JP2016056340A - Composition for heat cycle system and heat cycle system - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a composition for a heat cycle system capable of replacing R410A, containing an actuation medium for a heat cycle having small global warming coefficient and good in lubrication property and a heat cycle system using the composition.SOLUTION: There is provided a composition for a heat cycle system containing an actuation medium for a heat cycle containing an unsaturated fluorinated hydrocarbon compound having a specific structure, a refrigeration oil having dielectric breakdown voltage of 25 kV or more and hydroxyl value of 0.1 mgKOH/g or less, where a mixture of the actuation medium for a heat cycle is a two layers separation condition in all temperature range from condensation temperature to evaporation temperature of the actuation medium for a heat cycle and the heat cycle system using the composition for a heat cycle system.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a composition for a heat cycle system and a heat cycle system using the composition.

In the present specification, for halogenated hydrocarbons, the abbreviations of the compounds are shown in parentheses after the compound names. In the present specification, the abbreviations are used in place of the compound names as necessary.
Conventionally, working mediums for heat cycle systems such as refrigerants for refrigerators, refrigerants for air conditioning equipment, working media for power generation systems (waste heat recovery power generation, etc.), working media for latent heat transport devices (heat pipes, etc.), secondary cooling media, etc. As such, chlorofluorocarbons (CFC) such as chlorotrifluoromethane and dichlorodifluoromethane, and hydrochlorofluorocarbons (HCFC) such as chlorodifluoromethane have been used. However, CFCs and HCFCs are currently subject to regulation because of their impact on the stratospheric ozone layer.

  From such circumstances, the working medium for the heat cycle system is difluoromethane (HFC-32), tetrafluoroethane, pentafluoroethane (HFC-125), which has little influence on the ozone layer, instead of CFC or HCFC. And other hydrofluorocarbons (HFCs) have been used. For example, R410A (a pseudo-azeotropic mixture of HFC-32 and HFC-125 having a mass ratio of 1: 1) is a refrigerant that has been widely used. However, it has been pointed out that HFC may cause global warming.

  R410A has been widely used in ordinary air-conditioning equipment called so-called package air conditioners and room air conditioners because of its high refrigerating capacity. However, the global warming potential (GWP) is as high as 2088, and therefore development of a low GWP working medium is required. At this time, there is a demand for development of a working medium based on the premise that R410A is simply replaced and the devices that have been used so far continue to be used.

  Recently, hydrofluoro, which is a working medium that has a carbon-carbon double bond and the bond is easily decomposed by OH radicals in the atmosphere, has little influence on the ozone layer and has little influence on global warming. Expectations are gathered for olefins (HFO), that is, HFCs having carbon-carbon double bonds. In this specification, unless otherwise specified, saturated HFC is referred to as HFC, and is used separately from HFO. In some cases, HFC is specified as a saturated hydrofluorocarbon.

  As a working medium using HFO, for example, Patent Document 1 has a technique related to a working medium using 1,1,2-trifluoroethylene (HFO-1123) that has the above-described characteristics and can obtain excellent cycle performance. Is disclosed. Patent Document 2 discloses a technique related to a working medium using 1,2-difluoroethylene (HFO-1132) that has the above-described characteristics and can obtain excellent cycle performance. In these Patent Documents 1 and 2, an attempt is made to use HFO-1123 or HFO-1132 in combination with various HFCs or HFOs for the purpose of improving the nonflammability of the working medium, cycle performance, and the like. ing.

  However, HFOs such as these are compounds that contain unsaturated bonds in the molecule and have a very short lifetime in the atmosphere. Therefore, under conditions where compression and heating in a thermal cycle are repeated, It is inferior in stability to saturated hydrofluorocarbons and hydrochlorofluorocarbons such as HFC and HCFC, and lubricity may be reduced in the thermal cycle system.

  Therefore, in a thermal cycle system using HFO as a working medium, there has been a demand for a method capable of operating the thermal cycle system efficiently while maintaining lubricity while fully utilizing the excellent cycle performance of HFO.

International Publication No. 2012/157774 International Publication No. 2012/157765

  The present invention has been made from the above viewpoint, and in a composition for a thermal cycle system containing HFO, while making full use of the low global warming potential and excellent cycle performance possessed by HFO, HFO is more stably produced. Composition for thermal cycle system that can be lubricated, and thermal cycle system that uses the composition, has less impact on global warming, has high cycle performance, and further improves the lubricity of the working medium for thermal cycle The purpose is to provide.

The present invention provides a composition for a thermal cycle system and a thermal cycle system having the configurations described in [1] to [23] below.
[1] A heat cycle working medium comprising at least one unsaturated fluorinated hydrocarbon compound selected from compounds represented by the following general formula (I) and having one or more carbon-carbon unsaturated bonds in the molecule; ,
The dielectric breakdown voltage is 25 kV or more, the hydroxyl value is 0.1 mgKOH / g or less, and the mixture with the heat cycle working medium is in the entire temperature range from the condensation temperature to the evaporation temperature of the heat cycle working medium. Refrigeration oil in a two-layer separated state;
A composition for a heat cycle system, comprising:
C _x F _y R _z ............ (I)
(In the formula, R is H or Cl, x is an integer of 2 to 6, y is an integer of 1 to 12, z is an integer of 0 to 11, and 2x ≧ y + z ≧ 2.)

[2] The composition for a heat cycle system according to [1], comprising a compound wherein x in the general formula (I) is 2 or 3.
[3] The unsaturated fluorinated hydrocarbon compound is 1,1,2-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, at least one selected from the group consisting of (Z) -1,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropene, A composition for a thermal cycle system.
[4] The composition for a heat cycle system according to any one of [1] to [3], wherein the working medium for heat cycle further contains a saturated fluorinated hydrocarbon compound.

[5] The saturated fluorinated hydrocarbon compound is trifluoromethane, difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, trifluoroiodomethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, penta The composition for a heat cycle system according to [4], comprising at least one selected from the group consisting of fluorobutane and heptafluorocyclopentane.
[6] The unsaturated fluorinated hydrocarbon compound contains 1,1,2-trifluoroethylene, and the content of 1,1,2-trifluoroethylene with respect to 100% by mass of the working medium for heat cycle is 20 The composition for a heat cycle system according to any one of [1] to [5], which is -80% by mass.

[7] Any of [4] to [6], wherein the saturated fluorinated hydrocarbon compound contains difluoromethane, and the content of difluoromethane with respect to 100% by mass of the working medium for heat cycle is 20 to 80% by mass. A composition for a thermal cycle system according to claim 1.
[8] The unsaturated fluorinated hydrocarbon compound includes 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene, and the saturated fluorinated hydrocarbon compound includes difluoromethane,
The ratio of the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane to the total amount of the working medium for the heat cycle is more than 90% by mass and 100% by mass or less,
The ratio of mass to the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane,
1,1,2-trifluoroethylene is 10 mass% or more and less than 70 mass%,
2,3,3,3-tetrafluoropropene is more than 0% by mass and 50% by mass or less,
And the composition for thermal cycle systems as described in [4] or [5] whose difluoromethane is more than 30 mass% and 75 mass% or less.

[9] The unsaturated fluorinated hydrocarbon compound includes 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene, and the saturated fluorinated hydrocarbon compound includes difluoromethane,
The ratio of the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane to the total amount of the working medium for the heat cycle is more than 90% by mass and 100% by mass or less,
The ratio of mass to the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane,
The total amount of 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene is 70% by mass or more,
1,1,2-trifluoroethylene is 30% by mass or more and 80% by mass or less,
2,3,3,3-tetrafluoropropene is more than 0% by weight and 40% by weight or less,
Difluoromethane is more than 0% by mass and 30% by mass or less,
And the ratio of 1,1,2-trifluoroethylene to 2,3,3,3-tetrafluoropropene is 95/5 or less,
The composition for a heat cycle system according to [4] or [5].
[10] The composition for a heat cycle system according to any one of [1] to [9], wherein the refrigerating machine oil is at least one selected from polyol ester type refrigerating machine oil and polyvinyl ether type refrigerating machine oil.
[11] The refrigerating machine oil is kinematic viscosity of 5 to 200 mm ² / s at 40 ° C., a kinematic viscosity at 100 ° C. is 1 to 100 mm ² / s, according to any one of [1] to [10] A composition for a thermal cycle system.

[12] The composition for a heat cycle system according to any one of [1] to [11], wherein the refrigeration oil has an aniline point of −100 ° C. or higher and 0 ° C. or lower.
[13] The composition for a heat cycle system according to any one of [1] to [12], wherein the refrigerating machine oil has a water content of 300 ppm or less.
[14] The composition for a heat cycle system according to any one of [1] to [13], wherein the residual air partial pressure of the refrigerating machine oil is 10 kPa or less.
[15] The composition for a heat cycle system according to any one of [1] to [14], wherein the ash content of the refrigerating machine oil is 100 ppm or less.
[16] [1] to [15] including at least one additive selected from a copper deactivator, an extreme pressure agent, an oily agent, an antioxidant, an acid scavenger, an antifoaming agent, and a polymerization inhibitor. The composition for thermal cycle systems according to any one of the above.

[17] A thermal cycle system using the composition for thermal cycle system according to any one of [1] to [16].
[18] The thermal cycle system according to [17], wherein the thermal cycle system is at least one selected from refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers.
[19] The thermal cycle system has a compression mechanism, and the contact portion of the compression mechanism that comes into contact with the composition for the thermal cycle system is composed of at least one selected from engineering plastics, organic films, and inorganic films. , [18] The heat cycle system.
[20] The thermal cycle system according to [19], wherein the engineering plastic is at least one selected from polyamide resin, polyphenylene sulfide resin, polyacetal resin, and fluororesin.
[21] Heat formed using the organic film using a polytetrafluoroethylene coating film, a polyimide coating film, a polyamideimide coating film, and a resin coating material including a resin composed of a polyhydroxy ether resin and a polysulfone resin and a crosslinking agent The thermal cycle system according to [19], which is at least one selected from curable insulating films.
[22] The thermal cycle system according to [19], wherein the inorganic film is at least one selected from a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, and a molybdenum film.
[23] The contact portion has a seal portion, and the seal portion is made of at least one selected from polytetrafluoroethylene, polyphenylene sulfide, chloroprene rubber, silicon rubber, hydrogenated nitrile rubber, fluororubber, and hydrin rubber. The thermal cycle system according to [19].

  According to the present invention, in a composition for a thermal cycle system containing an unsaturated fluorinated hydrocarbon compound, the unsaturated fluorinated hydrocarbon compound is fully unsaturated while fully utilizing the low global warming potential and excellent cycle performance of the unsaturated fluorinated hydrocarbon compound. A composition for a heat cycle system that can more stably lubricate a working medium for heat cycle containing a fluorinated hydrocarbon compound can be provided.

  The thermal cycle system of the present invention is a thermal cycle system that has little influence on global warming, has high cycle performance, and further improves the lubrication characteristics of the working medium for thermal cycle.

It is the schematic block diagram which showed the refrigerating cycle system which is an example of the thermal cycle system of this invention. It is the cycle figure which described the state change of the working medium in the refrigeration cycle system of FIG. 1 on the pressure-enthalpy diagram.

Embodiments of the present invention will be described below.
[Composition for thermal cycle system]
The composition for a heat cycle system has a working fluid for a heat cycle containing the unsaturated fluorinated hydrocarbon compound represented by the general formula (I), a specific breakdown voltage, a hydroxyl value, and a predetermined temperature. And a refrigerating machine oil having a property incompatible with the working medium for heat cycle.

  As a heat cycle system to which the composition for a heat cycle system of the present invention is applied, a heat cycle system using a heat exchanger such as a condenser or an evaporator is used without particular limitation. In a heat cycle system, for example, a refrigeration cycle, a gas working medium is compressed by a compressor, cooled by a condenser to produce a high-pressure liquid, the pressure is reduced by an expansion valve, and vaporized at a low temperature by an evaporator. It has a mechanism that takes heat away with heat.

  Hereinafter, each component which the composition for thermal cycle systems of this invention contains is demonstrated.

<Working medium for thermal cycle>
The composition for a heat cycle system of the present invention is at least one unsaturated fluoride selected from compounds represented by the following general formula (I) as a working medium and having one or more carbon-carbon unsaturated bonds in the molecule. Contains hydrocarbon compounds.
C _x F _y R _z ............ (I)
(In the formula, R is H or Cl, x is an integer of 2 to 6, y is an integer of 1 to 12, z is an integer of 0 to 11, and 2x ≧ y + z ≧ 2.)

