JPH05261256A - Fluorine-containing copolymer film and separating membrane - Google Patents
Fluorine-containing copolymer film and separating membraneInfo
- Publication number
- JPH05261256A JPH05261256A JP9357192A JP9357192A JPH05261256A JP H05261256 A JPH05261256 A JP H05261256A JP 9357192 A JP9357192 A JP 9357192A JP 9357192 A JP9357192 A JP 9357192A JP H05261256 A JPH05261256 A JP H05261256A
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- Japan
- Prior art keywords
- copolymer
- film
- fluorine
- membrane
- containing copolymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は水処理用や医療用として
有効な耐熱水性、耐汚染性を有する、含フッ素共重合体
からなる膜及び該膜からなる分離膜に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a membrane comprising a fluorocopolymer and a separation membrane comprising the membrane, which is effective for water treatment and medical purposes and has hot water resistance and stain resistance.
【０００２】[0002]
【従来の技術及びその問題点】ポリビニルアルコール系
重合体を用いた膜は、その親水性や耐久性、耐溶剤性、
透明性、酸素不透過性、機械的強度などの性質を生かし
て、医療用、水処理用、包装用など広い分野で用いられ
ている。しかし、このような分野では、ポリビニルアル
コール自体は、水溶性であるため、膨潤或いは溶解のた
めそのままでは実用性膜として使用することはできな
い。2. Description of the Related Art Membranes made of polyvinyl alcohol-based polymers have the following properties: hydrophilicity, durability, solvent resistance,
It is used in a wide range of fields such as medical applications, water treatment, and packaging due to its properties such as transparency, oxygen impermeability and mechanical strength. However, in such a field, since polyvinyl alcohol itself is water-soluble, it cannot be used as a practical film as it is because it swells or dissolves.
【０００３】この点を改良するために種々の不溶化の手
段がとられている。不溶化方法としては、アセタール
化、或いはジアルデヒドやジカルボン酸を用いた架橋反
応などの反応によってその化学構造を一部変換する方法
や、熱処理や延伸によって結晶性を上げるといった物理
構造を変換する方法（特開昭５５−２８７４１）、なら
びにそれらを組み合わせた方法が知られている。しかし
先にあげた化学構造を変換する不溶化反応の場合は、反
応剤を膜面全体に均一に反応させるためには、反応温度
や時間といった条件を厳密に管理する必要があり、工程
が複雑になる上、反応終了後には反応に使用したアルデ
ヒドやカルボン酸などを洗浄除去すめための工程が必要
となる。また、熱処理や延伸により物理構造を変換する
方法においても、結晶化度の制御などの膜性能安定化の
ための煩雑な工程が必要となる。さらにこのようにして
得られた膜には、長期間の使用において架橋点の分解や
結晶化度の低下などによる経時的な性能低下を来すとい
う問題がある。In order to improve this point, various means of insolubilization are taken. As the insolubilization method, a method of partially converting the chemical structure by acetalization or a reaction such as a crosslinking reaction using a dialdehyde or a dicarboxylic acid, or a method of converting a physical structure such as increasing the crystallinity by heat treatment or stretching ( JP-A-55-28741) and methods combining them are known. However, in the case of the insolubilization reaction that converts the chemical structure mentioned above, it is necessary to strictly control the conditions such as reaction temperature and time in order to react the reactant uniformly on the entire film surface, which complicates the process. In addition, after the completion of the reaction, a step for washing and removing the aldehyde and carboxylic acid used in the reaction is required. Further, even in the method of converting the physical structure by heat treatment or stretching, complicated steps for stabilizing the film performance such as controlling the crystallinity are required. Further, the film obtained in this manner has a problem that it deteriorates in performance over time due to decomposition of cross-linking points, deterioration of crystallinity and the like after long-term use.
