JP2018030049A - Hollow fiber membrane module and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hollow fiber membrane module in which peeling between a case and a fixing portion is suppressed and a method for manufacturing the same. SOLUTION: A hollow fiber membrane bundle 10, a case 20 accommodating the hollow fiber membrane bundle 10, and a first fixing portion 32 and a second fixing portion 34 for fixing the hollow fiber membrane bundle 10 to the case 20 are provided. The hollow fiber membrane, in which the case 20 has a first primer layer 24 and a second primer layer 26 provided on the inner wall surface of the case body 22 so as to be interposed between the case body 22 and the fixing portion. A method of manufacturing the module 1, which is a step (a): a step of applying a primer containing an acid-modified polyolefin to the inner wall surface of the case body 22 to form a primer layer having a thickness of 2 μm or more and 13 μm or less, (B): a step of housing the hollow fiber membrane bundle 10 in the case 20, and a step (c): a step of injecting a potting material and curing it to form a fixed portion. [Selection diagram] Figure 1

Description

  The present invention relates to a hollow fiber membrane module and a method for producing the same.

  Membrane modules such as hollow fiber membrane modules and flat membrane modules are used in the medical field, food field, water treatment field, etc., in addition to filtering liquids, removing dissolved gases from liquids (degassing) or removing gas into liquids. Also used for supply (air supply). As the membrane module, a hollow fiber membrane module is often used because of its large membrane area per volume.

  The hollow fiber membrane module usually includes a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes, a case in which the hollow fiber membrane bundle is stored, and a fixing portion that fixes the hollow fiber membrane bundle to the case. The hollow fiber membrane module includes, for example, a step of storing a hollow fiber membrane bundle in a case; a potting material is injected between the hollow fiber membranes and between the hollow fiber membrane bundle and the case and cured to form a fixing portion. And a step of cutting the fixing portion together with the end of the hollow fiber membrane and opening the end of the hollow fiber membrane.

  When the adhesion between the case and the fixing part is insufficient in the hollow fiber membrane module, peeling may occur between the case and the fixing part when the fixing part is cut or after the hollow fiber membrane module is delivered. Depending on the combination of the case material and the potting material, the adhesive strength between the case and the fixed part will differ, but if the case material is difficult to adhere, the case and the fixed part will easily peel off. .

  As a method of increasing the adhesive force between the case and the fixing portion, a method of applying a primer in advance to the inner wall surface of the case is known (for example, Patent Documents 1 and 2).

JP 2000-342934 A JP 2001-276583 A

  However, there are many types of primers, and when a primer that does not match the combination of the case material and the potting material is selected, the effect of increasing the adhesive force between the case and the fixing portion cannot be obtained. Moreover, even if the primer layer is too thin or too thick, the effect of increasing the adhesive force between the case and the fixed portion cannot be exhibited.

  Therefore, in order to increase the adhesive force between the case and the fixing portion, it is necessary to select a primer suitable for the combination of the case material and the potting material and to control the thickness of the primer layer.

  The present invention provides a hollow fiber membrane module in which peeling between a case and a fixing portion is suppressed, and a method for manufacturing the same.

