JP5550417B2 - Refrigerator oil and working fluid composition for refrigerator - Google Patents

Description

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

  Due to the problem of ozone layer destruction in recent years, CFC (chlorofluorocarbon) and HCFC (hydrochlorofluorocarbon), which have been used as refrigerants in conventional refrigeration equipment, are subject to regulation, and HFC (hydrofluorocarbon) is used as a refrigerant instead. It is being done.

  When CFC or HCFC is used as a refrigerant, mineral oil or hydrocarbon oil such as alkylbenzene has been suitably used as the refrigeration oil. However, when the refrigerant is changed, the refrigeration oil used in the coexistence is compatible with the refrigerant, Refrigerating machine oil needs to be developed for each refrigerant in order to exhibit unpredictable behaviors such as lubricity, melt viscosity with refrigerant, and thermal and chemical stability. Therefore, as a refrigerating machine oil for HFC refrigerant, for example, polyalkylene glycol (see Patent Document 1), ester (see Patent Document 2), carbonate (see Patent Document 3), polyvinyl ether (see Patent Document 4) Etc. are being developed. Among these refrigerating machine oils, esters are widely used for refrigerators and air conditioners.

  Among HFC refrigerants, HFC-134a, R407C, and R410A, which are standardly used as refrigerants for car air conditioners, refrigerators, and room air conditioners, have zero ozone depletion potential (ODP) but have a global warming potential (GWP) Are becoming subject to regulation. Therefore, there is an urgent need to develop refrigerants that can replace these HFCs.

  Under such a background, as a refrigerant that replaces the HFC, both ODP and GWP are very small, non-flammable, and a thermodynamic characteristic that is a measure of refrigerant performance is approximately the same as that of the HFC. The use of propene refrigerants has been proposed. Furthermore, the use of a mixed refrigerant of fluoropropene and saturated hydrofluorocarbon, saturated hydrocarbon having 3 to 5 carbon atoms, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide or trifluoroiodomethane is also proposed ( (See Patent Document 5). In addition, difluoromethane refrigerant (HFC-32) is attracting attention because of its relatively low global warming potential and high refrigeration efficiency among HFC refrigerants.

  On the other hand, it can be used with fluoropropene refrigerant or a mixed refrigerant of fluoropropene and saturated hydrofluorocarbon, saturated hydrocarbon having 3 to 5 carbon atoms, dimethyl ether, carbon dioxide, bis (trifluoromethyl) sulfide or trifluoroiodomethane. Refrigerating machine oils include mineral oils, alkylbenzenes, polyalphaolefins, polyalkylene glycols, monoesters, diesters, polyol esters, phthalate esters, alkyl ethers, ketones, carbonate esters, and polyvinyl ethers. Refrigerating machine oil using the above has been proposed (see Patent Literature 5, Patent Literature 6, and 7).

Japanese Patent Laid-Open No. 02-242888 Japanese Patent Laid-Open No. 03-200895 Japanese Patent Laid-Open No. 03-217495 Japanese Patent Laid-Open No. 06-128578 International Publication WO2006 / 094303 Pamphlet JP-T-2006-512426 International Publication WO2005 / 103190 Pamphlet

  As described in Patent Documents 5, 6, and 7, in a refrigeration system using a fluoropropene refrigerant, mineral oil used in CFC and HCFC, hydrocarbons such as alkylbenzene, and polyphenol used in HFC. It is considered that any refrigerating machine oil such as alkylene glycol, polyol ester, and polyvinyl ether is applicable. However, according to the study by the present inventors, a high level of refrigerant compatibility and thermal / chemical stability can be obtained simply by diverting conventional refrigeration oil used in refrigerants such as CFC and HCFC to the system as it is. Can not be achieved. In particular, the fluoropropene refrigerant has a problem in stability, and the difluoromethane refrigerant has low compatibility with the refrigerating machine oil, and a refrigerating machine oil that can be used in common for both is not known at present.

  The present invention has been made in view of such circumstances, and achieves both refrigerant compatibility and thermal / chemical stability at a high level in a refrigeration system using a fluoropropene refrigerant, a difluoromethane refrigerant, or the like. It is an object of the present invention to provide a refrigerating machine oil and a working fluid composition for a refrigerating machine.

  As a result of intensive studies to achieve the above object, the present inventors have used an ester with a specific polyhydric alcohol having a specific fatty acid composition, so that coexistence with a fluoropropene refrigerant, a difluoromethane refrigerant, or the like. The inventors have found that a refrigerating machine oil having sufficient thermal and chemical stability and sufficient compatibility with a refrigerant can be realized, and the present invention has been completed.

That is, this invention provides the working fluid composition for refrigerators shown to following (1)-(4), and the refrigerator oil shown to following (5).
(1) An ester of a fatty acid and an alcohol, wherein the fatty acid has two or more branched chains in the fatty acid constituting the ester, and one of the branched chains is a branched chain bonded to the α-position carbon. Refrigerating machine oil containing an ester having a ratio of 10 mol% or more based on the total amount of the constituent fatty acids based on the total amount of the refrigerating machine oil, and a refrigerant containing unsaturated fluorinated hydrocarbon and / or difluoromethane And a working fluid composition for a refrigerator.
(2) The working fluid composition for a refrigerator according to (1), wherein the refrigerant contains an unsaturated fluorinated hydrocarbon.
(3) The working fluid composition for a refrigerator according to (1) or (2), wherein the refrigerant contains difluoromethane.
(4) The working fluid composition for a refrigerator according to any one of (1) to (3), wherein the refrigerant is a mixture of unsaturated fluorinated hydrocarbon and difluoromethane.
(5) An ester of a fatty acid and an alcohol, the fatty acid having two or more branched chains in the fatty acid constituting the ester, and one of the branched chains is a branched chain bonded to the α-position carbon. A ratio of 50 mol% or more of an ester having a ratio of 10 mol% or more based on the total amount of the constituent fatty acids, based on the total amount of refrigerating machine oil, and used together with a refrigerant containing unsaturated fluorinated hydrocarbon and / or difluoromethane, Refrigerator oil.

  According to the present invention, in a refrigeration system using a fluoropropene refrigerant or a difluoromethane refrigerant, a refrigerating machine oil that has excellent low temperature performance and can achieve both refrigerant compatibility and thermal / chemical stability at a high level, and A working fluid composition for a refrigerator is provided.

