Lubricating oil composition

Abstract: The invention concerns a lubricating oil composition in which a lubricating oil base contains 0.1% by weight to 20% by weight of an aromatic glycidyl carboxylate having the following general formula (1): wherein R is a C₆₋₁₄ aryl or alkylaryl group, and n represents an integer of 1 or 2, and/or 0.05% by weight to 10% by weight of a phosphonate type additive having the following general formula (2): wherein R₁ or R₂ is selected from the group consisting of alkyl, aralkyl, aryl and hydroxyalkyl groups that may or may not have a substitute, and two R₂ groups may be identical with or different from each other, and which is excellent in stability to hydrolysis, heat and oxidation as well as in lubricating properties, and so provides a particularly excellent refrigerating oil composition.

Description: The present invention relates generally to a refrigerating machine lubricating oil composition that is excellent in stability to hydrolysis, heat and oxidation as well as in lubricating properties, and is well compatible with a non-chlorine type of fluorine-containing refrigerant. So far, chlorine-containing refrigerants such as R11 (CCl 3 F), R12 (CCl 2 F 2 ), R123 (CF 3 CHCl 2 ) and R22 (CHClF 2 ) have been used as refrigerants for refrigerating machinery. In recent years in which the development of substitute flon is in urgent need in view of environmental problems, however, non-chlorine type fluorine-containing refrigerants such as 1.1.1.2-tetrafluoroethane (R134a), difluoromethane (R32) and 1.1.2.2.2-pentafluoroethane (R125) have attracted wide attention. It has also been proposed to use as refrigerating machine oil polyalkylene glycol or ester oils that are compatible with these refrigerants (R134a, R32, R125, and so on). As the efficiency of refrigerating machinery increases, such refrigerating machine oil is now required to have an increased heat stability, and ester or polyalkylene glycol oils that are excellent in stability are used to this end. However, these ester or polyalkylene glycol oils are still less than satisfactory, because they hydrolyze in the presence of small amounts of water or air, or oxidize, resulting in an increase in the acid number. Their stability increase may be achieved by the incorporation of an epoxy compound in them, but the resulting oils become insufficient in terms of compatibility with refrigerants or stability, although varying depending on the structure of epoxy. In the case of conventional chlorine-containing refrigerants, there is no need of taking any special care of their lubricating properties, because they possess some lubricating properties by themselves. However, non-chlorine type fluorine-containing refrigerants are required to be increased in lubricating properties for lack of lubricating properties. It has been known to incorporate a lubricant such as tricresyl phosphate in refrigerating machine lubricating oil, but this offers a problem that the resulting lubricating oil fails to produce its own lubricating properties sufficiently, when actually used with a non-chlorine type of fluorine-containing refrigerant. A general object of the invention is to provide a lubricating oil composition that is more excellent in stability to hydrolysis, heat and oxidation as well as in lubricating properties, and a particular object of the invention is to provide a refrigerating machine lubricating oil composition used with a non-chlorine type of fluorine-containing refrigerant, which is more excellent in stability to hydrolysis and heat, especially oxidation, as well as in lubricating properties, and which is more excellent in compatibility with the refrigerant. The present invention provides a refrigerating machine lubricating oil composition comprising a lubricating oil base consisting essentially of a polyester of an aliphatic polyhydric alcohol with linear or branched fatty acids having from 3 to 12 carbon atoms and having a viscosity in the range 10 mm 2 /s to 500 mm 2 /s at 40°C which contains 0.1% by weight to 20% by weight of an aromatic glycidyl carboxylate having the following general formula (1): wherein R is an aryl or alkylaryl group having 6 to 14 carbon atoms, and n represents an integer of 1 or 2. Thus, the present invention successfully provides a lubricating oil composition much more excellent in stability to hydrolysis, heat and oxidation than ever before. The present invention also provides a lubricating oil composition comprising a lubricating oil base which contains 0.05% by weight to 10% by weight of a phosphonate type additive having the following general formula (2): wherein R 1 or R 2 are selected from the group consisting of alkyl, aralkyl, aryl and hydroxyalkyl groups which may or may not have a substituent, and two R 2 groups may or may not be identical with each other. The lubricating oil composition with the phosphonate type additive incorporated in it exhibits particularly excellent lubricating properties, when used in an oxygen-free atmosphere, as experienced in the case of a sliding part in refrigerating machinery. In this connection, it is noted that phosphite type lubricants so far used as lubricants, like tricresyl phosphite, hardly exhibit lubricating properties