composition for thermal cycle system and thermal cycle system

专利摘要:
COMPOSITION FOR THERMAL CYCLE SYSTEM AND THERMAL CYCLE SYSTEM. The present invention relates to a composition for a thermal cycle system that has favorable lubricating properties and that comprises a working fluid for the thermal cycle that has a low global warming potential and that can replace R410A and a cycle system thermal that employs the composition. A composition for a thermal cycle system that comprises a working fluid for the thermal cycle that contains a fluorinated unsaturated hydrocarbon compound that has a specific structure and a refrigerant oil that has a rupture voltage of at least 25 kV, with a value hydroxyl maximum 0.1 mg KOH / g which has a minimum temperature on the high temperature side of the phase separation temperature of the working fluid for the thermal cycle of at least 35 ° C and a maximum temperature on the low side maximum temperature of -60 ° C and a thermal cycle system that uses the composition for a thermal cycle system.
公开号:BR112016018711B1
申请号:R112016018711-3
申请日:2015-02-19
公开日:2021-02-17
发明作者:Masato Fukushima；Hiroaki Mitsuoka；Mai TASAKA；Daisuke Shirakawa；Hirokazu Takagi；Takeaki Arai
申请人:AGC Inc.；
IPC主号:

专利说明:

[0001] [001] The present invention relates to a composition for a thermal cycle system and a thermal cycle system that employs the composition. BACKGROUND TECHNIQUE
[0002] [002] In the present specification, the abbreviated names of halogenated hydrocarbon compounds are described in parentheses after the compound names, and in this descriptive report, the abbreviated names are used, instead of the compound names, as the case requires.
[0003] [003] Until now, as a working fluid for a thermal cycle system, such as a refrigerant for a refrigerator, a refrigerant for an air conditioning device, a working fluid for a power generation system (such as generation of energy by exhaust heat recovery), a working fluid for a latent heat transport device (such as a thermal tube) or a cooling fluid, a chlorofluorocarbon (CFC), such as chlorotrifluoromethane or dichlorofluoromethane, or a hydrochlorofluorocarbon (HCFC), such as chlorodifluoromethane, has been used. However, the influences of CFCs and HCFCs on the ozone layer in the stratosphere have been pointed out and their use is currently regulated.
[0004] [004] Under the above conditions, as a working fluid for a thermal cycle system, a hydrofluorocarbon (HFC), which has less influence on the ozone layer, such as difluoromethane (HFC-32), tetrafluoroethane or pentafluoroethane ( HFC-125), has been used instead of CFCs and HCFCs. For example, R410A (a pseudoazeotropic mixture of HFC-32 and HFC-125 in a 1: 1 mass ratio) is a refrigerant which has been widely used. However, it is pointed out that HFC can cause global warming.
[0005] [005] R410A has been widely used for a common air conditioning unit, such as a so-called central air conditioner or individual air conditioner, due to its high cooling capacity. However, it has a global warming potential (Global Warming Potential - GWP) of as high as 2,088 and, consequently, the development of a low GWP working fluid has been desired. In addition, it has been desired to develop a working fluid in which the R410A is simply replaced and the existing devices are used as is.
[0006] [006] In recent years, a hydrofluoro-olefin (HFO) is envisaged, that is, an HFC that has a carbon-carbon double bond, which is a working fluid that has less influence on the ozone layer and that has less influence on global warming since the carbon-carbon double bond is likely to be decomposed by OH radicals in the air. In this specification, a saturated HFC will be said to be an HFC and distinct from an HFO, unless otherwise specified. In addition, an HFC can be said to be a saturated hydrofluorocarbon in some cases.
[0007] [007] As a working fluid that employs an HFO, for example, Patent Document 1 describes a technique referring to a working fluid that uses trifluoroethylene (HFO-1123), which has the above properties and with which excellent performance of cycle will be obtained. In addition, Patent Document 2 describes a technique for a working fluid that uses 1,2-difluoroethylene (HFO-1132), which has the above properties and with which excellent cycle performance will be obtained. Patent Documents 1 and 2 also describe an attempt to obtain a working fluid comprising HFO-1123 or HFO-1132 and several HFCs in combination for the purpose of increasing flame retardancy, cycle performance, etc. of the working fluid.
[0008] [008] However, such an HFO is a compound that has an unsaturated bond in its molecule and is a compound that has a very short life in the air and, consequently, under conditions under which compression and heating are repeatedly carried out in a thermal cycle, has lower instability than a saturated hydrofluorocarbon or hydrochlorofluorocarbon, such as a conventional HFC or HCFC, and lubrication properties can be decreased in the thermal cycle system.
[0009] [009] Thus, a method is provided to efficiently operate a thermal cycle system that employs an HFO as a working fluid, with retained lubricity and, at the same time, excellent HFO cycle performance. State of the Art Documents Patent Documents
[0010] [0010] Patent document 1: WO2012 / 157764
[0011] [0011] Patent document 2: WO2012 / 157765 DESCRIPTION OF THE INVENTION TECHNICAL PROBLEM
[0012] [0012] The present invention was made under these circumstances and its objective is to provide a composition for a thermal cycle system that comprises an HFO, with stable lubricity of the HFO, while allowing a low global warming potential and an excellent HFO cycle performance and a thermal cycle system that employs the composition, which has less influence on global warming and has a high cycle performance and in which the lubricity of the working fluid for the thermal cycle is improved. SOLUTION TO THE PROBLEM
[0013] [0013] The present invention provides a working fluid for a thermal cycle, a composition for a thermal cycle system and a thermal cycle system from [1] to [15] below.
[0014] [0014] [1] A composition for a thermal cycle system comprising a thermal cycling working fluid that contains at least one unsaturated fluorinated hydrocarbon compound selected from a compound that has at least one unsaturated carbon-carbon bond in its molecule represented by the following formula (I):
[0015] [0015] and a refrigerant oil that has a rupture voltage of at least 25 kV, has a hydroxyl value of at most 0.1 mg KOH / g and a minimum temperature on the high temperature side of the phase separation temperature a from the working fluid to the thermal cycle of at least 35 ° C and a maximum temperature above the low temperature side of a maximum of -60 ° C: CxFyRz (I)
[0016] [0016] where R is H or Cl, x is an integer from 2 to 6, y is an integer from 1 to 12, and z is an integer from 0 to 11, provided than 2x≥y + z≥2.
[0017] [0017] [2] The composition for a thermal cycle system according to [1], in which the compound of formula (I) in which x is 2 or 3 is contained.
[0018] [0018] [3] The composition for a thermal cycle system according to [2] in which, like the unsaturated fluorinated hydrocarbon compound, at least one element selected from the group consisting of trifluoroethylene, 2,3,3 , 3-tetrafluoropropene, 1,2-difluoroethylene, 2-fluoropropene, 1,1,2-trifluoropropene, (E) -1,2,3,3,3-pentafluoropropene, (Z) -1,2,3,3 , 3-pentafluoropropene, (E) -1,3,3,3-tetrafluoropropene, (Z) -1,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropene is contained.
[0019] [0019] [4] The composition for a thermal cycle system according to any one of [1] to [3], wherein the working fluid for the thermal cycle still contains a saturated fluorinated hydrocarbon compound.
[0020] [0020] [5] The composition for a thermal cycle system according to [4] in which, as the saturated fluorinated hydrocarbon compound, at least one element selected from the group consisting of trifluoromethane, difluoromethane, difluoroethane, trifluoroethane , tetrafluoroethane, pentafluoroethane, trifluoroiodomethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane and heptafluorocyclopentane are contained.
[0021] [0021] [6] The composition for a thermal cycle system according to any one of [1] to [5] in which, like the unsaturated fluorinated hydrocarbon compound, trifluoroethylene is contained and the trifluoroethylene content is from to from 20 to 80% by mass per 100% by weight of the working fluid for the thermal cycle.
[0022] [0022] [7] The composition for a thermal cycle system according to any one of [4] to [6] in which, like the saturated fluorinated hydrocarbon compound, difluoromethane is contained and the content of difluoromethane is from from 20 to 80% by mass per 100% by weight of the working fluid for the thermal cycle.
[0023] [0023] [8] The composition for a thermal cycle system according to [4] or [5], in which trifluoroethylene and 2,3,3,3-tetrafluoropropene are contained as the unsaturated fluorinated hydrocarbon compound and difluoromethane contained as the saturated fluorinated hydrocarbon compound,
[0024] [0024] the proportion of the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane based on the entire amount of the working fluid for the thermal cycle is greater than 90% by mass and at most 100% in mass, and
[0025] [0025] Based on the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane, the mass ratio of trifluoroethylene is at least 10% by mass and less than 70% by mass, the mass ratio to from 2,3,3,3-tetrafluoropropene is greater than 0% by mass and at most 50% by mass and the mass ratio of difluoromethane is greater than 30% by mass and at most 75% by mass.
[0026] [0026] [9] The composition for a thermal cycle system according to [4] or [5], in which trifluoroethylene and 2,3,3,3-tetrafluoropropene are contained as the unsaturated fluorinated hydrocarbon compound and difluoromethane contained as a saturated fluorinated hydrocarbon compound,
[0027] [0027] the proportion of the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane based on the entire amount of working fluid for the thermal cycle is greater than 90% by mass and at most 100% in pasta,
[0028] [0028] based on the total amount of trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane, the mass proportion of the total amount of trifluoroethylene and 2,3,3,3-tetrafluoropropene is at least 70% by mass, the mass proportion of trifluoroethylene is at least 30% by mass and at most 80% by mass, the mass proportion from 2,3,3,3-tetrafluoropropene is greater than 0% by mass and at most 40% by mass and the mass ratio of difluoromethane is greater than 0% by mass and at most 30% by mass,
[0029] [0029] and the ratio of trifluoroethylene to 2,3,3,3-tetrafluoropropene is at most 95/5.
[0030] [0030] [10] The composition for a thermal cycle system according to any one of [1] to [9], in which the refrigerant oil is at least one element selected from a polyol ester refrigerant oil and a polyvinyl ether refrigerant oil.
[0031] [0031] [11] The composition for a thermal cycle system according to any one of [1] to [10], in which the refrigerant oil has a kinematic viscosity at 40 ° C from 5 to 200 mm2 / s a kinematic viscosity at 100 ° C from 1 to 100 mm2 / s.
[0032] [0032] [12] The composition for a thermal cycle system according to any one of [1] to [11], in which the refrigerant oil has an aniline point of at least -100 ° C and at most 0 ° Ç.
[0033] [0033] [13] A thermal cycle system which employs composition for a thermal cycle system, as defined in any one of [1] to [12].
[0034] [0034] [14] The thermal cycle system according to [13], which is at least one element selected from a refrigeration appliance, an air conditioning appliance, a power generation system, an appliance heat transfer device and a secondary cooling machine.
[0035] [0035] [15] The thermal cycle system according to [14], in which the thermal cycle system has a compression mechanism that has a contact portion that is in contact with the composition for a thermal cycle system and the contact portion is composed of at least one element selected from an engineering plastic, an organic film and an inorganic film. ADVANTAGE EFFECTS OF THE INVENTION
[0036] [0036] According to the present invention, it is possible to provide a composition for a thermal cycle system comprising an unsaturated fluorinated hydrocarbon compound, with more stable lubricity than a working fluid for the thermal cycle containing the fluorinated hydrocarbon compound unsaturated, while allowing low global warming potential and excellent cycle performance of the unsaturated fluorinated hydrocarbon compound.
[0037] [0037] The thermal cycle system of the present invention is a thermal cycle system which has less influence on global warming and has high cycle performance and in which the lubrication properties of the working fluid for the thermal cycle are improved. BRIEF DESCRIPTION OF THE DRAWINGS
[0038] [0038] Figure 1 is a schematic construction view illustrating a refrigeration cycle system as an example of a thermal cycle system of the present invention.
[0039] [0039] Figure 2 is a cycle diagram that illustrates the change of state of a working fluid in a refrigeration cycle system in Figure 1 in a pressure-enthalpy graph. DESCRIPTION OF MODALITIES
[0040] [0040] Now, the present invention will be described in detail. Composition for the Thermal Cycle System
[0041] [0041] The composition for a thermal cycle system comprises a thermal cycle working fluid that contains an unsaturated fluorinated hydrocarbon compound and a refrigerant oil.
[0042] [0042] As a thermal cycle system to which the composition of a thermal cycle system of the present invention is applied, a thermal cycle system through a heat exchanger, such as a condenser or an evaporator, can be used without any particular restriction. The thermal cycle system, for example, a refrigeration cycle system, has a mechanism in which a gaseous working fluid is compressed by a compressor and cooled by a condenser to form a liquid at high pressure, the pressure of the liquid is reduced by an expansion valve and the liquid is vaporized at low temperature by an evaporator, so that the heat is removed by the heat of vaporization.
[0043] [0043] When an unsaturated fluorinated hydrocarbon compound is used as the working fluid for such thermal cycle system, depending on temperature conditions and pressure conditions, the unsaturated fluorinated hydrocarbon compound can be destabilized and self-decompose thereby, deteriorating the function of the working fluid for the thermal cycle. In the composition for a thermal cycle system of the present invention, by the coexistence of a refrigerant oil, the lubricity of the unsaturated fluorinated hydrocarbon compound as a working fluid for the thermal cycle is improved, so that efficient cycle performance can be exhibited.
[0044] [0044] Now, the components in the composition for a thermal cycle system of the present invention will be described. Working Fluid
[0045] [0045] The composition for a thermal cycle system of the present invention contains, as a working fluid, at least one unsaturated fluorinated hydrocarbon compound selected from a compound that has at least one unsaturated carbonocarbon bond in its molecule, represented by formula (I) below: CxFyRz (I) where R is H or Cl, x is an integer from 2 to 6, y is an integer from 1 to 12 and z is an integer from 0 and 11, as long as 2x≥y + z≥2.
[0046] [0046] The formula (I) above represents the types and numbers of elements in the molecule and the formula (I) represents a fluorinated organic compound in which the number x of carbon atoms is from 2 to 6. A fluorinated organic compound C2-6 can have the physical and chemical properties necessary for a working fluid, such as the boiling point, the freezing point and the latent heat of vaporization.
[0047] [0047] In formula (I), the bond form of x carbon atoms represented by Cx can be a single carbon-carbon bond, an unsaturated bond, such as a carbon-carbon double bond and so on and the compound has at least one unsaturated carbon-carbon bond. The unsaturated bond, such as a carbon-carbon double bond, is preferably a carbon-carbon double bond in view of stability and its number is preferably 1.
[0048] [0048] Furthermore, in formula (I), R is H or Cl and R is preferably H so it is less likely that such a compound will destroy the ozone layer.
[0049] [0049] Furthermore, in formula (I), in the range of y + z it is preferably at least 4. Unsaturated Fluorinated Hydrocarbon Compound
[0050] [0050] In the present invention, the unsaturated fluorinated hydrocarbon compound used as a working fluid for a thermal cycle system can be a compound represented by formula (I) and can be, for example, preferably a fluoride of a C2- 6 straight-chain or branched-chain olefin or a cyclic C4-6 olefin.
[0051] [0051] Specifically, it can be, for example, ethylene which has from 1 to 3 fluorine atoms introduced, propene which has from 1 to 5 fluorine atoms introduced, a butene which has from 1 to 7 fluorine atoms introduced, a pentene which has from 1 to 9 fluorine atoms introduced, a hexane which has from 1 to 11 fluorine atoms introduced, cyclobutene which has from 1 to 5 fluorine atoms introduced, cyclopenene which has from 1 to 7 fluorine atoms introduced or cyclohexene which has from 1 to 9 fluorine atoms introduced.
[0052] [0052] Among such unsaturated fluorinated hydrocarbon compounds, an unsaturated C2-3 fluorinated hydrocarbon compound is preferred, more preferred is an ethylene C2 fluoride. Such an unsaturated fluorinated C2-3 hydrocarbon compound can be, for example, trifluoroethylene (HFO-1123), 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2- fluoropropene (HFO-1261yf), 1,1,2-trifluoropropene (HFO-1243yc), (E) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), (Z) -1, 2,3,3,3-pentafluoropropene (HFO-1225ye (Z)), (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), (Z) -1,3,3, 3-tetrafluoropropene (HFO-1234ze (Z)) or 3,3,3-trifluoropropene (HFO-1243zf).
[0053] [0053] In the present invention, the unsaturated fluorinated hydrocarbon compound can be used individually or in combination of two or more.
[0054] [0054] The working fluid of the present invention may contain an optional component described hereinafter, as needed, in addition to the unsaturated fluorinated hydrocarbon compound of formula (I). The content of the unsaturated fluorinated hydrocarbon compound of formula (I) is preferably at least 10% by weight, more preferably from 20 to 80% by weight, even more preferably from 40 to 80% by weight, even more preferably from 40 to 60% by weight per 100% by weight of the working fluid. HFO-1123
[0055] [0055] Now, a working fluid containing HFO-1123 as an essential component will be described as an example of the unsaturated fluorinated hydrocarbon compound of formula (I). However, HFO-1123 can be replaced with another unsaturated fluorinated hydrocarbon compound of formula (I) other than HFO-1123.
[0056] [0056] First, the properties of HFO-1123 as a working fluid are shown in Table 1, particularly in terms of comparison with R410A (a pseudoazeotropic mixture of HFC-32 and HFC-125 in a mass ratio of 1 :1). Cycle performance is represented by the coefficient of performance and the cooling capacity obtained through the method mentioned below. The performance coefficient and cooling capacity of HFO-1123 are represented by relative values based on R410A (1,000) (hereinafter referred to as the relative performance coefficient and relative cooling capacity). Global warming potential (GWP) is a value (100 years) in the Intergornmentl Panel on Climate Change (IPCC), Fourth Assessment Report (2007) or a value measured accordingly. In this specification, GWP is such a value, unless otherwise specified. In cases where the working fluid is a mixture, the temperature variation is an important factor in the evaluation of the working fluid and is preferably less, as described here later.