The general formula (I) represents the type and number of elements in the molecule, and the formula (I) represents a fluorine-containing organic compound having 2 to 6 carbon atoms C. A fluorine-containing organic compound having 2 to 6 carbon atoms can have physical and chemical properties such as boiling point, freezing point, and latent heat of vaporization required as a working medium.
In the general formula (I), the bond form of x carbon atoms represented by C _x includes a carbon-carbon single bond, an unsaturated bond such as a carbon-carbon double bond, and the like. Has one or more unsaturated bonds. The unsaturated bond such as a carbon-carbon double bond is preferably a carbon-carbon double bond from the viewpoint of stability, and the number is preferably 1.
In general formula (I), R represents H or Cl, and any of these may be used, but R is preferably H because there is little risk of destroying the ozone layer. In the general formula (I), the range of y + z is preferably 4 or more.
Hereinafter, the unsaturated fluorinated hydrocarbon compound represented by the general formula (I) is also referred to as an unsaturated fluorinated hydrocarbon compound (I).

[Unsaturated fluorinated hydrocarbon compound (I)]
In the present invention, the unsaturated fluorinated hydrocarbon compound (I) contained in the working fluid for a heat cycle system is, for example, a linear or branched chain olefin having 2 to 6 carbon atoms or 4 to 6 carbon atoms. Fluorinated products of cyclic olefins can be mentioned as preferred.
Specifically, ethylene introduced with 1 to 3 fluorine atoms, propene introduced with 1 to 5 fluorine atoms, butene introduced with 1 to 7 fluorine atoms, 1 to 9 fluorines Penten with atoms introduced, hexene with 1 to 11 fluorine atoms introduced, cyclobutene with 1 to 5 fluorine atoms introduced, cyclopentene with 1 to 7 fluorine atoms introduced, 1 to 9 And cyclohexene introduced with a fluorine atom.

Among these unsaturated fluorinated hydrocarbon compounds (I), unsaturated fluorinated hydrocarbon compounds (I) having 2 to 3 carbon atoms are preferred, and ethylene fluorides having 2 carbon atoms are more preferred. Examples of the unsaturated fluorinated hydrocarbon compound (I) having 2 to 3 carbon atoms include 1,1,2-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)) and 3, , 3-trifluoropropene (HFO-1243zf), and the like.
In the present invention, this unsaturated fluorinated hydrocarbon compound (I) may be used alone or in combination of two or more.

  In addition to the unsaturated fluorinated hydrocarbon compound (I), the working medium according to the present invention may contain an optional component described later, if necessary. The content of the unsaturated fluorinated hydrocarbon compound (I) with respect to 100% by mass of the working medium is preferably 10% by mass or more, more preferably 20 to 80% by mass, even more preferably 40 to 80% by mass, and 40 to 40%. 60 mass% is more preferable.

(HFO-1123)
Hereinafter, a working medium containing HFO-1123 as an essential component as the unsaturated fluorinated hydrocarbon compound (I) will be described as an example. Here, HFO-1123 is an unsaturated fluorinated hydrocarbon other than HFO-1123. It can also be replaced by compound (I).

  First, the characteristics of HFO-1123 as a working medium are shown in Table 1 in a relative comparison with R410A (a pseudo-azeotropic mixture of HFC-32 and HFC-125 having a mass ratio of 1: 1). The cycle performance is indicated by a coefficient of performance and a refrigerating capacity obtained by a method described later. The coefficient of performance and the refrigeration capacity of HFO-1123 are shown as relative values (hereinafter referred to as the relative coefficient of performance and the relative refrigeration capacity) with R410A as a reference (1.000). The global warming potential (GWP) is a value of 100 years indicated in the Intergovernmental Panel on Climate Change (IPCC) Fourth Assessment Report (2007) or measured according to the method. In this specification, GWP refers to this value unless otherwise specified. When the working medium is composed of a mixture, the temperature gradient is an important factor in evaluating the working medium as described later, and a smaller value is preferable.

[Optional ingredients]
The working medium used in the present invention may optionally contain a compound used as a normal working medium in addition to HFO-1123 within a range not impairing the effects of the present invention. Examples of such an arbitrary compound (optional component) include HFO other than HFC and HFO-1123 (HFC having a carbon-carbon double bond), other components that are vaporized and liquefied together with HFO-1123 other than these, etc. Is mentioned. As an optional component, HFO other than HFC and HFO-1123 is preferable.

  As an optional component, a compound capable of keeping the GWP and the temperature gradient within an allowable range while having the effect of further increasing the relative coefficient of performance and the relative refrigeration capacity when used in a heat cycle in combination with HFO-1123 is preferable. . When the working medium contains such a compound in combination with HFO-1123, a better cycle performance can be obtained while keeping the GWP low, and the influence of the temperature gradient is small.

(Temperature gradient)
When the working medium contains an optional component, it has a considerable temperature gradient except when the HFO-1123 and the optional component have an azeotropic composition. The temperature gradient of the working medium varies depending on the type of the optional component and the mixing ratio of HFO-1123 and the optional component.

  When a mixture is used as the working medium, usually an azeotropic or pseudo-azeotropic mixture such as R410A is preferably used. Non-azeotropic mixtures have the problem of causing composition changes when filled from a pressure vessel to a refrigeration air conditioner. Furthermore, when refrigerant leakage from the refrigeration air conditioner occurs, the refrigerant composition in the refrigeration air conditioner is very likely to change, and it is difficult to restore the refrigerant composition to the initial state. On the other hand, the above problem can be avoided if the mixture is azeotropic or pseudo-azeotropic.

  In general, a “temperature gradient” is used as an index for measuring the availability of the mixture in the working medium. A temperature gradient is defined as the nature of heat exchangers, such as evaporation in an evaporator or condensation in a condenser, with different start and end temperatures. In the azeotrope, the temperature gradient is 0, and in the pseudoazeotrope, the temperature gradient is very close to 0, for example, the temperature gradient of R410A is 0.2.

  If the temperature gradient is large, for example, the inlet temperature in the evaporator decreases, which increases the possibility of frost formation. Furthermore, in a heat cycle system, in order to improve heat exchange efficiency, it is common to make the working medium flowing through the heat exchanger and a heat source fluid such as water or air counter flow, and in a stable operation state, Since the temperature difference of the heat source fluid is small, it is difficult to obtain an energy efficient heat cycle system in the case of a non-azeotropic mixture having a large temperature gradient. For this reason, when a mixture is used as a working medium, a working medium having an appropriate temperature gradient is desired.

(HFC)
The optional HFC is preferably selected from the above viewpoint. Here, HFC is known to have higher GWP than HFO-1123. Therefore, the HFC to be combined with HFO-1123 is appropriately selected from the viewpoint of improving the cycle performance as the working medium and keeping the temperature gradient within an appropriate range, and particularly keeping the GWP within an allowable range. It is preferred that

  Specifically, an HFC having 1 to 5 carbon atoms is preferable as an HFC that has little influence on the ozone layer and has little influence on global warming. The HFC may be linear, branched, or cyclic.

  Examples of HFCs include fluorides of alkanes having 1 to 5 carbon atoms, such as trifluoromethane, HFC-32, difluoroethane, trifluoroethane, tetrafluoroethane, HFC-125, trifluoroiodomethane, and pentafluoropropane. , Hexafluoropropane, heptafluoropropane, pentafluorobutane, heptafluorocyclopentane and the like are preferable.

Among these, HFC-32, 1,1-difluoroethane (HFC-152a), 1,1,1-trifluoroethane (HFC) have a small influence on the ozone layer and excellent refrigeration cycle characteristics as HFC. -143a), 1,1,2,2-tetrafluoroethane (HFC-134), 1,1,1,2-tetrafluoroethane (HFC-134a), and HFC-125 are preferred, HFC-32, HFC -152a, HFC-134a, and HFC-125 are more preferred.
One HFC may be used alone, or two or more HFCs may be used in combination.

  The content of HFC in the working medium (100% by mass) can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium composed of HFO-1123 and HFC-32, the coefficient of performance and the refrigerating capacity are improved when the content of HFC-32 is in the range of 1 to 99% by mass. In the case of a working medium composed of HFO-1123 and HFC-134a, the coefficient of performance improves when the content of HFC-134a is in the range of 1 to 99% by mass.

  The preferred HFC GWP is 675 for HFC-32, 1430 for HFC-134a, and 3500 for HFC-125. From the viewpoint of keeping the GWP of the resulting working medium low, the HFC-32 is most preferable as the optional component HFC.

  Moreover, HFO-1123 and HFC-32 can form a pseudo-azeotropic mixture close to azeotropic in a composition range of 99: 1 to 1:99 by mass ratio, and the mixture of both does not choose the composition range almost. The temperature gradient is close to zero. Also in this respect, HFC-32 is advantageous as an HFC combined with HFO-1123.

  In the working medium used in the present invention, when HFC-32 is used together with HFO-1123, the content of HFC-32 with respect to 100% by mass of the working medium is preferably 20% by mass or more, and preferably 20 to 80% by mass. % Is more preferable, and 40 to 60% by mass is more preferable.

(HFO other than HFO-1123)
HFOs other than HFO-1123 are also preferably selected from the same viewpoint as the HFC. In addition, even if it is other than HFO-1123, if it is HFO, GWP is remarkably low compared with HFC. Therefore, as HFOs other than HFO-1123 combined with HFO-1123, it is particularly noted that the cycle performance as the working medium is improved and the temperature gradient is kept within an appropriate range rather than considering GWP. These are preferably selected as appropriate.

  HFOs other than HFO-1123 include HFO-1234yf, HFO-1132, HFO-1261yf, HFO-1243yc, HFO-1225ye (E), HFO-1225ye (Z), HFO-1234ze (E), and HFO-1234ze ( Z), HFO-1243zf and the like.

  Among them, as HFOs other than HFO-1123, HFO-1234yf (GWP = 4), HFO-1234ze (E), HFO-1234ze (Z) have a high critical temperature and excellent durability and coefficient of performance. ) (GWP = 6 for both (E) and (Z) isomers) is preferred, and HFO-1234yf is more preferred. HFOs other than HFO-1123 may be used alone or in combination of two or more.

  The content of HFO other than HFO-1123 in the working medium (100% by mass) can be arbitrarily selected according to the required characteristics of the working medium. For example, in the case of a working medium composed of HFO-1123 and HFO-1234yf or HFO-1234ze, the coefficient of performance improves when the content of HFO-1234yf or HFO-1234ze is in the range of 1 to 99% by mass.

A preferred composition range in the case where the working medium used in the present invention contains HFO-1123 and HFO-1234yf is shown below as a composition range (S).
In each formula showing the composition range (S), the abbreviation of each compound indicates the ratio (% by mass) of the compound with respect to the total amount of HFO-1123, HFO-1234yf, and other components (such as HFC-32). .

<Composition range (S)>
HFO-1123 + HFO-1234yf ≧ 70% by mass
The ratio (mass%) of HFO-1123 with respect to the total amount of HFO-1123 and HFO-1234yf is 35 to 95 mass%.

  The working medium in the composition range (S) has a very low GWP and a small temperature gradient. In addition, from the viewpoint of coefficient of performance, refrigeration capacity, and critical temperature, refrigeration cycle performance that can be substituted for conventional R410A can be expressed.

  In the working medium having the composition range (S), the ratio of HFO-1123 to the total amount of HFO-1123 and HFO-1234yf is more preferably 40 to 95 mass%, further preferably 50 to 90 mass%, and more preferably 50 to 85 mass%. % Is particularly preferable, and 60 to 85% by mass is most preferable.

  Further, the total content of HFO-1123 and HFO-1234yf in 100% by mass of the working medium is more preferably 80 to 100% by mass, further preferably 90 to 100% by mass, and particularly preferably 95 to 100% by mass.

The working medium used in the present invention may be a combination of HFO-1123, HFC, and HFO other than HFO-1123. In this case, the working medium is preferably composed of HFO-1123, HFC-32, and HFO-1234yf, and the ratio of each compound in the total amount of the working medium is preferably in the following range.
10% by mass ≦ HFO-1123 ≦ 80% by mass
10% by mass ≦ HFC-32 ≦ 75% by mass
5% by mass ≦ HFO-1234yf ≦ 60% by mass

Furthermore, when the working medium used for this invention contains HFO-1123, HFO-1234yf, and HFC-32, a preferable composition range (P) is shown below.
In each formula showing the composition range (P), the abbreviation of each compound indicates the ratio (mass%) of the compound with respect to the total amount of HFO-1123, HFO-1234yf, and HFC-32. The same applies to the composition range (R), composition range (L), and composition range (M). In the composition range described below, the total amount of HFO-1123, HFO-1234yf, and HFC-32 specifically described is more than 90% by mass and less than 100% by mass with respect to the total amount of the working medium for heat cycle. Preferably there is.

<Composition range (P)>
70% by mass ≦ HFO-1123 + HFO-1234yf
30% by mass ≦ HFO-1123 ≦ 80% by mass
0% by mass <HFO-1234yf ≦ 40% by mass
0% by mass <HFC-32 ≦ 30% by mass
HFO-1123 / HFO-1234yf ≦ 95/5

  The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a well-balanced manner, and the disadvantages of each of them are suppressed. In other words, this working medium is a working medium that has a very low GWP, has a small temperature gradient, and has a certain capacity and efficiency when used in a thermal cycle, and can obtain good cycle performance.

