JP3205268B2 - Method for producing selectively permeable hollow fiber membrane - Google Patents
Method for producing selectively permeable hollow fiber membraneInfo
- Publication number
- JP3205268B2 JP3205268B2 JP24777096A JP24777096A JP3205268B2 JP 3205268 B2 JP3205268 B2 JP 3205268B2 JP 24777096 A JP24777096 A JP 24777096A JP 24777096 A JP24777096 A JP 24777096A JP 3205268 B2 JP3205268 B2 JP 3205268B2
- Authority
- JP
- Japan
- Prior art keywords
- hollow fiber
- polyhydric alcohol
- organic solvent
- producing
- fiber membrane
- 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 - Fee Related
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Description
【０００１】[0001]
【発明の属する技術分野】本発明は、特に血液浄化用に
有用な選択透過性中空糸膜の製造方法に関する。例え
ば、腎不全患者用の人工透析膜、特に最近透析患者の長
期合併症との関係で注目されているβ2 ―ミクログロブ
リンに代表される中高分子量物質の除去に適している中
空糸膜の製造方法に関する。また、単に血液濾過透析、
血液濾過にも適している中空糸膜の製造方法に関する。The present invention relates to a method for producing a selectively permeable hollow fiber membrane particularly useful for blood purification. For example, manufacture of artificial dialysis membranes for patients with renal insufficiency, especially hollow fiber membranes suitable for removing medium-high molecular weight substances such as β 2 -microglobulin, which has recently attracted attention in relation to long-term complications of dialysis patients About the method. Also, simply hemofiltration dialysis,
The present invention relates to a method for producing a hollow fiber membrane which is also suitable for hemofiltration.
【０００２】[0002]
【従来の技術】近年、透析患者の長期合併症と関連し
て、透析アミロイドシスの原因物質と考えられているβ
2 ―ＭＧ（分子量１１，８００）、掻痒感、高脂血症と
関係すると考えられる副甲状腺ホルモン（分子量約９，
５００）、関節痛、骨痛に係わると考えられる分子量２
〜４万の物質、など比較的中高分子量領域の有害物質の
除去の必要性がさけばれている。一方、人体に必須のア
ルブミン（分子量６６，０００）の損失は極力避けなけ
ればならない。2. Description of the Related Art In recent years, in connection with long-term complications of dialysis patients, β which is considered to be a causative substance of dialysis amyloidosis
2- MG (molecular weight 11,800), parathyroid hormone (molecular weight of about 9,
500), molecular weight 2 thought to be related to joint pain and bone pain
The need to remove harmful substances in the relatively medium to high molecular weight region, such as ~ 40,000 substances, has been avoided. On the other hand, loss of albumin (molecular weight: 66,000), which is essential for the human body, must be avoided as much as possible.
【０００３】すなわち、分子量４〜５万以下の物質の透
過性に優れ、一方分子量６万以上の物質の阻止性のよい
分画分子量のシャープカット性の良好な選択透過性膜が
望まれている。[0003] That is, there is a demand for a permselective membrane having excellent permeability for substances having a molecular weight of 40,000 or less and 50,000 or less, and having good rejection of substances having a molecular weight of 60,000 or more and having a good sharp cut of molecular weight. .
【０００４】従来からセルロース誘導体を原料とする中
空糸膜の開発は活発に行われてきたが、例えば特公昭５
８―２４１６５号公報に見られるように、中空糸を湿式
紡糸するときの芯剤として流動パラフィン、高級アルコ
ール、イソプロピルミリステートなど、トリアセテート
紡糸原液に対して凝固性のないものを使用するため、紡
糸時の曵糸性を高くするためには紡糸原液におけるトリ
アセテートの濃度を高めざるを得ず、また紡糸原液の凝
固は必然的にノズルから出糸後、中空糸外面から凝固液
で固化させることになるため、中空糸外面に緻密構造層
が形成される。Hitherto, the development of hollow fiber membranes using a cellulose derivative as a raw material has been actively conducted.
As disclosed in Japanese Patent Application Laid-Open No. 8-24165, spinning of a non-coagulable triacetate spinning solution such as liquid paraffin, higher alcohol, isopropyl myristate, etc. as a core agent for wet spinning a hollow fiber is required. In order to improve the spinnability at the time, it is necessary to increase the concentration of triacetate in the spinning dope, and coagulation of the spinning dope is inevitably performed by spinning out from the nozzle and solidifying with the coagulating liquid from the outer surface of the hollow fiber. Therefore, a dense structure layer is formed on the outer surface of the hollow fiber.
