JP2008247995A - Freezer oil composition and working fluid composition for freezer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a freezer oil composition enabling the lubricity and refrigerant compatibility of a freezer oil to coexist in the presence of a refrigerant, and to provide a working fluid composition for freezers. <P>SOLUTION: This freezer oil composition comprises a hydrocarbon oil and an oxygen-containing oil in amounts of 20 to 95 mass% and 5 to 80 mass% respectively, based on the total amount of the freezer oil composition and is used together with a hydrofluorocarbon refrigerant which has a dynamic viscosity of ≥20 mm<SP>2</SP>/s at 40°C and in which the number of fluorine atoms is less than the number of hydrogen atoms. The working fluid composition for freezers comprises the freezer oil composition and a hydrofluorocarbon refrigerant in which the number of fluorine atoms is less than the number of hydrogen atoms. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a refrigerator oil composition and a working fluid composition for a refrigerator.

  Due to the problem of ozone depletion in recent years, CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon), which have been used as refrigerants in conventional refrigeration and air-conditioning equipment, are subject to regulation, and HFC (hydrofluorocarbon) as a refrigerant instead. in use.

As refrigerating machine oils for HFC refrigerants, esters, carbonates, PAGs (polyalkylene glycols), polyvinyl ethers and the like that are compatible with HFC refrigerants have been studied or used (for example, see Patent Documents 1 to 10 below). . In particular, HFC-134a has moderate compatibility with these oxygenated oils and has been put to practical use in car air conditioners and the like.
Japanese National Patent Publication No. 3-505602 Japanese Unexamined Patent Publication No. 3-88892 Japanese Patent Laid-Open No. 3-128991 Japanese Patent Laid-Open No. 3-128992 JP-A-3-200955 Japanese Patent Laid-Open No. 3-227397 JP-A-4-20597 JP-A-4-72390 Japanese Patent Laid-Open No. 4-218592 Japanese Patent Laid-Open No. 4-249593

  In recent years, in addition to the problem of ozone layer destruction, the problem of global warming has become more serious, and a refrigerant with a low global warming potential has been demanded. Although HFC-134a has an ozone depletion potential (ODP) of 0, the global warming potential (GWP: Global. Warming Potential) is as high as 1,300.

  Then, although examination of the alternative refrigerant | coolant of HFC-134a is advanced, selecting the optimal refrigerating machine oil for every refrigerant | coolant is understood also from the example of refrigerant | coolant substitution from CFC and HCFC mentioned above to HFC. Not always easy.

  One of the factors that make it difficult to develop refrigerating machine oil due to refrigerant replacement is that the refrigerant compatibility and refrigerating solvent viscosity of refrigerating machine oil are in conflict.

  That is, in the refrigerant circulation system of the refrigerating and air-conditioning equipment, due to the mechanism, a part of the refrigerating machine oil in the refrigerant compressor is discharged together with the refrigerant to the circulation flow path, so that the amount of the refrigerating machine oil in the refrigerant compressor is insufficient. In order to prevent poor lubrication or the like, it is important that the discharged refrigeration oil returns to the refrigerant compressor through the circulation channel (oil returnability). Therefore, the refrigerating machine oil is required to have compatibility with the refrigerant.

  However, when the refrigerant compatibility of the refrigeration oil is high, the viscosity of the fluid composition (refrigerant dissolution viscosity), which is a mixture of the refrigeration oil and the refrigerant, tends to decrease due to the refrigerant being dissolved in the refrigeration oil in the refrigeration system. It is in. And if refrigerant melt viscosity falls, we are anxious about problems, such as blow-by in the compression part of a refrigerant compressor, and poor lubrication.

  In addition, refrigeration oil is used in the presence of a refrigerant, so that the usage environment is greatly different from other lubricating oils used in an air atmosphere or the like. This contributes to the fact that the lubricity improvement technology in other lubricating oil fields cannot be directly applied to refrigeration oil.

  The present invention has been made in view of such circumstances, and a refrigerating machine oil composition and a working fluid for a refrigerating machine that can achieve both lubricity and refrigerant compatibility of refrigerating machine oil in the presence of a refrigerant. An object is to provide a composition.

  As a result of intensive studies to achieve the above object, the present inventors have determined that a refrigerating machine oil containing a hydrocarbon oil and an oxygen-containing oil in a specific ratio and having a specific kinematic viscosity has a number of fluorine atoms and a hydrogen atom. It has been found that the above problems can be solved by using together with a hydrofluorocarbon refrigerant whose number satisfies a specific condition, and the present invention has been completed.

That is, this invention contains 20-95 mass% hydrocarbon oil and 5-80 mass% oxygen-containing oil on the basis of the refrigerator oil composition whole quantity, and kinematic viscosity in 40 degreeC is 20 mm < ² > /. Provided is a refrigerating machine oil composition characterized by being used together with a hydrofluorocarbon refrigerant having a number of s or more and a fluorine atom number less than a hydrogen atom number.

  The hydrofluorocarbon refrigerant used together with the refrigerating machine oil composition of the present invention is preferably 1,1-difluoroethane. The refrigerator oil composition of the present invention exhibits a particularly excellent effect in the presence of 1,1-difluoroethane. In addition, 1,1-difluoroethane may be used independently and may be used as a mixed refrigerant with another refrigerant.

  In the refrigerating machine oil composition of the present invention, the oxygen-containing oil is preferably at least one selected from esters, polyglycols and polyvinyl ethers.

  Moreover, this invention provides the working fluid composition for refrigerators containing the refrigerating machine oil composition of the said invention, and the hydrofluorocarbon refrigerant | coolant whose number of fluorine atoms is less than the number of hydrogen atoms.

  ADVANTAGE OF THE INVENTION According to this invention, the refrigerating machine oil composition and the working fluid composition for refrigerating machines which can make the lubricity and refrigerant | coolant compatibility of refrigerating machine oil compatible in the presence of a refrigerant are provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  The hydrocarbon oil used in the present invention includes both mineral oil and synthetic hydrocarbon oil. Specific examples include naphthenic and paraffinic mineral oils, olefin polymers, naphthalene compounds, alkylbenzenes, and mixtures of two or more thereof.

  Mineral oils include solvent removal, solvent extraction, hydrocracking, solvent removal from lubricating oil fractions obtained by atmospheric distillation and vacuum distillation of paraffinic, intermediate or naphthenic crudes. Mention may be made of paraffinic or naphthenic mineral oils obtained by applying a suitable combination of one or more refining means such as dewaxing, catalytic dewaxing, hydrorefining, sulfuric acid washing and clay treatment.

  Among these mineral oils, it is preferable to use highly refined mineral oil from the viewpoint of superior stability. The highly refined mineral oil used in the present invention preferably has a non-aromatic unsaturation (unsaturation) of 10% or less. If this degree of unsaturation is more than 10%, it may cause sludge generation and clogging of the capillary. From this point, in the present invention, the degree of unsaturation is more preferably 5% or less, still more preferably 1% or less, and most preferably 0.1% or less. Specific examples of such highly refined mineral oil include, for example, a distillate obtained by atmospheric distillation of paraffinic crude oil, intermediate crude oil or naphthenic crude oil, or distillation of residual oil of atmospheric distillation under reduced pressure. Examples include refined oil obtained by refining oil according to a conventional method, deep dewaxed oil obtained by further deep dewaxing after refining, and hydrotreated oil obtained by hydrotreatment. . In this case, the purification method is not particularly limited, and various methods are used.

  Usually, (a) hydrogenation treatment, (b) dewaxing treatment (solvent dewaxing or hydrodewaxing), (c) solvent extraction treatment, (d) alkali washing or sulfuric acid washing treatment, (e) white clay treatment alone Or in combination in an appropriate order. It is also effective to repeat the same process in multiple stages. For example, (i) a method for hydrotreating distillate oil, or a method for performing alkali washing or sulfuric acid washing treatment after hydrogenation treatment, and (ii) a method for dewaxing treatment after hydrogenating distillate oil. , (Iii) A method of subjecting the distillate to a hydrogenation treatment after solvent extraction treatment, (iv) A method of subjecting the distillate to a two-stage or three-stage hydrotreatment, or a subsequent alkali washing or sulfuric acid washing treatment Furthermore, (v) there is a method in which after the treatments (i) to (iv) described above, a dewaxing treatment is performed again to obtain a deep dewaxed oil.

  Among the above methods, as the highly refined mineral oil used in the present invention, naphthenic mineral oil and mineral oil obtained by deep dewaxing are preferable from the viewpoint of low temperature fluidity and no wax precipitation at low temperature. . This deep dewaxing process is performed by a solvent dewaxing process under severe conditions, a contact dewaxing process using a zeolite catalyst, or the like.

  Examples of the olefin polymer include those obtained by polymerizing olefins having 2 to 12 carbon atoms, and those obtained by subjecting this to hydrogenation treatment. Specific examples include polybutene, polyisobutene, and α having 5 to 12 carbon atoms. -Oligomeric oligomers (polyalphaolefins), ethylene-propylene copolymers, and those subjected to hydrogenation treatment are preferably used.

  The production method of the olefin polymer is not particularly limited, and can be produced by various known methods. As an example of this, for example, poly α olefin is produced from α olefin produced from ethylene as a raw material, and this is produced by a known polymerization method such as Ziegler catalyst method, radical polymerization method, aluminum chloride method, boron fluoride method and the like. .

［一般式（１）中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同一でも異なっていても良く、それぞれ水素原子又は炭素数１〜１０の炭化水素基を示し、かつＲ^１、Ｒ^２、Ｒ^３及びＲ^４の合計炭素数は１〜１０である。］ The naphthalene compound is not particularly limited as long as it has a naphthalene skeleton, but a naphthalene compound represented by the general formula (1) is preferable from the viewpoint of excellent compatibility with a refrigerant.

