JPH0347127B2 - - Google Patents
Info
- Publication number
- JPH0347127B2 JPH0347127B2 JP56031663A JP3166381A JPH0347127B2 JP H0347127 B2 JPH0347127 B2 JP H0347127B2 JP 56031663 A JP56031663 A JP 56031663A JP 3166381 A JP3166381 A JP 3166381A JP H0347127 B2 JPH0347127 B2 JP H0347127B2
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone
- membrane
- hollow fiber
- solvent
- water
- 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
- 239000012528 membrane Substances 0.000 claims description 41
- 229920002492 poly(sulfone) Polymers 0.000 claims description 39
- 239000012510 hollow fiber Substances 0.000 claims description 30
- 229920005989 resin Polymers 0.000 claims description 22
- 239000011347 resin Substances 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 239000000243 solution Substances 0.000 description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 20
- 230000035699 permeability Effects 0.000 description 11
- 238000000034 method Methods 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000002202 Polyethylene glycol Substances 0.000 description 6
- 238000005345 coagulation Methods 0.000 description 6
- 230000015271 coagulation Effects 0.000 description 6
- 229920001223 polyethylene glycol Polymers 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 230000001112 coagulating effect Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000012456 homogeneous solution Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007711 solidification Methods 0.000 description 3
- 230000008023 solidification Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000000578 dry spinning Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- -1 ZnCl 2 Chemical class 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明はポリスルホン系樹脂からなる中空糸膜
の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a method for manufacturing a hollow fiber membrane made of polysulfone resin.
（従来の技術）
従来より、中空糸膜の素材としてはポリスルホ
ン系、ポリアクリロニトリル系、酢酸セルロース
などのセルロース系、ポリアミド系、ポリカーボ
ネート系、ポリビニルアルコール系など多くの高
分子化合物が使用されてきた。ながでも、ポリス
ルホン系樹脂は耐熱性、耐酸性、耐アルカリ性、
耐酸化性などの耐薬品性が優れているので、酸化
剤、酸、アルカリなどによつて膜を薬洗すること
により再生しうるし、さらに加熱殺菌やホルマリ
ン、塩素など薬剤による殺菌も可能なことから、
最近中空糸膜素材として注目されている。(Prior Art) Conventionally, many polymeric compounds such as polysulfone, polyacrylonitrile, cellulose such as cellulose acetate, polyamide, polycarbonate, and polyvinyl alcohol have been used as materials for hollow fiber membranes. However, polysulfone resin is heat resistant, acid resistant, alkali resistant,
It has excellent chemical resistance such as oxidation resistance, so it can be regenerated by cleaning the membrane with oxidizing agents, acids, alkalis, etc., and it can also be sterilized by heat sterilization, formalin, chlorine, etc. from,
Recently, it has been attracting attention as a hollow fiber membrane material.
ポリスルホン系樹脂を用いて透水性の高い中空
糸膜を得る方法として従来より次のような方法が
提案されている。 The following methods have been proposed as methods for obtaining hollow fiber membranes with high water permeability using polysulfone resins.
(1) 異種ポリマー間のマクロ相分離を利用する方
法（特公昭48−176号公報、特開昭54−144456
号公報。）
(2) 製膜後、抽出・溶出操作を有する方法（特開
昭54−26283号公報）。(1) Method using macro phase separation between different types of polymers (Japanese Patent Publication No. 176-1976, Japanese Patent Application Laid-open No. 144456-1983
Publication No. ) (2) A method that includes extraction and elution operations after film formation (Japanese Patent Application Laid-Open No. 54-26283).
（発明が解決しようとする課題）
しかし、(1)の方法ではポリエチレングリコー
ル、ポリビニルピロリドン、ポリエチレンイミン
などの異種ポリマーを大量にブレンドするため、
ポリスルホン系樹脂の本来の良好な性能が失われ
やすい。また、(2)の方法は、ブレンドポリマーの
抽出操作が困難であつた。(Problem to be Solved by the Invention) However, in method (1), a large amount of different polymers such as polyethylene glycol, polyvinylpyrrolidone, and polyethyleneimine are blended;
The original good performance of polysulfone resin is likely to be lost. Furthermore, in method (2), extraction of the blended polymer was difficult.
