JPS58166902A - Semipermeable membrane module and its production - Google Patents

Abstract

PURPOSE:To improve heat resistance, chemical resistance and durability in a semipermeable membrane module by using an imidazole type curable epoxy resin of a toughness index having a specific value as a sealing and fixing material for end parts. CONSTITUTION:An epoxy resin of >=170 toughness index expressed by 1/2 X breaking strength (kg) X breaking elongation (%) cured by an imidazole curing agent as an essential component is packed in the clearances in the membrane end parts of a semipermeable membrane module, and is solidified at 0-50 deg.C in the 1st stage and is then post-cured at 60-150 deg.C, whereby the end parts of the semipermeable membrane module are sealed and fixed. Although the type of the module is not limited, a hollow fibrous membrane module is particularly advantageous.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a semipermeable membrane module using a sealing and fixing member having excellent heat resistance, chemical resistance, and durability, and a method for manufacturing the same.

In recent years, remarkable progress has been made in membrane separation technology that uses semipermeable membranes with selective permeability as a means of separating extremely small particles on the order of microns or less and dissolved substances. Although membrane separation technology has been put to practical use in various applications, it has not been put to practical use in fields where membrane separation technology is constantly used at high temperatures of 60° C. or higher or where organic liquid solutions are used. In the industrial field, the semipermeable membrane itself must of course have excellent heat resistance and chemical resistance, but the seal end that seals and fixes the membrane must also have similar heat resistance and chemical resistance. Of course it doesn't. Efforts are being made to improve the heat resistance and chemical resistance of the semipermeable membrane itself, and there are many reports. On the other hand, research on the sealed edges of semipermeable membranes tends to be neglected, and there is a tendency for membranes to not fully demonstrate their inherent excellent performance. In view of this situation, we have selected epoxy-based, polyurethane-based, silicone-based, unsaturated polyester-based, unsaturated epoxy-based (
Also called vinyl ester. ).

Acrylic (so-called (8 ecobdary)
generation Acryl +c Adhes
Eikuno investigated various adhesives such as the Schiff/7 acrylate series and the Schiff/7 acrylate series. The results showed that the epoxy system was the most superior in terms of curing behavior and properties of the cured product. Conventional epoxy resins have excellent adhesive properties,
Moreover, it is often used as a sealant because of its low curing shrinkage. Another feature of epoxy-based Sat is that the curing behavior (curing temperature, curing time, etc.) and resin properties (heat resistance, chemical resistance, etc.) can vary greatly depending on the properties of the curing agent. For example, aliphatic or aromatic polyamine curing agents and their modified products can be cured at relatively low temperatures, but the resulting epoxy resins tend to have poor heat resistance and chemical resistance, particularly acid resistance. On the other hand, anhydride-based curing agents and imidazole-based curing agents have excellent heat resistance and chemical resistance of the resulting epoxy tIIi resin, but their curing temperatures are high, making them inconvenient as sealing and fixing materials for the edges of semipermeable membranes. be. In particular, high-temperature liquid epoxy compounds act as good solvents for the polymers constituting the semipermeable membrane, so they cannot maintain the shape of the semipermeable membrane, and may not be used at all as sealing and fixing materials. In this way, it has been found that the conventionally well-known epoxy adhesive cannot be used as is as a sealing and fixing material for the ends of a semipermeable membrane.

Therefore, we further investigated various types of epoxy adhesives and found that epoxy adhesives with a specific formulation are superior in terms of curing behavior and properties of the cured product, which is different from the present invention. That is, the present invention is a semipermeable membrane module characterized in that the end sealing and fixing material of the semipermeable membrane is composed of an imidazole-based hardened epoxy resin having a toughness index of 170 or more. Here, the toughness index is expressed as T x breaking strength (kq) x breaking elongation (tjIt)), and is expressed as breaking strength (kg) and breaking elongation (%).
is an imidazole-based hardened epoxy resin with a diameter of 4 cm and a length of 21 mm.The initial load is 1 kg and the tensile speed is 4 in hot water at 95°C.
This is a value measured under the condition of t'V' minutes.

