RU2832046C2 - Composition containing refrigerant and method of cooling using said composition, method of operating refrigerating device and refrigerating device - Google Patents

Abstract

FIELD: refrigerating or freezing equipment.

SUBSTANCE: invention relates to a cooling method involving operation of a refrigeration cycle in which the evaporation temperature is from −75 °C to −5 °C, using a refrigerant composition containing a refrigerant and water. Coolant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), where HFO-1132 (E) is present in amount of 35.0 to 65.0 wt.%, and HFO-1234yf is present in amount of 65.0 to 35.0 wt.% based on total weight of HFO-1132 (E) and HFO-1234yf. Invention also relates to embodiments of a refrigerant composition, a method of cooling, a method of operating a refrigerating device and a refrigerating device.

EFFECT: composition has a refrigerating coefficient (RC (COP)) and a refrigerating capacity equivalent to or higher than the refrigerating coefficient and refrigerating capacity of R404A and R134a, and has a sufficiently low GWP.

23 cl, 1 dwg, 13 tbl

Description

Field of technology

[0001]

The present invention relates to a composition containing a refrigerant and to a method of refrigeration, a method of operating a refrigeration apparatus and a refrigeration apparatus, all of which use the composition.

State of the art

[0002]

In the context of the worldwide discussion about global warming as a very serious problem, the development of environmentally friendly air conditioners, refrigeration equipment, etc. is becoming increasingly important.

[0003]

At present, various mixed refrigerants that have low global warming potential (GWP) and that can replace R404A used as a refrigerant for air conditioners such as home air conditioners have been proposed. For example, Patent Document (PTL) 1 and PD 2 disclose a refrigerant composition containing difluoromethane (R32), pentafluoroethane (R125), 2,3,3,3-tetrafluoropropane (R1234yf), and 1,1,1,2-tetrafluoroethane (R134a) as an alternative refrigerant to R404A.

[0004]

In addition, various mixed refrigerants have been proposed that have low GWP and that can replace 1,1,1,2-tetrafluoroethane (HFC-134a or R134a) used as a refrigerant for air conditioners such as home air conditioners (e.g. PD 3).

Citation list

Patent document

[0005]

PD 1: WO 2010/059677

PD 2: WO 2011/163117

PD 3: WO 2005/105947

The essence of the invention

Technical task

[0006]

An object of the present invention is to provide a composition comprising a refrigerant having a coefficient of performance (COP) and a refrigerating capacity (which may be expressed as "cooling capacity" or "performance") equivalent to or higher than the COP and refrigerating capacity of R404A and having a sufficiently low GWP. Another object of the present invention is to provide a composition comprising a refrigerant having a coefficient of performance (COP) and a refrigerating capacity (which may be expressed as "cooling capacity" or "performance") equivalent to or higher than the COP and refrigerating capacity of R404A and having a sufficiently low GWP. Yet another object of the present invention is to provide a refrigeration method, a method of operating a refrigeration apparatus and a refrigeration apparatus, all of which use the above-mentioned composition.

Solution to the problem

[0007]

The present description provides the invention according to the following embodiments.

Point 1.

A composition containing a refrigerant,

wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 35.0 to 65.0 wt.%, and HFO-1234yf is present in an amount of from 65.0 to 35.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf, and

where the refrigerant is intended for use in a refrigeration cycle in which the evaporation temperature is between -75 and -5°C.

Point 2.

The composition according to paragraph 1, wherein HFO-1132(E) is present in an amount of from 41.3 to 53.5 wt.%, and HFO-1234yf is present in an amount of from 58.7 to 46.5 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 3.

The composition according to item 1 or 2, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 4.

A composition containing a refrigerant,

wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 40.5 to 49.2 wt.%, and HFO-1234yf is present in an amount of from 59.5 to 50.8 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 5.

The composition according to item 4, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 6.

A composition according to item 4 or 5, wherein the refrigerant is intended for use in a refrigeration cycle in which the evaporation temperature is from -75 to 15°C.

Item 7.

A composition according to any of paragraphs 1 to 6, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507 or R513A.

Item 8.

A composition containing a refrigerant,

wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 31.1 to 39.8 wt.%, and HFO-1234yf is present in an amount of from 68.9 to 60.2 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 9.

The composition according to paragraph 8, wherein HFO-1132(E) is present in an amount of from 31.1 to 37.9% by weight, and HFO-1234yf is present in an amount of from 68.9 to 62.1% by weight, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 10.

The composition according to item 8 or 9, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 11.

The composition according to any of paragraphs 8 to 10, wherein the refrigerant is intended for use in a refrigeration cycle in which the evaporation temperature is from -75 to 15°C.

Item 12.

A composition according to any of paragraphs 8 to 11, which is intended for use as an alternative refrigerant for R134a, R1234yf or CO2 (R744).

Item 13.

A composition containing a refrigerant,

wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 21.0 to 28.4 wt.%, and HFO-1234yf is present in an amount of from 79.0 to 71.6 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 14.

The composition according to item 13, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 15.

A composition according to paragraph 13 or 14, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze.

Item 16.

A composition containing a refrigerant,

wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 12.1 to 72.0 wt.%, and HFO-1234yf is present in an amount of from 87.9 to 28.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf, and

where the refrigerant is intended for use in the air conditioning system of vehicles.

Item 17.

The composition according to claim 16, wherein the air conditioning system is intended for vehicles with a gasoline engine, hybrid vehicles, electric vehicles or hydrogen vehicles.

Item 18.

The composition according to item 16 or 17, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 19.

A composition according to any of paragraphs 16 to 18, which is intended for use as an alternative refrigerant for R12, R134a or R1234yf.

Item 20.

A composition according to any one of paragraphs 1-19, comprising at least one substance selected from the group consisting of water, tracers, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors.

Item 21.

A composition according to any of paragraphs 1-20, wherein the composition additionally contains a refrigeration oil and is intended for use as a working fluid in a refrigeration apparatus.

Item 22.

The composition according to claim 21, wherein the refrigeration oil comprises at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE) and polyvinyl ether (PVE).

Item 23.

A method of cooling comprising operating a refrigeration cycle using a composition according to any of paragraphs 1-22.

Item 24.

A method of cooling comprising operating a refrigeration cycle in which the evaporation temperature is from -75 to -5°C using a composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 35.0 to 65.0 wt.%, and HFO-1234yf is present in an amount of from 65.0 to 35.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 25.

The cooling method according to paragraph 24, wherein HFO-1132(E) is present in an amount of from 41.3 to 53.5 wt.%, and HFO-1234yf is present in an amount of from 58.7 to 46.5 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 26.

The refrigeration method according to paragraphs 24 or 25, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 27.

A method of cooling comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 40.5 to 49.2 wt.%, and HFO-1234yf is present in an amount of from 59.5 to 50.8 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 28.

The cooling method according to item 27, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 29.

The cooling method according to paragraph 27 or 28, wherein the refrigerant has an evaporation temperature of from -75 to 15°C in the refrigeration cycle.

Item 30.

A method of cooling comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 31.1 to 39.8 wt.%, and HFO-1234yf is present in an amount of from 68.9 to 60.2 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 31.

The cooling method according to paragraph 30, wherein HFO-1132(E) is present in an amount of from 31.1 to 37.9 wt.%, and HFO-1234yf is present in an amount of from 68.9 to 62.1 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 32.

The refrigeration method according to item 30 or 31, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 33.

A refrigeration method according to any of paragraphs 30-32, wherein the refrigerant has an evaporation temperature of from -75 to 15°C in the refrigeration cycle.

Item 34.

A method of cooling comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 21.0 to 28.4 wt.%, and HFO-1234yf is present in an amount of from 79.0 to 71.6 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

Item 35.

The cooling method according to item 34, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 36.

A method of cooling comprising operating a refrigeration cycle using a composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf),

wherein HFO-1132(E) is present in an amount of from 12.1 to 72.0 wt.%, and HFO-1234yf is present in an amount of from 87.9 to 28.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf, and wherein the refrigerant is intended for use in an air conditioning system for vehicles.

Item 37.

The cooling method according to paragraph 36, wherein the air conditioning system is intended for gasoline-powered vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles.

Item 38.

The refrigeration method according to item 36 or 37, wherein the refrigerant consists of HFO-1132(E) and HFO-1234yf.

Item 39.

A method of operating a refrigeration apparatus designed with the possibility of carrying out a refrigeration cycle using a composition according to any of paragraphs 1-22.

Item 40.

A refrigeration apparatus containing a composition according to any one of paragraphs 1-22 as a working fluid.

Item 41.

A refrigeration apparatus according to item 40, which is an air-conditioning system, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerated display case, a freezer display case, a freezing and refrigeration unit, a refrigeration machine for freezing and refrigerating warehouses, an air-conditioning system for vehicles, a turbo refrigeration unit or a screw refrigeration machine.

Item 42.

A composition according to any of paragraphs 1 to 22, which is intended for use as a refrigerant.

Item 43.

A composition according to paragraph 42, which is intended for use as a coolant in a refrigeration apparatus.

Item 44.

The composition according to item 43, wherein the refrigeration apparatus is an air conditioning system, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerated display case, a freezer display case, a freezing and refrigeration unit, a refrigeration machine for freezing and refrigerated warehouses, an air conditioning system for vehicles, a turbo refrigeration unit or a screw refrigeration machine.

Item 45.

Use of a composition according to any of paragraphs 1-22 as a coolant.

Item 46.

Use in accordance with paragraph 45 in a refrigeration appliance.

Item 47.

Use according to item 46, where the refrigeration apparatus is an air conditioning system, a refrigerator, a freezer, a water chiller, an ice maker, a refrigerated display case, a freezer display case, a freezing and refrigeration unit, a refrigeration machine for freezer and cold storage warehouses, an air conditioning system for vehicles, a turbo refrigeration unit or a screw refrigeration machine.

Positive effects of the invention

[0008]

The composition containing the refrigerant according to the present invention is characterized by having a coefficient of performance (COP) and a refrigerating capacity equivalent to or higher than the coefficient of performance and refrigerating capacity of R404A, and has a sufficiently low GWP. In addition, the composition containing the refrigerant according to the present invention is characterized by having a coefficient of performance (COP) and a refrigerating capacity equivalent to or higher than the coefficient of performance and refrigerating capacity of R134a, and has a sufficiently low GWP.

Brief description of the drawings

[0009]

FIG. 1 is a diagram illustrating an experimental setup for evaluating flammability (flammable or nonflammable).

Description of embodiments

[0010]

In order to solve the above problem, intensive research was conducted and it was found that a composition containing a mixed refrigerant containing trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf) has the above characteristics.

[0011]

The present invention has been made as a result of further studies based on the above findings. The present invention covers the following embodiments.

[0012]

Definition of terms

A numerical range expressed using "up to" in this specification indicates a range that includes the numerical values before and after "up to", given as minimum and maximum values, respectively.

[0013]

In this description, the terms "comprises" and "includes" include the concepts of "consisting essentially of" and "consisting of."

[0014]

In this specification, the term "refrigerant" includes at least compounds that are defined in ISO817 (International Organization for Standardization) and that have been assigned a refrigerant number (ASHRAE number) indicating the type of refrigerant with the letter "R" at the beginning; and also includes refrigerants that have characteristics equivalent to those of such refrigerants, even if a refrigerant number has not yet been assigned.

[0015]

Refrigerants are broadly divided into fluorocarbon-based compounds and non-fluorocarbon compounds in terms of compound structure. Fluorocarbon compounds include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Non-fluorocarbon compounds include propane (R290), propylene (R1270), butane (R600), isobutane (R600a), carbon dioxide (R744), ammonia (R717), etc.

[0016]

The term "refrigerant-containing composition" as used in the present description at least includes:

(1) the refrigerant itself (including a mixture of refrigerants, i.e., mixed refrigerant);

(2) a composition that can be used to obtain a working fluid for a refrigeration apparatus by additionally including one or more other components and mixing with at least a refrigeration oil;

(3) working fluid for a refrigeration apparatus containing refrigeration oil.

[0017]

Of these three forms, the composition (2) is referred to as a "refrigerant composition" in the present description to distinguish it from the refrigerant itself (including the mixed refrigerant). In addition, the working fluid for the refrigeration apparatus (3) is referred to as a "working fluid containing refrigeration oil" to distinguish it from the "refrigerant composition".

[0018]

In the present description, when using the term "alternative" in the context in which the first coolant is replaced by a second coolant, the first type of alternative means that the equipment designed to operate using the first coolant can operate using the second coolant under optimal conditions, optionally with only a small number of components (at least one of the following: refrigeration oil, gasket, packing, expansion valve, dryer, other parts) and equipment adjustments. In other words, this type of alternative means that the same equipment operates with an alternative coolant. Embodiments of this type of alternative include a built-in alternative, a near-built alternative and partial modifications, in the order in which the degree of change and adjustment required to replace the first coolant with the second coolant is small.

[0019]

The term "alternative" also includes a second type of alternative, which means that equipment designed to use a second refrigerant operates in the same application as an existing application of the first refrigerant, using the second refrigerant. This type of alternative means that the same application is achieved using an alternative refrigerant.

[0020]

In this description, the term "refrigeration apparatus" in a broad sense refers to apparatuses in general that take heat from an object or space, making its temperature lower than the temperature of the surrounding air, and maintain a low temperature. In other words, refrigeration apparatuses in a broad sense refer to converting devices that receive energy from the outside to perform work and that perform energy conversion to transfer heat from a place where the temperature is lower to a place where the temperature is higher. In this description, "refrigeration apparatus" in a broad sense is synonymous with "heat pump".

[0021]

In the present invention, the term "refrigeration apparatus" is distinguished from the term "heat pump" in a narrow sense depending on the difference between the applied temperature range and the operating temperature. In this case, the apparatus whose low-temperature heat source is in a temperature range lower than the air temperature can be called a "refrigeration apparatus", while the apparatus whose low-temperature heat source is close to the air temperature in order to use the heat release caused by starting the refrigeration cycle can be called a "heat pump". In addition, there are such apparatuses that have both the function of refrigeration devices in a narrow sense and the function of heat pumps in a narrow sense, although they are one machine, for example, air conditioners that provide both a cooling mode and a heating mode. In the present description, unless otherwise specified, the terms "refrigeration apparatus" and "heat pump" are used in a broad sense throughout the description.

[0022]

In the present description, the term "temperature hysteresis" can be rephrased as the absolute value of the difference between the start temperature and the end temperature of the phase transition process of the composition containing the refrigerant according to the present invention in the constituent elements of the thermal cycle system.

[0023]

In the present description, the term "air conditioning system for vehicles" is a type of refrigeration device for use in vehicles such as gasoline vehicles, hybrid vehicles, electric vehicles or hydrogen vehicles. The air conditioning system for vehicles refers to a refrigeration device that has a refrigeration cycle in which heat exchange is performed by an evaporator using a liquid refrigerant, the evaporated gaseous refrigerant is absorbed by a compressor, the adiabatically compressed gaseous refrigerant is cooled and liquefied by a condenser, the liquefied refrigerant is adiabatically expanded by passing it through an expansion valve, and then the refrigerant is supplied again as a liquid to the evaporator.

[0024]

In this description, the term "turbo refrigeration machine" means a type of large refrigeration unit-chiller and refers to a refrigeration plant that has a refrigeration cycle in which heat exchange is carried out by an evaporator using a liquid refrigerant, the evaporated gaseous refrigerant is absorbed by a centrifugal compressor, the adiabatically compressed gaseous refrigerant is cooled and liquefied by a condenser, the liquefied refrigerant is adiabatically expanded by passing it through an expansion valve, and then the refrigerant is supplied again as a liquid to the evaporator. The term "large refrigeration machine-chiller" is a type of chiller and refers to a large air conditioner that is designed to condition the air in a separate section of a building.

[0025]

In this description, the term "saturation pressure" refers to the saturated vapor pressure. In this description, the term "saturation temperature" refers to the saturated vapor temperature.

