Polymer composite film, gas separator provided with polymer composite film, gas separator provided with polymer composite film, and method for producing polymer composite film

Abstract

[Problem] To provide a polymer composite film which has high gas permeability and selectivity and practical structural stability by combining two polymer films having different properties or by further combining a reinforcing material (reinforcing layer). [Solution] A polymer composite film (1) is configured from a first polymer film (2) having selective permeability to a predetermined gas, and a second polymer film (3) that is provided so as to overlap the first polymer film (2) and contains at least an ethylene oxide chain.

Description

Technical Field

[0001] The present invention mainly relates to a polymer composite film containing a polymer material, and particularly relates to a polymer composite film having high functionality and significantly improved film strength, a gas separation body and a gas separation device having the polymer composite film, and a method for manufacturing the polymer composite film. Background Art

[0002] Recently, as a main cause of climate change and global warming, an increase in the concentration of CO2 in the atmosphere has been pointed out. In view of such a situation, in order to substantially reduce the concentration of CO2 in the air, progress of a direct air capture (DAC) technology for directly capturing CO2 in the atmosphere and storing it safely and permanently is strongly desired.

[0003] Regarding DAC, a technology of air separation for separating gas components such as O2, N2, and CO2 contained in the atmosphere as needed and making them practical is known (for example, see "Air Separation: Materials, Methods, Principles and Applications - An Overview D Hazel and N Gobi Chem. Sci. Rev. Lett. 2017, 6(22), 864 - 8731").

[0004] As air separation technologies, specifically, the following technologies are known: cryogenic distillation, in which a gas mixture is cooled at normal temperature to become liquid or solid, and each component is separated by distillation or the like; pressure swing adsorption (PSA), in which a specific gas is adsorbed on an adsorbent under pressure or normal pressure, and after removing the unadsorbed components, the pressure is reduced to release the adsorbed gas; solid adsorption method, in which a solid adsorbent such as activated carbon or zeolite adsorbs CO2, and then CO2 is released by reducing the pressure or heating; and so on.

[0005] All of these methods have problems such as high energy consumption and high processing cost for gas separation. Here, gas separation based on polymer films has been widely studied as a means of creating a DAC technology or an air separation technology that is theoretically low in energy consumption and economically advantageous.

[0006] Regarding the technology related to gas separation membranes, a gas separation membrane is known, which is a membrane including a support layer and a selective polymer layer disposed on the support layer. The support layer includes a gas-permeable polymer and a hydrophilic additive dispersed in the gas-permeable polymer. The selective polymer layer includes a selective polymer matrix and carbon nanotubes dispersed in the selective polymer matrix. (Patent Document 1)

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 2020-531260 Summary of the Invention

[0010] Problems to be Solved by the Invention

[0011] According to the technology described in Patent Document 1, it is considered that the CO2 permeability of the membrane having a selective polymer layer containing carbon nanotubes (Examples 2B to 2D) is 617 to 807 GPU under reduced pressure, and the CO2 / N2 selectivity ratio is 161 to 187. It is considered that the reason for the difference from Example 2A in which the selective polymer layer does not contain carbon nanotubes (under reduced pressure, the CO2 permeability is 473 GPU, CO2 / N2 selectivity ratio = 194) is that the mechanical strength of the selective polymer layer is improved by the addition of carbon nanotubes, preventing it from being trapped in the pores of the support layer as a nanoporous substrate (see Patent Document 1 [Table 13], etc.).

[0012] However, although Patent Document 1 implies that carbon nanotubes improve the mechanical strength of the selective polymer layer, there is no hint regarding the further thinning of the selective polymer layer and the improvement of gas permeability by the addition of carbon nanotubes. However, Patent Document 1 considers that "preventing the selective polymer layer from being trapped in the pores of the support layer" is important. Due to the thinning, the selective polymer layer facing the pores becomes more likely to be trapped in the pores, increasing the risk of membrane fracture. Therefore, there is no motivation to actively pursue thinning.

[0013] The present invention has been developed to solve such problems of the prior art, and its object is to provide a polymer composite membrane having high permeability and selectivity for a specified gas and having practical structural stability (self-supporting property) by combining two polymer thin films having different properties or further combining a reinforcing material (composite), a gas separation body having the polymer composite membrane, a gas separation device having the polymer composite membrane, and a method for manufacturing the polymer composite membrane.

[0014] Means for Solving the Problems

[0015] The present invention, which has been completed to solve the foregoing problems, is a polymer composite film composed of a first polymer film having a selective permeability to a specified gas and a second polymer film provided overlapping the first polymer film and containing at least an ethylene oxide chain.

[0016] Thereby, two polymer films with different properties can be combined to obtain a polymer composite film that has good balance and possesses gas permeability and gas selectivity.

[0017] In addition, in the present invention, carbon nanotubes or cellulose nanofibers are dispersed in the second polymer film. Thereby, the mechanical strength of the second polymer film can be improved, and the film thickness of the polymer composite film can be reduced.

[0018] In addition, in the present invention, carbon nanotubes or cellulose nanofibers are dispersed in the first polymer film. Thereby, the mechanical strength of the first polymer film can be improved, and the film thickness of the polymer composite film can be reduced.

[0019] In addition, in the present invention, a reinforcing layer composed of carbon nanotubes or cellulose nanofibers is provided between the first polymer film and the second polymer film. Thereby, the mechanical strength of the polymer composite film including the reinforcing layer can be improved, and the film thickness of the polymer composite film can be reduced.

[0020] In addition, in the present invention, the second polymer film is composed of a crosslinked polymer containing the ethylene oxide chain. Thereby, the physical properties of the second polymer film are stable, and breakage and the like of the polymer composite film including the second polymer film can be suppressed.

[0021] In addition, in the present invention, the crosslinked polymer containing the ethylene oxide chain is made into a state of partial crosslinking. Thereby, the gas permeability of the second polymer film can be ensured.

[0022] In addition, in the present invention, the total film thickness of the first polymer film and the second polymer film is made to be 20 nm to 1000 nm. Thereby, a polymer composite film 1 that has self-supporting properties and high gas permeability and gas selectivity can be obtained.

[0023] In addition, the present invention is a polymer composite film that selectively permeates carbon dioxide and oxygen from air, exhaust gas, and other mixed gases. Thereby, carbon dioxide concentration, oxygen enrichment, and nitrogen enrichment can be achieved.

[0024] In addition, in the present invention, the first polymer film is mainly composed of polysiloxane. Thereby, the polymer composite film can be manufactured at a lower cost using commonly available general materials.

[0025] In addition, the present invention relates to a gas separation body which includes a polymer composite film and a support body that supports the aforementioned polymer composite film. Thus, a gas separation body can be formed by overlapping (transferring) the polymer composite film on the support body.

[0026] In addition, the present invention relates to a gas separation device which includes a gas separation body and a gas supply unit that supplies gas to the aforementioned gas separation body. Thus, a gas separation device capable of obtaining oxygen-enriched air, carbon dioxide-enriched air, and nitrogen-enriched air can be provided.

[0027] In the present invention, the aforementioned gas supply unit supplies gas in such a manner that the gas sequentially passes through the aforementioned second polymer film and the aforementioned first polymer film. Thus, oxygen-enriched air, carbon dioxide-enriched air, and nitrogen-enriched air can be obtained using a polymer composite film with excellent gas selectivity.

[0028] In the present invention, the aforementioned gas supply unit supplies gas in such a manner that the gas sequentially passes through the aforementioned first polymer film and the aforementioned second polymer film. Thus, oxygen-enriched air, carbon dioxide-enriched air, and nitrogen-enriched air can be obtained with high efficiency using a polymer composite film with excellent gas permeability.

[0029] In addition, the present invention relates to a method for manufacturing a polymer composite film, which includes: a first step of preparing a polymer solution containing an ethylene oxide chain and a polymer material solution containing a polymer material that has selective permeability to a specified gas when formed into a film; a second step of coating the polymer solution containing an ethylene oxide chain on a substrate having a sacrificial layer formed thereon so as to cover the aforementioned sacrificial layer, thereby forming a second polymer film; a third step of crosslinking the aforementioned second polymer film; a fourth step of coating the polymer material solution on the crosslinked second polymer film so as to cover it and curing it, thereby forming a first polymer film; and a fifth step of dissolving the aforementioned sacrificial layer and peeling off the polymer composite film composed of the aforementioned first polymer film and the aforementioned second polymer film from the substrate.

[0030] Thus, by combining two polymer films with different properties, a polymer composite film having good balance in gas permeability and gas selectivity can be manufactured.

[0031] Advantages of the Invention

[0032] As described above, according to the present invention, by combining two polymer films with different characteristics or further combining a reinforcing material (composite), a polymer composite film having high gas permeability and selectivity to a specified gas and having practical structural stability (self-supporting property), a gas separation body including the polymer composite film, a gas separation device including the polymer composite film, and a method for manufacturing the polymer composite film can be obtained. Description of the Drawings

[0033] Figure 1 Figure 1 In (a) and (b) thereof are explanatory diagrams showing the configuration of the polymer composite film 1 according to the first embodiment of the present invention and the gas separation body 6 including the polymer composite film 1

[0034] Figure 2 Figure 2 In (a) thereof is an explanatory diagram showing the configuration of the polymer composite film 1 according to the second embodiment of the present invention and the gas separation body 6 including the polymer composite film 1, Figure 2 In (b) thereof is an explanatory diagram showing the configuration of the polymer composite film 1 according to the third embodiment of the present invention and the gas separation body 6 including the polymer composite film 1, Figure 2 In (c) thereof is an explanatory diagram showing the configuration of the polymer composite film 1 according to the fourth embodiment of the present invention and the gas separation body 6 including the polymer composite film 1

[0035] Figure 3 is an explanatory diagram showing the configuration of the gas separation device 110 including the gas separation body 6 according to the present invention Detailed Description of the Invention

[0036] (First Embodiment)

[0037] Figure 1 In (a) and (b) thereof are explanatory diagrams showing the configuration of the polymer composite film 1 according to the first embodiment of the present invention and the gas separation body 6 including the polymer composite film 1. The gas separation body 6 is composed of the polymer composite film 1 and the support 5. The polymer composite film 1 is composed of a first polymer film 2 having selective permeability to a specified gas and a second polymer film 3 containing at least an ethylene oxide chain. Both the second polymer film 3 and the first polymer film 2 are non-porous bodies, and they are overlapped in contact with each other. The gas separation body 6 can be configured such that the first polymer film 2 is in contact with the support 5 as shown in Figure 1 (a) thereof, or can be configured such that the second polymer film 3 is in contact with the support 5 as shown in Figure 1 (b) thereof.