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

  The refrigerating machine oil according to the present embodiment is an ester of a fatty acid and an alcohol, and has two or more branched chains that occupy the constituent fatty acids of the ester, and one of the branched chains is an α-position carbon (on the carboxyl group). Esters having a proportion of fatty acids which are branched chains bonded to adjacent carbon atoms (hereinafter also referred to as “α-position branched chains”) of 10 mol% or more based on the total amount of fatty acids constituting the ester , "Esters according to this embodiment"). Moreover, the working fluid composition for refrigerators according to the present embodiment contains the ester according to the present embodiment and a refrigerant containing unsaturated fluorinated hydrocarbons. The refrigerant working fluid composition for a refrigerator includes an embodiment that includes a refrigerator oil containing an ester according to the present embodiment and a refrigerant containing an unsaturated fluorinated hydrocarbon. Furthermore, the working fluid composition for a refrigeration machine according to the present embodiment introduces refrigeration oil and a refrigerant separately into a refrigerant circulation cycle, and a mixture of the refrigeration oil and the refrigerant (that is, the working fluid for the refrigeration machine) in the cycle. A composition). Here, “refrigerator oil” means a refrigerant-free working fluid composition (usually a lubricant base oil or a mixture of a lubricant base oil and an additive) (the following). Same in description).

  The constituent fatty acid of the ester according to this embodiment has one α-position branched chain, and the content of fatty acids having a total of two or more branched chains is 10 mol% or more, preferably 20 mol% or more. Preferably it is 30 mol% or more. If these requirements are not satisfied, the performance of any one of refrigerant compatibility, refrigerant stability and lubricity is inferior.

  As the fatty acid having two or more branched chains and one of the branched chains is an α-position branched chain, those having 6 to 9 carbon atoms are preferably used. Specifically, for example, 2,3-dimethyl Butanoic acid, 2,3,3-trimethylbutanoic acid, 2-ethyl-3-methylbutanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethyl-2-ethylbutanoic acid, 3 -Methyl-2-isopropylbutanoic acid, 2,3,3-trimethylpentanoic acid, 2,3,4-trimethylpentanoic acid, 2,4,4-trimethylpentanoic acid, 2-methyl-3-ethylpentanoic acid, 2 -Ethyl-3-methylpentanoic acid, 2-ethyl-4-methylpentanoic acid, 2,3-dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 2,5-dimethylhexanoic acid, 3,3-dimethyl-2 -Iso Propylbutanoic acid, 2,3,3,4-tetramethylpentanoic acid, 2,3,4,4-tetramethylpentanoic acid, 2,3-dimethyl-3-ethylpentanoic acid, 2,4-dimethyl-3-ethyl Pentanoic acid, 3,3-dimethyl-2-ethylpentanoic acid, 3,4-dimethyl-2-ethylpentanoic acid, 4,4-dimethyl-2-ethylpentanoic acid, 2,3-diethylpentanoic acid, 2-methyl -3-propylpentanoic acid, 3-methyl-2-propylpentanoic acid, 4-methyl-2-propylpentanoic acid, 2-methyl-3-isopropylpentanoic acid, 3-methyl-2-isopropylpentanoic acid, 4-methyl 2-isopropylpentanoic acid, 2,3,3-trimethylhexanoic acid, 2,3,4-trimethylhexanoic acid, 2,3,5-trimethylhexanoic acid, 2,4,4- Trimethylhexanoic acid, 2,4,5-trimethylhexanoic acid, 2,5,5-trimethylhexanoic acid, 2-methyl-3-ethylhexanoic acid, 2-methyl-4-ethylhexanoic acid, 2-ethyl-3- Methylhexanoic acid, 2-ethyl-4-methylhexanoic acid, 2-ethyl-5-methylhexanoic acid, 2,3-dimethylheptanoic acid, 2,4-dimethylheptanoic acid, 2,5-dimethylheptanoic acid, 2, Examples include 6-dimethylheptanoic acid.

  Furthermore, as fatty acids other than fatty acids that have two or more branched chains and one of the branched chains may be included in the constituent fatty acids, fatty acids having 6 to 9 carbon atoms are preferable, 6-9 linear fatty acids, fatty acids having 6 to 9 carbon atoms having only one branched chain (including both those having and not having an α-position branched chain), having two or more branched chains, and Selected from fatty acids having 6 to 9 carbon atoms that do not have an α-branched chain, and fatty acids having 6 to 9 carbon atoms that have two or more branched chains and two or more of the branched chains are α-branched chains It is preferable to use 1 type, or 2 or more types. Specific examples of such fatty acids include pentanoic acid, 2,2-dimethylpropanoic acid, hexanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 2-ethylbutanoic acid, and heptanoic acid. 2,2-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, 2 -Ethylpentanoic acid, 3-ethylpentanoic acid, 1,1,2-trimethylbutanoic acid, 1,2,2-trimethylbutanoic acid, 1-ethyl-1 methylbutanoic acid, 1-ethyl-2-methylbutanoic acid, octanoic acid 2-ethylhexanoic acid, 3-ethylhexanoic acid, 3,5-dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 3,4-dimethylhexanoic acid, 4,5- Methylhexanoic acid, 2,2-dimethylhexanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2-propylpentanoic acid, nonanoic acid 2,2-dimethylheptanoic acid, 3,5,5-trimethylhexanoic acid, 2-methyloctanoic acid, 2-ethylheptanoic acid, 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,2,4,4-tetramethylpentanoic acid, 2,2,3,3-tetramethylpentanoic acid, 2,2,3,4-tetramethylpentanoic acid, 2,2-diisopropylpropionic acid, etc. .

  When a fatty acid other than a fatty acid having two or more branched chains and one of the branched chains is an α-position branched chain and other fatty acids are used in combination, the ratio of the other fatty acids is 90 mol% or less. And is preferably 80 mol% or less, more preferably 70 mol% or less. Outside this range, the stability in the presence of the unsaturated fluorinated hydrocarbon refrigerant will be low, or the compatibility with the difluoromethane refrigerant will be insufficient.

  Furthermore, the proportion of the fatty acid having 5 to 9 carbon atoms in the fatty acid constituting the ester according to this embodiment is preferably 60 mol% or more, more preferably 70 mol% or more, and 80 mol% or more. More preferably it is. If the ratio of these fatty acids is within the above range, both the stability in the presence of the refrigerant and the compatibility with the refrigerant tend to be compatible at a higher level.

