JP2525037B2 - Polysulfone hollow fiber membrane - Google Patents
Polysulfone hollow fiber membraneInfo
- Publication number
- JP2525037B2 JP2525037B2 JP63174356A JP17435688A JP2525037B2 JP 2525037 B2 JP2525037 B2 JP 2525037B2 JP 63174356 A JP63174356 A JP 63174356A JP 17435688 A JP17435688 A JP 17435688A JP 2525037 B2 JP2525037 B2 JP 2525037B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- membrane
- layer
- fiber membrane
- polysulfone
- 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.)
- Expired - Lifetime
Links
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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
Description
【発明の詳細な説明】 （イ）産業上の利用分野 本発明は、中空糸状分離膜として有用なポリスルホン
系中空糸膜に関し、更に詳しくは、優れた濾過特性と機
械強度とを有するとともに、一定の分画性能を維持しな
がら高透水性能を有するポリスルホン系中空糸膜に関す
るものである。TECHNICAL FIELD The present invention relates to a polysulfone-based hollow fiber membrane useful as a hollow fiber-shaped separation membrane, and more specifically, it has excellent filtration characteristics and mechanical strength, The present invention relates to a polysulfone-based hollow fiber membrane having high water permeability while maintaining the above fractionation performance.
（ロ）従来の技術 一般に、ポリスルホン系中空糸膜は、主に限外濾過膜
として優れた特性を示すことが知られている。その他、
逆浸透膜やガス分離膜の支持膜としても使用されてい
る。これは、ポリスルホン系樹脂が耐熱性、耐薬品性、
機械的強度に優れた性能を有しており、この特性が分離
膜になっても保持され生かされるためである。このため
限外濾過膜としても食品工業、医療分野、電子工業用な
どその用途は多岐にわたっている。(B) Conventional Technology Generally, it is known that polysulfone-based hollow fiber membranes exhibit excellent characteristics mainly as an ultrafiltration membrane. Other,
It is also used as a support membrane for reverse osmosis membranes and gas separation membranes. This is because polysulfone resin has heat resistance, chemical resistance,
This is because it has excellent mechanical strength and this property is retained and utilized even when it is used as a separation membrane. Therefore, the ultrafiltration membrane has a wide variety of uses such as food industry, medical field, and electronic industry.
一方、従来より一般的に用いられているポリスルホン
系分離膜は膜壁を厚くして機械強度を維持していた。On the other hand, a polysulfone-based separation membrane that has been generally used conventionally has a thicker membrane wall to maintain mechanical strength.
（ハ）発明が解決しようとする課題 しかしながらこのような構造を有する分離膜は、機械
的強度には優れるものの膜壁が通液の抵抗になるため、
単位面積当りの膜濾過速度が小さいという欠点があっ
た。(C) Problems to be Solved by the Invention However, since the separation membrane having such a structure has excellent mechanical strength, the membrane wall has a resistance to liquid passage.
There is a drawback that the membrane filtration rate per unit area is low.
本発明者らは、以上のような従来使用されている分離
膜の欠点を解決し、機械強度を高くでき、かつ濾過速度
を大きくできる分離膜について鋭意研究を進めた結果、
中空糸の内径と膜厚の比を一定の比の間に保つことで上
記問題を解決できることを見出し、更にこの知見に基づ
き、種々の検討を進めた結果、本発明に至った。The present inventors have solved the drawbacks of the separation membranes that have been conventionally used as described above, and as a result of earnest research on a separation membrane that can increase mechanical strength and increase the filtration rate,
It has been found that the above problem can be solved by keeping the ratio of the inner diameter of the hollow fiber to the film thickness within a certain ratio, and further various investigations have been made based on this finding, resulting in the present invention.
（ニ）課題を解決するための手段及び作用 すなわち、本発明は、中空糸の内径に対する膜厚の比
が0.22〜0.35であって、断面が外表面層、外指状構造
層、中間層、内指状構造層、内表面層の５層構造からな
り、前記内表面層のみにスキン層を有するポリスルホン
系中空糸膜を提供するものである。(D) Means and Actions for Solving the Problem That is, the present invention has a ratio of the film thickness to the inner diameter of the hollow fiber of 0.22 to 0.35, and the cross section has an outer surface layer, an outer finger-like structure layer, an intermediate layer, It is intended to provide a polysulfone-based hollow fiber membrane having a five-layer structure of an inner finger-like structure layer and an inner surface layer, and having a skin layer only on the inner surface layer.