[In General Formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and R ¹ , R ² , R ³ and R ⁴ have 1 to 10 total carbon atoms. ]

In the general formula (1), R ¹ , R ² , R ³ and R ⁴ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms. ing. Examples of the hydrocarbon group herein include an alkyl group, an alkenyl group, an aryl group, an alkylaryl group, and an aralkyl group.

Specific examples of preferred hydrocarbon groups represented by R ¹ , R ² , R ^3, and R ⁴ include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, linear or branched Carbon such as butyl group, linear or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group An alkyl group of 1 to 8; an ethenyl group (vinyl group), 1-propenyl group, 2-propenyl group (allyl group), 1-methylethenyl group (isopropenyl group), linear or branched butenyl group, 2 to 8 carbon atoms such as a linear or branched pentenyl group, a linear or branched hexenyl group, a linear or branched heptenyl group, a linear or branched octenyl group Alkenyl group: phenyl group, tolyl group, xylyl group, ethyl group Aryl groups or alkylaryl groups having 6 to 8 carbon atoms such as nyl group and vinylphenyl group; aralkyl groups having 7 to 8 carbon atoms such as benzyl group, 1-phenylethyl group and 1-phenylethyl group (phenethyl group); Etc. Among these, an alkyl group having 1 to 8 carbon atoms and an alkenyl group having 2 to 8 carbon atoms are particularly preferable, and most preferable is a branched one.

The total number of carbon atoms of R ¹ , R ² , R ³ and R ⁴ is 1-10, preferably 1-8. Within this range, R ¹ , R ² , R ³ and R ⁴ may be the same or different. That is, as the compound of the formula (1), R ¹ , R ² , R ³ and R ⁴ may all be hydrocarbon groups, and at least 1 of R ¹ , R ² , R ³ and R ⁴ One may be a hydrocarbon group and the other may be a hydrogen atom. From the point of compatibility with the refrigerant, ¹ to 3 of R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups and the others are hydrogen atoms, and R ¹ , R ² , R ³ and R ^4. It is preferable that the total carbon number of is 3-8.

When ^{two of} R ¹ , R ² , R ³ and R ⁴ are hydrocarbon groups, the combination is not particularly limited, and the same condensed ring (benzene ring) such that R ¹ and R ² are hydrocarbon groups is used. ) May be bonded to two hydrocarbon groups, and each hydrocarbon group may be bonded to a different condensed ring (benzene ring) such that R ¹ and R ³ are hydrocarbon groups. It may be.

  Specific examples of preferable naphthalene compounds represented by the general formula (1) include (n-propyl) naphthalene, isopropylnaphthalene, (n-butyl) naphthalene, isobutylnaphthalene, (sec-butyl) naphthalene, (Tert-butyl) naphthalene, (sec-pentyl) naphthalene, (1-ethylpropyl) naphthalene, (tert-pentyl) naphthalene, (1-methylpentyl) naphthalene, (1-ethylbutyl) naphthalene, (1,1-dimethyl) Butyl) naphthalene, (1-ethyl-1-methylpropyl) naphthalene, (1-methylhexyl) naphthalene, (1-ethylpentyl) naphthalene, (1-propylbutyl) naphthalene, (1,1-dimethylpentyl) naphthalene, (1-ethyl-1-methylbuty ) Naphthalene, (1,1-diethylpropyl) naphthalene, (1-methylheptyl) naphthalene, (1-ethylhexyl) naphthalene, (1-propylpentyl) naphthalene, (1,1-dimethylhexyl) naphthalene, (1-ethyl) -1-methylpentyl) naphthalene, (1-methyl-1-propylbutyl) naphthalene, (1,1-diethylbutyl) naphthalene, ethylmethylnaphthalene, diethylnaphthalene, methyl (n-propyl) naphthalene, methylisopropylnaphthalene, di (N-propyl) naphthalene, diisopropylnaphthalene, (n-butyl) methylnaphthalene, isobutylmethylnaphthalene, (sec-butyl) methylnaphthalene, (tert-butyl) methylnaphthalene, di (n-butyl) naphthalene, diisobutylene Naphthalene, di (sec-butyl) naphthalene, di (tert-butyl) naphthalene, trimethylnaphthalene, triethylnaphthalene, ethyldimethylnaphthalene, diethylmethylnaphthalene, dimethyl (n-propyl) naphthalene, dimethylisopropylnaphthalene, methyldi (n-propyl) Naphthalene, methyldiisopropylnaphthalene, (n-butyl) dimethylnaphthalene, isobutyldimethylnaphthalene, (sec-butyl) dimethylnaphthalene, (tert-butyl) dimethylnaphthalene, phenylnaphthalene, tolylnaphthalene, xylylnaphthalene, (ethylphenyl) naphthalene, (Vinylphenyl) naphthalene, benzylnaphthalene, phenethylnaphthalene, (1-phenylethyl) naphthalene and the like can be mentioned.

  The naphthalene compound is not limited to a compound having a single structure, but may be a mixture of two or more compounds having different structures.

  Moreover, the manufacturing method in particular of the said naphthalene compound is not restrict | limited, It can manufacture with a various well-known method. Examples of this include, for example, halogenated hydrocarbons having 1 to 10 carbon atoms, olefins having 2 to 10 carbon atoms, or styrenes having 8 to 10 carbon atoms, sulfuric acid, phosphoric acid, silicotungstic acid, and hydrofluoric acid. And a method of adding to naphthalene in the presence of an acid catalyst such as Friedel Crafts catalyst which is a solid acid substance such as mineral acid such as acid clay, acid clay and activated clay and metal halide such as aluminum chloride and zinc chloride.

  Any alkylbenzene can be used, but the component having a molecular weight of 200 to 350 is 60% by mass or more, preferably 65% because the possibility of seizure of the refrigerant compressor in a long-term operation is small. % Or more, more preferably 70% by mass or more, particularly preferably 80% by mass or more, and most preferably 100% by mass.

  In addition, the alkylbenzene is preferably a component having a molecular weight of 200 to 300, more preferably 30% by mass or more, more preferably 35% by mass or more, and particularly preferably, from the viewpoint of excellent seizure resistance of the refrigerant compressor under long-term operation. It is desirable to contain 40 mass% or more.

  The structure of the alkylbenzene having a molecular weight of 200 to 350 is not particularly limited as long as the molecular weight is within this range, but from the viewpoint of long-term reliability of the refrigeration system, 1 to 4 alkyl groups having 1 to 19 carbon atoms are used. It is preferably an alkylbenzene having 9 to 19 carbon atoms in the alkyl group (hereinafter referred to as “alkylbenzene (A)”), and further having 1 to 4 alkyl groups having 1 to 15 carbon atoms. It is more preferable that the alkyl group has 9 to 15 carbon atoms in the alkyl group.

  Specific examples of the alkyl group having 1 to 19 carbon atoms include a methyl group, an ethyl group, a propyl group (including all isomers), a butyl group (including all isomers), and a pentyl group. (Including all isomers), hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) ), Decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers), tetradecyl group (including all isomers) All isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octadecyl group (all isomers) Including), including nonadecyl group (including all isomers) and the like.

  The alkyl group may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.

  The alkylbenzene (A) has 1 to 4 alkyl groups. From the viewpoint of stability and availability, the alkylbenzene having 1 or 2 alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or these The mixture of is most preferably used.

  Moreover, as alkylbenzene (A), not only the alkylbenzene of a single structure but the mixture of 2 or more types of the alkylbenzene which has a different structure may be sufficient.

  The alkylbenzene used in the present invention desirably contains a component having a molecular weight of less than 200 or a molecular weight of more than 350, less than 40% by mass, preferably less than 35% by mass, and more preferably less than 30% by mass. These components are preferably alkylbenzenes having a molecular weight of more than 350 and not more than 450 from the viewpoint of reliability during long-term operation of the compressor, and are alkylbenzenes having a molecular weight of more than 350 and not more than 430. It is more preferable.

  The structure of the alkylbenzene having a molecular weight of more than 350 and not more than 450 is not particularly limited as long as the molecular weight is within this range, but from the viewpoint of stability and availability, an alkyl group having 1 to 40 carbon atoms is 1 It is preferable that it is an alkylbenzene (henceforth "alkylbenzene (B)") which has -4 and the total carbon number of the alkyl group is 20-40, Furthermore, 1-C30 alkyl group is 1 It is more preferable that the alkylbenzene has ˜4 and the total number of carbon atoms of the alkyl group is 20-30.

  Specific examples of the alkyl group having 1 to 40 carbon atoms include a methyl group, an ethyl group, a propyl group (including all isomers), a butyl group (including all isomers), and a pentyl group. (Including all isomers), hexyl group (including all isomers), heptyl group (including all isomers), octyl group (including all isomers), nonyl group (including all isomers) ), Decyl group (including all isomers), undecyl group (including all isomers), dodecyl group (including all isomers), tridecyl group (including all isomers), tetradecyl group (including all isomers) All isomers), pentadecyl group (including all isomers), hexadecyl group (including all isomers), heptadecyl group (including all isomers), octadecyl group (all isomers) ), Nonadecyl group (including all isomers), icosyl group (including all isomers), heicosyl group (including all isomers), docosyl group (including all isomers), tricosyl group (Including all isomers), tetracosyl group (including all isomers), pentacosyl group (including all isomers), hexacosyl group (including all isomers), heptacosyl group (including all isomers) ), Octacosyl group (including all isomers), nonacosyl group (including all isomers), triacontyl group (including all isomers), hentriacontyl group (including all isomers), dotriacontyl Groups (including all isomers), tritriacontyl groups (including all isomers), tetratriacontyl groups (including all isomers), Tatriacontyl group (including all isomers), Hexatriacontyl group (including all isomers), Heptatriacontyl group (including all isomers), Octatriacontyl group (including all isomers) ), Nonatoriacontyl group (including all isomers), tetracontyl group (including all isomers), and the like.

