JPS60168502A - Dialytic hollow yarn membrane - Google Patents
Dialytic hollow yarn membraneInfo
- Publication number
- JPS60168502A JPS60168502A JP2346884A JP2346884A JPS60168502A JP S60168502 A JPS60168502 A JP S60168502A JP 2346884 A JP2346884 A JP 2346884A JP 2346884 A JP2346884 A JP 2346884A JP S60168502 A JPS60168502 A JP S60168502A
- Authority
- JP
- Japan
- Prior art keywords
- hollow yarn
- heat
- heat treatment
- hollow fiber
- temp
- 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.)
- Pending
Links
Landscapes
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
本発明は、透析性能（除水量）が低下しない中空糸膜に
関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a hollow fiber membrane that does not reduce dialysis performance (amount of water removed).
近年人工腎臓における血液透析法や海水淡水化における
逆浸透法などミクロンオーダー以下の微小粒子を分離す
る手段として膜を用いる技術、すなわち膜分離技術が急
速に発達しつつある。この分離という目的を効率よく行
うために、しばしば有効膜面積の大きな中空糸型高分子
膜が用いられるが、特にセルロースエステル系中空糸膜
は食品工業、薬品工業、処理工業などの各方面に広く使
用されている。In recent years, technology that uses membranes as a means to separate microparticles on the order of microns or less, such as hemodialysis in artificial kidneys and reverse osmosis in seawater desalination, that is, membrane separation technology, is rapidly developing. In order to achieve this purpose of separation efficiently, hollow fiber polymer membranes with a large effective membrane area are often used, and cellulose ester hollow fiber membranes in particular are widely used in various fields such as the food industry, pharmaceutical industry, and processing industry. It is used.
血液透析法の発達で血液透析性能も向上してきているた
めに、腎不全で苦しむ患者の負担も以前に比べかなり軽
減されてきている。この血液透析性能で特に問題となり
１人命にかかわるものとして除水性能すなわち限外ｐ過
率（ＵＦＲ）がある。As hemodialysis performance has improved with the development of hemodialysis methods, the burden on patients suffering from renal failure has been significantly reduced compared to before. A particularly problematic aspect of hemodialysis performance that can be life-threatening is water removal performance, that is, ultrapolar fraction rate (UFR).
従来の透析用中空糸膜は、熱にかなり弱い。したがって
、それを充填したモジュールを医療機関に運搬したり為
そこで長期間保存したりする場合に、その環境が問題と
なる。もし、その環境が５０℃を越えるような高温状態
ではＶＦＲが著しく低下する不都合が派生していた。Conventional hollow fiber membranes for dialysis are quite sensitive to heat. Therefore, when a module filled with it is transported to a medical institution or stored there for a long period of time, the environment becomes a problem. If the environment was at a high temperature exceeding 50° C., there would be a disadvantage that the VFR would drop significantly.
本発明者らは、この問題について鋭意研究した結果、Ｖ
ＦＲの低下しない耐熱性のある中空糸膜を開発し、弾性
率が変化しない中空糸膜においては、そのＵＦＲが変化
しないことを見い出し本発明に到達した。As a result of intensive research into this problem, the inventors found that V
We have developed a heat-resistant hollow fiber membrane that does not cause a decrease in FR, and have discovered that in a hollow fiber membrane whose elastic modulus does not change, its UFR does not change, and we have arrived at the present invention.
すなわち本発明は、８０℃で２０時間定長で乾熱処理し
た際熱処理後の弾性率（Ｅｂ ： ｇ／−）が下記（１
）式を満たす透析用中空糸膜である。That is, in the present invention, the elastic modulus (Eb: g/-) after heat treatment is as follows (1
) is a hollow fiber membrane for dialysis that satisfies the formula.
ｏ、ｅｏ＜ −＜：Ｌ、１０ （１） −Ｈｈ − ただし、Ｅａは熱処理前の透析用中空糸膜の弾性率。o, eo<-<:L, 10 (1) -Hh- However, Ea is the elastic modulus of the hollow fiber membrane for dialysis before heat treatment.