  Moreover, as a more preferable composition of the working medium used for this invention, 30-70 mass% of HFO-1123 and 4-40 of HFO-1234yf are with respect to the total amount of HFO-1123, HFO-1234yf, and HFC-32. A composition containing 0% by mass to 30% by mass of HFC-32 and a content of HFO-1123 based on the total amount of the working medium is 70 mol% or less. The working medium in the above range is a highly durable working medium in which the above effect is enhanced and the self-decomposition reaction of HFO-1123 is suppressed. From the viewpoint of the relative coefficient of performance, the content of HFC-32 is preferably 5% by mass or more, and more preferably 8% by mass or more.

Moreover, although another preferable composition is shown when the working medium used in the present invention contains HFO-1123, HFO-1234yf and HFC-32, the content of HFO-1123 with respect to the total amount of the working medium should be 70 mol% or less. For example, the self-decomposition reaction of HFO-1123 is suppressed, and a highly durable working medium is obtained.
A more preferred composition range (R) is shown below.
<Composition range (R)>
10% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 50% by mass
30% by mass <HFC-32 ≦ 75% by mass

  The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a well-balanced manner, and the disadvantages of each of them are suppressed. That is, it is a working medium in which good cycle performance can be obtained by having a low temperature gradient and high performance and efficiency when used in a thermal cycle after GWP is kept low and durability is ensured.

In the working medium of the present invention having the composition range (R), preferred ranges are shown below.
20% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 40% by mass
30% by mass <HFC-32 ≦ 75% by mass

  The working medium having the above composition is a working medium in which the characteristics of HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of each of them are suppressed. That is, it is a working medium in which GWP is kept low and durability is ensured, and when used in a thermal cycle, the temperature gradient is smaller and the cycle performance is higher by having higher capacity and efficiency. is there.

In the working medium of the present invention having the composition range (R), a more preferred composition range (L) is shown below. The composition range (M) is more preferable.
<Composition range (L)>
10% by mass ≦ HFO-1123 <70% by mass
0% by mass <HFO-1234yf ≦ 50% by mass
30% by mass <HFC-32 ≦ 44% by mass

<Composition range (M)>
20% by mass ≦ HFO-1123 <70% by mass
5 mass% ≦ HFO-1234yf ≦ 40 mass%
30% by mass <HFC-32 ≦ 44% by mass

The working medium having the composition range (M) is a working medium in which the characteristics of the HFO-1123, HFO-1234yf, and HFC-32 are exhibited in a particularly well-balanced manner, and the disadvantages of the working medium are suppressed. In other words, this working medium has a GWP with an upper limit of 300 or less, and durability is ensured, and when used in a heat cycle, the temperature gradient is less than 5.8, and the relative coefficient of performance and relative This is a working medium having a refrigerating capacity close to 1 and good cycle performance.
When the composition of the working medium is within this range, the upper limit of the temperature gradient is lowered and the lower limit of the relative coefficient of performance x the relative refrigeration capacity is raised. From the viewpoint of a large relative coefficient of performance, 8% by mass ≦ HFO-1234yf is more preferable. Moreover, HFO-1234yf <= 35 mass% is more preferable from the point with a large relative freezing capacity.

(Other optional ingredients)
The working medium used for the composition for a heat cycle system of the present invention may contain carbon dioxide, hydrocarbon, CFO, HCFO, etc. in addition to the above optional components. Other optional components are preferably components that have little influence on the ozone layer and little influence on global warming.

Examples of the hydrocarbon include propane, propylene, cyclopropane, butane, isobutane, pentane, isopentane and the like.
A hydrocarbon may be used individually by 1 type and may be used in combination of 2 or more type.

  When the said working medium contains a hydrocarbon, less than 10 mass% is preferable with respect to 100 mass% of a working medium, 1-5 mass% is more preferable, 3-5 mass% is further more preferable. By containing the hydrocarbon, the solubility of the mineral refrigerating machine oil in the working medium becomes better.

Examples of CFO include chlorofluoropropene and chlorofluoroethylene. As the CFO, 1,1-dichloro-2,3,3,3-tetrafluoropropene (CFO-1214ya), 1 is easy to suppress the flammability of the working medium without greatly reducing the cycle performance of the working medium. , 3-dichloro-1,2,3,3-tetrafluoropropene (CFO-1214yb) and 1,2-dichloro-1,2-difluoroethylene (CFO-1112) are preferred.
One type of CFO may be used alone, or two or more types may be used in combination.

  When the working medium contains CFO, the content is preferably less than 10% by weight, more preferably 1 to 8% by weight, and even more preferably 2 to 5% by weight with respect to 100% by weight of the working medium. By containing CFO, it is easy to suppress the combustibility of the working medium. If the content of CFO is not more than the upper limit value, good cycle performance can be easily obtained.

Examples of HCFO include hydrochlorofluoropropene and hydrochlorofluoroethylene. As HCFO, 1-chloro-2,3,3,3-tetrafluoropropene (HCFO-1224yd), 1-chloro is easily used because flammability of the working medium can be easily suppressed without greatly reducing the cycle performance of the working medium. -1,2-difluoroethylene (HCFO-1122) is preferred.
HCFO may be used alone or in combination of two or more.

  When the working medium contains HCFO, the content of HCFO in 100% by mass of the working medium is preferably less than 10% by mass, more preferably 1 to 8% by mass, and even more preferably 2 to 5% by mass. By containing HCFO, it is easy to suppress the combustibility of the working medium. If the content of HCFO is not more than the upper limit value, good cycle performance can be easily obtained.

  When the working medium used in the composition for a heat cycle system of the present invention contains other optional components as described above, the total content of the other optional components in the working medium is 10% by mass with respect to 100% by mass of the working medium. % Is preferable, 8% by mass or less is more preferable, and 5% by mass or less is more preferable.

<Refrigerator oil>
The composition for a heat cycle system of the present invention contains a refrigerating machine oil that satisfies the following properties (O-1) to (O-3) in addition to the working medium for the heat cycle. The refrigerating machine oil is contained in the composition for a heat cycle system together with the working medium and circulates in the heat cycle system, and functions as a lubricating oil in the compressor in the heat cycle system.
(O-1) The dielectric breakdown voltage is 25 kV or more.
(O-2) The hydroxyl value is 0.1 mgKOH / g or less.
(O-3) The mixture with the working medium is in a two-layer separated state in the entire temperature range from the condensation temperature to the evaporation temperature of the working medium.

Hereinafter, the characteristics (O-1) to (O-3) will be described.
(Dielectric breakdown voltage)
By setting the dielectric breakdown voltage of the refrigerating machine oil to 25 kV or more, insulation can be maintained even in a heat cycle system in which the driving electromagnet and the refrigerating machine oil are in direct contact, and stable operation can be performed. The dielectric breakdown voltage is more preferably 30 kV or more, and further preferably 40 kV or more. In this specification, it is determined whether the breakdown voltage uses a catalog value or is a threshold value such as 25 kV or less by simple confirmation based on JIS C 2101.

(Hydroxyl value)
By setting the hydroxyl value of the refrigerating machine oil to 0.1 mgKOH / g or less, it is possible to suppress the generation of hydroxy radicals that cause deterioration due to polymerization and decomposition reaction of the refrigerating machine oil and the working medium for heat cycle. In a system using a working medium containing the unsaturated fluorinated hydrocarbon compound (I), it is presumed that the hydroxy radical attacks and decomposes the unsaturated bond, and an acid is generated at that time. When the acid is generated, there is a possibility that the members constituting the system are corroded or deteriorated in the thermal cycle system. By suppressing the generation of hydroxy radicals, the above degradation and the like can be suppressed, and the polymerization of the unsaturated fluorinated hydrocarbon compound (I) can also be suppressed.

  Therefore, in the present invention in which the hydroxyl value is lowered as described above, the generation of acid can be significantly suppressed, and the thermal cycle system can be stably operated. The hydroxyl value is more preferably 0.05 mgKOH / g or less. In the present specification, the hydroxyl value is measured according to JIS K 2501.

(Incompatible)
In the refrigerating machine oil, the mixture with the working medium is in a two-layer separated state in the entire temperature range from the condensation temperature to the evaporation temperature of the working medium. Hereinafter, the refrigerating machine oil having such properties is also referred to as an incompatible refrigerating machine oil. In addition, when the working medium and the refrigerating machine oil are mixed, the refrigerating machine oil is said to be compatible with the working medium if the working medium and the refrigerating machine oil become a uniform liquid.

  As the incompatible refrigerating machine oil, an oil that can be separated into two layers in the above temperature range regardless of the mixing ratio of the working medium and the refrigerating machine oil is preferable. The mixture of the working medium and the refrigerating machine oil may be one in which two layers are separated in the above temperature range in a mixture containing 10 to 50% by mass of the refrigerating machine oil in the mixture. A mixture containing 20% by mass may be separated into two layers within the above temperature range.

  The condensation temperature and evaporation temperature of the working medium refer to the condensation temperature and evaporation temperature when the working medium circulates in the heat cycle system. The condensing temperature and evaporating temperature of the working medium will be described below by taking a refrigeration cycle as an example with reference to the drawings.

  A refrigeration cycle system 10 shown in FIG. 1 cools and liquefies a compressor 11 that compresses the working medium vapor A into a high-temperature and high-pressure working medium vapor B and the working medium vapor B discharged from the compressor 11. The condenser 12 as a low-temperature and high-pressure working medium C, the expansion valve 13 that expands the working medium C discharged from the condenser 12 to form a low-temperature and low-pressure working medium D, and the working medium D discharged from the expansion valve 13 Is composed of an evaporator 14 that heats the working medium vapor A to a high-temperature and low-pressure working medium vapor A, a pump 15 that supplies a load fluid E to the evaporator 14, and a pump 16 that supplies a fluid F to the condenser 12. System.

In the refrigeration cycle system 10, the following cycles (i) to (iv) are repeated.
(I) The working medium vapor A discharged from the evaporator 14 is compressed by the compressor 11 into a high-temperature and high-pressure working medium vapor B (hereinafter referred to as “AB process”).
(Ii) The working medium vapor B discharged from the compressor 11 is cooled by the fluid F in the condenser 12 and liquefied to obtain a low temperature and high pressure working medium C. At this time, the fluid F is heated to become fluid F ′ and is discharged from the condenser 12 (hereinafter referred to as “BC process”).

(Iii) The working medium C discharged from the condenser 12 is expanded by the expansion valve 13 to obtain a low-temperature and low-pressure working medium D (hereinafter referred to as “CD process”).
(Iv) The working medium D discharged from the expansion valve 13 is heated by the load fluid E in the evaporator 14 to obtain high-temperature and low-pressure working medium vapor A. At this time, the load fluid E is cooled to become the load fluid E ′ and discharged from the evaporator 14 (hereinafter referred to as “DA process”).

  The refrigeration cycle system 10 is a cycle system including adiabatic / isentropic change, isoenthalpy change, and isobaric change. When the state change of the working medium is described on the pressure-enthalpy line (curve) diagram shown in FIG. 2, it can be expressed as a trapezoid having A, B, C, and D as vertices.

  The AB process is a process in which adiabatic compression is performed by the compressor 11 to convert the high-temperature and low-pressure working medium vapor A into a high-temperature and high-pressure working medium vapor B, which is indicated by an AB line in FIG. As will be described later, the working medium vapor A is introduced into the compressor 11 in an overheated state, and the obtained working medium vapor B is also an overheated vapor.

The BC process is a process in which the condenser 12 performs isobaric cooling to convert the high-temperature and high-pressure working medium vapor B into a low-temperature and high-pressure working medium C, and is indicated by a BC line in FIG. The pressure at this time is the condensation pressure. Pressure - of intersection of the enthalpy and BC line is the intersection T ₁ of the high enthalpy side "condensation temperature", low enthalpy side intersection T ₂ is the condensation boiling temperature. Here, when the working medium is a single compound or an azeotrope, T ₁ and T ₂ are equal. In the case of a non-azeotropic mixture, a difference occurs between T ₁ and T ₂ . In the present invention, in this case, a higher temperature of T ₁ and T ₂ is defined as a “condensation temperature”. Note that the temperature gradient in the case of a non-azeotropic mixture is shown as the difference between T ₁ and T ₂ .

The CD process is a process in which the enthalpy expansion is performed by the expansion valve 13 and the low-temperature and high-pressure working medium C is used as the low-temperature and low-pressure working medium D, and is indicated by a CD line in FIG. Incidentally, if Shimese the temperature in the working medium C of low temperature and high pressure at _{T 3, T} 2 -T ₃ is (i) ~ supercooling degree of the working medium in the cycle of (iv) (SC).

