Composition containing refrigerant, use thereof, refrigerator having same, and method for operating refrigerator

Abstract

The technical problem to be solved by the invention is to provide a novel low-GWP mixed refrigerant. The solution of the present invention is to provide a composition containing a refrigerant, the refrigerant containing trans-1, 2-difluoroethylene (HFO-132 (E)), 1, 1-difluoroethane (HFC-152a), and 1, 1-difluoroethylene (HFO-1132a).

Description

Technical Field

[0001] The present invention relates to a composition containing a refrigerant, use thereof, a refrigerator having the composition, and a method for operating the refrigerator. Background Art

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

[0003] Prior art literature Patent Literature Patent Document 1: International Publication No. 2015 / 141678 Summary of the Invention

[0004] Problems to be solved by the invention The object of the present invention is to provide a new low GWP mixed refrigerant.

[0005] Technical solutions to problems Item 1. A composition containing a refrigerant, wherein the refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), 1,1-difluoroethane (HFC-152a), and 1,1-difluoroethylene (HFO-1132a).

[0006] Item 2. The composition according to Item 1, wherein the refrigerant further comprises R32. In the above refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in the three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, When 0 < a ≤ 5.9, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2-1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0007] Item 3. The composition according to Item 1, wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, When 0 < a ≤ 5.9, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the following seven points, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1)、 Point F (0.0, -0.007a 2 -2.3826a +47.6, 0.007a 2 +1.3826a +52.4)、 Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EF, FB, BA, and AC connecting the following six points, or on the straight lines CD, DE, EF, and BA (excluding points C, F, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.0131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0008] Item 4. The composition according to Item 1, wherein, in the refrigerant, when the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, The coordinates (x, y, z) lie within the range of the figure enclosed by the straight lines CD, DE, EE', E'A', and A'C connecting the following five points, or lie on the straight lines CD, DE, EE', and E'A' (excluding points C and A') when 0 < a ≤ 5.9. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1) and Point A' (-a +55.6, 44.4, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EF, FB', B'A', and A'C connecting the following six points, or on the straight lines CD, DE, EF, and B'A' (excluding points C, F, B', and A'). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.00131a 2 +1.4253a +49.233) Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B' (0.0. -0.0137a 2 +0.4304a +31.164, 0.0137a 2 -1.4304a +68.836) and Point A' (-a +55.6, 44.4, 0.0).

[0009] Item 5. The composition according to Item 1, wherein the refrigerant further contains R32, and in the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, When the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the following four points, or on the straight lines D'D, DJ, JK, and KD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-10.625a +19.2, 5.625a +9.0, 15.25a +71.8), When 1.6 < a ≤ 1.7, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the following four points, or on the straight lines D'D, DJ, JK, and KD'. Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-22.0a +37.4, 0.0, 21.0a +62.6), When 1.7 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DO, OB'', and B''D' connecting the following four points, or on the straight lines D'D, DO, and B''D' (excluding points O and B''). Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100.0), Point B''(0.0, -0.0014a 2-0.2396a +4.657, 0.0014a 2 -1.2396a +95.343).

[0010] Item 6. The composition according to Item 1, wherein the refrigerant further comprises HFO-1132a, wherein in the refrigerant, when the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' connecting the following four points, or on the straight lines D'D, DL, LM, and MD' when 0 < a ≤ 5.9, Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (-1.6619a +16.92, -0.1522a +8.4929, 0.8141a +74.587) and Point M (0.0046a 2 -1.8915a +25.9, 0.0, -0.0462a 2 +0.8915a +74.1), When the coordinates (x, y, z) are 5.9 < a ≤ 10.0, they are within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' connecting the following four points, or on the straight lines D'D, DL, LM, and MD'. Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (0.0219a 2 -1.9578a +17.889, -0.005a 2 -0.0668a +8.1682, -0.0169a 2 +1.0246a +73.943) and Point M (0.0075a 2 -1.8998a +25.848, 0.0, -0.0075a 2 +0.8998a +74.152).

[0011] Item 7. A freezing method comprising the step of operating a freezing cycle using the composition according to any one of Items 1 to 6.

[0012] Item 8. A refrigeration device comprising the composition according to any one of Items 1 to 6 as a working fluid.

[0013] Item 9. A method for inhibiting the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using the composition according to any one of Items 1 to 6.

[0014] Item 10. Use of HFO-1123, R32, R152a, and HFO-1132a for inhibiting the disproportionation reaction of HFO-1132(E), wherein the inhibition of the disproportionation reaction is performed by mixing HFO-1123, R32, R152a, HFO-1132a, and HFO-1132(E) at the mixing ratio of the composition described in any one of Items 1 to 6.

[0015] Effects of the Invention The refrigerant of the present invention has a low GWP. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0017] Figure 2 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0018] Figure 3 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0019] Figure 4 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0020] Figure 5 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0021] Figure 6 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0022] Figure 7 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0023] Figure 8 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0024] Figure 9 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0025] Figure 10 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0026] Figure 11 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0027] Figure 12 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0028] Figure 13 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0029] Figure 14 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0030] Figure 15 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0031] Figure 16 It is a triangular diagram showing the composition of the refrigerant of the present invention.