したがつて本発明の目的は、上記従来技術の問
題点を解消した。特に透水性に優れたポリスルホ
ン系中空糸膜の製造方法を提供することにある。 Therefore, an object of the present invention is to eliminate the problems of the prior art described above. It is an object of the present invention to provide a method for producing a polysulfone hollow fiber membrane having particularly excellent water permeability.
（課題を解決するための手段）
本発明者らは、従来技術の限界を打破し、一層
の中空糸膜性能の改善を目的として、種々検討し
た結果、ポリスルホン溶液に親水性高分子と該ポ
リスルホン系樹脂の非溶剤を加えてゆくと、均一
溶液の領域から、相分離が生じる濁化濃度領域に
変化してゆくことを認めた。かかる濁化濃度領域
の溶液は、従来技術では製膜溶液としては全く使
用できないものとされていたが、驚くべきこと
に、該濁化濃度領域の溶液を、さらに冷却する
と、均一でかつ透明な溶液に変化し、この溶液は
製膜溶液として極めて良好に使用できることを見
い出した。溶解度を向上させるためには、通常は
温度を上げるべきであるが、上記製膜溶液では、
逆に冷却することにより均一溶液となるのであ
り、かかる事実は、全く予想できないことであつ
た。(Means for Solving the Problems) In order to overcome the limitations of the conventional technology and further improve the performance of hollow fiber membranes, the present inventors conducted various studies, and found that a hydrophilic polymer and the polysulfone were added to a polysulfone solution. It was observed that as a non-solvent for the system resin was added, the concentration changed from a homogeneous solution region to a turbid concentration region where phase separation occurred. In the prior art, it was believed that a solution in this turbid concentration range could not be used at all as a film forming solution, but surprisingly, when the solution in this turbid concentration range was further cooled, it became uniform and transparent. It was found that this solution can be used very well as a membrane forming solution. To improve solubility, the temperature should usually be increased, but in the above membrane-forming solution,
On the contrary, by cooling, the solution becomes a homogeneous solution, which was completely unexpected.
すなわち本発明は、ポリスルホン系樹脂、親水
性高分子、該ポリスルホン系樹脂の非溶剤および
それらの共通溶媒からなる、高温側でミクロ相分
離する製膜溶液を冷却して均一な溶液を調製した
後、製膜することを特徴とするポリスルホン系中
空糸膜の製造方法である。 That is, the present invention involves cooling a membrane-forming solution that undergoes microphase separation on the high temperature side, which is composed of a polysulfone resin, a hydrophilic polymer, a non-solvent for the polysulfone resin, and a common solvent thereof, to prepare a uniform solution. This is a method for producing a polysulfone-based hollow fiber membrane, which is characterized by forming a polysulfone-based hollow fiber membrane.
本発明で用いるポリスルホン系樹脂は、通常式
(1)、
または式(2)：
で示される繰り返し単位を有するものがあげられ
る。 The polysulfone resin used in the present invention has the usual formula
(1), Or formula (2): Examples include those having repeating units shown in the following.
それらのうち式(1)で示される繰返し単位を有す
るポリスルホン系樹脂は機械的強度、耐熱性、耐
薬品性および生体適合性などの基本的な特性に優
れており好ましく使用される。ポリスルホン系樹
脂は製膜可能で、かつ中空糸膜としての特性を有
する濃度範囲であればよく、通常５〜50重量％が
適当である。 Among them, a polysulfone resin having a repeating unit represented by formula (1) is preferably used because it has excellent basic properties such as mechanical strength, heat resistance, chemical resistance, and biocompatibility. The polysulfone resin may be used in any concentration range as long as it can be used to form a membrane and has properties as a hollow fiber membrane, and usually 5 to 50% by weight is appropriate.
親水性高分子はポリスルホン系樹脂と相溶性が
あり、かつ親水性を有する高分子であり、従来よ
りポリスルホン系中空糸膜の製膜溶液に用いられ
るポリエチレングリコール、ポリビニルピロリド
ン、ポリエチレンイミン等があげられるが、これ
らに限定されるものではない。通常ポリエチレン
グリコールが有利に用いられる。ポリエチレング
リコールは分子量600のものが市販されており、
これを使うのが便利であるが、もちろそれ以外の
分子量のものを使用してもかまわない。 Hydrophilic polymers are polymers that are compatible with polysulfone-based resins and have hydrophilic properties, and include polyethylene glycol, polyvinylpyrrolidone, polyethyleneimine, etc., which are conventionally used in membrane forming solutions for polysulfone-based hollow fiber membranes. However, it is not limited to these. Usually polyethylene glycol is advantageously used. Polyethylene glycol is commercially available with a molecular weight of 600.
