WO2017222004A1 - Huile pour machines frigorifiques et composition pour machines réfrigérantes - Google Patents

Huile pour machines frigorifiques et composition pour machines réfrigérantes Download PDF

Info

Publication number
WO2017222004A1
WO2017222004A1 PCT/JP2017/022949 JP2017022949W WO2017222004A1 WO 2017222004 A1 WO2017222004 A1 WO 2017222004A1 JP 2017022949 W JP2017022949 W JP 2017022949W WO 2017222004 A1 WO2017222004 A1 WO 2017222004A1
Authority
WO
WIPO (PCT)
Prior art keywords
refrigerating machine
machine oil
group
refrigerant
structural unit
Prior art date
Application number
PCT/JP2017/022949
Other languages
English (en)
Japanese (ja)
Inventor
中島　聡
知也 松本
Original Assignee
出光興産株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 出光興産株式会社 filed Critical 出光興産株式会社
Publication of WO2017222004A1 publication Critical patent/WO2017222004A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/20—Lubricating compositions characterised by the base-material being a macromolecular compound containing oxygen
    • C10M107/22—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M107/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds containing monomers having an unsaturated radical bound to an alcohol, aldehyde, ketonic, ether, ketal or acetal radical
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M129/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen
    • C10M129/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing oxygen having a carbon chain of less than 30 atoms
    • C10M129/04—Hydroxy compounds
    • C10M129/10—Hydroxy compounds having hydroxy groups bound to a carbon atom of a six-membered aromatic ring
    • 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
    • C10M137/04—Phosphate esters