The semipermeable membrane end sealing material of the present invention is composed of an imidazole-based hardened epoxy resin with a toughness index of 170 or more, so it has excellent heat resistance and chemical resistance, as well as extremely excellent durability. It is something that you have. Therefore, even if the obtained semipermeable membrane module is treated at high temperatures or in contact with chemicals such as alkalis and acids for a long period of time, the end sealing material may be damaged or deteriorated, or leaks may occur due to this. There is no connection,
It can be used extremely stably for a long period of time. It is preferable to use an imidazole-based cured epoxy resin having a toughness index of 200 to 700, since this provides a material for sealing and fixing the ends of a semipermeable membrane with even better heat resistance and chemical resistance. Toughness index is 1. , If it is less than Z-0, the durability is insufficient and it cannot be used at high temperatures for a long period of time.

Furthermore, it is difficult to manufacture imidazole-based cured epoxy resins with a toughness index exceeding 700 using conventional technology.

The imidazole-based cured epoxy resin in the present invention can be obtained by curing the following representative formulation. That is, epoxy base agent, 2 for its epoxy equivalent
Consisting of a polyamine curing agent having an amine equivalent of 5 to 70 mol% and an imidazole curing agent of 0.2 to 10% by weight relative to the epoxy base resin, and a weight ratio of polyamine curing agent/ξdazole curing agent is 100150~10
Obtained by curing a 0/1 epoxy formulation.

In the present invention, the imidazole-based cured epoxy resin means an epoxy resin cured with an imidazole-based curing agent as an essential component, and is hereinafter simply referred to as epoxy resin.7 In the present invention, the epoxy base resin refers to bisphenol A, hisphenol, ), refers to polyglycidyl compounds of polyhydric phenols such as novolac resins, oligomers of cholera, and polyglycidyl compounds of mixtures thereof, and in the case of a normal epoxy base agent, the epoxy equivalent is 150 to 200. The polyamine curing agent of the present invention refers to a polyamine compound having two or more amino groups with active hydrogen in its molecule that can react with an epoxy base resin at 0 to 50°C, preferably 10 to 40°C. It also includes modified products in which various substances are added to polyamines. The polyamine compound may be aliphatic or aromatic without any particular limitation, but aliphatic polyamine curing agents are preferred from the viewpoint of discoloration. Specific polyamine compounds include (1) chain aliphatic polyamines such as diethylenetriamine and triethylenetetramine (iDN-aminoethylpiperazine τ edition B l if
~Cycloaliphatic polyamines such as % laromine e-260 (
iii) Aliphatic polyamine adducts such as hydroxyethyldiethylenetriamine and bicyanoethyldiethylenetriamine (iv) Laccamite WH-2 manufactured by Dainippon Ink and Chemicals
40, modified aliphatic polyamine (V) such as Wli-, 101, and WH-241 Evotough Hardener 57 manufactured by Dainippon Ink and Chemicals
Polyamide amine (vl) such as -612; Aliphatic aromatic polyamine (via) such as metaxylylene diamine; Laccamite WH- manufactured by Dainippon Ink &Chemicals;
Examples include modified aromatic polyamines such as WH-301 and WH-501.

The imidazole curing agent of the present invention refers to a compound having the following imidazole ring.

≧ R+ Here, R11"?+ R51"4 is hydrogen, carbon number is 1~
20 alkyl groups, alkyl groups having aromatic rings, phenyl groups with or without various substituents, cyanoethyl groups, and hydroxymethyl groups.

alkyl groups, etc. Furthermore, modified imidazole compounds obtained by adding a carboxylic acid such as trimellitic acid or an organic acid such as isocyanuric acid to the above-mentioned imidazole compound are also included in the imidazole compound of the present invention. Among various imidazole compounds, 2-ethyl-4-methylimidazole, in which R, R3 is hydrogen, R2 is an ethyl group, and R4 is a methyl group, is liquid and has excellent solubility in epoxy base resins and polyamine curing agents. It is preferable in terms of ease of handling and work efficiency. In addition, when the amount of compounded per batch is large,
When using a polyamine compound that generates a large heat of curing, or an imidazole compound salted with trimellitic acid, it is relatively inert and has a high activation humidity. Only the curing agent contributes to the reaction, and the inert groups in the imidazole compound are thermally decomposed during the second step of high-temperature boss curing, resulting in an excellent reactivity that is almost equivalent to that of 2-ethyl-4-methylimidazole. In some cases, this is preferable because it results in a high-quality epoxy resin.

The epoxy resin for sealing and fixing the ends of the semipermeable membrane of the present invention is as described above.
In addition to whether or not other compounds must be mixed, the amount of these 5aIJ [incorporated] is also extremely important. An experimental example will be shown to concretely demonstrate this.

