JPH11315295A - Refrigerator oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a composition which has excellent lubricating properties and which can reduce abrasion of lubricating parts using aluminum materials when hydrocarbon-based refrigerants are used by blending a glyceryl ether compound with a base oil comprising mineral oils and/or synthetic oils in a specific ratio. SOLUTION: A compound of the formula: R<1> -OCH2 CH(OH)CH2 CH (wherein R<1> is a 10-22C alkyl) is blended in an amount of 0.01-10 wt.% based on the total amount of the composition. As a base oil, synthetic oils are more preferred than mineral oils and especially oxygen-containing synthetic oils are suitable. Among them, polyvinyl ethers, polyol esters and polyalkylene glycols are suitable. Especially, a polyvinyl ether copolymer having a structural unit of formula I (wherein R<42> is a 1-3C hydrocarbon which has or does not have an ether linkage) and a structural unit of formula II (wherein R<43> is a 3-20C hydrocarbon which has or does not have an ether linkage) is suitable.

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.
Ether-based, carbon dioxide-based or ammonia-based, preferably when using a hydrofluorocarbon-based refrigerant that can replace the chlorofluorocarbon-based refrigerant which is a problem with environmental pollution, it has excellent lubrication performance, In particular, the present invention relates to a refrigerating machine oil composition that can reduce wear of a lubricated portion using an aluminum material.

[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, their regulations are becoming 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 are attracting attention and are replacing them. This hydrofluorocarbon, especially R134a, R32, R125, R143a
Has no fear of destroying the ozone layer and is preferable as a refrigerant for a compression refrigerator. However, there is a problem when the hydrofluorocarbon is used alone, for example, "Energy and Resources", Vol. 16, No. 5,
Page 474 contains (1) R13 as an alternative to R22
When 4a is applied to an air conditioner, the operating pressure is low and R2
The capacity is reduced by about 40% and the efficiency is reduced by about 5% compared to 2.
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.

As a refrigerant for a compression type refrigerator, it is desirable that the refrigerant can be used without changing the current refrigeration system. However, due to the above-mentioned problem, a refrigerant in which the above-mentioned hydrofluorocarbon is mixed should actually be used. That is, the current R2
2, To replace R502 refrigerant, from the viewpoint of efficiency,
In order to use flammable R32 and R143a, and to make the refrigerant incombustible as a whole, it is desirable to mix R125 and R134a with the former. The International Symp
osium on R22 & R502 Alternative Refrigerants, 199
On page 4, 166, for the R32 / R134a mixture, R
It is shown that when the content of 32 is 56% by weight or more, it is flammable. 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
Base oils having a specific structure, such as polyalkylene glycols, polyol esters, and polyvinyl ethers, which have different properties from conventional refrigerants and are used in combination therewith, have been studied and used. However,
Hydrofluorocarbon-based refrigerants are inferior in lubricating performance as compared with conventional refrigerants. Therefore, development of an additive that is added to the above base oil to improve lubricity has been desired. Conventionally, neutral phosphate esters such as tricresyl phosphate (hereinafter, referred to as TCP) and triphenyl phosphate (hereinafter, referred to as TPP) have been generally used as lubricity improvers used in refrigerator oils. However, although these additives are effective for the combination of iron and iron,
In the case of aluminum material, there was no effect of reducing friction.

[0008] Therefore, when a hydrofluorocarbon-based refrigerant, which can be used in place of a chlorofluorocarbon-based refrigerant, is used, a refrigerating machine oil composition having excellent lubrication performance and capable of reducing abrasion of a lubricated portion particularly using an aluminum material is obtained. Was desired.

[0009]

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. The present invention provides a refrigerating machine oil composition having excellent lubricating performance when using a hydrofluorocarbon-based refrigerant which can be used in place of a chlorofluorocarbon-based refrigerant as a refrigerant, and capable of reducing abrasion of a lubricated portion particularly using an aluminum material. It is intended to do so.

