JP5509286B2 - Lubricating oil composition for refrigerator - Google Patents

Description

  The present invention relates to a lubricating oil composition for a refrigerator, and more specifically, for a refrigerator using a specific refrigerant such as a fluorinated ether compound, which is a refrigerant that has a low global warming potential and can be used particularly in current car air conditioner systems. The present invention relates to a lubricating oil composition for a refrigerator using a base oil mainly composed of a specific oxygen-containing compound.

  Generally, a compression type refrigerator is composed of at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), an evaporator, or a dryer, and a mixed liquid of refrigerant and lubricating oil (refrigerant oil) is hermetically sealed. It has a structure that circulates inside. In such a compressor type refrigerator, although it depends on the type of equipment, it is generally high temperature in the compressor and low temperature in the cooler, so refrigerant and lubricating oil are phase separated within a wide temperature range from low temperature to high temperature. It is necessary to circulate in this system without doing so. Generally, the refrigerant and the lubricating oil have a region where they are phase-separated into a low temperature side and a high temperature side, and the maximum temperature of the separation region on the low temperature side is preferably −10 ° C. or less, particularly preferably −20 ° C. or less. On the other hand, the minimum temperature of the separation region on the high temperature side is preferably 30 ° C. or higher, particularly preferably 40 ° C. or higher. If phase separation occurs during the operation of the refrigerator, the life and efficiency of the apparatus will be significantly adversely affected. For example, if phase separation of refrigerant and lubricating oil occurs in the compressor part, the moving part becomes poorly lubricated, causing seizure and the like, which significantly shortens the life of the device, while phase separation occurs in the evaporator In addition, since there is a lubricating oil having a high viscosity, the efficiency of heat exchange is reduced.

Conventionally, chlorofluorocarbon (CFC), hydrochlorofluorocarbon (HCFC), and the like have been mainly used as refrigerants for refrigerators. However, since they are chlorine-containing compounds that cause environmental problems, hydrofluorocarbon (HFC) Alternative refrigerants that do not contain chlorine, such as, have been studied. Examples of such hydrofluorocarbons include 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane, and 1,1,1-trifluoroethane (hereinafter referred to as R134a, R32, R125, and R143a, respectively). In particular, R134a has been used in a car air conditioner system.
However, since this HFC is also concerned about the impact of global warming, so-called natural refrigerants such as carbon dioxide are attracting attention as alternative refrigerants suitable for environmental protection. However, this carbon dioxide requires high pressure. Therefore, it cannot be used for the current car air conditioner system.
As a refrigerant that has a low global warming potential and can be used in the current car air conditioner system, for example, an unsaturated fluorinated hydrocarbon compound (for example, see Patent Document 1), a fluorinated ether compound (for example, see Patent Document 2), a fluorinated alcohol A refrigerant having a specific polar structure in a molecule such as a compound or a fluorinated ketone compound has been found.
With respect to lubricating oil for refrigerators using such a refrigerant, it has excellent compatibility with the refrigerant, has good sealing properties, has a low coefficient of friction at the sliding portion, and is excellent in stability. Required.

JP-T-2006-503961 JP 7-507342 A

  Under such circumstances, the present invention has a low global warming potential, and particularly for a refrigerator using a refrigerant having a specific polar structure, such as a fluorinated ether compound, which is a refrigerant that can be used in current car air conditioner systems. An object of the present invention is to provide a lubricating oil composition for a refrigerator that has excellent compatibility with the refrigerant used, has good sealing properties, has a low coefficient of friction at a sliding portion, and is excellent in stability. To do.

As a result of intensive research to achieve the above object, the present inventors have used a specific oxygen-containing compound as the base oil, and preferably used a specific material for the sliding part of the refrigerator. Found that it can be achieved. The present invention has been completed based on such findings.
That is, the present invention

(1) The following molecular formula (A)
C _p O _q F _r R _s (A)
[Wherein, R represents Cl, Br, I or H, p is 1 to 6, q is 0 to 2, r is 1 to 14, and s is an integer of 0 to 13. However, when q is 0, p is 2 to 6 and has one or more carbon-carbon unsaturated bonds in the molecule. ]
A lubricating oil composition for a refrigerator using a refrigerant comprising at least one fluorine-containing organic compound selected from the compounds represented by: or a combination of the fluorine-containing organic compound and a saturated fluorinated hydrocarbon compound, As the base oil, at least one oxygen-containing material selected from polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycols or their monoether and polyvinyl ether copolymers, polyol esters and polycarbonates A lubricating oil composition for a refrigerator, wherein the composition contains a compound as a main component,
(2) A refrigerant containing at least one fluorine-containing organic compound selected from a fluorinated ether compound, a fluorinated alcohol compound, and a fluorinated ketone compound, or a combination of the fluorinated organic compound and a saturated fluorinated hydrocarbon compound. A lubricating oil composition for a refrigerating machine using a polyoxyalkylene glycol, polyvinyl ether, poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether, polyol ester as a base oil And a lubricating oil composition for refrigerating machines, comprising a main component containing at least one oxygen-containing compound selected from polycarbonates,
(3) The lubricating oil composition for a refrigerator according to (1) or (2) above, wherein the base oil has a kinematic viscosity at 100 ° C. of ² to 50 mm ² / s,
(4) The lubricating oil composition for a refrigerator according to any one of the above (1) to (3), wherein the number average molecular weight of the base oil is 500 or more,
(5) The lubricating oil composition for a refrigerator according to any one of (1) to (4) above, wherein the flash point of the base oil is 150 ° C. or higher.

(6) The refrigeration according to any one of (1) to (5) above, which contains at least one additive selected from extreme pressure agents, oily agents, antioxidants, acid scavengers and antifoaming agents. Lubricating oil composition for machine,
(7) The lubricating oil composition for a refrigerator according to any one of (1) to (6), wherein the fluorinated ether compound of the refrigerant is fluorinated dimethyl ether,
(8) The lubricating oil composition for a refrigerator according to any one of (1) to (7), wherein the fluorinated alcohol compound of the refrigerant is fluorinated methyl alcohol,
(9) The lubricating oil composition for a refrigerator according to any one of (1) to (8) above, wherein the fluorinated ketone compound of the refrigerant is acetone fluoride,
(10) Any of the above (1) to (9), wherein the saturated fluorinated hydrocarbon compound of the refrigerant is at least one selected from 1,1-difluoroethane, trifluoroethane, tetrafluoroethane and pentafluoroethane A lubricating oil composition for a refrigerator according to claim 1,
(11) The lubricating oil composition for a refrigerator according to any one of (1) to (10) above, wherein the sliding portion of the refrigerator is made of an engineering plastic, or has an organic coating film or an inorganic coating film. object,
(12) The lubricating oil composition for a refrigerator according to the above (11), wherein the organic coating film is a polytetrafluoroethylene coating film, a polyimide coating film or a polyamideimide coating film,
(13) The lubricating oil composition for a refrigerator according to the above (11), wherein the inorganic coating film is a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, or a molybdenum film,
(14) Car air conditioner, electric car air conditioner, gas heat pump, air conditioning, refrigerator, vending machine or various hot water supply systems for showcases, or any one of the above (1) to (13) used for a refrigeration / heating system (15) The lubricating oil composition for a refrigerator according to (14), wherein the water content in the system is 300 ppm by mass or less and the residual air amount is 10 kPa or less,
Is to provide.

  According to the present invention, the refrigerant used for a refrigerator having a low global warming potential and using a refrigerant having a specific polar structure such as a fluorinated ether compound, which is a refrigerant that can be used particularly in current car air conditioner systems. It is possible to provide a lubricating oil composition for a refrigerating machine that has excellent compatibility with the above, has good sealing properties, has a low coefficient of friction at the sliding portion, and is excellent in stability.

The lubricating oil composition for refrigerators of the present invention has the following molecular formula (A)
C _p O _q F _r R _s (A)
[Wherein, R represents Cl, Br, I or H, p is 1 to 6, q is 0 to 2, r is 1 to 14, and s is an integer of 0 to 13. However, when q is 0, p is 2 to 6 and has one or more carbon-carbon unsaturated bonds in the molecule. ]
A lubricating oil composition for a refrigerator using a refrigerant containing at least one fluorine-containing organic compound selected from the compounds represented by: or a combination of the fluorine-containing organic compound and a saturated fluorinated hydrocarbon compound.

