JP2019025420A - Hollow fiber membrane module and production method of hollow fiber membrane module - Google Patents

Abstract

To provide a hollow fiber membrane module by which problems such as the reduction of strength and heat deformation of a membrane, a cylindrical case and the like caused by heat generation during curing at an adhesive and the constituent of a binding part can be solved without using other members such as a partition plate and the like.SOLUTION: In a hollow fiber membrane module including a cylindrical case and a hollow fiber membrane bundle housed in the cylindrical case, the hollow fiber membrane bundle is bundled with at least one binding part in a state of opening one or both ends of the hollow part of the hollow fiber membrane; the glass transition temperature of the binding part is less than 80°C; and the Mc of the binding part, the weight W of the binding part and the Vicat softening temperature VST of the hollow fiber membrane are satisfied with a specific equation.SELECTED DRAWING: None

Description

  The present invention relates to a hollow fiber membrane module used in the water treatment field, fermentation industry field, pharmaceutical / medical field, food industry field, and the like, and more specifically, has a binding portion with a small amount of curing heat generated when the adhesive is cured. The present invention relates to a hollow fiber membrane module. The present invention also relates to a method for producing the hollow fiber membrane module.

  As seen in Patent Document 1, generally, a hollow fiber membrane module accommodates a hollow fiber membrane bundle in which approximately several hundred to several tens of thousands of hollow fiber membranes are bundled in a cylindrical case. At least one end is bound and accommodated in a cylindrical case.

  Here, the bound hollow fiber membrane is open at at least one end, and the hollow portion becomes a flow path of the filtrate or the liquid to be filtered. Here, the bundling portion has a function of bundling the membrane and isolating the filtrate from the filtrate. This binding part is often formed using an adhesive, and among them, urethane resin or epoxy resin is widely used.

  Patent Document 2 actively discusses application of clarification of purified water or sewage using an ultrafiltration membrane module or a microfiltration membrane module; in such a field, treatment by increasing the size of the membrane module It is thought that cost reduction is necessary; there are several problems in increasing the size of the membrane module, and one of them is that the case is deformed if the case is made of a material having low heat resistance. And the problem of this deformation is that the amount of adhesive used increases in a quadratic curve, and that the heat of curing of the adhesive also increases in proportion. ing.

  Patent Document 2 discloses a technique of providing a partition plate that divides the adhesive into small amounts as a method for suppressing the heat generated by the adhesive in a large module.

International Publication No. 2010/014010 Japanese Unexamined Patent Publication No. 2000-185220

  However, if a partition plate is used like patent document 2, the hollow fiber membrane area which can be filled in a cylindrical case will reduce, and the filtration capability of a hollow fiber membrane module will fall. Further, since the number of members increases, the manufacturing cost of the hollow fiber membrane module increases.

  The present invention has been made in view of the above-described conventional situation, and the problem of strength reduction and thermal deformation of a film, a cylindrical case, and the like due to curing heat generation of constituent components of a binding portion including an adhesive is patented. It is an object of the present invention to provide a hollow fiber membrane module that can be solved without using a separate member such as a partition plate as in Document 2.

  The inventors of the present invention have selected the glass transition temperature in a specific range of the bundling portion, Mc represented by Formula 1, and the Vicat softening temperature VST of the hollow fiber membrane to satisfy Formula 2, thereby binding the hollow fiber membrane module. A new finding was obtained that heat generation during partial curing can be suppressed and the above problems can be solved.

The present invention is based on this new knowledge and provides the following techniques (1) to (9).
(1) A cylindrical case and a hollow fiber membrane bundle accommodated in the cylindrical case, wherein the hollow fiber membrane bundle includes a plurality of hollow fiber membranes, and the hollow fiber membrane is formed by at least one binding portion. The hollow portion is bound with one end or both ends thereof open, the glass transition temperature of the binding portion is less than 80 ° C., and the binding portion Mc represented by the following formula 1 and the binding portion A hollow fiber membrane module in which the weight W and the Vicat softening temperature VST of the hollow fiber membrane satisfy the following formula 2.

Mc = 2 (1 + μ) ρRT / E (Formula 1)
μ: Poisson's ratio, ρ: density (g / m ³ ), R: gas constant (J / K / mol),
T: Absolute temperature (K), E: Storage elastic modulus (Pa)
VST ≧ 5.78 × W / Mc + 420 (Formula 2)
VST: Vicat softening temperature (K) of the hollow fiber membrane,
W: Weight (g) of one binding part with an open hollow part
(2) The hollow fiber membrane module according to (1), wherein the Mc is 1000 or more and less than 5000.
(3) The hollow fiber membrane module according to (1) or (2), wherein the binding part contains (a) an epoxy resin and (b) an amine curing agent.
(4) The hollow according to any one of (1) to (3), wherein the binding part contains (a) a bisphenol type epoxy resin and (b) a curing agent having an aliphatic amine as a main skeleton. Yarn membrane module.
(5) The above (1) to (1), wherein the binding part contains particles having an average particle size of 40 μm or less with respect to 100 g of the adhesive constituting the binding part so that the sedimentation volume is 150 or more and less than 1000 ml. The hollow fiber membrane module according to any one of 4).
(6) The hollow fiber membrane module according to any one of (1) to (5), wherein the cylindrical case and the binding portion are fixed in a liquid-tight manner with a sealing material.
(7) The above (1) to (5), comprising a second cylindrical case housed in the cylindrical case, wherein the second cylindrical case and the bundling portion are liquid-tightly fixed by a sealing material. ) The hollow fiber membrane module according to any one of the above.

  In the hollow fiber membrane module of the present invention, since the glass transition temperature of the binding part is less than 80 ° C., the amount of heat generated during the curing of the constituent parts of the binding part including the adhesive can be suppressed, and the hollow part is hollow. When the Vicat softening temperature VST of the yarn membrane satisfies the formula 2, damage to the hollow fiber membrane module due to the heat generated by curing is suppressed, whereby a high product yield can be achieved during production.

FIG. 1 is a schematic cross-sectional view of a hollow fiber membrane module 100A according to the first embodiment of the present invention. FIG. 2 is a flowchart showing an example of a manufacturing method of the hollow fiber membrane module 100A according to the first embodiment of the present invention. FIG. 3 is a centrifugal potting device used in an example of a method for manufacturing the hollow fiber membrane module 100A according to the first embodiment of the present invention. FIG. 4 is a schematic cross-sectional view of a hollow fiber membrane module 100B according to the second embodiment of the present invention. FIG. 5 is a schematic longitudinal sectional view of the first end side of the hollow fiber membrane module 100C according to the third embodiment of the present invention.

  Below, the hollow fiber membrane module form of this invention is demonstrated in detail based on figures.

  In addition, this invention is not limited by this embodiment. Further, in the hollow fiber membrane module of the present invention, “upper” and “lower” are based on the state shown in the figure and are for convenience. The side where the filtrate flows out is the “up” direction.

Also, the direction from “down” to “up” is expressed as “height direction” for convenience. Usually, in the posture when the hollow fiber membrane module is used, the vertical direction coincides with the vertical direction in the figure.
[First Embodiment]
The configuration of the hollow fiber membrane module according to the first embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic longitudinal sectional view of an external pressure type hollow fiber membrane module 100A according to the first embodiment of the present invention.
<Hollow fiber membrane module structure>
The hollow fiber membrane module 100A according to the first embodiment includes a cylindrical case 1 having a first end and a second end in the height direction, and is accommodated in the cylindrical case 1, and an end portion on the first end side is A hollow fiber membrane bundle 12 having a plurality of hollow fiber membranes 2 that are open and closed on the second end side, and a first binding portion 3 that binds the end portions on the first end side of the hollow fiber membrane 2. And a second binding portion 4 for binding the end portion on the second end side.

  The cylindrical case 1 includes a hollow cylindrical case main body 1 and an upper cap 6 and a lower cap 7 provided at both ends of the cylindrical case main body 1.

  As shown in FIG. 1, an upper cap 6 having a filtrate outlet 8 is provided at the upper part of the cylindrical case body 1, and a lower cap 7 having a filtrate inlet 9 is provided at the lower part of the cylindrical case body 1. Are connected in a liquid-tight and air-tight manner. The upper cap 6 and the lower cap 7 use, for example, a gasket 10 as shown in FIG. 1 and are fixed to the cylindrical case body 1 with a clamp or the like.

