JP2003112060A - Ion adsorbing resin and ion adsorbing porous material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an ion adsorbing resin which can adsorb and remove ions in ultrapure water and shows little elution of fine particles, ions and TOC (total organic carbon), and a porous ion adsorbing material. SOLUTION: The ion adsorbing resin is prepared by introducing ion exchange groups into the surfaces of polymer resin particles having <=300 μm particle size and has 0.3 to 10 meq/g ion exchange capacity. The ion adsorbing porous material contains the ion adsorbing resin by 10 to 70 wt.% in the porous resin matrix including at least one thermoplastic resin particle having <=300 μm particle size.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to an ion-adsorbing resin capable of adsorbing and removing colloidal substances and ions to an extremely low concentration in a process for producing ultrapure water, and a porous ion-adsorbing body containing the same.

[0002]

2. Description of the Related Art In an ultrapure water production process, ion exchange resins are mainly used for removing ions in water.
In fields that use ultrapure water, including the semiconductor industry,
The demand for the purity of ultrapure water is increasing, and TOC elution from the ion exchange resin itself is becoming a problem. Conventional ion exchange resins generally have a particle size of 12
The resin is distributed in the range of 00 μm to 300 μm, and when such resin is packed in a resin tower and water to be treated is passed through, the gap (water passage) between the resins is large and the resin surface of ions in the water to be treated becomes large. The contact probability of was small, and the effect of removing ions was extremely poor, especially in water with a low ion concentration such as ultrapure water. Further, organic impurities (which are detected as TOC in the case of ultrapure water) formed inside the resin during the polymerization of the ion exchange resin are taken into the resin, and the resin has a large particle size and is a crosslinked polymer. Therefore, the diffusion speed of these impurities was low, and cleaning was extremely difficult.

Therefore, in order to meet the demand for high-purity ultrapure water with low TOC elution, an ultrapure water production system using an ion adsorption film has been researched and developed as a new deionization technique (Japanese Patent Laid-Open No. 5-209071). Japanese Patent Laid-Open No. 7-415
74, etc.). This ion adsorption membrane has advantages of higher ion removal efficiency and less TOC elution than an ion exchange resin. Ion adsorption membranes have shapes such as flat membranes, fibers, hollow fibers, etc., but the range of pore diameter and membrane thickness that can be manufactured is limited due to the balance of separation function, water permeability, mechanical strength, etc., to increase the surface area. The flat membrane is folded into a pleated cartridge and the hollow fibers are bundled into a module. As the ion adsorbent, one having good breakthrough characteristics and high water permeability is desirable, and one having a large film thickness and a large pore diameter is preferable, but it is difficult to manufacture the ion adsorbent.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an ion-adsorbing resin and a porous ion-adsorbing body having a very small TOC elution and excellent ion-removing performance.

[0005]

DISCLOSURE OF THE INVENTION The present inventor has found that a particle size of 300
The present invention has been achieved by paying attention to an ion-adsorbing resin in which a functional group having an ion-exchange function is introduced on the surface of polymer resin particles of μm or less and a porous ion-adsorbing body containing the ion-adsorbing resin.

That is, the present invention is as follows. (1) An ion-adsorbing resin in which functional groups having an ion-exchange function are introduced on the surface of polymer resin particles having a particle diameter of 300 μm or less, and the ion-exchange capacity is 0.3 to 10 meq /
An ion-adsorptive resin characterized by being g. (2) A functional group having an ion exchange function is a cation exchange group,
The ion adsorption resin according to (1), which is either an anion exchange group or a chelate exchange group. (3) The ion adsorption according to (1) or (2), wherein a functional group having an ion exchange function is introduced into polymer resin particles having a particle diameter of 300 μm or less by utilizing radiation graft polymerization. Resin manufacturing method. (4) Thermoplastic resin particles having a particle size of 300 μm or less,
(1) or (2) The ion-adsorbing resin is contained in the porous resin matrix integrally formed with the aggregate of the ion-adsorbing resin, and the ion-adsorbing resin is contained in an amount of 10 to 70 wt% of the total mass of the matrix. Ion adsorbent. (5) The average pore diameter of the porous ion adsorbent is 1 to 100 μm.
m, and the porosity is 20 to 60%, The porous ion adsorbent according to (4), characterized in that