<Refrigerant>
The molecular formula (A) represents the type and number of elements in the molecule, and the molecular formula (A) represents a fluorine-containing organic compound having 1 to 6 carbon atoms C. If it is a fluorine-containing organic compound having 1 to 6 carbon atoms, it can have physical and chemical properties such as boiling point, freezing point, and latent heat of vaporization required as a refrigerant.
In the molecular formula (A), the bond form of p carbon atoms represented by C _p includes a carbon-carbon single bond, an unsaturated bond such as a carbon-carbon double bond, a carbon-oxygen double bond, and the like. It is. The carbon-carbon unsaturated bond is preferably a carbon-carbon double bond from the viewpoint of stability, and the number thereof is one or more, but one is preferable.
In the molecular formula (A), the bonding form of q oxygen atoms represented by O _q is preferably oxygen derived from an ether group, a hydroxyl group or a carbonyl group. The number q of oxygen atoms may be 2 and includes the case of having two ether groups or hydroxyl groups.
Further, when _q in O _q is 0 and no oxygen atom is contained in the molecule, p is 2 to 6, and the molecule has one or more unsaturated bonds such as a carbon-carbon double bond. That is, at least one of the bonding forms of p carbon atoms represented by C _p needs to be a carbon-carbon unsaturated bond.
In the molecular formula (A), R represents Cl, Br, I, or H, and any of these may be used. However, since there is little risk of destroying the ozone layer, R may be H. preferable.
As described above, preferred examples of the fluorine-containing organic compound represented by the molecular formula (A) include a fluorinated ether compound, a fluorinated alcohol compound, a fluorinated ketone compound, and an unsaturated fluorinated hydrocarbon compound.
Hereinafter, these compounds will be described.

[Fluorinated ether compound]
In the present invention, examples of the fluorinated ether compound used as the refrigerant of the refrigerator include, in the molecular formula (A), R is H, p is 2 to 6, q is 1 to 2, r is 1 to 14, Examples include fluorinated ether compounds in which s is 0 to 13.
Preferably, such a fluorinated ether compound is, for example, a fluorinated product of a chain aliphatic ether having 2 to 6 carbon atoms, having 1 to 2 ether bonds, and an alkyl group being linear or branched. Further, there can be mentioned a fluorinated product of a cyclic aliphatic ether having 3 to 6 carbon atoms and having 1 to 2 ether bonds.
Specifically, dimethyl ether introduced with 1 to 6 fluorine atoms, methyl ethyl ether introduced with 1 to 8 fluorine atoms, dimethoxymethane introduced with 1 to 8 fluorine atoms, 1 to 10 Methyl propyl ethers having 1 fluorine atom introduced, methyl butyl ethers having 1 to 12 fluorine atoms introduced, ethyl propyl ethers having 1 to 12 fluorine atoms introduced, 1 to 6 fluorine atoms Examples include oxetane into which atoms are introduced, 1,3-dioxolane into which 1 to 6 fluorine atoms are introduced, and tetrahydrofuran into which 1 to 8 fluorine atoms are introduced.

Examples of these fluorinated ether compounds include hexafluorodimethyl ether, pentafluorodimethyl ether, bis (difluoromethyl) ether, fluoromethyl trifluoromethyl ether, trifluoromethyl methyl ether, perfluorodimethoxymethane, 1-trifluoromethoxy-1, 1,2,2-tetrafluoroethane, difluoromethoxypentafluoroethane, 1-trifluoromethoxy-1,2,2,2-tetrafluoroethane, 1-difluoromethoxy-1,1,2,2-tetrafluoroethane 1-difluoromethoxy-1,2,2,2-tetrafluoroethane, 1-trifluoromethoxy-2,2,2-trifluoroethane, 1-difluoromethoxy-2,2,2-trifluoroethane, perfluoro Kisetan, perfluoro-1,3-dioxolane, various isomers of pentafluoropropane oxetane, and the like tetrafluorooxetane of various isomers.
In the present invention, this fluorinated ether compound may be used alone or in combination of two or more.

[Fluoroalcohol compound]
In the present invention, examples of the fluorinated alcohol compound represented by the general formula (A) used as the refrigerant of the refrigerator include, for example, in the molecular formula (A), R is H, p is 1 to 6, and q is 1. -2, r is 1 to 13, and s is 1 to 13 fluorinated ether compound.
Preferable examples of such a fluorinated alcohol compound include a fluorinated product of a linear or branched aliphatic alcohol having 1 to 6 carbon atoms and having 1 to 2 hydroxyl groups.
Specifically, methyl alcohol introduced with 1 to 3 fluorine atoms, ethyl alcohol introduced with 1 to 5 fluorine atoms, propyl alcohols introduced with 1 to 7 fluorine atoms, 1 to Butyl alcohols with 9 fluorine atoms introduced, pentyl alcohols with 1 to 11 fluorine atoms introduced, ethylene glycol with 1 to 4 fluorine atoms introduced, 1 to 6 fluorine atoms Examples include propylene glycol introduced.

Examples of these fluorinated alcohol compounds include monofluoromethyl alcohol, difluoromethyl alcohol, trifluoromethyl alcohol, various isomers of difluoroethyl alcohol, various isomers of trifluoroethyl alcohol, various isomers of tetrafluoroethyl alcohol, Various isomers of pentafluoroethyl alcohol and difluoropropyl alcohol, various isomers of trifluoropropyl alcohol, various isomers of tetrafluoropropyl alcohol, various isomers of pentafluoropropyl alcohol, various isomers of hexafluoropropyl alcohol, hepta Fluoropropyl alcohol, difluorobutyl alcohol isomers, trifluorobutyl alcohol isomers, tetrafluorobutyl alcohol Isomers, various isomers of pentafluorobutyl alcohol, various isomers of hexafluorobutyl alcohol, various isomers of heptafluorobutyl alcohol, various isomers of octafluorobutyl alcohol, various isomers of nonafluorobutyl alcohol, difluoroethylene glycol , Trifluoroethylene glycol, tetrafluoroethylene glycol, various isomers of difluoropropylene glycol, various isomers of trifluoropropylene glycol, various isomers of tetrafluoropropylene glycol, various isomers of pentafluoropropylene glycol, hexa Fluorinated propylene glycol such as fluoropropylene glycol, and trimethylene glycol fluorinated corresponding to this fluorinated propylene glycol. It is.
In the present invention, these fluorinated alcohol compounds may be used alone or in combination of two or more.

[Fluorinated ketone compounds]
In the present invention, for example, in the molecular formula (A), R is H, p is 2 to 6, q is 1 to 2, r is 1 to 12, A fluorinated ketone compound in which s is 0 to 11 can be mentioned.
Preferable examples of such a fluorinated ketone compound include fluorinated products of aliphatic ketones having 3 to 6 carbon atoms and linear or branched alkyl groups.
Specifically, acetone introduced with 1 to 6 fluorine atoms, methyl ethyl ketone introduced with 1 to 8 fluorine atoms, diethyl ketone introduced with 1 to 10 fluorine atoms, 1 to 10 Examples include methyl propyl ketones into which fluorine atoms are introduced.

Examples of these fluorinated ketone compounds include hexafluorodimethyl ketone, pentafluorodimethyl ketone, bis (difluoromethyl) ketone, fluoromethyl trifluoromethyl ketone, trifluoromethyl methyl ketone, perfluoromethyl ethyl ketone, and trifluoromethyl-1,1. , 2,2-tetrafluoroethyl ketone, difluoromethyl pentafluoroethyl ketone, trifluoromethyl-1,1,2,2-tetrafluoroethyl ketone, difluoromethyl-1,1,2,2-tetrafluoroethyl ketone, Examples include difluoromethyl-1,2,2,2-tetrafluoroethyl ketone, trifluoromethyl-2,2,2-trifluoroethyl ketone, and difluoromethyl-2,2,2-trifluoroethyl ketone.
In the present invention, these fluorinated ketone compounds may be used alone or in combination of two or more.

[Unsaturated fluorinated hydrocarbon compound]
In the present invention, as an unsaturated fluorinated hydrocarbon compound used as a refrigerant for a refrigerator, for example, in the molecular formula (A), R is H, p is 2 to 6, q is 0, and r is 1 to 12. , S is an unsaturated fluorinated hydrocarbon compound having 0-11.
Preferable examples of such unsaturated fluorinated hydrocarbon compounds include fluorinated products of linear or branched chain olefins having 2 to 6 carbon atoms and cyclic olefins having 4 to 6 carbon atoms.
Specifically, ethylene introduced with 1 to 3 fluorine atoms, propene introduced with 1 to 5 fluorine atoms, butenes introduced with 1 to 7 fluorine atoms, 1 to 9 Pentenes introduced with fluorine atoms, hexenes introduced with 1 to 11 fluorine atoms, cyclobutene introduced with 1 to 5 fluorine atoms, cyclopentene introduced with 1 to 7 fluorine atoms, 1 And cyclohexene into which 9 fluorine atoms are introduced.
Among these unsaturated fluorinated hydrocarbon compounds, fluoride of propene is preferable, for example, various isomers of pentafluoropropene, 3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene. Is preferred.
In the present invention, this unsaturated fluorinated hydrocarbon compound may be used alone or in combination of two or more.

[Saturated fluorinated hydrocarbon compound]
This saturated fluorinated hydrocarbon compound is a refrigerant that can be mixed, if necessary, with at least one fluorine-containing organic compound selected from the compounds represented by formula (A).
As the saturated fluorinated hydrocarbon compound, a fluoride of an alkane having 2 to 4 carbon atoms is preferable, and 1,1-difluoroethane, 1,1,1-trifluoroethane, which is a fluoride of ethane, 2-trifluoroethane, 1,1,1,2-tetrafluoroethane, 1,1,2,2-tetrafluoroethane, 1,1,1,2,2-pentafluoroethane are preferred. These saturated fluorinated hydrocarbon compounds may be used alone or in combination of two or more.
The blending amount of the saturated fluorinated hydrocarbon compound is usually 30% by mass or less, preferably 20% by mass or less, more preferably 10% by mass or less, based on the total amount of the refrigerant.
The present invention also provides at least one fluorine-containing organic compound selected from the above-mentioned fluorinated ether compounds, fluorinated alcohol compounds, and fluorinated ketone compounds, or the fluorinated organic compound and the saturated fluorinated hydrocarbon compound. There is also provided a lubricating oil composition for a refrigerator using a refrigerant containing a combination of the above.

