JP3242983B2 - Fluorine-based hydrophilic microporous membrane and method for producing the same - Google Patents
Fluorine-based hydrophilic microporous membrane and method for producing the sameInfo
- Publication number
- JP3242983B2 JP3242983B2 JP12632392A JP12632392A JP3242983B2 JP 3242983 B2 JP3242983 B2 JP 3242983B2 JP 12632392 A JP12632392 A JP 12632392A JP 12632392 A JP12632392 A JP 12632392A JP 3242983 B2 JP3242983 B2 JP 3242983B2
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- Prior art keywords
- membrane
- ozone
- water
- treatment
- fluorine
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Description
【０００１】[0001]
【産業上の利用分野】本発明は、オゾンを含む水をろ過
処理するのに適した親水性膜及びその製造方法に関する
ものである。The present invention relates are those which relate to a hydrophilic membrane and its production how suitable for filtration of water containing ozone.
【０００２】[0002]
【従来の技術】河川水や工業廃水等を浄化するにあた
り、従来はポリ塩化アルミニウム等の凝集剤を用いて水
中の濁度物質を凝集、フロック形成させることによって
浄化を行っている。凝集剤添加による水の浄化法につい
ては、例えば、浄水の技術（丹保憲仁・小笠原紘一共
著，技報堂出版，1985）第２章に詳しい記述がある。し
かし、この様な方法では原水（河川水、地下水、廃水
等）の水質が変動した場合、このため有効な処理を行う
には、その変動に応じて添加する凝集剤の量やｐＨ等を
最適化していく必要があり、いわゆるジャーテストとい
った予備テストが要求される。この様に、従来法では操
作が煩雑である上にフロック形成池や沈澱池、砂ろ過設
備等の大型設備が必要であり、また、凝集剤添加により
生成した大量のスラッジの処理が問題となっている。2. Description of the Related Art In purifying river water, industrial wastewater, and the like, conventionally, purification is performed by coagulating turbid substances in water using flocculants such as polyaluminum chloride and forming flocs. The method of purifying water by adding a flocculant is described in detail in, for example, Chapter 2 of Water Purification Technology (Norihito Tanbo and Koichi Ogasawara, Gihodo Shuppan, 1985). However, in such a method, when the water quality of raw water (river water, groundwater, wastewater, etc.) fluctuates, in order to perform effective treatment, the amount and pH of the coagulant to be added should be optimized according to the fluctuation. It is necessary to make a preliminary test such as a so-called jar test. As described above, in the conventional method, the operation is complicated, and large facilities such as a floc forming pond, a sedimentation pond, and a sand filtration facility are required, and a large amount of sludge generated by adding a flocculant becomes a problem. ing.
【０００３】以上のような凝集沈澱法の持つ欠点を克服
し、コンパクトな設備でかつ原水変動に大きく左右され
ることなく安定した水質を得るために、多孔膜を用いた
新たなプロセスが提案されてきている。しかし、多孔膜
を用いた場合には処理水の透過流速が経時的に急減する
といった問題がある。（ニューメンブレンテクノロジー
シンポジウム’９２，日本膜学会・（社）日本能率協会
主催，予稿集 ＳＥＳＳＩＯＮ ３，１９９２）これら
の問題を解決するために、近年オゾンによって原水をあ
らかじめ処理することにより処理水の透過流速の経時的
減少を抑制したり（Ｊｏｕｒ．ＡＷＷＡ，ｖｏｌ．７
７，Ｎｏ．８，６０−６５，１９８５）、洗浄時や逆洗
時にオゾンを含む水を用いることにより（特開昭６３−
９３３１０号公報、特開平３−２４９９２７号公報）、
低下した透過流速の回復をはかる方法が提案されてい
る。また、特開平４−１０８５１８号公報においては、
オゾン注入装置を組み込んだろ過装置の開示がある。こ
うしたオゾン処理は膜の目詰まりが有機物質に起因する
場合に特に有効であるが、オゾンの強い酸化力により膜
自体が酸化劣化を受けるといった問題があり、使用でき
る膜としてはたとえばセラッミク膜やフッ素系の膜に限
られていた。ところが、これらの膜は、セラッミク膜に
おいては高価であり、かつ、設備のコンパクト化に限界
があるといった問題があり、フッ素系の膜においては膜
自体が疎水性であるため、使用に際し、あらかじめアル
コール処理などの前処理が必須であり、また、水処理中
に気泡が細孔内に入ることにより透過流速が低下すると
いった問題がある。A new process using a porous membrane has been proposed in order to overcome the above-mentioned drawbacks of the coagulation-sedimentation method and obtain stable water quality with compact equipment and without being largely affected by fluctuations in raw water. Is coming. However, when a porous membrane is used, there is a problem that the permeation flow rate of the treated water rapidly decreases with time. (New Membrane Technology Symposium '92, sponsored by The Japan Membrane Society / Japan Management Association, proceedings SESSION 3,1992) To solve these problems, in recent years, the permeated water has been treated by previously treating raw water with ozone. It is possible to suppress the time-dependent decrease in the flow rate (Jour. AWA, vol. 7).