The present invention has the following aspects.
<1> A hollow fiber membrane bundle comprising a plurality of hollow fiber membranes, a case in which at least a part of the hollow fiber membrane bundle is accommodated, and a fixing portion for fixing the hollow fiber membrane bundle to the case, A method for producing a hollow fiber membrane module, wherein the case has a case body and a primer layer provided on an inner wall surface of the case body so as to be interposed between the case body and the fixing portion, The manufacturing method of a hollow fiber membrane module which has the following process (a)-(c).
Step (a): A step of applying the primer containing acid-modified polyolefin to the inner wall surface of the case body to form a primer layer having a thickness of 2 μm to 13 μm to obtain the case.
Step (b): A step of storing at least a part of the hollow fiber membrane bundle in the case.
Step (c): A step of injecting a potting material between the hollow fiber membranes and between the hollow fiber membrane bundle and the primer layer of the case, and curing the potting material to form the fixing portion.
<2> The method for producing a hollow fiber membrane module according to <1>, wherein the primer has a concentration of the acid-modified polyolefin of 2.5 to 17% by mass out of 100% by mass of the primer.
<3> The method for producing a hollow fiber membrane module according to <1> or <2>, wherein the case body is made of polypropylene.
<4> The method for producing a hollow fiber membrane module according to any one of <1> to <3>, wherein a primer having a tensile shear adhesive strength measured by the following procedure of 2.0 MPa or more is used as the primer.
Procedure for measuring tensile shear bond strength:
-Prepare two test pieces (length: 100 mm x width: 20 mm x thickness: 2 mm) made of the same material as the case body.
-Adhesive part (length: 12.5 mm x width: 20 mm) at one end of each of the two test pieces is polished with # 240 abrasive paper and wiped with ethanol.
Apply the primer to each bonded part of the two test pieces and dry for 1 hour.
-After the centrifugal defoaming treatment of the potting material, the potting material is applied to the bonded portion of one test piece.
-The adhesive part of one test piece and the adhesive part of the other test piece face each other via a potting material, and the part other than the adhesive part of one test piece and the part other than the adhesive part of the other test piece face each other Two test pieces are stacked so that they do not.
-The potting material protruding from the two test pieces is wiped off, and the two test pieces are sandwiched between clips at the bonded portion and heated at 60 ° C for 6 hours to cure the potting material.
-In accordance with JIS K 6850: 1999, the end of each of the two test pieces opposite to the adhesion part is fixed with a chuck of a tensile tester so that the distance between the chucks is 115 mm, and the adhesion part The chuck of the tensile tester is moved at a pulling speed of 2 mm / min until peeling occurs.
・ Divide the maximum load when peeling occurs in the bonded area by the area of the bonded area to obtain the tensile shear bond strength.
<5> A hollow fiber membrane bundle comprising a plurality of hollow fiber membranes, a case in which at least a part of the hollow fiber membrane bundle is accommodated, and a fixing portion for fixing the hollow fiber membrane bundle to the case, The case has a case main body, and a primer layer provided on the inner wall surface of the case main body so as to be interposed between the case main body and the fixing portion, and the primer layer contains an acid-modified polyolefin, The hollow fiber membrane module whose thickness of the said primer layer is 2 micrometers or more and 13 micrometers or less.
<6> The hollow fiber membrane module according to <5>, wherein the material of the case body is polypropylene.

According to the method for manufacturing a hollow fiber membrane module of the present invention, it is possible to manufacture a hollow fiber membrane module in which peeling between the case and the fixed portion is suppressed.
In the hollow fiber membrane module of the present invention, peeling between the case and the fixed portion is suppressed.

It is sectional drawing which shows an example of the hollow fiber membrane module of this invention. It is a perspective view which shows the other example of the hollow fiber membrane module of this invention. It is sectional drawing which shows an example of the process (a) in the manufacturing method of the hollow fiber membrane module of this invention. It is sectional drawing which shows an example of the process (b) in the manufacturing method of the hollow fiber membrane module of this invention. It is sectional drawing which shows an example of the process (c) in the manufacturing method of the hollow fiber membrane module of this invention. It is sectional drawing which shows an example of the process (d) in the manufacturing method of the hollow fiber membrane module of this invention.

  The dimensional ratios in FIGS. 1 to 6 include those different from actual ones for convenience of explanation. Moreover, in FIGS. 2-6, the same code | symbol is attached | subjected to the same component as FIG. 1, and the description is abbreviate | omitted.

<Hollow fiber membrane module>
FIG. 1 is a cross-sectional view showing an example of the hollow fiber membrane module of the present invention.
The hollow fiber membrane module 1 includes a hollow fiber membrane bundle 10, a case 20 in which the hollow fiber membrane bundle 10 is accommodated, and a first end portion of the hollow fiber membrane bundle 10 in the length direction of the hollow fiber membrane 12. The first fixing portion 32 that is fixed to the first end portion side of the hollow fiber membrane bundle 10 and the second end portion in the length direction of the hollow fiber membrane 12 of the hollow fiber membrane bundle 10 are fixed to the second end portion side of the case 20. And a second fixing portion 34.

(Hollow fiber membrane bundle)
The hollow fiber membrane bundle 10 is obtained by converging a plurality of hollow fiber membranes 12 whose length directions are aligned in a cylindrical shape.

  Examples of the material of the hollow fiber membrane 12 include polyolefin (polyethylene, polypropylene, poly (4-methylpentene-1), etc.), fluorine-based resin (polytetrafluoroethylene, polyvinylidene fluoride, ethylenetetrafluoroethylene copolymer, etc.), Examples thereof include polystyrene resins, polysulfone, polyarylsulfone, polyethersulfone, polyetherketone, polyetheretherketone, polycarbonate, cellulose derivative, polyamide, polyester, polymethacrylate, and polyacrylate. The hollow fiber membrane may be a porous membrane or a non-porous membrane. When the hollow fiber membrane module 1 is used for deaeration or air supply, the hollow fiber membrane 12 is preferably a composite hollow fiber membrane having a homogeneous layer and a porous layer, and the homogeneous layer is sandwiched between the porous layers from both sides. A three-layered composite hollow fiber membrane is more preferred.

