A composition containing a refrigerant, its use, and a refrigerator having the same, and a method of operating the refrigerator.

Abstract

To provide a novel low-GWP mixed refrigerant. [Solution] A composition containing a refrigerant, wherein the refrigerant comprises trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf) and 1,1-difluoroethylene (HFO-1132a), and the mass % based on the sum of HFO-1132(E), R32, R1234yf and HFO-1132a is given as x, y and z, and a (where 0

Description

Technical Field

[0001] The present disclosure relates to a composition containing a refrigerant, its use, a refrigerator having the same, and a method for operating the refrigerator.

Background Art

[0002] As a working medium for a heat cycle that can replace R410A, a working medium for a heat cycle containing trifluoroethylene (HFO-1123) and 1,2-difluoroethylene (HFO-1132) has been proposed (Patent Document 1).

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] An object of the present disclosure is to provide a novel low-GWP mixed refrigerant.

Means for Solving the Problems

[0005] Item 1. A composition containing a refrigerant, where the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a), in the refrigerant, the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a based on their total sum are x, y, and z, and a (where 0 < a ≤ 10.0), respectively, in a ternary composition diagram in which the total sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are When 0 < a ≤ 0.4, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), point F(0.0, -1.5a + 15.5, 0.5a + 84.5), point B’’(0.0, 73.9, -a + 26.1) and point A’’(-a + 26.0, 74.0, 0.0) inside the range of the figure surrounded by the line segments CD, DE, EF, FB’’, B’’A’’ and A’’C connecting these six points respectively or on the line segments CD, DE, EF and B’’A’’ (excluding the points C, F, B’’ and A’’), When 0.4 < a ≤ 10.0, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a + 75.663), point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 +0.3516a + 84.561), point B’’(0.0, 73.9, -a + 26.1) and point A’’(-a + 26.0, 74.0, 0.0) inside the range of the figure surrounded by the line segments CD, DE, EF, FB’’, B’’A’’ and A’’C connecting these six points respectively or on the line segments CD, DE, EF and B’’A’’ (excluding the points C, F, B’’ and A’’), A composition characterized by the above. Item 2. In the refrigerant, let the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a, based on their total sum, be x, y, z, and a respectively (where 0 < a ≤ 10.0), in the ternary composition diagram in which the total sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are when 0 < a ≤ 0.4, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(1.25a 2 - 2.25a + 24.3, 0.0, - 1.25a 2 + 1.25a + 75.7), point F(0.0, - 1.5a + 15.5, 0.5a + 84.5), point B’(0.0, 44.1, - a + 55.9) and point A’(- a + 55.7, 44.3, 0.0) within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’, and A’C connecting these six points respectively, or on the line segments CD, DE, EF, and B’A’ (excluding the points C, F, B’, and A’), when 0.4 < a ≤ 10.0, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(-0.0013a 2 - 1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), point F(0.0, 0.0128a 2 - 1.3516a + 15.439, - 0.0128a 2 + 0.3516a + 84.561), point B’(0.0, 44.1, - a + 55.9) and point A’(-a + 55.7, 44.3, 0.0) The composition according to claim 1, which is within the range of the figure surrounded by the line segments CD, DE, EF, FB', B'A' and A'C connecting the six points respectively, or on the line segments CD, DE, EF and B'A' (excluding the points C, F, B' and A'). Claim 3. In the refrigerant, the mass percentages of HFO-1132(E), R32, R1234yf and HFO-1132a based on the sum thereof are x, y, z, and a respectively (where 0 < a ≤ 10.0). In the ternary composition diagram where the sum of HFO-1132(E), R32 and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are When 0 < a ≤ 0.4, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point E(1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), Point F(0.0, -1.5a + 15.5, 0.5a + 84.5) and Point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DE, EF, FB and BG connecting the five points respectively, or on the line segments GD, DE, EF and BG (excluding the points F and B), When 0.4 < a ≤ 10.0, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a + 75.663), Point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 +0.3516a + 84.561) and Point B(0.0, 21.8, -a + 78.2) Within the range of the figure surrounded by the line segments GD, DE, EF, FB, and BG connecting the five points respectively, or on the line segments GD, DE, EF, and BG (excluding points F and B), The composition according to claim 1. Item 4. A composition containing a refrigerant, where the refrigerant includes trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a), in the refrigerant, the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a based on their total sum are x, y, z, and a respectively (where 0 < a ≤ 10.0), In the ternary composition diagram where the total sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are When 0 < a ≤ 0.4, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point I(-1.5a + 8.4, 0.0, 0.5a + 91.6), point J(0.0, -a + 5.2, 94.8), and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DI, IJ, JB, and BG connecting the five points respectively, or on the line segments GD, DI, IJ, and BG (excluding points J and B), When 0.4 < a ≤ 5.5, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point I(0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 + 0.5508a + 91.58), point J(0.0, 0.0081a 2-0.9892a + 5.194, -0.0081a 2 -0.0108a + 94.806) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DI, IJ, JB, and BG connecting the five points respectively or on the line segments GD, DI, IJ, and BG (excluding points J and B), and when 5.5 < a ≤ 10.0, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DO, OB, and BG connecting the four points respectively or on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the above. Item 5. A composition containing a refrigerant, where the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a), in the refrigerant, taking the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a based on their total sum as x, y, z, and a respectively (where 0 < a ≤ 10.0), in the ternary composition diagram where the total sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, the coordinates (x, y, z) are when 0 < a ≤ 0.4, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-4a + 14.6, 0.0, 3a + 85.4), point L(0.0, -a + 5.2, 94.8) and Point B(0.0, 21.8, -a + 78.2) within or on the line segments GD, DK, KL, LB, and BG connecting the five points respectively (excluding points L and B), when 0.4 < a ≤ 3.5, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-0.0457a 2 -4.0153a + 14.613, 0.0, 0.0457a 2 + 3.0153a + 85.387), point L(0.0, 0.2245a 2 -3.1012a + 8.105, -0.2245a 2 + 2.1012a + 91.895) and point B(0.0, 21.8, -a + 78.2) within or on the line segments GD, DK, KL, LB, and BG connecting the five points respectively (excluding points L and B), and, when 3.5 < a ≤ 10.0, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) within or on the line segments GD, DO, OB, and BG connecting the four points respectively (excluding points O and B), A composition characterized by the above. Item 6. Furthermore, the composition according to any one of Items 1 to 5, which contains refrigerating machine oil and is used as a working fluid for a refrigerating machine. Item 7. The composition according to any one of Items 1 to 3, which is used as an alternative refrigerant for R410A. Item 8. Use of any one of the compositions described in items 1 to 3 as a substitute refrigerant for R410A. Section 9. The composition described in item 4, which is used as a substitute refrigerant for R404A. Section 10. Use of the composition described in item 4 as a substitute refrigerant for R404A. Section 11. The composition described in item 5, which is used as a substitute refrigerant for R1234yf. Section 12. Use of the composition described in item 5 as a substitute refrigerant for R1234yf. Section 13. A refrigerator comprising a composition described in any one of items 1 to 5 as a working fluid. Section 14. The method of operating a refrigerator, A method comprising the step of circulating a composition described in any one of items 1 to 5 as a working fluid in a refrigerator. [Effects of the Invention]

