JP2000256692A - Refrigerator oil composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a refrigerator oil composition which is excellent in decreasing friction in both the oily region and the extreme pressure region of a friction part between an Al material and an iron material by compounding a base oil comprising a mineral oil and/or a synthetic oil with a partial ester of a polyhydric alcohol and a fatty acid and an acidic phosphoric ester (amine salt), each in a specified amount. SOLUTION: Based on the composition, 0.01-5 wt.% partial ester of a polyhydric alcohol, preferably a tri- or tetrahydric alcohol, and a fatty acid, preferably a 12-24C fatty acid and 0.001-1 wt.% acidic phosphoric ester (amine salt) are compounded into a base oil. Preferably, the base oil is at least one oxygen-containing synthetic oil selected from among polyvinyl ethers, polyol esters, and polyalkylene glycols. A polyvinyl ether which is a copolymer having structural units represented by formula I and structural units represented by formula II is preferable. In the formulas, R45 is a 1-3C hydrocarbon group; and R46 is a 3-20C hydrocarbon group provided that R45 is not the same as R46.

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 refrigerating machine oil composition having excellent lubricating performance, particularly in a frictional portion between an aluminum material and an iron material, in either an oily region or an extreme pressure region. Can also exhibit good friction and wear reduction effects and does not cause environmental pollution.
The present invention relates to a refrigerating machine oil composition suitable as a lubricating oil for a refrigerating machine using a chlorine-free Freon refrigerant such as 4a.

[0002]

2. Description of the Related Art In general, a compression refrigerator comprises at least a compressor, a condenser, an expansion mechanism (such as an expansion valve), an evaporator, or a dryer, and a liquid mixture of refrigerant and lubricating oil is sealed. It has a structure that circulates through the system. In such a compression refrigerator, dichlorodifluoromethane (R12), chlorodifluoromethane (R22), and the like have been conventionally used in many cases as a refrigerant, and various mineral oils and synthetic oils have been used as a lubricating oil. .

However, since R12 and R22 may cause environmental pollution such as destruction of the ozone layer existing in the stratosphere, regulations thereof have recently become stricter worldwide. For this reason, non-chlorinated chlorofluorocarbon compounds such as hydrofluorocarbons have attracted attention as new refrigerants. This non-chlorinated Freon compound, especially R
Hydrofluorocarbons represented by 134a are preferable as compression type refrigerating machine oils, as they have no risk of destruction of the ozone layer and can be replaced with R12 or the like without substantially changing the structure of a conventional refrigerating machine. It is.

[0004] The new alternative CFC-based refrigerant has different properties from the conventional CFC-based refrigerant, and as a refrigerating machine oil used in combination therewith, for example, polyalkylene glycol, polyester, polyol ester, polycarbonate, polyvinyl having a specific structure. It is known that those obtained by using ether, alkylbenzene or the like as a base oil and blending various additives with the base oil 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 iron material of the compressor for an air conditioner refrigerator, and pose a serious problem in practical use. I have. There are rotary type, scroll type and reciprocating type compressors for air conditioner refrigerators. The friction part between aluminum and iron is a bearing part for rotary type, Oldham ring part for scroll type, and connecting rod (aluminum) / reciprocating type for reciprocating type. There is a piston pin (steel) part. In terms of lubrication conditions, the bearing and Oldham ring are
A region in which the oily effect of the lubricating oil can be exhibited in a lubricating portion having a relatively low surface pressure (hereinafter referred to as an oily region).
The piston pin portion is a region where the surface pressure is relatively high and the extreme pressure performance of the lubricating oil is required (hereinafter, referred to as an extreme pressure region).
Therefore, as a refrigerating machine oil, a specification that can be used for any type of compressor is desired. Therefore, the development of an additive exhibiting a good friction and wear reduction effect in both the oily region and the extreme pressure region is desired. . Conventionally, orthophosphoric 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, these additives are effective for the combination of iron and iron as the material of the friction portion, but do not have the effect of reducing friction in the extreme pressure region for the combination of iron and aluminum, An alternative extreme pressure agent is required.

[0006]

SUMMARY OF THE INVENTION The present invention has been made in view of the above, and has excellent lubricating performance. In particular, in a friction portion between an aluminum material and an iron material, either of an oily region or an extreme pressure region is used. It is an object of the present invention to provide a refrigerating machine oil composition which can exhibit a good friction reducing effect even in a refrigerating machine using a non-chlorinated chlorofluorocarbon refrigerant such as R134a which does not cause environmental pollution. It is.

