JP2003245528A - Method for manufacturing fiber reinforced porous hollow fiber membrane - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for a fiber reinforced porous hollow fiber membrane embedding a reinforcing fiber material in the central part of the cross section of the porous hollow fiber membrane, and the fiber reinforced porous hollow fiber membrane obtained by this manufacturing method. <P>SOLUTION: A film forming raw liquid is discharged from a spinning nozzle (1) and the hollow fiber membrane 5 is drawn up from a coagulation bath through the guide roller (3) in the coagulation bath and the drawing-up guide roller (4) provided outside a coagulation bath tank (2) to form the fiber reinforced porous hollow fiber membrane. In this manufacturing method, the reinforcing fiber material is introduced into the spinning nozzle (1) at an introducing angle α of 0-<180°, or 180-<360° non- parallel to the straight line connecting the discharge center point A of the spinning nozzle (1) and the hollow fiber membrane contact point B of the drawing-up guide roller (4). The obtained fiber reinforced porous hollow fiber membrane is characterized in that the reinforcing fiber material is embedded in the central part of the cross section of the hollow fiber membrane without being biased to the inner and outer surfaces of the hollow fiber membrane and has required strength and inner pressure burst strength. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a porous hollow fiber membrane used for water treatment and a porous hollow fiber membrane obtained by the method. More specifically, it relates to a method for producing a fiber-reinforced porous hollow fiber membrane in which a reinforcing fiber body is embedded, and a fiber-reinforced porous hollow fiber membrane produced by the same method.

[0002]

2. Description of the Related Art In recent years, due to increasing concern about environmental pollution and tightening of regulations, water treatment by a membrane method using a filtration membrane having excellent separation completeness and compactness, for example, industrial wastewater, wastewater, and purified water. Processing such as is attracting attention. In such a water treatment application, not only the separation characteristics and the permeation performance of the filtration membrane are excellent, but also higher mechanical characteristics than ever are required.

Conventionally, polysulfone, polyacrylonitrile, cellulose acetate produced by a wet or dry-wet spinning method has been used as a filtration membrane having an excellent permeation performance.
There is a filtration membrane made of a porous hollow fiber made of polyvinylidene fluoride or the like. These filtration membranes have a high porosity and an asymmetric structure due to their manufacturing method, but have a problem that they have essentially low mechanical strength.

As a method for improving the strength of these filtration membranes, for example, in Japanese Patent Application No. 2001-267301, the strength of the filtration membrane is obtained by arranging one or more reinforcing fiber bodies in a porous body in a direction orthogonal to the permeation direction. Is improving. The fiber reinforced porous hollow fiber membrane produced by this method ensures the strength required for the intended use such as treatment of industrial wastewater, wastewater, and purified water.

[0005]

However, the fiber-reinforced porous hollow fiber membrane produced by the above method is a fiber membrane contact between the discharge point A and the pulling guide roller 4 in the plan view of the spinning nozzle 1 shown in FIG. When the reinforcing fiber body is introduced into the spinning nozzle 1 from an angle parallel to the straight line connecting with B, the fiber-reinforced porous hollow fiber membrane discharged together with the reinforcing fiber body from the spinning nozzle 1 is still completely removed by the guide roller 3 in the bath. Is not completely solidified, tension is applied to the reinforcing fiber body in the hollow fiber membrane when the fiber membrane is pulled, and the embedding position of the reinforcing fiber body moves to the guide roller 3 side in the bath in the cross section of the hollow fiber membrane. Phenomenon occurs.

As a result, the embedding position of the reinforcing fiber body in the cross section of the yarn film may be imbalanced toward the inner surface side or the outer surface side. At the same time, the reinforcing fiber body is affected by the flow of the stock solution in the spinning nozzle due to the magnitude of the tension applied when the reinforcing fiber body is introduced into the spinning nozzle 1, and the reinforcing fiber body is cross-sectioned in the hollow fiber membrane cross section. A phenomenon occurs in which the embedding position of is biased from the center of the film thickness.