[0010]

As a result of intensive studies, the present inventors have found that the above-mentioned object of the present invention can be effectively achieved by blending a specific glyceryl ether compound with a base oil. The present invention has been completed. That is, the gist of the present invention is as follows. (1) a base oil comprising a mineral oil and / or synthetic oils, the following general formula _{^{(I) R 1 -OCH 2 CH}} (OH) CH 2 OH ··· (I) ( wherein, R ¹ is 10 carbon atoms A refrigeration oil composition comprising a glyceryl ether compound represented by the formula (1) wherein the glyceryl ether compound is represented by 0.01 to 10% by weight based on the total amount of the composition. (2) The refrigerator oil composition according to (1), wherein the base oil is an oxygen-containing synthetic oil. (3) The refrigerator oil composition according to (2), wherein the oxygen-containing synthetic oil is at least one selected from polyvinyl ether, polyol ester, and polyalkylene glycol. (4) The following general formula (XVI)

[0011]

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(Wherein R ⁴² 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)

[0013]

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(Wherein R ⁴³ represents a hydrocarbon group having or not having an ether bond in the molecule having 3 to 20 carbon atoms). A polyvinyl ether copolymer having a structural unit (B) represented by the following formula: [However, R ⁴³ to R ⁴² and structural units of the structural unit (a) (B) are not the same. Base oil containing
A glyceryl ether compound represented by the following general formula (I) R ¹ -OCH ₂ CH (OH) CH ₂ OH (I) wherein R ¹ represents an alkyl group having 10 to 22 carbon atoms. Is contained in an amount of 0.01 to 10% by weight based on the total amount of the composition. (5) The refrigerating machine oil composition according to (4), wherein in the structural unit (A), R ⁴² is an ethyl group, and in the structural unit (B), R ⁴³ is an isobutyl group.

[0015]

Embodiments of the present invention will be described below. In the refrigerator oil composition of the present invention, mineral oil and / or synthetic oil are used as the base oil. The mineral oil and the synthetic oil are not particularly limited as long as they are generally used as a base oil of a refrigerating machine oil.
Kinematic viscosity at ² ° C. is ² to 500 mm ² / s, especially 5 to ²
00mm 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 desirably −10 ° C. or less.

There are various types of such mineral oils and synthetic oils, and they may be appropriately selected according to the use and the like. As the mineral oil, mineral oils include, for example, paraffinic mineral oil, naphthenic mineral oil, intermediate mineral oil, and the like, while synthetic oils include oxygen-containing synthetic oils and hydrocarbon-based synthetic oils. Among the synthetic oils, the oxygen-containing synthetic oils include synthetic oils containing ether groups, ketone groups, ester groups, carbonate groups, hydroxyl groups, etc. in the molecule, and heteroatoms (S, P) together with these groups. , F, Cl, S
i, N etc.), specifically, polyvinyl ether, polyol ester,
Polyalkylene glycol, polyester, carbonate derivative, polyether ketone, fluorinated oil and the like.

The oxygen-containing synthetic oil 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 mineral oil may be used alone or in combination of two or more as the base oil, or the synthetic oil may be used alone or in combination of two or more. Alternatively, one or more mineral oils and one or more synthetic oils may be used in combination. Synthetic oils are preferred over mineral oils, but oxygen-containing synthetic oils are particularly preferred because they have good compatibility with Freon refrigerants such as R-134a and have excellent lubricating performance. Among them, polyvinyl ether, polyol ester and polyalkylene glycol are preferred.

Next, the glyceryl ether compound blended in the base oil will be described. The glyceryl ether compound is represented by the following general formula (I): R ¹ —OCH ₂ CH (OH) CH ₂ OH (I), wherein R ¹ is an alkyl group having 10 to 22 carbon atoms, However, it may be either branched or branched. 10 carbon atoms
If it is less than the above, the wear reducing effect is small, and if it exceeds 22, the friction reducing effect becomes small and the solubility in the base oil is inferior. Specifically, 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, various heneicosyl groups, and various docosyl groups. Among them, those having a tridecyl group, an isopentadecyl group or an isooctadecyl group are preferred.