7, No. 8, 60-65, 1985) by using water containing ozone during washing or back washing (Japanese Patent Laid-Open No.
No. 93310, JP-A-3-249927),
A method for recovering the reduced permeation flow rate has been proposed. Also, in JP-A-4-108518,
There is a disclosure of a filtration device incorporating an ozone injection device. Such an ozone treatment is particularly effective when clogging of the film is caused by an organic substance. However, there is a problem that the film itself is oxidized and degraded by the strong oxidizing power of ozone. Examples of usable films include a ceramic film and a fluorine film. The system was limited to membranes. However, these membranes are expensive in the case of ceramic membranes, and there is a problem in that there is a limit to downsizing of equipment.Because the membranes themselves are hydrophobic in fluorine-based membranes, alcoholic membranes must be used before use. Pretreatment such as treatment is indispensable, and there is a problem that the permeation flow rate decreases due to bubbles entering pores during water treatment.
【０００４】フッ素系の膜においては、その疎水性が故
の問題点を解消するために、表面を親水化する手法が検
討されている。フッ素系のポリマーに親水性を付与させ
る方法としては、たとえば、金属ナトリウム−アンモニ
ア法、ナトリウム−ナフタリン−テトラヒドロフラン法
等が提案されているが、これらの方法に関しては処理液
が水洗時に激しく反応する点、及び処理液の寿命が短く
処理能力が制限されてしまう点などの欠点を有してい
る。また、ＰＶｄＦに関してはアルカリ処理により表面
が親水化されることが、例えば特公昭４６−１１９９５
号公報、特公昭４６−１１９９６号公報および特公昭６
２−１７６１４号公報に開示されているが、これらの処
理により親水化された膜は膜の着色や、膜からの溶出が
あり問題となっている。[0004] In order to solve the problems caused by the hydrophobicity of the fluorine-based film, a method for making the surface hydrophilic has been studied. As a method for imparting hydrophilicity to a fluorine-based polymer, for example, a sodium metal-ammonia method, a sodium-naphthalene-tetrahydrofuran method, and the like have been proposed. And that the processing liquid has a short life and the processing capacity is limited. Regarding PVdF, it is known that the surface is made hydrophilic by alkali treatment, for example, Japanese Patent Publication No. 46-11995.
JP, JP-B-46-11996 and JP-B-6-1996
As disclosed in Japanese Patent Application Laid-Open No. 2-17614, the film hydrophilized by these treatments is problematic because the film is colored and eluted from the film.
【０００５】[0005]
【発明が解決しようとする課題】本発明は、河川水、地
下水または工業廃水等を多孔膜を用いて浄化するにあた
り、オゾン存在下にてろ過処理することによるろ過水量
低減の抑制、または、オゾン処理による膜の洗浄を含む
水処理プロセスにおいて有効であり、かつ、安価な耐オ
ゾン性を有するフッ素系親水性微多孔膜及びその製造方
法の提供を目的とするものである。SUMMARY OF THE INVENTION The present invention relates to a method for purifying river water, groundwater or industrial wastewater using a porous membrane, which suppresses a reduction in the amount of filtered water by performing a filtration treatment in the presence of ozone. Inexpensive ozone-resistant microporous fluorinated hydrophilic membrane that is effective in water treatment processes including membrane cleaning by treatment and method of producing the same
It is intended to provide the law .
