WO2020090494A1 - Filière à membrane à fibres creuses et procédé de fabrication de membrane à fibres creuses - Google Patents

Filière à membrane à fibres creuses et procédé de fabrication de membrane à fibres creuses Download PDF

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Publication number
WO2020090494A1
WO2020090494A1 PCT/JP2019/040860 JP2019040860W WO2020090494A1 WO 2020090494 A1 WO2020090494 A1 WO 2020090494A1 JP 2019040860 W JP2019040860 W JP 2019040860W WO 2020090494 A1 WO2020090494 A1 WO 2020090494A1
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Prior art keywords
hollow fiber
fiber membrane
discharge
injection liquid
spinning
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PCT/JP2019/040860
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English (en)
Japanese (ja)
Inventor
田宮竜太
山田誠之
上野良之
田中和実
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東レ株式会社
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Priority to KR1020217012215A priority Critical patent/KR20210079297A/ko
Priority to CN201980064273.3A priority patent/CN112789103B/zh
Priority to JP2019558641A priority patent/JPWO2020090494A1/ja
Publication of WO2020090494A1 publication Critical patent/WO2020090494A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/085—Details relating to the spinneret
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/50—Control of the membrane preparation process

Definitions

  • the present invention relates to a hollow fiber membrane spinneret and a method for manufacturing a hollow fiber membrane, in which spinning is performed using a spinning machine equipped with this hollow fiber membrane spinneret.
  • Hollow fiber membranes are widely used for medical purposes such as blood purifiers for renal failure patients and for water treatment such as water purifiers.
  • a method for producing the hollow fiber membrane there are a melt spinning / drawing aperture method, a heat-induced phase separation method, a non-solvent-induced phase separation method, and the like.
  • a spinneret with a double-tube structure in which an inner tube is inserted inside the outer tube is used.
  • the hollow fiber membrane is passed through an empty running section called a section and introduced into a coagulation bath to wind up the hollow fiber membrane.
  • Polysulfone-based polymers are often used in the non-solvent-induced phase separation method.
  • the characteristics required for a cartridge for a water purifier are that it has a high filtration flow rate, that it has high substance removal characteristics, and that it has a long cartridge life. Therefore, for water purifier applications, hollow fiber membranes having high water permeability and sharp material fractionation performance have been developed.
  • Hollow fiber membranes used for water purifiers are often used in the form of liquid passing from the outside to the inside of the hollow fiber membrane from the viewpoint that a large membrane area per unit volume can be obtained. From the viewpoint of fouling resistance, a dense layer is often provided on the outer surface of the hollow fiber membrane. Further, from the viewpoint of the product life of the water purifier cartridge, it is known that it is effective to reduce the outer diameter of the hollow fiber membrane to increase the membrane area per unit volume of the water purifier cartridge. However, as the outer diameter of the hollow fiber membrane becomes smaller, the risk of yarn breakage increases, so there is a demand for a spinneret having a double-tube structure capable of stably spinning hollow fiber membranes of various thread diameters.
  • the discharge port of the inner tube and the discharge port of the outer tube are often formed on the discharge surface at the same height.
  • the ejection port of the inner tube of the spinneret protrudes from 0.3 to 20 mm from the ejection port of the outer tube.
  • a spinneret having a double tube structure is disclosed. Further, a method is disclosed in which a hollow fiber membrane having sufficient mechanical properties is obtained by spinning at a draft rate of 0.95 to 1.3 even if the spinning speed is increased.
  • Patent Document 2 discloses a method for producing a hollow fiber membrane in which an electric field is applied to a spinneret having a double tube structure. Specifically, the inner tube and the outer tube are separated from each other by an insulator, and the tube has a double tube structure. Each tube is provided with an electrode. The inner tube and the outer tube do not protrude from the discharge surface, but the discharge surface does not extend outside the outer tube and is a narrow region.
  • the draft ratio is the ratio of the take-up speed to the linear discharge speed discharged from the spinneret.
  • Patent Document 1 With the spinning method disclosed in Patent Document 1, the range of draft ratio is extremely narrow, and it is difficult to collect hollow fiber membranes with various yarn diameters.
  • the ejection port of the inner tube is projected, but the ejection port of the outer tube is formed on the ejection surface, so the ejected solution spreads to the ejection surface due to surface tension, and spinning stability is improved. There were challenges. Further, in the spinneret disclosed in Patent Document 1, the ejection port of the inner tube is projected, and the thin metal portion between the undiluted solution and the injection liquid ejection port is exposed, so a slight impact from the outside There is a concern that it will be damaged.
  • the spinneret disclosed in Patent Document 2 has a structure in which the discharge ports of the undiluted solution and the injection liquid are projected (the discharge port does not project from the discharge surface, but the discharge surface is narrow and it seems to project).
  • the discharge port does not project from the discharge surface, but the discharge surface is narrow and it seems to project.
  • the outer tube is made thicker and the discharge surface is expanded, so that the discharge solution sticks to the discharge surface, the draft ratio becomes large, and thread breakage occurs.
  • the protruding metal part is exposed, there is a concern that the metal part may be damaged by a slight impact from the outside, as in Patent Document 1.
  • the hollow fiber membrane spinneret for solving the above-mentioned problems includes an injection liquid ejection port for ejecting an injection liquid on an ejection surface, and an annular slit (spinning stock solution) surrounding the injection liquid ejection port for ejecting a spinning dope.
  • the hollow fiber membrane spinneret has an area S1 of the ring surrounded by the inner diameter of the annular recess and the inner diameter of the annular slit on the ejection surface, and an area S2 of the annular slit on the ejection surface.
  • a hollow fiber membrane spinneret satisfying S2 / S1 ⁇ 0.4.
  • a method for producing a hollow fiber membrane for solving the above-mentioned problems using a spinning machine equipped with any one of the above hollow fiber membrane spinneret, the injection liquid from the injection liquid discharge port, the spinning stock solution from the annular slit Hollow fiber membrane that is discharged and spun so that the temporary discharge draft V2 / V1 which is the ratio of the temporary discharge linear velocity V1 [m / min] and the hollow fiber take-up velocity V2 [m / min] is 30 or less.
