JPH09208980A - Refrigerating machine oil composition and fluid composition for refrigerating machine - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a refrigerating machine oil composition excellent in valve caulking proofness, and useful in HFC cooling medium useful in e.g. refrigerators each equipped with reciprocating or rotary closed-type compressor, by incorporating an oxygen-contg. synthetic oil in a mineral oil and/or an olefin polymer as base oil. SOLUTION: This refrigerating machine oil composition is obtained by incorporating (A) a mineral oil (e.g. paraffin or naphthene-based one) and/or an olefin polymer (e.g. polybutene) as base oil with (B) an oxygen-contg. synthetic oil (e.g. an ester, polyglycol, ketone) at 1-30wt.% based on the whole amount of this composition. Incorporation of (C) 0.005-5.0wt.% of a phosphoric ester- based compound in this composition further improves the abrasion resistance and load resistance of this composition.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a refrigerating machine oil composition and a refrigerating machine fluid composition, and more particularly, to a refrigerating machine oil composition having a specific composition and useful as a hydrofluorocarbon refrigerant and a refrigerating machine oil composition thereof. A fluid composition for a refrigerator.

[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. As the refrigerating machine oil for this HFC refrigerant, PAG (polyalkylene glycol), ester, etc. which are compatible with HFC have been studied or used. For example, regarding PAG, US Pat. No. 4,755,316, JP-A 1-1
98694, 1-256594, 1-259093, 1-259094
No. 1-259095, 1-274191, 2-43290, 2-5
No. 5791, No. 2-84491, etc., and regarding ester, publication No. 3-505602, JP-A No. 3-88892, 2-128.
991, 3-128992, 3-200895, 3-227397,
4-20597, 4-72390, 4-218592, 4-249593
No. etc. However, PAG has a high hygroscopic property, and the electrical characteristics (volume resistivity) are not good. Ester oil may undergo hydrolysis due to its structure and generate an acid, and various inconveniences are expected to occur.
In addition, these oils are mineral oil / CFC, or mineral oil / H
There is a big problem that the lubricity is inferior to that of the CFC system. On the other hand, JP-A-5-157379 describes a refrigeration system for HFC-134a refrigerant, which uses refrigerating machine oil that is incompatible with the refrigerant. Further, JP-A-5-59386 describes a refrigerator oil for tetrafluoroethane using a mixed oil of a hydrocarbon compound and an ester or an ether. When a hydrocarbon oil is used as a refrigerating machine oil for HFC refrigerant, an oil having a relatively low viscosity tends to be used in order to secure oil return. However, it has been found that the use of low viscosity oil has the problem of valve coking, especially in the case of reciprocating compressors having a valve mechanism. We have
Focusing on hydrocarbon oils that have no concern about hydrolysis or hygroscopicity, as a result of intensive research, we found that the inclusion of specific compounds in hydrocarbon oils can significantly reduce valve coking when using HFC refrigerants. The present invention has been completed.

[0003]

DISCLOSURE OF THE INVENTION The present invention is directed to a refrigerating machine oil composition which can be used for an HFC refrigerant and has an excellent valve coking prevention property, and the refrigerating machine oil composition and HFC.
An object is to provide a fluid composition for a refrigerator, which comprises a refrigerant.

[0004]

That is, a refrigerating machine oil composition for a hydrofluorocarbon refrigerant according to the present invention uses a mineral oil and / or an olefin polymer as a base oil, and a synthetic oil containing oxygen as a basis of the total amount of the composition. 1 to 30 mass%
Is included. And the fluid composition for refrigerators concerning the present invention contains a hydrofluorocarbon refrigerant and the above-mentioned refrigerator oil composition for hydrofluorocarbon refrigerants.

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION The contents of the present invention will be described in detail below. A mineral oil and / or an olefin polymer can be used as the base oil (hereinafter referred to as “component (A)”) in the refrigerator oil composition of the present invention. As the mineral oil, specifically, for example, a lubricating oil fraction obtained by distilling crude oil under atmospheric pressure and vacuum distillation is used for solvent degassing, solvent extraction, hydrocracking, solvent dewaxing, catalytic dewaxing, hydrogenation. Oils such as paraffin-based and naphthene-based oils, which are refined by appropriately combining refining treatments such as purification, sulfuric acid washing, and clay treatment, can be used. Further, as the olefin polymer, those obtained by polymerizing olefins having 2 to 10 carbon atoms and those obtained by hydrogenating this can be used, and specifically, for example, polybutene, polyisobutene, and 5 to 10 carbon atoms can be used. [Alpha] -olefin oligomers, ethylene-propylene copolymers, and hydrogenated products thereof are preferably used. These mineral oils and olefin polymers may be used alone or in combination of two or more. The viscosity of component (A) is not particularly limited, 3 to 50 mm in the preferred kinematic viscosity 40 ° C. ² /
s, more preferably 4 to 40 mm ² / s, particularly preferably 5
~ 35 mm ² / s.

The refrigerator oil composition of the present invention contains oxygen-containing synthetic oil (hereinafter referred to as "component (B)") in addition to the above base oil. The synthetic oils preferable as the component (B) are specifically esters, polyglycols, ketones, polyphenyl ethers, silicones, polysiloxanes, perfluoroethers, etc. Among them, the (a) ester and (b) poly Glycol, (c) ketone and mixtures thereof are more preferably used.