【０００４】他方このような化学的、あるいは物理的不
溶化方法を経ないポリビニルアルコール系膜として、実
質的に水不溶性のエチレン−ビニルアルコール共重合体
（以下、ＥＶＡと略記する）を用いて湿式成膜して得ら
れた膜が開発されている（特公昭５６−１１２２号、特
開昭５８−４５２３９号など）。しかし、ＥＶＡを用い
て成膜する場合、溶媒としてジメチルスルホキシドある
いはこれと他の有機溶媒との混合溶媒が用いられ、また
凝固媒体としては凝固助剤である無機塩類を添加した水
が用いられている。このため、製膜後の凝固液中には少
なくとも、ジメチルスルホキシド、水、無機塩の三者が
混合されており、工業的な生産においては、これらの回
収あるいは除去に多くのエネルギーと労力を消費し、生
産効率が著しく悪いものとなっている。On the other hand, as a polyvinyl alcohol-based film that does not undergo such a chemical or physical insolubilization method, a substantially water-insoluble ethylene-vinyl alcohol copolymer (hereinafter abbreviated as EVA) is used for wet-forming. Membranes obtained by film formation have been developed (Japanese Patent Publication No. 56-1122, Japanese Patent Application Laid-Open No. 58-45239, etc.). However, when forming a film using EVA, dimethyl sulfoxide or a mixed solvent of this and another organic solvent is used as a solvent, and water to which an inorganic salt as a coagulation aid is added is used as a coagulation medium. There is. For this reason, at least the three components of dimethyl sulfoxide, water, and inorganic salt are mixed in the coagulation liquid after film formation, and in industrial production, much energy and labor are consumed to recover or remove these. However, the production efficiency is extremely poor.
【０００５】しかも、前記した如き従来のポリビニルア
ルコール系重合体を素材とする膜は、これを水処理用と
して使用する場合、その親水性ゆえに使用中に膜表面に
汚染物質の蓄積を生じ易く、またその汚染物質は洗浄に
おいても十分に除去する事が難しく、膜の寿命が短いと
いう欠点を有している。また血液透析あるいは血漿分離
用などの医療用として使用する場合には、膜表面への血
漿板の付着などの問題がある。このように、従来のポリ
ビニルアルコール系重合体を用いて得られる膜は、耐水
性、特に耐熱水性を付与するためには煩雑な工程を必要
とし、また使用中に膜性能の経時劣化を生じるという欠
点を有している。さらにその親水性故に膜表面の汚染を
生じ易い。In addition, the conventional membrane made of the polyvinyl alcohol-based polymer as described above, when used for water treatment, tends to cause accumulation of contaminants on the surface of the membrane during use due to its hydrophilicity. Further, it is difficult to sufficiently remove the pollutant even in washing, and the film has a short life. Further, when it is used for medical purposes such as hemodialysis or plasma separation, there is a problem such as adhesion of a plasma plate on the membrane surface. As described above, the film obtained using the conventional polyvinyl alcohol-based polymer requires a complicated process for imparting water resistance, particularly hot water resistance, and also causes deterioration in film performance over time during use. It has drawbacks. Further, due to its hydrophilicity, contamination of the film surface is likely to occur.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、従来のポリ
ビニルアルコール系重合体膜に見られる前記問題を解決
し、耐水性にすぐれるとともに、汚染されにくく、かつ
成膜の容易な含フッ素共重合体膜及びその膜を用いた分
離膜を提供することをその課題とする。DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned problems found in conventional polyvinyl alcohol-based polymer membranes, has excellent water resistance, is less likely to be contaminated, and is easy to form a fluorine-containing copolymer film. It is an object of the present invention to provide a polymer membrane and a separation membrane using the membrane.
