WO2021230112A1 - Method for manufacturing cartridge-type hollow fiber membrane module - Google Patents
Method for manufacturing cartridge-type hollow fiber membrane module Download PDFInfo
- Publication number
- WO2021230112A1 WO2021230112A1 PCT/JP2021/017219 JP2021017219W WO2021230112A1 WO 2021230112 A1 WO2021230112 A1 WO 2021230112A1 JP 2021017219 W JP2021017219 W JP 2021017219W WO 2021230112 A1 WO2021230112 A1 WO 2021230112A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- hollow fiber
- epoxy resin
- fiber membrane
- potting portion
- potting
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 205
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 194
- 238000000034 method Methods 0.000 title claims abstract description 62
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 48
- 238000004382 potting Methods 0.000 claims abstract description 387
- 239000003822 epoxy resin Substances 0.000 claims abstract description 157
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- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 20
- 125000002723 alicyclic group Chemical group 0.000 claims description 19
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 19
- 239000003566 sealing material Substances 0.000 claims description 19
- 230000003068 static effect Effects 0.000 claims description 16
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 14
- 239000004593 Epoxy Substances 0.000 claims description 10
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 10
- RNLHGQLZWXBQNY-UHFFFAOYSA-N 3-(aminomethyl)-3,5,5-trimethylcyclohexan-1-amine Chemical compound CC1(C)CC(N)CC(C)(CN)C1 RNLHGQLZWXBQNY-UHFFFAOYSA-N 0.000 claims description 9
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- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 4
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- DZIHTWJGPDVSGE-UHFFFAOYSA-N 4-[(4-aminocyclohexyl)methyl]cyclohexan-1-amine Chemical compound C1CC(N)CCC1CC1CCC(N)CC1 DZIHTWJGPDVSGE-UHFFFAOYSA-N 0.000 description 2
- 229920002943 EPDM rubber Polymers 0.000 description 2
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- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 1
- DNVXWIINBUTFEP-UHFFFAOYSA-N 2-[(2-phenylphenoxy)methyl]oxirane Chemical compound C1OC1COC1=CC=CC=C1C1=CC=CC=C1 DNVXWIINBUTFEP-UHFFFAOYSA-N 0.000 description 1
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 description 1
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
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Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/021—Manufacturing thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/02—Hollow fibre modules
- B01D63/04—Hollow fibre modules comprising multiple hollow fibre assemblies
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/02—Polycondensates containing more than one epoxy group per molecule
- C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
- C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/50—Amines
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/141—Feedstock
Definitions
- the present invention relates to a method for manufacturing a cartridge type hollow fiber membrane module used in a water treatment field, a fermentation industry field, a pharmaceutical manufacturing field, a food industry field, and the like.
- Filtration using a separation membrane is used in various fields such as drinking water production, water purification treatment, water treatment such as wastewater treatment, fermentation field involving cultivation of microorganisms and cultured cells, and food industry field.
- hollow fiber membrane modules used for food and pharmaceutical applications are biologically active by performing sterilization using hot water, sterilization using saturated water vapor, and chemical cleaning using acid or alkali. It can be used in a membrane treatment system that handles various liquids to be treated. For that purpose, not only the hollow fiber membrane but also all the members constituting the module are required to have heat resistance and chemical resistance.
- a hollow fiber membrane module in which a hollow fiber membrane bundle is fixed by an adhesive resin containing a heat-resistant epoxy resin as a main component is preferably used while using a module case made of stainless steel.
- a heat cycle generated by the temperature difference between the membrane filtration operation and saturated steam sterilization acts on the module peeling occurs due to the difference in thermal expansion of the epoxy resin that adheres to the stainless steel case. Occasionally, the filtrate to be treated was mixed with the undiluted solution.
- Patent Document 2 describes a hollow fiber membrane module in which the potting portion has a plurality of layers of two or more layers in order to secure the sealing property of the potting portion, and the dimensional change of the sealing portion due to the curing shrinkage of the potting agent is suppressed. It has been disclosed.
- these hollow fiber membrane modules have a configuration in which a bundle of hundreds to tens of thousands of hollow fiber membranes is bundled, stored in a cylindrical case, and the ends are bonded and fixed with resin.
- a centrifugal method is used in which a liquid uncured resin is permeated between the hollow fiber membranes using centrifugal force, and a liquid uncured resin is sent by a metering pump or a head and naturally.
- a static potting method in which the hollow fiber membrane is permeated between the hollow fiber membranes.
- the centrifugal method If you try to manufacture a hollow fiber membrane module by the centrifugal method, a large investment such as introduction of a centrifugal molding device is required. Further, it is necessary to maintain the centrifugal motion while the uncured resin is cured, which requires a large amount of power consumption and inevitably increases the cost. On the other hand, the latter static potting method has an advantage that the hollow fiber membrane module can be manufactured at low cost because it does not require a special and large-sized device such as the centrifugal method.
- the present invention provides a cartridge-type hollow fiber membrane module that can prevent leakage and contamination by germs due to peeling of the potting agent even when steam sterilization used for food and pharmaceutical applications is applied, and is a static potting method with a large cost merit. It is an object to provide a method of manufacturing by.
- the present invention provides the following method for manufacturing a cartridge type hollow fiber membrane module.
- the hollow fiber membrane is opened at at least one end of the housing, the hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and the plurality of hollow fiber membranes.
- a method for manufacturing a cartridge-type hollow fiber membrane module comprising: a first potting portion for adhering the hollow fiber membrane, and a sealing material for liquid-tightly fixing between the first potting portion and the housing.
- a step of forming the inner layer potting portion included in the first potting portion (A) A step of forming the inner layer potting portion included in the first potting portion, and (B) A step of forming an outer layer potting portion included in the first potting portion and covering the inner layer potting portion, and a step of forming the outer layer potting portion.
- step (a) is (A-1) An inner layer potting agent placement step of filling the inner layer potting agent forming the inner layer potting portion between the hollow fiber membranes, and (A-2) A curing step of curing the inner layer potting agent, Equipped with The step (b) is (B-1) After the curing step of (a-2), the outer layer potting portion is such that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion is in contact with the sealing material.
- Condition (p) The viscosity of the epoxy resin composition forming the inner layer potting portion at 25 ° C. is 400 mPa ⁇ s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less.
- the epoxy resin composition forming the outer layer potting portion contains an alicyclic polyamine composed of one cyclohexyl ring, the viscosity at 25 ° C. is 1200 mPa ⁇ s or less, and the glass of the cured product of the epoxy resin composition.
- the transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower.
- Condition (r) The relationship between the glass transition temperature Tg1 and the glass transition temperature Tg2 is 5 ⁇ Tg2-Tg1 ⁇ 20.
- the alicyclic polyamine composed of one cyclohexyl ring contained in the epoxy resin composition forming the outer layer potting portion is selected from the group consisting of isophoronediamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane.
- a cartridge type hollow fiber membrane module capable of preventing leakage of the potting portion even when steam treatment used for food and pharmaceutical applications is applied.
- FIG. 1 is a schematic vertical sectional view of the hollow fiber membrane cartridge of the present invention.
- FIG. 2 is a flowchart showing an example of the manufacturing method of the present invention.
- FIG. 3 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
- FIG. 4 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
- FIG. 5 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
- FIG. 6 is a schematic diagram illustrating an example of the manufacturing method of the present invention.
- FIG. 7 is a schematic vertical sectional view of the cartridge type hollow fiber membrane module according to the embodiment of the present invention.
- FIG. 8 is a cross-sectional view taken along the line AA of the cartridge type hollow fiber membrane module shown in FIG. 7.
- FIG. 9 is a cross-sectional view taken along the line BB of the cartridge type hollow fiber membrane module shown in FIG. 7.
- the manufacturing method of the cartridge type hollow fiber membrane module of the present invention (hereinafter, also referred to as “the manufacturing method of the present invention”) will be described with reference to the drawings.
- the directions such as “up” and “down” are based on the states shown in the drawings and are for convenience.
- the outflow side is the "upward” direction.
- the vertical direction thereof coincides with the vertical direction in the drawing.
- “mass” is synonymous with "weight”.
- the hollow fiber membrane cartridge 100 has a hollow fiber membrane bundle 2 having a plurality of hollow fiber membranes 1, and the hollow fiber membranes 1 are adhered to each other by potting portions at both ends of the hollow fiber membrane bundle 2.
- the manufacturing method of the present invention includes the following steps (a) and (b) in forming the potting portion (first potting portion 9) located on the side where the filtered liquid is discharged in the hollow fiber membrane cartridge. (A) Step of forming the inner layer potting portion included in the first potting portion (b) Step of forming the outer layer potting portion included in the first potting portion and covering the inner layer potting portion.
- the potting method is a centrifugal potting method in which a liquid potting agent is permeated between hollow fiber membranes using centrifugal force to cure it, and a hollow fiber is sent by sending a liquid potting agent with a metering pump or a head and allowing it to flow naturally.
- a static potting method in which the material is infiltrated between the filament membranes and then cured, and the production method of the present invention uses the static potting method.
- Step S1 the hollow fiber membrane bundle 2 including the plurality of hollow fiber membranes 1 is inserted into the first potting cap 15A, the inner layer potting agent is supplied, and the inner layer potting portion 9A is supplied.
- the first potting portion 9 is shown at the upper end, but in FIG. 3, it is shown downward as in the case of static potting.
- the end portion of the hollow fiber membrane on the side to be inserted into the first potting cap 15A (hereinafter, also referred to as "first end portion") is preliminarily sealed with a silicone adhesive.
- a pump for charging the potting agent is connected to the first potting cap 15A, and the potting agent for forming the inner layer (inner layer potting agent) can be supplied to the first potting cap 15A by the pump.
- the inner layer potting portion 9A is formed by allowing the potting agent to harden and stand still until it loses fluidity.
- the first potting cap 15A is removed to complete the curing of the inner layer potting portion 9A (step S2).
- heat treatment may be performed to promote the reaction.
- the dimensions of the first potting portion 9 can be stabilized.
- the steps of forming the inner layer potting portion include an inner layer potting agent placement step (step (a-1)) in which the inner layer potting agent is filled between the hollow fiber membranes and a curing step (step (a)) in which the potting agent is cured. -2)) and is included.
- the inner layer potting agent placement step is performed by the static potting in step S1. Then, a part of the curing step also proceeds in step S1. Further, the curing step is also performed in step S2, and the curing of the inner layer potting portion is completed.
- the heat treatment conditions for promoting curing differ depending on the type of potting agent used, it may be appropriately set according to the type of potting agent.
- an outer layer potting portion that covers the inner layer potting portion is formed.
- the outer layer potting portion is formed so that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion contacts the sealing material described later. It includes an outer layer potting agent placement step (step (b-1)) in which the outer layer potting agent to be formed is placed by a static potting method, and a curing step (step (b-2)) in which the potting agent is cured.
- the first end portion of the hollow fiber membrane bundle 2 in which the inner layer potting portion 9A is formed is attached to the first potting caps 15B and 15C, and the outer layer potting portion 9B is formed by static potting. Step S3).
- the first potting portion 9 is shown at the upper end, but in FIG. 4, it is shown downward as in the case of static potting.
- the first potting cap 15B and the first potting cap 15C are shown in FIG.
- the inner diameter of the cap is gradually increased or decreased.
- the clearance between the first potting caps 15B and 15C and the inner layer potting portion 9A is preferably 2 mm or more, and more preferably 4 mm or more.
- the clearance is preferably 8 mm or less, more preferably 6 mm or less.
- the air in the potting cap is discharged upward (in the direction in which the hollow fiber membrane extends). Therefore, in order to improve the discharge property of bubbles and prevent the bubbles from staying in the potting agent, it is preferable to add the potting agent from below (the end side of the hollow fiber membrane).
- step S3 the outer layer potting portion 9B is arranged so that the outer layer potting portion 9B covers the inner layer potting portion 9A at the portion in contact with the sealing material when the cartridge is incorporated in the module.
