JP2019209275A - Oxygen enrichment membrane, and method for producing the same - Google Patents

Abstract

To provide an oxygen enrichment membrane having an excellent gas separation function, and a method for producing the same.SOLUTION: The oxygen enrichment membrane has a gas separation layer and a porous base material layer supporting the gas separation layer, the surface roughness of the gas separation layer being 5 nm to 1 μm.SELECTED DRAWING: Figure 3

Description

  Embodiments described herein relate generally to an oxygen-enriched film and a method for manufacturing the same.

  As a deterioration factor of stored items such as food stored in a storage such as a refrigerator, there is oxidation due to oxygen present in the air. Therefore, by sucking the air inside the storage container through an oxygen-enriched membrane (oxygen separation membrane) by an exhaust means such as a pump, the high oxygen concentration air is discharged outside the storage container, and the oxygen concentration in the storage container There is known a storehouse that can suppress the oxidization of the stored product by reducing the level of the product and maintain the freshness of the stored product.

  As a method for producing an oxygen-enriched membrane used in such a storage, for example, a water surface expansion method is known in which a gas separation layer formed on the water surface is transferred to a substrate.

  However, in the water surface development method, since a thin film formed on the water surface is handled, the operation is complicated, and defects such as tearing of the film are likely to occur, which is not suitable for mass production.

  In addition to the water surface development method, for example, a mixed solution obtained by mixing a reaction accelerator such as a catalyst with a silicone-based composition containing a compound having a siloxane bond is applied to the porous base material layer and heated to crosslink. There is known a solution coating method in which a gas separation layer is formed on a porous base material layer by curing.

  However, when a silicone composition or the like is applied on the porous base material layer, the pores of the porous base material layer are impregnated with the silicone composition after application, so that fine irregularities are formed on the surface of the gas separation layer. There was. When irregularities are formed on the surface of the gas separation layer and the film thickness is not uniform, air permeation concentrates on the thin film thickness, so there is room for improvement in gas separation performance.

JP-A-5-111626

  The present invention has been made in view of the above, and an object thereof is to provide an oxygen-enriched membrane excellent in gas separation ability and a method for producing the same.

  The oxygen-enriched membrane of this embodiment is an oxygen-enriched membrane having a gas separation layer and a porous base material layer that supports the gas separation layer, and the surface roughness of the gas separation layer is 5 nm to It is 1 μm.

  The method for producing an oxygen-enriched membrane according to this embodiment is a method for producing an oxygen-enriched membrane having at least a gas separation layer and a porous base material layer that supports the gas separation layer, and a mold release treatment is performed. The gas separation layer composition includes the step of laminating the gas separation layer by applying the gas separation layer composition on the applied release film, and the gas separation layer laminated on the release film. Before the solvent to be completely volatilized, it includes a step of bonding to the porous substrate layer and a step of volatilizing the solvent contained in the gas separation layer composition.

Sectional drawing for demonstrating a refrigerator provided with the oxygen enrichment film | membrane which concerns on one Embodiment of this invention. FIG. 2 is a main part sectional view of FIG. 1. 1 is a schematic cross-sectional view of an oxygen-enriched film according to a first embodiment of the present invention. The schematic cross section of the oxygen enrichment film | membrane which concerns on 2nd Embodiment of this invention.

  Hereinafter, the refrigerator 1 provided with the oxygen enrichment film | membrane 62 of one Embodiment is demonstrated based on FIGS.

(1) About the refrigerator 1 provided with the oxygen enrichment film | membrane 62 The refrigerator 1 is provided with the cabinet 2 which consists of a heat insulation box opened to the front. The cabinet 2 has a heat insulating material such as a vacuum heat insulating material or a foam heat insulating material in a heat insulating space 5 formed between an outer box 3 made of steel plate and an inner box 4 made of synthetic resin. In the cabinet 2, a plurality of storage spaces are provided inside the inner box 4, and the storage spaces are partitioned vertically by a heat insulating partition wall 6.

