CN102191113B - Refrigerator oil and working fluid composition for refrigerating machine - Google Patents
Refrigerator oil and working fluid composition for refrigerating machine Download PDFInfo
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- CN102191113B CN102191113B CN201110063619.3A CN201110063619A CN102191113B CN 102191113 B CN102191113 B CN 102191113B CN 201110063619 A CN201110063619 A CN 201110063619A CN 102191113 B CN102191113 B CN 102191113B
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Abstract
The invention provides a kind of refrigerator oil and working fluid composition for refrigerating machine. Refrigerator oil of the present invention, it contains the ester more than benchmark 10 quality % taking refrigerator oil total amount, and use together with difluoromethane cold-producing medium, wherein said ester is the ester of dipentaerythritol and aliphatic acid, and the ratio of 2 methyl valeric acid is more than 20 % by mole in aliphatic acid. In addition, the refrigerator oil that working fluid composition for refrigerating machine of the present invention contains the invention described above and difluoromethane cold-producing medium.
Description
Technical field
The present invention relates to a kind of refrigerator oil and working fluid composition for refrigerating machine, in more detail, relate to a kind of withUseful refrigerator oil and used the refrigerator recruitment of this refrigerator oil when difluoromethane cold-producing medium (HFC-32) uses simultaneouslyMake fluid composition.
Background technology
Due to the problem of depletion of the ozone layer in recent years, in the past can be as the CFC (CFC) of the cold-producing medium of freezing machine andHCFC (HCFC) becomes the object of restriction, replaces them, is using HFC (hydrogen fluorohydrocarbon) as cold-producing medium.
In the situation that CFC and HCFC are cold-producing medium, as refrigerator oil, can suitably use mineral oil, alkylbenzeneDeng hydrocarbon ils, but replacing when cold-producing medium, owing to having shown at the refrigerator oil of the lower use that coexists and compatibility, the profit of cold-producing mediumSlip, with the unforeseeable behavior such as dissolving viscosity, heat/chemical stability of cold-producing medium, so that each cold-producing medium need to be developed is coldFreeze machine oil. Therefore,, as HFC cold-producing medium refrigerator oil, for example, developed poly-alkane glycol (with reference to Japanese kokai publication hei 02-No. 242888 communiques, ester (with reference to Japanese kokai publication hei 03-200895 communique), carbonic ester are (with reference to Japanese kokai publication hei 03-217495Number communique), polyvinylether (with reference to Japanese kokai publication hei 06-128578 communique) etc. In these refrigerator oils, ester is widely used inIn refrigerator, air-conditioning purposes etc.
In HFC cold-producing medium, that HFC-134a, R407C, R410A are typically used as is used for automobile air conditioning, refrigerator with or room conditioningUse cold-producing medium. But, although these HFC cold-producing medium ozone layer destroying coefficients (ODP) are 0 greenhouse effects of the earth coefficient (GWP) height, instituteTo become gradually the object of restriction. Therefore, the cold-producing medium of the alternative HFC of exploitation becomes the task of top priority.
Under such background, as the cold-producing medium of above-mentioned replacement HFC, propose to use the cold-producing medium of fluoropropenes class,The two is all very little for the ODP of the cold-producing medium of this fluoropropenes class and GWP, is flame retardancy, and as weighing refrigerant performanceThe thermodynamic behaviour of standard and above-mentioned HFC are roughly the same. In addition, use fluoropropenes and saturated hydrofluorocarbons have also been proposed, carbon is formerThe hybrid refrigeration of saturated hydrocarbons, dimethyl ether, carbon dioxide, two (trifluoromethyl) sulfide or the CF3I of subnumber 3～5Agent (with reference to International Publication WO2006/094303 brochure). Wherein, difluoromethane cold-producing medium (HFC-32) even if due toIn HFC cold-producing medium, greenhouse effects of the earth coefficient is also lower and freezing efficiency is higher, so attract attention.
, in the refrigerant circulation cycle of freezing machine, conventionally, refrigerator oil and the system of lubricated coolant compressorCryogen circulates together in the cycle, so require and the compatibility of cold-producing medium in refrigerator oil. But, will serve as HFC cold-producing mediumWith the refrigerator oil in the past using while using together with difluoromethane cold-producing medium, cannot obtain cold-producing medium and refrigerator oil is abundantCompatibility, be easily trapped in the cycle from the refrigerator oil of coolant compressor ejection, consequently produce refrigerant compressionRefrigerator oil mass in machine reduces and causes insufficient lubrication, or blocks such the asking of expansion mechanism such as capillary (capillary)Topic.
Therefore, for fear of this phenomenon, research and develop difluoromethane cold-producing medium refrigerator oil, for example, proposed ester systemRefrigerator oil is (with reference to Japanese kokai publication hei 6-17073 communique, Japanese kokai publication hei 10-298572 communique, TOHKEMY 2002-No. 060771 communique, TOHKEMY 2002-105471 communique, TOHKEMY 2002-129177 communique, TOHKEMY2002-129178 communique, TOHKEMY 2002-129179 communique).
Summary of the invention
The problem that invention will solve
But, even if while using above-mentioned ester to be in the past refrigerator oil, take into account with the compatibility of difluoromethane cold-producing medium andLubricity under difluoromethane cold-producing medium exists is also very difficult. For example, be in refrigerator oil with respect to ester in the pastDifluoromethane cold-producing medium shows the refrigerator oil of good compatibility, exists the lubricity under the existence of difluoromethane cold-producing medium not fillThe tendency of dividing. In addition, can enumerate viscosity (dynamic viscosity etc.) as the factor of influence of lubricity, exist at difluoromethane cold-producing mediumUnder lubricity in what become problem is because refrigerator oil and difluoromethane refrigerant mixture (being working fluid composition)Viscosity, its control may not be easy. And then, do not depend on that the object of controlling viscosity is refrigerator oil or working fluid combinationIn thing which and only adjust viscosity, cannot substantially improve lubricity.
In addition, the environment for use of the refrigerator oil in the refrigerant circulation cycle relates to the temperature of the wide region from high temperature to low temperatureDegree region, in addition, the ratio that exists of refrigerator oil and difluoromethane cold-producing medium has according to the position in refrigerant circulation cycleDifferent. But ester is in the past that refrigerator oil may not necessarily say sufficient to the adaptability of this environment for use. Especially lowThe inadequate situation of temperature mobility is more, and this problem is at TOHKEMY 2002-129177 communique and TOHKEMY 2002-In the situation of No. 129178 disclosed esters of communique, be obvious.
For the scheme of dealing with problems
The present invention makes in view of the problem that above-mentioned conventional art has, its objective is provide a kind of with difluoroWhen methane refrigerant is used together, can realize whole freezing of cold-producing medium compatibility, lubricity and low temperature flow by high levelMachine oil, and use its working fluid composition for refrigerating machine.
In order to address the above problem, the invention provides a kind of refrigerator oil, it is characterized in that, it contains with refrigerator oil totalAmount is ester more than benchmark meter 10 quality %, and uses together with difluoromethane cold-producing medium, and wherein said ester is dipentaerythritolWith the ester of aliphatic acid, and the ratio of 2 methyl valeric acid is more than 20 % by mole in above-mentioned aliphatic acid.
In addition, the invention provides a kind of working fluid composition for refrigerating machine, it is characterized in that, contain the invention described aboveRefrigerator oil and difluoromethane cold-producing medium.
Invention effect
According to refrigerator oil of the present invention and working fluid composition for refrigerating machine, in the time using difluoromethane cold-producing medium,Can realize cold-producing medium compatibility, lubricity and low temperature flow with high level whole.
Detailed description of the invention
Below the preferred embodiment of the present invention is elaborated.
The difluoromethane cold-producing medium refrigerator oil of present embodiment, it contains taking refrigerator oil total amount as benchmark 10 matterEster more than amount %, and use together with difluoromethane cold-producing medium, wherein said ester is the ester of dipentaerythritol and aliphatic acid. SeparatelyOutward, the refrigerator oil that the working fluid composition for refrigerating machine of present embodiment contains present embodiment and difluoromethane refrigerationAgent.