Although it is convenient to use this, it is of course possible to use molecules with other molecular weights.
溶媒はポリスルホン系樹脂および親水性高分子
を共に溶解する溶媒であり、ジメチルスルホキシ
ド、ジメチルアセトアミド、ジメチルホルムアミ
ド、Ｎ−メチル−２−ピロリドン、ジオキサン
等、多種の溶媒が用いられる。特にジメチルアセ
トアミド、ジメチルスルホキシド、ジメチルホル
ムアミド、Ｎ−メチル−２−ピロリドンが好まし
い。 The solvent is a solvent that dissolves both the polysulfone resin and the hydrophilic polymer, and various solvents such as dimethylsulfoxide, dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone, and dioxane are used. Particularly preferred are dimethylacetamide, dimethylsulfoxide, dimethylformamide, and N-methyl-2-pyrrolidone.
ポリスルホン系樹脂の非溶剤は、ポリスルホン
系樹脂の非溶媒または膨潤剤となるものであれば
何でもよく、通常特公昭48−176号公報などに記
載されているZnCl2等の無機塩、アルコール等の
有機物、水などがあげられる。生産コストの点で
は水が最も好ましく用いられる。非溶剤の種類と
量は、ポリスルホン系樹脂に対する凝固性を考え
合わせた上で選択すれば良い。本発明では、この
第４成分を添加した点に特徴を有しており、かか
る製膜溶液を使用することにより透水性の優れた
中空糸膜を得ることができる。 The non-solvent for the polysulfone-based resin may be anything as long as it serves as a non-solvent or a swelling agent for the polysulfone-based resin, and is usually inorganic salts such as ZnCl 2 , alcohol, etc. described in Japanese Patent Publication No. 176-1976. Examples include organic matter and water. Water is most preferably used in terms of production costs. The type and amount of the non-solvent may be selected in consideration of the coagulability of the polysulfone resin. The present invention is characterized by the addition of this fourth component, and by using such a membrane forming solution, a hollow fiber membrane with excellent water permeability can be obtained.
本発明で用いたポリスルホン系樹脂と溶媒およ
び親水性高分子およびポリスルホン系樹脂の非溶
剤と溶媒の溶解性は一般的にポリマー溶媒がそう
であるように高温程大となる。しかるに、本発明
の製膜溶液においては、これらとは全く逆に低温
で混合物の相溶性が大となり均一溶液が生成され
るという事実は本発明者らの全く新しい知見であ
る。 The solubility of the polysulfone resin used in the present invention in the solvent and the non-solvent of the hydrophilic polymer and polysulfone resin generally increases as the temperature increases, as in the case of polymer solvents. However, in the film-forming solution of the present invention, the fact that, on the contrary, the compatibility of the mixture increases at low temperatures and a homogeneous solution is produced is a completely new finding by the present inventors.
この新規な現象の原因は不明であるが、この現
象を利用することにより、従来の製法が得られた
中空糸膜よりも透水性の大きな中空糸膜を得るこ
とができる。 Although the cause of this novel phenomenon is unknown, by utilizing this phenomenon, it is possible to obtain a hollow fiber membrane with higher water permeability than hollow fiber membranes obtained by conventional manufacturing methods.
次に本発明によるポリスルホン系中空糸膜の製
造方法について述べる。 Next, a method for manufacturing a polysulfone hollow fiber membrane according to the present invention will be described.
ポリスルホン系中空糸膜の製膜方法としては、
製膜溶液を直接凝固浴に押し出す湿式法と、凝固
浴中に押出す前に一旦気相中に曝す乾湿式法を用
いることができる。 The method for producing polysulfone hollow fiber membranes is as follows:
A wet method in which the film-forming solution is directly extruded into a coagulation bath, and a wet-dry method in which it is once exposed to a gas phase before being extruded into a coagulation bath can be used.