[0057] [0057] The working fluid used in the present invention can optionally contain a compound commonly used for a working fluid, in addition to HFO-1123, within a range that does not impair the effects of the present invention. Such an optional compound (optional component) can, for example, be an HFC, another HFO (an HFC that has a carbon-carbon double bond) other than HFO-1123 or another component which is vaporized and liquefied together with HFO-1123 . The optional component is preferably an HFC or another HFO (an HFC that has a carbonocarbon double bond) other than HFO-1123.
[0058] [0058] The optional component is preferably a compound which can keep GWP and temperature variation within acceptable limits, while having an effect of further improving the relative performance coefficient and the ability to relative cooling when used for the thermal cycle in combination with HFO-1123. When the working fluid contains such a compound in combination with HFO-1123, a more favorable cycle performance will be obtained, while a low GWP is maintained and the influence on the temperature variation tends to be small. Temperature variation
[0059] [0059] In a case where the working fluid contains an optional component, it has a considerable temperature variation, except for a case where HFO-1123 and the optional component form an azeotropic composition. The temperature variation of the working fluid varies depending on the type of the optional component and the mixing ratio of HFO-1123 and the optional component.
[0060] [0060] In a case where a mixture is used as a working fluid, preferably it is usually an azeotropic mixture or a pseudoazeotropic mixture, such as R410A. A non-azeotropic composition has a problem with the fact that when it is placed in a refrigerator or an air conditioning unit from a pressure vessel, it undergoes a composition change. In addition, if a refrigerant leaks from a refrigerator or an air-conditioning appliance, it is very likely that the refrigerant composition in the refrigerator or air-conditioning appliance will change and a recovery to the initial refrigerant composition is almost impossible. Such problems can be avoided with an azeotropic or pseudoazeotropic mixture.
[0061] [0061] As an index for the applicability of a mixture as a working fluid, "temperature variation" is generally used. Temperature variation is defined as the property so that the start temperature and the end temperature of evaporation in an evaporator or condensation in a condenser, for example, as the heat exchanger, differ from one another. The temperature variation of an azeotropic mixture is 0 and the temperature variation of a pseudoazeotropic mixture is extremely close to 0, for example, the temperature variation of R410A is 0.2.
[0062] [0062] If the temperature variation is large, for example, the inlet temperature of an evaporator tends to be low and freezing is likely to occur. In addition, in a thermal cycle system, thermal exchange efficiency must be improved by making the flow of working fluid and heat source fluid, such as water or air, flowing in countercurrent heat exchangers. Since the temperature difference of the heat source fluid is small in a stable operating state, it is difficult to obtain a thermal cycle system with good energy efficiency with a non-azeotropic mixing fluid, with a wide range of temperatures. Consequently, when a mixture is used as a working fluid, a working fluid with a suitable temperature range is desired. HFC
[0063] [0063] HFC, as the optional component, is preferably selected from the point of view above. Here, an HFC is known to have a greater potential for global warming compared to HFO-1123. Consequently, the HFC to be used in combination with HFO-1123 is preferably selected appropriately, in particular with the aim of keeping the GWP within an acceptable range, in addition to improving cycle performance such as the working fluid and the keep the temperature variation within an appropriate range.
[0064] [0064] An HFC which has less influence on the ozone layer and which has less influence on global warming is, specifically preferably, a C1-5 HFC. HFC can be linear, branched or cyclic.
[0065] [0065] The HFC may, for example, be a fluorinated C1-5 alkane and may preferably be trifluoromethane, difluoromethane (HFC-32), difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane (HFC-125), trifluoroiodomethane, pentafluoropropane , hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane or the like.
[0066] [0066] Particularly, in view of less influence on the ozone layer and excellent refrigeration cycle performance, HFC is preferably HFC-32, 1,1-difluoroethane (HFC-152a), 1,1,1 - trifluoroethane (HFC-143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a) or 1,1,1,2,2-pentafluoroethane ( HFC-125), more preferably HFC 32, HFC-152a, HFC-134a or HFC-125.
[0067] [0067] HFC can be used individually or in combination of two or more.
[0068] [0068] The content of HFC in the working fluid (100% by mass) can be optionally selected depending on the properties required for the working fluid. For example, in the case of a working fluid comprising HFO-1123 and HFC-32, the coefficient of performance and cooling capacity will be improved with an HFC-32 content within a range of 1 to 99% by mass. In the case of a working fluid comprising HFO-1123 and HFC-134a, the performance coefficient will be improved with an HFC-134a content in the range of 1 to 99% by mass.
[0069] [0069] Furthermore, in relation to the preferred HFC GWP, the HFC-32 GWP is 675, the HFC-134a GWP is 1,430 and the HFC-125 GWP is 3,500. In order to keep the GWP of the obtainable working fluid low, HFC as the optional component is, more preferably, HFC-32.
[0070] [0070] In addition, HFO-1123 and HFC-32 can form a pseudoazeotropic mixture close to an azeotropic mixture within a composition range of a mass ratio of 99: 1 to 1:99 and the temperature variation of a Their mixture is close to 0, substantially independent of the range of compositions. From this point of view also, as the HFC to be used in combination with HFO-1123, HFC-32 is advantageous.
[0071] [0071] In a case where HFC-32 is used together with HFO-1123 for the working fluid of the present invention, the HFC-32 content is, specifically preferably, at least from 20% by mass, more preferably from 20 to 80% by weight, even more preferably from 40 to 60% by weight per 100% by weight of the working fluid. Other HFO Other than HFO-1123
[0072] [0072] HFO other than HFO-1123 is also preferably selected from the same point of view as the HFC above. Here, the GWP of the HFO other than HFO-1123 is an order of magnitude smaller than the HFC. Consequently, HFO other than HFO-1123 used in combination with HFO-1123 is preferably selected appropriately, particularly with the aim of improving cycle performance as the working fluid and maintaining temperature variation within an appropriate range, rather than considering the GWP.
[0073] [0073] HFO other than HFO-1123 may, for example, be 2,3,3,3-tetrafluoropropene (HFO-1234yf), 1,2-difluoroethylene (HFO-1132), 2-fluoropropene (HFO-1261yf ), 1,1,2-trifluoropropene (HFO-1243yc), (E) -1,2,3,3,3-pentafluoropropene (HFO-1225ye (E)), (Z) - 1,2,3,3 , 3-pentafluoropropene (HFO-1225ye (Z)), (E) -1,3,3,3-tetrafluoropropene (HFO-1234ze (E)), (Z) -1,3,3,3-tetrafluoropropene (HFO -1234ze (Z)) or 3,3,3-trifluoropropene (HFO-1243zf).
[0074] [0074] In particular, the HFO other than HFO-1123 is, in view of a high critical temperature and excellent durability and performance coefficient, preferably HFO-1234yf (GSP: 4), HFO-1234ze (E) or HFO- 1234ze (Z) (GWP of both (E) -form and (Z) -form being 6), more preferably HFO-1234yf. HFO other than HFO-1123 can be used individually or in combination of two or more.
[0075] [0075] The content of HFO other than HFO-1123 in the working fluid (100% by mass) can be optionally selected depending on the properties required for the working fluid. For example, in the case of a working fluid comprising HFO-1123 and HFO-1234yf or HFO-1234ze, the performance coefficient will be improved with a content of HFO-1234yf or HFO-1234ze in the range of 1 to 99% by mass .
[0076] [0076] A preferred composition range in the case where the working fluid used in the present invention contains HFO-1123 and HFO-1234yf will be described below as the composition range (S).
[0077] [0077] In formulas that indicate the composition range (S), the abbreviated names of the respective compounds indicate the proportions (% by mass) of the respective compounds based on the entire amount of HFO-1123, HFO-1234yf and other components ( such as HFC-32). Composition Range (S)
[0078] [0078] HFO-1123 + HFO-1234yf ≥ 70% by weight
[0079] [0079] 95% by mass ≥ HFO-1123 / (HFO-1123 + HFO-1234yf) ≥ 35% by mass
[0080] [0080] The working fluid in the composition range (S) has a very low GWP and has a small temperature variation. In addition, it has sufficient cooling cycle performance as an alternative to conventional R410A also from the point of view of the performance coefficient, the cooling capacity and the critical temperature.
[0081] [0081] In the working fluid in the composition range (S), based on the total amount of HFO-1123 and HFO-1234yf, the proportion of HFO-1123 is, more preferably, from 40 to 95% by weight, even more preferably from 50 to 90% by mass, especially preferably from 50 to 85% by mass, more preferably from 60 to 85% by mass.
[0082] [0082] Furthermore, the total content of HFO-1123 and HFO-1234yf in 100% by weight of the working fluid is, more preferably, from 80 to 100% by weight, even more preferably from 90 to 100 % by mass, particularly preferably from 95 to 100% by mass.
[0083] [0083] In addition, the working fluid used in the present invention can be a combination of HFO-1123, an HFC and another HFO other than HFO-1123. In such a case, the working fluid preferably comprises HFO-1123, HFC-32 and HFO-1234yf and the proportions of the respective compounds, based on the entire amount of working fluid, are preferably within the ranges to be used. follow:
[0084] [0084] 10% by mass ≤ HFO-1123 ≤ 80% by mass
[0085] [0085] 10% by mass ≤ HFC-32 ≤ 75% by mass
[0086] [0086] 5% by mass ≤ HFO-1234yf ≤ 60% by mass
[0087] [0087] In addition, in a case where the working fluid used in the present invention contains HFO-1123, HFO-1234yf and HFC-32, a preferred composition range (P) is shown below.
[0088] [0088] In the formulas below that indicate the composition ranges (P), the abbreviated names of the respective compounds indicate the proportions (% by mass) of the respective compounds based on the entire amount of HFO-1123, HFO-1234yf and HFC -32. The same applies to the composition tracks (R), (L) and (M). In addition, in the following composition range, the total content of HFO-1123, HFO-1234yf and HFC-32 specifically described is preferably greater than 90% by weight and at most 100% by weight based on the entire the amount of the working fluid for the thermal cycle. Composition Range (P)
[0089] [0089] 70% by mass ≤ HFO-1123 + HFO-1234yf
[0090] [0090] 30% by mass ≤ HFO-1123 ≤ 80% by mass
[0091] [0091] 0% by weight <HFO-1234yf ≤ 40% by weight
[0092] [0092] 0% by weight <HFC-32 ≤ 30% by weight
[0093] [0093] HFO-1123 / HFO-1234yf ≤ 95/5% by weight
[0094] [0094] The working fluid in the above composition is a working fluid that has the respective characteristics of HFO-1123, HFO-1234yf and HFC-32 in a balanced way and has the defects of the respective components suppressed. That is, the working fluid is a working fluid that has a very low global warming potential, has a small variation in temperature and has adequate performance and efficiency when used for the thermal cycle and thus with such a working fluid , favorable cycle performance will be obtained. Here, the total amount of HFO-1123 and HFO-1234yf based on the total amount of HFO-1123, HFO-1234yf and HFC-32 is preferably at least 70% by weight.
[0095] [0095] In addition, as a more preferred composition of the working fluid used in the present invention, a composition containing HFO-1123, in a proportion of 30 to 70% by weight, HFO-1234yf in a proportion from 4 to 40% by mass and HFC-32 in a proportion from 0-30% by mass based on the total amount of HFO-1123, HFO-1234yf and HFC-32, and which has an HFO-1123 content of at most 70 mol% based on the entire amount of working fluid, can be mentioned. A working fluid in the above range is a working fluid whose self-decomposition reaction of HFO-1123 is suppressed and has a high durability, in addition to the increased effects above. From the point of view of the relative coefficient of performance, the HFC-32 content is preferably at least 5% by weight, more preferably at least 8% by weight.
[0096] [0096] In addition, another preferred composition in a case where the working fluid used in the present invention contains HFO-1123, HFO-1234yf and HFC-32 will be shown and, when the HFO-1123 content based on the entire amount of working fluid is at most 70 mol%, a working fluid whose self-decomposition reaction of HFO-1123 is suppressed and which has a high durability can be obtained.
[0097] [0097] A more preferred composition track (R) will be described below. Composition Range (R)
[0098] [0098] 10% by mass ≤ HFO-1123 <70% by mass
[0099] [0099] 0% by mass <HFO-1234yf ≤ 50% by mass
[0100] [00100] 30% by mass <HFC-32 ≤ 75% by mass
[0101] [00101] The working fluid in the above composition is a working fluid that has the respective characteristics of HFO-1123, HFO-1234yf and HFC-32 in a balanced way and has the defects of the respective components suppressed. That is, it is a working fluid that has a low global warming potential, has guaranteed durability and has a small temperature variation and high performance and efficiency when used for the thermal cycle and, therefore, with such a working fluid, a favorable cycle performance will be obtained.
[0102] [00102] A preferred range of the working fluid of the present invention in the composition range (R) will be described below.
[0103] [00103] 20% by mass ≤ HFO-1123 <70% by mass
[0104] [00104] 0% by weight <HFO-1234yf ≤ 40% by weight
[0105] [00105] 30% by weight <HFC-32 ≤ 75% by weight
[0106] [00106] The working fluid in the above composition is a working fluid that has the respective characteristics of HFO-1123, HFO-1234yf and HFC-32 in a balanced way and has the defects of the respective components suppressed. That is, it is a working fluid that has a low global warming potential, has guaranteed durability and has less temperature variation and has a better performance and efficiency when used for the thermal cycle and, therefore, with such a working fluid, favorable cycle performance will be obtained.
[0107] [00107] A more preferred composition range (L) of the working fluid of the present invention in the above composition range (R) will be described below. A composition track (M) is even more preferred. Composition Range (L)
[0108] [00108] 10% by mass ≤ HFO-1123 <70% by mass
[0109] [00109] 0% by weight <HFO-1234yf ≤ 50% by weight
[0110] [00110] 30% by weight <HFC-32 ≤ 44% by weight Composition Range (M)
[0111] [00111] 20% by mass ≤ HFO-1123 <70% by mass
[0112] [00112] 5% by mass ≤ HFO-1234yf ≤ 40% by mass
[0113] [00113] 30% by weight <HFC-32 ≤ 44% by weight
[0114] [00114] The working fluid in the composition range (M) is a working fluid that has the respective characteristics of HFO-1123, HFO-1234yf and HFC-32 in a balanced way and has the defects of the respective components suppressed. That is, such a working fluid is a working fluid whose maximum GWP limit is suppressed to be as low as maximum 300, which has assured durability and has a small temperature variation of less than 5.8 and has a coefficient of relative performance and a relative cooling capacity close to 1 when used for the thermal cycle and, therefore, with such a working fluid, a favorable cycle performance will be obtained.
[0115] [00115] Within such a range, the upper limit of the temperature variation is reduced and the lower limit of the product of the relative performance coefficient and the relative cooling capacity is increased. In view of a high coefficient of relative performance, more preferably 8% by mass ≤ HFO-1234yf. In addition, in view of a high relative cooling capacity, more preferably HFO-1234yf ≤ 35% by mass. Other Optional Component
[0116] [00116] The working fluid to be used for the composition for a thermal cycle system of the present invention may contain, in addition to the optional component above, carbon dioxide, a hydrocarbon, a chlorofluoro-olefin (CFO), a hydrochlorofluoroolefin (HCFO ) or similar. This other optional component is preferably a component that has less influence on the ozone layer and which has less influence on global warming.
[0117] [00117] The hydrocarbon can be, for example, propane, propylene, cyclopropane, butane, isobutane, pentane or isopentane.
[0118] [00118] The hydrocarbon can be used individually or in combination of two or more.
[0119] [00119] In a case where the working fluid contains a hydrocarbon, its content is less than 10% by mass, preferably from 1 to 5% by mass, more preferably from 3 to 5% by mass per 100% by mass of the working fluid. When the hydrocarbon content is at least the minimum limit, the solubility of a mineral refrigerant oil in the working fluid will be more favorable.
[0120] [00120] The CFO can, for example, be chlorofluoropropene or chlorofluoroethylene. With the objective of suppressing the flammability of the working fluid without significantly decreasing the cycle performance of the working fluid, the CFO is preferably 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO- 1214ya), 1,3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) or 1,2-dichloro-1,2-difluoroethylene (CFO-1112).
[0121] [00121] The CFO can be used individually or in combination of two or more.
[0122] [00122] In a case where the working fluid contains the CFO, its content is less than 10% by mass, preferably from 1 to 8% by mass, more preferably from 2 to 5% by mass per 100% by mass of the working fluid. When the CFO content is at least the minimum limit, the flammability of the working fluid tends to be suppressed. When the CFO content is at most the maximum limit, it is possible to obtain favorable cycle performance.
[0123] [00123] HCFO can, for example, be hydrochlorofluoropropene or hydrochlorofluoroethylene. In order to suppress the flammability of the working fluid without significantly decreasing the cycle performance of the working fluid, HCFO is preferably 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd) or 1-chloro-1,2-difluoroethylene (HCFO-1122).
[0124] [00124] HCFO can be used individually or in combination of two or more.
[0125] [00125] In a case where the working fluid contains HCFO, the HCFO content per 100% by weight of the working fluid is less than 1% by weight, preferably from 1 to 8% by weight, more preferably from 2 to 5% by weight. When the HCFO content is at least the minimum limit, the flammability of the working fluid tends to be suppressed. When the HCFO content is at most the maximum limit, it is possible to obtain favorable cycle performance.
[0126] [00126] In a case where the working fluid to be used for the composition for a thermal cycle system of the present invention contains the other optional component above, the total content of such optional components in the working fluid is less than 10 % by weight, preferably not more than 8% by weight, more preferably not more than 5% by weight per 100% by weight of the working fluid. Refrigerant Oil
[0127] [00127] The composition for a thermal cycle system of the present invention comprises, in addition to the above working fluid, a refrigerant oil which can enhance the lubricating properties of the working fluid.
