JP3501258B2 - Refrigeration equipment and refrigerant compressor - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refrigeration system and a refrigerant compressor, and more specifically, as a refrigerant, a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or an ammonia type, preferably A refrigeration system and a refrigeration system using a polyvinyl ether type lubricating oil that uses a hydrofluorocarbon type that can substitute for chlorofluorocarbon, which is a problem in environmental pollution, and that has good compatibility with it and has excellent lubricating performance. The present invention relates to a refrigerant compressor used in an apparatus.

[0002]

2. Description of the Related Art Generally, a compression type refrigerator comprises at least a compressor, a condenser, an expansion mechanism (expansion valve etc.), an evaporator or a dryer, and a liquid mixture of a refrigerant and a lubricating oil is hermetically sealed. It has a structure that circulates in the system. In such a compression type refrigerator, it is generally high temperature in the compressor and low temperature in the cooler depending on the type of the device, so that the refrigerant and the 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. Generally, the refrigerant and the lubricating oil have a region where the low temperature side and the high temperature side are phase separated, and the maximum temperature of the separation region on the low temperature side is preferably -10 ° C or lower, and particularly -20 ° C.
C. or less is preferable. On the other hand, the minimum temperature of the separation region on the high temperature side is preferably 30 ° C or higher, and particularly preferably 40 ° C or higher. If phase separation occurs during operation of the refrigerator, the life and efficiency of the device will be significantly adversely affected. For example, when phase separation of the refrigerant and the lubricating oil occurs in the compressor part, the moving part becomes poorly lubricated, causing seizure, etc., and significantly shortening the life of the device, while phase separation occurs in the evaporator, The presence of high-viscosity lubricating oil causes a decrease in heat exchange efficiency.

Further, since the lubricating oil for a refrigerator is used for the purpose of lubricating the moving parts of the refrigerator, the lubricating performance is naturally important. In particular, since the temperature inside the compressor becomes high, the viscosity that can hold the oil film necessary for lubrication is important. The required viscosity depends on the type of compressor used and the conditions of use, but normally the viscosity (kinematic viscosity) of the lubricating oil before mixing with the refrigerant is preferably ² to 200 mm ² / sec at 40 ° C. It is preferably 5 to 100 mm ² / sec. If the viscosity is lower than this, the oil film becomes thin, and poor lubrication is likely to occur. Further, in an electric refrigerator and an air conditioner, since an electric motor (motor) and a compressor (compressor) are integrated, the lubricating oil thereof is required to have high electric insulation. Generally, the volume resistivity at 80 ° C. is required to be 10 ¹² Ω · cm or more, and if it is lower than this, there is a possibility of leakage. Further, the lubricating oil is required to have high stability. For example, when an organic acid is produced by hydrolysis or the like, the device is apt to be corroded or worn depending on its amount.

Conventionally, chlorodifluoromethane (hereinafter referred to as R22) or a chlorodifluoromethane / chloropentafluoroethane weight ratio of 48.8: 51.2 has been used as a refrigerant for a compression type refrigerator, particularly an air conditioner. Mixture (hereinafter,
It is called R502. ) Is often used, and as the lubricating oil, various mineral oils and synthetic oils satisfying the above-mentioned required characteristics have been used. However, since R22 and R502 may cause environmental pollution such as depletion of the ozone layer, their regulations are recently becoming strict worldwide. Therefore, 1,1,1,2-tetrafluoroethane; difluoromethane; pentafluoroethane; 1,1,1-trifluoroethane (hereinafter referred to as R134a, R32, R125, and R143a, respectively) are typical new refrigerants. Hydrofluorocarbons, which are said to have come to the spotlight. This hydrofluorocarbon, especially R134a, R32, R125, and R143a has no fear of destroying the ozone layer and is preferable as a refrigerant for a compression type refrigerator. However, there is a problem when the above hydrofluorocarbons are used alone. For example, in “Energy and Resources” Vol. 16, No. 5, 474, (1) R134 is used as an alternative to R22.
When a is applied to an air conditioner, the operating pressure is low and R22
Compared with, the capacity is reduced by about 40% and the efficiency is reduced by about 5%.
(2) R32 is more efficient than R22, but operating pressure is high and slightly flammable. (3) R125 is nonflammable, but critical pressure is low and efficiency is low. . Further, R143a has a problem of flammability as in R32.

As the refrigerant for the compression type refrigerator, it is desirable to be able to use it without changing the existing refrigeration system. However, due to the above problems, the refrigerant containing the above-mentioned hydrofluorocarbon should actually be used. That is, the current R
In order to substitute the R22 and R502 refrigerants, R32 and R143a which are flammable are used from the viewpoint of efficiency, and R125 and R134a are used to make the refrigerant as a whole nonflammable.
Is preferably mixed with the former. The International
Symposium on R22 & R502 Alternative Refrigerants,
(1994, p. 166), it is shown that the R32 / R134a mixture is flammable when the R32 content is 56% by weight or more. Although it cannot be specified unconditionally depending on the composition of the refrigerant, it can be said that a refrigerant containing 45% by weight or more of nonflammable hydrofluorocarbon such as R125 and R134a is preferable from the viewpoint of nonflammability.

On the other hand, since the refrigerant is used in the refrigeration system under various conditions, it is not preferable that the composition of the hydrofluorocarbon to be mixed is largely different in each part of the refrigeration system. In the refrigeration system, the refrigerant takes both a gas state and a liquid state. Therefore, if the boiling points of the hydrofluorocarbons to be mixed are significantly different, the composition of the mixed refrigerant can be greatly different in each part of the refrigeration system due to the above reasons. There is a nature. R32, R
The boiling points of 143a, R125, and R134a are −51.7 ° C., −47.4 ° C., −48.5 ° C., and −26.3 ° C., respectively, and R134 is added to the hydrofluorocarbon mixed refrigerant system.
Care must be taken in this respect when using a. Therefore, in the mixed refrigerant using R125, its content is preferably 20 to 80% by weight, particularly 40 to 70% by weight. If the content is less than 20% by weight, a large amount of refrigerants having greatly different boiling points, such as R134a, is required in order to impart nonflammability, which is not preferable for the above reason. Further, if the content of R125 exceeds 80% by weight, the efficiency decreases, which is not preferable.

From these points, as an alternative to the conventional R22 refrigerant, a mixture of R32, R125 and R134a in a weight ratio of 23:25:52 (hereinafter referred to as R407C).
Called. ), The weight ratio of R32 and R125 is 50:50
Mixture (hereinafter referred to as R410A), R32 and R
A mixture with 125 in a weight ratio of 45:55 (hereinafter, R410
It is called B. ) Is preferred, while as an alternative to the R502 refrigerant, a mixture of R125, R143a and R134a in a weight ratio of 44: 52: 4 (hereinafter referred to as R404A) and a weight ratio of R125 and R143a in a ratio of 50: 5.
A mixture of 0 (hereinafter referred to as R507) is preferable.
In addition, these mixed refrigerants are also suitable because the composition of the refrigerant is small when the refrigerant is filled in the apparatus or when the refrigerant leaks from the apparatus.