under such conditions. Although the detailed reason has yet to be clarified, it appears that there is a large difference in effect between when the lubricant is in the air and when it is in a refrigerant. This is because a fresh metal surface frictionally formed on the sliding part in the air is immediately covered with an oxide film, but a fresh metal surface frictionally formed on the sliding part in the refrigerant remains intact for an extended period of time, because the refrigerant forms an oxygen-free atmosphere. As a result of investigating the wear resistance of the sliding part when placed in an oxygen-free atmosphere, it has now been found that a lubricant oil containing a phosphonate type additive can exhibit excellent lubricating properties in an oxygen-free atmosphere. Further, the present invention provides a refrigerating machine lubricating oil composition comprising the specified lubricating oil base which contains 0.1% by weight to 20% by weigh of an aromatic glycidyl carboxylate having General Formula (1), 0.05% by weight to 10% by weight of a phosphonate type additive having General Formula (2), and 0.01% by weight to 5% by weight of a benzotriazole derivative having the following general formula (3): wherein R 1 is an alkyl or aryl group having 1 to 6 carbon atoms, R 2 is an alkylene or arylene group having 1 to 6 carbon atoms, R 3 or R 4 is an alkyl, aryl or alkylaryl group having 1 to 12 carbon atoms, or R 3 and R 4 may form together a heterocycle, and n is an integer of 0 or 1. This lubricating oil composition can prevent any side reaction of the aromatic glycidyl carboxylate with the phosphorous type additive, and so is much more improved in terms of stability to hydrolysis, heat and oxidation as well as in lubricating properties. The refrigerating machine oil composition according to the invention is much more improved in terms of stability to hydrolysis, heat and oxidation as well as in lubricating properties, and is much more excellent in compatibility with a fluorine type of aliphatic hydrocarbon refrigerant that does not contain any chlorine atom. Reference will now be made to the lubricating oil base in the lubricating oil compositions of the invention. The ester oils may include the following classes of esters. Among them, preference is given to polyol ester, fumaric acid ester polymers, and ester oils comprising combinations of these. (1) Polyesters of aliphatic polyhydric alcohols with linear or branched fatty acids deserve the first mention. Among the aliphatic polyhydric alcohols forming these polyesters, there are trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Among the fatty acids, mention is made of those having 3 to 12 carbon atoms, preferably, propionic acid, butyric acid, valeric acid, hexoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, isovaleric acid, neopentanoic acid, 2-methylbutyric acid, 2-ethylbutyric acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, 2,2'-dimethyloctanoic acid, 2-butyloctanoic acid, and 3,5,5-trimethylhexoic acid. Partial esters of aliphatic polyhydric alcohols with linear or branched fatty acids may also be used. The aliphatic polyhydric alcohols, for instance, may be trimethylolpropane, ditrimethylolpropane, trimethylolethane, ditrimethylolethane, pentaerythritol, dipentaerythritol, and tripentaerythritol. Among the fatty acids, mention is made of those having 3 to 9 carbon atoms, preferably, propionic acid, butyric acid, valeric acid, hexoic acid, heptanoic acid, octanoic acid, nonanoic acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, 2,2'-dimethyloctanoic acid, 2-butyloctanoic acid, and 3,5,5-trimethylhexoic acid. Most preferably, the esters of the aliphatic polyhydric alcohols with linear or branched fatty acids are those of pentaerythritol, dipentaerythritol, and tripentaerythritol with fatty acids having 5 to 12, preferably 5 to 7 carbon atoms, for instance, valeric acid, hexoic acid, heptanoic acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isononaoic acid, isodecanoic acid, 2,2'-dimethyloctanoic acid, 2-butyloctanoic acid, or their mixtures. These partial esters may be obtained by the reaction of a suitably regulated number of moles of the aliphatic polyhydric alcohol with a suitably regulated number of moles of the fatty acid. (2) Use may also be made of diesters of an aliphatic polyhydric alcohol represented by neopentyl glycol with a linear or branched fatty acid having 6 to 9 carbon atoms, for instance, hexoic acid, heptanoic acid, octanoic acid, nonanoic acid, 2-ethylbutyric acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isonoanoic acid, or 3,5,5-trimethylhexoic acid. (3) Complex esters of partial esters of aliphatic polyhydric alcohols with linear or branched fatty acids having 3 to 9 carbon atoms and linear or branched aliphatic dibasic acids or aromatic dibasic acids may be used as well. For such aliphatic polyhydric alochols, use may be made of e.g. trimethylolpropane, trimethylolethane, pentaerythritol and dipentaerythritol. For the fatty acids having 3 to 12 carbon atoms, use may be made e.g. of propionic acid, butyric acid, isobutyric acid, valeric acid, hexoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isononanoic acid, isodecanoic