  The space above the heat insulating partition wall 6 is a storage room that is cooled to a refrigeration temperature zone (for example, 1 to 4 ° C.), and the interior is further partitioned vertically by the partition wall 7. A refrigerator compartment 10 is provided above the partition wall 7, and a vegetable compartment 12 is provided below the partition wall 7.

  The inside of the refrigerator compartment 10 is divided into a plurality of stages by a plurality of shelves 9, and a refrigerator temperature sensor 25 that measures the temperature in the refrigerator compartment 10 is provided on the back of the refrigerator compartment 10.

  At the front opening of the refrigerating room 10, a rotating refrigerating room door 11 pivotally supported by a hinge is provided. The front opening of the vegetable compartment 12 is closed by a drawer-type vegetable compartment door 13. A pair of left and right support frames that hold the storage container 70 are fixed to the inside of the vegetable compartment door 13 so that the storage container 70 is pulled out of the storage as the door is opened. A door sensor 29 is provided at the peripheral edge of the front opening of the vegetable compartment 12 to detect whether the vegetable compartment door 13 is open or closed.

  The storage container 70 provided in the vegetable compartment 12 is a bottomed box-shaped container surrounded by a front wall, a rear wall 70a, and left and right side walls, and is provided with an upper surface opening that opens upward. A storage space S <b> 1 for storing stored items such as vegetables is formed inside the storage container 70, and the stored items are taken in and out from an upper surface opening of the storage container 70. The storage container 70 is closed so that its upper surface opening is openable and closable by a lid 72 and constitutes a closed container in which direct entry of air (wind) circulating through the vegetable compartment 12 is suppressed. An opening 70b is formed in the lower portion of the rear wall 70a of the storage container 70, and a wind direction plate 52 is provided so as to cover the storage space S1 side of the opening 70b with a space therebetween. . The wind direction plate 52 is inclined forward as it goes upward, and guides the air blown out from the opening 70b so as to blow out toward the ceiling surface of the storage container 70 (that is, the lid 72).

  In a space below the heat insulating partition wall 6, an ice making chamber (not shown) equipped with an automatic ice maker and a first freezing chamber 16 are provided on the left and right sides, and a second freezing chamber 17 is interposed below the first freezing chamber 17 via a partition plate 22. Is provided.

  The ice making room, the first freezing room 16 and the second freezing room 17 are all cooled to a freezing temperature zone (for example, −17 ° C. or lower). A freezing temperature sensor 26 for measuring the temperature in the second freezing chamber 17 is provided on the back surface of the second freezing chamber 17.

  The openings of the ice making room, the first freezing room 16, and the second freezing room 17 are closed by drawer type doors 18 and 19 as in the vegetable room 12. The storage containers 20 and 21 are held by a pair of left and right support frames fixed to the back surfaces of the doors 18 and 19, and the storage containers 20 and 21 are configured to be pulled out of the storage as the door is opened. Yes.

  At the rear of the refrigerator compartment 10 and the vegetable compartment 12, a refrigerator refrigerator chamber 32 is provided that is divided forward and backward by an evaporative cover 23.

  The refrigeration cooler chamber 32 houses the refrigeration cooler 30, the refrigeration fan 31, the drain pan 27, and the exhaust unit 90. The refrigeration cooler chamber 32 is connected to the refrigeration chamber 10 by a duct 33, and the air in the refrigeration cooler chamber 32 cooled by the refrigeration cooler 30 is supplied to the refrigeration chamber 10 through the duct 33 by the refrigeration fan 31. ing.

  The drain pan 27 is disposed below the refrigeration cooler 30 and receives dew condensation water (defrost water) generated from the refrigeration cooler 30 during the defrosting operation. Condensed water collected in the drain pan 27 is discharged via a drainage hose 28 to an evaporating dish 41 disposed in a machine room 38 provided at the lower back of the cabinet 2.

  The drainage hose 28 for discharging the condensed water accumulated in the drain pan 27 to the machine room 38 is inserted into the insertion hole 2a that connects the refrigeration cooler room 32 and the machine room 38 provided on the back wall of the cabinet 2 to be refrigerated. It is drawn out from the cooler chamber 32 to the machine chamber 38.