  The cylindrical case main body 1 has a flange 1A and a flange 1B over the entire circumference of the cylindrical case main body 1 at its upper and lower ends. Further, a filtrate outlet 11 is provided near the filtrate outlet 8 on the side of the cylindrical case body 1.

  The upper cap 6 has an inner diameter substantially equal to the inner diameter of the cylindrical case body 1, and the upper end side thereof is reduced in diameter to form the filtrate outlet 8. On the lower end side of the upper cap 6, a step portion 6 </ b> A for forming a groove when connected to the cylindrical case body 1 is formed over the entire circumference of the upper cap 6.

  The lower cap 7 has an inner diameter that is substantially equal to the inner diameter of the cylindrical case body 1, and the lower end side of the lower cap 7 has a reduced diameter to form a filtrate inlet 9.

  Furthermore, the hollow fiber membrane module 100 </ b> A includes a hollow fiber membrane bundle 12 including a plurality of hollow fiber membranes 2, and a bundling portion that binds the hollow fiber membranes 2 at the end of the hollow fiber membrane bundle 12. The binding portion includes a first binding portion 3 disposed on the filtrate outlet 8 side of the cylindrical case 1 and a second binding portion 4 disposed on the filtrate inlet 9 side of the cylindrical case 1. The second binding part 4 is provided with holes 5 that serve as a flow path for the liquid to be filtered.

Further, the hollow fiber membrane module 100A is disposed between the tubular case 1 and the hollow fiber membrane bundle 12 so as to be aligned in the radial direction of the filtrate outlet 11 and the tubular case 1, and has a plurality of side surfaces. A second cylindrical case 15 having a rectifying hole 14, and the second cylindrical case 15 is fixed to the first end side of the cylindrical case 1.
<Hollow fiber membrane>
The hollow fiber membrane module of this embodiment includes a hollow fiber membrane 2 as a separation membrane. A hollow fiber membrane is advantageous because it generally has a specific surface area larger than that of a flat membrane and a larger amount of liquid can be filtered per unit time. The structure of the hollow fiber membrane includes a symmetrical membrane with a uniform pore size as a whole, an asymmetric membrane whose pore size changes in the thickness direction of the membrane, and a separation for separating the support layer and the target substance to maintain strength. There are composite films having a functional layer.

  The average pore diameter of the hollow fiber membrane may be appropriately selected depending on the separation target, but is preferably 10 nm or more and 600 nm or less for the purpose of separation of microorganisms such as bacteria and fungi and animal cells. By setting the average pore size to 10 nm or more, high water permeability can be obtained, and by setting the average pore size to 600 nm or less, the possibility that microorganisms and the like leak to the filtrate can be suppressed. The average pore size in the present invention is the pore size of the dense layer having the smallest pore size.

  The material of the hollow fiber membrane is not particularly limited. Examples of the hollow fiber membrane include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, tetrafluoroethylene / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene. Contains fluororesins such as copolymers, cellulose esters such as cellulose acetate, cellulose acetate propionate, and cellulose acetate butyrate, polysulfone resins such as polysulfone and polyethersulfone, and resins such as polyacrylonitrile, polyimide, and polypropylene be able to.

  In particular, hollow fiber membranes made of fluororesin or polysulfone resin have high heat resistance, physical strength, and chemical durability. Therefore, fermentation industry, pharmaceutical manufacturing, food industry, water treatment that require hot water sterilization. It can be suitably used for a hollow fiber membrane module in a field or the like.

  The hollow fiber membrane may further contain a hydrophilic resin in addition to the fluorine-based resin or the polysulfone-based resin. The hydrophilic resin can increase the hydrophilicity of the hollow fiber membrane and improve the water permeability of the membrane.

  The hydrophilic resin may be any resin as long as it can impart hydrophilicity to the hollow fiber membrane, and is not limited to a specific compound. For example, cellulose ester, fatty acid vinyl ester, vinyl pyrrolidone, ethylene oxide , Propylene oxide, polymethacrylic acid ester resin, polyacrylic acid ester resin and the like are preferably used.

  When producing a hollow fiber membrane module, the hollow fiber membrane is bound by a binding portion containing an adhesive as a main component. In that case, the hollow fiber membrane is filled in the binding portion forming jig and fixed by forming the binding portion, but the hollow fiber membrane is dried in advance for handling and adhesion problems.

  However, most of the hollow fiber membranes have a problem that shrinkage occurs due to drying and water permeability is lowered. Therefore, a hollow fiber membrane is used after being dipped in an aqueous glycerin solution. When dried after immersing in an aqueous glycerin solution, glycerin remains in the pores, so that shrinkage due to drying can be prevented, and water permeability can be restored by performing immersion treatment with a solvent such as ethanol after that. .

  It is preferable that the area occupied by the hollow fiber membrane is 30% or more and less than 90% in the cross section in the direction perpendicular to the cylindrical case of the first bundling portion to be described later.

  If it is 30% or more, the membrane area per unit volume is large, and the production cost per membrane area can be reduced. Further, when the first bundling part is formed, heat generated by the curing reaction of the bundling part can be radiated by the hollow fiber membrane, and an excessive temperature rise can be suppressed.

  By making it less than 90%, it is possible to prevent the hollow fiber membranes from being pressed and crushed when the hollow fiber membrane module is manufactured.

  The hollow fiber membrane module can be used after being sterilized with hot water or used for filtration of hot water, but depending on the type of the hollow fiber membrane, contraction may occur due to contact with hot water. Therefore, if hot water sterilization or hot water filtration is performed after the hollow fiber membrane module is manufactured, the hollow fiber membrane may be damaged due to shrinkage of the hollow fiber membrane, or the hollow fiber membrane may fall off from the binding portion. Therefore, it is desirable to manufacture the hollow fiber membrane module by treating the hollow fiber membrane with steam treatment or warm water in advance and shrinking it before end binding.

  Hot water sterilization is generally performed at about 80 ° C., but the temperature is often changed depending on the process. Therefore, it is desirable to treat the hollow fiber membrane in advance with warm water that is higher than the assumed use temperature.

  Further, the hollow fiber membrane bundle 12 has a looseness through the binding portions 3 and 4 at both ends in view of workability for producing the hollow fiber membrane module 100A and cleanability of the hollow fiber membrane 2 in washing the hollow fiber membrane module. And is accommodated in the cylindrical case 1.

The looseness means that the length of the hollow fiber membrane 2 in the portion is longer than the linear distance from the second end side end surface of the first bundling portion 3 to the second bundling portion 4 first end side end surface. Point to.
<First binding part>
On the first end side of the cylindrical case 1, the first binding portion 3 that is the upper end side of the hollow fiber membrane module 100 </ b> A is disposed. The first bundling portion 3 is configured by bundling a hollow fiber membrane bundle 12 composed of a large number of hollow fiber membranes 2. Here, the hollow part of the hollow fiber membrane 2 is not sealed and is open, and the filtrate is taken out from the opening to the upper cap 6 side. Further, the outer diameter of the first binding portion 3 is smaller than the outer diameter of the cylindrical case 1.

  The binding portion includes an adhesive as a main component. Thereby, the hollow fiber membrane bundle 12 can be bundled. In addition, as described later, other components such as a filler, a rubber component, and rubber particles may be contained in accordance with a specific purpose.

  The binding portion needs to have a glass transition temperature of less than 80 ° C., but the glass transition temperature of the adhesive itself, which is the main component of the binding portion, is preferably less than 80 ° C.

  There are various methods for measuring the glass transition temperature. For example, differential scanning calorimetry (DSC) may be performed. The differential scanning calorimeter is commercially available, and for example, DSC-60 Plus manufactured by Shimadzu Corporation can be used. The glass transition temperature measured by this represents the glass transition temperature of the adhesive which is the main polymer component among the constituent components of the binding part. When the binding portion contains a polymer component other than the adhesive, the glass transition temperature of each polymer component is observed. In this case, since the adhesive generally occupies a majority of the binding portion composition, the glass transition temperature at which the maximum baseline shift occurs represents the glass transition temperature of the adhesive.

  It is known that the glass transition temperature of an adhesive, particularly an epoxy resin, which is a main component of the binding part, is as high as 250 ° C. depending on the selection of composition molecules. An adhesive exhibiting a high glass transition temperature has high heat resistance, but on the other hand, a high temperature is required for curing. In addition, an adhesive having a high glass transition temperature generates a large amount of heat during curing, and is particularly noticeable when curing an adhesive of several hundred grams or more.

