KR101280701B1 - Compressor for refrigerating air conditioning and refrigerating air conditioner - Google Patents

Abstract

An object of the present invention is to improve the wear resistance of a refrigeration air conditioning compressor and to realize high efficiency of the refrigeration air conditioning apparatus using the compressor.
In the refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene, etc., it contains the refrigeration oil main material, such as polyol ester oil, and the addition polyol ester oil. The refrigeration air conditioning compressor which mixed and enclosed the refrigeration oil is used. The composition of the added polyol ester oil is 1 to 30% by weight.

Description

Refrigeration and air conditioning compressors and refrigeration air conditioning units {COMPRESSOR FOR REFRIGERATING AIR CONDITIONING AND REFRIGERATING AIR CONDITIONER}

The present invention relates to a refrigeration air conditioning compressor and a refrigeration air conditioning apparatus using a heat pump cycle.

As a global environmental countermeasure in the field of refrigeration and air-conditioning equipment, the replacement of CFC (Chloro fluoro carbons) and HCFC (Hydro chloro fluoro carbons) used for refrigerants and heat insulators as ozone depleting substances, and for high efficiency and refrigerants as a global warming measure Substitution of HFC (Hydro fluoro carbons) is mentioned, and these have been actively progressed.

As a substitute for CFCs and HCFCs, which are ozone depleting substances, selection of refrigerants and heat insulators, and equipment development were carried out mainly with the aim of not destroying the ozone layer, having low toxicity and combustibility, and ensuring efficiency. As a result, in the heat insulating material of a refrigerator, CFC11 was replaced with a blowing agent in order of HCFC141b and cyclopentane, and it is shifting to combined use with a vacuum heat insulating material now.

As a refrigerant | coolant, CFC12C is replaced by HFC134a [Global Warming Potential (GWP) = 1430] in refrigerator and car air conditioner, and HCFC22 is replaced by R410A [HFC32 / HFC125 (50) in room air conditioner or package air conditioner. / 50% by weight) mixture: GWP = 2088].

However, at the 3rd Contracting State Conference on Climate Change Treaty (COP3) held in Kyoto in 1997, HFC emissions were converted into CO ₂ as greenhouse gases, which would be regulated.

Therefore, in the domestic refrigerator, it is judged that the amount of refrigerant filling is small and a flammable refrigerant can also be used in manufacturing, and HFC134a was replaced with flammable R600a (isobutane: GWP = 3). Also, due to rising public opinion, attention has now focused on HFC134a for car air conditioners and R410A for room air conditioners and package air conditioners. In addition, in the commercial refrigerator, the amount of encapsulation of R600a is large, and HFC134a is still used for flammability.

In reality, the recycling of equipment is mandated by the Household Appliances Recycling Act of 2001 (Special Household Appliances Re-Commercialization Act) or the Automobile Recycling Act of 2003 (Law on Recycling of Used Cars). Used HFCs are recovered and processed. However, in the European Union (EU), in 2006 Directive (Directive 2006/40 / EC), the use of refrigerants of GWP> 150 as refrigerants for car air conditioners has been banned since January 2011. This has led to various movements in the car air-conditioning industry, and there is a concern that room air conditioners may be regulated someday. In accordance with the EU Directive, there is also a possibility of a regulatory review including a stationary air conditioner in 2011, and the examination of alternative refrigerants is being accelerated.

These alternative refrigerants have the same thermal properties as HFC134a, and for reasons of low GWP, low toxicity, low ductility, etc., 2, 3, 3, 3-tetrafluoropropene [HFO1234yf (Hydro fluoro olefine) (GWP = 4) ] Or 1, 3, 3, 3-tetrafluoropropene (HFO1234ze) (GWP = 10) alone or a mixed refrigerant thereof is a candidate. As a refrigerant mixed with 2, 3, 3, 3-tetrafluoropropene, difluoro methane (HFC32) is mainly used.

It is also conceivable to mix HFC134a and HFC 125, depending on the GWP allowed for low combustion. Other refrigerants include hydrocarbons such as propane and propylene and low GWP hydrofluorocarbons such as fluoroethane (HFC161), difluoro ethane (HFC152a) and difluoromethane (HFC32).

On the other hand, the refrigeration oil is used in the hermetic electric compressor to play a role of lubrication, sealing and cooling of the sliding parts.

In the air conditioner, the APF (Annual Performance) Factor is adopted as an index indicating energy saving performance according to the actual use state by the Energy Saving Act (Act on the Rationalization of Energy Use), which has been revised since 2006. Increasing efficiency and high efficiency are needed. As the use conditions become strict in this manner, a refrigeration oil having good lubricity in terms of securing reliability is required.

Used in compressors using a single refrigerant of 2, 3, 3, 3-tetrafluoropropene (HFO1234yf) and 1, 3, 3, 3-tetrafluoropropene (HFO1234ze) or a mixed refrigerant comprising these refrigerants As said refrigeration oil, polyalkylene glycol oil, mineral oil, poly (alpha) olefin oil, and alkyl benzene oil are disclosed from the said situation (for example, patent document 1).

Patent Literature 2 discloses an oil having a boiling point of 50 to 250 ° C. and a viscosity of 5 centis / 40 ° C. or less in a refrigerator oil comprising at least one of paraffin type refrigerator oil, naphthenic refrigerator oil and synthetic refrigerator oil. A freezer oil composition is disclosed.

