JPS62221402A - Production of hollow fibrous separation membrane - Google Patents

Production of hollow fibrous separation membrane

Info

Publication number
JPS62221402A
JPS62221402A JP6421986A JP6421986A JPS62221402A JP S62221402 A JPS62221402 A JP S62221402A JP 6421986 A JP6421986 A JP 6421986A JP 6421986 A JP6421986 A JP 6421986A JP S62221402 A JPS62221402 A JP S62221402A
Authority
JP
Japan
Prior art keywords
blood
polysulfone
solvent
membrane
separation membrane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP6421986A
Other languages
Japanese (ja)
Other versions
JPH0563214B2 (en
Inventor
Yasunobu Izumi
泉 康伸
Ryoichi Awata
粟田 僚一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sumitomo Bakelite Co Ltd
Original Assignee
Sumitomo Bakelite Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Sumitomo Bakelite Co Ltd filed Critical Sumitomo Bakelite Co Ltd
Priority to JP6421986A priority Critical patent/JPS62221402A/en
Publication of JPS62221402A publication Critical patent/JPS62221402A/en
Publication of JPH0563214B2 publication Critical patent/JPH0563214B2/ja
Granted legal-status Critical Current

Links

Abstract

PURPOSE:To favorably keep the balance of both filter velocity of blood and a surface state of a membrane brought into contact with blood by using raw liquid mixed with polysulfone in proportion of not more than 1/9 weight of polyether sulfone and spinning hollow yarn. CONSTITUTION:Hollow yarn is produced in a wet spinning process by using raw liquid for spinning which consists of polyether sulfone, polysulfone and a solvent and a solvent and/or metallic salt and/or a non-solvent. Weight ratio of polysulfone to polyether sulfone is preferably regulated to not more than 1/9. Filter efficiency of blood and filter stability are remarkably enhanced by addition of polysulfone. Dimension of a hollow fibrous separation membrane is preferably regulated in the range of 200-300mum inside diameter of the membrane and 10-100mum membrane thickness.

Description

【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、血液浄化用の中空糸型人工臓器に関するもの
である。更に詳しくは、慢性あるいは急性の腎不全患者
の治療を目的とした、すぐれた濾過特性と安定性を有す
る血液透析器、血液濾過器、血圧駆動型血液濾過器等に
関するものである。
DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a hollow fiber type artificial organ for blood purification. More specifically, the present invention relates to hemodialyzers, hemofilters, blood pressure-driven hemofilters, etc. that have excellent filtration characteristics and stability and are intended for the treatment of patients with chronic or acute renal failure.

〔従来技術〕[Prior art]

現在、慢性腎不全患者の治療としては、血液ゼンプを使
用した間歇的な血液透析や血液濾過が一般的に行なわれ
ている。一方、手術後の倉併症等で生じる急性腎不全患
者の治療に対しては、迅速な水分及び溶質の大量の除去
が必要となってくるため、従来の間歇的な治療法では対
応できないことが多い。
Currently, intermittent hemodialysis and hemofiltration using Blood Zemp are commonly used to treat patients with chronic renal failure. On the other hand, for the treatment of patients with acute renal failure due to complications such as post-surgical complications, it is necessary to quickly remove large amounts of water and solutes, which cannot be treated with conventional intermittent treatment methods. There are many.

このような場合には連続的血液透析または血液濾過が効
果的であるが、1日〜2週間程度連続的に使用するため
、これに使用される膜には厳しい血液適合性が要求され
、また従来よシ用いられている血液透析器や血液濾過器
では、構造あるいは膜の特性から使用が不可能であった
。すなわち、従来の透析器や濾過器においては、その構
造のみならず使用される膜そのものKついても4〜5時
間という短時間の血液浄化を目的としたものであり、従
って濾過効率を中心に膜の設計がなされているため長時
間血液と接触していると膜表面に血栓が生じ易いという
欠点があった。
Continuous hemodialysis or hemofiltration is effective in such cases, but since they are used continuously for about 1 day to 2 weeks, the membrane used for this requires strict blood compatibility, and Conventionally used hemodialyzers and hemofilters cannot be used due to their structure or membrane characteristics. In other words, in conventional dialyzers and filters, not only the structure but also the membrane itself is aimed at purifying blood in a short time of 4 to 5 hours. Because of this design, there was a drawback that blood clots were likely to form on the membrane surface if it was in contact with blood for a long time.