  The refrigerating machine lubricating oil composition of the present invention (hereinafter sometimes referred to as “refrigerating machine oil composition”) is a refrigerating machine lubricating oil composition that uses the above-described refrigerant, and is used as a base oil. Oxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether, at least one oxygen-containing compound selected from among polyol esters and polycarbonates as a main component It is characterized by using what to do.

<Base oil>
[Polyoxyalkylene glycols]
Examples of the polyoxyalkylene glycols that can be used as the base oil in the refrigerating machine oil composition of the present invention include, for example, the general formula (I)
R ¹ − [(OR ² ) _m −OR ³ ] _n (I)
(Wherein R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R ² Is an alkylene group having 2 to 4 carbon atoms, R ³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, n is an integer of 1 to 6, and m is an average value of m × n Indicates a number from 6 to 80.)
The compound represented by these is mentioned.

In the general formula (I), the alkyl group in R ¹ and R ³ may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. When the number of carbon atoms in the alkyl group exceeds 10, compatibility with the refrigerant may be reduced, and rough separation may occur. The carbon number of a preferable alkyl group is 1-6.
In addition, the alkyl group portion of the acyl group in R ¹ and R ³ may be linear, branched, or cyclic. As specific examples of the alkyl group portion of the acyl group, various groups having 1 to 9 carbon atoms exemplified as specific examples of the alkyl group can be exemplified. When the acyl group has more than 10 carbon atoms, the compatibility with the refrigerant is lowered, and phase separation may occur. A preferable acyl group has 2 to 6 carbon atoms.
When R ¹ and R ³ are both alkyl groups or acyl groups, R ¹ and R ³ may be the same or different from each other.

Further, when n is 2 or more, a plurality of R ^{3 in} one molecule may be the same or different.
When R ¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites, the aliphatic hydrocarbon group may be a chain or cyclic Also good. Examples of the aliphatic hydrocarbon group having two bonding sites include an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a cyclopentylene group, and a cyclohexylene group. Etc. Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxycyclohexane; 1,3,5-trihydroxycyclohexane, etc. The residue which remove | excluded the hydroxyl group from the polyhydric alcohol of this can be mentioned.
When the number of carbon atoms of the aliphatic hydrocarbon group exceeds 10, compatibility with the refrigerant may be reduced, and phase separation may occur. A preferable carbon number is 2-6.

R ² in the general formula (I) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.
N in the general formula (I) in an integer of 1 to 6, it is determined in accordance with the number of binding sites of R ^1. For example, when R ¹ is an alkyl group or an acyl group, n is 1, and when R ¹ is an aliphatic hydrocarbon group having 2, 3, 4, 5, and 6 binding sites, n is 2, 3 respectively. , 4, 5 and 6. Moreover, m is a number with an average value of m × n of 6 to 80, and if the average value of m × n deviates from the above range, the object of the present invention cannot be sufficiently achieved.

The polyoxyalkylene glycol represented by the general formula (I) includes a polyoxyalkylene glycol having a hydroxyl group at the terminal, and the content of the hydroxyl group is 50 mol% or less with respect to all terminal groups. If it is the ratio which becomes, even if it contains, it can be used conveniently. If the hydroxyl group content exceeds 50 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable.
Such polyoxyalkylene glycols have the general formula

(In the formula, x represents a number of 6 to 80.)
Polyoxypropylene glycol dimethyl ether represented by the general formula

(In the formula, a and b each represent a number of 1 or more and a total of 6 to 80)
Polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the general formula

(In the formula, x represents a number of 6 to 80.)
In view of economy and effect, polyoxypropylene glycol monobutyl ether represented by the following formula is preferred.
As the polyoxyalkylene glycols represented by the above general formula (I), any of those described in detail in JP-A-2-305893 can be used.
In this invention, these polyoxyalkylene glycols may be used individually by 1 type, and may be used in combination of 2 or more type.

[Polyvinyl ethers]
In the refrigerating machine oil composition of the present invention, the polyvinyl ethers that can be used as the base oil include those represented by the general formula (II)

The main component is a polyvinyl compound having a structural unit represented by:
R ⁴ , R ⁵ and R ⁶ in the general formula (II) each represent a hydrogen atom or a hydrocarbon having 1 to 8 carbon atoms, and they may be the same or different.
Here, the hydrocarbon group specifically means methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups. Groups, various heptyl groups, alkyl groups of various octyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups Groups, aryl groups of various dimethylphenyl groups, benzyl groups, various phenylethyl groups, and arylalkyl groups of various methylbenzyl groups. R ⁴ , R ⁵ and R ⁶ are particularly preferably a hydrogen atom or a hydrocarbon group having 3 or less carbon atoms.

On the other hand, R ⁷ in the general formula (II) represents a divalent hydrocarbon group having 2 to 10 carbon atoms. Here, the divalent hydrocarbon group having 2 to 10 carbon atoms specifically refers to 1,2-propylene group; 2-phenyl-1,2-propylene group; 1,3-propylene group; various butylene groups; various pentylene groups; various hexylene groups; various heptylene groups; Various nonylene groups; divalent aliphatic groups of various decylene groups, cyclohexane; methylcyclohexane; ethylcyclohexane; dimethylcyclohexane; Various phenylene groups; Various methylphenylene groups; Various ethylphenylene groups; Various dimethylphenylene groups; Divalent aromatic hydrocarbon groups such as various naphthylenes Xylene; alkyl group part of a polyalkyl aromatic hydrocarbon such as diethylbenzene, xylene; alkyl aromatic group having a monovalent bonding site on each of the alkyl group and aromatic part of an alkyl aromatic hydrocarbon such as ethylbenzene And alkyl aromatic groups having a binding site. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred. A plurality of R ⁷ Os may be the same or different.
In addition, p in general formula (II) shows the number of repetitions, The average value is 0-10, Preferably it is a number of the range of 0-5.

Furthermore, R ⁸ in the general formula (II) represents a hydrocarbon group having 1 to 10 carbon atoms, and specifically, this hydrocarbon group is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, n -Butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, alkyl groups of various decyl groups, cyclopentyl groups, cyclohexyl groups, Various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, cycloalkyl groups such as various dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethyls Such as phenyl group, various butylphenyl groups, various naphthyl groups, etc. An aryl group such as an aryl group, a benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups. Among these, a hydrocarbon group having 8 or less carbon atoms is preferable. When p is 0, an alkyl group having 1 to 6 carbon atoms is particularly preferable, and when p is 1 or more, an alkyl group having 1 to 4 carbon atoms is particularly preferable.

The polyvinyl ether compound in the present invention has a structural unit represented by the above general formula (II), and the number of repetitions thereof (that is, the degree of polymerization) may be appropriately selected according to the desired kinematic viscosity. However, it is usually ² to 50 mm ² / s (100 ° C.), preferably 3 to 40 mm ² / s (100 ° C.).

  The polyvinyl ether compound of the present invention can be produced by polymerization of a corresponding vinyl ether monomer. The vinyl ether monomers that can be used here are represented by the general formula (III)

(In the formula, R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ and p are the same as described above.)
It is represented by Examples of the vinyl ether monomer include various monomers corresponding to the above-mentioned polyvinyl ether compounds, such as vinyl methyl ether; vinyl ethyl ether; vinyl n-propyl ether; vinyl isopropyl ether; vinyl n-butyl ether; Vinyl-sec-butyl ether; vinyl-tert-butyl ether; vinyl-n-pentyl ether; vinyl-n-hexyl ether; vinyl-2-methoxyethyl ether; vinyl-2-ethoxyethyl ether; Methoxy-1-methyl ethyl ether; vinyl-2-methoxy-propyl ether; vinyl-3,6-dioxaheptyl ether; vinyl-3,6,9-trioxadecyl ether; vinyl-1,4-dimethyl-3 6-dioxaheptyl ether; vinyl-1,4,7-trimethyl-3,6,9-trioxadecyl ether; vinyl-2,6-dioxa-4-heptyl ether; vinyl-2,6,9-trioxa 1-methoxypropene; 1-ethoxypropene; 1-n-propoxypropene; 1-isopropoxypropene; 1-n-butoxypropene; 1-isobutoxypropene; 1-sec-butoxypropene; 1 2-tert-butoxypropene; 2-methoxypropene; 2-ethoxypropene; 2-n-propoxypropene; 2-isopropoxypropene; 2-n-butoxypropene; 2-isobutoxypropene; 2-sec-butoxypropene; 2 -Tert-butoxypropene; 1-methoxy-1-butene; 1-ethoxy 1-butene; 1-n-propoxy-1-butene; 1-isopropoxy-1-butene; 1-n-butoxy-1-butene; 1-isobutoxy-1-butene; 1-sec-butoxy-1- 1-tert-butoxy-1-butene; 2-methoxy-1-butene; 2-ethoxy-1-butene; 2-n-propoxy-1-butene; 2-isopropoxy-1-butene; 2-n 2-butoxy-1-butene; 2-isobutoxy-1-butene; 2-sec-butoxy-1-butene; 2-tert-butoxy-1-butene; 2-methoxy-2-butene; 2-ethoxy-2-butene 2-n-propoxy-2-butene; 2-isopropoxy-2-butene; 2-n-butoxy-2-butene; 2-isobutoxy-2-butene; 2-sec-butoxy-2-butene; 2 -Tert-butoxy-2-butene and the like. These vinyl ether monomers can be produced by known methods.

