JP2909561B2 - Method for improving water permeability of porous plastic membrane - Google Patents
Method for improving water permeability of porous plastic membraneInfo
- Publication number
- JP2909561B2 JP2909561B2 JP21220990A JP21220990A JP2909561B2 JP 2909561 B2 JP2909561 B2 JP 2909561B2 JP 21220990 A JP21220990 A JP 21220990A JP 21220990 A JP21220990 A JP 21220990A JP 2909561 B2 JP2909561 B2 JP 2909561B2
- Authority
- JP
- Japan
- Prior art keywords
- olefin polymer
- fluorinated olefin
- water permeability
- membrane
- porous fluorinated
- 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.)
- Expired - Lifetime
Links
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、多孔質フッ化オレフィン重合体膜の透水性
改善方法に関する。Description: TECHNICAL FIELD The present invention relates to a method for improving water permeability of a porous fluorinated olefin polymer membrane.
従来の技術 多孔質フッ化オレフィン重合体膜は、耐薬品性、熱的
特性、生物化学的耐久性等にすぐれるところから、分離
膜素材として種々の工業分野で用いられているが、特
に、半導体関連分野においては、薬品中の微粒子等の異
物の除去に広く用いられている。2. Description of the Related Art Porous fluorinated olefin polymer membranes are used in various industrial fields as separation membrane materials because of their excellent chemical resistance, thermal properties, and biochemical durability. In the field of semiconductors, it is widely used for removing foreign substances such as fine particles in chemicals.
しかし、多孔質フッ化オレフィン重合体膜は、その臨
界界面張力が低いために、そのままでは表面張力の高い
液体、特に水溶液を濾過することができない。そこで、
従来、多孔質フッ化オレフィン重合体膜で表面張力の高
い液体を濾過しようとするときは、そのフッ化オレフィ
ン重合体膜を予めアルコール等の親水性有機溶剤て処理
し、膜中の微細孔を湿潤処理した後、この有機溶剤を濾
過対象である液体で置換することが行なわれている。し
かし、かかる方法は手間を要すると共に、環境安全性の
点からも必ずしも望ましい方法とはいえない。However, since the porous fluorinated olefin polymer membrane has a low critical interfacial tension, a liquid having a high surface tension, particularly an aqueous solution, cannot be filtered as it is. Therefore,
Conventionally, when it is intended to filter a liquid having a high surface tension with a porous fluorinated olefin polymer membrane, the fluorinated olefin polymer membrane is previously treated with a hydrophilic organic solvent such as alcohol to remove fine pores in the membrane. After the wet treatment, the organic solvent is replaced with a liquid to be filtered. However, such a method requires time and effort and is not always desirable from the viewpoint of environmental safety.
一方、既に、多孔質フッ化オレフィン重合体膜の透水
性を改善する方法として、特公昭53−31827号公報に記
載されているように、膜をスパッタエッチング処理する
方法が知られている。この方法によれば、膜表面がエツ
チングされて、水に対する濡れ性が改善されるものとみ
られるが、親水性基が膜に導入されることは少なく、か
くして、透水性の改善効果にも限度がある。On the other hand, as a method for improving the water permeability of a porous fluorinated olefin polymer film, a method of sputter etching a film has been known as described in JP-B-53-31827. According to this method, it is considered that the membrane surface is etched and the wettability to water is improved, but the hydrophilic group is rarely introduced into the membrane, and thus the effect of improving the water permeability is limited. is there.
また、多孔質フッ化オレフィン重合体膜の透水性を改
善する方法として、特開昭62−19207号公報に記載され
ているように、膜をコロナ放電処理する方法も知られて
いる。しかし、一般に、フッ化オレフィン重合体は、フ
ッ素原子が重合体主鎖をいわば保護しているために、重
合体主鎖に水酸基、カルボニル基、カルボキシル基等の
親水性基を導入することが、同様に、容易ではなく、前
述した方法と同じく、フッ化オレフィン重合体膜の透水
改善の効果に限界がある。As a method for improving the water permeability of a porous fluorinated olefin polymer membrane, there is also known a method of performing corona discharge treatment on a membrane as described in JP-A-62-19207. However, in general, a fluorinated olefin polymer has a fluorine atom protecting the polymer main chain, so to speak, it is possible to introduce a hydroxyl group, a carbonyl group, a hydrophilic group such as a carboxyl group into the polymer main chain, Similarly, it is not easy, and similarly to the above-described method, there is a limit to the effect of improving the water permeability of the fluorinated olefin polymer membrane.