The DA process is a process of performing isobaric heating in the evaporator 14 to return the low-temperature and low-pressure working medium D to the high-temperature and low-pressure working medium vapor A, and is indicated by a DA line in FIG. The pressure at this time is the evaporation pressure. Pressure - intersection T ₆ of the high enthalpy side of the intersection of the enthalpy and DA lines are "evaporation temperature". If Shimese the temperature of the working medium vapor A in _{T 7, T 7} -T ₆ is (i) ~ superheat of the working medium in the cycle of (iv) (SH). T ₄ indicates the temperature of the working medium D. Here, when the working medium is a single compound or an azeotrope, T ₄ and T ₆ are equal. In the case of a non-azeotropic mixture, a difference occurs between T ₄ and T ₆ . In the present invention, in this case, the lower temperature of T ₄ and T ₆ is referred to as “evaporation temperature”.

  Generally, in the composition for a heat cycle system, a refrigerating machine oil having high compatibility with a working medium is used. However, when such refrigerating machine oil is used, since the working medium dissolved in the refrigerating machine oil is large, the viscosity of the refrigerating machine oil is significantly reduced by the working medium dissolved in the refrigerating machine oil in the compressor. Therefore, in order to have a sufficient sliding resistance (or lubrication performance) in a state where the refrigerant is melted in the compressor, it is necessary to set the viscosity of the refrigerating machine oil to be high.

  As described above, in the composition for the heat cycle system using the refrigerating machine oil having high compatibility with the working medium, since the difference between the viscosity of the composition for the heat cycle system and the viscosity of the refrigerating machine oil is large, the pressure and temperature change. Then, the dissolution viscosity (kinematic viscosity) of the composition for a heat cycle system changes significantly due to the change in the amount of working medium dissolved in the refrigerating machine oil. Specifically, the viscosity of the composition for the heat cycle system is too high under the condition that the degree of superheating of the working medium gas in the compressor with a relatively small amount of dissolved working medium (difference from the boiling point of the superheated steam temperature) is too high. There was a problem that the viscosity of the composition for a heat cycle system was too low under the condition that the degree of superheat of the working medium gas in the compressor having a large amount of dissolution was small.

  Therefore, in the composition for a heat cycle system of the present invention, the refrigeration oil to be used satisfies the characteristic that the mixture with the working medium is in a two-layer separated state in the entire temperature range from the condensation temperature to the evaporation temperature of the working medium. It was supposed to be. By doing so, the solubility of the working medium in the refrigerating machine oil does not increase more than necessary in the compressor, and it is possible to prevent a significant decrease in the viscosity of the composition for the heat cycle system. That is, in the composition for a heat cycle system of the present invention, there is almost no decrease in viscosity in the compressor, and since it always has a sufficient sliding resistance, it is possible to increase the reliability of the sliding portion, Stable operation is possible from the initial operation of the system.

  In the composition for a heat cycle system of the present invention, the working medium and the refrigerating machine oil incompatible with the working medium are usually used so as to circulate in the heat cycle system in a suspended state.

  Note that the condensation temperature and evaporation temperature of the working medium in the heat cycle system are usually temperatures set in use according to various applications. For example, the condensation temperature is set to about 65 ° C. or less for an air conditioner and about 80 ° C. or less for a water heater, and the evaporation temperature is set to about −10 ° C. to −30 ° C. for an air conditioner and a water heater. In the composition for a heat cycle system of the present invention, the refrigerating machine oil is selected from the refrigerating machine oils satisfying the above (O-1) and (O-2) according to the use conditions of the heat cycle system used (O- Those satisfying the incompatibility according to 3) are appropriately selected.

Here, regarding the refrigeration capacity (Q) and coefficient of performance (COP) of the working medium described above, for example, A (after evaporation, high temperature and low pressure), B (compression) of the working medium described with reference to FIGS. Then, using each enthalpy, h _A , h _B , h _C , h _D in each state of C (after condensation, low temperature and high pressure), D (after expansion, low temperature and low pressure), the following formula (A) , (B). However, these are values that are obtained as if there is no loss due to equipment efficiency and no pressure loss in piping and heat exchangers.

  The thermodynamic properties necessary for calculating the cycle performance of the working medium can be calculated based on a generalized equation of state (Soave-Redrich-Kwong equation) based on the corresponding state principle and thermodynamic relational equations. If characteristic values are not available, calculation is performed using an estimation method based on the group contribution method.

Q = h _A −h _D (A)
COP = Q / compression work = (h _A −h _D ) / (h _B −h _A ) (B)

Q indicated by (h _A -h _D ) corresponds to the output (kW) of the refrigeration cycle, and is required for operating the compression work indicated by (h _B -h _A ), for example, the compressor. The amount of electric power corresponds to the consumed power (kW). Q means the ability to freeze the load fluid, and the higher Q means that more work can be done in the same system. In other words, a large Q indicates that the target performance can be obtained with a small amount of working medium, and the system can be miniaturized.

The refrigerating machine oil preferably has the following characteristics (O-4) and / or (O-5) in addition to the characteristics (O-1) to (O-3).
(O-4) a kinematic viscosity at 40 ° C. was 5 to 200 mm ² / s, kinematic viscosity at 100 ° C. is 1 to 100 mm ² / s.
(O-5) The aniline point is -100 ° C or higher and 0 ° C or lower.

(Kinematic viscosity)
The kinematic viscosity at 40 ° C. of the refrigerating machine oil is preferably in the above range from the viewpoint of suppressing lubrication failure of the refrigerating machine compressor and sufficiently performing heat exchange in the evaporator without reducing the lubricity and the hermeticity of the compressor. 5-100 mm < ² > / s is more preferable. The kinematic viscosity at 100 ° C. is preferably in the above range, more preferably ^{2 to} 30 mm ² / s from the viewpoint of maintaining power consumption and wear resistance within an appropriate range. The kinematic viscosity in this specification is measured in accordance with JIS K 2283.

(Aniline point)
The aniline point is defined as the lowest temperature at which equal volumes of aniline and sample exist as a homogeneous solution. In general, the sample is also used as a swelling index indicating how much rubber or resin swells. In the present specification, the temperature at which refrigeration oil is mixed with an equal volume of aniline to form a uniform solution and then becomes insoluble when they are cooled and starts to become cloudy is defined as the aniline point. In this specification, the aniline point is measured according to JIS K 2256.

  In general, in a thermal cycle system, a sliding member (bearing, etc.) provided in a sliding part of a compressor, a seal member for preventing leakage of a working medium, an insulating material provided in an electric motor, etc. are made of resin. The Moreover, since the said working medium which the composition for thermal cycle systems of this invention contains unsaturated fluorocarbon compound (I), in the thermal cycle system using this as mentioned later, in the said resin, It is preferable that the contact part which contacts the composition for thermal cycle systems containing each member made from at least 1 sort (s) chosen from an engineering plastic, an organic film, and an inorganic film | membrane.

  In a member made of engineering plastic or a member coated with an organic film (hereinafter referred to as a resin member), if the aniline point of the refrigerating machine oil is too low, the refrigerating machine oil easily penetrates into the resin member and swells easily. On the other hand, when the aniline point is too high, the refrigerating machine oil hardly penetrates into the resin member, and the resin member easily contracts. Therefore, by setting the aniline point of the refrigerating machine oil within the above range, swelling / shrinkage of the resin member can be suppressed. As a result, the durability of the resin member is improved and the reliability of the thermal cycle system is improved.

Further, the contents of impurities other than the refrigerating machine oil contained in the refrigerating machine oil, such as moisture and ash, are preferably as follows.
(impurities)
The water content of the refrigerating machine oil is not particularly limited, but is preferably 300 ppm or less, more preferably 200 ppm or less, and most preferably 100 ppm or less based on the total amount of the refrigerating machine oil. In particular, when used for closed-type refrigerators, it is required that the moisture content is low from the viewpoint of decomposition stability of the working medium and influence on the thermal / chemical stability and electrical insulation of the refrigerator oil. . In the present specification, the water content is measured in accordance with JIS K 2275.

  Further, the residual air partial pressure of the refrigerating machine oil is not particularly limited, but is preferably 10 kPa or less, and more preferably 5 kPa or less.

  Further, the ash content of the refrigerating machine oil used here is not particularly limited, but in order to increase the thermal and chemical stability of the refrigerating machine oil and suppress the generation of sludge and the like, it is preferably 100 ppm or less, more preferably 50 ppm or less. it can. In addition, in this specification, an ash content means the value of the ash content measured based on JISK2272.

  The refrigerating machine oil used in the present invention is not particularly limited as long as it is a refrigerating machine oil having the characteristics (O-1) to (O-3). Specifically, in the oxygen-containing synthetic oil (ester-based refrigerating machine oil, ether-based refrigerating machine oil, polyglycol oil, etc.), hydrocarbon-based refrigerating machine oil, etc., the characteristics (O-1) to (O-3) described above are used. The refrigerating machine oil which has is mentioned. These preferably have the characteristics (O-4) and / or (O-5) described above, and the impurities and the like are preferably within the above range.

  Among these, ester-based refrigerating machine oils and ether-based refrigerating machine oils having the characteristics (O-1) to (O-3) are suitable. In addition, although only the classification as a compound of refrigeration oil is described in the following description, it is essential that these have the characteristics (O-1) to (O-3) as the refrigeration oil used in the present invention. It is a condition. Further, polyol ester type refrigerating machine oil is preferable as the ester type refrigerating machine oil, and polyvinyl ether type refrigerating machine oil is preferable as the ether type refrigerating machine oil.

  In particular, in the case of ester-based refrigerating machine oils and ether-based refrigerating machine oils, carbon atoms and oxygen atoms are typically cited as the atoms constituting the refrigerating machine oil. If the ratio of carbon atoms to oxygen atoms (carbon / oxygen molar ratio) is too small, the hygroscopicity is increased. From this viewpoint, the molar ratio of the carbon atom and oxygen atom in the refrigerating machine oil is suitably 2 or more.

[Ester-based refrigerating machine oil]
As ester-based refrigerating machine oil, in terms of chemical stability, dibasic acid ester-based refrigerating machine oil of dibasic acid and monohydric alcohol, polyol ester refrigerating machine oil of polyol and fatty acid, or polyol and polyvalent base Examples include complex ester refrigerating machine oil of acid and monohydric alcohol (or fatty acid), polyol carbonate refrigerating machine oil, and the like.

(Dibasic acid ester refrigerating machine oil)
Dibasic acid ester refrigerating machine oils include dibasic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, etc. In particular, divalent acids having 5 to 10 carbon atoms (glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, etc.) and monovalent C 1-15 having a linear or branched alkyl group Esters with alcohols (methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, etc.) are preferred. Specific examples of the dibasic ester-based refrigerating machine oil include ditridecyl glutarate, di (2-ethylhexyl) adipate, diisodecyl adipate, ditridecyl adipate, di (3-ethylhexyl) sebacate and the like.

(Polyol ester refrigerating machine oil)
The polyol ester type refrigerating machine oil is an ester synthesized from a polyhydric alcohol and a fatty acid (carboxylic acid).

  Examples of the polyhydric alcohol constituting the polyol ester refrigerating machine oil include diols (ethylene glycol, 1,3-propanediol, propylene glycol, 1,4-butanediol, 1,2-butanediol, 2-methyl-1,3. -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, 1,12-dodecanediol, etc.), polyol having 3 to 20 hydroxyl groups (trimethylol eta) , Trimethylolpropane, trimethylolbutane, di- (trimethylolpropane), tri- (trimethylolpropane), pentaerythritol, di- (pentaerythritol), tri- (pentaerythritol), glycerol, polyglycerol (glycerin 2 -Trimer), 1,3,5-pentanetriol, sorbitol, sorbitan, sorbitol glycerin condensate, polyhydric alcohols such as adonitol, arabitol, xylitol, mannitol, xylose, arabinose, ribose, rhamnose, glucose, fructose, galactose , Sugars such as mannose, sorbose, cellobiose, maltose, isomaltose, trehalose, sucrose, raffinose, gentianose, merentoose, etc. Partially etherified products and the like). Examples of the polyhydric alcohol constituting the ester may be a one of the above, it may contain two or more kinds.

