JP3497593B2 - Hollow fiber membrane module - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a hollow fiber membrane module having excellent heat resistance.

[0002]

2. Description of the Related Art A hollow fiber membrane module in which a plurality of hollow fiber membranes are bundled and at least one end thereof is bonded and fixed while maintaining an open state has a large effective membrane area per unit volume. , Because it has excellent filtration performance,
Filtration equipment, ultrapure water production equipment, sterile water production equipment, water purifier,
It is widely used as an apparatus for filtration or separation with various liquids or gases for industrial use such as a gas-liquid separator, food, medical or household. With the increase in the range of application, it is desired that the application conditions also endure use under high temperatures such as hot water filtration at 80 to 90 ° C. and high temperature sterilization with steam.

As an adhesive for fixing the end portions of the bundled hollow fiber membranes in an open state, that is, a so-called potting agent,
Generally, urethane resin and epoxy resin are used, and particularly urethane resin is widely used because it is excellent in flexibility and adhesiveness at room temperature. However, since urethane resin is inferior in heat resistance, it is hydrolyzed and deteriorated at a high temperature in applications where heat resistance is required, or the mechanical strength such as swelling, cracking, and softening of the resin decreases, and thus the adhesive fixing part. There is a problem in that the peeling occurs and the sealing property of other than the hollow fiber membrane which should function is impaired.

On the other hand, an epoxy resin is excellent in heat resistance, but since it is cured at a high temperature, it is heated to a higher temperature due to the reaction heat during the curing to cause many fine cracks on the surface or inside of the resin, or due to volume shrinkage at the time of curing. Since the stress strain is large, the adhesiveness to the module case is deteriorated, and further, the flexibility at the normal temperature is poor and the adhesive is very hard to cut at the adhesive fixing portion when the module is formed.

In order to improve the properties of such an epoxy resin, the crosslinking density is lowered by (1) blending a plasticizing component or using a monofunctional epoxy compound together. (2) A liquid rubber having a reactive functional group introduced into the molecule is reacted and modified. (3) There is a proposal to add an inorganic filler. According to these methods, the adhesiveness and the hard and brittle property of the epoxy resin are considerably improved, but the heat resistance is lowered and the elution from the plasticizing component is extremely increased, and further the physical properties of the resin are deteriorated. The range is limited.

[0006]

The present invention can withstand long-term use without deteriorating the adhesiveness of a hollow fiber membrane such as a module case to a support member under high temperature such as hot water filtration or high temperature sterilization. In addition, it was made as a result of diligent studies on an epoxy resin potting agent with extremely little elution,
An object of the present invention is to provide a hollow fiber membrane module having excellent heat resistance that can be used even at high temperatures.

[0007]

According to the present invention, a plurality of hollow fiber membranes are bundled, and at least one end of the hollow fiber membranes holds the open state of the hollow fiber membranes and is adhesively fixed to a support by an epoxy resin. In the hollow fiber membrane module configured, a hollow fiber membrane module is characterized in that rubber particles having a particle diameter of 20 μm or less are dispersed in an epoxy resin.

The epoxy resin in which the rubber particles are dispersed in the present invention is not particularly limited and may be appropriately selected and used according to its use and required performance. For example, bisphenol A, bisphenol F, phenol novolac, cresol novolac, etc. Examples thereof include glycidyl ethers of phenols, glycidyl ethers of alcohols such as butanediol, polyethylene glycol, and the like. These may be used alone or in combination of two or more.

The rubber particles dispersed in the epoxy resin in the present invention are synthetic rubbers such as (meth) acrylic ester type polymers, organic silicon type polymers (silicone), fluorine type polymers and butadiene type polymers, preferably Is a (meth) acrylic ester-based polymer, silicone particles are used, and a (meth) acrylic resin can be easily dispersed in the epoxy resin solution because a functional group reactive with the epoxy resin can be easily introduced. Ester polymer particles are particularly preferably used.

For example, the monomer used to obtain the (meth) acrylic ester polymer has 1 to 18 carbon atoms.
(Meth) acrylic esters, which are esters of aliphatic alkyl alcohol with (meth) acrylic acid,
Contains hydroxyl groups such as monoesters of hydroxylethyl acrylate and polypropylene glycol (meth)
Examples include polyfunctional (meth) acrylic esters having two or more polymerizable unsaturated groups in the molecule such as acrylic esters, esters of (meth) acrylic acid with polyhydric alcohols such as ethylene glycol and trimethylolpropane. The
These are polymerized alone or in combination of two or more to obtain a (meth) acrylic ester polymer.