(Case)
The case 20 includes a cylindrical case main body 22 having an open first end and a second end; a case main body 22 and a first fixing portion 32 on an inner wall surface in the vicinity of the first end of the case main body 22. A first primer layer 24 provided so as to be interposed between the case body 22 and the inner wall surface in the vicinity of the second end of the case body 22 between the case body 22 and the second fixing portion 34. And a second primer layer 26 provided on the substrate.

The case main body 22 is formed with a first fluid inlet / outlet port 22 a and a second fluid inlet / outlet port 22 b that protrude outward from the outer wall surface and communicate with the inside of the case main body 22.
The material of the case body 22 is preferably a resin from the viewpoint of processability and cost, and from the viewpoint of mechanical strength and durability, polyolefin, polycarbonate, polysulfone, polyvinyl chloride, acrylic resin, ABS resin, modified polyphenylene ether. Is more preferable, and from the viewpoint of heat resistance and solvent resistance, polyolefin is more preferable, and polypropylene is particularly preferable.

  The first primer layer 24 and the second primer layer 26 (hereinafter collectively referred to as “primer layer”) are layers formed by applying a primer described later to the inner wall surface of the case body 22. . Therefore, the primer layer contains an acid-modified polyolefin described later.

  The acid-modified polyolefin is excellent in the effect of improving the adhesiveness of various materials, and in particular, is excellent in the effect of improving the adhesiveness of polyolefin (especially polypropylene) which is the same olefin type. The case main body 22 and the first fixing portion 32 and the second fixing portion 34 (hereinafter, collectively referred to as “fixing portion”) made of a potting material have low adhesive strength as they are, and in particular, the case main body. When the material of 22 is polypropylene, peeling occurs immediately. When the primer layer contains the acid-modified polyolefin, the case body 22 and the fixing portion are sufficiently bonded.

  The thickness of the primer layer is 2 μm or more and 13 μm or less, preferably 3 μm or more and 10 μm or less, from the viewpoint of the adhesive force between the case body 22 and the fixing portion. Even if the primer layer is too thin or too thick, the effect of increasing the adhesive force between the case main body 22 and the fixing portion cannot be exhibited. That is, the primer layer merely improves the adhesion between the case main body 22 and the fixing portion, and the case main body 22 and the primer layer and the fixing portion and the primer layer are not connected. Therefore, if the primer layer is too thick, a distance is generated between the case main body 22 and the fixed portion, and the adhesive force is reduced. On the other hand, if the primer layer is too thin, the effect as the primer layer cannot be exhibited, and the adhesive strength is not improved.

(Fixed part)
The first fixing portion 32 is a case on the first end side of the case 20 with the first end of the hollow fiber membrane bundle 10 kept open at the first opening end of the hollow fiber membrane 12. The space inside the case 20 and the space outside the case 20 are liquid-tightly partitioned.
The second fixing portion 34 is a case on the second end side of the case 20 with the second end of the hollow fiber membrane bundle 10 kept open at the second opening end of the hollow fiber membrane 12. The space inside the case 20 and the space outside the case 20 are liquid-tightly partitioned.

  The fixing part is made of a cured product of a potting material described later, and the potting material is injected between the hollow fiber membranes 12 and between the hollow fiber membrane bundle 10 and the primer layer of the case 20 and cured. It is a member to be formed.

(Mechanism of action)
In the hollow fiber membrane module 1 described above, the primer layer provided so as to be interposed between the case main body 22 and the fixing portion contains acid-modified polyolefin and has a thickness of 2 μm or more and 13 μm or less. For this reason, the adhesive force between the case main body 22 and the fixed portion is high. Therefore, in the hollow fiber membrane module 1, peeling between the case 20 and the fixed portion is suppressed.

(Other embodiments)
The hollow fiber membrane module of the present invention includes a hollow fiber membrane bundle composed of a plurality of hollow fiber membranes, a case in which at least a part of the hollow fiber membrane bundle is accommodated, and a fixing portion that fixes the hollow fiber membrane bundle to the case. And the case has a case body, and a primer layer provided on the inner wall surface of the case body so as to be interposed between the case body and the fixing portion, the primer layer containing an acid-modified polyolefin, and a primer layer The thickness is not limited to the hollow fiber membrane module 1 of FIG. 1 as long as it is 2 μm or more and 13 μm or less.