Examples of the above-mentioned (a) ester include:
Examples thereof include aromatic esters, dibasic acid esters, polyol esters, complex esters, polyol carbonic acid esters, and mixtures thereof. As the aromatic ester, 1 to 6 valent, preferably 1 to 4 valent, more preferably 1 to 3 valent aromatic carboxylic acid, and 1 to 1 carbon atoms
8, preferably 2 to 15, saturated or unsaturated aliphatic 1
Esters with a polyhydric alcohol are used. Specific examples of the 1- to 6-valent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid. The aliphatic monohydric alcohol having 1 to 18 carbon atoms may be saturated or unsaturated, but is preferably saturated. As such a monohydric alcohol of fat,
It may be linear or branched, and specific examples thereof include methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched. Pentanol, straight-chain or branched hexanol, straight-chain or branched heptanol, straight-chain or branched octanol, straight-chain or branched nonanol, straight-chain or branched decanol, straight Chain or branched undecanol, straight chain or branched dodecanol, straight chain or branched tridecanol, straight chain or branched tetradecanol, straight chain or branched pentadecanol, straight chain Examples include linear or branched hexadecanol, linear or branched heptadecanol, and linear or branched octadecanol. When a divalent or higher valent aromatic carboxylic acid is used, it may be a complete ester or a partial ester, but it is preferably a complete ester. here. The complete ester means a complete ester in which all of the carboxyl groups in the aromatic carboxylic acid are esterified, and the partial ester is one in which at least one carboxyl group in the aromatic carboxylic acid is not esterified and Means ester remaining in shape. Also,
When a divalent or higher aromatic carboxylic acid is used, it may be an ester consisting of one type of alcohol residue or an ester consisting of two or more types of alcohol residue. Specific examples of the aromatic ester include diethyl phthalate, dipropyl phthalate (linear or branched), dibutyl phthalate (linear or branched), dipentyl phthalate (linear or branched) ), Dihexyl phthalate (linear or branched), diheptyl phthalate (linear or branched), dioctyl phthalate (linear or branched), dinonyl phthalate (linear or branched), Didecyl phthalate (straight or branched), diundecyl phthalate (straight or branched), didodecyl phthalate (straight or branched), ditridecyl phthalate (straight or branched), phthalic acid Ditetradecyl (straight or branched), Dipentadecyl phthalate (straight or branched), Diethyl isophthalate, Dipropyl isophthalate (straight or branched) Is branched), dibutyl isophthalate (straight or branched), dipentyl isophthalate (straight or branched), dihexyl isophthalate (straight or branched), diheptyl isophthalate (straight or branched) Form), dioctyl isophthalate (linear or branched), dinonyl isophthalate (linear or branched), didecyl isophthalate (linear or branched),
Diundecyl isophthalate (linear or branched), didodecyl isophthalate (linear or branched), ditridecyl isophthalate (linear or branched), ditetradecyl isophthalate (linear or branched), isophthalic acid Dipentadecyl (linear or branched), diethyl terephthalate, dipropyl terephthalate (linear or branched), dibutyl terephthalate (linear or branched), dipentyl terephthalate (linear or branched), Dihexyl terephthalate (linear or branched), Diheptyl terephthalate (linear or branched), Dioctyl terephthalate (linear or branched), Dinonyl terephthalate (linear or branched),
Didecyl terephthalate (linear or branched), diundecyl terephthalate (linear or branched), didodecyl terephthalate (linear or branched), ditridecyl terephthalate (linear or branched), terephthalic acid Ditetradecyl (linear or branched), dipentadecyl terephthalate (linear or branched), triethyl trimellitate, tripropyl trimellitate (linear or branched), tributyl trimellitate (linear or branched) Branched), Tripentyl trimellitate (straight or branched), Trihexyl trimellitate (straight or branched), Triheptyl trimellitate (straight or branched), Trioctyl trimellitate (straight) Or branched), Trinonyl trimellitate (straight or branched), trimellitate Tridecyl tomate (straight or branched), Triundecyl trimellitate (straight or branched), Tridodecyl trimellitate (straight or branched), Tritridecyl trimellitate (straight or branched) ), Tritetradecyl trimellitate (linear or branched), tripentadecyl trimellitate (linear or branched), tetraethyl pyromellitic acid, tetrapropyl pyromellitic (linear or branched) , Tetrabutyl pyromellitic acid (linear or branched), tetrapentyl pyromellitic acid (linear or branched),
Tetrahexyl pyromellitic acid (linear or branched), tetraheptyl pyromellitic acid (linear or branched), tetraoctyl pyromellitic acid (linear or branched), tetranonyl pyromellitic acid (linear) Or branched), tetradecyl pyromellitic acid (linear or branched), tetraundecyl pyromellitic acid (linear or branched), tetradodecyl pyromellitic acid (linear or branched), pyromellitic acid Examples include tetratridecyl (linear or branched), tetratetradecyl pyromellitic acid (linear or branched), tetrapentadecyl pyromellitic acid (linear or branched), and the like. Further, as a matter of course, the aromatic ester may be a single compound or a mixture of two or more compounds. Examples of the dibasic acid ester include dibasic acids having 5 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid, and methanol, ethanol, propanol, butanol, pentanol, hexanol, Preferred are esters with monohydric alcohols having a linear or branched alkyl group having 1 to 15 carbon atoms such as heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, and pentadecanol, and mixtures thereof. More specifically, ditridecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di2-ethylhexyl sebacate, and mixtures thereof can be used. As the polyol ester, 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- Examples include dodecanediol. 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 condensates, 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). Specific examples of the fatty acid include pentanoic acid,
Hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, icosanoic acid, oleic acid, etc. Examples thereof include chains or branched ones, so-called neo acids having a quaternary α carbon atom, and the like. More specifically, valeric acid, isopentanoic acid, capric acid, pelargonic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, caprylic acid, 2-ethylhexanoic acid,
More preferred are normalnonanoic acid and 3,5,5-trimethylhexanoic acid. The polyol ester may have a free hydroxyl group. Incidentally, as particularly preferable ones, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane,
Esters of hindered alcohols such as di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol) and tri- (pentaerythritol), specifically, neopentyl glycol. 2-ethylhexanoate, trimethylolpropane caprylate, trimethylolpropane pelargonate, pentaerythritol 2
-Ethyl hexanoate, pentaerythritol pelargonate, and mixtures thereof and the like. The complex ester is an ester of a fatty acid and a dibasic acid with a monohydric alcohol and a polyol, and as the fatty acid, the dibasic acid, the monohydric alcohol and the polyol, a dibasic acid ester and a polyol ester are used. The same thing as illustrated can be used. Further, the polyol carbonate ester is an ester of carbonic acid with a monohydric alcohol and a polyol,
As the monohydric alcohol and polyol here,
The same as those exemplified above, polyglycol obtained by homopolymerization or copolymerization of diol, or those obtained by adding polyglycol to the polyol exemplified above can be used.

