JP6161766B2 - Working fluid composition for refrigerator - Google Patents

Description

  The present invention relates to a working fluid composition for a refrigerator, and more particularly to a working fluid composition for a refrigerator containing a refrigerant containing monofluoroethane (also referred to as “HFC-161” or “R161”).

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

  Among HFC refrigerants, HFC-134a, R407C, and R410A are standardly used as refrigerants for car air conditioners, refrigerators, and room air conditioners. However, these HFC refrigerants are becoming subject to regulation because of their high global warming potential (GWP) although their ozone depletion potential (ODP) is zero. Difluoromethane has been studied as one of the alternative candidates for these refrigerants, but the global warming potential is not sufficiently low, the boiling point is too low, and the thermodynamic characteristics cannot be applied to the current refrigeration system as it is, In addition, there is a problem that it is difficult to be compatible with lubricating oil (refrigeration machine oil) such as polyol ester and polyvinyl ether used in conventional HFC refrigerants. On the other hand, unsaturated fluorinated hydrocarbons are very small in both ODP and GWP, and are nonflammable depending on the structure. Among them, HFO-1234yf has a thermodynamic characteristic that is a measure of refrigerant performance as HFC-134a. Since it is substantially the same or more, use as a refrigerant | coolant is proposed (patent documents 1-3).

  In addition, as the first component, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoro-2-monofluoroethane (HFC-134a), 1,1,1-trifluoro-2,2- There has been proposed a working medium composed of 80% by mass or more of one or more first components selected from difluoroethane (HFC-125) and 20% by mass or less of carbon dioxide (R744) as the second component (Patent Document 4).

  In addition, hydrocarbons such as isobutane (R600a) and propane (R290) that are flammable but have an ODP of 0 and an extremely low GWP of about 3 have been studied (Patent Documents 5 to 7).

International Publication WO2004 / 037913 Pamphlet International Publication WO2005 / 105947 Pamphlet International Publication WO2009 / 057475 Pamphlet JP-A-10-265771 JP 2000-044937 A JP 2000-274360 A JP 2010-031728 A

  The problem with the refrigeration and air conditioning system is that the refrigerant has a low global warming potential (GWP), has little adverse effect on the environment, is difficult to burn and explode, can be used safely, and has thermodynamic characteristics suitable for the application. The chemical structure is simple and a large amount can be supplied at low cost. The characteristics of the system in which refrigerant and refrigerating machine oil coexist are mutually soluble (compatible), excellent in stability, and maintain an oil film that does not wear. Is to find a working fluid that satisfies all of the many properties of being lubricated.

  As described above, HFC-32 (GWP: 675), HFO-1234yf (GWP: 4), HFC-152a (GWP: 120), as the low-GWP next-generation refrigerant, which replaces the existing HFC refrigerant with a large GWP, Propane (R290, GWP: 3) and the like have been studied as promising candidates, but each has a problem.

  In the refrigerant circulation cycle of the refrigeration / air conditioning equipment, since the refrigeration oil that lubricates the refrigerant compressor circulates in the cycle together with the refrigerant, the refrigeration oil is required to have compatibility with the refrigerant. However, the refrigeration / air conditioning system using HFC-32 has a problem that it is difficult to be compatible with refrigeration oil. In refrigeration and air conditioning equipment, depending on the selection of the refrigeration oil used for the refrigerant, sufficient compatibility between the refrigerant and the refrigeration oil is not obtained, and the refrigeration oil discharged from the refrigerant compressor is placed at a low temperature in the cycle. It becomes easy to stay. As a result, the amount of oil in the refrigerant compressor decreases, causing problems due to wear due to poor lubrication and closing of an expansion mechanism such as a capillary that is a narrow tube having an inner diameter of 1 mm or less. Moreover, HFC-32 has a boiling point of −52 ° C., which is about 10 ° C. lower than the current refrigerant HCFC-22 used in room air conditioners, packaged air conditioners, etc., and the discharge temperature is higher at the same temperature. There is also a problem of thermodynamic characteristics that it is too high, and GWP is not sufficiently small as 675.

