JP2003245524A - Method for manufacturing hollow fiber type blood cleaning membrane - Google Patents
Method for manufacturing hollow fiber type blood cleaning membraneInfo
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- JP2003245524A JP2003245524A JP2002366428A JP2002366428A JP2003245524A JP 2003245524 A JP2003245524 A JP 2003245524A JP 2002366428 A JP2002366428 A JP 2002366428A JP 2002366428 A JP2002366428 A JP 2002366428A JP 2003245524 A JP2003245524 A JP 2003245524A
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- Prior art keywords
- spinning
- hollow fiber
- blood purification
- spinneret
- discharge
- 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.)
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- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- External Artificial Organs (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、中空糸型血液浄化膜の
製造方法に関する。FIELD OF THE INVENTION The present invention relates to a method for producing a hollow fiber type blood purification membrane.
【０００２】[0002]
【従来の技術】従来、血液浄化用の中空糸膜として、セ
ルロース系、セルロースアセテート系、ポリアミド系、
ポリアクリロニトリル系などのポリマーを素材とする中
空糸膜が知られており、これらはチューブインオリフィ
ス型と呼ばれる二重紡糸口金を用いて製造されている。
例えば、特許文献１には、血液浄化用のポリアクリロニ
トリル系中空糸膜の製造方法が記載されている。また、
特許文献２〜４には、血液浄化用のポリスルホン系中空
糸膜の製造方法が記載されている。2. Description of the Related Art Conventional hollow fiber membranes for blood purification include cellulose-based, cellulose acetate-based, polyamide-based,
Hollow fiber membranes made of polyacrylonitrile-based polymers and the like are known, and these are manufactured using a double spinneret called a tube-in-orifice type.
For example, Patent Document 1 describes a method for producing a polyacrylonitrile-based hollow fiber membrane for blood purification. Also,
Patent Documents 2 to 4 describe a method for producing a polysulfone-based hollow fiber membrane for blood purification.
【０００３】しかしながら、慢性腎不全患者数の増加に
伴う生産性向上の一手段として、高速紡糸技術が必要で
あるにもかかわらず、従来技術で開示されている紡糸速
度はせいぜい５０ｍ／分と概して低いものであった。こ
のような低速の紡糸速度で生産性を上げようとすると、
必然的に紡糸錘数をかせがねばならず、その結果生産設
備を拡大せざるを得なかった。また、上記のように紡糸
速度を高くすると、膜の微細構造が部分的に破壊される
ことにより、得られる中空糸膜の機械的特性や膜の分画
性が損なわれることもあった。この問題に対しては、紡
糸制御因子を如何様に制御しても紡糸速度が高い限りは
膜の伸度や分子量分画性の低下を抑制することができ
ず、血液浄化膜としては満足すべきものが得られなかっ
た。このため、５０ｍ／分以下というあまり高くない紡
糸速度で生産性を犠牲にしながら血液浄化用の中空糸膜
が製造されているのが現状である。However, in spite of the need for high-speed spinning technology as one means for improving productivity with the increase in the number of patients with chronic renal failure, the spinning speed disclosed in the prior art is generally at most 50 m / min. It was low. When trying to increase productivity at such a low spinning speed,
Inevitably, the number of spinning spindles had to be increased, and as a result, production facilities had to be expanded. Further, when the spinning speed is increased as described above, the microstructure of the membrane is partially destroyed, which may impair the mechanical properties of the resulting hollow fiber membrane and the fractionation of the membrane. To solve this problem, no matter how the spinning control factor is controlled, the elongation of the membrane and the reduction of the molecular weight fractionation cannot be suppressed as long as the spinning speed is high, and it should be satisfied as a blood purification membrane. I couldn't get the kimono. For this reason, the present situation is that hollow fiber membranes for blood purification are manufactured at a spinning speed of 50 m / min or less, which is not so high while sacrificing productivity.
【０００４】[0004]
【特許文献１】特開平２−２７３５２２号公報[Patent Document 1] Japanese Unexamined Patent Publication No. 2-273522
【特許文献２】特公平２−０１８６９５号公報[Patent Document 2] Japanese Patent Publication No. 2-018695
【特許文献３】特公平５−０５４３７３号公報[Patent Document 3] Japanese Patent Publication No. 05-054733
【特許文献４】特開平６−１６５９２６号公報[Patent Document 4] JP-A-6-165926
【０００５】[0005]
【発明が解決しようとする課題】本発明は従来技術の問
題点を解消し、生産性を上げるために、紡糸速度を高め
ても十分な糸伸度を持ち、分子量分画性に優れた中空糸
型血液浄化膜の製造方法を提供することを課題とする。DISCLOSURE OF THE INVENTION The present invention solves the problems of the prior art and, in order to increase the productivity, has a sufficient yarn elongation even if the spinning speed is increased, and has a high molecular weight fractionation. An object of the present invention is to provide a method for producing a thread-type blood purification membrane.
【０００６】[0006]
【課題を解決するための手段】本発明者は、中空糸型血
液浄化膜の高速紡糸方法を確立すべく、種々の紡糸制御
因子について鋭意検討した結果、紡糸口金直下で起こる
バラス効果を抑制することにより、膜の微細構造の破壊
によって生じる機械的強度や分画性の低下を抑制できる
ことを見出した。なお、バラス効果とは、紡糸原液が紡
糸口金から吐出された直後に径の外方向に膨らむことを
いう。そして、ドラフト率を、従来知られているノズル
ドラフト率（所謂みかけのドラフト率：巻き取り速度／
ノズル吐出線速度（[Means for Solving the Problems] The inventors of the present invention diligently studied various spinning control factors in order to establish a high-speed spinning method for a hollow fiber type blood purification membrane, and as a result, suppressed the ballast effect occurring directly under the spinneret. By doing so, it was found that it is possible to suppress the deterioration of the mechanical strength and the fractionation property caused by the destruction of the fine structure of the film. The term "balus effect" means that the spinning dope swells outward in the diameter immediately after being discharged from the spinneret. Then, the draft ratio is calculated by comparing the conventionally known nozzle draft ratio (so-called apparent draft ratio: winding speed /
Nozzle discharge linear velocity (
【００１２】））ではなく、紡糸口金直下のドラフト率
（落下部ドラフト率）として特定すると、伸度低下を起
さずしかもシャープな分画性を有する膜が得られること
を見出して本発明を完成するに至った。The present invention has been found out that a film having a sharp fractionation property without causing a decrease in elongation can be obtained by specifying the draft ratio (falling part draft ratio) just below the spinneret instead of the above). It came to completion.
