JP2019018142A - Hollow fiber membrane module and method for producing the same - Google Patents

Abstract

To provide a hollow fiber membrane module having a plurality of hollow fiber membranes which are less likely to be broken when receiving bending and tension forces, and a method for producing the same.SOLUTION: A hollow fiber membrane module includes a plurality of hollow fiber membranes, and an adhesion-fixing part that fixes at least one end of the hollow fiber membranes with a sealing resin and a casing, where a coating layer that is brought into direct contact with the hollow fiber membranes is formed on a part of the outer periphery of at least one end of the hollow fiber membrane, the adhesion-fixing part is arranged so that the outermost end of the adhesion-fixing part positioned on an opposite side to the opening end of the hollow fiber membranes in a longitudinal direction of the hollow fiber membrane is not brought into direct contact with the hollow fiber membrane.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a hollow fiber membrane module and a method for producing the same, and more particularly to a hollow fiber membrane module including a plurality of hollow fiber membranes that are not easily broken even when subjected to bending or tensile force, and a method for producing the same.

  In recent years, hollow fiber membranes having various separation characteristics such as reverse osmosis type, ion exchange type, pervaporation type and ultrafiltration type have been developed. The hollow fiber membrane modules using these hollow fiber membranes have the advantage that the membrane surface area per unit volume of the device can be increased, so that the efficiency and size of the device can be reduced, and medical, physics, precision electronics industry, food Used in fields such as industry.

  A hollow fiber membrane is comprised by the support layer which exists in the outer side of the hollow part through which a to-be-processed fluid passes, and a hollow part. For example, in the dehumidifying module, water vapor in the fluid to be processed that passes through the hollow portion selectively permeates the support layer and flows out to the permeation side space through which the processing fluid flows.

  As a method of manufacturing a hollow fiber membrane module including a plurality of such hollow fiber membranes, a converging body formed of a plurality of hollow fiber membranes is stored in a cylindrical casing, and the stored portion is fixed with an adhesive. A method is known (Cited document 1).

Japanese Patent Laid-Open No. 06-063368

  Incidentally, air cylinders such as air chucks and rotary actuators are used for unmanned processes in a work process in which repeated operation is continuously performed by driving with air pressure (pneumatic pressure).

  In an apparatus driven by air pressure as described above, if water vapor is contained in the compressed air that is the driving source, malfunction or failure may occur, and therefore it is necessary to dehumidify the air before introduction. If the dehumidifier for dehumidifying the air is large and stationary, there will be restrictions on the device operating area, installation location, and production line design, so a small, movable or deformable device is required. Yes.

  However, in the conventional hollow fiber membrane module, there is often a problem that the dehumidifying function is lowered due to the breakage or breakage of the hollow fiber membrane because the air cylinder cannot sufficiently follow the movement of the air cylinder.

  The present inventors have observed a hollow fiber membrane that has been broken or broken, and these phenomena occur at the interface between the hollow fiber membrane that is adhesively fixed to the casing with an adhesive and the adhesively fixed portion. I found out. Furthermore, the present inventors have found that the adhesive having fluidity before solidifying crawls up the outer peripheral portion of the hollow fiber membrane by capillary action, and the scooped adhesive solidifies to form a thin film layer (hereinafter referred to as `` adhesive '' It was found that when the thin film layer is formed, the adhesive thin film layer is likely to be broken or broken.

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a hollow fiber membrane module including a plurality of hollow fiber membranes that are difficult to break even when subjected to bending or tensile force, and a method for manufacturing the same.

The present invention includes the following [1] to [10].
[1] A hollow fiber membrane module comprising a plurality of hollow fiber membranes, an adhesive fixing portion for fixing at least one end of the hollow fiber membrane with an adhesive, and a casing, wherein at least one of the hollow fiber membranes A coating layer that is in direct contact with the hollow fiber membrane is formed on a part of the outer periphery of the end, and the adhesive fixing portion is located on the opposite side of the open end of the hollow fiber membrane in the longitudinal direction of the hollow fiber membrane. A hollow fiber membrane module, wherein the end portion of the adhesive fixing portion is arranged so as not to directly contact the hollow fiber membrane.

  [2] The hollow fiber membrane module according to [1], wherein the entire surface of the coating layer is not covered with the adhesive fixing portion.

  [3] The hollow fiber membrane module according to [1] or [2], wherein the hollow fiber membrane has a region in direct contact with the adhesive fixing portion.