As the polyglycol (b), polyalkylene glycol, etherified products thereof, modified compounds thereof and the like are preferably used. As the polyalkylene glycol, those obtained by homopolymerizing or copolymerizing alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide are used. In the polyalkylene glycol, when alkylene oxides having different structures are copolymerized, the polymerization form of the oxyalkylene group is not particularly limited, and may be random copolymerization or block copolymerization.
The etherified product of polyalkylene glycol is an etherified product of the above hydroxyl groups of polyalkylene glycol. Specific examples of the etherified product of polyalkylene glycol include monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether,
Monopentyl ether, monohexyl ether, monoheptyl ether, monooctyl ether, monononyl ether, monodecyl ether, dimethyl ether, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, di Examples thereof include nonyl ether and didecyl ether. Further, examples of the modified compound of polyglycol include an alkylene oxide 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.

As the above-mentioned (c) ketone, a compound having at least one ketone bond between carbon and carbon can be used, but preferably, the following general formulas (1) and (2) are used. Alternatively, each ketone compound represented by the general formula (3) and a mixture thereof are used. In the above general formula (1), X represents a (m + n) -valent aromatic ring having 6 to 50 carbon atoms, preferably 6 to 20 carbon atoms or an alkyl group-substituted aromatic ring. R ¹ and R ² may be the same or different and each represents a hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, preferably an alkyl group, a phenyl group or an alkylphenyl group.
m and n may be the same or different and each is 1
It shows the integer of -20, preferably 1-10. Preferred examples of the substituent X include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring and the like, and one or more hydrogen atoms of these aromatic rings are substituted with an alkyl group having 1 to 20 carbon atoms. And alkyl-substituted aromatic rings. Further, preferred specific examples of the substituents R ¹ and R ² include
For example, methyl group, ethyl group, straight-chain or branched propyl group, straight-chain or branched butyl group, straight-chain or branched pentyl group, straight-chain or branched hexyl group, straight-chain Linear or branched heptyl group, straight chain or branched octyl group, straight chain or branched nonyl group, straight chain or branched decyl group, straight chain or branched undecyl group, straight chain Linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group,
Linear or branched hexadecyl group, linear or branched heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, A straight-chain or branched henicosyl group, a straight-chain or branched docosyl group, a straight-chain or branched tricosyl group, a straight-chain or branched tetracosyl group, a straight-chain or branched pentacosyl group, Linear or branched hexacosyl group, linear or branched heptacosyl group, linear or branched octacosyl group, linear or branched nonacosyl group, linear or branched triacontyl group, Phenyl group, tolyl group (including all substituted isomers), xylyl group (including all substituted isomers), ethylphenyl group (including all substituted isomers), direct Linear or branched propylphenyl group (including all substituted isomers), linear or branched ethylmethylphenyl group (including all substituted isomers), linear or branched butylphenyl group ( (Including all substituted isomers), diethylphenyl group (including all substituted isomers), linear or branched pentylphenyl group (including all substituted isomers), linear or branched hexyl Phenyl group (including all substituted isomers), linear or branched heptylphenyl group (including all substituted isomers), linear or branched octylphenyl group (including all substituted isomers) ), A linear or branched nonylphenyl group (including all substituted isomers), a linear or branched decylphenyl group (including all substituted isomers), a linear or Branched undecylphenyl group (including all substituted isomers), linear or branched dodecylphenyl group (including all substituted isomers), linear or branched tridecylphenyl group (all , Including a substituted isomer of), a linear or branched tetradecylphenyl group (including all substituted isomers), a linear or branched pentadecylphenyl group (including all substituted isomers), Linear or branched hexadecylphenyl group (including all substituted isomers), linear or branched heptadecylphenyl group (including all substituted isomers), linear or branched octadecyl Phenyl group (including all substituted isomers), linear or branched nonadecylphenyl group (including all isomers), linear or branched icosylphenyl group (all All substituted isomers), linear or branched henicosylphenyl groups (including all substituted isomers), linear or branched docosylphenyl groups (including all substituted isomers) ), A linear or branched tricosylphenyl group (including all substituted isomers),
A linear or branched tetracosylphenyl group (including all substituted isomers) and the like can be mentioned.