[0038] ​​​​​As the material for forming the first polymer thin film 2, for example, vinyl polymers, polysiloxanes, and crosslinkable polymers can be used. In particular, polydimethylsiloxane (hereinafter referred to as "PDMS") can be preferably used. Here, it is considered that when the film thickness of vinyl polymers and polysiloxanes is, for example, 10 nm or less, the mechanical strength is low in the case of the film alone, and self-supportability cannot be ensured. In this case, as described later, for example, by adding a reinforcing material 10 to the first polymer thin film 2 mainly composed of vinyl polymers and polysiloxanes, or by laminating a reinforcing layer 4 on the first polymer thin film 2, functionality and self-supportability can be achieved simultaneously.

[0039] On the other hand, it is considered that crosslinkable polymers have self-supportability even when the film thickness at which functionality can be effectively exhibited (for example, 100 nm or less) is used. Here, the crosslinkable polymer (crosslinked polymer) refers to a polymer having a three-dimensional network structure (crosslinked structure) formed by bonding multiple linear polymer chains in a chemical reaction, and includes, for example, free radical crosslinking of linear polymers and epoxy resins obtained by crosslinking an epoxy group as a functional group and an amino group through a chemical reaction.

[0040] It should be noted that an example of a self-supporting polymer thin film formed with a film thickness of 20 nm is published in A Large, Freestanding, 20nm Thick Nanomembrane Based on an Epoxy Resin, H. Watanabe T. Kunitake, ADVANCED MATERIALS Volume 19, Issue 7, Pages 909 - 912, 2007 (https: / / onlinelibrary.wiley.com / doi / abs / 10.1002 / adma.200601630).

[0041] As the material for forming the second polymer thin film 3, a compound containing an ethylene oxide chain can be preferably used. The ethylene oxide chain has gas separation characteristics regardless of whether it is contained in the main chain or the side chain of the polymer. As the polymer material in the case of being contained in the main chain, poly(ethylene glycol) diacrylate (hereinafter sometimes referred to as "PEGDA"), poly(ethylene glycol) dimethacrylate, polyethylene glycol, and poly(ethylene oxide) can be mentioned.

[0042] In addition, as the polymer material in the case of being included in the side chain, for example, poly(ethylene glycol)methyl ether acrylate (hereinafter sometimes referred to as "PEGMA"), poly(ethylene glycol)methyl ether methacrylate can be cited. In particular, the exemplified acrylates can be easily polymerized, and various acrylates can be arbitrarily combined, so they are preferred. When these polymer materials are polymerized, the materials can be mixed and then polymerized, or various materials can be polymerized and then mixed. Here, when PEGMA and PDGDA are mixed, the volume ratio is preferably set in the range of PEGMA:PEGDA = 10:0 to 5:5. The compound containing an ethylene oxide chain can be in any form of a so-called main chain type, side chain type, or star type, and also includes an ethylene oxide polymer that is easily crosslinked by a radical reaction.

[0043] The acrylate as the polymer raw material can be easily polymerized by using a polymerization initiator. The method of polymerization is not particularly limited. For example, the reaction can be carried out by using benzoyl peroxide and heating. In addition, for example, the reaction can be carried out by using 1-hydroxycyclohexyl phenyl ketone and irradiating light.

[0044] In addition, as the material constituting the second polymer film 3, polyallylamine, polyethyleneimine, etc. can be added. In this case, the addition amount of polyallylamine, etc. can be about 10 wt% relative to PEG MA.

[0045] The first polymer film 2 mainly composed of a vinyl polymer and a polysiloxane has excellent gas permeability. In particular, the thinner the layer, the higher the gas permeability. In addition, the first polymer film 2 has selectivity for specified gases (CO2, O2), but CO2 / N2 is limited to about 10. On the other hand, the second polymer film 3 containing an ethylene oxide chain has excellent gas separation performance (selectivity), especially high CO2 / N2. However, in order to maintain sufficient gas permeability, it is necessary to make the layer as thin as possible and (or) reduce the crosslinking degree. Therefore, by combining the first polymer film 2 with different characteristics (selectivity) and the second polymer film 3 (laminating two polymer layers), a polymer composite film 1 having both excellent gas permeability and gas selectivity can be obtained.

[0046] Here, from the perspective of ensuring a CO₂ permeability of around 1000 GPU, the total film thickness of the first polymer film 2 and the second polymer film 3 is preferably set to 10 nm to 2 μm, and more preferably set to 20 nm to 1000 nm (the same applies to the second to fourth embodiments). It should be noted that, for the first embodiment, from the perspective of the polymer composite film 1 as a whole having self-supporting properties, more preferably, the film thickness of the first polymer film 2 is set to 30 nm or more (e.g., 120 to 1300 nm), and the film thickness of the second polymer film 3 is set to 10 nm or more (e.g., 18 to 113 nm).

[0047] As the support 5, for example, a polyacrylonitrile (hereinafter sometimes referred to as "PAN") layer having countless fine voids and high gas permeability, or a porous PAN membrane composed of a composite film having a PAN layer on the outermost surface can be used. In addition, as the support 5, an anodized alumina sheet (commercial example: Anodisc) can also be used. Furthermore, so-called membrane filters such as polyethersulfone, polycarbonate, and polyimide can be used.

[0048] When a specified gas (here, air) is supplied to the gas separation body 6 including the first polymer film 2 and the second polymer film 3, carbon dioxide (CO₂) and oxygen (O₂) in the air are further selectively permeated (the same applies to the second to fourth embodiments). Thereby, CO₂ can be effectively recovered from the air, or the concentration of O₂ can be increased.

[0049] Hereinafter, the manufacturing process of the polymer composite film 1 and the gas separation body 6 including the polymer composite film 1 in the first embodiment will be described.

[0050] <Preliminary preparation>

[0051] As a preliminary preparation for obtaining a polymer solution containing an ethylene oxide chain, first, an operation of polymerizing PEGMA as a monomer is performed. The polymer containing an ethylene oxide chain is prepared by radical polymerization of PEGMA. Toluene is used as the reaction solvent, and after the polymerization reaction, powdered polymerized PEGMA (hereinafter sometimes referred to as "P(PEGMA)") is obtained through a reprecipitation operation using hexane and drying of the precipitate.

[0052] <The first step>

[0053] The first step is the following steps: Prepare a poly(ethylene oxide) chain-containing polymer solution containing an ethylene oxide chain, and prepare a polymer material-containing solution containing a polymer material that has selective permeability to a specified gas when thinned. Note that the "preparation" in the first step includes preparation or purchase of commercially available products. Here, prepare a poly(ethylene oxide) chain-containing polymer solution obtained by dissolving a powder of P(PEGMA) and a photoinitiator in a specified solvent, and a PDMS preparation solution (polymer material-containing solution) obtained by mixing PDMS, a PDMS curing agent, and a solvent in a specified ratio. Note that the photoinitiator may be included in a range of 0.01 to 20 wt% with respect to P(PEGMA). In addition, as the solvent for preparing the poly(ethylene oxide) chain-containing polymer solution, for example, ethanol, toluene, xylene, or a mixed solvent of ethanol and water can be used. In addition, as the solvent for preparing the polymer material-containing solution, for example, hexane, toluene, or cyclohexane can be used.

[0054] <The second step>

[0055] The second step is the following steps: On a substrate on which a sacrificial layer is formed, coat a poly(ethylene oxide) chain-containing polymer solution so as to cover the sacrificial layer, thereby forming a second polymer film 3. First, coat a water-soluble polymer on a cleaned glass substrate (hereinafter sometimes referred to as "substrate") by spin coating to form a sacrificial layer. Next, by spin coating, coat the poly(ethylene oxide) chain-containing polymer solution prepared in advance in the first step so as to cover the sacrificial layer, thereby forming a second polymer film 3.

[0056] <The third step>

[0057] The third step is a step of crosslinking the second polymer film 3. As described above, a photoinitiator is included in the poly(ethylene oxide) chain-containing polymer solution, and crosslinking is initiated and carried out by UV (ultraviolet) irradiation. That is, the second polymer film 3 is composed of a crosslinked polymer containing an ethylene oxide chain (a polymer layer obtained by crosslinking P(PEGMA) as linear polymer chains with each other).

[0058] Note that the crosslinking is preferably carried out in a nitrogen atmosphere (an atmosphere excluding O2). Thereby, polymerization inhibition caused by O2 can be prevented. In addition, preferably, the irradiation time (or energy) of UV is controlled, and the crosslinking is stopped in a state where the second polymer film 3 is in a rubber state (that is, a state maintaining entropy elasticity, or a state where functional groups contributing to the crosslinking reaction remain in the second polymer film 3). In this case, the crosslinked polymer containing an ethylene oxide chain constitutes the second polymer film 3 in a partially crosslinked state.

