JPH03188927A - Production of hollow-fiber membrane module - Google Patents

Abstract

PURPOSE:To obtain the module having heat resistance and low elution property and effective in the production of semiconductors and medicine by using epoxy resin as the main agent and an acid anhydride compd. as the curing agent in the adhesive sealing medium for sealing the ends of plural hollow-fiber membranes. CONSTITUTION:Epoxy resin is used as the main agent and an acid anhydride compd. as the curing agent in the adhesive sealing medium for sealing the ends of plural hollow-fiber membranes to obtain the desired hollow-fiber membrane module. An epoxy resin having at least three glycidyl groups in the fundamental unit is preferably used, and a phenolic novolac-type epoxy resin, triphenylglycidyl ether methane, etc., are exemplified. When an acid anhydride compd. is used as the curing agent an adhesive with low elution property is obtained. A liq. acid anhydride compd. is preferably used, and methyltetrahydrophthalic anhydride, etc., are exemplified.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an adhesive sealant used for sealing the ends of hollow fiber membranes and a method for adhesively sealing the ends of hollow fiber membranes using the same. .

[Conventional technology]

Hollow fiber membrane modules have a large membrane area per unit volume, so they are used in fields that require a large amount of membrane processing, such as the manufacturing process of ultrapure water for wafer cleaning in semiconductor manufacturing processes, and injections in the pharmaceutical manufacturing industry. It is expected to be used as a production process for distilled water (pyrogen-free water).

In the production of hollow fiber membrane modules, it is essential to adhesively seal the hollow fiber membranes and the housing, and polyurethane-based or epoxy-based resins are used as the adhesive sealant. In particular, epoxy resins are widely used in applications requiring heat resistance due to their heat resistance and dimensional stability.

Until now, studies on adhesive sealants have focused on suppressing heat generation during curing of adhesive sealants, imparting impact resistance after curing, preventing peeling of cured products, and improving mechanical properties (Japanese Patent Laid-Open No. 61-141
904, JP 61-157307, JP 61-15
7308).

[Problem to be solved by the invention]

Microbial control is essential for ultrapure water for wafer cleaning in the semiconductor manufacturing industry and distilled water for injection in the pharmaceutical manufacturing industry. That is, if microorganisms are present in the ultrapure water for cleaning, they become foreign substances on the wafer and cause a decrease in the yield of semiconductor products. On the other hand, if microorganisms are present in distilled water for injection, pyrogen is generated as the microorganisms multiply, and when administered intravenously, it has a serious effect on patients. As described above, microbial control is essential in the semiconductor manufacturing industry and the pharmaceutical manufacturing industry. For this microbial control, 80 to 95
℃ hot water is required to be used at all times in the system.

However, in ultrapure water and distilled water for injection, in addition to microorganisms, substances eluted from membranes are strictly limited, and the level thereof is becoming increasingly high. In order to meet these strict water quality requirements, a hollow fiber membrane module that is both heat resistant and elution resistant is required. However, there is a problem in that there is no hollow fiber membrane module that satisfies this requirement.

The present invention relates to a method for manufacturing a hollow fiber membrane module that satisfies heat resistance and low elution properties, and particularly to an adhesive sealant and an adhesive sealing method thereof.

[Means to solve the problem]

That is, the adhesive sealant used for sealing the ends of hollow fiber membranes of the present invention and the method for adhesively sealing the ends of hollow fiber membranes using the same are as follows: (1) For sealing the ends of a plurality of hollow fiber membranes. A method for manufacturing a hollow fiber membrane module, characterized in that the adhesive sealant used is an epoxy resin as a main ingredient and an acid anhydride compound as a curing agent.

It is.

Epoxy resins consist of a combination of a polyfunctional epoxy compound as a main ingredient and various curing agents.

Curing agents are broadly classified into polyaddition type and catalytic type based on the reaction mechanism, and the former type is by far the most common.

