JPH10237477A - Refrigerator oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a refrigerator oil composition which improves lubrication between the aluminum and steel materials of a refrigerator using a hydrofluorocarbon refrigerant as a substitute for a chlorofluorocarbon refrigerant to inhibit their abrasion and seldom stops the capillary tube by mixing a base oil comprising a synthetic oil with a polyalkylene glycol derivative having a specified molecular weight. SOLUTION: Although the synthetic oil used as the base oil is not particularly limited, it is desirably one having a kinematic viscosity in the range of 10-100mm<2> /s at 40 deg.C. The polyalkylene glycol derivative used is represented by the formula (wherein R<1> and R<4> are each a 1-30C hydrocarbon group, an acyl or hydrogen; R<2> is a 2-4C alkylene; R<3> is a 2 or 30C alkylene or substituted alkylene; m and n are numbers to give a number-average molecular weight of 200-3,000 provided that n may be 0; and at least one of R<1> , R<3> and R<4> is a 6C or higher hydrocarbon group). The amount of addition is 0.1-30wt.%, desirably 0.5-10wt.% based on the entire weight of the composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a refrigerating machine oil composition, and more particularly, to a refrigerant containing hydrofluorocarbon, fluorocarbon, hydrocarbon, or the like.
When using ether-based, carbon dioxide-based or ammonia-based ones, preferably hydrofluorocarbon-based ones that can substitute for chlorofluorocarbons as refrigerants that are a problem due to environmental pollution, they have excellent lubricating properties, especially aluminum. The present invention relates to a refrigerating machine oil composition that can improve lubricity between steel materials, suppress abrasion, and hardly block capillary tubes.

[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. Conventionally, as a refrigerant for a compression refrigerator, particularly an air conditioner, chlorodifluoromethane (hereinafter, referred to as R22) or a mixture of chlorodifluoromethane and chloropentafluoroethane in a weight ratio of 48.8: 51.2 (hereinafter, referred to as R22). R502), and various mineral oils and synthetic oils satisfying the above-mentioned required characteristics have been used as lubricating oils.
However, since R22 and R502 may cause environmental pollution such as destruction of the ozone layer existing in the stratosphere, the regulations thereof 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.

[0003] As a refrigerant for a compression type refrigerator, it is desirable to be able to use it without changing the current refrigerating apparatus. 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.

[0004] 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, R143a, R125 and R13
The boiling points of 4a are −51.7 ° C., −47.4 ° C., −
48.5 ° C. and −26.3 ° C., and when R134a is used in the hydrofluorocarbon mixed refrigerant system,
Attention should be paid to this point. Therefore, in the mixed refrigerant using R125, the content is 20 to 80% by weight,
In particular, it is preferably from 40 to 70% by weight. If the content is less than 20% by weight, further R
A large amount of refrigerant having a significantly different boiling point, such as 134a, is required, which is not preferable for the above reasons. 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. ), A mixture in a weight ratio of 25:15:60, R3
2 and R125 in a weight ratio of 50:50 (hereinafter referred to as R)
Called 410A. ), Weight ratio of R32 to R125 4
A 5:55 mixture (hereinafter referred to as R410B) is preferred, while an alternative to the R502 refrigerant is R
Weight ratio of 125: R143a: R134a: 44: 5
A mixture of 2: 4 (hereinafter, referred to as R404A) and R1
A mixture of 25 and R143a in a weight ratio of 50:50 (hereinafter, referred to as R507) is preferable.

[0007] The hydrofluorocarbon refrigerant is
Refrigeration oils differing in properties from conventional refrigerants are used in combination with, for example, polyalkylene glycols, polyesters, polyol esters, polycarbonates, polyvinyl ethers and the like having a specific structure as a base oil, and an antioxidant, It is known that those containing various additives such as an extreme pressure agent, an antifoaming agent and a hydrolysis inhibitor are useful.

However, these refrigerating machine oils are inferior in lubricating performance under the above-described refrigerant atmosphere, and in particular, increase the wear between the aluminum material and the steel material of refrigerators such as car air conditioners, electric refrigerators, room air conditioners, etc. It is a big problem. The frictional part between this aluminum material and steel material is reciprocating type compressor (especially swash plate type)
In rotary type compressors such as piston and piston shoes, swash plate and shoe parts, they are used in the vane and housing parts, and in scroll type compressors, they are used in the Oldham ring and the orbiting scroll receiving part. Element.

[0009] The refrigerator has an expansion valve called a capillary tube in the refrigeration cycle. Since the capillary tube is a thin tube having a diameter of about 0.7 mm, it is easily closed. The clogging phenomenon of the capillary tube is the biggest factor that determines the life of the refrigeration cycle. Therefore, when a hydrofluorocarbon-based refrigerant that can substitute for the chlorofluorocarbon of the refrigerant is used, it has excellent lubrication performance, and in particular, improves the lubricity with the aluminum steel material, can suppress abrasion, and has a capillary. There has been a demand for a refrigerating machine oil that does not easily block the pipe.

[0010]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above, and has a problem in that the refrigerant is a hydrofluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based or ammonia-based refrigerant, and is preferably environmentally polluted. When using a hydrofluorocarbon-based material that can be a substitute for chlorofluorocarbon for the refrigerant, it has excellent lubricating performance, improving lubricity especially with aluminum steel materials, and suppressing wear, It is another object of the present invention to provide a refrigerating machine oil composition in which a capillary tube is hardly clogged.

[0011]

Means for Solving the Problems As a result of intensive studies, the present inventors have achieved the above object of the present invention effectively by blending a specific polyalkylene glycol derivative with a base oil composed of synthetic oil. It has been found that the present invention can be performed and the present invention has been completed. That is, the present invention provides a refrigerating machine oil composition obtained by blending a polyalkylene glycol derivative represented by the following general formula (I) having a number average molecular weight of 200 to 3,000 with a base oil composed of a synthetic oil. Things.

R ^1- (OR ² ) _m- (OR ³ ) _n -OR ⁴ (I) (R ¹ and R ⁴ each represent a hydrocarbon group or an acyl group having 1 to 30 carbon atoms, or hydrogen And R ² has ² carbon atoms
To 4 alkylene groups, R ³ represents an alkylene group having 2 to 30 carbon atoms or a substituted alkylene group, m and n each represent a number satisfying the above molecular weight, and n may be 0 in some cases. However, at least one of R ¹ , R ³ and R ⁴ has 6 carbon atoms.
It has the above hydrocarbon groups. )

[0013]

Embodiments of the present invention will be described below. First, in the refrigerator oil composition of the present invention, a synthetic oil is used as a base oil. About this synthetic oil,
There is no particular limitation as long as it is generally used as a base oil for refrigerating machine oil.
500 mm ² / s, especially 5 to 200 mm ² / s, those especially in the range of 10 to 100 mm ² / s are preferred. The pour point, which is an index of the low-temperature fluidity of the base oil, is not particularly limited, but is preferably −10 ° C. or less.