【０００５】これらの理由により、従来セルロース誘導
体中空糸は、合成ポリマーの膜に比べて、緻密層と多孔
層の密度差が小さく、全体として均一層に近く、物質の
透過性能が十分とはいえなかった。[0005] For these reasons, the conventional cellulose derivative hollow fiber has a smaller density difference between the dense layer and the porous layer than the synthetic polymer membrane, is close to a uniform layer as a whole, and has a sufficient substance permeability. Did not.
【０００６】ポリサルホンなどの合成高分子では、例え
ば特公平２―１８６９５号や特公平５―５４３７３号公
報に見られるように、比較的上記要求を満たしたものが
得られている。[0006] Synthetic polymers such as polysulfone have been obtained which relatively satisfy the above requirements as seen in, for example, Japanese Patent Publication No. 2-18695 and Japanese Patent Publication No. 5-54337.
【０００７】一方特開平８―９７０号公報には、芯剤に
Ｎ2 ガスを使用し、セルロース誘導体、特にトリアセテ
ートの透過性を向上させた中空糸膜が開示されている。
これによると、純水の限外濾過係数１０〜２００ｍｌ／
ｍ2 ・ｍｍＨｇ・ｈｒで、β2 ―ＭＧの篩係数０．２以
上の中空糸膜であって、血液濾過開始後４時間経過して
も膜の血液透水性と、β2 ―ＭＧの篩係数が血液濾過開
始時の値に比べて９０％以上を示すことを特徴とする血
液透析膜が得られている。On the other hand, Japanese Patent Application Laid-Open No. 8-970 discloses a hollow fiber membrane in which N 2 gas is used as a core agent to improve the permeability of cellulose derivatives, particularly triacetate.
According to this, the ultrafiltration coefficient of pure water is 10 to 200 ml /
A hollow fiber membrane having a m 2 · mmHg · hr and a β 2 -MG sieving coefficient of 0.2 or more. Even after 4 hours from the start of blood filtration, the blood permeability of the membrane and the β 2 -MG sieve A hemodialysis membrane having a coefficient of 90% or more as compared with the value at the start of hemofiltration is obtained.
【０００８】しかし、該公報に開示されている、気体を
芯材としたトリアセテートの紡糸法では、紡糸が難しい
ため、低ポリマー濃度での紡糸が困難であり、水の限外
濾過係数は実施例に示されている如く、１０〜１２０ｍ
ｌ／Ｈｒ・ｍｍＨｇ・ｍ2 と比較的低く、高い限外濾過
係数の中空糸が得がたい。また、芯剤として気体を用い
る場合は、芯剤に凝固性がないため、内面緻密層の形成
は難しく、膜構造としては緻密層と、多孔層との密度差
が小さく、透過性の優れた合成ポリマーの様な２層構造
の膜が得られない。そのため血液透析での長期合併症で
問題になっているβ2 ―ＭＧに代表される中高分子量物
質の除去を大幅にできる膜を得ることは困難である。However, in the spinning method of triacetate using a gas as a core material disclosed in the publication, spinning at a low polymer concentration is difficult because spinning is difficult. 10 to 120m as shown in
1 / Hr · mmHg · m 2 is relatively low, and it is difficult to obtain a hollow fiber having a high ultrafiltration coefficient. When a gas is used as the core material, since the core material does not have coagulation properties, it is difficult to form an inner dense layer, and as a film structure, the density difference between the dense layer and the porous layer is small, and the permeability is excellent. A two-layer film like a synthetic polymer cannot be obtained. Therefore, it is difficult to obtain a membrane capable of greatly removing medium-high molecular weight substances such as β 2 -MG, which is a problem due to long-term complications in hemodialysis.
【０００９】この様に従来の製造方法で得られるセルロ
ース誘導体特にトリアセテートからなる膜は膜構造とし
ては緻密層と多孔層との密度差が不明確であり、その為
透過性及び分画性においてもポリスルホンのような合成
ポリマーからなる膜に比べ十分とは言えなかった。[0009] As described above, the membrane made of the cellulose derivative, particularly triacetate, obtained by the conventional production method has a film structure in which the density difference between the dense layer and the porous layer is unclear, and therefore the permeability and the fractionability are also low. It was not enough compared to a membrane made of a synthetic polymer such as polysulfone.
