WO2004029182A1 - Huile pour machine frigorifique - Google Patents

Huile pour machine frigorifique Download PDF

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Publication number
WO2004029182A1
WO2004029182A1 PCT/JP2003/012020 JP0312020W WO2004029182A1 WO 2004029182 A1 WO2004029182 A1 WO 2004029182A1 JP 0312020 W JP0312020 W JP 0312020W WO 2004029182 A1 WO2004029182 A1 WO 2004029182A1
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WO
WIPO (PCT)
Prior art keywords
refrigerating machine
ester
machine oil
oil
acid
Prior art date
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PCT/JP2003/012020
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English (en)
Japanese (ja)
Inventor
Yuji Shimomura
Katsuya Takigawa
Original Assignee
Nippon Oil Corporation
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 Nippon Oil Corporation filed Critical Nippon Oil Corporation
Priority to AU2003264527A priority Critical patent/AU2003264527A1/en
Publication of WO2004029182A1 publication Critical patent/WO2004029182A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • C09K5/044—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds
    • C09K5/045—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems comprising halogenated compounds containing only fluorine as halogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/32—Esters
    • C10M105/36—Esters of polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28—Esters
    • C10M2207/282—Esters of (cyclo)aliphatic oolycarboxylic acids
    • C10M2207/2825—Esters of (cyclo)aliphatic oolycarboxylic acids used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
    • C10N2020/09—Characteristics associated with water
    • C10N2020/097—Refrigerants
    • C10N2020/101—Containing Hydrofluorocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
    • C10N2030/06—Oiliness; Film-strength; Anti-wear; Resistance to extreme pressure
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/30—Refrigerators lubricants or compressors lubricants

