KR20180103922A - Manufacturing method of hollow fiber membrane module and hollow fiber membrane module - Google Patents

Abstract

The present invention provides a hollow fiber membrane module comprising a normal case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the ordinary case, and at least one binding portion binding the plurality of hollow fiber membranes, wherein the binding portion contains an adhesive, Of the hollow fiber membrane has a glass transition temperature of 80 ° C or more and less than 160 ° C, and the weight Mc of the adhesive, which is expressed by a specific formula, the weight W of the binding portion bound in a state where the hollow portion of the hollow fiber membrane is opened, The Vicat softening temperature VST satisfies a specific formula.

Description

Manufacturing method of hollow fiber membrane module and hollow fiber membrane module

The present invention relates to a hollow fiber membrane module for use in a water treatment field, a fermentation industry field, a medicament / medical field, a food industry field, and the like, and more particularly to a hollow fiber membrane module having a binding portion with high heat resistance. The present invention also relates to a method for producing the hollow fiber membrane module.

As disclosed in Patent Document 1, a hollow fiber membrane module generally includes a hollow fiber membrane bundle in which about several hundred to several tens of thousands of hollow fiber membranes are bundled, and at least one end portion of the hollow fiber membrane bundle is bundled, It is a configuration that is accommodated.

Here, the bundled hollow fiber membrane is opened at at least one end, and the hollow part serves as a channel for the filtrate or the flux-overflow. Here, the binding portion has a function of binding the membrane and isolating the filtrate and the filtrate. In many cases, the binding portion is formed using an adhesive, and in particular, urethane resin or epoxy resin is widely used.

Patent Document 2 discloses that the application of the ultrafiltration membrane module or the microfiltration membrane module to purification of purified water or sewage is actively conducted; In such fields, it is considered necessary to reduce the cost of the processing cost due to the enlargement of the membrane module; There are several problems with the enlargement of the membrane module. One of them is that when the case is made of a material with low heat resistance, a problem arises that the case is deformed; And the problem of this deformation is that the amount of the adhesive to be used increases in a quadratic curve and the curing heat generation of the adhesive increases proportionally.

Patent Document 2 discloses a technique of providing a partition plate for dividing an adhesive into small amounts as a method for suppressing the curing heat generation of an adhesive in a large module.

International Publication No. 2010/014010 Japanese Patent Application Laid-Open No. 2000-185220

However, when the partition plate is used as in Patent Document 2, the hollow fiber membrane area that can be normally filled in the case is reduced, and the filtration ability of the hollow fiber membrane module is lowered. In addition, since the number of members increases, the manufacturing cost of the hollow fiber membrane module increases.

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-described conventional problems, and it is an object of the present invention to solve the problem of strength reduction and thermal deformation of a film, a housing, and the like caused by curing heat of an adhesive without using a separate member such as a partition plate The hollow fiber membrane module comprising:

The present inventors have found that by selecting the glass transition temperature of a specific range of the adhesive, Mc represented by the formula 1, and Vicat softening temperature VST of the hollow fiber membrane to satisfy the formula 2, heat resistance of the hollow fiber membrane module is realized, And it is possible to solve the above problems.

The present invention is based on this new knowledge and provides the following techniques (1) to (11).

(1) A hollow fiber membrane module comprising a normal case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the ordinary case, and at least one binding portion for binding the plurality of hollow fiber membranes, wherein the binding portion contains an adhesive, A glass transition temperature of 80 ° C or more and less than 160 ° C, and a value of Mc represented by the formula 1 of the adhesive, a weight W of the binding portion bound in a state where the hollow portion of the hollow fiber membrane is opened, Wherein the softening temperature VST satisfies the following equation (2).

  Mc = 2 (1 + μ) ρRT / E (Equation 1)

(g / m ³ ), R is the gas constant (J / K / mol), μ is the Poisson's ratio,

T: absolute temperature (K), E: storage elastic modulus (Pa)

  VST? 5.78 × W / Mc + 420 (Equation 2)

VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g)

(2) The hollow fiber membrane module according to (1), wherein the adhesive has Mc of 140 or more and less than 1760 represented by the formula (1).

(3) The hollow fiber membrane module according to (1) or (2), wherein the binding portion comprises (a) an epoxy resin and (b) an amine curing agent.

(4) The hollow member according to any one of (1) to (3), wherein the binding portion contains a curing agent having at least one of a bisphenol type epoxy resin (a) and an alicyclic amine and / Desert module.

(5) The epoxy resin composition as described in any one of (1) to (4) above, wherein the binding portion (a) has an epoxy equivalent of 150 or more and less than 250 and at least one of bis (4-aminocyclohexyl) methane and bis The hollow fiber membrane module according to any one of (1) to (4), wherein the hollow fiber membrane module further comprises a curing agent.

(6) The epoxy resin composition according to any one of the above items (1) to (4), wherein the binding portion in the bisphenol-type epoxy resin (a) having an epoxy equivalent of 150 or more and less than 250 is modified with bis (4-aminocyclohexyl) (A) the bisphenol-type epoxy resin having an epoxy equivalent of 150 or more and less than 250, wherein the value of (a) the epoxy group equivalent of the epoxy group-containing epoxy resin is in the range of 6 or more and 20 or less divided by the number of amino groups in the curing agent having at least one of .

(7) The hollow fiber membrane module according to any one of (1) to (6), wherein the binding portion contains particles having an average particle size of 40 μm or less so that the sedimentation volume is less than 150 ml and less than 1000 ml per 100 g of the adhesive.

(8) The hollow fiber membrane module according to any one of (1) to (7), wherein the ordinary case and the coupling portion are liquid-tightly fixed by a sealing material.

(9) The hollow fiber membrane according to any one of (1) to (8), further comprising a second ordinary case housed in the ordinary case, wherein the second ordinary case and the binding portion are liquid- module.

(10) A method for producing a hollow fiber membrane module including a normal case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the ordinary case, and at least one binding portion for binding the plurality of hollow fiber membranes, Wherein the adhesive has a glass transition temperature of 80 DEG C or more and less than 160 DEG C and is characterized by having a relationship of Mc represented by the formula 1 of the adhesive and weight W of the binding portion bound in a state in which the hollow portion of the hollow fiber membrane is opened And the adhesive and the hollow fiber membrane are selected so that the Vicat softening temperature VST of the hollow fiber membrane satisfies the following equation (2).

  Mc = 2 (1 + μ) ρRT / E (Equation 1)

(g / m ³ ), R is the gas constant (J / K / mol), μ is the Poisson's ratio,

T: absolute temperature (K), E: storage elastic modulus (Pa)

  VST? 5.78 × W / Mc + 420 (Equation 2)

VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g)

(11) The method for producing a hollow fiber membrane module according to claim 10, wherein an adhesive having Mc of 140 or more and less than 1760 is selected as the adhesive.

In the hollow fiber membrane module of the present invention, since the adhesive contained in the binding portion has a glass transition temperature of 80 DEG C or more, heat resistance that does not cause leakage of raw water during sterilization at high temperature and sterilization can be realized, When the softening temperature VST satisfies the formula 2, damage of the hollow fiber membrane module due to heat generation at the time of curing of the adhesive can be suppressed.

Further, when the glass transition temperature of the adhesive is less than 160 캜, thermal damage during curing of the adhesive can be further suppressed.

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

Hereinafter, the mode of the hollow fiber membrane module of the present invention will be described in detail with reference to the drawings.

Further, in the hollow fiber membrane module of the present invention, the terms "upper side" and "lower side" are based on the state shown in the drawing and are convenient, and the side to which the lead overflow is introduced is referred to as " Quot; upper side " direction.

Further, the direction from "lower side" to "upper side" is expressively referred to as "height direction". Normally, in the posture of the hollow fiber membrane module, the vertical direction coincides with the vertical direction in the drawing.

[First Embodiment]

The construction 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 vertical sectional view of an external pressure type hollow fiber membrane module 100A according to a first embodiment of the present invention.

<Structure of Hollow Fiber Membrane Module>

The hollow fiber membrane module 100A according to the first embodiment includes a normal case 1 having a first end and a second end in the height direction and a cylindrical case 1 housed in the ordinary case 1, A hollow fiber membrane bundle (12) having a plurality of hollow fiber membranes (2) having open ends and closed at the ends of the second end sides, and a first binding section 3 and a second binding portion 4 for binding the end portion on the second end side.