[0128] [00128] The refrigerant oil in the present invention has a rupture voltage of at least 25 kV. When using a refrigerant oil that has a rupture voltage of at least 25 kV, the insulation is maintained even in a thermal cycle system in which a conduction electromagnet and the refrigerant oil are kept in direct contact with each other and the system of thermal cycle will be operated in a stable way. The breakdown voltage is, more preferably, at least 30 kV, even more preferably at least 40 kV. The breakdown voltage of a refrigerant oil in this specification is either a value in a catalog or is assessed whether it is 25 kV or 50 kV or above or below through simplified confirmation according to JIS C2101.
[0129] [00129] In addition, the refrigerant oil has a hydroxyl value of a maximum of 0.1 mg KOH / g. When the refrigerant oil has a sufficiently low hydroxyl value of a maximum of 0.1 mg KOH / g, it is possible to prevent the formation of hydroxyl radicals which can cause deterioration by polymerization or decomposition of the refrigerant oil or working fluid for the thermal cycle. Hydroxyl radicals, in a system that uses a working fluid that has a carbon-carbon double bond, are believed to attack and break down the double bond, thereby generating an acid. If an acid is generated, corrosion or deterioration of the elements that make up the thermal cycle system can occur. Consequently, in the present invention, where the hydroxyl value is low, as mentioned above, the generation of an acid can be suppressed significantly and the thermal cycle system can be operated in a stable manner. The hydroxyl value is more preferably at most 0.05 mg KOH / g. The hydroxyl value in this specification is measured according to JIS K2501.
[0130] [00130] In addition, the refrigerant oil has a minimum temperature on the high temperature side of at least 35 ° C and a maximum temperature on the low temperature side of a maximum - 60 ° C, of the phase separation temperature from the working fluid for the thermal cycle of formula (I) used above in combination. That is, this means that the working fluid for the thermal cycle and the refrigerant oil are present as being compatible with each other under the operating conditions of the thermal cycle system, and in such a case, the thermal cycle system can be operated in a stable way, since the composition for a thermal cycle system in the liquid state does not undergo phase separation and is uniform. The minimum temperature on the high temperature side of the phase separation temperature is at least 35 ° C, preferably at least 40 ° C. The maximum temperature on the low temperature side is a maximum of -60 ° C, preferably a maximum of -70 ° C. Here, a mixture of the working fluid for the thermal cycle and the refrigerant oil used to measure the phase separation temperature is normally a mixture that contains from 10 to 50% by weight of refrigerant oil and is preferably, a mixture that has a refrigerant oil content from 10 to 20% by mass. The phase separation temperature in this specification is a value measured in accordance with JIS K2211.
[0131] [00131] Furthermore, the kinematic viscosity of the refrigerant oil at 40 ° C is preferably 5 to 200 mm2 / s, more preferably between 5 and 100 mm2 / s, due to the fact that the lubricity of a compressor is not reduced, the lubricating oil is satisfactorily compatible with the working fluid under low temperature conditions and it is possible to avoid the lubricity failure of a refrigerator or a compressor and the heat exchange of an evaporator can be sufficiently conducted. In addition, the kinematic viscosity at 100 ° C is preferably from 1 to 100 mm2 / s, more preferably from 2 to 30 mm2 / s, in order to maintain electrical energy consumption and resistance to abrasion within appropriate ranges. The kinematic viscosity in this specification is a value measured in accordance with JIS K2283.
[0132] [00132] In addition, the refrigerant oil preferably has an aniline point of at least -100 ° C and at most 0 ° C. "The aniline point" is a value that indicates the solubility of a hydrocarbon-based solvent, for example, it is a value measured according to JIS K2256, so that equal volumes of a sample (the refrigerant oil) and aniline are mixed and cooled and the temperature at which they are no longer miscible with each other and turbidity begins to be observed is recorded as the aniline point. This value is a value of the refrigerant oil itself in which no working fluid for the thermal cycle is dissolved.
[0133] [00133] In a thermal cycle system to which the composition for a thermal cycle system comprising the working fluid for thermal cycle represented by the formula (I) of the present invention, since the working fluid has a double carbon bond -carbon, as described below, usually an acid-resistant resin material or similar, as described in [Thermal Cycle System] is employed somewhere, instead of an element made of a metal, such as copper, normally used as an element that constitutes a thermal cycle system. However, even with such a resin material, depending on the type of refrigerant oil used, the resin material may have disadvantages in some cases due, for example, to contraction or expansion resulting from the refrigerant oil. Consequently, by using refrigerant oil with an aniline point within the predetermined range above (at least -100 ° C and at most 0 ° C), expansion / contraction deformation of the resin material can be avoided and failure can be avoided. or deterioration of a sliding element in a compression mechanism, an insulation material in an electric motor, a sealing element within a thermal cycle system, and so on.
[0134] [00134] The refrigerant oil used in the present invention can, for example, be specifically a synthetic oil containing oxygen (an ester refrigerant oil, an ether refrigerant oil or a polyglycol refrigerant oil).
[0135] [00135] Among them, from the point of view of compatibility with the fluorinated hydrocarbon compound as an essential component of the working fluid in the present invention, an ester refrigerant oil or an ether refrigerant oil is suitable. In addition, the ester refrigerant oil is preferably a polyol ester refrigerant oil and the ether refrigerant oil is preferably a polyvinyl ether refrigerant oil.
[0136] [00136] Particularly, in the case of an ester refrigerant oil or an ether refrigerant oil, as constituent atoms of the refrigerant oil, carbon atoms and oxygen atoms are representative mentioned. If the proportion (molar ratio of carbon / oxygen) of carbon atoms to oxygen atoms is very low, the moisture absorption capacity tends to be high and, if the proportion is very high, compatibility with the working fluid will be decreased. From this point of view, the ratio of carbon atoms to oxygen atoms in the refrigerant oil is, appropriately, a molar ratio of 2 to 7.5. Ester Refrigerant Oil
[0137] [00137] Like ester refrigerant oil, in view of chemical stability, a dibasic acid ester refrigerant oil of a dibasic acid and a monohydric alcohol, a polyol polyester ester refrigerant oil and a fatty acid, a polyol ester complex refrigerant oil, a polybasic acid and a monohydric alcohol (or a fatty acid), a polyol carbonate ester refrigerant oil or the like can be mentioned as the base oil component. Dibasic Acid Ester Refrigerant Oil
[0138] [00138] Dibasic acid ester refrigerant oil is preferably an dibasic acid ester, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, acid sebacic, phthalic acid, isophthalic acid or terephthalic acid, especially a C5-10 dibasic acid (eg glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid or sebacic acid) with a C1-15 monohydric alcohol o which has a linear or branched alkyl group (such as methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol or pentadecanol). Such dibasic acid ester refrigerant oil can be, for example, specifically ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate or di (3-ethylhexyl) sebacate . Polyol Ester Refrigerant Oil
[0139] [00139] Polyol ester refrigerant oil is an ester synthesized from a polyhydric alcohol and a fatty acid (a carboxylic acid).
[0140] [00140] The polyhydric alcohol that constitutes the polyol ester refrigerant oil may be a diol (such as ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2 -methyl1,3-propanediol, 1,5-pentanediol, neopentyl-glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl -1,3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol or 1,12-dodecanediol), a polyol with 3 to 20 hydroxy groups (such as trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol), glycerin, a polyglycerin or a polyglycerin glycerin trimer), 1,3,5-pentanotriol, sorbitol, sorbitan, a sorbitol / glycerin condensate, a polyhydric alcohol, such as adonitol, arabitol, xylitol or mannitol, a saccharide, such as xylose, arabinose, ribose , rhamnose, glucose, fructose, galactose, mannose, sorbose, c elobiosis, maltose, isomaltose, trehalose, sucrose, raffinose, melezitosis or gentianose or a partially esterified product thereof and the polyhydric alcohol that constitutes the ester can be used individually or in combination of two or more.
[0141] [00141] The number of carbon atoms in the polyol fatty acid that constitutes the refrigerant ester oil is not particularly limited but, normally, a C1-24 fatty acid is employed. A linear fatty acid or branched fatty acid is preferred. Linear fatty acid can be, for example, acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic , hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid or linoleic acid and the hydrocarbon group attached to the carboxyl group can be a fully saturated hydrocarbon or it can be an unsaturated hydrocarbon. In addition, the branched fatty acid can be, for example, 2-methylpropanoic acid, 2-methylbutanoic acid, 3-methylbutanoic acid, 2,2-dimethylpropanoic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, 4-methylpentanoic acid, 2,2-dimethylbutanoic acid, 2,3-dimethylbutanoic acid, 3,3-dimethylbutanoic acid, 2-methylhexanoic acid, 3-methylhexanoic acid, 4-methylhexanoic acid, 5-methylhexanoic acid, 2,2-dimethyl acid -pentanoic acid, 2,3-dimethyl-pentanoic acid, 2,4-dimethyl-pentanoic acid, 3,3-dimethyl-pentanoic acid, 3,4-dimethyl-pentanoic acid, 4,4-dimethyl-pentanoic acid, 2 - ethylpentanoic acid, 3-ethylpentanoic acid, 2,2,3-trimethylbutanoic acid, 2,3,3-trimethylbutanoic acid, 2-ethyl-2-methylbutanoic acid, 2-ethyl-3-methylbutanoic acid, 2-methyl-heptanoic acid , 3-methyl-heptanoic acid, 4-methyl-heptanoic acid, 5-methyl-heptanoic acid, 6-methyl-heptanoic acid, 2-ethyl-hexanoic acid, 3-ethyl-hexanoic acid, 4-ethyl-hexanoic acid, 2,2-dimethylhexanoic acid, 2,3-dimethylhexanoic acid, 2,4-dimethylhexanoic acid, 2,5-dimethylhexanoic acid, 3,3-dimethylhexanoic acid, 3,4-dimethylhexanoic acid, 3,5- dimethylhexanoic acid, 4,4-dimethylhexanoic acid, 4,5-dimethylhexanoic acid, 5,5-dimethylhexanoic acid, 2-propylpentanoic acid, 2-methyloctanoic acid, 3-methyloctanoic acid, 4-methyloctanoic acid, 5-methyloctanoic acid, 6-methyloctanoic acid, 7-methyloctanoic acid, 2,2-dimethyl-heptanoic acid, 2,3-dimethyl-heptanoic acid, 2,4-dimethyl-heptanoic acid, 2,5-dimethyl-heptanoic acid, 2 , 6-dimethyl-heptanoic acid, 3,3-dimethyl-heptanoic acid, 3,4-dimethyl-heptanoic acid, 3,5-dimethyl-heptanoic acid, 3,6-dimethyl-heptanoic acid, 4,4-dimethyl-heptanoic acid, 4,5-dimethyl-heptanoic acid, 4,6-dimethyl-heptanoic acid, 5,5-dimethyl-heptanoic acid, 5,6-dimethyl-heptanoic acid, 6,6-dimethyl-heptanoic acid, 2-methyl- 2-ethylhexanoic acid, 2-methyl-3-ethylhexanoic acid, 2-methyl-4-ethylhexanoic acid, 3-methyl-2-ethyl acid -hexanoic acid, 3-methyl-3-ethylhexanoic acid, 3-methyl-4-ethylhexanoic acid, 4-methyl-2-ethylhexanoic acid, 4-methyl-3-ethylhexanoic acid, 4- methyl-4-ethylhexanoic acid, 5-methyl-2-ethylhexanoic acid, 5-methyl-3-ethylhexanoic acid, 5-methyl-4-ethylhexanoic acid, 2-ethylheptanoic acid, 3-methyloctanoic acid , 3,5,5-trimethylhexanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,2,4,4-tetramethylpentanoic acid, 2,2,3,3-tetramethylpentanoic acid, 2, 2,3,4-tetramethylpentanoic or 2,2-diisopropylpropanoic acid. The ester can be an ester of one or more of such fatty acids.
[0142] [00142] The polyol that constitutes the ester can be used individually or as a mixture of two or more. In addition, the fatty acid that constitutes the ester can be a single component or it can be two or more types. In addition, fatty acid can be used individually or as a mixture of two or more. In addition, the polyol ester refrigerant oil may have a free hydroxyl group.
[0143] [00143] Among them, a particularly preferred polyol ester refrigerant oil is characterized by containing an ester obtained using the following compounds (a) to (c):
[0144] [00144] (a) a compound that has at least two hydroxyl groups or derivatives thereof,
[0145] [00145] (b) a compound that has at least two carboxyl groups or derivatives thereof and
[0146] [00146] (c) a compound that has a carboxyl group or derivative thereof and / or a compound that has a hydroxyl group or derivative thereof,
[0147] [00147] and being used in conjunction with the working fluid of formula (I) above and can satisfy the properties of lubricity, sealing, compatibility with the working fluid, chemical / thermal stability, electrical insulating properties, etc. sufficiently in a balanced manner, and can sufficiently prevent a compressor's lubricity failure and a reduction in cooling efficiency.
[0148] [00148] The compound (a) that constitutes the ester is a compound that has at least two hydroxyl groups or derivatives thereof. The number of hydroxyl groups is preferably from 2 to 6, so that an appropriate viscosity is ensured and in view of the compatibility with the working fluid of formula (I) above. In addition, if only a compound that has a hydroxyl group or derivative thereof is used as the alcohol component, the ester obtained is unlikely to have sufficient viscosity and lubrication failure or a reduction in cooling efficiency tends to occur and thermal stability / chemistry or fluidity at low temperature tends to be insufficient.
[0149] [00149] The compound (a) can be, for example, specifically a polyhydric alcohol, a polyhydric phenol, a polyhydric amino alcohol or a condensate thereof or a compound that has the hydroxyl groups of such compound esterified by a carboxylic acid, such as acetic acid and, among them, a polyhydric alcohol, its condensate or derivative is preferred, in which the degree of compatibility with the working fluid, electrical insulation properties and thermal stability tends to be more enhanced.
[0150] [00150] The number of carbon atoms in such a polyhydric alcohol is not particularly limited and, preferably, a C2-12 polyhydric alcohol is used. As such a polyhydric alcohol, a dihydric alcohol (diol) can, for example, be specifically ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl1 , 3-propanediol, 1,5-pentanediol, neopentyl-glycol, 1,6-hexanediol, 2-ethyl-2-methyl-1,3-propanediol, 1,7-heptanediol, 2-methyl-2-propyl-1 , 3-propanediol, 2,2-diethyl-1,3-propanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol or 1,12-dodecanediol. In addition, a trihydric alcohol or higher may, for example, be specifically a polyhydric alcohol, such as trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di (pentaerythritol), tri- (pentaerythritol), glycerin, polyglycerin (a glycerin dimer or trimer), 1,3,5-pentanotriol, sorbitol, sorbitan, a sorbitol / glycerin condensate, adonitol, arabitol, xylitol or mannitol, a saccharide, such as xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose, mannose, sorbose or cellobiose or a partially esterified product thereof. Among them, a sterically hindered alcohol, such as neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol or di (pentaerythritol) is preferred.
[0151] [00151] In addition, for the ester as described above, as the compound (a), a compound that has hydroxyl groups esterified by a carboxylic acid can be used. Such a derivative is preferably a compound having hydroxyl groups esterified by a lower carboxylic acid and, specifically, an acetate or propionate of the compound exemplified as the polyhydric alcohol above is preferably used.
[0152] [00152] The compound (b) that constitutes the above ester is a compound that has at least two carboxyl groups or a derivative thereof. The number of carboxyl groups is preferably from 2 to 6. If only a compound that has a carboxyl group or a derivative thereof is used as the acid component, the ester obtained is unlikely to have sufficient viscosity and lack of lubricity or a reduction in cooling efficiency tends to occur and thermal / chemical stability or low temperature fluidity tends to be insufficient.
[0153] [00153] Compound (b) can, for example, be a bivalent to hexavalent carboxylic acid or a carboxylic acid derivative, such as its acid anhydride, ester or acid halide.
[0154] [00154] The number of carbon atoms in a bivalent to hexavalent carboxylic acid is not particularly limited and, preferably, a C2-10 bivalent carboxylic acid is used. Such a bivalent to hexavalent carboxylic acid may, for example, be specifically a saturated aliphatic dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, methylmalonic acid , ethylmalonic acid, dimethylmalonic acid, methyl succinic acid, 2,2-dimethyl succinic acid, 2,3-dimethyl succinic acid, 2-ethyl-2-methyl succinic acid, 2-methylglutaric acid, 3-methylglutaric acid or 3-methyladipic acid; an unsaturated aliphatic dicarboxylic acid, such as maleic acid, fumaric acid, itaconic acid, citraconic acid or mesaconic acid; an alicyclic dicarboxylic acid, such as 1,2-cyclohexanedicarboxylic acid or 4-cyclohexene-1,2-dicarboxylic acid; or an aromatic polyvalent carboxylic acid, such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid or pyromelitic acid and, among them, a divalent carboxylic acid is preferred and a saturated aliphatic dicarboxylic acid is more preferred in view of the oxidation stability.
[0155] [00155] In addition, for the ester, as described above, as the compound (b), a derivative of a compound that has two carboxyl groups can be used. Such a derivative can, for example, be an ester, an acid anhydride or an acid halide and, among them, an ester of the above divalent carboxylic acid and a lower alcohol (more preferably methanol or ethanol) is preferably used.
[0156] [00156] The compound (c) that constitutes the above ester is a compound that has a carboxyl group or a derivative thereof and / or a compound that has a hydroxyl group or a derivative thereof. As such, a compound (c) or a compound that has a carboxyl group or a derivative of the same and a compound that has a hydroxyl group or a derivative of the same can be used individually or can be used in a mixture of both. If only a compound that has at least two carboxyl groups or a derivative of it is used as the acid component and only a compound that has at least two hydroxyl groups or a derivative of the same is used as the alcohol component, the ester obtained tends to have insufficient thermal / chemical stability.
[0157] [00157] The compound that has a carboxyl group or a derivative thereof, for example, can be specifically a monovalent fatty acid or its acid anhydride, ester or acid halide. The number of carbon atoms in such a monovalent fatty acid is not particularly limited and a C1-24 fatty acid is commonly used; however, the number of carbon atoms in the monovalent fatty acid is preferably at least 3, more preferably at least 4, even more preferably at least 5, particularly preferably at least 8. If the number of carbon atoms in monovalent fatty acid is less than 3, the lubricity that the obtained ester has inherently tends to be insufficient and, in addition, the compatibility of the obtained ester with the working fluid of formula (I) above will be excessively high, so the ester will be diluted in the working fluid and the viscosity tends to be low, thus leading to a decrease in cooling efficiency and failure of lubricity due to a reduction in the sealing property.