【０００７】即ち、本発明は、以下の（１）〜（７）に
関するものである。
（１）紡糸原液をチューブインオリフィスよりなる紡糸
口金より中空内液とともに吐出して、紡糸する中空糸型
血液浄化膜の製造方法であって、紡糸原液吐出部の長さ
／径が０．５以上２．５以下である紡糸口金を使用し
て、落下部ドラフト率を２．０以下で紡糸することを特
徴とする中空糸型血液浄化膜の製造方法。
（２）５０ｍ／分を超える巻き取り速度で紡糸すること
を特徴とする（１）記載の中空糸型血液浄化膜の製造方
法。
（３）紡糸原液の粘度が１０００ｍＰａ・ｓ以上３５０
０ｍＰａ・ｓ以下であることを特徴とする（１）または
（２）記載の中空糸型血液浄化膜の製造方法。
（４）中空内液の吐出線速度を紡糸原液の落下部吐出線
速度で除した線速度比が５以上１０以下で紡糸すること
を特徴とする（１）〜（３）のいずれかに記載の中空糸
型血液浄化膜の製造方法。
（５）紡糸原液吐出部の面積を内液吐出部の面積で除し
た値が４．０以上９．０以下である紡糸口金を使用して
紡糸する（１）〜（４）のいずれかに記載の中空糸型血
液浄化膜の製造方法。
（６）紡糸原液吐出部のスリット幅を中空糸膜厚に対し
て±２０％以内にして紡糸することを特徴とする（１）
〜（５）のいずれかに記載の中空糸型血液浄化膜の製造
方法。
（７）ポリスルホンとポリビニルピロリドンと溶剤より
なる紡糸原液を用いてポリスルホン系血液浄化膜を製造
する（１）〜（６）のいずれかに記載の方法。That is, the present invention relates to the following (1) to (7). (1) A method for producing a hollow fiber type blood purification membrane, in which a spinning dope is discharged together with a hollow inner liquid from a spinneret consisting of a tube-in-orifice, and a spinning dope discharge part has a length / diameter of 0.5. A method for producing a hollow fiber type blood purification membrane, which comprises spinning at a draft ratio of 2.0 or less using a spinneret having a ratio of 2.5 or less. (2) The method for producing a hollow fiber type blood purification membrane according to (1), which comprises spinning at a winding speed of more than 50 m / min. (3) Viscosity of the spinning solution is 1000 mPa · s or more 350
The method for producing a hollow fiber blood purification membrane according to (1) or (2), which is 0 mPa · s or less. (4) Spinning is performed at a linear velocity ratio of 5 or more and 10 or less, which is obtained by dividing the linear velocity of discharge of the liquid in the hollow by the linear velocity of discharge of the stock solution for spinning. 1. A method for producing a hollow fiber type blood purification membrane. (5) Spinning is performed using a spinneret having a value obtained by dividing the area of the spinning stock solution discharge part by the area of the internal liquid discharge part of 4.0 or more and 9.0 or less. A method for producing the hollow fiber blood purification membrane described. (6) Spinning is performed with the slit width of the spinning solution discharge part within ± 20% of the hollow fiber film thickness (1)
~ The method for producing a hollow fiber blood purification membrane according to any one of (5). (7) The method according to any one of (1) to (6), wherein a polysulfone-based blood purification membrane is produced using a spinning dope containing polysulfone, polyvinylpyrrolidone and a solvent.
【０００８】[0008]
【発明の実施の形態】以下、本発明の詳細を述べる。本
発明に用いられる中空糸膜の素材としては、適当な溶媒
に可溶性であり、適切な中空内液が選定される高分子材
料であれば任意のものが用いられる。例えば、ポリスル
ホン、ポリエーテルスルホン、ポリアクリロニトリル、
ポリカーボネート、エチレン−ビニルアルコール共重合
体、ポリアミド、ポリメチルメタクリレート等が挙げら
れ、これらを単独に用いて膜としても、これらを主体成
分として副次成分を含む膜としてもよい。中でも、ポリ
スルホンを主体とし、親水化材としてポリビニルピロリ
ドンを添加した場合は、血液浄化膜としての生体適合性
が高まるため、特に好ましく用いられる。以下、中空糸
膜素材にポリスルホンを用いる場合を例として説明す
る。本発明で言うポリスルホン（以下ＰＳｆ）とは、ス
ルホン結合を有する高分子結合物の総称であり特に規定
するものでないが、例を挙げるとBEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. As the material of the hollow fiber membrane used in the present invention, any material can be used as long as it is a polymer material that is soluble in a suitable solvent and a suitable hollow liquid is selected. For example, polysulfone, polyether sulfone, polyacrylonitrile,
Examples thereof include polycarbonate, ethylene-vinyl alcohol copolymer, polyamide, and polymethylmethacrylate. These may be used alone to form a film, or a film containing these as a main component and a subsidiary component. Among them, when polysulfone is mainly used and polyvinylpyrrolidone is added as a hydrophilizing material, biocompatibility as a blood purification membrane is increased, and therefore, it is particularly preferably used. Hereinafter, a case where polysulfone is used as the hollow fiber membrane material will be described as an example. The polysulfone (hereinafter referred to as PSf) referred to in the present invention is a general term for polymer-bound substances having a sulfone bond and is not particularly limited, but examples thereof are as follows.
【化１】 または[Chemical 1] Or
【化２】
に示される繰り返し単位をもつポリスルホン樹脂が広く
市販されており、入手も容易なため好ましく用いられ
る。前者の構造を持つポリスルホンはＡＭＯＣＯ社より
「ユーデル」の商標名で、またＢＡＳＦ社より「ウルト
ラゾーン」の商標名で市販されており、重合度等によっ
ていくつかの種類が存在する。[Chemical 2] The polysulfone resin having the repeating unit shown in is commercially available widely and is easily available, and thus is preferably used. The polysulfone having the former structure is commercially available from AMOCO under the trade name of "Udel" and from BASF under the trade name of "Ultrazone", and there are several types depending on the degree of polymerization and the like.
【０００９】また、本発明のポリビニルピロリドン（以
下ＰＶＰ）は、Ｎ−ビニルピロリドンをビニル重合させ
た水溶性の高分子化合物であり、ＩＳＰ社より「プラス
ドン」の商標名で、また、ＢＡＳＦ社より「コリドン」
の商標名で、市販されており、それぞれいくつかの分子
量のＰＶＰがある。The polyvinylpyrrolidone (hereinafter, PVP) of the present invention is a water-soluble polymer compound obtained by vinyl-polymerizing N-vinylpyrrolidone, which is a trade name of "Plasdone" from ISP and from BASF. "Kolidon"
Are commercially available under the trade name of PVP, each of which has several molecular weights.
【００１０】これらＰＳｆとＰＶＰを両方に共通溶媒に
溶解し、均一な紡糸原液を調整する。共通溶媒として
は、例えば、ジメチルアセトアミド（以下ＤＭＡＣと呼
ぶ）、ジメチルスルホキシド（以下ＤＭＳＯと呼ぶ）、
Ｎ−メチル−２−ピロリドン、ジメチルホルムアミド、
スルホラン、ジオキサン等の多種の溶媒あるいは上記２
種以上の混合液からなる溶媒が挙げられる。また、孔径
制御のため、紡糸原液には水などの添加物を加えても良
い。Both PSf and PVP are dissolved in a common solvent to prepare a uniform spinning dope. Examples of the common solvent include dimethylacetamide (hereinafter referred to as DMAC), dimethyl sulfoxide (hereinafter referred to as DMSO),
N-methyl-2-pyrrolidone, dimethylformamide,
Various solvents such as sulfolane and dioxane or the above 2
A solvent composed of a mixed liquid of at least one species may be mentioned. Further, in order to control the pore diameter, an additive such as water may be added to the spinning dope.
