JPS62294404A - Porous hollow membrane - Google Patents
Porous hollow membraneInfo
- Publication number
- JPS62294404A JPS62294404A JP13557386A JP13557386A JPS62294404A JP S62294404 A JPS62294404 A JP S62294404A JP 13557386 A JP13557386 A JP 13557386A JP 13557386 A JP13557386 A JP 13557386A JP S62294404 A JPS62294404 A JP S62294404A
- Authority
- JP
- Japan
- Prior art keywords
- poly
- hollow fiber
- porous
- peripheral wall
- hollow
- 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.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 33
- -1 polypropylene Polymers 0.000 claims abstract description 55
- 230000002093 peripheral effect Effects 0.000 claims abstract description 28
- 239000000758 substrate Substances 0.000 claims abstract description 22
- 239000012510 hollow fiber Substances 0.000 claims description 51
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 claims description 21
- 230000000149 penetrating effect Effects 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000011148 porous material Substances 0.000 abstract description 13
- 239000000243 solution Substances 0.000 abstract description 13
- 239000004743 Polypropylene Substances 0.000 abstract description 11
- 229920001155 polypropylene Polymers 0.000 abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 9
- 238000000108 ultra-filtration Methods 0.000 abstract description 7
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 5
- 238000007605 air drying Methods 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 239000002904 solvent Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 5
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 102000009027 Albumins Human genes 0.000 description 2
- 108010088751 Albumins Proteins 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229920001903 high density polyethylene Polymers 0.000 description 2
- 239000004700 high-density polyethylene Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 229920005597 polymer membrane Polymers 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 238000011282 treatment Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
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
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
Abstract
Description
【発明の詳細な説明】
３、発明の詳細な説明
「産業上の利用分野］
本発明は、流体特に水の浄化のための分〜膜として好適
な中空糸膜に関するものであり、史に詳しくは親水性を
水曜的に白しさせ、またポリ（２−ヒドロキシエチルメ
タクリレート）の被覆状態を変化させるたけで精密濾過
から限外濾過までの広範囲の一過能を有する中空糸に関
するものである。Detailed Description of the Invention 3. Detailed Description of the Invention "Field of Industrial Application" The present invention relates to a hollow fiber membrane suitable as a separation membrane for purifying fluids, especially water. This patent relates to a hollow fiber having a wide range of transitivity from microfiltration to ultrafiltration by simply changing the hydrophilicity and changing the coating state of poly(2-hydroxyethyl methacrylate).
［従来の技術］
高分子材料からなる中空糸膜製精密濾過膜、限外濾過膜
は水、溶液の分離精製、処理等の分野や医療分野て利用
されている。[Prior Art] Microfiltration membranes and ultrafiltration membranes made of hollow fiber membranes made of polymeric materials are used in fields such as separation and purification and treatment of water and solutions, and in the medical field.