In addition, Patent Documents 3 and 4 to 9 disclose HFO-1234yf, HFO-1225yeZ, trans-1, 3, 3, 3-pentafluoro propane (trans HFO-1234ze), 1, 1-difluoro ethane ( HFC-152a), 1, 1, 1, 2, 3, 3, 3-heptafluoro propane (HFC-227ea), 1, 1, 1, 2-tetrafluoroethane (HFC-134a), 1, 1 , Azeotropic mixture compositions (AZEOTROPIC MIXTURE-LIKE COMPOSITION) and mineral oils (including paraffinic or naphthenic oils), silicone oils, polyalkylbenzenes, including 1, 2, 2-pentafluoroethane (HFC-125), and the like. , Lubricants such as polyol esters, polyalkylene glycols, polyalkylene glycol esters, polyvinyl ethers, poly (α-olefins), halocarbon oils and the like are disclosed.

[Patent Document 1]: Japanese Patent Application Publication No. 2009-540170 [Patent Document 2] Japanese Unexamined Patent Application Publication No. 58-93796 [Patent Document 3] Japanese Patent Application Publication No. 2007-532767 [Patent Document 4] Japanese Patent Application Publication No. 2007-538115 [Patent Document 5] Japanese Patent Application Publication No. 2008-504374 [Patent Document 6] Japanese Patent Application Publication No. 2008-505989 [Patent Document 7]: Japanese Patent Application Publication No. 2008-506793 Patent Document 8: Japanese Patent Application Publication No. 2008-524433 [Patent Document 9] Japanese Patent Application Publication No. 2008-239814

Since 2, 3, 3, 3-tetrafluoropropene (HFO1234yf) and 1, 3, 3, 3-tetrafluoropropene (HFO1234ze) are low pressure refrigerants compared to R410A, the compressor is exhausted to obtain refrigerant circulation. High capacity and high speed rotation is essential. For this reason, in the case of the said refrigeration oil, the subject regarding abrasion resistance remains in sliding parts, such as a compressor bearing.

In addition, refrigerants such as HFO1234yf, HFO1234ze, propane, propylene, fluoroethane and the like have very high solubility with the above-mentioned refrigerator oil and have a large dissolution of the refrigerant in the compressor, so that the refrigerant melt viscosity in the refrigerator oil is lowered. For this reason, the problem of the fall of the sealing part of a compression part and the increase of the wear amount of a sliding part arises.

For the reason mentioned above, it is preferable to use the refrigerating and air-conditioning apparatus which uses the refrigerator oil which can make both the efficiency improvement of an apparatus, and abrasion resistance compatible.

An object of the present invention is a refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene or the like as a refrigerant, or hydrocarbon, fluoro such as propane, propylene, etc. Refrigeration and air conditioning equipment using the compressor while improving the wear resistance of the refrigeration air conditioning compressor using a refrigerant for refrigeration air conditioning, such as furnace ethane (HFC161), difluoro ethane (HFC152a), difluoro methane (HFC32), and R410A To achieve high efficiency.

Refrigeration and air conditioning compressor of the present invention is a refrigerant oil, such as polyol ester oil in a refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene, etc. And a refrigerator oil containing the added polyol ester oil are mixed and enclosed, and the composition of the added polyol ester oil is 1 to 30% by weight.

According to the present invention, it is possible to obtain a compressor having both improved performance and wear resistance of the compressor without using a phosphorous extreme pressure agent which is harmful to the environment as an additive of the refrigeration oil.

According to the present invention, it is possible to obtain a refrigeration air conditioner in consideration of an environment capable of achieving both improved performance and long-term reliability of a refrigeration air conditioner without using a phosphorus extreme pressure agent that is harmful to the environment as an additive of refrigeration oil.

1 is a schematic configuration diagram showing a room air conditioner.
2 is a cross-sectional view showing a scroll hermetic compressor for a room air conditioner.

EMBODIMENT OF THE INVENTION Hereinafter, the refrigeration air conditioning compressor which concerns on one Embodiment of this invention, and the refrigeration air conditioning apparatus using the same are demonstrated.

The refrigeration air conditioning compressor is a refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene or difluoro methane or an encapsulated refrigerant R410A, Refrigerator oil containing at least one kind of base oil selected from the group consisting of polyol ester oils represented by formulas (1) and (2), wherein R ₁ represents an alkyl group having 5 to 9 carbon atoms And a refrigeration oil containing an additive polyol ester oil represented by the following general formula (3), wherein R ₂ represents an alkyl group having 7 to 9 carbon atoms.

The refrigeration air conditioning compressor is a refrigerant containing an refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene, propane, propylene or fluoroethane, Mineral oil or polyvinyl ether oil or at least one base oil selected from the group consisting of polyol ester oils represented by the formulas (1) and (2), wherein R ₁ represents an alkyl group having 5 to 9 carbon atoms And a refrigeration oil main body having a low temperature side critical dissolution temperature of -30 ° C or less, and a refrigeration oil containing an additive polyol ester oil represented by the above formula (3), wherein R ₂ represents an alkyl group having 7 to 9 carbon atoms. It is sealed. And the composition of the added polyol ester oil is 1 to 30% by weight.

In the said refrigeration air-conditioning compressor, it is preferable that dynamic viscosity in 40 degreeC of refrigeration oil main body is 25-120 mm <2> / s, and dynamic viscosity in 40 degreeC of addition polyol ester oil is 180 mm <2> / s or more.

The refrigeration and air conditioning apparatus includes: a refrigeration air conditioning compressor, a heat exchanger for radiating heat of encapsulated refrigerant discharged from the refrigeration air conditioning compressor, a decompression unit for decompressing encapsulated refrigerant flowing out of the heat exchanger, and a decompression unit. It is provided with a heat exchanger for heating the sealed refrigerant reduced in pressure.

