EP0699742B1 - Kältemaschinenölzusammensetzung und Kältemittelzusammensetzung für Kältemaschine - Google Patents

Kältemaschinenölzusammensetzung und Kältemittelzusammensetzung für Kältemaschine Download PDF

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Publication number
EP0699742B1
EP0699742B1 EP95112085A EP95112085A EP0699742B1 EP 0699742 B1 EP0699742 B1 EP 0699742B1 EP 95112085 A EP95112085 A EP 95112085A EP 95112085 A EP95112085 A EP 95112085A EP 0699742 B1 EP0699742 B1 EP 0699742B1
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weight
isomers
oil
hfc
component
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EP95112085A
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French (fr)
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EP0699742A2 (de
EP0699742A3 (de
Inventor
Katsuya c/o Nippon Oil Co. Ltd. Takigawa
Umekichi C/O Nippon Oil Co. Ltd. Sasaki
Satoshi c/o Nippon Oil Co. Ltd. Suda
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Eneos Corp
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Nippon Oil Corp
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Priority claimed from JP20132294A external-priority patent/JP3465760B2/ja
Priority claimed from JP20132394A external-priority patent/JP3384512B2/ja
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/02—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having no phosphorus-to-carbon bonds
    • C10M2223/04—Phosphate esters
    • C10M2223/045—Metal containing thio derivatives
    • 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
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • 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
    • 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
    • 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
    • C10N2040/32—Wires, ropes or cables lubricants
    • 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
    • C10N2040/34—Lubricating-sealants
    • 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
    • C10N2040/36—Release agents or mold release agents
    • 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
    • C10N2040/38—Conveyors or chain belts
    • 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
    • C10N2040/40—Generators or electric motors in oil or gas winning field
    • 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
    • C10N2040/42—Flashing oils or marking oils
    • 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
    • C10N2040/44—Super vacuum or supercritical use
    • 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
    • C10N2040/50—Medical uses

Definitions

  • This invention relates to a refrigerator oil composition and a fluid composition for a refrigerator, and in particular to a refrigerator oil composition and a fluid composition containing said oil composition for use in a refrigerator, the refrigerator oil comprising a mixed base oil consisting essentially of an alkyl benzene oil having specific features and a synthetic oil and being suited for use in combination with an HFC refrigerant containing 1,1,1,2-tetrafluoroethane (HFC-134a) and/or pentafluoroethane (HFC-125).
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • HFC-125 pentafluoroethane
  • PAG polyalkylene glycol
  • esters which are compatible with HFC have been studied or used as an oil for a refrigerator using an HFC refrigerant.
  • PAG polyalkylene glycol
  • esters which are compatible with HFC have been studied or used as an oil for a refrigerator using an HFC refrigerant.
  • PAG polyalkylene glycol
  • esters which are compatible with HFC have been studied or used as an oil for a refrigerator using an HFC refrigerant.
  • esters is proposed in PCT.Publication No. Hei 3-505602 as well as in Japanese Patent Unexamined Publications Nos. Hei 3-88892, Hei 2-128991, Hei 3-128992, Hei 3-200895, Hei 3-227397, Hei 4-20597, Hei 4-72390, Hei 4-218592 and Hei 4-249593.
  • ester-based oils are readily hydrolyzed to generate an acid thus possibly giving rise to various problems.
  • these oils are accompanied with a serious problem that they are inferior in lubricity as compared with a mineral oil/CFC or a mineral oil/HCFC.
  • Japanese Patent Unexamined Publication No. Hei 5-157379 describes a refrigerating system for an HFC-134a refrigerant wherein there is used a refrigerator oil which is incompatible with a refrigerant; as an example of such an incompatible oil, an alkylbenzene oil is disclosed therein.
  • Japanese Patent Unexamined Publication No. Hei 5-59386 describes a mixed oil comprising a hydrocarbon compound and ester or ether, which is useful as a refrigerator oil for a refrigerator using tetrafluoroethane.
  • alkylbenzene oil (alkylbenzenes) which is free from hydrolysis and hygroscopicity and made an extensive study to finally find out that if a mixture comprising an alkylbenzene oil having a specific property and a specific synthetic oil is used as a refrigerator oil for HFC-134a and/or HFC-125, the seizure of the refrigerating compressor can be avoided, thus indicating an excellent lubricity of the alkylbenzene oil, and that the alkylbenzene oil is capable of maintaining a high reliability for a long period of time.
  • This invention has thus been accomplished in one aspect.
  • the object of the present invention is to provide a refrigerator oil composition to be used with an HFC refrigerant containing HFC-134a and/or HFC-125, which enables a refrigerating compressor to be prevented from its seizure, is excellent in lubricity and retains high reliability for a long period of time.
  • Another object of the present invention is to provide a fluid composition for use in a refrigerator, which comprises the above refrigerator oil composition and an HFC refrigerant containing HFC-134a and/or HFC-125.
  • a refrigerator oil composition for use with an HFC refrigerant containing HFC-134a and/or HFC-125 which comprises:
  • an oil composition according to such first aspect of the invention further comprising component (C), wherein said component (C) is 0.005 to 5.0 parts by weight (based on 100 parts by weight of the mixed base oil) of a phosphorus compound.
