JP2019051516A - Composite membrane - Google Patents

Composite membrane Download PDF

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JP2019051516A
JP2019051516A JP2018222770A JP2018222770A JP2019051516A JP 2019051516 A JP2019051516 A JP 2019051516A JP 2018222770 A JP2018222770 A JP 2018222770A JP 2018222770 A JP2018222770 A JP 2018222770A JP 2019051516 A JP2019051516 A JP 2019051516A
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moisture
membrane
porous membrane
permeable resin
resin
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JP6667603B2 (en
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渓太 平井
Keita Hirai
渓太 平井
浩良 藤本
Hiroyoshi Fujimoto
浩良 藤本
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Japan Gore KK
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Abstract

To provide a composite membrane excellent in both durability and moisture permeability.SOLUTION: A composite membrane is formed of a porous film for reinforcement; a hydrophobic porous membrane; a layer of a moisture-permeable resin; and a voluntarily additive permeable reinforcement material, where the layer of the moisture-permeable resin is formed on the upper surface of the porous membrane for reinforcement and is exposed from the upper surface of the porous membrane for reinforcement so that the moisture-permeable resin can be brought into direct contact with raw water, the moisture-permeable resin is impregnated in the porous membrane for reinforcement and the layer of the moisture-permeable resin is exposed from the lower surface of the porous membrane for reinforcement, the lower surface of the porous membrane for reinforcement is stuck to the hydrophobic porous membrane through the layer of the moisture-permeable resin, and the permeable reinforcement material is laminated on the lower surface of the hydrophobic porous membrane opposite to the upper surface of the hydrophobic porous membrane to which the porous membrane for reinforcement is stuck.SELECTED DRAWING: None

Description

本発明は、新規な複合膜に関し、詳しくは、疎水性多孔質膜の片面に透湿性樹脂層を積層してなる複合膜であって、該透湿性樹脂層は補強用多孔質膜に含まれることを特徴とする、複合膜であり、特に水蒸気分離特性に優れた性能を有する複合膜に関する。   The present invention relates to a novel composite membrane, and more specifically, a composite membrane obtained by laminating a moisture permeable resin layer on one surface of a hydrophobic porous membrane, the moisture permeable resin layer being included in the reinforcing porous membrane. The present invention relates to a composite membrane having a performance excellent in water vapor separation characteristics.

近年深刻化してきている干ばつ、砂漠化、水環境の悪化などに伴い、これまで以上に水処理技術が重要になってきており、分離膜利用技術が幅広く利用されて来ている。海水淡水化については、逆浸透法の技術進歩による信頼性の向上やコストダウンが進み、逆浸透膜を用いた淡水化プロセスが採用され、水資源が極端に少ない中東地域やカリブ諸島や地中海エリアなどで多数の逆浸透法海水淡水化プラントが建設、稼働するに至っている。   With drought, desertification, and deterioration of the water environment that have become increasingly serious in recent years, water treatment technology has become more important than ever, and separation membrane utilization technology has been widely used. As for seawater desalination, improvements in reliability and cost reduction have progressed due to technological advances in reverse osmosis, and a desalination process using reverse osmosis membranes has been adopted, resulting in extremely low water resources in the Middle East, the Caribbean and Mediterranean areas. A number of reverse osmosis seawater desalination plants have been constructed and put into operation.

一方、海水から淡水を得る技術としては、蒸発法と同じく、熱を駆動力とし、膜を介して淡水を得る、膜蒸留法というプロセスが提案、検討されている。   On the other hand, as a technique for obtaining fresh water from seawater, a process called membrane distillation, in which heat is used as a driving force and fresh water is obtained through a membrane, has been proposed and studied, as in the evaporation method.

膜蒸留法は、一般に多孔質疎水性膜の性質を利用した膜分離法である(特許文献1)。図1を参照しつつ、膜蒸留法の仕組みを説明する。この多孔質疎水性膜の一方の面に高温一次水(海水などの溶液)を、この膜のもう一方の面に低温の淡水(純水)を接触させると、膜が疎水性であるために、一次水が膜面で阻止され、一次水は(液体として)膜を透過することができない。一方、気体は多孔質である膜内を透過することができるため、高温一次水から蒸発してくる水蒸気を膜内で透過させ、透過した水蒸気を低温部で凝縮させることによって、一次水(溶液)から水だけを分離することが可能である。すなわち、膜蒸留法は、膜を介して一方に高温供給水を流し、膜のもう一方に冷却面を設けることにより、生じる温度差に基づく蒸気圧差を蒸気透過のドライビングフォースとする。膜蒸留法は、高温供給水が揮発成分を含む場合、その揮発成分が透過しやすいという課題はあるが、不揮発性の溶質分離性能は極めて高く、例えば、不揮発性の塩分が溶質の主体である海水からは、高純度の淡水を得ることができる。   The membrane distillation method is generally a membrane separation method utilizing the properties of a porous hydrophobic membrane (Patent Document 1). The mechanism of the membrane distillation method will be described with reference to FIG. When one side of this porous hydrophobic membrane is contacted with high temperature primary water (solution such as seawater) and the other side of this membrane is contacted with low temperature fresh water (pure water), the membrane is hydrophobic. Primary water is blocked at the membrane surface and the primary water cannot penetrate the membrane (as a liquid). On the other hand, since the gas can permeate through the porous membrane, the water vapor evaporating from the high temperature primary water is allowed to permeate through the membrane, and the permeated water vapor is condensed at the low temperature portion, so that the primary water (solution It is possible to separate only water from That is, in the membrane distillation method, high temperature feed water is allowed to flow through one side of the membrane and a cooling surface is provided on the other side of the membrane, so that the vapor pressure difference based on the generated temperature difference becomes the driving force for vapor transmission. In the membrane distillation method, when the high-temperature feed water contains a volatile component, there is a problem that the volatile component easily permeates, but the non-volatile solute separation performance is extremely high, for example, the non-volatile salt content is mainly the solute. High purity fresh water can be obtained from seawater.

膜蒸留法は、基本原理としては蒸発法と同じであるが、蒸発法に比べて、以下のように様々な利点が挙げられる。
・膜の形状に自由度が大きく、装置の形の制限が小さい。
・膜の充填率を高くすることにより、装置体積の小型化が可能。
・蒸気圧差に基づくため、沸点以下の比較的低温での利用の可能性があり、排熱を利用したり、温度の異なる水源を利用したりすることができれば、エネルギー的なメリットが大きい。
・溶液と透過水が直接接触しないので、逆浸透法のような浸透圧を考慮する必要が少なく、動力費は非常に低い。
The membrane distillation method is the same as the evaporation method in terms of the basic principle, but has various advantages over the evaporation method as follows.
-The degree of freedom in the shape of the membrane is large, and the restrictions on the shape of the device are small.
・ By increasing the membrane filling rate, the device volume can be reduced.
・ Because it is based on the difference in vapor pressure, it can be used at relatively low temperatures below the boiling point. If exhaust heat can be used or water sources with different temperatures can be used, there are significant energy benefits.
-Since the solution and the permeated water do not come into direct contact, there is little need to consider osmotic pressure as in the reverse osmosis method, and the power cost is very low.

特開昭61−57205号公報JP 61-57205 A 特開昭59−203602号公報JP 59-203602 A 特開2010−5515号公報JP 2010-5515 A

一方、膜蒸留法における最も大きな課題は、膜表面が汚れると、水蒸気の蒸発面が汚れによって閉塞するばかりでなく、膜の疎水性が失われ、最後には供給水が多孔質疎水性膜に侵入し、冷却側(透過側)に漏れだしてくる危険性があるという本質的な問題を抱えている。   On the other hand, the biggest problem in the membrane distillation method is that when the membrane surface becomes dirty, not only does the evaporation surface of the water vapor become clogged but also the hydrophobicity of the membrane is lost, and finally the feed water becomes a porous hydrophobic membrane. There is an essential problem that there is a risk of intrusion and leakage to the cooling side (transmission side).

この問題を解決するために、多孔質疎水性膜の表面に親水性樹脂膜を載せて複合膜化(特許文献2)する方法が提案されている。   In order to solve this problem, a method of forming a composite film by placing a hydrophilic resin film on the surface of a porous hydrophobic film has been proposed (Patent Document 2).

しかし、この方法では、親水性樹脂膜が一次水と接触する際に膨潤するため、強度が低下し、一次水の流速によって摩耗したり、膜に亀裂が入る、ピンホールがあくなどの問題がある。   However, in this method, the hydrophilic resin film swells when it comes into contact with the primary water, so that the strength is reduced, the film is worn out by the flow rate of the primary water, the film is cracked, and pinholes are opened. is there.

この親水性樹脂膜の使用時の強度低下の問題を解決するために、親水性樹脂膜の表面にも疎水性多孔質膜を配置し、疎水性多孔質膜によって親水性樹脂膜を挟み込む方法(特許文献3)が提案されている。   In order to solve the problem of strength reduction when using the hydrophilic resin film, a method in which a hydrophobic porous film is arranged on the surface of the hydrophilic resin film and the hydrophilic resin film is sandwiched between the hydrophobic porous films ( Patent Document 3) has been proposed.

この方法では、親水性樹脂層は直接一次水には接触せず、また、親水性樹脂層の表面が疎水性多孔質膜により補強される効果もあり、複合膜の耐久性は向上できるが、原水に親水性樹脂層が直接接触していないため、水蒸気の透過速度が十分でない場合があるという問題があった。   In this method, the hydrophilic resin layer is not in direct contact with primary water, and the surface of the hydrophilic resin layer is also reinforced by the hydrophobic porous membrane, so that the durability of the composite membrane can be improved. Since the hydrophilic resin layer is not in direct contact with the raw water, there is a problem that the water vapor transmission rate may not be sufficient.

