JPS6339264Y2 - - Google Patents

Description

[Detailed Description of the Invention] The present invention relates to a spinneret device for producing hollow fibers. More specifically, the present invention relates to a spinneret device for producing hollow fibers for dialysis used in artificial kidney devices and the like.

In recent years, artificial kidney devices that utilize osmotic action, extraocular filtration action, etc. have made remarkable progress and are widely used in the medical world. Therefore, in such an artificial kidney device, the extremely thin hollow fiber for dialysis is the most important component.

Typical hollow fibers for dialysis include (1) fiber length and circumference ranging from several μm to
Made from copper ammonia cellulose fibers that have a uniform wall thickness of 60 μm, a uniform perfect circular cross section with an outer diameter of 10 μm to several hundred μm, and have hollow portions that extend continuously over the entire length of the stretched and oriented fibers. Hollow fiber (Special Publication No. 50-40168), (2) Copper ammonia regenerated cellulose having a cross-sectional structure in which the constituent parts near the outer surface have a denser porous structure than the constituent parts near the inner surface and the middle part. (Special Publication No. 55-1363), (3) Electron microscopic observation of a copper ammonia regenerated cellulose tubular body having a hollow core when wet, shows that the entire cross-sectional and vertical cross-sections are at most 200 Å or less. Hollow fibers for dialysis made of copper ammonia regenerated cellulose (Japanese Patent Application Laid-open No. 134920/1983), etc., are made of copper ammonia regenerated cellulose, which has a substantially homogeneous and dense porous structure with fine pores, and has smooth and skinless surfaces on both the inner and outer surfaces. . Therefore, in both of these hollow fibers, the cuprammonium cellulose spinning dope is extruded into the air through the annular spinning hole and allowed to fall under its own weight. Introducing and filling a non-coagulable liquid into the spinning stock solution and discharging it,
After that, it is sufficiently stretched by falling under its own weight, and then immersed in a dilute sulfuric acid solution for solidification and regeneration.

Therefore, while falling through the gaseous atmosphere, the ammonia separates to some extent and begins to solidify from the surface. As a result, skins are formed on the outer surface of the hollow fibers obtained to varying degrees depending on the method of manufacture, so that both the inner and outer surfaces and the interior of the hollow fibers cannot be homogeneous. Therefore, when such a hollow fiber is used in a dialysis device, the diameter of the micropores generated on the inner surface and inside and outside surfaces are different, so the performance is inconsistent and a good dialysis effect cannot be obtained. The drawback was that it was difficult.

As described in Japanese Patent Publication No. 52-42883, for example, the hollow fiber described above has a storage chamber for a spinning dope and a non-coagulable liquid introduction pipe disposed inside the chamber. The apparatus is manufactured by an apparatus in which a spinneret plate having double spinnerets arranged concentrically at the lower end of the storage chamber is attached by a fastener. However, this apparatus had the drawback that it could only produce hollow fibers with a skin on the outer surface as described above.

The purpose of this invention is to eliminate the various drawbacks of the conventional products as described above, and to manufacture hollow fibers used in the production of hollow fiber membranes for dialysis that do not produce skin on the outer surface and are uniform on both the inner and outer surfaces as well as the inside. The present invention provides a spinneret device for use in the present invention.

A device that achieves the above object includes a lower nozzle body having a first circular hole at the bottom that communicates with the lower end, a recess at the top that communicates with the first circular hole, and a lower nozzle body that is inserted into the first circular hole of the lower nozzle body. a funnel-shaped first spinner having a lower tubular portion and an upper body portion inserted into the recess of the lower nozzle body; a second spinner inserted into the first spinner; and a second circular spinner communicating with the lower end. an upper nozzle body provided with a hole at the bottom and removably fixed on the lower nozzle body, the upper nozzle body further comprising a first spinner formed by a lower end opening of the second spinner; A first inlet for introducing the first non-coagulable liquid that communicates with the non-coagulable liquid discharge hole, and between the second spinner and the first spinner through the second circular hole. a second inlet for introducing the spinning dope that communicates with the spinning dope discharge hole, and a second non-coagulable part formed between the first circular hole of the lower nozzle body and the lower tubular part of the first spinner; a third inlet for introducing the second non-coagulable liquid that communicates with an annular space formed between the upper body of the first spinner and the recess of the lower nozzle body that communicates with the liquid discharge hole; This is a non-concentric spinneret device for manufacturing hollow fibers.