発明が解決しようとする課題 本発明者らは、多孔質フッ化オレフィン重合体膜の透
水性改善における上記した問題を解決するために鋭意研
究した結果、スパッタエッチング処理及びコロナ放電処
理がいずれも、それら単独ではフッ化オレフィン重合体
膜の透水性の改善効果に限界があるにもかかわらず、多
孔質フッ化オレフィン重合体膜を先ずスパッタエッチン
グ処理し、次いで、コロナ放電処理することによって、
多孔質フッ化オレフィン重合体の透水性を予期し得ない
ことに著しく改善し得ることを見出して、本発明に至っ
たものである。Problems to be Solved by the Invention The present inventors have conducted intensive studies to solve the above-mentioned problems in improving the water permeability of the porous fluorinated olefin polymer film, and as a result, both the sputter etching treatment and the corona discharge treatment were performed. Despite the limited effect of improving the water permeability of the fluorinated olefin polymer film alone, the porous fluorinated olefin polymer film is first sputter-etched, and then subjected to corona discharge treatment.
The inventors have found that the water permeability of the porous fluorinated olefin polymer can be remarkably improved unexpectedly, and have led to the present invention.
課題を解決するための手段 本発明による多孔質フッ化オレフィン重合体膜の透水
性改善方法は、多孔質フッ化オレフィン重合体膜をスパ
ッタエッチング処理し、次いで、コロナ放電処理するこ
とを特徴とする。Means for Solving the Problems The method for improving the water permeability of a porous fluorinated olefin polymer film according to the present invention is characterized in that the porous fluorinated olefin polymer film is subjected to sputter etching treatment, and then to corona discharge treatment. .
本発明の方法において、多孔質フッ化オレフィン重合
体膜として、ポリテトラフルオロエチレン、ポリフッ化
ビニリデン、四フッ化エチレン−六フッ化ピロピレン共
重合体、パーフルオロアルコキシ樹脂、エチレン−四フ
ッ化エチレン共重合体等からなる膜を挙げることができ
る。In the method of the present invention, as the porous fluorinated olefin polymer film, polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene-hexafluoropyrene copolymer, perfluoroalkoxy resin, ethylene-tetrafluoroethylene copolymer may be used. A film made of a polymer or the like can be given.
かかる多孔質フッ化オレフィン重合体膜は、平均孔径
0.01〜100μｍ、好ましくは0.1〜10μｍ、膜厚100〜500
μｍ、好ましくは50〜200μｍ、多孔度１〜90％、好ま
しくは10〜70％の範囲にある。Such a porous fluorinated olefin polymer membrane has an average pore size
0.01-100 μm, preferably 0.1-10 μm, film thickness 100-500
μm, preferably 50-200 μm, porosity 1-90%, preferably 10-70%.
本発明において、このような多孔質フッ化オレフィン
重合体膜のスパッタエッチング処理は、雰囲気圧0.0005
〜1Torrの下で電力密度と処理時間との積で表わされる
処理量を0.1〜50W・秒／cm2の範囲とすることが好まし
い。電源としては、数百KHz乃至数十MHzの高周波電力が
用いられる。電極間距離は雰囲気圧Ｐの1/√Ｐに比例
し、例えば、雰囲気圧0.005Torrのとき、30cm以上であ
る。雰囲気ガスは、特に限定されるものではないが、通
常、不活性ガス、空気、水蒸気、炭酸ガス等が好ましく
用いられる。In the present invention, the sputter etching of such a porous fluorinated olefin polymer film is performed at an atmospheric pressure of 0.0005.
It is preferable that the processing amount represented by the product of the power density and the processing time under 1 Torr is in the range of 0.1 to 50 W · sec / cm 2 . As a power supply, high-frequency power of several hundred KHz to several tens MHz is used. The distance between the electrodes is proportional to 1 / √P of the atmospheric pressure P, and is, for example, 30 cm or more when the atmospheric pressure is 0.005 Torr. The atmosphere gas is not particularly limited, but usually, an inert gas, air, water vapor, carbon dioxide gas or the like is preferably used.
本発明の方法によれば、このようなスパッタエッチン
グ処理によつて、多孔質フッ化オレフィン重合体膜をエ
ッチングした後、その膜に更にコロナ放電処理が施され
る。コロナ放電処理は、膜表面をコロナ放電に曝すよう
に電極を設け、ギャップ長さ１〜5mmで出力１〜1000W/m
2・分を印加し、処理すればよい。According to the method of the present invention, after the porous fluorinated olefin polymer film is etched by such a sputter etching treatment, the film is further subjected to a corona discharge treatment. In the corona discharge treatment, electrodes are provided so that the film surface is exposed to corona discharge, and the output is 1 to 1000 W / m with a gap length of 1 to 5 mm.
