JPH09296320A - Spinneret - Google Patents
SpinneretInfo
- Publication number
- JPH09296320A JPH09296320A JP11260696A JP11260696A JPH09296320A JP H09296320 A JPH09296320 A JP H09296320A JP 11260696 A JP11260696 A JP 11260696A JP 11260696 A JP11260696 A JP 11260696A JP H09296320 A JPH09296320 A JP H09296320A
- Authority
- JP
- Japan
- Prior art keywords
- spinneret
- polymer
- hollow fiber
- annular
- spinning
- 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
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は中空糸紡糸用の口金に関
する。さらに詳しくは、紡糸口金内部に滞留する空気等
の気体の混入に起因する中空糸の欠点を解消する紡糸口
金に関する。The present invention relates to a spinneret for hollow fiber spinning. More specifically, the present invention relates to a spinneret that eliminates the drawbacks of hollow fibers caused by the inclusion of gas such as air that accumulates inside the spinneret.
【０００２】[0002]
【従来の技術】近年、高分子からなる中空糸は種々の目
的・用途に開発され、使用されている。特に、中空糸状
の高分子分離膜は、精密濾過膜、限外濾過膜、逆浸透
膜、気体分離膜、窒素富化膜、酸素富化膜、または、血
液浄化膜、人工肺等の様々な用途で実用化され、最近で
は浄水プロセスや各種水処理分野でも使用されるように
なってきている。2. Description of the Related Art In recent years, polymer hollow fibers have been developed and used for various purposes and applications. In particular, hollow fiber polymer separation membranes are used in various types of membranes such as microfiltration membranes, ultrafiltration membranes, reverse osmosis membranes, gas separation membranes, nitrogen-enriched membranes, oxygen-enriched membranes, blood purification membranes and artificial lungs. It has been put to practical use and has recently come to be used in water purification processes and various water treatment fields.
【０００３】これらの中空糸膜は一般的に湿式法もしく
は乾湿式法と呼ばれる紡糸方法、および溶融紡糸法で製
糸される。These hollow fiber membranes are generally produced by a spinning method called a wet method or a dry-wet method, and a melt spinning method.
【０００４】上述のような用途に使用される中空糸膜に
要求される必要条件として、供給側と透過側とを中空糸
膜で完全に隔離して、供給液もしくは供給ガスと透過液
もしくは透過ガスとが相互に混合・接触しないよう、無
欠点であることである。As a necessary condition for the hollow fiber membrane used for the above-mentioned applications, the supply side and the permeation side are completely separated by the hollow fiber membrane so that the supply liquid or the supply gas and the permeation liquid or the permeation liquid may be separated. That is, it is flawless so that the gas does not mix and contact with each other.
【０００５】中空糸の欠点の原因には種々あるが、紡糸
口金に起因する欠点が各種あり、紡糸口金の外観から判
断できる欠点については比較的に容易に改善され得る
が、外観から判断・推定できない欠点は改善が困難であ
る。There are various causes of the defects of the hollow fiber, but there are various defects caused by the spinneret, and the defects that can be judged from the appearance of the spinneret can be improved relatively easily. The drawbacks that cannot be solved are difficult to improve.
【０００６】従来、このような考え方から、近接したス
リットからポリマ流体を吐出させて吐出直後相互に融着
させるスリット式口金の採用を避けて、環状オリフィス
の中心に中空糸製糸の際に中心部の中空部を形成させる
流体を注入する中心パイプを備えた、二重環式の紡糸口
金が使用されてきている。例えば、特公昭４３−２５９
２８およぶ米国特許３，６３０，８２４には、図２に示
すような構造の中空糸紡糸用口金が示されている。ま
た、特公昭５０−４０１６８、同５４−１５１５７４、
および特公平７−５３９２５にはポリマ溶液を紡糸口金
の側方から供給して、注入液体を紡糸口金上方から中心
パイプに供給する構造の紡糸口金が示されている。特公
昭５３−３５６１３に示されている紡糸口金は特公昭５
０−４０１６８、同５４−１５１５７４、および特公平
７−５３９２５等に示された構造の紡糸口金を多ホール
化した構造のものである。[0006] Conventionally, from such an idea, the use of a slit type spinneret in which a polymer fluid is discharged from adjacent slits and fused to each other immediately after discharge is avoided, and a central portion is formed at the center of the annular orifice at the time of hollow fiber spinning. Dual-spindle spinnerets have been used with a central pipe for injecting a fluid that forms the hollow portion of the. For example, Japanese Patent Publication No. 43-259
28 and U.S. Pat. No. 3,630,824 show a hollow fiber spinning die having a structure as shown in FIG. In addition, Japanese Examined Patent Publications No. 50-40168, No. 54-151574,
And Japanese Patent Publication No. 7-53925 discloses a spinneret having a structure in which a polymer solution is supplied from the side of the spinneret and an injecting liquid is supplied to a central pipe from above the spinneret. The spinneret shown in JP-B-53-35613 is
0-40168, 54-151574, and Japanese Patent Publication No. 7-53925 have a spinneret having multiple holes.