The normal case 1 is composed of a hollow normal case main body 1 and upper and lower caps 6 and 7 provided at both ends of the normal case main body 1.

1, an upper cap 6 having a filtrate outlet 8 is provided at an upper portion of the case body 1 and a lower cap 6 having a filtrate outlet 9 at a lower portion of the case body 1, And the caps 7 are tightly and liquid-tightly connected. The upper cap 6 and the lower cap 7 are fixed to the case body 1 by a clamp or the like, for example, using a gasket 10 as shown in Fig.

Normally, the case body 1 has a flange portion 1A and a flange portion 1B at the upper and lower ends thereof, over the entire circumference of the case body 1 in general. Normally, on the side of the case main body 1, a supercritical fluid outlet 11 is provided near the filtrate outlet 8.

The upper cap 6 usually has an inner diameter substantially equal to the inner diameter of the case body 1, and the upper end thereof is reduced in diameter to form the filtrate outlet 8. A stepped portion 6A for molding the groove is formed on the lower end side of the upper cap 6 over the entire circumference of the upper cap 6 when the case is connected to the case body 1. [

The lower cap 7 usually has an inner diameter substantially equal to the inner diameter of the case body 1, and the lower end of the lower cap 7 is reduced in diameter to mold the supernatant fluid inlet 9.

The hollow fiber membrane module 100A further includes a hollow fiber membrane bundle 12 including a plurality of hollow fiber membranes 2 and a binding portion for binding between the end portions of the hollow fiber membrane bundle 12 and the hollow fiber membranes 2 . The binding portion includes a first binding portion 3 normally disposed on the filtrate outlet 8 side of the case 1 and a second binding portion 4 disposed on the side of the overflow inlet 9 of the ordinary case 1 ). The second binding portion 4 is provided with a hole 5 serving as a flow path for the overflowing liquid.

The hollow fiber membrane module 100A is provided with a superfluous fluid outlet 11 and a plurality of hollow fiber membranes 11 arranged between the normal case 1 and the hollow fiber membrane bundle 12 so as to lie in the radial direction of the normal case 1, And the second normal case 15 is fixed to the first end side of the normal case 1. The second normal case 15 has the rectifying hole 14 of the first case 15,

<Hollow fiber membrane>

The hollow fiber membrane module of this embodiment has a hollow fiber membrane 2 as a separation membrane. The hollow fiber membrane is generally advantageous because it has a larger specific surface area than a flat membrane and has a large amount of filtrate per unit time. As the structure of the hollow fiber membrane, a symmetric membrane having a uniform pore diameter as a whole, an asymmetric membrane having a pore diameter varying in the thickness direction of the membrane as a whole, a composite membrane having a support layer for maintaining strength and a separation- And so on.

The average pore diameter of the hollow fiber membrane may be appropriately selected depending on the subject to be separated, but it is preferably 10 nm or more and 600 nm or less when it is intended to separate microorganisms such as bacteria or fungi or animal cells. If the average pore diameter is less than 10 nm, the water permeability is lowered. If the average pore diameter exceeds 600 nm, microorganisms may leak. The average pore diameter in the present invention is defined as the pore diameter of the dense layer having the smallest pore diameter.

The material of the hollow fiber membrane is not particularly limited, but examples of the hollow fiber membrane include polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene tetrafluoride · hexafluoropropylene copolymer, ethylene · tetrafluoroethylene copolymer Based resin, cellulose ester such as cellulose acetate, cellulose acetate propionate and cellulose acetate butyrate, polysulfone-based resin such as polysulfone and polyethersulfone, resin such as polyacrylonitrile, polyimide and polypropylene .

Particularly, since hollow fiber membranes containing fluorine resins or polysulfone resins are highly resistant to heat, physical strength and chemical durability, hollow fiber membranes, such as fermentation industry, pharmaceutical manufacturing industry, food industry and water treatment industry, which require steam sterilization or hot water sterilization Suitable for desert modules.

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

The hydrophilic resin may be a resin capable of imparting hydrophilicity to the hollow fiber membrane, and is not limited to a specific compound. For example, a cellulose ester, a fatty acid vinyl ester, vinyl pyrrolidone, ethylene oxide, propylene oxide, polymethacrylic acid ester Based resin and a polyacrylic ester-based resin are suitably used.

When fabricating a hollow fiber membrane module, the hollow fiber membrane is bound using an adhesive. In this case, the hollow fiber membrane is filled in the jig for forming a binding portion and fixed with an adhesive, but the hollow fiber membrane is dried in advance from the problem of handling or adhesion.

However, most of the hollow fiber membranes have shrinkage due to drying and deteriorate water permeability. Therefore, the hollow fiber membranes are preferably immersed in an aqueous glycerin solution and then dried. When it is immersed in an aqueous solution of glycerin and then dried, glycerin remains in the pores to prevent shrinkage due to drying, and then permeability can be restored by immersion treatment with a solvent such as ethanol.

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

If it is 30% or more, the film area per unit volume is large, and the manufacturing cost per film area can be reduced. Further, when forming the first binding portion, the heat generated by the curing reaction of the adhesive can be dissipated by the hollow fiber membrane to suppress the excessive temperature rise.

By making the amount less than 90%, it is possible to prevent the hollow fiber membranes from being squeezed out of each other 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, shrinkage may occur due to steam sterilization or hot water sterilization. Therefore, if steam sterilization or hot water sterilization is performed after the production of the hollow fiber membrane module, there is a possibility that the hollow fiber membrane is damaged due to shrinkage of the hollow fiber membrane or the hollow fiber membrane is separated from the binding part. Therefore, it is preferable that the hollow fiber membrane module is manufactured by treating the hollow fiber membrane with a vapor treatment or hot water in advance, shrinking it, and then performing end binding.

Generally, steam sterilization is carried out at 121 占 폚 or higher, and therefore, it is preferable to carry out pretreatment with a steam of 121 占 폚 or higher. The sterilization of hot water is generally carried out at about 80 DEG C, but the temperature is often changed depending on the process. Therefore, it is preferable to treat the hollow fiber membrane in advance with hot water at an expected use temperature or higher.

The hollow fiber membrane bundle 12 is formed in a state of being loose in view of workability of manufacturing the hollow fiber membrane module 100A and cleaning property of the hollow fiber membrane 2 in washing of the hollow fiber membrane module, Is normally accommodated in the case (1) through the connecting portion (3) or the connecting portion (4).

The reason for the slackness is that the length of the hollow fiber membrane 2 at that portion is smaller than the straight line distance from the second end side face of the first binding portion 3 to the first end side end face of the second binding portion 4 It says a long state.

&Lt; First binding portion &

Normally, on the first end side of the case 1, the first binding portion 3 which is the upper end side of the hollow fiber membrane module 100A is disposed. The first binding portion 3 is constituted by binding a hollow fiber membrane bundle 12 including a plurality of hollow fiber membranes 2. Here, the hollow portion of the hollow fiber membrane 2 is not sealed, but is in an open state, and the filtrate is taken out to the side of the upper cap 6 from the opening portion. The outer diameter of the first binding portion 3 is generally smaller than the outer diameter of the case 1. [

The binding portion contains an adhesive having a glass transition temperature of 80 DEG C or more and less than 160 DEG C or less. There are various methods of measuring the glass transition temperature, for example, differential scanning calorimetry (DSC) may be performed. The differential scanning calorimeter is commercially available, for example, DSC-60 Plus manufactured by Shimadzu Corporation.

As the glass transition temperature is 80 ° C or higher, it can be used under high temperature conditions such as filtration of hot liquid, hot water sterilization, and steam sterilization. Further, when the glass transition temperature is lower than 160 占 폚, the high-capacity adhesive can be cured and molded without deteriorating the hollow fiber membrane made of the polymer due to the curing heat. Further, the stress acting on the hardening shrinkage is suppressed, and when the binding portion and the case are bonded, the peeling of the adhesive can be prevented.

It is preferable that the binding portion contains an adhesive having Mc of 140 or more and less than 1760 represented by the formula (1). When Mc is 140 or more, curing heat generation is more likely to be suppressed. Further, when Mc is less than 1760, it is likely that the adhesive having an appropriate glass transition temperature range can be cured and molded.