[0059] By making the second polymer film 3 in a rubber state, when separating the polymer composite film 1 from the substrate in the fifth process described below, dissolution of the second polymer film 3 in water can be suppressed. That is, by crosslinking P(PEGMA) with each other, the physical properties of the second polymer film 3 are stabilized, and the polymer composite film 1 including the second polymer film 3 can be manufactured without breakage or the like. In addition, by stopping the progress of crosslinking in a rubber state (forming a partially crosslinked state), gas permeability of the second polymer film 3 can be ensured.

[0060] <Fourth Process>

[0061] The fourth process is the following process: A PDMS preparation solution, that is, a polymer material-containing solution, is coated so as to cover the crosslinked second polymer film 3 and cured to form the first polymer film 2. By spin coating, the polymer material-containing solution (PDMS preparation solution) prepared in the first process is coated so as to cover the crosslinked second polymer film 3, and further cured.

[0062] <Fifth Process>

[0063] The fifth process is the following process: The sacrificial layer is dissolved, and the polymer composite film 1 composed of the first polymer film 2 and the second polymer film 3 is peeled off from the substrate. By the above process, on the substrate, the sacrificial layer, the second polymer film 3, and the first polymer film 2 are formed in this order from the closest to the substrate. By immersing the substrate on which the polymer composite film 1 is formed in water, the sacrificial layer is dissolved in water, and thus the polymer composite film 1 is peeled off from the substrate.

[0064] Then, the polymer composite film 1 peeled off from the substrate is transferred to the support 5, whereby the gas separation body 6 can be obtained. When performing the transfer, the configuration shown in (a) in Figure 1 or the configuration shown in (b) in Figure 1 can be selected. As described later, in the gas separation body 6, the gas separation characteristics are different depending on whether the gas permeates in the order from the first polymer film 2 to the second polymer film 3 or in the order from the second polymer film 3 to the first polymer film 2, and the user can select the configuration of the gas separation body 6 according to the required characteristics.

[0065] Example 1

[0066] According to the above process, first, a polymer solution containing an oxyethylene chain is prepared by dissolving it in ethanol such that the content of P(PEGMA) becomes 0.05 g / mL and the content of the photoinitiator becomes 0.0005 g / mL.

[0067] Prepare a PDMS preparation solution (a solution containing a polymer material) by dissolving it in hexane such that the content of poly(dimethylsiloxane) with a hydroxyl end (PDMS) becomes 0.038 g / mL, the content of trimethoxy(methyl)silane becomes 0.0016 g / mL, and the content of diisopropoxybis(ethyl acetoacetate)titanium becomes 0.0008 g / mL.

[0068] On a substrate on which a layer of sodium polystyrene sulfonate (hereinafter sometimes referred to as "PSS") (sacrificial layer) is formed, coat the ethylene oxide chain-containing polymer solution prepared by the above operation by spin coating (3000 rpm / 1 minute). Then, leave the substrate standing in an N2 atmosphere for 30 minutes. Then, perform UV irradiation in the same atmosphere to form the second polymer thin film 3.

[0069] Next, coat the PDMS preparation solution prepared by the above operation by spin coating (3000 rpm / 1 minute) so as to cover the second polymer thin film 3. Then, leave the substrate standing in the atmosphere for one day to cure the PDMS and form the first polymer thin film 2.

[0070] Next, immerse the substrate in water to dissolve the sacrificial layer, and peel the polymer composite film 1 from the substrate. Then, transfer the polymer composite film 1 to the support 5 such that the first polymer thin film 2 in the polymer composite film 1 contacts the support 5 to obtain a gas separation body 6.

[0071] Example 2

[0072] An ethylene oxide chain-containing polymer solution with the content of P(PEGMA) being 0.04 g / mL and the content of the photoinitiator being 0.0004 g / mL was used, and except for this, the polymer composite film 1 and the gas separation body 6 were prepared under the same conditions as in Example 1.

[0073] Example 3

[0074] An ethylene oxide chain-containing polymer solution with the content of P(PEGMA) being 0.03 g / mL and the content of the photoinitiator being 0.0003 g / mL was used, and except for this, the polymer composite film 1 and the gas separation body 6 were prepared under the same conditions as in Example 1.

[0075] Example 4

[0076] An ethylene oxide chain-containing polymer solution with the content of P(PEGMA) being 0.005 g / mL and the content of the photoinitiator being 0.00005 g / mL, and a PDMS preparation solution with the content of PDMS being 0.076 g / mL were used, and except for this, the polymer composite film 1 and the gas separation body 6 were prepared under the same conditions as in Example 1.

[0077] Example 5

[0078] A high molecular weight solution containing ethylene oxide chains with a P(PEGMA) content of 0.005 g / mL and a photoinitiator content of 0.00005 g / mL, and a PDMS preparation solution with a PDMS content of 0.114 g / mL were used. Except for this, a polymer composite film 1 and a gas separator 6 were prepared under the same conditions as in Example 1.

[0079] Example 6

[0080] A high molecular weight solution containing ethylene oxide chains with a P(PEGMA) content of 0.01 g / mL and a photoinitiator content of 0.0001 g / mL, and a PDMS preparation solution with a PDMS content of 0.2 g / mL were used. Except for this, a polymer composite film 1 and a gas separator 6 were prepared under the same conditions as in Example 1.

[0081] (Comparative Example)

[0082] Hereinafter, the comparative example will be described. A PDMS preparation solution was obtained in the same manner as in Example 1. The substrate was washed with O2 plasma, and an aqueous PSS solution (15 wt%) was spin-coated (3000 rpm / 1 minute) on the substrate. After forming a sacrificial layer, it was heated and dried.

[0083] Next, the PDMS preparation solution was coated by spin coating (3000 rpm / 1 minute) so as to cover the sacrificial layer. Then, the substrate was left standing in the atmosphere for one day to cure the PDMS. Next, the substrate was immersed in water to dissolve the sacrificial layer, and the polymer film was peeled off from the substrate. Then, the PDMS film was transferred to the support 5 to obtain a gas separator 6. Hereinafter, the polymer film of the comparative example may sometimes be referred to as the "PDMS film". It should be noted that the PDMS film corresponds to the first polymer film 2 described above.

[0084] Hereinafter, in [Table 1], for Examples 1 to 6 and Comparative Examples, the presence or absence of self-supportability, the film thickness of the first polymer film 2, the film thickness of the second polymer film 3, the CO2 permeability, the N2 permeability, the O2 permeability, the selectivity ratios CO2 / N2, O2 / N2, and CO2 / O2 are shown. It should be noted that regarding the film thicknesses of the first polymer film 2 and the second polymer film 3, the results were obtained by fabricating a plurality of gas separation elements 6 under the same conditions and observing the cross-section of the polymer composite film 1 using a scanning electron microscope (SEM). Additionally, regarding the gas permeability, the results were obtained by conducting a gas permeability test in which CO2 gas, N2 gas, and O2 gas at a constant pressure were respectively supplied to the gas separation element 6, and the volume of gas passing through the second polymer film 3 and the first polymer film 2 with a membrane area of 0.785 cm -10 mol·m -2 ·s -1 ·Pa -1 。

[0085] It should be noted that regarding the gas permeability test, specifically, CO2 gas, N2 gas, and O2 gas at a constant pressure were respectively supplied to the gas separation element 6, and the volume of gas passing through the second polymer film 3 and the first polymer film 2 with a membrane area of 0.785 cm 2 was measured using a soap film flowmeter.

[0086] [Table 1]

[0087]

[0088] As shown in [Table 1], the polymer composite films 1 of Examples 1 to 6 and the Comparative Examples all have self-supportability. It should be noted that the presence or absence of self-supportability is judged according to the following criteria: after peeling the film (membrane) from the substrate in the stripping solution, whether it can maintain the flat film shape without breaking independently even when the film floating in the liquid is lifted into the air. That is, the case where the film structure is maintained without breaking even in the air is judged as having "self-supportability", and the case where the film structure is maintained in the state of floating in the stripping solution after peeling but is prone to breakage when taken out into the air is judged as having "no" self-supportability.

[0089] In Examples 1 to 3, the thickness of the first polymer film 2 containing PDMS was substantially the same as that of the PDMS film in the comparative example, and in terms of structure, it can be considered as a film obtained by overlapping the second polymer film 3 on the PDMS film in the comparative example. The thinner the film thickness of the second polymer film 3, the higher the gas permeability. However, since the second polymer film 3 is overlapped on the first polymer film 2, the film thickness of the polymer composite film 1 also increases, resulting in a decrease in the CO2, N2, and O2 permeabilities compared to the comparative example. However, it is known that the gas selectivity CO2 / N2 is significantly improved compared to the comparative example, and O2 / N2 is also improved.

[0090] In addition, the second polymer film 3 containing P(PEGMA), that is, an ethylene oxide chain, is very soft and fragile when alone. However, by overlapping with the first polymer film 2 as shown in Examples 4 to 6, the second polymer film 3 can be formed very thinly (20 nm or less). Thus, self-supportability can be ensured for the film as a whole, and high gas selectivity can be exhibited.

[0091] Example 7

[0092] A polymer composite film 1 and a gas separation body 6 were prepared under the same conditions as in Example 1, except that a polymer solution containing ethylene oxide chains with a P(PEGMA) content of 0.03 g / mL and a photoinitiator content of 0.0003 g / mL, and a PDMS preparation solution with a PDMS content of 0.076 g / mL were used.