そこで本発明は、前述したような問題点を解決するためになされたものであり、耐久性および透湿性がともに優れた、複合膜を提供することを目的とする。   Accordingly, the present invention has been made to solve the above-described problems, and an object of the present invention is to provide a composite film excellent in both durability and moisture permeability.

本発明により以下が提供される。   The present invention provides the following.

(1)疎水性多孔質膜の片面に透湿性樹脂の層を積層してなる複合膜であって、該透湿性樹脂の層は補強用多孔質膜に含まれることを特徴とする、複合膜。   (1) A composite membrane obtained by laminating a layer of moisture permeable resin on one surface of a hydrophobic porous membrane, wherein the layer of moisture permeable resin is included in the reinforcing porous membrane .

(2)該透湿性樹脂の層が該補強用多孔質膜の上表面から露出していることを特徴とする、(1)に記載の複合膜。   (2) The composite membrane according to (1), wherein the moisture-permeable resin layer is exposed from the upper surface of the reinforcing porous membrane.

(3)該透湿性樹脂の層が該補強用多孔質膜の下面から露出していることを特徴とする、(1)または(2)に記載の複合膜。   (3) The composite membrane according to (1) or (2), wherein the moisture-permeable resin layer is exposed from the lower surface of the reinforcing porous membrane.

(4)該補強用多孔質膜の下面から露出した該透湿性樹脂の層の少なくとも一部が、該疎水性多孔質膜内に入り込んでいるが、該疎水性多孔質膜の下面から露出していないことを特徴とする、(3)に記載の複合膜。   (4) At least a part of the layer of the moisture-permeable resin exposed from the lower surface of the reinforcing porous membrane has entered the hydrophobic porous membrane, but is exposed from the lower surface of the hydrophobic porous membrane. The composite membrane according to (3), wherein the composite membrane is not.

(5)該透湿性樹脂の層の厚みが25μm以下であることを特徴とする、(1)〜(4)のいずれか1つに記載の複合膜。   (5) The composite membrane according to any one of (1) to (4), wherein the thickness of the moisture-permeable resin layer is 25 μm or less.

(6)該透湿性樹脂の層の厚みが10μm以下であることを特徴とする、(1)〜(5)のいずれか1つに記載の複合膜。   (6) The composite membrane according to any one of (1) to (5), wherein the thickness of the moisture-permeable resin layer is 10 μm or less.

(7)該透湿性樹脂の層の厚みが5μm以下であることを特徴とする、(1)〜(6)のいずれか1つに記載の複合膜。   (7) The composite membrane according to any one of (1) to (6), wherein the thickness of the moisture-permeable resin layer is 5 μm or less.

(8)該透湿性樹脂が、以下の耐水性試験前後の樹脂の体積変化から求まる膨潤度が2倍以上且つ20倍以下の膨潤性を示し、
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
耐水性試験:温度120℃、水蒸気圧0.23MPaの環境下に樹脂を24時間放置し、次いで温度25℃の水に15分間浸漬すること、
を特徴とする、(1)〜(7)のいずれか1つに記載の複合膜。
(8) The moisture-permeable resin exhibits a swellability that is 2 to 20 times the swelling degree obtained from the volume change of the resin before and after the following water resistance test,
Swelling degree = volume of resin after water resistance test / volume of resin before water resistance test Water resistance test: The resin is left in an environment at a temperature of 120 ° C. and a water vapor pressure of 0.23 MPa for 24 hours, and then water at a temperature of 25 ° C. Soak in for 15 minutes,
The composite membrane according to any one of (1) to (7), wherein

(9)該透湿性樹脂がポリスチレンスルホン酸、ポリビニルアルコール、ビニルアルコール共重合体、フッ素系イオン交換樹脂、繰り返し単位にプロトン性親水性基を有する樹脂、繰り返し単位に非プロトン性親水性基を有する樹脂のいずれかであることを特徴とする、(1)〜(8)のいずれか1つに記載の複合膜。   (9) The moisture-permeable resin has polystyrene sulfonic acid, polyvinyl alcohol, vinyl alcohol copolymer, fluorine ion exchange resin, a resin having a protic hydrophilic group in a repeating unit, and an aprotic hydrophilic group in a repeating unit. The composite film according to any one of (1) to (8), wherein the composite film is any one of resins.

(10)該透湿性樹脂がフッ素系イオン交換樹脂、ポリビニルアルコール、ポリウレタンのいずれかであることを特徴とする、(1)〜(9)のいずれか1つに記載の複合膜。   (10) The composite membrane according to any one of (1) to (9), wherein the moisture-permeable resin is any one of a fluorine-based ion exchange resin, polyvinyl alcohol, and polyurethane.

(11)該補強用多孔質膜が、延伸PTFE膜であることを特徴とする、(1)〜(10)のいずれか1つに記載の複合膜。   (11) The composite membrane according to any one of (1) to (10), wherein the reinforcing porous membrane is an expanded PTFE membrane.

(12)通気性補強材を、該疎水性多孔質膜の該透湿性樹脂の層が積層されている面と逆の面に積層していることを特徴とする、(1)〜(11)のいずれか1つに記載の複合膜。   (12) The breathable reinforcing material is laminated on a surface opposite to the surface on which the moisture-permeable resin layer of the hydrophobic porous membrane is laminated, (1) to (11), A composite membrane according to any one of the above.

(13)該通気性補強材が織布、不織布、ネットのいずれかであることを特徴とする、(12)に記載の複合膜。   (13) The composite membrane according to (12), wherein the breathable reinforcing material is any one of a woven fabric, a nonwoven fabric, and a net.

(14)水蒸気分離膜として使用することを特徴とする、(1)〜(13)のいずれか1つに記載の複合膜。   (14) The composite membrane according to any one of (1) to (13), which is used as a water vapor separation membrane.

膜蒸留の仕組みを説明する概略図である。It is the schematic explaining the mechanism of membrane distillation. 本発明の複合膜の一例を示す概略断面図である。It is a schematic sectional drawing which shows an example of the composite film of this invention. (a)は補強用多孔質膜で補強された透湿性樹脂の層の概略断面図であり、(b)はさらに疎水性多孔質膜を備えた複合膜の概略断面図である。(A) is a schematic sectional drawing of the layer of the moisture-permeable resin reinforced with the porous membrane for reinforcement, (b) is a schematic sectional drawing of the composite membrane further provided with the hydrophobic porous membrane. 水分量調整モジュールの一例を示す概略斜視断面図である。It is a schematic perspective sectional view which shows an example of a moisture content adjustment module. 耐久試験装置の概略を示す図である。It is a figure which shows the outline of a durability test apparatus.

(i)複合膜
以下、図を参照しつつ、本発明の複合膜について詳細に説明する。
(I) Composite Film Hereinafter, the composite film of the present invention will be described in detail with reference to the drawings.

図2は、本発明の複合膜の一例を示す概略断面図である。図2に示すように、本発明の複合膜では、疎水性多孔質膜の片面に透湿性樹脂の層(機能層)が積層され、さらに、透湿性樹脂の層が補強用多孔質膜に含まれている。   FIG. 2 is a schematic cross-sectional view showing an example of the composite membrane of the present invention. As shown in FIG. 2, in the composite membrane of the present invention, a layer of moisture permeable resin (functional layer) is laminated on one side of the hydrophobic porous membrane, and the layer of moisture permeable resin is further included in the reinforcing porous membrane. It is.

本発明の複合膜は、透湿性樹脂の層が補強用多孔質膜で補強されていることにより、外部材と接触したときの表面耐久性に優れている。したがって、磨耗したり、亀裂が入ったり、ピンホールを生じたりすることがない。磨耗、亀裂、ピンホール等が生じると、ガスバリア性が低下し、そこから気体や液体が透過する。磨耗、亀裂、ピンホール等を防止して、ガスバリア性を確保するためには、透湿性樹脂の層の厚み全体を厚く形成しなければならず、その場合透湿性が低下してしまう。しかし、本発明の複合膜は、表面耐久性に優れているため、透湿性樹脂の層を薄くでき、したがって透湿性も高い。   The composite membrane of the present invention is excellent in surface durability when it comes into contact with the outer member, because the moisture-permeable resin layer is reinforced with the reinforcing porous membrane. Therefore, it is not worn out, cracked or pinholed. When wear, cracks, pinholes, etc. occur, the gas barrier properties decrease, and gas and liquid permeate there from. In order to prevent wear, cracks, pinholes, etc., and to secure gas barrier properties, the entire thickness of the moisture-permeable resin layer must be formed thickly, in which case the moisture permeability is reduced. However, since the composite membrane of the present invention is excellent in surface durability, the moisture-permeable resin layer can be made thin, and therefore the moisture permeability is high.