  • the temporary ejection linear velocity V1 Q / S3 Q [cm 3 / min]: Total discharge amount of stock solution for spinning and injected liquid S 3 [mm 2 ]: Area surrounded by inner diameter of annular recess.
  • the injection liquid has a coagulation number of 10 or more.
  • the phenomenon that the solution discharged from the discharge port of the die sticks to the discharge surface immediately after discharge is unlikely to occur, and it is possible to prevent the discharged solution from spreading to the discharge surface due to surface tension, resulting in yarn breakage.
  • a hollow fiber membrane spinneret capable of stable spinning without generation. Further, a hollow fiber membrane spinneret with less risk of damage to the discharge port due to impact is provided. By using a spinning machine equipped with this hollow fiber membrane spinneret, it is possible to stabilize hollow fiber membranes of various yarn diameters that have the necessary fractionation performance (removal performance of particles of 0.3 ⁇ m or more) and water permeability required for a water purifier. Can be manufactured in a simple manner.
  • FIG. 3 is a schematic diagram showing a state in which a spinning dope and an injection liquid are discharged from the hollow fiber membrane spinneret of the present invention.
  • FIG. 3 is a schematic diagram showing a state in which a spinning dope and an injection liquid are discharged from the hollow fiber membrane spinneret of the present invention.
  • FIG. 3 is a schematic diagram showing a state in which a spinning dope and an injection liquid are discharged from the hollow fiber membrane spinneret of the present invention.
  • Performances required for hollow fiber membranes used for water purifiers mainly include water permeability and fractionation performance.
  • the water permeability of the hollow fiber membrane for a water purifier is preferably 80 ml / (Pa ⁇ hr ⁇ m 2 ) or more when the outer diameter of the hollow fiber membrane is 450 ⁇ m or more. It is more preferably 90 ml / (Pa ⁇ hr ⁇ m 2 ) or more, still more preferably 100 ml / (Pa ⁇ hr ⁇ m 2 ). If the outer diameter of the hollow fiber membrane is reduced, the membrane area per unit volume can be increased, and therefore, it is preferable to reduce the diameter from the viewpoint of extending the life.
  • a hollow fiber membrane having an outer diameter reduced to 300 ⁇ m preferably has a water permeability of 30 ml / (Pa ⁇ hr ⁇ m 2 ) or more. It is more preferably 40 ml / (Pa ⁇ hr ⁇ m 2 ) or more, still more preferably 50 ml / (Pa ⁇ hr ⁇ m 2 ).
  • Hollow fiber membranes for water purifiers are required to be able to remove bacteria. Therefore, as the fractionation performance, it is preferable that the removal rate of the latex bead particles having a particle diameter of 0.3 ⁇ m is 99% or more regardless of the outer diameter of the hollow fiber membrane.
  • a non-solvent-induced phase separation method is used to produce a hollow fiber membrane having an asymmetric structure by a liquid injection method using a hollow-fiber membrane spinneret having a double-tube structure.
  • a spinning stock solution is injected into an annular slit 1 part of a hollow fiber membrane spinneret, and a non-coagulating liquid or the like is injected into an injection liquid discharge port to form a hollow shape of a hollow fiber membrane.
  • the spinning dope is discharged from the annular slit 1 of the hollow fiber membrane spinneret together with, for example, a non-coagulating liquid, idles in a predetermined section, and is then introduced into a coagulating bath provided on the downstream side. Then, the spinning dope is coagulated into a hollow shape by a coagulation bath to form a hollow fiber membrane. Then, this hollow fiber membrane is washed with water and then wound into a skein.
  • double-tube structure hollow fiber membrane spinneret includes an injection liquid discharge port and a spinning dope discharge port (annular slit 1), and the spinning dope discharge port (annular slit 1) A die that surrounds the liquid ejection port and has a double-layered ejection port.
  • the “ejection surface” is a flat surface including an ejection port for ejecting a solution.
  • the ejection surface refers to a flat portion that extends around the ejection port and has the same height.
  • An injection liquid ejection port from which the solution is ejected and a spinning stock solution ejection port (annular slit 1) are opened in the die, and at the same time the solution is ejected from the injection liquid ejection port, the spinning dope solution ejection port (annular slit 1).
  • Another solution is discharged from.
  • the solution discharged from the spinning dope discharge port (annular slit 1) forms a hollow film, that is, a hollow fiber film having a hollow center through a film forming process.
  • the hollow-fiber membrane spinneret with a double-tube structure has a hole for forming a spinning stock solution discharge port (annular slit 1) on the discharge surface, and an inner tube for forming an injection liquid discharge port inside thereof. ..
  • the outer tube forms the outer periphery of the spinning dope discharge port (annular slit 1). That is, the outer tube may have an annular shape or a wide flat surface integrated with the discharge surface and / or the mouthpiece.
  • the annular slit 1 refers to a ring-shaped gap that surrounds the injection liquid discharge port and discharges the spinning solution.
  • the ring-shaped gap between the inner pipe and the outer pipe is called "annular slit 1".
  • the annular slit 1 is a space surrounded by the outer side of the inner tube and the inner side of the outer tube when viewed from the center of the cross section of the hollow fiber.
  • the spinneret includes a flow path for the discharge solution, a filter, and the like.
  • the whole is called a cap structure.
  • Each die of the die structure includes at least each ejection surface, each injection liquid ejection port, and each spinning stock solution ejection port (annular slit 1).
  • the ejection surface may be evenly spread and may be a plane common to the adjacent mouthpieces.
  • annular recess 2 surrounding the annular slit 1 on the ejection surface in the present invention will be described with reference to the drawings.
  • FIG. 1 is a schematic plan view of a hollow fiber membrane spinneret observed from the direction in which a solution is discharged.
  • reference numeral 4 is a metal part, but the first ring-shaped metal part 4 in the innermost layer from the center is the inner pipe.
  • the second ring-shaped metal part 4 from the center is the outer tube.
  • the outer tube forms the outer periphery of the spinning solution discharge port on the discharge surface.
  • the ejection surface may be circular or polygonal.
