JP2003126664A - Method for producing semipermeable membrane and dialyzer using the semipermeable membrane - Google Patents
Method for producing semipermeable membrane and dialyzer using the semipermeable membraneInfo
- Publication number
- JP2003126664A JP2003126664A JP2001325059A JP2001325059A JP2003126664A JP 2003126664 A JP2003126664 A JP 2003126664A JP 2001325059 A JP2001325059 A JP 2001325059A JP 2001325059 A JP2001325059 A JP 2001325059A JP 2003126664 A JP2003126664 A JP 2003126664A
- Authority
- JP
- Japan
- Prior art keywords
- polysulfone
- semipermeable membrane
- average molecular
- molecular weight
- weight
- 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.)
- Granted
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 13
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 59
- 239000011347 resin Substances 0.000 claims abstract description 31
- 229920005989 resin Polymers 0.000 claims abstract description 31
- 239000011550 stock solution Substances 0.000 claims abstract description 24
- 229920001477 hydrophilic polymer Polymers 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 23
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 23
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 23
- 238000002156 mixing Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 38
- 230000035699 permeability Effects 0.000 abstract description 18
- 239000000243 solution Substances 0.000 abstract description 7
- 238000009987 spinning Methods 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 18
- 239000012510 hollow fiber Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 16
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 210000003734 kidney Anatomy 0.000 description 5
- 239000008280 blood Substances 0.000 description 4
- 210000004369 blood Anatomy 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 230000005251 gamma ray Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000010828 elution Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 102000004169 proteins and genes Human genes 0.000 description 3
- 108090000623 proteins and genes Proteins 0.000 description 3
- 102000009027 Albumins Human genes 0.000 description 2
- 108010088751 Albumins Proteins 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005345 coagulation Methods 0.000 description 2
- 230000015271 coagulation Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical group O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 101001094026 Synechocystis sp. (strain PCC 6803 / Kazusa) Phasin PhaP Proteins 0.000 description 1
- FHKPLLOSJHHKNU-INIZCTEOSA-N [(3S)-3-[8-(1-ethyl-5-methylpyrazol-4-yl)-9-methylpurin-6-yl]oxypyrrolidin-1-yl]-(oxan-4-yl)methanone Chemical group C(C)N1N=CC(=C1C)C=1N(C2=NC=NC(=C2N=1)O[C@@H]1CN(CC1)C(=O)C1CCOCC1)C FHKPLLOSJHHKNU-INIZCTEOSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 208000020832 chronic kidney disease Diseases 0.000 description 1
- 208000022831 chronic renal failure syndrome Diseases 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- 229920002545 silicone oil Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000000772 tip-enhanced Raman spectroscopy Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Landscapes
- External Artificial Organs (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Artificial Filaments (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、ポリスルホン系樹
脂を用いた半透膜の製造方法に関するものであり、特に
透水性能の高い半透膜を効率的に製造する方法に関す
る。TECHNICAL FIELD The present invention relates to a method for producing a semipermeable membrane using a polysulfone resin, and more particularly to a method for efficiently producing a semipermeable membrane having high water permeability.
【０００２】[0002]
【従来の技術】これまで慢性腎不全患者の血液処理膜を
人腎レベルに近づけるために、様々な透析方法・膜の性
能向上技術が開発されてきた。血液処理膜としては、例
えばポリスルホンとともに、造孔剤としてポリビニルピ
ロリドンを用いて製膜する方法が、特開平9-70524号公
報などにおいて知られている。2. Description of the Related Art Various dialysis methods and various techniques for improving the performance of membranes have been developed so far in order to bring blood treatment membranes of patients with chronic renal failure closer to the human kidney level. As a blood treatment membrane, for example, Japanese Patent Laid-Open No. 9-70524 discloses a method of forming a membrane by using polyvinylpyrrolidone as a pore-forming agent together with polysulfone.
【０００３】また、特開平4-338224号公報や特開平11-3
09355号公報のようにポリスルホンとして低分子量タイ
プを用いたもの、特開平9-70524号公報のように高分子
量タイプを単独で用いたものがあった。Further, JP-A-4-338224 and JP-A-11-3
Some of them use a low molecular weight type as polysulfone as in 09355, and some use a high molecular weight type alone as in JP-A-9-70524.
【０００４】[0004]
【発明が解決しようとする課題】しかし、特開平4-3382
24号公報、特開平11-309355号公報、特開平9-70524号公
報などの方法では、いづれの場合も、孔径のコントロー
ルを製膜原液中のポリスルホンをパラメータとする場
合、ポリスルホン濃度を変更する必要があった。すなわ
ち、透水性能を上げる場合、ポリスルホン濃度を下げる
必要があるが、その場合、中空糸強度が低下する、紡糸
性が悪くなるなどの欠点があった。[Problems to be Solved by the Invention] However, JP-A-4-3382
No. 24, JP-A No. 11-309355, JP-A No. 9-70524, etc., in any case, when the control of the pore size is the polysulfone in the membrane forming stock solution as a parameter, the polysulfone concentration is changed. There was a need. That is, in order to improve the water permeability, it is necessary to reduce the polysulfone concentration, but in that case, there are drawbacks such as a decrease in hollow fiber strength and a deterioration in spinnability.