There are various types of such synthetic oils, and they may be appropriately selected according to the use and the like. Examples thereof include oxygen-containing organic compounds and hydrocarbon-based synthetic oils. Among synthetic oils, oxygen-containing organic compounds include ether groups in the molecule,
Synthetic oils containing ketone groups, ester groups, carbonate groups, hydroxyl groups and the like, and synthetic oils containing heteroatoms (S, P, F, Cl, Si, N, etc.) in addition to these groups. Specifically, polyvinyl ether, polyhydric alcohol ester, polyester, polyol ester, carbonate derivative, polyether ketone and fluorinated oil, polyalkylene glycol and the like are used.

The oxygen-containing organic compound will be described in detail at the end. Examples of the hydrocarbon synthetic oil include olefin polymers such as poly-α-olefin, alkylbenzene, and alkylnaphthalene. In the refrigerating machine oil composition of the present invention, the above-mentioned synthetic oil may be used alone or in combination of two or more as the base oil. The oxygen-containing organic compound has good compatibility with the refrigerant,
Also, it has excellent lubrication performance and is suitable. Particularly, polyvinyl ether and polyhydric alcohol ester are preferable.

If necessary, a mixture of mineral oils may be used. Examples of the mineral oils include paraffinic mineral oils, naphthenic mineral oils, and intermediate mineral oils. next,
The polyalkylene glycol derivative blended in the base oil composed of a synthetic oil is represented by the general formula (I). In the general formula (I), the hydrocarbon groups having 1 to 30 carbon atoms of R ¹ and R ⁴ are as follows. (I) represents a saturated or unsaturated, linear or branched aliphatic hydrocarbon group, and is an alkyl group derived from an aliphatic monohydric alcohol, specifically, a methyl group, an ethyl group, an n- Propyl group, isopropyl group, various butyl groups,
Various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various undecyl groups, various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyls (Ii) substituted or unsubstituted aromatic hydrocarbon groups, preferably phenyl and alkylphenyl groups, specifically, methylphenyl, ethylphenyl, propylphenyl, etc. groups, various octadecyl groups, various nonadecyl groups, etc. Butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonylphenyl, decylphenyl, dodecylphenyl, pentadecylphenyl, hexadecylphenyl, dinonylphenyl and the like.

The acyl group represented by R ¹ and R ⁴ is
Carboxylic acids, especially those derived from saturated or unsaturated monocarboxylic acids, are preferred. Specific examples include acetic acid, propionic acid, butyric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like. Can be mentioned. In the general formula (I), R ²
Is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group.

In the general formula (I), R ³ is an alkylene group or a substituted alkylene group having 2 to 30 carbon atoms, and examples of the substituent include an alkyl group, a phenyl group and an alkylphenyl group. OR ² and O
R ³ may be a random form or a block form, but is preferably a block form in terms of molecular weight.

Further, at least one of R ¹ , R ³ and R ⁴ needs to have a hydrocarbon group having 6 or more carbon atoms. As the hydrocarbon group, a phenyl group or an alkylphenyl group is preferable. Specific examples of the polyalkylene glycol derivative of the general formula (I) include polyethylene glycol di-sec-butylphenyl methyl ether; polypropylene glycol di-sec-butylphenyl methyl ether; polyethylene glycol polypropylene glycol di-sec-butyl. Phenyl methyl ether; polyethylene glycol nonyl
Methyl ether; polypropylene glycol nonyl methyl ether; polyethylene glycol polypropylene glycol nonyl methyl ether; polyethylene glycol nonyl phenyl methyl ether; polypropylene glycol nonyl phenyl methyl ether; polyethylene glycol polypropylene glycol nonyl phenyl methyl ether; polyethylene glycol polynonylene Glycol dimethyl ether; and polypropylene glycol polynonylene glycol dimethyl ether.

In the present invention, the number average molecular weight of the alkylene glycol derivative represented by the general formula (I) is 20
It must be limited to 0-3,000. If it is less than 200, the effect of improving lubricity and the effect of preventing capillary clogging are small, and if it exceeds 3,000, the compatibility with the refrigerant (two-layer separation temperature) is undesirably reduced. Moreover, kinematic viscosity at 40 ° C. of the alkylene glycol derivative is preferably in the range of 5 to 200 mm ² / s, more preferably from 10 to 100 mm ² / s.

In the refrigerating machine oil composition of the present invention, the above-mentioned polyalkylene glycol derivatives may be used alone or in combination of two or more. Further, the amount is preferably in the range of 0.1 to 30% by weight based on the total amount of the composition. When the amount is less than 0.1% by weight, the object of the present invention is not sufficiently exhibited. When the amount exceeds 30% by weight, the effect is not improved for the amount, and the solubility in the base oil decreases. May be. A more preferred amount is in the range of 0.1 to 15% by weight, particularly 0.5 to 15% by weight.
A range of 10% by weight is preferred.

The refrigerating machine oil composition of the present invention may contain, if necessary, various known additives such as extreme pressure agents such as phosphate esters and phosphite esters; phenolic and amine antioxidants; and phenyl. Stabilizers such as epoxy compounds such as glycidyl ether, cyclohexene oxide, and epoxidized soybean oil; copper deactivators such as benzotriazole and benzotriazole derivatives; and defoamers such as silicone oil and fluorinated silicone oil. be able to.

As the refrigerant used in the refrigerator to which the refrigerator oil composition of the present invention is applied, a hydrofluorocarbon-based, fluorocarbon-based, hydrocarbon-based, ether-based, carbon dioxide-based or ammonia-based refrigerant is used. Among them, a hydrofluorocarbon-based refrigerant is preferable. As the hydrofluorocarbon-based refrigerant, for example, 1,1,1,2-tetrafluoroethane (R
134a), 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 and R125.
And a mixture of R134a in a weight ratio of 23:25:52 (hereinafter referred to as R407C), and a weight ratio of 25:15:60.
, A mixture of R32 and R125 in a weight ratio of 50:50 (hereinafter referred to as R410A), and R32 and R12.
5 (hereinafter, referred to as R410B), a mixture of R125, R143a, and R134a in a weight ratio of 44: 52: 4 (hereinafter, referred to as R404A), and a weight of R125 and R143a. And a mixture having a ratio of 50:50 (hereinafter, referred to as R507). Lastly, among the aforementioned base oils, an oxygen-containing organic compound-based synthetic oil will be described in detail. As the polyvinyl ether, for example, a compound represented by the general formula (II)

[0024]

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(Wherein, R ^{5 to} R ⁷ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁸ represents a C 1 to C 10 carbon atom). A divalent hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, R ⁹ represents a hydrocarbon group having 1 to 20 carbon atoms, and a represents a number having an average value of 0 to 10 , R ⁵ ~
R ⁹ may be the same as or different from each other in each structural unit, also in the case where R ⁸ O is plural, plural R ⁸ O may be the same or different. And a polyvinyl ether-based compound (1) having a structural unit represented by formula (1).
Further, the structural unit represented by the general formula (II) and the structural unit represented by the general formula (III)

[0026]

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(Wherein, R ^{10 to} R ¹³ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R ^{10 to} R ¹³ have the same structure A polyvinyl ether compound (2) composed of a block or a random copolymer having a structural unit represented by formula (1) may be the same or different for each unit. Further, a polyvinyl ether compound (3) comprising a mixture of the above polyvinyl ether compound (1) and the polyvinyl ether compound (2) can also be used.

