WO2017131126A1 - Hollow fiber membrane module and method for producing hollow fiber membrane module - Google Patents

Abstract

The present invention relates to a hollow fiber membrane module which is provided with a cylindrical case, a hollow fiber membrane bundle composed of multiple hollow fiber membranes enclosed in the cylindrical case and one or more binding parts for binding the multiple hollow fiber membranes, wherein each of the binding parts contains an adhesive agent, the adhesive agent has a glass transition temperature of 80ºC or higher and lower than 160ºC, and the Mc value, which is represented by a specific formula, of the adhesive agent, the weight W of the individual binding parts each of which can bind the hollow fiber membranes in a state such that the hollow parts of the hollow fiber membranes are opened and the Vicat softening temperature VST of the hollow fiber membranes satisfy a specific formula.

Description

Hollow fiber membrane module and method for producing hollow fiber membrane module

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 particularly to a hollow fiber membrane module having a bundling portion having high heat resistance. The present invention also relates to a method for producing the hollow fiber membrane module.

As seen in Patent Document 1, a hollow fiber membrane module generally contains 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, and the hollow fiber membrane bundle At least one end is bound and accommodated in a cylindrical case.

Here, the bundled hollow fiber membranes are opened at at least one end, and the hollow portion becomes a flow path for 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.

Further, 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 generation of the adhesive in the large module.

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

However, when a partition plate is used as in Patent Document 2, 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.

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 casing, and the like due to the heat generated by curing of the adhesive is separated from a partition plate or the like as in Patent Document 2. It aims at providing the hollow fiber membrane module which can be solved without using a member.

The present inventors have selected the glass transition temperature of the adhesive in a specific range and Mc shown by Formula 1 and the Vicat softening temperature VST of the hollow fiber membrane to satisfy Formula 2, and thereby the heat resistance of the hollow fiber membrane module. New knowledge that heat generation at the time of curing of the adhesive can be suppressed while realizing the above properties and the above-mentioned problems can be solved.

The present invention is based on this new knowledge and provides the following techniques (1) to (11).
(1) A cylindrical case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes accommodated in the cylindrical case, and at least one binding portion for binding the plurality of hollow fiber membranes, the binding Part contains an adhesive, and the adhesive has a glass transition temperature of 80 ° C. or higher and lower than 160 ° C., and Mc indicated by Formula 1 of the adhesive and a hollow part of the hollow fiber membrane are opened. A hollow fiber membrane module in which the weight W of the one binding portion to be bound and the Vicat softening temperature VST of the hollow fiber membrane satisfy Expression 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 where the hollow part is opened
(2) The hollow fiber membrane module according to (1), wherein the adhesive has an Mc of the formula 1 of 140 or more and less than 1760.
(3) The hollow fiber membrane module according to (1) or (2), wherein the binding portion contains (a) an epoxy resin and (b) an amine curing agent.
(4) The binding portion contains (a) a bisphenol-type epoxy resin and (b) a curing agent having at least one of an alicyclic amine and an aromatic amine as a main skeleton. The hollow fiber membrane module as described in any one of these.
(5) The binding portion mainly comprises (a) a bisphenol type epoxy resin having an epoxy equivalent of 150 to less than 250, and (b) at least one of bis (4-aminocyclohexyl) methane and bis (4-aminophenyl) methane. The hollow fiber membrane module according to any one of (1) to (4), comprising a curing agent as a skeleton.
(6) The bundling portion has the number of epoxy groups in the (a) bisphenol-type epoxy resin having an epoxy equivalent of 150 or more and less than 250, and (b) bis (4-aminocyclohexyl) methane and bis (4 (Amino) a bisphenol type epoxy resin having an epoxy equivalent of 150 or more and less than 250, wherein the value obtained by dividing at least one of the methane by the number of amino groups of the curing agent having a main skeleton is 6 or more and less than 20 The hollow fiber membrane module as described in 5).
(7) Any one of (1) to (6), wherein the binding portion contains particles having an average particle size of 40 μm or less so that a sedimentation volume is 150 or more and less than 1000 ml with respect to 100 g of the adhesive. The hollow fiber membrane module described in 1.
(8) The hollow fiber membrane module according to any one of (1) to (7), wherein the cylindrical case and the bundling portion are liquid-tightly fixed by a sealing material.
(9) A second cylindrical case housed in the cylindrical case is provided, and the second cylindrical case and the bundling portion are liquid-tightly fixed by a sealing material. (1) to (8) The hollow fiber membrane module as described in any one.
(10) A hollow fiber membrane comprising a cylindrical case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes accommodated in the cylindrical case, and at least one binding part for binding the plurality of hollow fiber membranes A method for manufacturing a module, wherein the binding portion contains an adhesive, and the glass transition temperature of the adhesive is 80 ° C. or higher and lower than 160 ° C., and Mc represented by Formula 1 of the adhesive and the hollow The adhesive and the hollow fiber membrane are selected so that the weight W of the one binding portion to be bound in a state where the hollow portion of the yarn membrane is open and the Vicat softening temperature VST of the hollow fiber membrane satisfy Expression 2. The manufacturing method of a hollow fiber membrane module.
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 where the hollow part is opened
(11) The method for producing a hollow fiber membrane module according to claim 10, wherein an adhesive having an Mc represented by the formula 1 of 140 or more and less than 1760 is selected as the adhesive.