[0158] [00158] Furthermore, the number of carbon atoms in monovalent fatty acid is preferably at most 22, more preferably at most 20, even more preferably at most 18. If the number of carbon atoms in monovalent fatty acid exceeds 22, the compatibility of the ester obtained with the working fluid tends to be insufficient, thus leading to a compressor lubrication failure and a reduction in cooling efficiency due to a decrease in the oil return property.
[0159] [00159] Monovalent fatty acid as compound (c) can be linear or branched, however, a monovalent linear fatty acid is preferable in view of lubricity and a monovalent branched fatty acid is preferable in view of thermal stability / hydrolysis. In addition, the monovalent fatty acid can be a saturated fatty acid or an unsaturated fatty acid.
[0160] [00160] The monovalent fatty acid as the compound () can, for example, be specifically a straight or branched chain fatty acid, such as pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid , dodecanoic acid, tridecanoic acid, tetradecanoic acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid or oleic acid or a fatty acid with a quaternary α carbon atom (and one of them) valeric acid (n-pentanoic acid), caproic acid (n-hexanoic acid), enanthic acid (n-heptanoic acid), caprylic acid (n-octanoic acid), pelargonic acid (n-nonanoic acid), capric acid (n -decanoic acid), lauric acid (n-dodecanoic acid), myristic acid (n-tetradecanoic acid), palmitic acid (n-hexadecanoic acid), stearic acid (n-octadecanoic acid), oleic acid (cis-9-octadecenoic acid) , isopentanoic acid ( Preferably 3-methylbutanoic acid), 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid or 3,5,5-trimethylhexanoic acid are preferably used.
[0161] [00161] Furthermore, the compound that has a hydroxyl group or derivative thereof, for example, can be specifically a monohydric alcohol, a monohydric phenol, a monohydric amino alcohol or a compound that has the hydroxyl groups of such a compound esterified by a carboxylic acid, such as acetic acid. The number of carbon atoms in such a compound is not particularly limited and, in order to further improve both the lubricity and the compatibility with the working fluid of the ester obtained, a C1-24 compound is preferred and, among them, is preferred is a C3-18 linear monohydric alcohol, C3-18 branched monohydric alcohol or a C5-10 monohydric cycloalcohol.
[0162] [00162] Monohydric alcohol that has carbon atoms within the preferred range above can, for example, be specifically a straight or branched chain propanol (including n-propanol, 1-methylethanol and so on), chain butanol straight or branched (including n-butanol, 1-methylpropanol, 2-methylpropanol and so on), straight or branched chain pentanol (including n-pentanol, 1-methyl-butanol, 2-methyl-butanol, 3-methyl- butanol and so on), straight or branched chain hexanol (including n-hexanol, 1-methylpentanol, 2-methylpentanol, 3-methylpentanol and so on), straight or branched chain heptanol (including n-heptanol, 1- methylhexanol, 2-methylhexanol, 3-methylhexanol, 4-methylhexanol, 5-methylhexanol, 2,4-dimethylpentanol and so on), straight or branched chain octanol (including n-octanol, 2 -ethylhexanol, 1-methylheptanol, 2-methylheptanol and so on), straight or branched chain nonanol (including n-nonanol, 1-methyl l-octanol, 3,5,5-trimethylhexanol, 1- (2'-methylpropyl) -3-methyl-butanol and so on), straight or branched chain decanol (including n-decanol, isodecanol and so on on), straight or branched chain undecanol (including n-undecanol, isoundecanol and so on) or straight or branched chain dodecanol (including n-dodecanol, isododecanol and so on), straight or branched chain tridecanol (including n -tridecanol, isotridecanol and so on), straight or branched chain tetradecanol (including n-tetradecanol, isotetradecanol and so on), straight or branched chain pentadecanol (including npentadecanol, isopentadecanol and so on), straight chain hexadecanol or branched (including n-hexadecanol, isohexadecanol and so on), straight or branched chain heptadecanol (including n-heptadecanol, iso-heptadecanol and so on), straight or branched chain octadecanol (including n-octadecanol, iso-octadecanol and so on), cyclohexanol, methylcyclohexanol or dimethylcyclohexanol.
[0163] [00163] In addition, as the compound (c), a derivative that has the hydroxyl group esterified by a carboxylic acid can be used. Such a derivative is preferably an acetate, propionate or similar to the exemplified compound as monohydric alcohol.
[0164] [00164] As the ester, particularly preferred is an ester obtained using the following compounds (a '), (b') and (c '):
[0165] [00165] (a ') at least one element selected from the group consisting of ethylene glycol, propylene glycol, butylene glycol, glycerin, neopentyl glycol, diethylene glycol, dipropylene glycol, dibutylene glycol and dibutylene glycol,
[0166] [00166] (b ') at least one element selected from the group consisting of oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid and sebacic acid; and
[0167] [00167] (c ') at least one element selected from the group consisting of valeric acid, caproic acid, enantic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic, isopentanoic acid, 2-methylhexanoic acid, 2-ethylpentanoic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, n-butanol, n-pentanol, n-hexanol, n-heptanol , n-octanol, n-nonanol, n-decanol, n-undecanol, n-dodecanol, n-tridecanol, n-tetradecanol, n-pentadecanol, n-hexadecanol, n-heptadecanol, n-octadecanol, isobutanol, isopentanol, iso -hexanol, iso-heptanol, 2-ethylhexanol, 3,5,5-trimethylhexanol, isodecanol, isododecanol, isotetradecanol and isohexadecanol. When an ester obtained using the compounds (a ') to (c') above is incorporated into the refrigerant oil, lubricity, sealing property, compatibility with the working fluid, thermal / chemical stability, electrical insulation properties , etc. tend to be satisfied in a balanced way.
[0168] [00168] The composition ratio of compounds (a) to (c) above is not particularly limited, however, the proportions of compounds (a) to (c) are preferably within the following ranges, respectively, based on in the total amount of compounds (a) to (c), where lubricity, sealing property, compatibility with the working fluid, thermal / chemical stability, electrical insulation properties, etc. tend to be satisfied in a more balanced way:
[0169] [00169] Compound (a): from 3 to 55 mol%, preferably from 5 to 50 mol%, more preferably from 10 to 45 mol%.
[0170] [00170] Compound (b): from 3 to 55 mol%, preferably from 5 to 50 mol%, more preferably from 10 to 45 mol%.
[0171] [00171] Compound (c): from 3 to 90 mol%, preferably from 5 to 80 mol%, more preferably from 10 to 70 mol%.
[0172] [00172] The ester described above is prepared by esterifying compounds (a) to (c) above according to a conventional method, preferably in an atmosphere of an inert gas, such as nitrogen, in the presence of a catalyst of esterification or without a catalyst, with heating.
[0173] [00173] Furthermore, in a case where an acetate, propionate or similar of an alcohol is used as the compound (a) or (c) or in the case where a lower or similar alcohol ester of a carboxylic acid is used as the compound (b) or (c), the ester can be obtained by means of a transesterification reaction.
[0174] [00174] The esterification catalyst used in the above esterification reaction can, for example, be specifically a Lewis acid, such as an aluminum derivative, a tin derivative or a titanium derivative; an alkali metal salt, such as sodium alkoxide or potassium alkoxide; or a sulfonic acid, such as p-toluenesulfonic acid, methanesulfuric acid or sulfuric acid and, among them, a Lewis acid is preferred, such as an aluminum derivative, a tin derivative or a titanium derivative, through which the the ester obtained has a higher thermal / hydrolysis stability and a tin derivative is particularly preferred in view of the reaction efficiency. The amount of the esterification catalyst is, for example, at a level of 0.1 to 1% by mass based on the total amount of compounds (a) to (c) as raw materials.
[0175] [00175] The reaction temperature in the above esterification reaction can, for example, be 150 to 230 ° C and, in general, the reaction is completed in 3 to 30 hours.
[0176] [00176] In addition, after the completion of the esterification reaction, excess raw materials can be removed by distillation under reduced pressure or under normal pressure and then a conventional purification method, such as liquid-liquid extraction, vacuum distillation or adsorption purification treatment, such as activated carbon treatment, can be performed to purify the ester.
[0177] [00177] Here, the esterification reaction using the specific compounds (a) to (c) has been described, however, in still other cases, the reaction product obtained may be a mixture. Furthermore, in a case where the ester is a mixture of at least two compounds, in view of the balance between compatibility with the working fluid and different performances and ease of production, the content of an ester with compound (a) and the directly bound compound (b) is preferably from 10 to 100% by weight, more preferably from 20 to 100% by weight, even more preferably from 25 to 100% by weight based on the entire amount of the mixture. Complex Ester Refrigerant Oil
[0178] [00178] Complex ester refrigerant oil is an ester of a fatty acid and a dibasic acid, and a monohydric alcohol and a polyol. The fatty acid, dibasic acid, monohydric alcohol and polyol can be the same as described above.
[0179] [00179] The fatty acid can be a fatty acid exemplified for the polyol ester above.
[0180] [00180] Dibasic acid can be, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pyelic acid, submeric acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid or terephthalic acid.
[0181] [00181] The polyol can be a polyol according to the polyhydric alcohol exemplified for the polyol ester above. The complex ester is an ester of a fatty acid, a dibasic acid and a polyol, and each compound can consist of a single component or several components. Polyol Carbonate Refrigerant Oil
[0182] [00182] Polyol carbonate refrigerant oil is an ester of carbonic acid and a polyol.
[0183] [00183] The polyol can, for example, be a polyglycol (such as polyalkylene glycol, its ether compound or a modified compound) obtained by homopolymerizing or copolymerizing a diol (as described above), a polyol (as described above ) or a polyglycol ether added to a polyol.
[0184] [00184] Polyalkylene glycol can, for example, be obtained by polymerizing a C2-4 alkylene oxide (such as ethylene oxide or propylene oxide) using water or an alkali metal hydroxide as an initiator. In addition, it can be one that has an hydroxyl group of etherified polyalkylene glycol. A polyalkylene glycol molecule can contain single oxyalkylene units or two or more types of oxyalkylene units. It is preferred that at least the oxypropylene units are contained in a molecule. In addition, the polyol carbonate refrigerant oil may be a ring opening polymer of a cyclic alkylene carbonate. Ether Refrigerant Oil
[0185] [00185] The ether refrigerant oil can, for example, be a polyvinyl ether refrigerant oil or a polyalkylene glycol refrigerant oil. Polyvinyl Ether Refrigerant Oil
[0186] [00186] Polyvinyl ether refrigerant oil can be obtained by polymerizing a vinyl ether monomer obtained by copolymerizing a vinyl ether monomer and a hydrocarbon monomer that has an olefinic double bond or a copolymer of a polyvinyl ether and an alkylene glycol, or a polyalkylene glycol, or a monoether of the same.
[0187] [00187] Such polyvinyl ether refrigerant oil is preferably a polyvinyl ether compound which has a structure represented by the following formula (1) and which has a molecular mass from 300 to 3000:
[0188] [00188] The C1-8 hydrocarbon group as each from R1 to R3 can be, for example, an alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n- butyl, an isobutyl group, a sec-butyl group, a tert-butyl group, various forms of a pentyl group, various forms of a hexyl group, various forms of a heptyl group or various types of octyl group, a cycloalkyl group, such such as a cyclopentyl group, a cyclohexyl group, various forms of a methylcyclohexyl group, various forms of an ethylcyclohexyl group or various forms of a dimethylcyclohexyl group, an aryl group, such as a phenyl group, various forms of a methylphenyl group, various forms of an ethylphenyl group or various forms of a dimethylphenyl group or an arylalkyl group, such as a benzyl group, various forms of a phenylethyl group or various forms of a methylbenzyl group. Each of R1, R2 and R3 is, particularly preferably, a hydrogen atom.
[0189] The divalent C2-4 hydrocarbon group represented by Rb is specifically a divalent alkylene, such as a methylene group, an ethylene group, a propylene group, a trimethylene group or various forms of a butylene group.
[0190] [00190] m in formula (1) represents the RBO repetition number and its average is within a range from 1 to 50, preferably from 2 to 20, more preferably from 2 to 10, particularly preferably from 2 to 5. In a case where there is a plurality of RBO, the plurality of RBO can be the same or different.
[0191] [00191] Furthermore, o is a number from 1 to 50, preferably from 1 to 10, more preferably from 1 to 2, especially preferably 1, and p is a number from 2 to 25 , preferably from 5 to 15 and, in a case where there is a plurality of each of oep, the units can be in blocks or random, respectively.
[0192] [00192] The C1-20 aliphatic or alicyclic hydrocarbon group such as Ra may preferably be a C1-10 alkyl group or a C5-10 cycloalkyl group, specifically a methyl group, an ethyl group, an n-propyl group, a isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, various forms of a pentyl group, various forms of a hexyl group, various forms of a heptyl group, various forms of a octyl group, various forms of a nonyl group, various forms of a decila group, a cyclopentyl group, a cyclohexyl group, various forms of a methylcyclohexyl group, various forms of an ethylcyclohexyl group, various forms of a group propylcyclohexyl or various forms of a dimethylcyclohexyl group.
[0193] [00193] The aromatic group that may have a C1-20 substituent such as Ra may, for example, be specifically an aryl group, such as a phenyl group, various forms of a tolyl group, various forms of an ethylphenyl group, various forms of a xylyl group, various forms of a trimethylphenyl group, various forms of a butylphenyl group or various forms of a naphthyl group or an arylalkyl group, such as a benzyl group, various forms of a phenylethyl group, various forms of a methylbenzyl group, various forms of a phenylpropyl group or various forms of a phenylbutyl group.
[0194] [00194] Furthermore, the C2-20 group acyls as Ra may, for example, be an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a valeryl group, an isovaleryl group, a pivaloyl group, a group benzoyl or a toluoyl group.
[0195] [00195] The C2-50 oxygen-containing hydrocarbon group such as Ra can be, for example, specifically preferably, a methoxymethyl group, a methoxyethyl group, a methoxypropyl group, a 1,1-bismetoxypropyl group, a 1,2- bismetoxypropyl, an ethoxypropyl group, a (2-methoxyethoxy) propyl group or a (1-methyl-2-methoxy) propyl group.
[0196] [00196] In formula (1), the C1-10 hydrocarbon group represented by R4 can, for example, be an alkyl group, such as a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a group n-butyl, an isobutyl group, various forms of a pentyl group, various forms of a hexyl group, various forms of a heptyl group, various forms of an octyl group, various forms of a nonyl group or various forms of a decila group, a cycloalkyl group, such as a cyclopentyl group, a cyclohexyl group, various forms of a methylcyclohexyl group, various forms of an ethylcyclohexyl group, various forms of a propylcyclohexyl group or various forms of a dimethylcyclo group -hexyl, an aryl group, such as a phenyl group, various forms of a methylphenyl group, various forms of an ethylphenyl group, dimethylphenyl group, propylphenyl group, various forms of a trimethylphenyl group, various forms of a butylphenyl group or various forms of a naphthyl group or an aryl group alkyl, such as various forms of a benzyl group, various forms of a phenylethyl group, various forms of a methylbenzyl group, various forms of a phenylpropyl group or various forms of a phenylbutyl group.
[0197] [00197] R1 to R3, Ra, Rb, m and R1 to R4 can be, respectively, the same or different from each other in relation to the respective structural units.
[0198] [00198] The polyvinyl ether compound can be obtained, for example, by copolymerizing a vinyl ether compound represented by the formula (2) below and a vinyl ether compound represented by the formula (3) below :
[0199] [00199] In the previous formulas, Ra, Rb, m and R1 to R4 are as defined above.
[0200] [00200] The vinyl ether compound represented by the formula (2) can be, for example, an alkylene glycol monovinyl ether, a polyoxyalkylene glycol monovinyl ether, an alkylene glycol vinyl ether alkyl or an alkyl vinyl ether polyoxyalkylene glycol. Specifically, it can be, for example, ethylene glycol monovinyl ether, ethylene glycol methyl vinyl ether, diethylene glycol monovinyl ether, diethylene glycol methyl vinyl ether, triethylene glycol monovinyl ether, methyl ether ether triethylene glycol vinyl, propylene glycol monovinyl ether, propylene glycol methyl ether, dipropylene glycol monovinyl ether, dipropylene glycol methyl ether, tripropylene glycol monovinyl ether or tripropylene glycol methyl ether.
[0201] [00201] Furthermore, the vinyl ether compound represented by formula (3) can be, for example, a vinyl ether, such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl ether vinyl, n-butyl vinyl ether, isobutyl vinyl ether, sec-butyl vinyl ether, vinyl tert-butyl ether, n-pentyl vinyl ether or n-hexyl vinyl ether; a propene, such as 1-methoxypropene, 1-ethoxypropene, 1-n-propoxypropene, 1-isopropoxypropene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 2-methoxypropene, 2 -ethoxypropene, 2-n-propoxypropene, 2-isopropoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-secbutoxypropene or 2-tert-butoxypropene; or a butene, such as 1-methoxy-1-butene, 1-ethoxy-1-butene, 1-n-propoxy-1-butene, 1-isopropoxy-1-butene, 1-n-butoxy-1-butene, 1-isobutoxy-1-butene, 1-sec-butoxy-1-butene, 1-tert-butoxy-1-butene, 2-methoxy-1-butene, 2-ethoxy-1-butene, 2- n-propoxy- 1-butene, 2-isopropoxy-1-butene, 2-n-butoxy-1-butene, 2-isobutoxy-1-butene, 2-sec-butoxy-1-butene, 2-tert-butoxy-1-butene, 2-methoxy-2-butene, 2-ethoxy-2-butene, 2-n-propoxy-2-butene, 2-isopropoxy2-butene, 2-n-butoxy-2-butene, 2-isobutoxy-2-butene, 2-sec-butoxy-2-butene or 2-tert-butoxy-2-butene. Such a vinyl ether monomer can be prepared by a known method.
[0202] [00202] The vinyl ether compound above can be produced, for example, through radical polymerization, cationic polymerization or radiation polymerization of a corresponding vinyl ether compound and a hydrocarbon monomer that has a used olefinic double bond, if desired. For example, a vinyl ether monomer is polymerized using the following method to obtain a polymer that has a desired viscosity. To initiate polymerization, a combination of a Brönsted acid, a Lewis acid or an organic metallic compound, with water, an alcohol, a phenol, an acetal or a vinyl ether and a carboxylic acid addition product can be used. Brönsted acid can be, for example, hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid or trifluoroacetic acid. Lewis acid can be, for example, boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride or ferric chloride and, among such Lewis acids, boron trifluoride is particularly suitable. In addition, the organic metal compound can, for example, be diethyl aluminum chloride, aluminum chloride or diethyl zinc acetate.
