JP2000334281A - Hollow fiber membrane for artificial kidney made of polysulfone and its production - Google Patents
Hollow fiber membrane for artificial kidney made of polysulfone and its productionInfo
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- JP2000334281A JP2000334281A JP11150096A JP15009699A JP2000334281A JP 2000334281 A JP2000334281 A JP 2000334281A JP 11150096 A JP11150096 A JP 11150096A JP 15009699 A JP15009699 A JP 15009699A JP 2000334281 A JP2000334281 A JP 2000334281A
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- Prior art keywords
- hollow fiber
- fiber membrane
- polysulfone
- artificial kidney
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリビニルピロリ
ドン（ＰＶＰ）を含有するポリスルホン（ＰＳ）製人工
腎臓用中空糸膜に関するものである。更に詳しくは、破
断強度と破断伸度に優れた良好な取扱性能を有する、血
液透析、血液濾過透析等の人工腎臓に適したポリスルホ
ン製人工腎臓用中空糸膜を提供するものである。TECHNICAL FIELD The present invention relates to a hollow fiber membrane for artificial kidney made of polysulfone (PS) containing polyvinylpyrrolidone (PVP). More specifically, the present invention provides a polysulfone hollow fiber membrane for artificial kidneys having excellent handling performance with excellent breaking strength and breaking elongation and suitable for artificial kidneys such as hemodialysis and hemofiltration dialysis.
【０００２】[0002]
【従来技術】人工腎臓用中空糸膜は、血液透析や血液濾
過、同時血液透析濾過等により腎不全患者の血液を浄化
するために、現在では広く使用されている。通常、円筒
状の筐体の中に中空糸の膜を多数本収納し、その中空内
部に患者の血液を流し、外部、即ち中空糸間隙部に透析
液を流して、中空糸膜壁を介して透析することによっ
て、血液中の老廃物を除去し、また、中空糸膜を隔てて
圧力差を設け限外濾過によって血液中の余剰水分およ
び、水分とともに血液中の老廃物を除去するものであ
る。BACKGROUND ART Hollow fiber membranes for artificial kidneys are now widely used for purifying blood of patients with renal failure by hemodialysis, hemofiltration, simultaneous hemodiafiltration and the like. Normally, a large number of hollow fiber membranes are housed in a cylindrical housing, the patient's blood is allowed to flow inside the hollow, and the dialysate is allowed to flow outside, that is, into the hollow fiber gap, through the hollow fiber membrane wall. Dialysis to remove waste products in blood, and a pressure difference across the hollow fiber membrane to remove excess water in blood and ultra-filtration to remove waste products in blood with ultrafiltration. is there.
【０００３】近年、透析患者の透析アミロイドシスの原
因物質と考えられるβ2-ミクログロブリン（β2ＭＧ、
分子量：１１，８００）をはじめとした比較的中高分子
量領域の有害物質の除去が求められている。一方、人体
にとって有効な成分であるアルブミン（分子量：６６，
０００）の損失は極力避けなければならない。従って、
シャープな分画分子量曲線を有する中空糸膜が望まれて
いる。Recently, β 2 -microglobulin (β 2 MG, which is considered to be a causative substance of dialysis amyloidosis in dialysis patients,
(Molecular weight: 11,800) and the removal of harmful substances in a relatively medium-high molecular weight region. On the other hand, albumin, a component effective for the human body (molecular weight: 66,
000) must be avoided as much as possible. Therefore,
A hollow fiber membrane having a sharp molecular weight cutoff curve is desired.
【０００４】このように人工腎臓用の中空糸は、素材、
空孔率（中空糸膜中の孔の割合）、孔径、膜厚などが重
要な要因である。この目的の為に、従来から、ポリスル
ホンなどの合成高分子では、例えば特公平２−１８６９
５号や特公平５−５４３７３号に見られるように、比較
的上記の要求を満たしたものが得られている。しかし、
該合成高分子の膜は高い空孔率を有している為か、ある
いは膜が紡糸原液から凝固液によって凝固する際の状態
に起因するかどうかは不明であるが、中空糸膜の破断強
度および破断伸度が低く、取扱いが大変難しいものであ
った。[0004] As described above, hollow fibers for artificial kidneys are made of materials,
The porosity (the ratio of the pores in the hollow fiber membrane), the pore diameter, the film thickness, and the like are important factors. For this purpose, conventionally, synthetic polymers such as polysulfone have been used, for example,
As can be seen in Japanese Utility Model No. 5 and Japanese Patent Publication No. 5-54373, those which relatively satisfy the above requirements have been obtained. But,
It is not known whether the membrane of the synthetic polymer has a high porosity or whether the membrane is caused by a state of coagulation from a spinning solution by a coagulation solution, but the breaking strength of the hollow fiber membrane is unknown. And the elongation at break was low and handling was very difficult.
【０００５】従来より、破断強度の高い人工腎臓用中空
糸膜の素材として再生セルロースが用いられているが、
シャープな分画分子量曲線と中高分子量の透過性を両立
させることは困難であった。Conventionally, regenerated cellulose has been used as a material for hollow fiber membranes for artificial kidneys having high breaking strength.
It was difficult to achieve both a sharp molecular weight cutoff curve and a medium high molecular weight permeability.