  The insertion hole 2a provided in the cabinet 2 has a larger diameter than the drainage hose 28 to be inserted. Therefore, in a state where the drainage hose 28 is inserted into the insertion hole 2 a, a continuous gap is formed between the insertion hole 2 a and the drainage hose 28 from the refrigeration cooler chamber 32 to the machine chamber 38. That is, the gap formed between the insertion hole 2 a and the drain hose 28 functions as a vent hole 2 c that communicates the vegetable compartment 12 and the machine compartment 38.

  At the rear of the ice making room, the first freezing room 16 and the second freezing room 17, there are a freezing cooler room 36 divided forward and backward by an evaporative cover 24, an ice making room, the first freezing room 16 and the second freezing room 17. And a duct 37 connecting the refrigeration cooler chamber 36 is formed. The refrigeration cooler chamber 36 accommodates a refrigeration cooler 34 and a refrigeration fan 35, and the air in the refrigeration cooler chamber 36 cooled by the refrigeration cooler 34 is refrigerated by the refrigeration fan 35 through the duct 37, The first freezer 16 and the second freezer 17 are supplied.

  The refrigeration cooler 30 and the refrigeration cooler 34 constitute a refrigeration cycle together with a compressor 39 and a condenser (not shown) housed in the machine room 38. In the refrigeration cycle, the refrigerant discharged from the compressor 39 is supplied to one of the refrigeration cooler 30 and the refrigeration cooler 34 by a switching valve (not shown), so that the refrigeration cooler 30 and the refrigeration cooler 34 are cooled to a predetermined temperature. Is done.

  The refrigeration cooler 30 cools the air in the refrigeration cooler chamber 32 to generate cold air of, for example, −10 to −20 ° C. The cold air generated in the refrigerator compartment 32 is supplied to the refrigerator compartment 10 through the duct 33 by the rotation of the refrigerator fan 31, and cools the refrigerator compartment 10.

  A part of the cold air flowing through the refrigerating chamber 10 returns to the refrigerating cooler chamber 32 from the suction port provided at the rear portion of the partition wall 7, and the remaining air passes through the communication path 7 a provided in the partition wall 7 and is vegetable. It flows into the rear upper part of the chamber 12.

  The cold air that has flowed into the vegetable compartment 12 cools the inside of the vegetable compartment 12 while flowing outside the storage container 70 provided in the vegetable compartment 12, thereby cooling the inside indirectly from the outside of the storage container 70. The cold air that has flowed through the vegetable compartment 12 returns to the refrigerated cooler compartment 32 from the suction port. The cold air that has returned to the refrigeration cooler chamber 32 is cooled again by exchanging heat with the refrigeration cooler 30.

  The refrigeration cooler 34 cools the air in the refrigeration cooler chamber 36 to generate, for example, cold air of −20 to −30 ° C. The generated cold air is supplied to the ice making room, the first freezing room 16 and the second freezing room 17 through the duct 37 by the rotation of the freezing fan 35, and cools these storage rooms. The air that has cooled the ice making chamber and the first freezing chamber 16 flows into the second freezing chamber 17 through a through hole (not shown), merges with the cold air supplied to the second freezing chamber 17, and then the second freezing chamber. 17 is returned to the refrigeration cooler chamber 36 from the suction port provided on the back surface of the heat exchanger 17, and is cooled again by exchanging heat with the refrigeration cooler 34.

(2) About Oxygen Separation Module 60 In the refrigerator 1 having such a configuration, as shown in FIGS. 1 and 2, the oxygen separation module 60 including the oxygen-enriched membrane 62 is disposed in the vegetable compartment 12, for example, the evaporative cover 23. It is provided below the partitioned refrigeration cooler chamber 32 so as to face the rear wall 70a of the storage container 70.