  Mc = 2 (1 + μ) ρRT / E (Equation 1)

(g / m ³ ), R is the gas constant (J / K / mol), μ is the Poisson's ratio,

T: absolute temperature (K), E: storage elastic modulus (Pa)

For the measurement, a cured adhesive is used. In fact, when a hollow fiber membrane module is actually fabricated, it is possible to cut out the section from the bundling section and perform measurement. The Poisson's ratio can be obtained by performing a tensile test according to JIS K 7161. The density can be obtained by using a pycnometer method in accordance with JIS K 0061. The storage elastic modulus can be determined by performing a dynamic viscoelasticity test according to JIS K 7244. All of the measured values at or above the glass transition temperature are used, and the measured temperature is substituted into Equation 1 to calculate.

The molecular weight Mc between the crosslinking points is represented by Formula 1 by the classical rubber theory (Flory, P.J .: Chem. Rev. 35 (1944), 51). The molecular weight of the crosslinked point estimated by this method includes not only crosslinking derived from chemical bonds but also physical crosslinking such as entanglement of molecular chains.

The hollow fiber membrane module member such as the hollow fiber membrane and the ordinary case is preferably made of a material having heat resistance capable of withstanding sterilization by hot water or steam sterilization.

Among the materials having heat resistance, in the case of using a material made of a polymer having a relatively low heat resistance as compared with metals or ceramics, the temperature during curing of the adhesive is preferably lower than the Vicat softening temperature of the hollow fiber membrane. If the temperature during the curing of the adhesive is below the Vicat softening temperature of the hollow fiber membrane, the polymeric hollow fiber membrane can maintain strength, water permeability and separation performance. More preferably, when the temperature during curing of the adhesive agent is less than 130 캜, a wider range of materials can be used, such as a hollow fiber membrane module or a jig used for molding a binding portion.

The temperature during curing of the adhesive can be measured by placing a thermocouple in the hollow fiber membrane.

The Vicat softening temperature of the hollow fiber membrane can be measured in accordance with JIS K7206. The Vicat softening temperature measuring instrument is commercially available, for example, a 3M-2 type HDT testing device such as a Toyo Seiki Seisakusho Co., Ltd. can be used. The Vicat softening temperature of the hollow fiber membrane may be measured by melting the raw material for producing the hollow fiber membrane or the section of the hollow fiber membrane itself, shaping the hollow fiber membrane into a plate shape.

Since the adhesiveness of the adhesive during curing is smaller in heat radiation and higher in heat generation temperature in the vicinity of the center of the binding portion, it is preferable that the Vicat softening temperature of the hollow fiber membrane is lower than the heat generation temperature in the vicinity of the center.

It is known that the glass transition temperature of an adhesive, particularly an epoxy resin, is from 250 ° C to 250 ° C depending on the selection of composition molecules. Adhesives that exhibit high glass transition temperatures have high heat resistance, while requiring high temperatures to cure. Further, an adhesive having a high glass transition temperature generates a large amount of heat at the time of curing, and is remarkable particularly when curing an adhesive of several hundred grams or more.

The hollow fiber membrane made of a polymer is inferior in heat resistance as compared with a hollow fiber membrane made of ceramic, but can be produced at low cost and is easily used industrially. When thermal degradation occurs in the polymer hollow fiber membrane, there arises a problem that the liquid to be filtered leaks. As a result of intensive studies, the inventors of the present invention have been able to disclose the starting principle in which leakage of the filtrate due to thermal degradation occurs in the hollow fiber membrane module.

The polymer hollow fiber membrane is different in heat resistance depending on the material, but it is important that the Vicat softening temperature of the hollow fiber membrane is higher than the curing heat generation temperature, especially in the binding portion having the opening portion, in order to maintain the mechanical strength. The hardening heat of the binding portion was found to be related to the Mc of the adhesive and its weight, and Formula 2 was derived as a method of selecting a hollow fiber membrane optimum for manufacturing a hollow fiber membrane module having desired heat resistance.

That is, according to the present invention, the adhesive constituting the binding portion having the desired heat resistance is obtained by firstly calculating Mc according to Formula 1, and using the formula 2 as an index to select an adhesive constituting the hollow fiber membrane and the binding portion, The hollow fiber membrane module having heat resistance can be obtained in a satisfactory yield without deteriorating the membrane.

  VST? 5.78 × W / Mc + 420 (Equation 2)

VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g)

Further, as disclosed in Patent Document 2, there is disclosed a technique of providing a partition plate for dividing epoxy resin into small amounts in order to suppress curing heat generation causing thermal degradation of the hollow fiber membrane. However, when the partition plate is used, the hollow fiber membrane area that can be normally filled in the case is reduced, and the filtration ability of the hollow fiber membrane module is lowered. In addition, since the number of members increases, the manufacturing cost of the hollow fiber membrane module increases.

Generally, as a method for curing an adhesive having a high glass transition temperature of 80 캜 or more, a method of increasing the crosslinking point, that is, a method of reducing Mc in the present invention can be mentioned. However, when Mc is smaller than 140, the glass transition temperature is increased, but the heat of curing is increased, which tends to lead to deterioration of hollow fiber membrane module members such as hollow fiber membranes.

Further, when Mc is 140 or more, not only suppression of heat at the time of curing is suppressed, but sufficient toughness is easily provided. When Mc is less than 1760, it becomes easy to realize a glass transition temperature of 80 캜 or higher.

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.

When Mc is in this range, it is easy to realize an appropriate glass transition temperature of the adhesive and a curing heat generating temperature.

The adhesive suitably used for membrane bonding of the hollow fiber membrane module is an epoxy resin or a urethane resin. Of these, epoxy resins are suitably used because they have relatively high heat resistance.

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

It is easy to realize a favorable glass transition temperature of the adhesive and suppression of curing heat by mixing the epoxy resin and the amine curing agent (a) and (b) and curing them.

The epoxy resin (a) is more preferably (a) a bisphenol-type epoxy resin. The amine curing agent (b) is more preferably a curing agent having at least one of (b) 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 an epoxy equivalent of 150 or more and less than 250 (the following formula (a)). The amine curing agent (b) is more preferably at least one selected from the group consisting of bis (4-aminocyclohexyl) methane (the following formula (b1)) and bis (4-aminophenyl) It is a hardening agent having one side as a main skeleton.

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

Examples of the alicyclic amine include N-aminoethylpiperazine, bis (4-amino-3-methylcyclohexyl) methane, mencenediamine, isophoronediamine, bis Hexane and the like.

Examples of the aromatic amine include m-xylylenediamine, xylylenediamine derivative, xylylenediamine trimer, m-phenylenediamine, bis (4-aminophenyl) methane, diaminodiphenylsulfone and the like. These may be used alone or in combination of plural kinds.

There are various bisphenol-type epoxy resins, but bisphenol F type having X = H or bisphenol A type having X = CH ₃ is liquid and easy to handle.

(a) the bisphenol type epoxy resin (a) having an epoxy equivalent of 150 or more and 250 or less (a) is preferably contained in an amount of 60% or more.

(b1) and bis (4-aminophenyl) methane (the above formula (b2)) among the amine curing agents (b) The curing agent is preferably contained in an amount of 40% or more. at least one of (b) bis (4-aminocyclohexyl) methane (formula (b1)) and bis (4-aminophenyl) methane (formula (b2)) among the amine curing agents (b) The curing agent which is not particularly limited is preferably an aliphatic amine.

(b) bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4-aminocyclohexyl) methane in an amount of (a) an epoxy equivalent in the bisphenol- Amino phenyl) methane (the above formula (b2)) divided 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 a curing agent such as a chain aliphatic amine is 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 symmetry of the cured repeating unit of the epoxy resin becomes low, The glass transition temperature of the adhesive is lowered.

Further, in the case where 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, Is lowered.

(b2), bis (4-aminocyclohexyl) methane (the above formula (b1)) and bis (4-aminophenyl) methane (the above formula (b2) ), All of the carbon rings have a good symmetry, and the epoxy resin cured by this combination tends to cause the packing of the repeating units of the polymer chain to take place regularly.

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

On the other hand, the curing agent having at least one of (b) bis (4-aminocyclohexyl) methane (formula (b1)) and bis (4-aminophenyl) methane (formula (b2) The active hydrogen equivalent is larger than that of the curing agent, and thus the molecular weight between the crosslinking points becomes larger. As a result, it is easy to obtain an adhesive having a glass transition temperature of less than 160 캜 and a Mc of less than 1760.