Definitions

  • the present invention t relates refrigerating machine oil and the refrigerating machine fluid composition
  • refrigerating machine oils for alternative refrigerants.
  • the characteristics required for refrigerating machine oil include lubricity, refrigerant compatibility, heat and hydrolysis stability, electrical insulation, and low hygroscopicity.These properties can be met depending on the type and application of the refrigerant.
  • a substrate is selected.
  • base materials for HFC refrigerating machine oils include oxygen-containing compounds such as esters, ethers, and carbonates that are compatible with refrigerants, or alkylbenzenes that have poor refrigerant compatibility but have excellent lubricity and thermal and hydrolytic stability. Etc. are used.
  • esters include polyol esters obtained by reacting aliphatic polyhydric alcohols with fatty acids described in JP-A-3-505602 and JP-A-3-128899, etc. — Alicyclic polycarboxylates described in, for example, Japanese Patent Publication No. 221690 are known.
  • an alkyl group is used as a fatty acid for the raw material.
  • the viscosity of the refrigerating machine oil can be reduced.
  • the alkyl group of the fatty acid is reduced, the stability of the obtained ester by thermal hydrolysis is reduced.
  • the alicyclic polycarboxylic acid esters described in JP-A-9-1221690 and the like exhibit relatively good heat-hydrolysis stability, Those having a large number of carbon atoms in the terminal alkyl group have insufficient compatibility with the refrigerant, while those having a small number of carbon atoms in the terminal alkyl group are inferior in heat and hydrolysis stability and have insufficient lubricity.
  • the present invention has been made in view of the above-mentioned problems of the related art, and has a lubricating property, a heat-hydrolysis stability, a refrigerant compatibility, and an electric power even when the viscosity is reduced.
  • a refrigerating machine oil and a fluid composition for a refrigerating machine that maintain a high level of insulation and can achieve both high efficiency and improved reliability in a refrigeration system using HFC refrigerant / natural refrigerant. The purpose is to provide.
  • the refrigerating machine oil of the present invention is characterized by containing an ester of a branched chain alcohol having 9 carbon atoms and adipic acid.
  • the fluid composition for a refrigerator according to the present invention is characterized by containing an ester of a branched-chain alcohol having 9 carbon atoms and adipic acid, and a refrigerant.
  • lubricating properties, heat 'hydrolysis stability, refrigerant compatibility, and electrical insulation can be obtained by incorporating an ester of a branched chain alcohol having 9 carbon atoms and adipic acid into refrigerating machine oil.
  • the viscosity of the refrigerating machine oil can be sufficiently reduced without impairing the properties. Therefore, by using the refrigerating machine oil of the present invention in a refrigeration system using an HFC refrigerant / natural refrigerant, it is possible to achieve both high efficiency and improved reliability in the system.
  • the refrigerating machine oil of the present invention contains an ester of a branched alcohol having 9 carbon atoms and adipic acid (hereinafter referred to as “ester according to the present invention”).
  • the alcohol component of the ester according to the present invention is a branched-chain anolecol having 9 carbon atoms. If the alcohol component is a straight-chain alcohol, the resulting ester will have insufficient refrigerant compatibility. Even when the alcohol component is a branched-chain alcohol, when the number of carbon atoms is 8 or less, the lubricating properties of the obtained ester are insufficient, and when the number of carbon atoms is 10 or more, the obtained refrigerant of the ester is not sufficient. Poor compatibility.
  • the branched-chain alcohol having 9 carbon atoms may be either a saturated alcohol or an unsaturated alcohol, but is preferably a saturated alcohol from the viewpoint of thermal stability.
  • the number of carbon atoms in the main chain of the branched alcohol having 9 carbon atoms is not particularly limited, but is preferably 7 or less from the viewpoint of refrigerant compatibility. Further, from the viewpoint of lubricity, the number of carbon atoms in the main chain is preferably 5 or more.
  • the side chain in the branched alcohol having 9 carbon atoms a methyl group or an ethyl group is preferable, and a methyl group is more preferable, from the viewpoint of refrigerant compatibility.
  • the number of side chains in the branched alcohol having 9 carbon atoms is not particularly limited, but is preferably 2 or more, more preferably 3 or more, from the viewpoint of thermal and hydrolytic stability.
  • Examples of the branched-chain alcohol having 9 carbon atoms include tetramethylpentanol (the substitution position of a methyl group is arbitrary) and ethyldimethylpentanol (a methyl group and a methyl group).
  • the substitution position is arbitrary), trimethylhexanol (the substitution position of methyl group is arbitrary), ethylmethylhexanol (the substitution position of methyl group and ethyl group is arbitrary), dimethylheptanol (methyl group The replacement position of ), And ethylheptanol (the substitution position of the ethyl group is arbitrary).
  • trimethylhexanol (the substitution position of the methyl group is arbitrary) and dimethylheptanol (the substitution position of the methyl group is arbitrary) are preferable, and trimethylhexanol (the substitution position of the methyl group is arbitrary). Is more preferred, and 3,5,5-trimethylhexanol is particularly preferred.