  [4] The hollow fiber membrane module according to [1] to [3], wherein the coating layer has a width of 5 to 20 mm in the longitudinal direction of the hollow fiber membrane.

  [5] The hollow fiber membrane module according to [1] to [4], wherein the coating layer is a fluoropolymer.

  [6] The hollow fiber membrane module according to [1] to [5], in which the fluid to be processed that passes through the hollow fiber membrane is caused to flow through a drive unit that continuously performs repeated operations.

  [7] A method for producing a hollow fiber membrane module according to [1] to [6], wherein a part of the outer periphery of at least one end of the hollow fiber membrane is treated with a coating agent to form a coating layer. A method for producing a hollow fiber membrane module, comprising: obtaining a hollow fiber membrane, housing an end of the hollow fiber membrane in a casing, and fixing the hollow fiber membrane with an adhesive to form an adhesive fixing portion.

  [8] The method according to [7], wherein the coating agent contains a fluoropolymer.

  [9] The method according to [7] or [8], wherein the coating agent is an aqueous solution.

  [10] The method according to [7] to [9], wherein the adhesive fixing part is formed so that the entire surface of the coating layer is not covered with the adhesive fixing part.

  ADVANTAGE OF THE INVENTION According to this invention, the hollow fiber membrane module provided with the hollow fiber membrane which is hard to fracture | rupture even when it receives the force of bending and a tension | pulling can be provided. Moreover, according to this invention, the hollow fiber membrane module provided with the hollow fiber membrane which is hard to fracture | rupture even when it receives the force of bending and a tension | pulling can be manufactured.

Partial schematic sectional drawing which shows an example of the hollow fiber membrane module of one embodiment of this invention (Example 1) Partial schematic sectional view showing tensile test (Examples 2 and 4) Partial schematic cross-sectional view of a hollow fiber membrane module of one embodiment of the present invention showing a location where the hollow fiber membrane is broken by a tensile test (Example 2) Partial schematic sectional view showing an example of a conventional hollow fiber membrane module (Example 3) Partial schematic cross-sectional view of a conventional hollow fiber membrane module showing a location where the hollow fiber membrane is broken by a tensile test (Example 4)

Hereinafter, the present invention will be described in detail with reference to the drawings as necessary.
1 to 5, similar elements and members are denoted by the same reference numerals.
In the present specification, a numerical range represented by “to” means a numerical range in which numerical values before and after “−” are a lower limit value and an upper limit value.

  The hollow fiber membrane module of the present invention is a hollow fiber membrane module comprising a plurality of hollow fiber membranes 7, an adhesive fixing portion 8 for fixing at least one end of the hollow fiber membrane 7 with an adhesive, and a casing 6. A coating layer 12 that is in direct contact with the hollow fiber membrane 7 is formed on a part of the outer periphery of at least one end of the hollow fiber membrane 7, and the adhesive fixing portion 8 is formed in the longitudinal direction of the hollow fiber membrane 7. In this embodiment, the outermost end portion 5 of the adhesive fixing portion located on the side opposite to the opening end portion 4 of the hollow fiber membrane is arranged so as not to directly contact the hollow fiber membrane 7.

FIG. 1 is a partial schematic cross-sectional view showing an example of the hollow fiber membrane module of the present invention.
As shown in FIG. 1, the hollow fiber membrane 7 has its ends fixed in the casing 6 with an adhesive, and both ends of the casing 6 are provided with fitting joints (not shown). If necessary, an elastic body such as an O-ring can be disposed as a sealing member at the intersection between the fitting joint and the adhesive fixing portion 8. In the hollow fiber membrane module, the end of the hollow fiber membrane 7 is opened to form an open end 4.

  The material of the hollow fiber membrane 7 may be a fluororesin. Examples of the fluororesin include polytetrafluoroethylene, polychlorotrifluoroethylene, polyvinylidene fluoride, tetrafluoroethylene (hereinafter referred to as TFE) -ethylene copolymer, TFE-perfluoroalkyl vinyl ether copolymer, Fluorine ion exchange resin is mentioned. When used as a dehumidifying module, the fluorine-containing ion exchange resin is preferable because of the good selectivity of water vapor.