[0007]

Due to the combination of these phenomena, the embedding position of the reinforcing fiber body becomes significantly deviated, the reinforcing fiber body peels from the hollow fiber, pinholes are generated, the membrane strength and the internal pressure burst strength are increased. There was a risk that it would drop.

That is, the present invention is manufactured by a method for manufacturing a fiber-reinforced porous hollow fiber membrane in which the reinforcing fiber body is embedded in the inner surface side or the outer surface side in the membrane cross section of the porous hollow fiber membrane without unevenness, and a method for manufacturing the same. The present invention aims to provide a fiber-reinforced porous hollow fiber membrane.

[0009]

Means and Actions for Solving the Problems As a result of intensive studies on the above problems, as a result of controlling the angle and the tension when supplying the reinforcing fiber body to the spinning nozzle, It was discovered that it is possible to embed a reinforcing fiber body in the center of the film thickness.

That is, the first basic constitution of the present invention is to discharge the film-forming stock solution from the spinning nozzle, and through the guide roller in the coagulation bath and the pull-up guide roller outside the coagulation bath, the hollow fiber membrane from the coagulation bath. In the method for producing a hollow fiber membrane for pulling up the hollow fiber membrane in a plan view of the spinning nozzle, it is larger than 0 ° and 180 ° which is non-parallel to a straight line connecting the discharge point A of the spinning nozzle and the hollow fiber membrane contact point B of the pulling guide roller. Less than or 180
The method for producing a fiber-reinforced porous hollow fiber membrane is characterized by including introducing the reinforcing fiber body into the spinning nozzle at an introduction angle α of more than 360 ° and less than 360 °.

When introducing the reinforcing fiber body into the spinning nozzle,
The reinforcing fiber body is applied to the spinning nozzle along a straight line connecting the discharge point A of the spinning nozzle and the hollow fiber membrane contact point B of the pulling guide roller on a plane orthogonal to the discharge direction of the stock solution for film formation from the spinning nozzle. Introduce (Introduction angle α = 0 °, 180
°, 360 °), the reinforcing fiber body is biased toward the inner wall side of the discharge port of the spinning nozzle, and the membrane strength and the internal pressure burst strength are reduced.

As in the present invention, when the introduction angle α is in the range of more than 0 ° and less than 180 ° or more than 180 ° and less than 360 °, the discharge point A of the spinning nozzle and the hollow fiber membrane contact point B of the pulling guide roller are set. When the reinforcing fiber body is introduced into the spinning nozzle so as to intersect with the projection line of the straight line connecting the two, the reinforcing fiber body is separated from the direction of the porous hollow fiber membrane by the introduction angle α in the plan view of the spinning nozzle. In the spinning nozzle, the forces that tend to bias the embedding position of the reinforcing fiber body in the spinning nozzle due to the pulling force of the hollow fiber membrane cancel each other out, and the bias is reduced. The introduction angle α
Is preferably 30 ° to 150 ° or 210 ° to 330 °.

The second basic structure of the present invention is that the continuous reinforcing fibrous body is linearly discharged from the spinning nozzle together with the film-forming stock solution, and then the film-forming stock solution is made porous and the structure is fixed. A method for producing a porous hollow fiber membrane, which is characterized by including setting an introduction angle β of the reinforcing fiber body with respect to a center line of the stock solution discharge from the spinning nozzle in a range of 0 ° to 150 °. That is, in the side view of the spinning nozzle, the introduction angle β with respect to the stock solution discharge center line.
When the reinforcing fiber body is introduced in the range of, the fiber reinforcing body flows down the middle of the inner and outer walls of the spinning nozzle along with the flow of the film forming stock solution in the spinning nozzle, and the embedding position of the reinforcing fiber body is increased. In the cross section of the hollow fiber membrane, the phenomenon of deviating from the center of the membrane thickness is reduced.