  Examples of fatty acids other than fatty acids having 5 to 9 carbon atoms that can be included in the constituent fatty acids include linear fatty acids having 10 to 24 carbon atoms and branched fatty acids having 10 to 24 carbon atoms. More specifically, linear or branched decanoic acid, linear or branched undecanoic acid, linear or branched dodecanoic acid, linear or branched tridecanoic acid, linear or Branched tetradecanoic acid, linear or branched pentadecanoic acid, linear or branched hexadecanoic acid, linear or branched heptadecanoic acid, linear or branched octadecanoic acid, linear or Branched nonadecanoic acid, linear or branched icosanoic acid, linear or branched henicoic acid, linear or branched docosanoic acid, linear or branched tricosanoic acid, linear or Examples thereof include branched tetracosanoic acid.

  Moreover, as a polyhydric alcohol which comprises the ester which concerns on this embodiment, the polyhydric alcohol which has 2-6 hydroxyl groups is used preferably.

  Specific examples of the dihydric alcohol (diol) include ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, and 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, Examples thereof include 12-dodecanediol. Specific examples of trihydric or higher alcohols include trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- ( Pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (glycerin 2-3 trimer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, adonitol, arabitol, xylitol, mannitol Polysaccharides such as xylose, arapinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose, cellobiose, and partially etherified products thereof It is. Among these, since it is more excellent in hydrolysis stability, neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, di- (trimethylol propane), tri- (trimethylol propane), pentaerythritol, di More preferred are esters of hindered alcohols such as-(pentaerythritol), tri- (pentaerythritol), neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane and pentaerythritol, esters of di- (pentaerythritol) Is more preferred, neopentyl glycol, trimethylolpropane, pentaerythritol, di- (pentaerythritol) is more preferred, compatibility with the refrigerant and hydrolysis Since particularly excellent qualitative, pentaerythritol or pentaerythritol and di - mixed esters of (pentaerythritol) is most preferred.

  The method for producing an ester according to this embodiment is arbitrary. For example, after first synthesizing a carboxylic acid, the ester can be produced by an esterification reaction with a polyhydric alcohol.

  Although the synthesis method of carboxylic acid is arbitrary, it can manufacture by oxo reaction or aldol condensation, for example. More specifically, as an oxo reaction, an aldehyde is produced by reacting an olefin such as ethylene, propylene, butene, isobutylene, or a dimer thereof with hydrogen and carbon monoxide. In addition, as the aldol condensation, one or two or more aldehydes are reacted at 40 to 100 ° C. in the presence of an alkali catalyst, and then a hydrogen pressure of 2 to 10 MPa and a reaction temperature of 60 in the presence of a catalyst such as palladium on activated carbon. A hydrogenation reaction is performed at ˜150 ° C. for 1 to 5 hours to synthesize aldehyde, and then the desired product can be obtained by air oxidation or the like.

  The method for synthesizing the ester is also arbitrary. For example, the target ester is obtained by reacting an alcohol and a carboxylic acid at 200 to 300 ° C. in a nitrogen stream and performing the reaction for 10 to 40 hours while dehydrating.

  When the ester according to this embodiment is a polyol ester (that is, when the constituent alcohol is a polyhydric alcohol), the polyol ester remains as a hydroxyl group without being partly esterified. May be a partial ester, a complete ester in which all hydroxyl groups are esterified, or a mixture of partial esters and complete esters, but preferably has a hydroxyl value of 10 mgKOH / g or less Further, it is preferably 5 mgKOH / g or less, and most preferably 3 mgKOH / g or less.

  As ester which concerns on this embodiment, what consists of 1 type of ester of a single structure may be contained, and the mixture of 2 or more types of ester from which a structure differs may be contained.

  In addition, the ester according to this embodiment is an ester of one fatty acid and one polyhydric alcohol, an ester of two or more fatty acids and one polyhydric alcohol, one fatty acid and two or more fatty acids. Either an ester with a polyhydric alcohol, an ester of two or more fatty acids and two or more polyhydric alcohols may be used. Among these, an ester using a mixed fatty acid, in particular, an ester composed of two or more fatty acids in the ester molecule is excellent in low temperature characteristics and compatibility with a refrigerant.

  In the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment, the content of the ester according to the present embodiment is not particularly limited, but low temperature performance, lubricity, refrigerant compatibility, thermal / chemical stability, electricity From the point of being superior by various performances such as insulation, it is preferable to contain 50% by mass or more, more preferably 70% by mass or more, and even more preferably 80% by mass or more, based on the total amount of refrigerating machine oil. The content is most preferably 90% by mass or more.

  Of the components of the working fluid composition for a refrigerator according to the present embodiment, the refrigerator oil may be composed only of the ester according to the present invention, but further includes a base oil and various additives other than the ester. You may contain. In the following description, the contents of base oils and additives other than esters according to the present invention are shown on the basis of the total amount of refrigerating machine oil, but the contents of these components in the refrigerating machine fluid composition are When the total amount of machine oil is used as a reference, it is desirable to select so as to be within a preferable range described later.

  Base oils that can be used in combination with the ester according to the present embodiment include mineral oils, hydrocarbon-based oils such as olefin polymer alkyldiphenylalkanes, alkylnaphthalenes, and alkylbenzenes, and ester-based base oils other than polyol esters according to the present invention (mono Esters, polyol esters containing only linear fatty acids as constituent fatty acids, alkyl aromatic esters, alicyclic carboxylic acid esters, etc.), polyglycols, polyvinyl ethers, ketones, polyphenyl ethers, silicones, polysiloxanes, perfluoroethers, etc. A synthetic oil containing oxygen may be used in combination. As the synthetic oil containing oxygen, among the above, esters other than the ester according to the present embodiment, polyglycol, and polyvinyl ether are preferably used.

  Among the other oxygen-containing synthetic oils described above, particularly preferred are polyol esters other than the esters according to the present invention. Examples of polyol esters other than the esters according to the present invention include esters of polyhydric alcohols and fatty acids such as neopentyl glycol, trimethylol ethane, trimethylol propane, trimethylol butane, dipentaerythritol, and particularly preferred ones. An ester of neopentyl glycol and a fatty acid and an ester of dipentaerythritol and a fatty acid.