[0032] Figure 17 It is a triangular diagram showing the composition of the refrigerant of the present invention. DETAILED DESCRIPTION

[0033] In order to solve the above-mentioned technical problems, the inventors of the present invention have conducted intensive studies and found that various mixed refrigerants described below have the above-mentioned characteristics.

[0034] The present invention has been completed through further research based on the above findings. The present invention includes the following embodiments.

[0035] Definition of terms In this manual, the term "refrigerant" includes at least compounds designated by an ASHRAE number (preceding "R"), as defined by ISO 817 (International Organization for Standardization), and also includes substances without an ASHRAE number but exhibiting equivalent refrigerant properties. Based on their structure, refrigerants are broadly categorized as "fluorocarbon compounds" and "non-fluorocarbon compounds." "Fluorocarbon compounds" include chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs).

[0036] In this specification, the term "refrigerant-containing composition" includes at least: (1) the refrigerant itself (including a mixture of refrigerants); (2) a composition that also contains other components and can be used to obtain a working fluid for a refrigerator by mixing with at least refrigeration oil; and (3) a working fluid for a refrigerator containing refrigeration oil. In this specification, of these three types, the composition in (2) is distinguished from the refrigerant itself (including a mixture of refrigerants) and expressed as a "refrigerant composition." Furthermore, the working fluid for a refrigerator in (3) is distinguished from the "refrigerant composition" and expressed as a "working fluid containing refrigeration oil."

[0037] In this specification, the term "replacement," when used in the context of "replacing" a first refrigerant with a second refrigerant, refers to a first type of operation in equipment designed to operate with the first refrigerant. By making only a few component changes and adjustments (at least one of the following: refrigeration oil, gaskets, packings, expansion valves, dryers, or other components) as needed, the equipment can be operated under optimal conditions using the second refrigerant. In other words, this type of operation allows the same equipment to operate by "replacing" the refrigerant. This type of "replacement" can be classified into "drop-in replacement," "nearly drop-in replacement," and "retrofit," depending on the degree of change or adjustment required when switching to the second refrigerant.

[0038] The second type, using a second refrigerant to adapt equipment designed to operate with it for the same purpose as the first refrigerant, also falls under the term "substitution." This type means the "substitution" refrigerant serves the same purpose.

[0039] In this specification, the term "refrigerator" refers to any device that removes heat from an object or space, bringing it to a lower temperature than the surrounding air, and maintaining that lower temperature. In other words, a refrigerator is a device that converts energy from an external source to produce work, moving heat from a lower temperature to a higher temperature.

[0040] In this specification, "vehicle air conditioning equipment" refers to a type of refrigeration system used in gasoline-powered vehicles, hybrid vehicles, electric vehicles, hydrogen-powered vehicles, and other vehicles. This refers to a refrigeration system that utilizes a refrigeration cycle. This refrigeration cycle uses an evaporator to exchange heat with a liquid refrigerant, a compressor to draw in the evaporated refrigerant gas, adiabatically compressed refrigerant gas to cool and liquefy it in a condenser, and then adiabatically expands it through an expansion valve before supplying it back to the evaporator as liquid refrigerant.

[0041] The pressure described in this specification is absolute pressure unless otherwise specified.

[0042] 1. refrigerant The refrigerant of the present invention contains HFO-1132(E), HFC-152a, and HFO-1132a. The refrigerant of the present invention may further contain difluoromethane (R32).

[0043] The refrigerant of the present invention is a low GWP mixed refrigerant.

[0044] In the refrigerant of the present invention, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0<a≤10.0), respectively, if the coordinates (x, y, z) in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100-a) mass % satisfy the following conditions, no disproportionation reaction occurs at 5 MPa and 150°C, and the GWP is 400 or less.

[0045] <Conditions> 0<a≤5.9, it is within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), 5.9<a≤10.0, the object is within the range of the figure enclosed by straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, -0.0019a2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0046] In the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150° C., the GWP is 400 or less, and the refrigeration capacity (Cap) ratio relative to R410A is 70% or more.

[0047] <Conditions> 0<a≤5.9, within the range of the figure enclosed by straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the following seven points, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1)、 Point F (0.0, -0.007a 2 -2.3826a +47.6, 0.007a 2 +1.3826a +52.4)、 Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), 5.9<a≤10.0, within the range of the figure enclosed by straight lines CD, DE, EF, FB, BA, and AC connecting the following six points, or on the straight lines CD, DE, EF, and BA (excluding points C, F, B, and A); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.0131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0048] In the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150° C., the GWP is 300 or less, and the refrigeration capacity (Cap) ratio relative to R410A is 70% or more.