【００１０】[0010]
【発明が解決しようとする課題】本発明は、この様な従
来技術の問題点の解決を目的としたものであって、特に
血液透析や血液濾過透析において、β2 ―ＭＧ等の中分
子量領域の有害物質の除去性能と尿素等の低分子量領域
の有害物質の除去性能の両方に優れ、しかもアルブミン
の損失の少いセルローズ誘導体からなる選択透過性中空
糸膜を得る製造方法を提供することを目的としている。SUMMARY OF THE INVENTION An object of the present invention is to solve such problems of the prior art. Particularly, in hemodialysis or hemofiltration dialysis, a medium molecular weight region such as β 2 -MG is used. To provide a method for obtaining a selectively permeable hollow fiber membrane comprising a cellulose derivative which is excellent in both the performance of removing harmful substances of the above and the performance of removing harmful substances in a low molecular weight region such as urea, and has a small loss of albumin. The purpose is.
【００１１】[0011]
【課題を解決するための手段】本発明者は、かかる目的
を達成するために鋭意努力した結果、芯剤と凝固液とを
特定の関係に調整して紡糸することにより、膜構造を従
来の均一性膜ではなく、内面に極薄膜の特定空隙率の緻
密層を有し、支持層が多孔層である２層構造にすること
ができ、透過性能及び分画性能共に優れたセルロース誘
導体選択透過性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 As a result of the inventor's intense efforts to achieve the above object, the present inventors have adjusted the core structure and the coagulating solution to a specific relationship and spun to thereby achieve a conventional membrane structure. Rather than a uniform membrane, it has a dense layer with a specific porosity of an ultra-thin film on the inner surface, and the support layer can have a two-layer structure of a porous layer. The present inventors have found that a hydrophilic hollow fiber membrane can be obtained, and have reached the present invention.
【００１２】即ち本発明は、多価アルコールを０〜５０
ｗｔ％含有するセルロース誘導体溶解性有機溶剤溶液
に、セルロース誘導体を５〜１８ｗｔ％溶解した紡糸原
液を、多価アルコールと上記有機溶剤とを合計で５〜３
０ｗｔ％含有する水溶液を芯剤として用いて、チューブ
インオリフィス状ノズルより吐出させ、気体中を通過さ
せた後、多価アルコールと上記有機溶剤との合計の濃度
が芯剤よりも２０〜４５ｗｔ％高い水溶液からなる凝固
液中に通し、固化させることを特徴とする選択透過性中
空糸の製造方法である。That is, the present invention provides a method for preparing a polyhydric alcohol from 0 to 50
In a solution of a cellulose derivative-soluble organic solvent containing 5% by weight of a cellulose derivative, 5 to 18% by weight of a cellulose derivative was dissolved.
Using an aqueous solution containing 0 wt% as a core, the mixture is discharged from a tube-in-orifice-shaped nozzle and passed through a gas, and then the total concentration of the polyhydric alcohol and the organic solvent is 20 to 45 wt% as compared with the core. This is a method for producing a permselective hollow fiber, characterized in that the fiber is passed through a coagulation liquid composed of a high aqueous solution and solidified.
【００１３】かかる本発明によって得られる中空糸膜の
代表的なものとしては、内径が１００〜３００μｍ、膜
厚が３０〜６０μｍ、空孔率が６０〜９０％、純水の限
外濾過係数が２００〜８００ｍｌ／ｍ2 ・ｍｍＨｇ・ｈ
ｒ、かつβ2 ―ミクログロブリンの篩係数が０．６以上
で更にアルブミンの損失量が少ないという選択透過性中
空糸が挙げられる。Typical examples of the hollow fiber membrane obtained by the present invention include an inner diameter of 100 to 300 μm, a thickness of 30 to 60 μm, a porosity of 60 to 90%, and an ultrafiltration coefficient of pure water. 200-800 ml / m 2 · mmHg · h
and permselective hollow fibers in which the sieving coefficient of r and β 2 -microglobulin is 0.6 or more and the loss of albumin is further reduced.
