WO2019012727A1 - Hollow fiber membrane and method for manufacturing hollow fiber membrane - Google Patents

Hollow fiber membrane and method for manufacturing hollow fiber membrane Download PDF

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Publication number
WO2019012727A1
WO2019012727A1 PCT/JP2018/006770 JP2018006770W WO2019012727A1 WO 2019012727 A1 WO2019012727 A1 WO 2019012727A1 JP 2018006770 W JP2018006770 W JP 2018006770W WO 2019012727 A1 WO2019012727 A1 WO 2019012727A1
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Prior art keywords
support
hollow fiber
fiber membrane
bonding layer
sheet
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PCT/JP2018/006770
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French (fr)
Japanese (ja)
Inventor
大輝 宮田
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住友電気工業株式会社
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Priority to CN201880035340.4A priority Critical patent/CN110691641B/en
Publication of WO2019012727A1 publication Critical patent/WO2019012727A1/en

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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
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • 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
    • B01D69/12—Composite membranes; Ultra-thin 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/36—Polytetrafluoroethene

Definitions

  • the present invention relates to a hollow fiber membrane and a method for producing the hollow fiber membrane.
  • hollow fiber membranes are known as filtration membranes for water treatment.
  • the hollow fiber membrane is an elongated tubular filtration membrane closed at one end, which filters the water to be treated coming in contact from the outside to obtain filtrate water inside.
  • a porous stretched tube made of polytetrafluoroethylene is used as a support, and a filter layer is provided on the outer surface of the support layer (Patent Document 1), and a yarn composed of plural resin fine wires The thing which equips the outer surface of this support body with a porous membrane layer is proposed as a support body (patent document 2).
  • a strip-like porous resin sheet (filtration layer) is spirally wound on the outer surface of a porous stretched tube (support) made of polytetrafluoroethylene, and the support and filtration layer are formed. It welds at temperature (350 degreeC) more than these melting
  • a membrane forming solution of a porous membrane layer is applied to the outer surface of a hollow braid (support) which is knitted with a plurality of resin fine wires, and a membrane is formed in the support
  • the porous membrane layer is formed by coagulating the membrane-forming undiluted solution in a state in which the undiluted solution has entered, and the adhesive strength of the support and the porous membrane layer is improved.
  • the hollow fiber membrane according to one aspect of the present invention is formed of one or more cords, and is laminated on a porous hollow support and the outer surface of the support, at least a portion of which is on the support.
  • a method of manufacturing a hollow fiber membrane according to another aspect of the present invention comprises the steps of: thermally laminating a porous bonding layer and a porous filtration sheet; and hollow having porosity and being knitted with one or more strands. Contacting the outer surface of the support and the bonding layer side of the sheet after the heat lamination step, and thermally laminating the support and the sheet after the heat lamination step.
  • a hollow fiber membrane for water treatment is required to have mechanical permeability and chemical resistance as well as constant water permeability.
  • the hollow fiber membrane of Patent Document 1 has a configuration in which a filtration layer is directly bonded to the support using a stretched porous body having a not very high tensile strength as a support, so the machine when the hollow fiber membrane is bent and deformed Further improvements are needed to improve the durability.
  • the hollow fiber membrane of Patent Document 2 it is necessary to select a film forming solution which can be solidified as a material of the porous membrane layer, and therefore, polytetrafluoroethylene or the like having high chemical resistance can be used as the porous membrane layer.
  • the material of the porous membrane layer is limited.
  • the present invention has been made based on the above circumstances, and it is an object of the present invention to provide a hollow fiber membrane compatible with both chemical resistance and mechanical durability and a method for producing the hollow fiber membrane. .
  • the present invention can provide a hollow fiber membrane compatible with chemical resistance and mechanical durability.
  • the hollow fiber membrane according to one aspect of the present invention is formed of one or more cords, and is laminated on a porous hollow support and the outer surface of the support, at least a portion of which is on the support.
  • the hollow fiber membrane comprises a bonding layer between the support and the filtration sheet, and the bonding layer is welded to the support and the filtration sheet to bond them, so that the support and the filtration sheet can be strongly bonded, and the support And the material of the filter sheet can be selected relatively freely.
  • the support of the hollow fiber membrane is knitted with one or more cords, it has high tensile strength and appropriate flexibility.
  • the hollow fiber membrane uses a support having high tensile strength as a substrate, and the filtration sheet is bonded to the support via the bonding layer, so that the filtration sheet peels off from the support even when it is bent and deformed. It is difficult, and the pressure resistance at the time of filtration or backwashing is high. That is, since the hollow fiber membrane can be selected as one having high chemical resistance as the material of the support and the filter sheet, and structurally improves the mechanical durability, the chemical resistance and the mechanical can be improved. It is compatible with durability.
  • the support is formed in a tubular shape, the filter sheet is formed in a band shape, and the filter sheet is wound in a spiral and in a stripe shape on the outer surface of the support via the bonding layer. Good to be turned. Thus, the support and the filter sheet are easily and reliably bonded via the bonding layer.
  • the said string body prefferably knitted by 8 or more and 32 or less resin fine wire.
  • the mechanical strength of the support is further improved by the cords that knit the support being knitted with 8 or more and 32 or less resin thin wires.
  • the bonding layer may be a non-woven fabric or a porous resin.
  • the main component of the filter sheet is polytetrafluoroethylene.
  • the hollow fiber membrane is improved in chemical resistance by being used for a filtration sheet on which polytetrafluoroethylene having high chemical resistance is disposed on the outer surface.
  • the main component indicates a component with the highest content, for example, a component with a content of 50% by mass or more.
  • the average thickness of the filtration sheet may be 12 ⁇ m to 100 ⁇ m
  • the average pore diameter of the filtration sheet may be 0.01 ⁇ m to 0.45 ⁇ m
  • the bubble point of the hollow fiber membrane may be 80 kPa to 200 kPa.
  • the average pore diameter refers to a value obtained by microscopically observing 10 or more holes and averaging the average value of the maximum diameter of the holes and the diameter in the direction orthogonal to the maximum diameter in the entire sample.
  • the bubble point is a value measured according to JIS-K 3832 (1990) using isopropyl alcohol.
  • a method for producing a hollow fiber membrane according to another aspect of the present invention is a method for producing a hollow fiber membrane, comprising the steps of: thermally laminating a porous bonding layer and a porous filtration sheet; The outer surface of a hollow support which is knitted with a cord and has porosity is brought into contact with the bonding layer side of the sheet after the heat lamination step, and the support and the sheet after the heat lamination step are thermally laminated And a process.
  • the bonding layer of the sheet is welded to the support, so that the support and the filtration sheet are relatively easy to form via the bonding layer.
  • the method for producing a hollow fiber membrane can relatively easily produce a hollow fiber membrane having both chemical resistance and mechanical durability.
  • the hollow fiber membrane 1 of FIG. 1 and FIG. 2 is knitted with one or more cords and is laminated on a porous hollow support 2 and the outer surface of the support 2, at least a part of which is the support 2. And a porous filtration sheet 4 laminated on the side opposite to the support 2 side of the bonding layer 3 and in which at least a part of the bonding layer 3 is welded.
  • the cords for knitting the support 2 are knitted with 8 or more and 32 or less resin thin wires, and the support 2 is formed in a tubular shape.
  • the bonding layer 3 is a non-woven fabric or a porous resin.
  • the filtration sheet 4 is formed in a band shape.
  • the main component of the filtration sheet 4 is polytetrafluoroethylene, the average thickness of the filtration sheet 4 is 12 ⁇ m to 100 ⁇ m, and the average pore diameter of the filtration sheet 4 is 0.01 ⁇ m to 0.45 ⁇ m.
  • the filter sheet 4 is wound in a spiral and in a stripe shape on the outer surface of the support 2 via the bonding layer 3.
  • the bubble point of the hollow fiber membrane 1 is 80 kPa or more and 200 kPa or less.
  • the hollow fiber membrane 1 is a hollow fiber membrane used for water treatment, and as shown in FIG. 1, the bonding layer 3 and the filtration sheet 4 are laminated on the outer surface of the support 2 in this order. . As shown in FIG. 2, the hollow fiber membrane 1 is formed in a cylindrical shape so as to filter the water to be treated coming in contact with the filtration sheet 4 and obtain filtered water in the hollow portion 5 inside the support 2. .
  • the lower limit of the bubble point of the hollow fiber membrane 1 is preferably 80 kPa, more preferably 100 kPa, and still more preferably 120 kPa.
