JPH0333208A - Production of hollow fiber - Google Patents
Production of hollow fiberInfo
- Publication number
- JPH0333208A JPH0333208A JP16604389A JP16604389A JPH0333208A JP H0333208 A JPH0333208 A JP H0333208A JP 16604389 A JP16604389 A JP 16604389A JP 16604389 A JP16604389 A JP 16604389A JP H0333208 A JPH0333208 A JP H0333208A
- Authority
- JP
- Japan
- Prior art keywords
- spinning
- fluid
- hollow fibers
- nozzle
- spinneret
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Landscapes
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明は、２重管型口金を用いた中空繊維の製造方法に
関する。さらに詳細には特定の紡糸条件を用いた多孔性
中空繊維状の分離膜の製造方法に関する。DETAILED DESCRIPTION OF THE INVENTION <Industrial Application Field> The present invention relates to a method for producing hollow fibers using a double tube type die. More specifically, the present invention relates to a method for producing a porous hollow fiber separation membrane using specific spinning conditions.
〈従来技術〉
一般に、多孔性中空繊維状の分離膜の製造に用いられる
２重管型口金は紡糸口金孔に細管を挿入し紡糸時に液体
あるいは気体を芯剤として注入する方法がある。複数ホ
ールをもつ２重管型口金の場合、内側管より流体を注入
した場合、流体の配分斑が発生しやすく、特に紡糸用ポ
リマー原液の粘度が低い場合は、該口金部の各ホール部
の温度斑、ポリマーの粘度斑、及び流体の吐出圧力の変
動により中空繊維の糸径に変動が誘発されやすい。<Prior Art> In general, a double-tube type spinneret used for producing a porous hollow fiber separation membrane has a method in which a thin tube is inserted into the spinneret hole and a liquid or gas is injected as a core agent during spinning. In the case of a double-tube type nozzle with multiple holes, when fluid is injected from the inner tube, uneven distribution of fluid tends to occur.Especially when the viscosity of the polymer stock solution for spinning is low, each hole in the nozzle Fluctuations in the diameter of the hollow fibers are likely to occur due to variations in temperature, viscosity of the polymer, and fluid discharge pressure.
このため、種々の条件管理が必要で且つ複雑化する等の
問題があった。For this reason, there are problems such as the necessity of managing various conditions and the complexity of the management.
〈発明の目的〉
本発明者はかかる従来の問題点を解消することを目的に
して、鋭意研究した結果、２重管型口金において、流体
を流す際の内側管の流体の圧損Ａ（ｍｍＨｚ Ｏ／ｃｌ
）を、吐出後において所定の中空繊維の内径に保持す
るに要するための圧力Ｂ（ｍｍＨｚＯ／ｃｄ）と等しい
か、それよりも高くすることにより流体の各ホールへの
分配を均一化することが容易となり、該中空繊維の内径
斑が改善されることを見出だして本発明に到達した。<Purpose of the Invention> With the aim of solving such conventional problems, the present inventor conducted extensive research and found that the pressure drop A (mmHz O /cl
) is equal to or higher than the pressure B (mmHzO/cd) required to maintain the inner diameter of the hollow fiber at a predetermined value after ejection, thereby uniformizing the distribution of the fluid to each hole. The present invention has been achieved by discovering that the inner diameter unevenness of the hollow fibers can be improved.
〈発明の構成〉
本発明は、２重管壁紡糸口金を用い、該紡糸口金の内側
管の内部から芯剤としての流体を流出させながら紡糸を
行う中空繊維の製造方法において、該紡糸口金の内側管
の内部から該流体が流出する際の圧力損失Ａ ［ｍｍＨ
２Ｏ／ｃｍ２］と該合糸口金より吐出されて中空繊維状
をなす成形物の内部における該流体の圧力Ｂ ［ｍｍＨ
ｚＯ／ｃｆｆｌ］が下記式（１）％式％
（）
を満たすことを特徴とする中空繊維の製造方法を提供す
るものである。<Structure of the Invention> The present invention provides a hollow fiber manufacturing method in which a double-walled spinneret is used and spinning is performed while a fluid as a core material flows out from the inside of the inner tube of the spinneret. Pressure loss A [mmH] when the fluid flows out from the inside of the inner tube
2O/cm2] and the pressure B [mmH
zO/cffl] satisfies the following formula (1) % formula % ().
