KR20200070487A - Method for preparing a boron selective adsorption resin for use in the production of ultra pure water - Google Patents

Abstract

The present invention relates to a method for producing a boron selective adsorption resin used in the production of ultrapure water. More particularly, the present invention relates to a method for producing a boron selective adsorption resin, wherein the boron selective adsorption resin is washed with alcohol and treated with alkali metal hydroxide, so that total organic carbon (TOC) elution is low, and a resistivity value of ultrapure water and boron removal efficiency can be improved.

Description

Method for preparing a boron selective adsorption resin for use in the production of ultra pure water}

The present invention relates to a method for producing a boron-selective adsorption resin used in the production of ultrapure water, and more specifically, after washing the boron-selective adsorption resin with alcohol and treating it with an alkali metal hydroxide, elution of total organic carbon (TOC) It relates to a method for producing a boron-selective adsorption resin which can improve the specific resistance value of ultra-pure water and boron removal efficiency.

In the field of semiconductor manufacturing, along with the high integration of semiconductor devices, high purity has been required for the purity of the product along with production machinery, gas, and chemicals used in the manufacturing process, and ultrapure water (sometimes referred to as ultra pure water) is used. Very high purity water is required. The demand for high purity of this water is expected to increase further in the future, and in this process, very small amounts of impurities such as particulates and colloidal substances, which have not been noticed so far, are attracting attention as new target materials for removal, and boron is one of those materials. Can be mentioned.

Boron is an element that is difficult to measure in a very small amount, and it is not clear whether boron is contained in ultrapure water manufactured using various devices for removing ionic or nonionic substances, and thus has not been noted as an evaluation item of water quality in ultrapure water. However, as the measurement technology has been developed, it has recently been possible to detect the presence of impurities at the ppt level. As a result, it has become clear that boron is contained in the manufactured ultrapure water depending on the structure of the manufacturing apparatus such as water quality or ultrapure water.

In addition, when such boron is used while being contained in a significant amount in ultrapure water, for example, considering the case where it is used over a long period of time as a washing water in a semiconductor device manufacturing process, boron adheres at a high concentration to the wafer surface, resulting in the semiconductor device A problem has arisen that the fear of impairing characteristics cannot be ignored.

For this reason, as it is recognized that removing boron from ultrapure water is very important, a method of removing boron using a reverse osmosis membrane or a method of removing boron using a boron selective adsorption resin has been studied. The boric acid ion selectively combines polyhydric alcohol, sugars, cellulose, and the like having a plurality of hydroxyl groups to form a boric acid complex. There is a quantitative method of boron using a complex formation reaction with boric acid ions using mannitol, a kind of saccharide, and it is also known that a polysaccharide polymer based on dextran gel adsorbs boron. As a boron-selective adsorption resin incorporating polyhydric alcohols, for example, copolymers of styrene and divinyl benzene combined with a glucamine structure are commercially available. When ultrapure water is treated using such a boron selective adsorption resin, organic carbon elutes from the boron selective adsorption resin. Ultrapure water used for cleaning semiconductor substrates for semiconductors requires a boron concentration of 10 ng/liter (ppt) or less and a specific resistance of 18 MΩ·cm or higher. By combining the boron-selective adsorption resin for removal of trace boron to the primary pure water device or subsystem, the boron concentration can be reduced, but the organic carbon is eluted by 1 μg/liter (ppb) or more, and the eluted organic carbon is not removed from the subsystem. Since it does not, there is a problem that the resistivity of the ultrapure water at the end decreases. Japanese Patent Laid-Open Publication No. Hei 8-238478 discloses a method of reducing TOC elution from boron-selective ion-exchange resins used in combination with ultrapure water production equipment, adjusting the boron-selective adsorption resins to the free base type, and the strong basic exchanger to the salt type. A method of coordination and use is disclosed. However, in this method, since the boron-selective adsorption resin is contacted with an aqueous sodium hydroxide solution and then contacted with an aqueous sodium hydrogencarbonate solution, the adjustment of the boron-selective adsorption resin is carried out in two stages, resulting in complicated processing and a large amount of waste solution. There is a losing problem.