Definitions

  • the present invention relates to a refrigerator oil and a refrigerator composition containing a refrigerant and a refrigerator oil.
  • a compression refrigerator includes at least a compressor, a condenser, an expansion mechanism (an expansion valve, etc.), an evaporator, and the like, and a sealed system is mixed with a mixture of refrigerant and refrigerating machine oil (hereinafter, “ It also has a structure in which the composition for the refrigerator is also circulated.
  • a refrigerant used in a compression refrigerator HFC (hydrofluorocarbon) that does not destroy the ozone layer is widely used.
  • HFC, R134a and the like are often used, but in recent years, the use of difluoromethane (R32) having a lower global warming potential is being studied.
  • difluoromethane (R32) is also referred to as “R32 refrigerant”.
  • R32 refrigerant difluoromethane
  • additives such as antioxidants, acid scavengers, extreme pressure agents, etc. are blended with polyvinyl ether compounds such as polyethyl vinyl ether, copolymers of ethyl vinyl ether and isobutyl vinyl ether, etc.
  • polyvinyl ether compounds such as polyethyl vinyl ether, copolymers of ethyl vinyl ether and isobutyl vinyl ether, etc.
  • the R32 refrigerant has a compressor discharge temperature of 20 ° C. or higher compared to R134a or the like. Therefore, the refrigerating machine oil used for the R32 refrigerant is likely to increase in acid value due to decomposition at a high temperature. In order to suppress such an increase in acid value, refrigerating machine oils are required to have excellent high-temperature oxidation stability. Moreover, since the inside of a compressor becomes high temperature, the refrigerating machine oil also needs lubricity under high temperature. Furthermore, the refrigeration oil is generally required to circulate in the system of the compression refrigeration machine without phase separation from the refrigerant. In a compression refrigerator, the inside of a compressor becomes high temperature and the inside of a cooler becomes low temperature. Therefore, the refrigerating machine oil is required to have a property compatible with the refrigerant from a high temperature to a low temperature.
  • the present inventors have found that a refrigerating machine oil containing a polyvinyl ether-based compound having a methoxyethyl group and a specific additive can solve the above problems, and completed the present invention. That is, the present invention provides the following [1] and [2].
  • a refrigerating machine composition comprising the refrigerating machine oil according to the above [1] and a refrigerant.
  • the refrigerating machine oil of the present invention is excellent in oxidation stability and lubricity even at high temperatures and has good compatibility with a refrigerant containing R32 over a wide temperature range from high temperature to low temperature.
  • the refrigerating machine oil is a refrigerating machine oil for refrigerant containing R32 refrigerant, and includes a polyvinyl ether compound (A) containing a structural unit (a1) having a methoxyethyl group in the side chain, and an oxidation product.
  • a refrigerating machine oil comprising at least one selected from the group consisting of an inhibitor (B) and an acid scavenger (C).
  • the polyvinyl ether compound (A) is a compound having a polyvinyl ether structure and includes a structural unit (a1) having a methoxyethyl group in the side chain.
  • a polyvinyl ether type compound (A) comprises the base oil of refrigerating machine oil.
  • the refrigerating machine oil contains the polyvinyl ether compound (A) as a base oil, so that it is excellent in compatibility with the R32 refrigerant even in a low temperature environment, and can suppress the phase separation between the refrigerating machine oil and the refrigerant. is there.
  • the content of the polyvinyl ether compound (A) is preferably 70 to 99.7% by mass, more preferably 75 to 99.3% by mass, and still more preferably 80 to 80%, based on the total amount (100% by mass) of the refrigerating machine oil. It is 98.4 mass%.
  • a polyvinyl ether type compound (A) may be contained individually by 1 type in refrigerating machine oil, and may be contained in combination of 2 or more type.
  • the kinematic viscosity at 40 ° C. of the polyvinyl ether compound (A) is preferably 10 to 400 mm 2 / s, more preferably 15 to 220 mm 2 / s, and still more preferably 28 to 110 mm 2 / s.
  • the viscosity index (VI) of the polyvinyl ether compound (A) is preferably 90 or more, more preferably 100 or more, and still more preferably 110 or more.
  • the polyvinyl ether compound (A) contains the structural unit (a1) having a methoxyethyl group in the side chain, the viscosity index tends to increase. Therefore, it becomes easy to improve the lubricity of the refrigerating machine oil, such that the kinematic viscosity becomes an appropriate value both at a low temperature and a high temperature, and the wear resistance of the refrigerating machine oil at a high temperature is improved.
  • the kinematic viscosity and the viscosity index mean values measured according to JIS K2283: 2000.
  • the number average molecular weight (Mn) of the polyvinyl ether compound (A) may be in the range where the kinematic viscosity at 40 ° C. falls within the above range, but from the viewpoint of improving the lubricating performance of the refrigerating machine oil, preferably 300 to 3000, More preferably, it is 350-2500, and still more preferably 400-2000.
  • the number average molecular weight is a value in terms of standard polystyrene measured by a gel permeation chromatography (GPC) method, and specifically means a value measured by the method described in Examples. To do.
  • the structural unit (a1) of the polyvinyl ether compound (A) is preferably one represented by the following general formula (1).
  • R 1 to R 3 each independently represent a hydrogen atom or a carbon number of 1 to 8 (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2).
  • a hydrocarbon group is shown.
  • Examples of the hydrocarbon group that can be selected as R 1 to R 3 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.
  • R 1 to R 3 are preferably either a hydrogen atom or an alkyl group, and more preferably all are hydrogen atoms.
  • R 1 to R 3 in the general formula (1) may be the same or different for each structural unit. That is, the polyvinyl ether compound (A) can include copolymers in which any or all of R 1 to R 3 are different for each structural unit.
  • a polyvinyl ether type compound (A) has another structural unit different from a structural unit (a1) with a structural unit (a1).
  • the content of the structural unit (a1) is all structural units (100 mol%) of the polyvinyl ether compound (A) from the viewpoint of compatibility with the R32 solvent and a refrigerating machine oil excellent in lubricity at high temperatures. On the basis, it is preferably 1 mol% or more, more preferably 10 mol% or more, still more preferably 20 mol% or more. Further, the content of the structural unit (a1) is preferably 100 mol% or less, more preferably 70 mol% or less, and still more preferably 50 mol% or less, from the viewpoint of increasing the volume resistivity of the refrigerating machine oil.