  • the acid component of the ester according to the present invention is adipic acid. If the acid component is a dibasic acid having a smaller number of carbon atoms than adipic acid, the resulting ester will have insufficient thermal stability. When the acid component is a dibasic acid having a larger number of carbon atoms than adipic acid, the resulting ester has insufficient refrigerant compatibility. Further, when the acid component is a branched dibasic acid, the resulting ester has insufficient lubricity.
  • the ester according to the present invention is an ester of the above-mentioned branched alcohol having 9 carbon atoms and adipic acid.
  • the ester may be either a partial ester (monoester) or a complete ester (diester), but is preferably a complete ester (diester) from the viewpoint of refrigerant compatibility and thermal stability.
  • the two branched alcohols may be the same or different.
  • the ratio of the partial ester to the complete ester in the mixture is not particularly limited, but the compatibility between the refrigerant and the heat From the viewpoint of hydrolysis stability, the total ester is preferably at least 80% by mass, more preferably at least 90% by mass, and preferably at least 90% by mass, based on the total amount of the partial ester and the complete ester. %, More preferably at least 98% by mass, even more preferably at least 98% by mass, particularly preferably at least 99% by mass, most preferably at least 99.5% by mass. preferable.
  • the ester according to the present invention is prepared by subjecting a predetermined acid component and an alcohol component to a conventional method (preferably under an atmosphere of an inert gas such as nitrogen under an atmosphere of an esterification catalyst). (With heating in the presence or without a catalyst).
  • the total amount of the alcohol component is, for example, 1.0 to 1.5 equivalents, preferably 1.05 to 1.2 equivalents, per equivalent of the acid component. .
  • a lower alcohol ester of the acid component and / or an acetic acid ester or a propionic acid ester of the alcohol is used, and the ester of the present invention is subjected to a transesterification reaction. It is also possible to obtain
  • Examples of the esterification catalyst used in the esterification reaction include Lewis acids, alkali metal salts, and sulfonic acids. More specifically, examples of the Lewis acid include an aluminum derivative, a tin derivative, and a titanium derivative, and examples of the alkali metal salt include a sodium alkoxide and a potassium alkoxide. Examples of the sulfonic acids include p-toluenesulfonic acid, methanesulfonic acid, and sulfuric acid. Among these, Lewis acids such as aluminum derivatives, tin derivatives, and titanium derivatives are preferable in consideration of the effect of the resulting ester on the thermal and hydrolytic stability, and tin derivatives are particularly preferable in terms of reaction efficiency. .
  • the amount of the esterification catalyst used is, for example, about 0.1 to 1% by mass relative to the total amount of the acid component and the alcohol component as the raw materials.
  • the reaction temperature in the esterification reaction is, for example, 150 to 230 ° C, and the reaction is usually completed in 3 to 30 hours.
  • the excess raw material is distilled off under reduced pressure or normal pressure, and subsequently purified by a conventional purification method such as liquid-liquid extraction, vacuum distillation, and activated carbon treatment.
  • the ester compound can be purified.
  • the refrigerating machine oil of the present invention may be composed only of the ester according to the present invention, and may be a mixture of the ester and another base oil and / or additive.
  • the content of the ester according to the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and more preferably 30% by mass or more based on the total amount of the refrigerating machine oil. And more preferably 60% by mass or more.
  • a base oil other than the ester according to the present invention can be used.
  • base oils include esters other than the esters according to the present invention, such as polyol esters and complex esters, polyglycols, polyvinylinoleethers, ketones, polyphenylene-1-enoles, silicones, polysiloxanes, perfluoroethers. And other synthetic oils containing oxygen.
  • the content of the synthetic oil is not particularly limited.
  • the content of the synthetic oil in terms of mass is equivalent to the content of the ester according to the present invention. It is preferably 1.5 times or less, more preferably 1 time or less, still more preferably 0.5 times or less, still more preferably 0.25 times or less, and 0.2 times or less. It is more preferably at most 1 times, particularly preferably at most 0.05 times.
  • the refrigerating machine oil of the present invention contains the ester of the present invention and, if necessary, other synthetic oils containing oxygen, and these components are mainly used as a base oil.
  • the refrigerating machine oil of the present invention can be suitably used in a state where no additives are added (that is, 100% by mass of base oil). it can.
  • a phosphate ester in order to further improve the abrasion resistance and load bearing capacity of the refrigerating machine oil of the present invention, a phosphate ester, an acid phosphate ester, and an acid phosphate ester And at least one phosphorus compound selected from chlorinated phosphates, chlorinated phosphates, phosphites and thiophosphates.
