JPH10147682A - Refrigeration unit and refrigerant compressor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a refrigeration unit that uses, as refrigerant, a hydrofluorocarbon substitutable for chlorofluorocarbon which is problematic in environmental pollution and additionally uses a lubricant oil which has good compatibility to be refrigerant and excellent lubricity. SOLUTION: This refrigerator is equipped with at least a compressor, a condenser, an expansion mechanism and an evaporator as a refrigeration cycle, and uses a refrigerant of hydrofluorocarbon, fluorocarbon, hydrocarbon, ether, carbon dioxide or ammonia and a lubricant oil that mainly contains a polyvinyl ether compound and has a dynamic viscosity of 2-200mm<2> /sec at 40 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

2. Description of the Related Art In general, a compression refrigerator comprises at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), an evaporator, or a dryer, and a liquid mixture of refrigerant and lubricating oil is sealed. It has a structure that circulates through the system. In such a compression type refrigerator, although it depends on the type of equipment, the temperature is generally high in the compressor and low in the cooler, so that the refrigerant and the lubricating oil phase-separate within a wide temperature range from low to high. It is necessary to circulate in this system without doing. Generally, the refrigerant and the lubricating oil have a region where phase separation occurs on a low temperature side and a high temperature side, and the maximum temperature of the low temperature side separation region is preferably -10 ° C or less, particularly -20 ° C.
C. or less is preferred. 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 the operation of the refrigerator, the life and efficiency of the device will be significantly adversely affected. For example, when the phase separation of the refrigerant and the lubricating oil occurs in the compressor part, the moving part becomes inadequately lubricated, causing seizure or the like to significantly shorten the life of the device, while the phase separation occurs in the evaporator, The presence of the lubricating oil having a high viscosity causes a reduction in the efficiency of heat exchange.

[0003] Further, since lubricating oil for refrigerators is used for lubricating movable parts of the refrigerator, lubrication performance is naturally important. In particular, since the temperature inside the compressor becomes high, a viscosity capable of holding an oil film required for lubrication is important. The required viscosity varies depending on the type of compressor used and operating conditions, but usually the viscosity (kinematic viscosity) of the lubricating oil before mixing with the refrigerant is preferably from ² to 200 mm ² / sec at 40 ° C., especially 5~100mm ² / sec is preferred. If the viscosity is lower than this, the oil film becomes thin and lubrication failure easily occurs, and if it is higher, the efficiency of heat exchange decreases. In electric refrigerators and air conditioners, since the electric motor (motor) and the compressor (compressor) are integrated, the lubricating oil is required to have high electrical 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 risk of electric leakage. Further, lubricating oils are required to have high stability. For example, when an organic acid is generated by hydrolysis or the like, corrosion or abrasion of the device is easily caused, depending on the amount thereof.

Conventionally, as a refrigerant for a compression refrigerator, particularly an air conditioner, chlorodifluoromethane (hereinafter referred to as R22) or a chlorodifluoromethane / chloropentafluoroethane having a weight ratio of 48.8: 51.2. Mixture (hereinafter,
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 destruction of the ozone layer, their regulations have recently become stricter worldwide. Therefore, as a new refrigerant, 1,1,1,2-tetrafluoroethane; difluoromethane; pentafluoroethane; 1,1,1-trifluoroethane (hereinafter, referred to as R134a, R32, R125, and R143a, respectively). Hydrofluorocarbons have been attracting attention. This hydrofluorocarbon, particularly 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 hydrofluorocarbon is used alone. For example, in “Energy and Resources”, Vol. 16, No. 5, pp. 474, (1) R134 is used instead of R22.
When a is applied to an air conditioner, the operating pressure is low and R22
Approximately 40% less capacity and 5% less efficiency than
It has been reported that (2) R32 is more efficient than R22, but has a higher operating pressure and is slightly flammable, and (3) R125 is nonflammable but has a lower critical pressure and lower efficiency. . Further, R143a has a flammability problem like R32.

[0005] As a refrigerant for a compression type refrigerator, it is desirable to be able to use it without changing the current refrigeration system. However, due to the above-mentioned problem, a refrigerant mixed with the above-mentioned hydrofluorocarbon should be actually used. That is, the current R
In order to substitute the refrigerants R22 and R502, flammable R32 and R143a are used from the viewpoint of efficiency, and the refrigerant is made nonflammable as a whole.
Is desirably mixed with the former. The International
Symposium on R22 & R502 Alternative Refrigerants,
1994, p. 166) shows that the R32 / R134a mixture is flammable when the R32 content is 56% by weight or more. Although it cannot be unconditionally specified depending on the refrigerant composition, it can be said that a refrigerant containing 45% by weight or more of nonflammable hydrofluorocarbons such as R125 and R134a is preferable from the viewpoint of nonflammability.