What is necessary is just to apply 2 minutes and process.
発明の効果 本発明によれば、多孔質フッ化オレフィン重合体膜を
スパッタエッチング処理して、エッチング効果によっ
て、膜の数千Å以下の表面層の構造を変化させる。即
ち、重合体膜の表面の重合体鎖を囲んでいるフッ化原子
等の疎水性基の規則性を変更させる。このような多孔質
フッ化オレフィン重合体膜に更にコロナ放電処理を施す
ことによって、膜面に水酸基が容易に導入され、その結
果として、透水性が飛躍的に高められる。Effects of the Invention According to the present invention, a porous fluorinated olefin polymer film is subjected to sputter etching treatment, and the structure of the surface layer having a thickness of several thousand mm or less is changed by the etching effect. That is, the regularity of a hydrophobic group such as a fluorine atom surrounding the polymer chain on the surface of the polymer film is changed. By further performing corona discharge treatment on such a porous fluorinated olefin polymer membrane, hydroxyl groups are easily introduced into the membrane surface, and as a result, the water permeability is drastically increased.
実施例 以下に実施例を挙げて本発明を説明するが、本発明は
これら実施例により何ら限定されるものではない。EXAMPLES Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
第１表に示す多孔質フッ化オレフィン重合体膜を下記
に示す条件でスパッタエッチング処理し、次いで、コロ
ナ放電処理した。また、比較のために、スパッタエッチ
ング処理又はコロナ放電処理のみを行なった。これらの
膜について、純粋透水速度を第１表に示す。The porous fluorinated olefin polymer films shown in Table 1 were sputter-etched under the conditions shown below, and then subjected to corona discharge treatment. For comparison, only a sputter etching process or a corona discharge process was performed. Table 1 shows the pure water permeation rates for these membranes.
スパッタエッチング処理 雰囲気圧 ５×10-2Torr 雰囲気ガス アルゴン 放電電力密度（供給電力／電極面積）×放電時間 3W・
秒／cm2 コロナ放電処理 出力 150W/m2・分 ギャップ長さ 2mm 処理時間 0.5秒 Sputter etching process Atmospheric pressure 5 × 10 -2 Torr Atmospheric gas Argon Discharge power density (supply power / electrode area) × discharge time 3W
Sec / cm 2 Corona discharge treatment Output 150W / m 2 · min Gap length 2mm Treatment time 0.5sec
───────────────────────────────────────────────────── フロントページの続き (58)調査した分野(Int.Cl.6，ＤＢ名) B01D 71/32 - 71/36 B01D 67/00 500 B01D 69/02 ──────────────────────────────────────────────────続 き Continued on the front page (58) Field surveyed (Int. Cl. 6 , DB name) B01D 71/32-71/36 B01D 67/00 500 B01D 69/02
Claims (1)
タエッチング処理し、次いで、コロナ放電処理すること
を特徴とする多孔質フッ化オレフィン重合体膜の透水性
改善方法。1. A method for improving the water permeability of a porous fluorinated olefin polymer film, which comprises subjecting the porous fluorinated olefin polymer film to a sputter etching treatment, followed by a corona discharge treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21220990A JP2909561B2 (en) | 1990-08-10 | 1990-08-10 | Method for improving water permeability of porous plastic membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21220990A JP2909561B2 (en) | 1990-08-10 | 1990-08-10 | Method for improving water permeability of porous plastic membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0494724A JPH0494724A (en) | 1992-03-26 |
| JP2909561B2 true JP2909561B2 (en) | 1999-06-23 |
Family
ID=16618736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21220990A Expired - Lifetime JP2909561B2 (en) | 1990-08-10 | 1990-08-10 | Method for improving water permeability of porous plastic membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2909561B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5626269B2 (en) | 2011-06-22 | 2014-11-19 | ダイキン工業株式会社 | Polymer porous membrane and method for producing polymer porous membrane |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5331827B2 (en) | 2011-01-12 | 2013-10-30 | 株式会社日立メディアエレクトロニクス | Optical pickup device and optical component bonding method |
-
1990
- 1990-08-10 JP JP21220990A patent/JP2909561B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5331827B2 (en) | 2011-01-12 | 2013-10-30 | 株式会社日立メディアエレクトロニクス | Optical pickup device and optical component bonding method |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0494724A (en) | 1992-03-26 |
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