【００１１】本発明においては、紡糸口金から凝固液に
浸漬される前に空気中を通過させる乾湿式法で紡糸する
のが好ましい。具体的には、中空糸膜を製膜するに際し
てはチューブインオリフィス型の紡糸口金を用い、該紡
糸口金から紡糸原液と該紡糸原液を凝固させる為の中空
内液とを同時に空中に押し出し、５０〜１５０ｃｍの空
走部を走行させた後、紡糸口金下部に設置した水を主体
とする凝固浴中へ浸漬、凝固させた後巻き取る。中空内
液は紡糸原液を凝固させる液体であり、膜素材の貧溶媒
を含む液体である。通常、水または水を主体とした凝固
液が使用でき、目的とする中空糸膜の膜性能に応じてそ
の組成等は決めていけば良く一概には決められないが、
一般的には紡糸原液に使った溶剤と水との混合溶液が好
適に使用される。例えば０〜６０重量％のＤＭＡＣ水溶
液などが用いられる。In the present invention, it is preferable to carry out spinning by a dry-wet method in which air is passed through the spinning nozzle before being immersed in the coagulating liquid. Specifically, when forming a hollow fiber membrane, a tube-in-orifice type spinneret is used, and a spinning dope and a hollow liquid for coagulating the spinning dope are simultaneously extruded into the air through the spinneret, and 50 After running in an idle section of up to 150 cm, it is immersed in a coagulation bath mainly composed of water installed under the spinneret, coagulated, and then wound up. The hollow internal liquid is a liquid that solidifies the spinning dope and is a liquid containing a poor solvent for the membrane material. Usually, water or a coagulating liquid mainly composed of water can be used, and its composition etc. may be decided depending on the membrane performance of the target hollow fiber membrane, but it cannot be decided unconditionally.
Generally, a mixed solution of the solvent used for the spinning dope and water is preferably used. For example, a 0-60 wt% DMAC aqueous solution or the like is used.
【００１２】この時、巻き取り速度が５０ｍ／分に満た
ない低紡速の場合は、ノズルドラフト率を従来技術の範
囲（およそ０．９５以上）に設定することで、伸度や分
子量分画性を損なわない範囲で中空糸の形成が可能であ
った。ここでいうノズルドラフト率とは、巻き取り速度
を紡糸原液の吐出線速度で割った値（みかけのドラフト
率）である。また、ここで言う紡糸原液の吐出線速度と
は紡糸時に紡糸口金から紡糸原液が吐出される時の線速
度で、単位時間当たりの紡糸原液の吐出流量を紡糸口金
の原液吐出断面積で割った値である。At this time, when the winding speed is a low spinning speed of less than 50 m / min, the elongation and the molecular weight fraction are set by setting the nozzle draft rate within the range of the prior art (about 0.95 or more). It was possible to form hollow fibers within a range that does not impair the properties. The nozzle draft ratio here is a value (apparent draft ratio) obtained by dividing the winding speed by the linear discharge velocity of the spinning dope. In addition, the linear velocity of the spinning dope discharged here is the linear velocity at which the spinning dope is discharged from the spinneret during spinning, and the discharge flow rate of the spinning dope per unit time is divided by the cross-section of the spinning dope. It is a value.
【００１３】一方、巻き取り速度が５０ｍ／分を超えそ
れ以上の高紡速で紡糸する場合、ノズルドラフト率を従
来技術の範囲に設定しても伸度の低下が著しく、また、
分子量分画性も損なわれるため、血液浄化用膜として満
足できるものではなかった。On the other hand, when the winding speed exceeds 50 m / min and the spinning speed is higher than that, even if the nozzle draft ratio is set within the range of the prior art, the elongation is remarkably lowered, and
Since the molecular weight fractionation property is also impaired, it was not satisfactory as a blood purification membrane.
【００１４】本発明者は、この問題を解決すべく、紡糸
口金直下の紡糸原液の流れを解析した。その結果、本発
明のようなチューブインオリフィス型紡糸口金を用いる
中空糸膜の紡糸工程においても、従来の繊維紡糸工程に
おいて知られていた、紡糸原液が紡糸口金から吐出され
た直後に径の外方向に膨らむ「バラス効果」が生じるこ
とを確認した。即ち、図１に示すように、紡糸原液が紡
糸口金から吐出された直後に、紡糸原液が流れる紡糸口
金のスリット幅より径の外方向に大幅に膨らみ、その
後、延伸によって所定の幅に戻る。この事は、紡糸口金
直下で紡糸原液の線速度が大幅に低下することを示して
いる。このようにバラス効果によって紡糸口金直下での
原液吐出線速度が変わってしまい、また、紡糸速度が高
くなるほどバラス効果がより顕著になるので、従来のノ
ズルドラフト率を特定するだけでは、膜物性や膜構造を
制御するうえで不十分であることが分かった。In order to solve this problem, the present inventor analyzed the flow of the spinning dope just below the spinneret. As a result, even in the process of spinning a hollow fiber membrane using the tube-in-orifice type spinneret as in the present invention, it is known in the conventional fiber spinning process that the spinning stock solution has a diameter outside the diameter immediately after being discharged from the spinneret. It was confirmed that a "ballast effect" that swells in the direction occurs. That is, as shown in FIG. 1, immediately after the spinning dope is discharged from the spinneret, the spinning dope swells to the outside of the diameter of the slit width of the spinning die, and then returns to a predetermined width by stretching. This indicates that the linear velocity of the spinning dope is greatly reduced just below the spinneret. In this way, the raw material discharge linear velocity directly below the spinneret changes due to the ballast effect, and the higher the spinning speed, the more pronounced the ballast effect becomes. It was found to be insufficient in controlling the membrane structure.
【００１５】本発明者はここで新たに真のドラフト率と
いう概念を提案し、落下部ドラフト率と定義する。本発
明でいう落下部ドラフト率とは、巻き取り速度を落下部
吐出線速度で除した値であり、ここで、落下部吐出線速
度は、マイクロスコープ等で実際に紡糸口金直下のバラ
ス効果状態を確認したときに、紡糸原液吐出流量を図１
に示すようなバラス部の径が最大となる部分（ｂ）の断
面積で除して求める。図１の例では、下記の式（１）よ
り求め、次元をｍ／分に合わせた数値を言う。落下部吐
出線速度＝原液吐出流量／[π（ｂ／2）2−π（ｃ／2）
2] （１）落下部ドラフト率は巻き取り速度と凝固開
始直後の紡糸原液の流れが最も遅い部分の比であるた
め、紡糸原液がどれだけ延伸されているかを実質的に表
しており、真のドラフト率と言うことができる。The present inventor newly proposes the concept of the true draft rate and defines it as the falling portion draft rate. The drop portion draft rate in the present invention is a value obtained by dividing the winding speed by the drop portion discharge linear velocity, where the drop portion discharge linear velocity is actually a ballast effect state directly below the spinneret with a microscope or the like. When confirming the
It is obtained by dividing by the cross-sectional area of the portion (b) where the diameter of the ballast portion is the maximum as shown in FIG. In the example of FIG. 1, it is a numerical value obtained by the following equation (1) and the dimension is adjusted to m / min. Droplet discharge linear velocity = stock solution discharge flow rate / [π (b / 2) 2 −π (c / 2)
2 ] (1) Since the draft ratio of the falling portion is the ratio of the winding speed to the slowest portion of the spinning dope immediately after the start of solidification, it substantially represents how much the spinning dope is stretched. It can be said that the draft rate.
