Patent Application
20180209707
One or more embodiments of the present invention relate to a method of manufacturing an evaporator for a refrigeration apparatus.
Conventionally, copper is sometimes used in a state where its surface is covered with a rust inhibitor in order to reduce its corrosion.
For example, in the examples described in Patent Document 1 (Japanese Unexamined Patent Publication No. 2011-184714), an example in which a rust preventive film is provided on the surface of a copper wire rod is introduced. The rust inhibitor used for forming the rust preventive film is the one obtained by dissolving benzotriazole in water, alcohol, and other.
Here, a copper piping used in a refrigeration apparatus often suffers from not only rusting on the surface, but also from ant nest-shaped corrosion that occurs on the outer surface due to dew condensation water generated during refrigeration cycles or rainwater or the like, and thereby a hole penetrating the copper piping may occur. If the hole is formed in the copper piping in this way, the refrigerant circulating inside will leak out.
For this reason, it is required to form the rust preventive film on the outer surface of the copper piping used in the refrigeration apparatus to reduce corrosion.
However, since the benzotriazole described in Patent Document 1 is water-soluble, when the piping is used in an environment where dew condensation water is generated or in an environment the piping is exposed to rainwater, the benzotriazole dissolves out and the rust prevention effect may decrease.
One or more embodiments of the present invention provide a method of manufacturing an evaporator for a refrigeration apparatus capable of reducing corrosion.
A method of manufacturing an evaporator for a refrigeration apparatus according to a first aspect includes a first step, a second step, and a third step. In the first step, a coating agent containing a benzotriazole-based compound having a structure represented by the following formula (I):
(wherein R1 to R4 each independently represent hydrogen or a methyl group, and R5 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms or (CH2)n—N—R6-R7, n being an integer of 1 to 3, R6 and R7 being each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms), and a metal working oil is applied to an outer surface of a heat transfer pipe to form a rust preventive film.
In the second step, the heat transfer pipe having the rust preventive film formed thereon is inserted into a hole of a heat transfer fin. In the third step, the heat transfer pipe inserted the heat transfer fin is expanded.
In this method of manufacturing the evaporator for a refrigeration apparatus, even when the manufactured evaporator may be exposed to dew condensation water or rainwater, since the benzotriazole-based compound is difficult to elute, it becomes possible to sustain the rust prevention effect.
A method of manufacturing an evaporator for a refrigeration apparatus according to a second aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to the first aspect, and the heat transfer pipe is made of copper or a copper alloy. The heat transfer fin is made of aluminum or an aluminum alloy. The heat transfer fins into which the heat transfer pipe is inserted in the second step have the metal working oil applied thereon.
A method of manufacturing an evaporator for a refrigeration apparatus according to a third aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to the first aspect or the second aspect, and R5 is CH2—N—(CH2—CH(C2H5)—CH2—CH2—CH2—CH3)2.
In this method of manufacturing the evaporator for the refrigeration apparatus, it becomes possible to sufficiently dissolve the benzotriazole-based compound in the metal working oil.
A method of manufacturing an evaporator for a refrigeration apparatus according to a fourth aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to the third aspect, and the benzotriazole-based compound is a mixture of N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methanamine and N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methanamine.
A method of manufacturing an evaporator for a refrigeration apparatus according to a fifth aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to the fourth aspect, and the blending ratio of the mixture in the coating agent is 0.2% by weight or more and 1.0% by weight or less.
In this method of manufacturing the evaporator for the refrigeration apparatus, the occurrence of the origin of a corrosion hole that may develop into a through hole can be effectively reduced.
A method of manufacturing an evaporator for a refrigeration apparatus according to a sixth aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to a third aspect, and the benzotriazole-based compound is N,N-bis(2-ethylhexyl)-1H-benzotriazole-1-methanamine. The blending ratio of the benzotriazole-based compound in the coating agent is 0.4% by weight or more and 1.0% by weight or less.
In this method of manufacturing the evaporator for the refrigeration apparatus, the occurrence of the origin of the corrosion hole that may develop into the through hole can be effectively reduced.
A method of manufacturing an evaporator for a refrigeration apparatus according to a seventh aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to any one of the first aspect to the sixth aspect, and it further includes a step of drying the applied coating agent. In the drying step, the drying is performed under a condition of a surface temperature of 130° C. or more and 200° C. or less.
A method of manufacturing an evaporator for a refrigeration apparatus according to an eighth aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to any one of the first aspect to the seventh aspect, and the metal working oil is volatile.