  As the fluorine-containing ion exchange resin, a copolymer having a repeating unit based on TFE and a repeating unit having an ion exchange group is preferable, and since it easily permeates water vapor, it has a repeating unit based on TFE and a sulfonic acid group. A copolymer having a repeating unit based on perfluorovinyl ether is more preferable. The fluororesin constituting the hollow fiber membrane 7 is preferably non-porous because the selectivity of the permeating compound is high.

The outer diameter of the hollow fiber membrane 7 is preferably 0.2 to 5 mm, and more preferably 0.4 to 4.1 mm. If it is in the said range, the intensity | strength of the hollow fiber membrane 7 will be easy to be acquired, and it will become easy to become strong to a bending and a tension | pulling.
The inner diameter of the hollow fiber membrane 7 is preferably 0.1 to 3 mm, and more preferably 0.2 to 2.5 mm. If it is in the said range, a surface area will become large enough and it will be easy to obtain favorable processing efficiency.

  A plurality of hollow fiber membranes 7 may be converged to form a converging body. The number of hollow fiber membranes 7 to be converged can be appropriately selected depending on the processing efficiency and the size of the casing 6. The number of the hollow fiber membranes 7 in the bundle is preferably 3 to 500, more preferably 10 to 400, and still more preferably 20 to 250. If it is in the said range, a surface area will become large enough and it will be easy to process efficiently.

A coating layer 12 that is in direct contact with the hollow fiber membrane 7 is formed on a part of the outer periphery of at least one end of the hollow fiber membrane 7. The coating layer 12 is preferably a fluoropolymer because it is easy to prevent the adhesive having fluidity before solidifying from creeping up to the hollow fiber membrane 7. The coating layer 12 is formed by a coating agent.
The coating agent preferably contains a fluoropolymer, and more preferably contains a water-soluble fluoropolymer.

  The coating layer 12 can be formed by treating the coating agent at the end of the hollow fiber membrane 7 by a method such as dipping, coating, or spraying and drying. The coating agent is preferably an aqueous solution because the coating layer 12 can be formed without causing the treated portion of the hollow fiber membrane 7 to swell.

  Examples of the coating agent containing a fluoropolymer include SF coat SWK-601 and SF coat SW-26H (both trade names) manufactured by AGC Seimi Chemical Co., Ltd. You may use what diluted these with the solvent. The solvent to be diluted is preferably water, a water-soluble organic solvent, or a mixture of water and a water-soluble organic solvent. Examples of the water-soluble organic solvent include aliphatic alcohols having 1 to 8 carbon atoms such as methanol, ethanol, propyl alcohol, isopropyl alcohol, and isobutyl alcohol, acetone, acetonitrile, dimethyl sulfoxide, ethylene glycol, and ethylene glycol monomethyl ether. Can be mentioned.

  When a water-soluble organic solvent is included, the content of the water-soluble organic solvent in the coating agent is preferably less than 10% by mass, and more preferably less than 3% by mass. Since it is easy to suppress swelling of the hollow fiber membrane 7 in the treated portion, it is more preferable not to contain a water-soluble organic solvent. Since it is easy to suppress the swelling of the hollow fiber membrane 7 in the treated portion and to suppress a decrease in strength, it is preferable to use an aqueous solution of SF coated SW-26H.

  The coating layer 12 is formed on a part of the outer periphery of at least one end of the hollow fiber membrane 7. The coating layer 12 preferably has a width of 5 to 20 mm in the longitudinal direction of the hollow fiber membrane 7. The width of the coating layer 12 in the longitudinal direction of the hollow fiber membrane 7 is preferably smaller than the width of the adhesive fixing portion 8. The coating layer 12 is preferably formed between 10 and 50 mm in the longitudinal direction from the open end 4 of the hollow fiber membrane. Since the hollow fiber membrane 7 is easily fixed to the casing 6 with an adhesive, the coating layer 12 is preferably not formed on the outer periphery of the open end 4 of the hollow fiber membrane.

  Examples of the adhesive that forms the adhesive fixing portion 8 that fixes the end of the hollow fiber membrane 7 to the casing 6 include epoxy resins, vinyl ester resins, urethane resins, silicone resins, and olefin polymers. An epoxy resin is preferred because of good adhesion.