より好ましい：［Ｃｂ／Ｋａの範囲は０．９５〜１．０
５であるＣ即ち、本発明でＸｌ）／Ｅａが０．９０に満
たない中空糸膜では糸強力が小さく使用中リークをおこ
す危険が考えられ、又Ｋｂ／ｌ１ｉａが１．１０を越え
る中空糸では除水性能が著しく低下し好ましくない。More preferable: [Cb/Ka range is 0.95 to 1.0
5, that is, in the present invention, hollow fiber membranes with Xl)/Ea of less than 0.90 have low fiber strength and are likely to cause leaks during use, and hollow fibers with Kb/l1ia of more than 1.10 This is not preferable because the water removal performance is significantly reduced.
ここで言うところの定長とは、透析用中空糸膜を収納す
るケースの両端で中空糸膜を熱により変性しない接着剤
により固定し、一定の長さに保持されている状態を言う
。したがって乾熱処理は、この中空糸膜を充填したケー
スごと行うことになる。この乾熱処理の条件は、８０℃
で２０時間であり、温度を場所によらず常に一定に保つ
ために、乾燥器内の空気を循環させて１中空糸膜のまわ
りの環境を安定させることが必要であった。次に弾性率
の測定条件をのべる。弾性率の値は、万能引張試験機に
より、中空糸膜長５０闘、引張速度１０１！Ｉ！ｌ／ｌ
ｌｌＩｎの条件により測定して得た応力−歪曲線から計
算することにより得た。この測定には、１つの試料につ
いて３０本行い、３０個の弾性率を平均をとって目的の
値とした。測定時における温度は２０℃で、中空糸膜に
対する熱の影響を無視できるような環境条件下で測定を
行った。The term "fixed length" as used herein refers to a state in which the hollow fiber membrane is fixed at both ends of the case containing the hollow fiber membrane for dialysis with an adhesive that does not denature due to heat, and is maintained at a constant length. Therefore, the dry heat treatment is performed for each case filled with the hollow fiber membrane. The conditions for this dry heat treatment are 80℃
In order to keep the temperature constant regardless of the location, it was necessary to circulate the air in the dryer to stabilize the environment around each hollow fiber membrane. Next, the conditions for measuring the elastic modulus will be described. The elastic modulus value was determined by a universal tensile tester at a hollow fiber membrane length of 50 mm and a tensile speed of 101! I! l/l
It was obtained by calculating from the stress-strain curve obtained by measurement under the conditions of llIn. This measurement was performed on 30 samples for each sample, and the elastic modulus of the 30 samples was averaged to obtain the desired value. The temperature at the time of measurement was 20° C., and the measurement was performed under environmental conditions such that the influence of heat on the hollow fiber membrane could be ignored.
本発明で言うところの透析用中空糸膜とは、ポリエチレ
ン、ポリプロピレン、ポリ塩化ビニリデン、ポリテトラ
フルオロエチレン、ポリエステル、セルロースエステル
等のいずれでも良いが、特に好適なものとしてセルロー
スエステル系の中空糸を挙げることができる。The hollow fiber membrane for dialysis referred to in the present invention may be made of polyethylene, polypropylene, polyvinylidene chloride, polytetrafluoroethylene, polyester, cellulose ester, etc., but cellulose ester-based hollow fibers are particularly preferred. can be mentioned.
状ノズルから吐出し、空気中を通過させた後、凝固浴工
程１水洗工程、グリセリン処理、乾燥工程、ヒートセッ
ト工程をほどこすことにより得られる。It is obtained by discharging it from a shaped nozzle and passing it through the air, followed by a coagulation bath step 1, a washing step, a glycerin treatment, a drying step, and a heat setting step.
