JP3360999B2 - Lubricating oil for refrigerator, composition for refrigerator and refrigerator - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a refrigerating machine lubricating oil, a refrigerating machine composition, and a refrigerating machine, and more particularly, a refrigerating machine useful as a refrigerating machine oil for a fluoroalkane and / or a chlorofluorofluoroalkane refrigerant. Lubricating oil, a refrigerator composition comprising a mixture of the refrigerator lubricating oil and an alkane fluoride and / or chlorofluoroalkane refrigerant, and a lubricating oil for the refrigerator and a fluorine refrigerant. The present invention relates to refrigeration equipment using alkanes and / or chlorofluoroalkanes.

[0002]

2. Description of the Related Art Due to the problem of ozone layer depletion in recent years, CFCs (chlorofluorocarbons) and HCFCs (hydrochlorofluorocarbons), which have been conventionally used as refrigerants for refrigeration equipment, are subject to regulation. Fluorocarbons) are being used as refrigerants.

Refrigerating machine oil for this HFC refrigerant is H
PAG (polyalkylene glycol) compatible with FC,
Esters are being studied or used. For example P
Regarding AG, U.S. Pat. No. 4,755,316, JP-A-1-198694, 1-256594 and 1-2.
No. 59093, No. 1-259094, No. 1-2590
No. 95, No. 1-274191, No. 2-43290,
No. 2-55791, No. 2-84491, etc., and regarding ester, it is described in Tokuhyo 3-505602.
No. 3, JP-A-3-88892, JP-A-2-128991,
No. 3-128992, No. 3-200895, No. 3-
No. 227397, No. 4-20597, No. 4-7239.
No. 0, No. 4-218592, No. 4-249959, and the like.

However, since PAG has high hygroscopicity and poor electric characteristics (volume resistivity), leakage current is caused when it is used in a hermetic compressor having a structure in which oil and electrodes come into contact with each other, which is used in refrigerators and room air conditioners. May cause

For this reason, as a hermetic compressor oil for HFC refrigerant, ester oil, which is compatible with HFC, has a lower hygroscopicity than PAG and has excellent electric characteristics, is effective. However, the ester oil may undergo hydrolysis due to its structure and generate an acid, which is expected to cause various inconveniences.

On the other hand, a PAG having low water absorption and high volume resistivity has been proposed (Japanese Patent Laid-Open No. 4-1529).
5, No. 4-39394, No. 4-130188).
However, this PAG does not fully satisfy all of high compatibility with HFC, low hygroscopicity, and high electric insulation.

[0007]

SUMMARY OF THE INVENTION The present invention is based on the HFC-1.
Refrigerant lubricating oil having excellent compatibility with fluorinated alkane refrigerants such as 34a and chlorofluorinated alkane refrigerants and having excellent electrical characteristics, the refrigerator lubricating oil and the fluorinated alkane and / or chlorofluorinated alkane refrigerants. It is an object of the present invention to provide a refrigerating machine composition comprising the mixture of 1. and a refrigerating machine using the refrigerating machine lubricating oil as a lubricating oil and a fluoroalkane and / or a chlorofluoroalkane as a refrigerant.

[0008]

DISCLOSURE OF THE INVENTION The present inventors have focused their attention on ethers which have no fear of hydrolysis, and have conducted diligent research to overcome the drawbacks of the above-mentioned conventional compounds. As a result, polyoxyalkylenes having a specific structure have been obtained. We found that the compound dissolves in a wide temperature range with HFC and has excellent electrical characteristics.
The present invention has been completed.

That is, the lubricating oil for refrigerator of the present invention has the following general formula (I):

[0010]

[Chemical 2] [In the formula (I), A has a heterocycle having an ether bond in the molecule and has 2 to 20 hydroxyl groups, and has 4 to 40 carbon atoms.
Showing a residue obtained by removing a hydroxyl group from the compound of R ¹ and R
² may be the same or different, each having 2 to 2 carbon atoms
6 represents an alkylene group, R ³ represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a and b are respectively positive numbers, l and m , N is 0 or a positive number, and a · l + b · m =
2 to 100 and 1 + m + n = indicates an integer satisfying the condition of 2 to 20], which is a main component of one compound or a mixture of two or more compounds selected from the polyoxyalkylene compounds represented by The polyoxyalkylene compound or the mixture of two or more polyoxyalkylene compounds has (a) a hydroxyl value of 0 to 30.0 mgKOH / g, and (b) R ¹ and R in the general formula (I). The ratio of butylene groups in all alkylene groups represented by ² must satisfy the following mathematical formula (1).

[0011]

[Equation 2] [Wherein p represents the number of butylene groups and q represents the number of alkylene groups having 2 to 6 carbon atoms excluding the butylene group in the formula (1)], and both conditions are simultaneously satisfied.

Further, the composition for a refrigerator of the present invention comprises (A) the lubricating oil for a refrigerator described above, and (B) a fluorinated alkane and / or
Alternatively, it is characterized by comprising a mixture with a chlorofluoroalkane.

Further, the refrigerating apparatus of the present invention uses (A) the above-mentioned refrigerating machine lubricating oil as a lubricating oil, and uses (B) a fluorinated alkane and / or a chlorofluoroalkane as a refrigerant. It is a thing.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be described in more detail below.

The polyoxyalkylene compound according to the present invention is a compound represented by the following general formula (I).