[0006] On the other hand, since the refrigerant is used under various conditions in the refrigeration system, it is not preferable that the composition of the hydrofluorocarbon to be mixed greatly differs at various points in the refrigeration system. In the refrigeration system, the refrigerant takes both gas and liquid states. Therefore, if the boiling points of the mixed hydrofluorocarbons are significantly different, the composition of the mixed refrigerant may be significantly different at various points in the refrigeration system for the above-described reasons. There is. 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.
Care must be taken in this regard when using a. Therefore, the content of the mixed refrigerant using R125 is preferably 20 to 80% by weight, particularly preferably 40 to 70% by weight. If the content is less than 20% by weight, a large amount of a refrigerant having a significantly different boiling point, such as R134a, is required for imparting nonflammability, which is not preferable for the above-mentioned reason. On the other hand, when the content of R125 exceeds 80% by weight, the efficiency is lowered, 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) is used.
Called. ), 50:50 weight ratio of R32 to R125
(Hereinafter, referred to as R410A), R32 and R32.
And a mixture having a weight ratio of 45:55 to R.125 (hereinafter referred to as R410
Called B. On the other hand, 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 to R143a of 50: 5 are preferable.
0 (hereinafter, referred to as R507) is preferred.
Further, these mixed refrigerants are also suitable from the viewpoint that the change in refrigerant composition is small when the refrigerant is charged into the device or when the refrigerant leaks from the device.

On the other hand, R22 and R5
02, etc., are used instead of the above-mentioned R404A, R410A, R410B,
When R507 or the like is adopted, the lubricating oil is naturally excellent in compatibility with these hydrofluorocarbon mixed refrigerants and has the above-mentioned required performance, that is, the volume resistivity of 10 ¹² Ω · cm (80 ° C.). ) And those having excellent stability and lubricating performance are required. However, lubricating oils that have been used with conventional R22, R502, etc., are R404A, R410A, R410.
Since the compatibility with a mixed refrigerant of hydrofluorocarbon such as B and R507 is not good, a new lubricating oil suitable for these mixed refrigerants is required. In this case, particularly when replacing R22 or R502, it is demanded that the structure of the device be hardly changed.
It is not desirable to significantly change the structure of the current device.

Polyalkylene glycols, polyol esters and carbonates are known as lubricating oils which are compatible with these hydrofluorocarbon mixed refrigerants. Polyalkylene glycols have low volume resistivity, and have a low volume resistivity. Ester and carbonate systems are easily hydrolyzed and have a problem of stability. Accordingly, there has been a demand for a lubricating oil which is compatible with the above-mentioned hydrofluorocarbon mixed refrigerant, has high volume specific resistance, and is excellent in stability and lubricating performance.

[0010]

SUMMARY OF THE INVENTION The present invention has been developed under the above circumstances.
Use and be compatible with fluorocarbon, hydrocarbon, ether, carbon dioxide, or ammonia-based ones, preferably hydrofluorocarbon-based ones that can substitute for chlorofluorocarbons in refrigerants that are problematic for environmental pollution It is an object of the present invention to provide a refrigerant device using a lubricating oil having good volume resistivity, high stability and excellent lubrication performance, and a refrigerant compressor suitable for forming a refrigeration cycle of the refrigeration device. It is.

[0011]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and as a result, as a lubricating oil, polyvinyl ether comprising a homopolymer or a copolymer having a specific structural unit has been used. It has been found that the object can be achieved by using a compound having a predetermined viscosity containing a system compound as a main component. 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, an evaporator, and, if necessary, a drier, and further comprises a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type. Kinematic viscosity at a temperature of 40 ° C. containing a system-based, carbon dioxide-based or ammonia-based refrigerant and a polyvinyl ether-based compound as main components is 2 to 3.
An object of the present invention is to provide a refrigeration apparatus having a lubricating oil of 200 mm ² / sec.

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

[0013]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the refrigerating apparatus and the refrigerant compressor of the present invention, the refrigerant is of a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or an ammonia type, preferably a hydrofluorocarbon type. Is used. On the other hand, as the lubricating oil, those having a polyvinyl ether compound as a main component are used. As the polyvinyl ether-based compound, a compound represented by the general formula (I)

[0014]

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[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 atom. A divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-linked oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R ⁵ has 1 to 10 carbon atoms;
20 hydrocarbon groups, m represents a number having an average value of 0 to 10, R ^{1 to} R ⁵ may be the same or different for each structural unit, and when there are a plurality of R ⁴ O In
A plurality of R ⁴ O may be the same or different. A) a polyvinyl ether compound (1) comprising a polymer having a structural unit represented by the following general formula (I): (a) a structural unit represented by the general formula (I);

[0016]

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[0017] wherein, R ⁶ to R ⁹ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms and may be the same with or different from each other, also R ⁶ to R ⁹ is configured It may be the same or different for each unit. And (A) the polyvinyl ether compound (1) and (B) the polyvinyl ether compound (2). Are preferably used. The polyvinyl ether compound (1) comprises a polymer having a structural unit represented by the general formula (I),
¹ , R ² and R ³ each represent a hydrogen atom or a carbon number of 1 to 8;
And they may be the same or different. Here, the hydrocarbon group specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group,
-Butyl group, isobutyl group, sec-butyl group, ter
cycloalkyl groups such as 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, Aryl groups of phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, benzyl groups, various phenylethyl groups, and arylalkyl groups of various methylbenzyl 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, and a hydrogen atom or an aliphatic hydrocarbon group having 3 or less carbon atoms is more 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-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms is shown. Here, the divalent hydrocarbon group having 1 to 10 carbon atoms specifically means 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; various divalent aliphatic groups of decylene groups, cyclohexane; methylcyclohexane; ethylcyclohexane; dimethylcyclohexane An alicyclic group having two binding sites to an alicyclic hydrocarbon such as propylcyclohexane, various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups, various divalent groups such as naphthylene groups; Aromatic hydrocarbon group, toluene; xylene; alkyl aromatic group such as ethylbenzene and the like having an alkyl group portion and an aromatic portion each having a monovalent bonding site; xylene; polyalkyl aromatic hydrocarbon such as diethylbenzene Alkyl part of hydrogen It is an alkyl aromatic group having a binding site. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred.