[0006] The refrigerant in this disclosure is low GWP. [Brief explanation of the drawing]

[0007] [Figure 1] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 2] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 3] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 4] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 5] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 6] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 7] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 8] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 9] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 10] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 11] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 12] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 13] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 14] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 15] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 16] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 17] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 18] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Figure 19] This is a triangular diagram showing the composition of the refrigerant of this disclosure. [Modes for carrying out the invention]

[0008] The present inventors conducted diligent studies to solve the above problems and found that various mixed refrigerants described below possess the above characteristics. This disclosure was completed by further studies based on these findings and includes the following embodiments.

[0009] <Definition of Terms> In this specification, the term "refrigerant" includes at least compounds that have been assigned a refrigerant number (ASHRAE number) beginning with R, as defined by ISO 817 (International Organization for Standardization), and also includes compounds that have equivalent refrigerant properties even if they have not yet been assigned a refrigerant number. Refrigerants are broadly classified into "fluorocarbon compounds" and "non-fluorocarbon compounds" in terms of their compound structure. "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0010] In this specification, the term "composition containing a refrigerant" includes at least (1) the refrigerant itself (including a mixture of refrigerants), (2) a composition further containing other components that can be used to obtain a working fluid for a refrigerator by mixing with at least refrigerant oil, and (3) a working fluid for a refrigerator containing refrigerant oil. In this specification, of these three embodiments, composition (2) is referred to as "refrigerant composition" to distinguish it from the refrigerant itself (including a mixture of refrigerants). Also, working fluid for a refrigerator (3) is referred to as "refrigerant oil-containing working fluid" to distinguish it from "refrigerant composition".

[0011] In this specification, when the term “substitute” is used in the context of “substituting” a first refrigerant with a second refrigerant, the first type means that equipment designed to operate using the first refrigerant can be operated under optimal conditions using the second refrigerant with only minor changes to components (at least one of the following: refrigerant oil, gaskets, packings, expansion valves, dryers, and other components) and equipment adjustments as needed. In other words, this type refers to operating the same equipment with a “substitute” refrigerant. The forms of “substitution” in this type may be, in order of increasing degree of change or adjustment required when replacing with the second refrigerant, “drop-in substitution,” “nearly drop-in substitution,” and “retrofit.”

[0012] A second type of "substitution" includes using equipment designed to operate with a second refrigerant, but for the same existing applications as the first refrigerant, by installing the second refrigerant. This type refers to providing the same application by "substituting" a refrigerant.

[0013] In this specification, the term "refrigeration unit" refers to any device that removes heat from an object or space to a temperature lower than the surrounding ambient air and maintains that low temperature. In other words, a refrigerator is a conversion device that obtains energy from an external source, performs work, and converts energy in order to transfer heat from a lower temperature to a higher temperature.

[0014] In this specification, "in-vehicle air conditioning equipment" refers to a type of refrigeration system used in automobiles such as gasoline cars, hybrid cars, electric cars, and hydrogen cars. In-vehicle air conditioning equipment refers to a refrigeration system consisting of a refrigeration cycle in which a liquid refrigerant undergoes heat exchange in an evaporator, the evaporated refrigerant gas is drawn in by a compressor, the adiabatically compressed refrigerant gas is cooled and liquefied in a condenser, and then passed through an expansion valve to undergo adiabatically expanded refrigerant before being supplied back to the evaporator as liquid refrigerant.

[0015] In this specification, temperature glide can be rephrased as the absolute difference between the start temperature and the end temperature of the phase change process of a composition containing the refrigerant of this disclosure within a component of a thermal cycle system.

[0016] 1. refrigerant The refrigerants of this disclosure include trans-1,2-difluoroethylene (HFO-1132(E), E-HFO-1132), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a).

[0017] The refrigerant in this disclosure is a low GWP mixed refrigerant.

[0018] In the refrigerant of the present disclosure, taking the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a based on their total sum as x, y, z, and a respectively (where 0 < a ≤ 10.0), in the ternary composition diagram (see FIGS. 1 to 5) where the sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, disproportionation reaction does not occur at 3.0 MPa and 150 °C, the GWP is 500 or less, and the refrigerating capacity (Cap) ratio to R410A is 60% or more.

[0019] <Requirements> When 0 < a ≤ 0.4, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(1.25a 2 - 2.25a + 24.3, 0.0, - 1.25a 2 + 1.25a + 75.7), point F(0.0, - 1.5a + 15.5, 0.5a + 84.5), point B’’(0.0, 73.9, - a + 26.1) and point A’’(- a + 26.0, 74.0, 0.0) within the range of the figure surrounded by the line segments CD, DE, EF, FB’’, B’’A’’, and A’’C connecting these six points respectively or on the line segments CD, DE, EF, and B’’A’’ (excluding points C, F, B’’, and A’’), When 0.4 < a ≤ 10.0, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(-0.0013a 2 - 1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), point F(0.0, 0.0128a 2 - 1.3516a + 15.439, - 0.0128a 2 + 0.3516a + 84.561), Point B’’(0.0, 73.9, -a + 26.1) and Point A’’(-a + 26.0, 74.0, 0.0) within the range of the figure surrounded by line segments CD, DE, EF, FB’’, B’’A’’, and A’’C connecting the six points respectively, or on the line segments CD, DE, EF, and B’’A’’ (excluding points C, F, B’’, and A’’).

[0020] In the refrigerant of the present disclosure, taking the mass percentages of HFO - 1132(E), R32, R1234yf, and HFO - 1132a based on their total sum as x, y, z, and a respectively (where 0 < a ≤ 10.0), in the ternary composition diagram (see FIGS. 1 - 5) where the sum of HFO - 1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150 °C, the GWP is 300 or less, and the refrigerating capacity (Cap) ratio to R410A is 60% or more.

