WO2012108413A1 - 編紐引き出し方法、多孔質膜の製造方法及び編紐供給装置 - Google Patents

編紐引き出し方法、多孔質膜の製造方法及び編紐供給装置 Download PDF

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Publication number
WO2012108413A1
WO2012108413A1 PCT/JP2012/052701 JP2012052701W WO2012108413A1 WO 2012108413 A1 WO2012108413 A1 WO 2012108413A1 JP 2012052701 W JP2012052701 W JP 2012052701W WO 2012108413 A1 WO2012108413 A1 WO 2012108413A1
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WO
WIPO (PCT)
Prior art keywords
string support
storage container
braided
string
support
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PCT/JP2012/052701
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English (en)
French (fr)
Japanese (ja)
Inventor
隅　敏則
泰夫 広本
倉科　正樹
勝彦 品田
Original Assignee
三菱レイヨン株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
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Application filed by 三菱レイヨン株式会社 filed Critical 三菱レイヨン株式会社
Priority to CN201280016877.9A priority Critical patent/CN103492296B/zh
Priority to JP2012511854A priority patent/JPWO2012108413A1/ja
Priority to KR1020137021782A priority patent/KR101560074B1/ko
Publication of WO2012108413A1 publication Critical patent/WO2012108413A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H49/00—Unwinding or paying-out filamentary material; Supporting, storing or transporting packages from which filamentary material is to be withdrawn or paid-out
    • B65H49/02—Methods or apparatus in which packages do not rotate
    • B65H49/04—Package-supporting devices
    • B65H49/10—Package-supporting devices for one operative package and one or more reserve packages
    • B65H49/12—Package-supporting devices for one operative package and one or more reserve packages the reserve packages being mounted to permit manual or automatic transfer to operating position
    • 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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H57/00—Guides for filamentary materials; Supports therefor
    • B65H57/18—Guides for filamentary materials; Supports therefor mounted to facilitate unwinding of material from packages
    • B65H57/20—Flyers
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65H—HANDLING THIN OR FILAMENTARY MATERIAL, e.g. SHEETS, WEBS, CABLES
    • B65H2701/00—Handled material; Storage means
    • B65H2701/30—Handled filamentary material
    • B65H2701/31—Textiles threads or artificial strands of filaments

Definitions

  • the present invention relates to a method for producing a porous membrane (porous hollow fiber membrane) having a hollow strength support therein, and a knitting for supplying a knitted string support in the porous membrane (porous hollow fiber membrane) to a spinning nozzle.
  • the present invention relates to a string supply device.
  • porous hollow fiber membranes for the purpose of concentrating and recovering useful components, removing unnecessary components, desalinating, etc.
  • Microfiltration membranes, ultrafiltration membranes, reverse osmosis filtration membranes, etc. are frequently used.
  • a porous hollow fiber membrane for example, a hollow braided string support obtained by braiding a plurality of yarns, or a hollow braided string support obtained by circular knitting a single thread (hereinafter referred to as braided string support and braided string support)
  • a porous hollow fiber membrane is known in which a porous membrane layer is formed on the outside of the substrate. Since this porous hollow fiber membrane has a support, it has excellent mechanical properties, and it is difficult for defects such as breakage to occur even under more severe conditions.
  • Such a porous hollow fiber membrane is spun so that a film-forming stock solution for forming a support and a porous membrane layer is supplied to a spinning nozzle, and the film-forming stock solution is applied to the outside of the support by the spinning nozzle. Then, after coagulating with a coagulating liquid, it is obtained by washing, drying, etc. (for example, Patent Document 1).
  • the porous membrane requires not only high separation characteristics and excellent water permeability, but also mechanical strength that prevents the porous membrane from breaking against the tensile force acting on the porous membrane when used under severe conditions. Be done
  • a hollow porous membrane in which a porous membrane layer is formed on the outer peripheral surface of a support made of a hollow braid formed by braiding yarn is often used.
  • the support is drawn into the center of the spinning nozzle, and a membrane-forming stock solution shaped hollow by the spinning nozzle is applied to the outer peripheral surface of the support.
  • a porous membrane layer on the outer peripheral surface of the support solidification step.
  • the porous membrane is dried by a drying process.
  • a braid used as a support is usually manufactured by a string making machine, and then wound and stored on a winder such as a storage container or a bobbin. Therefore, when the braid is used for manufacturing the porous membrane, the support is pulled out from the winder and supplied to the spinning nozzle.
  • the following methods are used as a method of winding a braid without high twist and twisting that impedes storage stability.
  • the storage container when a cylindrical storage container is used as a winder, the storage container is first placed on a turntable that rotates at a rotational speed set according to the braid manufacturing speed, and the storage container is rotated. Next, the braid is supplied into the rotating storage container from a fixed guide installed on the upper opening surface of the storage container. At that time, by shifting the center of the storage container and the center of rotation of the turntable to some extent, the braid draws a loop-like arrangement locus and is laminated from the bottom to the top of the storage container while shifting in the rotation direction of the storage container. Stored.
  • the braid stored in the storage container in such a form is pulled out from the storage container and supplied to the spinning nozzle, if it is pulled out as it is from the end (end end) of the braid storage, one braid loop is unwound.
  • the braid is twisted once, and the twist guide easily prevents the twist from accumulating, for example, a portion where the tension acting on the braid is low or the braid is not twisted.
  • twist of the braid that accumulates in the downstream of the braid cannot be maintained in the form of twist around the central axis of the braid, a twist occurs, and finally a twisted hump (also called a twisted hump part) is generated and the braid moves At the same time, the twisted hump portion moves downstream.
  • a twisted hump also called a twisted hump part
  • Such a cause is considered as follows. That is, when the energy accumulated in the form of twisting around the central axis of the braid increases, a part of the braid forms a ring, which is considered to be a form that can store more energy at an energy level smaller than twisting. Then, the braids that form the ring are twisted to change into a double spiral twisted hump portion like a stranded wire.
  • a bobbin when used as a winder, braided cords and braided cords (hereinafter collectively referred to as “hollow cords”) wound around the bobbin while the bobbin is rotated.
  • the support used in manufacturing the porous hollow fiber membrane is usually stored in a cylindrical storage container after being manufactured by a string making machine, and drawn out from the storage container during the manufacturing of the porous hollow fiber membrane.
  • the following method is used to store the support.
  • a cylindrical storage container provided with a core rod in the center is placed on a turntable and rotated, and a support is supplied into the storage container. At this time, the center of the storage container and the rotation center of the turntable are shifted to some extent.
  • the support is stacked and stored while drawing a loop-shaped arrangement trajectory so that the support surrounds the core rod from the bottom to the top of the storage container (Patent Document 5).
  • the hollow string wound around the winder has a finite length, in order to continuously draw out the hollow string and supply it to the spinning nozzle, the hollow string wound around an arbitrary winder can be wound. It is necessary to connect the end of this and the winding start end (start end) of the hollow string wound by the next winding tool. Normally, while the winder is rotating, it is difficult to connect the end of the hollow string and the start of the next hollow string, so the winder stops rotating to connect them. To do.
  • a hollow table is simultaneously supplied to the number of spinning nozzles corresponding to the number of the porous membranes. Is required.
  • the number of connections increases as the number of storage containers increases. In particular, the faster the pulling speed, the shorter the time for one loop of the hollow string in the storage container to open, so the connection of the hollow string must be completed in a shorter time.
  • the support housed by the method of Patent Document 5 may be entangled by being caught on the trunk or core rod of the storage container when being pulled out from the storage container and supplied to the spinning nozzle. If the support becomes entangled, the support supply tension will rise rapidly, the support will slip at the support feed mechanism, and it will not be possible to supply the support downstream, or the storage container will rise and collide with the support guide and be damaged. When the entangled part is removed and sent downstream, problems such as being caught by the support guide or the spinning nozzle and stopping traveling occur.
  • the present invention has been made in view of the above circumstances, and even when the support is pulled out continuously, the support is supplied with a simple mechanism and effective use of space while suppressing the occurrence of twisting. And it aims at provision of the method which can manufacture a porous membrane stably.
  • the present invention also relates to an apparatus for supplying a knitted string support to a spinning nozzle, the knitted string support being less likely to be entangled, and providing an excellent process stability in the production of a porous hollow fiber membrane.
  • the purpose is to provide.
  • a braid formed by braiding a plurality of yarns is excellent in torsional resistance, but easily stretches (is inferior in stretch resistance) when pulled, whereas a knitting in which one yarn is circularly knitted.