【０００５】そこで、本発明は、上記従来技術の欠点を
解消しようとするものであり、ポリスルホン濃度を変え
ずに、平均分子量の異なる２種類以上のポリスルホン系
樹脂を使用することにより、透水性能を向上させること
を目的とする。Therefore, the present invention is intended to solve the above-mentioned drawbacks of the prior art, and by using two or more kinds of polysulfone-based resins having different average molecular weights without changing the polysulfone concentration, the water permeability is improved. The purpose is to improve.
【０００６】[0006]
【課題を解決するための手段】本発明は、上記課題を達
成するために、下記の構成を有する。すなわち、本発明
は、重量平均分子量の異なる２種類以上のポリスルホン
系樹脂、親水性高分子および溶媒を含み、該２種類以上
のポリスルホン系樹脂の中で最小の重量平均分子量を持
つポリスルホン系樹脂の全ポリスルホン系樹脂に対する
混合比率が１０〜７０重量％である製膜原液を用いるこ
とを特徴とする半透膜の製造方法をその骨子とする。To achieve the above object, the present invention has the following constitution. That is, the present invention provides a polysulfone-based resin containing two or more kinds of polysulfone-based resins having different weight average molecular weights, a hydrophilic polymer and a solvent, and having the smallest weight-average molecular weight among the two or more kinds of polysulfone-based resins. A skeleton is a method for producing a semipermeable membrane, which comprises using a membrane-forming undiluted solution having a mixing ratio of 10 to 70% by weight to all polysulfone-based resins.
【０００７】[0007]
【発明の実施の形態】本発明に使用するポリスルホン系
樹脂としてはポリスルホン骨格を有するポリマーであれ
ば特に限定されず、共重合ポリスルホンや変性ポリスル
ホンなども用いることができる。例えばベンゼン環部分
をアミノ基やスルホン酸基で置換修飾したものも用いる
ことができる。本発明では、ポリスルホンまたはポリエ
ーテルスルホンが好ましく用いられるが、ポリスルホン
が特に好ましい。BEST MODE FOR CARRYING OUT THE INVENTION The polysulfone resin used in the present invention is not particularly limited as long as it is a polymer having a polysulfone skeleton, and copolymerized polysulfone, modified polysulfone and the like can also be used. For example, it is also possible to use a benzene ring part which is modified by substitution with an amino group or a sulfonic acid group. In the present invention, polysulfone or polyether sulfone is preferably used, but polysulfone is particularly preferable.
【０００８】本発明に使用する製膜原液におけるポリス
ルホン系樹脂の濃度としては、濃度を上げるに従って製
膜性は良くなるが逆に膜における空孔率は減少し、透水
性が低下する傾向がある。そのため、ポリスルホン系樹
脂の濃度は、製膜原液中、10〜30重量％であることが好
ましく、さらには15〜21重量％であることがより好まし
い。Regarding the concentration of the polysulfone resin in the membrane-forming stock solution used in the present invention, the film-forming property improves as the concentration increases, but conversely the porosity of the membrane decreases and the water permeability tends to decrease. . Therefore, the concentration of the polysulfone-based resin is preferably 10 to 30% by weight, and more preferably 15 to 21% by weight in the membrane-forming stock solution.
【０００９】本発明においては、ポリスルホン系樹脂と
して重量平均分子量の異なる２種類以上のものを用い
る。重量平均分子量の異なる２種類以上のポリスルホン
系樹脂を用いることで、効果的に透水性能を向上させる
ことができる。その作用機構は定かではないが、ポリス
ルホン系樹脂の重量平均分子量の高いものを用いた場
合、内表面スキン層の粒子が大きくなり、大きな孔を得
ることができるが、逆にポリスルホン系ポリマー微粒子
からポリビニルピロリドンが脱離しにくくなってしまう
ことによるものと推定される。In the present invention, two or more kinds of polysulfone resins having different weight average molecular weights are used. By using two or more types of polysulfone-based resins having different weight average molecular weights, it is possible to effectively improve the water permeability. The mechanism of action is not clear, but when a polysulfone-based resin having a high weight average molecular weight is used, the particles of the inner surface skin layer become large and large pores can be obtained. It is presumed that this is because polyvinylpyrrolidone becomes difficult to be detached.
【００１０】本発明において、ポリスルホン系樹脂の中
で最小の重量平均分子量を持つポリスルホン系樹脂の全
ポリスルホン樹脂に対する混合比率が10〜70％である必
要があり、好ましくは25〜50％である。In the present invention, the mixing ratio of the polysulfone resin having the smallest weight average molecular weight among the polysulfone resins to the total polysulfone resin needs to be 10 to 70%, preferably 25 to 50%.
