CN102191114B - 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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- CN102191114B CN102191114B CN201110065387.5A CN201110065387A CN102191114B CN 102191114 B CN102191114 B CN 102191114B CN 201110065387 A CN201110065387 A CN 201110065387A CN 102191114 B CN102191114 B CN 102191114B
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Abstract
The present invention is a kind of refrigerator oil and working fluid composition for refrigerating machine.Refrigerator oil of the present invention, the ester that it contains in refrigerator oil total amount is more than benchmark 10 quality %, and use together with methylene fluoride refrigeration agent, this ester is the ester of tetramethylolmethane and lipid acid, wherein, in described lipid acid, the carbonatoms with side chain is the lipid acid and 3 of 6,5, the mol ratio of 5-tri-methyl hexanoic acid is 20: 80 ~ 80: 20, carbonatoms is the lipid acid of 6 and the ratio of the summation of 3,5,5 Trimethylhexanoic acid shared by described lipid acid is more than 20 % by mole.In addition, working fluid composition for refrigerating machine of the present invention contains refrigerator oil and the methylene fluoride refrigeration agent of the invention described above.
Description
Technical field
The present invention relates to a kind of refrigerator oil and working fluid composition for refrigerating machine, specifically, a kind of useful refrigerator oil and employ the working fluid composition for refrigerating machine of this refrigerator oil when using together with methylene fluoride refrigeration agent (HFC-32) is related to.
Background technology
Due to the problem of depletion of the ozone layer in recent years, the object of restriction can be become as the CFC (Chlorofluorocarbons (CFCs)) of the refrigeration agent of freezing machine and HCFC (Hydrochlorofluorocarbons) in the past, replace them, use HFC (hydrogen fluorohydrocarbon) as refrigeration agent gradually.
When CFC and HCFC is refrigeration agent, as refrigerator oil, can suitably use the hydrocarbon ils such as mineral oil, alkylbenzene, but when replacing refrigeration agent, due to show at the refrigerator oil of the lower use that coexists with the consistency of refrigeration agent, oilness, with the unforeseeable behavior such as dissolving viscosity, heat/chemical stability of refrigeration agent, thus each refrigeration agent needs to develop refrigerator oil.Therefore, as HFC refrigeration agent refrigerator oil, such as, poly-alkane glycol is developed (with reference to Japanese Unexamined Patent Publication 02-242888 publication, ester (with reference to Japanese Unexamined Patent Publication 03-200895 publication), carbonic ether (with reference to Japanese Unexamined Patent Publication 03-217495 publication), polyvinyl ether (with reference to Japanese Unexamined Patent Publication 06-128578 publication) etc.In these refrigerator oils, ester is widely used in refrigerator, air-conditioning purposes etc.
In HFC refrigeration agent, HFC-134a, R407C, R410A be typically used as used for automobile air conditioning, refrigerator with or room conditioning refrigeration agent.But although these HFC refrigeration agent ozone destruction coefficient (ODP) are zero, greenhouse effects of the earth coefficient (GWP) is high, so become all the more the object of restriction.Therefore, the refrigeration agent of the alternative HFC of exploitation becomes the task of top priority.
In this context, the instead refrigeration agent of HFC, propose the refrigeration agent using fluoropropenes class, both ODP and GWP of the refrigeration agent of this fluoropropenes class are all very little, flame retardancy, and roughly the same with above-mentioned HFC as the thermodynamic behaviour of the standard weighing refrigerant performance.In addition, also proposed the mix refrigerant (reference International Publication W02006/094303 brochure) using fluoropropenes and saturated hydrofluorocarbons, the stable hydrocarbon of carbonatoms 3 ~ 5, dimethyl ether, carbonic acid gas, two (trifluoromethyl) sulfide or CF3I.Wherein, methylene fluoride refrigeration agent (HFC-32) even if due in HFC refrigeration agent greenhouse effects of the earth coefficient also lower and freezing efficiency is higher, so attract attention all the more.
, in the refrigerant circulation cycle of freezing machine, usually, the refrigerator oil of lubrication coolant compressor circulates during the course together with refrigeration agent, so require the consistency with refrigeration agent in refrigerator oil.But, using when using together with methylene fluoride refrigeration agent as the refrigerator oil used of HFC refrigeration agent in the past, refrigeration agent and the sufficient consistency of refrigerator oil cannot be obtained, easily be trapped in the cycle from the refrigerator oil of coolant compressor ejection, the refrigerator oil mass consequently produced in coolant compressor reduces and causes insufficient lubrication, or blocks the problem of the expansion mechanisms such as kapillary.
Therefore, in order to avoid this phenomenon, carry out the exploitation of methylene fluoride refrigeration agent refrigerator oil, such as, ester system refrigerator oil (with reference to Japanese Unexamined Patent Publication 6-17073 publication, Japanese Unexamined Patent Publication 10-298572 publication, Japanese Unexamined Patent Publication 2002-060771 publication, Japanese Unexamined Patent Publication 2002-105471 publication, Japanese Unexamined Patent Publication 2002-129177 publication, Japanese Unexamined Patent Publication 2002-129178 publication, Japanese Unexamined Patent Publication 2002-129179 publication) is proposed.
Summary of the invention
the problem that invention will solve
But, even if when using above-mentioned ester system refrigerator oil in the past, the oilness taken into account under existing with the consistency of methylene fluoride refrigeration agent and methylene fluoride refrigeration agent is also very difficult.Such as, the refrigerator oil showing good consistency relative to the methylene fluoride refrigeration agent in ester system refrigerator oil in the past exist methylene fluoride refrigeration agent exist under the insufficient tendency of oilness.In addition, factor of influence as oilness can enumerate viscosity (kinetic viscosity etc.), what become problem in the oilness under methylene fluoride refrigeration agent exists is the viscosity of refrigerator oil and methylene fluoride refrigerant mixture (i.e. working fluid composition), and its control may not be easy.And then any one not relying in the refrigerator oil of object or working fluid composition controlling viscosity only adjusts viscosity and then cannot substantially improve oilness.
