WO2000058425A1

WO2000058425A1 - Refrigerating machine oil composition

Info

Publication number: WO2000058425A1
Application number: PCT/JP1999/004496
Authority: WO
Inventors: Yuji Shimomura; Satoshi Suda; Hiroyuki Hirano
Original assignee: Nippon Mitsubishi Oil Corporation
Priority date: 1999-03-26
Filing date: 1999-08-20
Publication date: 2000-10-05
Also published as: JP2000273477A; AU5303099A

Abstract

A refrigerating machine oil composition which comprises an alicyclic dicarboxylic acid ester compound having an alicyclic ring and two ester groups which are represented by the following general formula (1) and are bonded respectively to carbon atoms adjacent to each other on the ring, wherein the ester compound is cis with respect to the configuration of the two ester groups: -COOR1 (wherein R1 represents a C¿1-30? hydrocarbon group and R?1¿s of all the ester groups may be the same or different).

Description

Akitoda

Refrigeration oil composition

Technical field

The present invention relates to a refrigerator oil composition, and more particularly to a refrigerator oil composition containing an alicyclic dicarboxylic acid ester compound.

Background art

In view of the recent problems of ozone depletion and global warming, alternatives to refrigerants and higher efficiency of refrigeration systems are being studied. In the replacement of refrigerants, switching from chlorine-containing refrigerants such as CFCs (fluorocarbons) and HFCs (fluorocarbons) to HFCs (fluorocarbons) is being promoted. On the other hand, HFC refrigerants can also be subject to regulation from the perspective of global warming, and the use of natural refrigerants such as carbon dioxide, ammonia, and hydrodynamic hydrogen is being considered.

In response to this trend of refrigerant substitution, development of refrigeration oil for alternative refrigerants is underway. Refrigeration oil requires many performances such as lubricity, refrigerant compatibility, heat and hydrolysis stability, electrical insulation, and low moisture absorption. A compound is selected. For example, refrigeration oils for HFCs include oxygen-containing compounds such as esters, ethers, and carbonates that are compatible with refrigerants, or alkylbenzenes that have poor refrigerant compatibility but have excellent lubricity and thermal and hydrolytic stability. Etc. are used.

From the viewpoint of increasing the efficiency of the refrigeration system, studies have been made to reduce the viscosity of the refrigeration oil. An ester-based refrigerating machine oil is obtained by reacting an aliphatic polyhydric alcohol with a fatty acid as disclosed in Japanese Patent Application Laid-Open Publication No. Hei 3 (1993) -502602. Polyol esters are known, and such ester-based refrigerating machine oils have a low viscosity. One of the effective measures is to select a fatty acid having a small carbon number in the alkyl group of the fatty acid used as a raw material. However, generally, when the alkyl group of the fatty acid becomes small, a problem occurs in that the heat and hydrolysis stability of the obtained ester is reduced.

Japanese Patent Application Laid-Open No. 9-122211 is an ester refrigerating machine oil with excellent heat and hydrolysis stability.

Although an alicyclic polycarboxylic acid ester as disclosed in 90 is known, even if the ester has such a structure, when the viscosity is reduced, the heat and hydrolysis stability is low. It is not enough.

As described above, an ester-based refrigerating machine oil that satisfies both low viscosity for high efficiency and high thermal stability with hydrolysis while satisfying other required performances has not yet been developed. Disclosure of the invention

The present invention has been made in view of the above-mentioned problems of the related art, and when used together with HFC refrigerant and natural refrigerants such as carbon dioxide and hydrodynamic carbon, lubricity, refrigerant compatibility, heat · It is an object of the present invention to provide a refrigerating machine oil composition which is excellent in hydrolytic stability, electric insulation properties, etc. and enables high efficiency of a refrigerating system.

The present inventors have conducted intensive studies to achieve the above object, and as a result, have found that a refrigerating machine oil composition excellent in various performances can be obtained by using a base oil containing a specific ester oil. .

The refrigerator oil composition of the present invention has an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are adjacent to each other on the alicyclic ring. A cis-type alicyclic dicarboxylic acid ester compound which is bonded to a carbon atom and is cis-form with respect to two orientations of the ester group

-COOR ¹ (1)

(In the formula, R ¹ represents a hydrocarbon group having 0 to 3 carbon atoms, R ¹ for each ester group They may be the same or different. )

It contains.

The refrigerator oil composition of the present invention preferably further contains an epoxy compound and / or a phosphorus compound. As such an epoxy compound, at least one compound selected from the group consisting of a phenylglycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound and an epoxidized fatty acid monoester is preferable. Type epoxy compounds and / or alicyclic epoxy compounds are more preferred.

A fluid composition for a refrigerator according to the present invention contains the refrigerator oil composition of the present invention and a non-chlorine-containing chlorofluorocarbon. BEST MODE FOR CARRYING OUT THE INVENTION

Hereinafter, preferred embodiments of the present invention will be described in detail.

The cis-type alicyclic dicarboxylic acid ester compound according to the present invention refers to an alicyclic ring and two ester groups represented by the following general formula (1), and two of the ester groups are alicyclic rings. It bonds to adjacent carbon atoms on the formula ring and is cis-form with respect to the two orientations of the ester group.

-C 0 0 R ¹ (1)

(In the formula, R ¹ represents a hydrocarbon group having 0 to 3 carbon atoms, R ¹ for each ester group may be the same or different.)

The alicyclic ring referred to here includes a cyclopentane ring, a cyclopentene ring, a cyclohexane ring, a cyclohexene ring, a cycloheptane ring, a cycloheptene ring, and the like, and a cyclohexane ring and a cyclohexene ring are preferable. . Further, among these, a cyclohexane ring is more preferable because of a small increase in viscosity when used under long-term or severe conditions, and a cyclohexene ring is preferably used when a long-term or severe condition is used. It is more preferable because the increase in the value is small. The cis-type alicyclic dicarboxylic acid ester compound needs to have two alicyclic rings and two ester groups represented by the above formula (1). It is not preferred that the number of ester groups is one, because the compatibility with the refrigerant and the stability of heat and hydrolysis are insufficient. When the number of ester groups is 3 or more, it is not preferable from the viewpoint of low-temperature fluidity.

