベンゾトリアゾール系化合物を配合して冷凍機油を製造するものである。また、本方法では、多リン酸エステル系化合物及びベンゾトリアゾール系化合物以外にも、上記した各種添加剤のいずれか1種又は2種以上を配合してもよい。基油、多リン酸エステル系化合物、ベンゾトリアゾール系化合物、及び各種添加剤の詳細な説明は、上記と同様であるので、その説明は省略する。
JIS K2283:2000に準じ、ガラス製毛管式粘度計を用いて測定した。
(2)潤滑性試験
密閉式にしたブロックオンリング摩擦試験機(LFW-1)を用いて、R32(ジフルオロメタン)冷媒環境下で、各冷凍機用組成物の摺動部分の摩擦係数、及びリング摩耗量を以下の条件で測定した。
リング:FC250 ブロック:SKH51 回転数:1000rpm
馴らし:荷重300N×1分間 荷重:500N 時間:30分 油温:80℃
冷媒圧力:0.4MPa
表1に示す各実施例、比較例の冷凍機油、及びその冷凍機油を使用した冷凍機用組成物を各々調整して、潤滑性試験を実施した。その結果を表1に示す。
[基油]
PVE:エチルビニルエーテルとイソブチルビニルエーテルとの共重合体(モル比9:1、100℃動粘度7.8mm2/s)、両末端はそれぞれ一般式(A-1-i)及び一般式(A-1-ii)に示すものであり、R6a~R8a、R11a~R13aが水素原子となるとともに、r1及びr2のいずれもが0であり、R10a及びR15aはエチル基又はイソブチル基である。
PAG:ポリオキシプロピレングリコール(100℃動粘度9.8mm2/s)
ECP:ポリプロピレングリコール(PPG)/ポリエチルビニルエーテル(PEV)共重合体(PPG/PEVモル比5/5、100℃動粘度11.2mm2/s)
POE:ペンタエリスリトールオクタン酸(C8酸)ノナン酸(C9酸)エステル(C8酸/C9酸モル比1/1.1、100℃動粘度8.6mm2/s)
[添加剤]
多リン酸エステル系化合物1:上記一般式(5)においてnが1~3の混合物である化合物
多リン酸エステル系化合物2:上記一般式(5)においてnが1~8の混合物である化合物
多リン酸エステル系化合物3:上記一般式(6)で示される化合物
多リン酸エステル系化合物4:上記一般式(1)で示される化合物であって、R1、R3、R5、R7が水素原子であり、R2、R4、R6、R8が炭素数1~20のアルキル基、R9が炭素数2~20の二価の炭化水素基、nが1~8の混合物である化合物。
ベンゾトリアゾール系化合物1:1,2,3-ベンゾトリアゾール
ベンゾトリアゾール系化合物2:メチルベンゾトリアゾール
ベンゾトリアゾール系化合物3:1-[N,N-ビス(2-エチルヘキシル)アミノメチル]メチルベンゾトリアゾール
酸化防止剤:2,6-ジ-tert-ブチル-4-メチルフェノール(DBPC)
酸捕捉剤:2-エチルヘキシルグリシジルエーテル
消泡剤:シリコーン系消泡剤
それに対して、比較例1~16に示すように、冷凍機油に、多リン酸エステル系化合物及びベンゾトリアゾール系化合物のいずれか一方又は両方を含有させない場合には、耐摩耗性、及び摩擦係数の両方を良好にすることができなかった。
Claims (13)
- 含酸素有機化合物を含む基油と、多リン酸エステル系化合物と、ベンゾトリアゾール系化合物とを含む冷凍機油。
- 前記多リン酸エステル系化合物の含有量が、冷凍機油全量に対して0.01~5.0質量%である請求項1に記載の冷凍機油。
- 前記ベンゾトリアゾール系化合物の含有量が、冷凍機油全量に対して0.01質量%以上である請求項1又は2に記載の冷凍機油。
- 前記含酸素有機化合物が、ポリビニルエーテル類、ポリオキシアルキレングリコール類、ポリ(オキシ)アルキレングリコール又はそのモノエーテルとポリビニルエーテルとの共重合体、及びポリオールエステル類からなる群から選択される少なくとも1種である請求項1~3のいずれか1項に記載の冷凍機油。
- 一般式(1)においてR9がアリーレン基を含む請求項5に記載の冷凍機油。
- 冷媒と、請求項1~9のいずれか1項に記載される冷凍機油とを含む冷凍機用組成物。
- 前記冷媒が、フッ化炭化水素、二酸化炭素、炭化水素、及びアンモニアからなる群から選択される1種又は2種以上を含む請求項10に記載の冷凍機用組成物。
- 前記冷媒が、飽和フッ化炭化水素化合物を含む請求項10又は11に記載の冷凍機用組成物。
- 含酸素有機化合物を含む基油に、多リン酸エステル系化合物と、ベンゾトリアゾール系化合物とを少なくとも配合して冷凍機油を得る、冷凍機油の製造方法。
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US16/063,883 US20180371355A1 (en) | 2016-01-15 | 2017-01-13 | Refrigeration oil, and composition for use in refrigerating machine |
CN201780006502.7A CN108473907A (zh) | 2016-01-15 | 2017-01-13 | 冷冻机油、和冷冻机用组合物 |