透湿性樹脂の層は、補強用多孔質膜の上表面から露出することもできる。これにより、複合膜を気体や液体に含まれる水を選択的に透過させるための分離膜(水分量調整モジュール用分離膜)、例えば膜蒸留用の膜として用いたときに、透湿性樹脂が一次水に直接接触することができ、優れた透湿性能が実現できる。特許文献3は、疎水性多孔質膜によって樹脂膜を挟み込む方法を提案しており、原水に直接接触することができない。この点で、本発明の複合膜の透湿性能は、特許文献3のものより、一層向上する。   The layer of moisture-permeable resin can also be exposed from the upper surface of the reinforcing porous membrane. As a result, when the composite membrane is used as a separation membrane for selectively allowing water contained in gas or liquid (separation membrane for water content adjustment module), for example, a membrane for membrane distillation, the moisture-permeable resin is primary. It can be in direct contact with water and can achieve excellent moisture permeability. Patent Document 3 proposes a method of sandwiching a resin film with a hydrophobic porous film and cannot directly contact raw water. In this respect, the moisture permeability of the composite membrane of the present invention is further improved than that of Patent Document 3.

透湿性樹脂の層は、該補強用多孔質膜の下面から露出することもできる。この透湿性樹脂の層の露出した部分は、補強用多孔質膜および疎水性多孔質膜と接して存在する。透湿性樹脂が、不織布等の繊維径の比較的大きな材料と接している場合には、不織布の繊維との境界部分に、透湿樹脂液の液溜まりが形成され、透湿樹脂の厚みが不均一となることがある。この厚みが不均一である場合、厚みの比較的薄い部分でピンホールが生じやすいという懸念がある。その場合、ピンホールを防ぐために、透湿性樹脂の層の厚みを全体的に厚くするなどの対応がされてきた。本発明では、透湿性樹脂が多孔質膜と接しており、多孔質膜の表面の凹凸(孔径)は、不織布等の繊維径に比べて遙かに小さいので、透湿樹脂液の液溜まりを防止できる。そのため透湿樹脂が均一な厚みで存在でき、ピンホールの発生を防ぐことができる。ひいては、透湿性樹脂の層を厚くする必要がないので、高い透湿性を実現できる。   The layer of the moisture permeable resin can be exposed from the lower surface of the reinforcing porous membrane. The exposed portion of the moisture permeable resin layer exists in contact with the reinforcing porous membrane and the hydrophobic porous membrane. When the moisture-permeable resin is in contact with a material having a relatively large fiber diameter, such as a nonwoven fabric, a liquid reservoir of moisture-permeable resin liquid is formed at the boundary between the nonwoven fabric and the moisture-permeable resin. May be uniform. If this thickness is non-uniform, there is a concern that pinholes are likely to occur at relatively thin portions. In that case, in order to prevent pinholes, measures such as increasing the thickness of the moisture-permeable resin layer as a whole have been taken. In the present invention, the moisture-permeable resin is in contact with the porous membrane, and the unevenness (pore diameter) on the surface of the porous membrane is much smaller than the fiber diameter of the nonwoven fabric or the like. Can be prevented. Therefore, the moisture-permeable resin can exist with a uniform thickness, and the occurrence of pinholes can be prevented. As a result, it is not necessary to increase the thickness of the moisture-permeable resin layer, so that high moisture permeability can be realized.

透湿性樹脂の層は、疎水性多孔質膜に入り込むことなく、その表面上に形成されていてもよい。また、透湿性樹脂の層の少なくとも一部が疎水性多孔質膜の内部に入り込んでいてもよい。透湿性樹脂の層が疎水性多孔質膜に入り込むと、疎水性多孔質膜内の小孔へのアンカー効果を発揮し、耐久性が向上する。ただし、疎水性多孔質膜の内部に入り込んだ透湿性樹脂の層は、疎水性多孔質膜の下面から露出はしない。すなわち、本発明の複合膜には、全面にわたって疎水性多孔質膜のみで構成される層状部分が存在し、この部分により液体の透過が阻止される。   The layer of moisture-permeable resin may be formed on the surface without entering the hydrophobic porous membrane. Further, at least a part of the moisture-permeable resin layer may enter the inside of the hydrophobic porous membrane. When the moisture-permeable resin layer enters the hydrophobic porous membrane, the anchor effect to the small holes in the hydrophobic porous membrane is exhibited and the durability is improved. However, the moisture-permeable resin layer that has entered the inside of the hydrophobic porous membrane is not exposed from the lower surface of the hydrophobic porous membrane. That is, the composite membrane of the present invention has a layered portion composed only of the hydrophobic porous membrane over the entire surface, and this portion prevents liquid from permeating.

複合膜は、例えば、予め透湿性樹脂を含む液を補強用多孔質膜に塗布または含浸し、塗布または含浸した液から溶剤を洗浄、乾燥等により除去した後に、疎水性多孔質膜と熱圧着する方法などによって製造できる。   For example, the composite membrane is preliminarily coated or impregnated with a liquid containing moisture-permeable resin on the reinforcing porous membrane, and the solvent is removed from the applied or impregnated solution by washing, drying, etc., and then thermocompression bonded with the hydrophobic porous membrane. Can be manufactured by a method of

複合膜は、図2に示すように、通気性補強材を、該疎水性多孔質膜の該透湿性樹脂の層が積層されている面と逆の面に積層していてもよい。また、通気性補強材は、補強用多孔質膜の疎水性多孔質膜が積層されている面と逆の面に積層してもよい。この場合、補強用多孔質膜の上面から露出した親水性樹脂の層を介して、通気性補強材が積層されてもよい。通気性補強材は、例えば、熱融着などによって疎水性多孔質膜、補強用多孔質膜または親水性樹脂の層のいずれか、またはそれらの組み合わせに接着して、積層することができる。通気性補強材を積層することによって、複合膜の強度を高めることができる。   As shown in FIG. 2, the composite membrane may have a breathable reinforcing material laminated on a surface opposite to the surface of the hydrophobic porous membrane on which the moisture-permeable resin layer is laminated. Further, the breathable reinforcing material may be laminated on a surface opposite to the surface on which the hydrophobic porous membrane of the reinforcing porous membrane is laminated. In this case, a breathable reinforcing material may be laminated via a hydrophilic resin layer exposed from the upper surface of the reinforcing porous membrane. The breathable reinforcing material can be laminated by adhering to one of a hydrophobic porous membrane, a reinforcing porous membrane, a hydrophilic resin layer, or a combination thereof by, for example, heat sealing. By laminating a breathable reinforcing material, the strength of the composite membrane can be increased.

以下、複合膜を構成する各膜や層についてより詳細に説明する。   Hereinafter, each film and layer constituting the composite film will be described in more detail.

(ii)透湿性樹脂の層(機能層)
透湿性樹脂の層の平均厚さは、25μm以下、好ましくは10μm以下、さらに好ましくは5μm以下である。平均厚さを薄くすることで、水蒸気の透過性を向上できる。平均厚さは、ピンホールが発生しない限り薄いほど好ましいが、その下限は、例えば、1μm以上(特に2μm以上)である。
(Ii) Moisture permeable resin layer (functional layer)
The average thickness of the moisture-permeable resin layer is 25 μm or less, preferably 10 μm or less, and more preferably 5 μm or less. By reducing the average thickness, water vapor permeability can be improved. The average thickness is preferably as thin as possible so long as no pinhole is generated, but the lower limit is, for example, 1 μm or more (particularly 2 μm or more).

透湿性樹脂の層の平均厚さtは、複合膜の断面を走査型電子顕微鏡で観察し、透湿性樹脂の層の断面積Aと透湿性樹脂の層の長さ(幅)Lを求め、下記式に従って算出できる。
平均厚さt=面積A/長さL
The average thickness t of the moisture permeable resin layer is obtained by observing the cross section of the composite film with a scanning electron microscope, and obtaining the cross sectional area A of the moisture permeable resin layer and the length (width) L of the layer of the moisture permeable resin. It can be calculated according to the following formula.
Average thickness t = area A / length L

好ましい透湿樹脂は、耐水性に優れた耐水透湿性樹脂である。耐水性が高いと、高温多湿環境下で使用したときの耐久性(耐高温多湿特性)を高めることができる。また高温多湿環境下での透湿性も高まる。   A preferred moisture permeable resin is a water permeable resin having excellent water resistance. When the water resistance is high, durability (high temperature and humidity resistance) when used in a high temperature and high humidity environment can be improved. In addition, the moisture permeability in a high temperature and high humidity environment is increased.

耐水透湿性樹脂の耐水性は、以下の耐水性試験から求まる膨潤度に基づいて評価できる。   The water resistance of the water and moisture permeable resin can be evaluated based on the degree of swelling determined from the following water resistance test.

耐水透湿樹脂の膨潤度は、例えば、20倍以下、好ましくは15倍以下、さらに好ましくは10倍以下である。膨潤度の下限は特に限定されないが、2倍以上(特に5倍以上)であってもよい。   The degree of swelling of the water-resistant moisture-permeable resin is, for example, 20 times or less, preferably 15 times or less, and more preferably 10 times or less. The lower limit of the degree of swelling is not particularly limited, but may be 2 times or more (particularly 5 times or more).