  • each metal part 4 The space from the center to the inner side of the first ring-shaped metal portion 4 in the innermost layer is the injection liquid ejection port 3 and is a hole for ejecting the injection liquid.
  • the gap between the first ring-shaped metal part 4 and the second ring-shaped metal part 4 in the innermost layer is an annular slit 1 from which the spinning dope is discharged. Is.
  • the region sandwiched by the outer wall on the outer side when viewed from the center of the second ring-shaped metal part 4 and the third ring-shaped metal part 4 is an annular recess 2.
  • the annular recess 2 is recessed low from the discharge plane toward the inside of the die (toward the back of the paper in FIG.
  • the height of the ring-shaped metal portion 4 which is second from the center is higher than that of the recess, but it is on the same plane as the ejection surface and does not protrude from the ejection surface (Fig. 2).
  • the action and effect of the annular recess 2 will be described later.
  • the third link-shaped metal part 4 from the center is a protection part that further surrounds the outside of the annular recess 2 on the ejection surface.
  • the protective portion is preferably on the ejection surface, outside the annular recess 2 and at the same height as the ejection surface. The same height may differ by about 1 mm as long as the effect of the present invention is not impaired.
  • the protection part has the same height as the ejection surface.
  • the material of the hollow fiber membrane, the spinning stock solution discharged from the annular slit 1 (that is, the spinning stock solution discharge port), and the injection liquid discharged from the injection liquid discharge port will be described.
  • the above hollow fiber membrane contains a hydrophobic polymer, and this hydrophobic polymer constitutes the base material of the hollow fiber membrane.
  • the hydrophobic polymer it is preferable to use polysulfone-based polymers such as polysulfone, polyether sulfone, and polyarylate. Among these, polysulfone is more preferably used.
  • a fluorine-based resin such as polyvinylidene difluoride, a cellulose-based resin such as cellulose triacetate or cellulose diacetate, polymethyl methacrylate, polyacrylonitrile, or polyamide can be appropriately selected.
  • the hollow fiber membrane components such as polysulfone-based polymer are dissolved in the spinning dope.
  • the solvent for dissolving the polymer various solvents such as dimethyl sulfoxide, N, N-dimethylacetamide, dimethylformamide, N-methyl-2-pyrrolidone and dioxane are used.
  • N, N-dimethylacetamide, dimethylsulfoxide, dimethylformamide, and N-methyl-2-pyrrolidone are preferable, and they may be appropriately selected depending on the viscosity of the spinning dope and the coagulability of the injection liquid.
  • the liquid injected into the injection liquid discharge port 3 at the center of the hollow-fiber membrane spinneret having the double-tube structure should be coagulable or non-coagulable depending on the desired form of the hollow-fiber membrane. It can be appropriately selected.
  • the injection liquid containing the poor solvent is discharged from the injection liquid discharge port 3 and brought into contact with the spinning dope to make the poor solvent Solidify in a coagulation bath consisting of. Since the poor solvent is supplied into the hollow fiber membrane by diffusion, the supply amount of the poor solvent changes in the thickness direction of the hollow fiber membrane. Therefore, the pore diameter of the cross section in the thickness direction of the hollow fiber membrane becomes large from one surface of the hollow fiber membrane toward the other surface. Therefore, it is preferable that the injection liquid containing the poor solvent and the spinning dope are brought into contact immediately after discharge. If the concentration is adjusted by using the injection liquid as a mixed liquid of a poor solvent and a good solvent, the coagulability changes, and the minor diameter of the pores on the surface on the side in contact with the injection liquid and the thickness of the dense layer can be controlled.
  • a coagulating liquid When a coagulating liquid is used as the injection liquid, coagulation starts from the inner surface, so a dense layer is formed on the inner surface side of the hollow fiber membrane.
  • a non-coagulating liquid when used as the injection liquid, the coagulation is started by the cold air containing the poor solvent supplied in the idle portion up to the coagulation bath and the coagulation bath made of the poor solvent provided on the downstream side.
  • a dense layer is formed on the outer surface side of the hollow fiber membrane. Therefore, in the case of a water purifier used in a flow of filtering from the outer surface side to the inner surface side of the hollow fiber membrane, a non-coagulating liquid is preferably used as the injection liquid.
  • the composition of the spinning dope In the production method of the present invention, the composition of the spinning dope, the composition of the injection liquid, the ejection amount when ejecting the spinning dope or the injection liquid from the spinneret, the dew point / temperature / speed of the cold air of the dry part after ejection, the spinning dope ejection time
  • a hollow fiber membrane having desired characteristics can be obtained by controlling the draft ratio, the coagulation bath temperature, and the like.
  • the concentration of the poor solvent in the coagulation bath is preferably 30% by mass or more, more preferably 50% by mass or more, even more preferably 80% by mass or more, based on the whole coagulation liquid.
  • the spinning stock solution when the spinning stock solution is discharged from the annular slit 1, the spinning stock solution may stick to the discharge surface.
  • a non-coagulating liquid is used as the injection liquid, solidification of the spinning dope does not proceed immediately below the spinneret, the wettability of the spinning dope on the solid surface becomes strong, and the outer circumference of the annular slit 1 (spinning dope discharge port) The phenomenon of sticking to the outer tube or the discharge surface that forms the bubble is likely to occur.
  • the discharge amount of the spinning dope is small, and this phenomenon easily occurs.
  • the discharge volume of the spinning dope is small, the surface tension of the spinning dope immediately after discharge is weak and the weight of the spinning dope becomes light, so that the spinning dope that does not solidify spreads on the ejection surface and sticks to the ejection surface. ..
  • FIG. 4 and 5 are schematic views illustrating an example of a conventional hollow fiber membrane spinneret.
  • FIG. 4 is a schematic view of the discharge surface of the hollow fiber membrane spinneret observed from the direction in which the solution is discharged
  • FIG. 5 is a sectional view taken along a plane perpendicular to the discharge surface.
  • a ring-shaped slit 1 serving as a spinning stock solution discharge port is provided so as to surround the injection liquid discharge port 3, and the spinning stock solution 5 is discharged from the annular slit 1. Further, the injection liquid 6 is ejected from the injection liquid ejection port 3.
