JP2008178863A - Method for producing selectively permeable membrane structure, selectively permeable membrane structure, and air conditioning system - Google Patents

Abstract

The present invention provides a method for producing a selectively permeable membrane structure having a gas selective permeability and a function of removing SPM and nSPM, and having a strength capable of withstanding various uses.
A method of manufacturing a selectively permeable membrane structure 40a having a reinforcing mesh material 302 and a selectively permeable membrane 13a laminated on the reinforcing mesh material 302 includes a sealing material 332 in an opening 302b of the reinforcing mesh material 302. , The step of shrinking the volume of the sealing material 332 filled in the opening 302b, the exposed portion 302c of the reinforcing mesh material 302 not covered with the sealing material 332, and the opening 302b. A step of forming the permselective membrane 13a from the permselective material 13s so as to cover the exposed portion 332a of the permeation material 332, and the formation of the permute from the opening 302b of the reinforcing mesh material 302 after the permselective membrane 13a is formed. Removing the material 332.
[Selection] Figure 1

Description

  The present invention relates to a method for manufacturing a selectively permeable structure, a selectively permeable membrane structure, and an air conditioning system.

  In recent years, with the advance of technology, for example, it has become possible to improve airtightness even in a space where it was difficult to improve airtightness such as an automobile. If a large number of passengers ride in such highly airtight vehicles for a long time, the oxygen concentration may decrease or the carbon dioxide concentration may increase, causing a headache or discomfort to the passengers. It is necessary to introduce outside air.

  However, since urban roads and main roads are contaminated with pollutants such as dust, it is a big problem to introduce the outside air into the vehicle as it is for the health of passengers. As one method for solving this problem, there is a method in which a filter for removing pollutants in the atmosphere, for example, suspended substances, is installed at an intake for introducing outside air.

Conventionally, a nonwoven fabric, a mechanical filter, or the like has been used as such a filter. In Patent Document 1, an air conditioning system for the entire automobile is proposed.
JP 2004-203367 A

  However, conventional filters such as nonwoven fabrics and mechanical filters have a particle size of 10 μm or less (hereinafter referred to as “SPM”) among suspended substances in the atmosphere, particularly those having a particle size of 100 nm or less (hereinafter referred to as “nSPM”). .) Was very difficult to remove. Moreover, even if a gas selective permeable membrane made of a polymer material is applied to the filter, SPM and nSPM can be removed, but the gas permeability is insufficient and the object of sufficiently introducing outside air is achieved. There was a problem that I could not.

  In recent years, as the airtightness of automobiles has increased, it is required to equip the above-mentioned filters and gas selective permeable membranes not only in the air conditioning system but also in various parts of the entire automobile. In order to equip filters and gas selective permeable membranes in a wide variety of locations, the filter and gas selective permeable membrane can withstand not only SPM and nSPM removal functions and gas permeability, but also various uses. There was also a need to impart mechanical strength.

  The present invention has been made in view of the above circumstances, and has a selective permeability of gas and a function of removing SPM and nSPM, and a method of manufacturing a selectively permeable membrane structure having strength that can withstand various uses, An object is to provide a selectively permeable membrane structure and an air conditioning system including the selectively permeable membrane structure.

  In order to achieve the above object, a first method for producing a permselective membrane structure of the present invention includes a step of filling a sealing material in an opening of a reinforcing mesh material, and a volume of the sealing material filled in the opening. A permselective membrane is formed from a permselective material so as to cover the shrinking step, the exposed portion of the reinforcing mesh material not covered with the seam, and the exposed portion of the seam filled in the opening. And a step of removing the sealing material from the openings of the reinforcing mesh material after forming the permselective membrane. In the present invention, the permselective membrane structure includes a reinforcing mesh material and a permselective membrane laminated on the reinforcing mesh material. In the present invention, the “opening of the reinforcing mesh material” corresponds to the eyes of the reinforcing mesh material.

  In the present invention, the reinforcing mesh material is sealed by filling the openings of the reinforcing mesh material with the sealing material, and a smooth flat surface is formed on the reinforcing mesh material. Therefore, by forming the permselective membrane from the permselective material after filling the openings of the reinforcing mesh material with the sealing material, the permselective material is excessively contained in the openings of the reinforcing mesh material. ) Can be prevented, and a permselective membrane having a uniform thickness and a smooth surface can be formed.

  Further, in the present invention, after forming the permselective membrane, the gas permeability in the permselective membrane facing the opening of the reinforcing mesh material is secured by removing the sealing material from the opening of the reinforcing mesh material. can do.

  Further, in the present invention, since the volume shrinkage rate of the sealing material can be adjusted when the volume of the sealing material filled in the opening is contracted, the inside of the opening of the reinforcing mesh material is reduced along with the volume shrinkage of the sealing material. The volume of the space formed can be adjusted. Therefore, the volume of the permselective material introduced into the space formed in the opening of the reinforcing mesh material as the volume of the sealing material shrinks can also be adjusted. As a result, it is possible to adjust the thickness of the selectively permeable membrane after film formation, particularly the thickness of the selectively permeable membrane at a position facing the opening. In addition, when a permselective material is introduced into the space formed in the opening of the reinforcing mesh material due to the shrinkage of the volume of the sealing material, a structure in which the reinforcing mesh material is embedded in the permselective film after film formation is formed. The structure has an anchor effect, and the permselective membrane can be firmly adhered to the reinforcing mesh material.

  The second method for producing a permselective membrane structure of the present invention includes a step of filling the opening in the reinforcing mesh material with a sealing material, and an exposed portion of the sealing material filled in the opening. A step of forming an intermediate layer having both adhesiveness and adhesiveness with a selectively permeable material, a step of shrinking the volume of the sealing material filled in the opening, and a reinforcing mesh material not covered with the sealing material. Forming a permselective membrane from the permselective material so as to cover the exposed portion and the intermediate layer, and removing the sealing material and the intermediate layer from the openings of the reinforcing mesh material after the permselective membrane is formed; .

  In the said 2nd manufacturing method, there can exist an effect similar to the said 1st manufacturing method. Furthermore, in the second manufacturing method, since the permselective material is formed into a film on the intermediate layer that adheres to the sealant and has adhesion to the permselective material, the thickness is uniform and the surface is smooth. It becomes easy to form a selective permselective membrane. If a permselective material is formed that directly covers the exposed portion of the reinforcing mesh material and the exposed portion of the sealing material filled in the opening, using a selectively permeable material that is difficult to adhere to the sealing material. The sealing material and the permselective material are difficult to adhere to each other, and the permselective material tends to be difficult to be formed into a film on the seaming material. Such a problem does not occur because the permselective material is formed on the intermediate layer having adhesiveness with the permselective material.

  In the present invention, in the step of shrinking the volume of the sealing material filled in the opening, by exposing a part of the reinforcing mesh material covered with the sealing material along with the volume shrinkage of the sealing material, It is preferable to form an exposed portion of the reinforcing mesh material.

  The sealing material easily shrinks in volume by a process of drying it. Therefore, the exposed portion of the reinforcing mesh material can be easily formed by utilizing the volume shrinkage of the sealing material. Moreover, if volume shrinkage of the sealing material is used, a part of the sealing material covering the reinforcing mesh material is removed in order to form the exposed portion of the reinforcing mesh material before the formation of the permselective membrane. And the step of flattening the surface of the reinforcing mesh material by removing the sealing material becomes unnecessary.

［式中、Ｐ（Ｏ_２）は酸素の透過係数、Ｐ（Ｎ_２）は窒素の透過係数を示す。］ The permselective membrane structure of the present invention is a permselective membrane structure obtained by any one of the first and second manufacturing methods of the permselective membrane structure of the present invention, for forming the permselective membrane. The permselective material is a polymer having an organosiloxane skeleton (hereinafter sometimes referred to as “silicone polymer”) in which a solid additive is dispersed, and oxygen is added to a membrane (selective permeation membrane) formed from the permselective material. When nitrogen and nitrogen are permeated, the permeability coefficient of oxygen and nitrogen (cm ³ · cm · sec ^-1 · cm ^-2 · cmHg ^{-1) at} 23 ± 2 ° C and a pressure difference of 1.05 to 1.20 atm between the membranes. ) Is expressed by the following formula (1), the opening diameter of the reinforcing mesh material is larger than the film thickness of the permselective membrane, and the opening ratio of the reinforcing mesh material is 30% or more.

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ]

  In the present invention, “solid additive” refers to an additive that is solid at normal temperature and pressure, and does not include liquid substances such as plasticizers and ionic liquids.

［式中、Ｐ（Ｏ_２）は酸素の透過係数、Ｐ（Ｎ_２）は窒素の透過係数を示す。］ Alternatively, the permselective membrane structure of the present invention is a permselective membrane structure obtained by any one of the first and second manufacturing methods of the permselective membrane structure of the present invention, and forms a permselective membrane. The selective permeation material for this is formed by adding an ionic liquid to the silicone polymer, and the membrane (selective permeation membrane) formed from the permselective material allows oxygen and nitrogen to permeate at 23 ± 2 ° C. The relationship between oxygen and nitrogen permeability coefficients (cm ³ · cm · sec ^-1 · cm ^-2 · cmHg ^-1 ) at a pressure difference of 1.05 to 1.20 atm is expressed by the following formula (1) and is used for reinforcement. The opening diameter of the mesh material is larger than the film thickness of the permselective membrane, and the opening ratio of the reinforcing mesh material is 30% or more.

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ]

  The permselective membrane included in the permselective membrane structure of the present invention is formed from the above-described permselective material (a material containing either a solid additive or an ionic liquid and a silicone-based polymer), and thus penetrates the membrane. The Knudsen flow is dominant in the flowing gas. According to the permselective membrane structure including such a permselective membrane, it is possible to remove airborne substances such as SPM and nSPM, and to sufficiently ensure gas permeability.

In this specification, “Knudsen flow” refers to a flow of gas that is so thin that the movement of molecules becomes a problem (Chemical Dictionary 3, Chemistry Dictionary Editorial Board, edited version). 44)), and the gas permeation rate depends on its molecular weight. Further, “the Knudsen flow is dominant” means that the gas permeation rate becomes dependent on the molecular weight. Further, “sufficient gas permeability” means that the permeability coefficient of oxygen and nitrogen at 23 ± 2 ° C. and a pressure difference between membranes of 1.05 to 1.20 atm is 8.0 × 10 ⁻⁸ cm ^3. cm · sec ⁻¹ · cm ⁻² · cmHg ⁻¹ or more, preferably 1.0 × 10 ⁻⁷ cm ³ · cm ⁻¹ · cm ⁻² · cmHg ⁻¹ or more. Further, in this specification, “it is possible to remove airborne substances such as SPM and nSPM” means that the blocking rate of nSPM is 80 wt% or more (preferably 90 wt% or more, more preferably 99 wt% or more. ). When the blocking rate of nSPM is 80 wt% or more, naturally, suspended substances in the atmosphere such as SPM having a particle size larger than that of nSPM can be blocked. The blocking rate of nSPM can be measured, for example, by the method described in the examples.

  In order to improve the gas permeability in the permselective membrane, it is necessary to reduce the thickness of the permselective membrane. However, the thinner the permselective membrane, the better the gas permeability, but the membrane strength tends to decrease and the membrane tends to break. Therefore, in the present invention, the permselective membrane formed into a thin film can be reinforced by laminating the permselective membrane on the reinforcing mesh material to form a permselective membrane structure. Such a selectively permeable membrane structure can have a strength that can withstand a wide variety of applications.

  Further, in the present invention, as a reinforcing material for the selectively permeable membrane, a reinforcing mesh material having an opening diameter larger than the thickness of the selectively permeable membrane and an opening ratio of 30% or more is used. Thus, the permselective membrane can be reinforced without impairing the gas permeation function as a whole and the permselective membrane structure. Thus, in the permselective membrane structure using the reinforcing mesh material that is superior in gas permeability compared to the porous film or the nonwoven fabric, the permselective membrane structure in which the permselective membrane is reinforced with the porous film or the nonwoven fabric. Compared to the above, the gas permeation function of the permselective membrane structure as a whole can be improved.

The solid additive is preferably a filler, a conductive polymer, or a mixture thereof. From the viewpoint of further improving gas permeability in the membrane, the filler is preferably a silica-based filler, and particularly preferably a porous filler. In addition, when a solid additive is a filler, it is preferable to satisfy | fill the conditions in any one of the following (1)-(3).
(1) The filler is porous silica particles, and the addition amount of the solid additive is 25 to 1560 parts by mass with respect to 100 parts by mass of the silicone-based polymer.
(2) The filler is non-porous silica particles having an average particle size of 10 to 120 nm and having a hydrophobic or hydrophilic surface, and the solid additive content is 65 to 100 parts by mass of the silicone-based polymer. 3800 parts by mass
(3) The filler is non-porous titanium oxide particles having a hydrophilic surface with an average particle diameter of 10 to 60 nm, and the content of the solid additive with respect to 100 parts by mass of the silicone-based polymer is 330 to 6400 parts by mass. is there.

  As the conductive polymer, polyaniline or acid-treated polyarinin can also be employed. Polyaniline or acid-treated polyaniline is soluble in a solvent such as toluene, as with the silicone-based polymer. For this reason, mixing and dispersion | distribution with a silicone type polymer can be performed easily and stably by dissolving polyaniline in a solvent.

  The air conditioning system of the present invention includes the above-described selectively permeable membrane structure of the present invention as a selectively permeable membrane structure in which gas is supplied to and / or discharged from the air conditioned space. According to this, since the permselective membrane structure of the present invention is used, it is possible to prevent inflow of airborne substances such as SPM and nSPM into the air-conditioning target space. If there is a suspended substance such as SPM or nSPM, it can be removed.

  ADVANTAGE OF THE INVENTION According to this invention, it has the selective permeability of gas, the removal function of SPM, nSPM, and the manufacturing method of the selectively permeable membrane structure which has the intensity | strength which can endure various uses, The selective transmission obtained by the said manufacturing method A membrane structure and an air conditioning system including the permselective membrane structure can be provided.

  Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the drawings depending on cases, but the present invention is not limited thereto.

［式中、Ｐ（Ｏ_２）は酸素の透過係数、Ｐ（Ｎ_２）は窒素の透過係数を示す。］ (Selective membrane structure)
As shown in FIG. 1, the selectively permeable membrane structure 40 a of this embodiment includes a reinforcing mesh material 302 and a selectively permeable membrane 13 a laminated on the reinforcing mesh material 302. The permselective material for forming the permselective membrane 13a is composed of a silicone polymer and an additive (solid additive or ionic liquid), and transmits oxygen and nitrogen to the permselective membrane 13a formed from the permselective material. The oxygen and nitrogen permeation coefficients (cm ³ · cm · sec ^-1 · cm ^-2 · cmHg ^-1 ) at 23 ± 2 ° C and pressure difference between membranes of 1.05 to 1.20 atm. It is represented by the following formula (1). The opening diameter 302a of the reinforcing mesh material 302 is larger than the film thickness 13t of the permselective membrane 13a, and the opening ratio of the reinforcing mesh material is 30% or more.