  • the string is excellent in stretch resistance, attention was paid to the fact that no large reaction force (torsion torque) like that of a braid is generated when the knitted string is twisted. If the knitting cord has a small reaction force when twisted, it is pulled out from the winder in a stationary state, and even if twisting occurs in the knitting cord, it is stably sent out downstream in the form of twisting.
  • the present inventors have found that the string that can be pulled out stably can be pulled out stably. As a result, the present inventors have found that there is a certain relationship with respect to the degree (twisting restoration rate ⁇ twisting torque), thereby completing the present invention.
  • the present invention has the following aspects.
  • a first aspect of the present invention is a method of pulling a knitted string from a winder, This is a method for pulling out a knitted string from the winder while the winder is stationary.
  • a second aspect of the present invention is the knitted string pulling method according to the first aspect, wherein the knitted string has a torsion pulling stability value X defined below of 14 g ⁇ cm or less.
  • Twist restoration rate A (A ratio obtained by dividing the number of times the twist returned after attaching a 30 g weight on a 30 cm long braided string at the lower end and twisting the braided string in the vertical direction 5 times )
  • Twisting torque B (When a 30 g weight is attached to the lower end of a braided string of 30 cm and twisted five times with the braided string suspended in the vertical direction, it acts in a direction opposite to the direction twisted on the braided string.
  • Load (g) x distance from the center of the braided string to the load measurement point (cm) twisting torque (g ⁇ cm)
  • Twisted drawer stable value X twisting recovery rate A ⁇ twisting torque B (g ⁇ cm)
  • a hollow knitted string support is pulled out from a winder, and a film-forming solution is applied to the outer peripheral surface of the knitted string support and solidified to solidify the outer peripheral surface of the knitted string support.
  • a fourth aspect of the present invention is the method for producing a porous membrane according to the first aspect, wherein the hollow knitted string support has a twist-drawing stability value X specified below of 14 g ⁇ cm or less. is there.
  • Twist restoration rate A (Number of times the twist was restored when the force was released after attaching a 30 g weight to the lower end of the 30 cm long braid and twisting it 5 times with the braid suspended in the vertical direction. Divided by 5 times)
  • Torsional torque B (When a 30 g weight is attached to the lower end of a 30 cm long braid and is twisted five times with the braid suspended in a vertical direction, it acts in a direction opposite to the direction twisted on the braid.
  • Load (g) x distance from the center of the braided string to the load measurement point (cm) twisting torque (g ⁇ cm)
  • Twisted drawer stable value X twisting recovery rate A ⁇ twisting torque B (g ⁇ cm)
  • the braided string support is supplied to a spinning nozzle that spins so as to apply a film-forming stock solution for forming a porous membrane layer on the outer peripheral surface of the hollow braided string support.
  • a braided string supply device A winder for storing the braided string support;
  • a guide member The braided string supply device is a braided string supply device in which the braided string support is pulled out from the winder toward the guide member.
  • Another preferred aspect of the present invention is the winding of the braided string support wound on an arbitrary winding tool so that the braided string supports wound on a plurality of winding tools are connected. It is preferable that the start end is connected to the winding end of the braided string support wound on the next winding tool.
  • the winder is a cylindrical storage container, and the knitted string support is stacked and stored from the bottom to the top of the storage container while drawing a loop-shaped arrangement locus,
  • the axial direction of the storage container in which the braided string support is stored is oriented in the vertical direction, and the braided string support is pulled out in the vertical direction.
  • a core rod is attached to the central portion of the storage container, and an arrangement locus of the braided string support body surrounds the core rod.
  • the winder is a bobbin, the knitted string support is wound around the bobbin, and the knitted string support is pulled out in the central axis direction of the bobbin around which the knitted string support is wound.
  • the knitting string supply device includes a spinning nozzle that performs spinning so that a film-forming solution for forming a porous film layer is applied to the outside of the hollow knitted string support.
  • a braided string supply device for supplying a string support, A cylindrical storage container for storing the braided string support, and a guide member provided on the storage container; The braided string support is a device that is pulled out from the storage container toward the guide member.
  • the knitted string supply device of the present invention further includes tension applying means for applying tension to the knitted string support drawn from the storage container before being supplied to the spinning nozzle.
  • the support is supplied with a simple mechanism and effectively using space while suppressing the occurrence of twisting. And a porous membrane can be manufactured stably.
  • the knitted string supply device of the present invention when used, the knitted string support to be supplied to the spinning nozzle is hardly entangled, and excellent process stability can be obtained in the production of the porous hollow fiber membrane.
  • connection apparatus used for the connection of a braided string support body. It is a figure which shows the state which inserted the braided string support body in the connection jig of the connection apparatus of FIG. 8A. It is a schematic sectional drawing which shows an example of a porous membrane. It is a schematic block diagram which shows an example of the apparatus which forms a porous membrane layer in the outer peripheral surface of a braided string support body. It is the schematic which showed an example of the braided string supply apparatus of this invention. It is a schematic block diagram which shows an example of the winding apparatus used when winding a braided string support body around a bobbin.
  • the knitted string used in the knitted string drawing method according to the present invention was evaluated by the following evaluation method 1 or evaluation method 2, for example.
  • Twist drawer stability (twist recovery rate x twist torque)
  • the torsional pulling stability (twisting recovery rate ⁇ twisting torque) was determined. The results are shown in Table 3.
  • the torsional recovery rate A ⁇ torsion torque B of the string used in the present invention is 14 g ⁇ cm or less, it is smooth without producing a twisted hump portion that is generated when a string in a stationary state is pulled out. I was able to pull it out. Further, the inventors have intensively studied and found that the twist-drawing stability value X is more preferably 10 g ⁇ cm or less, and most preferably 5 g ⁇ cm or less. Such a characteristic that the twisted hump portion does not occur was not observed in the braid, but was observed only in the braid.
  • a first embodiment of a method for producing a porous membrane (also referred to as a porous hollow fiber membrane) of the present invention will be described in detail with reference to the drawings.
  • the method for producing a porous membrane of the present invention according to the first embodiment uses a storage container as a winder, and draws out a hollow braided string support from the storage container (drawing process), and is drawn out A step (coagulation step) of forming a porous membrane layer on the outer peripheral surface of the knitted string support by applying the film forming stock solution to the outer peripheral surface of the knitted string support and solidifying it.
  • FIG. 1 shows the structure of a braided string support 110 used in the present invention.
  • the knitted string support 110 is a cylindrical (hollow) knitted string obtained by circularly knitting a single yarn 111. Circular knitting is the knitting of a cylindrical weft fabric using a circular knitting machine. As shown in FIG. 1, the yarn 111 is bent to form a continuous loop 112 extending in a spiral shape. The loop 112 is connected vertically and horizontally, and has stitches 113 in the loop 112 and at the connecting portion between the loops 112.
  • the braided string support 110 is different in structure from the braided string support 12 having a structure in which a plurality of yarns 11, 11,.
  • the knitted string support 110 is made of the original cylindrical knitted string heated to a temperature lower than the melting point of the fibers constituting the knitted string after the yarn 111 is circularly knitted by a circular knitting machine to produce a cylindrical knitted string. It is preferable that an extension compression heating process is performed in which a drawing die having an outlet hole diameter smaller than the diameter is passed and drawn by a take-off roll downstream of the die outlet. By performing the extension and compression heat treatment, the elongation of the knitted string can be greatly reduced and the stability of the diameter can be imparted.
  • Examples of the form of the yarn 111 include multifilament, monofilament, spun yarn and the like.
  • Examples of the fibers constituting the yarn 111 include synthetic fibers, semi-synthetic fibers, regenerated fibers, and natural fibers.
  • the yarn 111 may be a combination of a plurality of types of fibers.
  • synthetic fibers include polyamide fibers such as nylon 6, nylon 66, and aromatic polyamide; polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and polyglycolic acid; acrylic fibers such as polyacrylonitrile; polyethylene, Polyolefin fibers such as polypropylene; polyvinyl alcohol fibers; polyvinylidene chloride fibers; polyvinyl chloride fibers; polyurethane fibers; phenol resin fibers; fluororesin fibers such as polyvinylidene fluoride and polytetrafluoroethylene; Examples include paraoxybenzoate fibers.
  • polyester fibers such as polyethylene terephthalate, polybutylene terephthalate, polylactic acid, and polyglycolic acid
  • acrylic fibers such as polyacrylonitrile
  • polyethylene Polyolefin fibers such as polypropylene
  • polyvinyl alcohol fibers polyvinylidene chloride fibers
  • semi-synthetic fibers include cellulose derivative fibers made from cellulose diacetate, cellulose triacetate, chitin, chitosan, and the like; protein fibers called promixes, and the like.