耐水性試験:温度120℃、水蒸気圧0.23MPaの環境下に樹脂を24時間放置し、次いで温度25℃の水に15分間浸漬する。試験前後の樹脂の体積変化を測定し、下記式に基づいて膨潤度を算出する。
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
Water resistance test: The resin is left for 24 hours in an environment of a temperature of 120 ° C. and a water vapor pressure of 0.23 MPa, and then immersed in water at a temperature of 25 ° C. for 15 minutes. The volume change of the resin before and after the test is measured, and the degree of swelling is calculated based on the following formula.
Swelling degree = volume of resin after water resistance test / volume of resin before water resistance test

透湿性樹脂の具体例としては、ポリスチレンスルホン酸、ポリビニルアルコール、ウレタン、ビニルアルコール共重合体(エチレン−ビニルアルコール共重合体、テトラフルオロエチレン−ビニルアルコール共重合体)、フッ素系イオン交換樹脂(デュポン社製「ナフィオン(登録商標)」、旭硝子株式会社製「フレミオン(登録商標)」など)、ジビニルベンゼンスルホン酸共重合体、ジビニルベンゼンカルボン酸共重合体などのイオン交換樹脂などの繰り返し単位にプロトン性親水性基を有する樹脂(プロトン性親水性樹脂)、ポリエチレンオキサイド、ポリビニルピリジン、ポリビニルエーテル、ポリビニルピロリドン、ピロリドンなどの繰り返し単位に非プロトン性親水性基を有する樹脂(非プロトン性親水性樹脂)などが挙げられる。   Specific examples of the moisture permeable resin include polystyrene sulfonic acid, polyvinyl alcohol, urethane, vinyl alcohol copolymer (ethylene-vinyl alcohol copolymer, tetrafluoroethylene-vinyl alcohol copolymer), fluorine ion exchange resin (DuPont). "Nafion (registered trademark)" manufactured by Asahi Glass Co., Ltd., "Flemion (registered trademark)" manufactured by Asahi Glass Co., Ltd.), proton exchange units such as ion exchange resins such as divinylbenzene sulfonic acid copolymer and divinylbenzene carboxylic acid copolymer Resin having a protic hydrophilic group (protic hydrophilic resin), a resin having an aprotic hydrophilic group in a repeating unit such as polyethylene oxide, polyvinyl pyridine, polyvinyl ether, polyvinyl pyrrolidone, pyrrolidone (aprotic hydrophilic resin) Etc. .

また前記透湿性樹脂は、三次元架橋構造を形成していてもよい。三次元架橋型透湿性樹脂には、前記プロトン性親水性樹脂の架橋体、前記非プロトン性親水性樹脂の架橋体などが挙げられる。三次元架橋型透湿性樹脂は、耐水性に優れている。   The moisture-permeable resin may form a three-dimensional crosslinked structure. Examples of the three-dimensional crosslinked moisture-permeable resin include a crosslinked product of the protic hydrophilic resin and a crosslinked product of the aprotic hydrophilic resin. The three-dimensional crosslinked moisture-permeable resin is excellent in water resistance.

前記透湿性樹脂(三次元架橋型透湿性樹脂を含む)は、単独で又は2種以上を組み合わせて使用できる。好ましい透湿性樹脂は、ポリビニルアルコールの架橋体(例えば、グルタルアルデヒドとHClとの混合液による架橋体、ホルムアルデヒドによる架橋体、ブロックドイソシアネートによる架橋体など)、ポリウレタンの架橋体(例えば、両末端にヒドロキシ基をもつポリエーテルやポリエステルと、芳香族ジアミンや多価アルコールとによる架橋体など)、フッ素系イオン交換樹脂である。ポリビニルアルコールの架橋体は、耐水性に優れているだけでなく、塗布操作が容易であって、透湿樹脂層の薄膜化を容易に達成できる。ポリウレタンの架橋体は、耐水性に優れているだけでなく、耐摩耗性、耐酸化性、耐油性、耐老化性にも優れる。フッ素系イオン交換樹脂は、耐熱性・耐薬品性に優れるため、高温・高湿下や、酸・アルカリなどが存在する系などで耐久性が高く、より過酷な環境下での使用に適している。   The moisture-permeable resin (including a three-dimensional cross-linked moisture-permeable resin) can be used alone or in combination of two or more. Preferred moisture-permeable resins include polyvinyl alcohol cross-linked products (for example, cross-linked products of a mixture of glutaraldehyde and HCl, cross-linked products of formaldehyde, cross-linked products of blocked isocyanate, etc.), polyurethane cross-linked products (for example, at both ends). A crosslinked product of a hydroxy group-containing polyether or polyester and an aromatic diamine or polyhydric alcohol), or a fluorine ion exchange resin. The cross-linked polyvinyl alcohol is not only excellent in water resistance but also easy to apply and can easily achieve a thin moisture-permeable resin layer. The crosslinked polyurethane is not only excellent in water resistance but also excellent in abrasion resistance, oxidation resistance, oil resistance, and aging resistance. Fluorine ion exchange resins have excellent heat resistance and chemical resistance, so they are highly durable in high temperatures, high humidity, and systems where acids and alkalis exist, making them suitable for use in harsh environments. Yes.

(iii)補強用多孔質膜   (Iii) Reinforcing porous membrane

透湿性樹脂の層は、補強用多孔質膜に含まれており、これにより補強されている。このような透湿性樹脂の層を備えた複合膜の一例を図3に図示する。図3(a)は、補強用多孔質膜で補強された透湿性樹脂の層の概略断面図であり、図3(b)は、この透湿性樹脂の層を備えた複合膜の概略断面図である。図3(b)の複合膜は、補強用多孔質膜全体に透湿性樹脂を含む液を塗布または含浸させた後、補強用多孔質膜の片面を疎水性多孔質膜でカバーし、次いで溶剤を除去することによって製造できる。または、疎水性多孔質膜の片面に、透湿性樹脂を含む液を塗布または含浸させた後、その塗布または含浸させた面を補強用多孔質膜でカバーし、次いで溶剤を除去することによっても製造できる。さらに、補強用多孔質膜の上面側に、透湿性樹脂を含む液を塗布または含浸させてもよい。   The layer of moisture-permeable resin is included in the reinforcing porous membrane and is reinforced thereby. An example of a composite film provided with such a layer of moisture-permeable resin is shown in FIG. FIG. 3A is a schematic cross-sectional view of a layer of moisture-permeable resin reinforced with a reinforcing porous membrane, and FIG. 3B is a schematic cross-sectional view of a composite membrane provided with the layer of moisture-permeable resin. It is. In the composite membrane of FIG. 3 (b), after applying or impregnating a liquid containing moisture-permeable resin to the entire reinforcing porous membrane, one side of the reinforcing porous membrane is covered with a hydrophobic porous membrane, and then the solvent It can manufacture by removing. Alternatively, after applying or impregnating a liquid containing a moisture-permeable resin to one surface of the hydrophobic porous membrane, the coated or impregnated surface is covered with a reinforcing porous membrane, and then the solvent is removed. Can be manufactured. Furthermore, a liquid containing a moisture-permeable resin may be applied or impregnated on the upper surface side of the reinforcing porous membrane.

なお補強用多孔質膜としては、後述する疎水性多孔質膜と同様のものが使用できる。補強用多孔質膜の厚さは、所望の均一な透湿性樹脂の層の厚さを得られるように、適宜調整することができる。   As the reinforcing porous membrane, those similar to the hydrophobic porous membrane described later can be used. The thickness of the reinforcing porous membrane can be appropriately adjusted so that a desired uniform moisture-permeable resin layer thickness can be obtained.

(iv)疎水性多孔質膜   (Iv) Hydrophobic porous membrane

疎水性多孔質膜は、複合膜の一部を構成し、複合膜に疎水性をもたらしつつ通気性を維持する。疎水性多孔質膜は、疎水性と通気性を有する限り該疎水性多孔質膜を構成する樹脂の種類は特に限定されない。具体的には、耐熱性や耐腐食性を有するものが好ましく、ポリエチレン、ポリプロピレン等のポリオレフイン類;ポリカーボネート;ポリスチレン;ポリ塩化ビニル;ポリ塩化ビニリデン;ポリエステル;ポリテトラフルオロエチレン、テトラフルオロエチレン/ヘキサフルオロプロピレン共重合体、ポリフッ化ビニル、ポリフッ化ビニリデン等のフッ素樹脂等が使用出来る。   The hydrophobic porous membrane constitutes a part of the composite membrane and maintains air permeability while providing hydrophobicity to the composite membrane. The type of resin constituting the hydrophobic porous membrane is not particularly limited as long as the hydrophobic porous membrane has hydrophobicity and air permeability. Specifically, those having heat resistance and corrosion resistance are preferable. Polyolefins such as polyethylene and polypropylene; polycarbonate; polystyrene; polyvinyl chloride; polyvinylidene chloride; polyester; polytetrafluoroethylene, tetrafluoroethylene / hexafluoro Fluorine resins such as propylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride can be used.

好ましい疎水性多孔質膜は、フッ素樹脂製多孔質膜である。フッ素樹脂は、耐熱性および耐腐食性が優れ、且つ臨界表面張力が極めて低い、すなわち疎水性(撥水性)が高い。特に好ましい疎水性多孔質膜は、延伸されたポリテトラフルオロエチレン(PTFE)製の多孔質膜(以下、「ePTFE膜」、「延伸多孔質PTFE膜」などと称することがある)である。ePTFE膜は、極めて微細な孔を形成でき、表面の平滑性を高めることができるため、透湿樹脂層を容易に薄く均一に形成できる。また、ePTFE膜は、空孔率を高くすることが可能であり、得られる複合膜の透湿性を高くできる。さらに、ePTFE膜は、極めて優れた疎水性を備えており、このため、得られる複合膜は確実に液体の浸透を阻止することができる。   A preferred hydrophobic porous membrane is a fluororesin porous membrane. The fluororesin is excellent in heat resistance and corrosion resistance, and has extremely low critical surface tension, that is, high hydrophobicity (water repellency). A particularly preferred hydrophobic porous membrane is a stretched porous membrane made of polytetrafluoroethylene (PTFE) (hereinafter sometimes referred to as “ePTFE membrane”, “stretched porous PTFE membrane”, etc.). Since the ePTFE membrane can form extremely fine pores and can improve the smoothness of the surface, the moisture-permeable resin layer can be formed easily and uniformly. In addition, the ePTFE membrane can increase the porosity, and can increase the moisture permeability of the resulting composite membrane. Furthermore, the ePTFE membrane has extremely excellent hydrophobicity, so that the resulting composite membrane can reliably prevent liquid penetration.

