Refrigerant-containing composition, freezing method using same, method for operating freezing device, and freezing device

Abstract

The present invention provides a refrigerant-containing composition which has a low GWP and which has the characteristics of cooling capacity and COP equivalent to those of R410A. Specifically, the present invention provides a composition which contains difluoromethane (R32) and pentafluoroethane (R125), the total concentration of R32 and R125 being 99.5 mass% or more, and the content ratio of R32 being 53.1-56.0 mass% and the content ratio of R125 being 44.0-46.9 mass% with respect to the total mass of R32 and R125.

Description

[0001] (This application is a divisional application of application 201980054059.X, filed on June 5, 2019, entitled "Composition containing refrigerant, freezing method using the composition, operation method of freezing apparatus and freezing apparatus") Technical Field

[0002] This invention relates to compositions containing refrigerants, freezing methods using the compositions, operating methods of freezing apparatuses, and freezing apparatuses. Background Technology

[0003] In recent years, mixtures of fluorinated hydrocarbons such as difluoromethane (CH2F2, R32, boiling point -52℃), pentafluoroethane (CF3CHF2, R125, boiling point -48℃), 1,1,1,2-tetrafluoroethane (CF3CH2F, R134a, boiling point -26℃), 2,3,3,3-tetrafluoropropylene (CF3CF=CH2, R1234yf, boiling point -29℃), and E- or Z-1,3,3,3-tetrafluoropropylene (CF3CH=CHF, R1234ze, boiling point -19℃) have been used as refrigerants in air conditioners, refrigeration units, refrigerators, etc.

[0004] Patent Document 1 describes a two-component mixed refrigerant composed of R32 / R125 from the aforementioned fluorinated hydrocarbons, with a composition of 50 / 50% by mass (R410A).

[0005] Existing technical documents Patent documents Patent Document 1: International Publication No. 1991 / 005027 Summary of the Invention

[0006] The technical problem that the invention aims to solve The object of the present invention is to provide a composition containing a refrigerant that uses a refrigerant having the same refrigeration capacity and coefficient of performance (COP) as R410A, and a low GWP (below 2000).

[0007] The present invention also aims to provide a freezing method using the composition, a method for operating a freezing apparatus, and a freezing apparatus.

[0008] Technical means for solving technical problems This invention provides the following method of invention.

[0009] Item 1. A composition containing a refrigerant, wherein the refrigerant contains difluoromethane (R32) and pentafluoroethane (R125), the total concentration of R32 and R125 is 99.5% by mass or more, and the content of R32 is 53.1 to 56.0% by mass and the content of R125 is 44.0 to 46.9% by mass relative to the total mass of R32 and R125.

[0010] Item 2. A composition containing a refrigerant, wherein the refrigerant contains difluoromethane (R32) and pentafluoroethane (R125), the total concentration of R32 and R125 is 99.5% by mass or more, and the content of R32 is 60.5 to 62.5% by mass and the content of R125 is 37.5 to 39.5% by mass relative to the total mass of R32 and R125.

[0011] Item 3. The composition as described in Item 1 or 2, wherein the refrigerant consists only of R32 and R125.

[0012] Item 4. A composition containing a refrigerant, wherein the refrigerant comprises difluoromethane (R32), pentafluoroethane (R125), and 2,3,3,3-tetrafluoropropylene (R1234yf), the total concentration of the three components being 99.5% by mass or more, and the mass ratio of the three components being within the area enclosed by the quadrilateral with vertices A, B, C, and D in a triangular composition diagram with the three components as vertices. Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point C (R32 / R125 / R1234yf=26.2 / 57.5 / 16.3 mass%) Point D (R32 / R125 / R1234yf=45.8 / 53.2 / 1.0 mass%).

[0013] Item 5. The composition as described in Item 4, wherein the refrigerant contains R32, R125, and R1234yf, the total concentration of the three components being 99.5% by mass or more, and the mass ratio of the three components is within the area enclosed by the quadrilateral with points A, B, E, and F as vertices in a triangular composition diagram with the three components as vertices. Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point E (R32 / R125 / R1234yf=28.3 / 51.6 / 20.1 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0014] Item 6. The composition as described in Item 4 or 5, wherein the refrigerant contains R32, R125, and R1234yf, the total concentration of the three components being 99.5% by mass or more, and the mass ratio of the three components is within the area enclosed by the quadrilateral with points A, G, H, and F as vertices in a triangular composition diagram with the three components as vertices. Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point G (R32 / R125 / R1234yf=35.4 / 50.3 / 14.3 mass%) Point H (R32 / R125 / R1234yf=43.0 / 31.7 / 25.3 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0015] Item 7. The composition of any one of items 4 to 6, wherein the refrigerant consists only of R32, R125 and R1234yf.

[0016] Item 8. A composition containing a refrigerant, characterized in that, The aforementioned refrigerant contains difluoromethane (R32), pentafluoroethane (R125), and trans-1,3,3,3-tetrafluoropropylene (R1234ze(E)), with a total concentration of these three components of 99.5% by mass or more. Furthermore, the mass ratio of these three components falls within the area enclosed by the quadrilateral with vertices P, Q, R, and S in the triangular composition diagram of these three components. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point R (R32 / R125 / R1234ze (E) = 29.9 / 56.7 / 13.4 mass%) Point S (R32 / R125 / R1234ze (E) = 45.8 / 53.2 / 1.0 mass%).

[0017] Item 9. The composition as described in Item 8, wherein the refrigerant contains R32, R125, and R1234ze (E), the total concentration of the three components being 99.5% by mass or more, and the mass ratio of the three components is within the area enclosed by the quadrilateral with points P, Q, T, and U as vertices in a triangular composition diagram with the three components as vertices. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point T (R32 / R125 / R1234ze (E) = 33.4 / 50.6 / 16.0 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0018] Item 10. The composition as described in Item 8 or 9, wherein the refrigerant contains R32, R125, and R1234ze (E), the total concentration of the three components being 99.5% by mass or more, and the mass ratio of the three components being within the area enclosed by the quadrilateral with the following four points as vertices in a triangular composition diagram with the three components as vertices. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point V (R32 / R125 / R1234ze (E) = 49.0 / 32.0 / 19.0 mass%) Point W (R32 / R125 / R1234ze (E) = 39.2 / 49.5 / 11.3 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0019] Item 11. The composition of any one of items 8 to 10, wherein the refrigerant consists only of R32, R125 and R1234ze (E).

[0020] Item 12. The composition of any one of items 1 to 11, wherein the refrigerant is used as an alternative refrigerant to R410A.

[0021] Item 13. The composition of any one of items 1 to 12, wherein it contains at least one substance selected from water, tracer, ultraviolet fluorescent dye, stabilizer and polymerization inhibitor.

[0022] Item 14. The composition of any one of items 1 to 13, further comprising refrigeration oil, wherein the composition is used as a working fluid for a refrigeration unit.

[0023] Item 15. The composition of Item 14, wherein the refrigeration oil contains at least one polymer selected from polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0024] Item 16. A freezing method comprising the step of running a freezing cycle using the composition described in any one of items 1 to 15.

[0025] Item 17. A method of operating a refrigeration apparatus, wherein the refrigeration cycle is operated using any one of items 1 to 15.

[0026] Item 18. A refrigeration apparatus comprising, as any one of items 1 to 15, the composition as the working fluid.

[0027] Item 19. The refrigeration apparatus as described in Item 18, wherein the refrigeration apparatus is an air conditioning unit, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerator cabinet, a freezer cabinet, a refrigeration unit, a refrigeration unit for refrigerated warehouses, a vehicle-mounted air conditioning unit, a turbine refrigeration unit, or a screw refrigeration unit.

[0028] Item 20. The composition of any one of items 1 to 15, which is used as a refrigerant.

[0029] Item 21. The composition as described in Item 20, which is used as a refrigerant in a refrigeration apparatus.

