JPS62180703A - Porous hollow yarn membrane - Google Patents
Porous hollow yarn membraneInfo
- Publication number
- JPS62180703A JPS62180703A JP2131286A JP2131286A JPS62180703A JP S62180703 A JPS62180703 A JP S62180703A JP 2131286 A JP2131286 A JP 2131286A JP 2131286 A JP2131286 A JP 2131286A JP S62180703 A JPS62180703 A JP S62180703A
- Authority
- JP
- Japan
- Prior art keywords
- ethyl cellulose
- hollow fiber
- porous
- peripheral wall
- hollow yarn
- 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
- 239000012528 membrane Substances 0.000 title claims abstract description 35
- 239000001856 Ethyl cellulose Substances 0.000 claims abstract description 35
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims abstract description 35
- 229920001249 ethyl cellulose Polymers 0.000 claims abstract description 35
- 235000019325 ethyl cellulose Nutrition 0.000 claims abstract description 35
- 230000002093 peripheral effect Effects 0.000 claims abstract description 27
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 239000011148 porous material Substances 0.000 claims abstract description 15
- 239000012510 hollow fiber Substances 0.000 claims description 58
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Natural products CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 13
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 230000000149 penetrating effect Effects 0.000 claims description 3
- 125000003944 tolyl group Chemical group 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 24
- -1 polypropylene Polymers 0.000 abstract description 12
- 239000004743 Polypropylene Substances 0.000 abstract description 11
- 229920001155 polypropylene Polymers 0.000 abstract description 11
- 238000001914 filtration Methods 0.000 abstract description 7
- 238000000108 ultra-filtration Methods 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 abstract description 4
- 239000011248 coating agent Substances 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 4
- 230000008021 deposition Effects 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 238000000034 method Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 5
- 238000001471 micro-filtration Methods 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000010586 diagram Methods 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
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 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
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 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
- 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
- 238000002156 mixing Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002504 physiological saline solution Substances 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
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920000306 polymethylpentene Polymers 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
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 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
- 230000009466 transformation Effects 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
- 239000008096 xylene 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】 ［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離膜と。[Detailed description of the invention] [Industrial application field] The present invention relates to a separation membrane for the purification of fluids, especially water.
して好適な中空糸膜に関するものてあり、更に詳しくは
親水性を飛躍的に向上させ、またエチルセルロースの被
覆状態を変化させるだけで精密濾過から限外濾過までの
広範囲の濾過能を有する中空糸に関するものである。This article relates to hollow fiber membranes suitable for this purpose, and more specifically, hollow fibers that dramatically improve hydrophilicity and have a wide range of filtration performance from microfiltration to ultrafiltration by simply changing the coating state of ethyl cellulose. It is related to.
［従来の技術］
高分子材料からなる中空糸膜製精密症過膜、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で利用
されている。[Prior Art] Precision filtration 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、限外濾過する場合
、膜は親木性を有することか心安てあり、従来、親木性
を有する精密濾過膜、限外臨過膜を製造するための方法
として、親木性高分子Ｉ＋り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、凝固浴中に浸漬
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ｎ！
２シた後、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が知られている。（以下、従来方
法１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ができ、力学的特性に優れ
た多孔質中空糸膜を得ることが可能となっている。（以
下、従来方法２とする。）
［発明が解決しようとする問題点］
しかしながら、親木性を付与するための従来方法ｌ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、
その結果コスト面て難点かある。When performing precision filtration or ultrafiltration of water or an aqueous solution, it is safe to know that the membrane has wood-philicity, and conventional methods for producing microfiltration membranes and ultrafiltration membranes that have wood-philicity have been used. As a solvent and a swelling agent,
Alternatively, the stock solution is prepared by dissolving it in a non-solvent mixed solvent system to make a homogeneous solution, casting this stock solution into a film, partially or completely evaporating the volatile solvent, and then immersing it in a coagulation bath. A method using phase transformation, such as extracting and removing the solvent to form a porous membrane, or a method of mixing the substance to be eluted with the polymer membrane material.
