JPH0661432B2 - Water resistant yarn bundle element - Google Patents

Description

TECHNICAL FIELD The present invention relates to a large number of hollow fibers having sufficient selective permeability for permeating and separating and removing water from a mixed vapor of an organic material containing water. The present invention relates to a water-resistant yarn bundle element in which a yarn bundle made of (3) is integrally fixed to a resin plate which is heat-cured with a specific water-resistant epoxy resin composition.

The yarn bundle element of the present invention is excellent in water resistance, even if it is used for separating a mixture containing moisture, the resin plate of the yarn bundle element is not easily deteriorated by moisture. .

[Description of Prior Art]

In recent years, a membrane separation process using a permselective separation membrane to dehydrate an organic solvent containing water and the like to purify and recover a highly pure organic solvent is being proposed.

The separation membrane module used in the process includes a plate and frame type, a tubular type, a hollow fiber bundle type, and the like, and the hollow fiber bundle type has the largest membrane area per unit volume, which is advantageous. Needless to say, in the production of the hollow fiber type separation membrane module, it is necessary to fix both ends of the yarn bundle with the curing plate (resin plate) of the casting resin to bind them together. And there was a problem in performance.

Generally, in the method of gas separation (vapor separation) of the vapor of a mixture of water and organic matter, it is necessary to make the temperature of the vapor gas equal to or higher than the boiling point, so that the gas separation is usually performed at a high temperature of 100 ° C. or higher. However, as the casting resin, unsaturated polyester resin, polyurethane resin and the like are generally known, but since they are poor in heat resistance and solvent resistance, they are hydrolyzed and deteriorated at high temperatures, cracks are generated, and the resin is Therefore, it could not be used to fix both ends of the hollow fiber bundle for gas separation.

Further, recently, a modified epoxy obtained by reacting a liquid polybutadiene having a reactive functional group (for example, a carboxyl group) with a phenol novolac type epoxy resin as a resin composition formed on both ends of a yarn bundle element. It is possible to use an epoxy resin composition comprising a resin, a heat-curable curing agent, and a curing accelerator.
Although disclosed in Japanese Patent No. 74434, this known yarn bundle element is not always sufficient in water resistance, and is not practical in membrane separation of vapor of a water-containing organic substance.

[Problems to be solved]

That is, the object of the present invention is, for example, "a hollow fiber having a selective permeability of water" in the vapor of an organic substance containing water.
A yarn bundle element in which both ends of the yarn bundle are fixed by casting resin and bound, and the resin plate has sufficient water resistance even under a condition of being exposed to moisture at high temperature for a long time. It is an object of the present invention to provide a yarn bundle element which is a high resin plate and can be used for a long period of time also in gas separation such as dehydration of organic vapor containing water.

[Means for solving problems]

That is, according to the present invention, both ends of a yarn bundle composed of a large number of hollow fibers having selective permeability have the general formula I [However, R is a divalent residue obtained by removing a diamino group from at least one diamine compound selected from the group consisting of diaminodiphenylmethane, bis (aminomethyl) cyclohexane, and xylylenediamine. ] The epoxy resin and the aromatic diamine compound or the alicyclic diamine compound represented by the above are such that the amount of the diamine compound used is from chemical equivalent to 60% of the chemical equivalent to the amount of the epoxy resin used. The present invention relates to a water resistant yarn bundle element, characterized in that an epoxy resin composition blended in a proportion is integrally fixed by a resin plate formed by heat curing and bound. Hereinafter, the present invention will be described in more detail with reference to the drawings.

FIG. 1 is a perspective view showing an example of a water resistant yarn bundle element in the present invention, and FIG. 2 is a perspective view of a separation membrane module incorporating the yarn bundle element of FIG. 1 used for dehydration of organic vapor. It is sectional drawing which shows an example.

As shown in FIG. 1, the yarn bundle element used in the yarn bundle element of the present invention can selectively permeate moisture from a mixed vapor of an organic substance such as an organic solvent containing moisture, A large number of hollow fiber-shaped separation membranes (hollow fiber membranes) formed of asymmetric separation membranes, porous membranes, composite separation membranes, etc., bundled and cut yarn bundle 1, and the yarn bundle 1 The yarn bundle element 3 may be a thermosetting resin plate 2 for fixing and binding provided at both ends or a yarn bundle element 3 made of 2 '.