[0021] <Requirement> When 0 < a ≤ 0.4, Point C(-a + 60.0, 40.0, 0.0), Point D(-a + 44.0, 0.0, 56.0), Point E(1.25a 2 - 2.25a + 24.3, 0.0, - 1.25a 2 + 1.25a + 75.7), Point F(0.0, - 1.5a + 15.5, 0.5a + 84.5), Point B’(0.0, 44.1, -a + 55.9) and Point A’(-a + 55.7, 44.3, 0.0) within the range of the figure surrounded by line segments CD, DE, EF, FB’, B’A’, and A’C connecting the six points respectively, or on the line segments CD, DE, EF, and B’A’ (excluding points C, F, B’, and A’), When 0.4 < a ≤ 10.0, Point C(-a + 60.0, 40.0, 0.0), Point D(-a + 44.0, 0.0, 56.0), Point E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), Point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 + 0.3516a + 84.561), Point B’(0.0, 44.1, -a + 55.9) and Point A’(-a + 55.7, 44.3, 0.0) are within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’ and A’C connecting these six points respectively, or on the line segments CD, DE, EF and B’A’ (excluding the points C, F, B’ and A’).

[0022] In the refrigerant of the present disclosure, taking the mass percentages of HFO-1132(E), R32, R1234yf and HFO-1132a based on their total sum as x, y and z, and a (where 0 < a ≤ 10.0) respectively, in the ternary composition diagram (see Figures 1 to 5) where the sum of HFO-1132(E), R32 and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150 °C, the GWP is 150 or less, and the refrigerating capacity (Cap) ratio to R410A is 60% or more.

[0023] <Requirements> When 0 < a ≤ 0.4, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point E(1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 + 1.25a + 75.7), Point F(0.0, -1.5a + 15.5, 0.5a + 84.5) and Point B(0.0, 21.8, -a + 78.2) Within the range of the figure surrounded by the line segments GD, DE, EF, FB, and BG connecting the five points respectively, or on the line segments GD, DE, EF, and BG (excluding the points F and B), When 0.4 < a ≤ 10.0, Point G( -a + 52.8, 22.0, 25.2), Point D( -a + 44.0, 0.0, 56.0), Point E( -0.0013a 2 - 1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), Point F(0.0, 0.0128a 2 - 1.3516a + 15.439, -0.0128a 2 + 0.3516a + 84.561) and Point B(0.0, 21.8, -a + 78.2) is within the range of the figure surrounded by the line segments GD, DE, EF, FB, and BG connecting the five points respectively, or on the line segments GD, DE, EF, and BG (excluding the points F and B).

[0024] In the refrigerant of the present disclosure, taking the mass percentages of HFO - 1132(E), R32, R1234yf, and HFO - 1132a based on their total sum as x, y, z, and a (where 0 < a ≤ 10.0) respectively, in a ternary composition diagram (see FIGS. 6 - 12) where the sum of HFO - 1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, no disproportionation reaction occurs at 3.0 MPa and 150 °C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio to R404A is 60% or more.

[0025] <Requirement> When 0 < a ≤ 0.4, Point G( -a + 52.8, 22.0, 25.2), Point D( -a + 44.0, 0.0, 56.0), Point I( -1.5a + 8.4, 0.0, 0.5a + 91.6), Point J(0.0, -a + 5.2, 94.8) and Point B (0.0, 21.8, -a + 78.2) Within the range of the figure enclosed by the line segments GD, DI, IJ, JB, and BG connecting the five points respectively, or on the line segments GD, DI, IJ, and BG (excluding points J and B), When 0.4 < a ≤ 5.5, Point G (-a + 52.8, 22.0, 25.2), Point D (-a + 44.0, 0.0, 56.0), Point I (0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 + 0.5508a + 91.58), Point J (0.0, 0.0081a 2 -0.9892a + 5.194, -0.0081a 2 -0.0108a + 94.806) and Point B (0.0, 21.8, -a + 78.2) Within the range of the figure enclosed by the line segments GD, DI, IJ, JB, and BG connecting the five points respectively, or on the line segments GD, DI, IJ, and BG (excluding points J and B), and, When 5.5 < a ≤ 10.0, Point G (-a + 52.8, 22.0, 25.2), Point D (-a + 44.0, 0.0, 56.0), Point O (0.0, 0.0, -a + 100.0) and Point B (0.0, 21.8, -a + 78.2) Within the range of the figure enclosed by the line segments GD, DO, OB, and BG connecting the four points respectively, or on the line segments GD, DO, and BG (excluding points O and B).

[0026] In the refrigerant of the present disclosure, let the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a based on their total be x, y, z, and a respectively (where 0 < a ≤ 10.0). In the ternary composition diagram (see FIGS. 13 to 19) where the total of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, disproportionation reaction does not occur at 3.0 MPa and 150 °C, the GWP is 150 or less, and the boiling point is -40 °C or less. When the boiling point is -40.0 °C or less, there is an advantage that it is easy to use in heating by a heat pump. For example, the refrigerant of the present disclosure has an advantage that by being used to operate the refrigeration cycle of in-vehicle air conditioning equipment, heating by a heat pump with less power consumption compared to an electric heater becomes possible. Examples of in-vehicle air conditioning equipment include those for gasoline vehicles, hybrid vehicles, electric vehicles, or hydrogen vehicles.

[0027] <Requirement> When 0 < a ≤ 0.4, the line segments GD, DK, KL, LB, and BG connecting the five points of point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-4a + 14.6, 0.0, 3a + 85.4), point L(0.0, -a + 5.2, 94.8) and point B(0.0, 21.8, -a + 78.2) are within the range of the figure surrounded by these line segments or on the line segments GD, DK, KL, and BG (excluding points L and B), When 0.4 < a ≤ 3.5, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-0.0457a 2 -4.0153a + 14.613, 0.0, 0.0457a 2 + 3.0153a + 85.387), point L(0.0, 0.2245a 2-3.1012a + 8.105, -0.2245a 2 +2.1012a + 91.895) and point B(0.0, 21.8, -a + 78.2) within or on the line segments GD, DK, KL, LB, and BG connecting the five points respectively (excluding points L and B), and when 3.5 < a ≤ 10.0, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) within or on the line segments GD, DO, OB, and BG connecting the four points respectively (excluding points O and B).

[0028] The refrigerant of the present disclosure may contain additional refrigerant in addition to the essential refrigerant, as long as the above characteristics and effects are not impaired. In this regard, in one aspect, it is preferable that the refrigerant of the present disclosure contains 99.5% by mass or more, more preferably 99.75% by mass or more, still more preferably 99.9% by mass or more, even more preferably 99.999% by mass or more, and most preferably 99.9999% by mass or more of the total essential refrigerant with respect to the entire refrigerant. The refrigerant of the present disclosure may consist essentially of only the essential refrigerant, and in this case, the refrigerant of the present disclosure may consist of only the essential refrigerant and inevitable impurities. Also, the refrigerant of the present disclosure may consist of only the essential refrigerant.