疎水性多孔質膜と透湿性樹脂の層を積層加工する際は、熱融着により積層加工してもよいが、疎水性多孔質膜の耐熱性が透湿性樹脂の耐熱性を下回ると、融着加工が困難になる。そのため耐熱性に優れた素材を疎水性多孔質膜に使用すれば、透湿性樹脂の層との融着加工が容易となり、また透湿性樹脂の材質選択の自由度が大きくなる。   When laminating a hydrophobic porous membrane and a layer of moisture-permeable resin, the layers may be laminated by thermal fusion. However, if the heat resistance of the hydrophobic porous membrane is lower than the heat resistance of the moisture-permeable resin, the layer is melted. The dressing process becomes difficult. Therefore, if a material excellent in heat resistance is used for the hydrophobic porous membrane, it is easy to fuse with the moisture-permeable resin layer, and the degree of freedom in selecting the material of the moisture-permeable resin is increased.

ePTFE膜は、PTFEのファインパウダーを成形助剤と混合して得られるペーストを成形し、該成形体から成形助剤を除去した後、高温高速度で延伸し、さらに必要に応じて焼成することにより得られる。その詳細は、例えば特公昭51−18991号公報に記載されている。なお、延伸は、1軸延伸であってもよいし、2軸延伸であってもよい。1軸延伸多孔質PTFEフィルムは、ミクロ的には延伸方向と略直交する細い島状のノード(折り畳み結晶)が存在し、このノード間を繋ぐようなすだれ状のフィブリル(前記折り畳み結晶が延伸により溶けて引き出された直鎖状の分子束)が延伸方向に配向している点に特徴がある。一方、2軸延伸多孔質PTFEフィルムは、フィブリルが放射状に拡がり、フィブリルを繋ぐノードが島状に点在してフィブリルとノードとで分画された空間が多数存在するクモの巣状の繊維質構造となっている点にミクロ的な特徴がある。2軸延伸多孔質PTFEフィルムは、1軸延伸多孔質PTFEフィルムよりも広幅化が容易であり、縦方向・横方向の物性バランスに優れ、単位面積あたりの生産コストが安くなるため、特に好適に用いられる。   The ePTFE membrane is obtained by molding a paste obtained by mixing PTFE fine powder with a molding aid, removing the molding aid from the molded body, stretching at a high temperature and high speed, and further firing if necessary. Is obtained. The details are described in, for example, Japanese Patent Publication No. 51-18991. The stretching may be uniaxial stretching or biaxial stretching. In the uniaxially stretched porous PTFE film, there are micro island-like nodes (folded crystals) that are substantially perpendicular to the stretching direction in a microscopic manner, and interdigital fibrils (the folded crystals are stretched by stretching). It is characterized in that the linear molecular bundles (melted and drawn) are oriented in the stretching direction. On the other hand, the biaxially stretched porous PTFE film has a cobweb-like fibrous structure in which fibrils spread radially, nodes connecting the fibrils are scattered in islands, and there are many spaces divided by the fibrils and nodes. There is a micro feature in the point. The biaxially stretched porous PTFE film is particularly suitable because it is easier to widen than the uniaxially stretched porous PTFE film, has an excellent balance of physical properties in the vertical and horizontal directions, and lowers the production cost per unit area. Used.

疎水性多孔質膜の最大孔径は、例えば、15μm以下、好ましくは10μm以下、さらに好ましくは5μm以下である。最大孔径が大きすぎると、複合膜の製造時に透湿性樹脂を含む混合液を塗布または含浸させたときに、この透湿性樹脂が疎水性多孔質膜の細孔内に入り込み易くなるため、透湿性樹脂の層の形成が困難となる場合がある。最大孔径が小さくなるほど、透湿樹脂層の均一化が容易になり、ピンホールの発生を抑制することができる。ePTFE膜の最大孔径は延伸倍率等によって適宜制御できる。   The maximum pore diameter of the hydrophobic porous membrane is, for example, 15 μm or less, preferably 10 μm or less, and more preferably 5 μm or less. If the maximum pore size is too large, the moisture permeable resin will easily enter the pores of the hydrophobic porous membrane when a mixed solution containing the moisture permeable resin is applied or impregnated during the production of the composite membrane. Formation of the resin layer may be difficult. As the maximum hole diameter decreases, the moisture-permeable resin layer becomes easier to uniform, and the generation of pinholes can be suppressed. The maximum pore diameter of the ePTFE membrane can be appropriately controlled by the draw ratio or the like.

前記最大孔径は、イソプロパノールを用いたバブルポイント法(JISK3832)に従ってバブルポイント値を求め、下記式によって決定できる。
d=4γIPAcosθ/PB
(式中、dは最大孔径、γIPAはイソプロパノールの表面張力、θはイソプロパノールと疎水性多孔質膜の接触角(但し、疎水性多孔質膜がIPAで濡れている場合は、cosθ=1)、PBはバブルポイント値を示す)
The maximum pore diameter can be determined by the following formula by obtaining the bubble point value according to the bubble point method (JISK3832) using isopropanol.
d = 4γ IPA cos θ 1 / PB
(Where d is the maximum pore size, γ IPA is the surface tension of isopropanol, θ 1 is the contact angle between isopropanol and the hydrophobic porous membrane (provided that cos θ 1 = 1), PB indicates bubble point value)

なお、疎水性多孔質膜の平均孔径が小さくなりすぎると、疎水性多孔質膜の通気性、ひいては透湿性が低下し、複合膜の透湿能力が低下する。したがって、疎水性多孔質膜の平均細孔径は、例えば、0.05μm以上、好ましくは0.1μm以上、さらに好ましくは0.2μm以上である。   If the average pore size of the hydrophobic porous membrane is too small, the air permeability and consequently the moisture permeability of the hydrophobic porous membrane are lowered, and the moisture permeability of the composite membrane is lowered. Therefore, the average pore diameter of the hydrophobic porous membrane is, for example, 0.05 μm or more, preferably 0.1 μm or more, and more preferably 0.2 μm or more.

平均孔径は、細孔分布(細孔径に対する容積分布)から求めた値である。すなわち多孔質膜の全ての細孔を円筒形と仮定して細孔分布を測定し、細孔容積の中間値に対応する細孔径を平均孔径として求めた。なお本明細書において、疎水性多孔質膜の平均細孔径は、コールターエレクトロニクス社のコールターポロメーターを使用して平均孔径を求めた。   The average pore diameter is a value obtained from the pore distribution (volume distribution with respect to the pore diameter). That is, the pore distribution was measured on the assumption that all the pores of the porous membrane were cylindrical, and the pore diameter corresponding to the intermediate value of the pore volume was determined as the average pore diameter. In the present specification, the average pore diameter of the hydrophobic porous membrane was determined using a Coulter Porometer manufactured by Coulter Electronics.

疎水性多孔質膜の空孔率は前記平均孔径に応じて適宜設定できるが、例えば、40%以上(好ましくは50%以上)である。また前記空孔率は、例えば、98%以下(好ましくは90%以下)程度である。なお、ePTFE膜の空孔率は、上記平均細孔径と同様、延伸倍率等によって適宜調整できる。   The porosity of the hydrophobic porous membrane can be appropriately set according to the average pore diameter, and is, for example, 40% or more (preferably 50% or more). The porosity is, for example, about 98% or less (preferably 90% or less). Note that the porosity of the ePTFE membrane can be adjusted as appropriate by the draw ratio and the like, as with the average pore diameter.

疎水性多孔質膜の空孔率は、疎水性多孔質膜の質量Wと、空孔を含む見かけの体積Vとを測定することによって求まる嵩密度D(D=W/V:単位はg/cm)と、全く空孔が形成されていないときの密度Dstandard(PTFE樹脂の場合は2.2g/cm)を用い、下記式に基づいて算出できる。なお、体積Vを算出する際の疎水性多孔質膜の厚みは、ダイヤルシックネスゲージで測定した(テクロック社製「SM−1201」を用い、本体バネ荷重以外の荷重をかけない状態で測定した)平均厚みによる。
空孔率(%)=[1−(D/Dstandard)]×100
The porosity of the hydrophobic porous membrane is determined by measuring the mass W of the hydrophobic porous membrane and the apparent volume V including the pores, and the bulk density D (D = W / V: unit is g / cm 3 ) and density D standard (2.2 g / cm 3 in the case of PTFE resin) when no pores are formed at all, can be calculated based on the following formula. In addition, the thickness of the hydrophobic porous membrane at the time of calculating the volume V was measured with a dial thickness gauge (measured in a state where a load other than the main body spring load was applied using “SM-1201” manufactured by Teclock Corporation). Depending on the average thickness.
Porosity (%) = [1- (D / D standard )] × 100

疎水性多孔質膜の通気度(JISP8117:1998)は、例えば、500sec以下、好ましくは10sec以下である。通気度の値が大きすぎると、複合膜の透湿性が低くなり、得られる複合膜の透湿性が不充分となる。また複合膜を熱交換膜や膜蒸留用の膜として使用したときに、熱交換能力の低下や分離効率の低下が生じる。なお、通気度はガーレー数を意味する。ガーレー数とは、100cmの空気が1平方インチ(642mm)当たりの面積を流れるのに要する時間である。本明細書において、特に断りのない限り、通気度は旭精工社製王研式透気度測定器「KG1(商品名)」を用いて測定したものである。 The air permeability (JISP 8117: 1998) of the hydrophobic porous membrane is, for example, 500 sec or less, preferably 10 sec or less. When the value of the air permeability is too large, the moisture permeability of the composite membrane becomes low, and the moisture permeability of the resulting composite membrane becomes insufficient. Further, when the composite membrane is used as a heat exchange membrane or a membrane for membrane distillation, the heat exchange capacity and the separation efficiency are lowered. Air permeability means the Gurley number. The Gurley number is the time required for 100 cm 3 of air to flow over an area per square inch (642 mm 2 ). In this specification, unless otherwise specified, the air permeability is measured using an Oken type air permeability measuring device “KG1 (trade name)” manufactured by Asahi Seiko Co., Ltd.