In the hollow fiber membrane module of the present invention, the glass transition temperature of the adhesive contained in the binding portion is 80 ° C. or higher, so that heat resistance that does not cause leakage of raw water during sterilization at high temperature and sterilization can be realized, When the Vicat softening temperature VST of the hollow fiber membrane satisfies Expression 2, it is possible to suppress damage to the hollow fiber membrane module due to heat generation during curing of the adhesive.
Moreover, the glass transition temperature of an adhesive agent is less than 160 degreeC, and the heat_generation | fever damage at the time of adhesive agent hardening can be suppressed further.

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.
Incidentally, 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 “bottom” to “top” 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 substantially equal to the inner diameter of the cylindrical case body 1, and the lower end side thereof is reduced in diameter to form the filtrate inlet 9.

Furthermore, the hollow fiber membrane module 100A includes a hollow fiber membrane bundle 12 including a plurality of hollow fiber membranes 2 and a binding 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 object to be separated, 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. If the average pore diameter is less than 10 nm, the water permeability becomes low, and if it exceeds 600 nm, microorganisms and the like may leak. 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 fluorine resins 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 fluororesins and polysulfone resins have high heat resistance, physical strength, and chemical durability. Therefore, the fermentation industry, pharmaceutical manufacturing, and food industries that require steam sterilization and hot water sterilization. It can be suitably used for a hollow fiber membrane module in the water treatment field or the like.

Further, the hollow fiber membrane may further contain a hydrophilic resin in addition to the fluorine resin or the polysulfone 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 using an adhesive. In that case, the binding part forming jig is filled with a hollow fiber membrane and fixed with an adhesive, but the hollow fiber membrane is dried in advance for handling and adhesion problems.

However, many of the hollow fiber membranes have a problem that shrinkage occurs due to drying and water permeability is lowered. Therefore, a membrane that has been dried after being immersed in an aqueous glycerin solution is used. 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 binding portion is molded, heat generated by the curing reaction of the adhesive can be dissipated 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 steam sterilization or hot water sterilization, but depending on the type of the hollow fiber membrane, there is a contraction caused by steam sterilization and hot water sterilization. Therefore, if steam sterilization or hot water sterilization 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.

Generally, since steam sterilization is performed at 121 ° C. or higher, it is desirable to perform pretreatment with steam at 121 ° C. or higher. In general, hot water sterilization is 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.

In addition, the hollow fiber membrane bundle 12 has a bundling portion 3 or a bundling portion 4 at both ends in a loose state in view of the workability for producing the hollow fiber membrane module 100A and the detergency of the hollow fiber membrane 2 in washing the hollow fiber membrane module. It is accommodated in the cylindrical case 1 via.
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 bundling portion contains an adhesive having a glass transition temperature of 80 ° C. or higher and lower than 160 ° C. There are various methods for measuring the glass transition temperature. For example, differential scanning calorimetry (DSC) may be performed. A differential scanning calorimeter is commercially available, and for example, DSC-60 Plus manufactured by Shimadzu Corporation can be used.