The above glyceryl ether compounds may be used alone or in combination of two or more. The amount of the glyceryl ether compound is 0.0% based on the total amount of the composition.
1 to 10% by weight. When the amount is less than 0.01% by weight, the object of the present invention is not sufficiently exhibited. When the amount exceeds 10% by weight, the effect is not improved for the amount, and the solubility in the base oil decreases. I do. The preferred amount is 0.1
-3% by weight.

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; phenol-based and amine-based antioxidants; 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, a mixture having a weight ratio of 45:55 (hereinafter, referred to as R410B), a mixture of R125, R143a, and R134a having 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). Finally, the oxygen-containing synthetic oil used as the base oil will be described in detail. As the polyvinyl ether, for example, a compound represented by the general formula (II)

[0022]

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(Wherein, R ^{2 to} R ⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, which may be the same or different, and R ⁵ represents a 1 to 10 carbon atom. A divalent hydrocarbon group or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, R ⁶ is a hydrocarbon group having 1 to 20 carbon atoms, and a is a number having an average value of 0 to 10 , R ² ~
R ⁶ may be the same as or different from each other in each structural unit, also in the case where R ⁵ O is plural, plural R ⁵ O may be the same or different. And a polyvinyl ether-based compound (1) having a structural unit represented by formula (1).
Further, a structural unit represented by the above general formula (II) and

[0024]

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(Wherein, R ^{7 to} R ¹⁰ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different, and R ^{7 to} R ¹⁰ are 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 ^{2 to} R ⁴ 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 ^{2 to} R ⁴
Is particularly preferably a hydrogen atom.

On the other hand, R ⁵ 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 ⁵ 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 ⁵ O is plural, plural R ⁵ O may be the same or different.

Further, R ⁶ 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. The polyvinyl ether compound has a carbon / oxygen molar ratio of 4.2 to 7.0.
Those in the range of 0 are preferred. 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 ^{7 to} R ¹⁰ 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 ⁶ in the general formula (II).
R ^{7 to} R ¹⁰ 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 (II) and the structural unit represented by the general formula (III) is as follows: What is necessary is just to select suitably according to the desired kinematic viscosity. In addition, this polyvinyl ether compound,
Those having a carbon / oxygen molar ratio in the range of 4.2 to 7.0 are preferred. 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 (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)

[0034]

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(Wherein, R ^{2 to} R ⁶ 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)

[0036]

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(Wherein R ^{7 to} R ¹⁰ 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)

[0038]

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[0039] (wherein, R ¹¹ to R ¹³ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ¹¹ to R ¹³ may be the same with or different from each other, R ¹⁶ to R ¹⁹ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^{16 to} R ¹⁹ may be the same or different from each other, and R ¹⁴ 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 ¹⁵ is a hydrocarbon group having 1 to 20 carbon atoms, b has an average value thereof indicates the number of 0, when R ¹⁴ O is plural, plural R ¹⁴ O may be the same or different . ),
And the remaining terminal is the general formula (VIII) or (IX)

[0040]

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[0041] (wherein, R ²⁰ to R ²² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, R ²⁰ to R ²² may be the same as or different from each other, R ²⁵ to R ²⁸ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ^{25 to} R ²⁸ may be the same or different from each other, and R ²³ 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 ²⁴ represents the number of hydrocarbon groups having 1 to 20 carbon atoms, c is the average value 0, when R ²³ O is plural, plural R ²³ 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)

[0042]