【０００７】ポリマ溶液を紡糸口金の側方から供給し
て、注入液体を紡糸口金上方から中心パイプに供給する
構造の紡糸口金を使用する場合、溶融ポリマもしくはポ
リマ溶液の粘性が高い場合には環状オリフィスから吐出
される溶融ポリマもしくはポリマ溶液がポリマ供給孔に
近い方に多く偏り、中空糸の壁厚が不均一になるという
欠点を有している。When a spinneret having a structure in which the polymer solution is supplied from the side of the spinneret and the injecting liquid is supplied to the central pipe from above the spinneret, when the viscosity of the molten polymer or the polymer solution is high, a ring shape is used. There is a drawback that the molten polymer or polymer solution discharged from the orifice is largely concentrated near the polymer supply hole, and the wall thickness of the hollow fiber becomes uneven.
【０００８】図３に示すような構造の従来の中空糸紡糸
用口金を使用する場合、紡糸口金の内部に滞留する空気
等の気体が、紡糸中に微量の気泡として長時間にわたっ
て、中空糸の膜壁の中に取込まれ、中空糸内外に貫通し
た孔となるかあるいは容易に破損して貫通孔の原因とな
り、前述のポリマ溶液を紡糸口金の側方から供給して、
注入液体を紡糸口金上方から中心パイプに供給する構造
の紡糸口金に於ても同様に、この様な欠点を完全に避け
ることが極めて困難であった。このような欠点は、中空
糸の上述の様な用途での機能に対して、性能低下および
信頼性低下の原因になり、かかる欠点のない中空糸を紡
糸する技術が求められているのである。When a conventional hollow fiber spinning spinneret having a structure as shown in FIG. 3 is used, a gas such as air staying inside the spinneret becomes a small amount of bubbles during spinning for a long time to form a hollow fiber. It is taken into the membrane wall and becomes a hole penetrating in and out of the hollow fiber, or it easily breaks causing a through hole, and the polymer solution is supplied from the side of the spinneret,
Similarly, in the spinneret having a structure in which the injected liquid is supplied from above the spinneret to the central pipe, it is extremely difficult to completely avoid such defects. Such a defect causes deterioration of performance and reliability with respect to the function of the hollow fiber in the above-mentioned applications, and a technique for spinning a hollow fiber without such a defect is required.
【０００９】[0009]
【発明が解決しようとする課題】すなわち、紡糸口金内
部に満たせされた空気もしくは気体を容易に紡糸口金の
外に押出すことのできて、中空糸の膜壁の中に気泡を巻
き込むおそれのない紡糸口金を提供するのが本発明の課
題である。That is, the air or gas filled inside the spinneret can be easily extruded out of the spinneret, and there is no risk of entraining air bubbles in the membrane wall of the hollow fiber. It is an object of the present invention to provide a spinneret.
【００１０】[0010]
【課題を解決するための手段】本発明の目的は、基本的
には以下の構成により、達成される。即ち「紡糸方向に
供給されたポリマ流に対して４５〜９０°の角度をなす
環状の棚面が環状オリフィス上部に存在することを特徴
とする中空糸紡糸用口金。」である。The object of the present invention is basically achieved by the following constitutions. That is, "a hollow-fiber spinning spinneret characterized in that an annular shelf surface forming an angle of 45 to 90 ° with respect to the polymer flow supplied in the spinning direction is present in the upper part of the annular orifice."
【００１１】[0011]
【発明の実施の形態】本発明の紡糸方向に供給されたポ
リマ流に対して４５〜９０°の角度をなす環状の棚面
は、ポリマ流がそのまま真っ直ぐに環状オリフィスに流
出するのを遮り、少なくともいったん流束の方向を大き
く変えることができる口金外径側の内表面の構造であ
る。BEST MODE FOR CARRYING OUT THE INVENTION The annular shelf surface forming an angle of 45 to 90 ° with respect to the polymer flow supplied in the spinning direction of the present invention prevents the polymer flow as it is from flowing straight to the annular orifice, At least once, the structure of the inner surface on the outer diameter side of the mouthpiece can change the direction of the flux largely.
【００１２】ここで「４５〜９０°の角度をなす」に関
して、角度の定義方法は、口金の縦断面上で、該棚面の
接線を中心パイプの中心線まで延長した線分と、前記線
分と中心線の交点からポリマ流の上流へ向かう半直線の
なす角により与えられる。なお、以下同様にして他の角
度も定義されるものとする。即ち、口金の構造や各部位
の場合は、それらの表面（特に口金の外径側の内表面）
の接線を中心パイプの中心線まで延長した線分により同
様にして定義できる。Here, with respect to "form an angle of 45 to 90 °", the angle is defined by a line segment in which the tangent line of the shelf surface is extended to the center line of the central pipe on the longitudinal section of the die, and the line. It is given by the angle formed by the half line from the intersection of the minute and the center line to the upstream of the polymer flow. Note that other angles will be defined in the same manner below. That is, in the case of the structure of the base and each part, their surface (especially the inner surface on the outer diameter side of the base)
It can be similarly defined by a line segment extending the tangent line to the center line of the central pipe.