【０００６】[0006]
【課題を解決するための手段】本発明者らは、上記の目
標を達成すべく鋭意研究を行った結果、以下の手段によ
り目的を達成することができることを見出した。本発明
者らは、耐オゾン性には優れるが疎水性であるフッ素系
微多孔膜を、あらかじめオゾン処理することにより、膜
の細孔表面に親水性が付与された、耐オゾン性を有する
フッ素系親水性微多孔膜が得られることを見出した。こ
うして得られた親水性膜は、特にアルコール処理などの
前処理を必要としなくとも濾過処理を開始することがで
き、また、水処理中に気泡などが細孔内に入ったとして
も、細孔表面が親水性であるため、その気泡は容易に細
孔外へ出され透過流量の低下にはつながらない。このよ
うな効果を得るためには、親水性は高いほうが好まし
く、たとえば親水化率７０％以上が良い。 Means for Solving the Problems The present inventors have made intensive studies to achieve the above-mentioned object, and as a result, have found that the object can be achieved by the following means. The present inventors have developed a microporous fluorine-based membrane that is excellent in ozone resistance but is hydrophobic by applying ozone treatment in advance to impart hydrophilicity to the pore surfaces of the membrane. It has been found that a hydrophilic microporous membrane can be obtained. The hydrophilic membrane thus obtained can be subjected to a filtration treatment without particularly requiring a pretreatment such as an alcohol treatment, and even if air bubbles and the like enter the pores during the water treatment, the pores are reduced. Since the surface is hydrophilic, the air bubbles are easily out of the pores and do not lead to a decrease in the permeation flow rate. This
In order to obtain such effects, higher hydrophilicity is preferred.
For example, the hydrophilicity is preferably 70% or more.
【０００７】この様に、従来の濾過膜にみられない優れ
たフッ素系親水性微多孔膜を発明するに至った。即ち、
本発明は、 １）、フッ素系ポリマーよりなる微多孔膜を、オゾンを
含む水で処理することを特徴とするフッ素系親水性微多
孔膜の製造方法。As described above, an excellent fluorine-based hydrophilic microporous membrane not found in a conventional filtration membrane has been invented. That is,
The present invention is, 1), a microporous film made of fluorine-based polymer, ozone
A method for producing a fluorine-containing hydrophilic microporous membrane , characterized by treating with water containing water .
【０００８】２）、フッ素系ポリマーよりなる微多孔膜
を、アルカリ処理したのちオゾン処 理することを特徴と
するフッ素系親水性微多孔膜の製造方法。に関するもの
である。2), a microporous membrane made of a fluoropolymer
And a characterized in that the ozone treatment After alkali treatment
Of producing a fluorine-containing hydrophilic microporous membrane. It is about.
【０００９】以下、本発明について具体的に説明する。
本発明に使用される微多孔膜としては、いわゆる限外ろ
過膜やマイクロフィルターが挙げられ、それらの孔径は
限外ろ過膜で５０〜５００オングストローム、マイクロ
フィルターで５００オングストローム〜５ミクロン程度
といわれている。（膜分離技術マニュアル，木村ら編，
アイピーシー出版，ｐ．４１，１９９０）また、その形
状としては逆洗、クロスフロー及びコンパクト化の容易
な中空糸状膜が好ましい。Hereinafter, the present invention will be described in detail.
Examples of the microporous membrane used in the present invention include so-called ultrafiltration membranes and microfilters, and their pore diameters are said to be about 50 to 500 angstroms for ultrafiltration membranes and about 500 angstroms to 5 microns for microfilters. I have. (Membrane separation technology manual, edited by Kimura et al.,
IPC Publishing, p. 41, 1990) Further, the shape is preferably a hollow fiber membrane which is easy to backwash, cross-flow and compact.
【００１０】膜の材質としては耐オゾン性が要求される
ためフッ素系のポリマーでなくてはならないが、オゾン
処理により膜の細孔表面が親水化される必要性があるた
め、ポリマー中に水素原子が存在することが好ましい。
たとえば、ポリビニルフルオライド（ＰＶＦ），ポリビ
ニリデンフルオライド（ＰＶｄＦ）等のように水素原子
を少なくとも１つは含むモノマーから重合されたフッ素
系ポリマーや、テトラフルオロエチレンーエチレン共重
合体（ＥＴＦＥ），クロロトリフルオロエチレンーエチ
レン共重合体（ＥＣＴＦＥ）等に代表される炭化水素系
オレフィンとフッ素系オレフィンとの共重合体、また、
エチレンに代表される炭化水素系オレフィンや、ビニル
フルオライド（ＶＦ），ビニリデンフルオライド（Ｖｄ
Ｆ）に代表される水素原子を１つ以上を含むフッ素系モ
ノマーをポリマーのエレメントとして含むフッ素系ポリ
マーがあげられる。製膜の容易さ及び機械的強度などの
点より、ポリビニリデンフルオライド膜はさらに好適で
ある。ポリテトラフルオロエチレン（ＰＴＦＥ）に代表
されるような水素原子を含まないポリマーはオゾンによ
る表面酸化が起こりにくく、親水化処理に要するオゾン
処理に時間がかかるため好ましくない。[0010] The material of the membrane must be a fluorine-based polymer because ozone resistance is required. However, since it is necessary to make the pore surface of the membrane hydrophilic by ozone treatment, hydrogen is contained in the polymer. Preferably, atoms are present.
