WO2006030490A1 - 冷凍機油組成物 - Google Patents
冷凍機油組成物 Download PDFInfo
- Publication number
- WO2006030490A1 WO2006030490A1 PCT/JP2004/013367 JP2004013367W WO2006030490A1 WO 2006030490 A1 WO2006030490 A1 WO 2006030490A1 JP 2004013367 W JP2004013367 W JP 2004013367W WO 2006030490 A1 WO2006030490 A1 WO 2006030490A1
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- WIPO (PCT)
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- sulfur compound
- oil composition
- machine oil
- refrigerating machine
- mass
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- 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
- C09K5/042—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 compounds containing carbon and hydrogen only
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- C10M169/00—Lubricating compositions characterised by containing as components a mixture of at least two types of ingredient selected from base-materials, thickeners or additives, covered by the preceding groups, each of these compounds being essential
- C10M169/04—Mixtures of base-materials and additives
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- C10M171/00—Lubricating compositions characterised by purely physical criteria, e.g. containing as base-material, thickener or additive, ingredients which are characterised exclusively by their numerically specified physical properties, i.e. containing ingredients which are physically well-defined but for which the chemical nature is either unspecified or only very vaguely indicated
- C10M171/008—Lubricant compositions compatible with refrigerants
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- C10M2203/00—Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
- C10M2203/04—Well-defined cycloaliphatic compounds
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- C10M2203/10—Petroleum or coal fractions, e.g. tars, solvents, bitumen
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- C10M2205/02—Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing acyclic monomers
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- C10M2205/22—Alkylation reaction products with aromatic type compounds, e.g. Friedel-crafts
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- C10M2207/283—Esters of polyhydroxy compounds
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/1033—Polyethers, i.e. containing di- or higher polyoxyalkylene groups used as base material
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- C10M2209/104—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
- C10M2209/1045—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only used as base material
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C10M2209/103—Polyethers, i.e. containing di- or higher polyoxyalkylene groups
- C10M2209/105—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only
- C10M2209/1055—Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing three carbon atoms only used as base material
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- C10M2209/10—Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- C10M2209/108—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified
- C10M2209/1085—Polyethers, i.e. containing di- or higher polyoxyalkylene groups etherified used as base material
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
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- C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
- C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
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- C10M2219/10—Heterocyclic compounds containing sulfur, selenium or tellurium compounds in the ring
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- C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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- C10N2020/00—Specified physical or chemical properties or characteristics, i.e. function, of component of lubricating compositions
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- C10N2030/00—Specified physical or chemical properties which is improved by the additive characterising the lubricating composition, e.g. multifunctional additives
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- C10N2040/00—Specified use or application for which the lubricating composition is intended
- C10N2040/30—Refrigerators lubricants or compressors lubricants
Definitions
- the present invention relates to a novel refrigeration oil composition, and particularly to a refrigeration oil composition excellent in lubricity using a natural refrigerant.
- a mixed liquid of refrigerant and lubricating oil circulates in the sealed system. It has a structure to do.
- conventional chlorofluorocarbons such as dichlorodifluoromethane (R-12) and chlorodifluoromethane (R-22) have been used as refrigerants, and a number of lubricants used in combination with them. Oil has been produced and used.
- fluorocarbon compounds that have been used as conventional refrigerants may cause environmental pollution such as destruction of the ozone layer in the stratosphere when released into the atmosphere.
- Hydride fluorocarbons and fluorocarbons such as 1, 1, 1, 2—tetrafluoroethane (R—134a) have come to be used.
- Hydrofluorocarbons, etc. have no risk of destroying the ozone layer, but they have a long life in the atmosphere and are therefore feared to have an impact on global warming.
- the use of refrigerants has been considered.
- phosphorus-based additives typified by tricresyl phosphate (TCP) have been used as an extreme pressure agent in refrigerator oil compositions.
- TCP tricresyl phosphate
- phosphorus-based extreme pressure agents have the problem that they are denatured and sludged due to pyrolysis, calo-hydrolysis, and tribochemical reaction on the friction surface.
- the phosphorus additive is consumed when it is altered and sludged, the lubrication performance over a long period of time cannot be maintained, and seizure and wear may occur.
- Refrigerator lubricating oil compositions using conventional chlorofluorocarbon refrigerants have been added chlorofluorocarbons that have an organic sulfur compound added, are excellent in heat resistance and wear resistance, and are less susceptible to changes in temperature.