Thus, by controlling not only the molecular weight between the crosslinking points but also the symmetry and rigidity of the main skeleton, it is possible to obtain an adhesive having an appropriate glass transition temperature and Mc of not less than 140 and less than 1760 of not less than 80 DEG C and less than 160 DEG C, It becomes easy to suppress.

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

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

In addition, the viscosity may be adjusted in consideration of the fluidity into the hollow fiber membrane at the time of curing molding of the adhesive and the handling property at the time of mixing, and a filler, a surfactant, a silane coupling agent and the like may be added.

In the case where the toughness-improving adhesive tends to be tough, rubber components or rubber particles are often added. Among them, the core-shell type rubber particles are effective because the toughness can be improved without deteriorating the heat resistance.

Silica, talc, zeolite, calcium hydroxide, calcium carbonate and the like fillers are sometimes added for various purposes such as suppression of curing heat generation, strength improvement, and thickening. However, when added in a large amount, the viscosity is increased and the handling property is lowered, which is not preferable.

There is a case where over-penetration of an adhesive agent, in which an adhesive passes through the pores and blocks the hollow portion, may occur from the outside of the hollow fiber membrane to the hollow portion side. And penetration occurs in the first binding portion, the flow path of the filtrate disappears, and filtration can not be performed.

In order to suppress penetration of the binder, the binding portion may contain particles having an average particle size of 40 탆 or less so that the sedimentation volume is less than 150 ml and less than 1000 ml per 100 g of the adhesive.

More preferably, the binding portion may contain particles having an average particle size of 20 占 퐉 or less so that the sedimentation volume is less than 200 ml and less than 500 ml per 100 g of the adhesive.

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

The sedimentation volume can be obtained as the volume of particles when the particles are put in an empty measuring cylinder and allowed to stand. When the sedimentation volume is less than 150 ml, it is difficult to completely prevent over-penetration of the adhesive.

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 into the hollow fiber membrane and the handling property at the time of mixing are impaired.

The material of the particles to be added does not need to satisfy the size and the sedimentation volume, but silica is suitably used because viscosity control is easy to control with other components such as a silane coupling agent.

The particles to be added may be dispersed beforehand in any of the (a) epoxy resin and (b) amine curing agent before curing by mixing the (a) epoxy resin and (b) amine curing agent. Usually, particles are added to the epoxy resin (a) and the amine curing agent (b) in a higher viscosity, so that the particles are hardly precipitated in the liquid even after storage for a long period of time. When the viscosity is adjusted by adding a silane coupling agent, it is preferable to add the silane coupling agent in advance in the same liquid as the particles.

The adhesives thus obtained can be used for cleaning membranes used for general purposes in a process using a hollow fiber membrane module, specifically inorganic acids such as hydrochloric acid and sulfuric acid, organic acids such as acetic acid, citric acid and lactic acid, and sodium hypochlorite, sodium hydroxide , Alkali such as sodium carbonate, and also a reducing agent such as sodium hydrogensulfite is also high in chemical durability. Therefore, even when the hollow fiber membrane module is used in the fields of food, biotechnology, medicine, etc., there is little concern about the elution.

The first binding portion is usually formed into a shape close to a cylinder, but it may be a rectangular parallelepiped or a shape close to a cube. In the case of a shape close to a cylinder, it is preferable to make the case easy to be normal, and to easily connect with a pipe for draining raw water or the like. The first binding portion formed into a cylindrical shape may have an outer diameter of 70 mm or more and less than 250 mm. 70 mm or more, it is possible to increase the film area per unit volume and to suppress the manufacturing cost of the apparatus per film area.

Since the adhesive obtained by the above method has high heat resistance and suppresses the heat generation at the time of curing, even if the outer shape of the first binding portion is 70 mm or more, the adhesive does not cause an excessive temperature rise at the time of curing. Further, by making the outer diameter less than 250 mm, the weight of the apparatus itself can be suppressed, and the load on the piping or the like to be connected can be suppressed.

In the fermentation industry or the medical or medical field, it is necessary to prevent contaminants from entering the filtration fluids or the filtration liquid (contamination). When using the hollow fiber membrane module in such fields, it is necessary to sterilize the hollow fiber membrane module A sterilization operation is performed.

Examples of general sterilization and sterilization methods include hot water sterilization, dry heat sterilization, boiling sterilization, steam sterilization, ultraviolet sterilization, gamma sterilization and gas sterilization. In particular, in the case of sterilization or sterilization of a large-sized jaw, piping and membrane module connected to a tank, hot water sterilization (usually 80 ° C for 1 hour) or steam sterilization (usually 121 ° C for 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 liquid tightly in 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 at the time of curing.

&Lt; Second binding portion &

The second binding portion 4 disposed on the side of the supernatant liquid inlet 9 of the case 1, that is, the lower end side of the hollow fiber membrane module 100A, is configured to close the hollow portion at the second end portion of the hollow fiber membrane 2, It is bound in one state.

The binding method is not particularly limited as long as the binding strength of the binding portion satisfies the mechanical strength, chemical durability, thermal durability, etc. However, a method of covering the outer periphery of the hollow fiber membrane bundle 12 with a heat shrinkable tube or the like and heating and binding, A method of arranging and bonding them in the form of a bean sprout, a method of bonding using an adhesive, and the like.

The adhesive may 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 the first binding portion 3 as the main component of the polymer. The polymer main component refers to a component containing the largest amount of the polymer among the polymers contained in the contained component. The second binding portion 4 may be fixed to the case 1 in a liquid-tight manner or in a communicable manner, and its fixing method has nothing to do with the present invention.

&Lt; Through hole in second binding portion >

The second binding section (4) has a hole (5) serving as a fluid flow path, such as a bonded superfluid. The total area of the holes 5 in the cross section perpendicular to the height direction is set to be smaller than the total area of the holes 5 in the cross section perpendicular to the height direction in order to reduce the stay of the flow in the vicinity of the end surface on the side of the first end side of the second fastening portion 4, Is preferably 2% or more and less than 35% with respect to the area of the inside of the normal case at a 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, which can become the retention position, can be reduced. Further, the pressure loss when the fluid passes through the hole 5 is reduced, and when the fluid flows from below to below, the pump power cost can be reduced. Further, when the fluid flows from the top to the bottom, the flow is likely to occur, and the possibility that the contaminants clog the hole 5 is suppressed. When the second binding portion is formed by using an adhesive in the same manner as the first binding portion, the hole 5 serves to dissipate the heat generated by the curing heat generation.

On the other hand, when the total area of the holes 5 is less than 35%, the cross-sectional area of the portion other than the hollow fiber membranes 2 in the second binding portion 4 becomes large, so that the hollow fiber membranes 2 become dense, It is possible to prevent the occurrence of defective sealing on the second side of the hollow fiber membrane 2 or difficulty in discharging the suspended matter deposited between the hollow fiber membranes 2. Further, if there is a bias in the flow that flows in the case where the fluid flows from the bottom to the top of the hole 5, the retentive portion is liable to occur, and the contaminants are liable to deposit. If the total area of the holes 5 is less than 35%, the pressure loss of the fluid is sufficient, and the imbalance to the flow into the hole 5 is small.

It is preferable that a plurality of holes 5 are present and the arrangement of the holes 5 is arbitrary such as a position of a vertex of a plurality of equilateral triangles, a position of an intersection point of radiation and a concentric circle, If there is a deviation in the interval between the adjacent ones, it is preferable that the interval is larger than the other interval because they are easy to stay.

It is more preferable that the end portion of at least one hole 5 is disposed in a region within a height of 3 mm from the lowest portion of the first end side end face of the second binding portion 4. If the first end side end face of the second binding portion 4 is not horizontal in the case where the fluid flows down from the top to the bottom, the staying portion is likely to occur at the lowest portion, To do.

In the case where the first end side end face of the second binding portion 4 is not horizontal, for example, the following cases can be mentioned. When the second binding portion 4 is formed by an adhesive, and in particular, centrifugal potting is performed, a concave portion is formed in the central portion of the second end side of the first binding portion due to the centrifugal force. Further, due to the influence of gravity, a slope is formed in the upper direction and the lower direction at the time of bonding.

On the other hand, in the potting method, the second end side end face of the first binding portion 3 may be horizontal, but when the second binding portion forming jig 17 is potted in the vertical direction, And an inclination is formed on the second end side end face.