When the glass transition temperature is 80 ° C. or higher, it can be used under high temperature conditions such as high temperature liquid filtration, hot water sterilization, and steam sterilization. In addition, when the glass transition temperature is less than 160 ° C., the polymer hollow fiber membrane can be cured and molded with a large-capacity adhesive without being deteriorated by heat generated by curing. Furthermore, the stress acting on the curing shrinkage can be suppressed, and the adhesive peeling can be prevented when the binding portion and the case are bonded.

The bundling portion preferably contains an adhesive having Mc of 140 or more and less than 1760 represented by Formula 1. When Mc is 140 or more, the heat generated by curing is further suppressed. Further, when Mc is less than 1760, it is easy to cure and form an adhesive having a suitable glass transition temperature range.

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)

Measured using a hardened adhesive. 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 K 0061. The storage elastic modulus can be obtained by performing 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 molecular weight Mc between cross-linking points is expressed as shown in Formula 1 by 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 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 sterilization, steam sterilization, and the like.
When using a polymer material with relatively low heat resistance compared to metals and ceramics among the heat resistant materials, the temperature during curing of the adhesive is less than the Vicat softening temperature of the hollow fiber membrane. Preferably there is. If the temperature during curing of the adhesive 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. More preferably, if the temperature during curing of the adhesive is less than 130 ° C., a wider range of materials can be used for the jig used for forming the hollow fiber membrane module or the binding portion.

The temperature during curing of the adhesive can be measured, for example, 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. For example, a 3M-2 type HDT testing apparatus manufactured by Toyo Seiki Seisakusho 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 curing adhesive has a smaller heat release near the center of the binding portion and a higher heat generation temperature, the Vicat softening temperature of the hollow fiber membrane is preferably lower than the heat generation temperature near the center.

It is known that the glass transition temperature of adhesives, particularly epoxy resins, 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.

Also, 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 the Mc of the adhesive and its weight, and as a method for selecting the optimum hollow fiber membrane for manufacturing a hollow fiber membrane module having a desired heat resistance, 2 was derived.

In other words, according to the present invention, the adhesive constituting the binding part having the desired heat resistance is first calculated Mc according to Equation 1, and further selecting the adhesive constituting the hollow fiber membrane and the binding part using Equation 2 as an index. According to the method, it becomes possible to obtain a heat-resistant hollow fiber membrane module with good yield without deterioration of the membrane.

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

Also, as can be seen in Patent Document 2, a technique is disclosed in which a partition plate that divides the epoxy resin into small portions is provided 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.

Generally, as a method of curing an adhesive having a high glass transition temperature of 80 ° C. or higher, a method of increasing the crosslinking point, that is, a method of reducing Mc in the present invention can be mentioned. However, if Mc is smaller than 140, the glass transition temperature becomes high, but on the other hand, the heat generated by curing becomes large, which tends to lead to deterioration of a hollow fiber membrane module member such as a hollow fiber membrane.

Moreover, since Mc is 140 or more, it is easy to provide sufficient toughness as well as suppression of heat generation during curing. It becomes easy to implement | achieve a glass transition temperature of 80 degreeC or more because Mc is less than 1760.
Mc is more preferably 200 or more, and still more preferably 250 or more. Further, Mc is more preferably less than 1600, and still more preferably less than 1500.
It becomes easy to implement | achieve the suitable glass transition temperature of an adhesive agent, 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 to Mc, it is preferable to control the symmetry and rigidity 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 adhesive and suppression of curing heat generation. 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) at least one of an alicyclic amine and an aromatic amine as a main skeleton.

(A) The epoxy resin is more preferably (a) a bisphenol-type epoxy resin having the epoxy equivalent of 150 or more and less than 250 (the following formula (a)). The (b) amine curing agent is more preferably at least one of (b) bis (4-aminocyclohexyl) methane (the following formula (b1)) and bis (4-aminophenyl) methane (the following formula (b2)). A curing agent having one main skeleton.