  When the glass transition temperature is less than 80 ° C., the amount of heat generated when the bundling portion is cured can be suppressed. Especially when the hollow fiber membrane is made of a polymer, the hollow fiber membrane is not deteriorated due to the heat generated by curing. The capacity binding portion can be cured and molded. Furthermore, since the stress acting on the curing shrinkage is suppressed, it is possible to prevent the occurrence of cracks in the binding portion and the adhesion peeling when the binding portion and the case are bonded. As described above, when producing the hollow fiber membrane module, a high production yield can be achieved while suppressing damage to the hollow fiber membrane module.

  The glass transition temperature of the binding portion is more preferably 40 ° C. or higher, further preferably 50 ° C. or higher, and further preferably 60 ° C. or higher. When the glass transition temperature is in this region, it can be used for hot water filtration and hot water sterilization in addition to filtration of room temperature liquid.

  The molecular weight Mc between the cross-linking points is expressed as in the formula 1 by the classical rubber theory (Flory, PJ: Chem. Rev. 35 (1944), 51). The molecular weight between crosslinking points estimated by this method includes not only chemical bond-derived crosslinking but also physical crosslinking such as entanglement of molecular chains.

  The bundling portion preferably has an Mc expressed by the formula 1 of 1000 or more and less than 5000. When Mc is 1000 or more, curing heat generation is further suppressed, and stress acting on curing shrinkage can be suppressed. In addition, when Mc is less than 5000, it is easy to cure and form a bound portion having a suitable glass transition temperature range. Furthermore, since it is the adhesive that contributes to the curing heat generation amount of the binding part and the glass transition temperature of the binding part among the constituent parts of the binding part, it is further preferable that the Mc of the adhesive itself is 1000 or more and less than 5000. preferable.

Mc = 2 (1 + μ) ρRT / E (Formula 1)
μ: Poisson's ratio, ρ: density (g / m ³ ), R: gas constant (J / K / mol),
T: Absolute temperature (K), E: Storage elastic modulus (Pa)
The molecular weight between crosslinking points can be calculated by measuring each physical property value constituting the formula 1 by the following method. The measurement uses a cured binding part. When a hollow fiber membrane module is actually manufactured, a section can be cut out from the binding portion and measured. The Poisson's ratio can be obtained by conducting a tensile test according to JIS K 7161. The density can be determined using a pycnometer method according to JIS K0061. The storage elastic modulus can be obtained by conducting a dynamic viscoelasticity test according to JIS K 7244. In either case, the measured value above the glass transition temperature is used, and the measured temperature is substituted into Equation 1 for calculation.

  The hollow fiber membrane and the hollow fiber membrane module member such as a cylindrical case are preferably made of a heat-resistant material that can withstand hot water filtration and hot water sterilization.

  When using a polymer material that has a relatively low heat resistance compared to metals and ceramics among the heat-resistant materials, the temperature during curing of the bundling portion is less than the Vicat softening temperature of the hollow fiber membrane. Preferably there is. If the temperature during curing of the binding portion is lower than the Vicat softening temperature of the hollow fiber membrane, the polymer hollow fiber membrane can maintain strength, water permeability, and separation performance.

  The temperature during curing of the binding portion can be measured by installing a thermocouple in the hollow fiber membrane.

  Moreover, the Vicat softening temperature of the hollow fiber membrane can be measured according to JISK7206. Vicat softening temperature measuring instruments are commercially available, and for example, a 3M-2 type HDT testing apparatus manufactured by Toyo Seiki Seisakusho, etc. can be used. The Vicat softening temperature of the hollow fiber membrane may be measured by melting a raw material for producing the hollow fiber membrane or a section of the hollow fiber membrane itself, and forming it into a plate shape.

  Since the heat of the binding portion during curing is smaller in the vicinity of the center of the binding portion and the heat generation temperature becomes higher, the Vicat softening temperature of the hollow fiber membrane is preferably lower than the heat generation temperature in the vicinity of the center.

  In addition, polymer hollow fiber membranes are inferior in heat resistance to ceramic hollow fiber membranes and the like, but can be manufactured at low cost and are easily used industrially. When thermal degradation occurs in the polymer hollow fiber membrane, problems such as leakage of the liquid to be filtered occur. As a result of intensive studies, the present inventors have been able to clarify the starting principle in which leakage of the liquid to be filtered due to thermal degradation occurs in the hollow fiber membrane module.

  The heat resistance of polymer hollow fiber membranes varies depending on the material, but it is important that the vicat softening temperature of the hollow fiber membrane is higher than the curing exotherm temperature, especially in the binding portion having openings, in order to maintain the mechanical strength. is there. Then, it is found that the curing heat generation of the binding portion is related to Mc and the weight of the binding portion, and the optimum hollow fiber membrane for manufacturing the hollow fiber membrane module without deteriorating the hollow fiber membrane due to the curing heat generation. Formula 2 was derived as a selection method.

  That is, according to the present invention, the component constituting the binding portion that can achieve a desired curing heat generation temperature is calculated by first calculating Mc according to Equation 1, and further by selecting a hollow fiber membrane using Equation 2 as an index, by a hollow fiber Membrane modules can be produced with good yield without membrane degradation. On the contrary, by selecting the component constituting the binding portion using the formula 2 as an index from the bigat softening temperature of the hollow fiber membrane to be mounted on the hollow fiber membrane module, the hollow fiber membrane module can be used for the deterioration of the membrane, etc. Therefore, it is possible to produce with good yield.

VST ≧ 5.78 × W / Mc + 420 (Formula 2)
VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g) of one binding part where the hollow part is opened
Moreover, as seen in Patent Document 2, a technique for providing a partition plate that divides an epoxy resin into small portions is disclosed in order to suppress curing heat generation that causes thermal degradation of the hollow fiber membrane. However, when a partition plate is used, the hollow fiber membrane area that can be filled in the cylindrical case is reduced, and the filtration capacity of the hollow fiber membrane module is reduced. Further, since the number of members increases, the manufacturing cost of the hollow fiber membrane module increases.

  As a general method for curing a binder having a low glass transition temperature of less than 80 ° C. containing an adhesive as a main component, there is a method of reducing the crosslinking point, that is, a method of increasing Mc in the present invention. . If Mc is less than 1000, the glass transition temperature becomes high and the heat generated by curing increases, which tends to lead to deterioration of a hollow fiber membrane module member such as a hollow fiber membrane in the production process.

  When Mc is 1000 or more, it is easy to provide sufficient toughness as well as suppression of heat generation during curing. It becomes easy to implement | achieve the glass transition temperature of a more preferable temperature range because Mc is less than 5000.

  Mc is more preferably 1030 or more, and further preferably 1760 or more. Further, Mc is more preferably less than 4000, and still more preferably less than 3000.

  It becomes easy to implement | achieve the suitable glass transition temperature of a bundling part, and hardening exothermic temperature because Mc exists in this range.

  An adhesive suitably used for membrane binding of the hollow fiber membrane module is an epoxy resin or a urethane resin. Among these, epoxy resins are preferably used because of their relatively high heat resistance. In addition, urethane is more desirable for enhancing productivity because it cures quickly.

  In addition to Mc, it is preferable to control the asymmetry and flexibility of the main skeleton in order to have an appropriate glass transition temperature and suppress heat generation from curing.

  The binding part contains (a) an epoxy resin and (b) an amine curing agent, and they are mixed and cured to achieve a suitable glass transition temperature for the binding part and suppression of heat generation by curing. Cheap.

  (A) The epoxy resin is more preferably (a) a bisphenol type epoxy resin. The (b) amine curing agent is more preferably a curing agent having (b) an aliphatic amine as a main skeleton.

  (A) The epoxy resin is more preferably a bisphenol type epoxy resin (the following formula (a)) having an epoxy equivalent of 150 or more and less than 250. The (b) amine curing agent is more preferably (b) a chain aliphatic amine. (B) The amine curing agent may contain either or both of an alicyclic amine and an aromatic amine in addition to the chain aliphatic amine as long as the target glass transition temperature can be achieved.

  In said formula (a), n is an integer greater than or equal to 0, and X is a hydrogen atom or a methyl group.