  • regenerated fiber include cellulosic regenerated fibers (rayon, cupra, polynosic, etc.) obtained by the viscose method, the copper-ammonia method, and the organic solvent method.
  • polyester fiber As the fiber constituting the yarn 111, a multifilament of synthetic fiber is preferable because the effect of the above-described stretching and compression heat treatment is easily exhibited.
  • polyester fiber, acrylic fiber, polyvinyl alcohol fiber, polyamide fiber, and polyolefin fiber are preferable from the viewpoint of excellent chemical resistance, and polyester fiber or acrylic fiber is particularly preferable.
  • the fineness of the yarn 111 is preferably 150 to 1000 dtex from the viewpoint of improving the durability of the hollow porous membrane (porous hollow fiber membrane) and the adhesion to the porous membrane layer. If the fineness of the yarn is 150 dtex or more, although depending on the outer diameter, the crushing pressure of the resulting porous membrane is improved. When the fineness of the yarn is 1000 dtex or less, a decrease in water permeability due to a reduction in the inner diameter can be suppressed.
  • the number of stitches 113 is preferably 5 or more per round.
  • the number of stitches 113 is the same as the number of knitting needles (knitting needles) of the circular knitting machine.
  • the number of stitches 113 is 5 or more, the cross-sectional shape of the hollow portion of the knitted string support 110 is circular, and a decrease in water permeability due to a reduction in the inner diameter is suppressed.
  • the upper limit of the number of stitches 113 is determined by the outer diameter of the knitted string support 110, the fineness of the yarn 111, the size of the stitch 113 (the size of the loop 112), and the like.
  • the stitch 113 When the stitch 113 is large, when a film-forming stock solution described later is applied to the knitted string support 110, the film-forming stock solution may flow into the knitted string support 110 and the hollow portion may be blocked. Therefore, when manufacturing the braided string support body 110 having the same outer diameter, the number of stitches needs to be set large when the fineness of the yarn 111 is high, and the number of stitches needs to be set large when the fineness is low.
  • the outer diameter of the braided string support 110 is determined by the outer diameter of the finally obtained hollow porous membrane (porous hollow fiber membrane).
  • the outer diameter of the porous membrane is preferably 0.9 to 6.0 mm, more preferably 1.0 to 3.5 mm, from the required filtration area in the membrane module formed by bundling the porous membrane. Accordingly, the outer diameter of the braided string support 110 is preferably 0.7 to 5.0 mm, and more preferably 0.9 to 3.0 mm.
  • Examples of the use of the knitted string used in the present invention include (a) to (e) below, but are not limited thereto.
  • A Porous membrane support
  • Precursor is made flame-resistant after stringing, or carbonized hollow flame-resistant string or carbon fiber string
  • c fiber reinforced pipe (for example, carbon fiber (Cylinder knitted, high-strength PET, etc., hardened with thermoplastic or thermosetting resin)
  • D Artificial blood vessel skeleton (for example, titanium fiber, PTFE fiber tube knitting, PET resin binding, etc.)
  • E Fiber reinforced hose (for example, blade hose) Among these, it is preferable to use a braided string for the production of a porous membrane.
  • FIG. 2 shows an example of the storage container 120 used in the present invention.
  • the storage container 120 in this example has a cylindrical shape, and a core rod 121 is attached to the center.
  • the minimum diameter of the loop that the braided string support naturally draws is roughly determined by the flexibility of the braided string support.
  • the storage container There may be a space where the braided string support is not arranged at the center of 120. If the core rod 121 is attached to the storage container 120, the part where the braided string support body is not disposed can be filled, and the storage form is more stable.
  • the material of the storage container 120 is not particularly limited, and examples thereof include paper, plastics such as polyethylene and polyethylene terephthalate (PET), iron, and stainless steel.
  • the inner diameter and depth of the storage container 120 can be appropriately determined depending on the storage amount of the braided string support 110 and the like.
  • the outer diameter and height of the core rod 121 of the storage container 120 can be appropriately determined depending on the storage amount of the braided string support 110 and the like.
  • the outer diameter of the storage container 120 is appropriately selected depending on the storage amount of the knitted string support, the pulling form of the knitted string support, and the like.
  • FIG. 4 is a schematic configuration diagram illustrating an example of a storage device used when storing the braided string support.
  • the storage device 130 of this example includes a cylindrical storage container 120 that stores the braid string support 110, a rotary table 131 that rotates the storage container 120, and a supply guide 132 that fixes the supply position of the braid string support 110. It has.
  • the rotary table 131 for rotating the storage container 120 is not particularly limited as long as the storage container 120 can be easily installed and the rotation speed R can be periodically changed.
  • the rotary table 131 is of a drive system having a controller function that can preset a fluctuation pattern of the rotational speed R of the storage container 120 and can input a program of the fluctuation pattern of the rotational speed R.
  • the supply guide 132 is attached above the storage container 120 and near the inner wall surface of the storage container 120.
  • “near the inner wall surface” means a range within 20 mm from the inner wall surface.
  • the supply guide 132 is not particularly limited as long as the supply guide 132 can pass the knitted string support 110 and can fix the supply position of the knitted string support 110.
  • the supply guide 132 has a ring shape larger than the outer diameter of the knitted string support 110. Is preferable.
  • the ring-shaped surface has a smooth shape without burrs or the like.
  • the braided string support 110 is stored in the storage container 120 in the braided string support 110 while being supplied into the rotating storage container 120 via the supply guide 132 at a constant speed. Since it becomes easier to prevent the braided string support 110 from being entangled when it is pulled out, as shown in FIG. Are preferably stacked and stored from the bottom 122 to the top 123 of the storage container 120 while shifting in the direction around the rotation axis of the storage container 120. Further, if the knitted string support 110 is stored so that the arrangement trajectory of the knitted string support 110 surrounds the core rod 121, the loop is shifted during transportation or container handling, and the upper and lower sides are switched, and the knitted string support is moved when pulled out.
  • the method for housing the braided string support 110 in the storage container 120 is not limited to the method shown in FIG. 5 as long as it is a method for preventing the braided string support from being entangled when pulled out.
  • the end (winding start end) of the knitted string support 110 is brought out of the storage container 120. If the starting end protrudes outside the storage container 120, it is easy to connect the knitted string support body stored in the next storage container in the connection of the knitted string support body described later. That is, the storage start end and the storage end of the knitted string support 110 stored in the next storage container 120 can be easily connected, and the knitted string support 110 is continuously and rapidly supplied to the spinning nozzles 161 and 220. It becomes easy.
  • the braided string support 110 is pulled out from the storage container 120 in the winding axis direction while the storage container 120 is stationary. Specifically, as shown in FIG. 6, it is preferable to draw the braided string support 110 upward in the vertical direction with the axial direction of the storage container 120 oriented in the vertical direction. In addition, the braided string support body 110 is pulled out from the end of storage in the storage container 120 (winding end).
  • the storage container 120 is stored several times to several tens of times the diameter of the core rod 121 above the storage container 120, that is, substantially on the extension line of the storage container 120 in the direction in which the braided string support 110 is pulled out.
  • a drawer guide 124 for fixing the position of the braided string support 110 in the horizontal direction is preferably attached to a position away from the container 120, and the braided string support 110 is preferably pulled out through the drawer guide 124. If the drawer guide 124 is attached in this way, when the loop of the braided string support body 110 stored in the storage container 120 is unwound and pulled out, the pulling speed and the resistance to unravel the loop are easily stabilized.
  • the drawer guide 124 is not particularly limited as long as it can pass the knitted string support 110 and can fix the position of the drawn knitted string support 110 in the horizontal direction.
  • a larger ring shape is preferred.
  • the ring-shaped surface has a smooth shape without burrs or the like.
  • the storage container 120 is preferably placed on a floor or the like in a stationary state in that the apparatus can be simplified and the space can be effectively utilized.
  • the support body is stored in a storage container so as to draw a loop-like arrangement locus and pulled out as it is, each time the braid loop is pulled out, one twist is generated in the braid, When such a twist accumulates, a twisted hump portion is irregularly formed, and the twisted hump portion moves downstream as the braid moves and may be caught by the spinning nozzle.
  • a method of eliminating this twist there is a method of pulling out the support while rotating the storage container in the opposite direction to the storage container using a turntable or the like. Cannot be used effectively.
  • the braided string support 110 unlike the braided string support 8, as described above, generates a large torsional reaction force like a braided string when the braided string is twisted despite its excellent stretch resistance. Therefore, even if twisting occurs by pulling out from the stationary storage container 120 as it is, the twist is not accumulated in a specific part, and the twisted knitted string is stably carried away with the movement of the string. Twisted bumps are difficult to form.