In addition, the two ester groups represented by the above formula (1) are bonded to mutually adjacent carbon atoms on the alicyclic ring from the viewpoint of thermal and hydrolytic stability, and furthermore, the two ester groups It is necessary to be a cis-body with respect to the orientation of.

R ¹ in the above formula (1) represents a hydrocarbon group having ¹ to 30 carbon atoms, preferably 2 to 24 carbon atoms, and more preferably 3 to 18 carbon atoms. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, an alkylcycloalkyl group, an aryl group, an alkylaryl group, and an arylalkyl group. Among these, an alkyl group, a cycloalkyl group or an alkylcycloalkyl group is preferred from the viewpoint of stability of hydrothermal decomposition.

The alkyl group may be linear or branched. Examples of the alkyl group having 3 to 18 carbon atoms include, for example, a linear or branched propyl group, a linear or branched butyl group, a linear or branched pentyl group , Linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear Or a branched decyl group, a linear or branched pendecyl group, a linear or branched dodecyl group, a linear or branched tridecyl group, a linear or branched Tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched hepdecyl decyl group, linear or branched And a decyl group.

Among them, the linear alkyl group is preferably a group having 5 or more carbon atoms from the viewpoint of thermal and hydrolytic stability, and is preferably a group having 18 carbon atoms or less from the viewpoint of refrigerant compatibility. Good. The branched alkyl group preferably has 3 or more carbon atoms from the viewpoint of heat and hydrolysis stability, and has 18 or less carbon atoms from the viewpoint of refrigerant compatibility.

Examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group and the like, and a cyclohexyl group is preferred from the viewpoint of heat and hydrolysis stability. The alkylcycloalkyl group is a group in which an alkyl group is bonded to a cycloalkyl group, and is preferably a group in which an alkyl group is bonded to a cyclohexyl group from the viewpoint of heat and hydrolysis stability. Further, the alkylcycloalkyl group preferably has a total carbon number of 6 or more from the viewpoint of heat and hydrolysis stability, and preferably has a total carbon number of 10 or less from the viewpoint of refrigerant compatibility and low-temperature fluidity. .

Further, as the cis-type alicyclic dicarboxylic acid ester compound, one or more hydrocarbon groups may be bonded to a carbon atom on the alicyclic ring. As such a hydrocarbon group, an alkyl group is preferable, and a methyl group is particularly preferable. The cis-type alicyclic dicarboxylic acid ester compound referred to in the present invention has the above-mentioned structure. Such an ester compound is prepared by converting a predetermined acid component and an alcohol component according to a conventional method, preferably using nitrogen or the like. It is prepared by esterification while heating under an inert gas atmosphere, under an atmosphere of an esterification catalyst or under no catalyst. Here, from the viewpoints of heat / hydrolysis stability and electric insulation, it is preferable to prepare by an esterification reaction in the absence of a catalyst.

The acid component of the cis-type alicyclic dicarboxylic acid ester compound is cis-cycloalkanedicarboxylic acid, cis-cycloalkenedicarboxylic acid or an acid anhydride thereof, and two ester groups are formed on the alicyclic ring. And those bonded to carbon atoms adjacent to each other, and these can be used as one kind or as a mixture of two or more kinds. Specifically, cis-1,2-cyclohexanedicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, cis-1-cyclohexene-1,2-dicarboxylic acid, cis-3 —Methyl-1, 2-cyclohexa. Carboxylic acid, cis-4-methyl-1-, 2-cyclohexanedicarboxylic acid, cis-3-methyl-4-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-4-cyclohexene-1 , 2-Dicarboxylic acids and their anhydrides are disclosed. Among them, cis-1,2-cyclohexanedicarboxylic acid, cis-3-methyl-1,1,1-methyl-1,1,2-cyclohexyldicarboxylic acid are used from the viewpoint of suppressing the increase in viscosity of the prepared ester compound when used under long-term or severe conditions. 2-cyclohexanedicarboxylic acid, cis-4-methyl-1,2-cyclohexanedicarboxylic acid and their acid anhydrides are preferred, while increasing the total acid value when used under long-term or severe conditions. From the viewpoint of suppression, cis-4-cyclohexene-1,2-dicarboxylic acid, cis-1-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-11,2-cyclohexanedicarboxylic acid Preferred are cis-3-methyl-4-cyclohexene-1,2-dicarboxylic acid, cis-4-methyl-14-cyclohexene-1,2-dicarboxylic acid and their anhydrides.

The method for producing these cis-type alicyclic dicarboxylic acids and anhydrides is not particularly limited, and those obtained by any method can be used. Specifically, for example, cis_4-cyclohexene-1,2-dicarboxylic acid can be obtained by reacting butadiene and maleic anhydride at 100 ° C. in a benzene solvent.

