JPH0221930A - Polysulfone-based hollow yarn membrane - Google Patents
Polysulfone-based hollow yarn membraneInfo
- Publication number
- JPH0221930A JPH0221930A JP17356988A JP17356988A JPH0221930A JP H0221930 A JPH0221930 A JP H0221930A JP 17356988 A JP17356988 A JP 17356988A JP 17356988 A JP17356988 A JP 17356988A JP H0221930 A JPH0221930 A JP H0221930A
- Authority
- JP
- Japan
- Prior art keywords
- layer
- membrane
- surface layer
- polysulfone
- hollow fiber
- 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 38
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 18
- 239000010410 layer Substances 0.000 claims abstract description 56
- 239000002344 surface layer Substances 0.000 claims abstract description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012510 hollow fiber Substances 0.000 claims description 28
- 238000000926 separation method Methods 0.000 claims description 14
- 239000011148 porous material Substances 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 abstract description 16
- 230000035699 permeability Effects 0.000 abstract description 15
- 238000009987 spinning Methods 0.000 abstract description 13
- 239000011347 resin Substances 0.000 abstract description 9
- 229920005989 resin Polymers 0.000 abstract description 9
- 229920000642 polymer Polymers 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000002904 solvent Substances 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 239000002202 Polyethylene glycol Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 abstract description 3
- 229920001223 polyethylene glycol Polymers 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract 2
- 239000000701 coagulant Substances 0.000 abstract 2
- 238000005345 coagulation Methods 0.000 description 9
- 230000015271 coagulation Effects 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 5
- 239000011550 stock solution Substances 0.000 description 5
- 238000000108 ultra-filtration Methods 0.000 description 5
- 230000001112 coagulating effect Effects 0.000 description 3
- 108010088751 Albumins Proteins 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108010026206 Conalbumin Proteins 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
Description
【発明の詳細な説明】
（イ）産業上の利用分野
本発明は、限外濾過膜として有用な、透水速度が大きく
、かつ機械的強度に優れたポリスルホン系中空糸膜に関
するものである。DETAILED DESCRIPTION OF THE INVENTION (a) Field of Industrial Application The present invention relates to a polysulfone-based hollow fiber membrane useful as an ultrafiltration membrane, which has a high water permeation rate and excellent mechanical strength.
（ロ）従来の技術
従来より、ポリスルホン系樹脂を素材とする中空糸膜に
関する研究は行なわれ、限外濾過膜としても既に実用化
されている。その製造法に関する特許等の文献も数多く
報告されているが、膜構造を変化させることにより透水
性能を向上させようとした試みは少ない。(b) Prior art Research has been conducted on hollow fiber membranes made from polysulfone resins, and they have already been put into practical use as ultrafiltration membranes. Although many patents and other documents related to the manufacturing method have been reported, there are few attempts to improve water permeability by changing the membrane structure.
（ハ）発明が解決しようとする課題
特開昭５８−１３２１１１号公報や特開昭５８−１５６
０１８号公報、特開昭５６−１１５６０２号公報、特開
昭５４１４３７７７号公報等には、はぼ同じ目的で研究
された結果が述べられているが、透水性は、まだ小さく
、特に限外濾過膜として純水化のために使用される場合
にはさらに高透水性が要求される様になった。(c) Problems to be solved by the invention JP-A-58-132111 and JP-A-58-156
No. 018, JP-A-56-115602, JP-A-54143777, etc. describe the results of research aimed at the same purpose, but the water permeability is still small, especially for ultrafiltration. When used as a membrane for water purification, even higher water permeability is required.
この高透水性は、通常、分画分子量や機械的強度を犠牲
にすれば、容易に得られるが、これでは実用性に乏しく
、実質的に有用なものではない。This high water permeability can usually be easily obtained by sacrificing the molecular weight cut-off and mechanical strength, but this is impractical and is not substantially useful.
本発明は、限外濾過膜として使用される中空糸膜におい
て、分画分子量を１０万以下に保持しながら機械的強度
に優れ、かつ高透水性が付与されたものを提供するもの
である。The present invention provides a hollow fiber membrane used as an ultrafiltration membrane that has excellent mechanical strength and high water permeability while maintaining a molecular weight cut-off of 100,000 or less.
（ニ）課題を解決するための手段
本発明者らは数多くの中空糸膜を作成し、これを限外濾
過膜として使用してその特性を測定した結果、中空糸膜
の構造を制御することにより解決できることが可能であ
ることを解明し、本発明に至った。(d) Means for Solving the Problems The present inventors created a number of hollow fiber membranes, used them as ultrafiltration membranes, and measured their characteristics. As a result, the structure of the hollow fiber membranes can be controlled. The present inventors have discovered that the problem can be solved by the following methods, and have arrived at the present invention.