疎水性多孔質膜の厚みは特に限定されないが、例えば、100μm以下、好ましくは50μm以下、さらに好ましくは25μm以下である。厚くなりすぎると複合膜の透湿能力が低下し、膜蒸留用の膜として使用したときに、熱交換能力の低下や分離効率の低下が生じる。但し、薄くなりすぎるとガスバリア性が低下し、液体や塩が透過してしまったり、また、加工性を損なったりする。よって疎水性多孔質膜の厚さは、例えば、5μm以上、好ましくは10μm以上、さらに好ましくは20μm以上である。   The thickness of the hydrophobic porous membrane is not particularly limited, but is, for example, 100 μm or less, preferably 50 μm or less, and more preferably 25 μm or less. If it is too thick, the moisture permeability of the composite membrane is lowered, and when used as a membrane for membrane distillation, the heat exchange capability and the separation efficiency are lowered. However, if the film is too thin, the gas barrier properties are lowered, and liquids and salts can permeate, and workability can be impaired. Therefore, the thickness of the hydrophobic porous membrane is, for example, 5 μm or more, preferably 10 μm or more, and more preferably 20 μm or more.

上述した様に、本発明では、疎水性多孔質膜と、補強用多孔質膜によって補強された透湿性樹脂の層とを複合化する。多孔質膜の表面の凹凸(孔径)は、不織布の繊維径に比べて遙かに小さく、透湿樹脂液の液溜まりを防ぐことができる。これにより、透湿性樹脂の層を薄く均一にし、ひいては高耐久性にしている。また、疎水性多孔質膜自体が、複合膜全体を補強している。   As described above, in the present invention, the hydrophobic porous membrane and the moisture-permeable resin layer reinforced by the reinforcing porous membrane are combined. The unevenness (pore diameter) on the surface of the porous membrane is much smaller than the fiber diameter of the nonwoven fabric, and it is possible to prevent the moisture-permeable resin liquid from collecting. Thereby, the layer of the moisture-permeable resin is made thin and uniform, and as a result, highly durable. Further, the hydrophobic porous membrane itself reinforces the entire composite membrane.

(v)通気性補強材   (V) Breathable reinforcement

通気性補強材は、通常、繊維状の樹脂で形成されている。繊維状の樹脂を使用することによって、通気性と強度とを兼ね備えた補強材を簡便に製造できる。繊維状樹脂によって形成される通気性補強材は、織布、編布、不織布(例えば、サーマルボンド方式、スパンボンド方式などの製法によって形成された不織布など)、ネットのいずれであってもよい。特に好ましい通気性補強材は、不織布である。   The breathable reinforcing material is usually formed of a fibrous resin. By using a fibrous resin, a reinforcing material having both air permeability and strength can be easily produced. The breathable reinforcing material formed by the fibrous resin may be any of a woven fabric, a knitted fabric, a non-woven fabric (for example, a non-woven fabric formed by a manufacturing method such as a thermal bond method or a spun bond method), or a net. A particularly preferable breathable reinforcing material is a nonwoven fabric.

(vi)用途   (Vi) Application

本発明の複合膜は、ガスバリア性が高く、透湿度も高い。そのため気体や液体に含まれる水蒸気を選択的に透過させるための分離膜(水分量調整モジュール用分離膜)として有利に使用でき、例えば、パーベーパレーション膜[例えば海水淡水化や水と他の液体(エタノールなどのアルコールなど)を分離するための膜]、除湿膜、加湿膜などとして使用できる。   The composite membrane of the present invention has high gas barrier properties and high moisture permeability. Therefore, it can be advantageously used as a separation membrane (separation membrane for moisture amount adjustment module) for selectively permeating water vapor contained in gas or liquid, for example, pervaporation membrane [eg seawater desalination or water and other liquids It can be used as a membrane for separating (alcohol such as ethanol), a dehumidifying membrane, a humidifying membrane or the like.

なお前記水分量調整モジュールでは、複合膜の透水性樹脂の層側の面に水を供給する側の流体(脱水される側の流体を含む)が流され、複合膜の他方の面に水を受け取る側の流体(脱水する側の流体を含む)が流され、これら給水側の流体と受水側の流体とが混ざらないように流路制御されている。好ましい水分量調整モジュールは、平膜スタック型モジュールであり、給水側流体と受水側流体は向流方向に流される。   In the moisture amount adjustment module, the fluid (including the fluid to be dehydrated) is supplied to the surface of the composite membrane on the layer side of the water-permeable resin, and water is supplied to the other surface of the composite membrane. The receiving side fluid (including the dehydrating side fluid) is flowed, and the flow path is controlled so that the water supply side fluid and the water receiving side fluid are not mixed. A preferable moisture amount adjustment module is a flat membrane stack type module, and the water supply side fluid and the water reception side fluid are caused to flow in the counterflow direction.

水分透過モジュールでは、複合膜が積み重ねられており、この積み重ねられた複合膜はスペーサーなどによって所定間隔で隔てられている。例えば、図4に示されるような、複合膜10および波形のスペーサー50を積層する態様がある。複合膜の両側に間隙が形成されることによって、この間隙を流体流路として使用でき、この両側の流体間で水分を交換することで、水分調整ができる。   In the moisture permeation module, composite membranes are stacked, and the stacked composite membranes are separated at a predetermined interval by a spacer or the like. For example, as shown in FIG. 4, there is a mode in which the composite film 10 and the corrugated spacer 50 are laminated. By forming a gap on both sides of the composite membrane, this gap can be used as a fluid flow path, and moisture can be adjusted by exchanging moisture between the fluids on both sides.

また本発明の複合膜は、透湿性樹脂として耐水透湿性樹脂を使用することによって、高温多湿下でも、ガスバリア性と透湿性を高めることができる。そのため高温多湿ガスから水蒸気を選択的に透過させる為の分離膜(例えば燃料電池電極の排ガス(特に空気極側の排ガス)に含まれる水蒸気を燃料極又は空気極(特に燃料極)に供給するガスの加湿に使用するための加湿膜)としても有利に使用できる。   Moreover, the composite film of this invention can improve gas-barrier property and moisture permeability even under high temperature and high humidity by using water-resistant moisture-permeable resin as moisture-permeable resin. Therefore, a gas for selectively supplying water vapor to a fuel electrode or an air electrode (especially a fuel electrode) contained in a separation membrane (for example, exhaust gas of a fuel cell electrode (especially exhaust gas on the air electrode side)) for selectively permeating water vapor from a hot and humid gas. It can also be advantageously used as a humidifying film for use in humidification of water.

以下、実施例を挙げて本発明をより具体的に説明するが、本発明はもとより下記実施例によって制限を受けるものではなく、前・後記の趣旨に適合し得る範囲で適当に変更を加えて実施することも勿論可能であり、それらはいずれも本発明の技術的範囲に包含される。   EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited by the following examples, but may be appropriately modified within a range that can meet the purpose described above and below. Of course, it is possible to implement them, and they are all included in the technical scope of the present invention.