  • a fluid composition for use in a refrigerator which comprises:
  • a fluid composition according to such third aspect of the invention further comprising component (C), wherein said component (C) is 0.005 to 5.0 parts by weight (based on 100 parts by weight of the mixed base oil) of a phosphorus compound.
  • the component (A) of the refrigerator oil or oil composition (these expressions will hereinafter be collectively referred to simply as a refrigerator oil composition) proposed by this invention comprises an alkylbenzene oil containing at least 60% by weight (based on total weight of the component (A)) of alkylbenzenes having a molecular weight of 200 to 350.
  • the alkylbenzene oil it is required for the alkylbenzene oil to contain, based on total weight of the component (A), at least 60% by weight, preferably at least 65% by weight, more preferably at least 70% by weight, still more preferably at least 80% by weight, most preferably 100% by weight of alkylbenzenes having a molecular weight of 200 to 350. If there is employed an alkylbenzene oil which does not meet the above requirements, the seizure of a refrigerating compressor used may possibly be caused after a long period of its operation, thus undesirably affecting the reliability of the refrigerator oil.
  • the alkylbenzene oil may desirably be selected from those containing, based on total weight of the component (A), at least 30% by weight, more preferably at least 35% by weight, most preferably at least 40% by weight of alkylbenzenes having a molecular weight of 200 to 300.
  • the alkylbenzene oil constituting the component (A) of the refrigerator oil composition of this invention there is no restriction with respect to the molecular structure of the component alkylbenzenes as far as the molecular weight thereof falls within the range of from 200 to 350.
  • an alkylbenzene oil (a) composed of alkylbenzenes having 1 to 4 alkyl groups, each group containing 1 to 19 carbon atoms and the total amount of carbon atoms in the alkyl group being 9 to 19, and more preferably to select alkylbenzenes having 1 to 4 alkyl groups, each group containing 1 to 15 carbon atoms and the total amount of carbon atoms in the alkyl group being 9 to 15.
  • alkyl groups containing 1 to 19 carbon atoms are methyl, ethyl, propyl (including all isomers), butyl (including all isomers), pentyl (including all isomers), hexyl (including all isomers), heptyl (including all isomers), octyl (including all isomers), nonyl (including all isomers), decyl (including all isomers), undecyl (including all isomers), dodecyl (including all isomers), tridecyl (including all isomers), tetradecyl (including all isomers), pentadecyl (including all isomers), hexadecyl (including all isomers), heptadecyl (including all isomers), octadecyl (including all isomers) and nonadecyl (including all isomers).
  • alkyl groups may be straight-chain or branched-chain ones. However, in view of the stability and viscosity of the alkylbenzenes, branched-chain alkyl groups are preferable, and the branched-chain alkyl groups that are derived from oligomers of olefins such as propylene, butene and isobutylene in view of availability.
  • the number of alkyl groups in the alkylbenzenes defined in the above (a) is confined to 1 to 4. However, in view of the stability and availability of the alkylbenzenes, it is the most preferable to select alkylbenzenes having one or two of alkyl groups, i.e., a monoalkylbenzene, a dialkylbenzene or a mixture of them.
  • alkylbenzenes defined in the above (a) which have the same molecular structure, but also those having different molecular structures as long as there are satisfied the conditions that they contain 1 to 4 alkyl groups, each group containing 1 to 19 carbon atoms and the total amount of carbon atoms in the alkyl group being 9 to 19.
  • the alkylbenzene oil constituting the component (A) may contain less than 40% by weight, preferably less than 35% by weight, or more preferably less than 30% by weight, of alkylbenzenes having a molecular weight of less than 200 or more than 350.
  • the molecular weight of such alkylbenzenes be confined to a range of more than 350 to 450, more preferably more than 350 to 430 in view of retaining reliability during a long period of operation of a compressor used.
  • alkylbenzenes having a molecular weight ranging from more than 350 to 450 there are no restrictions imposed on the molecular structure thereof as far as the molecular weights fall within this range.
  • alkylbenzenes (b) having 1 to 4 alkyl groups, each group containing 1 to 40 carbon atoms and the total amount of carbon atoms in the alkyl group being 20 to 40 and more preferably to select alkylbenzenes having 1 to 4 alkyl groups, each group containing 1 to 30 carbon atoms and the total amount of carbon atoms in the alkyl group being 20 to 30.
  • alkyl groups containing 1 to 40 carbon atoms are methyl, ethyl, propyl (including all isomers), butyl (including all isomers), pentyl (including all isomers), hexyl (including all isomers), heptyl (including all isomers), octyl (including all isomers), nonyl (including all isomers), decyl (including all isomers), undecyl (including all isomers), dodecyl (including all isomers), tridecyl (including all isomers), tetradecyl (including all isomers), pentadecyl (including all isomers), hexadecyl (including all isomers), heptadecyl (including all isomers), octadecyl (including all isomers), nonadecyl (including all isomers), icosyl groups (including all isomers), henicosyl groups (including
  • alkyl groups may be straight-chain or branched-chain ones. However, in view of the stability and viscosity of the alkylbenzene, branched-chain alkyl groups are preferable; and branched-chain alkyl groups that are derived from an oligomer of an olefin such as propylene, butene or isobutylene are more preferable in view of their availability.