  In refrigeration and air conditioning systems using HFO-1234yf, which is an unsaturated fluorohydrocarbon and extremely small GWP, it is compatible with refrigeration machine oils such as polyol esters and ether compounds currently used in HFC, and can be applied. Has been considered. However, according to the study by the present inventors, since the unsaturated fluorinated hydrocarbon has an unstable double bond in the molecule, the problem in terms of stability is inferior in thermal and chemical stability. Became. HFO-1234yf has a boiling point of −25 ° C. and can be applied to the car air conditioner and refrigerator fields where HFC-134a having a boiling point of −26 ° C. is used. The high efficiency of HCFC-22 or the like in which the amount of refrigerant is used is not applicable to room air conditioners, packaged air conditioners, industrial refrigerators, etc., because the efficiency is too low.

  HFC-152a is a refrigerant with a small GWP and a good balance of properties, except that it is flammable. However, it has a boiling point of −25 ° C. and is applicable only to the field of HFC-134a because of its thermodynamic characteristics. Among the main fields where HFC-134a is used, in the refrigerator field where the refrigerant charge amount is small, switching to isobutane (R600a) having a small GWP of 3 is already in progress. However, isobutane also has a problem that it cannot be applied to uses with a large amount of refrigerant charge in terms of thermodynamic characteristics and safety.

  Propane has a boiling point of -42 ° C, GWP is very small, HCFC-22 and its alternative ODP is 0, and R410A, a mixed refrigerant with 50% by mass of HFC-32 and HFC-125, is used. Excellent refrigerant characteristics. However, it is highly flammable and highly explosive, and there are safety issues.

  In the case of a refrigerant composed of 80% by mass or more such as 1,1-difluoroethane as the first component and 20% by mass or less of carbon dioxide as the second component as described in Patent Document 4, the ODP is 0. Although there is GWP, it is not small enough.

  The present invention has been made in view of such circumstances, and can achieve compatibility, thermal / chemical stability, and lubricity at a high level in a highly efficient system with little adverse effect on the environment. An object is to provide a working fluid composition for a refrigerator.

  As a result of intensive investigations to achieve the above object, the present inventors have found that a refrigerant containing monofluoroethane (HFC-161) and a refrigerating machine oil based on a specific mineral oil and / or synthetic hydrocarbon oil. It was found that the refrigerant compatibility and the thermal / chemical stability can be achieved at a high level by using in combination, and the present invention has been completed.

That is, the present invention
A refrigerant containing monofluoroethane;
n-d-M% in ring analysis C _N 10-60 and mineral oil pour point of -15 ° C. or less and pour point are contained as base oil at least one kind of selected from -15 ° C. or less of the synthetic hydrocarbon oil A refrigerating machine oil having a kinematic viscosity at 40 ° C. of 3 to 500 mm ² / s,
The working fluid composition for refrigerators containing the is provided.

  The mass ratio of the refrigerant to the refrigerating machine oil is preferably 90:10 to 30:70.

  The content ratio of monofluoroethane in the refrigerant is preferably 50% by mass or more, and the global warming potential of the refrigerant is preferably 300 or less.

  The refrigerant preferably further contains carbon dioxide.

  When the base oil contains a synthetic hydrocarbon oil, the synthetic hydrocarbon oil is preferably at least one selected from alkylbenzene, alkylnaphthalene and poly-α-olefin.

  According to the present invention, in a refrigeration / air conditioning system using a refrigerant containing monofluoroethane, compatibility, thermal / chemical stability, and lubricity are achieved at a high level without requiring significant changes to existing systems. It is possible to provide a working fluid composition for a refrigeration / air conditioner that can be used.

  In addition, according to the working fluid composition for a refrigerator of the present invention, it is possible to achieve low GWP and non-combustibility of the refrigerant, and to operate the refrigeration / air conditioning system safely and with high efficiency.

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

A working fluid composition for a refrigerator according to an embodiment of the present invention,
A refrigerant containing monofluoroethane;
n-d-M% in ring analysis C _N 10-60 and mineral oil pour point of -15 ° C. or less and pour point are contained as base oil at least one kind of selected from -15 ° C. or less of the synthetic hydrocarbon oil A refrigerating machine oil having a kinematic viscosity at 40 ° C. of 3 to 500 mm ² / s,
Containing.

  In the working fluid composition for a refrigerator according to this embodiment, the mixing ratio of the refrigerant and the refrigerator oil is not particularly limited, but the mass ratio of the refrigerant and the refrigerator oil is preferably 90:10 to 30:70, and more Preferably it is 80: 20-40: 60.

  Next, the components contained in the working fluid composition for refrigerators will be described in detail.

[Refrigerant]
The refrigerant in this embodiment contains monofluoroethane (HFC-161). Monofluoroethane has one fluorine in its molecule and exhibits characteristic properties.