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(Where R²⁹~ R³¹Is 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)^Two~ R ^FourIs
A hydrogen atom, a is a number from 0 to 4, R^FiveIs two to four carbon atoms
Divalent hydrocarbon groups and R⁶Is 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)^Two~ R^FourAre both hydrogen atoms,
a is a number from 0 to 4, R ^FiveIs a divalent hydrocarbon having 2 to 4 carbon atoms
Group and R⁶Is 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). ^{2 to} R ⁴ are each a hydrogen atom, a is a number of 0 to 4, R ⁵ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁶ 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 ^{2 to} R ⁴ are both hydrogen atoms, a is a number of 0 to 4, R ⁵ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ⁶ 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)

[0045]

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(Wherein, R ^{32 to} 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 ³⁵ and R ³⁷ each represent a carbon atom And a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different; R ³⁶ and R ³⁸ each represent a hydrocarbon group having 1 to 10 carbon atoms; And d and e each have an average value of 0 to 10, each of which may be the same or different, and when there are a plurality of R ³⁵ O, a plurality of R ³⁵ O ³⁵ O is may be the same or different, may use polyvinyl ether compound having a structure more R ³⁷ O represented by may be the same or different.) If there is more than one R ³⁷ O can do. Further, in the present invention, the following general formula (XII) or (XIII)

[0047]

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(Wherein R ³⁹ represents a hydrocarbon group having 1 to 8 carbon atoms) and has a weight average molecular weight of 300 to 3,000 (preferably 300 to 2,000).
000), and one end is represented by the general formula (XIV) or (X
V)

[0049]

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(Wherein, R ⁴⁰ represents an alkyl group having 1 to 3 carbon atoms, and R ⁴¹ 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)

[0051]

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(Wherein R ⁴² represents a hydrocarbon group having or not having an ether bond in a molecule having 1 to 3 carbon atoms) and a structural unit (A) represented by the following general formula (XVII)

[0053]

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(Wherein R ⁴³ represents a hydrocarbon group having or not having an ether bond in the molecule having 3 to 20 carbon atoms). A polyvinyl ether copolymer having a structural unit (B) represented by the following formula: [However, R ^{42 of} the structural unit (A) and R ⁴³ of the structural unit (B) are not the same. ] Is particularly preferably used. R ⁴² is an alkyl group having 1 to 3 carbon atoms, R ^{43 is} 3 to 3 carbon atoms
Is the alkyl group of 20, more preferably, in particular R ⁴² is a methyl group or an ethyl group, when R ⁴³ is a polyvinyl ether copolymer in the case of the alkyl group having 3 to 6 carbon atoms is preferred, and among them, R ⁴² is A polyvinyl ether copolymer in which an ethyl group and R ⁴³ are an isobutyl group is optimal. In this case, the ratio of the structural unit (A) to the structural unit (B) is 9 in a molar ratio.
The range of 5: 5 to 50:50 is preferable, and 95: 5 to 7
A range of 0:30 is more preferred. Incidentally, the copolymer,
It may be a random body or a block body.

The above-mentioned 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 Lewis acids include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride,
Examples thereof include zinc dichloride and ferric chloride. Among these Lewis acids, boron trifluoride is particularly 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; 2-methylbutyric 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 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.

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 used acetals when acetal is used. 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-based 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 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 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 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.
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 polymerization method of the vinyl ether monomer, water, alcohols, phenols, acetals and adducts of vinyl ethers with carboxylic acids, which are 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 polyol ester include a carboxylic acid ester of a polyhydric hydroxy compound containing at least two hydroxyl groups. For example, a general formula (XVIII) R ⁴⁴ [OCOR ⁴⁵ ] _f. Wherein R ⁴⁴ is a hydrocarbon group, R ⁴⁵ 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 ⁴⁵ may be the same or different.) Can be used.

In the general formula (XVIII), R ⁴⁴ represents a hydrocarbon group, which may be linear or branched, and preferably an alkyl group having 2 to 10 carbon atoms. R ⁴⁵ 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 polyol ester represented by the general formula (XVIII) has a general formula (XI
X) R ⁴⁴ (OH) _f ... (XIX) (wherein R ⁴⁴ and f are the same as described above) and a general formula (XX) R ⁴⁵ COOH. (XX) (in the formula, R ⁴⁵ is the same as described above), and can be obtained by reacting with a reactive derivative such as a carboxylic acid or an ester or an acid halide thereof.

