CN102191114A - Refrigerating machine oil and working fluid composition for refrigerator - Google Patents
Refrigerating machine oil and working fluid composition for refrigerator Download PDFInfo
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- CN102191114A CN102191114A CN2011100653875A CN201110065387A CN102191114A CN 102191114 A CN102191114 A CN 102191114A CN 2011100653875 A CN2011100653875 A CN 2011100653875A CN 201110065387 A CN201110065387 A CN 201110065387A CN 102191114 A CN102191114 A CN 102191114A
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Abstract
The invention discloses refrigerating machine oil and a working fluid composition for a refrigerator. The refrigerating machine oil of the invention contains ester which is above 10% of the total amount of the refrigerating machine oil by weight and used together with difluoromethane refrigerating medium. The ester is ester of pentaerythritol and fatty acid. Wherein in the fatty acid, the mol ratio of fatty acid with a branched chain and whose carbon atom number is 6 to 3,5,5-trimethyl caproic acid is (20:80)-(80:20); the sum of the fatty acid whose carbon atom number is 6 and the 3,5,5-trimethyl caproic acid is above 20 mol% in the fatty acid; furthermore, the working fluid composition for the refrigerator contains the refrigerating machine oil and the difluoromethane refrigerating medium in the invention.
Description
Technical field
The present invention relates to a kind of refrigerator oil and working fluid composition for refrigerating machine, specifically, relate to a kind of with methylene fluoride refrigeration agent (HFC-32) useful refrigerator oil and the working fluid composition for refrigerating machine that has used this refrigerator oil when using.
Background technology
Because the problem of in recent years depletion of the ozone layer, can replace them as the CFC (Chlorofluorocarbons (CFCs)) of the refrigeration agent of freezing machine and the object that HCFC (Hydrochlorofluorocarbons) becomes restriction in the past, use HFC (hydrogen fluorohydrocarbon) as refrigeration agent gradually.
At CFC and HCFC is under the situation of refrigeration agent, as refrigerator oil, can suitably use hydrocarbon ils such as mineral oil, alkylbenzene, yet when replacing refrigeration agent, since the refrigerator oil that under coexistence, uses shown with the consistency of refrigeration agent, oilness, with unforeseeable behaviors such as the dissolving viscosity of refrigeration agent, heat/chemical stability, thereby each refrigeration agent need be developed refrigerator oil.Therefore, as HFC refrigeration agent refrigerator oil, for example, developed poly-alkane glycol (with reference to Japanese kokai publication hei 02-242888 communique, ester (with reference to Japanese kokai publication hei 03-200895 communique), carbonic ether (with reference to Japanese kokai publication hei 03-217495 communique), polyvinyl ether (with reference to Japanese kokai publication hei 06-128578 communique) etc.In these refrigerator oils, ester is widely used in refrigerator, the air-conditioning purposes etc.
In the HFC refrigeration agent, HFC-134a, R407C, R410A usually as used for automobile air conditioning, refrigerator with or the room conditioning refrigeration agent.But though these HFC refrigeration agent ozone layer destroying coefficients (ODP) are zero, greenhouse effects of the earth coefficient (GWP) height is so become the object of restriction all the more.Therefore, the refrigeration agent of the alternative HFC of exploitation becomes the task of top priority.
Under such background, the refrigeration agent of HFC has instead proposed to use the refrigeration agent of fluoropropenes class, and the two is all very little for the ODP of the refrigeration agent of this fluoropropenes class and GWP, be flame retardancy, and roughly the same as the thermodynamic behaviour and the above-mentioned HFC of the standard of weighing refrigerant performance.The mix refrigerant (with reference to international open W02006/094303 brochure) of stable hydrocarbon, dimethyl ether, carbonic acid gas, two (trifluoromethyl) sulfide or the CF3I of use fluoropropenes and saturated hydrofluorocarbons, carbonatoms 3～5 has also been proposed in addition.Wherein, methylene fluoride refrigeration agent (HFC-32) even if since in the HFC refrigeration agent greenhouse effects of the earth coefficient also lower and freezing efficiency is higher, so gazed at all the more.
, in the refrigeration agent loop cycle of freezing machine, usually, the refrigerator oil of lubricated coolant compressor circulate during the course with refrigeration agent, so require in the refrigerator oil and the consistency of refrigeration agent.Yet, in the time of will using with the methylene fluoride refrigeration agent as the refrigerator oil that used that the HFC refrigeration agent is used in the past, can't obtain the sufficient consistency of refrigeration agent and refrigerator oil, be trapped in the cycle easily from the refrigerator oil of coolant compressor ejection, the refrigerator oil mass reduction that consequently produces in the coolant compressor causes insufficient lubrication, the problem of perhaps blocking expansion mechanisms such as kapillary.
Therefore, for fear of this phenomenon, carried out of the exploitation of methylene fluoride refrigeration agent with refrigerator oil, for example, having proposed ester is refrigerator oil (with reference to Japanese kokai publication hei 6-17073 communique, Japanese kokai publication hei 10-298572 communique, TOHKEMY 2002-060771 communique, TOHKEMY 2002-105471 communique, TOHKEMY 2002-129177 communique, TOHKEMY 2002-129178 communique, TOHKEMY 2002-129179 communique).
Summary of the invention
The problem that invention will solve
Yet,, take into account that to have oilness down with the consistency of methylene fluoride refrigeration agent and methylene fluoride refrigeration agent also be very difficult even if when using above-mentioned ester in the past to be refrigerator oil.For example, be that methylene fluoride refrigeration agent in the refrigerator oil shows that there be the oilness inadequate tendency of methylene fluoride refrigeration agent under existing in the refrigerator oil of good consistency with respect in the past ester.In addition, can enumerate viscosity (kinetic viscosity etc.) as the factor of influence of oilness, what become problem in the oilness in the presence of the methylene fluoride refrigeration agent is the viscosity of refrigerator oil and methylene fluoride refrigerant mixture (being working fluid composition), and its control may not be easy.And then, do not rely on the refrigerator oil of object of control viscosity or in the working fluid composition any and only adjust viscosity and then can't substantially improve oilness.
In addition, the environment for use of the refrigerator oil in the refrigeration agent loop cycle relates to the temperature province from high temperature to cryogenic wide region, and in addition, the ratio that exists of refrigerator oil and methylene fluoride refrigeration agent has more different according to the position of refrigeration agent loop cycle.But ester in the past is that refrigerator oil may not necessarily be said so with respect to the suitability of this environment for use fully.Especially the inadequate situation of low-temperature fluidity is more, and this problem is tangible in the situation of TOHKEMY 2002-129177 communique and the disclosed ester of TOHKEMY 2002-129178 communique.
The scheme that is used to deal with problems
The present invention makes in view of the problem with above-mentioned conventional art, its objective is provides a kind of when using with the methylene fluoride refrigeration agent, can realize refrigeration agent consistency, oilness and the whole refrigerator oil of low-temperature fluidity by high level, and the working fluid composition for refrigerating machine that uses it.
In order to address the above problem, the invention provides a kind of refrigerator oil, it contains in the refrigerator oil total amount is ester more than the benchmark 10 quality %, and use with the methylene fluoride refrigeration agent, this ester is the ester of tetramethylolmethane and lipid acid, wherein, in described lipid acid, carbonatoms with side chain is 6 lipid acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid is 20: 80～80: 20, and carbonatoms is 6 lipid acid and 3,5, the summation of 5-tri-methyl hexanoic acid shared ratio in described lipid acid is 20 moles more than the %.
Refrigerator oil of the present invention preferably provides with methylene fluoride and is sealing in the encloses container, and temperature remains on 40 ℃, when pressure remains on 2MPa, methylene fluoride is 25～35 quality % to the dissolution rate of refrigerator oil.