  • the storage container 120 may be placed on the turntable and the storage container 120 may be rotated in the direction opposite to the storage direction when the braided string support 110 is pulled out.
  • the braided string supply device 210 is characterized in that a guide member 214 is provided on the storage container 120.
  • a guide member 214 is provided on the storage container 120.
  • the braided string support 110 pulled up from the storage container 120 is caught on the trunk portion, the core rod 121, etc. of the storage container 120, or the trunk portion, the core rod 121, etc. It can suppress that force is irregularly applied by contact with. Thereby, it is suppressed that the braided string support body 110 pulled out from the storage container 120 is entangled.
  • the guide member 214 include metal or ceramic guide rolls, plastic guide rolls such as polyethylene, PET, and Teflon (registered trademark).
  • the height of the guide member 214 is preferably 1.5 m or more from the viewpoint that it is easy to prevent the drawn knitted string support 110 from being caught by the trunk of the storage container 120 or the core rod 121 and the like. The above is more preferable.
  • the height of the guide member 214 is preferably 5.0 m or less, more preferably 4.0 m or less, from the viewpoint of improving workability such as maintenance.
  • the height of the guide member 214 means the distance from the bottom 122 of the storage container 120 to the guide member 214.
  • an angle ⁇ formed by the straight line m and the bottom 122 of the storage container 120 (FIG. 1). Is preferably 60 ° or more, and more preferably 70 ° or more, from the viewpoint that it is easy to prevent the drawn knitted string support 110 from being caught by the trunk of the storage container 120, the core rod 121, or the like.
  • the angle ⁇ is preferably 85 ° or less, and more preferably 80 ° or less from the viewpoint that the guide member 214 is easily prevented from becoming too high.
  • the knitted string supply device 210 of this example it is preferable to have tension applying means 216 that applies tension to the knitted string support 110 pulled out from the storage container 120 before being supplied to the spinning nozzle 220. .
  • tension applying means 216 that applies tension to the knitted string support 110 pulled out from the storage container 120 before being supplied to the spinning nozzle 220.
  • the tension applying means 216 for example, as in this example, a metal is provided between two guide members 218 that regulate the travel of the braided string support 110 between the guide member 214 on the storage container 120 and the spinning nozzle 220.
  • bars 216a and 216b are provided and tension is applied by meandering the running of the braided string support 110.
  • tensile_strength provision means 216 should just be a thing which can provide tension
  • the guide member 218 regulates the travel of the braided string support 110 until it is supplied to the spinning nozzle 220, and the same members as those described for the guide member 214 can be used.
  • the braided string support 110 pulled out from the storage container 120 is supplied to the next coagulation step.
  • the braided string support body 110 accommodated in the storage container 120 has a finite length, in order to continuously draw the braid string support body 110 and supply it to the coagulation step, each braid stored in a plurality of storage containers is used. What is necessary is just to connect and use a string support body.
  • the winding start end (also referred to as storage start end) a11 of the string support 110a is connected to the winding end (also referred to as storage end) b12 of the knitted string support 110b stored in the next storage container 120b.
  • the winding start end b11 of the knitted string support 110b stored in the storage container 120b and the winding end c12 of the knitted string support 110c stored in the next storage container 120c are connected.
  • the braided string support 110 stored in the plurality of storage containers 120 are connected in this way, the braided string support is supported from the next storage container 120b after all the braided string supports 110a are pulled out from the arbitrary storage container 120a. After the body 110b is pulled out and all the knitted string support body 110b is pulled out, a continuous pulling operation such that the knitted string support body 110c is pulled out from the next storage container 120c becomes possible.
  • the method for connecting the knitted string support is not particularly limited as long as the connected knitted string support can pass through the steps after the solidification step stably, and examples thereof include the following methods.
  • a method in which the ends of two knitted string supports to be connected are overlapped with each other by several mm to several tens of mm, and the overlapped portions are fused and connected by ultrasonic waves.
  • Each of the knitted string supports inserted into the hollow portions of the two knitted string supports is inserted with a dozen mm of string having excellent flexibility, and the string is inserted from the surface of the knitted string support.
  • An elastic adhesive is applied to the outer periphery of the string-like material having excellent flexibility, and is inserted into the hollow part of the two braided string supports that connect the adhesive-applied part of the string-like object, and connected by adhesion. how to.
  • a method in which the ends of two knitted string supports to be connected are butted together and both ends are connected by a metal connecting member such as a stapler.
  • connection methods a secondary member is not required for connection, the connection can be made in a short time, and the diameter of the knitted string support after the connection can be accurately suppressed below the diameter of the knitted string support before the connection. Therefore, the ultrasonic wave of (1) is used because the knitted string support after connection is excellent in the ability to pass through the nozzle (spinning nozzle) and / or it is difficult to form a bump on the formed porous hollow fiber membrane.
  • a method of connection is preferred.
  • connection device shown in FIG. 8A may be used as the connection method using ultrasonic waves.
  • the connection device 140 in this example includes an ultrasonic horn 141 and a connection jig 142.
  • the ultrasonic horn 141 has a lower surface 141a that is in contact with the braided string support, and transmits ultrasonic waves from the lower surface to the braided string support.
  • the connecting jig 142 is a rectangular plate, and a groove 142a is linearly formed from one side of the plate to a side opposite to the side, and the depth of the groove 142a defines a pair of braided string supports. It can be stacked and stored.
  • the braided string support is inserted into the groove 142a of the connection jig 142.
  • the braided string supports 110a and 110b are inserted such that the winding start end (also referred to as storage start end) a11 of 110a and the winding end end (also referred to as storage end end) b12 of the knitted string support 110b overlap.
  • both ends the winding start end a11 and the winding end end b12 (hereinafter collectively referred to as “both ends”) are pressed against the bottom of the groove 142a. To compress and deform. Then, while maintaining the compression deformation state, ultrasonic waves are transmitted to both ends to be fused and connected.
  • the braided string supports 110a and 110b are fused and connected to each other using the ultrasonic horn 141, local heat generation due to friction occurs in the braided string supports 110a and 110b, and the connected portion is deformed.
  • a liquid such as water may be present between the fibers of the braided string supports 110a and 110b, the porous portion, and the like, and may be wet.
  • the two knitted string supports to be connected are connected in a superimposed state, but the present invention is not limited to this.
  • the hollow part diameter of one braided string support body is expanded so as to be larger than the outer diameter, and the other braided string support body is several in the hollow part. It may be inserted from mm to several tens of mm, and ultrasonic waves are transmitted to the inserted portion to be fused and connected.
  • connection part of the braided string support bodies in the obtained porous hollow fiber membrane does not express sufficient water permeability, the connection part is removed after manufacture. At this time, since it becomes easy to determine the connection part of the knitted string supports in the obtained porous hollow fiber membrane, the storage start end and the storage end of the knitted string support are colored with ink or the like It is preferable to connect later.
  • a porous film is formed on the outer peripheral surface of the knitted string support 110 as shown in FIG. 9 by applying a film-forming stock solution to the outer peripheral surface of the knitted string support supplied in the above-described drawing step and solidifying it.
  • the porous membrane 150 in which the layer 151 is formed is obtained.
  • the film-forming stock solution usually contains a hydrophobic polymer and a hydrophilic polymer.
  • the hydrophobic polymer is not particularly limited as long as it can form a porous film by a coagulation process, and can be used without particular limitation as long as it is such as polysulfone resin such as polysulfone or polyethersulfone, polyvinylidene fluoride, etc. And fluororesin, polyacrylonitrile, cellulose derivatives, polyamide, polyester, polymethacrylate, polyacrylate, and the like. Further, copolymers of these resins may be used, and those having a substituent introduced into a part of these resins and copolymers can also be used.
  • fluororesins especially polyvinylidene fluoride and copolymers comprising vinylidene fluoride alone and other monomers have excellent durability against oxidizing agents such as hypochlorous acid. Therefore, for example, in the case of producing a porous film that is treated with an oxidant in the removing step described later, it is preferable to select a fluororesin as the hydrophobic polymer.
  • the hydrophilic polymer is added to adjust the viscosity of the film-forming stock solution to a range suitable for the formation of a porous film and to stabilize the film-forming state, and polyethylene glycol, polyvinyl pyrrolidone, etc. are preferable. used.
  • polyvinylpyrrolidone and a copolymer obtained by copolymerizing other monomers with polyvinylpyrrolidone are preferable from the viewpoint of controlling the pore diameter of the porous membrane and the strength of the porous membrane.
  • 2 or more types of resin can also be mixed and used for a hydrophilic polymer.