  The oxygen separation module 60 includes a cell 63 provided with an oxygen-enriched film 62 inside a box-shaped case 61. The cell 63 includes a regulation space S3, an exhaust space S4, and an oxygen-enriched film 62 that partitions both the spaces S3 and S4. The oxygen separation module 60 may be provided with a plurality of cells 63 stacked in the thickness direction of the oxygen-enriched film 62 inside the case 61.

  When a pressure difference occurs between the adjustment space S3 and the exhaust space S4, the oxygen-enriched film 62 diffuses and moves in the high-pressure side air from the low-pressure side surface by diffusing and moving inside the film. Reduce the oxygen concentration on the side.

  The adjustment space S3 provided in the cell 63 is a duct-like space partitioned between the partition walls arranged in parallel and close to the oxygen-enriched film 62, and an introduction channel 198 is connected to one end thereof. ing. The introduction flow path 198 is a flow path formed by joining two air supply flow paths 98 connected to exhaust sections 90A and 90B, which will be described later.

  The other end of the adjustment space S3 opens at a position facing the opening 70b provided in the rear wall 70a of the storage container 70 in the front-rear direction, and a rubber-like elastic body such as rubber or silicone so as to surround the periphery of the opening. The sealing material 66 which consists of is provided.

  In a state where the storage container 70 as shown in FIG. 1 is housed in the vegetable compartment 12, the sealing material 66 abuts against the rear wall 70a of the storage container 70 so as to surround the opening 70b. As a result, the opening 70b of the storage container 70 and the tip of the adjustment space S3 are connected by the sealing material 66, and are provided in the case 61 at the lower part of the storage space S1 (below the center in the height direction of the storage space S1). The adjusted adjustment space S3 communicates with the storage space S1 of the storage container 70.

  Further, an exhaust port 65 for connecting the suction flow path 197 is provided in the exhaust space S4 of the cell 63.

  The oxygen separation module 60 is connected to the exhaust unit 90, and the air inside the storage container 70 that has permeated the oxygen-enriched membrane 62 is exhausted to the outside of the storage container 70 by the exhaust unit 90. Reduce oxygen concentration.

  The exhaust part 90 includes a plurality of exhaust means, in the present embodiment, a first exhaust pump 90A and a second exhaust pump 90B.

  The outlet channel 96 of the first exhaust pump 90A and the outlet channel 96 of the second exhaust pump 90B merge in the middle to form one external exhaust channel 196, and the vegetable compartment 12 provided on the back wall of the cabinet 2 Is inserted into the insertion hole 2 b that communicates with the machine room 38, and is drawn from the refrigeration cooler room 32 to the machine room 38.

  The first exhaust pump 90 </ b> A and the second exhaust pump 90 </ b> B have the same basic configuration, and the air in the exhaust space S <b> 4 of the cell 63 passes through the suction flow path 197 and the inlet flow path 97 in the exhaust pump 90. The intake operation for taking in the cylinder chamber (not shown) and the exhaust operation for discharging the taken air from the cylinder chamber to the machine chamber 38 through the outlet passage 96 and the external exhaust passage 196 are repeated.

  The first exhaust pump 90A adjusts the oxygen separation module 60 via the air supply passage 98 and the introduction passage 198 when air is taken into the cylinder chamber from the inlet passage 97. Send to space S3.

  A control unit 50 that controls the overall operation of the refrigerator 1 is provided at the upper back of the cabinet 2 (see FIG. 1). The control unit 50 is based on signals input from various sensors such as the refrigeration temperature sensor 25, the refrigeration temperature sensor 26, and the door sensor 29, and a control program stored in a memory formed of a nonvolatile recording medium such as an EEPROM. By controlling various electric components such as a refrigeration fan 31, a refrigeration fan 35, a compressor 39, a switching valve (not shown) provided in the refrigeration cycle, and an exhaust pump 90, each chamber can be cooled to a predetermined temperature, vegetable The oxygen concentration of the storage space S1 inside the storage container 70 provided in the chamber 12 is reduced.