For example, a fluoropolymer polymerized from a monomer containing at least one hydrogen atom such as polyvinyl fluoride (PVF), polyvinylidene fluoride (PVdF), etc., a tetrafluoroethylene-ethylene copolymer (ETFE), Copolymers of hydrocarbon olefins and fluorinated olefins represented by chlorotrifluoroethylene-ethylene copolymer (ECTFE) and the like,
Hydrocarbon olefins represented by ethylene, vinyl fluoride (VF), vinylidene fluoride (Vd
Examples of the fluorine-based polymer include a fluorine-based monomer containing at least one hydrogen atom represented by F) as a polymer element. The polyvinylidene fluoride film is more preferable from the viewpoints of ease of film formation and mechanical strength. Polymers containing no hydrogen atoms, such as polytetrafluoroethylene (PTFE), are not preferred because surface oxidation by ozone hardly occurs and ozone treatment required for hydrophilization takes time.
【００１１】膜の親水化方法に関しては、オゾンを含む
水に膜を浸漬またはオゾンを含む水を膜に通水しながら
行うが、処理効率の点から後者の方が好ましい。また、
オゾンを含む水を膜に通水する場合、膜をモジュール化
した後に行うと更に効率的である。オゾン処理の際の水
中オゾンの下限濃度は０．１ｐｐｍ以上、好ましくは
０．５ｐｐｍ以上、さらに好ましくは２ｐｐｍ以上であ
る。又、水中オゾンの上限濃度は、好ましくは５０ｐｐ
ｍ以下、より好ましくは３０ｐｐｍ以下、さらに好まし
くは２０ｐｐｍ以下である。オゾン濃度が低すぎると膜
の表面に親水性を付与するまでに時間がかかりすぎ実用
的ではなく、また、高濃度のオゾンで処理する場合には
通常のオゾン発生機では対応できず装置が特殊化するた
め好ましくない。The method for hydrophilizing the membrane is carried out by immersing the membrane in water containing ozone or by passing water containing ozone through the membrane. The latter is preferred from the viewpoint of processing efficiency. Also,
In the case where water containing ozone is passed through the membrane, it is more efficient if the membrane is modularized. The lower limit concentration of ozone in water at the time of ozone treatment is 0.1 ppm or more, preferably 0.5 ppm or more, and more preferably 2 ppm or more. The upper limit concentration of ozone in water is preferably 50 pp.
m, preferably 30 ppm or less, more preferably 20 ppm or less. If the ozone concentration is too low, it takes too much time to impart hydrophilicity to the surface of the film, and it is not practical. Is not preferred because
【００１２】本発明において使用される、水素原子を含
有するフッ素系ポリマーは耐酸化性が比較的高いため、
オゾン処理に先だって、あらかじめアルカリ処理を施す
ことが好ましい。この処理は特に、ＰＶｄＦ，ＰＶＦか
らなる膜及び膜を形成するポリマー骨格にＶｄＦまたは
ＶＦエレメントが含まれている場合に有効である。アル
カリ試薬としては、例えば水酸化ナトリウム、水酸化カ
リウム等のアルカリ金属水酸化物、水酸化マグネシウ
ム、水酸化カルシウム等のアルカリ土類金属水酸化物、
テトラブチルアンモニウムヒドロキシドで代表される４
級アンモニウム水酸化物、アルカリ金属またはアルカリ
土類金属アルコキシド類、トリエチルアミン、１，４−
Ｄｉａｚａｂｉｃｙｃｌｏ［２．２．２］ｏｃｔａｎ
ｅ、１，８−Ｄｉａｚａｂｉｃｙｃｌｏ［５．４．０］
ｕｎｄｅｃ−７−ｅｎｅ、１，５−Ｄｉａｚａｂｉｃｙ
ｃｌｏ［４．３．０］ｎｏｎ−５−ｅｎｅ等の有機アミ
ン類があげられる。これらのアルカリ試薬のうち、液体
状のものをそのまま膜のアルカリ処理に用いることもで
きるが、あまりアルカリ処理が強すぎた場合には膜強度
に問題をきたすため、反応のコントロールを容易にする
ために、上記アルカリ試薬の水溶液またはエタノール等
の極性有機溶媒溶液を用いることが好ましい。The fluorine-containing polymer containing a hydrogen atom used in the present invention has relatively high oxidation resistance.