In the above formula (a), n is an integer of 0 or more, and X is a hydrogen atom or a methyl group.

Cycloaliphatic amines include N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, mensendiamine, isophoronediamine, bis (4-aminophenyl) methane, 1,3-bisaminomethyl And cyclohexane.

Examples of aromatic amines include m-xylylenediamine, xylylenediamine derivatives, xylylenediamine trimers, m-phenylenediamine, bis (4-aminophenyl) methane, diaminodiphenylsulfone, and the like. These may be used alone or in combination.

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.

In (a) epoxy resin, it is preferable that 60% or more of (a) bisphenol type epoxy resin having the epoxy equivalent of 150 or more and less than 250 (the above formula (a)) is contained.
(B) In the amine curing agent, (b) at least one of bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4-aminophenyl) methane (the above formula (b2)) is a main skeleton. It is preferable that 40% or more of the curing agent is contained. (B) In the amine curing agent, (b) at least one of bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4-aminophenyl) methane (the above formula (b2)) is not a main skeleton. The curing agent is not particularly limited, but an aliphatic amine is preferably used.

(A) The number of epoxy groups in the bisphenol-type epoxy resin having the epoxy equivalent of 150 or more and less than 250 (the above formula (a)) is changed to (b) bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4 The value obtained by dividing at least one of -aminophenyl) methane (the above formula (b2)) by the number of amino groups in the component having the main skeleton is preferably 6 or more and less than 20. More preferably, it is 8 or more and less than 13.

When other curing agents such as chain aliphatic amines are used in combination, the value calculated by dividing the number of epoxy groups in (a) by the number of amino groups in (b) becomes large, and the repeating unit of the cured epoxy resin is symmetrical. And the polymer chain packing is difficult to order and the glass transition temperature of the adhesive is lowered.

In addition, 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 small. In this case, the added curing agent The glass transition temperature of the adhesive is lowered.

(A) bisphenol type epoxy resin (formula (a) above) and (b) bis (4-aminocyclohexyl) methane (formula (b1)) and bis (4-aminophenyl) methane (formula (b2)) At least one of the main skeletons has a six-membered carbon ring with good symmetry, and an epoxy resin cured by this combination tends to orderly repeat units of polymer chains.

Further, (a) the epoxy resin has an aromatic ring, and (b) the amine curing agent has at least one of an aliphatic six-membered ring and an aromatic ring, and therefore is more rigid than a chain aliphatic. Furthermore, since the bisphenol-type epoxy resin (the above formula (a)) having an epoxy equivalent of 150 or more and less than 250 has a relatively low epoxy equivalent, the number of crosslinking points increases among epoxy resins using the same main skeleton. As a result, an adhesive having a high glass transition temperature of 80 ° C. or higher and Mc of 70 or higher can be obtained.

On the other hand, (b) a curing agent having at least one of bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4-aminophenyl) methane (the above formula (b2)) as a main skeleton The active hydrogen equivalent is larger than that of the amine-based curing agent, and thus the molecular weight between crosslink points is increased. Thereby, it is easy to obtain an adhesive having a glass transition temperature of less than 160 ° C. and an Mc of less than 1760.

In this way, by controlling not only the molecular weight between the crosslinking points but also the symmetry and rigidity of the main skeleton, an appropriate glass transition temperature of 80 ° C. or higher and lower than 160 ° C. and an adhesive having Mc of 140 or higher and lower than 1760 are obtained. This makes it easier to suppress the heat of curing of the adhesive.

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 adhesive, 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 during the curing of the adhesive and the handleability during mixing, and fillers, surfactants, silane coupling agents, etc. may be added. Also good.
When improvement of the toughness of the cured adhesive is a problem, a rubber component and rubber particles are often added. Among these, core-shell type rubber particles are effective because they can improve toughness without impairing heat resistance.

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

The adhesive may permeate through the pores from the outside of the hollow fiber membrane to the side of the hollow part and the hollow part may be blocked, resulting in excessive penetration of the adhesive. 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.
More preferably, the binding part may contain particles having an average particle diameter 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.