In the above-mentioned refrigeration and air conditioning apparatus, the kinematic viscosity at 40 ° C. of the refrigeration oil main body is 25 to 120 mm 2 / s, and the adsorption capacity of the added polyol ester oil to the iron-based material is preferably two times or more higher than that of the refrigeration oil base.

The refrigeration air conditioning compressor is a polyol ester oil represented by the above formulas (1) and (2) in a refrigerant having a global warming coefficient of 1000 or less, or a refrigerant for refrigeration air conditioning of R410A (wherein, R ₁ represents a carbon number of 5 to 9). A refrigeration oil main body containing at least one kind of base oil selected from the group consisting of alkyl groups and having a kinematic viscosity at 40 ° C of 25 to 120 mm 2 / s, and an additional polyol ester oil represented by the above formula (3) Among them, R ₂ is a mixture of a refrigeration oil containing an alkyl group having 7 to 9 carbon atoms and sealed.

It is preferable that the composition of addition polyol ester oil is 1-30 weight%.

The compressor for refrigeration and air conditioning is a scroll or rotary hermetic compressor with a built-in motor, a twin rotary compressor, a two-stage compressed rotary compressor, and a swing compressor integrating rollers and vanes. It is preferable that dynamic viscosity in ° C is 25 mm <2> / s-120 mm <2> / s or less, and kinematic viscosity in 40 degreeC of addition polyol ester oil is 180 mm <2> / s or more.

The said refrigeration and air conditioning compressor includes the sliding part formed from iron-type material, and the contact surface pressure in a sliding part is 10 Mpa or more.

In the above-mentioned refrigeration and air conditioning compressor, the added polyol ester oil has an adsorption capacity to iron-based material more than twice as high as that of the refrigeration oil. Moreover, 2 times or more are preferable and, as for the adsorption capacity of the added polyol ester oil with respect to the iron type material, 4 times or more are more preferable.

The refrigeration and air conditioning apparatus uses the scroll or rotary compressor.

Hereinafter, the present invention will be described in detail with reference to examples.

Examples include 2, 3, 3, 3-tetrafluoropropene or 1, 3, 3, 3-tetrafluoropropene or mixed refrigerants comprising them, or propane, propylene, fluoroethane, di Disclosed is a compressor using fluoromethane or R410A and a refrigeration air conditioning system using the compressor.

In the present specification, the refrigerant for refrigeration air conditioning is 2, 3, 3, 3-tetrafluoropropene or 1, 3, 3, 3-tetrafluoropropene or a mixed refrigerant containing them, or propane, propylene, fluoro R410A and a refrigerant having a GWP of 1000 or less, such as ethane, difluoromethane and the like.

The refrigeration oil of the Example contains the addition polyol ester oil whose adsorption capacity with respect to an iron type material is much higher than base oil.

Examples of the base oil having a lower adsorption capacity compared to the added polyol ester oil include mineral oil, polyvinyl ether oil, and polyol ester oil having an ester group in its molecular structure.

As mineral oil, a naphthenic mineral oil and a paraffinic mineral oil can be used. As these mineral oils, the effluent oil which can be obtained by atmospheric distillation of paraffinic crude oil, an intermediate mechanical crude oil, or a naphthenic crude oil, or vacuum-distillation of the residual oil of atmospheric distillation is a commercial method, for example. And refined oils obtained by refining according to the present invention, deep de dewaxed oils obtained by deep dewaxing after refining, and hydrogenated oils obtained by hydrogenation. There is no restriction | limiting in particular in the purification method at that time, Various methods are used.

Polyol ester oil can be obtained by condensation reaction of polyhydric alcohol and monovalent fatty acid.

As polyol ester oil, hindered which is excellent in thermal stability is preferable, and what is preferable as polyhydric alcohol is neopentyl glycol, trimethylol propane, pentaerythritol, etc., for example.

As monovalent fatty acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methyl butanoic acid, 2-methyl pentanic acid, 2-methyl hexanoic acid, 2-ethyl hexanoic acid, isooctane Acids, 3, 5, 5-trimethyl hexanoic acid, and the like, and these are used alone or in combination of two or more thereof.

As addition polyol ester oil which has high adsorption ability to iron type material, the polyol ester oil which contains many ester groups in molecular structure is preferable, and dipentaerythritol which is a hinder synthesize | combined with a polyhydric alcohol and monovalent fatty acid is mentioned.

As monovalent fatty acid, n-pentanoic acid, n-hexanoic acid, n-heptanoic acid, n-octanoic acid, 2-methyl butanoic acid, 2-methyl pentanic acid, 2-methyl hexanoic acid, 2-ethyl hexanoic acid, isooctane Acids, 3, 5, 5-trimethyl hexanoic acid, and the like, and these are used alone or in combination of two or more thereof.

Although the viscosity grade of the refrigeration oil used for the air conditioning apparatus and the refrigerator of an Example changes with kinds of compressor, the dynamic viscosity in 40 degreeC of a scroll type compressor is preferable in the range of 46-120 mm <2> / s. Moreover, in a rotary compressor, the range of 25-70mm <2> / s of dynamic viscosity in 40 degreeC is preferable.