以下、詳細に本発明の説明を行う。 Hereinafter, the present invention will be described in detail.
本発明で使用されるポリスルホン系中空糸は、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下記
の構造からなるポリスルホン系樹脂およびその誘導体か
ら作られるものである。As the polysulfone-based hollow fiber used in the present invention, those known per se can be used. The polysulfone-based resin is made of a polysulfone-based resin having the following structure and a derivative thereof.
このようなポリスルホン樹脂を用いて中空糸膜を製造
するが、この時得られる中空糸の内径に対する膜厚の比
が0.22〜0.35の範囲にあれば、どのような方法によって
製造しても良い。 A hollow fiber membrane is produced using such a polysulfone resin, but any method may be used so long as the ratio of the membrane thickness to the inner diameter of the hollow fiber obtained at this time is in the range of 0.22 to 0.35.
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：ジメチルホ
ルムアミド、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：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：水ある
いは有機・無機水溶液）中に導くことによって得ること
ができる。The polysulfone-based hollow fiber membrane of the present invention is prepared by, for example, dissolving a raw material polysulfone-based resin in a polar organic solvent (eg, dimethylformamide, dimethylsulfoxide) in the presence of an appropriate additive (eg, polyethylene glycol) to prepare a spinning dope. This stock solution is extruded with an internal coagulating liquid (eg, a mixture of dimethyl sulfoxide and water) through a double-ring nozzle, run in air, and then into an external coagulating liquid (eg, water or organic / inorganic aqueous solution). Can be obtained by guiding.
ここで中空糸の内径に対する膜厚の比とは、膜厚みを
内径で除算した値を指して言い、この比が0.22より小さ
いと機械的強度が小さいか、あるいは膜の欠陥の多いも
のとなり、実用上問題がある。一方、比が0.35より大き
い場合には、機械的強度には優れるものの、濾過速度の
小さな膜となるだけでなく、膜厚みが大きいために、同
じ膜面積をもつ膜モジュールを作成する時、コンパクト
性に欠けるものとなってしまう。しかも、内径と膜厚の
比を0.22〜0.35の範囲にした時、濾過速度を高めるため
には、膜の断面構造を外表面層、外指状構造層、内指状
構造層、中間層、内表面層からなる５層構造を有する
膜、あるいは、外表面層、指状構造層、内表面層からな
る３層構造を有する膜であることが望ましい。ここで言
う外指状構造層ならびに内指状構造層とは、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。また、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、紡糸原液組成、凝固液温度および空中走
行距離によって変化する。Here, the ratio of the membrane thickness to the inner diameter of the hollow fiber refers to a value obtained by dividing the membrane thickness by the inner diameter.If this ratio is less than 0.22, the mechanical strength is low, or the membrane has many defects, There are practical problems. On the other hand, when the ratio is larger than 0.35, the membrane has excellent mechanical strength, but not only a small filtration rate but also a large membrane thickness, which makes it compact when creating a membrane module with the same membrane area. It lacks sex. Moreover, when the ratio of the inner diameter to the film thickness is in the range of 0.22 to 0.35, in order to increase the filtration rate, the cross-sectional structure of the film has an outer surface layer, an outer finger-like structure layer, an inner finger-like structure layer, an intermediate layer, It is desirable that the film has a five-layer structure including an inner surface layer, or a film having a three-layer structure including an outer surface layer, a finger-like structure layer, and an inner surface layer. The outer finger-like structure layer and the inner finger-like structure layer here are layers mainly contributing to maintenance of the hollow fiber membrane structure. On the other hand, the outer surface layer, the intermediate layer, and the inner surface layer are layers having a relatively dense structure, and their separation characteristics and water permeability are determined. Further, the intermediate layer of the hollow fiber membrane is formed as a boundary layer between the hollow fiber and the outer surface of the hollow fiber, because the solvent and the additive in the spinning dope can penetrate into the hollow fiber and the outer surface of the hollow fiber. The thickness of the intermediate layer is determined by the moving speeds in both directions, and varies depending on the spinning solution composition, the internal coagulation solution composition, the external coagulation solution composition, the spinning dope composition, the coagulation solution temperature, and the running distance in the air.