更に、長時間の連続使用では患者の心臓に大きな負担が
かかる血液ダンプの使用は好ましくなく、患者自身の血
圧のみによって体外循環を行う治療法、すなわち血圧駆
動型血液濾過も検討されており、この場合患者の血圧に
応じた血流変動、特に血流低下によシ膜内に血栓が生じ
易いことから、従来の血液浄化器の使用は不可能であっ
た。
Furthermore, it is not desirable to use a blood dump, which puts a heavy burden on the patient's heart when used continuously for a long period of time, and a treatment method that performs extracorporeal circulation using only the patient's own blood pressure, that is, blood pressure-driven hemofiltration, is also being considered. In this case, it has been impossible to use conventional blood purifiers because blood flow fluctuates depending on the patient's blood pressure, and in particular blood flow decreases, which tends to cause thrombi to form within the membrane.

〔発明の目的〕[Purpose of the invention]

本発明者らは、以上のような長時間の連続的血液透析ま
九は血液濾過、更には血液ダンプを使用しない血圧駆動
による血液濾過を安定して行うことができる中空糸型血
液浄化器を得るべく鋭意研究を進め九結果、特定の樹脂
及び樹脂原液組成を用いることによシ、すぐれた性能を
有する分離膜が得られることを見出し、更にこの知見に
基づき種々の検討を行い本発明に至っ九ものである。
The present inventors have developed a hollow fiber blood purifier that can stably perform continuous hemodialysis and hemofiltration as described above, as well as blood filtration driven by blood pressure without using a blood dump. As a result of our intensive research, we discovered that a separation membrane with excellent performance could be obtained by using a specific resin and resin stock solution composition.Based on this knowledge, we conducted various studies and developed the present invention. There are nine things in total.

〔発明の構成〕[Structure of the invention]

即ち本発明は、2重管構造の中空繊維製造用ノズルを用
い、外側の環状口から紡糸原液を、芯部から凝固液を凝
固浴中へ吐出し凝固せしめる湿式紡糸法において、紡糸
原液が、f リエーテルスルホン1,617スルホン及
び溶剤、及び/又は金属塩、及び/又は非溶剤からなシ
、コリエーテルスルホンに対するセリスルホンの重量比
が1/9以下であることを特徴とする中空繊維状分離膜
の製造方法である。
That is, the present invention provides a wet spinning method in which a hollow fiber manufacturing nozzle with a double tube structure is used, and a spinning stock solution is discharged from an outer annular port and a coagulation solution is discharged from a core into a coagulation bath and coagulated. f Liethersulfone 1,617 sulfone and a solvent, and/or a metal salt, and/or a non-solvent, and a hollow fiber separation characterized in that the weight ratio of serisulfone to coryethersulfone is 1/9 or less This is a method for manufacturing a membrane.

中空繊維状分離膜の寸法は通常、膜内径が200〜30
0μm1膜厚が10〜100μmの範囲で作成が可能で
あるが、膜の強度やハウジングに挿入する際の充填率を
向上させるために膜内径は210〜240μm1膜厚は
30〜50薊の範囲が望ましい0 本発明で使用するピリエーテルスルホン及びセリスルホ
ンは、それぞれ し単位よシなる構造を有する重合体である。
The dimensions of hollow fibrous separation membranes are usually 200 to 30 mm in inner diameter.
Although it is possible to create a membrane with a thickness of 10 to 100 μm, the inner diameter of the membrane is 210 to 240 μm and the thickness is 30 to 50 μm in order to improve the strength of the membrane and the filling rate when inserting it into the housing. Desirable 0 Pyriether sulfone and seris sulfone used in the present invention are polymers each having a structure consisting of units.