  • a metal portion 4 is formed between the injection liquid discharge port 3 and the annular slit 1 and around the annular slit 1. That is, on the ejection surface, the metal portion 4 between the injection liquid ejection port 3 and the annular slit 1 is the inner tube, and the outer side of the annular slit 1 is the outer tube.
  • the outer tube extending outside the annular slit 1 is a flat surface having a uniform height with respect to the ejection surface.
  • FIG. 6 is a schematic view showing a state in which the spinning dope 5 and the injection liquid 6 are discharged from the conventional hollow fiber membrane spinneret.
  • the spinning stock solution 5 is attached to this portion so as to spread. ing.
  • the apparent discharge diameter immediately after discharge becomes large, resulting in a high draft condition.
  • the yarn may be stretched and strongly drawn, the membrane structure may be destroyed, and the desired removal performance may not be satisfied.
  • the drawing is remarkable, the yarn is stretched, and the yarn breaks.
  • the occurrence of this sticking phenomenon is also related to the coagulability of the injected liquid.
  • the coagulation value is an index of the coagulability of the injected liquid.
  • the coagulation number represents the added mass of the injected liquid at the time when the system became cloudy by adding the injected liquid little by little to 50 g of a solution having a concentration of the main polymer constituting the film of 1% by mass. The smaller the coagulation value, the higher the coagulability of the injected liquid.
  • the coagulation value is 10 or more, the sticking phenomenon is likely to occur, and when the coagulation value is 30 or more, depending on the conditions, sticking occurs immediately after the spinning dope is discharged, which leads to yarn breakage.
  • a coagulating injection liquid having a coagulation value of less than 10 When a coagulating injection liquid having a coagulation value of less than 10 is used, the spinning dope is coagulated immediately below the spinneret, so that the spinning dope does not stick to the ejection surface and the temporary ejection draft does not increase.
  • a dense layer with a small pore size is formed not only on the outer surface of the hollow fiber membrane, but also on the inner surface side, so when high water permeability such as for a water purifier is required, It cannot satisfy the desired water permeability. That is, in the present invention, an injection liquid having a coagulation number of 10 or more is more preferably used.
  • the metal portion around the annular slit 1 on the discharge surface may be narrowed to reduce the area where the spinning dope can stick.
  • the metal portion on the outer periphery of the annular slit 1 is narrowed, the portion where the spinning stock solution and the injection liquid are discharged, that is, the inner pipe forming the outer periphery of the injection liquid discharge port 3 and the outer portion forming the outer periphery of the annular slit 1 Only the tube projects from the discharge surface. With such a spinneret, the inner tube and the outer tube of the thin tube wall are exposed, and are easily damaged by a slight impact.
  • FIG. 1 and 2 are schematic views illustrating the hollow fiber membrane spinneret of the present invention.
  • FIG. 1 is a view of the ejection surface observed from the direction in which the solution is ejected
  • FIG. 2 is a cross-sectional view taken along a plane perpendicular to the ejection surface.
  • an annular slit 1 is provided so as to surround the injection liquid ejection port 3, and an annular recess 2 that surrounds the annular slit 1 is formed.
  • the protective portion the third metal portion 4 from the center in FIG. 1 is formed on the ejection surface so as to surround the annular recess 2, the area of the ejection surface is large.
  • the outer tube is formed with an annular recess 2 one step lower than the discharge surface. Therefore, the spinning dope spreads up to the metal portion 4 (the ring-shaped metal portion 4 located second from the center in FIG. 1) on the outer periphery of the annular slit, but in the annular recess 2 portion surrounding the annular slit 1. Does not spread.
  • FIG. 3 is a schematic diagram showing a state in which the spinning dope 5 and the injection liquid 6 are discharged from the hollow fiber membrane spinneret of the present invention.
  • the metal portion on the outer periphery of the annular slit 1 is narrow, the spreading of the spinning dope 5 is suppressed.
  • the hollow fiber membrane spinneret of the present invention has the area S1 of the portion surrounded by the inner diameter of the annular recess and the inner diameter of the annular slit 1 on the ejection surface and the ejection surface from the viewpoint of reducing the area where the spinning dope spreads. It is preferable that the area S2 of the annular slit 1 in 3 satisfies S2 / S1 ⁇ 0.4.
  • S2 / S1 is 0.4 or more, the area S2 of the annular slit, that is, the area S1 of the metal portion on the outer periphery is sufficiently small with respect to the discharge amount of the spinning dope, so that the spreading of the spinning dope is suppressed.
  • the destruction of the membrane structure of the hollow fiber membrane does not occur, and the desired fractionation performance can be obtained. Further, spreading of the spinning dope is suppressed, yarn breakage is unlikely to occur, and the hollow fiber membrane can be stably spun.
  • the area S1 [mm 2 ] is the sum of the area of the annular slit 1 and the area of the metal portion 4 forming the outer periphery thereof.
  • the ratio of S2 / S1 obtained by dividing the area S2 [mm 2 ] by the area S1 is related to the thickness of the tube wall of the outer tube.
  • the ratio of S2 / S1 decreases as the thickness of the tube wall of the outer tube increases and the spread on the discharge surface increases. As described above, when the ratio of S2 / S1 is larger than 0.4, the thickness of the outer wall of the outer tube is small, and the spread of the outer surface to the discharge surface is suppressed.
  • the upper limit of the S2 / S1 ratio is less than 1.0, but 0.95 or less is preferable in consideration of the thickness of the outer tube.
  • the width of the metal portion between the inner diameter of the annular recess 2 and the outer diameter of the annular slit 1, that is, the thickness of the tube wall of the outer tube is preferably 50 ⁇ m or more from the viewpoint of maintaining the physical strength. Further, it is preferably 250 ⁇ m or less in terms of suppressing yarn breakage due to high draft conditions.
  • the shape of the annular recess 2 is such that the width of the recess is set to a distance such that the discharged solution does not spread to the outer discharge surface, and is generally several 100 ⁇ m to several mm. Further, the depth of the groove-shaped indentation that forms the recess may be such that the discharged solution forms a step that does not spread on the discharge surface, and generally, a depth of about 0.3 mm to 30 mm may be used. ..