- a sulfur-containing lubricating oil having performance with excellent solubility has been proposed (Patent Document 1).
- Patent Document 1 in the lubricating oil composition for chlorofluorocarbon refrigerators, an organic sulfur compound is used. The content is important, and the organic sulfur compound may be naturally present in the mineral oil when, for example, mineral oil is used as the base oil.
- sufficient wear resistance and extreme pressure cannot be imparted only by controlling the sulfur content. I got it.
- Patent Document 1 Japanese Patent Laid-Open No. 58-103594
- the present invention has been made to solve the above-described problems, and is a refrigerator using a natural refrigerant that can maintain lubricating performance for a long period of time and does not block capillaries in the refrigeration cycle. It is an object of the present invention to provide a lubricating oil composition.
- a refrigerator oil containing a specific organic sulfur compound in a specific base oil is a natural refrigerant. It has been found that the use of can keep the lubrication performance over a long period of time and does not block the capillary in the freezing cycle. The present invention has been completed based on such knowledge.
- the present invention relates to (A) a polyalkylene glycol, polyol ester, poly- ⁇ - olefin, alkylbenzene, and a base oil having at least one kind of power selected from mineral oil, and (ii) organic sulfur having a sulfur content of 35% by mass or less.
- a refrigerating machine oil composition comprising a compound and a refrigerant comprising at least one selected from (C) carbon dioxide, hydrocarbons and ammonia, wherein the total sulfur content is the total amount of ( ⁇ ) component and ( ⁇ ) component
- the refrigerating machine oil composition is provided in an amount of 0.01 to 0. 1% by mass.
- FIG. 1 is a view showing a clogging clog tester.
- the lubricating oil composition of the present invention uses at least one selected from (A) polyalkylene glycol, polyol ester, poly- ⁇ -olefin, alkylbenzene, and mineral oil as the base oil.
- the polyalkylene glycol is preferably one represented by the following general formula (I).
- R 1 is hydrogen, an alkyl group having 1 to 10 carbon atoms, an acyl group or an aliphatic hydrocarbon group having 2 to 6 bonding sites
- R 2 is an alkylene group having 2 to 4 carbon atoms
- R 3 is hydrogen, an alkyl group or acyl group having 1 to 10 carbon atoms
- n is an integer of 1 to 6
- m is an integer having an average value of m X n of 6 to 80.
- the alkyl group may be linear, branched, cyclic, or misaligned. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, a cyclopentyl group, a cyclohexyl group, and the like.
- the carbon number of the alkyl group is preferably 10 or less, and if it is 10 or less, sufficient compatibility with the refrigerant can be obtained.
- the alkyl part of the acyl group may be linear, branched, or cyclic, and may be shifted! /.
- alkyl moiety of the acyl group examples include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, a cyclopentyl group, a cyclohexyl group, and the like.
- the number of carbon atoms of the acyl group is the same as that of the alkyl group. It is preferable that it is 10 or less. If it is 10 or less, sufficient compatibility with the refrigerant can be obtained.
- R 1 and R 3 may be the same or different from each other.
- R 1 or R 3 is hydrogen and the other is an alkyl group. 1 to 3 alkyl groups, particularly a methyl group is preferred. In addition, it is preferable that both R 1 and R 3 are alkyl groups having 1 to 3 carbon atoms, and it is particularly preferable that both of R 1 and R 3 are methyl groups.
- the base oil of the present invention a mixture of plural types of polyalkylene glycols can be used.
- polyol ester examples include carboxylic acid esters of polyhydric hydroxy compounds containing at least two hydroxyl groups.
- those represented by the following general formula (II) are preferable.
- R 4 is a hydrocarbon group
- R 5 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms
- f is an integer of 2-6
- a plurality of [OCOR 5 ] may be the same or different! /.
- the hydrocarbon group represented by R 4 is linear or branched! /, And may be any alkyl group having 2 to 10 carbon atoms. It is.
- R 5 is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, preferably an alkyl group having 2 to 16 carbon atoms.
- the polyol ester represented by the general formula (II) is represented by the following general formula (III):
- R 5 is the same as defined above and can be obtained by reacting a reactive derivative such as an ester thereof or an acid halide.
- polyhydric alcohol represented by the general formula (III) various alcohols can be used.
