JPS61125408A - Method for making porous polyolefin hollow yarn hydrophilic - Google Patents
Method for making porous polyolefin hollow yarn hydrophilicInfo
- Publication number
- JPS61125408A JPS61125408A JP59245606A JP24560684A JPS61125408A JP S61125408 A JPS61125408 A JP S61125408A JP 59245606 A JP59245606 A JP 59245606A JP 24560684 A JP24560684 A JP 24560684A JP S61125408 A JPS61125408 A JP S61125408A
- Authority
- JP
- Japan
- Prior art keywords
- vinyl acetate
- hollow yarn
- ethylene
- acetate copolymer
- wall surface
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
Abstract
Description
【発明の詳細な説明】
〔技術分野］
本発明は多孔質ポリオレフィン中空糸の親水化処理方法
に関する。DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for hydrophilizing porous polyolefin hollow fibers.
〔従来の技１１
純水製造や水中のコロイド状物の濾過等に用いる限外濾
過膜や精密症過膜としては種々の膜が知られているが、
その１つとしてポリオレフィン膜が知られている。ポリ
オレフィン膜は耐薬品性に債れる、溶融賦形法により膜
を製造できる等の利点から重用されており、本出願人も
特公昭５Ｂ−５２１２３号、特開昭５７−４２９１９号
において孔径０．０１〜１ルｍの微小空孔が中空糸の内
壁面と外壁面との間を連通ずる多孔質ポリオレフィン中
空糸を提案、した。[Conventional Technique 11 Various membranes are known as ultrafiltration membranes and precision filtration membranes used for pure water production, filtration of colloidal substances in water, etc.
Polyolefin membranes are known as one of them. Polyolefin membranes are widely used due to their advantages such as good chemical resistance and the ability to manufacture membranes by melt-forming. We have proposed a porous polyolefin hollow fiber in which micropores of 0.01 to 1 μm communicate between the inner and outer wall surfaces of the hollow fiber.
しかし、これは疎水性の多孔質ポリオレフィン中空糸で
あるので、使用前にアルコール等で一時的に親水化して
そのまま水と置換して用いるが、使用中に気泡が混入し
たり、保管時に水を抜いたりして多孔質ポリオレフィン
中空糸表面を空気と接触させて乾燥すると、！過性が低
下する問題があり、この様な問題のない親木性多孔質ポ
リオレフィン中空糸の開発が強く要望されていた。However, since this is a hydrophobic porous polyolefin hollow fiber, it is used by temporarily making it hydrophilic with alcohol etc. and replacing it with water before use. When the porous polyolefin hollow fiber surface is brought into contact with air and dried, the! There is a problem that the permeability decreases, and there has been a strong demand for the development of a wood-philic porous polyolefin hollow fiber that does not have this problem.
［解決しようとする問題点］
本発明の目的は多孔質ポリオレフィン中空糸を恒久的に
親水化する処理方法を提供することにある。[Problems to be Solved] An object of the present invention is to provide a treatment method for permanently making porous polyolefin hollow fibers hydrophilic.
ｃ問題点を解決するための手段］
本発明の上記目的は中空糸内壁面より外壁面へつながっ
た微小空孔を有するポリオレフィン中空糸の微小空孔を
形成している壁面の少なくとも１部にエチレン−ビニル
アセテート共重合体からなる薄膜を形成した後、該エチ
レン−ビニルアセテート共重合体を鹸化することを特徴
とする多孔質ポリオレフィン中空糸の親水化処理方法に
よって達成される。C. Means for Solving Problems] The above-mentioned object of the present invention is to contain ethylene in at least a portion of the wall surface forming the micropores of a polyolefin hollow fiber having micropores connected from the inner wall surface of the hollow fiber to the outer wall surface. - This is achieved by a method for hydrophilizing porous polyolefin hollow fibers, which is characterized by forming a thin film made of a vinyl acetate copolymer and then saponifying the ethylene-vinyl acetate copolymer.
中空糸内壁面より外壁面へつながった微小空孔を有する
ポリオレフィン中空糸としては中空系のほぼ長手方向に
配列した多数のフィブリル相互間に形成されている微小
空孔が中空糸の内壁面と外壁面との間を連通している多
孔質中空糸であることが好ましい、このような中空糸は
例えば特開昭５７−４２９１９号に記載された方法によ
り製造することができる。ポリオレフィンとしてはポリ
エチレン、ポリプロピレン、ポリ−４−メチルペンテン
、ポリテトラフルオロエチレン等を挙げることができる
。Polyolefin hollow fibers have micropores that connect from the inner wall surface to the outer wall surface of the hollow fiber. Preferably, the porous hollow fibers communicate with the wall surface, and such hollow fibers can be manufactured, for example, by the method described in JP-A No. 57-42919. Examples of polyolefins include polyethylene, polypropylene, poly-4-methylpentene, polytetrafluoroethylene, and the like.