The polyvinyl ether compound having the structural unit represented by the general formula (II) used as the main component in the refrigerating machine oil composition of the present invention has a desired end by a method shown in the present disclosure example and a known method. Can be converted into a structure. Examples of the group to be converted include saturated hydrocarbons, ethers, alcohols, ketones, amides, and nitriles.
As the polyvinyl ether compound used for the base oil in the refrigerating machine oil composition of the present invention, those having the following terminal structure are suitable.
That is, (1) one terminal is represented by the general formula (IV)

(In the formula, R ⁹ , R ¹⁰ and R ¹¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ¹² represents the number of carbon atoms. 2-10 divalent hydrocarbon group, R ¹³ represents the number of hydrocarbon groups having 1 to 10 carbon atoms, q has an average value from 0 to 10, a plurality if R ¹² O is more R ¹² O may be the same or different.
And the remaining ends are represented by the general formula (V)

(In the formula, R ¹⁴ , R ¹⁵ and R ¹⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ¹⁷ represents the number of carbon atoms. A divalent hydrocarbon group of 2 to 10, R ¹⁸ is a hydrocarbon group having 1 to 10 carbon atoms, r is an average value of 0 to 10 and when there are a plurality of R ¹⁷ O, a plurality of R ^{17 17} O may be the same or different.
Having a structure represented by
(2) One terminal is represented by the general formula (IV) and the other terminal is the general formula (VI).

(In the formula, R ¹⁹ , R ²⁰ and R ²¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ²² and R ²⁴ may be different. Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different, and R ²³ and R ²⁵ each represent a hydrocarbon group having 1 to 10 carbon atoms. , They may be the same or different, and s and t each represent an average value of 0 to 10, and they may be the same or different, and it is more R ²² O if there are R ²² O may be the same or different and a plurality of R ²⁴ in the case where there are multiple R ²⁴ O May be the same or different. )
Having a structure represented by
(3) One end of which is represented by the general formula (IV) and the other end has an olefinically unsaturated bond,
(4) One end thereof is represented by the above general formula (IV), and the other end is represented by the general formula (VII)

(In the formula, R ²⁶ , R ²⁷ and R ²⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different.)
Of the structure represented by
It is.
The polyvinyl ether-based mixture may be a mixture of two or more selected from those having the terminal structures (1) to (4). Preferred examples of such a mixture include a mixture of the above (1) and (4), and a mixture of (2) and (3).

As the polyvinyl ether compound, since the kinematic viscosity of the refrigerating machine oil composition before mixing with the refrigerant is preferably ² to 50 mm ² / s at 100 ° C., the above-mentioned polyvinyl ether compound is produced so as to produce a polyvinyl ether compound in this viscosity range. It is preferable to select raw materials, initiators and reaction conditions. Moreover, the number average molecular weight of this polymer is 500 or more normally, Preferably it is 600-3000. In addition, it is also possible to adjust the viscosity within the kinematic viscosity range by mixing the polymer outside the kinematic viscosity range with a polymer having another kinematic viscosity.
In this invention, this polyvinyl ether type compound may be used individually by 1 type, and may be used in combination of 2 or more type.

[Copolymer of poly (oxy) alkylene glycol or its monoether and polyvinyl ether]
Poly (oxy) alkylene glycol refers to both polyalkylene glycol and polyoxyalkylene glycol.
The copolymer of poly (oxy) alkylene glycol or its monoether and polyvinyl ether that can be used as the base oil in the refrigerating machine oil composition of the present invention includes general formula (VIII) and general formula (IX).

(Hereinafter, referred to as polyvinyl ether copolymer I and polyvinyl ether copolymer II), respectively.
In the general formula (VIII), R ²⁹ , R ³⁰ and R ³¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ³³ has 2 carbon atoms. -4 divalent hydrocarbon group, R ³⁴ is an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group optionally having a substituent having 1 to 20 carbon atoms, 2 carbon atoms ~ 20 acyl group or oxygen containing hydrocarbon group having 2 to 50 carbon atoms, R ³² represents a hydrocarbon group having 1 to 10 carbon atoms, and R ³⁴ , R ³³ and R ³² are each in the case where there are a plurality of them. It may be the same or different.
Here, the hydrocarbon group having 1 to 8 carbon atoms of R ^{29 to} R ³¹ is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, sec-. Butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, alkyl groups of various octyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, various dimethyls An arylalkyl group such as an aryl group of a phenyl group, a benzyl group, various phenylethyl groups, and various methylbenzyl groups is shown. In addition, as each of these R <^29> , R <^30> and R < ³¹ >, a hydrogen atom is especially preferable.

On the other hand, examples of the divalent hydrocarbon group having 2 to 4 carbon atoms represented by R ³³ include divalent alkylene groups such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and various butylene groups. .
In addition, v in general formula (VIII) shows the repeating number of R ^<33 > O, The average value is 1-50, Preferably it is 1-20, More preferably, it is 1-10, Most preferably, it is the range of 1-5. Is a number. When the R ³³ O is plural, plural R ³³ O may be the same or different.
K is 1-50, preferably 1-10, more preferably 1-2, particularly preferably 1, u is 0-50, preferably 2-25, more preferably 5-15, If there are a plurality of k and u, each of them may be block or random.

Further, R ³⁴ in the general formula (VIII) preferably represents an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms.
Specific examples of the alkyl group having 1 to 10 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, and various pentyl groups. Group, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, etc. .
Examples of the acyl group having 2 to 10 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, piperoyl group, benzoyl group, and toluoyl group.
Further, specific examples of the oxygen-containing hydrocarbon group having 2 to 50 carbon atoms include methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxypropyl group, ethoxy A propyl group, a (2-methoxyethoxy) propyl group, a (1-methyl-2-methoxy) propyl group and the like can be preferably exemplified.

In the general formula (VIII), the hydrocarbon group having 1 to 10 carbon atoms represented by R ³² specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. , Various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various Aryl groups such as cycloalkyl groups such as dimethylcyclohexyl group, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, Benzyl group, various phenylethyl groups, various methyl Benzyl group, various phenylpropyl groups, arylalkyl groups of various phenylbutyl groups and the like are shown.
R ^{29 to} R ³¹ , R ³⁴ , R ³³ and v and R ^{29 to} R ³² may be the same or different for each structural unit.

  By making the polyvinyl ether copolymer I having the structural unit represented by the general formula (VIII) into a copolymer, it is possible to improve lubricity, insulation, hygroscopicity, etc. while satisfying compatibility. There is an effect that can be done. At this time, by selecting the kind of raw material monomer, the kind of initiator, and the ratio of the copolymer, the performance of the oil can be adjusted to the target level. Therefore, there is an effect that an oil agent can be freely obtained in accordance with requirements such as lubricity and compatibility that differ depending on the type of compressor, the material of the lubrication part, the refrigerating capacity, the type of refrigerant, and the like in the refrigeration system or the air conditioning system.

On the other hand, in the polyvinyl ether copolymer II represented by the general formula (IX), R ^{29 to} R ³² , R ³³ and v are the same as described above. R ³³ and R ³² may be the same or different when there are a plurality of them. x and y each represent a number from 1 to 50, and when there are a plurality of x and y, each may be a block or random. X and Y each independently represent a hydrogen atom, a hydroxyl group or 1 to 20 hydrocarbon groups.

