JP4806967B2 - Lubricating oil composition for refrigerator - Google Patents

Description

  The present invention uses a lubricating oil composition for a refrigerator, in particular, a lubricating oil composition for a refrigerator for a non-chlorine fluorocarbon refrigerant, a refrigerator working fluid containing the lubricating oil composition, and the refrigerator working fluid. The present invention relates to a refrigeration apparatus.

  CFC-containing refrigerants have been used in refrigerators, air conditioners, and the like. However, in recent years, due to problems such as destruction of the ozone layer, 1,1,1,2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), difluoroethane ( R-32) and further conversion to non-chlorine-based chlorofluorocarbon refrigerants such as these mixed solvents. Accordingly, various lubricating oil compositions for refrigerating machines (hereinafter sometimes referred to as refrigerating machine oils) based on polyol esters having good compatibility with non-chlorine fluorocarbons have been proposed.

  In order to ensure the stability of the refrigerator, air conditioner, etc., the refrigerating machine oil has compatibility with the non-chlorine fluorocarbon refrigerant, thermal stability, hydrolysis resistance, low-temperature fluidity, electrical insulation, etc. Various performances are required. Among these, from the viewpoint of hydrolysis resistance and compatibility with non-chlorinated chlorofluorocarbons, a hindered ester having excellent heat resistance composed of a branched carboxylic acid and pentaerythritol has been put into practical use. For example, Patent Document 1 discloses a refrigerating machine oil mainly composed of an ester composed of pentaerythritol, a mixed fatty acid of 2-ethylhexanoic acid and 3,5,5-trimethylhexanoic acid, and is stable at a high temperature. Is described as being improved. Patent Document 2 describes that an ester composed of neopentyl glycol and a branched carboxylic acid is excellent in compatibility with chlorofluorocarbon, thermal stability, and the like. Moreover, in patent document 3, the refrigerating machine oil which added the linear fatty acid is described as a refrigerating machine oil excellent in lubricity.

  On the other hand, due to the recent increase in environmental awareness, refrigerators and air conditioners are required to save energy. In refrigerating machine oil, in order to contribute to energy saving, lowering the viscosity is the most effective means, and lowering the viscosity of refrigerating machine oil is aimed at. In order to achieve low viscosity of refrigerating machine oil, use an ester made of dihydric alcohol such as neopentyl glycol, which has lower viscosity than pentaerythritol ester and is superior in hydrolysis resistance, thermal stability, viscosity, etc. It is effective to do. However, these esters may have low viscosity and insufficient lubricity.

  As a method of improving lubricity, there is a method of using an ester of a linear fatty acid as in Patent Document 3 described above. However, it is generally known that an ester using this linear fatty acid has crystallinity, and thus the long-term stability at a low temperature is lowered.

Thus, a lubricating oil for a refrigerator that has excellent low-temperature stability, low viscosity, and excellent lubricity is desired.
Japanese Patent Laid-Open No. 10-8084 JP-A-5-209171 Japanese Patent Laid-Open No. 11-228984

  An object of the present invention is a lubricating oil composition for a refrigerator that has a low viscosity, good lubricity, and excellent long-term stability in a low temperature region, and in particular, a lubricating oil for a refrigerator that uses a non-chlorofluorocarbon refrigerant. It is to provide a composition. Another object of the present invention is to provide a refrigerator working fluid using the above lubricating oil composition for a refrigerator and a refrigerant compression refrigeration apparatus using the above refrigerator working fluid.

  The present inventors diligently studied the lubricity and low-temperature stability of a low-viscosity lubricating oil composition used in a refrigerator using a non-chlorine fluorocarbon refrigerant, and combined various polyhydric alcohols and carboxylic acids to form esters. The molecular design of As a result, a mixed alcohol composed of a specific amount of neopentyl glycol, pentaerythritol and dipentaerythritol, a specific amount of pentanoic acid (saturated linear carboxylic acid having 5 carbon atoms), heptanoic acid (saturated linear chain having 7 carbon atoms) Ester obtained by reacting carboxylic acid) and mixed saturated linear carboxylic acid composed of caprylic acid (saturated linear carboxylic acid having 8 carbon atoms) to satisfy a certain quantitative relationship solves the above problems As a result, the present invention has been completed.