中空糸内壁面より外壁面へつながった微小空孔を有する
ポリオレフィン中空糸の微小空孔を形成している壁面の
少なくとも１部にエチレン−ビニルアセテート共重合体
からなる薄膜を形成して恒久的に親水化されたポリオレ
フィン中空糸を得る方法としては例えばエチレン−ビニ
ルアセテート共重合体を含有する溶液を多孔質ポリオレ
フィン中空糸の微小空孔を形成している壁面の少なくと
も１部に付着させた後、乾燥して溶剤を除去するが、あ
るいは該エチレン−ビニルアセテート共重合体の１Ｍ固
剤溶液に浸漬し、急速凝固処理を行なうことによって水
不溶性有機高分子の薄膜を形成し、これを乾燥すること
により得られる。該エチレン−ビニルアセテート共重合
体のエチレン鎖は多孔質ポリオレフィン中空糸に対し優
れた親和性を示ｔため、エチレン−どニルアセテート共
重合体重は多孔質ポリオレフィン中空糸膜の微細孔表面
に強固に付着する。但し、エチレン−ビニルアセテート
共重合体のエチレン含有率が多くなると接着性は向上す
るが、親木性が低下するのでエチレン−ビニルアセテー
ト共重合体のビニルアセテートの含有率は２０％重量以
上であることが好ましい、エチレン−どニルアセテート
共重合体を含有する溶液のエチレン−ビニルアセテート
共重合体濃度は１．０〜５．０重量％であることが好ま
しい。A thin film made of ethylene-vinyl acetate copolymer is permanently formed on at least a part of the wall surface forming the micropores of a polyolefin hollow fiber having micropores connected from the inner wall surface of the hollow fiber to the outer wall surface. A method for obtaining a hydrophilized polyolefin hollow fiber is, for example, by applying a solution containing an ethylene-vinyl acetate copolymer to at least part of the wall surface forming micropores of a porous polyolefin hollow fiber, and then Drying to remove the solvent, or forming a thin film of water-insoluble organic polymer by immersing it in a 1M solid solution of the ethylene-vinyl acetate copolymer and performing rapid solidification treatment, and drying this. It is obtained by Since the ethylene chains of the ethylene-vinyl acetate copolymer exhibit excellent affinity for porous polyolefin hollow fibers, the ethylene-vinyl acetate copolymer weight firmly adheres to the micropore surface of the porous polyolefin hollow fiber membrane. adhere to. However, as the ethylene content of the ethylene-vinyl acetate copolymer increases, the adhesion improves, but the wood affinity decreases, so the vinyl acetate content of the ethylene-vinyl acetate copolymer should be 20% or more by weight. Preferably, the ethylene-vinyl acetate copolymer concentration of the solution containing the ethylene-vinyl acetate copolymer is preferably 1.0 to 5.0% by weight.
１．０重量％未満ではエチレン−ビニルアセテート共重
合体を鹸化処理後の親木性が充分得られないので好まし
くない、一方５．０１１量％ｅ越えるとポリエチレン中
空糸の微細孔が閉塞し、癌過性が低下するので好ましく
ない。If it is less than 1.0% by weight, the ethylene-vinyl acetate copolymer will not have sufficient wood-philicity after saponification treatment, which is undesirable.On the other hand, if it exceeds 5.011% by weight, the micropores of the polyethylene hollow fibers will be blocked. This is not preferred because it reduces cancer hyperactivity.
これらの水不溶性有機高分子薄膜は多孔質中空糸の微小
空孔を形成している壁面に、できるだけ均一にしかもそ
の付着量を最小限度に留め、付着処理による中空糸微細
空孔の閉塞をできるだけ少なくすることが好ましい。These water-insoluble organic polymer thin films are applied as uniformly as possible to the wall surface forming the micropores of the porous hollow fibers, and the amount of adhesion is kept to a minimum, thereby preventing the blockage of the hollow fiber micropores as much as possible due to the adhesion treatment. It is preferable to reduce the amount.
鹸化処理を行なう方法としては水酸化ナトリウム等のア
ルカリ水溶液中で一定時間加熱処理し。The saponification treatment is carried out by heating in an alkaline aqueous solution such as sodium hydroxide for a certain period of time.
ビニルアセテート部分のアセチル基を水酸基に添加すれ
ばよい。The acetyl group of the vinyl acetate moiety may be added to the hydroxyl group.
〔実施例］ 以下、本発明を実施例によって説明する。〔Example] Hereinafter, the present invention will be explained by examples.