(3) Oxygen-enriched film 62 (first embodiment)
As shown in FIG. 3, the oxygen-enriched film 62 according to the first embodiment includes a gas separation layer 101 and a porous base material layer 102 that supports the gas separation layer 101, and the porous base material layer 102. The hole portion is provided with an impregnation portion (not shown) impregnated with the gas separation layer composition constituting the gas separation layer 101.

  As the gas separation layer composition constituting the gas separation layer 101, a solution obtained by dissolving a silicone-based composition, disubstituted polyacetylene or the like in a solvent can be used, and if necessary, a reaction accelerator is contained. Also good.

  In the present specification, “silicone composition” refers to all substances that contain a compound having a siloxane bond and can form a film by dehydration condensation reaction, crosslinking, solvent removal, etc., and “silicone resin” The silicone-based composition generally refers to those that have lost fluidity due to solvent removal or the like, and includes both those in which a crosslinked structure is formed by addition of a reaction accelerator and those that are not formed.

  Examples of the disubstituted polyacetylene include poly (1-trimethylsilyl-1-propyne).

  Here, the reaction accelerator refers to all substances that promote the crosslinking reaction of the silicone composition, such as a crosslinking agent, a catalyst, and a radical initiator, and two or more kinds may be used in combination. As the silicone composition, A two-component curing type in which a crosslinking reaction proceeds by mixing with such a reaction accelerator may be used.

  Examples of the crosslinking agent include, but are not limited to, silane-based crosslinking agents such as trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, and tetrabutoxysilane.

  As the catalyst, a metal catalyst such as a platinum catalyst usually used for addition reaction or dealcoholization condensation reaction can be used.

  As the radical initiator, organic peroxides such as acyl organic peroxides and alkyl organic peroxides, azo compounds, and the like can be used.

  In addition, the silicone-based composition contains monomers or prepolymers that do not have a siloxane structure, as well as additives commonly used in compositions that form an oxygen-enriched film, as long as the effects of the present invention are not impaired. You may do it.

  Although it does not specifically limit as said solvent, From the viewpoint of solubility, such as a silicone type composition and a reaction accelerator, and volatility of a solvent, hydrocarbons, such as hexane, octane, heptane, cyclohexane, benzene, toluene, xylene And alcohols such as methanol, ethanol, n-propanol, isopropanol, and butanol are preferable.

  The surface roughness of the gas separation layer 101 is not particularly limited as long as it is 5 nm to 1 μm, but is preferably 5 nm to 500 nm, and more preferably 5 nm to 100 nm. Here, “surface roughness” in this specification refers to arithmetic surface roughness Ra, and is a value measured by a contact-type surface roughness meter. In addition, when the gas separation layer is produced by the water surface development method or the solution coating method, the surface roughness usually exceeds 1 μm. Therefore, in the water surface development method or the solution coating method, the gas separation layer having a surface roughness within the above range is used. It is difficult to manufacture.

  Although the viscosity at 25 ° C. of the gas separation layer composition is not particularly limited, from the viewpoint of forming the gas separation layer 101 having a uniform film thickness on the porous base material layer 102, 0.5 Pa · s to 40 Pa · s. Preferably, it is 10 Pa · s to 20 Pa · s. Here, in this specification, “viscosity” is a value measured at a rotational speed of 100 rpm using a conical plate type rotational viscometer.

  Although the film thickness of the gas separation layer 101 is not specifically limited, It is preferable that they are 1 nm-1 micrometer, and it is more preferable that they are 50 nm-500 nm. Here, the “film thickness” in this specification is a value measured by an optical film thickness measuring device that measures the film thickness by light interference. In the solution coating method, the thinner the gas separation layer 101, the more difficult it is to form the gas separation layer 101 with a uniform film thickness. When the gas separation layer 101 is formed with the above film thickness, The effect of this embodiment is noticeable.

  The average pore diameter of the pores formed in the porous base material layer 102 is not particularly limited, but is preferably 0.001 μm to 1 μm, and more preferably 0.01 μm to 0.1 μm.