On the other hand, until now, R22 and R5 have been used as refrigerants.
No. 02 etc. have been used in the compression type refrigerator, and in place of them, the above-mentioned R404A, R410A, R410B,
When R507 or the like is adopted, as a lubricating oil, it is naturally excellent in compatibility with these hydrofluorocarbon mixed refrigerants, and the above-mentioned required performance, that is, volume resistivity is 10 ¹² Ω · cm (80 ° C.). ) Above, and those having excellent stability and lubricating performance are required. However, the lubricating oil that has been used with the conventional R22, R502, etc. is R404A, R410A, R410.
Since the compatibility with hydrofluorocarbon mixed refrigerants such as B and R507 is not good, new lubricating oil suitable for these mixed refrigerants is required. In this case, it is demanded that the structure of the device is hardly changed particularly when replacing R22 or R502, and when changing the lubricating oil,
It is not desirable to significantly change the structure of existing devices.

As the lubricating oil compatible with these hydrofluorocarbon mixed refrigerants, polyalkylene glycol type, polyol ester type and carbonate type are known, but the polyalkylene glycol type has a low volume resistivity and a polyol. The ester type and carbonate type are easily hydrolyzed and have a problem of stability. Therefore, a lubricating oil having compatibility with the hydrofluorocarbon mixed refrigerant, high volume resistivity, and excellent stability and lubrication performance has been desired.

[0010]

SUMMARY OF THE INVENTION Under the above circumstances, the present invention provides a refrigerant containing a hydrofluorocarbon-based material,
Fluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based, or ammonia-based ones, preferably hydrofluorocarbon-based ones that can substitute for chlorofluorocarbons which are a problem in environmental pollution, and are compatible with them The present invention aims to provide a refrigerant device using a lubricating oil having high volume resistivity, high stability, and excellent lubricating performance, and a refrigerant compressor suitable for forming a refrigeration cycle of this refrigeration device. Is.

[0011]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the present inventors have found that as a lubricating oil, a polyvinyl ether comprising a homopolymer or a copolymer having a specific constitutional unit. It has been found that the object can be achieved by using a compound containing a system compound as a main component and having a predetermined viscosity. The present invention has been completed based on such findings. That is, the present invention comprises a refrigeration cycle including at least a compressor, a condenser, an expansion mechanism and an evaporator, and if necessary, a dryer, and a hydroflurocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type. -Based, carbon dioxide-based or ammonia-based refrigerant and polyvinyl ether-based compound as a main component, and the kinematic viscosity at a temperature of 40 ° C is 2 to
A refrigeration system provided with a lubricating oil of 200 mm ² / sec.

The present invention also relates to an internal high-pressure type or internal low-pressure type hermetic compressor in which a compressor and an electric motor are enclosed in a single cover, which is a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, Also provided is a refrigerant compressor having an ether-based, carbon dioxide-based or ammonia-based refrigerant and a lubricating oil containing a polyvinyl ether compound as a main component and having a kinematic viscosity at a temperature of 40 ° C. of ² to 200 mm ² / sec. To do.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION In the refrigerating apparatus and the refrigerant compressor of the present invention, the refrigerant is a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or an ammonia type, and preferably a hydrofluorocarbon type. What is used. On the other hand, as the lubricating oil, one containing a polyvinyl ether compound as a main component is used. The polyvinyl ether-based compound has the general formula (I)

[0014]

[Chemical 7]

[In the formula, R ¹ , R ² and R ³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁴ is a carbon number. 1-10 divalent hydrocarbon group or 2-20 carbon atoms
A divalent ether-bonded oxygen-containing hydrocarbon group, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and m has an average value of 0 to 10
Indicates the number of, R ¹ to R ⁵ may be different from each be the same for each structural unit, also in the case where R ⁴ O have multiple, even if a plurality of R ⁴ O are identical or different Good. ] It is essential that the polyvinyl ether compound (1) is composed of a polymer having a structural unit represented by
Further, (a) a structural unit represented by the general formula (I) and (b) a general formula (II)

[0016]

[Chemical 8]

[In the formula, R ^{6 to} R ⁹ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and R ^{6 to} R ⁹ are constituted. The units may be the same or different. ] The polyvinyl ether type compound (2) which consists of a block or a random copolymer which has the structural unit represented by these, and (A) the said polyvinyl ether type compound (1) and (B) polyvinyl ether type compound (2). A polyvinyl ether compound (3) composed of a mixture of is preferably used. The polyvinyl ether compound (1) is composed of a polymer having a structural unit represented by the general formula (I), and R in the general formula (I)
¹ , R ² and R ³ are each a hydrogen atom or a carbon number of 1 to 8
Of hydrocarbon groups, which may be the same or different from each other. Here, the hydrocarbon group specifically includes methyl group, ethyl group, n-propyl group, isopropyl group, n
-Butyl group, isobutyl group, sec-butyl group, ter
t-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl group alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, and other cycloalkyl groups, The aryl groups of phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, benzyl group, various phenylethyl groups, and various methylbenzyl group arylalkyl groups are shown. As R ¹ , R ² , and R ³ , a hydrogen atom or an aliphatic hydrocarbon group having 5 or less carbon atoms is preferable, a hydrogen atom or an aliphatic hydrocarbon group having 3 or less carbon atoms is more preferable, and hydrogen is particularly preferable. Atoms are preferred.

On the other hand, R ⁴ in the general formula (I) has 1 carbon atom.
A divalent hydrocarbon group having 10 to 10 carbon atoms or a divalent ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon atoms is shown. Here, the divalent hydrocarbon group having 1 to 10 carbon atoms is specifically Is a methylene group; an ethylene group; a phenylethylene group; a 1,2-propylene group; a 2-phenyl-1,2-propylene group;
3-propylene group; various butylene groups; various pentylene groups; various hexylene groups; various heptylene groups; various octylene groups; various nonylene groups; divalent aliphatic groups of various decylene groups, cyclohexane; methylcyclohexane; ethylcyclohexane; dimethylcyclohexane Alicyclic groups having two bonding sites on alicyclic hydrocarbons such as propylcyclohexane, various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, and divalent naphthylene groups Aromatic hydrocarbon group, toluene; xylene; alkyl aromatic group such as ethylbenzene, etc. Alkyl aromatic group having monovalent bonding sites in the alkyl group portion and aromatic portion, xylene; polyalkyl aromatic carbonization such as diethylbenzene Alkyl group part of hydrogen It is an alkyl aromatic group having a binding site. Of these, an aliphatic group having 2 to 4 carbon atoms is particularly preferable.