- the first potting caps 15B and 15C are removed to complete the curing of the outer layer potting portion 9B (step S4).
- heat treatment may be performed to promote the reaction.
- step S3 the step of arranging the potting agent for forming the outer layer potting portion 9B on the outer side of the inner layer potting portion 9A is performed in step S3, and a part of the step of curing the potting agent also proceeds in step S3.
- step S4 the curing is further advanced to complete the curing.
- the end portion of the hollow fiber membrane 1 (hereinafter, also referred to as “second end portion”) on the side opposite to the side on which the first potting portion 9 is formed is the second potting portion case. It is inserted in 11.
- the pin 17 is inserted into the through hole at the bottom of the second potting portion case 11, and the second potting portion case 11 and the pin 17 are housed inside the second potting cap 16.
- static potting is performed to form the second potting portion 10 (step S5).
- the hollow portion of the second end portion of the hollow fiber membrane 1 is sealed with a potting agent.
- the curing of the second potting portion 10 is completed (step S6). When curing, heat treatment may be performed to promote the reaction.
- the CC line portion at a desired position from the tip of the first potting portion 9 is cut with a tip saw type rotary blade or the like to open the first end portion of the hollow fiber membrane 1 ( By step S7), the hollow fiber membrane cartridge 100 can be manufactured.
- the hollow fiber membrane cartridge 100 manufactured by the above method is inserted into the housing body 3, fixed with a sealing material (for example, O-ring 13), and the upper cap 4 and the lower cap 5 are attached. Therefore, the cartridge type hollow fiber membrane module 101A shown in FIG. 7 can be manufactured.
- a sealing material for example, O-ring 13
- the surface of the inner layer potting portion 9A and the inner surface of the second potting portion case 11 may be filed, plasma-treated, primer-treated, or the like in order to improve the adhesiveness.
- the cartridge-type hollow fiber membrane module has a housing, a hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and at least one end of the plurality of hollow fiber membranes.
- a first potting portion for adhering the hollow fiber membrane and a sealing material for liquidally fixing the space between the hollow fiber membrane and the housing are provided so that the hollow fiber membrane is opened.
- the cartridge type hollow fiber membrane module 101A includes a housing and the hollow fiber membrane cartridge 100 shown in FIG. 1 housed in the housing.
- the housing is composed of a hollow housing body 3, an upper cap 4 and a lower cap 5 provided at both ends of the housing body 3.
- the upper part of the housing body 3 has an upper cap 4 having a filtrate outlet 7 and the lower part of the housing body 3 has a lower cap 5 having an undiluted solution inlet 6. It is tightly and airtightly connected.
- the upper cap 4 and the lower cap 5 use a gasket 14 as shown in FIG. 7, for example, and are fixed to the housing body 3 with a clamp or the like.
- the housing body 3 has flanges 3A and 3B at the upper and lower ends thereof over the entire circumference of the housing body 3. Further, on the side portion of the housing body 3, an undiluted liquid outlet 8 is provided near the filter liquid outlet 7.
- the upper cap 4 has an inner diameter substantially equal to the inner diameter of the housing body 3, and the upper end side thereof is reduced in diameter to form the filtrate outlet 7.
- a step portion 4A for forming a groove when connected to the housing body 3 is formed over the entire circumference of the upper cap 4.
- the lower cap 5 has an inner diameter substantially equal to the inner diameter of the housing body 3, and the lower end side thereof is reduced in diameter to form the stock solution inlet 6.
- FIG. 8 is a cross-sectional view taken along the line AA at the first potting position of the cartridge type hollow fiber membrane module 101A shown in FIG. 7.
- the hollow fiber membrane cartridge 100 is provided at both ends of a hollow fiber membrane bundle 2 including a plurality of hollow fiber membrane bundles 1 and both ends of the hollow fiber membrane bundle 2, and potting between the hollow fiber membranes 1 is adhered to each other. It has a part.
- the hollow fiber membrane cartridge 100 has a first potting portion 9 arranged on the filter liquid outlet 7 side of the housing and a second potting portion 10 arranged on the stock solution inlet 6 side of the housing. ..
- the first potting portion 9 arranged on the filter liquid outlet 7 side of the housing, that is, on the upper end side of the hollow fiber membrane cartridge 100, is a potting that adheres between the hollow fiber membranes 1 at the first end portion of the hollow fiber membrane bundle 2. It is formed of an agent.
- the hollow fiber membrane bundle 2 is bundled with the upper end face of the hollow fiber membrane 1 opened.
- the first potting portion 9 has a columnar shape, and a flange portion 9C is provided at the upper end portion thereof over the entire circumference of the first potting portion 9. Further, on the side surface of the first potting portion 9, a step portion 9D is provided over the entire circumference. By providing the step portion 9D, the outer diameter of the upper portion of the first potting portion 9 is larger than the outer diameter of the lower portion.
- the flange portion 9C of the first potting portion 9 is inserted into a groove (fixed portion) formed between the housing body 3 and the upper cap 4 by attaching the upper cap 4 to the housing body 3. In this way, the first potting portion 9 is fixed to the upper end portion of the housing body 3.
- An O-ring 13 as a sealing material is installed between the stepped portion 9D of the first potting portion 9 and the housing body 3, and the first potting portion 9 is fixed liquidtightly and airtightly.
- the first potting portion 9 is liquid-tightly and airtightly fixed by crushing the O-ring 13 in the radial direction (horizontal direction in FIG. 1) of the hollow fiber membrane module.
- the crushing allowance of the O-ring 13 is preferably 8% or more and 30% or less.
- the first potting portion 9 is not directly adhered to the housing body 3, but is liquid-tightly and airtightly fixed by the O-ring 13.
- fixing the first potting portion with a sealing material such as an O-ring in a liquid-tight and airtight manner is referred to as a seal
- a portion fixed with the sealing material is referred to as a sealing portion.
- Epoxy resin is used as the potting agent, and these potting agents mix and cure the two liquids, but the volume shrinks at the time of curing. If the size of the step 9D changes due to shrinkage or strain occurs, it cannot be sealed by a sealing material such as an O-ring, and the undiluted solution may leak to the filtered solution side.
- the first potting portion 9 includes an inner layer potting portion 9A and an outer layer potting portion 9B.
- the outer layer potting portion 9B is formed on the outside of the inner layer potting portion 9A after the inner layer potting portion 9A is sufficiently cured and shrunk.
- the inner layer potting portion 9A has already been cured and shrunk. Therefore, the dimensional deviation that occurs in the final outer shape of the first potting portion 9 is derived only from the curing shrinkage of the outer layer potting portion 9B. do. In this way, the dimensional deviation can be suppressed to be smaller than when the potting portion is composed of a single layer.
- both the inner layer potting portion and the outer layer potting portion are formed in the portion where the first potting portion is in contact with the sealing material. Must be.
- the inner layer potting portion may have a simple shape such as a cylinder.
- the structures such as the flange portion 9C and the step portion 9D provided on the surface of the first potting portion 9 are formed by the outer layer potting portion 9B.
- the present invention is not limited to this, and for example, the inner layer potting portion 9A may also have a structure such as a step portion or a flange portion.
- the outer layer potting portion 9B is in contact with the sealing material. That is, the outer layer potting portion 9B is arranged so as to cover the inner layer potting portion 9A, and the outer surface of the first potting portion 9 is formed by the outer layer potting portion 9B.
- An epoxy resin composition is used as the potting agent for forming the inner layer potting portion and the outer layer potting portion.
- the glass transition temperature of the cured product of the epoxy resin composition forming the inner layer potting portion of the present embodiment (hereinafter referred to as Tg1) and the glass transition temperature of the cured product of the epoxy resin composition forming the outer layer potting portion (hereinafter referred to as Tg2). Satisfies the following equation (i) (condition (r)). 5 ⁇ Tg2-Tg1 ⁇ 20 ⁇ ⁇ ⁇ (i)
- the difference in glass transition temperature of the cured product of the epoxy resin composition forming the inner layer potting part and the outer layer potting part in the range of 5 ° C to 20 ° C, high temperature conditions such as filtration of high temperature liquid, hot water sterilization, steam sterilization, etc. It is possible to suppress the generation of cracks due to the difference in expansion and contraction due to the heat of the inner layer and the outer layer when used in.
- the curing calorific value Q1 of the epoxy resin composition forming the inner layer potting portion of the present embodiment is preferably 350 mJ / mg or less.
- the curing heat generation amount of the epoxy resin composition is more preferably 280 mJ / mg or less.
- the method for measuring the calorific value of curing is differential scanning calorimetry (DSC).
- the curing calorific value Q1 [mJ / mg] ⁇ mass W1 [g] (hereinafter, Q1 ⁇ W1 value) of the epoxy resin composition forming the inner layer potting portion of the present embodiment is preferably 500 kJ or less.
- the mass W1 of the epoxy resin composition forming the inner layer potting portion (hereinafter, also referred to as epoxy mass W1) is the mass W2 of the epoxy resin composition forming the outer layer potting portion (hereinafter, epoxy mass W2).
- the same amount or more is preferable, and more is more preferable. Further, as the amount of epoxy resin increases, heat generation during curing tends to increase, which deteriorates the hollow fiber membrane. Therefore, deterioration of the hollow fiber membrane can be suppressed by setting the Q1 ⁇ W1 value to 500 kJ or less.
- the Q1 ⁇ W1 value is more preferably 400 kJ or less.
- the viscosity of the epoxy resin composition forming the inner layer potting portion of the present embodiment at 25 ° C. is 400 mPa ⁇ s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less (conditions). (P)).
- the viscosity in the present invention is "cone-plate type" in JISZ8803 (1991) using an E-type viscometer (TVE-30H manufactured by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 ° 34'x R24). Measure at a measurement temperature of 25 ° C. according to "Viscosity measurement method using a rotational viscometer”. The viscosity of the present invention is one minute after the start of measurement.
- the glass transition temperature Tg1 When the glass transition temperature Tg1 is 95 ° C or higher, it can be used under high temperature conditions such as high temperature liquid filtration, hot water sterilization, and steam sterilization. Further, when the glass transition temperature Tg1 is 160 ° C. or lower, the residual stress of the cured product of the epoxy resin composition forming the inner layer potting portion is reduced, and the mechanical properties of the potting portion tend to be improved.
- the glass transition temperature Tg1 is more preferably 100 ° C. or higher, and even more preferably 105 ° C. or higher. Further, 150 ° C. or lower is more preferable, and 140 ° C. or lower is further preferable.
- the method for measuring the glass transition temperature is differential scanning calorimetry (DSC).
- composition of the epoxy resin composition of the inner layer potting portion is not limited, and various known epoxy resins can be used.
- the epoxy resin composition of the inner layer potting portion preferably contains an alicyclic polyamine containing two or more cyclohexyl rings.
- the alicyclic polyamine containing two or more cyclohexyl rings include 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane and 4,4'-diaminodicyclohexylmethane. Of these, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane is preferable.
- the alicyclic polyamine containing two or more cyclohexyl rings is preferably contained in an aliphatic amine-based curing agent in an amount of 50% by mass or more, more preferably 60% by mass or more, and contained in an amount of 95% by mass or less. Is preferable, and 90% by mass or less is more preferable.
- the epoxy resin composition forming the outer layer potting portion of the present embodiment contains an alicyclic polyamine composed of one cyclohexyl ring, has a viscosity at 25 ° C. of 1200 mPa ⁇ s or less, and is a glass of a cured product of the epoxy resin composition.
- the transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower (condition (q)).
- the viscosity By setting the viscosity to 1200 mPa ⁇ s or less, it is possible to suppress the residual of air bubbles in the outer layer potting portion even when manufactured by static potting, and it is possible to secure the sealing property. It is more preferably 1000 mPa ⁇ s or less, and further preferably 800 mPa ⁇ s or less.