  The alkyl group may be linear or branched, but a branched alkyl group is preferable from the viewpoint of stability, viscosity characteristics, etc., and propylene, Branched alkyl groups derived from olefin oligomers such as butene and isobutylene are more preferred.

  The alkylbenzene (B) has 1 to 4 alkyl groups. From the viewpoint of stability and availability, the alkylbenzene having 1 or 2 alkyl groups, that is, monoalkylbenzene, dialkylbenzene, or these The mixture of is most preferably used.

  Moreover, as alkylbenzene (B), not only the alkylbenzene of a single structure but the mixture of 2 or more types of the alkylbenzene which has a different structure may be sufficient.

  Although the manufacturing method of the said alkylbenzene is arbitrary and is not limited at all, generally, it can manufacture by the synthesis method shown below.

  Specific examples of the aromatic compound used as a raw material include benzene, toluene, xylene, ethylbenzene, methylethylbenzene, diethylbenzene, and mixtures thereof. As the alkylating agent, specifically, for example, a linear or branched olefin having 6 to 40 carbon atoms obtained by polymerization of a lower monoolefin (preferably propylene) such as ethylene, propylene, butene, and isobutylene. Linear or branched olefins having 6 to 40 carbon atoms obtained by thermal decomposition of wax, heavy oil, petroleum fraction, polyethylene, polypropylene, etc .; n-paraffins are separated from petroleum fractions such as kerosene and light oil In addition, linear olefins having 9 to 40 carbon atoms obtained by olefination with a catalyst; and mixtures thereof can be used.

  Further, as alkylation catalysts in the alkylation, Friedel-Crafts type catalysts such as aluminum chloride and zinc chloride; acidic catalysts such as sulfuric acid, phosphoric acid, silicotungstic acid, hydrofluoric acid and activated clay; These catalysts are used.

  The alkylbenzene can be obtained, for example, by separately mixing a component having a molecular weight of 200 to 350 and a component having a molecular weight of less than 200, or a component having a molecular weight of more than 350 in a ratio defined in the present invention. In practice, there is a method in which an alkylbenzene mixture obtained by the method exemplified in the above or a commercially available alkylbenzene mixture is separated by distillation or chromatography to obtain a fraction containing 60% by mass or more of a component having a molecular weight of 200 to 350. Convenient.

  Examples of the oxygen-containing oil used in the working fluid composition for a refrigerator according to the present invention include esters, polyoxyalkylene glycols, polyvinyl ethers, ketones, polyphenyl ethers, silicones, polysiloxanes, and perfluoroethers. Among these, esters, polyoxyalkylene glycols, polyvinyl ethers, and mixtures thereof are preferably used. The oxygen-containing oil used in the present invention may be either a natural product or a synthetic product. For example, the ester may be extracted from fats and oils derived from animals and plants, or may be a synthetic ester.

  Examples of the esters include aromatic esters, dibasic acid esters, polyol esters, complex esters, carbonate esters, and mixtures thereof.

  As an aromatic ester, ester of 1-6 valent, preferably 1-4 valent, more preferably 1-3 valent aromatic carboxylic acid and C1-C18, preferably 1-12 aliphatic alcohol, etc. Is used. Specific examples of the monovalent to hexavalent aromatic carboxylic acid include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, and mixtures thereof. In addition, the aliphatic alcohol having 1 to 18 carbon atoms may be linear or branched, and specifically, for example, methanol, ethanol, linear or branched propanol , Linear or branched butanol, linear or branched pentanol, linear or branched hexanol, linear or branched heptanol, linear or branched Octanol, linear or branched nonanol, linear or branched decanol, linear or branched undecanol, linear or branched dodecanol, linear or branched Tridecanol, linear or branched tetradecanol, linear or branched pentadecanol, linear or branched hexadecanol, linear or branched heptadecanol, Linear or branched octadecanol and Such as a mixture of these and the like. Specific examples of the aromatic ester include dibutyl phthalate, di (2-ethylhexyl) phthalate, dinonyl phthalate, didecyl phthalate, didodecyl phthalate, ditridecyl phthalate, tributyl trimellitic acid, and trimellitic acid trimethyl. (2-ethylhexyl), trinonyl trimellitic acid, tridecyl trimellitic acid, tridodecyl trimellitic acid, tritridecyl trimellitic acid and the like. Of course, when a divalent or higher valent aromatic carboxylic acid is used, it may be a simple ester composed of one kind of aliphatic alcohol, or a complex ester composed of two or more kinds of aliphatic alcohol. May be.

  Dibasic acid esters include dibasic acids having 5 to 10 carbon atoms such as glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, methanol, ethanol, propanol, butanol, pentanol, hexanol, Preferred are esters with monohydric alcohols having 1 to 15 carbon atoms having a linear or branched alkyl group such as heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, and the like, and mixtures thereof. More specifically, for example, ditridecyl glutarate, di2-ethylhexyl adipate, diisodecyl adipate, ditridecyl adipate, di-2-ethylhexyl sebacate, and a mixture thereof can be mentioned.

  As the polyol ester, an ester of a polyol having 3 to 20 diols or hydroxyl groups and a fatty acid having 6 to 20 carbon atoms is preferably used. Here, specific examples of the diol include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-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, 1,12- And dodecanediol. Specific examples of the polyol include, for example, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (Pentaerythritol), glycerin, polyglycerin (2-20 mer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohol such as adonitol, arabitol, xylitol, mannitol, Xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffino Scan, gentianose, sugars such as melezitose, and their partially etherified products and methyl glucosides (glycosides) and the like. Among these, as a polyol, since it is more excellent in hydrolysis stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), Hindered alcohols such as pentaerythritol, di- (pentaerythritol) and tri- (pentaerythritol) are preferred.

  As the fatty acid, the number of carbon atoms is not particularly limited, but those having 1 to 24 carbon atoms are usually used. Among the fatty acids having 1 to 24 carbon atoms, those having 3 or more carbon atoms are preferable from the viewpoint of lubricity, those having 4 or more carbon atoms are more preferable, those having 5 or more carbon atoms are still more preferable, and those having 10 or more carbon atoms are more preferable. Is most preferred. Moreover, from a compatibility point with a refrigerant | coolant, a C18 or less thing is preferable, a C12 or less thing is more preferable, and a C9 or less thing is still more preferable.

  Moreover, any of a linear fatty acid and a branched fatty acid may be sufficient, a linear fatty acid is preferable from the point of lubricity, and a branched fatty acid is preferable from the point of hydrolysis stability. Furthermore, either saturated fatty acid or unsaturated fatty acid may be used.

  Specific examples of fatty acids include, for example, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid Examples thereof include linear or branched acid such as acid, nonadecanoic acid, icosanoic acid and oleic acid, or so-called neoacid having a quaternary α-carbon atom. More specifically, valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid) Capric acid (n-decanoic acid), oleic acid (cis-9-octadecenoic acid), isopentanoic acid (3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3, 5,5-trimethylhexanoic acid and the like are preferred.

  Specific examples of preferred polyol esters include neopentyl glycol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2 -Diester with one or more fatty acids selected from ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, trimethylolethane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, One or more fatty acids selected from capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and Triester, trimethylolpropane and valeric acid, caproic acid, enanthic acid, caprylic acid, pe One or more selected from lugonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid Triesters with fatty acids, trimethylolbutane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethyl Triester with one or more fatty acids selected from hexanoic acid, 3,5,5-trimethylhexanoic acid, pentaerythritol and valeric acid, isopentanoic acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid , Capric acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5, - trimethyl hexanoate, and a tetraester of oleic acid, one or more fatty acids selected from the.

  The ester with two or more fatty acids may be a mixture of two or more esters of one fatty acid and a polyol, or may be an ester of two or more mixed fatty acids and a polyol. In addition, the ester with 2 or more types of fatty acid, especially the ester of mixed fatty acid and polyol are excellent in low temperature characteristics and compatibility with the refrigerant.

  The polyol ester may be a partial ester remaining without all the hydroxyl groups of the polyol being esterified, or may be a complete ester in which all the hydroxyl groups are esterified, or a partial ester and a complete ester. A complete ester is preferable.

  The complex ester is an ester of a fatty acid and a dibasic acid, and a monohydric alcohol and a polyol. The fatty acid, the dibasic acid, the monohydric alcohol, and the polyol are an explanation regarding the dibasic acid ester and the polyol ester. The thing similar to what was illustrated in can be used.

The carbonate ester is a compound having a carbonate ester structure represented by the following formula (A) in the molecule. One carbonate ester structure or a plurality of carbonate ester structures may be included in one molecule.

  As alcohol which comprises carbonate ester, the above-mentioned aliphatic alcohol, polyol, etc. can be used, and what added polyglycol to polyglycol and polyol can also be used. Moreover, you may use what used carbonic acid and a fatty acid, and / or a dibasic acid.

  As a matter of course, the ester referred to in the present invention may be a single ester having a single structure or a mixture of two or more esters having different structures.

  Among these ester-based lubricating base oils, polyol esters and carbonates are preferred because of excellent compatibility with refrigerants.

  Among polyol esters, since they are more excellent in hydrolytic stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), penta More preferred are esters of hindered alcohols such as erythritol, di- (pentaerythritol), tri- (pentaerythritol), and even more preferred are esters of neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol. The ester of pentaerythritol is most preferred because it is particularly excellent in compatibility with the refrigerant and hydrolytic stability.

  Specific examples of preferred polyol esters include neopentyl glycol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2 -Diester with one or more fatty acids selected from ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, trimethylolethane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, One or more fatty acids selected from capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, and Triester, trimethylolpropane and valeric acid, caproic acid, enanthic acid, caprylic acid, pe One or more selected from lugonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid Triesters with fatty acids, trimethylolbutane and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethyl Triester with one or more fatty acids selected from hexanoic acid, 3,5,5-trimethylhexanoic acid, pentaerythritol and valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid Oleic acid, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexane , Tetra-esters of one or more fatty acids selected from among 3,5,5-trimethyl hexanoic acid.