【００１６】本発明者の検討によると、５０ｍ／分を超
えそれ以上の高速紡糸において、中空糸の伸度、分子量
分画性を損なわずに紡糸するには、落下部ドラフト率を
２．０以下にすることが必要であることが分かった。落
下部ドラフト率を２．０よりも大きくすると、延伸の効
果で糸の伸度が低下すること、部分的な構造破壊から分
子量分画性が悪化し、アルブミン等の有用蛋白のリーク
が避けられない事、等の問題が生じてしまう。落下部ド
ラフト率の下限は特に限定しないが、中空糸膜を全く引
張らずに弛ませて紡糸すると、糸道が安定せず錘間トラ
ブル等が発生するおそれがあるので、落下部ドラフト率
の範囲は１．０を越えて２．０以下としておくと好まし
い。According to the study of the present inventor, in high-speed spinning at a speed of more than 50 m / min or more, in order to carry out spinning without impairing the elongation and the molecular weight fractionation property of the hollow fiber, the falling portion draft ratio is 2.0. I found it necessary to do the following: When the draft ratio of the falling portion is larger than 2.0, the elongation of the yarn is lowered by the effect of the drawing, and the molecular weight fractionation property is deteriorated due to the partial structural destruction, so that the leakage of useful proteins such as albumin can be avoided. There will be problems such as not being. The lower limit of the draft ratio of the falling portion is not particularly limited, but if the hollow fiber membrane is loosened without being stretched at all and spun, the yarn path may not be stable, and problems such as inter-weight problems may occur. The range is preferably more than 1.0 and 2.0 or less.
【００１７】紡糸口金から吐出される中空内液および紡
糸原液の吐出線速度は、各々絶対値としては重要ではな
いので範囲を特に限定しないが、相対的なこれらの線速
度比を特定することはバラス効果を抑制する上で重要で
ある。紡糸口金から吐出された紡糸原液は、自重に加え
て中空内液の流れの影響も受けながら空走部を経て凝固
浴に導かれるため、中空内液の吐出線速度を落下部吐出
線速度に比して相対的に高めることが、紡糸原液が必要
以上に延伸される作用を緩和する上で好ましい。この線
速度比、即ち、中空内液の吐出線速度を紡糸原液の落下
部吐出線速度で除した値は、５倍以上１０倍以下である
ことが好ましく、中空内液の吐出線速が遅いと巻き取り
の力で延伸され、膜構造の破壊が生じて中空糸の伸度が
低下する。反対に、中空内液の吐出線速が紡糸原液の落
下部吐出線速度よりも速すぎると、中空内液と紡糸原液
の速度差から、中空糸内表面の構造破壊、構造の不均一
化が起こるので好ましくない。従って、線速度比は５倍
以上１０倍以下が好ましく、より好ましくは６倍以上
９．５倍以下である。The discharge linear velocities of the hollow internal liquid and the spinning dope which are discharged from the spinneret are not particularly limited in terms of absolute values, so the ranges are not particularly limited, but it is not possible to specify the relative linear velocity ratios thereof. It is important for suppressing the balass effect. The spinning dope discharged from the spinneret is guided to the coagulation bath through the idle section while being affected by the flow of the hollow internal liquid in addition to its own weight, so the discharge linear velocity of the hollow internal liquid becomes the discharge linear velocity of the falling part. It is preferable to relatively increase the ratio in order to alleviate the effect that the spinning dope is drawn more than necessary. This linear velocity ratio, that is, the value obtained by dividing the discharge linear velocity of the hollow inner liquid by the drop linear discharge linear velocity is preferably from 5 times to 10 times, and the discharge linear velocity of the hollow internal liquid is slow. The film is stretched by the force of winding and the membrane structure is broken, and the elongation of the hollow fiber is reduced. On the other hand, if the discharge linear velocity of the hollow inner liquid is too fast than the discharge linear velocity of the spinning stock solution at the falling portion, structural damage and non-uniform structure of the inner surface of the hollow fiber may occur due to the difference in velocity between the hollow inner liquid and the spinning stock solution. It is not preferable because it will occur. Therefore, the linear velocity ratio is preferably 5 times or more and 10 times or less, more preferably 6 times or more and 9.5 times or less.
【００１８】また、この時、落下部の空走距離も重要で
あり、空走距離が短すぎると紡糸口金から吐出した紡糸
原液の落下部吐出線速がまだ遅いうちに凝固浴に入り、
凝固するため、巻き取りからの力で延伸され、中空糸の
伸度が低下する。また、空走距離が長すぎると凝固浴に
進入する速度が速すぎて、落下部及び凝固浴上で中空糸
が激しく動き、生産性に問題が生じる。従って空走距離
は５０ｃｍ〜１５０ｃｍが好ましく、より好ましくは８
０ｃｍ〜１１０ｃｍである。At this time, the idling distance of the falling portion is also important. If the idling distance is too short, the spinning stock solution discharged from the spinneret enters the coagulation bath while the linear velocity of the dropping portion is still slow.
Since it solidifies, it is stretched by the force from the winding, and the elongation of the hollow fiber decreases. Further, if the idle running distance is too long, the speed of entering the coagulation bath is too high, and the hollow fibers move violently on the falling part and on the coagulation bath, causing a problem in productivity. Therefore, the free running distance is preferably 50 cm to 150 cm, more preferably 8 cm.
It is 0 cm to 110 cm.
【００１９】落下部ドラフト率を２．０以下にするため
に重要なことは、紡糸原液の粘度を適切な範囲に設定す
ることである。紡糸原液粘度が低い方が、バラス効果の
影響が少なく、落下部ドラフト率は低くなるのである
が、紡糸原液粘度が低すぎる場合、膜内部に大きなマク
ロボイドが顕著に現れるようになる。血液浄化用の中空
糸膜の場合、こうしたマクロボイドが多数存在すると、
血液透析中に血液凝固が起こりやすくなり、血液透析に
用いる中空糸膜においてはマクロボイドがないことが好
ましい。ここで言うマクロボイドとは膜内でポリマーが
存在しない空間のうち、その最大径が５μｍ以上のもの
を言う。一方、原液粘度が高くなりすぎると紡糸原液吐
出時のバラス効果が大きくなり、落下部ドラフト率が上
昇するだけでなく、紡糸口金前の圧力が上がりすぎ、安
定な紡糸ができなくなってくる。従って、本発明では、
紡糸原液粘度は１０００ｍＰａ・ｓ以上３５００ｍＰａ
・ｓ以下の範囲が好ましい。本発明で言う粘度とは、製
膜条件下の紡糸口金温度と同温度で紡糸原液を回転式の
粘度計で測定したものである。What is important for setting the draft ratio of the falling portion to 2.0 or less is to set the viscosity of the spinning dope to an appropriate range. The lower the viscosity of the spinning dope, the less the influence of the ballast effect and the lower the draft ratio of the falling portion. However, if the viscosity of the spinning dope is too low, large macrovoids will appear remarkably inside the film. In the case of hollow fiber membranes for blood purification, if there are many such macrovoids,
Blood coagulation easily occurs during hemodialysis, and it is preferable that the hollow fiber membrane used for hemodialysis has no macrovoids. The term "macrovoid" used herein refers to a space having a maximum diameter of 5 µm or more in a space where no polymer exists in the film. On the other hand, if the viscosity of the stock solution is too high, the dispersion effect at the time of discharging the stock solution for the spinning becomes great, and not only the draft ratio at the falling portion rises, but also the pressure before the spinneret rises too much to make stable spinning impossible. Therefore, in the present invention,
The spinning solution viscosity is 1000 mPa · s or more and 3500 mPas.