Prior to the ozone treatment, an alkali treatment is preferably performed in advance. This treatment is particularly effective when the film composed of PVdF or PVF and the polymer skeleton forming the film contain VdF or VF element. As the alkaline reagent, for example, sodium hydroxide, alkali metal hydroxides such as potassium hydroxide, magnesium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide,
4 represented by tetrabutylammonium hydroxide
Secondary ammonium hydroxide, alkali metal or alkaline earth metal alkoxides, triethylamine, 1,4-
Diabiccyclo [2.2.2] octan
e, 1,8-Diazabicyclo [5.4.0]
undec-7-ene, 1,5-Diazabicy
and organic amines such as clo [4.3.0] non-5-ene. Of these alkali reagents, the liquid reagent can be used as it is for the alkali treatment of the membrane, but if the alkali treatment is too strong, there is a problem in the membrane strength, and in order to facilitate the control of the reaction. It is preferable to use an aqueous solution of the above alkaline reagent or a solution of a polar organic solvent such as ethanol.
【００１３】本発明により、耐オゾン性を有し、かつ、
親水性で溶出の少ない膜の提供が可能となり、これによ
り長期にわたるオゾン含有水の膜処理及びオゾン含有水
による繰り返し洗浄（逆洗を含む）が可能となるため、
その水処理分野へ与える貢献度には絶大なものがある。
また、本発明において得られる膜はその溶出性が低いこ
とより、超純水製造分野においても有効であり、特にオ
ゾン共存系で使用される場合にその特性を生かすことが
できる。According to the present invention, it has ozone resistance and
It is possible to provide a hydrophilic and less eluting membrane, which enables long-term ozone-containing water membrane treatment and repeated washing (including backwashing) with ozone-containing water.
Its contribution to the water treatment field is enormous.
In addition, the membrane obtained in the present invention is effective in the field of ultrapure water production because of its low elution property, and can make use of its properties particularly when used in an ozone coexisting system.
【００１４】[0014]
【実施例】以下に実施例を用いて本発明をより具体的に
説明するが、本発明の範囲がこれらの実施例に限定され
るものではない。本実施例において用いられる膜の親水
化率とは、以下のようにして求めたものである。各例で
得られた各微多孔膜を、まず、乾燥した中空糸膜の内側
から限外ろ過膜で処理した純水を注入し、２ｋｇ／ｃｍ
2 に加圧し、５分間圧力を保持する。その後、圧力を１
ｋｇ／ｃｍ2 に設定し透水量Ａ（リットル／ｍ2 ・ｈｒ
・ａｔｍ ａｔ ２５℃）を求める。次に、該各微多孔
膜をあらかじめエタノールに浸漬した中空糸膜を限外ろ
過膜で処理した純水に浸漬、乾燥させることなく差圧１
ｋｇ／ｃｍ2 にて透水量Ｂを測定する。ここで、 親水化率＝（透水量Ａ÷透水量Ｂ）×１００ である。The present invention will be described in more detail with reference to the following examples, but the scope of the present invention is not limited to these examples. The hydrophilicity of the film used in the present example was determined as follows. First, pure water treated with an ultrafiltration membrane was injected from the inside of the dried hollow fiber membrane into each microporous membrane obtained in each example , and 2 kg / cm
Pressurize to 2 and hold pressure for 5 minutes. Then the pressure is increased to 1
Set to kg / cm 2 and permeate A (liter / m 2 · hr
・ Atm at 25 ° C). Next, each of the microporous membranes was immersed in ethanol beforehand, and the hollow fiber membrane was immersed in pure water treated with an ultrafiltration membrane, and dried without drying.