  • the shape of the wall of the recess on the outer side of the outer tube is not particularly limited, but may be vertical, or may be a tapered shape including an inclined surface as shown in FIG.
  • the ratio of the outer diameter (d4) of the annular recess 2 to the inner diameter (d3) of the annular recess 2, that is, the ratio of d4 / d3 is preferably 1.5 to 7.5 times.
  • the ejection surface may extend further outside the annular recess 2.
  • the ejection surface is preferably formed wider outside the annular recess 2.
  • a temporary discharge draft which is a ratio of the temporary discharge linear velocity V1 [m / min] and the hollow fiber take-up velocity V2 [m / min]. It is preferable to perform spinning so that V2 / V1 is 30 or less from the viewpoint of preventing sticking of the spinning dope to the discharge surface. If the provisional ejection draft is larger than 30, the apparent ejection diameter immediately after ejection becomes large, and under high draft conditions, the yarn may be stretched and strongly stretched, and the film structure may be destroyed. It is more preferable to perform spinning so that the temporary discharge draft V2 / V1 is 20 or less, and particularly preferably 15 or less. Further, in particular, when the temporary discharge draft is 100 or more, the yarn may be severely stretched and the yarn may be stretched in the longitudinal direction, which may cause yarn breakage.
  • the temporary discharge linear velocity V1 [m / min] is the total discharge amount Q [cm 3 / min] of the spinning dope and the injection liquid, and the polymer solution obtained by combining the spinning dope and the injection liquid on the die discharge surface. Calculated from the spread area.
  • the area of this expanded polymer solution is the total area of the part surrounded by the outer diameter of the annular slit 1 and the part where the polymer solution sticks to the discharge surface of the die beyond the outer diameter of the annular slit 1. is there.
  • the discharged polymer solution travels in the dry section from directly below the spinneret to the coagulation bath.
  • the dry section it is preferable to provide a running section in which the temperature and humidity are positively controlled, because it is effective for controlling the opening of the hollow fiber membrane and variation in the performance of the obtained hollow fiber membrane can be reduced.
  • this humidity control method include a method in which cold air tubes are provided on both sides of the spinning stock solution discharged from the hollow fiber membrane spinneret, and a method in which the spinning stock solution discharged from the double tube structure spinneret is surrounded by an annular cold air tube. is there.
  • cold air tubes When installing cold air tubes on both sides of the spinning dope discharged from the double-pipe structure spinneret, cool air is supplied from one side of the cold air tube and cold air is exhausted from the other side, or cold air is supplied from both sides.
  • the method is preferable because the humidity of the dry part atmosphere can be controlled more positively.
  • the dry section is less likely to be affected by the outside air, and it is possible to reduce the performance variation of the obtained hollow fiber membrane, which is preferable. ..
  • the dry section it is effective to adjust the dew point temperature and the wind speed of the cold air and to supply water, which is a poor solvent, in an appropriate amount in order to increase the hole diameter on the outer surface and increase the open area ratio.
  • the dew point temperature of the dry section is preferably 18 ° C or higher, more preferably 21 ° C or higher.
  • the length of the dry portion is preferably 200 mm or less in order to make the pore diameter on the surface of the hollow fiber membrane suitable and prevent the yarn from shaking during membrane formation.
  • Hollow fiber membranes for water purifiers are often used in a dry state.
  • the hydrophilic polymer is unevenly distributed on the surface of the hollow fiber membrane, which results in the water permeability of the hollow fiber membrane.
  • the filtration flow rate when modularized decreases. Therefore, it is preferable to wash the obtained hollow fiber membrane with warm water as a pretreatment.
  • the temperature of the warm water is preferably 60 ° C or higher, more preferably 70 ° C or higher, even more preferably 80 ° C or higher.
  • the hollow fiber membrane spun using the hollow fiber membrane spinneret of the present invention can be suitably used for a water purifier cartridge.
  • the water purifier cartridge having the hollow fiber membrane can be manufactured by a conventionally used method.
  • the hollow fiber membrane was cut with a single blade in the thickness direction and set on a micro watcher (VH-Z100 manufactured by KEYENCE). When the hollow fiber cross section was crushed by the cutting, the cutting was repeated until it became a substantially perfect circle.
  • the cross section of the hollow fiber membrane was observed with a 1000 ⁇ lens, the thickness range of the hollow fiber membrane was specified on the monitor screen on which the cross section was projected, and the numerical value displayed on the monitor screen was read. In addition, a numerical value is displayed on the monitor screen for the inner diameter of the hollow fiber membrane by specifying the width of the hollow portion. The same measurement was performed on 30 hollow fiber membranes, and the average value of the measurement data of a total of 30 was calculated to obtain the inner diameter (ID) and the film thickness (WT) of the hollow fiber membranes.
  • the discharge flow rate (g / min) was measured with an electronic balance, and the discharge flow rate (g / min) of the injection liquid was subtracted, and the remainder was taken as the discharge flow rate (g / min) of the spinning dope.
  • the discharge flow rate per minute (cm 3 / min) was calculated from the composition ratio and specific gravity of the spinning dope. With respect to the above, the same measurement was performed 5 times, and the average value of the measurement data for each 5 was calculated to be the discharge amount of the injected liquid (cm 3 / min) and the discharge flow rate of the spinning dope (cm 3 / min).
  • the hollow fiber membrane take-up speed in the present invention is determined by the solidification of the polymer solution composed of the spinning dope and the injection liquid discharged from the hollow fiber membrane spinneret in the coagulation bath, and the coagulation taken first.
  • ⁇ Hollow fiber membrane take-up speed (m / min) (L ⁇ C) / M
  • L Perimeter of coagulation bath roller (m)
  • C Coagulation bath roller rotation speed (times)
  • M rotation time (minutes).
  • UFRS water permeability
  • a small module was prepared in the same manner as in (5) above.
  • a polystyrene latex bead suspension having a concentration of 200 ppm (manufactured by Invitrogen, Sulfate latex) was supplied from the outside of the hollow fiber membrane, and the concentration of the suspension that had permeated inward through the hollow fiber membrane was measured.