コリエーテルスルホン及びコリスルホ/を溶解する極性
有機溶剤としては、例としてジメチルホルムアミド、N
−メチル−2−ピロリドンなどがあるが、コリエーテル
スルホン及びポリスルホンを溶解するものであればこれ
らに限定されない。
Examples of polar organic solvents that dissolve coliethersulfone and colisulfone include dimethylformamide, N
Examples include -methyl-2-pyrrolidone, but are not limited to these as long as they can dissolve coryethersulfone and polysulfone.

また、紡糸原液または凝固液に含まれる非溶剤は、アル
コール系、ケトン系などがあるがこれらに限定されず、
また2種以上の非溶剤の組合わせも使用できる。
In addition, non-solvents contained in the spinning dope or coagulation solution include, but are not limited to, alcohol-based, ketone-based, etc.
A combination of two or more types of non-solvents can also be used.

コリエーテルスルホンに対するポリスルホンの重量比は
1/9以下とするのが好ましい。1/9を越える場合は
、紡糸原液において両樹脂の相分離が生じ易くなシ、こ
の結果、安定な紡糸が困難となることが多い。仮に、紡
糸が可能な場合でも、中空繊維状分離膜の表面が例えば
凹凸状のような粗な構造となシ、このために実際の血液
を濾過する際に膜表面に血栓が生じ易く、本発明の目的
とする長時間の安定な血液濾過が不可能となる。
The weight ratio of polysulfone to coliether sulfone is preferably 1/9 or less. If it exceeds 1/9, phase separation of both resins is not likely to occur in the spinning dope, and as a result, stable spinning is often difficult. Even if spinning were possible, the surface of the hollow fibrous separation membrane would have a rough structure, such as an uneven surface, which would easily cause blood clots to form on the membrane surface during actual blood filtration. Stable blood filtration over a long period of time, which is the object of the invention, becomes impossible.

一方、ytrリスルホン/&lJエーテルスルホンの重
量比が1/9以下の場合は両樹脂の相溶性は良好で、し
かもセリエーテルスルホン単独の紡糸原液組成に比べて
、ポリスルホンをわずかに添加することにより血液のp
過特性、すなわち濾過効率及び濾過安定性が大巾に向上
するものである。更に、紡糸原液及び凝固液に金属塩ま
たは非溶剤を適度に組合わせて用いることによって、血
液濾過効率にすぐれ、しかも極めて血栓が生じにくく、
従って長時間の安定な濾過が可能な中空繊維状分離膜を
得ることができる。
On the other hand, when the weight ratio of ytr risulfone/&lJ ether sulfone is 1/9 or less, the compatibility of both resins is good, and compared to the spinning dope composition of serie ether sulfone alone, the addition of a small amount of polysulfone increases blood flow. p of
The filtration characteristics, ie, filtration efficiency and filtration stability, are greatly improved. Furthermore, by using a suitable combination of metal salts or non-solvents in the spinning dope and coagulation solution, it has excellent blood filtration efficiency and is extremely resistant to thrombus formation.
Therefore, a hollow fibrous separation membrane capable of stable filtration for a long period of time can be obtained.

紡糸原液または凝固液に含まれる金属塩は、Lict、
 LiBr%NaC11NaBr、 KCl、 KBr
、MgC/4、MgBr2、CaCl2、CaBr2の
少くとも1種より選ばれたものである。
The metal salts contained in the spinning dope or coagulation solution are Lict,
LiBr%NaC11NaBr, KCl, KBr
, MgC/4, MgBr2, CaCl2, and CaBr2.