[0093] Example 8

[0094] A polymer composite film 1 and a gas separation body 6 were prepared under the same conditions as in Example 1, except that a polymer solution containing ethylene oxide chains with a P(PEGMA) content of 0.03 g / mL and a photoinitiator content of 0.0003 g / mL, and a PDMS preparation solution with a PDMS content of 0.114 g / mL were used.

[0095] Example 9

[0096] A gas separation body 6 was prepared under the same conditions as in Example 7, except that the polymer composite film 1 was transferred to the support 5 in such a manner that the second polymer film 3 in the polymer composite film 1 was in contact with the support 5.

[0097] Example 10

[0098] A gas separation body 6 was prepared under the same conditions as in Example 8, except that the polymer composite film 1 was transferred to the support 5 in such a manner that the second polymer film 3 in the polymer composite film 1 was in contact with the support 5.

[0099] Hereinafter, in [Table 2], for Examples 7 to 10, the presence or absence of self-supporting property, the film thickness of the first polymer film 2, the film thickness of the second polymer film 3, the CO2 permeability, the N2 permeability, the O2 permeability, the selectivity ratios CO2 / N2, O2 / N2, and CO2 / O2 are shown.

[0100] [Table 2]

[0101]

[0102] Here, regarding the gas permeability, in Examples 7 and 8 where the second polymer film 3 is in contact with the support 5, the gas permeability test is carried out by allowing the gas to permeate in the order from the second polymer film 3 to the first polymer film 2 (see Figure 1 (a) therein), and in Examples 9 and 10 where the first polymer film 2 is in contact with the support 5, the gas permeability test is carried out by allowing the gas to permeate in the order from the first polymer film 2 to the second polymer film 3 (see Figure 1 (b) therein). As can be seen from [Table 2], when the gas permeates in the order from the second polymer film 3 to the first polymer film 2, the gas selectivity is more excellent. On the other hand, when the gas permeates in the order from the first polymer film 2 to the second polymer film 3, the gas permeability is more excellent.

[0103] (Second Embodiment)

[0104] Figure 2 (a) in [ ] is an explanatory diagram showing the structure of the polymer composite film 1 and the gas separation body 6 including the polymer composite film 1 according to the second embodiment of the present invention. In the second embodiment, the constituent elements of the gas separation body 6 are the same as those in the first embodiment, but the second embodiment is different from the first embodiment in that a reinforcing material 10 is dispersed in the second polymer film 3. Here, as the reinforcing material 10, carbon nanotubes 11 and cellulose nanofibers 12 can be preferably used. The carbon nanotubes 11 and cellulose nanofibers 12 have high mechanical strength as materials, and the second polymer film 3 obtained by dispersing them exhibits high mechanical strength.

[0105] As the carbon nanotube 11, any one of single-walled carbon nanotubes (SWNTs) and multi-walled carbon nanotubes (MWNTs) can be used (hereinafter, they may be collectively referred to as "CNTs"). Due to its high aspect ratio (in SWNTs, the diameter is 0.5 to 3 nm and the length is ~10 μm; in MWNTs, the diameter is 5 to 100 nm and the length is ~20 μm), CNTs can form a network of tubes, and their mechanical properties can be obtained through a combination of rigidity, strength, and tensile strength.

[0106] Among the cellulose nanofibers 12, oxidized cellulose nanofibers are included. Furthermore, as the organic polymer, a mixture of cellulose nanofibers 12 and oxidized cellulose nanofibers can also be used (hereinafter, they may be collectively referred to as "CNFs"). CNFs form fibrils as small fibers (fibrous structures). The fibrils have high mechanical strength as materials. By dispersing the reinforcing material 10 composed of CNFs in the second polymer film 3, the overall mechanical strength is extremely high. In addition, CNFs can be manufactured at low cost from resources such as wood, which is abundant, through mechanical fibrillation, etc. Moreover, since they are plant fibers, they are environmentally friendly materials.

[0107] CNT and CNF preferably have a diameter smaller than the film thickness of the polymer composite film 1 (for example, ~200 nm), more preferably have a diameter smaller than the film thickness of the second polymer film 3 in the above first embodiment (for example, ~70 nm), and furthermore, more preferably have a diameter smaller than the film thickness of the second polymer film 3 in the second embodiment (for example, ~35 nm). By selecting CNTs and CNFs with a diameter smaller than the film thickness of the polymer composite film 1, the mechanical strength is improved, and the functionality of the entire polymer composite film 1 (here, gas permeability and gas selectivity) can be exerted. In addition, by using CNTs and CNFs with a diameter smaller than the film thickness of the second polymer film 3 (or the first polymer film 2), the functionality of the second polymer film 3 (the first polymer film 2) can be fully exerted. (The same applies to the third and fourth embodiments)

[0108] It should be noted that Figure 2 in (a) Figure 2 in (b), Figure 2 in (c) is the same), it is described that the reinforcing material 10 with the same fiber length is arranged in a specific direction, but it is only schematically described after all. The lengths of CNTs and CNFs are various, and in addition, they are oriented in all directions and become a tangled state (tube network or fiber network), and are included in the second polymer film 3 ( Figure 2the first polymer thin film 2 in (b) thereof, Figure 2 in the reinforcing layer 4 in (c) thereof (hereinafter, they may be collectively referred to as "thin film · layer"). However, by adjusting the addition amounts of CNT and CNF, the distribution of CNT and CNF is restricted (controlled) in such a manner that the density of the network in the thin film · layer becomes extremely sparse. Thereby, a decrease in the functionality (here, particularly the permeability) of the polymer composite thin film 1 can be prevented.

[0109] In the network with sparse density, in plane A thereof, in the thickness direction of the thin film · layer, there are mixedly present a first region A1 of a plurality of reinforcing materials 10, a second region A2 of a single reinforcing material 10, and a third region A3 where no reinforcing material 10 exists. This can also be described in other words as: in a part of the plane formed by the thin film · layer, in the thickness direction of the thin film · layer, there are regions where a plurality of reinforcing materials 10 do not overlap with each other. Further, when the area of the first region A1 is set as S1, the area of the second region A2 is set as S2, and the area of the third region A3 is set as S3, the thin film · layer is formed in such a manner that S1 < S2 < S3. Here, if the ratio of S3 in plane A is taken as the porosity, the porosity is preferably greater than 90%.

[0110] Hereinafter, the manufacturing process of the polymer composite thin film 1 in the second embodiment and the gas separator 6 including the polymer composite thin film 1 will be described.

[0111] <The first process>

[0112] It is the following process: Prepare a solution containing an ethylene oxide chain-containing polymer and a reinforcing material 10, that is, a solution containing an ethylene oxide chain-containing polymer - reinforcing material, and prepare a solution containing a polymer material that has a selective permeability to a specified gas when made into a thin film.

[0113] Similar to the first process of the first embodiment, to the powder of P(PEGMA), a photoinitiator of 1 wt% relative to P(PEGMA) is added and dissolved in a specified amount of ethanol, thereby preparing a solution of an ethylene oxide chain-containing polymer. When using a carbon nanotube 11 as the reinforcing material 10, the carbon nanotube 11 is previously dispersed in ethanol to prepare a CNT dispersion.

[0114] On the other hand, when using a cellulose nanofiber 12 as the reinforcing material 10, the cellulose nanofiber 12 is previously dispersed in ethanol to prepare a CNF dispersion. At this time, it is preferable to previously prepare the CNF dispersion in such a manner that there are no aggregates that would cause film defects during film formation.

[0115] By mixing the above-mentioned poly(ethylene oxide) chain-containing polymer solution with a CNT dispersion or a CNF dispersion, a solution containing a poly(ethylene oxide) chain-containing polymer-reinforcement material, which contains a poly(ethylene oxide) chain-containing polymer and a reinforcement material 10, is prepared. It should be noted that the step of "preparing a polymer material-containing solution containing a polymer material that has selective permeability to a specified gas when made into a thin film" is the same as the first step described in the first embodiment, and thus the description thereof is omitted.

[0116] <Second Step>

[0117] The second step is the following step: On a substrate on which a sacrificial layer is formed, a solution containing a poly(ethylene oxide) chain-containing polymer-reinforcement material is coated so as to cover the sacrificial layer, thereby forming a second polymer thin film 3. Similar to the second step of the first embodiment, a sacrificial layer made of PSS is formed on the substrate. Next, a solution containing a poly(ethylene oxide) chain-containing polymer-reinforcement material prepared in the first step is coated so as to cover the sacrificial layer, thereby forming a second polymer thin film 3. Then, the second polymer thin film 3 is allowed to stand in a N2 atmosphere for about 30 minutes.

[0118] By using spin coating when coating the solution containing a poly(ethylene oxide) chain-containing polymer-reinforcement material, a strong external force acts on the reinforcement material 10 contained in the solution, and the carbon nanotubes 11 or cellulose nanofibers 12 contained in the reinforcement material 10 cannot form a tube (fiber) network three-dimensionally, that is, in the thickness direction of the film. As a result, the reinforcement material 10 is impacted by the solvent (here ethanol) and is arranged in a plane, forming a substantially two-dimensional tube (fiber) network (the above-mentioned network with a sparse density).

[0119] <Third Step to Fifth Step>

[0120] The third step is a step of crosslinking the second polymer thin film 3, the fourth step is a step of coating a polymer material-containing solution so as to cover the crosslinked second polymer thin film 3 and curing it to form a first polymer thin film 2, and the fifth step is a step of dissolving the sacrificial layer to peel the polymer composite film 1 composed of the first polymer thin film 2 and the second polymer thin film 3 from the substrate. These steps are the same as the third step to the fifth step described in the first embodiment, and thus the description thereof is omitted. Then, the polymer composite film 1 peeled from the substrate is transferred to a support 5, whereby a gas separation body 6 can be obtained. It should be noted that, as described in the first embodiment, when transferring, it can be configured such that the first polymer thin film 2 is in contact with the support 5, or it can be configured such that the second polymer thin film 3 is in contact with the support 5.