In this method of manufacturing the evaporator for the refrigeration apparatus, it becomes possible to make the metal working oil unlikely to remain on the surface of the piping body by drying the coating agent applied to the piping body.
A method of manufacturing an evaporator for a refrigeration apparatus according to a ninth aspect is the method of manufacturing the evaporator for the refrigeration apparatus according to any one of the first aspect to the eighth aspect, and it further includes a step of bending the heat transfer pipe coated with the coating agent by 180 degrees, between the first step and the second step.
In the method of manufacturing the evaporator for the refrigeration apparatus according to the first aspect, even when the manufactured evaporator is exposed to dew condensation water or rainwater, since the benzotriazole-based compound is difficult to elute, the rust prevention effect can be sustained.
In the method of manufacturing the evaporator for the refrigeration apparatus according to the third aspect, it becomes possible to sufficiently dissolve the benzotriazole-based compound in the metal working oil.
In the method of manufacturing the evaporator for the refrigeration apparatus according to the fifth aspect, the occurrence of the origin of the corrosion hole that may develop into the through hole can be effectively reduced.
In the method of manufacturing the evaporator for the refrigeration apparatus according to the sixth aspect, the occurrence of the origin of the corrosion hole that may develop into the through hole can be effectively reduced.
In the method of manufacturing the evaporator for the refrigeration apparatus according to the eighth aspect, it becomes possible to make the metal working oil unlikely to remain on the surface of the piping body.
Hereinafter, one or more embodiments of each of a method of manufacturing a refrigerant piping, a refrigerant piping, and an air conditioner will be described as an example, but the present invention is not limited thereto.
The refrigerant piping has a piping body and a rust preventive film.
The piping body is a cylindrical piping, and is made of copper or a copper alloy. Examples of the copper or copper alloy include, for example, pure copper, brass, and bronze. Here, as the copper alloy, an alloy containing copper principally may be used.
The rust preventive film is formed by applying a coating agent to an outer surface of the piping body.
Here, the rust preventing film may be obtained by drying the coating agent applied to the outer surface of the piping body. As a method of drying, heat drying may be performed, such that the surface temperature reaches 130° C. or more and 200° C. or less.
The coating agent is obtained by dissolving a benzotriazole-based compound in a metal working oil. The method of dissolving the benzotriazole-based compound in the metal working oil is not particularly limited, but the benzotriazole-based compound may be dispersed by stirring with a magnetic stirrer or the like, for example.
The benzotriazole-based compound has a structure represented by the following formula (I):
(wherein R1 to R4 each independently represent a hydrogen or a methyl group, and R5 represents an aliphatic hydrocarbon group having 1 to 18 carbon atoms or (CH2)n—N—R6-R7 (n is an integer of 1 to 3, R6 and R7 are each independently an aliphatic hydrocarbon group having 1 to 18 carbon atoms)). The benzotriazole-based compound may be constituted by one kind of a mixture or two or more kinds of mixtures.
In the above formula, R1 to R4 may be each independently the hydrogen or the methyl group and R5 is the aliphatic hydrocarbon group having 8 to 18 carbon atoms or (CH2)n—N—R6-R7 (n is the integer of 1 to 3, and R6 and R7 are each independently the aliphatic hydrocarbon group having from 8 to 18 carbon atoms) from the viewpoint of increasing the solubility into the metal working oil.
Here, examples of the benzotriazole-based compound include, for example, N,N-dimethylbenzotriazole-1-methanamine, N,N-diethylbenzotriazole-1-methanamine, N,N-dipropylbenzotriazole-1-methanamine, N,N-dibutylbenzotriazole-1-methanamine, N,N-dihexylbenzotriazole-1-methanamine, N,N-dioctylbenzotriazole-1-methanamine, 1-[N,N-bis(2-ethylhexyl)aminomethyl]-1H-benzotriazole, N,N-dimethyl-4-benzotriazole-1-methanamine, N,N-dimethyl-5-benzotriazole-1-methanamine, N,N-diethyl-4-benzotriazole-1-methanamine, N,N-diethyl-5-benzotriazole-1-methanamine, N,N-dipropyl-4-benzotriazole-1-methanamine, N,N-dipropyl-5-benzotriazol-1-methanamine, N,N-dibutyl-4-benzotriazol-1-methanamine, N,N-dibutyl-5-benzotriazol-1-methanamine, N,N-dihexyl-4-benzotriazole-1-methanamine, N,N-dihexyl-5-benzotriazole-1-methanamine, N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methanamine, N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methanamine, N,N-dioleyl-4-methylbenzotriazole-1-methanamine, N,N-dioleyl-5-methylbenzotriazole-1-methanamine, N,N-distearyl-4-methylbenzotriazole-1-methanamine, N,N-distearyl-5-methylbenzotriazole-1-methanamine, and a mixture thereof.