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ]

  Since the permselective membrane 13a included in the permselective membrane structure 40a of the present embodiment is formed from the above-described permselective material, when the gas is transmitted through the permselective membrane 13a, The Knudsen flow becomes dominant. According to the permselective membrane structure 40a provided with such a permselective membrane 13a, it is possible to remove suspended substances in the atmosphere such as SPM, and to sufficiently ensure gas permeability.

  In order to improve the gas permeability in the selectively permeable membrane 13a, it is necessary to make the selectively permeable membrane 13a thin. However, the thinner the selective permeable membrane 13a, the better the gas permeability. However, the membrane strength tends to decrease and the membrane tends to break. Therefore, in the present embodiment, the selectively permeable membrane 13a can be reinforced by laminating the selectively permeable membrane 13a on the reinforcing mesh material 302 to form the selectively permeable membrane structure 40a. Such a selectively permeable membrane structure 40a can have a strength that can withstand a wide variety of uses.

  The thickness 13t of the selectively permeable membrane 13a is preferably 0.1 to 10 μm, and more preferably 1 to 5 μm. In the permselective membrane 13a formed of the permselective material of the present embodiment, the Knudsen flow is dominant in the flow of gas that permeates the membrane regardless of the film thickness, but the thickness 13t of the permselective membrane 13a is reduced to 0. By setting the thickness to 1 to 10 μm, it becomes easy to achieve both gas permeability and film formability (ease of film formation of the selectively permeable film 13a) of the selectively permeable film 13a. In particular, by setting the thickness 13t of the selectively permeable membrane 13a to 1 to 5 μm, it is possible to secure a sufficient amount of gas permeation through the selectively permeable membrane 13a, and it is difficult for the selectively permeable membrane 13a to have defects, and it is formed. It becomes easy.

The reinforcing mesh material 302 preferably has a gas permeation performance (gas permeation amount) that does not decrease the gas permeability of the selectively permeable membrane 13a laminated thereon. O ₂ or N ₂ in the reinforcing mesh material 302 Is preferably 1.0 × 10 ⁻⁴ cm ³ · sec ⁻¹ · cm ⁻² or more, and 1.0 × 10 ⁻² cm ³ · sec ⁻¹ · cm ^−2. More preferably. As such a reinforcing mesh material 302, a screen mesh material shown in Table 1 is preferably used. In Table 1, a porous film and a non-woven fabric that can be used as a reinforcing material for the selectively permeable membrane 13a instead of the reinforcing mesh material 302 included in the selectively permeable membrane structure 40a of the present invention are also shown as reference examples. However, in the present invention, a reinforcing mesh material 302 that is more excellent in gas permeability than a porous film and a nonwoven fabric is used as a reinforcing material for the selectively permeable membrane 13a.

<Measurement conditions of gas permeation amount in Table 1>
Temperature: 23 ± 2 ° C
Pressure downstream of membrane (total pressure): approx. 1 atm
Pressure upstream of membrane (total pressure): about 1 atm
Pressure difference between membranes (total pressure): 0
O ₂ partial pressure (partial pressure) downstream of the membrane: about 19% (the rest is N ₂ )
O ₂ partial pressure upstream of the membrane (partial pressure): about 20.9% (the rest is N ₂ )
O ₂ pressure difference between membranes (partial pressure): 1.9%.

  In the present embodiment, as the reinforcing material for the selectively permeable membrane 13a, the reinforcing mesh material 302 having an opening diameter 302a larger than the film thickness 13t of the selectively permeable membrane 13a and an opening ratio of 30% or more is used. It is possible to reinforce the selectively permeable membrane 13a without impairing the gas permeability in 13a and the gas permeable function of the entire selectively permeable membrane structure. As described above, in the selectively permeable membrane structure 40a using the reinforcing mesh material 302 having excellent gas permeability as compared with the porous film or the nonwoven fabric, the selectively permeable membrane 13a is reinforced with the porous membrane or the nonwoven fabric. Compared with the membrane structure, the gas permeation function of the entire selectively permeable membrane structure can be improved.

(Selective transmission material)
Next, the permselective material for forming the permselective membrane 13a included in the permselective membrane structure 40a of the present embodiment will be described in detail.

The permselective material is either a permselective material in which a solid additive is dispersed in a silicone polymer or a permselective material in which an ionic liquid is added to a silicone polymer. When oxygen and nitrogen are permeated through the selectively permeable membrane 13a formed from any of these selectively permeable materials, the oxygen and nitrogen permeate at 23 ± 2 ° C. and a pressure difference between the membranes of 1.05 to 1.20 atm. The relationship of the coefficient (cm ³ · cm · sec ⁻¹ · cm ⁻² · cmHg ⁻¹ ) is expressed by the following formula (1).

［式中、Ｐ（Ｏ_２）は酸素の透過係数、Ｐ（Ｎ_２）は窒素の透過係数を示す。］

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ]

Hereinafter, the value obtained by dividing the oxygen permeability coefficient in the above formula (1) by the nitrogen permeability coefficient (P (O ₂ ) / P (N ₂ ): hereinafter also referred to as “separation ratio α”) is 0.94. If it is less than 1, it can be said that the Knudsen flow is dominant in the flow of gas that permeates the membrane (the selectively permeable membrane 13a) made of the selectively permeable material. As described above, the “Knusen flow” is a flow in which the gas permeation rate depends on its molecular weight, but when the gas flow through the membrane is an ideal Knudsen flow, the gas permeability coefficient P is inversely proportional to the square root of its molecular weight. For example, when the permeating gas components are oxygen and nitrogen, their separation ratio α is 0.935 as represented by the following formula (2).

［式中、Ｐ（Ｏ_２）及びＰ（Ｎ_２）はそれぞれ酸素及び窒素の透過係数を示し、Ｍ（Ｏ_２）及びＭ（Ｎ_２）はそれぞれ酸素及び窒素の分子量を示す。］

[Wherein, P (O ₂ ) and P (N ₂ ) represent oxygen and nitrogen permeability coefficients, respectively, and M (O ₂ ) and M (N ₂ ) represent molecular weights of oxygen and nitrogen, respectively. ]

  On the other hand, there is a gas flow called “dissolved diffusion flow”. The dissolved diffusion flow refers to a flow that depends on the product of the solubility of the gas in the membrane and the diffusion coefficient of the gas in the membrane, and generally has a slower gas permeation rate in the membrane than the Knudsen flow. In a conventional membrane containing a silicone-based polymer, it is known that the dissolved diffusion flow is dominant in the gas flow passing through the membrane, and the separation ratio α of oxygen and nitrogen is 1 or more.

From these facts, in the permselective membrane provided in the permselective membrane structure of the present invention, the separation ratio α (P (O ₂ ) / P (N ₂ )) is represented by the above formula (1). Thus, it is considered that a Knudsen flow is generated when the gas passes through the membrane, and the gas permeability is dramatically improved as compared with the conventional one.

  The reason why the Knudsen flow is generated by the permselective membrane formed from the permselective material described above is not necessarily clear, but the present inventors' idea will be described below with reference to FIG. FIG. 2 is a schematic cross-sectional view of a permselective membrane 13a formed from the permselective material.

  When the permselective material includes a silicone polymer and a solid additive, the permselective membrane 13a is composed of a silicone polymer 321 and a solid additive 323, and a boundary between them (the silicone polymer 321 and the solid additive 323). At the interface), there are voids 325 (for example, voids of 1 to 100 nm) that generate Knudsen flow. It is considered that the void 325 is generated due to the low affinity between the silicone polymer 321 and the solid additive 323. In addition, it is preferable that the space | gap which a Knudsen flow produces is formed also in solid additive 323 itself.

  In such a selectively permeable membrane 13a, the gas permeates through the silicone polymer 321 by a dissolved diffusion flow and through the void 325 by a Knudsen flow. In addition, when the solid additive 323 itself has a property of allowing a gas to pass therethrough, such as a porous body, the gas may be transmitted through the solid additive 323. Furthermore, when the solid additives 323 are adjacent to each other, it is also considered that gas permeates through the void formed at the interface between the adjacent solid additives 323 by the Knudsen flow. In the case where is present, gas may be transmitted through the air bubbles by the Knudsen flow.

  When the permselective material contains a silicone polymer and an ionic liquid, the reason why the Knudsen flow is generated by the permselective membrane 13a formed from the permselective material is not necessarily clear, but the ionic liquid is dispersed in the silicone polymer. It is inferred to be due to the existence in the state. In particular, when the permselective material is produced using an ionic liquid and an organic solvent that solidify, such dispersion becomes significant. That is, when an organic solvent insoluble in the ionic liquid is used as a solvent for the silicone polymer (the ionic liquid is usually insoluble in a nonpolar organic solvent such as toluene), the ionic liquid is in such a solvent. Disperse and separate in a suspended state in a polymer dissolved in When the solvent is volatilized in this state, the ionic liquid is fixed in the silicone polymer in a separated state. Thereafter, by setting the temperature of the membrane below the melting point of the ionic liquid, the ionic liquid is solidified, and a gap is formed at the interface between the silicone polymer and the ionic liquid and inside the ionic liquid. It is thought that it is flowing.

  The reason why the Knudsen flow is generated by the selectively permeable film 13a formed from the selectively permeable material when the selectively permeable material includes a silicone polymer and an ionic liquid will be described with reference to FIG. It is composed of a polymer 321 and an ionic liquid 323, and there is a void 325 (for example, a void of 1 to 100 nm) that generates a Knudsen flow at the boundary (interface between the polymer 321 and the ionic liquid 323). It is considered that the void 25 is generated due to the low affinity between the silicone polymer 321 and the ionic liquid 323.

  In such a selectively permeable membrane 13a, the gas permeates through the silicone polymer 321 by a dissolved diffusion flow and through the void 325 by a Knudsen flow. In addition, when the ionic liquid 323 has a property of allowing a gas to pass through like a porous body or the like, the gas may be transmitted through the ionic liquid 323. Furthermore, when the ionic liquids 323 are adjacent to each other, it is also possible that the gas permeates through the void formed at the interface between the adjacent ionic liquids 323 by the Knudsen flow. In the case where is present, gas may be transmitted through the air bubbles by the Knudsen flow.

  As described above, the permselective material is formed from the permselective material of the present invention regardless of whether the permselective material includes a silicone-based polymer and a solid additive, or when the permselective material includes a silicone-based polymer and an ionic liquid. In the permselective membrane 13a, the distance through which the gas permeates through the Knudsen flow is longer than the distance through which the gas permeates through the dissolved diffusion flow. In addition, since the SPM and the nSPM are blocked at the portion where the gas permeates through the dissolved diffusion flow, it is considered that the suspended substances in the atmosphere such as the SPM and the nSPM can be removed.

The “silicone polymer” includes a siloxy group represented by the following general formulas (3), (4), (5) and (6) (in the formula, each R is independently an alkyl having 1 to 30 carbon atoms. A group, an aryl group, an aralkyl group, an alkenyl group, and the above-described substituents substituted with a halogen atom, etc.). Copolymers of organosiloxy units and organic polymers other than silicone, such as silicone-modified cycloolefin polymers, silicone-modified pullulan polymers (for example, those described in JP-A-8-208989) and silicone-modified polyimide polymers (for example, special And those described in Japanese Unexamined Patent Publication No. 2002-332305.
R ₃ SiO _1/2 (3)
R ₂ SiO _2/2 (4)
RSiO _3/2 (5)
SiO _4/2 (6)

  The “solid additive” is preferably a filler, a conductive polymer, or a mixture thereof. As the “filler”, an organic filler or an inorganic filler can be used, and an inorganic filler having a hydrophilic surface is preferable. Examples of such inorganic fillers include oxide fillers made of oxides such as silica, zeolite, alumina, titanium oxide, magnesium oxide and zinc oxide, which have a hydrophilic surface due to the presence of surface hydroxyl groups. . Among these, a silica filler is preferable from the viewpoint of wettability with a silicone polymer. Examples of the silica filler include spherical silica, porous silica (including zeolite and mesoporous silica), quartz powder, glass powder, glass beads, talc, and silica nanotube.

  In addition, it is preferable that the surface of the filler added is not hydrophobized. As needed, you may use the filler which performed the surface treatment using a coupling agent etc., or the hydrophilization by the hydration process.

  From the viewpoint of gas permeability, the filler is preferably a porous filler. As the porous filler, mesoporous silica and zeolite are preferable. As for the shape of the filler, from the viewpoint of wettability with the silicone-based polymer, it is preferable that the surface irregularity is so small that it can be ignored practically, the surface area is small, and the spherical shape does not affect the characteristics due to orientation.

  The particle diameter of the filler is preferably 1 nm to 100 μm, and particularly preferably 10 nm to 10 μm, from the viewpoint of reducing the thickness of the film formed from the selected material. When the filler is a non-porous silica particle having a hydrophobic or hydrophilic surface, the average particle size is preferably 10 to 120 nm from the viewpoint of further improving the gas permeability in the membrane. 10 to 60 nm is more preferable. Furthermore, when the filler is non-porous titanium oxide particles having a hydrophilic surface, the average particle diameter is preferably 10 to 60 nm from the viewpoint of further improving gas permeability in the membrane.

  When such a filler is added to the silicone-based polymer, the addition amount is preferably 1 to 500 parts by mass, and 10 to 300 parts by mass with respect to 100 parts by mass of the silicone-based polymer. More preferred. When the added amount of the filler is less than 1 part by mass, the effect of improving the gas permeability of the formed film tends to be difficult to obtain, and when it exceeds 500 parts by mass, There is a tendency that the mechanical strength is lowered and it is difficult to form a thin film.

  Examples of the “conductive polymer” include polyaniline, polyacetylene, polythiophene and polypyrrole, and polyaniline is preferable. Polyaniline has a low affinity for the silicone-based polymer, and the good solvent is different from that of the silicone-based polymer. Thereby, the space | gap between polyaniline and a silicone type polymer becomes large, and it is thought that the gas permeability improves.

  From the viewpoint of gas permeability, the conductive polymer is preferably added after being treated with an acid. When a conductive polymer such as polyaniline comes into contact with an acid, a leuco-emeraldine salt and / or an emeraldine salt are formed, and the affinity for the silicone-based polymer is significantly reduced. Thereby, it is thought that the space | gap between a silicone type polymer and a conductive polymer becomes larger, and the gas permeability improves. Examples of the acid to be added include hydrochloric acid, perchloric acid, sulfuric acid, nitric acid, vinylphosphonic acid, and acrylic acid.