[0007]

Means for Solving the Problems As a result of intensive studies, the present inventors have found that the use of an additive in which a partial ester of a specific polyhydric alcohol and an acidic phosphoric acid ester are combined allows the present invention to be used. It has been found that the object can be effectively achieved, and the present invention has been completed. That is, the gist of the present invention is as follows. (1) 0.01 to 5% by weight of (a) a partial ester of a polyhydric alcohol and a fatty acid and (b) acidic phosphates, based on the total amount of the composition, in a base oil composed of mineral oil and / or synthetic oil Alternatively, a refrigerator oil composition comprising 0.001 to 1% by weight of an amine salt thereof. (2) The refrigerator oil composition according to the above (1), wherein the component (a) is a partial ester of a tri- or tetrahydric polyhydric alcohol and a fatty acid having 12 to 24 carbon atoms. (3) The refrigerating machine oil composition according to the above (1) or (2), wherein the base oil is an oxygen-containing synthetic oil. (4) The refrigerating machine oil composition according to the above (3), wherein the oxygen-containing synthetic oil is at least one selected from polyvinyl ether, polyol ester and polyalkylene glycol. (5) The polyvinyl ether has the following general formula (XIX)

[0008]

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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 (XX):

[0010]

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(Wherein, R ⁴⁶ represents a hydrocarbon group having or not having an ether bond in the molecule having 3 to 20 carbon atoms) and a structural unit (B) represented by the following formula: [However, R ⁴⁵ of the structural unit (A) and R ⁴⁶ of the structural unit (B) are not the same. ] The refrigerating machine oil composition according to the above (4), wherein (6) The refrigerating machine oil composition according to the above (5), wherein in the structural unit (A), R ⁴⁵ is an ethyl group, and in the structural unit (B), R ⁴⁶ is an isobutyl group.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. 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 may be those generally used as a base oil of a refrigerator oil, and are not particularly limited, but have a kinematic viscosity at 40 ° C of ² to 500 mm ² / s, particularly 5 to 200 m
Those in the range of m ² / s, 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. Mineral oils include, for example, paraffinic mineral oils, naphthenic mineral oils, intermediate mineral oils, 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, Si, N, etc.), specifically, polyvinyl ethers, polyol esters, polyalkylene glycols, polyesters, carbonate derivatives,
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, (a) and (b) blended in the base oil
The components will be described. (A ) Component The component ( a) constituting the refrigerator oil composition of the present invention is a partial ester of a polyhydric alcohol and a fatty acid, and is trivalent or tetravalent polyvalent in terms of friction reduction effect and volume resistivity. Partial esters of alcohols and fatty acids having 12 to 24 carbon atoms are preferred. Specific examples of the trihydric or tetrahydric polyhydric alcohol include trimethylolethane, trimethylolpropane, glycerin, erythritol, and pentaerythritol. Among them, glycerin, trimethylolpropane, and trimethylolethane are particularly preferable. Glycerin is preferred.

The fatty acid having 12 to 24 carbon atoms may be linear or branched, and may be saturated or unsaturated. Specific examples of linear saturated fatty acids include lauric acid, tridecylic acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, nonadecylic acid, arachiic acid, behenic acid, and lignoceric acid. it can. As a linear unsaturated fatty acid, specifically,
Lindelic acid, 5-lauroleic acid, tuzuic acid, myristolic acid, zomaric acid, petroselinic acid, oleic acid,
Examples thereof include elaidic acid, codoic acid, erucic acid, and seracoleic acid.