The method for producing the polyvinyl ether copolymer I represented by the general formula (VIII) is not particularly limited as long as it is a method by which it can be obtained. Can be manufactured.
(Production method 1 of polyvinyl ether copolymer I)
In this production method 1, the general formula (X)
R ³⁴ — (OR ³³ ) _v —OH (X)
(Wherein R ³³ , R ³⁴ and v are the same as above).
A poly (oxy) alkylene glycol compound represented by general formula (XI)

(Wherein R ^{29 to} R ³² are the same as described above.)
By polymerizing a vinyl ether compound represented by the formula (I), a polyvinyl ether copolymer I can be obtained.
Examples of the poly (oxy) alkylene glycol compound represented by the general formula (X) include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, and tripropylene glycol. (Oxy) alkylene glycol monoethers such as monomethyl ether and the like can be mentioned.
Examples of the vinyl ether compound represented by the general formula (XI) include vinyl methyl ether, vinyl ethyl ether, vinyl-n-propyl ether, vinyl-isopropyl ether, vinyl-n-butyl ether, vinyl-isobutyl ether, Vinyl ethers such as vinyl-sec-butyl ether, vinyl-tert-butyl ether, vinyl-n-pentyl ether, vinyl-n-hexyl ether; 1-methoxypropene, 1-ethoxypropene, 1-n-propoxypropene, 1-iso Propoxypropene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 2-methoxypropene, 2-ethoxypropene, 2-n-propoxypropene, 2- Propenes such as sopropoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-sec-butoxypropene, 2-tert-butoxypropene; 1-methoxy-1-butene, 1-ethoxy-1-butene 1-n-propoxy-1-butene, 1-isopropoxy-1-butene, 1-n-butoxy-1-butene, 1-isobutoxy-1-butene, 1-sec-butoxy-1-butene, 1- tert-butoxy-1-butene, 2-methoxy-1-butene, 2-ethoxy-1-butene, 2-n-propoxy-1-butene, 2-isopropoxy-1-butene, 2-n-butoxy-1 -Butene, 2-isobutoxy-1-butene, 2-sec-butoxy-1-butene, 2-tert-butoxy-1-butene, 2-methoxy-2-butene , 2-ethoxy-2-butene, 2-n-propoxy-2-butene, 2-isopropoxy-2-butene, 2-n-butoxy-2-butene, 2-tert-butoxy-2-butene, etc. Kind. These vinyl ether monomers can be produced by a known method.

(Method 2 for producing polyvinyl ether copolymer I)
In this production method 2, the general formula (XII)

(In the formula, R ^{29 to} R ³⁴ and v are the same as described above.)
A polyvinyl ether copolymer I can be obtained by polymerizing the vinyl ether compound represented by the general formula (XI) using the acetal compound represented by formula (II) as an initiator.
Examples of the acetal compound represented by the general formula (XII) include acetaldehyde methyl (2-methoxyethyl) acetal, acetaldehyde ethyl (2-methoxyethyl) acetal, acetaldehyde methyl (2-methoxy 1-methylethyl) acetal, and acetaldehyde. Ethyl (2-methoxy-1-methylethyl) acetal, acetaldehyde methyl [2- (2-methoxyethoxy) ethyl] acetal, acetaldehyde ethyl [2- (2-methoxyethoxy) ethyl] acetal, acetaldehyde methyl [2- (2 -Methoxyethoxy) -1-methylethyl] acetal, acetaldehyde ethyl [2- (2-methoxyethoxy) -1-methylethyl] acetal, and the like.
The acetal compound represented by the general formula (XII) includes, for example, one molecule of a poly (oxy) alkylene glycol compound represented by the general formula (X) and a vinyl ether type represented by the general formula (XI). It can also be produced by reacting one molecule of the compound. The obtained acetal compound can be isolated or used as it is as an initiator.

(Method 3 for producing polyvinyl ether copolymer I)
In this production method 3, the general formula (XIII)

(Wherein R ^{29 to} R ³¹ , R ³³ , R ³⁴ and v are the same as described above.)
The vinyl ether copolymer I can be obtained by polymerizing the vinyl ether compound represented by the general formula (XI) using the acetal compound represented by formula (II) as an initiator.
Examples of the acetal compound represented by the general formula (XIII) include acetaldehyde di (2-methoxyethyl) acetal, acetaldehyde di (2-methoxy-1-methylethyl) acetal, acetaldehyde di [2- (2-methoxyethoxy ) Ethyl] acetal, acetaldehyde di [2- (2-methoxyethoxy) -1-methylethyl] acetal, and the like.
Further, the acetal compound represented by the general formula (XIII) includes, for example, one molecule of a poly (oxy) alkylene glycol compound represented by the general formula (X) and the general formula (XIV).

(Wherein R ^{29 to} R ³¹ , R ³³ , R ³⁴ and v are the same as described above.)
It can also be produced by reacting with one molecule of a vinyl ether compound represented by the formula: The obtained acetal compound can be isolated or used as it is as an initiator.
One end of the vinyl ether copolymer I represented by the general formula (VIII) is represented by the general formula (XV) or (XVI).

(In the formula, R ^{29 to} R ³⁴ and v are the same as described above.)
And the remaining ends are represented by the general formula (XVII) or (XVIII)

(In the formula, R ^{29 to} R ³⁴ and v are the same as described above.)
It can be set as the polyvinyl ether type copolymer I which has a structure represented by these.
Among such polyvinyl ether copolymers 1, the following are particularly suitable as base oils for the refrigerating machine oil composition of the present invention.
(1) One terminal is represented by the general formula (XV) or (XVI), and the remaining terminal is a structure represented by the general formula (XVII) or (XVIII). R ²⁹ , R ³⁰ and R ³¹ are both hydrogen atoms, v is a number from 1 to 4, R ³³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, R ³⁴ is an alkyl group having 1 to 10 carbon atoms, and R ³² is a hydrocarbon group having 1 to 10 carbon atoms.
(2) One terminal is represented by the general formula (XV) and the other terminal is represented by the general formula (XVIII), and R ²⁹ , R ³⁰ and R ³¹ in the general formula (VIII) are used. Are both hydrogen atoms, v is a number of 1 to 4, R ³³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, R ³⁴ is an alkyl group having 1 to 10 carbon atoms, and R ³² is a group having 1 to 10 carbon atoms. A hydrocarbon group.
(3) One terminal is represented by the general formula (XVI) and the other terminal is represented by the general formula (XVII), and R ²⁹ , R ³⁰ and R ³¹ in the general formula (VIII) Are both hydrogen atoms, v is a number of 1 to 4, R ³³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, R ³⁴ is an alkyl group having 1 to 10 carbon atoms, and R ³² is a group having 1 to 10 carbon atoms. A hydrocarbon group.

On the other hand, the method for producing the polyvinyl ether copolymer II represented by the general formula (IX) is not particularly limited as long as it is a method by which it can be obtained. can do.
(Production method of polyvinyl ether copolymer II)
The polyvinyl ether copolymer II represented by the general formula (IX) is represented by the general formula (XIX)
HO- (R ³³ O) _v -H (XIX)
(Wherein R ³³ and v are the same as described above.)
It can obtain by polymerizing the vinyl ether compound represented by the said general formula (XI), using poly (oxy) alkylene glycol represented by these as an initiator.
Examples of the poly (oxy) alkylene glycol represented by the general formula (XIX) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, and polypropylene glycol.
In the present invention, this poly (oxy) alkylene glycol or a copolymer of its monoether and polyvinyl ether may be used singly or in combination of two or more.

[Polyol esters]
In the refrigerating machine oil composition of the present invention, as a polyol ester that can be used as a base oil, an ester of a diol or a polyol having about 3 to 20 hydroxyl groups and a fatty acid having about 1 to 24 carbon atoms is preferably used. . Here, as the diol, for example, ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5- Pentanediol, neopentylglycol, 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, etc. Can be mentioned. Examples of the polyol include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), and tri- (pentaerythritol). Glycerin, polyglycerin (glycerin 2-20 mer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyvalent alcohols such as adonitol, arabitol, xylitol, mannitol, xylose, arabinose, Ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gen Anosu, saccharides such as Merenjitosu, and their partially etherified products and methyl glucosides (glycosides) and the like. Among these, as the polyol, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di- (pentaerythritol), tri Hindered alcohols such as-(pentaerythritol) are preferred.

As the fatty acid, the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used. Among the fatty acids having 1 to 24 carbon atoms, those having 3 or more carbon atoms are preferable, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are even more preferable, and those having 10 or more carbon atoms are more preferable. The above is most preferable. Moreover, from a compatible point with a refrigerant | coolant, a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is still more preferable.
Moreover, any of a linear fatty acid and a branched fatty acid may be sufficient, a linear fatty acid is preferable from the point of lubricity, and a branched fatty acid is preferable from the point of hydrolysis stability. Furthermore, either saturated fatty acid or unsaturated fatty acid may be used.

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 , Linear or branched ones such as icosanoic acid and oleic acid, or so-called neoacids in which the α carbon atom is quaternary. More specifically, valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid) Capric acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3, 5,5-trimethylhexanoic acid and the like are preferable.
The polyol ester may be a partial ester remaining without all the hydroxyl groups of the polyol being esterified, or may be a complete ester in which all the hydroxyl groups are esterified, or a partial ester and a complete ester. A complete ester is preferable.

  Among these polyol esters, since they are more excellent in hydrolysis stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol. More preferred are esters of hindered alcohols such as di- (pentaerythritol), tri- (pentaerythritol), and even more preferred are esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, The ester of pentaerythritol is most preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.

  Specific examples of preferred polyol esters include neopentyl glycol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2 -Diester with one or more fatty acids selected from ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, trimethylolethane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, caprin Tritates with one or more fatty acids selected from acids, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid Esters, trimethylolpropane and valeric acid, caproic acid, enanthic acid, caprylic acid, pe One or more selected from lugonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid Triesters with fatty acids, trimethylolbutane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexane Acid, triester with one or more fatty acids selected from 3,5,5-trimethylhexanoic acid, pentaerythritol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, olein Acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexane , 3,5,5 tetraester of one or two or more fatty acids selected from the trimethylhexanoic acid.