【００１１】本発明においては、重量平均分子量が５０
００以上異なるポリスルホン系樹脂を少なくとも１種用
いることが好ましい。重量平均分子量が５０００以上異
なるポリスルホン系樹脂を使用することで、透水性を効
果的に向上させることができる。In the present invention, the weight average molecular weight is 50.
It is preferable to use at least one polysulfone-based resin that is different by at least 00. Water permeability can be effectively improved by using polysulfone-based resins having different weight average molecular weights of 5,000 or more.
【００１２】本発明に使用する親水性高分子は、例え
ば、ポリビニルピロリドン、ポリエチレングリコール、
ポリビニルアルコール、カルボキシメチルセルロースな
どが挙げられる。中でも、ポリビニルピロリドンが好ま
しく用いられる。ポリビニルピロリドンを使用すること
で、製膜性や透水性を向上させることができる。The hydrophilic polymer used in the present invention is, for example, polyvinylpyrrolidone, polyethylene glycol,
Examples thereof include polyvinyl alcohol and carboxymethyl cellulose. Among them, polyvinylpyrrolidone is preferably used. By using polyvinylpyrrolidone, film forming properties and water permeability can be improved.
【００１３】ポリスルホン系樹脂の分子量は一般に低い
ことから、親水性高分子としてポリビニルピロリドンを
使用した場合、製膜原液の粘度は、ポリビニルピロリド
ンの分子量に依存する傾向がある。製膜原液粘度が低い
場合、製膜時に糸切れ、糸揺れなどを起こし製糸安定性
に劣る場合があるため、ポリビニルピロリドンの平均分
子量は高いことが好ましく、４万以上が好ましい。Since the molecular weight of polysulfone resin is generally low, when polyvinylpyrrolidone is used as the hydrophilic polymer, the viscosity of the stock solution for film formation tends to depend on the molecular weight of polyvinylpyrrolidone. If the viscosity of the stock solution for film formation is low, yarn breakage, yarn sway, etc. may occur during film formation, resulting in poor yarn forming stability. Therefore, the average molecular weight of polyvinylpyrrolidone is preferably high, and 40,000 or more is preferable.
【００１４】製膜原液における親水性高分子の濃度は、
上げるに従って粘度が上昇し製膜性が良くなるが、逆に
大部分は造孔材として使用された後に洗い流されるため
廃棄すべき親水性高分子の量は増加する。そのため、製
膜原液における親水性高分子の濃度は2〜20重量％が好
ましく、さらには3〜9重量％が好ましい。The concentration of the hydrophilic polymer in the stock solution for film formation is
Although the viscosity increases and the film-forming property improves as the temperature is increased, the amount of hydrophilic polymer to be discarded increases because most of it is used as a pore-forming material and then washed away. Therefore, the concentration of the hydrophilic polymer in the membrane-forming stock solution is preferably 2 to 20% by weight, more preferably 3 to 9% by weight.
【００１５】また、製膜された半透膜中における親水性
高分子の含有率は、1〜15重量％であることが好まし
い。１重量%未満の場合、水濡れ性が不十分となり、例
えば血液と接触した際にエアーロックのために凝固を引
き起こす可能性がある。The content of the hydrophilic polymer in the formed semipermeable membrane is preferably 1 to 15% by weight. If it is less than 1% by weight, the wettability becomes insufficient and, for example, when it comes into contact with blood, it may cause coagulation due to airlock.
【００１６】さらに、本発明の製造方法で製造された半
透膜を人工腎臓として用いる場合、中高分子尿毒蛋白を
選択的に透過し、アルブミン透過性を極力抑えることが
好ましい。この点で、親水性高分子としてポリビニルピ
ロリドンを使用した場合、製膜原液中に分子量10万以上
のポリビニルピロリドンが1.8〜20重量％含有されてい
ることが好ましい。ここで、20重量％を越えると、原液
粘度が上昇し、製膜が難しくなるだけでなく、透水性、
拡散性能が低下する傾向がある。また、1.8重量％未満
では、例えば、中高分子尿毒蛋白を透過させるための適
当な孔を有する膜構造が形成しにくくなる。Further, when the semipermeable membrane produced by the production method of the present invention is used as an artificial kidney, it is preferable to selectively permeate medium and high molecular weight uremic proteins and suppress albumin permeability as much as possible. In this respect, when polyvinylpyrrolidone is used as the hydrophilic polymer, it is preferable that the film-forming stock solution contains 1.8 to 20% by weight of polyvinylpyrrolidone having a molecular weight of 100,000 or more. Here, if it exceeds 20% by weight, the viscosity of the undiluted solution increases, making not only film formation difficult but also water permeability,
Diffusion performance tends to decrease. On the other hand, if it is less than 1.8% by weight, for example, it becomes difficult to form a membrane structure having appropriate pores for permeating a medium- and high-molecular-weight uremic protein.