For example, the shape of the case is not limited to a cylindrical shape, and various shapes can be selected according to the use of the hollow fiber membrane module.
The fixing portion may be accommodated in the case, or a part thereof may protrude from the case.
Further, the hollow fiber membrane module of the present invention is not limited to one in which both ends of the hollow fiber membrane bundle are fixed to the first fixing portion and the second fixing portion. Only the end part of this may be fixed to the fixing part.

The hollow fiber membrane module of the present invention is not limited to the cylindrical hollow fiber membrane module, and may be a flat hollow fiber membrane module 2 as shown in FIG.
The hollow fiber membrane module 2 includes a sheet-like hollow fiber membrane bundle 11 in which a plurality of hollow fiber membranes 12 are aligned in one direction and both ends in the lengthwise direction of the hollow fiber membrane 12 are bound by binding yarns 14. A first housing 40 (case) in which a first end in the length direction of the hollow fiber membrane 12 of the hollow fiber membrane bundle 11 is inserted; and a length direction of the hollow fiber membrane 12 of the hollow fiber membrane bundle 11 A second housing 50 (case) in which the second end portion of the hollow fiber membrane bundle 11 is inserted into the first housing 40 from an opening formed in the side wall of the first housing 40. A first fixing portion 62 for fixing the first end portion liquid-tightly to the first housing 40 in a state where the opening of the first opening end portion of the hollow fiber membrane 12 is maintained; A second bundle of hollow fiber membrane bundles 11 inserted into the second housing 50 from the opening formed in the side wall. Part of, and a second fixing portion for fixing to the second open end the second housing 50 while maintaining the opening of the hollow fiber membrane 12 in a fluid-tight manner (not shown).

The first housing 40 (case) includes a cylindrical housing body 42 in which an opening for inserting the first end of the hollow fiber membrane bundle 11 is formed on the side wall; A primer layer 44 is provided on the wall surface so as to be interposed between the housing main body 42 and the first fixing portion 62.
The second housing 50 (case) includes a cylindrical housing body 52 in which an opening for inserting the second end of the hollow fiber membrane bundle 11 is formed on the side wall; The wall surface has a primer layer (not shown) provided so as to be interposed between the housing main body 52 and a second fixing portion (not shown).

<Method for producing hollow fiber membrane module>
The manufacturing method of the hollow fiber membrane module of this invention has the following process (a)-(d).
Step (a): A step of applying a primer containing acid-modified polyolefin to the inner wall surface of the case body to form a primer layer having a thickness of 2 μm or more and 13 μm or less to obtain a case.
Step (b): A step of storing at least a part of the hollow fiber membrane bundle in the case.
Step (c): A step of injecting a potting material between the hollow fiber membranes and between the hollow fiber membrane bundle and the primer layer of the case and curing to form a fixing portion.
Step (d): A step of cutting the fixing portion together with the end of the hollow fiber membrane and opening the end of the hollow fiber membrane as necessary.

  Hereinafter, as an example of the method for producing the hollow fiber membrane module of the present invention, a method for producing the hollow fiber membrane module 1 shown in FIG. 1 will be described.

(Process (a))
As shown in FIG. 3, a primer is applied to the inner wall surface in the vicinity of the first end of the case body 22 to form a first primer layer 24. Similarly, a primer is applied to the inner wall surface in the vicinity of the second end portion of the case body 22 to form a second primer layer (not shown) to form the case 20.

The primer application method may be appropriately selected according to the type of primer, the shape, size, material, surface roughness, etc. of the case body. Examples of the primer application method include a method of applying with a spatula, a method of applying with a brush, and a method of applying with a hand roller.
It is preferable to dry the primer after applying the primer. The drying temperature is preferably 15 to 30 ° C., and the drying time is preferably 15 minutes to 1 hour.

  The primer is a base paint for modifying the surface of the member. There are various types of primers depending on the material of the applied member and the required performance. Examples of the primer type include a conductive primer, an insulating primer, an elastic primer, an adhesive primer, and a permeable primer. Among these, the primer in the present invention is an adhesive primer, and improves the adhesion of the surface of a hardly adhesive member. By applying the primer between the adhesive and the material to be bonded, the adhesive force is increased, and even when pressure, thermal load, or the like is applied to the bonded portion, it is possible to prevent the bonded portion from peeling off.