  The fatty acid constituting the polyol ester type refrigerating machine oil is not particularly limited, but those having 1 to 24 carbon atoms are usually used. Straight chain fatty acids and branched fatty acids are preferred. Linear fatty acids include 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 acid, hexadecanoic acid , Heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, oleic acid, linoleic acid, linolenic acid, etc., and the hydrocarbon group bonded to the carboxy group may be all saturated hydrocarbons or unsaturated hydrocarbons You may have. Furthermore, as the branched fatty acid, 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-dimethylpentanoic acid, 2,3-dimethylpentanoic acid, 2,4-dimethylpentanoic acid, 3,3-dimethylpentanoic acid, 3,4-dimethylpentanoic acid, 4,4-dimethylpentanoic acid, 2-ethyl Pentanoic acid, 3-ethylpentanoic acid, 2,2,3-trimethylbutanoic acid, 2,3,3-trimethylbutanoic acid, 2-ethyl-2-methylbutanoic acid, -Ethyl-3-methylbutanoic acid, 2-methylheptanoic acid, 3-methylheptanoic acid, 4-methylheptanoic acid, 5-methylheptanoic acid, 6-methylheptanoic acid, 2-ethylhexanoic acid, 3-ethylhexanoic acid, 4-ethylhexanoic 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-dimethylhepta Acid, 2,3-dimethylheptanoic acid, 2,4-dimethylheptanoic acid, 2,5-dimethylheptanoic acid, 2,6-dimethylheptanoic acid, 3,3-dimethylheptanoic acid, 3,4-dimethylheptanoic acid, 3,5-dimethylheptanoic acid, 3,6-dimethylheptanoic acid, 4,4-dimethylheptanoic acid, 4,5-dimethylheptanoic acid, 4,6-dimethylheptanoic acid, 5,5-dimethylheptanoic acid, 5, 6-dimethylheptanoic acid, 6,6-dimethylheptanoic acid, 2-methyl-2-ethylhexanoic acid, 2-methyl-3-ethylhexanoic acid, 2-methyl-4-ethylhexanoic acid, 3-methyl-2- Ethylhexanoic 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-methyl Octanoic acid, 3,5,5-trimethylhexanoic acid, 2-ethyl-2,3,3-trimethylbutyric acid, 2,2,4,4-tetramethylpentanoic acid, 2,2,3,3-tetramethylpentane Examples include acid, 2,2,3,4-tetramethylpentanoic acid, 2,2-diisopropylpropanoic acid and the like. The fatty acid may be an ester with one or more fatty acids selected from these.

  The polyol constituting the ester may be one kind or a mixture of two or more kinds. The fatty acid constituting the ester may be a single component or an ester with two or more fatty acids. Each of the fatty acid and the fatty acid may be one kind or a mixture of two or more kinds. The polyol ester refrigerating machine oil may have a free hydroxyl group.

Especially, as a particularly preferable polyol ester type refrigerating machine oil, the following compounds (a) to (c):
(A) a compound having two or more hydroxyl groups or a derivative thereof,
(B) a compound having two or more carboxy groups or a derivative thereof; and (c) a compound having one carboxy group or a derivative thereof; and / or a compound having one hydroxyl group or a derivative thereof;
Which is characterized in that it is used together with a working medium containing the unsaturated fluorinated hydrocarbon compound (I), and has lubricity, sealing properties, thermal / chemical stability, The electric insulation is satisfactorily satisfied in a well-balanced manner, and it is possible to sufficiently prevent poor lubrication of the compressor and a decrease in refrigeration efficiency.

  Specific examples of the compound (a) include polyhydric alcohols, polyhydric phenols, polyhydric amino alcohols and condensates thereof, and compounds in which the hydroxyl groups of these compounds are esterified with a carboxylic acid such as acetic acid. Among them, it is preferable to use a polyhydric alcohol or a condensate thereof or a derivative thereof because electric insulation and thermal stability tend to be further improved.

  Further, as the compound (a), a compound in which a hydroxyl group is esterified with a carboxylic acid can be used. As such a derivative, a compound in which a hydroxyl group is esterified with a lower carboxylic acid is preferable, and specifically, an acetate or propionate of a polyhydric alcohol is preferably used.

  The compound (b) constituting the ester is a compound having two or more carboxy groups or a derivative thereof. Specific examples of the compound (b) include carboxylic acids having a valence of 2 or more, and carboxylic acid derivatives such as acid anhydrides, esters, and acid halides thereof.

  The compound (c) constituting the ester is a compound having one carboxy group or a derivative thereof and / or a compound having one hydroxyl group or a derivative thereof. As this compound (c), any one of a compound having one carboxy group or a derivative thereof and a compound having one hydroxyl group or a derivative thereof may be used alone or as a mixture of both. Good. If only a compound having two or more carboxy groups or its derivative is used as the acid component and only a compound having two or more hydroxyl groups or its derivative is used as the alcohol component, the thermal / chemical stability is poor. It will be enough.

  Specific examples of the compound having one carboxy group or a derivative thereof include monovalent fatty acids and acid anhydrides, esters and acid halides thereof. The number of carbon atoms of the monovalent fatty acid is not particularly limited.

  The monovalent fatty acid as the compound (c) may be either linear or branched, but is preferably a linear monovalent fatty acid from the viewpoint of lubricity, and has heat and hydrolysis stability. From this point, a branched monovalent fatty acid is preferable. The monovalent fatty acid may be either a saturated fatty acid or an unsaturated fatty acid.

  Further, as the compound having one hydroxyl group or a derivative thereof, specifically, monohydric alcohol, monohydric phenol, monovalent amino alcohol, and the hydroxyl group of these compounds are esterified with carboxylic acid such as acetic acid. Compounds and the like. The number of carbon atoms in these compounds is not particularly limited.

  In addition, as the compound (c), a derivative in which a hydroxyl group is esterified with a carboxylic acid can also be used. As such derivatives, acetates, propionates and the like of the compounds exemplified in the description of the monohydric alcohol are preferably used.

  The ester described here is esterified by heating the compounds (a) to (c) according to a conventional method, preferably in an inert gas atmosphere such as nitrogen, in the presence of an esterification catalyst or in the absence of a catalyst. It is prepared by.

  In addition, when an alcohol acetate or propionate is used as the compound (a) or (c), or when a lower alcohol ester or the like of a carboxylic acid is used as the compound (b) or (c), a transesterification reaction is performed. It is possible to obtain this ester.

  Specific examples of esterification used in the above esterification reaction include Lewis acids such as aluminum derivatives, tin derivatives and titanium derivatives; alkali metal salts such as sodium alkoxide and potassium alkoxide; paratoluenesulfonic acid and methanesulfonic acid And sulfonic acids such as sulfuric acid are exemplified, but among these, use of Lewis acids such as aluminum derivatives, tin derivatives and titanium derivatives is preferable because the thermal and hydrolytic stability of the resulting ester is further enhanced. Furthermore, tin derivatives are particularly preferable from the viewpoint of reaction efficiency. The usage-amount of said esterification catalyst is about 0.1-1 mass% with respect to the total amount of compound (a)-(c) which is a raw material, for example.

  As reaction temperature in said esterification reaction, 150-230 degreeC is illustrated, and reaction is normally completed in 3 to 30 hours.

  In addition, after the esterification reaction is completed, excess raw materials are distilled off under reduced pressure or normal pressure, followed by a conventional purification method, for example, liquid purification, vacuum distillation, activated purification treatment such as activated carbon treatment, etc. The ester can be purified.

(Complex ester type refrigerating machine oil)
The complex ester refrigerating machine oil is an ester of a fatty acid and a dibasic acid, a monohydric alcohol and a polyol. As the fatty acid, dibasic acid, monohydric alcohol, and polyol, the same ones as described above can be used.

As fatty acid, what was shown with the fatty acid of the said polyol ester is mentioned.
Examples of the dibasic acid include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid and the like.

  Examples of the polyol include those shown as the polyhydric alcohol of the polyol ester. Complex esters are esters of these fatty acids, dibasic acids, and polyols, and each may be a single component or an ester composed of a plurality of components.

(Polyol carbonate refrigerating machine oil)
The polyol carbonate type refrigerating machine oil is an ester of carbonic acid and polyol.
Polyols include polyglycols (polyalkylene glycols, ether compounds thereof, modified compounds thereof, etc.) obtained by homopolymerization or copolymerization of diols (same as above), polyols (same as above), polyols and polyglycols. And the like added.

  As polyalkylene glycol, what was obtained by the method etc. which superpose | polymerize C2-C4 alkylene oxide (ethylene oxide, propylene oxide, etc.) using water or alkali hydroxide as an initiator is mentioned. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used. The oxyalkylene units in the polyalkylene glycol may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule. The polyol carbonate refrigerating machine oil may be a ring-opening polymer of cyclic alkylene carbonate.

[Ether refrigeration oil]
Examples of ether refrigerating machine oil include polyvinyl ether refrigerating machine oil and polyalkylene glycol refrigerating machine oil.

(Polyvinyl ether refrigerating machine oil)
Polyvinyl ether refrigerating machine oils obtained by polymerizing vinyl ether monomers, those obtained by copolymerizing vinyl ether monomers and hydrocarbon monomers having an olefinic double bond, and polyvinyl ether and alkylene glycol Or there are polyalkylene glycols or their copolymers with monoethers.

  Preferable examples of the polyvinyl ether refrigerating machine oil include polyvinyl ether compounds having a structure represented by the following general formula (1) and having a molecular weight of 300 to 3,000.

(In the formula ^{(1), R 1, R} 2 and ^{R 3} each represent a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms, they may be the same or different, ^{R b} is a carbon number from 2 to 4 A divalent hydrocarbon group, R ^a is a hydrogen atom, an aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms, an aromatic group optionally having a substituent having 1 to 20 carbon atoms, carbon An acyl group having 2 to 20 carbon atoms or an oxygen-containing hydrocarbon group having 2 to 50 carbon atoms, R ⁴ represents a hydrocarbon group having 1 to 10 carbon atoms, and R ^a , R ^b , and R ⁴ are a plurality of them. May be the same or different, m is an average value of 1 to 50, o is a number of 1 to 50, p is a number of 0 to 50, and o and p are a plurality when they are plural Each block may be random.)

Here, the hydrocarbon group having 1 to 8 carbon atoms of R ^{1 to} R ³ is specifically a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec. -Butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups and other alkyl groups, cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various dimethylcyclohexyl groups, etc. An aryl group such as a cycloalkyl group, a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, and the like, and an arylalkyl group such as a benzyl group, various phenylethyl groups, and various methylbenzyl groups. In addition, as each of these R < ¹ >, R < ² > and R < ³ >, a hydrogen atom is especially preferable.

On the other hand, examples of the divalent hydrocarbon group having 2 to 4 carbon atoms represented by R ^b include divalent alkylene groups such as a methylene group, an ethylene group, a propylene group, a trimethylene group, and various butylene groups. .
Incidentally, m in the general formula (1) represents the number of repetitions of ^{R b} O, the average value thereof is 1 to 50, preferably 2 to 20, more preferably 2 to 10, particularly preferably from 2 to 5 Is a number. When R b ^O is plural, plural R ^{b O} may be the same or different.
O is 1 to 50, preferably 1 to 10, more preferably 1 to 2, particularly preferably 1, and p is 0 to 50, preferably 2 to 25, more preferably 5 to 15, And p may be either block or random when there are a plurality of them.

Among R ^a , the aliphatic or alicyclic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 10 carbon atoms or a cycloalkyl group having 5 to 10 carbon atoms, specifically Is methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various Nonyl group, various decyl groups, cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various dimethylcyclohexyl groups, and the like.

Specific examples of the aromatic group that may have a substituent having 1 to 20 carbon atoms in ^Ra include a phenyl group, various tolyl groups, various ethylphenyl groups, various xylyl groups, and various trimethylphenyl groups. Aryl groups such as various butylphenyl groups and various naphthyl groups, arylalkyl groups such as benzyl group, various phenylethyl groups, various methylbenzyl groups, various phenylpropyl groups, various phenylbutyl groups, and the like.

Examples of the acyl group having 2 to 20 carbon atoms in ^Ra include acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, benzoyl group, and toluoyl group.
Further, specific examples of the oxygen-containing hydrocarbon group having 2 to 50 carbon atoms in R ^a include methoxymethyl group, methoxyethyl group, methoxypropyl group, 1,1-bismethoxypropyl group, 1,2-bismethoxy group. Preferable examples include propyl group, ethoxypropyl group, (2-methoxyethoxy) propyl group, (1-methyl-2-methoxy) propyl group and the like.

In the general formula (1), the hydrocarbon group having 1 to 10 carbon atoms represented by R ⁴ specifically includes a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group. Various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, various alkyl groups such as decyl, cyclopentyl group, cyclohexyl group, various methylcyclohexyl groups, various ethylcyclohexyl groups, various propylcyclohexyl groups, various Aryl groups such as cycloalkyl groups such as dimethylcyclohexyl group, phenyl groups, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups, various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, various naphthyl groups, Benzyl group, various phenylethyl groups, various methylbennes An arylalkyl group such as a dil group, various phenylpropyl groups, and various phenylbutyl groups is shown.
R ^{1 to} R ³ , R ^a , R ^b and m and R ^{1 to} R ⁴ may be the same or different for each structural unit.

  The polyvinyl ether compound is obtained, for example, by polymerizing a vinyl ether compound represented by the following general formula (3) using an alkylene glycol compound or a polyoxyalkylene glycol compound represented by the following general formula (2) as an initiator. be able to.

上記式において、Ｒ^ａ、Ｒ^ｂ、ｍおよびＲ^１〜Ｒ^４は前記で説明した通りである。

In the above formula, R ^a , R ^b , m and R ^{1 to} R ⁴ are as described above.