[0026]

In this description, the expression "evaporation temperature in a refrigeration cycle" refers to the temperature at which the refrigerant liquid absorbs heat and turns into vapor in the evaporation stage of the refrigeration cycle. The evaporation temperature in a refrigeration cycle can be determined by measuring the inlet temperature of the evaporator and/or outlet temperature of the evaporator. The evaporation temperature of a simple refrigerant or an azeotropic refrigerant is constant. However, the evaporation temperature of a non-azeotropic refrigerant is the average of the inlet temperature of the evaporator and the dew point temperature. More specifically, the evaporation temperature of a non-azeotropic refrigerant can be calculated using the following equation:

Evaporation temperature = (evaporator inlet temperature + dew point temperature)/2.

[0027]

In this description, the term "discharge temperature" refers to the temperature of the mixed refrigerant at the compressor outlet.

[0028]

In this description, the term "evaporation pressure" refers to the saturation pressure at the evaporation temperature. In this description, the term "condensation pressure" refers to the saturation pressure at the condensation temperature.

[0029]

In this description, the term "critical temperature" refers to the temperature at the critical point and the temperature boundary; that is, until the temperature is equal to or lower than the critical temperature, the gas will not be converted into a liquid by compression of the gas.

[0030]

In this description, the term "non-flammable" refrigerants refers to refrigerants whose worst case flammability composition (WCF), which corresponds to the most flammable point in the allowable concentration range of the refrigerant in accordance with US ANSI/ASHRAE Standard 34-2013, is classified as Class 1.

[0031]

As used herein, the term "flame-resistant refrigerants" refers to refrigerants whose WCF composition is classified as Class 2L according to ANSI/ASHRAE Standard 34-2013.

[0032]

As used herein, the term "flammable refrigerants" refers to refrigerants whose WCF composition is classified as Class 2 according to ANSI/ASHRAE Standard 34-2013.

[0033]

In this description, GWP (AR4) is estimated based on the values presented in the Fourth Report of the Intergovernmental Panel on Climate Change (IPCC).

[0034]

1. Composition

The composition according to the present invention contains a coolant. Examples of the coolant include Coolant 1, Coolant 2, Coolant 3, Coolant 4 and Coolant 5. Coolant 1, Coolant 2, Coolant 3, Coolant 4 and Coolant 5 are described below. In the present description, the "coolant according to the present invention" refers to Coolant 1, Coolant 2, Coolant 3, Coolant 4 or Coolant 5.

[0035]

1.1 Coolant 1

In an embodiment of the invention, the refrigerant present in the composition according to the present invention comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of from 35.0 to 65.0 wt. %, and HFO-1234yf is present in an amount of from 65.0 to 35.0 wt. %, based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 1".

[0036]

In the present invention, Refrigerant 1 is intended for use in a refrigeration cycle in which the evaporation temperature is from -75 to -5°C.

[0037]

Refrigerant 1 has the attributes described above and therefore has the following characteristics: (1) it has a sufficiently low GWP (100 or less); (2) it has a refrigeration capacity equivalent to or higher than that of R404A; and (3) it has a refrigeration capacity equivalent to or higher than that of R404A.

[0038]

Since Refrigerant 1 contains HFO-1132 (E) in an amount of 35.0 mass% or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 1 has a refrigerating capacity equivalent to or higher than that of R404A. Moreover, since Refrigerant 1 contains HFO-1132 (E) in an amount of 65.0 mass% or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of Refrigerant 1 at a saturation temperature of 40°C in a refrigeration cycle can be maintained within an acceptable range (specifically, 2.10 MPa or less).

[0039]

Refrigerant 1 may have a refrigerating capacity of 95% or more, preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more, compared with the refrigerating capacity of R404A.

[0040]

Since the GWP is 100 or less, Refrigerant 1 can significantly reduce the environmental burden from a global warming perspective compared to other general-purpose refrigerants.

[0041]

In the refrigerant 1, the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle (coefficient of performance (COP)) relative to the COP of R404A is preferably high from the viewpoint of energy efficiency. Specifically, the COP, compared with the COP of R404A, is preferably 98% or more, more preferably 100% or more, and particularly preferably 102% or more.

[0042]

In Refrigerant 1, it is preferable that HFO-1132 (E) is present in an amount of 40.5 to 59.0 mass %, and HFO-1234yf is present in an amount of 59.5 to 41.0 mass %, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigerating capacity of 99% or more relative to the refrigerating capacity of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and therefore is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0043]

In Refrigerant 1, it is more preferable that HFO-1132 (E) is present in an amount of 41.3 to 59.0 mass %, and HFO-1234yf is present in an amount of 58.7 to 41.0 mass %, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigerating capacity of 99.5% or more relative to the refrigerating capacity of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and therefore is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0044]

In Refrigerant 1, it is also preferable that HFO-1132 (E) is present in an amount of 41.3 to 55.0 mass %, and HFO-1234yf is present in an amount of 58.7 to 45.0 mass %, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigerating capacity of 99.5% or more relative to the refrigerating capacity of R404A. Further, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40°C, and therefore is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0045]

In Refrigerant 1, it is particularly preferable that HFO-1132 (E) is present in an amount of 41.3 to 53.5 mass%, and HFO-1234yf is present in an amount of 58.7 to 46.5 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0046]

In Refrigerant 1, it is particularly preferable that HFO-1132 (E) is present in an amount of 41.3 to 51.0 mass%, and HFO-1234yf is present in an amount of 58.7 to 49.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0047]

In Refrigerant 1, it is most preferable that HFO-1132 (E) is present in an amount of 41.3 to 49.2% by weight, and HFO-1234yf is present in an amount of 58.7 to 50.8% by weight, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has the characteristics of a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0048]

In Refrigerant 1, the saturation pressure at a saturation temperature of 40°C is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40°C is within the above range, Refrigerant 1 is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0049]

In Refrigerant 1, the saturation pressure at a saturation temperature of 40°C is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40°C is within the above range, Refrigerant 1 is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0050]

In the present invention, when Refrigerant 1 is used for the operation of the refrigeration cycle, the discharge temperature is preferably 150°C or less, more preferably 140°C or less, even more preferably 130°C or less, and particularly preferably 120°C or less from the viewpoint of extending the service life of the components of a commercially available refrigeration apparatus for R404A.

[0051]

The use of refrigerant 1 for the operation of a refrigeration cycle in which the evaporation temperature is between -75 and -5°C is advantageous in terms of providing a refrigeration capacity equivalent to or higher than that of R404A.

[0052]

In the refrigeration cycle using Refrigerant 1 according to the present invention, when the evaporation temperature exceeds -5°C, the compression ratio becomes less than 2.5, which reduces the efficiency of the refrigeration cycle. In the refrigeration cycle using Refrigerant 1 according to the present invention, when the evaporation temperature is less than -75°C, the evaporation pressure becomes less than 0.02 MPa, which makes it difficult for the refrigerant to be sucked into the compressor. The compression ratio is calculated using the following equation:

Compression ratio = condensation pressure (MPa) / evaporation pressure (MPa).

[0053]

In the refrigeration cycle using Refrigerant 1 of the present invention, the evaporation temperature is preferably -7.5°C or less, more preferably -10°C or less, and even more preferably -35°C or less.

[0054]

In the refrigeration cycle using Refrigerant 1 of the present invention, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0055]

In the refrigeration cycle using Refrigerant 1 according to the present invention, the evaporation temperature is preferably -65°C or more and -5°C or less, more preferably -60°C or more and -5°C or less, even more preferably -55°C or more and -7.5°C or less, and particularly preferably -50°C or more and -10°C or less.

[0056]

In the refrigeration cycle using Refrigerant 1 according to the present invention, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more from the viewpoint of improving the suction of the refrigerant into the compressor.

[0057]

In the refrigeration cycle using Refrigerant 1 according to the present invention, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more from the viewpoint of improving the efficiency of the refrigeration cycle. In the refrigeration cycle using Refrigerant 1 according to the present invention, the compression ratio is preferably 200 or less, more preferably 150 or less, even more preferably 100 or less, and particularly preferably 50 or less from the viewpoint of improving the efficiency of the refrigeration cycle.

[0058]

The refrigerant 1 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% by mass or more. In the present invention, the sum of HFO-1132 (E) and HFO-1234yf 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 of the entire refrigerant 1.

[0059]

The refrigerant 1 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above characteristics are not deteriorated. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less of the entire refrigerant 1. The additional refrigerant is not limited and can be selected from a wide range of known refrigerants widely used in this field. The refrigerant 1 may contain one additional refrigerant or two or more additional refrigerants.

[0060]

It is particularly preferable that the Refrigerant 1 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the Refrigerant 1 is particularly preferably equal to 100% by mass of the entire Refrigerant 1.

[0061]

When Refrigerant 1 is composed of HFO-1132(E) and HFO-1234yf, HFO-1132(E) is typically present in an amount of from 35.0 to 65.0 wt.% and HFO-1234yf is typically present in an amount of from 65.0 to 35.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. Refrigerant 1 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CC equivalent to or higher than that of R404A; and (3) it has a refrigeration capacity equivalent to or higher than that of R404A.

[0062]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 40.5 to 59.0 mass%, and HFO-1234yf is present in an amount of 59.5 to 41.0 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigerating capacity of 99% or more relative to the refrigerating capacity of R404A. In addition, in this case, Refrigerant 1 has a saturation pressure of 1.75 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0063]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 41.3 to 59.0 mass%, and HFO-1234yf is present in an amount of 58.7 to 41.0 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigerating capacity of 99.5% or more relative to the refrigerating capacity of R404A. In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 2.00 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0064]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is also preferable that HFO-1132 (E) is present in an amount of 41.3 to 55.0 mass%, and HFO-1234yf is present in an amount of 58.7 to 45.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has a GWP of 100 or less, a CR of 101% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A. In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.95 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0065]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferable that HFO-1132 (E) is present in an amount of 41.3 to 53.5 mass%, and HFO-1234yf is present in an amount of 58.7 to 46.5 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.94 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0066]

When Refrigerant 1 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferable that HFO-1132 (E) is present in an amount of 41.3 to 51.0 mass%, and HFO-1234yf is present in an amount of 58.7 to 49.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 1 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.90 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0067]

When Refrigerant 1 is composed of HFO-1132(E) and HFO-1234yf, it is most preferable that HFO-1132(E) is present in an amount of 41.3 to 49.2% by mass, and HFO-1234yf is present in an amount of 58.7 to 50.8% by mass, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 1 has properties such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 1 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0068]

1.2 Coolant 2

In an embodiment of the invention, the refrigerant present in the composition according to the present invention comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of from 40.5 to 49.2 wt. %, and HFO-1234yf is present in an amount of from 59.5 to 50.8 wt. %, based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 2".

[0069]

Refrigerant 2 has the above-described features and therefore has the following characteristics: (1) it has a sufficiently low GWP (100 or less); (2) it has a refrigeration coefficient equivalent to or higher than that of R404A; (3) it has a refrigeration capacity equivalent to or higher than that of R404A; and (4) it is flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and therefore is applicable in commercially available refrigeration units for R404A without significant design changes.

[0070]

Since Refrigerant 2 contains HFO-1132 (E) in an amount of 40.5 mass% or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 2 has a refrigerating capacity equivalent to or higher than that of R404A. Moreover, since Refrigerant 2 contains HFO-1132 (E) in an amount of 49.2 mass% or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the saturation pressure of Refrigerant 2 at a saturation temperature of 40°C in a refrigeration cycle can be maintained within an acceptable range (specifically, 2.10 MPa or less).

[0071]

Refrigerant 2 may have a refrigerating capacity of 99% or more, preferably 100% or more, more preferably 101% or more, even more preferably 102% or more, and particularly preferably 103% or more relative to the refrigerating capacity of R404A.

[0072]

Since the GWP is 100 or less, Refrigerant 2 can significantly reduce the environmental burden from a global warming perspective compared to other general-purpose refrigerants.

[0073]

In the refrigerant, the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle (coefficient of performance (COP)) compared to the COP of R404A is preferably high from the viewpoint of energy efficiency. Specifically, the COP relative to the COP of R404A is preferably 98% or more, more preferably 100% or more, even more preferably 101% or more, and particularly preferably 102% or more.

[0074]

In Refrigerant 2, it is preferable that HFO-1132 (E) is present in an amount of 41.3 to 49.2% by mass, and HFO-1234yf is present in an amount of 58.7 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0075]

In the refrigerant, it is preferable that HFO-1132 (E) is present in an amount of 43.0 to 49.2% by mass, and HFO-1234yf is present in an amount of 57.0 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has the characteristics of a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 101% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0076]

In Refrigerant 2, it is also preferable that HFO-1132 (E) is present in an amount of 44.0 to 49.2% by mass, and HFO-1234yf is present in an amount of 56.0 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has properties such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 101% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0077]

In Refrigerant 2, it is particularly preferable that HFO-1132 (E) is present in an amount of 45.0 to 49.2% by mass, and HFO-1234yf is present in an amount of 55.0 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has properties such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 102% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0078]

In Refrigerant 2, it is particularly preferable that HFO-1132 (E) is present in an amount of 45.0 to 48.0 mass%, and HFO-1234yf is present in an amount of 55.0 to 52.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102.5% or more relative to the CR of R404A, and a refrigeration capacity of 102.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0079]

In Refrigerant 2, it is most preferable that HFO-1132 (E) is present in an amount of 45.0 to 47.0 mass%, and HFO-1234yf is present in an amount of 55.0 to 53.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has the characteristics of a GWP of 100 or less, a CR of 102.5% or more relative to the CR of R404A, and a refrigeration capacity of 102.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.85 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0080]

In Refrigerant 2, the saturation pressure at a saturation temperature of 40°C is usually 2.10 MPa or less, preferably 2.00 MPa or less, more preferably 1.95 MPa or less, even more preferably 1.90 MPa or less, and particularly preferably 1.88 MPa or less. If the saturation pressure at a saturation temperature of 40°C is within the above range, Refrigerant 2 is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0081]

In Refrigerant 2, the saturation pressure at a saturation temperature of 40°C is usually 1.70 MPa or more, preferably 1.73 MPa or more, more preferably 1.74 MPa or more, even more preferably 1.75 MPa or more, and particularly preferably 1.76 MPa or more. If the saturation pressure at a saturation temperature of 40°C is within the above range, Refrigerant 2 is applicable to commercially available refrigeration apparatuses for R404A without significant changes in structure.

[0082]

In the present invention, when Refrigerant 2 is used for the operation of the refrigeration cycle, the discharge temperature is preferably 150°C or less, more preferably 140°C or less, even more preferably 130°C or less, and particularly preferably 120°C or less from the viewpoint of extending the service life of the components of a commercially available refrigeration apparatus for R404A.

[0083]

In the present invention, Refrigerant 2 is preferably used for operating a refrigeration cycle in which the evaporation temperature is from -75 to 15°C from the viewpoint of obtaining a refrigeration capacity equivalent to or higher than that of R404A.

[0084]

In the refrigeration cycle using Refrigerant 2 according to the present invention, the evaporation temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less.

[0085]

In the refrigeration cycle using Refrigerant 2 of the present invention, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0086]

In the refrigeration cycle using Refrigerant 2 according to the present invention, the evaporation temperature is preferably -65°C or more and 10°C or less, more preferably -60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and particularly preferably -50°C or more and -5°C or less.

[0087]

In the refrigeration cycle using Refrigerant 2 according to the present invention, the evaporation pressure is preferably 0.02 MPa or more, more preferably 0.03 MPa or more, even more preferably 0.04 MPa or more, and particularly preferably 0.05 MPa or more from the viewpoint of improving the suction of the refrigerant into the compressor.

[0088]

In the refrigeration cycle using Refrigerant 2 according to the present invention, the compression ratio is preferably 2.5 or more, more preferably 3.0 or more, even more preferably 3.5 or more, and particularly preferably 4.0 or more from the viewpoint of improving the efficiency of the refrigeration cycle.

[0089]

The refrigerant 2 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% by mass or more. In the present invention, the sum of HFO-1132 (E) and HFO-1234yf 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 of the entire refrigerant 2.

[0090]

The refrigerant 2 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above characteristics are not deteriorated. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less of the entire refrigerant 2. The additional refrigerant is not limited and can be selected from a wide range of known refrigerants widely used in this field. The refrigerant 2 may contain one additional refrigerant or two or more additional refrigerants.