[0029] The additional refrigerants are not particularly limited and can be broadly selected. The mixed refrigerants may contain one additional refrigerant alone or two or more additional refrigerants. Examples of additional refrigerants include acetylene, methylamine, fluoroethylene (HFO-1141), trifluoroethylene (HFO-1123), 1,1,1-trifluoroethane (HFC-143a), 1,1,1,2-tetrafluoroethane (HFC-134a), cis-1,2-difluoroethylene (Z-HFO-1132), 3,3,3-trifluoropropene (HFO-1243zf), 1,1,1,2,2-pentafluoropropane (HFC-245cb), 2,2-difluoro-1-chloroethylene (HCFC-1122), and 1-chloro-1,2,2,2-tetrafluoroethane (HCFC- Examples include chlorotrifluoroethylene (CFC-1113), 3,3,3-trifluoropropyne, 1-chloro-1,1,2-trifluoroethane (HCFC-133), 2-chloro-1,1,1-trifluoroethane (HCFC-133b), 1,1-dichloro-2,2,2-trifluoroethane (HCFC-123), 1,2-difluoroethane (HFC-152), 1,1,2-trifluoroethane (HFC-143), fluoromethane (HFC-41), chlorodifluoromethane (HCFC-22), ethylene, and 1-chloro-1,2-difluoroethane (HCFC-142a).

[0030] 1.2 Purpose The refrigerants of this disclosure include, for example, R12, R22, R134a, R404A, R407A, R407C, R407F, R407H, R410A, R413A, R417A, R422A, R422B, R422C, R422D, R423A, R424A, R426A, R427A, R430A, R434A, and R437A. It can be used as a substitute refrigerant for R438A, R448A, R449A, R449B, R449C, R452A, R452B, R454A, R454B, R454C, R455A, R465A, R474A, R479A, R502, R507, R513A, R1234yf, or R1234ze(E). Among these, it is preferable to use it as a substitute refrigerant for at least one of R410A, R404A, and R1234yf.

[0031] The refrigerant of this disclosure can preferably be used as a working fluid in a refrigerator.

[0032] 2. Refrigerant composition The refrigerant compositions of this disclosure contain at least the refrigerant of this disclosure and can be used for the same purposes as the refrigerant of this disclosure. Furthermore, the refrigerant compositions of this disclosure can be used to obtain a working fluid for a refrigeration system by further mixing them with at least refrigerant oil.

[0033] The refrigerant compositions of this disclosure contain, in addition to the refrigerant of this disclosure, at least one other component. The refrigerant compositions of this disclosure may optionally contain at least one of the following other components. As described above, when the refrigerant compositions of this disclosure are used as working fluids in a refrigerator, they are usually used in mixture with at least refrigerant oil. Therefore, the refrigerant compositions of this disclosure preferably contain substantially no refrigerant oil. Specifically, the refrigerant composition of this disclosure preferably contains 1% by mass or less, and more preferably 0.1% by mass or less, of refrigerant oil relative to the total refrigerant composition.

[0034] 2.1 water The refrigerant composition of this disclosure may contain trace amounts of water. Preferably, the water content in the refrigerant composition is 0.1% by mass or less relative to the total refrigerant. The inclusion of trace amounts of water in the refrigerant composition stabilizes the intramolecular double bonds of unsaturated fluorocarbon compounds that may be contained in the refrigerant, and also reduces the likelihood of oxidation of unsaturated fluorocarbon compounds, thereby improving the stability of the refrigerant composition.

[0035] 2.2 tracer The tracer is added to the refrigerant composition of the Disclosure at a detectable concentration so that any changes to the refrigerant composition of the Disclosure can be tracked if it is diluted, contaminated, or otherwise altered.

[0036] The refrigerant composition of this disclosure may contain one tracer alone or two or more tracers.

[0037] The tracer is not particularly limited and can be appropriately selected from among commonly used tracers.

[0038] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluoroethers, brominated compounds, iodized compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluoroethers are particularly preferred as tracers.

[0039] The following compounds are preferred as tracers. FC-14 (tetrafluoromethane, CF4), HCC-40 (chloromethane, CH3Cl), HFC-23 (trifluoromethane, CHF3), HFC-41 (fluoromethane, CH3F), HFC-125 (pentafluoroethane, CF3CHF2), HFC-134a (1,1,1,2-tetrafluoroethane, CF3CH2F), HFC-134 (1,1,2,2-tetrafluoroethane, CHF2CHF2), HFC-143a (1,1,1-trifluoroethane, CF3CH3), HFC-143 (1,1,2-trifluoroethane, CHF2CH2F), HFC-152a (1,1-difluoroethane, CHF2CH3) HFC-152 (1,2-difluoroethane, CH2FCH2F), 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), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane, CF3CHFCF3), HCFC-22 (chlorodifluoromethane, CHClF2), HCFC-31 (chlorofluoromethane, CH2ClF), CFC-1113 (chlorotrifluoroethylene, CF2=CClF), HFE-125 (trifluoromethyl-difluoromethyl ether, CF3OCHF2), HFE-134a (trifluoromethyl-fluoromethyl ether, CF3OCH2F), HFE-143a (trifluoromethyl methyl ether, CF3OCH3), HFE-227ea (trifluoromethyl-tetrafluoroethyl ether, CF3OCHFCF3), HFE-236fa (trifluoromethyl-trifluoroethyl ether, CF3OCH2CF3).

[0040] The refrigerant composition of this disclosure may contain tracers in total at about 10 parts by weight per million (ppm) or more relative to the entire refrigerant composition. Alternatively, the refrigerant composition of this disclosure may contain tracers in total at about 1000 ppm or less relative to the entire refrigerant composition. The refrigerant composition of this disclosure may contain tracers in total at preferably about 30 ppm or more, more preferably about 50 ppm or more, relative to the entire refrigerant composition. The refrigerant composition of this disclosure may contain tracers in total at preferably about 500 ppm or less, and may also contain about 300 ppm or less, relative to the entire refrigerant composition.

[0041] 2.3 UV fluorescent dyes The refrigerant composition of this disclosure may contain one ultraviolet fluorescent dye alone, or it may contain two or more ultraviolet fluorescent dyes.

[0042] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0043] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as their derivatives. Naphthalimide and coumarin, or either or both, are particularly preferred as ultraviolet fluorescent dyes.

[0044] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, naphthoxanthene, and fluorescein, as well as their derivatives. Naphthalimide and coumarin, or either or both, are particularly preferred as ultraviolet fluorescent dyes.

[0045] 2.4 Stabilizer The refrigerant composition of this disclosure may contain one stabilizer alone or two or more stabilizers.