The (meth) acrylic ester polymer may be copolymerized with other copolymerizable monomers such as (meth) acrylonitrile, styrene and vinyl acetate. The polymerization method for obtaining the (meth) acrylic ester polymer is not particularly limited and, for example, a conventionally known emulsion polymerization method or the like is applied.

The rubber particles dispersed in the epoxy resin are strains caused by curing shrinkage of the resin when the epoxy resin is cured, mechanical stress from the outside under high temperature such as hot water filtration and high temperature sterilization, a tubular case, a plate. The hollow fiber membrane supporting member such as the module, and the module that absorbs and disperses the stress strain inside the epoxy resin that adheres and fixes the hollow fiber membrane caused by the difference in the coefficient of linear thermal expansion from the housing case member in which the module is mounted. The hollow fiber membrane module is endowed with heat resistance such that the hollow fiber membrane supporting member such as a case is fixed and adhered.

In order to absorb and disperse stress and strain inside the epoxy resin and maintain a good adhesive and fixed state with a hollow fiber membrane support member such as a cylindrical case, the particle size is 20 μm or less, preferably 10 to 10. It must be 0.1 μm. The amount of rubber particles dispersed in the epoxy resin is preferably 1 to 30 parts by weight, and more preferably 5 to 20 parts by weight, based on 100 parts by weight of the epoxy resin.

The dispersion of the rubber particles in the epoxy resin is carried out by adding the rubber particles to the epoxy resin solution, but it may be mixed with the epoxy resin solution as an emulsion in the state where the rubber particles are formed. In the epoxy resin solution, as a curing agent, generally used amines, acid anhydrides and the like are mixed alone or mixed in consideration of the chemical equivalents of the epoxy groups of the epoxy resin and the functional groups of the curing agent.

The hollow fiber membrane module of the present invention is, for example,
After inserting the hollow fiber membranes that have been aligned and bundled to a specified length into the cylindrical case, inject the epoxy resin solution in which rubber particles are dispersed by the centrifugal molding method and heat-cure, then cut the adhesive fixing part of the hollow fiber membranes. Then, it can be obtained by forming an open state of the hollow fiber membrane on the end face.

As the hollow fiber membrane in the hollow fiber membrane module of the present invention, a known hollow fiber membrane is generally used as a liquid or gas separation membrane, and any one such as a single layer membrane, an asymmetric membrane and a composite membrane is used. In the present invention, the hollow fiber membrane is preferably composed of a heat-resistant material such as polysulfone, polyether sulfone, poly-4-methylpentene-1, polyallyl sulfone, or polyimide, but polyethylene, It may be a hollow fiber membrane made of polyolefin such as polypropylene, or a hollow fiber membrane obtained by further crosslinking or hydrophilizing this.

The hollow fiber membrane support such as the cylindrical case in the hollow fiber membrane module is, of course, made of a material having an adhesive property with an epoxy resin which is a potting agent, but is preferably heat resistant, It is composed of a polysulfone resin, a polyethersulfone resin, a polypropylene resin, an ABS resin, a polyphenylene ether resin, or the like, which has good chemical resistance.

[0018]

EXAMPLES The present invention will be specifically described below with reference to examples. In the examples, parts and% mean parts by weight and% by weight.

Example 1 85 parts of ethyl acrylate, 10 parts of methacrylic acid and 5 parts of methacrylglycidyl were polymerized at 70 ° C. using ion-exchanged water and a modified polyamine as an emulsifier to give a non-volatile content of 45% (meth). ) An acrylic ester polymer emulsion was obtained. Epicoat 828 (bisphenol A type epoxy resin manufactured by Yuka Shell Epoxy Co., Ltd.) was added to this emulsion and stirred to obtain a uniform viscous liquid. Then, remove water while depressurizing at 70 ° C,
An epoxy resin solution having 10% of (meth) acrylic acid ester-based polymer particles having a particle size of 0.3 μm dispersed therein was obtained.

On the other hand, 240 polysulfone hollow fiber membranes having an outer diameter of 470 μm and a thickness of 75 μm are bundled to form an outer diameter of 70 mm,
It was stored in a cylindrical case made of polysulfone resin with an inner diameter of 63 mm and a length of 258 mm, placed in a centrifugal molding machine heated to 40 ° C., and bis-P-aminocyclohexylmethane was added as a curing agent while applying a centrifugal force of 20 G. After the epoxy resin solution was injected and the mixture was centrifugally molded for 2 hours, it was post-cured at 80 ° C. for 6 hours. After that, the end portion of the adhesive fixing portion between the epoxy resin and the hollow fiber membrane bundle is cut to form an opening state of the hollow fiber membrane on the end surface, and the hollow fiber membrane module in which the epoxy resin of the adhesive fixing portion and the case member are adhered is formed. I made it.