[0091]

It is particularly preferable that the Refrigerant 2 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the Refrigerant is particularly preferably equal to 100% by mass of the entire Refrigerant 2.

[0092]

When Refrigerant 2 is composed of HFO-1132(E) and HFO-1234yf, HFO-1132(E) is typically present in an amount of 40.5 to 49.2 wt.% and HFO-1234yf is typically present in an amount of 59.5 to 50.8 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. Refrigerant 2 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CC equivalent to or higher than that of R404A; (3) it has a refrigeration capacity equivalent to or higher than that of R404A; and (4) it is flame retardant in accordance with ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.75 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0093]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 41.3 to 49.2% by mass, and HFO-1234yf is present in an amount of 58.7 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 99.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.76 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0094]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is preferable that HFO-1132 (E) is present in an amount of 43.0 to 49.2% by mass, and HFO-1234yf is present in an amount of 57.0 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 101% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.78 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C, and therefore is applicable in commercially available refrigeration apparatus for R404A without significant changes in structure.

[0095]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is also preferable that HFO-1132 (E) is present in an amount of 44.0 to 49.2% by mass, and HFO-1234yf is present in an amount of 56.0 to 50.8% by mass, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has properties such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 101% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.80 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0096]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferable that HFO-1132 (E) is present in an amount of 45.0 to 49.2 mass%, and HFO-1234yf is present in an amount of 55.0 to 50.8 mass%, based on the total mass of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102% or more relative to the CR of R404A, and a refrigeration capacity of 102% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.88 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0097]

When Refrigerant 2 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferable that HFO-1132 (E) is present in an amount of 45.0 to 48.0 mass%, and HFO-1234yf is present in an amount of 55.0 to 52.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 2 has characteristics such as a GWP of 100 or less, a CR of 102.5% or more relative to the CR of R404A, and a refrigeration capacity of 102.5% or more relative to the refrigeration capacity of R404A, and is also flame retardant according to ASHRAE Standards (Class 2L). In addition, in this case, Refrigerant 2 has a saturation pressure of 1.81 MPa or more and 1.87 MPa or less at a saturation temperature of 40°C and is therefore applicable in commercially available refrigeration apparatus for R404A without significant changes in design.

[0098]

1.3 Coolant 3

In an embodiment of the invention, the refrigerant present in the composition according to the present invention comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of from 31.1 to 39.8 wt.%, and HFO-1234yf is present in an amount of from 68.9 to 60.2 wt.%, based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 3".

[0099]

Refrigerant 3 has the above-described features and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has a refrigeration coefficient that is almost equivalent to the refrigeration coefficient of R134a; (3) it has a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a; and (4) the discharge temperature is 90°C or less.

[0100]

Since Refrigerant 3 contains HFO-1132 (E) in an amount of 31.1% by mass or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 3 has a refrigerating capacity of 150% or more relative to the refrigerating capacity of R134a. Moreover, since Refrigerant 3 contains HFO-1132 (E) in an amount of 39.8% by mass or less based on the total mass of HFO-1132 (E) and HFO-1234yf, the discharge temperature of Refrigerant 3 in the refrigeration cycle can be maintained at 90°C or less, and a long service life of the components of the refrigeration system for R134a can be ensured.

[0101]

The refrigerant 3 may have a refrigerating capacity of 150% or more, preferably 151% or more, more preferably 152% or more, even more preferably 153% or more, and particularly preferably 154% or more relative to the refrigerating capacity of R134a.

[0102]

The refrigerant 3 has a discharge temperature of preferably 90.0°C or less, more preferably 89.7°C or less, even more preferably 89.4°C or less, and particularly preferably 89.0°C or less in the refrigeration cycle.

[0103]

Since the GWP is 100 or less, Refrigerant 3 can significantly reduce the environmental burden from a global warming perspective compared to other general-purpose refrigerants.

[0104]

In the refrigerant 3, the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle (coefficient of performance (COP)) relative to the COP of R134a is preferably high from the viewpoint of energy consumption efficiency. Specifically, the COP, compared with the COP of R134a, is preferably 90% or more, more preferably 91% or more, even more preferably 91.5% or more, and particularly preferably 92% or more.

[0105]

In Refrigerant 3, HFO-1132(E) is typically present in an amount of 31.1 to 39.8% by weight, and HFO-1234yf is typically present in an amount of 68.9 to 60.2% by weight, based on the total weight of HFO-1132(E) and HFO-1234yf. Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CC almost equivalent to the CC of R134a; (3) it has a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a; and (4) the discharge temperature is 90.0°C or less.

[0106]

In Refrigerant 3, it is preferable that HFO-1132 (E) is present in an amount of 31.1 to 37.9 mass%, and HFO-1234yf is present in an amount of 68.9 to 62.1 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0107]

In Refrigerant 3, it is more preferable that HFO-1132 (E) is present in an amount of 32.0 to 37.9 mass%, and HFO-1234yf is present in an amount of 68.0 to 62.1 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 151% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less, and (5) the critical temperature is 81°C or more.

[0108]

In Refrigerant 3, it is also preferable that HFO-1132 (E) is present in an amount of 33.0 to 37.9 mass%, and HFO-1234yf is present in an amount of 67.0 to 62.1 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 152% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0109]

In Refrigerant 3, it is even more preferable that HFO-1132 (E) is present in an amount of 34.0 to 37.9 mass% and HFO-1234yf is present in an amount of 66.0 to 62.1 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 153% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0110]

In Refrigerant 3, it is particularly preferable that HFO-1132 (E) is present in an amount of 35.0 to 37.9 mass%, and HFO-1234yf is present in an amount of 65.0 to 62.1 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 155% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0111]

In the present invention, when Refrigerant 3 is used for the operation of the refrigeration cycle, the discharge temperature is preferably 90.0°C or less, more preferably 89.7°C or less, even more preferably 89.4°C or less, and particularly preferably 89.0°C or less from the viewpoint of extending the service life of the components of a commercially available refrigeration apparatus for R134a.

[0112]

In the present invention, when the refrigerant 3 is used for the operation of the refrigeration cycle, the refrigeration cycle requires a liquefaction (condensation) process of the refrigerant; that is, the critical temperature must be remarkably higher than the temperature of the cooling water or the cooling air to liquefy the refrigerant. From this point of view, in the refrigeration cycle in which the refrigerant 3 of the present invention is used, the critical temperature is preferably 80°C or more, more preferably 81°C or more, even more preferably 81.5°C or more, and particularly preferably 82°C or more.

[0113]

In the present invention, Refrigerant 3 is generally used for the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 15°C, from the viewpoint of obtaining a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a.

[0114]

In the refrigeration cycle using the refrigerant 3 according to the present invention, the evaporation temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less.

[0115]

In the refrigeration cycle using Refrigerant 3 of the present invention, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0116]

In the refrigeration cycle using the refrigerant 3 according to the present invention, the evaporation temperature is preferably -65°C or more and 15°C or less, more preferably -60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and particularly preferably -50°C or more and -5°C or less.

[0117]

In the refrigeration cycle using the refrigerant 3 according to the present invention, the critical temperature of the refrigerant is preferably 80°C or more, more preferably 81°C or more, even more preferably 81.5°C or more, and particularly preferably 82°C or more from the viewpoint of improving the performance.

[0118]

The refrigerant 3 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% by mass or more. In the present invention, the sum of HFO-1132 (E) and HFO-1234yf 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 of the entire refrigerant 3.

[0119]

The refrigerant 3 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above characteristics are not deteriorated. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less of the entire refrigerant 3. The additional refrigerant is not limited and can be selected from a wide range of known refrigerants widely used in this field. The refrigerant 3 may contain one additional refrigerant or two or more additional refrigerants.

[0120]

It is particularly preferable that the refrigerant 3 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the refrigerant 3 is particularly preferably equal to 100% by mass of the entire refrigerant 3.

[0121]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, HFO-1132(E) is typically present in an amount of 31.1 to 39.8% by weight and HFO-1234yf is typically present in an amount of 68.9 to 60.2% by weight, based on the total weight of HFO-1132(E) and HFO-1234yf. Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CC almost equivalent to the CC of R134a; (3) it has a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a; and (4) the discharge temperature is 90°C or less.

[0122]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, it is preferable that HFO-1132(E) is present in an amount of 31.1 to 37.9% by mass and HFO-1234yf is present in an amount of 68.9 to 62.1% by mass, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 150% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0123]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, it is more preferable that HFO-1132(E) is present in an amount of 32.0 to 37.9% by mass and HFO-1234yf is present in an amount of 68.0 to 62.1% by mass, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 151% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0124]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, it is even more preferable that HFO-1132(E) is present in an amount of 33.0 to 37.9% by mass and HFO-1234yf is present in an amount of 67.0 to 62.1% by mass, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 152% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0125]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, it is also preferable that HFO-1132(E) is present in an amount of 34.0 to 37.9% by mass and HFO-1234yf is present in an amount of 66.0 to 62.1% by mass, based on the total mass of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigeration capacity of 153% or more relative to the refrigeration capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0126]

When Refrigerant 3 is composed of HFO-1132(E) and HFO-1234yf, it is particularly preferable that HFO-1132(E) is present in an amount of 35.0 to 37.9 mass%, and HFO-1234yf is present in an amount of 65.0 to 62.1 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 3 has the features described above and therefore has the following characteristics: (1) the GWP is sufficiently low (100 or less); (2) it has a CR of 92% or more relative to the CR of R134a; (3) it has a refrigerating capacity of 155% or more relative to the refrigerating capacity of R134a; (4) the discharge temperature is 90.0°C or less; and (5) the critical temperature is 81°C or more.

[0127]

1.4 Coolant 4

In an embodiment of the invention, the refrigerant present in the composition according to the present invention comprises HFO-1132(E) and HFO-1234yf, wherein HFO-1132(E) is present in an amount of from 21.0 to 28.4 wt.%, and HFO-1234yf is present in an amount of from 79.0 to 71.6 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 4."

[0128]

Refrigerant 4 has the above-described features and therefore has the following characteristics: (1) it has a sufficiently low GWP (100 or less); (2) it has a refrigeration coefficient that is almost equivalent to that of R1234yf; (3) it has a refrigeration capacity of 140% or more relative to that of R1234yf; and (4) it is flame retardant according to ASHRAE standards (Class 2L). In addition, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10°C and therefore is applicable in commercially available refrigeration apparatus for R1234yf without significant design changes.

[0129]

Since Refrigerant 4 contains HFO-1132 (E) in an amount of 21.0 mass% or more based on the total mass of HFO-1132 (E) and HFO-1234yf, Refrigerant 4 has a refrigeration capacity of 140% or more relative to that of R1234yf. Moreover, Refrigerant 4 contains HFO-1132 (E) in an amount of 28.4 mass% or less based on the total mass of HFO-1132 (E) and HFO-1234yf. This makes it possible to easily ensure a critical temperature of 83.5°C or more.

[0130]

Refrigerant 4 may have a refrigerating capacity of 140% or more, preferably 142% or more, more preferably 143% or more, even more preferably 145% or more, and particularly preferably 146% or more, relative to the refrigerating capacity of R1234yf.

[0131]

Since the GWP is 100 or less, Refrigerant 4 can significantly reduce the environmental burden from a global warming perspective compared to other general-purpose refrigerants.

[0132]

In the refrigerant 4, the ratio of the refrigeration capacity to the power consumed in the refrigeration cycle (coefficient of performance (COP)) relative to the COP of R1234yf is preferably high from the viewpoint of energy efficiency. Specifically, the COP relative to the COP of R1234yf is preferably 95% or more, more preferably 96% or more, even more preferably 97% or more, and particularly preferably 98% or more.

[0133]

In Refrigerant 4, it is preferable that HFO-1132 (E) is present in an amount of 21.5 to 28.0 mass%, and HFO-1234yf is present in an amount of 78.5 to 72.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0134]

In Refrigerant 4, it is more preferable that HFO-1132 (E) is present in an amount of 22.0 to 27.7 mass%, and HFO-1234yf is present in an amount of 78.0 to 72.3 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0135]

In Refrigerant 4, it is even more preferable that HFO-1132 (E) is present in an amount of 22.5 to 27.5 mass% and HFO-1234yf is present in an amount of 77.5 to 72.5 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; a CC of 98% or more relative to the CC of R1234yf; a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); a discharge temperature of 64.8°C or less; and a critical temperature of 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0136]

In Refrigerant 4, it is particularly preferable that HFO-1132 (E) is present in an amount of 23.0 to 27.2 mass%, and HFO-1234yf is present in an amount of 77.0 to 72.8 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 141% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and therefore is applicable in commercially available refrigeration apparatuses for R1234yf without significant changes in structure.

[0137]

In Refrigerant 4, it is also particularly preferable that HFO-1132 (E) is present in an amount of 23.5 to 27.0 mass %, and HFO-1234yf is present in an amount of 76.5 to 73.0 mass %, based on the total weight of HFO-1132 (E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CR of 98% or more relative to the CR of R1234yf; it has a refrigeration capacity of 142% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0138]

In Refrigerant 4, it is most preferable that HFO-1132(E) is present in an amount of 24.0 to 26.7% by weight and HFO-1234yf is present in an amount of 76.0 to 73.3% by weight, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; a CC of 98% or more relative to the CC of R1234yf; a refrigeration capacity of 144% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); a discharge temperature of 64.6°C or less; and a critical temperature of 84.0°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0139]

In Refrigerant 4, the saturation pressure at a saturation temperature of -10°C is usually 0.420 MPa or less, preferably 0.418 MPa or less, more preferably 0.417 MPa or less, even more preferably 0.415 MPa or less, and particularly preferably 0.413 MPa or less. When the saturation pressure is within this range, Refrigerant 4 is applicable to commercially available refrigeration apparatuses for R1234yf without significant changes in structure.

[0140]

In Refrigerant 4, the saturation pressure at a saturation temperature of -10°C is usually 0.380 MPa or more, preferably 0.385 MPa or more, more preferably 0.390 MPa or more, even more preferably 0.400 MPa or more, and particularly preferably 0.410 MPa or more. In these cases, Refrigerant 4 is applicable to commercially available refrigeration apparatuses for R1234yf without significant changes in structure.

[0141]

In the present invention, when Refrigerant 4 is used for the operation of the refrigeration cycle, the discharge temperature is preferably 65°C or less, more preferably 64.8°C or less, even more preferably 64.7°C or less, and particularly preferably 64.5°C or less from the viewpoint of extending the service life of the components of a commercially available refrigeration apparatus for R1234yf.

[0142]

In the present invention, Refrigerant 4 is preferably used for the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 20°C, from the viewpoint of obtaining a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf.

[0143]

In the refrigeration cycle using Refrigerant 4 of the present invention, the evaporation temperature is preferably 20°C or less, more preferably 15°C or less, even more preferably 10°C or less, and particularly preferably 5°C or less from the viewpoint of obtaining a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf.

[0144]

In the refrigeration cycle using Refrigerant 4 of the present invention, the evaporation temperature is preferably from -75 to 20°C, more preferably from -65 to 15°C, even more preferably from -60 to 10°C, also preferably from -55 to 7.5°C, and particularly preferably from -50 to 5°C, from the viewpoint of obtaining a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf.

[0145]

In the refrigeration cycle using Refrigerant 4 according to the present invention, the evaporation temperature is preferably -75°C or more and 20°C or less, more preferably -65°C or more and 10°C or less, also preferably -60°C or more and 5°C or less, even more preferably -55°C or more and 0°C or less, and particularly preferably -50°C or more and -5°C or less, from the viewpoint of obtaining a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf.

[0146]

In the refrigeration cycle using Refrigerant 4 according to the present invention, the discharge temperature is preferably 65.0°C or less, more preferably 64.9°C or less, even more preferably 64.8°C or less, and particularly preferably 64.7°C or less, from the viewpoint of extending the service life of the components of a commercially available refrigeration apparatus for R1234yf.