- the glass transition temperature Tg2 When the glass transition temperature Tg2 is 110 ° C or higher, it can be used under high temperature conditions such as high temperature liquid filtration, hot water sterilization, and steam sterilization. Further, when the glass transition temperature Tg2 is 160 ° C. or lower, the residual stress of the epoxy resin composition forming the outer layer potting portion is reduced, and the mechanical properties of the potting portion tend to be improved.
- the glass transition temperature Tg2 is more preferably 115 ° C. or higher, further preferably 120 ° C. or higher, still more preferably 155 ° C. or lower, still more preferably 150 ° C. or lower.
- the curing calorific value Q2 of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 1000 mJ / mg or less.
- the curing heat generation amount of the epoxy resin composition is preferably 1000 mJ / mg or less.
- the curing calorific value Q2 [mJ / mg] ⁇ mass W2 [g] (hereinafter, Q2 ⁇ W2 value) of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 400 kJ or less.
- Q2 ⁇ W2 value The curing calorific value Q2 [mJ / mg] ⁇ mass W2 [g] (hereinafter, Q2 ⁇ W2 value) of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 400 kJ or less.
- the Q2 ⁇ W2 value is more preferably 300 kJ or less.
- the bending fracture strain of the cured product of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 4% or more. By setting the bending fracture strain to 4% or more, it is possible to suppress the generation of cracks due to fatigue when the hollow fiber membrane module is repeatedly used, and it becomes easy to obtain a hollow fiber membrane module having excellent durability.
- the bending strength of the cured product of the epoxy resin composition forming the outer layer potting portion of the present embodiment is preferably 90 MPa or more.
- the flange portion 9C of the first potting portion is sandwiched between the flange portion 3A of the housing body 3 and the step portion 4A of the upper cap 4, so that the first potting portion can be moved in the axial direction.
- stress is generated that pushes the flange portion 9C of the first potting portion upward or downward.
- the epoxy resin composition forming the outer layer potting portion is preferably an epoxy resin composition containing at least the following component [A] and the following component [B].
- the component [A] is a bisphenol type epoxy resin.
- the bisphenol type epoxy resin is not particularly limited as long as it is converted into a glycidyloxy group by reacting two phenolic hydroxyl groups of the bisphenol compound with epichlorohydrin, and the bisphenol type epoxy resin is, for example, bisphenol A type. Examples thereof include epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, and bisphenol S type epoxy resin.
- the bisphenol type epoxy resin is preferably used because it has an excellent balance between toughness and heat resistance of the cured product of the obtained epoxy resin composition. In particular, a liquid bisphenol type epoxy resin is preferable because it can suppress the residual air bubbles in the outer layer potting portion.
- liquid means that the viscosity at 25 ° C. is 1000 Pa ⁇ s or less
- solid state means that there is no fluidity at 25 ° C. or extremely low fluidity. It means that the viscosity at 25 ° C. is larger than 1000 Pa ⁇ s.
- This embodiment preferably includes the following component [A1] as the component [A].
- [A1] Bisphenol F type epoxy resin
- the bisphenol F type epoxy resin is preferable because it can reduce the viscosity of the epoxy resin composition while maintaining heat resistance and can effectively suppress the residual air bubbles in the outer layer potting portion.
- the content of the component [A1] is preferably in the range of 10% by mass or more and 60% by mass or less in 100% by mass of the total bisphenol type epoxy resin.
- an epoxy resin other than the component [A] may be contained as long as the effect of the present invention is not impaired.
- Epoxy resins other than the component [A] can be preferably used because the process compatibility such as mechanical properties, heat resistance and viscosity can be adjusted according to the purpose.
- Examples of the epoxy resin other than the component [A] include phenylglycidyl ether type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, aminophenol type epoxy resin, phenol novolac type epoxy resin, and epoxy resin containing dicyclopentadiene skeleton.
- Examples thereof include a phenylglycidyl ether type epoxy resin and a reactive diluent having an epoxy group. These may be used alone or in combination of two or more.
- the component [B] is an aliphatic amine-based curing agent.
- the aliphatic amine-based curing agent is a compound having one or more primary or secondary amino groups in the molecule.
- Examples of the aliphatic amine-based curing agent include isophoronediamine, diethylenetriamine, triethylenetetramine, hexamethylenediamine, N-aminoethylpiperazine, 4,4'-methylenebiscyclohexylamine, and 2,2'-dimethyl-4,4.
- '-Diaminodicyclohexylmethane, cyclohexanediamine, 1,3-bisaminomethylcyclohexane, aliphatic polyamines having an alkylene glycol structure and the like can be mentioned.
- the aliphatic amine-based curing agent of the component [B] contains an alicyclic polyamine composed of one cyclohexyl ring.
- the alicyclic polyamine containing a cyclohexyl ring has a more rigid molecular chain than the chain polyamine, and the alicyclic polyamine consisting of one cyclohexyl ring has a smaller molecular weight between cross-linking points than the polyamine consisting of two or more cyclohexyl rings.
- Examples of the alicyclic polyamine composed of one cyclohexyl ring include isophorone diamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane.
- the alicyclic polyamine composed of one cyclohexyl ring is preferably contained in an amount of 50% by mass or more, more preferably 60% by mass or more, and 90% by mass or less with respect to the total aliphatic amine-based curing agent component. Is preferable.
- This embodiment preferably contains an aliphatic polyamine having an alkylene glycol structure in addition to the alicyclic polyamine composed of one cyclohexyl ring as the component [B].
- Aliphatic polyamines having an alkylene glycol structure are preferably used because the viscosity of the obtained epoxy resin composition can be lowered and the residual air bubbles in the outer layer potting portion can be suppressed.
- the alkylene glycol structure include polyoxyethylene, polyoxypropylene, and a copolymer of polyoxyethylene and polyoxypropylene.
- the aliphatic polyamine having an alkylene glycol structure is preferably contained in an amount of 10% by mass or more, more preferably 20% by mass or more.
- the component [B] preferably contains isophorone diamine and an aliphatic polyamine having an alkylene glycol structure.
- the total amount of amine used as a curing agent is preferably such that the active hydrogen equivalent is 0.6 equivalents or more and 1.2 equivalents or less with respect to the epoxy groups of all the epoxy resin components contained in the epoxy resin composition. Within this range, it becomes easy to obtain an epoxy resin composition that provides an outer layer potting portion having an excellent balance between heat resistance and mechanical properties.
- the epoxy resin composition of the present embodiment can contain a thermoplastic resin as long as the effects of the present invention are not impaired.
- the thermoplastic resin may contain a thermoplastic resin soluble in an epoxy resin, organic particles such as rubber particles and thermoplastic resin particles, and the like.
- thermoplastic resin soluble in the epoxy resin examples include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinylpyrrolidone, and polysulfone.
- polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral, polyvinyl alcohol, phenoxy resin, polyamide, polyimide, polyvinylpyrrolidone, and polysulfone.
- Examples of the rubber particles include crosslinked rubber particles and core-shell rubber particles obtained by graft-polymerizing a dissimilar polymer on the surface of the crosslinked rubber particles.
- This embodiment includes a second potting portion that bundles the hollow fiber membrane in a sealed state on the facing surface of the first potting portion, and the second potting portion is formed of the hollow fiber membrane and the potting agent.
- a second potting portion 10 which is a lower end side of the hollow fiber membrane cartridge 100 is arranged on the stock solution inlet 6 side of the housing.
- the second potting portion 10 where the second end portion of the hollow fiber membrane 1 is located is formed by adhering a hollow fiber membrane bundle 2 composed of a large number of hollow fiber membranes 1 and a second potting portion case 11 with a potting agent.
- the hollow portion of the hollow fiber membrane 1 is sealed with a potting agent so that it does not open.
- the second potting portion case 11 has a cylindrical shape having a bottom portion below, and its outer diameter is smaller than the inner diameter of the housing body 3.
- the second potting portion 10 has a through hole 12 and plays a role of a flow path of the undiluted solution.
- the type of potting agent used in the second potting portion of the cartridge type hollow fiber membrane module is not particularly limited as long as it satisfies the adhesive strength, heat resistance, chemical durability, etc. with the member to be bonded, but for example, epoxy resin or polyurethane resin. Etc. can be used.
- FIG. 9 is a sectional view taken along line BB at the second potting position of the module of FIG. 7.
- the cartridge type hollow fiber membrane module of the present embodiment includes a hollow fiber membrane as a separation membrane.
- the structure of the hollow fiber membrane is a symmetric membrane with a uniform pore diameter as a whole, an asymmetric membrane whose pore diameter changes in the thickness direction of the membrane, and a support membrane layer for maintaining strength and a target substance for separation.
- the material of the separation film is not particularly limited, but the separation film is, for example, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride / propylene hexafluoride copolymer, ethylene / ethylene tetrafluoride copolymer.
- Fluoro-based resins such as, cellulose acetate, cellulose acetate propionate, cellulose esters such as cellulose acetate butyrate, polysulfone-based resins such as polysulfone and polyethersulfone, and resins such as polyacrylonitrile, polyimide and polypropylene can be contained. ..
- the separation membrane made of a fluorine-based resin or a polysulfone-based resin has high heat resistance, physical strength, and chemical durability, and thus can be suitably used for a cartridge type hollow fiber module.
- the hollow fiber membrane may further contain a hydrophilic resin in addition to the fluororesin and the polysulfone resin.
- the hydrophilic resin can increase the hydrophilicity of the separation membrane and improve the water permeability of the membrane.
- the hydrophilic resin may be any resin that can impart hydrophilicity to the separation film, and is not limited to a specific compound, but for example, cellulose ester, fatty acid vinyl ester, vinylpyrrolidone, ethylene oxide, and the like.
- a propylene oxide, a polymethacrylic acid ester-based resin, a polyacrylic acid ester-based resin, and the like are preferably used.
- the material of the sealing material such as the O-ring and the gasket used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororubber, silicone rubber, ethylene propylene diene rubber (EPDM) Etc. can be used.
- the material of the housing used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororesins such as polysulfone resin, polytetrafluoroethylene, perfluoroalkoxy fluororesin, etc. Examples thereof include polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, and aluminum.
- the material of the tubular case and the second potting portion case used in the cartridge type hollow fiber membrane module is not particularly limited, but can be selected from, for example, the same materials as the housing.
- ⁇ Viscosity measurement of epoxy resin composition> The viscosity of the epoxy resin composition prepared according to the above ⁇ Preparation method of epoxy resin composition> is adjusted to the standard cone rotor (1 ° 34'in accordance with the "viscosity measurement method using a cone-plate type rotational viscometer" in JIS Z8803 (2011). Using a TVE-30H manufactured by an E-type viscometer (Toki Sangyo Co., Ltd.) equipped with ⁇ R24), the measurement was performed at a rotation speed of 10 rotations / minute. The viscosity was read 1 minute after the epoxy resin composition was put into an apparatus set at 25 ° C.
- ⁇ Measurement of curing calorific value of epoxy resin composition> Weigh 3 mg of the epoxy resin composition prepared according to the above ⁇ Preparation method of epoxy resin composition> into a sample pan, and use a differential scanning calorimeter (DSC-60 Plus: manufactured by Shimadzu Corporation) from 0 ° C. to 200 ° C. The measurement was carried out under the condition of constant rate temperature rise up to 10 ° C./min. The calorific value of curing was calculated from the obtained DSC curve according to JIS K0129 (1994).
- ⁇ Method for producing a cured product of an epoxy resin composition> The epoxy resin composition prepared according to the above ⁇ Method for preparing an epoxy resin composition> is defoamed in a vacuum and then poured into a silicon sheet hollowed out to a width of 10 mm, a length of 80 mm and a thickness of 4 mm to form a plate-shaped epoxy resin composition. A cured product was obtained. The curing conditions were that the mixture was allowed to stand at room temperature for 24 hours and then cured at 100 ° C. for 5 hours.