【００１７】本発明における製膜原液には、溶媒が含ま
れている必要がある。すなわち、ポリスルホン系樹脂お
よび親水系樹脂の良溶媒が用いられる。具体的には、ジ
メチルアセトアミド、ジメチルホルムアミド、ジメチル
スルホキシド、アセトン、アセトアルデヒド、2-メチル
ピロリドンなどであるが、危険性、安全性、毒性の面か
らジメチルアセトアミドが好ましい。The stock solution for film formation in the present invention must contain a solvent. That is, a good solvent for the polysulfone resin and the hydrophilic resin is used. Specific examples thereof include dimethylacetamide, dimethylformamide, dimethylsulfoxide, acetone, acetaldehyde, and 2-methylpyrrolidone, but dimethylacetamide is preferable in terms of danger, safety and toxicity.
【００１８】製膜原液には、さらに、ポリスルホンの貧
溶媒で、かつ、ポリビニルピロリドンと相溶性を持つ添
加剤が好ましく用いられる。具体的には、アルコール、
グリセリン、水、エステル類などであるが、プロセス適
性の面から特に水が好ましい。In the film-forming stock solution, an additive which is a poor solvent for polysulfone and which is compatible with polyvinylpyrrolidone is preferably used. Specifically, alcohol,
Glycerin, water, esters and the like are preferable, but water is particularly preferable from the viewpoint of process suitability.
【００１９】本発明の製造方法で製造される半透膜は、
中空糸膜、平膜等として好適に用いられる。中空糸膜と
して用いる場合の好ましい製膜例を以下に示す。The semipermeable membrane produced by the production method of the present invention is
It is preferably used as a hollow fiber membrane, a flat membrane or the like. Preferred examples of membrane production when used as a hollow fiber membrane are shown below.
【００２０】まず、ポリスルホンとポリビニルピロリド
ンを含む製膜原液と、芯液とを、同時に二重スリット管
構造の口金から同時にドライゾーンに吐出させる。ここ
で、芯液とは、例えば、ジメチルスルオキシド、ジメチ
ルアセトアミド、水からなる溶液であり、製膜された状
態で半透膜の担時体となるものである。ドライゾーンの
雰囲気を特定の条件に保つことで、季節変動による性能
の変化を抑制することができる。すなわち、ドライゾー
ン温度、相対湿度が高すぎると中空糸膜内部において相
分離が起こる前に外表面は凝固し、緻密層ができる。ま
た、ドライゾーン温度、相対湿度が低すぎると相分離す
る前に水中に浸漬されるため、外表面は凝固し、緻密層
ができる。ゆえにドライゾーン温度は、紡糸口金部温度
−40℃≦ドライゾーンの温度≦紡糸口金部温度−15℃の
条件を満たすことが好ましい。また、相対湿度は、60％
以上、95％以下であることが好ましい。ここで、相対湿
度とは、水蒸気圧と飽和水蒸気圧の比を％で表したもの
をいう。First, a film-forming stock solution containing polysulfone and polyvinylpyrrolidone and a core solution are simultaneously discharged from a die having a double slit tube structure to a dry zone at the same time. Here, the core liquid is, for example, a solution composed of dimethylsulfoxide, dimethylacetamide, and water, and serves as a semipermeable membrane supporting member in a film-formed state. By maintaining the atmosphere in the dry zone under specific conditions, it is possible to suppress changes in performance due to seasonal variations. That is, if the dry zone temperature and the relative humidity are too high, the outer surface is solidified before the phase separation occurs inside the hollow fiber membrane to form a dense layer. If the dry zone temperature and relative humidity are too low, the outer surface is solidified because it is immersed in water before phase separation, and a dense layer is formed. Therefore, it is preferable that the dry zone temperature satisfy the condition of the temperature of the spinneret part −40 ° C. ≦ the temperature of the dry zone ≦ the temperature of the spinneret part −15 ° C. Also, the relative humidity is 60%
It is preferably at least 95%. Here, the relative humidity means the ratio of the water vapor pressure and the saturated water vapor pressure expressed in%.
【００２１】上記条件により紡糸した後、所定の水洗工
程を経た後、巻き取られ、乾燥した後にモジュール化さ
れる。巻き取られた中空糸膜は人工腎臓用に用いる場
合、このままではポリビニルピロリドンの溶出が多く、
装置型人工腎臓承認基準に記載された数値を満たさない
傾向があるため、γ線、電子線、熱、化学的処理などに
より架橋し、溶出物を低減させることが好ましい。架橋
処理により、ポリスルホンとポリビニルピロリドンが結
合することでポリビニルピロリドンの溶出が減少する。
さらにポリビニルピロリドンの溶出を防ぐためには、γ
線照射前に、脱気膜を通過した水でモジュールを洗浄す
ることが好ましい。After spinning under the above-mentioned conditions, a predetermined water washing process is performed, and then the film is wound, dried and then modularized. When the wound hollow fiber membrane is used for artificial kidneys, polyvinylpyrrolidone is often eluted as it is,
Since the numerical value described in the device type artificial kidney approval standard tends not to be satisfied, it is preferable to crosslink by γ ray, electron beam, heat, chemical treatment or the like to reduce the eluate. The cross-linking treatment reduces the elution of polyvinylpyrrolidone due to the binding of polysulfone and polyvinylpyrrolidone.