[0147]

In the present invention, when the refrigerant 4 is used for the operation of the refrigeration cycle, the refrigeration cycle requires a liquefaction (condensation) process of the refrigerant; that is, the critical temperature must be remarkably higher than the temperature of the cooling water or the cooling air to liquefy the refrigerant. From this point of view, in the refrigeration cycle in which the refrigerant 4 of the present invention is used, the critical temperature is preferably 83.5°C or more, more preferably 83.8°C or more, even more preferably 84.0°C or more, and particularly preferably 84.5°C or more.

[0148]

The refrigerant 4 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above characteristics are not deteriorated. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less of the entire refrigerant 4. The additional refrigerant is not limited and can be selected from a wide range of known refrigerants widely used in this field. The refrigerant 4 may contain one additional refrigerant or two or more additional refrigerants.

[0149]

It is particularly preferable that the refrigerant 4 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the refrigerant 4 is particularly preferably 100% by weight of the entire refrigerant 4.

[0150]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, HFO-1132(E) is typically present in an amount of 21.0 to 28.4 wt.% and HFO-1234yf is typically present in an amount of 79.0 to 71.6 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. Refrigerant 4 has the features described above and therefore has the following characteristics: (1) the GWP is reasonably low (100 or less); (2) it has a CC nearly equivalent to the CC of R1234yf; (3) it has a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; and (4) it is flame retardant according to ASHRAE standards (Class 2L). In addition, in this case, Refrigerant 4 has a saturation pressure of 0.380 MPa or more and 0.420 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0151]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is preferable that HFO-1132(E) is present in an amount of 21.5 to 28.0 mass% and HFO-1234yf is present in an amount of 78.5 to 72.0 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.383 MPa or more and 0.418 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0152]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is more preferable that HFO-1132(E) is present in an amount of 22.0 to 27.7 mass%, and HFO-1234yf is present in an amount of 78.0 to 72.3 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 140% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 65.0°C or less; and the critical temperature is 83.5°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.385 MPa or more and 0.417 MPa or less at a saturation temperature of -10°C, and therefore is applicable in commercially available refrigeration apparatus for R1234yf without significant changes in structure.

[0153]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is even more preferable that HFO-1132(E) is present in an amount of 22.5 to 27.5 mass% and HFO-1234yf is present in an amount of 77.5 to 72.5 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigerating capacity of 140% or more relative to the refrigerating capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.388 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and therefore is applicable to commercially available refrigeration apparatus for R1234yf without significant changes in structure.

[0154]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is particularly preferable that HFO-1132(E) is present in an amount of 23.0 to 27.2 mass%, and HFO-1234yf is present in an amount of 77.0 to 72.8 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CR of 98% or more relative to the CR of R1234yf; it has a refrigeration capacity of 141% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0155]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is also particularly preferable that HFO-1132(E) is present in an amount of 23.5 to 27.0 mass% and HFO-1234yf is present in an amount of 76.5 to 73.0 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CC of 98% or more relative to the CC of R1234yf; it has a refrigeration capacity of 142% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.8°C or less; and the critical temperature is 83.8°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.390 MPa or more and 0.414 MPa or less at a saturation temperature of -10°C, and therefore is applicable to commercially available refrigeration apparatus for R1234yf without significant changes in structure.

[0156]

When Refrigerant 4 is composed of HFO-1132(E) and HFO-1234yf, it is most preferable that HFO-1132(E) is present in an amount of 24.0 to 26.7 mass% and HFO-1234yf is present in an amount of 76.0 to 73.3 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf. In this case, Refrigerant 4 has the following characteristics: a GWP of 100 or less; it has a CR of 98% or more relative to the CR of R1234yf; it has a refrigeration capacity of 144% or more relative to the refrigeration capacity of R1234yf; it is hardly flammable according to ASHRAE standards (Class 2L); the discharge temperature is 64.6°C or less; and the critical temperature is 84.0°C or more. In addition, in this case, Refrigerant 4 has a saturation pressure of 0.396 MPa or more and 0.411 MPa or less at a saturation temperature of -10°C and is therefore applicable in commercially available refrigeration apparatus for R1234yf without significant changes in design.

[0157]

The refrigerant 5 according to the present invention is described below.

[0158]

Technical description

Before describing Refrigerant 5, the differences between gasoline-powered vehicles and electric vehicles and the advantages of heat pumps are discussed.

[0159]

The difference between gasoline powered vehicles and electric powered vehicles

Gasoline-powered vehicles reuse engine exhaust gases to provide warm air for the heating function, while electric vehicles do not have a heat source to reuse and therefore use electricity for heating. In conventional air conditioners with an electric heater, the use of the heater directly results in energy consumption, which significantly reduces the actual driving range. Heat pumps, which heat the interior using the temperature difference between the refrigerant and the outside air, provide a heating effect that is higher than the power consumed, making it possible to heat the interior of the vehicle with less power than before.

[0160]

Advantages of Heat Pumps

In heating, the following steps take place: (a) a stage of compression of the gaseous refrigerant, which is evaporated by absorbing heat from the outside air in the heat exchanger, in the compressor to form a high-temperature, high-pressure gas, and (b) turning the cold air inside the vehicle into warm air by heat exchange and blowing the warm air into the vehicle from the vents of the air conditioner. This corresponds to the reverse cycle with respect to the cycle in which the heat absorbed from the vehicle interior is released from the outside heat exchanger to provide the cooling and heating function in summer. Heat pumps, which can be used for both cooling and heating with a single refrigerant circulation system, feature a higher coefficient of performance (COP) than the COP of heating with conventional electric heaters.

[0161]

1.5 Coolant 5

In an embodiment of the invention, the refrigerant present in the composition according to the present invention comprises HFO-1132 (E) and HFO-1234yf, wherein HFO-1132 (E) is present in an amount of from 12.1 to 72.0 wt. %, and HFO-1234yf is present in an amount of from 87.9 to 28.0 wt. %, based on the total weight of HFO-1132 (E) and HFO-1234yf. This refrigerant may be referred to as "Refrigerant 5."

[0162]

In the present invention, Refrigerant 5 is used for the air conditioning system of vehicles.

[0163]

Refrigerant 5 has the above-described features and therefore has the following characteristics: (1) the GWP is quite low (100 or less); (2) it has a refrigeration coefficient that is almost equivalent to the refrigeration coefficient of R1234yf; (3) it has a refrigeration capacity of 128% or more relative to the refrigeration capacity of R1234yf; and (4) the combustion velocity is less than 10.0 cm/sec.

[0164]

Refrigerant 5 contains HFO-1132 (E) in an amount of 12.1% by mass or more based on the total mass of HFO-1132 (E) and HFO-1234yf. This makes it possible to achieve a boiling point of -40°C or less, which is useful when a vehicle with an electric motor is heated using a heat pump. A boiling point of -40°C or less means that the saturation pressure is equal to or higher than the atmospheric pressure at -40°C. For the above application, a lower boiling point that is not higher than -40°C is preferable.

[0165]

Since the boiling point of HFO-1234yf is -29°C, the saturation pressure at an evaporation temperature of -30°C or less is equal to or less than the atmospheric pressure. Therefore, there is a problem that the heating operation cannot be performed using a heat pump in an electric motor vehicle. Even if the heating operation can be performed, there is a problem that the suction pressure of the compressor is very low, resulting in insufficient performance, requiring a long period of time for heating as a result. In this case, since a heat pump with high heating efficiency cannot be used in an electric motor vehicle, there is a problem that heating must be performed using an inefficient electric heater. In contrast, with a refrigerant having a boiling point of -40°C or less, the heating operation can be performed using a heat pump in an electric motor vehicle at an evaporation temperature of up to -40°C. Therefore, heat pump heating may be possible in electric vehicles in almost all regions of the world.

[0166]

Refrigerant 5 contains HFO-1132(E) in an amount of 72.0% by mass or less, based on the total mass of HFO-1132(E) and HFO-1234yf. This enables a combustion velocity of less than 10.0 cm/sec, which contributes to safety when used in the air conditioning system of vehicles.

[0167]

Refrigerant 5 may have a refrigerating capacity of 128% or more, preferably 130% or more, more preferably 140% or more, even more preferably 150% or more, and particularly preferably 160% or more relative to the refrigerating capacity of R1234yf.

[0168]

Since the GWP is 5 or more and 100 or less, Refrigerant 5 can significantly reduce the environmental burden from a global warming perspective compared to other general-purpose refrigerants.

[0169]

In Refrigerant 5, the ratio of the cooling capacity to the power consumed in the refrigeration cycle (coefficient of performance (COP)) relative to R1234yf can be 100% or more in terms of energy efficiency.

[0170]

Using refrigerant 5 for vehicle air conditioning systems provides heating via a heat pump, which uses less energy than electric heaters.

[0171]

The air conditioning system using Refrigerant 5 is preferably for gasoline-powered vehicles, hybrid vehicles, electric-powered vehicles, or hydrogen-powered vehicles. From the viewpoint of improving the travel distance of a vehicle when the interior of the vehicle is heated by a heat pump, the air conditioning system using Refrigerant 5 is particularly preferable for electric-powered vehicles among others. More specifically, in the present invention, Refrigerant 5 is particularly preferably used in the case of electric-powered vehicles.

[0172]

In the present invention, Refrigerant 5 is used for air conditioning systems of vehicles. In the present invention, Refrigerant 5 is preferably used for air conditioning systems for vehicles with a gasoline engine, air conditioning systems for hybrid vehicles, air conditioning systems for vehicles with an electric motor, or air conditioning systems for hydrogen vehicles. In the present invention, Refrigerant 5 is particularly preferred in air conditioning systems for vehicles with an electric motor.

[0173]

In the present invention, Refrigerant 5 is preferably used for a refrigeration apparatus for vehicles such as gasoline-powered vehicles, hybrid vehicles, plug-in hybrid vehicles, electric-powered vehicles, hydrogen-powered vehicles, and fuel cell vehicles. Of these, Refrigerant 5 is particularly preferably used for a refrigeration apparatus for electric-powered vehicles that cannot utilize the exhaust heat of the engine.

[0174]

In addition, in a situation in which the heat of the engine exhaust gases cannot be utilized, such as due to a malfunction of the thermostat when starting the engine, the use of heat pump heating with Refrigerant 5 can immediately heat the interior of vehicles even when the vehicles are gasoline-powered vehicles, hybrid vehicles, plug-in hybrid vehicles, hydrogen vehicles, and fuel cell vehicles.

[0175]

In the present invention, the refrigerant 5 has a boiling point of preferably -51.2 to -40.0°C, more preferably -50.0 to -42.0°C, and even more preferably -48.0 to -44.0°C, since at -40°C a pressure equal to or higher than the atmospheric pressure is required when heating the interior of a vehicle using a heat pump.

[0176]

In Refrigerant 5, it is preferred that HFO-1132(E) is present in an amount of 15.0 to 65.0 wt.%, and HFO-1234yf is present in an amount of 85.0 to 35.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0177]

In Refrigerant 5, it is more preferred that HFO-1132(E) is present in an amount of 20.0 to 55.0 wt.%, and HFO-1234yf is present in an amount of 80.0 to 45.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0178]

In Refrigerant 5, it is even more preferred that HFO-1132(E) is present in an amount of 25.0 to 50.0 wt.%, and HFO-1234yf is present in an amount of 75.0 to 50.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0179]

In Refrigerant 5, it is particularly preferred that HFO-1132 (E) is present in an amount of 30.0 to 45.0 mass%, and HFO-1234yf is present in an amount of 70.0 to 55.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0180]

In Refrigerant 5, it is most preferred that HFO-1132(E) is present in an amount of 35.0 to 40.0 wt.% and HFO-1234yf is present in an amount of 65.0 to 60.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0181]

In the present invention, the combustion speed of the refrigerant 5 is preferably less than 10.0 cm/sec, more preferably less than 5.0 cm/sec, even more preferably less than 3.0 cm/sec, and particularly preferably less than 2.0 cm/sec.

[0182]

In the present invention, Refrigerant 5 is preferably used for operating a refrigeration cycle in which the evaporation temperature is from -40 to 10°C, from the viewpoint of obtaining a refrigeration capacity equivalent to or higher than that of R1234yf.

[0183]

In the present invention, when Refrigerant 5 is used for the operation of the refrigeration cycle, the discharge temperature is preferably 79°C or less, more preferably 75°C or less, even more preferably 70°C or less, and particularly preferably 67°C or less.

[0184]

The refrigerant 5 may contain HFO-1132 (E) and HFO-1234yf in such an amount that the sum of their concentrations is usually 99.5% by mass or more. In the present invention, the sum of HFO-1132 (E) and HFO-1234yf 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 of the entire refrigerant 5.

[0185]

The refrigerant 5 may also contain an additional refrigerant in addition to HFO-1132 (E) and HFO-1234yf, as long as the above characteristics are not deteriorated. In this case, the content of the additional refrigerant is preferably 0.5 mass % or less, more preferably 0.3 mass % or less, even more preferably 0.2 mass % or less, and particularly preferably 0.1 mass % or less of the entire refrigerant 5. The additional refrigerant is not limited and can be selected from a wide range of known refrigerants widely used in this field. The refrigerant 5 may contain one additional refrigerant or two or more additional refrigerants.

[0186]

It is particularly preferable that the refrigerant 5 consists of HFO-1132 (E) and HFO-1234yf. In other words, the total concentration of HFO-1132 (E) and HFO-1234yf in the refrigerant 5 is particularly preferably 100% by mass of the entire refrigerant 5.

[0187]

When Refrigerant 5 consists of HFO-1132(E) and HFO-1234yf, HFO-1132(E) is typically present in an amount of 12.1 to 72.0 wt.%, and HFO-1234yf is typically present in an amount of 87.9 to 28.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0188]

When Refrigerant 5 is composed of HFO-1132(E) and HFO-1234yf, it is preferred that HFO-1132(E) is present in an amount of 15.0 to 65.0 mass%, and HFO-1234yf is present in an amount of 85.0 to 35.0 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0189]

When Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is more preferable that HFO-1132 (E) is present in an amount of 20.0 to 55.0 mass%, and HFO-1234yf is present in an amount of 80.0 to 45.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0190]

When Refrigerant 5 is composed of HFO-1132(E) and HFO-1234yf, it is even more preferable that HFO-1132(E) is present in an amount of 25.0 to 50.0 mass%, and HFO-1234yf is present in an amount of 75.0 to 50.0 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0191]

When the Refrigerant 5 is composed of HFO-1132 (E) and HFO-1234yf, it is particularly preferable that HFO-1132 (E) is present in an amount of 30.0 to 45.0 mass%, and HFO-1234yf is present in an amount of 70.0 to 55.0 mass%, based on the total weight of HFO-1132 (E) and HFO-1234yf.

[0192]

When Refrigerant 5 consists of HFO-1132(E) and HFO-1234yf, it is most preferable that HFO-1132(E) is present in an amount of 35.0 to 40.0 mass%, and HFO-1234yf is present in an amount of 65.0 to 60.0 mass%, based on the total weight of HFO-1132(E) and HFO-1234yf.

[0193]

1.6 Application

The composition containing the refrigerant according to the present invention can be widely used as a working fluid for known areas of application of the refrigerant in 1) a cooling method including the operation of a refrigeration cycle, and 2) a method of operating a refrigeration apparatus that controls the refrigeration cycle.

[0194]

The refrigeration cycle in this case means carrying out the conversion of energy by circulating in the refrigeration apparatus a refrigerant (Refrigerant 1, 2, 3, 4 or 5 in accordance with the present invention) in the state of a simple refrigerant or in the state of a refrigerant composition or a working fluid containing refrigeration oil, discussed below, through a compressor.

[0195]

The composition containing the refrigerant according to the present invention has no limitations; however, it is suitable for use in a vapor-compression refrigeration cycle. The vapor-compression refrigeration cycle includes a series of cycles of (1) compressing the refrigerant in a gaseous state in a compressor, (2) cooling the refrigerant to convert it into a high-pressure liquid state in a condenser, (3) reducing the pressure using an expansion valve, and (4) evaporating the liquid refrigerant at a low temperature in an evaporator and removing heat due to the heat of evaporation. Depending on the compression system of gaseous refrigerants, vapor-compression refrigeration cycles can be classified into a turbo cycle (centrifugal), a reciprocating cycle, a twin-screw cycle, a single-screw cycle, a scroll compressor cycle, etc., and can be selected depending on the heat capacity, the compression ratio and the size.