The heat resistance class of electric insulation is prescribed by heat resistance class of heat insulation and heat resistance evaluation JEC-6147 (Electrical Society investigation standard standard), and the insulation material employ | adopted in the compressor for refrigeration and air conditioner is also according to the heat-resistant type of the said specification Is selected. However, in the case of the organic insulating material for refrigeration and air conditioning equipment, since it is used in a special environment called a refrigerant atmosphere, it is necessary to consider suppressing deformation and modification by pressure in addition to temperature. In addition, contact with polar compounds such as refrigerant and refrigeration oil, so solvent resistance, extraction resistance, thermal, chemical and mechanical stability, refrigerant resistance [crazing (fine stress generated when immersed in the refrigerant after stress Corrugated box-shaped cracks), blisters (the refrigerant absorbed in the film, bubbles in the film caused by the temperature rise), and the like.

For this reason, it is necessary to use the insulating material of high heat resistance class (E class 120 degreeC or more).

The insulation material most used in a compressor is PET (polyethylene terephthalate). As a use, the film material is used for the coil insulation with the iron core of a distribution winding motor, and the fibrous PET is used for the coating material of the coil ties and the lead wire of a motor.

As an insulation film other than this, PPS (polyphenylene sulfide), PEN (polyethylene naphthalate), PEEK (polyether ether ketone), PI (polyimide), PA (polyamide), etc. are mentioned.

Moreover, THEIC modified polyester, polyamide, polyamideimide, polyesterimide, polyesteramideimide, etc. are used for the main insulation coating material of a coil, The double-coated copper wire which double-coated polyesterimide- amideimide is preferable. Is used.

There is no problem even if it adds a lubrication improver, antioxidant, an acid trapping agent, an antifoamer, a metal deactivator, etc. to the said refrigeration oil. In particular, since polyol ester oils deteriorate due to hydrolysis in the presence of water, the combination of an antioxidant and an acid trapping agent is essential.

As antioxidant, DBPC (2, 6-di-t-butyl- p-cresol) which is a phenol type is preferable.

As the acid trapping agent, an aliphatic epoxy compound or a carbodiimide compound is generally used as a compound having an epoxy ring. In particular, the carbodiimide compound has a very high reactivity with a fatty acid and captures hydrogen ions dissociated from the fatty acid, and thus has a great effect of suppressing the hydrolysis reaction of the polyol ester oil.

Examples of the carbodiimide compound include bis (2, 6-isopropyl phenyl) carbodiimide. It is preferable that the compounding quantity of an acid trapping agent shall be 0.05-1.0 weight% with respect to refrigerator oil.

Moreover, in general, the extreme pressure agent may be mixed with the refrigerant used for the compressor. As the extreme pressure agent, tertiary phosphates such as tricredyl phosphate and triphenyl phosphate are conventionally used.

In the refrigeration and air conditioning compressor of the present invention, since the wear resistance can be improved by using the refrigerant and the refrigeration oil, it is not necessary to use an extreme pressure agent.

(1st to 12th Example)

(Refrigerator oil component)

The melt viscosity (hereinafter, simply referred to as "dissolved viscosity") in the state where the refrigerant and the refrigeration oil are dissolved becomes an important factor in increasing the efficiency of the refrigeration air conditioning compressor.

When the low temperature critical melting temperature at which the liquid-liquid two-layer separation starts to occur at low temperature is combined with a refrigerant having a temperature of −30 ° C. or lower, and the refrigerant oil is dissolved in a large amount, the melt viscosity is drastically reduced. do. When the melt viscosity in the compressor is low, not only the compression part sealing property is lowered, but also the oil film strength in the compressor sliding part decreases, so that wear progresses and the reliability of the refrigeration and air conditioning apparatus also decreases. For this reason, the adsorption property of the refrigeration oil component to the sliding part becomes an important variable.

The sliding part has many parts which consist of iron-type materials, and iron oxide is formed in the surface.

The adsorption capacity of the refrigerator oil to the iron-based material in the present specification is considered to be substantially the adsorption capacity of the refrigerator oil to iron oxide.

Based on this way of thinking, in the present embodiment by using the powder (specific surface area 1.57㎡ / g) of a mean particle size of 1㎛ Fe ₃ O ₄ (Black Oxide) were evaluated of the refrigeration oil absorption ability.

The concentration before and after adsorption of the refrigeration oil component diluted in the solvent was quantified by nuclear magnetic resonance analysis (NMR) to calculate the amount adsorbed on the iron oxide powder. Hexane was used as a solvent, and it adjusted so that each refrigeration oil component might be 0.3 mol-ppm. After 3g of iron oxide powder was collected in a 20 ml screw tube, 10 g of a solution of a refrigeration oil component was added, dispersed for 30 minutes in an ultrasonic washing machine, and subjected to 1 H-NMR analysis of the supernatant liquid after standing for 48 hours.

Where mol-ppm is ppm on the molar basis (parts per million). In other words, the mole number of the solution (mixture of solvent and solute) is the denominator, and the mole fraction is calculated using the number of moles of the solute as a molecule.

The base oil used as a refrigeration oil component is as follows. Here, 40 degreeC dynamic viscosity means dynamic viscosity in 40 degreeC.