[0016]

[Chemical 3] In formula (I), A has a heterocycle having an ether bond in the molecule, and has 2 to 20, preferably 2 to 15, and more preferably 2 to 10 hydroxyl groups, and has 4 carbon atoms. ~ 4
0, preferably 5 to 30, and more preferably 5 to 20 compounds in which a hydroxyl group is removed are shown. The compound having a heterocycle having an ether bond in the molecule and having 2 to 20 hydroxyl groups and having 4 to 40 carbon atoms is specifically, for example, isosorbide (1, 4,
3,6-sorbide), hexitan, mannitan, mannid, dulcitan, dehydrated polyhydric alcohols such as dulcide; xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose and the like having a cyclic structure. Monosaccharides, cellobiose, maltose, isomaltose,
Disaccharides such as trehalose and sucrose, and saccharides represented by trisaccharides such as raffinose, gentianose and melezitose; and the like.

The compound in which the residue represented by A in the formula (I) is a residue of a polyhydric alcohol which does not satisfy the above-mentioned conditions relating to the compound of the present invention is a fluoroalkane and / or a chlorinated refrigerant. It is not preferable because it has poor compatibility with the fluorinated alkane compound.

In the formula (I), R ¹ and R ² may be the same or different and each represents an alkylene group having 2 to 6 carbon atoms. The compound having an alkylene group having 7 or more carbon atoms as R ¹ and R ² in the formula (I) is not preferable because it has poor compatibility with the fluoroalkane and / or the chlorofluoroalkane compound as a refrigerant.

Specific examples of R ¹ and R ² include ethylene group, propylene group (1-methylethylene group, 2-methylethylene group), trimethylene group, butylene group (1-ethylethylene group, 2-methylethylene group, 2-methylethylene group). Ethylethylene group), 1,2-dimethylethylene group, 2,2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group, pentylene group (1 -Propylethylene group, 2-
Propylethylene group), 1-ethyl-1-methylethylene group, 1-ethyl-2-methylethylene group, 1,1,2
-Trimethylethylene group, 1,2,2-trimethylethylene group, 1-ethyltrimethylene group, 2-ethyltrimethylene group, 3-ethyltrimethylene group, 1,1-dimethyltrimethylene group, 1,2-dimethyl Trimethylene group,
1,3-dimethyltrimethylene group, 2,3-dimethyltrimethylene group, 3,3-dimethyltrimethylene group, 1-
Methyltetramethylene group, 2-methyltetramethylene group, 3-methyltetramethylene group, 4-methyltetramethylene group, pentamethylene group, hexylene group (1-butylethylene group, 2-butylethylene group), 1-methyl-
1-propylethylene group, 1-methyl-2-propylethylene group, 2-methyl-2-propylethylene group, 1,
1-diethylethylene group, 1,2-diethylethylene group, 2,2-diethylethylene group, 1-ethyl-1,2
-Dimethylethylene group, 1-ethyl-2,2-dimethylethylene group, 2-ethyl-1,1-dimethylethylene group, 2-ethyl-1,2-dimethylethylene group, 1,
1,2,2-tetramethylethylene group, 1-propyltrimethylene group, 2-propyltrimethylene group, 3-propyltrimethylene group, 1-ethyl-1-methyltrimethylene group, 1-ethyl-2-methyl Trimethylene group, 1-
Ethyl-3-methyltrimethylene group, 2-ethyl-1-
Methyltrimethylene group, 2-ethyl-2-methyltrimethylene group, 2-ethyl-3-methyltrimethylene group, 3
-Ethyl-1-methyltrimethylene group, 3-ethyl-2
-Methyltrimethylene group, 3-ethyl-3-methyltrimethylene group, 1,1,2-trimethyltrimethylene group,
1,1,3-trimethyltrimethylene group, 1,2,2-
Trimethyltrimethylene group, 1,2,3-trimethyltrimethylene group, 1,3,3-trimethyltrimethylene group, 2,2,3-trimethyltrimethylene group, 2,3
3-trimethyltrimethylene group, 1-ethyltetramethylene group, 2-ethyltetramethylene group, 3-ethyltetramethylene group, 4-ethyltetramethylene group, 1,1-
Dimethyltetramethylene group, 1,2-dimethyltetramethylene group, 1,3-dimethyltetramethylene group, 1,4
-Dimethyltetramethylene group, 2,2-dimethyltetramethylene group, 2,3-dimethyltetramethylene group, 2,
4-dimethyltetramethylene group, 3,3-dimethyltetramethylene group, 3,4-dimethyltetramethylene group,
4,4-dimethyltetramethylene group, 1-methylpentamethylene group, 2-methylpentamethylene group, 3-methylpentamethylene group, 4-methylpentamethylene group, 5-
Examples thereof include a methylpentamethylene group and a hexamethylene group.

Further, as R ¹ and R ² , an alkylene group having 2 to 4 carbon atoms is preferable, and an alkylene group having 3 to 4 carbon atoms, from the viewpoint of being excellent in compatibility with a fluoroalkane and / or chlorofluoroalkane compound as a refrigerant. An alkylene group of 4,
Specifically, for example, propylene group (1-methylethylene group, 2-methylethylene group), trimethylene group, butylene group (1-ethylethylene group, 2-ethylethylene group), 1,2-dimethylethylene group, 2 , 2-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 3-methyltrimethylene group, tetramethylene group and the like are more preferable.

In the polyoxyalkylene compound represented by the formula (I) according to the present invention, the general formula:-(R ¹ O) _a
The polyoxyalkylene group represented by — and — (R ² O) _b — may be a polyoxyalkylene group consisting of an oxyalkylene group having a single structure, or may have two or more kinds of structures. It may be a polyoxyalkylene group in which oxyalkylene groups are mixed, that is, a polyoxyalkylene group in the form of a random copolymer or block copolymer of two or more kinds of alkylene oxides.