In addition, the environment for use of the refrigerator oil in the refrigerant circulation cycle relates to the temperature province of the wide region from high temperature to low temperature, and in addition, the ratio that exists of refrigerator oil and methylene fluoride refrigeration agent has relatively big difference according to the position in refrigerant circulation cycle.But ester system refrigerator oil in the past may not talkatively be sufficient relative to the suitability of this environment for use.Especially the situation that low-temperature fluidity is insufficient is more, and the situation of this problem ester disclosed in Japanese Unexamined Patent Publication 2002-129177 publication and Japanese Unexamined Patent Publication 2002-129178 publication is obvious.
for the scheme of dealing with problems
The present invention makes in view of the problem with above-mentioned conventional art, its objective is and provide a kind of when using together with methylene fluoride refrigeration agent, the whole refrigerator oil of refrigeration agent consistency, oilness and low-temperature fluidity can be realized by high level, and use its working fluid composition for refrigerating machine.
In order to solve the problem, the invention provides a kind of refrigerator oil, the ester that it contains in refrigerator oil total amount is more than benchmark 10 quality %, and use together with methylene fluoride refrigeration agent, this ester is the ester of tetramethylolmethane and lipid acid, wherein, in described lipid acid, the carbonatoms with side chain is the lipid acid and 3 of 6, the mol ratio of 5,5-tri-methyl hexanoic acid is 20: 80 ~ 80: 20, and carbonatoms is the lipid acid and 3 of 6, the ratio that the summation of 5,5-tri-methyl hexanoic acid is shared in described lipid acid is more than 20 % by mole.
Refrigerator oil of the present invention preferably provides and is sealing in encloses container together with methylene fluoride, and temperature remains on 40 DEG C, pressure is when remaining on 2MPa, and 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 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 methylene fluoride refrigeration agent, all refrigeration agent consistency, oilness and low-temperature fluidity can be realized by high level.
Embodiment
Below, the preferred embodiment of the present invention is described in detail.
The refrigerator oil of present embodiment, the ester that it contains in refrigerator oil total amount is more than benchmark 10 quality %, this ester is the ester (being according to circumstances called below " pentaerythritol fatty ester ") of tetramethylolmethane and lipid acid, in above-mentioned lipid acid, the carbonatoms with side chain is the lipid acid and 3 of 6,5, the mol ratio of 5-tri-methyl hexanoic acid be 20: 80 ~ 80: 20 and carbonatoms be 6 lipid acid and 3, the ratio of 5,5-tri-methyl hexanoic acid summation shared by above-mentioned lipid acid is more than 20 % by mole.
In the refrigerator oil of present embodiment, the content of pentaerythritol fatty ester for refrigerator oil total amount for benchmark counts more than 10 quality %, preferably more than 30 quality %, more preferably more than 50 quality %, further preferred more than 70 quality %.The refrigerator oil of present embodiment as described later, containing the lubricant base beyond pentaerythritol fatty ester and additive, when pentaerythritol fatty ester is less than 10 quality %, can also can cannot take into account oilness and consistency with high level.In addition, in pentaerythritol fatty ester, the mixture of the esterified full ester of whole hydroxyls of tetramethylolmethane, the not esterified and partial ester that retains of a part of the hydroxyl of tetramethylolmethane and full ester and partial ester can be comprised, preferably ester entirely.
In addition, in the lipid acid forming pentaerythritol fatty ester, the carbonatoms with side chain is the lipid acid of 6 and the mol ratio of 3,5,5 Trimethylhexanoic acid is 20: 80 ~ 80: 20, preferably 25: 75 ~ 75: 25, more preferably 30: 70 ~ 70: 30.In addition, the ratio shared by summation of to form carbonatoms in the lipid acid of pentaerythritol fatty ester be 6 lipid acid and 3,5,5 Trimethylhexanoic acid is more than 20 % by mole.When not meeting the above-mentioned condition of related lipase fat acid composition, be difficult to high level take into account with the sufficient consistency of methylene fluoride refrigeration agent, with the solubleness of methylene fluoride refrigeration agent appropriateness and low-temperature fluidity.In addition, the ratio of the said lipid acid of the present invention, refers to that the fatty acid total amount of the formation pentaerythritol fatty ester contained by refrigerator oil is the value of benchmark.
Be the lipid acid of 6 as the carbonatoms with side chain, specifically can enumerate such as, 2 methyl valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyls, 2,3-acid dimethyl etc., wherein preferred 2 methyl valeric acid and 2 Ethylbutanoic acid.
As long as the pentaerythritol fatty ester of present embodiment is the lipid acid and 3 of 6 at the carbonatoms with side chain, 5, the mol ratio of 5-tri-methyl hexanoic acid is in the scope of 20: 80 ~ 80: 20, can also be the lipid acid and 3 of 6 containing the carbonatoms with side chain, lipid acid beyond 5,5-tri-methyl hexanoic acid is as constituent.
As the carbonatoms with side chain be 6 lipid acid and 3,5,5 Trimethylhexanoic acid beyond lipid acid, specifically can enumerate, acetic acid, propionic acid, butyric acid, 2 Methylpropionic acid, valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, PA, caproic 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-ethylpentanoic, 3-ethylpentanoic, 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, 3-thylhexoic acid, 3,5-dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 3,4-dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 2,2-dimethylhexanoic acid, 2-methyl enanthic acid, 3-methyl enanthic acid, 4-methyl enanthic acid, 5-methyl enanthic acid, 6-methyl enanthic acid, valproic acid, n-nonanoic acid, 2,2-dimethyl enanthic acid, 2-methyloctanoic acid, 2-ethyl enanthic acid, 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, the lipid acid of the carbonatomss 2 ~ 9 such as 2,2-di-isopropyl propionic acid, the lipid acid etc. of the carbonatomss 10 ~ 20 such as the acid of capric acid, undecyl, dodecyl is sour, tridecyl is sour, tetradecyl is sour, pentadecyl is sour, hexadecyl is sour, heptadecyl is sour, Eighteen alkyl acid, nonadecyl sour, eicosyl is sour, oleic acid.
Combinationally use the carbonatoms with side chain be 6 lipid acid and 3,5,5 Trimethylhexanoic acid and lipid acid in addition time, as lipid acid in addition, preferably use the lipid acid of carbonatoms 5 ~ 7 and/or the branched chain fatty acid of carbonatoms 8 ~ 9.In addition, in the following description, do not comprise in " lipid acid of carbonatoms 5 ~ 7 " " carbon atom with side chain is the lipid acid of several 6 ", in addition, do not comprise " 3,5,5 Trimethylhexanoic acid " in " branched chain fatty acid of carbonatoms 8 ~ 9 ".