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the present invention, the particle size is 300 μm.
By introducing a functional group having an ion exchange function to the surface of polymer resin particles of m or less, the flow path of the water to be treated between the resin particles is narrow, and therefore the efficiency of contact of ions in the water to be treated with the ion-adsorbing resin is high. It is possible to obtain an ion-adsorbing resin having excellent ion removal efficiency (excellent breakthrough property). Further, since the functional group having an ion exchange function substantially exists only on the resin surface, rinsing after resin regeneration is easy,
Almost no elution of TOC (contaminant organic matter) is observed.

The present invention also provides at least one particle size of 30
Provided is a porous ion adsorbent containing 10 to 70 wt% of the ion adsorption resin in the total mass of the matrix in a porous matrix containing thermoplastic resin particles of 0 μm or less and the ion adsorption resin. The porous ion adsorbent can be formed into various shapes such as a sheet shape, a block shape, a pipe shape, and a cylindrical shape, and can be made into a shape that can be easily handled when it is used at the point of use of ultrapure water. With
It also has the advantages of high ion removal effect and almost no TOC elution.

The present invention will be described in more detail below. The polymer resin particles referred to in the present invention include, in addition to natural resins such as cellulose, thermosetting resins typified by phenol resins, urea resins, melamine resins, polyester resins, allyl resins, epoxy resins, polychlorinated resins, etc. Examples thereof include particles of a thermoplastic resin represented by vinyl, polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyamide, polyacetal, polycarbonate and the like.

Of these, polyolefin resins typified by polyethylene and polypropylene are more preferable in view of their excellent chemical resistance, small amount of elution, and the method of introducing functional groups to the surface of resin particles. As the polyolefin resin, polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, ethylene-hexene-1 copolymer, ethylene-
Pentene-1 copolymer, ethylene-octene-1 copolymer, ethylene-4-methylpentene-1 copolymer, ethylene-vinyl acetate copolymer, ethylene- (meth) acrylic acid copolymer, ethylene- ( Examples thereof include (meth) acrylic acid ester copolymers. Among them, polyethylene is more preferable because it is easy to obtain a powder having a particle size of 300 μm or less, has excellent chemical resistance, and has little elution.

Further, in the present invention, graft polymerization by irradiation with radiation may be used as one of the methods for introducing an ion-exchange group. Considering the generation rate / retention rate of radicals as a graft initiation point in this method, Polyolefins represented by polyethylene, polypropylene, and ethylene-propylene copolymers are preferable, and polyethylene is particularly preferable. The particle size of the polymer resin particles of the present invention is preferably 300 μm or less from the viewpoint of ion adsorption efficiency, and more preferably 10 to 100 μm. The average particle diameter is shown by the average value of the minor axis and the major axis of 50 or more particles individually measured from an enlarged photograph of the resin particles.

The method of introducing the functional group having an ion exchange function is preferably a method of uniformly introducing the ion exchange group onto the surface of the polymer resin particles. For example, a method in which radicals are uniformly generated even inside the polymer resin particles, the radicals are used as a starting point to graft a monomer and a crosslinking agent, and then an exchange group is introduced is suitable. Alternatively, there is a method of directly grafting a monomer having an exchange group. As a method for uniformly generating radicals on the entire surface, a method using plasma, a method using light, a method using radiation or a method using various radical initiators is preferable, but when it is particularly intended to ensure uniformity, irradiation with radiation is preferable. The most suitable method is to generate radicals.

Ionizing radiation used for radiation graft polymerization suitable for introducing many ion exchange groups is α,
There are β, γ rays, electron rays, ultraviolet rays, and the like, and any of them can be used, but γ rays are suitable for more uniformly generating radicals to the inner surface. An economical irradiation dose that provides a sufficient amount of radicals for graft polymerization and does not cause unnecessary crosslinking or partial decomposition is 10 kGy to 300 kGy.
And preferably 50 kGy to 100 kGy.