Examples of the polyhydric alcohol represented by the general formula (XIX) 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, as the carboxylic acid represented by (XX), for example, propionic acid, butyric acid, pivalic acid, valeric acid, caproic acid, heptanoic acid, 3-methylhexanoic acid, 2-ethylhexanoic acid, caprylic acid, pelargonic acid, Examples thereof include capric acid, lauric acid, myristic acid, and palmitic acid.

The above polyalkylene glycol is represented by the following general formula (XXI) R ⁴⁶ -[(OR ⁴⁷ ) _g -OR ⁴⁸ ] _h (XXI) (where R ⁴⁶ is a hydrogen atom, carbon number An alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding portions, R ⁴⁷ is an alkylene group having 2 to 4 carbon atoms, R ⁴⁸ Is a hydrogen atom, having 1 to 1 carbon atoms
0 alkyl group or acyl group having 2 to 10 carbon atoms, h is 1
G is an integer of 6 to 80, and g is an integer of 6 to 80. )).

In the general formula (XXI), the alkyl group for R ⁴⁶ and R ⁴⁷ 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 portion of the acyl group in R ⁴⁶ and R ⁴⁸ 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.

R⁴⁶And R⁴⁸Is an alkyl group or
When it is an acyl group, R⁴⁶And R ⁴⁸Identical to each other
May also be different. When h is 2 or more,
Multiple Rs in one molecule⁴⁸May be the same or different.
R⁴⁶Having 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 ^{47 in} I) is an alkylene group having 2 to 4 carbon atoms, and examples of the oxyalkylene group of the repeating unit include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same or 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.

H in the general formula (XXI) is an integer of 1 to 6, and is determined according to the number of the binding sites of R ⁴⁶ . For example, R
If ⁴⁶ is an alkyl group or an acyl group, h is 1, R ⁴⁶
Is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 bonding sites, h is 2, 3, 4, 5 and 6 respectively
Becomes Further, g is a number such that the average value of g × h is 6 to 80. If the average value of g × h is out of the above range, the object of the present invention may not be sufficiently achieved.

The polyalkylene glycol represented by the general formula (XXI) 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.

The polyalkylene glycol represented by the general formula (XXI) includes polyoxypropylene glycol dimethyl ether, polyoxyethylene polyoxypropylene glycol monomethyl ether, polyoxyethylene polyoxypropylene glycol dimethyl ether,
Polyoxyethylene polyoxypropylene glycol monobutyl ether, polyoxypropylene glycol monobutyl ether, and polyoxypropylene glycol diacetate are preferred in terms of economy and effect. As the polyester, for example, the general formula (XXII)

[0077]

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(Wherein, R ⁴⁹ represents an alkylene group having 1 to 10 carbon atoms, and R ⁵⁰ represents an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms). And an aliphatic polyester derivative having a molecular weight of 300 to 2,000.