  • an upper limit of the bubble point of hollow fiber 1 200 kPa is preferred, 180 kPa is more preferred, and 160 kPa is still more preferred. If the bubble point of the hollow fiber membrane 1 does not reach the above lower limit, the water to be treated may not be filtered sufficiently. Conversely, if the bubble point of the hollow fiber membrane 1 exceeds the above upper limit, the water flow resistance may increase, and the filtration efficiency may decrease.
  • the support 2 is a member to be a base of the hollow fiber membrane 1 and is formed in a tubular shape.
  • the support 2 is knitted with one or more cords, and has a porosity that allows filtered water to permeate through the interstices of the cords.
  • a hollow portion 5 is formed inside the support 2.
  • the lower limit of the average thickness (average thickness) of the support 2 is preferably 0.1 mm, more preferably 0.3 mm, and still more preferably 0.5 mm.
  • the upper limit of the average thickness of the support 2 is preferably 2 mm, more preferably 1.7 mm, and still more preferably 1.5 mm. If the average thickness of the support 2 is less than the above lower limit, the mechanical strength of the support 2 may be insufficient. Conversely, when the average thickness of the support 2 exceeds the above upper limit, the hollow fiber membrane 1 becomes too thick, and the number density of the hollow fiber membranes 1 decreases when a plurality of hollow fiber membranes 1 are used, The filtration efficiency may be reduced.
  • the cords for knitting the support 2 are knitted with a plurality of resin thin wires in order to improve the mechanical strength.
  • the material of the resin fine wire is not particularly limited, but for example, polyester such as polyethylene terephthalate, or a resin containing polyethylene or polypropylene as a main component is used.
  • the number of resin thin lines which knit a string As a minimum of the number of resin thin lines which knit a string, eight are preferred, ten are more preferred, and 12 are still more preferred. On the other hand, as a maximum of the number of resin thin lines which knit a string, 32 are preferred, 28 are more preferred, and 24 is more preferred. If the number of resin thin wires for knitting the cords is less than the above lower limit, the mechanical strength of the cords may be insufficient. On the contrary, when the number of resin thin wires which knit a string exceeds the above-mentioned upper limit, there is a possibility that the manufacturing cost of a string may increase.
  • the bonding layer 3 is an intermediate layer for bonding the support 2 and the filtration sheet 4 by welding the surface in contact with the support 2 to the support 2 and welding the surface in contact with the filtration sheet 4 to the filtration sheet 4. It is laminated between the outer surface of the cylindrical support 2 and the inner surface of the filtration sheet 4.
  • the bonding layer 3 dissolves by a predetermined thickness from the surface in contact with the support 2, is bonded to the support 2 in this dissolved thickness region, and dissolves by a predetermined thickness from the surface in contact with the filtration sheet 4, It is joined to filtration sheet 4 in this dissolved thickness field.
  • As the bonding layer 3 a porous resin or non-woven fabric obtained by heat-treating a resin powder is used.
  • the material of the porous resin or the non-woven fabric is not particularly limited.
  • a porous resin containing polyester such as polyethylene terephthalate, polyethylene or polypropylene as a main component is used.
  • the bonding layer 3 is preferably made of the same material as the support 2 from the viewpoint of improving the affinity for bonding with the support 2.
  • the lower limit of the average thickness of the bonding layer 3 is preferably 10 ⁇ m, more preferably 20 ⁇ m, and still more preferably 30 ⁇ m.
  • the upper limit of the average thickness of the bonding layer 3 is preferably 200 ⁇ m, more preferably 150 ⁇ m, and still more preferably 100 ⁇ m. If the average thickness of the bonding layer 3 is less than the above lower limit, welding to the support 2 and the filtration sheet 4 may be insufficient, and the bonding strength of the bonding layer 3 may be insufficient. Conversely, when the average thickness of the bonding layer 3 exceeds the above upper limit, the hollow fiber membrane 1 becomes too thick, and the number density of the hollow fiber membrane 1 decreases when a plurality of hollow fiber membranes 1 are used, The filtration efficiency may be reduced.
  • the melting point is preferably equal to or lower than the melting point of the support 2 and lower than the melting point of the filtration sheet 4.
  • the filter sheet 4 when polytetrafluoroethylene (melting point about 327 ° C.) is used as the filter sheet 4 and polyethylene terephthalate, polyethylene or polypropylene (melting point about 110 ° C. to 260 ° C.) is used as the support 2, the support 2 is used as the bonding layer 3. It is preferable to use the same material as that of the above or the melting point of the support 2 or less.
  • the filtration sheet 4 is a strip-like porous sheet disposed on the outer surface of the bonding layer 3 and having a function of filtering the water to be treated. It is preferable that a porous resin having chemical resistance be used as the filtration sheet 4, and a porous resin containing polytetrafluoroethylene as a main component is used.
  • the filtration sheet 4 is disposed so as to cover the outer surface of the hollow fiber membrane 1 by being wound around the outer surface of the cylindrical support 2 in a spiral shape and in a stripe shape.
  • the filter sheet 4 is wound on the outer surface of the support 2 without gaps so that the side portions overlap.
  • the hollow fiber membrane 1 has the overlapping portion 6 in which the filtration sheet 4 is overlapped in a spiral shape and a stripe shape.
  • the support 2, the bonding layer 3, the filtration sheet 4, the bonding layer 3 and the filtration sheet 4 are bonded in this order.
  • the lower limit of the average thickness of the filtration sheet 4 is preferably 12 ⁇ m, more preferably 15 ⁇ m, and still more preferably 18 ⁇ m.
  • an upper limit of average thickness of filtration sheet 4 100 micrometers is preferred, 80 micrometers are more preferred, and 60 micrometers is still more preferred. If the average thickness of the filtration sheet 4 is less than the above lower limit, the water to be treated may not be filtered sufficiently. Conversely, if the average thickness of the filtration sheet 4 exceeds the above upper limit, the water flow resistance may increase, and the filtration efficiency may decrease.
  • the lower limit of the average pore diameter of the filtration sheet 4 is preferably 0.01 ⁇ m, more preferably 0.05 ⁇ m, and still more preferably 0.10 ⁇ m.
  • the upper limit of the average pore diameter of the filtration sheet 4 is preferably 0.45 ⁇ m, more preferably 0.40 ⁇ m, and still more preferably 0.35 ⁇ m. If the average pore diameter of the filtration sheet 4 is less than the above lower limit, the water flow resistance may be increased, and the filtration efficiency may be reduced. Conversely, if the average pore diameter of the filtration sheet 4 exceeds the above upper limit, the water to be treated may not be filtered sufficiently.
  • the method for producing the hollow fiber membrane is a method for producing the hollow fiber membrane 1, and the first laminating step of thermally laminating the porous bonding layer 3 and the porous filtration sheet 4; and one or more cords Forming an outer surface of the hollow support 2 having porosity and contacting the bonding layer 3 side of the sheet after the first lamination step, and thermally laminating the support 2 and the sheet after the first lamination step And 2) laminating.
  • the bonding layer 3 and the filtration sheet 4 are thermally laminated in a state where the bonding layer 3 is laminated so as to overlap in plan view on one surface of the filtration sheet 4.
  • Weld As the bonding layer 3, one having a melting point lower than that of the filtration sheet 4 is used.
  • the method of thermal lamination is not particularly limited.
  • a method of welding the bonding layer 3 to the filtration sheet 4 by melting one surface side of the bonding layer 3 by a predetermined thickness and then cooling in a state where the filtration sheet 4 is in contact with the melting surface
  • heating is performed from the filtration sheet 4 side to dissolve the bonding layer 3 in the vicinity of the filtration sheet 4 by a predetermined thickness, and then cooled.
  • the method of welding is used.
  • the bonding layer 3 preferably has a predetermined thickness dissolved at a temperature about 10 ° C. to 50 ° C. higher than the melting point of the bonding layer 3.
  • the laminated sheet after the first laminating step is processed into a band shape using a method such as cutting before the second laminating step.
  • a method such as cutting before the second laminating step.
  • the shape of the lamination sheet after the 1st lamination process should just be strip shape, it changes to the method of processing the lamination sheet after the 1st lamination step, for example, uses the strip-shaped filtration sheet 4 for the 1st lamination process.
  • a method may be employed to obtain a band-like laminated sheet by performing.
  • the laminated sheet and the support 2 are thermally laminated in a state where the bonding layer 3 side of the laminated sheet after the first laminating step is in contact with the outer surface of the cylindrical support 2. Thereby, the bonding layer 3 is welded to the support 2.