As a method for performing radiation grafting on the polymer resin particles, a simultaneous irradiation method of irradiating the polymer resin particles with the monomer in the coexistence, or a method of irradiating the polymer resin particles with the radiation in advance and then contacting with the monomer There is a pre-irradiation method, but the pre-irradiation method is preferred because it produces less homopolymer of the monomer. As the ion exchange group, from the viewpoint of ion exchangeability and thermochemical stability, the cation exchange group is preferably a sulfonic acid type which is a strong acid, and the anion exchange group is a quaternary ammonium salt type or a pyridinium salt type which is a strong base. preferable.

The ion exchange capacity to be introduced is preferably 0.3 to 10 meq / g, more preferably 0.5 to 5 meq / g, from the viewpoint of ion removal capacity. In general ultrapure water, metal ions are present at a concentration of 1 ppt level, and most of them are Na ions. An ion such as Na ion having a low valence with a proton and having a low selectivity with respect to a proton has a proton concentration (about 10 ^-7 eq) that competes during ion exchange at a 1 ppt level (that is, a concentration of 10 ^-10 eq / L level).
/ L), the utilization efficiency of ion-exchange groups becomes extremely low. (Theoretical calculation shows a utilization efficiency of about 1/1000) Therefore, at an ion exchange capacity of 0.3 meq / g or less, almost no ion removal effect is observed unless a considerably large amount of ion adsorption resin is used. Further, when the ion exchange group is introduced at 10 meq / g or more, the layer of the ion exchange group introduced on the resin surface becomes too thick, and it becomes difficult to suppress the elution of impurities mixed during the synthesis.

Any method may be used for introducing the cation exchange group. A sulfonation reagent such as sulfuric acid, fuming sulfuric acid, sulfur trioxide, chlorosulfuric acid, fluorosulfuric acid or amidosulfuric acid is used to form an aromatic compound by a substitution reaction. There are a method of introducing a sulfonic acid group and a method of adding a sulfite. For example, after polymerizing styrene or glycidyl methacrylate and a cross-linking agent onto γ-irradiated polymer resin particles, chlorosulfonic acid is used for styrene, and glycidyl methacrylate is reacted with an aqueous sodium sulfite solution to form a sulfo group. Introduce. A monomer having a sulfonic acid group,
For example, there is a method of directly graft-polymerizing styrene sulfonate.

Any method may be used for introducing the anion exchange group. For example, after chloromethylstyrene or glycidyl methacrylate is graft-polymerized on the polymer resin particles irradiated with γ-ray, a quaternary ammonium group is introduced. In the case of chloromethylstyrene, it is treated with trimethylamine. In the case of glycidyl methacrylate, a quaternary ammonium group is introduced by reaction with trimethylamine hydrochloride. There is also a method of directly graft-polymerizing a monomer having a quaternary ammonium group, for example, vinylbenzyltrimethylammonium salt, onto polymer resin particles.

In the case of a chelate exchange group, any method may be used as long as a functional group having a function of forming a chelate with a metal ion in water such as iminodiacetic acid group, mercapto group and ethylenediamine can be introduced. For example, γ-irradiated polymer resin particles are graft-polymerized with an ethanol solution in which glycidyl methacrylate and divinylbenzene are dissolved, and then a 1: 1 mixture of dimethyl sulfoxide containing sodium iminodiacetate and water is reacted. A method of introducing a chelate exchange group can be mentioned.

The porous ion adsorbent of the present invention comprises a porous resin matrix formed by integrating at least one thermoplastic resin particle having a particle size of 300 μm or less and an aggregate of the ion adsorbent resin of the present invention. The ion-adsorbing resin (1) is present in an amount of 10 to 70 wt% in the total mass of the matrix. That is, it can be obtained by uniformly mixing the ion-adsorbing resin of the present invention and the thermoplastic resin particles, placing the mixture in a mold and sintering it. Further, the shape of the ion adsorbent is not particularly limited to a sheet shape, a block shape, a pipe shape, a cylindrical shape, and any shape is possible.