Combinationally use the lipid acid, 3 that the carbonatoms with side chain is 6,5, 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 combinationally use the lipid acid, 3 that the carbonatoms with side chain is 6,5, compare when 5-tri-methyl hexanoic acid and lipid acid beyond the lipid acid of carbonatoms 5 ~ 7 and/or the branched chain fatty acid of carbonatoms 8 ~ 9, there is methylene fluoride refrigeration agent and there is lower oilness and the tendency that improve further with the consistency of methylene fluoride refrigeration agent.In addition, combinationally use the lipid acid, 3 that the carbonatoms with side chain is 6,5, 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 forming the branched chain fatty acid of the carbonatoms 8 ~ 9 in the lipid acid of pentaerythritol fatty ester is necessary for less than 80 % by mole, preferably less than 75 % by mole, more preferably less than 70 % by mole.When the ratio of the branched chain fatty acid of carbonatoms 8 ~ 9 is more than 80 % by mole and the consistency of methylene fluoride refrigeration agent become insufficient.
In addition, except the lipid acid of carbonatoms 5 ~ 7 and/or the branched chain fatty acid of carbonatoms 8 ~ 9, when using the lipid acid beyond these lipid acid, the lipid acid of carbonatoms 5 ~ 7 in the lipid acid of formation pentaerythritol fatty ester and/or the ratio of the branched chain fatty acid of carbonatoms 8 ~ 9 are preferably more than 60 % by mole, are more preferably more than 70 % by mole, more preferably more than 80 % by mole.When the ratio of the lipid acid of carbonatoms 5 ~ 7 and/or the branched chain fatty acid of carbonatoms 8 ~ 9 is in aforementioned range, there is the tendency taking into account the oilness under the existence of methylene fluoride refrigeration agent and the consistency with methylene fluoride refrigeration agent with higher level.
In the pentaerythritol fatty ester of present embodiment, from take into account methylene fluoride refrigeration agent exist oilness and consider with the consistency aspect of methylene fluoride refrigeration agent, particularly preferably sour constituent is only the lipid acid and 3 of 6 by the carbonatoms with side chain, the material that 5,5-tri-methyl hexanoic acid is formed.
The pentaerythritol fatty ester of present embodiment can also be the mixture of the different ester of molecular structure of more than two kinds, in this case, each molecule does not necessarily all meet above-mentioned condition, as long as meet above-mentioned condition as the lipid acid entirety of formation pentaerythritol fatty ester contained in refrigerator oil.
As mentioned above, the pentaerythritol fatty ester of present embodiment to be the carbonatoms with side chain be 6 lipid acid and 3,5,5 Trimethylhexanoic acid as essential component, as required containing other lipid acid as the material of constituent.Namely, the pentaerythritol fatty ester of present embodiment can be only a kind of lipid acid as the material of sour constituent, also can be lipid acid that two or more structure the is different material as sour constituent, this pentaerythritol fatty ester be preferably only containing the lipid acid that the carbon atom (α position carbon atom) adjacent with carbonyl carbon as sour constituent is not quaternary carbon.Form in the lipid acid of pentaerythritol fatty ester, when being the lipid acid of quaternary carbon containing α position carbon atom, the oilness often under the existence of methylene fluoride refrigeration agent becomes insufficient.
As the preferred example of the sour constituent of formation pentaerythritol fatty ester of the present invention, following material can be enumerated.
(i) be selected from 1 ~ 6 kind in 2 methyl valeric acid, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2,2-acid dimethyls and 2,3-acid dimethyl with the combination of 3,5,5 Trimethylhexanoic acid;
(ii) 2 methyl valeric acid is selected from, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2, 2-acid dimethyl and 2, 1 ~ 6 kind in 3-acid dimethyl, 3, 5, 5-tri-methyl hexanoic acid, with be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, 2, 2-neopentanoic acid, caproic acid, 2 methyl valeric 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-ethylpentanoic, 3-ethylpentanoic, 1, 1, 2-trimethylammonium butyric acid, 1, 2, 2-trimethylammonium butyric acid, the combination of 1 ~ 30 kind in 1-ethyl-1 methylbutyric and 1-Ethyl-2-Methyl butyric acid,
(iii) 2 methyl valeric acid is selected from, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 2, 2-acid dimethyl and 2, 1 ~ 6 kind in 3-acid dimethyl, 3, 5, 5-tri-methyl hexanoic acid be selected from 2 ethyl hexanoic acid, 3-thylhexoic acid, 3, 5-dimethylhexanoic acid, 2, 4-dimethylhexanoic acid, 3, 4-dimethylhexanoic acid, 4, 5-dimethylhexanoic acid, 2, 2-dimethylhexanoic 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, 2-methyloctanoic acid, 2-ethyl enanthic acid, 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, the combination of 1 ~ 22 kind in 2-di-isopropyl propionic acid,
(iv) 2 methyl valeric acid is selected from, 3 methylvaleric acid, 4-methylvaleric acid, 2 Ethylbutanoic acid, 1 ~ 6 kind in 2,2-acid dimethyl and 2,3-acid dimethyl, 3,5,5 Trimethylhexanoic acid and be selected from valeric acid, 2-Methyl Butyric Acid, 3 Methylbutanoic acid, PA, caproic acid, 2 methyl valeric 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-ethylpentanoic, 3-ethylpentanoic, 1,1,2-trimethylammonium butyric acid, 1,2,2-trimethylammonium butyric acid, 1 ~ 30 kind in 1-ethyl-1 methylbutyric and 1-Ethyl-2-Methyl butyric acid, with be selected from 2 ethyl hexanoic acid, 3-thylhexoic acid, 3,5-dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 3,4-dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 2,2-dimethylhexanoic 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, 2-methyloctanoic acid, 2-ethyl enanthic acid, 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, the combination of 1 ~ 22 kind in 2,2,3,4-tetramethyl-valeric acid and 2,2-di-isopropyl propionic acid.
In the refrigerator oil of present embodiment, above-mentioned pentaerythritol fatty ester is mainly used in base oil.As the base oil of the refrigerator oil of present embodiment, only can be used alone above-mentioned pentaerythritol fatty ester (namely the content of the pentaerythritol fatty ester of present embodiment is 100 quality %), in addition, in the degree of performance not damaging its excellence, can also and with other polyol ester beyond above-mentioned pentaerythritol fatty ester, complex ester, the esters such as ester ring type dicarboxylic ester, polyoxyethylene glycol, polyvinyl ether, ketone, polyphenylene oxide, silicone, polysiloxane, the oxygen containing synthetic oils such as perfluor ether (being according to circumstances called below " other contain oxygen synthetic oil ").