  • the number of alkyl groups in the alkylbenzenes defined in the above (b) is confined to 1 to 4. However, in view of the stability and availability of the alkylbenzenes, it is the most preferable to select alkylbenzenes having one or two alkyl groups, i.e., a monoalkylbenzene, a dialkylbenzene and a mixture thereof.
  • alkylbenzenes defined in the above (b) which have the same molecular structure, but also those having different molecular structures as long as there are satisfied the conditions that they contain 1 to 4 alkyl group, each group containing 1 to 40 carbon atoms and the total amount of carbon atoms in the alkyl group being 20 to 40.
  • alkylbenzenes constituting the component (A) of the refrigerator oil composition of this invention
  • alkylbenzene oil constituting the component (A) of the refrigerator oil composition of this invention
  • the alkylbenzene oil can be manufactured according to the following synthesizing methods.
  • Aromatic compounds which may be used as a raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene and a mixture thereof.
  • Alkylating agents which may be used herein include a lower mono-olefin such as ethylene, propylene, butene or isobutylene; preferably an olefin of a straight-chain or branched-chain type having 6 to 40 carbon atoms that is obtained by the polymerization of propylene; an olefin of a straight-chain or branched-chain type having 6 to 40 carbon atoms that is obtained by the thermal decomposition of wax, heavy oil, a petroleum fraction, polyethylene, polypropylene or the like; an olefin of a straight-chain type having 6 to 40 carbon atoms that is obtained by separating n-paraffin from a petroleum fraction such as kerosine or gas oil and then catalytic
  • An alkylating catalyst for use in the alkylation includes a conventional catalyst exemplified by a Friedel-Crafts catalyst such as aluminum chloride or zinc chloride; or an acidic catalyst such as sulfuric acid, phosphoric acid, silico-tungstic acid, hydrofluoric acid or activated clay.
  • a Friedel-Crafts catalyst such as aluminum chloride or zinc chloride
  • an acidic catalyst such as sulfuric acid, phosphoric acid, silico-tungstic acid, hydrofluoric acid or activated clay.
  • the alkylbenzene oil constituting the component (A) of the refrigerator oil composition of this invention may be obtained by mixing separately prepared alkylbenzenes having a molecular weight ranging from 200 to 350 with alkylbenzenes having a molecular weight of less than 200 or more than 350 in a ratio as defined by this invention.
  • the component (B) of the refrigerator oil composition of this invention is a synthetic oil containing oxygen.
  • this component (B) are an ester, polyglycol, ketone, polyphenyl ether, silicone, polysiloxane and perfluoro ether.
  • (c) ester, (d) polyglycol, (e) ketone and a mixture of them are especially preferable.
  • esters are a dibasic ester, a polyol ester, a complex ester, a polyol carbonate and a mixture of them.
  • dibasic esters are those that can be obtained by reacting a dibasic acid having 5 to 10 carbon atoms such as glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid with a monohydric alcohol having 1 to 15 carbon atoms and an alkyl group of a straight-chain or branched-chain type, such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol or pentadecanol.
  • a dibasic acid having 5 to 10 carbon atoms such as glutamic acid, adipic acid, pimelic acid, suberic acid, azelaic acid or sebacic acid
  • esters may also be used as a mixture. More particularly, these esters include ditridecyl glutarate, di 2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di 2-ethylhexyl sebacate and a mixture of them.
  • polyol esters are esters between a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 6 to 20 carbon atoms. More particularly, such diols include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol-, 1,9-nonanediol, 1,10-decanediol, 1,11-unde
  • polyol examples include polyalcohols such as trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol), tri-(pentaerythritol), glycerin, polyglycerin (glycerin dimer to icosamer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol-glycerin condensate, adonitol, arabitol, xylitol and mannitol; saccharides such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose,
  • such fatty acids include pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid (these fatty acids may be of a straight-chain or branched-chain type), or a neo acid where ⁇ carbon atom thereof is quaternary.
  • valeric acid isopentanoic acid, caproic acid, enanthic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, 3,5,5-trimethylhexanoic acid may be preferably empoyed as a fatty acid.
  • Polyolester may contain a free hydroxyl group.
  • the polyol ester are esters of a hindered alcohol such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol) and tri-(pentaerythritol).
  • a hindered alcohol such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di-(trimethylolpropane), tri-(trimethylolpropane), pentaerythritol, di-(pentaerythritol) and tri-(pentaerythritol).
  • neopentylglycol 2-ethylhexanoate trimethylolpropane caprate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, pentaerythritol pelargonate or a mixture of them.
  • a complex ester is an ester obtained by reacting a fatty acid and a dibasic acid with a monohydric alcohol and a polyol.
  • fatty acids, dibasic acids, monohydric alcohols and polyols useful in this case may be the same as exemplified above with reference to dibasic esters and polyol esters.
  • a polyol carbonate ester is an ester obtained by reacting carbonic acid with a monohydric alcohol and a polyol.
  • monohydric alcohols and polyols useful in this case may be not only the same as exemplified above, but also polyglycol obtained through homopolymerization or copolymerization of a diol, and products which are obtainable by the addition reaction of polyglycol with the polyol mentioned above.