The thermoplastic resin particles for obtaining the porous ion adsorbent of the present invention include polyvinyl chloride, polyethylene, polypropylene, polystyrene, polymethylmethacrylate, polyamide, polyacetal, polycarbonate, polyvinylidene fluoride, ethylene- Thermoplastic resins represented by tetrafluoroethylene copolymer and the like can be mentioned. The ion-adsorbing resin of the present invention easily decomposes at high temperatures. In particular, at a high temperature of 180 ° C. or higher, the tendency is strong and the decomposition becomes severe. Therefore, it is preferable to set the heating temperature at the time of molding the sintered body to 180 ° C. or lower.
Further, considering the application to ultrapure water which is the object of the present invention, it is desirable to use a thermoplastic resin with less elution,
Among the above thermoplastic resins, it is preferable to use a polyvinylidene fluoride or the like having a relatively low melting point among polyolefin thermoplastic resins and fluorine resins.

The ratio of the ion-adsorbing resin particles of the present invention mixed with the thermoplastic resin particles is 10 to 70 wt.
% Is preferred. 10 wt% or more from the viewpoint of ion adsorption capacity, 70 wt% from the viewpoint of strength of the porous ion adsorbent
The following are preferred. The porosity of the porous ion adsorbent of the present invention is preferably 20 to 60%, more preferably 30 to 50% from the viewpoint of the amount of treated water and the strength of the structure. The porosity is determined by the difference in mass between the state of being impregnated with water and the state of dryness. That is, the sintered body is dipped in ethanol for 1 hour and then dipped in pure water for 20 minutes × 5 times to remove water from the surface of the sintered body, and then the mass is measured. Then, it is again immersed in ethanol and dried at 50 ° C. for 10 hours, and the mass after drying is measured to determine the porosity from the difference between the two. Alternatively, the specific gravity of the resin portion forming the sintered body can be determined by the specific gravity bin, and the porosity can be determined in relation to the volume occupied by the sintered body.

The method of forming a porous ion adsorbent by using the ion adsorbent resin as a matrix with thermoplastic resin particles in the present invention is generally carried out by heating and sintering. That is, the above-mentioned resin particle mixture is filled in a mold, and heated above the melting point of the thermoplastic resin to be sintered. The mold is preferably filled uniformly using a commercially available vibration device. As the heating method, any controllable heating means is used. There are methods such as hot air dryer, electric dielectric heating, and electric resistance overheating.

When the cation adsorbing resin is sintered, the H type can be used as a counter ion. However, in the H type, a decomposition reaction easily occurs at a high temperature. Therefore, when the sintering temperature is high, an alkali metal salt such as Na or Ca is used. It is preferable to perform the sintering in an isoalkaline earth metal salt type. Similarly, in the case of sintering an anion exchange resin, it is preferable to perform sintering with a halogen salt type such as Cl rather than with an OH type because thermal decomposition does not occur at high temperatures. INDUSTRIAL APPLICABILITY The ion adsorbent resin and porous ion adsorbent according to the present invention can remove cation components, anion components, ionic components such as alkali and alkaline earth metals, and transition metals to a very low concentration, and TOC is extremely eluted. Since it is small, it can be applied mainly to the field of ultrapure water.

[0024]