  • These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkynol or polyether alcohol or derivatives thereof.
  • the phosphate ester used in the present invention includes triptyl phosphate, tripentyl phosphate, trihexynolephosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecinolephosphate, and tridecyl phosphate.
  • Pendecinolephosphate tridodecinolephosphate, tritridecylphosphate, tritetradecylphosphate, trilipidadecyl phosphate, trihexadecinolephosphate, triheptadecinolephosphate, trioctadedeci Norephosphate, Trioleinolephosphate, Trifininolephosphate, Tricresinolephosphate, Trixyleninolephosphate, Cresinole Dipheninolephosphate, Xyleni / Resifenino Hosufue one door and the like;
  • Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentinourea acid phosphate, monohexinorea acid phosphate, monoheptinorea acid phosphate, monooctayl acid phosphate, monononyl acid phosphate, and monodecanolate.
  • the amine salts of the acidic phosphoric acid esters include the above-mentioned acidic phosphoric acid ester, methinoleamine, ethamine, propylamine, butyramine, pentylamine, hexylamine, heptylamine, otatylamine, dimethylamine, getylamine, dipropylamine. , Dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, trippropinoleamine, triptylamine, tripentylamine, trihexylamine, tripheptylamine, trioctylamine, etc. , Salt of etc .;
  • chlorinated phosphoric acid ester examples include Tris' dichloro propyl phosphate, Tris. Chloroethynole phosphate, Tris chloro pheninole phosphate, polyoxyalkylene bis [di (chloroalkyl)] Phosphite and the like; [0380] Phosphite esters include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl / phosphite, and the like.
  • Examples of the thiophosphoric acid esters include tributylphosphorothionate, tripentylphosphorothionate, trihexynolephosphorothionate, triheptinolephosphorothionate, and trioctinolephosphoronate. Chionnay , Trinonylphosphorothionate, tridecylphosphorochonate, tridecylphosphorochonate, tridodecylphosphorochonate, tritridecylphosphorochonate, tritetradecylphosphorochonate.
  • the content of the phosphorus compound in the refrigerating machine oil of the present invention is not particularly limited, but is preferably from 0.01 to 5.0% by mass, more preferably from 0 to 5.0% by mass, based on the total amount of the refrigerating machine oil. 0.22 to 3.0% by mass.
  • phenyldaricidyl ether type epoxy compound examples include phenylglycidyl ether and alkylphenylglycidyl ether.
  • the alkylphenyldaricidyl ether referred to herein includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, among which those having one alkyl group having 4 to 10 carbon atoms, for example, n -Butylphenylglycidyl ether, i-butylphenylglycidyl ether, sec-butylphenyldaricidyl ether, tert-butylphenyldaricidyl ether, pentylphenyldaricidyl ether, hexylphenyldaricidyl ether Heptylphenylglycidinoleatenole, octinolepheninoleleglycidinole ether, noninolepheninoleleglycid
  • alkyl glycidyl ether type epoxy compound examples include decyl glycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, and tetradecyl glycidyl.
  • Ether 2-ethynolehexyl glycidinole ether, neopentinole glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1, 6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether And polyalkylene glycol monoglycidyl ether and polyalkylene glycol diglycidyl ether.
  • R represents a hydrocarbon group having 1 to 18 carbon atoms.
  • examples of the hydrocarbon group represented by R include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a hydrocarbon group having 5 to 7 carbon atoms. Cycloalkyl group, alkyl group with 6 to 18 carbon atoms, alkyl group with 6 to 10 carbon atoms, aryl group with 6 to 10 carbon atoms, arylalkyl group with 7 to 18 carbon atoms, aryl alkyl with 7 to 18 carbon atoms And the like.
  • an alkyl group having 5 to 15 carbon atoms an alkenyl group having 2 to 15 carbon atoms, a phenyl group, and an alkylphenyl group having an alkyl group having 1 to 4 carbon atoms are preferable.
  • glycidyl ester type epoxy compounds preferred are, for example, glycidyl-1,2-dimethyloctanoate, glycidinolebenzoate, glycidinole-tert-butynolebe, and the like.
  • examples include zonzoate, glycidyl acrylate, and glycidyl methacrylate.
  • aryloxysilane compound examples include 1,2-epoxystyrene, alkyl-1,2-epoxystyrene, and the like.
  • (V) As the alkyloxysilane compound, specifically, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxypandecane, 1,2-epoxidedodecane, 1,2-epoxytridecane, 1,2-epoxy 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1, 21-epoxy silicone.
  • Examples of such alicyclic epoxy compounds include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyi / re3, 4-epoxycyclohexancarboxylate, bis (3,4-epoxycyclohexylmethyl) adipate, exo-1,2,3-epoxynonolevonolenane, bis (3,4-epoxy-6-methynolecyclohexynolemethyl) adipate , 2- (7-oxabicyclo [4.1.0] hept-1-inole) -spiro (1,3-dioxane-1,5,3,1- [7] oxabicyclo [4.1.0] heptane, 4- ( 1,1-Methylepoxyethyl) 1,2-epoxy-12-methynolecyclohexane, 4-epoxyethyl-1,2-e
  • epoxidized fatty acid monoester examples include an epoxidized fatty acid having 12 to 20 carbon atoms and an alcohol or phenol or alkyl phenol having 1 to 8 carbon atoms.
  • Esters and the like can be exemplified.
  • butynoleestenolate, hexinoleestenole, benzinoleestenole, cyclohexenolate ester, methoxyxenolate ester, octinoleestenole, phenyl ester, and butylphenyl estenolate of epoxystearic acid Is preferably used.
  • epoxidized vegetable oil examples include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.
  • epoxy compounds such as soybean oil, linseed oil, and cottonseed oil.