すなわち、本発明によれば、外表面層、外歯状構造層、
中間層、内積状構造層、内表面層の５層構造からなり、
外表面層又は内表面層の一方が最小孔径を有する分離活
性層を有することを特徴とするポリスルホン系中空糸膜
が提供される。That is, according to the present invention, the outer surface layer, the outer tooth-like structure layer,
Consists of a 5-layer structure: an intermediate layer, an inner stacked structure layer, and an inner surface layer.
Provided is a polysulfone-based hollow fiber membrane characterized in that either the outer surface layer or the inner surface layer has a separation active layer having a minimum pore size.
本発明のポリスルホン系中空糸膜に使用するポリスルホ
ン系樹脂は、それ自体公知のものが利用できる。ポリス
ルホン系樹脂は、少なくとも高分子構造の基本ユニット
の１つとして下記の構造を有するものである。As the polysulfone resin used in the polysulfone hollow fiber membrane of the present invention, any known polysulfone resin can be used. The polysulfone resin has the following structure as at least one of the basic units of the polymer structure.
なお、ポリスルホン系樹脂は、耐熱性、耐薬品性、機械
的強度に優れ、エンジニアリングプラスチックスの１つ
として有用な樹脂であり、これらの樹脂から製造した中
空糸膜においても優れた性能を発揮しうるものである。Polysulfone resins have excellent heat resistance, chemical resistance, and mechanical strength, and are useful as engineering plastics, and hollow fiber membranes made from these resins also exhibit excellent performance. It is something that can be used.
本発明のポリスルホン系中空糸膜は、たとえば原料のポ
リスルホン系樹脂を適当な添加剤（例：ポリエチレング
リコール）の存在下で極性有機溶媒（例ニジメチルスル
ホキシド）に溶解して紡糸原液を作り、この原液を内部
凝固液（例ニジメチルスルホキシドと水の混液）ととも
に、二重環ノズルを通して押出し、空気中を走行させた
後、外部凝固液（例：水）中に導くことによって得るこ
とかできる。The polysulfone-based hollow fiber membrane of the present invention can be produced by, for example, preparing a spinning stock solution by dissolving the raw material polysulfone-based resin in a polar organic solvent (e.g., dimethyl sulfoxide) in the presence of an appropriate additive (e.g., polyethylene glycol). It can be obtained by extruding a stock solution together with an internal coagulating liquid (eg, a mixture of dimethyl sulfoxide and water) through a double-ring nozzle, running it through air, and then introducing it into an external coagulating liquid (eg, water).
上記の工程において、中空糸膜の中間層は、紡糸原液中
の溶媒と添加剤が中空糸の中空側へぬけるものと外表面
側にぬけるものがあるためにその境界層として形成され
る。中間層の厚みは、両方向への移動速度によって決定
され、紡糸溶液組成内部、外部凝固液組成、紡糸原液、
凝固液温度および空中走行距離によって変化する。In the above process, the intermediate layer of the hollow fiber membrane is formed as a boundary layer between the solvent and additives in the spinning dope, because some of the solvent and additives pass through to the hollow side of the hollow fiber and others to the outer surface side. The thickness of the intermediate layer is determined by the speed of movement in both directions, depending on the spinning solution composition: internal spinning solution composition, external coagulation solution composition, spinning stock solution,
It varies depending on the temperature of the coagulating liquid and the distance traveled in the air.
分離活性層となる緻密層は、紡糸原液中の溶媒が水と交
換する際にポリスルホン系ポリマーが凝固しで表面層に
形成される。この時ポリマーが凝縮してできるポリマー
粒子が小さい程、より緻密な層が形成されることになる
。また、ポリスルホン系高分子膜の形成においては凝固
液中の水分量か多いほど、またポリマーの相分離速度を
抑え、凝固粒子径が小さくなる様に凝固温度を低くした
り、紡糸原液組成を変化させるほど緻密層ができやすく
なる。A dense layer serving as a separation active layer is formed on the surface layer by coagulation of the polysulfone polymer when the solvent in the spinning dope is exchanged with water. At this time, the smaller the polymer particles formed by condensation of the polymer, the more dense the layer will be formed. In addition, when forming a polysulfone-based polymer film, the higher the water content in the coagulation solution, the lower the coagulation temperature and the composition of the spinning stock solution to suppress the phase separation rate of the polymer and reduce the coagulation particle size. The more you do it, the more likely it is that a dense layer will form.