  As the primer in the present invention, (1) it is a liquid that flows easily, (2) it has a capillary action that flows well into fine irregularities on the surface of the member, and (3) the adhesive and the adherend are fixed. Those satisfying the three conditions of having a certain strength (cohesive force) later are preferable. In particular, the condition (2) is important in that the entire surface of the member is well wetted so that the material of the member and the molecules of the primer can approach each other.

As the primer, a primer containing acid-modified polyolefin is used because it is excellent in the effect of improving the adhesiveness between the case body 22 (adhesive material) and the fixing portion (adhesive).
Examples of the acid-modified polyolefin include non-chlorine acid-modified polyolefin and acid-modified chlorinated polyolefin.
Examples of the non-chlorine acid-modified polyolefin include maleic anhydride-modified polyolefin.

  As the primer, it is preferable to use a primer having a tensile shear bond strength measured by the following procedure of 2.0 MPa or more, and more preferably a primer having a tensile shear bond strength of 2.2 MPa or more.

Procedure for measuring tensile shear bond strength:
-Prepare two test pieces (length: 100 mm x width: 20 mm x thickness: 2 mm) made of the same material as the case body.
-Adhesive part (length: 12.5 mm x width: 20 mm) at one end of each of the two test pieces is polished with # 240 abrasive paper and wiped with ethanol.
Apply primer to each bonded part of two test pieces and dry for 1 hour.
-After the centrifugal defoaming treatment of the potting material, apply it to the bonded part of one test piece.
-The adhesive part of one test piece and the adhesive part of the other test piece face each other via a potting material, and the part other than the adhesive part of one test piece and the part other than the adhesive part of the other test piece face each other Two test pieces are stacked so that they do not.
-The potting material protruding from the two test pieces is wiped off, and the two test pieces are sandwiched between clips at the bonded portion and heated at 60 ° C for 6 hours to cure the potting material.
-In accordance with JIS K 6850: 1999, the end of each of the two test pieces opposite to the adhesion part is fixed with a chuck of a tensile tester so that the distance between the chucks is 115 mm, and the adhesion part The chuck of the tensile tester is moved at a pulling speed of 2 mm / min until peeling occurs.
・ Divide the maximum load when peeling occurs in the bonded area by the area of the bonded area to obtain the tensile shear bond strength.

  The concentration of the acid-modified polyolefin in the primer is preferably 2.5 to 17% by mass, more preferably 3 to 15% by mass, and particularly preferably 5 to 10% by mass, out of 100% by mass of the primer. If the concentration of the acid-modified polyolefin is not less than the lower limit of the above range, a primer layer having a desired thickness can be easily formed. If the concentration of the acid-modified polyolefin exceeds the upper limit of the above range, the viscosity of the primer becomes too high, so that it becomes difficult to control the amount of primer applied, and the primer layer becomes thick. When the concentration of the acid-modified polyolefin exceeds the upper limit of the above range, it is preferable to dilute the primer with a solvent to lower the viscosity of the primer.

  The amount of primer applied is such that the thickness of the primer layer falls within the above range. The primer merely improves the adhesiveness between the adhesive and the material to be bonded, and the case body 22 and the primer, and the fixing portion and the primer are not connected. Therefore, if the primer layer is too thick, a distance is generated between the case main body 22 and the fixed portion, and the adhesive force is reduced. On the other hand, if the primer layer is too thin, the effect as a primer cannot be exhibited, and the adhesive strength is not improved.

(Process (b))
As shown in FIG. 4, the hollow fiber membrane bundle 10 is stored in the case 20 so that the first end of the hollow fiber membrane bundle 10 and the first end of the case 20 are aligned.
As a method for storing the hollow fiber membrane bundle 10, a known method is used. The hollow fiber membrane bundle 10 converges the hollow fiber membrane 12 by a known method, and if necessary, binds one or both of the first end and the second end, or the whole by a known method. Then insert it into the case.

(Process (c))
As shown in FIG. 5, the potting material is injected between the hollow fiber membranes 12 and between the hollow fiber membrane bundle 10 and the first primer layer 24 of the case 20, and cured to be the first fixing portion 32. Form. Similarly, the potting material is injected between the hollow fiber membranes 12 and between the hollow fiber membrane bundle 10 and the second primer layer (not shown) of the case 20 and cured to be a second fixing portion (shown). Abbreviation).

  A known method is used as the potting material injection method. As a potting material injection method, the case containing the hollow fiber membrane bundle 10 is rotated and the potting material is injected by centrifugal force; the potting material is injected by gravity generated by a drop; the potting material using a syringe or the like And the like.