  • the polyvinyl ether compound (A) preferably contains a structural unit (a2) represented by the following general formula (2), which is different from the structural unit (a1), together with the structural unit (a1).
  • a structural unit (a2) represented by the following general formula (2), which is different from the structural unit (a1), together with the structural unit (a1).
  • R 4 to R 6 are each independently a hydrogen atom or a carbon number of 1 to 8 (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2).
  • a hydrocarbon group is shown.
  • examples of the hydrocarbon group that can be selected as R 4 to R 6 include the same hydrocarbon groups as those described above as R 1 to R 3 .
  • all of R 4 to R 6 are preferably either a hydrogen atom or an alkyl group, and more preferably all are hydrogen atoms.
  • R 7 represents a divalent hydrocarbon group having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4).
  • R represents an integer of 0 to 10, preferably 0 to 3, more preferably 0 to 2, still more preferably 0 to 1, and still more preferably 0.
  • the plurality of R 7 may be the same or different from each other.
  • Examples of the divalent hydrocarbon group that can be selected as R 7 include an ethylene group, a phenylethylene group, a 1,2-propylene group, a 2-phenyl-1,2-propylene group, a 1,3-propylene group, and various types.
  • Alkylene groups such as butylene group, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, various nonylene groups, various decylene groups; cyclohexylene group, methylcyclohexylene group, ethylcyclohexylene group, dimethylcyclohexylene group, Divalent alicyclic hydrocarbon groups such as propylcyclohexylene group; divalent aromatic hydrocarbon groups such as various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups and various naphthylene groups; toluene Alkyl groups and aromatics of alkyl aromatic hydrocarbons such as ethylbenzene A divalent alkyl aromatic hydrocarbon group having a monovalent bonding site in each moiety; a divalent alkyl aromatic hydrocarbon group having a bonding site in the alkyl group moiety of a polyalky
  • R 8 represents a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4).
  • the hydrocarbon group that can be selected as R 8 includes, for example, various nonyl groups and various decyl groups in addition to the groups exemplified as the hydrocarbon group having 1 to 8 carbon atoms that can be selected as R 1 to R 3 described above.
  • Alkyl groups such as: various propyl cyclohexyl groups, cycloalkyl groups such as various trimethyl cyclohexyl groups; aryl groups such as various propyl phenyl groups, various trimethyl phenyl groups, various butyl phenyl groups, various naphthyl groups; various phenyl propyl groups, various phenyls Arylalkyl groups such as butyl group; and the like.
  • R 8 an alkyl group is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable.
  • R 7 in the general formula (2) is an ethylene group (—CH 2 CH 2 —), and When R 8 is a methyl group, r is not 1.
  • the structural unit (a2) is more preferably a structural unit (a2-1) represented by the following general formula (2-1).
  • a2-1 a structural unit represented by the following general formula (2-1).
  • R 8 is the same as defined in the general formula (2).
  • the content of the structural unit (a2-1) is preferably 70 based on the total amount (100 mol%) of the structural unit (a2) contained in the polyvinyl ether compound (A). To 100 mol%, more preferably 80 to 100 mol%, still more preferably 90 to 100 mol%.
  • the content of the structural unit in which R 8 in the general formulas (2) and (2-1) is an ethyl group is the total amount (100 mol%) of the structural unit (a2) contained in the polyvinyl ether compound (A). ), Preferably 50 to 100 mol%, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol%, particularly preferably 100 mol%. Further, when the polyvinyl ether compound (A) is the structural unit (a2-1) represented by the general formula (2-1), the structural unit (a1) represented by the general formula (1) is used. In particular, all of R 1 to R 3 are preferably hydrogen atoms.
  • the content of the structural unit (a2) is preferably 0 to 99 mol%, more preferably 30 to 90 mol%, still more preferably 50, based on the total structural unit (100 mol%) of the polyvinyl ether compound (A). ⁇ 80 mol%.
  • the polyvinyl ether compound (A) may have other structural units other than the structural unit (a1) and the structural unit (a2).
  • the total content of the structural unit (a1) and the structural unit (a2) is preferably 70 to 100 mol%, more preferably based on the total structural unit (100 mol%) of the polyvinyl ether compound (A). It is 80 to 100 mol%, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol%, particularly preferably 100 mol%.
  • 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 polyvinyl ether compound (A).
  • at least one of the terminal portions of the polyvinyl ether compound (A) is preferably a group represented by the following general formula (3-1).
  • R 11 to R 13 are each independently a hydrogen atom or 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2).
  • R 14 represents a divalent hydrocarbon group having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4).
  • r1 represents an integer of 0 to 10, preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1. When r1 is 2 or more, the plurality of R 14 may be the same or different from each other.
  • R 15 represents a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4). * Represents a binding moiety.
  • one of the terminal portions of the polyvinyl ether compound (A) is a group represented by the general formula (3-1), and the other is the following general formula (3-1a), A group having any one of (3-1b) and (3-1c) or a group having an olefinically unsaturated bond is preferable, and a group of the following general formula (3-1a) is more preferable.
  • R 11a to R 13a are each independently a hydrogen atom or 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2).
  • R 14a represents a divalent hydrocarbon group having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4).
  • r2 represents an integer of 0 to 10, preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1. When r2 is 2 or more, the plurality of R 14a may be the same or different from each other.
  • R 15a represents a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8, more preferably 1 to 6, and still more preferably 1 to 4). * Represents a binding moiety.
  • R 11b to R 13b each independently represent a hydrogen atom or 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2).
  • R 14b and R 16b each independently represent a divalent hydrocarbon group having 2 to 10 carbon atoms (preferably 2 to 6, more preferably 2 to 4).
  • r3 and r4 each independently represents an integer of 0 to 10, preferably 0 to 3, more preferably 0 to 2, and still more preferably 0 to 1.
  • the plurality of R 14b and R 16b may be the same or different from each other.
  • R 15b and R 17b each independently represent a hydrocarbon group having 1 to 10 carbon atoms (preferably 1 to 8, more preferably 1 to 6, and further preferably 1 to 4). * Represents a binding moiety.