- ⁇ Measurement method of glass transition temperature of cured product of epoxy resin composition> Small pieces (5 mg to 10 mg) were collected from the cured product of the epoxy resin composition prepared according to the above ⁇ Method for producing a cured product of the epoxy resin composition>, and the intermediate point glass transition temperature was measured according to JIS K7121 (1987). A differential scanning calorimeter DSC-60 Plus (manufactured by Shimadzu Corporation) was used for the measurement, and the measurement was performed at a heating rate of 10 ° C./min under a nitrogen gas atmosphere.
- the hollow fiber membrane As the hollow fiber membrane, a hollow fiber membrane having a bubble point of 200 kPa or more is used, and since the pores are filled with water, air does not permeate through the pores of the hollow fiber membrane.
- the bubble point is the pressure at which the solvent in the pores of the membrane is pushed out and the air permeates when the pressure is applied to the hollow fiber membrane with compressed air.
- Example 1 ⁇ Preparation of polyvinylidene fluoride microfiltration hollow fiber membrane> 38 parts by mass of vinylidene fluoride homopolymer having a weight average molecular weight of 417,000 and 62 parts by mass of ⁇ -butyrolactone were mixed and dissolved at 160 ° C. This polymer solution was discharged from the mouthpiece of a double tube with an 85% by mass ⁇ -butyrolactone aqueous solution as a hollow fiber forming liquid, and an 85% by mass ⁇ -butyrolactone aqueous solution having a temperature of 5 ° C. was placed 30 mm below the mouthpiece.
- PVDF polyvinylidene fluoride
- ⁇ Making a hollow fiber membrane cartridge> The hollow fiber membrane was cut to a length of 1800 mm, immersed in a 30 mass% glycerin aqueous solution for 1 hour, and then air-dried. This hollow fiber membrane was heat-treated with steam at 125 ° C. for 1 hour, then air-dried, and cut into a length of 1200 mm. The 5400 hollow fiber membrane bundles thus obtained were bundled into one bundle. The first end side of the hollow fiber membrane bundle was sealed with a silicone adhesive (manufactured by Toray Dow Corning Co., Ltd., SH850A / B, which was a mixture of two agents so that the mass ratio was 50:50).
- a silicone adhesive manufactured by Toray Dow Corning Co., Ltd., SH850A / B, which was a mixture of two agents so that the mass ratio was 50:50.
- the hollow fiber membrane sealing the first end side was inserted into a polypropylene first potting cap 15A (inner diameter 139.3 mm, inner length 92 mm).
- Liquid bisphenol A type epoxy resin (“jER®” 828, manufactured by Mitsubishi Chemical Corporation) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (“Baxxodur®” EC331, BASF Japan Co., Ltd.) and polyetheramine (“JEFFAMIN (registered trademark)” D230) were mixed so as to have a mass ratio of 100: 19.2: 12.8.
- the obtained epoxy resin composition was injected into the first potting cap 15A at a rate of 10 g / min using a tube pump. 1020 g of a potting agent was put into the first potting cap 15A. After charging, the potting agent was cured by allowing it to stand at room temperature for 24 hours.
- the first potting cap 15A was removed, and further heat treatment was performed at 100 ° C. for 5 hours. As a result, the inner layer potting portion 9A of the first potting portion 9 was formed. Then, the surface of the inner layer potting portion 9A was sanded with sandpaper (# 80) and degreased with ethanol.
- the inner layer potting portion 9A of the first potting portion is inserted into the polypropylene first potting caps 15B and 15C as shown in FIG. 4, and 10 g / min using a tube pump as in the case of the inner layer potting portion 9A.
- the epoxy resin composition was injected at the speed of.
- the minimum inner diameter portion of the first potting cap 15B shown in FIG. 4 is 149.3 mm, and the maximum inner diameter portion is 167 mm.
- the minimum inner diameter portion of the first potting cap 15B is an O-ring seal surface forming portion.
- the maximum outer diameter portion of the first potting cap 15C is the forming portion of the flange portion 9C of the outer layer potting portion.
- the second end side of the hollow fiber membrane was inserted into the second potting part case 11 (inner diameter 149 mm, outer diameter 155 mm, inner length 40 mm) made of polysulfone.
- the inside of the second potting portion case 11 made of polysulfone was sanded in advance with sandpaper (# 80) and degreased with ethanol.
- a second potting cap 16 was attached to the outside of the second potting portion case 11.
- 36 pins for forming through holes were inserted into the holes at the bottom of the second potting portion case 11 and fixed.
- the pins were cylindrical with a diameter of 8 mm and a length of 100 mm, respectively.
- Bisphenol A type epoxy resin (“jER (registered trademark)” 828, manufactured by Mitsubishi Chemical Corporation) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane (“Baxxodur (registered trademark)” EC331, BASF Japan Co., Ltd.) and polyether amine (“JEFFAMIN®” D230) were mixed so that the mass ratio was 100: 19.2: 12.8.
- the obtained epoxy resin composition was poured into the second potting cap 16 at a speed of 10 g / min using a tube pump.
- the first potting portion was cut with a tip saw type rotary blade along the CC line of FIG. 6, and the first end portion of the hollow fiber membrane was opened to obtain a hollow fiber membrane cartridge.
- the viscosity of the epoxy resin composition forming the inner layer potting portion of the hollow fiber membrane cartridge at 25 ° C. was 1420 mPa ⁇ s, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition was 110 ° C.
- the calorific value for curing was 240 mJ / mg, which satisfied the condition (p).
- the viscosity of the epoxy resin composition forming the outer layer potting portion at 25 ° C. was 1050 mPa ⁇ s
- the glass transition temperature Tg2 of the cured product of the epoxy resin composition was 121 ° C., which satisfied the condition (q). ..
- the bending strength was 122 MPa and the bending breaking strain was 4.1%.
- the difference between Tg2 and Tg1 was 11 ° C., which satisfied the formula (i) of the condition (r).
- This cartridge type hollow fiber membrane module 101A was steam-heated (125 ° C., 60 minutes) 50 times by the above-mentioned method, and then an air leak test was performed by the above-mentioned method. As a result, the decrease in pressure was 0 kPa in 5 minutes, and it was confirmed that the sealing property was secured.
- Example 2 The resin compositions of the outer layer potting portion and the inner layer potting portion were set as shown in Table 1, respectively, and a hollow fiber membrane cartridge was produced by the same method as in Example 1.
- the evaluation results are shown in Table 1.
- the viscosity of the outer layer potting portion at 25 ° C. was 1200 mPa ⁇ s or less in all the examples, and the glass transition temperature Tg2 of the cured product of the epoxy resin composition was contained in the range of 110 ° C. or higher and 160 ° C. or lower. , The condition (q) was satisfied. Further, the difference between Tg2 and Tg1 was 5 ° C. or higher and 15 ° C. or lower, satisfying the condition (r). All of the obtained hollow fiber membrane cartridges had good heat resistance and air bubble removal property of the outer layer potting portion, as in Example 1. In addition, the sealing performance of the obtained cartridge-type hollow fiber membrane module was also good.
- Example 1 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
- the viscosity of the epoxy resin composition forming the outer layer potting portion was as high as 1420 mPa ⁇ s, and bubbles remained in the outer layer potting portion.
- the decrease in pressure was 100 kPa in 5 minutes.
- the air bubbles remaining in the outer layer potting portion deteriorated the sealing property of the O-ring seal portion and caused a leak.
- Example 3 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
- the glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 47 ° C.
- the decrease in pressure was 100 kPa in 5 minutes.
- Example 4 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
- the epoxy resin composition forming the inner layer potting portion had a low viscosity of 320 mPa ⁇ s at 25 ° C., and over-penetration occurred, so that filtration could not be performed.
- Example 5 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
- the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting portion was 47 ° C.
- the decrease in pressure was 100 kPa in 5 minutes.
- Example 6 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin compositions of the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2. The difference in glass transition temperature between the epoxy resin composition forming the inner layer potting portion and the cured product of the epoxy resin composition forming the outer layer potting portion was as large as -19 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. A leak occurred because a crack was generated in the first potting portion when steam heating was performed.
- Example 7 A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2.
- the glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 69 ° C.
- the decrease in pressure was 100 kPa in 5 minutes.
- Example 8 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
- the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 69 ° C.
- the decrease in pressure was 100 kPa in 5 minutes.
- Example 9 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the amounts of resin in the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2.
- the Q2 ⁇ W2 value of the epoxy resin composition forming the outer layer potting portion is as large as 729 kJ, and the maximum heat generation temperature of the epoxy resin composition reached at the time of curing becomes 260 ° C., the polyacetal potting case is deformed, and the inner layer potting portion is formed.
- the hollow fiber membrane of the above was partially melted.
- Example 10 A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2.
- the glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 107 ° C.
- the decrease in pressure was 100 kPa in 5 minutes.
- the method for producing a hollow fiber membrane module of the present invention is to be filtered in various fields such as drinking water production, water purification treatment, water treatment such as wastewater treatment, fermentation field involving cultivation of microorganisms and cultured cells, and food industry field. It is preferably applied to the filtration treatment of liquids.
- Hollow Fiber Membrane Cartridge 101A Cartridge-type Hollow Fiber Membrane Module 1 Hollow Fiber Membrane 2 Hollow Fiber Membrane Bundle 3 Housing Body 3A Gasket 3B Gasket 4 Upper Cap 4A Step 5 Lower Cap 6 Stock Solution Inlet 7 Filter Solution Outlet 8 Stock Solution Outlet 9 1st potting part 9A Inner layer potting part 9B Outer layer potting part 9C Filtration part 9D Step part 10 2nd potting part 11 2nd potting part Case 12 Through hole 13 O ring 14 Gasket 15A 1st potting cap 15B 1st potting cap 15C 1st potting cap 16 2nd potting cap 17 pin
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Abstract
Description
(1)筐体と、前記筐体内に配置される複数の中空糸膜を有する中空糸膜束と、前記複数の中空糸膜の少なくとも一方の端部において、中空糸膜が開口するように、前記中空糸膜を接着する第1ポッティング部と、前記第1ポッティング部と前記筐体との間を液密に固定するシール材と、を備えるカートリッジ式中空糸膜モジュールの製造方法であって、
(a)前記第1ポッティング部に含まれる内層ポッティング部を形成する工程と、
(b)前記第1ポッティング部に含まれ、前記内層ポッティング部を覆う外層ポッティング部を形成する工程と、
を含み、
前記工程(a)は、
(a-1)前記中空糸膜の間に前記内層ポッティング部を形成する内層ポッティング剤を充填する内層ポッティング剤配置ステップと、
(a-2)前記内層ポッティング剤を硬化させる硬化ステップと、
を備え、
前記工程(b)は、
(b-1)前記(a-2)の硬化ステップの後に、少なくとも前記第1ポッティング部が前記シール材と接する部分において、前記外層ポッティング部が前記内層ポッティング部を覆うように、前記外層ポッティング部を形成する外層ポッティング剤を静置ポッティング法にて配置する外層ポッティング剤配置ステップと、
(b-2)前記外層ポッティング剤を硬化させる硬化ステップと、
を備え、
前記内層ポッティング剤と前記外層ポッティング剤は、下記条件(p)ないし(r)を満たすエポキシ樹脂組成物である、カートリッジ式中空糸膜モジュールの製造方法。
条件(p)前記内層ポッティング部を形成するエポキシ樹脂組成物の25℃における粘度が400mPa・s以上であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg1が95℃以上160℃以下である。
条件(q)前記外層ポッティング部を形成するエポキシ樹脂組成物がシクロヘキシル環1つからなる脂環式ポリアミンを含み、25℃における粘度が1200mPa・s以下であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg2が110℃以上160℃以下である。
条件(r)前記ガラス転移温度Tg1と、前記ガラス転移温度Tg2の関係が5≦Tg2-Tg1≦20である。 In order to solve such a problem, the present invention provides the following method for manufacturing a cartridge type hollow fiber membrane module.