Specific examples of the divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include a methoxymethylene group; a methoxyethylene group; a methoxymethylethylene group; a 1,1-bismethoxymethylethylene group; 1,2-
Bismethoxymethylethylene group; ethoxymethylethylene group; (2-methoxyethoxy) methylethylene group;
A (1-methyl-2-methoxy) methylethylene group can be preferably exemplified. In the general formula (I), m represents the number of repetitions of R ⁴ O, and the average value thereof is 0 to
It is a number in the range of 10, preferably 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, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, and tert- Butyl 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 And aryls such as 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, etc. Group, benzyl group, various phenylethyl Group shown, various methylbenzyl groups, various phenylpropyl groups, and arylalkyl groups various phenylbutyl groups. Note that R ^{1 to} R ⁵ may be the same or different for each structural unit.

This polyvinyl ether compound (1)
Has a structural unit represented by the above general formula (I), and the number of repetitions (that is, the degree of polymerization) may be appropriately selected according to a desired kinematic viscosity. Is selected so that the kinematic viscosity at ^{2 to 2} mm2 / sec. In addition, the polyvinyl ether compound preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If the molar ratio is less than 4.2, the hygroscopicity may be increased, and if it exceeds 7.0, the compatibility with the CFC-based refrigerant tends to decrease. Further, the polyvinyl ether compound (2) may be a block or random copolymer having (a) a structural unit represented by the general formula (I) and (b) a structural unit represented by the general formula (II). And R ^{6 to} R in the general formula (II)
⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different. Examples of the hydrocarbon group having 1 to 20 carbon atoms may include the same as those exemplified in the description of R ⁵ in the above general formula (I). Note that 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 structural unit represented by the general formula (I) and the structural unit represented by the general formula (II) is as follows: The kinematic viscosity may be appropriately selected depending on the desired kinematic viscosity.
It is selected 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 7, the hygroscopicity may increase, and if it exceeds 7.0, the compatibility with the chlorofluorocarbon-based refrigerant tends to decrease. Further, the polyvinyl ether compound (3)
(A) The polyvinyl ether compounds (1) and (B)
It is composed of a mixture with the above-mentioned polyvinyl ether compound (2), and the mixing ratio is not particularly limited. The polyvinyl ether compounds (1) and (2) are produced by polymerization of the corresponding vinyl ether monomers and copolymerization of the corresponding vinyl ether monomers with the corresponding hydrocarbon monomers having an olefinic double bond. Can be. The vinyl ether-based monomer that can be used here has the general formula (IX)

[0022]

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[Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and m are the same as above. ].
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;
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;
-Ethoxyethyl ether; vinyl-2-methoxy-1
-Methylethyl 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
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;
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
2-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 monomers can be produced by a known method.

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

[0025]

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

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

[0028]

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[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,
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. . R ⁴¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms or 2 to 20 carbon atoms.
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 there are a plurality of R ⁴¹ O, R ⁴¹ O may be the same or different. And the remaining terminal is represented by the general formula (V) or (VI)

[0030]

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[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,
R ⁶² , R ⁷² , R ⁸² and R ⁹² each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁶² , R ⁷² , R ⁸² and R ⁹² may be the same or different from each other . R ⁴² is several hydrocarbon group or C divalent C1-10 2-20
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 there are a plurality of R ⁴² O, of R ⁴² O may be the same or different. And one end thereof is represented by the above general formula (III) or (IV), and the other end is represented by the general formula (VII)

[0032]

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Wherein 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. ] Are preferred. Further, it has only the structural unit represented by the general formula (I), one end of which is represented by the general formula (III), and the other end is represented by the general formula (VIII)

[0034]

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[0035] (wherein, R ^14, R ²⁴ and R ³⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be different even identical to each other, 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. And they may be the same or different, and q and r each have an average value of 0 to 10
And they may be the same or different, and when there are a plurality of R ⁴⁴ O, a plurality of R ⁴⁴ O
⁴⁴ O may be the same or different;
^When there is ⁶⁴ O, a plurality of R ⁶⁴ O may be the same or different. And those having one end represented by the general formula (III) and the other end having an olefinically unsaturated bond.