  Examples of chain aliphatic amines include diethylaminopropylamine, dipropylenediamine, triethylenetetramine, tetraethylenepentamine, and the like. When a chain aliphatic amine is used as a curing agent, the value calculated by dividing the number of epoxy groups in (a) by the number of amino groups in (b) is large, and the symmetry of the repeating unit of the cured epoxy resin is low. As a result, packing of polymer chains is difficult to occur in an orderly manner, and the glass transition temperature of the binding portion can be lowered. An amine hardening | curing agent may be used independently and may mix multiple types.

There are various types of bisphenol type epoxy resins, but bisphenol F type with X = H or bisphenol A type with X = CH ₃ is preferable because it is liquid and easy to handle.

  (A) In addition to the bisphenol-type epoxy resin (the above formula (a)) having an epoxy equivalent of 150 or more and less than 250, the epoxy resin may contain a reaction diluent or the like. The reactive diluent includes alkyl monoglycidyl ether, alkylphenol monoglycidyl ether, alkyl diglycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, 1,6-hexanediol diglycidyl ether, and the like.

  When a curing agent having a large active hydrogen equivalent is added, the value calculated by dividing the number of epoxy groups in (a) by the number of amino groups in (b) becomes smaller. And the glass transition temperature of the binding portion is lowered.

  Thus, by controlling not only the molecular weight between cross-linking points but also the asymmetry and flexibility of the main skeleton, an appropriate glass transition temperature of less than 80 ° C. and a binding part having an Mc of 1000 or more and less than 5000 can be obtained. This makes it easier to suppress the heat generated by curing the bundling portion.

  When the main component of the binding part is (a) an epoxy resin, the binding part may contain components other than (a) the epoxy resin and (b) the amine curing agent.

  For example, tertiary amines for controlling the curing reaction time of the binding part, a curing accelerator such as imidazole, a reactive diluent, a filler, or the like may be added.

  In addition, the viscosity may be adjusted in view of the fluidity between the hollow fiber membranes at the time of curing and forming the bundling part and the handling property at the time of mixing, and fillers, surfactants, silane coupling agents, etc. may be added. Also good.

  When improvement of the toughness of the cured part is a problem, rubber components and rubber particles are often added. Among these, core-shell type rubber particles are effective because they can improve toughness without impairing heat resistance.

  Fillers such as silica, talc, zeolite, calcium hydroxide, and calcium carbonate may be added for various purposes such as suppression of curing heat generation, improvement of strength, and thickening. However, the addition of a large amount is not preferable because the viscosity increases and the handleability may decrease.

  From the outside of the hollow fiber membrane to the hollow portion side, the component of the binding portion permeates through the pores and the hollow portion is blocked, and the binding portion may be excessively permeated. When excessive permeation occurs in the first binding part, the flow path of the filtrate disappears and filtration is impossible.

  In order to suppress this excessive permeation, the binding part may contain particles having an average particle size of 40 μm or less so that the sedimentation volume is 150 ml or more and less than 1000 ml with respect to 100 g of the adhesive constituting the binding part.

  More preferably, the binding part may contain particles having an average particle size of 20 μm or less so that the sedimentation volume is 200 ml or more and less than 500 ml with respect to 100 g of the adhesive constituting the binding part.

  The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring apparatus. For example, a commercially available product such as Partica mini LA-350 manufactured by Horiba, Ltd. may be used.

  The sedimentation volume can be determined as the particle volume when particles are placed in an empty graduated cylinder and allowed to stand. When the sedimentation volume is less than 150 ml, it is difficult to completely prevent the excessive penetration of the constituent components of the binding portion.

  Moreover, when the sedimentation volume is 1000 ml or more, the viscosity of the binding part to which the particles are added is high, and the fluidity between the hollow fiber membranes and the handling property at the time of mixing are impaired.

  The material of the particles to be added may satisfy the size and the sedimentation volume, but silica is preferably used because viscosity control can be easily adjusted with other components such as a silane coupling agent.

  Further, the particles to be added are dispersed in advance, for example, in any one of (a) epoxy resin and (b) amine curing agent before curing by mixing (a) epoxy resin and (b) amine curing agent. It is good to leave. Usually, by adding particles to the higher viscosity of (a) epoxy resin and (b) amine curing agent, the particles are difficult to settle in the liquid even if stored for a long time. When adjusting the viscosity by adding a silane coupling agent, it is preferable to add it in advance in the same liquid as the particles.

  The bundling portion thus obtained is a membrane cleaning chemical that is generally used in the process of using the hollow fiber membrane module, specifically, inorganic acids such as hydrochloric acid and sulfuric acid, acetic acid, citric acid, lactic acid, etc. Chemical durability to organic acids, alkalis such as sodium hypochlorite, sodium hydroxide and sodium carbonate, and reducing agents such as sodium hydrogen sulfite is also high. Therefore, even when this hollow fiber membrane module is used in the fields of food, biotechnology, medicine, etc., there are few concerns about the eluate.

  The first bundling portion is usually formed in a shape close to a cylinder, but may be a shape close to a rectangular parallelepiped or a cube. A shape close to a cylinder is preferable because the case can be easily formed into a cylindrical shape and easily connected to a pipe for transferring raw water or the like. The first bundling portion formed in a columnar shape preferably has an outer diameter of 70 mm or more and less than 250 mm. By being 70 mm or more, the film area per apparatus volume can be increased, and the apparatus manufacturing cost per film area can be suppressed.

  Since the bundling portion obtained by the above method suppresses heat generation during curing, even if the outer shape of the first bundling portion is as large as 70 mm or more, an excessive temperature rise does not occur during curing. Further, by setting the outer diameter to less than 250 mm, the weight of the device itself can be suppressed, and the load on the pipes to be connected can be suppressed.

  In the fermentation industry and the pharmaceutical / medical field, it is necessary to prevent contamination of the filtrate or the filtrate (contamination). When using a hollow fiber membrane module in such a field, before use Sterilization in the hollow fiber membrane module or sterilization operation is performed.

Examples of general sterilization and sterilization methods include hot water sterilization, ultraviolet sterilization, gamma ray sterilization, and gas sterilization. In particular, when sterilizing or sterilizing a large tank, piping connected to the tank, or separation membrane module, hot water sterilization (usually 80 ° C., 1 hour) is an effective method.
<Second binding unit>
The second bundling portion 4 disposed on the filtrate inlet 9 side of the cylindrical case 1, that is, on the lower end side of the hollow fiber membrane module 100 </ b> A, closes the hollow portion at the second end of the hollow fiber membrane 2. They are united together.

  The bundling method is not particularly limited as long as the mechanical strength, chemical durability, thermal durability, and the like of the bundling portion are satisfied, but the outer periphery of the hollow fiber membrane bundle 12 is covered with a heat shrinkable tube or the like, and heated and bundled And a method of arranging hollow fiber membranes on a sheet and binding them in a wound form, a method of bonding using an adhesive, and the like.

The binding portion can contain a silicone resin, an epoxy resin, a polyurethane resin, or the like as a main component, but it is preferable that the same adhesive as that of the first binding portion 3 is a polymer main component. In addition, a polymer main component refers to the component with most mass contained in the polymer contained in a containing component. The second binding portion 4 may be fixed to the cylindrical case 1 in a liquid-tight or liquid-permeable manner, and the fixing method has nothing to do with the present invention.
<Through hole in the second binding part>
The 2nd binding part 4 has the hole 5 used as fluid flow paths, such as to-be-filtered liquid. In order to reduce the flow retention portion in the vicinity of the first end side end surface of the second binding portion 4, the total area of the holes 5 in the cross section perpendicular to the height direction includes the second binding portion, It is preferable that it is 2% or more and less than 35% with respect to the area inside the cylindrical case in the cross section perpendicular to the height direction.

  By setting the total area of the holes 5 to 2% or more, it is possible to reduce the area between the holes 5 that may be a staying place. Further, the pressure loss when the fluid passes through the hole 5 can be reduced, and the pump power cost can be reduced when the fluid flows from the bottom to the top. Further, when the fluid flows from the top to the bottom, the flow is likely to occur, and the possibility that turbidity blocks the holes 5 can be suppressed. Further, when the second bundling portion is formed using an adhesive in the same manner as the first bundling portion, the hole 5 plays a role of radiating heat generated by the heat generated by curing.