Note that the ester with two or more fatty acids may be a mixture of two or more esters of one type of fatty acid and polyol. An ester of two or more types of mixed fatty acid and polyol, particularly an ester of mixed fatty acid and polyol, Excellent low temperature characteristics and compatibility with refrigerants.
[Polycarbonates]
In the refrigerating machine oil composition of the present invention, the polycarbonates that can be used as the base oil include polycarbonates having two or more carbonate bonds in one molecule, that is, the general formula (XX)

(In the formula, Z is a residue obtained by removing a hydroxyl group from an e-valent alcohol having 1 to 12 carbon atoms, R ³⁵ is a linear or branched alkylene group having 2 to 10 carbon atoms, and R ³⁶ is 1 to 12 carbon atoms. Monovalent hydrocarbon group or R ³⁸ (O—R ³⁷ ) _f — (where R ³⁸ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 12 carbon atoms, and R ³⁷ is a straight chain having 2 to 10 carbon atoms. A chain or branched alkylene group, f represents an integer of 1 to 20), a group containing an ether bond, c is an integer of 1 to 30, d is an integer of 1 to 50, and e is an integer of 1 to 6. Is shown.)
And (b) the general formula (XXI)

Wherein R ³⁹ is a linear or branched alkylene group having 2 to 10 carbon atoms, g is an integer of 1 to 20, and Z, R ³⁵ , R ³⁶ , c, d and e are the same as above. is there.)
Preferable examples include at least one selected from the compounds represented by:
In the general formula (XX) and the general formula (XXI), Z is a residue obtained by removing a hydroxyl group from a monovalent to hexavalent alcohol having 1 to 12 carbon atoms. A residue obtained by removing a hydroxyl group from the alcohol is preferable.

Examples of monovalent to hexavalent alcohols having 1 to 12 carbon atoms having Z as a residue include, for example, methyl alcohol, ethyl alcohol, n- or isopropyl alcohol, various butyl alcohols, various pentyl alcohols, and various monovalent alcohols. Aliphatic monohydric alcohols such as hexyl alcohol, various octyl alcohols, various decyl alcohols and various dodecyl alcohols, alicyclic monohydric alcohols such as cyclopentyl alcohol and cyclohexyl alcohol, aromatic alcohols such as phenol, cresol, xylenol, butylphenol and naphthol Araliphatic alcohols such as benzyl alcohol and phenethyl alcohol as dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, neope Aliphatic alcohols such as tylene glycol and tetramethylene glycol, alicyclic alcohols such as cyclohexanediol and cyclohexanedimethanol, aromatic alcohols such as catechol, resorcinol, hydroquinone and dihydroxydiphenyl, and trivalent alcohols such as glycerin and trimethylol Propylene, trimethylolethane, trimethylolbutane, aliphatic alcohols such as 1,3,5-pentanetriol, alicyclic alcohols such as cyclohexanetriol and cyclohexanetrimethanol, aromatic alcohols such as pyrogallol and methylpyrogalol, etc. Divalent to hexavalent alcohols such as pentaerythritol, diglycerin, triglycerin, sorbitol, dipentaerythritol, etc. Or the like can be mentioned aliphatic alcohol.
As such a polycarbonate compound, as a compound represented by the general formula (XX), the general formula (XX-a)

(In the formula, R ⁴⁰ is a residue obtained by removing a hydroxyl group from a monohydric alcohol having 1 to 12 carbon atoms, and R ³⁵ , R ³⁶ , c and d are the same as described above.)
And / or a compound represented by the general formula (XXI) is a compound represented by the general formula (XXI-a):

(Wherein R ³⁵ , R ³⁶ , R ³⁹ , R ⁴⁰ , c, d and g are the same as above).
The compound represented by these can be mentioned.
In the general formula (XX-a) and general formula (XXI-a), the residue obtained by removing the hydroxyl group from the monovalent alcohol having 1 to 12 carbon atoms represented by R ⁴⁰ includes a methyl group, an ethyl group, n -Aliphatic hydrocarbon groups such as propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various octyl groups, various decyl groups, various dodecyl groups, cyclopentyl group, cyclohexyl group, methylcyclohexyl group, dimethylcyclohexyl Group, alicyclic hydrocarbon group such as decahydronaphthyl group, phenyl group, various tolyl groups, various xylyl groups, mesityl group, various naphthyl groups and other aromatic hydrocarbon groups, benzyl group, methylbenzyl group, phenethyl group, Examples thereof include araliphatic hydrocarbon groups such as various naphthylmethyl groups. Among these, a linear or branched alkyl group having 1 to 6 carbon atoms is preferable.

R ³⁵ is a straight chain or branched alkylene group having 2 to 10 carbon atoms, preferably 2 to 6 carbon atoms, particularly ethylene and propylene groups from the viewpoint of performance and ease of production. Is preferred. R ³⁶ is a monovalent hydrocarbon group having 1 to 12 carbon atoms or R ³⁸ (O—R ³⁷ ) _f — (where R ³⁸ is a hydrogen atom or 1 to 12 carbon atoms, preferably 1 to 6 carbon atoms. Valent hydrocarbon group, R ³⁷ is a linear or branched alkylene group having 2 to 10 carbon atoms, and f is an integer of 1 to 20). Examples of the monovalent hydrocarbon group of ˜12 include the same ones as exemplified in the description of R ⁴⁰ . In addition, the linear or branched alkylene group having 2 to 10 carbon atoms represented by R ³⁷ is preferably one having 2 to 6 carbon atoms for the same reason as in the case of R ³⁵ , particularly ethylene group and propylene. Groups are preferred.

R ³⁶ is particularly preferably a linear or branched alkyl group having 1 to 6 carbon atoms.
In the general formula (XXI-a), the linear or branched alkylene group having 2 to 10 carbon atoms represented by R ³⁹ includes those having 2 to 6 carbon atoms for the same reason as in the case of R ^35. An ethylene group and a propylene group are particularly preferable.
Such a polycarbonate compound can be produced by various methods. Usually, a carbonate ester-forming derivative such as a carbonic acid diester or phosgene is reacted with an alkylene glycol or a polyoxyalkylene glycol according to a known method. The polycarbonate compound can be produced.
In this invention, these polycarbonates may be used individually by 1 type, and may be used in combination of 2 or more type.

In the refrigerating machine oil composition of the present invention, as the base oil, the above-mentioned polyoxyalkylene glycols, polyvinyl ethers, poly (oxy) alkylene glycols or their monoether and polyvinyl ether copolymers, polyol esters and polycarbonates Those containing at least one oxygen-containing compound selected from among these as a main component are used. Here, containing as a main component means containing the said oxygen-containing compound in the ratio of 50 mass% or more. The content of the oxygen-containing compound in the base oil is preferably 70% by mass or more, more preferably 90% by mass or more, and still more preferably 100% by mass.
In the present invention, the kinematic viscosity at 100 ° C. of the base oil is preferably ² to 50 mm ² / s, more preferably 3 to 40 mm ² / s, and further preferably 4 to 30 mm ² / s. When the kinematic viscosity is 2 mm ² / s or more, good lubrication performance (load resistance) is exhibited, the sealing property is good, and when it is 50 mm ² / s or less, the energy saving property is also good.
Further, the number average molecular weight of the base oil is preferably 500 or more, more preferably 600 to 3000, and further preferably 700 to 2500. The flash point of the base oil is preferably 150 ° C. or higher. If the number average molecular weight of the base oil is 500 or more, desired performance as a refrigerating machine oil can be exhibited, and the flash point of the base oil can be set to 150 ° C. or more.

In the present invention, if the base oil has the above-mentioned properties, it is 50% by mass or less, preferably 30% by mass or less, more preferably 10% by mass or less, together with the oxygen-containing compound. Those containing a base oil can be used, but those containing no other base oil are more preferred.
Examples of the base oil that can be used in combination with the oxygen compound include other polyesters, hydrides of α-olefin oligomers, mineral oils, alicyclic hydrocarbon compounds, alkylated aromatic hydrocarbon compounds, and the like.
The refrigerating machine oil composition of the present invention may contain at least one additive selected from among extreme pressure agents, oiliness agents, antioxidants, acid scavengers and antifoaming agents.
Examples of the extreme pressure agent include phosphorus extreme pressure agents such as phosphate esters, acid phosphate esters, phosphite esters, acid phosphite esters, and amine salts thereof.
Among these phosphorous extreme pressure agents, tricresyl phosphate, trithiophenyl phosphate, tri (nonylphenyl) phosphite, dioleyl hydrogen phosphite, 2-ethylhexyl diphenyl phosphite in terms of extreme pressure and friction characteristics Etc. are particularly preferred.