Furthermore, to prevent the elution of polyvinylpyrrolidone, γ
It is preferable to wash the module with water that has passed through the degassing membrane before the irradiation with rays.
【００２２】ここで、γ線照射は、水充填でのγ線照
射、または不活性ガス下で半透膜に水分を抱液させた状
態でのγ線照射が好ましい。この時、半透膜は100％以
上、600％未満の水分を含んでいることが好ましい。γ
線照射量は10〜50KGy、さらには10〜40KGyが好ましい。
これらの方法で作成された人工腎臓は、尿毒物質の拡
散、有用蛋白であるアルブミンの阻止などの性能に優
れ、かつ、ポリビニルピロリドンの溶出が少ない。Here, the γ-ray irradiation is preferably γ-ray irradiation with water filling or γ-ray irradiation in a state where water is contained in the semipermeable membrane under an inert gas. At this time, the semipermeable membrane preferably contains water of 100% or more and less than 600%. γ
The radiation dose is preferably 10 to 50 KGy, more preferably 10 to 40 KGy.
The artificial kidneys produced by these methods have excellent properties such as diffusion of uremic substances and inhibition of albumin, which is a useful protein, and little elution of polyvinylpyrrolidone.
【００２３】本発明の製造方法により得られる半透膜
は、例えば、透析器、血漿分離器等の血液浄化膜、限外
濾過膜などとして、好適に用いられ、特に透析器用に好
ましく使用される。The semipermeable membrane obtained by the production method of the present invention is suitably used, for example, as a blood purification membrane such as a dialyzer and a plasma separator, an ultrafiltration membrane, and particularly preferably for a dialyzer. .
【００２４】[0024]
【実施例】次に、実施例に基づき本発明を説明する。実
施例において、「部」は「重量部」を意味する。なお、
実施例で用いた測定方法は以下の通りである。EXAMPLES Next, the present invention will be explained based on examples. In the examples, "parts" means "parts by weight". In addition,
The measuring method used in the examples is as follows.
【００２５】（1）製膜原液の粘度の測定
東機産業（株）製Ｂ型回転粘度計Ｂ８タイプを用いて測
定を行った。温度制御装置付きシリコンオイルバスに原
液の入ったサンプルビンを入れ、温度を所定温度にし
て、５点測定し、その平均値とした。(1) Measurement of viscosity of stock solution for film formation Measurement was carried out using a B-type rotational viscometer B8 type manufactured by Toki Sangyo Co. A sample bottle containing the undiluted solution was placed in a silicone oil bath equipped with a temperature control device, the temperature was set to a predetermined temperature, and 5 points were measured to obtain the average value.
【００２６】（2）透水性能の測定
中空糸（半透膜）を３６本入れ、中空糸両端部を封止し
たガラス管モジュール（有効長100mm）に中空糸内側に
水圧１６kPaをかけ、外側に流出してくる単位時間当た
りの濾過量を測定した。透水性能は下記の式で算出し
た。
透水性能（ml/hr/ｍ2/kPa）= QW/（T・A・P）
ここで、QW：濾過量（ml/min）
T：流出時間（hr）
P：圧力（kPa）
A：膜面積（ｍ2）（中空糸内表面積換算）。(2) Measurement of water permeation performance A glass tube module (effective length 100 mm) in which 36 hollow fibers (semi-permeable membranes) were placed, and both ends of the hollow fibers were applied with a water pressure of 16 kPa on the inner side of the hollow fiber and on the outer side The amount of filtration per unit time flowing out was measured. The water permeability was calculated by the following formula. Water permeability (ml / hr / m 2 / kPa) = QW / (T ・ A ・ P) where QW: Filtration amount (ml / min) T: Outflow time (hr) P: Pressure (kPa) A: Membrane Area (m 2 ) (in terms of hollow fiber internal surface area).
【００２７】（3）ポリスルホンの重量平均分子量の測
定
ポリスルホン（アモコ社 ”Udel”-P1700）、ポリスル
ホン（アモコ社 ”Udel”-P3500）の重量平均分子量
は、ゲル浸透クロマトグラフ装置 ＧＰＣ−５１０（WA
TERS社）、カラム TSK-gel-GMH6（東ソー社製 内径
７．５ｍｍ、長さ６０ｃｍ）を用いて、溶媒にテトラヒ
ドロフランを使用し、流速１．０ml/min、温度２３℃、
注入量０．３ｍｌの条件で示唆屈折率検出器で測定し
た。分子量較正には、１０種の単分散ポリスチレンを用
い、試料は０．１％可溶分に２３℃で攪拌溶解し、０．
５μｍフィルター（TOSOH−H−１３−５）で濾過したも
のを用いた。(3) Measurement of weight average molecular weight of polysulfone The weight average molecular weight of polysulfone (Amoco "Udel" -P1700) and polysulfone (Amoco "Udel" -P3500) was determined by gel permeation chromatograph GPC-510 (WA).