R ^{5 to} R ⁷ in the general formula (II) each represent a hydrogen atom or a hydrocarbon group having 1 to 8, preferably 1 to 4 carbon atoms. Here, the hydrocarbon group is specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups,
Cycloalkyl groups such as various heptyl groups, various octyl alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, phenyl groups,
Examples include various methylphenyl groups, various ethylphenyl groups, aryl groups of various dimethylphenyl groups, benzyl groups, various phenylethyl groups, and arylalkyl groups of various methylbenzyl groups. Note that these R ^{5 to} R ⁷
Is particularly preferably a hydrogen atom.

On the other hand, R ⁸ in the general formula (II) has 1 carbon atom.
A divalent hydrocarbon group having 10 to 10, preferably 2 to 10 or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, wherein a divalent hydrocarbon group having 1 to 10 carbon atoms Specifically, methylene group; ethylene group; phenylethylene group; 1,2-propylene group; 2-phenyl-1,2
-Propylene group; 1,3-propylene group; various butylene groups; various pentylene groups; various hexylene groups; various heptylene groups; various octylene groups; various nonylene groups; divalent aliphatic groups of various decylene groups; cyclohexane; methylcyclohexane Alicyclic groups having two binding sites to an alicyclic hydrocarbon such as ethylcyclohexane; dimethylcyclohexane; propylcyclohexane; various phenylene groups; various methylphenylene groups; various ethylphenylene groups; various dimethylphenylene groups; various naphthylene Aromatic hydrocarbon group such as a group, toluene; xylene; an alkyl aromatic group having a monovalent bonding site in each of an alkyl group portion and an aromatic portion of an alkyl aromatic hydrocarbon such as ethylbenzene, xylene; diethylbenzene, etc. Polyalkyl aromatic carbonization An alkyl aromatic group having a bonding site in the alkyl group moiety containing can be mentioned.
Among these, an aliphatic group having 2 to 4 carbon atoms is particularly preferred.

Specific examples of the divalent ether-linked 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 (II), a represents the number of repetitions of R ⁸ O, and the average value thereof is 0 to 1
It is a number in the range of 0, preferably 0-5. When the R ⁸ O is plural, plural R ⁸ O may be the same or different.

Further, R ⁹ in the general formula (II) represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, specifically, a methyl group, an ethyl group, n-propyl group, isopropyl group, various butyl groups,
Various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl group alkyl groups, cyclopentyl groups, cyclohexyl groups, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethyl groups Aryl groups such as cycloalkyl groups such as cyclohexyl 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 benzyl groups Groups, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, arylalkyl groups of various phenylbutyl groups, and the like.

This polyvinyl ether compound (1)
Has a structural unit represented by the general formula (II), and the number of repetitions (degree of polymerization) may be appropriately selected according to a desired kinematic viscosity. May be selected to be ² to 500 mm ² / s. 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 increase, and if it exceeds 7.0, the compatibility with the refrigerant may decrease.

Further, a polyvinyl ether compound (2)
Is composed of a block or random copolymer having a structural unit represented by the general formula (II) and a structural unit represented by the general formula (III), and in the general formula (III) , R ^{10 to} R ¹³ each represent a hydrogen atom or a carbon atom 1
Represent up to 20 hydrocarbon groups, which may be the same or different. Here, examples of the hydrocarbon group having 1 to 20 carbon atoms include the same as those exemplified in the description of R ⁹ in the general formula (II).
R ^{10 to} R ¹³ may be the same or different for each structural unit.

The degree of polymerization of the polyvinyl ether compound (2) comprising a block or a random copolymer having the structural unit represented by the general formula (II) and the structural unit represented by the general formula (III) is as follows: The kinematic viscosity may be appropriately selected depending on the desired kinematic viscosity.
What is necessary is just to select so that it may become 00 mm < ² > / s. 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 increase,
If it exceeds 7.0, the compatibility with the refrigerant may decrease.

Further, a polyvinyl ether compound (3)
Is a mixture of the polyvinyl ether-based compound (1) and the polyvinyl ether-based compound (2), but the mixing ratio is not particularly limited. The polyvinyl ether-based compounds (1) and (2) used in the present invention are obtained by polymerization of the corresponding vinyl ether-based monomer, and copolymerization of the corresponding hydrocarbon monomer having an olefinic double bond with the corresponding vinyl ether-based monomer. It can be produced by polymerization. The vinyl ether monomer that can be used here is represented by the following general formula (IV)

[0036]

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(Wherein, R ^{5 to} R ⁹ and a are the same as described above). As the vinyl ether-based monomer, there are various kinds corresponding to the 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-methylethyl ether; 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
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-
2-butene; 2-n-butoxy-1-butene; 2-isobutoxy-1-butene; 2-sec-butoxy-1-butene; 2-tert-butoxy-1-butene; 2-methoxy-2-butene; Ethoxy-2-butene; 2-n-
2-propene-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 following general formula (V)

[0038]

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Wherein R ^{10 to} R ¹³ are the same as described above. Examples of the monomer include ethylene, propylene, various butenes, various pentenes, various hexenes, various heptene, Examples include various octenes, diisobutylene, triisobutylene, styrene, and various alkyl-substituted styrenes. As the polyvinyl ether compound used in the present invention, those having the following terminal structure, that is, one terminal of which is represented by the general formula (VI) or (VII)

[0040]

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[0041] (wherein, R ¹⁴ to R ¹⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ¹⁴ to R ¹⁶ may be the same with or different from each other, R ¹⁹ to R ²² represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^{19 to} R ²² may be the same or different, and R ¹⁷ is 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,
R ¹⁸ represents the number of hydrocarbon groups having 1 to 20 carbon atoms, b has an average value 0, when R ¹⁷ O is plural, plural R ¹⁷ O may be the same or different . ),
And the remaining terminal is the general formula (VIII) or (IX)

[0042]

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[0043] (wherein, R ²³ to R ²⁵ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ²³ to R ²⁵ may be the same as or different from each other, R ²⁸ to R ³¹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^{28 to} R ³¹ may be the same or different, and R ²⁶ is 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,
R ²⁷ represents the number of hydrocarbon groups having 1 to 20 carbon atoms, c is the average value 0, when R ²⁶ O is plural, plural R ²⁶ O may be the same or different . ) And one end thereof is represented by the above general formula (VI) or (VII), and the other end is represented by the general formula (X)

[0044]

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(Where R³²~ R³⁴Is a hydrogen atom
Or a hydrocarbon group having 1 to 8 carbon atoms,
May be the same or different. )
Are preferred. Such polyvinyl ether type
Among the compounds, particularly the following are refrigeration oils of the present invention.
It is suitable as a base oil for the composition. (1) One end thereof is represented by the general formula (VI) or (VII)
And the remaining terminal is represented by the general formula (VIII) or (IX).
Having the structure represented by the general formula (II)^Five~ R ⁷Is
A hydrogen atom, a is a number from 0 to 4, R⁸Is two to four carbon atoms
Divalent hydrocarbon groups and R⁹Is a hydrocarbon group having 1 to 20 carbon atoms
What is. (2) having only the structural unit represented by the general formula (II)
Wherein one end thereof is represented by the general formula (VI),
And the other end has a structure represented by the general formula (VIII).
And R in the general formula (II)^Five~ R⁷Are both hydrogen atoms,
a is a number from 0 to 4, R ⁸Is a divalent hydrocarbon having 2 to 4 carbon atoms
Group and R⁹Is a hydrocarbon group having 1 to 20 carbon atoms.