【０００７】[0007]
【課題を解決するための手段】本発明者らは前記課題を
解決すべく鋭意検討を重ねた結果、本発明を完成するに
至った。即ち、本発明によれば、テトラフルオロエチレ
ンと酢酸ビニルとの共重合体又は該共重合体に含まれる
アセテート基の少なくとも一部をケン化した共重合体か
らなり、該共重合体中に含まれるテトラフルオロエチレ
ン含有率が１〜７０モル％であることを特徴とする含フ
ッ素共重合体膜が提供される。また、本発明によれば、
前記含フッ素共重合体膜からなる分離膜が提供される。Means for Solving the Problems The present inventors have completed the present invention as a result of intensive studies to solve the above problems. That is, according to the present invention, a copolymer of tetrafluoroethylene and vinyl acetate or a copolymer obtained by saponifying at least a part of the acetate group contained in the copolymer is contained in the copolymer. There is provided a fluorocopolymer membrane characterized in that the content of tetrafluoroethylene is 1 to 70 mol%. Further, according to the present invention,
A separation membrane comprising the above-mentioned fluorine-containing copolymer membrane is provided.
【０００８】本発明で製膜材料として用いる含フッ素共
重合体は、テトラフルオロエチレン（以下、ＴＦＥと略
記する）と酢酸ビニル（以下、ＶＡｃと略記する）との
共重合体（以下、ＴＦＥ／ＶＡｃ共重合体と略記する）
又はその共重合体に含まれるアセテート基の少なくとも
一部をケン化した共重体からなるものである。ＴＦＥ／
ＶＡｃ共重合体は、ＴＦＥとＶＡｃとを従来公知の方法
で共重合させることによって得ることができる。また、
アセテート基のケン化も従来良く知られており、アルコ
リシスや加水分解等の従来公知の方法によって行うこと
ができる。このケン化によって、アセテート基（−ＯＣ
ＯＣＨ3）は、水酸基（ＯＨ）に変換される。The fluorine-containing copolymer used as the film-forming material in the present invention is a copolymer of tetrafluoroethylene (hereinafter abbreviated as TFE) and vinyl acetate (hereinafter abbreviated as VAc) (hereinafter TFE / (Abbreviated as VAc copolymer)
Alternatively, it is a copolymer obtained by saponifying at least a part of the acetate group contained in the copolymer. TFE /
The VAc copolymer can be obtained by copolymerizing TFE and VAc by a conventionally known method. Also,
Saponification of the acetate group is well known in the art, and can be carried out by a conventionally known method such as alcoholysis or hydrolysis. By this saponification, an acetate group (-OC
OCH 3 ) is converted into a hydroxyl group (OH).
【０００９】本発明で製膜材料として用いるＴＦＥ／Ｖ
Ａｃ共重合体において、その粘度平均分子量は２０，０
００以上、通常１００，０００〜１０００，０００であ
る。また、そのＴＦＥ含有率は、１〜７０モル％である
が、１０モル％未満では熱水と接触させた場合に溶出現
象を生じるようになり、一方、５０モル％を超えると親
水性が低下し、得られた膜の透水性が低下するので、そ
の含有率は１０〜５０モル％の範囲に保持するのが好ま
しい。本発明で製膜材料として用いるＴＦＥ／ＶＡｃ共
重合体のアセテート基の少なくとも一部をケン化した共
重合体において、そのケン化度は５０〜１００％、好ま
しくは７０〜１００％である。TFE / V used as a film-forming material in the present invention
The viscosity average molecular weight of the Ac copolymer is 20,0.
00 or more, usually 100,000 to 1,000,000. The TFE content is 1 to 70 mol%, but if it is less than 10 mol%, an elution phenomenon occurs when it is brought into contact with hot water, while if it exceeds 50 mol%, the hydrophilicity decreases. However, since the water permeability of the obtained membrane decreases, it is preferable to keep the content in the range of 10 to 50 mol%. In the copolymer obtained by saponifying at least a part of the acetate group of the TFE / VAc copolymer used as the film-forming material in the present invention, the saponification degree is 50 to 100%, preferably 70 to 100%.