[0036] Such polyvinyl ether compounds
Among them, the following are especially the main components of the lubricating oil in the present invention.
Suitable as a component. (1) One terminal is represented by the general formula (III) or (IV)
And the remaining terminal is represented by the general formula (V) or (VI)
Having a structure represented by the general formula (I)¹, R^TwoAnd R
^ThreeAre 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 groups. (2) having only the structural unit represented by the general formula (I)
Wherein one end thereof 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, R^TwoAnd R^ThreeAre both hydrogen sources
Child, m is a number from 0 to 4, R^FourIs a divalent carbon having 2 to 4 carbon atoms
Hydrogen group and R^FiveIs a hydrocarbon group having 1 to 20 carbon atoms
of. (3) One end thereof is represented by the general formula (III) or (IV)
And the remaining terminal has a structure represented by the general formula (VII).
And R in the general formula (I)¹, R^TwoAnd R^ThreeBut water together
An element atom, m is a number of 0 to 4, R^FourIs a divalent C 2-4
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)
Wherein one end thereof 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, R^TwoAnd R^ThreeAre both hydrogen sources
Child, m is a number from 0 to 4, R^FourIs a divalent carbon having 2 to 4 carbon atoms
Hydrogen group and R^FiveIs a divalent hydrocarbon group having 1 to 20 carbon atoms and
And R^FiveIs a hydrocarbon group having 1 to 20 carbon atoms.

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

The alcohols include, for example, those having 1 carbon atom such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols and various octanols. And unsaturated aliphatic alcohols having 3 to 10 carbon atoms, such as saturated aliphatic alcohols having up to 20 and allyl alcohol. When an adduct of a vinyl ether and a carboxylic acid is used, examples of the carboxylic acid include acetic acid; propionic acid; n-butyric acid; isobutyric acid;
Isovaleric acid; 2-methylbutyric acid; pivalic acid; n-caproic acid; 2,2-dimethylbutyric acid; 2-methylvaleric acid; 3-methylvaleric acid; 4-methylvaleric acid; Caprylic acid; 2-ethylcaproic acid; 2
-N-propylvaleric acid; n-nonanoic acid; 3,5,5-trimethylcaproic acid; caprylic acid; undecanoic acid and the like. The vinyl ethers may be the same as those used for the polymerization, or may be different. The adduct of the vinyl ether and the carboxylic acid is obtained by mixing the two and reacting at a temperature of about 0 to 100 ° C., separated by distillation or the like, and used for the reaction, but separated as it is. It can also be used for the reaction without any. The polymerization initiation terminal of the polymer is
When water, alcohols, or phenols are used, hydrogen bonds. When acetal is used, one of the alkoxy groups is eliminated from hydrogen or the used acetal. When an adduct of a vinyl ether and a carboxylic acid is used, an alkylcarbonyloxy group derived from the carboxylic acid moiety is eliminated from the adduct of the vinyl ether and the carboxylic acid.

On the other hand, when water, alcohols, phenols, and acetals are used, the terminating terminals are acetal, olefin, or aldehyde. In the case of an adduct of a vinyl ether and a carboxylic acid, a carboxylic acid ester of hemiacetal is obtained. The terminal of the polymer thus obtained can be converted to a desired group by a known method. Examples of the desired group include residues of saturated hydrocarbons, ethers, alcohols, ketones, nitriles, amides and the like, and preferred are residues of saturated hydrocarbons, ethers and alcohols.

The polymerization of the vinyl ether monomer represented by the general formula (IX) depends on the type of the raw material and the initiator.
It can start between 80-150 ° C., usually -8
It can be performed at a temperature in the range of 0 to 50 ° C. The polymerization reaction is completed in about 10 seconds to 10 hours after the start of the reaction. Regarding the adjustment of the molecular weight in this polymerization reaction, the amount of water, alcohols, phenols, acetals and adducts of vinyl ethers and carboxylic acids is increased with respect to the vinyl ether monomer represented by the above general formula (IX). By doing so, a polymer having a low average molecular weight can be obtained. Further, by increasing the amount of the Bronsted acids or 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 a required amount of a reaction raw material and is inert to the reaction, and is not particularly limited. For example, hydrocarbon solvents such as hexane, benzene, and toluene, and ethyl ether, 1,2- Ether solvents such as dimethoxyethane and tetrahydrofuran can be suitably used.
This polymerization reaction can be stopped by adding an alkali. After the completion of the polymerization reaction, the desired polyvinyl ether compound having the structural unit represented by the general formula (I) can be obtained by performing a usual separation / purification method as required.

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 in the above range can be produced. That is, if the ratio of the monomer having a large carbon / oxygen molar ratio is large, a polymer having a large carbon / oxygen molar ratio is obtained, and if the ratio of the monomer having a small carbon / oxygen molar ratio is large, a polymer having a small carbon / oxygen molar ratio is obtained. Is obtained. Further, as shown in the above-mentioned polymerization method of vinyl ether-based monomers, it is also possible to use water, alcohols, phenols, acetals, and adducts of vinyl ethers with carboxylic acids, which are used as initiators, in combination with monomers. It is. Carbon / monomer
If an alcohol or phenol having a high oxygen molar ratio is used as the initiator, a polymer having a higher carbon / oxygen molar ratio than the starting monomer can be obtained. By using these, a polymer having a smaller carbon / oxygen molar ratio than the starting monomer can be obtained.

Further, when a vinyl ether monomer and a hydrocarbon monomer having an olefinic double bond are copolymerized, a polymer having a carbon / oxygen molar ratio larger than that of the vinyl ether monomer can be obtained. The proportion can be adjusted by the proportion of the hydrocarbon monomer having an olefinic double bond and the number of carbon atoms thereof. The lubricating oil in the present invention contains the above-mentioned polyvinyl ether-based compound as a main component. The kinematic viscosity of the lubricating oil before mixing with the refrigerant is 2-20 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 from 150 to 2,000. In addition, even if the polymer is outside the above kinematic viscosity range, by mixing with other kinematic viscosity polymers,
It is also possible to adjust the viscosity within the above kinematic viscosity range.