  Thus, although the preferable addition amount of the acid in the case of processing a conductive polymer with an acid changes with combinations of a silicone type polymer and a conductive polymer, it is 0.5-45 with respect to 100 mass parts of conductive polymers. It is preferably 6 parts by mass. In particular, when the silicone-based polymer is a silicone-modified pullulan polymer and the conductive polymer is polyaniline, 0.9 to 1.4 parts by mass of 2N hydrochloric acid is added to 100 parts by mass of the conductive polymer. Is preferred. When the silicone polymer is a silicone-modified cycloolefin polymer and the conductive polymer is polyaniline, 4.6 to 9.1 parts by mass of 2N hydrochloric acid is added to 100 parts by mass of the conductive polymer. It is preferable.

  When such a conductive polymer (solution prepared by dissolving polyaniline (made by Aldrich, molecular weight: 20,000) as a conductive polymer in cyclohexanone and adjusting the solid content to 2 wt%) is added to the silicone polymer. The addition amount is preferably 2.2 to 80.0 parts by mass, more preferably 5.0 to 30 parts by mass with respect to 100 parts by mass of the silicone-based polymer. When the addition amount of the conductive polymer is less than 2.2 parts by mass, the effect of improving the gas permeability of the formed film tends to be difficult to obtain, and when it exceeds 80.0 parts by mass In addition, it is difficult to obtain the effect of improving the gas permeability of the film to be formed, the film formability is lowered, and the mechanical strength of the formed film tends to be lowered.

An “ionic liquid” is an ionic compound that is composed of an anion and a cation and dissolves in a region where it does not thermally decompose itself without being dissolved in a solvent. Examples of the cation in the ionic liquid include an imidazolium cation, a pyridinium cation, and a quaternary ammonium ion. Examples of anions in the ionic liquid include Cl ⁻ , Br ⁻ , BF ₄ ⁻ , PF ₆ ⁻ , NO ₃ ⁻ , and CF ₃ SO ₃ ⁻ . Specific examples of the ionic liquid include 1-ethyl-4-methylimidazolium-nitrate represented by the following formula (A) and 1-ethyl-4-methylimidazolium-phosphate represented by the following formula (B). The ionic liquid added to the permselective material of the present invention preferably has a melting point of 20 (normal temperature) to 100 ° C, more preferably 40 to 60 ° C.

  A solvent may be added to the permselective material as necessary. Examples of the solvent include toluene, methyl ethyl ketone, ethyl acetate, N-methylpyrrolidone (hereinafter referred to as “NMP”), cyclohexane, and cyclohexanone. The type of solvent can be selected according to the type of silicone polymer. For example, in the case of a silicone-modified pullulan polymer, toluene, methyl ethyl ketone, ethyl acetate, NMP, or the like can be used. Moreover, when adding conductive polymers, such as polyaniline, it is preferable to mix, after dissolving a silicone type polymer and a conductive polymer in a separate solvent. For example, it is preferable to mix after dissolving a silicone polymer in toluene and polyaniline in cyclohexanone.

  The permselective material may be mixed as necessary. For example, when the silicone polymer is in the form of pellets, it may be mixed with other components using an extruder, kneader or the like. Further, when the silicone polymer is dissolved in a solvent, it may be mixed by adding other components to the solution and stirring. Furthermore, the solvent may be removed after mixing.

  When a film is formed using the above-described permselective material, a film forming method corresponding to the component to be used can be used. For example, when the silicone polymer is in the form of pellets, a film can be obtained by a processing method such as a melt extrusion method or a calendar. In addition, when the silicone polymer is dissolved in a solvent, a film can be obtained by a processing method such as a casting method, a coater method, a water surface development method, or the like.

(Method for producing selectively permeable membrane structure)
The permselective membrane structure 40a according to the present embodiment is obtained by any one of the first manufacturing method, the second manufacturing method, or the third manufacturing method of the present embodiment. Hereinafter, the first and second manufacturing methods will be described.

  The first manufacturing method of the selectively permeable membrane structure 40a according to the present embodiment includes a step of filling the opening material of the reinforcing mesh material 302 with a sealing material and a step of shrinking the volume of the sealing material filled in the opening. Then, the permselective membrane 13a is formed from the permselective material so as to cover the exposed portion of the reinforcing mesh material 302 that is not covered with the sealing material and the exposed portion of the sealing material filled in the opening. And a step of removing the sealing material from the opening of the reinforcing mesh material 302 after forming the selectively permeable membrane 13a. Hereinafter, each process will be described with reference to FIGS.

  First, as shown in FIG. 3, a reinforcing mesh material 302 is installed on the PET film 330. Next, a sealing material 332 is applied to the reinforcing mesh material 302 installed on the PET film 330 with a wire coater, and the opening 302b of the reinforcing mesh material 302 is filled with the sealing material 332 (see FIG. 4). ).

As the sealing material 332, N, N-diethylacrylamide, (chemical formula: CH ₂ = C—ONHC ₂ H ₅ C ₂ H ₅ , hereinafter referred to as DEAA), diethylene glycol monovinyl ether (chemical formula: CH ₂ = C— (OCH) ₂ CH _{2) 2} -OH, hereinafter referred to as DEGV), polyethylene glycol (chemical _{formula: HO- (CH 2 -CH 2 -O} ) n -H (n = 300), hereinafter referred to as PEG), n, N- hydroxy At least one of ethyl acrylamide (chemical formula: CH ₂ = C—ONHC ₂ H ₅ OH, hereinafter referred to as HEAA) or a paint obtained by diluting these with an organic solvent or the like may be used. In particular, HEAA is preferable as the sealing material 332. By using HEAA, the reinforcing mesh material 302 can be more reliably spotted. When HEAA is used as the sealing material 332, for example, HEAA may be diluted with ethanol so as to have a paint form so that the concentration of HEAA is 80 wt%. By adjusting the amount of the solvent (ethanol) for diluting HEAA, it is possible to adjust the sealing position of the reinforcing mesh material 302 (filling amount of the sealing material 332 into the opening 302b), and as a result The thickness of the selectively permeable membrane 13a to be formed can be adjusted.

  Next, as shown in FIG. 5, the sealing material 332 applied to the reinforcing mesh material 302 is heat-treated to volatilize the diluting solvent (ethanol) from the sealing material 332 filled in the opening 302a. The volume of the fastening material 332 is contracted. In the step of shrinking the volume of the sealing material 332 filled in the opening 302a, a part of the reinforcing mesh material 302 covered with the sealing material 332 is exposed as the volume of the sealing material 332 shrinks. Thus, the exposed portion 302c of the reinforcing mesh material 302 is preferably formed.

  The sealing material 332 shrinks in volume by a heat treatment for drying it. Therefore, the exposed portion 302c of the reinforcing mesh material 302 can be easily formed by utilizing the volume shrinkage of the sealing material 332. Further, if the volume shrinkage of the sealing material 332 is used, a part of the sealing material 332 that covers the reinforcing mesh material 302 is removed in order to form the exposed portion 302c before the selective permeable membrane 13a is formed. Is no longer necessary. In the subsequent process, the selectively permeable membrane 13a is fixed to the reinforcing mesh material 302 by bonding the exposed portion 302c and the selectively permeable material. Further, the method of forming the exposed portion 302 c of the reinforcing mesh material 302 is not limited to the volume shrinkage of the sealing material 332.

  After shrinking the volume of the sealing material 332, as shown in FIG. 6, the exposed portion 302c of the reinforcing mesh material 302 and the exposed portion 332a of the sealing material 332 filled in the opening 302b are covered. Then, a paint-like selective transmission material 13s is applied with a wire coater or the like. Next, the selective permeable film 13a is formed from the selectively permeable material 13s by removing the solvent component of the selectively permeable material 13s by heat treatment. The paint-like selectively permeable material 13s may further contain a leveling agent. Since the paint-like selectively permeable material 13s further contains a leveling agent, the selectively permeable membrane 13a having a smooth surface can be obtained even when the adhesive property between the selectively permeable material 13s and the sealing material 332 is not good. A film can be formed.

  Next, the PET film 330 is peeled from the reinforcing mesh material 302 on which the permselective membrane 13a is laminated. Then, the sealing material 332 filled in the openings 302b of the reinforcing mesh material 302 is removed by washing with water from the surface of the reinforcing mesh material 302 opposite to the surface on which the selectively permeable membrane 13a is laminated. . After removing the sealing material 332, the reinforcing mesh material 302 and the selectively permeable membrane 13a are dried to remove moisture, thereby obtaining the selectively permeable membrane structure 40a shown in FIG.

  The method for removing the sealing material 332 filled in the openings 302b of the reinforcing mesh material 302 is not limited to cleaning with water. For example, the sealing material 332 may be washed and removed with a solvent or chemicals in which the components of the sealing material 332 are soluble. Alternatively, only the portion to be removed of the sealing material 332 applied to the reinforcing mesh material 302 is modified to be easily removed by irradiation with UV (ultraviolet light) or EB (electron beam), and then removed. Only the power portion may be removed.

  In the present embodiment, the reinforcing mesh material 302 is filled by filling the opening 302 b of the reinforcing mesh material 302 with the sealing material 332, and a substantially smooth flat surface is formed on the reinforcing mesh material 302. Then, after filling the opening 302 b of the reinforcing mesh material 302 with the sealing material 332, the selective permeable film 13 a is formed from the selective permeable material 13 s so that the paint-like selectively permeable material 13 s becomes the opening 302 b of the reinforcing mesh material 302. The selective permeation film 13a having a uniform thickness and a smooth surface can be formed because it can be prevented from flowing excessively (to the extent that the opening 302b is filled).

  In a multilayer film formation on a substrate by a general coater method, a film forming material whose solution viscosity is adjusted with a solvent or the like is used in order to adjust to an optimum processing condition. In particular, in the formation of a thin film, it is common to use a film-forming material adjusted to a low viscosity by relatively increasing the amount of solvent of the film-forming material. However, with a low-viscosity film-forming material, it has been difficult to apply to a substrate having a large opening diameter, such as a reinforcing mesh material, from the viewpoint of surface tension and fluidity. That is, since the applied film forming material flows into the openings of the reinforcing mesh material, the laminated state of the reinforcing mesh material and the film cannot be obtained, and the film forming accuracy (thickness adjustment, thickness variation) Thus, a good film could not be obtained. On the other hand, in this embodiment, the selectively permeable material 13s is applied to the reinforcing mesh 13a by forming the selectively permeable film 13a from the selectively permeable material 13s after filling the openings 302b of the reinforcing mesh material 302 with the sealing material 332. Since it can suppress flowing into the opening part 302b of the material 302, the problem which the above-mentioned general coater method has can be solved.

  Further, in the present embodiment, after forming the permselective membrane 13a, the permeation material 332 is removed from the opening 302b of the reinforcing mesh material 302 to thereby remove the permselective membrane 13a facing the opening 302b of the reinforcing mesh material 302. The gas permeability in can be ensured.

  Furthermore, in this embodiment, the volume shrinkage rate of the sealant 332 is reduced when the volume of the sealant 332 filled in the opening 302b is contracted by adjusting the amount of the solvent that dilutes the paint-like sealant 332. Can be adjusted. Therefore, the volume of the space formed in the opening 302b of the reinforcing mesh material 302 can be adjusted with the volume shrinkage of the sealing material 332, and the volume of the selectively permeable material 13s introduced into this space can also be adjusted. As a result, it is possible to adjust the thickness of the selectively permeable film 13a after film formation, particularly the thickness of the selectively permeable film 13a facing the opening 302b (the thickness of the selectively permeable film 13a positioned inside the opening 302b). Further, when the permselective material 13s is introduced into the space formed in the opening 302b of the reinforcing mesh material 302 due to the volume shrinkage of the sealing material 332, the reinforcing mesh material 302 is embedded in the selectively permeable film 13a after film formation. You can make a structure. This structure has an anchor effect, and the permselective membrane 13a can be firmly adhered to the reinforcing mesh material 302.

  Next, the 2nd manufacturing method of the permselective membrane structure 40a which concerns on this embodiment is demonstrated. Hereinafter, differences between the first manufacturing method and the second manufacturing method described above will be described, and description of common points between the first manufacturing method and the second manufacturing method will be omitted. In the first manufacturing method, the permselective film 13a is formed so as to directly cover the exposed portion 332a of the sealing material 332 filled in the opening 302b, whereas in the second manufacturing method, the opening 302b is filled. The first manufacturing method is different from the second manufacturing method in that the permselective film 13a is formed so as to cover the intermediate layer after the intermediate layer is formed on the exposed portion 332a of the sealing material 332. .

  That is, the second manufacturing method of the permselective membrane structure 40a of the present embodiment includes the step of filling the opening 302b of the reinforcing mesh material 302 with the sealing material 332 and the sealing material 332 filled in the opening 302b. A step of forming an intermediate layer 334 having both adhesiveness to the sealing material 332 and adhesiveness to the selective transmission material 13s on the exposed portion 332a, and a step of shrinking the volume of the sealing material 332 filled in the opening 302b. A step of forming the selectively permeable film 13a from the selectively permeable material 13s so as to cover the exposed portion 302c of the reinforcing mesh material 302 and the intermediate layer 334 that are not covered with the sealing material, and the selectively permeable film 13a is formed. And removing the sealing material 332 and the intermediate layer 334 from the opening 302b of the reinforcing mesh material 302. Below, each process of the 2nd manufacturing method which concerns on this embodiment is demonstrated, referring FIGS.

  First, as shown in FIG. 8, after the reinforcing mesh material 302 is installed on the PET film 330, a sealing material 332 is applied to the reinforcing mesh material 302 installed on the PET film 330 by a wire coater. The sealing material 332 is filled in the opening 302b of the reinforcing mesh material 302.

  Next, a coating material having both adhesiveness with the sealing material 332 and adhesiveness with the selectively permeable material 13s is applied onto the reinforcing mesh material 302 to which the sealing material 332 is applied, and the intermediate layer 334 is applied from this coating material. Form. As a result, the exposed portion 332 a of the sealing material 332 filled in the opening 302 b of the reinforcing mesh material 302 is covered with the intermediate layer 334. The intermediate layer 334 may be a layer having both adhesiveness with the sealing material 332 and adhesiveness with the selective transmission material 13s. For example, a layer containing polyvinyl alcohol (hereinafter referred to as PVA) or the like is an intermediate layer. It may be 334. Since PVA is less soluble in water than a sealing material 332 such as HEAA, it is preferable to make the intermediate layer 334 containing PVA thinner in order to facilitate removal of the intermediate layer 334 in a later step. The thickness is preferably about 0.01 to 30 μm.