As the base oil beyond the pentaerythritol fatty ester of present embodiment, can also also with mineral oil, olefin polymer alkyl diphenyl base alkane, alkyl naphthene, the hydrocarbon system oil of alkylbenzene etc., and the ester system base oil (monoesters beyond the pentaerythritol fatty ester of present embodiment, polyvalent alcohol beyond tetramethylolmethane and the ester of lipid acid, lipid acid composition does not meet the lipid acid of above-mentioned condition and the ester of tetramethylolmethane, 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, in the middle of above-mentioned, preferably use ester, polyoxyethylene glycol, the polyvinyl ether beyond polyol ester of the present invention.
Above-mentioned other contains in oxygen synthetic oil the polyol ester particularly preferably be beyond pentaerythritol fatty ester.As the polyol ester beyond pentaerythritol fatty ester, the ester of the polyvalent alcohols such as neopentyl glycol, trimethylolethane, TriMethylolPropane(TMP), tri hydroxy methyl butane, Dipentaerythritol and lipid acid can be enumerated, particularly preferably be the ester of neopentyl glycol and lipid acid and the ester of Dipentaerythritol and lipid acid.
As DOPCP, the fatty acid ester of preferred carbonatoms 5 ~ 9.As such DOPCP, specifically can enumerate such as, neopentyl glycol two (3, 5, 5-trimethylammonium is own) ester, neopentyl glycol two (2-ethyl hexyl) ester, neopentyl glycol two (2-methyl is own) ester, neopentyl glycol two (2-ethyl penta) ester, the ester of neopentyl glycol and 2 methyl caproic acid and 2-ethylpentanoic, 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-dimethylhexanoic acid, 4, 5-dimethylhexanoic acid and 3, the ester of 4-dimethylhexanoic acid, 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 ester of the lipid acid of preferred Dipentaerythritol and carbonatoms 5 ~ 7, Dipentaerythritol and the lipid acid of 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-ethylpentanoic, 2 methyl caproic acid, 3, the ester of the lipid acid of more than a kind in 5,5-tri-methyl hexanoic acid and 2 ethyl hexanoic acid.
The refrigerator oil of present embodiment coordinate except pentaerythritol fatty ester containing oxygen synthetic oil time, the use level containing oxygen synthetic oil beyond pentaerythritol fatty ester only otherwise be then not particularly limited in the oilness of refrigerator oil excellence of infringement present embodiment and the scope of consistency, coordinate present embodiment pentaerythritol fatty ester beyond polyol ester time, with refrigerator oil total amount for benchmark, needing is below 90 quality %, preferably below 85 quality %, more preferably below 80 quality %, preferred below 70 quality % further, further preferred below 60 quality %, most preferably below 50 quality %, time beyond cooperation polyol ester containing oxygen synthetic oil, with refrigerator oil total amount for benchmark, needing is below 50 quality %, preferably below 40 quality %, more preferably below 30 quality %.When polyol ester beyond pentaerythritol fatty ester or other the use level containing oxygen synthetic oil exceed aforementioned higher limit, feature of the present invention cannot be obtained.
In addition, polyol ester beyond the pentaerythritol fatty ester of present embodiment can be that of the hydroxyl of polyvalent alcohol is esterified and the partial ester that hydroxyl directly retains, also can be the esterified full ester of whole hydroxyl, or the mixture of partial ester and full ester, preferred below the 10mgKOH/g of hydroxyl value, more preferably below 5mgKOH/g, most preferably below 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 containing the material be made up of 1 in the polyol ester of single structure kind, in addition, the mixture of the different polyol ester of structure of more than two kinds can also be contained.
In addition, the polyol ester beyond the pentaerythritol fatty ester of present embodiment can be any one in the ester of the ester of the ester of a kind of lipid acid and a kind of polyvalent alcohol, lipid acid of more than two kinds and a kind of polyvalent alcohol, a kind of lipid acid and the ester of polyvalent alcohol of more than two kinds, lipid acid of more than two kinds and polyvalent alcohol of more than two kinds.
The refrigerator oil of present embodiment can also be the material be only made up of pentaerythritol fatty ester, in addition, also can be the material 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, various additive can also be contained further.In addition, in the following description, for the content of additive, illustrate for benchmark with refrigerator oil total amount, but it is desirable that the content of these compositions in working fluid composition for refrigerating machine with refrigerator oil total amount for selecting in preferred scope described later during benchmark.
In order to resistance to abrasion, the resistance to loading of the refrigerator oil and working fluid composition for refrigerating machine of improveing present embodiment further, the phosphorus compound of at least a kind in the group being selected from and being made up of the ammonium salt of phosphoric acid ester, phosphate ester acid, thiophosphatephosphorothioate, phosphate ester acid, chlorinated phosphate ester and phosphorous acid ester can be coordinated.These phosphorus compounds are phosphoric acid or phosphorous acid and alkanol, the ester of polyether-type alcohol or its derivative.
Specifically, as phosphoric acid ester, can enumerate such as, 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, tricresyl phosphate grease, triphenylphosphate, tritolyl phosphate, three (dimethylbenzene) phosphoric acid ester, cresyl diphenyl phosphate, xylyl diphenyl phosphate etc.
As phosphate ester acid, acid phosphate mono—n—butylester can be listed, acid phosphate list pentyl ester, the own ester of acid phosphate list, acid phosphate list heptyl ester, acid phosphate mono octyl ester, acid phosphate list ester in the ninth of the ten Heavenly Stems, acid phosphate list ester in the last of the ten Heavenly stems, acid phosphate list undecyl ester, acid phosphate list dodecyl ester, acid phosphate list tridecyl ester, acid phosphate list tetradecyl ester, acid phosphate list pentadecyl ester, acid phosphate list cetyl ester, acid phosphate list heptadecyl ester, mono phosphoric acid ester octadecyl acid ester, acid phosphate list oil base ester, dibutyl acid phosphate, acid phosphate diamyl ester, acid phosphate dihexyl, acid phosphate two heptyl ester, acid phosphate dioctyl ester, acid phosphate two ester in the ninth of the ten Heavenly Stems, acid phosphate didecyl, acid phosphate two (undecyl) ester, acid phosphate two (dodecyl) ester, acid phosphate two (tridecyl) ester, acid phosphate two (tetradecyl) ester, ) acid phosphate two (pentadecyl) ester, acid phosphate two (hexadecyl) ester, acid phosphate two (heptadecyl) ester, acid phosphate two (octadecyl) ester, acid phosphate two oil base ester etc.