[0196]

The composition containing the refrigerant according to the present invention has no limitations and is suitable as a refrigerant used for large chiller refrigerators, and especially turbo compressors (centrifugal).

[0197]

The present invention includes the use of a refrigerant (or a refrigerant-containing composition) according to the present invention in a cooling method, the use of a refrigerant (or a refrigerant-containing composition) according to the present invention in a method for operating a refrigeration apparatus, etc., and a refrigeration apparatus or the like containing a refrigerant (or a refrigerant-containing composition) according to the present invention.

[0198]

The composition containing Coolant 1 according to the present invention is used for operation of a refrigeration cycle in which the evaporation temperature is from -75 to -5°C.

[0199]

By using the composition containing Refrigerant 1 of the present invention to operate a refrigeration cycle in which the evaporation temperature is -75 to -5°C, there is an advantage that a refrigeration capacity that is equivalent to or higher than that of R404A can be obtained. In the refrigeration cycle in which the composition containing Refrigerant 1 of the present invention is used, the evaporation temperature is preferably -65 to -5°C, more preferably -60 to -7.5°C, even more preferably -55 to -10°C, and particularly preferably -50 to -35°C.

[0200]

In a refrigeration cycle in which the composition containing Refrigerant 1 according to the present invention is used, the evaporation temperature is preferably -7.5°C or less, more preferably -10°C or less, even more preferably -35°C or less.

[0201]

In a refrigeration cycle in which the composition containing Refrigerant 1 according to the present invention is used, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0202]

From the viewpoint of obtaining a refrigeration capacity that is equivalent to or higher than that of R404A, the composition containing Refrigerant 2 according to the present invention is preferably used for the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 15°C. In the refrigeration cycle in which the composition containing Refrigerant 2 according to the present invention is used, the evaporation temperature is preferably from -65 to 10°C, more preferably from -60 to 5°C, even more preferably from -55 to 0°C, and particularly preferably from -50 to -5°C.

[0203]

In a refrigeration cycle in which the composition containing Refrigerant 2 according to the present invention is used, the evaporation temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less.

[0204]

In the refrigeration cycle in which the composition containing Refrigerant 2 according to the present invention is used, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0205]

From the viewpoint of obtaining a refrigeration performance that is equivalent to or higher than that of R134a, the composition containing the refrigerant 3 of the present invention is preferably used for the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 15°C. In the refrigeration cycle in which the composition containing the refrigerant 3 according to the present invention is used, the evaporation temperature is preferably from -65 to 15°C, more preferably from -60 to 5°C, even more preferably from -55 to 0°C, and particularly preferably from -50 to -5°C.

[0206]

In a refrigeration cycle in which the composition containing Refrigerant 3 according to the present invention is used, the evaporation temperature is preferably 15°C or less, more preferably 5°C or less, even more preferably 0°C or less, and particularly preferably -5°C or less.

[0207]

In a refrigeration cycle in which the composition containing Refrigerant 3 of the present invention is used, the evaporation temperature is preferably -65°C or more, more preferably -60°C or more, even more preferably -55°C or more, and particularly preferably -50°C or more.

[0208]

In a refrigeration cycle in which the composition containing Refrigerant 3 of the present invention is used, the evaporation temperature is preferably from -65°C or more to 15°C or less, more preferably from -60°C or more to 5°C or less, even more preferably from -55°C or more to 0°C or less, and particularly preferably from -50°C or more to -5°C or less.

[0209]

From the viewpoint of obtaining a refrigeration capacity of 140% or more compared with that of R1234yf, the composition containing Refrigerant 4 of the present invention is preferably used for the operation of a refrigeration cycle in which the evaporation temperature is from -75 to 20°C. In the refrigeration cycle in which the composition containing Refrigerant 4 of the present invention is used, the evaporation temperature is preferably from -65 to 15°C, more preferably from -60 to 10°C, even more preferably from -55 to 7.5°C, and particularly preferably from -50 to 5°C.

[0210]

From the viewpoint of obtaining a refrigeration capacity of 140% or more compared with that of R1234yf in a refrigeration cycle using a composition containing Refrigerant 4 of the present invention, the evaporation temperature is preferably 20°C or less, more preferably 15°C or less, even more preferably 10°C or less, and particularly preferably 5°C or less.

[0211]

From the viewpoint of obtaining a refrigeration capacity of 140% or more compared with that of R1234yf in a refrigeration cycle using a composition containing Refrigerant 4 of the present invention, the evaporation temperature is preferably -75°C or more, more preferably -60°C or more, even more preferably

-55°C or more, and particularly preferably -50°C or more.

[0212]

Preferred examples of refrigeration apparatuses to which Coolant 1, 2, 3 or 4 (or a composition containing the coolant) according to the present invention can be used include air conditioning systems, refrigerators, freezers, water coolers, ice makers, refrigerated display cases, freezer display cases, freezing and refrigerating units, refrigeration machines for freezing and refrigerating warehouses, air conditioning systems for vehicles, turbo refrigeration machines or screw refrigeration machines. Of these, air conditioning systems for vehicles are preferable. Of the air conditioning systems for vehicles, air conditioning systems for gas-powered vehicles, air conditioning systems for hybrid vehicles, air conditioning systems for vehicles with an electric motor and air conditioning systems for hydrogen vehicles are more preferable. Of the air conditioning systems for vehicles, an air conditioning system for vehicles with an electric motor is particularly preferable.

[0213]

The composition containing Refrigerant 1 or 2 according to the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507 or R513A. The composition containing Refrigerant 1 or 2 of the present invention is suitably used as an alternative refrigerant for R22, R404A, R407F, R407H, R448A, R449A, R454C, R455A or R465A. In addition, since the composition containing Refrigerant 1 or 2 of the present invention has a refrigeration capacity equivalent to R404A, which has found wide application, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R404A.

[0214]

The composition containing Refrigerant 3 of the present invention is suitably used as an alternative refrigerant for R134a, R1234yf or CO2. The composition containing Refrigerant 3 of the present invention is suitably used as an alternative refrigerant for R134a. In addition, since the composition containing Refrigerant 3 of the present invention has a refrigeration capacity of 150% or more relative to that of R134a, which has found wide application, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R134a.

[0215]

The composition containing Refrigerant 4 according to the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze. The composition containing Refrigerant 4 of the present invention is suitably used as an alternative refrigerant for R12, R134a, R404A, R407C, R449C, R454C, R1234yf or R1234ze. In addition, since the composition containing Refrigerant 4 of the present invention has a refrigeration capacity of 140% or more relative to that of R1234yf, which has found wide application, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.

[0216]

The composition containing Refrigerant 5 according to the present invention is suitably used as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze. The composition containing Refrigerant 5 of the present invention is suitably used as an alternative refrigerant for R12, R134a or R1234yf. In addition, since the composition containing Refrigerant 5 of the present invention has a refrigeration capacity of 140% or more relative to that of R1234yf, which has found wide application, and a sufficiently low GWP, it is particularly suitable as an alternative refrigerant for R1234yf.

[0217]

The composition containing the refrigerant 5 according to the present invention is preferably used in an air conditioning system for vehicles. The air conditioning systems for vehicles are preferably air conditioning systems for gas-powered vehicles, air conditioning systems for hybrid vehicles, air conditioning systems for vehicles with an electric motor, or air conditioning systems for hydrogen vehicles. Of the air conditioning systems for vehicles, air conditioning systems for vehicles with an electric motor are particularly preferred. That is, in the present invention, the composition containing the refrigerant 5 is particularly preferably used for vehicles with an electric motor.

[0218]

2. Composition of the refrigerant

The refrigerant composition of the present invention comprises at least the refrigerant according to the present invention and can be used for the same applications as the refrigerant of the present invention.

[0219]

In addition, the refrigerant composition according to the present invention is mixed with at least a refrigeration oil. Therefore, the refrigerant composition can be used to obtain a working fluid for a refrigeration unit.

[0220

The refrigerant composition according to the present invention further comprises at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may optionally comprise at least one component from among the other components described below.

[0221]

As described above, when the refrigerant composition according to the present invention is used as a working fluid for a refrigeration apparatus, it is usually mixed with at least a refrigeration oil for use.

[0222]

Preferably, the refrigerant composition according to the present invention is substantially free of refrigeration oil. More specifically, in the refrigerant composition according to the present invention, the amount of refrigeration oil relative to the entire refrigerant composition is preferably from 0 to 1% by mass, more preferably from 0 to 0.5% by mass, even more preferably from 0 to 0.25% by mass, and particularly preferably from 0 to 0.1% by mass.

[0223]

2.1 Water

The refrigerant composition according to the present invention may contain a small amount of water.

[0224]

The water content in the refrigerant composition is preferably from 0 to 0.1% by mass, more preferably from 0 to 0.075% by mass, even more preferably from 0 to 0.05% by mass, and particularly preferably from 0 to 0.025% by mass, relative to the total refrigerant.

[0225]

A small amount of water present in the refrigerant composition stabilizes the double bonds in the molecules of unsaturated fluorocarbon compounds that may be present in the refrigerant and makes oxidation of the unsaturated fluorocarbon compounds less likely, thereby increasing the stability of the refrigerant composition. In order to achieve the above-described effects obtained due to the presence of water, the lower limit of the water content is approximately 0.001% by weight. For example, the water content can be adjusted in the range from 0.001 to 0.1% by weight, from 0.001 to 0.075% by weight, from 0.001 to 0.05% by weight and from 0.001 to 0.025% by weight.

[0226]

2.2 Tracer

The tracer is added to the refrigerant composition of the present invention in a detectable concentration so that if the composition is diluted, contaminated, or otherwise changes, the tracer can track these changes.

[0227]

The refrigerant composition according to the present invention may comprise a single tracer or two or more tracers.

[0228]

The tracer is not limited and may be appropriately selected from commonly used tracers. Preferably, a compound that cannot become an impurity inevitably mixed into the refrigerant of the present invention may be selected as the tracer.

[0229]

Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrogen oxides (N2O). Of these, hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are preferred.

[0230]

More specifically, the following compounds (sometimes referred to as "tracer compounds" below) are preferred as tracers:

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 (chlorodifluoromethane, CHClF2), HCFC-31 (chlorofluoromethane, CH2ClF), CFC-1113 (chlorotrifluoroethylene, CF2=CClF), HFE-125 (trifluoromethyldifluoromethyl ether, CF3OCHF2), HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F), HFE-143a (trifluoromethyl methyl ethyl ether, CF3OCH3), HFE-227ea (trifluoromethyl tetrafluoroethyl ether, CF3OCHFCF3) and HFE-236fa (trifluoromethyl tetrafluoroethyl ether, CF3OCH2CF3).

[0231]

The tracer compound may be present in the refrigerant composition in a total concentration of 10 to 1000 ppm. The tracer compound is preferably present in the refrigerant composition in a total concentration of 30 to 500 ppm, more preferably 50 to 300 ppm, even more preferably 75 to 250 ppm, and particularly preferably 100 to 200 ppm.

[0232]

2.3 Ultraviolet fluorescent dye

The refrigerant composition of the present invention may contain one ultraviolet fluorescent dye, or two or more ultraviolet fluorescent dyes.

[0233]

The ultraviolet fluorescent dye is not limited and can be appropriately selected from among commonly used ultraviolet fluorescent dyes.

[0234]

Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, fluorescein and their derivatives. Of these, naphthalimide and coumarin are preferred.

[0235]

The amount of the ultraviolet fluorescent dye is not limited and is usually 0.01 to 5 mass%, preferably 0.05 to 3 mass%, more preferably 0.1 to 2 mass%, even more preferably 0.25 to 1.5 mass%, and particularly preferably 0.5 to 1 mass% relative to the total refrigerant.

[0236]

2.4 Stabilizer

The refrigerant composition of the present invention may contain one stabilizer, or two or more stabilizers.

[0237]

The stabilizer has no limitation and can be appropriately selected from among commonly used stabilizers.

[0238]

Examples of stabilizers include nitro compounds, ethers, and amines.

[0239]

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

[0240]

Examples of ethers include 1,4-dioxane.

[0241]

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

[0242]

Examples of stabilizers besides nitro compounds, ethers and amines also include butylhydroxyxylene and benzotriazole.

[0243]

The amount of the stabilizer is not limited. Usually, the amount of the stabilizer is 0.01 to 5% by mass, 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 relative to the total refrigerant.

[0244]

The stability of the refrigerant composition of the present invention can be assessed by generally known methods without limitation. Examples of such methods include the assessment method using free fluoride ions as an indicator in accordance with ASHRAE Standard 97-2007, etc. There is, for example, another assessment method using total acid number as an indicator. This method can be performed, for example, according to ASTM D 974-06.

[0245]

2.5 Polymerization inhibitor

The refrigerant composition of the present invention may contain one polymerization inhibitor, or two or more polymerization inhibitors.

[0246]

The polymerization inhibitor is not limited and can be appropriately selected from among commonly used polymerization inhibitors.

[0247]

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

[0248]

The amount of the polymerization inhibitor is not limited. Usually, the amount of the polymerization inhibitor is 0.01 to 5% by mass, 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 relative to the total refrigerant.

[0249]

2.6 Other components that may be present in the refrigerant composition

The refrigerant composition of the present invention may also contain the following components.

[0250]

For example, fluorinated hydrocarbons other than the refrigerants mentioned above may be present. Examples of fluorinated hydrocarbons used as other components are not limited. At least one fluorinated hydrocarbon selected from the group consisting of HCFC-1122, HCFC-124, and CFC-1113 may be used.

[0251]

As another component, there may be present at least one halogenated organic compound represented by the formula (A): CmHnXp, wherein each X independently represents fluorine, chlorine or bromine; m has a value of 1 or 2; 2m+2 has a value greater than or equal to n+p; and p has a value greater than or equal to 1. The halogenated organic compound is not limited, and preferred examples include difluorochloromethane, chloromethane, 2-chloro-1,1,1,2,2-pentafluoroethane, 2-chloro-1,1,1,2-tetrafluoroethane, 2-chloro-1,1-difluoroethylene and trifluoroethylene.

[0252]

As another component, there may be present at least one organic compound represented by the formula (B): CmHnXp, wherein each X independently represents an atom other than a halogen atom; m has a value of 1 or 2; 2m+2 has a value greater than or equal to n+p; and p has a value greater than or equal to 1. The organic compound is not limited, and preferred examples include propane and isobutane.

[0253]

The amount of the fluorinated hydrocarbon, the halogenated organic compound represented by formula (A), and the organic compound represented by formula (B) is not limited. The total amount thereof is preferably 0.5 mass% or less, more preferably 0.3 mass% or less, and particularly preferably 0.1 mass% or less relative to the total amount of the refrigerant composition.

[0254]

3. Working fluid containing refrigeration oil

The refrigeration oil-containing working fluid according to the present invention includes at least a refrigerant or a refrigerant composition according to the present invention and a refrigeration oil, and is used as a working fluid in a refrigeration apparatus. More specifically, the refrigeration oil-containing working fluid according to the present invention can be obtained by mixing together a refrigerant or a refrigerant composition with a refrigeration oil used in a compressor of a refrigeration apparatus.

[0255]

The amount of the refrigeration oil is not limited and is usually 10 to 50% by mass, 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, relative to the total working fluid containing the refrigeration oil.

[0256]

3.1 Refrigeration oil

The composition of the present invention may comprise one refrigeration oil, or two or more refrigeration oils.

[0257]

The refrigeration oil is not limited and can be appropriately selected from among commonly used refrigeration oils. In this case, for example, refrigeration oils that are excellent in terms of improving the miscibility with the refrigerant mixture of the present invention (the mixed refrigerant of the present invention) and the stability of the mixed refrigerant are appropriately selected as necessary.

[0258]

The base oil of the refrigeration oil is preferably, for example, at least one component selected from the group consisting of polyalkylene glycols (PAG), polyol esters (POE) and polyvinyl ethers (PVE).