  The neopentyl glycol ester is preferably a fatty acid ester having 5 to 9 carbon atoms. Specific examples of such neopentyl glycol esters include neopentyl glycol di 3,5,5-trimethyl hexanate, neopentyl glycol di 2-ethyl hexanate, neopentyl glycol di 2-methyl hexanate, Neopentyl glycol di-2-ethylpentanoate, neopentyl glycol and 2-methylhexanoic acid 2-ethylpentanoic acid ester, neopentyl glycol and 3-methylhexanoic acid 5-methylhexanoic acid ester, neopentyl glycol Esters of 2-methylhexanoic acid, 2-ethylhexanoic acid, neopentyl glycol and 3,5-dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 3,4-dimethylhexanoic acid, neopentyl glycol dipentanate , Neo Emissions chill glycol di-2-ethyl pig sulfonate, neopentyl glycol di-2-methyl-pentanate, neopentyl glycol di-2-methyl-pig sulfonate, neopentyl glycol di methyl-pig sulfonates, and the like.

As dipentaerythritol esters, dipentaerythritol and esters of fatty acids having 5 to 7 carbon atoms, dipentaerythritol and esters of fatty acids having 5 to 7 carbon atoms and fatty acids having 8 to 9 carbon atoms are preferable. Specific examples of such dipentaerythritol esters include esters of dipentaerythritol and the following fatty acids.
2-methylbutanoic acid; 3-methylbutanoic acid; hexanoic acid; 2-methylpentanoic acid; 2-ethylbutanoic acid; 2-ethylpentanoic acid; 2-methylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutane 2 types selected from the group consisting of acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid and hexane 3 types selected from the group consisting of acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2 -From methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid Selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 5 types selected: 6 selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid Species: Seven types selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid; Acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid and 2-ethylbutane And 2-ethylpentanoic acid and 2-methylhexanoic acid; pentanoic acid and 3,5,5-trimethylhexanoic acid; 2-methylbutanoic acid and 3,5,5-trimethylhexanoic acid; 3-methylbutanoic acid and 3,5,5 5-trimethylhexanoic acid; hexanoic acid and 3,5,5-trimethylhexanoic acid; 2-methylpentanoic acid and 3,5,5-trimethylhexanoic acid; 2-ethylbutanoic acid and 3,5,5-trimethylhexanoic acid; 2-ethylpentanoic acid and 3,5,5-trimethylhexanoic acid; 2-methylhexanoic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid and 2-ethylhexanoic acid; 2-methylbutanoic acid and 2-ethylhexane Acid; 3-methylbutanoic acid and 2-ethylhexanoic acid; hexanoic acid and 2-ethylhexanoic acid; 2-methylpentanoic acid and 2-ethylhexanoic acid; 2 -Ethylbutanoic acid and 2-ethylhexanoic acid; 2-ethylpentanoic acid and 2-ethylhexanoic acid; 2-methylhexanoic acid and 2-ethylhexanoic acid; pentanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethyl Hexanoic acid; 2-methylbutanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; 3-methylbutanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; hexanoic acid and 2- Ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; 2-methylpentanoic acid and 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; 2-ethylbutanoic acid and 2-ethylhexanoic acid and 3,5 , 5-trimethylhexanoic acid; 2-ethylpentanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; 2-methylhexane And 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2 types selected from the group consisting of 2-methylhexanoic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid And 2-ethylhexanoic acid selected from the group consisting of 2-ethylpentanoic acid and 2-methylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2 2-ethyl and 2-ethyl selected from the group consisting of ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid Xanthic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexane 3 types selected from the group consisting of acids and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethyl 3 types selected from the group consisting of pentanoic acid and 2-methylhexanoic acid and 2-ethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 3 types selected from the group consisting of 2-ethylpentanoic acid and 2-methylhexanoic acid, 2-ethylhexanoic acid and 3, 5,5-trimethylhexanoic acid; from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 4 types selected and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2- 4 types selected from the group consisting of methylhexanoic acid and 2-ethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid And 4 selected from the group consisting of 2-methylhexanoic acid, 2-ethylhexanoic acid and 3,5,5-trimethyl 5-Hexane selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid; 3,5,5-trimethylhexanoic acid; consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 5 types selected from the group and 2-ethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexane 5 types selected from the group consisting of acids, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid 6 and 3,5 selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid , 5-trimethylhexanoic acid; selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 6 types and 2-ethylhexanoic acid; consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 6 types selected from the group, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid, 2 7 types selected from the group consisting of -methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid and 3,5,5-trimethyl Hexanoic acid; seven kinds selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid; 2-ethylhexanoic acid; selected from the group consisting of pentanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid and 2-methylhexanoic acid 7 types, 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid; pentanoic acid and 2-methylbutane And 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid; pentanoic acid and 2-methylbutanoic acid 3-methylbutanoic acid, hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 2-ethylhexanoic acid; pentanoic acid, 2-methylbutanoic acid, and 3-methylbutanoic acid Hexanoic acid, 2-methylpentanoic acid, 2-ethylbutanoic acid, 2-ethylpentanoic acid, 2-methylhexanoic acid, 3,5,5-trimethylhexanoic acid and 2-ethylhexanoic acid.

  In this embodiment, the blending amount in the case of blending other oxygen-containing synthetic oil is not particularly limited as long as the excellent lubricity and compatibility as a refrigerating machine oil is not impaired, but other than the ester according to the present embodiment. When blending the ester, it is necessary to be 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, and 70% by mass or less, based on the total amount of refrigerating machine oil. More preferably, it is still more preferably 60% by mass or less, and most preferably 50% by mass or less; when blending oxygen-containing synthetic oil other than ester, it is 50 based on the total amount of refrigerating machine oil. It is necessary to be not more than mass%, preferably not more than 40 mass%, more preferably not more than 30 mass%. If the blending amount of an ester other than the ester according to this embodiment or other oxygen-containing synthetic oil exceeds the upper limit, the characteristics of the present invention cannot be obtained.

  In the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment, the ester content according to the present embodiment is not particularly limited, but lubricity, refrigerant compatibility, thermal / chemical stability, electrical insulation, etc. From the point that it is more excellent in various performances, it is preferable to contain 50% by mass or more, more preferably 70% by mass or more, still more preferably 80% by mass or more, more preferably 90% by mass, based on the total amount of refrigerating machine oil. It is most preferable to contain the above.

  Moreover, the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment can be used in a form in which various additives are further blended as necessary.

  In order to further improve the wear resistance and load resistance of the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment, phosphoric acid ester, acidic phosphoric acid ester, thiophosphoric acid ester, amine salt of acidic phosphoric acid ester , At least one phosphorus compound selected from the group consisting of chlorinated phosphates and phosphites can be blended. These phosphorus compounds are esters of phosphoric acid or phosphorous acid with alkanols and polyether type alcohols or derivatives thereof.