Examples of benzotriazole-based compounds include N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methanamine (CAS:80584-90-3), N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methanamine (CAS:80595-74-0), a mixture thereof, or 1-[N,N-bis(2-ethylhexyl)aminomethyl]-1H-benzotriazole (CAS:80301-64-0).
The benzotriazole-based compound having the above structure is composed of a BTA moiety which is relatively hydrophilic benzotriazole and a lipophilic moiety which is relatively lipophilic.
As the benzotriazole-based compound, a commercially available product may be used. Such a commercially available product is not particularly limited, but examples thereof include OA-386 (product name) manufactured by Daiwa Fine Chemicals Co., Ltd., BT-LX (product name) manufactured by Johoku Chemical Co., Ltd., and the like.
The lower limit of the blend concentration of the benzotriazole-based compound in the coating agent may be 0.1 wt % or more from the viewpoint of making corrosion holes less likely to occur. The upper limit of the blend concentration of the benzotriazole-based compound in the coating agent may be 1 wt % or less, for example 0.5 wt % or less, because no higher limit than this seems to increase the effect of reducing the occurrence of corrosion holes, and because this limit can keep the cost low.
When a mixture of N,N-bis(2-ethylhexyl)-4-methyl-1H-benzotriazole-1-methanamine and N,N-bis(2-ethylhexyl)-5-methyl-1H-benzotriazole-1-methanamine is used as the benzotriazole-based compound, the blend concentration of the mixture in the coating agent may be 0.2 wt % or more and 0.6 wt % or less.
Regardless of the type of the benzotriazole-based compound, from the viewpoint of reducing the occurrence of corrosion holes, the blend concentration of the benzotriazole-based compound in the coating agent may be 0.4 wt % or more and 1.0 wt % or less, for example 0.4 wt % or more and 0.6 wt % or less.
The metal working oil is not particularly limited, but a processing oil may be used for metal processing and is not corrosive to (unlikely to rust) metals such as aluminum and copper.
The metal working oil may volatilize at 180° C. or higher under atmospheric pressure so that it can be substantially burned off by heating and drying after processing. When the metal working oil can be substantially burned out in this way by heating and drying after processing, it is possible to reduce the generation of organic substances such as formic acid caused by deterioration or decomposition of the residual substances, leading to reduction of ant nest-shaped corrosion that is easily caused by the organic substances.
Note that when only the benzotriazole-based compound is applied to the piping body, the high viscosity tends to cause material loss during processing, and lowers the coating efficiency, and thereby the benzotriazole-based compound is coated in the state of being dissolved in the metal working oil.
The metal working oil may have a kinematic viscosity of, at 40° C., 1.0 mm2/s or more and 5.0 mm2/s or less, for example 1.2 mm2/s or more and 2.5 mm2/s or less. The kinematic viscosity is a value measured in accordance with JIS K2283.
Further, the metal working oil may have a density of, at 15° C., 0.75 g/cm3 or more and 0.79 g/cm3 or less. The density is a value measured in accordance with JIS K2249.
Also, the metal working oil may have an acid value of 0 mgKOH/g. Such a metal working oil may contain no lower carboxylic acid such as formic acid or acetic acid.
A commercially available product may be used as the above metal working oil. Examples of the commercially available product include Daphne Punch Oil AF-A series manufactured by Idemitsu Kosan Co., Ltd., and Proformer series manufactured by N S Lubricants Co., Ltd. Among them, the product names “AF-2A”, “AF-2AS” manufactured by Idemitsu Kosan Co., Ltd., and the product names “Proformer RF520”, “Proformer RF510” manufactured by N⋅S Lubricants, Co., Ltd. may be used. The product name “AF-2A” manufactured by Idemitsu Kosan Co., Ltd. may be used.
The refrigerant piping is manufactured, for example, as follows.
First, the above-described piping body composed of copper or copper alloy, the above-described benzotriazole-based compound, and the metal working oil are prepared.
The prepared benzotriazole-based compound is dissolved in the metal working oil to obtain the coating agent.