Specific examples of branched saturated fatty acids include various methylundecanoic acids, various propylnonanoic acids,
Various methyl dodecanoic acids, various propyl decanoic acids, various methyl tridecanoic acids, various methyl tetradecanoic acids, various methyl pentadecanoic acids, various ethyl tetradecanoic acids, various methyl hexadecanoic acids, various propyl tetradecanoic acids,
Various ethyl hexadecanoic acids, various methyl heptadecanoic acids, various butyl tetradecanoic acids, various methyl octadecanoic acids, various ethyl octadecanoic acids, various methyl nonadecanoic acids, various ethyl octadecanoic acids, various methyl eicoic acids, various propyl octadecanoic acids, various butyl octadecanoic acids, Various methyl docosanoic acids, various pentyl octadecanoic acids, various methyl tricosanoic acids, various ethyl docosanoic acids, various propyl hexaeicosanoic acids, various hexyl octadecanoic acids; 4,4-dimethyldecanoic acid; 2-ethyl-3-methylnonanoic acid; 2-dimethyl-4-ethyloctanoic acid; 2-propyl-3-methylnonanoic acid; 2,
3-dimethyldodecanoic acid; 2-butyl-3-methylnonanoic acid; 3,7,11-trimethyldodecanoic acid; 4,4-
Dimethyltetradecanoic acid; 2-butyl-2-pentylheptanoic acid; 2,3-dimethyltetradecanoic acid;
12-trimethyltridecanoic acid; 14,14-dimethylpentadecanoic acid; 3-methyl-2-heptylnonanoic acid;
2,2-dipentylheptanoic acid; 2,2-dimethylhexadecanoic acid; 2-octyl-3-methylnonanoic acid;
3-dimethylheptadecanoic acid; 2,4-dimethyloctadecanoic acid; 2-butyl-2-heptylnonanoic acid;
20-dimethylheneicoic acid and the like can be mentioned.

As branched unsaturated fatty acids, 5-methyl-2-undecenoic acid, 2-methyl-2-dodecenoic acid,
Examples thereof include 5-methyl-2-tridecenoic acid, 2-methyl-9-octadecenoic acid, 2-ethyl-9-octadecenoic acid, 2-propyl-9-octadecenoic acid, and 2-methyl-2-eicosenoic acid. . 12 or more carbon atoms
Among the 24 fatty acids, stearic acid, oleic acid, 16
-Methylheptadecanoic acid (isostearic acid) and the like are preferred.

The partial ester is preferably a monocarboxylic acid ester, a dicarboxylic acid ester or a mixture thereof. As partial esters of fatty acids of polyhydric alcohols,
Specifically, glycerin monooleate, glycerindiolate, glycerin monostearate, glycerin distearate, glycerin monoisostearate, glycerin dimonoisostearate and the like can be mentioned as preferable examples.

The above component (a) may be used alone or in combination of two or more. The amount of the component (a)
It is 0.01 to 5% by weight based on the total amount of the composition. If the amount is too small, the object of the present invention is not sufficiently exhibited,
If the amount is too large, the effect is not improved for the amount, and the solubility in the base oil decreases. The preferred amount is in the range of 0.1 to 2% by weight. ( B) Component Next, as the acidic phosphoric acid ester of the component (b) constituting the lubricating oil composition for metal working of the present invention, the following general formulas (I) and (II)

[0021]

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(Wherein R ¹ and R ² represent an alkyl group, an alkenyl group, an alkylaryl group, and an arylalkyl group having 4 to 30 carbon atoms, and may be the same or different). Acid ester and the following general formula (III)

[0023]

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(Wherein, R ³ and R ⁴ represent an alkyl group, an alkenyl group, an alkylaryl group, and an arylalkyl group having 4 to 30 carbon atoms, and may be the same or different). There are acid esters. The orthophosphoric ester is obtained by mixing the diester of the above general formula (I) with the general formula (II)
Is a mixture of monoesters. Specifically, for example,
2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate, isostearyl acid phosphate, oleic acid And the like.

Specific examples of the phosphite include dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, and diphenyl hydrogen phosphite. Among the above acidic phosphates, for example, 2
-Ethylhexyl acid phosphate, stearyl acid phosphate, oleyl acid phosphate and the like.

Examples of amines which form an amine salt with these include, for example, the following general formula (IV): R _n NH _3-n (IV) (where R is an alkyl group having 3 to 30 carbon atoms) Or an alkenyl group, an aryl group or an arylalkyl group having 6 to 30 carbon atoms, or a hydroxyalkyl group having 2 to 30 carbon atoms, and n represents 1, 2 or 3. When there are a plurality of R, a plurality of R May be the same or different.), A monosubstituted amine, a disubstituted amine or a trisubstituted amine. The alkyl group or alkenyl group having 3 to 30 carbon atoms in R in the general formula (IV) may be linear, branched, or cyclic.

Here, examples of the monosubstituted amine include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, benzylamine, and the like. Examples include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine. Benzyl monoethanolamine, phenyl monoethanolamine, tolyl monopropanol and the like. Examples of trisubstituted amines include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl.・ Monopropanolamine, dioctyl monoethanolamine,
Dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine,
Examples include stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine, and tripropanolamine. it can.