In the formula (I), R ³ is an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to ³ carbon atoms. A compound having an alkyl group having 7 or more carbon atoms, another alkenyl group or an aryl group as R ³ in the formula (I) has poor compatibility with a fluoroalkane and / or a chlorofluoroalkane compound as a refrigerant. Not preferable.

Specific examples of R ³ include methyl group, ethyl group, propyl group, isopropyl group, butyl group (including all isomers), pentyl group (including all isomers) and hexyl group. (Including all isomers) and the like.

In the formula (I), R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably 1 to 3 carbon atoms. A compound having an alkyl group having 7 or more carbon atoms, another alkenyl group or an aryl group as R ⁴ in the formula (I) has poor compatibility with a fluoroalkane and / or a chlorofluoroalkane compound as a refrigerant. Not preferable.

Specific examples of R ⁴ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group (including all isomers), and a pentyl group (including all isomers). , Hexyl groups (including all isomers), and the like. In the formula (I), a, b
Each is a positive number, l, m, and n are each 0 or a positive number, and a · l + b · m = 2 to 100, preferably 2 to 50, more preferably 2 to 30, most preferably 2 to 20, and 1 + m + n = 2 to 20, preferably 2
˜15, more preferably an integer satisfying the conditions of 2 to 10 is shown.

The refrigerating machine lubricating oil of the present invention is selected from one compound selected from the polyoxyalkylene compounds represented by the above formula (I) or a polyoxyalkylene compound represented by the above formula (I). The main component is a mixture of two or more compounds. Further, in the present invention, when the above-mentioned one kind of the polyoxyalkylene compound is used alone, the polyoxyalkylene compound is used, and when the mixture of the two or more kinds of polyoxyalkylene compound is used, the mixture is It is important to satisfy both conditions a) and (b) at the same time. (A) The lower limit is 0 mgKOH / g and the upper limit is 30.0 mgKOH / g, preferably 20.0 mgKOH.
Have a hydroxyl value of / g. (B) In the general alkylene group represented by R ¹ and R ² in the formula (I), when the number of butylene groups is p and the number of alkylene groups having 2 to 6 carbon atoms excluding butylene group is q, The value of p / (p + q) (ratio of butylene groups in all alkylene groups represented by R ¹ and R ² ) is 0.5 to 1.
0, preferably 0.7 to 1.0, more preferably 0.8
~ 1.0, most preferably 1.0.

In the present invention, the hydroxyl value of the above (a) is ideally 0 mgKOH / g, but the actual lower limit value is generally 0. It becomes about 5 mgKOH / g. In addition, (a) above
When the hydroxyl value of is over 30.0 mgKOH / g,
The compound obtained is inferior in electrical characteristics and lubricity, which is not preferable.

In the present invention, p / in (b) above is also used.
When the value of (p + q) is less than 0.5, a compound satisfying both excellent compatibility with the fluoroalkane and / or chlorofluoroalkane compound as a refrigerant and excellent electrical properties cannot be obtained, which is preferable. Absent.

The method for producing the polyoxyalkylene compound represented by the formula (I) or the mixture thereof according to the present invention is arbitrary, and specifically, for example, a complex having an ether bond in the molecule as described above is used. It can be obtained by reacting a compound having a ring and having 2 to 20 hydroxyl groups with an alkylating agent at 0 to 100 ° C. in the presence of a phase transfer catalyst. In this case, the compound having 2 to 20 hydroxyl groups and the alkylating agent may be one kind of compound or a mixture of two or more kinds of compounds. Further, the obtained polyoxyalkylene compound may be further purified to remove by-products and unreacted substances, but a small amount of by-products and unreacted substances are contained in the refrigerator lubricating oil of the present invention. As long as it does not impair excellent performance, it does not matter if it exists.

The molecular weight of the polyoxyalkylene compound or the mixture thereof according to the present invention is not particularly limited, but the number average molecular weight (M _n ) is preferably from the viewpoint of further improving the sealing performance of the refrigerator compressor. Those with 200 to 4000 are preferably used, and those with M _n of 300 to 3000 are more preferably used. Furthermore, M _w (weight average molecular weight) is more excellent because it is more compatible with the fluoroalkane and / or chlorofluoroalkane compound that is the refrigerant.
It is preferable that / M _n = 1.0 to 1.2.

Furthermore, the kinematic viscosity of the polyoxyalkylene compound or the mixture thereof according to the present invention is arbitrary, but it is more excellent in compatibility and lubricity with the fluoroalkane and / or chlorofluoroalkane compound as a refrigerant. Therefore, at 40 ° C., preferably 3 to 2000 mm ² /
s, more preferably 5 to 1500 mm ² / s, and at 100 ° C. preferably ^{2 to} 100 mm ² / s,
More preferably, it has a kinematic viscosity of 3 to 50 mm ² / s.

The refrigerator lubricating oil of the present invention has the above formula (I).
The polyoxyalkylene compound represented by or a mixture thereof is a main component, and the polyoxyalkylene compound represented by the above formula (I) or a mixture thereof can be used alone, but is required. Other lubricating oils may be blended and used according to the above.

Other lubricating oils that can be blended in this case include oxygen-containing lubricating oils for refrigerators, specifically, esters, polyglycols, polyphenyl ethers, silicates, polysiloxanes, and perfluoroethers. Ester or polyglycol is more preferable.

Specific examples of the ester as used herein include dibasic acid ester, polyol ester, complex ester, and polyol carbonate ester.