The cross-sectional shape perpendicular to the height direction of the hole 5 is arbitrary such as circular, elliptical, polygonal, and star-shaped.

&Lt; Normal Case, Material of Second Normal Case >

The material of the ordinary case 1 used in the hollow fiber membrane module is not particularly limited as long as it meets the mechanical strength, chemical durability, thermal durability and the like. For example, a vinyl chloride resin, a polypropylene resin, Fluorine resins such as tetrafluoroethylene and perfluoroalkoxy fluorine resin, polycarbonate, polypropylene, polymethylpentene, polyphenylene sulfide, polyether ketone, stainless steel, aluminum and the like.

The material of the second ordinary case 15 used in the hollow fiber membrane module is not particularly limited, but can be selected from the same materials as the case 1, for example.

<Manufacturing Method of Hollow Fiber Membrane Module>

Hereinafter, a method of manufacturing the hollow fiber membrane module according to the first embodiment will be described. In addition, the manufacturing method described here is not limited to the first embodiment, and any of the later-described embodiments can produce the hollow fiber membrane module by the same method.

Hereinafter, the first binding portion 3 and the second binding portion 4 are cured by using an adhesive, and then the hollow fiber membrane 2 is potted.

As a potting method, a centrifugal potting method in which a liquid adhesive is infiltrated between hollow fiber membranes by using centrifugal force and then cured, and a liquid adhesive is fed by a metering pump or a head to naturally flow to penetrate between the hollow fiber membranes 2, May be used.

When porting is carried out, it is preferable to control the ambient temperature at 0 캜 or more and less than 60 캜. By setting the temperature to 0 占 폚 or higher, the curing reaction of the adhesive can be promoted. In the epoxy resin, the reaction between the epoxy group and the amine can be promoted. More preferably, the reaction time can be shortened by 5 DEG C or more. In addition, when the temperature is lower than 60 DEG C, excessive curing heat generation can be suppressed. More preferably, the temperature is less than 50 占 폚, so that the worker can take a slight heat-resistant measure, and the workability is good.

The cured adhesive can increase its strength by heating in a subsequent step. Concretely, it is preferable to perform heat treatment at 80 占 폚 or higher. By performing the heat treatment at 80 占 폚 or more, the strength of the adhesive has a sufficient strength even in a high-temperature operation such as in hot water sterilization. Further, by heat treatment at a temperature not higher than the Vicat softening temperature of the hollow fiber membrane, it is possible to prevent damage to the members other than the adhesive such as the hollow fiber membrane due to heat. More preferably, by heat treatment at 90 占 폚 or higher, the adhesive has a sufficient strength, and damage by heat of members other than the adhesive can be prevented.

Further, the heat treatment may be carried out by increasing the temperature stepwise. For example, it is preferable to perform heat treatment at a plurality of temperature steps at 80 ° C, 100 ° C, and 120 ° C after heat treatment at 60 ° C for a certain period of time.

In the centrifugal potting method, the adhesive tends to penetrate between the hollow fiber membranes due to the centrifugal force, and an adhesive having a high viscosity can also be used. When a polyurethane resin is used as the adhesive for bonding the hollow fiber membrane 2, since water contained in the hollow fiber membrane 2 reacts with isocyanate to generate carbon dioxide and foam, the polyurethane resin is obtained by the potting method It is difficult to use.

In the centrifugal potting method, a pressure is generated in the end direction of the hollow fiber membrane module by the centrifugal force, and the bubble falls inward, so that a polyurethane resin can be used as an adhesive for bonding the hollow fiber membrane 2. On the other hand, in the political porting, a large facility such as a centrifugal molding machine is unnecessary.

After the potting is completed and the adhesive is cured, the end surface of the hollow fiber membrane 2 is opened by cutting the binding portion at the first end side of the first binding portion 3. It is preferable that the hollow portion at the first end of the hollow fiber membrane 2 is sealed with a silicone adhesive or the like before the porting. By performing the eye sticking treatment, it is possible to prevent the penetration of the potting agent into the hollow portion, and to prevent the occurrence of the hollow yarn in which the hollow portion is filled with the potting agent and the permeated liquid does not come out.

In the case of bonding the first binding portion 3 to the inside of the second ordinary case 15 and fixing the binding portion by bonding to the ordinary case 1, 15, and the inner surface of the ordinary case 1 may be subjected to a sandblasting, a plasma treatment, a primer treatment, or the like.

Next, a method of 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 is also applicable to the hollow fiber membrane module of any of the embodiments described below.

First, the hollow fiber membrane bundle 12 is installed in a centrifugal potting apparatus shown in Fig. 3, centrifugal potting is performed, and the first binding section and the second binding section are formed (step S1).

Here, the hollow fiber membrane bundle 12 is normally housed in the case 1, the first end of the hollow fiber membrane bundle 12 is connected to the second ordinary case 15, and the second ordinary case 15 is connected to the first binding The second end portion of the hollow fiber membrane bundle 12 is inserted into the second binding portion molding jig 17 in the auxiliary molding jig 16, respectively. In addition, a pin 18 is inserted into the through hole at the bottom of the second binding section molding jig 17. The first end of the hollow fiber membrane 2 is pre-treated with a silicone adhesive in advance.

The potting agent dispenser 19 is normally connected to the case 1. By rotating the entire apparatus in the centrifugal molding machine, the potting agent is rotated by the centrifugal force in the first binding part case 16 and the second binding part forming jig 19, (17). The potting agent may be supplied to the first binding part forming jig 16 and the second binding part forming jig 17 at the same time or separately.

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

C-C line portion of Fig. 3 is cut off by a chip sole type rotary blade, and the first end of the hollow fiber membrane 2 is opened (step S2).

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

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

The material of the fin is not particularly limited as long as heat resistance, chemical durability, and the like are satisfied. For example, a material similar to that of the jig for binding part can be used. In the case of using a metal, a coating of a fluorine resin or the like may be performed in order to improve releasability.

&Lt; Operation method of hollow fiber membrane module >

During the filtration operation using the hollow fiber membrane module 100A, the overflow liquid enters the overflow liquid inflow port 9 and passes through the hole 5 from the second end side of the second binding section 4, (12). After passing through the hollow fiber membrane 2, the filtrate passes through a space surrounded by the first binding portion 3 and the upper cap 6 as a filtrate, and then is taken out of the hollow fiber membrane module from the filtrate outlet 8 .

In the case of performing dead-end filtration, a part of the surplus fluid introduced into the ordinary case 1 is taken out from the surplus superfluous fluid outlet 11 in the case of performing cross-flow filtration although the surplus fluid overflow outlet 11 is abolished, The taken-out excess liquid is again introduced into the hollow fiber membrane module from the feed-through liquid inlet 9.

By performing cross-flow filtration, a flow easily occurs in the hollow fiber membrane module, and the effect of reducing the surface sedimentation and cleaning the membrane surface by the flow near the membrane surface is obtained. Cross-flow filtration is widely used, particularly in fermentation industry, medicine and medical field, and food industry.

In general, after the filtration operation is performed using the hollow fiber membrane module for a certain period of time, a step of cleaning the interior of the hollow fiber membrane module is provided, and water, a chemical liquid, gas, or the like is supplied from the filtrate fluid inlet 9. Especially, in a process requiring hot water sterilization, hot water of about 80 캜 is supplied.

On the other hand, in the cleaning process, when a method of introducing a filtrate, water, or a cleaning liquid from the filtrate outlet 8 and discharging the hollow fiber membrane 2 outward from the hollow portion of the hollow fiber membrane 2, In the case of sterilization or the like, drainage flows from the top to the bottom of the hole 5, and the vapor drain is discharged to the outside of the hollow fiber membrane module from the influent inlet 9.

[Second Embodiment]

The structure of the hollow fiber membrane module 100B according to the second embodiment of the present invention will be described with reference to the drawings. 4 is a schematic vertical sectional view of the hollow fiber membrane module 100B according to the second embodiment. The structure of the hollow fiber membrane module 100B not mentioned below can be applied to the structure of the hollow fiber membrane module 100A of the first embodiment. Members having the same functions as those of the members described in the first embodiment are denoted by the same reference numerals and the description thereof will be omitted.