The yarn bundle has, for example, (1) each hollow fiber having a length of 10 to 50.
0 cm, especially about 20-300 cm, (2) the outer diameter of each hollow fiber is 100-1500 μm, especially 20
0 to 1000 μm, and (3) the thickness of each hollow fiber is 30 to 300 μm, especially 40 to 2
A large number of hollow fiber separation membranes having a diameter of about 00 μm (for example, 10 to 500,000, particularly 100 to 200,000).
Book) is a bundle of yarn bundles that is bundled by an appropriate bundle-consolidating means and then cut to form flat opening surfaces at both ends of the bundle of yarns. A diameter of 0.5 to 100 cm, particularly about 1.0 to 60 cm is preferable.

The hollow fiber may be a hollow fiber separation membrane formed of cellulose acetate, polyamide, polysulfone, polyimide or the like, in particular, heat resistance, solvent resistance, and a polyimide hollow excellent in permeation performance. Thread separation membranes are most suitable.

As the polyimide, for example, 2,3,3 ', 4'- or 3,
3 ', 4,4'-biphenyltetracarboxylic acid or its acid dianhydride, 2,3,3', 4'- or 3,3 ', 4,4'-benzophenonetetracarboxylic acid or its acid dianhydride Alternatively, a tetracarboxylic acid component containing an aromatic tetracarboxylic acid such as pyromellitic acid or an acid dianhydride as a main component, and 4,4 ′
-Diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenylmethane,
3,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenoxy) benzene, bis (aminophenoxy-phenyl) methane, bis (aminophenoxy-phenyl) Sulfone,
Diamine containing an aromatic diamine compound as a main component such as o-tolidine and o-tolidine sulfone,
An aromatic polyimide obtained by polymerization and imidization in an organic solvent can be mentioned.

As the diamine component, in addition to the aromatic diamine, for example, one benzene ring such as o-, m- or p-phenylenediamine, 2,4-diaminotoluene, and 3,5-diaminobenzoic acid. The aromatic diamine which it has may be contained in the ratio within about 20 mol% with respect to all the diamine components.

In the present invention, the hollow fiber comprises a tetraralbonic acid component containing biphenyltetracarboxylic dianhydride as a main component, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl ether, 4,4 ′. -Using a solution of an aromatic polyimide obtained by polymerization and imidization from a diamine component containing at least one aromatic diamine selected from the group consisting of diaminodiphenylmethane as a main component, as a dope solution for film formation Therefore, an asymmetric hollow fiber separation membrane made of aromatic polyimide, which is produced by a wet membrane production method using a coagulating liquid, is preferable in terms of separation performance, heat resistance, durability and the like.

In the yarn bundle element of the present invention, for example, the yarn bundle of the hollow fibers described above is arranged in a mold of a centrifugal molding machine, and then the mold provided in the yarn bundle is rotated to make the yarn bundle. 35 to 120 ° C., in particular, by supplying a specific epoxy resin composition to the tip of the mold and applying a centrifugal force due to the rotation of the mold to the epoxy resin composition at the tip of the yarn bundle in the mold. Four
It may be produced by heating to a temperature of 0 to 100 ° C. and thermosetting to form resin plates at both ends of the yarn bundle.

It should be noted that the resin plates at both ends of the yarn bundle formed by the above-mentioned centrifugal molding have a temperature more than 10 within the temperature range in the above-mentioned centrifugal molding.
It is appropriate to carry out post-curing in the "temperature range of 120 to 250 ° C", which is about 100 ° C higher, from the viewpoint of durability and mechanical properties of the resin plate.

The epoxy resin composition used in this invention has the general formula I [However, R is a divalent residue obtained by removing a diamino group from at least one diamine compound selected from the group consisting of diaminodiphenylmethane, bis (aminomethyl) cyclohexane, and xylylenediamine. ] The epoxy resin and the aromatic diamine compound or the alicyclic diamine compound represented by], so that the amount of the diamine compound used is from "chemical equivalent to 60% of the chemical equivalent" with respect to the amount of the epoxy resin used. It is an epoxy resin composition that is blended at a ratio of "4, preferably a chemical equivalent to 80% of the chemical equivalent".