  • phenyldaricidyl ether-type epoxy compounds, glycidyl ester-type epoxy compounds, alicyclic epoxy compounds, and epoxidized fats can further improve the thermal stability of hydrolysis. Acid monoesters are preferred, and glycidyl ester type epoxy compounds and alicyclic epoxy compounds are more preferred.
  • the content of the epoxy compound in the refrigerating machine oil of the present invention is not particularly limited, but is preferably from 0.1 to 5. ⁇ % by mass, more preferably from 0.2 to 5% by mass, based on the total amount of the refrigerating machine oil. 2.0% by mass.
  • one of the above epoxy compounds may be used alone, or two or more may be used in combination.
  • refrigerating machine oil additives such as di-tert-butyl-p-cresol and bisphenol may be used, if necessary.
  • Phenol-based antioxidants such as A; Phenylenol ⁇ -naphthinoleamine, ⁇ , (-(2-naphthyl) - ⁇ -phenylenediamine, etc .; amine-based antioxidants; anti-wear agents such as zinc dithiophosphate Extreme pressure agents such as chlorinated paraffins and sulfur compounds; oily agents such as fatty acids; antifoaming agents such as silicone compounds; metal deactivators such as benzotriazole; viscosity index improvers; pour point depressants: cleaning One of additives such as a dispersant can be used alone or in combination of two or more.
  • the total content of these additives in the refrigerating machine oil for difluoromethane refrigerant of the present invention is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less based on the total amount of the refrigerating machine oil. is there.
  • the kinematic viscosity of the refrigerating machine oil of the present invention is not particularly limited, but is preferably a kinematic viscosity that put in 40 ° C is 3 ⁇ 1 0 Omm 2 Z s, more preferably 4 ⁇ 50 mm 2 / s, most preferably Is 5-4 It can be.
  • the kinematic viscosity at 100 ° C. can be preferably 1 to 2 OmmVs, more preferably 2 to 10 mm 2 / s. Furthermore, even if the viscosity is reduced, the heat and hydrolysis stability is good.
  • 5 to 35 is preferably a kinematic viscosity at 40 ° C mms, more preferably 5 to 25 mm 2 // s, even more preferably 5 ⁇ 20 mm 2 / s, most preferably say It becomes more remarkable in the case of 5 to 15 mm 2 Zs.
  • the volume resistivity of the refrigerating machine oil of the present invention is not particularly limited, it is preferably l. OX l O HQ 'cm or more, more preferably 1.0 1.10 12 ⁇ ⁇ (: ⁇ or more, most preferably to 1. OX 1 0 13 ⁇ ⁇ cm or more. particularly, when used for hermetic refrigeration tends to be required Kore, electrical insulation properties. in the present invention
  • the volume resistivity means a value measured at 25 ° C in accordance with JISC2101 “Electrical insulating oil test method”.
  • the water content of the refrigerating machine oil of the present invention is not particularly limited, but can be preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerating machine oil.
  • the total acid value of the refrigerator oil of the present invention is not particularly limited, but is preferably 0.1 mg KOH / g or less, more preferably 0.1 mg KOH / g or less, in order to prevent corrosion of metals used in the refrigerator or piping. Can be 0.0 SmgKOHZg or less.
  • the total acid value refers to the value of the total acid value measured in accordance with JIS K2501 "Petroleum products and lubricating oils-Neutralization value test method".
  • the ash content of the refrigerating machine oil of the present invention is not particularly limited. However, in order to enhance the thermal and hydrolytic stability of the refrigerating machine oil of the present invention and suppress the generation of sludge, it is preferably 10 Oppm or less. , More preferably 50 ppm or less.
  • the ash refers to a value of ash measured in accordance with JIS K 2272 “Test method for ash and sulfated ash of crude oil and petroleum products”.
  • the refrigerating machine oil of the present invention includes a HFC refrigerant, a fluorine-containing ether-based refrigerant such as perfluoroethers, a non-fluorine-containing ether-based refrigerant such as dimethyl ether, and the like. It is suitably used with natural refrigerants such as carbon dioxide and hydrocarbons. One of these refrigerants may be used alone, or a mixture of two or more thereof may be used.
  • HFC refrigerant examples include fluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HF C-32), trifluoromethane (HF C-23), and pentafunoroletan (HF
  • HFC-134 1,1,2,2-tetrafluroethane
  • HFC-134a 1,1,1,2, tetrafluoroethane
  • 1, 1 And HFCs such as 1,1-trifluorophenol (HF C-143a) and 1,1-difluorene (HFC-152a), or a mixture of two or more thereof.
  • One 32 60 to 80% by mass 40 to 20% by mass of a mixture
  • HFC-32 / HF C- 125 40 to 70% by mass A mixture of 60 to 30% by mass
  • HFC-125 / HFC- 143a 40 to 60% by mass of a mixture of 60 to 40% by mass
  • HF C_134a / HFC—32 / HFC—125 60% by mass 30% by mass. /.
  • Examples of the natural refrigerant include carbon dioxide and hydrocarbons.
  • a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant.
  • it is an alkin having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms, a cycloalkali, an alkene or a mixture thereof.
  • propane, butane, isobutane or a mixture thereof is preferred.
  • the refrigerating machine oil of the present invention is usually present in a refrigerating system in the form of a refrigerating machine fluid composition mixed with the above refrigerant.
  • the content ratio of the refrigeration oil and the refrigerant in the fluid composition is not particularly limited, but the content of the refrigeration oil is preferably 0.01 to 5 times the content of the refrigerant in terms of mass, and 0.02. It is preferably up to 4 times.