１亙ｌ」
エチレン−ビニルアセテート共重合体（組成比５５：４
５）３重量部をトルエン９７重量部に溶解して得た２５
℃の溶液中に中空糸のほぼ長手方向に配列した多数のフ
ィブリル相互間に形成されている微小空孔が中空糸の内
壁面と外壁面との間を連通しているポリエチレン多孔質
中空糸（三菱レイヨン■製、商品名ＥＨＦ）を３０秒間
浸潰した後、真空乾燥機により５０℃で３時間乾燥して
溶剤の除去を行なった。1" ethylene-vinyl acetate copolymer (composition ratio 55:4
5) 25 obtained by dissolving 3 parts by weight in 97 parts by weight of toluene
A polyethylene porous hollow fiber (with micropores formed between a large number of fibrils arranged approximately in the longitudinal direction of the hollow fiber in a solution at ℃) communicates between the inner wall surface and the outer wall surface of the hollow fiber. Mitsubishi Rayon (trade name: EHF) was soaked for 30 seconds, and then dried at 50° C. for 3 hours in a vacuum dryer to remove the solvent.
次に水酸化ナトリウム１０ｇを１９．の水に溶解したア
ルカリ水溶液中に浸漬し、６０℃で１時間鹸化処理を行
なった後水洗、乾燥して親水性多孔質ポリエチレン中空
糸を得た。Next, add 10g of sodium hydroxide to 19. The fibers were immersed in an alkaline aqueous solution dissolved in water, saponified at 60° C. for 1 hour, washed with water, and dried to obtain hydrophilic porous polyethylene hollow fibers.
この中空糸１００本をＵ字型に束ね、中空糸端部を樹脂
でハウジングに固定して中空糸有効長１０ｃｍの鑓過モ
ジュールを作成した。このモジュールに０．４ ｋｇ／
ｃｒｎ’という低い水圧で水を癌過したところ優れた透
水性を示した。100 of these hollow fibers were bundled into a U-shape, and the ends of the hollow fibers were fixed to a housing with resin to create a filter module with an effective hollow fiber length of 10 cm. 0.4 kg/ for this module
When water was passed through it at a low water pressure of crn', it showed excellent water permeability.
さらに水圧１ ｋｇ／ｃｒｎ’で水を１時間濾過した後
。After further filtering the water for 1 hour at a water pressure of 1 kg/crn'.
水を抜き取り、５０℃の真空乾燥機で２０時間乾燥した
後、水を癌過して耐水圧 、透水量を調・べたところ乾
燥による性濠の低下は見られなかった。After removing the water and drying it in a vacuum dryer at 50°C for 20 hours, we checked the water pressure resistance and water permeability by passing the water through the tube, and found that no decrease in the moat quality was observed due to drying.
塩艶１
親水化されていない実施例１で用いたと同様のポリエチ
レン中空糸を用い、実施例１と同様の濾過モジュールを
作成し、水を濾過しようとしたが、水圧３ ｋｌ／ｃｒ
ｒｒ’以下では水は全く濾過されなかった。Salt Gloss 1 A filtration module similar to that used in Example 1 was created using polyethylene hollow fibers similar to those used in Example 1, which had not been made hydrophilic, and an attempt was made to filter water, but the water pressure was 3 kl/cr.
Below rr' no water was filtered at all.
［発明の効果］
本発明の方法で親水化された多孔質ポリオレフィン中空
糸は優れた親木性を有しており、エタノール等による親
水化前処理を行なわすとも良好な透水性を示し、濾過中
又は濾過後に膜が乾燥しても濾過性能の低下はほとんど
認められず、その実用的効果は極めて大きい。[Effects of the Invention] The porous polyolefin hollow fibers made hydrophilic by the method of the present invention have excellent wood-philicity, and exhibit good water permeability even when pre-treated with ethanol etc. to make them hydrophilic. Even if the membrane dries during or after filtration, there is hardly any decrease in filtration performance, and its practical effects are extremely large.