また、中空糸の内径は、２重環ノズルの口径、中空糸
の巻き取り速度および紡糸原液の吐出速度によって変化
する。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糸膜を形成することが
できる。The inner diameter of the hollow fiber changes depending on the diameter of the double ring nozzle, the winding speed of the hollow fiber, and the discharge speed of the spinning dope. Therefore, in consideration of the above, a desired hollow fiber membrane can be formed by appropriately setting these conditions.
このような構造を有する膜では、発達した指状構造層
が透過流速を高め、指状構造層におけるボイド周囲の組
織が機械強度に優れるため中空糸膜の機械強度も合わせ
持つことになる。In the membrane having such a structure, the developed finger-like structure layer increases the permeation flow velocity, and the tissue around the void in the finger-like structure layer has excellent mechanical strength, so that it also has the mechanical strength of the hollow fiber membrane.
又、工業的に限外濾過膜として使用される中空糸膜は
引張り強度で100g/本以上であることが望ましく、さら
に望ましくは、120g/本以上である。The hollow fiber membrane used industrially as an ultrafiltration membrane preferably has a tensile strength of 100 g / piece or more, more preferably 120 g / piece or more.
（ホ）実施例 以下、本発明を具体例によって示し、さらに詳細な説
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 shown in more detail with reference to specific examples, but the present invention is not limited thereto.
実施例１〜２ ポリエーテルスルホン（ICI社製,Victrex5200P）を20
重量％、溶媒剤としてジメチルスルホキシドを60重量
％、添加剤としてポリエチレングリコール（三洋化成製
分子量400）を20重量％の割合でそれぞれ混合し、均
一溶液とした。そして、この紡糸原液は、内部凝固液と
してのジメチルスルホキシド50％水溶液を２重環ノズル
の中央口から吐出しながら、２重環ノズルの外側環状口
から空中を走行させた後、水からなる凝固液へ浸漬する
ようにして導かれるものである。この際、巻き取り速度
を10m/分で行い、内径500〜800μｍ、肉厚150〜250μｍ
の中空糸膜とした。Examples 1-2 Polyether sulfone (ICI, Victrex 5200P) 20
% By weight, dimethylsulfoxide as a solvent agent at 60% by weight, and polyethylene glycol (Molecular weight 400 manufactured by Sanyo Kasei Co., Ltd. as an additive) at 20% by weight, respectively, to prepare a uniform solution. Then, this spinning dope was run in the air from the outer annular opening of the double ring nozzle while discharging 50% aqueous solution of dimethyl sulfoxide as the internal solidifying solution from the central opening of the double ring nozzle, and then solidified with water. It is guided so as to be immersed in the liquid. At this time, the winding speed is 10 m / min, the inner diameter is 500 to 800 μm, and the wall thickness is 150 to 250 μm.
Of the hollow fiber membrane.
得られた中空糸の性能を表１にまとめて示す。 The performance of the obtained hollow fibers is summarized in Table 1.
実施例３ 上記実施例１及び２で用いたドープを用い、芯液とし
てジメチルスルホキシド50重量部、水50重量部からなる
混合溶液を使用して、60℃の温水から成る外部凝固槽中
へ２重環ノズルから押し出した。得られた中空糸は膜厚
140μｍ、内径400μｍの中空糸膜であり、断面は５層構
造であった。この膜の純水透水速度は1120/m2・hr・k
g/cm2（水温25℃）と高く、また、分子量84,000のコン
アルブミンを90％排除する膜であった。機械強度も引張
り強度で120g/本であり、工業的に充分実用化できるも
のであった。Example 3 Using the dope used in Examples 1 and 2 above, a mixed solution of 50 parts by weight of dimethyl sulfoxide and 50 parts by weight of water was used as the core liquid, and the mixture was placed in an external coagulation bath of warm water at 60 ° C. It was extruded from the heavy ring nozzle. The resulting hollow fiber has a thickness
The hollow fiber membrane had a diameter of 140 μm and an inner diameter of 400 μm, and its cross section had a five-layer structure. The pure water permeation rate of this membrane is 1120 / m 2 · hr · k.