Further, a third basic structure of the present invention is the above first
And a method for producing a fiber-reinforced porous hollow fiber membrane, which is a combination of the second basic constitution. That is, according to the third basic configuration, the functions obtained by the first and second basic configurations are combined, and the reinforcing fiber body is not biased on both the front and back sides of the hollow fiber membrane, and the central portion Can be buried in.

For the reasons described below, the supply tension of the reinforcing fiber body is preferably more than 0.2 N / fil, and particularly preferably set in the range of 0.2 N / fil to 0.8 N / fil. Further, it is preferable to set the introduction points of the reinforcing fiber body to the spinning nozzle at 1 to 6 points, and the winding speed of the membrane exceeds 20 m / min.
Set within the range of min or less.

The fiber-reinforced porous hollow fiber membrane produced in this manner has an outer surface side end d and an inner surface side end e of the fiber membrane in a membrane cross section cut at right angles to the longitudinal direction of the hollow fiber membrane.
The shortest distance to the outermost edge f of the introduced reinforcing fiber body is in the range of 20% to 80% of the film thickness, and specifically, the shortest distance is in the range of 35 μm to 80 μm, respectively, The required strength and internal pressure burst strength of the reinforced porous hollow fiber membrane are secured.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The features of the method for producing a fiber-reinforced hollow fiber membrane of the present invention and the advantages obtained by the production method will be described in detail below with reference to typical embodiments.

◇ Production method As a production method of the hollow fiber membrane in the present invention, a stock solution which is a porous body of the hollow fiber membrane is supplied between the inner and outer walls of a spinning nozzle having a double annular structure and is compatible with the stock solution. Then, the core liquid that coagulates the stock solution from the inside is supplied into the inner wall of the spinning nozzle having a double annular structure, and the core solution is discharged into the air from the spinning nozzle together with the stock solution. It can be obtained by winding. At that time, introducing a reinforcing fiber body into the stock solution discharge layer of the spinning nozzle,
A fiber-reinforced porous hollow fiber membrane is obtained by spinning at the same time.

Porous Material The material of the porous material of the hollow fiber membrane in the present invention is not particularly limited, but polysulfone resin, polyacrylonitrile, cellulose derivative, polyolefin such as polyethylene and polypropylene, polyvinylidene fluoride or poly (vinylidene fluoride). Examples thereof include fluororesins such as tetrafluoroethylene, polyamides, polyesters, polymethacrylates and polyacrylates. Further, copolymers of these resins or those in which a substituent is partially introduced may be used. Further, it may be a mixture of two or more kinds of resins.

As a specific example thereof, 18 wt% of polyvinylidene fluoride as a main component and 10 wt% of a water-soluble polymer are used.
% And 78% by weight of a solvent such as alcohol, acetone, DMAC or the like, which is optionally compatible with water, as a stock solution, and the above solution is 30% by weight, water 30% by weight, glycerin 40% by weight.
The case where it is produced by the above-mentioned production method by using as the core liquid agitated in 1.

Form of Reinforcing Fiber Body The form of the reinforcing fiber body in the present invention may be any of monofilament, multifilament and spun yarn. Further, it may be a round cross section, a hollow fiber, or a modified cross section thread. Also, although the material is not particularly limited,
Natural fibers, semi-synthetic fibers, synthetic fibers, recycled fibers, inorganic fibers and the like can be used.

The monofilament, the multifilament, or the spun yarn may be introduced at any place, and it may be appropriately changed depending on the physical properties required for the intended use, but preferably 1 to 6 A range of points is preferred.

◇ Spinning Nozzle The structure of the spinning nozzle is not particularly limited, but it has a double annular structure, and the reinforcing fiber body is provided in the sheath portion in the same direction from the horizontal direction orthogonal to the center line of the spinning solution discharge of the spinning nozzle. It is preferable that the structure is such that a plurality of lines can be simultaneously supplied around the stock solution discharge center line with a required pitch. At this time, the introduction port of the reinforcing fiber body is not limited to the horizontal position of the spinning nozzle, and may have a structure that can be introduced from an oblique direction intersecting the center line of the stock solution discharge. However, it is desirable that the angle be 0 ° or more and 150 ° or less with respect to the angle at which the undiluted solution is discharged. Is preferred.