  • R 11c to R 13c each independently represents a hydrogen atom or 1 to 8 carbon atoms (preferably 1 to 6, more preferably 1 to 4, more preferably 1 to 2). Represents a hydrocarbon group.
  • R 11 to R 13 , R 11a to R 13a , R 11b to R 13b , and the hydrocarbon group having 1 to 8 carbon atoms that can be selected as R 11c to R 13c is the same as the hydrocarbon group having 1 to 8 carbon atoms that can be selected as R 4 to R 6 in the general formula (2).
  • suitable groups are the same.
  • the divalent hydrocarbon group having 2 to 10 carbon atoms that can be selected as R 14 , R 14a , R 14b , and R 16b includes 2 carbon atoms that can be selected as R 7 in the general formula (2).
  • the same as the divalent hydrocarbon group of ⁇ 10 can be mentioned, and preferable groups are also the same. Furthermore, as the hydrocarbon group having 1 to 10 carbon atoms that can be selected as R 15 , R 15a , R 15b , and R 17b , the hydrocarbon group having 1 to 10 carbon atoms that can be selected as R 8 in the general formula (2). The same thing as a hydrocarbon group is mentioned, A suitable group is also the same.
  • the vinyl ether type monomer represented by the following general formula (I) is mentioned, for example.
  • R 1 to R 3 are the same as defined in the general formula (1).
  • the vinyl ether type monomer represented by the following general formula (II) is mentioned, for example.
  • R 4 to R 8 and r are the same as defined in the general formula (2).
  • the synthesis method of the polyvinyl ether compound (A) is to add a raw material monomer into the system in the presence of a polymerization catalyst and a polymerization initiator, A method of allowing the polymerization reaction to proceed is preferred.
  • Examples of the polymerization catalyst include Bronsted acids, Lewis acids, and organometallic compounds, and Lewis acids are preferable.
  • Examples of Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid, and the like.
  • Examples of Lewis acids include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, ferric chloride and the like, and boron trifluoride is preferable.
  • Examples of the organometallic compound include diethyl aluminum chloride, ethyl aluminum chloride, diethyl zinc and the like.
  • polymerization initiator examples include water, alcohols, phenols, acetals, adducts of vinyl ethers and carboxylic acids, and these may be used alone or in combination of two or more. Depending on the type of these polymerization initiators, the terminal portion of the resulting polyvinyl ether compound (A) is formed.
  • alcohols include saturated fats having 1 to 20 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols, and various octanols.
  • An unsaturated alcohol having 3 to 10 carbon atoms such as allyl alcohol; an ether-bonded oxygen-containing alcohol having 14 or less carbon atoms such as ethylene glycol monoalkyl ether and ethylene glycol monoaryl ether;
  • phenols include phenol and various cresols.
  • acetals include acetaldehyde dimethyl acetal, acetaldehyde diethyl acetal, acetaldehyde methyl ethyl acetal, acetaldehyde bis (methoxyethyl) acetal, and the like.
  • adduct of vinyl ethers and carboxylic acid include adducts such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, and 3,5,5-trimethylcaproic acid.
  • the polymerization initiation terminal of the obtained polyvinyl ether compound (A) is bonded with hydrogen when water, alcohols or phenols are used.
  • acetals When acetals are used, one alkoxy group eliminated from the acetals is bonded.
  • an adduct of vinyl ethers and carboxylic acid When an adduct of vinyl ethers and carboxylic acid is used, an alkylcarbonyloxy group derived from the carboxylic acid moiety eliminated from the adduct of vinyl ethers and carboxylic acid is bonded.
  • the stop terminal of the polyvinyl ether compound (A) becomes an acetal, an olefin, or an aldehyde when water, alcohols, phenols, or acetals are used.
  • an adduct of vinyl ethers and carboxylic acid it becomes a carboxylic acid ester of hemiacetal, and becomes an aldehyde when hydrolyzed in the presence of an acid.
  • the polymerization reaction depends on the type of raw material monomer and polymerization initiator used, it is usually at a temperature of ⁇ 80 to 150 ° C. (preferably 0 to 100 ° C.) and about 10 seconds to 10 hours after the reaction starts. It is preferable to end.
  • the said polymerization reaction is normally performed in presence of a solvent.
  • the solvent to be used is not particularly limited as long as it can dissolve the required amount of the reaction raw material and is inert to the polymerization reaction.
  • hydrocarbon solvents such as hexane, benzene and toluene
  • ether solvents such as ether, 1,2-dimethoxyethane, tetrahydrofuran and the like.
  • the polymer obtained after the polymerization reaction has an unsaturated bond, an acetal, and an aldehyde
  • the hydrogenation treatment is performed at a reaction temperature of 10 to 250 ° C. (preferably 50 to 200 ° C.) by introducing hydrogen gas at a hydrogen pressure of 0.1 to 10 MPa (preferably 1 to 6 MPa) in the presence of a hydrogenation catalyst.
  • the hydrogenation catalyst include metal catalysts such as nickel-based catalysts, platinum-based catalysts, palladium-based catalysts, and ruthenium-based catalysts. Catalysts in which these metal catalysts are supported on alumina or diatomaceous earth, Raney-type catalysts, and the like Can also be used.
  • the refrigerating machine oil may contain only the polyvinyl ether compound (A) as the base oil, but may contain a base oil other than the polyvinyl ether compound (A) as long as the effects of the present invention are not impaired.
  • Other base oils include, for example, polyvinyl ether compounds not containing the structural unit (a1), polyalkylene glycol compounds, poly (oxy) alkylene glycol or monoethers thereof, and polyvinyl ethers not containing the structural unit (a1) And a copolymer of polyol ester and the like. These other base oils may be used alone or in combination of two or more. These other base oils may be those having the same 40 ° C.
  • kinematic viscosity as the polyvinyl ether compound (A), and the specific 40 ° C. kinematic viscosity is preferably 10 to 400 mm 2 / s, more preferably. Is 15 to 220 mm 2 / s, more preferably 28 to 110 mm 2 / s.
  • the content of the base oil other than the polyvinyl ether compound (A) is based on 100 parts by mass of the polyvinyl ether compound (A) from the viewpoint of a refrigerating machine oil excellent in compatibility with the R32 refrigerant.
  • the amount is preferably 0 to 30 parts by mass, more preferably 0 to 20 parts by mass, still more preferably 0 to 10 parts by mass, and still more preferably 0 to 3 parts by mass.
  • the refrigerating machine oil which concerns on one Embodiment of this invention contains an additive.
  • the refrigerating machine oil contains an antioxidant (B), an acid scavenger (C), or both as an additive, but preferably contains both.
  • Refrigerating machine oil contains an antioxidant (B) or an acid scavenger (C), thereby preventing the acid value of the refrigerating machine oil from increasing at high temperatures and improving the high-temperature oxidation stability of the refrigerating machine oil. Is possible.