As thiophosphatephosphorothioate, tributyl thiophosphate can be enumerated, thiophosphoric acid triamyl, the own ester of tri o cresyl thiophosphate, tri o cresyl thiophosphate heptyl ester, 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, 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, the ammonium salt of the amine of the straight or branched alkyl base of primary, secondary, the uncle of phosphate ester acid and carbonatoms 1 ~ 24, preferably 5 ~ 18 can be enumerated.
As the amine of the ammonium salt of formation phosphate ester acid, the methylamine with straight or branched can be enumerated, 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 the amine such as three (24) amine.Amine can be independent compound, also can be the mixture of compound of more than two kinds.
As chlorinated phosphate ester, 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. can be enumerated.As phosphorous acid ester, dibutyl phosphite can be enumerated, phosphorous acid diamyl ester, phosphorous acid dihexyl, phosphorous acid two heptyl ester, dioctyl phosphite, phosphorous acid two ester in the ninth of the ten Heavenly Stems, didecyl phosphite, phosphorous acid two (undecyl) ester, phosphorous acid two (dodecyl) ester, phosphorous acid two grease, diphenyl phosphite, phosphorous acid two (cresols) ester (dicresylphosphite), tributyl phosphate, tricresyl phosphite pentyl ester, the own ester of tricresyl phosphite, tricresyl phosphite heptyl ester, 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, their mixture can also be used.
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 refrigerator oil total amount for benchmark (base oil with always coordinate total metering of additive for benchmark), preferably 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, in order to improve its heat/chemical stability further, can add terpene compound.The present invention's said " terpene compound " refers to compound and their derivative of isoprene polymerization, 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), the monoterpene such as borneol, the joyous alkene of alloy, FARNESOL, nerolidol, neotonin (Juvenilehormone), humulone, sub-cloves alkene, Elemenum, cadinol, cadinene, half terpenes such as tutin (tutin), trans-Geranylgeraniol (geranylgeraniol), phytol, sylvic acid, pimaradiene, daphnetoxin (daphnetoxin), taxol, sylvic acid, pimaric acid etc. two terpenes, the sesterterpenes such as the joyous alkene of geranyl alloy, squalene, obacalactone (Limonin), camellia sapogenol, what handkerchief alkane (Hopane), the triterpenes such as lanosterol (lanosterol), the tetraterpene etc. such as carotenoid (carotenoid).
In these terpene compounds, preferred monoterpene, half terpenes, two terpenes, more preferably half terpenes, the particularly preferably joyous alkene (3 of α-alloy, 7,11-trimethyldodecane-1,3,6,10-tetraene) and/or the joyous alkene (7 of β-alloy, 11-dimethyl-3-methyne dodecane-1,6,10-triolefin).In the present invention, terpene compound can be used alone a kind, also can combine two or more and use.
The content of the terpene compound of the refrigerator oil in present embodiment is not particularly limited, with refrigerator oil total amount for benchmark, and preferably 0.001 ~ 10 quality %, more preferably 0.01 ~ 5 quality %, further preferred 0.05 ~ 3 quality %.When the content of terpene compound is less than 0.001 quality %, it is insufficient that often heat/chemical stability improves effect, and in addition, during more than 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, it is desirable to refrigerator oil total amount as selecting in above-mentioned preferred scope during benchmark.
In addition, the refrigerator oil of present embodiment and working fluid composition for refrigerating machine, can containing the epoxy compoundss of at least a kind be selected from phenyl glycidyl ether type epoxy compounds, alkyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compound, allyloxy silane compound, alkyl oxy silane compound, cycloaliphatic epoxy, epoxidized fat acid monoester and epoxidized vegetable oil in order to improve its heat/chemical stability further.
As phenyl glycidyl ether type epoxy compounds, phenyl glycidyl ether or alkyl phenyl glycidyl ether specifically can be exemplified.Alkyl phenyl glycidyl ether herein can list the compound of the alkyl of the carbonatoms 1 ~ 13 with 1 ~ 3, wherein, the compound with the alkyl of the carbonatoms 4 ~ 10 of 1 can illustrate preference 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 glyceryl ether, decyl phenyl glycidyl ether etc.
Specifically can illustrate as alkyl glycidyl ether type epoxy compounds, decyl glycidyl ether, undecyl glycidyl ether, lauryl diglycidyl ether, tridecyl glycidyl ether, tetradecyl glycidyl ether, 2-hexyl glycidyl ether, neopentylglycol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, tetramethylolmethane four glycidyl ether, 1,6-hexanediol diglycidyl ether, sorbitol polyglycidylether, poly-alkane glycol monoglycidyl ether, poly-alkane Hexanediol diglycidyl ether etc.
Specifically can list as glycidyl ester type epoxy compound, phenyl glycidyl ester, alkyl glycidyl ester, alkenyl-glycidyl esters etc., 2,2-dimethyl-octa acid glycidyl ester, glycidyl benzoate, glycidyl acrylate, glycidyl methacrylate etc. can be illustrated as preferred glycidyl ester type epoxy compound.
Specifically can illustrate as allyloxy silane compound, 1,2-epoxy styrene, alkyl-1,2-epoxy styrene etc.
As alkyl oxosilane compound, specifically can illustrate, 1,2-butylene oxide ring, 1,2-epoxypentane, 1,2-oxepane, 1,2-oxepane, 1,2-octylene oxide, 1,2-epoxy nonane, 1,2-decamethylene, 1,2-epoxyundecyl, 1,2-Epoxydodecane, 1,2-epoxy tridecane, 1, the 2-epoxy tetradecane, 1,2-epoxy pentadecane, 1,2-epoxyhexadecane, 1,2-epoxy heptadecane, 1,1,2-epoxy octadecane, 2-Disparmone, 1,2-epoxy eicosane etc.