  Specifically, for example, as phosphate ester, tryptyl phosphate, tripentyl phosphate, trihexyl phosphate, triheptyl phosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, triundecyl phosphate, tridodecyl phosphate, tritridecyl phosphate Decyl phosphate, tritetradecyl phosphate, tripentadecyl phosphate, trihexadecyl phosphate, triheptadecyl phosphate, trioctadecyl phosphate, trioleyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, And xylenyl diphenyl phosphate.

  Examples of acidic phosphate esters include monobutyl acyl 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 tryptyl phosphorothioate, tripentyl phosphorothionate, trihexyl phosphorothioate, triheptyl phosphorothionate, trioctyl phosphorothionate, trinonyl phosphorothionate, tridecyl 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 an acidic phosphate ester include an amine salt of an acidic phosphate ester and an amine having a primary or tertiary alkyl group having 1 to 24 carbon atoms, preferably 5 to 18 carbon atoms.

  The amine constituting the acid phosphate ester salt includes linear or branched methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecyl. Amine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, oleylamine, tetracosylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, dihexylamine, di Heptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipenta Silamine, dihexadecylamine, diheptadecylamine, dioctadecylamine, dioleylamine, ditetracosylamine, trimethylamine, triethylamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine , Trinonylamine, tridecylamine, triundecylamine, tridodecylamine, tritridecylamine, tritetradecylamine, tripentadecylamine, trihexadecylamine, triheptadecylamine, trioctadecylamine, trioleylamine tritetra And salts with amines such as cosylamine. The amine may be a single compound or a mixture of two or more compounds.

  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, triptyl phosphite, tripentyl phosphite, trihexyl phosphite, triheptyl phosphite, trioctyl phosphite, trinonyl phosphite, tridecyl phosphite, triundecyl Examples thereof include phosphite, tridodecyl phosphite, trioleyl phosphite, triphenyl phosphite, and tricresyl phosphite. Mixtures of these can also be used.

  When the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment contain the phosphorus compound, the content of the phosphorus compound is not particularly limited, but is based on the total amount of the refrigerating machine oil (the total amount of the base oil and all the blended additives). Standard), it is preferably 0.01 to 5.0% by mass, more preferably 0.02 to 3.0% by mass. In addition, the said phosphorus compound may be used individually by 1 type, and may use 2 or more types together.

  In addition, a terpene compound can be added to the refrigerating machine oil and the working fluid composition for the refrigerating machine according to the present embodiment in order to further improve the thermal and chemical stability. The “terpene compound” in the present invention means a compound obtained by polymerizing isoprene and a derivative thereof, and a dimer to octamer of isoprene is preferably used. Specific examples of the terpene compound include graniol, nerol, linalool, citral (including granial), citronellol, menthol, limonene, terpineol, carpon, yonon, tuyon, camphor, borneol and other monoterpenes, farnesene, Farnesol, nerolidol, juvenile hormone, humulene, cariophyllene, elemen, casinol, casquitene, tutin and other sesquiterpenes, granyl graniol, phytol, abietic acid, pimaragen, daphnetoxin, taxol, abietic acid, pimaric acid and other diterpenes, Sesterterpenes such as nilfarnesene, triterpenes such as squalene, limonin, cameliagenin, hopane and lanosterol, and tetraterpenes such as carotenoids And the like.

  Among these terpene compounds, monoterpenes, sesquiterpenes and diterpenes are preferable, sesquiterpenes are more preferable, α-farnesene (3,7,11-trimethyldodeca-1,3,6,10-tetraene) and / or β-farnesene. (7,11-dimethyl-3-methylidene deca-1,6,10-triene) is particularly preferred. In this invention, a terpene compound may be used individually by 1 type, and may be used in combination of 2 or more type.

  The content of the terpene compound in the refrigerating machine oil according to the present invention is not particularly limited, but is preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, and still more preferably 0.00% based on the total amount of the refrigerating machine oil. It is 05-3 mass%. When the content of the terpene compound is less than 0.001% by mass, the effect of improving the thermal and chemical stability tends to be insufficient, and when it exceeds 10% by mass, the lubricity tends to be insufficient. is there. Further, the content of the terpene compound in the working fluid composition for a refrigerator of the present invention is desirably selected so as to be within the above preferable range when the total amount of the refrigerator oil is used as a reference.

  In addition, the refrigerating machine oil and the working fluid composition for the refrigerating machine according to the present embodiment include a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, and a glycidyl ester type in order to further improve the thermal and chemical stability. It can contain at least one epoxy compound selected from an epoxy compound, an allyloxirane compound, an alkyloxirane compound, an alicyclic epoxy compound, an epoxidized fatty acid monoester, and an epoxidized vegetable oil.

  Specific examples of the phenyl glycidyl ether type epoxy compound include phenyl glycidyl ether and alkylphenyl glycidyl ether. As used herein, the alkylphenyl glycidyl ether includes 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-ptylphenyl glycidyl. Ether, i-butyl phenyl glycidyl ether, SeC-butyl phenyl glycidyl ether, tert-butyl phenyl glycidyl ether, pentyl phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, decyl phenyl 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 include trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidyl ether, polyalkylene glycol monoglycidyl ether, polyalkylene glycol diglycidyl ether, and the like.

  Specific examples of the glycidyl ester type epoxy compound include phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester and the like, and preferable ones include 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, 1,2-epoxyoctadecane, 1,2-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, bis (3, 4-epoxycyclohexylmethyl) adipate, exo-2,3-epoxynorpolnan, bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, 2- (7-oxabicyclo [4.1.0] hepto 3-yl) -spiro (1,3-dioxane-5,3 ′-[7] oxabicyclo [4.1.0] heptane, 4- (1′-methylepoxyethyl) -1,2-epoxy-2- Examples thereof include methylcyclohexane and 4-epoxyethyl-1,2-epoxycyclohexane.

  Specific examples of the epoxidized fatty acid monoester include esters 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, ptyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl, phenyl and ptylphenyl esters of epoxy stearic acid 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, butyl phenyl glycidyl ether, alkyl glycidyl esters or mixtures thereof are particularly preferred.

  When the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment contain the epoxy compound, the content of the epoxy compound is not particularly limited, but is 0.1 to 5.0% by mass based on the total amount of the refrigerating machine oil. It is preferable that 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.

  In addition, the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment can contain conventionally known additives for refrigerating machine oil as necessary in order to further enhance the 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 refrigerating machine oil.