Example 1 Polyethylene powder "Sunfine UH901" (trademark) manufactured by Asahi Kasei Co., Ltd. was sieved with a 200-mesh wire mesh to obtain polyethylene powder having a particle size of 100 μm or less. 250 g of this powder was put in a bag of polyethylene vapor-deposited with aluminum, sealed with nitrogen gas, and irradiated with 100 kGy of γ-rays. Styrene 300g, divinylbenzene 43.6g (purity 5
5%) is dissolved in 1 L of isopropyl alcohol and heated to 50 ° C.
Then, dissolved oxygen was removed by nitrogen bubbling for 30 minutes. "Sunfine UH901" after γ-ray irradiation was put into this monomer solution under nitrogen bubbling. After stirring for 3 hours, the reaction slurry was filtered through a Buchner funnel, washed with 3 L of dichloromethane, and dried under vacuum. The yield of this graft body was 410 g. 200 g of the grafted product was added to a reaction solution prepared by dissolving 71 g of chlorosulfonic acid in 1 L of dichloromethane, and the mixture was stirred for 3 hours. 500 mL of isopropyl alcohol was added to this reaction solution, and the mixture was stirred for a while, filtered through a Buchner funnel, then washed with 1 L of isopropyl alcohol and 10 L of pure water, and vacuum dried.
The yield of the obtained cation-type ion adsorption resin is about 240 g.
Met. After taking 10 g of the ion-adsorbing resin and immersing it in pure water, it was placed in a glass chromatographic column and 1 N Na was added.
Wash in order of OH solution, pure water, 1N nitric acid solution, pure water,
A 1N NaCl solution was passed through, and the resulting permeated water was titrated with 1N NaOH to determine the ion exchange capacity. The ion exchange capacity of the resin was 2.4 meq / g, and was 0.87 meq / mL when calculated in terms of the wet volume of the resin.

[0025]

[Example 2] 100 mL of the ion-adsorbing resin obtained in Example 1
Was packed in a glass column having an inner diameter of 15 mmφ, regenerated with 1N nitric acid, and hot ultrapure water at 80 ° C. was passed through at a flow rate of 100 mL / min for 48 hours. The TOC of the ultrapure water at the column inlet and the TOC at the column outlet are the TOC meter A1 manufactured by Anatelle.
It was measured at 000 XP, and ΔTOC was determined from the difference. ΔTOC was about 500 ppb at the beginning of washing, but 24
After the time, it became stable at about 20 ppb. After that, when ultrapure water at room temperature was passed through, ΔTOC became 1 ppb or less.

[0026]

[Comparative Example 1] Instead of the ion-adsorbing resin of Example 2, an ion exchange resin "DIAION PK21" manufactured by Mitsubishi Chemical Corporation.
2 ”(trademark) was used, and ΔTOC of the ion exchange resin was evaluated in the same manner as in Example 2. 4 for hot ultrapure water
The ΔTOC was 120 to 150 ppb even after passing water for 8 hours, and the ΔTOC was 10 to 15 after passing ultrapure water at room temperature.
ppb was observed.

[0027]

[Example 3] As in Example 1, polyethylene powder "Sunfine SH801" (registered trademark) 2 manufactured by Asahi Kasei Corporation was used.
50 g was irradiated with 100 kGy gamma rays. 300 g of chloromethylstyrene and 43.6 g of divinylbenzene were dissolved in 1 L of isopropyl alcohol, nitrogen bubbling was carried out at 50 ° C. for 30 minutes, and 250 g of polyethylene powder after γ-ray irradiation was added. After 3 hours, the mixture was filtered through a Buchner funnel, washed with 1 L of methylene chloride, and dried under vacuum. The obtained graft copolymer was immersed in isopropyl alcohol in which 30% of trimethylamine was dissolved and reacted at 35 ° C. for 50 hours to form a quaternary ammonium. The obtained anion-type ion-adsorbing resin was washed with ethanol and water, replaced with ethanol, and dried with a vacuum dryer. The ion exchange capacity of the anion-type ion adsorption resin was determined by a titration method, and as a result, it was 3.26 meq / g (wet volume conversion 1.2 meq / mL). The TOC elution of this anion-type ion-adsorbing resin was evaluated by the same method as in Example 2. As a result, ΔTOC after washing with hot ultrapure water at 80 ° C. for 48 hours was evaluated.
Was less than 1 ppb.