  That is, first, in the field where HCFC-22 has been used as a refrigerant, propane (R290) is most suitable as a low GWP refrigerant because of its thermodynamic characteristics. However, since propane is highly flammable, there is a big problem in safety, and when coexisting with refrigerating machine oil, there is a problem that it is excessively dissolved in refrigerating machine oil and drastically lowers the viscosity of the oil and lowers lubricity.

  On the other hand, monofluoroethane has a GWP as small as 100 or less, a boiling point of −37 ° C., close to the boiling point of −41 ° C. of HCFC-22, has similar thermodynamic characteristics, and can be used alone as a refrigerant. Good mechanical properties, compatibility with refrigerating machine oil, and stability. In addition, although it is flammable, HFC-161 has a lower explosion limit of 5.0% by volume, compared with 2.1% by volume, which is the lower limit of explosion of propane. Refrigerant leakage is difficult to occur and it is much safer. The refrigerant concentration in the room hardly reaches 5.0% by volume. In addition, since fluorine is contained in the molecule, the amount dissolved in refrigerating machine oil is much less than that of propane, and the amount of refrigerant charge per refrigeration / air-conditioning device can be reduced. It is considered possible. Since the amount of the dissolved refrigeration oil in the coexisting refrigeration oil is small, the decrease in the viscosity of the refrigeration oil is small and the lubricity is advantageous, and there is no problem in stability because there is no double bond in the molecule.

  In addition, by further containing other refrigerant components in the refrigerant containing HFC-161, the characteristics of the refrigerant (mixed refrigerant) can be made more suitable according to the purpose and application. Examples of the refrigerant to be blended include hydrofluorocarbon (HFC), hydrofluoroolefin (HFO), carbon dioxide (R744), ammonia (R717), and fluorinated ether compounds.

  Here, among the above refrigerant components, HFC and HFO have lower compatibility with mineral oil and synthetic hydrocarbon oil as the number of fluorine atoms in the molecule increases, that is, as the proportion of fluorine atoms in one molecule increases. To do. Therefore, depending on the blending ratio with HFC-161, when the refrigerant and the refrigerating machine oil partially separate into two layers, it is necessary to deal with the system.

  For preferred components combined with monofluoroethane, the boiling point, GWP, and flammability are listed in parentheses, and HFC-32 (-52 ° C., 675, slightly flammable), HFC-152a (−25 ° C., 120, Flammable), HFC-143a (-47 ° C, 4300, slightly flammable), HFC-134a (-26 ° C, 1300, nonflammable), HFC-125 (-49 ° C, 3400, nonflammable), HFO-1234ze (-19 ° C, 6, slightly flammable), HFO-1234yf (-29 ° C, 4, flammable), propane (-42 ° C, 3, flammable), isobutane (-12 ° C, 3, flammable) ), Carbon dioxide (-78 ° C., 1, nonflammability). Two or more of these components may be combined.

For example, in order to improve the safety of the refrigerant (mixed refrigerant) in the present embodiment, a nonflammable refrigerant may be blended, but the nonflammable HFC refrigerant generally has a high GWP. Therefore, there is a method of balancing the characteristics by blending a slightly flammable refrigerant. In particular, since carbon dioxide is nonflammable and is as small as 1 as a GWP reference compound, blending in a range that does not affect thermodynamic properties is effective.
In order to increase efficiency, a high-pressure refrigerant, that is, a refrigerant having a low boiling point, is blended. However, since propane is highly flammable, HFC-32, HFC-143a, and HFC-125 are candidates. .

  In order to reduce GWP, HFO-1234ze, HFO-1234yf, carbon dioxide, propane, and isobutane are preferable.

  In addition, when reducing the pressure of the mixed refrigerant for application to fields other than where HCFC-22 has been used, HFC-134a, HFO-1234ze having a boiling point higher than −30 ° C. A refrigerant having a relatively low pressure such as HFO-1234yf is selected.

  When the refrigerant in the present embodiment is a mixed refrigerant of monofluoroethane and the above components, the content ratio of monofluoroethane in the mixed refrigerant is preferably 50% by mass or more, and more preferably 70% by mass or more. preferable. Moreover, about GWP, it is preferable to set it as 300 or less from a viewpoint of global environment protection, 200 or less, and 150 or less are more preferable. When the refrigerant used in the present embodiment is a mixed refrigerant, the mixed refrigerant is preferably an azeotrope, but need not be an azeotrope as long as it has physical properties necessary as a refrigerant.