The alcohol component of the cis-type alicyclic dicarboxylic acid ester compound includes a linear alcohol having 3 to 18 carbon atoms, a branched alcohol having 3 to 18 carbon atoms, and a cycloalcohol having 5 to 10 carbon atoms. Is mentioned. Specific examples include linear or branched propanol (including n-propanol and 1-methylethanol), and linear or branched butanol (n-butanol and 1-methylpropanol). , 2-methylpropanol, etc.), linear or branched pentanols (including n-phenol, 1-methylbutanol, 2-methylbutanol, 3-methylbutanol, etc.), Linear or branched hexanols (including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol, etc.) ), Linear or branched heptanol (n-hepanol, 1-methylhexanol, 2-methylhexanol, 3-methylhexanol, 4-methylhexanol, 5-methylhexanol) Includes xanol, 2,4-dimethylpentanol, etc., linear or branched octanol (n-octanol, 2-ethylhexanol, 1-methylheptanol, 2-methylheptanol, etc.) ), Linear or branched nonanol (n-nonanol, 1-methyloctanol, 3,5,5-trimethylhexanol, 11- (2'-methylpropyl) -13-methylbutanol, etc. ), Linear or branched decanol (including n-decanol, iso-decanol, etc.), linear or branched decanol (including n-decanol, etc.) ), Linear Or branched dodecanol (including n-dodecanol, iso-dodecanol, etc.), linear or branched tridecanol, linear or branched tetradecanol (n-tetradecanol) Octanol, iso-tetradecanol, etc.), linear or branched pentadecanol, linear or branched hexadecanol, n-hexanol, iso-hexade Linear or branched heptane decanol, linear or branched octadecanol (n- or octadecanol, etc.) Hex), methylhexanol, methylcyclohexanol, dimethylcyclohexanol, and the like.

In carrying out the esterification reaction, the alcohol component is used, for example, in an amount of 1.0 to 1.5 equivalents, preferably 1,05 to L.2 equivalents, per equivalent of the acid.

Further, instead of the acid component and the alcohol component, a lower alcohol ester of the acid component and / or an acetic acid ester or a propionic acid ester of the alcohol are used, and a cis-type aliphatic dicarboxylic acid ester compound is subjected to a transesterification reaction. It is also possible to get

Examples of the esterification catalyst include Lewis acids, alkali metal salts, and sulfonic acids. Specific examples of the Lewis acid include aluminum derivatives, tin derivatives, and titanium derivatives. Examples of the alkali metal salts include sodium alkoxide and potassium alkoxide, and examples of the sulfonic acids include paratoluenesulfonic acid, methanesulfonic acid, and sulfuric acid. The amount used is, for example, about 0.1 to 1% by mass based on the total amount of the raw material acid component and alcohol component.

The temperature for esterification is, for example, 150 ° C. to 230 ° C., and the reaction is usually completed in 3 to 30 hours.

After completion of the esterification reaction, the excess raw material is distilled off under reduced pressure or steam pressure, and then the ester compound is purified by a conventional purification method, for example, adsorption purification treatment such as liquid-liquid extraction, reduced pressure distillation, and activated carbon treatment. can do.

Although the content of the cis-type alicyclic dicarboxylic acid ester compound in the refrigerator oil composition of the present invention is not particularly limited, the excellent various performances of the cis-type alicyclic dicarboxylic acid ester compound can be further derived. It is preferably contained in an amount of at least 5% by mass, more preferably at least 10% by mass, even more preferably at least 30% by mass, more preferably at least 50% by mass, based on the total amount of the refrigerator oil composition. Is most preferred.

In the refrigerator oil composition of the present invention, the cis-type alicyclic dicarboxylic acid ester compound is mainly used as a base oil. As the base oil of the refrigerator oil composition of the present invention, only the cis-type alicyclic dicarboxylic acid ester compound may be used, but in addition to the cis-type alicyclic dicarboxylic acid ester compound specified in the present invention such as a polyol ester or a complex ester. Synthetic oils containing oxygen such as esters other than cyclic dicarboxylic acid ester compounds, polyglycols, polyvinyl ethers, ketones, polyphenylene ethers, silicones, polysiloxanes, and perfluoroethers may be used in combination. . The amount of the synthetic oil containing oxygen is not particularly limited. However, from the viewpoint of improving the thermal efficiency and the stability of heat and hydrolysis of the refrigerating machine oil, 100 parts by weight of the cis-type alicyclic dicarboxylic acid ester compound is The amount of the synthetic oil containing oxygen is preferably at most 150 parts by weight, more preferably at most 100 parts by weight.

The refrigerating machine oil composition of the present invention contains a cis-type alicyclic dicarboxylic acid ester compound and, if necessary, a synthetic oil containing oxygen, and is mainly used as a base oil. The refrigerating machine oil composition of the present invention can be suitably used in a state in which no additives are added, but may be used in a form in which various additives are blended as necessary.

In order to further improve the wear resistance and load bearing capacity of the refrigerator oil composition of the present invention, a phosphate ester, an acid phosphate, an amine salt of an acid phosphate, a chlorinated phosphate and a phosphite are used. At least one phosphorus compound selected from the group consisting of: These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanol or polyether-type alcohol or derivatives thereof.

Specifically, for example, phosphate esters include triptyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, and tridecyl phosphate. , Tridecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate, tripene decyl phosphate, trihexadecyl phosphate, trihepdecyl decyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate , Tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate and the like. Examples of the acidic phosphoric acid ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, and monodecyl. Acid phosphate, monoundecyl acid phosphate, mono Dodecyl acid phosphate, mono tridecyl acid phosphate, monotetradecyl acid phosphate, monopen decyl acid phosphate, monohexadecyl acid phosphate, monohepcyl decyl acid phosphate, monooctyl decyl acid phosphate Phosphate, mono-oleic acid phosphate, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate Didecyl acid phosphate, didecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipen Decyl acid phosphate Hue Ichito, hexadecyl acid phosphate to di-, Jihepu evening decyl Acid phosphatase We over preparative, di O Kuta decyl Acid phosphatase We Ichito, like Jiorei Rua Cid phosphate. Examples of the amine salt of the acidic phosphoric acid ester include the acidic phosphoric acid ester methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, getylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine. And diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, and trioctylamine. Examples of chlorinated phosphates include tris-dichloro propyl phosphate, tris-chloroethyl phosphate, tris-chloro phenyl phosphate, polyoxyalkylene bis [di (chloroalkyl). ] Phosphates and the like. Examples of phosphites include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, octyl phosphite, dinonyl phosphite, didecyl phosphite, and didecyl phosphite. Phyto, didodecyl phosphite, giorail phosphite, diphenyl phosphite, dicresyl phosphite, tributyl Phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, trindecyl phosphite, tri Dodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite and the like can be mentioned. Also, a mixture of these can be used.