[0049] <Conditions> 0<a≤5.9, within the range of the figure enclosed by the straight lines CD, DE, EE', E'A' and A'C connecting the following five points, or on the straight lines CD, DE, EE' and E'A' (excluding points C and A'), Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1) and Point A' (-a +55.6, 44.4, 0.0), 5.9<a≤10.0, within the range of the figure enclosed by straight lines CD, DE, EF, FB', B'A' and A'C connecting the following six points, or on the straight lines CD, DE, EF and B'A' (excluding points C, F, B' and A'); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.00131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B' (0.0. -0.0137a 2 +0.4304a +31.164, 0.0137a 2 -1.4304a +68.836) and Point A' (-a +55.6, 44.4, 0.0).

[0050] In the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150° C., the GWP is 150 or less, and the boiling point is −40° C. or less.

[0051] <Conditions> 0<a≤1.6, it is located within the range of the figure enclosed by the straight lines D'D, DJ, JK and KD' connecting the following four points, or on the straight lines D'D, DJ, JK and KD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-10.625a +19.2, 5.625a +9.0, 15.25a +71.8), 1.6<a≤1.7, within the range of the figure enclosed by the straight lines D'D, DJ, JK and KD' connecting the following four points, or on the straight lines D'D, DJ, JK and KD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-22.0a +37.4, 0.0, 21.0a +62.6), 1.7<a≤10.0, within the range of the figure enclosed by the straight lines D'D, DO, OB'', and B''D' connecting the following four points, or on the straight lines D'D, DO, and B''D' (excluding points O and B''); Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100.0) Point B''(0.0, -0.0014a 2 -0.2396a +4.657, 0.0014a 2 -1.2396a +95.343).

[0052] The refrigerant of the present invention may contain HFO-1132(E) and HFC-152a. The refrigerant may further contain R32.

[0053] In the above embodiment, regarding the refrigerant of the present invention, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0<a≤10.0), respectively, in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100-a) mass%, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio relative to R404A is 70% or more.

[0054] <Conditions> 0<a≤5.9, it is located within the range of the figure enclosed by the straight lines D'D, DL, LM and MD' connecting the following four points, or on the straight lines D'D, DL, LM and MD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (-1.6619a +16.92, -0.1522a +8.4929, 0.8141a +74.587) and Point M (0.0046a 2 -1.8915a +25.9, 0.0, -0.0462a 2 +0.8915a +74.1), 5.9<a≤10.0, within the range of the figure enclosed by the straight lines D'D, DL, LM and MD' connecting the following four points, or on the straight lines D'D, DL, LM and MD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (0.0219a 2 -1.9578a +17.889, -0.005a 2 -0.0668a +8.1682, -0.0169a 2 +1.0246a +73.943) and Point M (0.0075a 2 -1.8998a +25.848, 0.0, -0.0075a 2 +0.8998a +74.152).

[0055] The refrigerant of the present invention may contain 10% by mass or more of HFO-1132(E), 20% by mass or more, 30% by mass or more, 40% by mass or more, or even 50% by mass or more, based on the entire refrigerant.

[0056] The refrigerant of the present invention may contain 10% by mass or more of R32, 20% by mass or more, 30% by mass or more, 40% by mass or more, or even 50% by mass or more, based on the entire refrigerant.

[0057] The refrigerant of the present invention may contain more than 10% by mass of R152a, more than 20% by mass, more than 30% by mass, more than 40% by mass, more than 50% by mass, more than 60% by mass, more than 70% by mass, more than 80% by mass, or more than 90% by mass, relative to the total refrigerant.

[0058] The refrigerant of the present invention may contain additional refrigerants in addition to HFO-1132(E), R32, HFC-152a, and HFO-1132a, as long as the aforementioned properties and effects are not impaired. In this regard, in one embodiment, the refrigerant of the present invention preferably contains 99.5% by mass or more of HFO-1132(E), R32, HFC-152a, and HFO-1132a, more preferably 99.75% by mass or more, even 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. The refrigerant of the present invention may also consist essentially solely of HFO-1132(E), R32, HFC-152a, and HFO-1132a. In this case, the refrigerant of the present invention may consist solely of HFO-1132(E), R32, HFC-152a, and HFO-1132a, along with unavoidable impurities. The refrigerant of the present invention may be composed only of HFO-1132(E), R32, HFC-152a, and HFO-1132a.

[0059] The additional refrigerant is not particularly limited and can be selected from a wide range. The mixed refrigerant may contain one type of additional refrigerant alone or two or more types.

[0060] Examples of the additional refrigerant include methylamine, acetylene, HFO-1141, HFO-1123, HFC-143a, HFC-134a, Z-HFO-1132, HFO-1243zf, HFC-245cb, HCFC-1122, HCFC-124, CFC-1113, and 3,3,3-trifluoropropyne.

[0061] 2. Refrigerant composition The refrigerant composition of the present invention contains at least the refrigerant of the present invention and can be used for the same purposes as the refrigerant of the present invention. In addition, the refrigerant composition of the present invention can also be used to obtain a refrigerator working fluid by mixing with at least refrigerator oil.