水又は水溶液を精密濾過、あるいは、限外−過する場合
、膜は親木性を有することか必要てあり、従来、親水性
を有する精密濾過膜、限外症過膜を製造するだめの方法
として、親木性高分子膜素材を溶媒および膨潤剤、また
は非溶媒の混合溶媒系に溶解して均一溶液としたものを
原液とし、この原液を膜状にキャストし、揮発性溶媒を
一部あるいは完全に蒸発させた後、凝固浴中に侵漬して
溶媒を抽出除去して多孔質膜とする等の相転換による方
法や、高分子−膜素材に被溶出物質を混合して成膜した
後、膜中から被溶出物質を溶出させて多孔質膜とする抽
出による方法等か知られている。（以下、従来方法ｌと
する。）
一方、高密度ポリエチレン、ポリプロピレン、ポリ（４
−メチル−ペンテン−１）等の熱可塑性樹脂からなる多
孔質膜は、前記の方法の外、中空原糸を紡糸した後、特
定温度範囲及び／又は特定媒体中で延伸により多孔質化
する方法により製造することかでき、力学的特性に優れ
た多孔質中空糸膜を得ることか可能となっている。（以
下、従来方？ｊ：２とする。）
［発明か解決しようとする問題点］
、 しかしなから、親木性をイ・１与するための従来方
法１にあっては、前記の通り極めて複雑な処理工程を必
要とし・、その結果コスト面で難点かある。When performing precision filtration or ultrafiltration of water or an aqueous solution, it is necessary for the membrane to have phyllophilic properties, and conventional methods for manufacturing microfiltration membranes and ultrafiltration membranes that have hydrophilic properties have been difficult. As a stock solution, a wood-philic polymer membrane material is dissolved in a mixed solvent system of a solvent and a swelling agent, or a non-solvent to make a homogeneous solution, and this stock solution is cast into a film shape, and some of the volatile solvent is removed. Alternatively, after complete evaporation, the solvent can be extracted and removed by immersion in a coagulation bath to form a porous membrane, or a membrane can be formed by mixing the substance to be eluted with the polymer-membrane material. After that, there is a known extraction method in which the substance to be eluted is eluted from the membrane to form a porous membrane. (Hereinafter referred to as conventional method 1.) On the other hand, high-density polyethylene, polypropylene, poly(4
- Porous membranes made of thermoplastic resins such as methyl-pentene-1) can be produced by, in addition to the above-mentioned method, a method in which hollow filaments are spun and then made porous by stretching in a specific temperature range and/or in a specific medium. It has become possible to obtain porous hollow fiber membranes with excellent mechanical properties. (Hereinafter, the conventional method ?j: 2.) [Problems to be solved by the invention] However, in the conventional method 1 for giving the parent tree property of i.1, as mentioned above, It requires an extremely complicated processing process, and as a result, there are some drawbacks in terms of cost.
また従来方υ、２においても、製造される多孔質中空糸
膜自体は疎水性であって、水又は水溶液の濾過に使用す
る際、アルコール等により親水化処理する必要かあり、
住つ常に湿潤状態を保持する必要かあること等、その維
持管理か煩雑となっている。In addition, in conventional method υ, 2, the porous hollow fiber membrane itself produced is hydrophobic, and when used for filtration of water or an aqueous solution, it is necessary to make it hydrophilic with alcohol or the like.
Maintenance and management is complicated, as it is necessary to keep the area moist at all times.
し問題点を解決するだめの手段コ
本発明は、上記した従来の多孔質膜の改良を目的とする
もので、貫通微細孔を有する中空糸基体にポリ（２−ヒ
ドロキシエチルメタクリレ−１へ）を被覆することによ
り、水、又は水溶液の濾過に必要かつ十分な親木性を有
し、更に精密濾過から限外濾過までの広範囲に亘る濾過
能を有する多孔質中空糸膜か得られることを見出し、本
発明に到達した。The present invention aims to improve the above-mentioned conventional porous membrane, and it is intended to improve the above-mentioned conventional porous membrane. ), it is possible to obtain a porous hollow fiber membrane that has sufficient wood-philicity necessary for filtration of water or aqueous solutions and also has a wide range of filtration ability from microfiltration to ultrafiltration. They discovered this and arrived at the present invention.
即ち、本発明によれば、周壁部に多数の貫通微細孔を有
する中空糸基体であって、その周壁部表面及び該微細孔
内表面をポリ（２−ヒドロキシエチルメタクリレート）
により被覆してなる多孔質中空糸膜か提供される。That is, according to the present invention, there is provided a hollow fiber substrate having a large number of penetrating micropores in the peripheral wall, and the surface of the peripheral wall and the inner surface of the micropores are coated with poly(2-hydroxyethyl methacrylate).
A porous hollow fiber membrane coated with is provided.