[0203] [00203] As the water, alcohol, phenol, acetal or addition product of a vinyl ether and a carboxylic acid to be combined with them, an option can be selected. The alcohol can, for example, be a saturated C1-20 aliphatic alcohol, such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various forms of pentanol, various forms of hexanol, various forms of heptanol or various forms of octanol, a c3-10 unsaturated aliphatic alcohol, such as allyl alcohol or an alkylene glycol monoether, such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene monomethyl ether glycol, dipropylene glycol monomethyl ether or tripropylene glycol monomethyl ether. In a case where a vinyl ether and carboxylic acid addition product is used, the carboxylic acid can be, for example, acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid , 2-methylbutyric acid, pivalic acid, n-caproic acid, 2,2-dimethylbutyric acid, 2-methylvaleric acid, 3-methylvaleric acid, 4-methylvaleric acid, enanthic acid, 2-methylcaproic acid, caprylic acid, 2- ethylcaproic, 2-n-propylvaleric acid, n-nonanoic acid, 3,5,5-trimethylcaproic acid, caprylic acid or undecanoic acid.
[0204] [00204] In addition, in a case where a product with the addition of a vinyl ether and a carboxylic acid is used, the vinyl ether can be the same or different from that used for polymerization. The product of adding a vinyl ether and a carboxylic acid can be obtained by mixing them to allow them to react at a temperature of about 0 to about 100 ° C and the adduct can be separated, for example, by means of distillation and used for the reaction, or can be used for the reaction as is, without separation.
[0205] [00205] The polymerization initiation end of the resulting polymer has hydrogen bonded in a case where water, an alcohol or a phenol is used and, in a case where acetal is used, it has hydrogen or one of the alkoxy groups of the acetal used. In addition, in a case where a vinyl ether addition product and a carboxylic acid is used, it has an alkylcarbonyloxy group derived from the carboxylic acid portion left from the addition product of a vinyl ether and a carboxylic acid.
[0206] [00206] In addition, the termination end is an acetal, an olefin or an aldehyde in a case where water, an alcohol, a phenol or an acetal is used. In addition, in the case of a vinyl ether and a carboxylic acid addition product, it is a hemiacetal carboxylate. The end of the polymer thus obtained can be converted to a desired group by means of a known method. Such a desired group can, for example, be a residue, for example a saturated hydrocarbon, an ether, an alcohol, a ketone, a nitrile or an amide and is preferably a residue of a saturated hydrocarbon, an ether or an alcohol .
[0207] [00207] The polyvinyl ether compound contained in the refrigerant oil used in the present invention has a molar carbon / oxygen ratio of at least 4. If the molar ratio is greater than 4, compatibility with the working fluid of the formula ( I) will be decreased. Regarding the adjustment of the molar ratio, a polymer that has a molar ratio within the above range can be produced by adjusting the molar ratio of carbon / oxygen of the raw material monomer. That is, a polymer that has a high molar proportion of carbon / oxygen will be obtained when the proportion of a monomer that has a high molar proportion of carbon / oxygen is high and a polymer that has a low molar proportion of carbon / oxygen will be obtained. when the molar ratio of a monomer that has a low carbon / oxygen molar ratio is high.
[0208] [00208] In addition, the molar proportion of carbon / oxygen can also be adjusted through a combination of the monomers with water, an alcohol, a phenol, an acetal or an addition product of a vinyl ether and a carboxylic acid used as the initiator, as described for the polymerization method of the vinyl ether monomer. A polymer that has a molar proportion of carbon / oxygen greater than the monomer of raw material will be obtained using, as an initiator, an alcohol, a phenol or similar that has a molar proportion of carbon / oxygen greater than the monomer to be polymerized and a polymer that has a lower molar carbon / oxygen ratio than the raw material monomer will be obtained using an alcohol that has a low molar carbon / oxygen ratio, such as methanol or methoxyethanol.
[0209] [00209] In addition, in a case where a vinyl ether monomer and a hydrocarbon monomer that has an olefinic double bond are copolymerized, a polymer will be obtained that has a molar carbon / oxygen ratio greater than the molar ratio of carbon / oxygen of the vinyl ether monomer and the ratio can be adjusted by the proportion of the hydrocarbon monomer that has an olefinic double bond used and its number of carbon atoms. Polyalkylene Glycol Refrigerant Oil
[0210] [00210] Polyalkylene glycol refrigerant oil can, for example, be obtained by polymerizing a C2-4 alkylene oxide (such as ethylene oxide or propylene oxide), using water or an alkali metal hydroxide as an initiator . In addition, it can be an etherified hydroxyl group of a polyalkylene glycol. A polyalkylene glycol refrigerant oil molecule can contain single oxyalkylene units or two or more types of oxyalkylene units. It is preferred that at least oxypropylene units are contained in a molecule.
[0211] [00211] A specific polyalkylene glycol refrigerant oil can, for example, be a compound represented by the following formula (4): R101 - [(OR102) k-OR103] l (4) where R101 is a hydrogen atom, a C1-10 alkyl group, a C2-10 acyl group or a C1-10 aliphatic hydrocarbon group that has 2 to 6 bonding sites, R102 is a C2-4 alkylene group, R103 represents a hydrogen atom, a C1-10 alkyl group or a C2-10 acyl group, I is an integer from 1 to 6 and k is a number that makes the average of k × I = 6 to 80.
[0212] [00212] In the above formula (4), the alkyl group as each of R101 and R103 can be linear, branched or cyclic. The alkyl group can, for example, specifically a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various forms of a butyl group, various forms of a pentyl group, various forms of a hexyl group, various forms of a heptyl group, various forms of an octyl group, various forms of a nonyl group, various forms of a decila group, a cyclopentyl group or a cyclohexyl group. If the number of carbon atoms in the alkyl group is greater than 10, compatibility with the working fluid will be decreased, thus leading to phase separation. The number of carbon atoms in the alkyl group is preferably from 1 to 6.
[0213] [00213] The alkyl group portion in the acyl group, as in each of R101 and R103, can be linear, branched or cyclic. As specific examples of the alkyl group in the acyl group, several C1-9 groups mentioned as specific examples of the alkyl group can be cited. If the number of carbon atoms in the acyl group is greater than 10, compatibility with the working fluid will be decreased, thus leading to phase separation. The number of carbon atoms in the acyl group is preferably from 2 to 6.
[0214] [00214] In a case where both R101 and R103 are an alkyl group or an acyl group, R101 and R103 can be the same or different from each other.
[0215] [00215] Furthermore, in a case where I is at least 2, the plurality of R103 in a molecule can be the same or different.
[0216] [00216] In a case where R101 is a C1-10 aliphatic hydrocarbon group that has from 2 to 6 attachment sites, the aliphatic hydrocarbon group can be cyclic or similar. The aliphatic hydrocarbon group that has two attachment sites can be, for example, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a group decylene, a cyclopentylene group or a cyclohexylene group. In addition, an aliphatic hydrocarbon group having 3 to 6 attachment sites can be, for example, trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxylacyclohexane; or a residue that has a hydroxyl group removed from a polyhydric alcohol, such as 1,3,5-trihydroxylacyclohexane.
[0217] [00217] If the number of carbon atoms in the aliphatic hydrocarbon group is greater than 10, compatibility with the working fluid will be decreased, thus leading to phase separation. The number of carbon atoms is preferably from 2 to 6.
[0218] [00218] R102, in the above formula (4) is a C2-4 alkylene group and the oxyalkylene group, as a repeating unit, can be an oxyethylene group, an oxypropylene group or an oxybutylene group. A molecule of the compound of formula (4) can contain a single type of oxyalkylene group or groups of two or more types of oxyalkylene groups. It is preferred that at least oxypropylene units are contained in a single molecule and it is particularly preferred that at least 50 mol% of oxypropylene units are contained in the oxyalkylene units.
[0219] [00219] In formula (4) above, I is an integer from 1 to 6 and is defined, depending on the number of R101 binding sites. For example, in a case where R101 is an alkyl group or an acyl group, l is 1 and, in a case where R101 is an aliphatic hydrocarbon group with 2, 3, 4, 5 or 6 attachment sites, I is 2, 3, 4, 5 or 6, respectively. Furthermore, k is a number that makes the average of k × l = 6 to 80 and, if the average of k × l is outside the above range, the objective of the present invention will not be sufficiently achieved.
[0220] [00220] The structure of the polyalkylene glycol is suitably a polyethylene glycol dimethyl ether represented by formula (5) below or poly (oxyethylene oxypropylene) glycol dimethyl ether represented by formula (6) in view of economic efficiency and of the effects described above and is more preferably polypropylene glycol monobutyl ether represented by the formula (7) below, even more appropriately polypropylene glycol monomethyl ether represented by the formula (8) below, poly (oxyethylene oxypropylene) glycol monomethyl ether represented by the formula (9) below, monobutyl poly (oxyethylene oxypropylene) glycol represented by the formula (10) below or polypropylene glycol diacetate represented by the formula (11) below in view of economic efficiency, etc. CH3O- (C3H6O) h-CH3 (5) (Where h is a number from 6 to 80) CH3O- (C2H4O) i- (C3H6O) j-CH3 (6) (Where each of i and j is a number of at least 1, since the sum of i and j is 6 to 80) C4H9O- (C3H6O) hH (7) (Where h is a number from 6 to 80) CH3O- (C3H6O) hH (8) (Where h is a number from 6 to 80) CH3O- (C2H4O) i- (C3H6O) jH (9) (Where each of i and j is a number of at least 1, since the sum of i and j is 6 to 80) C4H9O- (C2H4O) i- (C3H6O) jH (10) (Where each of i and j is a number of at least 1, since the sum of i and j is 6 to 80) CH3COO- (C3H6O) h-COCH3 (11) (Where h is a number from 6 to 80)
[0221] [00221] Such polyoxyalkylene glycols can be used individually or in combination of two or more.
[0222] [00222] The cooling oils above can be used individually or in combination of two or more.
[0223] [00223] Such refrigerant oil is preferably used as a composition for a thermal cycle system as mixed with the working fluid. In this case, the proportion of the refrigerant oil is preferably from 5 to 60% by weight, more preferably from 10 to 50% by weight based on the entire amount of the composition for a thermal cycle system.
[0224] [00224] Furthermore, the moisture content of the refrigerant oil is not particularly limited and is preferably at most 300 ppm, more preferably at most 200 ppm, even more preferably at most 100 ppm, based on the total amount of oil soda. Particularly in the case where a closed cooler is used, a low moisture content is required from the point of view of the decomposition stability of the working fluid and the influence of the refrigerant oil on the thermal / chemical stability and electrical insulation properties. In this specification, the moisture content was measured according to the JIS K2275 standard.
[0225] [00225] The partial air pressure remaining from the refrigerant oil is not particularly limited and is preferably at most 10 kPa, more preferably at most 5 kPa.
[0226] [00226] Furthermore, the ash content of the used refrigerant oil is not particularly limited and is preferably at most 100 ppm, more preferably at most 50 ppm, in order to increase the thermal / chemical stability of the refrigerant and avoid the occurrence of sediment and so on. In this specification, the ash content means an ash value measured in accordance with JIS K2272. Other Optional Component
[0227] [00227] The composition for a thermal cycle system may contain a known optional component, added in a range that does not detract from the effects of the present invention. Such an optional component can, for example, be an additive that causes refrigerant oil to be stably contained in the composition for a thermal cycle system and such an additive can, for example, be a copper deactivator, an extreme pressure agent , an oily agent, an antioxidant, an acid remover, an anti-foam agent or a polymerization inhibitor. Each additive can be added as appropriate and the amount of each additive is adjusted to be at least 0.01% by weight and at most 5% by weight per 100% by weight of the composition for a thermal cycle system. Here, the amount of acid remover and the amount of antioxidant are preferably within a range of at least 0.05% by weight and at most 5% by weight.
[0228] [00228] As the copper deactivator, benzotriazole, a derivative of the same or similar can be used. As the antifoaming agent, a silicon compound can be used. As the oily agent, a higher alcohol can be used.
[0229] [00229] In addition, as the extreme pressure agent, one that contains a phosphoric acid ester can be used. As the phosphoric acid ester, a phosphate, a phosphite, an acid phosphate, an acid phosphite or the like can be used. In addition, as the extreme pressure agent, one that contains an amine salt of a phosphate, a phosphite, an acid phosphate or an acid phosphite can be used.
[0230] [00230] The phosphate may, for example, be triaryl phosphate, trialkyl phosphate, trialkyl aryl phosphate, triaryl alkyl phosphate or trialkenyl phosphate. In addition, the phosphate can be, for example, specifically triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, diphenyl ethyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, diphenyl cresyl phosphate, dicresyl phenyl phosphate, phosphate ethylphenyl diphenyl, diethylphenyl phenyl phosphate, propylphenyl diphenyl phosphate, dipropylphenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenyl phosphate triphenylphenyl phosphate, tributylphenyl phosphate, tributyl (2-ethylhexyl), tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate or trioleyl phosphate.
[0231] [00231] In addition, the phosphite may be, for example, specifically triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, phosphite of tridecyl, trilauryl phosphite, tri-iso-octyl phosphite, diphenyl isodecyl phosphite, tristearyl phosphite or trioleyl phosphite.
[0232] [00232] In addition, the acid phosphate can be, for example, 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, phosphate lauryl acid, tridecyl acid phosphate, stearyl acid phosphate or isostearyl acid phosphate.
[0233] [00233] Furthermore, acid phosphite may, for example, dibutyl hydrogen phosphite, dilauryl phosphite hydrogen, dioleyl hydrogen phosphite, distearyl phosphite hydrogen or diphenyl phosphite hydrogen. Among the phosphoric acid esters above, oleyl acid phosphate or stearyl acid phosphate is suitable.
[0234] [00234] Furthermore, among the amines to be used for the amine salt of a phosphate, a phosphite, an acid phosphate or an acid phosphite, a monosubstituted amine can be, for example, specifically butylamine, pentylamine, hexylamine, cyclo- hexylamine, octylamine, laurylamine, stearylamine, oleylamine or benzylamine. In addition, a disubstituted amine can be, for example, specifically dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl monopropanolamine, benzyl monopropanolamine, benzyl monopropanolamine, benzyl monopropanolamine, benzyl monoethanolamine tolyl monopropanol. In addition, a tri-substituted amine can, for example, be specifically tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenylamine, dioleyl monoethanolamine, dilauryl monopropanolamine, dioctyl monoethylamine, diopropylamine, dipropyl monoethylamine; monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, triethanolamine or tripropanolamine.
[0235] [00235] In addition, an extreme pressure agent different from those mentioned above can be added. For example, it is possible to use a type of extreme pressure agent compound that contains organic sulfur, such as a monosulfide, a polysulfide, a sulfoxide, a sulfone, a thiosulfinate, a sulfurized oil, a thiocarbonate, a thiophene, a thiazole or a methanesulfonate, an extreme pressure agent of the thiophosphate type, such as a triester of thiophosphoric acid, an extreme pressure agent of the ester type, such as a higher fatty acid, a hydroxyaryl fatty acid, a polyhydric alcohol ester or a acrylate, an organic chlorine-type extreme pressure agent, such as a chlorinated hydrocarbon or a chlorinated carboxylic acid derivative, a fluorinated organic compound-type extreme pressure agent, such as a fluorinated aliphatic carboxylic acid, a fluorinated ethylene resin, a fluorinated alkylpolysiloxane or fluorinated graphite, an alcohol-like extreme pressure agent, such as a higher alcohol or a metal-compounded extreme pressure agent, such as such as a naphthenate (such as lead naphthenate), a fatty acid salt (such as the lead fatty acid salt), a thiophosphate (such as zinc dialcyldithiophosphate), a thiocarbamate, an organic molybdenum compound, a compound of organic tin, an organic germanium compound or a borate ester.
[0236] [00236] In addition, as the antioxidant, a phenol-type antioxidant or an amine-type antioxidant can be used. The phenol-type antioxidant can be, for example, 2,6-di-tert-butyl-4-methylphenol (DBPC), 2,6-di-tert-butyl-4-ethylphenol, 2,2'-methylene-bis (4-methyl-6-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol or 2,6-di-tert-butylphenol. In addition, the amine-type antioxidant can be, for example, N, N'-diisopropyl-p-phenylenediamine, N, N'-di-sec-butyl-p-phenylenediamine, N-phenyl1-naphthylamine or N, N ' -diphenyl-p-phenylenediamine. In addition, as an antioxidant, an acid remover can also be used to eliminate oxygen.
[0237] [00237] As the acid remover, an epoxide compound, such as a phenyl glycidyl ether, an alkyl glycidyl ether, an alkylene glycol glycidyl ether, cyclohexene oxide, an α-olefin oxide or oil can be used epoxidized soybean. Among them, from the point of view of compatibility, preferred as an acid-removing agent is a phenyl glycidyl ether, an alkyl glycidyl ether, an alkylene glycol glycidyl ether, cyclohexene oxide or an α-olefin oxide. The alkyl group in the alkyl glycidyl ether and the alkylene group in the glycidyl alkylene glycol ether can be branched. The number of carbon atoms in such a compound is at least 3 and at most 30, preferably at least 4 and at most 24, more preferably at least 6 and at most 16. In addition, the total number of carbon atoms in the oxide αolefin is at least 4 and at most 50, preferably at least 4 and at most 24, more preferably at least 6 and at most 16. Such acid removers can be used individually or in combination of two or more.
[0238] [00238] In addition, as the polymerization inhibitor, a polymerization inhibitor such as 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butyl phenol, 2,6-di-tert-butyl- p-cresol or benzotriazole can be used.