When these phosphorus compounds are blended with the refrigerator oil composition of the present invention, the amount of the phosphorus compound is not particularly limited. However, the content is usually based on the total amount of the refrigerator oil composition (based on the total weight of the base oil and all the blended additives). It is desirable to add a phosphorus compound in such an amount that the amount becomes 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass.

Further, in the refrigerator oil composition of the present invention, in order to further improve its thermal and hydrolytic stability,

(1) Phenyl glycidyl ether type epoxy compound

(2) Alkyl glycidyl ether type epoxy compound

(3) glycidyl ester type epoxy compound

(4) aryloxy compounds

(5) Alkoxylan compound

(6) Alicyclic epoxy compound

(7) Epoxidized fatty acid monoester

(8) Epoxidized vegetable oil

At least one epoxy compound selected from the group consisting of:

D) Specific examples of the phenylglycidyl ether type epoxy compound include phenylglycidyl ether and alkylphenylglycidyl ether. The alkylphenyl glycidyl ether referred to herein includes those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, among which those having 1 alkyl group having 4 to 10 carbon atoms, for example, n-butylphenylglycidyl ether, i-butyl R-phenylglycidyl ether, S-C-butylphenylglycidyl ether, tert-butylphenylglycidylether, pentylphenylglycidylether, hexylphenyldaricidylether, heptylphenylglycidylether, octylphenylglycidylether Monoter, nonylphenylglycidylether, decylphenylglycidylether and the like can be exemplified as preferable ones.

(2) Specific examples of the alkylglycidyl ether type epoxy compound include decyl glycidyl ether, pendecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, Ethyl hexyl glycidyl ether, neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, erythritol pentayl glycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether And polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether and the like.

(3) Specific examples of the glycidyl ester type epoxy compound include compounds represented by the following general formula (2).

R— C-1 0— C-1 C-1 C

o

... General formula (2) (In the above formula, R represents a hydrocarbon group having 1 to 18 carbon atoms.)

In the above formula, R represents a hydrocarbon group having 1 to 18 carbon atoms. Examples of such a hydrocarbon group include an alkyl group having 1 to 18 carbon atoms, an alkenyl group having 2 to 18 carbon atoms, and a carbon atom. Cycloalkyl group having 5 to 7 carbon atoms, alkylcycloalkyl group having 6 to 18 carbon atoms, aryl group having 6 to 10 carbon atoms, alkyl aryl group having 7 to 18 carbon atoms, 7 carbon atoms To 18 arylalkyl groups. Of these, an alkyl group having 5 to 15 carbon atoms, an alkenyl group having 2 to 15 carbon atoms, a phenyl group and an alkyl group having an alkyl group having 1 to 4 carbon atoms are preferable.

Of the glycidyl ester type epoxy compounds, preferred are, for example, glycidyl-1,2,2-dimethyloctanoate, glycidylbenzoate, glycidyl-tert-butylbenzoate, glycidylacrylate, glycidylmethacrylate An evening create can be exemplified.

(4) Specific examples of aryloxysilane compounds include 1,2-epoxystyrene

(5) As the alkyloxysilane compound, specifically, 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxy Octane, 1,2-epoxynonane, 1,2-epoxydecane, 1,2-epoxydedecane, 1,2-epoxidededecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,, Examples thereof include 2-epoxy pen decane, 1,2-epoxyhexadecane, 1,2-epoxyhepcane decane, 1,1,2-epoxy octane decane, 2-epoxynonadecane, and 1,2-epoxy icosane.

(6) Examples of the alicyclic epoxy compound include compounds in which carbon atoms constituting an epoxy group directly constitute an alicyclic ring, such as a compound represented by the following general formula (3).

'General formula (3) Specific examples of the alicyclic epoxy compound include, for example, 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-1,3,4-epoxycyclohexanecarboxy. Rate, bis (3,4-epoxycyclohexylmethyl) adipate, exo-1,2,3-epoxynorbornane, bis (3,4_epoxy-16-methylcyclohexylmethyl) adipate, 2--(7- Oxabicyclo [4.1.0] hept-1-yl) spiro (1,3-dioxane-5,3,1- [7] oxabicyclo [4.1.0] heptane, 4- (1, -methylepoxy) Ethyl-1,2-epoxy-12-methylcyclohexane, 4-epoxyethyl-1,2-epoxycyclohexane, and the like.

(7) Specific examples of the epoxidized fatty acid monoester include esters of epoxidized fatty acids having 12 to 20 carbon atoms and alcohols or phenols having 1 to 8 carbon atoms, and alkylphenols. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used.

(8) Specific examples of epoxidized vegetable oils include epoxy compounds of vegetable oils such as soybean oil, linseed oil, and cottonseed oil.

Among these epoxy compounds, a phenylglycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound, and an epoxidized fatty acid monoester are preferable because the thermal / hydrolytic stability can be further improved. And glycidyl ester type epoxy compounds and alicyclic epoxy compounds are more preferable.

When these epoxy compounds are blended with the refrigerator oil composition of the present invention, the blending amount is not particularly limited, but usually the content is based on the total amount of the refrigerator oil composition (based on the total amount of the base oil and all the blended additives). It is desirable to mix the epoxy compound in such an amount that the amount becomes 0.1 to 5.0% by mass, more preferably 0.2 to 2.0% by mass.

Also, that two or more of the above phosphorus compounds and epoxy compounds may be used in combination Of course.