[0121] Example 11

[0122] 1 g of P(PEGMA) powder and 0.01 g of a photoinitiator were dissolved in ethanol to prepare a poly(ethylene oxide)-chain-containing polymer solution in which the content of P(PEGMA) was 0.01 g / mL and the content of the photoinitiator was 0.0001 g / mL. Further, a CNT dispersion was added to the poly(ethylene oxide)-chain-containing polymer solution to prepare a solution containing a poly(ethylene oxide)-chain-containing polymer-reinforcement material including 0.00003 g / mL of carbon nanotubes 11. Separately therefrom, a PDMS preparation solution was prepared in the same manner as in Example 1.

[0123] Next, a sacrificial layer was formed on the substrate using PSS in the same manner as in Example 1. Further, on the substrate on which the sacrificial layer was formed, the solution containing the poly(ethylene oxide)-chain-containing polymer-reinforcement material prepared by the above operation was applied by spin coating. The substrate coated with the solution containing the poly(ethylene oxide)-chain-containing polymer-reinforcement material was allowed to stand in an N2 atmosphere for 30 minutes.

[0124] Then, UV irradiation was performed in the same atmosphere to crosslink the layer containing the poly(ethylene oxide)-chain-containing polymer-reinforcement material, thereby forming the second polymer film 3. It should be noted that in Example 4, the crosslinking was also stopped in a state where the second polymer film 3 was rubbery by controlling the UV irradiation time.

[0125] Next, the PDMS preparation solution prepared by the above operation was applied by spin coating (3000 rpm / 1 minute) so as to cover the second polymer film 3. Then, the substrate was allowed to stand in the atmosphere for one day to cure the PDMS, thereby forming the first polymer film 2.

[0126] Next, the substrate was immersed in water to dissolve the sacrificial layer, and the polymer composite film 1 was peeled off from the substrate. Then, in the same manner as in Example 1, the polymer composite film 1 was transferred to the support 5 such that the first polymer film 2 in the polymer composite film 1 was in contact with the support 5, thereby obtaining the gas separator 6.

[0127] Example 12

[0128] A solution containing a poly(ethylene oxide)-chain-containing polymer-reinforcement material including 0.000015 g / mL of carbon nanotubes 11 was used, and the polymer composite film 1 and the gas separator 6 were produced under the same conditions as in Example 11 except for this.

[0129] Example 13

[0130] A solution containing a poly(ethylene oxide)-chain-containing polymer-reinforcement material including 0.0000039 g / mL of carbon nanotubes 11 was used, and the polymer composite film 1 and the gas separator 6 were produced under the same conditions as in Example 11 except for this.

[0131] Example 14

[0132] 0.5 g of P(PEGMA) powder and 0.005 g of a photoinitiator were dissolved in ethanol to prepare a poly(ethylene oxide) chain-containing polymer solution with a P(PEGMA) concentration of 0.03 g / mL and a photoinitiator content of 0.0003 g / mL. Further, a CNF dispersion was added to the poly(ethylene oxide) chain-containing polymer solution to prepare a solution containing a poly(ethylene oxide) chain-containing polymer - reinforcing material containing 0.00024 g / mL of cellulose nanofibers 12. In addition, a PDMS preparation solution was prepared in the same manner as in Example 1 separately.

[0133] Next, a sacrificial layer was formed on the substrate using PSS in the same manner as in Example 1. In the same manner as in Example 11, on top of the sacrificial layer, a second polymer film 3 was made using the solution containing the poly(ethylene oxide) chain-containing polymer - reinforcing material, and the crosslinking was stopped in the rubber state. Further, a first polymer film 2 was made using the PDMS preparation solution so as to coat the second polymer film 3. Next, the polymer composite film 1 composed of the second polymer film 3 and the first polymer film 2 was peeled off from the sacrificial layer. Then, the polymer composite film 1 was transferred to the support 5 in the same manner as in Example 1 to obtain a gas separation body 6.

[0134] Hereinafter, in [Table 3], for Examples 11 to 14, the presence or absence of self - standing property, the film thickness of the first polymer film 2, the film thickness of the second polymer film 3, the reinforcing material 10 added to the second polymer film 3, the addition amount of the reinforcing material 10, the CO2 permeability, the N2 permeability, the O2 permeability, the selectivity CO2 / N2, O2 / N2, and CO2 / O2 are shown. The data of the comparative examples are also shown in [Table 3].

[0135] [Table 3]

[0136]

[0137] As shown in [Table 3], the polymer composite films 1 of Examples 11 to 14 all have self - standing property. In any of them, the thickness of the first polymer film 2 containing PDMS is substantially the same as that of the PDMS film of the comparative example. The polymer composite films 1 of Examples 11 to 14 can be considered to be films obtained by overlapping a second polymer film 3 containing a reinforcing material 10 on the PDMS film of the comparative example in terms of composition.

[0138] Since the second polymer film 3 is stacked on the first polymer film 2, the overall film thickness also increases, resulting in a decrease in the CO2, N2, and O2 permeabilities in Examples 11 and 14 compared to the comparative examples. On the other hand, in Examples 12 and 13, the CO2 permeability is greater than 10,000 GPU, achieving values not inferior to those of the comparative examples. In addition, it can be seen that the gas selectivity CO2 / N2 is significantly improved compared to the comparative examples, and O2 / N2 is also improved.

[0139] Here, in Examples 11 to 13, carbon nanotubes 11 were added to the second polymer film 3. When comparing this with Examples 1 to 3 (the second polymer film 3 does not contain the reinforcing material 10), in Examples 11 to 13, the film thickness of the second polymer film 3 is 38 nm, and in Examples 1 to 3, the film thickness of the second polymer film 3 is 113 nm to 74 nm. That is, in Examples 11 to 13, by adding carbon nanotubes 11 as the reinforcing material 10 to the second polymer film 3, the mechanical strength is improved, and the second polymer film 3 (as a result, the polymer composite film 1) can be formed thinner.

[0140] In addition, in Example 14, cellulose nanofibers 12 were added to the second polymer film 3. The film thickness of the second polymer film 3 in Example 14 is 74 nm, which is the same as the film thickness of the second polymer film 3 in Example 3. It is considered that the cellulose nanofibers 12 added to the second polymer film 3 function as a barrier, resulting in a decrease in the CO2 permeability (5459 GPU in Example 3 and 3586 GPU in Example 14). However, it is clear that the mechanical strength of the second polymer film 3 is improved by using cellulose nanofibers 12, and the configuration of Example 14 can be preferably used, for example, in cases where the pressure difference between the upstream and downstream is large across the gas separation body 6.

[0141] (Third Embodiment)

[0142] Figure 2Figure (b) is an explanatory diagram showing the structure of the polymer composite film 1 and the gas separation body 6 including the polymer composite film 1 according to the third embodiment of the present invention. In the third embodiment, the components of the gas separation body 6 are the same as those in the first embodiment, but the third embodiment is different from the first and second embodiments in that the reinforcing material 10 is dispersed in the first polymer film 2. As the reinforcing material 10, CNT or CNF can be preferably used as in the second embodiment. The first polymer film 2 obtained by dispersing CNT or CNF exhibits extremely high mechanical strength. In particular, by selecting CNT or CNF having a diameter smaller than the film thickness of the first polymer film 2, the functionality of the first polymer film 2 can be fully exerted. It should be noted that in the first polymer film 2, the reinforcing material 10 also constitutes the above-mentioned sparse network of density.

[0143] Hereinafter, the manufacturing process of the polymer composite film 1 and the gas separation body 6 including the polymer composite film 1 in the third embodiment will be described.

[0144] <The first process>

[0145] The following steps are as follows: Prepare a polyoxyethylene chain-containing polymer solution containing an oxyethylene chain, and prepare a polymer material-containing solution containing a polymer material and a reinforcing material 10 that has a selective permeability to a specified gas when formed into a film.

[0146] Similar to the first process of the first embodiment, a photoinitiator of 1 wt% relative to P(PEGMA) is added to the powder of P(PEGMA), and it is dissolved in a specified amount of ethanol to prepare a polyoxyethylene chain-containing polymer solution.

[0147] Similar to the second embodiment, a CNT dispersion (or CNF dispersion) and a polymer material-containing solution (PDMS preparation solution) are prepared. By mixing the above-mentioned polymer material-containing solution with the CNT dispersion or CNF dispersion, a polymer material-containing solution containing a polymer material (here PDMS) and a reinforcing material 10 is prepared.

[0148] <The second process, the third process>

[0149] The second process is the following step: On a substrate on which a sacrificial layer is formed, a polyoxyethylene chain-containing polymer solution is coated so as to cover the sacrificial layer to form a second polymer film 3. In addition, the third process is a process of crosslinking the second polymer film 3. The second process and the third process are the same as those in the first embodiment, so the description is omitted.

[0150] <The fourth process>

[0151] The following steps are carried out: A solution containing a polymer material - reinforcing material is coated in the form of the second crosslinked polymer film 3 and cured to form the first polymer film 2. A solution containing a polymer material - reinforcing material prepared in the first step is coated in the form of the second crosslinked polymer film 3. Then, it is left standing in the atmosphere for 1 day to cure the first polymer film 2.

