【発明の詳細な説明】 「発明の目的」 本発明は膜状素材の創案に係り、各種液体、気体の処理
操作に適した比較的薄層な機能性膜状素材を提供しよう
とするものである。DETAILED DESCRIPTION OF THE INVENTION “Object of the Invention” The present invention relates to the invention of a film material, and is intended to provide a relatively thin functional film material suitable for processing various liquids and gases. is there.
（産業上の利用分野） 各種液体、気体の分離、機能的処理ないし脱気や給気な
どに用いられる膜材。(Industrial field of application) Membrane materials used for separation of various liquids and gases, functional treatment, degassing and air supply.
（従来の技術） 各種液体、気体の分離、機能的処理、脱気または散気目
的において各種合成樹脂膜が採用されている。例えば電
池などのセパレータとしてイオン交換樹脂膜、又セロフ
ァンなどの微孔性天然高分子フィルムやプラスチックフ
ィルムにアクリル酸やメタクリル酸をグラフト重合させ
た膜などが知られている。又液体に対する散気ないし脱
気に関する多孔質樹脂フィルムを用いることが行われて
いる。(Prior Art) Various synthetic resin membranes have been adopted for the purpose of separating various liquids and gases, functional treatment, deaeration or air diffusion. For example, ion-exchange resin membranes as separators for batteries, and membranes obtained by graft-polymerizing acrylic acid or methacrylic acid on a microporous natural polymer film or plastic film such as cellophane are known. Further, it is practiced to use a porous resin film for diffusing or degassing a liquid.
更に各種フィルターとしても多孔質樹脂フィルムが用い
られている。Further, porous resin films are also used as various filters.
また各種混合液体、気体の特定成分の分離に関しても夫
々の分離機能を有する樹脂膜が利用されている。Further, resin films having respective separating functions are also used for separating specific components of various mixed liquids and gases.
（発明が解決しようとする問題点） 然し上記したような従来のものにおいてはなお問題点が
多い。即ちイオン交換樹脂を製膜したものは薄膜状とな
し、あるいは交換容量を上げたりするとその強度や液中
における安定性に劣ることとなる不利がある。微孔性天
然高分子フィルムによるものでは酸化剤により酸化され
て劣化する傾向が大であり、プラスチックフィルムにア
クリル酸などをグラフト重合させたものにおいては活物
質の拡散が起ったり、腐食性に問題がある。更にこのよ
うな樹脂フィルムは一般的に撥水性を有し、微細化され
た気体粒子に種々の影響を与え、充分に均一微細で効率
のよい散気目的を達し得ない。(Problems to be Solved by the Invention) However, there are still many problems in the related art as described above. That is, if the ion exchange resin is formed into a thin film, or if the exchange capacity is increased, there is a disadvantage that its strength and stability in liquid are deteriorated. The microporous natural polymer film tends to be oxidized and deteriorated by an oxidizing agent, and the plastic film graft-polymerized with acrylic acid causes diffusion of the active material and corrosion resistance. There's a problem. Further, such a resin film generally has water repellency, exerts various influences on the finely divided gas particles, and cannot achieve a sufficiently uniform fine particle and efficient air diffusion purpose.
なお疏水性多孔質樹脂フィルムを水系フィルターとして
使用するときは高い透水圧の適用が必要である等の問題
がある。また水分の選択的透過性が高く、耐熱性のある
分離膜は極めて限られている。When using the hydrophobic porous resin film as an aqueous filter, there is a problem that it is necessary to apply high water permeability. In addition, the number of heat-resistant separation membranes that have high selective permeability of water is extremely limited.
「発明の構成」 （問題点を解決するための手段） ポリテトラフルオロエチレンの延伸多孔質フィルムに対
し重量比で１０〜３０％のパーフロロ系イオン交換樹脂
を均一状態に添着一体化し膜厚３〜５０μｍとされたこ
とを特徴とする膜状素材。[Structure of the Invention] (Means for Solving Problems) Perfluoro-based ion exchange resin in a weight ratio of 10 to 30% by weight with respect to a stretched porous film of polytetrafluoroethylene is uniformly attached and integrated to a film thickness of 3 to 3. Membrane material characterized by having a thickness of 50 μm.