【００１３】なお図３は従来例であり、本発明の環状の
棚面を有しない。前記環状の棚面とは、図１に示したと
おり、環状口金内の外径側の内表面形状である。環状の
棚面は、口金縦断面上において、好ましくは直線形状で
あるが、場合によっては緩やかな曲線形状であっても良
い。あるいは該棚面には多少の凹凸や溝があっても良
い。また、紡糸方向に対して４５〜９０°の角度をなす
ことが好ましくは、６０〜９０°の角度がより好まし
い。FIG. 3 shows a conventional example, which does not have the annular shelf surface of the present invention. As shown in FIG. 1, the annular shelf surface is the inner surface shape on the outer diameter side in the annular die. The annular shelf surface preferably has a linear shape on the vertical cross section of the die, but may have a gentle curved shape in some cases. Alternatively, the shelf surface may have some irregularities or grooves. Moreover, it is preferable to form an angle of 45 to 90 ° with respect to the spinning direction, and it is more preferable to form an angle of 60 to 90 °.
【００１４】なお、環状オリフィス直前の紡糸方向に供
給されたポリマ流の長さは特に限定されるものではない
が、口金の構成上の利便などを考慮すると０．５cm以上
であることが好ましく、１．０cm以上であることがより
好ましく、２．０cm以上であることがさらに好ましい。The length of the polymer flow supplied in the spinning direction immediately before the annular orifice is not particularly limited, but it is preferably 0.5 cm or more considering the convenience of the structure of the die. It is more preferably 1.0 cm or more, further preferably 2.0 cm or more.
【００１５】また本発明におけるポリマ流とは、一定方
向性を有するポリマ流体の流れを指し、主にポリマ流体
供給孔を流れるポリマ流体の流れを指す。また、ポリマ
流体とは中空糸の素材原料となるポリマに流動性が付与
された形態を意味し、具体的には当該ポリマを高温にし
て溶融したもの又は適当な溶媒に溶解した溶液が挙げら
れる。Further, the polymer flow in the present invention means a flow of a polymer fluid having a certain directionality, and mainly a flow of the polymer fluid flowing through the polymer fluid supply hole. Further, the polymer fluid means a form in which fluidity is imparted to a polymer which is a raw material of a hollow fiber, and specific examples thereof include a polymer melted at a high temperature or a solution dissolved in a suitable solvent. .
【００１６】またかかるポリマとしては、特に限定しな
いが、ポリエチレン、ポリプロピレン、ポリスルホン、
ポリエーテルスルホン、ポリビニルアルコール、セルロ
ースアセテート、ポリアクリロニトリル、その他の材質
を選択することができる。アクリロニトリル系重合体の
中でも最も好ましいものとしては、アクリロニトリルを
少なくとも５０モル％以上、好ましくは６０モル％以上
と該アクリロニトリルに対して共重合性を有するビニル
化合物一種または二種以上を５０モル％以下、好ましく
は０〜４０モル％とからなるアクリロニトリル系重合体
である。また、これらアクリロニトリル系重合体二種以
上、さらに他の重合体との混合物でも良い。上記ビニル
化合物としては、アクリロニトリルに対して共重合性を
有する公知の化合物であればよく、特に限定されない
が、好ましい共重合体成分としては、アクリル酸、イタ
コン酸、アクリル酸メチル、酢酸ビニル、アリルスルホ
ン酸ソーダー、ｐ−スチレンスルホン酸ソーダー等を例
示することができる。他に好ましい中空糸膜素材として
は、エチレンプロピレンまたは４メチルペンテンなどの
単独または二種以上のオレフィン系重合体が適当であ
る。本発明は特に粘度が高い場合に好適にその効果が発
揮され、例えば、極限粘度が２．０以上である超高重合
度のアクリロニトリル系重合体の濃度が５〜１５重量で
ある有機溶媒溶液のような粘度を有するポリマ流体が挙
げられる。The polymer is not particularly limited, but polyethylene, polypropylene, polysulfone,
Polyether sulfone, polyvinyl alcohol, cellulose acetate, polyacrylonitrile, and other materials can be selected. The most preferable acrylonitrile-based polymer is at least 50 mol% or more of acrylonitrile, preferably 60 mol% or more, and 50 mol% or less of one or more vinyl compounds having copolymerizability with the acrylonitrile. It is preferably an acrylonitrile polymer composed of 0 to 40 mol%. Further, a mixture of two or more of these acrylonitrile-based polymers and further a mixture with another polymer may be used. The vinyl compound may be any known compound having copolymerizability with acrylonitrile, and is not particularly limited, but preferable copolymer components include acrylic acid, itaconic acid, methyl acrylate, vinyl acetate, and allyl. Examples thereof include sodium sulfonate and sodium p-styrenesulfonate. As another preferable hollow fiber membrane material, a single or two or more kinds of olefin polymers such as ethylene propylene or 4-methylpentene are suitable. The present invention exerts its effect preferably when the viscosity is particularly high. Polymer fluids having such viscosities are included.