(複合膜の調製) 実施例1
補強用多孔質膜として、ePTFE膜(ジャパンゴアテックス株式会社製、平均厚さ4μm、平均孔径0.3μm、最大孔径0.5μm、空孔率80%、ガーレー数0.9秒、引張強度MD1.0N、TD1.2N)を用意した。
疎水性多孔質膜として、ePTFE膜(ジャパンゴアテックス株式会社製、平均厚さ40μm、平均孔径0.2μm、最大孔径0.4μm、空孔率86%、ガーレー数5.4秒、引張強度MD1.2N、TD1.8N)を用意した。
透湿性樹脂溶液として、フッ素系イオン交換樹脂(旭硝子株式会社製「フレミオン(商品名)」、固形分9%エタノール溶媒(EtOH/HO=50/50))を用意した。
透湿性樹脂を、補強用多孔質膜の両面から、含浸させた。含浸と同時に、疎水性多孔質膜を、補強用多孔質膜の片面に載せ貼り合わせた。塗布した透湿性樹脂を130℃で1分間乾燥させた。
通気性補強材として、ポリエステル繊維(ユニチカファイバー株式会社製「メルティ(商品名)」、2.2dtex)を用いたサーマルボンド不織布(シンワ株式会社製「9820F(商品名)」)を用意した。通気性補強材を疎水性多孔質膜の透湿性樹脂を塗布した面とは反対の面に熱融着し(500kPaの荷重をかけながら150°Cで3分間)、実施例1の不織布付複合膜を形成した。
(Preparation of composite membrane) Example 1
As a porous membrane for reinforcement, ePTFE membrane (manufactured by Japan Gore-Tex Co., Ltd., average thickness 4 μm, average pore diameter 0.3 μm, maximum pore diameter 0.5 μm, porosity 80%, Gurley number 0.9 seconds, tensile strength MD1 .0N, TD1.2N).
As a hydrophobic porous membrane, ePTFE membrane (manufactured by Japan Gore-Tex Co., Ltd., average thickness 40 μm, average pore size 0.2 μm, maximum pore size 0.4 μm, porosity 86%, Gurley number 5.4 seconds, tensile strength MD1 .2N, TD1.8N).
As the moisture-permeable resin solution, fluorine-based ion-exchange resin (manufactured by Asahi Glass Co., Ltd. "Flemion (trade name)", 9% solids ethanol solvent (EtOH / H 2 O = 50 /50)) was prepared.
A moisture permeable resin was impregnated from both sides of the reinforcing porous membrane. Simultaneously with the impregnation, the hydrophobic porous membrane was placed on one side of the reinforcing porous membrane and bonded together. The applied moisture-permeable resin was dried at 130 ° C. for 1 minute.
As a breathable reinforcing material, a thermal bond nonwoven fabric (“9820F (trade name)” manufactured by Shinwa Co., Ltd.) using polyester fibers (“Melty (trade name)” manufactured by Unitika Fiber Co., Ltd., 2.2 dtex) was prepared. The breathable reinforcing material was thermally fused to the surface opposite to the surface coated with the moisture-permeable resin of the hydrophobic porous membrane (3 minutes at 150 ° C. while applying a load of 500 kPa), and the composite with nonwoven fabric of Example 1 A film was formed.

比較例1
補強用多孔質膜を使用しなかったことを除いて、実施例1と同様にして複合膜を形成した。
Comparative Example 1
A composite membrane was formed in the same manner as in Example 1 except that the reinforcing porous membrane was not used.

(評価)
実施例1および比較例1の複合膜の、透湿度、機械的強度、ならびに耐久性について評価を行った。以下に、それぞれの評価方法および評価結果について詳述する。
(Evaluation)
The composite membranes of Example 1 and Comparative Example 1 were evaluated for moisture permeability, mechanical strength, and durability. Below, each evaluation method and evaluation result are explained in full detail.

(1)透湿度
得られた不織布付複合膜の室温透湿性(JISL1099B−1法に依る)を測定した。測定結果を表1に示す。
(1) Moisture permeability The room temperature moisture permeability (depending on JISL1099B-1 method) of the obtained composite membrane with nonwoven fabric was measured. The measurement results are shown in Table 1.

この結果から、補強層の有無による透湿性への影響はほぼ無いことが分かった。   From this result, it was found that there is almost no influence on moisture permeability by the presence or absence of the reinforcing layer.

(2)機械的強度
補強用多孔質膜の有無が透湿性樹脂の層(機能層)の機械的強度に与える影響を評価した。疎水性多孔質膜、通気性補強材による機械的強度向上の影響を除くために、実施例1および比較例1の不織布付複合膜から、疎水性多孔質膜、通気性補強材を除いたものを試料として用意した。引っ張り試験機にて、常温条件での環境温湿度(23℃、50%RH)又は高温多湿条件での環境温湿度(60℃、100%RH)において、初期チャック間距離:80mm、試験片形状:10mm幅矩形、引張速度200mm/minにて測定を行った。引っ張り強度が最大になった時点での強度及び試料が破断した時点での伸度を求めた。また、弾性率は伸度が2%の時点での値を用いた。結果を表2に示す。
(2) Mechanical Strength The influence of the presence or absence of the reinforcing porous membrane on the mechanical strength of the moisture permeable resin layer (functional layer) was evaluated. In order to remove the influence of the mechanical strength improvement due to the hydrophobic porous membrane and the breathable reinforcing material, the hydrophobic porous membrane and the breathable reinforcing material are removed from the composite membrane with nonwoven fabric of Example 1 and Comparative Example 1. Was prepared as a sample. Using a tensile tester, the initial chuck-to-chuck distance: 80 mm at the ambient temperature and humidity (23 ° C., 50% RH) under normal temperature conditions or the ambient temperature and humidity (60 ° C., 100% RH) under high temperature and high humidity conditions. : Measurement was carried out at a 10 mm width rectangle and a tensile speed of 200 mm / min. The strength when the tensile strength reached the maximum and the elongation when the sample broke were determined. The elastic modulus was the value when the elongation was 2%. The results are shown in Table 2.

この結果から、補強用多孔質膜を有することにより、機械的強度が大幅に向上することが分かった。すなわち、透湿性樹脂の層(機能層)が補強用多孔質膜に含まれることにより、耐久性が大幅に向上した。   From this result, it was found that the mechanical strength was significantly improved by having the reinforcing porous membrane. That is, durability was significantly improved by including a layer (functional layer) of the moisture-permeable resin in the reinforcing porous membrane.

注目すべきことに、高温多湿条件において、補強用多孔質膜を有するものの機械的強度が向上している。本発明の複合膜を、水分量調整モジュール用分離膜、例えば、除湿膜、加湿膜、パーベーパレーション膜として実際に使用する場合、高温多湿条件であることが予想される。すなわち、実際の使用条件に近い高温多湿条件において、本発明の複合膜の機械的強度が高いことが示された。   It should be noted that the mechanical strength of the reinforcing porous membrane is improved under high temperature and high humidity conditions. When the composite membrane of the present invention is actually used as a separation membrane for a moisture amount adjusting module, for example, a dehumidifying membrane, a humidifying membrane, or a pervaporation membrane, it is expected to be a hot and humid condition. That is, it was shown that the mechanical strength of the composite membrane of the present invention is high under high temperature and high humidity conditions close to actual use conditions.

(3)耐久性
図5に示す耐久試験装置を用いて、実施例1および比較例1の不織布付複合膜の耐久性を試験した。耐久試験装置において、不織布付複合膜を配置し、水を注入し、そして試験用粉体を10wt%で水中に分散させた。耐久試験装置は、Airをバブリングすることができ、これにより試験用粉体を14日間攪拌させた。攪拌された試験用粉体は、耐久試験装置に配置した不織布付複合膜と接触した。耐久試験前後の不織布付複合膜について、フーリエ変換型赤外分光(FT−IR)による分析を行った。(FT−IRの測定装置:PerkinElmer社製Spectrum100、測定条件(ATR法により4000-400cm-1範囲で測定を実施。))
なお、試験用粉体の組成は、SiOが95%であり、Fe、Al、TiOおよびMgOの強熱減量が5%以下であった。試験用粉体の粒子密度は、2.6−2.7g/cmであった。粒径分布は、表3に示したとおりであり、表中のオーバーサイズ(%)とは、全粉体(粒子)に対して、指示されている粒径よりも大きな粒径の粉体(粒子)の割合を意味する。例えば、全粉体に対して、粒径が45μmより大きな粉体の割合は100%であり、粒径が75μmより大きな粉体の割合はおよそ90%である。したがって、45〜75μmの粉体の割合は、およそ10%(100−90)である。また、粒径が106μmより大きな粉体の割合はおよそ80%であり、したがって粒径が75〜106μmの粉体の割合は、およそ10%(90−80)である。
(3) Durability The durability of the composite membrane with nonwoven fabric of Example 1 and Comparative Example 1 was tested using the durability test apparatus shown in FIG. In the durability test apparatus, a composite membrane with a nonwoven fabric was placed, water was injected, and the test powder was dispersed in water at 10 wt%. The durability test apparatus was able to bubble Air, thereby stirring the test powder for 14 days. The agitated powder for testing contacted the composite membrane with nonwoven fabric placed in the durability test apparatus. The composite film with a nonwoven fabric before and after the durability test was analyzed by Fourier transform infrared spectroscopy (FT-IR). (Measurement device for FT-IR: Spectrum 100 manufactured by PerkinElmer, measurement conditions (measured in the range of 4000-400 cm -1 by ATR method))
The composition of the test powder, SiO 2 is 95%, Fe 2 O 3, Al 2 O 3, TiO 2 and MgO ignition loss was 5% or less. The particle density of the test powder was 2.6-2.7 g / cm 3 . The particle size distribution is as shown in Table 3, and the oversize (%) in the table is a powder having a particle size larger than the indicated particle size (%) with respect to the total powder (particles). The ratio of particles). For example, the proportion of powder having a particle size larger than 45 μm is 100% and the proportion of powder having a particle size larger than 75 μm is approximately 90% with respect to the total powder. Therefore, the proportion of 45-75 μm powder is approximately 10% (100-90). Further, the proportion of powder having a particle size larger than 106 μm is approximately 80%, and therefore the proportion of powder having a particle size of 75 to 106 μm is approximately 10% (90-80).

不織布付複合膜について耐久試験前後でFT−IR分析を行った。不織布付き複合膜は、実施例1の補強層ありのものと、比較例1の補強層なしのものを用いた。補強なしのものは、耐久前後のFT−IRチャート上でピーク高さの変化が見られた。特に、500cm−1付近の谷が耐久後に大きくなっている、および1000cm−1付近の谷が小さくなっているなどの変化が見られた。補強ありのものは、耐久前後のFT−IR上でピークの変化がほとんど見られなかった。すなわち、補強無しの複合膜の表面は、耐久前後で変化したと考えられるが、補強ありの複合膜の表面は、耐久前後でほとんど変化しなかったと考えられる。 The composite membrane with nonwoven fabric was subjected to FT-IR analysis before and after the durability test. As the composite membrane with a nonwoven fabric, the one with the reinforcing layer of Example 1 and the one without the reinforcing layer of Comparative Example 1 were used. A peak height change was observed on the FT-IR chart before and after endurance without reinforcement. In particular, changes such as a valley near 500 cm −1 increased after the endurance and a valley near 1000 cm −1 decreased. In the case of reinforcement, almost no peak change was observed on the FT-IR before and after durability. That is, it is considered that the surface of the composite membrane without reinforcement changed before and after the endurance, but the surface of the composite membrane with reinforcement hardly changed before and after the endurance.