  The outermost end portion 5 of the adhesive fixing portion 8 located on the opposite side of the opening end portion 4 of the hollow fiber membrane in the longitudinal direction of the hollow fiber membrane 7 is formed so as not to directly contact the hollow fiber membrane 7. The adhesive fixing part 8 is preferably formed so as to have a region in direct contact with the hollow fiber membrane 7. The coating layer 12 is preferably formed on the outer peripheral portion of the hollow fiber membrane 7 and the entire surface thereof is not covered with the adhesive fixing portion 8. The hollow fiber membrane 7 preferably has a region in direct contact with the adhesive fixing portion 8.

  The adhesive fixing portion 8 and the coating layer 12 are regions in which the adhesive fixing portion 8 and the hollow fiber membrane 7 are in direct contact, the coating layer 12 is in direct contact with the hollow fiber membrane 7, and the adhesive fixing portion 8 It is formed in the outer peripheral part of the said hollow fiber membrane 7 so that it may have the area | region which contacts directly, and the said coating layer 12 may contact the said hollow fiber membrane 7 directly, and may not contact the said adhesion fixing part 8. Is preferred.

In the hollow fiber membrane module, it is preferable that at least one end of the hollow fiber membrane 7 is fixed to the casing 6 by the adhesive fixing portion 8.
In the casing 6, the fluid to be treated is supplied to the hollow fiber membrane 7 from the fluid supply direction 10 on the joint side. The casing 6 flows out of the permeation-side space 11 and the permeation-side space 11 through which the processing fluid and a fluid containing water vapor selectively permeated from the fluid to be processed that passes through the hollow portion of the hollow fiber membrane 7 pass. An outlet 9 is provided.
The shape of the casing 6 can be selected according to the application, but a cylindrical shape is preferable.

  The material of the casing 6 can be selected according to the type of fluid to be treated and the type of separation component, for example, synthetic resins such as polyurethane, polyamide, polyolefin, polyvinyl chloride, polycarbonate, acrylic resin, methacrylic resin, polysulfone, and polyethersulfone. It may be a metal such as stainless steel. Since the material of the casing 6 has good solvent resistance, polyurethane, polyamide, polyolefin, polysulfone, polyethersulfone, and stainless steel are more preferable.

The casing 6 is preferably a soft tube made of a thermoplastic resin such as polyurethane, polyamide, or polyolefin. As the soft tube, for example, in the case of a soft tube having an outer diameter of 8 mm and an inner diameter of 5 mm, a mandrel radius at a deformation rate of 25% according to JIS B 8381 is preferably 15 mm or less for polyurethane, 24 mm or less for polyamide, and 23 mm or less for polyolefin. . Polyurethane is preferred because strength against bending and tension can be obtained.
The casing 6 may be able to depressurize the permeation side space 11 through the outlet 9 as necessary, and may be disposed in a depressurizable chamber.

  As the fluid to be treated, gas or liquid can be used depending on the separation characteristics of the hollow fiber membrane 7. Examples of the gas include air, oxygen, and nitrogen. Examples of liquids include water; alcohols such as methanol, ethanol and isopropyl alcohol; ethers such as diethyl ether, dipropyl ether and butyl ether; esters such as methyl acetate, ethyl acetate, butyl acetate and ethyl propionate; ketones such as acetone and methyl ethyl ketone. Organic acids such as acetic acid, acetic anhydride and propionic acid; amines such as diethylamine and aniline; aliphatic hydrocarbons such as hexane and octane; aromatic hydrocarbons such as benzene and toluene; alicyclic hydrocarbons such as cyclohexane; chloroform , Halogenated hydrocarbons such as carbon tetrachloride and trichlorethylene, and liquids obtained by mixing these.

  When the coating layer 12 is not formed on the hollow fiber membrane 7, when an adhesive is used to form the adhesive fixing portion 8 on at least one end of the hollow fiber membrane 7, the fluidity before solidification is increased. The adhesive possessed rises up to the outer layer at the end of the hollow fiber membrane 7. As shown in FIG. 4, the adhesive scooped up on the outer layer at the end of the hollow fiber membrane 7 is solidified to form an adhesive thin film layer 14. The end portion of the hollow fiber membrane 7 on which the adhesive thin film layer 14 is formed loses flexibility, and is easily broken by a force such as bending or pulling. When the coating layer 12 is formed on the hollow fiber membrane 7, it is difficult for the adhesive having fluidity before solidification to scoop up the hollow fiber membrane 7, and the formation of the adhesive thin film layer 14 can be suppressed. The end portion of the film 7 is not lost in flexibility and is not easily broken by bending or pulling.