Thickness of Membrane and Fiber Although the thickness of the hollow fiber membrane and the thickness of the reinforcing fiber body are not particularly specified, a shape in which the reinforcing fiber body is uniformly wrapped within the thickness of the hollow fiber membrane. From the viewpoint of embedding in, the area occupied by the reinforcing fiber body in the film thickness direction is preferably 60% or less. Further, in the formed hollow fiber membrane, the shortest distance between the outer surface side end portion and the inner surface side end portion of the membrane and the outermost edge portion of the introduced reinforcing fiber body is 20% to 50% of the film thickness, respectively. It is desirable to have a thickness within the range. More preferably, it is 20% to 40%.

Specifically, as shown in FIG. 3, the shortest distance between the outer surface side end portion d and the inner surface side end portion e of the hollow fiber membrane and the outermost edge portion f of the reinforcing fiber body introduced is determined. It is preferable that the thickness is in the range of 20% to 80% of the film thickness, and specifically, the shortest distance is in the range of 35 μm to 80 μm. Here, in the cross section of the hollow fiber membrane, when a straight line is drawn in a radial direction from the center point in the cross section of the hollow fiber membrane, the film thickness is the distance connecting the inner surface interface and the outer surface interface of the membrane on the straight line. To do.

◇ Introduction angle From the viewpoint of embedding the reinforcing fiber body closer to the center of the film thickness, with respect to the introducing angle of the reinforcing fiber body, the raw liquid discharge center point A of the spinning nozzle 1 and the pull-up guide roller 4 in FIG. With respect to the straight line connecting the contact point B with the introduction point α of the reinforcing fiber body introduced into the spinning nozzle (greater than 0 ° and less than 180 °, or greater than 180 ° and 360 °).
Less than) and preferably its angle α
1 in FIG. 1 and c on the diagonal thereof are 30 ° to 1
It is desirable to set it in the range of 50 °.

This is because when the reinforcing fiber body is introduced into the spinning nozzle 1, the tension for drawing the membrane is concentrated on the reinforcing fiber body in the hollow fiber membrane which is not completely solidified at the position of the guide roller 3 in the bath. As a result, the phenomenon that the embedding position of the reinforcing fiber body moves toward the guide roller 3 side in the bath in the cross section of the hollow fiber membrane occurs. When the introduction angle α of the reinforcing fiber body is parallel to the straight line connecting the points A and B (α = 0 °, 180 °, 360 °), the embedding position of the reinforcing fiber body is the center of the membrane cross section. Since it is on the straight line connecting point A and point B or in the vicinity thereof, the movement distance until the outer edge portion of the reinforcing fiber body is exposed on the outer surface or inner surface of the membrane is minimized, and even if it is a minute movement, the embedding position The bias increases.

On the other hand, when the introduction angle α for supplying the reinforcing fiber body to the spinning nozzle 1 is set to the angle range b shown in FIG. 1 and the diagonal angle range c between 30 ° and 150 °, the membrane In the cross section of, the moving distance until the outer edge of the reinforcing fiber body is exposed on the outer surface or the inner surface of the membrane is parallel to the introduction angle α (α = 0 °, 180 °, 360 °)
Since it is longer than that of the above, even if the distance that the reinforcing fiber body moves is about the same, the influence on the deviation of the embedding position is small. As a result, the embedding position of the reinforcing fiber body can be arranged closer to the center of the film thickness. When the reinforcing fiber body is introduced with the introduction angle α outside the range, the influence on the bias of the embedding position becomes large, and the embedding position of the reinforcing fiber body in the membrane cross section is unevenly embedded toward the inner surface side or the outer surface side. ,
There is a risk that the reinforcing fibrous body is peeled from the hollow fiber and the membrane strength and the internal pressure burst strength are reduced.