  Specific alkylene glycol compounds and polyoxyalkylene glycol compounds include ethylene glycol, ethylene glycol monomethyl ether, diethylene glycol, diethylene glycol monomethyl ether, triethylene glycol, triethylene glycol monomethyl ether, propylene glycol, propylene glycol monomethyl ether, dipropylene glycol. , Alkylene glycols such as dipropylene glycol monomethyl ether, tripropylene glycol and tripropylene glycol monomethyl ether, polyoxyalkylene glycols and monoether compounds thereof.

  On the other hand, examples of the vinyl ether compound represented by the general formula (3) include vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n butyl ether, vinyl isobutyl ether, vinyl. Vinyl ethers such as -sec-butyl ether, vinyl-tert-butyl ether, vinyl-n-pentyl ether, vinyl-n-hexyl ether; 1-methoxypropene, 1-ethoxypropene, 1-n-propoxypropene, 1-isopropoxy Propene, 1-n-butoxypropene, 1-isobutoxypropene, 1-sec-butoxypropene, 1-tert-butoxypropene, 2-methoxypropene, 2-ethoxypropene, 2-n-propoxypropene, 2-iso Propene such as lopoxypropene, 2-n-butoxypropene, 2-isobutoxypropene, 2-sec-butoxypropene, 2-tert-butoxypropene; 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, -Ethoxy-2-butene, 2-n-propoxy-2-butene, 2-isopropoxy-2-butene, 2-n-butoxy-2-butene, 2-isobutoxy-2-butene, 2-sec-butoxy- Examples include butenes such as 2-butene and 2-tert-butoxy-2-butene. These vinyl ether monomers can be produced by known methods.

  The vinyl ether compound can be produced by polymerizing the corresponding vinyl ether compound and a hydrocarbon monomer having an olefinic double bond, which is optionally used, by radical polymerization, cationic polymerization, radiation polymerization or the like. For example, a vinyl ether monomer can be polymerized using the method shown below to obtain a polymer having a desired viscosity. For the initiation of polymerization, a combination of Bronsted acids, Lewis acids or organometallic compounds with an adduct of water, alcohols, phenols, acetals or vinyl ethers and a carboxylic acid may be used. it can. Examples of Bronsted acids include hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, nitric acid, sulfuric acid, trichloroacetic acid, trifluoroacetic acid and the like. Examples of Lewis acids include boron trifluoride, aluminum trichloride, aluminum tribromide, tin tetrachloride, zinc dichloride, and ferric chloride. Among these Lewis acids, boron trifluoride is particularly preferred. Is preferred. Examples of the organometallic compound include diethyl aluminum chloride, ethyl aluminum chloride, diethyl zinc and the like.

  Any adduct of water, alcohols, phenols, acetals or vinyl ethers and a carboxylic acid in combination with these can be selected. Here, examples of the alcohols include those having 1 to 20 carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, various pentanols, various hexanols, various heptanols, and various octanols. C3-C10 unsaturated aliphatic alcohols such as saturated aliphatic alcohols and allyl alcohols, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, tripropylene glycol Examples thereof include monoethers of alkylene glycols such as monomethyl ether. Examples of the carboxylic acid in the case of using an adduct of vinyl ethers and carboxylic acid include 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 acid, 2-n -Propylvaleric acid, n-nonanoic acid, 3,5,5-trimethylcaproic acid, caprylic acid, undecanoic acid and the like.

In addition, the vinyl ether used in the case of using an adduct of vinyl ether and carboxylic acid may be the same as that used for the polymerization, or may be different. This adduct of vinyl ethers and the carboxylic acid is obtained by mixing and reacting at a temperature of about 0 to 100 ° C., and can be separated by distillation or the like and used for the reaction, but separated as it is. It can also be used for the reaction without.
The polymerization initiation terminal of the polymer is such that when water, alcohols or phenols are used, hydrogen is bonded, and when acetals are used, one alkoxy group is eliminated from hydrogen or the used acetals. When an adduct of vinyl ethers and carboxylic acid is used, the alkylcarbonyloxy group derived from the carboxylic acid moiety is eliminated from the adduct of vinyl ethers and carboxylic acid.

  On the other hand, when water, alcohols, phenols, or acetals are used, the terminal ends are acetals, olefins, or aldehydes. In the case of an adduct of vinyl ethers and carboxylic acid, it becomes a carboxylic acid ester of hemiacetal. The terminal of the polymer thus obtained can be converted into a desired group by a known method. Examples of the desired group include residues of saturated hydrocarbons, ethers, alcohols, ketones, nitriles, amides and the like, but saturated hydrocarbon, ether and alcohol residues are preferable.

  The polyvinyl ether compound can adjust the compatibility with the working medium containing the unsaturated fluorinated hydrocarbon compound (I) by adjusting the carbon / oxygen molar ratio. In the present invention, by adjusting the carbon / oxygen molar ratio, a polyvinyl ether compound that achieves the incompatible characteristics of (O-3) is obtained. About adjustment of this molar ratio, the polymer which has this molar ratio in the said range can be manufactured by adjusting carbon / oxygen molar ratio of a raw material monomer. That is, if the ratio of the monomer having a large carbon / oxygen molar ratio is large, a polymer having a large carbon / oxygen molar ratio is obtained, and if the ratio of the monomer having a small carbon / oxygen molar ratio is large, the polymer having a small carbon / oxygen molar ratio is obtained. Is obtained.

  The adjustment of the carbon / oxygen molar ratio is carried out by using water, alcohols, phenols, acetals, and adducts of vinyl ethers and carboxylic acids used as initiators as shown in the polymerization method of vinyl ether monomers. The combination with monomers is also possible. If alcohols or phenols having a larger carbon / oxygen molar ratio than the monomer to be polymerized are used as initiators, a polymer having a larger carbon / oxygen molar ratio than the raw material monomer can be obtained, while carbon / such as methanol or methoxyethanol can be obtained. If an alcohol having a small oxygen molar ratio is used, a polymer having a carbon / oxygen molar ratio smaller than that of the raw material monomer can be obtained.

  Furthermore, when a vinyl ether monomer and a hydrocarbon monomer having an olefinic double bond are copolymerized, a polymer having a carbon / oxygen molar ratio larger than the carbon / oxygen molar ratio of the vinyl ether monomer is obtained. Can be adjusted by the ratio of the hydrocarbon monomer having an olefinic double bond to be used and the number of carbon atoms.

(Polyalkylene glycol refrigerating machine oil)
Examples of the polyalkylene glycol refrigerating machine oil include those obtained by a method of polymerizing alkylene oxide having 2 to 4 carbon atoms (ethylene oxide, propylene oxide, etc.) using water or alkali hydroxide as an initiator. Moreover, what etherified the hydroxyl group of polyalkylene glycol may be used. The oxyalkylene units in the polyalkylene glycol refrigerating machine oil may be the same in one molecule, or two or more oxyalkylene units may be included. It is preferable that at least an oxypropylene unit is contained in one molecule.

Specific examples of the polyoxyalkylene glycol refrigerating machine oil include compounds represented by the following general formula (4).
R ¹⁰¹ -[(OR ¹⁰² ) _k -OR ¹⁰³ ] _l (4)
(In the formula, R ¹⁰¹ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an acyl group having 2 to 10 carbon atoms, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding parts, R ¹⁰² Is an alkylene group having 2 to 4 carbon atoms, R ¹⁰³ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms or an acyl group having 2 to 10 carbon atoms, l is an integer of 1 to 6, and k is an average value of k × l Indicates a number from 6 to 80.)

In the general formula (4), the alkyl group in R ¹⁰¹ and R ¹⁰³ may be linear, branched or cyclic. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, various nonyl groups, and various decyl groups. , Cyclopentyl group, cyclohexyl group and the like.

Further, the alkyl group portion of the acyl group in R ¹⁰¹ and R ¹⁰³ may be linear, branched or cyclic. As specific examples of the alkyl group portion of the acyl group, various groups having 1 to 9 carbon atoms exemplified as specific examples of the alkyl group can be exemplified.

When R ¹⁰¹ and R ¹⁰³ are both alkyl groups or acyl groups, R ¹⁰¹ and R ¹⁰³ may be the same or different from each other.
Further, when l is 2 or more, a plurality of R ^{103 in} one molecule may be the same or different.

When R ¹⁰¹ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms having 2 to 6 bonding sites, the aliphatic hydrocarbon group may be chain-like or cyclic. Also good. Examples of the aliphatic hydrocarbon group having two binding sites include ethylene group, propylene group, butylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, cyclopentylene group, and cyclohexylene. Groups and the like. Examples of the aliphatic hydrocarbon group having 3 to 6 binding sites include trimethylolpropane, glycerin, pentaerythritol, sorbitol; 1,2,3-trihydroxycyclohexane; 1,3,5-trihydroxycyclohexane. Examples thereof include residues obtained by removing hydroxyl groups from polyhydric alcohols such as

R ^<102 > in the said General formula (4) is a C2-C4 alkylene group, and an oxyethylene group, an oxypropylene group, and an oxybutylene group are mentioned as an oxyalkylene group of a repeating unit. The oxyalkylene groups in one molecule may be the same or two or more oxyalkylene groups may be contained, but those containing at least an oxypropylene unit in one molecule are preferred, and in particular, oxyalkylene units. Those containing 50 mol% or more of oxypropylene units are preferred.

In the general formula (4), l is an integer of 1 to 6, and is determined according to the number of R ¹⁰¹ binding sites. For example, when R ¹⁰¹ is an alkyl group or an acyl group, l is 1, and when R ¹⁰¹ is an aliphatic hydrocarbon group having 2, 3, 4, 5 and 6 binding sites, l is 2, 3 respectively. 4, 5 and 6. In addition, k is a number where the average value of k × l is 6 to 80. If the average value of k × l deviates from the above range, the object of the present invention may not be sufficiently achieved.

  The structure of the polyalkylene glycol is preferably a polypropylene glycol dimethyl ether represented by the following general formula (5) and a polyethylene polypropylene glycol dimethyl ether represented by the following general formula (6) in terms of economy and the above-mentioned effects. Also, polypropylene glycol monobutyl ether represented by the following general formula (7), further polypropylene glycol monomethyl ether represented by the following general formula (8), polyethylene polypropylene glycol monomethyl ether represented by the following general formula (9), Polyethylene polypropylene glycol monobutyl ether represented by the following general formula (10) and polypropylene glycol diacetate represented by the following general formula (11) are preferable in terms of economy and the like.

_{CH 3 O- (C 3 H 6} O) h -CH 3 ... (5)
(In the formula, h represents a number of 6 to 80.)
_{CH 3 O- (C 2 H 4} O) i - (C 3 H 6 O) j -CH 3 ... (6)
(In the formula, i and j are each 1 or more, and the total of i and j is 6 to 80.)
_{C 4 H 9 O- (C 3} H 6 O) h -H ... (7)
(In the formula, h represents a number of 6 to 80.)
_{CH 3 O- (C 3 H 6} O) h -H ... (8)
(In the formula, h represents a number of 6 to 80.)

_{CH 3 O- (C 2 H 4} O) i - (C 3 H 6 O) j -H ... (9)
(In the formula, i and j are each 1 or more, and the total of i and j is 6 to 80.)
_{C 4 H 9 O- (C 2} H 4 O) i - (C 3 H 6 O) j -H ... (10)
(In the formula, i and j are each 1 or more, and the total of i and j is 6 to 80.)
_{CH 3 COO- (C 3 H 6} O) h -COCH 3 ... (11)
(In the formula, h represents a number of 6 to 80.)
These polyoxyalkylene glycols may be used individually by 1 type, and may be used in combination of 2 or more type.

<Hydrocarbon refrigeration oil>
Alkylbenzene can be used as the hydrocarbon refrigerating machine oil.

  As the alkyl benzene, branched alkyl benzene synthesized using propylene polymer and benzene as raw materials using a catalyst such as hydrogen fluoride, and linear alkyl benzene synthesized using normal paraffin and benzene as raw materials using the same catalyst can be used. . The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 4 to 20, from the viewpoint of obtaining a viscosity suitable as a lubricating base oil. Further, the number of alkyl groups in one molecule of alkylbenzene is preferably 1 to 4, more preferably 1 to 3, in order to keep the viscosity within a set range although it depends on the number of carbon atoms of the alkyl group.

  These refrigeration oils may be used alone or in combination of two or more. These refrigerating machine oils are preferably mixed with a working medium and used as a composition for a heat cycle system. At this time, the blending ratio of the refrigerating machine oil is desirably 5 to 60% by mass, and more preferably 10 to 50% by mass with respect to the total amount of the composition for a heat cycle system.