[0062] The refrigerant composition of the present invention may contain at least one other component in addition to the refrigerant of the present invention. The refrigerant composition of the present invention may contain at least one of the following other components as needed. As described above, when the refrigerant composition of the present invention is used as a working fluid for a refrigerator, it is usually mixed with at least one refrigerator oil. Therefore, the refrigerant composition of the present invention preferably does not substantially contain refrigerator oil. Specifically, with respect to the refrigerant composition of the present invention, the content of refrigerator oil relative to the total refrigerant composition is preferably 1% by mass or less, more preferably 0.1% by mass or less.

[0063] 2.1 water The refrigerant composition of the present invention may contain a trace amount of water. The water content in the refrigerant composition is preferably 0.1% by mass or less relative to the total refrigerant. The presence of a trace amount of water in the refrigerant composition stabilizes the intramolecular double bonds of the unsaturated fluorocarbon compound that may be contained in the refrigerant, and reduces the likelihood of oxidation of the unsaturated fluorocarbon compound, thereby improving the stability of the refrigerant composition.

[0064] The composition of the present invention also includes a composition containing a refrigerant containing HFO-1132(E), R32, and R1234yf, and 0.1% or less of water.

[0065] 2.2 tracer In order to track the changes in the refrigerant composition of the present invention when it undergoes dilution, contamination, or other changes, a tracer is added to the refrigerant composition of the present invention at a detectable concentration.

[0066] The refrigerant composition of the present invention may contain one type of tracer alone or two or more types of tracers.

[0067] The tracer is not particularly limited and can be appropriately selected from commonly used tracers.

[0068] Examples of tracers include hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, deuterated hydrocarbons, deuterated hydrofluorocarbons, perfluorocarbons, fluorinated ethers, brominated compounds, iodinated compounds, alcohols, aldehydes, ketones, and nitrous oxide (N2O). Particularly preferred tracers are hydrofluorocarbons, hydrochlorofluorocarbons, chlorofluorocarbons, hydrochlorocarbons, fluorocarbons, and fluorinated ethers.

[0069] As the tracer, the following compounds are preferred.

[0070] FC-14 (tetrafluoromethane, CF4) HCC-40 (Methyl Chloride, CH3Cl) HFC-23 (trifluoromethane, CHF3) HFC-41 (fluoromethane, CH3Cl) 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-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) The refrigerant composition of the present invention may contain a total of about 10 parts per million (ppm) by weight or more of the tracer relative to the total refrigerant composition. Furthermore, the refrigerant composition of the present invention may contain a total of about 1000 ppm or less of the tracer relative to the total refrigerant composition. The refrigerant composition of the present invention may contain a total of preferably about 30 ppm or more, more preferably about 50 ppm or more of the tracer relative to the total refrigerant composition. The refrigerant composition of the present invention may contain a total of preferably about 500 ppm or less of the tracer relative to the total refrigerant composition, and may also contain a total of about 300 ppm or less of the tracer relative to the total refrigerant composition.

[0071] 2.3 UV fluorescent dye The refrigerant composition of the present invention may contain a single type of ultraviolet fluorescent dye or two or more types of ultraviolet fluorescent dye.

[0072] The ultraviolet fluorescent dye is not particularly limited and can be appropriately selected from commonly used ultraviolet fluorescent dyes.

[0073] Examples of ultraviolet fluorescent dyes include naphthalimide, coumarin, anthracene, phenanthrene, xanthene, thioxanthene, benzoxanthene, fluorescein, and derivatives thereof. As ultraviolet fluorescent dyes, either or both of naphthalimide and coumarin are particularly preferred.

[0074] 2.4 stabilizer The refrigerant composition of the present invention may contain one type of stabilizer alone or two or more types of stabilizers.

[0075] The stabilizer is not particularly limited and can be appropriately selected from commonly used stabilizers.

[0076] Examples of the stabilizer include nitro compounds, ethers, and amines.

[0077] Examples of the nitro compound include aliphatic nitro compounds such as nitromethane and nitroethane, and aromatic nitro compounds such as nitrobenzene and nitrostyrene.

[0078] Examples of the ethers include 1,4-dioxane and the like.

[0079] Examples of the amines include 2,2,3,3,3-pentafluoropropylamine and diphenylamine.

[0080] Other examples include butylated hydroxyxylene and benzotriazole.

[0081] The content of the stabilizer relative to the total refrigerant is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and preferably 5% by mass or less, more preferably 2% by mass or less.

[0082] 2.5 polymerization inhibitors The refrigerant composition of the present invention may contain one type of polymerization inhibitor alone or two or more types thereof.

[0083] The polymerization inhibitor is not particularly limited and can be appropriately selected from commonly used polymerization inhibitors.

[0084] Examples of the polymerization inhibitor include 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole.

[0085] The content of the polymerization inhibitor is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, relative to the total refrigerant, and preferably 5% by mass or less, more preferably 2% by mass or less.