この最終工程であるヒートセット工程は、乾燥工程温度
以上の高温で行われることが必要であり、通常の乾燥工
程温度が６０ ”０〜９０℃であることからヒートセッ
ト工程温度は６０℃〜１５０℃の範囲から選択する。こ
のようにして得られた中空糸膜は、ヒートセット工程前
の中空糸に比べ耐熱性の高いものとなっている。ここで
セルロースエステル、特にセルロースアセテートを例に
とる０この中空糸膜に関する限り、その紡糸工程におい
て、ヒートセット工程をガラス転移温度以下で行うこと
によりセルロースアセテート膜のミクロ構造をかなり安
定化させることができる。このヒートセット工程の最適
温度範囲は、乾燥工程温度が６０℃の場合６０℃〜１２
０℃であり、好ましくは７０℃である。これにより構造
を安定化させ、その後中空糸膜を透析用モジュールに組
込んだ後８０℃で２０時間乾熱処理を行い、その熱処理
前後でＶＦＲが低下せす）かつ弾性率も（１）式に従う
ことが確められた。ここで熱処理温度を８０℃と設定し
たのは、中空糸膜を透析用として臨床で用いる場合およ
びそれを保存する場合において、その中空糸膜を取り巻
く環境を考慮してのことである。This final step, the heat-setting step, needs to be carried out at a high temperature higher than the drying process temperature.Since the normal drying process temperature is 60" to 90°C, the heat-setting process temperature is 60" to 150°C. ℃.The hollow fiber membrane obtained in this way has higher heat resistance than the hollow fiber before the heat setting process.Here, let us take cellulose ester, especially cellulose acetate, as an example. 0 As far as this hollow fiber membrane is concerned, the microstructure of the cellulose acetate membrane can be considerably stabilized by performing the heat setting step at a temperature below the glass transition temperature in the spinning process.The optimum temperature range for this heat setting step is: If the drying process temperature is 60℃, 60℃~12
The temperature is 0°C, preferably 70°C. This stabilizes the structure, and after incorporating the hollow fiber membrane into a dialysis module, dry heat treatment is performed at 80°C for 20 hours, and the VFR decreases before and after the heat treatment), and the elastic modulus also follows equation (1). This was confirmed. The heat treatment temperature was set at 80°C in consideration of the environment surrounding the hollow fiber membrane when the hollow fiber membrane is used clinically for dialysis and when stored.
本発明において紡糸される中空糸膜には、多孔質構造を
補強するためのものとして、グリセリンと水が適当な割
合で含まれている０そのグリセリンおよび水の（ポリマ
ー、グリセリン、水）に対する重量分率は、グリセリン
４０〜５０％、水５〜１０％である。ヒートセット工程
をほどこす場合、この水とグリセリンの重量分率を変化
させないように行われることが好ましい。したがってガ
ラス転移温度以下の温度でヒートセットを行うといって
も１２０℃以上になると好ましくない。The hollow fiber membrane spun in the present invention contains glycerin and water in an appropriate ratio to reinforce the porous structure. The fractions are 40-50% glycerin and 5-10% water. When applying the heat setting step, it is preferable to perform the heat setting step so as not to change the weight fraction of water and glycerin. Therefore, even if heat setting is performed at a temperature below the glass transition temperature, it is not preferable to heat the film at a temperature above 120°C.
このようにヒートセット工程を最適湿度に従い行うこと
により、力学的には（１）式を満足し、ＶＦＲも低下し
ないすぐれた透析用中空糸膜を得ることがはじめてでき
た。By performing the heat-setting step in accordance with the optimum humidity in this way, it was possible for the first time to obtain an excellent hollow fiber membrane for dialysis that mechanically satisfies formula (1) and does not reduce VFR.
次に実施例を示し、本発明を説明する。Next, examples will be shown to explain the present invention.
実施例
セルロースジアセテート３１．５重量ノぐ−セント、Ｎ
−メチルピロリドン５４．８重量ノぜ一セント、エチレ
ングリコール１３．７重量ノぐ−セントよりなるドープ
を円環状ノズルから吐出し、凝固浴、水洗浴、グリセリ
ン処理、乾燥工程を経て、ボビンとして巻取った後ヒー
トセット工程をほどこした。Example Cellulose diacetate 31.5 weight cents, N
- A dope consisting of 54.8 cents by weight of methylpyrrolidone and 13.7 cents by weight of ethylene glycol is discharged from an annular nozzle, subjected to a coagulation bath, a water washing bath, a glycerin treatment, and a drying process, and then wound as a bobbin. After removing it, a heat setting process was applied.