Next, the cap device of the present invention will be described in detail with reference to the drawings.

FIG. 1 is a cross-sectional view of one embodiment of the spinneret device for manufacturing hollow fibers of the present invention.

This spinneret device 26 for producing hollow fibers includes a lower nozzle body 31 having a first circular hole 3 at the bottom that communicates with the lower end and a recess 2 at the top that communicates with the first circular hole 3; A funnel-shaped first spinner 4 having a lower tubular part 6 inserted into the first circular hole 3 and an upper main body part inserted into the recess 2 of the lower nozzle body 31; A spinner 16 and a second circular hole 12 communicating with the lower end are provided at the bottom, and on the lower nozzle body 31,
an upper nozzle body 13 which is abutted and removably fixed;
a first inlet 21 for introducing the first non-coagulable liquid that communicates with the first non-coagulable liquid discharge hole 20 formed by the lower end opening of the second spinner 16;
Spinning dope discharge hole 1 formed between second spinner 16 and first spinner 4 via circular hole 12
8 and a second non-coagulable liquid formed between the first circular hole 3 of the lower nozzle body 31 and the lower tubular part of the first spinner 4. A third inlet 10 for introducing the second non-coagulable liquid, which communicates with the annular space formed between the upper body part of the first spinner 4 and the recess 2 of the lower nozzle body 31, which communicates with the discharge hole 7; and non-concentrically.

This will be explained in detail with reference to FIG.

The nozzle device of the present invention comprises a lower nozzle body 31 and
The upper nozzle body 13 is fixed on the lower nozzle body, the first spinner 4, and the second
It is formed by a spinner 16 .

The upper nozzle main body 13 includes a first inlet 21 for introducing the first non-coagulating liquid, a second inlet 25 for introducing the spinning dope, and an inlet for introducing the second non-coagulating liquid. The third inlet 10 is provided non-concentrically. Further, a first spinner 4 and a second spinner 16 are inserted into a recess formed in the lower nozzle main body 31.

To explain more specifically, the lower nozzle body 31
A recess 2 is formed in the upper center of the recess 2 , and a first circular hole 3 is formed in the bottom of the recess 2 and opens at the lower end of the lower nozzle body 31 . A funnel-shaped first spinner 4 is inserted into this recess 2 and is stopped by a key 5.
The lower tubular part 6 of the first spinner 4 is inserted into the circular hole 3, and the lower end of the lower tubular part 6 reaches the lower surface of the lower nozzle body 31. Therefore, an annular second non-coagulating liquid discharge hole 7 is formed between the inner wall surface of the circular hole 3 and the outer wall surface of the lower tubular portion 6.
Moreover, this first spinner 4 and the lower nozzle body 31
An annular space 8 formed between the upper nozzle main body 13 and the second non-coagulable liquid discharge hole 7 communicates with the third inlet 10 provided in the upper nozzle body 13 via a passage 9. A second connector 11 is screwed onto the tip of the third inlet 10 and connected to a second non-coagulable liquid supply source via a conduit (not shown).

Above this lower nozzle body 31 is an upper nozzle body 13 having a second circular hole 12 bored in the center.
is removably locked and fixed by fixing means such as an annular pressing member 14 and a hexagon head bolt 15. Also, between the lower nozzle body 31 and the upper nozzle body 13, a key 35 and O-rings 23, 2
4 is provided to seal between the two.