In the above epoxy resin composition, the use ratio of the diamine compound for curing is stoichiometry calculated from the epoxy equivalent of the epoxy resin and the active hydrogen equivalent of the diamine compound, or about 60% of the stoichiometric amount. It is preferable, however, that if a stoichiometric amount or more of a diamine compound is used, the amount of heat generated during curing of such an epoxy resin composition becomes too large, and a highly durable resin plate may not be formed. However, it is not preferable, and if the proportion of the diamine compound used is too small, the curing of such an epoxy resin composition becomes insufficient and a strong resin plate is not formed, which is not preferable. Further, in order to impart appropriate flexibility to the molded resin plate, a modified epoxy resin obtained by reacting an epoxy resin with liquid polybutadiene having a reactive functional group may be used.

Examples of the epoxy resin represented by the general formula I include N, N, N ', N'-tetraglycidyl-m-xylylenediamine, N, N, N', N'-tetraglycidyl-p-xylyl. Tetraglycidyl-xylylenediamine-based epoxy resin such as diamine, bis such as 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane (N, N-diglycidylaminomethyl) cyclohexane-based epoxy resin,
N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N, N', N'-tetraglycidyl-3,4 '
-Tetraglycidyl such as diaminodiphenylmethane-
Examples thereof include diaminodiphenylmethane-based epoxy resin.

The epoxy resin represented by the general formula I has an average molecular weight of 250 to 800, particularly 300 to 500, and an epoxy equivalent of 60 to 150, particularly about 80 to 140,
It is preferably liquid at temperatures between 0 and about 50 ° C.

Examples of the epoxy resin represented by the general formula I include N, N, N ', N'-tetraglycidyl-m-xylylenediamine (trade name; TETRAD-X) and 1 manufactured by Mitsubishi Gas Chemical Co., Inc. ,
3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name; TETRAD-C), N, N, N ', manufactured by Ciba-Geigy
N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name; Araldite MY-720) and the like are preferable.

Further, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane is a trade name of Toto Kasei Co., Ltd .; Epotote YH-434, a product of Yuka Shell Epoxy Co., Ltd. Examples thereof include Epicoat 604, trade name of Dainippon Ink and Chemicals Co., Ltd., Epiclon 403, and the like.

Examples of the aromatic diamine (curing agent) include 1,4-
Bis (aminophenoxy) benzene, 1,3-bis (aminophenoxy) benzene, 4,4′-diaminodiphenylmethane, 4,4′-diamino-3,3′-dimethyldiphenylmethane, 3,4′-diaminodiphenylmethane, 4 4,4'-diamidinophenyl ether, 3,4'-diaminodiphenyl ether, m-phenylenediamine, m-xylylenediamine, m-xylylenediamine modified product consisting of a condensation oligomer of m-xylylenediamine and epichlorohydrin, And so on.

Further, as the alicyclic diamine (curing agent),
Examples thereof include 3-bis (aminomethyl) cyclohexane and bis (4-amino-3-methylcyclohexyl) methane.

In the yarn bundle element of the present invention, since the resin plate has sufficient heat resistance, water resistance, mechanical strength and solvent resistance, the "raw material supply port 4, non-permeability" as shown in FIG. As a separation membrane module in which a yarn bundle element 3 (consisting of the yarn bundle 1 and the resin plates 2 and 2 ') of the present invention is incorporated inside a container having a material take-out port 6 and a permeate take-out port 5 " After being formed, the separation membrane module can be used for a long period of time in dehydration operations with various water-containing organic solvents.

The organic solvent dehydrated using the separation membrane module containing the yarn bundle element of the present invention includes methanol,
Ethanol, n-propanol, isopropanol, n
-Butanol, sec-butanol, tert-butanol, aliphatic alcohols such as ethylene glycol, alicyclic alcohols such as cyclohexanol, aromatic alcohols such as benzyl alcohol, formic acid, acetic acid, propionic acid,
Organic carboxylic acids such as butyric acid, organic acid esters such as butyl acetate and ethyl acetate, ketones such as acetone and methyl ethyl ketone, cyclic ethers such as tetrahydrofuran and dioxane, organic amines such as butylamine and aniline, and mixtures of the above compounds. Can be mentioned.

The present invention can be preferably used for dehydration of an aqueous solution containing alcohol among the above-mentioned organic substances, and can be particularly preferably used for dehydration of an aqueous solution containing ethanol or isopropanol.