In Japanese Patent Laid-Open Publication No. Hei 13-17866, as a method of reducing TOC elution amount from boron-selective ion exchange resin, a boron-selective adsorption resin is used as a column method to pass low-concentration alkali metal hydroxide aqueous solution and ultrapure water downwardly at high temperature. Methods are disclosed. However, in this method, the effect of reducing the TOC elution amount of the boron-selective ion-exchange resin is not high, a problem of a decrease in specific resistance occurs, and there is a problem in stability because the method proceeds by a column method at high temperature.

For this reason, there has been a demand for a manufacturing method that reduces total organic carbon (TOC) elution from the boron selective adsorption resin by a simpler treatment, has a high specific resistance, and has a high boron removal efficiency.

An object of the present invention, after washing the boron-selective adsorption resin with alcohol, treatment with an alkali metal hydroxide, the total organic carbon (TOC) elution is small, the specific resistance of ultrapure water and boron selective adsorption that can improve the removal efficiency of boron It is to provide a method for producing a resin.

The present invention to solve the above technical problem, (1) providing a boron selective adsorption resin; (2) washing the provided boron selective adsorption resin with alcohol; And (3) treating the boron-selective adsorption resin washed with alcohol with an alkali metal hydroxide; provides a method for producing a boron-selective adsorption resin comprising a.

According to another aspect of the present invention, ultrapure water prepared using a boron selective adsorption resin prepared according to the method of the present invention is provided.

Boron selective adsorption resin prepared according to the method of the present invention has a low total organic carbon (TOC) elution, excellent resistivity and boron removal efficiency of ultrapure water produced using the same, and boron selective adsorption resin prepared by a general method. Compared, it shows an excellent effect.

Hereinafter, the present invention will be described in more detail.

The method for producing a boron selective adsorption resin of the present invention comprises the steps of (1) providing a boron selective adsorption resin; (2) washing the provided boron selective adsorption resin with alcohol; And (3) treating the boron selective adsorption resin washed with alcohol with an alkali metal hydroxide.

The boron-selective adsorption resin prepared by the method of the present invention has ultra-pure water having a total organic carbon (TOC) elution of 1 μg/liter (ppb) or less, a specific resistance of 18 MΩ·cm or more, and a boron concentration of 10 ng/liter (ppt) or less. Can be stably manufactured, and the ultrapure water can be used as ultrapure water for semiconductor manufacturing.

The method for producing a boron selective adsorption resin of the present invention includes (1) providing a boron selective adsorption resin. The boron selective adsorption resin provided in the present invention is not particularly limited, but may be provided by a method including the following steps:

(a) glycidyl methacrylate; Dissolving a trifunctional or higher polyfunctional vinyl monomer and a polymerization initiator in an organic solvent to prepare a mixture;

(b) dispersing the prepared mixture in water to prepare porous polymer particles by suspension polymerization; And

(c) reacting the prepared porous polymer particles with a compound having at least one amino group and two or more hydroxyl groups in the molecule to introduce a chelating group into the polymer particles.

In step (a), the mixture is, for example, 60 to 95 parts by mass of glycidyl methacrylate, 5 to 40 parts by mass of polyfunctional vinyl monomer having at least 3 functionalities (however, at least 3 functionalities with glycidyl methacrylate) The total amount of the polyfunctional vinyl monomer is 100 parts by mass), and may include 0.05 to 5 parts by mass of the polymerization initiator.

The trifunctional or higher polyfunctional vinyl monomer may have three or more (meth)acryloyl groups or three or more allyl groups in one molecule, and three or more (meth) acryloyl groups in one molecule, eg For example, trimethyrolpropane tri(meth)acrylate, tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethyrolpropane EO addition tri( Meta)acrylate, glycerin PO addition tri(meth)acrylate, tris(meth)acryloyloxyethyl phosphate, urethane(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth) )Acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, and the like. Among these, dipentaerythritol hexa(meth)acrylate and tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate are preferable for the obtained particle strength.

Further, as having three or more allyl groups in one molecule, for example, triallyl cyanurate, triallyl isocyanurate, and the like can be used, and these may be used alone or in mixtures of two or more.