凝固液は、溶媒とは混和するが、ポリスルホン
系樹脂に対しては凝固能を有する非溶剤が用いら
れる。非溶剤は単独又は２種以上を混合し用いる
ことができ、非溶媒に無機又は有機塩や溶剤を混
合すると好ましい場合がある。これらのうち取扱
い性等から水が好ましい。 Although the coagulating liquid is miscible with the solvent, a non-solvent having coagulating ability is used for polysulfone resin. The non-solvent can be used alone or in combination of two or more types, and it may be preferable to mix an inorganic or organic salt or a solvent with the non-solvent. Among these, water is preferred from the viewpoint of ease of handling.
中空糸の場合、中空系の外部と内部から同時
に、または内部と外部のどちらか一方から凝固が
行なわれる。内部凝固液は外部凝固液と同一で
も、また異なつたものでもよい。この他に気体を
注入してもよい。乾湿式紡糸による中空糸の場
合、内部凝固注入液として、凝固能の小さいエタ
ノール等の有機溶剤単独または水との混合液、さ
らにはジメチルホルムアミド等のポリスルホン系
樹脂の溶媒と水との混合液を用いた場合、透水性
がさらに向上することがある。 In the case of hollow fibers, coagulation is carried out simultaneously from the outside and the inside of the hollow system, or from either the inside or the outside. The internal coagulating liquid may be the same as the external coagulating liquid or may be different. In addition to this, gas may also be injected. In the case of hollow fibers produced by dry-wet spinning, an organic solvent such as ethanol with low coagulation ability alone or a mixture with water is used as the internal coagulation injection liquid, or a mixture of a polysulfone resin solvent such as dimethylformamide and water is used. When used, water permeability may be further improved.
凝固後、洗浄が行なわれる。 After solidification, washing is performed.
また必要に応じ水を主成分とした浴中で湿熱処
理を行なうことができる。通常湿潤膜を乾燥する
と透水性が低下するが、湿熱処理により乾燥後も
透水性を保持できる場合があり有効である。 Further, if necessary, moist heat treatment can be carried out in a bath containing water as a main component. Normally, when a wet membrane is dried, its water permeability decreases, but moist heat treatment may be effective in maintaining water permeability even after drying.
また本発明において用いられる製膜溶液は低温
状態で安定であるため、温度の調節が容易で中空
糸膜を安定に製造できる。 Furthermore, since the membrane forming solution used in the present invention is stable at low temperatures, the temperature can be easily adjusted and hollow fiber membranes can be stably manufactured.
本発明により得られる中空糸膜は、ポリスルホ
ン系樹脂からなつているため、耐熱性、耐薬品
性、機械的性質に優れ、しかも新規な製膜溶液を
用いて製膜したため、膜の透過性能、特に透水性
に非常に優れ各種の精密過および限外去分野
に用いることができる。また本発明で得られたポ
リスルホン系中空糸膜は膜中に親水性高分子を存
在させることもできる。 Since the hollow fiber membrane obtained by the present invention is made of polysulfone resin, it has excellent heat resistance, chemical resistance, and mechanical properties.Moreover, since the membrane was formed using a new membrane forming solution, the permeation performance of the membrane is In particular, it has excellent water permeability and can be used in various precision filtering and ultrafiltration fields. Further, the polysulfone hollow fiber membrane obtained in the present invention can also have a hydrophilic polymer present in the membrane.
（実施例）
以下実施例によつて、本発明のポリスルホン系
中空糸膜の製造方法を説明する。(Example) The method for producing the polysulfone hollow fiber membrane of the present invention will be described below with reference to Examples.