本発明において用いられる、周壁部に多数の貫通微細孔
を有する中空糸基体の材質については特に制限されるも
のではない。高分子材料を素材とするものの例としては
、ポリオレフィン（高密度ポリエチレン、ポリプロピレ
ン、ポリ（４−メチル−ベンゾン−１）など）、フッ素
含有高分子化合物、ポリスルポン、ポリカーボネート、
ポリ塩化ビニル、等の多孔質中空糸を挙げることがてき
る。また無機材料を素材とするものの例としては、ガラ
ス、セラミックス、炭素などの多孔質中空糸又は多孔質
チューブを挙げることかてきる。多孔質中空糸基体の外
径、周壁部厚さ、孔径も特に制限されるものてはないか
、一般には外径は１０〜１０００ミク℃１ン、周壁部厚
さは１０〜５００ミクロン、孔径は０．０１〜５０ミク
ロンのものか好ましい。There are no particular limitations on the material of the hollow fiber substrate, which is used in the present invention and has a large number of through-holes in its peripheral wall. Examples of polymer materials include polyolefins (high-density polyethylene, polypropylene, poly(4-methyl-benzone-1), etc.), fluorine-containing polymer compounds, polysulfone, polycarbonate,
Examples include porous hollow fibers such as polyvinyl chloride. Examples of materials made of inorganic materials include porous hollow fibers or porous tubes made of glass, ceramics, carbon, and the like. There are no particular restrictions on the outer diameter, peripheral wall thickness, and pore diameter of the porous hollow fiber substrate; generally, the outer diameter is 10 to 1,000 microns, the peripheral wall thickness is 10 to 500 microns, and the pore diameter is 10 to 1,000 microns. is preferably 0.01 to 50 microns.
次に本発明の多孔質中空糸）漠の製造方法を説明する。Next, the manufacturing method of the porous hollow fiber of the present invention will be explained.
ポリ（２−ヒドロキシエチルメタクリレート）をポリ（
２−ヒドロキシエチルメタクリレート）可溶な溶媒に溶
解する。溶媒としては、メタノールか好ましい。また、
溶液の濃度は０１０５〜７ｗｔ％の範囲、好ましくは０
．１〜５ ｗ ｔ％の範囲である。Poly(2-hydroxyethyl methacrylate) is converted into poly(2-hydroxyethyl methacrylate)
2-Hydroxyethyl methacrylate) dissolved in a soluble solvent. Methanol is preferred as the solvent. Also,
The concentration of the solution is in the range of 0.1 to 7 wt%, preferably 0.
．． It ranges from 1 to 5 wt%.
次いて、該ポリ（２−ヒドロキシエチルメタクリレート
）溶液に多孔質中空糸基体を浸漬し、多孔質中空糸基体
の微細孔内にも十分類ポリ（２−ヒトロキシエチルメタ
クリレート）溶液を行き渡らせた後、風乾又は水による
凝固あるいは風乾と水による凝固の組合せにより該ポリ
（２−ヒドロキシエチルメタクリレート）を多孔質中空
糸基体上に析出させた後、十分に水洗する。Next, the porous hollow fiber substrate was immersed in the poly(2-hydroxyethyl methacrylate) solution, and the poly(2-hydroxyethyl methacrylate) solution was spread throughout the micropores of the porous hollow fiber substrate. Thereafter, the poly(2-hydroxyethyl methacrylate) is precipitated on the porous hollow fiber substrate by air drying, coagulation with water, or a combination of air drying and coagulation with water, and then thoroughly washed with water.