〔Example〕

Example 1 Tetracarboxylic acid component consisting only of 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 60 mol% of 4,4'-diaminodiphenyl ether and 40 mol of 4,4'-diaminophenylmethane % Of the diamine component, p-
A p-chlorophenol solution of an aromatic polyimide obtained by polymerization and imidization at a temperature of about 150 ° C. in a chlorophenol melt was used, and the solution was extruded from a hollow fiber spinning nozzle to use a coagulation liquid. A hollow fiber separation membrane made of aromatic polyimide was produced by the wet spinning method.

The hollow fiber separation membrane (length: 30 cm, outer diameter: 540 μ)
m, inner diameter; 300 μm) are bundled and placed in a mold installed in the centrifugal molding machine, and the mold in the centrifugal molding machine is 8
(A) N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane [Yukaka Shell Epoxy Co., Ltd., Epicoat 604 (viscosity at 50 ° C .: 60 poise, epoxy equivalent: 119)] 100 parts by weight, and (b) bis (4-amino-3-methylcyclohexyl) methane (manufactured by BASF, trade name; Laromin C-260). An epoxy resin composition consisting of 43 parts by weight is fed into a mold and centrifugally molded for 3 hours to form resin plates on both ends of a bundle of hollow fibers, and the yarn as shown in FIG. Manufacture bundle elements,
Furthermore, the yarn bundle element is heated at 150 ° C. for 3 hours,
The resin plate was post-cured.

Using the yarn bundle element manufactured as described above,
The yarn bundle element is arranged inside a "container 7 having a raw material supply port 4, a non-permeate take-out port 6, a permeate take-out port 5 and the like" as shown in FIG. , A separation membrane module was manufactured.

Then, in a state where the inside of each hollow fiber of the yarn bundle element 3 incorporated in the separation membrane module is depressurized to 5 mmHg, the water-ethanol mixed vapor (150 ° C.) heated to 150 ° C. is fed to the raw material supply port 4 of the separation membrane module. Concentration of ethanol: 80
(% By weight) is supplied at a pressure of 4 kg / cm ² G to flow along the outside of each hollow fiber of the yarn bundle element and permeate from the outside of each hollow fiber to the inside “permeation containing water as the main component”. steam"
Is taken out from the permeate take-out port 5, condensed and collected as a permeate by a trap containing dry ice and ethanol, and at the same time, the non-permeated vapor is taken out from the non-permeate take-out port 6, and the same trap as above. It was condensed and collected as a non-permeate by.

The separation operation of the water-ethanol mixed vapor by the separation membrane module was continuously performed for 1000 hours, and the composition and amount of the collected permeate and non-permeate were measured several times in the middle, From the result calculated from the measurement result, the water vapor transmission rate (PH ₂ O; cm ³ / cm ² · sec · cmH
g), the selective permeability indicated by the ratio of the water vapor permeation rate to the ethanol permeation rate (PH ₂ O / PEtOH) was calculated.

As a result, the water vapor transmission rate was 0.7 × 10 ⁻³ cm ³ / cm ²
The "separation performance", which is -sec-cmHg and the selective permeability is 103, was maintained substantially stable from the beginning of the above separation operation up to 1000 hours.

After performing the above separation operation, the used separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance of the resin plate was inspected, but no fine cracks and cracks were observed at all, and no abnormal changes were observed. Was not found.

On the other hand, the same epoxy resin composition used for forming the resin plate of the yarn bundle element was poured into a test tube, and the test tube was heated at 85 ° C. for 3 hours and at 150 ° C. for 3 hours.
A resin rod for a sample having a diameter of 18 mm and a length of 30 mm was manufactured by heating and curing. The resin rod for this sample was immersed in a 60 wt% ethanol aqueous solution, and then the immersed ethanol aqueous solution was heated to a temperature of 130 ° C.
After maintaining for a period of time, its appearance changed (cracks and cracks generated) and weight changed (degree of swelling of resin rod)
I checked.