In addition, the invention provides a kind of working fluid composition for refrigerating machine, it contains the refrigerator oil and the methylene fluoride refrigeration agent of the invention described above.
The effect of invention
According to refrigerator oil of the present invention and working fluid composition for refrigerating machine, when using the methylene fluoride refrigeration agent, all high level is realized refrigeration agent consistency, oilness and low-temperature fluidity.
Embodiment
Below, the preferred embodiment of the present invention is elaborated.
The refrigerator oil of present embodiment, it contains in the refrigerator oil total amount is ester more than the benchmark 10 quality %, this ester is the ester (following according to circumstances be called " pentaerythritol fatty ester ") of tetramethylolmethane and lipid acid, in above-mentioned lipid acid, carbonatoms with side chain is 6 lipid acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid is that 20: 80～80: 20 and carbonatoms are 6 lipid acid and 3,5,5-tri-methyl hexanoic acid summation shared ratio in above-mentioned lipid acid is 20 moles more than the %.
In the refrigerator oil of present embodiment, the content of pentaerythritol fatty ester for the refrigerator oil total amount be benchmark count more than the 10 quality %, more than the preferred 30 quality %, more preferably more than the 50 quality %, further more than the preferred 70 quality %.The refrigerator oil of present embodiment can also be as described later, can contain lubricant base and additive beyond the pentaerythritol fatty ester, and pentaerythritol fatty ester can't be taken into account oilness and consistency with high level during less than 10 quality %.In addition, in the pentaerythritol fatty ester, the mixture of the part of hydroxyl of the esterified full ester of whole hydroxyls, tetramethylolmethane that can comprise tetramethylolmethane not esterified and the partial ester that keeps and full ester and partial ester, preferably ester entirely.
In addition, in constituting the lipid acid of pentaerythritol fatty ester, the carbonatoms with side chain is that 6 the lipid acid and the mol ratio of 3,5,5 Trimethylhexanoic acid are 20: 80～80: 20, preferred 25: 75～75: 25, more preferably 30: 70～70: 30.In addition, constituting carbonatoms in the lipid acid of pentaerythritol fatty ester is that the shared ratio of summation of 6 lipid acid and 3,5,5 Trimethylhexanoic acid is 20 moles more than the %.During the above-mentioned condition that do not satisfy that related lipase fat acid forms, be difficult to high level take into account with the sufficient consistency of methylene fluoride refrigeration agent, with the solubleness and the low-temperature fluidity of methylene fluoride refrigeration agent appropriateness.In addition, the ratio of the said lipid acid of the present invention, the fatty acid total amount that is meant the formation pentaerythritol fatty ester that refrigerator oil is contained is the value of benchmark.
As carbonatoms 6 lipid acid with side chain, particularly for example can enumerate 2 methyl valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl, 2,3-acid dimethyl etc., wherein preferred 2 methyl valeric acid and 2 Ethylbutanoic acid.
The pentaerythritol fatty ester of present embodiment is as long as be 6 lipid acid and 3 at the carbonatoms with side chain, 5, the mol ratio of 5-tri-methyl hexanoic acid is in 20: 80～80: 20 the scope, can also contain carbonatoms and be 6 lipid acid and 3 with side chain, 5, the lipid acid beyond the 5-tri-methyl hexanoic acid is as constituent.
As carbonatoms 6 lipid acid and 3 with side chain, 5, lipid acid beyond the 5-tri-methyl hexanoic acid, specifically can enumerate, acetate, propionic acid, butyric acid, 2 Methylpropionic acid, valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, the 2-neopentanoic acid, caproic acid, enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 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-ethyl valeric acid, 3-ethyl valeric acid, 1,1,2-trimethylammonium butyric acid, 1,2,2-trimethylammonium butyric acid, 1-ethyl-1-methylbutyric, 1-ethyl-2-Methyl Butyric Acid, sad, 2 ethyl hexanoic acid, the 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, the 2-methyl enanthic acid, the 3-methyl enanthic acid, the 4-methyl enanthic acid, the 5-methyl enanthic acid, the 6-methyl enanthic acid, the 2-Valproic acid, n-nonanoic acid, 2,2-dimethyl enanthic acid, the 2-methyloctanoic acid, 2-ethyl enanthic acid, the 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethylammonium 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 lipid acid of carbonatomss 2～9 such as 2-di-isopropyl propionic acid; The lipid acid of carbonatomss 10～20 such as capric acid, undecyl acid, dodecyl acid, tridecyl acid, tetradecyl acid, pentadecyl acid, hexadecyl acid, heptadecyl acid, octadecyl acid, nonadecyl acid, eicosyl acid, oleic acid etc.
When being used in combination carbonatoms and being 6 lipid acid and 3,5,5 Trimethylhexanoic acid and lipid acid in addition,, preferably use the lipid acid of carbonatoms 5～7 and/or the branched chain fatty acid of carbonatoms 8～9 as lipid acid in addition with side chain.In addition, in the following description, do not comprise " carbon atom with side chain is several 6 lipid acid " in " lipid acid of carbonatoms 5～7 ", in addition, do not comprise " 3,5,5 Trimethylhexanoic acid " in " branched chain fatty acid of carbonatoms 8～9 ".
Be used in combination carbonatoms and be 6 lipid acid, 3 with side chain, 5, during the branched chain fatty acid of the lipid acid of 5-tri-methyl hexanoic acid and carbonatoms 5～7 and/or carbonatoms 8～9, with being used in combination the carbonatoms with side chain is 6 lipid acid, 3,5, compare during lipid acid beyond the branched chain fatty acid of the lipid acid of 5-tri-methyl hexanoic acid and carbonatoms 5～7 and/or carbonatoms 8～9, exist the methylene fluoride refrigeration agent exist oilness down and with the further tendency of raising of the consistency of methylene fluoride refrigeration agent.In addition, be used in combination carbonatoms and be 6 lipid acid, 3 with side chain, 5, during the branched chain fatty acid of the lipid acid of 5-tri-methyl hexanoic acid and carbonatoms 5～7 and/or carbonatoms 8～9, the ratio that constitutes the branched chain fatty acid of the carbonatoms 8～9 in the lipid acid of pentaerythritol fatty ester is necessary for 80 moles below the %, and preferred 75 moles of % are following, more preferably 70 moles below the %.When the ratio of the branched chain fatty acid of carbonatoms 8～9 surpasses 80 moles of % and the consistency of methylene fluoride refrigeration agent become insufficient.
In addition, except the branched chain fatty acid of the lipid acid of carbonatoms 5～7 and/or carbonatoms 8～9, when using the lipid acid beyond these lipid acid, the ratio that constitutes the branched chain fatty acid of the lipid acid of the carbonatoms 5～7 in the lipid acid of pentaerythritol fatty ester and/or carbonatoms 8～9 be preferably 60 moles of % above, more preferably 70 moles of % above, more preferably 80 moles more than the %.The ratio of the branched chain fatty acid of the lipid acid of carbonatoms 5～7 and/or carbonatoms 8～9 is in aforementioned range the time, exist with higher level take into account the methylene fluoride refrigeration agent under existing oilness and with the tendency of the consistency of methylene fluoride refrigeration agent.
In the pentaerythritol fatty ester of present embodiment, from take into account the methylene fluoride refrigeration agent exist oilness down and with the consistency aspect consideration of methylene fluoride refrigeration agent, special preferred acid constituent only is 6 lipid acid and 3 by the carbonatoms with side chain, 5, the material that the 5-tri-methyl hexanoic acid constitutes.
The pentaerythritol fatty ester of present embodiment can also be the mixture of the different esters of molecular structure more than 2 kinds, in this case, each molecule may not all satisfy above-mentioned condition, as long as all satisfy above-mentioned condition as the lipid acid of formation pentaerythritol fatty ester contained in the refrigerator oil.