[0030] Item 22. The composition as described in Item 21, wherein the refrigeration device is an air conditioning unit, a refrigerator, a freezer, a chiller, an ice maker, a refrigerator cabinet, a freezer cabinet, a refrigeration unit, a refrigeration unit for cold storage warehouses, an air conditioning unit for vehicles, a turbine refrigeration unit, or a screw refrigeration unit.

[0031] Item 23. Use of the composition described in any one of items 1 to 15 as a refrigerant.

[0032] Item 24. Use as described in Item 23, wherein it is used in a refrigeration apparatus.

[0033] Item 25. The use as described in Item 24, wherein the refrigeration device is an air conditioning unit, refrigerator, freezer, chiller, ice maker, refrigerated cabinet, freezer, refrigeration unit, refrigeration unit for refrigerated warehouse, vehicle air conditioning unit, turbine refrigeration unit, or screw refrigeration unit.

[0034] Invention Effects Compositions containing the refrigerant of the present invention have the characteristics of having the same cooling capacity and COP as R410A, and having a low GWP (2000 or less). Attached Figure Description

[0035] Figure 1 It is a diagram showing the mass ratio of R32, R125 and R1234yf contained in the refrigerant of the present invention (the area enclosed by the quadrilateral with points A, B, C and D as vertices) in a triangular composition diagram of R32, R125 and R1234yf.

[0036] Figure 2 It is a diagram showing the mass ratio of R32, R125 and R1234ze(E) contained in the refrigerant of the present invention (the area enclosed by the quadrilateral with points P, Q, R and S as vertices) in the triangular composition diagram of R32, R125 and R1234ze(E).

[0037] Figure 3 This is a schematic diagram of an experimental apparatus used to determine flammability (combustible or non-combustible). Detailed Implementation

[0038] In order to solve the above-mentioned technical problems, the inventors of the present invention conducted in-depth research and found that refrigerant compositions containing R32 and R125 at specific concentrations have the above-mentioned characteristics.

[0039] This invention was developed based on further and repeated research into this insight. It includes the following embodiments.

[0040] <Definition of Terms> In this specification, the terms “contains” and “includes” are used with the intent to include the concepts of the terms “substantially constitutes…” and “consistent solely of…”.

[0041] In this specification, the term "refrigerant" includes at least compounds with refrigerant numbers (ASHRAE numbers) beginning with R as specified by ISO 817 (National Organization for Standardization) to indicate the type of refrigerant, and also compounds that, although not marked with a refrigerant number, have the same properties as them as refrigerants.

[0042] From the perspective of compound structure, refrigerants are broadly classified into "fluorinated hydrocarbon compounds" and "non-fluorinated hydrocarbon compounds." "Fluorinated hydrocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Examples of "non-fluorinated hydrocarbon compounds" include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), and ammonia (R717).

[0043] In this specification, the term "composition containing refrigerant" includes at least: (1) the refrigerant itself (including mixtures of refrigerants, i.e., "mixed refrigerants"); (2) a composition that also contains other components and is capable of being mixed with at least refrigeration oil to obtain a working fluid for a refrigeration unit; and (3) a working fluid for a refrigeration unit containing refrigeration oil.

[0044] In this specification, of the three methods, the composition in (2) is referred to as "refrigerant composition" to distinguish it from the refrigerant itself (including mixed refrigerants). In addition, the refrigeration device in (3) is referred to as "working fluid containing refrigeration oil" to distinguish it from "refrigerant composition".

[0045] In this specification, the term "replacement" refers to the first type of operation where, in a context where a second refrigerant is "replaced" by a first refrigerant, equipment designed to operate using the first refrigerant can be operated under optimal conditions using the second refrigerant with only minor changes and adjustments to components (refrigeration oil, gaskets, liners, expansion valves, dryers, and at least one of other components) as required. That is, this type refers to operation after "replacing" the refrigerant in the same equipment. As methods of this type of "replacement," in order of increasing degree of change and adjustment required when replacing with the second refrigerant, there are "drop-in replacement," "nealydrop-in replacement," and "retrofit."

[0046] As a second type, the term "substitute" also includes situations where a second refrigerant is used in a machine designed to operate using a second refrigerant for the same purpose as the known uses of the first refrigerant. This type refers to "substituting" the refrigerant for the same purpose.

[0047] In this specification, the term "refrigeration device" refers to any device that creates and maintains a temperature lower than the surrounding external atmosphere by extracting heat from an object or space. In other words, broadly speaking, a refrigeration device is a conversion device that obtains energy from the outside to perform its function and convert it in order to move heat from a low-temperature side to a high-temperature side. In this invention, broadly speaking, the meaning of a refrigeration device is the same as that of a heat pump.

[0048] Furthermore, in this invention, in a narrow sense, the terms "refrigeration device" and "heat pump" are used interchangeably due to the different temperature ranges and operating temperatures utilized. In this context, a device that places a low-temperature heat source in a temperature range below atmospheric temperature is sometimes called a refrigeration device, while a device that places a low-temperature heat source in a temperature close to atmospheric temperature and drives a refrigeration cycle, utilizing the resulting heat release, is called a heat pump. Additionally, there are devices such as air conditioners with "cooling mode" and "heating mode," which, although identical devices, combine the functions of both a refrigeration device and a heat pump in the narrow sense. In this specification, unless otherwise specified, "refrigeration device" and "heat pump" are used in their broadest sense.

[0049] In this manual, "vehicle air conditioning equipment" refers to a type of refrigeration device used in vehicles such as gasoline vehicles, hybrid vehicles, electric vehicles, and hydrogen-powered vehicles. Vehicle air conditioning equipment refers to a refrigeration device that includes a refrigeration cycle. This cycle utilizes an evaporator to exchange heat with liquid refrigerant, a compressor draws in evaporated refrigerant gas, a condenser cools and liquefies the compressed refrigerant gas, and then, after thermal expansion through an expansion valve, supplies it back to the evaporator as liquid refrigerant.

[0050] In this specification, "turbo chiller" is a type of large-scale refrigeration unit, referring to a refrigeration unit that includes a refrigeration cycle. This cycle utilizes an evaporator to exchange heat with liquid refrigerant, a centrifugal compressor draws in the evaporated refrigerant gas, a condenser cools and liquefies the compressed refrigerant gas, and then expands it through an expansion valve, supplying it back to the evaporator as liquid refrigerant. The aforementioned "large-scale refrigeration unit" refers to a large air conditioning unit intended for air conditioning within a building unit.

[0051] The technical significance of "non-flammable" and "slightly flammable" in this instruction manual is as follows.

[0052] In this specification, "non-flammable" for refrigerant means that, in the US ANSI / ASHRAE 34-2013 standard, the WCF (Worst case of formulation for flammability) composition, which is the most flammable component in the permissible concentration of the refrigerant, is classified as "Class 1".

[0053] In this instruction manual, "micro-flammable" refrigerant means that, according to the American ANSI / ASHRAE 34-2013 standard, the WCF composition is judged to be "2L level".

[0054] In this specification, GWP (AR4) refers to the value obtained based on the IPCC (Intergovernmental Panel on Climate Change) Fourth Report.

[0055] In this specification, GWP (AR5) refers to the value obtained based on the IPCC Fifth Report.

[0056] 1. Composition The composition of the present invention contains a refrigerant, and the refrigerant can be listed as "refrigerant 1", "refrigerant 2", "refrigerant 3" and "refrigerant 4". Refrigerant 1, refrigerant 2, refrigerant 3 and refrigerant 4 will be described below respectively.

[0057] Hereinafter, in this specification, "the refrigerant of the present invention" means refrigerant 1, refrigerant 2, refrigerant 3 and refrigerant 4.

[0058] The refrigerant of the present invention can be broadly classified into embodiments 1, 2, 3 and 4 (also referred to as refrigerant 1, refrigerant 2, refrigerant 3 and refrigerant 4, respectively) according to the implementation method.

[0059] 1.1 Refrigerant Composition 1.1.1 Implementation Method 1: Refrigerant 1 (R32 / R125) Refrigerant 1 contains R32 and R125 as essential components.