[0046] The stabilizer is not particularly limited and can be appropriately selected from among commonly used stabilizers.

[0047] Examples of stabilizers include nitro compounds, ethers, and amines.

[0048] Examples of nitro compounds include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0049] Examples of ethers include 1,4-dioxane.

[0050] Examples of amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0051] Other examples include butylhydroxyxylene and benzotriazole.

[0052] The stabilizer content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant. The stabilizer content is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant.

[0053] 2.5 Polymerization inhibitors The refrigerant composition of this disclosure may contain one polymerization inhibitor alone or two or more polymerization inhibitors.

[0054] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0055] Examples of polymerization inhibitors include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-t-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0056] The polymerization inhibitor content is preferably 0.01% by mass or more, and more preferably 0.05% by mass or more, relative to the total refrigerant. The polymerization inhibitor content is preferably 5% by mass or less, and more preferably 2% by mass or less, relative to the total refrigerant.

[0057] 3. Working fluid containing refrigeration oil The refrigerant oil-containing working fluid of this disclosure comprises at least the refrigerant or refrigerant composition of this disclosure and refrigerant oil, and is used as a working fluid in a refrigerator. Specifically, the refrigerant oil-containing working fluid of this disclosure is obtained by mixing refrigerant oil used in the compressor of a refrigerator with the refrigerant or refrigerant composition. The refrigerant oil-containing working fluid generally contains 10% by mass or more of refrigerant oil. The refrigerant oil-containing working fluid generally contains 50% by mass or less of refrigerant oil.

[0058] 3.1 Refrigerating machine oil The composition of this disclosure may contain one type of refrigeration oil alone, or it may contain two or more types.

[0059] The refrigerating oil is not particularly limited and can be appropriately selected from commonly used refrigerating oils. In that case, a refrigerating oil that is superior in terms of compatibility with the mixture and its ability to improve the stability of the mixture can be appropriately selected as needed.

[0060] As the base oil for the refrigeration oil, at least one selected from the group consisting of polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferred.

[0061] Refrigerant oil may contain additives in addition to the base oil. The additives may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper deactivators, rust inhibitors, oiliness agents, and defoaming agents.

[0062] For refrigeration oil, a kinematic viscosity of 5 cSt or higher at 40°C is preferable from a lubrication standpoint. Furthermore, for refrigeration oil, a kinematic viscosity of 400 cSt or lower at 40°C is preferable from a lubrication standpoint.

[0063] The refrigerant oil-containing working fluid of this disclosure may optionally further contain at least one additive. Examples of additives include the following compatibilizers.

[0064] 3.2 Compatibilizer The refrigerant oil-containing working fluid of this disclosure may contain one type of compatibilizer alone, or it may contain two or more types of compatibilizers.

[0065] The compatibilizer is not particularly limited and can be appropriately selected from among commonly used compatibilizers.

[0066] Examples of compatibilizers include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as compatibilizers.

[0067] 4. How to operate a refrigerator The method for operating the refrigerator described herein is a method for operating the refrigerator using the refrigerant described herein.

[0068] Specifically, the method for operating the refrigerator of this disclosure includes a step of circulating the refrigerant of this disclosure in the refrigerator.

[0069] 5. Methods for suppressing disproportionation reactions The method for suppressing the disproportionation reaction of HFO-1132(E) in this disclosure is a method for suppressing the disproportionation reaction of HFO-1132(E), which includes the step of operating a refrigeration cycle using the refrigerant of this disclosure.

[0070] In the method for suppressing disproportionation reactions of the present disclosure, the effect is obtained that the disproportionation reaction of HFO-1132(E) does not occur even when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0071] The method for suppressing disproportionation reactions disclosed herein makes it possible to suppress disproportionation reactions and operate the refrigeration cycle even in refrigerators that do not have means for suppressing disproportionation reactions.

[0072] 6. Use for suppressing disproportionation reactions The use of the present disclosure is for the purpose of suppressing the disproportionation reaction of HFO-1132(E) with respect to R32, R1234yf, and HFO-1132a, which is achieved by mixing R32, R1234yf, and HFO-1132a, as well as HFO-1132(E), in the refrigerant mixture ratio of the present disclosure.

[0073] In its use for suppressing disproportionation reactions, the HFO-1132(E) disproportionation reaction is particularly effective when the refrigerant pressure is 3.0 MPa and the refrigerant temperature is 150°C.

[0074] Although embodiments have been described above, it should be understood that various modifications to the form and details are possible without departing from the spirit and scope of the claims. [Examples]

[0075] The following provides further details with reference to examples. However, this disclosure is not limited to these examples.

[0076] A refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf was mixed with one of the following refrigerants: HFO-1132a, HFO-1123, Z-HFO-1132, HFC-161, or ethylene, in the mass percentages shown in Table 1.

[0077] For each of these refrigerant mixtures, the GWP, COP ratio to R410A, refrigeration capacity ratio, and temperature glide were investigated (Table 1).

[0078] The GWP of HFO-1132(E) was set to 1, and the GWPs of R32, R1234yf, HFO-1132a, HFO-1123, Z-HFO-1132, HFC-161, and ethylene were evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. Furthermore, the COP and refrigeration capacity of each refrigerant mixture were determined by performing theoretical refrigeration cycle calculations using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) under the following conditions. The physical property data for HFO-1132(E) used in the theoretical refrigeration cycle calculations were obtained through actual measurements and added to Refprop 10.0. <Compared to R410A> Evaporation temperature 5℃ Condensation temperature 45℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency: 70%

[0079] In Table 1 below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage relative to R410A.

[0080] The coefficient of performance (COP) was calculated using the following formula. COP = (Refrigeration capacity or heating capacity) / Energy consumption

[0081] [Table 1]

[0082] In mixed refrigerants (Examples 1 and 2, and Comparative Examples 3 and 4) prepared by adding HFO-1132a or HFO-1123 to a refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf, the temperature glide was similar to that of a refrigerant composition consisting only of HFO-1132(E), R32, and R1234yf (Comparative Example 2), while the refrigeration capacity ratio to R410A was improved. Furthermore, HFO-1132a improved the refrigeration capacity ratio of the mixed refrigerant to R410A with a smaller addition amount compared to HFO-1123. The results in Table 1 show that HFO-1132a is a superior additive compared to HFO-1123, Z-HFO-1132, HFC-161, and ethylene, in that it can improve the refrigeration capacity ratio to R410A while maintaining a similar temperature glide to refrigerant compositions consisting only of HFO-1132(E), R32, and R1234yf.