-A range of s or less is preferable. The term “viscosity” as used in the present invention means that the spinning dope is measured with a rotary viscometer at the same temperature as the spinneret temperature under film forming conditions.
【００２０】なお、紡糸原液の粘度は、原液に溶解する
ポリマーの分子量、及び濃度、紡糸原液の温度等に依存
し、どの要因も膜構造の形成に重大な影響を及ぼす。紡
糸原液の組成も原液粘度を左右するが、本発明の紡糸原
液の組成は公知の組成のものなら何でもよく、特に組成
範囲を設けない。用いる原料を適切に選択し、濃度およ
び温度の条件を設定することにより、上記の範囲に原液
粘度を調整すればよい。The viscosity of the stock solution for spinning depends on the molecular weight and concentration of the polymer dissolved in the stock solution, the temperature of the stock solution for spinning, and any factor has a significant influence on the formation of the membrane structure. The composition of the spinning dope also influences the viscosity of the dope, but the composition of the spinning dope of the present invention may be any known composition, and no particular composition range is set. The stock solution viscosity may be adjusted to the above range by appropriately selecting the raw material to be used and setting the concentration and temperature conditions.
【００２１】落下部ドラフト率を２．０以下にする上で
次に重要なことは、紡糸口金の設計である。中空内液の
吐出線速度もバラス効果に影響し、線速度が大きいほど
バラス効果を抑制することができる。中空内液の吐出線
速度は紡糸口金の中空内液吐出部の断面積を制御するこ
とによって達成され、吐出面積を小さくすれば吐出線速
度は速くなり、吐出面積を大きくすれば吐出線速度は遅
くなる。面積範囲は、設定する中空糸の内径、膜厚によ
って決めれば良いが、通常の血液浄化用途に用いる場
合、０．５×１０−４ｃｍ２〜３．０×１０−４ｃｍ２
の範囲が好ましい。また、この時、原液吐出部の面積と
の比すなわち原液吐出部の面積を内液吐出部の面積で除
した値が４．０〜９．０の範囲にあることが好ましい。
この範囲にすることにより、紡糸時に内液吐出線速度を
原液吐出線速度で除した値を５倍以上、１０倍以下にす
ることができる。なお、原液原液吐出部の面積は、図１
によれば、π（a／2）２−π（ｃ／2） ２であり、内液
吐出部の面積はπ（d／2）2である。In order to make the draft ratio of the falling part 2.0 or less,
Next important is the design of the spinneret. Of hollow liquid
The discharge linear velocity also affects the ballast effect, and the higher the linear velocity
The crowbar effect can be suppressed. Discharge line for hollow liquid
The speed can control the cross-sectional area of the liquid discharge part in the hollow of the spinneret.
The linear velocity of discharge can be achieved by reducing the discharge area.
The discharge linear velocity becomes slower if the discharge area is increased.
Become The area range depends on the inner diameter and thickness of the hollow fiber to be set.
However, if you use it for normal blood purification purposes,
0.5 x 10-4cmTwo~ 3.0 x 10-4cmTwo
Is preferred. At this time, the area of the stock solution discharge part
Ratio, that is, the area of the stock solution discharge part is divided by the area of the inner solution discharge part.
It is preferable that the above value is in the range of 4.0 to 9.0.
By setting this range, the internal liquid discharge linear velocity during spinning
The value divided by the stock solution discharge linear velocity should be 5 times or more and 10 times or less.
You can In addition, the area of the undiluted solution undiluted solution discharge part is shown in FIG.
According to, π (a / 2)Two-Π (c / 2) TwoAnd the internal liquid
Area of discharge part is π (d / 2)2Is.
【００２２】一方、紡糸原液に関しては、紡糸原液吐出
スリット幅の中空糸膜厚に対する割合（膜厚比）が±２
０％以内にあることが好ましい。中空糸膜厚に対して＋
２０％より大きい場合、延伸しなければ設定膜厚になら
ないため、落下部ドラフト率が大きくなってしまう。ま
た、−２０％以下になると、落下部ドラフト率は低く設
定できるが、紡糸原液吐出スリット幅が狭くなりすぎる
ため、紡糸口金での圧損が大きくなり、紡糸が不安定に
なりやすい。また、原液の吐出ムラが生じるため、膜構
造が乱れ、透水性能、溶質透過性能のバラツキも大きく
なる。さらに、スリット幅が狭いため、紡糸口金の芯合
わせが困難になること、紡糸口金の作成自体が困難にな
り高コストになることなどの問題が指摘される。On the other hand, for the spinning dope, the ratio of the width of the spinning dope discharge slit to the hollow fiber film thickness (film thickness ratio) is ± 2.
It is preferably within 0%. + For hollow fiber membrane thickness
If it is more than 20%, the set film thickness cannot be achieved unless it is stretched, so that the draft ratio of the falling portion becomes large. When it is -20% or less, the draft ratio of the falling portion can be set to be low, but the width of the spinning stock solution discharge slit is too narrow, resulting in a large pressure loss at the spinneret, and the spinning tends to be unstable. Moreover, since the discharge of the undiluted solution occurs, the membrane structure is disturbed, and the variations in water permeability and solute permeability become large. Furthermore, since the slit width is narrow, it is pointed out that it is difficult to align the cores of the spinneret, and it is difficult to manufacture the spinneret itself, resulting in high cost.
【００２３】また、バラス効果を抑制するための紡糸口
金の設計に関しては、紡糸原液吐出部の長さ／径の比で
あるＬ／Ｄが０．５以上２．５以下である紡糸口金を使
用して紡糸する事が必要である。Ｌ／Ｄが０．５以下で
は、紡糸原液の直線性が不十分で中空糸形状が安定せ
ず、偏芯が起こりやすい。また、Ｌ／Ｄが２．５以上で
は紡糸口金での圧損が大きくなり、紡糸が不安定とな
る。尚、ここでいう紡糸原液吐出部のＬ／Ｄとは、図２
に示すように、紡糸口金中の紡糸原液の流路のうち、吐
出までの直線部分の長さを径で除した値である。Regarding the design of the spinneret for suppressing the loosening effect, a spinneret having a length / diameter ratio L / D of the spinning solution discharge portion of 0.5 or more and 2.5 or less is used. Then it is necessary to spin. When L / D is 0.5 or less, the linearity of the spinning dope is insufficient, the hollow fiber shape is not stable, and eccentricity is likely to occur. On the other hand, when L / D is 2.5 or more, pressure loss in the spinneret becomes large, and spinning becomes unstable. In addition, the L / D of the spinning dope ejecting section referred to here means
As shown in (3), it is a value obtained by dividing the length of the straight line portion up to discharge in the flow path of the spinning dope in the spinneret by the diameter.