acid, 2,2'-dimethyloctanoic acid, 2-butyloctanoic acid and 3,5,5-trimethylhexoic acid. For these complex esters, it is desired to use fatty acids having 5 to 7, preferably 5 to 6 carbon atoms. For such fatty acids, use may be made of valeric acid, hexoic acid, isovaleric acid, 2-methylbutyric acid, 2-ethylbutyric acid, or their mixture. In this regard, it is preferable that the fatty acids consisting of five carbon atoms and six carbon atoms are mixed together at a weight ratio of 10:90 to 90:10 for use. For the aliphatic dibasic acids used with such fatty acids for estrification with polyhydric alcohols, use may be made of e.g. succinic acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic diacid, dodecanoic diacid, tridecanoic diacid, carboxyoctadecanoic acid, carboxymethyloctadecanoic acid and docosanoic diacid. For example phthalic acid and isophthalic acid, may be used for the aromatic dibasic acids; trimellitic acid for the aromatic tribasic acids; and pyromellitic acid for the aromatic tetrabasic acids. For the esterification reaction, the polyhydric alcohol and the aliphatic or aromatic dibasic acid may first be allowed to react with each other at a given ratio for partial esterification. Then, the resulting partial ester may be allowed to react with the fatty acid. Alternatively, the dibasic and fatty acids may be reversed in order, or mixtures of such acids may be used for estrification. (4) Dialkyl esters (having 16 to 22 carbon atoms) of linear or branched aliphatic dibasic acids may be used as well. For the aliphatic dibasic acids, use may be made of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic diacid, dodecanoic diacid, tridecanoic diacid, carboxyoctadecanoic acid, carboxymethyloctadecanoic acid, docosanoic diacid, and acids that are similar in property to these. Preferable aliphatic dibasic acids are succinic acid, adipic acid, sebacic acid, undecanoic diacid, dodecanoic diacide, carboxyoctadecanoic acid, and carboxymethyloctadecanoic acid. The alcohol component used has 5 to 8 carbon atoms, and may be amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, and their isomers. Among others, isoamyl alcohol, isohexyl alcohol and octyl alcohol are preferable. Examples of the dialkyl ester are dioctyl adipate, di-isoheptyl adipate, dihexyl sebacate, and diheptyl succinate. (5) Dialkyl esters (having 18 to 26 carbon atoms) of aromatic dibasic acids may be used as well. For the aromatic dibasic acids, mention is made of phthalic acid, isophthalic acid, and their equivalents. For the alcohol components in the dialkyl esters, use may be made of alcohols having 5 to 8 carbon atoms, for instance, amyl alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, and their isomers. Preferable alcohols are isoamyl alcohol, isoheptyl alcohol and octyl alcohol. The aromatic diesters may include dioctyl phthalate, di-isoheptyl phthalate and diisoamyl phthalate. (6) For the alcohol component, use is made of adducts of a monohydric alcohol selected from methanol, ethanol, propanol, butanol or like alcohol and their isomers, or a trihydric alochol such as glycerin and trimethylolpropane with 1 mole to 10 moles, preferably 1 to 6 moles of an alkylene oxide selected from ethylene oxide, propylene oxide, butylene oxide, amylene oxide or like oxide, and their isomers. Organic carboxylates include diesters obtained by the esterification of adducts of monohydric alcohols with alkylene oxides with aliphatic dibasic acids such as adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanoic diacid, dodecanoic diacid, carboxyoctadecanoic acid, carboxymethyloctadecanoic acid and docosanic diacid, or with aromatic dibasic acids such as phthalic acid. Use may be made of esters obtained by the esterification of adducts of polyhydric alcohols such as glycerin and trimethylolpropane with 1 to 10 moles of alkylene oxides with the use of, e.g., propionic acid, valeric acid, hexoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, dodecanoic acid, 2-methylhexoic acid, 2-ethylhexoic acid, isooctanoic acid, isononaoic acid, isodecanoic acid, 2,2'-dimethyloctanoic acid, and 2-butyloctanoic acid. For the fatty acids constituting the organic carboxylates, use may be made of linear or branched fatty acids. However, preference is given to using branched fatty acids, because they make a greater contribution to stability to hydrolysis. The organic carboxylates mentioned above may be used alone. However, it is preferable to use them in combination of two or more for viscosity regulation depending on the purposes. In the case of a complex type of organic carboxylate (3) having a high viscosity, for instance, its viscosity regulation depending on the purposes may be achieved by using an ester oil of an aliphatic polyhydric alcohol with a fatty acid having 3 to 9 carbon atoms, which has a viscosity of up to 120 mm 2 /s at 40°C. In the case of an organic carboxylate having a low viscosity, on the other hand, it is preferable to add a polymer to it for its viscosity regulation. The polymer used has preferably a viscosity of 500 mm 2 /s or higher, as measured at 40°C. For such polymers, use may be made e.g. of polyalkyl methacrylates (with the alkyl group having 4 to 8 carbon atoms), polyalkylene