(A) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of 2-methyl hexanoic acid / 2-ethyl hexanoic acid of pentaerythritol type | system | group): 40 degreeC dynamic viscosity 31.8mm <2> / s

(B) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of 2-ethylhexanoic acid / 3, 5, 5-trimethyl hexanoic acid of neopentyl glycol / pentaerythritol system): 40 degreeC kinematic viscosity 46.9mm <2> / s

(C) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of 2-ethylhexanoic acid / 3, 5, 5-trimethyl hexanoic acid of neopentyl glycol / pentaerythritol system): 40 degreeC kinematic viscosity 64.8mm <2> / s

(D) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of pentaerythritol 2-ethyl hexanoic acid / 3, 5, 5-trimethyl hexanoic acid): 40 degreeC dynamic viscosity 91.3mm <2> / s

(E) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of 2-ethylhexanoic acid / 3, 5, 5-trimethyl hexanoic acid of dipentaerythritol type | system | group): 40 degreeC dynamic viscosity 190mm <2> / s

(F) Hindered polyol ester oil (POE) (mixed fatty acid ester oil of 2-ethylhexanoic acid / 3, 5, 5-trimethyl hexanoic acid of dipentaerythritol system): 40 degreeC kinematic viscosity 217 mm <2> / s

(G) Hindered polyol ester oil (POE) (3, 5, 5-trimethyl hexanoic acid ester oil of dipentaerythritol system): 40 degreeC dynamic viscosity 417mm <2> / s

(H) Polyvinyl ether oil (PVE): 40 ° C kinematic viscosity 50.1 mm2 / s

(I) Polyvinyl ether oil (PVE): 40 ° C kinematic viscosity 65 mm2 / s

(J) Polyalkylene glycol oil (PAG) (polypropylene glycol dimethyl ether): 40 degreeC dynamic viscosity 112 mm <2> / s

(K) Naphthenic mineral oil: 40 ℃ kinematic viscosity 54.1㎡ / s

(L) Polyαolefin oil: 40 ° C kinematic viscosity 61.8 mm2 / s

The adsorption amount of the compound on the iron oxide powder was measured and the results are shown in Table 1.

It is understood that the amount of adsorption (adsorption capacity) to the iron oxide powder varies depending on each compound, so that the polar compound is easily adsorbed to the iron-based material.

Also in a polar compound, it turns out that compound (E), (F), and (G) which have many ester groups in a molecular structure especially have a large adsorption amount. That is, (E), (F) and (G) are 2.0 times higher than the other refrigeration oil components (A) to (D) and (H) to (L), which have an adsorption capacity for iron-based materials (iron oxide). It can be seen that.

From this, the refrigerator oil components (E), (F), and (G) are considered to be easy to form a film | membrane in a compressor sliding part.

This is considered to be for the following reason.

Oxygen of carbonyl (C = O) contained in the ester group tends to be negatively charged. On the other hand, the surface of iron oxide is generally hydrated and has a structure which has a hydroxyl group. For this reason, it is thought that the attraction force by a Coulomb force arises between hydrogen contained in the hydroxyl group on the iron oxide surface, and oxygen contained in an ester group, and it becomes easy to adsorb | suck.

From this result, (E), (F) and (G) were used as the additive polyol ester oil in this invention.

(Thirteenth to 25th Examples)

The refrigerant and the refrigeration oil are enclosed in the refrigeration air conditioning compressor.

The compatibility between the refrigerant and the refrigeration oil is one of important characteristics in ensuring the reliability of the compressor, such as returning oil from the refrigeration cycle to the compressor (securing the flow rate inside the compressor) or lowering the heat exchange efficiency. However, since the refrigerant is present, the melt viscosity of the mixed liquid is drastically changed depending on the amount of the refrigerant dissolved in the refrigerator oil. When the amount of the melt is large, the viscosity decrease of the oil becomes remarkable, and a sufficient oil film strength cannot be obtained in the sliding part. The function as the seal member of the compression section is impaired.

The compatibility evaluation of refrigerant | coolant and refrigeration oil was measured according to JISKK2211.

The refrigerant | coolant was enclosed in the pressure-resistant glass container in arbitrary oil concentration, the temperature was changed, and the contents were observed. At this time, it was determined that the contents were cloudy and separated in two layers, and when they were transparent, they were dissolved. The oil concentration dependence of the temperature separated by these two layers becomes a curve which generally has a maximum value. This maximum value was made into the low temperature side critical melting temperature. The low temperature side critical melting temperature is a variable indicating the degree of compatibility between the refrigerant and the refrigeration oil.

Table 2 shows the results of selecting refrigeration oil compatible with each refrigerant and measuring the critical melting temperature at the low temperature side.

Depending on the degree of compatibility between the refrigerant and the refrigeration oil, the low temperature side critical dissolution temperature varies greatly. In particular, when HFO1234yf, propane, propylene, or fluoroethane is used as the refrigerant, the solubility in refrigeration oil is very high, causing a significant decrease in viscosity in the operating conditions of the compressor. Usually, although the viscosity grade of refrigeration oil is raised and respond | corresponds, in the operating conditions of the refrigeration and air conditioning compressor, the amount of refrigerant melted increases with temperature and pressure, and the viscosity does not actually increase so much.

(26th to 31st Examples, 1st to 6th Comparative Examples)

The lubricity of the refrigeration oil was evaluated using the shell-type sand dune friction wear tester.

Using a 1 / 2-inch SUJ2 steel ball as a test piece, the wear tread diameter (average of three) and the coefficient of friction of the fixed test piece were measured after testing at a load of 280 N, a temperature of 120 ° C., a rotational speed of 1200 / min, and a time of 10 minutes. did.

As the main subject of the refrigeration oil, a polyol ester oil (A) to (D), a polyvinyl ether oil (I), and a naphthenic mineral oil (K) were used, and a compound containing 5.0 wt% of the added polyol ester oil (F) was added thereto. Evaluated.

As a comparative example, the polyol ester oils (A) to (D) were evaluated individually in the case of polyvinyl ether oil (I) alone and in the case of naphthenic mineral oil (K) alone.

Table 3 shows the results of evaluating the lubricity of each refrigerator oil.

