JP2001038170A - Hollow fiber membrane - Google Patents
Hollow fiber membraneInfo
- Publication number
- JP2001038170A JP2001038170A JP21991299A JP21991299A JP2001038170A JP 2001038170 A JP2001038170 A JP 2001038170A JP 21991299 A JP21991299 A JP 21991299A JP 21991299 A JP21991299 A JP 21991299A JP 2001038170 A JP2001038170 A JP 2001038170A
- Authority
- JP
- Japan
- Prior art keywords
- membrane
- pvp
- hollow fiber
- fiber membrane
- polyvinylpyrrolidone
- 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
- 239000012528 membrane Substances 0.000 claims abstract description 82
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 80
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 80
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 80
- 239000012510 hollow fiber Substances 0.000 claims abstract description 34
- 229920000642 polymer Polymers 0.000 claims abstract description 28
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims description 29
- 239000002158 endotoxin Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 238000009987 spinning Methods 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 14
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 208000003455 anaphylaxis Diseases 0.000 abstract description 8
- 206010002198 Anaphylactic reaction Diseases 0.000 abstract description 6
- 238000000502 dialysis Methods 0.000 abstract description 5
- 206010037660 Pyrexia Diseases 0.000 abstract description 2
- 230000014509 gene expression Effects 0.000 abstract description 2
- 230000036783 anaphylactic response Effects 0.000 abstract 1
- 230000027950 fever generation Effects 0.000 abstract 1
- 230000004044 response Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 20
- 239000008280 blood Substances 0.000 description 19
- 210000004369 blood Anatomy 0.000 description 19
- 239000003795 chemical substances by application Substances 0.000 description 19
- 238000005345 coagulation Methods 0.000 description 11
- 230000015271 coagulation Effects 0.000 description 11
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 8
- 238000000862 absorption spectrum Methods 0.000 description 8
- 238000005191 phase separation Methods 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 6
- 238000012545 processing Methods 0.000 description 6
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 5
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 238000011109 contamination Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 238000012937 correction Methods 0.000 description 3
- 238000001631 haemodialysis Methods 0.000 description 3
- 230000000322 hemodialysis Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 206010002199 Anaphylactic shock Diseases 0.000 description 2
- 102000004506 Blood Proteins Human genes 0.000 description 2
- 108010017384 Blood Proteins Proteins 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000010828 elution Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002223 polystyrene Polymers 0.000 description 2
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000239218 Limulus Species 0.000 description 1
- 101100545275 Mus musculus Znf106 gene Proteins 0.000 description 1
- 208000001647 Renal Insufficiency Diseases 0.000 description 1
- 229920003350 Spectratech® Polymers 0.000 description 1
- 101001094026 Synechocystis sp. (strain PCC 6803 / Kazusa) Phasin PhaP Proteins 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000004840 adhesive resin Substances 0.000 description 1
- 229920006223 adhesive resin Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005465 channeling Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000001891 gel spinning Methods 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 201000006370 kidney failure Diseases 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical group O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 125000006850 spacer group Chemical group 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004368 synchrotron infrared microspectroscopy Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は新規な中空糸膜に関
する。詳しくは腎不全などの治療に用いる膜であり、ア
ナフィラキシー反応の発生が少なく、エンドトキシンの
混入を吸着によって阻止することができるため安全性が
高く、かつモジュール組立性に優れた血液浄化膜に関す
る。[0001] The present invention relates to a novel hollow fiber membrane. More specifically, the present invention relates to a blood purification membrane that is used for treatment of renal failure and the like, has low anaphylactic reaction, can prevent endotoxin from being mixed by adsorption, has high safety, and has excellent module assemblability.
【０００２】[0002]
【従来の技術】ポリスルホン系ポリマーを原料とする血
液浄化膜には、膜の親水化剤としてポリビニルピロリド
ン（ＰＶＰ）を使用するのがほとんどである。ＰＶＰを
使用すると膜が親水化されるために、膜面への血漿蛋白
の吸着を抑制することができ、膜の分画特性が向上し、
血液浄化膜としての性能が向上する。ＰＶＰを膜内に入
れる方法は、ポリマーとＰＶＰを共通溶媒に溶解させ、
場合によっては非溶媒を加えて紡糸原液とし、ノズルか
ら吐出すると同時に内液から凝固性内液を送り出すこと
で相分離を引き起こし膜形成させて、膜内にＰＶＰを閉
じこめる方法が一般的である。2. Description of the Related Art In most cases, a blood purification membrane made of a polysulfone-based polymer uses polyvinylpyrrolidone (PVP) as a hydrophilic agent for the membrane. When PVP is used, since the membrane is hydrophilized, adsorption of plasma proteins to the membrane surface can be suppressed, and the fractionation characteristics of the membrane are improved.
The performance as a blood purification membrane is improved. The method of putting PVP into the membrane is to dissolve the polymer and PVP in a common solvent,
In some cases, a non-solvent is added to form a spinning stock solution, and a method of discharging a coagulable inner solution from the inner solution at the same time as discharging from a nozzle to cause phase separation to form a film, thereby closing PVP in the film is general.
【０００３】しかし、相分離においてＰｏｌｙｍｅｒ−
ｒｉｃｈ相に存在するＰＶＰはポリマー内にてポリマー
と相溶状態にあるが、Ｐｏｌｙｍｅｒ−ｌｅａｎ相にお
けるＰＶＰは凝固後にフリーのＰＶＰとなる。フリーの
ＰＶＰは血液接触時に血液中へと溶出しアナフィラキシ
ー反応を起こす危険性がある。しかも本来ならば、ポリ
スルホン系ポリマーはエンドトキシンを吸着する特性を
有しているが、ＰＶＰを加えて親水化することで、吸着
特性を失い、エンドトキシンの混入がみられ、透析患者
が発熱する場合が見受けられる。場合によってはＰＶＰ
の溶出とエンドトキシンの混入が同時に起こることでア
ナフィラキシー反応が生じるとの報告もあり、ＰＶＰの
溶出とエンドトキシンの混入は絶対に避けるべき課題で
ある。However, in phase separation, Polymer-
PVP present in the rich phase is compatible with the polymer in the polymer, but PVP in the Polymer-lean phase becomes free PVP after solidification. Free PVP may be eluted into blood upon blood contact and cause an anaphylactic reaction. Moreover, polysulfone-based polymers originally had the property of adsorbing endotoxin, but by adding PVP to make it hydrophilic, the polysulfone polymer lost its adsorbing properties, endotoxin was mixed in, and the dialysis patient may generate heat. Can be seen. In some cases PVP
It has been reported that the anaphylactic reaction occurs due to simultaneous elution of endotoxin and contamination of endotoxin, and elution of PVP and contamination of endotoxin are issues that must be absolutely avoided.