[0083] Mixed refrigerants were prepared by mixing HFO-1132(E), R32, R1234yf, and HFO-1132a in the mass percentages shown in Tables 2 to 5, based on their sum.

[0084] For each of these mixed refrigerants, the presence or absence of disproportionation reactions was investigated using the following test methods and conditions. Test method The refrigerant composition to be tested was transferred to a test container, heated to 150°C, and then 30 J of energy was applied to the refrigerant composition by applying voltage to a Pt wire inside the container to melt it. The presence or absence of a disproportionation reaction was determined by the rapid increase in pressure and temperature inside the apparatus. Test conditions Test container: 38cc stainless steel container Test temperature: 150℃ Pressure: 3.0 MPa Judgment criteria "Non-explosive": The temperature or pressure after Pt wire cutting is less than twice the original temperature, and no rapid disproportionation reaction has occurred. "Explosion": The temperature or pressure after the Pt wire cutting reached more than twice its original level, causing a rapid disproportionation reaction.

[0085] [Table 2] [Table 3] [Table 4] [Table 5]

[0086] From the results shown in Tables 2 to 5, it can be seen that the refrigerant of this disclosure does not undergo a disproportionation reaction at 3.0 MPa and 150°C when the region shown in the triangular diagrams in Figures 1 to 19, specifically when the coordinates (x, y, z) are on the line CD or below the line CD.

[0087] The GWP of HFO-1132(E) was set to 1, and the GWPs of R32, R1234yf, and HFO-1132a were evaluated based on the values ​​from the IPCC (Intergovernmental Panel on Climate Change) Fourth Assessment Report. Furthermore, the COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were determined by performing theoretical calculations of the refrigeration cycle under the following conditions using the National Institute of Science and Technology (NIST) Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0). The physical property data for HFO-1132(E) used in the theoretical calculations were obtained through actual measurements and added to Refprop 10.0. <Compared to R410A> Evaporation temperature 5℃ Condensation temperature 45℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency: 70% <Compared to R404A> Evaporation temperature: -40℃ Condensation temperature 40℃ Superheat temperature 20K Supercooling temperature 0K Compressor efficiency: 70% <Ratio to R1234yf> Evaporation temperature: -30℃ Condensation temperature: 30℃ Superheat temperature 5K Supercooling temperature 5K Compressor efficiency: 70%

[0088] In the table below, "COP ratio" and "refrigeration capacity ratio" refer to the percentage (%) relative to R410A, R404A, or R1234yf. Also, in the table, "boiling point (°C)" refers to the temperature at which the liquid phase of the refrigerant mixture reaches atmospheric pressure (101.33 kPa).

[0089] The coefficient of performance (COP) was calculated using the following formula. COP = (Refrigeration capacity or heating capacity) / Power consumption

[0090] These values, along with the GWP for each refrigerant mixture, are shown in the table below.

[0091] [Table 6]

[0092] [Table 7]

[0093] [Table 8]

[0094] [Table 9]

[0095] [Table 10]

[0096]

Table 11

[0097] Note that the coordinates of each point were obtained based on the least squares method as follows.

[0098]

Table 12

Table 13

Table 14

Table 15

Table 16

Table 17

[0099] In the above aspect, the refrigerant of the present disclosure is HFO-1132(E), R32, R1234yf, and HFO-1132a, and the mass percentages based on the sum of these are x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a ternary composition diagram (see FIGS. 1 to 5) where the sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that disproportionation reaction does not occur at 3.0 MPa and 150 °C, the GWP is 500 or less, and the refrigerating capacity (Cap) ratio to R410A is 60% or more.

[0100] <Requirements> When 0 < a ≤ 0.4, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(1.25a2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), Point F(0.0, -1.5a + 15.5, 0.5a + 84.5), Point B’’(0.0, 73.9, -a + 26.1) and Point A’’(-a + 26.0, 74.0, 0.0) within the range of the figure surrounded by the line segments CD, DE, EF, FB’’, B’’A’’, and A’’C connecting these six points respectively or on the line segments CD, DE, EF, and B’’A’’ (however, excluding points C, F, B’’, and A’’), when 0.4 < a ≤ 10.0, Point C(-a + 60.0, 40.0, 0.0), Point D(-a + 44.0, 0.0, 56.0), Point E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 +0.841a + 75.663), Point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 +0.3516a + 84.561), Point B’’(0.0, 73.9, -a + 26.1) and Point A’’(-a + 26.0, 74.0, 0.0) within the range of the figure surrounded by the line segments CD, DE, EF, FB’’, B’’A’’, and A’’C connecting these six points respectively or on the line segments CD, DE, EF, and B’’A’’ (however, excluding points C, F, B’’, and A’’).

[0101] In the above aspect, for the refrigerant of the present disclosure, the mass percentages of HFO-1132(E), R32, R1234yf, and HFO-1132a, based on the sum thereof, are x, y, z, and a respectively (where 0 < a ≤ 10.0). In a ternary composition diagram (see FIGS. 1 to 5) where the sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that disproportionation reaction does not occur at 3.0 MPa and 150 °C, the GWP is 300 or less, and the refrigerating capacity (Cap) ratio with respect to R410A is 60% or more.

[0102] <Requirement> When 0 < a ≤ 0.4, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 + 1.25a + 75.7), point F(0.0, -1.5a + 15.5, 0.5a + 84.5), point B’(0.0, 44.1, -a + 55.9) and point A’(-a + 55.7, 44.3, 0.0) It is within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’, and A’C connecting these six points respectively or on the line segments CD, DE, EF, and B’A’ (excluding the points C, F, B’, and A’), When 0.4 < a ≤ 10.0, point C(-a + 60.0, 40.0, 0.0), point D(-a + 44.0, 0.0, 56.0), point E(-0.0013a 2 -1.841a + 24.337, 0.0, 0.0013a 2 + 0.841a + 75.663), point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 + 0.3516a + 84.561), Point B’(0.0, 44.1, -a + 55.9) and Point A’(-a + 55.7, 44.3, 0.0) within the range of the figure surrounded by the line segments CD, DE, EF, FB’, B’A’ and A’C connecting the six points respectively, or on the line segments CD, DE, EF and B’A’ (excluding the points C, F, B’ and A’).

[0103] In the above aspect, the refrigerant of the present disclosure is HFO - 1132(E), R32, R1234yf and HFO - 1132a, and the mass percentages based on the sum of these are x, y, z, and a respectively (where 0 < a ≤ 10.0). In the ternary composition diagram (see Figures 1 - 5) where the sum of HFO - 1132(E), R32 and R1234yf is (100 - a) mass%, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that disproportionation reaction does not occur at 3.0 MPa and 150 °C, the GWP is 150 or less, and the refrigerating capacity (Cap) ratio to R410A is 60% or more.