[0010]

Embedded image In the above general formula (2), R ³ and R ⁵ may be the same or different and each is a hydrocarbon group having 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, preferably an alkyl group, a phenyl group or An alkylphenyl group, R ⁴
Represents an alkylene group having 1 to 19 carbon atoms, preferably 1 to 10 carbon atoms, and o represents an integer of 1 to 5, preferably 1 to 3. Preferable specific examples of the substituents R ³ and R ⁵ include the preferable alkyl group, phenyl group and alkylphenyl group exemplified for the substituents R ¹ and R ² in the general formula (1). In addition, specific preferred examples of the substituent R ⁴ include, for example, a methylene group, a linear or branched ethylene group, a linear or branched propylene group, a linear or branched butylene group, a linear group. Linear or branched pentylene group, linear or branched hexylene group, linear or branched heptylene group, linear or branched octylene group, linear or branched nonylene group, Examples thereof include linear or branched decylene groups.

[0011]

Embedded image In the general formula (3), A represents a 1-20 valent alcohol residue, R ⁶ , R ⁷ and R ⁸ may be the same or different and each represents an alkylene group having 1 to 4 carbon atoms, R ⁹ has 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms
Represents a hydrocarbon group, preferably an alkyl group, a phenyl group or an alkylphenyl group, and p and q may be the same or different and each is 0 to 30, preferably 0 to
The integer of 20 is shown and r has shown the integer of 1-20.
Preferred specific examples of the alcohol from which the alcohol residue A is derived include, for example, methanol, ethanol, linear or branched propanol, linear or branched butanol, linear or branched pentanol, Linear or branched hexanol, linear or branched heptanol, linear or branched octanol, linear or branched nonanol, linear or branched decanol, linear or branched Undecanol, straight-chain or branched dodecanol, straight-chain or branched tridecanol, straight-chain or branched tetradecanol, straight-chain or branched pentadecanol, straight-chain or branched Hexadecanol, linear or branched heptadecanol, linear or branched octadecanol, linear or Varied nonadecanol, linear or branched icosanol, linear or branched henicosanol, linear or branched docosanol, linear or branched tricosanol, linear or branched tetracosa Aliphatic monohydric alcohols such as norol; 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- Nanjioru, 1,10-decanediol, 1,11-decanediol, 1,12-diols such as dodecanediol; trimethylolethane, trimethylolpropane,
Trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri-
(Pentaerythritol), glycerin, polyglycerin (2-20 mer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, polyhydric alcohol such as mannitol, Xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose,
Polyols such as sugars such as trehalose, sucrose, raffinose, gentianose, and melezitose; and their partially etherified products, and methyl glucosides (glycosides). Alkylene group R ⁶ , R ⁷
Specific preferred examples of R ⁸ and R ⁸ include a methylene group, a linear or branched ethylene group, a linear or branched propylene group, and a linear or branched butylene group. Preferable specific examples of the substituent R ⁹ include the preferable alkyl group, phenyl group and alkylphenyl group exemplified for the substituents R ¹ and R ² in the general formula (1).