glycols (e.g., copolymers consisting of polypropylene or polyethylene glycol components and polypropylene glycol components, or polypropylene glycol components and polytetramethylene glycol components) and polyesters consisting of neopentyl glycol and an aliphatic dibasic acid and having the following formula: where m is an integer of 1 to 20 and n is an integer of 1 to 10. The amount of the polymer added, although not critical if an ester oil having a desired viscosity is obtainable, lies usually in the range of 1% by weight to 99% by weight. Other esters such as fumarate polymers may be used as well. The fumarate polymers are fumarate homopolymers or copolymers of fumarates with unsaturated aliphatic hydrocarbons, and has the following general formula: where R 1 and R 2 may be identical with or different from each other, and each stands for a linear or branched alkyl or allyl group having 1 to 9 carbon atoms, or a polyalkylene oxide group that may or may not be substituted at the terminals, R 3 represents an alkylene group, an unsubstituted alkylene group, or an alkylene oxide group, provided that R 3 accounts for 50 mole % or less of the whole, m is an integer greater than 0, and n is an integer of 1 or more, preferably 1 to 12. In this connection, it is noted that both terminals of the copolymer represented by the above formula are residues used for polymerization reaction, and are not shown for simplicity. More illustratively, mention is made of ester oligomers of e.g. diethyl fumarate and dibutyl fumarate. The lubricating oil bases have a viscosity lying in the range of 10 mm 2 /s to 500,000 mm 2 /s at 40°C. In the case of a refrigerating machine lubricating oil in particular, the oil base composed mainly of an ester oil having a viscosity lying in the range of 10 mm 2 /s to 500 mm 2 /s at 40°C is preferably used as the synthetic oil. In this case, the ester oil may be used alone. In this regard, it is preferable that the ester oil accounts for 100% by weight of the oil. In the following description, the additive or additives used with the lubricating oil compositions of the invention will be explained at great length. Aromatic Glycidyl Carboxylate Represented by General Formula (1) where R is a C 6-14 aryl or alkylaryl group, and n stands for an integer of 1 or 2, preferably 1. This aromatic glycidyl carboxylate is added to the lubricating oil composition so as to impart stability to hydrolysis thereto. When R is an aryl group, it may be phenyl and naphthyl. When R is an alkylaryl, it may be e.g. alkylated phenyl and naphthyl. More illustratively and more preferably, glycidyl benzoate, glycidyl terephthalate, glycidyl orthophthalate and alkylated glycidyl benzoate are used. These aromatic glycidyl carboxylates are much higher in reactivity with water than aliphatic glycidyl carboxylates or glycidyl ethers, for instance, and are excellent in compatibility with a non-chlorine type of fluorine-containing refrigerants, when formulated into a refrigerating machine oil composition. Preferably, the content of chlorine in these aromatic glycidyl carboxylates is 0.5% by weight or below. A chlorine content exceeding 0.5% by weight often results in precipitation. The aromatic glycidyl carboxylate may be added to the lubricating oil base in an amount of preferably 0.1% by weight to 20% by weight, more preferably 0.5% by weight to 5% by weight. At higher than 20% by weight, the glycidyl carboxylate offers some problems such as a lowering of the flash point of the resulting composition, a lowering of the compatibility of the composition with refrigerants or degradation of the stability of the composition itself. Now, explanation will be given to the phosphonate type additive having General Formula (2): where R 1 or each R 2 is selected from alkyl, aralkyl, aryl or hydroxyalkyl groups which may or may not have a substituent, and two R 2 's may be identical with or different from each other. The groups R 1 or R 2 may have hydroxyl, acyl, alkoxylcarbonyl, glycidyloxycarbonyl or other groups as substituents, and preferable examples of the substituents are hydroxyl, acyl, alkoxycarbonyl and glycidyloxycarbonyl groups. Specific but not exclusive examples of such a phosphonate type additive are dioctyl methylphosphonate, dioctyl hydroxymethylphosphonate, ethyl 3-phosphonopropionate, glycidyl σ,σ-dibutylphosphono-2-methylpropionate, dioctyl phenylphosphonate, diethyl phenylphosphonate and diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate. When the lubricating oil composition is formulated into a refrigerating machine oil composition, it is preferable that each R 2 in General Formula (2) is an alkyl group having 12 or less carbon atoms. Such a phosphonate type additive is well compatible with a refrigerant such as R134a, and lends itself particularly fit for being added to refrigerating machine oil. These phosphorous type additives may be used alone or in admixture. While phosphorous type additives represented by (RO) 3 P = O and (RO) 3 P where R has the same meanings as defined in connection with R 2 in General Formula (2) may be used in place of the phosphonate type additive having General Formula (2), it is understood that it is preferable to use the additives having