A funnel-shaped second spinner 1 is inserted into the second circular hole 12 provided in the center of the upper nozzle body 13.
6 is inserted into the first spinner 4 so that the tubular portion 17 at its tip is fitted into the first spinner 4 , and the lower end of the tubular portion 17 of the second spinner 16 reaches the lower surface of the lower nozzle body 31 . Therefore, an annular spinning dope discharge hole 18 is formed between the inner wall surface of the first spinner 4 and the outer wall surface of the second spinner 16. This spinning dope discharge hole 18 communicates with the second circular hole 12 of the upper nozzle body 13,
Furthermore, it communicates with a second introduction port 25 via a passage 19 . Further, the second inlet 25 is connected to a spinning dope supply source via a conduit (not shown).

The lower end opening of the second spinner 16 forms a first non-coagulable liquid discharge hole 20, and the upper end opening forms a first introduction port 21. Screwed first connector 2
2 to a first non-coagulable liquid source.

In this mouthpiece device, the upper nozzle body 1
3 and the lower nozzle body 31 can be easily disassembled by removing the hexagon head bolts 15. To explain, the lower nozzle body 31 can be removed from the upper nozzle body 13 by removing the hexagon head bolt 15, and further, by removing the first spinner inserted inside the lower nozzle body 31. , the inside of the first circular hole 3 can be cleaned, and substances that cause nozzle clogging can be removed very easily. Furthermore, this cap device 26
Now, on the upper nozzle body, non-concentrically, separately 3
Since two liquid inlets are provided, a conduit communicating with a liquid supply source can be easily connected to each inlet.

Further, in the mouthpiece device according to the present invention, each annular discharge hole is formed by inserting the first funnel-shaped spinner into the circular hole in the lower nozzle body and further inserting the second spinner into the first spinner as described above. Because of this, the flow passages of each discharge hole can be the same distance and long, and therefore, when discharging liquids of different viscosities, the flow velocity can be adjusted to a constant value by the flow passages.

The spinneret device 26 configured in this manner is used in the following manner. That is, as shown in FIGS. 1 and 2, the cuprammonium cellulose spinning dope supplied from the spinning dope supply source (not shown) is
The spinning stock solution is extruded from the second inlet 25 through the passage 19 and from the spinning dope discharge hole 18 in an annular shape. At this time, the non-coagulant liquid for the copper ammonia cellulose spinning dope supplied from the first non-coagulable liquid supply source (not shown) passes through the first inlet 21 and from the first non-coagulable liquid discharge hole 20. The spinning dope is injected into the center of the annularly extruded spinning dope and discharged. Further, the non-coagulable liquid for the copper ammonia cellulose-based spinning dope supplied from the second non-coagulable liquid supply source (not shown) passes through the third inlet 10 and the passage 9 to the second non-coagulable liquid discharge hole. 7, it is discharged in an annular manner surrounding the outside of the spinning dope that has been extruded in an annular manner. The linear spinning dope 27 extruded in a circular shape with its inner and outer surfaces sealed with the non-coagulating liquid does not coagulate at all, and is a coagulable liquid relative to the copper ammonia cellulose spinning dope filled in the bathtub 28. 29
The coagulable liquid 29 is introduced between the direction change rod 30 and another direction change rod 31 provided as necessary.
For example, 50-120m/min, preferably 60-100m/min
After solidifying as it advances at a linear speed of m/min, it is pulled up from the roll 32 and sent to the next process.

Various types of cellulose can be used, but one example is a cellulose with an average degree of polymerization of 500 to 500.
2500 is preferably used. Thus, the cuprammonium cellulose solution is prepared by a conventional method. For example, first, aqueous ammonia, a basic aqueous copper sulfate solution, and water are mixed to prepare an aqueous cupric ammonia solution, an antioxidant (e.g., sodium sulfite) is added thereto, then raw cellulose is added and dissolved with stirring, and then An aqueous sodium hydroxide solution is added to completely dissolve undissolved cellulose to obtain a cuprammonium cellulose solution. This cuprammonium cellulose solution may further be mixed with a permeation performance controlling agent for coordination bonding.