このようにして得られた、ポリ（２−ヒドロキシエチル
メタクリレート）によって被覆された多孔質中空糸は、
ポリ（２−ヒドロキシエチルメタクリレート）溶液の濃
度、多孔質中空糸基体の微細孔内てのポリ（２−ヒドロ
キシエチルメタクリレート）溶液の濃度勾配（多孔質中
空糸基体を該溶液に浸漬する際、濃度の異なる該溶液に
二回以上浸漬する等により濃度勾配を作る）等の条件及
び風乾、水による析出又は両者の組合せ等の析出条件、
及び該溶液への浸漬−析出一水洗一乾燥等の工程の複数
回実施等を適宜調節、変化させることにより、中空糸基
体の周壁部表面及びその微細孔内表面のみか極薄膜に覆
われ、十分な親木性を示すか、その孔径か元の多孔質中
空糸基体の孔径とほとんど変りかないものから、中空糸
基体周壁部の内外表面のうち少なくともその一表面側に
非孔性シート層を有するもの、さらには微細孔内かポリ
（２−ヒドロキシエチルメタクリレート）で閉塞されて
いるものまて得ることができる。The porous hollow fibers coated with poly(2-hydroxyethyl methacrylate) thus obtained were
Concentration of poly(2-hydroxyethyl methacrylate) solution, concentration gradient of poly(2-hydroxyethyl methacrylate) solution within the micropores of the porous hollow fiber substrate (when the porous hollow fiber substrate is immersed in the solution, the concentration gradient conditions such as creating a concentration gradient by immersing the solution twice or more in different solutions, and precipitation conditions such as air drying, precipitation with water, or a combination of the two,
By appropriately adjusting and changing the steps of immersion in the solution, precipitation, washing, and drying multiple times, only the surface of the peripheral wall of the hollow fiber substrate and the inner surfaces of its micropores are covered with an extremely thin film. A non-porous sheet layer is formed on at least one surface of the inner and outer surfaces of the peripheral wall of the hollow fiber substrate, which exhibits sufficient wood-philicity or whose pore diameter is almost the same as that of the original porous hollow fiber substrate. It is also possible to obtain one in which the micropores are blocked with poly(2-hydroxyethyl methacrylate).
次に未発ＩＪ１１の多孔質中空糸膜の構造を第１〜３図
に基いて説明する。Next, the structure of the porous hollow fiber membrane of undeveloped IJ11 will be explained based on FIGS. 1 to 3.
図中、■は中空糸膜な軸方向に直角に切断した一部断面
部を示す。In the figure, ■ indicates a partial cross section cut at right angles to the axial direction of the hollow fiber membrane.
第１区は一部拡大断面図であって、周壁部２に多数の貫
通微細孔７を有する中空糸基体４てあって、その周壁部
２及び微細孔７内表面がポリ（２−ヒドロキシエチルメ
タクリレート）層３により被覆されたものを示している
。即ち、第１図はポリ（２−ヒドロキシエチルメタクリ
レート）の被覆状態として薄膜の状態を示す。The first section is a partially enlarged cross-sectional view showing a hollow fiber substrate 4 having a large number of through micropores 7 in the peripheral wall 2, and the inner surface of the peripheral wall 2 and the micropores 7 are poly(2-hydroxyethyl). methacrylate) layer 3 is shown. That is, FIG. 1 shows the state of a thin film coated with poly(2-hydroxyethyl methacrylate).
第２図は第１図と異なり、中空糸膜周壁部の内外表面の
うち、少なくともその一表面側をポリ（２−ヒドロキシ
エチルメタクリレ・−ト）の非孔性シート層５て被覆し
たものを示す。Fig. 2 differs from Fig. 1 in that at least one surface of the inner and outer surfaces of the peripheral wall of the hollow fiber membrane is covered with a non-porous sheet layer 5 of poly(2-hydroxyethyl methacrylate). shows.
第３図は、微細孔７内をポリ（２−ヒドロキシエチルメ
タクリレート）で閉塞（図中、６）した場合を示す。FIG. 3 shows a case where the inside of the micropore 7 is closed with poly(2-hydroxyethyl methacrylate) (6 in the figure).
［実施例］
以下、本発明を実施例によりさらに具体的に説明するが
、本発明かこれに限定されないことは明らかてあろう。[Examples] Hereinafter, the present invention will be explained in more detail with reference to Examples, but it will be clear that the present invention is not limited thereto.