  The ester with two or more fatty acids may be a mixture of two or more esters of one fatty acid and a polyol, or may be an ester of two or more mixed fatty acids and a polyol. In addition, the ester with 2 or more types of fatty acid, especially the ester of mixed fatty acid and polyol are excellent in low temperature characteristics and compatibility with the refrigerant.

［上記式（Ａ−１）中、Ｘ^１は水素原子、アルキル基、シクロアルキル基又は下記一般式（Ａ−２）：
Ｙ^２−（ＯＡ^３）ｅ− （Ａ−２）
（上記式（Ａ−２）中、Ｙ^２は水素原子、アルキル基又はシクロアルキル基を示し、Ａ^３は炭素数２〜４のアルキレン基を示し、ｅは１〜５０の整数を示す）で表される基を示し、Ａ^１及びＡ^２は同一でも異なっていてもよく、それぞれ炭素数２〜４のアルキレン基を示し、Ｙ^１は水素原子、アルキル基又はシクロアルキル基を示し、Ｂは水酸基３〜２０個を有する化合物の残基を示し、ａは１〜２０、ｂは０〜１９でかつａ＋ｂ＝３〜２０となる整数を示し、ｃは０〜５０の整数、ｄは１〜５０の整数をそれぞれ示す］ Of the carbonic acid esters, those having a structure represented by the following general formula (1) are preferred.

[In the above formula (A-1), X ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group or the following general formula (A-2):
Y ^2- (OA ³ ) e- (A-2)
(In the above formula (A-2), Y ² represents a hydrogen atom, an alkyl group or a cycloalkyl group, A ³ represents an alkylene group having 2 to 4 carbon atoms, and e represents an integer of 1 to 50). A ¹ and A ² may be the same or different and each represents an alkylene group having 2 to 4 carbon atoms, Y ¹ represents a hydrogen atom, an alkyl group or a cycloalkyl group, and B represents A represents a residue of a compound having 3 to 20 hydroxyl groups, a represents an integer of 1 to 20, b represents 0 to 19 and a + b = 3 to 20; c represents an integer of 0 to 50; Each represents an integer of 50]

In the general formula (A-1), X ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a group represented by the general formula (A-2). Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. Moreover, it may be linear or branched.

  Specific examples of the alkyl group having 1 to 24 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Chain or branched pentyl group, linear or branched hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, linear or Branched undecyl group, linear or branched dodecyl group, linear or branched tridecyl group, linear or branched tetradecyl group, linear or branched pentadecyl group, linear or branched hexadecyl group, linear or branched Heptadecyl group, linear or branched octadecyl group, linear or branched nonadecyl group, linear or branched icosyl group, linear or branched heicosyl group, linear or branched docosyl group, linear or branched tricosyl group , Linear or minute Tetracosyl and the like group, and the like.

  Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

In formula (A-2), the alkylene group having 2 to 4 carbon atoms represented by A ^3, an ethylene group, a propylene group, trimethylene group, butylene group, tetramethylene group, 1-methyltrimethylene group, Examples include 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene group and the like.

Y ² in the general formula (A-2) is a hydrogen atom, an alkyl group, or a cycloalkylalkyl group. Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. Moreover, it may be linear or branched. Specific examples of the alkyl group having 1 to 24 carbon atoms include the groups listed in the description relating to X ¹ .

  Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

Among these, Y ² is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or iso-dodecyl group More preferably, it is either. E represents an integer of 1 to 50.

X ¹ is preferably a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or a group represented by the general formula (2), and includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso group. -Propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n -Heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n It is more preferably any one of a group represented by -dodecyl group, iso-dodecyl group or general formula (2).

  Specific examples of the compound having 3 to 20 hydroxyl groups having B as a residue include the aforementioned polyols.

A ¹ and A ² may be the same or different and each represents an alkylene group having 2 to 4 carbon atoms. Specifically, for example, ethylene group, propylene group, trimethylene group, butylene group, tetramethylene group, 1-methyltrimethylene group, 2-methyltrimethylene group, 1,1-dimethylethylene group, 1,2-dimethylethylene. Examples include groups.

Y ¹ represents a hydrogen atom, an alkyl group, or a cycloalkylalkyl group. Although carbon number of an alkyl group here is not restrict | limited in particular, Usually, 1-24, Preferably it is 1-18, More preferably, it is 1-12. Moreover, it may be linear or branched. Specific examples of the alkyl group having 1 to 24 carbon atoms include the groups listed in the description relating to X ¹ .

  Specific examples of the cycloalkyl group include a cyclopentyl group, a cyclohexyl group, and a cycloheptyl group.

Among these, Y ¹ is preferably a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and includes a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, an n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, iso-pentyl group, neo-pentyl group, n-hexyl group, iso-hexyl group, n-heptyl group, iso-heptyl group, n-octyl group, iso-octyl group, n-nonyl group, iso-nonyl group, n-decyl group, iso-decyl group, n-undecyl group, iso-undecyl group, n-dodecyl group or iso-dodecyl group More preferably, it is either.

  In the above general formulas (A-1) and (A-2), c, d and e represent the degree of polymerization of the polyoxyalkylene moiety, and the polyoxyalkylene moiety may be the same or different in the molecule. In the case of having a plurality of different polyoxyalkylene moieties, there is no particular limitation on the polymerization mode of the oxyalkylene group, and random copolymerization or block copolymerization may be performed.

  The method for producing the carbonic acid ester used in the present invention is arbitrary. For example, a polyalkylene glycol polyol ether is produced by adding an alkylene oxide to a polyol compound, and this and chloroformate are mixed with sodium hydroxide or potassium hydroxide. It is obtained by reacting at 0 to 30 ° C. in the presence of an alkali metal hydroxide such as sodium alkoxide, an alkali metal alkoxide such as sodium methoxide or sodium ethoxide, or an alkali such as metal sodium. Alternatively, a polyalkylene glycol polyol ether, a carbonic acid diester, a source of carbonic acid such as phosgene, an alkali metal hydroxide such as sodium hydroxide and potassium hydroxide, an alkali metal alkoxide such as sodium methoxide and sodium ethoxide, or metal sodium It can be obtained by reacting at 80 to 150 ° C. in the presence of an alkali. Thereafter, the free hydroxyl group is etherified as necessary.

  By-products and unreacted substances may be removed by purifying the product obtained from the raw materials as described above, but a small amount of by-products and unreacted substances are excellent performance of the lubricating oil of the present invention. As long as it is not damaged, there is no problem even if it exists.

  In the present invention, the carbonate ester may be used in the form of a mixture or as a single product. Although the molecular weight of the carbonate ester according to the present invention is not particularly limited, those having a number average molecular weight of 200 to 4000 are preferably used from the viewpoint of further improving the sealing performance of the compressor, and the number average molecular weight is 300 to 3000 is more preferably used.

  In the present invention, one of the above ester-based lubricating base oils may be used alone, or two or more may be used in combination.

As a polyoxyalkylene glycol used for the working fluid composition for refrigerators of this invention, the compound represented, for example by general formula (B-1) is mentioned.
R ⁵ - ^[(OR ₆₎ f -OR ^7] _g (B-1)
(In formula (B-1), R ⁵ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or a residue of a compound having 2 to 8 hydroxyl groups, and R ⁶ is the number of carbon atoms. 2 to 4 alkylene groups, R ⁷ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, f is an integer of 1 to 80, and g is an integer of 1 to 8)

In the general formula (B-1), the alkyl group in R ⁵ and R ⁷ 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, a linear or branched butyl group, a linear or branched pentyl group, a linear or branched group. Hexyl group, linear or branched heptyl group, linear or branched octyl group, linear or branched nonyl group, linear or branched decyl group, cyclopentyl Group, cyclohexyl group and the like. When the alkyl group has more than 10 carbon atoms, the compatibility with the refrigerant is lowered, and phase separation may occur. The carbon number of a preferable alkyl group is 1-6.

Moreover, the alkyl group part of the acyl group in R ⁵ and R ⁷ may be linear, branched or cyclic. As specific examples of the alkyl group portion of the acyl group, various groups having 1 to 9 carbon atoms exemplified as the specific examples of the alkyl group can be exemplified. When the number of carbon atoms in the acyl group exceeds 10, compatibility with the refrigerant may be reduced, and phase separation may occur. A preferable acyl group has 2 to 6 carbon atoms.

When R ⁵ and R ⁷ are both alkyl groups or acyl groups, R ¹ and R ³ may be the same or different from each other. Further, when g is 2 or more, a plurality of R ^{3 in} one molecule may be the same or different.

When R ⁵ is a residue of a compound having 2 to 8 hydroxyl groups, this compound may be a chain or cyclic. Examples of the compound having two hydroxyl groups include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3-propanediol, 1, 5-pentanediol, neopentyl glycol, 1,6-hexanediol, 2-ethyl-2-methyl-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, 1,12-dodecanediol Etc.

  Examples of the compound having 3 to 8 hydroxyl groups include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, and di- (pentaerythritol). , Tri- (pentaerythritol), glycerin, polyglycerin (2-6 mer of glycerin), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol, etc. Dihydric alcohol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, la Inosu, gentianose, sugars such as melezitose, and their partially etherified products and methyl glucosides (glycosides) and the like.

  In the present invention, the residue of a compound having a hydroxyl group means a residue excluding the hydroxyl group.

In the present invention, at least one of R ⁵ and R ⁷ is preferably an alkyl group, particularly an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group from the viewpoint of viscosity characteristics. Further, for the same reason as described above, both R ⁵ and R ⁷ are preferably alkyl groups, particularly alkyl groups having 1 to 4 carbon atoms, and particularly preferably methyl groups.