As the permeation performance controlling agent, for example, an agent having a number average molecular weight of 500 and containing 10 to 70 equivalent %, preferably 15 to 50 equivalent % of carboxyl groups in the constituent monomer units is used.
200,000, preferably 1,000 to 100,000. There are various types of such polymers, but examples include copolymers of carboxyl group-containing unsaturated monomers such as acrylic acid and methacrylic acid with other copolymerizable monomers, and polyacrylonitrile. There are partial hydrolysis products.
Therefore, particularly preferred copolymerizable monomers are alkyl acrylate and alkyl methacrylate. Therefore, the most preferred copolymers are acrylic acid-alkyl acrylate (or methacrylate) copolymers, methacrylic acid-alkyl acrylate (or methacrylate) copolymers, and partial hydrolysis products of polyalkyl acrylates (or methacrylates). It is. These permeability control agents are used generally in an amount of 1 to 40 parts by weight, preferably 2 to 30 parts by weight, and most preferably 3 to 15 parts by weight, per 100 parts by weight of cellulose. For example, this permeability control agent is mixed and dissolved in a cupric ammonia cellulose solution, and the mixture is heated at a temperature of 8 to 30°C, preferably 14 to 25°C, for 20 to 120 minutes, preferably 60°C.
A spinning stock solution is obtained by stirring for ~100 minutes and coordinating mixing with the copper ammonia cellulose.

The coagulating liquid for the copper ammonia cellulose spinning stock solution has a concentration of, for example, 5 to 40%, preferably 8 to 40%.
25% aqueous sulfuric acid solution, concentration 5-50%, preferably 10
-30% nitric acid aqueous solution, 6-47% concentration, preferably 9-30% phosphoric acid aqueous solution, etc.

The selection of the non-coagulating liquid used in the above manufacturing process greatly influences the maintenance of the hollow portion of the hollow fiber and the presence or absence of irregularities on the wall surface of the hollow fiber. That is, when the non-coagulable liquid filled in the hollow fibers passes through the membrane and rapidly escapes to the outside during drying of the hollow fibers, negative pressure is created within the hollow fibers, causing collapse of the hollow fibers or unevenness on the inner walls. The non-coagulating liquid used is selected to have low permeability during drying. Suitable non-coagulating liquids include benzene, toluene, xylene, styrene, perchlorethylene, trichlorethylene, light oil, kerosene, heptane, octane, dodecane, liquid paraffin, isopropyl myristate, and the like. Moreover, these non-coagulable liquids may contain a small amount of coagulable liquid. These non-coagulable liquids have a specific gravity lower than that of the coagulable liquid 29 so that the non-coagulable liquid 33 surrounding the linear spinning dope and falling forms an upper layer of the coagulable liquid as shown in FIG. is desirable. Therefore, the non-coagulable liquid in the upper layer is
It is removed from the discharge port 34 if necessary.

The hollow fibers that have been coagulated and regenerated in this way are washed with water to remove the coagulable liquid that has adhered to them, and then
If necessary, a decopper treatment is performed to remove copper remaining in the hollow fibers, and then the hollow fibers are washed with water. Copper removal treatment is usually carried out by immersion in a dilute sulfuric acid solution or nitric acid solution with a concentration of 3 to 30%. If the spinning stock solution contains a permeability control agent as described above, the hollow fibers are immersed in an aqueous copper alkaline solution to remove the control agent, thereby reducing the molecular weight of the polymer used. Corresponding micropores are formed in the tube wall of the hollow fiber.

The hollow fibers after washing with water or after removing the permeability control agent may be further treated with warm water at 5 to 100°C, preferably 50 to 80°C, or 1 to 10% by weight, preferably 2 to 5% by weight. % concentration of glycerin aqueous solution to remove remaining copper, cupric sulfate, copper hydrogen sulfate, and medium-low molecular weight cellulose, and then dried and wound to form the desired hollow fiber. obtain.

Examples of strong alkalis include sodium hydroxide, potassium hydroxide, lithium hydroxide, ammonium hydroxide, etc., with a concentration of 0.1 to 20%, preferably 1 to 15%.
% aqueous solution.