As the dibasic acid ester, glutaric acid,
Adipic acid, pimelic acid, suberic acid, azelaic acid,
Dibasic acids having 5 to 10 carbon atoms such as sebacic acid, and methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol,
Carbon number 1 having a linear or branched alkyl group such as nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.
An ester with a monohydric alcohol of about 15 is preferably used, and specific examples thereof include ditridecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, and di-3-ethylhexyl sebacate.

The polyol ester referred to here is
An ester of a diol or a polyol having 3 to 20 hydroxyl groups and a fatty acid having 6 to 20 carbon atoms is preferably used. Here, as the diol, specifically, for example, 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-undecanediol, 1,12-dodecanediol and the like. Specific examples of the polyol include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), and tri-
(Trimethylolpropane), pentaerythritol,
Di- (pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (2-20 mer of glycerin), 1,3,5-pentanetriol,
Sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose,
Examples include sugars such as sucrose, raffinose, gentianose, and melezitose, and partial etherified products thereof, and methyl glucoside (glycoside). As the fatty acid, specifically, for example, hexanoic acid,
Heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid,
Examples thereof include linear or branched ones such as pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid and oleic acid, and so-called neo acids having a quaternary α carbon atom. The polyol ester may have a free hydroxyl group. In addition, particularly preferred are neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), triethyl An ester of a hindered alcohol such as-(pentaerythritol), and specific examples thereof include trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2-ethylhexanoate, and pentaerythritol pelargonate.

The complex ester as used herein means
Esters of fatty acids and dibasic acids with monohydric alcohols and polyols, and fatty acids, dibasic acids, monohydric alcohols and polyols include those similar to those exemplified for dibasic acid esters and polyol esters. Can be used.

The polyol carbonic acid ester as used herein is an ester of carbonic acid and a polyol, and the polyol as used herein is the same as those exemplified for the polyol ester, or a polyamine obtained by homopolymerizing or copolymerizing a diol. Glycol, or the above-exemplified polyol to which polyglycol is added can be used.

As the polyglycol, polyalkylene glycol, etherified products thereof, and modified compounds thereof are preferably used. As the polyalkylene glycol, one obtained by homopolymerizing or copolymerizing a diol is used, and as the diol, the same ones as those exemplified for the polyol ester can be used.
Also, ethers of polyalkylene glycol having hydroxyl groups can be used. Specific examples of the etherified product of polyalkylene glycol, monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monopentyl ether, monohexyl ether, monoheptyl ether, monooctyl ether, monononyl ether, monodecyl ether, Examples thereof include dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dinonyl ether and didecyl ether. Examples of the modified compound of polyglycol include a polyalkylene glycol adduct of polyol or an etherified product thereof. As the polyol mentioned here, the same ones as those exemplified for the polyol ester can be used. In the above polyalkylene glycol, when diols having different structures are copolymerized, the polymerization form of the oxyalkylene group is not particularly limited,
It may be either random copolymerization or block copolymerization.

In the refrigerating machine lubricating oil of the present invention, the compounding ratio when these other oxygen-containing refrigerating machine lubricating oils are blended with the polyoxyalkylene compound of the present invention or a mixture thereof, is used. The amount is 100 parts by weight or less, preferably 40 parts by weight or less, relative to 100 parts by weight of the polyoxyalkylene compound or the mixture thereof according to the present invention. Further, in the refrigerating machine lubricating oil of the present invention, a mineral oil-based lubricating oil, a hydrocarbon-based synthetic lubricating oil, or the like may be mixed and used with the polyoxyalkylene compound or the mixture thereof according to the present invention, if necessary. It doesn't matter. As the mineral oil-based lubricating oil, for example, a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and vacuum distillation, solvent degassing, solvent extraction,
A base oil of paraffin type or naphthene type, which is refined by appropriately combining refining treatments such as hydrocracking, solvent dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing, and clay treatment, can be used. Further, as the hydrocarbon-based synthetic lubricating oil, for example, poly α-olefin (polybutene, 1-octene oligomer, 1-decene oligomer, etc.), alkylbenzene, alkylnaphthalene, or a mixture of two or more thereof can be used.

However, since these oils have poor compatibility with the hydrogen-containing CFC refrigerant, the blending ratio is 40 parts by weight or less, preferably 30 parts by weight with respect to 100 parts by weight of the polyoxyalkylene compound according to the present invention or a mixture thereof. It is below the weight part.

The refrigerating machine lubricating oil of the present invention is obtained by adding another oxygen-containing refrigerating machine lubricating oil or mineral oil-based lubricating oil to the polyoxyalkylene compound of the present invention or a mixture thereof as described above. In the case of blending a hydrocarbon-based synthetic lubricating oil, the kinematic viscosity of the refrigerator lubricating oil after blending is optional, but from the viewpoint of excellent sealing performance and heat transfer efficiency of the refrigeration compressor,
At 40 ° C., it is preferably 3 to 2000 mm ² / s, more preferably 5 to 1500 mm ² / s, and 10
It is desirable to have a kinematic viscosity at 0 ° C. of preferably ² to 100 mm ² / s, more preferably 3 to 50 mm ² / s.

In the refrigerating machine lubricating oil of the present invention, in order to further improve its wear resistance and load bearing capacity, phosphoric acid ester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, and chlorinated phosphoric acid are used. At least one phosphorus compound selected from the group consisting of esters and phosphites can be blended.

These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols, polyether type alcohols, or derivatives of such esters.