かかる本発明の中空繊維の製造方法には、芯剤としての
流体に気体を用いることを特徴とした方法が含まれる。The method for producing hollow fibers of the present invention includes a method characterized in that a gas is used as a fluid as a core material.
さらに本発明の中空繊維の製造方法には、２重管壁紡糸
口金から吐出する際の紡糸用原液の粘度を５０〜１００
０ ｐｏｉｓｅの範囲内となるようにすることを特徴と
した製造方法が含まれる。尚かかる中空繊維の製造方法
には、紡糸原液としてセルロースエステル及びその可塑
剤を含有した可塑化溶融液を用いる方法が含まれる。Furthermore, in the method for producing hollow fibers of the present invention, the viscosity of the spinning stock solution when discharged from the double-walled spinneret is 50 to 100.
This includes a manufacturing method characterized in that the poise is within a range of 0 poise. The method for manufacturing such hollow fibers includes a method using a plasticized melt containing cellulose ester and its plasticizer as a spinning dope.
またかかる本発明の中空繊維の製造方法には、流体分離
用の多孔性中空繊維の製造方法が含まれる。The method for producing hollow fibers of the present invention also includes a method for producing porous hollow fibers for fluid separation.
以下、本発明についてさらに詳細に説明する。The present invention will be explained in more detail below.
本発明の１例として、セルロースジアセテートの可塑化
溶融紡糸の場合について説明する。As an example of the present invention, a case of plasticized melt spinning of cellulose diacetate will be described.
セルロースジアセテート１００重量部に対して、可塑剤
を１５０重量部の混合物をエクストルーダー溶融混練し
、溶融ポリマーを複数ホールを備えた従来の２重管型口
金を用いて、内側の管内より窒素ガスを注入しながら外
側の管状スリットよりポリマーの可塑化溶融液を中空繊
維状に吐出し、口金直下で風で冷却固化した後、該中空
繊維を捲取った。A mixture of 100 parts by weight of cellulose diacetate and 150 parts by weight of plasticizer is melt-kneaded using an extruder, and the molten polymer is heated with nitrogen gas from the inner tube using a conventional double-tube nozzle equipped with multiple holes. The plasticized molten liquid of the polymer was discharged in the form of hollow fibers from the outer tubular slit while being injected, and after being cooled and solidified by air directly under the nozzle, the hollow fibers were wound up.
かかる可塑化溶融紡糸では通常、可塑化溶融液の粘度が
１００ ｐｏｉｓｅ程度と低く、２重管型口金の内側管
より気体を注入して、中空繊維の内径を保持するための
気体の注入圧力（分配圧力〉は約５ｍｍＨ２Ｏ／−で、
内側管内での圧力損失が約１ ｍｍＨｚＯ／ｃｇｌと低
い。このため可塑化溶融液の吐出時における粘度斑、口
金部の各ホール間の吐出斑及び気体の注入圧力変動等の
微少な変動により気体の分配変動が生じやすい。その結
果、口金吐出面で吐出された中空繊維の内径が脈動状に
樹膜・収縮する現象を誘発し、得られる中空繊維の糸径
に変動を生じる。In such plasticized melt spinning, the viscosity of the plasticized melt is usually as low as about 100 poise, and gas is injected from the inner tube of a double tube type spinneret to maintain the inner diameter of the hollow fiber. Distribution pressure> is approximately 5 mmH2O/-,
The pressure loss within the inner tube is as low as approximately 1 mmHzO/cgl. Therefore, fluctuations in gas distribution tend to occur due to minute fluctuations such as viscosity irregularities during discharge of the plasticized melt, discharge irregularities between holes in the mouthpiece, and fluctuations in gas injection pressure. As a result, the inner diameter of the hollow fibers discharged from the nozzle discharge surface induces a phenomenon in which the inner diameter of the hollow fibers pulsates and contracts, causing fluctuations in the diameter of the hollow fibers obtained.