◇ Introducing tension The tension applied to the reinforcing fiber body when the reinforcing fiber body is introduced is more than 0.2 N / fil and is less than 0.2 N / fil from the viewpoint of embedding the reinforcing fiber body closer to the center of the film thickness. 8 N / fi
It is desirable to be 1 or less. When the tension is 0.2 N / fil or less, the reinforcing fiber body is embedded unevenly toward the inner surface side of the hollow fiber cross section under the influence of the flow of the stock solution in the spinning nozzle.
With a tension of 0.8 N / fil or more, in a polymer gel having a slow coagulation rate, the point at which the reinforcing fiber body is discharged from the spinning nozzle due to the force of pulling the film and the contact point between the in-bath guide roller 3 and the film The stress that tries to take the shortest position between them acts, and it is unevenly embedded on the outer surface side of the hollow fiber membrane, which is not preferable.

◇ Number The number of reinforcing fiber bodies to be introduced into the hollow fiber membrane is not particularly limited as long as it is 1 or more. However, when introducing a plurality of reinforcing fibers, a plurality of locations are provided within the range of the introduction angle α. It is preferable to disperse each of the reinforcing fiber bodies, and the introduction position of the reinforcing fiber body at that time is also not particularly limited, but within the same introduction angle range as when introducing one reinforcing fiber body, each reinforcing fiber body is It is desirable to introduce the hollow fiber membrane at symmetrical positions with the centerline of the hollow fiber membrane sandwiched therebetween. Further, with respect to a straight line connecting the discharge center point A of the spinning nozzle 1 and the yarn film contact point B of the pulling guide roller 4 in FIG. The reinforcing fiber bodies may be symmetrically positioned and supplied. Of course, it may be asymmetric as long as the required strength is obtained.

◇ Spinning speed The spinning speed is more than 2 m / min and 20 m / mi from the viewpoint of embedding the reinforcing fiber body in the center of the film thickness.
The range is preferably n or less.

The present invention will be specifically described below based on Examples and Comparative Examples. (Example 1) 18 parts by mass of polyvinylidene fluoride (Kainer 460 manufactured by Atsina Japan) and 9 parts by mass of polyvinylpyrrolidone (K-90) were dissolved in 73 parts by mass of N, N-dimethylacetamide under heating and stirring at 80 ° C. A spinning dope was prepared. On the other hand, N, N-dimethylacetamide 30
A coagulation liquid composed of parts by mass, 30 parts by mass of water, and 40 parts by mass of glycerin was prepared.

The above spinning dope has an outer diameter of 1.6 mm and an inner diameter of 0.
The coagulation liquid is discharged through the core of the double annular spinning nozzle, which is kept at 30 ° C. and is 8 mm. At the same time, polyester multifilament (110 dtex / 48 fil,
A reinforcing fiber body having a tensile breaking strength of 4.7 N and a tensile breaking elongation of 50%) is applied under a tension of 0.3 N / fil to the stock solution discharge center point A of the nozzle 1 and the hollow of the drawer guide roller 4 in FIG. 9 in the direction of the line connecting the thread film contact point B
The introduction angle α is 0 ° and the introduction angle β is 90 ° with respect to the line direction in which the stock solution is vertically discharged from the spinning nozzle 1 in FIG. 2.

The yarn film discharged from the spinning nozzle 1 is introduced into a coagulation bath consisting of 30 parts by mass of N, N-dimethylacetamide at 65 ° C. and 70 parts by mass of water and placed 4 cm below the nozzle ejection surface, and further coagulation bath. The fiber-reinforced porous hollow fiber membrane was spun by winding at a speed of 7 m / min via a bath guide roller 3 placed 70 cm below the surface and a pull-up guide roller 4 placed outside the bath.