(1) The hollow fiber membrane is opened at at least one end of the housing, the hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and the plurality of hollow fiber membranes. A method for manufacturing a cartridge-type hollow fiber membrane module, comprising: a first potting portion for adhering the hollow fiber membrane, and a sealing material for liquid-tightly fixing between the first potting portion and the housing.
(A) A step of forming the inner layer potting portion included in the first potting portion, and
(B) A step of forming an outer layer potting portion included in the first potting portion and covering the inner layer potting portion, and a step of forming the outer layer potting portion.
Including
The step (a) is
(A-1) An inner layer potting agent placement step of filling the inner layer potting agent forming the inner layer potting portion between the hollow fiber membranes, and
(A-2) A curing step of curing the inner layer potting agent,
Equipped with
The step (b) is
(B-1) After the curing step of (a-2), the outer layer potting portion is such that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion is in contact with the sealing material. The outer layer potting agent placement step of arranging the outer layer potting agent forming the above by the static potting method, and
(B-2) A curing step of curing the outer layer potting agent,
Equipped with
A method for manufacturing a cartridge-type hollow fiber membrane module, wherein the inner layer potting agent and the outer layer potting agent are epoxy resin compositions satisfying the following conditions (p) to (r).
Condition (p) The viscosity of the epoxy resin composition forming the inner layer potting portion at 25 ° C. is 400 mPa · s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less.
Condition (q) The epoxy resin composition forming the outer layer potting portion contains an alicyclic polyamine composed of one cyclohexyl ring, the viscosity at 25 ° C. is 1200 mPa · s or less, and the glass of the cured product of the epoxy resin composition. The transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower.
Condition (r) The relationship between the glass transition temperature Tg1 and the glass transition temperature Tg2 is 5 ≦ Tg2-Tg1 ≦ 20.
(3)前記外層ポッティング部における、硬化発熱量Q2×エポキシ質量W2が400kJ以下である、上記(1)または(2)に記載のカートリッジ式中空糸膜モジュールの製造方法。
(4)前記内層ポッティング部を形成するエポキシ樹脂組成物の硬化発熱量が350mJ/mg以下である、上記(1)から(3)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(5)前記内層ポッティング部における、硬化発熱量Q1×エポキシ質量W1が500kJ以下である、上記(1)から(4)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(6)前記外層ポッティング部を形成するエポキシ樹脂組成物がアルキレングリコール構造を有する脂肪族ポリアミンを含む、上記(1)から(5)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(7)前記外層ポッティング部の全脂肪族アミン系硬化剤成分に対して、前記シクロヘキシル環1つからなる脂環式ポリアミンを50質量%以上90質量%以下含有する、上記(1)から(6)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(8)前記外層ポッティング部を形成するエポキシ樹脂組成物に含まれる前記シクロヘキシル環1つからなる脂環式ポリアミンが、イソホロンジアミン、シクロヘキサンジアミンおよび1,3-ビスアミノメチルシクロヘキサンからなる群から選ばれる、上記(1)から(7)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(9)前記外層ポッティング部を形成するエポキシ樹脂組成物がイソホロンジアミンを含む、上記(8)に記載のカートリッジ式中空糸膜モジュールの製造方法。
(10)前記内層ポッティング部を形成するエポキシ樹脂組成物がシクロヘキシル環を2つ以上含有する脂環式ポリアミンを含む、上記(1)から(9)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。
(11)前記外層ポッティング部を形成するエポキシ樹脂組成物100質量部中、ビスフェノールA型エポキシ樹脂を40質量部以上80質量部以下、ビスフェノールF型エポキシ樹脂を20質量部以上60質量部以下含む、上記(1)から(10)のいずれか1つに記載のカートリッジ式中空糸膜モジュールの製造方法。 (2) The method for manufacturing a cartridge-type hollow fiber membrane module according to (1) above, wherein the epoxy resin composition forming the outer layer potting portion has a curing calorific value of 1000 mJ / mg or less.
(3) The method for manufacturing a cartridge-type hollow fiber membrane module according to (1) or (2) above, wherein the curing calorific value Q2 × epoxy mass W2 in the outer layer potting portion is 400 kJ or less.
(4) Manufacture of the cartridge-type hollow fiber membrane module according to any one of (1) to (3) above, wherein the epoxy resin composition forming the inner layer potting portion has a curing calorific value of 350 mJ / mg or less. Method.
(5) The method for manufacturing a cartridge-type hollow fiber membrane module according to any one of (1) to (4) above, wherein the curing calorific value Q1 × epoxy mass W1 in the inner layer potting portion is 500 kJ or less.
(6) The cartridge-type hollow fiber membrane module according to any one of (1) to (5) above, wherein the epoxy resin composition forming the outer layer potting portion contains an aliphatic polyamine having an alkylene glycol structure. Method.
(7) From (1) to (6) above, the alicyclic polyamine composed of one cyclohexyl ring is contained in an alicyclic polyamine of 50% by mass or more and 90% by mass or less with respect to the total aliphatic amine-based curing agent component of the outer layer potting portion. ). The method for manufacturing a cartridge type hollow fiber membrane module according to any one of the above.
(8) The alicyclic polyamine composed of one cyclohexyl ring contained in the epoxy resin composition forming the outer layer potting portion is selected from the group consisting of isophoronediamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane. , The method for manufacturing a cartridge type hollow fiber membrane module according to any one of (1) to (7) above.
(9) The method for manufacturing a cartridge-type hollow fiber membrane module according to (8) above, wherein the epoxy resin composition forming the outer layer potting portion contains isophorone diamine.
(10) The cartridge-type hollow fiber according to any one of (1) to (9) above, wherein the epoxy resin composition forming the inner layer potting portion contains an alicyclic polyamine containing two or more cyclohexyl rings. How to manufacture a membrane module.
(11) In 100 parts by mass of the epoxy resin composition forming the outer layer potting portion, 40 parts by mass or more and 80 parts by mass or less of the bisphenol A type epoxy resin and 20 parts by mass or more and 60 parts by mass or less of the bisphenol F type epoxy resin are contained. The method for manufacturing a cartridge type hollow thread film module according to any one of (1) to (10) above.
また、本明細書において、「質量」は「重量」と同義である。 The manufacturing method of the cartridge type hollow fiber membrane module of the present invention (hereinafter, also referred to as “the manufacturing method of the present invention”) will be described with reference to the drawings. In the present specification, the directions such as "up" and "down" are based on the states shown in the drawings and are for convenience. The outflow side is the "upward" direction. Normally, in the posture when the cartridge type hollow fiber membrane module is used, the vertical direction thereof coincides with the vertical direction in the drawing.
Further, in the present specification, "mass" is synonymous with "weight".
(a)第1ポッティング部に含まれる内層ポッティング部を形成する工程
(b)第1ポッティング部に含まれ、内層ポッティング部を覆う外層ポッティング部を形成する工程 The hollow
(A) Step of forming the inner layer potting portion included in the first potting portion (b) Step of forming the outer layer potting portion included in the first potting portion and covering the inner layer potting portion.
<<工程(a)>>
本発明の製造方法では、図3に示すように、まず、複数の中空糸膜1を含む中空糸膜束2を第1ポッティングキャップ15Aに挿入し、内層ポッティング剤を供給し、内層ポッティング部9Aを形成する(ステップS1)。図1においては第1ポッティング部9は上端に示すが、図3においては静置ポッティングする際と同様、下向きに示す。なお、第1ポッティングキャップ15Aに挿入される側の中空糸膜の端部(以下、「第1端部」ともいう。)は、予めシリコーン接着剤で目止め処理されている。目止め処理を行うと、それ以上中空部にポッティング剤が侵入することを防ぎ、中空部がポッティング剤で満たされてろ過液が出なくなる不通糸の発生を防止することができる。第1ポッティングキャップ15Aにはポッティング剤投入のためのポンプが接続されており、ポンプにより内層形成用のポッティング剤(内層ポッティング剤)を第1ポッティングキャップ15Aに供給することができる。 <Formation of the first potting part>
<< Process (a) >>
In the manufacturing method of the present invention, as shown in FIG. 3, first, the hollow
続いて、内層ポッティング部を覆う外層ポッティング部を形成する。
外層ポッティング部を形成する工程は、工程(a)の硬化ステップの後に、少なくとも第1ポッティング部が後述するシール材と接する部分において、外層ポッティング部が内層ポッティング部を覆うように、外層ポッティング部を形成する外層ポッティング剤を静置ポッティング法にて配置する外層ポッティング剤配置ステップ(工程(b-1))と、そのポッティング剤を硬化させる硬化ステップ(工程(b-2))とを含む。 << Process (b) >>
Subsequently, an outer layer potting portion that covers the inner layer potting portion is formed.
In the step of forming the outer layer potting portion, after the curing step of the step (a), the outer layer potting portion is formed so that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion contacts the sealing material described later. It includes an outer layer potting agent placement step (step (b-1)) in which the outer layer potting agent to be formed is placed by a static potting method, and a curing step (step (b-2)) in which the potting agent is cured.
上記で第1ポッティング部9が形成された側とは反対側の中空糸膜1の端部(以下、「第2端部」ともいう。)は、図5に示すように第2ポッティング部ケース11に挿入されている。ここで第2ポッティング部ケース11底部の貫通孔にピン17が挿入されており、第2ポッティングキャップ16の内部に第2ポッティング部ケース11とピン17が収められている。この状態で静置ポッティングを行い、第2ポッティング部10を形成させる(ステップS5)。このとき中空糸膜1の第2端部の中空部はポッティング剤で封止される。その後、第2ポッティング部10の硬化を完了させる(ステップS6)。硬化をさせる際は反応を促進するため熱処理を行ってもよい。 <Formation of the second potting part>
As shown in FIG. 5, the end portion of the hollow fiber membrane 1 (hereinafter, also referred to as “second end portion”) on the side opposite to the side on which the
図7に示したように、カートリッジ式中空糸膜モジュール101Aは、筐体と、筐体内に収容された図1に示した中空糸膜カートリッジ100とを備える。 <Module structure>
As shown in FIG. 7, the cartridge type hollow
図1に示したように、中空糸膜カートリッジ100は、複数の中空糸膜1を含む中空糸膜束2と、中空糸膜束2の両端に設けられ、中空糸膜1間を接着するポッティング部とを備える。ポッティング部として、中空糸膜カートリッジ100は、筐体のろ過液出口7側に配置される第1ポッティング部9と、筐体の原液流入口6側に配置される第2ポッティング部10とを有する。 <Hollow fiber membrane cartridge>
As shown in FIG. 1, the hollow
筐体のろ過液出口7側、つまり中空糸膜カートリッジ100の上端側に配置される第1ポッティング部9は、中空糸膜束2の第1端部において、中空糸膜1間を接着するポッティング剤で形成されている。 <1st potting part>
The
本実施形態の内層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度(以下、Tg1とする)および外層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度(以下、Tg2とする)は下記式(i)を満たす(条件(r))。
5≦Tg2-Tg1≦20 ・・・(i) An epoxy resin composition is used as the potting agent for forming the inner layer potting portion and the outer layer potting portion.
The glass transition temperature of the cured product of the epoxy resin composition forming the inner layer potting portion of the present embodiment (hereinafter referred to as Tg1) and the glass transition temperature of the cured product of the epoxy resin composition forming the outer layer potting portion (hereinafter referred to as Tg2). Satisfies the following equation (i) (condition (r)).