KR1020187019684A KR20180101383A (ko) | 2016-01-15 | 2017-01-13 | 냉동기유, 및 냉동기용 조성물 |
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JP2016006596A JP6657538B2 (ja) | 2016-01-15 | 2016-01-15 | 冷凍機油、及び冷凍機用組成物 |
JP2016-006596 | 2016-01-15 |
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US (1) | US20180371355A1 (ja) |
JP (1) | JP6657538B2 (ja) |
KR (1) | KR20180101383A (ja) |
CN (1) | CN108473907A (ja) |
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CA3192341A1 (en) * | 2020-09-09 | 2022-03-17 | Citizen Watch Co., Ltd. | Industrial oil composition |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08259980A (ja) * | 1995-03-17 | 1996-10-08 | Tonen Corp | 潤滑油組成物 |
WO2011118708A1 (ja) * | 2010-03-26 | 2011-09-29 | 株式会社Adeka | 潤滑油添加剤及びそれを含有する潤滑油組成物 |
JP2012107108A (ja) * | 2010-11-17 | 2012-06-07 | Adeka Corp | 摩耗防止剤組成物及び該摩耗防止剤組成物を含有する潤滑油組成物 |
Family Cites Families (3)
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JP3173684B2 (ja) | 1992-06-04 | 2001-06-04 | 出光興産株式会社 | 圧縮型冷凍機用潤滑油 |
JP3133201B2 (ja) | 1993-10-29 | 2001-02-05 | 日石三菱株式会社 | 作動油組成物 |
JP2859253B2 (ja) | 1997-12-08 | 1999-02-17 | 出光興産株式会社 | フッ化アルカン冷媒用冷凍機油 |
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2016
- 2016-01-15 JP JP2016006596A patent/JP6657538B2/ja active Active
-
2017
- 2017-01-13 WO PCT/JP2017/001042 patent/WO2017122786A1/ja active Application Filing
- 2017-01-13 US US16/063,883 patent/US20180371355A1/en not_active Abandoned
- 2017-01-13 CN CN201780006502.7A patent/CN108473907A/zh active Pending
- 2017-01-13 KR KR1020187019684A patent/KR20180101383A/ko unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH08259980A (ja) * | 1995-03-17 | 1996-10-08 | Tonen Corp | 潤滑油組成物 |
WO2011118708A1 (ja) * | 2010-03-26 | 2011-09-29 | 株式会社Adeka | 潤滑油添加剤及びそれを含有する潤滑油組成物 |
JP2012107108A (ja) * | 2010-11-17 | 2012-06-07 | Adeka Corp | 摩耗防止剤組成物及び該摩耗防止剤組成物を含有する潤滑油組成物 |
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JP6657538B2 (ja) | 2020-03-04 |
CN108473907A (zh) | 2018-08-31 |
US20180371355A1 (en) | 2018-12-27 |
KR20180101383A (ko) | 2018-09-12 |
JP2017125161A (ja) | 2017-07-20 |
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