During the filtration operation using the pressure-resistant hollow fiber membrane module 100B according to the second embodiment, the surplus overflow enters from the supernatant fluid inlet 21 and flows from the second end of the second binding portion 4 to the hollow fiber membrane 2 Passes through the hollow portion, and is taken out of the hollow fiber membrane module from the supercritical fluid outlet 20. The filtrate passes through the hollow fiber membrane 2 and is taken out between the hollow fiber membrane bundles 12 usually surrounded by the case 1 as a filtrate and then taken out of the hollow fiber membrane module from the filtrate outlet 22, do.

In the case of performing the dead-end filtration, the filtration fluid outlet 20 is abolished, but in the case of performing cross-flow filtration, the filtrate filtrate taken out from the filtration fluid outlet 20 again flows from the filtrate fluid inlet 21 to the hollow fiber membrane module Lt; / RTI &gt;

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

Generally, after the filtration operation is performed using the hollow fiber membrane module for a certain period of time, a step of cleaning the inside of the hollow fiber membrane module is provided, and water, a chemical solution, gas, or the like is supplied from the filtrate overflow inlet 21. Especially, in a process requiring hot water sterilization, hot water of about 80 캜 is supplied.

On the other hand, in the cleaning step, a method is adopted in which a filtrate, water, or a cleaning liquid is introduced from the filtrate outlet 22 or the filtrate outlet 23 and is discharged from the hollow portion of the hollow fiber membrane 2 inward The steam drain is discharged to the outside of the hollow fiber membrane module from the filtrate outlet 23 or the fed excessive fluid inlet 21 in the case of steam sterilization in the hollow fiber membrane module.

[Third embodiment]

A hollow fiber membrane module 100C according to a third embodiment of the present invention will be described with reference to the drawings. 5 is a schematic vertical sectional view of the first end side of the hollow fiber membrane module 100C according to the third embodiment. The structure of the hollow fiber membrane module 100C not described below can be applied to the structure of the hollow fiber membrane module 100A of the first embodiment. Members having the same functions as those of the members described in the first embodiment are denoted by the same reference numerals and the description thereof will be omitted.

In the hollow fiber membrane module 100C according to the third embodiment, the first binding portion 3 squashes the sealing material 25 and the sealing material 26, and the second normal case 15 and the upper cap 6 As shown in Fig.

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

Except for the method of fixing the first binding portion 3 and the second ordinary case 15, the structure, operating method, and manufacturing method are the same as those of the hollow fiber membrane module 100A of the first embodiment. The first bonding portion 3 is liquid tightly fixed to the second normal case 15 through the sealing material so that the bonding surface between the first binding portion 3 and the second normal case 15 does not exist, There is no case where defective peeling occurs.

Thus, even when an adhesive having a high glass transition temperature is used, the influence of the curing shrinkage can be suppressed, and adhesion peeling can be prevented when the first binding portion 3 and the ordinary case 1 are bonded .

It is also possible to reuse the second ordinary case 15 and the ordinary case 1 when deterioration of the hollow fiber membrane bundle 12 bound to the first binding portion 3 occurs.

The second normal case 15 is normally used to control the liquid flow outside the hollow fiber membrane 2 in the case 1. When the flow rate of the liquid flow at that portion is small, 15) may not be used. In this case, normally the case 1 and the first binding portion 3 are liquid-tightly fixed by a sealing material, and there is no bonding surface, so that there is no case where defective adhesive peeling occurs.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

(a) Preparation of hollow fiber membrane

38 parts by mass of a vinylidene fluoride homopolymer having a weight average molecular weight of 417,000 and 62 parts by mass of? -Butyrolactone were mixed and dissolved at 160 占 폚. This polymer solution was discharged from a spinneret of a double tube while causing an aqueous solution of 85% by mass of gamma -butyrolactone as a hollow portion forming liquid, and an aqueous solution of 85% by mass of gamma -butyrolactone having a temperature of 20 DEG C , Thereby preparing a hollow fiber membrane having a spherical structure.

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

The membrane-forming raw 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 prepare a hollow fiber membrane 2 having a three-dimensional structure on the spherical structure layer.

The resultant hollow fiber membrane 2 had an outer diameter of 1350 mu m and an inner diameter of 800 mu m and an average pore diameter of the membrane surface of 40 nm. The hollow fiber membrane slice was melted and formed into a plate, and an HDT tester (3M-2 type available from Toyo Seiki Seisaku- ) Was used to measure Vicat softening temperature, which was 170 ° C.

(b) Production of hollow fiber membrane module

The hollow fiber membrane (2) obtained in the above (a) was cut into a length of 1800 mm, immersed in a 30% by mass aqueous glycerin solution for 1 hour, and air dried. The hollow fiber membrane 2 was heat-treated for 1 hour with water vapor at 125 캜, air-dried, and cut into a length of 1200 mm.

Thereafter, the first end side of the hollow fiber membrane 2 was visually infused with a silicone adhesive (SH850A / B, manufactured by Toray Dow Corning Toray Co., Ltd., two components were mixed so as to have a mass ratio of 50:50).

Thereafter, as shown in Fig. 3, 5,000 of the hollow fiber membranes 2 described above were filled in a stainless steel case 1 (inner diameter: 145 mm, outer diameter: 155 mm, length: 1000 mm, division die).

In addition, a polysulfone second normal case 15 was arranged on the first end side in the stainless steel case 1.

The first binding part forming jig 16 and the second binding part forming jig 17 were disposed at both ends of the stainless steel case 1. A pin 18 was inserted into the through hole at the bottom of the jig 17 for forming the second binding portion.

(Example 1)

(a) Measurement of curing temperature of epoxy resin

As a bonding agent (potting agent) for forming a binding portion, a bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and an aliphatic cyclic amine type curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylene bis Cyclohexylamine)) and an aliphatic chain amine curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylenetriamine) were mixed in a total weight of 2000 g (1000 g per one end) so that the mass ratio was 100: 22: And placed in a dispenser 19.

The value obtained by dividing the epoxy group number 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 exothermic temperature of the adhesive reached at the time of curing was 158 DEG C, and no damage due to heat generation was given to the members of the hollow fiber membrane module 100A.

Subsequently, the centrifugal molding machine was rotated, and the adhesive agent was filled in the jig (16, 17) for binding part 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 number of revolutions was 350 rpm, and the centrifugal time was 5 hours. At this time, the temperature change during curing was measured by inserting a thermocouple at the center of the adhesive, and the maximum temperature reached 151 占 폚. No damage due to heat was observed in each member.

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

After the jig 16 and 17 and the pin 18 are removed, the end of the first binding portion 3 (the CC side shown in Fig. 3) is cut into a chip sole type rotary knife, The end surface of the desert 2 was opened.

Subsequently, an upper cap 6 and a lower cap 7 were provided at both ends to form a hollow fiber membrane module 100A as shown in Fig. Thereafter, ethanol was fed to the hollow fiber membrane module 100A to perform filtration, and the pores of the hollow fiber membrane 2 were filled with ethanol. Then, RO (Reverse Osmosis) water was fed to perform filtration, and ethanol was replaced with RO water.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (a) was cut out, and the amount of heat when the temperature was elevated from 25 占 폚 to 300 占 폚 at 10 占 폚 / min using DSC-60 Plus manufactured by Shimadzu Seisakusho Co., The transition temperature was determined.

The results are shown in Table 1. The glass transition temperature was 103 占 폚, and it was possible to perform sterilization or the like by filtering hot water at 80 占 폚.

(c) Tensile test

Five test pieces No. 1 according to JIS K7113 were prepared under the same composition and curing conditions as in (a), and tensile tests were conducted in accordance with JIS K7161. The dumbbell was subjected to a tensile test with N = 5 at 5 mm / min in a thermostatic ceylon controlled at 180 캜 atmosphere. Using a strain gauge, the Poisson's ratio was 0.5.

(d) Density measurement

A sheet was prepared under the same composition and curing conditions as in (a). Twenty cubes of 7 mm on each side were cut out from the sheet and the density at 180 캜 was calculated by the pycnometer method according to JISK0061 to be 1.2 g / ml. The measurement was performed with N = 2.

(e) Viscoelasticity measurement

A sheet was prepared under the same composition and curing conditions as in (a). A test piece having a thickness of 1 mm, a width of 10 mm and a length of 50 mm was cut out from the sheet and heated at a temperature raising rate of 5 캜 / min in a temperature range of 25 to 200 캜 using a dynamic viscoelastic device (Rheogel-E4000, The temperature dependency of the storage elastic 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 carried out at N = 3, and the average storage elastic modulus at 180 캜 was 22 MPa.