Specific examples of the phosphoric acid ester include 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, trixylyl phosphate, cresyl diphenyl phosphate ,
Examples include xylyl diphenyl phosphate. Examples of the acidic phosphate ester include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, and 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 reed Dohosufeto, diheptyl acid phosphate, dioctyl acid phosphate,
Dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid phosphate, dihexadecyl acid phosphate, diheptadecyl acid phosphate, di Examples include octadecyl acid phosphate and dioleyl acid phosphate. The amine salt of acidic phosphoric acid ester includes methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine of the acidic phosphoric acid ester. Examples thereof include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine and trioctylamine. Examples of the chlorinated phosphoric acid ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate and the like. As the phosphite, 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,
Examples include trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite, and the like. Also, a mixture of these can be used.

When these phosphorus compounds are compounded in the refrigerator lubricating oil of the present invention, the compounding amount is arbitrary, but preferably 0.01 to 100 parts by weight with respect to 100 parts by weight of the refrigerator lubricating oil of the present invention. 5.0 parts by weight, more preferably 0.02
It is desirable to mix them in a ratio of 3.0 parts by weight.

In the lubricating oil for refrigerator of the present invention, in order to further improve its stability, phenylglycidyl ether type epoxy compound alkyl glycidyl ether type epoxy compound glycidyl ester type epoxy compound aryloxirane compound alkyloxirane compound oil Cyclic epoxy compound Epoxidized fatty acid monoester At least one epoxy compound selected from the group consisting of epoxidized vegetable oils can be blended.

Specific examples of the phenylglycidyl ether type epoxy compound include phenylglycidyl ether and alkylphenylglycidyl ether. The alkylphenyl glycidyl ether as used herein has 1 to 3 alkyl groups having 1 to 13 carbon atoms, and particularly has 1 alkyl group having 4 to 10 carbon atoms, for example, n-butylphenyl glycidyl ether. , I-butylphenyl glycidyl ether, sec
-Butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, pentyl phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, decyl phenyl glycidyl ether, etc. can be illustrated.

Specific examples of the alkyl glycidyl ether type epoxy compound include decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol glycidyl. Ether, trimethylolpropane triglycidyl ether,
Pentaerythritol tetraglycidyl ether, 1,
Examples thereof include 6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.

Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester, and the like. Preferred are glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, Examples thereof include glycidyl acrylate and glycidyl methacrylate.

Specific examples of the aryl oxirane include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.

Specific examples of the alkyloxirane include 1,2-epoxybutane, 1,2-epoxypentane, 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-
Epoxy pentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-
Examples thereof include epoxy eicosane.

Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and bis ( 3,4-epoxycyclohexylmethyl)
Adipate, exo-2,3-epoxy norbornane,
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- (1'-methylepoxyethyl) -1,
2-epoxy-2-methylcyclohexane, 4-epoxyethyl-1,2-epoxycyclohexane and the like can be exemplified.

Specific examples of the epoxidized fatty acid monoester include epoxidized fatty acid having 12 to 20 carbon atoms and alcohol or phenol having 1 to 8 carbon atoms,
Examples thereof include esters with alkylphenols. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used.

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

Among these epoxy compounds, preferred are phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds and epoxidized fatty acid monoesters. Among them, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferable, and phenyl glycidyl ether, butyl phenyl glycidyl ether, alkyl glycidyl ester or a mixture thereof is particularly preferable.

When these epoxy compounds are blended with the lubricating oil for refrigerator of the present invention, the blending amount is optional,
It is preferably 0.1 to 5.0 parts by weight, more preferably 0.2 to 2 parts by weight, based on 100 parts by weight of the refrigerator lubricating oil of the present invention.
It is desirable to mix it in a proportion of 0 parts by weight.

Further, in order to further enhance the performance of the refrigerator lubricating oil of the present invention, conventionally known refrigerator oil additives such as di-tert-butyl-p-cresol, bisphenol A, etc. Phenolic, phenyl-α-naphthylamine, N, N-di (2
-Naphthyl) -p-phenylenediamine and other amine-based antioxidants, zinc dithiophosphate and other antiwear agents, chlorinated paraffins, sulfur compounds and other extreme pressure agents, fatty acids and other oil-based agents, silicone-based and other antioxidants Additives such as a foaming agent, a metal deactivator such as benzotriazole, a viscosity index improver, a pour point depressant, and a detergent dispersant can be blended alone or in combination of several kinds. The total blending amount of these additives is usually 10 parts by weight or less, preferably 5 parts by weight or less, relative to 100 parts by weight of the refrigerator lubricating oil according to the present invention.

The refrigerator lubricating oil containing the polyoxyalkylene compound or the mixture thereof as the main component of the present invention may have a pour point that is generally used as a refrigerator oil, but at a low temperature. In order to prevent the solidification of the lubricating oil, the pour point is -10 ° C or lower, preferably -20 ° C to -80 ° C.
Is desirable.