In the general formula (XXII), R⁴⁹Has 1 to 1 carbon atoms
10 alkylene groups, specifically, a methylene group,
Ethylene group, propylene group, ethylmethylene group, 1,1
-Dimethylethylene group, 1,2-dimethylethylene group,
n-butylethylene group, isobutylethylene group, 1-d
Tyl-2-methylethylene group, 1-ethyl-1-methyl
Ethylene group, trimethylene group, tetramethylene group, pen
A tamethylene group and the like can be mentioned, but preferably
It is an alkylene group having 6 or less carbon atoms. Also, R ⁵⁰Is carbon
An alkylene group having 2 to 10 carbon atoms or an oxa having 4 to 20 carbon atoms
Shows an alkylene group. The alkylene group is specifically R⁴⁹
Is the same as the specific example (excluding the methylene group) of
Preferably, it is an alkylene group having 2 to 6 carbon atoms,
The alkylene group is specifically 3-oxa-1,5-pentene
A 3,6-dioxa-1,8-octylene group;
3,6,9-trioxa-1,11-undecylene group;
3-oxa-1,4-dimethyl-1,5-pentylene
A group; 3,6-dioxa-1,4,7-trimethyl-1,
8-octylene group; 3,6,9-trioxa-1,4,4
7,10-tetramethyl-1,11-undecylene group;
3-oxa-1,4-diethyl-1,5-pentylene
A group; 3,6-dioxa-1,4,7-triethyl-1,
8-octylene group; 3,6,9-trioxa-1,4,4
7,10-tetraethyl-1,11-undecylene group;
3-oxa-1,1,4,4-tetramethyl-1,5-
Pentylene group; 3,6-dioxa-1,1,4,4
7,7-hexamethyl-1,8-octylene group; 3,
6,9-trioxa-1,1,4,4,7,7,10,
10-octamethyl-1,11-undecylene group; 3-
Oxa-1,2,4,5-tetramethyl-1,5-pen
Tylene 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-o
Octamethyl-1,11-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-me
Tyl-4-ethyl-1,5-pentylene group; 4-oxa
-2,2,6,6-tetramethyl-1,7-heptylene
Group; 4,8-dioxa-2,2,6,6,10,10-
Hexamethyl-1,11-undecylene group and the like
be able to. Note that R⁴⁹, R⁵⁰Is the same for each constituent unit
May also be different.

Further, the aliphatic polyester derivative represented by the general formula (XXII) desirably 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. As the carbonate derivative, for example, a compound represented by the general formula (XXIII)

[0081]

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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, i is may be mentioned an integer of 1 to 100, polycarbonate j is represented by the indicating.) an integer from 1 to 10.

In the general formula (XXIII), 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.

[0084] The hydrocarbon group having an ether bond having 2 to 30 carbon atoms, for example, the general formula ^{(XXIV) - (R 54 -O} ) k -R 55 ··· (XXIV) 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 ), k 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 general formula (XXIII), 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 (XXIII) 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,
General formula (XXV) R ⁵⁶ -O- (R ⁵⁸ O) _p -CO- (OR ⁵⁹ ) _q -OR ⁵⁷ (XXV) (wherein R ⁵⁶ and R ⁵⁷ each have 1 carbon atom) Represents up to 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 p and q each represent a number of 1 to 100. ) Can be used.

In the above formula (XXV), R ⁵⁶ and R ⁵⁷
Specific examples of the aliphatic hydrocarbon group in the above 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 (XXV) 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-3-149295.
Any of those described in detail in the publication can be used. Further, as a carbonate derivative, a compound represented by the general formula (XXVI)

[0091]

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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, r is also possible to use a carbonic ester represented by an integer of 0 to 30.).

In the general formula (XXVI), R ⁶⁰ and R
⁶¹ has 1 to 15 carbon atoms, preferably 2 to 2 carbon atoms.
9 alkyl groups or 2-12 carbon atoms, preferably 2-9
Wherein R ⁶² has 2 to 12 carbon atoms;
It preferably represents 2 to 9 alkylene groups, and r represents 0 to 3
0, preferably 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, an n-pentyl group, an n-hexyl group, and an n-alkyl group. Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n
-Undecyl group, n-dodecyl group, n-tridecyl group,
n-tetradecyl group, n-pentadecyl group, isopropyl group, isobutyl group, tert-butyl group, isopentyl group, isohexyl group, isoheptyl group, isooctyl group, isononyl group, isodecyl group, isoundecyl group,
Examples include an isododecyl group, an isotridecyl group, an isotetradosyl group, and an isopentadecyl group.