[0060] In refrigerant 1 as a whole, the total concentration of R32 and R125 is 99.5% by mass or more. In other words, refrigerant 1 contains R32 and R125 with a total concentration of 99.5% by mass or more.

[0061] In refrigerant 1, the proportion of R32 is 53.1 to 56.0% by mass and the proportion of R125 is 44.0 to 46.9% by mass relative to the total mass of R32 and R125.

[0062] Refrigerant 1 has such a composition that it possesses: (1) low GWP (AR4) (below 2000), (2) non-flammable, and (3) when used as a substitute refrigerant for R410A, it has the same refrigeration capacity and COP as R410A.

[0063] Furthermore, refrigerant 1, by having the above-described structure, possesses the characteristics of having a GWP (AR4) of 1800 to 2000 and being non-flammable.

[0064] The refrigerant 1 has a cooling capacity of 85% or more relative to R410A, preferably 90% or more, more preferably 95% or more, and particularly preferably 100% or more.

[0065] Refrigerant 1 has a GWP (AR4) of less than 2000, and therefore, from the perspective of global warming, it can significantly control environmental load compared with other general-purpose refrigerants.

[0066] From the perspective of energy efficiency, it is preferable that refrigerant 1 has a higher ratio of power consumed in the refrigeration cycle to refrigeration capacity (coefficient of performance (COP)) compared to R410A. Specifically, the COP compared to R410A is preferably 98% or more, more preferably 99% or more, and particularly preferably 100% or more.

[0067] In refrigerant 1, the preferred proportions of R32 (53.2–55.9% by mass) and R125 (44.1–46.8% by mass) relative to the total mass of R32 and R125 are:

[0068] In refrigerant 1, the preferred proportions of R32 and R125 relative to the total mass of R32 and R125 are 53.5% to 55.5% by mass and 44.5% to 46.5% by mass. At this point, the refrigerant 1 has a GWP (AR4) of less than 2000, is non-flammable, has a COP equivalent to that of R410A, and has superior cooling capacity compared to R410A.

[0069] The refrigerant 1 contains R32 and R125 with a total concentration of 99.5% by mass or more. In the refrigerant 1 as a whole, the total amount of R32 and R125 is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and even more preferably 99.9% by mass or more.

[0070] Without impairing the aforementioned properties, refrigerant 1 may contain other refrigerants besides R32 and R125. In this case, the proportion of other refrigerants in the total refrigerant 1 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. There are no particular limitations on the other refrigerants, and a wide range of well-known refrigerants widely used in the art can be selected. Refrigerant 1 may contain only one other refrigerant, or it may contain two or more other refrigerants.

[0071] Refrigerant 1 is particularly preferred to consist only of R32 and R125. In other words, the total concentration of R32 and R125 in refrigerant 1 is particularly preferred to be 100% by mass.

[0072] When refrigerant 1 consists only of R32 and R125, the preferred content of R32 is 53.1 to 56.0% by mass and the content of R125 is 44.0 to 46.9% by mass relative to the total mass of R32 and R125. In this case, refrigerant 1 has the following characteristics: (1) low GWP (AR4) (below 2000), (2) non-flammable, and (3) when used as a substitute refrigerant for R410A, it has the same refrigeration capacity and COP as R410A.

[0073] When refrigerant 1 consists only of R32 and R125, it is more preferable that the content of R32 is 53.2 to 55.9% by mass and the content of R125 is 44.1 to 46.8% by mass relative to the total mass of R32 and R125. In this case, the GWP (AR4) of refrigerant 1 is below 2000, it is non-flammable, it has the same COP as R410A, and its cooling capacity is superior to that of R410A.

[0074] When refrigerant 1 consists only of R32 and R125, it is further preferred that the content of R32 is 53.5 to 55.5% by mass and the content of R125 is 44.5 to 46.5% by mass relative to the total mass of R32 and R125. At this time, the GWP (AR4) of refrigerant 1 is below 2000, it is non-flammable, it has the same COP as R410A, and its refrigeration capacity is superior to that of R410A.

[0075] Refrigerant 1, like R410A, is non-flammable (classified as ASHRAE flammability class 1 in the American ANSI / ASHRAE 34-2013 standard), thus offering higher safety and a wider range of applications compared to flammable refrigerants.

[0076] Additionally, for refrigerant 1, when using a testing apparatus based on ASTM E681-09 (refer to...) Figure 3 When the flammability range was measured, it was found to be non-flammable under hypothetical high temperature and high humidity conditions (50% relative humidity at 36°C). Therefore, refrigerant 1 is non-flammable even under hypothetical high temperature and high humidity conditions (50% relative humidity at 36°C) and is a safe refrigerant from a flammability point of view.

[0077] That is, refrigerant 1 has the characteristics of being ASHRAE Combustion Component Class 1 in the American ANSI / ASHRAE 34-2013 standard, and is non-flammable even under assumed high temperature and high humidity conditions (50% relative humidity at 36°C).

[0078] 1.1.2 Implementation Method 2: Refrigerant 2 (R32 / R125) Refrigerant 2 contains R32 and R125 as essential components.

[0079] In refrigerant 2 as a whole, the total concentration of R32 and R125 is 99.5% by mass or more. In other words, refrigerant 2 contains R32 and R125 with a total concentration of 99.5% by mass or more.

[0080] In refrigerant 2, the proportion of R32 is 60.5 to 62.5% by mass relative to the total mass of R32 and R125, and the proportion of R125 is 37.5 to 39.5% by mass.

[0081] Refrigerant 2 has such a composition that it possesses: (1) low GWP (AR4) (below 1800), (2) non-flammable (ASHRAE flammability classification of 1 in the American ANSI / ASHRAE 34-2013 standard), and (3) when used as a substitute refrigerant for R410A, it has the same refrigeration capacity and COP as R410A.

[0082] The refrigerant 2 has a cooling capacity of 85% or more relative to R410A, preferably 90% or more, more preferably 95% or more, even more preferably 100% or more, and particularly preferably 103% or more.

[0083] Refrigerant 2 has a GWP of less than 1800, and therefore, from the perspective of global warming, it can significantly control environmental impact compared with other general-purpose refrigerants.

[0084] From the viewpoint of energy efficiency, it is preferred that refrigerant 2 has a higher ratio of power consumed in the refrigeration cycle to refrigeration capacity (coefficient of performance (COP)) compared to R410A. Specifically, the COP compared to R410A is preferably 98% or more, more preferably 100% or more, and particularly preferably 101% or more.

[0085] In refrigerant 2, the preferred proportions of R32 and R125 relative to the total mass of R32 and R125 are 61-62.5% by mass and 37.5-39% by mass. At this point, refrigerant 2 has a GWP (AR4) of less than 1800, is non-flammable, has a COP equivalent to R410A, and exhibits superior cooling capacity compared to R410A.

[0086] In refrigerant 2, the preferred proportions of R32 and R125 relative to the total mass of R32 and R125 are 61.5 to 62.5% by mass and 37.5 to 38.5% by mass. At this point, the refrigerant 2 has a GWP (AR4) of less than 1800, is non-flammable, has a COP equivalent to R410A, and has superior cooling capacity compared to R410A.

[0087] The refrigerant 2 contains R32 and R125 with a total concentration of 99.5% by mass or more. In the refrigerant 2 as a whole, the total amount of R32 and R125 is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and even more preferably 99.9% by mass or more.

[0088] Without impairing the aforementioned properties, refrigerant 2 may contain other refrigerants besides R32 and R125. In this case, the proportion of other refrigerants in the overall refrigerant 2 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. There are no particular limitations on the other refrigerants, and a wide range of well-known refrigerants widely used in the art can be selected. Refrigerant 2 may contain only one other refrigerant, or it may contain two or more other refrigerants.

[0089] Refrigerant 2 is particularly preferred to consist only of R32 and R125. In other words, the total concentration of R32 and R125 in refrigerant 2 is particularly preferred to be 100% by mass.