【００１０】なお、前記ケン化度は、次式により表わさ
れる。 前記式中、各符号は次のことを意味する。 Ｒ：ケン化度（％） ｐ：共重合体中の酢酸ビニル成分のモル数 ｑ＝共重合体中に含まれるビニルアルコールの成分のモ
ル数The saponification degree is represented by the following equation. In the above formula, each symbol means the following. R: Degree of saponification (%) p: Number of moles of vinyl acetate component in the copolymer q = Number of moles of vinyl alcohol component contained in the copolymer
【００１１】本発明の含フッ素共重合体膜は、種々の膜
厚で用いられるが、ロエブ（Ｌｏｅｂ）型と称される非
対称の膜体として用いる場合、ステン層厚０．１〜１０
μｍ、膜全体厚さ５０〜５００μｍで用いられ、均質膜
の場合は、数μｍ〜数百μｍで用いられる。The fluorine-containing copolymer film of the present invention is used in various film thicknesses, but when it is used as an asymmetric film body called Loeb type, the thickness of the stainless steel layer is 0.1 to 10.
μm, the entire film thickness is 50 to 500 μm, and in the case of a homogeneous film, it is used in several μm to several hundred μm.
【００１２】前記含フッ素共重合体を成膜するための方
法としては、一般に湿式もしくは乾湿式法と呼ばれる方
法あるいは溶融押出し法を採用することができる。以下
にこれら成膜法の例をあげるが、本発明はこれらの成膜
法に限定されるものではない。As a method for forming the above-mentioned fluorine-containing copolymer, a method generally called a wet or dry-wet method or a melt extrusion method can be adopted. Examples of these film forming methods are given below, but the present invention is not limited to these film forming methods.
【００１３】湿式あるいは乾湿式法による成膜に際して
使用される含フッ素共重合体の溶媒としては、メタノー
ル、エタノール、アセトンなどの極性溶媒や、ジメチル
スルホキシド、Ｎ，Ｎ−ジメチルホルムアミド、Ｎ−メ
チルピロリドンといった非プロトン性極性溶媒、あるい
はこれらと水との混合溶媒、さらにこれらの中から選ば
れた溶媒の混合溶媒が使用できるが、本発明で用いる含
フッ素共重合体の溶解性や溶液粘度、凝固液中への分散
性などの点から、ジメチルスルホキシド、Ｎ，Ｎ−ジメ
チルホルムアミドが好適に使用される。本発明で用いる
凝固液としては、水を用いることができ、その他、硫酸
ソーダ等の無機塩を溶解させた水溶液を用いることがで
きる。含フッ素共重合体を湿式法で製膜するには、含フ
ッ素共重合体を溶媒に溶解し、ドープ液を作る。この場
合、得られる膜の透水性（多孔度）を調整するために、
ポリビニルアルコールやポリビニルピロリドン、ポリエ
チレングリコールの如き水溶性高分子をドープ液に添加
することができる。次に、このドープ液を膜状物とし
て、これを凝固液と接触させる。Solvents for the fluorine-containing copolymer used for film formation by the wet or dry-wet method include polar solvents such as methanol, ethanol and acetone, dimethyl sulfoxide, N, N-dimethylformamide and N-methylpyrrolidone. An aprotic polar solvent such as, or a mixed solvent of these and water, and a mixed solvent of solvents selected from these can be used, but the solubility or solution viscosity and coagulation of the fluorocopolymer used in the present invention can be used. Dimethyl sulfoxide and N, N-dimethylformamide are preferably used from the viewpoint of dispersibility in the liquid. As the coagulating liquid used in the present invention, water can be used, and in addition, an aqueous solution in which an inorganic salt such as sodium sulfate is dissolved can be used. To form a film of the fluorinated copolymer by a wet method, the fluorinated copolymer is dissolved in a solvent to prepare a dope solution. In this case, in order to adjust the water permeability (porosity) of the obtained membrane,
Water-soluble polymers such as polyvinyl alcohol, polyvinylpyrrolidone, and polyethylene glycol can be added to the dope solution. Next, this dope liquid is made into a film-like substance, and this is brought into contact with the coagulating liquid.