（作用） 延伸による多孔質ポリテトラフルオロエチレンフィルム
は撥水性を有し、液体中において充分な機械的強度や寸
法安定性を得しめる。又このような延伸多孔質ポリテト
ラフルオロエチレンフィルムを基体とすることによりパ
ーフロロ系イオン交換樹脂膜が薄膜として、又部分的に
多孔質ポリテトラフルオロエチレン組織中によく進入結
合して安定に形成される。前記パーフロロ系イオン交換
樹脂膜は親水性を有し、撥水性の上記ポリテトラフルオ
ロエチレンフィルムにこのような親水性薄膜が形成され
ることにより液体に対する特性が変化せしめられる。即
ち充実膜においては水等のパーフロロ系イオン交換樹脂
に対する親和成分の選択透過能のある膜となる。またハ
ーフロロ系イオン交換樹脂によって方面が均一に蔽われ
た連続多孔質膜にあっては表面特性の変化によって透水
圧が下って水の透過が容易となり、水系のフィルターと
しての適性がが向上する。更に水系での散気用に使用す
るときはパーフロロ系イオン交換樹脂被覆のない場合に
比し遥かに微細均一な効率のよい散気を可能とする。ま
た延伸多孔質ポリテトラフルオロエチレンフィルムは官
能基がないので化学処理には適さないが、パーフロロ系
イオン交換樹脂は官能基を有するのでこれとの複合化に
より酵素固定等の官能基を利用した各種機能化が可能と
なる。(Operation) The stretched porous polytetrafluoroethylene film has water repellency and can obtain sufficient mechanical strength and dimensional stability in a liquid. Further, by using such a stretched porous polytetrafluoroethylene film as a substrate, the perfluoro-based ion exchange resin membrane is formed as a thin film, or partially penetrates well into the porous polytetrafluoroethylene structure and is stably formed. It The perfluoro-based ion exchange resin membrane has hydrophilicity, and by forming such a hydrophilic thin film on the water-repellent polytetrafluoroethylene film, the characteristics for liquid can be changed. That is, the solid membrane has a capability of selectively permeating an affinity component such as water for the perfluoro-based ion exchange resin. Further, in the case of a continuous porous membrane whose surface is uniformly covered with a half-rollo type ion exchange resin, the water permeation pressure is lowered due to the change in surface characteristics, water is easily permeated, and the suitability as an aqueous filter is improved. Further, when it is used for air diffusion in a water system, far finer and more uniform and efficient air diffusion is possible as compared with the case where there is no perfluoro type ion exchange resin coating. In addition, stretched porous polytetrafluoroethylene film is not suitable for chemical treatment because it has no functional group, but perfluoro-based ion exchange resin has a functional group, so it can be used in combination with various functional groups such as enzyme immobilization. Functionalization is possible.
このパーフロロ系イオン交換樹脂膜の量がポリテトラフ
ルオロエチレン多孔質フィルムの１０％以上とされるこ
とにより上記した液体に対する特性変化を適切に図らし
め、またこの量を３０％以下とすることにより延伸多孔
質ポリテトラフルオロエチレンフィルムを基材とした機
械的強度ないし寸法安定性を有効に得しめる。The amount of this perfluoro ion exchange resin membrane is 10% or more of that of the polytetrafluoroethylene porous film, so that the characteristic change with respect to the above liquid can be appropriately achieved, and the amount of the perfluoro type ion exchange resin membrane can be stretched by setting it to 30% or less. It is possible to effectively obtain mechanical strength or dimensional stability based on a porous polytetrafluoroethylene film.
膜厚３μｍ以上とすることにより上記したような特性を
有し且つ好ましい寸法安定性をもった膜材として得し
め、またこの膜厚を５０μｍ以下とすることにより、特
にその多孔質組織と相俟って好ましい気液の接触を効率
的に図り、目的とする分離ないし機能的処理、脱気、散
気などを能率的に得しめる。By setting the film thickness to 3 μm or more, a film material having the above-mentioned characteristics and having preferable dimensional stability can be obtained, and by setting the film thickness to 50 μm or less, particularly, it is associated with the porous structure. Therefore, preferable contact of gas and liquid can be efficiently achieved, and the desired separation or functional treatment, deaeration, aeration and the like can be efficiently obtained.
（実施例） 上記した本発明によるものの具体的な実施態様を説明す
ると、本発明によるものは気孔率３５％以上、特に４０
％以上のポリテトラフルオロエチレンの延伸加工フィル
ムにパーフロロ系イオン交換樹脂を均一状態に添着一体
化する。この添着一体化はパーフロロ系イオン交換樹脂
のフィルムを融着し、あるいはその樹脂液コーティング
の何れによってもよい。このようなポリテトラフルオロ
エチレン延伸フィルムとパーフロロ系イオン交換樹脂と
の接着一体化をなす代表的方法の若干は以下の如くで、
その何れによってもよい。(Example) A concrete embodiment of the above-described one according to the present invention will be described. The one according to the present invention has a porosity of 35% or more, particularly 40%.