(3) One of the terminals has a structure represented by the general formula (VI) or (VII) and the other terminal has a structure represented by the general formula (X). ^{5 to} R ⁷ are both hydrogen atoms, a is a number of 0 to 4, R ⁸ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁹ is a hydrocarbon group having 1 to 20 carbon atoms. (4) having only the structural unit represented by the general formula (II), one end of which is represented by the general formula (VI),
And the remaining terminal has a structure represented by the general formula (IX),
In the general formula (II), R ^{5 to} R ⁷ are both hydrogen atoms, a is a number of 0 to 4, R ⁸ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁹ is a carbon atom having 1 to 20 carbon atoms. Those that are hydrogen groups. Further, in the present invention, there is a structural unit represented by the general formula (II), one end of which is represented by the general formula (VI), and the other end is represented by the general formula (XI)

[0047]

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(Wherein, R ^{35 to} R ³⁷ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ³⁸ and R ⁴⁰ each represent a carbon atom And a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different; R ³⁹ and R ⁴¹ each represent a hydrocarbon group having 1 to 10 carbon atoms; D and e each represent an average number of 0 to 10, each of which may be the same or different, and when there are a plurality of R ³⁸ O, a plurality of R ³⁸ O ³⁸ O is may be the same or different, may use polyvinyl ether compound having a structure more R ⁴⁰ O represented by may be the same or different.) If there is more than one R ⁴⁰ O can do. Further, in the present invention, a polyvinyl ether compound described in the specification of Japanese Patent Application No. 8-18837 can be used, and particularly, a compound represented by the general formula (XII) or (XIII)

[0049]

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(Wherein R ⁴² represents a hydrocarbon group having 1 to 8 carbon atoms), and has a weight average molecular weight of 300 to 3000 (preferably 300 to 200).
0) wherein one terminal is represented by the general formula (XIV) or (XV)

[0051]

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(Wherein, R ⁴³ represents an alkyl group having 1 to 3 carbon atoms, and R ⁴⁴ represents a hydrocarbon group having 1 to 8 carbon atoms). A polyvinyl ether compound composed of a polymer can also be used. In addition, the following general formula (XVI)

[0053]

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(Wherein R ⁴⁵ represents a hydrocarbon group having or not having an ether bond in the molecule having 1 to 3 carbon atoms) and a structural unit (A) represented by the following general formula (XVII)

[0055]

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(Wherein R⁴⁶Is in a molecule having 3 to 20 carbon atoms
Indicates a hydrocarbon group with or without an ether bond
You. Having the structural unit (B) represented by
Ether compound [provided that R in structural unit (A)⁴⁵as well as
R of (B)⁴⁶Are not the same) are preferably used, especially
R ⁴⁵Is a methyl or ethyl group, R⁴⁶Has 3 to 6 carbon atoms.
In the case of a alkyl group, a polyvinyl ether compound is preferred.
Suitable, especially R⁴⁵Is an ethyl group, R⁴⁶Is an isobutyl group
Polyvinyl ether compound is the best
The ratio between the unit (A) and the structural unit (B) is 9 in molar ratio.
The range of 5: 5 to 50:50 is preferred.

The above polyvinyl ether compounds are described in JP-A-6-128578 and JP-A-6-2578.
34814, JP-A-6-234815, JP-A-8-
Any of those described in detail in each of the specifications of 193196 can be used. 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 polymerization, use is made of a combination of Brönsted acids, Lewis acids or organometallic compounds with an adduct of a carboxylic acid with water, alcohols, phenols, acetals or vinyl ethers. can do. 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.

Water, alcohols,
Adducts of phenols, acetals or vinyl ethers with carboxylic acids can be selected arbitrarily. Here, examples of the alcohols include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, and te.
Examples include saturated aliphatic alcohols having 1 to 20 carbon atoms such as rt-butanol, various pentanols, various hexanols, various heptanols, various octanols, and unsaturated aliphatic alcohols having 3 to 10 carbon atoms such as 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; n-valeric acid; isovaleric acid; Acid; n-caproic acid;
2,2-dimethylbutyric acid; 2-methylvaleric acid; 3-methylvaleric acid; 4-methylvaleric acid; enanthic acid; 2-methylcaproic acid; caprylic acid;
-Propylvaleric acid; n-nonanoic acid; 3,5,5-trimethylcaproic acid; caprylic acid; undecanoic acid and the like.

The vinyl ethers may be the same or different from those used for polymerization. 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.

Polymerization initiation terminals of the polymer are those in which hydrogen is bonded when water, alcohols or phenols are used, and when one of the alkoxy groups is eliminated from hydrogen or the used acetal when using acetal. Becomes 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 (IV) 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 control of the molecular weight in this polymerization reaction, the amount of water, alcohols, phenols, acetal and adducts of vinyl ethers and carboxylic acids is increased with respect to the vinyl ether monomer represented by the above general formula (IV). 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 carried out 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.
For example, hydrocarbons such as hexane, benzene, and toluene, and ethyl ether, 1,2-dimethoxyethane,
An ether solvent such as 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-based compound having the structural unit represented by the general formula (II) can be obtained by subjecting it to a usual separation / purification method as required.

The polyvinyl ether compound used in the present invention has a carbon / oxygen molar ratio of 4.2 to 7.0 as described above.
0 is preferable, but the carbon /
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 can be obtained, and if the ratio of the monomer having a small carbon / oxygen molar ratio is large, the carbon / oxygen molar ratio can be increased.
A polymer having a small oxygen molar ratio is obtained.

Further, as shown in the above-mentioned polymerization method of vinyl ether monomer, water, alcohols, phenols, acetals, adducts of vinyl ethers with carboxylic acids used as initiators, and combinations of monomers with monomers. Is also possible. 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.

Examples of the polyhydric alcohol ester include esterified products of a dihydric to hexahydric polyhydric alcohol and one or more monohydric fatty acids having 2 to 18 carbon atoms. Polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane,
Trimethylolpropane, pentaerythritol, erythritol, arabitol, sorbitol, mannitol and the like can be mentioned. The fatty acid having 2 to 18 carbon atoms may be linear or branched, and may be a saturated fatty acid or an unsaturated fatty acid. Specifically, acetic acid, propionic acid, isopropionic acid, butanoic acid, isobutanoic acid, pentanoic acid, isopentanoic acid, hexanoic acid, isohexanoic acid, heptanoic acid, isoheptanoic acid, octanoic acid,
Isooctanoic acid, 2-ethylhexanoic acid, nonanoic acid,
Examples include 3,5,5-trimethylhexanoic acid, decanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linolenic acid, and the like. Further, succinic acid, adipic acid, glutaric acid, sebacic acid,
Polybasic acids such as maleic acid may be used. The polyhydric alcohol ester may be appropriately selected depending on the desired kinematic viscosity, but is usually selected so that the kinematic viscosity at a temperature of 40 ° C. is ² to 500 mm ² / s. Examples of the polyester include those represented by the general formula (XVIII)