Kinematic viscosity of the refrigerating machine oil according to the present embodiment is not particularly limited, the kinematic viscosity at 40 ° C., preferably 3~1000mm ² / s, more preferably 4~500mm ² / s, and most preferably 5~400mm ² / s. The kinematic viscosity at 100 ° C. is preferably 1 to 100 mm ² / s, more preferably ² to 50 mm ² / s. When the kinematic viscosity is less than the lower limit value, the lubricity tends to be insufficient. On the other hand, when the kinematic viscosity exceeds the upper limit value, the compatibility with the difluoromethane refrigerant tends to be insufficient.

Further, the volume resistivity of the refrigerating machine oil according to the present embodiment is not particularly limited, but is preferably 1.0 × 10 ¹² Ω · cm or more, more preferably 1.0 × 10 ¹³ Ω · cm or more, most preferably 1. 0.0 × 10 ¹⁴ Ω · cm or more. In particular, when it is used for a hermetic refrigerator, high electrical insulation tends to be required. In the present invention, the volume resistivity means a value at 25 ° C. measured in accordance with JIS C2101 “Electrical Insulating Oil Test Method”.

  In addition, the water content of the refrigerating machine oil according to the present embodiment is not particularly limited, but is preferably 200 ppm or less, more preferably 100 ppm or less, and most preferably 50 ppm or less based on the total quantity of refrigerating machine oil. In particular, when it is used for a hermetic type refrigerator, the moisture content is required to be small from the viewpoint of the influence on the thermal / chemical stability and electrical insulation of the refrigerator oil.

  Further, the acid value of the refrigerating machine oil according to the present embodiment is not particularly limited, but is contained in the refrigerating machine oil for fluoropropene refrigerant according to the present embodiment in order to prevent corrosion to the metal used in the refrigerating machine or piping. In order to prevent degradation of the ester oil, it is preferably 0.1 mgKOH / g or less, more preferably 0.05 mgKOH / g or less. In addition, in this invention, an acid value means the acid value measured based on JISK2501 "Petroleum product and lubricating oil one-neutralization number test method".

  Further, the ash content of the refrigerating machine oil according to the present embodiment is not particularly limited, but is preferably 100 ppm or less in order to increase the thermal and chemical stability of the fluoropropene refrigerant refrigerating machine oil according to the present embodiment and suppress the generation of sludge and the like. More preferably, it can be 50 ppm or less. In the present invention, the ash means the value of ash measured in accordance with JIS K2272 “Testing method for ash and sulfated ash of crude oil and petroleum products”.

  The refrigerating machine oil according to the present embodiment exhibits sufficiently high stability and sufficiently high compatibility when used together with various refrigerants, and can be widely used as refrigerating machine oil. Specific examples of refrigerators in which the refrigerating machine oil of the present invention is used include room air conditioners, packaged air conditioners, refrigerators, automotive air conditioners, dehumidifiers, freezers, refrigerated warehouses, vending machines, showcases, chemical plants, etc. Among them, it is particularly preferably used in a refrigerator having a hermetic compressor. Further, the refrigerating machine oil of the present invention can be used for any type of compressor such as a reciprocating type, a rotary type, a centrifugal type and the like.

  That is, when using the refrigerator oil containing the ester which concerns on this invention as a fluid composition for refrigerators, it contains the refrigerator oil and the refrigerant | coolant containing the said ester of the said invention, It is characterized by the above-mentioned. Here, the blending ratio of the refrigerating machine oil containing the ester according to the present invention and the refrigerant is not particularly limited, but the blending quantity of the refrigerating machine oil is usually 1 to 1000 parts by weight, preferably 100 parts by weight of the refrigerant. 2 to 800 parts by weight.

  In the fluid composition for a refrigerator according to the present invention, an HFC refrigerant, an unsaturated fluorinated hydrocarbon (HFO) refrigerant, a trifluoroiodomethane refrigerant, a fluorinated ether refrigerant such as perfluoroethers, dimethyl ether, etc. Non-fluorine-containing ether refrigerants such as ammonia, natural refrigerants such as ammonia, carbon dioxide and hydrocarbons may be contained.

  Examples of the HFC refrigerant include hydrofluorocarbons having 1 to 3 carbon atoms, preferably 1 to 2 carbon atoms. Specifically, for example, difluoromethane (HFC-32), trifluoromethane (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1, 1,1,2-tetrafluoroethane (HFC-134a), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1 1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3 , 3,3-hexafluoropropane (HFC-236fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa), and 1,1 1,3,3-pentafluorobutane (HFC-365mfc), or a mixture of two or more thereof. These refrigerants are appropriately selected depending on the application and required performance. For example, HFC-32 alone; HFC-23 alone; HFC-134a alone; HFC-125 alone; HFC-134a / HFC-32 = 60 to 80 mass % / 40-20 mass% mixture; HFC-32 / HFC-125 = 40-70 mass% / 60-30 mass% mixture; HFC-125 / HFC-143a = 40-60 mass% / 60-40 mass % Mixture; HFC-134a / HFC-32 / HFC-125 = 60 wt% / 30 wt% / 10 wt% mixture; HFC-134a / HFC-32 / HFC-125 = 40-70 wt% / 15- 35 mass% / 5 to 40 mass% mixture; HFC-125 / HFC-134a / HFC-143a = 35-55 mass% / 1-15 mass% / 40-60 mass Such as a mixture of preferred examples include. More specifically, a mixture of HFC-134a / HFC-32 = 70/30 mass%; a mixture of HFC-32 / HFC-125 = 60/40 mass%; HFC-32 / HFC-125 = 50/50 mass % Mixture (R410A); HFC-32 / HFC-125 = 45/55 wt% mixture (R410B); HFC-125 / HFC-143a = 50/50 wt% mixture (R507C); HFC-32 / HFC -125 / HFC-134a = 30/10/60 wt% mixture; HFC-32 / HFC-125 / HFC-134a = 23/25/52 wt% mixture (R407C); HFC-32 / HFC-125 / HFC-134a = 25/15/60 mass% mixture (R407E); HFC-125 / HFC-134a / HFC-143a = Mixtures of 4/4/52 wt% (R404A), and the like.

  Of the HFC refrigerants, saturated hydrofluorocarbons include difluoromethane (HFC-32), pentafluoroethane (HFC-125), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1. , 1,2-Tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,2,3,3-hexafluoropropane (HFC-236ea), 1,1,1,3,3,3-hexafluoropropane (HFC-236fa), 1, 1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365 fc) is preferably one or a mixture of two or more, and from the viewpoint of refrigerant physical properties, HFC-32, HFC-125, HFC-134a, HFC-152a, or HFC-32 and HFC- A mixture of 134a is preferred. Among these, HFC-32 is particularly preferable in terms of low global warming potential and efficiency.