The former can be divided into basic, acidic, and neutral types based on their chemical properties. Basic types include primary and secondary amines and polyamides, acidic types include polycarboxylic acids (especially their anhydrides) and phenols (especially phenol novolacs), and neutral types include polymercaptans. . Further, the appropriate curing temperature range differs depending on the type of curing agent. The excellent adhesion, heat resistance, and elution resistance of epoxy resins depend on the three-dimensional network structure formed by the curing reaction, mainly the crosslink density (or molecular weight between crosslinking points) and the chemical structure of the chains. The curing reaction mechanism of epoxy resins consists of a polymerization initiation reaction in which a curing agent is added through a ring-opening reaction with an epoxy group to produce hydroxyl groups, and a chain extension reaction in which the curing agent is polyadded to the hydroxyl groups generated by the initiation reaction. It consists of a cross-linking reaction in which a functional group containing active hydrogen generated by epoxy reacts with an epoxy group. Therefore, in order to consider adhesive sealants to be applied to heat-resistant and low-leaching hollow fiber membrane modules, it is necessary to select an epoxy resin curing agent and curing conditions that can control the chain extension reaction and cross-linking reaction in the curing reaction. There is. In other words, in a reaction system in which the chain extension reaction is extremely dominant over the crosslinking reaction at the initial stage of the curing reaction, the molecular weight between the crosslinking points increases (the crosslinking density decreases) and at the same time the mobility of the molecular chains decreases. Cross-linking reactions are less likely to occur and the degree of curing is also reduced. This leads to a decrease in the heat resistance of the adhesive sealant and an increase in eluable substances. In order to solve this problem, it is sufficient to use a curing agent with a low curing reaction rate in the initial stage of the reaction, and we have found that using an acid anhydride type curing agent in particular can yield an adhesive sealant with low elution properties. . It has also been found that it is desirable for the epoxy resin to have at least three or more glycidyl groups in its basic unit.

The curing agent used in the present invention is not particularly limited as long as it is an acid anhydride type, but it is preferably a curing agent that is liquid under working conditions.

For example, methyltetrahydrophthalic anhydride (MeTHP)
A>, methylhexahydrophthalic anhydride (MeHHPA)
), methyl nazic anhydride (MNA>), dodecyl succinic anhydride (DDSA), etc. Similarly, epoxy resins are not particularly limited, but include trifunctional or higher polyfunctional novolak type, aromatic glycidyl Ether type and aromatic glycidylamine type epoxy resins are desirable. For example, phenol novolac type epoxy resin (EPN), Talesol novolak type epoxy resin (
ECN), I-rephenyl glycidyl ether methane (
TPOEM), tetraglycidyldiaminodiphenylmethane (TGDDM), and the like.

〔Example〕

(Example 1) A phenol-novolac type multifunctional epoxy (Epicoat 152; oil-based shell epoxy) heated to 60°C in advance and a high temperature curing acid anhydride type curing agent [Evocure H
Y307; made by Yuka Shell Epoxy], curing accelerator (EM
124i Oil Shell Epoxy] were mixed and defoamed at 100 parts by weight, 110 parts by weight, and 1 part by weight, respectively, and then heated at 60°C.
The hollow fiber membrane bundle, whose ends had been sealed by reacting for 1 hour, and the module housing were adhesively sealed. Further, post-curing was performed at 80°C for 3 hours and at 150°C for 5 hours.

(Comparative Example 1) A phenol/novolac type multifunctional epoxy (Epicote 152; Yuka Shell epoxies) heated to 60°C in advance and a room temperature-curing modified alicyclic amine type curing agent [Ebicure 113; Yuka Shell 100 parts by weight, 11.5 parts by weight, and 17.8 parts by weight of a room-temperature-curing modified aliphatic amine curing agent [Epoxies] and 17.8 parts by weight, respectively, were mixed and defoamed, and then reacted at 80°C for 1 hour. The hollow fiber membrane bundle, whose ends were sealed, and the module housing were adhesively sealed. Further, post-curing was performed at 80°C for 3 hours and at 150°C for 5 hours.

(Comparative Example 2) A phenol-novolak type multifunctional epoxy [Epicoat 152; oil-based shell epoxy] and a room-temperature curing modified alicyclic amine type curing agent [Ebicure 113; oil-based shell epoxy] were used, respectively. After mixing and degassing 100 parts by weight and 32 parts by weight, the hollow fiber membrane bundle, whose ends had been sealed by reacting at room temperature for 1 hour, and the module housing were adhesively sealed. Further, post-curing was performed at 80°C for 3 hours and at 150°C for 5 hours.