[0070]

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(Where R⁴⁷Is an alkylene having 1 to 10 carbon atoms
Group, R⁴⁸Is an alkylene group having 2 to 10 carbon atoms or carbon number
4-20 oxaalkylene groups are shown. )
It has a constitutional unit and has a molecular weight of 300 to 2,000.
Aliphatic polyester derivatives can be mentioned. this
R in the general formula (XVIII)⁴⁷Is alkylene having 1 to 10 carbon atoms
A methylene group, an ethylene group,
Pyrene group, ethylmethylene group, 1,1-dimethylethylene
Group, 1,2-dimethylethylene group, n-butylethyl
Group, isobutylethylene group, 1-ethyl-2-methyl
Ethylene group, 1-ethyl-1-methylethylene group, tri
Methylene group, tetramethylene group, pentamethylene group, etc.
Among them, preferred are those having 6 or less carbon atoms.
It is a alkylene group. Also, R ⁴⁸Is an alkyl having 2 to 10 carbon atoms
Represents a kylene group or an oxaalkylene group having 4 to 20 carbon atoms
You. The alkylene group is specifically R⁴⁷Example (However,
(Excluding a methylene group), preferably having 2 carbon atoms.
To 6 alkylene groups, and the oxaalkylene group is
Specifically, a 3-oxa-1,5-pentylene group;
Dioxa-1,8-octylene group; 3,6,9-trio
Oxa-1,11-undecylene group; 3-oxa-1,4
-Dimethyl-1,5-pentylene group; 3,6-dioxa
-1,4,7-trimethyl-1,8-octylene group;
3,6,9-trioxa-1,4,7,10-tetrame
Tyl-1,11-undecylene group; 3-oxa-1,4
-Diethyl-1,5-pentylene group; 3,6-dioxa
-1,4,7-triethyl-1,8-octylene group;
3,6,9-trioxa-1,4,7,10-tetrae
Tyl-1,11-undecylene group; 3-oxa-1,
1,4,4-tetramethyl-1,5-pentylene group;
3,6-dioxa-1,1,4,4,7,7-hexame
Tyl-1,8-octylene group; 3,6,9-trioxa
-1,1,4,4,7,7,10,10-octamethyl
-1,1,1-undecylene group; 3-oxa-1,2,2
4,5-tetramethyl-1,5-pentylene group; 3,6
-Dioxa-1,2,4,5,7,8-hexamethyl-
1,8-octylene group; 3,6,9-trioxa-1,
2,4,5,7,8,10,11-octamethyl-1,
1,1-undecylene group; 3-oxa-1-methyl-
1,5-pentylene group; 3-oxa-1-ethyl-1,
5-pentylene group; 3-oxa-1,2-dimethyl-
1,5-pentylene group; 3-oxa-1-methyl-4-
Ethyl-1,5-pentylene group; 4-oxa-2,2,2
6,6-tetramethyl-1,7-heptylene group; 4,8
-Dioxa-2,2,6,6,10,10-hexamethyl
And a 1,11-undecylene group.
You. Note that R⁴⁷, R⁴⁸Is the same or different for each structural unit
May be.

Further, the aliphatic polyester derivative represented by the above general formula (XVIII) preferably has a molecular weight (measured by GPC) of 300 to 2,000. Here, if the molecular weight is less than 300, the kinematic viscosity is too small,
On the other hand, if it exceeds 2,000, it becomes waxy, and all of them are not preferable as refrigerating machine oil. Such polyesters are described in International Publication WO 91/07479.
Any of those described in detail in the publication can be used.

Examples of the polyol ester include a carboxylic acid ester of a polyvalent hydroxy compound containing at least two hydroxyl groups. For example, the general formula (XIX) R ⁴⁹ [OCOR ⁵⁰ ] _f (XIX) Wherein R ⁴⁹ is a hydrocarbon group, R ⁵⁰ is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, f is an integer of 2 to 6, and a plurality of —OCOR ⁵⁰ may be the same or different.) Can be used.

In the general formula (XIX), R ⁴⁹ represents a hydrocarbon group, which may be linear or branched, and is preferably an alkyl group having 2 to 10 carbon atoms. R ⁵⁰ is a hydrogen atom or a hydrocarbon group having 1 to 22 carbon atoms, preferably an alkyl group having 2 to 16 carbon atoms. The above general formula (XI
The polyol ester represented by X) is a polyhydric alcohol represented by the general formula (XX) R ⁴⁹ (OH) _f ... (XX) (where R ⁴⁹ and f are the same as described above). And a carboxylic acid represented by the general formula (XXI) R ⁵⁰ COOH (XXI) (wherein R ⁵⁰ is the same as described above) or a reactive derivative such as an ester or an acid halide thereof. Can be obtained.

Examples of the polyhydric alcohol represented by the general formula (XX) include ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, trimethylolethane, trimethylolpropane,
Glycerin, pentaerythritol, dipentaerythritol, sorbitol and the like can be mentioned. On the other hand, carboxylic acids represented by (XXI) include, for example, propionic acid, butyric acid, pivalic acid, valeric acid, caproic acid, heptanoic acid, 3-methylhexanoic acid, 2-ethylhexylic acid, caprylic acid, decanoic acid, lauryl Acids, myristic acid, palmitic acid and the like. As the carbonate derivative, for example, a compound represented by the general formula (XXII)

[0076]

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(Wherein, R ⁵¹ and R ⁵³ each represent a hydrocarbon group having 30 or less carbon atoms or a hydrocarbon group having an ether bond having 2 to 30 carbon atoms, and they may be the same or different. well, R ⁵² is an alkylene group having 2 to 24 carbon atoms, g may be mentioned an integer of 1 to 100, polycarbonate h is represented by an integer from 1 to 10.).

In the general formula (XXII), R ⁵¹ and R
⁵³ is a hydrocarbon group having 30 or less carbon atoms or a hydrocarbon group having an ether bond having 2 to 30 carbon atoms,
Specific examples of the hydrocarbon group having 30 or less carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, and various nonyl groups. Various decyl groups; various undecyl groups; various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, various eicosyl groups, and other aliphatic carbonized groups. Alicyclic hydrocarbon groups such as hydrogen group, cyclohexyl group, 1-cyclohexenyl group, methylcyclohexyl group, dimethylcyclohexyl group, decahydronaphthyl group, tricyclodecanyl group, phenyl group, various tolyl groups, various xylyl groups, Aromatic hydrocarbon groups such as mesityl group and various naphthyl groups, Group, methylbenzyl group, phenylethyl group, 1-methyl-1-phenylethyl group, a styryl group, and the like aromatic aliphatic hydrocarbon groups such as cinnamyl group.