5 ≦ Tg2-Tg1 ≦ 20 ・ ・ ・ (i)
本実施形態の内層ポッティング部を形成するエポキシ樹脂組成物の硬化発熱量Q1は350mJ/mg以下が好ましい。エポキシ樹脂組成物の硬化発熱量を350mJ/mg以下とすることで、エポキシ樹脂組成物の硬化発熱による樹脂の温度上昇を抑制することができ、ポリマー製の中空糸膜が硬化発熱によって劣化することなくポッティング部を硬化形成することができる。エポキシ樹脂組成物の硬化発熱量は、280mJ/mg以下がより好ましい。ここで硬化発熱量の測定方法は示差走査熱量測定(DSC)にて行う。 <Inner layer potting part of the first potting part>
The curing calorific value Q1 of the epoxy resin composition forming the inner layer potting portion of the present embodiment is preferably 350 mJ / mg or less. By setting the curing heat generation amount of the epoxy resin composition to 350 mJ / mg or less, it is possible to suppress the temperature rise of the resin due to the curing heat generation of the epoxy resin composition, and the hollow filament film made of the polymer is deteriorated by the curing heat generation. The potting portion can be hardened and formed without any problem. The curing calorific value of the epoxy resin composition is more preferably 280 mJ / mg or less. Here, the method for measuring the calorific value of curing is differential scanning calorimetry (DSC).
本発明における粘度は、標準コーンローター(1°34’×R24)を装備したE型粘度計(東機産業(株)製、TVE-30H)を用い、JISZ8803(1991)における「円すい-板形回転粘度計による粘度測定方法」に従い、測定温度25℃で測定する。本発明の粘度は、測定開始から1分後の粘度とする。 By setting the viscosity to 400 mPa · s or more, over-penetration can be suppressed. Hyperpermeation refers to a phenomenon in which the epoxy resin composition permeates through the pores from the outside of the hollow fiber membrane to the hollow portion side to close the hollow portion, and when hyperpermeation occurs in the first potting portion, filtration occurs. Filtration is not possible because there is no liquid flow path.
The viscosity in the present invention is "cone-plate type" in JISZ8803 (1991) using an E-type viscometer (TVE-30H manufactured by Toki Sangyo Co., Ltd.) equipped with a standard cone rotor (1 ° 34'x R24). Measure at a measurement temperature of 25 ° C. according to "Viscosity measurement method using a rotational viscometer". The viscosity of the present invention is one minute after the start of measurement.
本実施形態の外層ポッティング部を形成するエポキシ樹脂組成物は、シクロヘキシル環1つからなる脂環式ポリアミンを含み、25℃における粘度が1200mPa・s以下であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg2が110℃以上160℃以下である(条件(q))。 <Outer layer potting part of the first potting part>
The epoxy resin composition forming the outer layer potting portion of the present embodiment contains an alicyclic polyamine composed of one cyclohexyl ring, has a viscosity at 25 ° C. of 1200 mPa · s or less, and is a glass of a cured product of the epoxy resin composition. The transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower (condition (q)).
[A]ビスフェノール型エポキシ樹脂
[B]脂肪族アミン系硬化剤 The epoxy resin composition forming the outer layer potting portion is preferably an epoxy resin composition containing at least the following component [A] and the following component [B].
[A] Bisphenol type epoxy resin [B] Aliphatic amine-based curing agent
[A1]ビスフェノールF型エポキシ樹脂 This embodiment preferably includes the following component [A1] as the component [A].
[A1] Bisphenol F type epoxy resin
本実施様態は、第1ポッティング部の対向面に中空糸膜を封止した状態で束ねる第2ポッティング部を備え、第2ポッティング部は中空糸膜とポッティング剤で形成されている。 <Second potting part>
This embodiment includes a second potting portion that bundles the hollow fiber membrane in a sealed state on the facing surface of the first potting portion, and the second potting portion is formed of the hollow fiber membrane and the potting agent.
本実施形態のカートリッジ式中空糸膜モジュールは、分離膜として、中空糸膜を備える。中空糸膜の構造としては、全体的に孔径が一様な対称膜や、膜の厚み方向で孔径が変化する非対称膜、強度を保持するための支持膜層と対象物質の分離を行うための分離機能層を有する複合膜などが存在する。 <Hollow fiber membrane>
The cartridge type hollow fiber membrane module of the present embodiment includes a hollow fiber membrane as a separation membrane. The structure of the hollow fiber membrane is a symmetric membrane with a uniform pore diameter as a whole, an asymmetric membrane whose pore diameter changes in the thickness direction of the membrane, and a support membrane layer for maintaining strength and a target substance for separation. There is a composite membrane or the like having a separating functional layer.
カートリッジ式中空糸膜モジュールで使用するOリングやガスケットなどのシール材の材質は耐熱性、化学的耐久性などを満たせば特に限定されないが、例えばフッ素ゴム、シリコーンゴム、エチレンプロピレンジエンゴム(EPDM)などを使用することができる。 <Seal material>
The material of the sealing material such as the O-ring and the gasket used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororubber, silicone rubber, ethylene propylene diene rubber (EPDM) Etc. can be used.
カートリッジ式中空糸膜モジュールで使用する筐体の材質は耐熱性、化学的耐久性などを満たせば特に限定されないが、例えばポリスルホン系樹脂、ポリテトラフルオロエチレン、ペルフルオロアルコキシフッ素樹脂などのフッ素系樹脂、ポリカーボネート、ポリプロピレン、ポリメチルペンテン、ポリフェニレンサルファイド、ポリエーテルケトン、ステンレス、アルミニウムなどを挙げることができる。またカートリッジ式中空糸膜モジュールで使用する筒状ケースおよび第2ポッティング部ケースの材質は特に限定されないが、例えば筐体と同様の材料から選択することができる。 <Material of housing and cylindrical case>
The material of the housing used in the cartridge type hollow thread film module is not particularly limited as long as it satisfies heat resistance, chemical durability, etc., but for example, fluororesins such as polysulfone resin, polytetrafluoroethylene, perfluoroalkoxy fluororesin, etc. Examples thereof include polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, and aluminum. The material of the tubular case and the second potting portion case used in the cartridge type hollow fiber membrane module is not particularly limited, but can be selected from, for example, the same materials as the housing.
<使用した材料>
・構成要素[A1]:ビスフェノールF型エポキシ樹脂
・“jER(登録商標)”806(液状ビスフェノールF型エポキシ樹脂、三菱ケミカル(株)製)
・構成要素[A1]以外のビスフェノール型エポキシ樹脂(構成要素[A])
・“jER(登録商標)”828(液状ビスフェノールA型エポキシ樹脂、三菱ケミカル(株)製)
・構成要素[B]:脂肪族アミン系硬化剤
[B]-1“JEFFAMINE(登録商標)”D230(ポリエーテルアミン、ハンツマン・ジャパン(株)製)、
[B]-2“JEFFAMINE(登録商標)”D400(ポリエーテルアミン、ハンツマン・ジャパン(株)製)、
[B]-3“Baxxodur(登録商標)”EC201(イソホロンジアミン、BASFジャパン(株)製)、
[B]-4“Baxxodur(登録商標)”EC331(3,3’-ジメチル-4,4’-ジアミノジシクロヘキシルメタン、BASFジャパン(株)製)
・構成要素[A]以外のエポキシ樹脂
・“デナコール(登録商標)”EX-141(フェニルグリシジルエーテル、ナガセケムテックス(株)製)
・“デナコール(登録商標)”EX-142(o-フェニルフェノールグリシジルエーテル、ナガセケムテックス(株)製) The components used in this embodiment are as follows.
<Material used>
-Component [A1]: Bisphenol F type epoxy resin-"jER (registered trademark)" 806 (liquid bisphenol F type epoxy resin, manufactured by Mitsubishi Chemical Corporation)
-Bisphenol type epoxy resin other than the component [A1] (component [A])
・ "JER (registered trademark)" 828 (liquid bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation)
-Component [B]: Aliphatic amine-based curing agent [B] -1 "JEFFAMIN (registered trademark)" D230 (polyetheramine, manufactured by Huntsman Japan Corporation),
[B] -2 "JEFFAMIN (registered trademark)" D400 (polyetheramine, manufactured by Huntsman Japan Corporation),
[B] -3 "Baxxodur (registered trademark)" EC201 (isophorone diamine, manufactured by BASF Japan Ltd.),
[B] -4 "Baxxodur (registered trademark)" EC331 (3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, manufactured by BASF Japan Ltd.)
-Epoxy resin other than the component [A] -"Denacol (registered trademark)" EX-141 (Phenylglycidyl ether, manufactured by Nagase ChemteX Corporation)
・ "Denacol (registered trademark)" EX-142 (o-phenylphenol glycidyl ether, manufactured by Nagase ChemteX Corporation)
予め40℃に加温し真空乾燥器で脱泡した構成要素[A]、[B]およびその他の成分をポリプロピレン製カップに投入し、攪拌混合機にて混合した。 <Preparation method of epoxy resin composition>
The components [A], [B] and other components that had been preheated to 40 ° C. and defoamed with a vacuum dryer were put into a polypropylene cup and mixed with a stirring mixer.
上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物の粘度を、JIS Z8803(2011)における「円錐-平板形回転粘度計による粘度測定方法」に従い、標準コーンローター(1°34’×R24)を装着したE型粘度計(東機産業(株))製、TVE-30Hを使用して、回転速度10回転/分で測定した。なお、粘度はエポキシ樹脂組成物を25℃に設定した装置に投入してから1分後の数値を読み取った。 <Viscosity measurement of epoxy resin composition>
The viscosity of the epoxy resin composition prepared according to the above <Preparation method of epoxy resin composition> is adjusted to the standard cone rotor (1 ° 34'in accordance with the "viscosity measurement method using a cone-plate type rotational viscometer" in JIS Z8803 (2011). Using a TVE-30H manufactured by an E-type viscometer (Toki Sangyo Co., Ltd.) equipped with × R24), the measurement was performed at a rotation speed of 10 rotations / minute. The viscosity was read 1 minute after the epoxy resin composition was put into an apparatus set at 25 ° C.
上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物3mgをサンプルパンに量り取り、示差走査熱量分析計(DSC-60 Plus:(株)島津製作所製)を用い、0℃から200℃まで10℃/分の等速昇温条件で測定した。硬化発熱量は、得られたDSC曲線から、JIS K0129(1994)に従い算出した。 <Measurement of curing calorific value of epoxy resin composition>
Weigh 3 mg of the epoxy resin composition prepared according to the above <Preparation method of epoxy resin composition> into a sample pan, and use a differential scanning calorimeter (DSC-60 Plus: manufactured by Shimadzu Corporation) from 0 ° C. to 200 ° C. The measurement was carried out under the condition of constant rate temperature rise up to 10 ° C./min. The calorific value of curing was calculated from the obtained DSC curve according to JIS K0129 (1994).
上記<エポキシ樹脂組成物の調製方法>に従い調製したエポキシ樹脂組成物を、真空中で脱泡した後、幅10mm、長さ80mmおよび厚み4mmにくり抜いたシリコンシートに流し込み、板状のエポキシ樹脂組成物の硬化物を得た。硬化条件は、室温で24時間静置後、100℃で5時間硬化とした。 <Method for producing a cured product of an epoxy resin composition>
The epoxy resin composition prepared according to the above <Method for preparing an epoxy resin composition> is defoamed in a vacuum and then poured into a silicon sheet hollowed out to a width of 10 mm, a length of 80 mm and a thickness of 4 mm to form a plate-shaped epoxy resin composition. A cured product was obtained. The curing conditions were that the mixture was allowed to stand at room temperature for 24 hours and then cured at 100 ° C. for 5 hours.
上記<エポキシ樹脂組成物の硬化物の作製方法>に従い作製したエポキシ樹脂組成物の硬化物から、小片(5mgから10mg)を採取し、JISK7121(1987)に従い、中間点ガラス転移温度を測定した。測定には示差走査熱量計DSC-60 Plus((株)島津製作所製)を用い、窒素ガス雰囲気下において、昇温速度10℃/分で測定した。 <Measurement method of glass transition temperature of cured product of epoxy resin composition>
Small pieces (5 mg to 10 mg) were collected from the cured product of the epoxy resin composition prepared according to the above <Method for producing a cured product of the epoxy resin composition>, and the intermediate point glass transition temperature was measured according to JIS K7121 (1987). A differential scanning calorimeter DSC-60 Plus (manufactured by Shimadzu Corporation) was used for the measurement, and the measurement was performed at a heating rate of 10 ° C./min under a nitrogen gas atmosphere.