【００１７】図１は本発明の紡糸口金の全体構造を縦断
面Ａ、横断面Ｂに分けて示した図である。１は口金ボデ
ィーであり、４はポリマ流体供給孔であり、８は中空糸
膜の中空部に流体を注入するための供給孔である。ポリ
マ流体供給孔４は好ましくは２〜８本、より好ましくは
４〜６本を環状にほぼ等間隔で設けるのが好適であるが
特に限定されるものではない。ポリマ流体供給孔４の下
端の開口面５と環状オリフィス部７との間に、ポリマ供
給孔４からポリマ合流部６に流入してきた溶融ポリマ流
体の流れを遮る環状の棚面１０を備えている。８は中空
糸膜の中空部に流体を注入する中心パイプである。Ｂは
口金ボディーを上から見た図であり、縦断面Ａの注入液
体供給孔８付近で切断した横断面である。FIG. 1 is a view showing the overall structure of the spinneret of the present invention divided into a vertical section A and a horizontal section B. Reference numeral 1 is a base body, 4 is a polymer fluid supply hole, and 8 is a supply hole for injecting a fluid into the hollow portion of the hollow fiber membrane. The polymer fluid supply holes 4 are preferably provided in an amount of preferably 2 to 8, more preferably 4 to 6 in a ring shape at substantially equal intervals, but are not particularly limited. Between the opening surface 5 at the lower end of the polymer fluid supply hole 4 and the annular orifice portion 7, there is provided an annular shelf surface 10 that blocks the flow of the molten polymer fluid flowing into the polymer merging portion 6 from the polymer supply hole 4. . Reference numeral 8 is a central pipe for injecting a fluid into the hollow portion of the hollow fiber membrane. B is a view of the die body as seen from above, which is a transverse section of the longitudinal section A taken in the vicinity of the injection liquid supply hole 8.
【００１８】図２は本発明を詳細に説明するための口金
内部の詳細図である。環状の棚面１０の幅ｂは広いほど
効果はあるが、ポリマ合流部６が大きいと最初に滞留す
る空気が多くなり、また空気が残留しやすくなるので、
自ずと好適な範囲がある。すなわち、本発明者が鋭意検
討した結果、棚面１０の幅ｂはポリマ供給孔の直径ｄの
１／２以上である場合に極めてよい結果が得られた。棚
面１０は紡糸口金中心部に向って勾配がついていてもよ
い。また、棚面の一部分にだけ勾配を付けた構造であっ
てもポリマ流体の流れを遮り、棚面上を横方向に流れて
ポリマ合流部を満たし、最初に充満していた空気を押出
してから、ポリマ流体が環状オリフィス部へ流出する効
果を示す限り、何等支障はない。FIG. 2 is a detailed view of the inside of the die for explaining the present invention in detail. The wider the width b of the annular shelf surface 10 is, the more effective it is. However, when the polymer merging portion 6 is large, the amount of air that initially stays is large, and the air tends to remain.
Naturally, there is a suitable range. That is, as a result of diligent studies by the present inventor, extremely good results were obtained when the width b of the shelf surface 10 was 1/2 or more of the diameter d of the polymer supply hole. The shelf surface 10 may have a slope toward the center of the spinneret. In addition, even if the structure has a slope only on a part of the shelf surface, it blocks the flow of polymer fluid, flows laterally on the shelf surface to fill the polymer confluence, and then pushes out the initially filled air. As long as the polymer fluid has the effect of flowing out to the annular orifice portion, there is no problem.
【００１９】なお、環状の棚面を設けた場合には、環状
の棚面の内側端部と中心パイプ外側との間のポリマ流路
部の面積が環状の棚面の構造のものと比較して小さくな
る。極端な場合には、環状オリフィスのポリマ吐出部の
断面積より小さくなる場合も考えられるが、その場合に
はポリマ合流部の空気の押出しが難しくなるので、環状
の棚面の内側端部と中心パイプ外側との間のポリマ流路
部の面積は、環状オリフィスのポリマ流路部の断面積以
上になるようにすることが好ましい。When the ring-shaped shelf surface is provided, the area of the polymer passage between the inner end of the ring-shaped shelf surface and the outside of the central pipe is smaller than that of the ring-shaped shelf surface structure. Becomes smaller. In extreme cases, it may be smaller than the cross-sectional area of the polymer discharge part of the annular orifice, but in that case it is difficult to push out air at the polymer merging part, so the inner edge of the annular shelf surface and the center It is preferable that the area of the polymer flow passage portion between the outside of the pipe and the cross-sectional area of the polymer flow passage portion of the annular orifice is equal to or larger than the area.