[0079] The hydrocarbon group having an ether bond having 2 to 30 carbon atoms, for example, the general formula ^{(XXIII) - (R 54 -O} ) i -R 55 ··· (XXIII) wherein, R ⁵⁴ Is an alkylene group having 2 or 3 carbon atoms (ethylene group, propylene group, trimethylene group), and R ⁵⁵ is an aliphatic, alicyclic or aromatic hydrocarbon group having 28 or less carbon atoms (R ⁵¹
And the same as the groups exemplified in the specific examples of ^R53 ), i is 1 to
Indicates an integer of 20. ], Specifically, ethylene glycol monomethyl ether group, ethylene glycol monobutyl ether group, diethylene glycol mono n-butyl ether group, triethylene glycol monoethyl ether group, propylene glycol monomethyl ether group, propylene glycol monobutyl ether Group, dipropylene glycol monoethyl ether group, and tripropylene glycol mono n-butyl ether group. For R ⁵¹ and R ⁵³ , among these, n-butyl group; isobutyl group; isoamyl group; cyclohexyl group; isoheptyl group; 3-methylhexyl group; 1,3-dimethylbutyl group; hexyl group; Alkyl groups such as 2-ethylhexyl group, ethylene glycol monomethyl ether group, ethylene glycol monobutyl ether group, diethylene glycol monomethyl ether group, triethylene glycol monomethyl ether group, propylene glycol monomethyl ether group, propylene glycol monobutyl ether group, dipropylene glycol monoethyl group Preferred are an alkylene glycol monoalkyl ether group such as an ether group and a tripropylene glycol mono n-butyl ether group.

In the above formula (XXII), R ⁵²
Is an alkylene group having 2 to 24 carbon atoms, and specific examples thereof include an ethylene group, a propylene group, a butylene group, an amylene group, a methylamylene group, an ethylamylene group, a hexylene group, a methylhexylene group, an ethylhexylene group, and an octamethylene group. , Nonamethylene group, decamethylene group, dodecamethylene group, tetradecamethylene group and the like. When there are a plurality of R ⁵² O, the plurality of R ⁵² may be the same or different.

The polycarbonate represented by the general formula (XXII) has a molecular weight (weight average molecular weight) of 300 to 3.0.
00, preferably 400 to 1,500. If the molecular weight is less than 300, the kinematic viscosity is too small to be suitable as a lubricating oil, while if it exceeds 3,000, it becomes waxy and difficult to use as a lubricating oil.

This polycarbonate can be produced by various methods. Usually, it is produced using a carbonate-forming derivative such as diester carbonate or phosgene and an aliphatic dihydric alcohol as raw materials. In order to produce a polycarbonate using these, a normal polycarbonate production method may be used, and generally, a transesterification method or a phosgene method may be used.

The above polycarbonate is disclosed in JP-A-3-217.
Any of those described in detail in Japanese Patent Publication No. 495 can be used. Further, as a carbonate derivative,
Formula ^{(XXIV) R 56 -O- (R} 58 O) j -CO- (OR 59) k -O-R 57) ··· (XXIV) ( wherein, R ⁵⁶ and R ⁵⁷ are each carbon atoms 1-20 aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon groups, which may be the same or different;
⁵⁸ and R ⁵⁹ each represent an ethylene group or an isopropylene group, which may be the same or different, and j and k each represent a number of 1 to 100. ) Can be used.

In the general formula (XXIV), R ⁵⁶ and R
Specific examples of the aliphatic hydrocarbon group in ⁵⁷ include methyl group, ethyl group, n-propyl group, isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups; various nonyl groups Various decyl groups; various undecyl groups; various dodecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various nonadecyl groups, various eicosyl groups, and the like. . Specific examples of the alicyclic hydrocarbon group,
Examples include a cyclohexyl group, a 1-cyclohexenyl group, a methylcyclohexyl group, a dimethylcyclohexyl group, a decahydronaphthyl group, and a tricyclodecanyl group. Specific examples of the aromatic hydrocarbon include a phenyl group, various tolyl groups, various xylyl groups, mesityl groups, and various naphthyl groups. Specific examples of the araliphatic hydrocarbon group include a benzyl group, a methylbenzyl group, a phenylethyl group, a styryl group, and a cinnamyl group.

The glycol ether carbonate represented by the general formula (XXIV) can be produced, for example, by subjecting a polyalkylene glycol monoalkyl ether to interesterification in the presence of an excess of a relatively low-boiling alcohol carbonate. it can. The above glycol ether carbonate is disclosed in JP-A-3-14929.
Any of those described in detail in Japanese Patent Publication No. 5 can be used. Further, as a carbonate derivative,
General formula (XXV)

[0086]

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(Wherein R ⁶⁰ and R ⁶¹ each represent an alkyl group having 1 to 15 carbon atoms or a monovalent alcohol residue having 2 to 12 carbon atoms, which may be the same or different. , R ⁶² represents an alkylene group having 2 to 12 carbon atoms, p is also possible to use a carbonic ester represented by an integer of 0 to 30.).

In the above formula (XXV), R ⁶⁰ and R ⁶¹
Each have 1 to 15 carbon atoms, preferably 2 to 9 carbon atoms
Represents an alkyl group or a monohydric alcohol residue having 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms; R ⁶² represents an alkylene group having 2 to 12 carbon atoms, preferably 2 to 9 carbon atoms;
It preferably represents an integer of 1 to 30. It is not preferable to use a carbonate ester that does not satisfy the above conditions, because various properties such as compatibility with the refrigerant are inferior. Specific examples of the alkyl group having 1 to 15 carbon atoms for R ⁶⁰ and R ⁶¹ include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a
-Pentyl group, n-hexyl group, n-heptyl group, n-
Octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, isopropyl, isobutyl, tert-butyl, isopentyl Group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group, isododecyl group, isotridecyl group, isotetradosyl group, isopentadecyl group and the like.

The dihydric alcohol residue having 2 to 12 carbon atoms specifically includes ethylene glycol;
3-propanediol; propylene glycol; 1,4
1,2-butanediol; 8-methyl-1,3-propanediol; 1,5-pentanediol; neopentyl glycol; 1,6-hexanediol; 2-ethyl-2-methyl-1, 1,7-heptanediol; 2-methyl-2-propyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; 1,8-octanediol; 1,9 -Nonanediol; 1,10-decanediol; 1,11-undecanediol; and 1,12-dodecanediol.

Further, specific examples of the alkylene group having 2 to 12 carbon atoms represented by R ⁶² include ethylene group; trimethylene group; propylene group; tetramethylene group; butylene group; Pentamethylene group;
2,2-dimethyltrimethylene group; hexamethylene group;
2-ethyl-2-methyltrimethylene group; heptamethylene group; 2-methyl-2-propyltrimethylene group;
Examples thereof include those having a linear or branched structure such as a 2-diethyltrimethylene group; an octamethylene group; a nonamethylene group; a decamethylene group; an undecamethylene group;

The molecular weight of the carbonate ester is not particularly limited, but those having a number average molecular weight of 200 to 3,000 are preferably used from the viewpoint of further improving the sealing property of the compressor, and the number average molecular weight is preferably used. Those having a molecular weight of 300 to 2,000 are more preferably used. As the carbonate ester, any of those described in detail in JP-A-4-63893 can be used. As the polyether ketone, for example, a compound represented by the general formula (XXVI)

[0092]

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(Wherein Q is a 1-8 valent alcohol residue;
R ⁶³ is an alkylene group having 2 to 4 carbon atoms, R ⁶⁴ is a methyl group or an ethyl group, R ⁶⁵ and R ⁶⁷ are each a hydrogen atom, an aliphatic, aromatic or araliphatic hydrocarbon group having 20 or less carbon atoms. , Which may be the same or different,
⁶⁶ represents an aliphatic, aromatic or araliphatic hydrocarbon group having 20 or less carbon atoms, r and s are numbers from 0 to 30, and u is from 1 to 8
, V is a number from 0 to 7, and u + v satisfies 1 to 8,
t represents 0 or 1. )).