General Formula (2). The phosphonate type additive having General Formula (2) may be used either alone or in admixture with the phosphorous additives mentioned above, and is used at a proportion of 0.05% by weight to 10% by weight relative to the lubricating oil base. At higher than 5% by weight, this additive poses a metal corrosion problem. The phosphonate type additive having General Formula (2) can well produce its own effect, when used in an oxygen-free atmosphere. In the present disclosure, the term "oxygen-free atmosphere" is understood to be applied generally to lubricating oil used in a closed system and, more specifically, to refrigerating machine oil used in a refrigerant, or to lubricating oil used in a nitrogenous atmosphere or in vacuo. This type of lubricating oil is used under conditions that are usually defined by partial oxygen pressure having an initial value of up to 10 -1 torr, preferably up to 10 -2 torr. A lubricating oil composition having much more improved stability is obtainable by the addition of a nitrogenous compound having General Formula (3): where R 1 is an alkyl or aryl group having 1 to 6 carbon atoms, R 2 is an alkylene or arylene group having 1 to 6 carbon atoms, and R 3 and R 4 are each an alkyl, aryl or alkylaryl having 1 to 12 carbon atoms and may form together a heterocycle, and n stands for an integer of 0 or 1. More specifically but not exclusively, R 1 and R 2 may be methyl, ethyl, and phenyl. Similarly, R 2 may be methylene, ethylene, and phenylene. R 3 and R 4 may independently be methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, and phenyl, and may form together a heterocyle such as a pyrrolidine or piperidine ring. More specifically but not exclusively, particular preference is given to 1-dioctylaminomethyl-4-methylbenzotriazole and 1-dioctylaminomethyl-5-methylbenzotriazole. The nitrogenous compound having General Formula (3) is added to the lubricating oil base in an amount of 0.01% by weight to 5% by weight. At higher than 5% by weight, the nitrogenous compound offers discoloration or other problems. Explanation will then be given to how the additives act in the lubricating oil composition of the invention. The lubricating oil composition is improved in terms of stability to hydrolysis by containing the aromatic glycidyl carboxylate having General Formula (1). Especially when the lubricating oil composition is used in the form of a refrigerating machine oil composition, it can exhibit excellent compatibility with a refrigerant. When the lubricating oil composition is used in the form of a refrigerating machine oil composition, it contains the phosphorous additive having General Formula (2) so as to reduce its action on wearing metals forming refrigerating machinery, e.g., aluminum and iron materials. In some cases, however, the aromatic glycidyl carboxylate reacts with the phosphorous additive to form by-products, which then settle down, resulting in pipe clogging occuring in refrigerating machinery. To ward off such undesired side reactions, the nitrogenous compound having General Formula (3) is added. The nitrogenous compound having General Formula (3), at the same time, acts to deactivate metals forming refrigerating machinery, e.g., inhibit copper from discoloring, thus providing a more stable refrigerating machine oil composition. The lubricating oil composition of the invention may additionally contain antioxidants, for instance, represented by amine type antioxidants such as di(alkylphenyl)amine (with the alkyl group having 4 to 20 carbon atoms), phenyl-α-naphthylamine, alkyldiphenylamine (with the alkyl group having 4 to 20 carbon atoms), N-nitroso-diphenylamine, phenothiazine, N,N'-dinaphthyl-p-phenylenediamine, acridine, N-methylphenothiazine, N-ethylphenothiazine, dipyridylamine, diphenylamine, phenolamine and 2,6-di-t-butyl-α-dimethylamino p-cresol; phenolic antioxidants such as 2,6-di-t-butyl p-cresol, 4,4'-methylenebis(2,6-di-t-butylphenol), 2,6-di-t-butyl-4-N,N-dimethylaminomethylphenol and 2,6-di-t-butylphenol; organic metal compound type antioxidants such as organic iron salt, e.g., iron octoate, ferrocene and iron naphthoate, organic cerium salts, e.g., cerium naphthoate and cerium toluate, and organic zirconium salts, e.g., zirconium octoate; and phosphites such as tri-di-t-butylphenyl phosphite and trioctyl phosphite. These antioxidants may be used alone or in combination of two or more. The antioxidant(s) mentioned above may be used in an amount of 0.001% by weight to 5% by weight, preferably 0.01 to 2% by weight relative to the oil base. Moreover, the lubricating oil composition of the invention may contain some other additives such as detergent-dispersants, corrosion inhibitors, anti-defoaming agents, metal deactivators and rust preventives. The refrigerating machine lubricating oil composition of the invention may contain corrosion inhibitors, wear preventives, anti-foaming agents, metal deactivators and rust preventives. The detergent-dispersant used includes e.g. an imide succinate or alkylbenzene sulfonate. The corrosion inhibitor used includes isostearate, n-octadecyl ammonium stearate, Duomin T·dioleate, lead naphthenate, sorbitan oleate, pentaerythritol·oleate, oleyl-sarcosine, alkyl