【０００６】これらの理由により、従来、ポリスルホン
製の中空糸膜は、物質の透過性能は十分であるが、破断
強度や破断伸度は十分とは言えなかった。[0006] For these reasons, polysulfone hollow fiber membranes have heretofore been satisfactory in permeation performance for substances, but not sufficient in breaking strength and elongation at break.
【０００７】[0007]
【発明が解決しようとする課題】本発明の目的は、この
ような従来技術の問題点を解決することを目的とするも
のであって、破断強度と破断伸度に優れた良好な取扱性
能を有する、血液透析、血液濾過透析等の人工腎臓に適
したポリスルホン製人工腎臓用中空糸膜を提供すること
である。SUMMARY OF THE INVENTION An object of the present invention is to solve such problems of the prior art, and to provide good handling performance excellent in breaking strength and breaking elongation. An object of the present invention is to provide a polysulfone hollow fiber membrane for artificial kidney suitable for artificial kidney such as hemodialysis and hemofiltration dialysis.
【０００８】[0008]
【課題を解決するための手段】本発明は、かかる目的を
達成するために以下の構成を有する。The present invention has the following arrangement in order to achieve the above object.
【０００９】（１） ポリビニルピロリドンを含有する
ポリスルホン製人工腎臓用中空糸膜において、破断強度
が２０ｇｆ／本以上、破断伸度が３０％以上であること
を特徴とするポリスルホン製人工腎臓用中空糸膜。(1) A hollow fiber for polysulfone artificial kidney comprising polyvinylpyrrolidone having a breaking strength of not less than 20 gf / piece and a breaking elongation of not less than 30%. film.
【００１０】（２） ポリビニルピロリドンを含有する
ポリスルホン製人工腎臓用中空糸膜において、中空糸膜
の内径と外径から求めた中空糸膜断面積に換算し、４７
０ｇｆ／ｍｍ２以上、破断伸度が３０％以上であること
を特徴とするポリスルホン製人工腎臓用中空糸膜。(2) In a polysulfone hollow fiber membrane containing polyvinylpyrrolidone for artificial kidney, which is converted into a hollow fiber membrane cross-sectional area obtained from the inner diameter and outer diameter of the hollow fiber membrane, 47
A polysulfone hollow fiber membrane for an artificial kidney made of 0 gf / mm 2 or more and elongation at break of 30% or more.
【００１１】（３） 前記中空糸膜の内径が１５０μｍ
から２５０μｍ、膜厚が３５μｍから５５μｍであるこ
とを特徴とする（１）または（２）に記載のポリスルホ
ン製人工腎臓用中空糸膜。(3) The hollow fiber membrane has an inner diameter of 150 μm.
The hollow fiber membrane for polysulfone-made artificial kidney according to (1) or (2), wherein the hollow fiber membrane has a thickness of 35 μm to 250 μm and a thickness of 35 μm to 55 μm.
【００１２】（４） ポリスルホンが少なくとも１５ｗ
ｔ％、ポリビニルピロリドンが少なくとも３ｗｔ％およ
びジメチルアセトアミドからなる紡糸溶液１００重量部
に対して、水を０．５重量部から１．１重量部含有する
紡糸原液、および、水分量４５ｗｔ％から６５ｗｔ％の
ジメチルアセトアミド水溶液からなる中空部形成液を、
２重管状ノズルから吐出し、１℃から８℃の水性凝固浴
へ導入して乾湿式紡糸法により紡糸することを特徴とす
るポリスルホン製人工腎臓用中空糸膜の製造方法。(4) at least 15 w of polysulfone
t%, a spinning solution containing 0.5 to 1.1 parts by weight of water with respect to 100 parts by weight of a spinning solution composed of at least 3% by weight of polyvinylpyrrolidone and dimethylacetamide, and a water content of 45 to 65% by weight. A hollow part forming solution comprising a dimethylacetamide aqueous solution of
A method for producing a hollow fiber membrane for a polysulfone artificial kidney, comprising discharging from a double tubular nozzle, introducing into an aqueous coagulation bath at 1 ° C to 8 ° C, and spinning by a dry-wet spinning method.
【００１３】（５） 上記紡糸原液においてポリスルホ
ンが１５ｗｔ％から１８ｗｔ％、ポリビニルピロリドン
が３ｗｔ％から５ｗｔ％、ジメチルアセトアミドが７７
ｗｔ％から８２ｗｔ％であることを特徴とする（４）に
記載のポリスルホン製人工腎臓用中空糸膜の製造方法。(5) In the above spinning dope, polysulfone is 15 to 18 wt%, polyvinyl pyrrolidone is 3 to 5 wt%, and dimethylacetamide is 77.
The method for producing a polysulfone hollow fiber membrane for an artificial kidney according to (4), wherein the amount is from 82 wt% to 82 wt%.