上記<エポキシ樹脂組成物の硬化物の作製方法>の方法で作製したエポキシ樹脂組成物の硬化物を、万能材料試験機5566型(インストロン社製)を用い、JIS K7171(1994)に従って3点曲げを実施し、曲げ強度および曲げ破断ひずみを測定した。 <Measurement method of bending strength and bending breaking strain of cured product of epoxy resin composition>
Using the universal material testing machine 5566 type (manufactured by Instron), the cured product of the epoxy resin composition produced by the method of the above <Method for producing the cured product of the epoxy resin composition> was used at 3 points according to JIS K7171 (1994). Bending was performed and bending strength and bending breaking strain were measured.
実施例における中空糸膜モジュールの蒸気加熱は以下の方法で実施した。原液出口8より125℃の蒸気を供給し、原液流入口6およびろ過液出口7を開放して3分間蒸気ブローを行った。その後ろ過液出口7を閉止し、原液流入口6より下方にはスチームトラップを設置して、発生したスチームドレインを排出した。その後125℃で60分間蒸気加熱を継続した。 <Steam heating of hollow fiber membrane module>
Steam heating of the hollow fiber membrane module in the examples was carried out by the following method. Steam at 125 ° C. was supplied from the
上述の蒸気加熱を50回実施した後に、中空糸膜モジュールのシール性を評価するためのエアリークテストを実施した。原液流入口6を密閉し、ろ過液出口7を開放した状態で原液出口8より100kPaの圧縮空気を供給した。中空糸膜モジュールの原液側に存在する水がすべてろ過された後に原液出口8を密閉し、中空糸膜モジュール原液側の5分間の圧力推移を測定した。第1ポッティング部のシール性が不十分な場合、ろ過液側に空気が漏れるため、モジュール原液側の圧力が低下する。なお中空糸膜はバブルポイントが200kPa以上の中空糸膜を使用し、細孔内が水で満たされた状態のため、中空糸膜の細孔を空気が透過することはない。ここでバブルポイントとは、圧縮空気で中空糸膜に圧力をかけたときに、膜の細孔内の溶媒が押し出されて、空気が透過する圧力のことである。
エアリークがないものを「リークなし(良):A」、エアリークがあったものを「リークあり(不良):B」と評価した。 <Air leak test after steam heating>
After the above-mentioned steam heating was carried out 50 times, an air leak test for evaluating the sealing property of the hollow fiber membrane module was carried out. Compressed air of 100 kPa was supplied from the
Those without air leaks were evaluated as "no leaks (good): A", and those with air leaks were evaluated as "with leaks (bad): B".
<ポリフッ化ビニリデン精密ろ過中空糸膜の作製>
重量平均分子量41.7万のフッ化ビニリデンホモポリマー38質量部と、γ-ブチロラクトン62質量部とを混合し、160℃で溶解した。この高分子溶液を、γ-ブチロラクトン85質量%水溶液を中空部形成液体として随伴させながら、二重管の口金から吐出し、口金の30mm下方に設置した温度5℃のγ-ブチロラクトン85質量%水溶液からなる冷却浴中で凝固させて、ポリフッ化ビニリデン(以下、PVDF)精密ろ過中空糸膜を作製した。得られたPVDF中空糸膜は、外径1250μm、内径800μm、平均孔径は0.3μmであった。 (Example 1)
<Preparation of polyvinylidene fluoride microfiltration hollow fiber membrane>
38 parts by mass of vinylidene fluoride homopolymer having a weight average molecular weight of 417,000 and 62 parts by mass of γ-butyrolactone were mixed and dissolved at 160 ° C. This polymer solution was discharged from the mouthpiece of a double tube with an 85% by mass γ-butyrolactone aqueous solution as a hollow fiber forming liquid, and an 85% by mass γ-butyrolactone aqueous solution having a temperature of 5 ° C. was placed 30 mm below the mouthpiece. By coagulating in a cooling bath made of, a polyvinylidene fluoride (hereinafter referred to as PVDF) microfiltration hollow fiber membrane was prepared. The obtained PVDF hollow fiber membrane had an outer diameter of 1250 μm, an inner diameter of 800 μm, and an average pore diameter of 0.3 μm.
中空糸膜を長さ1800mmにカットし、30質量%グリセリン水溶液に1時間浸漬後、風乾した。この中空糸膜を125℃の水蒸気で1時間加熱処理した後に風乾させ、長さ1200mmにカットした。こうして得られた中空糸膜束5400本を1束に束ねた。シリコーン接着剤(東レ・ダウコーニング(株)製、SH850A/B、2剤を質量比が50:50となるように混合したもの)で中空糸膜束の第1端部側を封止した。 <Making a hollow fiber membrane cartridge>
The hollow fiber membrane was cut to a length of 1800 mm, immersed in a 30 mass% glycerin aqueous solution for 1 hour, and then air-dried. This hollow fiber membrane was heat-treated with steam at 125 ° C. for 1 hour, then air-dried, and cut into a length of 1200 mm. The 5400 hollow fiber membrane bundles thus obtained were bundled into one bundle. The first end side of the hollow fiber membrane bundle was sealed with a silicone adhesive (manufactured by Toray Dow Corning Co., Ltd., SH850A / B, which was a mixture of two agents so that the mass ratio was 50:50).
第1ポッティングキャップ15Aには1020gのポッティング剤を投入した。投入後、室温で24時間静置することにより、ポッティング剤を硬化させた。硬化後、第1ポッティングキャップ15Aを取り外し、さらに100℃で5時間の熱処理を行った。これにより第1ポッティング部9の内層ポッティング部9Aが形成された。その後サンドペーパー(#80)で内層ポッティング部9Aの表面のヤスリがけを行い、エタノールで脱脂した。 Liquid bisphenol A type epoxy resin ("jER®" 828, manufactured by Mitsubishi Chemical Corporation) and 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane ("Baxxodur®" EC331, BASF Japan Co., Ltd.) and polyetheramine ("JEFFAMIN (registered trademark)" D230) were mixed so as to have a mass ratio of 100: 19.2: 12.8. The obtained epoxy resin composition was injected into the
1020 g of a potting agent was put into the
ここで図4に示した第1ポッティングキャップ15Bの最小内径部は149.3mm、最大内径部は167mmである。第1ポッティングキャップ15Bの最小内径部はOリングシール面形成部である。また第1ポッティングキャップ15Cの最大外径部は外層ポッティング部の鍔部9Cの形成部である。 Subsequently, the inner
Here, the minimum inner diameter portion of the
続いて第1ポッティング部にOリングを取り付け、作製した中空糸膜カートリッジを図7に示したようにステンレス製の筐体本体3(内径159.2mm)に装着し、上部キャップ4、下部キャップ5を取り付けてカートリッジ式中空糸膜モジュール101Aとした。このカートリッジ式中空糸膜モジュール101Aにエタノールを送液した後に、続いて水を送液した。 <Evaluation of sealing performance of cartridge type hollow fiber membrane module>
Subsequently, an O-ring is attached to the first potting portion, and the produced hollow fiber membrane cartridge is attached to the stainless steel housing body 3 (inner diameter 159.2 mm) as shown in FIG. 7, and the
外層ポッティング部および内層ポッティング部の樹脂組成をそれぞれ表1に示した通りとし、実施例1と同じ方法で中空糸膜カートリッジを作製した。評価結果は表1に示した。
外層ポッティング部の25℃における粘度はいずれの実施例も1200mPa・s以下であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg2はいずれも110℃以上、160℃以下の範囲に含まれており、条件(q)を満たしていた。さらに、Tg2とTg1の差はいずれも5℃以上15℃以下であり、条件(r)を満たしていた。得られた中空糸膜カートリッジは、いずれも実施例1と同様、耐熱性、外層ポッティング部の気泡抜け性ともに良好であった。また、得られたカートリッジ式中空糸膜モジュールのシール性も良好であった。 (Examples 2 to 5)
The resin compositions of the outer layer potting portion and the inner layer potting portion were set as shown in Table 1, respectively, and a hollow fiber membrane cartridge was produced by the same method as in Example 1. The evaluation results are shown in Table 1.
The viscosity of the outer layer potting portion at 25 ° C. was 1200 mPa · s or less in all the examples, and the glass transition temperature Tg2 of the cured product of the epoxy resin composition was contained in the range of 110 ° C. or higher and 160 ° C. or lower. , The condition (q) was satisfied. Further, the difference between Tg2 and Tg1 was 5 ° C. or higher and 15 ° C. or lower, satisfying the condition (r). All of the obtained hollow fiber membrane cartridges had good heat resistance and air bubble removal property of the outer layer potting portion, as in Example 1. In addition, the sealing performance of the obtained cartridge-type hollow fiber membrane module was also good.
外層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同じ方法で中空糸膜カートリッジを作製した。外層ポッティング部を形成するエポキシ樹脂組成物の粘度が1420mPa・sと高く、外層ポッティング部に気泡が残存した。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。外層ポッティング部に残存した気泡によりOリングシール部のシール性が低下しリークが発生した。 (Comparative Example 1)
A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2. The viscosity of the epoxy resin composition forming the outer layer potting portion was as high as 1420 mPa · s, and bubbles remained in the outer layer potting portion. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. The air bubbles remaining in the outer layer potting portion deteriorated the sealing property of the O-ring seal portion and caused a leak.
内層ポッティング部の樹脂組成を表2に示したように変更し、内層ポッティング部のみで第1ポッティング部を作製した。内層ポッティング部を形成するエポキシ樹脂組成物の硬化発熱量は、325mJ/mgと大きく、硬化時に達したエポキシ樹脂組成物の最高発熱温度が214℃となり、中空糸膜モジュール100Aのポリフッ化ビニリデン製中空糸膜1が溶解した。 (Comparative Example 2)
The resin composition of the inner layer potting portion was changed as shown in Table 2, and the first potting portion was prepared only by the inner layer potting portion. The calorific value of curing of the epoxy resin composition forming the inner layer potting portion is as large as 325 mJ / mg, the maximum calorific value of the epoxy resin composition reached at the time of curing is 214 ° C., and the hollow fiber membrane module 100A is made of polyvinylidene fluoride. The
内層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同じ方法で中空糸膜カートリッジを作製した。内層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度Tg1は47℃であった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際にエポキシ樹脂の強度が著しく低下しリークが発生した。 (Comparative Example 3)
A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2. The glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 47 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. When steam heating was performed, the strength of the epoxy resin was significantly reduced and a leak occurred.
内層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同じ方法で中空糸膜カートリッジを作製した。内層ポッティング部を形成するエポキシ樹脂組成物の25℃における粘度が320mPa・sと低く、過浸透が発生したため、ろ過ができなかった。 (Comparative Example 4)
A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2. The epoxy resin composition forming the inner layer potting portion had a low viscosity of 320 mPa · s at 25 ° C., and over-penetration occurred, so that filtration could not be performed.
外層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同様の方法で中空糸膜カートリッジを作製した。外層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度Tg2は47℃であった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際にエポキシ樹脂の強度が著しく低下しリークが発生した。 (Comparative Example 5)
A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2. The glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting portion was 47 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. When steam heating was performed, the strength of the epoxy resin was significantly reduced and a leak occurred.
内層ポッティング部および外層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同様の方法で中空糸膜カートリッジを作製した。内層ポッティング部を形成するエポキシ樹脂組成物と外層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度の差が-19℃と大きかった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際に第1ポッティング部にクラックが発生したため、リークが発生した。 (Comparative Example 6)
A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin compositions of the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2. The difference in glass transition temperature between the epoxy resin composition forming the inner layer potting portion and the cured product of the epoxy resin composition forming the outer layer potting portion was as large as -19 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. A leak occurred because a crack was generated in the first potting portion when steam heating was performed.