The content of the ester (being according to circumstances called below " dipentaerythritol fatty acid ester ") of dipentaerythritol and aliphatic acid, withRefrigerator oil total amount is benchmark, contain 10 quality % above, preferably contain 15 quality % above, more preferably contain 20 quality % withAbove, more than further preferably containing 30 quality %. The difluoromethane cold-producing medium of present embodiment can also contain with refrigerator oilBase oil, additive beyond dipentaerythritol fatty acid ester as described later, but the content of dipentaerythritol fatty acid ester is less thanWhen 10 quality %, cannot realize the profit under existing with compatibility, the difluoromethane cold-producing medium of difluoromethane cold-producing medium with high levelSlip and low temperature flow whole, particularly take into account compatibility and lubricity and become very difficult.
In addition, all hydroxyls that the dipentaerythritol fatty acid ester of present embodiment can comprise dipentaerythritol are by esterThe part of the hydroxyl of full ester, the dipentaerythritol of changing not esterified and the partial ester that retains and the mixture of full ester and partial ester,The preferably full ester of dipentaerythritol fatty acid ester.
Form in the aliphatic acid of dipentaerythritol fatty acid ester, the ratio of 2 methyl valeric acid is more than 20 % by mole, preferablyMore than 25 % by mole, more preferably more than 30 % by mole. When the ratio of 2 methyl valeric acid is less than aforementioned lower limit, cannot be with high levelRealize the whole of lubricity under existing with the compatibility of difluoromethane cold-producing medium, difluoromethane cold-producing medium and low temperature flow,Particularly take into account compatibility and lubricity and become very difficult. In addition, the ratio of the said 2 methyl valeric acid of the present invention refer toThe value that the fatty acid total amount of the contained formation dipentaerythritol fatty acid ester of refrigerator oil is benchmark.
The dipentaerythritol fatty acid ester of present embodiment is as long as the scope more than 20 % by mole contains 2-methylpentAcid, can also contain 2 methyl valeric acid aliphatic acid in addition as forming sour composition.
As the aliphatic acid beyond 2 methyl valeric acid, particularly, can enumerate acetic acid, propionic acid, butyric acid, 2 Methylpropionic acid,Valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, PA, caproic acid, 3 methylvaleric acid, 4-methylvaleric acid, 2,2-diformazanBase butyric acid, 2,3-acid dimethyl, 2,4-acid dimethyl, 3,3-acid dimethyl, 2 Ethylbutanoic acid, enanthic acid, 2-methyl oneselfAcid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2,4-dimethylValeric acid, 3,3-dimethyl valeric acid, 3,4-dimethyl valeric acid, 4,4-dimethyl valeric acid, 2-ethyl valeric acid, 3-ethyl valeric acid, 1,1,2-trimethyl butyric acid, 1,2,2-trimethyl butyric acid, 1-ethyl-1 methylbutanoic acid, 1-Ethyl-2-Methyl butyric acid, sad, 2-ethylCaproic acid, 3-thylhexoic acid, 3,5-dimethyl caproic acid, 2,4-dimethyl caproic acid, 3,4-dimethyl caproic acid, 4,5-dimethyl caproic acid,2,2-dimethyl caproic acid, 2-methyl enanthic acid, 3-methyl enanthic acid, 4-methyl enanthic acid, 5-methyl enanthic acid, 6-methyl enanthic acid, 2-propyl groupValeric acid, n-nonanoic acid, 2,2-dimethyl enanthic acid, 3,5,5-tri-methyl hexanoic acid, 2-methyloctanoic acid, 2-ethyl enanthic acid, 3-methyloctanoic acid, 2-Ethyl-2,3,3-trimethyl butyric acid, 2,2,4,4-tetramethyl valeric acid, 2,2,3,3-tetramethyl valeric acid, 2,2,3,4-tetramethyl pentaAcid, 2, the aliphatic acid of the carbon numbers 2～9 such as 2-diisopropyl propionic acid; Capric acid, undecyl acid, dodecyl acid, tridecylAcid, myristyl is sour, pentadecyl is sour, cetyl is sour, heptadecyl is sour, Eighteen alkyl acid, nonadecyl acid, eicosylThe aliphatic acid of the carbon numbers such as acid, oleic acid 10～20 etc.
When combination 2 methyl valeric acid and the aliphatic acid beyond it, as the aliphatic acid beyond 2 methyl valeric acid, preferably useThe branched chain fatty acid of the aliphatic acid of carbon number 5～7 and/or carbon number 8～9. Be used in combination 2 methyl valeric acid and carbon atomWhen the branched chain fatty acid of several 5～7 aliphatic acid and/or carbon number 8～9, be used in combination 2 methyl valeric acid, with except carbon atomWhen aliphatic acid beyond the branched chain fatty acid of several 5～7 aliphatic acid and/or carbon number 8～9, compare, often further improveLubricity under difluoromethane cold-producing medium exists and with the compatibility of difluoromethane cold-producing medium. In addition, be used in combination 2-firstWhen the branched chain fatty acid of the aliphatic acid of base valeric acid and carbon number 5～7 and/or carbon number 8～9, form dipentaerythritol fatThe ratio of the branched chain fatty acid of the carbon number 8～9 in the aliphatic acid of fat acid esters need to be, below 80 % by mole, preferably 75 to rubBelow you %, more preferably below 70 % by mole. When the ratio of the branched chain fatty acid of carbon number 8～9 exceedes 80 % by mole, with twoThe compatibility of fluoromethane cold-producing medium becomes insufficient.
In addition, except the aliphatic acid of carbon number 5～7 and/or the branched chain fatty acid of carbon number 8～9, use thisWhen aliphatic acid beyond a little aliphatic acid, form dipentaerythritol fatty acid ester aliphatic acid carbon number 5～7 aliphatic acid and/Or the ratio of the branched chain fatty acid of carbon number 8～9 is preferably more than 60 % by mole, more preferably more than 70 % by mole, further excellentSelect more than 80 % by mole. The ratio of the branched chain fatty acid of the aliphatic acid of carbon number 5～7 and/or carbon number 8～9 is aforementionedIn scope time, often can higher level take into account the lubricity of difluoromethane cold-producing medium under existing and with difluoromethane cold-producing mediumCompatibility both.
In the dipentaerythritol fatty acid ester of present embodiment, from take into account difluoromethane cold-producing medium exist lubricity withConsider the thing that sour constituent is particularly preferably only made up of 2 methyl valeric acid with the compatibility aspect of difluoromethane cold-producing mediumMatter and the material being formed by the aliphatic acid of 2 methyl valeric acid and carbon number 5～7.
In present embodiment, form the aliphatic acid of dipentaerythritol fatty acid ester as long as meeting the scope of above-mentioned conditionIn, the molecular structure of dipentaerythritol fatty acid ester can be single, in addition, can be also molecular structure of more than two kindsThe mixture of different esters.
When the molecular structure of dipentaerythritol fatty acid ester is single, dipentaerythritol fatty acid ester is only divided by a kind of esterWhen son forms, this ester molecule must meet above-mentioned condition in its molecular structure certainly. On the other hand, dipentaerythritol aliphatic acidWhen ester is the mixture of the different ester of molecular structure of more than two kinds, each molecule is not necessarily needed all to meet above-mentioned condition, onlyTo meet above-mentioned condition as the aliphatic acid entirety of formation dipentaerythritol fatty acid ester contained in refrigerator oil.
As mentioned above, the dipentaerythritol fatty acid ester of present embodiment is taking 2 methyl valeric acid as essential component, and rootThe material that the aliphatic acid that contains other according to needs is constituent. , dipentaerythritol fatty acid ester can be a kind of fat onlyAcid is as the material of sour constituent, can be also aliphatic acid that two or more structure the is different material as sour constituent, shouldDipentaerythritol fatty acid ester preferably as sour constituent only contain with the carbon atom (α position carbon atom) of the carbon adjacency of carbonyl noThe aliphatic acid of quaternary carbon. Form in the aliphatic acid of dipentaerythritol fatty acid ester, contain the aliphatic acid that α position carbon atom is quaternary carbonTime, the lubricity under difluoromethane cold-producing medium exists often becomes insufficient.
As the preferred example of sour constituent that forms dipentaerythritol fatty acid ester of the present invention, can enumerate followingMaterial.