As mentioned above, the pentaerythritol fatty ester of present embodiment is to be 6 lipid acid and 3,5,5 Trimethylhexanoic acid as must composition with the carbonatoms with side chain, contains the material of other lipid acid as constituent as required.Promptly, the pentaerythritol fatty ester of present embodiment can be only a kind of lipid acid as the material of sour constituent, can be structure is different more than 2 kinds the lipid acid material as sour constituent, it be the lipid acid of quaternary carbon that this pentaerythritol fatty ester preferably only contains as sour constituent and the carbon atom carbonyl carbon adjacency (α position carbon atom) yet.Constitute in the lipid acid of pentaerythritol fatty ester, when containing α position carbon atom and being the lipid acid of quaternary carbon, the oilness under often the methylene fluoride refrigeration agent exists becomes insufficient.
As the preferred example of the sour constituent that constitutes pentaerythritol fatty ester of the present invention, can enumerate following material.
(i) be selected from 2 methyl valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl and 2, in the 3-acid dimethyl 1～6 kind combination with 3,5,5 Trimethylhexanoic acid;
(ii) be selected from 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl and 2, in the 3-acid dimethyl 1～6 kind, 3,5, the 5-tri-methyl hexanoic acid, with be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, the 2-neopentanoic acid, caproic acid, 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2, the 2-acid dimethyl, 2, the 3-acid dimethyl, 2, the 4-acid dimethyl, 3, the 3-acid dimethyl, 2 Ethylbutanoic acid, enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 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-ethyl valeric acid, 3-ethyl valeric acid, 1,1,2-trimethylammonium butyric acid, 1,2,2-trimethylammonium butyric acid, 1～30 kind combination in 1-ethyl-1 methylbutyric and the 1-ethyl-2-Methyl Butyric Acid;
(iii) be selected from 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl and 2, in the 3-acid dimethyl 1～6 kind, 3,5, the 5-tri-methyl hexanoic acid be selected from 2 ethyl hexanoic acid, the 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, the 2-methyl enanthic acid, the 3-methyl enanthic acid, the 4-methyl enanthic acid, the 5-methyl enanthic acid, the 6-methyl enanthic acid, the 2-Valproic acid, 2,2-dimethyl enanthic acid, the 2-methyloctanoic acid, 2-ethyl enanthic acid, the 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethylammonium butyric acid, 2,2,4,4-tetramethyl-valeric acid, 2,2,3,3-tetramethyl-valeric acid, 2,2,3,4-tetramethyl-valeric acid and 2,1～22 kind combination in the 2-di-isopropyl propionic acid;
(iv) be selected from 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyl and 2, in the 3-acid dimethyl 1～6 kind, 3,5,5-tri-methyl hexanoic acid and be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, the 2-neopentanoic acid, caproic acid, 2 methyl valeric acid, 3 methylvaleric acid, the 4-methylvaleric acid, 2, the 2-acid dimethyl, 2, the 3-acid dimethyl, 2, the 4-acid dimethyl, 3, the 3-acid dimethyl, 2 Ethylbutanoic acid, enanthic acid, 2 methyl caproic acid, the 3-methylhexanoic acid, the 4-methylhexanoic acid, the 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-ethyl valeric acid, 3-ethyl valeric acid, 1,1,2-trimethylammonium butyric acid, 1,2,2-trimethylammonium butyric acid, in 1-ethyl-1 methylbutyric and the 1-ethyl-2-Methyl Butyric Acid 1～30 kind, with be selected from 2 ethyl hexanoic acid, the 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, the 2-methyl enanthic acid, the 3-methyl enanthic acid, the 4-methyl enanthic acid, the 5-methyl enanthic acid, the 6-methyl enanthic acid, the 2-Valproic acid, 2,2-dimethyl enanthic acid, the 2-methyloctanoic acid, 2-ethyl enanthic acid, the 3-methyloctanoic acid, 2-ethyl-2,3,3-trimethylammonium butyric acid, 2,2,4,4-tetramethyl-valeric acid, 2,2,3,3-tetramethyl-valeric acid, 2,2,3,4-tetramethyl-valeric acid and 2,1～22 kind combination in the 2-di-isopropyl propionic acid.
In the refrigerator oil of present embodiment, above-mentioned pentaerythritol fatty ester is mainly used in base oil.Base oil as the refrigerator oil of present embodiment, can only use above-mentioned pentaerythritol fatty ester (content that is the pentaerythritol fatty ester of present embodiment is 100 quality %) separately, in addition, on the degree of not damaging its excellent performance, can also and with oxygen containing synthetic oils such as ester, polyoxyethylene glycol, polyvinyl ether, ketone, polyphenylene oxide, silicone, polysiloxane, perfluor ether such as in addition other polyol ester of above-mentioned pentaerythritol fatty ester, complex ester, ester ring type dicarboxylic ester (followingly according to circumstances being called " other contain oxygen synthetic oil ").
As the base oil beyond the pentaerythritol fatty ester of present embodiment, can also and use mineral oil, olefin polymer alkyl diphenyl base alkane, alkyl naphthene, the hydrocarbon system oil of alkylbenzene etc., and the ester beyond the pentaerythritol fatty ester of present embodiment is a base oil (monoesters, the polyvalent alcohol beyond the tetramethylolmethane and the ester of lipid acid, the lipid acid composition does not satisfy the lipid acid of above-mentioned condition and the ester of tetramethylolmethane, the alkyl aromatic ester, ester ring type carboxylicesters etc.), polyoxyethylene glycol, polyvinyl ether, ketone, polyphenylene oxide, silicone, polysiloxane, the oxygen containing synthetic oil of perfluor ether etc.As oxygen containing synthetic oil, above-mentioned in the middle of, preferably use ester, polyoxyethylene glycol, polyvinyl ether beyond the polyol ester of the present invention.
Above-mentioned other contains the polyol ester that particularly preferably is in the oxygen synthetic oil beyond the pentaerythritol fatty ester.As the polyol ester beyond the pentaerythritol fatty ester, the ester of polyvalent alcohols such as neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, Dipentaerythritol and lipid acid be can enumerate, the ester of neopentyl glycol and lipid acid and the ester of Dipentaerythritol and lipid acid particularly preferably are.
As DOPCP, the fatty acid ester of preferred carbonatoms 5～9.As such DOPCP, specifically for example can enumerate, neopentyl glycol two (3,5, the 5-trimethylammonium is own) ester, neopentyl glycol two (the 2-ethyl is own) ester, neopentyl glycol two (the 2-methyl is own) ester, neopentyl glycol two (2-ethyl penta) ester, the ester of neopentyl glycol and 2 methyl caproic acid and 2-ethyl valeric acid, the ester of neopentyl glycol and 3-methylhexanoic acid and 5-methylhexanoic acid, neopentyl glycol and 2 methyl caproic acid, the ester of 2 ethyl hexanoic acid, neopentyl glycol and 3,5-dimethyl caproic acid, 4,5-dimethyl caproic acid and 3, the ester of 4-dimethyl caproic acid, the neopentyl glycol diamyl ester, neopentyl glycol two (2-ethyl fourth) ester, neopentyl glycol two (2-methylpent) ester, neopentyl glycol two (2-methyl fourth) ester, neopentyl glycol two (3-methyl fourth) ester etc.
As dipentaerythritol ester, the ester of the lipid acid of ester, Dipentaerythritol and the carbonatoms 5～7 of the lipid acid of preferred Dipentaerythritol and carbonatoms 5～7 and the lipid acid of carbonatoms 8～9.As this dipentaerythritol ester, specifically can enumerate Dipentaerythritol, be selected from 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, 3,5, the ester of the lipid acid more than a kind in 5-tri-methyl hexanoic acid and the 2 ethyl hexanoic acid.