The refrigerant used in the refrigerator using the refrigerator lubricating oil of the present invention has 1 to 3 carbon atoms, preferably 1 carbon atoms.
˜2 fluoroalkanes and / or chlorofluoroalkanes. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-2)
3), pentafluoroethane (HFC-125), 1,
1,2,2-Tetrafluoroethane (HFC-13
4), 1,1,1,2-tetrafluoroethane (HFC
-134a), 1,1,1-trifluoroethane (HF
C-143a), 1,1-difluoroethane (HFC-
HFCs such as 152a), monochlorodifluoromethane (HCFC-22), 1-chloro-1,1-difluoroethane (HCFC-142b), dichlorotrifluoroethane (HCFC-123), monochlorotetrafluoroethane (HCFC-124), etc. HCFC, trichloromonofluoromethane (CFC-11), dichlorodifluoromethane (CFC-12), monochlorotrifluoromethane (CFC-13), monochloropentafluoroethane (CFC-115), or other CFC, or two or more of these. HFC and / or HCFC, particularly HFC-3, from the viewpoint of environmental problems.
2, HFC-23, HFC-125, HFC-134,
HFC-134a, HFC-143a, HFC-152
It is preferable to use an HFC such as a. These refrigerants are appropriately selected according to the use and the required performance.
C-134a alone; HFC-125 alone; or HF
C-134a / HFC-32 = 60-80 mass% / 40
~ 20 wt% mixture; HFC-32 / HFC-125
= 40 to 70% by mass / 60 to 30% by mass mixture; HF
C-125 / HFC-143a = 40-60% by mass / 6
Mixture of 0-40% by mass; HFC-134a / HFC-
32 / HFC-125 = 60% by mass / 30% by mass / 10
Mass% mixture; HFC-134a / HFC-32 / H
FC-125 = 40-70 mass% / 15-35 mass% /
5-40 mass% mixture; HFC-125 / HFC-1
34a / HFC-143a = 35 to 55 mass% / 1 to 1
A mixture of 5% by mass / 40 to 60% by mass; and the like.

As a mixture of HFC refrigerants, more specifically, a mixture of HFC-134a / HFC-32 = 70/30 mass%; HFC-32 / HFC-125 = 60 /
40% by weight of mixture; HFC-32 / HFC-125 =
50/50 mass% mixture (R410A; Genetron AZ-20 manufactured by Allied Signal Co.); HFC-3
2 / HFC-125 = 45/55 mass% mixture (R4
10B; DuPont SUVA AC9100); HF
C-125 / HFC-143a = 50/50 mass% mixture (R507C; Allied Signal, Genet)
ron AZ-50); HFC-32 / HFC-125
/ HFC-134a = 30/10/60 mass% mixture; HFC-32 / HFC-125 / HFC-134a
= 23/25/52 mass% mixture (R407C; DuPont SUVA AC9000); HFC-125
/ HFC-134a / HFC-143a = 44/4/5
2% by mass mixture (R404A; SUV manufactured by DuPont)
A HP-62) and the like. The refrigerator lubricating oil according to the present invention is usually present in a refrigerator in the form of a refrigerator composition mixed with the above-mentioned fluoroalkane and / or chlorofluoroalkane. The composition ratio of the refrigerating machine oil and the refrigerant in this composition is arbitrary, but normally, 1 to 50 refrigerating machine oil to 100 parts by weight of the refrigerant.
It is 0 part by weight, preferably 2 to 400 parts by weight.

The lubricating oil for a refrigerator of the present invention is a reciprocating or rotating hermetic compressor using a fluoroalkane and / or a chlorofluoroalkane as a refrigerant because of its excellent electric characteristics and low hygroscopicity. It is particularly preferably used for refrigeration equipment such as an air conditioner and a refrigerator having a. Also, it is preferably used for refrigeration equipment such as automobile air conditioners, dehumidifiers, freezers, freezers / refrigerators, vending machines, showcases, chemical plants, and other cooling devices that use alkane fluorides and / or alkane chlorides as refrigerants. In addition, it is also preferably used for a refrigerating machine having a centrifugal compressor using a fluorinated alkane and / or a fluorinated chloroalkane as a refrigerant.

[0063]

EXAMPLES The contents of the present invention will be described more specifically below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

The method for producing the lubricating oil used in Examples 1 to 5 and Comparative Examples 1 to 3 will be described below.

Synthesis Example 1 300 ml equipped with a stirrer, a liquid introducing tube and a pressure gauge
In a stainless steel autoclave, potassium hydroxide 0.8
4 g (0.015 mol) and 58.3 g (0.3 mol) of methyl-α-D-glucoside were added and the mixture was sealed. Next, the autoclave was slightly depressurized, and then 173.1 g (2.4 mol) of 1,2-butylene oxide was added to the autoclave by suctioning the whole amount. Gradually raise the temperature of the contents of the autoclave while stirring them at 120 ° C for 1
The reaction was carried out for 5 hours.

In a 1 liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 77 g of the reaction product obtained by the above reaction, 180 g of sodium hydroxide and 1 g of pure water were added.
60 ml was put and stirred well. Methyl iodide 11
6.3 g (0.8 mol), tetrabutylammonium bromide 9.67 g (0.03 mol) as a phase transfer catalyst, and 300 ml of toluene as a solvent were added, and 40
The reaction was carried out at 20 ° C. for 20 hours to methylate the terminal hydroxyl group of the above reaction product.

Transfer all the contents of the flask to a 1 liter separating funnel, add 200 ml of toluene, and add 250 ml.
It was washed 5 times with pure water. The toluene solution was separated and dehydrated, and then the solvent was removed under the conditions of 120 ° C. and 1 mmHg or less. The obtained liquid was treated with low temperature activated clay at 60 ° C. for 30 minutes. The clay was separated to obtain 80 g of a mixture of the polyoxyalkylene compound according to the present invention as a colorless transparent liquid.

Synthesis Example 2 The addition amount of 1,2-butylene oxide was 129.8 g.
Addition polymerization of 1,2-butylene oxide having methyl-α-D-glucoside as the end group and the end of the reaction product by the same apparatus, conditions, and method as in Synthesis Example 1 except that the amount was (1.8 mol). Methyl etherification of hydroxyl groups and post-treatment of the reaction product were carried out to obtain 75 g of a mixture of the polyoxyalkylene compound according to the present invention as a colorless transparent liquid.