The reinforcing fiber body of the obtained hollow fiber membrane is completely embedded inside the porous body of the membrane, and the outer surface end and the inner surface end of the hollow fiber membrane and the outer edge portion of the reinforcing fiber body are formed. The shortest distance between them is 25% of the film thickness, and the thickness is 50μ.
had secured m. A cross-sectional photograph of the obtained hollow fiber membrane is shown in FIG.
Is shown in. (Comparative Example 1) In Example 1, the point A in FIG.
A hollow fiber membrane was spun in the same manner as in Example 1 except that the reinforcing fiber body was introduced from an angle parallel to the line connecting the points B. The shortest distance between the outer surface end of the reinforcing fiber body embedded in the obtained hollow fiber membrane and the outer edge of the reinforcing fiber body was 15%, which was about 30 μm. A cross-sectional photograph of the obtained hollow fiber membrane is shown in FIG. (Comparative Example 2) A hollow fiber membrane was spun in the same manner as in Example 1 except that the reinforcing fiber body was supplied without applying tension. The reinforcing fiber body of the obtained hollow fiber membrane was embedded evenly at the inner surface side interface of the hollow fiber membrane. A cross-sectional photograph of the obtained hollow fiber membrane is shown in FIG. (Example 2) In Example 1, two reinforcing fiber bodies were installed at an introduction angle α of 90 ° with respect to the line direction connecting the point A and the point B in FIG. 1 and 270 ° of a diagonal portion thereof. A hollow fiber membrane was spun in the same manner as in Example 1 except that the reinforcing fiber bodies were introduced diagonally. The two reinforcing fiber bodies of the obtained hollow fiber membrane are completely embedded inside the porous body of the membrane, and the shortest distances between the outer surface end portion and the inner surface end portion and the outer edge portion of the reinforcing fiber bundle are respectively. 20% or more of the film thickness and 50 μm or more were secured.

As can be understood from the above description, in the fiber-reinforced porous hollow fiber membrane produced by the production method according to the present invention, the reinforcing fiber body is embedded without being biased toward the inner surface side or the outer surface side in the thread membrane cross section. To be done. Therefore, like the fiber-reinforced porous hollow fiber membrane obtained by the conventional manufacturing method, pinholes and exposure caused by uneven embedding position of the reinforcing fiber body, reduction in tensile strength, peeling of the reinforcing fiber body and the porous body. It is possible to obtain a high-quality fiber-reinforced porous hollow fiber membrane in which the above problems have been solved.

[Brief description of drawings]

FIG. 1 is a top view showing an outline of a spinning process in the present invention.

FIG. 2 is a side view of the spinning process.

FIG. 3 is an enlarged view schematically showing a partial cross section of a fiber-reinforced porous hollow fiber membrane obtained by the spinning method of the present invention.

FIG. 4 is an enlarged cross-sectional photograph of the fiber-reinforced porous hollow fiber membrane obtained in Example 1 of the present invention.

FIG. 5 is an enlarged cross-sectional photograph of the fiber-reinforced porous hollow fiber membrane obtained in Comparative Example 1.

6 is an enlarged cross-sectional photograph of the fiber-reinforced porous hollow fiber membrane obtained in Comparative Example 2. FIG.

[Explanation of symbols]

1 Spinning nozzle 2 coagulation bath 3 Guide roller during bath 4 Lifting roller 5 Discharged stock solution and film Introducing angle of α, β reinforcing fiber d Outer surface side end of hollow fiber membrane e Inner surface side end of hollow fiber membrane f Outer edge of reinforcing fiber body

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hiroyuki Fujiki             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Otake Office (72) Inventor Hideaki Habara             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Otake Office (72) Inventor Teruyuki Yamada             20-1 Miyuki-cho, Otake-shi, Hiroshima Mitsubishi Rayo             Central Technology Research Institute F-term (reference) 4D006 MA01 MA40 MC11X MC23X                       MC29X MC30X MC37X MC39X                       MC48X MC54X MC62X MC90                       NA05 NA75 PB02 PB08                 4L045 AA02 BA24 DC01

Claims (11)