Specific examples of the divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include methoxymethylene group; methoxyethylene group; methoxymethylethylene group; 1,1-bismethoxymethylethylene group; 1,2-
Bismethoxymethylethylene group; ethoxymethylethylene group; (2-methoxyethoxy) methylethylene group;
Preferable examples include (1-methyl-2-methoxy) methylethylene group. Incidentally, m in the general formula (I) represents a repeating number of R ⁴ O, the average value is 0
10, preferably a number in the range 0-5. When R ⁴ O is plural, plural R ⁴ O may be the same or different. Further, R ⁵ in the general formula (I) has 1 carbon atom.
The hydrocarbon groups are specifically represented by methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group and tert-hydrocarbon group. 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 trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, and other aryls Group, benzyl group, various phenyl ethyl Group shown, various methylbenzyl groups, various phenylpropyl groups, and arylalkyl groups various phenylbutyl groups. The R ^{1 to} R ⁵ may be the same or different for each structural unit.

This polyvinyl ether compound (1)
Has a constitutional unit represented by the general formula (I), and the number of repetitions (that is, the degree of polymerization) may be appropriately selected according to the desired kinematic viscosity, but usually at a temperature of 40 ° C. At a kinematic viscosity of ² to 200 mm ² / sec. The polyvinyl ether compound preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If this molar ratio is less than 4.2, the hygroscopicity may be high, and if it exceeds 7.0, the compatibility with the fluorocarbon refrigerant tends to decrease. The polyvinyl ether compound (2) is a block or random copolymer having (a) the structural unit represented by the general formula (I) and (b) the structural unit represented by the general formula (II). A compound of the formula (II), wherein R ^{6 to} R
⁹ each represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Here, as the hydrocarbon group having 1 to 20 carbon atoms, the same ones as exemplified in the description of R ⁵ in the above general formula (I) can be mentioned. In addition, R ^{6 to} R ⁹
May be the same or different for each structural unit.

The degree of polymerization of the polyvinyl ether compound (2) comprising a block or random copolymer having the constitutional unit represented by the general formula (I) and the constitutional unit represented by the general formula (II) is It may be appropriately selected according to the desired kinematic viscosity, but normally the kinematic viscosity at a temperature of 40 ° C is 2 to 2
It is chosen to be 00 mm ² / sec. The polyvinyl ether compound has a carbon / oxygen molar ratio of 4.
It is preferably in the range of 2 to 7.0. This molar ratio is 4.2
If it is less than 1.0, the hygroscopicity tends to be high, and if it exceeds 7.0, the compatibility with the chlorofluorocarbon refrigerant tends to decrease. Furthermore, the polyvinyl ether compound (3) is
(A) The polyvinyl ether compound (1) and (B)
It is composed of a mixture with the polyvinyl ether compound (2), and the mixing ratio thereof is not particularly limited. The polyvinyl ether compounds (1) and (2) are produced by polymerizing the corresponding vinyl ether monomers and copolymerizing the corresponding hydrocarbon monomers having an olefinic double bond with the corresponding vinyl ether monomers. You can The vinyl ether-based monomer that can be used here is represented by the general formula (IX)

[0022]

[Chemical 9]

[In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m are the same as described above. ] Is represented.
As the vinyl ether-based monomer, there are various ones corresponding to the above-mentioned polyvinyl ether-based compounds (1) and (2). For example, vinyl methyl ether; vinyl ethyl ether; vinyl-n-propyl ether; vinyl-
Isopropyl ether; Vinyl-n-butyl ether;
Vinyl-isobutyl 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; vinyl-2-methoxy-1
-Methyl ethyl ether; vinyl-2-methoxy-2-
Methyl 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-4-decyl ether; 1-methoxypropene; 1-ethoxypropene; 1-n-propoxypropene; 1-isopropoxypropene; 1-n-butoxypropene; 1-isobutoxypropene; 1-sec-butoxypropene. 1-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-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-isobutoxy-2-butene; 2-sec-butoxy-2-butene; 2-tert-butoxy-2-butene and the like. These vinyl ether type monomers can be produced by a known method.

The hydrocarbon monomer having an olefinic double bond is represented by the general formula (X)

[0025]

[Chemical 10]

[In the formula, R ^{6 to} R ⁹ are the same as defined above. ], Examples of the monomer include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptenes, various octenes, diisobutylene, triisobutylene, styrene, and various alkyl-substituted styrenes. .

The polyvinyl ether compound used as the main component in the lubricating oil of the present invention has the following terminal structure, that is, one of the terminals has the general formula
(III) or (IV)

[0028]

[Chemical 11]

[0029] wherein, R ^11, R ²¹ and R ³¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ^11,
R ²¹ and R ³¹ may be the same or different from each other,
R ⁶¹ , R ⁷¹ , R ⁸¹ and R ⁹¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶¹ , R ⁷¹ , R ⁸¹ and R ⁹¹ may be the same or different from each other. . R ⁴¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
A divalent ether-bonded oxygen-containing hydrocarbon group, R ⁵¹ is a hydrocarbon group having 1 to 20 carbon atoms, n is a number having an average value of 0 to 10, and when R ⁴¹ O is plural, plural R ⁴¹ O are plural. R ⁴¹ O in may be the same or different. ] And the remaining terminal is represented by the general formula (V) or (VI)

[0030]

[Chemical 12]

[0031] wherein, R ^12, R ²² and R ³² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ^12,
R ²² and R ³² may be the same or different from each other,
R ^62, R ^72, R ⁸² and R ⁹² each represent a hydrogen atom or a hydrocarbon group having a carbon number of ^{1~20, R 62, R 72,} R 82 and R ⁹² may be the same with or different from each other . R ⁴² is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
A divalent ether-bonded oxygen-containing hydrocarbon group, R ⁵² is a hydrocarbon group having 1 to 20 carbon atoms, p is a number having an average value of 0 to 10, and when R ⁴² O is plural, plural R ⁴² O are plural. R ⁴² O in may be the same or different. ] Having a structure represented by, and one end thereof is represented by the above general formula (III) or (IV), and the remaining end is represented by the general formula (VII)

[0032]

[Chemical 13]

[In the formula, R ¹³ , R ²³ and R ³³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different. ] The one having a structure represented by Further, it has only the constitutional unit represented by the general formula (I), one end of which is represented by the general formula (III), and the remaining end is represented by the general formula (VIII)

[0034]

[Chemical 14]

(In the formula, R ¹⁴ , R ²⁴ and R ³⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁴⁴ And R ⁶⁴ each represent a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different, and R ⁵⁴ and R ⁷⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms. A group, which may be the same or different from each other, and q and r each have an average value of 0 to 10
, Which may be the same or different from each other, and when plural R ⁴⁴ O are present, plural R ^44
44 O may be the same or different, and a plurality of R
^{When 64} O is present, a plurality of R ⁶⁴ O may be the same or different. ), And those having a structure represented by the general formula (III) at one end and an olefinically unsaturated bond at the other end.