実施例
ポリスルホン（UCC社製、Ｐ−1700）４Kg、
分子量600のポリエチレングリコール6.8Kg、水
0.02Kg、およびＮ，Ｎ−ジメチルホルムアミド
（DMF）9.2Kgを100℃で３時間加熱撹拌後18℃に
冷却し、18℃で16時間脱泡して均一透明な製膜溶
液を得た。この製膜溶液は20.5℃に昇温すると白
濁し、ミクロ相分離を起こした。この製膜溶液を
18℃とし、孔径1.0mm、ニードル径0.5mmの環状ノ
ズルより乾湿式紡糸を行なつた。この際ニードル
に注入する注入液として20℃のDMF／水＝90／
10のDMF水溶液を使用し、温度15℃、湿度80％
の乾式部の長さを１cmとし、凝固液として20℃の
水を使用した。また原液流量は2.8c.c.／min、捲
取速度6.3ｍ／minであつた。凝固後水洗し、さ
らに98℃の熱水で２時間定長湿熱処理を施こし
た。得られたポリスルホン系中空糸膜の外径は
800μ、内径は550μ、透水率は1420／m2hrKg／
cm2であつた。この中空糸膜5000本を束ね、接着剤
でシールし、中空糸有効長が100cmが片端開口、
他端フリーシールの中空糸束を得た。この中空糸
束を直胴部が４インチの筐体に装着し、２インチ
の水道蛇口を直結し、過圧1.4Kg／cm2、温度12
〜14℃で１ケ月間連続で水道水の外圧全過を行
なつた。この際平均５m2／hrの浄水が得られ、そ
の水質は完全除菌されていた。Example Polysulfone (manufactured by UCC, P-1700) 4 kg,
6.8Kg of polyethylene glycol with a molecular weight of 600, water
0.02 kg and 9.2 kg of N,N-dimethylformamide (DMF) were heated and stirred at 100°C for 3 hours, cooled to 18°C, and defoamed at 18°C for 16 hours to obtain a homogeneous and transparent membrane forming solution. When this membrane forming solution was heated to 20.5°C, it became cloudy and microphase separation occurred. This film forming solution
Wet-dry spinning was carried out at 18°C using an annular nozzle with a hole diameter of 1.0 mm and a needle diameter of 0.5 mm. At this time, the injection liquid to be injected into the needle is DMF/water at 20℃ = 90/
10 DMF aqueous solution, temperature 15℃, humidity 80%
The length of the dry section was 1 cm, and water at 20°C was used as the coagulating liquid. The flow rate of the stock solution was 2.8 cc/min, and the winding speed was 6.3 m/min. After solidification, it was washed with water and further subjected to a moist heat treatment for 2 hours with hot water at 98°C. The outer diameter of the obtained polysulfone hollow fiber membrane is
800μ, inner diameter 550μ, water permeability 1420/m 2 hrKg/
It was warm in cm2 . 5,000 of these hollow fiber membranes are bundled and sealed with adhesive, and the effective length of the hollow fibers is 100cm with one end open.
A hollow fiber bundle with a free seal at the other end was obtained. This hollow fiber bundle was attached to a case with a 4-inch straight body, and a 2-inch water faucet was directly connected to it, with an overpressure of 1.4 Kg/cm 2 and a temperature of 12
The entire external pressure of tap water was passed continuously for one month at ~14°C. At this time, an average of 5 m 2 /hr of purified water was obtained, and the water quality was completely sterilized.
比較例
ポリスルホン（UCC社製、Ｐ−1700）200ｇ、
分子量600のポリエチレングリコール300ｇおよび
DMF500ｇを加熱撹拌、冷却、脱泡して製膜溶液
を得た。この製膜溶液を30℃とし実施例１と同様
に乾湿式紡糸を行なつた。この際注入液および凝
固液として20℃の水を使用し、乾式部の長さを25
cmとし乾式部の温度を20℃、相対湿度を65％に保
つた。凝固後水洗し、さらに98℃の熱水で２時間
湿熱処理を施こした。得られたポリスルホン系中
空糸膜の外径は0.6mm、内径は0.45mmであり、透
水率は540／m2hrKg／cm2であつた。Comparative example: 200 g of polysulfone (manufactured by UCC, P-1700),
300g of polyethylene glycol with a molecular weight of 600 and
500 g of DMF was heated, stirred, cooled, and defoamed to obtain a membrane forming solution. This membrane-forming solution was heated to 30° C. and wet-dry spinning was performed in the same manner as in Example 1. At this time, water at 20℃ was used as the injection liquid and coagulation liquid, and the length of the dry section was adjusted to 25℃.
cm, and the temperature of the dry section was maintained at 20°C and relative humidity at 65%. After solidification, it was washed with water and further subjected to a moist heat treatment with hot water at 98°C for 2 hours. The obtained polysulfone hollow fiber membrane had an outer diameter of 0.6 mm, an inner diameter of 0.45 mm, and a water permeability of 540/m 2 hrKg/cm 2 .
（発明の効果）
本発明は高温側でミクロ相分離する製膜溶液を
用いるので、ポリスルホン系中空糸膜の、透水性
を向上させることができ、かつ得られるポリスル
ホン系中空糸膜は、目づまり、汚れに対して強い
ため、一般産業用途及びメデイカル用途等に使用
することができる。(Effects of the Invention) Since the present invention uses a membrane-forming solution that undergoes microphase separation on the high temperature side, the water permeability of polysulfone-based hollow fiber membranes can be improved, and the resulting polysulfone-based hollow fiber membranes are free from clogging. Since it is resistant to stains, it can be used for general industrial purposes and medical purposes.