- ethylene glycol, propylene glycol, butylene glycol, neopentinoglycolanol, trimethylolethane, trimethylolpropane examples include glycerin, pentaerythritol, dipentaerythritol, and sorbitol.
- the carboxylic acid represented is not particularly limited.
- propionic acid for example, propionic acid, butyric acid, bivalric acid, valeric acid, caproic acid, heptanoic acid, 3-methylhexanoic acid, 2-ethylhexanoic acid, force prillic acid,
- Examples include pelargonic acid, decanoic acid, lauric acid, myristic acid, palmitic acid.
- a plurality of types of polyol esters can be mixed and used.
- Poly- ⁇ -year-old refin is an oligomer of ⁇ -olefin having about 3-12 carbon atoms, preferably having a molecular weight of 200-5000, and having a molecular weight of 300-2000. preferable.
- the base oil of the present invention it is possible to use a mixture of a plurality of types of poly- ⁇ -age refin.
- Alkylbenzene is obtained by polymerizing aromatics such as benzene, toluene, xylene, ethylbenzene, methylethylbenzene, jetylbenzene and mixtures thereof, lower monoolefins such as ethylene, propylene, butene, and isobutylene, and propylene.
- the number of alkyl groups contained in the benzene of the alkyl benzene is 1 to 3, and those containing many alkyl benzenes having two alkyl groups are particularly preferable.
- the base oil of the present invention can be used by mixing a plurality of types of alkylbenzenes.
- the mineral oil used as the base oil of the present invention is not particularly limited, and examples thereof include paraffinic mineral oil, naphthenic mineral oil and the like. Those having a sulfur content of 200 mass ppm or less are preferred.
- the sulfur content in the mineral oil varies depending on the sulfur content in the crude oil used as a raw material, but it is preferable to refine it so that it becomes 200 mass ppm or less.
- As the base oil of the present invention plural kinds of mineral oils can be mixed and used.
- the base oil (A) used in the present invention those described above are preferably used.
- polyalkylene glycol, polyol ester, poly ⁇ -olefin, Alkylbenzene is particularly preferable from the viewpoints of stability and evaporation loss.
- these can be used individually by 1 type or in mixture of 2 or more types.
- the base oil used in the present invention has a kinematic viscosity at 40 ° C of 3-1000 mm 2 Zs Is preferred. If it is 3 mm 2 Zs or more, sufficient lubrication performance can be obtained, and if it is 1000 mm 2 Zs or less, energy efficiency is increased without applying excessive load force. From the above viewpoints, the kinematic viscosity of the base oil at 40 ° C is preferably in the range of 5 – 500 mm 2 Zs, and more preferably in the range of 5 to 150 mm 2 / s! /.
- the present invention is characterized in that the component (B) contains an organic sulfur compound having a sulfur content of 35% by mass or less. If the sulfur content exceeds 35 mass%, alteration or sludge formation may occur. Specifically, polysulfide containing 3 or more sulfur in one molecule has such a risk. In addition, it is preferable that the sulfur content is more than 5% by mass because the amount of component (B) can be reduced.
- Examples of the (B) organic sulfur compound preferably used in the present invention include an aliphatic sulfur compound, a bicyclic sulfur compound, and an aromatic sulfur compound.
- the aliphatic sulfur compound preferably has 12 or more carbon atoms, more preferably 14 or more, and particularly preferably 18 or more. Specific examples include dioctylsulfide, didodecylsulfide, ditetradecylsulfide and the like.
- the heterocyclic sulfur compound preferably has 8 or more carbon atoms, more preferably 10 or more carbon atoms, and more preferably 12 or more carbon atoms. preferable. Specific examples include benzothiophene, dibenzothiophene, phenothiazine, benzothiapyran, thiapyran, thianthrene, dibenzothiapyran, diphenol-disulfide, and alkyl derivatives thereof.
- the aromatic sulfur compound preferably has 12 or more carbon atoms, and more preferably has 16 or more carbon atoms.
- Specific examples include 4,4′-thiobis (3-methyl-6-tert-butylphenol), diphenylsulfuride, dioctyldisulfursulfide, and dialkyldiphenylsulfane sulfide.
- organic sulfur compounds other than aliphatic sulfur compounds, heterocyclic sulfur compounds, and aromatic sulfur compounds having 8 or more carbon atoms can also be used.