[0090] When refrigerant 2 consists only of R32 and R125, the preferred content of R32 is 60.5 to 62.5% by mass and the content of R125 is 37.5 to 39.5% by mass relative to the total mass of R32 and R125. In this case, refrigerant 2 has the following characteristics: (1) low GWP (AR4) (below 1800), (2) non-flammable, and (3) when used as a substitute refrigerant for R410A, it has the same refrigeration capacity and COP as R410A.

[0091] When refrigerant 2 consists only of R32 and R125, it is more preferable that the content of R32 is 61 to 62.5% by mass and the content of R125 is 37.5 to 39% by mass relative to the total mass of R32 and R125. In this case, the refrigerant 2 has a GWP (AR4) of less than 1800, is non-flammable, has a COP equivalent to R410A, and has superior cooling capacity compared to R410A.

[0092] When refrigerant 2 consists only of R32 and R125, it is further preferred that the content of R32 is 61.5 to 62.5% by mass and the content of R125 is 37.5 to 38.5% by mass relative to the total mass of R32 and R125. At this time, the GWP (AR4) of refrigerant 2 is below 1800, it is non-flammable, it has the same COP as R410A, and its refrigeration capacity is superior to that of R410A.

[0093] Refrigerant 2, like R410A, is non-flammable (classified as ASHRAE flammability level 1 in the American ANSI / ASHRAE 34-2013 standard), thus it is safer and has a wider range of applications compared to flammable refrigerants.

[0094] 1.1.3 Implementation Method 3: Refrigerant 3 (R32 / R125 / R1234yf) Refrigerant 3 contains R32, R125, and R1234yf as essential components. Hereinafter, R32, R125, and R1234yf will also be referred to as the "three components" in this project.

[0095] In refrigerant 3, the total concentration of the three components is 99.5% by mass or more. In other words, refrigerant 3 contains three components with a total concentration of 99.5% by mass or more.

[0096] In refrigerant 3, the mass ratio of the three components is within the area enclosed by the quadrilateral with the following four points A, B, C and D as vertices in the triangular composition diagram with the three components as vertices.

[0097] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point C (R32 / R125 / R1234yf=26.2 / 57.5 / 16.3 mass%) Point D (R32 / R125 / R1234yf=45.8 / 53.2 / 1.0 mass%).

[0098] In this project, a triangulation diagram with three vertices means: (e.g., ...) Figure 1 As shown, the above three components (R32, R125 and R1234yf) are used as vertices, and the sum of the concentrations of R32, R125 and R1234yf is used as the three-component composition diagram at 100% by mass.

[0099] Refrigerant 3 has the following composition, and therefore possesses: (1) a low GWP (AR5) (below 2000), (2) non-flammability, and (3) the same refrigeration capacity and COP as R410A when used as a replacement refrigerant for R410A. Refrigerant 3 is also non-flammable like R410A, and therefore has higher safety and a wider range of applications compared to flammable refrigerants.

[0100] Straight line a passing through points A and B is the non-flammable boundary line. In the region closer to vertex R125 of the triangular composition diagram than straight line a, the three-component refrigerant mixture is non-flammable.

[0101] The straight line b passing through points B and C represents the mass ratio of the cooling capacity to R410A, which is 85%. In the region closer to vertex R32 of the triangular composition diagram than line b, the cooling capacity of the three-component refrigerant mixture exceeds 85% of that of R410A.

[0102] The straight line c passing through points C and D represents the mass ratio where the GWP (AR5) is 2000. In the regions closer to vertices R32 and R1234yf of the triangular composition diagram than line c, the GWP (AR5) of the three-component mixed refrigerant is lower than 2000.

[0103] The straight line d passing through points A and D represents the mass ratio of R1234yf concentration (mass%) to 1 mass%. In the region closer to the vertex R1234yf of the triangular composition diagram than straight line d, the R1234yf of the three-component mixed refrigerant exceeds 1 mass.

[0104] Refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, has a GWP (AR5) of less than 2000, is non-flammable, and has a cooling capacity of more than 85% relative to R410A when the mass ratio is within the area (ABCD region) enclosed by the quadrilateral with points A, B, C and D as vertices.

[0105] In refrigerant 3, the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points A, B, E and F as vertices in the triangular composition diagram with the three components as vertices.

[0106] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point E (R32 / R125 / R1234yf=28.3 / 51.6 / 20.1 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0107] Regarding the triangular composition diagram with the above three components as each vertex, as described above.

[0108] Regarding the line a passing through points A and B, as described above.

[0109] Point E lies on line b, which passes through points B and C. Regarding line b, as described above.

[0110] The straight line e passing through points E and F represents the mass ratio where the GWP (AR4) is 2000. In the regions closer to vertices R32 and R1234yf in the triangular composition diagram than line e, the GWP (AR4) of the three-component refrigerant mixture is below 2000. Point E is the intersection of line b and line e.

[0111] Point F lies on line d, which passes through points A and D. Line d is as described above. Point F is the intersection of line d and line e.

[0112] Refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, has a GWP (AR4) of less than 2000, is non-flammable, and has a cooling capacity of more than 85% relative to R410A when the mass ratio is within the area enclosed by the quadrilateral with points A, B, E and F as vertices (ABEF region).

[0113] In refrigerant 3, the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points A, G, H and F as vertices in the triangular composition diagram with the three components as vertices.

[0114] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point G (R32 / R125 / R1234yf=35.4 / 50.3 / 14.3 mass%) Point H (R32 / R125 / R1234yf=43.0 / 31.7 / 25.3 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0115] Regarding the triangular composition diagram with the above three components as each vertex, as described above.

[0116] Point G lies on line a, which passes through points A and B. Regarding line a, as described above.

[0117] The straight line f passing through points G and H represents the refrigeration capacity relative to R410A at a mass ratio of 90%. In the region closer to vertex R32 of the triangular composition diagram than line f, the refrigeration capacity of the three-component refrigerant mixture exceeds 90% of that of R410A. Point G is the intersection of lines a and f.

[0118] Point H lies on line e, which passes through points E and F. Regarding line e, as described above, point H is the intersection of line e and line f.

[0119] Point F lies on line d, which passes through points A and D. Line d is as described above. Point F is the intersection of line d and line e.

[0120] Refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, has a GWP (AR4) of less than 2000, is non-flammable, and has a cooling capacity of more than 90% relative to R410A when the mass ratio is within the area enclosed by the quadrilateral with points A, G, H and F as vertices (AGHF area).

[0121] The refrigerant 3 contains R32, R125 and R1234yf with a total concentration of 99.5% by mass or more. The total amount of R32, R125 and R1234yf in the refrigerant 3 is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and even more preferably 99.9% by mass or more.

[0122] Without impairing the aforementioned properties, refrigerant 3 may contain other refrigerants besides R32, R125, and R1234yf. In this case, the proportion of other refrigerants in the overall refrigerant 2 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. There are no particular limitations on the other refrigerants; a wide range of well-known refrigerants widely used in the art can be selected. Refrigerant 3 may contain only one other refrigerant or two or more other refrigerants.

[0123] Refrigerant 3 is particularly preferred to consist only of R32, R125, and R1234yf. In other words, the total concentration of R32, R125, and R1234yf in refrigerant 3 is particularly preferred to be 100% by mass.

[0124] When refrigerant 3 is composed only of R32, R125 and R1234yf, the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points A, B, C and D as vertices in the triangular composition diagram with the three components as vertices.

[0125] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point C (R32 / R125 / R1234yf=26.2 / 57.5 / 16.3 mass%) Point D (R32 / R125 / R1234yf=45.8 / 53.2 / 1.0 mass%).

[0126] At this point, when the mass ratio of refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, is within the area (ABCD region) enclosed by the quadrilateral with points A, B, C and D as vertices, the GWP (AR5) is less than 2000, it is non-flammable, and its cooling capacity is more than 85% of that of R410A.

[0127] When refrigerant 3 is composed only of R32, R125 and R1234yf, the mass ratio of the three components is more preferably within the area enclosed by the quadrilateral with the following four points A, B, E and F as vertices in the triangular composition diagram with the three components as each vertex.