  On the other hand, by setting the total area of the holes 5 to less than 35%, the cross-sectional area of the second binding portion 4 other than the hollow fiber membrane 2 is increased. It is possible to prevent problems such as occurrence of a second end side sealing failure or difficulty in discharging turbidity deposited between the hollow fiber membranes 2. Furthermore, when the fluid flows through the holes 5 from the bottom to the top, if there is a bias in the inflowing flow, a stagnant portion is likely to occur and turbidity is likely to accumulate. If the total area of the holes 5 is less than 35%, the pressure loss of the fluid is sufficient, and the flow flowing into the holes 5 is less biased.

  It is preferable that a plurality of holes 5 exist, and the arrangement of each hole 5 is arbitrary, such as the positions of the vertices of many equilateral triangles, the positions of intersections of radiation and concentric circles, and the positions of intersections on the lattice. If there is a deviation in the interval between the matching holes, a portion where the interval is larger than the others tends to stay. Therefore, it is preferable to make the interval equal so that there is no great difference in the interval.

  Furthermore, it is more preferable that the terminal end of at least one hole 5 is arranged in a region within a range of 3 mm in height from the lowest portion of the first end side end surface of the second binding portion 4. In the case where the fluid flows down from the top, if the first end side end surface of the second bundling portion 4 is not horizontal, a stagnant portion is likely to occur at the lowest portion, and the drainage from the portion is reliably performed. is there.

  When the 1st end side end surface of the 2nd binding part 4 is not horizontal, the following cases are mentioned, for example. When the 2nd binding part 4 is shape | molded with an adhesive agent and especially the centrifugal potting method was performed, a dent will be made in the 2nd end side center part of a 1st binding part by the influence of centrifugal force. In addition, an inclination is formed in the upward and downward directions due to the influence of gravity.

  On the other hand, in the stationary potting method, the second end side end face of the first binding part 3 can be horizontal, but when the second binding part forming jig 17 is tilted from the vertical direction, potting is performed. In this case, an inclination is formed on the second end side end face.

Moreover, the cross-sectional shape perpendicular | vertical to the height direction of the hole 5 is arbitrary, such as circular, an ellipse, a polygon, and a star shape.
<Material of cylindrical case and second cylindrical case>
The material of the cylindrical case 1 used in the hollow fiber membrane module is not particularly limited as long as it satisfies mechanical strength, chemical durability, thermal durability, etc. For example, vinyl chloride resin, polypropylene resin, polysulfone resin Fluorine resins such as polytetrafluoroethylene and perfluoroalkoxy fluororesin, polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, aluminum and the like.

Further, the material of the second cylindrical case 15 used in the hollow fiber membrane module is not particularly limited, but can be selected from the same material as that of the cylindrical case 1, for example.
<Method for producing hollow fiber membrane module>
Below, the manufacturing method of the hollow fiber membrane module concerning 1st Embodiment is demonstrated. In addition, the manufacturing method described here is not limited to 1st Embodiment, A hollow fiber membrane module can be manufactured with the same method also in any embodiment mentioned later.

  Below, the 1st binding part 3 and the 2nd binding part 4 are hardened using an adhesive agent, and the method of potting the hollow fiber membrane 2 is demonstrated.

  The potting method includes centrifugal potting, in which liquid adhesive penetrates between hollow fiber membranes using centrifugal force and then hardens, and liquid adhesive is fed by a metering pump or head to flow naturally. Any of the stationary potting methods in which the hollow fiber membrane 2 is allowed to penetrate and then cured can be used.

  When potting is performed, it is preferable to control the ambient temperature between 0 ° C. and less than 60 ° C. By setting the temperature to 0 ° C. or higher, the curing reaction of the adhesive can be advanced. In the epoxy resin, the reaction between the epoxy group and the amine can proceed. More preferably, reaction time can be shortened by being 5 degreeC or more. Moreover, excessive hardening heat_generation | fever can be suppressed by setting it as less than 60 degreeC. More preferably, by setting the temperature to less than 50 ° C., the heat resistance measures of the worker are slight and workability is good.

  The cured adhesive can be increased in strength by heating in a subsequent step. Specifically, it is preferable to perform heat treatment at 80 ° C. or higher. By heat-treating at 80 ° C. or higher, the strength of the adhesive has a sufficient strength even in a heating operation such as during hot water sterilization. Further, heat treatment at a temperature equal to or lower than the Vicat softening temperature of the hollow fiber membrane can prevent damage to members other than the adhesive such as the hollow fiber membrane due to heat. More preferably, by performing the heat treatment at 90 ° C. or higher, the adhesive has sufficient strength, and damage to other members other than the adhesive due to heat can be prevented.

  In addition, the temperature of the heat treatment should be raised stepwise. For example, it is preferable to perform heat treatment at a plurality of temperature steps of 80 ° C., 100 ° C., and 120 ° C. after heat treatment at 60 ° C. for a certain time.

  In the centrifugal potting method, the adhesive easily penetrates between the hollow fiber membranes by centrifugal force, and a highly viscous adhesive can also be used. In addition, when a polyurethane resin is used as an adhesive for adhering the hollow fiber membrane 2, since the moisture and isocyanate contained in the hollow fiber membrane 2 react to generate carbon dioxide and foam, the polyurethane resin is formed by a stationary potting method. It is difficult to use.

  If the centrifugal potting method is used, pressure is generated in the end direction of the hollow fiber membrane module due to centrifugal force, and bubbles are released in the inner direction. Therefore, polyurethane resin can be used as an adhesive for bonding the hollow fiber membrane 2. On the other hand, stationary potting does not require large equipment such as a centrifugal molding machine.

  When the potting is finished and the adhesive is cured, the end surface of the hollow fiber membrane 2 is opened by cutting the binding portion on the first end side of the first binding portion 3. Prior to potting, it is desirable to carry out a sealing process for sealing the hollow portion of the first end side end portion of the hollow fiber membrane 2 with a silicone adhesive or the like. When the sealing treatment is performed, it is possible to prevent the potting agent from further entering the hollow portion, and to prevent the occurrence of thread breakage in which the hollow portion is filled with the potting agent and the permeate does not come out.

  Further, when the first binding portion 3 is bonded to the inner side of the second cylindrical case 15 and when the binding portion is fixed by bonding to the cylindrical case 1, the second cylindrical case 15 and the The inner surface of the cylindrical case 1 may be filed and subjected to plasma treatment, primer treatment, or the like.

  Next, the manufacturing method of the hollow fiber membrane module 100A concerning 1st Embodiment is demonstrated with reference to the flowchart of FIG. However, the manufacturing method described below can be applied to the hollow fiber membrane module of any embodiment described later.

  First, the hollow fiber membrane bundle 12 is installed in the centrifugal potting apparatus shown in FIG. 3 and centrifugal potting is performed to form the first and second binding portions (step S1).

  Here, the hollow fiber membrane bundle 12 is housed in the cylindrical case 1, the first end of the hollow fiber membrane bundle 12 is used as the second cylindrical case 15, and the second cylindrical case 15 is used for forming the first binding unit. The second end portion of the hollow fiber membrane bundle 12 is inserted into the jig 16 into the second binding portion forming jig 17. A pin 18 is inserted into the through hole at the bottom of the second binding part forming jig 17. The first end portion of the hollow fiber membrane 2 is preliminarily treated with a silicone adhesive.

  A potting agent feeder 19 is connected to the cylindrical case 1, and by rotating the entire apparatus in a centrifugal molding machine, the potting agent is treated by the centrifugal force to form the first binding part case 16 and the second binding part molding treatment. The tool 17 can be supplied. The potting agent can be supplied simultaneously to the first bundling part forming jig 16 and the second bundling part forming jig 17 or separately.

  After the adhesive is cured, the first binding part forming jig 16, the second binding part forming jig 17, and the pin 18 are removed. Since the time and temperature required for curing vary depending on the components of the adhesive, suitable conditions may be applied as appropriate.

  The CC line part of FIG. 3 is cut | disconnected with a tip-saw type rotary blade, and the 1st end part of the hollow fiber membrane 2 is opened (step S2).

  Finally, the hollow cap membrane module 100A can be manufactured by fixing the upper cap 6 to the first end side of the cylindrical case 1 and the lower cap 7 to the second end side (step S3).

  The material of the binding part forming jig is not particularly limited as long as it satisfies heat resistance, chemical durability, and the like. For example, vinyl chloride resin, nylon resin, fluorine resin, polypropylene resin, polyacetal resin, polyethylene Resins, silicone resins and the like are excellent in releasability and are preferably used. The potting part forming jig may be made of a single material or a combination of a plurality of materials so as to include at least one material as described above.