As the polymerization initiator, peroxide-based, azobis-based, or the like can be used. Examples of the peroxide system include benzoyl peroxide, lauroyl peroxide, octanoyl peroxide, orthochlorobenzoyl peroxide, orthomethoxy benzoyl peroxide, methyl ethyl ketone peroxide, diisopropyl peroxy dicarbonate, cumene hydroperoxide, and cyclo And hexanone peroxide, t-butyl hydroperoxide, and diisopropylbenzene hydroperoxide. As the azobis type, 2,2'-azobis isobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (2,3,3-trimethyl butyronitrile), 2,2'-azobis (2-isopropyl butyronitrile), 1,1'-azobis (cyclohexane-1- Carbonitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2-(carbamoyl azo)isobutyronitrile, dimethyl-2,2'-azobis iso And butylate. These polymerization initiators may be used alone or in combination of two or more.

The organic solvent is used as a porous agent, and as a good solvent for the glycidyl methacrylate and a polyfunctional vinyl monomer having three or more functionalities, it can be used without particular limitation when it is a poor solvent for the resulting porous polymer particles. Specifically, for example, aliphatic hydrocarbon-based organic solvents such as n-hexane, n-heptane, n-octane and isomers thereof; non-aqueous alcohol-based solvents such as n-butanol, n-hexanol, 2-ethyl hexanol, n-octanol and isomers thereof; Ester organic solvents such as ethyl acetate and butyl acetate; And aromatic hydrocarbon-based organic solvents such as benzene, toluene, and xylene. These organic solvents may be used alone or in combination of two or more.

In step (b), the mixture prepared in step (a) can be dispersed in water to prepare porous polymer particles by suspension polymerization.

Suspension polymerization is an aqueous suspension polymerization method and can be carried out by a known method. For example, first, water and a dispersion stabilizer are added to the reaction tank and stirred to disperse or dissolve the dispersion stabilizer in water. Subsequently, a solution containing a glycidyl methacrylate, a polyfunctional vinyl monomer having a trifunctional or higher functionality, and an organic solvent and a polymerization initiator are added and dispersed to a desired particle diameter, then heated to a reaction temperature and polymerization is started. At this time, the reaction temperature may be 40 ~ 80 ℃. After the polymerization reaction is completed, the organic solvent is removed by distillation under reduced pressure, the reaction product is taken out, the produced polymer particles are separated by filtration, the dispersion stabilizer is removed by washing the polymer particles, and dried to obtain porous polymer particles. have.

In step (c), a chelate-forming group may be introduced into the polymer particle by reacting the porous polymer particle prepared in step (b) with a compound having at least one amino group and two or more hydroxyl groups in the molecule.

As a compound having one amino group and two or more hydroxyl groups used in the present invention, N-methyl-D-glucamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2-amino-2 -Methyl-1,3-propanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, 3-diethyl amino- 1,2-propanediol; and the like. Among them, N-methyl-D-glucamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol is particularly preferable from the viewpoint of having a high boron adsorption function.

The method for producing a boron selective adsorption resin of the present invention includes (2) washing the provided boron selective adsorption resin with alcohol. The boron selective adsorption resin may be provided by the above-described method.

The alcohol used in step (2) may be an alcohol represented by the formula R1-OH (R1 is an aliphatic alkyl group having 1 to 8 carbon atoms), specifically methanol, ethanol, propanol, butanol, pentanol, hexanol, heptane It may be any one selected from the group consisting of all, octanol, or a combination thereof.

The alcohol used in step (2) is 50 to 100°C or more, for example, by using an alcohol aqueous solution having an alcohol content of 50 to 100% by weight, for example, 60 to 90% by weight, or 70 to 85% by weight, for example, The boron selective adsorption resin may be washed at a temperature of 55°C or higher, 60°C or higher, or 70°C or higher. When the content of alcohol is less than 50% by weight, total organic carbon (TOC) elution of the boron selective adsorption resin may not be reduced.