[0104] <Requirements> When 0 < a ≤ 0.4, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point E(1.25a 2 - 2.25a + 24.3, 0.0, - 1.25a 2 + 1.25a + 75.7), Point F(0.0, - 1.5a + 15.5, 0.5a + 84.5) and [[ID=二十九]]Point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DE, EF, FB and BG connecting the five points respectively, or on the line segments GD, DE, EF and BG (excluding the points F and B), When 0.4 < a ≤ 10.0, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point E(-0.0013a 2-1.841a + 24.337, 0.0, 0.0013a 2 +0.841a + 75.663), point F(0.0, 0.0128a 2 -1.3516a + 15.439, -0.0128a 2 +0.3516a + 84.561) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DE, EF, FB, and BG connecting these five points respectively or on the line segments GD, DE, EF, and BG (excluding points F and B).

[0105] As described above, the test results for each mixed refrigerant are shown (compared with R404A).

[0106]

Table 18

[0107]

Table 19

[0108]

Table 20

[0109]

Table 21

[0110]

Table 22

[0111]

Table 23

[0112]

Table 24

[0113] [Table 25]

[0114] [Table 26]

[0115] [Table 27]

[0116] Note that the coordinates of each point were obtained based on the least squares method as follows.

[0117] [Table 28] [[ID=​​​​​​​​​​​​​​​​​​​​​​​Point D(-a + 44.0, 0.0, 56.0), Point I(-1.5a + 8.4, 0.0, 0.5a + 91.6), Point J(0.0, -a + 5.2, 94.8) and Point B(0.0, 21.8, -a + 78.2) Inside the figure surrounded by the line segments GD, DI, IJ, JB, and BG connecting these five points respectively, or on the line segments GD, DI, IJ, and BG (excluding points J and B), When 0.4 < a ≤ 5.5, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point I(0.0036a 2 -1.5508a + 8.42, 0.0, -0.0036a 2 + 0.5508a + 91.58), Point J(0.0, 0.0081a 2 -0.9892a + 5.194, -0.0081a 2 -0.0108a + 94.806) and Point B(0.0, 21.8, -a + 78.2) Inside the figure surrounded by the line segments GD, DI, IJ, JB, and BG connecting these five points respectively, or on the line segments GD, DI, IJ, and BG (excluding points J and B), and, When 5.5 < a ≤ 10.0, Point G(-a + 52.8, 22.0, 25.2), Point D(-a + 44.0, 0.0, 56.0), Point O(0.0, 0.0, -a + 100.0) and Point B(0.0, 21.8, -a + 78.2) Inside the figure surrounded by the line segments GD, DO, OB, and BG connecting these four points respectively, or on the line segments GD, DO, and BG (excluding points O and B).

[0121] As described above, the test results for each mixed refrigerant are shown (R1234yf ratio).

[0122] Table 30

[0123] Table 31

[0124] Table 32

[0125] Table 33

[0126] Table 34

[0127] Table 35

[0128] Table 36

[0129] Table 37

[0130] Table 38

[0131] Table 39

[0132] The coordinates of each point were determined based on the least squares method as follows.

[0133]

Table 40

[0134] In the above aspect, the refrigerant of the present disclosure is such that the mass % based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are x, y, z, and a respectively (where 0 < a ≤ 10.0), and in the ternary composition diagram (see FIGS. 13 to 19) where the sum of HFO-1132(E), R32, and R1234yf is (100 - a) mass %, when the coordinates (x, y, z) satisfy the following requirements, it can be seen that no disproportionation reaction occurs at 3.0 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less.

[0135] <Requirements> When 0 < a ≤ 0.4, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-4a + 14.6, 0.0, 3a + 85.4), point L(0.0, -a + 5.2, 94.8) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DK, KL, LB, and BG connecting these five points respectively or on the line segments GD, DK, KL, and BG (excluding points L and B), When 0.4 < a ≤ 3.5, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point K(-0.0457a 2 -4.0153a + 14.613, 0.0, 0.0457a 2 + 3.0153a + 85.387), point L(0.0, 0.2245a 2-3.1012a + 8.105, -0.2245a 2 +2.1012a + 91.895) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DK, KL, LB, and BG connecting the five points respectively or on the line segments GD, DK, KL, and BG (excluding points L and B), and when 3.5 < a ≤ 10.0, point G(-a + 52.8, 22.0, 25.2), point D(-a + 44.0, 0.0, 56.0), point O(0.0, 0.0, -a + 100.0) and point B(0.0, 21.8, -a + 78.2) within the range of the figure surrounded by the line segments GD, DO, OB, and BG connecting the four points respectively or on the line segments GD, DO, and BG (excluding points O and B).

[0136] HFO - 1132(E), R32, R1234yf, and HFO - 1132a were mixed in the mass percentages shown in Tables 41 and 42 based on their total sum, and the content and appearance of the acid component in the resulting composition were evaluated as follows respectively.

[0137] In the stability test of the composition, the analysis of the acid component in the gas was carried out by the following method. After cooling, the above - mentioned tube was used with liquid nitrogen to completely freeze the gas remaining in the tube. Then, the tube was opened and gradually thawed to collect the gas into a Tedlar bag. 5 g of pure water was injected into this Tedlar bag, and the acid component was extracted into the pure water while making it contact well with the recovered gas. The extract was detected by ion chromatography to measure the content (mass ppm) of fluoride ions (F - ).

[0138]

Table 41

[0139] [Table 42]

[0140] As shown in Tables 41 and 42, the formation of oxidative decomposition products can be confirmed in the presence of 0.01 mol% or more of oxygen. Furthermore, it can be seen that the amount of oxidative decomposition products is suppressed when the amount of water added is at least 10 ppm by mass in the presence of 0.01 mol% or more of oxygen. In addition, it can be seen that the formation of solid matter is suppressed when the amount of water added is less than 2000 ppm by mass in the presence of 0.01 mol% or more of oxygen.

Claims

1. A composition containing a refrigerant, The refrigerant includes trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a). In the aforementioned refrigerants, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: If 0 < a ≤ 0.4, Point C (-a+60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), Point F (0.0, -1.5a+15.5, 0.5a+84.5), Point B'' (0.0, 73.9, -a+26.1) and Point A'' (-a+26.0, 74.0, 0.0) The figure is located within the area enclosed by the line segments CD, DE, EF, FB'', B''A'' and A''C that connect the six points, or on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), If 0.4 < a ≤ 10.0, Point C (-a+60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (-0.0013a) 2 -1.841a+24.337, 0.0, 0.0013a 2 +0.841a+75.663), Point F (0.0, 0.0128a) 2 -1.3516a+15.439, -0.0128a 2 +0.3516a+84.561), Point B'' (0.0, 73.9, -a+26.1) and Point A'' (-a+26.0, 74.0, 0.0) The area enclosed by the line segments CD, DE, EF, FB'', B''A'' and A''C connecting the six points, or the area on the line segments CD, DE, EF and B''A'' (excluding points C, F, B'' and A''), A composition characterized by the following features.