【００１４】溶融押出し法では、ケン化度５０〜８０％
の含フッ素共重合体が好適に用いられるが、高ケン化度
の共重合体、例えば、ケン化度９０〜１００％のものを
用いた場合、流動開始温度が２００℃以上となり、溶融
押出しが困難となることがある。このような場合には、
可塑剤を添加する事ができる。可塑剤としては、エチレ
ングリコール、ジエチレングリコールといったポリエチ
レングリコールや、グリセリン、１，３−ブタンジオー
ル、トリメチロールプロパンのような多価アルコール類
などがある。可塑剤の添加量は、共重合体に対して０．
１〜５０重量％、好ましくは０．５〜３０重量％であ
る。In the melt extrusion method, the saponification degree is 50 to 80%.
The fluorine-containing copolymer of is preferably used, but when a copolymer having a high saponification degree, for example, a saponification degree of 90 to 100% is used, the flow starting temperature becomes 200 ° C. or higher, and melt extrusion is performed. It can be difficult. In such cases,
A plasticizer can be added. Examples of the plasticizer include polyethylene glycol such as ethylene glycol and diethylene glycol, polyhydric alcohols such as glycerin, 1,3-butanediol, and trimethylolpropane. The amount of the plasticizer added was 0.
It is 1 to 50% by weight, preferably 0.5 to 30% by weight.
【００１５】本発明により得られる含フッ素共重合体膜
において、その共重合体のケン化処理は、前記したよう
に、成膜前の共重合体に対して行うことができる他、成
膜後の共重合体膜に対して行うこともできる。ケン化度
が９５％以上の含フッ素共重合体膜を溶融押出し法で製
造する場合には、ケン化度５０〜８０％の共重合体を溶
融押出し法で成膜した後、得られた膜をケン化処理して
目的の製品膜を得ることができる。湿式法、乾湿式法、
溶融押し出し法のいずれにおいても平膜、チューブ、あ
るいは中空糸の形態が生産可能であり、その用途によっ
て適宜選択される。In the fluorine-containing copolymer film obtained by the present invention, the saponification treatment of the copolymer can be carried out on the copolymer before film formation as described above, or after film formation. Can also be applied to the copolymer film of When a fluorine-containing copolymer film having a saponification degree of 95% or more is produced by the melt extrusion method, a film obtained by forming a copolymer having a saponification degree of 50 to 80% by the melt extrusion method. Can be saponified to obtain the desired product film. Wet method, dry-wet method,
A flat membrane, a tube, or a hollow fiber can be produced by any of the melt extrusion methods, and is appropriately selected depending on its application.
【００１６】[0016]
【実施例】以下、実施例により本発明を具体的に説明す
る。 実施例１ ＴＦＥとＶＡｃとの共重合体１００重量部（粘度平均分
子量：２２万、ＴＦＥ：ＶＡｃのモル比＝２２：７８）
を加水分解し、ケン化度９７％の含フッ素共重合体６２
重量部を得た。得られた共重合体１５重量部を、ポリビ
ニルアルコール（重合度約５００）１５重量部とＮ，Ｎ
−ジメチルホルムアミド７０重量部に加えて均一に溶解
し、ドープ液１００重量部を得た。ドープ液を脱泡、濾
過後ガラス板上に厚さ２００μｍとなるように流延した
のち、０℃の冷水中に静かに入れ、凝固させた。得られ
た膜をガラス板から剥し、透水速度を測定すると、２２
０リットル／ｍ2・ｈｒ・ａｔｍであった。さらに９０
℃の熱水の透過速度を測定すると２３２リットル／ｍ2
・ｈｒ・ａｔｍであった。これを２４時間続けた後の熱
水の透過速度は１４２リットル／ｍ2・ｈｒ・ａｔｍで
あった。透水性の測定に用いられた膜の重量変化は見ら
れず、共重合体の水への溶出は検出されなかった。EXAMPLES The present invention will be specifically described below with reference to examples. Example 1 100 parts by weight of a copolymer of TFE and VAc (viscosity average molecular weight: 220,000, TFE: VAc molar ratio = 22: 78)
To give a fluorine-containing copolymer 62 having a saponification degree of 97%.