After the end of the hot ethanol aqueous solution immersion test, no change in the appearance of the sample resin rod was observed, and the weight of the sample resin rod was slightly increased by 2.10% by weight. It was

Example 2 As an epoxy resin composition, Mitsubishi Gas Chemical Co., Inc. N, N,
Epoxy resin composition at the time of centrifugal formation using 100 parts by weight of N ', N'-tetraglycidyl-m-xylylenediamine (trade name; TETRAD-X) and 44.6 parts by weight of 4,4'-diaminodiphenylmethane A yarn bundle element was manufactured in the same manner as in Example 1 except that the curing temperature of the product was set to 50 ° C., and then a separation membrane module was manufactured in the same manner as in Example 1.

A separation operation was performed in the same manner as in Example 1 except that the separation membrane module manufactured as described above was used, and as a result, the water vapor transmission rate was 0.7 × 10 ⁻³ cm ³ / cm ^2.
The "separation performance", which was -sec-cmHg and the selective permeability was 110, was maintained substantially stable for 1000 hours from the beginning of the separation operation.

After performing the above separation operation, the used separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance of the resin plate was inspected, but no fine cracks and cracks were observed at all, and no abnormal changes were observed. Was not found.

On the other hand, the same "hot ethanol aqueous solution immersion test" as in Example 1 was conducted except that the above epoxy resin composition was used, and as a result, the resin rod for sample after immersion was free from cracks, and The weight of the sample resin rod was increased by 2.84% by weight.

Example 3 As an epoxy resin composition, 100 parts by weight of 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (trade name; TETRAD-C) of Mitsubishi Gas Chemical Co., Inc. and m-xylenediamine were used. Using 43.0 parts by weight of a modified product (trade name: Gaskamine 328, manufactured by Mitsubishi Gas Chemical Co., Inc.), the curing temperature of the epoxy resin composition during centrifugal formation is 45
A yarn bundle element was manufactured in the same manner as in Example 1 except that the temperature was set to ° C, and then a separation membrane module was manufactured in the same manner as in Example 1.

A separation operation was performed in the same manner as in Example 1 except that the separation membrane module manufactured as described above was used, and as a result, the water vapor transmission rate was 0.7 × 10 ⁻³ cm ³ / cm ^2.
The "separation performance", which was -sec-cmHg and the selective permeability was 92, was maintained almost stable for 1000 hours from the beginning of the separation operation.

After performing the above separation operation, the used separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance of the resin plate was inspected, but no fine cracks and cracks were observed at all, and no abnormal changes were observed. Was not found.

On the other hand, the same "hot ethanol aqueous solution immersion test" as in Example 1 was conducted except that the above epoxy resin composition was used, and as a result, the resin rod for sample after immersion did not have cracks, and The weight of the sample resin rod was increased by 2.98% by weight.

Comparative Example 1 Phenolic novolac type epoxy resin as an epoxy resin composition (produced by Yuka Shell Epoxy Co., Ltd., Epicoat 15)
4 (viscosity at 52 ° C .: 350 to 700 poise, epoxy equivalent: 176 to 181) 100 parts by weight, and bis (4-amino-3-methylcyclohexyl) methane 4,4′-diamino-
A yarn bundle element was manufactured in the same manner as in Example 1 except that an epoxy resin composition consisting of 28 parts by weight of 3,3′-dimethyldiphenylmethane (manufactured by BASF, trade name; Laromin C-260) was used. Then, a separation membrane module was manufactured in the same manner as in Example 1.

A separation operation was performed in the same manner as in Example 1 except that the separation membrane module produced as described above was used. However, since the selective permeability was 10 or less from the beginning of the separation operation, the separation operation was performed. 100 hours after the start of the operation, the separation operation was stopped, the separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance was observed. As a result, there was a peeled portion on the surface of the resin plate and There were many fine cracks and cracks inside.

On the other hand, the same "hot ethanol aqueous solution immersion test" as in Example 1 was carried out except that the above epoxy resin composition was used, and as a result, a large number of cracks were generated in the resin rod for sample after immersion, and , The weight of the resin rod for sample is 4.63% by weight
Was increasing.