The average particle size can be measured using a laser diffraction / scattering particle size distribution measuring device. 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 adhesive.
Moreover, when the sedimentation volume is 1000 ml or more, the viscosity of the adhesive to which the particles are added is high, and the fluidity between the hollow fiber membranes and the handling property during 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 adhesive obtained in this way is a membrane cleaning chemical that is widely 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 adhesive obtained by the above method has high heat resistance and heat generation at the time of curing is suppressed, even if the outer shape of the first binding portion is as large as 70 mm or more, an excessive temperature at the time of curing. Does not raise. 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 The inside of the hollow fiber membrane module is sterilized or sterilized.

General sterilization and sterilization methods include hot water sterilization, dry heat sterilization, boiling sterilization, steam sterilization, ultraviolet sterilization, gamma ray sterilization, gas sterilization, and the like. In particular, when sterilizing or sterilizing a large tank, piping connected to the tank, or separation membrane module, warm water sterilization (usually 80 ° C, 1 hour) or steam sterilization (usually 121 ° C, 20 minutes) Is the most effective method. However, when the glass transition temperature of the adhesive is low, the mechanical strength is remarkably lowered in the hot water sterilization or steam sterilization operation, and it is difficult to isolate the space in a liquid-tight manner at the binding portion.

On the other hand, the adhesive having the glass transition temperature and Mc in the specific range described above has good heat resistance and hardly causes deterioration of other members due to heat generation during curing.

<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 adhesive can contain a silicone resin, an epoxy resin, a polyurethane resin, or the like as a main component, but it is preferable to use the same adhesive as that of the first binding part 3 as 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 end surface on the first end side 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, the area between the holes 5 that can be a staying place can be reduced. 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 end of at least one hole 5 is arranged in a region within a range of 3 mm in height from the lowest part of the first end side end face 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.

Hereinafter, a description will be given of a method in which the first bundling portion 3 and the second bundling portion 4 are cured using an adhesive and the hollow fiber membrane 2 is potted.

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 performing potting, it is preferable to control the ambient temperature at 0 ° C. or more 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 sufficient strength even in high-temperature 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 direction of the end 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 completed and the adhesive is hardened, 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, a method for manufacturing the hollow fiber membrane module 100A according to the first embodiment will be described 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 has hardened, 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.

Cut the CC line portion of FIG. 3 with a tip saw type rotary blade to open the first end of the hollow fiber membrane 2 (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.

Also, 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 cleaning the membrane surface by reducing the turbidity accumulation and 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 process, when the filtrate, water, or the 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 inside of the hollow fiber membrane module is steam sterilized. In such a case, drainage flows through the hole 5 from the top to the bottom, and the steam drain is discharged from the filtrate inlet 9 to the outside of the hollow fiber membrane module.

[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 cross flow filtration, the effect of washing 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 the filtrate, water, or washing liquid is introduced from the filtrate outlet 22 or the filtrate outlet 23 and discharged from the hollow portion of the hollow fiber membrane 2 to the inside, the hollow fiber membrane When steam sterilization is performed inside the module, the steam drain is discharged from the filtrate outlet 23 or 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.

Thereby, even when an adhesive having a high glass transition temperature is used, the influence of curing shrinkage is suppressed, and when the first binding portion 3 and the cylindrical case 1 are bonded, it is possible to prevent adhesion peeling. .
Further, when the hollow fiber membrane bundle 12 bound to the first binding part 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 417,000 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 of polyoxyethylene sorbitan fatty acid ester (manufactured by Sanyo Chemical Industries, Ltd., Ionet (registered trademark) T-20C) and 3 parts by weight 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 slice is melted and formed into a plate shape, and HDT test apparatus (manufactured by Toyo Seiki Seisakusho 3M- 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.

The first binding part forming jig 16 and the second binding part forming jig 17 were arranged 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) 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.) Company made 4,4-methylenebis (cyclohexylamine)) and aliphatic chain amine curing agent (Wako Pure Chemical Industries, Ltd., diethylenetriamine) in a total mass of 2000 g (one end) Per 1000 g) and mixed in a potting agent feeder 19.
The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was 11.3. The maximum heat generation temperature of the adhesive reached at the time of curing was 158 ° 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. At this time, the temperature transition during curing was measured by inserting a thermocouple in the center of the adhesive, and as a result, the maximum temperature reached 151 ° C. Each member was not damaged by heat generation.