  The method for producing the oxygen-enriched film 62 according to the present embodiment is not particularly limited. For example, the gas separation layer 101 is laminated by applying a gas separation layer composition on a release film subjected to a release treatment. Attaching the gas separation layer 101 laminated on the release film to the porous substrate layer 102 before the solvent contained in the gas separation layer composition is completely volatilized, It may have a step of volatilizing the solvent contained in the gas separation layer composition.

  Thus, before the solvent contained in the gas separation layer composition is completely volatilized, the gas separation layer composition is attached to the pores of the porous base material layer 102 by being bonded to the porous base material layer 102. An anchor effect can be obtained by impregnation, and the roughness of the surface of the gas separation layer 101 can be within a predetermined range even after the gas separation layer composition has been impregnated into the pores of the porous base material layer 102. The gas separation layer 101 having a uniform film thickness and excellent gas separation ability can be obtained.

  Even in the solution coating method, although the anchor effect is obtained by impregnating the pores of the porous base material layer 102 with the gas separation layer composition, the surface of the porous base material layer 102 is formed on the surface of the gas separation layer 101. Since fine irregularities are formed under the influence of the irregular shape, the gas separation ability is poor. In addition, when the solvent contained in the gas separation layer composition is bonded together in a completely volatilized state, the gas separation layer 101 with a uniform film thickness is obtained, but the adhesion with the porous substrate layer 102 is poor, A separate adhesive is required, and the gas separation ability is greatly reduced by the presence of the adhesive between the gas separation layer 101 and the porous substrate layer 102.

  When a silicone composition is used as the gas separation layer composition, the silicone composition may be crosslinked from the viewpoint of increasing the strength of the gas separation layer 101, and the method of crosslinking is not particularly limited. Select according to the type. In other words, when using a crosslinking agent or catalyst capable of proceeding a crosslinking reaction at room temperature as a reaction accelerator, it should be left at room temperature. When using a radical initiator, is it irradiated with energy rays such as ultraviolet rays or electron beams? What is necessary is just to heat, and when using the catalyst which needs a heating, what is necessary is just to heat.

  What is necessary is just to select other reaction conditions, such as reaction temperature, according to the method used conventionally.

  The method for applying the gas separation layer composition onto the release film is not particularly limited, and methods such as coater coating using a die coater or roll coater, spray coating, brush coating, dipping, pouring, and the like can be used as appropriate.

(Second Embodiment)
As for the oxygen-enriched film 62 according to the second embodiment, only differences from the oxygen-enriched film 62 according to the first embodiment will be described.

  As shown in FIG. 4, the oxygen-enriched film 62 according to the second embodiment includes a gas separation layer 101, a porous substrate layer 102 that supports the gas separation layer 101, a gas separation layer 101, and a porous substrate. The intermediate layer 103 is provided between the layer 102 and the pores of the porous base material layer 102 are provided with impregnated portions impregnated with the intermediate layer composition constituting the intermediate layer 103.

  The intermediate layer composition constituting the intermediate layer 103 is preferably one having high gas permeability, and as such a material, for example, a material in which disubstituted polyacetylene or the like is dissolved in a solvent can be used. Moreover, the intermediate | middle layer composition may contain the adhesiveness imparting agent as needed.

  The viscosity at 25 ° C. of the intermediate layer composition is not particularly limited, but is 0.5 Pa · s to 40 Pa · s from the viewpoint of forming the intermediate layer 103 having a uniform film thickness on the porous base material layer 102. Is preferable, and 10 Pa · s to 20 Pa · s is more preferable.

  Although the film thickness of the intermediate | middle layer 103 is not specifically limited, From a gas-permeable viewpoint, it is preferable that it is 10 nm-5 micrometers, and it is more preferable that it is 100 nm-1 micrometer.

  The method for producing the oxygen-enriched film 62 according to the present embodiment is not particularly limited. For example, the step of laminating the intermediate layer 103 by applying the intermediate layer composition on the release film subjected to the release treatment. Bonding the intermediate layer 103 laminated on the release film to the porous base material layer 102 before the solvent contained in the intermediate layer composition completely volatilizes, and the porous base material layer. The step of laminating the gas separation layer 101 by applying the gas separation layer composition to the intermediate layer 103 bonded to 102, and the step of volatilizing the solvent contained in the intermediate layer composition and the gas separation layer composition It can have.