  • the rejection rate was calculated by the following equation using the values of the supply side concentration of 200 ppm and the permeation side concentration.
  • the latex beads used had a particle diameter of 0.3 ⁇ m.
  • -Rejection rate (%) (1-Cp / Cf) x 100
  • Cp concentration on the transmission side
  • Cf concentration on the supply side
  • the relationship between the absorbance at 260 nm and the concentration of latex beads was measured in advance, and the concentration was determined by measuring the absorbance of the suspension on the transmission side.
  • the absorbance was measured using a spectrophotometer (U-5100 manufactured by Hitachi Ltd.).
  • Example 1 The hollow fiber membrane spinneret having the double tube structure shown in FIGS. 1 and 2 was used.
  • the injection liquid discharge port 3 had a diameter of 0.5 mm
  • the annular slit 1 had an inner diameter of 0.7 mm and an outer diameter of 1.0 mm
  • the annular recess 2 had an inner diameter of 1.1 mm and an outer diameter of 4.7 mm.
  • the ejection surface was further expanded to the outside of the annular recess 2.
  • a non-coagulable liquid consisting of 55 parts by mass of DMAc, 30 parts by mass of polyvinylpyrrolidone (K30 manufactured by BASF, weight average molecular weight 40,000) and 15 parts by mass of glycerin was used as an injection liquid.
  • the coagulation number of the injected liquid was 61.
  • the injected liquid was discharged from the injected liquid discharge port 3 at 1.1 cm 3 / min.
  • the base was kept warm at 40 ° C.
  • a cold air tube was installed in the dry part, and a predetermined dry length was passed while supplying cold air, and it was immersed in a coagulation bath at 85 ° C. containing a mixed solution of 90 parts of water and 10 parts of DMAc to coagulate. Then, after a washing step with water, it was wound around a cassette frame at a take-up speed of 40 m / min to obtain a wet hollow fiber membrane.
  • the wound hollow fiber membrane had an outer diameter of 305 ⁇ m and a thickness of 55 ⁇ m (shown in Table 3).
  • the injection liquid immediately after discharge spread to the inner diameter of the annular slit 1
  • the spinning dope spread from the inner diameter of the annular slit 1 to the inner diameter of the annular recess 2.
  • the area of the portion surrounded by the outer diameter of the annular slit 1 and the area of the portion where the polymer solution sticks to the ejection surface beyond the outer diameter of the annular slit 1 are combined, and hereafter, The discharge area of the polymer solution ".
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 3.26 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 12. 3 (shown in Table 2). Since S2 / S1 was set to 0.71 and the temporary discharge draft was set to 12.3, the yarn breakage did not occur during the sample collection for 5 hours, and the hollow fiber membrane could be collected stably.
  • the obtained hollow fiber membrane was cut into 30 cm in the longitudinal direction and washed with warm water at 80 ° C. for 5 hours.
  • the hollow fiber membrane was dried in a dryer to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained dry hollow fiber membrane was 61 (mL / (hr ⁇ Pa ⁇ m 2 )), and the particle removal rate of 0.3 ⁇ m was 100% (shown in Table 3).
  • Example 2 The hollow fiber membrane spinneret having the double tube structure shown in FIGS. 1 and 2 was used.
  • the injection liquid discharge port 3 had a diameter of 0.5 mm
  • the annular slit 1 had an inner diameter of 0.7 mm and an outer diameter of 1.0 mm
  • the annular recess 2 had an inner diameter of 1.2 mm and an outer diameter of 4.8 mm.
  • the ejection surface was further expanded to the outside of the annular recess 2.
  • the area of the portion surrounded by the inner diameter of the annular slit 1 and the inner diameter of the annular recess 2 on the ejection surface was S1, and the area of the portion surrounded by the inner diameter and the outer diameter of the annular slit 1 on the ejection surface was S2. At that time, S2 / S1 was 0.54.
  • Example 2 The same spinning stock solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3, respectively. At this time, the flow rate of the spinning dope was 2.0 cm 3 / min, and the flow rate of the injection liquid was 1.1 cm 3 / min. The base was kept warm at 40 ° C.
  • Example 2 In the same manner as in Example 1, after passing through a coagulation bath having a predetermined dry length, it was washed with water and wound around a mould frame at a take-up speed of 40 m / min to obtain a hollow fiber membrane in a wet state.
  • the hollow fiber membrane wound up had an outer diameter of 305 ⁇ m and a film thickness of 55 ⁇ m.
  • the injected liquid immediately after discharge spread to the inner diameter of the annular slit 1, and the spinning dope spread from the inner diameter of the annular slit 1 to the inner diameter of the annular recess 2.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 2.74 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 14. It was 6. Since S2 / S1 was set to 0.54 and the temporary discharge draft was set to 14.6, the yarn breakage did not occur during the sample collection for 5 hours, and the hollow fiber membrane could be collected stably.
  • the obtained hollow fiber membrane was dried in the same manner as in Example 1 to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained hollow fiber membrane in the dry state was 61 (mL / (hr ⁇ Pa ⁇ m 2 )), and the particle removal rate of 0.3 ⁇ m was 100%.
  • Example 3 The same hollow fiber membrane spinneret as in Example 2 was used. The same spinning solution as in Example 1 was prepared and discharged from the annular slit 1 at 2.0 cm 3 / min. A non-solidifying liquid consisting of 92 parts by mass of DMAc and 8 parts by mass of water was used as an injection liquid. The coagulation number of the injected liquid was 61. The injected liquid was discharged from the injected liquid discharge port 3 at 1.1 cm 3 / min. The base was kept warm at 40 ° C.
  • Example 2 In the same manner as in Example 1, after passing through a coagulation bath having a predetermined dry length, it was washed with water and wound around a mould frame at a take-up speed of 40 m / min to obtain a hollow fiber membrane in a wet state.
  • the wound hollow fiber membrane had an outer diameter of 300 ⁇ m and a thickness of 55 ⁇ m.
  • the injection liquid immediately after discharge spread to the inner diameter of the annular slit 1, and the spinning solution was spread from the inner diameter of the annular slit 1 to the inner diameter of the annular recess 2.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 2.74 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 14. It was 6. Since S2 / S1 was set to 0.54 and the temporary discharge draft was set to 14.6, the yarn breakage did not occur during the sample collection for 5 hours, and the hollow fiber membrane could be collected stably.