As the lubricating oil in the present invention, the above-mentioned polyvinyl ether compounds may be used alone or in combination of two or more. Further, it can be used by mixing with other lubricating oils such as esters, polyalkylene glycol, mineral oil and the like. When the polyvinyl ether-based compound is mixed with another lubricating oil, the polyvinyl ether-based compound is preferably contained at least 50% by weight in the mixed lubricating oil. The lubricating oil of the present invention includes various additives used in conventional lubricating oils, such as load-bearing additives, chlorine scavengers, antioxidants,
Add metal deactivator, defoamer, detergent / dispersant, viscosity index improver, oil agent, anti-wear additive, extreme pressure agent, rust inhibitor, corrosion inhibitor, pour point depressant, etc. as required. can do. Examples of the load-bearing additive include monosulfides,
Organic sulfur compounds such as polysulfides, sulfoxides, sulfones, thiosulfinates, sulfurized fats and oils, thiocarbonates, thiophenes, thiazoles, methanesulfonates, phosphoric acid monoesters, phosphoric acid Phosphate esters such as diesters and phosphate triesters (tricresyl phosphate etc.), and phosphite esters such as phosphite monoesters, phosphite diesters and phosphite triesters Thiophosphates such as thiophosphate triesters, esters such as higher fatty acids, hydroxyaryl fatty acids, polyhydric alcohol esters, acrylates, chlorinated hydrocarbons, chlorinated Organochlorine compounds such as carboxylic acid derivatives, fluorinated aliphatic carboxylic acids, Organic fluorinated compounds such as fluorinated ethylene resins, fluorinated alkyl polysiloxanes, fluorinated graphite, alcoholic compounds such as higher alcohols, naphthenates (such as lead naphthenate), fatty acid salts (such as lead fatty acid) ), Thiophosphates (such as zinc dialkyldithiophosphate), thiocarbamates, organic molybdenum compounds, organic tin compounds, organic germanium compounds, and boric acid esters.

Examples of the chlorine scavenger include glycidyl ether group-containing compounds, epoxidized fatty acid monoesters, epoxidized oils and fats, and epoxycycloalkyl group-containing compounds. As antioxidants, phenols (2,6-
Di-tert-butyl-p-cresol, etc.) and aromatic amines (such as α-naphthylamine). Examples of the metal deactivator include a benzotriazole derivative. Examples of the antifoaming agent include silicone oil (such as dimethylpolysiloxane) and polymethacrylates. Detergents include sulfonates, phenates, succinimides and the like. Examples of the viscosity index improver include polymethacrylate, polyisobutylene, an ethylene-propylene copolymer, and a styrene-diene hydrogenated copolymer.

In the refrigeration apparatus and the refrigerant compressor of the present invention, a hydrofluorocarbon-based, fluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based or ammonia-based refrigerant is used as a refrigerant. A system refrigerant is preferred. As the hydrofluorocarbon-based refrigerant, for example, 1,1,1,2-tetrafluoroethane (R134
a), difluoromethane (R32), pentafluoroethane (R125) and 1,1,1-trifluoroethane (R143a) are preferred, and these may be used alone or in combination of two or more. . These hydrofluorocarbons have no risk of destroying the ozone layer and are preferred as refrigerants for compression refrigerators.
Examples of the mixed refrigerant include R32, R125, and R1.
34a and a mixture having a weight ratio of 23:25:52 (hereinafter referred to as R)
407C. ), Weight ratio of R32 to R125 5
0:50 mixture (hereinafter referred to as R410A), R
32 and a mixture of R125 in a weight ratio of 45:55 (hereinafter, referred to as a mixture)
Called R410B. ), R125, R143a and R1
34a and a mixture having 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 configuration in which 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 are essential. And a lubricating oil having a kinematic viscosity of ² to 200 mm ² / sec at a temperature of 40 ° C. containing the above-mentioned polyvinyl ether compound as a main component as a lubricating oil (refrigerating machine oil). Hydrofluorocarbon, fluorocarbon,
A hydrocarbon-based, ether-based, carbon dioxide-based or ammonia-based refrigerant, preferably a hydrofluorocarbon-based refrigerant is used. Here, the pore size is 3.
It is preferable to fill a desiccant consisting of 5% or less zeolite. Examples of the zeolite include natural zeolites and synthetic zeolites.

In the present invention, when such a desiccant is used, moisture can be efficiently removed without absorbing the refrigerant in the refrigeration cycle, and powdering due to deterioration of the desiccant itself is suppressed. This eliminates the risk of blockage of the pipe caused by the gasification and abnormal wear due to intrusion into the sliding portion of the compressor, and allows the refrigeration apparatus to operate stably for a long period of time. Further, the refrigerant compressor of the present invention constitutes a refrigeration cycle of the refrigeration apparatus, wherein the compressor and the electric motor are enclosed in a single cover, and the internal high-pressure or internal low-pressure hermetic compression is used. Machine.