TERS), column TSK-gel-GMH6 (Tosoh Corp. inner diameter 7.5 mm, length 60 cm), using tetrahydrofuran as a solvent, flow rate 1.0 ml / min, temperature 23 ° C.,
It was measured with a suggested refractive index detector under the condition of an injection amount of 0.3 ml. For the molecular weight calibration, 10 kinds of monodisperse polystyrenes were used, and the sample was dissolved in 0.1% soluble component by stirring at 23 ° C.
The one filtered with a 5 μm filter (TOSOH-H-13-5) was used.
【００２８】実施例１
ポリスルホン（アモコ社 ”Udel”-P1700 重量平均分
子量4万7000）4部、ポリスルホン（アモコ社 ”Udel”
-P3500 重量平均分子量5万9000）12部、ポリビニルピ
ロリドン（BASF社 K90 重量平均分子量１２０万）6部
をジメチルアセトアミド54.3部、ジメチルスルホキシド
21.7部、水2部に加え、80℃12時間、加熱溶解した。得
られた製膜原液の粘度は、22℃で46ポイズであった。こ
の製膜原液を温度50℃の紡糸口金部へ送り、外径0.40m
m、内径0.25mmの2重スリット管から芯液としてジメチル
スルオキシド37部、ジメチルアセトアミド37部、水26部
からなる溶液を吐出させ、内径210μm膜厚40μmの中空
糸膜を形成させた後、加湿された（霧状の水を中空糸に
当てる）室温の300mmのドライゾーンを通過させ、ジメ
チルスルホキシド11部、ジメチルアセトアミド30部、水
59部からなる40℃の凝固浴、50℃の水洗工程、を経て得
られた中空糸膜を巻き取り束とした後、熱風乾燥機にて
100℃、12時間乾燥した。この中空糸の透水性能を測定
したところ2288ml/hr/ｍ2/kPaと高い値を示した。Example 1 4 parts of polysulfone (Amoco "Udel" -P1700 weight average molecular weight 47,000), polysulfone (Amoco "Udel"
-P3500 Weight average molecular weight 59,000) 12 parts, Polyvinylpyrrolidone (BASF K90 weight average molecular weight 1.2 million) 6 parts dimethylacetamide 54.3 parts, dimethyl sulfoxide
21.7 parts and 2 parts of water were added, and the mixture was heated and dissolved at 80 ° C. for 12 hours. The viscosity of the obtained stock solution for film formation was 46 poise at 22 ° C. This stock solution for film formation was sent to the spinneret part at a temperature of 50 ° C and the outer diameter was 0.40 m.
m, the solution consisting of dimethylsulfoxide 37 parts, dimethylacetamide 37 parts, water 26 parts as core liquid from a double slit tube with an inner diameter of 0.25 mm was discharged to form a hollow fiber membrane having an inner diameter of 210 μm and a film thickness of 40 μm, Pass through a humidified (mist water is applied to the hollow fiber) room temperature 300 mm dry zone, 11 parts of dimethylsulfoxide, 30 parts of dimethylacetamide, water
The hollow fiber membrane obtained through the coagulation bath of 59 parts at 40 ° C and the washing step at 50 ° C was wound into a bundle and then dried with a hot air dryer.
It was dried at 100 ° C for 12 hours. When the water permeability of this hollow fiber was measured, it showed a high value of 2288 ml / hr / m 2 / kPa.
【００２９】実施例２
ポリスルホン（アモコ社 ”Udel”-P1700 重量平均分
子量4万7000）8部、ポリスルホン（アモコ社 ”Udel”
-P3500 重量平均分子量5万9000）8部、ポリビニルピロ
リドン（BASF社 K90 重量平均分子量１２０万）6部を
ジメチルアセトアミド54.3部、ジメチルスルホキシド2
1.7部、水2部に加え、80℃12時間、加熱溶解した。得ら
れた製膜原液の粘度は、22℃で46.5ポイズであった。こ
の製膜原液を実施例１と同様にして製膜し、熱風乾燥機
にて100℃、12時間乾燥した。この中空糸の透水性能を
測定したところ1913ml/hr/ｍ2/kPaと高い値を示した。Example 2 8 parts of polysulfone (Amoco "Udel" -P1700 weight average molecular weight 47,000), polysulfone (Amoco "Udel"
-P3500 Weight average molecular weight 59,000) 8 parts, Polyvinylpyrrolidone (BASF K90 weight average molecular weight 1.2 million) 6 parts, dimethylacetamide 54.3 parts, dimethyl sulfoxide 2
1.7 parts and 2 parts of water were added, and the mixture was heated and dissolved at 80 ° C. for 12 hours. The viscosity of the obtained stock solution for film formation was 46.5 poise at 22 ° C. This stock solution for film formation was formed into a film in the same manner as in Example 1, and dried at 100 ° C. for 12 hours with a hot air dryer. When the water permeability of this hollow fiber was measured, it showed a high value of 1913 ml / hr / m 2 / kPa.