As cycloaliphatic epoxy, specifically can illustrate 1, 2-epoxy cyclohexane, 1, 2-cyclopentane epoxide, 3, 4-epoxycyclohexyl-methyl-3, 4-epoxycyclohexane carboxylate, two (3, 4-epoxycyclohexyl-methyl) adipic acid ester, outward-2, 3-epoxy norcamphane, two (3, 4-epoxy-6-methylcyclohexylmethyl) adipic acid ester, 2-(7-oxabicyclo [4.1.0]-3-in heptan base)-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 epoxidized fat acid monoester, specifically can illustrate, the ester etc. of the lipid acid of epoxidised carbonatoms 12 ~ 20 and the alcohol of carbonatoms 1 ~ 8 or phenol, alkylphenol.Particularly preferably use the ester of the butyl of epoxystearic acid, hexyl, benzyl, cyclohexyl, methoxyethyl, octyl group, phenyl and butyl phenyl.
As epoxidized vegetable oil, specifically can illustrate, the epoxy compounds etc. of soybean oil, linseed oil, cottonseed wet goods vegetables oil.
In these epoxy compoundss, preferred material is phenyl glycidyl ether type epoxy compounds, glycidyl ester type epoxy compound, cycloaliphatic epoxy and epoxidized fat acid monoester.Wherein more preferably phenyl glycidyl ether type epoxy compounds and glycidyl ester type epoxy compound, particularly preferably 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 contain above-mentioned epoxy compounds, the content of epoxy compounds is not particularly limited, with refrigerator oil total amount for benchmark, and preferably 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, in order to improve its performance further, can contain known refrigerator oil additive as required.As described additive, the antioxidant of the such as phenol such as two-tert-butyl-p-cresol, dihydroxyphenyl propane system, phenyl-a-naphthylamine, N, N-bis-(2-naphthyl)-to the metal such as defoamer, benzotriazole inerting agent, viscosity index improving agent, pour point depressant, cleaning dispersion agents etc. such as the oiliness improver such as extreme pressure agent, lipid acid, the silicone-based such as wear-resistant dose of antioxidant, zinc dithiophosphate etc., chloroparaffin, sulphur compound of the amine systems such as phenylenediamine can be enumerated.These additives can be used alone a kind, also can combine two or more and use.The content of these additives is not particularly limited, and with refrigerator oil total amount for benchmark, is preferably below 10 quality %, more preferably below 5 quality %.
The kinetic viscosity of the refrigerator oil of present embodiment is not particularly limited, and the kinetic viscosity at 40 DEG C can preferred 3 ~ 1000mm
2/ s, more preferably 4 ~ 500mm
2/ s, most preferably 5 ~ 400mm
2/ s.In addition, the kinetic viscosity at 100 DEG C can preferred 1 ~ 100mm
2/ s, more preferably 2 ~ 50mm
2/ s.When kinetic viscosity is less than aforementioned minimum value, often oilness becomes insufficient, on the other hand, often becomes insufficient with the consistency of methylene fluoride refrigeration agent when exceeding aforementioned higher limit.
In addition, the volume specific resistance of the refrigerator oil of present embodiment is not particularly limited, can preferably 1.0 × 10
12more than Ω cm, more preferably 1.0 × 10
13more than Ω cm, most preferably 1.0 × 10
14more than Ω cm.High electrical insulating property is often needed during refrigerator purposes especially for hermetic type.In addition, in the present invention, volume specific resistance refers to the value at 25 DEG C 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, with refrigerator oil total amount for benchmark, and can preferably below 200ppm, more preferably below 100ppm, most preferably below 50ppm.During refrigerator purposes especially for hermetic type, from the viewpoint of on the heat/chemical stability of refrigerator oil, the impact of electrical insulating property, require that moisture content is few.
In addition, the acid number of the refrigerator oil of present embodiment is not particularly limited, in order to prevent the corrosion of metal for refrigerator or pipe arrangement, and preferred below 0.1mgKOH/g, more preferably below 0.05mgKOH/g.In addition, in the present invention, acid number refers to based on JISK2501 " petroleum product and the lubricating oil one neutralization value test method " acid number of mensuration.
In addition, the ash content of the refrigerator oil of present embodiment is not particularly limited, in order to improve the heat/chemical stability of refrigerator oil and suppress the generation of deposition etc., and can preferably below 100ppm, more preferably below 50ppm.In addition, in the present invention, ash content refers to the ash value measured based on JISK2272 " ash content of crude oil and petroleum product and sulphated ash test method ".
Show fully high oilness and fully high consistency when the refrigerator oil of present embodiment uses together with methylene fluoride refrigeration agent, the refrigerator oil of methylene fluoride refrigeration agent refrigerator can be widely used in.As the refrigerator of the refrigerator oil of use present embodiment, specifically can enumerate the refrigerating units etc. such as room conditioning, box air-conditioning, refrigerator, automative air conditioning, dehumidifier, freezer, freezing and refrigeration warehouse, vending machine, show window, chemical industry equipment, wherein, the refrigerator with hermetic type compressor is particularly preferably used.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 as described later, may be used for the working fluid composition for refrigerating machine with methylene fluoride refrigerant mixed.
That is, the working fluid composition for refrigerating machine of present embodiment contains methylene fluoride refrigeration agent refrigerator oil and the methylene fluoride refrigeration agent of the invention described above.Herein, the proportioning of the 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 relative to methylene fluoride 100 weight part usually, preferably 2 ~ 800 weight parts.
In addition, in the working fluid composition for refrigerating machine of present embodiment, fully high oilness and fully high consistency can not be obtained from the view point of when cannot take into account use refrigerator oil in the past, its availability can be more played as the situation of refrigerant composition only containing methylene fluoride refrigeration agent, but also can containing the HFC refrigeration agent beyond methylene fluoride refrigeration agent, unsaturated fluorinated hydrocarbons (HFO) refrigeration agent, borontrifluoride methyl iodide refrigeration agent, the fluorine-containing ether series coolants such as perfluor ethers, dimethyl ethers etc. are containing non-fluorine ether series coolant, ammonia, carbonic acid gas, the natural series coolant such as hydrocarbon.