Further, the material of the pin is not particularly limited as long as it satisfies heat resistance, chemical durability, and the like. For example, the same material as that for the binding portion forming jig can be used. In the case of using a metal, a fluororesin coating or the like is preferably performed in order to improve releasability.
<Operation method of hollow fiber membrane module>
During the filtration operation using the hollow fiber membrane module 100A, the filtrate to be filtered enters from the filtrate inlet 9 and passes through the hole 5 from the second end side of the second bundling portion 4 from the bottom to the hollow. It is introduced between the yarn membrane bundles 12. The filtrate to be filtered passes through the hollow fiber membrane 2 and moves as a filtrate into a space surrounded by the first binding portion 3 and the upper cap 6 and then is taken out from the filtrate outlet 8 to the outside of the hollow fiber membrane module.

  When performing dead-end filtration, the filtrate outlet 11 is closed, but when performing cross-flow filtration, the filtrate to be filtered introduced into the cylindrical case 1 from the filtrate outlet 11 is used. A part is taken out, and the taken out filtrate is again introduced into the hollow fiber membrane module from the filtrate inlet 9.

  By performing the cross flow filtration, a flow easily occurs in the hollow fiber membrane module, and the effect of reducing the turbidity accumulation and the membrane surface cleaning by the flow in the vicinity of the membrane surface can be obtained. Cross flow filtration is widely used particularly in the fermentation industry, the pharmaceutical / medical field, and the food industry.

  Moreover, generally, after performing a filtration operation using a hollow fiber membrane module for a certain period of time, a step of washing the inside of the hollow fiber membrane module is provided, and water, a chemical solution, Gas etc. are supplied. In particular, in a process that requires hot water sterilization, hot water of about 80 ° C. is supplied.

On the other hand, in the washing step, when the filtrate, water, or washing liquid is introduced from the filtrate outlet 8 and discharged from the hollow portion of the hollow fiber membrane 2 to the outside, the hole 5 is lowered from the top to the bottom. The drainage flows, and the drainage is discharged out of the hollow fiber membrane module from the filtrate inlet 9.
[Second Embodiment]
The configuration of the hollow fiber membrane module 100B according to the second embodiment of the present invention will be described with reference to the drawings. FIG. 4 is a schematic longitudinal sectional view of a hollow fiber membrane module 100B according to the second embodiment. In addition, about the structure of the hollow fiber membrane module 100B which is not mentioned below, the structure similar to the hollow fiber membrane module 100A of 1st Embodiment is applicable. Members having the same functions as those described in the first embodiment are given the same reference numerals, and descriptions thereof are omitted.

  During the filtration operation using the internal pressure type hollow fiber membrane module 100B according to the second embodiment, the liquid to be filtered enters from the liquid inlet 21 and the hollow fiber membrane from the second end side of the second binding unit 4. 2 passes through the hollow portion 2 and is taken out from the filtrate outlet 20 to the outside of the hollow fiber membrane module. The liquid to be filtered passes through the hollow fiber membrane 2 and is taken out as a filtrate between the hollow fiber membrane bundles 12 surrounded by the tubular case 1 and then taken out from the filtrate outlets 22 and 23 to the outside of the hollow fiber membrane module. .

  When performing dead-end filtration, the filtrate outlet 20 is closed. However, when performing cross-flow filtration, the filtrate extracted from the filtrate outlet 20 is again filtered into the filtrate inlet. 21 is introduced into the hollow fiber membrane module.

  By performing the cross flow filtration, the effect of cleaning the membrane surface by the flow in the vicinity of the membrane surface can be obtained. Cross flow filtration is widely used particularly in the fermentation industry, the pharmaceutical / medical field, and the food industry.

  Moreover, generally, after performing a filtration operation using a hollow fiber membrane module for a certain period of time, a step of washing the inside of the hollow fiber membrane module is provided, and water, a chemical solution, Gas etc. are supplied. In particular, in a process that requires hot water sterilization, hot water of about 80 ° C. is supplied.

On the other hand, in the washing step, when taking a method of introducing the filtrate, water, or the washing liquid from the filtrate outlets 22 and 23 and discharging it from the hollow portion of the hollow fiber membrane 2 to the inside, the filtrate outlet 23 or Waste water is discharged from the filtrate inlet 21 to the outside of the hollow fiber membrane module.
[Third Embodiment]
A configuration of a hollow fiber membrane module 100C according to the third embodiment of the present invention will be described with reference to the drawings. FIG. 5 is a schematic longitudinal sectional view of the first end side of the hollow fiber membrane module 100C according to the third embodiment. In addition, about the structure of the hollow fiber membrane module 100C which is not mentioned below, the structure similar to the hollow fiber membrane module 100A of 1st Embodiment is applicable. Members having the same functions as those described in the first embodiment are given the same reference numerals, and descriptions thereof are omitted.

  In the hollow fiber membrane module 100 </ b> C according to the third embodiment, the first bundling portion 3 crushes the sealing material 25 and the sealing material 26 and is liquid-tightly fixed to the second cylindrical case 15 and the upper cap 6.

  The second cylindrical case 15 is fixed to the cylindrical case 1 in a liquid-tight manner by crushing the gasket 10 and the sealing material 24.

  The structure, operation method, and manufacturing method are the same as those of the hollow fiber membrane module 100A of the first embodiment except for the fixing method of the first binding unit 3 and the second cylindrical case 15. Since the first binding part 3 is liquid-tightly fixed to the second cylindrical case 15 via a sealing material, there is no bonding surface between the first binding part 3 and the second cylindrical case 15, and hence the bonding No peeling failure occurs.

  As a result, when the hollow fiber membrane bundle 12 bound to the first binding portion 3 is deteriorated, the second cylindrical case 15 and the cylindrical case 1 can be reused.

  The second cylindrical case 15 is used to control the liquid flow inside the cylindrical case 1 and outside the hollow fiber membrane 2. However, when the flow rate of the liquid flow in the portion is small, the second cylindrical case 15 is used. Case 15 may not be used. In that case, the cylindrical case 1 and the first bundling portion 3 are fixed in a liquid-tight manner by the sealing material, and there is no adhesive surface.

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto.
(A) Production of Hollow Fiber Membrane 38 parts by mass of vinylidene fluoride homopolymer having a weight average molecular weight of 41,000 and 62 parts by mass of γ-butyrolactone were mixed and dissolved at 160 ° C. This polymer solution was discharged from a double-tube base while an 85% by mass γ-butyrolactone aqueous solution was accompanied as a hollow portion forming liquid, and from an 85% by mass γ-butyrolactone aqueous solution at a temperature of 20 ° C. placed 30 mm below the base. A hollow fiber membrane having a spherical structure was produced by solidifying in a cooling bath.

  Subsequently, 14 parts by mass of vinylidene fluoride homopolymer having a weight average molecular weight of 284,000, 1 part by mass of cellulose acetate propionate (manufactured by Eastman Chemical Co., CAP482-0.5), 77 parts by mass of N-methyl-2-pyrrolidone Part, 5 parts by mass of polyoxyethylene sorbitan fatty acid ester (manufactured by Sanyo Chemical Industries, Ionet (registered trademark) T-20C) and 3 parts by mass of water were mixed and dissolved at 95 ° C. to prepare a polymer solution.

  This membrane-forming stock solution was uniformly applied to the surface of the hollow fiber membrane having the spherical structure obtained above, and immediately solidified in a water bath to form a three-dimensional stitch structure on the spherical structure layer. A thread membrane 2 was produced.

The obtained hollow fiber membrane 2 has an outer diameter of 1350 μm, an inner diameter of 800 μm, and an average pore diameter of the membrane surface of 40 nm. The hollow fiber membrane section is melted and formed into a plate shape. The Vicat softening temperature was measured using a second type and found to be 170 ° C.
(B) Production of hollow fiber membrane module The hollow fiber membrane 2 obtained in the above (a) was cut to a length of 1800 mm, immersed in a 30% by mass glycerin aqueous solution for 1 hour, and then air-dried. The hollow fiber membrane 2 was heat-treated with steam at 125 ° C. for 1 hour, air-dried, and cut into a length of 1200 mm.