【００２０】環状の棚面とポリマ供給孔の開口端面から
の距離ａは、ポリマ合流部に充満する空気の押出され方
に影響する因子である。ａが大きすぎると環状の棚面を
設けた効果が小さくなり、ａが小さすぎると溶融ポリマ
流体の流動抵抗が大きくなるばかりか環状の棚面から環
状オリフィスに至る部分の空気が残留しやすくなるの
で、適当な距離とする必要がある。すなわち、環状の棚
面とポリマ供給孔の開口端面からの距離ａは、ポリマ供
給孔の直径ｄの１／２以上３倍以下であるのが好まし
く、１倍以上２倍以下がより好ましい。The distance a from the annular shelf surface and the opening end surface of the polymer supply hole is a factor that influences how the air that fills the polymer merging portion is extruded. If a is too large, the effect of providing the annular shelf surface will be small, and if a is too small, not only will the flow resistance of the molten polymer fluid increase, but the air from the annular shelf surface to the annular orifice will easily remain. Therefore, it is necessary to set an appropriate distance. That is, the distance a from the annular shelf surface to the opening end surface of the polymer supply hole is preferably 1/2 or more and 3 times or less, and more preferably 1 time or more and 2 times or less, the diameter d of the polymer supply hole.
【００２１】また、ポリマ供給孔の開口端面のポリマ供
給孔の外縁部と、中心パイプの外周部との距離ｃもポリ
マ合流部の空気の残留と紡糸中の気泡の発生を左右する
因子である。距離ｃが大きくポリマ供給孔の外縁部と中
心パイプの外周部とが離れすぎていると、ポリマ合流部
の空気が残留しやすく、中空糸の膜壁の中に気泡を巻き
込み易くなり、著しく長時間にわたり気泡を発生させる
ことになる。したがって、ポリマ供給孔の開口端面のポ
リマ供給孔の外縁部と中心パイプの外周部との距離ｃ
は、おおよそポリマ供給孔の直径ｄ以下であることが好
ましい。Further, the distance c between the outer edge of the polymer supply hole on the opening end surface of the polymer supply hole and the outer peripheral portion of the central pipe is also a factor that influences the residual air in the polymer merging portion and the generation of bubbles during spinning. . If the distance c is large and the outer edge of the polymer supply hole and the outer periphery of the center pipe are too far apart, the air at the polymer merging portion is likely to remain and air bubbles are likely to be trapped in the membrane wall of the hollow fiber, resulting in extremely long length. Bubbles will be generated over time. Therefore, the distance c between the outer edge of the polymer supply hole on the opening end face of the polymer supply hole and the outer peripheral portion of the center pipe.
Is preferably approximately equal to or smaller than the diameter d of the polymer supply hole.
【００２２】なお、ｅは環状オリフィス８の外側の直径
であり、ｆは内側の直径である。Note that e is the outside diameter of the annular orifice 8 and f is the inside diameter.
【００２３】本発明は、その主旨から中空糸の素材や使
用目的に限定されるものでないことは明らかであり、ま
た、溶融紡糸法および溶液紡糸法等の紡糸方法にも限定
されないことは明らかである。From the gist of the invention, it is clear that the present invention is not limited to the material and purpose of use of the hollow fiber, and it is also clear that the present invention is not limited to the spinning method such as the melt spinning method and the solution spinning method. is there.
【００２４】また、ポリマ流を調整するために、該環状
の棚面と環状オリフィスとの間に、環状の傾斜面を設け
ることが好ましく、紡糸方向に対して１５〜６０°の角
度をなすのがより好ましく、２０〜５０°がさらに好ま
しい。なお、その機能上、棚面の角度よりも傾斜面の角
度を小さく調整することが好ましい。そして該環状の傾
斜面の幅はポリマ供給孔の直径の１／２以上が好まし
く、１倍以上がより好ましい。Further, in order to adjust the polymer flow, it is preferable to provide an annular inclined surface between the annular shelf surface and the annular orifice, and an angle of 15 to 60 ° is formed with respect to the spinning direction. Is more preferable and 20-50 degrees is still more preferable. In terms of its function, it is preferable to adjust the angle of the inclined surface to be smaller than the angle of the shelf surface. The width of the annular inclined surface is preferably 1/2 or more of the diameter of the polymer supply hole, and more preferably 1 time or more.