2 methyl valeric acid;
2 methyl valeric acid with select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 Ethylbutanoic acid, 2-ethyl pentaThe combination of 1～7 kind in the group of acid and 2 methyl caproic acid composition;
The combination of 2 methyl valeric acid and 3,5,5-tri-methyl hexanoic acid;
2 methyl valeric acid and freely 3,5,5-tri-methyl hexanoic acid, valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-of choosingThe combination of 1～7 kind in the group of ethyl butyric acid, 2-ethyl valeric acid and 2 methyl caproic acid composition;
The combination of 2 methyl valeric acid and 2 ethyl hexanoic acid;
The free valeric acid of 2 methyl valeric acid, 2 ethyl hexanoic acid and choosing, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-ethyl fourthThe combination of 1～7 kind in the group of acid, 2-ethyl valeric acid and 2 methyl caproic acid composition;
The combination of 2 methyl valeric acid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid;
2 methyl valeric acid, 2 ethyl hexanoic acid, 3,5,5-tri-methyl hexanoic acid with select free valeric acid, 2-Methyl Butyric Acid, 3-methylThe combination of 1～7 kind in the group of butyric acid, caproic acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition;
2 methyl valeric acid be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, PA, caproic acid, 3-methylValeric acid, 4-methylvaleric acid, 2,2-acid dimethyl, 2,3-acid dimethyl, 2,4-acid dimethyl, 3,3-acid dimethyl,2 Ethylbutanoic acid, enanthic acid, 2 methyl caproic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethyl valeric acid, 2,3-dimethyl valeric acid, 2,4-dimethyl valeric acid, 3,3-dimethyl valeric acid, 3,4-dimethyl valeric acid, 4,4-dimethyl valeric acid, 2-secondBase valeric acid, 3-ethyl valeric acid, 1,1,2-trimethyl butyric acid, 1,2,2-trimethyl butyric acid, 1-ethyl-1 methylbutanoic acid, 1-ethyl-The combination of the aliphatic acid of a kind～29 kinds in 2-Methyl Butyric Acid;
2 methyl valeric acid be selected from 2 ethyl hexanoic acid, 3-thylhexoic acid, 3,5-dimethyl caproic acid, 2,4-dimethyl caproic acid,3,4-dimethyl caproic acid, 4,5-dimethyl caproic acid, 2,2-dimethyl caproic acid, 2-methyl enanthic acid, 3-methyl enanthic acid, 4-methyl heptanAcid, 5-methyl enanthic acid, 6-methyl enanthic acid, valproic acid, 2,2-dimethyl enanthic acid, 3,5,5-tri-methyl hexanoic acid, 2-methyl are pungentAcid, 2-ethyl enanthic acid, 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethyl butyric acid, 2,2,4,4-tetramethyl valeric acid, 2,2,3,3-Tetramethyl valeric acid, 2,2,3,4-tetramethyl valeric acid, 2, the combination of the aliphatic acid of a kind～23 kinds in 2-diisopropyl propionic acid;
And 2 methyl valeric acid and be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, PA, caproic acid,3 methylvaleric acid, 4-methylvaleric acid, 2,2-acid dimethyl, 2,3-acid dimethyl, 2,4-acid dimethyl, 3,3-dimethylButyric acid, 2 Ethylbutanoic acid, enanthic acid, 2 methyl caproic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethyl-pentenAcid, 2,3-dimethyl valeric acid, 2,4-dimethyl valeric acid, 3,3-dimethyl valeric acid, 3,4-dimethyl valeric acid, 4,4-dimethyl-pentenAcid, 2-ethyl valeric acid, 3-ethyl valeric acid, 1,1,2-trimethyl butyric acid, 1,2,2-trimethyl butyric acid, 1-ethyl-1 methylbutanoic acid,In 1-Ethyl-2-Methyl butyric acid a kind～29 kinds and be selected from 2 ethyl hexanoic acid, 3-thylhexoic acid, 3,5-dimethyl oneselfAcid, 2,4-dimethyl caproic acid, 3,4-dimethyl caproic acid, 4,5-dimethyl caproic acid, 2,2-dimethyl caproic acid, 2-methyl enanthic acid, 3-Methyl enanthic acid, 4-methyl enanthic acid, 5-methyl enanthic acid, 6-methyl enanthic acid, valproic acid, 2,2-dimethyl enanthic acid, 3,5,5-tri-Methylhexanoic acid, 2-methyloctanoic acid, 2-ethyl enanthic acid, 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethyl butyric acid, 2,2,4,4-tetra-Methylvaleric acid, 2,2,3,3-tetramethyl valeric acid, 2,2,3,4-tetramethyl valeric acid, 2, a kind～23 kinds of 2-diisopropyl propionic acidThe combination of aliphatic acid.
In the refrigerator oil of present embodiment, above-mentioned dipentaerythritol fatty acid ester can use mainly as base oil. AsThe base oil of the refrigerator oil of present embodiment, can only use separately above-mentioned dipentaerythritol fatty acid ester (is dipentaerythritolThe content of fatty acid ester is 100 quality %). Or, except dipentaerythritol fatty acid ester, do not damaging its excellent propertiesDegree on can be used together polyol ester beyond above-mentioned dipentaerythritol fatty acid ester, complex ester, ester ring type dicarboxylic ester etc.The oxygen containing artificial oils such as ester, polyethylene glycol, polyvinylether, ketone, polyphenylene oxide, silicone, polysiloxanes, perfluor ether are (below according to feelingsCondition is called " other containing oxygen artificial oil ").
As the base oil beyond the dipentaerythritol fatty acid ester of present embodiment, can be used together and use mineral oil, alkeneThe dipentaerythritol fat of the hydrocarbon system oil such as polymer alkyl diphenyl base alkane, alkyl naphthene, alkylbenzene and present embodimentEster beyond fat acid esters be base oil (monoesters, as the polyol ester, the alkyl aromatic that form aliphatic acid and only contain straight chain fatty acidEster, ester ring type carboxylate etc.), polyglycols, polyvinylether, ketone, polyphenylene oxide, silicone, polysiloxanes, perfluor ether etc. are oxygen containing syntheticOil. As oxygen containing artificial oil, the ester, poly-two in above-mentioned beyond the dipentaerythritol fatty acid ester of preferred present embodimentAlcohol, polyvinylether, the particularly preferably polyol ester beyond dipentaerythritol fatty acid ester.
As the polyol ester beyond dipentaerythritol fatty acid ester, can enumerate neopentyl glycol, trimethylolethane, three hydroxylsThe ester of the polyalcohols such as methylpropane, tri hydroxy methyl butane, pentaerythrite and aliphatic acid, particularly preferably is neopentyl glycol and fatThe ester of acid and the ester of pentaerythrite and aliphatic acid.
As DOPCP, the preferably fatty acid ester of carbon number 5～9. As such DOPCP, specifically canFor example list neopentyl glycol two (3,5,5-trimethyl is own) ester, neopentyl glycol (two 2-ethyl hexyls) acid esters, neopentyl glycol (two2-methyl oneself) ester, new penta 2 of ester, neopentyl glycol two (2-ethyl penta) ester, neopentyl glycol and 2 methyl caproic acid/2-ethyl valeric acidThe ester of ester, neopentyl glycol and the 2 methyl caproic acid/2 ethyl hexanoic acid of alcohol and 3-methylhexanoic acid/5-methylhexanoic acid, neopentyl glycol and3,5-dimethyl caproic acid/4,5-dimethyl caproic acid/3, the ester of 4-dimethyl caproic acid, neopentyl glycol diamyl ester, neopentyl glycol two 2-Ethyl butyl ester, neopentyl glycol two (2-methylpent) ester, neopentyl glycol two (2-methyl fourth) ester, neopentyl glycol two (3-methyl fourth) esterDeng.
As pentaerythritol ester, preferably ester, pentaerythrite and the carbon of the aliphatic acid of pentaerythrite and carbon number 5～7 are formerThe ester of the branched chain fatty acid of the aliphatic acid of subnumber 5～7 and carbon number 8～9. As such pentaerythritol ester, specifically can be listed asLift the ester of pentaerythrite and following aliphatic acid.