As the HFC refrigeration agent beyond methylene fluoride, can enumerate carbonatoms 1 ~ 3, preferably 1 ~ 2 hydrogen fluorohydrocarbon.Specifically can enumerate such as, 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 of more than two kinds.These refrigeration agents according to purposes and can require that performance is suitably selected, and include, for example HFC-32 independent; HFC-23 is independent; HFC-134a is independent; HFC-125 is independent; The mixture of quality %/40 ~ 20, HFC-134a/HFC-32=60 ~ 80 quality %; The mixture of quality %/60 ~ 30, HFC-32/HFC-125=40 ~ 70 quality %; The mixture of quality %/60 ~ 40, HFC-125/HFC-143a=40 ~ 60 quality %; The mixture of HFC-134a/HFC-32/HFC-125=60 quality %/30 quality %/10 quality %; The mixture of quality %/15 ~ 35, HFC-134a/HFC-32/HFC-125=40 ~ 70 quality %/5 ~ 40 quality %; The mixtures of quality %/1 ~ 15, HFC-125/HFC-134a/HFC-143a=35 ~ 55 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) etc. of HFC-125/HFC-134a/HFC-143a=44/4/52 quality %.
As unsaturated fluorinated hydrocarbons (HFO) refrigeration agent, the fluoropropenes of preferred number of fluorine atoms 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, the mixture one kind or two or more arbitrarily of 3-tetra-fluoropropenes (HFO-C1234ye) and 3,3,3-tri-fluoropropenes (HFO-1243zf).From the view point of physical properties, what be preferably selected from HFO-1225ye, HFO-1234ze and HFO-1234yf is one kind or two or more.As the material of preferably methylene fluoride/1234yf=40 ~ 60/60 ~ 40 % by weight of the mix refrigerant with HFO refrigeration agent, the wherein material of preferred methylene fluoride/123,4yf,=50,/50 % by weight.
As hydrocarbon coolant, the hydrocarbon of preferred carbonatoms 3 ~ 5, specifically can enumerate such as, methane, ethene, ethane, propylene, propane, cyclopropane, normal butane, Trimethylmethane, tetramethylene, methyl cyclopropane, 2-methylbutane, Skellysolve A or the mixture of more than two kinds in these.Wherein, be preferably the material of gas under use 25 DEG C, 1 normal atmosphere, preferably propane, normal butane, Trimethylmethane, 2-methylbutane or their mixture.
As fluorine-containing ether series coolant, specifically can enumerate such as, 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 according to purposes and can require that performance is suitably selected.
The refrigerator oil of present embodiment, usually in refrigerating and air conditioning machine, exists with methylene fluoride refrigeration agent or methylene fluoride refrigeration agent and the form of working fluid composition for refrigerating machine that mixes with the mix refrigerant of refrigeration agent as described above.In the refrigerator oil of said composition and the mixing ratio of refrigeration agent and working fluid composition for refrigerating machine of the present invention, the mixing ratio of refrigerator oil and refrigeration agent is not particularly limited, relative to refrigeration agent 100 mass parts, refrigerator oil is 1 ~ 1000 mass parts preferably, 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 the opening or hermetic type with hermetic type compressor.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 are preferably also for having 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 as the representational structure in the refrigerant circulation cycle that this refrigerator possesses, can illustrate and possess compressor, condenser, expansion mechanism and vaporizer, and the equipment of moisture eliminator as required.
As compressor, following compressor can be illustrated: receive in the encloses container storing refrigerator oil: the motor be made up of with stator rotor, be embedded in the turning axle of foregoing rotor and the compressor section be connected with aforementioned motors by this turning axle, and be trapped in the compressor of the high pressure vessel mode in encloses container from the higher pressure refrigerant gas that aforementioned compressor section sprays; The motor be made up of rotor and stator is received in the encloses container storing refrigerator oil, the compressor section be embedded in the turning axle of foregoing rotor, being connected by this turning axle with aforementioned motors, and the compressor etc. being directly discharged to the low pressure vessel mode encloses container from the higher pressure refrigerant gas that aforementioned compressor section sprays.
As the insulating film of the electrical machine insulation system material of motor part, from tensile strength characteristics, be difficult to produce the specific degradation phenomena of electrical isolation, preferred use second-order transition temperature is the crystalline plastic film of more than 50 DEG C, and concrete example is as being selected from the insulating film of at least one in the group of polyethylene terephthalate, polybutylene terephthalate, polyphenylene sulfide, polyether-ether-ketone, Polyethylene Naphthalate, polyamidoimide, polyimide composition or being coated to the composite membrane of the high resin layer of glass transition temp on the film that glass transition temp is low.In addition, as the magnet-wire (MagnetWire) for motor part, preferred use second-order transition temperature is the individual layer of magnet-wire, the such as polyester, polyester-imide, polymeric amide and polyamidoimide etc. that the enamel of more than 120 DEG C is coated to, or the low layer of second-order transition temperature be lower floor, high layer is that the composite coated of upper strata has the coating magnet-wire of enamel.As composite coated enamel line, lower floor can be set forth in and be coated to polyester-imide, be coated to the enamel line (AI/EI) of polyamide-imide on upper strata, be coated to polyester in lower floor, be coated to the enamel line (AI/PE) etc. of polyamide-imide on upper strata.
As the siccative being filled in moisture eliminator, preferably use following synthetic zeolite: by below fine pore 3.3 dust, 25 DEG C of carbon dioxides divide the dioxide absorption capacity be pressed under 250mmHg to be the silicic acid of less than 1.0%, the synthetic zeolite of alkali aluminate metal composite salt formation.Specifically can enumerate such as, the trade(brand)name XH-9 of UNIONSHOWAK.K, XH-10, XH-11, XH-600 etc.
[embodiment]
Carry out more specific description based on embodiment and comparative example to the present invention below, the present invention is not by any restriction of following examples.
[embodiment 1 ~ 10 and comparative example 1 ~ 11]
In embodiment 1 ~ 10 and comparative example 1 ~ 11, respectively the following base oil 1 ~ 13 that illustrates and additive 1 ~ 4 are coordinated modulation test portion oil according to the ratio of components shown in table 1 or 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 (mixture of 2 methyl valeric acid 70 % by mole, 3,5,5 Trimethylhexanoic acid 30 % by mole)
Base oil 2: four esters of tetramethylolmethane and fatty acid mixt (mixture of 2 methyl valeric acid 30 % by mole, 3,5,5 Trimethylhexanoic acid 70 % by mole)
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 (2 methyl caproic acid 70 % by mole, 2-ethylpentanoic 30 % by mole)
Base oil 11: four esters of tetramethylolmethane and fatty acid mixt (2 ethyl hexanoic acid 50 % by mole, 3,5,5 Trimethylhexanoic acid 50 % by mole)
Base oil 12: four esters of tetramethylolmethane and fatty acid mixt (mixture of 2 methyl valeric acid 90 % by mole, 3,5,5 Trimethylhexanoic acid 10 % by mole)
Base oil 13: four esters of tetramethylolmethane and fatty acid mixt (mixture of 2 methyl valeric acid 10 % by mole, 3,5,5 Trimethylhexanoic acid 90 % by mole)
(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 the following test illustrated is carried out to above-mentioned each test portion oil.