[0128] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point B (R32 / R125 / R1234yf=36.5 / 30.0 / 33.5% mass) Point E (R32 / R125 / R1234yf=28.3 / 51.6 / 20.1 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0129] At this point, when the mass ratio of refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, is within the area (ABEF region) enclosed by the quadrilateral with points A, B, E and F as vertices, the GWP (AR4) is less than 2000, it is non-flammable, and its cooling capacity is more than 85% of that of R410A.

[0130] When refrigerant 3 is composed only of R32, R125 and R1234yf, the mass ratio of the three components is further preferably within the area enclosed by the quadrilateral with the following four points A, G, H and F as vertices in the triangular composition diagram with the three components as each vertex.

[0131] Point A (R32 / R125 / R1234yf=62.2 / 36.8 / 1.0 mass%) Point G (R32 / R125 / R1234yf=35.4 / 50.3 / 14.3 mass%) Point H (R32 / R125 / R1234yf=43.0 / 31.7 / 25.3 mass%) Point F (R32 / R125 / R1234yf=51.9 / 47.1 / 1.0 mass%).

[0132] At this point, when the mass ratio of refrigerant 3, which is a ternary mixed refrigerant of R32, R125 and R1234yf, is within the area (AGHF region) enclosed by the quadrilateral with points A, G, H and F as vertices, the GWP (AR4) is less than 2000, it is non-flammable, and its cooling capacity is more than 90% of that of R410A.

[0133] 1.1.4 Implementation Method 4: Refrigerant 4 (R32 / R125 / R1234ze(E)) Refrigerant 4 contains R32, R125, and R1234ze(E) as essential components. Hereinafter, R32, R125, and R1234ze(E) will also be referred to as the "three components" in this project.

[0134] In refrigerant 4, the total concentration of the three components is 99.5% by mass or more. In other words, refrigerant 4 contains three components with a total concentration of 99.5% by mass or more.

[0135] In refrigerant 4, the mass ratio of the three components is within the area enclosed by the quadrilateral with the following four points as vertices: P, Q, R, and S, in the triangular composition diagram with the three components as vertices.

[0136] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point R (R32 / R125 / R1234ze (E) = 29.9 / 56.7 / 13.4 mass%) Point S (R32 / R125 / R1234ze (E) = 45.8 / 53.2 / 1.0 mass%).

[0137] In this project, a triangulation diagram with three components as vertices means, for example... Figure 2 The diagram shows the composition of the three components (R32, R125, and R1234ze(E)) with the above three components as vertices and the sum of the concentrations of R32, R125, and R1234ze(E) set to 100% by mass.

[0138] Refrigerant 4 has the following composition, and therefore possesses: (1) a low GWP (AR5) (below 2000), (2) non-flammability, and (3) the same refrigeration capacity and COP as R410A when used as a substitute refrigerant for R410A. Refrigerant 4 is also non-flammable like R410A, and therefore has higher safety and a wider range of applications compared to flammable refrigerants.

[0139] The straight line g passing through points P and Q is the non-flammable boundary line. In the region closer to vertex R125 of the triangular composition diagram than straight line g, the three-component mixed refrigerant is non-flammable.

[0140] The straight line h passing through points Q and R represents the refrigeration capacity relative to R410A at a mass ratio of 85%. In the region closer to vertex R32 of the triangular composition diagram than line h, the refrigeration capacity of the three-component refrigerant mixture exceeds 85% of that of R410A.

[0141] The straight line i passing through points R and S represents the mass ratio where the GWP (AR5) is 2000. In the regions closer to vertex R32 and vertex R1234ze (E) of the triangular composition diagram than the straight line i, the GWP (AR5) of the three-component mixed refrigerant is lower than 2000.

[0142] The straight line j passing through points S and P represents the mass ratio of R1234ze(E) concentration (mass%) to 1 mass%. In the region closer to the vertex R1234ze(E) of the triangular composition diagram than straight line j, the R1234ze(E) of the three-component mixed refrigerant exceeds 1 mass.

[0143] Refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze (E), has a GWP (AR5) of less than 2000, is non-flammable, and has a cooling capacity of more than 85% relative to R410A when the mass ratio is within the area enclosed by the quadrilateral with points P, Q, R and S as vertices (PQRS area).

[0144] In refrigerant 4, the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points as vertices: P, Q, T, and U, in the triangular composition diagram with the three components as vertices.

[0145] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point T (R32 / R125 / R1234ze (E) = 33.4 / 50.6 / 16.0 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0146] Regarding the triangular composition diagram with the above three components as each vertex, as described above.

[0147] Regarding the line g passing through points P and Q, as described above.

[0148] Point T lies on the straight line h that passes through points Q and R. The straight line h is as described above.

[0149] The straight line k passing through points T and U represents the mass ratio where the GWP (AR4) is 2000. In the regions closer to vertex R32 and vertex R1234ze (E) of the triangular composition diagram than line k, the GWP (AR4) of the three-component refrigerant mixture is below 2000. Point T is the intersection of line h and line k.

[0150] Point U lies on line j, which passes through points S and P. Regarding line j, as described above.

[0151] Refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze (E), has a GWP (AR4) of less than 2000, is non-flammable, and has a cooling capacity of more than 85% relative to R410A when the mass ratio is within the area enclosed by the quadrilateral with points P, Q, T and U as vertices (PQTU area).

[0152] In refrigerant 4, the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points as vertices: P, V, W, and U, in the triangular composition diagram with the three components as vertices.

[0153] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point V (R32 / R125 / R1234ze (E) = 49.0 / 32.0 / 19.0 mass%) Point W (R32 / R125 / R1234ze (E) = 39.2 / 49.5 / 11.3 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0154] Regarding the triangular composition diagram with the above three components as each vertex, as described above.

[0155] Point V lies on line g, which passes through points P and Q. Regarding line g, as described above, point V is the intersection of line g and line l, which passes through points V and W.

[0156] Point W lies on line l, which passes through points V and W. Line l represents the refrigeration capacity relative to 90% of the mass of R410A. In the region closer to vertex R32 of the triangular composition diagram than line l, the refrigeration capacity of the three-component refrigerant mixture exceeds 90% of that of R410A. Point W is the intersection of line l and line k, which passes through points T and U.

[0157] Point U lies on line j, which passes through points S and P. Regarding line j, as described above, point U is the intersection of line j and line k.

[0158] Refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze (E), has a GWP (AR4) of less than 2000, is non-flammable, and has a cooling capacity of more than 90% relative to R410A when the mass ratio is within the area enclosed by the quadrilateral with points P, V, W and U as vertices (PVWU region).

[0159] The refrigerant 4 contains R32, R125 and R1234ze(E) with a total concentration of 99.5% by mass or more. In the refrigerant 4 as a whole, the total amount of R32, R125 and R1234ze(E) is preferably 99.7% by mass or more, more preferably 99.8% by mass or more, and even more preferably 99.9% by mass or more.

[0160] Without compromising the aforementioned properties, refrigerant 4 may contain other refrigerants besides R32, R125 and R1234ze (E).

[0161] At this point, the proportion of other refrigerants in the overall refrigerant 4 is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, even more preferably 0.2% by mass or less, and particularly preferably 0.1% by mass or less. There are no particular limitations on the other refrigerants, and a wide range of well-known refrigerants widely used in the art can be selected. Refrigerant 4 may contain only one other refrigerant, or it may contain two or more other refrigerants.

[0162] It is particularly preferred that refrigerant 4 consists only of R32, R125, and R1234ze(E). In other words, it is particularly preferred that the total concentration of R32, R125, and R1234ze(E) in the refrigerant 4 is 100% by mass.

[0163] When refrigerant 4 is composed only of R32, R125 and R1234ze (E), the mass ratio of the three components is preferably within the area enclosed by the quadrilateral with the following four points as vertices in the triangular composition diagram with the three components as vertices.