Experimental Examples The compounds shown in Table 1 as representative examples of the epoxy base agent, polyamine curing agent, and imidazole curing agent were mixed in the proportions shown in Table 21, defoamed, and poured into a PVC tube with an inner diameter of 4 mm. C and allowed to solidify. Next, this tube was immersed in hot water at 95°C for post-curing,
Fully cured. The PVC tube was then peeled off to obtain a bubble-free, uniform epoxy resin outer frame with a diameter of 4 and 9 p.m. The breaking strength, breaking elongation, and initial elastic modulus were determined from the stress strain curve when this round bar was pulled in 95°C hot water with a test length of 2 cm, an initial load of 1 #, and a tensile rate of 41/min. Determination 1 is shown in Table 1. Furthermore, the toughness index was determined from the strength and elongation using the following formula and is shown in Table 1.

Breaking strength x breaking elongation toughness index = Table 1 Blend amount of epoxy base agent, polyamine hardener, and imidazole hardener and physical properties in 95°C water Compound A, epoxy base agent... Dainippon Ink Chemical Industry - Epiclon asp (Bisphenol-based 1 poxy base agent (epoxy equivalent: 190)) B, polyamine curing agent: Laccamite WE-240 manufactured by Dainippon Ink & Chemicals (modified aliphatic polyamine (amine value 420)) C, imidazole curing agent ...Cure Sea JL/2E4MZ manufactured by VE Kokusei Co., Ltd. (2-Fk-4-)F-4Midazole) From the results in Table 1 and other experiments, the polyamine curing agent has a 25 to 70 It was found that it was necessary to blend the amount of amine in mol%. If the blending amount of the polyamine curing agent exceeds 70 mol % based on the epoxy equivalent, both the strength 9 modulus of elasticity and the toughness index will be low, and only an epoxy resin with low heat resistance will be obtained.

This is because the glycidyl group in the epoxy base agent is #! It is consumed in the solidification reaction caused by the reaction with the polyamine curing agent in the first step, and even if the imidazole curing agent in the second step tries to react in the post cure reaction, there are few remaining glycidyl groups, so the reaction with imidazole is difficult. Therefore, it is not possible to obtain an epoxy wm with excellent heat resistance. Polyamine 2, on the other hand! ; If the amount of the hardening agent is imol% based on the epoxy equivalent, it will not solidify at low temperatures below 50°C, and the elongation at break will be low, the toughness index will also be low, and fatigue will be reduced. There are concerns about its durability and impact strength. It is difficult to predict that the performance of the cured product would be better under specific conditions for a polyamine-imidazole mixed system than for an imidazole-only system, and although the cause of this synergistic effect is not well understood, the imidazole-based system is reacts with a liquid epoxy base agent, whereas in a mixed system it reacts with a solid epoxy base agent, so the mobility and density of the glycidyl group of the epoxy base agent at the time of reaction are different, and imidazole in a mixed system reacts with a solid epoxy base agent. It is presumed that this is because it reacts more effectively with glycidyl groups. It is more preferable that the amount of the polyamine curing agent is 50 to 50 mol % based on the epoxy equivalent in terms of the balance between curing behavior and performance of the cured product. Further, the amount of the imidazole curing agent added must be 0.2 to 10% by weight based on the epoxy base resin.

If it is less than 0.2%, there will be little reaction with glycidyl groups, making it impossible to obtain a cured product with excellent performance. Even if the amount of the imidazole curing agent exceeds 10%, the performance of the cured product will not improve. Imidazole curing agents are generally much more expensive than epoxy base agents or polyamine curing agents, and from an industrial perspective, it is preferable to use them in as small a quantity as possible. Therefore 10%
There is no advantage to mixing in an amount exceeding this amount. It is more preferable that the amount of the imidazole curing agent is 0.5 to 4% by weight in terms of performance and cost balance of the cured product. Furthermore, the superposition ratio of polyamine curing agent/imidazole curing agent is 10.
Must be 0.150 to 10/1.

50° if there is more imidazole curing agent than 100150
This is not preferable because it tends to be difficult to solidify at a temperature below C, the synergistic effect of mixing with a self-hardening agent tends to be small, and the cost tends to increase.