  As the PVA used as the intermediate layer 334, for example, a known PVA having a degree of polymerization of about 400 to 4000 and a degree of saponification of 80 mol% or more can be used. In this embodiment, PVA having high water solubility is used. More specifically, it is preferable to use PVA having a degree of polymerization of about 100 to 400 and a degree of saponification of about 0 to 90 mol%. More specifically, the polymerization degree is about 200 to 250 and the saponification degree is about 81 mol% PVA (JL-05E manufactured by Nippon Vinegar Poval Co.), or the polymerization degree is about 200 to 250 and the saponification degree is about It is preferable to use PVA (ASP05 manufactured by Nippon Vinegar Poval) which is about 88 mol%. Moreover, you may use the modified PVA which has functional groups other than the hydroxyl group and acetic acid group of general PVA.

  After the formation of the intermediate layer 34, the sealing material 332 filled in the opening 302b and the solvent component contained in the intermediate layer 334 are removed by heat treatment, and the volume of the sealing material 332 and the intermediate layer 334 is contracted, thereby reinforcing the mesh. An exposed portion 302c of the material 302 is formed (see FIG. 9).

  Next, a paint-like selective transmission material 13s is applied by a wire coater or the like so as to cover the exposed portion 302c of the reinforcing mesh material 302 and the intermediate layer 334. Next, a selective permeable film 13a is formed from the selectively permeable material 13s by removing the solvent component of the selectively permeable material 13s by heat treatment (see FIG. 10).

  After forming the selectively permeable membrane 13a, the PET film 330 is peeled from the reinforcing mesh material 302 on which the selectively permeable membrane 13a is laminated. Then, from the side of the reinforcing mesh material 302 opposite to the surface on which the selectively permeable membrane 13a is laminated, the sealing material 332 filled in the openings 302b of the reinforcing mesh material 302, and the intermediate layer behind the sealing material 332 334 is removed by washing with water or the like. After removing the sealing material 332 and the intermediate layer 334, the reinforcing mesh material 302 and the selectively permeable membrane 13a are dried to remove moisture, thereby obtaining the selectively permeable membrane structure 40a shown in FIG.

  In the said 2nd manufacturing method, there can exist an effect similar to the said 1st manufacturing method. Furthermore, in the second manufacturing method, the selectively permeable material 13s is formed on the surface of the intermediate layer 334 that adheres to the sealing material 332 and also has adhesiveness to the selectively permeable material 13s. It is easy to form a permselective membrane 13a having a uniform thickness and a smooth surface. Temporarily, using the selectively permeable material 13s that is difficult to adhere to the sealing material 332, the exposed portion 302c of the reinforcing mesh material 302 and the exposed portion 332a of the sealing material 332 filled in the opening 302b are directly covered. When the permselective membrane 13a is formed, the sealing material 332 and the permselective material 13s are difficult to adhere to each other, and it is difficult to form the permselective material 13s into a film shape on the surface of the sealing material 332. In the manufacturing method, the permselective material 13s is formed on the surface of the intermediate layer 334 that adheres to the sealing material 332 and also has the adhesiveness to the permselective material 13s, so that such a problem does not occur. That is, in the second manufacturing method, the wettability of the selective transmission material 13s to the sealing material 332 (film formation) is provided via the intermediate layer 334 compatible with both the sealing material 332 and the selective transmission material 13s. The film forming accuracy of the selective transmission material 13s can be improved. In addition, when the sealing material 332 and the intermediate layer 334 are removed from the opening 302b after the selective permeable film 13a is formed, the reinforcing mesh material 302 is used as a mask and the intermediate layer 334 is etched. A part of the intermediate layer 334 may remain between the permselective membrane 13a and the reinforcing mesh material 302. In this case, if a material having an adhesive effect (a material that develops an adhesive property by a secondary load such as heat) is used as the intermediate layer 334, the selectively permeable membrane 13a and the reinforcing mesh material 302 are bonded (immobilized). Is also possible.

(Air conditioning system)
The permselective membrane structure 40a according to the present embodiment described above can be used, for example, in an air conditioning system described below. This air conditioning system includes a selectively permeable membrane structure 40a as a membrane for supplying gas to the air conditioned space and / or discharging gas from the air conditioned space. As this air-conditioning system, for example, a system in which the above-mentioned selective permeable membrane structure 40a is installed at an intake for introducing outside air (outside air introduction port) can be mentioned. As the air-conditioning target space, for example, a space such as an automobile, a house, a bullet train, an airplane, and the like that needs to exchange the gas in the space with the outside air can be cited, and a specific example thereof is as shown in FIG. An automobile is mentioned.

  FIG. 11 is a schematic cross-sectional view of an automobile, which is one form of an air conditioning system, cut in the front-rear direction. The vehicle compartment 19 of the automobile 10 includes the compartment wall 11 and the permselective membrane structure 40a, and is substantially free from outside air at portions other than the permselective membrane structure 40a installed at the intake for introducing the external air. Blocked.

  The vehicle interior wall 11 is made of a material that does not substantially transmit gas, such as iron, aluminum, and glass. The thickness of the selectively permeable membrane 13a included in the selectively permeable membrane structure 40a is preferably 0.1 to 10 μm. As a specific installation location of the selectively permeable membrane structure 40a in the automobile 10, for example, there is an intake for introducing outside air in the air conditioner unit shown in FIG.

  FIG. 12 is a schematic cross-sectional view showing a part of an air conditioner unit 30 in an automobile which is an embodiment of the air conditioning system of the present invention. As shown in FIG. 12, the air conditioner unit 30 includes an air conditioner unit case 35, a centrifugal blower fan 37, and a selectively permeable membrane structure 40a. The air conditioner unit case 35 has an outside air inlet 35a, an inside air inlet 35b, and an opening 35c. The blower fan 37 is installed in the air conditioner unit case 35 on a path through which the inside air circulates. The selectively permeable membrane structure 40a is installed in the air conditioner unit case 35 so as to close the outside air inlet 35a.

  According to such an air conditioner unit 30, outside air is introduced from the outside air introduction port 35a through the permselective membrane structure 40a, and inside air is introduced from the inside air introduction port 35b into the air conditioner unit. / Or inside air is supplied. In some cases, the inside air is discharged from the outside air inlet 35a through the selectively permeable membrane structure 40a to the outside of the vehicle.

  The air conditioner unit case 35 is made of a resin having a certain degree of elasticity such as polypropylene and having excellent mechanical strength. As the centrifugal blower fan 37, those conventionally used for circulating the inside air in an automobile can be used.

  In addition to the above, the specific permeable membrane structure 40a in the vehicle 10 is installed in place of the pressure adjusting ventilator (FIG. 13), the ceiling (FIGS. 14 to 16), the windshield (FIG. 17), the pillar ( 20 and 21), a floor (FIG. 22), a door (FIGS. 23 to 27), and the like. Hereinafter, detailed examples of these installation locations will be described.

(Configuration of pressure adjustment ventilator)
FIG. 13 is a schematic configuration diagram showing an embodiment of a vehicle provided with the permselective membrane structure of the present invention in a pressure adjusting ventilator.

  As shown in FIG. 13A, the pressure adjusting ventilator 110 of the present embodiment is disposed on both left and right side surfaces in the vicinity of the bumper 34 at the rear of the vehicle 10. As shown in FIG. 13B, which is a cross-sectional view of the rear portion of the vehicle 10 as viewed from the rear of the vehicle 10, the pressure adjusting ventilator 110 includes a housing 38, a damper 32, and a selectively permeable membrane structure. 40a.

  The pressure adjusting ventilator 110 is attached to a body 122 portion of the vehicle 10 that is partially cut into a substantially rectangular shape so as to be embedded inside the body 122. That is, the casing 38 of the pressure adjusting ventilator 110 is formed in a rectangular tube shape, and a flange is provided on an end surface of the casing 38 formed in the rectangular tube shape on the outside of the vehicle 10. The flange is fixed to the body 122 by welding or the like.

  In the housing 38, the lower surface of the end (back end) opposite to the end fixed to the body 122 is bent obliquely upward toward the passenger compartment 19. This bent portion is called a damper receiving portion 38a. As will be described later, the lower end portion of the damper 32 comes into contact with the damper receiving portion 38a from the outside of the vehicle 10 toward the vehicle compartment 19 with the door closed.

  The damper 32 is attached to the housing 38 with a hinge 32a. Specifically, the upper side portion of the damper 32 and the inner inner upper wall of the rectangular tubular casing 38 are coupled by a hinge 32a, and the damper 32 is attached to be rotatable about the hinge 32a. Yes.

  In the pressure adjusting ventilator 110, when the door (not shown) of the vehicle 10 is closed, the pressure in the passenger compartment 19 increases. Then, the damper 32 is pushed toward the vehicle 10 outer side from the vehicle interior 19 side by the increased pressure. Then, the damper 32 is rotated about the hinge 32a and is in an open state, that is, a state β in FIG.

  When the damper 32 is in the open state, an air flow occurs when the door is closed as indicated by an arrow in FIG. 13A, and the air in the passenger compartment 19 escapes outside the passenger compartment 19. As described above, when the door is closed, the damper 32 is opened, and the rise in the pressure inside the passenger compartment 19 is alleviated.

  On the other hand, in the state where the door is closed, there is no pressure increase in the compartment 19, so no pressure is applied to the damper 32 from the compartment 19 side. If pressure is not applied to the damper 32 from the vehicle compartment 19 side, the damper 32 rotates to the vehicle compartment 19 side with the hinge 32a as a center by its own weight. When the damper 32 rotates and the lower end portion of the damper 32 comes into contact with the damper receiving portion 38a, it cannot be rotated any further. Therefore, the damper 32 is in a closed state, that is, the state of α in FIG.

  Even when pressure is applied to the damper 32 from the outside of the vehicle 10 toward the vehicle compartment 19, the damper 32 tries to rotate toward the vehicle compartment 19 around the hinge 32 a. The portion contacts the damper receiving portion 38a. Therefore, since the damper 32 cannot rotate any more, the damper 32 is in a closed state, and the vehicle compartment 19 is in a sealed state.

(ceiling)
FIGS. 14-16 is a schematic block diagram which shows the vehicle which is one form of the air conditioning system of this invention provided with the permselective membrane structure of this invention in a ceiling part. As shown to Fig.14 (a), the vehicle 10 in this embodiment is provided with the permselective membrane structure 40a in the ceiling part. Hereinafter, the specific form of the ceiling part in this embodiment is demonstrated.

[Embodiment 1A]
As shown in FIG. 14B, the ceiling portion of the embodiment 1A includes a cavity 70 provided in the ceiling portion of the vehicle 10, an outside air inlet 26 and an outside air outlet provided in a part of the outer wall 22 of the vehicle 10. 28, a selectively permeable membrane structure 40a provided in a part of the cavity 70, and the like.

  The cavity 70 is formed by an inner wall 24 that faces the interior of the vehicle compartment 19 and an outer wall 22 that faces the exterior of the vehicle interior 19. The outer wall 22 and the inner wall 24 are made of a material that does not substantially transmit gas, such as iron, aluminum, and glass.

  The outside air inlet 26 is a hole provided in the outer wall 22 that forms the cavity 70 in order to introduce outside air into the cavity 70 from the traveling direction side of the vehicle 10, and the outside air outlet 28 is the outside air introduced into the cavity 70. Is a hole provided in the outer wall 22 that forms the cavity 70 to discharge the vehicle 10 to the opposite side of the traveling direction of the vehicle 10.

  The outside air inlet 26 and the outside air outlet 28 are substantially rectangular elongated holes formed with the lateral direction of the vehicle 10 as the longitudinal direction, and the lengths in the longitudinal direction and the lateral direction are introduced into the vehicle type and the cavity 70. Determined by the amount of outside air.

  In the selectively permeable membrane structure 40a, at least a part of the selectively permeable membrane structure 40a is in contact with the outside air introduced into the cavity 70 by the outside air inlet 26 on the inner wall 24 forming the cavity 70, and the other portion is in the vehicle interior 19. It is arranged in contact with the air inside.

  Specifically, as shown in FIG. 14B, a part of the inner wall 24 of the vehicle 10 is cut into a substantially square shape. Then, the permselective membrane structure 40a is formed in a substantially square plate shape having the same size as the inner wall 24 portion cut out in a substantially square shape, and the periphery is reinforced with a reinforcing material. Here, among the reinforcing materials that reinforce the periphery of the selectively permeable membrane structure 40a, the reinforcing material in the traveling direction of the vehicle 10 is referred to as a front reinforcing material 12a, and the reinforcing material on the opposite side of the traveling direction of the vehicle 10 is referred to as a rear reinforcing material 12b.

  Then, a permselective membrane structure 40a whose periphery is reinforced with a reinforcing material is attached to a portion obtained by cutting the inner wall 24 into a substantially square shape. Here, the inner wall 24 is cut into a substantially square shape, but it is not particularly necessary to cut it into a substantially square shape. The inner wall 24 is made of another shape such as a circle, a trapezoid, or a plurality of straight lines or curves according to the shape of the ceiling. You may cut out to a more complicated shape.

  Next, an air conditioning system that prevents water droplets from entering the cavity 70 from the outside air inlet 26 and the outside air outlet 28 will be described with reference to FIG. FIGS. 15A to 15C are diagrams illustrating a structure for preventing water droplets from entering the cavity 70. FIG.

[Embodiment 2A]
FIG. 15A is a view showing a form (Embodiment 2A) in which a front opening / closing door 27a and a rear opening / closing door 27c are provided as means for preventing water droplets from entering the cavity 70, that is, as water drop intrusion prevention means. . The front opening / closing door 27a and the rear opening / closing door 27c are attached to the outer wall 22 by hinges 27b, 27d, respectively, and open / close along the traveling direction of the vehicle 10 by rotating around the hinges 27b, 27d.

  The attachment position of the hinge 27b is behind the outside air inlet 26 and in front of the front reinforcing member 12a of the selectively permeable membrane structure 40a along the traveling direction of the vehicle 10. The attachment position of the hinge 27d is in front of the outside air outlet 28 along the traveling direction of the vehicle 10 and behind the rear reinforcing member 12b of the selectively permeable membrane structure 40a.

  The front opening / closing door 27a and the rear opening / closing door 27c are opened and closed by the pressure of the outside air. That is, outside air is introduced into the cavity 70 from the outside air inlet 26 when the vehicle 10 travels. The outside air introduced from the outside air inlet 26 strikes the front opening / closing door 27a. Then, since pressure is generated by the outside air on the surface of the front opening / closing door 27a on the outside air inlet 26 side, the front opening / closing door 27a is opened by the pressure.