【００２４】本発明の紡糸速度範囲は５０ｍ／分を超え
それ以上の高速であり、生産性の点から好ましくは６０
ｍ／分以上、より好ましくは７０ｍ／以上である。上限
は特に設けないが、落下部ドラフト率を２．０以下にし
ても、紡糸速度が極端に速くなると、伸度低下を起こし
たり、分子量分画性や紡糸安定性が悪化傾向を示すの
で、上限が１５０ｍ／分以下であることが好ましく、よ
り好ましくは１２０ｍ／分以下である。ノズルドラフト
については、紡糸性の点から０．９５以上であればよい
が、ノズルドラフトが大き過ぎると、膜の微細構造が破
壊される傾向にあるので、上限を１．３に留めることが
好ましい。The spinning speed range of the present invention is higher than 50 m / min, and is higher than 50 m / min. From the viewpoint of productivity, it is preferably 60.
m / min or more, more preferably 70 m / min or more. Although the upper limit is not particularly set, even if the draft ratio of the falling portion is 2.0 or less, if the spinning speed becomes extremely high, the elongation may decrease, and the molecular weight fractionation property and the spinning stability tend to deteriorate. The upper limit is preferably 150 m / min or less, more preferably 120 m / min or less. The nozzle draft may be 0.95 or more from the viewpoint of spinnability, but if the nozzle draft is too large, the fine structure of the film tends to be destroyed, so it is preferable to keep the upper limit to 1.3. .
【００２５】上記のようにして、紡糸され、巻き取られ
た中空糸は公知の方法で後処理される。すなわち、熱水
等による洗浄で溶剤及び過剰なＰＶＰが除去され、乾熱
乾燥される。また、中空糸を巻き取った後に後処理する
のでなく、熱水等による洗浄や乾熱乾燥した後に巻き取
る方法も本発明の範囲内である。The hollow fiber which has been spun and wound up as described above is post-treated by a known method. That is, the solvent and excess PVP are removed by washing with hot water or the like, and dry heating is performed. Further, it is within the scope of the present invention to use a method in which the hollow fiber is not subjected to post-treatment after being wound up, but is washed with hot water or the like and dried and dried to be wound up and then wound up.
【００２６】[0026]
【実施例】以下に実施例及び比較例を用いて本発明を詳
細に説明するが、本発明はこれにより何ら限定されるも
のではない。本発明での透水量および篩い係数は、以下
のように測定したものである。すなわち、乾燥させたポ
リスルホン中空糸膜１００本からなるミニモジュール
（有効長１８ｃｍ）を組立成型し、膜間圧力差を２００
ｍｍＨｇとしてストップ法にて透水量を測定した（単位
はｍｌ／Ｈｒ／ｍ2／ｍｍＨｇ）。続いてさらに、人血
清を用いてβ２−ミクログロブリン（以下β２−ｍ
ｇ）、アルブミン（以下Ａｌｂ）の篩い係数を測定し
た。篩い係数の測定は、０．４ｃｍ／ｓｅｃの線速にな
るように流量を調整し、膜間圧力差２５ｍｍＨｇの濾過
圧力をかけて次式から算出した。β２−ｍｇおよびＡｌ
ｂの濃度は、それぞれＥＩＡ法、ＢＣＧ法を用いて求め
た。
篩い係数 ＝ 濾液の濃度 ／ 元液の濃度
尚、人血清は使用前、生理食塩水を加えて総タンパク濃
度を６．５ｇ／ｄｌになるように調整したものを用い
た。中空糸の伸度はＯＲＩＥＮＴＥＣ社ＴＥＮＳＩＬＯ
Ｎ；ＲＴＣ−１２１０を用い、中空糸膜を破断するまで
引っ張り、その時の伸びを伸度とした。The present invention will be described in detail below with reference to examples and comparative examples, but the present invention is not limited thereto. The water permeability and the sieving coefficient in the present invention are measured as follows. That is, a mini-module (effective length 18 cm) consisting of 100 dried polysulfone hollow fiber membranes was assembled and molded, and the transmembrane pressure difference was set to 200.
The water permeation rate was measured by the stop method as mmHg (unit: ml / Hr / m 2 / mmHg). Subsequently, using human serum, β 2 -microglobulin (hereinafter β 2 -m
g), the sieving coefficient of albumin (hereinafter referred to as Alb) was measured. The sieving coefficient was measured by adjusting the flow rate so that the linear velocity was 0.4 cm / sec, applying a filtration pressure with a transmembrane pressure difference of 25 mmHg, and calculating from the following equation. β 2 -mg and Al
The concentration of b was determined using the EIA method and the BCG method, respectively. Sieving coefficient = Concentration of filtrate / Concentration of original solution Human serum was used before use, which was adjusted to have a total protein concentration of 6.5 g / dl by adding physiological saline. The elongation of the hollow fiber is TENSILO of ORITEC
N; RTC-1210 was used to pull the hollow fiber membrane until it broke, and the elongation at that time was taken as the elongation.
【００２７】[0027]
【実施例１】ポリスルホン（Ｐ−１７００：ＡＭＯＣＯ
社製）１８重量部、ＰＶＰ（Ｋ−９０：ＩＳＰ社製）
４．２重量部、ＤＭＡＣ７７．８重量部を１０時間攪拌
して紡糸原液とした。この紡糸原液の粘度は、４０℃で
２６００ｍＰａ・ｓであった。この紡糸原液を５０％Ｄ
ＭＡＣ水溶液を中空内液とし、中空内液吐出面積０．７
９×１０−４ｃｍ２、落下部（ｃ）２００μｍ、紡糸原
液吐出部のスリット幅５０μｍ、紡糸原液吐出部の長さ
（Ｌ）が３００μｍ、径（Ｄ）が３００μｍ、Ｌ／Ｄが
１．０の環状口金より吐出して８５ｃｍ下方に設置した
５５℃の水中に浸漬し、巻き取り速度８０ｍ／分で巻き
取った。乾燥後の中空糸膜厚を４5μｍ、内径を２００
μｍに合わせるように紡糸原液、中空内液の吐出量を調
製したので、この時の中空内液の吐出線速度は４０８ｍ
／分、バラス効果による最も膨らんだ径（ｂ）は３５４
μｍ、落下部吐出線速度は５２．３ｍ／分で線速度比は
７．９倍であった。９５００フィラメント巻き取ったと
ころで、ロープを３００ｍｍに切断し、８５℃にて７時
間熱風乾燥させた。乾燥後、中空糸膜を二亜硫酸ナトリ
ウム３００ｐｐｍと炭酸ナトリウム１００ｐｐｍを溶解
させた水溶液に浸漬させ、２５ｋＧｙのγ線を照射し、
中空糸型ポリスルホン系血液浄化膜を得た。得られた中
空糸膜の伸度の測定、透過性能の測定を行った。これら
の結果を表１に示す。Example 1 Polysulfone (P-1700: AMOCO
18 parts by weight, PVP (K-90: manufactured by ISP)
4.2 parts by weight and 77.8 parts by weight of DMAC were stirred for 10 hours to prepare a spinning dope. The viscosity of this spinning dope was 2600 mPa · s at 40 ° C. 50% D of this spinning solution
The MAC aqueous solution is used as the hollow internal liquid, and the hollow internal liquid discharge area is 0.7
9 × 10 −4 cm 2 , falling part (c) 200 μm, slit width of spinning stock solution discharge part 50 μm, length of spinning stock solution discharge part (L) 300 μm, diameter (D) 300 μm, L / D 1. It was discharged from an annular spinneret No. 0, immersed in water at 55 ° C. installed 85 cm below, and wound at a winding speed of 80 m / min. Hollow fiber thickness after drying is 45 μm, inner diameter is 200
Since the discharge amount of the spinning dope and the hollow inner liquid were adjusted so as to be adjusted to μm, the discharge linear velocity of the hollow inner liquid at this time was 408 m.