  A lubricating oil composition for a refrigerator according to the present invention comprises a mixed alcohol comprising 10 to 50 mol% neopentyl glycol, 50 to 89 mol% pentaerythritol, and 0.03 to 3 mol% dipentaerythritol, and 70 A lubricating oil composition for a refrigerator comprising an ester obtained from -95 mol% pentanoic acid and heptanoic acid and a mixed saturated linear carboxylic acid consisting of 5-30 mol% caprylic acid, The following relation:

And the kinematic viscosity at 40 ° C. of the composition is 6 to 28 mm ² / s.

  The present invention also provides a refrigerator working fluid, and the refrigerator working fluid is composed of the above lubricating oil composition for a refrigerator and a non-chlorine-based chlorofluorocarbon solvent.

  The present invention also provides a refrigeration apparatus, which is a refrigerant compression refrigeration apparatus including a compressor, a condenser, an expansion mechanism, and an evaporator, and uses the above-described refrigerator working fluid.

  The lubricating oil composition for refrigerators of the present invention has a low viscosity, good lubricity, and excellent long-term low-temperature stability. This composition is further excellent in compatibility with a non-chlorine-based chlorofluorocarbon refrigerant required as a lubricating oil composition for refrigerators, heat resistance, and electrical insulation. Accordingly, the composition of the present invention is a lubricating oil for a refrigerator using a non-chlorine-based fluorocarbon refrigerant, particularly a non-chlorine-based fluorocarbon refrigerant containing at least one of 1,1,1,2-tetrafluoroethane and difluoromethane, Alternatively, it is useful as a refrigerator working fluid mixed with a non-chlorine-based chlorofluorocarbon refrigerant, and contributes to fuel saving of various refrigeration apparatuses.

  Hereinafter, an ester contained in the composition of the present invention, a lubricating oil composition for a refrigerator containing the ester, a refrigerator working fluid containing the composition, and a refrigerant compression refrigeration apparatus using the refrigerator working fluid Will be described.

(I) Ester The ester contained in the lubricating oil composition for a refrigerator of the present invention is obtained from three types of alcohol (mixed alcohol) and three types of saturated linear carboxylic acid (mixed saturated linear carboxylic acid). It is a mixture of esters. Specifically, the ester is a mixed alcohol composed of 10 to 50 mol% neopentyl glycol, 50 to 89 mol% pentaerythritol, and 0.03 to 3 mol% dipentaerythritol, and 70 to 95 mol. Mixed saturated linear carboxylic acid consisting of 5% pentanoic acid and heptanoic acid, and 5-30 mol% caprylic acid:

It is obtained by reacting to satisfy. When reacting the mixed alcohol and the mixed saturated linear carboxylic acid, the present inventors, among these components, neopentyl glycol in the mixed alcohol, pentanoic acid in the mixed saturated linear carboxylic acid, and It has been found that the quantitative relationship with caprylic acid affects the long-term low-temperature stability and lubricity of the resulting low viscosity ester. That is, it has been found that an ester having a low viscosity, good lubricity, and excellent long-term low-temperature stability can be obtained by designing an ester molecule so as to satisfy the above relational expression.

  As described above, the mixed alcohol that is a raw material for the ester is composed of neopentyl glycol, pentaerythritol, and dipentaerythritol. In the present invention, pentaerythritol is used for the purpose of obtaining an ester having excellent electrical insulation, neopentyl glycol is used for the purpose of achieving low viscosity, and dipentaerythritol is used for the purpose of improving long-term low-temperature stability.

  The content of neopentyl glycol in the mixed alcohol serving as the raw material for the ester is 10 to 50 mol%, preferably 12 to 48 mol%, more preferably 15 to 46 mol%. When the content of neopentyl glycol is less than 10 mol%, the long-term low-temperature stability of the obtained ester becomes insufficient, and the desired viscosity may not be obtained. When it exceeds 50 mol%, the lubricity of the ester obtained is insufficient, and the electrical insulation is also insufficient.

  The content of pentaerythritol in the mixed alcohol serving as the raw material for the ester is 50 to 89 mol%, preferably 52 to 85 mol%, more preferably 54 to 80 mol%. When the content of pentaerythritol is less than 50 mol%, the resulting ester has insufficient lubricity and insufficient electrical insulation. If it exceeds 89 mol%, the long-term low-temperature stability of the resulting ester will be insufficient.