The refrigerator oil of present embodiment cooperate except pentaerythritol fatty ester contain the oxygen synthetic oil time, contain the olefiant use level of oxygenate only otherwise then be not particularly limited in the scope of the oilness of the refrigerator oil excellence of infringement present embodiment and consistency beyond the pentaerythritol fatty ester, when cooperating the polyol ester beyond the pentaerythritol fatty ester of present embodiment, with the refrigerator oil total amount is benchmark, need be for below the 90 quality %, below the preferred 85 quality %, more preferably below the 80 quality %, further below the preferred 70 quality %, below the further preferred 60 quality %, most preferably below the 50 quality %; When cooperating polyol ester to contain the oxygen synthetic oil in addition, be benchmark with the refrigerator oil total amount, need be for below the 50 quality %, below the preferred 40 quality %, more preferably below the 30 quality %.During the containing the olefiant use level of oxygenate and surpass aforementioned higher limit of the polyol ester beyond the pentaerythritol fatty ester or other, can't obtain feature of the present invention.
In addition, polyol ester beyond the pentaerythritol fatty ester of present embodiment can be esterified and the partial ester that hydroxyl directly keeps of of hydroxyl groups, also can be the esterified full esters of whole hydroxyls, the perhaps mixture of partial ester and full ester, the preferred 10mgKOH/g of hydroxyl value is following, more preferably 5mgKOH/g following, most preferably below the 3mgKOH/g.
The refrigerator oil of present embodiment and working fluid composition for refrigerating machine, respectively as the polyol ester beyond the pentaerythritol fatty ester of present embodiment, can contain by a kind of material that constitutes in the polyol ester of single structure, the mixture that also can contain in addition, the different polyol ester of structure more than 2 kinds.
In addition, the polyol ester beyond the pentaerythritol fatty ester of present embodiment can be any in the ester of ester, the lipid acid more than 2 kinds and the polyvalent alcohol more than 2 kinds of the ester of ester, the lipid acid more than 2 kinds and a kind of polyvalent alcohol of a kind of lipid acid and a kind of polyvalent alcohol, a kind of lipid acid and the polyvalent alcohol more than 2 kinds.
The refrigerator oil of present embodiment can also be the material that only is made of pentaerythritol fatty ester, in addition, also can be the material that is formed by pentaerythritol fatty ester and other base oil, can also contain various additive described later.In addition, in the working fluid composition for refrigerating machine of present embodiment, can also further contain various additives.In addition, in the following description, for content of additive, be that benchmark illustrates with the refrigerator oil total amount, but it is desirable to, select in preferred range described later when the content of these compositions in the working fluid composition for refrigerating machine is benchmark with the refrigerator oil total amount.
For the further refrigerator oil of improvement present embodiment and the antifriction consumption of working fluid composition for refrigerating machine, anti-loading, can cooperate at least a kind the phosphorus compound that is selected from the group of forming by ammonium salt, chloro phosphoric acid ester and the phosphorous acid ester of phosphoric acid ester, phosphate ester acid, thiophosphatephosphorothioate, phosphate ester acid.These phosphorus compounds are ester or its derivative of phosphoric acid or phosphorous acid and alkanol, polyether-type alcohol.
Particularly, as phosphoric acid ester, for example can enumerate tributyl phosphate, TNPP tri n pentyl phosphate, tri hexyl phosphate, THP triheptylphosphate, trioctyl phosphate, trinonyl phosphate, tridecyl phosphate, tricresyl phosphate (undecyl) ester, tricresyl phosphate (dodecyl) ester, tricresyl phosphate (tridecyl) ester, tricresyl phosphate (tetradecyl) ester, tricresyl phosphate (pentadecyl) ester, tricresyl phosphate (hexadecyl) ester, tricresyl phosphate (heptadecyl) ester, tricresyl phosphate (octadecyl) ester, the tricresyl phosphate grease, triphenylphosphate, tritolyl phosphate, three (dimethylbenzene) phosphoric acid ester, cresyl diphenyl phosphate, xylyl diphenyl phosphate etc.
As phosphate ester acid, can list acid mono phosphoric acid ester butyl ester, the acid phosphoric acid single fifth ester, the own ester of acid mono phosphoric acid ester, acid mono phosphoric acid ester heptyl ester, the 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 undecyl ester, acid mono phosphoric acid ester dodecyl ester, acid mono phosphoric acid ester tridecyl ester, acid mono phosphoric acid ester tetradecyl ester, acid mono phosphoric acid ester pentadecyl ester, acid mono phosphoric acid ester cetyl ester, acid mono phosphoric acid ester heptadecyl ester, mono phosphoric acid ester octadecyl ester acid, acid 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, the acid dioctylphosphoric acid ester, acid di(2-ethylhexyl)phosphate ester in the ninth of the ten Heavenly Stems, the 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 (tetradecyl) ester,) acid di(2-ethylhexyl)phosphate (pentadecyl) ester, acid di(2-ethylhexyl)phosphate (hexadecyl) ester, acid di(2-ethylhexyl)phosphate (heptadecyl) ester, acid di(2-ethylhexyl)phosphate (octadecyl) ester, acid di(2-ethylhexyl)phosphate oil base ester etc.
As thiophosphatephosphorothioate, can enumerate tributyl thiophosphate, the thiophosphoric acid triamyl, the own ester of tri o cresyl thiophosphate, the tri o cresyl thiophosphate heptyl ester, the 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 (undecyl) ester, tri o cresyl thiophosphate (dodecyl) ester, tri o cresyl thiophosphate (tridecyl) ester, tri o cresyl thiophosphate (tetradecyl) ester, tri o cresyl thiophosphate (pentadecyl) ester, tri o cresyl thiophosphate (hexadecyl) ester, tri o cresyl thiophosphate (heptadecyl) ester, tri o cresyl thiophosphate (octadecyl) ester, the tri o cresyl thiophosphate grease, triphenyl-thiophosphate, tri o cresyl thiophosphate cresols ester, tri o cresyl thiophosphate (dimethylbenzene) ester, thiophosphoric acid toluene diphenyl ester, thiophosphoric acid dimethylbenzene diphenyl ester etc.
As the ammonium salt of phosphate ester acid, can enumerate phosphate ester acid and carbonatoms 1～24, preferred 5～18 primary, the ammonium salt of the amine of secondary, uncle's straight or branched alkyl base.
As the amine of the ammonium salt that constitutes phosphate ester acid, can enumerate methylamine with straight or branched, ethamine, propylamine, butylamine, amylamine, hexylamine, heptyl amice, octylame, nonyl amine, decyl amine, undecyl amine, lauryl amine, tridecyl amine, tetradecylamine, pentadecyl amine, hexadecylamine, heptadecyl amine, octadecylamine, oil base amine, two tetradecy lamines, dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, two heptyl amices, Di-Octyl amine, nonyl amine, didecylamine, two (undecyl) amine, two (dodecyl) amine, two (tridecyl) amine, two (tetradecyl) amine, two (pentadecyl) amine, two (hexadecyl) amine, two (heptadecyl) amine, two (octadecyl) amine, two oleyl amines, two (tetracosyl) amine, Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, triamylamine, trihexylamine, three heptyl amices, trioctylamine, TNA trinonylamine, tridecylamine, three (undecyl) amine, tridodecylamine, three (tridecyl) amine, three (tetradecyl) amine, three (pentadecyl) amine, three (hexadecyl) amine, three (heptadecyl) amine, three (octadecyl) amine, three oleyl amines, the salt of amine such as three (24) amine.Amine can be independent compound, also can be the mixture of the compound more than 2 kinds.