/ Min, the most swollen diameter (b) due to the ballast effect is 354
.mu.m, the discharge part discharge linear velocity was 52.3 m / min, and the linear velocity ratio was 7.9 times. After winding 9500 filaments, the rope was cut into 300 mm and dried with hot air at 85 ° C. for 7 hours. After drying, the hollow fiber membrane was immersed in an aqueous solution in which 300 ppm of sodium disulfite and 100 ppm of sodium carbonate were dissolved, and irradiated with 25 kGy of γ-rays,
A hollow fiber type polysulfone blood purification membrane was obtained. The elongation and permeability of the obtained hollow fiber membrane were measured. The results are shown in Table 1.
【００２８】[0028]
【実施例２】紡糸原液吐出部のスリット幅５０μｍ、紡
糸原液吐出部のＬ／Ｄが１．２の環状口金を使用し、巻
き取り速度９０ｍ／分で実施例１と同様な方法で中空糸
型ポリスルホン系血液浄化膜を得た。得られた中空糸膜
の伸度の測定、透過性能の測定を行った。その他の条件
とともにこれらの結果を表１に示す。Example 2 A hollow fiber was used in the same manner as in Example 1 at a winding speed of 90 m / min using an annular spinneret having a slit width of 50 μm at the spinning dope discharge part and an L / D of 1.2 at the spinning dope discharge part. A type polysulfone-based blood purification membrane was obtained. The elongation and permeability of the obtained hollow fiber membrane were measured. The results are shown in Table 1 together with other conditions.
【００２９】[0029]
【実施例３】紡糸原液の吐出温度を６０℃とし、４８％
ＤＭＡＣ水溶液よりなる中空内液とともに紡糸口金より
吐出し、巻き取り速度１１０ｍ／分で実施例１と同様の
方法で中空糸型ポリスルホン系血液浄化膜を得た。得ら
れた中空糸膜の伸度の測定、透過性能の測定を行った。
これらの結果を表１に示す。Example 3 The discharge temperature of the spinning dope was set to 60 ° C. and 48%
A hollow fiber polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 at a winding speed of 110 m / min by discharging together with a hollow inner liquid composed of a DMAC aqueous solution. The elongation and permeability of the obtained hollow fiber membrane were measured.
The results are shown in Table 1.
【００３０】[0030]
【実施例４】中空内液吐出面積０．７９×１０−４ｃｍ
２、紡糸原液吐出部のスリット幅３５．５μｍ、紡糸原
液吐出部のＬ／Ｄが１．0の環状口金を使用して実施例
１と同様な方法で中空糸型ポリスルホン系血液浄化膜を
得た。得られた中空糸膜の伸度の測定、透過性能の測定
を行った。これらの結果を表１に示す。Ａｌｂのリーク
量がやや多いが、これは紡糸口金での圧損が大きく、紡
糸原液の吐出ムラが起こり、部分的な構造破壊が起きた
ものと推測される。[Embodiment 4] Liquid discharge area in hollow 0.79 × 10 −4 cm
2. A hollow fiber polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 by using an annular spinneret having a slit width of the spinning stock solution discharge part of 35.5 μm and an L / D of the spinning stock solution discharge part of 1.0. It was The elongation and permeability of the obtained hollow fiber membrane were measured. The results are shown in Table 1. Although the leak amount of Alb was rather large, it is presumed that this was due to large pressure loss at the spinneret, uneven discharge of the spinning dope, and partial structural destruction.
【００３１】[0031]
【実施例５】中空内液吐出面積０．４２×１０−４ｃｍ
２の紡糸口金を用いて実施例１と同様な方法で中空糸型
ポリスルホン系血液浄化膜を得た。この時の中空内液の
吐出線速度７１１ｍ／分、落下部吐出線速度５３．０ｍ
／分で線速度比は１３．４倍であった。Ａｌｂのリーク
量がやや多いが、これは線速度比が大きすぎるため、中
空糸内表面に部分的な構造破壊が生じたためと思われ
る。[Embodiment 5] Liquid discharge area in hollow 0.42 × 10 −4 cm
A hollow fiber type polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 using the spinneret No. 2 . The discharge linear velocity of the liquid in the hollow at this time was 711 m / min, and the discharge portion linear velocity of 53.0 m
The linear velocity ratio was 13.4 times / min. Although the leak amount of Alb was rather large, it is considered that this is because the linear velocity ratio was too large and a partial structural destruction occurred on the inner surface of the hollow fiber.
【００３２】[0032]
【比較例１】中空内液吐出面積１．８×１０−４ｃ
ｍ２、紡糸原液吐出部のスリット幅６０μｍ、紡糸原液
吐出部のＬ／Ｄが１．0の環状口金を使用し、８０ｍ／
分の紡速で実施例１と同様な方法で中空糸型ポリスルホ
ン系血液浄化膜を得た。得られた中空糸膜の伸度の測
定、透過性能の測定を行った。これらの結果を表１に示
す。紡糸原液吐出部のスリット幅が広いために落下部ド
ラフト率が高くなり、糸伸度が低下している。また、Ａ
ｌｂのリーク量もやや多いが、これは落下部ドラフト率
が大きく、部分的な構造破壊が起こったためと推察され
る。[Comparative Example 1] Discharge area of liquid in the hollow 1.8 × 10 −4 c
m 2, the slit width 60μm of spinning solution discharge portion, the L / D of the spinning dope discharged unit by using an annular die of 1.0, 80 m /
A hollow fiber type polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 at a spinning speed of 1 minute. The elongation and permeability of the obtained hollow fiber membrane were measured. The results are shown in Table 1. Since the slit width of the spinning dope discharge portion is wide, the draft ratio of the falling portion is high and the yarn elongation is low. Also, A
The leak amount of lb is also slightly large, but it is presumed that this is because the draft ratio of the falling portion is large and partial structural destruction occurs.
【００３３】[0033]
【比較例２】中空内液吐出面積０．７９×１０−４ｃｍ
２、紡糸原液吐出部のＬ／Ｄが０．３の紡糸口金を使用
して実施例１と同様な方法で中空糸型ポリスルホン系血
液浄化膜を得た。得られた中空糸膜は中空形状が安定せ
ず、厚い部分と薄い部分が脈動していたため、透過性能
の評価を省略した。[Comparative Example 2] Liquid discharge area in hollow 0.79 × 10 −4 cm
2. A hollow fiber type polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 using a spinneret having an L / D of 0.3 at the spinning dope discharge portion. Since the hollow shape of the obtained hollow fiber membrane was not stable and the thick and thin portions were pulsating, the evaluation of the permeation performance was omitted.
【００３４】[0034]
【比較例３】中空内液吐出面積０．７９×１０−４ｃｍ
２、紡糸原液吐出部のＬ／Ｄが２．７の紡糸口金を使用
して実施例１と同様な方法で中空糸型ポリスルホン系血
液浄化膜を得た。紡糸口金での圧損が大きく、吐出が不
安定、脈動、糸切れ多発等を繰り返し、また、紡糸原液
ラインからの紡糸原液漏れも多発し、紡糸の継続ができ
なかった。[Comparative Example 3] Liquid discharge area in hollow 0.79 × 10 −4 cm
2. A hollow fiber type polysulfone-based blood purification membrane was obtained in the same manner as in Example 1 by using a spinneret with an L / D of the spinning solution dosing part of 2.7. The pressure loss at the spinneret was large, discharge was unstable, pulsation, frequent yarn breakage, etc. were repeated, and spinning stock solution leaked frequently from the spinning stock solution line, making it impossible to continue spinning.