従って上記のことを考慮し、適宜これらの条件の設定を
することにより所望の中空系膜を形成することができる
。Therefore, by considering the above and appropriately setting these conditions, a desired hollow film can be formed.
本発明の中空糸膜は、中空糸の断面構造において、外表
面層、外歯状構造層、中間層、内積状構造層、内表面層
からなる５層構造を有する。ここで言う外歯状構造層な
らびに内積状構造層とは、それぞれ主に中空糸膜構造の
維持に寄与する層である。一方、外表面層、中間層、内
表面層は比較的緻密な構造を有し、分離特性や透水性が
決定される層である。従来の５層構造を有する膜は、こ
のうち上述した内・外表面層の両層に分離活性層を有し
ており、分離活性層を２層有することが透水性を低下さ
せる一因となっていた。しかしながら、分離活性層は一
層あれば、その目的は充分に達成されるため、２層も分
離活性層があることは必要以上に透水性の低下を招くお
それがある。The hollow fiber membrane of the present invention has a five-layer structure in the cross-sectional structure of the hollow fiber, consisting of an outer surface layer, an outer tooth-like structure layer, an intermediate layer, an inner laminated structure layer, and an inner surface layer. The outer tooth-like structure layer and the inner laminated structure layer mentioned here are layers that each mainly contribute to maintaining the hollow fiber membrane structure. On the other hand, the outer surface layer, intermediate layer, and inner surface layer have relatively dense structures, and are layers that determine separation characteristics and water permeability. Conventional membranes with a five-layer structure have separation active layers on both the inner and outer surface layers mentioned above, and having two separation active layers is a factor in reducing water permeability. was. However, since the purpose of having one separation active layer is sufficiently achieved, the presence of two separation active layers may lead to an unnecessarily low water permeability.
本発明においては、内表面層あるいは外表面層のいずれ
か一方が分離活性層であり、一方、他のつは多孔質層で
あって、これは分離特性にはほとんど寄与しない層であ
る。これらの各層は薄いものほど、透水性が高まるため
好ましく、特に活性層となる内表面層あるいは外表面層
は、その分離機能さえ発揮するものであれば、薄ければ
薄いほど良い。しかし、あまりに薄いと膜の欠陥も生じ
易いため、分離活性層が０．０１〜０，００１．ｕ）１
７１表面層の全体が５〜２０磨であることが望ましい。In the present invention, either the inner surface layer or the outer surface layer is a separation active layer, while the other is a porous layer, which hardly contributes to the separation properties. The thinner each of these layers is, the better the water permeability increases, and the thinner the inner surface layer or the outer surface layer, which serves as the active layer, the better, as long as it can exhibit its separation function. However, if the separation active layer is too thin, defects are likely to occur in the membrane. u)1
It is desirable that the entire 71 surface layer has a roughness of 5 to 20 polishes.
本発明における外歯状構造層および内積状構造層は、で
きるだけ発達した構造であることが好ましいが、高透水
性能という観点からだけで言えば、特にその構造、層の
厚みを制限する必要はない。It is preferable that the outer tooth-like structure layer and the inner laminar structure layer in the present invention have a structure as developed as possible, but from the viewpoint of high water permeability, there is no particular need to limit the structure or the thickness of the layer. .
上記のような５層構造を有する中空糸膜は、高透水性能
が期待でき、特に純水での膜透過速度は、内表面積基準
で１０００ρ冶（内表面ン・ｈｒ−ａｔｍ以上であるこ
とが実用性の点において望まれる。また、機械同強度は
、膜の厚み等によっても異なるが、中空糸１本当りの引
張破断強度が、ｉｏｏｇ以上であれば良い。The hollow fiber membrane with the above-mentioned five-layer structure can be expected to have high water permeability, and in particular, the membrane permeation rate for pure water is 1000 rh-atm or more based on the inner surface area. This is desired from the point of view of practicality.Furthermore, the mechanical strength varies depending on the thickness of the membrane, etc., but it is sufficient as long as the tensile strength at break per hollow fiber is ioog or more.
（ホ）実施例
以下、本発明を具体例によって示し、さらに詳細に説明
するが本発明はこれに何等限定されない。(E) Examples Hereinafter, the present invention will be illustrated by specific examples and explained in further detail, but the present invention is not limited thereto.