In order to further enhance the performance of the refrigerating machine oil composition of the present invention, if necessary, a conventionally known refrigerating machine oil additive, for example, a phenolic compound such as di-tert-butyl-p-cresol, bisphenol A, etc. Antioxidants, phenyl mono-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, etc., antioxidants based on amines, antiwear agents such as zinc dithiophosphate, chlorinated paraffin, sulfur Additives such as extreme pressure agents such as compounds, oil agents such as fatty acids, antifoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, cleaning dispersants, etc. Alternatively, it is also possible to mix several types. The total blended amount of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less based on the total amount of the refrigerating machine oil composition (based on the total amount of the base oil and all the blended additives). is there.

The kinematic viscosity of the refrigerator oil composition of the present invention is not particularly limited, but the kinematic viscosity at 40 ° C. is preferably 3 to L 00 mm ² / s, more preferably 4 to 50 mm ² / s, and most preferably 5 to 50 mm ² / s. 4040 mm ² / s. Further, the kinematic viscosity at 100 ° C preferably 1 to 20 mm ² / s, more preferably, to 2 to 10 mm ² / s. Further, a feature of the refrigerating machine oil of the present invention that the heat and hydrolysis stability is good even when the viscosity is reduced is that the kinematic viscosity at 40 ° C is preferably 5 to 35 mm ² / s, more preferably 5 to 25 mm ² / s. ² Zs, even more preferably between 5 and 20 mm ² / s, most preferably between 5 and 15 mm ² / s.

The volume resistivity of the refrigerating machine oil composition of the present invention is not particularly limited, but is preferably not less than 1.0Ο, more preferably not less than 1.0χ10 ¹² Ω · m, and most preferably not less than 1.0χ10 ¹² Ω · 〇m. Preferably, it can be 1.0 × 10 ¹³ Ω · cm or more. In particular, when used for hermetic refrigerators, high electrical insulation tends to be required. In the present invention, the volume resistivity means a value at 25 ° C. measured in accordance with JISC2101 “Electric insulating oil test method”. The water content of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerator oil composition. be able to. In particular, when used for hermetic refrigerators, it is required that the water content be low from the viewpoint of the thermal and hydrolytic stability of the oil and the effect on the electrical insulation.

Further, the total acid value of the refrigerator oil composition of the present invention is not particularly limited, but is preferably 0.1 mgCOH / g or less, more preferably, in order to prevent corrosion of metal used in the refrigerator or piping. 0.05 mgKOH / g or less. In the present invention, the total acid value refers to the value of the total acid value measured in accordance with JIS K 2501 “Testing Method for Neutralization Value of Petroleum Products and Lubricating Oils”.

The ash content of the refrigerating machine oil composition of the present invention is not particularly limited. However, in order to enhance the thermal and hydrolytic stability of the refrigerating machine oil composition of the present invention and suppress the generation of sludge, it is preferably 100 ppm. Or less, more preferably 50 ppm or less. In the present invention, the ash refers to the value of ash measured in accordance with JIS K 2272 "Test method for ash and sulfated ash of crude oil and petroleum products".

Refrigerants used in refrigerators using the refrigerator composition of the present invention include HFC refrigerants, fluorinated ether-based refrigerants such as monofluoroethers, non-fluorine-containing ether-based refrigerants such as dimethyl ether, and carbon dioxide and the like. These are natural refrigerants such as hydrocarbons, and these may be used alone or as a mixture of two or more.

Examples of the HFC refrigerant include hydrofluorcarbon having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pendufluorene (HFC-125), 1,1,2,2-tetrafluoroethane (HF C-134) ), 1, 1, 1, 2—tetrafluorene (HFC-134a), 1,1,1-trifluorene (HFC—143a), 1,1-difluorene (HFC—152a), etc. of HFC, or a mixture of two or more thereof. These refrigerants are appropriately selected according to the required performance for the application. For example, HF C_32 alone; HF C-23 alone; HFC-134a alone; HFC-125 alone; HFC-134 a / HF C_32 = 60-80% by mass / 40-20% by mass of a mixture; HFC-32 / HF C-125 = 40-70% by mass / 60-30% by mass of a mixture; HF C-125 HFC_143a = 40-60% by mass HFC-134a / HFC-32 / HFC-125 = 60% by mass / 30% by mass / 10% by mass mixture; HFC-134a / HFC-32 / HFC — 1 25 = 40 to 70% by mass / 15 to 35% by mass / 5 to 40% by mass; HFC—125 / HFC—134a / HFC-143a = 35 to 55% by mass / 1 to 15% by mass A preferable example is a mixture of / 40 to 60% by mass. More specifically, a mixture of HFC-134a / HFC-32 = 70/30% by mass; a mixture of HFC-32 / HFC-125 = 60/40% by mass; HFC-32 / HFC-125 = 50 / 50% by weight of a mixture (R41 OA); HFC-32 / HFC- 125 = 45/5 5% by weight of a mixture (R410B); HFC- 125 / HFC- 143a = 50Z 50% by weight of a mixture (R507 C); HFC-32 / HFC- 125 / HF C- 134 a = mixture of 30/10/60% by mass; HFC-32 / HFC- 125Z HFC-134a = mixture of 23/25/52% by mass ( R407 C); HF C— 32 / HF C- 125 / HF C- 134 a = 25/1 5/60% by mass (R407 E); HFC- 125 / HF C- 134 a / HF C- 143 a = 44

/ 4/52% by mass of a mixture (R404A).