【００３５】[0035]
【表１】 [Table 1]
【００３６】[0036]
【発明の効果】以上述べたように、本発明の中空糸型ポ
リスルホン系血液浄化膜は従来技術の問題点を解消し、
紡速６０ｍ／分以上の高紡速においても糸伸度が低下す
ることなく、分子量分画性にも優れた中空糸膜を提供す
ることが可能となり、生産性に大きく寄与することが期
待できる。As described above, the hollow fiber type polysulfone-based blood purification membrane of the present invention solves the problems of the prior art,
It is possible to provide a hollow fiber membrane excellent in molecular weight fractionation without lowering the yarn elongation even at a high spinning speed of 60 m / min or more, which can be expected to greatly contribute to productivity. .
【図１】紡糸原液吐出部における紡糸原液の流れを示す
模式図である。FIG. 1 is a schematic diagram showing a flow of a spinning dope in a spinning dope discharge part.
【図２】紡糸口金の断面図を示す。FIG. 2 shows a cross-sectional view of a spinneret.
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） // Ｄ０１Ｄ 4/02 Ｄ０１Ｄ 4/02 Ｆターム(参考） 4C077 AA05 BB01 CC01 LL05 PP15 4D006 GA13 MA01 MB06 MB09 MC34 MC37 MC39 MC40X MC49 MC54 MC62X MC63 MC83 NA04 NA19 NA54 NA64 PA01 PB09 PB52 PB70 PC47 4L035 BB04 BB06 BB07 BB22 CC13 DD03 FF07 MF02 4L045 AA03 BA24 BA58 CB08 DC02Front page continuation (51) Int.Cl. 7 Identification code FI theme code (reference) // D01D 4/02 D01D 4/02 F term (reference) 4C077 AA05 BB01 CC01 LL05 PP15 4D006 GA13 MA01 MB06 MB09 MC34 MC37 MC39 MC40X MC49 MC54 MC62X MC63 MC83 NA04 NA19 NA54 NA64 PA01 PB09 PB52 PB70 PC47 4L035 BB04 BB06 BB07 BB22 CC13 DD03 FF07 MF02 4L045 AA03 BA24 BA58 CB08 DC02
Claims (7)
なる紡糸口金より中空内液とともに吐出して紡糸する中
空糸型血液浄化膜の製造方法であって、紡糸原液吐出部
の長さ／径が０．５以上２．５以下である紡糸口金を使
用して、落下部ドラフト率を２．０以下で紡糸すること
を特徴とする中空糸型血液浄化膜の製造方法。1. A method for producing a hollow fiber type blood purification membrane in which a spinning dope is discharged together with a hollow inner liquid from a spinneret having a tube-in orifice for spinning, and the spinning dope discharge part has a length / diameter of 0. A method for producing a hollow fiber blood purification membrane, which comprises spinning at a falling portion draft ratio of 2.0 or less using a spinneret of 5 or more and 2.5 or less.
することを特徴とする請求項１記載の中空糸型血液浄化
膜の製造方法。2. The method for producing a hollow fiber type blood purification membrane according to claim 1, wherein the spinning is performed at a winding speed exceeding 50 m / min.
上３５００ｍＰａ・ｓ以下であることを特徴とする請求
項１または２記載の中空糸型血液浄化膜の製造方法。3. The method for producing a hollow fiber blood purification membrane according to claim 1 or 2, wherein the spinning dope has a viscosity of 1000 mPa · s or more and 3500 mPa · s or less.
部吐出線速度で除した線速度比が５以上１０以下で紡糸
することを特徴とする請求項１〜３のいずれかに記載の
中空糸型血液浄化膜の製造方法。4. The spinning according to any one of claims 1 to 3, wherein the linear velocity ratio obtained by dividing the discharge linear velocity of the hollow internal liquid by the drop linear discharge linear velocity of the spinning dope is 5 or more and 10 or less. 1. A method for producing a hollow fiber type blood purification membrane.
で除した値が４．０以上９．０以下である紡糸口金を使
用して紡糸する請求項１〜４のいずれかに記載の中空糸
方血液浄化膜の製造方法5. The spinning spinneret according to claim 1, wherein a value obtained by dividing the area of the spinning stock solution discharge part by the area of the internal liquid discharge part is 4.0 or more and 9.0 or less. Method for producing hollow fiber type blood purification membrane described
厚に対して±２０％以内にして紡糸することを特徴とす
る請求項１〜５のいずれかに記載の中空糸型血液浄化膜
の製造方法。6. The hollow fiber type blood purification membrane according to any one of claims 1 to 5, wherein the spinning stock solution discharge part has a slit width within ± 20% of the hollow fiber membrane thickness for spinning. Manufacturing method.
溶剤よりなる紡糸原液を用いてポリスルホン系血液浄化
膜を製造する請求項１〜６のいずれかに記載の方法。7. The method according to any one of claims 1 to 6, wherein a polysulfone-based blood purification membrane is produced using a spinning dope containing polysulfone, polyvinylpyrrolidone and a solvent.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006187768A (en) * | 2004-12-09 | 2006-07-20 | Toray Ind Inc | Production method of polysulfone type hollow fiber membrane and production method of module for medical care using it |
| US7786233B2 (en) | 2007-01-26 | 2010-08-31 | Nippon Shokubai Co., Ltd. | Polyvinylpyrrolidone powder compositions |
| JP2013509502A (en) * | 2009-10-29 | 2013-03-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing hyperbranched hollow fiber |
| US9616393B2 (en) | 2007-12-06 | 2017-04-11 | Asahi Kasei Medical Co., Ltd. | Porous hollow fiber membrane for treating blood |
| CN110064310A (en) * | 2019-05-15 | 2019-07-30 | 海宁一泓环境科技有限公司 | A kind of production technology of fiber tube enhancement type doughnut composite biological film |
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2002
- 2002-12-18 JP JP2002366428A patent/JP4036740B2/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2006187768A (en) * | 2004-12-09 | 2006-07-20 | Toray Ind Inc | Production method of polysulfone type hollow fiber membrane and production method of module for medical care using it |
| US7786233B2 (en) | 2007-01-26 | 2010-08-31 | Nippon Shokubai Co., Ltd. | Polyvinylpyrrolidone powder compositions |
| US9616393B2 (en) | 2007-12-06 | 2017-04-11 | Asahi Kasei Medical Co., Ltd. | Porous hollow fiber membrane for treating blood |
| JP2013509502A (en) * | 2009-10-29 | 2013-03-14 | ビーエーエスエフ ソシエタス・ヨーロピア | Method for producing hyperbranched hollow fiber |
| US9234302B2 (en) | 2009-10-29 | 2016-01-12 | Basf Se | Process for the preparation of hyperbranched hollow fibers |
| CN110064310A (en) * | 2019-05-15 | 2019-07-30 | 海宁一泓环境科技有限公司 | A kind of production technology of fiber tube enhancement type doughnut composite biological film |
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