【０００４】また、膜を乾燥させたときに膜の外側に溶
出したＰＶＰが介在して糸同士がくっつき（固着）、糸
の間隙に接着樹脂が浸透しないためにバンドルをモジュ
ールとしたときにリークが生じる。また本モジュール製
作が可能だったとしても固着部分は膜の有効面積となら
ないために溶質除去性能に劣る。固着を防ぐために糸に
スペーサーヤーンを巻き付ける方法も採用されている
が、非常に手間がかかる工程であると同時にコストがか
かる。Also, when the membrane is dried, the PVP eluted outside the membrane is interposed, and the yarns stick to each other (stick), and the adhesive resin does not penetrate into the gaps between the yarns, so that when the bundle is made into a module, the leakage occurs. Occurs. Even if this module can be manufactured, the fixed portion does not have an effective area of the film, so that the solute removal performance is poor. In order to prevent sticking, a method of winding a spacer yarn around the yarn is also adopted, but it is a very laborious process and also costs high.
【０００５】このように膜内のＰＶＰの存在状態は非常
に重要な問題であり、ＰＶＰは性能発現の面で必要な物
質であるが、フリーのＰＶＰが多いとアナフィラキシー
反応や固着の原因となるとともにエンドトキシン吸着能
力が失われることが、ポリスルホン系中空糸膜に共通の
問題となっている。[0005] As described above, the presence state of PVP in the membrane is a very important problem. PVP is a necessary substance in terms of performance, but if there is a lot of free PVP, it causes anaphylactic reaction and fixation. In addition, the loss of endotoxin adsorption ability is a common problem with polysulfone-based hollow fiber membranes.
【０００６】[0006]
【発明が解決しようとする課題】アナフィラキシー反
応、透析中の発熱の危険性を低減すると同時に、モジュ
ール組立性に優れた中空糸膜を得る。An object of the present invention is to provide a hollow fiber membrane which is excellent in module assemblability while reducing the risk of anaphylactic reaction and heat generation during dialysis.
【０００７】[0007]
【課題を解決するための手段】本発明は以下のものであ
る。 実質的にポリスルホン系ポリマーとポリビニルピロ
リドンからなる膜であり、膜内表面のポリビニルピロリ
ドン含有率（Ｃｉ）と膜外表面のポリビニルピロリドン
含有率（Ｃｏ）、膜内の平均ポリビニルピロリドン含有
率（Ｃａｖｅ）の関係が下式で表されることを特徴とす
る中空糸膜。 Ｃｉ≧Ｃｏ×３、Ｃｉ≧Ｃａｖｅ×２ 膜のエンドトキシン吸着能力が２０００ＥＵ／m2以
上である上記記載の中空糸膜。 膜外表面の開孔率が２５% 以上である上記または
記載の中空糸膜。 エアーギャップ滞留時間０．５秒以上、凝固浴温度
７０℃以上、ノズル温度が凝固浴温度より２０℃以上低
い紡糸方法にて製造する上記ないしのいずれかに記
載の中空糸膜。 紡糸工程において４０℃以上の水で１分以上洗浄し
た後、８０℃以上の熱水中で３０秒以上、該中空糸膜を
洗浄することによって得られる上記ないしのいずれ
かに記載の中空糸膜。The present invention is as follows. A membrane substantially comprising a polysulfone-based polymer and polyvinylpyrrolidone, wherein the content of polyvinylpyrrolidone on the inner surface of the film (Ci), the content of polyvinylpyrrolidone on the outer surface of the film (Co), and the average content of polyvinylpyrrolidone in the film (Cave) Is represented by the following formula: Ci ≧ Co × 3, Ci ≧ Cave × 2 The hollow fiber membrane as described above, wherein the endotoxin adsorption capacity of the membrane is 2000 EU / m 2 or more. The hollow fiber membrane according to the above or the above, wherein the porosity of the outer surface of the membrane is 25% or more. The hollow fiber membrane according to any one of the above, which is produced by a spinning method in which an air gap residence time is 0.5 seconds or more, a coagulation bath temperature is 70 ° C. or more, and a nozzle temperature is 20 ° C. or more lower than the coagulation bath temperature. The hollow fiber membrane according to any one of the above or the above, which is obtained by washing the hollow fiber membrane in hot water at 80 ° C. or more for 30 seconds or more after washing with water at 40 ° C. or more for 1 minute or more in the spinning step. .
【０００８】[0008]
【発明の実施の形態】本発明における血液浄化膜は実質
的にポリスルホン系ポリマーとポリビニルピロリドン
（ＰＶＰ）からなる。ポリスルホン系ポリマーは生体適
合性と膜の分画特性に優れる膜素材である。ポリスルホ
ン系ポリマーの中でも、ポリエーテルスルホン（ＰＥ
Ｓ）が生体適合性と耐熱性の面から血液透析膜の素材と
して好ましい。ポリスルホン系ポリマーを血液透析膜に
使用する場合、血漿蛋白の膜への付着を抑制するため膜
の親水化剤としてＰＶＰを使用することが多い。ＰＶＰ
を膜内に含ませて親水化することで血液透析膜としての
実力を発揮することができる。BEST MODE FOR CARRYING OUT THE INVENTION The blood purification membrane of the present invention substantially comprises a polysulfone-based polymer and polyvinylpyrrolidone (PVP). Polysulfone-based polymers are membrane materials that are excellent in biocompatibility and membrane fractionation characteristics. Among polysulfone polymers, polyethersulfone (PE
S) is preferable as a material for the hemodialysis membrane in view of biocompatibility and heat resistance. When a polysulfone-based polymer is used for a hemodialysis membrane, PVP is often used as a hydrophilic agent for the membrane in order to suppress the adhesion of plasma proteins to the membrane. PVP
Is included in the membrane to make it hydrophilic, so that the ability as a hemodialysis membrane can be exhibited.