そこで、２重管壁紡糸口金の気体注入管における気体の
流れの圧力損失について種々検討した結果、気体注入管
における気体の流れの圧力損失を適正にすることにより
、紡糸原液側の粘度斑や紡糸口金の温度斑、吐出斑等の
影響を軽減することが可能であって、中空繊維の糸径の
均一化がはかれる。Therefore, as a result of various studies on the pressure loss of the gas flow in the gas injection tube of a double-walled spinneret, we found that by optimizing the pressure loss of the gas flow in the gas injection tube, viscosity unevenness on the spinning dope side could be reduced. It is possible to reduce the influence of temperature unevenness of the die, ejection unevenness, etc., and the diameter of the hollow fibers can be made uniform.
この場合の２重管壁紡糸口金の内側管内での気体流れの
圧力損失Ａ （ｍｍＨｚｏ／ｃｄ）と、口金より吐出さ
れたポリマー含有液からなる中空繊維状物の内径を所定
の大きさに保持するのに要する気体の圧力をＢ （ｍｄ
ｂｏ／ａｌりとの関係がＢ≦Ａ≦１０Ｂの範囲であれば
、中空繊維の糸径斑の少ない良好なものが得られること
を見出だし、本発明に至ったものである。Ａ＜Ｈの条件
下では、紡糸原液の吐出斑、２重管壁紡糸口金の温度斑
、気体の注入圧変動等の影響を受けて、中空繊維の糸径
斑が発生しやすい。Ａ＞ＩＯＢの条件下については、気
体流通時の圧損をもたすために気体注入管の口径を小さ
くすることが必要であるが、管径が小さくなり過ぎるた
め、工作上の問題を生じ好ましくない。In this case, the pressure loss A (mmHz/cd) of the gas flow within the inner tube of the double-walled spinneret and the inner diameter of the hollow fibrous material made of the polymer-containing liquid discharged from the spinneret are maintained at a predetermined size. B (md
It has been discovered that if the relationship between bo/al is within the range of B≦A≦10B, good hollow fibers with less unevenness in yarn diameter can be obtained, leading to the present invention. Under the condition of A<H, uneven yarn diameter of the hollow fibers is likely to occur due to the effects of uneven discharge of the spinning dope, uneven temperature of the double-walled spinneret, fluctuations in gas injection pressure, and the like. Under the condition of A>IOB, it is necessary to reduce the diameter of the gas injection pipe to reduce the pressure drop during gas flow, but since the pipe diameter becomes too small, this causes problems in construction and is not desirable. do not have.
本発明の中空繊維の製造方法における２重管紡糸口金の
内側管の内部から芯剤として流出させる流体としては、
液体であっても気体であってもよい。かかる流体が圧縮
性である場合、即ち気体の場合には、得られる中空繊維
の内径の変動を生じやすいことから、本発明を適用する
ことが有効となる。またかかる芯剤としての流体として
は、吐出された中空繊維用素材に対して悪影響を与える
ことのない不活性なものが好ましく、例えば気体の場合
には窒素ガスがあげられる。In the method for producing hollow fibers of the present invention, the fluid discharged as a core agent from the inside of the inner tube of the double-tube spinneret includes:
It may be a liquid or a gas. When such a fluid is compressible, that is, when it is a gas, it is effective to apply the present invention because the inner diameter of the resulting hollow fibers tends to vary. The fluid used as the core material is preferably an inert fluid that does not have an adverse effect on the discharged hollow fiber material, such as nitrogen gas.