  • the same material as that of the bonding layer 3 may be used, or a material of the melting point or more of the bonding layer 3 may be used.
  • the strip-like laminated sheet and the support 2 are laminated, as shown in FIG. 2, the strip-like laminated sheet is wound in a spiral shape and a stripe form on the outer surface of the cylindrical support 2.
  • the bonding layer 3 and the filtration sheet 4 are laminated in this order on the outer surface of the support 2.
  • the outer surface of the manufactured hollow fiber membrane 1 needs to be covered with the filtration sheet 4 without a gap, so the strip-like laminated sheet has a spiral shape and a stripe shape with respect to the support 2 so that the side portions overlap. It is wound around.
  • the method of thermal lamination is not particularly limited.
  • the strip-shaped laminated sheet is formed on the support 2 while bringing the outer surface of the support 2 and the upper surface of the laminated sheet into contact with the dissolution surface.
  • a method of welding the bonding layer 3 to the support 2 by winding in a spiral shape and a stripe shape is used.
  • the bonding layer 3 preferably has a predetermined thickness dissolved at a temperature about 10 ° C. to 50 ° C. higher than the melting point of the bonding layer 3.
  • the hollow fiber membrane 1 includes the bonding layer 3 between the support 2 and the filtration sheet 4, and the bonding layer 3 is welded to the support 2 and the filtration sheet 4 to bond them, so the support 2 and the filtration sheet Bond 4 strongly.
  • the support 2 of the hollow fiber membrane 1 has high tensile strength and appropriate flexibility because it is knitted by a cord body knitted with 8 or more and 32 or less resin fine wires. Since the bonding layer 3 of the hollow fiber membrane 1 is a non-woven fabric or a porous resin, when the hollow fiber membrane 1 is bent and deformed, it is appropriately deformed to disperse stress.
  • the hollow fiber membrane 1 uses the support 2 having high tensile strength as a base, and the filtration sheet 4 is joined to the support 2 via the bonding layer 3, so that the filtration sheet 4 is also deformed when bending. And the joining layer 3 is hard to peel from the support body 2, and the pressure resistance at the time of filtration or backwashing is high.
  • the polytetrafluoroethylene with high chemical resistance is used for the filtration sheet 4 of the said hollow fiber membrane 1, the said hollow fiber membrane 1 makes chemical resistance and mechanical durability compatible.
  • the hollow fiber membrane 1 has a bubble point of 80 kPa or more and 200 kPa or less, water permeability and impurity removal performance are adjusted in a well-balanced manner.
  • the welding layer 3 is welded to the filtration sheet 4 and then the welding layer 3 of this sheet is welded to the support 2.
  • the filter sheet 4 can be joined relatively easily. Further, according to the method of manufacturing the hollow fiber membrane, since the strip-shaped filtration sheet 4 is spirally and stripe-shaped so that the side portions overlap with the outer surface of the cylindrical support 2, the outer surface is The hollow fiber membrane 1 covered with the filtration sheet 4 without any gap can be manufactured, and the support 2 and the filtration sheet 4 can be joined easily and reliably through the joining layer 3.
  • the hollow part 5 should just be formed inside the support body 2, and the shape of the support body 2 is not limited to a cylinder shape.
  • the strip-shaped filtration sheet 4 is spirally wound around the outer surface of the cylindrical support 2 in the form of stripes, but the filtration sheet 4 is supported via the bonding layer 3 As long as it is a laminated structure bonded to the outer surface of the body 2, the support 2, the bonding layer 3 and the filtration sheet 4 may be bonded by another procedure.
  • the hollow fiber membrane of the present invention and the hollow fiber membrane produced by the method of producing a hollow fiber membrane of the present invention can achieve both chemical resistance and mechanical durability.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

A hollow fiber membrane according to an embodiment of the present invention is provided with: a porous hollow support body that is formed by one or a plurality of string bodies; a porous joining layer that is laminated to the outer surface of the support body and at least part of which is fused to the support body; and a porous filtration sheet that is laminated on the side of the joining layer opposite from the support body and at least part of which is fused to the joining layer.

Description

中空糸膜及び中空糸膜の製造方法Hollow fiber membrane and method for producing hollow fiber membrane
　本発明は、中空糸膜及び中空糸膜の製造方法に関する。本出願は、２０１７年０７月１１日出願の日本出願第２０１７－１３５３６６号に基づく優先権を主張し、上記日本出願に記載された全ての記載内容を援用するものである。 The present invention relates to a hollow fiber membrane and a method for producing the hollow fiber membrane. This application claims the priority based on Japanese Patent Application No. 2017-135366 filed on Jul. 11, 2017, and incorporates all the contents described in the above-mentioned Japanese application.
　従来、水処理用の濾過膜として中空糸膜が知られている。中空糸膜は、一端が閉止された細長い管状の濾過膜であり、外側から接触する被処理水を濾過し、内側に濾過水を得るものである。 Conventionally, hollow fiber membranes are known as filtration membranes for water treatment. The hollow fiber membrane is an elongated tubular filtration membrane closed at one end, which filters the water to be treated coming in contact from the outside to obtain filtrate water inside.
　中空糸膜としては、例えば、ポリテトラフルオロエチレンからなる多孔質延伸チューブを支持体とし、この支持層の外表面に濾過層を備えるもの（特許文献１）、複数の樹脂細線からなる糸で編成された中空状組紐を支持体とし、この支持体の外表面に多孔質膜層を備えるもの（特許文献２）が提案されている。 As a hollow fiber membrane, for example, a porous stretched tube made of polytetrafluoroethylene is used as a support, and a filter layer is provided on the outer surface of the support layer (Patent Document 1), and a yarn composed of plural resin fine wires The thing which equips the outer surface of this support body with a porous membrane layer is proposed as a support body (patent document 2).
　特許文献１の中空糸膜は、ポリテトラフルオロエチレンからなる多孔質延伸チューブ（支持体）の外表面に帯状の多孔質樹脂シート（濾過層）を螺旋状に巻回し、支持体及び濾過層をこれらの融点以上の温度（３５０℃）で溶着して両者を一体化するものであり、機械的耐久性及び耐薬品性を向上させたものである。 In the hollow fiber membrane of Patent Document 1, a strip-like porous resin sheet (filtration layer) is spirally wound on the outer surface of a porous stretched tube (support) made of polytetrafluoroethylene, and the support and filtration layer are formed. It welds at temperature (350 degreeC) more than these melting | fusing point, integrates both, and improves mechanical durability and chemical resistance.
　また、特許文献２の中空糸膜は、複数の樹脂細線からなる糸で編成された中空状組紐（支持体）の外表面に多孔質膜層の製膜原液を塗布し、支持体内に製膜原液が進入した状態で製膜原液を凝固させて多孔質膜層を形成するものであり、支持体及び多孔質膜層の接着強度を向上させたものである。 Further, in the hollow fiber membrane of Patent Document 2, a membrane forming solution of a porous membrane layer is applied to the outer surface of a hollow braid (support) which is knitted with a plurality of resin fine wires, and a membrane is formed in the support The porous membrane layer is formed by coagulating the membrane-forming undiluted solution in a state in which the undiluted solution has entered, and the adhesive strength of the support and the porous membrane layer is improved.
特開２００４－１４１７５３号公報Unexamined-Japanese-Patent No. 2004-141753 特許第５３４１７６０号公報Patent No. 5341760
[課題を解決するための手段]
　本発明の一態様に係る中空糸膜は、１又は複数の紐体で編成され、多孔性を有する中空の支持体と、上記支持体の外表面に積層され、少なくとも一部が上記支持体に溶着する多孔性の接合層と、上記接合層の上記支持体側とは逆側に積層され、上記接合層の少なくとも一部が溶着する多孔性の濾過シートとを備える。 [Means for Solving the Problems]
The hollow fiber membrane according to one aspect of the present invention is formed of one or more cords, and is laminated on a porous hollow support and the outer surface of the support, at least a portion of which is on the support. A porous bonding layer to be welded, and a porous filtration sheet laminated on the opposite side of the bonding layer to the support side and to which at least a part of the bonding layer is welded.