After curing, heat treatment was performed at 100 ° C. for 24 hours.
Thereafter, after the binding portion forming jigs 16 and 17 and the pin 18 are removed, the end portion (the CC 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 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) Glass transition temperature measurement When a part of the adhesive cured in (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 103 ° C., and it was possible to perform sterilization by filtering hot water at 80 ° C.

(C) Tensile test Five dumbbell test pieces No. 1 based on JISK7113 were produced with 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 at 180 ° 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 180 ° C. was calculated by the pycnometer method in accordance with JISK0061. As a result, it was 1.2 g / ml. The measurement was performed at N = 2.

(E) Viscoelasticity measurement The sheet | seat was produced with the same composition and hardening conditions as (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 a dynamic viscoelastic device (Rheogel-E4000, manufactured by UBM) was used 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 elastic modulus at 22O 0 C was 22 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 593.

(Example 2)
(A) Measurement of curing temperature of epoxy resin As an adhesive (potting agent) for molding the binding portion, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., JER825) and aliphatic cyclic amine curing agent (Wako Pure Chemical Industries Ltd.) 4,4-methylenebis (cyclohexylamine) manufactured by the company and an aliphatic chain amine-based curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) were mixed so that the mass ratio was 100: 20: 11. Other than the above, the second embodiment is the same as the first embodiment.

The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was 11.3. The maximum heat generation temperature of the adhesive reached at the time of curing was 153 ° 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 99 ° C., and it was possible to sterilize with warm water of 80 ° 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 A viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus was 11 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 1020.

(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.) The same as Example 1, except that 4,4-methylenebis (cyclohexylamine) manufactured by the company was mixed so that the mass ratio was 100: 31.

The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was 7.9. The maximum heat generation temperature of the adhesive reached at the time of curing was 167 ° 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 glass transition temperature was 148 ° C., and a high glass transition temperature was exhibited by using a large amount of alicyclic amine. It was possible to sterilize with hot water at 80 ° C., and sterilize with steam at 125 ° 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 36 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 300.

Example 4
(A) Measurement of curing temperature of epoxy resin As an adhesive (potting agent) for molding the binding portion, bisphenol A type epoxy resin (Mitsubishi Chemical Co., Ltd., JER828) and aromatic amine curing agent (Wako Pure Chemical Industries, Ltd.) Manufactured in the same manner as in Example 1 except that bis (4-aminophenyl) methane) was mixed so that the mass ratio was 100: 29.

The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminophenyl) methane as the main skeleton was 9.6. The maximum heat generation temperature of the adhesive reached at the time of curing was 154 ° 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 glass transition temperature was 152 ° C., and a high glass transition temperature was exhibited by using a large amount of aromatic amine. It was possible to sterilize with hot water at 80 ° C., and sterilize with steam at 125 ° 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 13 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 902.

(Example 5)
(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 The same as Example 1 except that a total of 6000 g (3000 g per one end) of the adhesive for forming the binding portion 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 176 ° 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 103 ° C., and it was possible to perform sterilization by filtering hot water at 80 ° 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 In the same manner as in Example 1, the density was calculated by the pycnometer method and found to be 1.2 g / ml.

(F) Viscoelasticity measurement As a result of performing a viscoelasticity test like Example 1, the average storage elastic modulus was 22 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 593.

(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 at the time of curing was 191 ° C., and the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A was melted. Further, peeling occurred between the polysulfone second cylindrical case 15 and the first binding portion 3.

(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. When sterilization was performed with warm water at 80 ° C., the fluid on the raw water side flowed out to the filtrate side from the separation between the second tubular case 15 made of polysulfone and the first binding portion 3.

(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 The viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus 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 low as 130.

(Comparative Example 2)
(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.) The same as Example 1, except that Tetraethylenepentamine (made by Co., Ltd.) was mixed so that the mass ratio was 100: 15.

The maximum exothermic temperature of the adhesive reached at the time of curing was 200 ° C., and the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A was melted. Further, peeling occurred between the polysulfone second cylindrical case 15 and the first binding portion 3.