【００１４】[0014]
【発明の実施の形態】本発明における中空糸膜は、人工
腎臓に用いるものであるので生体の有効成分であるアル
ブミンの損失の少ないものである。具体的には抗凝固さ
れた牛血液（ヘマトクリット３０％、血漿総タンパク質
濃度６．５ｇ／ｄｌ）を用い、血液流速Ｑｂ＝２００ｍ
ｌ／ｍｉｎ、濾過流速Ｑｆ＝１０ｍｌ／ｍｉｎで１時間
血液濾過を行ったときのアルブミンの篩係数が０．０２
から０．００２、好ましくは０．０１５から０．００５
である。篩係数が上限値よりも大きい場合は、血液中の
栄養素としてのアルブミンの機能が低下し、患者の負担
となり、下限値よりも小さい場合は、中高分子量の物質
除去が不足する。BEST MODE FOR CARRYING OUT THE INVENTION The hollow fiber membrane of the present invention is used for an artificial kidney, and therefore has a small loss of albumin, which is an active ingredient of a living body. Specifically, using anticoagulated bovine blood (hematocrit 30%, plasma total protein concentration 6.5 g / dl), blood flow rate Qb = 200 m
The sieving coefficient of albumin was 0.02 when blood filtration was performed for 1 hour at l / min and filtration flow rate Qf = 10 ml / min.
To 0.002, preferably 0.015 to 0.005
It is. When the sieving coefficient is larger than the upper limit, the function of albumin as a nutrient in blood is reduced, and the burden is placed on the patient. When the sieving coefficient is smaller than the lower limit, removal of medium-high molecular weight substances is insufficient.
【００１５】また、β２ミクログロブリン（β２ＭＧ）
の篩係数は、０．５から１．０、好ましくは０．８から
１．０である。尚、測定にはラテックス凝集免疫法を用
いる。測定方法は、抗凝固された牛血液（ヘマトクリッ
ト３０％、血漿総タンパク質濃度６．５ｇ／ｄｌ）にヒ
トβ２ＭＧを濃度１２００μｇ／ｌとなるように添加
し、血液流速Ｑｂ＝２００ｍｌ／ｍｉｎ、濾過流速Ｑｆ
＝１０ｍｌ／ｍｉｎで１時間血液濾過を行い、人工腎臓
の入口側血液、出口側血液および濾液を採取して測定す
る。Further, β 2 microglobulin (β 2 MG)
Has a sieve coefficient of 0.5 to 1.0, preferably 0.8 to 1.0. In addition, latex agglutination immunoassay is used for the measurement. The measurement method was as follows: human β 2 MG was added to anticoagulated bovine blood (hematocrit 30%, plasma total protein concentration 6.5 g / dl) to a concentration of 1200 μg / l, and blood flow rate Qb = 200 ml / min. Filtration flow rate Qf
Blood filtration is performed at 10 ml / min for 1 hour, and the blood on the inlet side, the blood on the outlet side, and the filtrate of the artificial kidney are collected and measured.
【００１６】ポリスルホンは、具体的には下記の繰り返
し単位を有する重合体に代表される。The polysulfone is specifically represented by a polymer having the following repeating unit.
【００１７】[0017]
【数１】 (Equation 1)
【００１８】数平均分子量は１５，０００から３０，０
００が好ましく、１８，０００から、２３，０００がよ
り好ましい。また、本発明の中空糸膜は、孔形成剤とし
て紡糸原液に含有するポリビニルピロリドン（ＰＶＰ）
が中空糸膜に一部残存している。中空糸膜に残存する該
ＰＶＰはＰＳに対して、好ましくは１ｗｔ％から５ｗｔ
％である。より好ましくは２ｗｔ％から４ｗｔ％であ
る。The number average molecular weight is from 15,000 to 30,0
00 is preferable, and 18,000 to 23,000 is more preferable. In addition, the hollow fiber membrane of the present invention is obtained by using polyvinylpyrrolidone (PVP) contained in a spinning solution as a pore-forming agent.
Partially remain in the hollow fiber membrane. The PVP remaining in the hollow fiber membrane is preferably 1 wt% to 5 wt% with respect to PS.
%. More preferably, the content is 2 wt% to 4 wt%.
【００１９】また、本発明の中空糸膜の膜壁の構造は、
物質の分離透過特性を担う緻密層と機械特性を担う多孔
層を有する。本発明の中空糸膜の緻密層は中空糸膜内面
に形成される。該多孔層は、機械的に流体圧力に耐えら
れるが、物質の透過抵抗には殆んど影響しないものであ
る。該多孔層は中空糸内面の緻密層から中空糸膜の外面
方向に向かって徐々に大きな孔となり、中空糸膜断面の
内面から外面に向かう途中から、外面に向かって徐々に
小さくなる孔を有する。すなわち、中空糸膜断面におい
て、内面から外面へ向かう途中に最大孔径を有する。The structure of the membrane wall of the hollow fiber membrane of the present invention is as follows:
It has a dense layer responsible for the separation and permeation properties of substances and a porous layer responsible for the mechanical properties. The dense layer of the hollow fiber membrane of the present invention is formed on the inner surface of the hollow fiber membrane. The porous layer mechanically withstands fluid pressure but has little effect on the permeation resistance of the substance. The porous layer gradually increases in size from the dense layer on the inner surface of the hollow fiber toward the outer surface of the hollow fiber membrane, and has holes gradually decreasing from the inner surface to the outer surface of the cross section of the hollow fiber membrane toward the outer surface. . That is, in the cross section of the hollow fiber membrane, it has a maximum pore diameter on the way from the inner surface to the outer surface.