[Claims] 1. Production of a hollow fiber membrane in which a stock solution for film formation is discharged from a spinning nozzle 1 and a hollow fiber membrane is pulled up from a coagulation bath through a guide roller 3 in the coagulation bath and a pulling guide roller 4 outside the coagulation bath. In the method, in plan view of the spinning nozzle, it is larger than 0 ° and less than 180 ° or 180 ° which is non-parallel to a straight line connecting the discharge point A of the spinning nozzle 1 and the hollow fiber membrane contact B of the pulling guide roller 4.
A method for producing a fiber-reinforced porous hollow fiber membrane, which comprises introducing the reinforcing fiber body into the spinning nozzle 1 at an introduction angle α of greater than 360 °. 2. A method for producing a fiber-reinforced porous hollow fiber membrane, wherein a continuous reinforcing fibrous body is linearly discharged from a spinning nozzle 1 together with a membrane-forming stock solution, and then the membrane-forming stock solution is made porous and its structure is fixed. In addition, in the side view of the spinning nozzle 1, the fiber is characterized by including setting the introduction angle β of the reinforcing fibrous body with respect to the stock solution discharge center line of the spinning nozzle 1 in the range of 0 ° to 150 °. A method for producing a reinforced porous hollow fiber membrane. 3. A continuous reinforcing fiber body is linearly discharged from a spinning nozzle 1 together with a stock solution for film formation, and then pulled up from a coagulation bath via a guide roller 3 in the coagulation bath and a pulling guide roller 4 outside the coagulation bath. In a method for producing a fiber-reinforced porous hollow fiber membrane, in which the membrane-forming stock solution is made porous while the film is wound up and the structure is fixed, in a plan view of the spinning nozzle, the ejection point A of the spinning nozzle 1 and the pull-up point are pulled up. Greater than 0 ° and less than 180 ° or 180 ° that is non-parallel to the straight line connecting the guide roller 4 to the hollow fiber membrane contact point B
Introducing the reinforcing fiber body into the spinning nozzle 1 with a larger introduction angle α of less than 360 °, and, in a side view of the spinning nozzle 1, the introduction angle β of the reinforcing fiber body with respect to the stock solution discharge center line is 0 ° to 150 °. The method for producing a fiber-reinforced porous hollow fiber membrane, comprising: 4. The introduction angle α of the reinforcing fiber body introduced into the spinning nozzle 1 is 30 ° to 150 ° or 210 ° to 330.
4. Setting within the range of °
A method for producing the fiber-reinforced porous hollow fiber membrane described. 5. The method for producing a fiber-reinforced porous hollow fiber membrane according to claim 2, wherein the stock solution discharge center line is a vertical line. 6. The supply tension of the reinforcing fiber body is 0.2 N /
The method for producing a fiber-reinforced porous hollow fiber membrane according to any one of claims 1 to 5, characterized in that it comprises exceeding fil. 7. The supply tension of the reinforcing fiber body is 0.2 N /
The method for producing a fiber-reinforced porous hollow fiber membrane according to any one of claims 1 to 5, characterized in that it is set in a range of fil to 0.8 N / fil. 8. The fiber-reinforced porous hollow fiber according to any one of claims 1 to 7, further comprising setting the number of introduction points of the reinforcing fiber body to the spinning nozzle at 1 to 6 points. Membrane manufacturing method. 9. The fiber reinforced according to any one of claims 1 to 8, further comprising setting a winding speed of the membrane to more than 2 m / min and not more than 20 m / min. A method for producing a porous hollow fiber membrane. 10. A fiber-reinforced porous hollow fiber membrane produced by the production method according to any one of claims 1 to 6, wherein the fiber membrane has a cross section cut at right angles to the longitudinal direction of the hollow fiber membrane. The shortest distance between the outer surface side end d and the inner surface side end e and the outermost edge f of the introduced reinforcing fiber body is in the range of 20% to 80% of the film thickness, respectively. Quality hollow fiber membrane. 11. The shortest distance is 35 μm to 8 each.
The fiber-reinforced porous hollow fiber membrane according to claim 10, which is in a range of 0 μm.