Comparative Example 2 As an epoxy resin composition, (a) a liquid cis-polybutadiene having a carboxyl group, and a phenol novolac type epoxy resin (produced by Yuka Shell Epoxy Co., Ltd., Epicoat 154 (viscosity at 52 ° C .:
350-700 Poise, Epoxy Equivalent: 176-18
1)] in a ratio of 1 to 10 (weight ratio), 100 parts by weight of a modified epoxy resin, (b) as a curing agent, 80 parts by weight of methyl nadic acid anhydride, and (c) as a curing accelerator. , 2-ethyl-4-methylimidazole, except that an epoxy resin composition consisting of 1 part by weight was used, a yarn bundle element was produced in the same manner as in Example 1, and the yarn bundle element was used. A separation membrane module was manufactured in the same manner as in Example 1.

A separation operation was performed in the same manner as in Example except that the separation membrane module produced as described above was used. However, since the selective permeability was 10 or less from the beginning of the separation operation, the separation operation was performed. 100 hours after the start, the separation operation was stopped, the separation membrane module was disassembled, the yarn bundle element was taken out, and the appearance was observed. As a result, there was a peeled portion on the surface of the resin plate, and the surface and inside of the resin plate There were many fine cracks and cracks on the surface.

On the other hand, as a result of performing the “hot ethanol aqueous solution immersion test” as in Example 1 except that the above epoxy resin was used,
After the immersion, the sample resin rod had many cracks, and the weight of the sample resin rod was increased by 8.60% by weight.

Reference Examples 1 to 17 An epoxy resin composition comprising an epoxy resin and a diamine compound having the compositions shown in Table 1 was poured into a test tube, and 85
The resin rod for a sample having a diameter of 18 mm and a length of 30 mm was manufactured by heat-curing at 3 ° C. for 3 hours and post-curing at 150 ° C. for 3 hours.

Each resin rod for the sample was immersed in a 60 wt% ethanol aqueous solution, and then the immersed ethanol aqueous solution was
After heating to a temperature of 30 ° C. and maintaining at that temperature for 70 hours, changes in the appearance (cracks and the occurrence of cracks) and weight of the resin rods (degree of swelling of the resin rods)
Were observed and measured, respectively. The results are shown in Table 1.

In the reference examples shown in Table 1, the epoxy resin compositions in Reference Examples 1 to 13 had sufficiently high water resistance and could be used for producing the yarn bundle element of the present invention, but Reference Examples 14 to 17 The epoxy resin composition in 1) had a considerably poor water resistance and could not be used for producing the yarn bundle element of the present invention.

The abbreviations in Table 1 have the following meanings.

C-260; bis (4-amino-3-methylcyclohexyl) methane [manufactured by BASF, trade name; Laromin-C-260] DDM; 4,4'-diaminodiphenylmethane 3,4'-DE; 3,4 ' -Diaminodiphenyl ether MPD; m-phenylenediamine MXDA; m-xylylenediamine G-328; m-xylylenediamine modified product (Mitsubishi Gas Chemical Co., Ltd.
Gascamine-328) 13-BAC; 1,3-bis (aminomethyl) cyclohexane [Function and Effect of the Present Invention] The yarn bundle element of the present invention has extremely high water resistance because the resin plates at both ends of the yarn bundle are centrifugally formed using an epoxy resin composition having a special composition, The separation membrane module as shown in FIG. 2 in which the yarn bundle element is provided in the container can withstand a long-term separation operation of the water-containing organic matter, and is excellent in durability in which the separation performance is maintained.

[Brief description of drawings]

FIG. 1 is a perspective view showing an example of a water resistant yarn bundle element in the present invention, and FIG. 2 is a perspective view of a separation membrane module incorporating the yarn bundle element of FIG. 1 used for dehydration of organic vapor. It is sectional drawing which shows an example. 1; a bundle of hollow fibers, 2; a resin plate, 3; a bundle element,
4; raw material supply port, 5; permeate takeout port, 6; non-permeate takeout port, 7; container.

Claims (1)

[Claims] 1. A yarn bundle consisting of a large number of hollow fibers having selective permeability has the general formula I [However, R is a divalent residue obtained by removing a diamino group from at least one diamine compound selected from the group consisting of diaminodiphenylmethane, bis (aminomethyl) cyclohexane, and xylylenediamine. ] The epoxy resin and the aromatic diamine compound or the alicyclic diamine compound represented by] are such that the amount of the diamine compound used is from chemical equivalent to 60% of the chemical equivalent to the amount of the epoxy resin used. A water resistant yarn bundle element, characterized in that an epoxy resin composition blended in a proportion is integrally fixed and bound by a resin plate formed by heating and curing.