【００２０】中空糸膜の膜厚は、一般に物質の透過性か
らみれば薄いのが望ましいが、本発明に係わる人工腎臓
用中空糸膜は、本発明の有する破断強度と破断伸度を生
かして、実際の作業性を向上させるために、３０μｍか
ら５５μｍであり、好ましくは３５μｍから５０μｍで
ある。膜厚が３０μｍ以下では十分な強度が得られず、
５５μｍ以上では透析効率が低下するという問題点が生
じる。The thickness of the hollow fiber membrane is generally desirably thin in view of the permeability of the substance. However, the hollow fiber membrane for an artificial kidney according to the present invention takes advantage of the breaking strength and breaking elongation of the present invention. In order to improve the actual workability, the thickness is 30 μm to 55 μm, preferably 35 μm to 50 μm. If the film thickness is less than 30 μm, sufficient strength cannot be obtained,
If it is 55 μm or more, there is a problem that the dialysis efficiency is reduced.
【００２１】また、本発明の中空糸膜の内径は１５０〜
２５０μｍ、更には１８０〜２２０μｍが好ましい。内
径が１５０μｍ以下では中空糸膜の曲折等により血液流
露が狭小化する可能性高くなり、中空糸膜の閉塞を招
く。また内径が２５０μｍ以上であると血液流路容量に
比べ血液と接触する膜面積の比が小さくなり、透析や濾
過の効率が低下する。The hollow fiber membrane of the present invention has an inner diameter of 150 to 150.
It is preferably 250 μm, more preferably 180 to 220 μm. When the inner diameter is 150 μm or less, there is a high possibility that the blood flow will be narrowed due to the bending of the hollow fiber membrane, and the hollow fiber membrane will be blocked. On the other hand, if the inner diameter is 250 μm or more, the ratio of the membrane area in contact with blood becomes smaller than the volume of the blood channel, and the efficiency of dialysis and filtration is reduced.
【００２２】本発明の中空糸膜の破断強度は、中空糸膜
１本あたり２０ｇ以上であり、好ましくは２０ｇ以上３
０ｇ以下である。２０ｇ未満では、良好な作業性は得ら
れず、また、あまりに高すぎる場合、中空糸膜全体が緻
密になりすぎている可能性があり、３０ｇ以下が好まし
い。また、同様の理由により、本発明の中空糸膜の破断
強度は、中空糸膜の内径と外径から求めた中空糸膜断面
積に換算し、４７０ｇｆ／ｍｍ２以上である。好ましく
は４７０ｇｆ／ｍｍ２から７１０ｇｆ／ｍｍ２である。
破断伸度は３０％以上である。好ましくは３５％以上、
より好ましくは４０％以上である。破断伸度が３０％未
満の場合、組立作業あるいは組立後の滅菌、運搬等によ
って膜に加えられる物理的衝撃、温度変化による中空糸
膜の破損の可能性が高くなる。破断強度および破断伸度
は、中空糸膜１本を測定長さ５０ｍｍ、引き張り速度５
０ｍｍ／ｍｉｎで測定する。The breaking strength of the hollow fiber membrane of the present invention is 20 g or more per hollow fiber membrane, preferably 20 g or more.
0 g or less. If the amount is less than 20 g, good workability cannot be obtained, and if it is too high, the entire hollow fiber membrane may be too dense, and the amount is preferably 30 g or less. For the same reason, the breaking strength of the hollow fiber membrane of the present invention is 470 gf / mm 2 or more in terms of the hollow fiber membrane cross-sectional area obtained from the inner diameter and the outer diameter of the hollow fiber membrane. Preferably it is 470 gf / mm 2 to 710 gf / mm 2 .
The breaking elongation is 30% or more. Preferably 35% or more,
It is more preferably at least 40%. When the elongation at break is less than 30%, the possibility of breakage of the hollow fiber membrane due to a physical impact applied to the membrane due to assembling work or sterilization or transportation after assembling or a temperature change increases. The breaking strength and breaking elongation were measured for one hollow fiber membrane with a measuring length of 50 mm and a pulling speed of 5
Measure at 0 mm / min.
【００２３】本発明の上記中空糸膜の束を用いて組み立
てた透析器における透水速度（ＵＦＲ）は、８０ｍｌ／
ｈｒ・ｍｍＨｇ・ｍ２ 以上６００ｍｌ／ｈｒ・ｍｍＨ
ｇ・ｍ２以下であり、好ましくは１００ｍｌ／ｈｒ・ｍ
ｍＨｇ・ｍ２ 以上３００ｍｌ／ｈｒ・ｍｍＨｇ・ｍ２
であり、より好ましくは１３０ｍｌ／ｈｒ・ｍｍＨｇ・
ｍ２ 以上２００ｍｌ／ｈｒ・ｍｍＨｇ・ｍ２である。
下限値未満では、尿毒性の中高分子量領域の有害物質の
除去が不十分となり、上限値を越えると透析液側と血液
側の間の物質移動が必要以上に起こってしまう。尚、Ｕ
ＦＲの測定法は、透析医学会誌２９（８）、１２３１〜
１２４５頁、１９９６の「各種の血液浄化法の機能と適
応−血液浄化器の性能評価法と機能分類」に基づいて行
う。The water permeation rate (UFR) of the dialyzer assembled using the hollow fiber membrane bundle of the present invention is 80 ml /
hr · mmHg · m 2 or more 600ml / hr · mmH
g · m 2 or less, preferably 100 ml / hr · m
mHg · m 2 or more and 300 ml / hr · mmHg · m 2
And more preferably 130 ml / hr · mmHg ·
m 2 or more and 200 ml / hr · mmHg · m 2 .