In addition, examples of natural refrigerants include carbon dioxide and hydrocarbons. Here, a gaseous refrigerant at 25 ° C. and 1 atm is preferably used as the hydrocarbon refrigerant. Specifically, it is an alkane, cycloalkane, alkane or a mixture thereof having 1 to 5, preferably 1 to 4 carbon atoms. Specifically, for example, methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, Methylcyclopropane or a mixture of two or more thereof is mentioned. Among these, propane, butane, isobutane or a mixture thereof is preferred. The refrigerating machine oil composition according to the present invention is usually present in a refrigerating machine in the form of a refrigerating machine fluid composition mixed with the above-described refrigerant. The mixing ratio of the refrigerating machine oil composition and the refrigerant in the fluid composition is not particularly limited, but the refrigerating machine oil composition is preferably 1 to 500 parts by weight, more preferably 100 to 100 parts by weight of the refrigerant. It is 2 to 400 parts by weight.

The refrigerating machine oil composition of the present invention can be used as a lubricating oil for a refrigerant compressor of any refrigerating machine due to its excellent electrical properties and low moisture absorption. Refrigerators used are, specifically, room air conditioners, package air conditioners, refrigerators, automotive air conditioners, dehumidifiers, freezers, freezer and refrigerated warehouses, vending machines, showcases, cooling equipment for chemical plants, etc. Is mentioned. Further, the refrigerator oil composition of the present invention is particularly preferably used for a refrigerator having a hermetic compressor. Furthermore, the refrigerating machine oil composition of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, and a centrifugal type.

[Example]

Hereinafter, the content of the present invention will be described more specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Examples 1 to 4 and Comparative Example 1

The base oils and additives shown below were blended as shown in Tables 1 to 12, and sample oils of Examples 1 to 44 and Comparative Example 1 were prepared. Tables 1 to 12 show the properties (kinematic viscosity at 40 ° C and 100 ° C and total acid value) of each of the obtained sample oils.

(Base oil)

Base oil 1: diisoheptyl cis-1,2-cyclohexanedicarboxylate

Base oil 2: di (2-ethylhexyl) cis-1,2-cyclohexanedicarboxylate Base oil 3: di (3,5,5-trimethylhexyl) cis-1,2-cyclohexanedicarboxylate Base oil 4: cis-1,2-cyclohexanedicarboxylic acid di (2,6-14-1heptyl)

Base oil 5: diisodecyl cis-1,2-cyclohexanedicarboxylate

Base oil 6: cis-4-cyclohexene-1,2,2-diisoheptyl dicarboxylate Base oil 7: cis-4-cyclohexene-1,1,2 di (2-ethylhexyl) dicarboxylate

Base oil 8: cis-4-cyclohexene-1-dicarboxylic acid di (3,5,5-trimethylhexyl)

Base oil 10: diisoheptyl cis-1,3-cyclohexanedicarboxylate

Base oil 11: tetraester of erythritol with a mixed fatty acid (weight ratio = 50:50) of erythritol and 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid Base oil 12: penyu Erythritol and n-pentanoic acid, n-heptanoic acid and 3,

Tetraester of 5,5-trimethylhexanoic acid mixed fatty acid (weight ratio = 50:30:20)

Base oil 13: Copolymer of vinyl ethyl ether and vinyl butyl ether (ethyl / isobutyl = 7: 1, average molecular weight 900)

(Additive)

Additive 1: phenyl glycidyl ether

Additive 2: Glycidyl _2,2-dimethyl oxalate

Additive 3: Cyclohexenoxide

Additive 4: Tricresyl phosphate

Next, the following tests were performed on each of the above sample oils.

(Compatibility test with refrigerant)

JI SK-2 2 1 1 1 g of each sample oil was mixed with 29 g of HF C134a refrigerant in accordance with the `` Refrigeration oil '' The oils were observed to be mutually soluble at 0 ° C, separated or cloudy. Profit The results obtained are shown in Tables 1 to 11.

(Insulation property test)

The volume resistivity of each sample oil at 25 ° C was measured according to JIS-C-2 101 “Electrical Insulating Oil Test Method”. Tables 1 to 11 show the obtained results.

(Heat / hydrolysis stability test I)

90 g of the sample oil whose water content was adjusted to 1000 ppm was weighed into an autoclave, 10 g of HFC134a refrigerant and a catalyst (iron, copper, and aluminum wires) were sealed, and then heated to 200 ° C. Two weeks later, the appearance of the sample oil, the appearance of the catalyst, the volume resistivity of the sample oil, and the total acid value of the sample oil were measured. Tables 1 to 5 show the obtained results.

(Lubricity test)

In accordance with AS TM D 2670 "FALEX WEAR TE ST", after running-in for 1 minute under the condition of sample oil temperature of 100 ° C and under the load of 1501 b, 2 The time test machine was operated. The wear of the test journal (pin) after the test was measured for each sample oil. The results obtained are shown in Tables 1-5.

(Heat / hydrolysis stability test II)

90 g of the sample oil whose water content was adjusted to 1000 ppm was weighed into a autoclave, filled with 10 g of HFC134a refrigerant and a catalyst (iron, copper, and aluminum wires), and then heated to 200 ° C. After 2000 hours, the appearance of the sample oil, the appearance of the catalyst, the volume resistivity of the sample oil, and the total acid value of the sample oil were measured. Tables 6 to 11 show the obtained results.