Valeric acid; 2-Methyl Butyric Acid; 3 Methylbutanoic acid; Caproic acid; 2 methyl valeric acid; 2 Ethylbutanoic acid; 2-ethyl valeric acid; 2-firstBase caproic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acidWith in the group of 2 methyl caproic acid composition 2 kinds; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid,In the group of 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 3 kinds; Select free valeric acid, 2-Methyl Butyric Acid, 3-methylIn the group of butyric acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 4 kinds; Choosing freelyValeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acidComposition group in 5 kinds; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid,In the group of 2-ethyl valeric acid and 2 methyl caproic acid composition 6 kinds; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid,In the group of 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 7 kinds; Valeric acid, 2-Methyl Butyric Acid,3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid; Valeric acid and 3,5,5-front threeBase caproic acid; 2-Methyl Butyric Acid and 3,5,5-tri-methyl hexanoic acid; 3 Methylbutanoic acid and 3,5,5-tri-methyl hexanoic acid; Caproic acid and 3,5,5-Tri-methyl hexanoic acid; 2 methyl valeric acid and 3,5,5-tri-methyl hexanoic acid; 2 Ethylbutanoic acid and 3,5,5-tri-methyl hexanoic acid; 2-ethyl pentaAcid and 3,5,5-tri-methyl hexanoic acid; 2 methyl caproic acid and 3,5,5-tri-methyl hexanoic acid; Valeric acid and 2 ethyl hexanoic acid; 2-Methyl Butyric AcidWith 2 ethyl hexanoic acid; 3 Methylbutanoic acid and 2 ethyl hexanoic acid; Caproic acid and 2 ethyl hexanoic acid; 2 methyl valeric acid and 2 ethyl hexanoic acid;2 Ethylbutanoic acid and 2 ethyl hexanoic acid; 2-ethyl valeric acid and 2 ethyl hexanoic acid; 2 methyl caproic acid and 2 ethyl hexanoic acid; Valeric acid, 2-Thylhexoic acid and 3,5,5-tri-methyl hexanoic acid; 2-Methyl Butyric Acid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; 3-methyl fourthAcid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; Caproic acid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; 2 methyl valeric acid,2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; 2 Ethylbutanoic acid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; 2-ethyl pentaAcid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; 2 methyl caproic acid, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; Be selected fromOwn by valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2-methyl2 kinds and 3,5,5-tri-methyl hexanoic acid in the group of acid composition; Valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-methylpent2 kinds and 2 ethyl hexanoic acid in the group of acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition; Select free valeric acid, 2-The group of methylbutanoic acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid compositionIn 2 kinds, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-In the group of methylvaleric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 3 kinds and 3,5,5-tri-methyl hexanoic acid; ChoosingFree valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2-methyl3 kinds and 2 ethyl hexanoic acid in the group of caproic acid composition; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-methylpentIn the group of acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 3 kinds, 2 ethyl hexanoic acid and 3,5,5-trimethylCaproic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid andIn the group of 2 methyl caproic acid composition 4 kinds and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid,4 kinds and 2 ethyl hexanoic acid in the group of caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition;Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2-firstIn the group of base caproic acid composition 4 kinds, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3-firstIn the group of base butyric acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 5 kinds and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-second5 kinds and 2 ethyl hexanoic acid in the group of base valeric acid and 2 methyl caproic acid composition; Select free valeric acid, 2-Methyl Butyric Acid, 3-methyl fourth5 kinds, 2-ethyl hexyl in the group of acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid compositionAcid and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2-ethylIn the group of butyric acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 6 kinds and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-firstIn the group of base butyric acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition6 kinds and 2 ethyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2-ethyl fourthIn the group of acid, 2-ethyl valeric acid and 2 methyl caproic acid composition 6 kinds, 2 ethyl hexanoic acid and 3,5,5-tri-methyl hexanoic acid; Choosing freelyValeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acidComposition group in 7 kinds and 3,5,5-tri-methyl hexanoic acid; Select free valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-first7 kinds and 2 ethyl hexanoic acid in the group of base valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid composition; Choosing free pentaAcid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid and 2 methyl caproic acid group7 kinds, 2 ethyl hexanoic acid in the group becoming and 3,5,5-tri-methyl hexanoic acid; Valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, caproic acid, 2-Methylvaleric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid, 2 methyl caproic acid, 3,5,5-tri-methyl hexanoic acid; Valeric acid, 2-Methyl Butyric Acid, 3-Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid, 2 methyl caproic acid, 2 ethyl hexanoic acid; Valeric acid, 2-Methylbutanoic acid, 3 Methylbutanoic acid, caproic acid, 2 methyl valeric acid, 2 Ethylbutanoic acid, 2-ethyl valeric acid, 2 methyl caproic acid, 3,5,5-tri-Methylhexanoic acid, 2 ethyl hexanoic acid.
In present embodiment, while coordinating the polyol ester beyond dipentaerythritol fatty acid ester, taking refrigerator oil total amount asBenchmark, need to be below 90 quality %, preferably below 85 quality %, and more preferably below 80 quality %, further preferred 70 matterBelow amount %, further more preferably below 60 quality %, most preferably below 50 quality %. In addition, coordinate beyond polyol esterDuring containing oxygen artificial oil, taking refrigerator oil total amount as benchmark, need to be below 90 quality %, preferably below 50 quality %, more preferablyBelow 40 quality %, further preferably below 30 quality %. Polyol ester beyond dipentaerythritol fatty acid ester, other containWhen the use level of oxygen artificial oil exceedes aforementioned higher limit, be difficult to take into account and compatibility and the profit of difluoromethane cold-producing medium with high levelSlip.
In addition, polyol ester of the present invention can be that a part of hydroxyl of wherein polyalcohol is not esterified, hydroxyl former state is protectedThe partial ester staying, or the esterified full ester of all hydroxyls, in addition, can be the mixture of partial ester and full ester, and hydroxyl value is preferredBelow 10mgKOH/g, more preferably, below 5mgKOH/g, most preferably be below 3mgKOH/g.
The refrigerator oil of present embodiment and working fluid composition for refrigerating machine are as dipentaerythritol fat separatelyPolyol ester beyond acid esters, can contain by a kind of material forming in the polyol ester of single structure, in addition, also canThe mixture that contains the polyol ester of more than two kinds that structure is different.
In addition, the polyol ester beyond dipentaerythritol fatty acid ester can be the ester, 2 of a kind of aliphatic acid and a kind of polyalcoholThe ester of kind of above aliphatic acid and the ester of a kind of polyalcohol, a kind of aliphatic acid and two or more polyalcohol, two or more aliphatic acid and 2 kinds withIn the ester of upper polyalcohol any. Wherein, in polyol ester, the especially ester molecule that uses fatty acid mixed to form, contain 2 kindsThe low-temperature characteristics of above aliphatic acid and the polyol ester that forms, with the compatibility excellence of cold-producing medium.
The refrigerator oil of present embodiment and working fluid composition for refrigerating machine can further contain various additives.In addition, in the following description, the content of additive is illustrated taking refrigerator oil total amount as benchmark, it is desirable to refrigeratorWith the content of these compositions in working fluid composition during taking refrigerator oil total amount as benchmark in preferred scope described laterSelect.
For further the improvement refrigerator oil of present embodiment and the abrasion performance of working fluid composition for refrigerating machine,Resistance to loading, can also coordinate phosphate, phosphate ester acid, thiophosphate, phosphate ester acid ammonium salt, chloro phosphate andThe phosphorus compound of at least a kind in the group of phosphite ester composition. These phosphorus compounds are phosphoric acid or phosphorous acid and alkanol, polyether-typeThe ester of alcohol or its derivative.
As phosphate, can enumerate tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate, tricresyl phosphate pungentEster, trinonyl phosphate, tridecyl phosphate, tricresyl phosphate (undecyl) ester, tricresyl phosphate (dodecyl) ester, tricresyl phosphate (tridecaneBase) ester, tricresyl phosphate (myristyl) ester, tricresyl phosphate (pentadecyl) ester, tricresyl phosphate (cetyl) ester, tricresyl phosphate (heptadecaneBase) ester, tricresyl phosphate (octadecyl) ester, tricresyl phosphate grease, triphenyl phosphate, tricresyl phosphate, three (dimethylbenzene) phosphate,Cresyl diphenyl phosphate, xylyl diphenyl phosphate etc.