If it is less than the lower limit, harmful substances in the urine toxic medium-high molecular weight region will not be sufficiently removed. If it exceeds the upper limit, mass transfer between the dialysate side and the blood side will occur more than necessary. In addition, U
The method for measuring FR is described in the Japanese Society for Dialysis Therapy 29 (8), 1231-
1245, 1996, "Functions and Adaptations of Various Blood Purification Methods-Performance Evaluation Methods and Function Classification of Blood Purifiers".
【００２４】本発明の中空糸膜の製造方法は、ポリスル
ホンが少なくとも１５ｗｔ％、ポリビニルピロリドンが
少なくとも３ｗｔ％およびジメチルアセトアミドからな
る紡糸溶液１００重量部に対して、水を０．５重量部か
ら１．１重量部の割合で含有する紡糸原液、および、水
分量４５ｗｔ％から６５ｗｔ％のジメチルアセトアミド
水溶液からなる中空部形成液を、２重管状ノズルから吐
出し、乾湿式紡糸法により紡糸する。上記紡糸溶液にお
いて好ましくは、ポリスルホンが１５ｗｔ％から１８ｗ
ｔ％、ポリビニルピロリドンが３ｗｔ％から５ｗｔ％、
ジメチルアセトアミドが７７ｗｔ％から８２ｗｔ％であ
る。The method for producing a hollow fiber membrane according to the present invention is characterized in that water is used in an amount of 0.5 to 1.50 parts by weight based on 100 parts by weight of a spinning solution comprising at least 15% by weight of polysulfone, at least 3% by weight of polyvinylpyrrolidone and dimethylacetamide. A spinning stock solution containing 1 part by weight and a hollow part forming solution composed of a dimethylacetamide aqueous solution having a water content of 45 wt% to 65 wt% are discharged from a double tubular nozzle and spun by a dry-wet spinning method. In the above spinning solution, preferably, the polysulfone is 15 wt% to 18 w%.
t%, polyvinylpyrrolidone is 3 wt% to 5 wt%,
Dimethylacetamide is 77 wt% to 82 wt%.
【００２５】本発明の紡糸原液の水分量は、上記紡糸溶
液１００重量部に対して０．５重量部から１．１重量部
である。ポリビニルピロリドンは吸水性が高く、保存中
は環境により一定の水分を含んでいる。従って、本発明
の中空糸膜の製造方法においては、使用するポリビニル
ピロリドンの状態を厳密に制御することにより、紡糸原
液中の水分量を、最終的に０．５重量部から１．１重量
部の割合に調節するものである。理由は不明であるが、
本発明者らは、紡糸原液中の水分量をこの範囲に調節す
ることにより、破断強度および破断伸度がともに優れた
ポリスルホン製人工腎臓用中空糸膜を得ることができる
ことを解明した。紡糸原液中のさらに好ましい水分量は
０．８重量部から１．０５重量部である。紡糸原液中の
水分量が上限値を越えた場合、破断伸度が低下する。ま
た、下限値未満では、ポリビニルピロリドンの保管状態
を調節するための操作が煩雑となり、また、本発明の中
空部形成液の水分量が高いため、紡糸原液が凝固する
際、緻密層の孔径が小さくなりすぎるため、物質除去性
能が低下する。The water content of the stock solution for spinning of the present invention is 0.5 to 1.1 parts by weight based on 100 parts by weight of the spinning solution. Polyvinylpyrrolidone has high water absorption, and contains a certain amount of moisture depending on the environment during storage. Therefore, in the method for producing a hollow fiber membrane of the present invention, by strictly controlling the state of the polyvinylpyrrolidone used, the water content in the spinning dope is finally adjusted to 0.5 to 1.1 parts by weight. The ratio is adjusted. For unknown reasons,
The present inventors have elucidated that by adjusting the amount of water in the spinning solution to this range, it is possible to obtain a polysulfone hollow fiber membrane for artificial kidney having excellent breaking strength and breaking elongation. The more preferable amount of water in the spinning dope is 0.8 parts by weight to 1.05 parts by weight. If the amount of water in the spinning dope exceeds the upper limit, the elongation at break decreases. Further, when the lower limit is less than the lower limit, the operation for adjusting the storage state of polyvinylpyrrolidone becomes complicated, and since the water content of the hollow part forming solution of the present invention is high, the pore diameter of the dense layer is reduced when the spinning solution is solidified. Because it is too small, the material removal performance is reduced.
【００２６】また、本発明は中空部形成液に水分量４５
ｗｔ％から６５ｗｔ％のジメチルアセトアミド水溶液を
用いる。紡糸原液中の水分量と中空部形成液中の水分量
の組み合わせにより、破断強度および破断伸度がともに
優れた中空糸膜を提供することができる。In the present invention, the water content of the hollow part forming liquid is 45%.