  The content of dipentaerythritol in the mixed alcohol used as the raw material of the ester is 0.03 to 3 mol%, preferably 0.04 to 2.8 mol%, more preferably 0.05 to 2.5 mol%. It is. When the content of dipentaerythritol is less than 0.03 mol%, the low-temperature stability of the resulting ester becomes insufficient. When it exceeds 3 mol%, the chlorofluorocarbon compatibility of the resulting ester is deteriorated, and the desired viscosity may not be obtained.

  The mixed saturated linear carboxylic acid (mixed saturated linear monocarboxylic acid) used as the raw material of the ester is composed of pentanoic acid, heptanoic acid, and caprylic acid as described above. In the present invention, in order to obtain high lubricity, a linear fatty acid, particularly caprylic acid having a good lubricity (saturated linear carboxylic acid having 8 carbon atoms) is used as an essential component, and further caprylic acid is used. In order to improve the low temperature stability, linear odd-numbered acids that are inferior to caprylic acid but have relatively high lubricity and excellent low temperature stability, ie, pentanoic acid (saturated linear carboxylic acid having 5 carbon atoms) and heptane An acid (saturated linear carboxylic acid having 7 carbon atoms) is used. By using such a mixed saturated linear carboxylic acid, an ester having a desired viscosity and excellent lubricity can be obtained.

  The total content of pentanoic acid and heptanoic acid in the mixed saturated linear carboxylic acid used as the raw material for the ester is 70 to 95 mol%, preferably 72 to 93 mol%, more preferably 74 to 91 mol%. . When the total amount of pentanoic acid and heptanoic acid is less than 70 mol%, the long-term low-temperature stability of the resulting ester becomes insufficient, and when it exceeds 95 mol%, the lubricity of the obtained ester becomes insufficient.

  In order to obtain the ester contained in the composition of the present invention, the mixed alcohol and the mixed saturated linear carboxylic acid are represented by the following relational formula:

React to meet. If the value of this relational expression is in the range of 5 to 25, an ester excellent in lubricity and long-term low-temperature stability can be obtained.

  The reaction for producing the ester is carried out by a normal esterification reaction or transesterification reaction. The ratio of the mixed alcohol and the mixed fatty acid is preferably adjusted as appropriate so that the resulting mixed ester has a hydroxyl value of 5.0 mgKOH / g or less and an acid value of 0.05 mgKOH / g or less.

  The ester production method used in the present invention may be produced by any method as long as the above performance is not impaired, and is not particularly limited. The ester is obtained as follows, for example. First, from the viewpoint of production efficiency and economy, preferably 1.05 so that the carboxyl group of the mixed saturated linear carboxylic acid is 1.0 to 1.5 equivalents relative to 1 equivalent of the hydroxyl group of the mixed alcohol. Mix to ˜1.3 equivalents and add catalyst if necessary. The mixture is reacted at 220 to 260 ° C. for 3 to 15 hours under a nitrogen stream, and when the hydroxyl value becomes 2.0 mgKOH / g or less, excess carboxylic acid is removed under reduced pressure. Then, after deoxidizing with alkali, operations such as adsorption treatment using activated clay, acid clay, and synthetic adsorbent, and steaming are performed alone or in combination.

(II) Refrigerating machine lubricating oil composition The refrigerating machine lubricating oil composition of the present invention preferably contains 80% by mass or more, more preferably 90% by mass or more of the ester, based on the mass of the entire composition. In addition to this, other esters, additives and the like can be included within the range not impairing the performance of the present invention.

  Examples of the other ester include esters containing neopentyl glycol having 5 to 10 carbon atoms and monocarboxylic acid having 5 to 10 carbon atoms.

  The lubricating oil composition for refrigerators of the present invention is a known additive, for example, a phenolic antioxidant, a metal deactivator such as benzotriazole, thiadiazole or dithiocarbamate, an acid supplement such as an epoxy compound or carbodiimide. Additives such as agents and phosphorus-based extreme pressure agents can be appropriately contained depending on the purpose. The ratio contained is arbitrary.

The lubricating oil composition for a refrigerator of the present invention has a kinematic viscosity at 40 ° C. of 6 to 28 mm ² / s. Further, from the viewpoint of obtaining excellent lubricity and compatibility with a non-chlorine-based chlorofluorocarbon refrigerant, and from the viewpoint of good startability and energy saving of a refrigerator by using the lubricating oil composition, preferably 7 to ²⁰ mm ² / s, more preferably 8 to 18 mm ² / s.