  Thereafter, the first end side of the hollow fiber membrane 2 was spotted with a silicone adhesive (made by Toray Dow Corning Co., Ltd., SH850A / B, in which two components were mixed so that the mass ratio was 50:50). .

  Thereafter, as shown in FIG. 3, 5000 stainless steel cylindrical cases 1 (inner diameter 145 mm, outer diameter 155 mm, length 1000 mm, split mold) were filled with 5000 of the aforementioned hollow fiber membranes 2.

  Furthermore, the polysulfone 2nd cylindrical case 15 was arrange | positioned at the 1st end side in the stainless steel cylindrical case 1. FIG.

A first bundling part forming jig 16 and a second bundling part forming jig 17 are disposed at both ends of the stainless steel cylindrical case 1. A pin 18 was inserted into the through hole at the bottom of the second binding part forming jig 17.
Example 1
(A) Curing temperature measurement of epoxy resin As an adhesive (potting agent) for molding a binding part, a bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828) and an aliphatic curing agent (manufactured by Wako Pure Chemical Industries, Ltd.) , Diethylaminopropylamine) was mixed in a total of 2000 g (1000 g per one end) so that the mass ratio was 100: 35, and placed in the potting agent feeder 19. The maximum heat generation temperature of the adhesive reached at the time of curing was 150 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.

  Subsequently, the centrifugal molding machine was rotated, and the adhesive was filled into the binding part forming jigs 16 and 17 at both ends to form the first binding part 3 and the second binding part 4, and the adhesive was cured. The temperature in the centrifugal molding machine was 35 ° C., the rotation speed was 350 rpm, and the centrifugation time was 5 hours.

  After curing, heat treatment was performed at 100 ° C. for 24 hours.

  Thereafter, the binding portion forming jigs 16 and 17 and the pin 18 are removed, and then the end portion (the C-C surface shown in FIG. 3) of the first binding portion 3 is cut with a tip saw type rotary blade, and the hollow fiber membrane 2 is cut. The end face of was opened.

  Subsequently, an upper cap 6 and a lower cap 7 were attached to both ends to obtain a hollow fiber membrane module 100A as shown in FIG. Thereafter, ethanol was fed to the hollow fiber membrane module 100A and filtered, and the pores of the hollow fiber membrane 2 were filled with ethanol. Subsequently, RO (Reverse Osmosis) water was fed and filtered, and ethanol was replaced with RO water.

(B) When a part of the adhesive cured in the glass transition temperature measurement (a) is cut out and the temperature is increased from 25 ° C. to 300 ° C. at 10 ° C./min using DSC-60 Plus manufactured by Shimadzu Corporation. The amount of heat was measured and the glass transition temperature was determined.

  The results are shown in Table 1. The glass transition temperature was 43 ° C.

(C) Tensile test Five dumbbell test pieces No. 1 based on JISK7113 were manufactured under the same composition and curing conditions as in (a), and a tensile test was performed based on JISK7161. The dumbbell was subjected to a tensile test at 5 mm / min and N = 5 with a constant temperature tensilon controlled in an 80 ° C. atmosphere. When calculated using a strain gauge, the Poisson's ratio was 0.5.
(D) Density measurement A sheet was produced with the same composition and curing conditions as in (a). 20 cubes each having a side of 7 mm were cut out from the sheet, and the density at 80 ° C. was calculated by the pycnometer method in accordance with JISK0061. As a result, it was 1.0 g / ml. The measurement was performed at N = 2.

(E) Viscoelasticity measurement A sheet was produced with the same composition and curing conditions as in (a). A test piece having a thickness of 1 mm, a width of 10 mm, and a length of 50 mm was cut out from the sheet, and using a dynamic viscoelastic device (Rheogel-E4000, manufactured by UBM) at a temperature increase rate of 5 ° C./min in a temperature range of 25 to 200 ° C. While heating, the temperature dependence of the storage modulus (E) was measured. At this time, the measurement length was 20 mm, the frequency was 10 Hz, and the tensile strain was 0.05%. The measurement was performed at N = 3, and the average storage modulus at 80 ° C. was 7 MPa.

(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was 1781.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
(Example 2)
(A) Curing temperature measurement of epoxy resin As an adhesive (potting agent) for forming a binding part, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER828) and aliphatic chain amine curing agent (Tokyo Chemical Industry Co., Ltd.) (Company, Tetraethylenepentamine) is the same as Example 1 except that the mass ratio is 100: 16.

The maximum heat generation temperature of the adhesive reached at the time of curing was 155 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.
(B) Measurement of glass transition temperature A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 78 ° C.
(C) Tensile test A tensile test was performed in the same manner as in Example 1 with the same composition as in (a). As a result, the Poisson's ratio was 0.5.
(D) Density measurement It was 1.1 g / ml as a result of calculating a density by the pycnometer method similarly to Example 1. FIG.
(E) Viscoelasticity measurement A viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus was 9 MPa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was 1765.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
(Example 3)
(A) Measurement of curing temperature of epoxy resin As an adhesive (potting agent) for molding the binding part, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., JER828) and aliphatic cyclic amine curing agent (Wako Pure Chemical Industries Ltd.) 4,4-methylenebis (cyclohexylamine) manufactured by company and aliphatic chain amine curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) were mixed so that the mass ratio was 100: 11: 25. Other than the above, the second embodiment is the same as the first embodiment.

The maximum heat generation temperature of the adhesive reached at the time of curing was 148 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.
(B) Measurement of glass transition temperature A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 60 ° C.
(C) Tensile test A tensile test was performed in the same manner as in Example 1 with the same composition as in (a). As a result, the Poisson's ratio was 0.5.
(D) Density measurement It was 1.3 g / ml as a result of calculating a density by the pycnometer method similarly to Example 1. FIG.
(E) Viscoelasticity measurement The viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus was 8 MPa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was 1776.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
Example 4
(A) Curing temperature measurement of epoxy resin As an adhesive (potting agent) for molding a binding part, bisphenol A type epoxy resin (Mitsubishi Chemical Corporation, JER828) and alkyl monoglycidyl ether (Mitsubishi Chemical Corporation, YED111N) And an aliphatic chain amine curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) are the same as in Example 1 except that the mass ratio is 85:15:36.

  The maximum heat generation temperature of the adhesive reached at the time of curing was 140 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.

(B) Glass transition temperature measurement A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 40 ° C. (c) A tensile test was conducted in the same manner as in Example 1 under the same composition and curing conditions as in the tensile test (a). As a result, the Poisson's ratio was 0.5.
(D) Density measurement It was 1.2 g / ml as a result of calculating the density in 80 degreeC by the pycnometer method like Example 1. FIG. The measurement was performed at N = 2.
(E) Viscoelasticity measurement As a result of conducting a viscoelasticity test in the same manner as in Example 1, the average storage elastic modulus at 8O 0 C was 8 MPa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was 1790.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
(Example 5)
(A) Curing temperature measurement of epoxy resin As an adhesive (potting agent) for forming a binding part, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., JER828) and aliphatic chain amine curing agent (Wako Pure Chemical Industries, Ltd.) Co., Ltd., diethylaminopropylamine) was mixed so that the mass ratio was 100: 35. A hollow fiber membrane module was produced in the same manner as in Example 1 except that the heat treatment step was not performed after the adhesive was cured using a centrifugal molding machine.