As phosphate ester acid, can enumerate acid mono phosphoric acid ester butyl ester, acid phosphoric acid single fifth ester, the own ester of acid mono phosphoric acid ester, acidFormula mono phosphoric acid ester heptyl ester, acid mono-octyl phosphate, acid mono phosphoric acid ester ester in the ninth of the ten Heavenly Stems, acid mono phosphoric acid ester ester in the last of the ten Heavenly stems, acid mono phosphoric acid ester undecylEster, acid mono phosphoric acid ester dodecyl ester, acid mono phosphoric acid ester tridecyl ester, acid mono phosphoric acid ester myristyl ester, acid mono phosphoric acid esterPentadecyl ester, acid mono phosphoric acid ester cetyl ester, acid mono phosphoric acid ester heptadecyl ester, mono phosphoric acid ester octadecyl acid ester, acidFormula mono phosphoric acid ester oil base ester, dibutyl acid phosphate, acid di(2-ethylhexyl)phosphate pentyl ester, acid phosphoric acid dihexyl, acid di(2-ethylhexyl)phosphate heptyl ester, acidFormula dioctylphosphoric acid ester, acid di(2-ethylhexyl)phosphate ester in the ninth of the ten Heavenly Stems, acid phosphoric acid didecyl ester, acid di(2-ethylhexyl)phosphate (undecyl) ester, acid di(2-ethylhexyl)phosphate(dodecyl) ester, acid di(2-ethylhexyl)phosphate (tridecyl) ester, acid di(2-ethylhexyl)phosphate (myristyl) ester) acid di(2-ethylhexyl)phosphate (pentadecaneBase ester, acid di(2-ethylhexyl)phosphate (cetyl) ester, acid di(2-ethylhexyl)phosphate (heptadecyl) ester, acid di(2-ethylhexyl)phosphate (octadecyl) ester, acidFormula di(2-ethylhexyl)phosphate oil base ester etc.
As thiophosphate, can enumerate tributyl thiophosphate, D2EHDTPA triamyl, the own ester of tri o cresyl thiophosphate, sulphurFor THP triheptylphosphate, tri o cresyl thiophosphate monooctyl ester, tri o cresyl thiophosphate ester in the ninth of the ten Heavenly Stems, tri o cresyl thiophosphate ester in the last of the ten Heavenly stems, tri o cresyl thiophosphate (hendecaneBase) ester, tri o cresyl thiophosphate (dodecyl) ester, tri o cresyl thiophosphate (tridecyl) ester, tri o cresyl thiophosphate (myristyl) ester, sulphurFor tricresyl phosphate (pentadecyl) ester, tri o cresyl thiophosphate (cetyl) ester, tri o cresyl thiophosphate (heptadecyl) ester, tri o cresyl thiophosphate(octadecyl) ester, tri o cresyl thiophosphate grease, trithiophenyl phosphate, tri o cresyl thiophosphate cresols ester, tri o cresyl thiophosphate (diformazanBenzene) ester, D2EHDTPA toluene diphenyl ester, D2EHDTPA dimethylbenzene diphenyl ester etc.
As the ammonium salt of phosphate ester acid, can enumerate phosphate ester acid and carbon number 1～24, preferably 5～18 primary,The ammonium salt of the amine of the second month in a season, uncle's straight or branched alkyl.
As the amine of ammonium salt that forms phosphate ester acid, the methylamine of straight or branched, ethamine, propylamine, butylamine, amylamine, oneselfAmine, heptyl amice, octylame, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl amine, tetradecylamine, pentadecylAmine, hexadecylamine, heptadecyl amine, octadecylamine, oil base amine, two tetradecy lamines, dimethylamine, diethylamine, di-n-propylamine, two fourthsAmine, diamylamine, dihexylamine, two heptyl amices, dioctylamine, nonyl amine, didecylamine, two (undecyl) amine, two (dodecyl) amine, two(tridecyl) amine, two (myristyl) amine, two (pentadecyl) amine, two (cetyl) amine, two (heptadecyl) amine, two(octadecyl) amine, two oleyl amines, two (tetracosyl) amine, trimethylamine, triethylamine, tripropyl amine (TPA), tri-n-butylamine, triamylamine, three oneselfAmine, three heptyl amices, trioctylamine, TNA trinonylamine, tridecylamine, three (undecyl) amine, tridodecylamine, three (tridecyl) amine,Three (myristyl) amine, three (pentadecyl) amine, three (cetyl) amine, three (heptadecyl) amine, three (octadecyl) amine, threeThe salt of the amine such as oleyl amine, three (24) amine. Amine can be independent compound, can be also the mixing of compound of more than two kindsThing.
As chloro phosphate, can enumerate tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (chlorobenzeneBase) two [two (chlorine the alkyl)] esters of ester, phosphoric acid polyoxyalkylene etc. As phosphite ester, can enumerate dibutyl phosphite, sub-phosphorusAcid diamyl ester, phosphorous acid dihexyl, phosphorous acid two heptyl esters, dioctyl phosphite, phosphorous acid ester in two ninth of the ten Heavenly Stems, didecyl phosphite, AsiaDi(2-ethylhexyl)phosphate (undecyl) ester, phosphorous acid two (dodecyl) ester, phosphorous acid two greases, diphenyl phosphite, phosphorous acid two (firstPhenol) ester (dicresylphosphite), tributyl phosphite, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite heptanEster, tricresyl phosphite monooctyl ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, tricresyl phosphite (undecyl) ester, tricresyl phosphite (12Alkyl) ester, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite (cresols) ester etc. In addition, can also use the mixed of themCompound.
When the refrigerator oil of present embodiment and working fluid composition for refrigerating machine contain above-mentioned phosphorus compound, phosphatization is closedThe content of thing is not particularly limited, taking refrigerator oil total amount as benchmark (taking base oil with all coordinate total metering of additive as baseAccurate) meter, preferably 0.01～5.0 quality %, more preferably 0.02～3.0 quality %. In addition, can use separately a kind of above-mentioned phosphatizationCompound, also two or more kinds may be used.
In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine for further its heat of improvement/Chemical stability, can add terpene compound. The present invention's said " terpene compound " refers to what isoprene polymerization formedCompound and their derivative, preferably use 2 aggressiveness～8 aggressiveness of isoprene. As terpene compound, specifically can be listed asLift geraniol, nerol, linalool, citral (comprising citronellal (geranial)), citronellol, menthol, citrene, terpeneMonoterpene, the joyous alkene of alloy such as terpinolene, carvol, irisone, absinthol (thujone), camphor (camphor), borneol, closeThe joyous alcohol of gold, nerolidol, juvenile hormone (Juvenilehormone), humulene, sub-cloves alkene, elemene, cadinol, needle juniperHalf terpenes such as alkene, corriamytrin (tutin), trans-Geranylgeraniol (geranylgeraniol), phytol, rosin acid, pimaradiene,The sesterterpene such as two terpenes such as daphnetoxin (daphnetoxin), taxol, rosin acid, pimaric acid, the joyous alkene of geranyl alloyAlkene, squalene, limonin (Limonin), camellia sapogenol, what handkerchief alkane (Hopane), lanosterol (lanosterol) etc.The tetraterpenes such as triterpene, carotenoid (carotenoid) etc.
In these terpene compounds, preferably monoterpene, half terpenes, two terpenes, more preferably half terpenes, particularly preferably α-closeThe joyous alkene (3,7,11-trimethyldodecane-1,3,6,10-tetraene) of gold and/or the joyous alkene of β-alloy (7,11-dimethyl-3-methineDodecane-1,6,10-triolefin). In the present invention, terpene compound can use separately a kind, also can combine two or more use.
The content of the terpene compound in the refrigerator oil of present embodiment is not particularly limited, taking refrigerator oil total amount asBenchmark, preferably 0.001～10 quality %, more preferably 0.01～5 quality %, further preferred 0.05～3 quality %. Terpenes chemical combinationWhen the content of thing is less than 0.001 quality %, exist heat/chemical stability to improve the inadequate tendency of effect, in addition, exceed 10 matterWhen amount %, there is the inadequate tendency of lubricity. In addition, it is desirable to, to the working fluid used for refrigerator of present embodimentThe content of terpene compound in composition is selected during taking refrigerator oil total amount as benchmark in above-mentioned preferred scope.