(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 119 ° C. When sterilization was performed with warm water at 80 ° C., the fluid on the raw water side flowed out to the filtrate side from the separation between the second tubular case 15 made of polysulfone and the first binding portion 3.

(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 As a result of conducting a viscoelasticity test like Example 1, the average storage elastic modulus was 117 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 low as 109.

(Comparative Example 3)
(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.) The same as Example 1 except that the mass ratio was 100: 35.

The maximum heat generation temperature of the adhesive reached upon 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., and when sterilization or the like was performed with hot water at 80 ° C., the strength of the epoxy resin was significantly reduced, and the raw water side fluid flowed out to the filtrate side.

(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 ambient temperature of 80 ° C with the same composition as (a).

(D) Density measurement The density was calculated to be 1.0 g / ml by the pycnometer method in the same manner as in Example 1 except that the measurement was performed at an ambient temperature of 80 ° C.

(E) Viscoelasticity measurement As a result of conducting a viscoelasticity test like Example 1, the average storage elastic modulus in 80 degreeC 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 as large as 1781.

(Comparative Example 4)
(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 the company was mixed so that the mass ratio was 100: 44.

The maximum exothermic temperature of the adhesive reached at the time of curing was 195 ° C., and the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A was melted. Further, peeling occurred between the polysulfone second cylindrical case 15 and the first binding portion 3.

(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. When sterilization was performed with warm water at 80 ° C., the fluid on the raw water side flowed out to the filtrate side from the separation between the second tubular case 15 made of polysulfone and the first binding portion 3.

(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 The viscoelasticity test was conducted in the same manner as in Example 1. As a result, the average storage elastic modulus 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.

(Comparative Example 5)
(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 the company and an aromatic amine-based curing agent (manufactured by Mitsubishi Chemical Corporation, JER Cure W) were mixed so that the mass ratio was 100: 79: 20. Same as Example 1.

The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was 3.1. The maximum heat generation temperature of the adhesive reached at the time of curing was 130 ° 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 measured in the same manner as in Example 1. As a result, it was 70 ° C. When sterilization or the like was performed with hot water at 80 ° C., the strength of the epoxy resin was significantly reduced, and the raw water side fluid flowed out to the filtrate side.
This is probably because the value obtained by dividing the number of epoxy groups in the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was as small as 3.1.

(C) Tensile test As a result of conducting a tensile test in the same manner as in Example 1 except that the composition was the same as in (a) at an ambient temperature of 25 ° C., the dumbbell specimen was damaged when gripped with a chuck, Measurement was impossible. It is expected that the strength is extremely low.

(D) Density measurement As a result of calculating the density by the pycnometer method in the same manner as in Example 1, it was 1.2 g / ml.

(E) Viscoelasticity measurement As a result of performing a viscoelasticity test in the same manner as in Example 1, the test piece was damaged when gripped with a chuck, and measurement was impossible. It is expected that the strength is extremely low.

(Comparative Example 6)
(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 the company and an aliphatic chain amine-based curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) were mixed so that the mass ratio was 100: 11: 25. .

The value obtained by dividing the number of epoxy groups of the bisphenol A type epoxy resin by the number of amino groups in the component having bis (4-aminocyclohexyl) methane as the main skeleton was 25.9. 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., and when sterilization or the like was performed with warm water at 80 ° C., the strength of the epoxy resin was remarkably reduced, and the raw water side fluid flowed out to the filtrate side.

(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 ambient temperature of 80 ° C with the same composition as (a).

(D) Density measurement The density was calculated to be 1.3 g / ml by the pycnometer method in the same manner as in Example 1 except that the measurement was performed at an ambient temperature of 80 ° C.

(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 as large as 1776.

(Comparative Example 7)
(A) Curing temperature measurement of epoxy resin It is the same as Example 1 except having mixed a total of 6000 g (3000 g per one end) of the adhesive for forming the binding portion. The maximum exothermic temperature of the adhesive reached at the time of curing was 176 ° C., and the hollow fiber membrane 2 made of polyvinylidene fluoride of the hollow fiber membrane module 100A was partially melted.