The above component (b) may be used alone or in combination of two or more. The amount of the component (b)
It is 0.001 to 1% by weight based on the total amount of the composition. If the amount is too small, the object of the present invention is not sufficiently exhibited. If the amount is too large, the effect is not improved for the amount, and the solubility in the base oil decreases. The preferred amount is in the range of 0.003 to 0.05% 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 tricresiphosphate; phenolic and amine antioxidants; furthermore, phenylglycidyl ether and cyclohexene oxide. And acid scavengers such as epoxy compounds such as epoxidized soybean oil; copper deactivators such as benzotriazole and benzotriazole derivatives; and defoamers such as silicone oil and fluorinated silicone oil.

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. A mixture having a ratio of 50:50 (hereinafter, referred to as R507) can be given. Finally, the oxygen-containing synthetic oil used as the base oil will be described in detail. As the polyvinyl ether, for example, the general formula (V)

[0031]

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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 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 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 the polyvinyl ether compound (1) having the structural unit represented by the formula (1). Further, a structural unit represented by the above general formula (V) and the following general formula (VI)

[0033]

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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 (V) 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 (V) represents a divalent hydrocarbon group having 1 to 10, preferably 2 to 10 carbon atoms or a divalent ether-bonded oxygen-containing carbon group having 2 to 20 carbon atoms. A hydrogen group is shown. Here, the divalent hydrocarbon group having 1 to 10 carbon atoms specifically means a methylene group; an ethylene group; a phenylethylene group; a 1,2-propylene group;
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; ethylcyclohexane; dimethylcyclohexane; an alicyclic group having two binding sites to an alicyclic hydrocarbon such as propylcyclohexane, various phenylene groups, various methylphenylene groups, various ethylphenylene groups, various dimethylphenylene groups; Divalent aromatic hydrocarbon groups such as various naphthylene groups; toluene; xylene; alkyl aromatic groups having a monovalent bonding site in the alkyl group portion and the aromatic portion of an alkyl aromatic hydrocarbon such as ethylbenzene, xylene; ; Polyalkyl fragrances such as diethylbenzene An alkyl aromatic group having a bonding site in the alkyl group moiety of the hydrocarbon can be exemplified. 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 (V), a represents the number of repetitions of R ⁸ O, and the average value is 0.
It is a number ranging from 10 to 10, preferably from 0 to 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 (V) represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, specifically, a methyl group or 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 methyl cyclohexyl groups , Various ethylcyclohexyl groups, various propylcyclohexyl groups, various cycloalkyl groups such as dimethylcyclohexyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various Aryl groups such as butylphenyl group and various naphthyl groups, Jill group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups,
Examples include various arylalkyl groups of a phenylbutyl group.

This polyvinyl ether compound (1)
Has a structural unit represented by the general formula (V), 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 3.5 to 7.0.
Those in the range of 0 are preferred. If the molar ratio is less than 3.5, the hygroscopicity may increase, and if it exceeds 7.0, the compatibility with the refrigerant may decrease.

Further, a polyvinyl ether compound (2)
Is a block or random copolymer having a structural unit represented by the general formula (V) and a structural unit represented by the general formula (VI), and in the general formula (VI) , 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 (V).
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 random copolymer having the structural unit represented by the general formula (V) and the structural unit represented by the general formula (VI) is as follows: It may be appropriately selected according to the desired kinematic viscosity. The polyvinyl ether compound preferably has a carbon / oxygen molar ratio in the range of 3.5 to 7.0. If the molar ratio is less than 3.5, 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 which can be used here is represented by the following general formula (VII)

[0043]

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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 can be mentioned. 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 (VI
II)

[0045]

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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 has the general formula (IX) or (X)

[0047]

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[0048] (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 represented by the general formula (XI) or (XII)

[0049]

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[0050] (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 general formula (IX) or (X), and the other end is represented by the general formula (XIII)

[0051]

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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 from each other). Are preferred. Among such polyvinyl ether compounds, the following compounds are particularly suitable as the base oil of the refrigerator oil composition of the present invention. (1) one end of which is represented by the general formula (IX) or (X) and the other end has a structure represented by the general formula (XI) or (XII); 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 hydrocarbon group having 1 to 20 carbon atoms. (2) having only the structural unit represented by the general formula (V), one end of which is represented by the general formula (IX),
And the remaining terminal has a structure represented by the general formula (XI),
In the general formula (V), 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.