  The acid value of the lubricating oil composition for a refrigerator of the present invention is not particularly limited. Preferably it is 0.05 mgKOH / g or less, More preferably, it is 0.03 mgKOH / g or less, More preferably, it is 0.01 mgKOH / g or less. When an acid value exceeds 0.05 mgKOH / g, there exists a possibility that a metal may be corroded and hydrolysis resistance may become inadequate.

  The hydroxyl value of the lubricating oil composition for a refrigerator of the present invention is not particularly limited. Preferably it is 5.0 mgKOH / g or less, More preferably, it is 3.0 mgKOH / g or less, More preferably, it is 2.0 mgKOH / g or less, Most preferably, it is 1.0 mgKOH / g. When the hydroxyl value exceeds 5.0 mgKOH / g, there is a risk of adversely affecting a sealing agent or the like used as an organic material in an apparatus in which the composition is used. Furthermore, the additive contained may be adversely affected.

(III) Refrigerator Working Fluid The refrigerator working fluid of the present invention is composed of the above-described lubricating oil composition for a refrigerator and a non-chlorine fluorocarbon refrigerant. Although there is no restriction | limiting in particular in the content ratio of the lubricating oil composition for refrigerators, and a non-chlorine system Freon refrigerant, Preferably, the lubricating oil composition for refrigerators: a non-chlorine system Freon refrigerant is 10: 90-90: by mass ratio. The ratio is 10. When the blending ratio of the non-chlorine-based chlorofluorocarbon refrigerant is higher than the above range, the viscosity of the resulting refrigerator working fluid is lowered, and there is a risk of causing poor lubrication. When it is lower than the above range, there is a possibility that the refrigeration efficiency may be lowered when the obtained refrigerator working fluid is used in equipment.

  Examples of the non-chlorofluorocarbon refrigerant include 1,1,1,2-tetrafluoroethane (R-134a), pentafluoroethane (R-125), difluoroethane (R-32), and trifluoroethane (R- 23), 1,1,2,2-tetralofluoroethane (R-134), 1,1,1-trifluoroethane (R-143a), 1,1-difluoroethane (R-152a) and the like. . These may be used alone or as a mixed refrigerant of two or more.

  The mixed refrigerant is commercially available, for example, R-407C (R-134a / R-125 / R-32 = 52/25/23 mass%), R-410A (R-125 / R-32 = 50 / 50 mass%), R-404A (R-125 / R-143a / R-134a = 44/52/4 mass%), R-407E (R-134a / R-125 / R-32 = 60/15 / 25 mass%), R-410B (R-32 / R-125 = 45/55 mass%), etc. are used. Particularly preferred is a mixed refrigerant containing at least one of R-134a and R-32.

(IV) Refrigerant compression type refrigerating apparatus The composition for a refrigerator working fluid of the present invention or the refrigerant working fluid of the present invention containing the composition has at least a compressor, an aggregator, an expansion mechanism, and an evaporator. Accordingly, it can be used in a refrigeration apparatus having a dryer. Specific examples of such a refrigeration apparatus include low-temperature equipment such as refrigerators, industrial refrigerators, air conditioners such as room air conditioners and packaged air conditioners, car air conditioners for hybrid cars and electric vehicles.

  EXAMPLES The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples.