Synthesis Example 3 The addition amount of 1,2-butylene oxide was 216.3 g.
Addition polymerization of 1,2-butylene oxide having methyl-α-D-glucoside as the end group and the end of the reaction product by the same apparatus, conditions, and method as in Synthesis Example 1 except that the amount was (3.0 mol). Methyl etherification of hydroxyl groups and post-treatment of the reaction product were carried out to obtain 88 g of a mixture of the polyoxyalkylene compound according to the present invention as a colorless transparent liquid.

Synthetic Example 4 An autoclave similar to Synthetic Example 1 was charged with potassium hydroxide.
84 g (0.015 mol) and isosorbide (1,4,4)
3,6-sorbide) 43.8 g (0.3 mol) was added,
Sealed. Next, after depressurizing the autoclave to some extent, 194.7 g (2.7 mol) of 1,2-butylene oxide was added.
Was added to the autoclave by suctioning the entire volume. The contents of the autoclave were gradually heated with stirring and reacted at 120 ° C. for 15 hours.

80 g of the reaction product obtained by the above reaction, 180 g of sodium hydroxide and 160 ml of pure water were placed in the same four-necked flask as in Synthesis Example 1 and well stirred. Here, 56.8 g (0.4 mol) of methyl iodide and 9.67 of tetrabutylammonium bromide as a phase transfer catalyst.
g (0.03 mol) and toluene 300 ml as a solvent
Was added and reacted at 40 ° C. for 24 hours to methylate the hydroxyl group at the terminal of the above reaction product.

Transfer the entire contents of the flask to a 1 liter separating funnel, add 200 ml of toluene, and add 250 ml.
It was washed 5 times with pure water. The toluene solution was separated and dehydrated, and then the solvent was removed under the conditions of 120 ° C. and 1 mmHg or less. The obtained liquid was treated with low temperature activated clay at 60 ° C. for 30 minutes. The clay was separated to obtain 79 g of a mixture of the polyoxyalkylene compound according to the present invention as a colorless transparent liquid.

Synthesis Example 5 The amount of 1,2-butylene oxide added was 173.1 g.
Isosorbide (1,4,3,6--) was prepared by the same apparatus, conditions and method as in Synthesis Example 4 except that the amount was (2.4 mol).
Sorbide) -terminated 1,2-butylene oxide addition polymerization, methyl etherification of the terminal hydroxyl groups of the reaction product, and post-treatment of the reaction product to obtain a polyoxyalkylene compound according to the present invention as a colorless transparent liquid. Mixture of 7
2 g was obtained.

Synthesis Example 6 Potassium methoxide 6 was placed in a 1 liter stainless steel autoclave equipped with a stirrer, a liquid introducing tube and a pressure gauge.
1.36 g (0.87 mol) was added and the mixture was sealed. Further, 300 ml of toluene as a solvent was added to the autoclave, and the mixture was heated to 120 ° C. while stirring. Next, 504.8 g (7.0 mol) of 1,2-butylene oxide was injected from a liquid introduction tube by a pump for 6 hours to cause a reaction.

Without opening the autoclave, 184.5 g (1.3 mol) of methyl iodide was added from the liquid introduction tube and sealed, and the temperature was gradually raised with stirring and the reaction was carried out at 90 ° C. for 3 hours.

The autoclave was opened, and the 2 liter separating funnel was washed with 500 ml of toluene and washed with 5
It was washed 5 times with 00 ml of pure water. The toluene solution was separated and dehydrated, and then the solvent and light components were removed under the conditions of 120 ° C. and 1 mmHg or less. The obtained liquid was treated with low temperature activated clay for 60 minutes at 60 ° C., and the clay was separated to obtain 530 g of a compound containing dimethyl ether of polyoxybutylene glycol as a main component as a colorless transparent liquid.

Synthetic Example 7 By the same apparatus, conditions and method as in Synthetic Example 1 except that methyl etherification of the terminal hydroxyl group of the reaction product with methyl iodide and tetrabutylammonium bromide as a phase transfer catalyst is not carried out. Methyl-α-D-glucoside-terminated 1,2-butylene oxide is subjected to addition polymerization and the reaction product is subjected to post-treatment to obtain a methyl-α-D-glucoside-terminated polyoxy as a colorless transparent liquid. 75 g of a mixture of alkylene compounds was obtained.

Synthesis Example 8 173.1 g (2.4 mol) of 1,2-butylene oxide
By the same apparatus, conditions and method as in Synthesis Example 1 except that 139.4 g (2.4 mol) of propylene oxide was used instead of propylene oxide, addition polymerization and reaction of propylene oxide having methyl-α-D-glucoside as an end group. Methyl etherification of the terminal hydroxyl groups of the product and post-treatment of the reaction product were performed to obtain 78 g of a mixture of polyoxyalkylene compounds as a colorless transparent liquid.