  • the refrigerating machine oil contains both the antioxidant (B) and the acid scavenger (C), thereby further suppressing the increase in the acid value of the refrigerating machine oil and further improving the high-temperature oxidation stability of the refrigerating machine oil. It becomes possible to make it.
  • antioxidant (B) examples include phenolic antioxidants and amine antioxidants.
  • examples of phenolic antioxidants include monophenolic antioxidants and polyphenolic antioxidants.
  • Monophenol antioxidants include n-octyl-3- (3,5-di-t-butyl 4-hydroxyphenyl) propionate, 6-methylheptyl-3- (3,5-di-t-butyl- Alkyl-3- (3,5-di-t-butyl-4-hydroxy) such as 4-hydroxyphenyl) propionate and n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate
  • Phenyl) propionate alkyl groups include those having 4 to 20 carbon atoms, preferably 8 to 18 carbon atoms); 2,6-di-t-butyl-4-methylphenol, 2,6 -2,6-di-t-butyl-4-alkylphenol (dialkyl having 1 to 4 carbon atoms) such as di-t-butyl-4-ethylphenol; 2,4-dimethyl-6-t- Butylphenol, 2,6-di -t- amy
  • Polyphenol antioxidants include 4,4′-methylenebis (2,6-di-t-butylphenol), 4,4′-bis (2,6-di-t-butylphenol), 4,4 ′.
  • -Bis (2-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), 4,4′-isopropylidenebis (2,6-di-tert-butylphenol), 2,2′-methylenebis (4-6) -Nonylphenol), 2,2'-isobutylidenebis (4,6-dimethylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 4, '-Thiobis (2-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-buty
  • amine-based antioxidants examples include dialkyldiphenylamines such as 4,4′-dibutyldiphenylamine and 4,4′-dioctyldiphenylamine, and phenyl- ⁇ -naphthylamines such as alkylphenyl- ⁇ -naphthylamine and phenyl- ⁇ -naphthylamine. N, N′-di-phenyl-p-phenylenediamine and the like.
  • antioxidant (B) a phenolic antioxidant is preferable.
  • 2,6-di-t-butyl-4-alkylphenol is more preferable, and 2,6-di-t-butyl-4-methylphenol is most preferable.
  • the content of the antioxidant (B) in the refrigerating machine oil is preferably 0.1 to 5% by mass, more preferably 0.1 to 3% by mass, based on the total amount of the refrigerating machine oil, and 0.15 More preferably, it is ⁇ 1% by mass.
  • the antioxidant sufficiently suppresses an increase in the acid value of the refrigerating machine oil and facilitates enhancing high-temperature stability. Moreover, it becomes easy to exhibit the effect corresponding to content by setting it as these upper limit values or less.
  • an antioxidant (B) may be used individually by 1 type, and may use 2 or more types together.
  • acid scavenger (C) examples include epoxy compounds, and more specifically, glycidyl ether compounds, cyclohexene oxide, ⁇ -olefin oxide, epoxidized soybean oil, and the like, with glycidyl ether compounds being preferred.
  • examples of the glycidyl ether compound include aliphatic mono- or polyhydric alcohols having 3 to 30, preferably 4 to 24, more preferably 6 to 16 carbon atoms, or an aromatic compound-derived glycidyl derived from an aromatic compound. Ether.
  • the aliphatic mono- or polyhydric alcohol may be linear, branched or cyclic, and may be saturated or unsaturated, but is preferably a saturated aliphatic monoalcohol.
  • an aromatic polyhydric alcohol or an aromatic compound containing two or more hydroxyl groups it is preferable that all of the hydroxyl groups are glycidyl etherified from the viewpoint of suppressing the stability of the refrigerating machine oil and the hydroxyl value.
  • the glycidyl ether compound include phenyl glycidyl ether, alkyl glycidyl ether, and alkylene glycol glycidyl ether.
  • glycidyl ether that is, alkyl glycidyl ether having an alkyl group having 6 to 16 carbon atoms
  • examples of such glycidyl ether include 2-ethylhexyl glycidyl ether, isononyl glycidyl ether, decyl glycidyl ether, lauryl glycidyl ether, myristyl glycidyl ether, and 2-ethylhexyl glycidyl ether is most preferable.
  • an alkyl glycidyl ether such as 2-ethylhexyl glycidyl ether, an increase in the acid value of the refrigerating machine oil can be appropriately prevented, and oxidation stability at high temperatures can be easily improved.
  • the content of the acid scavenger (C) in the refrigerating machine oil is preferably 0.1 to 10% by mass based on the total amount of the refrigerating machine oil.
  • the content of the acid scavenger (C) is more preferably 0.4 to 5% by mass, further preferably 0.5 to 5% by mass, particularly preferably 0.5 to 3% by mass, and most preferably 0.5 to 2% by mass.
  • an acid capture agent (C) may be used individually by 1 type, and may use 2 or more types together.
  • an acid scavenger (C) can further suppress an increase in acid value by using together with the above-mentioned antioxidant (B).
  • the refrigerating machine oil preferably further contains an extreme pressure agent (D).
  • the refrigerating machine oil has good wear resistance at high temperatures and can further improve lubricity.
  • the extreme pressure agent (D) include phosphorus-based extreme pressure agents.
  • the phosphorus extreme pressure agent include phosphoric acid esters, phosphorous acid esters, acidic phosphoric acid esters, acidic phosphorous acid esters, and amine salts thereof.
  • phosphate esters include triaryl phosphate, trialkyl phosphate, monoalkyl diaryl phosphate, dialkyl monoaryl phosphate, and trialkenyl phosphate.
  • the “aryl” described in the extreme pressure agent (D) is a concept including not only a functional group consisting of only an aromatic ring but also alkylaryl and arylalkyl.
  • phosphate esters include triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, propyl phenyl diphenyl phosphate, dipropyl phenyl phenyl phosphate, and ethyl phenyl diphenyl phosphate.
  • Examples of acidic phosphate esters include various alkyl acid phosphates and dialkyl acid phosphates.
  • Examples of phosphites include various trialkyl phosphites, triaryl phosphites, monoalkyl diaryl phosphites, dialkyl monoaryl phosphites, and trialkenyl phosphites.
  • Examples of the acidic phosphite include various dialkyl hydrogen phosphites, dialkenyl hydrogen phosphites, and diaryl hydrogen phosphites.
  • the phosphorus extreme pressure agent may be a phosphate ester containing a sulfur atom such as trithiophenyl phosphate.
  • the amine salt of acidic phosphate ester or acidic phosphite is mentioned.
  • the amine salt that forms the amine salt may be a primary, secondary, or tertiary amine.
  • phosphate esters are preferable, triaryl phosphate is more preferable, and tricresyl phosphate is most preferable.
  • a triaryl phosphate such as tricresyl phosphate
  • lubricity at a high temperature tends to be good.
  • Other preferable examples include trithiophenyl phosphate, tri (nonylphenyl) phosphite, dioleyl hydrogen phosphite, and 2-ethylhexyl diphenyl phosphite.
  • the content of the extreme pressure agent (D) in the refrigeration oil is preferably 0.1 to 5% by mass based on the total amount of the refrigeration oil.
  • the content of the extreme pressure agent (D) is more preferably 0.3 to 3% by mass, further preferably 0.5 to 3% by mass, and most preferably 0.5 to 2% by mass.