(f) Calculation of Mc

Mc was calculated by substituting the values measured in (c), (d), and (e) in (Equation 1). The results are shown in Table 1. Mc was 593.

(Example 2)

(a) Measurement of curing temperature of epoxy resin

(JER 825, manufactured by Mitsubishi Chemical Corporation) and an alicyclic amine-based curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylenebis (triphenylphosphine)) as an adhesive (potting agent) Cyclohexylamine)) and an aliphatic chain amine-based curing agent (manufactured by Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) were mixed so that the mass ratio thereof was 100: 20: 11.

The value obtained by dividing the epoxy group number 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 DEG C, and damage to the members of the hollow fiber membrane module 100A by heat was not given.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 占 폚, and sterilization with hot water at 80 占 폚 was possible.

(c) Tensile test

(a) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1 and found to be 1.0 g / ml.

(e) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and 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) in (Equation 1). The results are shown in Table 1. Mc was 1020.

(Example 3)

(a) Measurement of curing temperature of epoxy resin

As a bonding agent (potting agent) for forming a binding portion, a bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and an aliphatic cyclic amine type curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylene bis Cyclohexylamine)) were mixed in a mass ratio of 100: 31.

The value obtained by dividing the epoxy group number 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 exothermic temperature of the adhesive reached at the time of curing was 167 DEG C, and the member of the hollow fiber membrane module 100A was not damaged by heat generation.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 DEG C and a high glass transition temperature was exhibited by using a large amount of alicyclic amine. It was possible to perform sterilization by hot water at 80 DEG C, further sterilization by steam at 125 DEG C, and the like.

(c) Tensile test

(a), a tensile test was conducted in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1 and found to be 1.0 g / ml.

(e) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and 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) in (Equation 1). The results are shown in Table 1. Mc was 300.

(Example 4)

(a) Measurement of curing temperature of epoxy resin

(4-aminophenyl) methane (manufactured by Wako Pure Chemical Industries, Ltd.) as an adhesive (potting agent) for forming a binding portion, a bisphenol A type epoxy resin (JER828 made by Mitsubishi Chemical Co., )) Were mixed so as to have a mass ratio of 100: 29.

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-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 deg. C, and the member of the hollow fiber membrane module 100A was not damaged by heat generation.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 캜, and a high glass transition temperature was exhibited by using a large amount of aromatic amine. It was possible to perform sterilization by hot water at 80 DEG C, further sterilization by steam at 125 DEG C, and the like.

(c) Tensile test

(a), a tensile test was conducted in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1 and found to be 1.0 g / ml.

(e) Viscoelasticity measurement

As a result of performing a viscoelasticity test in the same manner as in Example 1, 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) in (Equation 1). The results are shown in Table 1. Mc was 902.

(Example 5)

(a) Preparation 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 were mixed and dissolved, Discharged from the cage, and immediately solidified in water at a temperature of 20 캜. The obtained hollow fiber separation membrane was immersed in ethanol, further immersed in hexane and dehydrated. Thereafter, heat treatment was performed for 2 hours in an atmosphere of 150 ° C to crosslink polyvinylpyrrolidone. The hollow fiber membrane slice was melted and molded into a plate, and the Vicat softening temperature was measured at 220 캜 using an HDT tester (Model 3M-2, manufactured by Toyo Seiki Seisakusho Co., Ltd.).

(b) Curing temperature measurement of epoxy resin

The same as Example 1 except that a total of 6000 g (3000 g per one end) of an adhesive for forming a binding portion and a polyethersulfone hollow fiber membrane were used. The maximum exothermic temperature of the adhesive reached at the time of curing was 176 DEG C, and no damage due to heat was given to the members of the hollow fiber membrane module 100A.

(c) Glass transition temperature measurement

a portion 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 占 폚, and it was possible to perform sterilization or the like by filtering hot water at 80 占 폚.

(d) Tensile test

(b) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(e) Density measurement

The density was calculated by the pycnometer method in the same manner as in Example 1. The result was 1.2 g / ml.

(f) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and the average storage elastic modulus was 22 MPa.

(g) Production of Mc

Mc was calculated by substituting the values measured in (d), (e), and (f) in (Formula 1). The results are shown in Table 1. Mc was 593.

(Comparative Example 1)

(a) Measurement of curing temperature of epoxy resin

As the adhesive (potting agent) for forming the binding portion, bisphenol A type epoxy resin (JER828 made by Mitsubishi Chemical Co., Ltd.) and an aliphatic chain amine curing agent (diethylene triamine made by Wako Pure Chemical Industries, Ltd.) Was 100: 11.

The maximum exothermic temperature of the adhesive reached at the time of curing was 191 ° C, and the polyvinylidene fluoride hollow fiber membrane 2 of the hollow fiber membrane module 100A was melted. Further, peeling occurred between the polysulfone second case (15) and the first binding portion (3).

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 占 폚. After sterilizing with hot water at 80 캜, the raw water-side fluid flowed out to the filtrate side from the separation between the polysulfone second case 15 and the first binding portion 3.

(c) Tensile test

(a) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1. As a result, it was 1.1 g / ml.

(e) Viscoelasticity measurement

As a result of performing a viscoelasticity test in the same manner as in Example 1, 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) in (Equation 1). The results are shown in Table 1. Mc was as low as 130.

(Comparative Example 2)

(a) Measurement of curing temperature of epoxy resin

A bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Co., Ltd.) and an aliphatic chain amine curing agent (tetraethylenepentamine, manufactured by Wako Pure Chemical Industries, Ltd.) were mixed in a mass ratio Was 100: 15, as in Example 1.

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

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 占 폚. After sterilizing with hot water at 80 캜, the raw water-side fluid flowed out to the filtrate side from the separation between the polysulfone second case 15 and the first binding portion 3.

(c) Tensile test

(a) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1. As a result, it was 1.1 g / ml.

(e) Viscoelasticity measurement

As a result of the viscoelasticity test in the same manner as in 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) in (Equation 1). The results are shown in Table 1. Mc was as low as 109.

(Comparative Example 3)

(a) Measurement of curing temperature of epoxy resin

(JER 828, manufactured by Mitsubishi Chemical Corporation) and an aliphatic chain amine-based curing agent (diethylaminopropylamine, manufactured by Wako Pure Chemical Industries, Ltd.) as an adhesive (potting agent) Was mixed so that the weight ratio was 100: 35.

The maximum heat generation temperature of the adhesive reached at the time of curing was 150 DEG C, and no damage due to heat generation was given to the members of the hollow fiber membrane module 100A.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 캜. When sterilization was conducted with hot water at 80 캜, the strength of the epoxy resin remarkably decreased, and the fluid on the raw water side flowed out toward the filtrate.

(c) Tensile test

A Poisson's ratio was 0.5 as a result of carrying out a tensile test in the same manner as in Example 1, except that the composition was the same composition as that of Example 1 (a) at an ambient temperature of 80 캜.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1, except that the operation was carried out at an ambient temperature of 80 캜. As a result, the density was 1.0 g / ml.

(e) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and the average storage elastic modulus at 80 캜 was 7 MPa.

(f) Calculation of Mc

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

(Comparative Example 4)

(a) Measurement of curing temperature of epoxy resin

(JER 604, manufactured by Mitsubishi Chemical Corporation) and an aliphatic cyclic amine-based curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylenebis (cyclohexane) Hexylamine)) were mixed in a mass ratio of 100: 44.

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

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 占 폚. After sterilizing with hot water at 80 캜, the raw water-side fluid flowed out to the filtrate side from the separation between the polysulfone second case 15 and the first binding portion 3.

(c) Tensile test

(a) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1. As a result, it was 1.1 g / ml.

(e) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and 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) in (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 a bonding agent (potting agent) for forming a binding portion, a bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and an aliphatic cyclic amine type curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylene bis Cyclohexylamine)) and an aromatic amine-based curing agent (JER CURE W manufactured by Mitsubishi Chemical Corporation) so as to have a mass ratio of 100: 79: 20.

The value obtained by dividing the epoxy group number 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 exothermic temperature of the adhesive reached at the time of curing was 130 DEG C, and no damage due to heat was given to the members of the hollow fiber membrane module 100A.

(b) Glass transition temperature measurement

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, and as a result, it was 70 ° C. The strength of the epoxy resin was remarkably lowered and the fluid on the raw water side flowed out to the filtrate side when sterilized by hot water at 80 ° C.