If the amount of the imidazole curing agent is less than 10Ω/1, the performance of the cured product will deteriorate, which is not preferable. The weight ratio of polyamine curing agent/imidazole curing agent is 100, /25 ~
10015 is more preferable in terms of curing behavior, cured product performance, and balance of price. As described above, the present invention uses a polyamine curing agent that solidifies at room temperature and an imidazole curing agent that has excellent cured physical properties (especially heat resistance and chemical resistance) as a curing agent for the epoxy base resin. By using both amount and mixture, you can always get a! We have discovered that it can be used as a semipermeable membrane end sealing material that has assimilability, synergistically excellent performance (especially heat resistance, chemical resistance, and toughness index), and is relatively inexpensive. It is something that The epoxy compound of the present invention may contain other substances in addition to the above-mentioned essential ingredients depending on the purpose of the epoxy compound. For example, various diluents and thickeners may be added as viscosity modifiers. Silica is also used to improve strength, prevent heat generation, and improve thixotropy.

Fillers such as silica fine powder and mica may be added.

Next, a method for sealing and fixing the ends of a semipermeable membrane using the epoxy resin of the present invention will be described. That is, the epoxy base resin, a polyamine curing agent having an amine equivalent of 25 to 70 mol % with respect to the epoxy equivalent, and 0.5 to the epoxy base resin.
~10% by weight of an imidazole curing agent, and the weight ratio of polyamine curing agent/imidazole curing agent is 1.
00150 to 10 units/unit weight 1 A liquid epoxy compound was filled into the gap between the ends of the semipermeable membrane. ,,0 as a stage
This is a method for sealing and fixing the end of a semipermeable membrane, which is characterized by solidifying at ~50°C and then post-curing at 60-150°C. The composition of the liquid epoxy formulation has already been described. The liquid epoxy formulation must fill the gaps in the semipermeable membrane without leaving any gaps. If the filling is incomplete, the completed semipermeable membrane module will leak, which is not preferable because it will not function as a separator. There are various methods for filling the liquid epoxy compound throughout, such as manually applying it to the gaps between multiple semipermeable membranes using a brush or spatula, or filling it all at once using centrifugal force. In the case of the present invention, any method may be applied, but
Filling using centrifugal force of 5 to 200 G (G is gravitational acceleration) ensures reliable filling, reduces the need to handle the semipermeable membrane by hand, prevents damage to the semipermeable membrane, and improves the quality of the finished semipermeable membrane. This is preferable because the defect rate of the module is low and the appearance is excellent.

If the eccentric force exceeds 200 G, an excessive force is applied to the membrane itself, which is not only undesirable, but also undesirable in terms of energy saving. It is more preferable to fill with a centrifugal force of 10 to 60G.

The present invention is characterized in that the liquid epoxy compound is filled into the gap between the semipermeable membranes and then cured in two stages. The first stage is a curing reaction in which the liquid resin is solidified at a relatively low humidity of 0 to 50°C. At this stage, the epoxy base resin and polyamine curing agent mainly react. Fluidity is lost, and although it has been assimilated, the glycidyl groups in the epoxy base agent remain (L), resulting in low heat resistance and brittleness at this stage. If the temperature is lower than 0°C, it will not solidify, which is not preferable. 50°
If it exceeds C, most of the imidazole curing agent will react at the same time due to the reaction heat of the polyamine curing agent, which is not preferable. It is more preferable that the I@1 stage is solidified at 10 to 40°C. It is also preferable to heat the mixture at 15 to 35°C in terms of the balance between assimilation and simultaneous imidazole reactivity. Furthermore, it is desirable to dissipate and remove the heat of reaction with the polyamine curing agent as much as possible so as not to increase the temperature within the system. After solidification, raise the temperature to 60-1508C and #! 2-step Bost key r must be performed, 606G or higher,
By doing so, the glycidyl group and imidazole group that were unreacted in the first step react in solid phase (or semi-solid phase),
Epoxy resin with excellent heat resistance and chemical resistance.

As mentioned above, the heat resistance and chemical resistance are not lowered than when glycidyl groups and imidazole groups undergo a liquid phase reaction (a liquid phase reaction occurs when a polyamine curing agent is not included). A synergistic effect can be obtained in which the shoulder strength of apricots is significantly improved. If the post cure humidity is less than 608G, the curing effect will be small and a product with excellent heat resistance and chemical resistance will not be obtained.