[0152] <The fifth step>

[0153] The following steps are carried out: The sacrificial layer is dissolved, and the polymer composite film 1 composed of the first polymer film 2 and the second polymer film 3 is peeled off from the substrate. The fifth step is the same as that of the first embodiment, so the description is omitted. The polymer composite film 1 peeled off from the substrate is transferred to the support 5, whereby the gas separation body 6 can be obtained.

[0154] Example 15

[0155] A polymer solution containing an oxyethylene chain with a P(PEGMA) content of 0.01 g / mL and a photoinitiator content of 0.0001 g / mL was prepared in the same manner as in Example 11. In addition, a PDMS preparation solution was prepared in the same manner as in Example 1. Further, a CNT dispersion was added to the PDMS preparation solution to prepare a solution containing a polymer material - reinforcing material containing 0.000015 g / mL of carbon nanotubes 11.

[0156] Next, a sacrificial layer was formed on the substrate using PSS in the same manner as in Example 1. Further, on the substrate on which the sacrificial layer was formed, the polymer solution containing an oxyethylene chain prepared by the above operation was coated by spin coating. The substrate coated with the polymer solution containing an oxyethylene chain was left standing in an N2 atmosphere for 30 minutes. Then, UV irradiation was carried out in the same atmosphere to crosslink the polymer containing an oxyethylene chain and form the second polymer film 3.

[0157] Next, the solution containing a polymer material - reinforcing material prepared by the above operation was coated by spin coating (3000 rpm / 1 minute) so as to cover the second polymer film 3. Then, the substrate was left standing in the atmosphere for one day to cure the solution containing a polymer material - reinforcing material and form the first polymer film 2. Next, the substrate was immersed in water to dissolve the sacrificial layer and peel the polymer composite film 1 from the substrate. Then, the polymer composite film 1 was placed on the support 5 in the same manner as in Example 1 to obtain the gas separation body 6.

[0158] Example 16

[0159] In the same manner as in Example 3, a poly(ethylene oxide) chain-containing polymer solution with a P(PEGMA) content of 0.03 g / mL and a photoinitiator content of 0.0003 g / mL was prepared. Additionally, a PDMS preparation solution was prepared in the same manner as in Example 1. Further, a CNF dispersion was added to the PDMS preparation solution to prepare a polymer material-reinforcement material-containing solution containing 0.0000004 g / mL of cellulose nanofibers 12. Keeping other conditions the same as in Example 15, a polymer composite film 1 and a gas separator 6 were obtained.

[0160] Example 17

[0161] As the poly(ethylene oxide) chain-containing polymer solution, a poly(ethylene oxide) chain-containing polymer solution with a P(PEGMA) content of 0.01 g / mL and a photoinitiator content of 0.0001 g / mL was used. Otherwise, the same operations as in Example 16 were performed to obtain a polymer composite film 1 and a gas separator 6.

[0162] Hereinafter, in [Table 4], for Examples 15 to 17, the presence or absence of self-supportability, the film thickness of the first polymer film 2, the film thickness of the second polymer film 3, the reinforcement material 10 added to the first polymer film 2, the addition amount of the reinforcement material 10, the CO2 permeability, the N2 permeability, the O2 permeability, the selectivity ratio CO2 / N2, O2 / N2, and CO2 / O2 are shown. The data of the comparative examples are also recorded in [Table 4].

[0163] [Table 4]

[0164]

[0165] As shown in [Table 4], the polymer composite films 1 of Examples 15 to 17 all have self-supportability. In any of them, the thickness of the first polymer film 2 containing PDMS is approximately the same as that of the PDMS film of the comparative example. The polymer composite films 1 of Examples 15 to 17 can be considered in terms of composition as films obtained by adding the reinforcement material 10 to the PDMS film of the comparative example and overlapping the second polymer film 3 thereon.

[0166] Since the second polymer film 3 is overlapped on the first polymer film 2 containing PDMS and the reinforcement material 10, the overall film thickness also increases, resulting in a decrease in the CO2, N2, and O2 permeabilities in Examples 15 to 17 compared to the comparative example. On the other hand, it can be seen that the gas selectivity CO2 / N2 is significantly improved compared to the comparative example, and O2 / N2 is also improved.

[0167] Here, in Example 15, carbon nanotubes 11 were added to the first polymer film 2, and in Example 17, cellulose nanofibers 12 were added to the first polymer film 2. When compared with Examples 1 to 3 (where the first polymer film 2 does not contain the reinforcing material 10), in Examples 15 and 17, the film thickness of the second polymer film 3 is 38 nm, and in Examples 1 to 3, the film thickness of the second polymer film 3 is 113 nm to 74 nm. That is, in Examples 15 and 17, by using the first polymer film 2 containing the reinforcing material 10 to support the second polymer film 3, the overall mechanical strength is improved, and the second polymer film 3 (as a result, the polymer composite film 1) can be formed thinner.

[0168] (Fourth Embodiment)

[0169] Figure 2 In (c), it is an explanatory diagram showing the configuration of the polymer composite film 1 according to the fourth embodiment of the present invention and the gas separation body 6 including the polymer composite film 1. In the fourth embodiment, the gas separation body 6 is composed of the polymer composite film 1 and the support 5. Moreover, the polymer composite film 1 is composed of the first polymer film 2, the reinforcing layer 4, and the second polymer film 3, and the reinforcing layer 4 is provided between the first polymer film 2 and the second polymer film 3. Here, the reinforcing layer 4 is composed of the reinforcing material 10 such as carbon nanotubes 11 and cellulose nanofibers 12. That is, the fourth embodiment is different from each embodiment in that the reinforcing layer 4 composed of the reinforcing material 10 is independently provided. The carbon nanotubes 11 and cellulose nanofibers 12 have high mechanical strength as materials, and the reinforcing layer 4 composed of them exhibits extremely high mechanical strength. As a result, the strength of the entire polymer composite film 1 is improved. It should be noted that in the reinforcing layer 4, the reinforcing material 10 also forms the above-mentioned sparse network of density.

[0170] In the fourth embodiment, the configurations of the first polymer film 2, the second polymer film 3, and the support 5 are the same as those in the first embodiment, so the description is omitted. Hereinafter, the manufacturing process of the polymer composite film 1 and the gas separation body 6 including the polymer composite film 1 in the fourth embodiment will be described.

[0171] <First Step>

[0172] It is the following steps: Prepare a reinforcing material dispersion liquid containing the reinforcing material 10, a polyoxyethylene chain-containing polymer solution containing an oxyethylene chain, and a polymer material solution containing a polymer material that has selective permeability to a specified gas when thinned.

[0173] Similar to the first step of the first embodiment, a photoinitiator at 1 wt% relative to P(PEGMA) was added to the powder of P(PEGMA), and it was dissolved in a specified amount of ethanol to prepare a polymer solution containing an ethylene oxide chain. The same operations as in the second embodiment were performed to prepare a CNT dispersion or a CNF dispersion (hereinafter, sometimes collectively referred to as "reinforcement material dispersions"), and a polymer material solution (PDMS preparation solution).

[0174] <Second Step, Third Step>

[0175] The second step is the following step: On the substrate on which the sacrificial layer is formed, the polymer solution containing an ethylene oxide chain is coated in a manner to cover the sacrificial layer, thereby forming the second polymer film 3. In addition, the third step is a step of crosslinking the second polymer film 3. The second step and the third step are the same as those in the first embodiment, so the description is omitted.

[0176] <Fourth Step>

[0177] It is the following step: The reinforcement material dispersion is coated in a manner to cover the crosslinked second polymer film 3, thereby forming the reinforcement layer 4. When forming the reinforcement layer 4, the reinforcement material dispersion prepared in the first step is coated in a manner to cover the crosslinked second polymer film 3.

[0178] <Fifth Step>

[0179] It is the following step: The polymer material solution is coated in a manner to cover the reinforcement layer 4 and cured, thereby forming the first polymer film 2. The polymer material solution (PDMS preparation solution) prepared in the first step is coated in a manner to cover the reinforcement layer 4 to form the first polymer film 2. Then, the first polymer film 2 is left standing in the air for 1 day to cure the first polymer film 2.

[0180] <Sixth Step>

[0181] It is the following step: The sacrificial layer is dissolved, and the polymer composite film 1 is peeled off from the substrate. On the substrate, the sacrificial layer, the second polymer film 3, the reinforcement layer 4, and the first polymer film 2 are formed in order from near to far from the substrate, and they constitute the polymer composite film 1. By immersing the substrate in water, the sacrificial layer is dissolved in water, thereby peeling the polymer composite film 1 from the substrate. Then, the polymer composite film 1 peeled off from the substrate is transferred to the support 5, whereby the gas separation body 6 can be obtained.

[0182] Note that, for the fourth embodiment, the reinforcing layer 4 may also be formed after the sacrificial layer is formed (the fourth step). Then, an ethylene oxide chain-containing polymer solution is coated so as to cover the reinforcing layer 4 to form the second polymer film 3 and crosslink it (the second step and the third step). Further, a PDMS preparation solution is coated so as to cover the second polymer film 3 to form the first polymer film 2 (the fifth step), thereby forming the polymer composite film 1. Moreover, the gas separation body 6 may be configured such that the reinforcing layer 4 constituting the polymer composite film 1 is in contact with the support 5, or the gas separation body 6 may be configured such that the first polymer film 2 is in contact with the support 5.

[0183] Example 18

[0184] In the same manner as in Example 11, an ethylene oxide chain-containing polymer solution with a P(PEGMA) content of 0.01 g / mL and a photoinitiator content of 0.0001 g / mL was prepared. In addition, a PDMS preparation solution was prepared in the same manner as in Example 1. Further, a reinforcing material dispersion containing 0.00003 g / mL of carbon nanotubes 11 was prepared.