【００１４】本発明の製造方法によって得られる中空糸
膜の膜壁の構造は、内面に物質の分離透過特性を決定す
る極薄の緻密層を有し、その外側に膜の機械特性を分担
する支持層を有するものであり、該支持層は、対象物質
の透過抵抗の殆んどない多孔層である、２層又は多層構
造となっている。The structure of the membrane wall of the hollow fiber membrane obtained by the production method of the present invention has an extremely thin dense layer which determines the separation and permeation characteristics of a substance on the inner surface, and shares the mechanical properties of the membrane on the outer side. It has a support layer, and the support layer has a two-layer or multilayer structure, which is a porous layer having almost no permeation resistance of the target substance.
【００１５】以下、本発明について更に詳細に説明す
る。本発明における中空糸膜を形成する素材は、セルロ
ース誘導体であり、特にアセチルセルロースである。そ
の中でも一般的に使用されるものとしては、実質的にセ
ルロースジアセテート、セルローストリアセテートから
なるポリマーである。これらの中でもセルローストリア
セテートが特に好ましい。なお、実質的とは、このセル
ロース誘導体の特性を損なわない範囲で、他の高分子量
物質や添加物を含有してもよいことを意味する。Hereinafter, the present invention will be described in more detail. The material forming the hollow fiber membrane in the present invention is a cellulose derivative, particularly acetyl cellulose. Among them, those generally used are polymers substantially consisting of cellulose diacetate and cellulose triacetate. Among these, cellulose triacetate is particularly preferred. Note that “substantially” means that other high molecular weight substances and additives may be contained as long as the properties of the cellulose derivative are not impaired.
【００１６】本発明の中空糸紡糸原液に使用できる溶剤
は、セルロース誘導体溶解性有機溶剤であり、これは更
に水混和性でもある。具体的には、Ｎ―メチルピロリド
ン、ジメチルホルムアミド、ジメチルスルホキシド、ジ
メチルアミド、ジメチルアセトアミド等が挙げられる。
特に好ましくはＮ―メチルピロリドンである。また、該
有機溶剤に混合しうる多価アルコールは、セルロース誘
導体の非溶剤として作用するものである。かかる多価ア
ルコールとしてはプロピレングリコール、エチレングリ
コール、トリエチレングリコール、ポリエチレングリコ
ール等が挙げられ、特に好ましくはプロピレングリコー
ルである。The solvent that can be used in the hollow fiber spinning solution of the present invention is a cellulose derivative-soluble organic solvent, which is also water-miscible. Specific examples include N-methylpyrrolidone, dimethylformamide, dimethylsulfoxide, dimethylamide, dimethylacetamide and the like.
Particularly preferred is N-methylpyrrolidone. The polyhydric alcohol that can be mixed with the organic solvent acts as a non-solvent for the cellulose derivative. Examples of such polyhydric alcohols include propylene glycol, ethylene glycol, triethylene glycol, polyethylene glycol and the like, with propylene glycol being particularly preferred.
【００１７】該有機溶剤と多価アルコールの組合せとし
ては、好ましくはＮ―メチルピロリドンとプロピレング
リコールの組合せである。The combination of the organic solvent and the polyhydric alcohol is preferably a combination of N-methylpyrrolidone and propylene glycol.
【００１８】紡糸原液中のセルロース誘導体濃度は５〜
１８ｗｔ％であり、好ましくは１０〜１５ｗｔ％であ
る。１８ｗｔ％を越えると支持層である多孔層が緻密化
する傾向を示し、β2 ―ＭＧ等の除去性能が大きく低下
する。５ｗｔ％より低いと紡糸原液の粘度が低くなりす
ぎ、製糸が困難となる。The concentration of the cellulose derivative in the spinning dope is 5 to 5.
18 wt%, preferably 10 to 15 wt%. If it exceeds 18% by weight, the porous layer as the support layer tends to be densified, and the performance of removing β 2 -MG or the like is greatly reduced. If the amount is less than 5 wt%, the viscosity of the spinning dope becomes too low, and the spinning becomes difficult.