An aqueous solution of dimethylacetamide of from wt% to 65 wt% is used. The combination of the amount of water in the spinning solution and the amount of water in the hollow part forming solution can provide a hollow fiber membrane excellent in both breaking strength and breaking elongation.
【００２７】本発明の中空糸膜の製造方法においては、
２重管状の吐出ノズルの外管から上記紡糸原液を、内管
から中空部形成液を同時に空中へ吐出し、水性凝固浴に
導入して凝固させる。その際、１℃から８℃の水性凝固
浴に中空糸膜を導入することが好ましい。さらに好まし
くは４℃から８℃である。In the method for producing a hollow fiber membrane of the present invention,
The spinning stock solution is simultaneously discharged into the air from the outer tube of the double tubular discharge nozzle, and the hollow forming liquid is simultaneously discharged from the inner tube into the aqueous coagulation bath, where it is coagulated. At that time, it is preferable to introduce the hollow fiber membrane into an aqueous coagulation bath at 1 ° C. to 8 ° C. More preferably, the temperature is from 4 ° C to 8 ° C.
【００２８】[0028]
【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。EXAMPLES The present invention will be described more specifically below with reference to examples.
【００２９】［実施例１］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ１７００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）３．５ｗｔ％、
ジメチルアセトアミド８０．５ｗｔ％からなる紡糸溶液
１００重量部、水１．０重量部の割合からなる紡糸原液
を調整し、また、水を５０ｗｔ％含有するジメチルアセ
トアミド溶液を中空部形成液として調整した。２重管状
ノズルの外管（吐出空間の外径０．４５ｍｍ、内径０．
２６ｍｍ）より紡糸原液を、内管（吐出空間の外径０．
１６ｍｍ）より中空部形成液を同時に２５℃の空気中に
吐出したのち、５℃の水性（実質的に水のみ）凝固浴に
導入し凝固させた。さらに、３０℃から４５℃の温水で
洗浄し、枷に巻き取った。その後、中空糸膜の束を作製
し、乾燥した。得られた中空糸膜は、内径１９７μｍ、
膜厚４３μｍであった。Example 1 Polysulfone (Amoco:
UDEL P1700) 16 wt%, polyvinylpyrrolidone (BASF: Kollidon 90F) 3.5 wt%,
A spinning stock solution consisting of 100 parts by weight of a spinning solution composed of 80.5 wt% of dimethylacetamide and 1.0 part by weight of water was prepared, and a dimethylacetamide solution containing 50 wt% of water was prepared as a hollow part forming liquid. Outer tube of double tubular nozzle (outer diameter of discharge space 0.45 mm, inner diameter 0.
26 mm) from the inner tube (the outer diameter of the discharge space is 0.2 mm).
16 mm), the liquid was simultaneously discharged into air at 25 ° C., and then introduced into an aqueous (substantially water only) coagulation bath at 5 ° C. for coagulation. Further, it was washed with warm water of 30 ° C. to 45 ° C. and wound up with a shackle. Thereafter, a bundle of hollow fiber membranes was prepared and dried. The obtained hollow fiber membrane has an inner diameter of 197 μm,
The film thickness was 43 μm.
【００３０】［実施例２］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ３５００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）４．０ｗｔ％、
ジメチルアセトアミド８０ｗｔ％からなる紡糸溶液１０
０重量部、水１．０重量部の割合からなる紡糸原液を調
整し、その他の条件は、実施例１と同様にして中空糸膜
を得た。得られた中空糸膜は、内径２０４μｍ、膜厚４
５μｍであった。Example 2 Polysulfone (Amoco:
UDEL P3500) 16 wt%, polyvinylpyrrolidone (manufactured by BASF: Kollidon 90F) 4.0 wt%,
Spinning solution 10 consisting of 80% by weight of dimethylacetamide
A spinning dope comprising 0 parts by weight and 1.0 part by weight of water was prepared, and the other conditions were the same as in Example 1 to obtain a hollow fiber membrane. The obtained hollow fiber membrane has an inner diameter of 204 μm and a thickness of 4 μm.
It was 5 μm.
【００３１】［比較例１］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ１７００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）３．５ｗｔ％、
ジメチルアセトアミド８０．５ｗｔ％からなる紡糸溶液
１００重量部、水１．６重量部の割合からなる紡糸原液
を調整し、その他の条件は、実施例１と同様にして中空
糸膜を得た。得られた中空糸膜は、内径１９８μｍ、膜
厚４４μｍであった。Comparative Example 1 Polysulfone (Amoco:
UDEL P1700) 16 wt%, polyvinylpyrrolidone (BASF: Kollidon 90F) 3.5 wt%,
A spinning stock solution consisting of 100 parts by weight of a spinning solution consisting of 80.5 wt% of dimethylacetamide and 1.6 parts by weight of water was prepared, and the other conditions were the same as in Example 1 to obtain a hollow fiber membrane. The obtained hollow fiber membrane had an inner diameter of 198 μm and a thickness of 44 μm.