  • the obtained hollow fiber membrane was dried in the same manner as in Example 1 to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained hollow fiber membrane in the dry state was 61 (mL / (hr ⁇ Pa ⁇ m 2 )), and the particle removal rate of 0.3 ⁇ m was 100%.
  • Example 4 The same hollow fiber membrane spinneret as in Example 2 was used.
  • the same spinning stock solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3, respectively.
  • the flow rate of the spinning solution at this time is 2.9 cm 3 / min, the flow rate of the injected liquid was 1.4 cm 3 / min.
  • the base was kept warm at 40 ° C.
  • a wet hollow fiber membrane was obtained by winding it through a water washing step at a take-up speed of 50 m / min.
  • the wound hollow fiber membrane had an outer diameter of 310 ⁇ m and a thickness of 60 ⁇ m.
  • the injection liquid immediately after discharge spread to the inner diameter of the annular slit 1
  • the spinning solution was spread from the inner diameter of the annular slit 1 to the inner diameter of the annular recess 2.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 3.80 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 13. It was 2. Since S2 / S1 was set to 0.54 and the temporary discharge draft was set to 13.2, the yarn breakage did not occur during the sample collection for 5 hours, and the hollow fiber membrane could be collected stably.
  • the obtained hollow fiber membrane was dried in the same manner as in Example 1 to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained dry hollow fiber membrane was 54 (mL / (hr ⁇ Pa ⁇ m 2 )), and the particle removal rate of 0.3 ⁇ m was 100%.
  • Example 5 The hollow fiber membrane spinneret having the double tube structure shown in FIGS. 1 and 2 was used.
  • the injection liquid discharge port 3 had a diameter of 0.3 mm
  • the annular slit 1 had an inner diameter of 0.5 mm and an outer diameter of 0.7 mm
  • the annular recess 2 had an inner diameter of 0.9 mm and an outer diameter of 4.5 mm.
  • the ejection surface was further expanded to the outside of the annular recess 2.
  • S1 the area of the portion surrounded by the inner diameter of the annular recess 2 and the inner diameter of the annular slit 1 on the ejection surface
  • S2 / S1 was 0.43.
  • Example 2 The same spinning stock solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3, respectively. At this time, the flow rate of the spinning dope was 2.0 cm 3 / min, and the flow rate of the injection liquid was 1.1 cm 3 / min.
  • Example 2 In the same manner as in Example 1, after passing through a coagulation bath having a predetermined dry length, it was washed with water and wound around a mould frame at a take-up speed of 40 m / min to obtain a hollow fiber membrane in a wet state.
  • the wound hollow fiber membrane had an outer diameter of 290 ⁇ m and a thickness of 55 ⁇ m.
  • the injection liquid immediately after discharge spread to the inner diameter of the annular slit 1, and the spinning solution was spread from the inner diameter of the annular slit 1 to the inner diameter of the annular recess 2.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 4.72 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 8. It was 5.
  • the obtained hollow fiber membrane was dried in the same manner as in Example 1 to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained dry hollow fiber membrane was 51 (mL / (hr ⁇ Pa ⁇ m 2 )), and the particle removal rate of 0.3 ⁇ m was 100%.
  • the hollow fiber membrane spinneret having the double tube structure shown in FIGS. 4 and 5 was used.
  • the injection liquid discharge port 3 had a diameter of 0.5 mm
  • the annular slit 1 had an inner diameter of 0.7 mm and an outer diameter of 1.0 mm.
  • the ejection surface was expanded outside the annular slit 1, but the annular recess was not provided outside the annular slit 1.
  • Example 2 The same spinning stock solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3, respectively. At this time, the flow rate of the spinning dope was 2.0 cm 3 / min, and the flow rate of the injection liquid was 1.1 cm 3 / min.
  • Example 2 After passing through the coagulation bath for a predetermined dry length in the same manner as in Example 1, an attempt was made to wind it around a maze frame at a take-up speed of 40 m / min after passing through a water washing process. The yarn was broken and the hollow fiber membrane could not be collected.
  • Photographing the appearance of the polymer solution, which was a mixture of the spinning solution and the injection liquid, stuck to the discharge surface, and the sticking outer diameter was calculated from the photograph, and it was 9 mm.
  • the injected liquid immediately after discharge was spread to the inner diameter of the annular slit 1, and the spinning solution was spread to the outside from the inner diameter of the annular slit 1 to the outer diameter of the annular slit 1.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid is 0.05 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity is 800. there were. Since the temporary discharge draft was 800, the spinning dope was largely stuck to the discharge surface, and yarn breakage occurred, so that a stable hollow fiber membrane could not be collected.
  • An area obtained by combining the area of the opening of the annular slit 1 and the area where the spinning dope is stuck to the ejection surface (hereinafter, referred to as “the ejection area of the spinning dope immediately after ejection”) is the hollow of Examples 1 to 5. Assuming that the area S1 ′ corresponds to the area S1 in the spinneret, S2 / S1 ′ was 0.006.
  • Comparative example 2 The same hollow fiber membrane spinneret as in Comparative Example 1 was used.
  • the same spinning stock solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3, respectively.
  • the flow rate of the spinning solution at this time is 2.9 cm 3 / min, the flow rate of the injected liquid was 1.4 cm 3 / min.
  • Example 2 After passing a coagulation bath for a predetermined dry length in the same manner as in Example 1, an attempt was made to wind it around a maze frame at a take-up speed of 50 m / min through a water washing process. The yarn was broken and the hollow fiber membrane could not be collected.
  • the injected liquid immediately after discharge was spread to the inner diameter of the annular slit 1
  • the spinning solution was spread to the outside from the inner diameter of the annular slit 1 to the outer diameter of the annular slit 1.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning solution and the injection liquid was 0.08 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 625. there were. Since the temporary discharge draft was 625, the spinning solution was stuck to the discharge surface, and yarn breakage occurred, so that a stable hollow fiber membrane could not be collected.