  The hollow fiber membrane module of the present invention provides a hollow fiber membrane 7 in which a coating layer 12 is formed by treating a part of the outer periphery of at least one end of the hollow fiber membrane 7 with a coating agent. It can be manufactured by a method in which the opening end 4 of the thread membrane is accommodated in the casing 6 and fixed with an adhesive to form the adhesive fixing portion 8.

  As shown in FIG. 1, the outermost end portion 5 of the adhesive fixing portion located on the opposite side of the open end portion 4 of the hollow fiber membrane in the longitudinal direction of the hollow fiber membrane 7 is disposed so as not to directly contact the hollow fiber membrane 7. It is preferable to be formed in such a manner. The hollow fiber membrane 7 preferably has a region in direct contact with the adhesive fixing portion 8. The coating layer 12 is preferably formed on the outer peripheral portion of the hollow fiber membrane 7 so that the entire surface thereof is not covered with the adhesive fixing portion 8.

  The adhesive fixing portion 8 and the coating layer 12 include an area where the adhesive fixing portion 8 is in direct contact with the hollow fiber membrane 7, and the coating layer 12 is in direct contact with the hollow fiber membrane 7 and the adhesive fixing portion 8 It may be formed on the outer peripheral portion of the hollow fiber membrane 7 so as to have a direct contact region and a region where the coating layer 12 is in direct contact with the hollow fiber membrane 7 and not in contact with the adhesive fixing portion 8. preferable.

As the coating agent, the same coating agent as described above can be used, and preferred embodiments are also the same.
Since the coating agent can form the coating layer 12 without swelling the hollow fiber membrane 7 in the treated portion, an aqueous solution is preferable, and an aqueous solution containing a fluoropolymer is more preferable. When the coating agent is an aqueous solution containing a fluoropolymer, the content of the fluoropolymer in the aqueous solution is preferably 1 to 20% by mass, and more preferably 4 to 12% by mass. If it is in the said range, it is easy to form the coating layer 12 uniformly.

  When the coating agent contains a water-insoluble organic solvent, the content of the organic solvent in the coating agent is preferably less than 3% by mass. More preferably, it does not contain an organic solvent. When the content of the organic solvent is within the above range, the hollow fiber membrane 7 is unlikely to swell, easily returns to its original shape when dried, and the strength of the hollow fiber membrane 7 is unlikely to decrease.

  At least one end portion of the hollow fiber membrane 7 is only required to have a part of the outer periphery treated with the coating agent, and the coating agent does not adversely affect the separation performance. It may penetrate.

  It is preferable to treat the coating agent so that the coating layer 12 is not formed on the open end 4 of the hollow fiber membrane. The coating layer 12 is formed with a width of 5 to 20 mm in the longitudinal direction of the hollow fiber membrane 7 between the opening end 4 of the hollow fiber membrane and 10 to 50 mm in the longitudinal direction of the hollow fiber membrane 7. It is preferable to treat the coating agent. Examples of the treatment method using the coating agent include various methods such as dipping, coating, and spraying. The treatment with the coating agent may be performed once or a plurality of times. The coating layer 12 is formed by treating the desired part of the hollow fiber membrane 7 with the coating agent and then drying it. Drying may be performed at room temperature or heated in an oven or the like. Moreover, you may dry on pressure reduction conditions.

  As a method for fixing the hollow fiber membrane 7 provided with the coating layer 12 to the casing 6, known sealing such as means for sealing the end opening of the hollow fiber membrane 7 by applying a silicone resin as necessary After sealing by means, the hollow fiber membrane 7 is housed in the casing 6, and then the entire surface of the coating layer 12 formed on a part of the outer periphery of the end of the hollow fiber membrane 7 is covered with the adhesive fixing portion 8. There may be mentioned a method of injecting such an amount of adhesive into the casing 6 to form the adhesive fixing portion 8. Before the hollow fiber membrane 7 is accommodated in the casing 6, the adhesive fixing portion 8 may be formed in advance with an adhesive and then accommodated in the casing 6. The adhesive fixing portion 8 may be formed while supplying gas from one opening end portion 4 of the hollow fiber membrane 7 without sealing the end opening portion of the hollow fiber membrane 7.