<Other optional components>
In addition, the composition for thermal cycle systems can contain known optional components as long as the effects of the present invention are not impaired. As this optional component, for example, an additive for stably containing a refrigerating machine oil in the composition for a heat cycle system, such an additive includes a copper deactivator, an extreme pressure agent, an oily agent, Antioxidants, acid scavengers, antifoaming agents, polymerization inhibitors, drying agents and the like can be mentioned. Each additive may be added as necessary, and the blending amount of each additive is set to be, for example, 0.01% by mass or more and 5% by mass or less in 100% by mass of the composition for a heat cycle system. do it. In addition, the compounding amount of the acid scavenger and the compounding amount of the antioxidant are preferably in the range of 0.05% by mass or more and 5% by mass or less.

  Moreover, as a copper deactivator, benzotriazole, its derivative, etc. can be used. As the antifoaming agent, a silicon compound can be used. As the oily agent, higher alcohols can be used.

  In addition, what contains phosphate ester can be used for an extreme pressure agent. Examples of phosphoric acid esters that can be used include phosphoric acid esters, phosphorous acid esters, acidic phosphoric acid esters, and acidic phosphorous acid esters. Moreover, what contains the amine salt of phosphoric acid ester, phosphorous acid ester, acidic phosphoric acid ester, and acidic phosphorous acid ester can also be used for an extreme pressure agent.

  Phosphate esters include triaryl phosphates, trialkyl phosphates, trialkylaryl phosphates, triarylalkyl phosphates, trialkenyl phosphates, and the like. Further, phosphoric acid esters are specifically listed as triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate. , Diethylphenylphenyl phosphate, propylphenyldiphenyl phosphate, dipropylphenylphenyl phosphate, triethylphenyl phosphate, tripropylphenyl phosphate, butylphenyl diphenyl phosphate, dibutylphenylphenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) Hosphee There tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tri palmityl phosphate, tristearyl phosphate, and trioleyl phosphate and the like.

  Specific examples of phosphites include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, tridecyl. There are phosphites, trilauryl phosphites, triisooctyl phosphites, diphenylisodecyl phosphites, tristearyl phosphites, trioleyl phosphites and the like.

  Specific examples of the acidic phosphate ester include 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, Examples include stearyl acid phosphate and isostearyl acid phosphate.

  Specific examples of the acidic phosphite include dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, diphenyl hydrogen phosphite and the like. Among the above phosphoric acid esters, oleyl acid phosphate and stearyl acid phosphate are preferred.

  Specific examples of mono-substituted amines among the amines used in the amine salts of phosphoric acid ester, phosphorous acid ester, acidic phosphoric acid ester or acidic phosphorous acid ester include butylamine, pentylamine, hexylamine, cyclohexylamine, There are octylamine, laurylamine, stearylamine, oleylamine, benzylamine and the like. Specific examples of disubstituted amines include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanol. Examples include ethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanol. Specific examples of the tri-substituted amine include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, Dilauryl monopropanolamine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl Diethanolamine, phenyl diethanolamine, tolyl dipropanolamine, xylyl diethanolamine Emissions, triethanolamine, there is a tri-propanolamine and the like.

  It is also possible to add extreme pressure agents other than those described above. For example, extreme pressure agents based on organic sulfur compounds such as monosulfides, polysulfides, sulfoxides, sulfones, thiosulfinates, sulfurized fats and oils, thiocarbonates, thiophenes, thiazoles, methanesulfonate esters, Thiophosphate ester-type extreme pressure agents such as thiophosphate triesters, higher fatty acid, hydroxyaryl fatty acids, polyhydric alcohol esters, ester-type extreme pressure agents such as acrylate esters, chlorinated hydrocarbons, chlorine Organic chlorinated extreme pressure agents such as fluorinated carboxylic acid derivatives, fluorinated aliphatic carboxylic acids, fluorinated ethylene resins, fluorinated alkylpolysiloxanes, organic fluorinated extreme pressure agents such as fluorinated graphite, higher alcohols, etc. Alcohol-based extreme pressure agents, naphthenates (lead naphthenate, etc.), fatty acid salts (lead fatty acid, etc.), Phosphates (zinc dialkyl dithiophosphate, etc.), thiocarbamic acid salts, organomolybdenum compounds, organotin compounds, organogermanium compounds, it is possible to use extreme pressure metal compound-based, such as boric acid ester.

As the antioxidant, a phenol-based antioxidant or an amine-based antioxidant can be used. The phenolic antioxidants include 2,6-di-tert-butyl-4-methylphenol (DBPC), 2,6-di-tert-butyl-4-ethylphenol, 2,2′-methylenebis (4 -Methyl-6-tert-butylphenol), 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butylphenol and the like. Examples of the amine-based antioxidant include N, N′-diisopropyl-p-phenylenediamine, N, N′-di-sec-butyl-p-phenylenediamine, phenyl-α-naphthylamine, N, N′-. Examples include di-phenyl-p-phenylenediamine. The antioxidant includes an oxygen scavenger that traps oxygen.

  As the acid scavenger, epoxy compounds such as phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, α-olefin oxide, and epoxidized soybean oil can be used. Among these, preferred acid scavengers from the viewpoint of compatibility are phenyl glycidyl ether, alkyl glycidyl ether, alkylene glycol glycidyl ether, cyclohexene oxide, and α-olefin oxide. The alkyl group of the alkyl glycidyl ether and the alkylene group of the alkylene glycol glycidyl ether may have a branch. These carbon numbers should just be 3 or more and 30 or less, more preferably 4 or more and 24 or less, and still more preferably 6 or more and 16 or less. The α-olefin oxide may have a total carbon number of 4 or more and 50 or less, more preferably 4 or more and 24 or less, and even more preferably 6 or more and 16 or less. Only one type of acid scavenger may be used, or a plurality of types may be used in combination.

  In addition, polymerization inhibitors such as 4-methoxy-1-naphthol, hydroquinone, hydroquinone methyl ether, dimethyl-tert-butylphenol, 2,6-di-tert-butyl-p-cresol, and benzotriazole are used as the polymerization inhibitor. Can be used.

  In addition, the composition for a thermal cycle system of the present embodiment includes, as necessary, a load-bearing additive, a chlorine scavenger, a cleaning dispersant, a viscosity index improver, a rust inhibitor, a stabilizer, a corrosion inhibitor, and a flow. It is also possible to add a point depressant or the like. The compounding amount of each additive may be, for example, 0.01% by mass or more and 5% by mass or less, and 0.05% by mass or more and 2% by mass or less in 100% by mass of the composition for a heat cycle system. Is preferred.

  Furthermore, as an optional component to be blended in the composition for a thermal cycle system, for example, a leak detection substance can be mentioned, and as this optional leak detection substance, an ultraviolet fluorescent dye, an odor gas, an odor masking agent, etc. can be mentioned. .

  The ultraviolet fluorescent dye was described in U.S. Pat. No. 4,249,412, JP-T-10-502737, JP-T 2007-511645, JP-T 2008-500437, JP-T 2008-531836. Conventionally known ultraviolet fluorescent dyes used in thermal cycle systems together with working media composed of halogenated hydrocarbons, and the like.

  As the odor masking agent, conventionally known fragrances used in thermal cycle systems, together with working media made of halogenated hydrocarbons, such as those described in JP-T-2008-500337 and JP-T-2008-531836, are known. Can be mentioned.

  In the case of using a leak detection substance, a solubilizing agent that improves the solubility of the leak detection substance in the working medium may be used.

  Examples of the solubilizer include those described in JP-T-2007-511645, JP-T-2008-500437, JP-T-2008-531836.

  The content of the leak detection substance in the composition for a heat cycle system may be in a range that does not significantly reduce the effect of the present invention, and is preferably 2 parts by mass or less, based on 100 parts by mass of the working medium, and 0.5 mass. Part or less is more preferable.

[Thermal cycle system]
The thermal cycle system of the present invention is a system using the composition for a thermal cycle system of the present invention. The heat cycle system of the present invention may be a heat pump system that uses warm heat obtained by a condenser, or may be a refrigeration cycle system that uses cold heat obtained by an evaporator.

  Specific examples of the heat cycle system of the present invention include refrigeration / refrigeration equipment, air conditioning equipment, power generation systems, heat transport devices, and secondary coolers. Especially, since the thermal cycle system of the present invention can exhibit thermal cycle performance efficiently even in a higher temperature operating environment, it is preferably used as an air conditioner that is often installed outdoors. The thermal cycle system of the present invention is also preferably used as a refrigeration / refrigeration apparatus.

Specific examples of air conditioners include room air conditioners, packaged air conditioners (store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, etc.), gas engine heat pumps, train air conditioners, automobile air conditioners, and the like.
Specific examples of the refrigeration / refrigeration equipment include showcases (built-in showcases, separate showcases, etc.), commercial freezers / refrigerators, vending machines, ice makers, and the like.

As the power generation system, a power generation system using a Rankine cycle system is preferable.
Specifically, as a power generation system, the working medium is heated in the evaporator by geothermal energy, solar heat, medium to high temperature waste heat of about 50 to 200 ° C, etc., and the working medium that has become high-temperature and high-pressure steam is expanded. An example is a system in which power is generated by adiabatic expansion by a machine, and a generator is driven by work generated by the adiabatic expansion.

The heat cycle system of the present invention may be a heat transport device. As the heat transport device, a latent heat transport device is preferable.
Examples of the latent heat transport device include a heat pipe and a two-phase sealed thermosyphon device that transport latent heat using phenomena such as evaporation, boiling, and condensation of a working medium enclosed in the device. The heat pipe is applied to a relatively small cooling device such as a cooling device for a heat generating part of a semiconductor element or an electronic device. Since the two-phase sealed thermosyphon does not require a wig and has a simple structure, the two-phase sealed thermosyphon is widely used for a gas-gas heat exchanger, for promoting snow melting on roads, and for preventing freezing.

  According to the thermal cycle system of the present invention using the composition for thermal cycle system of the present invention, for example, in the refrigeration cycle system 10 shown in FIG. Compared to the case of using (a mixture of HFC-32 and HFC-125 at a mass ratio of 1: 1), both the Q and COP are at a high level, that is, equivalent to R410A, while keeping the global warming potential much lower. It is possible to set a level higher than that.

  Furthermore, it is possible to make the composition suppress the temperature gradient of the working medium containing the unsaturated fluorinated hydrocarbon compound (I) contained in the composition for the heat cycle system to be used, in that case, from the pressure vessel. It is possible to suppress the change in the composition of the refrigerant in the refrigerating and air-conditioning equipment when the composition changes when being charged into the refrigerating and air-conditioning equipment and the refrigerant leakage from the refrigerating and air-conditioning equipment.

  Moreover, according to the composition for thermal cycle systems of the present invention, the refrigerating machine oil having the characteristics (O-1) to (O-3) is contained together with the working medium containing the unsaturated fluorinated hydrocarbon compound (I). By doing so, there is almost no decrease in viscosity in the compressor, and since it always has sufficient sliding strength, it is possible to increase the reliability of the sliding portion, and therefore the thermal cycle system using the composition is A more efficient circulating state of the working medium can be maintained than before, and the system can be operated stably.

  In the heat cycle system, as described above, the working medium used in the present invention contains the unsaturated fluorinated hydrocarbon compound (I) having a carbon-carbon double bond, so that the system is in operation. The working medium can decompose and generate acid. In the present invention, the refrigerating machine oil used in combination with this working medium is configured to suppress acid generation. However, even when acid is generated for some reason, the heat cycle system can be stably operated. It is preferable that

  That is, it is preferable that the contact part which contacts the said composition for thermal cycle systems is comprised from at least 1 sort (s) chosen from an engineering plastic, an organic film, and an inorganic film | membrane. As this contact part, the sliding part in a compression mechanism, the seal part inside a heat cycle system, etc. are mentioned especially as what should be protected. More specifically, a sliding member (bearing, etc.) provided in the sliding portion of the compressor, a seal member for preventing leakage of the working medium in the gap of the compressor, an insulating material provided in the electric motor, etc. Is mentioned.

  The engineering plastic used here is preferably at least one material selected from polyamide resin, polyphenylene sulfide resin, polyacetal resin, and fluororesin.

  The organic film used here is formed by using a polytetrafluoroethylene coating film, a polyimide coating film, a polyamideimide coating film, or a resin paint containing a resin composed of a polyhydroxy ether resin and a polysulfone resin and a crosslinking agent. Preferably, the material is at least one material selected from thermosetting insulating films.

  The inorganic film used here is preferably at least one material selected from a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, and a molybdenum film.

  When the contact portion is a sliding member, for example, it is preferable to use any of polytetrafluoroethylene, polyphenylene sulfide, and polyamide. When the contact portion is a seal portion, for example, polytetrafluoroethylene, polyphenylene sulfide It is preferably at least one material selected from chloroprene rubber, silicon rubber, hydrogenated nitrile rubber, fluorine rubber, and hydrin rubber.

  Further, as an insulating material for an electric motor, there are an insulating coating material for a winding of a stator, an insulating film, and the like. These insulation coating materials and insulation films are resins that are not physically or chemically modified by the working medium even when they come into contact with a high-temperature / high-pressure working medium, especially solvent resistance, extraction resistance, thermal / chemical Resins having stability and resistance to foaming are used.