Claims (1)
ポリオレフィン中空糸の微小空孔を形成している壁面の
少なくとも１部にエチレン−ビニルアセテート共重合体
からなる薄膜を形成した後、該エチレン−ビニルアセテ
ート共重合体を鹸化することを特徴とする多孔質ポリオ
レフィン中空糸の親水化処理方法。After forming a thin film made of ethylene-vinyl acetate copolymer on at least a portion of the wall surface forming the micropores of the polyolefin hollow fiber having micropores connected from the inner wall surface of the hollow fiber to the outer wall surface, the ethylene - A method for hydrophilizing porous polyolefin hollow fibers, which comprises saponifying a vinyl acetate copolymer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59245606A JPS61125408A (en) | 1984-11-20 | 1984-11-20 | Method for making porous polyolefin hollow yarn hydrophilic |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59245606A JPS61125408A (en) | 1984-11-20 | 1984-11-20 | Method for making porous polyolefin hollow yarn hydrophilic |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61125408A true JPS61125408A (en) | 1986-06-13 |
| JPH041653B2 JPH041653B2 (en) | 1992-01-13 |
Family
ID=17136211
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59245606A Granted JPS61125408A (en) | 1984-11-20 | 1984-11-20 | Method for making porous polyolefin hollow yarn hydrophilic |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61125408A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161103A (en) * | 1985-01-10 | 1986-07-21 | Terumo Corp | Hydrophilic porous membrane and its preparation |
| JPS61271003A (en) * | 1985-05-27 | 1986-12-01 | Asahi Medical Co Ltd | Hydrophilic compound porous membrane and its preparation |
| JPH03258331A (en) * | 1990-03-08 | 1991-11-18 | Asahi Chem Ind Co Ltd | Method of treating condensed water |
| EP0498414A2 (en) * | 1991-02-08 | 1992-08-12 | Mitsubishi Rayon Co., Ltd. | Porous hollow fiber membrane of polypropylene and production thereof |
| US5330830A (en) * | 1992-02-07 | 1994-07-19 | Mitsubishi Rayon Co., Ltd. | Heat-resisting porous membrane, hydrophilized heat-resisting porous membrane and production processes thereof |
| CN102489184A (en) * | 2011-11-28 | 2012-06-13 | 北京碧水源膜科技有限公司 | Polyvinylidene difluoride hollow fiber micro-filtration membrane with permanent hydrophilicity, and preparation method thereof |
-
1984
- 1984-11-20 JP JP59245606A patent/JPS61125408A/en active Granted
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61161103A (en) * | 1985-01-10 | 1986-07-21 | Terumo Corp | Hydrophilic porous membrane and its preparation |
| JPH0451214B2 (en) * | 1985-01-10 | 1992-08-18 | Terumo Corp | |
| JPS61271003A (en) * | 1985-05-27 | 1986-12-01 | Asahi Medical Co Ltd | Hydrophilic compound porous membrane and its preparation |
| JPH0427891B2 (en) * | 1985-05-27 | 1992-05-13 | Asahi Medical Co | |
| JPH03258331A (en) * | 1990-03-08 | 1991-11-18 | Asahi Chem Ind Co Ltd | Method of treating condensed water |
| EP0498414A2 (en) * | 1991-02-08 | 1992-08-12 | Mitsubishi Rayon Co., Ltd. | Porous hollow fiber membrane of polypropylene and production thereof |
| US5330830A (en) * | 1992-02-07 | 1994-07-19 | Mitsubishi Rayon Co., Ltd. | Heat-resisting porous membrane, hydrophilized heat-resisting porous membrane and production processes thereof |
| CN102489184A (en) * | 2011-11-28 | 2012-06-13 | 北京碧水源膜科技有限公司 | Polyvinylidene difluoride hollow fiber micro-filtration membrane with permanent hydrophilicity, and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH041653B2 (en) | 1992-01-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4073733A (en) | PVA membrane and method for preparing the same | |
| US4851121A (en) | Process for rendering porous membrane hydrophilic | |
| JPH01104305A (en) | Membrane for separating liquid | |
| JPS61125408A (en) | Method for making porous polyolefin hollow yarn hydrophilic | |
| JP3216910B2 (en) | Porous hollow fiber membrane | |
| JPH0427891B2 (en) | ||
| JPS6214903A (en) | Process of turning hydrophobic microporous filter membrane hydrophilic | |
| JPH04346825A (en) | Production of hydrophilic porous membrane | |
| JPH08131793A (en) | Treatment film for donating hydrophilic effects | |
| JPH0470936B2 (en) | ||
| JP3358341B2 (en) | Hydrophilic membrane and its manufacturing method | |
| JPH05168878A (en) | Antimicrobial liquid separation membrane | |
| JP2813452B2 (en) | Method for producing hydrophilic membrane | |
| JPH054126B2 (en) | ||
| JP2883406B2 (en) | Hydrophilic membrane | |
| JPS6214904A (en) | Process of turning surface of hydrophobic microporous filter membrane hydrophilic | |
| JPH0693980B2 (en) | Composite ultrafiltration membrane | |
| JPH054127B2 (en) | ||
| JP3358339B2 (en) | Hydrophilic membrane and its manufacturing method | |
| JPH08131792A (en) | Film for donating hydrophilic effects | |
| JP2926082B2 (en) | Hydrophilic membrane | |
| JP2759339B2 (en) | Manufacturing method of hydrophilized porous membrane | |
| JP3385755B2 (en) | Hydrophilic membrane and method for producing the same | |
| JP3358340B2 (en) | Hydrophilic membrane and method for producing the same | |
| JP3358342B2 (en) | Hydrophilic membrane and method for producing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EXPY | Cancellation because of completion of term |