【００３０】比較例１
ポリスルホン（アモコ社 ”Udel”-P3500 重量平均分
子量5万9000）16部、ポリビニルピロリドン（BASF社 K
90 重量平均分子量１２０万）6部をジメチルアセトア
ミド部、ジメチルスルホキシド21.7部、水2部に加え、8
0℃12時間、加熱溶解した。得られた製膜原液の粘度
は、22℃で50ポイズであった。この製膜原液を実施例１
と同様にして製膜し、熱風乾燥機にて100℃、12時間乾
燥した。比較例１は、１種類のポリスルホンを使用した
例である。この中空糸の透水性能を測定したところ1185
ml/hr/ｍ2/kPaと低い値を示した。Comparative Example 1 16 parts of polysulfone ("Udel" -P3500, weight average molecular weight 59,000, Amoco), polyvinylpyrrolidone (K, BASF K
90 weight average molecular weight 1.2 million) 6 parts to dimethylacetamide part, dimethyl sulfoxide 21.7 parts, and water 2 parts,
It was dissolved by heating at 0 ° C for 12 hours. The viscosity of the obtained stock solution for film formation was 50 poise at 22 ° C. This stock solution for film formation was used in Example 1.
A film was formed in the same manner as above, and dried at 100 ° C. for 12 hours with a hot air dryer. Comparative Example 1 is an example using one type of polysulfone. The water permeability of this hollow fiber was measured to be 1185.
It showed a low value of ml / hr / m 2 / kPa.
【００３１】比較例2
ポリスルホン（アモコ社 ”Udel”-P1700 重量平均分
子量4万7000）16部、ポリビニルピロリドン（BASF社 K
90 重量平均分子量１２０万）6部をジメチルアセトア
ミド54.3部、ジメチルスルホキシド21.7部、水2部に加
え、80℃12時間、加熱溶解した。得られた製膜原液の粘
度は、22℃で60ポイズであった。この製膜原液を実施例
１と同様にして製膜し、熱風乾燥機にて100℃、12時間
乾燥した。比較例２は、比較例１とは別の１種のポリス
ルホンを使用した例である。この中空糸の透水性能を測
定したところ840ml/hr/ｍ2/kPaと低い値を示した。Comparative Example 2 16 parts of polysulfone ("Udel" -P1700, weight average molecular weight 47,000, Amco Co.), polyvinylpyrrolidone (K, BASF K
6 parts of 90 weight average molecular weight 1.2 million) were added to 54.3 parts of dimethylacetamide, 21.7 parts of dimethyl sulfoxide and 2 parts of water, and heated and dissolved at 80 ° C. for 12 hours. The viscosity of the obtained film-forming stock solution was 60 poise at 22 ° C. This stock solution for film formation was formed into a film in the same manner as in Example 1, and dried at 100 ° C. for 12 hours with a hot air dryer. Comparative Example 2 is an example using one kind of polysulfone different from Comparative Example 1. When the water permeability of this hollow fiber was measured, it showed a low value of 840 ml / hr / m 2 / kPa.
【００３２】比較例３
ポリスルホン（アモコ社 ”Udel”-P1700 重量平均分
子量4万7000）12部、ポリスルホン4（アモコ社 ”Ude
l”-P3500 重量平均分子量5万9000）部、ポリビニルピ
ロリドン（BASF社 K90 重量平均分子量１２０万）6部
をジメチルアセトアミド54.3部、ジメチルスルホキシド
21.7部、水2部に加え、80℃12時間、加熱溶解した。得
られた製膜原液の粘度は、22℃で46.5ポイズであった。
この製膜原液を実施例１と同様にして製膜し、熱風乾燥
機にて100℃、12時間乾燥した。比較例３は、最小の分
子量を持つポリスルホンの比率が本発明を外れた例であ
る。この中空糸の透水性能を測定したところ1133ml/hr/
ｍ2/kPaと低い値を示した。Comparative Example 3 12 parts of polysulfone ("Udel" -P1700, weight average molecular weight 47,000), polysulfone 4 (Amoco "Ude")
l "-P3500 Weight average molecular weight 59,000 parts, Polyvinylpyrrolidone (BASF K90 weight average molecular weight 1.2 million) 6 parts, dimethylacetamide 54.3 parts, dimethyl sulfoxide
21.7 parts and 2 parts of water were added, and the mixture was heated and dissolved at 80 ° C. for 12 hours. The viscosity of the obtained stock solution for film formation was 46.5 poise at 22 ° C.
This stock solution for film formation was formed into a film in the same manner as in Example 1, and dried at 100 ° C. for 12 hours with a hot air dryer. Comparative Example 3 is an example in which the ratio of the polysulfone having the minimum molecular weight is outside the present invention. The water permeability of this hollow fiber was measured to be 1133 ml / hr /
It showed a low value of m 2 / kPa.
【００３３】[0033]
【発明の効果】本発明により、簡便な方法でポリスルホ
ン系樹脂からなる半透膜の透水性能を向上させることが
できる。According to the present invention, the water permeability of a semipermeable membrane made of a polysulfone resin can be improved by a simple method.
フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｃ０８Ｌ 81/06 Ｃ０８Ｌ 81/06 // Ｄ０１Ｆ 6/76 Ｄ０１Ｆ 6/76 Ｄ Ｆターム(参考） 4C077 AA05 BB01 KK12 LL02 LL05 NN01 NN14 PP07 PP15 4D006 GA06 GA13 MA01 MA03 MB02 MB09 MC40X MC61 MC62X MC63 MC83 MC88 NA04 NA10 NA13 NA16 NA18 NA41 NA42 NA54 PB09 PB42 PB52 PC47 4F071 AA09 AA29 AA37 AA51 AA64 AA81 AF07 AF09 AH02 BB02 BB06 BC01 BC04 BC05 4J002 AB01X BE02X BJ00X CH01X CN03W GB01 GB02 GD05 4L035 BB04 BB11 BB17 DD03 EE04 FF07 GG01 HH01 MF01 Continuation of front page (51) Int.Cl. 7 Identification code FI theme code (reference) C08L 81/06 C08L 81/06 // D01F 6/76 D01F 6/76 DF term (reference) 4C077 AA05 BB01 KK12 LL02 LL05 NN01 NN14 PP07 PP15 4D006 GA06 GA13 MA01 MA03 MB02 MB09 MC40X MC61 MC62X MC63 MC83 MC88 NA04 NA10 NA13 NA16 NA18 NA41 NA42 NA54 PB09 PB42 PB52 PC47 4F071 AA09 AA29 AA37 B01 BC01 BC01 BC01 BC01 BC01 BC01 BC01 AF01 BB06 BC01 AF04 ABB02 AF04 AH02 BB02 AF01 BB06 AF02 AH02 BB02 GB01 GB02 GD05 4L035 BB04 BB11 BB17 DD03 EE04 FF07 GG01 HH01 MF01
Claims (5)
スルホン系樹脂、親水性高分子および溶媒を含み、該２
種類以上のポリスルホン系樹脂の中で最小の重量平均分
子量を持つポリスルホン系樹脂の全ポリスルホン系樹脂
に対する混合比率が１０〜７０重量％である製膜原液を
用いることを特徴とする半透膜の製造方法。1. A polysulfone-based resin having a different weight average molecular weight, a hydrophilic polymer and a solvent, and
Manufacture of a semipermeable membrane characterized by using a membrane-forming stock solution having a mixing ratio of the polysulfone-based resin having the smallest weight average molecular weight among the polysulfone-based resins of more than one kind to the total polysulfone-based resin is 10 to 70% by weight. Method.
を用いることを特徴とする請求項１に記載の半透膜の製
造方法。2. The method for producing a semipermeable membrane according to claim 1, wherein polyvinylpyrrolidone is used as the hydrophilic polymer.
スルホン系樹脂を少なくとも１種用いることを特徴とす
る請求項１または２に記載の半透膜の製造方法。3. The method for producing a semipermeable membrane according to claim 1, wherein at least one polysulfone-based resin having a weight average molecular weight different by 5,000 or more is used.
ことを特徴とする請求項１〜３のいずれかに記載の半透
膜の製造方法。4. The method for producing a semipermeable membrane according to claim 1, wherein the polysulfone resin is polysulfone.
された半透膜を用いた透析器。5. A dialyzer using the semipermeable membrane manufactured by the manufacturing method according to claim 1.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005131482A (en) * | 2003-10-29 | 2005-05-26 | Toray Ind Inc | Separation membrane |
| JP2008521598A (en) * | 2004-12-03 | 2008-06-26 | シーメンス・ウォーター・テクノロジーズ・コーポレイション | Membrane post-treatment |
| JP2016528360A (en) * | 2013-08-13 | 2016-09-15 | フレセニウス メディカル ケア ホールディングス インコーポレーテッド | Method for making polyaryl ethers and use in membrane preparation |
| WO2019017383A1 (en) * | 2017-07-18 | 2019-01-24 | 住友化学株式会社 | Aromatic polysulfone composition |
-
2001
- 2001-10-23 JP JP2001325059A patent/JP3770145B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005131482A (en) * | 2003-10-29 | 2005-05-26 | Toray Ind Inc | Separation membrane |
| JP2008521598A (en) * | 2004-12-03 | 2008-06-26 | シーメンス・ウォーター・テクノロジーズ・コーポレイション | Membrane post-treatment |
| JP2016528360A (en) * | 2013-08-13 | 2016-09-15 | フレセニウス メディカル ケア ホールディングス インコーポレーテッド | Method for making polyaryl ethers and use in membrane preparation |
| WO2019017383A1 (en) * | 2017-07-18 | 2019-01-24 | 住友化学株式会社 | Aromatic polysulfone composition |
| JP2019019219A (en) * | 2017-07-18 | 2019-02-07 | 住友化学株式会社 | Aromatic polysulfone composition |
| US11319443B2 (en) | 2017-07-18 | 2022-05-03 | Sumitomo Chemical Company, Limited | Aromatic polysulfone composition |
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