  The hydrocarbon refrigerant is preferably a hydrocarbon having 3 to 5 carbon atoms, specifically, for example, methane, ethylene, ethane, propylene, propane, cyclopropane, normal butane, isobutane, cyclobutane, methylcyclopropane, 2-methylbutane. , Normal pentane, or a mixture of two or more thereof. Among these, gas at 25 ° C. and 1 atm is preferably used, and propane, normal butane, isobutane, 2-methylbutane or a mixture thereof is preferable.

  Specific examples of the fluorinated ether refrigerant include HFE-134p, HFE-245mc, HFE-236mf, HFE-236me, HFE-338mcf, HFE-365mcf, HFE-245mf, HFE-347mmy, HFE-347mcc, HFE-125, HFE-143m, HFE-134m, HFE-227me, etc. are mentioned, These refrigerant | coolants are suitably selected according to a use or required performance.

  The blending ratio of the refrigerating machine oil and the refrigerant in the working fluid composition for a refrigerator according to the present embodiment, and the blending ratio of the refrigerating machine oil and the refrigerant in the working fluid composition for a refrigerator according to the present embodiment are not particularly limited, 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.

  The refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment are preferably used for an air conditioner, a refrigerator, or an open or sealed car air conditioner having a reciprocating or rotating hermetic compressor. Further, the refrigerating machine oil and the working fluid composition for the refrigerating machine according to the present embodiment are preferably used for a dehumidifier, a water heater, a freezer, a freezer / refrigerated warehouse, a vending machine, a showcase, a cooling device for a chemical plant, and the like. Furthermore, the refrigerating machine oil and the working fluid composition for a refrigerating machine according to the present embodiment are preferably used for those having a centrifugal compressor.

  The refrigerating machine oil and the refrigerating machine fluid composition according to the present embodiment can be suitably used for various unsaturated fluorocarbon refrigerant refrigerating machines as described above, but the refrigerant circulation cycle provided in the refrigerating machine. As a typical configuration, a compressor, a condenser, an expansion mechanism, an evaporator, and a dryer provided as necessary are exemplified.

  The compressor includes a motor composed of a rotor and a stator in a sealed container for storing refrigerating machine oil, a rotating shaft fitted to the rotor, and a compression connected to the motor via the rotating shaft. A high-pressure container type compressor in which high-pressure refrigerant gas discharged from the compressor unit stays in a sealed container, a motor composed of a rotor and a stator in a sealed container storing refrigerating machine oil, The rotary shaft fitted to the rotor and the compressor unit connected to the motor via the rotary shaft are housed, and the high-pressure refrigerant gas discharged from the compressor unit is outside the sealed container. Examples include a low-pressure container type compressor that is directly discharged.

  As an insulating film which is an electric insulation system material of a motor part, a crystalline plastic film having a glass transition point of 50 ° C. or more, specifically, for example, polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether ether ketone, polyethylene naphthalate, Polyamideimide, at least one insulating film selected from the group of polyimides, or a composite film in which a resin layer having a high glass transition temperature is coated on a film having a low glass transition temperature is less likely to cause deterioration of tensile strength characteristics and electrical insulation characteristics. Are preferably used. Moreover, as a magnet wire used for the motor part, an enamel coating having a glass transition temperature of 120 ° C. or higher, for example, a single layer such as polyester, polyesterimide, polyamide and polyamideimide, or a layer having a low glass transition temperature as a lower layer, Those having an enamel coating in which a high layer is composite-coated on the upper layer are preferably used. Examples of the composite enameled wire include polyester imide as a lower layer and polyamide imide as an upper layer (AI / EI), polyester as a lower layer and polyamide imide as an upper layer (AI / PE), and the like. .

  As the desiccant to be filled in the dryer, silicic acid and alkali metal aluminate composite salt having a pore diameter of 3.3 angstroms or less and a carbon dioxide absorption capacity at 25 ° C. carbon dioxide partial pressure of 250 mmHg is 1.0% or less. The synthetic zeolite is preferably used. Specifically, trade names XH-9, XH-10, XH-11, XH-600 manufactured by Union Showa Co., Ltd., and the like can be given.

  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.

[Example 1]
<Synthesis of 2-ethyl-4-methylpentanoic acid>
First, in order to synthesize 2-ethyl-4-methyl-2-pentenal, 100 ml (80 g, 1.11 mol) of n-butyraldehyde and 100 ml (79 g, 1.1 mol) of isobutyraldehyde were added to a stirrer and a condenser tube. Into a 500 ml four-necked flask, 200 ml of 2.5 mol% aqueous sodium hydroxide solution was added dropwise over 15 minutes while stirring at 80 ° C. Three hours after the start of dropping, the mixture was cooled to room temperature, the aqueous layer was separated, and the organic layer was washed with water three times. After confirming that the washing water was not alkaline, distillation was performed to obtain 50 g (0.40 mol) of 2-ethyl-4-methylpentenal.
Next, 50 g (0.4 mol) of 2-ethyl-4-methylpentenal was placed in an autoclave having an internal volume of 150 ml, 0.5 g of 5% by weight palladium-supported activated carbon was added as a catalyst, hydrogen pressure 5 MPa, reaction temperature 100 The hydrogenation reaction was carried out at 2 ° C. for 2 hours. 50 g of crude 2-ethyl-4-methylpentanal obtained by filtering the catalyst was put into a three-necked flask equipped with a cooling pipe and a gas introduction pipe, and air was blown at a flow rate of 80 ml / min at 40 ° C. The oxidation reaction was performed for 20 hours. Purification by distillation gave 40 g (0.28 mol) of 2-ethyl-4-methylpentanoic acid.
<Synthesis of ester>
2 g of pentaerythritol and 10.7 g of 2-ethyl-4-methylpentanoic acid were placed in a 100 ml three-necked flask equipped with a Dean-Stark oil / water separator and heated at 250 ° C. in a nitrogen atmosphere. When generation of water vapor became intense and bumping by water occurred, nitrogen was passed at 12.5 ml / min, and the reaction was carried out for 24 hours while dehydrating. Unreacted carboxylic acid was removed under reduced pressure under a nitrogen stream to obtain 9.3 g of tetraester of pentaerythritol and 2-ethyl-4-methylpentanoic acid.