また本発明の中空繊維の製造方法において、２重管壁紡
糸口金から吐出する際の紡糸原液の粘度が５（１−１０
００ｐｏｉｓｅである場合に、前記式（Ｉ）の範囲内の
条件下で紡糸することが有効である。即ちかかる紡糸原
液の粘度の範囲では、圧力損失Ａが流体圧力Ｂよりも小
さい場合に得られる中空繊維の内径の変動が生じやすい
。In addition, in the method for producing hollow fibers of the present invention, the viscosity of the spinning stock solution when discharged from the double-walled spinneret is 5 (1-10
00 poise, it is effective to perform spinning under conditions within the range of formula (I). That is, within such a range of viscosity of the spinning dope, when the pressure loss A is smaller than the fluid pressure B, the inner diameter of the hollow fiber obtained tends to fluctuate.
尚、本発明の製造方法における圧力損失Ａと流体の圧力
Ｂのより好ましい範囲として、下記式（ｎ）を満足する
範囲があげられる。In addition, a more preferable range of the pressure loss A and the fluid pressure B in the manufacturing method of the present invention is a range that satisfies the following formula (n).
２Ｂ≦Ａ≦６Ｂ ・・・（ＩＩ）かかる式を満た
す条件下で紡糸すれば、実用上より確実に変動の少ない
径をもつ中空繊維を製造することができる。尚本発明に
いう流体圧力Ｂ［＋１１１１１Ｈ２０／ｃｌ ］として
は、吐出直後における中空繊維の中空部内の静圧を意味
する。2B≦A≦6B (II) If spinning is performed under conditions that satisfy this formula, hollow fibers having a diameter with less variation can be produced more reliably than in practical use. Note that the fluid pressure B [+11111H20/cl] in the present invention means the static pressure within the hollow portion of the hollow fiber immediately after discharge.
本発明の中空繊維の製造方法に適用される紡糸形式とし
ては、可塑化溶融紡糸、溶融紡糸、湿式紡糸等があげら
れる。可塑化溶融紡糸の具体例としては、セルロースジ
アセテート等のセルロースエステル類なる有機重合体と
、エチレングリコール、ポリエチレングリコール等の水
溶性多価アルコールやグリセリン重合体等の可塑剤を含
み、必要に応じて他の添加剤を含む紡糸原液を用いる方
法や、ポリエーテルスルホン等の有機重合体とメチル２
−ピロリドン、ポリエチレングリコール等の可塑剤を含
む紡糸原液を用いる方法があげられる。湿式紡糸の具体
例としては、セルロースエステル類の有機重合体とエチ
レングリコール、Ｎ−メチル２−ピロリドン、アセトン
の溶媒等を含む紡糸原液を用いる方法があげられる。Examples of the spinning methods applied to the method for producing hollow fibers of the present invention include plasticized melt spinning, melt spinning, and wet spinning. Specific examples of plasticized melt spinning include organic polymers such as cellulose esters such as cellulose diacetate, and plasticizers such as water-soluble polyhydric alcohols such as ethylene glycol and polyethylene glycol, and glycerin polymers. A method using a spinning dope containing other additives, and a method using an organic polymer such as polyether sulfone and methyl 2
- A method using a spinning dope containing a plasticizer such as pyrrolidone or polyethylene glycol is mentioned. A specific example of wet spinning is a method using a spinning stock solution containing an organic polymer of cellulose esters and a solvent such as ethylene glycol, N-methyl 2-pyrrolidone, or acetone.
本発明の製造方法によって得られる中空繊維としては、
その断面形状が円状のものの他、例えば外側に軸方向に
延長された突起部を有した異形状のものがあげられる。The hollow fiber obtained by the production method of the present invention includes:
In addition to those having a circular cross-sectional shape, for example, those having an irregular shape having a protrusion extending outward in the axial direction can be mentioned.
これらの中空繊維の好ましい大きさとしては、内径が１
００〜９００μ程度、厚さ（突起部がある場合にはそれ
を除く厚さ）が５〜３０μ程度である。The preferred size of these hollow fibers is that the inner diameter is 1
The thickness (thickness excluding any protrusions) is about 5-30μ.