This coating agent is applied to the outer surface of the piping body to form the rust preventive film.
A side sectional view of the refrigerant piping 50 obtained as described above is shown in
Note that the coating agent may be applied directly to the outer surface of the prepared piping body, but the coating application may be conducted after the outer surface of the piping body undergoes some pretreatment. Here, examples of the pretreatment of the piping body include a degreasing treatment using a solvent such as acetone and a degreasing treatment using an alkaline liquid.
Here, in order to form the rust preventive film, the coating agent applied to the outer surface of the piping body may be heated and dried. After such heating and drying, the condition is not limited, but nitrogen atoms at a position farthest from a benzene ring in a benzotriazole moiety of the benzotriazole-based compound are considered to be bound to the copper of the piping body by coordination bond.
This refrigerant piping can be used as a pipe for flowing a refrigerant inside, but the section of the refrigerant circuit where the piping is used is not particularly limited, and it may be used, for example, as a heat transfer pipe of a heat exchanger, or as a connecting pipe that connects between the main components (compressor, expansion valve, heat exchanger and the like) in the refrigerant circuit.
When the refrigerant piping is used as the heat transfer pipe in the heat exchanger of the air conditioner, the coating agent may be applied to the heat transfer fins through which the heat transfer pipe is penetrated. Hereinafter, a method of manufacturing the heat exchanger is described in a case where the refrigerant piping is used as a heat transfer pipe in a heat exchanger of an air conditioner.
First, the coating agent obtained by dissolving the benzotriazole-based compound in the metal working oil is applied to the outer surface of the piping body 51. Then, as shown in
Here, as shown in
As shown in
The plurality of refrigerant pipings 50 and the plurality of heat transfer fins 60 obtained as described above are heated and dried. The surface temperature of the refrigerant pipings 50 and the heat transfer fins 60 at the time of heating and drying is not particularly limited, but it may be 130° C. or more and 200° C. or less, for example. Here, in the coating agent applied on the surface of the piping body 51 of the refrigerant pipings 50, the metal working oil is substantially burned off by volatilization or the like. In addition, the metal working oil and the other agent applied to the surface of the heat transfer fins 60 are also substantially burned off by volatilization or the like.
Note that, as shown in
An example of an air conditioner 100 including the heat exchangers 23 and 31 having the above-described refrigerant pipings is described below with reference to
The air conditioner 100 includes a refrigerant circuit 10, an outdoor fan 24, an indoor fan 32, and a control unit 7.
The refrigerant circuit 10 has a compressor 21, a four-way switching valve 22, an outdoor heat exchanger 23, an expansion valve 25, and an indoor heat exchanger 31. The refrigerant circuit 10 is configured to switch between cooling operation and heating operation by switching the connection state of the four-way switching valve 22.
Note that the indoor heat exchanger 31 and the indoor fan 32 are provided inside the indoor unit 30 that is to be installed in the air conditioning target space. The compressor 21, the four-way switching valve 22, the outdoor heat exchanger 23, the expansion valve 25, the outdoor fan 24, and the control unit 7 are provided inside the outdoor unit 20 that is to be installed outside an air conditioning target space.
During the cooling operation, the refrigerant discharged from the compressor 21 passes through one of the connection ports of the four-way switching valve 22 and is then sent to the outdoor heat exchanger 23 functioning as a radiator of the refrigerant. The refrigerant radiated heat in the outdoor heat exchanger 23 is decompressed when passing through the expansion valve 25 and sent to the indoor heat exchanger 31 functioning as an evaporator of the refrigerant. The refrigerant evaporated in the indoor heat exchanger 31 passes through another one of the connection ports of the four-way switching valve 22 and is sucked into the compressor 21 again.
During the heating operation, the refrigerant discharged from the compressor 21 passes through one of the connection ports of the four-way switching valve 22 and is then sent to the indoor heat exchanger 31 functioning as a radiator of the refrigerant. The refrigerant radiated heat in the indoor heat exchanger 31 is decompressed when passing through the expansion valve 25 and sent to the outdoor heat exchanger 23 functioning as an evaporator of the refrigerant. The refrigerant evaporated in the outdoor heat exchanger 23 passes through another one of the connection ports of the four-way switching valve 22 and is sucked into the compressor 21 again.
Note that the control unit 7 controls the drive frequency of the compressor 21, the valve opening degree of the expansion valve 25, the air volume of the outdoor fan 24, the air volume of the indoor fan 32, and the like, based on detection information of various sensors (not shown).