この後この中空糸膜を透析用モジュールとして組立て、
熱処理を行ってその前後でのＵＦＲおよび弾性′率を測
定した。After this, this hollow fiber membrane is assembled as a dialysis module,
The UFR and elastic modulus were measured before and after heat treatment.
このときの紡糸条件を第１表に示す。The spinning conditions at this time are shown in Table 1.
第 １ 表 ■■■の場合の結果を第２表に示す。Table 1 Table 2 shows the results for ■■■.
第 ２ 表
ここで
■■■においてＵＦＲの低下がほとんど見られず（１）
式を満しているのは■■の場合でありへそのときのヒー
トセット工程条件は、乾燥工ｍ温度以上の高温で行われ
ている０
特許出願人 東洋紡績株式会社Table 2 Here, there is almost no decrease in UFR in ■■■ (1)
The formula is satisfied in the case of ■■, and the heat setting process conditions at the navel are performed at a high temperature higher than the drying process temperature.0 Patent applicant: Toyobo Co., Ltd.
Claims (1)
性率（ｌｃｂ ： （／／ａｄ）が下記（１）式を満足
する透析用中空糸膜。 ０．９０（−（１，１０（１） −Ｐａ − ただし、 Ｅａは熱処理前の中空糸膜の弾性率。[Claims] A hollow fiber membrane for dialysis whose elastic modulus (lcb: (//ad) after heat treatment satisfies the following formula (1) when subjected to dry heat treatment at 80° C. for 20 hours at a constant length: 0.90 (-(1,10(1)-Pa-) where Ea is the elastic modulus of the hollow fiber membrane before heat treatment.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2346884A JPS60168502A (en) | 1984-02-10 | 1984-02-10 | Dialytic hollow yarn membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2346884A JPS60168502A (en) | 1984-02-10 | 1984-02-10 | Dialytic hollow yarn membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60168502A true JPS60168502A (en) | 1985-09-02 |
Family
ID=12111358
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2346884A Pending JPS60168502A (en) | 1984-02-10 | 1984-02-10 | Dialytic hollow yarn membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60168502A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60193504A (en) * | 1984-03-15 | 1985-10-02 | Toyobo Co Ltd | Hollow fiber membrane for dialysis |
| US8241466B2 (en) | 2006-08-31 | 2012-08-14 | Sanyo Electric Co., Ltd. | Distillation apparatus |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5387982A (en) * | 1977-01-12 | 1978-08-02 | Daicel Chem Ind Ltd | Regulating method for membrane performance of semi-permeable membrane |
| JPS55107505A (en) * | 1979-02-13 | 1980-08-18 | Nippon Zeon Co Ltd | Production of hollow fiber |
| JPS569420A (en) * | 1979-07-04 | 1981-01-30 | Nippon Zeon Co Ltd | Method of production of hollow fiber |
| JPS5742918A (en) * | 1980-08-29 | 1982-03-10 | Mitsubishi Rayon Co Ltd | Hollow cellulosic derivative fiber |
| JPS57133211A (en) * | 1981-02-09 | 1982-08-17 | Toyobo Co Ltd | Production of hollow fiber of cellulose ester |
-
1984
- 1984-02-10 JP JP2346884A patent/JPS60168502A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5387982A (en) * | 1977-01-12 | 1978-08-02 | Daicel Chem Ind Ltd | Regulating method for membrane performance of semi-permeable membrane |
| JPS55107505A (en) * | 1979-02-13 | 1980-08-18 | Nippon Zeon Co Ltd | Production of hollow fiber |
| JPS569420A (en) * | 1979-07-04 | 1981-01-30 | Nippon Zeon Co Ltd | Method of production of hollow fiber |
| JPS5742918A (en) * | 1980-08-29 | 1982-03-10 | Mitsubishi Rayon Co Ltd | Hollow cellulosic derivative fiber |
| JPS57133211A (en) * | 1981-02-09 | 1982-08-17 | Toyobo Co Ltd | Production of hollow fiber of cellulose ester |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60193504A (en) * | 1984-03-15 | 1985-10-02 | Toyobo Co Ltd | Hollow fiber membrane for dialysis |
| US8241466B2 (en) | 2006-08-31 | 2012-08-14 | Sanyo Electric Co., Ltd. | Distillation apparatus |
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