(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 103 ° C. When sterilization was performed with warm water at 80 ° C., the fluid on the raw water side flowed out to the filtrate side from the separation between the melted hollow fiber membrane 2 made of polyvinylidene fluoride and the first binding portion 3.

(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 As a result of calculating the density by the pycnometer method in the same manner as in Example 1, it was 1.2 g / ml.

(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 22 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 593.

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. This application is based on a Japanese patent application filed on Jan. 29, 2016 (Japanese Patent Application No. 2016-015154), the contents of which are incorporated herein by reference.

The hollow fiber membrane module of the present invention can be used in a high temperature range, and can be applied particularly to a process requiring high temperature sterilization or steam sterilization when the liquid to be filtered is at a high temperature. Furthermore, since the hollow fiber membrane module of the present invention can suppress heat generation during the curing of the adhesive, it is possible to simultaneously cure a large volume of the adhesive and bind the polymer hollow fiber membrane. A polymer hollow fiber membrane module having a large membrane area per volume can be produced at low cost.
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 (11)

A cylindrical case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the cylindrical case, and at least one binding portion for binding the plurality of hollow fiber membranes, wherein the binding portion is bonded The adhesive contains an agent, and the glass transition temperature is 80 ° C. or higher and lower than 160 ° C., and Mc is bound by the formula (1) of the adhesive and the hollow portion of the hollow fiber membrane is opened. A hollow fiber membrane module in which the weight W of one bundling portion and the Vicat softening temperature VST of the hollow fiber membrane satisfy Expression 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 where the hollow part is opened The hollow fiber membrane module according to claim 1, wherein the adhesive has an Mc represented by the formula 1 of 140 or more and less than 1760. The hollow fiber membrane module according to claim 1 or 2, wherein the binding part contains (a) an epoxy resin and (b) an amine curing agent. The said binding part contains either (a) bisphenol type epoxy resin and (b) the hardening | curing agent which has at least one of an alicyclic amine and an aromatic amine as a main skeleton. 2. The hollow fiber membrane module according to item 1. The binding portion has (a) a bisphenol type epoxy resin having an epoxy equivalent of 150 or more and less than 250, and (b) at least one of bis (4-aminocyclohexyl) methane and bis (4-aminophenyl) methane as a main skeleton. The hollow fiber membrane module of any one of Claims 1-4 containing a hardening | curing agent. The bundling portion has (a) the number of epoxy groups in the bisphenol-type epoxy resin having an epoxy equivalent of 150 or more and less than 250, and (b) bis (4-aminocyclohexyl) methane and bis (4-aminophenyl) in the curing agent. 6) The bisphenol type epoxy resin containing (a) an epoxy equivalent of 150 or more and less than 250, wherein the value obtained by dividing at least one of methane by the number of amino groups of the curing agent having a main skeleton is 6 or more and less than 20. The hollow fiber membrane module described. The said binding part contains the particle | grains with an average particle diameter of 40 micrometers or less so that a sedimentation volume may be 150-1000 ml with respect to the said adhesive 100g, The any one of Claims 1-6. Hollow fiber membrane module. The hollow fiber membrane module according to any one of claims 1 to 7, wherein the cylindrical case and the bundling portion are liquid-tightly fixed by a sealing material. 9. The device according to claim 1, further 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 Item. Production of a hollow fiber membrane module comprising a cylindrical case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the cylindrical case, and at least one binding part for binding the plurality of hollow fiber membranes A method in which the binding portion contains an adhesive, the glass transition temperature of the adhesive is 80 ° C. or higher and lower than 160 ° C., and Mc represented by Formula 1 of the adhesive is used. A hollow fiber in which the adhesive and the hollow fiber membrane are selected so that the weight W of the one binding portion to be bundled with the hollow portion opened and the Vicat softening temperature VST of the hollow fiber membrane satisfy Equation 2. Membrane module manufacturing method.
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 where the hollow part is opened The manufacturing method of the hollow fiber membrane module of Claim 10 which selects the adhesive agent whose Mc shown by said Formula 1 is 140 or more and less than 1760 as said adhesive agent.

Images