In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine for further its heat of improvement/Chemical stability, can contain be selected from phenyl glycidyl ether type epoxide, alkyl glycidyl ether type epoxide,Glycidyl ester type epoxide, allyloxy silane compound, alkoxysilane compound containing trialkylsilyl group in molecular structure, alicyclic epoxy compound,At least a kind of epoxide in epoxidized fatty acid monoesters and epoxidized vegetable oil.
As phenyl glycidyl ether type epoxide, specifically can exemplify phenyl glycidyl ether or alkyl phenyl contractingWater glycerin ether. The alkyl phenyl glycidol ether here can list the alkyl of the carbon number 1～13 with 1～3Compound, wherein, the compound with the alkyl of the carbon number 4～10 of 1 can illustrate preference and contract as n-butylphenylWater glycerin ether, isobutyl phenenyl glycidol ether, secondary butyl phenenyl glycidol ether, tert-butyl-phenyl glycidol ether, amyl groupPhenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidol ether, nonylPhenyl glycidyl ether, decyl phenyl glycidol ether etc.
Specifically can illustrate as alkyl glycidyl ether type epoxide, decyl glycidyl ether, undecyl shrinkGlycerin ether, lauryl diglycidyl ether, tridecyl glycidol ether, myristyl glycidol ether, the contracting of 2-ethylhexylWater glycerin ether, dimethyltrimethylene glycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, pentaerythrite four glycidolsEther, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidylether, poly-alkane glycol monoglycidyl ether, poly-alkane glycolDiglycidyl ether etc.
As glycidyl ester type epoxide, specifically can list phenyl glycidyl ester, alkyl glycidylEster, alkenyl ethylene oxidic ester etc., can illustrate 2 as preferred glycidyl ester type epoxide, the sad contracting of 2-dimethylWater glyceride, benzoic acid ethylene oxidic ester, glycidyl acrylate, GMA etc.
Specifically can illustrate 1,2-epoxy styrene, alkyl-1,2-epoxy styrene as allyloxy silane compoundDeng.
As alkyl oxosilane compound, specifically can illustrate, 1,2-epoxy butane, 1,2-epoxy pentane, 1,2-epoxy is ownAlkane, 1,2-epoxy heptane, 1,2-octylene oxide, 1,2-epoxy nonane, 1,2-epoxy decane, 1,2-epoxy hendecane, 1,2-ringOxygen dodecane, 1,2-epoxy tridecane, 1, the 2-epoxy tetradecane, 1,2-epoxy pentadecane, 1,2-epoxy hexadecane, 1,2-epoxyHeptadecane, 1,1,2-epoxy octadecane, 2-Disparmone, 1,2-epoxy eicosane etc.
As alicyclic epoxy compound, specifically can illustrate HEO, 1,2-cyclopentane epoxide, 3,4-epoxyCyclohexyl methyl-3,4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl methyl) adipate ester, outer-2,3-epoxy fallsCamphane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipate ester, 2-(7-oxabicyclo [4.1.0] heptan-3-yl)-spiral shell (1,3-diox-5,3 '-[7] oxabicyclo [4.1.0] heptane, 4-(1 '-methyl epoxy ethyl)-1,2-epoxy-2-methyl cyclohexaneAlkane, 4-epoxy ethyl-HEO etc.
As epoxidized fatty acid monoesters, specifically can illustrate, aliphatic acid and the carbon of epoxidised carbon number 12～20 are formerThe ester of the alcohol of subnumber 1～8 or phenol, alkylphenol etc. Particularly preferably use butyl, hexyl, benzyl, the hexamethylene of epoxystearic acidThe ester of base, methoxyethyl, octyl group, phenyl and butyl phenyl.
As epoxidized vegetable oil, specifically can illustrate the epoxy compound of soybean oil, linseed oil, cottonseed wet goods vegetable oilThing etc.
In these epoxides, preferred material is phenyl glycidyl ether type epoxide, glycidyl ester typeEpoxide, alicyclic epoxy compound and epoxidized fatty acid monoesters. Wherein more preferably phenyl glycidyl ether type epoxyCompound and glycidyl ester type epoxide, particularly preferably phenyl glycidyl ether, butylphenyl glycidyl ether, alkylEthylene oxidic ester or their mixture.
When the refrigerator oil of present embodiment and working fluid composition for refrigerating machine contain above-mentioned epoxide, epoxyThe content of compound is not particularly limited, taking refrigerator oil total amount as benchmark, and preferably 0.1～5.0 quality %, more preferably 0.2～2.0 quality %. In addition, above-mentioned epoxide can be used alone or two or more kinds may be used.
In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine are in order further to improve its propertyCan, can contain as required known refrigerator oil additive in the past. As described additive, for example can enumerate and can enumerateGo out antioxidant, PA, the N of the phenol such as two-tert-butyl group-paracresol, bisphenol-A system, N-bis-(2-naphthyl)-to phenyl twoExtreme pressure agent, the aliphatic acid etc. such as wear-resistant dose of antioxidant, the zinc dithiophosphate etc. of the amine such as amine system, chloralkane, sulphur compoundMetal inerting agent, viscosity index improving agent, pour-point depressant, the cleaning dispersants such as the defoamer such as oiliness improver, silicone-based, BTADeng. These additives can use separately a kind, also can combine two or more use. The not special limit of the content of these additivesFixed, taking refrigerator oil total amount as benchmark, be preferably below 10 quality %, more preferably below 5 quality %.
The dynamic viscosity of the refrigerator oil of present embodiment is not particularly limited, and the dynamic viscosity at 40 DEG C can be preferably 3～1000mm2/ s, more preferably 4～500mm2/ s, 5～400mm most preferably2/ s. In addition, the dynamic viscosity at 100 DEG C can be preferably 1～100mm2/ s, more preferably 2～50mm2/ s. When dynamic viscosity is less than aforementioned lower limit, often lubricity becomes insufficient, the opposing partyFace, often becomes insufficient with the compatibility of difluoromethane cold-producing medium while exceeding aforementioned higher limit.
In addition, the specific insulation of the refrigerator oil of present embodiment is not particularly limited, can be preferably 1.0 × 1012Ω·Cm is above, more preferably 1.0 × 1013Ω cm is above, most preferably 1.0 × 1014More than Ω cm. Be specially adapted to hermetic typeUnder situation used for refrigerator, often need high electrical insulating property. In addition, in the present invention, specific insulation refers to based on JISValue at 25 DEG C of C2101 " electric insulation oil test method " mensuration.
In addition, the moisture of the refrigerator oil of present embodiment is not particularly limited, taking refrigerator oil total amount as benchmark,Preferably 200ppm following, more preferably 100ppm following, most preferably below 50ppm. Particularly be applicable to the refrigerator of hermetic typeWith situation under, from the viewpoint of the impact of the heat/chemical stability on refrigerator oil, electrical insulating property, require moistureFew.
In addition, the acid number of the refrigerator oil of present embodiment is not particularly limited, in order to prevent for refrigerator or joinThe corrosion of metal of pipe, preferably 0.1mgKOH/g following, more preferably below 0.05mgKOH/g. In addition, in the present invention, acid numberRefer to the acid number of measuring based on JISK2501 " petroleum product and lubricating oil-neutralization number test method ".
In addition, the ash content of the refrigerator oil of present embodiment is not particularly limited, in order to improve the freezing of present embodimentHeat/the chemical stability of machine oil and suppress the generation such as deposit, preferably 100ppm below, more preferably below 50ppm. In addition,In the present invention, ash content refers to the ash of measuring based on JISK2272 " ash content of crude oil and petroleum product and sulfated ass test method "Score value.
When the refrigerator oil of present embodiment uses together with difluoromethane cold-producing medium, show fully high lubricity and fillDivide high compatibility, can be widely used in the refrigerator oil of difluoromethane cold-producing medium refrigerator. As using present embodimentThe refrigerator of refrigerator oil, specifically can enumerate room conditioning, box air-conditioning, refrigerator, air conditioning for automobiles, dehumidifier, freezer, coldFreeze the cooling devices such as cold store, automatic vending machine, show window, chemical industry equipment etc., wherein, be particularly preferred for having hermetic type and pressThe refrigerator of contracting machine. In addition, the refrigerator oil of present embodiment can also use reciprocating motion type, rotary, centrifugal etc.In the compressor of arbitrary form. In addition, in these refrigerators, the refrigerator oil of present embodiment as described later, can be forThe working fluid composition for refrigerating machine forming with difluoromethane refrigerant mixed.