  • the refrigerating machine oil of the present invention is used as a lubricating oil for refrigerant compressors of all refrigerating machines due to its excellent electrical properties and low moisture absorption.
  • refrigerators include room air conditioners, packaged air conditioners, refrigerators, automotive air conditioners, dehumidifiers, freezers, refrigerator-freezer warehouses, vending machines, showcases, and cooling equipment for chemical plants.
  • the refrigerating machine oil of the present invention is particularly preferably used for a refrigerating machine having a hermetic compressor.
  • the refrigerating machine oil of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, and a centrifugal type.
  • the refrigerating machine oil of the present invention can be suitably used for various refrigerating machines as described above, and a typical configuration of a refrigerant circulation cycle provided in the refrigerating machine includes a compressor, a condenser, and the like.
  • a compressor a condenser, and the like.
  • One having an expansion mechanism, an evaporator, and, if necessary, a dryer is exemplified.
  • a motor including a rotor and a stator in a closed container for storing refrigerating machine oil, a rotating shaft fitted to the rotor, and the rotating shaft
  • a high-pressure container type compressor in which a compressor unit connected to a motor is housed, and in which a high-pressure refrigerant gas discharged from the compressor unit stays in a closed container; and a rotor in a closed container that stores refrigerating machine oil.
  • a motor consisting of a stator, a rotating shaft fitted to the rotor, and a compressor unit connected to the motor via the rotating shaft.
  • the compressor is discharged from the compressor unit.
  • a compressor of a low-pressure container type in which high-pressure refrigerant gas is directly discharged to the outside of the closed container, and the like.
  • the insulating film which is a material for the electrical insulation system of the motor, is a crystalline plastic film having a glass transition point of 50 ° C or more, specifically, for example, polyethylene terephthalate, polybutylene terephthalate, A resin layer with a high glass transition temperature is coated on at least one type of insulating film selected from the group consisting of dilensanolef, polyetheretherketone, polyethylene naphthalate, polyamide imide, and polyimide, or a film with a low glass transition temperature
  • This composite film is preferably used because it hardly causes deterioration of the tensile strength characteristics and electrical insulation properties.
  • the magnet wire used for a part of the motor may be an enamel coating having a glass transition temperature of 120 ° C or more, for example, a single layer of polyester, polyesterimide, polyamide, polyamideamide, or a glass transition.
  • Those having an enamel coating in which a low-temperature layer is provided as a lower layer and a high-temperature layer is provided as an upper layer are preferably used.
  • Examples of composite-coated enameled wires are polyesterimide in the lower layer and polyamideamide in the upper layer (AIZE1), polyester in the lower layer and polyamideamide in the upper layer (AIZPE), etc. Is mentioned.
  • the desiccant to be filled in the dryer is as follows: a pore diameter of 3.3 angstroms or less, and a carbon dioxide gas absorption capacity at a carbon dioxide gas partial pressure of 25 ° C. and 25 O mmHg of 1.0. % Or less, a synthetic zeolite composed of an alkali metal aluminate complex salt of not more than 100% is preferably used. Specifically, for example, a trade name XH manufactured by Union Showa Co., Ltd. X 9, XH-10, XH-11, XH-600 and the like.
  • the base oils and additives used in Examples 1 to 5 and Comparative Examples 1 to 8 are as follows. These were blended to have the compositions shown in Tables 1 to 3 to prepare sample oils. Tables 1 to 3 show the kinematic viscosities at 40 ° C and 100 ° C and the total acid value of each of the obtained sample oils. -(Base oil)
  • Base oil 1 ester of adipic acid with 3,5,5-trimethylhexanol
  • Base oil 2 ester of adipic acid with 3,6-dimethylheptanol
  • Base oil 3 ester of 2,4-dimethylheptanol and adipic acid
  • Base oil 4 Esthenole of 2-ethynolehexanol and adipic acid
  • Base oil 5 Ester of 2-methylnonanol and adipic acid
  • Base oil 6 Ester of 3,5,5-trimethylhexanol and sebacic acid
  • Base oil 7 Ester of 2-ethylhexanol and terephthalic acid
  • Base oil 8 ester of 3,5,5-trimethylhexanol and oxalic acid
  • Base oil 9 ester of 3,5,5-trimethylhexanol and ethinolemalonic acid
  • Base oil 10 of ester of n-nonanol and adipic acid ester.
  • Additive 2 tricresyl phosphate.
  • Base oil 1 1-Base oil 2 1 1 Base oil 3 1 1-1 Base oil 4 100 1 1 unit / Yuichi 100 1 Composition Base oil 6-1 100 1
  • Base oil 8 11 Base oil 9 11-Base oil 10
  • Example 15 As is clear from the results shown in Table 1, the sample oil of Example 15 had a sufficiently low viscosity for increasing the efficiency of the refrigeration system, and was compatible with the refrigerant and the electrical insulation. The thermal stability and lubricity were achieved at a high level in a well-balanced manner.
  • the refrigerating machine oil of the present invention maintains lubricity, heat / hydrolysis stability, refrigerant compatibility and electrical insulation even at a low viscosity. It has excellent characteristics of Therefore, the refrigerating machine oil of the present invention is When used in a refrigeration system that uses a natural refrigerant, both high efficiency and improved reliability in the system can be achieved.