  Conversely, when the vehicle 10 stops, outside air is not introduced from the outside air inlet 26. Therefore, no pressure is generated on the surface of the front opening / closing door 27a on the outside air inlet 26 side, so the front opening / closing door 27a is closed.

  The rear opening / closing door 27c is also opened / closed by the outside air introduced into the cavity 70 in the same manner as the front opening / closing door 27a. The maximum angle θ when the front opening / closing door 27a is opened is determined by the position of the front reinforcing member 12a of the selectively permeable membrane structure 40a. That is, the maximum angle θ is determined so that the lower end portion of the front opening / closing door 27a is positioned on the traveling direction side of the vehicle 10 with respect to the front reinforcing member 12a when the front opening / closing door 27a is opened to the maximum.

  In this way, even when outside air hits the front opening / closing door 27a and the front opening / closing door 27a opens to the maximum angle θ, water droplets contained in outside air hit the front opening / closing door 27a. Even if a water droplet drops downward in the figure, it does not adhere to the surface of the selectively permeable membrane structure 40a. That is, since water droplets do not adhere to the surface of the selectively permeable membrane structure 40a, the gas permeable performance of the selectively permeable membrane structure 40a can be maintained.

[Embodiment 3A]
FIG. 15B shows a configuration using a weir as a water droplet intrusion preventing means, that is, a front weir 27e is disposed between the outside air inlet 26 and the front reinforcing member 12a of the permselective membrane structure 40a, and is selectively permeated. It is a figure which shows the form (Embodiment 3A) by which the rear part weir 27f is arrange | positioned between the back reinforcement material 12b of the membrane structure 40a, and the external air discharge port 28. FIG.

  The front weir 27e is composed of a pair of substantially rectangular strips arranged in the front-rear direction in the traveling direction of the vehicle 10. The pair of plate members are attached such that the longitudinal direction thereof is the vehicle width direction of the vehicle 10, and the plate member disposed on the outside air inlet 26 side of the pair of plate members is attached to the outer wall 22 of the vehicle 10. It is attached so that a gap may be formed between the inner wall 24 and the inner wall 24. Further, the plate material arranged on the selectively permeable membrane structure 40 a side is attached to the inner wall 24 of the vehicle 10 so that a gap is formed between the plate member and the outer wall 22. The longitudinal direction of each plate is slightly longer than the length of the selectively permeable membrane structure 40a in the vehicle width direction of the vehicle 10 in order to prevent water droplets from entering the selectively permeable membrane structure 40a.

  The rear weir 27f is composed of a single plate material. The plate material is attached to the end of the outer wall 22 that forms the outside air outlet 28 below the vehicle 10 and obliquely forward in the traveling direction of the vehicle 10. This plate material also has a length equal to or longer than the length of the selectively permeable membrane structure 40a in the vehicle width direction of the vehicle 10.

  According to such a front weir 27e, water drops contained in the outside air introduced into the cavity 70 are first removed by the plate on the outside air inlet 26 side of the plate constituting the front weir 27e, and the outer surface of the inner wall 24 is removed. Dropped upward, travels on the outer surface of the inner wall 24 and is discharged from the drain (not shown) to the outside of the vehicle 10. Further, the water droplets remaining without being separated by the plate on the outside air inlet 26 side are removed by the plate on the side of the permselective membrane structure 40a, and are transmitted along the outer surface of the inner wall 24 from the drain (not shown) to the outside of the vehicle 10. Is discharged. Accordingly, water drops do not enter the cavity 70 from the outside air inlet 26.

  In addition, since the outside air is discharged from the outside air discharge port 28 in the rear dam 27f, the splash of raindrops and the like from the outer plate forming the vehicle 10 is prevented rather than the ingress of water droplets accompanying the inflow of outside air to the outside air discharge port 28. I can do it. Therefore, if the plate material is attached to the end portion of the outside air outlet 28 as described above, it is possible to prevent water droplets from entering the cavity 70.

  As described above, since water droplets do not enter the cavity 70 from the outside air inlet 26 or the outside air outlet 28, the water droplets do not adhere to the surface of the selectively permeable membrane structure 40a installed in the cavity 70. Water droplets do not adhere to the surface of the selectively permeable membrane structure 40a. Therefore, it does not prevent the permselective membrane structure 40a from transmitting oxygen or carbon dioxide.

[Embodiment 4A]
Next, a case where outside air is introduced into the cavity 70 in accordance with the oxygen concentration in the passenger compartment 19 (Embodiment 4A) will be described with reference to FIGS. 14 and 15C.

(Constitution)
As shown in FIGS. 14 and 15C, the air conditioning system in Embodiment 4A includes a front fan 29a, a rear fan 29b, an oxygen sensor 18, and a control unit 90 in addition to the air conditioning systems shown in Embodiments 1A to 3A. It is the composition which was made.

  The front fan 29a and the rear fan 29b are for adjusting the amount of outside air introduced into the cavity 70 based on an outside air introduction command for introducing outside air.

  As shown in FIG. 15C, the front fan 29a is disposed between the outside air inlet 26 and the front reinforcing member 12a in the cavity 70, similarly to the front weir 27e (see FIG. 15B). ing. Further, as shown in FIG. 15C, the rear fan 29b is disposed in the cavity 70 between the outside air outlet 28 and the rear reinforcing member 12b of the selectively permeable membrane structure 40a.

The oxygen sensor 18 is for detecting the oxygen concentration in the passenger compartment 19 and is embedded in the dashboard of the vehicle 10 as shown in FIG.
The control unit 90 outputs an outside air introduction command for introducing outside air to the front fan 29a and the rear fan 29b when the oxygen concentration in the passenger compartment 19 detected by the oxygen sensor 18 is a predetermined concentration. It consists of a CPU (Central Processing Unit), ORM (Object / Relational Mapping), RAM (Random Access Memory), I / O (Input / Output), etc. (not shown). The control unit 90 is stored inside the dashboard of the vehicle 10 as shown in FIG.

(Operation and features)
In the air conditioning system configured as described above, the oxygen concentration detected by the oxygen sensor 18 is sent to the control unit 90.

  The controller 90 determines whether or not the oxygen concentration is equal to or lower than a predetermined value based on the oxygen concentration information sent from the oxygen sensor 18. When it is determined that the oxygen concentration is equal to or lower than the predetermined value, an outside air introduction command is output to the front fan 29a and the rear fan 29b, and the outside air is introduced into the cavity 70. On the other hand, when the control unit 90 determines that the oxygen concentration exceeds the predetermined value, the outside air introduction command is not output to the front fan 29a and the rear fan 29b. It should be noted that the “predetermined value” of the oxygen concentration indicates the oxygen concentration required for maintaining the comfort in the passenger compartment 19.

  The front fan 29a and the rear fan 29b operate when receiving a command from the control unit 90, and introduce more outside air into the cavity 70 than when the outside air introduction port 26 is simply provided.

  Thus, according to the air conditioning system of Embodiment 4A, outside air is introduced into the cavity 70 only when the oxygen concentration in the passenger compartment 19 is equal to or lower than a predetermined value. Therefore, since the outside air containing a certain amount of hydrocarbon or the like is not always in contact with the selectively permeable membrane structure 40a, the hydrocarbon or the like is not always adsorbed or absorbed by the selectively permeable membrane structure 40a. Therefore, the deterioration of the selective separation performance of the selectively permeable membrane structure 40a is delayed, that is, the lifetime of the selectively permeable membrane structure 40a can be extended.

  Although the case where the oxygen sensor 18 is used has been described here, a carbon dioxide sensor is used instead of the oxygen sensor 18, and the front fan 29a and the rear fan 29b are used when the carbon dioxide concentration in the passenger compartment 19 increases. May be activated to introduce outside air into the cavity 70.

  In addition to the oxygen sensor 18 and the carbon dioxide sensor described above, a sensor that detects the concentration of a minute solid component, a sensor that counts the number of minute solid components, and the like are used, and the outside air is hollowed according to the concentration and the like. You may make it introduce in 70.

[Other Embodiments]
(1) In Embodiments 1A to 4A described above, a part of the inner wall 24 of the ceiling portion of the vehicle 10 is formed by the selectively permeable membrane structure 40a. However, as shown in FIG. May be opened.

  That is, as shown in FIG. 16A, a large number of small holes are formed in the ceiling portion of the inner wall 24, and the perforated portion is covered with the selectively permeable membrane structure 40a. At this time, all of the many small holes opened are covered with the selectively permeable membrane structure 40a, and the reinforcing material 12 for reinforcing the periphery of the selectively permeable membrane structure 40a is in close contact with the inner wall 24, so that the outside air The outside air introduced from the introduction port 26 is prevented from entering the vehicle compartment 19 directly.

  At this time, as shown in FIG. 16B, a filter for removing dust and the like as compared with the minute solid component may be provided on the surface of the selectively permeable membrane structure 40a. Furthermore, instead of the small holes described above, as shown in FIG. 16 (c), the ceiling portion of the inner wall 24 is cut off, the portion is closed with a mesh-like material, and the permselective membrane structure 40a is disposed on the surface. May be.

(Glass)
[Embodiment 1B: Windshield]
FIG. 17 is a schematic configuration diagram showing a vehicle (Embodiment 1B) that is an embodiment of the air-conditioning system of the present invention that includes the selectively permeable membrane structure of the present invention in a windshield portion. As shown in FIG. 17B, a selectively permeable membrane structure 40a is provided at the lower part of the windshield of the vehicle 10, and includes a cover 112, an outside air inlet 126, an outside air outlet 128, a front weir 127a, a rear weir. 127b, a selectively permeable membrane structure 40a, and the like are provided.

  The cover 112 covers the side of the selectively permeable membrane structure 40a that contacts the outside air in order to block water droplets. The cover 112 is formed to be substantially rectangular when viewed from the front of the vehicle 10 and to be curved along the windshield 130 when viewed from the lateral direction of the vehicle 10.

  The length in the longitudinal direction and the short direction of the cover 112 is slightly longer than the length in the longitudinal direction and the short direction of the selective permeable membrane structure 40a formed in a flat plate shape to be described later. The entire surface of the permeable membrane structure 40a can be covered.

  An outside air inlet 126 for introducing outside air into a space 120 (hereinafter simply referred to as the space 120) covered with the cover 112 is provided at an end of the cover 112 on the vehicle traveling direction side. An outside air discharge port 128 for discharging outside air introduced into the space 120 is provided at the opposite end.

  The outside air introduction port 126 and the outside air discharge port 128 are substantially rectangular elongated holes that are bored with the lateral direction of the vehicle 10 as the longitudinal direction, and the sizes of the holes, that is, the lengths of the holes in the longitudinal direction and the transverse direction are as follows. It is determined by the vehicle type and the amount of outside air introduced into the space 120.

  Further, a front weir 127a is disposed in the vicinity of the space 120 side of the outside air inlet 126, and the rear portion is disposed outside the windshield 130 in the space 120 near the upper boundary between the windshield 130 and the selectively permeable membrane structure 40a. A weir 127b is arranged.

  The front weir 127 a is configured by a substantially rectangular long and narrow plate member disposed in the front-rear direction in the traveling direction of the vehicle 10. The plate material is attached so that the longitudinal direction thereof is the vehicle width direction of the vehicle 10, and is attached so that a gap is formed between the plate material and the selectively permeable membrane structure 40a. The longitudinal direction of the plate material is slightly longer than the length of the selectively permeable membrane structure 40a in the 10 vehicle width direction of the vehicle in order to prevent water droplets from entering the selectively permeable membrane structure 40a.

  The rear dam 127b is made of the same plate material as the front dam 127a. This plate material also has a length equal to or longer than the length of the selectively permeable membrane structure 40a in the vehicle width direction of the vehicle 10. The water droplets contained in the outside air introduced into the space 120 by the front dam 127a are removed by the front dam 127a, dropped on the outer surface of the body of the vehicle 10, and transferred to the drain (see FIG. From the vehicle 10 to the outside of the vehicle 10.

  Further, the rear weir 127b blocks water droplets that try to enter the space 120 along the outer surface of the windshield 130, and the blocked water droplets are discharged to the outside of the vehicle 10 by a drain (not shown).

  The selectively permeable membrane structure 40a is disposed so as to constitute a part of the windshield 130 of the vehicle 10. Specifically, as shown in FIG. 17B, a part of the lower portion of the windshield 130 of the vehicle 10 is cut into a substantially rectangular shape so that the vehicle width direction is the longitudinal direction. Then, the permselective membrane structure 40a is formed in a substantially rectangular flat plate having the same size as the front glass 130 cut into a substantially rectangular shape, and the front glass 130 is cut out of the permselective membrane structure 40a formed in a substantially rectangular flat plate shape. Fit in the part.

  The size of the selectively permeable membrane structure 40 a, that is, the length in the longitudinal direction and the short direction is determined by the vehicle type of the vehicle 10 and the amount of outside air introduced into the space 120.

[Embodiment 2B: Rear window]
Next, the form (Embodiment 2B) in which the permselective membrane structure 40a is mounted on the porous glass 132 and the rear window 139 is formed will be described with reference to FIG. FIG. 18 is a schematic configuration diagram when the rear window 139 is configured by the porous glass 132 to which the selectively permeable membrane structure 40a is attached.

  In the vehicle air-conditioning system of the present embodiment, the glass portion of the rear window 139 as shown in FIG. 18A is replaced with the porous glass 132 having the selectively permeable membrane structure 40a as shown in FIG. 18B. It is a replacement.

  The porous glass 132 has pores in the entire material, and has a function of allowing air to pass in both directions inside and outside the vehicle compartment 19.

  The permselective membrane structure 40a is mounted in close contact with the entire surface of the porous glass 132 on the vehicle compartment 19 side. In addition, a reinforcing material 134 made of a mesh-like material is attached to the selectively permeable membrane structure 40a attached to the porous glass 132 on the side of the passenger compartment 19 to reinforce the selectively permeable membrane structure 40a. Yes.

  As shown in FIG.18 (c), you may use what is provided with the filter 136 for dust prevention between the mesh-shaped reinforcing material 134 and the permselective membrane structure 40a in FIG.18 (b). By providing the dustproof filter 136, it is possible to prevent dust or the like in the passenger compartment 19 from directly attaching to the selectively permeable membrane structure 40a.

  Further, as shown in FIG. 18 (d), instead of using the mesh-like reinforcing material 134 in FIG. 18 (b), the permselective membrane structure 40a is sandwiched between two porous glasses 132a and 132b, and porous. The porous glass 132a, the permselective membrane structure 40a, and the porous glass 132b may be laminated in this order.

[Embodiment 3B: Sunroof]
Next, an embodiment (embodiment 2B) in which the sunroof 138 is formed by attaching the permselective membrane structure 40a to the porous glass 132 will be described with reference to FIG. FIG. 19 is a configuration diagram when the sunroof 138 is configured by the porous glass 132 on which the permselective membrane structure 40a is mounted.