  • the hollow fiber membrane spinneret having the double tube structure shown in FIGS. 4 and 5 was used.
  • the injection liquid discharge port 3 had a diameter of 0.3 mm, and the annular slit 1 had an inner diameter of 0.5 mm and an outer diameter of 0.7 mm.
  • the ejection surface was expanded outside the annular slit 1, but the annular recess was not provided outside the annular slit 1.
  • Example 2 The same spinning solution and injected liquid as in Example 1 were prepared and discharged from the annular slit 1 and the injected liquid discharge port 3 of the die, respectively. At this time, the flow rate of the spinning dope was 2.0 cm 3 / min, and the flow rate of the injection liquid was 1.1 cm 3 / min.
  • Example 2 After passing through the coagulation bath for a predetermined dry length in the same manner as in Example 1, an attempt was made to wind it around a maze frame at a take-up speed of 40 m / min after passing through a water washing process. The yarn was broken and the hollow fiber membrane could not be collected.
  • the injected liquid immediately after discharge was spread to the inner diameter of the annular slit 1
  • the spinning solution was spread to the outside from the inner diameter of the annular slit 1 to the outer diameter of the annular slit 1.
  • the temporary discharge linear velocity calculated from the discharge area of the polymer solution immediately after discharge and the total flow rate of the spinning dope and the injection liquid was 0.06 m / min, and the temporary discharge draft obtained by dividing the take-up speed by the temporary discharge linear velocity was 666. It was 7. Since the provisional discharge draft was 666.7, the spinning dope was stuck to the discharge surface, and yarn breakage occurred, and stable hollow fiber membranes could not be collected.
  • a coagulable liquid composed of 68 parts by mass of DMAc and 32 parts by mass of water was used as an injection liquid.
  • the coagulation number of the injected liquid was 8.
  • the injected liquid was discharged from the injected liquid discharge port 3 at 1.3 cm 3 / min.
  • the base was kept warm at 50 ° C.
  • Example 2 In the same manner as in Example 1, after passing through a coagulation bath having a predetermined dry length, the product was washed with water and wound on a cassette frame at a take-up speed of 40 m / min to obtain a wet hollow fiber membrane.
  • the wound hollow fiber membrane had an outer diameter of 310 ⁇ m and a film thickness of 55 ⁇ m, and no yarn breakage occurred during sample collection for 5 hours.
  • the obtained hollow fiber membrane was dried in the same manner as in Example 1 to obtain a dry hollow fiber membrane.
  • the water permeability of the obtained dry hollow fiber membrane was 27 (mL / (hr ⁇ Pa ⁇ m 2 )), which was a low value.
  • the particle removal rate of 0.3 ⁇ m was 100%.
  • the present invention can be applied to a spinneret used in a dry-wet spinning method.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

Un objectif de la présente invention est de fournir une filière à membrane à fibres creuses où il y a peu de préoccupations concernant des dommages de sortie en raison d'un impact, et où une rupture de fibre est peu susceptible de se produire même à des rapports de tirage élevés. Un autre objectif est de comprendre la filière à membrane à fibres creuses de la présente invention et de fournir un procédé de fabrication d'une membrane à fibres creuses ayant la capacité de séparation et les performances de perméabilité à l'eau requises pour un filtre à eau. À cet effet, la présente invention est conçue comme suit. La filière à membrane à fibres creuses de la présente invention est une filière à membrane à fibres creuses ayant, dans une face de sortie, une structure de tuyau à double paroi où une sortie de liquide d'injection pour évacuer un liquide d'injection et une fente annulaire (sortie de solution de filage), entourant la sortie de liquide d'injection, pour évacuer la solution de filage, un évidement annulaire entourant la fente annulaire étant en outre formé dans la face de sortie.
PCT/JP2019/040860 2018-10-30 2019-10-17 Filière à membrane à fibres creuses et procédé de fabrication de membrane à fibres creuses WO2020090494A1 (fr)

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CN201980064273.3A CN112789103B (zh) 2018-10-30 2019-10-17 中空纤维膜纺丝喷嘴及中空纤维膜的制造方法
JP2019558641A JPWO2020090494A1 (ja) 2018-10-30 2019-10-17 中空糸膜紡糸口金および中空糸膜の製造方法

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JPS61133390A (ja) * 1984-12-03 1986-06-20 Hitachi Cable Ltd めつきされた金の剥離方法
JP2001254221A (ja) * 2000-03-10 2001-09-21 Toray Ind Inc 中空糸紡糸口金の製造方法および中空糸紡糸口金
JP2008231639A (ja) * 2007-03-23 2008-10-02 Toray Ind Inc 紡出糸条の製造方法

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JPS6147079U (ja) * 1984-08-31 1986-03-29 ユニチカ株式会社 紡糸用ノズルプレ−ト
JP2527465B2 (ja) * 1988-07-05 1996-08-21 ダイセル化学工業株式会社 膜製造装置
JP2805873B2 (ja) * 1989-08-04 1998-09-30 東洋紡績株式会社 中空糸型血漿分離膜
JP3418430B2 (ja) 1993-08-11 2003-06-23 日東電工株式会社 マイクロカプセルの処理方法
JP2004305953A (ja) 2003-04-09 2004-11-04 Asahi Medical Co Ltd 中空糸膜の製造法
JP2009000614A (ja) * 2007-06-21 2009-01-08 Toray Ind Inc 中空糸膜の製造方法
JPWO2010029908A1 (ja) * 2008-09-10 2012-02-02 東レ株式会社 中空糸膜及び中空糸膜の製造方法

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JPS6197412A (ja) * 1984-10-12 1986-05-15 Toa Nenryo Kogyo Kk 炭素繊維用ピッチのための紡糸口金
JPS61133390A (ja) * 1984-12-03 1986-06-20 Hitachi Cable Ltd めつきされた金の剥離方法
JP2001254221A (ja) * 2000-03-10 2001-09-21 Toray Ind Inc 中空糸紡糸口金の製造方法および中空糸紡糸口金
JP2008231639A (ja) * 2007-03-23 2008-10-02 Toray Ind Inc 紡出糸条の製造方法

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