【００３２】［比較例２］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ１７００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）３．５ｗｔ％、
ジメチルアセトアミド８０．５ｗｔ％からなる紡糸溶液
１００重量部、水２．０重量部の割合からなる紡糸原液
を調整し、その他の条件は、実施例１と同様にして中空
糸膜を得た。得られた中空糸膜は、内径２００μｍ、膜
厚４４μｍであった。Comparative Example 2 Polysulfone (Amoco:
UDEL P1700) 16 wt%, polyvinylpyrrolidone (BASF: Kollidon 90F) 3.5 wt%,
A spinning solution consisting of 100 parts by weight of a spinning solution composed of 80.5 wt% of dimethylacetamide and 2.0 parts by weight of water was prepared, and the other conditions were the same as in Example 1 to obtain a hollow fiber membrane. The obtained hollow fiber membrane had an inner diameter of 200 μm and a thickness of 44 μm.
【００３３】［実験例１］実施例１、２、および比較例
１、２で得られた中空糸膜の破断強度と破断伸度を、中
空糸膜１本で測定長さ５０ｍｍ、引き張り速度５０ｍｍ
／ｍｉｎの条件で測定し、各２０本の平均値を求めた。
結果を表１にまとめた。[Experimental Example 1] The breaking strength and breaking elongation of the hollow fiber membranes obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were measured using a single hollow fiber membrane for a length of 50 mm and a pulling speed. 50mm
/ Min, and the average value of each of the 20 samples was determined.
The results are summarized in Table 1.
【００３４】[0034]
【表１】 [Table 1]
【００３５】［比較例３］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ１７００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）３．５ｗｔ％、
ジメチルアセトアミド８０．５ｗｔ％からなる紡糸溶液
１００重量部、水０．３重量部の割合からなる紡糸原液
を調整し、その他の条件は、実施例１と同様にして中空
糸膜を得た。得られた中空糸膜は、内径１９８μｍ、膜
厚４３μｍであった。Comparative Example 3 Polysulfone (Amoco:
UDEL P1700) 16 wt%, polyvinylpyrrolidone (BASF: Kollidon 90F) 3.5 wt%,
A spinning solution consisting of 100 parts by weight of a spinning solution consisting of 80.5 wt% of dimethylacetamide and 0.3 parts by weight of water was prepared, and the other conditions were the same as in Example 1 to obtain a hollow fiber membrane. The obtained hollow fiber membrane had an inner diameter of 198 μm and a thickness of 43 μm.
【００３６】［比較例４］ポリスルホン（アモコ社製：
ＵＤＥＬ Ｐ１７００）１６ｗｔ％、ポリビニルピロリ
ドン（ＢＡＳＦ社製：コリドン９０Ｆ）３．５ｗｔ％、
ジメチルアセトアミド８０．５ｗｔ％からなる紡糸溶液
１００重量部、水１．０重量部の割合からなる紡糸原液
を調整し、また、水を３５ｗｔ％含有するジメチルアセ
トアミド溶液を中空部形成液としその他の条件は、実施
例１と同様にして中空糸膜を得た。得られた中空糸膜
は、内径１９９μｍ、膜厚４５μｍであった。Comparative Example 4 Polysulfone (Amoco:
UDEL P1700) 16 wt%, polyvinylpyrrolidone (BASF: Kollidon 90F) 3.5 wt%,
A spinning stock solution consisting of 100 parts by weight of a dimethylacetamide 80.5 wt% spinning solution and 1.0 parts by weight of water was prepared, and a dimethylacetamide solution containing 35 wt% of water was used as a hollow part forming solution, and other conditions were used. A hollow fiber membrane was obtained in the same manner as in Example 1. The obtained hollow fiber membrane had an inner diameter of 199 μm and a thickness of 45 μm.
【００３７】［実験例２］実施例１、２、および比較例
３、４で得られた中空糸膜を用いて、中空糸膜の内径を
基準とした有効膜面積３００ｃｍ２のミニモジュールを
作製し、前記測定方法に従い牛血液のアルブミン篩係
数、およびβ２ミクログロブリンの篩係数を測定した。
結果を表２にまとめた。[Experimental Example 2] Using the hollow fiber membranes obtained in Examples 1 and 2 and Comparative Examples 3 and 4, mini-modules having an effective membrane area of 300 cm 2 based on the inner diameter of the hollow fiber membrane were produced. and, albumin sieving coefficient of bovine blood, and β 2 microglobulin sieving coefficient was measured according to the measuring methods.
The results are summarized in Table 2.
【００３８】[0038]
【表２】 [Table 2]
【００３９】[0039]
【発明の効果】本発明のポリスルホン製人工腎臓用中空
糸膜は、破断強度および判断伸度に優れ、本発明の中空
糸膜を用いて人工腎臓を組み立てた場合、作業性に優
れ、また、アルブミンの損失が少なく、β２ミクログロ
ブリンをはじめとする中高分子量の除去物質の高い除去
性能を有するという効果を奏するものである。Industrial Applicability The hollow fiber membrane for artificial kidney made of polysulfone of the present invention is excellent in breaking strength and judgment elongation, and excellent in workability when an artificial kidney is assembled using the hollow fiber membrane of the present invention. less loss of albumin, in which the effect of having a high removal performance of removing material of high molecular weight in, including beta 2 microglobulin.