  • the extreme pressure agent (D) is added to the refrigerating machine oil, the acid value tends to increase, but by using the antioxidant (B) and the acid scavenger (C) in combination, the extreme pressure agent (D ) Can be suppressed more appropriately.
  • the refrigerating machine oil in the present embodiment particularly preferably contains any of the antioxidant (B), the acid scavenger (C), and the extreme pressure agent (D).
  • the contents of the components (D) to (D) are also as described above. That is, the content of each of the polyvinyl ether compound (A), the antioxidant (B), the acid scavenger (C), and the extreme pressure agent (D) is 70 to 99.7% by mass based on the total amount of refrigerating machine oil, It is preferably 0.1 to 5% by mass, 0.1 to 10% by mass, and 0.1 to 5% by mass, preferably 75 to 99.3% by mass, 0.1 to 3% by mass, 0.4 to 5%.
  • the antioxidant (B) is a phenolic antioxidant
  • the acid scavenger (C) is a glycidyl ether compound
  • the extreme pressure agent (D) is a phosphate ester
  • the antioxidant (B) is 2 , 6-di-t-butyl-4-alkylphenol
  • the acid scavenger (C) is preferably alkyl glycidyl ether
  • the extreme pressure agent (D) is triaryl phosphate
  • the antioxidant (B) is 2, More preferably, 6-di-t-butyl-4-methylphenol
  • the acid scavenger (C) is 2-ethylhexyl glycidyl ether
  • the extreme pressure agent (D) is tricresyl phosphate.
  • the refrigerating machine oil may be composed of a base oil and (B) or (C) component or both, or from a base oil, (B) or (C) component or both, and (D) component.
  • additives other than these components (B) to (D) may be further contained. Examples of such additives include oxygen scavengers, oiliness improvers, copper deactivators, rust inhibitors, and antifoaming agents. These additives may be used alone or in combination of two or more.
  • 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.
  • oil improvers 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, Aliphatic saturated and unsaturated monoalcohols such as lauryl alcohol, oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine, oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide, oleic acid amide, Examples thereof include partial esters of polyhydric alcohols such as glycerin and sorbitol and aliphatic saturated or unsaturated monocarboxylic acids.
  • Examples of the copper deactivator include N- [N, N′-dialkyl (alkyl group having 3 to 12 carbon atoms) aminomethyl] triazole.
  • Examples of the rust inhibitor include metal sulfonates, aliphatic amines, organic sulfonic acid metal salts, organic phosphoric acid metal salts, alkenyl succinic acid esters, and polyhydric alcohol esters.
  • Examples of the antifoaming agent include silicone oils such as dimethylpolysiloxane, polymethacrylates, and the like. The content of each of these refrigerating machine oil additives is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total amount (100% by mass) of the refrigerating machine oil.
  • Refrigerating machine oil is excellent in compatibility with R32 refrigerant having a low global warming potential even in a low temperature environment.
  • the two-layer separation temperature on the low temperature side of the refrigerating machine oil with the R32 refrigerant is preferably ⁇ 15 ° C. or lower, more preferably ⁇ 30 ° C. or lower, and further preferably ⁇ 40 ° C. or lower.
  • the manufacturing method of the refrigerating machine oil which concerns on one Embodiment of this invention is a manufacturing method of the refrigerating machine oil for refrigerant
  • a refrigerating machine oil is produced by blending at least one selected from the group consisting of an antioxidant (B) and an acid scavenger (C) with an ether compound (A).
  • the polyvinyl ether compound (A) is further blended with additives other than the antioxidant (B) and the acid scavenger (C) such as the extreme pressure agent (D) as described above.
  • a base oil other than the compound (A) may be blended.
  • the details of the components (A) to (D), other additives, other base oils, and the obtained refrigerating machine oil are as described above.
  • composition for refrigerator The refrigerating machine oil is used by being mixed with a refrigerant.
  • a mixture of refrigerant in refrigeration oil is referred to as a “composition for a refrigeration machine”. That is, the composition for refrigerators which concerns on one Embodiment of this invention contains the refrigerant
  • the content ratio between the refrigerator oil and the refrigerant is preferably 1/99 to 99/1, more preferably 5/95 to 60/40, in mass ratio. .
  • the refrigerant may be composed of the R32 refrigerant alone, but may be a mixture of the R32 refrigerant and other refrigerants.
  • refrigerants include fluorinated hydrocarbon refrigerants, natural refrigerants such as hydrocarbon refrigerants, carbon dioxide, and ammonia.
  • Other refrigerants may be used alone or in combination of two or more.
  • the content of the R32 refrigerant is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, still more preferably 30 to 100% by mass, and still more preferably, based on the total amount (100% by mass) of the refrigerant. Is 50 to 100% by mass, particularly preferably 70 to 100% by mass.
  • coolant of R32 independent is the most preferable.
  • Examples of the fluorinated hydrocarbon refrigerant include a saturated fluorinated hydrocarbon refrigerant and an unsaturated fluorinated hydrocarbon refrigerant.
  • Examples of the saturated fluorinated hydrocarbon refrigerant include fluorides of alkanes having 1 to 4 carbon atoms other than R32, preferably fluorides of alkanes having 2 to 3 carbon atoms, and fluorides of alkane (ethane) having 2 carbon atoms. Is more preferable.
  • 1,1,1,2,2-pentafluoroethane (R125), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2,2-tetrafluoroethane (R134), 1 , 1,1-trifluoroethane (R143a), 1,1,2-trifluoroethane (R143), 1,1-difluoroethane (R152a), among which R125 and R134a are preferred.
  • These saturated fluorinated hydrocarbon refrigerants can be used as a mixture of two or more.
  • the refrigerant used in this embodiment is specifically a mixture of R32, R125, and R134a such as R407A, R407C, and R407E, and a mixture of R32 and R125 such as R410A. Etc. are mentioned as preferred examples, and among these, R410A is more preferred.
  • Examples of the unsaturated fluorinated hydrocarbon refrigerant include those having a carbon-carbon double bond, such as a linear or branched chain olefin having 2 to 6 carbon atoms and a fluorinated product of a cyclic olefin having 4 to 6 carbon atoms. It is done. Of these, propene fluoride is preferred, propene having 3 to 5 fluorine atoms introduced therein is more preferred, and propene having 4 fluorine atoms introduced is most preferred. As other than propene fluoride, ethylene fluoride is also preferred, ethylene having 1 to 3 fluorine atoms introduced is more preferred, and ethylene having 3 fluorine atoms introduced is most preferred.
  • preferable unsaturated fluorinated hydrocarbon refrigerants include 1,2,3,3,3-pentafluoropropene (R1225ye), 2,3,3,3-tetrafluoropropene (R1234yf), 1,3,3, 3,3-tetrafluoropropene (R1234ze), 1,2,3,3-tetrafluoropropene (R1234yz), 1,1,2-trifluoroethylene (R1123) and the like, among which R1234yf, R1234ze , R1123 is preferred.