Examples and Comparative Examples of refrigerant piping are shown below, but the present invention is not limited thereto.
The coating agent was obtained by dissolving the benzotriazole-based compound of the product name OA-386 manufactured by Daiwa Fine Chemicals Co., Ltd. in the metalworking oil of the product name AF-2A manufactured by Idemitsu Kosan Co., Ltd. The coating agent was applied to the outer surface of a grooved copper pipe manufactured by Shanghai Longyang Precise Composite Copper Pipe Co., Ltd. as a piping body, and was dried for 3 minutes in an environment of 130° C. to obtain the refrigerant piping.
Here, an example in which the weight ratio of the benzotriazole-based compound in the coating agent was 0.1 wt % is referred to as Example 1a, an example in which the weight ratio was 0.2 wt % is referred to as Example 1b, an example in which the weight ratio was 0.3 wt % is referred to as Example 1c, an example in which the weight ratio was 0.4 wt % is referred as Example 1d, an example in which the weight ratio was 0.5 wt % is referred to as Example 1e, and an example not blended with the benzotriazole-based compound is referred to as Comparative Example 1.
The coating agent was obtained by dissolving the benzotriazole-based compound of the product name BT-LX manufactured by Johoku Chemical Industry Co., Ltd. in the metalworking oil with the product name AF-2A manufactured by Idemitsu Kosan Co., Ltd. The coating agent was applied to the outer surface of the grooved copper pipe manufactured by Shanghai Longyang Precise Composite Copper Pipe Co., Ltd. as a piping body, and was dried for 3 minutes in the environment of 130° C. to obtain the refrigerant piping.
Here, an example in which the weight ratio of the benzotriazole-based compound in the coating agent was 0.1 wt % is referred to as Example 2a, an example in which the weight ratio was 0.2 wt % is referred to as Example 2b, an example in which the weight ratio was 0.3 wt % is referred to as Example 2c, an example in which the weight ratio was 0.4 wt % is referred to as Example 2d, and an example in which the weight ratio was 0.5 wt % is referred to as Example 2e.
For each of these Examples 1a to 1e, 2a to 2e, and Comparative Example 1, a test was conducted to check the degree of corrosion occurrence after exposure to the environment shown in
As shown in
Here, in Comparative Example 1, nine refrigerant pipings 50 of the same condition were prepared and tested, and in Examples 1a to 1e and 2a to 2e, eight refrigerant pipings 50 of the same condition were prepared and tested. Note that it was believed that formic acid would be generated from the organic substances such as the hot melt resin 93 in the sealed spaces to cause corrosion of the refrigerant pipings 50.
Whether corrosion holes (origins) occurred or not was confirmed by visually checking for discoloration, and corrosion holes (origins) of several tens of micrometers or more were observed with a microscope. For finer corrosion holes (origins), the presence or absence of corrosion holes (origins) was confirmed by observation with a SEM. Whether cuprous oxide was generated or not was visually checked and it was determined that there was generation of cuprous oxide when dark discoloration occurred on the appearance.
As shown in
According to Examples 1a to 1e using the benzotriazole-based compound with the product name OA-386 manufactured by Daiwa Fine Chemicals Co., Ltd., as shown in
According to Examples 2a to 2e using the benzotriazole-based compound with the product name BT-LX manufactured by Johoku Chemical Co., Ltd., as shown in
In one or more embodiments, the refrigerant piping is able to sustain the rust prevention effect even when exposed to dew condensation water or rainwater, since the benzotriazole-based compound is difficult to elute.
Further, when the refrigerant piping is used in the heat exchanger of the air conditioner, the refrigerant piping is able to sustain the rust prevention effect even if dew condensation water is generated on the surface of the heat exchanger when the heat exchanger is used to function as an evaporator of the refrigerant.
Furthermore, in one or more embodiments, when the refrigerant piping is adopted in the outdoor heat exchanger constituting the outdoor unit of the air conditioner or various pipings, the refrigerant piping is able to sustain the rust prevention effect even if it is installed outdoors and exposed to rainwater.
Although the disclosure has been described with respect to only a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that various other embodiments may be devised without departing from the scope of the present invention. Accordingly, the scope of the invention should be limited only by the attached claims.
[Patent Document 1] Japanese Unexamined Patent Publication No. 2011-184714
| Number | Date | Country | Kind |
|---|---|---|---|
| 2015-106795 | May 2015 | JP | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/JP2016/065429 | 5/25/2016 | WO | 00 |