The refrigerating machine oil composition of the present invention can be obtained by adding a base oil which is the component (A) and an oxygen-containing synthetic oil which is the component (B) as an essential component. In this case, what kind of component (A) is combined with what kind of component (B) can be arbitrarily selected. The specific examples of the combinations are as follows. 1-1. (A) Refined paraffinic mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C. and (B) aromatic ester 1-2. (A) Kinematic viscosity at 40 ° C. of 5-35 mm ² / s refined paraffinic mineral oil and (B) dibasic acid ester 1-3. (A) Refined paraffinic mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C. and (B) polyol ester 1-4. (A) Refined paraffinic mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) complex ester 1-5. (A) Refined paraffinic mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol carbonate ester 1-6. (A) Kinematic viscosity at 40 ° C. of 5-35 mm ² / s refined paraffinic mineral oil, and (B) polyalkylene glycol 1-7. (A) Kinetic viscosity at 40 ° C. of 5 to 35 mm ² / s refined paraffinic mineral oil, and (B) ether compound of polyalkylene glycol 1-8. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., refined paraffinic mineral oil, and (B) modified compound of polyalkylene glycol 1-9. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., refined paraffinic mineral oil, and (B) ketone compound represented by formula (1) 1-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Paraffinic refined mineral oil of (1), and (B) a ketone compound represented by the formula (2) 1-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Paraffinic refined mineral oil of 1. and (B) ketone compound represented by formula (3) 2-1. (A) Kinematic viscosity at 40 ° C. of 5 to 35 mm ² / s refined naphthenic mineral oil, and (B) aromatic ester 2-2. (A) Kinematic viscosity at 40 ° C. of 5-35 mm ² / s naphthenic refined mineral oil, and (B) dibasic acid ester 2-3. (A) Kinematic viscosity at 40 ° C. of 5-35 mm ² / s naphthenic refined mineral oil, and (B) polyol ester 2-4. (A) Kinematic viscosity at 40 ° C. of 5 to 35 mm ² / s refined naphthenic mineral oil, and (B) complex ester 2-5. (A) Kinematic viscosity at 40 ° C. of 5-35 mm ² / s naphthenic refined mineral oil, and (B) polyol carbonate ester 2-6. (A) naphthenic refined mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyalkylene glycol 2-7. (A) Kinetic viscosity at 40 ° C. of 5-35 mm ² / s refined naphthene-based mineral oil, and (B) etherified product of polyalkylene glycol 2-8. (A) Modified naphthenic mineral oil having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a modified compound of polyalkylene glycol 2-9. (A) Kinematic viscosity at 40 ° C. of 5 to 35 mm ² / s refined naphthenic mineral oil, and (B) ketone compound represented by general formula (1) 2-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Naphthenic refined mineral oil of No. 2, and (B) a ketone compound represented by the general formula (2) 2-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Naphthenic refined mineral oil of 1. and (B) ketone compound represented by general formula (3) 3-1. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) aromatic ester 3-2. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) dibasic acid ester 3-3. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol ester 3-4. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) complex ester 3-5. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol carbonate ester 3-6. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyalkylene glycol 3-7. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C. and (B) an etherified product of polyalkylene glycol 3-8. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a modified compound of polyalkylene glycol 3-9. (A) Polybutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a ketone compound represented by the general formula (1) 3-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
And the ketone compound represented by the general formula (2) (B) 3-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Polybutene of (4) and a ketone compound (B) represented by the general formula (3) 4-1. (A) Kinematic viscosity at 40 ° C. of 5 to 35 mm ² / s, polyisobutene, and (B) aromatic ester 4-2. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) dibasic acid ester 4-3. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol ester 4-4. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) complex ester 4-5. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol carbonate ester 4-6. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyalkylene glycol 4-7. (A) Kinetic viscosity at 40 ° C. of 5-35 mm ² / s polyisobutene, and (B) ether compound of polyalkylene glycol 4-8. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C. and (B) a modified compound of polyalkylene glycol 4-9. (A) Polyisobutene having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a ketone compound represented by the general formula (1) 4-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Polyisobutene of (4), and (B) a ketone compound represented by the general formula (2) 4-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Polyisobutene of (5) and a ketone compound (B) represented by the general formula (3) 5-1. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) aromatic ester 5-2. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) dibasic acid ester 5-3. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol ester 5-4. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) complex ester 5-5. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol carbonate ester 5-6. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyalkylene glycol 5-7. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) an etherified product of polyalkylene glycol 5-8. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a modified compound of polyalkylene glycol 5-9. (A) 1-octene oligomer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a ketone compound represented by the general formula (1) 5-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
1-octene oligomer, and (B) a ketone compound represented by the general formula (2) 5-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
1-octene oligomer, and (B) a ketone compound represented by the general formula (3) 6-1. (A) Kinetic viscosity at 40 ° C. of 5-35 mm ² / s ethylene-propylene copolymer, and (B) aromatic ester 6-2. (A) Kinetic viscosity at 40 ° C. of 5 to 35 mm ² / s ethylene-propylene copolymer, and (B) dibasic acid ester 6-3. (A) Ethylene-propylene copolymer having kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol ester 6-4. (A) Kinetic viscosity at 40 ° C. of 5 to 35 mm ² / s ethylene-propylene copolymer, and (B) complex ester 6-5. (A) Ethylene-propylene copolymer having kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) polyol carbonate ester 6-6. (A) an ethylene-propylene copolymer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a polyalkylene glycol 6-7. (A) Ethylene-propylene copolymer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) an etherified product of polyalkylene glycol 6-8. (A) Kinetic viscosity at 40 ° C. of 5-35 mm ² / s, ethylene-propylene copolymer, and (B) polyalkylene glycol modified compound 6-9. (A) an ethylene-propylene copolymer having a kinematic viscosity of 5 to 35 mm ² / s at 40 ° C., and (B) a general formula (1).
A ketone compound 6-10. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Ethylene-propylene copolymer of No. 6, and (B) a ketone compound represented by the general formula (2) 6-11. (A) Kinematic viscosity of 5 to 35 mm ² / s at 40 ° C
Ethylene-propylene copolymer and (B) a ketone compound represented by the general formula (3)

The upper limit of the content of component (B) in the refrigerator oil composition of the present invention is 30% by mass, preferably 25% by mass, more preferably 20% by mass, based on the total amount of the composition. On the other hand, the lower limit value is 1% by mass, preferably 5% by mass, more preferably 10% by mass. When the content of the component (B) exceeds 30% by mass, it is not preferable because the refrigeration compressor lacks long-term reliability. Further, if the content of the component (B) is less than 1% by mass, the valve coking prevention performance is not sufficient, which is not preferable. The upper limit of the content of the component (A) which is the base oil in the refrigerator oil composition is 99% by mass, preferably 95% by mass, more preferably 90% by mass, based on the total amount of the composition, and the lower limit is It is desirable that the total amount of the composition is 70% by mass, preferably 75% by mass, more preferably 80% by mass.