  • the low molecular weight hydrophilic polymer is preferable in that it is more easily removed from the porous membrane in the hydrophilic polymer removing step described later. Therefore, the same kind of hydrophilic polymers having different molecular weights may be appropriately blended depending on the purpose.
  • a film-forming stock solution can be prepared by mixing the above-described hydrophobic polymer and hydrophilic polymer in a solvent in which they are soluble (good solvent). Other additive components may be added to the film-forming stock solution as necessary. There are no particular restrictions on the type of solvent, but when the coagulation process is carried out by dry and wet spinning, the pore size of the porous membrane is adjusted by absorbing the membrane-forming stock solution in the idle running section, so that it is mixed uniformly with water. It is preferable to select a solvent that can be easily treated.
  • Examples of such a solvent include N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N-methylmorpholine-N-oxide, and the like. Can be used. Moreover, you may mix and use the poor solvent of a hydrophobic polymer or a hydrophilic polymer in the range which does not impair the solubility of the hydrophobic polymer or hydrophilic polymer to a solvent.
  • the temperature of the film-forming stock solution is not particularly limited, but is usually 20 to 40 ° C.
  • the concentration of the hydrophobic polymer in the film-forming stock solution is too thin or too thick, the stability during film formation tends to be low and it is difficult to form a suitable porous film structure.
  • % By mass is preferable, and 15% by mass is more preferable.
  • the upper limit is preferably 30% by mass, and more preferably 25% by mass.
  • the lower limit of the concentration of the hydrophilic polymer is preferably 1% by mass and more preferably 5% by mass in order to make the porous film easier to form.
  • the upper limit of the concentration of the hydrophilic polymer is preferably 20% by mass, and more preferably 12% by mass from the viewpoint of the handleability of the film-forming stock solution.
  • the membrane-forming stock solution thus prepared is applied to the outer peripheral surface of the braided string support to form a porous membrane layer.
  • a porous film layer forming apparatus shown in FIG. 10 may be used to form the porous film layer.
  • the porous membrane layer forming apparatus 160 of this example includes an annular spinning nozzle 161 for applying a film-forming stock solution to a braided string support 110 drawn from a storage container (not shown), and a film-forming stock solution to the spinning nozzle 161.
  • a guide roll 164 to be introduced.
  • a conduit through which the braided string support 110 passes is formed.
  • the inner diameter of the pipe is slightly larger than the outer diameter of the braided string support 110, and the inner peripheral surface of the pipe of the spinning nozzle 161 and the braided string support 110 have a certain gap.
  • the gap is determined by the thickness of the coating film, the viscosity of the stock solution, the running speed of the braided string support 110, and is usually 0.15 to 0.25 mm. If a spinning nozzle in which two slit-shaped film forming solution discharge ports are formed on the upstream side and the downstream side in the circumferential direction of the pipe line is used in the middle of the pipe line, two types of film forming stock solutions having different compositions are used. Can be applied to the braided string support 110.
  • the porous membrane layer forming apparatus 160 When the porous membrane layer forming apparatus 160 is used, when the braided string support 110 passes through the spinning nozzle 161, a constant amount of the film-forming stock solution is supplied from the stock solution supplying means 162, and the braided string support 110 A film-forming stock solution is applied to the outer peripheral surface to form a coating film having a predetermined film thickness. In addition, when two types of film-forming stock solutions are applied, first, the first film-forming stock solution is applied to the outer peripheral surface of the braided string support, and then the second film-forming stock solution is formed on the first film-forming stock solution. Stock solution is applied.
  • the braided string support 110 to which the film-forming stock solution has been applied is guided by a guide roll 164 to a coagulation tank 163 containing a coagulation liquid.
  • a coagulation tank 163 containing a coagulation liquid.
  • the hydrophobic polymer and the hydrophilic polymer undergo phase separation, respectively, and the hydrophobic polymer is coagulated.
  • the porous membrane layer having a three-dimensional network structure in which the hydrophobic polymer and the gel-like hydrophilic polymer interpenetrate each other on the outer peripheral surface of the knitted string support.
  • the formed porous membrane 150 is obtained.
  • the coagulation liquid used here is a non-solvent for the hydrophobic polymer and needs to be a good solvent for the hydrophilic polymer, and examples thereof include water, ethanol, methanol, and mixtures thereof.
  • a mixed solution of a solvent and water is preferable from the viewpoint of safety and operation management.
  • the porous membrane formed by the above-mentioned coagulation process generally has a large pore size and potentially has high water permeability, but a large amount of hydrophilic polymer in solution remains in the porous membrane. Therefore, it may be difficult to exert sufficient high water permeability as it is. Further, when the hydrophilic polymer is dried in the film, it also causes a decrease in the mechanical strength of the film. Therefore, after the solidification step, a removal step for removing the hydrophilic polymer remaining in the porous membrane is usually performed, and then the porous membrane is dried.
  • the hydrophilic polymer remains in the membrane (porous portion) in a high concentration solution state.
  • a high concentration of hydrophilic polymer is relatively easily removed by immersing the porous membrane in a cleaning solution. Therefore, in the removal process, the porous membrane is first washed with a washing liquid, and then the hydrophilic polymer is lowered in molecular weight using an oxidizing agent, and then the lowered hydrophilic polymer is removed. It is preferable to do this.
  • the cleaning solution used for cleaning the porous membrane is not particularly limited as long as it is a clear and hydrophilic liquid in which the hydrophilic polymer is dispersed or dissolved, but water is preferable because of its high cleaning effect.
  • water to be used include tap water, industrial water, river water, well water, and the like, and alcohols, inorganic salts, oxidizing agents, surfactants, and the like may be mixed and used.
  • a mixed liquid of a good solvent for the hydrophobic polymer and water can be used as the cleaning liquid.
  • Examples of the method for washing the porous film with the washing liquid include a method for immersing the porous film in the washing liquid and a method for running the porous film in a washing tank in which the washing liquid is stored.
  • the washing temperature is preferably high, preferably 50 ° C. or higher, more preferably 80 ° C. or higher, in order to keep the viscosity of the hydrophilic polymer solution low and prevent a decrease in diffusion transfer rate.
  • the outer surface of the porous film can be scraped off by bubbling due to boiling, so that efficient cleaning is possible.
  • the hydrophilic polymer remaining in the porous membrane is in a relatively low concentration state.
  • the solvent used in the film forming stock solution remains in the porous film formed by the coagulation process, but the solvent remaining in the porous film is removed by the porous film washing process. Is done.
  • a hydrophilic polymer As a method of lowering the molecular weight of a hydrophilic polymer, first, a chemical solution containing an oxidizing agent is held in a porous membrane, and then the porous membrane holding the chemical solution is heated in a gas phase.
  • the method is preferred.
  • the oxidizing agent ozone, hydrogen peroxide, permanganate, dichromate, persulfate, etc. can be used, but it has strong oxidizing power and excellent decomposition performance, excellent handleability, and low cost. Of these, hypochlorite is particularly preferable. Examples of hypochlorite include sodium hypochlorite and calcium hypochlorite, with sodium hypochlorite being particularly preferred.
  • the temperature of the chemical solution is preferably 50 ° C. or less, and more preferably 30 ° C. or less.
  • the temperature is higher than 50 ° C., oxidative decomposition is promoted during the immersion of the porous membrane, and the hydrophilic polymer that has fallen into the chemical solution is further oxidatively decomposed, leading to waste of the oxidizing agent.
  • the temperature of the chemical solution is preferably 0 ° C. or higher, and more preferably 10 ° C. or higher.
  • the hydrophilic polymer is oxidized and decomposed by heating the porous membrane in the gas phase.
  • the chemical liquid retained in the porous film is not significantly diluted or the chemical liquid is almost not dropped and eluted into the heating medium, and the oxidizing agent in the chemical liquid is porous film. It is preferable because it is efficiently used for decomposing the hydrophilic polymer remaining therein.
  • the porous film As a specific heating method, it is preferable to heat the porous film using a heating fluid under atmospheric pressure. It is preferable to use a fluid having a high relative humidity as the heating fluid, that is, heating under humid heat conditions, because drying of an oxidizing agent such as hypochlorite is prevented and efficient decomposition treatment is possible.
  • the relative humidity of the fluid is preferably 80% or more, more preferably 90% or more, and most preferably in the vicinity of 100%.
  • the lower limit of the heating temperature is preferably 50 ° C., more preferably 80 ° C., because the treatment time can be shortened when continuous treatment is performed.
  • the upper limit of the temperature is preferably 100 ° C. in the atmospheric pressure state.