- organic sulfur compounds diphenol-disulfide, phenothiazine, and dialkyl-lenssulfide are preferably used.
- the sulfur content in the refrigerating machine oil composition of the present invention must be 0.01 to 0.1% by mass based on the total amount of the component (A) and the component (B). To do. If the sulfur content is 0.01 mass% or more, sufficient lubrication performance can be achieved, and if it is 0.1 mass% or less, generation of sludge due to alteration or the like can be sufficiently suppressed. . From the above viewpoint, the sulfur content is 0. 02-0. 05 mass 0/0 of that force element Mashiku range, more preferably in the range of 035 wt% 0. 025- 0..
- the lubricating oil composition of the present invention can be mixed with additives usually used in refrigerating machine oil compositions, and in particular, an antioxidant, an acid scavenger and an antifoaming agent. Is preferred.
- the anti-oxidation agent there are no particular restrictions on the anti-oxidation agent, and for example, phenol-based anti-oxidation agents and amine-based antioxidants can be used.
- the acid scavenger is blended in the refrigerator oil composition for the purpose of caro-water decomposition stability.
- phenol glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, ⁇ - And epoxy compounds such as olefin oxide and epoxidized soybean oil.
- phenol glycidyl ether alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, and ⁇ -olefin oxide are preferred in terms of compatibility.
- the antifoaming agent include silicone oil and fluorosilicone oil.
- additives such as a copper deactivator such as benzotriazole or a derivative thereof can be added as long as the object of the present invention is not impaired.
- a copper deactivator such as benzotriazole or a derivative thereof
- Each of these additives is usually added in the range of 0.005 to 5% by mass.
- the refrigerant used in the lubricating oil composition of the present invention is at least one selected from carbon dioxide, hydrocarbons and ammonia power.
- the hydrocarbon is usually used as a refrigerant, and examples thereof include propane, butane, and a mixture thereof.
- the content of these refrigerants in the refrigerator oil composition is usually in the range of 10-99% by mass. The If it is 10% by mass or more, sufficient refrigeration capacity can be exhibited. If it is 99% by mass or less, a sufficient amount of lubricating oil is present and there is no problem of seizure or wear. From the above viewpoint, the range of 30 to 95% by mass is more preferable.
- the refrigerating machine oil composition of the present invention can be used for various applications, for example, for air conditioning, refrigerator, gas heat pump (GHP), vending machine, showcase freezing, car air conditioner. It can be used for water heating, floor heating, etc.
- GTP gas heat pump
- a refrigerator oil composition prepared by the method described in each example and comparative example was placed in a glass tube having an internal volume of 10 ml, and copper, aluminum, and iron metal catalysts were added.
- the glass tube was sealed and kept at 175 ° C for 30 days, and then the appearance of the refrigerating machine oil composition, the appearance of copper, and the presence or absence of sludge were evaluated.
- the amount of wear was determined according to ASTM D2670 using a sealed Falex friction tester.
- the test conditions were a load of 1335 N, a rotation speed of 300 rpm, a temperature of 80 ° C., a test time of 1 hour, a pin force of SAISIC1137, and a block of SAE3135.
- This test apparatus 1 is disclosed in Japanese Patent Application Laid-Open No. 11-183334, and includes a compressor 2, a capillary pipe 3 serving as a means for reducing temperature and pressure, a discharge port 2A of the compressor 2, and an inlet 3 of the capillary pipe 3 In the middle of the high-temperature side flow path 4 that connects A, the low-temperature side flow path 5 that connects the outlet 3B of the exhaust pipe 3 and the suction port 2B of the compressor 2, and the high-temperature side flow path 4 and the low-temperature side flow path 5.
- a heat exchanger 6 for exchanging heat between refrigerants between the flow paths 4 and 5, and on the high-temperature side flow path 4 between the compressor 2 and the heat exchange 6 on the discharge side.
- a pressure gauge 7 is provided, and a suction side pressure gauge 8 is provided between the heat exchanger 6 and the compressor 2 on the low temperature side flow path 5, and below it.
- a valve 9 for connecting a vacuum pump is provided on the flow side.
- the suction side pressure (Ps) is 0.4 MPa
- the discharge side pressure (Pd) is 3.3 MPa
- the heat exchange m «inlet temperature (Td) is 110 ° C
- the heat exchange outlet temperature (Ts) is 30. ° C.