Of such polyvinyl ether compounds
Among them, the following are the main components of the lubricating oil in the present invention.
It is suitable as an ingredient. (1) One terminal is represented by the general formula (III) or (IV)
And the remaining end is represented by the general formula (V) or (VI)
R in the general formula (I)¹, R²And R
³Are both hydrogen atoms, m is a number from 0 to 4, R^FourHas 2 to 2 carbon atoms
A divalent hydrocarbon group of 4 and R^FiveIs carbonized with 1 to 20 carbon atoms
Those that are hydrogen radicals. (2) having only the structural unit represented by the general formula (I)
And one of its terminals is represented by the general formula (III),
And the remaining terminal has a structure represented by the general formula (V),
R in the general formula (I)¹, R²And R³Together with hydrogen
Child, m is a number from 0 to 4, R^FourIs a divalent carbonization having 2 to 4 carbon atoms
Hydrogen radical and R^FiveIs a hydrocarbon group having 1 to 20 carbon atoms
of. (3) One terminal is represented by the general formula (III) or (IV)
And the remaining end has a structure represented by the general formula (VII).
R in the general formula (I)¹, R²And R³Together with water
Elementary atom, m is a number from 0 to 4, R^FourIs a C2-C4 divalent
Hydrocarbon group and R ^FiveIs a hydrocarbon group having 1 to 20 carbon atoms.
Things. (4) having only the structural unit represented by the general formula (I)
And one of its terminals is represented by the general formula (III),
And the remaining terminal has a structure represented by the general formula (VII),
R in the general formula (I)¹, R²And R³Together with hydrogen
Child, m is a number from 0 to 4, R^FourIs a divalent carbonization having 2 to 4 carbon atoms
Hydrogen radical and R^FiveIs a divalent hydrocarbon group having 1 to 20 carbon atoms
And R^FiveIs a hydrocarbon group having 1 to 20 carbon atoms.

The polyvinyl ether compound can be produced by radical polymerization, cationic polymerization, radiation polymerization or the like of the above-mentioned monomer. For example, a vinyl ether-based monomer is polymerized by the method described below to obtain a polymer having a desired viscosity. For the initiation of polymerization, it is possible to use a combination of Bronsted acids, Lewis acids or organometallic compounds with adducts of water, alcohols, phenols, acetals or vinyl ethers and carboxylic acids. it can. Examples of Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid and trifluoroacetic acid. Examples of Lewis acids include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, and ferric chloride. Among these Lewis acids, boron trifluoride is particularly preferable. Is preferred. Examples of the organometallic compound include diethyl aluminum chloride, ethyl aluminum chloride, diethyl zinc and the like. Any adduct of water, alcohols, phenols, acetals or vinyl ethers and carboxylic acid to be combined therewith can be selected.

Here, as the alcohols, for example, methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols, various octanols, etc. Examples of the saturated aliphatic alcohol having 20 to 20 carbon atoms, unsaturated aliphatic alcohol having 3 to 10 carbon atoms such as allyl alcohol, and the like. Examples of the carboxylic acid in the case of using an adduct of vinyl ethers and carboxylic acid include acetic acid; propionic acid; n-butyric acid; isobutyric acid; n-valeric acid;
Isovaleric acid; 2-methylbutyric acid; pivalic acid; n-caproic acid; 2,2-dimethylbutyric acid; 2-methylvaleric acid; 3-methylvaleric acid; 4-methylvaleric acid; enanthate; 2-methylcaproic acid Caprylic acid; 2-ethylcaproic acid; 2
Examples include -n-propylvaleric acid; n-nonanoic acid; 3,5,5-trimethylcaproic acid; caprylic acid; and undecanoic acid. The vinyl ethers may be the same as or different from those used for the polymerization. The adduct of the vinyl ether and the carboxylic acid is obtained by mixing both and reacting at a temperature of about 0 to 100 ° C., and can be separated by distillation or the like and used for the reaction, but it is separated as it is. It can also be used in the reaction without. The polymerization initiation end of the polymer is
When water, alcohols, or phenols are used, hydrogen is bonded, and when acetals are used, one of the alkoxy groups is eliminated from hydrogen or the used acetal. When an adduct of vinyl ether and carboxylic acid is used, the alkylcarbonyloxy group derived from the carboxylic acid moiety is eliminated from the adduct of vinyl ether and carboxylic acid.

On the other hand, the terminating end becomes acetal, olefin or aldehyde when water, alcohols, phenols or acetals are used. Further, in the case of an adduct of vinyl ethers and carboxylic acid, it becomes a carboxylic acid ester of hemiacetal. The terminal of the polymer thus obtained can be converted into a desired group by a known method. Examples of the desired group include residues of saturated hydrocarbons, ethers, alcohols, ketones, nitriles, amides, etc., but saturated hydrocarbons, ethers and alcohol residues are preferable.

The polymerization of the vinyl ether type monomer represented by the general formula (IX) depends on the kinds of the raw materials and the initiator,
It can be started between 80 and 150 ° C, usually -8
It can be carried out at a temperature in the range of 0 to 50 ° C. The polymerization reaction is completed within 10 seconds to 10 hours after the start of the reaction. Regarding the control of the molecular weight in this polymerization reaction, the amount of water, alcohols, phenols, acetals and adducts of vinyl ethers and carboxylic acid with respect to the vinyl ether-based monomer represented by the above general formula (IX) is increased. By doing so, a polymer having a low average molecular weight can be obtained. Further, by increasing the amounts of the above Bronsted acids and Lewis acids, a polymer having a low average molecular weight can be obtained. This polymerization reaction is usually performed in the presence of a solvent. The solvent is not particularly limited as long as it dissolves the reaction raw materials in a necessary amount and is inert to the reaction, but is not particularly limited, and examples thereof include hydrocarbon systems such as hexane, benzene and toluene, and ethyl ether, 1,2- Ether-based solvents such as dimethoxyethane and tetrahydrofuran can be preferably used.
The polymerization reaction can be stopped by adding an alkali. After completion of the polymerization reaction, an ordinary polyvinyl ether-based compound having a structural unit represented by the general formula (I) can be obtained by subjecting to a usual separation / purification method.

The polyvinyl ether compound used as the main component in the lubricating oil of the present invention preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0 as described above. By adjusting the oxygen molar ratio, a polymer having the molar ratio within the above range can be produced. That is, a polymer having a large carbon / oxygen molar ratio is obtained when the ratio of the monomer having a large carbon / oxygen molar ratio is large, and a polymer having a small carbon / oxygen molar ratio is obtained when the ratio of the monomer having a small carbon / oxygen molar ratio is large. Is obtained. Further, as shown in the above-mentioned method for polymerizing vinyl ether-based monomers, it is possible to combine water, alcohols, phenols, acetals and adducts of vinyl ethers and carboxylic acid used as initiators with monomers. Is. Carbon from polymerizing monomer /
If alcohols or phenols with a large oxygen molar ratio are used as the initiator, a polymer with a larger carbon / oxygen molar ratio than the raw material monomer can be obtained, while alcohols with a small carbon / oxygen molar ratio such as methanol or methoxyethanol are obtained. Polymers having a carbon / oxygen molar ratio smaller than that of the raw material monomer can be obtained by using these compounds.