A mixture of the base oil (A) and the oxygen-containing synthetic oil (B) is HF even when no additive is added.
It can be suitably used as a refrigerating machine oil composition for C refrigerant, but can also be used by blending various additives as necessary. In particular, in order to further improve the wear resistance and load resistance of the refrigerating machine oil composition, it is preferable to add a phosphate ester compound (hereinafter, referred to as component (C)). Examples of the phosphoric acid ester-based compound include phosphoric acid triester, acidic phosphoric acid ester, amine salt of acidic phosphoric acid ester, chlorinated phosphoric acid ester, phosphorous acid triester and hydrogenated phosphorous acid ester. It The above-mentioned phosphoric acid ester compound is represented by the following general formula (4)
Can be used. (O =) _s P (-OR ¹¹ ) _t (-OH) _3-t (4) In the above general formula (4), R ¹¹ is an alkyl group having 1 to 18 carbon atoms or an alkenyl having 2 to 18 carbon atoms. Group, a phenyl group, an alkylaryl group having 7 to 10 carbon atoms and a polyoxyalkylene group represented by the following formula (5), s represents an integer of 0 or 1, and t represents 1 ~
Represents an integer of 3. However, when t is 2 or 3, R ¹¹ may be the same or different in the same molecule. -(OR < ¹² >) _u- OR < ¹³ > ... (5) (In formula (5), R < ¹² > represents a C2-C4 alkylene group, R < ¹³ > represents a hydrogen atom or a C1-C18 alkyl group. , U represents an integer of 1 to 20.) In the general formula (4), the alkyl group having 1 to 18 carbon atoms represented by R ¹¹ is, for example, a methyl group, an ethyl group, or a direct group. Linear or branched propyl group, linear or branched butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, direct A chain or branched octyl group,
A straight-chain or branched nonyl group, a straight-chain or branched decyl group, a straight-chain or branched undecyl group, a straight-chain or branched dodecyl group, a straight-chain or branched tridecyl group, Straight-chain or branched tetradecyl group, straight-chain or branched pentadecyl group, straight-chain or branched hexadecyl group, straight-chain or branched heptadecyl group, straight-chain or branched octadecyl group, etc. Is mentioned. Specific examples of the alkenyl group having 2 to 18 carbon atoms represented by R ¹¹ include ethenyl group (vinyl group),
A linear or branched propenyl group, a linear or branched butenyl group, a linear or branched pentenyl group,
Straight-chain or branched hexenyl group, straight-chain or branched heptenyl group, straight-chain or branched octenyl group, straight-chain or branched nonenyl group, straight-chain or branched decenyl group, A straight-chain or branched undecenyl group, a straight-chain or branched dodecenyl group, a straight-chain or branched tridecenyl group, a straight-chain or branched tetradecenyl group, a straight-chain or branched pentadecenyl group,
Examples thereof include a linear or branched hexadecenyl group, a linear or branched heptadecenyl group, and a linear or branched octadecenyl group. Specific examples of the alkylaryl group having 7 to 10 carbon atoms represented by R ¹¹ include tolyl group (including all substituted isomers), xylyl group (including all substituted isomers), and ethylphenyl. Group (including all substituted isomers), trimethylphenyl group (including all substituted isomers), ethylmethylphenyl group (including all substituted isomers), linear or branched propylphenyl group (all (Including all substituted isomers), tetramethylene group (including all substituted isomers), ethyldimethylphenyl group (including all substituted isomers), diethylphenyl group (including all substituted isomers), propylmethyl Examples thereof include a phenyl group (including all substituted isomers), a linear or branched butylphenyl group (including all substituted isomers), and the like. Further, R ¹¹ may be a polyoxyalkylene group represented by the above formula (5). In the above formula (5), R ¹² represents an alkylene group having 2 to 4 carbon atoms, and specific examples of such an alkylene group include a methylmethylene group (ethylidene group) and an ethylene group. 2 alkylene group; C3 alkylene group such as ethylmethylene group (propylidene group), dimethylmethylene group (isopropylidene group), methylethylene group (propylene group), trimethylene group; n-propylmethylene group (butylidene group) , Isopropylmethylene group (isobutylidene group), ethylmethylmethylene group, ethylethylene group (butylene group), 1,1-dimethylethylene group,
Examples include 1,4-dimethylethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, alkylene group having 4 carbon atoms such as tetramethylene group, and mixtures thereof. Among them, ethylene group, propylene group , Butylene groups are preferred. R ¹³ is a hydrogen atom or has 1 to 18 carbon atoms
The alkyl group represented by R ¹¹ is exemplified, and specific examples of such an alkyl group include the groups enumerated for R ¹¹ . In the general formula (4), the compound in which s is 1 and t is 3 is a phosphoric acid triester, and specific examples thereof 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, Trio Rail phosphate,
Examples thereof include triphenyl phosphate, tricresyl phosphate, trixylyl phosphate, cresyl diphenyl phosphate, xylyl diphenyl phosphate and the like. Further, in the general formula (4), the compound in which s is 1 and t is 1 or 2 is an acidic phosphate ester, and specific examples thereof include monobutyl acid phosphate, monopentyl acid phosphate, mono Hexyl Acid Phosphate, Monoheptyl Acid Phosphate, Monooctyl Acid Phosphate, Monononyl Acid Phosphate, Monodecyl Acid Phosphate, Monoundecyl Acid Phosphate, Monododecyl Acid Phosphate, Monotridecyl Acid Phosphate, Monotetradecyl Acid Phosphate, Monopentadecyl Acid Phosphate, Monohexadecyl Acid Phosphate, Monoheptadecyl Acid Phosphate, Monooctadecyl Acid Phosphate, Monooleyl Acid Sufeto, dibutyl acid phosphate, dipentyl acid phosphate, dihexyl acid phosphate, 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. General formula (4)
In the above, the compound in which s is 0 and t is 3 is a phosphorous acid triester, and specific examples thereof include tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, Trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite, tridodecyl phosphite, trioleyl phosphite,
Examples thereof include triphenyl phosphite and tricresyl phosphite. In the general formula (4), s is 0, t
The compound wherein is 1 or 2 is a hydrogenated phosphite, and specific examples thereof include dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl. Examples thereof include phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl phosphite, diphenyl phosphite and dicresyl phosphite. The component (C) may also be a salt of the acidic phosphate ester and an alkylamine having 1 to 3 alkyl groups having 1 to 8 carbon atoms. Specific examples of such an alkylamine include, for example, methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, Dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine,
Examples include tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine and the like. Further, the component (C) may be a chlorinated phosphoric acid ester in which at least one hydrogen atom of at least one substituent R ^{11 in} the above general formula (4) is substituted with a chlorine atom. Examples of such a compound include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxypropylene bis [di (chloroethyl)] phosphate, polyoxypropylene bis [di (chloropropyl). ] Phosphate, polyoxypropylene bis [di (chlorophenyl)] phosphate, and the like. When blending the component (C), it is needless to say that one kind or two or more thereof can be used, and the blending amount thereof can be arbitrarily selected, but in general, the base oil which is the component (A) and ( B)
0.005 to 5.0% by mass, preferably 0.01 to 5.0% by mass of the composition containing the oxygen-containing synthetic oil as a component.
It is preferably 3.0% by mass. When the blending amount of the component (C) is less than 0.005% by mass, the effect of improving the wear resistance and load resistance brought about by the addition of the component is poor, while the blending amount is 5.0% by mass. If it exceeds the limit, corrosion may occur in the refrigeration system after long-term use, which is not preferable. It is one of the features of the refrigerating machine oil composition of the present invention that the wear resistance and load bearing capacity are greatly improved by blending the phosphate compound as the component (C). PAG (polyalkylene glycol) and ester, which are known as HFC refrigerating machine oil compositions, are improved in wear resistance and load resistance to some extent by blending a phosphate compound, but the degree of the improvement is the present invention. It is extremely small as compared with the refrigerating machine oil composition.