- the test was conducted using isobutane (R600a) as the refrigerant, mixing 400 g of sample oil (total amount of component (A) and component (B)) and the amount of refrigerant.
- Refrigerating machine oil composed of (A) base oil and (B) specific organic compound shown in Table 1 was prepared and evaluated by the above evaluation method. The results are shown in Table 1.
- A-2 Polyethylene glycol polypropylene glycol copolymer dimethyl ether (40 ° C viscosity; 100mm 2 Zs)
- A- -6 Norafine mineral oil (40 ° C viscosity; 90mm 2 Zs, sulfur content 5 mass ppm or less)
- A--7 naphthenic mineral oil (viscosity at 40 ° C; 10mm 2 Zs, sulfur content 107 mass ppm)
- A- -8 naphthenic mineral oil (40 ° C viscosity; 56mm 2 Zs, sulfur content 3000 mass ppm)
- the novel refrigerating machine oil composition of the present invention can maintain lubrication performance for a long period without environmental problems such as destruction of the ozone layer and global warming, and does not clog the cavities in the refrigeration cycle. Therefore, for air conditioning, refrigerator, gas heat pump (GHP), It can be suitably used for refrigeration such as vending machines and showcases, for car air conditioners, for hot water supply, and for floor heating.
- GFP gas heat pump
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- Combustion & Propulsion (AREA)
- Thermal Sciences (AREA)
- Materials Engineering (AREA)
- Lubricants (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/575,172 US7718083B2 (en) | 2004-09-14 | 2004-09-14 | Refrigerator oil composition |
KR1020077005368A KR101156388B1 (ko) | 2004-09-14 | 2004-09-14 | 냉동기유 조성물 |
PCT/JP2004/013367 WO2006030490A1 (ja) | 2004-09-14 | 2004-09-14 | 冷凍機油組成物 |
JP2006534974A JP4630283B2 (ja) | 2004-09-14 | 2004-09-14 | 冷凍機油組成物 |
CNA2004800439988A CN101018844A (zh) | 2004-09-14 | 2004-09-14 | 冷冻机油组合物 |
EP04822285A EP1792970B1 (en) | 2004-09-14 | 2004-09-14 | Refrigerator oil composition containing an aromatic sulfur compound |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/JP2004/013367 WO2006030490A1 (ja) | 2004-09-14 | 2004-09-14 | 冷凍機油組成物 |
Publications (1)
Publication Number | Publication Date |
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WO2006030490A1 true WO2006030490A1 (ja) | 2006-03-23 |
Family
ID=36059757
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2004/013367 WO2006030490A1 (ja) | 2004-09-14 | 2004-09-14 | 冷凍機油組成物 |
Country Status (6)
Country | Link |
---|---|
US (1) | US7718083B2 (ja) |
EP (1) | EP1792970B1 (ja) |
JP (1) | JP4630283B2 (ja) |
KR (1) | KR101156388B1 (ja) |
CN (1) | CN101018844A (ja) |
WO (1) | WO2006030490A1 (ja) |
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CN110699158B (zh) * | 2019-10-21 | 2022-11-22 | 中国石油化工股份有限公司 | 一种冷冻机油、其制备方法及应用 |
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US11365368B2 (en) | 2017-12-08 | 2022-06-21 | Eneos Corporation | Refrigerator oil and hydraulic fluid composition for refrigerators |
JP7146391B2 (ja) | 2017-12-08 | 2022-10-04 | Eneos株式会社 | 冷凍機油及び冷凍機用作動流体組成物 |
KR102617816B1 (ko) | 2017-12-08 | 2023-12-27 | 에네오스 가부시키가이샤 | 냉동기유 및 냉동기용 작동 유체 조성물 |
Also Published As
Publication number | Publication date |
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EP1792970B1 (en) | 2013-01-23 |
KR101156388B1 (ko) | 2012-06-13 |
EP1792970A4 (en) | 2010-07-14 |
JP4630283B2 (ja) | 2011-02-09 |
EP1792970A1 (en) | 2007-06-06 |
JPWO2006030490A1 (ja) | 2008-05-08 |
US20070213239A1 (en) | 2007-09-13 |
KR20070052295A (ko) | 2007-05-21 |
US7718083B2 (en) | 2010-05-18 |
CN101018844A (zh) | 2007-08-15 |
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