When the temperature exceeds 150°O, the membrane performance of the semipermeable membrane deteriorates, which is not preferable. Curing temperature of IN2 stage is 75-125
More preferably, the temperature is °C.

Next, the atmosphere during the curing reaction will be described. #1! Step i is performed at the same time as filling the gap at the end of the semipermeable membrane, so if filling is performed under centrifugal force, the centrifugal force continues to be applied to solidify the liquid epoxy compound. Post-curing may be performed by increasing the temperature after solidification, but
Since the epoxy compound usually does not flow after solidification, the centrifugal force is stopped and the mixture is taken out, followed by a second stage of post-curing in an atmosphere maintained at 60-150°C, preferably 75-125°C. At this time, post-kinealing may be performed in air, but in the case of reverse osmosis membranes, ultrafiltration membranes, precision r-filtration membranes, dialysis membranes, and ion exchange membranes that treat hydrogen liquid, hot water or steam In particular, it is advantageous to carry out post-curing in pressurized steam, since it is possible to post-cure the film without drying it (once it dries, the performance of the film often deteriorates). When the second stage post-cure is carried out in hot water, the preferred temperature is 75 to 1 oo'o. It is also preferable to perform post-curing in hot water because the semipermeable membrane module is washed with hot water, and the washing step can be omitted or simplified. Further, when post-curing the second Jfil in steam or pressurized steam, the preferred temperature is 90 to 125°C. Furthermore, when post-cured in dry heat, the epoxy compound turns reddish-brown and gray, which is characteristic of imidasol-based curing agents, and the appearance tends to deteriorate. The unique reddish-brown color of this imidasol-based curing agent is the best.
There have also been cases where heat removal is not sufficient in the step-by-step solidification reaction and heat is generated partially, causing the imitazole curing agent to react in the first step. In this case, local discoloration often occurs unevenly.

In addition, when performing a two-step post-cure, the treatment is first carried out at a low temperature, e.g. 60-80°G, for about 30 minutes to about 5 hours, and then at a high temperature, e.g. 90-125°C hot water or pressurized water. The process can be carried out in two stages, or even ink stages, while raising the temperature, such as approximately 30 minutes in steam - day and night (24 hours), or iI2
It is preferable to carry out the post-curing step while gradually raising the temperature, since it is possible to prevent discoloration and foaming of the partially sealed fixing material of the semipermeable membrane, and further to prevent the semipermeable membrane from dissolving.

Next, the state of the semipermeable membrane used in the present invention will be described. Conventionally, when sealing and fixing the ends of a semipermeable membrane using a polyurethane adhesive, for example, if the semipermeable membrane contains water, the isocyanate reacts with the water and foams, making it impossible to seal and fix the ends. Therefore, the semipermeable membrane needed to be completely dry. However, if the semipermeable membrane is made of a hydrophobic material, the membrane performance will deteriorate if it dries completely, so a method is used in which the semipermeable membrane is dried after adhering to a hydrophilic substance such as glycerin, and then sealed and fixed with an adhesive. This method also requires a glycerin adhesion step and washing again after sealing, and also requires countermeasures against COD of the washing wastewater. Further, since unsaturated polyester adhesives and unsaturated epoxy (vinyl ester) adhesives are also radical polymerized, if the semipermeable membrane contains water, curing will be poor, resulting in similar problems. In addition, if the material of the semipermeable membrane is a hydrophilic material, the membrane itself will easily become wet even if it is completely dried, and there will be no deterioration in membrane performance. Therefore, the dimensions (vertical and horizontal length and film thickness for flat membranes, and inner diameter for hollow delicate membranes.

The outer diameter, fiber length) will change, and abnormal stress will be applied at the boundary between the adhesive and the membrane, which may cause problems such as membrane damage. It was desired to provide constant sealing at the edges while the membrane remained wet. Under these circumstances, we investigated the possibility of sealing and fixing the edges of a semipermeable membrane in a wet state using the epoxy compound of the present invention, and unexpectedly found that it cured sufficiently. .

The wet state of the semipermeable membrane in the present invention means that the semipermeable membrane is 5 to 90% wet.
This refers to a state in which the water content is . Here, the moisture content refers to a value calculated using the following formula.

-D Moisture content = -X 100 ~■; Total weight of semipermeable membrane containing water (f) D + Wg Dry weight after drying the semipermeable membrane containing water at 100°C for 24 hours (f) Moisture content is If it is less than 5%, the effect of moisture content is not sufficient, which is not preferable. Moreover, if the water content exceeds 90%, the epoxy compound will not be sufficiently cured, which is not preferable. More preferably, it is 20 to 75%.