As the chloro phosphoric acid ester, can enumerate tricresyl phosphate (two chloropropyls) ester, tricresyl phosphate (chloroethyl) ester, tricresyl phosphate (chloro-phenyl-) ester, two [two (chlorine the alkyl)] esters of phosphoric acid polyoxyalkylene etc.As phosphorous acid ester, can enumerate dibutyl phosphite, the phosphorous acid diamyl ester, the phosphorous acid dihexyl, phosphorous acid two heptyl esters, dioctyl phosphite, phosphorous acid ester in two ninth of the ten Heavenly Stems, didecyl phosphite, phosphorous acid two (undecyl) ester, phosphorous acid two (dodecyl) ester, phosphorous acid two greases, the phosphorous acid diphenyl ester, phosphorous acid two (cresols) ester (dicresyl phosphite), tributyl phosphate, the tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, the tricresyl phosphite heptyl ester, the tricresyl phosphite monooctyl ester, tris(nonyl phenyl) phosphate, tridecyl phosphite, tricresyl phosphite (undecyl) ester, tricresyl phosphite (dodecyl) ester, trioleyl phosphite, triphenyl phosphite, tricresyl phosphite (cresols) ester etc.In addition, can also use their mixture.
When the refrigerator oil of present embodiment and working fluid composition for refrigerating machine contain above-mentioned phosphorus compound, the content of phosphorus compound is not particularly limited, with the refrigerator oil total amount is benchmark (base oil is a benchmark with the total metering that always cooperates additive), preferred 0.01～5.0 quality %, more preferably 0.02～3.0 quality %.In addition, above-mentioned phosphorus compound 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 can add terpene compound in order further to improve its heat/chemical stability.The present invention's said " terpene compound " is meant compound that isoprene polymerization forms and their derivative, preferably uses 2 aggressiveness～8 aggressiveness of isoprene.As terpene compound, specifically can enumerate Geraniol, vernol, phantol, citral (comprising geranial (geranial)), geraniol, mentha camphor, limonene, terpinolene, Karvon, jononeionone, thujone (thujone), camphor (camphor), monoterpene such as borneol, the joyous alkene of alloy, alloy is alcohol vigorously, nerolidol, neotonin (Juvenile hormone), humulone, sub-cloves alkene, Elemenum, cadinol, cadinene, tutin hemiterpene alkene such as (tutin), trans-Geranylgeraniol (geranylgeraniol), phytol, sylvic acid, pimaradiene, daphnetoxin (daphnetoxin), taxol, sylvic acid, two terpenes such as pimaric acid, sesterterpenes such as the joyous alkene of geranyl alloy, squalene, obacalactone (Limonin), camellia sapogenol, what handkerchief alkane (Hopane), lanosterol triterpenes such as (lanosterol), carotenoid tetraterpene such as (carotenoid) etc.
In these terpene compounds, preferred monoterpene, hemiterpene alkene, two terpenes, more preferably hemiterpene alkene, the especially preferably joyous alkene (3 of α-alloy, 7,11-trimethyldodecane-1,3,6, the 10-tetraene) and/or the joyous alkene of β-alloy (7,11-dimethyl-3-methyne dodecane-1,6,10-triolefin).Among the present invention, terpene compound can use a kind separately, also can make up more than 2 kinds and use.
The content of the terpene compound of the refrigerator oil in the present embodiment is not particularly limited, and is benchmark with the refrigerator oil total amount, preferred 0.001～10 quality %, more preferably 0.01～5 quality %, further preferred 0.05～3 quality %.The content of terpene compound is during less than 0.001 quality %, and it is insufficient that often heat/chemical stability improves effect, and in addition, when surpassing 10 quality %, often oilness is insufficient.In addition, the content of the terpene compound in the working fluid composition for refrigerating machine of present embodiment is selected in above-mentioned preferred range when it is desirable to be benchmark with the refrigerator oil total amount.
In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine can contain at least a kind the epoxy compounds that is selected from phenyl glycidyl ether type epoxy compounds, alkyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, allyloxy silane compound, alkyl oxy silane compound, alicyclic epoxy compound, epoxidized fatty acid monoesters and the epoxidized vegetable oil in order further to improve its heat/chemical stability.
As phenyl glycidyl ether type epoxy compounds, specifically can phenyl glycidyl ether or alkyl phenyl glycidyl ether be shown example.Alkyl phenyl glycidyl ether herein can list the compound of the alkyl of the carbonatoms 1～13 with 1～3, wherein, having the compound of alkyl of 1 carbonatoms 4～10 can the illustration preference such as n-butylphenyl glycidyl ether, isobutyl phenenyl glycidyl ether, secondary butyl phenenyl glycidyl ether, tert-butyl-phenyl glycidyl ether, amyl group phenyl glycidyl ether, hexyl phenyl glycidyl ether, heptyl phenyl glycidyl ether, octyl phenyl glycidyl ether, nonyl phenyl glycidyl ether, decyl phenyl glycidyl ether etc.
But as the concrete illustration of alkyl glycidyl ether type epoxy compounds, decyl glycidyl ether, undecyl glycidyl ether, lauryl diglycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-ethylhexyl glycidyl ether, neopentylglycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane four glycidyl ethers, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidylether, poly-alkane glycol monoglycidyl ether, poly-alkane glycol diglycidylether etc.
Specifically can list as the glycidyl ester type epoxy compounds, phenyl glycidyl ester, alkyl glycidyl ester, alkenyl glycidyl ester etc., but as preferred glycidyl ester type epoxy compounds illustration 2,2-dimethyl-octa acid glycidyl ester, phenylformic acid glycidyl ester, glycidyl acrylate, glycidyl methacrylate etc.
But as the concrete illustration of allyloxy silane compound, 1,2-epoxy styrene, alkyl-1,2-epoxy styrene etc.
As alkyl oxosilane compound, but concrete illustration, 1,2-butylene oxide ring, 1,2-epoxy pentane, 1,2-epoxy hexane, 1,2-epoxy heptane, 1,2-octylene oxide, 1,2-epoxy nonane, 1,2-epoxy decane, 1,2-epoxy undecane, 1,2-epoxy dodecane, 1,2-epoxy tridecane, 1, the 2-epoxy tetradecane, 1,2-epoxy pentadecane, 1,2-epoxy n-Hexadecane, 1,2-epoxy heptadecane, 1,1,2-epoxy octadecane, 2-Disparmone, 1,2-epoxy eicosane etc.
As the alicyclic epoxy compound, but concrete illustration 1, the 2-epoxy cyclohexane, 1, the 2-cyclopentane epoxide, 3,4-epoxycyclohexyl methyl-3, the 4-epoxycyclohexane carboxylate, two (3,4-epoxycyclohexyl methyl) adipic acid ester, outward-2,3-epoxy norcamphane, two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid 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-methylcyclohexane, 4-epoxy ethyl-1,2-epoxy cyclohexane etc.
As the epoxidized fatty acid monoesters, but concrete illustration, the ester of the alcohol of the lipid acid of epoxidised carbonatoms 12～20 and carbonatoms 1～8 or phenol, alkylphenol etc.Especially preferably use the ester of butyl, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl group, phenyl and the butyl phenyl of epoxystearic acid.
As epoxidized vegetable oil, but concrete illustration, the epoxy compounds of soybean oil, linseed oil, cottonseed wet goods vegetables oil etc.
In these epoxy compoundss, preferred material is phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compounds, alicyclic epoxy compound and epoxidized fatty acid monoesters.Wherein more preferably phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compounds, preferred especially phenyl glycidyl ether, butylphenyl glycidyl ether, alkyl glycidyl ester or their mixture.