[Example 2]
<Synthesis of 2-propyl-4-methylpentanoic acid>
2-propyl-4-methylpentanoic acid was synthesized in the same manner as in Example 1 except that valeraldehyde was used in place of n-butyraldehyde. As a result, 39 g (0.25 mol) of 2-propyl-4-methylpentanoic acid was obtained.
<Synthesis of ester>
Tetraester of pentaerythritol and 2-propyl-4-methylpentanoic acid in the same manner as in Example 1 except that 2-propyl-4-methylpentanoic acid was used instead of 2-ethyl-4-methylpentanoic acid. Got.

[Example 3]
Instead of 2-ethyl-4-methylpentanoic acid, a carboxylic acid mixture of 2-ethyl-4-methylpentanoic acid and 3,5,5-trimethylhexanoic acid (50% by mole of 2-ethyl-4-methylpentanoic acid) , 3,5,5-trimethylhexanoic acid 50 mol%) was used in the same manner as in Example 1 to obtain a tetraester of pentaerythritol and the above carboxylic acid mixture.

[Example 4]
Instead of 2-ethyl-4-methylpentanoic acid, a carboxylic acid mixture of 2-ethyl-4-methylpentanoic acid and 2-propyl-4-methylpentanoic acid (50% by mole of 2-ethyl-4-methylpentanoic acid) The tetraester of pentaerythritol and the above carboxylic acid mixture was obtained in the same manner as in Example 1 except that 2-propyl-4-methylpentanoic acid (50 mol%) was used.

[Example 5]
Instead of 2-ethyl-4-methylpentanoic acid, a carboxylic acid mixture of 2-ethyl-4-methylpentanoic acid and 2-ethylhexanoic acid (50% by mole of 2-ethyl-4-methylpentanoic acid, 2-ethyl A tetraester of pentaerythritol and the above carboxylic acid mixture was obtained in the same manner as in Example 1 except that 50 mol% of hexanoic acid was used.

[Example 6]
Instead of 2-ethyl-4-methylpentanoic acid, a carboxylic acid mixture of 2-ethylhexanoic acid and 2-propyl-4-methylpentanoic acid (2-ethylhexanoic acid 50 mol%, 2-propyl-4-methyl A tetraester of pentaerythritol and the above carboxylic acid mixture was obtained in the same manner as in Example 1 except that 50 mol% of pentanoic acid was used.

[Comparative Example 1]
A tetraester of pentaerythritol and 2-ethylhexanoic acid was obtained in the same manner as in Example 1 except that 2-ethylhexanoic acid was used instead of 2-ethyl-4-methylpentanoic acid.

[Comparative Example 2]
Instead of 2-ethyl-4-methylpentanoic acid, a carboxylic acid mixture of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid (2-ethylhexanoic acid 50 mol%, 3,5,5-trimethyl) A tetraester of pentaerythritol and the above carboxylic acid mixture was obtained in the same manner as in Example 1 except that 50 mol% of hexanoic acid was used.

[Comparative Example 3]
In the same manner as in Example 1 except that 3,5,5-trimethylhexanoic acid was used in place of 2-ethyl-4-methylpentanoic acid, a tetraethyl pentaerythritol and 3,5,5-trimethylhexanoic acid was used. An ester was obtained.

The molecular structure of 2-propyl-4-methylpentanoic acid obtained in Example 1, 2-ethyl-4-methylpentanoic acid obtained in Example 2, and each ester obtained in Examples 1-6 is They were identified by performing ¹ H-NMR analysis under the following measurement conditions. The results of ¹ H-NMR analysis are shown in Table 1. In addition, Tables 2 and 3 show kinematic viscosities and viscosity indices at 40 ° C. and 100 ° C. of the esters of Examples 1 to 6, respectively.
Measurement condition:
Device name: VARIAN INOVA 600 MHZ NMR
Solvent: CDCl ₃
Temperature: Room temperature

Formulas (1) to (8) in Table 1 are as follows.

  Next, the evaluation test as the refrigerating machine oil shown below was performed for the esters of Examples 1 to 6 and Comparative Examples 1 to 3.

<Compatibility test with refrigerant>
In accordance with JIS-K-2211 “Refrigerating machine oil” “Compatibility testing method with refrigerant”, the mixture of refrigerant 16 g and refrigerant oil 4 g shown in the table is gradually cooled from 30 ° C. to −40 ° C. The temperature at which phase separation or cloudiness occurred was measured. The obtained results are shown in Tables 2 and 3. In Tables 2 and 3, “HFO-1234yf + R32” means a mixed refrigerant (HFO-1234yf / R32 = 50/50 mass%) of HFO-1234yf and R32. In Tables 2 and 3, “<−40” indicates that phase separation and cloudiness were not observed in the measurement temperature range of this test. In Table 3, “separation” means that phase separation or cloudiness has already occurred at 30 ° C.

<Stability test>
In a 200 ml autoclave, 30 g of refrigerating machine oil whose water content was adjusted to 1000 ppm, 30 g of HFO-1234yf and 90 ml of air were sealed, and the acid value of the refrigerating machine oil after heating at 175 ° C. for 336 hours was measured. The obtained results are shown in Tables 2 and 3.

Claims (5)

The ratio of the fatty acid and alcohol ester, the fatty acid having two or more branched chains in the fatty acid constituting the ester and a branched chain in which one of the branched chains is bonded to the α-position carbon, Refrigerating machine oil containing 50% by mass or more of an ester that is 10 mol% or more based on the total amount of the constituent fatty acids,
A refrigerant comprising an unsaturated fluorinated hydrocarbon and / or difluoromethane ;
A working fluid composition for a refrigerator, comprising:   The working fluid composition for a refrigerator according to claim 1, wherein the refrigerant includes an unsaturated fluorinated hydrocarbon.   The working fluid composition for a refrigerator according to claim 1 or 2, wherein the refrigerant contains difluoromethane.   The working fluid composition for a refrigerator according to any one of claims 1 to 3, wherein the refrigerant is a mixture of unsaturated fluorinated hydrocarbon and difluoromethane. The ratio of the fatty acid and alcohol ester, the fatty acid having two or more branched chains in the fatty acid constituting the ester and a branched chain in which one of the branched chains is bonded to the α-position carbon, An ester that is 10 mol% or more based on the total amount of the constituent fatty acids , 50% by mass or more based on the total amount of refrigerating machine oil
Refrigerating machine oil used with refrigerants containing unsaturated fluorinated hydrocarbons and / or difluoromethane .