Claims (1)
スルホン系樹脂の非溶剤およびそれらの共通溶媒
からなる、高温側でミクロ相分離する製膜溶液を
冷却して均一な溶液に調製した後、製膜すること
を特徴とするポリスルホン系中空糸膜の製造方
法。1. A membrane forming solution that undergoes microphase separation on the high temperature side, which consists of a polysulfone resin, a hydrophilic polymer, a non-solvent for the polysulfone resin, and a common solvent thereof, is cooled to a uniform solution, and then a membrane is formed. A method for producing a polysulfone hollow fiber membrane, characterized by:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3166381A JPS57147488A (en) | 1981-03-04 | 1981-03-04 | Preparation of purified water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3166381A JPS57147488A (en) | 1981-03-04 | 1981-03-04 | Preparation of purified water |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP10612590A Division JPH0368433A (en) | 1990-04-20 | 1990-04-20 | Production of polysulfone hollow fiber membrane for production clean water |
| JP10612490A Division JPH0379668A (en) | 1990-04-20 | 1990-04-20 | Solution for preparing film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57147488A JPS57147488A (en) | 1982-09-11 |
| JPH0347127B2 true JPH0347127B2 (en) | 1991-07-18 |
Family
ID=12337373
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3166381A Granted JPS57147488A (en) | 1981-03-04 | 1981-03-04 | Preparation of purified water |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57147488A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018159353A1 (en) | 2017-03-01 | 2018-09-07 | Nok株式会社 | Method for preparing polyphenylsulfone porous hollow fiber membrane |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS58163406A (en) * | 1982-03-23 | 1983-09-28 | Nitto Electric Ind Co Ltd | Filtration of liquid |
| JPS61164602A (en) * | 1985-01-17 | 1986-07-25 | Daicel Chem Ind Ltd | Hllow yarn membrane made of polysulfone resin and its preparation |
| JPH0675667B2 (en) * | 1985-04-17 | 1994-09-28 | 東レ株式会社 | Method for producing semi-permeable membrane of polysulfone resin |
| JPS6397205A (en) * | 1986-10-15 | 1988-04-27 | Toray Ind Inc | Treatment of polysulfone resin semipermeable membrane |
| JP2505428B2 (en) * | 1986-10-15 | 1996-06-12 | 東レ株式会社 | Low-temperature dissolving stock solution and method for producing the same |
| JPH0729030B2 (en) * | 1986-11-05 | 1995-04-05 | ダイセル化学工業株式会社 | Method for producing hollow fiber membrane module |
| JPH0379668A (en) * | 1990-04-20 | 1991-04-04 | Kuraray Co Ltd | Solution for preparing film |
| JPH0368433A (en) * | 1990-04-20 | 1991-03-25 | Kuraray Co Ltd | Production of polysulfone hollow fiber membrane for production clean water |
| EP0750938B1 (en) * | 1995-06-30 | 2005-02-16 | Toray Industries, Inc. | Manufacture of a polysulfone hollow fiber semipermeable membrane |
| JP2012061383A (en) * | 2010-09-14 | 2012-03-29 | Kobelco Eco-Solutions Co Ltd | Hollow fiber membrane unit, water treatment apparatus, and water treatment method |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5439952A (en) * | 1977-09-05 | 1979-03-28 | Kuraray Co Ltd | Method of producing purified water |
| JPS55132603A (en) * | 1979-04-04 | 1980-10-15 | Kuraray Co Ltd | Purifying method of water for dialysis |
-
1981
- 1981-03-04 JP JP3166381A patent/JPS57147488A/en active Granted
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5439952A (en) * | 1977-09-05 | 1979-03-28 | Kuraray Co Ltd | Method of producing purified water |
| JPS55132603A (en) * | 1979-04-04 | 1980-10-15 | Kuraray Co Ltd | Purifying method of water for dialysis |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018159353A1 (en) | 2017-03-01 | 2018-09-07 | Nok株式会社 | Method for preparing polyphenylsulfone porous hollow fiber membrane |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57147488A (en) | 1982-09-11 |
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