実施例１
溶媒としてジメチルスルホキシド、添加剤としてポリエ
チレングリコール２００、樹脂としてポリエーテルスル
ホン（ＩＣＩ社製５２００Ｐパウダー）を、この順に６
０：１８：２２の重量比で混合し、均なポリマー溶液を
作成した。このポリマー溶液を、内部凝固液であるジメ
チルスルホキシド５０％水溶液とともに二重環ノズルよ
り押し出した。空気中を２０ ｃｍ走行させた後、外部
凝固槽である水中に導き、内外両方向より凝固させ、中
空糸膜を作成した。Example 1 Dimethyl sulfoxide was used as a solvent, polyethylene glycol 200 was used as an additive, and polyether sulfone (5200P powder manufactured by ICI) was used as a resin.
They were mixed at a weight ratio of 0:18:22 to create a homogeneous polymer solution. This polymer solution was extruded from a double ring nozzle together with a 50% dimethyl sulfoxide aqueous solution as an internal coagulation liquid. After traveling 20 cm in the air, it was introduced into water, which is an external coagulation tank, and coagulated from both the inside and outside directions to create a hollow fiber membrane.
得られた中空糸膜は、内径０．４ｍｍ、外径０．６８ｍ
Ｉｎであり、純水の透水速度は１１００（２４（内表面
〉・ｈｒ−ａｔｍであった。また、分子ｉ６５，０００
の蛋白質（アルブミン）を５５％以上カットした。中空
糸の引張強度は破断強度が１２０ｇであり、伸度は３２
％であった。The obtained hollow fiber membrane had an inner diameter of 0.4 mm and an outer diameter of 0.68 m.
In, the water permeation rate of pure water was 1100 (24 (inner surface) hr-atm. Also, the molecule i was 65,000
protein (albumin) has been cut by more than 55%. The tensile strength of the hollow fiber is 120 g at break and the elongation is 32
%Met.
中空糸の断面構造は、第１図（Ｃ）に示すように、本発
明の５層構造よりなるが、内表面層（第１図（ω参照）
にのみ活性層を有し、中間層、外表面層（第１図（ｂ）
参照）はスポンジ状の層からなり５００〜２０００人の
孔径を有するものであった。The cross-sectional structure of the hollow fiber has a five-layer structure according to the present invention, as shown in FIG. 1 (C), but the inner surface layer (see FIG.
It has an active layer only in the middle layer and the outer surface layer (Fig.
Reference) was composed of a sponge-like layer and had a pore size of 500 to 2,000 pores.
実施例２
紡糸原液の組成をジメチルスルホキシド：ポリエチレン
グリコール：ポリエーテルスルホン−６０二２０：２０
となるようにし、内部凝固液にジメチルスルホキシド７
０％水溶液を用いた他は上記実施例１と同様にして、同
じ大きさの中空糸膜を作成した。Example 2 The composition of the spinning stock solution was dimethyl sulfoxide: polyethylene glycol: polyether sulfone-6020:20.
Add dimethyl sulfoxide 7 to the internal coagulation solution.
Hollow fiber membranes of the same size were prepared in the same manner as in Example 1 above, except that a 0% aqueous solution was used.
得られた中空糸は内表面層が緻密な層である５層構造を
有し、外表面層には最大０．２）ａ程度の孔が観察され
た。純水透水速度は１３００ρ冶（内表面）−ｈｒ−ａ
ｔｍ テあり、分子３８７，０００の蛋白質（コンアル
ブミン）を９０％以上カットした。また、破断強度は１
１５Ｑであり、伸度は３０％であった。The obtained hollow fiber had a five-layer structure in which the inner surface layer was a dense layer, and pores with a maximum size of about 0.2)a were observed in the outer surface layer. Pure water permeation rate is 1300rho (inner surface)-hr-a
With tmte, more than 90% of the 387,000 molecule protein (conalbumin) has been cut. Also, the breaking strength is 1
15Q, and the elongation was 30%.
比較例
紡糸ノズルを水中に入れ、水中で紡糸原液と内部凝固液
を吐出させた他は上記実施例２と全く同じ条件で紡糸し
、中空糸を得た。電子顕微鏡により、中空糸の構造を調
べたところ、内表面層、外表面層に緻密な活性層を有す
る５層構造からなる膜であった。この膜はアルブミンの
透過率は３５％であったが、純水透水速度は３５０ｌ／
ｍ２（内表面）・ｈｒ−ａｔｍと低いものであった。こ
のように、内・外画表面層に活性層を有するためにフラ
ックスが著しく低くなる。Comparative Example A hollow fiber was obtained by spinning under exactly the same conditions as in Example 2 above, except that the spinning nozzle was placed in water and the spinning dope and internal coagulation liquid were discharged in the water. When the structure of the hollow fiber was examined using an electron microscope, it was found to be a five-layer membrane having a dense active layer on the inner surface layer and the outer surface layer. This membrane had an albumin permeability of 35%, but a pure water permeation rate of 350 l/
m2 (inner surface)・hr-atm was low. As described above, since the inner and outer image surface layers have active layers, the flux becomes extremely low.