R ⁶ in the general formula (B-1) is an alkylene group having 2 to 4 carbon atoms, and examples thereof include an ethylene group, a propylene group, and a butylene group. Examples of the oxyalkylene group of the repeating unit represented by (OR ⁶ ) include an oxyethylene group, an oxypropylene group, and an oxybutylene group. The oxyalkylene groups in one molecule may be the same, or two or more oxyalkylene groups may be contained.

  From the viewpoint of refrigerant compatibility and hygroscopicity, a copolymer containing an oxyethylene group (EO) and an oxypropylene group (PO) is preferable. In such a case, EO / (PO + EO) from the viewpoint of seizure load and viscosity characteristics. Is preferably in the range of 0.1 to 0.8, and more preferably in the range of 0.3 to 0.6.

  In terms of hygroscopicity and thermal oxidation stability, the value of EO / (PO + EO) is preferably in the range of 0 to 0.5, more preferably in the range of 0 to 0.2, and the PO homopolymer is Most preferred.

F in the said general formula (B-1) is an integer of 1-80. Moreover, g in the said general formula (B-1) is an integer of 1-8. For example, when R ⁵ is an alkyl group or an acyl group, g is 1. When R ⁵ is a residue of a compound having 2 to 8 hydroxyl groups, g is the number of the hydroxyl groups.

  Moreover, although it does not restrict | limit especially about fxg, In order to satisfy | fill the required performance as above-mentioned lubricating oil for refrigerators with sufficient balance, it is preferable to make it the average value of fxg become 6-80.

  The polyoxyalkylene glycol represented by the general formula (B-1) includes a polyoxyalkylene glycol having a hydroxyl group at the terminal, and the hydroxyl group content is 50 mol% or less with respect to all terminal groups. If it is the ratio which becomes, even if it contains, it can be used conveniently. If the hydroxyl group content exceeds 50 mol%, the hygroscopicity increases and the viscosity index decreases, which is not preferable.

Examples of the polyoxyalkylene glycol according to the present invention include polyoxypropylene glycol dimethyl ether represented by the following general formula (I-1) and polyoxyethylene polyoxypropylene glycol dimethyl ether represented by the following general formula (I-2). It is preferable in terms of economy and effect, and polyoxypropylene glycol monobutyl ether represented by the following general formula (I-3), and further polyoxypropylene glycol diacetate are preferable in terms of economy and the like. It is.
_{CH 3 O- (C 3 H 6} O) h -CH 3 (I-1)
(In the formula, h represents a number of 6 to 80.)
_{CH 3 O- (C 3 H 6} O) i - (C 2 H 4 O) j -CH 3 (I-2)
(In the formula, i and j each represent a number that is 1 or more and the sum thereof is 6 to 80).
_{C 4 H 9 O- (C 3} H 6 O) k -H (I-3)
(In the formula, k represents a number of 6 to 80.)

［式（ＩＩ）中、Ｒ^８〜Ｒ^１１はそれぞれ水素原子、炭素数１〜１０の一価の炭化水素基又は一般式（ＩＩＩ）：

（式（ＩＩＩ）中、Ｒ^１２及びＲ^１３はそれぞれ水素原子、炭素数１〜１０の一価炭化水素基又は炭素数２〜２０のアルコキシアルキル基を示し、Ｒ^１４は炭素数２〜５のアルキレン基、アルキル基を置換基として有する総炭素数２〜５の置換アルキレン基又はアルコキシアルキル基を置換基として有する総炭素数４〜１０の置換アルキレン基を示し、ｐは０〜２０の整数、Ｒ^１５は炭素数１〜１０の一価炭化水素基を示す）で表される基であり、Ｒ^８〜Ｒ^１１の少なくとも１つが一般式（ＩＩＩ）で表される基である］ In the present invention, a polyoxyalkylene glycol derivative having at least one structural unit represented by the general formula (II) can be used as the polyoxyalkylene glycol.

[In the formula (II), R ^{8 to} R ¹¹ are each a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or a general formula (III):

(In the formula (III), R ¹² and R ¹³ each represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms or an alkoxyalkyl group having 2 to 20 carbon atoms, and R ¹⁴ has 2 to 5 carbon atoms. An alkylene group, a substituted alkylene group having a total carbon number of 2 to 5 having an alkyl group as a substituent or a substituted alkylene group having a total carbon number of 4 to 10 having an alkoxyalkyl group as a substituent, p is an integer of 0 to 20, R ¹⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms), and at least one of R ^{8 to} R ¹¹ is a group represented by the general formula (III).

Here, in formula (II), R ^{8 to} R ¹¹ are each represented by a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or the above general formula (III). Specific examples of the monovalent hydrocarbon group include a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkenyl group having 2 to 10 carbon atoms, and carbon. Examples thereof include a cycloalkyl group or an alkylcycloalkyl group having 5 to 10 carbon atoms, an aryl group or alkylaryl group having 6 to 10 carbon atoms, and an arylalkyl group having 7 to 10 carbon atoms. Among these, a monovalent hydrocarbon group having 6 or less carbon atoms can be preferably used, and an alkyl group having 3 or less carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is most suitable.

In the general formula (III), R ¹² and R ¹³ each represent a hydrogen atom, a monovalent hydrocarbon group having 1 to 10 carbon atoms, or an alkoxyalkyl group having 2 to 20 carbon atoms. An alkyl group of 3 or less or an alkoxyalkyl group having 6 or less carbon atoms is preferred. Specific examples of the alkyl group having 3 or less carbon atoms include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. Examples of the alkoxyalkyl group having 2 to 6 carbon atoms include methoxymethyl group, ethoxymethyl group, n-propoxymethyl group, isopropoxymethyl group, n-butoxymethyl group, isobutoxymethyl group, sec-butoxymethyl. Group, tert-butoxymethyl group, pentoxymethyl group (including all isomers), methoxyethyl group (including all isomers), ethoxyethyl group (including all isomers), propoxyethyl group (all ), Butoxyethyl group (including all isomers), methoxypropyl group (including all isomers), ethoxypropyl group (including all isomers), propoxypropyl group (all isomers) Body), methoxybutyl group (including all isomers), ethoxybutyl group (including all isomers) Such as methoxy pentyl group (including all isomers) are included.

R ¹⁴ represents an alkylene group having 2 to 5 carbon atoms, a substituted alkylene group having 2 to 5 carbon atoms having an alkyl group as a substituent, or a substituted alkylene group having 4 to 10 carbon atoms having an alkoxyalkyl group as a substituent. Are preferably an alkylene group having 2 to 4 carbon atoms and a substituted ethylene group having 6 or less carbon atoms in total. Specific examples of the alkylene group having 2 to 4 carbon atoms include an ethylene group, a propylene group, and a butylene group. Specific examples of the substituted ethylene group having 6 or less total carbon atoms include 1- (methoxymethyl) ethylene group, 2- (methoxymethyl) ethylene group, 1- (methoxyethyl) ethylene group, and 2- (methoxyethyl). ) Ethylene group, 1- (ethoxymethyl) ethylene group, 2- (ethoxymethyl) ethylene group, 1-methoxymethyl-2-methylethylene group, 1,1-bis (methoxymethyl) ethylene group, 2,2-bis (Methoxymethyl) ethylene group, 1,2-bis (methoxymethyl) ethylene group, 1-methyl-2-methoxymethylethylene group, 1-methoxymethyl-2-methylethylene group, 1-ethyl-2-methoxymethylethylene Group, 1-methoxymethyl-2-ethylethylene group, 1-methyl-2-ethoxymethylethylene group, 1-ethoxymethyl-2-methyl Ethylene, 1-methyl-2-methoxyethyl ethylene group, 1-methoxyethyl-2-methylethylene group.

R ¹⁵ represents a monovalent hydrocarbon group having 1 to 10 carbon atoms, and specifically, for example, a linear or branched alkyl group having 1 to 10 carbon atoms or a linear chain having 2 to 10 carbon atoms. Or branched alkenyl groups, cycloalkyl groups having 5 to 10 carbon atoms or alkylcycloalkyl groups, aryl groups having 6 to 10 carbon atoms or alkylaryl groups, arylalkyl groups having 7 to 10 carbon atoms, and the like. . Among these, a monovalent hydrocarbon group having 6 or less carbon atoms can be preferably used, and an alkyl group having 3 or less carbon atoms, specifically, a methyl group, an ethyl group, an n-propyl group, or an isopropyl group is most suitable.

Note that at least one of R ^{8 to} R ¹¹ in the general formula (II) is a group represented by the general formula (III). In particular, any one of R ⁸ and R ¹⁰ is a group of the general formula (III), and R ⁸ and the remaining one of R ¹⁰ and R ⁹ and R ¹¹ are each a hydrogen atom or a carbon number of 1 to 10 A monovalent hydrocarbon group is preferred.

（式（ＩＶ）中、Ｒ^１６〜Ｒ^１９はそれぞれ水素原子又は炭素数１〜３のアルキル基を示す。） The polyoxyalkylene glycol derivative contains at least one structural unit represented by the general formula (II). More specifically, a homopolymer composed of the structural unit represented by the general formula (II), A copolymer comprising two or more different structural units contained in the formula (II), and a structural unit of the general formula (II) and other structural units, for example, a structural unit represented by the following general formula (IV) It can be roughly divided into three types of copolymers.

(In formula (IV), R ^{16 to} R ¹⁹ each represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.)

  Preferred examples of the homopolymer have 1 to 200 structural units A represented by the general formula (II), and the terminal groups each have a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, and a 1 to 10 carbon atom. The thing which consists of an alkoxy group or an aryloxy group can be mentioned. On the other hand, suitable examples of the copolymer include 1 to 200 of the two types of structural units A and B represented by the general formula (II), or the structural unit A represented by the general formula (II). 1 to 200 and 1 to 200 structural units C represented by the general formula (IV), and each terminal group is a hydroxyl group, an acyloxy group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or aryloxy The thing which consists of groups can be mentioned. These copolymers include alternating copolymerization of the structural unit A and the structural unit B (or the structural unit C), a random copolymer, a block copolymer, or a graft in which the structural unit B is graft-bonded to the main chain of the structural unit A. There are various types such as copolymers.