The lower limit of the alcohol content of the aqueous alcohol solution may be, for example, 50% or more, 55% or more, 60% or more, 65% or more, 70% or more, or 75% or more, and the upper limit is 100% by weight. Hereinafter, it may be 95% by weight or less, 90% by weight or less, or 85% by weight or less.

In step (2), there is no particular limitation on the method of washing the boron-selective adsorption resin with alcohol, that is, the method of heating by contacting the boron-selective adsorption resin with an aqueous alcohol solution, but both the batch method and the column method can be used. It is preferable that the adsorbent resin is heated by contacting the boron-selective adsorbent resin with alcohols in a batch mode.

The method for producing a boron selective adsorption resin of the present invention includes (3) treating the boron selective adsorption resin washed with alcohol with an alkali metal hydroxide.

The alkali metal hydroxide used in step (3) may be used selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, or a combination thereof, preferably using an aqueous sodium hydroxide solution Can be.

In step (3), the alkali metal hydroxide to be used may be an alkali metal hydroxide aqueous solution having an alkali metal hydroxide content of 1 to 10% by weight, for example, 2 to 8% by weight or 3 to 7% by weight, and 60°C. The reaction may be performed at the above temperature, for example, 70°C or higher, 80°C or higher, or 90°C or higher. When the content of the alkali metal hydroxide in the aqueous alkali metal hydroxide solution is less than 1% by weight, the specific resistance value of ultrapure water produced from the boron-selective adsorption resin to be produced may be lowered or the boron removal efficiency may be poor, and if the content exceeds 10% by weight, further improvement It is difficult to obtain an effect.

The lower limit of the content of the alkali metal hydroxide in the aqueous alkali metal hydroxide solution may be, for example, 1 wt% or more, 2 wt% or more, 3 wt% or more, 4 wt% or more, or 5 wt% or more, and the upper limit is 10 wt% % Or less, 9% or less, 8% or less, or 7% or less.

Washing using a boron-selective adsorption resin prepared according to the method of the present invention washes ultrapure water having a water quality of less than or equal to 1ppb of total organic carbon (TOC) and a resistivity of 18.20 MΩ·cm or more for 5 to 15 hours with SV=20h ^-1 Can be.

In the step (3), the method for treating the boron-selective adsorption resin with an alkali metal hydroxide, that is, the method for heating the boron-selective adsorption resin in contact with an aqueous alkali metal hydroxide solution is not particularly limited, but both the batch method and the column method can be used. , Preferably, the boron selective adsorption resin can be heated by contacting the boron selective adsorption resin with a metal hydroxide aqueous solution in a batch manner.

According to the method of the present invention, the resin is adjusted by a simple operation of washing the provided boron-selective adsorption resin with alcohol and treating the boron-selective adsorption resin washed with alcohol with an alkali metal hydroxide, so that total organic carbon (TOC) elution is achieved. It is possible to produce ultrapure water of good water quality, which has a low specific resistance value and a high boron removal efficiency, and the ultrapure water can be suitably used in a semiconductor manufacturing process or the like.

Accordingly, according to another aspect of the present invention, ultrapure water prepared using a boron selective adsorption resin prepared according to the method of the present invention is provided.

When ultrapure water is treated using a boron-selective adsorption resin prepared by the treatment of the above step, the elution amount of organic carbon in the treated water can be maintained at 1 μg/liter (ppb) or less, and resistivity of 18 MΩ·cm or more, and also treated The boron concentration in the water may also be 10 ng/liter (ppt) or less.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[ Example ]

Example One

Preparation of boron selective adsorption resin: step (1)

90% by weight of glycidyl methacrylate, 10% by weight of dipentaerythritol hexaacrylate as a polyfunctional vinyl monomer having a tri- or higher functionality, 1% by weight of BPO as a polymerization initiator, and 40% by weight of iso-octane as an organic solvent [ A mixture was prepared by mixing mass ratio: glycidyl methacrylate/dipentaerythritol hexa acrylate (trifunctional or higher polyfunctional vinyl monomer) = 90:10]. This mixture was added under stirring in water containing 0.2% by weight of polyvinyl alcohol as a dispersing agent, dispersed to form a suspension, and subjected to suspension polymerization at 70°C for 15 hours. Stirring was performed at 135 rpm using a stirrer with an anchor blade.