  In order to prevent the potting material from entering the hollow fiber membrane 12 during the injection of the potting material, it is preferable that the end of the hollow fiber membrane 12 is closed by some method. A known method is used as the sealing method. As a sealing method, a method of sealing the open end of the hollow fiber membrane 12 with a resin or the like; a method of crushing the open end of the hollow fiber membrane 12 by heat fusion or the like; For example, a method of folding in a U-shape.

Examples of the potting material include an adhesive containing a known thermosetting resin. Examples of the thermosetting resin include polyurethane resin, epoxy resin, unsaturated polyester resin, and the like. A thermosetting resin may be used individually by 1 type, and may use 2 or more types together. The thermosetting resin may be selected in consideration of the adhesion to the hollow fiber membrane 12 and the case 20, the heat resistance of the cured product, the chemical resistance, and the like. As the thermosetting resin, a polyurethane resin or an epoxy resin is preferable because a wide range of curing reaction conditions can be selected.
Specific examples of the potting material include a potting material described in International Publication No. 2015/186705.

(Process (d))
As shown in FIG. 6, the first fixing portion 32 is cut together with the first end of the case 20 and the first end of the hollow fiber membrane bundle 10 to open the end of the hollow fiber membrane 12. Similarly, the second fixing portion (not shown) is cut along with the second end portion of the case 20 and the second end portion of the hollow fiber membrane bundle 10 so that the end portion of the hollow fiber membrane 12 is opened. The yarn membrane module 1 is obtained.

(Mechanism of action)
In the method for producing a hollow fiber membrane module of the present invention described above, after applying a primer containing acid-modified polyolefin to the inner wall surface of the case body, a primer layer having a thickness of 2 μm to 13 μm is formed. Since the potting material is injected between the hollow fiber membrane and between the hollow fiber membrane bundle and the primer layer of the case and cured to form the fixed part, the bonding between the case body and the fixed part Power is high. Therefore, it is possible to manufacture a hollow fiber membrane module in which peeling between the case and the fixing portion is suppressed. That is, the hollow fiber membrane module can be manufactured efficiently and with a high yield without impairing the function of the hollow fiber membrane module.

(Other embodiments)
The manufacturing method of the hollow fiber membrane module of this invention should just be a method which has process (a)-(c) mentioned above, and is not limited to the manufacturing method of the example of illustration.
For example, a method in which step (a) in the present invention is combined with a known method described in JP-A-10-18389 or the like may be used.

  Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited thereto.

(Tensile shear bond strength)
(I) Sample preparation:
The test pieces and potting materials used for measuring the tensile shear bond strength are as follows.
Test piece: A test piece (length: 100 mm × width: 20 mm × thickness: 2 mm) made of polypropylene (manufactured by Sumitomo Chemical Co., Ltd., Nobrene (registered trademark) AZ564).
Potting material: Potting material having the composition shown in Table 1.

  Adhesive portions (length: 12.5 mm × width: 20 mm) at one end of each of the two test pieces were polished with # 240 abrasive paper and wiped with ethanol. A primer described later was applied to each bonded portion of the two test pieces so as to have a predetermined thickness, and was dried for 1 hour. After the potting material was subjected to centrifugal defoaming treatment, it was applied to the bonded portion of one test piece. The bonding part of one test piece and the bonding part of the other test piece face each other via a potting material, and the part other than the bonding part of one test piece does not face the part other than the bonding part of the other test piece. Thus, two test pieces were stacked. The potting material protruding from the two test pieces was wiped off, the two test pieces were sandwiched between the clips at the bonded portion, and heated at 60 ° C. for 6 hours to cure the potting material, thereby obtaining a sample.

(Ii) Measurement of tensile shear bond strength:
In accordance with JIS K 6850: 1999, a tensile tester (A & D Co., Ltd.) was formed so that the distance between the two test pieces in the sample on the opposite side of the bonded portion was 115 mm between the chucks. The chuck of the tensile tester was moved at a tensile speed of 2 mm / min until peeling occurred at the bonded portion. The maximum load when peeling occurred at the bonded portion was divided by the area of the bonded portion to determine the tensile shear bond strength.

(Iii) Confirmation of the broken state of the bonded part:
The primer adheres to the adherend, and the primer itself aggregates and acts to resist deformation and breakage. And the destruction state of the adhesion | attachment part adhere | attached using the primer is divided roughly into three types. The first is interfacial fracture that breaks at the interface between the adhesive and the adherend, the second is cohesive fracture that breaks in the primer layer, and the third is material breakage that the adherend itself breaks. If the adhesive force is weak, interface peeling occurs, but if the adhesive force is sufficient, cohesive failure occurs. Therefore, it can be determined whether the adhesive force is sufficient by checking the destruction state of the bonded portion.