ノズル芯部よシ吐出し紡糸原液の内部よシ凝固せしめる
内部凝固液、及び外部より凝固せしめる凝固液の組成は
、操作性の点からは水単独であることが望ましいが、水
に金属塩及び/又はコリエーテルスルホン及びコリスル
ホンの溶剤、及び/又は非溶剤を加えることKよシ、分
離膜の中間層の構造を変えることが可能である。ここで
用いられる金属塩、溶剤及び非溶剤は紡糸原液に用いる
ものと同様であるがこれらに限定されない。
From the viewpoint of operability, it is desirable that the composition of the internal coagulating liquid that coagulates the spinning stock solution discharged from the nozzle core and the coagulating liquid that coagulates from the outside is water alone, but it is preferable that the water contains metal salts and It is possible to change the structure of the intermediate layer of the separation membrane by adding a solvent and/or a non-solvent for coliethersulfone and colisulfone. The metal salt, solvent, and nonsolvent used here are the same as those used in the spinning dope, but are not limited thereto.

〔発明の効果〕〔Effect of the invention〕

以上のように、コリエーテルスルホン及びノリスルホン
を含む特定な樹脂原液組成よシ得られた中空繊維状分離
膜は、血液と接触する膜の表面状態と血液濾過速度、す
なわち除水能とのバランスが良好に保たれ、この結果血
液透析または血液濾過を極めて効率よくかつ安定に行い
得るものである。従って、慢性あるいは急性腎不全患者
の治療において、従来困難とされていた長時間の連続的
血液透析または血液濾過、更には血液ピンクを使用しな
い血圧駆動による血液濾過に対しても効果的である。
As described above, the hollow fibrous separation membrane obtained with a specific resin stock solution composition containing coryether sulfone and noris sulfone has a balance between the surface condition of the membrane in contact with blood and the blood filtration rate, that is, water removal ability. is maintained well, and as a result, hemodialysis or hemofiltration can be performed extremely efficiently and stably. Therefore, in the treatment of patients with chronic or acute renal failure, it is effective for long-term continuous hemodialysis or hemofiltration, which has been considered difficult in the past, as well as blood pressure-driven hemofiltration that does not use blood pink.

実施例1 コリエーテルスルホン14重量%、コリスルホン1重k
 % 、NaBr 5重tチ及びジメチルホルムアミド
80重fi%を溶解混合した。この溶液を紡糸原液とし
て、中空繊維製造用ノズルの外側の環状口から紡糸原液
を、また芯部からは水を吐出し、水からなる凝固浴中へ
導いて凝固せしめ、40m/分の速度で巻取りを行った
。ここで紡糸温度、すなわち紡糸原液及び内部凝固液の
温度は40℃であった。巻取った中空繊維状分離膜は6
0℃の温水中に7時間、更に流水中に10時間の浸漬を
行った。得られた中空繊維状分離膜は内径220/’m
 1膜厚30I!rr1であった。
Example 1 Coryethersulfone 14% by weight, Corysulfone 1wk
%, 5% NaBr and 80% dimethylformamide were dissolved and mixed. Using this solution as a spinning stock solution, the spinning stock solution was discharged from the outer annular opening of the hollow fiber production nozzle, and water was discharged from the core, which was introduced into a coagulation bath consisting of water and coagulated at a speed of 40 m/min. I took up the winding. Here, the spinning temperature, that is, the temperature of the spinning dope and the internal coagulation liquid, was 40°C. The rolled hollow fibrous separation membrane is 6
It was immersed in warm water at 0° C. for 7 hours and then in running water for 10 hours. The obtained hollow fibrous separation membrane has an inner diameter of 220/'m
1 film thickness 30I! It was rr1.

この中空繊維状分離膜3000本をピリカーボネート製
の円筒カラムに挿入し、両端をコリウレタンによシ接着
固定した後、両端部を切断し中空繊維状分離膜の開口部
を得た。中空繊維状分離膜の有効長は10信であった。
3,000 of these hollow fibrous separation membranes were inserted into a cylindrical column made of pyricarbonate, both ends of which were adhesively fixed with courethane, and then both ends were cut to obtain openings in the hollow fibrous separation membranes. The effective length of the hollow fibrous separation membrane was 10 threads.