When the refrigerator oil of present embodiment and working fluid composition for refrigerating machine contained above-mentioned epoxy compounds, the content of epoxy compounds was not particularly limited, and is benchmark with the refrigerator oil total amount, preferred 0.1～5.0 quality %, more preferably 0.2～2.0 quality %.In addition, above-mentioned epoxy compounds 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 can contain known in the past refrigerator oil additive as required in order further to improve its performance.As described additive, can enumerate antioxidant, phenyl-a-naphthylamine, the N of phenol systems such as for example two-tertiary butyl-p-cresols, dihydroxyphenyl propane, N-two (2-naphthyl)-to metal inerting agents such as defoamers such as oiliness improvers such as extreme pressure agent, lipid acid, silicone-based, benzotriazole, viscosity index rising agent, pour point depressant, cleaning dispersion agents etc. such as wear-resistant dose of the antioxidant of amine such as phenyl diamines system, zinc dithiophosphate etc., chloroparaffin, sulphur compounds.These additives can use a kind separately, also can make up more than 2 kinds and use.These content of additive are not particularly limited, and are benchmark with the refrigerator oil total amount, are preferably below the 10 quality %, more preferably below the 5 quality %.
The kinetic viscosity of the refrigerator oil of present embodiment is not particularly limited, and the kinetic viscosity under 40 ℃ can preferred 3～1000mm
2/ s, more preferably 4～500mm
2/ s, 5～400mm most preferably
2/ s.In addition, the kinetic viscosity under 100 ℃ can preferred 1～100mm
2/ s, more preferably 2～50mm
2/ s.Kinetic viscosity during less than aforementioned lower value often oilness become insufficient, on the other hand, often become insufficient when surpassing aforementioned higher limit with the consistency of methylene fluoride refrigeration agent.
In addition, the volume specific resistance of the refrigerator oil of present embodiment is not particularly limited, can preferred 1.0 * 10
12Ω cm is above, more preferably 1.0 * 10
13Ω cm is above, most preferably 1.0 * 10
14More than the Ω cm.Often need high electrical insulating property during especially for the refrigerator purposes of hermetic type.In addition, among the present invention, volume specific resistance is meant the value under 25 ℃ that measure based on JISC2101 " electric insulation oil test method ".
In addition, the moisture content of the refrigerator oil of present embodiment is not particularly limited, and is benchmark with the refrigerator oil total amount, preferably 200ppm following, more preferably 100ppm following, most preferably below the 50ppm.During especially for the refrigerator purposes of hermetic type, consider, require moisture content few from viewpoint to the influence of the heat/chemical stability of refrigerator oil, electrical insulating property.
In addition, the acid number of the refrigerator oil of present embodiment is not particularly limited, and in order to prevent being used for the corrosion of metal of refrigerator or pipe arrangement, preferred 0.1mgKOH/g is following, more preferably below the 0.05mgKOH/g.In addition, among the present invention, acid number is meant " petroleum product and the lubricating oil one neutralization value test method " acid number of mensuration based on JISK2501.
In addition, the ash content of the refrigerator oil of present embodiment is not particularly limited, for heat/chemical stability of improving refrigerator oil and suppress the generation of deposition etc., preferably below the 100ppm, more preferably below the 50ppm.In addition, among the present invention, ash content is meant the ash value of measuring based on JISK2272 " ash content of crude oil and petroleum product and sulphated ash test method ".
Show fully high oilness and abundant high consistency when the refrigerator oil of present embodiment uses with the methylene fluoride refrigeration agent, can be widely used in the refrigerator oil of methylene fluoride refrigeration agent with refrigerator.Refrigerator as the refrigerator oil that uses present embodiment, specifically can enumerate refrigerating units such as room conditioning, box air-conditioning, refrigerator, automative air conditioning, dehumidifier, freezer, freezing and refrigeration warehouse, vending machine, show window, chemical industry equipment etc., wherein, preferred especially the refrigerator that uses with hermetic type compressor.In addition, the refrigerator oil of present embodiment can also use in the compressor of reciprocating motion type, rotary, centrifugal etc. arbitrary form.In addition, in these refrigerators, the refrigerator oil of present embodiment can be used for the working fluid composition for refrigerating machine that forms with the methylene fluoride refrigerant mixed as described later.
That is, the working fluid composition for refrigerating machine of present embodiment contains methylene fluoride the refrigeration agent refrigerator oil and the methylene fluoride refrigeration agent of the invention described above.Herein, the proportioning of refrigerator oil in the working fluid composition for refrigerating machine of present embodiment and methylene fluoride refrigeration agent is not particularly limited, the use level of refrigerator oil is 1～1000 weight part with respect to methylene fluoride 100 weight parts usually, preferred 2～800 weight parts.
In addition, in the working fluid composition for refrigerating machine of present embodiment, can not obtain the viewpoint of fully high oilness and fully high consistency from can't take into account in the past refrigerator oil of use the time, the situation that only contains the methylene fluoride refrigeration agent as the refrigeration agent composition can more be brought into play its availability, but also can contain the HFC refrigeration agent beyond the methylene fluoride refrigeration agent, unsaturated fluorinated hydrocarbons (HFO) refrigeration agent, three fluoridize the methyl iodide refrigeration agent, fluorine-containing ether series coolants such as perfluor ethers, dimethyl ethers etc. contain non-fluorine ether series coolant, ammonia, carbonic acid gas, natural series coolant such as hydrocarbon.
As the HFC refrigeration agent beyond the methylene fluoride, can enumerate carbonatoms 1～3, preferred 1～2 hydrogen fluorohydrocarbon.Specifically for example can enumerate trifluoromethane (HFC-23), pentafluoride ethane (HFC-125), 1,1,2,2-Tetrafluoroethane (HFC-134), 1,1,1,2-Tetrafluoroethane (HFC-134a), 1,1,1-Halothane (HFC-143a), 1,1-C2H4F2 C2H4F2 (HFC-152a), fluoroethane (HFC-161), 1,1,1,2,3,3,3-heptafluoro-propane (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), with 1,1,1,3,3-3-pentafluorobutane (HFC-365mfc), or their mixture more than 2 kinds.These refrigeration agents can and require performance suitably to select according to purposes, and it is independent for example can to enumerate HFC-32; HFC-23 is independent; HFC-134a is independent; HFC-125 is independent; The mixture of HFC-134a/HFC-32=60～80 quality %/40～20 quality %; The mixture of HFC-32/HFC-125=40～70 quality %/60～30 quality %; The mixture of HFC-125/HFC-143a=40～60 quality %/60～40 quality %; The mixture of HFC-134a/HFC-32/HFC-125=60 quality %/30 quality %/10 quality %; The mixture of HFC-134a/HFC-32/HFC-125=40～70 quality %/15～35 quality %/5～40 quality %; The mixtures of HFC-125/HFC-134a/HFC-143a=35～55 quality %/1～15 quality %/40～60 quality % etc. are as preferred example.And then more specifically can enumerate the mixture of HFC-134a/HFC-32=70/30 quality %; The mixture of HFC-32/HFC-125=60/40 quality %; The mixture (R410A) of HFC-32/HFC-125=50/50 quality %; The mixture (R410B) of HFC-32/HFC-125=45/55 quality %; The mixture (R507C) of HFC-125/HFC-143a=50/50 quality %; The mixture of HFC-32/HFC-125/HFC-134a=30/10/60 quality %; The mixture (R407C) of HFC-32/HFC-125/HFC-134a=23/25/52 quality %; The mixture (R407E) of HFC-32/HFC-125/HFC-134a=25/15/60 quality %; The mixture (R404A) of HFC-125/HFC-134a/HFC-143a=44/4/52 quality % etc.