As the adhesive, the same ones as described above can be used, and the preferred embodiments are also the same. The adhesive can be injected by a conventionally known method such as a centrifugal injection method.
By performing the same operation as described above for both ends of the hollow fiber membrane 7, a hollow fiber membrane module having the adhesive fixing portion 8 at both ends can be obtained.
When a gap is generated between the inner wall of the casing 6 and the adhesive fixing portion 8, the gap may be sealed with the adhesive, or may be sealed with a sealing member such as an elastic O-ring. Also good.

Before the hollow fiber membrane 7 is fixed to the casing 6, in the end opening of the hollow fiber membrane 7 that is not sealed, a part of the end opening may be blocked by an adhesive. The end opening thus closed and the sealed end opening do not flow into the hollow portion of the hollow fiber membrane 7 and cannot function as a hollow fiber membrane module. After forming the adhesive fixing portion 8, the end opening portion closed together with the adhesive fixing portion 8 or the sealed end opening portion is cut, whereby a hollow fiber membrane module in which the end of the hollow fiber membrane 7 is opened is obtained. Can be obtained.
In the method for producing a hollow fiber membrane module of the present invention, the hollow fiber membrane 7 and the casing 6 can be the same as described above, and the preferred embodiments are also the same.

  The hollow fiber membrane module of the present invention can be used for, for example, membrane separation of liquid, membrane separation of gas, membrane separation of gas component from liquid, such as medical, precision electronics industry, food industry, physics and chemicals as humidification module and dehumidification module Available in the field. In particular, it is suitable as a dehumidifying module used in a drive unit that continuously performs repeated operations in an air cylinder such as an air chuck or a rotary actuator.

  Examples of application of the present invention are shown below, but the present invention is not limited thereto. Examples 1 and 2 are examples, and examples 3 and 4 are comparative examples.

(Example 1)
Example 1 is an example in which the hollow fiber membrane module shown in FIG. 1 was manufactured.
As the hollow fiber membrane 7, a hollow fiber membrane made of a fluororesin (outer diameter 0.58 mm, inner diameter 0.36 mm, length 280 mm) was used. As the adhesive, an epoxy resin (trade name: jER-828, jER Cure-ST12, manufactured by Mitsubishi Chemical Corporation) was used. As a coating agent, a 10 mass% aqueous solution (hereinafter referred to as “coating agent aqueous solution A”) manufactured by AGC Seimi Chemical Co., Ltd., trade name: SF coat SW-26H was used.

  40 of the hollow fiber membranes 7 were converged to obtain a convergent body. The end of the convergent body is sealed with a silicone resin, and an aqueous coating agent solution A is applied so that the width of the hollow fiber membrane 7 is about 10 mm in the longitudinal direction around the position 30 mm from the end. The coating layer 12 was formed by drying for a period of time.

  The converging body is accommodated in a urethane soft tube (casing 6), and the end portion 5 of the adhesive fixing portion located on the opposite side of the opening end 4 is disposed at a position 30 mm from the end of the converging body. An amount of adhesive was injected. The converging body was housed in a jig for a centrifuge, and the hollow fiber membrane module into which the adhesive was injected was fixed and centrifuged at 60 ° C. and 900 rpm for 90 minutes. By the centrifugal separation, the adhesive reached the inside of the casing 6, the bubbles in the adhesive were removed, and the interface between the adhesive and air became smooth. It was made to dry at 65 degreeC for 10 hours, and the adhesive fixing | fixed part 8 was formed. Subsequently, it cut | disconnected in 10 mm from the terminal of the soft tube with which the said convergence body was fixed by the adhesive fixing | fixed part 8, and the hollow fiber membrane module shown in FIG. 1 was obtained.

  After the hollow fiber membrane 7 portion of the obtained hollow fiber membrane module is bent along the semicircular outer peripheral curved surface of a semicylindrical jig having a radius of 24 mm, the semicylindrical shape is maintained while maintaining the bent state. The hollow fiber membrane module was rotated once in the direction perpendicular to the longitudinal direction of the hollow fiber membrane 7 (hereinafter referred to as “bending test”). A pressure resistance test was performed by supplying 0.98 MPa of air from the supply port 10 of the hollow fiber membrane module subjected to the bending test. When the same pressure resistance test was performed on 300 of the hollow fiber membrane modules prepared as described above, no breakage of the hollow fiber membrane 7 was confirmed in all the hollow fiber membrane modules.

(Example 2)
After producing the hollow fiber membrane module of Example 1, the joint (not shown) and the casing 6 were removed. As shown in FIG. 1, a coating layer 12 was formed between the adhesive fixing portion 8 and the hollow fiber membrane 7.