[0164] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point R (R32 / R125 / R1234ze (E) = 29.9 / 56.7 / 13.4 mass%) Point S (R32 / R125 / R1234ze (E) = 45.8 / 53.2 / 1.0 mass%).

[0165] At this point, when the mass ratio of refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze(E), is within the region (PQRS region) enclosed by the quadrilateral with points P, Q, R and S as vertices, is less than 2000, non-flammable, and has a cooling capacity of more than 85% relative to R410A.

[0166] When refrigerant 4 is composed only of R32, R125 and R1234ze (E), the mass ratio of the three components is more preferably within the area enclosed by the quadrilateral with points P, Q, T and U as vertices in the triangular composition diagram with the three components as vertices.

[0167] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point T (R32 / R125 / R1234ze (E) = 33.4 / 50.6 / 16.0 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0168] At this point, when the mass ratio of refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze (E), is within the region (PQTU region) enclosed by the quadrilateral with points P, Q, T and U as vertices, is less than 2000, non-flammable, and has a cooling capacity of more than 85% relative to R410A.

[0169] When refrigerant 4 is composed only of R32, R125 and R1234ze (E), the mass ratio of the three components is more preferably within the area enclosed by the quadrilateral with the following four points as vertices in the triangular composition diagram with the three components as vertices.

[0170] Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point V (R32 / R125 / R1234ze (E) = 49.0 / 32.0 / 19.0 mass%) Point W (R32 / R125 / R1234ze (E) = 39.2 / 49.5 / 11.3 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

[0171] At this point, when the mass ratio of refrigerant 4, which is a ternary mixed refrigerant of R32, R125 and R1234ze (E), is within the region (PVWU region) enclosed by the quadrilateral with points P, V, W and U as vertices, is less than 2000, non-flammable, and has a cooling capacity of more than 90% relative to R410A.

[0172] 1.2 Applications Refrigerant 1, Refrigerant 2, Refrigerant 3 and Refrigerant 4 each have the same refrigeration capacity as the currently used R410A, and have a low GWP (below 2000), making them particularly suitable as replacement refrigerants for R410A.

[0173] Furthermore, the compositions of the present invention containing these refrigerants can be widely used as working fluids in: 1) refrigeration methods including processes for running refrigeration cycles, 2) methods for operating refrigeration apparatuses for running refrigeration cycles, etc., as existing refrigerants.

[0174] Here, the above-mentioned refrigeration cycle means: using a compressor, the composition of the present invention is circulated inside the refrigeration unit in a state consisting only of the above-mentioned refrigerants (refrigerant 1, refrigerant 2, refrigerant 3 and refrigerant 4), or the refrigerant composition described later, or a working fluid containing refrigeration oil, thereby performing energy conversion.

[0175] Therefore, the present invention also includes inventions of the use of the compositions of the present invention in freezing methods, inventions of the use of the compositions of the present invention in methods of operating freezing apparatus, and freezing apparatus having the compositions of the present invention.

[0176] Furthermore, there are no limitations on the types of refrigeration equipment that can be used, such as air conditioning equipment, refrigerators, freezers, chillers, ice makers, refrigerated cabinets, freezers, refrigeration and freezing units, refrigeration units for cold storage warehouses, vehicle-mounted air conditioning equipment, turbine refrigeration units, or screw refrigeration units.

[0177] 2. Refrigerant composition The refrigerant composition of the present invention, as long as it contains the refrigerant of the present invention, can be used for the same purpose as the refrigerant of the present invention.

[0178] In addition, the refrigerant composition of the present invention can also be used to obtain a working fluid for a refrigeration unit by mixing with at least refrigeration oil.

[0179] The refrigerant composition of the present invention contains, in addition to the refrigerant of the present invention, at least one other component. The refrigerant composition of the present invention may, as needed, contain at least one of the following other components.

[0180] As described above, when the refrigerant composition of the present invention is used as the working fluid in a refrigeration unit, it is typically used in combination with at least refrigeration oil.

[0181] Here, the refrigerant composition of the present invention preferably contains substantially no refrigeration oil. Specifically, in the refrigerant composition of the present invention, the content of refrigeration oil relative to the total refrigerant composition is preferably 0 to 1% by mass, more preferably 0 to 0.5% by mass, further preferably 0 to 0.25% by mass, and particularly preferably 0 to 0.1% by mass.

[0182] 2.1 Water The refrigerant composition of the present invention may contain trace amounts of water.

[0183] Regarding the water content in the refrigerant composition, it is preferably 0 to 0.1% by mass relative to the total refrigerant, more preferably 0 to 0.075% by mass, even more preferably 0 to 0.05% by mass, and particularly preferably 0 to 0.025% by mass.

[0184] By including trace amounts of moisture in the refrigerant composition, the intramolecular double bonds of the unsaturated fluorinated hydrocarbon compounds in the refrigerant are stabilized, and the oxidation of the unsaturated fluorinated hydrocarbon compounds is less likely to occur, thus improving the stability of the refrigerant composition.

[0185] 2.2 Tracers In order to track changes in the refrigerant composition of the present invention in the event of dilution, contamination, or any other alterations, a tracer may be added to the refrigerant composition of the present invention at a detectable concentration.

[0186] In the refrigerant composition of the present invention, the tracer may be one type or two or more types.

[0187] There are no particular limitations on the tracer used, and it can be appropriately selected from commonly used tracers. Preferably, a compound that is unlikely to be an unavoidable impurity in the refrigerant of the present invention is selected as the tracer.

[0188] Examples of tracers that can be used include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorohydrocarbons, fluorinated hydrocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorinated ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N₂O). Among these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorohydrocarbons, fluorinated hydrocarbons, and fluorinated ethers are preferred.

[0189] As the tracer described above, the following compounds (hereinafter also referred to as tracer compounds) are more preferred.

[0190] HCC-40 (chloromethane, CH3Cl) HFC-41 (fluoromethane, CH3F) HFC-161 (fluoroethane, CH3CH2F) HFC-245fa (1,1,1,3,3-pentafluoropropane, CF3CH2CHF2) HFC-236fa (1,1,1,3,3,3-hexafluoropropane, CF3CH2CF3) HFC-236ea (1,1,1,2,3,3-hexafluoropropane, CF3CHFCHF2) HCFC-22 (dichlorofluoromethane, CHClF2) HCFC-31 (chlorofluoromethane, CH2ClF) CFC-1113 (chlorotrifluoroethylene, CF2=CClF) HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2) HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F) HFE-143a (trifluoromethyl-methyl ether, CF3OCH3) HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3) HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3) The tracer compound described above can be present in the refrigerant composition at a total concentration of 10 parts per million (ppm) to 1000 ppm. Preferably, the tracer compound is present in the refrigerant composition at a total concentration of 30 ppm to 500 ppm, more preferably at a total concentration of 50 ppm to 300 ppm, even more preferably at a total concentration of 75 ppm to 250 ppm, and particularly preferably at a total concentration of 100 ppm to 200 ppm.

[0191] 2.3 Ultraviolet Fluorescent Dyes In the refrigerant composition of the present invention, the ultraviolet fluorescent dye may contain one type alone or two or more types.

[0192] There are no particular limitations on the aforementioned ultraviolet fluorescent dyes; they can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0193] Examples of ultraviolet fluorescent dyes mentioned above include naphthalenediimide, coumarin, anthracene, phenanthrene, xanthracene, thioxanthene, benzoxanthene, and fluorescein, as well as their derivatives. Among these, naphthalenediimide and coumarin are preferred.

[0194] 2.4 Stabilizers In the refrigerant composition of the present invention, the stabilizer may be one type or two or more types.

[0195] There are no particular limitations on the stabilizers mentioned above; any commonly used stabilizers may be appropriately selected.

[0196] Examples of stabilizers mentioned above include nitro compounds, ethers, and amines.

[0197] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0198] Examples of ethers include 1,4-dioxane.

[0199] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0200] In addition to the aforementioned nitro compounds, ethers, and amines, other examples of stabilizers include butylated hydroxyl xylene and benzotriazole.