As unsaturated fluorinated hydrocarbons (HFO) refrigeration agent, the fluoropropenes of preferred number of fluorine atoms 3～5, preferred 1,2,3,3,3-five fluoropropenes (HFO-1225ye), 1,3,3, the 3-tetrafluoro is for propylene (HFO-1234ze), 2,3,3, the 3-tetrafluoro is for propylene (HFO-1234yf), 1,2,3, the 3-tetrafluoro is for propylene (HFO-C1234ye) and 3,3, the mixture more than a kind or 2 kinds arbitrarily of 3-three fluoro propylene (HFO-1243zf).From the viewpoint of refrigeration agent rerum natura, be preferably selected among HFO-1225ye, HFO-1234ze and the HFO-1234yf more than a kind or 2 kinds.As with the mix refrigerant of the HFO refrigeration agent material of methylene fluoride/1234yf=40～60/60～40 weight % preferably, the material of wherein preferred methylene fluoride/1234yf=50/50 weight %.
As hydrocarbon coolant, the hydrocarbon of preferred carbonatoms 3～5, specifically for example can enumerate methane, ethene, ethane, propylene, propane, cyclopropane, normal butane, Trimethylmethane, tetramethylene, methyl cyclopropane, 2-methylbutane, Skellysolve A or the mixture more than 2 kinds in these.Wherein, preferably use 25 ℃, the following material of 1 normal atmosphere, preferably propane, normal butane, Trimethylmethane, 2-methylbutane or their mixture as gas.
As fluorine-containing ether series coolant, specifically for example can 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 refrigeration agents can and require performance suitably to select according to purposes.
The refrigerator oil of present embodiment is usually in the refrigerating and air conditioning machine, and the form of the working fluid composition for refrigerating machine that mixes with methylene fluoride refrigeration agent or methylene fluoride refrigeration agent with the mix refrigerant of refrigeration agent as described above exists.Cooperate at the refrigerator oil of said composition and refrigeration agent that refrigerator oil is not particularly limited with the ratio that cooperates of refrigeration agent in ratio and the working fluid composition for refrigerating machine of the present invention, with respect to refrigeration agent 100 mass parts, preferred 1～1000 mass parts of refrigerator oil, more preferably 2～800 mass parts.
The working fluid composition for refrigerating machine of present embodiment is preferred in the automative air conditioning of reciprocating motion type or revolving air-conditioning, refrigerator or style of opening with hermetic type compressor or hermetic type.In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine are preferred in refrigerating units such as dehumidifier, water-heater, freezer, freezing and refrigeration warehouse, vending machine, show window, chemical plant installations etc.And then the refrigerator oil of present embodiment and working fluid composition for refrigerating machine preferably also are used to have the equipment of radial compressor.
The refrigerator fluid composition of present embodiment can be preferred for foregoing various unsaturated fluorinated hydrocarbons refrigeration agent refrigerator, but representational structure as the refrigeration agent loop cycle that this refrigerator possessed, but illustration possesses compressor, condensing machine, expansion mechanism and vaporizer, and the equipment of moisture eliminator as required.
As compressor, but the compressor that illustration is following: in storing the encloses container of refrigerator oil, take in: the motor, turning axle that is embedded in aforementioned rotor and the compressor section that is connected with aforementioned motor by this turning axle that constitute by rotor and stator, and be trapped in the compressor of the high pressure vessel mode in the encloses container from the higher pressure refrigerant gas of aforementioned compressor section ejection; In storing the encloses container of refrigerator oil, take in the motor that constitutes by rotor and stator, the compressor section that is embedded in the turning axle of aforementioned rotor, is connected with aforementioned motor by this turning axle, and directly be discharged to the compressor etc. of the low pressure vessel mode outside the encloses container from the higher pressure refrigerant gas that aforementioned compressor section sprays.
Insulating film as the electrical machine insulation system material of motor part, from tensile strength characteristics, be difficult to produce the specific degradation phenomena of electrical isolation, the preferred second-order transition temperature that uses is a crystalline plastic film more than 50 ℃, and concrete example is as at least a insulating film in the group that is selected from polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether-ether-ketone, Polyethylene Naphthalate, polyamidoimide, polyimide and forms or the composite membrane that the high resin layer of lining glass transition temp forms on the low film of glass transition temp.In addition, as the magnet-wire that is used for motor part (Magnet Wire), preferred use second-order transition temperature is the individual layer of magnet-wire, for example polyester, polyester-imide, polymeric amide and the polyamidoimide etc. of the enamel lining more than 120 ℃, and perhaps the layer that second-order transition temperature is low is the composite coated magnet-wire with enamel lining that forms on upper strata for lower floor, high layer.As composite coated enamel line, can be set forth in lower floor lining polyester-imide, the enamel line (AI/EI) that forms at upper strata lining polyamide-imide, at lower floor's lining polyester, the enamel line (AI/PE) that forms at upper strata lining polyamide-imide etc.
As the siccative that is filled in moisture eliminator, preferably use following synthetic zeolite: by below fine pore 3.3 dusts, the carbon dioxide absorption capacity that is pressed under the 250mmHg of 25 ℃ of carbon dioxide branches is the silicic acid below 1.0%, the synthetic zeolite of alkali aluminate metal composite salt formation.Specifically for example can enumerate trade(brand)name XH-9, XH-10, XH-11, the XH-600 etc. of UNION SHOWA K.K system.
[embodiment]
Below based on embodiment and comparative example the present invention is carried out more specific description, the present invention is not subjected to any restriction of following examples.
[embodiment 1～10 and comparative example 1～11]
In embodiment 1～10 and the comparative example 1～11, base oil 1～13 that illustrates below inciting somebody to action respectively and additive 1～4 cooperate modulation test portion oil according to the ratio of components shown in table 1 or the table 2.The proterties of each test portion oil is shown in table 1～4.
(base oil)
Base oil 1: four esters of tetramethylolmethane and fatty acid mixt (mixtures of 70 moles of % of 2 methyl valeric acid, 30 moles of % of 3,5,5 Trimethylhexanoic acid)
Base oil 2: four esters of tetramethylolmethane and fatty acid mixt (mixtures of 30 moles of % of 2 methyl valeric acid, 70 moles of % of 3,5,5 Trimethylhexanoic acid)
Base oil 3: four esters of tetramethylolmethane 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(TMP) and 2 methyl valeric acid
Base oil 7: four esters of tetramethylolmethane and 2 methyl valeric acid
Base oil 8: four esters of tetramethylolmethane and 2 Ethylbutanoic acid
Base oil 9: six esters of Dipentaerythritol and 2 Ethylbutanoic acid
Base oil 10: four esters of tetramethylolmethane and fatty acid mixt (70 moles of % of 2 methyl caproic acid, 30 moles of % of 2-ethyl valeric acid)
Base oil 11: four esters of tetramethylolmethane and fatty acid mixt (50 moles of % of 2 ethyl hexanoic acid, 50 moles of % of 3,5,5 Trimethylhexanoic acid)
Base oil 12: four esters of tetramethylolmethane and fatty acid mixt (mixtures of 90 moles of % of 2 methyl valeric acid, 10 moles of % of 3,5,5 Trimethylhexanoic acid)
Base oil 13: four esters of tetramethylolmethane and fatty acid mixt (mixtures of 10 moles of % of 2 methyl valeric acid, 90 moles of % of 3,5,5 Trimethylhexanoic acid)
(additive)
Additive 1: tritolyl phosphate
Additive 2: triphenyl-thiophosphate
Additive 3:2,2-dimethyl-octa acid glycidyl ester
Additive 4:p-tert-butyl-phenyl glycidyl ether
Then each above-mentioned test portion oil is carried out the following test that illustrates.