またかかる中空繊維の好ましいものとして、その壁部が
多孔質である多孔性中空繊維であって、血液透析、血漿
分離、人工肺等の血液処理や、逆浸透、限外濾過等の水
処理等の流体分離用多孔性中空繊維が特に好適なものと
してあげられる。尚、多孔性中空繊維を製造方法の場合
には、壁部を多孔化するための処理が必要である。例え
ば可塑化溶融紡糸の場合には、前記し、た如き所定の条
件下で紡糸した後、冷却して固化し、次いで水等に浸漬
することによって可塑剤を抽出除去して多孔性を付与す
る方法が用いられる。湿式紡糸の場合には、通常用いら
れるように、紡糸後、凝固浴に浸漬して凝固しながら紡
糸原液中の溶媒を抽出除去することによって多孔性を付
与する方法等を用いることができる。Preferable examples of such hollow fibers include porous hollow fibers whose walls are porous, and which are used for blood processing such as hemodialysis, plasma separation, and artificial lungs, and for water processing such as reverse osmosis and ultrafiltration. Porous hollow fibers for fluid separation are particularly preferred. In addition, in the case of a method for manufacturing porous hollow fibers, a treatment to make the wall portion porous is required. For example, in the case of plasticized melt spinning, after spinning under the predetermined conditions as described above, the fiber is cooled and solidified, and then the plasticizer is extracted and removed by immersion in water etc. to impart porosity. method is used. In the case of wet spinning, a commonly used method can be used in which, after spinning, the spinning stock solution is immersed in a coagulation bath to coagulate while extracting and removing the solvent in the spinning dope, thereby imparting porosity.
以下に本発明の実施例と比較例を示すが、本発明はそれ
らによって何ら限定されるものではない。Examples and comparative examples of the present invention are shown below, but the present invention is not limited thereto.
〈実施例〉
セルロースジアセテート１００重量部に対してポリエチ
レングリコールとジグリセリンからなる可塑剤を１５０
重量部の混合物（吐出時の温度約１９０℃における粘度
が約１００ ｐｏｉ！ｌｅ）をルーダ−で溶融混練した
後ギアーポンプをへて、２重管型口金の内側の管より抽
を注入しながら、外側の円形状スリットよりポリマーを
吐出し、風で冷却し該中空繊維を捲取った。２重管型口
金の内側の管より恥の注入時の圧損は管径を種々に変え
て変更した。<Example> 150 parts of a plasticizer consisting of polyethylene glycol and diglycerin was added to 100 parts by weight of cellulose diacetate.
Part by weight of the mixture (viscosity at about 190° C. at discharge temperature is about 100 poi! le) is melted and kneaded in a Ruder, passed through a gear pump, and while injecting bleed through the inner tube of the double tube type nozzle, The polymer was discharged from the outer circular slit, cooled with air, and the hollow fiber was wound up. The pressure loss during injection from the inner tube of the double-tube type mouthpiece was varied by varying the tube diameter.
得られた中空繊維の糸径については、スケール付の顕微
鏡により中空繊維の断面部の糸径を測定した。得られた
結果を第１表に示す。Regarding the thread diameter of the obtained hollow fibers, the thread diameter of the cross section of the hollow fibers was measured using a microscope equipped with a scale. The results obtained are shown in Table 1.
尚、これらの中空繊維の厚みは約１５μであった。Note that the thickness of these hollow fibers was approximately 15μ.
〈発明の効果〉
本発明の中空繊維の製造方法によれば、２重管型口金を
用いて、中空繊維を紡糸する場合低粘度の紡糸原液でも
、糸径斑等の少ない中空繊維が容易に製造できる。<Effects of the Invention> According to the method for producing hollow fibers of the present invention, when hollow fibers are spun using a double tube type spinneret, hollow fibers with less yarn diameter unevenness can be easily produced even with a low viscosity spinning dope. Can be manufactured.