───────────────────────────────────────────────────── フロントページの続き Ｆターム(参考） 4C077 AA05 BB01 KK12 KK13 KK25 LL05 LL22 NN05 NN18 PP15 PP18 4D006 GA13 MA01 MA25 MA31 MA33 MB02 MB06 MB16 MC40X MC62X MC88 NA04 NA10 NA17 NA18 PA05 PB09 PB52 PB59 PC47 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4C077 AA05 BB01 KK12 KK13 KK25 LL05 LL22 NN05 NN18 PP15 PP18 4D006 GA13 MA01 MA25 MA31 MA33 MB02 MB06 MB16 MC40X MC62X MC88 NA04 NA10 NA17 NA18 PA05 PB09 PB52 PB59 PC47
Claims (5)
ルホン製人工腎臓用中空糸膜において、破断強度が２０
ｇｆ／本以上、破断伸度が３０％以上であることを特徴
とするポリスルホン製人工腎臓用中空糸膜。1. A hollow fiber membrane for artificial kidney made of polysulfone containing polyvinylpyrrolidone having a breaking strength of 20
A polysulfone hollow fiber membrane for artificial kidney, wherein the hollow fiber membrane has gf / piece or more and elongation at break of 30% or more.
ルホン製人工腎臓用中空糸膜において、中空糸膜の内径
と外径から求めた中空糸膜断面積に換算し、４７０ｇｆ
／ｍｍ２以上、破断伸度が３０％以上であることを特徴
とするポリスルホン製人工腎臓用中空糸膜。2. In a hollow fiber membrane for an artificial kidney made of polysulfone containing polyvinylpyrrolidone, 470 gf is calculated as the hollow fiber membrane cross-sectional area obtained from the inner diameter and outer diameter of the hollow fiber membrane.
/ Mm 2 or more, and the elongation at break is 30% or more.
５０μｍ、膜厚が３５μｍから５５μｍであることを特
徴とする請求項１または２に記載のポリスルホン製人工
腎臓用中空糸膜。3. The hollow fiber membrane has an inner diameter of 150 μm to 2 μm.
The hollow fiber membrane for artificial kidney made of polysulfone according to claim 1 or 2, wherein the membrane has a thickness of 50 µm and a thickness of 35 µm to 55 µm.
ポリビニルピロリドンが少なくとも３ｗｔ％およびジメ
チルアセトアミドからなる紡糸溶液１００重量部に対し
て、水を０．５重量部から１．１重量部含有する紡糸原
液、および、水分量４５ｗｔ％から６５ｗｔ％のジメチ
ルアセトアミド水溶液からなる中空部形成液を、２重管
状ノズルから吐出し、１℃から８℃の水性凝固浴へ導入
して乾湿式紡糸法により紡糸することを特徴とするポリ
スルホン製人工腎臓用中空糸膜の製造方法。4. The polysulfone is at least 15% by weight,
A spinning solution containing 0.5 to 1.1 parts by weight of water with respect to 100 parts by weight of a spinning solution containing at least 3 wt% of polyvinylpyrrolidone and dimethylacetamide, and dimethylacetamide having a water content of 45 to 65 wt% A hollow fiber membrane for an artificial kidney made of polysulfone, wherein a hollow part forming liquid comprising an aqueous solution is discharged from a double tubular nozzle, introduced into an aqueous coagulation bath at 1 ° C to 8 ° C, and spun by a dry-wet spinning method. Manufacturing method.
５ｗｔ％から１８ｗｔ％、ポリビニルピロリドンが３ｗ
ｔ％から５ｗｔ％、ジメチルアセトアミドが７７ｗｔ％
から８２ｗｔ％であることを特徴とする請求項４に記載
のポリスルホン製人工腎臓用中空糸膜の製造方法。5. The method according to claim 1, wherein the polysulfone is 1 in the spinning solution.
5wt% to 18wt%, polyvinylpyrrolidone 3w
5% by weight to 5% by weight, 77% by weight of dimethylacetamide
The method for producing a hollow fiber membrane for an artificial kidney made of polysulfone according to claim 4, wherein the content is from 2 to 82 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150096A JP2000334281A (en) | 1999-05-28 | 1999-05-28 | Hollow fiber membrane for artificial kidney made of polysulfone and its production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11150096A JP2000334281A (en) | 1999-05-28 | 1999-05-28 | Hollow fiber membrane for artificial kidney made of polysulfone and its production |
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| Publication Number | Publication Date |
|---|---|
| JP2000334281A true JP2000334281A (en) | 2000-12-05 |
Family
ID=15489435
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11150096A Pending JP2000334281A (en) | 1999-05-28 | 1999-05-28 | Hollow fiber membrane for artificial kidney made of polysulfone and its production |
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| Country | Link |
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| JP (1) | JP2000334281A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010227932A (en) * | 2005-10-13 | 2010-10-14 | Asahi Kasei Chemicals Corp | Porous multilayered hollow-fiber membrane and process for producing the same |
| US9616393B2 (en) | 2007-12-06 | 2017-04-11 | Asahi Kasei Medical Co., Ltd. | Porous hollow fiber membrane for treating blood |
-
1999
- 1999-05-28 JP JP11150096A patent/JP2000334281A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010227932A (en) * | 2005-10-13 | 2010-10-14 | Asahi Kasei Chemicals Corp | Porous multilayered hollow-fiber membrane and process for producing the same |
| US9616393B2 (en) | 2007-12-06 | 2017-04-11 | Asahi Kasei Medical Co., Ltd. | Porous hollow fiber membrane for treating blood |
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