Parts by weight were obtained. 15 parts by weight of the obtained copolymer was mixed with 15 parts by weight of polyvinyl alcohol (polymerization degree: about 500) and N, N.
-Adding to 70 parts by weight of dimethylformamide and uniformly dissolving, 100 parts by weight of a dope solution was obtained. After defoaming and filtering the dope solution, the dope solution was cast on a glass plate so as to have a thickness of 200 μm, and then gently poured into cold water at 0 ° C. to solidify. The obtained film was peeled off from the glass plate and the water permeation rate was measured.
It was 0 liter / m 2 · hr · atm. 90 more
The permeation rate of hot water at ℃ is 232 liters / m 2
・ It was hr ・ atm. After continuing this for 24 hours, the permeation rate of hot water was 142 liter / m 2 · hr · atm. No change in weight of the membrane used for water permeability measurement was observed, and elution of the copolymer into water was not detected.
【００１７】実施例２ 加水分解反応に用いた共重合体の粘度平均分子量が３４
万で、反応後のケン化度が９８％である以外は、実施例
１と同様にドープ液を調製し、内管の外径が０．６ｍ
ｍ、外管の内径が１．０ｍｍの２重管ノズルを用い、乾
湿法により中空糸を調製した。この中空糸を束ね、膜面
積２５１ｃｍ2のモジュールを作製し、透水速度を測定
すると、１７４リットル／ｍ2・ｈｒ・ａｔｍであっ
た。さらにこのモジュールで３５℃の水を７日間濾過
し、膜表面の汚れのため透水速度が８２リットル／ｍ2
・ｈｒ・ａｔｍまで低下した時点で膜表面の洗浄を行っ
た結果、透水度は１５２リットル／ｍ2・ｈｒ・ａｔｍ
に回復した。Example 2 The copolymer used in the hydrolysis reaction had a viscosity average molecular weight of 34.
However, the dope solution was prepared in the same manner as in Example 1 except that the saponification degree after the reaction was 98%, and the outer diameter of the inner tube was 0.6 m.
m, a hollow fiber was prepared by a dry-wet method using a double-tube nozzle having an outer tube with an inner diameter of 1.0 mm. The hollow fibers were bundled to prepare a module having a membrane area of 251 cm 2 , and the water permeation rate was measured and found to be 174 liter / m 2 · hr · atm. Furthermore, water at 35 ° C. was filtered for 7 days with this module, and the water permeation rate was 82 liters / m 2 due to dirt on the membrane surface.
・ When the membrane surface was washed at the time when it dropped to hr ・ atm, the water permeability was 152 liters / m 2・ hr ・ atm.
Recovered.
【００１８】実施例３ 粘度平均分子量４２万、ＴＦＥ：ＶＡｃのモル比が２
３：７７のＴＦＥ／ＶＡｃ共重合体を加水分解し、ケン
化度８２％の含フッ素共重合体を得た。この共重合体に
ジエチレングリコールを助剤として加え、溶融押出し法
で厚さ２０μｍの膜を調製した。この膜を十分に水洗し
た後、１２１℃のオートクレーブ中で１５分間滅菌し
て、抗血栓性テストの試料とした。滅菌時における含フ
ッ素共重合体の溶出は検出されなかった。この膜に対
し、ヒト新鮮静脈血を３７℃で６分間接触させた後、生
理食塩水で洗浄し血餅の付着量を観察した結果、血餅の
付着はみられなかった。Example 3 Viscosity average molecular weight of 420,000, TFE: VAc molar ratio of 2
The 3:77 TFE / VAc copolymer was hydrolyzed to obtain a fluorine-containing copolymer having a saponification degree of 82%. Diethylene glycol was added as an auxiliary agent to this copolymer, and a film having a thickness of 20 μm was prepared by a melt extrusion method. After thoroughly washing this membrane with water, it was sterilized in an autoclave at 121 ° C. for 15 minutes to prepare a sample for the antithrombotic test. No elution of the fluorocopolymer during sterilization was detected. Human fresh venous blood was brought into contact with this membrane at 37 ° C. for 6 minutes, washed with physiological saline, and the amount of clot adhered was observed. As a result, no clot adhered was observed.