補強なしの複合膜の表面の変化について調べるために、補強なしの複合膜およびePTFE単体のFT−IRチャートを比較した。補強なし複合膜は、耐久後に、500cm−1付近の谷が大きくなっていた。これは、ePTFEの500cm−1付近の谷とよく似ていた。このことから、補強されていない機能層(透湿性樹脂の層)が、耐久試験により減耗し、機能層の下にある疎水性多孔質膜(ePTFE膜)が露出してきたと考えられる。また、補強なし複合膜は、耐久後に、1000cm−1付近の谷が小さくなっていた。ePTFEは、1000cm−1付近で平坦なチャートを示し、ピークを示していない。このことから、1000cm−1付近で見られる谷は、機能層(透湿性樹脂の層)の材料に起因するものと考えられ、それが耐久試験により減耗し、1000cm−1付近で見られる谷が小さくなったと考えられる。 In order to investigate the change of the surface of the composite membrane without reinforcement, the composite membrane without reinforcement and the FT-IR chart of ePTFE alone were compared. The composite membrane without reinforcement had a large trough in the vicinity of 500 cm −1 after durability. This was very similar to the valley around 500 cm −1 of ePTFE. From this, it is considered that the unreinforced functional layer (moisture-permeable resin layer) was worn out by the durability test, and the hydrophobic porous membrane (ePTFE membrane) under the functional layer was exposed. Further, the unreinforced composite membrane had a small valley near 1000 cm −1 after durability. ePTFE shows a flat chart around 1000 cm −1 and does not show a peak. From this, the valley seen near 1000 cm −1 is considered to be caused by the material of the functional layer (moisture-permeable resin layer), and it is worn out by the durability test, and the valley seen near 1000 cm −1 It seems that it has become smaller.

これらの結果から、補強なしの複合膜は耐久試験によって機能層(透湿性樹脂の層)が減耗し、機能層の下にある疎水性多孔質膜(ePTFE膜)が露出してきたと考えられる。一方、補強ありの複合膜では耐久試験後もほとんど表面成分の変化が見られなかった、すなわち、機能層(透湿性樹脂の層)が減耗することなく、健全な状態を維持したと考えられる。   From these results, it is considered that in the composite membrane without reinforcement, the functional layer (moisture-permeable resin layer) was depleted by the durability test, and the hydrophobic porous membrane (ePTFE membrane) under the functional layer was exposed. On the other hand, it was considered that the composite film with reinforcement hardly changed the surface components even after the durability test, that is, the functional layer (moisture-permeable resin layer) did not wear out and maintained a healthy state.

10 複合膜
50 スペーサー
10 Composite membrane 50 Spacer

Claims (11)

溶液から水蒸気を分離する分離膜として使用する複合膜であって、
補強用多孔質膜;疎水性多孔質膜;および透湿性樹脂の層からなり、
該透湿性樹脂の層が、該補強用多孔質膜の上面に形成され且つ該補強用多孔質膜内に含浸し、
該透湿性樹脂の層が該補強用多孔質膜の下面から露出し、
該透湿性樹脂の層を介して、該補強用多孔質膜の下面が該疎水性多孔質膜に貼り付けられていることを特徴とする、複合膜。
A composite membrane used as a separation membrane for separating water vapor from a solution,
A reinforcing porous membrane; a hydrophobic porous membrane; and a layer of moisture-permeable resin,
The moisture-permeable resin layer is formed on the upper surface of the reinforcing porous membrane and impregnated in the reinforcing porous membrane;
A layer of the moisture permeable resin is exposed from the lower surface of the reinforcing porous membrane;
A composite membrane, wherein a lower surface of the reinforcing porous membrane is attached to the hydrophobic porous membrane via a layer of the moisture-permeable resin.
該補強用多孔質膜の下面から露出した該透湿性樹脂の層の少なくとも一部が、該疎水性多孔質膜内に入り込んでいるが、該疎水性多孔質膜の下面から露出していないことを特徴とする、請求項1に記載の複合膜。   At least part of the layer of the moisture-permeable resin exposed from the lower surface of the reinforcing porous membrane enters the hydrophobic porous membrane, but is not exposed from the lower surface of the hydrophobic porous membrane. The composite membrane according to claim 1, wherein 該透湿性樹脂の層の厚みが25μm以下であることを特徴とする、請求項1または2に記載の複合膜。   The composite membrane according to claim 1 or 2, wherein the moisture-permeable resin layer has a thickness of 25 µm or less. 該透湿性樹脂の層の厚みが10μm以下であることを特徴とする、請求項1〜3のいずれか1項に記載の複合膜。   The thickness of the layer of this moisture-permeable resin is 10 micrometers or less, The composite film of any one of Claims 1-3 characterized by the above-mentioned. 該透湿性樹脂の層の厚みが5μm以下であることを特徴とする、請求項1〜4のいずれか1項に記載の複合膜。   The composite membrane according to any one of claims 1 to 4, wherein a thickness of the moisture-permeable resin layer is 5 µm or less. 該透湿性樹脂が、以下の耐水性試験前後の樹脂の体積変化から求まる膨潤度が2倍以上且つ20倍以下の膨潤性を示し、
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
耐水性試験:温度120℃、水蒸気圧0.23MPaの環境下に樹脂を24時間放置し、次いで温度25℃の水に15分間浸漬すること、
を特徴とする、請求項1〜5のいずれか1項に記載の複合膜。
The moisture-permeable resin has a swelling degree of not less than 2 times and not more than 20 times the swelling degree obtained from the volume change of the resin before and after the following water resistance test,
Swelling degree = volume of resin after water resistance test / volume of resin before water resistance test Water resistance test: The resin is left in an environment at a temperature of 120 ° C. and a water vapor pressure of 0.23 MPa for 24 hours, and then water at a temperature of 25 ° C. Soak in for 15 minutes,
The composite membrane according to any one of claims 1 to 5, wherein
該透湿性樹脂がポリスチレンスルホン酸、ポリビニルアルコール、ビニルアルコール共重合体、フッ素系イオン交換樹脂、繰り返し単位にプロトン性親水性基を有する樹脂、繰り返し単位に非プロトン性親水性基を有する樹脂のいずれかであることを特徴とする、請求項1〜6のいずれか1項に記載の複合膜。   The moisture-permeable resin is any of polystyrene sulfonic acid, polyvinyl alcohol, vinyl alcohol copolymer, fluorine ion exchange resin, resin having a protic hydrophilic group in a repeating unit, and resin having an aprotic hydrophilic group in a repeating unit. The composite membrane according to any one of claims 1 to 6, wherein the composite membrane is any one of the above. 該透湿性樹脂がフッ素系イオン交換樹脂、ポリビニルアルコール、ポリウレタンのいずれかであることを特徴とする、請求項1〜7のいずれか1項に記載の複合膜。   The composite membrane according to any one of claims 1 to 7, wherein the moisture-permeable resin is any one of a fluorine ion exchange resin, polyvinyl alcohol, and polyurethane. 該補強用多孔質膜が、延伸PTFE膜であることを特徴とする、請求項1〜8のいずれか1項に記載の複合膜。   The composite membrane according to any one of claims 1 to 8, wherein the reinforcing porous membrane is an expanded PTFE membrane. その上に該補強用多孔質膜を貼り付けられた該疎水性多孔質膜の上面と逆の、該疎水性多孔質膜の下面に積層された通気性補強材をさらに含むことを特徴とする、請求項1〜9のいずれか1項に記載の複合膜。   It further comprises a breathable reinforcing material laminated on the lower surface of the hydrophobic porous membrane opposite to the upper surface of the hydrophobic porous membrane on which the reinforcing porous membrane is attached. The composite membrane according to any one of claims 1 to 9. 該通気性補強材が織布、不織布、ネットのいずれかであることを特徴とする、請求項10に記載の複合膜。   The composite membrane according to claim 10, wherein the breathable reinforcing material is any one of a woven fabric, a nonwoven fabric, and a net.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246550A1 (en) * 2019-06-06 2020-12-10 東洋紡株式会社 Porous membrane for membrane distillation
CN114361494A (en) * 2020-09-28 2022-04-15 未势能源科技有限公司 Composite bipolar plate and preparation method and application thereof
CN114471191A (en) * 2021-12-13 2022-05-13 华南理工大学 Anti-adhesion coating composite film with high moisture permeability and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020246550A1 (en) * 2019-06-06 2020-12-10 東洋紡株式会社 Porous membrane for membrane distillation
CN114361494A (en) * 2020-09-28 2022-04-15 未势能源科技有限公司 Composite bipolar plate and preparation method and application thereof
CN114471191A (en) * 2021-12-13 2022-05-13 华南理工大学 Anti-adhesion coating composite film with high moisture permeability and preparation method thereof
CN114471191B (en) * 2021-12-13 2022-11-04 华南理工大学 Anti-adhesion coating composite film with high moisture permeability and preparation method thereof

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