In the refrigerating machine oil composition of the present invention, in order to further improve its stability, a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an allyl oxirane compound, an alkyl oxirane compound, and an alicyclic epoxy compound. Epoxidized fatty acid monoester At least one epoxy compound selected from 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,
Among them, those having one alkyl group having 4 to 10 carbon atoms,
For example, n-butyl phenyl glycidyl ether, i-butyl phenyl 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 Examples thereof include phenylglycidyl ether and decylphenylglycidyl ether. As the alkyl glycidyl ether type epoxy compound, specifically, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether,
Tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether,
Neopentyl glycol diglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, etc. It can be illustrated. Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester, and the like. Preferred examples are glycidyl 2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate, Examples thereof include glycidyl methacrylate. Specific examples of the allyloxirane include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene. Specific examples of the alkyloxirane include 1,2-
Epoxy butane, 1,2-epoxy pentane, 1,2-
Epoxy hexane, 1,2-epoxy heptane, 1,2
-Epoxyoctane, 1,2-epoxynonane, 1,2
-Epoxydecane, 1,2-epoxyundecane, 1,
2-epoxydodecane, 1,2-epoxytridecane,
1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2-epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyico Sun etc. can be illustrated. Specific examples of the alicyclic epoxy compound include 1,2
-Epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,
4-epoxycyclohexanecarboxylate, bis (3.4-epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxa) Bicyclo [4.1.
0] hept-3-yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2 −
Examples thereof include epoxy-2-methylcyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane. Specific examples of the epoxidized fatty acid monoester include esters of epoxidized fatty acid having 12 to 20 carbon atoms and alcohol or phenol having 1 to 8 carbon atoms, and alkylphenol. Particularly, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxystearic acid are preferably used. 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, preferred are phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic 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 compounded in the refrigerator oil composition of the present invention, the compounding amount is arbitrary, but 0.1 to 5.0% by mass based on the total amount of the composition,
It is preferably 0.2 to 2.0% by mass. Of course, two or more epoxy compounds may be used in combination.

Further, in order to further improve the performance of the refrigerating machine oil composition of the present invention, conventionally known refrigerating machine oil additives such as di-tert-butyl-p-cresol, bisphenol A and the like are added. Phenolic, phenyl-α-naphthylamine, N, N-di (2-
Naphtyl) -p-phenylenediamine and other amine-based antioxidants, zinc dithiophosphate and other anti-wear agents, chlorinated paraffins, sulfur compounds and other extreme pressure agents, fatty acid and other oil agents, silicone-based defoaming agents, etc. Additives, metal deactivators such as benzotriazole, viscosity index improvers, pour point depressants, detergent dispersants and the like may be added alone or in combination of several kinds. The total compounding amount of these additives is preferably 10% by mass or less, and more preferably 5% by mass or less, based on the total amount of the composition.