The value obtained by dividing the epoxy group number 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.

(c) Tensile test

A tensile test was carried out in the same manner as in Example 1 except that the test piece was subjected to the same composition as in Example 1 (a) at an atmospheric temperature of 25 캜. As a result, the dumbbell test piece was broken when held by a chuck. It is expected that the strength is remarkably low.

(d) Density measurement

The density was calculated by the pycnometer method in the same manner as in Example 1. The result was 1.2 g / ml.

(e) Viscoelasticity measurement

As a result of performing the viscoelasticity test in the same manner as in Example 1, the test piece was broken when it was held by the chuck, and measurement was impossible. It is expected that the strength is remarkably low.

(Comparative Example 6)

(a) Measurement of curing temperature of epoxy resin

As a bonding agent (potting agent) for forming a binding portion, a bisphenol A type epoxy resin (JER828, manufactured by Mitsubishi Chemical Corporation) and an aliphatic cyclic amine type curing agent (manufactured by Wako Pure Chemical Industries, Ltd., 4,4-methylene bis Cyclohexylamine) and an aliphatic chain amine-based curing agent (Wako Pure Chemical Industries, Ltd., diethylaminopropylamine) were mixed in a mass ratio of 100: 11: 25.

The value obtained by dividing the epoxy group number 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 deg. C, and no damage due to heat was given to the members of the hollow fiber membrane module 100A.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 캜. When sterilization with hot water at 80 캜 was carried out, the strength of the epoxy resin remarkably decreased, and the fluid on the raw water side flowed out toward the filtrate.

(c) Tensile test

A Poisson's ratio was 0.5 as a result of carrying out a tensile test in the same manner as in Example 1, except that the composition was the same composition as that of Example 1 (a) at an ambient temperature of 80 캜.

(d) Density measurement

The density was calculated by a pycnometer method in the same manner as in Example 1, except that the operation was performed at an ambient temperature of 80 캜, and as a result, it was 1.3 g / ml.

(e) Viscoelasticity measurement

As a result of performing a viscoelasticity test in the same manner as in Example 1, 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) in (Equation 1). The results are shown in Table 1. Mc was big at 1776.

(Comparative Example 7)

(a) 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. The maximum exothermic temperature of the adhesive reached at the time of curing was 176 DEG C, and the polyvinylidene fluoride hollow fiber membrane 2 of the hollow fiber membrane module 100A partially melted.

(b) Glass transition temperature measurement

a part of the adhesive cured in step (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 占 폚. The fluid at the raw water side flowed out to the filtrate side from the peeling between the molten polyvinylidene fluoride hollow fiber membrane 2 and the first binding portion 3 as a result of sterilization with hot water at 80 ° C.

(c) Tensile test

(a) was subjected to a tensile test in the same manner as in Example 1. As a result, the Poisson's ratio was 0.5.

(d) Density measurement

The density was calculated by the pycnometer method in the same manner as in Example 1. The result was 1.2 g / ml.

(e) Viscoelasticity measurement

A viscoelasticity test was conducted in the same manner as in Example 1, and 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) in (Equation 1). The results are shown in Table 1. Mc was 593.

Although the present invention has been described in detail with reference to specific embodiments thereof, 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 present invention. The present application is based on Japanese Patent Application (Japanese Patent Application No. 2016-015154) filed on January 29, 2016, 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 processes requiring a high temperature of the feed liquid, hot water sterilization, and steam sterilization. In addition, since the hollow fiber membrane module of the present invention can suppress the heat generation at the time of curing of the adhesive, it is possible to simultaneously cure the adhesive of a large capacity to bind the hollow fiber membrane made of the polymer, The polymer hollow fiber membrane module can be manufactured at low cost.

This makes it possible to reduce the manufacturing cost per membrane area of the hollow fiber membrane module and reduce the number of the hollow fiber membrane modules used in the process. Therefore, it is possible to simultaneously reduce the number of valves, management devices, and the like, .

100A: Hollow Fiber Membrane Module
100B: Hollow Fiber Membrane Module
100C: Hollow Fiber Membrane Module
1: Normal Case
1A: flange portion
1B: flange portion
2: hollow fiber membrane
3: first binding portion
4: second binding portion
5: hole
6: Upper cap
6A:
7: Lower cap
8: Filtrate outlet
9: overflow inlet
10: Gasket
11: Excess payment amount exit
12: Hollow fiber membrane bundle
14: rectification hole
15: Second Normal Case
16: jig for forming first binding part
17: jig for forming the second binding portion
18: pin
19: Potting agent
20: Excess payment amount exit
21: Fluid overflow inlet
22: Filtrate outlet
23: Filtrate outlet
24: Seal material
25: Seal material
26: Seal material

Claims (11)

A hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the ordinary case, and at least one binding section for binding the plurality of hollow fiber membranes, wherein the binding section contains an adhesive agent, and the adhesive agent has a glass transition temperature Is not less than 80 DEG C and not more than 160 DEG C, and Mc is expressed by the formula (1) of the adhesive, the weight W of the binding portion binding in a state in which the hollow portion of the hollow fiber membrane is opened and the Vicat softening temperature VST Wherein the hollow fiber membrane module satisfies equation (2).
Mc = 2 (1 + μ) ρRT / E (Equation 1)
(g / m ³ ), R is the gas constant (J / K / mol), μ is the Poisson's ratio,
T: absolute temperature (K), E: storage elastic modulus (Pa)
VST? 5.78 × W / Mc + 420 (Equation 2)
VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g) The hollow fiber membrane module according to claim 1, wherein the adhesive has Mc of 140 or more and less than 1760 represented by the formula (1). The hollow fiber membrane module according to claim 1 or 2, wherein the binding portion (a) contains an epoxy resin and (b) an amine curing agent. The hollow fiber membrane according to any one of claims 1 to 3, wherein the binding portion comprises a curing agent having at least one of (a) a bisphenol-type epoxy resin and (b) an alicyclic amine and / module. 5. The epoxy resin composition according to any one of claims 1 to 4, wherein the binding portion (a) is a bisphenol-type epoxy resin having an epoxy equivalent of 150 or more and less than 250, and (b) bis (4-aminocyclohexyl) Aminophenyl) methane as a main skeleton. 6. The epoxy resin composition according to claim 5, wherein the binding portion is an epoxy group in the bisphenol-type epoxy resin (a) having an epoxy equivalent of 150 or more and 250 or less, (A) an epoxy equivalent of not less than 150 but not more than 250, wherein the value of (a) bisphenol-type epoxy resin having a value of not less than 6 but not more than 20 divided by the number of amino groups of a curing agent having at least one of The hollow fiber membrane module according to any one of claims 1 to 6, wherein the binding portion contains particles having an average particle diameter of 40 탆 or less so that the sedimentation volume is less than 150 ml and less than 1000 ml per 100 g of the adhesive. The hollow fiber membrane module according to any one of claims 1 to 7, wherein the ordinary case and the coupling portion are liquid-tightly fixed by a sealing material. 9. The hollow fiber membrane module according to any one of claims 1 to 8, further comprising a second normal case housed in the ordinary case, wherein the second normal case and the binding portion are liquid- . A hollow fiber membrane module comprising a normal case, a hollow fiber membrane bundle having a plurality of hollow fiber membranes housed in the ordinary case, and at least one binding portion for binding the plurality of hollow fiber membranes, wherein the binding portion contains an adhesive , A glass transition temperature of the adhesive is 80 ° C or more and less than 160 ° C, and Mc is expressed by the formula 1 of the adhesive, the weight W of the binding portion bound in a state where the hollow portion of the hollow fiber membrane is opened, Wherein the adhesive agent and the hollow fiber membrane are selected so that the Vicat softening temperature VST of the hollow fiber membrane satisfies the formula (2).
Mc = 2 (1 + μ) ρRT / E (Equation 1)
(g / m ³ ), R is the gas constant (J / K / mol), μ is the Poisson's ratio,
T: absolute temperature (K), E: storage elastic modulus (Pa)
VST? 5.78 × W / Mc + 420 (Equation 2)
VST: Vicat softening temperature (K) of the hollow fiber membrane, W: Weight (g) The method for producing a hollow fiber membrane module according to claim 10, wherein an adhesive having Mc of 140 or more and less than 1760 is selected as the adhesive.

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