Further, when the vinyl ether-based monomer and the hydrocarbon monomer having an olefinic double bond are copolymerized, a polymer having a carbon / oxygen molar ratio larger than that of the vinyl ether-based monomer can be obtained. The ratio can be adjusted by the ratio of the hydrocarbon monomer having an olefinic double bond used and the number of carbon atoms. The lubricating oil in the present invention contains the polyvinyl ether compound as a main component. The kinematic viscosity of the lubricating oil before mixing with the refrigerant is 2 to 20 at 40 ° C.
In the range of 0 mm ² / s, in particular 5 to 100 mm ² / sec is preferred. The average molecular weight of this polymer is usually 150 to 2000. In addition, even if the polymer is out of the above kinematic viscosity range, by mixing with a polymer having another kinematic viscosity,
It is also possible to adjust the viscosity within the above kinematic viscosity range.

In the lubricating oil of the present invention, the above-mentioned polyvinyl ether compounds may be used alone or in combination of two or more kinds. Further, it can be used as a mixture with other lubricating oils such as esters, polyalkylene glycols and mineral oils. When the polyvinyl ether compound is mixed with another lubricating oil, the polyvinyl ether compound is preferably contained in the mixed lubricating oil in an amount of at least 50% by weight. Further, the lubricating oil in the present invention includes various additives used in conventional lubricating oils, such as load bearing additives, chlorine scavengers, antioxidants,
Add metal deactivators, defoamers, detergent dispersants, viscosity index improvers, oiliness agents, antiwear agents, extreme pressure agents, rust inhibitors, corrosion inhibitors, pour point depressants, etc. as desired. can do. The above load-bearing additives include monosulfides,
Organic sulfur compounds such as polysulfides, sulfoxides, sulfones, thiosulfinates, sulfurized fats, thiocarbonates, thiophenes, thiazoles, methanesulfonic acid esters, phosphoric acid monoesters, phosphoric acid Phosphoric acid ester-based compounds such as diesters and phosphoric acid triesters (tricresyl phosphate, etc.), Phosphorous acid ester compounds such as phosphorous acid monoesters, phosphorous acid diesters and phosphorous acid triesters , Thiophosphoric acid ester-based compounds such as thiophosphoric acid triesters, higher fatty acids, hydroxyaryl fatty acids, polyhydric alcohol esters, ester-based compounds such as acrylic acid esters, chlorinated hydrocarbons, chlorination Organochlorine compounds such as carboxylic acid derivatives, fluorinated aliphatic carboxylic acids, Organic fluorinated compounds such as fluorinated ethylene resins, fluorinated alkyl polysiloxanes, fluorinated graphite, alcohols such as higher alcohols, naphthenates (lead naphthenate, etc.), fatty acid salts (lead fatty acid, etc.) ), Thiophosphates (zinc dialkyldithiophosphate, etc.), thiocarbamates, organomolybdenum compounds, organotin compounds, organogermanium compounds, and borate esters.

Examples of chlorine scavengers include glycidyl ether group-containing compounds, epoxidized fatty acid monoesters, epoxidized fats and oils, epoxy cycloalkyl group-containing compounds. As antioxidants, phenols (2,6-
Ditertiary butyl-p-cresol, etc.), aromatic amines (α-naphthylamine, etc.), and the like. Examples of the metal deactivator include benzotriazole derivatives. Examples of the defoaming agent include silicone oil (dimethyl polysiloxane etc.) and polymethacrylates. Examples of detergent dispersants include sulfonates, phenates, and succinimides. Examples of the viscosity index improver include polymethacrylate, polyisobutylene, ethylene-propylene copolymer, styrene-diene hydrogenated copolymer and the like.

In the refrigerating apparatus and the refrigerant compressor of the present invention, hydrofluorocarbon-based, fluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based or ammonia-based refrigerants are used as the refrigerant. Among these, hydrofluorocarbons are used. System refrigerants are preferred. Examples of the hydrofluorocarbon-based refrigerant include 1,1,1,2-tetrafluoroethane (R134
a), difluoromethane (R32), pentafluoroethane (R125) and 1,1,1-trifluoroethane (R143a) are preferable, and these may be used alone or in combination of two or more kinds. . These hydrofluorocarbons are preferable as a refrigerant for a compression refrigerator, because they do not have a risk of destroying the ozone layer.
Further, as an example of the mixed refrigerant, R32, R125, and R1
34a in a weight ratio of 23:25:52 (hereinafter R
407C. ), R32 and R125 weight ratio 5
0:50 mixture (hereinafter referred to as R410A), R
A mixture of 32 and R125 in a weight ratio of 45:55 (hereinafter,
It is called R410B. ), R125, R143a and R1
34a in a weight ratio of 44: 52: 4 (hereinafter referred to as R4
04A. ), A mixture of R125 and R143a in a weight ratio of 50:50 (hereinafter referred to as R507), and the like.

Next, the refrigerating apparatus of the present invention has a refrigerating cycle including a compressor, a condenser, an expansion mechanism (expansion valve, etc.), a dryer and an evaporator, and a lubricating oil (refrigerating machine oil). ) As a main component, a lubricating oil having a kinematic viscosity of ² to 200 mm ² / sec at a temperature of 40 ° C. as a main component is used, and a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type is used as a refrigerant. , Carbon dioxide-based or ammonia-based refrigerants, preferably hydrofluorocarbon-based refrigerants are used. Here, it is preferable to fill the desiccant with a desiccant composed of zeolite having a pore size of 3.5 Å or less. In addition, examples of this zeolite include natural zeolite and synthetic zeolite.

In the present invention, when such a desiccant is used, water can be efficiently removed without absorbing the refrigerant in the refrigeration cycle, and at the same time, the desiccant itself is prevented from being pulverized due to deterioration, and thus the powder is This eliminates the risk of abnormal wear and the like due to blockage of the pipes and invasion of the sliding parts of the compressor, which can operate the refrigeration apparatus stably over a long period of time. Further, the refrigerant compressor of the present invention constitutes a refrigeration cycle of the above refrigeration system, and is an internal high pressure type or internal low pressure type hermetic compressor in which the compressor and the electric motor are covered in one cover. It is a machine.

In any of the above formats, an electric motor
In which the windings of the stator, (such as magnet wire) core wire was coated with a glass transition temperature of 130 ° C. or more enamel
It is necessary to be. Further , it is preferable that the enamel wire is fixed with a varnish having a glass transition temperature of 50 ° C. or higher.
Further, the enamel coating is comprised of polyester, polyimide, polyamide or polyamideimide
It must be at least one monolayer or composite layer selected from the group . In particular, the enamel coating, which has a lower glass transition temperature as the lower layer and a higher glass transition temperature as the upper layer, has excellent water resistance, softening resistance, and swelling resistance, as well as mechanical strength, rigidity, and insulation. High and practically useful. Further, in the refrigerant compressor of the present invention, the insulating film which is the electric insulating material of the motor portion is preferably made of a crystalline plastic film having a glass transition temperature of 60 ° C. or higher. In particular, this crystalline plastic film has an oligomer content of 5% by weight.
The following are preferred: Such a glass transition temperature 6
Examples of the crystalline plastic having a temperature of 0 ° C. or higher include polyether nitrile, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide,
Suitable examples include polyether ether ketone, polyethylene naphthalate, polyamide imide or polyimide. The insulating film of the motor may be composed of a single layer of the above-mentioned crystalline plastic film, or may be a composite film in which a plastic layer having a high glass transition temperature is coated on a film having a low glass transition temperature. it can.