  • polyglycol (d) suitable in this case are polyalkylene glycols, ethers thereof and modified compounds thereof.
  • polyalkylene glycols are homopolymers or copolymers of an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • an alkylene oxide such as ethylene oxide, propylene oxide or butylene oxide.
  • a polyalkylene glycol is formed of a copolymer of alkylene oxides different in structure from each other, there is no restriction placed on the polymerization form of oxyalkylene groups, i.e., the form may be random copolymerization or block copolymerization.
  • An ether of the polyalkylene glycol is a compound wherein the hydroxyl group of the polyalkylene glycol is etherified.
  • ethers of the polyalkylene glycol are monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monopentyl ether, monohexyl ether, monoheptyl ether, monooctyl ether, monononyl ether, monodecyl ether, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether and didecyl ether.
  • modified compounds of polyglycol are an adduct of polyol with an alkylene oxide or an etherified product of polyol.
  • polyol useful in this case may be the same as those exemplified in reference to polyol esters.
  • ketones (e) mentioned above are ones which contain in the molecule at least one group represented by the following general formula: (More particularly, the ketones (e) include ketone compounds represented by the following formulas (1), (2) and (3), and a mixture of these ketone compounds.
  • X is an m+n valent aromatic ring or an alkyl-substituted aromatic ring having 6 to 50 carbon atoms, preferably 6 to 20 carbon atoms;
  • R 1 and R 2 may be the same or different and are each a hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, preferable examples thereof being an alkyl, phenyl or alkylphenyl group;
  • m and n may be the same or different integers and are each 1 to 20, preferably 1 to 10.
  • aromatic ring representing X are a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and an alkyl-substituted aromatic ring wherein at least one hydrogen atom on said aromatic rings is substituted by an alkyl group having 1 to 20 carbon atoms.
  • R 1 and R 2 are methyl, ethyl, propyl (including all isomers), butyl (including all isomers), pentyl (including all isomers), hexyl (including all isomers), heptyl (including all isomers), octyl (including all isomers), nonyl (including all isomers), decyl (including all isomers), undecyl (including all isomers), dodecyl (including all isomers), tridecyl (including all isomers), tetradecyl (including all isomers), pentadecyl (including all isomers), hexadecyl (including all isomers), heptadecyl (including all isomers), octadecyl (including all isomers), nonadecyl (including all isomers), icosyl (including all isomers), henicosyl (including all isomers), do
  • R 3 and R 5 may be the same or different and are individually a hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, preferably an alkyl, a phenyl or an alkylphenyl group;
  • R4 is an alkylene group having 1 to 19 carbon atoms, preferably 1 to 10 carbon atoms;
  • L is an integer of 1 to 5, preferably 1 to 3.
  • R 3 and R 5 are alkyl, phenyl and alkylphenyl groups by which are exemplified R 1 and R 2 in the compounds represented by the general formula (1).
  • R 4 is preferably an alkylene group which includes methylene, ethylene (including all isomers), propylene (including all isomers), butylene (including all isomers), pentylene (including all isomers), hexylene (including all isomers), heptylene (including all isomers), octylene (including all isomers), nonylene (including all isomers) or decylene group (including all isomers).
  • A is a monohydric to icosahydric alcohol residue
  • R 6 , R 7 and R 8 may be the same or different and are individually an alkylene group having 1 to 4 carbon atoms
  • R 9 is a hydrocarbon group, preferably an alkyl, phenyl or alkylphenyl group each having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms
  • p and q may be the same or different integers and are individually 0 to 30, preferably 0 to 20
  • r is an integer of 1 to 20.
  • Alcohols for the alcohol residue A include aliphatic monohydric alcohols such as methanol, ethanol, propanol (including all isomers), butanol (including all isomers), pentanol (including all isomers), hexanol (including all isomers), heptanol (including all isomers), octanol (including all isomers), nonanol (including all isomers), decanol (including all isomers), undecanol (including all isomers), dodecanol (including all isomers), tridecanol (including all isomers), tetradecanol (including all isomers), pentadecanol (including all isomers), hexadecanol (including all isomers), heptadecanol (including all isomers), octadecanol (including all isomers), nonadecanol (including all isomers), icosanol (including all is
  • alkylene groups representing R 6 , R 7 and R 8 are methylene, ethylene (including all isomers), propylene (including all isomers) and butylene (including all isomers).
  • R 9 are alkyl, phenyl and alkylphenyl groups by which are exemplified R 1 and R 2 in the compounds represented by the general formula (1).
  • the lower limit of the content of the component (A) in a refrigerator oil (a mixed base oil) of this invention comprising the components (A) and (B) is at least 70% by weight, preferably at least 75% by weight, more preferably at least 80% by weight, based on the total weight of the components (A) and (B), while the upper limit of the content of the component (B) is not more than 30% by weight, preferably not more than 25% by weight, more preferably not more than 20% by weight, based on the total weight of the components (A) and (B).