  As shown in FIG. 2, one hollow fiber membrane 7 is formed at an angle formed by the hollow fiber membrane 7 and the outermost end portion 5 of the adhesive fixing portion located on the opposite side of the open end portion 4 of the hollow fiber membrane (a in FIG. ) Was 45 °, and the force applied at that time was measured with a spring balance 13 (hereinafter referred to as “tensile test”). In addition, the dotted line b in FIG. 2 is a dotted line which extrapolated the surface in the outermost part 5 of the said adhesion fixing part horizontally. As shown in FIG. 3, the hollow fiber membrane 7 was broken at a portion of the hollow fiber membrane 7 where the coating layer 12 was not formed. The force applied when the hollow fiber membrane 7 broke was 5.9N.

(Example 3)
The hollow fiber membrane module of FIG. 4 was obtained in the same manner as in Example 1 except that the coating agent aqueous solution A was not applied. Since the hollow fiber membrane 7 of Example 3 does not include the coating layer 12, the fluid adhesive before solidifying rises to the hollow fiber membrane 7 by capillary action, and the adhesive thin film layer 14 is formed. It was.

  Similarly to Example 1, after performing a bending test, 0.98 MPa of air was supplied from the supply port 10 to perform a pressure resistance test. When a pressure resistance test was performed on 300 of the hollow fiber membrane modules produced as described above, breakage of the hollow fiber membrane 7 was confirmed in 250 hollow fiber membrane modules.

(Example 4)
A tensile test was conducted in the same manner as in Example 2 except that the hollow fiber membrane module obtained in Example 3 was used. The hollow fiber membrane 7 was broken at the interface portion between the hollow fiber membrane 7 and the adhesive fixing part 8 as shown in FIG. The force applied when the hollow fiber membrane 7 was broken was 0.98 N.

DESCRIPTION OF SYMBOLS 4 ... Open end part of hollow fiber membrane 5 ... Endmost part of adhesion | attachment fixing | fixed part 6 ... Casing 7 ... Hollow fiber membrane 8 ... Adhesion fixing | fixed part 9 ... Outlet 10 ... Fluid to be processed supply direction 11 ... Permeation side space 12 ... Coating Layer 13 ... Spring balance 14 ... Adhesive thin film layer

Claims (10)

A hollow fiber membrane module comprising a plurality of hollow fiber membranes, an adhesive fixing portion for fixing at least one end of the hollow fiber membrane with an adhesive, and a casing,
A coating layer in direct contact with the hollow fiber membrane is formed on a part of the outer periphery of at least one end of the hollow fiber membrane,
The adhesive fixing portion is arranged so that the outermost end portion of the adhesive fixing portion located on the opposite side of the opening end portion of the hollow fiber membrane in the longitudinal direction of the hollow fiber membrane does not directly contact the hollow fiber membrane. A hollow fiber membrane module.   The hollow fiber membrane module according to claim 1, wherein the entire surface of the coating layer is not covered with the adhesive fixing portion.   The hollow fiber membrane module according to claim 1 or 2, wherein the hollow fiber membrane has a region in direct contact with the adhesive fixing portion.   The said coating layer is a hollow fiber membrane module as described in any one of Claims 1-3 which has a width | variety of 5-20 mm in the longitudinal direction of a hollow fiber membrane.   The hollow fiber membrane module according to any one of claims 1 to 4, wherein the coating layer is a fluoropolymer.   The hollow fiber membrane module according to any one of claims 1 to 5, wherein the fluid to be processed that passes through the hollow fiber membrane is caused to flow to a drive unit that continuously performs repeated operations. It is a manufacturing method of the hollow fiber membrane module according to any one of claims 1 to 6,
A part of the outer periphery of at least one end of the hollow fiber membrane is treated with a coating agent to obtain a hollow fiber membrane having a coating layer formed thereon,
Storing the end of the hollow fiber membrane in a casing;
A method for producing a hollow fiber membrane module, wherein an adhesive fixing part is formed by fixing with an adhesive.   The manufacturing method according to claim 7, wherein the coating agent contains a fluoropolymer.   The manufacturing method according to claim 7 or 8, wherein the coating agent is an aqueous solution.   The manufacturing method as described in any one of Claims 7-9 which forms an adhesion fixing part so that the whole surface of the said coating layer may not be covered with an adhesion fixing part.

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