  • the content is preferably 20% by mass or more based on the total amount of refrigerant (100% by mass).
  • These unsaturated fluorinated hydrocarbon refrigerants may be used in combination with the above-mentioned saturated fluorinated hydrocarbon refrigerant.
  • Natural refrigerants include hydrocarbon refrigerants such as propane (R290), n-butane, isobutane (R600a), 2-methylbutane, n-pentane, cyclopentaneisobutane, normal butane, carbon dioxide (carbon dioxide), and ammonia. Among these, propane, isobutane, carbon dioxide, and ammonia are preferable. These natural refrigerants may be used in combination with the above-mentioned fluorinated hydrocarbon refrigerant.
  • a refrigerator according to an embodiment of the present invention uses the above-described refrigerator oil or refrigerator oil composition, and the refrigerator oil or refrigerator oil composition is used by filling the refrigerator. That is, the refrigerator which concerns on one Embodiment of this invention is a refrigerator containing the above-mentioned refrigerator oil or refrigerator oil composition.
  • a compression type refrigerator is preferable, and a refrigeration cycle including a compressor, a condenser, an expansion mechanism (an expansion valve, etc.), and an evaporator, or a compressor, a condenser, an expansion mechanism, a dryer, and evaporation It is more preferable to have a refrigeration cycle equipped with a vessel.
  • Refrigerator oil is used, for example, to lubricate sliding portions provided in a compressor or the like.
  • the sliding portion is not particularly limited, but any of the sliding portions preferably contains a metal such as iron, and preferably slides between metal and metal.
  • the refrigerator for example, it is applied to a car air conditioner, an air conditioner, a gas heat pump (GHP), a refrigerator, a vending machine, a refrigeration system such as a showcase, a hot water supply system such as a water heater, floor heating, a heating system, etc. However, it is preferably applied to air conditioning applications.
  • the temperature was raised from room temperature at a rate of 1 ° C./min, and the two-layer separation temperature on the high temperature side was measured.
  • the acid value was measured by the indicator method according to “Lubricating oil neutralization test method” defined in JIS K 2501: 2003.
  • (6) Lubricity test Using a sealed block-on-ring friction tester (LFW-1), the amount of ring wear when each refrigeration oil was used was measured under the following conditions in an R32 refrigerant environment.
  • Ring FC250 Block: SKH51 Rotation speed: 1000rpm Familiarization: Load 300N x 1min Load: 500N Time: 60min Oil temperature: 80 ° C Refrigerant pressure: 0.4MPa
  • Preparation Example 1 [Preparation of catalyst] 6 g of nickel diatomaceous earth catalyst (manufactured by JGC Catalysts & Chemicals, trade name “N113”) and 300 g of isooctane were added to a 2 L autoclave made of SUS316L. The inside of the autoclave was purged with nitrogen and then purged with hydrogen, then heated to 140 ° C. with a hydrogen pressure of 3.0 MPaG, held at 140 ° C. for 30 minutes, and then cooled to room temperature.
  • Ni113 nickel diatomaceous earth catalyst
  • Example 1 Synthesis of polyvinyl ether (A) (PVE1)
  • PVE1 polyvinyl ether
  • the stirrer was activated, and the monomer mixture in the Erlenmeyer flask was supplied to the stirred system of the 300 mL flask by a pump over 4 hours, and stirring was further continued for 5 minutes after the completion of the supply.
  • the system was constantly stirred, and the temperature in the system was controlled at 25 ° C. using a water bath.
  • 5 g of an adsorbent manufactured by Kyowa Chemical Industry Co., Ltd., product name “KYOWARD 500SH” was added to the 300 mL flask system and stirred for 1 hour.
  • reaction liquid was filtered, the solvent and the light part were removed from the said filtrate using the rotary evaporator, and the crude product was obtained.
  • 120 g of the obtained crude product and 300 g of isooctane were added to the 2 L autoclave containing the catalyst prepared in Preparation Example 1, and the atmosphere inside the autoclave was replaced with hydrogen.
  • the hydrogen pressure was maintained at 3.5 MPa, and the system was stirred.
  • the temperature was raised to 140 ° C. over 30 minutes, and further reacted at 140 ° C. for 3 hours.
  • the reaction solution was cooled to room temperature and depressurized to normal pressure. And the reaction liquid was filtered, the solvent, the water
  • PVE1 includes a structural unit (a1) in which R 1 to R 3 in general formula (1) are hydrogen atoms, R 4 to R 6 in general formula (2) are hydrogen atoms, r is 0, and R 8 is The structural unit (a2) which is an ethyl group is included. Further, the content of the structural unit (a1) is 10 mol% and the content of the structural unit (a2) is 90 mol% with respect to all the structural units (100 mol%) of PVE1 estimated from the charged amount. .
  • Examples 2-8 The amount of methoxyethyl vinyl ether added to the Erlenmeyer flask was changed to 0.4 to 2.0 mol so that each structural unit in the polyvinyl ether compound (A) would be the mol% shown in Table 1, The same operation as in Example 1 was carried out except that the addition amount was changed to 1.6 to 0 mol to obtain PVE2 to PVE8.
  • Table 1 shows the properties of PVE2 to PVE8 used in Examples 2 to 8, respectively.
  • Comparative Examples 1 and 2 It implemented like Example 1 except having changed the base oil to be used to the following PVE9 and 10 as shown in Table 1, respectively.
  • the properties of the base oils used in Comparative Examples 1 and 2 are as shown in Table 1.
  • PVE10 Polyethyl vinyl ether
  • MeOEt represents the structural unit (a1) in which R 1 to R 3 in the general formula (1) are hydrogen atoms
  • Et represents R 4 to R 6 in the general formula (2)
  • iBu is a hydrogen atom
  • r is 0, and R 8 is an isobutyl group in R 4 to R 6 in the general formula (2) Is the structural unit (a2).
  • Examples 15 to 18 and Comparative Example 4 Using the above-described PVE3, PVE10, antioxidant, acid scavenger, and extreme pressure agent, refrigerating machine oils having the composition shown in Table 3 were prepared, and a lubricity test was performed on each refrigerating machine oil. Table 3 shows the ring wear after the lubricity test.
  • the polyvinyl ether compound constituting the base oil of the refrigerating machine oil contains the structural unit (a1) having a methoxyethyl group in the side chain, whereby the R32 refrigerant is used. It was possible to improve the compatibility, particularly in a low temperature environment. Moreover, as shown in Table 2, even after the refrigeration oil is heat-degraded by blending an antioxidant, an acid scavenger, or both of them into the base oil composed of the polyvinyl ether compound (A). The acid value was lowered and the high-temperature oxidation stability was improved. When an extreme pressure agent is blended, the high-temperature oxidation stability tends to be low.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Emergency Medicine (AREA)
  • Physics & Mathematics (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Materials Engineering (AREA)
  • Lubricants (AREA)