[0259]

In addition to the base oil, refrigeration oil may also contain an additive.

[0260]

The additive may be at least one component selected from the group consisting of antioxidants, anti-seize agents, acid scavengers, oxygen scavengers, copper deactivators, anti-corrosion agents, lubrication agents and anti-foaming agents.

[0261]

Refrigeration oil with a kinematic viscosity of 5 to 400 cSt at 40°C is preferred from a lubrication point of view.

[0262]

The refrigeration oil-containing working fluid of the present invention may optionally further comprise at least one additive. Examples of additives include the compatibility enhancing agents described below.

[0263]

3.2 Compatibility enhancing agents

The refrigeration oil-containing working fluid according to the present invention may contain one compatibilizing agent, or two or more compatibilizing agents.

[0264]

The compatibility-enhancing agent is not limited and can be appropriately selected from among commonly used compatibility-enhancing agents.

[0265]

Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkane. Of these, polyoxyalkylene glycol ether is preferred.

Examples

[0266]

Below is a more detailed explanation with reference to examples. However, the present invention is not limited to the examples below.

[0267]

Test Example 1-1

The GWP of each mixed refrigerant presented in Examples 1-1 to 1-13, Comparative Examples 1-1 and 1-2, and Reference Example 1-1 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0268]

The coefficient of performance (COP), refrigeration capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the conditions given below.

Evaporation temperature: -50°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0269]

“Evaporating temperature -50°C” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration appliance is -50°C. In addition, “condensing temperature 40°C” means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration appliance is 40°C.

[0270]

Table 1 shows the results of Test Example 1-1. Table 1 shows examples and comparative examples for refrigerant 1 of the present invention. In Table 1, "CR ratio" and "cooling capacity ratio" mean the ratio (%) when compared with R404A. In Table 1, "saturation pressure (40°C)" refers to the saturation pressure at a saturation temperature of 40°C. In Table 1, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical calculation of the refrigeration cycle for a mixed refrigerant.

[0271]

The coefficient of performance (COP) is calculated using the following equation:

ХК = (cooling capacity or heat capacity)/amount of consumed electricity.

[0272]

The compression ratio is calculated using the following equation:

Compression ratio = condensation pressure (MPa) / evaporation pressure (MPa)

[0273]

The flammability of a mixed refrigerant is determined by fractionating the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate of 0 to 10 cm/sec is classified as Class 2L (hardly flammable), a refrigerant with a burning rate greater than 10 cm/sec is classified as Class 2 (slightly flammable), and a refrigerant with no flame spread is classified as Class 1 (non-flammable). Table 1 of the ASHRAE flammability classification shows the results based on these criteria.

[0274]

The combustion rate test is carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is deaerated by repeating a freeze-pump-thaw cycle until no traces of air are noted on the vacuum gauge. The combustion rate is measured by a closed method. The initial temperature is the ambient temperature. Ignition is carried out by creating an electric spark between the electrodes in the center of the sample cell. The discharge duration is from 1.0 to 9.9 msec, and the ignition energy is usually about 0.1 to 1.0 J. The flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light is used as a sample cell, and a xenon lamp is used as a light source. The schlieren image of the flame is recorded using a high-speed digital video camera at a frame rate of 600 frames/sec and stored in a PC.

[0275]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0276]

More precisely, a spherical glass flask of 12 liters capacity is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is created in the glass flask during combustion, the gas is allowed to leave the flask through the top cap. Ignition is carried out by means of an electric discharge from electrodes placed one-third of the way from the bottom.

[0277]

Test conditions

Test vessel: diameter 280 mm, spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio of refrigerant composition/air: 1% by volume with a step of ±0.2% by volume.

Refrigerant composition mixture: ±0.1% by weight.

Ignition method: AC discharge, voltage 15 kV, electric current 30 mA, neon converter

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Evaluation criteria

When the flame propagates at an angle greater than 90° from the ignition point, it is assessed that flame propagation is present (flammable).

When the flame propagates at an angle of 90° or less from the ignition point, it is rated as no flame propagation (non-flammable).

[0278]

Table 1

Position Unit of measurement Sp. pr. 1-1 (R404A) Wed. pr. 1-1 Ex. 1-1 Ex. 1-2 Ex. 1-3 Ex. 1-4 Ex. 1-5 Ex. 1-6 Ex. 1-7 Ex. 1-8 Ex. 1-9 Ex. 1-10 Ex. 1-11 Ex. 1-12 Ex. 1-13 Wed. pr. 1-2 Ratio of components HFO-1132(E) %mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 100.6 108.6 114.7 115.0 115.5 116.5 117.6 118.8 120,0 121.0 122.4 123.3 124.4 125.5 126.0 131.7 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.082 0.063 0.072 0.073 0.074 0.075 0,077 0,079 0.081 0.083 0.085 0.086 0.088 0,090 0.091 0.099 Compression ratio - 22.2 25.3 24.1 24.0 23.9 23.8 23.6 23.4 23.1 23.0 22.8 22.6 22.5 22.3 22.2 21.6 HC ratio (compared to R404A) % 100 106.2 106.2 106.2 106.2 106.2 106.2 106.2 106.2 106.3 106.3 106.3 106.3 106.4 106.4 106.7 Cooling capacity ratio (compared to R404A) % 100 86.2 98.5 99.1 100 102.1 104.5 106.9 109.5 111.7 114.6 116.4 118.7 121 122.2 133.3 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

Sp. ex. - reference example; Cf. ex. - comparative example

[0279]

Test example 1-2

The GWP of each mixed refrigerant presented in Examples 1-14 to 1-26, Comparative Examples 1-3 and 1-4, and Reference Example 1-2 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0280]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0 under the following conditions.

Evaporation temperature: -35°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0281]

The definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0282]

Table 2 shows the results of Test Example 1-2. Table 2 shows examples and comparative examples regarding Refrigerant 1 of the present invention. In Table 2, the definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0283]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0284]

The flammability of the mixed refrigerant is assessed as in Test Example 1-1. The burning rate tests are carried out as in Test Example 1-1.

[0285]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0286]

Table 2

Position Units of measurement Sp. pr. 1-2 (R404A) Wed. pr.
1-3 Pr.
1-14 Pr.
1-15 Pr.
1-16 Pr.
1-17 Pr.
1-18 Pr.
1-19 Pr.
1-20 Pr.
1-21 Pr.
1-22 Pr.
1-23 Pr.
1-24 Pr.
1-25 Pr.
1-26 Wed. pr.
1-4 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 89.1 95.8 100.6 100.8 101.2 102.0 102.9 103.8 104.7 105.5 106.6 107.3 108.1 109.0 109.5 113.9 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.165 0.131 0.148 0.149 0.151 0.154 0.157 0,160 0.164 0.167 0.171 0.174 0.177 0,180 0.181 0.196 Compression ratio - 11.0 12.2 11.8 11.7 11.7 11.6 11.6 11.5 11.4 11.4 11.3 11.2 11.2 11.1 11.1 10.8 HC ratio (compared to R404A) ％ 100 105.1 104.8 104.7 104.7 104.7 104.6 104.5 104.5 104.4 104.4 104.4 104.3 104.3 104.3 104.3 Cooling capacity ratio (compared to R404A) ％ 100 87.7 98.5 99.0 99.8 101.6 103.7 105.7 108.0 109.8 112.3 113.8 115.7 117.7 118.6 128.0 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0287]

Test Example 1-3

The GWP of each mixed refrigerant presented in Examples 1-27 to 1-39, Comparative Examples 1-5 and 1-6, and Reference Example 1-3 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0288]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0 under the following conditions.

Evaporation temperature: -10°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0289]

The definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0290]

Table 3 shows the results of Test Example 1-3. Table 3 shows examples and comparative examples regarding Refrigerant 1 of the present invention. In Table 3, the definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0291]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0292]

The flammability of the mixed refrigerant is assessed as in Test Example 1-1. The burning rate tests are carried out as in Test Example 1-1.

[0293]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0294]

Table 3

Position Unit
change Sp. pr.
1-3 (R404A) Wed. pr.
1-5 Pr.
1-27 Pr.
1-28 Pr.
1-29 Pr.
1-30 Pr.
1-31 Pr.
1-32 Pr.
1-33 Pr.
1-34 Pr.
1-35 Pr.
1-36 Pr.
1-37 Pr.
1-38 Pr.
1-39 Wed. pr.
1-6 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature oC 75.8 80.8 83.7 83.9 84.1 84.5 85.1 85.6 86.2 86.6 87.3 87.7 88.2 88.7 88.9 91.5 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.434 0.357 0.399 0.401 0.404 0.411 0.419 0.427 0.436 0.443 0.452 0.457 0.465 0.472 0.475 0.509 Compression ratio - 4.2 4.5 4.4 4.4 4.4 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.2 4.2 4.2 HC ratio (compared to R404A) % 100 103.8 102.9 102.9 102.8 102.7 102.5 102.4 102.2 102.1 102.0 101.9 101.8 101.7 101.6 101.3 Cooling capacity ratio (compared to R404A) % 100 89.8 98.7 99.1 99.8 101.2 102.8 104.5 106.2 107.7 109.6 110.8 112.3 113.8 114.5 121.7 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0295]

Test Example 1-4

The GWP of each mixed refrigerant presented in Comparative Examples 1-7 to 1-21 and Reference Example 1-4 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0296]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0, under the following conditions.

Evaporation temperature: -80°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0297]

The definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0298]

Table 4 shows the results of Test Example 1-4. Table 4 shows comparative examples regarding Refrigerant 1 of the present invention. In Table 4, the definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0299]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0300]

The flammability of the mixed refrigerant is assessed as in Test Example 1-1. The burning rate tests are carried out as in Test Example 1-1.

[0301]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0302]

Table 4

Position Units of measurement Sp. pr. 1-4 (R404A) Wed. pr.
1-7 Wed. pr.
1-8 Wed. pr.
1-9 Wed. pr.
1-10 Wed. pr.
1-11 Wed. pr.
1-12 Wed. pr.
1-13 Wed. pr.
1-14 Wed. pr.
1-15 Wed. pr.
1-16 Wed. pr.
1-17 Wed. pr.
1-18 Wed. pr.
1-19 Wed. pr.
1-20 Wed. pr.
1-21 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 136.7 146.0 157.7 158.1 158.8 160.4 162.1 163.9 165.8 167.4 169.6 170.9 172.6 174.3 175.2 184.0 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0,014 0,011 0,012 0,012 0,012 0,012 0,013 0,013 0,013 0,014 0,014 0,014 0,015 0,015 0,015 0,017 Compression ratio - 134.6 149.1 150.8 150.2 149.3 147.2 145.0 142.8 140.5 138.7 136.3 134.9 133.2 131.5 130.7 123.8 HC ratio (compared to R404A) % 100 112.6 110.3 110.3 110.4 110.6 110.8 111,0 111.3 111.4 111.7 111.9 112.1 112.3 112.4 113.5 Cooling capacity ratio (compared to R404A) % 100 91.7 99.3 100.2 101.5 104.4 107.8 111.3 115.1 118.2 122.5 125.2 128.6 132.1 133.8 151.0 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0303]

Test Example 1-5

The GWP of each mixed refrigerant presented in Comparative Examples 1-22 to 1-36 and Reference Example 1-5 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0304]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each of the mixed refrigerants are determined by performing theoretical calculations of the refrigeration cycle for mixed refrigerants using NIST and Refprop, 10.0, under the following conditions.

Evaporation temperature: 10°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0305]

The definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0306]

Table 5 shows the results of Test Example 1-5. Table 5 shows comparative examples regarding Refrigerant 1 of the present invention. In Table 5, the definitions of terms are the same as the definitions of terms in Test Example 1-1.

[0307]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 1-1.

[0308]

The flammability of the mixed refrigerant is assessed as in Test Example 1-1. The burning rate tests are carried out as in Test Example 1-1.

[0309]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 1-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0310]

Table 5

Position Units of measurement Sp. pr.
1-5 (R404A) Wed. pr.
1-22 Wed. pr.
1-23 Wed. pr.
1-24 Wed. pr.
1-25 Wed. pr.
1-26 Wed. pr.
1-27 Wed. pr.
1-28 Wed. pr.
1-29 Wed. pr.
1-30 Wed. pr.
1-31 Wed. pr.
1-32 Wed. pr.
1-33 Wed. pr.
1-34 Wed. pr.
1-35 Wed. pr.
1-36 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 68.5 72.4 74.0 74.1 74.2 74.4 74.7 74.9 75.2 75.5 75.8 76.0 76.2 76.5 76.6 77.9 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.820 0.694 0.768 0.772 0.777 0.789 0.803 0.817 0.832 0.844 0,860 0,870 0.882 0.895 0.901 0.959 Compression ratio - 2.2 2,3 2,3 2,3 2,3 2,3 2,3 2,3 2,3 2,2 2,2 2,2 2,2 2,2 2,2 2,2 HC ratio (compared to R404A) % 100,0 103.1 101.9 101.8 101.7 101.5 101.3 101.1 100.9 100.8 100.6 100.4 100.3 100.1 100.1 99.5 Cooling capacity ratio (compared to R404A) % 100,0 91.2 98.9 99.3 99.8 101,0 102.5 103.8 105.3 106.5 108.2 109.1 110.4 111.6 112.3 118.2 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0311]

Test Example 2-1

The GWP of each mixed refrigerant presented in Examples 2-1 to 2-6, Comparative Examples 2-1 to 2-9, and Reference Example 2-1 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0312]

The coefficient of performance (COP), refrigeration capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: -50°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0313]

“Evaporating temperature -50°C” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration appliance is -50°C. In addition, “condensing temperature 40°C” means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration appliance is 40°C.

[0314]

Table 6 shows the results of Test Example 2-1. Table 6 shows examples and comparative examples with respect to Refrigerant 2 of the present invention. In Table 6, "CR ratio" and "cooling capacity ratio" mean the ratio (%) compared with R404A. In Table 6, "saturation pressure (40°C)" refers to the saturation pressure at a saturation temperature of 40°C. In Table 6, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0315]

The coefficient of performance (COP) is calculated using the following equation:

ХК = (cooling capacity or heat capacity)/amount of consumed electricity.

[0316]

The compression ratio is calculated using the following equation:

Compression ratio = condensation pressure (MPa) / evaporation pressure (MPa).

[0317]

The flammability of a mixed refrigerant is determined by fractionating the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate between 0 cm/sec and 10 cm/sec is classified as Class 2L (hardly flammable), a refrigerant with a burning rate greater than 10 cm/sec is classified as Class 2 (slightly flammable), and a refrigerant with no flame spread is classified as Class 1 (non-flammable). Table 6 of the ASHRAE flammability classifications shows the results based on these criteria.

[0318]

The combustion rate test is carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is deaerated by repeating a freeze-pump-thaw cycle until no traces of air are noted on the vacuum gauge. The combustion rate is measured by a closed method. The initial temperature is the ambient temperature. Ignition is carried out by creating an electric spark between the electrodes in the center of the sample cell. The discharge duration is from 1.0 to 9.9 msec, and the ignition energy is usually about 0.1 to 1.0 J. The flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light is used as a sample cell, and a xenon lamp is used as a light source. The schlieren image of the flame is recorded using a high-speed digital video camera at a frame rate of 600 frames/sec and stored in a PC.

[0319]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0320]

More precisely, a spherical glass flask of 12 liters capacity is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is created in the glass flask during combustion, the gas is allowed to leave the flask through the top cap. Ignition is carried out by means of an electric discharge from electrodes placed one-third of the way from the bottom.

[0321]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio of refrigerant composition/air: 1% by volume with a step of ±0.2% by volume.

Refrigerant composition mixture: ±0.1% by weight.

Ignition method: AC discharge, voltage 15 kV, electric current 30 mA, neon converter

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Evaluation criteria

When the flame propagates at an angle greater than 90° from the ignition point, it is assessed that flame propagation is present (flammable).

When the flame propagates at an angle of 90° or less from the ignition point, it is rated as no flame propagation (non-flammable).