[0086] 3. Working fluid containing refrigeration oil The working fluid containing refrigerator oil of the present invention contains at least refrigerant or refrigerant composition of the present invention and refrigerator oil, and is used as the working fluid in refrigerator. Specifically, the working fluid containing refrigerator oil of the present invention is obtained by mixing the refrigerator oil used in the compressor of refrigerator with the refrigerant or refrigerant composition. In the working fluid containing refrigerator oil, the refrigerator oil of more than 10 mass % is usually contained. In the working fluid containing refrigerator oil, the refrigerator oil of less than 50 mass % is usually contained.

[0087] 3.1 Refrigeration oil The composition of the present invention may contain one type of refrigeration oil alone or two or more types of refrigeration oil.

[0088] The refrigeration oil is not particularly limited and can be appropriately selected from commonly used refrigeration oils. If necessary, a refrigeration oil that is superior in improving compatibility with the mixture and stability of the mixture can be appropriately selected.

[0089] As the base oil of the refrigeration oil, for example, at least one selected from polyalkylene glycol (PAG), polyol ester (POE), and polyvinyl ether (PVE) is preferably used.

[0090] In addition to the base oil, the refrigeration oil may contain additives. The additive may be at least one selected from the group consisting of antioxidants, extreme pressure agents, acid scavengers, oxygen scavengers, copper passivators, rust inhibitors, oiliness agents, and defoaming agents.

[0091] From the perspective of lubrication, the refrigeration oil preferably has a kinematic viscosity of 5 cSt or more at 40° C. From the perspective of lubrication, the refrigeration oil preferably has a kinematic viscosity of 400 cSt or less at 40° C.

[0092] The working fluid containing refrigeration oil of the present invention may further contain at least one additive as needed. Examples of the additive include the following solubilizers.

[0093] 3.2 solubilizer The refrigeration oil-containing working fluid of the present invention may contain one type of solubilizing agent alone or two or more types of solubilizing agents.

[0094] The solubilizing agent is not particularly limited and can be appropriately selected from commonly used solubilizing agents.

[0095] Examples of the solubilizing agent include polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorinated hydrocarbons, esters, lactones, aryl ethers, fluorinated ethers, and 1,1,1-trifluoroalkanes. Polyoxyalkylene glycol ethers are particularly preferred as the solubilizing agent.

[0096] 4. How to operate a freezer The method for operating a refrigerator of the present invention is a method for operating a refrigerator using the refrigerant of the present invention.

[0097] Specifically, the method for operating a refrigerator of the present invention includes a step of circulating the refrigerant of the present invention in the refrigerator.

[0098] 5. Methods for inhibiting disproportionation reactions The method for suppressing the disproportionation reaction of the present invention is a method for suppressing the disproportionation reaction of HFO-1132(E), comprising the step of operating a refrigeration cycle using the refrigerant of the present invention.

[0099] The method for suppressing the disproportionation reaction of the present invention can achieve the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring, particularly when the refrigerant pressure is 5.0 to 3.0 MPa and the refrigerant temperature is 150°C.

[0100] According to the method for suppressing the disproportionation reaction of the present invention, it is possible to operate the refrigeration cycle while suppressing the disproportionation reaction, particularly in a refrigerator not provided with a unit for suppressing the disproportionation reaction.

[0101] 6. Use for inhibiting disproportionation reaction The present invention relates to the use of HFO-1123, R32, R152a, and HFO-1132a for inhibiting the disproportionation reaction of HFO-1132(E). The disproportionation reaction is inhibited by mixing HFO-1123, R32, R152a, HFO-1132a, and HFO-1132(E) at the refrigerant mixing ratio of the present invention.

[0102] In the application of the present invention for suppressing the disproportionation reaction, the effect of preventing the disproportionation reaction of HFO-1132(E) from occurring can be achieved, particularly when the refrigerant pressure is 5.0 to 3.0 MPa and the refrigerant temperature is 150°C.

[0103] Although the embodiments have been described above, it should be understood that various changes in form and details may be made without departing from the spirit and scope of the scope of the claims.

[0104] Example The following examples are given to further explain the present invention in detail, but the present invention is not limited to these examples.

[0105] HFO-1132(E), R32, R152a, and HFO-1132a were mixed at the mass % shown in Tables 1 to 3 based on the total of these components to prepare mixed refrigerants.

[0106] For each of these mixed refrigerants, the presence or absence of disproportionation reaction was examined using the following test method and test conditions.

[0107] Test methods The refrigerant composition to be tested was transferred and filled into a test container. After heating to 150°C, a voltage was applied to the Pt wire inside the container to cause it to fuse, thereby supplying 30 J of energy to the refrigerant composition. The occurrence of a disproportionation reaction was determined by the rapid increase in pressure and temperature within the apparatus.

[0108] Test conditions Test container: 38cc SUS container; Test temperature: 150℃; Pressure: 53 MPa Judgment Criteria “No explosion”: The temperature or pressure after the Pt wire melts is less than 2 times, and no rapid disproportionation reaction occurs.

[0109] "Explosion": After the Pt wire melts, the temperature or pressure reaches more than 2 times, and a rapid disproportionation reaction occurs.