【０００９】しかし、ＰＶＰが膜から溶出し透析患者の
血液に入るとアナフィラキシーショック反応を引き起こ
す危険性がある。また、膜の外側に溶出したＰＶＰは糸
の間隙に介在して、糸同士がくっつく（糸の固着）。固
着したバンドルはモジュール組立の際に糸の間隙に接着
樹脂が浸入せずリークが起こる。すなわちＰＶＰは性能
発現の点で非常に重要であるにもかかわらず、必要以上
のＰＶＰは安全性やモジュール組立性の面で問題があ
る。特に、血液接触面において、膜に保持されたＰＶＰ
は溶質透過性能を発現するためには不可欠であるもの
の、その他の膜支持層部分でＰＶＰが存在する意味はな
い。However, when PVP elutes from the membrane and enters the blood of a dialysis patient, there is a risk of causing an anaphylactic shock reaction. Further, the PVP eluted outside the membrane is interposed in the gap between the yarns and the yarns stick to each other (the yarns are fixed). The adhesive bundle does not penetrate into the gap between the yarns during the assembly of the fixed bundle, so that a leak occurs. That is, although PVP is very important in terms of performance, PVP more than necessary has problems in safety and module assemblability. In particular, at the blood contact surface, the PVP retained on the membrane
Although PVP is indispensable for exhibiting solute permeation performance, there is no meaning in the presence of PVP in other membrane support layers.
【００１０】また、ポリスルホン系ポリマーにはエンド
トキシン吸着能があることが知られている。膜の支持層
部分にＰＶＰが多く存在すると、ＰＶＰの親水化効果に
より、エンドトキシン吸着能が損なわれる。透析液中に
存在するエンドトキシンが膜を介して血液中に入ると患
者が発熱、中には溶出したＰＶＰとの相乗効果によりア
ナフィラキシーショック反応を引き起こすとの報告もあ
る。各透析施設は透析液の清浄化に取り組んでいるもの
の、エンドトキシンが全くない透析液を得ることは事実
上不可能である。そこで、膜にエンドトキシン吸着能力
があれば、エンドトキシンが患者の血液中へ入るのを阻
止できる。よって、ＰＶＰは血液接触面には絶対必要で
あるが、その他の部分には存在しない方がよい。It is known that polysulfone polymers have endotoxin adsorption ability. If PVP is present in a large amount in the support layer portion of the membrane, the endotoxin-adsorbing ability is impaired due to the hydrophilic effect of PVP. It has been reported that when endotoxin present in the dialysate enters the blood through the membrane, the patient generates fever, and a synergistic effect with the eluted PVP causes an anaphylactic shock reaction. Although each dialysis facility is working on purifying the dialysate, it is virtually impossible to obtain a dialysate that is completely free of endotoxin. Thus, if the membrane has the ability to adsorb endotoxin, endotoxin can be prevented from entering the patient's blood. Therefore, PVP is absolutely necessary for the blood contact surface, but should not be present in other parts.
【００１１】血液接触面だけにＰＶＰを存在させようと
すると、中空糸を紡糸してから中空糸内面に固定する方
法が考えられるが、コストの面、技術的な面で非常に困
難である。よって、ポリマーとＰＶＰを紡糸原液の中に
投入しておき、紡糸工程において血液接触面である中空
糸の内面に局在化させる方法が効果的である。If PVP is to be present only on the blood contact surface, a method of spinning the hollow fiber and fixing it on the inner surface of the hollow fiber is conceivable, but it is very difficult in terms of cost and technology. Therefore, it is effective to put the polymer and PVP into the spinning solution and localize the polymer and PVP on the inner surface of the hollow fiber which is the blood contact surface in the spinning process.
【００１２】本発明における中空糸膜は、ポリマーと非
溶媒とＰＶＰと溶媒からなる紡糸原液を二重紡糸口金の
外側から押し出し、内側から凝固性液体を吐出し、エア
ギャップ部を経て凝固浴へと浸漬した後、水洗して得る
ことができる。押し出された紡糸原液は凝固性内液によ
って相分離が始める。相分離におけるＰｏｌｙｍｅｒ−
ｒｉｃｈ相に存在するＰＶＰはポリマー内にてポリマー
と相溶状態にあり、凝固後はポリマー内に閉じこめられ
て、膜が血液と接触しても、血液中へと溶出しない。し
かし、Ｐｏｌｙｍｅｒ−ｌｅａｎ相におけるＰＶＰはフ
リーであり、紡糸工程における水洗浴にて洗い流す必要
がある。フリーのＰＶＰを洗い流した結果、血液接触面
の緻密層にＰＶＰが局在化し、膜の支持層部分にはＰＶ
Ｐの含有率が低い膜が得られる。In the hollow fiber membrane of the present invention, a spinning solution comprising a polymer, a non-solvent, PVP and a solvent is extruded from the outside of a double spinneret, a coagulable liquid is discharged from the inside, and the coagulated liquid is passed through an air gap to a coagulation bath. After immersion, it can be obtained by washing with water. The extruded spinning dope starts phase separation due to the coagulable inner solution. Polymer- in phase separation
The PVP present in the rich phase is in a compatible state with the polymer in the polymer, is confined in the polymer after coagulation, and does not elute into the blood even if the membrane comes into contact with blood. However, PVP in the Polymer-lean phase is free and needs to be washed away in a washing bath in the spinning process. As a result of washing away free PVP, PVP is localized in the dense layer on the blood contact surface, and PV
A film having a low P content is obtained.
【００１３】1Ｈ−ＮＭＲおよび、表面赤外吸収スペク
トルより求められるポリスルホン系ポリマーに対するＰ
ＶＰの含有率において、膜内表面のポリマーに対するＰ
ＶＰ含有率（Ｃｉ）と膜外表面のＰＶＰ含有率（Ｃ
ｏ）、膜内の平均ＰＶＰ含有率（Ｃａｖｅ）の関係が Ｃｉ≧Ｃｏ×３、Ｃｉ≧Ｃａｖｅ×２ （式１） のとき、血液接触面である膜内表面にＰＶＰが集中して
おり、支持層部分のＰＶＰ含有量が低くなり、好まし
い。[0013] P for a polysulfone-based polymer determined from 1 H-NMR and surface infrared absorption spectrum
In terms of VP content, P with respect to the polymer on the inner surface of the film
VP content (Ci) and PVP content (C
o), when the relationship of the average PVP content (Cave) in the membrane is Ci ≧ Co × 3, Ci ≧ Cave × 2 (Equation 1), PVP is concentrated on the inner surface of the membrane which is the blood contact surface, The PVP content in the support layer portion is low, which is preferable.
【００１４】フリーのＰＶＰを十分に洗い流す方法であ
るが、ただ単に洗浄を強化するだけでは不十分である。
最も重要なことは、膜の構造において外表面を大きく開
孔させることである。外表面を開孔させることで洗浄効
率が向上し、フリーのＰＶＰを十分に除去できる。外表
面に開孔がみられない場合は、膜内のフリーのＰＶＰが
膜外へと出ていくのが妨げられる。その場合、血液中へ
のＰＶＰ溶出量が増大すると同時に、糸の固着が発生す
る。Although this is a method of sufficiently washing free PVP, it is not enough to simply enhance the washing.