succinate, alkenyl succinate, and their derivatives. These inhibitors may be used in an amount of 0.001% by weight to 1.0% by weight, preferably 0.01% by weight to 0.5% by weight relative to the oil base. The anti-foaming agent may be silicone, and may be used in an amount of 0.0001% by weight to 0.003% by weight, preferably 0,0001% by weight to 0.001% by weight relative to the oil base. The metal deactivators used, for instance, may be thiadiazoles, thiadiazole derivatives, triazoles, triazole derivatives and dithiocarbamates, and may be used in an amount of 0.01% by weight to 10% by weight, preferably 0.01% by weight to 1.0% by weight relative to the oil base. The corrosion inhibitors used, for instance, may be succinic acid, succinates, oleic acid tallow amide, barium sulfonate and calcium sulfonate, and may be used in an amount of 0.01% by weight to 10% by weight, preferably 0.01% by weight to 1.0% by weight relative to the oil base. In the following description, the viscosity range of the lubricating oil composition according to the invention will be explained at great length. As already mentioned, the lubricating oil composition of the invention has a viscosity lying in the range of 10 to 500,000 mm 2 /s at 40°C. When used in the form of a refrigerating machine oil composition, the lubricating oil composition of the invention has a viscosity lying in the range of 10 to 500 mm 2 /s, preferably 20 to 480 mm 2 /s at 40°C, whereas when used for a refrigerator, it has a viscosity lying in the range of 10 mm 2 /s to 40 mm 2 /s, preferably 15 mm 2 /s to 35 mm 2 /s at 40°C. In order for the lubricating oil composition of the invention to be used in the form of refrigerating machine oil for a refrigerating machine of a car air conditioner, it has preferably a viscosity in the range of 40 mm 2 /s to 500 mm 2 /s. When used for a reciprocation type compressor of a car air conditioner, it has preferably a viscosity in the range of 40 mm 2 /s to 120 mm 2 /s, desirously 80 mm 2 /s to 100 mm 2 /s, and when used for a rotary type compressor, it has preferably a viscosity in the range of 80 mm 2 /s to 500 mm 2 /s, desirously 100 mm 2 /s to 450 mm 2 /s. At less than 10 mm 2 /s, the lubricating oil composition of the invention is well compatible with refrigerants at elevated temperatures, but poses some problems in connection with lubricating properties, sealing properties and heat stability due to its low viscosity. A lubricating oil composition having a viscosity exceeding 500 mm 2 /s is not preferable, because its compatibility with refrigerants becomes low. Even within the range of 10 to 500 mm 2 /s, the viscosity of the lubricating oil composition of the invention varies depending on what types of machinery are used with it. For instance, the lubricating oil composition for refrigerators gives rise to large friction loss at sliding portions, when its viscosity exceeds 40 mm 2 /s. Further, the lubricating oil composition for a reciprocation type of car air conditioner offers a problem in connection with lubricating properties, when its viscosity becomes less than 40 mm 2 /s, whereas it gives rise to large friction loss at sliding portions, when its viscosity exceeds 120 mm 2 /s. Still further, the lubricating oil composition for a rotary type of air conditioner poses a problem in connection with sealing properties, when its viscosity becomes below 80 mm 2 /s, whereas it offers a problem in connection with compatibility with refrigerants, when its viscosity exceeds 500 mm 2 /s. While the present invention will now be explained with reference to some examples, it is understood that the "stability to hydrolysis", "stability to oxidation", "lubricating properties" and "compatibility" referred to therein were measured by the following procedures. Stability to Hydrolysis Sample or control oil (250 ml), one copper wire, one aluminum wire, one iron wire, (all serving as catalysts and of 8 mm in inner diameter and 30 mm in length), water (1,000 ppm) and a refrigerant flon 134a (40g) were placed in an iron vessel having an inner volume of 350 ml, which was heated at 175°C for 20 days, and from which the oil was then removed to determine the total acid number, in mg KOH/g, by the JIS K 2501 neutralization number testing procedure. Stability to Oxidation Sample or control oil (250 ml), one copper wire, one aluminum wire, one iron wire, (all serving as catalysts and of 8 mm in inner diameter and 30 mm in length), water (1,000ppm), a refrigerant flon 134a (40g) and air (100 ml) were placed in an iron vessel having an inner volume of 350 ml, which was heated at 175°C for 20 days, and from which the oil was then removed to determine the total acid number, in mg KOH/g, by the JIS K 2501 neutralization number testing procedure. Apart from this, suspended solids in the oil were visually observed to determine whether or not there was precipitation. Lubricating Properties of Oil or Abrasion Loss of Test Pieces Aluminum and cast iron sheets were used with a ball-on-disk type of abrasion testing machine under the following condition, thereby determining the abrasion widths in mm. Abrasion Testing Conditions Load: 12.7 N Friction Speed: 3 mm/s Disk: A390 Balls: 1/4-inch bearing balls of SUS440C