[0110] [Table 1] [Table 2] [Table 3] According to the results in Tables 1 to 3, it can be seen that the refrigerant of the present invention Figures 1 to 17 No disproportionation occurs in the region shown in the triangular diagram shown in FIG16 .

[0111] The GWP of the mixed refrigerant was evaluated based on the values of 1 for HFO-1132(E) and the GWPs of R32 and HFO-1234yf in the Fourth Report of the Intergovernmental Panel on Climate Change (IPCC). The COP, refrigeration capacity, discharge temperature, and boiling point of the mixed refrigerant were calculated using the Reference Fluid Thermodynamic and Transport Properties Database (Refprop 10.0) of the National Institute of Science and Technology (NIST) under the following conditions using theoretical calculations of the mixed refrigerant's refrigeration cycle. The physical properties of HFO-1132(E) were obtained using measured values.

[0112] <Performance comparison with R410A> Evaporation temperature 5℃ Condensation temperature 45℃ Overheat temperature 5K Supercooling temperature 5K Compressor efficiency 70% <Performance comparison with R1234yf> Evaporation temperature -30℃ Condensation temperature 30℃ Overheat temperature 5K Supercooling temperature 5K Compressor efficiency 70% <Performance comparison with R404A> Evaporation temperature -40℃ Condensation temperature 40℃ Overheat temperature 20K Supercooling temperature 0K Compressor efficiency 70% In the following tables, “COP ratio” and “refrigeration capacity ratio” indicate the ratio (%) relative to each designated refrigerant.

[0113] In the table, "Boiling Point (°C)" indicates the temperature at which the liquid phase of the mixed refrigerant reaches atmospheric pressure (101.33 kPa). "Power Consumption (%)" indicates the amount of electricity used to operate an electric vehicle, expressed as a ratio to this electricity consumption when the refrigerant is R1234yf. "Heating Power Consumption (%)" indicates the amount of electricity used to operate an electric vehicle, expressed as a ratio to this electricity consumption when the refrigerant is R1234yf.

[0114] In the following table, "Drivable distance (with)" indicates the distance that can be traveled with heating, expressed as a relative percentage (%), for an electric vehicle equipped with a secondary battery with a certain charge level, with the distance (without) when traveling without heating (heating power consumption is 0) set as 100%.

[0115] Regarding the heating method, an electric heater method is used for heating of refrigerants with a boiling point exceeding -40°C, while a heat pump method is used for heating of refrigerants with a boiling point below -40°C.

[0116] The power consumption during heating is calculated using the following formula: Heating COP stands for "heating efficiency."

[0117] Electricity consumption during heating = Heating capacity / Heating COP Regarding heating efficiency, in the case of an electric heater, heating COP = 1, and heating consumes electricity equivalent to power. In other words, heating power consumption is E = E / (1 + COP).

[0118] On the other hand, in the case of a heat pump, Refprop 10.0 (manufactured by NIST) was also used to perform theoretical calculations of a refrigeration cycle of a mixed refrigerant under the following conditions to determine the heating COP.

[0119] Evaporation temperature -30℃; Condensation temperature 30℃; Overheat temperature 5K; Supercooling temperature 5K; Compressor efficiency is 70%.

[0120] The drivable distance is calculated using the following formula.

[0121] Driving distance = (battery capacity) / (power consumption for driving + power consumption for heating) These values are shown in the following table together with the GWP of each mixed refrigerant. The COP ratio and refrigeration capacity ratio are shown as a ratio relative to R410A, R1234yf, or R404A.

[0122] The coefficient of performance (COP) is calculated using the following formula.

[0123] COP = (cooling capacity or heating capacity) / electricity consumption [Table 4] [Table 5] [Table 6] [Table 7] [Table 8] [Table 9] Use the following procedure to find the coordinates of each point using the least squares method.

[0124] [Table 10] [Table 11] [Table 12] [Table 13] The above results show that, in the refrigerant of the present invention, when the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0 < a ≤ 10.0), respectively, and in a three-component composition diagram where the sum of HFO-1132(E), R32, and HFC-152a is (100 - a) mass %, the following conditions are met at the coordinates (x, y, z) in the diagram: no disproportionation reaction occurs at 53 MPa and 150°C, and the GWP is 400 or less.

[0125] <Conditions> 0<a≤5.9, it is within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), 5.9<a≤10.0, the object is within the range of the figure enclosed by straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA (excluding points C, O, B, and A). Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0126] It is found that in the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 5 MPa and 150°C, the GWP is 400 or less, and the refrigeration capacity (Cap) ratio relative to R410A is 70% or more.

[0127] <Conditions> 0<a≤5.9, within the range of the figure enclosed by straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the following seven points, or on the straight lines CD, DE, EE', E'F, and BA (excluding points C, F, B, and A); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1)、 Point F (0.0, -0.007a 2 -2.3826a +47.6, 0.007a 2 +1.3826a +52.4)、 Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), 5.9<a≤10.0, within the range of the figure enclosed by straight lines CD, DE, EF, FB, BA, and AC connecting the following six points, or on the straight lines CD, DE, EF, and BA (excluding points C, F, B, and A); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.0131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

[0128] It is found that in the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150°C, the GWP is 300 or less, and the refrigeration capacity (Cap) ratio relative to R410A is 70% or more.