As described above, the spinneret device for producing hollow fibers according to the present invention includes a lower nozzle body that has a first circular hole at the bottom that communicates with the lower end and a recess that communicates with the first circular hole at the top; a funnel-shaped first spinner having a lower tubular part inserted into a first circular hole of a lower nozzle body and an upper body part inserted into a recessed part of the lower nozzle body; and a second funnel-shaped spinner inserted into the first spinner. a spinner; and an upper nozzle body that is provided with a second circular hole in its bottom portion that communicates with the lower end and that is abutted and removably fixed on the lower nozzle body; a first inlet for introducing a first non-coagulable liquid that communicates with a first non-coagulable liquid discharge hole formed by a lower end opening of the spinner; a second inlet for introducing the spinning dope that communicates with a spinning dope discharge hole formed between the first spinner and the first spinner; a first circular hole in the lower nozzle body and the lower tubular portion of the first spinner; A second non-coagulable liquid that communicates with an annular space formed between the upper body part of the first spinner and the recess of the lower nozzle body, which communicates with a second non-coagulable liquid discharge hole formed by the second non-coagulable liquid discharge hole. Since it has a third inlet for introducing it non-concentrically, the spinning dope before coagulation is extruded with the first non-coagulable liquid filled in the center to maintain the hollow part. Furthermore, since the outside is surrounded and sealed by the second non-coagulating liquid and extruded, the ammonia contained in the spinning dope does not volatilize into the air and changes its composition until it comes into contact with the coagulating liquid. It is possible to produce a hollow fiber that does not undergo any change, has no skin layer, is homogeneous on its inner and outer surfaces, and has excellent dialysis and filtration performance.

Further, in this mouthpiece device, the lower nozzle body can be removed from the upper nozzle body by releasing the fixation between the upper nozzle body and the lower nozzle body. It can also be easily removed. Therefore, the inside of the first circular hole of the lower nozzle main body and the inside of the first spinner can be easily cleaned, and substances that cause clogging of the nozzle can be removed.

Furthermore, this mouthpiece device has an upper nozzle body with
Since there are three separate, non-concentric liquid inlets, each inlet can be easily connected to a conduit communicating with a liquid source.

[Brief explanation of the drawing]

FIG. 1 is a sectional view showing an embodiment of a spinneret device for producing hollow fibers according to the present invention, and FIG. 2 is a schematic diagram showing an example of a hollow fiber spinning device using the spinneret device of the present invention. 31...Lower nozzle main body, 4...First spinner, 7...Second non-coagulating liquid discharge hole, 10...Third
Inlet port, 13... Upper nozzle body, 16... Second
Spinner, 18... Spinning stock solution discharge hole, 20... First non-coagulable liquid discharge hole, 21... First introduction port, 25
...Second introduction port, 26...Spinneret device for producing hollow fibers.

Claims (1)

[Scope of utility model registration request] a lower nozzle body having a first circular hole in the bottom portion communicating with the lower end and a recessed portion communicating with the first circular hole in the upper portion; a lower tubular portion inserted into the first circular hole of the lower nozzle body; and the lower part. a funnel-shaped first spinner having an upper main body inserted into the recess of the nozzle body; a second spinner inserted into the first spinner; and a second circular hole in the bottom that communicates with the lower end; It consists of an upper nozzle body that abuts and is removably fixed on the nozzle body,
Furthermore, the upper nozzle body has a first non-coagulable liquid discharge hole for introducing a first non-coagulable liquid that communicates with a first non-coagulable liquid discharge hole formed by a lower end opening of the second spinner.
a second inlet for introducing a spinning dope that communicates with a spinning dope discharge hole formed between the second spinner and the first spinner through the inlet and the second circular hole; and the lower part. an upper body portion of the first spinner and a recessed portion of the lower nozzle body that communicate with a second non-coagulable liquid discharge hole formed between a first circular hole of the nozzle body and a lower tubular portion of the first spinner; 1. A spinneret device for producing hollow fibers, comprising a third inlet for introducing a second non-coagulable liquid that communicates with an annular space formed by a spinneret device for producing hollow fibers.