[0028]

[Example 4] In the same manner as in Example 1, 250 g of polyethylene powder (Sun Fine SH801 manufactured by Asahi Kasei) was added to 100 g.
Irradiation with γ-rays of kGy. 300 g of glycidyl methacrylate and 43.6 g of divinylbenzene were dissolved in 1 L of isopropyl alcohol, dissolved oxygen was removed by nitrogen bubbling at 30 ° C., and 250 g of polyethylene powder after γ-ray irradiation was added. The reaction was carried out for 0.5 hour, and the grafted resin powder was taken out and washed with isopropyl alcohol. The obtained graft copolymer was put into a mixed solution of dimethylsulfoxide in which 10 wt% of sodium iminodiacetate was dissolved and water in a volume ratio of 1: 1 and the mixture was heated at 80 ° C.
And reacted for 72 hours. The ion exchange capacity of the chelate-type ion-adsorbing resin thus obtained was 0.86 meq.
/ G (wet volume conversion 0.34 meq / mL).
The TOC elution of this chelate-type ion-adsorbing resin was carried out in Example 2
When evaluated by the same method as in 48
ΔTOC after the time washing was 1 ppb or less.

[0029]

[Example 5] The cation-type ion-adsorbing resin and polyethylene powder synthesized in Example 1 ("Sunfine SH8
01 "was sieved with a 200-mesh wire net) and mixed at a mass ratio of 50/50. Outer diameter / inner diameter = 80mmφ / 70
Outside diameter / inner diameter = 60 mmφ inside an aluminum extruded tube of mmφ
/ 50mmφ aluminum extruded tubes are installed concentrically as a mold, and the powder mixture is put in the gap (the vibration is slightly vibrated to make the packing dense) in a hot air dryer at 150 ° C.
It hold | maintained for 0 minute and sintered. A plate made of polyethylene and a filtered water port were fused to the upper and lower sides of the obtained cylindrical cation type porous ion adsorbent to obtain a cartridge type filter as shown in FIG. This filter was placed in a commercially available PFA cartridge filter housing, and after regenerating by passing 1N nitric acid, TOC elution was evaluated in the same manner as in Example 2, and was washed with hot ultrapure water at 80 ° C. for 48 hours. The subsequent ΔTOC was 1 ppb or less. In addition, the ion exchange capacity of the obtained cation-type porous ion adsorbent was 0.7.
It was 2 meq / g.

[0030]

Example 6 An anionic porous ion adsorbent was prepared in the same manner as in Example 5, except that the anionic ion adsorbent resin synthesized in Example 3 was used instead of the cationic ion adsorbent resin synthesized in Example 1. Obtained. The TOC elution of this anion-type porous ion adsorbent was evaluated by the same method as in Example 5. As a result, ΔT after washing with hot ultrapure water at 80 ° C. for 48 hours was evaluated.
OC was 1 ppb or less. The ion exchange capacity of the obtained anion type porous ion adsorbent was 0.96 me.
It was q / g.

[0031]

Example 7 A chelate-type porous ion adsorbent was prepared in the same manner as in Example 5 except that the chelate-type ion adsorbent resin synthesized in Example 4 was used instead of the cation-type ion adsorbent resin synthesized in Example 1. Obtained. The TOC elution of this chelate-type porous ion adsorbent was evaluated in the same manner as in Example 5. As a result, ΔT after washing with hot ultrapure water at 80 ° C. for 48 hours was evaluated.
OC was 1 ppb or less. The ion exchange capacity of the obtained porous ion adsorbent was 0.36 meq / g.

[0032]

Example 8 As shown in FIG. 2, the filters of Examples 5 and 7 were installed in the ultrapure water line, and at the same time, a pencil type hollow fiber cation membrane module was installed to measure the water quality before and after the filter. Metal ions in ultrapure water were captured and concentrated. Water was passed through the filters of Examples 5 and 7 at 20 L / min, and at 50 mL / min through the pencil-type hollow fiber cation membrane module for 50 days. After that, the pencil-type hollow fiber cation membrane module was removed and eluted with 1N nitric acid to remove Zn and Na ions in the eluent from ICP manufactured by Yokogawa Analytical Systems.
-Z before and after the filter of Examples 5 and 7 quantified by MS
The n-ion concentration and Na-ion concentration were determined. The results are shown in Table 1.
Shown in.