[0239] [00239] In addition, the composition for a thermal cycle system according to this modality may contain, as the case may be, a load-bearing additive, an oxygen removing agent, a chlorine remover, a detergent-dispersant, a viscosity index enhancer, an anti-corrosion agent, a stabilizer, a corrosion inhibitor, a spill point depressant or the like. The oxygen remover is an additive to eliminate oxygen. The amount of each additive is at least 0.01% by weight and at most 5% by weight, preferably at least 0.05% by weight and at most 2% by weight per 100% by weight of the composition for a system of thermal cycle.
[0240] [00240] In addition, as an optional component that must be mixed in the composition for a thermal cycle system, for example, a leak detection substance can be mentioned and such leak detection substance optionally contained can be, for example, an ultraviolet fluorescent dye, an odorous gas or an odor-masking agent.
[0241] [00241] The fluorescent ultraviolet dye can be any known ultraviolet fluorescent dye that has been used for a thermal cycle system in conjunction with a working fluid comprising a halogenated hydrocarbon, such as the dyes described, for example, in the United States Patent United No. 4,249,412, JP-A-10-502737, JP-A-2007-511645, JP-A-2008-500437 and JP-A-2008-531836.
[0242] [00242] The odor-masking agent can be any known perfume that has been used for a thermal cycle system in conjunction with a working fluid comprising a halogenated hydrocarbon, such as the perfumes described, for example, in A JP documents -A-2008-500437 and JP-A-2008-531836.
[0243] [00243] In a case where the leak detection substance is used, a solubilizing agent that improves the solubility of the substance to detect leaks in the working fluid can be used.
[0244] [00244] The solubilizing agent can be that as described, for example, in documents JP-A-2007-511645, JP-A-2008-500437 and JP-A-2008-531836.
[0245] [00245] The content of the substance to detect leakages in the composition for a thermal cycle system is not particularly limited within a range so as not to noticeably diminish the effects of the present invention and is preferably at most 2 parts by weight, more preferably at most 0.5 parts by weight per 100 parts by weight of the working fluid. Thermal Cycle System
[0246] [00246] The thermal cycle system of the present invention is a system that employs the composition for a thermal cycle system of the present invention. The thermal cycle system of the present invention can be a heat pump system that uses the heat obtained by a condenser or it can be a refrigeration cycle system that uses the cold obtained by an evaporator.
[0247] [00247] The thermal cycle system of the present invention can be, for example, specifically a refrigerator, an air conditioning device, a power generation system, a heat transfer device and a secondary refrigeration machine. Among them, the thermal cycle system of the present invention, which exhibits efficient thermal cycle performance in a working environment at a higher temperature, is preferably used as an air conditioning device that will be located outdoors in many cases. In addition, the thermal cycle system of the present invention is also preferably used for a refrigerator.
[0248] [00248] The air conditioning unit can be, for example, specifically an individual air conditioning unit, a central air conditioning unit (such as an air conditioning unit for a store, an air conditioning unit) for a factory building or air conditioning unit, a gasoline engine thermal pump, a train air conditioning system, or an automotive air conditioning system).
[0249] [00249] The refrigerator may, for example, be specifically a display refrigerator (such as a built-in display refrigerator or a separate display refrigerator), an industrial refrigerator, a vending machine or an ice maker.
[0250] [00250] The power generation system is preferably a power generation system using the Rankine cycle system.
[0251] [00251] The power generation system can be, for example, specifically a system in which, in an evaporator, a working fluid is heated, for example, by geothermal energy, solar heat or residual heat over a medium temperature range -high at a level from 50 to 200 ° C, and the working fluid vaporized in a state of high temperature and high pressure is adiabatically expanded by an expansion device, so that an energy generator is triggered by the work generated adiabatic expansion to generate energy.
[0252] [00252] Furthermore, the thermal cycle system of the present invention can be a heat transport device. The heat transfer device is preferably a latent heat transfer device.
[0253] [00253] The latent heat transport device can be, for example, a thermal transport tube that conducts latent heat using evaporation, boiling, condensation, etc. of a working fluid filled in an apparatus and a closed two-phase thermal siphon. A thermal tube is applied to a relatively small refrigeration apparatus, such as a refrigeration apparatus for a heating portion of a semiconductor device and electronic equipment. A closed two-stage thermal trap is widely used for a gaseous / gaseous heat exchanger to accelerate snow melting and prevent road freezing, as it does not require a wick and its structure is simple.
[0254] [00254] Now, as an example of the thermal cycle system according to the embodiment of the present invention, a refrigeration cycle system will be described with reference to a refrigeration cycle system 10, which was roughly described above, of which the schematic construction view is shown in Figure 1 as an example. A refrigeration cycle system is a system that uses the cold obtained by an evaporator.
[0255] [00255] A refrigeration cycle system 10 shown in Figure 1 is a general system comprising a compressor 11 to compress a vapor of working fluid A to form a vapor of working fluid B at high temperature / high pressure, a condenser 12 to cool and liquefy the working fluid vapor B discharged from the compressor 11 to form a working fluid C at low temperature / high pressure, an expansion valve 13 to allow the working fluid C discharged from the condenser 12 if expand to form a working fluid D at low temperature / low pressure, an evaporator 14 to heat working fluid D discharged from expansion valve 13 to form a vapor of working fluid A at high temperature / low pressure, a pump 15 to supply a charge fluid E to the evaporator 14 and a pump 16 to supply a fluid F to the condenser 12.
[0256] [00256] In the refrigeration cycle system 10, a cycle with (i) to (iv) below is repeated.
[0257] [00257] (i) A working fluid vapor discharged from an evaporator 14 is compressed by a compressor 11 in order to form a working fluid B at high temperature / high pressure (hereinafter referred to as "AB process").
[0258] [00258] (ii) The working fluid B discharged from the compressor 11 is cooled and liquefied by a condenser 12 of fluid F to form a working fluid C at low temperature / high pressure. At this point, fluid F is heated to form fluid F ', which is discharged from condenser 12 (hereinafter referred to as "BC process").
[0259] [00259] (iii) The working fluid C discharged from the condenser 12 is expanded in an expansion valve 13 to form a working fluid D at low temperature / low pressure (hereinafter referred to as "process CD").
[0260] [00260] (iv) The working fluid D discharged from the expansion valve 13 is heated by a charging fluid E in the evaporator 14 to form a working temperature vapor A at high temperature / low pressure. At this point, the charging fluid E is cooled and becomes a charging fluid E, which is discharged from the evaporator 14 (hereinafter referred to as "process AD").
[0261] [00261] The refrigeration cycle system 10 is a cycle system that comprises an adiabatic isentropic change, an isentalpical change and an isobaric change. The change in the state of the working fluid, as represented on a pressure / enthalpy (curve) graph as shown in Figure 2, can be represented as a trapezoid that has points A, B, C and D as vertices.
[0262] [00262] The AB process is a process in which adiabatic compression is performed by the compressor 11 to change the vapor of working fluid A at high temperature / low pressure to a vapor of working fluid B at high temperature / high pressure and is represented by line AB in Figure 2.
[0263] [00263] The BC process is a process in which isobaric cooling is carried out on the condenser 12 to change the working fluid B at high pressure / high temperature to a working fluid C at low temperature / high pressure and is represented by the line AC at Figure 2. The pressure in the present process is the condensation pressure. Of the two points of intersection of the enthalpy / pressure graph and the BC line, the point of intersection T1 on the side of high enthalpy is the condensing temperature and the point of intersection T2 on the side of low enthalpy is the temperature of the boiling point of condensation. Here, in a case where the working fluid is a single compound or an azeotropic mixture, T1 and T2 are the same. In a case where the working fluid is a non-azeotropic mixture, T1 and T2 are different from each other. In the present invention, in such a case, the highest temperature between T1 and T2 is taken as the "condensing temperature". In addition, the temperature variation in the case of a non-azeotropic mixing fluid is represented by the difference between T1 and T2.
[0264] [00264] The CD process is a process in which the isenthalpal expansion is performed by the expansion valve 13 to change the working fluid C at high pressure / low temperature to a working fluid D at low temperature / low pressure and is represented by line CD in Figure 2. T2-T3 corresponds to the degree of supercoiling (hereinafter referred to as "SC", as needed) of the working fluid in the cycle from (i) to (iv), where T3 is the temperature of the fluid working temperature C at low temperature / high pressure.
[0265] [00265] The DA process is a process in which the isobaric heating is carried out on the evaporator 14 to have the working fluid D at low temperature / low pressure returned to a working fluid vapor A at high temperature / low pressure and is represented line DD in Figure 2. The pressure in the present process is the evaporation pressure. Of the two points of intersection of the enthalpy / pressure graph and the DA line, the point of intersection T6 on the high enthalpy side is the evaporation temperature. T7-T6 corresponds to the degree of superheating (hereinafter referred to as "SH", as the case may be) of the working fluid in the cycle from (i) to (iv), where T7 is the temperature of the working fluid vapor A. T4 indicates the temperature of the working fluid D. Here, in a case where the working fluid is a single compound or an azeotropic mixture, T4 and T6 are equal to each other. In a case where the working fluid is a non-azeotropic mixture, T4 and T6 are different from each other. In the present invention, in such a case, the lowest temperature between T4 and T6 is taken as the "evaporation temperature".
[0266] [00266] Here, the cycle performance of the working fluid is assessed, for example, by the cooling capacity (hereinafter referred to as "Q" as the case may be) and the performance coefficient (hereinafter referred to as "COP" , as the case may be) of the working fluid. Q and COP of the working fluid are obtained, respectively, according to formulas (A) and (B) below from the enthalpies hA, hB, hC and hD in their respective states A (after evaporation, at high temperature and low pressure), B (after compression, at high temperature and high pressure), C (after condensation, at low temperature and high pressure) and D (after expansion, at low temperature and low pressure) of the working fluid: Q = hA-hD (A) COP = Q / compression work = (hA-hD) / (hB-hA) (B)
[0267] [00267] COP means efficiency in the refrigeration cycle system and a higher COP means that higher productivity, for example, Q, can be obtained by a smaller input, for example, the electrical energy needed to operate a compressor.
[0268] [00268] In addition, Q means the ability to freeze a charge fluid and a higher Q means that more work can be done on the same system. In other words, this means that, with a working fluid that has a higher Q, the desired performance can be achieved with a smaller amount, so the system can be reduced.
[0269] [00269] In the thermal cycle system of the present invention that employs the composition for a thermal cycle system of the present invention, in a refrigeration cycle system 10 shown in Figure 1, for example, when compared to a case where R410 (a mixed liquid of HFC-32 and HFC-125 in a mass ratio of 1: 1) that has been used for an air conditioning device or similar, it is possible to achieve high levels of Q and COP, that is, equal to or greater than those of R410A, while remarkably suppressing the potential for global warming.
[0270] [00270] Furthermore, since the working fluid contained in the composition for a thermal cycle system to be used can have a composition with which the temperature variation of the working fluid is suppressed at a certain level or less and, in such a case, the composition change when the composition for a thermal cycle system is placed in a refrigerator or air conditioning device from a pressure vessel and a change in the composition of the refrigerant in the refrigerator or an appliance of air conditioning when refrigerant leaks out of the refrigerator or air conditioning unit, can be suppressed to lower levels. In addition, according to the composition for a thermal cycle system of the present invention, the lubrication properties of the fluorinated hydrocarbon compound contained as the working fluid are improved, and consequently, a thermal cycle system that employs the composition can maintain a more efficient circulation state of the working fluid compared to a conventional system and can be operated in a stable manner.
[0271] [00271] In the thermal cycle system as described above, since the working fluid used in the present invention contains a carbon-carbon double bond, the working fluid can be decomposed to generate an acid at the time of operating the system. In the present invention, a refrigerant oil is used in combination with the working fluid to suppress the generation of an acid, however, it is preferred to constitute the thermal cycle system so that it is stably operated, even if an acid is generated by any reason.
[0272] [00272] That is, the contact portion that will be in contact with the composition for a thermal cycle system is preferably composed of at least one element selected from an engineering plastic, an organic film and an inorganic film . As the contact portion, in particular, a sliding element in a case where the system has a compression mechanism, a sealing element within the thermal cycle system and so on, can be mentioned as elements to be protected. More particularly, a sliding element (such as a bearing) provided on a sliding portion of a compressor, a sealing element to prevent leakages of the compressor's working fluid, an insulating material provided on an electric motor, etc. can be mentioned.
[0273] [00273] The engineering plastic used is preferably at least one element selected from a polyamide resin, a polyphenylene sulfide resin, a polyacetal resin and a fluororesin.
[0274] [00274] In addition, the organic film used is preferably at least one film selected from a polytetrafluoroethylene coated film, a polyimide coated film, a polyamideimide coated film and an insulating thermal curing film formed using a resin coating composition that contains a resin comprising a polyhydroxy ether resin and a polysulfone resin and a crosslinking agent.
[0275] [00275] In addition, the inorganic film used is at least one selected from a graphite film, a diamond-like carbon film, a tin film, a chrome film, a nickel film and a carbon film. molybdenum.
[0276] [00276] Furthermore, in a case where the contact portion is a sliding element, for example, it is preferred to use any of polytetrafluoroethylene, polyphenylene sulfide and polyamide and, in a case where it is a sealing part, for example , it is preferably made of at least one element selected from polytetrafluoroethylene, polyphenylene sulfide, chloroprene rubber, silicone rubber, hydrogenated nitrile rubber, fluorocarbon rubber and epichlorohydrin rubber.
[0277] [00277] In addition, as the insulation material on an electric motor, an insulation covering material for a stator coil, an insulating film and so on can be mentioned. Such insulation cover material and an insulating film are made of a resin that will not be physically or chemically degenerated, even when placed in contact with a working fluid at an elevated temperature under high pressure, by the working fluid, particularly a resin that has solvent resistance, extraction resistance, thermal / chemical stability and bubbling resistance.
[0278] [00278] Specifically, for an insulating cover material for a stator coil, any one of formal polyvinyl, polyester, THEIC-modified polyester, polyamide, polyamideimide, polyesterimide and polyesteramideimide is used. A double coated film consisting of polyamideimide as an upper layer and polyesterimide as a lower layer is preferred. In addition, in addition to the above material, a coating varnish with a glass transition temperature of at least 120 ° C can be used.
[0279] [00279] In addition, as an insulating film, any of polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyphenylene sulfide (PPS) and polybutylene terephthalate (PBT) is used. In addition, for the insulation film, it is possible to use a foam film whose foam material is the same as the working fluid for a refrigeration cycle. For an insulation material used in a stator coil, polyether ether ketone (PEEK) or a liquid crystal polymer (LCP) is used. For a varnish, an epoxy resin is used.
[0280] [00280] When operating the thermal cycle system, in order to avoid inconveniences due to the inclusion of moisture or the inclusion of non-condensed gas, such as oxygen, it is preferred to provide a means to suppress this inclusion.
[0281] [00281] If moisture is included in the thermal cycle system, a problem can occur, particularly when the thermal cycle system is used at low temperature. For example, problems such as freezing in a capillary tube, hydrolysis of the working fluid or coolant, deterioration of materials by an acidic component formed in the cycle, the formation of contaminants, etc., can arise. In particular, if the refrigerant oil is a polyglycol refrigerant oil or a polyol ester refrigerant oil, it has extremely high moisture-absorbing properties and is likely to undergo hydrolysis, and the inclusion of moisture decreases the properties of the refrigerant oil and can be a major cause that undermines the long-term reliability of a compressor. Consequently, in order to suppress the hydrolysis of the refrigerant oil, it is necessary to control the moisture concentration in the thermal cycle system.
[0282] [00282] As a method to control the moisture concentration in the thermal cycle system, a method of using a moisture removal medium, such as a drying agent (such as silica gel, activated aluminum or zeolite) can be mentioned . The drying agent is preferably contacted with the composition for a thermal cycle system in the liquid state in view of the dehydration efficiency. For example, the drying agent is located at the outlet of the condenser 12 or at the inlet of the evaporator 14 to be kept in contact with the composition for a thermal cycle system.
[0283] [00283] The drying agent is preferably a zeolite drying agent in view of the chemical reactivity of the drying agent and the composition for a thermal cycle system and the drying capacity of the drying agent.