(3) One of the terminals has a structure represented by the general formula (IX) or (X), and the other terminal has a structure represented by the general formula (XIII). ^{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 (V), one end of which is represented by the general formula (IX),
And the remaining terminal has a structure represented by the general formula (XII),
In the general formula (V), 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.

In the present invention, there is provided a structural unit represented by the general formula (V), one end of which is represented by the general formula (IX) and the other end is represented by the general formula (XIV)

[0055]

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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; 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, the following general formula (XV) or (XVI)

[0057]

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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 3,000 (preferably 300 to 2,000).
000), wherein one end is represented by the general formula (XVII) or (XVIII)

[0059]

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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 (XIX)

[0061]

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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), a polyvinyl ether homopolymer having a structural unit (A) represented by the following formula: Or the structural unit (A) and the following general formula (XX)

[0063]

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(Wherein R ⁴⁶ 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 ^{45 of} the structural unit (A) and R ⁴⁶ of the structural unit (B) are not the same. ] Is particularly preferably used. R ⁴⁵ is an alkyl group having 1 to 3 carbon atoms, and R ⁴⁶ is an alkyl group having 3 carbon atoms.
More preferably an alkyl group having from 20 to 20, particularly a homopolymer wherein R ⁴⁵ is an ethyl group or a copolymer wherein R ⁴⁵ is a methyl or ethyl group and R ⁴⁶ is an alkyl group having 3 to 6 carbon atoms In the case where R ⁴⁵ is an ethyl group and R ⁴⁶ is an isobutyl group, a copolymer is most suitable, and in this case, the ratio of the structural unit (A) to the structural unit (B) is 95% by mole. : 5
５０50: 50 is preferable, and 95: 5 to 70:30.
Is more preferable. The copolymer may be in a random form or a block form.

The polyvinyl ether compound can be produced by subjecting the above-mentioned monomer to radical polymerization, cationic polymerization, radiation polymerization, or the like. For example, a vinyl ether-based monomer is polymerized by the following method to obtain a polymer having a desired viscosity. For the initiation of the polymerization, it is possible to use a combination of an adduct of a carboxylic acid with water, an alcohol, a phenol, an acetal or a vinyl ether with a Bronsted acid, Lewis acid or organometallic compound. it can. Examples of Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid,
Sulfuric acid, trichloroacetic acid, trifluoroacetic acid and the like. Examples of 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; 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 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 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 monomer represented by the general formula (VII) can be started at a temperature of -80 to 150 ° C., and usually at a temperature of -80 to 150 ° C., depending on the type of the raw material and the initiator. It can be performed at a temperature in the range of 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-based monomer represented by the general formula (VII). 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, a usual separation / purification method is applied as necessary to obtain the desired polyvinyl ether compound having the structural unit represented by the general formula (V).

As described above, the polyvinyl ether compound used in the present invention has a carbon / oxygen molar ratio of 3.5 to 7.0.
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-based 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 polyol ester include a carboxylic acid ester of a polyvalent hydroxy compound containing at least two hydroxyl groups. For example, the general formula (XXI) R ⁴⁷ [OCOR ⁴⁸ ] _f. Wherein R ⁴⁷ is a hydrocarbon group, R ⁴⁸ 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 ⁴⁸ may be the same or different.) Can be used.

In the general formula (XXI), R ⁴⁷ represents a hydrocarbon group, which may be linear or branched, and is preferably an alkyl group having 2 to 10 carbon atoms. R ⁴⁸ 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 (XX
The polyol ester represented by I) is a polyhydric alcohol represented by the general formula (XXII) R ⁴⁷ (OH) _f (XXII) (wherein R ⁴⁷ and f are the same as described above). And a carboxylic acid represented by the general formula (XXIII) R ⁴⁸ COOH (XXIII) (where R ⁴⁸ is the same as described above) or a reactive derivative thereof such as an ester or an acid halide. Can be obtained.