(with the compatibility test of refrigeration agent)
" with the compatibility test method of refrigeration agent " based on JIS-K-2211 " refrigerator oil ", the mixture of methylene fluoride refrigeration agent (HFC-32) 18g and test portion oil 2g is cooled to-40 ℃ from 30 ℃ lentamente, mixture is separated or the temperature of gonorrhoea is estimated as two layers of separation temperature.In addition, "＜-40 " are represented in the mensuration temperature province of this test unconfirmed to being separated and gonorrhoea.In addition, " separation " in the table 4 is illustrated in 30 ℃ and has been separated or gonorrhoea.
(lubricity test)
Install in the inside of encloses container the upside test film use push rod (bane) (SKH-51), the downside test film uses the frictional testing machines of disk (disc) (FC250 HRC40).Import test portion oil 600g at the rub(bing)test position, after vacuum outgas in the system, import HFC-32 and heat.Temperature in the encloses container is after 100 ℃, refrigerant pressure are 1.5Mpa, to 100kgf, carries out 60 minutes abrasion test with the interim increase loading of loading step 10kgf (the step time is 2 minutes) under 100kgf.To the abrasion width of the blade after 60 minutes the test of each test portion oil measurement and the abrasion degree of depth of disk.
(test of the low temperature property separated out)
Test portion oil is put into developmental tube, putting into the ethanol bath of dry ice (70 ℃) dipping 24 hours, observation has or not gonorrhoea.
[table 1]
[table 2]
[table 3]
[table 4]
Claims (2)
1. refrigerator oil, it contains in the refrigerator oil total amount is ester more than the benchmark 10 quality %, and uses with the methylene fluoride refrigeration agent, and this ester is the ester of tetramethylolmethane and lipid acid, wherein, in described lipid acid, the carbonatoms with side chain is 6 lipid acid and 3,5, the mol ratio of 5-tri-methyl hexanoic acid is 20: 80～80: 20, and carbonatoms is that summation shared ratio in described lipid acid of 6 lipid acid and 3,5,5 Trimethylhexanoic acid is 20 moles more than the %.
2. working fluid composition for refrigerating machine, it contains described refrigerator oil of claim 1 and methylene fluoride refrigeration agent.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580308A1 (en) * | 1992-07-04 | 1994-01-26 | Kao Corporation | Working fluid composition for refrigeration machine |
| EP0653479A1 (en) * | 1993-05-27 | 1995-05-17 | Tonen Corporation | Refrigerator oil |
| CN1232865A (en) * | 1998-01-21 | 1999-10-27 | 三菱电机株式会社 | Lubricant composition for refrigerating machine employing HFC-32, HFC-125 or HFC-134a |
| JP2002129177A (en) * | 2000-10-30 | 2002-05-09 | Nippon Mitsubishi Oil Corp | Refrigerator oil |
| CN1354776A (en) * | 1999-06-09 | 2002-06-19 | 科金斯公司 | Method of improving performance of refrigerant systems |
| CN1629263A (en) * | 2003-11-21 | 2005-06-22 | 日本油脂株式会社 | Refrigeration lubricant composition |
| CN101544925A (en) * | 2008-03-26 | 2009-09-30 | 日本能源株式会社 | Refrigerator oil for refrigerant |
| CN101970624A (en) * | 2007-11-22 | 2011-02-09 | 出光兴产株式会社 | Lubricating oil composition for refrigerator and compressor using the same |
| CN102292420A (en) * | 2009-01-26 | 2011-12-21 | 科聚亚公司 | Production of polyol ester lubricants for refrigeration systems |
| CN102712862A (en) * | 2009-10-07 | 2012-10-03 | 科聚亚公司 | Polyolester lubricants for refrigeration systems |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4936656B2 (en) * | 2003-11-21 | 2012-05-23 | 日油株式会社 | Lubricating oil composition for refrigerator |
-
2010
- 2010-03-17 JP JP2010061201A patent/JP5525877B2/en active Active
-
2011
- 2011-03-17 CN CN201110065387.5A patent/CN102191114B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0580308A1 (en) * | 1992-07-04 | 1994-01-26 | Kao Corporation | Working fluid composition for refrigeration machine |
| EP0653479A1 (en) * | 1993-05-27 | 1995-05-17 | Tonen Corporation | Refrigerator oil |
| CN1232865A (en) * | 1998-01-21 | 1999-10-27 | 三菱电机株式会社 | Lubricant composition for refrigerating machine employing HFC-32, HFC-125 or HFC-134a |
| CN1354776A (en) * | 1999-06-09 | 2002-06-19 | 科金斯公司 | Method of improving performance of refrigerant systems |
| JP2002129177A (en) * | 2000-10-30 | 2002-05-09 | Nippon Mitsubishi Oil Corp | Refrigerator oil |
| CN1629263A (en) * | 2003-11-21 | 2005-06-22 | 日本油脂株式会社 | Refrigeration lubricant composition |
| CN101970624A (en) * | 2007-11-22 | 2011-02-09 | 出光兴产株式会社 | Lubricating oil composition for refrigerator and compressor using the same |
| CN101544925A (en) * | 2008-03-26 | 2009-09-30 | 日本能源株式会社 | Refrigerator oil for refrigerant |
| CN102292420A (en) * | 2009-01-26 | 2011-12-21 | 科聚亚公司 | Production of polyol ester lubricants for refrigeration systems |
| CN102712862A (en) * | 2009-10-07 | 2012-10-03 | 科聚亚公司 | Polyolester lubricants for refrigeration systems |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102191113A (en) * | 2010-03-17 | 2011-09-21 | 吉坤日矿日石能源株式会社 | Freezer oil and work fluid composition for freezer |
| WO2013051271A1 (en) * | 2011-10-06 | 2013-04-11 | パナソニック株式会社 | Refrigeration device |
| US10273394B2 (en) | 2011-10-26 | 2019-04-30 | Jx Nippon Oil & Energy Corporation | Refrigerating machine working fluid composition and refrigerant oil |
| CN105505326A (en) * | 2011-10-26 | 2016-04-20 | 吉坤日矿日石能源株式会社 | Refrigerating machine working fluid composition and application thereof |
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| US10414962B2 (en) | 2012-03-27 | 2019-09-17 | Jxtg Nippon Oil & Energy Corporation | Working fluid composition for refrigerator |
| CN106103668A (en) * | 2014-03-14 | 2016-11-09 | 捷客斯能源株式会社 | Refrigerator oil and working fluid composition for refrigerating machine |
| US10550351B2 (en) | 2014-03-14 | 2020-02-04 | Jx Nippon Oil & Energy Corporation | Refrigerator oil and refrigerator working fluid composition |
| CN105331422A (en) * | 2014-08-08 | 2016-02-17 | 百达精密化学股份有限公司 | High-performance refrigeration lubricating oil composition |
| CN107001970A (en) * | 2014-11-18 | 2017-08-01 | Jxtg能源株式会社 | Refrigerator oil and working fluid composition for refrigerating machine |
| CN109536259A (en) * | 2018-12-19 | 2019-03-29 | 上海森帝润滑技术有限公司 | Centrifugal compressed machine oil and preparation method thereof |
| CN109536259B (en) * | 2018-12-19 | 2021-06-11 | 上海森帝润滑技术有限公司 | Centrifugal compressor oil and preparation method thereof |
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| CN115443323B (en) * | 2020-04-30 | 2024-03-15 | 引能仕株式会社 | Refrigerator oil and working fluid composition for refrigerator |
| CN112126495A (en) * | 2020-09-01 | 2020-12-25 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigerating machine oil composition |
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| CN102191114B (en) | 2015-12-02 |
| JP5525877B2 (en) | 2014-06-18 |
| JP2011195631A (en) | 2011-10-06 |
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