  Thus, before the solvent contained in the intermediate layer composition is completely volatilized, the intermediate layer composition is impregnated into the pores of the porous base layer 102 by being bonded to the porous base layer 102. The anchor effect can be obtained, and even after the intermediate layer composition is impregnated in the pores of the porous base material layer 102, the film thickness of the intermediate layer 103 can be kept uniform and laminated thereon. The gas separation layer 101 having a uniform film thickness can be formed by setting the surface roughness of the gas separation layer 101 within a predetermined range.

  As another manufacturing method of the oxygen-enriched film 62, a step of laminating the gas separation layer 101 by applying a gas separation layer composition on a release film subjected to a release treatment, In addition, the step of laminating the intermediate layer 103 by applying the intermediate layer composition and the intermediate layer 103 laminated on the release film before the solvent contained in the intermediate layer composition is completely volatilized. The step of bonding to the porous substrate layer 102 and the step of volatilizing the solvent contained in the intermediate layer composition and the gas separation layer composition may be included.

  By using such a manufacturing method, an anchor effect is obtained by impregnating the pores of the porous base material layer 102 with the intermediate layer composition. Even after the impregnation, the gas separation layer 101 laminated thereon is obtained. The film thickness can be kept uniform.

  The method of applying the intermediate layer composition on the release film is not particularly limited, and a method such as coater coating using a die coater or roll coater, spray coating, brush coating, dipping, pouring, or the like may be appropriately used. it can.

(4) About execution of oxygen reduction operation of refrigerator 1 In order to execute the oxygen reduction operation to reduce the oxygen concentration inside the storage container 70, the door sensor 29 detects that the vegetable compartment door 13 is in a closed state. The exhaust unit 90 is operated when

  Specifically, the first exhaust pump 90A and the second exhaust pump 90B constituting the exhaust unit 90 are operated. When the first exhaust pump 90A and the second exhaust pump 90B operate, the air in the exhaust space S4 of the oxygen separation module 60 flows from the exhaust port 65 through the suction flow path 197 to the first exhaust pump 90A and the second exhaust pump 90B. It is taken into the cylinder chamber and discharged from the cylinder chamber to the machine chamber 38 via the external exhaust passage 196.

  As a result, the exhaust space S4 has a lower pressure than the adjustment space S3 that faces the oxygen-enriched film 62, so that oxygen in the adjustment space S3 passes through the oxygen-enriched film 62 and moves to the exhaust space S4. The oxygen concentration of S3 decreases.

  In addition, with the operation of the first exhaust pump 90A and the second exhaust pump 90B, the air in the drive chamber of each pump 90A, 90B is provided in the oxygen separation module 60 via the air supply passage 98 and the introduction passage 198. Is supplied to the adjustment space S3 of the cell 63.

  The air supplied to the adjustment space S3 is reduced in oxygen concentration by flowing along the oxygen-enriched film 62 while oxygen is discharged into the exhaust space S4, and then an opening provided in the rear wall 70a of the storage container 70. Supplied from the section 70b to the storage space S1.

  Thereby, the oxygen concentration of storage space S1 falls, the oxidation of the stored goods accommodated in storage space S1 can be suppressed, and the freshness of stored goods can be maintained.

  Then, when a predetermined end condition such as a predetermined time elapses after the operation of the first exhaust pump 90A and the second exhaust pump 90B is started, the first exhaust pump 90A and the second exhaust pump 90B are stopped. End hypoxic operation.

  As mentioned above, although embodiment of this invention was described, these embodiment was shown as an example and is not intending limiting the range of invention. These embodiments can be implemented in various other forms, and various omissions, replacements, and changes can be made without departing from the spirit of the invention. These embodiments and modifications thereof are included in the invention described in the claims and equivalents thereof as well as included in the scope and gist of the invention.