There are known methods such as extraction, in which the substance to be eluted is eluted from the membrane after 2 hours 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, referred to as conventional method 2.) [Problems to be solved by the invention] However, as mentioned above, the conventional method 1 for imparting tree parentness requires extremely complicated processing steps,
As a result, there are some drawbacks in terms of cost.
また従来方法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、且
つ常に湿潤状態を保持する必要かあること等、その維持
管理が煩雑となっている。Furthermore, in conventional method 2, the porous hollow fiber membrane itself is hydrophobic, and when used for filtration of water or an aqueous solution, it needs to be treated with alcohol or the like to make it hydrophilic, and it always maintains a wet state. Maintenance and management has become complicated.
［問題点を解決するための手段］
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エチルセルロ
ースを被覆することにより、水、又は水溶液の慮過に必
要かつ十分な親水性を有し、更に精密濾過から限外濾過
までの広範囲に亘る癌過渣を有する多孔質中空糸膜が得
られることを見出し、本発明に到達した。[Means for Solving the Problems] The present invention aims to improve the above-described conventional porous membrane, and by coating a hollow fiber substrate having penetrating micropores with ethyl cellulose, it can be used in water or an aqueous solution. The present inventors have discovered that it is possible to obtain a porous hollow fiber membrane that has the necessary and sufficient hydrophilicity for consideration of the above conditions, and further has a wide range of cancerous residues from microfiltration to ultrafiltration, and has 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
内表面をエチルセルロースにより被覆してなる多孔質中
空糸膜が提供される。That is, according to the present invention, a porous hollow fiber membrane is provided, which is 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 ethyl cellulose. Ru.
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−ペンテン−１）など）、フ・
ン素含有高分子化合物、ポリスルホン、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
できる。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ができる。多孔質中空糸基体
の外径、周壁部厚さ２孔径も特に制限されるものてはな
いか、−藤には外径は１０〜１０ｏｏミクロン、周壁部
厚さは１０〜５ｏ。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 products made from polymeric materials include polyolefins (high-density polyethylene, polypropylene, poly(4-methyl-pentene-1), etc.),
Examples include porous hollow fibers made of carbon-containing polymer compounds, polysulfone, polycarbonate, polyvinyl chloride, and the like. Examples of products made from inorganic materials include:
Examples include porous hollow fibers or porous tubes made of glass, ceramics, carbon, and the like. There are no particular restrictions on the outer diameter of the porous hollow fiber substrate, the thickness of the peripheral wall, and the pore diameter.
ミクロ：ン、孔径は０．０１〜５０ミクロンのものか好
ましい。Preferably, the pore size is 0.01 to 50 microns.
本発明で用いられるエチルセルロースのエトキシ基含有
♀：は、４５〜５０％であり、２５℃におけるトルエン
８０％、エタノール２０％の混合溶媒の５％溶液の粘度
が４〜１０ｏｃｐｓ、好ましくは４− ｌ Ｏｃ ｐ
ｓである。 □次に本発明の多孔質中空糸膜の製造
方法を説明する。The ethoxy group content of the ethyl cellulose used in the present invention is 45 to 50%, and the viscosity of a 5% solution of a mixed solvent of 80% toluene and 20% ethanol at 25°C is 4 to 10 ocps, preferably 4-l. Oc p
It is s. □Next, the method for producing the porous hollow fiber membrane of the present invention will be explained.
上述した特定のエチルセルロースを、エチルセルロース
可溶な溶媒に０．１〜５ｗｔ％の濃度となるよう溶解す
る。溶媒としては、アセトン、７セトンー水、メタノー
ル、エタノール等のアルコール、アルコール−水、ベン
ゼン、トルエン、キシレン、クロロホルム等が好ましい
。The specific ethyl cellulose mentioned above is dissolved in an ethyl cellulose-soluble solvent to a concentration of 0.1 to 5 wt%. Preferred solvents include alcohols such as acetone, acetone-water, methanol, and ethanol, alcohol-water, benzene, toluene, xylene, and chloroform.