In the refrigerant compressor of the present invention, a vibration isolating rubber material can be arranged inside the compressor. In that case, the vibration isolating rubber material is acrylonitrile-butadiene rubber (NBR), ethylene-propylene. -Diene rubber (E
PDM, EPM), hydrogenated acrylonitrile-butadiene rubber (HNBR), silicone rubber and fluororubber (FKM) are preferably used, and particularly those having a rubber swelling ratio of 10% by weight or less are preferable. Further, in the refrigerant compressor of the present invention, various organic materials (for example, lead wire coating material, binding thread, enamel wire, insulating film, etc.) can be arranged inside the compressor. As a material, its tensile strength reduction rate is 20%
The following are preferably used. Furthermore, in the refrigerant compressor of the present invention, the swelling rate of the gasket in the compressor is 2
It is preferably 0% or less.

Next, specific examples of the refrigerant compressor of the present invention include hermetic scroll compressors, hermetic swing compressors, hermetic reciprocating compressors, hermetic rotary compressors and the like. Here, an example of the hermetic rotary compressor will be described with reference to the accompanying drawings. FIG. 1 is a longitudinal sectional view of an essential part of an example of a hermetic twin rotary type compressor, which is a kind of a refrigerant compressor of the present invention, in which a motor part is provided in an upper stage in a case 1 which is a hermetic container also serving as an oil reservoir. (Electric motor section) and the compressor section are stored in the lower stage. The motor section includes a stator (stator) 2 and a motor rotor (rotor) 3, and a rotation shaft 4 is fitted to the motor rotor 3. The core wire of the winding part 5 of the stator 2 is usually covered with an enameled wire, and an electrically insulating film is inserted between the core part and the winding part of the stator 2. On the other hand, the compressor section is composed of two compression chambers, an upper compression chamber 6 and a lower compression chamber 7. In this compressor, the compressed refrigerant gas is alternately discharged from the upper and lower compression chambers 6 and 7 with a phase difference of 180 degrees. In the compression chamber, a cylindrical rotary piston is driven by a crank fitted inside, and rotates eccentrically in contact with a point on the wall surface of the cylinder. Further, the blade is pressed by a spring and reciprocates so that the tip is always in contact with the rotary piston. Here, when the rotary piston eccentrically rotates, the volume of one of the two spaces divided by the blade decreases, and the refrigerant gas is compressed. When the pressure reaches a predetermined value, the valve provided on the bearing flange surface opens and the refrigerant gas is discharged to the outside.

[0051]

EXAMPLES The present invention will now be described in more detail by way of examples, which should not be construed as limiting the invention thereto.

Example 1 Using polyethyl vinyl ether, kinematic viscosity, R134
The compatibility with a, the volume resistivity, and the hydrolysis stability were measured, and an organic material compatibility test and a rubber swelling test were performed. The results obtained are shown in Table 1. The measurement conditions are as follows. Kinematic viscosity According to JIS K2283-1983, it was measured using a glass capillary viscometer. Compatibility (a) R134a 1,1,1,2-tetrafluoroethane (R134a)
On the other hand, a predetermined amount of the sample was added to the pressure resistant glass ampoule so that the weight became 5% by weight and 10% by weight, and this was connected to the vacuum pipe and the R134a gas pipe. The ampoule was vacuum degassed at room temperature and then cooled with liquid nitrogen to collect a predetermined amount of R134a. Then, the ampoule is sealed and the compatibility on the low temperature side is gradually cooled from room temperature to −60 ° C. in the constant temperature bath, while the compatibility on the high temperature side is increased from room temperature to + 60 ° C.
The temperature at which phase separation started was measured by gradually heating to 80 ° C. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. (b) A predetermined amount of a sample was added to a pressure-resistant glass ampoule so as to be 10% by weight and 20% by weight with respect to R32 difluoromethane (R32), and this was connected to a vacuum pipe and an R32 gas pipe. The ampoule was vacuum degassed at room temperature and then cooled with liquid nitrogen to collect a predetermined amount of R32. Then, the ampoule is sealed and the compatibility on the low temperature side is gradually cooled from room temperature in the constant temperature bath, while the compatibility on the high temperature side is gradually heated from room temperature to + 40 ° C. to start phase separation. The temperature was measured. On the low temperature side, the lower the phase separation temperature,
On the high temperature side, the higher the phase separation temperature, the more preferable.

The volume resistivity sample was dried under reduced pressure (0.3 to 0.8 mmHg) at 100 ° C. for 1 hour and then enclosed in a liquid cell for measuring the volume resistivity in an 80 ° C. thermostat. After keeping in a constant temperature bath of 80 ° C. for 40 minutes, measurement was performed with an applied voltage of 250 V using an R8340 super insulation meter manufactured by Advantest. 75 g of the sample, 25 g of water and copper (13 mm × 50 mm) were put in a pressure resistant bottle having a hydrolysis stability capacity of 250 ml, and the inside of the container was made a nitrogen atmosphere. The temperature was kept at 102 ° C. for 192 hours in a rotary constant temperature bath. Then, the appearance of the sample oil, the total acid value, and the state of the copper pieces were observed. Organic oil compatibility test 50g sample oil, R4 in autoclave of 250ml capacity
20A of 10A and each organic material were enclosed, and the mixture was kept at 120 ° C for 72 hours. As the organic material, an enamel wire (material: polyamideimide) and an insulating film (material: polyethylene terephthalate) were used. For the enamel wire, the appearance after the test was visually observed, and for the insulating film, an oligomer against the amount of oil was used. Was measured. Rubber swelling test 50g sample oil, R4 in autoclave with 250ml capacity
20 A of 10 A and a rubber material (O-ring: HNBR) were enclosed and the mixture was kept at 120 ° C. for 72 hours. After the test was completed, the weight change rate of the rubber was measured.

Examples 2 to 4 In Example 1, instead of polyethyl vinyl ether, polyisopropyl vinyl ether (Example 2), polymethyl vinyl ether (Example 3) or polyethyl vinyl ether polyisopropyl vinyl ether copolymer (ethyl vinyl: Isopropyl vinyl = 5: 5)
The kinematic viscosity, compatibility with R134a, volume resistivity and hydrolysis stability were measured in the same manner as in Example 1 except that (Example 4) was used, and an organic material compatibility test and a rubber swelling test were performed. went. The results obtained are shown in Table 1.

Comparative Example 1 Example 1 was carried out using a commercially available paraffinic mineral oil (VG32).
The kinematic viscosity, the compatibility with R134a, the volume resistivity, and the hydrolysis stability were measured in the same manner as in 1. and the organic material compatibility test and the rubber swelling test were performed. The results obtained are shown in Table 1.