It was as high as g / cm 2 (water temperature 25 ° C), and it was a membrane that eliminated 90% of conalbumin with a molecular weight of 84,000. The mechanical strength was 120 g / piece in tensile strength, which was industrially sufficiently practical.
そして、実施例１〜３の各断面構造はそれぞれ５層構
造であった。いずれの膜も、内表面層のみにスキン層を
有する膜であった。 And each cross-sectional structure of Examples 1-3 was a 5-layer structure, respectively. All films were films having a skin layer only on the inner surface layer.
比較例１ 上記実施例１及び２と全く同じ操作により、内径400
μｍ、膜厚80μｍ、従って内径に対する膜厚の比が0.20
の中空糸膜を得た。この膜の純水透水速度は1120/m2
・hr・atm（25℃）であったが、引張り強度が70g/本と
低いものであり、工業的に長期に亘って信頼して使用で
きるものではないことが分かった。Comparative Example 1 The same operation as in Examples 1 and 2 above was performed to obtain an inner diameter of 400
μm, film thickness 80 μm, so the ratio of film thickness to inner diameter is 0.20
A hollow fiber membrane of The pure water permeability of this membrane is 1120 / m 2
・ It was hr ・ atm (25 ℃), but the tensile strength was as low as 70g / piece, and it was found that it cannot be used reliably for a long time industrially.
（ヘ）発明の効果 以上述べた様に、本発明により、中空糸の内径に対す
る膜厚の比を0.22〜0.35に設定したので、高透水性と実
用上必要な強度を有する中空糸膜を得ることができる効
果がある。(F) Effect of the invention As described above, according to the present invention, the ratio of the film thickness to the inner diameter of the hollow fiber is set to 0.22 to 0.35, so that a hollow fiber membrane having high water permeability and practically necessary strength is obtained. There is an effect that can be.
Claims (2)
35であって、断面が外表面層、外指状構造層、中間層、
内指状構造層、内表面層の５層構造からなり、前記内表
面層のみにスキン層を有することを特徴とするポリスル
ホン系中空糸膜。1. The ratio of the film thickness to the inner diameter of the hollow fiber is 0.22 to 0.
35, the cross-section is an outer surface layer, an outer finger structure layer, an intermediate layer,
A polysulfone-based hollow fiber membrane comprising a five-layer structure of an inner finger structure layer and an inner surface layer, and having a skin layer only on the inner surface layer.
ある請求項１記載のポリスルホン系中空糸膜。2. The polysulfone-based hollow fiber membrane according to claim 1, wherein the tensile strength of the hollow fiber at break is 100 g / strand or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174356A JP2525037B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63174356A JP2525037B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0226627A JPH0226627A (en) | 1990-01-29 |
| JP2525037B2 true JP2525037B2 (en) | 1996-08-14 |
Family
ID=15977195
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63174356A Expired - Lifetime JP2525037B2 (en) | 1988-07-12 | 1988-07-12 | Polysulfone hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2525037B2 (en) |
Families Citing this family (2)
| 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 |
| CN113522050B (en) * | 2020-04-14 | 2023-07-21 | Nok株式会社 | Polysulfone-based hollow fiber membrane and hollow fiber membrane module |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60246812A (en) * | 1984-05-18 | 1985-12-06 | Daicel Chem Ind Ltd | Hollow polysulfone based resin fiber |
| JPS61103504A (en) * | 1984-10-29 | 1986-05-22 | Sumitomo Bakelite Co Ltd | Preparation of hollow fibrous separation membrane |
| JPS61164602A (en) * | 1985-01-17 | 1986-07-25 | Daicel Chem Ind Ltd | Hllow yarn membrane made of polysulfone resin and its preparation |
-
1988
- 1988-07-12 JP JP63174356A patent/JP2525037B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0226627A (en) | 1990-01-29 |
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