From this result, the refrigeration oil of the 1st-4th comparative example which does not mix | blend the addition polyol ester oil (F) has a large wear scar diameter, and has a high friction coefficient. In the case of the fifth and sixth comparative examples, the test was stopped because the sieve occurred immediately after the start of the test.

On the other hand, in the refrigeration oil which mix | blended the addition polyol ester oil (F) shown in Examples 26-31, regardless of the kind of oil of the refrigeration oil, abrasion trace diameter and a friction coefficient are suppressed and the lubricity improves The effect was obtained. This is because the adsorption capacity of the added polyol ester oil (F) to the iron-based material is larger than that of the refrigeration oil, so that the friction surface becomes low surface energy, and the effect of reducing the wear resistance and the friction coefficient is obtained. No refrigeration occurred in the refrigeration oil main polyvinyl ether oil (I) and naphthenic mineral oil (K). In particular, when the refrigeration oil main subject is polyvinyl ether oil (I) or naphthenic mineral oil (K) which has less adsorption amount compared to the added polyol ester oil (F) as shown in Table 1, the added polyol ester oil (F) is a friction surface. Since it becomes easy to adsorb | suck to, the effect of a lubricity improvement is easy to be acquired.

(32th to 37th Examples, 7th to 8th Comparative Examples)

In order to confirm the effect of the added polyol ester oils (E) and (G), the same test as in Example 26 was carried out by changing the type and amount of the added polyol ester oil by using a shell-type sand dune friction wear tester.

Table 4 shows the results of evaluating the lubricity of each refrigerator oil.

The refrigeration oil of Examples 32-37 shown in this table is a wear mark diameter and a friction coefficient compared with the refrigeration oil of the 3rd comparative example (shown in Table 3) which uses (C) as a main subject of refrigeration oil, and does not add an additive. Was suppressed and the improvement effect of lubricity was confirmed.

In addition, in the case of the seventh and eighth comparative examples, in which the addition amount of the added polyol ester oil (F) is small, the wear scar diameter is large and the friction coefficient is high, so that the effect of improving lubricity is hardly expressed. On the other hand, in the refrigerator oil which mix | blended 1.0 weight% or more of the addition polyol ester oil (F) shown in Examples 32-35 with respect to the main subject of refrigerator oil, abrasion mark diameter and a friction coefficient are suppressed, and the lubricity improves the effect Was obtained.

(38th, 39th Example, 9th, 10th Comparative Example)

Fig. 1 shows an outline of a room air conditioner for both heating and cooling used in the present embodiment.

When cooling the room, the high temperature and high pressure refrigerant gas (encapsulated refrigerant) compressed adiabatically in the discharge pipe of the compressor 1 is an outdoor heat exchanger 3 (used as a condensing means) through the four-way valve 2. It cools in and becomes a high pressure liquid refrigerant. The refrigerant is expanded by means of expansion means 4 (e.g., a capillary tube, a thermal expansion valve, etc., also called a decompression section), and becomes a low temperature low pressure liquid containing some gas to evaporate the indoor heat exchanger 5 (evaporation). Used as a means) to obtain heat from the indoor air and back to the compressor 1 via a four-way valve 2 in the state of low temperature gas. When the room is heated, the flow of the refrigerant is changed in the opposite direction by the four-way valve 2, and the opposite action is performed.

In this embodiment, a scroll compressor was used as the compressor.

2 shows the schematic structure.

The compressor is a swivel scroll member 9 having a spiral wrap 8 standing upright on the end plate 7 of the fixed scroll member 6 and a wrap 10 substantially the same shape as the fixed scroll member 6. ) Is engaged with the wrap 8 and the wrap 10 to face each other to form a compression mechanism, and the swing scroll member 9 is pivoted by the crankshaft 11. Among the compression chambers 12a and 12b formed by the fixed scroll member 6 and the swinging scroll member 9, the compression chamber located at the outermost side has a fixed scroll member 6 while the volume gradually decreases with the swinging movement. ) And moving toward the center constituted by the turning scroll member 9. When the compression chambers 12a and 12b reach the vicinity of the center portion composed of the fixed scroll member 6 and the swinging scroll member 9, the compression chambers 12a and 12b communicate with the discharge port 13, so that the compression chamber 12a 12b), the compressed gas is discharged from the discharge pipe 16 out of the compressor.

In the compressor of this embodiment, the electric motor 17 is incorporated in the pressure vessel 15, and the compressor rotates the crankshaft 11 at a rotational speed according to a constant speed or a voltage controlled by an inverter (not shown). , The compression operation is performed. Moreover, the oil storage part 20 is provided below the motor 17, and the oil of the oil storage part 20 turns scrolling through the oil hole 19 provided in the crankshaft 11 by the pressure difference. It is provided for the lubrication of the sliding part of the member 9, the crankshaft 11, the sliding bearing 18, and the like.

In the thirty-eighth, thirty-ninth, ninth, and tenth comparative examples, a practical test performed by using an air conditioner shown in FIG. 1 to operate an indoor unit in a constant temperature room (35 ° C., 75% humidity) for 2160 hours. Was performed.

Heat-resistant PET film (Class B 130 ° C) was used for coil insulation with the iron core of the motor 17, and double-coated copper wire coated with a double coat of polyesterimide-amideimide was used for coil main insulation.

In evaluating the room air conditioner, attention is paid to the wear state of the scroll compressor, and the gap increase amount due to the wear between the frame 14 and the crankshaft 11 (between the frame 14 and the crankshaft 11) before and after the test. Was measured. As the gap increase amount between the frame 14 and the crankshaft 11 (hereinafter also referred to as between the frame and the shaft) increases, it indicates that the wear amount is large, and in general, vibration or noise increases with the increase in the gap increase amount.