[Refrigerator oil]
Refrigerating machine oil in this embodiment, at least% C _N 10 to 60 and mineral oil pour point of -15 ° C. or less and pour point of n-d-M ring analysis is selected from -15 ° C. or less of the synthetic hydrocarbon oil One type is a base oil.

  For mineral oil, lubricating oil fractions obtained by atmospheric distillation and vacuum distillation of paraffinic and naphthenic crude oil are removed from the solvent, solvent refining, hydrorefining, hydrocracking, solvent dewaxing, hydrogenation One type or two or more types of purification of dewaxing, clay treatment, and sulfuric acid washing can be appropriately combined.

The ndM ring analysis is defined by ASTM D-3238, and the refractive index, density and sulfur content of oil at 20 ° C., viscosity (40 ° C. and 100 ° C.) are measured, and the aromatic carbon number ( % C _A ), naphthene carbon number (% C _N ), paraffin carbon number (% C _P ), and the total of the three types of carbon is 100%, which is an index of the composition type of oil. . If the% C _N value of the mineral oil is less than 10,% C _P is the compatibility of many becomes refrigerant and oil drops. On the other hand,% C _N of mineral oil is less the% C _P exceeds 60, such as viscosity index decreases, lowering the viscosity characteristics, i.e. lubricity decreases. % _{C N} is preferably 20 to 50.

  Examples of the synthetic hydrocarbon oil include alkylbenzene, alkylnaphthalene, poly-α-olefin (PAO), polybutene, and ethylene-α-olefin copolymer. For example, polybutene becomes a solid when the molecular weight increases. The pour point must be −15 ° C. or lower. Of these, alkylbenzene, alkylnaphthalene, and PAO are preferable from the viewpoint of compatibility and viscosity index when coexisting with HFC-161 refrigerant.

Alkylbenzene is an aromatic hydrocarbon having an alkyl group bonded to the benzene ring. Depending on the chemical structure of the alkyl group, there are a straight-chain type and a branched type, and it is called mono-, di-, tri-, or tetraalkylbenzene depending on the number of substituted alkyl groups. The alkylbenzene is preferably one having 1 to 4 alkyl groups having 1 to 30 carbon atoms and 3 to 30 carbon atoms in total. As the alkyl group, depending on the carbon number, methyl group, ethyl group, linear or branched propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, There are dodecyl group, tridecyl group, tetradecyl group, heptadecyl group, octadecyl group and the like. Of these, branched alkyl groups derived from oligomers of olefins such as propylene, butene and isobutylene are preferable, and those having a kinematic viscosity at 40 ° C. of 3 to 50 mm ² / s are more preferable.

Alkylnaphthalene is an aromatic hydrocarbon having an alkyl group bonded to the naphthalene ring, and the alkyl group is the same as alkylbenzene. It is preferable that the naphthalene ring has 1 to 4 alkyl groups having 1 to 10 carbon atoms and the total number of carbon atoms in the alkyl group is 1 to 20, and the naphthalene ring is stable. Excellent. Moreover, the thing whose kinematic viscosity in 40 degreeC is 10-100 mm < ² > / s is preferable.

  Poly-α-olefin (PAO) is a colorless and transparent polymer obtained by polymerizing a limited number of olefins having a straight chain of 6 to 18 carbon atoms and having a double bond at one of both ends, and then hydrogenating the polymer. It is a liquid. For example, it is isoparaffin distributed around the trimer or tetramer of α-decene having 10 carbon atoms and α-dodecene having 12 carbon atoms, and has higher purity and narrow molecular weight distribution than mineral oil. Its molecular structure has comb-like branches, a high viscosity index, a low pour point, and a high flash point for its viscosity.

The kinematic viscosity of the refrigerating machine oil in the present embodiment is not particularly limited, but the kinematic viscosity at 40 ° C. can be preferably 3 to 500 mm ² / s, more preferably 5 to 400 mm ² / s. The kinematic viscosity at 100 ° C. is preferably 1 to 50 mm ² / s, more preferably ² to 30 mm ² / s.

The volume resistivity of the refrigerating machine oil in the present embodiment is not particularly limited, but is preferably 1.0 × 10 ¹⁰ Ω · m or more, more preferably 1.0 × 10 ¹¹ Ω · m or more. In particular, when it is used for a hermetic refrigerator, high electrical insulation tends to be required. In the present invention, the volume resistivity means a value at 25 ° C. measured in accordance with JIS C 2101 “Electrical insulating oil test method”.