  In this air conditioning system, the glass portion of the sunroof 138 as shown in FIG. 19B is replaced with the porous glass 132 having the selectively permeable membrane structure 40a as shown in FIG. 19A, and the sunroof 138 is formed. A large number of holes are provided in the inner wall 24 of the vehicle 10.

  In this way, outside air flows from the vehicle traveling direction toward the opposite direction of the vehicle traveling direction along the outer surface of the porous glass 132 constituting the sunroof 138. At this time, the air in the passenger compartment 19 and the outside air are exchanged via the selectively permeable membrane structure 40a.

(Pillar)
FIG. 20 is a schematic cross-sectional view showing a vehicle, which is an embodiment of the air conditioning system of the present invention, provided with the permselective membrane structure of the present invention in the pillar portion. As shown in FIG. 20, the vehicle 10 is surrounded by wall surfaces such as aluminum and glass that are substantially impermeable to air, and the vehicle 10 in which outside air does not enter and the vehicle compartment such as a trunk and an engine room in which outside air can enter. It consists of 19 outside spaces.

  In addition, pillars 50, 52, and 54 are provided as part of the wall surface constituting the passenger compartment 19. The pillars 50, 52, 54 include a front pillar 50 provided at both end portions of the windshield at the front of the vehicle compartment 19, and a center pillar 52 provided at a substantially central portion in the vehicle 10 longitudinal direction of the windows on both sides of the vehicle 10. There are rear pillars 54 provided at both ends of the rear window at the rear of the passenger compartment 19.

  Further, the vehicle 10 is provided with an air conditioner (not shown). This air conditioner has only the inside air circulation mode.

  Next, the configuration of the air conditioning system will be described with reference to FIG. 21A is a schematic configuration diagram of the vehicle 10 and the pillars 50, 52, and 54 provided in the vehicle 10, and FIG. 21B is a schematic configuration diagram schematically illustrating the structure of the center pillar 52. It is.

  As shown in FIG. 21A, the vehicle 10 includes a front pillar 50, a center pillar 52, and a rear pillar 54. Since the pillars 50, 52, and 54 have the same structure, the details will be described below using the center pillar 52 as an example.

  As shown in FIG. 21B, the center pillar 52 is formed in a hollow columnar shape in which an upper end portion 52e and a lower end portion 52f are elliptical. An outer air intake port 52a and an outdoor air discharge port 52b are provided on the side surface of the cylindrical casing 19 outside, and an inner air intake port 52c and an internal air discharge port 52d are provided on the inner side surface of the vehicle casing 19.

  The outside air inlet 52 a is provided at the lower part of the center pillar 52, and the outside air outlet 52 b is provided at the upper part of the center pillar 52. Further, the inside air intake port 52 c is provided at the upper part of the center pillar 52, and the inside air discharge port 52 d is provided at the upper part of the center pillar 52.

  In addition, the hollow portion of the center pillar 52 is taken in from the outside air intake port 52a and separates the outside air discharged from the outside air outlet port 52b from the inside air discharged from the inside air inlet port 52c and discharged from the inside air outlet port 52d. The permselective membrane structure 40a is installed in the above.

  Specifically, the selectively permeable membrane structure 40a is arranged so that the upper and lower ends of the selectively permeable membrane structure 40a coincide with the longitudinal axes of the upper and lower ends 52e and 52f of the elliptical shape of the center pillar 52, respectively. The upper end portion of the selectively permeable membrane structure 40a is fixed in close contact with the inside of the elliptical upper end portion 52e of the center pillar 52 with an adhesive, and the lower end portion of the selectively permeable membrane structure 40a is the elliptical shape of the center pillar 52. The lower end portion 52f of the slab is fixed in close contact with an adhesive.

  Further, the upper and lower end portions of the selectively permeable membrane structure 40a folded in a bellows shape are in close contact with the inner surface of the subarc arc portion of the side surface of the cylinder having the elliptical cross section of the center pillar 52 with an adhesive in the central axis direction of the column. It is fixed.

  In addition, in FIG.21 (b), although the permselective membrane structure 40a is typically illustrated in flat form, you may have the shape folded in the shape of a bellows.

  Further, a temperature sensor 60 is provided on the surface of the selectively permeable membrane structure 40 a on the outer side of the passenger compartment 19, and two fans 56 a and 56 b are provided inside the center pillar 52. The temperature sensor 60 is for measuring the surface temperature of the selectively permeable membrane structure 40a, and converts the surface temperature of the selectively permeable membrane structure 40a such as a thermocouple or a Peltier element into an electrical signal and outputs it. is there.

  The fans 56a and 56b are installed in the outside air introduction path from the outside air intake port 52a to the outside air discharge port 52b and the inside air circulation path from the inside air intake port 52c to the inside air discharge port 52d. Then, it operates when the surface temperature of the selectively permeable membrane structure 40a measured by the temperature sensor 60 reaches a predetermined temperature of the selectively permeable membrane structure 40a, and the outside air is taken in from the outside air inlet 52a and the inside air is taken in from the inside air inlet 52c. The selectively permeable membrane structure 40a is cooled (air cooled).

  Although the center pillar 52 has been described above as an example, the same applies to the front pillar 50 and the rear pillar 54.

(floor)
FIG. 22 is a schematic cross-sectional view showing a vehicle, which is an embodiment of the air conditioning system of the present invention, provided with the permselective membrane structure of the present invention on the floor portion. FIG. 22A is a schematic longitudinal sectional view of the vehicle 10, and FIG. 22B is an enlarged view of the floor 150.

  As shown in FIG. 22 (a), the vehicle 10 is surrounded by a wall surface such as aluminum or glass that is substantially impermeable to air, and a vehicle compartment 19 into which outside air does not enter and a trunk or engine room into which outside air can enter. And the space outside the vehicle compartment 19.

  Further, as shown in FIG. 22B, a space 151 is formed between the floor plate 152 and the outer plate 154 in the floor portion 150 of the vehicle compartment 19. Further, the vehicle 10 is provided with an air conditioner (not shown). This air conditioner has only the inside air circulation mode.

(Structure of air conditioning system)
Next, the configuration of the air conditioning system will be described. FIG. 22B is a schematic structural diagram schematically showing the structure of the floor 150.

  As shown in FIG. 22B, the floor 150 is composed of a floor plate 152 facing the inside of the vehicle compartment 19 and an outer plate 154 facing the outside of the vehicle compartment 19. A space 151 is formed between the floor plate 152 and the outer plate 154 by the floor plate 152, the outer plate 154, and the side plates 153a and 153b, and the selectively permeable membrane structure 40a is disposed in the space 151.

  The floor plate 152 is provided with an inside air intake port 152a for taking in the inside air from the inside of the vehicle compartment 19 into the space 151 and an inside air discharge port 152b for discharging the inside air taken into the space 151 into the inside of the vehicle compartment 19.

  The inside air intake port 152a is disposed in front of the driver's seat with respect to the traveling direction of the vehicle 10, specifically, below the driver's feet. Further, the inside air discharge port 152b is provided behind the driver's seat with respect to the traveling direction of the vehicle 10, specifically, immediately before the rear seat.

  The outer plate 154 includes an outer plate 154 that forms the space 151, an outside air intake 154 c for taking outside air into the space 151 from the outside of the vehicle compartment 19, and outside air taken into the space 151 to the outside of the vehicle compartment 19. An outside air outlet 154d is provided.

  The outside air inlet 154c is disposed in front of the driver's seat with respect to the traveling direction of the vehicle 10, specifically, below the driver's feet. Further, the outside air discharge port 154d is provided behind the driver's seat with respect to the traveling direction of the vehicle 10, specifically, immediately before the rear seat.

  In the space 151, a selectively permeable membrane structure 40a is disposed so as to separate the inside of the vehicle compartment 19 from the outside of the vehicle compartment 19. Specifically, the permselective membrane structure 40a is formed in a flat plate shape, and the side edges of the side plates 153a and 153b that form the space 151 are closely fixed to the surface of the space 151 with an adhesive or a sealing material. Has been.

  In addition, in FIG.22 (b), although the permselective membrane structure 40a is typically illustrated in flat form, you may have the shape folded in the shape of a bellows.

  Further, a temperature sensor 60 is provided on the surface of the selectively permeable membrane structure 40a on the outer side of the passenger compartment 19, and two fans 56a and 56b are provided in the space 151. The temperature sensor 60 is for measuring the surface temperature of the selectively permeable membrane structure 40a, and converts the surface temperature of the selectively permeable membrane structure 40a such as a thermocouple, a platinum resistor, and a thermistor into an electrical signal and outputs the electrical signal. To do.

  The fans 56a and 56b are installed in the inside air circulation path from the inside air intake port 152a to the inside air discharge port 152b and the outside air introduction path from the outside air intake port 154c to the outside air discharge port 154d. Then, it operates when the surface temperature of the permselective membrane structure 40a measured by the temperature sensor 60 reaches a predetermined temperature of the permselective membrane structure 40a, and takes outside air from the outside air inlet 154c and inside air from the inside air inlet 152a. The selectively permeable membrane structure 40a is cooled (air cooled).

(door)
[Embodiment 1C]
(Configuration of air conditioning system)
FIG. 23 (a) is a side view of the vehicle 10 as an embodiment of the air-conditioning system of the present invention provided with the selectively permeable membrane structure of the present invention at the door portion, and FIG. FIG. 10 is a schematic cross-sectional view taken in the 10 vehicle width direction.

  As shown in FIG. 23, the air conditioning system includes an interior material 164 provided on the door 140, a selectively permeable membrane structure 40a, an outside air inlet 52a, and an outside air outlet 52b. Further, a window 80 made of glass or the like is attached on a substantially center line of the door 140. The outside air intake 52a is a hole provided in the upper part of the door 140 outside the vehicle compartment 19 rather than the window 80 of the door 140 in order to take outside air from the outside of the vehicle compartment 19. The outside air discharge port 52b is a hole provided in the lower portion of the door 140 outside the vehicle compartment 19 than the window 80 of the door 140 in order to discharge the outside air taken in from the outside air intake port 52a to the outside of the vehicle compartment 19.

  The interior material 164 is mounted facing the inside of the passenger compartment 19 and is formed of a material that allows air to pass therethrough. Specifically, an inorganic compound and an organic compound are formed in one of a porous shape, a fiber shape, or a thin film shape or a composite shape thereof. The interior material 164 is not particularly limited as long as air can permeate through the pores. Preferably, several tens of nanometers to several hundreds of nanometers are preferable.

  Further, as shown in FIG. 23 (d), the deodorizing material 17 is carried on the interior material 164 on the wall surfaces of the pores inside the interior material 164.

  The deodorizing material 17 is a deodorizing material by a heating catalyst, and is an oxide obtained by combining one or more of copper, manganese, platinum, nickel, iron, tantalum, aluminum, and titanium. The deodorizing material 17 is supported on an inorganic compound porous body which is an interior material 164 having pores. The pore size of the inorganic porous material may be any pore size as long as it does not interfere with the gas supply to the selectively permeable membrane. As an example, tens to hundreds of micrometers are preferable.

  The selectively permeable membrane structure 40 a is disposed in close contact with the outside of the interior 19 of the interior material 164.

  As shown in FIG. 23 (c), the permselective membrane structure 40a formed in a flat plate shape has a substantially flat plate surface parallel to the direction in which the outside air introduced from the outside of the passenger compartment 19 flows. In other words, the bellows convex portion is folded in a bellows shape so as to be substantially parallel to the flow of outside air.

  As described above, the permselective membrane structure 40a is disposed in close contact with the outside of the interior 19 of the interior material 164, and the outside air intake 52a and the outside air outlet 52b are provided outside the interior of the door 80 of the window 80 of the door 140. In the door 140, the outside air taken in from the outside air intake port 52a is applied to the surface of the selectively permeable membrane structure 40a outside the compartment 19 with the inside of the compartment 19 and the outside of the compartment 19 separated.

(Operation and features of air conditioning system)
In the air conditioning system configured as described above, the outside air taken in from the outside air inlet 52a comes into contact with the surface of the selectively permeable membrane structure 40a on the outer side of the vehicle compartment 19. The outside air that has come into contact with the surface of the selectively permeable membrane structure 40a outside the vehicle compartment 19 is discharged from the outside air discharge port 52b.

  While the vehicle 10 is traveling, the amount of outside air taken in from the outside air intake 52a increases, so that the outside air continues to hit the surface of the selectively permeable membrane 13 outside the vehicle compartment 19 while the vehicle 10 is traveling. That is, outside air having a constant concentration of oxygen, carbon dioxide, and minute solid components continues to be supplied to the surface of the selectively permeable membrane 13 outside the vehicle compartment 19.

  Therefore, the oxygen and carbon dioxide concentrations inside the compartment 19 can be kept at the same concentration as the outside air by the selectively permeable membrane 13 even when the outside air is not introduced into the compartment 19 by a blower or the like while the vehicle 10 is traveling. it can. And since it is not necessary to operate a blower, the load with respect to a vehicle-mounted battery can be reduced.

  Further, since the deodorizing material 17 is carried in the pores of the porous body of the interior material 164, bad smell is generated in the outside air that has permeated the permselective membrane structure 40a and reached the inside of the cabin 19 of the permselective membrane structure 40a. Even if the component is contained, the malodorous component is removed by the deodorizing material 17, and therefore, the malodorous component does not enter the interior of the passenger compartment 19, so that the interior of the passenger compartment 19 can be kept comfortable.

  Further, since the selectively permeable membrane 13 is folded in a bellows shape, the surface area of the selectively permeable membrane 13 is large. If the surface area of the selectively permeable membrane 13 is large, the amount of exchange of oxygen and carbon dioxide increases, so even if there is a change in the concentration of oxygen or carbon dioxide inside the passenger compartment 19, these concentrations can be kept constant in a short time. Can be returned.

[Embodiment 2C]
Next, what arrange | positioned the functional material etc. which have a various function in the permselective membrane structure 40a is demonstrated based on FIG.25 and FIG.26. FIG. 24A is a side view of the vehicle 10, and FIG. 24B is a schematic cross-sectional view in which the door 140 is cut in the vehicle width direction of the vehicle 10. FIG. 25 is a schematic cross-sectional view in which the door 140 is cut in the vehicle width direction of the vehicle 10.

  In the air conditioning system according to Embodiment 2C, as shown in FIG. 24B, the dust filter 14 is attached in close contact with the outside of the cabin 19 of the selectively permeable membrane structure 40a.

  The dust filter 14 is made of a material having pores larger than the pores of the selectively permeable membrane structure 40a. For example, the dust filter 14 is made of a membrane material such as activated carbon fiber, nonwoven fabric, resin fiber, and charged fiber, It is composed of a non-woven fabric, plate, corrugated plate or granular substrate.