HFO1234yf (2, 3, 3, 3-tetrafluoropropene) was used alone as the refrigerant. HFO1234yf is a low pressure refrigerant and the pressure loss in the piping is large because the refrigerant circulation amount is small. For this reason, it evaluated by the specification which made the compressor exhaust volume double the normal and enlarged the diameter of a connection pipe, increased the number of passes of a heat exchanger, and adjusted distribution balance.

In the refrigeration air conditioning cycle using HFO1234yf and HFO1234ze and the mixed refrigerant containing them, the compatibility between the refrigerant and the refrigeration oil is an important characteristic for securing the oil return amount to the compressor. In the refrigeration air conditioning cycle, the refrigerant oil must be circulated like the refrigerant. When the compatibility is low, the refrigeration oil discharged by the mechanical element from the compressor is not circulated, and in particular, the oil separated in the low temperature portion stays, so that the amount of oil in the compressor decreases, which causes lubricating oil problems in the sliding parts. For this reason, it is preferable that a refrigerant | coolant and refrigeration oil melt | dissolve in the operating condition temperature range in a cycle.

With respect to HFO1234yf, hydrocarbon oils such as naphthenic mineral oil, paraffinic mineral oil, alkyl benzene oil, and polyαolefin oil are difficult to be compatible, and therefore, polyol ester oil or polyvinyl ether oil is preferable.

In Example 38, evaluation was performed using the refrigerator oil [(C) + (F)] employed in Example 28 having compatibility with HFO1234yf. In Example 39, evaluation was performed using the refrigerator oil [(I) + (F)] employed in Example 30.

Using (C) or (I) as the main subject of refrigeration oil, 5% by weight of (F) having a high adsorption capacity was blended with these, and the kinematic viscosity at 40 ° C was 68.6 mm 2 / s or 68.9 mm 2 / s. The test was carried out with freezer oil.

In the ninth and tenth comparative examples, in the thirty-eighth and thirty-ninth examples, the refrigerating oil was not formulated with the added polyol ester oil.

The target value of this test is 100 micrometers or less of clearance increase by the abrasion between shafts in a frame after a test.

Table 5 shows the results of the 38th, 39th examples, and the 9th and 10th comparative examples.

As apparent from Table 5, the room air conditioners of the 38th and 39th embodiments can significantly reduce the amount of increase in the gap between the shafts in the frame and suppress wear, as compared with the ninth and tenth comparative examples. High reliability can be obtained in an air conditioner.

Table 5 also shows the effect of measuring the viscosity and the efficiency in the cooling intermediate condition with respect to the combination of the refrigerant and the refrigeration oil.

The viscosity measurement used the piston type viscometer of Japan Control.

In addition, efficiency was expressed as the ratio using the 9th comparative example as the reference | standard 100 using the performance coefficient (COP: Coefficient_of_Performance).

From this result, in the 9th and 10th comparative examples, the fall of a viscosity has generate | occur | produced and sufficient sealing property is not acquired in a compression part. In contrast, in the 38th and 39th examples, the viscosity is increased.

In addition, as shown in the 28th and 30th examples of Table 3, since the friction suppressing effect by the added polyol ester oil was expressed, the coefficient of performance was improved as compared with the ninth comparative example (reference 1).

As a result of the above example, it was found that a refrigeration air conditioning apparatus capable of suppressing wear of the compressor and sufficiently securing long-term insulation reliability can be obtained.

Although not shown in the drawing, the same practicality is achieved in the combination of the refrigerant refrigerant HFO1234yf and HFC32 (20 wt% and 40 wt%) and the refrigerant oil [(C) + (F)] employed in Example 28. Although it evaluated by the test, the result similar to the 38th and 39th Example was obtained, the effect was acquired even if a mixed refrigerant was used, and it confirmed that there was no problem.

(Examples 40-42, Eleventh-13 Comparative Examples)

In Examples 40-42, propane and R410A were used for the refrigerant | coolant, the refrigeration cycle suitable for each refrigerant | coolant was comprised, and it evaluated by the practical skill test similar to Example 38.

In Example 40, the refrigerant oil which mix | blended 5.0 weight% of propane as a refrigerant | coolant, (C) as a main body of refrigeration oil, and (F) as addition polyol ester oil was used, respectively.

In Example 41, the refrigerant oil which mix | blended 5.0 weight% of propane as refrigerant | coolant, (K) as main body refrigeration oil, and (F) as addition polyol ester oil was used, respectively.

In the 42nd Example, the refrigerator oil which mix | blended R410A as refrigerant | coolant, (C) as main body of refrigeration oil, and 5.0 weight% of (F) as addition polyol ester oil was used, respectively.

In Comparative Examples 40-42, the refrigerator oil to which the additional polyol ester oil was not mix | blended was evaluated, respectively.

The evaluation results are shown in Table 5.

Propane has a high solubility in polyol ester oil, mineral oil and the like, as shown in the evaluation results of compatibility in Table 2, and causes a significant decrease in viscosity in the compressor. In addition, since the halogen structure is not included in the molecular structure, iron halides that contribute to lubricity at the frictional sites are not produced, and as shown in the 11th and 12th comparative examples, The gap increase amount is greatly increased.