（実施例１）
ポリプロピレン（ＩＩＢＥ−ＰＰ−Ｊ１０９Ｇ、商品名
：宇部興産（株）製、ＭＦＩ−９ｇ／１０分）を、直径
３３ ｍ ｍ、内径２７ ｍ ｍの気体供給管を備えた
中空糸製造用ノズルを使用し、紡糸温度２００℃、引取
り速度１１６ｍ／分の条件で紡糸した。得られたポリプ
ロピレン中空糸を１４５℃の加熱空気槽て６分間加熱処
理し、次いて液体窒素（−１９５°Ｃ）中で、初期長さ
に対し２０％延伸し、延伸状態を保ったまま１４５°Ｃ
の加熱空気槽内て２分間熱処理を行なった。(Example 1) Polypropylene (IIBE-PP-J109G, trade name: manufactured by Ube Industries, Ltd., MFI-9g/10 min) was formed into a hollow fiber equipped with a gas supply pipe having a diameter of 33 mm and an inner diameter of 27 mm. Using a production nozzle, spinning was carried out at a spinning temperature of 200° C. and a take-off speed of 116 m/min. The obtained polypropylene hollow fibers were heat treated in a heated air tank at 145°C for 6 minutes, then stretched in liquid nitrogen (-195°C) to 20% of the initial length, and then stretched to 145°C while maintaining the stretched state. °C
Heat treatment was performed for 2 minutes in a heated air bath.
この中空糸を１３０℃の空気雰囲気て４００％の熱延伸
を行なった後、延伸状態を保ったまま１４５°Ｃの加熱
空気槽内て１５分間熱処理を行ない多孔質ポリプロピレ
ン中空糸を製造した。This hollow fiber was hot-stretched by 400% in an air atmosphere at 130°C, and then heat-treated for 15 minutes in a heated air bath at 145°C while maintaining the stretched state to produce a porous polypropylene hollow fiber.
得られた多孔質ポリプロピレン中空糸の平均透孔径を水
銀圧入法（測定はカルロエルハ（ＣＡＲＩ、０ＥＲＢＡ
）社（イタリア）製のポロシメトロ シリーズ（ＰＯＲ
Ｏ３ＩＮＥＴＩＩＯ５ＥＲＩＥＳ）１５００を使用して
行った。The average pore diameter of the obtained porous polypropylene hollow fibers was measured using a mercury intrusion method (measured using CARI, 0ERBA).
) (Italy) made Porosimetro series (POR
The test was carried out using O3INETIIO5ERIES) 1500.
以下同様）て測定したところ、０．３７７％ｍであり、
空隙率は７４％゛Ｃあった。The same applies hereafter) and it was measured to be 0.377%m,
The porosity was 74%゛C.
上記の多孔質ポリプロピレン中空糸の周壁部を電子顕微
鏡により観察したところ、周壁部に多数の大きな透孔か
均一に形成されており、また透孔径も全体にわたってほ
ぼ一定していた。また、この多孔質ポリプロピレン中空
糸の外径は４００ミクロン、内径は３００ミクロンてあ
った。When the peripheral wall of the above porous polypropylene hollow fiber was observed using an electron microscope, it was found that many large pores were uniformly formed in the peripheral wall, and the diameter of the pores was also approximately constant throughout. The porous polypropylene hollow fibers had an outer diameter of 400 microns and an inner diameter of 300 microns.
次に、」−記多孔質ボリブロピレン中空糸を先ずポリ（
２−ヒドロキシエチルメタクリレート）（ジャンセン
キミカ（ＪＡＮＳＳＥＮ （１：ＨＩＭＩｃＡ）社製、
ベルギー国））の濃度か１．５ｗｔ％のメタノール溶液
に浸漬し、中空糸の孔内部及び中空糸内径部まて十分に
溶液を行渡らせた後、水に浸漬しポリ（２−ヒドロキシ
エチルメタクリレート）を析出し、水洗後乾燥した。Next, the porous polypropylene hollow fibers were first
2-Hydroxyethyl methacrylate) (Janssen
Manufactured by KIMICA (JANSSEN (1:HIMIcA)),
Poly(2-hydroxyethyl methacrylate) was precipitated, washed with water, and then dried.