Atmosphere: in the air or R134a under 700 mmHg Temperature: room temperature (25°C) Compatibility Testing Procedure Sample or control oil (11.7% by weight) and a refrigerant (1.1.1.2-tetrafluoroethane) were mixed together at a total amount of 2 ml in a glass tube. The glass tube is placed in a constant temperature bath having a heater and a cooler to measure the temperature at which the sample oil separates from the refrigerant. Sealed Tube Testing Sample oil (1 g), 1.1.1.2-tetrafluoroethane (1 g) and each of iron, copper and aluminum test metal pieces (of 1.7 mm in diameter and 40 mm in length) were heat-sealed in a glass tube. After this, the glass tube was heated at the temperature of 175°C for 14 days (366 hours). After the completion of the testing, the degree of discoloration of the test oil was measured, and the state of the metal piece was observed. Example 1 Antioxidants di(octylphenyl)amine (0.20% by weight) and 2,6-di-t-butyl-4-N,N-dimethylaminomethylphenol (0.10% by weight), and glycidyl benzoate with a chlorine content of 0.1% by weight (2.0% by weight) were added to an ester obtained by the reaction of dipentaerythritol with C 5 (30% by weight) - C 6 (70% by weight) fatty acids at the ratio of 1:6, said ester having a viscosity of 72 mm 2 /s at 40°C), thereby preparing Sample Oil 1. In addition, trioctyl phosphate (0.5% by weight) and the nitrogenous compound (0.1% by weight), given below, were added to Sample Oil 1 to prepare Sample Oil 2. Example 2 As in the case of Sample Oil 2, Sample Oil 3 was prepared with the exception that diglycidyl terephthalate was used in place of the glycidyl benzoate. Example 3 As in the case of Sample Oils 1 and 2, Sample Oils 4 and 5 were prepared with the exception that no antioxidants were used at all. Comparative Example 1 As in the case of Sample Oil 2, Comparative Oil 1 was prepared with the exception that phenyl glycidyl ether was used in lieu of the glycidyl benzoate. Comparative Example 2 As in the case of Sample Oil 2, Comparative Oil 2 was prepared with the exception that glycidyl 2-ethylhexoate was used in lieu of the glycidyl benzoate. Comparative Example 3 As in the case of Sample Oil 3, Comparative Oil 3 was prepared with the exception that the nitrogenous compound was not used at all. Comparative Example 4 As in the case of Sample Oil 3, Comparative Oil 4 was prepared with the exception that benzotriazole was used in place of the nitrogenous compound. Sample Oils 1-5 and Comparative Oils 1-4 were tested as to their stability to hydrolysis and compatibility with a refrigerant. The results are set out in Table 1. Stability Compatibility with Refrigerant T.A.N. Precipitation L.T. H.T. S.O. 1 0.07 not found -40°C or below 80°C or more 2 0.07 - - - 3 0.04 - - - 4 0.07 - - - 5 0.07 - - - C.O. 1 0.30 - - - 2 0.30 - clouding found at room temperature 3 0.04 found -40°C or below 80°C or more 4 0.04 found - - T.A.N.: Total Acid Number in mg KOH/g L.T.: Low Temperature in °C H.T.: High Temperature in °C S.O.: Sample Oil C.O.: Comparative Oil As can be seen from Table 1, the lubricating oil compositions of the invention are excellent in stability to hydrolysis and well compatible with the R134a refrigerant, and so provide excellent refrigerating machine oil compositions. Example 4 Antioxidants di(octylphenyl)amine (0.20% by weight) and 2,6-di-t-butyl-4-N,N-dimethylaminomethylphenol (0.10% by weight), and glycidyl σ,σ-dibutylphosphono-2-methylpropionate (2.0% by weight), given below, were added to an ester obtained by the reaction of dipentaerythritol with 2-methylhexoic acid at the molar ratio of 1:6, said ester having a viscosity of 72 mm 2 /s at 40°C, thereby preparing Sample Oil 6. Example 5 As in the case of Sample Oil 6, Sample Oil 7 was prepared with the exception that 2% by weight of dioctyl hydroxymethylphosphonate was used in place of the glycidyl σ,σ-dibutylphosphono-2-methylpropionate. Example 6 As in the case of Sample Oil 6, Sample Oil 8 was prepared with the exception that 2% by weight of ethyl 3-diethylphosphonopropionate, given below, was used in place of the glycidyl σ,σ-dibutylphosphono-2-methylpropionate. Example 7 As in the case of Sample Oil 6, Sample Oil 7 was prepared with the exception that 2% by weight diethyl phenylphosphonate, given below, was used in place of the glycidyl σ,σ-dibutylphosphono-2-methylpropionate. Example 8 As in the case of Sample Oil 6, Sample Oil 10 was prepared with the exception that 2% by weight of diethyl 3,5-di-t-butyl-4-hydroxybenzylphosphonate, given below, was used in place of the glycidyl σ,σ-dibutylphosphono-2-methyl-propionate. Example 9 As in the case of Sample Oil 6, Sample Oil 11 was prepared with the exception that no antioxidant was used at all. Example 10 Glycidyl benzoate with a chlorine content of 0.1% by weight (2.0% by weight) and ethyl 3-diethylphosphonopropionate (2% by weight) were added to an ester obtained by the reaction of dipentaerythritol with C 5 (30% by weight) - C 6 (70% by weight) fatty acids at the ratio of 1:6, said ester having a viscosity of 72 mm 2 /s at 40°C), thereby preparing Sample Oil 12. In addition, 0.1% by weight of the nitrogenous compound, given below, was added to Sample Oil 19 to prepare Sample Oil 13. Comparative Example 5 As