  The water content of the refrigerating machine oil in the present embodiment is not particularly limited, but can be preferably 100 ppm or less, more preferably 50 ppm or less, and most preferably 30 ppm or less based on the total quantity of refrigerating machine oil. In particular, when it is used for a hermetic type refrigerator, the moisture content is required to be small from the viewpoint of the influence on the thermal / chemical stability and electrical insulation of the refrigerator oil.

  The acid value of the refrigerating machine oil in the present embodiment is not particularly limited, but is preferably 0.1 mgKOH / g in order to prevent corrosion of the metal used in the refrigerating machine or piping and to prevent deterioration of the refrigerating machine oil. Hereinafter, more preferably 0.05 mgKOH / g or less. In addition, in this invention, an acid value means the acid value measured based on JISK2501 "Petroleum products and lubricating oil-neutralization value test method".

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

  The working fluid composition for a refrigerator according to this embodiment can be used in a form in which various additives are further blended as necessary. In addition, content of the following additives is 5 mass% or less on the basis of the refrigerating machine oil composition whole quantity, and 2 mass% or less is especially preferable.

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

  In addition, the working fluid composition for a refrigerator according to the present embodiment has a phenyl glycidyl ether type epoxy compound, an alkyl glycidyl ether type epoxy compound, a glycidyl ester type epoxy compound, in order to further improve its thermal and chemical stability. It can contain at least one epoxy compound selected from allyl oxirane compounds, alkyl oxirane compounds, alicyclic epoxy compounds, epoxidized fatty acid monoesters and epoxidized vegetable oils.

  In addition, the working fluid composition for a refrigerator according to the present embodiment can contain a conventionally known additive for refrigerator oil as necessary in order to further enhance the performance. Examples of such additives include di-tert. Phenolic antioxidants such as butyl-p-cresol and bisphenol A, amine antioxidants such as phenyl-α-naphthylamine and N, N-di (2-naphthyl) -p-phenylenediamine, dithiophosphoric acid Antiwear agents such as zinc, extreme pressure agents such as chlorinated paraffin and sulfur compounds, oily agents such as fatty acids, antifoaming agents such as silicones, metal deactivators such as benzotriazole, viscosity index improvers, pour points Depressants, cleaning dispersants and the like. These additives may be used individually by 1 type, and may be used in combination of 2 or more type.

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

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

[Refrigerator oil]
First, the base oils 1-4 shown below are added to di-tert. Refrigerating machine oils 1 to 4 were prepared by adding 0.1% by mass of -butyl-p-cresol (DBPC). Table 1 shows various properties of the refrigerating machine oils 1 to 4.
[Base oil]
Base oil 1: Base oil (manufactured by JX Nippon Oil & Energy Co., Ltd.) purified by furfural extraction and hydrorefining of vacuum distillate from naphthenic crude oil
Base oil 2: Base oil refined by hydrocracking and hydrodewaxing distillate from paraffin crude oil (Korea, manufactured by SK Lubricans)
Base oil 3: Branched alkylbenzene (manufactured by JX Nippon Oil & Energy Corporation)
Base oil 4: poly-α-olefin (manufactured by ExxonMobil)

[Examples 1-8, Comparative Examples 1-10]
In Examples 1-8 and Comparative Examples 1-10, the evaluation shown below about the working fluid composition for refrigerators which combined either the said refrigerator oil 1-4, and the refrigerant | coolant shown in Tables 2-4, respectively. The test was conducted. In addition, as will be described later, the mass ratio between the refrigerant and the refrigerating machine oil in the working fluid composition for the refrigerating machine was changed for each test.

As the refrigerant, HFC-161 alone and mixed refrigerant A in which carbon dioxide (R744) was blended with HFC-161 and the flammability was suppressed were used in the examples. In addition, since the fixed value of HFC-161 was not announced about GWP, it calculated using 100 which is the maximum value.
As comparative examples, HFC-134a, which is currently widely used, and propane (R290), HFC-32, and HFO-1234yf, which are promising candidates, were used as new refrigerants based on GWP values, combustibility, and thermodynamic characteristics.
[Refrigerant]
HFC-161: Monofluoroethane (GWP: about 100)
R744: Carbon dioxide (GWP: 1)
R290: Propane (GWP: 3)
HFC-134a: 1,1,1,2-tetrafluoroethane (GWP: 1300)
HFC-32: Difluoromethane (GWP: 675)
HFO-1234yf: 2,3,3,3-tetrafluoropropene (GWP: 4)
Mixed refrigerant A: HFC-161 / R744 = 80/20 (mass ratio, GWP: about 80)

Next, the following evaluation tests were performed on the working fluid compositions for refrigerators of Examples 1 to 8 and Comparative Examples 1 to 10. The results are shown in Tables 2-4.