[0322]

Table 6

Position Unit
change Sp. pr. 2-1 (R404A) Wed. pr.
2-1 Wed.
etc.
2-2 Pr.
2-1 Pr.
2-2 Pr.
2-3 Pr.
2-4 Pr.
2-5 Pr.
2-6 Wed. pr.
2-3 Wed. pr.
2-4 Wed. pr.
2-5 Wed. pr.
2-6 Wed. pr.
2-7 Wed. pr.
2-8 Wed. pr.
2-9 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 100.6 108.6 114.7 115.0 115.5 116.5 117.6 118.8 120,0 121.0 122.4 123.3 124.4 125.5 126.0 131.7 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.082 0.063 0.072 0.073 0.074 0.075 0,077 0,079 0.081 0.083 0.085 0.086 0.088 0,090 0.091 0.099 Compression ratio - 22.2 25.3 24.1 24.0 23.9 23.8 23.6 23.4 23.1 23.0 22.8 22.6 22.5 22.3 22.2 21.6 HC ratio (compared to R404A) % 100 106.2 106.2 106.2 106.2 106.2 106.2 106.2 106.2 106.3 106.3 106.3 106.3 106.4 106.4 106.7 Cooling capacity ratio (compared to R404A) % 100 86.2 98.5 99.1 100 102.1 104.5 106.9 109.5 111.7 114.6 116.4 118.7 121 122.2 133.3 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0323]

Test Example 2-2

The GWP of each mixed refrigerant presented in Examples 2-7 to 2-12, Comparative Examples 2-10 to 1-18, and Reference Example 2-2 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0324]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0, under the following conditions.

Evaporation temperature: -35°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0325]

The definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0326]

Table 7 shows the results of Test Example 2-2. Table 7 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 7, the definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0327]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0328]

The flammability of the mixed refrigerant is assessed as in Test Example 2-1. The burning rate tests are conducted as in Test Example 2-1.

[0329]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0330]

Table 7

Position Units of measurement Sp. pr.
2-2 (R404A) Wed. pr.
2-10 Wed. pr.
2-11 Pr.
2-7 Pr.
2-8 Pr.
2-9 Pr.
2-10 Pr.
2-11 Pr.
2-12 Wed. pr.
2-12 Wed. pr.
2-13 Wed. pr.
2-14 Wed. pr.
2-15 Wed. pr.
2-16 Wed. pr.
2-17 Wed. pr.
2-18 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 89.1 95.8 100.6 100.8 101.2 102.0 102.9 103.8 104.7 105.5 106.6 107.3 108.1 109.0 109.5 113.9 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.165 0.131 0.148 0.149 0.151 0.154 0.157 0,160 0.164 0.167 0.171 0.174 0.177 0,180 0.181 0.196 Compression ratio - 11.0 12.2 11.8 11.7 11.7 11.6 11.6 11.5 11.4 11.4 11.3 11.2 11.2 11.1 11.1 10.8 HC ratio (compared to R404A) % 100 105.1 104.8 104.7 104.7 104.7 104.6 104.5 104.5 104.4 104.4 104.4 104.3 104.3 104.3 104.3 Cooling capacity ratio (compared to R404A) % 100 87.7 98.5 99.0 99.8 101.6 103.7 105.7 108.0 109.8 112.3 113.8 115.7 117.7 118.6 128.0 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0331]

Test example 2-3

The GWP of each mixed refrigerant presented in Examples 2-13 to 2-18, Comparative Examples 2-19 to 2-27, and Reference Example 2-3 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0332]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0, under the following conditions.

Evaporation temperature: -10°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0333]

The definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0334]

Table 8 shows the results of Test Example 2-3. Table 8 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 8, the definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0335]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0336]

The flammability of the mixed refrigerant is assessed as in Test Example 2-1. The burning rate tests are conducted as in Test Example 2-1.

[0337]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0338]

Table 8

Position Unit
change Sp. pr.
2-3 (R404A) Wed. pr.
2-19 Wed. pr.
2-20 Pr.
2-13 Pr.
2-14 Pr.
2-15 Pr.
2-16 Pr.
2-17 Pr.
2-18 Wed. pr.
2-21 Wed. pr.
2-22 Wed. pr.
2-23 Wed. pr.
2-24 Wed. pr.
2-25 Wed. pr.
2-26 Wed. pr.
2-27 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature oC 75.8 80.8 83.7 83.9 84.1 84.5 85.1 85.6 86.2 86.6 87.3 87.7 88.2 88.7 88.9 91.5 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.434 0.357 0.399 0.401 0.404 0.411 0.419 0.427 0.436 0.443 0.452 0.457 0.465 0.472 0.475 0.509 Compression ratio - 4.2 4.5 4.4 4.4 4.4 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.3 4.2 4.2 4.2 HC ratio (compared to R404A) % 100 103.8 102.9 102.9 102.8 102.7 102.5 102.4 102.2 102.1 102.0 101.9 101.8 101.7 101.6 101.3 Cooling capacity ratio (compared to R404A) % 100 89.8 98.7 99.1 99.8 101.2 102.8 104.5 106.2 107.7 109.6 110.8 112.3 113.8 114.5 121.7 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0339]

Test Example 2-4

The GWP of each mixed refrigerant presented in Examples 2-19 to 2-24, Comparative Examples 2-28 to 2-36, and Reference Example 2-4 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0340]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0, under the following conditions.

Evaporation temperature: -80°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0341]

The definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0342]

Table 9 shows the results of Test Example 2-4. Table 9 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 9, the definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0343]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0344]

The flammability of the mixed refrigerant is assessed as in Test Example 2-1. The burning rate tests are conducted as in Test Example 2-1.

[0345]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1 using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0346]

Table 9

Position Unit
change Sp. pr.
2-4 (R404A) Wed. pr.
2-28 Wed. pr.
2-29 Pr.
2-19 Pr.
2-20 Pr.
2-21 Pr.
2-22 Pr.
2-23 Pr.
2-24 Wed. pr.
2-30 Wed. pr.
2-31 Wed. pr.
2-32 Wed. pr.
2-33 Wed. pr.
2-34 Wed. pr.
2-35 Wed. pr.
2-36 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 136.7 146.0 157.7 158.1 158.8 160.4 162.1 163.9 165.8 167.4 169.6 170.9 172.6 174.3 175.2 184.0 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0,014 0,011 0,012 0,012 0,012 0,012 0,013 0,013 0,013 0,014 0,014 0,014 0,015 0,015 0,015 0,017 Compression ratio - 134.6 149.1 150.8 150.2 149.3 147.2 145.0 142.8 140.5 138.7 136.3 134.9 133.2 131.5 130.7 123.8 HC ratio (compared to R404A) % 100 112.6 110.3 110.3 110.4 110.6 110.8 111,0 111.3 111.4 111.7 111.9 112.1 112.3 112.4 113.5 Cooling capacity ratio (compared to R404A) % 100 91.7 99.3 100.2 101.5 104.4 107.8 111.3 115.1 118.2 122.5 125.2 128.6 132.1 133.8 151.0 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0347]

Test Example 2-5

The GWP of each mixed refrigerant presented in Examples 2-25 to 2-30, Comparative Examples 2-37 to 2-45, and Reference Example 2-5 (R404A) is estimated based on the values of the Fourth IPCC Report.

[0348]

The coefficient of performance (COP), cooling capacity, discharge temperature, saturation pressure at 40°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using NIST and Refprop 10.0, under the following conditions.

Evaporation temperature: 10°C

Condensation temperature: 40°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0349]

The definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0350]

Table 10 shows the results of Test Example 2-5. Table 10 shows examples and comparative examples regarding Refrigerant 2 of the present invention. In Table 10, the definitions of terms are the same as the definitions of terms in Test Example 2-1.

[0351]

The coefficient of performance (COP) and compression ratio are determined as in Test Example 2-1.

[0352]

The flammability of the mixed refrigerant is assessed as in Test Example 2-1. The burning rate tests are conducted as in Test Example 2-1.

[0353]

The flammability range of the mixed refrigerant is measured in the same manner and under the same conditions as in Test Example 2-1, using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0354]

Table 10

Position Unit
change Sp. pr.
2-5 (R404A) Wed. pr.
2-37 Wed. pr.
2-38 Pr.
2-25 Pr.
2-26 Pr.
2-27 Pr.
2-28 Pr.
2-29 Pr.
2-30 Wed. pr.
2-39 Wed. pr.
2-40 Wed. pr.
2-41 Wed. pr.
2-42 Wed. pr.
2-43 Wed. pr.
2-44 Wed. pr.
2-45 Ratio of components HFO-1132(E) % mass. 0 30.0 40.0 40.5 41.3 43.0 45.0 47.0 49.2 51.0 53.5 55.0 57.0 59.0 60.0 70.0 HFO-1234yf % mass. 0 70.0 60.0 59.5 58.7 57.0 55.0 53.0 50.8 49.0 46.5 45.0 43.0 41.0 40.0 30.0 HFC-134a % mass. 4.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-143a % mass. 52.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 HFC-125 % mass. 44.0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 PGP (AR4) - 3922 6 6 6 6 7 7 7 7 7 7 7 7 8 8 8 Discharge temperature °C 68.5 72.4 74.0 74.1 74.2 74.4 74.7 74.9 75.2 75.5 75.8 76.0 76.2 76.5 76.6 77.9 Saturation pressure (40°C) MPa 1,822 1,592 1,745 1,752 1,764 1,788 1,817 1,844 1,874 1,898 1,931 1,950 1,975 2,000 2,012 2,128 Evaporation pressure MPa 0.820 0.694 0.768 0.772 0.777 0.789 0.803 0.817 0.832 0.844 0,860 0,870 0.882 0.895 0.901 0.959 Compression ratio - 2,2 2,3 2,3 2,3 2,3 2,3 2,3 2,3 2,3 2,2 2,2 2,2 2,2 2,2 2,2 2,2 HC ratio (compared to R404A) % 100,0 103.1 101.9 101.8 101.7 101.5 101.3 101.1 100.9 100.8 100.6 100.4 100.3 100.1 100.1 99.5 Cooling capacity ratio (compared to R404A) % 100,0 91.2 98.9 99.3 99.8 101,0 102.5 103.8 105.3 106.5 108.2 109.1 110.4 111.6 112.3 118.2 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2 Class 2 Class 2 Class 2 Class 2

[0355]

Test example 3

The GWP of each mixed refrigerant presented in Examples 3-1 to 3-5, Comparative Examples 3-1 to 3-5, and Reference Examples 3-1 (R134a) and 3-2 (R404A) are estimated based on the values of the Fourth IPCC Report.

[0356]

The coefficient of performance (COP), refrigeration capacity, discharge temperature, saturation pressure at 45°C saturation temperature, condensing pressure, and evaporating pressure of each mixed refrigerant are determined by performing theoretical refrigeration cycle calculations for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: -10°C

Condensation temperature: 45°C

Overheating temperature: 20K

Supercooling temperature: 0K

Compressor efficiency: 70%

[0357]

“Evaporating temperature -10°C” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration appliance is -10°C. In addition, “condensing temperature 45°C” means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration appliance is 45°C.

[0358]

Table 11 shows the results of Test Example 3. Table 11 shows examples and comparative examples with respect to Refrigerant 3 of the present invention. In Table 11, "CR ratio" and "cooling capacity ratio" mean a ratio (%) compared with R134a. In Table 11, "saturation pressure (45°C)" refers to the saturation pressure at a saturation temperature of 45°C. In Table 11, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the refrigeration cycle according to the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0359]

The coefficient of performance (COP) is calculated using the following equation:

ХК = (cooling capacity or heat capacity)/amount of consumed electricity.

[0360]

The critical temperature is determined by performing calculations using the National Institute of Science and Technology (NIST) database of thermodynamic and transport properties of reference liquids (Refprop 10.0).

[0361]

The flammability of a mixed refrigerant is determined by fractionating the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate between 0 cm/sec and 10 cm/sec is classified as Class 2L (hardly flammable), a refrigerant with a burning rate greater than 10 cm/sec is classified as Class 2 (slightly flammable), and a refrigerant with no flame spread is classified as Class 1 (non-flammable). Table 11 of the ASHRAE flammability classification shows the results based on these criteria.

[0362]

The combustion rate test is carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is deaerated by repeating a freeze-pump-thaw cycle until no traces of air are noted on the vacuum gauge. The combustion rate is measured by a closed method. The initial temperature is the ambient temperature. Ignition is carried out by creating an electric spark between the electrodes in the center of the sample cell. The discharge duration is from 1.0 to 9.9 msec, and the ignition energy is usually about 0.1 to 1.0 J. The flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light is used as a sample cell, and a xenon lamp is used as a light source. The schlieren image of the flame is recorded using a high-speed digital video camera at a frame rate of 600 frames/sec and stored in a PC.

[0363]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0364]

More precisely, a spherical glass flask of 12 liters capacity is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is created in the glass flask during combustion, the gas is allowed to leave the flask through the top cap. Ignition is carried out by means of an electric discharge from electrodes placed one-third of the way from the bottom.

[0365]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio of refrigerant composition/air: 1% by volume with a step of ±0.2% by volume.

Refrigerant composition mixture: ±0.1% by weight.

Ignition method: AC discharge, voltage 15 kV, electric current 30 mA, neon converter

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Evaluation criteria

When the flame propagates at an angle greater than 90° from the ignition point, it is assessed that flame propagation is present (flammable).

When the flame propagates at an angle of 90° or less from the ignition point, it is rated as no flame propagation (non-flammable).

[0366]

Table 11

Position Units of measurement Sp. pr.
3-1 (R134a) Wed. pr. 3-1 Wed. pr. 3-2 Pr.
3-1 Pr.
3-2 Pr.
3-3 Pr.
3-4 Pr.
3-5 Wed. pr. 3-3 Wed. pr. 3-4 Wed. pr. 3-5 Sp. pr.
3-2 (R404A) Ratio of components HFO-1132(E) % mass. 0 20.0 30.0 31.1 33.0 35.0 37.9 39.8 40.0 50.0 0,0 0 HFO-1234yf % mass. 0 80.0 70.0 68.9 67.0 65.0 62.1 60.2 60.0 50.0 100,0 0 HFC-134a % mass. 100,0 0 0 0 0 0 0 0 0 0 0 4.0 HFC-143a % mass. 0 0 0 0 0 0 0 0 0 0 0 52.0 HFC-125 % mass. 0 0 0 0 0 0 0 0 0 0 0 44.0 PGP (AR4) - 1430 5 6 6 6 6 6 6 6 7 4 3922 Discharge temperature °C 86.9 86.3 86.9 87.2 87.9 88.5 89.4 90.0 90.1 93.0 72.2 81.7 Saturation pressure (45oC) MPa 1,160 1,607 1,795 1,814 1,848 1,883 1,930 1,963 1,966 2,123 1,154 2,052 Evaporation pressure MPa 0.201 0.311 0.355 0.360 0.368 0.376 0.388 0.397 0.397 0.437 0.222 0.434 Critical temperature °C 101.1 84.6 83.0 82.7 82.2 81.7 81.0 80.5 80.5 78.7 94.7 72.0 HC ratio (compared to R134a) % 100,0 93.6 92.7 92.6 92.4 92.2 92.0 91.8 91.8 91.0 95.7 88.6 Cooling capacity ratio (compared to R134a) % 100,0 132.3 148.3 150,0 152.8 155.8 159.8 162.7 162.9 176.6 96.2 164.4 ASHRAE Flammability Classification - Class 1 Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 1

[0367]

Test example 4

The GWP of each refrigerant blend presented in Examples 4-1 to 4-7 and Comparative Examples 4-1 to 4-5 is estimated based on the values of the Fourth IPCC Report.

[0368]

The coefficient of performance (COP), refrigeration capacity, discharge temperature, and saturation pressure at a saturation temperature of -10°C of each of the mixed refrigerants are determined by performing theoretical calculations of the refrigeration cycle for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: 5°C

Condensation temperature: 45°C

Overheating temperature: 5K

Supercooling temperature: 5K

Compressor efficiency: 70%

[0369]

“Evaporating temperature 5°C” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration appliance is 5°C. In addition, “condensing temperature 45°C” means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration appliance is 45°C.