[0284] [00284] The zeolite drying agent is, in a case where a refrigerant oil that has a high moisture absorption, compared to a conventional mineral refrigerant oil is preferably used, a zeolite drying agent that contains has a compound represented by the formula (C) below as the main component in view of the excellent moisture absorption capacity. M2 / nO · Al2O3 · xSiO2 · yH2O (C) where M is an element of Group 1, such as Na or K or an element of Group 2, such as Ca, n is the valence of M, and i and i are the values determined by the crystalline structure. The pore size can be adjusted by varying M.
[0285] [00285] To select the drying agent, the pore size and fracture resistance are important.
[0286] [00286] In a case where a drying agent that has a pore size larger than the molecular size of the working fluid and the refrigerant oil contained in the composition for a thermal cycle system is used, the working fluid and the refrigerant oil is adsorbed on the drying agent and as a result, the chemical reaction between the working fluid and the refrigerant oil and the drying agent will occur, thus leading to undesirable phenomena, such as the formation of non-condensable gas, a decrease in the strength of the drying agent , and a decrease in the adsorption capacity.
[0287] Consequently, it is preferred to use, as the drying agent, a zeolite drying agent with a small pore size. Particularly preferred is type A synthetic sodium / potassium zeolite with a maximum pore size of 3.5 Å. By using a type A synthetic sodium / potassium zeolite salt with a pore size smaller than the molecular size of the working fluid and coolant, it is possible to selectively adsorb and remove only moisture in the thermal cycle system without adsorbing the working fluid and the refrigerant oil. In other words, the working fluid and the refrigerant oil are less likely to be adsorbed on the drying agent, and thermal decomposition is less likely to occur and, as a result, the deterioration of the materials that make up the thermal cycle system and the formation of contaminants can be suppressed.
[0288] [00288] The size of the zeolite drying agent is preferably from about 0.5 to about 5 mm, since if it is too small, a valve or a thin part in pipes of the thermal cycle system can obstructed and, if it is too large, the drying capacity will be decreased. Its shape is preferably granular or cylindrical.
[0289] [00289] The zeolite drying agent can be formed in an optional form by solidifying a powdered zeolite through a binding agent (such as bentonite). Thus, since the drying agent is comprised mainly of the zeolite drying agent, another drying agent (such as silica gel or activated alumina) can be used in combination.
[0290] [00290] The proportion of the zeolite drying agent based on the composition for a thermal cycle system is not particularly limited.
[0291] [00291] If non-condensed gas is included in the thermal cycle system, it has adverse effects, such as failure of heat transfer in the condenser or evaporator and an increase in working pressure, and it is necessary to suppress its inclusion as much as possible. possible.
[0292] [00292] Particularly, oxygen is one of the non-condensing gases that reacts with the working fluid or refrigerant and promotes its decomposition.
[0293] [00293] The concentration of non-condensed gas is preferably at most 1.5% by volume, especially preferably at most 0.5% by volume per cycle volume based on the working fluid, in a gaseous phase of the working fluid.
[0294] [00294] According to the thermal cycle system described above in the present invention which employs the composition for a thermal cycle system of the present invention, favorable lubrication properties are obtained, thermal cycle performance practically sufficient can be obtained with suppression of the influence about global warming and there is substantially no problem with temperature variation. EXAMPLES
[0295] [00295] Now, the present invention will be described in more detail with reference to the Examples of the present invention, Examples and Comparative Conventional Examples. In each example, one of the working fluids 1 to 64 below was selected and one of the cooling oils A to I below, 50 g of the working fluid and 50 g of the refrigerant oil were mixed and dissolved to prepare 576 types of composition for a thermal cycle system. Consequently, the composition for a thermal cycle system in the Examples comprises 50% by weight of the working fluid and 50% by weight of the refrigerant oil. In addition, for some working fluids, an antioxidant was added to constitute the composition for a thermal cycle system, as described below.
[0296] [00296] The following working fluids and cooling oils were used. The compounds that make up the working fluids are shown in Table 2 and the compounds that make up the refrigerant oils are shown in Table 3.
[0297] [00297] Refrigerant oil A: polyol ester refrigerant oil (trade name: Unister RH-208BRS, manufactured by NOF CORPORATION)
[0298] [00298] Refrigerant oil B: polyol ester refrigerant oil (trade name: Unister RH-481R, manufactured by NOF CORPORATION)
[0299] [00299] Refrigerant oil C: polyol ester refrigerant oil (trade name: Unister RHR-32, manufactured by NOF CORPORATION)
[0300] [00300] Refrigerant oil D: polyol ester refrigerant oil (trade name: Unister RHR-64, manufactured by NOF CORPORATION)
[0301] [00301] Refrigerant oil E: polyol ester refrigerant oil (trade name: Unister RHR-200, manufactured by NOF CORPORATION)
[0302] [00302] Refrigerant oil F: polyol ester refrigerant oil (trade name: Unister RHR-609BR, manufactured by NOF CORPORATION)
[0303] [00303] Refrigerant oil G: refrigerant oil that contains a polyol ester as the main component (trade name: Ze-GLES RB-68, manufactured by JX Nippon Oil & Energi Corporation)
[0304] [00304] Refrigerant oil H: refrigerant oil containing polyvinyl ether as the main component (trade name: Daphne Hermetic Oil FVC68D, manufactured by Idemitsu Kosan Co., Ltda.)
[0305] [00305] Refrigerant oil I: naphthene-type refrigerant oil (trade name: SUNISO 4GS, manufactured by Idemitsu Kosan Co., Ltda.)
[0306] [00306] In addition, for each of the refrigerant oils A to F, as an additive, an antioxidant (2,6-di-tert-butyl-4-methylphenol) was added in an amount of 0.5% by weight per 100% by mass of the total amount of refrigerant oil and antioxidant to form a refrigerant oil composition, which was used for production and evaluated. In the following test examples, even in a case where such a refrigerant oil composition was used, the refrigerant oil composition was represented as "refrigerant oil". Essay Compatibility with the working fluid
[0307] [00307] Using the working fluid and coolant oil described above, the compatibility of each test oil with the working fluid was assessed according to the test method for determining coolant compatibility in JIS K 2211 "Coolant Oils" . The working fluid and the refrigerant oil were mixed in a proportion of the refrigerant oil of 15% by mass and the state of phase separation was visually confirmed at -60 ° C and at 35 ° C and evaluated based on the following standards.
[0308] [00308] O: The working fluid and the refrigerant oil were compatible with each other at both temperatures.
[0309] [00309] △: The working fluid and the refrigerant oil have become cloudy at both temperatures.
[0310] [00310] X: The working fluid and the refrigerant oil separated from each other at both temperatures. Coolant oil aniline point
[0311] [00311] Using the refrigerant oil above, the aniline point of each test oil was evaluated according to the JIS K2256 standard "Determination of aniline point and mixed aniline point of petroleum products". The aniline and the refrigerant oil were mixed in a mass ratio of 50% by mass: 50% by mass, the mixture obtained was refrigerated from 0 ° C to -100 ° C and the state of phase separation was visually confirmed and evaluated according to the following standards.
[0312] [00312] O: An aniline point has occurred within a range of - 100 to 0 ° C.
[0313] [00313] X: There was no aniline point within a range of -100 to 0 ° C. Change in weight by immersion test
[0314] [00314] The test was carried out according to the JIS K7114 standard "Plastics - Test methods for determining the effects of immersion in liquid chemical products". The composition for a thermal cycle system was placed in a 200 ml pressure-resistant stainless steel container in which a 150 ml glass tube was placed and about 10 g of a nylon-11 test specimen were placed and the container was closed. Then, the pressure-resistant container was stored in a constant temperature chamber (Perfect Oven PHH-202, manufactured by ESPEC CORP.) At 175 ° C for 14 days and the change in weight of the test specimen was confirmed and evaluated accordingly with the following standards.
[0315] [00315] O: No change in weight equal to or greater than 1%.
[0316] [00316] X: Weight change of 1% or more confirmed.
[0317] [00317] A change in weight indicates that the resin has expanded by the immersion test. Cooling oil circulation status
[0318] [00318] Each composition for a thermal cycle system was introduced in a thermal cycle system 10 shown in Figure 1 and the thermal cycle system was operated continuously. To assess the circulation status of the composition for a thermal cycle system, part of a flow path from an evaporator 14 to a compressor 11 in the thermal cycle system consisted of a glass tube. Through the glass tube, the interior was observed to evaluate the circulation status of the composition for a thermal cycle system in the thermal cycle system. Circulation status was visually assessed based on the following standards.
[0319] [00319] O: Circulation of refrigerant oil has been confirmed.
[0320] [00320] △: Although the circulation of refrigerant oil has been confirmed, the amount of circulation was very small.
[0321] [00321] X: Circulation of refrigerant oil has not been confirmed. Stability test
[0322] [00322] The stability test was performed according to the chemical stability test method of refrigerant and refrigerant oil (autoclave) described in standard JIS K2211. The composition for a thermal cycle system was placed in a 200 ml pressure-resistant stainless steel container in which a 150 ml glass tube was placed and, as a catalyst, iron, copper and aluminum test specimens were placed in a pressure-resistant container and the container was closed. Then, the closed pressure-resistant container was stored in a constant temperature chamber (Perfect Oven PHH-202, manufactured by ESPEC CORP.) At 175 ° C for 14 days and the acid content in the working fluid was measured, the hue of the refrigerant oil was observed and the change in the external appearance of the catalyst was observed as follows.
[0323] [00323] In addition, as metal specimens as the catalyst were used the following:
[0324] [00324] a) Iron: a cold-rolled carbon steel plate test specimen (as stipulated in JIS G3141, SPCC-SB), 30 mm x 25 mm x 3.2 mm thick
[0325] [00325] b) Copper: a hard copper test specimen (as stipulated in JIS H3100, alloy number C1100, C1100P), 30 mm x 25 mm x 2 mm thick
[0326] [00326] c) Aluminum: a test specimen of pure aluminum (as stipulated in JIS H4000, alloy number 1050, A1050P), 30 mm x 25 mm x 2 mm thick Coolant oil shade
[0327] [00327] After the stability test, the remaining refrigerant oil in the pressure-resistant container from which the working fluid was removed was removed and the shade of the refrigerant oil was evaluated according to the ASTM-D156 standard.
[0328] [00328] O: No changes observed.
[0329] [00329] X: Coloring continued.
[0330] [00330] In the case where the coloring continued, the composition for a thermal cycle system was deteriorated by the stability test. Alteration of the external appearance of the catalyst
[0331] [00331] The external appearance of the catalyst metal after the stability test has been confirmed visually and the change in the external appearance of the catalyst has been evaluated based on the following standards.
[0332] [00332] O: No changes have been confirmed.
[0333] [00333] X: Catalyst brightness has disappeared or the catalyst has darkened.
[0334] [00334] In a case where the catalyst gloss has disappeared or the catalyst has darkened, the composition for a thermal cycle system has been deteriorated by the stability test. Sediments
[0335] [00335] The presence or absence of sediment was assessed based on the standards to be followed by visual observation of the container after the stability test.
[0336] [00336] O: No sediment observed.
[0337] [00337] X: Observed sediments.
[0338] [00338] In a case where sediments were observed, the composition for a thermal cycle system was subjected to the decomposition of a type of polymerization reaction by the stability test. Test Results Compatibility with the working fluid
[0339] [00339] The results are presented in Tables 4 and 5. Only refrigerant oil I separated from the working fluid and favorable compatibility of refrigerant oils of polyol ester and polyvinyl ether was confirmed. However, no notable difference between the types of working fluid has been confirmed and the same result according to working fluid 11 (R-410), which is a commercially available composition, has been obtained. However, refrigerant oils E and F, which had a high kinematic viscosity, tended to become cloudy, although they were of the polyol ester type.
[0340] [00340] The results are shown in Table 6. Only refrigerant oil I had an aniline point of 80 ° C and a clear difference between refrigerant oils of polyol ester and polyvinyl ether was confirmed. TABLE 6
[0341] [00341] The results are shown in Tables 7 and 8. A change in weight occurred only in refrigerant oil I, which does not have aniline point at -100 to 0 ° C and a clear difference between the refrigerant ester oils of polyol and polyvinyl ether. However, no notable difference between the types of working fluid has been confirmed and the same result as working fluid 11 (R-410), which is a commercially available composition, has been obtained.
[0342] [00342] The results are shown in Tables 9 and 10. No sufficient amount of flow has been confirmed with refrigerant oil I alone and a clear difference between refrigerant oils of polyol ester and polyvinyl ether has been confirmed. However, no notable difference between the types of working fluid has been confirmed and the same result as working fluid 11 (R-410), which is a commercially available composition, has been obtained. However, with refrigerant oils E and F, which had a high kinematic viscosity, despite being polyol ester type, the amount of circulation tended to be slightly small.
[0343] [00343] The stability test was carried out with refrigerant oils, except refrigerant oil I, with which no sufficient amount of flow could be maintained. Coolant oil hue
[0344] [00344] The results are shown in Tables 11 and 12. Favorable results were obtained for all combinations of working fluids, except for working fluid 11 (R-410) and refrigerant oils A, C and E and G to H. Notable color progress has been confirmed in relation to combinations with refrigerant oils B and F.
[0345] [00345] The results are shown in Tables 13 and 14. Likewise, according to the shade test, favorable results were obtained for all combinations of working fluids, except for working fluid 11 (R-410) and refrigerant oils A, C to E and G to H. A noticeable change in the external appearance of the catalyst has been confirmed in relation to combinations with refrigerant oils B and F.
[0346] [00346] The results are shown in Tables 15 and 16. Likewise, according to the shade test, favorable results were obtained in relation to all combinations of working fluids, except for working fluid 11 (R-410) and refrigerant oils A, C to E and G to H. A remarkable sediment was confirmed in relation to the combinations with refrigerant oils B and F.
[0347] [00347] It has been confirmed that, with the composition for a thermal cycle system comprising a polyol ester refrigerant oil or polyvinyl ether that has high compatibility with a working fluid that contains an unsaturated fluorinated hydrocarbon compound, an amount of sufficient circulation, which is the same as working fluid 11 (R-410A), which is a commercially available composition, can be ensured from the results of measuring the state of circulation. However, from the results of the stability test, staining of the refrigerant oil, decolorization of catalyst and formation of sediment was confirmed, specifically in relation to the combinations of the working fluids containing a fluorinated hydrocarbon compound with the cooling oils B and F that have a high hydroxyl value. It is estimated that the double bond contained in its working fluid, except for working fluid 11, suffered decomposition of some kind or polymerization reaction due to the hydroxyl groups. Consequently, it has been confirmed that a composition for a thermal cycle system that has favorable properties can be obtained using, as a refrigerant oil to be used in combination with a working fluid that contains an unsaturated fluorinated hydrocarbon compound that has a specific structure , a refrigerant oil that has favorable compatibility with the working fluid for the thermal cycle and that has a low hydroxyl value.
[0348] [00348] Furthermore, it has been confirmed that with the composition for a thermal cycle system that uses a polyol ester refrigerant oil or polyvinyl ether with high compatibility with a working fluid that contains an unsaturated fluorinated hydrocarbon compound, and with a kinematic viscosity at 40 ° C of a maximum of 200 mm2 / s, a sufficient amount of circulation, which is the same as working fluid 11 (R-410), which is a commercially available composition, can be ensured at from the results of measuring the state of circulation.
[0349] [00349] It has been confirmed that, with a composition for a thermal cycle system comprising a polyol ester refrigerant oil or polyvinyl ether that has an aniline point within a range of -100 to 0 ° C, the expansion of the resin was small with reference to nylon-11 as an example. In addition, from the results of the observation of the circulation state, it was confirmed that a sufficient amount of circulation, which is the same as the working fluid 11 (R-410), which is a commercially available composition, can be assured.
[0350] [00350] From the results above, it is evident that all the compositions for a thermal cycle system that comprise each of the working fluids 1 to 10 and 12 to 64 and each of the refrigerant oils A, C to D and G a H of the present invention have a favorable circulation state and also have excellent properties in terms of stability and are suitable as a composition for a thermal cycle system. INDUSTRIAL APPLICABILITY
[0351] [00351] The composition for a thermal cycle system and a thermal cycle system that employs the composition of the present invention are useful for a refrigerator (such as a built-in display case, a separate display case, an industrial refrigerator, a vending machine or an ice maker), an air conditioning device (such as an individual air conditioning device, an air conditioning device for a store, an air conditioning device for a building, an air conditioning device for a factory, a heat pump for a gasoline engine, an air conditioning device for a train or a power generation system (automotive air conditioning system), such as power generation for exhaust heat recovery or a transport device heat (such as a heat pipe).
[0352] [00352] Full descriptions of Japanese Patent Application No. 2014-030857 filed on February 20, 2014, Japanese Patent Application No. 2014-127744 filed on June 20, 2014, Japanese Patent Application No. 2014-148347 filed on July 18, 2014 and Japanese Patent Application No. 2014-187003 filed on September 12, 2014, including specifications, claims and drawings, summaries are hereby incorporated by reference in their entirety. REFERENCE SYMBOLS 10: refrigeration cycle system, 11: compressor, 12: condenser, 13: expansion valve, 14: evaporator, 15, 16: pump