The most important thing is to make the outer surface large open in the structure of the membrane. By opening the outer surface, the cleaning efficiency is improved, and free PVP can be sufficiently removed. If no pores are found on the outer surface, free PVP in the membrane is prevented from going out of the membrane. In this case, the amount of PVP eluted into the blood increases, and at the same time, the thread sticks.
【００１５】外表面の開孔率は２５％以上が好ましい。
２５％以下の場合は洗浄効率が落ち、ＰＶＰ溶出量が増
大すると同時に糸の固着が発生する。外表面開孔率の測
定方法は、中空糸サンプルの外表面を走査型電子顕微鏡
（ＳＥＭ）で倍率１０，０００倍にて撮影し、画像処理
装置を用いる方法、あるいはトレーシングペーパーでＳ
ＥＭ像を写しとって、開孔部分を切り取り、紙の重量を
測定して求める方法がある。その中でも画像処理で求め
る方法が定量性が高く好ましい。画像処理で求める方法
としては東洋紡績株式会社製画像処理装置イメージアナ
ライザーＶ２０を用いるのが好ましい。ＴＯＫＳ法自動
二値化法により開孔部を白色、その他を黒色とし、白色
部分の面積と全体の面積の比を求めて外表面開孔率とす
る。The porosity of the outer surface is preferably 25% or more.
If it is 25% or less, the washing efficiency is reduced, the amount of PVP eluted is increased, and at the same time, the yarn is fixed. The outer surface porosity can be measured by taking an image of the outer surface of the hollow fiber sample with a scanning electron microscope (SEM) at a magnification of 10,000 times and using an image processing device, or by using a tracing paper.
There is a method in which an EM image is copied, the opening is cut out, and the weight of the paper is measured. Among them, a method obtained by image processing is preferable because of its high quantitative property. It is preferable to use an image processing apparatus image analyzer V20 manufactured by Toyobo Co., Ltd. as a method of obtaining the image by image processing. The opening portion is white and the others are black by the TOKS automatic binarization method, and the ratio of the area of the white portion to the entire area is determined to be the outer surface opening ratio.
【００１６】外表面の開孔率をあげる手段は乾湿式紡糸
法におけるＡＧ長さを長くする、あるいは紡速を低下さ
せるのが有効である。すなわち、ＡＧ部の滞留時間を長
く、０．５秒以上とする。ＡＧ部滞留時間を長くするこ
とで凝固性内液によって膜の構造を決定させることがで
きる。すなわち、外表面からの強い凝固によって外表面
に緻密層が形成するのを避けるためにＡＧ滞留時間を長
くする。膜は内液によって構造が決定された後に凝固浴
へと導入される。この方法によって外表面に緻密層がな
く、開孔した膜が得られる。As a means for increasing the porosity of the outer surface, it is effective to lengthen the AG length or reduce the spinning speed in the dry-wet spinning method. That is, the residence time of the AG unit is long, and is set to 0.5 seconds or more. By increasing the residence time of the AG section, the structure of the film can be determined by the coagulable internal solution. That is, the AG residence time is lengthened in order to avoid formation of a dense layer on the outer surface due to strong solidification from the outer surface. The membrane is introduced into the coagulation bath after the structure has been determined by the internal solution. According to this method, an open film having no dense layer on the outer surface can be obtained.
【００１７】ＡＧ部の滞留時間を長くすることで、外表
面が開孔した膜が得られるが、開孔率を上げるために
は、それだけでは不十分である。外表面の開孔率を上げ
るためには、ＡＧ部における水分の存在が不可欠であ
る。二重紡糸口金から吐出した紡糸原液はＡＧ部に存在
する水蒸気を吸収して相分離がおこり、外表面が大きく
開孔した膜が得られる。具体的には、ＡＧ部の温度を４
０℃以上、湿度を９０％以上に保つことで、外表面開孔
率を２５％以上にすることができる。By increasing the residence time of the AG portion, a film having an open outer surface can be obtained, but this alone is not sufficient to increase the opening ratio. In order to increase the porosity of the outer surface, the presence of water in the AG portion is indispensable. The spinning dope discharged from the double spinneret absorbs water vapor present in the AG section and undergoes phase separation, resulting in a membrane having a large open outer surface. Specifically, the temperature of the AG section is set to 4
By keeping the temperature at 0 ° C. or more and the humidity at 90% or more, the outer surface porosity can be made 25% or more.
【００１８】ＡＧ部の温度を４０℃以上、湿度を９０％
以上にする具体的手段は凝固浴温度７０℃以上、ノズル
温度を凝固浴温度より２０℃以上低くする方法が有効で
ある。凝固浴から蒸発する水蒸気によって、外表面の相
分離を促進する。The temperature of the AG section is 40 ° C. or more and the humidity is 90%
As a specific means for achieving the above, a method of lowering the nozzle temperature by 20 ° C. or more from the coagulation bath temperature of 70 ° C. or more and the nozzle temperature is effective. The water vapor evaporating from the coagulation bath promotes phase separation on the outer surface.
【００１９】膜の外表面を２５％以上に開孔させたうえ
で、十分に洗浄を実施する必要がある。洗浄は紡糸工程
において、１分以上４０℃の水で洗浄した後、８０℃の
熱水中で３０秒以上洗浄する方法が効果的である。この
ように紡糸工程にて長時間洗浄するためにはネルソンロ
ーラーを用いるのが容易な方法である。It is necessary to sufficiently clean the membrane after opening the outer surface of the membrane to 25% or more. In the spinning process, a method of washing with water at 40 ° C. for 1 minute or more and then washing in hot water at 80 ° C. for 30 seconds or more is effective. As described above, it is an easy method to use a Nelson roller for washing for a long time in the spinning process.
【００２０】こうして得られた中空糸膜を所定の本数だ
け束ねて樹脂接着し、端部を切り出すことでモジュール
を得ることができる。モジュールのエンドトキシン吸着
量を測定するには、水道水と逆浸透（ＲＯ）水を適量混
合して約３０００ＥＵ／ＬのＥｔ液を５Ｌ調整してビー
カーに入れ、モジュールの透析液入口よりＥｔ液を５０
０ｍｌ／ｍｉｎの流速で導入し、濾過流量１００ｍｌ／
ｍｉｎで中空糸内側へと濾過し、濾過液と透析液出口液
を元のビーカーに戻し、二時間循環させた。循環前と循
環後のビーカー内のエンドトキシン濃度を測定すること
で、膜に吸着したエンドトキシン量を定量することがで
きる。エンドトキシン吸着量は高いほど、血液中へのエ
ンドトキシン混入を妨げるため好ましい。エンドトキシ
ン濃度の測定には和光純薬製のリムルスＥＳ−ＩＩテス
トワコーを用い、トキシノメーターＥＴ２０１にて比濁
時間の測定をすることで定量した。A module can be obtained by bundling a predetermined number of the obtained hollow fiber membranes, bonding them with a resin, and cutting out the ends. In order to measure the endotoxin adsorption amount of the module, tap water and reverse osmosis (RO) water are mixed in an appropriate amount, 5 L of about 3000 EU / L Et solution is adjusted and put into a beaker, and the Et solution is introduced from the dialysate inlet of the module. 50
It was introduced at a flow rate of 0 ml / min, and the filtration flow rate was 100 ml / min.