このようにして得られた中空糸膜の周壁部の内外表面、
及び周壁部断面を電子顕微鏡て観察したところ、周壁部
、周壁部断面も木質的に、原多孔質中空糸と同一の多数
の大きな透孔が保持された形態が観察された。The inner and outer surfaces of the peripheral wall of the hollow fiber membrane thus obtained,
When the cross-section of the peripheral wall was observed using an electron microscope, it was observed that the peripheral wall and the cross-section of the peripheral wall had a wood-like morphology in which the same large number of large pores as the original porous hollow fiber were retained.
得られた中空糸膜なアルコール等て前処理することなし
に水を濾過した際の透水量は１５．３１／ｍ１ｎ−ｓ２
・ａｔｍてあった。When water was filtered through the hollow fiber membrane without pretreatment with alcohol, the water permeability was 15.31/m1n-s2.
・There was an ATM.
（比較例）
実施例１に記載されている多孔質ポリプロピレン中空糸
膜のみをアルコール等て前処理することなしに、水を圧
力１ 、５ ｋｇ／ｃｍ２て濾過することを試みたか透
水量は０てあった。また、アルコールて親水化処理した
後、水を濾過するとその透水量は２５ 、５ （１／ｒ
ｓ２・ｍ’＋ｎ−ａｔ、ｔｒｒてあった。(Comparative Example) An attempt was made to filter water at a pressure of 1.5 kg/cm2 using only the porous polypropylene hollow fiber membrane described in Example 1 without pretreatment with alcohol or the like. There was. In addition, when water is filtered after being hydrophilized with alcohol, the water permeability is 25,5 (1/r
s2・m'+n-at, trr.
（実施例２）
ポリ（２−ヒＩ−： Ｃｆｆ−Ｖジエチルメタクリレー
ト）の濃度か３．０ｗｔ％のメタノール溶液に浸漬した
後、完全に風乾したこと以外は実施例１と同様の工程を
行９た。(Example 2) The same process as in Example 1 was performed except that the sample was immersed in a methanol solution with a concentration of 3.0 wt% poly(2-hyI-: Cff-V diethyl methacrylate) and then completely air-dried. It was 9.
得られた中空糸膜の周壁部の内外表面及び周壁部断面を
電子ＷＪ微鏡でｒＩＪｌ察したところ、内側周壁部表面
及び周壁部断面は木質的に原多孔質中空糸と同一の多数
の大きな透孔か保持された形態か観察されたか、外側周
壁部表面には、非孔性シート膜か形成されていた。When the inner and outer surfaces and the cross section of the peripheral wall of the obtained hollow fiber membrane were observed using an electronic WJ microscope, it was found that the surface of the inner peripheral wall and the cross section of the peripheral wall contained a large number of large wood grains that were the same as the original porous hollow fiber. A non-porous sheet film was formed on the surface of the outer peripheral wall, indicating that the pores were maintained.
得られた中空糸をアルコール等で前処理することなしに
水を濾過した際の透水にはＯ，Ｉｏｎ／ｍ２・ｌｌ１ｉ
ｎ−ａＬＩＩＩであった。また０、１％のアルラミンの
生理食塩水溶液を濾過したところ、アルブミンは完全に
遮断されていた。When water is filtered through the obtained hollow fiber without pretreatment with alcohol etc., the water permeability is O, Ion/m2・ll1i.
It was n-aLIII. Furthermore, when a 0.1% albumin saline solution was filtered, albumin was completely blocked.