The leak test of the hollow fiber membrane module is 1 kg.
Method / cm ² of water pressure over 3 minutes, if no leakage, to check for leakage of water perform leak check of each 3 minutes until water pressure 1 kg / cm ² increases the water pressure at 1 kg / cm ² increments According to.

After making the obtained hollow fiber membrane module hydrophilic with ethanol, hot water at 80 ° C. was passed through it at a differential pressure of 1 kg / cm ² for 6 months, after which the hollow fiber membrane module was dried and the above leak test was conducted. However, no water leakage occurred from the adhesive interface between the case member and the epoxy resin. Further, the obtained hollow fiber membrane module was subjected to steam sterilization treatment at 121 ° C. for 30 minutes 60 times, but there was no peeling between the case member and the epoxy resin or cracking of the epoxy resin, and the hollow fiber membrane bundle was adhesively fixed. The resulting hollow fiber membrane module had excellent heat resistance.

Comparative Example 1 In Example 1, (meta)
A hollow fiber membrane module was produced in the same manner as in Example 1 except that the epoxy resin solution in which acrylic acid ester-based polymer particles were dispersed was replaced with an epoxy resin solution that did not contain (meth) acrylic acid ester-based polymer particles. When hot water of 80 ° C. was passed, the case member and the epoxy resin were separated from each other after about 10 days of passing water, resulting in water leakage.

(Embodiment 2) Epicoat 828 and Trefeel E601 (silicone manufactured by Toray Silicone Co., Ltd.,
An average particle diameter of 3 μm) and a curing agent (bis P-aminocyclohexylmethane) were mixed in a composition shown in Table 1 and defoamed to obtain an epoxy resin solution in which silicone particles were dispersed.

On the other hand, 5000 pieces of EHF410C (polyethylene hollow fiber membrane manufactured by Mitsubishi Rayon Co., Ltd.) were bundled and housed in a cylindrical case made of polysulfone resin having an outer diameter of 70 mm, an inner diameter of 63 mm and a length of 258 mm, and heated at 40 ° C. It was placed in a warm centrifugal molding machine, the epoxy resin solution was injected while a centrifugal force of 40 G was applied, the mixture was centrifugally molded for 2 hours, and then post-cured at 80 ° C. for 6 hours. After that, the end of the adhesive fixing portion of the hollow fiber membrane bundle was cut to form an open state of the hollow fiber membrane on the end face, and a hollow fiber membrane module in which the epoxy resin of the adhesive fixing portion and the case member were adhered was manufactured.

After making the obtained hollow fiber membrane module hydrophilic with ethanol, hot water at 80 ° C. was passed for 30 minutes, and then,
Immediately, a heat cycle test was repeated 100 times, in which water at 25 ° C. was passed for 30 minutes as one cycle, and the above-mentioned leak test was performed at the bonding interface between the case member and the epoxy resin. The results of the leak inspection are shown in Table 1.

[0027]

[Table 1]

[0028]

In the hollow fiber membrane module of the present invention, the epoxy resin, which is a potting agent, has rubber particles dispersed therein, so that the epoxy resin has excellent durability and heat resistance with the support member such as the case and the hollow fiber membrane. Adhesive,
The hollow fiber membrane module provides heat resistance that can be used even at high temperatures, and the hollow fiber membrane module of the present invention can be used for a long time at high temperature such as hot water filtration or steam sterilization treatment requiring heat resistance. Even in use, it can be preferably used without causing water leakage or the like at the adhesive fixing portion between the support member such as the case and the hollow fiber membrane.

─────────────────────────────────────────────────── ─── Continued Front Page (72) Inventor Yoshio Chiga 4-chome, Sunadabashi 1-chome, Higashi-ku, Nagoya, Aichi Prefecture Mitsubishi Rayon Co., Ltd. Product Development Research Center (56) Reference JP-A-6-170176 (JP, A) JP-A-3-262522 (JP, A) Actual development Sho 61-171502 (JP, U) (58) Fields investigated (Int.Cl. ⁷ , DB name) B01D 61/00-71/82 B01D 53/22 C02F 1/44

Claims (3)

(57) [Claims] 1. A hollow fiber membrane module comprising a plurality of hollow fiber membranes bundled together, at least one end of which is held in an open state of the hollow fiber membranes and adhered and fixed to a support by an epoxy resin. , Epoxy resin particle size 20μm
A hollow fiber membrane module comprising the following rubber particles dispersed therein. 2. The hollow fiber membrane module according to claim 1, wherein the rubber particles are (meth) acrylic ester polymer particles or silicone particles. 3. A rubber particle in an amount of 1 to 30 parts by weight is dispersed in 100 parts by weight of an epoxy resin.
The hollow fiber membrane module described.