Examples of extreme pressure agents include metal salts of carboxylic acids. The metal salt of a carboxylic acid here is preferably a carboxylic acid having 3 to 60 carbon atoms, more preferably a metal salt of a fatty acid having 3 to 30 carbon atoms, particularly 12 to 30 carbon atoms. Moreover, the metal salt of the dimer acid and trimer acid of the said fatty acid, and C3-C30 dicarboxylic acid can be mentioned. Among these, a metal salt of a fatty acid having 12 to 30 carbon atoms and a dicarboxylic acid having 3 to 30 carbon atoms is particularly preferable.
On the other hand, as the metal constituting the metal salt, an alkali metal or an alkaline earth metal is preferable, and an alkali metal is particularly optimal.
In addition, as extreme pressure agents, as extreme pressure agents other than those described above, for example, sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiocarbamates, thioterpenes, dialkylthiodipropionates, etc. The sulfur type extreme pressure agent can be mentioned.
The blending amount of the extreme pressure agent is usually 0.001 to 5% by mass, particularly preferably 0.005 to 3% by mass based on the total amount of the composition from the viewpoint of lubricity and stability.
One of these extreme pressure agents may be used alone, or two or more thereof may be used in combination.

Examples of the oily agent include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid, Aliphatic saturated and unsaturated monoalcohols such as lauryl alcohol, oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine, oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide, oleic acid amide, Examples thereof include partial esters of polyhydric alcohols such as glycerin and sorbitol and aliphatic saturated or unsaturated monocarboxylic acids.
These may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, the compounding quantity is 0.01-10 mass% normally based on the composition whole quantity, Preferably it selects in the range of 0.1-5 mass%.

  Examples of the antioxidant include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4-methyl-6- It is preferable to add an amine-based antioxidant such as phenyl-α-naphthylamine or N, N′-di-phenyl-p-phenylenediamine. The antioxidant is usually blended in the composition in an amount of 0.01 to 5% by mass, preferably 0.05 to 3% by mass, from the viewpoints of effects and economy.

Examples of the acid scavenger include epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, α-olefin oxide, and epoxidized soybean oil. Of these, phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, and α-olefin oxide are preferable in terms of compatibility.
The alkyl group of the alkyl glycidyl ether and the alkylene group of the alkylene glycol glycidyl ether may have a branch, and the number of carbon atoms is usually 3 to 30, preferably 4 to 24, particularly 6 to 16. The α-olefin oxide generally has a total carbon number of 4 to 50, preferably 4 to 24, particularly 6 to 16. In the present invention, one type of acid scavenger may be used, or two or more types may be used in combination. Moreover, the compounding quantity is 0.005-5 mass% normally with respect to a composition from the point of an effect and suppression of sludge generation | occurrence | production, Especially the range of 0.05-3 mass% is preferable.

In the present invention, the stability of the refrigerating machine oil composition can be improved by blending this acid scavenger. By using the extreme pressure agent and the antioxidant in combination, the effect of further improving the stability is exhibited.
Examples of the antifoaming agent include silicone oil and fluorinated silicone oil.
In the refrigerating machine oil composition of the present invention, other known various additives such as N- [N, N′-dialkyl (C 3 -C 12 alkyl group) aminomethyl, as long as the object of the present invention is not impaired. A copper deactivator such as triazole can be appropriately blended.

The refrigerating machine oil composition of the present invention includes at least one fluorine-containing organic compound selected from the compounds represented by the molecular formula (A), or a combination of the fluorine-containing organic compound and a saturated fluorinated hydrocarbon compound. Applies to refrigerators using refrigerant.
The refrigerating machine oil composition of the present invention comprises at least one fluorinated organic compound selected from a fluorinated ether compound, a fluorinated alcohol compound and a fluorinated ketone compound, or the fluorinated organic compound and saturated fluorinated carbonization. The present invention is applied to a refrigerator using a refrigerant containing a combination with a hydrogen compound.
In the refrigerating machine lubrication method using the refrigerating machine oil composition of the present invention, the usage amount of the various refrigerants and the refrigerating machine oil composition is 99/1 to 10/90 in terms of the mass ratio of the refrigerating machine / refrigerating oil composition. It is preferably in the range of 95/5 to 30/70. When the amount of the refrigerant is less than the above range, the refrigerating capacity is lowered, and when it is more than the above range, the lubricating performance is lowered, which is not preferable. The refrigerating machine oil composition of the present invention can be used in various refrigerating machines, but can be preferably applied particularly to a compression refrigeration cycle of a compression refrigerating machine.

The refrigerating machine to which the refrigerating machine oil composition of the present invention is applied must include a compressor, a condenser, an expansion mechanism (such as an expansion valve) and an evaporator, or a compressor, a condenser, an expansion mechanism, a dryer and an evaporator. The refrigerating machine oil composition of the present invention described above is used as the refrigerating machine oil, and the various refrigerants described above are used as the refrigerant.
Here, the dryer is preferably filled with a desiccant made of zeolite having a pore diameter of 0.33 nm or less. Further, examples of the zeolite include natural zeolite and synthetic zeolite. Further, it is more preferable that the zeolite has a CO ₂ gas absorption capacity of 1.0% or less at 25 ° C. and a CO ₂ gas partial pressure of 33 kPa. is there. Examples of such synthetic zeolite include trade names XH-9 and XH-600 manufactured by Union Showa Co., Ltd.
In the present invention, when such a desiccant is used, moisture can be efficiently removed without absorbing the refrigerant in the refrigeration cycle, and at the same time, pulverization due to deterioration of the desiccant itself is suppressed, and thus is caused by pulverization. There is no risk of abnormal wear or the like due to blockage of piping or entry into the compressor sliding portion, and the refrigerator can be stably operated for a long time.

In a refrigerator to which the refrigerator oil composition of the present invention is applied, there are various sliding portions (for example, bearings) in the compressor. In the present invention, the sliding portion is made of an engineering plastic, or has an organic coating film or an inorganic coating film, particularly from the viewpoint of sealing properties.
Preferred examples of the engineering plastic include polyamide resin, polyphenylene sulfide resin, polyacetal resin, and the like in terms of sealing properties, slidability, wear resistance, and the like.
Examples of the organic coating film include a fluorine-containing resin coating film (polytetrafluoroethylene coating film, etc.), a polyimide coating film, a polyamideimide coating film, and the like in terms of sealing properties, slidability, and wear resistance. be able to.
On the other hand, examples of the inorganic coating film include a graphite film, a diamond-like carbon film, a nickel film, a molybdenum film, a tin film, and a chromium film in terms of sealing properties, slidability, and wear resistance. This inorganic coating film may be formed by plating, or may be formed by a PVD method (physical vapor deposition method).
As the sliding portion, a conventional alloy system such as an Fe-based alloy, an Al-based alloy, a Cu-based alloy, or the like can also be used.

The refrigerating machine oil composition of the present invention can be used for various hot water supply systems such as car air conditioners, electric car air conditioners, gas heat pumps, air conditioners, refrigerators, vending machines or showcases, or refrigeration / heating systems.
In the present invention, the water content in the system is preferably 300 ppm by mass or less, and more preferably 200 ppm by mass or less. The residual air amount in the system is preferably 10 kPa or less, and more preferably 5 kPa or less.
The refrigerating machine oil composition of the present invention contains a specific oxygen-containing compound as a base oil as a main component, has a low viscosity, can improve energy saving properties, and is excellent in sealing properties.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
The properties of the base oil and various characteristics of the refrigerator oil composition were determined according to the following procedure.
<Properties of base oil>
(1) 100 ° C. Kinematic viscosity Measured according to JIS K2283-1983 using a glass capillary viscometer.
(2) Flash point According to JIS K2265, C.I. O. It was measured by C method.
(3) Number average molecular weight It measured by GPC (gel permeation chromatograph) method.
<Various characteristics of frozen base oil composition>
(4) Two-layer separation temperature A two-layer separation temperature measuring tube (internal volume 10 mL) was filled with oil / refrigerant (0.6 g / 2.4 g) and held in a thermostatic bath. The temperature of the thermostatic chamber was increased from room temperature (25 ° C.) at a rate of 1 ° C./min, and the two-layer separation temperature was measured.
(5) Stability (shield tube test)
Glass tube is filled with oil / refrigerant 4mL / 1g (water content (200ppm) and metal catalyst of iron, copper, aluminum) and sealed for 10 days under conditions of air pressure 26.6kPa and temperature 175 ° C. Thereafter, the oil appearance, the catalyst appearance, and the presence or absence of sludge were visually observed, and the acid value was measured.