［発明の効果］
以上説明したように、本発明に係る多孔質中空糸膜は多
孔質中空糸基体の周壁部及び微細孔内をポリ（２−ヒ）
−ロキジエチルメタクリレート）によって被覆したこと
により、水又は水溶液の濾過に必要かつ上のな親木性を
有し、さらに前記のポリ（２−ヒドロキシエチルメタク
リレート）の被覆状態を調節、変化させることにより、
精密濾過から限外濾過までの広範囲の濾過、分離を達成
することができる。[Effects of the Invention] As explained above, the porous hollow fiber membrane according to the present invention contains poly(2-H) in the peripheral wall and inside the micropores of the porous hollow fiber substrate.
- By coating with poly(2-hydroxyethyl methacrylate), it has excellent wood-philic properties necessary for filtration of water or aqueous solutions, and further by adjusting and changing the coating state of the poly(2-hydroxyethyl methacrylate). ,
A wide range of filtration and separation can be achieved, from microfiltration to ultrafiltration.
第１図は本発明に係る多孔質中空糸膜の一実施例を示す
一部拡大断面説明ＩＡ、第２図及び第３図は各々本発明
の他の実施例を示ず一部拡大断面説明図を示す。
２・・・中空糸の周壁部、３・・・ポリ（２−ヒドロキ
シエチルメタクリレート）層、４・・・中空糸基体、５
・・・ポリ（２−ヒドロキシエチルメタクリレート）の
非孔性シー１一層。FIG. 1 is a partially enlarged cross-sectional explanation IA showing one embodiment of the porous hollow fiber membrane according to the present invention, and FIGS. 2 and 3 are partially enlarged cross-sectional explanations showing other embodiments of the present invention. Show the diagram. 2... Peripheral wall portion of hollow fiber, 3... Poly(2-hydroxyethyl methacrylate) layer, 4... Hollow fiber substrate, 5
... One layer of non-porous sheet of poly(2-hydroxyethyl methacrylate).
Claims (3)
あって、その周壁部表面及び該微細孔内表面をポリ（２
−ヒドロキシエチルメタクリレート）により被覆してな
ることを特徴とする多孔質中空糸膜。(1) A hollow fiber substrate having a large number of penetrating micropores in the peripheral wall, the surface of the peripheral wall and the inner surface of the micropores are
-Hydroxyethyl methacrylate).
もその一表面側をポリ（２−ヒドロキシエチルメタクリ
レート）の非孔性シート層で被覆したことを特徴とする
特許請求の範囲第１項記載の多孔質中空糸膜。(2) At least one surface of the inner and outer surfaces of the peripheral wall of the hollow fiber substrate is coated with a non-porous sheet layer of poly(2-hydroxyethyl methacrylate). The porous hollow fiber membrane described.
エチルメタクリレート）で閉塞したことを特徴とする特
許請求の範囲第１項記載の多孔質中空糸膜。(3) The porous hollow fiber membrane according to claim 1, wherein the micropores of the hollow fiber substrate are closed with poly(2-hydroxyethyl methacrylate).
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13557386A JPS62294404A (en) | 1986-06-11 | 1986-06-11 | Porous hollow membrane |
| US07/346,278 US4992332A (en) | 1986-02-04 | 1989-04-27 | Porous hollow fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13557386A JPS62294404A (en) | 1986-06-11 | 1986-06-11 | Porous hollow membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS62294404A true JPS62294404A (en) | 1987-12-21 |
Family
ID=15154974
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13557386A Pending JPS62294404A (en) | 1986-02-04 | 1986-06-11 | Porous hollow membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62294404A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61120602A (en) * | 1984-11-16 | 1986-06-07 | Mitsubishi Rayon Co Ltd | Hydrophilic heat resistant porous polyolefin hollow yarn |
-
1986
- 1986-06-11 JP JP13557386A patent/JPS62294404A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS61120602A (en) * | 1984-11-16 | 1986-06-07 | Mitsubishi Rayon Co Ltd | Hydrophilic heat resistant porous polyolefin hollow yarn |
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