[0201] The content of the stabilizer is not particularly limited, but is usually 0.01 to 5% by mass relative to the total refrigerant, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, even more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass.

[0202] The method for evaluating the stability of the refrigerant composition of the present invention is not particularly limited, and can be performed according to commonly used methods. As an example of such a method, the method of evaluation based on the amount of free fluoride ions according to ASHRAE Standard 97-2007 can be cited. Furthermore, the method of evaluation based on the total acid number can also be cited. This method can be performed, for example, according to ASTM D 974-06.

[0203] 2.5 Polymerization inhibitors In the refrigerant composition of the present invention, the polymerization inhibitor may be one type or two or more types.

[0204] There are no particular limitations on the above-mentioned polymerization inhibitors; they can be appropriately selected from commonly used polymerization inhibitors.

[0205] Examples of polymerization inhibitors mentioned above include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0206] The content of the above-mentioned polymerization inhibitor is not particularly limited, but is usually 0.01 to 5% by mass relative to the total refrigerant, preferably 0.05 to 3% by mass, more preferably 0.1 to 2% by mass, even more preferably 0.25 to 1.5% by mass, and particularly preferably 0.5 to 1% by mass.

[0207] 2.6 Other components contained in the refrigerant composition The refrigerant composition of the present invention may also include the following components as possible components.

[0208] For example, it may contain fluorinated hydrocarbons different from the refrigerants mentioned above. There are no particular limitations on the fluorinated hydrocarbons that may be used as other components, and at least one fluorinated hydrocarbon selected from HCFC-1122, HCFC-124 and CFC-1113 may be listed.

[0209] Additionally, as other components, it may contain, for example, formula (A): C m H n X p[In the formula, X independently represents a fluorine atom, a chlorine atom, or a bromine atom, m is 1 or 2, 2m+2≥n+p, p≥1] at least one of the halogenated organic compounds shown. The above-mentioned halogenated organic compounds are not particularly limited. For example, difluorochloromethane, chloromethane, 2-chloro-1,1,1,2,2-pentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene, trifluoroethylene, etc., are preferred.

[0210] Additionally, as other components, it may contain, for example, formula (B): C m H n X p [In the formula, X independently represents a non-halogen atom, m is 1 or 2, 2m+2≥n+p, p≥1] refers to at least one organic compound. The above organic compound is not particularly limited; for example, propane, isobutane, etc., are preferred.

[0211] The content of these fluorinated hydrocarbons, the halogenated organic compounds shown in formula (A) and the organic compounds shown in formula (B) is not limited, but the total amount of these compounds relative to the total amount of the refrigerant composition is preferably 0.5% by mass or less, more preferably 0.3% by mass or less, and particularly preferably 0.1% by mass or less.

[0212] 3. Working fluid containing refrigeration oil The working fluid containing refrigeration oil of the present invention comprises at least the refrigerant or refrigerant composition of the present invention and refrigeration oil, and is used as a working fluid in a refrigeration unit. Specifically, the working fluid containing refrigeration oil of the present invention is obtained by mixing refrigeration oil used in the compressor of the refrigeration unit with the refrigerant or refrigerant composition.

[0213] The content of the above-mentioned refrigeration oil is not particularly limited, but is usually 10 to 50% by mass relative to the total working fluid containing refrigeration oil, preferably 12.5 to 45% by mass, more preferably 15 to 40% by mass, even more preferably 17.5 to 35% by mass, and particularly preferably 20 to 30% by mass.

[0214] 3.1 Refrigeration oil In the composition of the present invention, the refrigeration oil may contain one type or two or more types.

[0215] There are no particular limitations on the aforementioned refrigeration oil. Any commonly used refrigeration oil can be appropriately selected. In this case, a refrigeration oil that is superior in improving the miscibility with the mixture of the refrigerant of the present invention (the mixed refrigerant of the present invention) and the stability of the mixed refrigerant of the present invention can be appropriately selected as needed.

[0216] As the base oil for the aforementioned refrigeration oil, it is preferably selected from at least one of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE).

[0217] In addition to the base oils mentioned above, the aforementioned refrigeration oils may also contain additives.

[0218] The additives mentioned above can be selected from at least one of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoamers.

[0219] From a lubrication point of view, a refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40°C is preferred as the aforementioned refrigeration oil.

[0220] The working fluid containing refrigeration oil of the present invention may further contain at least one additive as needed. Examples of additives include, for instance, compatibilizers.

[0221] 3.2 Compatible Solubilizer In the working fluid containing refrigeration oil of the present invention, the phase solubilizer may be a single type or two or more types.

[0222] There are no particular limitations on the solubilizers used above; any commonly used solubilizer can be appropriately selected.

[0223] Examples of such compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Among these, polyoxyalkylene glycol ethers are preferred.

[0224] Example The following examples provide a more detailed description. However, the present invention is not limited to these examples.

[0225] <Examples 1-25, Comparative Examples 1-7 and Reference Example 1> The GWP of the mixed refrigerants shown in the various embodiments, comparative examples and reference examples was evaluated based on the values ​​in the IPCC 4th Report and IPCC 5th Report.

[0226] The GWPs for R410A (R32 / R125 = 50 / 50 mass%), R32 (R32 = 100 mass%), R452B (R32 / R125 / R1234yf = 67 / 7 / 26 mass%), R454B (R32 / R1234yf = 68.9 / 31.1 mass%) and R447B (R32 / R125 / R1234ze(E) = 68 / 8 / 24 mass%) are also evaluated based on the values ​​in the IPCC Fourth Report or the IPCC Fifth Report.

[0227] The COP and refrigeration capacity of the mixed refrigerants shown in each embodiment, comparative example, and Reference Example 1, as well as the COP and refrigeration capacity of R410A, R32, R452B, R454B, and R447B, were obtained by performing theoretical calculations of the refrigeration cycle of the mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 9.0) under the following conditions.

[0228] Evaporation temperature 45℃ Condensation temperature 5℃ Superheating temperature 5K Supercooling temperature 5K Compressor efficiency 70% The GWP, COP, and cooling capacity calculated based on these results are shown in Tables 1-3 below. In Tables 1-3, the COP ratio and cooling capacity ratio are expressed as percentages relative to R410A.

[0229] The coefficient of performance (COP) for cooling is calculated using the following formula.

[0230] COP = (Cooling or Heating Capacity) / Power Consumption The flammability of mixed refrigerants is determined by measuring the combustion rate according to ANSI / ASHRAE 34-2013, using the mixture composition of the refrigerants as the WCF concentration. A combustion rate of 0 cm / s to 10 cm / s is classified as "2L Class (Slightly Flammable)," while no flame propagation is classified as "Class 1 (Non-flammable)." The "ASHRAE Flammability Classification" in Table 1 below represents the results based on this criterion.

[0231] The combustion rate test was conducted as follows. First, the mixed refrigerant used was kept at a purity of 99.5% or higher, and cycles of freezing, degassing, and thawing were repeatedly performed until no trace of air was visible on the vacuum gauge, thus degassing the refrigerant. The combustion rate was determined using a closed-circuit method. The initial temperature was ambient temperature. Ignition was achieved by generating an electric spark between the electrodes at the center of the sample cell. The discharge duration was 1.0–9.9 ms, and the ignition energy was typically approximately 0.1–1.0 J. The flame spread was visualized using schlieren photography. A cylindrical container (inner diameter: 155 mm, length: 198 mm) with two transparent acrylic windows was used as the sample cell, and a xenon lamp was used as the light source. Schlieren images of the flame were recorded at 600 fps using a high-speed digital camera and stored on a PC.

[0232] The flammability range of the mixed refrigerant was determined using a testing apparatus based on ASTM E681-09 (see reference). Figure 3 ).

[0233] Specifically, in order to visually observe and videotape the combustion process, a 12-liter spherical glass flask was used. When excessive pressure was generated in the flask due to combustion, gas was released from the top lid. Ignition was achieved using a discharge from an electrode positioned at a height of one-third of the way from the bottom. The test conditions for Examples 1-3, Comparative Examples 1-2, and Reference Example 1 are described below.