次いで、該エチルセルロース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該エチ
ルセルロ：−ス溶液を行き渡らせた後、風乾又は水によ
り、あ□るいは風乾と水による凝固により該エチルセル
ロースを多孔質中空糸基体」二に析出させた後、十分に
水洗する。Next, the porous hollow fiber substrate is immersed in the ethyl cellulose solution, and the ethyl cellulose solution is sufficiently spread into the micropores of the porous hollow fiber substrate, and then air-dried or air-dried with water. The ethyl cellulose is precipitated onto the porous hollow fiber substrate by coagulation with water and then thoroughly washed with water.
このようにして得られた。エチルセルロースによって被
覆された多孔質中空糸は、エチルセルロース溶液の濃度
、多孔質中空糸基体の微、細孔内でのエチルセルロース
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が
、その孔径が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
、さらには微細孔内がエチルセルロースで閉塞されてい
るものまで得ることができる。Obtained in this way. The porous hollow fibers coated with ethyl cellulose are characterized by the concentration of the ethyl cellulose solution, the fineness of the porous hollow fiber substrate, and the concentration gradient of the ethyl cellulose solution within the pores (when the porous hollow fiber substrate is immersed in the solution, Conditions such as (creating a concentration gradient by immersion in different solutions two or more times, etc.), precipitation conditions such as air drying, precipitation with water, or a combination of both, and steps such as immersion in the solution - precipitation, washing with water, and drying. By adjusting and changing the process 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, and exhibits sufficient wood-philicity. Those with a pore diameter that is almost the same as the hollow fiber substrate, those with a non-porous sheet layer on at least one surface of the inner and outer surfaces of the peripheral wall of the hollow fiber substrate, and those with micropores blocked with ethyl cellulose. You can get up to.
次に本発明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 the present invention 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図は一部拡大断面図てあって、周壁部２に多数の貫
通微細孔７を有する中空糸基体４であって、その周壁部
２及び微細孔７内表面がエチルセルロース層３により被
覆されたものを示している。即ち、第１図はエチルセル
ロースの被覆状態として薄膜の状態を示す。FIG. 1 is a partially enlarged cross-sectional view showing a hollow fiber substrate 4 having a large number of through-holes 7 in a peripheral wall 2, and the inner surface of the peripheral wall 2 and the micropores 7 are covered with an ethyl cellulose layer 3. It shows what is happening. That is, FIG. 1 shows the state of a thin film covered with ethyl cellulose.
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工壬ルセルロースの非
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 cellulose.
第３図は、微細孔７内をエチルセルロースで閉塞（図中
、６）した場合を示す。FIG. 3 shows a case in which the inside of the micropores 7 are closed with ethyl cellulose (6 in the figure).
［実施例コ
以丁、本発明を実施例によりさらに具体的に説明するが
、本発明がこれに限定されないことは明らかであろう。[Examples] 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（ＵＢＥ−ＰＰ−Ｊ１０９Ｇ、商品名：
宇部興産（株）製、ＭＦＩ＝９ｇ／１０分）を、直径３
３ｍｍ、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℃の加熱空気槽で６分間加熱処理し、
次いで液体窒素（−１９５℃）中で、初期長さに対し２
０％延伸し、延伸状態を保ったまま１４５℃の加熱空気
槽内で２分間熱処理を行なった。(Example 1) Polypropylene (UBE-PP-J109G, trade name:
Made by Ube Industries, Ltd., MFI=9g/10min), diameter 3
Using a hollow fiber manufacturing nozzle equipped with a gas supply pipe of 3 mm in diameter and 27 mm in inner diameter, spinning was carried out at a spinning temperature of 200° C. and a take-up 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, in liquid nitrogen (-195°C), the initial length was
The film was stretched by 0%, and heat-treated for 2 minutes in a heated air bath at 145° C. while maintaining the stretched state.