【００１９】[0019]
【発明の効果】本発明にかかる含フッ素共重合体膜は、
前記実施例からも明らかなように、従来のポリビニルア
ルコール系重合体膜の場合とは異なり、成膜後、なんら
化学的、物理的処理を施すことなく、製品膜とすること
ができる。この製品膜は、適度な親水性を保ちながら、
耐水性、特に耐熱水性、耐オートクレーブ性に極めて優
れている。また、さらに特筆すべきことに、高い耐汚染
性、抗血栓性を有しており、水処理、あるいは医療分野
での使用に非常に有効である。本発明の含フッ素共重合
体膜は、ガスや液体の分離膜として好適に用いられる。
このような分離膜には、例えば、血液透析用分離膜や、
血漿分離膜、水処理用精密濾過膜等が包含される。The fluorine-containing copolymer film according to the present invention is
As is clear from the above examples, unlike the conventional polyvinyl alcohol-based polymer film, a product film can be formed without any chemical or physical treatment after film formation. This product film keeps an appropriate hydrophilicity,
Excellent water resistance, especially hot water resistance and autoclave resistance. Moreover, it should be noted that it has high stain resistance and antithrombogenicity, and is very effective for water treatment or use in the medical field. The fluorine-containing copolymer membrane of the present invention is suitably used as a gas or liquid separation membrane.
Such a separation membrane includes, for example, a separation membrane for hemodialysis,
Plasma separation membranes, microfiltration membranes for water treatment, etc. are included.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.5 識別記号 庁内整理番号 ＦＩ 技術表示箇所 Ｃ０８Ｌ 27/18 ＬＧＬ 9166−4Ｊ ─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 5 Identification code Office reference number FI technical display location C08L 27/18 LGL 9166-4J
Claims (3)
の共重合体又は該共重合体に含まれるアセテート基の少
なくとも一部をケン化した共重合体からなり、該共重合
体中に含まれるテトラフルオロエチレン含有率が１〜７
０モル％であることを特徴とする含フッ素共重合体膜。1. A tetrafluoroethylene contained in the copolymer, which comprises a copolymer of tetrafluoroethylene and vinyl acetate or a copolymer obtained by saponifying at least a part of the acetate group contained in the copolymer. Ethylene content is 1 to 7
A fluorine-containing copolymer film, characterized in that it is 0 mol%.
ある請求項１の含フッ素共重合体膜。2. The fluorine-containing copolymer film according to claim 1, wherein the saponification degree of the copolymer is 50 to 100%.
らなる分離膜。3. A separation membrane comprising the fluorine-containing copolymer membrane according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9357192A JPH05261256A (en) | 1992-03-19 | 1992-03-19 | Fluorine-containing copolymer film and separating membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9357192A JPH05261256A (en) | 1992-03-19 | 1992-03-19 | Fluorine-containing copolymer film and separating membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH05261256A true JPH05261256A (en) | 1993-10-12 |
Family
ID=14085948
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9357192A Withdrawn JPH05261256A (en) | 1992-03-19 | 1992-03-19 | Fluorine-containing copolymer film and separating membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH05261256A (en) |
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