【００１９】紡糸原液中の該有機溶剤／多価アルコール
の割合（ｗｔ）は、通常１００／０〜５０／５０、好ま
しくは８５／１５〜６５／３５、特に好ましくは８３／
１７〜７５／２５である。The ratio (wt) of the organic solvent / polyhydric alcohol in the spinning dope is usually 100/0 to 50/50, preferably 85/15 to 65/35, and particularly preferably 83/50.
17-75 / 25.
【００２０】芯剤は中空糸の内面に分画性に優れた薄い
緻密層を形成させるものであり、上記紡糸原液に用いた
該有機溶剤と多価アルコールとを合計で５〜３０ｗｔ％
含有する水溶液が好ましく、更に好ましくは１０〜２０
ｗｔ％の低濃度で含有する水溶液である。３０ｗｔ％を
越えると凝固速度が極端に遅くなり緻密層を形成しにく
く、５ｗｔ％より低くなると緻密層の厚さが厚くなり過
ぎ、β2 ―ＭＧのような中高分子量蛋白の除去性能が悪
くなる。The core agent is for forming a thin dense layer having excellent fractionability on the inner surface of the hollow fiber. The organic solvent and the polyhydric alcohol used in the spinning solution are combined in a total amount of 5 to 30% by weight.
Preferably, the aqueous solution contains, more preferably, 10 to 20.
It is an aqueous solution containing a low concentration of wt%. The solidification rate exceeds 30 wt% is difficult to form an extremely slows down dense layer becomes lower than 5 wt% too thick thickness of the dense layer, removal performance of high molecular weight proteins in such as beta 2 -MG is poor .
【００２１】凝固浴は中空糸の外層をゆるやかに凝固さ
せることにより多孔層を形成させる必要があり、そのた
めに芯剤に比べて該有機溶剤と多価アルコール（非溶
性）の合計での濃度を２０〜４５ｗｔ％、好ましくは２
５〜４０ｗｔ％高くする必要がある。具体的には合計で
３０〜７０ｗｔ％、好ましくは４０〜６０ｗｔ％の高濃
度で含有する水溶液が好ましい。７０ｗｔ％を越えると
凝固が遅くなりすぎ製糸性が悪くなり、３０ｗｔ％より
低いと多孔層が緻密化傾向となり、β2 ―ＭＧ等の除去
性能が低くなる。本発明で得られた中空糸膜は少なくと
も内面に２μｍ以下の厚さの空隙率３０％以下の緻密層
を有する。In the coagulation bath, it is necessary to form a porous layer by slowly coagulating the outer layer of the hollow fiber. For this reason, the concentration of the organic solvent and the polyhydric alcohol (insoluble) in total is lower than that of the core agent. 20-45 wt%, preferably 2
It is necessary to increase by 5 to 40 wt%. Specifically, an aqueous solution containing a high concentration of 30 to 70 wt% in total, preferably 40 to 60 wt% is preferable. If it exceeds 70% by weight, the coagulation becomes too slow and the spinning properties deteriorate, and if it is less than 30% by weight, the porous layer tends to be densified, and the ability to remove β 2 -MG or the like becomes low. The hollow fiber membrane obtained in the present invention has a dense layer having a thickness of 2 μm or less and a porosity of 30% or less on at least the inner surface.
【００２２】該中空糸膜の性能の特徴は、従来の比較的
均一構造の膜では得られなかった高レベルのものであ
り、純水の限外濾過係数は２００〜８００ｍｌ／ｍ2 ・
ｍｍＨｇ・ｈｒ、でかつβ2 ―ＭＧの篩係数が０．６以
上であり、良好なアルブミン阻止率（例えば、牛血漿で
のアルブミンの篩係数が０．０２以下）を有し、透過性
能と分画性能共に優れた中空糸膜である。The characteristic of the performance of the hollow fiber membrane is a high level which cannot be obtained with a conventional membrane having a relatively uniform structure, and the ultrafiltration coefficient of pure water is 200 to 800 ml / m 2 ···
mmHg · hr, β 2 -MG has a sieving coefficient of 0.6 or more, has a good albumin rejection (for example, the sieving coefficient of albumin in bovine plasma is 0.02 or less), It is a hollow fiber membrane with excellent fractionation performance.