in the case of Sample Oil 6, Comparative Oil 5 was prepared with the exception that 2% by weight of tricresyl phosphate was used in place of the glycidyl o,o-dibutyl-phosphono-2-methylpropionate. Comparative Example 6 As in the case of Sample Oil 6, Comparative Example 6 was prepared with the exception that 2% by weight of tri-1,3-dichloropropylphosphate, given below, was used in the place of the glycidyl o,o-dibutylphosphono-2-methylpropionate. O = P - (OCHClCH 2 CH 2 Cl) 3 Comparative Example 7 Comparative Oil 7 was Sample Oil 6 free from glycidyl o,o-dibutylphosphono-2-methylpropionate. Sample Oils 6-13 and Comparative Oils 5-7 were subjected to abrasion testing. The results are set out in Table 3. Al Abrasion Loss (x 10 -3 mm 3 ) Fe Abrasion Dent Diameter (mm) in the air in R134a in the air in R134a S.O. 6 1.2 0.8 17 16 7 1.0 0.6 15 14 8 1.4 1.2 18 16 9 1.0 0.6 15 14 10 1.2 0.8 17 16 11 1.2 0.8 17 16 12 1.0 0.6 15 13 13 1.0 0.6 15 13 C.O. 5 0.6 2.3 15 21 6 1.5 3.1 17 21 7 2.1 2.3 20 21 S.O.: Sample Oil C.O.: Comparative Oil As can be seen from Table 3, the lubricating oil compositions of the invention exhibit excellent lubricating properties in the oxygen-free atmosphere, and so provide excellent refrigerating machine oil, for instance. Then, the capability of Sample Oils 6, 8 and 10-13 to be used as refrigerating oil was estimated by compatibility, stability-to-hydrolysis and sealed tube testings. It is noted that the compatibility testing was carried out as follows. Compatibility Testing Procedure A sample oil (3% by weight) and a refrigerant - 1.1.1.2-tetrafluoroethane (10% by weight) are mixed together in a glass tube at a total amount of 2 ml. The glass tube is then placed in a constant temperature bath having a heater and a cooler to measure the temperature at which the sample oil separates from the refrigerant. The results are set out in Tables 4 and 5. Sample Oil Sample Oil 6 Sample Oil 8 Sample Oil 10 Sample Oil 11 Compatibility with Refrigerant High-Temperature Phase Separation. Temperature ; Oil Fraction 10 wt % 90°C or More 90°C or More 90°C or More 90°C or More Low-Temperature Phase Separation Temperature; Oil Fraction 10 wt % -40°C -40°C -40°C -40°C Stability to Hyrolysis after Testing 0.05 0.05 0.05 0.08 Sealed Tube Testing Color (ASTM) 1.0 1.0 1.0 1.0 Catalyst Appearance Good Good Good Good Sample Oil Sample Oil 12 Sample Oil 13 Compatibility with Refrigerant High-Temperature Phase Separation Temperature; Oil Fraction 10 wt % 80°C or More 80°C or More Low-Temperature Phase Separation Temperature; Oil Fraction 10 wt % - 40°C or Less -40°C or Less Stability to Hyrolysis after Testing 0.07 0.07 Sealed Tube Testing Color (ASTM) 1.0 1.0 Catalyst Appearance Good Good As can be appreciated from Tables 4 & 5, the lubricating oil compositions of the invention are excellent in compatibility with the refrigerant, stability to hydrolysis and chemical and thermal stability at elevated temperatures and low temperatures as well, and provide particularly excellent refrigerating machine oil that is used with a refrigerant R134a.

Claims: A refrigerating machine lubricating oil composition comprising a lubricating oil base consisting essentially of a polyester of an aliphatic polyhydric alcohol with linear or branched fatty acids having from 3 to 12 carbon atoms and having a viscosity in the range of 10 mm 2 /s to 500 mm 2 /s at 40°C and which contains 0.1% by weight to 20% by weight relative to the weight of lubricating oil base of an aromatic glycidyl carboxylate having the following general formula (1): wherein R is an aryl or alkylaryl group having 6 to 14 carbon atoms, and n represents an integer of 1 or 2. A lubricating oil composition according to claim 1 which contains 0.05% by weight to 10% by weight relative to the weight of lubricating oil base of a phosphonate type additive having the following general formula (2): wherein R 1 or R 2 are selected from the group consisting of alkyl, aralkyl, aryl and hydroxyalkyl groups which may or may not have a substituent, and two R 2 groups may or may not be identical with each other. A lubricating oil composition according to any of the preceding claims which further contains 0.01% by weight to 5% by weight relative to the weight of lubricating oil base of a benzotriazole derivative having the following general formula (3): wherein R 1 is an alkyl or aryl group having 1 to 6 carbon atoms, R 2 is an alkylene or arylene group having 1 to 6 carbon atoms, R 3 and R 4 is an alkyl, aryl or alkylaryl group having 1 to 12 carbon atoms, or R 3 and R 4 may form together a heterocycle, and n is an integer of 0 or 1. A lubricating refrigerating composition comprising a lubricating oil composition as claimed in any one of claims 1 to 3 together with a refrigerant that is a non-chlorine type fluorine-containing refrigerant.

Inventors: KURIBAYASHI TOSHIAKI, SATO TAKEHISA, UEDA HIRONARI, KURIBAYASHI, TOSHIAKI, SATO, TAKEHISA, UEDA, HIRONARI, Kuribayashi, Toshiaki, c/o TONEN CORPORATION, Sato, Takehisa, c/o TONEN CORPORATION, UEDA, HIRONARI, C/O TONEN CORPORATION
Applicants: TONEN CORP, TONEN CORPORATION
Application year: 1993
Main classification: C10M129
IPC codes: C10M169, C10M129, C10N20, C10M137, C10N40, C10M141, C10M171, C10N30