Examples of the polyhydric alcohol represented by the general formula (XXII) 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 (XXIII) include, 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-mentioned polyalkylene glycol is represented by the following general formula (XXIV) R ⁴⁹ -[(OR ⁵⁰ ) _g -OR ⁵¹ ] _h (XXIV) (where R ⁴⁹ 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 ⁵⁰ is an alkylene group having 2 to 4 carbon atoms, R ⁵¹ 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 (XXIV), R ⁴⁹ and R ⁵¹
The alkyl group in may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like. 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 ⁴⁹ and R ⁵¹ 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.

R⁴⁹And R⁵¹Is an alkyl group or
When it is an acyl group, R⁴⁹And R ⁵¹Identical to each other
May also be different. When h is 2 or more,
Multiple Rs in one molecule⁵¹May be the same or different.
R⁴⁹Having 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.

When the number of carbon atoms in the aliphatic hydrocarbon group exceeds 10, the compatibility with the refrigerant is reduced, and phase separation may occur. The preferred number of carbon atoms is 2 to 6. The general formula (XX
R ^{50 in} IV) 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.

In the general formula (XXIV), h is an integer of 1 to 6, and is determined according to the number of R ⁴⁹ binding sites. For example, R
If ⁴⁹ is an alkyl group or an acyl group, h is 1, R ⁴⁹
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 (XXIV) 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 (XXIV) 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 (XXV)

[0087]

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(Wherein, R ⁵² represents an alkylene group having 1 to 10 carbon atoms, and R ⁵³ 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. R ⁵² in the general formula (XXV) represents an alkylene group having 1 to 10 carbon atoms, specifically, a methylene group, an ethylene group, a propylene group, an ethylmethylene group, a 1,1-dimethylethylene group, 2-dimethylethylene group, n-butylethylene group, isobutylethylene group, 1-ethyl-2-methylethylene group, 1-ethyl-1-methylethylene group, trimethylene group, tetramethylene group, pentamethylene group, and the like. But is preferably an alkylene group having 6 or less carbon atoms. R ⁵³ represents an alkylene group having 2 to 10 carbon atoms or an oxaalkylene group having 4 to 20 carbon atoms. The alkylene group is, specifically, a specific example of R ⁵² (however,
(Excluding a methylene group), preferably having 2 carbon atoms.
And the oxaalkylene group is specifically a 3-oxa-1,5-pentylene group;
Dioxa-1,8-octylene group; 3,6,9-trioxa-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-tetramethyl-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-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-1,2,2,
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,
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-methyl-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-
Examples thereof include a 1,11-undecylene group.
Note that R ⁵² and R ⁵³ may be the same or different for each structural unit.

The aliphatic polyester derivative represented by the general formula (XXV) 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. As the carbonate derivative, for example, a compound represented by the general formula (XXVI)

[0090]

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(Wherein R ⁵⁴ and R ⁵⁶ 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. Often, R ⁵⁵ is an alkylene group having 2 to 24 carbon atoms, i is an integer of 1 to 100, and j is an integer of 1 to 10.).

In the above general formula (XXVI), R ⁵⁴ and R
⁵⁶ 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.

[0093] The hydrocarbon group having an ether bond having 2 to 30 carbon atoms, for example, the general formula ^{(XXVII) - (R 57 -O} ) k -R 58 ··· (XXVII) wherein, R ⁵⁷ Is an alkylene group having 2 or 3 carbon atoms (ethylene group, propylene group, trimethylene group), and R ⁵⁸ is an aliphatic, alicyclic or aromatic hydrocarbon group having 28 or less carbon atoms (R ⁵⁴
And those similar to the groups mentioned in the specific examples of R ^56), k is 1
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 ⁵⁴ and R ^56, Among them, n- butyl group, an isobutyl group, an isoamyl group, a cyclohexyl group, isoheptyl group, 3-methylhexyl group; 1,3-dimethylbutyl group, a hexyl group, an octyl 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 Preferred are an alkylene glycol monoalkyl ether group such as an ether group and a tripropylene glycol mono n-butyl ether group.

Further, in the general formula (XXVI), R ⁵⁵
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 ⁵⁵ O, the plurality of R ⁵⁵ may be the same or different.