内層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同じ方法で中空糸膜カートリッジを作製した。内層ポッティング部を形成するエポキシ樹脂組成物の硬化物のガラス転移温度Tg1は69℃であった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際にエポキシ樹脂の強度が著しく低下しリークが発生した。 (Comparative Example 7)
A hollow fiber membrane cartridge was produced by the same method as in Example 1 except that the resin composition of the inner layer potting portion was changed as shown in Table 2. The glass transition temperature Tg1 of the cured product of the epoxy resin composition forming the inner layer potting portion was 69 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. When steam heating was performed, the strength of the epoxy resin was significantly reduced and a leak occurred.
外層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同様の方法で中空糸膜カートリッジを作製した。外層ポッティング剤を形成するエポキシ樹脂組成物の硬化物のガラス転移温度Tg2は69℃であった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際にエポキシ樹脂の強度が著しく低下しリークが発生した。 (Comparative Example 8)
A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2. The glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 69 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. When steam heating was performed, the strength of the epoxy resin was significantly reduced and a leak occurred.
内層ポッティング部と外層ポッティング部の樹脂量を表2に示したように変更した以外は、実施例1と同様の方法で中空糸膜カートリッジを作製した。外層ポッティング部を形成するエポキシ樹脂組成物のQ2×W2値は729kJと大きく、硬化時に達したエポキシ樹脂組成物の最高発熱温度が260℃となり、ポリアセタール製のポッティングケースが変形するとともに、内層ポッティング部の中空糸膜が一部溶融した。 (Comparative Example 9)
A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the amounts of resin in the inner layer potting portion and the outer layer potting portion were changed as shown in Table 2. The Q2 × W2 value of the epoxy resin composition forming the outer layer potting portion is as large as 729 kJ, and the maximum heat generation temperature of the epoxy resin composition reached at the time of curing becomes 260 ° C., the polyacetal potting case is deformed, and the inner layer potting portion is formed. The hollow fiber membrane of the above was partially melted.
外層ポッティング部の樹脂組成を表2に示したように変更した以外は、実施例1と同様の方法で中空糸膜カートリッジを作製した。外層ポッティング剤を形成するエポキシ樹脂組成物の硬化物のガラス転移温度Tg2は107℃であった。得られたカートリッジ式中空糸膜モジュールのエアリークテストを行った結果、圧力の低下は5分間で100kPaだった。蒸気加熱を行った際にエポキシ樹脂の強度が著しく低下しリークが発生した。 (Comparative Example 10)
A hollow fiber membrane cartridge was produced in the same manner as in Example 1 except that the resin composition of the outer layer potting portion was changed as shown in Table 2. The glass transition temperature Tg2 of the cured product of the epoxy resin composition forming the outer layer potting agent was 107 ° C. As a result of an air leak test of the obtained cartridge type hollow fiber membrane module, the decrease in pressure was 100 kPa in 5 minutes. When steam heating was performed, the strength of the epoxy resin was significantly reduced and a leak occurred.
101A カートリッジ式中空糸膜モジュール
1 中空糸膜
2 中空糸膜束
3 筐体本体
3A 鍔部
3B 鍔部
4 上部キャップ
4A 段部
5 下部キャップ
6 原液流入口
7 ろ過液出口
8 原液出口
9 第1ポッティング部
9A 内層ポッティング部
9B 外層ポッティング部
9C 鍔部
9D 段部
10 第2ポッティング部
11 第2ポッティング部ケース
12 貫通孔
13 Oリング
14 ガスケット
15A 第1ポッティングキャップ
15B 第1ポッティングキャップ
15C 第1ポッティングキャップ
16 第2ポッティングキャップ
17 ピン 100 Hollow
Claims (11)
- 筐体と、前記筐体内に配置される複数の中空糸膜を有する中空糸膜束と、前記複数の中空糸膜の少なくとも一方の端部において、中空糸膜が開口するように、前記中空糸膜を接着する第1ポッティング部と、前記第1ポッティング部と前記筐体との間を液密に固定するシール材と、を備えるカートリッジ式中空糸膜モジュールの製造方法であって、
(a)前記第1ポッティング部に含まれる内層ポッティング部を形成する工程と、
(b)前記第1ポッティング部に含まれ、前記内層ポッティング部を覆う外層ポッティング部を形成する工程と、
を含み、
前記工程(a)は、
(a-1)前記中空糸膜の間に前記内層ポッティング部を形成する内層ポッティング剤を充填する内層ポッティング剤配置ステップと、
(a-2)前記内層ポッティング剤を硬化させる硬化ステップと、
を備え、
前記工程(b)は、
(b-1)前記(a-2)の硬化ステップの後に、少なくとも前記第1ポッティング部が前記シール材と接する部分において、前記外層ポッティング部が前記内層ポッティング部を覆うように、前記外層ポッティング部を形成する外層ポッティング剤を静置ポッティング法にて配置する外層ポッティング剤配置ステップと、
(b-2)前記外層ポッティング剤を硬化させる硬化ステップと、
を備え、
前記内層ポッティング剤と前記外層ポッティング剤は、下記条件(p)ないし(r)を満たすエポキシ樹脂組成物である、カートリッジ式中空糸膜モジュールの製造方法。
条件(p)前記内層ポッティング部を形成するエポキシ樹脂組成物の25℃における粘度が400mPa・s以上であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg1が95℃以上160℃以下である。
条件(q)前記外層ポッティング部を形成するエポキシ樹脂組成物がシクロヘキシル環1つからなる脂環式ポリアミンを含み、25℃における粘度が1200mPa・s以下であり、エポキシ樹脂組成物の硬化物のガラス転移温度Tg2が110℃以上160℃以下である。
条件(r)前記ガラス転移温度Tg1と、前記ガラス転移温度Tg2の関係が5≦Tg2-Tg1≦20である。 The hollow fiber so that the hollow fiber membrane opens at at least one end of the housing, the hollow fiber membrane bundle having a plurality of hollow fiber membranes arranged in the housing, and the plurality of hollow fiber membranes. A method for manufacturing a cartridge-type hollow fiber membrane module, comprising: a first potting portion for adhering a membrane, and a sealing material for liquid-tightly fixing between the first potting portion and the housing.
(A) A step of forming the inner layer potting portion included in the first potting portion, and
(B) A step of forming an outer layer potting portion included in the first potting portion and covering the inner layer potting portion, and a step of forming the outer layer potting portion.
Including
The step (a) is
(A-1) An inner layer potting agent placement step of filling the inner layer potting agent forming the inner layer potting portion between the hollow fiber membranes, and
(A-2) A curing step of curing the inner layer potting agent,
Equipped with
The step (b) is
(B-1) After the curing step of (a-2), the outer layer potting portion is such that the outer layer potting portion covers the inner layer potting portion at least in the portion where the first potting portion is in contact with the sealing material. The outer layer potting agent placement step of arranging the outer layer potting agent forming the above by the static potting method, and
(B-2) A curing step of curing the outer layer potting agent,
Equipped with
A method for manufacturing a cartridge-type hollow fiber membrane module, wherein the inner layer potting agent and the outer layer potting agent are epoxy resin compositions satisfying the following conditions (p) to (r).
Condition (p) The viscosity of the epoxy resin composition forming the inner layer potting portion at 25 ° C. is 400 mPa · s or more, and the glass transition temperature Tg1 of the cured product of the epoxy resin composition is 95 ° C. or more and 160 ° C. or less.
Condition (q) The epoxy resin composition forming the outer layer potting portion contains an alicyclic polyamine composed of one cyclohexyl ring, the viscosity at 25 ° C. is 1200 mPa · s or less, and the glass of the cured product of the epoxy resin composition. The transition temperature Tg2 is 110 ° C. or higher and 160 ° C. or lower.
Condition (r) The relationship between the glass transition temperature Tg1 and the glass transition temperature Tg2 is 5 ≦ Tg2-Tg1 ≦ 20. - 前記外層ポッティング部を形成するエポキシ樹脂組成物の硬化発熱量が1000mJ/mg以下である、請求項1に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to claim 1, wherein the epoxy resin composition forming the outer layer potting portion has a curing calorific value of 1000 mJ / mg or less.
- 前記外層ポッティング部における、硬化発熱量Q2×エポキシ質量W2が400kJ以下である、請求項1または2に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to claim 1 or 2, wherein the curing calorific value Q2 × epoxy mass W2 in the outer layer potting portion is 400 kJ or less.
- 前記内層ポッティング部を形成するエポキシ樹脂組成物の硬化発熱量が350mJ/mg以下である、請求項1から3のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to any one of claims 1 to 3, wherein the epoxy resin composition forming the inner layer potting portion has a curing calorific value of 350 mJ / mg or less.
- 前記内層ポッティング部における、硬化発熱量Q1×エポキシ質量W1が500kJ以下である、請求項1から4のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to any one of claims 1 to 4, wherein the curing calorific value Q1 × epoxy mass W1 in the inner layer potting portion is 500 kJ or less.
- 前記外層ポッティング部を形成するエポキシ樹脂組成物がアルキレングリコール構造を有する脂肪族ポリアミンを含む、請求項1から5のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to any one of claims 1 to 5, wherein the epoxy resin composition forming the outer layer potting portion contains an aliphatic polyamine having an alkylene glycol structure.
- 前記外層ポッティング部の全脂肪族アミン系硬化剤成分に対して、前記シクロヘキシル環1つからなる脂環式ポリアミンを50質量%以上90質量%以下含有する、請求項1から6のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 One of claims 1 to 6, wherein the alicyclic polyamine composed of one cyclohexyl ring is contained in an amount of 50% by mass or more and 90% by mass or less with respect to the total aliphatic amine-based curing agent component of the outer layer potting portion. A method for manufacturing a cartridge-type hollow fiber membrane module according to the above.
- 前記外層ポッティング部を形成するエポキシ樹脂組成物に含まれる前記シクロヘキシル環1つからなる脂環式ポリアミンが、イソホロンジアミン、シクロヘキサンジアミンおよび1,3-ビスアミノメチルシクロヘキサンからなる群から選ばれる、請求項1から7のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 The claim that the alicyclic polyamine composed of one cyclohexyl ring contained in the epoxy resin composition forming the outer layer potting portion is selected from the group consisting of isophorone diamine, cyclohexanediamine and 1,3-bisaminomethylcyclohexane. The method for manufacturing a cartridge type hollow fiber membrane module according to any one of 1 to 7.
- 前記外層ポッティング部を形成するエポキシ樹脂組成物がイソホロンジアミンを含む、請求項8に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to claim 8, wherein the epoxy resin composition forming the outer layer potting portion contains isophorone diamine.
- 前記内層ポッティング部を形成するエポキシ樹脂組成物がシクロヘキシル環を2つ以上含有する脂環式ポリアミンを含む、請求項1から9のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 The method for manufacturing a cartridge-type hollow fiber membrane module according to any one of claims 1 to 9, wherein the epoxy resin composition forming the inner layer potting portion contains an alicyclic polyamine containing two or more cyclohexyl rings.
- 前記外層ポッティング部を形成するエポキシ樹脂組成物100質量部中、ビスフェノールA型エポキシ樹脂を40質量部以上80質量部以下、ビスフェノールF型エポキシ樹脂を20質量部以上60質量部以下含む、請求項1から10のいずれか1項に記載のカートリッジ式中空糸膜モジュールの製造方法。 Claim 1 comprises 100 parts by mass of the epoxy resin composition forming the outer layer potting portion, 40 parts by mass or more and 80 parts by mass or less of the bisphenol A type epoxy resin, and 20 parts by mass or more and 60 parts by mass or less of the bisphenol F type epoxy resin. To the method for manufacturing a cartridge type hollow thread film module according to any one of 10.
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