  • the upper limit of the content of the component (A) in a refrigerator oil (a mixed base oil) of this invention comprising the components (A) and (B) is not more than 99% by weight, preferably not more than 95% by weight, more preferably not more than 90% by weight, based on the total weight of the components (A) and (B), while the lower limit of the content of the component (B) is at least 1% by weight, preferably at least 5% by weight, more preferably at least 10% by weight, based on the total weight of the components (A) and (B).
  • the lower limit of the content of the component (A) is less than 70% by weight based on the total weight of the components (A) and (B), a long term reliability of the refrigerator oil composition will be undesirably deteriorated.
  • the upper limit of the content of the component (A) is more than 99% by weight based on the total weight of the components (A) and (B), the return of the refrigerator oil composition in a refrigerating system will be undesirably deteriorated.
  • the refrigerator oil of this invention comprises (A) an alkylbenzene oil (alkylbenzenes) and (B) a synthetic oil containing oxygen as defined above, which can be suitably used as a refrigerator oil for an HFC refrigerant containing HFC-134a and/or HFC-125 without accompaniment of an additive.
  • a refrigerator oil composition containing therein any of various additives as required.
  • a phosphorus compound (C) in view of improving the refrigerating apparatus in wear resistance and load resistance by the use of the refrigerator oil composition.
  • the phosphorus compound (C) means in this case at least one kind of a phosphorus compound selected from the group consisting of phosphoric esters, acidic phosphoric esters, amine salt of acidic phosphoric esters, chlorinated phosphoric esters and phosphorous esters.
  • These phosphorus compounds are esters obtained by a reaction between phosphoric acid or phosphorous acid and an alkanol or polyether type alcohol, and are also derivatives of said esters.
  • Examples of phosphoric esters are tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyldiphenyl phosphate and xyleyldiphenyl phosphate.
  • acidic phosphoric esters are monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate
  • amine salts of acidic phosphoric esters are methyl amine, ethyl amine, propyl amine, butyl amine, pentyl amine, hexyl amine, heptyl amine, octyl amine, dimethyl amine, diethyl amine, dipropyl amine, dibutyl amine, dipentyl amine, dihexyl amine, diheptyl amine, dioctyl amine, trimethyl amine, triethyl amine, tripropyl amine, tributyl amine, tripentyl amine, trihexyl amine, triheptyl amine and trioctyl amine of the acidic phosphoric ester.
  • chlorinated phosphoric esters are tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate and polyoxyalkylene bis[di(chloroalkyl)] phosphate.
  • Examples of phosphorous esters are dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl
  • These phosphorus compounds may be incorporated into a refrigerator oil composition in any desired mixing ratio. However, it is generally preferable to add these phosphorus compounds in the ratio of 0.005 to 5.0 parts by weight, more preferably 0.01 to 3.0 parts by weight, based on 100 parts by weight of the total amount of the alkylbenzene oil (A) and the synthetic oil containing oxygen (B).
  • the amount of the phosphorus compound added is less than 0.005 part by weight based on 100 parts by weight of the total amount of the components (A) and (B), any substantial effect on the improvement of wear resistance and loading resistance would not be attained by the addition of said compound.
  • the amount of the phosphorus compound added exceeds 5.0% by weight based on 100 parts by weight of the total amount of the components (A) and (B), it may give rise to undesirable corrosion in a refrigerating system during its use for a long period of time.
  • the improvement in wear resistance and loading resistance to be attained by the addition of the phosphorus compound is one of the features of the refrigerator oil composition of this invention. It is certainly possible to achieve more or less an improvement in wear resistance and loading resistance, even with the use of PAG (polyalkylene glycol) or an ester which is each known as useful for a refrigerator oil used with HFC. However, the effect that can be attained by the use of these conventional compounds is far less than the effect to be achieved by the use of the refrigerator oil composition of this invention.
  • phenylglycidyl ether type epoxy compounds (1) are phenylglycidyl ether and alkylphenylglycidyl ether.
  • the alkylphenylglycidyl ether used herein may be one having 1 to 3 alkyl groups each containing 1 to 13 carbon atoms, preferably one having one alkyl group containing 4 to 10 carbon atoms.
  • alkylphenylglycidyl ethers examples include n-butylphenylglycidyl ether, i-butylphenylglycidyl ether, sec-butylphenylglycidyl ether, tert-butylphenylglycidyl ether, pentylphenylglycidyl ether, hexylphenylglycidyl ether, heptylphenylglycidyl ether, octylphenylglycidyl ether, nonylphenylglycidyl ether and decylphenylglycidyl ether.
  • alkylglycidyl ether type epoxy compounds (2) are decylglycidyl ether, undecylglycidyl ether, dodecylglycidyl ether, tridecylglycidyl ether, tetradecylglycidyl ether, 2-ethylhexylglycidyl ether, neopentylglycoldiglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexadiol diglycidyl ether, sorbitol polyglycidyl ether, polyalkyleneglycol monoglycidyl ether and polyalkyleneglycol diglycidyl ether.
  • glycidyl ester type epoxy compounds (3) are phenylglycidyl ester, alkylglycidyl ester and alkenylglycidyl ester. Preferable examples thereof are glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate and glycidyl methacrylate.
  • aryl oxirane compounds (4) are 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.