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

Abstract

La présente invention concerne une huile pour machine frigorifique qui comprend un ester préparé à partir d'un alcool à chaîne ramifiée comptant neuf atomes de carbone et d'acide adipique. L'huile pour machine frigorifique est avantageuse en ce qu'elle présente une viscosité réduite et possède également un pouvoir lubrifiant, une résistance à la décomposition thermique et à l'hydrolyse, une compatibilité avec un réfrigérant et une propriété d'isolant électrique, toutes ces propriétés atteignant des niveaux élevés. Par conséquent, le fait d'utiliser ladite huile pour machine frigorifique dans un système de réfrigération utilisant un réfrigérant hydrofluorocarboné (HFC) ou un réfrigérant de type naturel permet de conférer au système à la fois une haute efficacité et une fiabilité accrue.
PCT/JP2003/012020 2002-09-24 2003-09-19 Huile pour machine frigorifique WO2004029182A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU2003264527A AU2003264527A1 (en) 2002-09-24 2003-09-19 Refrigerator oil

Applications Claiming Priority (2)

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JP2002277793A JP4156892B2 (ja) 2002-09-24 2002-09-24 冷凍機油
JP2002-277793 2002-09-24

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WO2004029182A1 true WO2004029182A1 (fr) 2004-04-08

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007155174A (ja) * 2005-12-02 2007-06-21 Showa Tansan Co Ltd 非共沸混合冷媒を使用するヒートポンプシステムまたは空調機若しくは冷凍機システム
JP5462995B2 (ja) * 2007-03-27 2014-04-02 Ｊｘ日鉱日石エネルギー株式会社 冷凍機油及び冷凍機用作動流体組成物

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991007479A1 (fr) * 1989-11-13 1991-05-30 Idemitsu Kosan Co., Ltd. Huile lubrifiante synthetique a base de polyester
EP0435253A1 (fr) * 1989-12-28 1991-07-03 Nippon Oil Company, Limited Huiles pour réfrigérateur utilisés avec des réfrigérants halogénocarbonés contenant de l'hydrogène
JPH10130673A (ja) * 1996-10-25 1998-05-19 New Japan Chem Co Ltd 潤滑油基油

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1991007479A1 (fr) * 1989-11-13 1991-05-30 Idemitsu Kosan Co., Ltd. Huile lubrifiante synthetique a base de polyester
EP0435253A1 (fr) * 1989-12-28 1991-07-03 Nippon Oil Company, Limited Huiles pour réfrigérateur utilisés avec des réfrigérants halogénocarbonés contenant de l'hydrogène
JPH10130673A (ja) * 1996-10-25 1998-05-19 New Japan Chem Co Ltd 潤滑油基油

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9410105B2 (en) 2012-11-16 2016-08-09 Basf Se Lubricant compositions comprising epoxide compounds

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JP4156892B2 (ja) 2008-09-24
JP2004115588A (ja) 2004-04-15

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