The polycarbonate represented by the general formula (XXVI) 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 (XXVIII) R ⁵⁹ -O- (R ⁶¹ O) _p -CO- (OR ⁶² ) _q -OR ⁶⁰ (XXVIII) (wherein R ⁵⁹ and R ⁶⁰ each have 1 carbon atom) Represents up to 20 aliphatic, cycloaliphatic, aromatic or araliphatic hydrocarbon groups, which may be the same or different;
⁶¹ and R ⁶² 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 general formula (XXVIII), specific examples of the aliphatic hydrocarbon group for R ⁵⁹ and R ⁶⁰ 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; 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 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 (XXVIII) 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-3-1492.
Any of those described in detail in Japanese Patent Publication No. 95 can be used. Further, as a carbonate derivative, a compound represented by the general formula (XXIX)

[0100]

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(Wherein, R ⁶³ and R ⁶⁴ 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 ⁶⁵ represents an alkylene group having 2 to 12 carbon atoms, and r represents an integer of 0 to 30).

In the general formula (XXIX), R ⁶³ and R ^63
64 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 ⁶⁵ 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 ⁶³ and R ⁶⁴ 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.

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; 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 ⁶⁵ include an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a butylene group, a 2-methyltrimethylene 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 above 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 (XXX)

[0106]

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(Wherein T is a monovalent to octavalent alcohol residue;
R ⁶⁶ is an alkylene group having 2 to 4 carbon atoms, R ⁶⁷ is a methyl group or an ethyl group, R ⁶⁸ and R ⁷⁰ 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,
⁶⁹ 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 (XXX), T is a monovalent to octahydric alcohol residue, and the alcohol having T as a residue is a monohydric alcohol such as methyl alcohol, ethyl alcohol, linear or branched alcohol. 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, straight or branched decyl alcohol, straight or branched undecyl alcohol, straight or branched dodecyl alcohol, straight or branched tridecyl alcohol, straight or branched tetradecyl alcohol, straight or branched Pentadecyl alcohol, linear or branched hexadecyl alcohol, linear or Aliphatic monohydric alcohols such as branched heptadecyl alcohol, linear or branched octadecyl alcohol, linear or branched nonadecyl alcohol, linear or branched eicosyl alcohol; phenol, methylphenol, nonylphenol, octylphenol, naphthol, etc. Aromatic alcohols such as benzyl alcohol and phenylethyl alcohol; and partially etherified products thereof as dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, neopentylene glycol, and tetramethylene glycol. Linear or branched aliphatic alcohols, such as aromatic alcohols such as catechol, resorcinol, bisphenol A, and bisphenyldiol; And the like as trihydric alcohols, for example, glycerin; trimethylolpropane; trimethylolethane; trimethylolbutane; linear or branched aliphatic alcohols such as 1,3,5-pentanetriol, pyrogallol, methylpyrogallol, Aromatic alcohols such as sec-butylpyrogallol and partially etherified products thereof are used as tetra- to octahydric alcohols, for example, pentaerythritol, diglycerin, sorbitan, triglycerin, sorbitol, dipentaerythritol, tetraglycerin, pentaglycerin. , Hexaglycerin, and tripentaerythritol, and their partially etherified products.

In the general formula (XXX), the alkylene group having 2 to 4 carbon atoms represented by R ⁶⁶ may be linear or branched, and specific examples include an ethylene group; Group; ethylethylene group; 1,1-dimethylethylene group; 1,2-dimethylethylene group and the like. In addition, carbon number 2 represented by R ^{68 to} R ⁷⁰
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 (XXX), s and u are 0
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, electric 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. Further, s × w R ⁶⁶ may be the same or different, and u × w R ⁶⁷ may be the same or different. When w is 2 or more, w s, u, v, R ⁶⁸ and R ⁶⁹ may be the same or different, and when x is 2 or more, x R ⁷⁰ may be the same or different. You may.

As a method for producing the polyether ketone represented by the general formula (XXX), 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 a secondary alkyloxy alcohol with zirconium hydroxide and a ketone (JP-A-3-1671)
49 publication) 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 (XXXI) (wherein, n represents an integer of _{6~20.) C n H 2n +} 2 ··· (XXXI) is represented by Perfluoroalkyl vinyl ether represented by the general formula (XXXII) CF ₂ ＣＦCFOC _m F _{2m + 1} ... (XXXII) (where m represents an integer of 1 to 4). resulting Te general formula _{(XXXIII) C n H (2n} + 2-y) (CF 2 -CFHOC m F 2m + 1) y ··· (XXXIII) ( 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 (XXXI) may be linear, branched or cyclic, and 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 (XXXII) include perfluoromethyl vinyl ether, perfluoroethyl vinyl ether, perfluoro n-propyl vinyl ether, and perfluoro n. -Butyl vinyl ether and the like.