  • alkyl oxirane compounds (5) are 1,2-epoxybutane, 1,2-epoxynonane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,2-epoxyoctadecane, 1,2-epoxynonadecane and 1,2-epoxyeicosane.
  • Examples of alicyclic epoxy compounds (6) are 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis(3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2-(7-oxabicyclo[4.1.0]hept-3-yl)-spiro(1,3-dioxane-5,3'-[7]oxabicyclo[4.1.0]) heptane, 4-(l'-methylepoxyethyl)-1,2-epoxy-2-methylcyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.
  • epoxidized fatty monoesters (7) are an ester formed by reacting an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol having 1 to 8 carbon atoms, phenol or an alkylphenol.
  • epoxystearates such as butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, phenyl and butylphenyl esters of epoxystearic acid are preferred.
  • Examples of epoxidized vegetable oils (8) are epoxy compounds of a vegetable oil such as soybean oil, linseed oil or cottonseed oil.
  • epoxy compounds the more preferred ones are phenylglycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds and epoxidized fatty monoester are preferred.
  • phenylglycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds with phenylglycidyl ether, butylphenylglycidyl ether and alkylglycidyl esters being the most preferred.
  • epoxy compounds may be incorporated into a refrigerator oil in any desired mixing ratio. However, it is generally preferable to incorporated these epoxy compounds in the ratio of 0.1 to 5.0% by weight, more preferably 0.2 to 2.0% by weight, based on 100 parts by weight of the total amount of the alkylbenzene oil (A) and the synthetic oil containing oxygen (B).
  • the suitable additives include, anti-oxidants of a phenol type such as di-tert-butyl-p-cresol and bisphenol A or of an amine type such as phenyl- ⁇ -naphthylamine and N,N-di(2-naphthyl)-p-phenylene diamine; anti-wear additives such as zinc dithiophosphate; extreme pressure agents such as chlorinated paraffin and sulfur compounds; an oiliness improvers such as a fatty acid; antifoaming agents such as silicone-type ones; metal inactivators such as benzotriazole; viscosity index improvers; pour point depressants; and detergent-dispersants.
  • anti-oxidants of a phenol type such as di-tert-butyl-p-cresol and bisphenol A
  • an amine type such as phenyl- ⁇ -naphthylamine and N,N-di(2-naphthyl)-p-phenylene diamine
  • additives may be used singly or in combination. These additives can be generally added in a ratio of not more than 10% by weight, more preferably not more than 5% by weight, based on 100 parts by weight of the total amount of the alkylbenzene oil (A) and the synthetic oil containing oxygen (B).
  • the refrigerants used, together with the refrigerator oil composition of this invention, in a rafrigerator include an alkane fluoride having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms and containing at least 40% by weight of 1,1,1,2-tetrafluoroethane (HFC-134a) and/or an alkane fluoride having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms and containing at least 20% by weight, preferably at least 30% by weight, more preferably at least 40% by weight of pentafluoroethane (HFC-125).
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • HFC hydrofluorocarbon
  • HFC-134a 1,1,2,2-tetrafluoroethane
  • HFC-152a 1,1-difluoroethane
  • HFC-134a 1,1,1,2-tetrafluoroethane
  • HFC-125 pentafluoroethane
  • HFC-134a alone HFC-125 alone
  • a mixture of HFC-134a/HFC-32 in a ratio of 60-80% by weight/40-20% by weight a mixture of HFC-134a/HFC-32/HFC-125 in a ratio of 40-70% by weight/15-35% by weight/5-40% by weight
  • the HFC refrigerant mixtures are R404A (HFC-125/HFC-143a/HFC-134a in a ratio of 44% by weight/52% by weight/4% by weight), R407C (HFC-32/HFC-125/HFC-134a in a ratio of 23% by weight/25% by weight/52% by weight), R410A (HFC-32/HFC-125 in a ratio of 50% by weight/50% by weight), R410B (HFC-32/HFC-125 in a ratio of 45% by weight/55% by weight) and R507 (HFC-125/HFC-143a in a ratio of 50% by weight/50% by weight.
  • R404A HFC-125/HFC-143a/HFC-134a in a ratio of 44% by weight/52% by weight/4% by weight
  • R407C HFC-32/HFC-125/HFC-134a in a ratio of 23% by weight/25% by weight/52% by weight
  • R410A HFC-32/H
  • the refrigerator oil composition according to this invention is generally present in a refrigerator in the form of a fluid composition in which the refrigerator oil composition is mixed with the alkane fluoride as mentioned above.
  • the mixing ratio of the refrigerator oil composition to the refrigerant (alkane fluoride) in this fluid composition may be optionally determined, but is generally a ratio of 1 to 500 parts by weight, of the refrigerator oil composition preferably 2 to 400 parts by weight, of the refrigerator oil composition per 100 parts by weight of the refrigerant.
  • the refrigerator oil composition according to this invention is excellent in electric properties and low in hygroscopicity, it is particularly suited for use in an air conditioner or a refrigerator provided with a sealed compressor of a reciprocating type or rotary type.
  • This refrigerator oil composition is also suited for use in an air conditioner or dehumidifier for vehicles, a freezer, a refrigerating chamber, an automatic vending machine, a show-case or a cooling system for a chemical plant.