【００２５】なお、棚面や傾斜面は、本発明の目的を達
成するのに差し支えない範囲内においていかなる形態を
有していても良い。例示するならば、棚面や傾斜面は、
角や辺により区切られ他の面と明確に区別できる面を形
成していても良い。あるいは部分的に曲面で棚面から傾
斜面さらに傾斜面から環状オリフィスに連続している形
態でも良いが、この場合加工がやや複雑となる。いずれ
にしても、特に限定されるものではないが、例えば前述
の通りの数値範囲の角度や大きさを有する平面、曲面、
部分乃至は構造が口金において認めうるのならば、いか
なる形態を有していても良い。The shelf surface and the inclined surface may have any shape as long as the object of the present invention can be achieved. For example, the shelves and slopes are
It is also possible to form a surface which is separated by a corner or a side and which can be clearly distinguished from other surfaces. Alternatively, the curved surface may be partially continuous from the shelf surface to the inclined surface, and further from the inclined surface to the annular orifice, but in this case, the processing becomes slightly complicated. In any case, although not particularly limited, for example, a plane, a curved surface having an angle or size in the numerical range as described above,
The part or structure may have any shape as long as it can be recognized in the base.
【００２６】さらに、紡糸方向に供給されたポリマ流
に、紡糸方向に対して４５〜９０°の角度をなす方向を
与えることができる構造であるのならば、構造上の角度
が前記角度に限定されなくとも良い。Further, if the structure is such that the polymer stream supplied in the spinning direction can be provided with a direction forming an angle of 45 to 90 ° with respect to the spinning direction, the structural angle is limited to the above angle. It doesn't have to be done.
【００２７】また、中空糸の寸法等にもよらないことは
説明を要しないが、比較的大孔径の紡糸口金を使用する
ような紡糸において、特に本発明が非常に有用となる。
これは、大孔径の紡糸口金の場合には、環状オリフィス
部分での溶融ポリマ流体の流動抵抗が比較的小さく、ポ
リマ合流部をポリマ流体が充満される前に環状オリフィ
ス部分から吐出されるためではないかと推量されるため
である。Although it does not need to be explained that it does not depend on the size of the hollow fiber or the like, the present invention is very useful especially for spinning using a spinneret having a relatively large hole diameter.
This is because, in the case of a spinneret having a large hole diameter, the flow resistance of the molten polymer fluid in the annular orifice portion is relatively small, and the polymer confluence is discharged from the annular orifice portion before being filled with the polymer fluid. This is because it is guessed that there may be.
【００２８】[0028]
【実施例】空気の残留の程度は、紡糸口金直下で観察さ
れる気泡個数で表わした。観察方法は、紡糸時に紡糸口
金直下を証明して気泡を観察し、３０分間に観察された
気泡の数を測定した。実験は、各寸法のそれぞれの構造
の紡糸口金を８種類８個同時に紡糸機に装着して、同時
に紡糸溶液を吐出させて比較した。紡糸原液の吐出量は
１口金当り７．５ｇ／分とした。EXAMPLE The degree of air remaining was expressed by the number of bubbles observed immediately below the spinneret. As the observation method, bubbles were observed by demonstrating just below the spinneret during spinning, and the number of bubbles observed in 30 minutes was measured. In the experiment, eight kinds of spinnerets having each structure of each size and eight kinds were simultaneously attached to the spinning machine, and the spinning solution was discharged at the same time for comparison. The discharge rate of the spinning dope was 7.5 g / min per spinneret.
【００２９】実施例１〜６、比較例１、２ 図２にその構造を示した口金を用いて、極限粘度３．２
のポリアクリロニトリルの１０．１重量％のＤＭＳＯ溶
液を紡糸原液として常温で紡糸実験を実施した。なお凝
固液として８２重量％のＤＭＳＯ水溶液を吐出量２．０
ｇ／min で用いた。ポリマ溶液吐出開始後、５０分、１
００分、２００分、および４００分経過後の、３０分当
りの気泡個数を測定した。比較例として、図３の構造の
紡糸口金を用いて実施例と全く同様に実験を行なった。
紡糸口金の寸法を表１に示した。Examples 1 to 6 and Comparative Examples 1 and 2 By using the die whose structure is shown in FIG. 2, the intrinsic viscosity is 3.2.
A spinning experiment was carried out at room temperature using a 10.1% by weight solution of polyacrylonitrile in DMSO as a stock solution for spinning. 82% by weight DMSO aqueous solution as the coagulation liquid was discharged in an amount of 2.0.
Used at g / min. 50 minutes after starting the polymer solution, 1
The number of bubbles per 30 minutes was measured after 00 minutes, 200 minutes, and 400 minutes. As a comparative example, an experiment was conducted in exactly the same manner as in the example using the spinneret having the structure shown in FIG.
The dimensions of the spinneret are shown in Table 1.
【００３０】[0030]
【表１】 また、得られた結果を表２に示した。[Table 1] The obtained results are shown in Table 2.