% Or more of the polytetrafluoroethylene stretched film, and perfluorinated ion-exchange resin is uniformly attached and integrated. This attachment and integration may be performed by fusing a film of a perfluoro-based ion exchange resin or coating the resin liquid. Some of the typical methods for bonding and integrating such a polytetrafluoroethylene stretched film and a perfluoro-based ion exchange resin are as follows.
Any of them may be used.
延伸処理して得られた多孔質ＰＴＦＥフィルムにパ
ーフロロ系イオン交換樹脂液を充分に含浸させて緻密な
隔膜とする。The porous PTFE film obtained by the stretching treatment is sufficiently impregnated with the perfluoro-based ion exchange resin liquid to form a dense diaphragm.
上記において、パーフロロ系イオン交換樹脂液を
不充分な状態に含浸させてなお多孔質性を有する隔膜と
する。In the above, the perfluoro-based ion exchange resin liquid is impregnated in an insufficient state to form a porous membrane.
ＰＴＦＥ樹脂にイオン交換樹脂液を混合し製膜に当
って延伸し多孔質の膜とする。An ion exchange resin liquid is mixed with the PTFE resin, and the resulting mixture is stretched to form a porous membrane.
イオン交換樹脂を先ず薄膜状に成形し、これを延伸
ＰＴＦＥ多孔質膜にラミネート接着する。First, the ion exchange resin is formed into a thin film, and this is laminated and adhered to the expanded PTFE porous membrane.
何れの場合においてもＰＴＦＥに対するパーフロロ系イ
オン交換樹脂との割合は前記のように重量比で１０〜３
０％とする。又膜全体の厚さについては３〜５０μｍで
ある。In any case, the ratio of the perfluoro-based ion exchange resin to PTFE is 10 to 3 by weight as described above.
0% The thickness of the entire film is 3 to 50 μm.
ポリテトラフルオロエチレン多孔質フィルムの厚さにつ
いても３〜５０μｍである。The thickness of the polytetrafluoroethylene porous film is also 3 to 50 μm.
上記のようにして得られた膜状素材は液中、気中におけ
る各種用途に利用することができ、例えば液中に存する
気体分の除去、液体に対する気体の添加、あるいは電解
隔膜、気体、液体の分離膜、特に水分の選択透過膜、フ
ィルター、酵素固定膜等の化学反応促進膜などの機能膜
として採用されるが、薄膜状であって好ましい機械的強
度、寸法安定性を有し、ポリテトラフルオロエチレン多
孔質フィルムに求められない多くの高機能を賦与し得
る。The membranous material obtained as described above can be used for various applications in liquid and in air, for example, removal of gas components present in liquid, addition of gas to liquid, or electrolytic diaphragm, gas, liquid. It is used as a functional membrane such as a separation membrane of water, a permselective membrane of water, a filter, a chemical reaction accelerating membrane such as an enzyme immobilization membrane, etc., but it has a preferable thin film-like mechanical strength and dimensional stability. It can impart many high functions which are not required for the tetrafluoroethylene porous film.
ハロゲン−亜鉛電池用セパレータとして用いた場合にお
いては上記のような機械的強度や寸法安定性と共に電解
質による劣化を受けることがなく、電気抵抗が低いと共
にクーロン効率に優れたものとして得られ、電池寿命も
高い。When used as a separator for a halogen-zinc battery, it is not affected by the electrolyte in addition to the mechanical strength and dimensional stability as described above, and has low electric resistance and excellent Coulombic efficiency. Is also high.
「発明の効果」 以上説明したような本発明によるときは機械的強度と寸
法的安定性に優れ、製造条件によって膜全体の親水性ま
たは撥水性と親水性の同時具備も可能であり、各種分離
膜、反応膜等の液体と気体とを処理する機器ないし設備
において利用し好ましい特性を示す膜材を提供し得るも
のであって、工業的にその効果の大きい発明である。[Advantages of the Invention] According to the present invention as described above, the mechanical strength and the dimensional stability are excellent, and the hydrophilicity of the entire membrane or the simultaneous provision of water repellency and hydrophilicity is possible depending on the production conditions. The present invention can provide a film material exhibiting preferable characteristics when used in equipment or equipment for treating liquid and gas such as a film and a reaction film, and is an invention having a great effect industrially.
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