Then, the filtrate and the dialysate outlet liquid were returned to the original beaker and circulated for 2 hours. By measuring the endotoxin concentration in the beaker before and after circulation, the amount of endotoxin adsorbed on the membrane can be determined. The higher the amount of endotoxin adsorbed, the more preferable it is to prevent endotoxin contamination into blood. The endotoxin concentration was quantified by measuring turbidity time with a toxinometer ET201 using Limulus ES-II Test Wako manufactured by Wako Pure Chemical.
【００２１】[0021]
【実施例】以下に実施例を挙げて、本発明を説明する
が、本発明はなんら限定されるものではない。EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited thereto.
【００２２】（実施例１）ポリエーテルスルホン（ＰＥ
Ｓ）が１７．０重量％、親水化剤にポリビニルピロリド
ン（Ｋ−９０）を３．０重量％、非溶媒として水を５．
０重量％、溶媒にジメチルアセトアミド（ＤＭＡＣ）７
５．０％、内液濃度（ＤＭＡＣ＋水）が５０％として、
紡糸原液を４０℃に保った二重紡糸口金の外側から、内
液を二重紡糸口金の内側から吐出し、ＡＧ長さ６００ｍ
ｍ、紡速６０ｍ／分、すなわちＡＧ滞留時間０．６秒と
したあと、７０℃の凝固浴濃度（ＤＭＡＣ＋水）１０％
の凝固浴へと浸漬した後、純水４５℃にて１分間、純水
８０℃にて４５秒間洗浄し、カセへと巻き取り、内径１
９８．２μm 、膜厚２９．４μｍの中空糸膜を得た。こ
のときのノズルから２５０ｍｍの部分におけるＡＧ部の
温度は４５℃、湿度は９５％であり、ＡＧ部の水分によ
って外表面の相分離を促進できていると考えられる。Example 1 Polyether sulfone (PE
S) is 17.0% by weight, polyvinylpyrrolidone (K-90) is 3.0% by weight as a hydrophilizing agent, and water is used as a non-solvent.
0% by weight, dimethylacetamide (DMAC) 7
5.0%, the internal solution concentration (DMAC + water) is 50%,
The inner solution is discharged from the outside of the double spinneret holding the spinning stock solution at 40 ° C. from the inside of the double spinneret, and the AG length is 600 m.
m, a spinning speed of 60 m / min, that is, an AG residence time of 0.6 second, and a coagulation bath concentration (DMAC + water) of 10% at 70 ° C.
After washing in a coagulation bath for 1 minute at 45 ° C. in pure water and 45 seconds in 80 ° C. in pure water, it is wound into a scalpel,
A hollow fiber membrane having a thickness of 98.2 μm and a thickness of 29.4 μm was obtained. At this time, the temperature of the AG portion at a portion 250 mm from the nozzle was 45 ° C. and the humidity was 95%, and it is considered that the phase separation on the outer surface was promoted by the moisture of the AG portion.
【００２３】得られた中空糸膜の外表面ＳＥＭ像（倍率
１０，０００倍）を図１に示す。外表面ＳＥＭ写真を、
東洋紡績株式会社製イメージアナライザーＶ２０を用い
ＴＯＫＳ法二値化にて画像処理を行った画像を図２に示
す。これから求めた外表面開孔率は３０．１％であっ
た。FIG. 1 shows an SEM image (magnification: 10,000 times) of the outer surface of the obtained hollow fiber membrane. The outer surface SEM photograph,
FIG. 2 shows an image obtained by performing image processing by TOKS binarization using an image analyzer V20 manufactured by Toyobo Co., Ltd. The outer surface porosity determined from this was 30.1%.
【００２４】糸の固着は全く観察されず、モジュール組
立は容易であると同時に、透析液のチャネリングはみら
れず、表１に示すように必要とされる溶質除去性能は発
現できていた。膜面積１．５m2のモジュールを組み立
て、４０％エタノール水溶液を使ってモジュールから溶
出するＰＶＰの量を測定したところ、１．５ｍｇとその
量は軽微であり、臨床で使用しても全く問題がないと考
えられた。Attachment of the thread was not observed at all, and the module was easy to assemble. At the same time, no channeling of the dialysate was observed, and as shown in Table 1, the required solute removal performance could be exhibited. When a module with a membrane area of 1.5 m 2 was assembled and the amount of PVP eluted from the module was measured using a 40% aqueous ethanol solution, the amount of PVP was as small as 1.5 mg. It was not considered.
【００２５】このときのＰＶＰ分布量を 1Ｈ−ＮＭＲス
ペクトルと赤外吸収スペクトルを用い、以下の要領で定
量した。 （１） 1Ｈ−ＮＭＲスペクトル 中空糸膜をＤＭＳＯ−ｄ6 に溶解させ、６０℃で1 Ｈ−
ＮＭＲスペクトルを測定した。測定にはＶａｒｉａｎ社
製Ｕｎｉｔｙ−５００（Ｈ測定時５００ＭＨｚ）を使用
した。1 Ｈ−ＮＭＲスペクトルにおける７．２ｐｐｍ付
近のポリスルホン系ポリマーの芳香環由来のピーク（プ
ロトン４個分／繰り返し単位）と１．８〜２．２ｐｐｍ
のＰＶＰのピロリドン環由来のピーク（プロトン４個分
／繰り返し単位）の積分強度比より、膜内の平均ＰＶＰ
含有率Ｃａｖｅ（ｗｔ％）を算出した。The amount of PVP distribution at this time was quantified using 1 H-NMR spectrum and infrared absorption spectrum in the following manner. (1) dissolving 1 H-NMR spectrum hollow fiber membrane DMSO-d 6, 1 H- at 60 ° C.
The NMR spectrum was measured. Varian Unity-500 (500 MHz at the time of H measurement) was used for the measurement. A peak (about 4 protons / repeating unit) derived from the aromatic ring of the polysulfone-based polymer at around 7.2 ppm in the 1 H-NMR spectrum and 1.8 to 2.2 ppm
From the integrated intensity ratio of the peak (4 protons / repeating unit) derived from the pyrrolidone ring of PVP, the average PVP in the membrane
The content Cave (wt%) was calculated.