After the reaction was completed, the resin suspension was distilled under reduced pressure to remove isooctane, followed by filtration and washing with water to remove the dispersant, and after washing, dried at 40°C to obtain porous polymer particles. The obtained polymer particles had an average particle diameter of 350 μm.

100 ml of each of the porous polymers was added to a flask, and 150 g of N-methyl-D-glucamine and 1,500 g of N,N-dimethylformamide were added and stirred slowly and maintained at 60°C for 8 hours. After the reaction was completed, the obtained particles were washed with water to remove N-methyl-D-glucamine, etc., and dried at 40°C after washing to obtain ion-exchange resin particles having an exchange capacity of 0.7 meq/ml.

Primary TOC Alcohol washing step for removal: step (2)

100 ml of the boron selective adsorption resin prepared in Example 1 was added to a 1 L reactor, and then an 80% by weight aqueous solution of methanol was added, and the temperature was raised to 70°C. After maintaining the temperature for 3 hours, it was cooled to room temperature. After draining the methanol filtrate (drain), 300ml of ultrapure water was added to the reactor and stirred for 1 hour. After removing the remaining methanol filtrate, 300 ml was added to the reactor and stirred for 1 hour.

Secondary TOC Remove and Specific resistance value Treatment with alkali metal hydrate for improvement: step (3)

In the 1L reactor, 100 ml of the boron-selective adsorption resin removed from the primary TOC in Example 1 was added, and then, an aqueous sodium hydroxide solution having a concentration of 4 wt% was added, and the temperature was raised to 100°C. After maintaining the temperature for 3 hours, it was cooled to room temperature. Thereafter, the sodium hydroxide filtrate was removed, and 300 ml of ultrapure water was added to the reactor and stirred for 1 hour. After removing the remaining sodium hydroxide filtrate, 300 ml was added to the reactor and stirred for 1 hour.

Ultrapure water cleaning method

After filling the column (L 500mm XD 20mm) with 100ml of boron-selective adsorption resin with primary and secondary TOC removed, the ultrapure water with a total organic carbon (TOC) of 1ppb or less and a resistivity of 18.20 MΩ·cm or more is downstream, SV=20h ^-1 Was passed through for 10 hours.

Resistivity and Total organic carbon ( TOC ) Assessment Methods

Organic carbon concentration was measured using a TOC analyzer (Anatel), and boron concentration was measured using a Sievers Boron Analyzer. Ultra-pure water of 0.5 to 1 ppb of total organic carbon (TOC) was downwardly flowed to the column (L 500 mm XD 20 mm) for 1 hour at SV=75 h ^-1 , and the resistivity and total organic carbon ( TOC) of the treated water flowing out of the column ) Was measured.

Boron adsorption evaluation method

After the column (L 500mmXD 20mm) was filled with 100 ml of boron-selective adsorption resin with primary and secondary TOC removed, 500 ppm of boron concentration was passed through the column at SV = 75 hr ^-1 . At this time, the boron concentration of the effluent from the column was measured in real time using a boron measurement equipment (Sievers Boron Analyzer, detection limit 15 ppt).

Example 2

In the step of treatment with alkali metal hydrate for removing the secondary TOC and improving the specific resistance value, the same procedure as in Example 1 was performed except that 2% by weight of sodium hydroxide was used. Then, the specific resistance and total organic carbon (organic) and boron adsorption evaluation were checked in the same manner as in Example 1.

Example 3

In the step of treatment with alkali metal hydrate for removing the secondary TOC and improving the specific resistance value, the procedure was carried out in the same manner as in Example 1, except that 6% by weight of sodium hydroxide was used. Then, the specific resistance and total organic carbon (organic) and boron adsorption evaluation were checked in the same manner as in Example 1.

Example 4

In the step of treatment with alkali metal hydrate for the removal of the secondary TOC and improvement of the specific resistance value, the procedure was carried out in the same manner as in Example 1, except that 8% by weight of sodium hydroxide was used. Then, the specific resistance and total organic carbon (organic) and boron adsorption evaluation were checked in the same manner as in Example 1.