Claims (5)
内部から芯剤としての流体を流出させながら紡糸を行う
中空繊維の製造方法において、該紡糸口金の内側管の内
部から該流体が流出する際の圧力損失Ａ［ｍｍＨ＿２Ｏ
／ｃｍ＾２］と該紡糸口金より吐出されて中空繊維状を
なす成形物の内部における該流体の圧力Ｂ［ｍｍＨ＿２
Ｏ／ｃｍ＾２］が下記式（ I ） Ｂ≦Ａ≦１０Ｂ・・・（ I ） を満足することを特徴とする中空繊維の製造方法。(1) A hollow fiber manufacturing method in which a double-walled spinneret is used and spinning is performed while a fluid as a core material flows out from inside the inner tube of the spinneret. Pressure loss A [mmH_2O when fluid flows out
/cm^2] and the pressure of the fluid inside the molded product discharged from the spinneret and forming a hollow fiber shape B [mmH_2
O/cm^2] satisfies the following formula (I): B≦A≦10B (I).
方法。(2) The method for producing hollow fibers according to claim 1, wherein the fluid is a gas.
粘度が５０〜１０００ｐｏｉｓｅである請求項１の中空
繊維の製造方法。(3) The method for producing hollow fibers according to claim 1, wherein the spinning dope has a viscosity of 50 to 1000 poise when discharged from the double-walled spinneret.
剤を含有した可塑化溶融液である請求項１の中空繊維の
製造方法。(4) The method for producing hollow fibers according to claim 1, wherein the spinning dope is a plasticized melt containing cellulose ester and its plasticizer.
請求項１の中空繊維の製造方法。(5) The method for producing hollow fibers according to claim 1, wherein the hollow fibers are porous hollow fibers for fluid separation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16604389A JPH0333208A (en) | 1989-06-28 | 1989-06-28 | Production of hollow fiber |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP16604389A JPH0333208A (en) | 1989-06-28 | 1989-06-28 | Production of hollow fiber |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0333208A true JPH0333208A (en) | 1991-02-13 |
Family
ID=15823893
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP16604389A Pending JPH0333208A (en) | 1989-06-28 | 1989-06-28 | Production of hollow fiber |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0333208A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995024262A1 (en) * | 1994-03-08 | 1995-09-14 | Teijin Limited | Hollow-fiber blood-purifying membrane and process for producing the same |
| JP2011005431A (en) * | 2009-06-26 | 2011-01-13 | Toyobo Co Ltd | Method for spinning hollow fiber membrane |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5255719A (en) * | 1975-10-31 | 1977-05-07 | Daicel Chem Ind Ltd | Hollow fibers having selective gas permeability and production thereof |
| JPS61274706A (en) * | 1985-05-30 | 1986-12-04 | Teijin Ltd | Cellulosic hollow yarn, its production and fluid separator |
| JPS6229523A (en) * | 1985-07-27 | 1987-02-07 | サンド・アクチエンゲゼルシヤフト | Novel use of dibenz(cd,f)indole |
| JPS6378724A (en) * | 1986-09-22 | 1988-04-08 | Asahi Chem Ind Co Ltd | Manufacture of hollow polyoxymethylene unstretched body |
-
1989
- 1989-06-28 JP JP16604389A patent/JPH0333208A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5255719A (en) * | 1975-10-31 | 1977-05-07 | Daicel Chem Ind Ltd | Hollow fibers having selective gas permeability and production thereof |
| JPS61274706A (en) * | 1985-05-30 | 1986-12-04 | Teijin Ltd | Cellulosic hollow yarn, its production and fluid separator |
| JPS6229523A (en) * | 1985-07-27 | 1987-02-07 | サンド・アクチエンゲゼルシヤフト | Novel use of dibenz(cd,f)indole |
| JPS6378724A (en) * | 1986-09-22 | 1988-04-08 | Asahi Chem Ind Co Ltd | Manufacture of hollow polyoxymethylene unstretched body |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995024262A1 (en) * | 1994-03-08 | 1995-09-14 | Teijin Limited | Hollow-fiber blood-purifying membrane and process for producing the same |
| JP2011005431A (en) * | 2009-06-26 | 2011-01-13 | Toyobo Co Ltd | Method for spinning hollow fiber membrane |
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