(Heat / hydrolysis stability test III)

In accordance with JISK 2540, weigh 30 g of sample oil in a 50 ml beaker, cover with aluminum foil, and leave it in a 150 ° C thermostat with a rotating plate. Was measured for appearance, viscosity and total acid number. Table 12 shows the obtained results. 【table 1】

Example 1 Example 2 Example 3 Example 4 Example 5 Base oil 1 2 3 4 5

(Normal amount%) 100 100 100 100 100 Additive-----

(% By mass)

Kinematic viscosity 40 ^o C (mm ² / s) 12.5 18.2 28.5 25.6 29.5

100 ° C (mm ² Zs) 2.9 3.5 4.7 4.5 4.7 Total acid value (mgKOH / g) 0.01 0.01 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Compatible Compatible Volume resistivity (Ωcm) 2.7 X 10 ' ³ 4.6 X 10 ' ³ 7.4 X 10 ¹³ 8.1 10' ³ 8.3 X 10 ' ² Heat and hydrolysis stable sample oil appearance No change No change No change No change No change Test I Catalyst appearance Cu Gloss decrease Gloss decrease Gloss decrease Gloss Decrease gloss decrease

Fe No change No change No change No change No change

Al No change No change No change No change No change No change Volume resistivity (Ωcm) 5.4 X 10 ' ² 6.3 X 10' ² 2.2 X 10 ' ³ 2.8 X 10 ¹³ 3.1 X 10' ² Total acid value (mgKOHZg) 0.60 0.74 0.52 0.56 0.63

FALEX test Pin wear (mg) 22 23 25 23 22

[Table 2]

Example 6 Example 7 Example 8 Example 9 Example 10 10 units / reason 6 7 8 1 1

(% By mass) 100 100 100 99.8 99.0 Additive 1 4

(Mass%) 0.2 1.0 Kinematic viscosity 40 ° C (mm ² / s) 12.8 18.9 29.5 12.4 12.4

100 ° C (mm ² / s) 2.8 3.6 4.7 2.8 2.7 Total acid value (mgKOHZg) 0.01 0.01 0.01 0.00 0.00 Compatible Compatible Compatible Compatible Compatible Compatible Neisso Volume resistivity (Ω -cm) 3.1 10 ' ² 6.1 X 10 ' ² 6.3 X 10' ² 2.5 X 10 ¹³ 2.1 10 ' ³ Heat and hydrolysis stable sample oil appearance No change No change No change No change No change Test I Catalyst appearance Cu Gloss decrease Gloss decrease Gloss decrease No change Gloss reduction

Fe No change No change No change No change No change

Al No change No change No change No change No change No change Volume resistivity (Ω 'cm) 1.1 X 10 "4.6x10" 3.8X10 "1.0X 10 ¹³ 1.2 X 10" Total acid value (mgKOH / g) 0.51 0.55 0.64 0.03 0.75

FALEX test Pin wear (mg) 20 24 22 22 9 [Table 3]

瞷瞷

Example 11 Example 12 Example 13 Base oil 2 2 2

49.9 49.9 49.9 Base oil 11 12 13

(Mass%) 49.9 49.9 49.9 Additive 2 2 2

(% By mass) 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 43.5 25.0 42.1

100 ° C (mm ² Zs) 6.0 4.7 5.8 Total acid value ( _mg KOH _g ) 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Volume resistivity (Ω-cr n) ι.οχ io ' ⁴ 2.8 X 10' ⁴ 1.0X 10 ¹⁴ Heat / hydrolysis stable sample oil appearance No change No change No change Sex test I Catalyst appearance Cu No change No change No change

Fe No change No change No change

Al No change No change No change Volume resistivity (Ω 'cm) 1.2 X 10' ³ 2.5 X 10 ' ³ 1.5 X 10 ¹³ Total acid value (mgKOHZg) 0.01 0.01 0.01

FALEX test Pin wear (mg) 13 14 13

[Table 4]

Example 14 Example 15 Example 16

(% By mass) 49.9 49.9 49.9 groups; 11 12 13

49.9 49.9 49.9 Additive 3 3 3

(% By mass) 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 43.5 25.0 42.1

100 ° C (mm ² / s) 6.0 4.7 5.8 Total acid value (mgKOH / g) 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Volume resistivity (Ω · err 1) 1.0X 10 ' ⁴ 2.8 X 10' ⁴ 1.0X 10 ¹⁴ Heat / Hydrolysis stable sample oil appearance No change No change No change Property test I Catalyst appearance Cu No change No change No change

Fe No change No change No change

Al No change No change No change Volume resistivity (Ω 'cm) 1.5 X 10 ¹³ 3.3 X 10' ³ 1.0X 10 ' ³ Total acid value (mgKOHZg) 0.01 0.01 0.01

FALEX test Pin wear (Tig) 13 14 13 [Table 5]

[Table 6]

Example 17 Example 18 Example 19 Example 20 Example 20 Example 21 Base oil 1 2 3 4 5

(% By mass) 99.8 99.8 99.8 99.8 99.8 Additive 1 1 1 1 1

(% By mass) 0.2 0.2 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 12.4 18.2 28.5 25.6 29.5

100 ° C (mm ² / s) 2.8 3.5 4.7 4.5 4.7 Total acid value (mgKOH / g) 0.01 0.01 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Compatible Negative Volume resistivity (Ω 'cm) 2.5 X 10 ¹³ 1.0X 10 ¹³ 2.5 X 10 ¹³ 3.0X 10 ¹³ 3.5 X 10 ¹³ Heat-hydrolysis stable sample oil appearance No change No change No change No change No change Sex test 触媒 Catalyst appearance Cu No change No change No change No change No change

Fe No change No change No change No change No change

Al No change No change No change No change No change No change Volume resistivity (Ω 'cm) 4.2X 10' ² 3.5 X 10 ¹² 4.0 X 10 ¹² 2.2X 10 ' ² 1.0X 10' ² Total acid value (mgKOHZg) 0.95 0.85 0.92 0.80 0.88 [Table 7]

Example 22 Example 23 Example 24 Example 24 Example 25 Example 26 Base oil 1 2 3 4 5

(% By mass) 99.8 99.8 99.8 99.8 99.8 Additive 2 2 2 2 2

(% By mass) 0.2 0.2 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 12.5 18.2 28.5 25.6 29.5

100 ° C (mm ² / s) 2.9 3.5 7 4.7 Total acid value (mgKOHZg) 0.01 Compatible Compatible Compatible Compatible Compatible Compatible. Volume resistivity (Ω-cr n) 7.0 X 10 ¹² 1.2X 10 ¹³ 3.0 X 10 ¹³ 3.0 X 10 ¹³ 3.4x10 "Heat / hydrolysis stable sample oil appearance No change No change No change No change No change Sex test 試験 Catalyst appearance Cu No change No change No change No change No change