【００３１】[0031]
【表２】 表から明らかなように、図３の構造の紡糸口金ではポリ
マ溶液吐出開始後２００分以上後でも、気泡が観察され
たのに対して、図２の構造の紡糸口金を使用した場合に
は、１００分程度で気泡が著しく減少し、２００分後に
はほとんど観察されなかった。即ち、本発明の構造の口
金を用いることにより、紡糸初期から気泡による欠点の
ない中空糸を紡糸することができることが分る。[Table 2] As is clear from the table, in the spinneret having the structure shown in FIG. 3, air bubbles were observed even 200 minutes or more after the start of discharging the polymer solution, whereas in the case where the spinneret having the structure shown in FIG. 2 was used, The bubbles were remarkably reduced in about 100 minutes, and hardly observed after 200 minutes. That is, by using the spinneret having the structure of the present invention, it is possible to spin a hollow fiber without defects due to air bubbles from the initial stage of spinning.
【００３２】[0032]
【発明の効果】本発明によりポリマ流に偏向あるいは乱
流が与えられるので、紡糸開始時に紡糸口金内部に満た
されている空気を容易に紡糸口金の外に押出すことので
きて、中空糸の膜壁の中に気泡を巻き込むおそれのない
紡糸口金を提供し、紡糸口金の内部に滞留する空気等の
気体が紡糸中に微量の気泡として長時間にわたって、中
空糸の膜壁の中に取込まれ、中空糸内外に貫通した孔と
なるかあるいは容易に破損して貫通孔の原因となるよう
な欠点のない中空糸を容易に紡糸することができる。ま
た、かかる構造によりポリマ供給孔から遠い近いにかか
わらず、口金のあらゆる部分でポリマ供給が平準化さ
れ、均一な厚みの中空糸を紡糸することが可能となる。According to the present invention, since the polymer flow is deflected or turbulent, the air filled in the spinneret at the start of spinning can be easily extruded out of the spinneret and the hollow fiber It provides a spinneret without the possibility of entraining air bubbles in the membrane wall, and gas such as air staying inside the spinneret is taken into the hollow fiber membrane wall for a long time as a small amount of bubbles during spinning. It is possible to easily spin a hollow fiber which is rare and has no defects such that it becomes a hole penetrating in and out of the hollow fiber or is easily broken to cause a through hole. Further, with such a structure, the polymer supply is leveled in all parts of the die regardless of the distance from the polymer supply hole, and it becomes possible to spin a hollow fiber having a uniform thickness.
【図１】 本発明の中空糸紡糸用口金の全体構造の縦横
断面を示した。FIG. 1 shows a vertical and horizontal cross section of the overall structure of a spinneret for hollow fiber spinning of the present invention.
【図２】 本発明の中空糸紡糸用口金の詳細構造の縦断
面を示した。FIG. 2 shows a vertical cross section of a detailed structure of a spinneret for hollow fiber spinning of the present invention.
【図３】 従来公知の中空糸紡糸用口金の内部構造を詳
細に示した。FIG. 3 shows in detail the internal structure of a conventionally known spinneret for hollow fiber spinning.
１：中空糸口金ボディ ２：プラグ ３：インサート ４：ポリマ流体供給孔 ５：ポリマ流体供給孔下端の開口面 ６：ポリマ流体合流部 ７：環状オリフィス部 ８：注入流体供給孔 ９：中心パイプ １０：環状棚面 Ａ：図１の縦断面図 Ｂ：図１の横断面図 ａ：ポリマ流体供給孔下端の開口面５と環状棚面１０と
の距離 ｂ：環状棚面１０の幅 ｃ：ポリマ流体供給孔４の外周部とポリマ流体供給孔下
端の開口面５における中心パイプ９の外縁部との距離1: Hollow fiber mouthpiece body 2: Plug 3: Insert 4: Polymer fluid supply hole 5: Opening surface at the lower end of polymer fluid supply hole 6: Polymer fluid confluence part 7: Annular orifice part 8: Injection fluid supply hole 9: Center pipe 10 : Annular shelf surface A: vertical sectional view of FIG. 1 B: lateral sectional view of FIG. 1 a: distance between the opening surface 5 at the lower end of the polymer fluid supply hole and the annular shelf surface b: width of the annular shelf surface c: polymer Distance between the outer periphery of the fluid supply hole 4 and the outer edge of the center pipe 9 on the opening surface 5 at the lower end of the polymer fluid supply hole
Claims (8)
４５〜９０°の角度をなす環状の棚面が環状オリフィス
上部に存在することを特徴とする中空糸紡糸用口金。1. A spinneret for hollow fiber spinning, characterized in that an annular shelf surface forming an angle of 45 to 90 ° with respect to the polymer flow supplied in the spinning direction is present above the annular orifice.
の１／２以上であることを特徴とする、請求項２記載の
中空糸紡糸用口金。2. The spinneret for hollow fiber spinning according to claim 2, wherein the width of the annular shelf surface is 1/2 or more of the diameter of the polymer supply hole.