[0129] <Conditions> 0<a≤5.9, within the range of the figure enclosed by the straight lines CD, DE, EE', E'A' and A'C connecting the following five points, or on the straight lines CD, DE, EE' and E'A' (excluding points C and A'), Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a+53.1) and Point A' (-a +55.6, 44.4, 0.0), 5.9<a≤10.0, within the range of the figure enclosed by straight lines CD, DE, EF, FB', B'A' and A'C connecting the following six points, or on the straight lines CD, DE, EF and B'A' (excluding points C, F, B' and A'); Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.00131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B' (0.0. -0.0137a 2 +0.4304a +31.164, 0.0137a 2 -1.4304a +68.836) and Point A' (-a +55.6, 44.4, 0.0).

[0130] As described above, the results of the tests on the respective mixed refrigerants are shown (ratios relative to R1234yf).

[0131] [Table 14] [Table 15] [Table 16] [Table 17] [Table 18] [Table 19] [Table 20] [Table 21] [Table 22] [Table 23] [Table 24] [Table 25] [Table 26] Use the following procedure to find the coordinates of each point using the least squares method.

[0132] [Table 27] [Table 28] [Table 29] The above results show that in the refrigerant of the present invention, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150°C, the GWP is 150 or less, and the boiling point is -40°C or less.

[0133] <Conditions> 0<a≤1.6, it is located within the range of the figure enclosed by the straight lines D'D, DJ, JK and KD' connecting the following four points, or on the straight lines D'D, DJ, JK and KD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-10.625a +19.2, 5.625a +9.0, 15.25a +71.8), 1.6<a≤1.7, within the range of the figure enclosed by the straight lines D'D, DJ, JK and KD' connecting the following four points, or on the straight lines D'D, DJ, JK and KD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-22.0a +37.4, 0.0, 21.0a +62.6), 1.7<a≤10.0, within the range of the figure enclosed by the straight lines D'D, DO, OB'', and B''D' connecting the following four points, or on the straight lines D'D, DO, and B''D' (excluding points O and B''); Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100.0), Point B''(0.0, -0.0014a 2 -0.2396a +4.657, 0.0014a 2 -1.2396a +95.343).

[0134] As described above, the results of the tests on the various mixed refrigerants are shown (ratios relative to R404A).

[0135] [Table 30] [Table 31] [Table 32] [Table 33] [Table 34] [Table 35] [Table 36] Use the following procedure to find the coordinates of each point using the least squares method.

[0136] [Table 37] In the above embodiment, regarding the refrigerant of the present invention, it can be seen that, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are x, y, z, and a (where 0<a≤10.0), respectively, in a three-component composition diagram in which the sum of HFO-1132(E), R32, and HFC-152a is (100-a) mass%, when the coordinates (x, y, z) satisfy the following conditions, no disproportionation reaction occurs at 53 MPa and 150°C, the GWP is 150 or less, and the refrigeration capacity (Cap) ratio relative to R404A is 70% or more.

[0137] <Conditions> 0<a≤5.9, it is located within the range of the figure enclosed by the straight lines D'D, DL, LM and MD' connecting the following four points, or on the straight lines D'D, DL, LM and MD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (-1.6619a +16.92, -0.1522a +8.4929, 0.8141a +74.587) and Point M (0.0046a 2 -1.8915a +25.9, 0.0, -0.0462a 2 +0.8915a +74.1) 5.9<a≤10.0, within the range of the figure enclosed by the straight lines D'D, DL, LM and MD' connecting the following four points, or on the straight lines D'D, DL, LM and MD', Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (0.0219a 2 -1.9578a +17.889, -0.005a 2 -0.0668a +8.1682, -0.0169a 2 +1.0246a +73.943) and Point M (0.0075a 2 -1.8998a +25.848, 0.0, -0.0075a 2 +0.8998a +74.152).

Claims

1. A composition containing a refrigerant, characterized in that: The refrigerant contains trans-1,2-difluoroethylene (HFO-1132(E)), 1,1-difluoroethane (HFC-152a) and 1,1-difluoroethylene (HFO-1132a).

2. The composition according to claim 1, wherein: The refrigerant also contains R32 or does not contain R32, In the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are 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 HFC-152a is (100-a) mass%, When 0 < a ≤ 5.9, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA, excluding points C, O, B, and A. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DO, OB, BA, and AC connecting the following five points, or on the straight lines CD, DO, and BA, excluding points C, O, B, and A. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100), Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

3. The composition according to claim 1, wherein: In the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are 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 HFC-152a is (100-a) mass%, When 0 < a ≤ 5.9, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EE', E'F, FB, BA, and AC connecting the following seven points, or on the straight lines CD, DE, EE', E'F, and BA, excluding points C, F, B, and A. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a +53.1)、 Point F (0.0, -0.007a 2 -2.3826a +47.6, 0.007a 2 +1.3826a +52.4)、 Point B (0.0, 0.006a 2 +0.185a +32.00, -0.006a 2 -1.185a +68.00) and Point A (-a +40.8, 59.2, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EF, FB, BA, and AC connecting the following six points, or on the straight lines CD, DE, EF, and BA, excluding points C, F, B, and A. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a + 50.767, 0.0, 0.0131a 2 + 1.4253a + 49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B (0.0, -0.0019a 2 +0.225a +32.038, 0.0019a 2 -1.225a +67.962) and Point A (-a +40.8, 59.2, 0.0).