　本発明の他の一態様に係る中空糸膜の製造方法は、多孔性の接合層及び多孔性の濾過シートを熱ラミネートする工程と、１又は複数の紐体で編成され、多孔性を有する中空の支持体における外表面及び上記熱ラミネート工程後のシートの上記接合層側を接触させ、上記支持体及び上記熱ラミネート工程後のシートを熱ラミネートする工程とを有する。 A method of manufacturing a hollow fiber membrane according to another aspect of the present invention comprises the steps of: thermally laminating a porous bonding layer and a porous filtration sheet; and hollow having porosity and being knitted with one or more strands. Contacting the outer surface of the support and the bonding layer side of the sheet after the heat lamination step, and thermally laminating the support and the sheet after the heat lamination step.
本発明の一実施形態に係る中空糸膜を長手方向に沿って切断した断面の一部を示す模式的断面図である。It is a schematic cross section which shows a part of cross section which cut | disconnected the hollow fiber membrane which concerns on one Embodiment of this invention along the longitudinal direction. 本発明の一実施形態に係る中空糸膜を示す模式的斜視断面図である。It is a typical perspective sectional view showing a hollow fiber membrane concerning one embodiment of the present invention.
[発明が解決しようとする課題]
　水処理用の中空糸膜には、一定の透水性能とともに機械的耐久性及び耐薬品性が求められる。特許文献１の中空糸膜は、引張強度があまり高くない延伸多孔質体を支持体として用い、この支持体に濾過層を直接接合した構成であるため、中空糸膜が曲げ変形する場合の機械的耐久性を向上させるにはさらなる工夫が必要である。また、特許文献２の中空糸膜は、凝固させることが可能な製膜原液を多孔質膜層の材料として選択する必要があるので、耐薬品性の高いポリテトラフルオロエチレン等を多孔質膜層に用いることができず、多孔質膜層の材料が制限される。 [Problems to be solved by the invention]
A hollow fiber membrane for water treatment is required to have mechanical permeability and chemical resistance as well as constant water permeability. The hollow fiber membrane of Patent Document 1 has a configuration in which a filtration layer is directly bonded to the support using a stretched porous body having a not very high tensile strength as a support, so the machine when the hollow fiber membrane is bent and deformed Further improvements are needed to improve the durability. Further, in the hollow fiber membrane of Patent Document 2, it is necessary to select a film forming solution which can be solidified as a material of the porous membrane layer, and therefore, polytetrafluoroethylene or the like having high chemical resistance can be used as the porous membrane layer. The material of the porous membrane layer is limited.
　本発明は、上述のような事情に基づいてなされたものであり、耐薬品性と機械的耐久性とを両立可能な中空糸膜及びこの中空糸膜の製造方法を提供することを目的とする。 The present invention has been made based on the above circumstances, and it is an object of the present invention to provide a hollow fiber membrane compatible with both chemical resistance and mechanical durability and a method for producing the hollow fiber membrane. .
[発明の効果]
　本発明は、耐薬品性と機械的耐久性とを両立可能な中空糸膜を提供できる。 [Effect of the invention]
The present invention can provide a hollow fiber membrane compatible with chemical resistance and mechanical durability.
［本発明の実施形態の説明］
　最初に本発明の実施態様を列記して説明する。 Description of the embodiment of the present invention
First, the embodiments of the present invention will be listed and described.
　本発明の一態様に係る中空糸膜は、１又は複数の紐体で編成され、多孔性を有する中空の支持体と、上記支持体の外表面に積層され、少なくとも一部が上記支持体に溶着する多孔性の接合層と、上記接合層の上記支持体側とは逆側に積層され、上記接合層の少なくとも一部が溶着する多孔性の濾過シートとを備える。 The hollow fiber membrane according to one aspect of the present invention is formed of one or more cords, and is laminated on a porous hollow support and the outer surface of the support, at least a portion of which is on the support. A porous bonding layer to be welded, and a porous filtration sheet laminated on the opposite side of the bonding layer to the support side and to which at least a part of the bonding layer is welded.
　当該中空糸膜は、支持体及び濾過シート間に接合層を備え、この接合層が支持体及び濾過シートに溶着してこれらを接合するので、支持体及び濾過シートを強く接合できるとともに、支持体及び濾過シートの材料を比較的自由に選択できる。また、当該中空糸膜の支持体は、１又は複数の紐体で編成されているので、高い引張強度と適度な柔軟性とを有する。このため、当該中空糸膜は、高い引張強度を有する支持体を基体とし、この支持体に接合層を介して濾過シートを接合するので、曲げ変形する際にも濾過シートが支持体から剥離し難く、濾過時又は逆洗時の耐圧性が高い。つまり、当該中空糸膜は、支持体及び濾過シートの材料として耐薬品性の高いものを選択可能であり、かつ構造的に機械的耐久性を向上させるものであるので、耐薬品性と機械的耐久性とを両立できる。 The hollow fiber membrane comprises a bonding layer between the support and the filtration sheet, and the bonding layer is welded to the support and the filtration sheet to bond them, so that the support and the filtration sheet can be strongly bonded, and the support And the material of the filter sheet can be selected relatively freely. In addition, since the support of the hollow fiber membrane is knitted with one or more cords, it has high tensile strength and appropriate flexibility. For this reason, the hollow fiber membrane uses a support having high tensile strength as a substrate, and the filtration sheet is bonded to the support via the bonding layer, so that the filtration sheet peels off from the support even when it is bent and deformed. It is difficult, and the pressure resistance at the time of filtration or backwashing is high. That is, since the hollow fiber membrane can be selected as one having high chemical resistance as the material of the support and the filter sheet, and structurally improves the mechanical durability, the chemical resistance and the mechanical can be improved. It is compatible with durability.
　上記支持体が筒状に形成されており、上記濾過シートが帯状に形成されており、上記濾過シートが、上記接合層を介し、上記支持体の外表面に対して螺旋状かつストライプ状に巻回されているとよい。これにより、支持体と濾過シートとが接合層を介して容易かつ確実に接合される。 The support is formed in a tubular shape, the filter sheet is formed in a band shape, and the filter sheet is wound in a spiral and in a stripe shape on the outer surface of the support via the bonding layer. Good to be turned. Thus, the support and the filter sheet are easily and reliably bonded via the bonding layer.
　上記紐体が８本以上３２本以下の樹脂細線で編成されているとよい。支持体を編成する紐体が、８本以上３２本以下の樹脂細線で編成されていることで、支持体の機械的強度が一層向上する。 It is good for the said string body to be knitted by 8 or more and 32 or less resin fine wire. The mechanical strength of the support is further improved by the cords that knit the support being knitted with 8 or more and 32 or less resin thin wires.
　上記接合層が不織布又は多孔性樹脂であるとよい。これにより、当該中空糸膜が曲げ変形する際に接合層が適度に変形して応力を分散させるので、濾過シートが支持体から一層剥離し難くなる。 The bonding layer may be a non-woven fabric or a porous resin. Thereby, when the said hollow fiber membrane bends and deform | transforms, since a joining layer deform | transforms moderately and disperses stress, it becomes difficult to peel a filtration sheet from a support body much more.
　上記濾過シートの主成分がポリテトラフルオロエチレンであるとよい。当該中空糸膜は、耐薬品性の高いポリテトラフルオロエチレンが外表面に配設される濾過シートに用いられることで、耐薬品性が向上する。ここで、主成分とは、最も含有量の多い成分を示し、例えば含有量が５０質量％以上の成分を示す。 Preferably, the main component of the filter sheet is polytetrafluoroethylene. The hollow fiber membrane is improved in chemical resistance by being used for a filtration sheet on which polytetrafluoroethylene having high chemical resistance is disposed on the outer surface. Here, the main component indicates a component with the highest content, for example, a component with a content of 50% by mass or more.
　上記濾過シートの平均厚さが１２μｍ以上１００μｍ以下であり、上記濾過シートの平均孔径が０．０１μｍ以上０．４５μｍ以下であり、当該中空糸膜のバブルポイントが８０ｋＰａ以上２００ｋＰａ以下であるとよい。これにより、当該中空糸膜の透水性能と不純物除去性能とがバランスよく調整される。ここで、平均孔径とは、１０以上の孔を顕微鏡観察し、孔の最大径とこの最大径に直交する方向の径との平均値をサンプル全体で平均した値を示す。また、バブルポイントとは、イソプロピルアルコールを用い、ＪＩＳ－Ｋ３８３２（１９９０）に準拠して測定される値を示す。 The average thickness of the filtration sheet may be 12 μm to 100 μm, the average pore diameter of the filtration sheet may be 0.01 μm to 0.45 μm, and the bubble point of the hollow fiber membrane may be 80 kPa to 200 kPa. Thereby, the water permeation performance and the impurity removal performance of the said hollow fiber membrane are adjusted with sufficient balance. Here, the average pore diameter refers to a value obtained by microscopically observing 10 or more holes and averaging the average value of the maximum diameter of the holes and the diameter in the direction orthogonal to the maximum diameter in the entire sample. The bubble point is a value measured according to JIS-K 3832 (1990) using isopropyl alcohol.