  As the resin fiber, polypropylene, nylon, polyester, polyvinyl chloride, polyvinylidene chloride, polyethylene, polyvinylidene fluoride, acrylic, or the like is used. Then, any one of them or a combination of two or more of them is knitted.

  In addition, as the charged fiber, there is an electret fiber in which a polymer fiber such as polypropylene is charged by using an electro-electret method in which ions are forcibly implanted from an external electrode. In addition to polypropylene, fluorine resin, silicon resin, epoxy resin, polyolefins, polystyrene derivatives, polystyrene, polyamide, polyvinyl halide, polyurethane, polyvinyl chloride, polycarbonate, and the like can be used as the polymer.

  In addition to the electro-electret method, the electrification method of charged fibers, photo-electret method of irradiating ultraviolet rays etc. under electric field, mechano-electret method of applying high stress to plastic polymer and plastic flow, raising the temperature A thermo-electret method in which a high electric field of a polymer is applied in a heated state, a magnet-electret method in which a temperature is increased and a magnetic field is applied, a radio-electret method in which electromagnetic waves such as γ rays are irradiated, and the like can be used. Thus, since the dust removal filter 14 is provided outside the vehicle compartment 19 of the selectively permeable membrane structure 40a, dust is removed from the outside air that contacts the surface of the selectively permeable membrane structure 40a outside the vehicle compartment 19. Therefore, dust does not adhere to the surface of the selectively permeable membrane structure 40a on the outer side of the cabin 19, so that the gas permeable performance of the selectively permeable membrane structure 40a does not deteriorate.

  Further, as shown in FIG. 25 (a), the dehumidifying material 16 may be disposed in close contact with the outside of the cabin 19 of the selectively permeable membrane structure 40a.

  The dehumidifying material 16 is disposed in close contact with the outer side of the casing 19 of the selectively permeable membrane structure 40a, and removes moisture contained in the outside air contacting the surface of the selectively permeable membrane structure 40a on the outer side of the casing 19. . Specifically, a water-absorbing polymer, cotton-like pulp, water supply paper, silica gel, calcium oxide, magnesium oxide or calcium chloride mixed with a porous body, or a water-absorbing polymer made of an electrolyte polymer or a hydrophilic polymer, An acrylic polymer, vinyl alcohol, acrylic acid polymer, or the like is laminated on the outer side of the casing 19 of the selectively permeable membrane structure 40a.

  In this way, moisture contained in the outside air contacting the surface of the selectively permeable membrane structure 40a outside the vehicle compartment 19 can be removed, so that moisture does not adhere to the surface of the selectively permeable membrane structure 40a. . Therefore, the gas permeation performance in the selectively permeable membrane structure 40a can be maintained at a predetermined performance.

  Moreover, since moisture does not enter the interior of the compartment 19 through the permselective membrane structure 40a, clouding of the window 80 in the compartment 19 can be prevented. Note that “removing moisture” does not mean that moisture is completely eliminated, but means that moisture is removed in order to keep the moisture within the allowable range.

  Furthermore, as shown in FIG. 25 (b), a blower 118 may be provided outside the vehicle compartment 19 of the selectively permeable membrane structure 40a.

  The blower 118 is provided outside the compartment 19 with respect to the selectively permeable membrane structure 40a, and supplies the outside air outside the compartment 19 taken from the outside air intake 52a to the surface outside the compartment 19 of the selectively permeable membrane structure 40a. Is to do.

  If it does in this way, the outside air of the vehicle interior 19 will be ventilated by the air blower 118 with respect to the selectively permeable membrane structure 40a. Accordingly, fresh outside air continues to strike the surface of the selectively permeable membrane structure 40a outside the vehicle compartment 19, so that the oxygen and carbon dioxide concentrations outside the compartment 19 of the selectively permeable membrane structure 40a are constant. Therefore, even if the concentration of oxygen and carbon dioxide in the passenger compartment 19 changes, it can be returned to a constant value even in a short time. Moreover, since moisture does not enter the interior of the compartment 19 through the permselective membrane structure 40a, clouding of the window 80 in the compartment 19 can be prevented.

[Embodiment 3C]
Next, instead of arranging the permselective membrane structure 40a in close contact with the interior material 164 as in Embodiments 1C and 2C described above, the outside air inlet 52a and the outside air outlet 52b are covered from the inside of the door 140. Arranged embodiments will be described with reference to FIGS. 26 and 27. FIG. FIG. 26A is a side view of the vehicle 10, and FIG. 26B is a schematic cross-sectional view in which the door 140 is cut in the vehicle width direction of the vehicle 10. FIG. 27 is a schematic cross-sectional view of the door 140 cut in the vehicle width direction of the vehicle 10.

  In the air conditioning system in Embodiment 3C, as shown in FIG. 26 (b), the door 140 has a space 151 composed of an outer wall 50a facing the outside of the passenger compartment 19 and an inner wall 50b facing the inner side of the passenger compartment 19. is doing. The outside air intake 52a is provided below the outside wall 50a above the outside air outlet 52b.

  Moreover, the outside air discharge port 52b is provided in the lower part of the outer wall 50a, and the permselective membrane structure 40a enters the space 151 from the upper right in the figure so that the space 151 covers the outside air intake port 52a and the outside air discharge port 52b. It is arranged diagonally in the lower left. Moreover, as for the selectively permeable membrane structure 40a, the whole one side by the side of the vehicle interior is reinforced with the reinforcing material 13c. Further, a heat storage body 15 is provided in a portion sandwiched between the selectively permeable membrane structure 40a and the outer wall 50a.

  As the material of the reinforcing material 13c, an organic polymer, an inorganic compound, or a material containing carbon can be used. For example, polyolefin, polycarbonate, polyethersulfone, polyvinylidene fluoride, polyethylene, fluororesin (for example, PTFE, PEF etc.), glass (for example, fibrous), single material selected from cellulose, etc., or two or more materials. The reinforcing material 13c preferably has a porous structure, and for example, pores having a diameter of several tens to several hundreds of nanometers are preferably formed.

  The heat storage body 15 heats the permselective membrane structure 40a directly or indirectly through the reinforcing material 13c. Moreover, the heat storage body 15 stores the heat supplied from the outside, and heats the permselective membrane structure 40a with the stored heat. Specifically, it is composed of a material having higher thermal conductivity than the selectively permeable membrane structure 40a or the reinforcing material 13c, in which a porous ceramic is supported by honeycomb structure ceramic, inorganic salt hydrate, paraffin or wax. ing.

  Moreover, the heat storage body 15 stores the radiant heat of sunlight as heat supplied from the outside. That is, when the selectively permeable membrane structure 40a is placed inside the door 140, the radiant heat of sunlight that illuminates the vehicle 10 is accumulated.

  As shown in FIG. 27 (a), when the dehumidifying material 16 is provided outside the casing 19 of the selectively permeable membrane structure 40a, outside air that contacts the surface of the selectively permeable membrane structure 40a outside the casing 19 is provided. Therefore, moisture does not adhere to the surface of the selectively permeable membrane structure 40a. Therefore, the gas permeation performance of the selectively permeable membrane structure 40a can be maintained.

  Further, as shown in FIG. 27 (b), a blower 118 may be mounted inside the vehicle compartment 19 of the reinforcing member 13c. In this way, when the outside air is sucked into the vehicle interior 19 by the blower 118, the amount of the external air that is taken in from the external air intake 52a and contacts the surface of the selectively permeable membrane structure 40a outside the vehicle interior 19 increases.

  Accordingly, the amount of oxygen taken into the passenger compartment 19 and the amount of carbon dioxide discharged outside the passenger compartment 19 increases, so that even if the concentration of oxygen or carbon dioxide inside the passenger compartment 19 changes, it returns to a constant value in a short time. be able to.

  According to the automobile equipped with the air conditioning system described above, it is possible to prevent inflow of floating substances in the atmosphere such as SPM into the passenger compartment, and to remove floating substances such as SPM in the vehicle. You can also.

(Example 1)
Pluronic P123 (manufactured by BASF, (ethylene oxide) ₂₀ (propylene oxide) ₇₀ (ethylene oxide) ₂₀ ), 88 g of water, 2640 g of water, and 453.5 ml of hydrochloric acid were stirred at room temperature using a mechanical stirrer to dissolve Pluronic P123 Then, 187.8 g of tetraethoxysilane (manufactured by Kanto Chemical Co., Inc.) was added dropwise, and the mixture was further stirred for 12 hours. Heating was performed in an oven maintained at 35 ° C. for 20 hours, and further heating was performed in an oven maintained at 100 ° C. for 24 hours. The produced white solid was washed with water, filtered, and dried using a vacuum pump. Thereafter, the mixture was baked in a baking furnace maintained at 550 ° C. for 6 hours to obtain mesoporous silica (56.3 g) which is an additive for the permselective material.

  Next, a silicone-modified pullulan polymer (X-22-8400, manufactured by Shin-Etsu Chemical Co., Ltd.), which is a silicone-based polymer, is dissolved in toluene, and the content of the silicone-modified pullulan polymer (solid content) contained in toluene is 10 wt%. Adjusted. The above-mentioned mesoporous silica 0.098g (mesoporous silica with an addition amount of 81.7 parts by weight with respect to 100 parts by mass of silicone-modified pullulan resin) is blended with 12 g of this solution, and mixed using an ultrasonic disperser. Thus, a permselective material was obtained.

  Next, after PET64-HC, which is a reinforcing mesh material, is placed on the PET film, a sealing material paint is applied to the PET64-HC placed on the PET film with a wire coater, and the opening of the PET64-HC The filler was filled with a sealing material paint and sealed. As the sealing material paint, an ethanol solution containing HEAA resin (solid content) at a content of 50 wt% was used.

  After filling the opening of PET64-HC with the sealing material paint, the sealing material paint applied to PET64-HC is heat-treated, and the dilution solvent ethanol is added from the sealing material paint filled in the opening of PET64-HC. By volatilizing, the volume of the sealing material was contracted to form an exposed portion of PET64-HC.

  Next, the above-mentioned permselective material was applied with a wire coater so as to cover the exposed portion of PET64-HC and the exposed portion of the filler filling the opening. Next, a selectively permeable film was formed from the selectively permeable material by removing the solvent component (toluene) of the selectively permeable material by heat treatment.

  Next, the PET film was peeled from the PET 64-HC on which the permselective membrane was laminated. Then, the sealing material filled in the opening of the PET 64-HC was removed from the surface of the PET 64-HC opposite to the surface on which the permselective membrane was laminated by washing with water. After removing the sealing material, the PET64-HC and the selectively permeable membrane were dried to remove moisture, thereby obtaining the selectively permeable membrane structure of Example 1. In addition, the average film thickness of the permselective membrane with which the permselective membrane structure is provided was 3.8 μm.

(Examples 2-4, 7-9)
Types of mesh materials for reinforcement, types of resins contained in sealant paints, resin (solid content) content (wt%) in sealant paints, types of additives contained in permselective materials, silicone-modified pullulan resin Examples 2 to 4, 7 to 9 using the same materials and production methods as in Example 1 except that the amount of additive (parts by mass) added to 100 parts by mass of the solid content is shown in Table 2. Each of the permselective membrane structures was prepared. In addition, NanoTek SiO ₂ shown in Table 2 is an additive manufactured by CI Kasei Co., Ltd.

(Example 5)
In Example 5, the type of reinforcing mesh material, the type of resin contained in the sealing material paint, the content (wt%) of the resin (solid content) in the sealing material paint, the type of additive contained in the permselective material A selectively permeable membrane structure was prepared using the same material as in Example 1 except that the additive amount (parts by mass) of the additive relative to 100 parts by mass of the silicone-modified pullulan resin solids was as shown in Table 2. . Moreover, the selectively permeable membrane structure of Example 5 was produced by a manufacturing method different from that of Example 1 as described below.

  First, PET85-HC, which is a reinforcing mesh material, is placed on a PET film, and then a sealing material paint is applied to the PET85-HC placed on the PET film with a wire coater to open the opening of the PET85-HC. The sealant paint was filled.

  Next, a coating having both adhesiveness to the sealing material and adhesiveness to the selectively permeable material was applied onto PET85-HC to which the sealing material coating was applied, and an intermediate layer was formed from this coating material. The thickness of the intermediate layer was about 2.6 μm. As a coating material for forming the intermediate layer, the content of PVA (product number: JL-05E, manufactured by Nihon Ventures & Poval Co., Ltd.) having both adhesiveness to the sealing material HEAA and the above-mentioned selective transmission material is 20 wt. % Aqueous solution was used.

  After the formation of the intermediate layer, the sealing material filled in the opening of the PET 85-HC and the solvent component contained in the intermediate layer are removed by heat treatment, and the volume of the sealing material and the intermediate layer is contracted to expose the PET 85-HC. Part was formed.

  Next, the above-mentioned permselective material was applied with a wire coater so as to cover the exposed portion and the intermediate layer of PET85-HC. Next, a selectively permeable film was formed from the selectively permeable material by removing the solvent component of the selectively permeable material by heat treatment.

  After the formation of the selectively permeable membrane, the PET film was peeled from the PET85-HC on which the selectively permeable membrane was laminated. Then, from the surface opposite to the surface of the PET 85-HC on which the permselective membrane is laminated, the sealing material filled in the opening of the PET 85-HC and the intermediate layer behind it are washed with water, etc. Removed by. After removing the sealing material and the intermediate layer, the PET85-HC and the selectively permeable membrane were dried to remove moisture, thereby obtaining the selectively permeable membrane structure of Example 5.

(Example 6)
As the coating material for forming the intermediate layer, the same materials and methods as in Example 5 were used, except that an aqueous solution having a PVA content (ASP05, manufactured by Nippon Vinegar Poval Co., Ltd.) was 20 wt%. Then, the permselective membrane structure of Example 6 was formed.

(Comparative Examples 1 and 2)
In Comparative Examples 1 and 2, the type of reinforcing mesh material, the type of resin contained in the sealing material paint, the content (wt%) of the resin (solid content) in the sealing material paint, and the additive contained in the permselective material The selectively permeable membrane structure was formed using the same material as in Example 1 except that the additive amount (parts by mass) of the additive relative to 100 parts by mass of the silicone-modified pullulan resin solids was as shown in Table 2. . Moreover, in Comparative Examples 1 and 2, the permselective membrane was created by directly applying the permselective material to the reinforcing mesh material without using the reinforcing mesh material to keep the mesh.

  In Examples 1 to 9 and Comparative Examples 1 and 2, when the permselective material was applied to the reinforcing mesh material to form the permselective film, the film formation state of the permselective film (thickness uniformity, surface Smoothness).