  • This refrigerator oil composition is also applicable to a compressor of a centrifugal type.
  • Fig. 1 is a schematic view of the testing apparatus used in the Evaluation Test Nos. 4 and 8, wherein the reference numeral 1 represents a refrigerating tank; 2, a copper conduit; 3, a flow meter; 4 and 6, manometers respectively; 5, a thermostatic tank; and 7, an oil pan.
  • the reference numeral 1 represents a refrigerating tank; 2, a copper conduit; 3, a flow meter; 4 and 6, manometers respectively; 5, a thermostatic tank; and 7, an oil pan.
  • Alkyl benzene (branched-chain type) 8.3 2.10 5 93 2 0
  • Alkyl benzene (branched-chain type) 15.3 2.94 4 68 14 14 C
  • Alkyl benzene (branched-chain type) 16.9 3.15 20 20 19
  • D Alkyl benzene (branched-chain type) 12.6 2.62 0 83 15 2
  • E Alkyl benzene (branched-chain type) 29.0 4.30 2 49 24 25 F Alkyl benzene (branched-chain type) 35.2 4.52 2 38 35 25 G Alkyl benzene (branched-chain type) 60.8 5.91 3 32 30 35 H Alkyl benzene (branched-chain type) 72.6 6.40 3 22 26 49 I Alkyl benzene (straight-chain type) 15.4 3.18 0 61 30 9 J Alkyl benzene (straight-chain type) 25.6
  • B A mixture of A and E (50% by weight:50% by weight).
  • G A product obatained by the re-distillation of H.
  • I and J These oils were produced by distilling a mixture of monoalkylbenzenes and dialkylbenzenes which had been prepared from, as raw materials, benzene and n-paraffin having 9 to 18 carbon atoms and separated from a kerosene fraction, by reacting them in the presence of hydrofluoric acid as an alkylating catalyst.
  • O An ester obtained by reacting adipic acid, neopentyl glycol and 3,5,5-trimethylhexanol together.
  • T A product obtained by reacting the alkylbenzenes of A with acetyl chloride in the presence of aluminum chloride.
  • Additive Name of Compound A Tricresyl phosphate B Dioleylhydrogen phosphate C Di(2-ethylhexyl) acid phosphate D Para-tertiarybutylphenylglycidyl ether E Neodecanoic glycidyl ester F 2,6-ditertiarybutyl-p-cresol
  • refrigerator oil compositions of this invention having the compositions shown in Tables 3 and 4, respectively.
  • the refrigerator oil compositions thus obtained were each subjected to an evaluation test for their long-term operability as illustrated in Tables 3 and 4 (Examples 1-26).
  • a household room air conditioner having a refrigerating capacity of 2.5kw was filled with 350g of a test oil and 1000g of a mixed refrigerant consisting of HFC-134a/HFC-32 in a ratio by weight of 70% to 30% was placed in a thermostatic room kept at an atmospheric temperature of 43°C and then subjected to a continuous operation of 500 hours while setting the air conditioner to maintain the room at 25°C, in order to evalutate the test oil for its operability.
  • a household three-door type refrigerator having an effective inner volume of 300 liters was filled with 180g of a refrigerant consisting of HFC-134a and 150g of a test oil, housed in a thermostatic room kept at an atmospheric temperature of 43°C and then subjected to a continuous operation of 500 hours while setting the temperatures of the freezing chamber and the cooling chamber to -18°C and 3°C respectively, in order to evaluate the test oil for its operability (or performance).
  • a household room air conditioner haivng a refrigerating capacity of 2.5kw was filled with 350g of a test oil and 1000g of a mixed refrigerant consisting of HFC-125/HFC-32/HFC-134a in a ratio of 25% by weight/52% by weight/23% by weight, was placed in a thermostatic room kept at an atmospheric temperature of 43°C, and then subjected to a continuous operation of 500 hours while setting the air conditioner to maintain the room at 25°C, in order to evaluate the test oil for its operability (or performance).
  • a household three-door type refrigerator having an effective inner volume of 300L was filled with 150g of a test oil, and 180g of a mixed refrigerant consisting of HFC-125/HFC-134a/HFC-143a in a ratio of 44% by weight/4% by weight/52% by weight, placed in a thermostatic room whose atmospheric temperature was kept at 43°C and then subjected to a continuous operation of 500 hours while setting the temperatures of the freezing chamber and the cooling chamber to - 18°C and 3°C respectively, in order to evaluate the test oil for operability (performance).
  • the refrigerator oil compositions of this invention did not cause the seizure of refrigerating compressor and were excellent in lubricity, thus making it possible to maintain a high reliability for a long period of time.
  • the refrigerator oil compositions of Examples 18 to 24, 26, 48 to 54 and 56, each containing a phosuphorus compound (C), indicated a remarkable improvement in the surface roughness of sliding surface portion of the compressor vanes over the refrigerator oil compositions of Examples 1 to 17, 25, 31 to 47 and 55, thus clearly demonstrating the remarkable effect of the phosuphorus compound on the improvement in wear resistance.
  • the refrigerator oil composition of this invention is far excellent in oil-return property of the refrigerator oil as compared with those of Comparative Examples 14 to 17 and 31 to 34, each containing only the component (A) as a base oil.