　本発明の他の一態様に係る中空糸膜の製造方法は、中空糸膜を製造する方法であって、多孔性の接合層及び多孔性の濾過シートを熱ラミネートする工程と、１又は複数の紐体で編成され、多孔性を有する中空の支持体における外表面と上記熱ラミネート工程後のシートの上記接合層側とを接触させ、上記支持体及び上記熱ラミネート工程後のシートを熱ラミネートする工程とを有する。 A method for producing a hollow fiber membrane according to another aspect of the present invention is a method for producing a hollow fiber membrane, comprising the steps of: thermally laminating a porous bonding layer and a porous filtration sheet; The outer surface of a hollow support which is knitted with a cord and has porosity is brought into contact with the bonding layer side of the sheet after the heat lamination step, and the support and the sheet after the heat lamination step are thermally laminated And a process.
　当該中空糸膜の製造方法は、接合層を濾過シートに対して溶着した後、このシートの接合層を支持体に対して溶着するので、接合層を介して支持体及び濾過シートを比較的容易に接合できる。つまり、当該中空糸膜の製造方法は、耐薬品性と機械的耐久性とを両立した中空糸膜を比較的容易に製造できる。 In the method of manufacturing the hollow fiber membrane, after the bonding layer is welded to the filtration sheet, the bonding layer of the sheet is welded to the support, so that the support and the filtration sheet are relatively easy to form via the bonding layer. Can be joined to That is, the method for producing a hollow fiber membrane can relatively easily produce a hollow fiber membrane having both chemical resistance and mechanical durability.
［本発明の実施形態の詳細］
　以下、適宜図面を参照しつつ、本発明の実施形態に係る中空糸膜及び中空糸膜の製造方法を説明する。 Details of the Embodiment of the Present Invention
Hereinafter, a hollow fiber membrane and a method of manufacturing the hollow fiber membrane according to an embodiment of the present invention will be described with reference to the drawings as appropriate.
［中空糸膜］
　図１及び図２の中空糸膜１は、１又は複数の紐体で編成され、多孔性を有する中空の支持体２と、支持体２の外表面に積層され、少なくとも一部が支持体２に溶着する多孔性の接合層３と、接合層３の支持体２側とは逆側に積層され、接合層３の少なくとも一部が溶着する多孔性の濾過シート４とを備える。 [Hollow fiber membrane]
The hollow fiber membrane 1 of FIG. 1 and FIG. 2 is knitted with one or more cords and is laminated on a porous hollow support 2 and the outer surface of the support 2, at least a part of which is the support 2. And a porous filtration sheet 4 laminated on the side opposite to the support 2 side of the bonding layer 3 and in which at least a part of the bonding layer 3 is welded.
　支持体２を編成する紐体は、８本以上３２本以下の樹脂細線で編成されており、支持体２は筒状に形成されている。接合層３は不織布又は多孔性樹脂である。濾過シート４は、帯状に形成されている。濾過シート４の主成分はポリテトラフルオロエチレンであり、濾過シート４の平均厚さは１２μｍ以上１００μｍ以下であり、濾過シート４の平均孔径は０．０１μｍ以上０．４５μｍ以下である。濾過シート４は、接合層３を介し、支持体２の外表面に対して螺旋状かつストライプ状に巻回されている。中空糸膜１のバブルポイントは８０ｋＰａ以上２００ｋＰａ以下である。 The cords for knitting the support 2 are knitted with 8 or more and 32 or less resin thin wires, and the support 2 is formed in a tubular shape. The bonding layer 3 is a non-woven fabric or a porous resin. The filtration sheet 4 is formed in a band shape. The main component of the filtration sheet 4 is polytetrafluoroethylene, the average thickness of the filtration sheet 4 is 12 μm to 100 μm, and the average pore diameter of the filtration sheet 4 is 0.01 μm to 0.45 μm. The filter sheet 4 is wound in a spiral and in a stripe shape on the outer surface of the support 2 via the bonding layer 3. The bubble point of the hollow fiber membrane 1 is 80 kPa or more and 200 kPa or less.
　中空糸膜１は、水処理に用いられる中空糸膜であり、図１に示すように、支持体２の外表面に接合層３及び濾過シート４がこの順で重畳するように積層している。中空糸膜１は、図２に示すように、濾過シート４側から接触する被処理水を濾過し、支持体２の内側の中空部５に濾過水を得るように筒状に構成されている。 The hollow fiber membrane 1 is a hollow fiber membrane used for water treatment, and as shown in FIG. 1, the bonding layer 3 and the filtration sheet 4 are laminated on the outer surface of the support 2 in this order. . As shown in FIG. 2, the hollow fiber membrane 1 is formed in a cylindrical shape so as to filter the water to be treated coming in contact with the filtration sheet 4 and obtain filtered water in the hollow portion 5 inside the support 2. .
　中空糸膜１のバブルポイントの下限としては、８０ｋＰａが好ましく、１００ｋＰａがより好ましく、１２０ｋＰａがさらに好ましい。一方、中空糸膜１のバブルポイントの上限としては、２００ｋＰａが好ましく、１８０ｋＰａがより好ましく、１６０ｋＰａがさらに好ましい。中空糸膜１のバブルポイントが上記下限に満たないと、被処理水が十分に濾過されないおそれがある。逆に、中空糸膜１のバブルポイントが上記上限を超えると、通水抵抗が増加し、濾過効率が低下するおそれがある。 The lower limit of the bubble point of the hollow fiber membrane 1 is preferably 80 kPa, more preferably 100 kPa, and still more preferably 120 kPa. On the other hand, as an upper limit of the bubble point of hollow fiber 1, 200 kPa is preferred, 180 kPa is more preferred, and 160 kPa is still more preferred. If the bubble point of the hollow fiber membrane 1 does not reach the above lower limit, the water to be treated may not be filtered sufficiently. Conversely, if the bubble point of the hollow fiber membrane 1 exceeds the above upper limit, the water flow resistance may increase, and the filtration efficiency may decrease.
＜支持体＞
　支持体２は、中空糸膜１の基体となる部材であり、筒状に形成されている。支持体２は、１又は複数の紐体で編成されており、濾過水が紐体の隙間を透過できる程度の多孔性を有している。また、支持体２の内側には中空部５が形成されている。 <Support>
The support 2 is a member to be a base of the hollow fiber membrane 1 and is formed in a tubular shape. The support 2 is knitted with one or more cords, and has a porosity that allows filtered water to permeate through the interstices of the cords. In addition, a hollow portion 5 is formed inside the support 2.
　支持体２の平均厚さ（平均肉厚）の下限としては、０．１ｍｍが好ましく、０．３ｍｍがより好ましく、０．５ｍｍがさらに好ましい。一方、支持体２の平均厚さの上限としては、２ｍｍが好ましく、１．７ｍｍがより好ましく、１．５ｍｍがさらに好ましい。支持体２の平均厚さが上記下限に満たないと、支持体２の機械的強度が不足するおそれがある。逆に、支持体２の平均厚さが上記上限を超えると、中空糸膜１が太くなり過ぎることで、複数の中空糸膜１が用いられる際に中空糸膜１の数密度が減少し、濾過効率が低下するおそれがある。 The lower limit of the average thickness (average thickness) of the support 2 is preferably 0.1 mm, more preferably 0.3 mm, and still more preferably 0.5 mm. On the other hand, the upper limit of the average thickness of the support 2 is preferably 2 mm, more preferably 1.7 mm, and still more preferably 1.5 mm. If the average thickness of the support 2 is less than the above lower limit, the mechanical strength of the support 2 may be insufficient. Conversely, when the average thickness of the support 2 exceeds the above upper limit, the hollow fiber membrane 1 becomes too thick, and the number density of the hollow fiber membranes 1 decreases when a plurality of hollow fiber membranes 1 are used, The filtration efficiency may be reduced.
（紐体）
　支持体２を編成する紐体は、機械的強度を向上させるために、複数本の樹脂細線で編成されている。樹脂細線の材料としては、特に限定されないが、例えばポリエチレンテレフタレート等のポリエステル、ポリエチレン又はポリプロピレンを主成分とした樹脂が用いられる。 (String body)
The cords for knitting the support 2 are knitted with a plurality of resin thin wires in order to improve the mechanical strength. The material of the resin fine wire is not particularly limited, but for example, polyester such as polyethylene terephthalate, or a resin containing polyethylene or polypropylene as a main component is used.