In any of the above types, an electric motor
The stator winding of which the core wire (magnet wire, etc.) is coated with enamel having a glass transition temperature of 130 ° C. or higher,
Alternatively, it is preferable that the enamel wire is fixed with a varnish having a glass transition temperature of 50 ° C. or higher. The enamel coating is preferably a single layer or a composite layer of polyesterimide, polyimide, polyamide or polyamideimide. In particular, enamel coatings with a lower glass transition temperature as the lower layer and a higher glass transition temperature as the upper layer have excellent water resistance, softening resistance and swelling resistance, as well as high mechanical strength, rigidity and insulation. High and practically useful. Further, in the refrigerant compressor of the present invention, the insulating film which is an 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, the crystalline plastic film preferably has an oligomer content of 5% by weight or less. Suitable examples of such a crystalline plastic having a glass transition temperature of 60 ° C. or higher include polyether nitrile, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, polyethylene naphthalate, polyamide imide, and polyimide. be able to. The insulating film of the motor may be a single layer of the crystalline plastic film described above, 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 rubber material for vibration isolation can be provided inside the compressor. In this case, the rubber material for vibration isolation is acrylonitrile-butadiene rubber (NBR), ethylene-propylene. -Diene rubber (E
PDM, EPM), hydrogenated acrylonitrile-butadiene rubber (HNBR), silicone rubber and fluoro rubber (FKM) are suitably used, and those having a rubber swelling ratio of 10% by weight or less are particularly preferred. Further, in the refrigerant compressor of the present invention, various organic materials (for example, a lead wire covering material, a binding yarn, an enamel wire, an insulating film, etc.) can be disposed inside the compressor. As material, its tensile strength reduction rate is 20%
The following are preferably used: Further, in the refrigerant compressor of the present invention, the swelling ratio of the gasket in the compressor is 2
Those having 0% or less are preferable.

Next, specific examples of the refrigerant compressor of the present invention include a closed scroll compressor, a closed swing compressor, a closed reciprocating compressor, a closed rotary compressor 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 closed type twin rotary type compressor which is a kind of a refrigerant compressor of the present invention, and a motor unit is provided at an upper stage in a case 1 which is a closed container also serving as an oil reservoir. (Electric motor part), and a compressor part are stored in the lower stage. The motor unit includes a stator (stator) 2 and a motor rotor (rotor) 3, and a rotating shaft 4 is fitted to the motor rotor 3. The core of the winding 5 of the stator 2 is usually covered with an enameled wire, and an electric insulating film is inserted between the core and the winding of the stator 2. On the other hand, the compressor section includes two compression chambers, an upper compression chamber 6 and a lower compression chamber 7. In this compressor, compressed refrigerant gas is alternately discharged from the upper and lower compression chambers 6, 7 with a phase difference of 180 degrees. In the compression chamber, a cylindrical rotating piston is driven by a crank fitted therein, and rotates eccentrically in contact with a point on the cylinder wall. In addition, the blade is pressed by a spring, and reciprocates so that the tip always contacts the rotating piston. Here, when the rotating piston rotates eccentrically, 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, a valve provided on the bearing flange surface opens, and the refrigerant gas is discharged to the outside.

[0051]

EXAMPLES Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

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. Table 1 shows the obtained results. In addition, each measurement condition is as follows. Kinematic viscosity was measured using a glass capillary viscometer according to JIS K2283-1983. Compatibility (a) R134a 1,1,1,2-tetrafluoroethane (R134a)
On the other hand, a predetermined amount of a sample was added to a pressure-resistant glass ampoule so as to be 5% by weight and 10% by weight, and this was connected to a vacuum pipe and an R134a gas pipe. After the ampoule was degassed in vacuum at room temperature, it was cooled with liquid nitrogen to collect a predetermined amount of R134a. Next, the ampoule is sealed, and the compatibility on the low temperature side is gradually cooled from room temperature to −60 ° C. in a constant temperature bath.
The temperature at which phase separation started by gradually heating to 80 ° C. was measured. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. (b) R32 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 based on difluoromethane (R32), and this was connected to a vacuum pipe and an R32 gas pipe. After the ampoule was degassed under vacuum at room temperature, it was cooled with liquid nitrogen to collect a predetermined amount of R32. Next, the ampoule is sealed, and the compatibility on the low temperature side is gradually cooled from room temperature in a thermostat, 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 better.

The sample was dried under reduced pressure (0.3 to 0.8 mmHg) at 100 ° C. for 1 hour, and then sealed in a liquid cell for measuring volume resistivity in a constant temperature bath at 80 ° C. After being kept in a constant temperature bath at 80 ° C. for 40 minutes, the measurement was performed at an applied voltage of 250 V using an R8340 super insulation meter manufactured by Advantest Corporation. Hydrolysis stability 75 g of a sample, 25 g of water and copper (13 mm x 50 mm) were placed in a pressure-resistant bottle having a capacity of 250 ml, and the atmosphere in the vessel was set to a nitrogen atmosphere. The temperature was kept at 102 ° C. for 192 hours in a rotary thermostat. Thereafter, the appearance of the sample oil, the total acid value, and the state of the copper pieces were observed. Organic material compatibility test In a 250 ml autoclave, sample oil 50 g, R4
20 g of 10A and each organic material were sealed and kept at 120 ° C. for 72 hours. As the organic material, an enameled wire (material: polyamide imide) and an insulating film (material: polyethylene terephthalate) were used. For the enameled wire, the appearance after the test was visually observed. Was measured. Rubber swelling test In a 250 ml autoclave, 50 g of sample oil, R4
20 g of 10A and a rubber material (O-ring: HNBR) were sealed and kept at 120 ° C. for 72 hours. After the test, 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 a polyethyl vinyl ether polyisopropyl vinyl ether copolymer (ethyl vinyl: Isopropyl vinyl = 5: 5)
Except that (Example 4) was used, the 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 performed. went. Table 1 shows the obtained results.