For semipermeable membranes whose dimensions change when the dry state is changed to the wet state, 2
! Sealing and fixing the ends in a 1 m barb condition reduces the possibility of membrane damage and is highly preferred.

In addition, in a module in which both ends of a semipermeable membrane are fixed to a ring body, the membrane will undulate due to dimensional changes, which may cause damage to the membrane, cause uneven fluid flow during use, and be unsightly. When bonded in a wet state, the film will not undulate. Furthermore, in cases where semipermeable membranes wfs or dissolve when the adhesive (epoxy compound) cures and heats up to high temperatures, for example, a polysulfone membrane is used as the semipermeable membrane, and a large number of semipermeable membranes (hollow fiber membranes) are used. etc.), it is very convenient to seal and fix the semipermeable membrane in a wet state. In this case, the water in the semipermeable membrane physically prevents the adhesive from entering the membrane, and because water is a strong coagulant for polysulfone, it chemically prevents the adhesive from entering the membrane. It also has an endothermic action that prevents melting and effectively absorbs the heat generated by curing.

It includes all membranes used to separate substances, such as ion exchange membranes. The shape of the membrane is a flat membrane.

There are spiral membranes, tubular expansion membranes, hollow fiber membranes, and the like, but there are no particular limitations. 1. Hollow A-thin membranes are often advantageous in that the apparatus can be made compact. The membrane material is cellulose-based or cellulose ester-based.

Polyacrylonitrile type, polyamide type, vinyl chloride type, polymethyl methacrylate type, fluoropolymer type. Polyolefin-based, polyvinyl alcohol-based (including vinyl alcohol-based copolymers such as ethylene-vinyl alcohol-based co-M combinations), polysulfone-based, silicon-based, polyimide-based, carbon-based.

Although it can be applied to all materials such as metal oxides, the present invention is characterized by obtaining a membrane module with excellent heat resistance and chemical resistance.

Polysulfone type, polyimide type, which has excellent chemical resistance.
It is more effective when applied to silicon-based, polyamide-based, fluoropolymer-based, polyvinyl alcohol-based, carbon-based, metal oxide-based, etc.

In the present invention, a semipermeable membrane module is one in which a large number of semipermeable membranes, especially a hollow fiber membrane bundle, at both ends or one end of which are sealed and fixed in a housing, or a large number of semipermeable membranes, especially a hollow fiber membrane bundle, are sealed and fixed at both ends or one end. Refers to a semipermeable membrane element that extends from both ends or one end of the membrane. The former case, in which a semipermeable membrane is sealed and fixed to a housing, becomes a fluid fibrillator by providing a header (cap, etc.) on the open fixed end of the semipermeable membrane. Moreover, the latter semipermeable membrane element becomes a fluid separation device by fixing it in a housing or in a tank. The former mainly uses artificial kidneys, plasma separation devices, and ascites Pij681. It is used as a separation device for body fluid treatment such as an ascites concentrator, or as a water purification device, and the latter is used as a variety of industrial separation devices such as precision P-filtration, external filtration, and reverse osmosis.

Next, the present invention will be further explained by examples.

In addition, in the embodiment, all the parts refer to the N-position parts.

\, ゝ・1, -'to1, ゛・\, 〜・, ゛・18, Example 1 1° Ebicuron 850J'- (Epoxy main agent manufactured by Dainippon Ink Chemical Co., Ltd. (epoxy equivalent: 190)'l 1001
i%.

[Lasokamide WH-240J (Daihon Ink Kagaku Kogyo Tetsu-made aliphatic polyamine curing agent (amine value approx. 420)
)l 14 parts, and [Curezol 2E4MZJ (2-ethyl-4-methylimidazole manufactured by Shill Kasei Co., Ltd.) 2
The parts were mixed so that the overlapping weight was 500 tons, and the temperature was set at 55°C. At this time, the weight ratio of amine polyamine curing agent/imidazole curing agent to epoxy equivalent was 14/2 to 100/14.