Examples of the divalent alcohol residue having 2 to 12 carbon atoms include ethylene glycol;
3-propanediol; propylene glycol; 1,4
1,2-butanediol; 8-methyl-1,3-propanediol; 1,5-pentanediol; neopentylene glycol; 1,6-hexanediol; 2-ethyl-2-methyl-1 1,3-propanediol; 1,7-heptanediol; 2-methyl-2-
Propyl-1,3-propanediol; 2,2-diethyl-1,3-propanediol; 1,8-octanediol; 1,9-nonanediol; 1,10-decanediol; 1,11-undecanediol; Residues such as 1,12-dodecanediol can be mentioned.

Further, specific examples of the alkylene group having 2 to 12 carbon atoms represented by R ⁶² include an ethylene group; a trimethylene group; a propylene group; a tetramethylene group; a 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. 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 (XXVII)

[0097]

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(Wherein T is a mono- to octavalent 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, s and u are numbers of 0 to 30, w is 1 to 8
, X is a number from 0 to 7, and w + x satisfies 1 to 8,
v represents 0 or 1. )).

In the general formula (XXVII), T is 1 to 8
The alcohol having a T as a residue is a monohydric alcohol 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 and araliphatic alcohols such as phenylethyl alcohol; and partially etherified products thereof as dihydric alcohols, for example, linear or branched such as ethylene glycol, propylene glycol, butylene glycol, neopentylene glycol, and tetramethylene glycol. Aromatic alcohols such as catechol, resorcinol, bisphenol A, bisphenyldiol, and their partially etherified products For example, glycerin; trimethylolpropane; trimethylolethane; trimethylolbutane; linear or branched aliphatic alcohols such as 1,3,5-pentanetriol, and aromatics such as pyrogallol, methylpyrogallol, and 5-sec-butylpyrogallol. Aliphatic alcohols and their partially etherified compounds as tetrahydric to octahydric alcohols such as pentaerythritol, diglycerin, sorbitan, triglycerin, sorbitol, dipentaerythritol, tetraglycerin, pentaglycerin, hexaglycerin, and tripentaerythritol And partially etherified products thereof.

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

As a method for producing the polyether ketone represented by the general formula (XXVII), 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 perfluoroalkylvinyl ether. Examples of reactive products of alkane and perfluoro alkyl vinyl ether of the general formula (XXVIII) (wherein, n represents an integer of _{6~20.) C n H 2n +} 2 ··· (XXVIII) is represented by (XXIX), wherein m is an integer of 1 to 4 and a perfluoroalkyl vinyl ether represented by the general formula (XXIX) CF ₂ = CFOC _m F _{2m + 1} . resulting Te general formula _{(XXX) C n H (2n} + 2-y) (CF 2 -CFHOC m F 2m + 1) y ··· (XXX) ( wherein, y represents an integer of 1 to 4, n and m are the same as those described above.).

The alkane represented by the general formula (XXVIII) may be linear, branched or cyclic, and specific examples thereof include n-octane; n-decane; n-dodecane; Cyclooctane; cyclododecane; 2,2,4
-Trimethylpentane and the like,
Specific examples of the perfluoroalkyl vinyl ether represented by the general formula (XXIX) include perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro n-propyl vinyl ether, and perfluoro n-
Butyl vinyl ether and the like can be mentioned. The refrigerating machine oil composition of the present invention has excellent lubricating performance, and in particular, can reduce wear of a lubricated portion using an aluminum material. In addition, in the present invention, since an additive having high oxidation stability is used as an additive, the oxidation stability of the refrigerator oil composition is also high.