Comparative Example 1 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 described above, and an organic material compatibility test and a rubber swelling test were performed. Table 1 shows the obtained results.

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. Table 1 shows the obtained results.

Comparative Example 3 Using a hindered ester, the 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 rubber swelling test were performed. Was done. Table 1 shows the obtained results.

[0058]

[Table 1]

[0059]

[Table 2]

[0060]

[Table 3]

Example 5 Polyisobutyl vinyl ether was measured for kinematic viscosity, compatibility with Freon 134a, volume resistivity, hydrolysis stability, and hygroscopicity, and an organic material compatibility test and a rubber swelling test were performed. Table 2 shows the obtained results. In addition, each measurement condition is as follows. (1) Kinematic viscosity: Same as in Example 1. (2) Compatibility test With respect to R134a, a predetermined amount of a sample was added to a pressure-resistant glass ampule, and this was connected to a vacuum pipe and a R134a gas pipe. After the ampoule was degassed in vacuum at room temperature, it was cooled with liquid nitrogen to collect a predetermined amount of R134a. Next, the ampoule is sealed, and the compatibility on the low temperature side is gradually cooled from room temperature to −50 ° C. in a thermostat, while the compatibility on the high temperature side is gradually heated from room temperature to + 90 ° C. Thus, the temperature at which phase separation started was measured. The lower the phase separation temperature on the low temperature side, the higher the phase separation temperature on the high temperature side. For R32 and R125, R134a
The measurement was performed in the same manner as in the case of. 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: Same as in the first embodiment. (4) Hydrolysis stability: Same as in Example 1. The total acid value of the sample oil before the test was 0.01 mgKOH / g.
Met. (5) Hygroscopicity test 20 g of sample oil was placed in a 50 cc sample bottle made of glass, and placed in a desiccator in which humidity and temperature were controlled to be constant.
The weight change was measured. The increased weight corresponds to the moisture absorbed. The temperature was controlled at 30 ° C. by placing the desiccator in a thermostat. Humidity was controlled at 81% by adding ammonium sulfate saturated water and ammonium sulfate powder to the bottom of the desiccator. (6) Organic material compatibility test: Same as in Example 1. (7) Rubber swelling test: Same as in Example 1.

Examples 6 to 9 In Example 5, instead of polyisobutyl vinyl ether, a 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, a higher molecular weight than in Example 7))
Except that (Example 9) was used, the kinematic viscosity, compatibility with R134a, volume resistivity, hydrolysis stability, and hygroscopicity were measured in the same manner as in Example 5, and the organic material compatible test rubber and A swelling test was performed. Table 2 shows the obtained results.

[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 refrigerating apparatus of the present invention has a high-pressure vessel type or low-pressure vessel type refrigerant compressor,
By using a lubricating oil (refrigeration 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 also has excellent lubricating performance. In the above, use of a hydrofluorocarbon-based refrigerant is preferable as the refrigerant. The refrigeration apparatus of the present invention has excellent performance and efficiency, and can be operated stably for a long period of time.

[Brief description of the drawings]

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

[Explanation of symbols]

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

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Toyowa Handa 1280 Kamiizumi, Sodegaura City, Chiba Prefecture (72) Inventor Masato Kaneko 24-4 Anesaki Beach, Ichihara City, Chiba Prefecture

Claims (26)