  • Removal of hydrophilic polymer As a method of removing the hydrophilic polymer having a reduced molecular weight, a method of washing the porous membrane with a washing solution under the same conditions as in the porous membrane washing step described above can be mentioned. If the hydrophilic polymer remains even after the low molecular weight hydrophilic polymer is removed, a depressurization step of depressurizing the outer peripheral side of the porous membrane may be further performed. By depressurizing the outer peripheral side of the porous membrane, the pressure on the outer peripheral side of the porous membrane becomes lower than the inner peripheral side, and the hydrophilic polymer remaining in the porous membrane moves to the outer peripheral side due to the pressure difference . Therefore, the hydrophilic polymer can be removed more effectively.
  • the braided string support is pulled out from the stationary storage container, so that there is no need to use a rotating means such as a turntable. Therefore, the braided string support can be supplied with a simple mechanism.
  • the storage containers can be placed directly on the floor, a large number of storage containers can be installed, and the space can be used effectively. Further, even when a plurality of porous membranes are manufactured at a time, it is easy to simultaneously supply a number of braided string supports corresponding to the number of porous membranes.
  • the braided string (knitted string support 110) is used as the support for the porous membrane, even if the storage container is pulled out as it is without being rotated, it is different from the case of the braid, that is, the case where the braid support 12 is employed.
  • the twist does not accumulate at a specific part of the support, and the generated twist moves as the knitted string travels. Therefore, twisting hardly occurs and the twisted hump portion is not easily formed. This is because when the braided string (braided string support body 12) has a large twisting torque, which is a reaction force when twisted, the braided string (braided string support body 110) has a small twisting torque, so that it is pulled out from the storage container 120.
  • knitted string support 110 itself twists with a weak force and can maintain its form, and is easily sent stably downstream as the knitted string travels while being twisted. Therefore, if it is this invention, a porous membrane can be manufactured stably.
  • the storage container when the knitted string support is pulled out, the storage container is in a stationary state, so that it can be easily connected to the knitted string support stored in the next storage container. Moreover, there is no need to worry about the connection timing or the time required for connection.
  • the storage containers in which the connected support bodies are stored must be placed on the same turntable. Since the number of storage containers that can be put on the turntable is limited, when the hollow string is pulled out and the number of hollow strings on the turntable decreases, the rotation stops again, and the empty storage container becomes the turntable. Therefore, it is necessary to repeat the operation of connecting the hollow string of the next storage container and placing the storage container on the turntable.
  • a large number of storage containers storing knitted string supports can be installed in a predetermined location in advance, and the knitted string supports stored in these storage containers are connected at a time. can do. And after all the braided string supports have been pulled out from any storage container, the storage container can be removed as necessary, and the next storage container can be shifted to the place where the arbitrary storage container is placed. Work is simple.
  • the braided string support 110 stored in the storage container 120 as described above is pulled out from the storage container 212 toward the guide member 214 provided on the storage container 212 as shown in FIG. At this time, the guide member 214 is provided, so that the braided string support 110 is prevented from being entangled due to the braided string support 110 being caught by the trunk of the storage container 120 or the core rod 121. It is preferable to pull out the braided string support 110 while the storage container 120 is stationary from the viewpoint that the facilities can be simplified and the space can be used effectively.
  • the braided string support 110 is pulled out from the end of storage when stored in the storage container 120.
  • the braided string support 110 pulled out from the storage container 120 is supplied to the spinning nozzle 220.
  • the braided string support 110 stored in the storage container 120 has a finite length.
  • the braided string supports 110 stored in the plurality of storage containers 120 may be connected and used.
  • the spinning nozzle 220 is spun so that the raw film forming solution 25 is applied to the outside of the supplied braided string support 110, and is immersed in the coagulating liquid 230b accommodated in the coagulating bath 230a.
  • the membrane-forming stock solution 25 is solidified to form the porous hollow fiber membrane 26.
  • the porous hollow fiber membrane 26 is obtained through steps such as washing and drying.
  • a film-forming stock solution containing a film-forming resin, a pore-opening agent and a solvent is used as the film-forming stock solution 25 .
  • this film-forming stock solution is immersed in the coagulation liquid, the coagulation liquid diffuses into the film-forming stock solution, and the film-forming resin and the pore-opening agent coagulate while causing phase separation, respectively.
  • a porous membrane layer is formed.
  • film-forming resin ordinary resins used for forming a porous film can be used, for example, polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride resin, polyacrylonitrile resin, polyimide resin, Polyamideimide resin, polyesterimide resin, etc. are mentioned. These can be appropriately selected and used as necessary, and among these, polyvinylidene fluoride resin is preferred because of excellent chemical resistance.
  • a film-forming resin may be used alone or in combination of two or more.
  • a hydrophilic polymer resin such as monool-based, diol-based, triol-based, or polyvinylpyrrolidone represented by polyethylene glycol can be used. These can be appropriately selected and used as necessary, and among these, polyvinylpyrrolidone is preferred because of its excellent thickening effect.
  • One type of pore-opening agent may be used alone, or two or more types may be used in combination.
  • the solvent is not particularly limited as long as it can dissolve both the film-forming resin and the pore opening agent.
  • dimethyl sulfoxide, N, N-dimethylacetamide, dimethylformamide can be used.
  • N, N-dimethylacetamide is preferable from the viewpoint that the film-forming resin can be more efficiently dissolved in the solvent.
  • a solvent may be used individually by 1 type and may use 2 or more types together. It should be noted that other materials and additives other than the pore-opening agent can be used as an optional component in the film-forming stock solution 25 as long as the control of phase separation is not hindered.
  • the content of the film-forming resin in the film-forming stock solution 25 (100% by mass) is preferably 10% by mass or more from the viewpoint that stability during film formation is improved and an excellent porous film structure is easily formed. 15 mass% or more is more preferable. Further, for the same reason, the content of the film-forming resin is preferably 30% by mass or less, and more preferably 25% by mass or less.
  • the content of the pore-opening agent in the membrane-forming stock solution 25 (100% by mass) is preferably 1% by mass or more and more preferably 5% by mass or more from the viewpoint that the formation of the porous membrane is facilitated. In addition, the content of the pore-opening agent is preferably 20% by mass or less, and more preferably 12% by mass or less from the viewpoint of the handleability of the film-forming stock solution.
  • the guide member is not provided on the storage container, and when the braided string support pulled out from the storage container is pulled up obliquely, the braided string support is attached to the trunk or core rod of the storage container.
  • the knitted string support may be entangled because it may be caught or a force may be applied irregularly by contact.
  • the guide member is provided on the storage container, and the knitted string support is pulled out from the storage container toward the guide member, so that the knitted string support is the storage container. It is suppressed that it gets tangled by being caught on the main body, core rod, etc. Therefore, excellent process stability can be obtained in the production of the porous hollow fiber membrane.
  • the knitted string supply device of the present invention is not limited to the knitted string supply device 210.
  • a braid supply device having a storage container that does not have a core bar may be used. *
  • FIG. 12A is a schematic configuration diagram illustrating an example of a winding device used when a braided string support is wound around a bobbin.
  • the winding device 180a of this example includes a bobbin 170 for winding the braid string support 110, a bobbin fixing jig 181 that rotatably supports the bobbin 170, and a supply guide 182 that supplies the braid string support to the bobbin 170. It has.
  • the bobbin 170 includes a cylindrical winding portion 171 around which the braided string support 110 is wound, and flange portions 172 and 173 that are detachably attached to both ends of the winding portion 171.
  • the diameter of the winding part 171 is appropriately selected depending on the winding amount of the knitted string support 110, the drawing form of the knitted string support, and the like.
  • a support shaft 181a extending horizontally is attached to the bobbin fixing jig 181, and the bobbin 170 is inserted into the support shaft 181a. Then, the bobbin 170 can also be rotated by the rotation of the support shaft 181a.
  • the supply guide 182 is not particularly limited as long as it can supply the braided string support 110 to the bobbin 170 while reciprocating in the central axis direction of the bobbin 170.
  • the bobbin 170 is fed at a constant speed to the winding portion 171 of the rotating bobbin 170 via the supply guide 182 that reciprocates in the central axis direction of the bobbin 170. Wrap around 170.
  • the winding method is not particularly limited, and examples thereof include parallel winding, twill winding, and ball winding that reduce the winding width with the number of winding steps of the braided string support.
  • the end of the braided string support 110 should be taken out so as not to be wound around the winding part 171 of the bobbin 170. It is preferable to keep. If the start end protrudes from the bobbin 170, it is easy to connect the braided string support housed in the next bobbin when connecting the braided string support described later.