(with the compatibility test of refrigeration agent)
Based on " with the compatibility test method of refrigeration agent " of JIS-K-2211 " refrigerator oil ", the mixture of methylene fluoride refrigeration agent (HFC-32) 18g and test portion oil 2g is cooled to-40 DEG C from 30 DEG C lentamente, mixture is separated or the temperature of gonorrhoea is evaluated as two layers of separation temperature.In addition, " <-40 " represents unconfirmed to being separated and gonorrhoea in the mensuration temperature province of this test.In addition, " separation " expression in table 4 has been separated or gonorrhoea at 30 DEG C.
(lubricity test)
The frictional testing machines that upside test film uses push rod (bane) (SKH-51), downside test film use disk (disc) (FC250HRC40) is installed in the inside of encloses container.Import test portion oil 600g at rub(bing)test position, after vacuum outgas in system, import HFC-32 and heat.Temperature in encloses container is 100 DEG C, refrigerant pressure is after 1.5Mpa, with the increase loading of loading step 10kgf (the step time is 2 minutes) stage to 100kgf, carries out the abrasion test of 60 minutes under 100kgf.To the abrasion width of blade after each test portion oil measurement test of 60 minutes and the abrasion degree of depth of disk.
(test of the low temperature property separated out)
Test portion oil is put into developmental tube, floods 24 hours in the ethanol bath (-70 DEG C) putting into dry ice, observe with or without gonorrhoea.
[table 1]
[table 2]
[table 3]
[table 4]
Claims (2)
1. a refrigerator oil, the ester that it contains in refrigerator oil total amount is more than benchmark 10 quality %, and use together with methylene fluoride refrigeration agent, this ester is the ester of tetramethylolmethane and lipid acid, wherein, in described lipid acid, the carbonatoms with side chain is the lipid acid and 3 of 6,5, the mol ratio of 5-tri-methyl hexanoic acid is 20: 80 ~ 80: 20, and carbonatoms is the lipid acid of 6 and the summation of 3,5,5 Trimethylhexanoic acid, and ratio shared in described lipid acid is more than 20 % by mole.
2. a working fluid composition for refrigerating machine, it contains refrigerator oil according to claim 1 and methylene fluoride refrigeration agent.
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| JP2010061201A JP5525877B2 (en) | 2010-03-17 | 2010-03-17 | Refrigerator oil and working fluid composition for refrigerator |
| JP2010-061201 | 2010-03-17 |
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| CN (1) | CN102191114B (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011195630A (en) * | 2010-03-17 | 2011-10-06 | Jx Nippon Oil & Energy Corp | Refrigerator oil and hydraulic fluid composition for refrigerator |
| JP2014240702A (en) * | 2011-10-06 | 2014-12-25 | パナソニック株式会社 | Refrigeration device |
| BR112014009738A2 (en) | 2011-10-26 | 2017-04-18 | Jx Nippon Oil & Energy Corp | working fluid composition for cooling machine and cooling oil |
| JP5989989B2 (en) * | 2011-12-27 | 2016-09-07 | 日本サン石油株式会社 | Refrigerator oil composition |
| EP2799527B1 (en) * | 2011-12-27 | 2022-02-02 | Japan Sun Oil Company, Ltd. | Refrigerator oil composition |
| KR101909545B1 (en) | 2012-03-27 | 2018-10-19 | 제이엑스티지 에네루기 가부시키가이샤 | Working fluid composition for refrigerator |
| CN104768915B (en) | 2012-10-24 | 2016-05-04 | Kh新化株式会社 | Six esters of bipentaerythrite monoformal |
| JP5538636B1 (en) * | 2012-10-24 | 2014-07-02 | Ｋｈネオケム株式会社 | Hexaester of bispentaerythritol monoformal |
| KR102041362B1 (en) * | 2012-10-31 | 2019-11-06 | 다이킨 고교 가부시키가이샤 | Refrigeration device |
| 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 |
| JP6343806B2 (en) * | 2014-05-12 | 2018-06-20 | パナソニックＩｐマネジメント株式会社 | Compressor and refrigeration cycle apparatus using the same |
| 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 |
| JP2016098256A (en) * | 2014-11-18 | 2016-05-30 | Ｊｘエネルギー株式会社 | Refrigeration oil and actuation 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 |
| JP2017075278A (en) * | 2015-10-16 | 2017-04-20 | 出光興産株式会社 | Refrigerator oil, composition for refrigerator, and refrigerator |
| CN108795391B (en) * | 2018-06-04 | 2020-07-28 | 北京中冷高科制冷设备有限公司 | Secondary refrigerant for refrigeration house refrigerating system |
| 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 |
| JPWO2021221058A1 (en) * | 2020-04-30 | 2021-11-04 | ||
| CN112126495B (en) * | 2020-09-01 | 2022-08-19 | 珠海格力节能环保制冷技术研究中心有限公司 | Refrigerating machine oil composition |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2613526B2 (en) * | 1992-07-04 | 1997-05-28 | 花王株式会社 | Composition for working fluid of refrigerator |
| EP0653479B1 (en) * | 1993-05-27 | 2004-06-30 | Tonen Corporation | Refrigerator oil |
| JP5265068B2 (en) * | 2000-10-30 | 2013-08-14 | Ｊｘ日鉱日石エネルギー株式会社 | Fluid composition for refrigerator |
| JP4936656B2 (en) * | 2003-11-21 | 2012-05-23 | 日油株式会社 | Lubricating oil composition for refrigerator |
| CA2487587C (en) * | 2003-11-21 | 2012-04-24 | Nof Corporation | A polyol ester for use within a refrigeration lubricant composition compatible with chlorine-free hydrofluorocarbon refrigerants |
-
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 (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
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| JP2011195631A (en) | 2011-10-06 |
| JP5525877B2 (en) | 2014-06-18 |
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