[Claims] 1. A refrigeration cycle comprising at least a compressor, a condenser, an expander groove, and an evaporator, and a hydrofluorocarbon-based, fluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based, or ammonia-based refrigerant. Kinematic viscosity at a temperature of 40 ° C. containing a polyvinyl ether compound as a main component is 2 to
A refrigeration apparatus having a lubricating oil of 200 mm ² / sec. 2. A polyvinyl ether compound represented by the general formula (I): [Wherein, 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 has 1 to 10 carbon atoms. A divalent hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms, and m is a number having an average value of 0 to 10. And 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 is plural, plural R ⁴ O
May be the same or different. The refrigeration apparatus according to claim 1, wherein the refrigeration apparatus comprises a polymer having a structural unit represented by the following formula: 3. The method according to claim 1, wherein the polyvinyl ether compound is (a)
A structural unit represented by the general formula (I);
I) [Wherein, R ^{6 to} R ⁹ each represent a hydrogen atom or a carbon atom 1
To 20 hydrocarbon groups, which may be the same or different, and R ^{6 to} R ⁹ may be the same or different for each structural unit. The refrigeration apparatus according to claim 1, wherein the refrigeration apparatus comprises a block or a random copolymer having the structural unit represented by the formula: 4. The method according to claim 1, wherein the polyvinyl ether compound is (A)
A polymer having a structural unit represented by the general formula (I), and (B) (a) a structural unit represented by the general formula (I) and (b)
The refrigeration apparatus according to claim 1, wherein the refrigeration apparatus is a mixture comprising a block or a random copolymer having the structural unit represented by the general formula (II). 5. The refrigeration apparatus according to claim 2, wherein the polyvinyl ether compound has a carbon / oxygen molar ratio of 4.2 to 7.0. 6. A polyvinyl ether compound having one terminal at one end represented by the general formula (III) or (IV): Wherein R ¹¹ , R ²¹ and R ³¹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ¹¹ , R ²¹ and R ³¹
Each may be the same or different, and R ⁶¹ , R ⁷¹ ,
R ⁸¹ and R ⁹¹ each represent a hydrogen atom or a carbon atom of 1 to 20;
Wherein 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 divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, 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 R
If ^{the 41} O is plural, plural R ⁴¹ O may be the same or different. And the remaining terminal is represented by the general formula (V) or (VI): (Wherein, 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
Each of which may be the same or different, R ⁶² , R ⁷² ,
R ⁸² and R ⁹² each represent 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
0 divalent hydrocarbon group or divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, 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 R
⁴² if O is plural, plural R ⁴² O may be the same or different. 5. The refrigerating apparatus according to claim 2, wherein the refrigerating apparatus has a structure represented by the following formula: 7. The polyvinyl ether compound has a structure in which one terminal is represented by the general formula (III) and the other terminal is represented by the general formula (V).
A refrigeration device as described. 8. The polyvinyl ether-based compound has one terminal represented by the general formula (III) or (IV) and the other terminal represented by the general formula (VII). [Wherein, 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. 5. The refrigerating apparatus according to claim 2, wherein the refrigerating apparatus has a structure represented by the following formula: 9. The polyvinyl ether compound has one end represented by the general formula (III) and the other end represented by the general formula (VIII). (Wherein, 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 represents 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. ,
They may be identical or different,
q and r each represent a number whose average value is from 0 to 10,
They may be identical 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. 3. The refrigeration apparatus according to claim 2, wherein the refrigeration apparatus has a structure represented by: 10. The refrigerating apparatus according to claim 2, wherein the polyvinyl ether compound has one terminal represented by the general formula (III) and the other terminal having an olefinically unsaturated bond. 11. In the formula (I), R ¹ , R ² and R ³ are all hydrogen atoms, m is 0 to 4, and R ⁴ is C 2 to C 4.
The refrigerating device according to any one of claims 6-10 divalent hydrocarbon group and R ⁵ is a hydrocarbon group having 1 to 20 carbon atoms. 12. The refrigerant is a hydrofluorocarbon-based refrigerant and comprises 1,1,1,2-tetrafluoroethane, difluoromethane, pentafluoroethane,
The refrigeration apparatus according to claim 1, wherein the refrigeration apparatus is at least one selected from 1,1-trifluoroethane. 13. The refrigeration apparatus according to claim 1, wherein the refrigerant cycle further has a dryer. 14. The desiccant is filled with a desiccant consisting of zeolite having a pore diameter of 3.5 mm or less.
3. The refrigeration apparatus according to 3. 15. An internal high-pressure hermetic compressor in which a compressor and an electric motor are covered by a single cover, wherein the compressor is a hydrofluorocarbon type, a fluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or an ammonia type. Kinematic viscosity at a temperature of 40 ° C. containing a polyether-based compound and a polyvinyl ether-based compound as main components is ² to 200 mm ² /
Refrigerant compressor having a second lubricating oil. 16. An internal low-pressure hermetic compressor in which a compressor and an electric motor are covered by a single cover, wherein the compressor is a hydrofluorocarbon type, fluorocarbon type, hydrocarbon type, ether type, carbon dioxide or ammonia type. A refrigerant compressor comprising: a refrigerant; and a lubricating oil containing a polyvinyl ether compound as a main component and having a kinematic viscosity of ² to 200 mm ² / sec at a temperature of 40 ° C. 17. The refrigerant compressor according to claim 15, wherein the winding of the stator of the electric motor has a core wire covered with enamel having a glass transition temperature of 130 ° C. or higher. 18. The refrigerant compressor according to claim 15, wherein an enameled wire of a stator of the electric motor is fixed with a varnish having a glass transition temperature of 50 ° C. or higher. 19. The refrigerant compressor according to claim 17, wherein the enamel coating comprises at least one insulating layer selected from the group consisting of polyesterimide, polyimide, polyamide, and polyamideimide. 20. The refrigerant compressor 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. 21. The refrigerant compressor according to claim 20, wherein the insulating film of the electric motor is a crystalline plastic film having a glass transition temperature of 60 ° C. or more, and the amount of oligomer in the film is 5% by weight or less. 22. 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. 22. The refrigerant compressor according to claim 20, wherein 23. The refrigerant compressor according to claim 15, wherein a rubber material for vibration isolation is provided inside the compressor. 24. The vibration-damping rubber material is acrylonitrile-
At least one rubber selected from the group consisting of butadiene rubber, ethylene-propylene-diene rubber, hydrogenated acrylonitrile-butadiene rubber, silicone rubber and fluororubber, having a rubber swelling ratio of 10% by weight or less. A refrigerant compressor according to claim 23. 25. The refrigerant compressor according to claim 15, wherein an organic material disposed inside the compressor has a tensile strength reduction rate of 20% or less. 26. The swelling ratio of the gasket in the compressor is 20.
%. The refrigerant compressor according to claim 15 or 16, wherein