【００２６】（２）赤外吸収スペクトル（ＦＴ−ＩＲス
ペクトル） 膜内外表面の測定はＡＴＲ法、膜全体の測定は透過法に
て行った。測定にはＳＰＥＣＴＲＡ ＴＥＣＨ社製 Ｉ
Ｒμｓ／ＳＩＲＭを使用した。ＡＴＲ法では内部反射エ
レメントとしてダイヤモンド４５°を使用した。赤外吸
収スペクトルにおける１６７５ｃｍ-1のＰＶＰのＣ＝Ｏ
に由来するピークの吸収強度Ａｐと１５８０ｃｍ-1付近
のポリスルホン系ポリマーが由来するピークの吸収強度
Ａｓの比Ａｐ／Ａｓを求めた。ＡＴＲ法においては吸収
強度が測定波数に依存しているため、補正値としてポリ
スルホン系ポリマーのピーク位置νｓおよびＰＶＰのピ
ーク位置νｐ（波数）の比νｐ／νｓを実測値にかけ
た。(2) Infrared absorption spectrum (FT-IR spectrum) Measurement of the inner and outer surfaces of the film was performed by the ATR method, and measurement of the entire film was performed by the transmission method. The measurement was performed by SPECTRA TECH I
Rμs / SIRM was used. In the ATR method, 45 ° diamond was used as an internal reflection element. C = O of PVP at 1675 cm -1 in infrared absorption spectrum
The ratio Ap / As of the absorption intensity Ap of the peak derived from the peak and the absorption intensity As of the peak derived from the polysulfone polymer near 1580 cm -1 was determined. In the ATR method, since the absorption intensity depends on the measured wave number, the ratio νp / νs of the peak position νs of the polysulfone-based polymer and the peak position νp (wave number) of PVP was multiplied by the measured value as a correction value.
【００２７】内表面ＰＶＰ含有率（Ｃｉ）および外表面
のＰＶＰ含有率（Ｃｏ）は以下の式より算出した。 Ｃｉ＝Ｃａｖｅ×Ｒｉ／Ｒｔ （式２） Ｃｏ＝Ｃａｖｅ×Ｒｏ／Ｒｔ （式３） Ｃａｖｅ： 1 Ｈ−ＮＭＲより求めたＰＶＰ含有率 Ｒｉ： ＦＴ−ＩＲ ＡＴＲ法における内表面のＰＶＰ
とポリスルホン系ポリマーの吸光度比（補正後） Ｒｏ： ＦＴ−ＩＲ ＡＴＲ法における外表面のＰＶＰ
とポリスルホン系ポリマーの吸光度比（補正後） Ｒｔ： ＦＴ−ＩＲ透過法におけるＰＶＰとポリスルホ
ン系ポリマーの吸光度比The PVP content (Ci) of the inner surface and the PVP content (Co) of the outer surface were calculated by the following equations. Ci = Cave × Ri / Rt (Equation 2) Co = Cave × Ro / Rt (Equation 3) Cave: PVP content determined from 1 H-NMR Ri: PVP on inner surface in FT-IR ATR method
Ratio of polystyrene and polysulfone-based polymer (after correction) Ro: PVP on outer surface in FT-IR ATR method
Ratio between polystyrene and polysulfone-based polymer (after correction) Rt: Absorbance ratio between PVP and polysulfone-based polymer in FT-IR transmission method
【００２８】上記紡糸条件にて得られた膜の 1Ｈ−ＮＭ
Ｒスペクトルを図３に、拡大図を図４に示す。赤外吸光
スペクトルＡＴＲ法によるチャートを図５に、赤外吸光
スペクトル透過法によるチャートを図６に示す。これら
のチャートから求めた平均ＰＶＰ含有率Ｃａｖｅは３．
０％、内表面と外表面のＰＶＰ含有率はそれぞれ８．３
％、１．７％であり、式１を満たしていた。 この中空
糸９９７６本をケースへ充填して樹脂で接着し、端部を
刃で切り出すことでモジュールを得た。モジュールの充
填率は５７％、有効長は２４．０ｃｍ、膜面積は１．４
９m2だった。このモジュールを用いてエンドトキシン吸
着テストを行った。 1 H-NM of the membrane obtained under the above spinning conditions
FIG. 3 shows the R spectrum and FIG. 4 shows an enlarged view. FIG. 5 shows a chart based on the infrared absorption spectrum ATR method, and FIG. 6 shows a chart based on the infrared absorption spectrum transmission method. The average PVP content Cave determined from these charts is 3.
0%, PVP content on the inner surface and outer surface is 8.3 each
%, 1.7%, which satisfied the expression 1. The module was obtained by filling 9976 of these hollow fibers into a case, bonding them with a resin, and cutting out the ends with a blade. Module filling rate 57%, effective length 24.0cm, membrane area 1.4
It was 9m 2. An endotoxin adsorption test was performed using this module.
【００２９】すなわち、水道水と逆浸透水を混ぜ合わせ
ることで、３１６０ＥＵ／ＬのＥｔ液を用い、透析液入
口流量５００ｍｌ／ｍｉｎ、濾過流量１００ｍｌ／ｍｉ
ｎで循環させた。二時間後のＥｔ液のエンドトキシン濃
度は２１４０ＥＵ／Ｌであり、エンドトキシン吸着量は
５１００ＥＵであり、単位膜面積あたりに直すと、３４
００ＥＵ／m2であった。なお、測定中の濾過液のＥｔ濃
度は検出限界以下でありエンドトキシン混入が抑えられ
ていた。That is, by mixing tap water and reverse osmosis water, a 3160 EU / L Et solution is used, a dialysate inlet flow rate is 500 ml / min, and a filtration flow rate is 100 ml / mi.
n cycled. After 2 hours, the endotoxin concentration of the Et solution was 2140 EU / L, and the endotoxin adsorption amount was 5100 EU.
It was 00 EU / m 2 . In addition, the Et concentration of the filtrate during the measurement was below the detection limit, and endotoxin contamination was suppressed.