Fe No change No change No change No change No change

Al No change No change No change No change No change No change Volume resistivity (Ω 3.6 10 "2.8 10 ¹² 1.0 10 ¹² 1.0 10 ¹² 1.5 X 10 ' ² Total acid value (mgKOHZg) 0.35 0.33 0.28 0.35 0.30

[Table 8]

Example 27 Example 28 Example 29 Example 29 Example 30 Example 31 Base oil 1 2 3 4 5

(% By mass) 99.8 99.8 99.8 99.8 99.8 Additive 3 3 3 3 3

(% By mass) 0.2 Kinematic viscosity 40 ° C (mm ² / s) 12.5 18.2 28.5 25.6 29.5

100 ° C (mm s) 2.9 3.5 4.7 4.5 4.7 Total acid value (mgKOH / g) 0.01 0.01 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Compatible Compatible Volume resistivity (Ω-cn n) 7.5 X 10 ' ² 1.5 X 10 ' ³ 3.2 X 10' ³ 3.0 X 10 ' ³ 3.0 X 10' ³ Heat-hydrolysis stable sample oil appearance No change No change No change No change No change Test 試験 Catalyst appearance Cu No change No change Change None No change No change

Fe No change No change No change No change No change

Al No change No change No change No change No change No change Volume resistivity (Ω 'cm) 3.3 X 10 ¹² 1.0X 10' ² 1.2X 10 ¹³ 1.2 X 10 ¹³ 1.0X 10 ' ² Total acid value (mgKOHZg) 0.34 0.36 0.35 0.30 0.35 [Table 9]

Example 32 Example 33 Example 34 units; 6 7 8

(% By mass) 99.8 99.8 99.8 Additive 1 1 1

(Mass%) 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 12.8 18.9 29.5

100 ° C (mm ² / s) 2.8 3.6 4.7 Total acid value (mgKOHZg) 0.01 0.01 0.01 Compatible Compatible Compatible Compatible Compatible Volume resistivity (Ωcm) 1.0X 10 ' ² 1.2X 10' ² 1.5X10 ' ² Heat-hydrolysis stable sample oil appearance No change No change No change Testability Π Catalyst appearance Cu No change No change No change

Fe No change No change No change

Al No change No change No change Volume resistivity (Ωcm) 1.1 10 "5.0X 10" 3.0X 10 "Total acid value (mgKOHZg) 0.95 1.00 1.02

[Table 10]

Example 35 Example 36 Example 37 Base oil 6 7 8

(% By mass) 99.8 99.8 99.8 Additive 2 2 2

(Mass%) 0.2 0.2 0.2 Kinematic viscosity 40 ° C (mm ² / s) 12.8 18.9 29.5

100 ° C (mm ² / s) 2.8 3.6 4.7 Total acid value (mgKOH / g) 0.01 0.01 0.01 Compatible Compatible Compatible 1 compatible Dissolution Volume resistivity (Ωcm) 1.2X 10 ' ² 1.5 X 10' ² 1.0 X 10 ' ² Heat / Hydrolysis stable sample oil appearance No change No change No change Sex test 触媒 Catalyst appearance Cu No change No change No change

Fe No change No change No change

Al No change No change No change Volume resistivity (Ω -cm) 1.4X10 "7.6X10" 2.8X10 "Total acid value (mgKOHZg) 0.50 0.44 0.36 [Table 1 1

As is clear from the results shown in Tables 1 to 12, the sample oils of Examples 1 to 44, which are the refrigerating machine oil compositions of the present invention, have kinematic viscosities and refrigerant compatibility when used together with HFC refrigerants. , Electrical insulation, hydrolysis resistance, heat stability and lubricity were all well-balanced and excellent.

As is clear from the results shown in Tables 6 to 11, glycidyl was used as an additive. It was found that when an ester type epoxy compound or an alicyclic epoxy compound was used, it was more excellent in heat and hydrolysis stability.

Further, the sample oils of Examples 41 and 2 containing an ester compound having a cyclohexane ring and the sample oils of Examples 43 and 44 containing an ester compound having a cyclohexene ring were thermally and hydrolyzed. Comparison in Stability Test III shows that the former has a small increase in viscosity and the latter has a small increase in total acid value. Industrial applicability

As described above, according to the refrigerating machine oil composition of the present invention, when used in combination with an HFC refrigerant and a natural refrigerant such as carbon dioxide or carbon at a hide port, lubricity, refrigerant compatibility, heat and water It excels in decomposition stability, electrical insulation, etc., and can achieve high efficiency of the refrigeration system.

Claims

Speculation of Word

1. It has two alicyclic rings and two ester groups represented by the following general formula (1), and two of the ester groups are bonded to mutually adjacent carbon atoms on the alicyclic ring; A cis-type alicyclic dicarboxylic acid ester compound that is cis-form with respect to two orientations of the ester group

-COOR ¹ (1)

A refrigerating machine oil composition containing:

2. The refrigerator oil composition according to claim 1, further comprising an epoxy compound.

3. The epoxy compound according to claim 2, wherein the epoxy compound is at least one compound selected from the group consisting of a phenyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an alicyclic epoxy compound and an epoxidized fatty acid monoester. The refrigerating machine oil composition according to the above.

4. The refrigerator oil composition according to claim 2, wherein the epoxy compound is at least one compound selected from the group consisting of a glycidyl ester type epoxy compound and an alicyclic epoxy compound.

5. The refrigerator oil composition according to any one of claims 1 to 4, further comprising a phosphorus compound.

6. A refrigerating machine fluid composition comprising the refrigerating machine oil composition according to any one of claims 1 to 5 and non-chlorine-containing Freon.