Moreover, the kind of each component used for preparation of a refrigerator oil composition is shown below.
(1) Base oil A1: Polypropylene glycol dimethyl ether, 100 ° C. kinematic viscosity 9.25 mm ² / s, flash point 212 ° C., number average molecular weight 1139
A2: Polypropylene glycol (PPG) / polyethylene glycol (PEG) dimethyl ether (PPG / PEG molar ratio 9/1), 100 ° C. kinematic viscosity 10.34 mm ² / s, flash point 223 ° C., number average molecular weight 1116
A3: Polypropylene glycol / polyethylene glycol dimethyl ether (PPG / PEG molar ratio 8/2), 100 ° C. kinematic viscosity 20.05 mm ² / s, flash point 230 ° C., number average molecular weight 1730
A4: Polypropylene glycol methylnonyl phenyl ether, 100 ° C. kinematic viscosity 11.76 mm ² / s, flash point 220 ° C., number average molecular weight 1100
A5: Polypropylene glycol dioctyl ether, 100 ° C. kinematic viscosity 11.31 mm ² / s, flash point 219 ° C., number average molecular weight 1090
A6: Polyethyl vinyl ether, 100 ° C. kinematic viscosity 15.97 mm ² / s, flash point 222 ° C., number average molecular weight 1250
A7: Polyethyl vinyl ether (PEV) / polyisobutyl vinyl ether (PIBV) copolymer (PEV / PIBV molar ratio 9/1), 100 ° C. kinematic viscosity 8.26 mm ² / s, flash point 206 ° C., number average molecular weight 830
A8: Polypropylene glycol (PPG) / polyethyl vinyl ether (PEV) copolymer (PPG / PEV molar ratio 7/11), 100 ° C. kinematic viscosity 9.56 mm ² / s, flash point 218 ° C., number average molecular weight 1200
A9: Polyethylene glycol (PEG) / polyethyl vinyl ether (PEV) copolymer (PEG / PEV molar ratio 3/21), 100 ° C. kinematic viscosity 17.64 mm ² / s, flash point 232 ° C., number average molecular weight 1680
A10: Polypropylene glycol (PPG) / polyethyl vinyl ether (PEV) copolymer (PPG / PEV molar ratio 16/5), 100 ° C. kinematic viscosity 13.49 mm ² / s, flash point 223 ° C., number average molecular weight 1280
A11: pentaerythritol octanoic acid (C8 acid) nonanoic acid (C9 acid) ester (C8 acid / C9 acid molar ratio 1 / 1.1), 100 ° C. kinematic viscosity 9.64 mm ² / s, flash point 268 ° C., number average Molecular weight 670
A12: pentaerythritol octanoic acid nonanoic acid ester (C8 acid / C9 acid molar ratio 1 / 1.7), 100 ° C. kinematic viscosity 15.99 mm ² / s, flash point 289 ° C., number average molecular weight 685
A13: Paraffin-based mineral oil, 100 ° C. kinematic viscosity 10.68 mm ² / s, flash point 266 ° C.
A14: Alkylbenzene, 100 ° C. kinematic viscosity 5.85 mm ² / s, flash point 196 ° C.
(2) Additives Extreme pressure agent B1: tricresyl phosphate acid scavenger B2: C14α-olefin oxide antioxidant B3: 2,6-di-t-butyl-4-methylphenol antifoam B4: silicone Foam

Moreover, the kind of used refrigerant | coolant is shown below.
Ref1-1: 1,1,1-trifluorodimethyl ether Ref1-2: 1,1,2-trifluorodimethyl ether Ref1-3: 1,1,1,2-tetrafluorodimethyl ether Ref1-4: 1,1,2 , 2-tetrafluorodimethyl ether Ref1-5: Ref1-2 / Ref1-4 mixture (mass ratio 1/1)
Ref2-1: trifluoromethyl alcohol Ref2-2: difluoromethyl alcohol Ref2-3: monofluoromethyl alcohol Ref2-4: 1,1,1-trifluoroethyl alcohol Ref2-5: 1,1,2-trifluoroethyl Alcohol Ref3-1: 1,1-difluoroacetone Ref3-2: 1,1,1-trifluoroacetone Ref3-3: 1,1,2-trifluoroacetone Ref3-4: 1,1,1,2-tetra Fluoroacetone Ref3-5: Ref3-1 / Ref3-3 mixture (mass ratio 1/1)

Examples 1 to 12 and Comparative Examples 1 and 2
A refrigerating machine oil composition having the composition shown in Table 1 was prepared, and Ref1-1, Ref1-2, Ref1-3, Ref1-4, and Ref1-5, which are refrigerants made of the fluorinated ether compound shown in Table 1, were used. The properties of the composition were evaluated. The results are shown in Table 1.

  As can be seen from Table 1, the refrigerating machine oil compositions (Examples 1 to 12) of the present invention have a two-layer separation temperature exceeding 40 ° C with respect to all the various refrigerants Ref1-1 to Ref1-5, and Excellent stability in shield tube test using Ref1-1. On the other hand, Comparative Examples 1 and 2 separate at room temperature with respect to all the refrigerants Ref1-1 to Ref1-5.

Examples 13 to 24 and Comparative Examples 3 and 4
A refrigerating machine oil composition having the composition shown in Table 2 was prepared, and Ref2-1, Ref2-2, Ref2-3, Ref2-4 and Ref2-5, which are refrigerants composed of the fluorinated alcohol compound shown in Table 2, were used. The properties of the composition were evaluated. The results are shown in Table 2.

  As can be seen from Table 2, the refrigerating machine oil compositions (Examples 13 to 24) of the present invention have a two-layer separation temperature exceeding 40 ° C with respect to all the various refrigerants Ref2-1 to Ref2-5, and It is excellent in stability in the shield tube test using Ref2-1. On the other hand, Comparative Examples 3 and 4 are separated at room temperature with respect to all the refrigerants Ref2-1 to Ref2-5.

Examples 25-36 and Comparative Examples 5 and 6
A refrigerating machine oil composition having the composition shown in Table 3 was prepared, and Ref3-1, Ref3-2, Ref3-3, Ref3-4 and Ref3-5, which are refrigerants composed of the fluorinated ketone compounds shown in Table 3, were used. The properties of the composition were evaluated. The results are shown in Table 3.

  As can be seen from Table 3, the refrigerating machine oil compositions (Examples 25 to 36) of the present invention have a two-layer separation temperature exceeding 40 ° C with respect to all of the various refrigerants Ref3-1 to Ref3-5, and It is excellent in stability in the shield tube test using Ref3-2. On the other hand, Comparative Examples 5 and 6 separate at room temperature with respect to all the refrigerants Ref3-1 to Ref3-5.

  The lubricating oil composition for a refrigerator of the present invention has a low global warming potential, and particularly for a refrigerator using a refrigerant having a specific polar structure, such as a fluorinated ether compound, which is a refrigerant that can be used in current car air conditioner systems and the like. Used as.

Claims (14)

A composition for a refrigerator including a refrigerant and a lubricating oil composition for the refrigerator,
The refrigerant has the following molecular formula (A)
C _p O _q F _r R _s (A)
[In the formula, R represents H, p is 2 to 6, q is 0, r is 1 to 12, and s is an integer of 0 to 11, and the molecule has one or more carbon-carbon unsaturated bonds. ]
A combination of at least one unsaturated fluorinated hydrocarbon compound and saturated fluorinated hydrocarbon compound selected from the compounds represented by:
The blending amount of the saturated fluorinated hydrocarbon compound in the combination of the unsaturated fluorinated hydrocarbon compound and the saturated fluorinated hydrocarbon compound is 30% by mass or less based on the total amount of the refrigerant,
The lubricating oil composition for refrigerating machine has polypropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol dimethyl ether , polypropylene glycol methyl nonyl phenyl ether, polypropylene glycol dioctyl ether, polyethyl vinyl ether, polyethyl vinyl ether and polyisobutyl vinyl ether as a base oil. And a copolymer of polypropylene glycol and polyethyl vinyl ether, a copolymer of polyethylene glycol and polyethyl vinyl ether, and at least one oxygen-containing compound selected from pentaerythritol octanoate nonanoate The composition for refrigerators using what was included as. The composition for a refrigerator according to claim 1, wherein the amount of the saturated fluorinated hydrocarbon compound is 10% by mass or less based on the total amount of the refrigerant . The composition for a refrigerator according to claim 1 or 2, wherein the unsaturated fluorinated hydrocarbon compound is propene fluoride . 4. The propene fluoride is at least one selected from various isomers of pentafluoropropene, 3,3,3-trifluoropropene and 1,3,3,3-tetrafluoropropene. Composition for refrigerator . The composition for a refrigerator according to any one of claims 1 to 4, wherein the base oil has a kinematic viscosity at 100 ° C of ² to 50 mm ² / s. The number average molecular weight of base oil is 500 or more, The composition for refrigerators in any one of Claims 1-5 . The flash point of a base oil is 150 degreeC or more, The composition for refrigerators in any one of Claims 1-6 . The composition for a refrigerator according to any one of claims 1 to 7 , comprising at least one additive selected from an extreme pressure agent, an oily agent, an antioxidant, an acid scavenger, and an antifoaming agent. Saturated fluorinated hydrocarbon compound is 1,1-difluoroethane refrigerant, trifluoroethane, for the refrigerator according to any one of claims 1-8 is at least one selected from tetrafluoroethane and pentafluoroethane Composition . The composition for a refrigerator according to any one of claims 1 to 9 , wherein the sliding portion of the refrigerator is made of an engineering plastic, or has an organic coating film or an inorganic coating film. The composition for a refrigerator according to claim 10 , wherein the organic coating film is a polytetrafluoroethylene coating film, a polyimide coating film or a polyamideimide coating film. The composition for a refrigerator according to claim 10 , wherein the inorganic coating film is a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, or a molybdenum film. The composition for a refrigerator according to any one of claims 1 to 12 , which is used for a car air conditioner, an electric car air conditioner, a gas heat pump, an air conditioner, a refrigerator, a vending machine, various hot water supply systems for showcases, or a freezing / heating system . . The composition for a refrigerator according to claim 13 , wherein the water content in the system is 300 ppm by mass or less and the residual air amount is 10 kPa or less.