この中空糸を１２５℃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℃の加熱空
気槽内で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 125°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（測定はカルロエルバ（ＣＡＲＬＯＥＲＢＡ）
社（イタリア）製のポロシメトロ シリーズＣＰＯｎＯ
３ＩＭＥＴＲＯ５ＥＲＩＥＳ）１５００を使用して行っ
た。The average pore diameter of the obtained porous polypropylene hollow fiber was measured by mercury intrusion method (measured by CARLOERBA).
Porosimetro series CPOnO made in Italy
The test was carried out using a METRO 5ERIES) 1500.
以下同様）で測定したところ、０．３２ｐｍであり、空
隙率は７５．２％であった。The same applies hereafter), it was 0.32 pm, and the porosity was 75.2%.
上記の多孔質ポリプロピレジ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ミクロンであ
った。When the peripheral wall of the above-mentioned porous polypropylene resin 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 almost constant throughout. Moreover, the outer diameter of this porous polypropylene hollow fiber was 400 microns, and the inner diameter was 300 microns.
次に、上記多孔質ポリプロピレン中空糸を先ず２５℃て
のトルエン８０％、エタノール２０％の混合溶媒の５％
溶液の粘度か７ｃｐｓ、エトキシ基含有量が４８〜４９
．５％であるエチルセルロース（ダウ ケミカル（ＤＯ
Ｗ ＣＩＩＥＭＩＣＡＬ）社製、エトセルＳＴＤ型ＰＲ
ＥＭＩＵＭ） （７）０ 、３５ｗｔ％７セトン溶液に
浸漬した後、中空糸内径部に存在する溶液がなくなるま
で風乾し、ついで木に浸漬し、エチルセルロースを析出
し、水洗後屹燥した。Next, the porous polypropylene hollow fibers were first mixed with 5% of a mixed solvent of 80% toluene and 20% ethanol at 25°C.
The viscosity of the solution is 7 cps, and the ethoxy group content is 48-49.
．． 5% ethylcellulose (Dow Chemical (DO
Etcel STD type PR manufactured by W CIIEMICAL)
EMIUM) (7)0, 35 wt % 7 setone solution, air-dried until the solution present in the inner diameter of the hollow fiber disappeared, then immersed in wood to precipitate ethyl cellulose, 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で観察したところ、周壁部
、周壁部断面も本質的に、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か観察された。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 essentially retained the same large number of pores as the original porous hollow fiber.
得られた中空糸膜な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量は３５文／１ｎ−１２・ａＬ
ｌｌであった。When water is filtered through the obtained hollow fiber membrane without pretreatment with alcohol, the water permeability is 35 g/1n-12・aL
It was ll.
（比較例）
実施例１に記・戎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／ｃｕｂ２で濾過することを試みた
が透水量は０であった。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２０１ ／ ｍ２
・ｍｉｎ・ａｔｍであった。(Comparative Example) An attempt was made to filter water at pressures of 1 and 5 kg/cub2 using only the porous polypropylene hollow fiber membrane described and described in Example 1 without pretreatment with alcohol, etc., but the water permeability was poor. The amount was 0. In addition, when water is filtered after being hydrophilized with alcohol, the water permeability is 201/m2.
・min・atm.
（実施例２）
実施例１で得られた中空糸を更にもう一回、エチルセル
ロース溶液に浸漬した後中空糸内径部に存在する溶液か
なくなるまで風乾し、ついて水により析出させ、水洗後
乾燥させる工程を追加した以外は実施例１と同様の工程
を行った。(Example 2) The hollow fiber obtained in Example 1 was immersed in the ethyl cellulose solution once more, and then air-dried until the solution present in the inner diameter of the hollow fiber disappeared, followed by precipitation with water, washed with water, and then dried. The same steps as in Example 1 were performed except for adding an additional step.