The water permeability B is measured at kg / cm 2 . Here, the ratio of hydrophilicity = (water permeability A 透 water permeability B) × 100.
【００１５】[0015]
【参考例１】特開平３−２１５５３５号公報（内容：Ｐ
ＶｄＦ多孔膜の製法）に開示されている方法に準拠し
て、平均孔径０．５μ、空孔率７０％のＰＶｄＦ中空糸
状多孔膜（外径：２．０ｍｍ、内径：１．１ｍｍ）を作
製した。ただし、シリカ抽出においてはアルカリ水溶液
を用いずにフッ酸水溶液を用いた。Reference Example 1 JP-A-3-215535 (contents: P
A PVdF hollow fiber-like porous membrane (outer diameter: 2.0 mm, inner diameter: 1.1 mm) having an average pore diameter of 0.5 μm and a porosity of 70% is produced according to the method disclosed in “VdF porous membrane production method”. did. However, in the silica extraction, a hydrofluoric acid aqueous solution was used without using an alkaline aqueous solution.
【００１６】得られた膜の親水化率は５％未満であっ
た。The degree of hydrophilicity of the obtained film was less than 5%.
【００１７】[0017]
【実施例１】参考例１で得られた膜をエタノール処理し
た後、限外ろ過膜で処理した純水に浸漬、更に乾燥させ
ることなくオゾン１０ｐｐｍを含む水中において１００
時間処理を行った。得られた膜は白色でその親水化率は
７０％であった。Example 1 After the membrane obtained in Reference Example 1 was treated with ethanol, the membrane was immersed in pure water treated with an ultrafiltration membrane, and further dried in water containing 10 ppm of ozone without drying.
Time processing was performed. The resulting film was white and had a hydrophilicity of 70%.
【００１８】[0018]
【実施例２】参考例１で得られた膜を１０％水酸化カリ
ウムエタノール溶液に浸漬し、室温下、超音波で１０分
間処理した。その後、限外ろ過膜で処理した純水で洗
浄、更に乾燥させることなくオゾン１０ｐｐｍを含む水
中において１時間処理を行った。得られた膜は白色でそ
の親水化率は７０％であった。Example 2 The film obtained in Reference Example 1 was immersed in a 10% ethanol solution of potassium hydroxide and treated with ultrasonic waves at room temperature for 10 minutes. Thereafter, the substrate was washed with pure water treated with an ultrafiltration membrane, and further treated in water containing 10 ppm of ozone for 1 hour without drying. The resulting film was white and had a hydrophilicity of 70%.
【００１９】[0019]
【比較例１】参考例１で得られた膜をエタノール処理し
た後、限外ろ過膜で処理した純水に浸漬、更に乾燥させ
ることなくオゾン１０ｐｐｍを含む水中において１時間
処理を行った。得られた膜の親水化率は５％未満であっ
た。COMPARATIVE EXAMPLE 1 The membrane obtained in Reference Example 1 was treated with ethanol, immersed in pure water treated with an ultrafiltration membrane, and further treated for 1 hour in water containing 10 ppm of ozone without drying. The hydrophilicity of the obtained film was less than 5%.
【００２０】[0020]
【参考例２】実施例１で得られた膜をエタノールに浸
漬、純水で洗浄後、更に乾燥させることなくオゾン１０
ｐｐｍを含む水中において５００時間処理を行った。得
られた膜の親水化率は７０％であり、機械物性上、顕著
な変化は認められなかった。また、本実施例におけるオ
ゾン処理の前後における膜の重量変化を測定したが、特
に差は認められなかった。REFERENCE EXAMPLE 2 The membrane obtained in Example 1 was immersed in ethanol, washed with pure water, and then dried without further drying.
The treatment was performed for 500 hours in water containing ppm. The hydrophilicity of the obtained film was 70%, and no remarkable change was recognized in mechanical properties. The weight change of the film before and after the ozone treatment in this example was measured, but no particular difference was observed.
【００２１】[0021]
【参考例３】実施例２で得られた膜をエタノールに浸
漬、純水で洗浄後、更に乾燥させることなくオゾン１０
ｐｐｍを含む水中において５００時間処理を行った。得
られた膜の親水化率は７０％であり、機械物性上、顕著
な変化は認められなかった。また、本実施例におけるオ
ゾン処理の前後における膜の重量変化を測定したが、特
に差は認められなかった。REFERENCE EXAMPLE 3 The membrane obtained in Example 2 was immersed in ethanol, washed with pure water, and then dried without further drying.