Examples 1 to 5 and Comparative Examples 1 to 4 Polyoxyalkylene compounds according to the present invention (Examples 1 to 5) obtained in the above Synthesis Examples 1 to 5 and the above Synthesis Examples 6 to 8
The following tests were carried out on the polyoxyalkylene compounds (Comparative Examples 1 to 3) outside the scope of the present invention obtained in 1. and the commercially available polypropylene glycol dimethyl ether (Comparative Example 4). Table 1 shows the properties and test results of these sample oils. (High-temperature two-layer separation temperature with HFC-134a) Capacity 10m
0.15 g of each sample oil of the example and the comparative example was put into a pressure-resistant glass tube of l, and a refrigerant (HFC-134a) was further added.
4.85 g of {refrigerant: sample oil = 100: 3.1 (parts by weight)}, and put each glass tube in a constant temperature bath at a predetermined temperature to see if the refrigerant and sample oil are mutually dissolved at high temperature. , It was observed whether it was separated or clouded. (Low temperature two-layer separation temperature with HFC-134a) JIS K
2211 4.12, using 5 g of each sample oil of Examples and Comparative Examples and 20 g of refrigerant (HFC-134a) {refrigerant: sample oil = 100: 25 (parts by weight)}, Whether they melt each other at low temperatures,
It was observed whether they were separated or clouded. (Volume resistivity) 25 ° C according to JIS C 2101
The volume resistivity of each sample oil was measured.

[0080]

[Table 1]

As is clear from the results of the examples and comparative examples shown in Table 1, the polyoxyalkylene compounds of Examples 1 to 5 according to the present invention are soluble in the HFC refrigerant in a wide temperature range and have an excellent electrical property. It combines good performance with being excellent.

On the other hand, Comparative Example 1 containing a dimethyl ether compound of polyoxybutylene glycol as a main component
Although the sample oil of No. 2 was excellent in electric characteristics, it was much inferior to the polyoxyalkylene compound according to the present invention in compatibility with the HFC refrigerant. In addition, the compound of Comparative Example 2 in which the terminal hydroxyl group is not methyl etherified (hydroxyl value is outside the range of the present invention), the compound of Comparative Example 3 obtained by using propylene oxide instead of butylene oxide (p
The value of / (p + q) is outside the range of the present invention) and the compound of Comparative Example 4 which is a commercially available polypropylene glycol dimethyl ether are both excellent in compatibility with the HFC refrigerant, but have electrical characteristics according to the present invention. It was much inferior to the oxyalkylene compound.

[0083]

As described above, the refrigerating machine lubricating oil of the present invention containing a polyoxyalkylene compound having a specific structure as a main component can be used in combination with a fluorinated alkane refrigerant such as HFC-134a or a chlorofluoroalkane refrigerant. It is a lubricating oil that dissolves in a wide temperature range and has excellent electrical characteristics, and that it does not hydrolyze.

Therefore, the refrigerating machine lubricating oil of the present invention is very useful especially as a refrigerating machine oil for use with a fluoroalkane refrigerant or a chlorofluoroalkane refrigerant refrigerant. The refrigerator of the present invention, which is stable and compatible with each other for a long period of time, has excellent electric characteristics, and does not generate an acid by hydrolysis by mixing with and / or a fluorinated alkane. A composition for use is obtained.

Further, by using the lubricating oil for a refrigerator of the present invention, there is no fear of electric leakage even in a hermetic compressor having a structure in which the oil and the electrode are in contact with each other, and corrosion by the acid generated by the hydrolysis of the lubricating oil is eliminated. Inconveniences such as are sufficiently prevented. Therefore, by using the lubricating oil for a refrigerating machine of the present invention as a lubricating oil in a refrigerating machine using a fluorinated alkane and / or a chlorofluoroalkane as a refrigerant, a long-term without causing leakage of electricity or corrosion by an acid, etc. Thus, the refrigeration equipment of the present invention can be obtained which can be stably operated over a long period of time.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI C10N 30:12 C10N 30:12 40:30 40:30 (72) Inventor Satoshi Suda 8 Chidori-cho, Naka-ku, Yokohama, Japan Japan (6) Reference JP 4-41591 (JP, A) JP 4-41592 (JP, A) JP 3-70794 (JP, A) JP 3 -70795 (JP, A) JP 4-20596 (JP, A) JP 3-47895 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C10M 105/18 C10M 107/34 C10N 30:00 C10N 30:12 C10N 40:30 C09K 5/04 F25B 1/00

Claims (3)

(57) [Claims] 1. The following general formula (I): [In the formula (I), A has a heterocycle having an ether bond in the molecule and has 2 to 20 hydroxyl groups, and has 4 to 40 carbon atoms.
Showing a residue obtained by removing a hydroxyl group from the compound of R ¹ and R
² may be the same or different, each having 2 to 2 carbon atoms
6 represents an alkylene group, R ³ represents an alkyl group having 1 to 6 carbon atoms, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, a and b are respectively positive numbers, l and m , N is 0 or a positive number, and a · l + b · m =
2 to 100 and 1 + m + n = indicates an integer satisfying the condition of 2 to 20], which is a main component of one compound or a mixture of two or more compounds selected from the polyoxyalkylene compounds represented by The polyoxyalkylene compound or the mixture of two or more polyoxyalkylene compounds has (a) a hydroxyl value of 0 to 30.0 mgKOH / g, and (b) R ¹ and R in the general formula (I). The ratio of butylene groups in the total alkylene groups represented by ² must satisfy the following mathematical formula (1). [In the formula (1), p represents the number of butylene groups and q represents the number of alkylene groups having 2 to 6 carbon atoms excluding the butylene group, respectively], both conditions are satisfied at the same time. . 2. A refrigerator composition comprising (A) a lubricating oil for refrigerators according to claim 1 and (B) a mixture of a fluorinated alkane and / or a chlorofluoroalkane. 3. A refrigerating machine using (B) a fluorinated alkane and / or a chlorofluorinated alkane as a refrigerant, characterized in that (A) the refrigerating machine lubricating oil according to claim 1 is used as a lubricating oil. .