4. The composition according to claim 1, wherein: In the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are 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 HFC-152a is (100-a) mass%, When 0 < a ≤ 5.9, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EE', E'A', and A'C connecting the following five points, or on the straight lines CD, DE, EE', and E'A', excluding point C and point A'. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0152a 2 -2.4021a +50.70, 0.0, 0.00152a 2 +1.4021a +49.30)、 Point E' (-0.0082a 2 -2.0196a +12.2, 0.0008a 2 -0.242a +34.7, 0.0074a 2 +1.2616a +53.1) and Point A' (-a +55.6, 44.4, 0.0), When 5.9 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines CD, DE, EF, FB', B'A', and A'C connecting the following six points, or on the straight lines CD, DE, EF, and B'A', excluding points C, F, B', and A'. Point C (-a +60.0, 40.0, 0.0), Point D (-a +57.0, 0.0, 43.0), Point E (-0.0131a 2 -2.4253a +50.767, 0.0, 0.00131a 2 +1.4253a +49.233), Point F (0.0, 0.0081a 2 -2.6415a +48.602, -0.0081a 2 +1.6415a +51.398)、 Point B' (0.

0. -0.0137a 2 +0.4304a +31.164, 0.0137a 2 -1.4304a +68.836) and Point A' (-a +55.6, 44.4, 0.0).

5. The composition according to claim 1, wherein: The refrigerant further contains R32. In the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are 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 HFC-152a is (100-a) mass%, When 0<a≤1.6, the coordinates (x, y, z) are located within the range of the figure enclosed by the straight lines D'D, DJ, JK and KD' connecting the following four points, or on the straight lines D'D, DJ, JK and KD'. Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-10.625a +19.2, 5.625a +9.0, 15.25a +71.8), The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DJ, JK, and KD' connecting the following four points, or on the straight lines D'D, DJ, JK, and KD', when 1.6 < a ≤ 1.7, Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point J (-17.625a +28.2, 3.1875a, 13.438a +71.8) and Point K (-22.0a +37.4, 0.0, 21.0a +62.6), When 1.7 < a ≤ 10.0, the coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DO, OB'', and B''D' connecting the following four points, or on the straight lines D'D, DO, and B''D', excluding point O and point B''. Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point O (0.0, 0.0, -a +100.0), Point B''(0.0, -0.0014a 2 -0.2396a +4.657, 0.0014a 2 -1.2396a +95.343).

6. The composition according to claim 1, wherein: The refrigerant further contains HFO-1132a. In the refrigerant, assuming that the mass percentages of HFO-1132(E), R32, HFC-152a, and HFO-1132a based on their sum are 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 HFC-152a is (100-a) mass%, The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DL, LM and MD' connecting the following four points, or on the straight lines D'D, DL, LM and MD' when 0 < a ≤ 5.9, Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (-1.6619a +16.92, -0.1522a +8.4929, 0.8141a +74.587) and Point M (0.0046a 2 -1.8915a +25.9, 0.0, -0.0462a 2 +0.8915a +74.1), The coordinates (x, y, z) are within the range of the figure enclosed by the straight lines D'D, DL, LM, and MD' connecting the following four points, or on the straight lines D'D, DL, LM, and MD' when 5.9 < a ≤ 10.0, Point D' (-a +58.3, 17.7, 24.0), Point D (-a +57.0, 0.0, 43.0), Point L (0.0219a 2 -1.9578a +17.889, -0.005a 2 -0.0668a +8.1682, -0.0169a 2 +1.0246a+73.943) and Point M (0.0075a 2 -1.8998a +25.848, 0.0, -0.0075a 2 +0.8998a +74.152).

7. A freezing method, characterized in that: The method comprises the step of operating a refrigeration cycle using the composition according to any one of claims 1 to 6.

8. A refrigeration device, characterized in that: The working fluid comprises the composition according to any one of claims 1 to 6.

9. A method for inhibiting the disproportionation reaction of HFO-1132(E), characterized by: The method comprises the step of operating a refrigeration cycle using the composition according to any one of claims 1 to 6.

10. Use of HFO-1123, R32, R152a and HFO-1132a in inhibiting the disproportionation reaction of HFO-1132(E), characterized in that: The disproportionation reaction is suppressed by mixing HFO-1123, R32, R152a, HFO-1132a, and HFO-1132(E) at a mixing ratio of the composition according to any one of claims 1 to 6.

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