１／２以上であり、環状の棚面の内側端部と中心パイプ
外側との間のポリマ流路部の面積が、環状オリフィスの
ポリマ流路部の断面積以上であることを特徴とする、請
求項３記載の中空糸紡糸用口金。3. The width of the annular shelf surface is ½ or more of the diameter of the polymer supply hole, and the area of the polymer flow path portion between the inner end of the annular shelf surface and the outside of the central pipe is an annular shape. The spinneret for hollow fiber spinning according to claim 3, wherein the orifice has a cross-sectional area equal to or larger than that of the polymer channel portion of the orifice.
らの距離が、ポリマ供給孔の直径の１／２以上３倍以下
であることを特徴とする、請求項１記載の中空糸紡糸用
口金。4. The hollow fiber spinning according to claim 1, wherein the distance between the annular shelf surface and the opening end surface of the polymer supply hole is 1/2 or more and 3 times or less the diameter of the polymer supply hole. Mouthpiece.
供給孔の外縁部と中心パイプの外周部との距離が、ポリ
マ供給孔の直径以下であることを特徴とする請求項１記
載の中空糸紡糸用口金。5. The distance between the outer edge portion of the polymer supply hole and the outer peripheral portion of the center pipe at the opening end surface of the polymer supply hole is equal to or less than the diameter of the polymer supply hole. Hollow fiber spinneret.
に、紡糸方向に対して１５〜６０°の角度をなす環状の
傾斜面を有することを特徴とする、請求項１記載の中空
糸紡糸用口金。6. The hollow fiber according to claim 1, characterized in that an annular inclined surface forming an angle of 15 to 60 ° with respect to the spinning direction is provided between the annular shelf surface and the annular orifice. Spinneret for spinning.
径の１／２以上であることを特徴とする、請求項７記載
の中空糸紡糸用口金。7. The hollow fiber spinning die according to claim 7, wherein the width of the annular inclined surface is 1/2 or more of the diameter of the polymer supply hole.
方向に対して４５〜９０°の角度をなす方向を与える構
造が存在する環状オリフィス上部空間を有することを特
徴とする中空糸紡糸用口金。8. A hollow fiber spinning machine characterized by having an annular orifice upper space in which a structure for giving a direction of an angle of 45 to 90 ° to the spinning direction is present in a polymer flow supplied in the spinning direction. Mouthpiece.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11260696A JPH09296320A (en) | 1996-05-07 | 1996-05-07 | Spinneret |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11260696A JPH09296320A (en) | 1996-05-07 | 1996-05-07 | Spinneret |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH09296320A true JPH09296320A (en) | 1997-11-18 |
Family
ID=14590946
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11260696A Pending JPH09296320A (en) | 1996-05-07 | 1996-05-07 | Spinneret |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH09296320A (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007239147A (en) * | 2006-03-09 | 2007-09-20 | Nok Corp | Spinning nozzle for producing hollow fiber membrane |
| CN106757437A (en) * | 2017-01-06 | 2017-05-31 | 东华大学 | A kind of porous spinneret of melt-spun hollow-fibre membrane |
| CN108411496A (en) * | 2018-04-17 | 2018-08-17 | 嘉兴学院 | A kind of device preparing not weaving fabric of superfine fiber using turbulent flow |
| CN109957847A (en) * | 2017-12-25 | 2019-07-02 | 宁波斯宾拿建嵘精密机械有限公司 | A kind of hollow tunica fibrosa spinneret that novel multifibres merges |
| WO2023027052A1 (en) | 2021-08-23 | 2023-03-02 | 東レ株式会社 | Hollow fiber microporous membrane, and gas separation membrane module with same built thereinto |
-
1996
- 1996-05-07 JP JP11260696A patent/JPH09296320A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007239147A (en) * | 2006-03-09 | 2007-09-20 | Nok Corp | Spinning nozzle for producing hollow fiber membrane |
| CN106757437A (en) * | 2017-01-06 | 2017-05-31 | 东华大学 | A kind of porous spinneret of melt-spun hollow-fibre membrane |
| CN109957847A (en) * | 2017-12-25 | 2019-07-02 | 宁波斯宾拿建嵘精密机械有限公司 | A kind of hollow tunica fibrosa spinneret that novel multifibres merges |
| CN108411496A (en) * | 2018-04-17 | 2018-08-17 | 嘉兴学院 | A kind of device preparing not weaving fabric of superfine fiber using turbulent flow |
| CN108411496B (en) * | 2018-04-17 | 2020-10-23 | 嘉兴学院 | Device for preparing superfine fiber non-woven fabric by utilizing turbulence |
| WO2023027052A1 (en) | 2021-08-23 | 2023-03-02 | 東レ株式会社 | Hollow fiber microporous membrane, and gas separation membrane module with same built thereinto |
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