  • the knitted string support 110 is pulled out from the bobbin 170 in the winding axis direction, that is, in the central axis direction of the bobbin 170 while the bobbin 170 is stationary.
  • the bobbin 170 is arranged on the floor, a pedestal, or the like with one flange portion 172 of the bobbin 170 facing downward so that the central axis direction of the bobbin 170 is vertical.
  • the braided string support body 110 vertically upward.
  • the other flange portion of the bobbin 170 is removed from the winding portion 171. Further, the braided string support 110 is pulled out from the end of winding around the bobbin 170 (winding end).
  • the diameter of the wound object of the knitted string support 110 wound around the bobbin 170 is above the bobbin 170, that is, substantially on the extension line of the bobbin 170 in the direction in which the knitted string support 110 is pulled out.
  • a drawer guide 124 for fixing the position of the braided string support 110 in the horizontal direction is attached at a position several to several tens of times away from the bobbin 170, and the braided string support 110 passes through the drawer guide 124. It is preferable to pull out.
  • pull-out guide 124 is attached in this way, when the loop of the braided string support body 110 housed in the bobbin 170 is unwound and pulled out, the pull-out speed and the resistance at which the loop can be unraveled are easily stabilized.
  • the braided string support 110 pulled out from the bobbin 170 is supplied to the next coagulation step.
  • the braided string support body 110 wound around the bobbin 170 has a finite length, in order to supply the braided string support body 110 continuously to the solidification step, each braid wound around a plurality of bobbins. What is necessary is just to connect and use a string support body.
  • a braided string support wound around an arbitrary bobbin 170 (170a) so that each braided string support 110 wound around a plurality of bobbins 170 is connected.
  • the winding start end a11 of 110a is connected to the winding end b12 of the braided string support 110b wound around the next bobbin 170b, and the winding of the braided string support 110b wound around the bobbin 170b is connected.
  • the start end b11 is connected to the winding end c12 of the braided string support 110c wound around the next bobbin 170c.
  • connection method of the braided string support include the connection methods described in the first embodiment. In particular, the method of connecting by ultrasonic waves of (1) is preferable.
  • the braided string support is pulled out from the bobbin in a stationary state, so there is no need to use a jig (rotating means) for rotating the bobbin. Therefore, the braided string support can be supplied with a simple mechanism.
  • the knitted string support wound around the next bobbin can be easily obtained without stopping the production of the porous membrane. Can be connected. Moreover, there is no need to worry about the connection timing or the time required for connection.
  • the winding of the braided string support around the bobbin is not limited to the method described above.
  • the knitted string support 110 is wound with the central axis direction of the bobbin 170 horizontal, but for example, using the winding device 180b shown in FIG.
  • the knitted string support 110 may be wound in the following manner with the central axis direction of the bobbin 170 vertical.
  • bobbin 170 includes a bobbin 170, a supply guide 182 for supplying the braided string support 110 to the bobbin 170, the supply guide 182 being rotatable along the periphery of the bobbin 170, and the central axis of the bobbin 170. And a guide fixing jig 183 that supports the reciprocating movement in the direction.
  • a guide fixing jig 183 that supports the reciprocating movement in the direction.
  • one flange portion 172 of the bobbin 170 is directed downward so that the central axis direction of the bobbin 170 is vertical.
  • the bobbin 170 is then placed on the floor or pedestal.
  • the braided string support 110 is wound around the bobbin 170 by a bobbin fixing jig 183 via a supply guide 182 that rotates around the bobbin 170 and reciprocates in the central axis direction of the bobbin 170. Are wound around the bobbin 170 while being fed at a constant speed.
  • the drawing of the braided string support from the bobbin is not limited to the method described above.
  • the bobbin 170 is installed on the floor or pedestal.
  • a bobbin fixing tool 190 to which a plurality of branches 191 are attached is used. 170a, 170b,...) May be inserted and the braided string support 110 may be pulled out in the direction of the central axis of the bobbin 170.
  • Example A1-1 ⁇ Porous membrane production equipment> As a porous membrane manufacturing apparatus, a porous membrane manufacturing apparatus 1100 shown in FIG. 15 was used. This porous membrane manufacturing apparatus 1100 is porous by applying a film-forming stock solution to a winder (storage container 120) around which a knitted string support 110 is wound and a knitted string support 110 pulled out from the storage container 120.
  • a drying unit 1120 for drying 150 and a winding unit 1130 for winding the dried porous membrane 150 are provided.
  • a dancer mechanism 1140 is provided between the storage container 120 and the porous film forming apparatus 160 to allow the braided string support 110 to pass through the spinning nozzle 161 of the porous film forming apparatus 160 with a constant tension. Yes.
  • a film-forming roll 1150 is provided between the porous film layer forming apparatus 160 and the removing means 1110 to take the porous film 150 from the porous film layer forming apparatus 160 at a constant speed and transfer it to the removing means 1110. It has been.
  • ⁇ Storage of braid support> (Knitted string support) As the knitted string support 110, polyester fibers (fineness: 420 dtex, number of filaments: 180) are circularly knitted with a circular knitting machine, and then continuously drawn with a metal die heated to 200 ° C. at a speed of about 3 m / min. Hollow braided string support with improved thermal characteristics, dimensional stability and mechanical properties (outer diameter: about 2.5 mm, hollow part diameter: about 1.5 mm, number of stitches per round: 12) Using. The twisted pull-out stability value X of the knitted string was 1.9 (g ⁇ cm).
  • Storage container 120 As the storage container 120, a paper-made cylindrical paper drum (drum inner diameter: 450 mm, depth: 800 mm) was used. A core rod 121 (outer diameter: 130 mm, height from the bottom of the drum 770 mm) is provided in the center of the drum.
  • the braided string support 110 was supplied to the storage container 120 installed on the turntable 131 under conditions of a supply speed of 3 m / min. Further, simultaneously with the supply of the knitted string support 110, the rotational speed during one rotation is periodically changed while the turntable 131 is rotated once in about 30 seconds, as shown in FIG. 110 is drawn from the bottom to the top of the storage container 120 so as to draw a loop-shaped arrangement trajectory, and while the arrangement trajectory surrounds the core rod 121, the adjacent loops are displaced in the direction around the rotation axis of the storage container 120.
  • the knitted string support 110 was stacked and stored. When the storage of the knitted string support 110 in the storage container 120 is started, the end (winding start end) of the knitted string support 110 is placed outside the storage container 120.
  • polyvinylidene fluoride A manufactured by Atofina Japan, trade name Kyner 301F
  • polyvinylidene fluoride B manufactured by Atofina Japan, trade name Kyner 9000LD
  • polyvinylpyrrolidone manufactured by ISP, trade name K-90
  • a porous membrane was produced as follows using the porous membrane production apparatus 1100 shown in FIG. With the axial direction of the storage container 120 in which the braided string support body 110 is stored oriented in the vertical direction and stationary, the braided string support body 110 is pulled out from the storage container 120 in the vertical direction at a speed of 10 m / min. The string support 110 was pulled out. The drawn braided string support 110 passes through a ring-shaped drawer guide 124 installed above the storage container 120, is changed in direction by a rotation guide 125, and is further adjusted in traveling speed by a support supply roll 126. Supplied to the dancer mechanism 1140.
  • the braided string support body 110 was supplied to the porous film layer forming apparatus 160.
  • the spinning nozzle 161 a hollow portion (pipe) is formed at the center, and a nozzle in which an annular discharge port is sequentially formed on the outside so that two kinds of liquids can be sequentially applied (Japanese Patent Laid-Open No. 2005). -See Fig. 1 of Japanese Patent No. 42074), and a braided string support was introduced into the hollow portion while keeping the temperature at 30 ° C.
  • the film-forming stock solutions (1) and (2) are supplied from the stock solution supply means 162 to the spinning nozzle 161, and the film-forming stock solution (2) and the film-forming stock solution (1) are placed on the outer periphery of the braided string support 110. It was applied from the inside in order and coagulated in a coagulation tank 163 containing a coagulation liquid (mixed solution of 5 parts by mass of N, N-dimethylacetamide and 95 parts by mass of water) kept at 80 ° C. In this way, as shown in FIG. 7, the knitted string support 110 is coated with the porous membrane layer 151 having an inclined structure having one fractional layer near the outer surface and increasing the pore diameter toward the inside. A porous membrane 150 was obtained.
  • a coagulation liquid mixed solution of 5 parts by mass of N, N-dimethylacetamide and 95 parts by mass of water
  • the main stock solution that forms the membrane structure of the porous membrane is the film-forming stock solution (1) applied to the outside.