次いで、体重約16吟の尿管結紮した雑種犬の頚部動、
静脈に外シャントを設置し、血圧駆動による血液濾過を
行った。その際へAIJンを400IU/時間で持続注
入を行った。その結果、700〜1500mt/時間の
除水が安定して得られ、100時間以上の連続濾過が可
能であシ、この量大の状態も良好であった。
Next, the cervical motion of a mongrel dog weighing approximately 16 gin with ureteral ligation,
An external shunt was placed in the vein, and blood pressure-driven blood filtration was performed. At that time, AIJ was continuously infused at 400 IU/hour. As a result, water removal of 700 to 1500 mt/hour was stably obtained, continuous filtration for 100 hours or more was possible, and conditions were good even with this large amount.

以下の実施例及び比較例においては、特に断らない限り
本実施例と同様にして紡糸、評価試験等を行うものとす
る。
In the following Examples and Comparative Examples, unless otherwise specified, spinning, evaluation tests, etc. will be conducted in the same manner as in this Example.

実施例2 コリエーテルスルホン15重量%、コリスルホン1.5
重量%、LiC44重量%及びN−メチル−2−ピロリ
ドン79.5重量%よりなる紡糸原液を用いた。巻取り
速度は50m/分であった。得られた膜は内径230薊
、膜厚35μmであった。犬による血液濾過試験では、
900〜1400fd/時間の除水で、100時間以上
の安定な連続濾過が可能であった。
Example 2 Coryethersulfone 15% by weight, colisulfone 1.5
A spinning dope consisting of 44% by weight of LiC and 79.5% by weight of N-methyl-2-pyrrolidone was used. The winding speed was 50 m/min. The obtained membrane had an inner diameter of 230 mm and a thickness of 35 μm. In a dog hemofiltration test,
Stable continuous filtration for 100 hours or more was possible with water removal of 900 to 1400 fd/hour.

実施例3 コリエーテルスルホン15重量%、コリスルホン1重量
%、エタノール3重量%及びN−メチル−2−ピロリド
ン81重i%の組成よりなる紡糸原液を用いた。犬によ
る血液濾過試験では除水能、長時間安定性ともに良好で
あった。
Example 3 A spinning dope having a composition of 15% by weight of coryethersulfone, 1% by weight of colisulfone, 3% by weight of ethanol, and 81% by weight of N-methyl-2-pyrrolidone was used. In a blood filtration test using dogs, both water removal ability and long-term stability were good.

比較例1 コリエーテルスルホン15重量%、NaBr3重量%及
びジメチルホルムアミド80重量%よりなる紡糸原液を
用いた。犬による血液濾過試験では、長時間の安定性で
は良好であったが、除水能が600rn1.7分以下と
低い値であった。この値は、腎不全患者の症状に対して
は除水能が不十分である。
Comparative Example 1 A spinning dope containing 15% by weight of coryethersulfone, 3% by weight of NaBr, and 80% by weight of dimethylformamide was used. In a blood filtration test using dogs, the long-term stability was good, but the water removal ability was low at 600 rn 1.7 minutes or less. This value indicates insufficient water removal ability for the symptoms of patients with renal failure.

比較例2 ポリエーテルスルホ/13重量%、ゴリスルホン2重量
%、NaBr3重量%及びジメチルホルムアミド80t
i%よりなる紡糸原液を用いた。血液濾過試験において
は、試験開始後約5時間は1000〜1300fd/時
間の高い除水能を示したが、その後急激に低下し、50
時間抜100mff1/時以下になったため実験を中止
した。使用した中空繊維状分離膜の内部に血栓が認めら
れ、これが除水量低下の原因であった。
Comparative Example 2 Polyether sulfo/13% by weight, gorisulfone 2% by weight, NaBr 3% by weight and dimethylformamide 80t
A spinning dope consisting of i% was used. In the blood filtration test, a high water removal ability of 1000 to 1300 fd/hour was shown for about 5 hours after the start of the test, but after that it rapidly decreased to 50 fd/hour.
The experiment was stopped because the time cutout became less than 100mff1/hour. Thrombus was observed inside the hollow fibrous separation membrane used, and this was the cause of the decrease in water removal.