[0105]

[Evaluation conditions]

Material: Aluminum (A-4032) / Aluminum (A-
4032) Combination Oil temperature: 50 ° C Load: 50N Sliding speed: 0.6m / sec Experiment time: 20min Atmosphere: R134a sealed, 0.5MPa

[0106]

[Table 1]

Example 3, Reference Example 3 and Comparative Example 2 As a base oil, a random copolymer of polyvinyl ethyl ether (a) and polyisobutyl ether (b) [a unit / b unit = 9/1, kinematic viscosity] 68 mm ² / s (40 ° C.), number average molecular weight 720, abbreviated as PVE. And a refrigeration oil composition was prepared using 1% by weight of glyceryl ether (isooctadecyl glyceryl ether) or TCP as an additive based on the total amount of the composition. The abrasion resistance performance of the composition was evaluated using a refrigerant-tight block-on-ring tester in the following manner. Table 2 shows the results. [Evaluation conditions] Material: Aluminum (A-4032) / Cast iron combination (Block; Aluminum ring; Cast iron) Oil temperature: 50 ° C Load: 100N Sliding speed: 0.6 m / sec Experiment time: 20 min Atmosphere: R134a sealed , 0.5MPa

[0108]

[Table 2]

Example 3, Reference Example 4 and Comparative Example 3 As a base oil, a random copolymer of polyvinyl ethyl ether (a) and polyisobutyl ether (b) [a unit / b unit = 9/1, kinematic viscosity] 68 mm ² / s (40 ° C.), number average molecular weight 720, abbreviated as PVE. And a refrigeration oil composition was prepared using 1% by weight of glyceryl ether (isooctadecyl glyceryl ether) or TCP as an additive based on the total amount of the composition. The abrasion resistance performance of the composition was evaluated using a refrigerant-tight block-on-ring tester in the following manner. Table 3 shows the results. [Evaluation conditions] Material: Combination of cast iron / high-speed steel (block; high-speed steel ring; cast iron) Oil temperature: 100 ° C Load: 1200N Sliding speed: 0.4 m / sec Experiment time: 120 min Atmosphere: R134a enclosed 0 .5MPa

[0110]

[Table 3]

[0111]

According to the present invention, a refrigerant of a hydrofluorocarbon type, a hydrocarbon type, an ether type, a carbon dioxide type or an ammonia type, preferably a chlorofluorocarbon type refrigerant which is a problem with environmental pollution is used as a refrigerant. When a hydrofluorocarbon-based material that can be used as a substitute is used, a refrigerating machine oil composition having excellent lubricating performance and capable of reducing abrasion of a lubricated portion using an aluminum material, in particular, can be provided.

Claims (5)

[Claims] 1. A base oil comprising mineral oil and / or synthetic oil,
A glyceryl ether compound represented by the following general formula (I) R ¹ -OCH ₂ CH (OH) CH ₂ OH (I) wherein R ¹ represents an alkyl group having 10 to 22 carbon atoms. Is contained in an amount of 0.01 to 10% by weight based on the total amount of the composition. 2. The refrigerating machine oil composition according to claim 1, wherein the base oil is an oxygen-containing synthetic oil. 3. The oxygen-containing synthetic oil is polyvinyl ether,
The refrigerating machine oil composition according to claim 2, which is at least one selected from a polyol ester and a polyalkylene glycol. 4. The following general formula (XVI): (Wherein R ⁴² represents a hydrocarbon group having or not having an ether bond in a molecule having 1 to 3 carbon atoms) and a structural unit (A) represented by the following general formula (XVII): (Wherein, R ⁴³ represents a hydrocarbon group having or not having an ether bond in a molecule having 3 to 20 carbon atoms.) A polyvinyl ether copolymer having a structural unit (B) represented by the following formula: R ⁴² of structural unit (A) and structural unit (B)
R ⁴³ are not the same. ] A base oil containing the following general formula _{^{(I) R 1 -OCH 2 CH}} (OH) CH 2 OH ··· (I) ( In the formula, R ¹ represents an alkyl group having 10 to 22 carbon atoms.) A refrigeration oil composition comprising 0.01 to 10% by weight of the glyceryl ether compound represented by the formula (1) based on the total amount of the composition. 5. The refrigerating machine oil composition according to claim 4, wherein in the structural unit (A), R ⁴² is an ethyl group, and in the structural unit (B), R ⁴³ is an isobutyl group.