  Specifically, any of polyvinyl formal, polyester, THEIC modified polyester, polyamide, polyamide imide, polyester imide, and polyester amide imide is used as an insulating coating material for the stator winding. It is preferable to use a double coated wire in which the upper layer is polyamideimide and the lower layer is polyesterimide. In addition to the above substances, an enamel coating having a glass transition temperature of 120 ° C. or higher may be used.

  As the insulating film, any of polyethylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, and polybutylene terephthalate is used. In addition, it is also possible to use the same foam film as the working medium of the refrigeration cycle for the insulating film. Polyether ether ketone or liquid crystal polymer is used as an insulating material for holding a winding such as an insulator. Epoxy resin is used for the varnish.

  In the heat cycle system in which the contact area between the composition for a heat cycle system and the resin member is increased in this way, there is a concern about the occurrence of problems due to swelling / shrinkage deformation of the resin member due to refrigeration oil. By setting the aniline point of the refrigerating machine oil within a predetermined range as in O-5), such a problem can be dealt with.

  In the operation of the heat cycle system, it is preferable to provide means for suppressing such contamination in order to avoid the occurrence of problems due to the mixing of moisture and non-condensable gases such as oxygen.

  If moisture is mixed into the thermal cycle system, problems may occur particularly when used at low temperatures. For example, there are problems such as freezing in the capillary tube, hydrolysis of the working medium and refrigerating machine oil, material deterioration due to acid components generated in the cycle, and generation of contamination. In particular, when the refrigerating machine oil is a polyglycol-based refrigerating machine oil, a polyol ester-based refrigerating machine oil, etc., the hygroscopic property is extremely high, the hydrolysis reaction is likely to occur, the characteristics as the refrigerating machine oil deteriorates, and the long-term operation of the compressor This is a major cause of loss of reliability. Therefore, in order to suppress hydrolysis of refrigeration oil, it is necessary to control the water concentration in the thermal cycle system.

  Examples of the method for controlling the water concentration in the thermal cycle system include a method using a water removing means such as a desiccant (silica gel, activated alumina, zeolite, etc.). The desiccant is preferably brought into contact with the liquid thermal cycle system composition in terms of dehydration efficiency. For example, it is preferable to place a desiccant at the outlet of the condenser 12 or the inlet of the evaporator 14 to contact the composition for the thermal cycle system.

  As the desiccant, a zeolitic desiccant is preferable from the viewpoint of chemical reactivity between the desiccant and the composition for the heat cycle system and the moisture absorption capacity of the desiccant.

As a zeolitic desiccant, in the case of using a refrigerating machine oil having a high moisture absorption compared to a conventional mineral refrigerating machine oil, the main component is a compound represented by the following formula (C) because it has a high hygroscopic capacity. Zeolite desiccants are preferred.
_{M 2 / n O · Al 2} O 3 · xSiO 2 · yH 2 O ... (C)
However, M is a Group 1 element such as Na or K, or a Group 2 element such as Ca, n is a valence of M, and x and y are values determined by a crystal structure. By changing M, the pore diameter can be adjusted.

In selecting a desiccant, pore diameter and breaking strength are important.
When the working medium or the desiccant having a pore size larger than the molecular diameter of the refrigerating machine oil contained in the composition for the heat cycle system is used, the working medium or the refrigerating machine oil is adsorbed in the desiccant, and as a result, the working medium or A chemical reaction occurs between the refrigerating machine oil and the desiccant, and undesired phenomena such as generation of non-condensable gas, a decrease in the strength of the desiccant, and a decrease in adsorption capacity occur.

  Therefore, it is preferable to use a zeolitic desiccant having a small pore size as the desiccant. In particular, a sodium / potassium A type synthetic zeolite having a pore diameter of 3.5 angstroms or less is preferable. By applying sodium / potassium type A synthetic zeolite having a pore size smaller than the molecular diameter of the working medium or refrigerating machine oil, only the water in the heat cycle system is selectively absorbed without adsorbing the working medium or refrigerating machine oil. Can be removed by adsorption. In other words, the adsorption of the working medium and the refrigerating machine oil to the desiccant is unlikely to occur, so that the thermal decomposition is difficult to occur. As a result, it is possible to suppress the deterioration of the materials constituting the thermal cycle system and the occurrence of contamination.

  If the size of the zeolitic desiccant is too small, it will cause clogging of the valves and piping details of the heat cycle system, and if it is too large, the drying ability will be reduced, so about 0.5 to 5 mm is preferable. The shape is preferably granular or cylindrical.

The zeolitic desiccant can be formed into an arbitrary shape by solidifying powdery zeolite with a binder (such as bentonite). Other desiccants (silica gel, activated alumina, etc.) may be used in combination as long as the zeolitic desiccant is mainly used.
The use ratio of the zeolitic desiccant with respect to the composition for a heat cycle system is not particularly limited.

  Furthermore, when non-condensable gas is mixed in the heat cycle system, it adversely affects heat transfer in the condenser and the evaporator and increases in operating pressure. Therefore, it is necessary to suppress mixing as much as possible. In particular, oxygen, which is one of non-condensable gases, reacts with the working medium and refrigerating machine oil to promote decomposition.

  The non-condensable gas concentration is preferably 1.5% by volume or less, particularly preferably 0.5% by volume or less in terms of the volume ratio with respect to the working medium in the gas phase part of the working medium.

  In the thermal cycle system of the present invention described above, by using the composition for the thermal cycle system of the present invention, the lubrication characteristics are good, and the practically sufficient cycle performance is suppressed while suppressing the influence on global warming. Is obtained, and there is almost no problem with the temperature gradient.

  The composition for a heat cycle system of the present invention and the heat cycle system using the composition are refrigeration / refrigeration equipment (built-in showcase, separate-type showcase, commercial refrigeration / refrigerator, vending machine, ice maker, etc.) , Air conditioners (room air conditioners, store packaged air conditioners, building packaged air conditioners, facility packaged air conditioners, gas engine heat pumps, train air conditioners, automotive air conditioners, etc.), power generation systems (waste heat recovery power generation, etc.), heat transport It can be used for equipment (heat pipe, etc.).

  DESCRIPTION OF SYMBOLS 10 ... Refrigeration cycle system, 11 ... Compressor, 12 ... Condenser, 13 ... Expansion valve, 14 ... Evaporator, 15, 16 ... Pump

Claims (23)

A working fluid for heat cycle comprising at least one unsaturated fluorinated hydrocarbon compound selected from compounds represented by the following general formula (I) and having one or more carbon-carbon unsaturated bonds in the molecule;
The dielectric breakdown voltage is 25 kV or more, the hydroxyl value is 0.1 mgKOH / g or less, and the mixture with the heat cycle working medium is in the entire temperature range from the condensation temperature to the evaporation temperature of the heat cycle working medium. Refrigeration oil in a two-layer separated state;
A composition for a heat cycle system, comprising:
C _x F _y R _z ............ (I)
(In the formula, R is H or Cl, x is an integer of 2 to 6, y is an integer of 1 to 12, z is an integer of 0 to 11, and 2x ≧ y + z ≧ 2.)   The composition for thermal cycle systems according to claim 1, comprising a compound wherein x in the general formula (I) is 2 or 3.   The unsaturated fluorinated hydrocarbon compound is 1,1,2-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 The thermal cycle according to claim 2, comprising at least one selected from the group consisting of 3-tetrafluoropropene, (Z) -1,3,3,3-tetrafluoropropene and 3,3,3-trifluoropropene. System composition.   The composition for thermal cycle systems according to any one of claims 1 to 3, wherein the thermal cycle working medium further comprises a saturated fluorinated hydrocarbon compound.   The saturated fluorinated hydrocarbon compound is trifluoromethane, difluoromethane, difluoroethane, trifluoroethane, tetrafluoroethane, pentafluoroethane, trifluoroiodomethane, pentafluoropropane, hexafluoropropane, heptafluoropropane, pentafluorobutane, The composition for thermal cycle systems according to claim 4, comprising at least one selected from the group consisting of heptafluorocyclopentane.   The unsaturated fluorinated hydrocarbon compound contains 1,1,2-trifluoroethylene, and the content of 1,1,2-trifluoroethylene with respect to 100% by mass of the heat cycle working medium is 20 to 80 mass. % The composition for a heat cycle system according to any one of claims 1 to 5.   The said saturated fluorohydrocarbon compound contains difluoromethane, and content of difluoromethane with respect to 100 mass% of the said working medium for heat cycles is 20-80 mass%, It is any one of Claims 4-6 A composition for a thermal cycle system. The unsaturated fluorinated hydrocarbon compound comprises 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene, the saturated fluorinated hydrocarbon compound comprises difluoromethane;
The ratio of the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane to the total amount of the working medium for the heat cycle is more than 90% by mass and 100% by mass or less,
The ratio of mass to the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane,
1,1,2-trifluoroethylene is 10 mass% or more and less than 70 mass%,
2,3,3,3-tetrafluoropropene is more than 0% by mass and 50% by mass or less,
And the composition for thermal cycle systems of Claim 4 or 5 whose difluoromethane is more than 30 mass% and 75 mass% or less. The unsaturated fluorinated hydrocarbon compound comprises 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene, the saturated fluorinated hydrocarbon compound comprises difluoromethane;
The ratio of the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane to the total amount of the working medium for the heat cycle is more than 90% by mass and 100% by mass or less,
The ratio of mass to the total amount of 1,1,2-trifluoroethylene, 2,3,3,3-tetrafluoropropene and difluoromethane,
The total amount of 1,1,2-trifluoroethylene and 2,3,3,3-tetrafluoropropene is 70% by mass or more,
1,1,2-trifluoroethylene is 30% by mass or more and 80% by mass or less,
2,3,3,3-tetrafluoropropene is more than 0% by weight and 40% by weight or less,
Difluoromethane is more than 0% by mass and 30% by mass or less,
And the ratio of 1,1,2-trifluoroethylene to 2,3,3,3-tetrafluoropropene is 95/5 or less,
The composition for a heat cycle system according to claim 4 or 5.   The composition for thermal cycle systems according to any one of claims 1 to 9, wherein the refrigerating machine oil is at least one selected from polyol ester type refrigerating machine oil and polyvinyl ether type refrigerating machine oil. The refrigerating machine oil is kinematic viscosity of 5 to 200 mm ² / s at 40 ° C., a kinematic viscosity at 100 ° C. is 1 to 100 mm ² / s, the thermal cycling according to any one of claims 1 to 10 System composition.   The composition for a heat cycle system according to any one of claims 1 to 11, wherein an aniline point of the refrigerating machine oil is -100 ° C or higher and 0 ° C or lower.   The composition for thermal cycle systems according to any one of claims 1 to 12, wherein the water content of the refrigerating machine oil is 300 ppm or less.   The composition for thermal cycle systems according to any one of claims 1 to 13, wherein a residual air partial pressure of the refrigerating machine oil is 10 kPa or less.   The composition for thermal cycle systems according to any one of claims 1 to 14, wherein the ash content of the refrigerating machine oil is 100 ppm or less.   The copper deactivator, the extreme pressure agent, the oiliness agent, the antioxidant, the acid scavenger, the antifoaming agent, and at least one additive selected from a polymerization inhibitor, and any one of claims 1 to 15. The composition for thermal cycle systems described in 1.   The thermal cycle system using the composition for thermal cycle systems as described in any one of Claims 1-16.   The thermal cycle system according to claim 17, wherein the thermal cycle system is at least one selected from refrigeration / refrigeration equipment, air conditioning equipment, power generation system, heat transport device, and secondary cooler.   The thermal cycle system has a compression mechanism, and the contact portion that contacts the composition for the thermal cycle system of the compression mechanism is composed of at least one selected from engineering plastics, organic films, and inorganic films. The thermal cycle system according to claim 18.   The thermal cycle system according to claim 19, wherein the engineering plastic is at least one selected from a polyamide resin, a polyphenylene sulfide resin, a polyacetal resin, and a fluororesin.   The organic film is a polytetrafluoroethylene coating film, a polyimide coating film, a polyamideimide coating film, and a thermosetting insulation formed using a resin composed of a polyhydroxy ether resin and a polysulfone resin and a crosslinking agent. The thermal cycle system according to claim 19, wherein the thermal cycle system is at least one selected from films.   The thermal cycle system according to claim 19, wherein the inorganic film is at least one selected from a graphite film, a diamond-like carbon film, a tin film, a chromium film, a nickel film, and a molybdenum film.   The contact portion has a seal portion, and the seal portion is composed of at least one selected from polytetrafluoroethylene, polyphenylene sulfide, chloroprene rubber, silicon rubber, hydrogenated nitrile rubber, fluorine rubber, and hydrin rubber. Item 20. The thermal cycle system according to Item 19.

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