Claims (3)

【特許請求の範囲】[Claims] (1)2重管構造の中空繊維製造用ノズルを用い、外側
の環状口から紡糸原液を、芯部から凝固液を凝固浴中へ
吐出し凝固せしめる湿式紡糸法において、紡糸原液がポ
リエーテルスルホン、ポリスルホン及び溶剤、及び/又
は金属塩、及び/又は非溶剤からなり、ポリエーテルス
ルホンに対するポリスルホンの重量比が1/9以下であ
ることを特徴とする中空繊維状分離膜の製造方法。
(1) In a wet spinning method in which a hollow fiber manufacturing nozzle with a double tube structure is used, the spinning stock solution is discharged from the outer annular port and the coagulation solution is discharged from the core into a coagulation bath and coagulated. , a method for producing a hollow fibrous separation membrane comprising polysulfone and a solvent, and/or a metal salt, and/or a non-solvent, characterized in that the weight ratio of polysulfone to polyethersulfone is 1/9 or less.
(2)凝固液の組成が水、または水、金属塩及び/又は
該樹脂の溶剤、及び/又は該樹脂の非溶剤からなること
を特徴とする、特許請求の範囲第(1)項記載の中空繊
維状分離膜の製造方法。
(2) The composition of the coagulating liquid is water, or water, a metal salt, and/or a solvent for the resin, and/or a non-solvent for the resin. A method for producing a hollow fibrous separation membrane.
(3)ポリエーテルスルホン及びポリスルホンが、それ
ぞれ ▲数式、化学式、表等があります▼及び ▲数式、化学式、表等があります▼のくり返 し単位を有する重合体よりなることを特徴とする、特許
請求の範囲第(1)項記載の中空繊維状分離膜の製造方
法。
(3) A patent claim characterized in that polyethersulfone and polysulfone are composed of polymers having repeating units of ▲ has a mathematical formula, chemical formula, table, etc. ▼ and ▲ has a mathematical formula, chemical formula, table, etc. ▼ A method for producing a hollow fibrous separation membrane according to scope (1).
JP6421986A 1986-03-24 1986-03-24 Production of hollow fibrous separation membrane Granted JPS62221402A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP6421986A JPS62221402A (en) 1986-03-24 1986-03-24 Production of hollow fibrous separation membrane

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6421986A JPS62221402A (en) 1986-03-24 1986-03-24 Production of hollow fibrous separation membrane

Publications (2)

Publication Number Publication Date
JPS62221402A true JPS62221402A (en) 1987-09-29
JPH0563214B2 JPH0563214B2 (en) 1993-09-10

Family

ID=13251767

Family Applications (1)

Application Number Title Priority Date Filing Date
JP6421986A Granted JPS62221402A (en) 1986-03-24 1986-03-24 Production of hollow fibrous separation membrane

Country Status (1)

Country Link
JP (1) JPS62221402A (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284137B1 (en) 1994-06-07 2001-09-04 Mitsubishi Rayon Co., Ltd. Polysulfone porous membrane and a method of manufacturing the same
CN1076630C (en) * 1997-12-17 2001-12-26 四川联合大学 Polyether sulphone hollow fibre film and its manufacturing method and use

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6284137B1 (en) 1994-06-07 2001-09-04 Mitsubishi Rayon Co., Ltd. Polysulfone porous membrane and a method of manufacturing the same
CN1076630C (en) * 1997-12-17 2001-12-26 四川联合大学 Polyether sulphone hollow fibre film and its manufacturing method and use

Also Published As

Publication number Publication date
JPH0563214B2 (en) 1993-09-10

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