The difluoromethane cold-producing medium that, the working fluid composition for refrigerating machine of present embodiment contains the invention described above is usedRefrigerator oil and difluoromethane cold-producing medium. Here the refrigerator oil in the working fluid composition for refrigerating machine of present embodiment,Be not particularly limited with the match ratio of difluoromethane cold-producing medium, the use level of refrigerator oil is conventionally with respect to difluoromethane 100 weightsAmount part is 1～1000 weight portion, preferably 2～800 weight portions.
In addition, in the working fluid composition for refrigerating machine of present embodiment, when taking into account refrigerator oil in the past of useThe viewpoint that can not obtain fully high lubricity and abundant high compatibility is set out, and only contains difluoromethane as cold-producing medium compositionThe situation of cold-producing medium can more be brought into play its serviceability, but also can contain HFC cold-producing medium, insatiable hunger beyond difluoromethane cold-producing mediumAnd fluorinated hydrocarbons (HFO) cold-producing medium, three is fluoridized the fluorine-containing ether such as iodomethane cold-producing medium, perfluor ethers series coolant, dimethyl ether etc. noThe natural series coolants such as fluorine-containing ether series coolant, ammonia, carbon dioxide, hydrocarbon.
As the HFC cold-producing medium beyond difluoromethane, can enumerate carbon number 1～3, preferred 1～2 hydrogen fluorohydrocarbon. SpecificallyFor example can enumerate, fluoroform (HFC-23), pentafluoroethane (HFC-125), 1,1,2,2-HFC-134a (HFC-134), 1,1,1,2-HFC-134a (HFC-134a), 1,1,1-HFC-143a (HFC-143a), 1,1-Difluoroethane (HFC-152a), fluoroethane(HFC-161), HFC-227ea (HFC-227ea), 1,1,1,2,3,3-HFC-236fa (HFC-236ea),1,1,1,3,3,3-HFC-236fa (HFC-236fa), 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-fiveFluorine butane (HFC-365mfc) or the mixture of more than two kinds in them. These cold-producing mediums can and require performance suitable according to purposesWork as selection, can enumerate for example HFC-32 independent; HFC-23 is independent; HFC-134a is independent; HFC-125 is independent; HFC-134a/HFC-The mixture of quality %/40～20,32=60～80 quality %; Quality %/60～30, HFC-32/HFC-125=40～70 matterThe mixture of amount %; The mixture of quality %/60～40, HFC-125/HFC-143a=40～60 quality %; HFC-134a/The mixture of HFC-32/HFC-125=60 quality %/30 quality %/10 quality %; HFC-134a/HFC-32/HFC-125=The mixture of 40～70 quality %/5～40, quality %/15～35 quality %; HFC-125/HFC-134a/HFC-143a=35～The preferred example of conduct of the mixture of 55 quality %/40～60, quality %/1～15 quality %. And then concrete enumeratingThe mixture of HFC-134a/HFC-32=70/30 quality %; The mixture of HFC-32/HFC-125=60/40 quality %; HFC-The mixture (R410A) of 32/HFC-125=50/50 quality %; The mixture of HFC-32/HFC-125=45/55 quality %(R410B); The mixture (R507C) of HFC-125/HFC-143a=50/50 quality %; HFC-32/HFC-125/HFC-134aThe mixture of=30/10/60 quality %; The mixture of HFC-32/HFC-125/HFC-134a=23/25/52 quality %(R407C); The mixture (R407E) of HFC-32/HFC-125/HFC-134a=25/15/60 quality %; HFC-125/HFC-The mixture (R404A) of 134a/HFC-143a=44/4/52 quality % etc.
As unsaturated fluorinated hydrocarbons (HFO) cold-producing medium, the fluoropropenes that preferably number of fluorine atoms is 3～5, preferably 1,2,3,3,3-five fluoropropenes (HFO-1225ye), 1,3,3,3-tetra-fluoropropenes (HFO-1234ze), 2,3,3,3-tetra-fluoropropenes(HFO-1234yf), 1,2,3, in 3-tetra-fluoropropenes (HFO-C1234ye) and 3,3,3-, tri-fluoropropenes (HFO-1243zf)Any one kind or two or more mixture. From the viewpoint of physical properties, be preferably selected from HFO-1225ye, HFO-One kind or two or more in 1234ze and HFO-1234yf. As with the preferred material of mix refrigerant of HFO cold-producing medium be twoThe material of fluoromethane/1234yf=40～60/60～40 % by weight, wherein preferred difluoromethane/1234yf=50/50 % by weightMaterial.
As the hydrocarbon of the preferred carbon number 3～5 of hydrocarbon coolant, specifically for example can enumerate, methane, ethene, ethane, propylene,Two or more of propane, cyclopropane, normal butane, iso-butane, cyclobutane, methyl cyclopropane, 2-methybutane, pentane or theyMixture. Wherein, preferably use the material of the gas under 25 DEG C, 1 atmospheric pressure, preferably propane, normal butane, iso-butane, 2-firstBase butane or their mixture.
As fluorine-containing ether series coolant, can for example specifically enumerate 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., these cold-producing mediums can and require performance suitably to select according to purposes.
The refrigerator oil of present embodiment is conventionally in refrigerating and air conditioning machine, with difluoromethane cold-producing medium or difluoromethaneThe form of cold-producing medium and the working fluid composition for refrigerating machine that mixes with the mix refrigerant of cold-producing medium as described aboveExist. In the refrigerator oil of said composition and the mixing ratio of cold-producing medium and working fluid combination used for refrigerator of the present inventionIn thing, the mixing ratio of refrigerator oil and cold-producing medium is not particularly limited. With respect to cold-producing medium 100 mass parts, refrigerator oil is preferred1～1000 mass parts, more preferably 2～800 mass parts.
The working fluid composition for refrigerating machine of present embodiment is preferred for having reciprocating motion type or revolving closeIn air-conditioning, refrigerator or the style of opening of closed form compressor or the air conditioning for automobiles of hermetic type. In addition, the refrigerator of present embodimentOil and working fluid composition for refrigerating machine are preferred for dehumidifier, water heater, freezer, freezing and refrigeration warehouse, automatic vendingIn the cooling devices such as machine, show window, chemical plant installations etc. And then, the refrigerator oil of present embodiment and working fluid group used for refrigeratorCompound is also preferred for having the equipment of centrifugal compressor.
The refrigerator fluid composition of present embodiment can be preferred for foregoing various unsaturated fluorinated hydrocarbons systemCryogen refrigerator, but as the preferred structure in refrigerant circulation cycle that possesses this refrigerator, can illustrate possess compressor,Condenser, expansion mechanism and evaporimeter, and the equipment of drier as required.
As compressor, can illustrate following compressor: in the closed container that stores refrigerator oil storage by rotor andThe motor that stator forms, is embedded in the rotating shaft of aforementioned rotor and the compressor section being connected with aforementioned motor by this rotating shaft, andAnd be trapped in the compressor of the high-pressure bottle mode in closed container from the higher pressure refrigerant gas of aforementioned compressor section ejection; ?Store the motor that in the closed container of refrigerator oil, storage is made up of rotor and stator, be embedded in aforementioned rotor rotating shaft, pass throughThe compressor section that this rotating shaft is connected with aforementioned motor, and directly arrange from the higher pressure refrigerant gas of aforementioned compressor section ejectionGo out the compressor of the low pressure vessel mode outside closed container etc.