(Comparative Example 3) A phenol/novolac type multifunctional epoxy preheated to 60°C [Epikoat 152; Yuka shell epoxies] and a room temperature curing modified heterocyclic amine type curing agent [Ebome] BOO2W; Yuka After degassing 100 parts by weight and 50 parts by weight of shell epoxies, respectively, the hollow fiber membrane bundle was reacted at room temperature for 1 hour to seal the ends of the hollow fiber membrane bundle and the module housing. Furthermore, at 40°C
Post-curing was carried out at 80°C for 3 hours.

(Comparative Example 4) Bisphenol-type bifunctional epoxy preheated to 60°C [Epikoat 828; Oilified shell epoxy]
, and high temperature curing acid anhydride curing agent [Epicure HY30
7i Yuka Shell Epoxy], hardening accelerator (EM124)
;Oilified shell epoxy], 100 parts by weight each,
After mixing 110 parts by weight and 1 part by weight and defoaming, it was heated to 1 at 60°C.
The hollow fiber membrane bundle whose ends were sealed by a time reaction was adhesively sealed to the module housing. Further, post-curing was performed at 80°C for 3 hours and at 150°C for 5 hours.

After curing, the adhesive sealant was subjected to two eluate tests based on the infusion plastic test (11th edition Japanese Pharmacopoeia, B-397): potassium permanganate reducing substance and ultraviolet absorption spectrum.

Table 1 shows the measurement results of potassium permanganate reducing substances. Table 2 shows the ultraviolet absorption spectrum measurement results.

Extraction conditions> The total area of the front and back is 600. Collect the cut pieces so that they are approximately 5cm long and 0.5cm wide. 5c+n
Cut into pieces, wash with water, and dry at room temperature. Put this in a hard glass container with a content of about 300 g, and add 20 g of water.
After adding 0- accurately and sealing with a stopper, heat at 1216 for 1 hour using a high-pressure steam sterilizer, and leave to stand until it reaches room temperature, and use this solution as the test solution.

<Judgment Criteria> If the difference in consumption of 0.0IN0 potassium permanganate solution between the test liquid 20- and the same amount of blank test liquid is 1.0- or less, the test is passed.

Table 2 Ultraviolet absorption spectrum measurement results <Judgment criteria> When testing the test solution using the absorbance measurement method with a blank test solution as a control, the absorbance at wavelengths of 220 nm or more and less than 241 nm is 0.08 or less, and for wavelengths of 241 nm or more and less than 350 nm.
If the absorbance at m or less is 0°05 or less, the test is passed.

In addition, the curing speed and degree of curing of the adhesive sealants were compared by dielectric measurement. The results are shown in Figures 1-3.

In this case, the curing rate is defined as the degree of decrease in ionic conductivity per unit time, and the degree of curing is defined as the magnitude of ionic conductivity after 6 hours. An acid anhydride type curing agent has a lower initial curing speed and a higher degree of curing than an aliphatic amine type curing agent or an alicyclic amine type curing agent.

The measurement was performed using an automatic polymer curing measurement system (Niemetric System ■ manufactured by Micromet Instruments).

〔Effect of the invention〕

According to the present invention, a heat-resistant and low-elution adhesive sealant for hollow fiber membrane modules can be obtained. Modules using this adhesive sealant can be applied to manufacturing processes that require microbial control using hot water, such as the manufacturing process of ultrapure water for wafer cleaning in semiconductor manufacturing processes and the manufacturing process of distilled water for injection in pharmaceutical manufacturing processes. It becomes possible.

[Brief explanation of drawings]

FIG. 1 shows the dielectric measurement data of Example 1, FIG. 2 shows the dielectric measurement data of Comparative Example 1, and FIG. 3 shows the dielectric measurement data of Comparative Example 2. The solid line shows the change in ionic conductivity over time, and the dotted line shows the change in temperature over time. Also,
Ionic conductivity was expressed logarithmically.

Claims (1)

[Claims] (1) A method for manufacturing a hollow fiber membrane module, characterized in that an epoxy resin is used as a main ingredient and an acid anhydride compound is used as a curing agent in the adhesive sealant used for sealing the ends of a plurality of hollow fiber membranes.