　紐体を編成する樹脂細線の本数の下限としては、８本が好ましく、１０本がより好ましく、１２本がさらに好ましい。一方、紐体を編成する樹脂細線の本数の上限としては、３２本が好ましく、２８本がより好ましく、２４本がさらに好ましい。紐体を編成する樹脂細線の本数が上記下限に満たないと、紐体の機械的強度が不足するおそれがある。逆に、紐体を編成する樹脂細線の本数が上記上限を超えると、紐体の製造コストが増加するおそれがある。 As a minimum of the number of resin thin lines which knit a string, eight are preferred, ten are more preferred, and 12 are still more preferred. On the other hand, as a maximum of the number of resin thin lines which knit a string, 32 are preferred, 28 are more preferred, and 24 is more preferred. If the number of resin thin wires for knitting the cords is less than the above lower limit, the mechanical strength of the cords may be insufficient. On the contrary, when the number of resin thin wires which knit a string exceeds the above-mentioned upper limit, there is a possibility that the manufacturing cost of a string may increase.
＜接合層＞
　接合層３は、支持体２と接触する面が支持体２に溶着し、濾過シート４と接触する面が濾過シート４に溶着することで、支持体２及び濾過シート４を接合する中間層であり、筒状の支持体２の外表面と濾過シート４の内側面との間に積層される。接合層３は、支持体２と接触する面から所定の厚み分だけ溶解し、この溶解した厚み領域で支持体２と接合され、濾過シート４と接触する面から所定の厚み分だけ溶解し、この溶解した厚み領域で濾過シート４と接合される。接合層３としては、樹脂粉末を熱処理して得られる多孔性樹脂又は不織布が用いられる。多孔性樹脂又は不織布の材料としては、特に限定されないが、例えばポリエチレンテレフタレート等のポリエステル、ポリエチレン又はポリプロピレンを主成分とした多孔性樹脂が用いられる。接合層３は、支持体２との接合における親和性を良好にする観点から、支持体２と同じ材料であると好ましい。 <Bonding layer>
The bonding layer 3 is an intermediate layer for bonding the support 2 and the filtration sheet 4 by welding the surface in contact with the support 2 to the support 2 and welding the surface in contact with the filtration sheet 4 to the filtration sheet 4. It is laminated between the outer surface of the cylindrical support 2 and the inner surface of the filtration sheet 4. The bonding layer 3 dissolves by a predetermined thickness from the surface in contact with the support 2, is bonded to the support 2 in this dissolved thickness region, and dissolves by a predetermined thickness from the surface in contact with the filtration sheet 4, It is joined to filtration sheet 4 in this dissolved thickness field. As the bonding layer 3, a porous resin or non-woven fabric obtained by heat-treating a resin powder is used. The material of the porous resin or the non-woven fabric is not particularly limited. For example, a porous resin containing polyester such as polyethylene terephthalate, polyethylene or polypropylene as a main component is used. The bonding layer 3 is preferably made of the same material as the support 2 from the viewpoint of improving the affinity for bonding with the support 2.
　接合層３の平均厚さの下限としては、１０μｍが好ましく、２０μｍがより好ましく、３０μｍがさらに好ましい。一方、接合層３の平均厚さの上限としては、２００μｍが好ましく、１５０μｍがより好ましく、１００μｍがさらに好ましい。接合層３の平均厚さが上記下限に満たないと、支持体２及び濾過シート４に対する溶着が不十分となり、接合層３の接合力が不足するおそれがある。逆に、接合層３の平均厚さが上記上限を超えると、中空糸膜１が太くなり過ぎることで、複数の中空糸膜１が用いられる際に中空糸膜１の数密度が減少し、濾過効率が低下するおそれがある。 The lower limit of the average thickness of the bonding layer 3 is preferably 10 μm, more preferably 20 μm, and still more preferably 30 μm. On the other hand, the upper limit of the average thickness of the bonding layer 3 is preferably 200 μm, more preferably 150 μm, and still more preferably 100 μm. If the average thickness of the bonding layer 3 is less than the above lower limit, welding to the support 2 and the filtration sheet 4 may be insufficient, and the bonding strength of the bonding layer 3 may be insufficient. Conversely, when the average thickness of the bonding layer 3 exceeds the above upper limit, the hollow fiber membrane 1 becomes too thick, and the number density of the hollow fiber membrane 1 decreases when a plurality of hollow fiber membranes 1 are used, The filtration efficiency may be reduced.
　接合層３は、中空糸膜１が製造される際に支持体２及び濾過シート４に溶着するため、融点が支持体２の融点以下かつ濾過シート４の融点以下であると好ましい。例えば濾過シート４としてポリテトラフルオロエチレン（融点約３２７℃）が用いられ、支持体２としてポリエチレンテレフタレート、ポリエチレン又はポリプロピレン（融点約１１０℃～２６０℃）が用いられる場合、接合層３として支持体２と同じ材料のもの又は支持体２の融点以下のものが用いられるとよい。 Since the bonding layer 3 is welded to the support 2 and the filtration sheet 4 when the hollow fiber membrane 1 is manufactured, the melting point is preferably equal to or lower than the melting point of the support 2 and lower than the melting point of the filtration sheet 4. For example, when polytetrafluoroethylene (melting point about 327 ° C.) is used as the filter sheet 4 and polyethylene terephthalate, polyethylene or polypropylene (melting point about 110 ° C. to 260 ° C.) is used as the support 2, the support 2 is used as the bonding layer 3. It is preferable to use the same material as that of the above or the melting point of the support 2 or less.
＜濾過シート＞
　濾過シート４は、接合層３の外表面に配設され、被処理水を濾過する機能を有する帯状の多孔性シートである。濾過シート４としては、耐薬品性を有する多孔性樹脂が用いられると好ましく、ポリテトラフルオロエチレンを主成分とした多孔性樹脂が用いられる。濾過シート４は、筒状の支持体２の外表面に対して螺旋状かつストライプ状に巻回されることにより、中空糸膜１の外表面を覆うように配設されている。また、濾過シート４は、側部が重畳するように支持体２の外表面に対して隙間なく巻回されている。つまり、中空糸膜１は、濾過シート４が螺旋状かつストライプ状に重畳した重畳部６を有している。なお、重畳部６では、支持体２、接合層３、濾過シート４、接合層３及び濾過シート４がこの順で接合されている。 <Filtration sheet>
The filtration sheet 4 is a strip-like porous sheet disposed on the outer surface of the bonding layer 3 and having a function of filtering the water to be treated. It is preferable that a porous resin having chemical resistance be used as the filtration sheet 4, and a porous resin containing polytetrafluoroethylene as a main component is used. The filtration sheet 4 is disposed so as to cover the outer surface of the hollow fiber membrane 1 by being wound around the outer surface of the cylindrical support 2 in a spiral shape and in a stripe shape. The filter sheet 4 is wound on the outer surface of the support 2 without gaps so that the side portions overlap. That is, the hollow fiber membrane 1 has the overlapping portion 6 in which the filtration sheet 4 is overlapped in a spiral shape and a stripe shape. In the overlapping portion 6, the support 2, the bonding layer 3, the filtration sheet 4, the bonding layer 3 and the filtration sheet 4 are bonded in this order.
　濾過シート４の平均厚さの下限としては、１２μｍが好ましく、１５μｍがより好ましく、１８μｍがさらに好ましい。一方、濾過シート４の平均厚さの上限としては、１００μｍが好ましく、８０μｍがより好ましく、６０μｍがさらに好ましい。濾過シート４の平均厚さが上記下限に満たないと、被処理水が十分に濾過されないおそれがある。逆に、濾過シート４の平均厚さが上記上限を超えると、通水抵抗が増加し、濾過効率が低下するおそれがある。 The lower limit of the average thickness of the filtration sheet 4 is preferably 12 μm, more preferably 15 μm, and still more preferably 18 μm. On the other hand, as an upper limit of average thickness of filtration sheet 4, 100 micrometers is preferred, 80 micrometers are more preferred, and 60 micrometers is still more preferred. If the average thickness of the filtration sheet 4 is less than the above lower limit, the water to be treated may not be filtered sufficiently. Conversely, if the average thickness of the filtration sheet 4 exceeds the above upper limit, the water flow resistance may increase, and the filtration efficiency may decrease.