  • the porous film 150 was taken up at a constant speed by the film forming roll 1150, and the hydrophilic polymer was removed by the removing means 1110. Specifically, first, the porous membrane 150 was washed in hot water at 98 ° C. for 3 minutes to remove a part of the remaining DMAc and polyvinylpyrrolidone. Thereafter, the step of immersing the porous membrane 150 in a 50000 mg / L sodium hypochlorite aqueous solution, the step of heating the porous membrane 150 in a 90 ° C.
  • Example A1-1 the storage container 120 is stably formed without forming a twisted hump portion on the knitted string support 110 even after 6 hours have elapsed after the knitted string support 110 is started to be pulled out from the storage container 120. I was able to pull it out from.
  • Example A1-2 A porous membrane was produced in the same manner as in Example A1-1, except that the drawing speed when drawing the braided string support 110 from the storage container 120 was changed to 20 m / min. As a result, even after 6 hours have passed since the drawing of the knitted string support 110 from the storage container 120, the knitted string support 110 can be stably pulled out from the storage container 120 without forming a twisted hump portion. did it.
  • Example A1-3 A porous membrane was produced in the same manner as in Example A1-1 except that the pulling speed when pulling the braided string support 110 out of the storage container 120 was changed to 50 m / min. As a result, even after 6 hours have passed since the drawing of the knitted string support 110 from the storage container 120, the knitted string support 110 can be stably pulled out from the storage container 120 without forming a twisted hump portion. did it.
  • Example A2-1 A bobbin is used instead of the storage container 120 as a winder, and the braided string support 110 is moved via a supply guide 182 that reciprocates in the central axis direction of the bobbin 170 using a winding device 180a shown in FIG. 12A.
  • the bobbin 170 was wound around the bobbin 170 while being supplied to the winding part 171 (outer diameter: 190 mm) of the rotating bobbin 170 at a constant speed.
  • the end of the braided string support 110 should be taken out so as not to be wound around the winding part 171 of the bobbin 170. Oita.
  • a porous membrane was produced in the same manner as in Example A1-1 except that the braided string support 110 was pulled out from the bobbin 170 around which the braided string support 110 was wound in this manner at a drawing speed of 15 m / min. did. As a result, the knitted string support 110 was stably pulled out from the bobbin 170 without forming a twisted hump portion on the knitted string support 110 even after 6 hours had passed after the knitted string support 110 started to be pulled out from the bobbin 170. .
  • Example A2-2 A porous membrane was produced in the same manner as in Example A2-1 except that the drawing speed when drawing the braided string support 110 from the bobbin 170 was changed to 30 m / min. As a result, the knitted string support 110 was stably pulled out from the bobbin 170 without forming a twisted hump portion on the knitted string support 110 even after 6 hours had passed after the knitted string support 110 started to be pulled out from the bobbin 170. .
  • Example A3-1 In the same manner as in Example A1-1, two storage containers 120 storing knitted string supports 110 were prepared. The winding start end of the knitted string support 110 stored in one storage container and the winding end of the knitting string support 110 stored in the other storage container were connected by ultrasonic waves. Except that the braided string support 110 was continuously pulled out from the two storage containers 120 to which the braided string support 110 was connected in this manner under the condition of a pulling speed of 30 m / min, the same as in Example A1-1. A porous membrane was manufactured.
  • the knitted string support body 110 can be stably pulled out from the storage container 120 without forming a twisted hump portion. did it.
  • Example A3-2 In the same manner as in Example A2-1, two bobbins 170 around which the braided string support 110 was wound were prepared. The winding start end of the braided string support 110 wound around one bobbin and the winding end of the braided string support 110 wound around the other bobbin were connected by ultrasonic waves. Except that the braided string support 110 was continuously pulled out from the two bobbins 170 to which the braided string support 110 was connected in this manner under the condition of a pulling speed of 30 m / min, the same as in Example A1-1. A porous membrane was produced.
  • Example B1 A porous hollow fiber membrane was manufactured as follows using the braided string supply device 210 illustrated in FIG. As the storage container 120, a paper-made cylindrical paper drum (drum inner diameter: 450 mm, depth: 900 mm) was used. A core rod 121 (outer diameter: 130 mm, height from the bottom 122 of the drum 880 mm) is provided in the center of the drum.
  • the guide member 214 As the guide member 214, a guide roll (made of polyethylene, roller groove diameter 80 mm, outer diameter 100 mm) was used. The height of the guide member 214 from the bottom 122 of the storage container 120 was 2.8 m. In addition, when a straight line connecting the guide member 214 and the lower corner 212d farthest from the guide member 214 in the storage container 120 is a straight line m, an angle ⁇ formed by the straight line m and the bottom 122 of the storage container 120 is 80 °. It was. As the braided string support 110, a braided string (manufactured by Mitsubishi Rayon Co., Ltd., trade name M1205) was used.
  • film-forming stock solution 25.7 kg of polyvinylidene fluoride PVDF301F manufactured by Arkema, which is a film-forming resin, and 15.6 kg of polyvinylpyrrolidone PVP-K79, manufactured by Nippon Shokubai Co., Ltd., which is a pore-opening agent, are used as solvents. , N-dimethylacetamide (DMAc, manufactured by Samsung Fine Chemical Co., Ltd.) dissolved in 112.2 L and defoamed was used.
  • DMAc N-dimethylacetamide
  • the storage container 120 is placed on the turntable, and the braided string support body 110 is supplied under the condition of a supply speed of 3 m / min while periodically rotating the rotation speed during one rotation while rotating once in about 13 seconds. As shown in FIG. 4, the adjacent loops deviate in the direction around the rotation axis of the storage container 120 so that the braided string support 110 draws a loop-shaped arrangement locus and the arrangement locus surrounds the core rod 121. As described above, the braided string support 110 was stacked and stored from the bottom portion 122 of the storage container 120 toward the upper portion 212c. When the storage of the knitted string support 110 in the storage container 120 is started, the storage start end of the knitted string support 110 is placed outside the storage container 120.
  • the braided string support 110 is pulled out from the stationary storage container 120 toward the guide member 214 at a pulling speed of 20 m / min, and is supplied to the spinning nozzle 220 while being tensioned by the tension applying means 216.
  • the film-forming stock solution 25 was spun so as to be applied to the outside of 110, and the membrane-forming stock solution 25 was coagulated in a coagulating solution 230b (8% DMAc aqueous solution) kept at 80 ° C. to form a porous hollow fiber membrane. Furthermore, washing with a washing solution (hot water at 90 ° C.), removal of the pore-opening agent with hypochlorite, and drying were performed to obtain a porous hollow fiber membrane.
  • Example B1 In the production of the porous hollow fiber membrane in Example B1, no entanglement occurred in the knitted string support 110 supplied to the spinning nozzle 220 by the knitted string supply device 210, and excellent process stability was obtained.
  • Example 1 A hollow braided support (outer diameter: about 2.2 mm, hollow part diameter: about) knitted by braiding 16 polyester fibers (fineness: 830 dtex, number of filaments: 96) instead of the braided support A porous membrane was produced in the same manner as in Example A1-1 except that 1.0 mm) was used.
  • the torsional pulling stability value X of the braid support was 14.7 (g ⁇ cm). As a result, the drawing speed of the braid support started to change from about 5 minutes after starting to draw the braid support from the storage container 120, and a weak twist was formed on the braid support drawn from the storage container 120. .
  • the method for pulling out the knitted string of the present invention supplies the support with a simple mechanism and effectively utilizing the space while suppressing the occurrence of twisting even when the knitted string support is pulled out continuously. Therefore, it can be suitably used for producing a porous membrane.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
  • Unwinding Of Filamentary Materials (AREA)
  • Tension Adjustment In Filamentary Materials (AREA)
  • Knitting Of Fabric (AREA)
  • Braiding, Manufacturing Of Bobbin-Net Or Lace, And Manufacturing Of Nets By Knotting (AREA)
PCT/JP2012/052701 2011-02-07 2012-02-07 編紐引き出し方法、多孔質膜の製造方法及び編紐供給装置 WO2012108413A1 (ja)

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JP2012511854A JPWO2012108413A1 (ja) 2011-02-07 2012-02-07 編紐引き出し方法、多孔質膜の製造方法及び編紐供給装置
KR1020137021782A KR101560074B1 (ko) 2011-02-07 2012-02-07 편뉴 인출 방법, 다공질막의 제조 방법 및 편뉴 공급 장치

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KR101560074B1 (ko) 2015-10-13
JPWO2012108413A1 (ja) 2014-07-03
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JP2016128166A (ja) 2016-07-14
CN103492296A (zh) 2014-01-01

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