Comparative Example 2 Using polypropylene glycol (manufactured by NOF CORPORATION, Unilube MB11), kinematic viscosity, compatibility with R134a, volume resistivity and hydrolysis stability were measured in the same manner as in Example 1. At the same time, an organic material compatibility test and a rubber swelling test were performed. The results obtained are shown in Table 1.

Comparative Example 3 Using a hindered ester, kinematic viscosity, compatibility with R134a, volume resistivity and hydrolysis stability were measured in the same manner as in Example 1, and an organic material compatibility test and a rubber swelling test were conducted. I went. The results obtained are shown in Table 1.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

Example 5 With respect to polyisobutyl vinyl ether, kinematic viscosity, compatibility with Freon 134a, volume resistivity, hydrolysis stability and hygroscopicity were measured, and an organic material compatibility test and a rubber swelling test were conducted. The results obtained are shown in Table 2. The measurement conditions are as follows. (1) Kinematic viscosity: The same as in Example 1. (2) Compatibility test With respect to R134a, a predetermined amount of sample was added to a pressure resistant glass ampoule, which was connected to a vacuum pipe and a R134a gas pipe. The ampoule was vacuum degassed at room temperature and then cooled with liquid nitrogen to collect a predetermined amount of R134a. Then, the ampoule is sealed, and the compatibility on the low temperature side is gradually cooled from room temperature to −50 ° C. in the constant temperature bath, while the compatibility on the high temperature side is gradually heated from room temperature to + 90 ° C. The temperature at which phase separation begins was measured. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. Also for R32 and R125, R134a
The measurement was performed in the same manner as in. In addition, about R32, only the low temperature side was measured, and about R125, the range of -50 degreeC to +50 degreeC was measured.

(3) Volume resistivity: The same as in Example 1. (4) Hydrolytic stability: The same as in Example 1. The total acid value of the sample oil before the test was 0.01 mgKOH / g.
Met. (5) Hygroscopic Test Sample oil 20 g was put in a glass 50 cc sample bottle and put in a desiccator whose humidity and temperature were controlled to be constant,
The weight change was measured. The increased weight corresponds to the absorbed moisture. The temperature was controlled at 30 ° C. by putting a desiccator in a constant temperature bath. Humidity was controlled at 81% by adding saturated ammonium sulfate water and ammonium sulfate powder to the bottom of the desiccator. (6) Organic material compatibility test: The same as in Example 1. (7) Rubber swelling test: The same as in Example 1.

Examples 6 to 9 In Example 5, instead of polyisobutyl vinyl ether, polyethyl vinyl ether polyisobutyl vinyl ether copolymer (ethyl vinyl: isobutyl vinyl = 4: 6) (Example 6), polyethyl vinyl ether polyisobutyl Vinyl ether copolymer (ethyl vinyl:
Isobutyl vinyl = 5: 5) (Example 7), polyethyl vinyl ether polyisobutyl vinyl ether copolymer (ethyl vinyl: isobutyl vinyl = 7: 3) (Example 8) or polyethyl vinyl ether polyisobutyl vinyl ether copolymer (ethyl vinyl: Isobutyl vinyl = 5: 5 (however, higher molecular weight than Example 7))
In the same manner as in Example 5 except that (Example 9) was used, the kinematic viscosity, the compatibility with R134a, the volume resistivity, the hydrolysis stability, and the hygroscopicity were measured, and an organic material compatibility test rubber and A swelling test was performed. The results obtained are shown in Table 2.

[0064]

[Table 4]

[0065]

[Table 5]

[0066]

[Table 6]

[0067]

[Table 7]

[0068]

[Table 8]

[0069]

[Table 9]

[0070]

[Table 10]

[0071]

[Table 11]

[0072]

The refrigeration system of the present invention comprises a high-pressure container type or low-pressure container type refrigerant compressor,
By using a lubricating oil (refrigerating machine oil) containing a polyvinyl ether-based compound as a main component, various refrigerants including a hydrofluorocarbon-based refrigerant can be used. In particular, the polyvinyl ether-based compound has good compatibility with a hydrofluorocarbon-based refrigerant that can be a substitute for chlorofluorocarbon, which is a problem in environmental pollution, and is excellent in lubrication performance. In the above, it is preferable to use a hydrofluorocarbon type refrigerant as the refrigerant. The refrigerating apparatus of the present invention has excellent performance and efficiency and can be stably operated for a long period of time.

[Brief description of drawings]

FIG. 1 is a longitudinal sectional view of an essential part of an example of a compression refrigerator according to the present invention.

[Explanation of symbols]

1: Case 2: Stator 3: Motor roller 4: rotating shaft 5: Winding part 6: Upper compression chamber 7: Lower compression chamber 8: Muffler 9: Accumulator 10: Suction pipe

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C10N 40:30 C10N 40:30 (72) Inventor Masato Kaneko 24 No. 4 Anezaki Kaigan, Ichihara City, Chiba Prefecture (56) References 6-128578 (JP, A) JP-A-8-193196 (JP, A) JP-A-6-240278 (JP, A) JP-A-6-240279 (JP, A) JP-A-8-73880 (JP, A) JP 8-209180 (JP, A) JP 8-170586 (JP, A) JP 8-176536 (JP, A) JP 9-272886 (JP, A) JP 10 -8082 (JP, A) JP 10-46169 (JP, A) JP 10-88161 (JP, A) JP 10-103279 (JP, A) Actual flat 4-39676 (JP, U) ) International publication 96/11246 (WO, A1) (58) Fields investigated (Int.Cl. ⁷ , DB name) F25B 1/00 C10M 107/24 C10N 20:02 C10N 30:00 C10N 40:30

Claims (21)