　濾過シート４の平均孔径の下限としては、０．０１μｍが好ましく、０．０５μｍがより好ましく、０．１０μｍがさらに好ましい。一方、濾過シート４の平均孔径の上限としては、０．４５μｍが好ましく、０．４０μｍがより好ましく、０．３５μｍがさらに好ましい。濾過シート４の平均孔径が上記下限に満たないと、通水抵抗が増加し、濾過効率が低下するおそれがある。逆に、濾過シート４の平均孔径が上記上限を超えると、被処理水が十分に濾過されないおそれがある。 The lower limit of the average pore diameter of the filtration sheet 4 is preferably 0.01 μm, more preferably 0.05 μm, and still more preferably 0.10 μm. On the other hand, the upper limit of the average pore diameter of the filtration sheet 4 is preferably 0.45 μm, more preferably 0.40 μm, and still more preferably 0.35 μm. If the average pore diameter of the filtration sheet 4 is less than the above lower limit, the water flow resistance may be increased, and the filtration efficiency may be reduced. Conversely, if the average pore diameter of the filtration sheet 4 exceeds the above upper limit, the water to be treated may not be filtered sufficiently.
［中空糸膜の製造方法］
　当該中空糸膜の製造方法は、中空糸膜１を製造する方法であって、多孔性の接合層３及び多孔性の濾過シート４を熱ラミネートする第１ラミネート工程と、１又は複数の紐体で編成され、多孔性を有する中空の支持体２における外表面と第１ラミネート工程後のシートの接合層３側とを接触させ、支持体２及び第１ラミネート工程後のシートを熱ラミネートする第２ラミネート工程とを有する。 [Method for producing hollow fiber membrane]
The method for producing the hollow fiber membrane is a method for producing the hollow fiber membrane 1, and the first laminating step of thermally laminating the porous bonding layer 3 and the porous filtration sheet 4; and one or more cords Forming an outer surface of the hollow support 2 having porosity and contacting the bonding layer 3 side of the sheet after the first lamination step, and thermally laminating the support 2 and the sheet after the first lamination step And 2) laminating.
＜第１ラミネート工程＞
　第１ラミネート工程では、濾過シート４の一方の面に接合層３を平面視で重畳するように積層した状態で接合層３及び濾過シート４を熱ラミネートすることにより、濾過シート４に接合層３を溶着する。接合層３としては、濾過シート４より融点が低いものが用いられる。 <First laminating process>
In the first laminating step, the bonding layer 3 and the filtration sheet 4 are thermally laminated in a state where the bonding layer 3 is laminated so as to overlap in plan view on one surface of the filtration sheet 4. Weld As the bonding layer 3, one having a melting point lower than that of the filtration sheet 4 is used.
　熱ラミネートの方法としては、特に限定されない。例えば接合層３の一方の面側を所定の厚み分だけ溶解した後、この溶解面に濾過シート４を接触させた状態で冷却することで濾過シート４に接合層３を溶着する方法や、接合層３及び濾過シート４を積層した状態で、濾過シート４側から加熱して濾過シート４近傍の接合層３を所定の厚み分だけ溶解した後、冷却することで濾過シート４に接合層３を溶着する方法が用いられる。なお、接合層３は、接合層３の融点より１０℃から５０℃程度高い温度で所定の厚み分が溶解されるとよい。 The method of thermal lamination is not particularly limited. For example, a method of welding the bonding layer 3 to the filtration sheet 4 by melting one surface side of the bonding layer 3 by a predetermined thickness and then cooling in a state where the filtration sheet 4 is in contact with the melting surface In a state in which the layer 3 and the filtration sheet 4 are laminated, heating is performed from the filtration sheet 4 side to dissolve the bonding layer 3 in the vicinity of the filtration sheet 4 by a predetermined thickness, and then cooled. The method of welding is used. The bonding layer 3 preferably has a predetermined thickness dissolved at a temperature about 10 ° C. to 50 ° C. higher than the melting point of the bonding layer 3.
　第１ラミネート工程後の積層シートは、第２ラミネート工程の前に、例えば裁断等の方法を用いて帯状に加工される。なお、第１ラミネート工程後の積層シートの形状が帯状であればよいので、第１ラミネート工程後の積層シートを加工する方法に替えて、例えば帯状の濾過シート４を用いて第１ラミネート工程を実行することにより帯状の積層シートを得る方法が採用されてもよい。 The laminated sheet after the first laminating step is processed into a band shape using a method such as cutting before the second laminating step. In addition, since the shape of the lamination sheet after the 1st lamination process should just be strip shape, it changes to the method of processing the lamination sheet after the 1st lamination step, for example, uses the strip-shaped filtration sheet 4 for the 1st lamination process. A method may be employed to obtain a band-like laminated sheet by performing.
＜第２ラミネート工程＞
　第２ラミネート工程では、第１ラミネート工程後の積層シートの接合層３側と筒状の支持体２の外表面とを接触させた状態で、積層シートと支持体２とを熱ラミネートする。これにより、支持体２に接合層３が溶着する。支持体２としては、接合層３と同じ材料が用いられてもよいし、接合層３の融点以上の材料が用いられてもよい。 <Second laminating process>
In the second laminating step, the laminated sheet and the support 2 are thermally laminated in a state where the bonding layer 3 side of the laminated sheet after the first laminating step is in contact with the outer surface of the cylindrical support 2. Thereby, the bonding layer 3 is welded to the support 2. As the support 2, the same material as that of the bonding layer 3 may be used, or a material of the melting point or more of the bonding layer 3 may be used.
　帯状の積層シートと支持体２とが積層される際には、図２に示すように、筒状の支持体２の外表面に対して帯状の積層シートが螺旋状かつストライプ状に巻回されることにより、支持体２の外表面に接合層３及び濾過シート４がこの順で積層される。製造された中空糸膜１の外表面は濾過シート４で隙間なく覆われている必要があるので、帯状の積層シートは、側部が重畳するように支持体２に対して螺旋状かつストライプ状に巻回される。 When the strip-like laminated sheet and the support 2 are laminated, as shown in FIG. 2, the strip-like laminated sheet is wound in a spiral shape and a stripe form on the outer surface of the cylindrical support 2. As a result, the bonding layer 3 and the filtration sheet 4 are laminated in this order on the outer surface of the support 2. The outer surface of the manufactured hollow fiber membrane 1 needs to be covered with the filtration sheet 4 without a gap, so the strip-like laminated sheet has a spiral shape and a stripe shape with respect to the support 2 so that the side portions overlap. It is wound around.
　熱ラミネートの方法としては、特に限定されない。例えば帯状の積層シートの接合層３側を所定の厚み分だけ溶解した後、この溶解面に支持体２の外表面及び積層シートの側部上面を接触させつつ帯状の積層シートを支持体２に対して螺旋状かつストライプ状に巻回することで支持体２に接合層３を溶着する方法が用いられる。なお、接合層３は、接合層３の融点より１０℃から５０℃程度高い温度で所定の厚み分が溶解されるとよい。 The method of thermal lamination is not particularly limited. For example, after dissolving the bonding layer 3 side of the strip-shaped laminated sheet by a predetermined thickness, the strip-shaped laminated sheet is formed on the support 2 while bringing the outer surface of the support 2 and the upper surface of the laminated sheet into contact with the dissolution surface. On the other hand, a method of welding the bonding layer 3 to the support 2 by winding in a spiral shape and a stripe shape is used. The bonding layer 3 preferably has a predetermined thickness dissolved at a temperature about 10 ° C. to 50 ° C. higher than the melting point of the bonding layer 3.