得られた中空糸膜の周壁部の内外表面及び周壁部所面を
電子顕微鏡で観察したところ、内側周壁部表面及び周壁
部所面は本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が、外側周壁部表面
には、非孔性シート膜が形成されていた。When the inner and outer surfaces of the peripheral wall and parts of the peripheral wall of the obtained hollow fiber membrane were observed using an electron microscope, it was found that the inner and outer peripheral wall surfaces and parts of the peripheral wall had essentially the same large number of transparent holes as the original porous hollow fiber. Although a configuration in which pores were observed was observed, a non-porous sheet film was formed on the surface of the outer peripheral wall.
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量は０．１ｉ１０＋”・ｍｉｎ−
ａｔｍであった。また０、１％のアルブミンの生理食塩
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 amount of water permeable is 0.1i10+"・min-
It was an ATM. Furthermore, when a physiological saline solution containing 0.1% albumin 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′ｅｋ細孔内をエチルセル
ロースによって被覆したことにより、水又は水溶液の濾
過に必要かつ十分な親水性を有し、さらに前記のエチル
セルロースの被覆状態を調節、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 coats the peripheral wall of the porous hollow fiber substrate and the inside of the 'ek pores with ethyl cellulose. and has sufficient hydrophilicity, and further by adjusting and changing the coating state of the ethyl cellulose,
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
一部拡大断面説明図、第２図及び第３図は各々本発明の
他の実施例を示す一部拡大断面説明図を示す。
２・・・中空糸の周壁部、３・・・エチルセルロース、
４・・・中空糸基体、５・・・エチルセルロースの非孔
性シート層。FIG. 1 is a partially enlarged cross-sectional explanatory diagram showing one embodiment of the porous hollow fiber membrane according to the present invention, and FIGS. 2 and 3 are partially enlarged cross-sectional explanatory diagrams showing other embodiments of the present invention, respectively. shows. 2... Peripheral wall portion of hollow fiber, 3... Ethyl cellulose,
4...Hollow fiber substrate, 5...Non-porous sheet layer of ethyl cellulose.
Claims (5)
あって、その周壁部表面及び該微細孔内表面をエチルセ
ルロース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 porous hollow fiber membrane, characterized in that it is a hollow fiber substrate having a large number of penetrating micropores in its peripheral wall, and the surface of the peripheral wall and the inner surface of the micropores are coated with ethyl cellulose.
もその一表面側をエチルセルロース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) The porous hollow fiber membrane according to claim 1, wherein 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 ethyl cellulose. .
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 plugged with ethyl cellulose.
０％、エタノール２０％の混合溶媒の５％溶液の粘度が
４〜１００ｃｐｓ、エトキシ基含有量が４５〜５０％で
ある特許請求の範囲第１項、第２項又は第３項記載の多
孔質中空糸膜。(4) Ethyl cellulose is toluene 8 at 25°C.
The porous material according to claim 1, 2 or 3, wherein a 5% solution of a mixed solvent of 0% ethanol and 20% ethanol has a viscosity of 4 to 100 cps and an ethoxy group content of 45 to 50%. Hollow fiber membrane.
０％、エタノール２０％の混合溶媒の５％溶液の粘度が
４〜１０ｃｐｓである特許請求の範囲第４項記載の多孔
質中空糸膜。(5) Ethylcellulose is toluene 8 at 25℃
5. The porous hollow fiber membrane according to claim 4, wherein a 5% solution of a mixed solvent of 0% ethanol and 20% ethanol has a viscosity of 4 to 10 cps.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2131286A JPH0636853B2 (en) | 1986-02-04 | 1986-02-04 | Porous hollow fiber 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 |
|---|---|---|---|
| JP2131286A JPH0636853B2 (en) | 1986-02-04 | 1986-02-04 | Porous hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62180703A true JPS62180703A (en) | 1987-08-08 |
| JPH0636853B2 JPH0636853B2 (en) | 1994-05-18 |
Family
ID=12051634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2131286A Expired - Fee Related JPH0636853B2 (en) | 1986-02-04 | 1986-02-04 | Porous hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0636853B2 (en) |
-
1986
- 1986-02-04 JP JP2131286A patent/JPH0636853B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0636853B2 (en) | 1994-05-18 |
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