[0114]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. [Example 1, Comparative Examples 1, 2 and Reference Example 1] As a base oil,
Polyvinyl ethyl ether (a) / polyisobutyl ether (b) random copolymer [a unit / b unit = 9 /
1, kinematic viscosity 68 mm ² / s (40 ° C), number average molecular weight 7
20], and to the base oil, the additives shown in Table 1
The composition was blended at the ratio shown in Table 1 based on the total amount of the composition to prepare a refrigerator oil composition. The lubricating performance of the composition in the extreme pressure region (hereinafter referred to as extreme pressure performance) in the following manner.
And an evaluation of lubrication performance in an oily region (hereinafter referred to as oily performance). Table 1 shows the results.

[Extreme pressure performance] Testing machine: Falex wear testing machine Material: Block / pin = A390 (aluminum) / AISI-3
135 (steel material) Oil temperature: room temperature Load: 1,000 lbs (4,450 N) Rotation speed: 290 rpm Experiment time: 30 min Atmosphere: R134a (blowing type) Evaluation item: Block wear width (mm) Test method: ASTM D 2670 −94

[Oil performance] Testing machine: Sealed block-on-ring testing machine Material: Block / ring = A4032 (aluminum material) / FC
250 (cast iron) Oil temperature: 70 ° C Load: 10 kg (100 N) Rotation speed: 300 rpm Experiment time: 30 min Atmosphere: R134a enclosure (0.6 MPa) Evaluation item: Block wear width (mm) Test method: Proceedings of the 1998 International Re
frigeration Conference at Purdue, (1998), p. 379

[0117]

[Table 1]

(Note) * 1: Glycerin monooleate * 2: Amine salt of oleyl acid phosphate * 3: Antioxidant (phenol type), acid scavenger (epoxy type) Antifoaming agent (silicone type) From Table 1 It can be seen that the refrigerating machine oil composition of the present invention has a synergistic effect of two kinds of additives in the polar performance and the oil performance.

[0119]

According to the present invention, it has excellent lubricating performance, and particularly in a friction portion between an aluminum material and an iron material.
Refrigeration oil composition suitable for lubricating oil of a refrigerator using a non-chlorinated chlorofluorocarbon refrigerant such as R134a, which can exhibit a good friction reducing effect in both the oily region and the extreme pressure region and does not cause environmental pollution. Things can be provided. Therefore, the refrigerating machine oil composition of the present invention can be applied to a refrigerating machine having all types of compressors such as a rotary type, a scroll type, and a reciprocating type.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C10M 105: 14 107: 24 129: 28 137: 04) C10N 30:02 30:06 40:30 (72) Inventor Shoichi Tominaga 3-1-1 Marunouchi, Chiyoda-ku, Tokyo F-term (reference) 4H104 BB33A BB34A BB35C BB37A BB44A BH02C BH03C BH05C CB02A CB13A CB14A CJ13A DA02A EB02 LA03 LA20 PA20

Claims (6)

[Claims] 1. A base oil comprising mineral oil and / or synthetic oil,
Based on the total amount of the composition, (a) 0.01 to 5% by weight of a partial ester of a polyhydric alcohol and a fatty acid and (b) 0.001 to 1% by weight of an acidic phosphate or an amine salt thereof.
A refrigerator oil composition characterized by being blended. 2. The refrigerating machine oil composition according to claim 1, wherein the component (a) is a partial ester of a trihydric or tetrahydric polyhydric alcohol and a fatty acid having 12 to 24 carbon atoms. 3. The oil according to claim 1, wherein the base oil is an oxygen-containing synthetic oil.
Or the refrigerator oil composition according to 2. 4. The refrigerating machine oil composition according to claim 3, wherein the oxygen-containing synthetic oil is at least one selected from polyvinyl ethers, polyol esters, and polyalkylene glycols. 5. The polyvinyl ether has the following general formula (XI)
X) (Wherein, R ⁴⁵ 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 (XX): (Wherein, R ⁴⁶ 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 ⁴⁵ of structural unit (A) and structural unit (B)
R ⁴⁶ are not the same. The refrigerating machine oil composition according to claim 4, wherein 6. The refrigerating machine oil composition according to claim 5, wherein in the structural unit (A), R ⁴⁵ is an ethyl group, and in the structural unit (B), R ⁴⁶ is an isobutyl group.