(57) [Claims] 1. A refrigeration cycle including at least a refrigerant compressor, a condenser, an expander groove , an evaporator and a dryer, and a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or A refrigeration apparatus comprising an ammonia-based refrigerant and a lubricating oil containing a polyvinyl ether compound as a main component and having a kinematic viscosity at a temperature of 40 ° C. of ² to 200 mm ² / sec , wherein the polyvinyl ether compound is one
General formula (I) ## STR1 ## [In the formula, R ¹ , R ² and R ³ are each a hydrogen atom.
Or represents a hydrocarbon group having 1 to 8 carbon atoms, which is
May be the same or different, and R ⁴ has 1 to 1 carbon atoms.
A divalent hydrocarbon group having 0 or a divalent hydrocarbon group having 2 to 20 carbon atoms
Ter-bonded oxygen-containing hydrocarbon group, R ⁵ has 1 to 20 carbon atoms
A hydrocarbon group of, m is a number having an average value of 0 to 10,
R ^{1 to} R ⁵ are different for each structural unit even if they are the same.
Or if there are a plurality of R ⁴ O's,
A plurality of R ⁴ O may be the same or different. ]
The refrigerant compression consisting of a polymer having a constitutional unit
The compressor and the electric motor are covered in one cover.
High pressure type hermetic compressor or internal low pressure hermetic compressor
In addition, the winding of the stator of the electric motor makes the core wire glass transition.
It is coated with enamel at a temperature of 130 ° C or higher.
Enamel coating is polyester imide, polyimide, poly
A small amount selected from the group consisting of amides and polyamideimides
Refrigeration equipment that consists of at least one type of insulating layer . 2. The polyvinyl ether compound is (a).
A structural unit represented by the general formula (I), and (b) a general formula (I
I) [Chemical 2] [In the formula, R ^{6 to} R ⁹ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and R ^{6 to} R ⁹ are the same as each other; The units may be the same or different. ]
The refrigerating apparatus according to claim 1, which comprises a block or random copolymer having a structural unit represented by: 3. A polyvinyl ether compound is (A).
A polymer having a structural unit represented by general formula (I), and (B) (a) a structural unit represented by general formula (I) and (b)
The refrigerating apparatus according to claim 1, which is a mixture of a block or random copolymer having a structural unit represented by the general formula (II). 4. A carbon / oxygen molar ratio of polyvinyl ether compound refrigeration system of claim 1, 2 or 3 wherein the 4.2 to 7.0. 5. A polyvinyl ether-based compound, one terminal of which is represented by the general formula (III) or (IV): [In formula, R < ¹¹ >, R <^21> and R < ³¹ > show a hydrogen atom or a C1-C8 hydrocarbon group, respectively, R < ¹¹ >, R <^21> and R <^31>.
They may be the same or different, and R ⁶¹ , R ⁷¹ ,
R ⁸¹ and R ⁹¹ are each a hydrogen atom or a carbon number of 1 to 20.
And R ⁶¹ , R ⁷¹ , R ⁸¹ and R ⁹¹ may be the same or different. R ⁴¹ has 1 to 1 carbon atoms
0 divalent hydrocarbon group or C 2-20 divalent ether bond oxygen-containing hydrocarbon group, R ⁵¹ is a C 1-20 hydrocarbon group, and n is a number whose average value is 0-10. Indicates R
^When there are plural ⁴¹ O, plural R ⁴¹ O may be the same or different. ] And the remaining terminal is represented by the general formula (V) or (VI) (In the formula, R ¹² , R ²² and R ³² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ¹² , R ²² and R ³²
They may be the same or different, and R ⁶² , R ⁷² ,
R ⁸² and R ⁹² are each a hydrogen atom or a carbon number of 1 to 20.
And R ⁶² , R ⁷² , R ⁸² and R ⁹² may be the same or different. R ⁴² has 1 to 1 carbon atoms
A divalent hydrocarbon group of 0 or a divalent ether bond oxygen-containing hydrocarbon group of 2 to 20 carbon atoms, R ⁵² is a hydrocarbon group of 1 to 20 carbon atoms, and p is a number whose average value is 0 to 10 Indicates R
⁴² if O is plural, plural R ⁴² O may be the same or different. ] The refrigeration equipment of Claim 1, 2 or 3 which has a structure represented by these. 6. A polyvinyl ether compound according to claim 1 of which one terminal is represented by formula (III), and those having a structure in which the other terminal is represented by the general formula (V)
The refrigeration system described. 7. A polyvinyl ether compound, one end of which is represented by the general formula (III) or (IV), and the other end is represented by the general formula (VII): [In the formula, R ¹³ , R ²³ and R ³³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different from each other. ] The refrigeration equipment of Claim 1, 2 or 3 which has a structure represented by these. 8. A polyvinyl ether compound, one end of which is represented by the general formula (III) and the other end is represented by the general formula (VIII): (In the formula, R ¹⁴ , R ²⁴ and R ³⁴ 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 ⁴⁴ and R ⁶⁴ Each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different from each other, and R ⁵⁴ and R ⁷⁴ each represent a hydrocarbon group having 1 to 10 carbon atoms. ,
They may be the same or different,
q and r are numbers each having an average value of 0 to 10,
They may be the same or different,
Further to the plurality of R ⁴⁴ O is when there are multiple R ⁴⁴ O may be the same or different and also the plurality of R ⁶⁴ O is when there are multiple R ⁶⁴ O be the same It may be different. ) The refrigerating apparatus according to claim 1, which has a structure represented by ( 4 ). 9. polyvinyl ether compound, of which one terminal is represented by formula (III), and the remaining terminal refrigeration system according to claim 1, wherein those having an olefinic unsaturated bond. 10. R ¹ , R ² and R ³ in the general formula (I) are all hydrogen atoms, m is 0 to 4 and R ⁴ is 2 carbon atoms.
10. The refrigerating apparatus according to any one of claims 5 to 9 , wherein the divalent hydrocarbon group of 4 to 4 and R ⁵ are hydrocarbon groups of 1 to 20 carbon atoms. 11. Polyvinyl ether compounds are poly
Methyl vinyl ether, polyethyl vinyl ether,
Reisopropyl vinyl ether, polyisobutyl vinyl
Ether, polyethyl vinyl ether polyisopropyl
Vinyl ether copolymer and polyethyl vinyl ether
A small amount selected from polyisobutyl vinyl ether copolymers
The refrigeration system according to claim 1, which is at least one compound. 12. The refrigerant is a hydrofluorocarbon type refrigerant, and 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane and 1,1.
The refrigeration system according to claim 1, which is at least one selected from 1,1-trifluoroethane. 13. drier, according to claim 1 is made by filling the desiccant consisting pore diameter 3.5Å following zeolites
The refrigeration system described. 14. Request enameled wire of a stator of the motor is obtained by fixing a glass transition temperature of 50 ° C. or more varnishes
The refrigerating apparatus according to Item 1 . 15. The insulating film for an electric motor is made of a crystalline plastic film having a glass transition temperature of 60 ° C. or higher.
The refrigeration system according to claim 1 . 16. The refrigerating apparatus according to claim 15 , wherein the insulating film of the electric motor is a crystalline plastic film having a glass transition temperature of 60 ° C. or higher, and the amount of oligomer in the film is 5% by weight or less. 17. The crystalline plastic film is at least one insulating film selected from the group consisting of polyether nitrile, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, polyethylene naphthalate, polyamide imide and polyimide. Claims that are
The refrigeration apparatus according to 15 or 16 . 18. The refrigeration apparatus of claim 1, wherein formed by disposing a vibration proof rubber material inside the refrigerant compressor. 19. A vibration-proof rubber material is acrylonitrile-
It is at least one rubber selected from the group consisting of butadiene rubber, ethylene-propylene-diene rubber, hydrogenated acrylonitrile-butadiene rubber, silicone rubber and fluororubber, and has a rubber swelling ratio of 10% by weight or less. The refrigeration apparatus according to claim 18 . 20. The refrigeration system of claim 1, wherein the tensile strength reduction rate of the organic material disposed therein a refrigerant compressor is of 20% or less. 21. The refrigeration apparatus of claim 1, wherein the swelling rate of the refrigerant compressor of the gasket is of 20% or less.