くべ）発明の詳細
な説明したように、本発明により、内表面層または外表
面層の一方が分離活性層を有する５Ｎ構造に構成したの
で、機械的強度および高透水性能の優れた膜を得ること
ができ、これにより膜分離工程での生産性を高めること
ができる効果がある。As described in detail, according to the present invention, since either the inner surface layer or the outer surface layer has a 5N structure having a separation active layer, a membrane with excellent mechanical strength and high water permeability can be obtained. This has the effect of increasing productivity in the membrane separation process.
第１図（ωは本発明の一実施例による繊維の形状を電子
顕微鏡により、ｉｏ、ｏｏｏ倍に拡大して示す内表面層
の内表面写真、第１図〈ｂ〉は上記実施例における繊維
の形状を電子顕微鏡によりｉｏ、ｏｏｏ倍に拡大して示
す外表面層の外表面写真、第１図（Ｃ）は上記実施例に
おける中空繊維の形状を電子顕微鏡により １００倍に
拡大して示す横断面写真である。
第
図（ａ）
第
図（ｂ）Fig. 1 (ω is an inner surface photograph of the inner surface layer showing the shape of the fiber according to an embodiment of the present invention magnified by io, ooo times using an electron microscope; Figure 1 (C) is a cross-sectional photograph of the outer surface layer showing the shape of the hollow fiber in the above example magnified 100 times using an electron microscope. These are side photographs. Figure (a) Figure (b)
Claims (1)
内表面層の５層構造からなり、外表面層又は内表面層の
一方が最小孔径を有する分離活性層であることを特徴と
するポリスルホン系中空糸膜。 ２、内表面層に分離活性層を有し、純水の透水速度が１
０００ｌ／ｍ＾２（内表面）・ｈｒ・ｋｇ／ｃｍ＾２以
上である請求項１記載のポリスルホン系中空糸膜。[Claims] 1. Outer surface layer, outer finger-like structure layer, intermediate layer, inner finger-like structure layer,
A polysulfone-based hollow fiber membrane comprising a five-layer structure including an inner surface layer, wherein one of the outer surface layer and the inner surface layer is a separation active layer having a minimum pore size. 2. Has a separate active layer on the inner surface layer, and the water permeation rate of pure water is 1.
2. The polysulfone-based hollow fiber membrane according to claim 1, wherein the polysulfone-based hollow fiber membrane has a viscosity of 000 l/m^2 (inner surface).hr.kg/cm^2 or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17356988A JPH0829241B2 (en) | 1988-07-11 | 1988-07-11 | Polysulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17356988A JPH0829241B2 (en) | 1988-07-11 | 1988-07-11 | Polysulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0221930A true JPH0221930A (en) | 1990-01-24 |
| JPH0829241B2 JPH0829241B2 (en) | 1996-03-27 |
Family
ID=15962992
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17356988A Expired - Lifetime JPH0829241B2 (en) | 1988-07-11 | 1988-07-11 | Polysulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0829241B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990058927A (en) * | 1997-12-30 | 1999-07-26 | 구광시 | Polysulfone hollow fiber membrane and its manufacturing method |
| KR100602429B1 (en) * | 1999-12-29 | 2006-07-20 | 주식회사 코오롱 | A polysulfone typed hollow fiber membrane, and a process of preparing for the same |
| JP2013052387A (en) * | 2011-09-01 | 2013-03-21 | Pall Corp | Multilayer microfiltration membrane |
-
1988
- 1988-07-11 JP JP17356988A patent/JPH0829241B2/en not_active Expired - Lifetime
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR19990058927A (en) * | 1997-12-30 | 1999-07-26 | 구광시 | Polysulfone hollow fiber membrane and its manufacturing method |
| KR100602429B1 (en) * | 1999-12-29 | 2006-07-20 | 주식회사 코오롱 | A polysulfone typed hollow fiber membrane, and a process of preparing for the same |
| JP2013052387A (en) * | 2011-09-01 | 2013-03-21 | Pall Corp | Multilayer microfiltration membrane |
| US8840791B2 (en) | 2011-09-01 | 2014-09-23 | Pall Corporation | Multilayer microfiltration membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0829241B2 (en) | 1996-03-27 |
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