[0370]

Table 12 shows the results of Test Example 4. Table 12 shows examples and comparative examples with respect to Refrigerant 4 of the present invention. In Table 12, "CR ratio" and "refrigeration capacity ratio" mean the ratio (%) compared with R1234yf. In Table 12, "saturation pressure (-10°C)" refers to the saturation pressure at a saturation temperature of -10°C, which is a typical value of the evaporation temperature under refrigeration conditions. In Table 12, "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the theoretical calculation of the mixed refrigerant refrigeration cycle.

[0371]

The coefficient of performance (COP) is calculated using the following equation:

ХК = (cooling capacity or heat capacity)/amount of consumed electricity.

[0372]

The critical temperature is determined by performing calculations using the National Institute of Science and Technology (NIST) database of thermodynamic and transport properties of reference liquids (Refprop 10.0).

[0373]

The flammability of a mixed refrigerant is determined by fractionating the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. A refrigerant with a burning rate of 0 to 10 cm/sec is classified as Class 2L (hardly flammable), a refrigerant with a burning rate greater than 10 cm/sec is classified as Class 2 (slightly flammable), and a refrigerant with no flame spread is classified as Class 1 (non-flammable). Table 12 of the ASHRAE flammability classification shows the results based on these criteria.

[0374]

The combustion rate test is carried out as follows. First, a mixed refrigerant having a purity of 99.5% or more is used, and the mixed refrigerant is deaerated by repeating a freeze-pump-thaw cycle until no traces of air are noted on the vacuum gauge. The combustion rate is measured by a closed method. The initial temperature is the ambient temperature. Ignition is carried out by creating an electric spark between the electrodes in the center of the sample cell. The discharge duration is from 1.0 to 9.9 msec, and the ignition energy is usually about 0.1 to 1.0 J. The flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light is used as a sample cell, and a xenon lamp is used as a light source. The schlieren image of the flame is recorded using a high-speed digital video camera at a frame rate of 600 frames/sec and stored in a PC.

[0375]

The flammability range of the mixed refrigerant is measured using a measuring device in accordance with ASTM E681-09 (see FIG. 1).

[0376]

More precisely, a spherical glass flask of 12 liters capacity is used so that the state of combustion can be observed visually and recorded photographically. When excess pressure is created in the glass flask during combustion, the gas is allowed to leave the flask through the top cap. Ignition is carried out by means of an electric discharge from electrodes placed one-third of the way from the bottom.

[0377]

Test conditions

Test vessel: diameter 280 mm spherical (internal volume 12 liters)

Test temperature: 60±3°C

Pressure: 101.3±0.7 kPa

Water: 0.0088±0.0005 g (water content at 50% relative humidity at 23°C) per gram of dry air

Mixing ratio of refrigerant composition/air: 1% by volume with a step of ±0.2% by volume.

Refrigerant composition mixture: ±0.1% by weight.

Ignition method: AC discharge, voltage 15 kV, electric current 30 mA, neon converter

Distance between electrodes: 6.4 mm (1/4 inch)

Spark: 0.4±0.05 sec

Evaluation criteria

When the flame propagates at an angle greater than 90° from the ignition point, it is assessed that flame propagation is present (flammable).

When the flame propagates at an angle of 90° or less from the ignition point, it is rated as no flame propagation (non-flammable).

[0378]

Table 12

Position Unit of measurement Comparative example 4-1 Comparative example 4-2 Example 4-1 Example4-2 Example4-3 Example4-4 Example4-5 Example4-6 Example4-7 Comparative example 4-3 Comparative example 4-4 Comparative example 4-5 Ratio of components HFO-1132(E) % mass. 0 15.0 21.0 23.6 24.3 25.1 26.7 27.5 28.4 30.0 40.0 50.0 HFO-1234yf % mass. 100,0 85.0 79.0 76.4 75.7 74.9 73.3 72.5 71.6 70.0 60.0 50.0 PGP (AR4) - 4 5 5 5 5 6 6 6 6 6 6 7 Discharge temperature °C 54.4 61.3 63.1 63.8 64.0 64.2 64.6 64.8 65.0 65.4 67.5 69.4 Saturation pressure
(-10 oC) MPa 0.222 0.350 0.383 0.396 0,400 0.403 0.411 0.414 0.418 0.425 0.461 0.492 Critical temperature °C 94.7 88.1 85.9 85.0 84.8 84.5 84.0 83.8 83.5 83.0 80.5 78.7 HC ratio (compared to R1234yf) % 100,0 99.1 98.8 98.6 98.5 98.4 98.3 98.2 98.2 98.0 97.2 96.6 Cooling capacity ratio (compared to R1234yf) % 100,0 129.8 140.0 144.2 145.4 146.6 149.1 150.3 151.7 154.1 168.2 181.3 ASHRAE Flammability Classification - Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L Class 2L

[0379]

Test example 5

The GWP of each refrigerant blend presented in Examples 5-1 to 5-13, Comparative Examples 5-1 to 5-3, and Reference Example 5-1 (R134a) is estimated based on the values of the Fourth IPCC Report.

[0380]

The coefficient of performance (COP), the refrigeration capacity, of each mixed refrigerant is determined by performing theoretical calculations of the refrigeration cycle for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions.

Evaporation temperature: -30°C

Condensation temperature: 30°C

Overheating temperature: 5K

Supercooling temperature: 5K

Compressor efficiency: 70%

[0381]

“Evaporating temperature -30°C” means that the evaporating temperature of the mixed refrigerant in the evaporator provided in the refrigeration appliance is -30°C. In addition, “condensing temperature 30°C” means that the condensing temperature of the mixed refrigerant in the condenser provided in the refrigeration appliance is 30°C.

[0382]

Table 13 shows the results of Test Example 5. Table 13 shows examples and comparative examples with respect to Refrigerant 5 of the present invention. In Table 13, the "CR ratio" and "refrigerating capacity ratio" mean a ratio (%) compared with R1234yf. In Table 13, the "discharge temperature (°C)" refers to the temperature at which the refrigerant has the highest temperature in the theoretical calculation of the refrigeration cycle of the mixed refrigerant. In Table 13, the "boiling point (°C)" means the temperature at which the liquid phase of the mixed refrigerant has the atmospheric pressure (101.33 kPa). In Table 13, the "engine power consumption amount (%)" refers to the electric energy used to ensure the operation of the electric vehicle, and is expressed as a ratio compared with the power consumption amount when the refrigerant is HFO-1234yf. In Table 13, the "heater power consumption amount (%)" refers to the electrical energy used to operate the heater, and is expressed as a ratio compared to the power consumption amount when the refrigerant is HFO-1234yf. In Table 13, the "driveable distance" refers to the distance that an electric vehicle equipped with a rechargeable battery having a constant electric capacity can travel when the heater is turned on, and is expressed as a ratio (%) compared to the distance that can be driven (100%) when the vehicle is running without the heater turned on (that is, the heater power consumption is 0).

[0383]

The coefficient of performance (COP) is calculated using the following equation:

ХК = (cooling capacity or heat capacity)/amount of consumed electricity.

[0384]

The flammability of a mixed refrigerant is determined by fractionating the mixed refrigerant to a WCF concentration and measuring the burning rate in accordance with ANSI/ASHRAE Standard 34-2013. The burning rate is measured as follows. A mixed refrigerant having a purity of 99.5% or greater is initially used and the mixed refrigerant is deaerated by repeating a freeze, pump, and thaw cycle until no traces of air are noted on a vacuum gauge. The burning rate is measured by a closed method. The initial temperature is the ambient temperature. Ignition is carried out by creating an electric spark between electrodes in the center of the sample cell. The discharge duration is from 1.0 to 9.9 msec, and the ignition energy is typically approximately 0.1 to 1.0 J. Flame propagation is visualized using schlieren photography. A cylindrical container (inner diameter 155 mm, length 198 mm) having two acrylic windows that transmit light is used as a sample cell, and a xenon lamp is used as a light source. The schlieren image of the flame is recorded using a high-speed digital video camera at a frame rate of 600 fps and stored in a PC.

[0385]

Heating is carried out using an electric heater in the case of a refrigerant having a boiling point greater than -40°C, and using a heat pump in the case of a refrigerant having a boiling point of -40°C or less.

[0386]

The amount of power consumed when using a heater is calculated using the following equation:

The amount of power consumed when using a heater = heat capacity / HC of the heater

The heater's HC refers to its heating capacity.

[0387]

In terms of heating performance, the heater efficiency is 1 in an electric heater, and the heater consumes an electrode equivalent to the motor power. That is, the heater power consumption is E=E/(1+efficiency). In the case of a heat pump, the heater efficiency is determined by performing theoretical calculations of the refrigeration cycle for mixed refrigerants using the National Institute of Science and Technology (NIST) and the Thermodynamic and Transport Properties of Reference Fluids Database (Refprop 10.0) under the following conditions.

Evaporation temperature: -30°C

Condensation temperature: 30°C

Overheating temperature: 5K

Supercooling temperature:5K

Compressor efficiency: 70%

[0388]

The distance traveled is calculated using the following equation:

Distance traveled = (battery capacity)/(engine power consumption + heater power consumption).

[0389]

Table 13 (EH - electric heater, TH - heat pump)

Position Unit of measurement Sp. pr.
5-1 Wed. pr.
5-1 Wed. pr.
5-2 Pr.
5-1 Pr.
5-2 Pr.
5-3 Pr.
5-4 Pr.
5-5 Pr.
5-6 Pr.
5-7 Pr.
5-8 Pr.
5-9 Pr.
5-10 Pr.
5-11 Pr.
5-12 Pr.
5-13 Wed. pr.
5-3 Ratio of components HFO-1132(E) % mass. 0,0 0 10.0 12.1 15.0 20.0 25.0 30.0 35.0 40.0 45.0 50.0 55.0 60.0 65.0 72.0 75.0 HFO-1234yf % mass. 0,0 100,0 90.0 87.9 85.0 80.0 75.0 70.0 65.0 60.0 55.0 50.0 45.0 40.0 35.0 28.0 25.0 HFC-134a % mass. 100,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 PGP (AR4) - 1430 4 5 5 5 5 6 6 6 6 7 7 7 8 8 8 9 HC ratio (compared to R1234yf) % 105 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Cooling capacity ratio (compared to 1234yf) % 99 100 123 128 134 145 155 165 175 185 194 203 212 220 229 240 245 The amount of engine power consumed % 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 The amount of power consumed by the heater % 95 100 100 33 33 33 33 33 33 33 33 33 33 33 33 33 33 Travel distance (without heater) % 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 Travel distance (with heater) % 50 50 50 84 84 84 84 84 84 84 84 84 84 84 84 84 84 Discharge temperature °C 66.0 48.0 54.8 56.0 57.5 59.8 61.9 63.9 65.8 67.6 69.3 70.9 72.6 74.2 75.9 78.2 79.2 Burning speed cm/sec 0,0 1.5 1.5 1.5 1.5 1.5 1.5 1.5 2.0 2.6 3.4 4.3 5.3 6.5 7.8 9.9 10.9 Boiling point °C -26.1 -29.5 -38.8 -40,0 -41.4 -43.3 -44.7 -45.9 -46.9 -47.7 -48.4 -49.1 -49.6 -50.2 -50.5 -51.2 -51.4 Saturation pressure at -40℃ kPa (excess) -50.1 -39 -4.4 0.9 7.5 17.2 25.3 32.3 38.4 43.9 48.8 53.4 57.5 61.4 65.0 69.6 71.5 Heating method System EN EN EN TN TN TN TN TN TN TN TN TN TN TN TN TN TN

Item numbers

[0390]

1: Feed line

2: Sampling line

3: Thermometer

4: Vacuum gauge

5: Electrode

6: Stirring paddle (made of PTFE)

Claims (37)

1. A cooling method comprising operating a refrigeration cycle in which the evaporation temperature is from -75 to -5°C, using a refrigerant composition containing a refrigerant and water, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), and wherein HFO-1132(E) is present in an amount of from 35.0 to 65.0 wt.%, and HFO-1234yf is present in an amount of from 65.0 to 35.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 2. The method of claim 1, wherein HFO-1132(E) is present in an amount of 41.3 to 53.5 wt.%, and HFO-1234yf is present in an amount of 58.7 to 46.5 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 3. The method according to claim 1 or 2, wherein the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 4. A refrigerant composition comprising a refrigerant and water, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerant contains HFO-1132(E) and HFO-1234yf in such amounts that the sum of HFO-1132(E) and HFO-1234yf is 99.5% by weight or more, and wherein HFO-1132(E) is present in an amount of from 40.5 to 49.2 wt.%, and HFO-1234yf is present in an amount of from 59.5 to 50.8 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 5. The composition according to claim 4, wherein the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 6. The composition according to claim 4 or 5, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507 or R513A. 7. A refrigerant composition comprising a refrigerant and water, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerant contains HFO-1132(E) and HFO-1234yf in such amounts that the sum of HFO-1132(E) and HFO-1234yf is 99.5% by weight or more, and wherein HFO-1132(E) is present in an amount of from 31.1 to 39.8 wt.%, and HFO-1234yf is present in an amount of from 68.9 to 60.2 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 8. The composition of claim 7, wherein HFO-1132(E) is present in an amount of 31.1 to 37.9% by weight, and HFO-1234yf is present in an amount of 68.9 to 62.1% by weight, based on the total weight of HFO-1132(E) and HFO-1234yf. 9. The composition according to claim 7 or 8, wherein the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 10. The composition according to claim 7 or 8, which is intended for use as an alternative refrigerant for R134a, R1234yf or CO ₂ . 11. A refrigerant composition comprising a refrigerant and water, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerant contains HFO-1132(E) and HFO-1234yf in such amounts that the sum of HFO-1132(E) and HFO-1234yf is 99.5% by weight or more, and wherein HFO-1132(E) is present in an amount of from 21.0 to 28.4 wt.%, and HFO-1234yf is present in an amount of from 79.0 to 71.6 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 12. The composition of claim 11, wherein the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 13. The composition according to claim 11 or 12, which is intended for use as an alternative refrigerant for R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, R437A, R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R502, R507, R513A, R1234yf or R1234ze. 14. A refrigerant composition comprising a refrigerant and water, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132 (E)) and 2,3,3,3-tetrafluoropropene (HFO-1234yf), wherein the refrigerant contains HFO-1132(E) and HFO-1234yf in such amounts that the sum of HFO-1132(E) and HFO-1234yf is 99.7% by weight or more, and wherein HFO-1132(E) is present in an amount of from 12.1 to 45.0 wt.%, and HFO-1234yf is present in an amount of from 87.9 to 55.0 wt.%, based on the total weight of HFO-1132(E) and HFO-1234yf. 15. The composition of claim 14, wherein the refrigerant consists of HFO-1132 (E) and HFO-1234yf. 16. The composition according to claim 14 or 15, which is intended for use as an alternative refrigerant for R12, R134a or R1234yf. 17. A composition according to any one of claims 4, 5, 7, 8, 11, 12, 14 or 15, containing at least one substance selected from the group consisting of a tracer, ultraviolet fluorescent dyes, stabilizers and polymerization inhibitors. 18. The composition according to any one of claims 4, 5, 7, 8, 11, 12, 14 or 15, wherein the composition additionally contains refrigeration oil and is intended for use as a working fluid in a refrigeration apparatus. 19. The composition according to claim 18, wherein the refrigeration oil comprises at least one polymer selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE). 20. A method of cooling comprising operating a refrigeration cycle using a refrigerant composition according to any one of paragraphs 4-19. 21. A method of operating a refrigeration apparatus designed with the possibility of implementing a refrigeration cycle using a refrigerant composition according to any of paragraphs. 4-19. 22. A refrigeration apparatus containing a refrigerant composition according to any one of paragraphs 4-19 as a working fluid. 23. The apparatus according to item 22, which is an air conditioning system, a refrigerator, a freezer, a water cooler, an ice maker, a refrigerated display case, a freezer display case, a freezer and refrigeration unit, a refrigeration unit for freezers and refrigerated warehouses, an air conditioning system for vehicles, a turbo refrigeration unit or a screw refrigeration machine.