[0185] Next, a sacrificial layer was formed on the substrate using PSS in the same manner as in Example 1. Further, on the substrate on which the sacrificial layer was formed, the ethylene oxide chain-containing polymer solution prepared by the above operation was coated by spin coating (3000 rpm, 1 minute). Then, the substrate coated with the ethylene oxide chain-containing polymer solution was allowed to stand in an N2 atmosphere for 30 minutes. Then, UV irradiation was performed in the same atmosphere to crosslink P(PEGMA) to form the second polymer film 3.

[0186] Next, the reinforcing material dispersion prepared by the above operation was coated by spin coating (3000 rpm / 1 minute) so as to cover the second polymer film 3 to form the reinforcing layer 4. Next, the PDMS preparation solution prepared by the above operation was coated by spin coating (3000 rpm / 1 minute) so as to cover the reinforcing layer 4. Then, the substrate was allowed to stand in the atmosphere for one day to cure the PDMS, thereby forming the first polymer film 2. Thus, a sacrificial layer and a polymer composite film 1 were formed on the substrate.

[0187] Next, the substrate was immersed in water to dissolve the sacrificial layer, and the polymer composite film 1 was peeled off from the substrate. Then, the polymer composite film 1 was transferred to the support 5 such that the first polymer film 2 in the polymer composite film 1 was in contact with the support 5 to obtain the gas separation body 6. Note that when observing the cross section of the polymer composite film 1 using SEM, the reinforcing layer 4 could not be clearly distinguished.

[0188] Example 19

[0189] An enhanced material dispersion containing 0.000015 g / mL of carbon nanotubes 11 was used. Except for this, a polymer composite film 1 and a gas separation body 6 were produced under the same conditions as in Example 18. In Example 19, in the SEM observation of the cross-section of the polymer composite film 1, the reinforcing layer 4 could not be clearly distinguished either.

[0190] Example 20

[0191] An enhanced material dispersion containing 0.0006 g / mL of cellulose nanofibers 12 was used. Except for this, a polymer composite film 1 and a gas separation body 6 were produced under the same conditions as in Example 18. In Example 20, when the cross-section of the polymer composite film 1 was observed by SEM, the reinforcing layer 4 could not be clearly distinguished either.

[0192] Hereinafter, in [Table 5], for Examples 18 to 20, the presence or absence of self-supportability, the film thickness of the first polymer film 2, the film thickness of the second polymer film 3, the material constituting the reinforcing layer 4, the addition amount of the reinforcing material 10, the CO2 permeability, the N2 permeability, the O2 permeability, the selectivity ratio CO2 / N2, O2 / N2, and CO2 / O2 are shown. It should be noted that the data of the comparative examples are also described in [Table 5].

[0193] [Table 5]

[0194]

[0195] As shown in [Table 5], the polymer composite films 1 of Examples 18 to 20 all have self-supportability. In any of them, the thickness of the first polymer film 2 containing PDMS is approximately the same as that of the PDMS film of the comparative example. The polymer composite films 1 of Examples 18 to 20 can be considered, in terms of constitution, as films obtained by making the reinforcing material 10 be biased on one side of the PDMS film of the comparative example and overlapping the second polymer film 3 thereon.

[0196] Since the second polymer film 3 is overlapped on the first polymer film 2 containing PDMS and the reinforcing material 10, the overall film thickness also becomes larger. As a result, the CO2, N2, and O2 permeabilities in Examples 18 to 20 are lower than those of the comparative example. On the other hand, it can be seen that the gas selectivity CO2 / N2 is significantly improved compared with the comparative example, and except for Example 20, O2 / N2 is also improved.

[0197] Here, in Example 18 and Example 19, the reinforcing layer 4 is formed by using carbon nanotubes 11, and in Example 20, the reinforcing layer 4 is formed by using cellulose nanofibers 12. When compared with Examples 1 to 3 (where the reinforcing material 10 is not included in the first polymer thin film 2 and the second polymer thin film 3), in Examples 18 and 19, the film thickness of the second polymer thin film 3 is 38 nm, while in Examples 1 to 3, the film thickness of the second polymer thin film 3 is 113 nm to 74 nm. That is, in Examples 18 and 19, by using the first polymer thin film 2 including the reinforcing layer 4 to support the second polymer thin film 3, the overall mechanical strength is improved, and the second polymer thin film 3 (as a result, the polymer composite film 1) can be formed thinner.

[0198] It should be noted that in the gas separation body 6 of the second to fourth embodiments, similar to the description in the first embodiment (Examples 7 to 10), when the gas permeates in the order from the second polymer thin film 3 to the first polymer thin film 2, the gas selectivity is more excellent. On the other hand, when the gas permeates in the order from the first polymer thin film 2 to the second polymer thin film 3, the gas permeability is more excellent.

[0199] As described above, according to the first to fourth embodiments, by combining two polymer thin films with different properties, or further combining the reinforcing material 10 (composite), or combining the structure of the reinforcing layer 4, the polymer composite film 1 with good balance of gas permeability and gas selectivity can be realized.

[0200] (Fifth Embodiment)

[0201] Figure 3 It is an explanatory diagram showing the structure of the gas separation device 110 including the gas separation body 6 according to the present invention. As Figure 3 shown, the gas separation device 110 is composed of a blower 114, a pre-filter 111, a dust collection filter 112, and a gas separation body 6, and an air flow path 119 is formed from the suction port 115 to the first blowout port 116a (and the second blowout port 116b).

[0202] The blower 114 is composed of, for example, an air compression mechanism. By driving the blower 114, the air inhaled from the suction port 115 passes through the flow path 119 in the order of the pre-filter 111, the dust collection filter 112, and the gas separation body 6 as the air flow AF.

[0203] The air that has passed through the gas separation body 6 is discharged as an air flow AFO from the first air outlet 116a provided downstream of the gas separation body 6. On the other hand, the air that has not passed through the gas separation body 6 is discharged as an air flow AFN from the second air outlet 116b provided upstream of the gas separation body 6.

[0204] Here, in order to perform gas separation, a pressure difference is required between the upstream space (the first space S1) and the downstream space (here, the external space S0) sandwiching the gas separation body 6. In the gas separation device 110 of the fifth embodiment, in order to ensure this pressure difference, an air valve 117 is connected to the second air outlet 116b to restrict the outflow amount of the air flow AFN, and the blower 114 is used to send compressed air and adjust it so that the first space S1 becomes a positive pressure with respect to the external space S0 (1 atmospheric pressure). It should be noted that for the polymer composite film with a high permeability in the polymer composite film 1 mounted on the gas separation body 6, the air pressure in the first space S1 can also be set to a moderate value such as about 2 atmospheric pressures (the pressure difference between the first space S1 and the external space S0 = 1 atmospheric pressure). In addition, since the gas selectivity of the polymer composite film 1 according to the present invention is very high, even if the pressure difference before and after the gas separation body 6 is small, the gas can be efficiently separated.

[0205] In addition, the polymer composite film 1 according to the present invention (especially the second to fourth embodiments) is configured to include a reinforcing material 10 in the polymer composite film 1, and thus has extremely high mechanical strength. Therefore, the pressure difference between the first space S1 and the external space S0 can also be set as high as about 10 atmospheric pressures.

[0206] The pre-filter 111 is a filter through which the air sucked by the blower 114 first passes, and captures relatively large dust contained in the air flow AF. The dust collection filter 112 is a filter through which the air that has passed through the pre-filter 111 then passes, and for example, a HEPA (High Efficiency Particulate Air) filter can be preferably used.

[0207] The gas separation body 6 internally includes the polymer composite film 1 described in the first to fourth embodiments. The gas supply unit (here, the blower 114) supplies gas so that the gas passes through the second polymer film 3 and the first polymer film 2 in this order (or in the order of the first polymer film 2 and the second polymer film 3). Thereby, the user of the gas separation device 110 can select the configuration of the gas separation body 6 with more excellent gas selectivity or gas permeability, and thus obtain oxygen-enriched air, carbon dioxide-enriched air, and nitrogen-enriched air.

[0208] As shown in [Table 1] to [Table 5], for the polymer composite film 1 involved in the present invention, the permeabilities of CO2 and O2 are higher than that of N2. Therefore, in the air flow AFO passing through the gas separator 6 and discharged from the first air outlet 116a, the concentrations of O2 and CO2 are higher than those in normal air (i.e., oxygen-enriched air, carbon dioxide-enriched air). On the other hand, in the air flow AFN discharged from the second air outlet 116b without passing through the gas separator 6, the concentration of nitrogen is higher than that in normal air (i.e., nitrogen-enriched air).

[0209] Regarding the air flow AFO, CO2 in the air is concentrated. Therefore, the gas separation device 110 can function as a CO2 recovery device for capturing carbon dioxide-enriched air. Here, in the gas separator 6, multiple segments of the polymer composite film 1 can also be arranged in series to form a multi-stage structure. Here, when the O2 / N2 selectivity ratio of a single polymer composite film 1 is 2.2, the O2 / N2 selectivity ratio of the entire gas separator 6 when the number of segments of the polymer composite film 1 is set to P becomes 2.2^P. By increasing the number of segments, the oxygen concentration can be further increased. Of course, when P is increased, the total gas permeability in the gas separator 6 decreases. In this case, it can be addressed by increasing the capacity of the air compressor constituting the blower 114.

[0210] It should be noted that the inventors of the present application reported the following content in, for example, "Polymer Journal (2021) 53:111-119 A new strategy for membrane-based direct air capture": By forming the polymer film in the gas separator 6 into a multi-stage structure, CO2 (0.04%) in the air can be concentrated to more than 40%. The gas separation device 110 obtained by multi-segmenting the polymer film can be introduced in various sizes and scales and can become a new CO2 recovery technology (DAC). The polymer composite film 1 involved in the present invention has high permeability, extremely high gas selectivity, and extremely high mechanical strength, and is therefore extremely useful for the concentration and recovery of CO2 and O2 in the air.