Below, the test method of ester manufactured by the present Example and the comparative example is described.
<Kinematic Viscosity and Viscosity Index> Based on JIS K-2283, the kinematic viscosity at 40 ° C. and 100 ° C. is measured using a Canon-Fenske viscometer, and the viscosity index is calculated.
<Acid Value> Measured according to JIS C-2101.
<Hydroxyl value> Measured according to JIS K-0070.
<Hue> Measured according to JOCS 2.2.1.4-1996.
<Volume Resistivity> Volume resistivity (TΩ · m) at 25 ° C. is measured according to JIS C-2101.
<Pour point> Measured according to JIS K-2269.
<Long-term low-temperature test> 400 g of a sample (ester) whose water content is adjusted to 100 ppm or less is put in a steel square can and left in a low temperature storage at -30 ° C. for 1000 hours to visually check whether crystals are precipitated. To do.
<Two-Phase Separation Temperature> A wall thickness Pyrex (registered trademark) tube in which 0.6 g of a sample (ester) and 2.4 g of refrigerant R-134a or R-407C are cooled in an ethanol bath containing dry ice ( It was enclosed in a total length of 300 mm, an outer diameter of 10 mm, and an inner diameter of 6 mm), heated or cooled at a rate of 1 ° C./min, and the two-phase separation temperature at a low temperature was visually measured in the range of −30 ° C. to 20 ° C.
<Shield tube test> 10 g of a sample (ester) whose moisture concentration was previously adjusted to 200 ppm or less in a glass tube, 5 g of Freon R-410A, 1.6 mm diameter, 50 mm length iron piece, copper piece, and aluminum Seal one piece each and seal. After heating this at 175 ° C. for 14 days, the acid value and hue (APHA) of the fluorocarbon-containing sample excluding the metal pieces are measured.
<Falex Friction Test> In accordance with ASTM D-2670, a Falex friction test is performed as follows while blowing R-134a into a sample at a rate of 150 mL / min. First, the sample temperature is set to 100 ° C., and after a trial run at a load of 150 pounds for 1 minute, the specimen is run for 1 hour under a load of 300 pounds.

Example 1.1: Preparation of ester
In a 1 liter four-necked flask equipped with a thermometer, a nitrogen inlet tube, a stirrer, and a cooling tube, the mixed alcohol and mixed carboxylic acid shown in Table 1 are equivalent to the hydroxyl group of the mixed alcohol and the carboxyl group of the mixed carboxylic acid. The mixture was charged so that the ratio was 1: 1.1, and the reaction was performed at 220 ° C. under atmospheric pressure while distilling off the reaction water. During the reaction, the hydroxyl value was monitored, and the reaction was stopped when it was below 2.0 mgKOH / g. Thereafter, stripping was performed under a reduced pressure of 1 to 5 kPa to remove unreacted carboxylic acid over 1 hour. The obtained reaction mixture was washed with an aqueous potassium hydroxide solution. Washing with water was repeated 5 times so that the pH of the wastewater was neutral. Next, the obtained ester layer was dehydrated under reduced pressure at 100 ° C. and 1 kPa, and acid clay and silica-alumina-based adsorbent were respectively added so as to be 1.0 mass% of the theoretically obtained ester amount. And adsorption treatment. The adsorption treatment temperature, pressure, and adsorption treatment time were 100 ° C., lkPa, and 3 hours, respectively. Finally, filtration was performed using a 1 micron filter to obtain an ester (referred to as ester A). The composition of the obtained ester A is shown in Table 1.

(Examples 1.2 to 1.6)
Ester (esters B to F) was obtained in the same manner as in Example 1 except that the mixed alcohol and the mixed carboxylic acid shown in Table 1 were used. The compositions of the obtained esters B to E are shown in Table 1.

(Comparative Examples 1.1 to 1.8)
An ester (esters G to N) was obtained in the same manner as in Example 1 except that the mixed alcohol and the mixed carboxylic acid shown in Table 1 were used. Table 1 shows the compositions of the obtained esters G to N.

  Esters A to N as shown in Table 1 were obtained. Of these, the esters G to N of Comparative Examples 1.1 to 1.8 do not satisfy the conditions for the esters used in the present invention. That is, in the esters G and H of Comparative Examples 1.1 and 1.2, the quantitative relationship (value of the relational expression) of pentanoic acid, heptanoic acid, and neopentyl glycol is not appropriate. Ester I of Comparative Example 1.3 does not contain pentanoic acid and heptanoic acid. The ester J of Comparative Example 1.4 does not contain dipentaerythritol. The ester K of Comparative Example 1.5 has a low content of neopentyl glycol and a high content of pentaerythritol. In the esters L and N of Comparative Examples 1.6 and 1.8, the total amount of pentanoic acid and heptanoic acid and the content of caprylic acid are out of the range, and the values of the relational expressions are not appropriate. The ester M of Comparative Example 1.7 has a high dipentaerythritol content.