DESCRIPTION OF SYMBOLS 1 ... Refrigerator, 2 ... Cabinet, 10 ... Refrigerator room, 12 ... Vegetable room, 30 ... Refrigerator cooler, 31 ... Refrigerator fan, 32 ... Refrigerator cooler room, 60 ... Oxygen separation module, 61 ... Case, 62 ... Oxygen rich Chemical membrane, 63 ... cell, 65 ... exhaust port, 66 ... sealing material, 70 ... storage container, 70a ... rear wall, 70b ... opening, 90 ... exhaust part, 90A ... first exhaust pump, 90B ... second exhaust pump , 96 ... outlet passage, 97 ... inlet passage, 98 ... air supply passage, 196 ... external exhaust passage, 197 ... exhaust passage, 198 ... introduction passage, S1 ... storage space, S3 ... adjustment space, S4 ... exhaust space, 101 ... gas separation layer, 102 ... porous substrate layer, 103 ... intermediate layer

Claims (11)

A gas separation layer;
An oxygen-enriched membrane having a porous substrate layer that supports the gas separation layer,
An oxygen-enriched membrane, wherein the gas separation layer has a surface roughness of 5 nm to 1 µm.   2. The oxygen-enriched membrane according to claim 1, further comprising an impregnated portion impregnated with a gas separation layer composition constituting the gas separation layer in a hole portion of the porous base material layer.   The oxygen-enriched membrane according to claim 1, further comprising an intermediate layer between the gas separation layer and the porous base material layer.   The oxygen-enriched film according to claim 3, further comprising an impregnated portion impregnated with an intermediate layer composition constituting the intermediate layer in a hole portion of the porous base material layer.   The oxygen-enriched membrane according to any one of claims 1 to 4, wherein the gas separation layer composition contains a silicone resin or a disubstituted polyacetylene.   The oxygen-enriched membrane according to any one of claims 1 to 5, wherein the gas separation layer has a thickness of 5 nm to 1 µm.   A refrigerator comprising the oxygen-enriched film according to any one of claims 1 to 6. A method for producing an oxygen-enriched membrane having at least a gas separation layer and a porous substrate layer that supports the gas separation layer,
A step of laminating the gas separation layer by applying the gas separation layer composition on the release film subjected to the release treatment;
Bonding the gas separation layer laminated on the release film to the porous substrate layer before the solvent contained in the gas separation layer composition is completely volatilized;
A method for producing an oxygen-enriched membrane, comprising a step of volatilizing a solvent contained in the gas separation layer composition. A method for producing an oxygen-enriched membrane having at least a gas separation layer, a porous substrate layer that supports the gas separation layer, and an intermediate layer interposed between the gas separation layer and the porous substrate layer There,
The step of laminating the intermediate layer by applying the intermediate layer composition on the release film subjected to the release treatment,
Bonding the intermediate layer laminated on the release film to the porous base material layer before the solvent contained in the intermediate layer composition completely volatilizes;
The step of laminating the gas separation layer by applying the gas separation layer composition to the intermediate layer bonded to the porous base material layer, and the solvent contained in the intermediate layer composition and the gas separation layer composition A method for producing an oxygen-enriched film, comprising a step of volatilizing. A method for producing an oxygen-enriched membrane having at least a gas separation layer, a porous substrate layer that supports the gas separation layer, and an intermediate layer interposed between the gas separation layer and the porous substrate layer There,
A step of laminating the gas separation layer by applying the gas separation layer composition on the release film subjected to the release treatment;
A step of laminating an intermediate layer by applying an intermediate layer composition on the gas separation layer;
A step of bonding the intermediate layer laminated on the release film to the porous base material layer before the solvent contained in the intermediate layer composition completely volatilizes; and the intermediate layer composition and the gas The manufacturing method of an oxygen enriched film | membrane which has the process of volatilizing the solvent which a separated layer composition contains. The method for producing an oxygen-enriched membrane according to any one of claims 8 to 10, wherein the gas separation layer composition contains a silicone resin or a disubstituted polyacetylene.

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