On the other hand, as shown in the forty-fourth and forty-first embodiments, for the combination in which the additive polyol ester oil (F) is added to the main body of the refrigeration oil, the amount of increase in the gap due to abrasion between the shafts in the frame is greatly reduced, thereby reducing friction. By relaxing, the coefficient of performance improved compared with the eleventh comparative example (reference 2).

In addition, in the forty-second example in which R410A was used for the refrigerant, the amount of increase in gap due to abrasion between the shafts in the frame was suppressed as compared with the thirteenth comparative example (reference 3), and the coefficient of performance was also improved.

From this, the same effect can be obtained also in refrigerant | coolants, such as difluoro methane, fluoroethane, and propylene, regardless of a kind of refrigerant | coolant.

In addition, the same effects can be obtained in a rotary compressor, a twin rotary compressor, a two-stage compression rotary compressor, and a swing compressor in which rollers and vanes are integrated.

The present invention is applicable to a refrigerant compressor for a refrigeration air conditioner and a refrigeration air conditioner.

1: Compressor
2: 4 way valve
3: outdoor heat exchanger
4: expansion means
5: indoor heat exchanger
6: fixed scroll member
7: end plate
8: wrap
9: turning scroll member
10: wrap
11: crankshaft
12a, 12b: compression chamber
13 discharge port
14: frame
15: pressure vessel
16: discharge pipe
17: electric motor
18: sliding bearing
19: oil hole
20: oil reservoir

Claims (11)

In a refrigerant containing 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene or difluoro methane or an encapsulated refrigerant R410A, the following formulas (1) and ( The refrigeration oil main body containing at least 1 sort (s) of base oil chosen from the group which consists of polyol ester oil represented by 2) (wherein R <_1> represents a C5-C9 alkyl group), and addition shown by following General formula (3) It is a refrigeration air-conditioning compressor which mixed and enclosed the refrigeration oil containing polyol ester oil (wherein, R <_2> represents a C7-9 alkyl group), The composition of the said addition polyol ester oil in the said refrigeration oil is 1-30. Weight percent,
The kinematic viscosity at 40 ° C of the refrigerating oil main is 25 to 120 mm 2 / s, and the adsorption capacity of the added polyol ester oil to the iron-based material is two or more times higher than that of the refrigerating oil main. Air conditioning compressor.
[Formula 1]

(2)

(3)

The kinematic viscosity at 40 ° C of the added polyol ester oil is 180 mm 2 / s or more, characterized in that the compressor for refrigeration and air conditioning. A refrigeration air conditioning compressor according to claim 1, a heat exchanger for dissipating heat of the encapsulated refrigerant discharged from the refrigeration air conditioning compressor, a decompression unit for depressurizing the encapsulated refrigerant flowing out of the heat exchanger, and And a heat exchanger for heating the encapsulated refrigerant decompressed in the decompression section. delete Mineral oil or polyvinyl ether oil in enclosed refrigerants which are refrigerants comprising 2, 3, 3, 3-tetrafluoropropene, 1, 3, 3, 3-tetrafluoropropene, propane, propylene or fluoroethane Or at least one kind of base oil selected from the group consisting of polyol ester oils represented by the following formulas (1) and (2), wherein R ₁ represents an alkyl group having 5 to 9 carbon atoms, For refrigeration air conditioning, which is a mixture of a refrigeration oil main material having a temperature of -30 ° C. or less and a refrigeration oil containing an additional polyol ester oil represented by the following general formula (3), wherein R ₂ represents an alkyl group having 7 to 9 carbon atoms. A compressor, wherein the composition of the added polyol ester oil in the refrigerator oil is 1 to 30% by weight,
The kinematic viscosity at 40 ° C of the refrigerating oil main is 25 to 120 mm 2 / s, and the adsorption capacity of the added polyol ester oil to the iron-based material is two or more times higher than that of the refrigerating oil main. Air conditioning compressor.
[Formula 1]

(2)

(3)

The kinematic viscosity at 40 ° C of the added polyol ester oil is 180 mm 2 / s or more, characterized in that the compressor for refrigeration and air conditioning. A refrigeration air conditioning compressor according to claim 5, a heat exchanger for dissipating heat of the encapsulated refrigerant discharged from the refrigeration air conditioning compressor, a decompression unit for depressurizing the encapsulated refrigerant flowing out of the heat exchanger, and And a heat exchanger for heating the encapsulated refrigerant decompressed in the decompression section. delete A group consisting of polyol ester oils represented by the following formulas (1) and (2) in a refrigerant having a global warming coefficient of 1000 or less, or a refrigerant for R410A, wherein R ₁ represents an alkyl group having 5 to 9 carbon atoms. A refrigeration oil main body containing at least one kind of base oil selected from the group having a kinematic viscosity at 40 ° C of 25 to 120 mm 2 / s, and an additional polyol ester oil represented by the following general formula (3), wherein R ₂ has 7 carbon atoms A refrigeration air-conditioning compressor in which a refrigeration oil containing an alkyl group of 9 to 9 is mixed and enclosed, wherein the composition of the added polyol ester oil in the refrigeration oil is 1 to 30% by weight,
Adsorption capacity of the added polyol ester oil to the iron-based material, characterized in that more than twice as high as the refrigeration oil main, compressor for refrigeration air conditioning.
[Formula 1]

(2)

(3)

A refrigeration air conditioning compressor according to claim 9, a heat exchanger for dissipating heat from the refrigeration air conditioning refrigerant discharged from said refrigeration air conditioning compressor, and a decompression for decompressing said refrigerant for cooling air conditioning flowing out of said heat exchanger. And a heat exchanger for heating the refrigerant for cooling air-conditioning reduced in the pressure-reducing unit. delete

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