[Compatibility evaluation]
In accordance with JIS-K-2211 “Refrigerating machine oil” “Compatibility test method with refrigerant”, 2 g of refrigerating machine oil is blended with 18 g of each of the above refrigerants including mixed refrigerant, and the refrigerant and refrigerating machine oil are at 0 ° C. It was observed whether they were dissolved in each other. The obtained results are shown in Tables 2-4. In the table, “compatible” means that the refrigerant and the refrigerating machine oil are dissolved in each other, and “separation” means that the refrigerant and the refrigerating machine oil are separated into two layers.

[Evaluation of thermal and chemical stability]
In accordance with JIS-K-2211, 1 g of refrigerating machine oil (initial hue L0.5) whose water content is adjusted to 100 ppm or less, 1 g of the above-mentioned various refrigerants, and catalysts (iron, copper, and aluminum wires) in a glass tube After sealing, it was placed in an iron protective tube, heated to 175 ° C. and held for 1 week for testing. After the test, the hue of the refrigerating machine oil and the color change of the catalyst were evaluated. The hue was evaluated according to ASTM D156. Further, the color change of the catalyst was visually observed for the appearance, and it was evaluated whether it corresponded to no change, no gloss, or blackening. In the case of no gloss and blackening, it can be said that the mixed liquid of the refrigerating machine oil and the refrigerant, that is, the working fluid is deteriorated. The obtained results are shown in Tables 2-4.

  In Examples 1 to 8 of the present invention shown in Table 2, the GWP of the refrigerant is as small as 150 or less, there is no problem in compatibility between the refrigerant and the refrigerating machine oil, and the thermal / chemical stability and lubricity are also good. It can be said that it is an excellent working fluid for refrigeration and air conditioners.

  On the other hand, in Comparative Examples 1 to 4, although any refrigeration oil is compatible with the refrigerant, it is difficult to use as a working fluid because the refrigerant is excessively dissolved and the viscosity is lowered to deteriorate the lubricity. Comparative Examples 5 to 8 cannot be used because GWP is large and refrigerant and refrigerating machine oil are not compatible. Although Comparative Examples 9 and 10 have a small GWP, the thermal and chemical stability when the refrigerator oil and the refrigerant coexist are poor, the copper and iron catalysts are discolored, and the oil is colored, that is, deteriorated. Since it is not soluble, it is not a suitable working fluid.

  The present invention is a working fluid composition used in a refrigeration / air conditioner in which a refrigerant containing HFC-161 is used, and includes a compressor, a condenser, a throttle device, an evaporator, and the like, and the refrigerant is between them. Refrigeration system with high cooling efficiency that circulates, and can be used as working fluid for refrigeration / air conditioners that have compressors such as rotary type, swing type, scroll type, reciprocating type compressor, etc., room air conditioner, package It can be suitably used in the fields of air conditioners, industrial refrigerators, refrigerators, car air conditioners and the like.

Claims (6)

n-d-M% in ring analysis C _N 10-60 and mineral oil pour point of -15 ° C. or less and pour point are contained as base oil at least one kind of selected from -15 ° C. or less of the synthetic hydrocarbon oil A refrigerating machine oil used together with a refrigerant containing monofluoroethane, wherein the content of the monofluoroethane in the refrigerant is 50% by mass or more . Global warming coefficient before Symbol refrigerant is 300 or less, the refrigerating machine oil according to claim 1.   The refrigerating machine oil according to claim 1 or 2, wherein the refrigerant further contains carbon dioxide.   The said base oil contains the said synthetic hydrocarbon oil, This synthetic hydrocarbon oil is at least 1 sort (s) chosen from alkylbenzene, an alkylnaphthalene, and a poly-alpha-olefin. Refrigeration oil. Refrigerating machine oil according to any one of claims 1 to 4,
A refrigerant-containing working fluid composition comprising: a refrigerant containing monofluoroethane, wherein the refrigerant contains a monofluoroethane in a proportion of 50% by mass or more .   The working fluid composition for a refrigerator according to claim 5, wherein a mass ratio of the refrigerant and the refrigerator oil is 90:10 to 30:70.