【００２３】[0023]
【実施例】以下、本発明について、実施例をあげて更に
具体的に説明するが、本発明はこれらの実施例によって
何ら限定されるものではない。β2 ―ＭＧの篩係数、ア
ルブミンの篩係数の測定方法は日本透析医学会学術委員
会の「血液浄化器の牛血漿ｉｎ―ｖｉｔｒｏ評価のプロ
トコールと機能分類」に基づいて行った。またＵＦＲは
日本人工臓器学会のダイアライザー性能評価基準（Ｓ５
７．９）の「Ｓｉｎｇｌｅ ｐａｓｓ方式の循環法」に
より求めた。EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The sieving coefficient of β 2 -MG and the sieving coefficient of albumin were measured based on “Protocol and Function Classification of Bovine Plasma in-vitro Evaluation of Blood Purifier” by the Scientific Committee of the Japan Society for Dialysis Therapy. The UFR is based on the dialyzer performance evaluation standard (S5
7.9), "Single pass circulation method".
【００２４】［実施例１〜３、比較例１］セルロースト
リアセテート（酢化度６０．５、重合度３６０、ダイセ
ル化学工業（株）製）を溶剤としてＮ―メチルピロリド
ン（ＮＭＰ）、非溶剤多価アルコールとしてのプロピレ
ングリコール（ＰＧ）を表１記載の割合で混合した系で
溶解した紡糸原液を用い、同様の表１記載のＮＭＰとＰ
Ｇの組成の水溶液を芯剤として用い、２重管ノズルより
空気中に吐出した後、表１記載の条件の凝固液の中に導
入し、固化させ、水洗し、グリセリン付着処理後捲取っ
た。得られた中空糸膜を乾燥後円管状のケースに挿入
し、両端をポリウレタンで接着固定し、有効面積が約
１．５ｍ2 の中空糸膜透析器を作製した。ｉｎ―ｖｉｔ
ｒｏで純水の限外濾過係数（ＵＦＲ）及びβ2 ―ＭＧの
篩係数及びアルブミンの篩係数を測定した。結果は表１
に示す。Examples 1 to 3 and Comparative Example 1 N-methylpyrrolidone (NMP) using cellulose triacetate (degree of acetylation: 60.5, degree of polymerization: 360, manufactured by Daicel Chemical Industries, Ltd.) as a solvent Using a spinning stock solution dissolved in a system in which propylene glycol (PG) as a polyhydric alcohol was mixed at the ratio shown in Table 1, NMP and P
The aqueous solution having the composition of G was used as a core material and discharged into the air from a double tube nozzle, introduced into a coagulating solution under the conditions shown in Table 1, solidified, washed with water, and wound after glycerin adhesion treatment. . The obtained hollow fiber membrane was dried, inserted into a circular tubular case, and both ends were adhered and fixed with polyurethane, thereby producing a hollow fiber membrane dialyzer having an effective area of about 1.5 m 2 . in-vit
The ultrafiltration coefficient (UFR) of pure water, the sieving coefficient of β 2 -MG and the sieving coefficient of albumin were measured by ro. Table 1 shows the results
Shown in
【００２５】［比較例２］芯剤として流動パラフィンを
使用し、膜厚を薄くした従来から得られている均一緻密
膜構造の中空糸を得た。結果を表１に示す。[Comparative Example 2] Using a liquid paraffin as a core agent, a conventionally obtained hollow fiber having a uniform and dense membrane structure with a reduced film thickness was obtained. Table 1 shows the results.
【００２６】[0026]
【表１】 [Table 1]
【００２７】［実施例４〜５、比較例３］溶剤としてジ
メチルスルホキシド（ＤＭＳＯ）、非溶剤多価アルコー
ルとしてトリエチレングリコールを用いる以外実施例１
と同様の操作を行い、中空糸膜透析器を作製した。結果
は表２に示す。Examples 4 and 5, Comparative Example 3 Example 1 except that dimethyl sulfoxide (DMSO) was used as a solvent and triethylene glycol was used as a non-solvent polyhydric alcohol.
The same operation as described above was performed to produce a hollow fiber membrane dialyzer. The results are shown in Table 2.