【００３０】（比較例１）ポリエーテルスルホン（ＰＥ
Ｓ）が１７．０重量％、親水化剤にポリビニルピロリド
ンＫ−９０（Ｋ９０）を３．０重量％、非溶媒として水
を５．０重量％、溶媒にジメチルアセトアミド（ＤＭＡ
Ｃ）７５．０％、内液濃度（ＤＭＡＣ＋水）が６０％と
して、紡糸原液を４０℃に保った二重紡糸口金の外側か
ら、内液を二重紡糸口金の内側から吐出し、ＡＧ長さ５
０ｍｍ、紡速３０ｍ／分、すなわちＡＧ滞留時間０．１
秒としたあと、４０℃の凝固浴濃度（ＤＭＡＣ＋水）３
０％の凝固浴へと浸漬した後、純水４５℃にて１分間、
純水８０℃にて４５秒間洗浄し、カセへと巻き取り、膜
厚３０μｍの中空糸膜を得た。このときのノズルから２
５ｍｍの部分におけるＡＧ部の温度は３８℃、湿度は８
０％であった。得られた中空糸膜の外表面ＳＥＭ像（倍
率１０，０００倍）を図７に示す。外表面には全く開孔
部がみられず、外表面開孔率は０％とみなされた。糸を
乾燥させたところ、糸の固着が激しくモジュール化は不
可能であった。Comparative Example 1 Polyethersulfone (PE
S) is 17.0% by weight, polyvinylpyrrolidone K-90 (K90) is 3.0% by weight as a hydrophilizing agent, water is 5.0% by weight as a non-solvent, and dimethylacetamide (DMA) is used as a solvent.
C) Assuming that the inner solution concentration (DMAC + water) was 60% and the inner solution concentration was 60%, the inner solution was discharged from the outside of the double spinneret where the stock spinning solution was kept at 40 ° C., and the inner solution was discharged from the inside of the double spinneret. Sa5
0 mm, spinning speed 30 m / min, ie AG residence time 0.1
Seconds, coagulation bath concentration at 40 ° C (DMAC + water) 3
After being immersed in a 0% coagulation bath, the solution was heated at 45 ° C. for 1 minute in pure water.
After washing with pure water at 80 ° C. for 45 seconds, the film was wound around a scalpel to obtain a hollow fiber membrane having a thickness of 30 μm. 2 from the nozzle at this time
The temperature of the AG section at a part of 5 mm is 38 ° C. and the humidity is 8
It was 0%. FIG. 7 shows an SEM image (magnification: 10,000 times) of the outer surface of the obtained hollow fiber membrane. No openings were found on the outer surface, and the outer surface opening ratio was regarded as 0%. When the yarn was dried, the fixing of the yarn was so severe that modularization was impossible.
【００３１】このときのＰＶＰ分布量を実施例１と同様
に 1Ｈ−ＮＭＲとＦＴ−ＩＲを用いて定量したところ、
膜内の平均ＰＶＰ含有率は４．０％であった。内表面と
外表面のＰＶＰ含有率はそれぞれ５．０％、６．０％で
あり、外表面のＰＶＰ含有量が非常に多かった。The amount of PVP distribution at this time was quantified using 1 H-NMR and FT-IR in the same manner as in Example 1.
The average PVP content in the membrane was 4.0%. The PVP content of the inner surface and the outer surface were 5.0% and 6.0%, respectively, and the PVP content of the outer surface was very large.
【００３２】[0032]
【表１】 [Table 1]
【図１】実施例１で得られた中空糸膜の外表面の走査型
電子顕微鏡写真（倍率１０，０００倍）を示す。FIG. 1 shows a scanning electron micrograph (magnification: 10,000) of the outer surface of the hollow fiber membrane obtained in Example 1.
【図２】図１の外表面走査型電子顕微鏡写真を、東洋紡
績株式会社製イメージアナライザーＶ２０を用いＴＯＫ
Ｓ法二値化にて画像処理を行った画像を示す。FIG. 2 is a TOK image of the outer surface scanning electron microscope photograph of FIG. 1 using an image analyzer V20 manufactured by Toyobo Co., Ltd.
5 shows an image subjected to image processing by S method binarization.
【図３】実施例１で得られた中空糸膜の 1Ｈ−ＮＭＲス
ペクトルを示す。FIG. 3 shows a 1 H-NMR spectrum of the hollow fiber membrane obtained in Example 1.
【図４】実施例１で得られた中空糸膜の 1Ｈ−ＮＭＲス
ペクトルの拡大図を示す。FIG. 4 is an enlarged view of the 1 H-NMR spectrum of the hollow fiber membrane obtained in Example 1.
【図５】実施例１で得られた中空糸膜の赤外吸光スペク
トルＡＴＲ法によるチャートを示す。FIG. 5 shows a chart of an infrared absorption spectrum ATR method of the hollow fiber membrane obtained in Example 1.
【図６】実施例１で得られた中空糸膜の赤外吸光スペク
トル透過法によるチャートを示す。FIG. 6 shows a chart of the hollow fiber membrane obtained in Example 1 by an infrared absorption spectrum transmission method.
【図７】比較例１で得られた中空糸膜の外表面の走査型
電子顕微鏡写真（倍率１０，０００倍）を示す。FIG. 7 shows a scanning electron micrograph (magnification: 10,000) of the outer surface of the hollow fiber membrane obtained in Comparative Example 1.
フロントページの続き Ｆターム(参考） 4D006 GA13 HA02 MA01 MA23 MA31 MA33 MA40 MB14 MC40X MC62 MC63X NA04 NA16 NA17 NA18 PA01 PB09 PB54 PC46 PC47 Continued on front page F-term (reference) 4D006 GA13 HA02 MA01 MA23 MA31 MA33 MA40 MB14 MC40X MC62 MC63X NA04 NA16 NA17 NA18 PA01 PB09 PB54 PC46 PC47
Claims (4)
ビニルピロリドンからなる膜であり、膜内表面のポリビ
ニルピロリドン含有率（Ｃｉ）と膜外表面のポリビニル
ピロリドン含有率（Ｃｏ）、膜内の平均ポリビニルピロ
リドン含有率（Ｃａｖｅ）の関係が下式で表されること
を特徴とする中空糸膜。 Ｃｉ≧Ｃｏ×３、Ｃｉ≧Ｃａｖｅ×２1. A membrane substantially comprising a polysulfone-based polymer and polyvinylpyrrolidone, wherein the content of polyvinylpyrrolidone on the inner surface of the film (Ci), the content of polyvinylpyrrolidone on the outer surface of the film (Co), and the average polyvinylpyrrolidone in the film A hollow fiber membrane, wherein the relationship of the content (Cave) is represented by the following formula. Ci ≧ Co × 3, Ci ≧ Cave × 2
ＥＵ／m2以上である請求項１記載の中空糸膜。2. The membrane has an endotoxin adsorption capacity of 2000.
2. The hollow fiber membrane according to claim 1, which has an EU / m 2 or more.
求項１または２記載の中空糸膜。3. The hollow fiber membrane according to claim 1, wherein the porosity of the outer surface of the membrane is 25% or more.