Abstract

La présente huile de machine frigorifique est une huile de machine frigorifique pour des réfrigérants contenant du difluorométhane (R32), et contient : un composé d'éther polyvinylique (A) comprenant une unité constitutive (a1) qui comporte un groupe méthoxyéthyle dans une chaîne latérale ; et au moins un agent choisi dans le groupe constitué par les antioxydants (B) et les capteurs d'acide (C).
PCT/JP2017/022949 2016-06-22 2017-06-22 Huile pour machines frigorifiques et composition pour machines réfrigérantes WO2017222004A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2016123645A JP2017226761A (ja) 2016-06-22 2016-06-22 冷凍機油、及び冷凍機用組成物
JP2016-123645 2016-06-22

Publications (1)

Publication Number Publication Date
WO2017222004A1 true WO2017222004A1 (fr) 2017-12-28

Family

ID=60784286

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2017/022949 WO2017222004A1 (fr) 2016-06-22 2017-06-22 Huile pour machines frigorifiques et composition pour machines réfrigérantes

Country Status (2)

Country Link
JP (1) JP2017226761A (fr)
WO (1) WO2017222004A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008108365A1 (fr) * 2007-03-08 2008-09-12 Idemitsu Kosan Co., Ltd. Lubrifiant pour machine de réfrigération de type à compression et système de réfrigération utilisant celui-ci
JP2011046880A (ja) * 2009-08-28 2011-03-10 Jx Nippon Oil & Energy Corp 冷凍機油および冷凍機用作動流体組成物
WO2013005647A1 (fr) * 2011-07-01 2013-01-10 出光興産株式会社 Composition d'huile lubrifiante pour réfrigérateur à compression

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008108365A1 (fr) * 2007-03-08 2008-09-12 Idemitsu Kosan Co., Ltd. Lubrifiant pour machine de réfrigération de type à compression et système de réfrigération utilisant celui-ci
JP2011046880A (ja) * 2009-08-28 2011-03-10 Jx Nippon Oil & Energy Corp 冷凍機油および冷凍機用作動流体組成物
WO2013005647A1 (fr) * 2011-07-01 2013-01-10 出光興産株式会社 Composition d'huile lubrifiante pour réfrigérateur à compression

Also Published As

Publication number Publication date
JP2017226761A (ja) 2017-12-28

Similar Documents

Publication Publication Date Title
JP5241262B2 (ja) 冷凍機用潤滑油組成物
JP5241263B2 (ja) 冷凍機用潤滑油組成物
WO2016190286A1 (fr) Huile pour machine frigorifique, composition d'huile pour machine frigorifique, et machine frigorifique
WO2018074584A1 (fr) Huile pour réfrigérateur et composition de fluide de travail pour réfrigérateur
EP3279296B1 (fr) Huile lubrifiante et composition mixte pour appareil réfrigérant
KR102442266B1 (ko) 냉동기유, 및 냉동기용 조성물
JP6631622B2 (ja) 冷凍機潤滑油及び冷凍機用混合組成物
EP3196277B1 (fr) Huile pour machine frigorifique, composition d'huile pour machine frigorifique, et machine frigorifique
US11015138B2 (en) Refrigerating machine oil, and composition for refrigerating machine
WO2017222004A1 (fr) Huile pour machines frigorifiques et composition pour machines réfrigérantes
WO2020166272A1 (fr) Composition pour machines frigorifiques
WO2017104789A1 (fr) Composé d'éther polyvinylique et procédé de production d'un lubrifiant

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 17815471

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 17815471

Country of ref document: EP

Kind code of ref document: A1