权利要求:
Claims (11)
[0001]
Composition for a thermal cycle system, characterized by the fact that it comprises a working fluid for thermal cycle that contains at least one unsaturated fluorinated hydrocarbon compound selected from a compound that has at least one unsaturated carbon-carbon bond in its molecule represented by the following formula (I): and a refrigerant oil that has a rupture voltage of at least 25 kV, has a hydroxyl value of at most 0.1 mg KOH / g and a minimum temperature on the high temperature side of the phase separation temperature from the fluid working temperature for the thermal cycle of at least 35 ° C and a maximum temperature on the low temperature side of at most -60 ° C, where the refrigerant oil is an ester refrigerant oil, an ether refrigerant oil, or an oil polyglycol refrigerant: CxFyRz (I) where R is H or Cl, x is an integer from 2 to 6, y is an integer from 1 to 12 and z is an integer between 0 and 11, as long as 2x≥y + z≥2, where the working fluid for the thermal cycle also contains a saturated fluorinated hydrocarbon compound, and wherein trifluoroethylene and 2,3,3,3-tetrafluorpropene are contained as the unsaturated fluorinated hydrocarbon compound, and difluoromethane is contained as the saturated fluorinated hydrocarbon compound, the proportion of the total amount of trifluoroethylene, 2,3,3,3-tetrafluorpropene and difluoromethane, based on the total amount of working fluid for the thermal cycle, is greater than 90% by mass and at most 100% by mass , and based on the total amount of trifluoroethylene, 2,3,3,3-tetrafluorpropene and difluoromethane, the mass ratio of trifluoroethylene is at least 10% by mass and less than 70% by mass, the mass ratio of 2.3 , 3,3-tetrafluoropropene is greater than 0% by mass and at most 50% by mass and the mass ratio of difluoromethane is greater than 30% by mass and at most 75% by mass.
[0002]
Composition for a thermal cycle system, characterized by the fact that it comprises a working fluid for thermal cycle that contains at least one unsaturated fluorinated hydrocarbon compound selected from a compound that has at least one unsaturated carbon-carbon bond in its molecule represented by the following formula (I): and a refrigerant oil that has a rupture voltage of at least 25 kV, has a hydroxyl value of at most 0.1 mg KOH / g and a minimum temperature on the high temperature side of the phase separation temperature from the fluid working temperature for the thermal cycle of at least 35 ° C and a maximum temperature on the low temperature side of at most -60 ° C, where the refrigerant oil is an ester refrigerant oil, an ether refrigerant oil, or an oil polyglycol refrigerant: CxFyRz (I) where R is H or Cl, x is an integer from 2 to 6, y is an integer from 1 to 12 and z is an integer between 0 and 11, as long as 2x≥y + z≥2, where the working fluid for the thermal cycle also contains a saturated fluorinated hydrocarbon compound, and wherein trifluoroethylene and 2,3,3,3-tetrafluorpropene are contained as the unsaturated fluorinated hydrocarbon compound, and difluoromethane is contained as the saturated fluorinated hydrocarbon compound, the proportion of the total amount of trifluoroethylene, 2,3,3,3-tetrafluorpropene and difluoromethane, based on the total amount of working fluid for the thermal cycle, is greater than 90% by mass and at most 100% by mass , and based on the total amount of trifluoroethylene, 2,3,3,3-tetrafluorpropene and difluoromethane, the mass proportion of the total amount of trifluoroethylene and 2,3,3,3-tetrafluorpropene is at least 70% by mass, the proportion in mass of trifluoroethylene is at least 30% by mass and at most 80% by mass, the mass proportion of 2,3,3,3-tetrafluoropropene is greater than 0% by mass and at most 40% by mass and the proportion by weight of difluoromethane is greater than 0% by mass and at most 30% by mass, and the ratio of trifluoroethylene to 2,3,3,3-tetrafluorpropene is at most 95/5.
[0003]
Composition for a thermal cycle system according to claim 1 or 2, characterized in that the compound of formula (I) in which x is 2 or 3, is contained.
[0004]
Composition for a thermal cycle system according to claim 3, characterized by the fact that as the unsaturated fluorinated hydrocarbon compound, at least one element selected from the group consisting of 1,2-difluoroethylene, 2-fluoropropene, 1,1,2-trifluoropropene, (E) -1,2,3,3,3- pentafluoropropene, (Z) -1,2,3,3,3-pentafluoropropene, (E) -1,3,3, 3- tetrafluoropropene, (Z) -1,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropene is contained.
[0005]
Composition for a thermal cycle system according to any one of claims 1 to 4, characterized in that, as the saturated fluorinated hydrocarbon compound, at least one element selected from the group consisting of trifluoromethane, difluoromethane, difluoroethane , trifluoroethane, tetrafluoroethane, pentafluoroethane, trifluoroiodomethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane and heptafluorocyclopentane are contained.
[0006]
Composition for a thermal cycle system according to any one of claims 1 to 5, characterized by the fact that the refrigerant oil is at least one element selected from a polyol ester refrigerant oil and a refrigerant oil from polyvinyl ether.
[0007]
Composition for a thermal cycle system according to any one of claims 1 to 6, characterized in that the refrigerant oil has a kinematic viscosity at 40 ° C from 5 to 200 mm2 / s and a kinematic viscosity at 100 ° C from 1 to 100 mm2 / s.
[0008]
Composition for a thermal cycle system according to any one of claims 1 to 7, characterized by the fact that the refrigerant oil has an aniline point of at least - 100 ° C and at most 0 ° C.
[0009]
Thermal cycle system characterized by the fact that it comprises the composition for a thermal cycle system as defined in any one of claims 1 to 8.
[0010]
Thermal cycle system, according to claim 9, characterized by the fact that it is at least one element selected from a refrigeration device, an air conditioning device, a power generation system, an air transport device heat and a secondary cooling machine.
[0011]
Thermal cycle system according to claim 10, characterized by the fact that the thermal cycle system has a compression mechanism with a contact portion that is in contact with the composition for a thermal cycle system and the contact portion it consists of at least one element selected from an engineering plastic, an organic film and an inorganic film.

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法律状态:
2019-03-19| B25D| Requested change of name of applicant approved|Owner name: AGC INC. (JP) |

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-24| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-02-17| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/02/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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JP2014-030857|2014-02-20|

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JP2014030857|2014-02-20|

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JP2014-127744|2014-06-20|

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JP2014127744|2014-06-20|

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JP2014148347|2014-07-18|

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JP2014-148347|2014-07-18|

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JP2014-187003|2014-09-12|

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JP2014187003|2014-09-12|

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PCT/JP2015/054653|WO2015125881A1|2014-02-20|2015-02-19|Composition for heat cycle system, and heat cycle system|

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