On the other hand, 5,000 highly crosslinked polyvinyl alcohol porous hollow fiber membranes with an outer diameter of 0.8 m and an inner diameter of 0.4 m were sufficiently wetted with water, and then dehydrated to the fullest extent. The moisture content at this time was 60%. The ends of this water-containing hollow fiber membrane bundle were centrifuged using the liquid epoxy formulation described above. The temperature of the centrifuge was 50°C, the centrifugal force was 30°C (J), and the centrifugal force was stopped after solidification for 4 hours.Then, while holding the hollow fiber membrane bundle vertically, the end sealed part was heated at 100°C.
Bost-cured for 2 hours in hot water at °C, the end face was cut to form an open end of the hollow fiber #lI membrane f) to obtain a polyvinyl alcohol-based hollow [14 module]. This module element had no leaks at all, filtered hot water at 95°C at a rate of 4 kg/d, and was successfully used. The toughness index of the epoxy resin used in Example 1 was 280.

Comparative Example 1 [100 parts of Epicron 850J and [Laccamite W]
tt-240J4G parts were mixed to have a total weight of 50 of, and the mixture was heated to 55°C. Note that the amine equivalent to the epoxy equivalent at this time was 90 mol%. This was subjected to centrifugal adhesion and post-curing in the same manner as in Example 1 to obtain a polyvinyl alcohol hollow fiber membrane module. This module element had no leaks and could be used smoothly at N temperature, but when 95°C hot water was filtered with 4 kgAd, the heat resistance of the adhesive was low.

The element was deformed and unusable. The toughness index of the epoxy resin used in Comparative Example 1 was 21.

Comparative Example 2 [100 parts of Epiclon 850J and [Curesol 2]
Mix 2 parts of E4MZJ so that the total weight is 50of,
The temperature was 55° C. and centrifugal bonding was carried out in the same manner as in Example 1.

When I stopped the centrifugal force for 16 hours and tried to take it out of the centrifuge, the adhesive had not solidified and flowed out.
It could not be modularized. Example 2 100 parts of [Epicron 850J ((Dainippon Ink Chemical Ball Toei epoxy agent (epoxy equivalent weight 180)), 14 parts of [Raccamite WH-2404], and [Cure Sol 2
The weight ratio of the mixed/imida pool curing agent was 14/2 to 100/14 so that the total weight of 2 parts of E4MZJ was 50 f.

After wetting 100 hollow fiber membranes as in Example 1 with water, they were uniformly dehydrated. The moisture content at this time is 60+
Met. This water contains 'g! The end of the trout sail was centrifuged for one hour using the above liquid epoxy formulation.

A centrifuge! The reaction was carried out at 20° C. and the centrifugal force was at a gravitational acceleration of 12 G, and the centrifugal force continued to be applied. After 16 hours, it had solidified, so I took it out of the centrifuge and heated it at 80℃ for 2 hours with the filling frame still attached, then at 100℃ for 2 hours with water.
At night, after the mold was cured for an hour, the mold was removed and the end face was cut to form an open end with a hollow edge i** to obtain a polyvinyl alcohol-based hollow fiber membrane module for laboratory testing. This module element was a good element with no leaks. The toughness index of the epoxy resin used in Example 2 was 460.

Example 5 “Epicron 850J 100% and Laccamite Wl
16 parts of 1-101J (modified aliphatic polyamine (amine 1 track 345) manufactured by Dainippon Ink Chemical Industry Co., Ltd.) and 2 parts of [Curesol 2E4MZJ] were mixed to a total weight of 50 of, and heated to 25°C.The epoxy equivalent at this time was The amine equivalent to
Met.

-75 external t40.75wm, 11145000 polysulfone thread hollow S fibers with an inner diameter of 0.4cm are immersed in a surfactant water bath solution, so that the 01tIa hole of @violet is also filled with water, and the surface active Fluid-containing flc4 was removed and excess water was removed by hand.

The moisture content of this polysulfone hollow fiber membrane was 71%. This water contains sky im! The @ part of the pongee membrane bundle was centrifugally adhered using the above liquid epoxy compound. The temperature of the centrifuge is 25℃
The centrifugal force was applied at a gravitational acceleration of 15Q, and the centrifugal force was continued to be applied for 8 hours to solidify.

Remove from the centrifuge and leave the formwork etc. in place for 75 minutes.
After post-curing for 2 hours at 75°C, the hollow fiber membrane was cut at 75°C to form open ends, and then post-cured for 2 hours in hot water at 100°C to obtain a polysulfonated hollow fiber membrane module. This module element is 18-51
One 6-piece housing was attached and subjected to hot water bathing at 95°C.