[0033]

[Table 1]

It was clearly observed that the concentration of Zn in ultrapure water was reduced in the cation type porous ion adsorbent and the chelate type porous ion adsorbent. In the cation adsorbent, a decrease in Na concentration was also seen.

[0035]

[Example 9] The cation-type ion-adsorbing resin synthesized in Example 1 was immersed in a 1N-NaOH aqueous solution and filtered to obtain Na-type. The Na-type cation adsorption resin dried in a vacuum dryer and polyethylene powder (“Sunfine UH901” sieved with a 200-mesh wire mesh) were mixed at a mass ratio of 50/50. Outer diameter / inner diameter =
80mmφ / 70mmφ aluminum extruded tube inside diameter /
An aluminum extruded tube having an inner diameter of 60 mmφ / 50 mmφ was installed concentrically, and the mold was used, and the powder mixture was put in the gap (the vibration was slightly vibrated to close the packing) in a hot air dryer at 180 ° C. It was held for minutes and sintered. A plate made of polyethylene and a filtered water port were fused to the upper and lower sides of the obtained cylindrical porous ion adsorbent to obtain a cartridge type filter as shown in FIG. This filter is a commercially available PF
After being placed in a cartridge filter housing made of A and regenerated by passing 1 N nitric acid, TOC elution was evaluated by the same method as in Example 2. ΔTOC after washing with hot ultrapure water at 80 ° C. for 48 hours was 1 ppb. It was below. The ion exchange capacity of the porous ion adsorbent is 0.93 meq /
It was g.

[0036]

Example 10 The anion-type ion-adsorbing resin synthesized in Example 3 was immersed in a 1N aqueous hydrochloric acid solution, filtered, washed with water, and washed with Cl.
Type The Cl-type anion adsorption resin was dried with a vacuum dryer, and an anion-type porous ion adsorption material was obtained in the same manner as in Example 9. T of the anion type porous ion adsorbent
When OC elution was evaluated in the same manner as in Example 9, it was 8
ΔTOC after washing with 0 ° C. hot ultrapure water for 48 hours was 1 ppb or less. The ion exchange capacity of the porous ion adsorbent was 0.65 meq / g.

[0037]

The ion-adsorbing resin according to the present invention can reduce metal ions in ultrapure water to an extremely low concentration. Further, the porous ion adsorbent obtained by sintering this can be freely processed into a sheet shape, a block shape, a pipe shape, a columnar shape, etc., and a high water permeation rate can be obtained, and fine particles, colloidal substances and metal ions can be eliminated. Can be adsorbed and removed to the level of 1 ppt digit.

[Brief description of drawings]

FIG. 1 is a schematic view of a cartridge type filter using a porous ion adsorbent.

FIG. 2 is a flow chart for measuring the ion adsorption capacity of a porous ion adsorbent filter.

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Claims (5)

[Claims] 1. An ion adsorption resin having functional groups having an ion exchange function introduced on the surface of polymer resin particles having a particle diameter of 300 μm or less, and having an ion exchange capacity of 0.3 to 10.
An ion-adsorbing resin, which is meq / g. 2. The ion adsorption resin according to claim 1, wherein the functional group having an ion exchange function is any of a cation exchange group, an anion exchange group and a chelate exchange group. 3. The ion according to claim 1, wherein a functional group having an ion exchange function is introduced into the polymer resin particles having a particle diameter of 300 μm or less by utilizing radiation graft polymerization. Method for producing adsorbent resin. 4. A porous resin matrix in which thermoplastic resin particles having a particle diameter of 300 μm or less and an aggregate of the ion adsorption resin according to claim 1 or 2 are integrated, and the ion adsorption resin is contained in the total mass of the matrix. A porous ion adsorbent characterized by containing 10 to 70 wt% thereof. 5. An average pore diameter of the porous ion adsorbent is 1 to 1.
The porous ion adsorbent according to claim 4, which has a porosity of 00 μm and a porosity of 20 to 60%.