（式（Ｖ）中、Ｒ^２０、Ｒ^２１及びＲ^２２はそれぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、Ｒ^２３は炭素数１〜１０の二価の炭化水素基又は炭素数２〜２０の二価のエーテル結合酸素含有炭化水素基、Ｒ^２４は炭素数１〜２０の炭化水素基、ｑはその平均値が０〜１０の数を示し、Ｒ^２０〜Ｒ^２４は構成単位毎に同一であってもそれぞれ異なっていてもよく、またＲ^２３Ｏが複数ある場合には、複数のＲ^２３Ｏは同一でも異なっていてもよい。） Moreover, as a polyvinyl ether used for the working fluid composition for refrigerators of this invention, the polyvinyl ether type compound which has a structural unit represented, for example by the following general formula (V) is mentioned.

(In the formula (V), R ²⁰ , R ²¹ and R ²² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ²³ has 1 carbon atom. 10 divalent hydrocarbon group or a divalent, ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon ^{atoms, R 24} is a hydrocarbon group having 1 to 20 carbon atoms, q is an average value of 0 represents a number, R ²⁰ to R ²⁴ may be the same or different may be the same for each structural unit, also in the case where R ^{23 O} there is a plurality, the plurality of R ^{23 O} may be the same or different .)

（式（ＶＩ）中、Ｒ^２１〜Ｒ^２４は、それぞれ水素原子又は炭素数１〜２０の炭化水素基を示し、それらはたがいに同一でも異なっていてもよく、またＲ^２１〜Ｒ^２４は構成単位毎に同一であってもそれぞれ異なっていてもよい。） Moreover, the polyvinyl ether type compound which consists of a block or random copolymer which has a structural unit represented by the said general formula (V), and a structural unit represented by the following general formula (VI) can also be used.

(In the formula (VI), R ^{21 to} R ²⁴ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different, and R ^{21 to} R ²⁴ are constituents. Each unit may be the same or different.)

R ²⁰ , R ²¹ and R ²² in the general formula (V) each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms, and they may be the same or different. The hydrocarbon group is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups. Group, various heptyl groups, various octyl groups and other alkyl groups, cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups and other cycloalkyl groups, phenyl groups, various methylphenyl groups, various ethyl groups An aryl group such as a phenyl group and various dimethylphenyl groups, an arylalkyl group such as a benzyl group, various phenylethyl groups, and various methylbenzyl groups. As R ¹⁶ , R ¹⁷ and R ¹⁸ , a hydrogen atom is particularly preferable.

On the other hand, R ²³ 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 hydrocarbon group having 2 to 20 carbon atoms. Here, the divalent hydrocarbon group having 1 to 10 carbon atoms specifically includes a methylene group, an ethylene group, a phenylethylene group, a 1,2-propylene group, and a 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, various decylene groups and the like, cyclohexane, methylcyclohexaneethylcyclohexane , Cycloaliphatic hydrocarbons such as dimethylcyclohexane, propylcyclohexane, alicyclic groups having two bonding sites, various phenylene groups, various methylphenylene groups , Divalent aromatic hydrocarbon groups such as various ethylphenylene groups, various dimethylphenylene groups, various naphthylene groups, etc., and alkyl groups and aromatic moieties of alkyl aromatic hydrocarbons such as toluene, xylene, ethylbenzene, etc. Examples thereof include an alkyl aromatic group having a binding site, and an alkyl aromatic group having a binding site in the alkyl group portion of a polyalkyl aromatic hydrocarbon such as xylene and diethylbenzene. Of these, aliphatic groups having 2 to 4 carbon atoms are particularly preferred.

Specific examples of the divalent ether bond oxygen-containing hydrocarbon group having 2 to 20 carbon atoms include methoxymethylene group, methoxyethylene group, methoxymethylethylene group, 1,1-bismethoxymethylethylene group, 1,2 Preferred examples include -bismethoxymethylethylene group, ethoxymethylethylene group, (2-methoxyethoxy) methylethylene group, (1-methyl-2-methoxy) methylethylene group and the like. In addition, q in general formula (V) shows the repeating number of R < ²³ > O, The average value is 0-10, Preferably it is the number of the range of 0-5. When the R ^{23 O} is plural, plural R ^{23 O} may be the same or different.

Further, R ²⁴ in the general formula (V) represents a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms. Specific examples of the hydrocarbon group include a methyl group, an ethyl group, and n-propyl. Group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, etc. , Cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups and other cycloalkyl groups, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, Various propylphenyl groups, various trimethylphenyl groups, various butylphenols An aryl group such as a nyl group and various naphthyl groups, an arylalkyl group such as a benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, and various phenylbutyl groups. R ^{20 to} R ²⁴ may be the same or different for each structural unit.

The polyvinyl ether compound (1) represented by the general formula (V) preferably has a carbon / oxygen molar ratio in the range of 4.2 to 7.0. If this molar ratio is less than 4.2, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with the refrigerant may be reduced. In the general formula (VI), R ^{25 to} R ²⁸ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and they may be the same or different. Examples of the hydrocarbon group having 1 to 20 carbon atoms may include the same as those exemplified in the description of R ²⁴ in formula (V). R ^{25 to} R ²⁸ may be the same or different for each structural unit.

（式（ＶＩＩ）、（ＶＩＩＩ）中、Ｒ^２５、Ｒ^２６及びＲ^２７は、それぞれ水素原子又は炭素数１〜８の炭化水素基を示し、Ｒ^２５、Ｒ^２６及びＲ^２７はたがいに同一でも異なっていてもよく、Ｒ^３０、Ｒ^３１、Ｒ^３２及びＲ^３３は、それぞれ水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^３０、Ｒ^３１、Ｒ^３２及びＲ^３３はたがいに同一でも異なっていてもよい。Ｒ^２８は炭素数１〜１０の二価の炭化水素基又は炭素数２〜２０の二価のエーテル結合酸素含有炭化水素基、Ｒ^２９は炭素数１〜２０の炭化水素基、ｒはその平均値が０〜１０の数を示し、Ｒ^２８Ｏが複数ある場合には、複数のＲ^２８Ｏは同一でも異なっていてもよい。）

（式（ＩＸ）、（Ｘ）中、Ｒ^３８、Ｒ^３９及びＲ^４０は、それぞれ水素原子又は炭素数１〜８の炭化水素基を示し、Ｒ^３８、Ｒ^３９及びＲ^４０はたがいに同一でも異なっていてもよく、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６は、それぞれ水素原子又は炭素数１〜２０の炭化水素基を示し、Ｒ^４３、Ｒ^４４、Ｒ^４５及びＲ^４６はたがいに同一でも異なっていてもよい。Ｒ^４１は炭素数１〜１０の二価の炭化水素基又は炭素数２〜２０の二価のエーテル結合酸素含有炭化水素基、Ｒ^４２は炭素数１〜２０の炭化水素基、ｓはその平均値が０〜１０の数を示し、Ｒ^４１Ｏが複数ある場合には、複数のＲ^４１Ｏは同一でも異なっていてもよい）

（式（ＸＩ）中、Ｒ^４７、Ｒ^４８及びＲ^４９は、それぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一でも異なっていてもよい。） A polyvinyl ether compound (hereinafter referred to as “polyvinyl ether compound (2)”) comprising 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 the carbon / oxygen molar ratio in the range of 4.2 to 7.0 is preferably used. If this molar ratio is less than 4.2, the hygroscopicity is high, and if it exceeds 7.0, the compatibility with the refrigerant may be reduced. Further, in the present invention, a mixture of the polyvinyl ether compound (1) and the polyvinyl ether compound (2) can also be used. The polyvinyl ether compounds (1) and (2) used in the present invention are each a polymer of a corresponding vinyl ether monomer and a copolymer of a corresponding hydrocarbon monomer having an olefinic double bond and a corresponding vinyl ether monomer. Can be manufactured. The polyvinyl ether compound used in the present invention has the following terminal structure, that is, one terminal is represented by the general formula (VII) or (VIII), and the remaining terminal is the general formula (IX). Or a structure having a structure represented by (X), and one end thereof represented by the above general formula (VII) or (VIII), and the other end represented by the general formula (XI). What has is preferable.

(In the formulas (VII) and (VIII), R ²⁵ , R ²⁶ and R ²⁷ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ²⁵ , R ²⁶ and R ²⁷ may be the same. R ³⁰ , R ³¹ , R ³² and R ³³ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ³⁰ , R ³¹ , R ³² and R ³³ are identical to each other. R ²⁸ is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R ²⁹ is a carbon atom having 1 to 20 carbon atoms. hydrogen group, r mean value thereof indicates the number of 0, when R ^{28 O} is plural, plural R ^{28 O} may be the same or different.)

(In formulas (IX) and (X), R ³⁸ , R ³⁹ and R ⁴⁰ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and R ³⁸ , R ³⁹ and R ⁴⁰ may be the same. R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ each represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R ⁴³ , R ⁴⁴ , R ⁴⁵ and R ⁴⁶ are identical to each other. R ⁴¹ is a divalent hydrocarbon group having 1 to 10 carbon atoms or a divalent ether-bonded oxygen-containing hydrocarbon group having 2 to 20 carbon atoms, and R ⁴² is a carbon atom having 1 to 20 carbon atoms. hydrogen group, s is an average value thereof indicates the number of 0, when R ^{41 O} is plural, plural R ^{41 O} may be the same or different)

(In formula (XI), R ⁴⁷ , R ⁴⁸ and R ⁴⁹ each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different.)