In the general formula (XXVI), Q is 1-8
Examples of the alcohol having Q as a residue include monohydric alcohols such as methyl alcohol, ethyl alcohol, linear or branched propyl alcohol, linear or branched butyl alcohol, linear or branched Pentyl alcohol, linear or branched hexyl alcohol, linear or branched heptyl alcohol, linear or branched octyl alcohol, linear or branched nonyl alcohol, linear or branched decyl alcohol, linear or branched Decyl alcohol, linear or branched dodecyl alcohol, linear or branched tridecyl alcohol, linear or branched tetradecyl alcohol, linear or branched pentadecyl alcohol, linear or branched hexadecyl alcohol, linear or Branched heptadecyl alcohol,
Aliphatic monohydric alcohols such as linear or branched octadecyl alcohol, linear or branched nonadecyl alcohol, linear or branched eicosyl alcohol; aromatic alcohols such as phenol, methylphenol, nonylphenol, octylphenol, naphthol; benzyl Alcohols, araliphatic alcohols such as phenylethyl alcohol; and partially etherified products thereof as dihydric alcohols, for example, straight-chain or branched such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, and tetramethylene glycol Aliphatic alcohol, catechol, resorcinol,
Aromatic alcohols such as bisphenol A and bisphenyldiol, and their partially etherified products
Examples of the polyhydric alcohol include glycerin; trimethylolpropane; trimethylolethane; trimethylolbutane; linear or branched aliphatic alcohols such as 1,3,5-pentanetriol, pyrogallol, methylpyrogallol, and 5-sec-butylpyrogallol. Aromatic alcohols and their partially etherified products as tetrahydric to octahydric alcohols such as pentaerythritol, diglycerin, sorbitan, triglycerin, sorbitol, dipentaerythritol, tetraglycerin, pentaglycerin, hexaglycerin, triglycerol, Examples thereof include aliphatic alcohols such as pentaerythritol and partially etherified products thereof.

In the above general formula (XXVI), R ⁶³
The alkylene group having 2 to 4 carbon atoms represented by may be linear or branched, and specific examples include an ethylene group; a propylene group; an ethylethylene group; a 1,1-dimethylethylene group; , 2-dimethylethylene group and the like. In addition, carbon number 2 represented by R ^{65 to} R ⁶⁷
Examples of the aliphatic, aromatic or araliphatic hydrocarbon group having 0 or less include a methyl group; an ethyl group; a propyl group; a butyl group; a pentyl group; a heptyl group; an octyl group;
Decyl group; undecyl group; lauryl group; myristyl group;
Palmityl group; linear alkyl group such as stearyl group, isopropyl group; isobutyl group; isoamyl group; 2-ethylhexyl group; isostearyl group; branched chain alkyl group such as 2-heptylundecyl group; phenyl group; And an arylalkyl group such as a benzyl group.

In the general formula (XXVI), r and s are 0 to
The number of 30 is shown, and when r and s exceed 30, the contribution of the ether group in the molecule increases, which is not preferable in terms of compatibility with the refrigerant, electric insulation, and hygroscopicity. U is a number of 1 to 8, v is a number of 0 to 7, and u + v satisfies the relationship of 1 to 8, and these numbers indicate an average value, and are not limited to integers. t is 0 or 1. Further, r × u R ⁶³ may be the same or different, and s × u R ⁶⁴ may be the same or different. When u is 2 or more, u r, s, t, R ⁶⁵ and R ⁶⁶ may be the same or different, and when v is 2 or more, v R ⁶⁷ may be the same or different. You may.

As a method for producing the polyether ketone represented by the general formula (XXVI), a known method can be employed. For example, a method of oxidizing a secondary alkyloxy alcohol with hypochlorite and acetic acid (JP-A-4-126716), or a method of oxidizing with a zirconium hydroxide and ketone (JP-A-3-167)
149) can be used.

Examples of the fluorinated oil include fluorinated silicone oil, perfluoropolyether, and a reaction product of an alkane and a perfluoroalkyl vinyl ether. An example of a reaction product of an alkane and a perfluoroalkyl vinyl ether is represented by a general formula (XXVII) C _n H _{2n + 2} ... (XXVII) (in the formula, n represents an integer of 6 to 20). (XXVIII) wherein CF ₂ ＣＦCFOC _m F _{2m + 1} (XXVIII) wherein m is an integer of 1 to 4. (XXIX) C _n H _{(2n + 2-w)} (CF ₂ -CFHOC _m F _{2m + 1} ) _w ... (XXIX) (where w represents an integer of 1 to 4, n and m are the same as those described above.).

The alkane represented by the general formula (XXVII) may be linear, branched or cyclic. Specific examples thereof include n-octane; n-decane; n-dodecane; Cyclooctane; cyclododecane; 2,2,4-
Examples of the perfluoroalkyl vinyl ether represented by the general formula (XXVIII) include perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro n-propyl vinyl ether, and perfluoro n. −
Butyl vinyl ether and the like can be mentioned. Examples of the polyalkylene glycol include a compound represented by the following general formula (XXX) R ⁶⁸ -[(OR ⁶⁹ ) _m -OR ⁷⁰ ] _n ... (XXX) (where R ⁶⁸ is a hydrogen atom and has 1 to 10 carbon atoms) An alkyl group, an acyl group having 2 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding portions, R ⁶⁹ is an alkylene group having 2 to 4 carbon atoms, and R ⁷⁰ is a hydrogen atom , Carbon number 1-1
0 alkyl group or acyl group having 2 to 10 carbon atoms, n is 1
And m is a number such that the average value of m × n is 6 to 80. )).

In the general formula (XXX), the alkyl group for R ⁶⁸ and R ⁷⁰ may be any of linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. If the carbon number of the alkyl group exceeds 10, the compatibility with the refrigerant is reduced, and phase separation may occur. The preferred alkyl group has 1 to 6 carbon atoms.

The alkyl group of the acyl group in R ⁶⁸ and R ⁷⁰ may be linear, branched or cyclic. Specific examples of the alkyl group portion of the acyl group include those having 1 to 9 carbon atoms mentioned as specific examples of the above alkyl group.
Various groups can be similarly mentioned. If the number of carbon atoms in the acyl group exceeds 10, the compatibility with the refrigerant may be reduced and phase separation may occur. A preferred acyl group has 2 carbon atoms.
~ 6.