(Experimental example 1)
Using a varnish containing non-chlorine acid-modified polyolefin as a primer (Mitsui Chemicals, Unistor (registered trademark) P501, concentration of acid-modified polyolefin: 8% by mass), measuring the tensile shear bond strength by the procedure described above. did. The results are shown in Table 2. The peeled adhesive part was coherently broken, and the polypropylene test piece and the potting material could be securely bonded.

(Experimental example 2)
Using a varnish (concentration of acid-modified polyolefin: 3.75% by mass) obtained by dissolving a non-chlorine acid-modified polyolefin (Nippon Paper Co., Ltd., Auroren (registered trademark) 500MX) in toluene as a primer, the above procedure was followed. Shear bond strength was measured. The results are shown in Table 2. The peeled adhesive part was coherently broken, and the polypropylene test piece and the potting material could be securely bonded.

(Experimental example 3)
Using a varnish containing non-chlorine acid-modified polyolefin as a primer (Nippon Paper Industries Co., Ltd., Auroren (registered trademark) 350MX, concentration of acid-modified polyolefin: 15% by mass), measuring the tensile shear bond strength by the procedure described above. did. The results are shown in Table 2. The peeled adhesive part was coherently broken, and the polypropylene test piece and the potting material could be securely bonded.

(Comparative Experimental Example 1)
Using a varnish containing non-chlorine acid-modified polyolefin as a primer (Nippon Paper Industries Co., Ltd., Auroren (registered trademark) 500MX, concentration of acid-modified polyolefin: 15% by mass), measuring the tensile shear bond strength by the procedure described above. did. The results are shown in Table 2.

(Comparative Experimental Example 2)
When the tensile shear adhesive strength was measured without using a primer, the adhesive strength was weak, and the test piece was peeled off even when pulled slightly. The results are shown in Table 2.

Example 1
The materials used for manufacturing the hollow fiber membrane module are as follows.
Hollow fiber membrane: A composite hollow fiber membrane having a three-layer structure (manufactured by Mitsubishi Rayon Co., Ltd., MHF200SD, a gas permeable composite membrane comprising a gas permeable homogeneous layer and a porous layer sandwiching the homogeneous layer).
Case: Cylindrical case (inner diameter: 20 mm, length: 86 mm) made of polypropylene (manufactured by Sumitomo Chemical Co., Ltd., Nobren (registered trademark) AZ564).
Potting material: Potting material having the composition shown in Table 1.
Primer: Varnish containing non-chlorine acid-modified polyolefin (Mitsui Chemicals, Unistor (registered trademark) P501, concentration of acid-modified polyolefin: 8% by mass).

  A primer was applied to the inner wall surfaces in the vicinity of both ends of the case and dried for 1 hour to form a primer layer (thickness: 6.4 μm). A plurality of hollow fiber membranes were converged in a cylindrical shape to produce a hollow fiber membrane bundle, which was stored in a case. Using a centrifugal potting injection device, a potting material was injected into both ends of the case and cured to form a fixed portion. The potting material was completely cured in a dryer at 60 ° C. for 6 hours. Then, using the guillotine blade, the fixing part was cut together with the end part of the case and the end part of the hollow fiber membrane bundle, and the end part of the hollow fiber membrane was opened to obtain a hollow fiber membrane module.

  The hollow fiber membrane module was subjected to a heat cycle test in which heating at 60 ° C. for 2 hours and cooling at −20 ° C. for 2 hours was taken as one cycle, and this cycle was repeated 30 times. As a result, the hollow fiber membrane module obtained by using the primer containing acid-modified polyolefin was not peeled off at the bonding portion between the case and the fixing portion, and leakage could be suppressed. It is assumed that stress is also applied between the case and the fixed part by the heat cycle test, but by using a primer containing acid-modified polyolefin, the adhesive force between the case and the fixed part is increased, and there is no peeling. Yarn membrane module could be manufactured.

(Comparative Example 1)
A hollow fiber membrane module was produced in the same manner as in Example 1 except that no primer was used. The case and the potting material were insufficiently bonded, and the hollow fiber membrane bundle could not be fixed to the case with the potting material.