[0234] <Experimental Conditions> Test container: 280mmφ spherical (internal volume: 12 liters) Test temperature: 60℃±3℃ Pressure: 101.3 kPa ± 0.7 kPa Moisture content (under high temperature and high humidity conditions): 0.0187g ± 0.0005g per 1g of dry air (moisture content at 36℃ and 50% relative humidity). Refrigerant composition / air mixing ratio: changed by 1 vol.% ± 0.2 vol.% each time. Refrigerant composition mixing: ±0.1% by mass Ignition method: AC discharge, voltage 15kV, current 30mA, neon transformer Electrode spacing: 6.4 mm (1 / 4 inch) Spark duration: 0.4 seconds ± 0.05 seconds Judgment criteria: • When the flame spreads beyond 90 degrees Celsius from the center of the fire, it is considered flame propagation (combustible). • If the flame spreads below 90 degrees Celsius from the center of the fire, the flame does not propagate (it does not burn). The test conditions for Examples 4-25, Comparative Examples 3-7, and Reference Example 1 are as follows.

[0235] The “Burning tests using the ASTM method” in Tables 2 and 3 below represent results based on the judgment criteria described in the following test conditions.

[0236] <Experimental Conditions> Test container: 280mmφ spherical (internal volume: 12 liters) Test temperature: 60℃±3℃ Pressure: 101.3 kPa ± 0.7 kPa Moisture content: 0.0088g ± 0.0005g per 1g of dry air (moisture content at 50% relative humidity at 23℃) Refrigerant composition / air mixing ratio: changed by 1 vol.% ± 0.2 vol.% each time. Refrigerant composition mixing: ±0.1% by mass Ignition method: AC discharge, voltage 15kV, current 30mA, neon transformer Electrode spacing: 6.4 mm (1 / 4 inch) Spark duration: 0.4 seconds ± 0.05 seconds Judgment criteria: • When the flame spreads beyond 90 degrees Celsius from the center of the fire, it is considered flame propagation (combustible). • If the flame spreads below 90 degrees Celsius from the center of the fire, the flame does not propagate (it does not burn). [Table 1] [Table 2] [Table 3] Symbol Explanation 1. Feeding pipe 2. Sampling tube 3. Thermometer 4. Pressure gauge 5. Electrodes 6. Agitator blades (made of PTFE) A: Non-flammable, R1234yf concentration (mass%) is 1% by mass. B: Non-flammable, with a cooling capacity that is 85% of the mass of R410A. C: The AR5 benchmark GWP is 2000, and its cooling capacity is 85% of that of R410A by weight. D: The mass ratio of AR5 standard GWP of 2000 and R1234yf concentration (mass%) of 1% mass. E: AR4 benchmark GWP is 2000, and its cooling capacity is 85% of that of R410A by weight. F: The mass ratio of AR4 standard GWP of 2000 and R1234yf concentration (mass%) of 1% mass. G: Non-flammable, with a cooling capacity that is 90% of that of R410A by weight. H: The GWP of AR4 is 2000, and its cooling capacity is 90% of that of R410A. a: Non-combustible boundary line b: A straight line representing the cooling capacity relative to 85% of the mass of R410A. c: Represents the straight line indicating the GWP (Gross Power Count) of the AR5 benchmark reaching 2000. d: Represents the straight line showing the mass ratio at which the concentration (mass%) of R1234yf reaches 1 mass%. e: Represents the straight line indicating the GWP (Gross Power Count) of the AR4 benchmark reaching 2000. f: A straight line representing the cooling capacity relative to 90% of the mass of R410A. P: Non-flammable, R1234ze(E) concentration (mass%) is 1 mass% of the mass ratio. Q: Non-flammable, with a cooling capacity that is 85% of that of R410A by weight. R: AR5 benchmark GWP is 2000, and its cooling capacity is 85% of that of R410A by weight. S: The GWP of AR5 is 2000, and the concentration (mass%) of R1234ze(E) is 1% by mass. T: AR4 benchmark GWP is 2000, and its cooling capacity is 85% of that of R410A by weight. U: The GWP of AR4 standard is 2000, and the concentration (mass%) of R1234ze(E) is 1 mass% of the mass ratio. V: Non-flammable, with a cooling capacity that is 90% of that of R410A by weight. W: The AR4 benchmark GWP is 2000, and its cooling capacity is 90% of that of the R410A. g: Non-combustible boundary line h: A straight line representing the cooling capacity relative to 85% of the mass of R410A. i: Represents the straight line indicating the GWP (Gross Power) ratio at which the AR5 benchmark reaches 2000. j: Represents the straight line where the concentration (mass%) of R1234ze(E) reaches 1 mass% of the mass ratio. k: Represents the straight line where the GWP reaches 2000 based on the AR4 benchmark. l: A straight line representing the cooling capacity relative to 90% of the mass of R410A.

Claims

1. A composition containing a refrigerant, characterized in that, The refrigerant contains difluoromethane R32, pentafluoroethane R125, and trans-1,3,3,3-tetrafluoropropylene R1234ze(E), and the total concentration of these three components in the refrigerant is 99.5% by mass or more. Furthermore, the mass ratio of these three components is within the region enclosed by the quadrilateral with the following four points as vertices: P, Q, R, and S, in the triangular composition diagram with these three components as vertices. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point R (R32 / R125 / R1234ze (E) = 29.9 / 56.7 / 13.4 mass%) Point S (R32 / R125 / R1234ze (E) = 45.8 / 53.2 / 1.0 mass%).

2. The composition of claim 1, wherein it is a composition containing a refrigerant, characterized in that, The refrigerant contains R32, R125, and R1234ze(E), and the total concentration of these three components in the refrigerant is 99.5% by mass or more. Furthermore, the mass ratio of these three components is within the region enclosed by the quadrilateral with the following four points as vertices: P, Q, T, and U, in the triangular composition diagram with these three components as vertices. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point Q (R32 / R125 / R1234ze (E) = 44.0 / 30.3 / 25.7 mass%) Point T (R32 / R125 / R1234ze (E) = 33.4 / 50.6 / 16.0 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

3. The composition of claim 1, wherein it is a composition containing a refrigerant, characterized in that, The refrigerant contains R32, R125, and R1234ze(E), and the total concentration of these three components in the refrigerant is 99.5% by mass or more. Furthermore, the mass ratio of these three components is within the region enclosed by the quadrilateral with the following four points as vertices: P, V, W, and U, in the triangular composition diagram with these three components as vertices. Point P (R32 / R125 / R1234ze (E) = 62.2 / 36.8 / 1.0 mass%) Point V (R32 / R125 / R1234ze (E) = 49.0 / 32.0 / 19.0 mass%) Point W (R32 / R125 / R1234ze (E) = 39.2 / 49.5 / 11.3 mass%) Point U (R32 / R125 / R1234ze (E) = 51.9 / 47.1 / 1.0 mass%).

4. The composition according to any one of claims 1 to 3, characterized in that, The refrigerant is used as an alternative to R410A.

5. The composition according to any one of claims 1 to 3, characterized in that, It contains at least one substance selected from water, tracer, ultraviolet fluorescent dye, stabilizer and polymerization inhibitor.

6. The composition according to any one of claims 1 to 3, characterized in that, It also contains refrigeration oil, and the composition is used as a working fluid for refrigeration equipment.

7. A freezing method, characterized in that, The process includes operating a freezing cycle using the composition of any one of claims 1 to 3.

8. A refrigeration apparatus, characterized in that, The composition according to any one of claims 1 to 3 is used as the working fluid.

9. The refrigeration apparatus as claimed in claim 8, characterized in that, The refrigeration device includes air conditioning equipment, refrigerator, cold storage, water chiller, ice maker, refrigerated cabinet, freezer, refrigeration unit, refrigeration unit for cold storage warehouse, vehicle-mounted air conditioning equipment, turbine refrigeration unit, or screw refrigeration unit.

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