R⁶⁸And R⁷⁰Is an alkyl group or
When it is an acyl group, R⁶⁸And R ⁷⁰Identical to each other
May also be different. Further, when n is 2 or more,
Multiple Rs in one molecule⁷⁰May be the same or different.
R⁶⁸Having 1 to 10 carbon atoms having 2 to 6 binding sites
If it is an aliphatic hydrocarbon group, this aliphatic hydrocarbon group
Or a ring. Two binding sites
As the aliphatic hydrocarbon group having, for example, an ethylene group,
Propylene, butylene, pentylene, hexylene
Group, heptylene group, octylene group, nonylene group, decile
Group, cyclopentylene group, cyclohexylene group, etc.
Can be mentioned. Also has 3 to 6 binding sites
As the aliphatic hydrocarbon group, for example, trimethylol pro
Bread, glycerin, pentaerythritol, sorbitol
1,2,3-trihydroxycyclohexane; 1,
Polyvalent alcohols such as 3,5-trihydroxycyclohexane
Residues obtained by removing hydroxyl groups from coal may be mentioned.

If the aliphatic hydrocarbon group has more than 10 carbon atoms, the compatibility with the refrigerant may be reduced and phase separation may occur. The preferred number of carbon atoms is 2 to 6. The general formula (XX
R ^{69 in} X) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same or may contain two or more oxyalkylene groups, but those containing at least oxypropylene units in one molecule are preferred, and particularly the oxyalkylene units Those containing at least 50 mol% of oxypropylene units are preferred. When two or more oxyalkylene groups are contained, they may be random copolymers or block copolymers.

[0104] n in the general formula (XXX) in an integer of 1 to 6, it is determined in accordance with the number of binding sites of R ^68. For example, R
If ⁶⁸ is an alkyl group or an acyl group, n is 1, R ⁶⁸
Is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 bonding sites, n is 2, 3, 4, 5 and 6 respectively
Becomes Further, m is a number such that the average value of m × n is 6 to 80, and if the average value of m × n is out of the range, the object of the present invention may not be sufficiently achieved.

The polyalkylene glycol represented by the general formula (XXX) includes a polyalkylene glycol having a hydroxyl group at a terminal, and the content of the hydroxyl group is 50 mol% or less based on all terminal groups. If it is such a ratio, it can be suitably used even if it is contained.
If the content of the hydroxyl group exceeds 50 mol%, the hygroscopicity may increase, and the viscosity index may decrease.

Examples of the polyalkylene glycol represented by the general formula (XXX) include polyoxypropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol dimethyl ether, polyoxypropylene glycol monobutyl ether, and polyoxypropylene glycol diacetate. It is suitable in terms of economy, effect and effect. The polyalkylene glycol represented by the general formula (XXX) is described in
Any of those described in detail in Japanese Patent Publication No. -305893 can be used.

[0107]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Examples 1 to 10 and Reference Examples 1 and 2 Additives of the type shown in Table 1 to base oils of the type shown in Table 1 were blended in the amounts shown in Table 1 based on the total weight of the composition, followed by freezing. A machine oil composition was prepared. With respect to this composition, the performance of the composition was evaluated by performing a sealed tube test, an abrasion test, and a test for evaluating the capillary obstruction after the actual machine test in the following manner. Table 2 shows the results. (1) Shield tube test A catalyst Fe / Cu / Al was put in a glass tube, and R410A /
The sample was filled with oil / water = 1 g / 4 g / 2,000 wtppm and sealed. After maintaining at 175 ° C. for 10 days, the appearance of oil, the appearance of catalyst, the increase in total acid value, and the presence or absence of sludge were determined. (2) Wear test Using a closed block-on-ring tester, the block / ring material was set to A4032 / SUJ2. Set the block / ring and put 100 g of sample oil and R
After filling 10 g of 410A, a wear test was performed under the conditions of a rotation speed of 500 rpm, an oil temperature of 50 ° C., a load of 80 kg and a test time of 60 minutes under a pressure of 0.3 MPa, and the block wear width was measured. (3) Actual machine test For each refrigerating machine oil composition to which 1% by weight of rust-preventive oil (oil coat Z5; manufactured by Idemitsu Kosan Co., Ltd.) was added, endurance for 6 months using a durability tester of a scroll compressor for packaged air conditioners. A test was performed to measure the capillary pressure loss (%: new product).

[0108]

[Table 1]

[Note] ・ Type of base oil 1: random copolymer of polyvinyl ethyl ether (A) and polyvinyl isobutyl ether (B), A unit / B unit (molar ratio) = 9/1 kinematic viscosity 68 mm ² / s (40 ° C.), number average molecular weight 720 2: polyvinyl ethyl ether (A) / polyvinyl isobutyl ether (B) random copolymer, A unit / B unit (molar ratio) = 7/3 kinematic viscosity 68 mm ² / s (40 C), number average molecular weight 710 3: random copolymer of polyvinyl ethyl ether (A) and polyvinyl isobutyl ether (B), A unit / B unit (molar ratio) = 5/5 kinematic viscosity 32 mm ² / s (40 ° C) , Number average molecular weight 430 4: ester of pentaerythritol with a mixed acid of 3,3,5-trimethylhexanoic acid / isooctanoic acid (molar ratio 5/5), kinematic viscosity 68 ^{m 2 / s (40 ℃)} 5: Type of trimethylolpropane of propane 3,3,5-trimethyl hexanoic acid ester kinematic viscosity ^{56mm 2 / s (40 ℃)} · Additives A1: polypropylene glycol nonyl methyl ether kinematic viscosity 20mm ² / s (40 ° C), number average molecular weight 400 A2: polypropylene glycol di-sec-butylphenyl methyl ether kinematic viscosity 30 mm ² / s (40 ° C), number average molecular weight 500 A3: polypropylene glycol nonylphenyl methyl ether dynamic Viscosity 10 mm ² / s (40 ° C.), number average molecular weight 250 A4: polypropylene glycol / polynonylene glycol dimethyl ether kinematic viscosity 43 mm ² / s (40 ° C.), number average molecular weight 700

[0110]

[Table 2]

[0111]

The refrigerating machine oil composition of the present invention has excellent lubricating performance, in particular, improves lubricating oil properties between an aluminum material and a steel material, can suppress abrasion, and does not cause environmental pollution. It is suitable as lubricating oil for refrigerators using a refrigerant. Therefore, the refrigerating machine oil composition of the present invention is particularly effective when used in a car air conditioner, a room air conditioner, a refrigerator, and the like, and its industrial utility value is extremely high.

Continued on the front page (51) Int.Cl. ⁶ Identification code FI C10N 40:30

Claims (1)

[Claims] 1. A base oil comprising a synthetic oil, having a number average molecular weight of 2
A refrigerating machine oil composition comprising a polyalkylene glycol derivative represented by the following general formula (I) having a number of from 0.00 to 3,000. R ^1- (OR ² ) _m- (OR ³ ) _n -OR ⁴ (I) (R ¹ and R ⁴ each represent a hydrocarbon group or an acyl group having 1 to 30 carbon atoms, or hydrogen; R ² has ² carbon atoms
To 4 alkylene groups, R ³ represents an alkylene group having 2 to 30 carbon atoms or a substituted alkylene group, m and n each represent a number satisfying the above molecular weight, and n may be 0 in some cases. However, at least one of R ¹ , R ³ and R ⁴ has 6 carbon atoms.
It has the above hydrocarbon groups. )