2. In the aforementioned refrigerants, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: If 0 < a ≤ 0.4, Point C (-a+60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), Point F (0.0, -1.5a+15.5, 0.5a+84.5), Point B' (0.0, 44.1, -a+55.9) and Point A' (-a+55.7, 44.3, 0.0) The figure is located within the area enclosed by the line segments CD, DE, EF, FB', B'A', and A'C that connect the six points, or on the line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A'), If 0.4 < a ≤ 10.0, Point C (-a+60.0, 40.0, 0.0), Point D (-a+44.0, 0.0, 56.0), Point E (-0.0013a) 2 -1.841a+24.337, 0.0, 0.0013a 2 +0.841a+75.663), Point F (0.0, 0.0128a) 2 -1.3516a+15.439, -0.0128a 2 +0.3516a+84.561), Point B' (0.0, 44.1, -a+55.9) and Point A' (-a+55.7, 44.3, 0.0) The composition according to claim 1, wherein the figure is located within the area enclosed by the line segments CD, DE, EF, FB', B'A', and A'C that connect the six points, or is located on the line segments CD, DE, EF, and B'A' (excluding points C, F, B', and A').

3. In the aforementioned refrigerants, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: If 0 < a ≤ 0.4, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point E (1.25a 2 -2.25a + 24.3, 0.0, -1.25a 2 +1.25a + 75.7), Point F(0.0, -1.5a+15.5, 0.5a+84.5) and Point B (0.0, 21.8, -a+78.2) The figure is located within the area enclosed by the line segments GD, DE, EF, FB, and BG connecting the five points, or on the line segments GD, DE, EF, and BG (excluding points F and B), If 0.4 < a ≤ 10.0, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point E (-0.0013a) 2 -1.841a+24.337, 0.0, 0.0013a 2 +0.841a+75.663), Point F (0.0, 0.0128a 2 -1.3516a+15.439, -0.0128a 2 (+0.3516a+84.561) and Point B (0.0, 21.8, -a+78.2) Within the area enclosed by the line segments GD, DE, EF, FB, and BG connecting the five points, or on the line segments GD, DE, EF, and BG (excluding points F and B), The composition according to claim 1.

4. A composition containing a refrigerant, The refrigerant includes trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a). In the aforementioned refrigerants, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: If 0 < a ≤ 0.4, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point I (-1.5a+8.4, 0.0, 0.5a+91.6), Point J (0.0, -a+5.2, 94.8) and Point B (0.0, 21.8, -a+78.2) The figure is located within the area enclosed by the line segments GD, DI, IJ, JB, and BG connecting the five points, or on the line segments GD, DI, IJ, and BG (excluding points J and B). If 0.4 < a ≤ 5.5, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point I (0.0036a) 2 -1.5508a+8.42, 0.0, -0.0036a 2 +0.5508a+91.58), Point J (0.0, 0.0081a 2 -0.9892a+5.194, -0.0081a 2 -0.0108a+94.806) and Point B (0.0, 21.8, -a+78.2) The area within the figure enclosed by the line segments GD, DI, IJ, JB, and BG connecting the five points, or the area on the line segments GD, DI, IJ, and BG (excluding points J and B), and, If 5.5 < a ≤ 10.0, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point O(0.0, 0.0, -a+100.0) and Point B (0.0, 21.8, -a+78.2) Within the area of ​​the figure enclosed by the line segments GD, DO, OB, and BG connecting the four points, or on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the following features.

5. A composition containing a refrigerant, The refrigerant includes trans-1,2-difluoroethylene (HFO-1132(E)), difluoromethane (R32), 2,3,3,3-tetrafluoro-1-propene (R1234yf), and 1,1-difluoroethylene (HFO-1132a). In the aforementioned refrigerants, the mass percentages based on the sum of HFO-1132(E), R32, R1234yf, and HFO-1132a are denoted as x, y, z, and a, respectively (where 0 < a ≤ 10.0). In a three-component composition diagram where the sum of HFO-1132(E), R32, and R1234yf is (100-a) mass%, the coordinates (x,y,z) are: If 0 < a ≤ 0.4, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point K (-4a+14.6, 0.0, 3a+85.4), Point L(0.0, -a+5.2, 94.8) and Point B (0.0, 21.8, -a+78.2) The figure is located within the area enclosed by the line segments GD, DK, KL, LB, and BG connecting the five points, or on the line segments GD, DK, KL, and BG (excluding points L and B), If 0.4 < a ≤ 3.5, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point K (-0.0457a) 2 -4.0153a+14.613, 0.0, 0.0457a 2 +3.0153a+85.387), Point L (0.0, 0.2245a 2 -3.1012a+8.105, -0.2245a 2 (+2.1012a+91.895) and Point B (0.0, 21.8, -a+78.2) The area within the figure enclosed by the line segments GD, DK, KL, LB, and BG connecting the five points, or the area on the line segments GD, DK, KL, and BG (excluding points L and B), and, If 3.5 < a ≤ 10.0, Point G (-a+52.8, 22.0, 25.2), Point D (-a+44.0, 0.0, 56.0), Point O(0.0, 0.0, -a+100.0) and Point B (0.0, 21.8, -a+78.2) Within the area of ​​the figure enclosed by the line segments GD, DO, OB, and BG connecting the four points, or on the line segments GD, DO, and BG (excluding points O and B), A composition characterized by the following features.

6. Furthermore, the composition according to any one of claims 1 to 5, which contains refrigeration oil and is used as a working fluid for a refrigeration unit.

7. A composition according to any one of claims 1 to 3, which is used as a substitute refrigerant for R410A.

8. Use of the composition according to any one of claims 1 to 3 as a substitute refrigerant for R410A.

9. The composition according to claim 4, which is used as a substitute refrigerant for R404A.

10. Use of the composition according to claim 4 as a substitute refrigerant for R404A.

11. The composition according to claim 5, which is used as a substitute refrigerant for R1234yf.

12. Use of the composition according to claim 5 as a substitute refrigerant for R1234yf.

13. A refrigerator comprising the composition according to any one of claims 1 to 5 as a working fluid.

14. The method of operating a refrigerator, A method comprising the step of circulating a composition according to any one of claims 1 to 5 as a working fluid in a refrigerator.

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