以上洗浄した後、８０℃以上の熱水中で３０秒以上、該
中空糸膜を洗浄することによって得られうる請求項１な
いし４のいずれかに記載の中空糸膜。4. The method according to claim 1, wherein in the spinning step, the hollow fiber membrane can be obtained by washing with water at 40 ° C. or more for 1 minute or more and then in hot water at 80 ° C. or more for 30 seconds or more. The hollow fiber membrane according to any one of the above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21991299A JP2001038170A (en) | 1999-08-03 | 1999-08-03 | Hollow fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21991299A JP2001038170A (en) | 1999-08-03 | 1999-08-03 | Hollow fiber membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2001038170A true JP2001038170A (en) | 2001-02-13 |
Family
ID=16742977
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21991299A Pending JP2001038170A (en) | 1999-08-03 | 1999-08-03 | Hollow fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2001038170A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005051460A1 (en) * | 2003-11-26 | 2005-06-09 | Toyo Boseki Kabushiki Kaisha | Polysulfone-based hollow-fiber membrane with selective permeability |
| JP2005329087A (en) * | 2004-05-20 | 2005-12-02 | Toyobo Co Ltd | Polysulfone base permselective hollow fiber membrane excellent in hemocompatibility |
| JP2005342102A (en) * | 2004-06-01 | 2005-12-15 | Toyobo Co Ltd | Polysulfone based permselective hollow yarn membrane with excellent blood compatibility |
| EP1634611A4 (en) * | 2003-08-29 | 2008-09-03 | Toyo Boseki | Highly water-permeable blood purifier of hollow-fiber membrane type |
| US7837042B2 (en) | 2004-08-10 | 2010-11-23 | Nipro Corporation | Polysulfone type selectively permeable hollow fiber membrane module and process for manufacturing the same |
| US7922007B2 (en) | 2004-03-22 | 2011-04-12 | Toyo Boseki Kabushiki Kaisha | Separation membrane with selective permeability and process for producing the same |
| CN113646067A (en) * | 2019-03-29 | 2021-11-12 | 旭化成医疗株式会社 | Porous membrane |
-
1999
- 1999-08-03 JP JP21991299A patent/JP2001038170A/en active Pending
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1634611A4 (en) * | 2003-08-29 | 2008-09-03 | Toyo Boseki | Highly water-permeable blood purifier of hollow-fiber membrane type |
| US7442302B2 (en) | 2003-08-29 | 2008-10-28 | Toyo Boseki Kabushiki Kaisha | Highly water-permeable blood purifier of hollow-fiber membrane type |
| WO2005051460A1 (en) * | 2003-11-26 | 2005-06-09 | Toyo Boseki Kabushiki Kaisha | Polysulfone-based hollow-fiber membrane with selective permeability |
| US7638052B2 (en) | 2003-11-26 | 2009-12-29 | Toyo Boseki Kabushiki Kaisha | Polysulfone-based hollow-fiber membrane with selective permeability |
| US7922007B2 (en) | 2004-03-22 | 2011-04-12 | Toyo Boseki Kabushiki Kaisha | Separation membrane with selective permeability and process for producing the same |
| JP2005329087A (en) * | 2004-05-20 | 2005-12-02 | Toyobo Co Ltd | Polysulfone base permselective hollow fiber membrane excellent in hemocompatibility |
| JP2005342102A (en) * | 2004-06-01 | 2005-12-15 | Toyobo Co Ltd | Polysulfone based permselective hollow yarn membrane with excellent blood compatibility |
| US7837042B2 (en) | 2004-08-10 | 2010-11-23 | Nipro Corporation | Polysulfone type selectively permeable hollow fiber membrane module and process for manufacturing the same |
| CN113646067A (en) * | 2019-03-29 | 2021-11-12 | 旭化成医疗株式会社 | Porous membrane |
| CN113646067B (en) * | 2019-03-29 | 2024-03-12 | 旭化成医疗株式会社 | Porous membrane |
| US12274985B2 (en) | 2019-03-29 | 2025-04-15 | Asahi Kasei Medical Co., Ltd. | Porous membrane |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3474205B2 (en) | Polysulfone hollow fiber type blood purification membrane and method for producing the same | |
| EP0509663B2 (en) | Dialysis module with a selectively transmissive polysulfonic hollow fiber membrane and method of manufacture thereof | |
| JP5754654B2 (en) | Porous hollow fiber membrane for protein-containing liquid treatment | |
| JP6433513B2 (en) | Porous hollow fiber filtration membrane | |
| EP2113298A9 (en) | Hollow fibre membrane with improved permeability and selectivity | |
| RU2667068C2 (en) | Porous membrane, blood purifying module incorporating porous membrane and method for producing porous membrane | |
| JPWO2002009857A1 (en) | Modified hollow fiber membrane | |
| WO2005051460A1 (en) | Polysulfone-based hollow-fiber membrane with selective permeability | |
| JP3580314B1 (en) | Polysulfone-based selectively permeable hollow fiber membrane bundle and method for producing the same | |
| EP1129738A1 (en) | Blood purifying apparatus | |
| JPWO2000027447A1 (en) | blood purifier | |
| JP2001038170A (en) | Hollow fiber membrane | |
| JP2003284931A (en) | Apparatus for drying hollow fiber membrane | |
| JP4352709B2 (en) | Polysulfone-based semipermeable membrane and artificial kidney using the same | |
| JP2000225326A (en) | Method for cleaning selective permeable membrane | |
| JP3684676B2 (en) | Method for producing polysulfone-based hollow fiber artificial kidney and artificial kidney | |
| JP2005137996A (en) | Permselective separation membrane | |
| JP3992186B2 (en) | Method for producing hollow fiber membrane | |
| JP3334705B2 (en) | Polysulfone-based selectively permeable hollow fiber membrane | |
| JP2001038171A (en) | Hollow fiber membrane | |
| JPH07289866A (en) | Polysulfone-based selective permeable membrane | |
| JP2003033632A (en) | Method for producing blood purifying membrane | |
| JP3659256B1 (en) | Polysulfone-based permselective hollow fiber membrane bundle and drying method thereof | |
| JP4843993B2 (en) | Blood purifier | |
| JP4386607B2 (en) | Polysulfone blood purification membrane production method and polysulfone blood purification membrane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20041018 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20041028 |
|
| A521 | Written amendment |
Effective date: 20041227 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A131 | Notification of reasons for refusal |
Effective date: 20061005 Free format text: JAPANESE INTERMEDIATE CODE: A131 |
|
| A521 | Written amendment |
Effective date: 20061204 Free format text: JAPANESE INTERMEDIATE CODE: A523 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20071018 |