【００２８】[0028]
【表２】 [Table 2]
フロントページの続き (56)参考文献 特開 昭63−28405（ＪＰ，Ａ) 特開 昭61−254201（ＪＰ，Ａ) 特開 昭61−200816（ＪＰ，Ａ) 特開 昭60−66755（ＪＰ，Ａ) 特開 昭55−24506（ＪＰ，Ａ) 特開 平２−135131（ＪＰ，Ａ) 特開 平６−343842（ＪＰ，Ａ) 特開 昭59−36715（ＪＰ，Ａ) 特開 昭62−30502（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) B01D 71/16 A61M 1/18 500 B01D 69/08 D01F 2/28 Continuation of the front page (56) References JP-A-63-28405 (JP, A) JP-A-61-254201 (JP, A) JP-A-61-200816 (JP, A) JP-A-60-66755 (JP, A) JP-A-55-24506 (JP, A) JP-A-2-135131 (JP, A) JP-A-6-343842 (JP, A) JP-A-59-36715 (JP, A) 62-30502 (JP, A) (58) Field surveyed (Int. Cl. 7 , DB name) B01D 71/16 A61M 1/18 500 B01D 69/08 D01F 2/28
Claims (4)
るセルロース誘導体溶解性有機溶剤溶液に、セルロース
誘導体を５〜１８ｗｔ％溶解した紡糸原液を、多価アル
コールと上記有機溶剤とを合計で５〜３０ｗｔ％含有す
る水溶液を芯剤として用いて、チューブインオリフィス
状ノズルより吐出させ、気体中を通過後、多価アルコー
ルと上記有機溶剤との合計の濃度が芯剤よりも２０〜４
５ｗｔ％高い水溶液からなる凝固液中に通し、固化させ
ることを特徴とする選択透過性中空糸の製造方法。1. A spinning solution in which a cellulose derivative is dissolved in an amount of 5 to 18 wt% in a cellulose derivative-soluble organic solvent solution containing a polyhydric alcohol in an amount of 0 to 50 wt%. An aqueous solution containing 30 wt% is used as a core material and discharged from a tube-in-orifice-shaped nozzle. After passing through a gas, the total concentration of the polyhydric alcohol and the organic solvent is 20 to 4 times higher than that of the core material.
A method for producing a permselective hollow fiber, comprising passing through a coagulation liquid comprising a 5 wt% higher aqueous solution and solidifying.
度が１５ｗｔ％〜３５ｗｔ％であることを特徴とする請
求項１記載の選択透過性中空糸の製造方法。2. The method for producing a permselective hollow fiber according to claim 1, wherein the concentration of the polyhydric alcohol in the organic solvent solution is 15 wt% to 35 wt%.
価アルコールがプロピレングリコールである請求項１又
は２記載の選択透過性中空糸の製造方法。3. The method for producing a selectively permeable hollow fiber according to claim 1, wherein the organic solvent is N-methylpyrrolidone and the polyhydric alcohol is propylene glycol.
価アルコールがトリエチレングリコールである請求項１
又は２記載の選択透過性中空糸の製造方法。4. The method according to claim 1, wherein the organic solvent is dimethyl sulfoxide and the polyhydric alcohol is triethylene glycol.
Or the method for producing a selectively permeable hollow fiber according to 2.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24777096A JP3205268B2 (en) | 1996-09-19 | 1996-09-19 | Method for producing selectively permeable hollow fiber membrane |
| CA002202969A CA2202969C (en) | 1996-04-19 | 1997-04-17 | Selectively permeable hollow fiber membrane and process for producing same |
| US08/837,475 US6013182A (en) | 1996-04-19 | 1997-04-18 | Selectively permeable hollow fiber membrane and process for producing same |
| EP97302660A EP0801973A1 (en) | 1996-04-19 | 1997-04-18 | Selectively permeable hollow fiber membrane and process for producing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24777096A JP3205268B2 (en) | 1996-09-19 | 1996-09-19 | Method for producing selectively permeable hollow fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH1085570A JPH1085570A (en) | 1998-04-07 |
| JP3205268B2 true JP3205268B2 (en) | 2001-09-04 |
Family
ID=17168399
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24777096A Expired - Fee Related JP3205268B2 (en) | 1996-04-19 | 1996-09-19 | Method for producing selectively permeable hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3205268B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5299617B2 (en) * | 2008-11-21 | 2013-09-25 | 東洋紡株式会社 | Method for producing hollow fiber membrane |
-
1996
- 1996-09-19 JP JP24777096A patent/JP3205268B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH1085570A (en) | 1998-04-07 |
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