Even after continuous use for 10 months, it was possible to perform fi- in perfect order, and it had extremely good heat resistance. The toughness index of the epoxy resin used in Example 6 was 250.

Example 4 [100 parts of Ebicuron 850J and [Raccamite]
240J 14 parts Oyohi [Curesol 2 E 4 M
Mix the Z-0NJA part so that the total weight is 5Or,
The temperature was 60°C. At this time, the amine equivalent relative to the epoxy equivalent was 51 mol %, and the weight ratio of polyamine curing agent/imidazole curing agent was 100/21.

The ends of 100 dried polyimide hollow polyimide tubes with an outer diameter of 0.8 mm and an inner diameter of 0.4111 mm were brushed with the liquid epoxy compound, and then poured into a 20 mm mold.
After being left to solidify at 60°C for 16 hours, it was then post-cured at 70°C for 3 hours, then re-bost-cured at 121°C for 1 hour in pressurized steam (autoclave), and the end sections were cut to form hollow fiber membranes. Open ends were formed to obtain a polyimide hollow fiber rutted membrane for laboratory testing. This module had resistance to ordinary solvents such as hatoluene and trichlene, and had excellent resistance to scrubber bath media. The toughness index of Ehokin flJM used in Example 4 was 620.

Special applicant: Rira Shi Co., Ltd. Agent: Ken Fuyo, patent attorney

Claims (1)

[Scope of Claims] (1) A semipermeable membrane module characterized in that the end sealing and fixing material of the semipermeable membrane is composed of an imidazole-based hardened epoxy resin having a toughness index of 170 or more. (2) The semipermeable membrane module according to claim 1, which is an imidazole-based cured epoxy resin having a toughness index of 200 to 700. (3) Epoxy base agent, 25 to 25% based on its epoxy equivalent
0.5 to 101 Eji% based on a polyamine curing agent having an amine equivalent of 70 mol% and an epoxy base resin.
imidazole curing agent, and the ajl ratio of polyamine curing agent/imidazole curing agent is 10015G.
A liquid epoxy formulation of ~100/1 was filled into the gap at the end of the semipermeable membrane, solidified at 0 to 50 °C as a first step, and then post-cured at 0 to 150 °C for 6 (1'). A method for manufacturing a semipermeable membrane module, characterized in that the ends of the semipermeable membrane are sealed and fixed. (4) The amount of the polyamine curing agent is 50 to 50 mol% of the amine equivalent based on the epoxy equivalent of the epoxy base ingredient. A method for producing a semipermeable membrane module according to claim 3. (5) Claims 5 to 5, wherein the amount of the imidazole curing agent is 0.5 to 4% by weight based on the epoxy base resin. Semipermeable membrane module according to item 4. (6) Polyamine curing agent/imidazole curing agent N
Claim #43 - Third to fifth semipermeable membrane modules having a storm ratio of 10Ω/25 to 10015. (7) Claims 5 to 5, wherein the semipermeable membrane is a hollow thin membrane.
#I Semipermeable membrane module according to item 6. (8) The method for producing a semipermeable membrane module according to claims 3 to 7, wherein the solidification temperature in the first stage is 10 to 40°C. (9) Bost cure temperature in the second stage is 75-125°C
A method for manufacturing a semipermeable membrane module according to claims 3 to 8. 01 The method for producing a semipermeable membrane module according to claims 5 to 9, wherein the second step of post-curing is carried out in hot water at 75 to 100°C. The method for manufacturing a semipermeable membrane module according to claims 6 to 9, wherein the second stage of post curing is carried out in steam at a temperature of 90 to 125°C. (6) A method for producing a semipermeable membrane module according to claims 3 to 11, characterized in that the semipermeable membrane is kept in a wet state and its ends are characterized. 0. The method for producing a semipermeable membrane module according to claim 12, wherein the semipermeable membrane is brought into a wet state with a water content of 5 to 90%, and the end portion thereof is characterized. α4 When filling the gap between the semipermeable membrane with the liquid epoxy compound, centrifugal force with a gravitational acceleration of 3 to 200 G is used to fill the gap, and the semipermeable membrane has an end portion.Claim 11!3~
A method for producing a semipermeable membrane module according to item 11813. (2) The method for manufacturing a semipermeable membrane module according to claim 14, wherein the gravitational acceleration is 10 to 60G.