Examples of the hydrofluorocarbon (HFC) refrigerant used in a refrigerator using the refrigerator lubricating oil of the present invention include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-1).
25), 1,1,2,2-tetrafluoroethane (HF
HFCs such as C-134), 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), and 1,1-difluoroethane (HFC-152a) Or these two
Examples include a mixture of two or more species. These refrigerants are appropriately selected according to the use and the required performance, and for example, HFC-
134a alone; HFC-125 alone; or HFC-
134a / HFC-32 = 60-80 mass% / 40-2
0% by weight of mixture; HFC-32 / HFC-125 = 4
Mixture of 0 to 70% by mass / 60 to 30% by mass; HFC-
125 / HFC-143a = 40-60 mass% / 60-
40 mass% mixture; HFC-134a / HFC-32
/ HFC-125 = 60% by mass / 30% by mass / 10% by mass mixture, HFC-134a / HFC-32 / HFC
-125 = 40 to 70% by mass / 15 to 35% by mass / 5
40% by weight mixture; HFC-125 / HFC-134
A preferable example is a mixture of a / HFC-143a = 35 to 55% by mass / 1 to 15% by mass / 40 to 60% by mass. More specifically, HFC-134a /
HFC-32 = 70/30 wt% mixture; HFC-3
2 / HFC-125 = 60/40 mass% mixture; HF
C-32 / HFC-125 = 50/50 mass% mixture (R410A; Allied Signal, Genetro)
n AZ-20); HFC-32 / HFC-125 = 4
5/55 mass% mixture (R410B; S manufactured by DuPont)
UVA AC9100); HFC-125 / HFC-1
43a = 50/50 mass% mixture (R507C; Genetron AZ-50 manufactured by Allied Signal Co.);
HFC-32 / HFC-125 / HFC-134a = 3
0/10/60 wt% mixture; HFC-32 / HFC
-125 / HFC-134a = 23/25/52 mass%
Mixture (R407C; DuPont SUVA AC
9000); HFC-125 / HFC-134a / HF
C-143a = 44/4/52 mass% mixture (R40
4A; DuPont SUVA HP-62) and the like. In addition, a small amount of these HFC refrigerants, for example, 1 to
It is also possible to mix 10% by weight of hydrocarbon refrigerants such as propane, cyclopropane, butane, isobutane, cyclobutane, n-pentane.

The refrigerator oil composition according to the present invention is usually
In the refrigerator, it exists in the form of a fluid composition for refrigerator mixed with HFC as described above. The mixing ratio of the refrigerating machine oil and the refrigerant in this fluid composition is arbitrary, but normally, the refrigerating machine oil is 1 to 50 relative to 100 parts by weight of the refrigerant.
It is 0 part by weight, preferably 2 to 400 parts by weight. The refrigerating machine oil composition of the present invention is particularly preferably used for an air conditioner or a refrigerator having a reciprocating or rotating hermetic compressor because of its excellent electric characteristics and low hygroscopicity. In addition, automotive air conditioners, dehumidifiers, freezers, freezers, refrigerators, vending machines,
It is particularly preferably used as a cooling device for showcases, chemical plants and the like. Further, it is also preferably used for those having a centrifugal compressor.

[0019]

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. Using the base oils shown in Table 1 and the additives shown in Table 2, refrigerating machine oil compositions having the compositions shown in Table 3 were prepared, and the following evaluation tests were performed on each composition. The test results are also shown in Table 3.

[0020]

[Table 1] Kinematic viscosity (mm ² / s) Base oil 40 ° C 100 ° C A Refined naphthenic mineral oil 9.3 2.45 B Refined naphthenic mineral oil 32.5 4.71 C 1-decene oligomer 5.13 1.72 D 1-decene oligomer 16.9 3.91 E pentaerythritol , 2-Ethylhexanoic acid / 3,5,5-trimethylhexanoic acid tetraester 66.9 8.18 F Polypropylene glycol monobutyl ether 32.5 6.71 G Di-2-ethylhexyl phthalate 27.0 4.17 H Tri-2-ethylhexyl trimellitate 84.7 9.28

[0021]

[Table 2] Additive compound name A tricresyl phosphate B dioleyl hydrogen phosphite C di (2-ethylhexyl) acid phosphate D paratertiary butyl phenyl glycidyl ether E neodecanoic acid glycidyl ester F 2,6-diter Shary butyl-p-cresol

[Evaluation Test 1] In a refrigerant atmosphere (HFC-1
34a is flown at a rate of 23 L / h) and a test piece is installed with an inclination, and test oil is dropped on the test piece at a rate of 30 drops / minute as shown in FIG. The oil is collected by an oil receiver and circulated by a pump. A high temperature thin film caulking test was conducted under the conditions of a test time of 6 hours, a test piece temperature of 270 degrees C, and a scraper frequency of 18 times / minute.
The weight of the deposit on the test piece after the test was measured. With [Evaluation Test 2] reciprocating compressor, filled with test oil 250g and HFC-134a100g, discharge pressure 16 kgf / cm ² G, the suction pressure 0 kgf / cm ² G, the rotation number 3000
Continuous operation was carried out for 1000 hours under the conditions of rpm and test temperature of 160 ° C., and the deposits on the valve of the compressor were observed after 1000 hours.

As is clear from the results of the evaluation test shown in Table 3, the refrigerator oil composition according to the present invention has a small amount of deposits on the test piece and a small amount of coke deposits on the valve of the compressor. I understand. On the other hand, the refrigerating machine oil compositions of Comparative Examples 1 to 4 are the cases where the synthetic oil containing the component (B) oxygen is not used, but the amount of deposits on the test piece is large, and It can be seen that the amount of coke deposited on the valve is large.

[Brief description of drawings]

FIG. 1 is an explanatory diagram of a test apparatus used for evaluation test 1.

[Explanation of symbols]

 1 Test piece 2, 3 Sample oil 4 Oil pan 5 Scraper

[Table 3]

Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display area C10M 107: 06 107: 08 107: 10 105: 34 105: 36 105: 38 105: 42 105: 18 105: 20 107: 34 107: 32) C10N 30:04 30:10 40:30

Claims (2)

[Claims] 1. A refrigerating machine oil composition for a hydrofluorocarbon refrigerant, comprising a mineral oil and / or an olefin polymer as a base oil, and a synthetic oil containing oxygen in an amount of 1 to 30% by mass based on the total amount of the composition. . 2. A fluid composition for a refrigerator containing [I] a hydrofluorocarbon refrigerant and the composition according to claim 1.