[0211] In addition, the air flow AFO can be applied in fish farms and other places that use oxygen-enriched air, oxygen combustion power plants, oxygen combustion boilers, etc. It should be noted that although the CO2 concentration in the air flow AFO is also increased, by, for example, passing it through activated carbon, water, etc., it is relatively easy to remove CO2 from the air flow AFO, and oxygen-enriched air with an increased CO2 concentration can be obtained in large quantities.

[0212] On the other hand, the air stream AFN can be used for, for example, fire extinguishing purposes. The three essential elements for combustion are a combustible substance, an oxygen supplier, and an ignition source. In air, the combustion of a combustible substance must continue above the limiting oxygen concentration. If the nitrogen concentration is higher than 85% (oxygen concentration lower than 14%), combustion can be suppressed for most combustible substances. In addition, the air stream AFN (nitrogen-rich air) can be applied to a corrosion and spoilage inhibition system (preservation system) for preventing the deterioration of foods, artworks, etc. caused by oxidation.

[0213] In addition, in a thermal power plant where fossil fuels such as coal, oil, and LNG gas are burned in a boiler and the force of the steam formed by the heat is used to rotate a turbine for power generation, etc., the air stream AFO (oxygen-rich air) is usually applied to improve the combustion efficiency. On the other hand, in a situation where the boiler or the like becomes abnormally hot due to a failure or the like, a fire can be prevented by supplying the air stream AFN (nitrogen-rich air).

[0214] It should be noted that as the air stream AFO, not only the above-mentioned air can be used, but also, for example, the exhaust gas of an internal combustion engine and other mixed gases can be used. In this case, carbon dioxide concentration, oxygen enrichment, and nitrogen enrichment can also be performed on the exhaust gas and other mixed gases.

[0215] In addition, among polysiloxanes, it is known that the proportion of the free volume of PDMS in particular is large. In fact, the cavity radius inside the polymer estimated by positron annihilation method is considered to be 1 nm or less (see Yampolskii, Pinnau, Freeman, 2006 John Wiley & Sons, Ltd “Materials Science of Membranes for Gas and Vapor Separation” p. 125). Therefore, so-called nanoparticles larger than this size are difficult to pass through the PDMS membrane, and the air stream AFO becomes clean air that does not contain nanoparticles either.

[0216] As described above, the gas separation device 110 equipped with the polymer composite film 1 according to the present invention not only has high permeability, selectivity, and mechanical strength, but also has the function of removing nanoparticles that cannot be removed by the above-mentioned dust collection filter 112. By applying the polymer composite film 1, a clean room system (air purifier) with extremely high cleanliness can be realized.

[0217] The polymer composite film 1 and the gas separation device 110 according to the present invention have been described based on specific embodiments or examples, but these are merely examples, and the present invention is not limited to these embodiments and examples.

[0218] Industrial Applicability

[0219] The polymer composite film 1 according to the present invention has high gas permeability, gas selectivity, and mechanical strength. In addition, the gas separation device 110 equipped with the polymer composite film 1 has high gas separation characteristics. Therefore, it can be preferably applied to, for example, CCS (Carbon Dioxide Capture and Storage) for separating and recovering CO2, which is a greenhouse gas generated by the combustion of fossil fuels, from sources such as power plants and factories, and DAC for directly recovering CO2 from the air.

[0220] Explanation of Reference Numerals

[0221] 1 Polymer composite film

[0222] 2 First polymer film

[0223] 3 Second polymer film

[0224] 4 Reinforcing layer

[0225] 5 Support

[0226] 6 Gas separation body

[0227] 10 Reinforcing material

[0228] 11 Carbon nanotube

[0229] 12 Cellulose nanofiber

[0230] 110 Gas separation device

[0231] 114 Blower

Claims

1. A polymer composite film, characterized in that, It is composed of a first polymer film having selective permeability to a specified gas and a second polymer film disposed overlapping the first polymer film and containing at least an ethylene oxide chain.

2. The polymer composite film according to claim 1, characterized in that, Carbon nanotubes or cellulose nanofibers are dispersed in the second polymer film.

3. The polymer composite film according to claim 1, wherein Carbon nanotubes or cellulose nanofibers are dispersed in the first polymer film.

4. The polymer composite film according to claim 1, wherein, A reinforcing layer made of carbon nanotubes or cellulose nanofibers is provided between the first polymer film and the second polymer film.

5. The polymer composite film according to any one of claims 1 to 4, characterized in that The second polymer film is composed of a crosslinked polymer containing the ethylene oxide chain.

6. The polymer composite film according to claim 5, wherein The crosslinked polymer containing the ethylene oxide chain is made into a partially crosslinked state.

7. The polymer composite film according to any one of claims 1 to 4, characterized in that The total film thickness of the first polymer film and the second polymer film is made 20 nm to 1000 nm.

8. The polymer composite film according to any one of claims 1 to 4, characterized in that Selectively permeate carbon dioxide and oxygen from air, exhaust gas, or other mixed gases.

9. The polymer composite film according to any one of claims 1 to 4, characterized in that The first polymer film is mainly composed of polysiloxane.

10. A gas separator, comprising: The polymer composite film according to any one of claims 1 to 4, and A support for supporting the polymer composite film.

11. Gas separation device, characterized in that, Comprising: The gas separator according to claim 10, and A gas supply unit for supplying gas to the gas separator, The gas supply unit supplies gas in such a manner that the gas sequentially permeates the second polymer film and the first polymer film.

12. Gas separation device, characterized in that, Comprising: The gas separator according to claim 9, and A gas supply unit for supplying gas to the gas separator, The gas supply unit supplies gas in such a manner that the gas sequentially permeates the first polymer film and the second polymer film.

13. A method for manufacturing a polymer composite film, characterized in that, Including: A first step of preparing a polymer solution containing an ethylene oxide chain and a polymer material solution containing a polymer material that has selective permeability to a specified gas when made into a film; A second step of coating the polymer solution containing an ethylene oxide chain on a substrate having a sacrificial layer so as to cover the sacrificial layer, thereby forming a second polymer film; A third step of crosslinking the second polymer film; A fourth step of coating the polymer material solution on the crosslinked second polymer film so as to cover it and curing it, thereby forming a first polymer film; and A fifth step of dissolving the sacrificial layer and peeling off the polymer composite film composed of the first polymer film and the second polymer film from the substrate.

14. A method for manufacturing a polymer composite film, characterized in that, Including: A first step of preparing a solution containing a polymer containing an ethylene oxide chain and a reinforcing material, i.e., a solution containing a polymer containing an ethylene oxide chain - reinforcing material, and a polymer material solution containing a polymer material that has selective permeability to a specified gas when made into a film; A second step of coating the solution containing a polymer containing an ethylene oxide chain - reinforcing material on a substrate having a sacrificial layer so as to cover the sacrificial layer, thereby forming a second polymer film; A third step of crosslinking the second polymer film; A fourth step of coating the polymer material solution on the crosslinked second polymer film so as to cover it and curing it, thereby forming a first polymer film; and In the fifth step, the sacrificial layer is dissolved, and the polymer composite film composed of the first polymer film and the second polymer film is peeled off from the substrate.

15. A method for manufacturing a polymer composite film, characterized in that, Comprising: In the first step, a polymer solution containing an oxyethylene chain is prepared, and a solution containing a polymer material - reinforcing material, which includes a polymer material having a selective permeability to a specified gas when formed into a film and a reinforcing material, is prepared; In the second step, the polymer solution containing an oxyethylene chain is coated on the substrate having a sacrificial layer formed thereon in such a manner as to cover the sacrificial layer, thereby forming a second polymer film; In the third step, the second polymer film is crosslinked; In the fourth step, the solution containing a polymer material - reinforcing material is coated and cured in such a manner as to cover the crosslinked second polymer film, thereby forming a first polymer film; and In the fifth step, the sacrificial layer is dissolved, and the polymer composite film composed of the first polymer film and the second polymer film is peeled off from the substrate.

16. A method for manufacturing a polymer composite film, characterized in that, Comprising: In the first step, a reinforcing material dispersion containing a reinforcing material, a polymer solution containing an oxyethylene chain, and a polymer material solution containing a polymer material having a selective permeability to a specified gas when formed into a film are prepared; In the second step, the polymer solution containing an oxyethylene chain is coated on the substrate having a sacrificial layer formed thereon in such a manner as to cover the sacrificial layer, thereby forming a second polymer film; In the third step, the second polymer film is crosslinked; In the fourth step, the reinforcing material dispersion is coated in such a manner as to cover the crosslinked second polymer film, thereby forming a reinforcing layer; In the fifth step, the polymer material solution is coated and cured in such a manner as to cover the reinforcing layer, thereby forming a first polymer film; and In the sixth step, the sacrificial layer is dissolved, and the polymer composite film composed of the first polymer film and the second polymer film is peeled off from the substrate.

17. The manufacturing method of the polymer composite film according to any one of claims 14 to 16, characterized in that, The reinforcing material is carbon nanotubes or cellulose nanofibers.

18. The manufacturing method of the polymer composite film according to any one of claims 13 to 16, characterized in that, In the third step, the second polymer film is crosslinked in a nitrogen atmosphere.

19. The manufacturing method of the polymer composite film according to any one of claims 13 to 16, characterized in that In the third step, the progress of crosslinking is stopped while functional groups contributing to the crosslinking reaction remain in the second polymer film.

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