The maximum heat generation temperature of the adhesive reached at the time of curing was 150 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.
(B) Measurement of glass transition temperature A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 43 ° C.
(C) Tensile test A tensile test was performed in the same manner as in Example 1 with the same composition as in (a). As a result, the Poisson's ratio was 0.5.
(D) Density measurement It was 1.0 g / ml as a result of calculating a density by the pycnometer method like Example 1. FIG.
(E) Viscoelasticity measurement The viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus was 7 MPa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was 1781.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
(Example 6)
(A) Production of hollow fiber membrane 20 parts by mass of polyethersulfone (Victres 200), 10 parts by mass of polyvinylpyrrolidone (weight average molecular weight 360,000), 65 parts by mass of N-methyl-2-pyrrolidone, and 5 parts by mass of isopropanol are mixed and dissolved. Then, it was discharged from a double tube cap and immediately solidified in water at a temperature of 20 ° C. The obtained hollow fiber separation membrane was immersed in ethanol and further immersed in hexane for dehydration. Thereafter, heat treatment was performed for 2 hours at 150 ° C. to crosslink polyvinylpyrrolidone. The hollow fiber membrane slice was melted and formed into a plate shape, and the Vicat softening temperature was measured using an HDT test apparatus (Model 3M-2 manufactured by Toyo Seiki Seisakusho).
(B) Measurement of curing temperature of epoxy resin Same as Example 1 except that a total of 6000 g (3000 g per one end) of the adhesive forming the binding part was mixed and a polyethersulfone hollow fiber membrane was used. . The maximum heat generation temperature of the adhesive reached at the time of curing was 152 ° C., and the members of the hollow fiber membrane module 100A were not damaged by heat generation.
(C) Glass transition temperature measurement A part of the adhesive cured in (b) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 42 ° C.
(D) Tensile test As a result of conducting a tensile test in the same manner as in Example 1 with the same composition as in (b), the Poisson's ratio was 0.5.
(E) Density measurement It was 1.0 g / ml as a result of calculating a density by the pycnometer method like Example 1. FIG.
(F) Viscoelasticity measurement A viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus was 7 MPa.
(G) Calculation of Mc Mc was calculated by substituting the values measured in (d), (e), and (f) into (Equation 1). The results are shown in Table 1. Mc was 1781.

(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, no damage was observed on each member of all hollow fiber membrane modules, and the second tube made of polysulfone No peeling occurred between the case 15 and the first binding part 3.
(Comparative Example 1)
(A) Curing temperature measurement of epoxy resin As an adhesive (potting agent) for forming a binding part, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., JER828) and aliphatic chain amine curing agent (Wako Pure Chemical Industries, Ltd.) Example 1 except that diethylenetriamine) was mixed so that the mass ratio was 100: 11.

The maximum exothermic temperature of the adhesive reached upon curing was 191 ° C.
(B) Measurement of glass transition temperature A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 117 ° C.
(C) Tensile test A Poisson's ratio was 0.5 as a result of conducting a tensile test in the same manner as in Example 1 except that the tensile test was performed at an atmospheric temperature of 180 ° C with the same composition as (a).
(D) Density measurement The density was calculated to be 1.1 g / ml by the pycnometer method in the same manner as in Example 1 except that the measurement was performed at an atmospheric temperature of 180 ° C.
(E) Viscoelasticity measurement As a result of conducting a viscoelasticity test like Example 1, the average storage elastic modulus in 180 degreeC was 98 Mpa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was as small as 130.
(G) Production yield evaluation According to the same procedure as in (a), 10 hollow fiber membrane modules were produced. As a result, 7 hollow fiber membrane modules were damaged. Of the seven damaged hollow fiber membrane modules, the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A melted. This is considered due to the fact that the curing exothermic temperature of the adhesive was higher than the softening temperature of the hollow fiber membrane. In addition, among the seven damaged hollow fiber membrane modules, peeling occurred between the second tubular case 15 made of polysulfone and the first binding portion 3 for four hollow fiber membrane modules. It was considered that cracking occurred as a result of a large stress acting during the curing shrinkage of the adhesive because the glass transition temperature of the adhesive was high.
(Comparative Example 2)
(A) Curing temperature measurement of epoxy resin Multifunctional epoxy resin (manufactured by Mitsubishi Chemical Corporation, JER604) and aliphatic cyclic amine curing agent (Wako Pure Chemical Industries, Ltd.) The same as Example 1, except that 4,4-methylenebis (cyclohexylamine) manufactured by company was mixed so that the mass ratio was 100: 44.

The maximum exothermic temperature of the adhesive reached upon curing was as high as 195 ° C.
(B) Measurement of glass transition temperature A part of the adhesive cured in (a) was cut out, and the glass transition temperature was determined in the same manner as in Example 1. The results are shown in Table 1. The glass transition temperature was 114 ° C.
(C) Tensile test A Poisson's ratio was 0.5 as a result of conducting a tensile test in the same manner as in Example 1 except that the tensile test was performed at an atmospheric temperature of 180 ° C with the same composition as (a).
(D) Density measurement The density was calculated to be 1.1 g / ml by the pycnometer method in the same manner as in Example 1 except that the measurement was performed at an atmospheric temperature of 180 ° C.
(E) Viscoelasticity measurement As a result of conducting a viscoelasticity test like Example 1, the average storage elastic modulus in 180 degreeC was 101 Mpa.
(F) Calculation of Mc Mc was calculated by substituting the values measured in (c), (d), and (e) into (Equation 1). The results are shown in Table 1. Mc was as small as 120.
(G) Production yield evaluation As a result of producing 10 hollow fiber membrane modules by the same procedure as in (a), damage was observed in 9 hollow fiber membrane modules. Of the nine damaged hollow fiber membrane modules, the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A melted. This is considered due to the fact that the curing exothermic temperature of the adhesive was higher than the softening temperature of the hollow fiber membrane. In addition, among the nine damaged hollow fiber membrane modules, peeling occurred between the second tubular case 15 made of polysulfone and the first binding portion 3 in six hollow fiber membrane modules. It was considered that cracking occurred as a result of a large stress acting during the curing shrinkage of the adhesive because the glass transition temperature of the adhesive was high.

  Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

  Since the hollow fiber membrane module of the present invention can suppress heat generation during curing of the binding portion, it can suppress damage to the hollow fiber membrane module main body that may occur in the production process, and can achieve a high yield. . In addition, the suppression of heat generated by curing enables the curing of large-capacity adhesives at the same time to bind polymer hollow fiber membranes, so that polymer hollow fiber membrane modules with a large membrane area per unit volume can be manufactured at low cost. can do.

  As a result, the manufacturing cost per membrane area of the hollow fiber membrane module can be reduced, and the number of hollow fiber membrane modules used during the process can be reduced. Is advantageous.

100A: hollow fiber membrane module 100B: hollow fiber membrane module 100C: hollow fiber membrane module 1: cylindrical case 1A: collar 1B: collar 2: hollow fiber membrane 3: first binding part 4: second binding part 5: Hole 6: Upper cap 6A: Step 7: Lower cap 8: Filtrate outlet 9: Filtrate inlet 10: Gasket 11: Filtrate outlet 12: Hollow fiber membrane bundle 14: Rectification hole 15: Second cylindrical shape Case 16: First binding part forming jig 17: Second binding part forming jig 18: Pin 19: Potting agent feeder 20: Filtrate outlet 21: Filtrate inlet 22: Filtrate outlet 23: Filtrate outlet 24: sealing material 25: sealing material 26: sealing material

Claims (7)

A cylindrical case, and a hollow fiber membrane bundle accommodated in the cylindrical case,
In the hollow fiber membrane bundle, a plurality of hollow fiber membranes are bound in a state where one or both ends of the hollow portion of the hollow fiber membrane are opened by at least one binding portion,
The glass transition temperature of the binding part is less than 80 ° C., and
A hollow fiber membrane module in which Mc of the binding portion represented by the following formula 1, the weight W of the binding portion, and the Vicat softening temperature VST of the hollow fiber membrane satisfy the following formula 2.
Mc = 2 (1 + μ) ρRT / E (Formula 1)
μ: Poisson's ratio, ρ: density (g / m ³ ), R: gas constant (J / K / mol),
T: Absolute temperature (K), E: Storage elastic modulus (Pa)
VST ≧ 5.78 × W / Mc + 420 (Formula 2)
VST: Vicat softening temperature (K) of the hollow fiber membrane,
W: Weight (g) of one binding part with an open hollow part   The hollow fiber membrane module according to claim 1, wherein the Mc is 1000 or more and less than 5000.   The hollow fiber membrane module according to claim 1 or 2, wherein the binding portion contains (a) an epoxy resin and (b) an amine curing agent.   The hollow fiber membrane module according to any one of claims 1 to 3, wherein the binding portion contains (a) a bisphenol-type epoxy resin and (b) a curing agent having an aliphatic amine as a main skeleton.   The said binding part contains a particle | grain with an average particle diameter of 40 micrometers or less so that a sedimentation volume may be 150-1000 ml with respect to 100g of adhesives which comprise the said binding part. The hollow fiber membrane module according to Item.   The hollow fiber membrane module according to any one of claims 1 to 5, wherein the cylindrical case and the binding portion are fixed in a liquid-tight manner by a sealing material.   The second cylindrical case accommodated in the cylindrical case, wherein the second cylindrical case and the bundling portion are fixed in a liquid-tight manner by a sealing material. The hollow fiber membrane module described in 1.