  • the refrigerator oil composition of this invention is suited for use in an HFC refrigerant containing HFC-134a and/or HFC-125, featured in that enables the generation of seizure of the refrigerating compressor to be avoided and excellent in lubricity, thus making it possible to maintain a high reliability for a long period of time. Therefore, the refrigerator oil composition of this invention is highly useful as a refrigerator oil composition to be utilized together with an HFC refrigerant containing HFC-134a and/or HFC-125.

Claims (4)

  1. Kältemaschinenölzusammensetzung zur Verwendung mit einem HFC-Kühlmittel, das HFC-134a und/oder HFC-125 enthält, dadurch gekennzeichnet, daß die Zusammensetzung ein Grundölgemisch umfaßt, das den Bestandteil (A) und den Bestandteil (B) umfaßt, wobei Bestandteil (A) 70 bis 99 Gewichtsprozent ausmacht und aus einem Alkylbenzolöl besteht, das wenigstens 60 Gewichtsprozent, bezogen auf das Gesamtgewicht des Bestandteils (A), an Alkylbenzolen mit einem Molekulargewicht von 200 bis 350 enthält, und wobei Bestandteil (B) 30 bis 1 Gewichtsprozent ausmacht und aus einem synthetischen sauerstoffhaltigen Öl besteht, unter dem Vorbehalt, daß eine Kältemaschinenölzusammensetzung, die aus dem Alkylbenzolöl und aus wenigstens einem Glied besteht, das aus der Gruppe gewählt ist, die aus einer Phosphorverbindung, einer Epoxyverbindung, anti-Oxidantien vom Phenoltyp, anti-Oxidantien vom Amintyp, anti-Verschleißzusätzen, Extremdruckmitteln, Öligkeitsverbesserern, anti-Schäumungsmitteln, Metallinaktivatoren, Viskositätsindexverbesserern, Gießpunktsenkern und Detergentien-Dispersionsmitteln besteht, ausgeschlossen ist.
  2. Kältemaschinenölzusammensetzung nach Anspruch 1, dadurch gekennzeichnet, daß die Zusammensetzung des weiteren einen Bestandteil (C) aus einer Phosphorverbindung zu 0,005 bis 5,0 Gewichtsanteilen, bezogen auf 100 Gewichtsanteile der Grundölmischung, umfaßt.
  3. Kältemaschinenfluidzusammensetzung, dadurch gekennzeichnet, daß die Zusammensetzung folgendes umfaßt:
    [I] ein HFC-Kühlmittel, das HFC-134a und/oder HFC-125 enthält, und
    [II] eine Kältemaschinenölzusammensetzung, die ein Grundölgemisch umfaßt, das den Bestandteil (A) und den Bestandteil (B) umfaßt, wobei Bestandteil (A) 70 bis 99 Gewichtsprozent ausmacht und aus einem Alkylbenzolöl besteht, das wenigstens 60 Gewichtsprozent, bezogen auf das Gesamtgewicht des Bestandteils (A), an Alkylbenzolen mit einem Molekulargewicht von 200 bis 350 enthält, und wobei Bestandteil (B) 30 bis 1 Gewichtsprozent ausmacht und aus einem synthetischen sauerstoffhaltigen Öl besteht, unter dem Vorbehalt, daß eine Kältemaschinenölzusammensetzung, die aus dem Alkylbenzolöl und aus wenigstens einem Glied besteht, das aus der Gruppe gewählt ist, die aus einer Phosphorverbindung, einer Epoxyverbindung, anti-Oxidantien vom Phenoltyp, anti-Oxidantien vom Amintyp, anti-Verschleißzusätzen, Extremdruckmitteln, Öligkeitsverbesserern, anti-Schäumungsmitteln, Metallinaktivatoren, Viskositätsindexverbesserern, Gießpunktsenkern und Detergentien-Dispersionsmitteln besteht, ausgeschlossen ist.
  4. Kältemaschinenfluidzusammensetzung nach Anspruch 3, dadurch gekennzeichnet, daß die Zusammensetzung des weiteren einen Bestandteil (C) aus einer Phosphorverbindung zu 0,005 bis 5,0 Gewichtsanteilen, bezogen auf 100 Gewichtsanteile der Grundölmischung, umfaßt.
EP95112085A 1994-08-03 1995-08-01 Kältemaschinenölzusammensetzung und Kältemittelzusammensetzung für Kältemaschine Expired - Lifetime EP0699742B1 (de)

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JP20132294A JP3465760B2 (ja) 1994-08-03 1994-08-03 冷凍機油組成物および冷凍機用流体組成物
JP20132394A JP3384512B2 (ja) 1994-08-03 1994-08-03 冷凍機油組成物および冷凍機用流体組成物
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CA2155166A1 (en) 1996-02-04
KR100195604B1 (ko) 1999-06-15
BR9503535A (pt) 1996-06-04
EP0699742A2 (de) 1996-03-06
EP0699742A3 (de) 1996-05-15
ES2131240T3 (es) 1999-07-16
DE69509716T2 (de) 1999-12-02
DE69509716D1 (de) 1999-06-24
CA2155166C (en) 2005-04-26

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