The treatment was performed for 500 hours in water containing ppm. The hydrophilicity of the obtained film was 70%, and no remarkable change was recognized in mechanical properties. The weight change of the film before and after the ozone treatment in this example was measured, but no particular difference was observed.
【００２２】上記各例から次のことを確認した。 ・オゾン処理による膜の親水化 実施例１と参考例１、実施例２と参考例１の結果を比較
することによりオゾン処理が膜の親水化に有効であるこ
とがわかる。 ・アルカリ処理効果 実施例２と比較例１の結果を比較することにより、アル
カリ処理を加える事によりオゾン処理時間が大幅に短縮
できることがわかる。The followings were confirmed from the above examples . Ozone treatment film hydrophilic Example 1 and Reference Example 1 by, it can be seen that ozone treatment by comparing the results of Example 2 and Reference Example 1 is effective in hydrophilizing the membrane. -Alkali treatment effect By comparing the results of Example 2 and Comparative example 1 , it can be seen that the ozone treatment time can be significantly reduced by adding the alkali treatment.
【００２３】・膜の耐オゾン性参考例２および３より、 実施例１及び実施例２で得られ
た膜が、オゾン１０ｐｐｍを含む水中に５００時間浸漬
された後に於いても、その親水性及び機械物性は変化せ
ず、またオゾン分解による膜の重量減少もないことがわ
かる。これらの結果、実施例１及び２で得られた膜が、
良好な耐オゾン性を示すことが判る。According to Reference Examples 2 and 3, the membranes obtained in Examples 1 and 2 exhibited hydrophilicity and hydrophilicity even after being immersed in water containing 10 ppm of ozone for 500 hours. It can be seen that the mechanical properties did not change and that the weight of the film did not decrease due to ozonolysis. As a result, the films obtained in Examples 1 and 2
It turns out that it shows good ozone resistance.
【００２４】[0024]
【発明の効果】本発明により、耐オゾン性に優れ、かつ
親水性の高分子多孔膜の提供が可能となる。According to the present invention, it is possible to provide a hydrophilic polymer porous membrane having excellent ozone resistance.
Claims (2)
オゾンを含む水で処理することを特徴とするフッ素系親
水性微多孔膜の製造方法。1. A microporous membrane comprising a fluoropolymer ,
A method for producing a fluorine-containing hydrophilic microporous membrane , characterized by treating with water containing ozone.
アルカリ処理したのちオゾン処理することを特徴とする
フッ素系親水性微多孔膜の製造方法。2. A microporous membrane comprising a fluoropolymer,
A method for producing a fluorine-based hydrophilic microporous membrane, which comprises performing an alkali treatment and then an ozone treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12632392A JP3242983B2 (en) | 1992-05-19 | 1992-05-19 | Fluorine-based hydrophilic microporous membrane and method for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12632392A JP3242983B2 (en) | 1992-05-19 | 1992-05-19 | Fluorine-based hydrophilic microporous membrane and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05317663A JPH05317663A (en) | 1993-12-03 |
| JP3242983B2 true JP3242983B2 (en) | 2001-12-25 |
Family
ID=14932345
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP12632392A Expired - Fee Related JP3242983B2 (en) | 1992-05-19 | 1992-05-19 | Fluorine-based hydrophilic microporous membrane and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3242983B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3727156B2 (en) * | 1997-10-22 | 2005-12-14 | オルガノ株式会社 | Desalination equipment |
| JP2006102721A (en) * | 2004-10-08 | 2006-04-20 | Nishi Nippon Filter Kk | Waste liquid treatment apparatus |
| JP2007313491A (en) * | 2006-04-25 | 2007-12-06 | Kureha Corp | Low stain resistance vinylidene fluoride family resin porosity water treatment membrane and its manufacturing method |
| JP6103794B1 (en) * | 2015-08-27 | 2017-03-29 | 三菱電機株式会社 | Water treatment method and water treatment apparatus |
| MY186114A (en) * | 2016-03-04 | 2021-06-22 | Mitsubishi Electric Corp | Membrane filtration device, filtration membrane cleaning method, and method for manufacturing filtration membrane |
-
1992
- 1992-05-19 JP JP12632392A patent/JP3242983B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05317663A (en) | 1993-12-03 |
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