Electrical machine insulation system material as motor part is dielectric film, from being difficult to produce tensile strength characteristics, electric insulation spyDetermine degradation phenomena and set out, preferably use 50 DEG C of above crystalline plastic films of glass transition temperature, concrete example is as poly-right in being selected fromPhthalic acid glycol ester, polybutylene terephthalate (PBT), polyphenylene sulfide, polyether-ether-ketone, PEN, polyamidesThe dielectric film of at least one in the group of amine imines, polyimides composition or on the low film of glass transition temperature coating glassThe composite membrane that the resin bed that glass conversion temperature is high forms. In addition, as the magnet-wire for motor part (magnetwire), preferablyUsing glass transition temperature is 120 DEG C of above enamel coating, for example polyester, polyester-imide, polyamide and polyamide-imidesDeng individual layer or the low layer of glass transition temperature there is enamel for what upper strata composite coated formed for the high layer of lower floorThe magnet-wire of coating. As composite coated enamel line, can be set forth in lower floor's coating polyester-imide, at upper strata coating polyamide-imideThe enamel line (AI/EI) forming; The enamel line (AI/PE) forming at lower floor's coating polyester, at upper strata coating polyamide-imide etc.
As the drier that is filled in drier, preferably use following synthetic zeolite: following by fine pore 3.3 dusts, 25DEG C carbon dioxide absorption capacity of partial pressure of carbon dioxide under 250mmHg is silicic acid, the alkali aluminate bimetallic salt complex below 1.0%The synthetic zeolite forming. Specifically for example can enumerate the trade name XH-9 of UNIONSHOWAK.K system, XH-10, XH-11, XH-600 etc.
[embodiment] is following more specifically to be illustrated the present invention based on embodiment and comparative example, and the present invention is not subject to following realityExecute any restriction of example.
[embodiment 1～2 and comparative example 1～9]
In embodiment 1～2 and comparative example 1～9, use respectively the following base oil illustrating 1～11 modulation test portion oil. To obtainThe proterties (dynamic viscosity at 40 DEG C and 100 DEG C, total acid number) of test portion oil be shown in table 1～3.
(base oil)
Base oil 1: six esters of dipentaerythritol and 2 methyl valeric acid
Base oil 2: dipentaerythritol and fatty acid mixt (50 % by mole of 2 methyl valeric acids, 50 % by mole of 2 Ethylbutanoic acidsMixture)
Base oil 3: four esters of pentaerythrite and positive valeric acid
Base oil 4: six esters of dipentaerythritol and positive valeric acid
Base oil 5: the diester of neopentyl glycol and 2 methyl valeric acid
Base oil 6: three esters of trimethylolpropane and 2 methyl valeric acid
Base oil 7: four esters of pentaerythrite and 2 methyl valeric acid
Base oil 8: four esters of pentaerythrite and 2 Ethylbutanoic acid
Base oil 9: six esters of dipentaerythritol and 2 Ethylbutanoic acid
Base oil 10: pentaerythrite and mixture of carboxylic acids (70 % by mole of 2 methyl caproic acids, 30 % by mole of 2-ethyl valeric acids)Four esters
Base oil 11: (50 % by mole of 2 ethyl hexanoic acids, 3,5,5-tri-methyl hexanoic acid 50 rubs for pentaerythrite and mixture of carboxylic acidsYour %) four esters
Above-mentioned each test portion oil is carried out to the following test illustrating below.
(with the compatibility test of cold-producing medium)
Based on JIS-K-2211 " refrigerator oil " " with the compatibility test method of cold-producing medium ", by difluoromethane cold-producing medium(HFC-32) mixture of 18g and test portion oil 2g is slowly cooled to-40 DEG C from 30 DEG C, measures that mixture is separated or the temperature of gonorrhoeaDegree. Gained the results are shown in table 1～3. In addition, in table 1～3, the mensuration temperature province that " <-40 " are illustrated in this test does not have reallyRecognize and be separated and gonorrhoea, " separation " has been separated or gonorrhoea at representing 30 DEG C.
(lubricity test)
Upside test film is installed in the inside of closed container uses push rod (bane, SKH-51), downside test film to use circleThe frictional testing machine of dish (disc, FC250HRC40). Import test portion oil 600g at friction test position, by de-vacuum in systemAfter, import HFC-32 heating. It is after 100 DEG C, refrigerant pressure are 1.5Mpa that system is closed temperature in container, loading stepWhat 10kgf (step application time is 2 minutes) was interim applies loading to 100kgf. Each test portion oil is measured after test in 60 minutesThe abrasion width of blade and the abrasion degree of depth of disk.
(test of the low temperature property separated out)
Test portion oil is put into developmental tube, packing in the ethanol bath of dry ice (70 DEG C) dipping 24 hours into, observe have or not whiteTurbid.
(stability test)
In the autoclave of 200ml, enclose the 85g test portion oil that moisture is adjusted into 1000ppm, 15gHFC-32, measuresAt 175 DEG C, heat the acid number of the test portion oil after 500 hours.
Table 1
Table 2
Table 3
Claims (3)
1. the application of ester in the refrigerator oil that uses independent difluoromethane cold-producing medium, wherein said ester was two seasons penta 4The ester of alcohol and aliphatic acid, and in described aliphatic acid, the ratio of 2 methyl valeric acid is more than 20 % by mole, with refrigerator oil total amountFor benchmark meter contains esters more than 10 quality %.
2. ester is in an application of manufacturing in the refrigerator oil that uses independent difluoromethane cold-producing medium, and wherein said ester was two seasonsThe ester of penta tetrol and aliphatic acid, and in described aliphatic acid, the ratio of 2 methyl valeric acid is more than 20 % by mole, with refrigerator oilTotal amount is that benchmark meter contains esters more than 10 quality %.
3. a working fluid composition for refrigerating machine, its contain independent difluoromethane cold-producing medium and with difluoromethane cold-producing mediumThe refrigerator oil using together, described refrigerator oil contains esters more than 10 quality %, institute taking refrigerator oil total amount as benchmarkState the ester that ester is dipentaerythritol and aliphatic acid, and the ratio of 2 methyl valeric acid is more than 20 % by mole in described aliphatic acid.
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| BR112014009738A2 (en) | 2011-10-26 | 2017-04-18 | Jx Nippon Oil & Energy Corp | working fluid composition for cooling machine and cooling oil |
| EP2799527B1 (en) * | 2011-12-27 | 2022-02-02 | Japan Sun Oil Company, Ltd. | Refrigerator oil composition |
| JP5989989B2 (en) * | 2011-12-27 | 2016-09-07 | 日本サン石油株式会社 | Refrigerator oil composition |
| US8691109B2 (en) * | 2012-02-15 | 2014-04-08 | Chemtura Corporation | Working fluids comprising difluoromethane and di-pentaerythritol ester |
| KR101909545B1 (en) | 2012-03-27 | 2018-10-19 | 제이엑스티지 에네루기 가부시키가이샤 | Working fluid composition for refrigerator |
| CN103525370A (en) * | 2013-08-01 | 2014-01-22 | 广东美芝制冷设备有限公司 | Composition, compressor adopting composition and refrigeration equipment adopting composition |
| EP3043124A4 (en) * | 2013-09-05 | 2017-04-26 | Toshiba Carrier Corporation | Compressor and refrigeration cycle device |
| WO2015128952A1 (en) * | 2014-02-26 | 2015-09-03 | 株式会社日立製作所 | Refrigerant oil and refrigerant/machine oil dimer structure |
| JP6262035B2 (en) * | 2014-03-14 | 2018-01-17 | Ｊｘｔｇエネルギー株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| WO2015140918A1 (en) * | 2014-03-18 | 2015-09-24 | 株式会社日立製作所 | Refrigerant device and compressor for refrigerant device |
| JP6605015B2 (en) * | 2015-02-20 | 2019-11-13 | Ｊｘｔｇエネルギー株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| WO2016147385A1 (en) * | 2015-03-19 | 2016-09-22 | ジョンソンコントロールズ ヒタチ エア コンディショニング テクノロジー （ホンコン） リミテッド | Compressor for refrigeration and air conditioning, and refrigeration and air conditioning device |
| JP6615526B2 (en) * | 2015-07-31 | 2019-12-04 | Ｊｘｔｇエネルギー株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| JP2017075278A (en) * | 2015-10-16 | 2017-04-20 | 出光興産株式会社 | Refrigerator oil, composition for refrigerator, and refrigerator |
| WO2021005986A1 (en) * | 2019-07-05 | 2021-01-14 | Ｊｘｔｇエネルギー株式会社 | Working fluid composition for refrigerator, and refrigerator oil |
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