（利点）
　当該中空糸膜１は、支持体２及び濾過シート４間に接合層３を備え、この接合層３が支持体２及び濾過シート４に溶着してこれらを接合するので、支持体２及び濾過シート４を強く接合する。当該中空糸膜１の支持体２は、８本以上３２本以下の樹脂細線で編成された紐体によって編成されているので高い引張強度と適度な柔軟性を有している。当該中空糸膜１の接合層３は、不織布又は多孔性樹脂であるので、当該中空糸膜１が曲げ変形する際に適度に変形して応力を分散させる。このため、当該中空糸膜１は、高い引張強度を有する支持体２を基体とし、この支持体２に接合層３を介して濾過シート４を接合するので、曲げ変形する際にも濾過シート４及び接合層３が支持体２から剥離し難く、濾過時又は逆洗時の耐圧性が高い。また、当該中空糸膜１の濾過シート４には、耐薬品性の高いポリテトラフルオロエチレンが用いられているので、当該中空糸膜１は、耐薬品性と機械的耐久性とを両立する。さらに、当該中空糸膜１は、バブルポイントが８０ｋＰａ以上２００ｋＰａ以下であるので、透水性能と不純物除去性能とがバランスよく調整される。 (advantage)
The hollow fiber membrane 1 includes the bonding layer 3 between the support 2 and the filtration sheet 4, and the bonding layer 3 is welded to the support 2 and the filtration sheet 4 to bond them, so the support 2 and the filtration sheet Bond 4 strongly. The support 2 of the hollow fiber membrane 1 has high tensile strength and appropriate flexibility because it is knitted by a cord body knitted with 8 or more and 32 or less resin fine wires. Since the bonding layer 3 of the hollow fiber membrane 1 is a non-woven fabric or a porous resin, when the hollow fiber membrane 1 is bent and deformed, it is appropriately deformed to disperse stress. For this reason, the hollow fiber membrane 1 uses the support 2 having high tensile strength as a base, and the filtration sheet 4 is joined to the support 2 via the bonding layer 3, so that the filtration sheet 4 is also deformed when bending. And the joining layer 3 is hard to peel from the support body 2, and the pressure resistance at the time of filtration or backwashing is high. Moreover, since the polytetrafluoroethylene with high chemical resistance is used for the filtration sheet 4 of the said hollow fiber membrane 1, the said hollow fiber membrane 1 makes chemical resistance and mechanical durability compatible. Furthermore, since the hollow fiber membrane 1 has a bubble point of 80 kPa or more and 200 kPa or less, water permeability and impurity removal performance are adjusted in a well-balanced manner.
　当該中空糸膜の製造方法は、接合層３を濾過シート４に対して溶着した後、このシートの接合層３を支持体２に対して溶着するので、接合層３を介して支持体２及び濾過シート４を比較的容易に接合できる。また、当該中空糸膜の製造方法は、筒状の支持体２の外表面に対して帯状の濾過シート４を側部が重畳するように螺旋状かつストライプ状に巻回するので、外表面が濾過シート４で隙間なく覆われた中空糸膜１を製造できるとともに、接合層３を介して支持体２及び濾過シート４を容易かつ確実に接合できる。 In the method of manufacturing the hollow fiber membrane, the welding layer 3 is welded to the filtration sheet 4 and then the welding layer 3 of this sheet is welded to the support 2. The filter sheet 4 can be joined relatively easily. Further, according to the method of manufacturing the hollow fiber membrane, since the strip-shaped filtration sheet 4 is spirally and stripe-shaped so that the side portions overlap with the outer surface of the cylindrical support 2, the outer surface is The hollow fiber membrane 1 covered with the filtration sheet 4 without any gap can be manufactured, and the support 2 and the filtration sheet 4 can be joined easily and reliably through the joining layer 3.
［他の実施形態］
　今回開示された実施の形態はすべての点で例示であって制限的なものではないと考えられるべきである。本発明の範囲は、上記実施形態の構成に限定されるものではなく、特許請求の範囲によって示され、特許請求の範囲と均等の意味及び範囲内での全ての変更が含まれることが意図される。 [Other embodiments]
It should be understood that the embodiments disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is not limited to the configurations of the above embodiments, but is indicated by the claims, and is intended to include all modifications within the meaning and scope equivalent to the claims. Ru.
　上記実施形態では、支持体２が筒状に形成されるものについて説明したが、支持体２は内側に中空部５が形成されていればよく、支持体２の形状は筒状に限定されない。 Although the said embodiment demonstrated the thing in which the support body 2 is formed in a cylinder shape, the hollow part 5 should just be formed inside the support body 2, and the shape of the support body 2 is not limited to a cylinder shape.
　上記実施形態では、帯状の濾過シート４が筒状の支持体２の外表面に対して螺旋状かつストライプ状に巻回されるものについて説明したが、濾過シート４が接合層３を介して支持体２の外表面に接合される積層構造であれば、他の手順で支持体２、接合層３及び濾過シート４が接合されてもよい。 In the above embodiment, the strip-shaped filtration sheet 4 is spirally wound around the outer surface of the cylindrical support 2 in the form of stripes, but the filtration sheet 4 is supported via the bonding layer 3 As long as it is a laminated structure bonded to the outer surface of the body 2, the support 2, the bonding layer 3 and the filtration sheet 4 may be bonded by another procedure.
　本発明の中空糸膜及び本発明の中空糸膜の製造方法で製造された中空糸膜は、耐薬品性と機械的耐久性とを両立できる。 The hollow fiber membrane of the present invention and the hollow fiber membrane produced by the method of producing a hollow fiber membrane of the present invention can achieve both chemical resistance and mechanical durability.
　１　中空糸膜
　２　支持体
　３　接合層
　４　濾過シート
　５　中空部
　６　重畳部 Reference Signs List 1 hollow fiber membrane 2 support 3 bonding layer 4 filtration sheet 5 hollow portion 6 overlapping portion

Claims (7)

  1. 　１又は複数の紐体で編成され、多孔性を有する中空の支持体と、
    　上記支持体の外表面に積層され、少なくとも一部が上記支持体に溶着する多孔性の接合層と、
    　上記接合層の上記支持体側とは逆側に積層され、上記接合層の少なくとも一部が溶着する多孔性の濾過シートと
    　を備える中空糸膜。     A hollow support having porosity and being organized in one or more strands;
    A porous bonding layer laminated on the outer surface of the support, at least a part of which is deposited on the support;
    A porous filtration sheet which is laminated on the side opposite to the support side of the bonding layer and to which at least a part of the bonding layer is welded.
  2. 　上記支持体が筒状に形成されており、
    　上記濾過シートが帯状に形成されており、
    　上記濾過シートが、上記接合層を介し、上記支持体の外表面に対して螺旋状かつストライプ状に巻回されている請求項１に記載の中空糸膜。     The support is formed in a tubular shape,
    The filter sheet is formed in a band shape,
    The hollow fiber membrane according to claim 1, wherein the filtration sheet is wound spirally and in a stripe form on the outer surface of the support via the bonding layer.
  3. 　上記紐体が８本以上３２本以下の樹脂細線で編成されている請求項１又は請求項２に記載の中空糸膜。 The hollow fiber membrane according to claim 1 or 2, wherein the cord body is knitted with 8 or more and 32 or less resin fine wires.
  4. 　上記接合層が不織布又は多孔性樹脂である請求項１、請求項２又は請求項３に記載の中空糸膜。 The hollow fiber membrane according to claim 1, 2 or 3, wherein the bonding layer is a non-woven fabric or a porous resin.
  5. 　上記濾過シートの主成分がポリテトラフルオロエチレンである請求項１から請求項４のいずれか１項に記載の中空糸膜。 The hollow fiber membrane according to any one of claims 1 to 4, wherein the main component of the filtration sheet is polytetrafluoroethylene.
  6. 　上記濾過シートの平均厚さが１２μｍ以上１００μｍ以下であり、
    　上記濾過シートの平均孔径が０．０１μｍ以上０．４５μｍ以下であり、
    　バブルポイントが８０ｋＰａ以上２００ｋＰａ以下である請求項１から請求項５のいずれか１項に記載の中空糸膜。     The average thickness of the filtration sheet is 12 μm to 100 μm,
    The average pore diameter of the filter sheet is 0.01 μm or more and 0.45 μm or less,
    The hollow fiber membrane according to any one of claims 1 to 5, which has a bubble point of 80 kPa or more and 200 kPa or less.
  7. 　中空糸膜を製造する方法であって、
    　多孔性の接合層及び多孔性の濾過シートを熱ラミネートする工程と、
    　１又は複数の紐体で編成され、多孔性を有する中空の支持体における外表面及び上記熱ラミネート工程後のシートの上記接合層側を接触させ、上記支持体及び上記熱ラミネート工程後のシートを熱ラミネートする工程と
    　を有する中空糸膜の製造方法。     A method of producing a hollow fiber membrane, comprising
    Heat laminating the porous bonding layer and the porous filter sheet;
    The outer surface of a hollow support having porosity and made up of one or a plurality of cords is brought into contact with the bonding layer side of the sheet after the heat lamination step, and the support and the sheet after the heat lamination step And a step of heat laminating.
PCT/JP2018/006770 2017-07-11 2018-02-23 Hollow fiber membrane and method for manufacturing hollow fiber membrane WO2019012727A1 (en)

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