Among such polyvinyl ether compounds, the following are particularly preferable in the present invention.
(1) One end thereof is represented by the general formula (VII) or (VIII), and the other end is represented by the general formula (IX) or (X). R ²⁰ , R ²¹ and R ²² are both hydrogen atoms, q is a number from 0 to 4, R ²³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R20 is a hydrocarbon group having 1 to 20 carbon atoms. thing.
(2) It has only the structural unit represented by the general formula (V), one end of which is represented by the general formula (VII), and the other end is represented by the general formula (IX). R ²⁰ , R ²¹ and R ²² in the general formula (V) are all hydrogen atoms, q is a number from 0 to 4, R ²³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ^24. Is a hydrocarbon group having 1 to 20 carbon atoms.
(3) One end thereof is represented by the general formula (VII) or (VIII), and the other end is represented by the general formula (XI), and R ²⁰ , R in the general formula (V) ²¹ and R ²² are both hydrogen atoms, q is a number of 0 to 4, R ²³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ²⁴ is a hydrocarbon group having 1 to 20 carbon atoms.
(4) It has only the structural unit represented by the general formula (V), one end of which is represented by the general formula (VII), and the other end is represented by the general formula (X). R ²⁰ , R ²¹ and R ²² in the general formula (V) are all hydrogen atoms, q is a number from 0 to 4, R ²³ is a divalent hydrocarbon group having 2 to 4 carbon atoms, and R ^24. Is a hydrocarbon group having 1 to 20 carbon atoms.

（式（ＸＩＩ）中、Ｒ^５０、Ｒ^５１及びＲ^５２は、それぞれ水素原子又は炭素数１〜８の炭化水素基を示し、それらはたがいに同一であっても異なっていてもよく、Ｒ^５３及びＲ^５５はそれぞれ炭素数２〜１０の二価の炭化水素基を示し、それらは互いに同一であっても異なっていてもよく、Ｒ^５４及びＲ^５６はそれぞれ炭素数１〜１０の炭化水素基を示し、それらは互いに同一であっても異なっていてもよく、ｔ及びｕはそれぞれその平均値が０〜１０の数を示し、それらは互いに同一であっても異なっていてもよく、また複数のＲ^５３Ｏがある場合には複数のＲ^５３Ｏは同一であっても異なっていてもよいし、複数のＲ^５３Ｏがある場合には複数のＲ^５３Ｏは同一であっても異なっていてもよい。） Moreover, in this invention, it has a structural unit represented by the said general formula (V), The one terminal is represented by general formula (VII), and the remaining terminal is represented by the following general formula (XII). Polyvinyl ether compounds having the structure described above can also be used.

(In formula (XII), R ⁵⁰ , R ⁵¹ and R ⁵² each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, and they may be the same or different, and R ⁵³ And R ⁵⁵ each represents a divalent hydrocarbon group having 2 to 10 carbon atoms, which may be the same or different from each other, and R ⁵⁴ and R ⁵⁶ are each a hydrocarbon group having 1 to 10 carbon atoms. They may be the same or different from each other, and t and u each represent an average value of 0 to 10, and they may be the same or different from each other, it is more R ^{53 O} if there are R ^{53 O} may be the same or different and when there are a plurality of R ^{53 O} is a plurality of R ^{53 O} are independently identical or different May be.)

（式（ＸＩＩＩ）、（ＸＩＶ）中、Ｒ^５７及びＲ^５８はそれぞれ炭素数１〜８の炭化水素基を示す。）

（式（ＸＶ）、（ＸＶＩ）中、Ｒ^５９は炭素数１〜３のアルキル基、Ｒ^６０及びＲ^６１はそれぞれ炭素数１〜８の炭化水素基を示す。） Furthermore, in this invention, it consists of a structural unit represented by the following general formula (XIII) or (XIV), and the weight average molecular weight is 300-5,000, and one terminal is the following general formula (XV) Alternatively, a polyvinyl ether compound comprising a homopolymer or copolymer of an alkyl vinyl ether having a structure represented by (XVI) can also be used.

(In formulas (XIII) and (XIV), R ⁵⁷ and R ⁵⁸ each represent a hydrocarbon group having 1 to 8 carbon atoms.)

(In formulas (XV) and (XVI), R ⁵⁹ represents an alkyl group having 1 to 3 carbon atoms, and R ⁶⁰ and R ⁶¹ each represents a hydrocarbon group having 1 to 8 carbon atoms.)

  In the refrigerating machine oil composition of the present invention (including the refrigerating machine oil composition contained in the working fluid composition for a refrigerating machine of the present invention, the same applies hereinafter), the hydrocarbon oil content is the total amount of the refrigerating machine oil composition. As a reference | standard, it is required that it is 20-95 mass%, Preferably it is 25-90 mass%, More preferably, it is 30-85 mass%. Further, the content of oxygen-containing oil is required to be 5 to 80% by mass, preferably 10 to 75% by mass, more preferably 15 to 70% by mass, based on the total amount of the refrigerating machine oil composition. Most preferably, it is 20 to 60% by mass. In addition, when content of hydrocarbon oil exceeds 95 mass% and content of oxygen-containing oil is 5 mass% or less, refrigerant | coolant compatibility becomes inadequate. Moreover, when content of hydrocarbon oil is less than 20 mass% and content of oxygen-containing oil exceeds 80 mass%, the fall of refrigerant | coolant melt viscosity becomes large and lubricity becomes inadequate.

Further, the kinematic viscosity at 40 ° C. of the refrigerating machine oil composition of the present invention is required to be 20 mm ² / s or more from the viewpoint of excellent lubricity, and is preferably 30 mm ² / s or more, preferably 40 mm ^2. / S or more is more preferable. For the same reason, the kinematic viscosity at 100 ° C. of the refrigerating machine oil composition of the present invention is preferably 3 mm ² / s or more, and more preferably 4 mm ² / s or more.

  The refrigerating machine oil composition of the present invention has a phosphoric acid ester, an acidic phosphoric acid ester, a thiophosphoric acid ester, an amine salt of an acidic phosphoric acid ester, and a chlorinated phosphoric acid ester in order to further improve the wear resistance and load resistance. And at least one phosphorus compound selected from the group consisting of phosphites can be blended. These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols and polyether type alcohols or derivatives thereof.

  Phosphate esters include tributyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate, tritetradecyl phosphate , Tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, etc. Can be mentioned.

  Examples of acidic phosphate esters include monobutyl acid phosphate, monopentyl acid phosphate, monohexyl acid phosphate, monoheptyl acid phosphate, monooctyl acid phosphate, monononyl acid phosphate, monodecyl acid phosphate, monoundecyl acid phosphate, monododecyl Acid phosphate, monotridecyl acid phosphate, monotetradecyl acid phosphate, monopentadecyl acid phosphate, monohexadecyl acid phosphate, monoheptadecyl acid phosphate, monooctadecyl acid phosphate, monooleyl acid phosphate, dibutyl acid phosphate, dipentyl acid , Dihexyl reed Dophosphate, diheptyl acid phosphate, dioctyl acid phosphate, dinonyl acid phosphate, didecyl acid phosphate, diundecyl acid phosphate, didodecyl acid phosphate, ditridecyl acid phosphate, ditetradecyl acid phosphate, dipentadecyl acid, dipentadecyl acid Examples include hexadecyl acid phosphate, diheptadecyl acid phosphate, dioctadecyl acid phosphate, dioleyl acid phosphate, and the like.

  Examples of thiophosphates include tributyl phosphorothioate, tripentyl phosphorothioate, trihexyl phosphorothioate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl phosphorothioate. Phosphorothioate, triundecyl phosphorothionate, tridodecyl phosphorothionate, tritridecyl phosphorothionate, tritetradecyl phosphorothionate, tripentadecyl phosphorothionate, trihexadecyl phosphorothionate, Triheptadecyl phosphorothioate, trioctadecyl phosphorothionate, trioleyl phosphorothionate, triphenyl phosphorothionate, tricresyl phosphorothionate, trixyl Cycloalkenyl phosphorothionate, cresyldiphenyl phosphorothionate, like carboxymethyl Les sulfonyl diphenyl phosphorothionate.

  Examples of the amine salt of acidic phosphate ester include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, Examples thereof include salts with amines such as dipentylamine, dihexylamine, diheptylamine, dioctylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine.

  Examples of the chlorinated phosphate ester include tris-dichloropropyl phosphate, tris-chloroethyl phosphate, tris-chlorophenyl phosphate, polyoxyalkylene bis [di (chloroalkyl)] phosphate, and the like. As phosphites, dibutyl phosphite, dipentyl phosphite, dihexyl phosphite, diheptyl phosphite, dioctyl phosphite, dinonyl phosphite, didecyl phosphite, diundecyl phosphite, didodecyl phosphite, dioleyl Phosphite, diphenyl phosphite, dicresyl phosphite, tributyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl phosphite Phyto, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite and the like can be mentioned. Mixtures of these can also be used.

  When the refrigerating machine oil composition of the present invention contains the above phosphorus compound, the content of the phosphorus compound is not particularly limited, but it is 0.00 on the basis of the total amount of the refrigerating machine oil composition (based on the total amount of the base oil and all the blended additives). The content is preferably 01 to 5.0 mass%, more preferably 0.02 to 3.0 mass%. In addition, the said phosphorus compound may be used individually by 1 type, and may use 2 or more types together.

  In addition, the refrigerating machine oil composition of the present invention has a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, an allyl oxirane compound, an alkyl oxirane compound, a fat, It can contain at least one epoxy compound selected from cyclic epoxy compounds, epoxidized fatty acid monoesters and epoxidized vegetable oils.

  Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. Examples of the alkylphenyl glycidyl ether herein include those having 1 to 3 alkyl groups having 1 to 13 carbon atoms, and those having one alkyl group having 4 to 10 carbon atoms, such as n-butylphenyl glycidyl. Ether, i-butylphenyl glycidyl ether, sec-butylphenyl glycidyl ether, tert-butylphenyl glycidyl ether, pentylphenyl glycidyl ether, hexylphenyl glycidyl ether, heptylphenyl glycidyl ether, octylphenyl glycidyl ether, nonylphenyl glycidyl ether, decylphenyl A glycidyl ether etc. can be illustrated as a preferable thing.

  As the alkyl glycidyl ether type epoxy compound, specifically, decyl glycidyl ether, undecyl glycidyl ether, dodecyl glycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentyl glycol diglycidyl ether, Examples thereof include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, and polyalkylene glycol diglycidyl ether.

  Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester, etc., and preferable ones are glycidyl-2,2-dimethyloctanoate, glycidyl benzoate, glycidyl acrylate. And glycidyl methacrylate.

  Specific examples of the allyloxirane compound include 1,2-epoxystyrene and alkyl-1,2-epoxystyrene.

  Specific examples of the alkyloxirane compound include 1,2-epoxybutane, 1,2-epoxypentane, 1,2-epoxyhexane, 1,2-epoxyheptane, 1,2-epoxyoctane, 1,2- Epoxy nonane, 1,2-epoxydecane, 1,2-epoxyundecane, 1,2-epoxydodecane, 1,2-epoxytridecane, 1,2-epoxytetradecane, 1,2-epoxypentadecane, 1,2- Examples include epoxyhexadecane, 1,2-epoxyheptadecane, 1,1,2-epoxyoctadecane, 2-epoxynonadecane, 1,2-epoxyicosane and the like.

  Specific examples of the alicyclic epoxy compound include 1,2-epoxycyclohexane, 1,2-epoxycyclopentane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and bis (3,4 -Epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorbornane, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hept-3- Yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2-methyl Examples include cyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

  Specific examples of the epoxidized fatty acid monoester include an ester of an epoxidized fatty acid having 12 to 20 carbon atoms with an alcohol or phenol having 1 to 8 carbon atoms or an alkylphenol. In particular, butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and butylphenyl esters of epoxy stearate are preferably used.

  Specific examples of the epoxidized vegetable oil include epoxy compounds of vegetable oils such as soybean oil, linseed oil and cottonseed oil.

  Among these epoxy compounds, phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compounds and epoxidized fatty acid monoesters are preferred. Of these, phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds are more preferred, and phenyl glycidyl ether, butylphenyl glycidyl ether, alkyl glycidyl esters or mixtures thereof are particularly preferred.

  When the refrigerating machine oil composition of the present invention contains the epoxy compound, the content of the epoxy compound is not particularly limited, but is preferably 0.1 to 5.0% by mass based on the total amount of the refrigerating machine oil composition, More preferably, it is 0.2-2.0 mass%. In addition, the said epoxy compound may be used individually by 1 type, and may use 2 or more types together.

  Furthermore, the refrigerating machine oil composition of the present invention can contain conventionally known refrigerating machine oil additives as necessary in order to further enhance its performance. Examples of such additives include phenolic antioxidants such as di-tert-butyl-p-cresol and bisphenol A, phenyl-α-naphthylamine, N, N-di (2-naphthyl) -p-phenylenediamine, and the like. Amine-based antioxidants, anti-wear agents such as zinc dithiophosphate, extreme pressure agents such as chlorinated paraffin and sulfur compounds, oil-based agents such as fatty acids, antifoaming agents such as silicones, metal inertness such as benzotriazole Agents, viscosity index improvers, pour point depressants, detergent dispersants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type. The content of these additives is not particularly limited, but is preferably 10% by mass or less, more preferably 5% by mass or less, based on the total amount of oxygenated oil.

  The water content of the refrigerating machine oil composition of the present invention is not particularly limited, but can be preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total amount of the refrigerating machine oil composition. In particular, when used for a closed-type refrigerator, a low water content is required from the viewpoint of the influence on the stability of the oxygen-containing oil.

  The refrigerating machine oil composition of the present invention exerts its excellent effect when used together with an HFC refrigerant having fewer fluorine atoms than the number of hydrogen atoms. The refrigerant used, that is, the operation of the refrigerating machine of the present invention The refrigerant contained in the fluid composition may be an HFC refrigerant having less fluorine atoms than the number of hydrogen atoms, a mixed refrigerant with other HFC refrigerants, or an HFC refrigerant having less fluorine atoms than the number of hydrogen atoms. It may be a mixed refrigerant with a refrigerant other than HFC. Examples of refrigerants other than HFC include fluorine-containing ether refrigerants such as perfluoroethers, dimethyl ether, ammonia, and hydrocarbon refrigerants.

Examples of the HFC refrigerant having less fluorine atoms than hydrogen atoms include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, fluoromethane (HFC-41: CH ₃ F), 1,2-difluoroethane (HFC-152: CH ₂ F—CH ₂ F), 1,1-difluoroethane (HFC-152a: CHF ₂ —) HFC such as CH ₃ ) can be mentioned, among which 1,1-difluoroethane (HFC-152a) is particularly preferable.

  As the HFC refrigerant other than the HFC refrigerant having a smaller number of fluorine atoms than the number of hydrogen atoms, a hydrofluorocarbon having 1 to 2 carbon atoms is preferably used. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1, Examples thereof include HFC refrigerants such as 1,1,2-tetrafluoroethane (HFC-134a) and 1,1,1-trifluoroethane (HFC-143a).

  Specific examples of the fluorinated ether-based refrigerant include HFE-134p, HFE-245mc, HFE-236mf, HFE-236me, HFE-338mcf, HFE-365mcf, HFE-245mf, HFE-347mmy, and HFE-. 347mcc, HFE-125, HFE-143m, HFE-134m, HFE-227me and the like.

  As the hydrocarbon refrigerant, a gas refrigerant at 25 ° C. and 1 atm is preferably used. Specifically, it is an alkane, cycloalkane, alkene or a mixture thereof having 1 to 5 carbon atoms, preferably 1 to 4 carbon atoms. Specific examples include methane, ethylene, ethane, propylene, propane, cyclopropane, butane, isobutane, cyclobutane, methylcyclopropane, and mixtures of two or more thereof. Among these, propane, butane, isobutane or a mixture thereof is preferable.

Mixing ratio of HFC refrigerant with fewer fluorine atoms than other hydrogen atoms and other refrigerants (HFC refrigerants other than HFC refrigerants with fewer fluorine atoms than hydrogen atoms, fluorine-containing ether refrigerants, dimethyl ether, ammonia, hydrocarbon refrigerants) May be blended at 100 parts by mass or less, preferably 40 parts by mass or less, and more preferably 20 parts by mass or less with respect to 100 parts by mass of the HFC refrigerant having less fluorine atoms than hydrogen atoms.

  The mixing ratio of the refrigerant and the refrigerating machine oil in the refrigerating machine fluid composition of the present invention is not particularly limited, but the refrigerating machine oil is preferably 1 to 500 parts by mass, more preferably 2 to 400 parts by mass with respect to 100 parts by mass of the refrigerant. Part.

  The refrigerating machine oil composition and the working fluid composition for a refrigerating machine of the present invention are preferably used for a reciprocating or rotating automotive air conditioner. Further, the refrigerator oil composition and the working fluid composition for the refrigerator of the present invention include a refrigerator, a room air conditioner, a packaged air conditioner, a dehumidifier, a hot water heater, a freezer / refrigerated warehouse, a vending machine, a showcase, a chemical plant, etc. Etc. are preferably used. Furthermore, the working fluid composition for a refrigerating machine oil refrigerating machine is also preferably used for those having a centrifugal compressor.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

[Examples 1-14, Comparative Examples 1-10]
In Examples 1-14 and Comparative Examples 1-10, refrigeration oil compositions shown in Tables 2-6 were prepared using base oils 1-12 shown in Table 1, respectively.

  Next, the following evaluation tests were performed on the refrigerator oil compositions of Examples 1 to 14 and Comparative Examples 1 to 10.

(Refrigerant compatibility)
In accordance with JIS-K-2211 “Refrigerating machine oil” “Compatibility testing method with refrigerant”, 2 g of 1,1-difluoroethane refrigerant is mixed with 2 g of 1,1-difluoroethane refrigerant, and 1,1-difluoroethane refrigerant and refrigerating machine oil are mixed. Were observed to be mutually dissolved at 20 ° C. and evaluated as “compatible”, “white turbidity”, and “separation”. The obtained results are shown in Tables 2 to 6.

(Lubricity (Amount of wear))
In accordance with ASTM D 2670 “FALEXWEAR TEST”, the running-in operation was performed for 1 minute under a load of 150 lb under the condition of the temperature of the refrigerator oil of 100 ° C. Next, while blowing 1,1-difluoroethane refrigerant 10 L / h, the test machine was operated under a load of 250 lb for 2 hours, and the amount of wear of the test journal (pin) after the test was measured. The obtained results are shown in Tables 2 to 6.

Claims (4)

Contains 20 to 95% by mass of hydrocarbon oil and 5 to 80% by mass of oxygen-containing oil, based on the total amount of the refrigerating machine oil composition, and has a kinematic viscosity at 40 ° C. of 20 mm ² / s or more, fluorine A refrigerating machine oil composition characterized by being used together with a hydrofluorocarbon refrigerant having a smaller number of atoms than a number of hydrogen atoms.   The refrigerating machine oil composition according to claim 1, wherein the hydrofluorocarbon refrigerant is 1,1-difluoroethane.   The refrigerating machine oil composition according to claim 1, wherein the oxygen-containing oil is at least one selected from esters, polyglycols and polyvinyl ethers. A working fluid composition for a refrigerating machine, comprising the refrigerating machine oil composition according to any one of claims 1 to 3 and a hydrofluorocarbon refrigerant having a number of fluorine atoms smaller than the number of hydrogen atoms.