(Summary)
The experimental examples 1 to 3 using the primer and the comparative experimental example 1 had higher adhesive strength than the comparative experimental example 2 not using the primer, and the test piece and the potting material were adhered. In Experimental Examples 1 to 3, in which the thickness of the primer layer is in the range of 2 μm or more and 13 μm or less, the adhesive force was higher than that of Comparative Experimental Example 1 in which the thickness of the primer layer exceeded 13 μm.
Moreover, when modularizing like Example 1, it became clear that leak generation | occurrence | production can also be suppressed because the case and the fixing | fixed part have adhere | attached firmly.

  The hollow fiber membrane module of the present invention is useful as a membrane module used for liquid filtration, removal of dissolved gas from liquid (deaeration), gas supply to liquid (air supply), and the like.

1 hollow fiber membrane module,
2 hollow fiber membrane module,
10 hollow fiber membrane bundle,
11 Hollow fiber membrane bundle,
12 hollow fiber membranes,
14 Tying yarn,
20 cases,
22 Case body
22a first fluid inlet / outlet;
22b second fluid inlet / outlet;
24 first primer layer,
26 second primer layer,
32 first fixing part,
34 second fixing part,
40 first housing;
42 housing body,
44 Primer layer,
50 second housing,
52 housing body,
62 1st fixing | fixed part.

Claims (6)

A hollow fiber membrane bundle comprising a plurality of hollow fiber membranes, a case in which at least a part of the hollow fiber membrane bundle is accommodated, and a fixing portion for fixing the hollow fiber membrane bundle to the case, the case comprising: A method for producing a hollow fiber membrane module, comprising: a case body; and a primer layer provided on an inner wall surface of the case body so as to be interposed between the case body and the fixing portion,
The manufacturing method of a hollow fiber membrane module which has the following process (a)-(c).
Step (a): A step of applying the primer containing acid-modified polyolefin to the inner wall surface of the case body to form a primer layer having a thickness of 2 μm to 13 μm to obtain the case.
Step (b): A step of storing at least a part of the hollow fiber membrane bundle in the case.
Step (c): A step of injecting a potting material between the hollow fiber membranes and between the hollow fiber membrane bundle and the primer layer of the case, and curing the potting material to form the fixing portion.   The method for producing a hollow fiber membrane module according to claim 1, wherein the primer has a concentration of the acid-modified polyolefin of 2.5 to 17% by mass out of 100% by mass of the primer.   The manufacturing method of the hollow fiber membrane module of Claim 1 or 2 whose material of the said case main body is a polypropylene. The manufacturing method of the hollow fiber membrane module as described in any one of Claims 1-3 using the primer from which the tensile shear adhesive strength measured in the following procedure is 2.0 Mpa or more as said primer.
Procedure for measuring tensile shear bond strength:
-Prepare two test pieces (length: 100 mm x width: 20 mm x thickness: 2 mm) made of the same material as the case body.
-Adhesive part (length: 12.5 mm x width: 20 mm) at one end of each of the two test pieces is polished with # 240 abrasive paper and wiped with ethanol.
Apply the primer to each bonded part of the two test pieces and dry for 1 hour.
-After the centrifugal defoaming treatment of the potting material, the potting material is applied to the bonded portion of one test piece.
-The adhesive part of one test piece and the adhesive part of the other test piece face each other via a potting material, and the part other than the adhesive part of one test piece and the part other than the adhesive part of the other test piece face each other Two test pieces are stacked so that they do not.
-The potting material protruding from the two test pieces is wiped off, and the two test pieces are sandwiched between clips at the bonded portion and heated at 60 ° C for 6 hours to cure the potting material.
-In accordance with JIS K 6850: 1999, the end of each of the two test pieces opposite to the adhesion part is fixed with a chuck of a tensile tester so that the distance between the chucks is 115 mm, and the adhesion part The chuck of the tensile tester is moved at a pulling speed of 2 mm / min until peeling occurs.
・ Divide the maximum load when peeling occurs in the bonded area by the area of the bonded area to obtain the tensile shear bond strength. A hollow fiber membrane bundle comprising a plurality of hollow fiber membranes;
A case in which at least a part of the hollow fiber membrane bundle is stored;
A fixing portion for fixing the hollow fiber membrane bundle to the case,
The case is
The case body,
A primer layer provided on an inner wall surface of the case main body so as to be interposed between the case main body and the fixing portion;
The primer layer comprises an acid-modified polyolefin;
The hollow fiber membrane module whose thickness of the said primer layer is 2 micrometers or more and 13 micrometers or less.   The hollow fiber membrane module according to claim 5, wherein a material of the case body is polypropylene.

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