(Example 2.1)
The ester A obtained in Example 1.1 was used as a lubricating oil (lubricating oil 1). For the lubricating oil 1, the kinematic viscosity, viscosity index, hue, acid value, hydroxyl value, volume resistivity, pour point, and two-phase separation temperature (low temperature) at 40 ° C. and 100 ° C. were measured by the above methods. Furthermore, a long-term low temperature test, a shield tube test, and a Falex friction test were performed. The results are shown in Table 2.

(Examples 2.2 to 2.6)
Esters B to F obtained in Examples 1.2 to 1.6 were used as lubricating oils (lubricating oils 2 to 6). Each lubricant was tested in the same manner as in Example 2.1. The results are also shown in Table 2.

(Comparative Examples 2.1 to 2.8)
The same tests as in Example 2.1 were performed on each lubricating oil, using the esters G to N obtained in Comparative Examples 1.1 to 1.8 as lubricating oils (lubricating oils 7 to 14). The results are also shown in Table 2.

As is apparent from the results in Table 2, the lubricating oils of the examples (lubricating oils 1 to 6) have a kinematic viscosity at 40 ° C. of 6 to 28 mm ² / s and a desired viscosity. From the test, it can be seen that it has excellent lubricity and also has excellent stability in which no precipitate is generated even in a long-term low-temperature test. These lubricating oils 1 to 6 further have a low pour point, excellent compatibility with the chlorofluorocarbon refrigerant from the two-phase separation temperature, and little thermal oxidative deterioration from the shield tube test, and as other lubricating oils for refrigerators In order to satisfy the required performance, it is clear that the lubricating oil is excellent for refrigeration machines, especially for chlorofluorocarbon refrigerant refrigerants.

  On the other hand, the lubricating oils of the comparative examples (lubricating oils 7 to 14) were insufficient in either lubricity or long-term low-temperature stability because the contained ester did not satisfy the scope of the present invention. . That is, the lubricating oils of Comparative Examples 2.1 and 2.4 to 2.6 (lubricating oils 7 and 10 to 12) were insufficient in stability because precipitates were formed in the long-term low-temperature stability test. In the lubricating oils of Comparative Examples 2.2, 2.3, and 2.8 (lubricating oils 8, 9, and 14), the pin was greatly worn in the Falex friction test, and the lubricity was insufficient. . Although the lubricating oil 13 of Comparative Example 2.7 was excellent in long-term low-temperature stability and lubricity, the two-layer separation temperature was high and the compatibility with the chlorofluorocarbon refrigerant was particularly poor.

  The lubricating oil composition for refrigerators of the present invention has a low viscosity, good lubricity, and excellent long-term low-temperature stability. This composition is further excellent in compatibility with a non-chlorine-based chlorofluorocarbon refrigerant required as a lubricating oil composition for refrigerators, heat resistance, and electrical insulation. Accordingly, the composition of the present invention is a lubricating oil for a refrigerator using a non-chlorine-based fluorocarbon refrigerant, particularly a non-chlorine-based fluorocarbon refrigerant containing at least one of 1,1,1,2-tetrafluoroethane and difluoromethane, Alternatively, it is useful as a refrigerator working fluid mixed with a non-chlorine-based chlorofluorocarbon refrigerant, and contributes to fuel saving of various refrigeration apparatuses. The refrigerator working fluid comprising the lubricating oil composition for a refrigerator of the present invention and the lubricating oil and the non-chlorine-based chlorofluorocarbon refrigerant specifically includes low-temperature equipment such as refrigerators, industrial refrigerators, room air conditioners, and package air conditioners. It can be used for air conditioners such as car air conditioners for hybrid cars and electric cars.

Claims (3)

A mixed alcohol consisting of 10-50 mol% neopentyl glycol, 50-89 mol% pentaerythritol, and 0.03-3 mol% dipentaerythritol, 70-95 mol% pentanoic acid and heptanoic acid, and A lubricating oil composition for a refrigerator comprising an ester obtained from a mixed saturated linear carboxylic acid composed of 5-30 mol% caprylic acid,
The ester has the following relationship:

And a kinematic viscosity at 40 ° C. of 6 to 28 mm ² / s.   A refrigerator working fluid comprising the lubricating oil composition for a refrigerator according to claim 1 and a non-chlorine fluorocarbon solvent.   It is a refrigerant | coolant compression-type refrigeration apparatus provided with a compressor, a condenser, an expansion mechanism, and an evaporator, Comprising: The refrigeration apparatus using the refrigerator working fluid of Claim 2.