  In Examples 1 to 9 in which the reinforcing mesh material is sealed with the sealing material, the selectively permeable material does not flow excessively into the openings of the reinforcing mesh material, and the selective permeable membrane has a uniform thickness and a smooth surface. A permselective membrane structure having the following characteristics was obtained. In particular, in Examples 1 to 6 using the ethanol solution containing the HEAA resin as the sealing material, it was confirmed that the sealing with the sealing material was ensured and the film formation state of the permselective membrane was good.

  On the other hand, in Comparative Examples 1 and 2 in which the permselective film was formed by directly applying the permselective material to the reinforcing mesh material without keeping the reinforcing mesh material with the seam material, the openings of the reinforcing mesh material were used. The permselective material excessively flowed in, and a permselective membrane having a uniform thickness and a smooth surface could not be obtained.

(Evaluation of gas permeability coefficient)
A selectively permeable membrane structure of Example 3a was formed in the same manner as in Example 3 except that the thickness of the selectively permeable membrane was changed to the value shown in Table 3. A selectively permeable membrane structure of Example 4a was formed in the same manner as in Example 4 except that the thickness of the selectively permeable membrane was changed to the value shown in Table 3. A selectively permeable membrane structure of Example 6a was formed in the same manner as in Example 6 except that the thickness of the selectively permeable membrane was changed to the value shown in Table 3. A selectively permeable membrane structure of Comparative Example 1a was formed in the same manner as Comparative Example 1 except that the thickness of the selectively permeable membrane was changed to the values shown in Table 3. About the film | membrane obtained by Example 3a, 4a, 6a and the comparative example 1a, the gas about oxygen and nitrogen was measured on the following measurement conditions using the gas-permeability measuring apparatus (the GTR tech company make, model number: GTR-20XAMDE). The transmission coefficient was measured. The obtained results are shown in Table 3.
<Measurement conditions>
Temperature: 23 ± 2 ° C
Pressure downstream of membrane: about 0.0013 atm
Pressure upstream of membrane: 1.05-1.20 atm
Pressure difference between membranes: 1.05-1.20 atm

(Evaluation of nSPM cutoff rate)
About the film | membrane obtained in Example 3a, 4a, 6a and Comparative Example 1a, the apparatus shown to the schematic of FIG. 28 was used and the nSPM interruption | blocking rate was measured with the process of following (1)-(5). . The obtained results are shown in Table 3.
(1) Carbon particles of 10 to 500 nm were generated by a nanoparticle generator (manufactured by Palas, model number: GFG-1000).
(2) The membrane was set in a sample holder (membrane area: MAX16 [cm ² ]), the valve (V1) was closed, and the B layer was depressurized (differential pressure 1 [kPa]).
(3) After depressurizing the B layer, the valve (V1) is opened, and the nanoparticles are supplied to the film on the gas that permeates when the inside of the B layer returns to the atmospheric pressure. Accumulated.
(4) The particle weight in the B layer was measured with a particle counter (manufactured by TSI, model number: SMPS-3034).
(5) The blocking rate was calculated based on the following formula.
nSPM cutoff rate [wt%] = 100 × {(Cin−Cout) / Cin}
(In the formula, “Cin” indicates the particle concentration [unit: μg / ml] upstream of the membrane, and “Cout” indicates the particle concentration after passing through the membrane [unit: μg / ml].)

(Reference Examples 1-3)
In Reference Examples 1 to 3, without using a sealing material, the type of reinforcing mesh material, the type of additive included in the permselective material, and the additive amount (100 parts by mass) relative to 100 parts by mass of the silicone-modified pullulan resin solid content The permselective membrane structure was made using the same material as in Example 1 except that the material shown in Table 3 was used. In Reference Examples 1 to 3, selectively permeable membrane structures were prepared by the following method different from Example 1. First, in Reference Examples 1 to 3, a water-soluble PVA film was formed on a release PET film as a support film by a coater method. The average film thickness of the PVA film was a value shown in Table 4. Next, the permselective material shown in Table 4 was applied on the PVA membrane by a coater method to form a permselective membrane. This selectively permeable membrane was transferred to a reinforcing mesh material (PET85-HC), and then immersed in water to dissolve the PVA membrane, thereby forming a selectively permeable membrane structure.

  Also in Reference Examples 1 to 3, the film formation state (thickness uniformity, surface smoothness) of the selectively permeable membrane was evaluated.

  In any of Reference Examples 1 to 3, a selectively permeable membrane structure having a selectively permeable membrane having a uniform thickness and a smooth surface could be obtained. In particular, it was confirmed that the thinner the water-soluble PVA membrane formed on the release PET film, the smaller the residue of the PVA membrane attached to the completed selectively permeable membrane structure.

FIG. 1 is a schematic perspective view of a selectively permeable membrane structure according to an embodiment of the present invention. FIG. 2 is an image diagram showing the flow of gas that permeates through the permselective membrane included in the permselective membrane structure according to one embodiment of the present invention. FIG. 3 is a schematic view showing steps included in the first method for producing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 4 is a schematic view showing steps included in the first method for manufacturing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 5 is a schematic view showing steps included in the first method for producing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 6 is a schematic view showing steps included in the first method for producing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 7 is a schematic cross-sectional view of a selectively permeable membrane structure according to an embodiment of the present invention. FIG. 8 is a schematic view showing the steps included in the second method for producing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 9 is a schematic view showing steps included in the second method for producing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 10 is a schematic view illustrating steps included in the second method for manufacturing a selectively permeable membrane structure according to one embodiment of the present invention. FIG. 11 is a diagram showing an embodiment of an air conditioning system including the selectively permeable membrane structure of the present invention. FIG. 12 is a schematic cross-sectional view showing a part of an air conditioner unit in an automobile which is an embodiment of the air conditioning system of the present invention including the selectively permeable membrane structure of the present invention. FIG. 13 (a) is a schematic configuration diagram showing an embodiment of a vehicle provided with the permselective membrane structure of the present invention in a pressure adjusting ventilator, and FIG. 13 (b) is a vehicle viewed from the rear of the vehicle. It is sectional drawing of the rear part. FIG. 14A is a schematic configuration diagram showing a vehicle provided with the permselective membrane structure of the present invention on the ceiling portion, and FIG. 14B is an enlarged sectional view of the ceiling portion shown in FIG. It is. 15 (a), 15 (b), and 15 (c) are enlarged cross-sectional views of a ceiling portion in a vehicle in which the permselective membrane structure of the present invention is provided on the ceiling portion. 16 (a), 16 (b), and 16 (c) are enlarged cross-sectional views of a ceiling portion in a vehicle in which the permselective membrane structure of the present invention is provided on the ceiling portion. FIG. 17 (a) is a schematic configuration diagram showing an embodiment of a vehicle provided with the permselective membrane structure of the present invention in the windshield portion, and FIG. 17 (b) is a front view of the vehicle shown in FIG. 17 (a). It is an expanded sectional view of a glass part. FIG. 18 is a schematic configuration diagram showing a vehicle which is one form of the air conditioning system of the present invention, and includes a permselective membrane made of the permselective material of the present invention in the rear window portion. FIG. 19A is a configuration diagram when the sunroof of the vehicle is made of porous glass equipped with the permselective membrane structure of the present invention, and FIG. 19B is the permselective membrane structure of the present invention. It is a schematic structure figure showing one form of vehicles provided with a body on a sunroof. FIG. 20 is a schematic cross-sectional view of a vehicle having a pillar including the selectively permeable membrane structure of the present invention. FIG. 21A is a schematic configuration diagram of a vehicle having a pillar including the selectively permeable membrane structure of the present invention and each pillar provided in the vehicle, and FIG. 21B is a selectively permeable membrane structure of the present invention. It is the schematic structure figure which showed typically the structure of the center pillar provided with a body. FIG. 22A is a schematic cross-sectional view of a vehicle provided with the permselective membrane structure of the present invention on the floor, and FIG. 22B is an enlarged view of the floor shown in FIG. FIG. 23A is a side view of a vehicle provided with the selectively permeable membrane structure of the present invention in a door, and FIG. 23B shows the door provided with the selectively permeable membrane structure of the present invention in the vehicle width direction. It is the schematic sectional drawing cut into two. FIG. 24A is a side view of a vehicle provided with the selectively permeable membrane structure of the present invention in a door, and FIG. 24B shows the door provided with the selectively permeable membrane structure of the present invention in the vehicle width direction of the vehicle. It is the schematic sectional drawing cut into two. 25 (a) and 25 (b) are schematic cross-sectional views in which a door provided with the permselective membrane structure of the present invention is cut in the vehicle width direction of the vehicle. FIG. 26A is a side view of a vehicle provided with the selectively permeable membrane structure of the present invention in a door, and FIG. 26B shows the door provided with the selectively permeable membrane structure of the present invention in the vehicle width direction. It is the schematic sectional drawing cut into two. 27 (a) and 27 (b) are schematic cross-sectional views in which a door provided with the permselective membrane structure of the present invention is cut in the vehicle width direction of the vehicle. FIG. 28 is a schematic diagram of an apparatus for measuring the nSPM cutoff rate.

Explanation of symbols

DESCRIPTION OF SYMBOLS 10 ... Vehicle, 11 ... Vehicle compartment wall, 12a ... Front reinforcement material, 12b ... Back reinforcement material, 13a ... Selective permeation membrane, 13c ... Reinforcement material, 13s ... Selective permeation material, 14, 36 ... Dust removal filter, DESCRIPTION OF SYMBOLS 16 ... Dehumidifying material, 17 ... Deodorizing material, 18 ... Oxygen sensor, 19 ... Car compartment, 22 ... Outer wall, 24 ... Inner wall, 26, 126 ... Outside air inlet, 27a ... Front opening door, 27b, 27d ... Hinge, 27c ... rear opening / closing door, 27e ... front dam, 27f ... rear dam, 28 ... outside air outlet, 29a ... front fan, 29b ... rear fan, 30 ... air conditioner unit, 32 ... damper, 32a ... hinge, 34 ... bumper, 35 ... Air conditioner unit case, 35a ... Outside air inlet, 35b ... Inside air inlet, 35c ... Opening, 37 ... Centrifugal blower fan, 38 ... Housing, 40a ... Selective permeable membrane structure, 50 ... Front pillar, 52 Center pillar, 52a, 154c ... Outside air inlet, 52b, 128,154d ... Outside air outlet, 52c, 152a ... Inside air inlet, 52d, 152b ... Inside air outlet, 52e ... Upper end, 52f ... Lower end, 53 ... Side plate , 54 ... Rear pillar, 60 ... Temperature sensor, 70 ... Cavity, 80 ... Window, 90 ... Control part, 110 ... Ventilator for pressure adjustment, 112 ... Cover, 118 ... Blower, 120 ... Space, 122 ... Body, 126 ... Outside air Inlet, 127a ... front weir, 127b ... rear weir, 130 ... windshield, 132 ... porous glass, 138 ... sunroof, 140 ... door, 150 ... floor, 151 ... space, 152 ... floor plate, 154 ... outer plate 156a, 156b ... fan, 164 ... interior material, 302 ... reinforcing mesh material, 302b ... opening of reinforcing mesh material, 302 ... exposed portion of the reinforcing mesh, 321 ... silicone polymer, 323 ... solid additives, 325 ... gap, 332 ... second closure member, the exposed portion of 332a ... first fastening member. 334: Intermediate layer.

Claims (6)

Filling the openings in the reinforcing mesh material with a sealing material;
Shrinking the volume of the sealing material filled in the opening;
Forming a permselective membrane from a permselective material so as to cover the exposed portion of the reinforcing mesh material not covered with the seam material and the exposed portion of the seam material filled in the opening. When,
After forming the permselective membrane, removing the sealing material from the opening of the reinforcing mesh material,
A method for producing a selectively permeable membrane structure comprising the reinforcing mesh material and the selectively permeable membrane laminated on the reinforcing mesh material. Filling the openings in the reinforcing mesh material with a sealing material;
Forming an intermediate layer having both adhesiveness with the sealing material and adhesiveness with the selectively permeable material at an exposed portion of the sealing material filled in the opening;
Shrinking the volume of the sealing material filled in the opening;
Forming a permselective membrane from the permselective material so as to cover the exposed portion of the reinforcing mesh material and the intermediate layer not covered with the sealing material;
After the selectively permeable membrane is formed, the step of removing the sealing material and the intermediate layer from the opening of the reinforcing mesh material,
A method for producing a selectively permeable membrane structure comprising the reinforcing mesh material and the selectively permeable membrane laminated on the reinforcing mesh material.   In the step of shrinking the volume of the sealing material filled in the opening, by exposing a part of the reinforcing mesh material covered with the sealing material along with the volume shrinkage of the sealing material, The method for producing a permselective membrane structure according to claim 1, wherein the exposed portion of the reinforcing mesh material is formed. A selectively permeable membrane structure obtained by the method for producing a selectively permeable membrane structure according to any one of claims 1 to 3,
The permselective material for forming the permselective membrane has a solid additive dispersed in a polymer having an organosiloxane skeleton,
When oxygen and nitrogen are allowed to permeate through the membrane made of the permselective material, the permeability coefficient of oxygen and nitrogen (cm ³ · cm · cm) at 23 ± 2 ° C. and a pressure difference between the membranes of 1.05 to 1.20 atm. sec ^-1 · cm ^-2 · cmHg ^-1 ) is expressed by the following formula (1):
An opening diameter of the reinforcing mesh material is larger than a film thickness of the selectively permeable membrane,
The permselective membrane structure, wherein the reinforcing mesh material has an aperture ratio of 30% or more.

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ] A selectively permeable membrane structure obtained by the method for producing a selectively permeable membrane structure according to any one of claims 1 to 3,
The permselective material for forming the permselective membrane is obtained by adding an ionic liquid to a polymer having an organosiloxane skeleton,
When oxygen and nitrogen are allowed to permeate through the membrane made of the permselective material, the permeability coefficient of oxygen and nitrogen (cm ³ · cm · cm) at 23 ± 2 ° C. and a pressure difference between the membranes of 1.05 to 1.20 atm. sec ^-1 · cm ^-2 · cmHg ^-1 ) is expressed by the following formula (1):
An opening diameter of the reinforcing mesh material is larger than a film thickness of the selectively permeable membrane,
The permselective membrane structure, wherein the reinforcing mesh material has an aperture ratio of 30% or more.

[Wherein, P (O ₂ ) represents an oxygen permeability coefficient, and P (N ₂ ) represents a nitrogen permeability coefficient. ] An air conditioning system comprising a selectively permeable membrane structure that supplies gas to and / or discharges gas from the air conditioning target space,
The air-conditioning system according to claim 4 or 5, wherein the selectively permeable membrane structure is the selectively permeable membrane structure.

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