Comparative example One

Except that the alcohol washing step for removing the primary TOC was not used, except that the step (2) was not performed, the same procedure as in Example 1 was performed. Then, the specific resistance and total organic carbon (organic) and boron adsorption evaluation were checked in the same manner as in Example 1.

Comparative example 2

The procedure was performed in the same manner as in Example 1, except that the sodium hydroxide contact method for removing the second TOC and improving the specific resistance value was not used (except that step (3) was not performed). Then, the specific resistance and total organic carbon (organic) and boron adsorption evaluation were checked in the same manner as in Example 1.

Comparative example 3

The method of batch treatment is performed without using the sodium hydroxide contact method for removing the secondary TOC and improving the specific resistance value (without performing step (3) above), and treating it with an alkali metal hydrate for removing the secondary TOC and improving the specific resistance value. The resistivity, total organic carbon (organic), and boron adsorption evaluations were checked in the same manner as in Example 1, except that the following procedure was performed as a non-column method.

1) Ultra-pure water at room temperature flowed upwards, LV=10 m hr ^-1 for 30 minutes, backwashing, 2) stabilized for 5 minutes, and then 3) ultra-pure water at 80°C downstream, SV=5 hr ^-1 for 30 minutes After passing through and raising the temperature of the resin, 4) a 2 wt% aqueous sodium hydroxide solution at 80°C was passed through a downflow and SV = 5 hr ^-1 for 120 minutes to adjust the boron selective adsorption resin. Subsequently, 5) ultrapure water at 80°C was passed through 60 minutes downflow with SV=5 hr ^-1 , and 6) ultrapure water at 80°C was flowed downward and washed with SV=5 hr ^-1 for 240 minutes. Subsequently, 7) the ultrapure water at room temperature was passed down-flow and SV=10 hr- for 60 minutes to cool the boron selective adsorption resin.

As shown in Table 1, in the case of Examples 1 to 4 according to the present invention, Example 1 is alcohol washed for removing the primary TOC through the boron selective adsorption resin manufacturing method of the present invention, and the secondary TOC is removed and In order to improve the specific resistance value, a final ultrapure water washing method was performed by treating with alkali metal hydrate, and as a result, the specific resistance and TOC were 18.20 18.cm or more and 1.0 ppb or less respectively within 1 hour, and the boron adsorption evaluation was also 15 ppt within 1 hour. Or less.

In the case of Examples 2, 3 and 4, the specific resistance is 18.15 to 18.20 ㏁.cm or more as the concentration of sodium hydroxide changes to 2 to 8% by weight in the treatment with alkali metal hydrate for the removal of secondary TOC and improvement of the specific resistance value. It was found that it exhibited high specific resistance.

On the other hand, in the case of Comparative Example 1, the primary TOC is not alcohol-cleaned for removal, and the TOC shows a 30 ppb elution within 1 hour, so the effect of removing TOC is low, and the adsorption capacity of boron is 20 ppt. Compared to the poor. In the case of Comparative Example 2, the second TOC removal and the treatment with alkali metal hydrate for improving the specific resistance value were not performed, and the TOC showed an elution of 20 ppb within 1 hour, so the TOC removal effect was low, and the specific resistance was also 17.00㏁.㎝ As a result, it showed a low value, and it was found that the boron removal ability was low at 50 ppt in the adsorption capacity of boron. In the case of Comparative Example 3, without performing the alcohol washing step for removing the primary TOC, the secondary TOC removal and alkali metal hydrate treatment for improving the specific resistance value were carried out by a column method instead of a batch method, and the TOC was 1 hour. Within 15ppb elution, the TOC removal effect was low, and it was found that the boron removal ability was low at 30 ppt in the adsorption capacity of boron.

Therefore, as can be seen from Examples 1 to 4 according to the present invention, the boron-selective adsorption resin prepared according to the method of the present invention has less total organic carbon (TOC) elution, and the resistivity of ultrapure water produced using the same And it was found that the boron removal efficiency is excellent, it shows a significantly superior effect compared to the boron selective adsorption resin prepared by a general method.

Claims (9)

(1) providing a boron selective adsorption resin;
(2) washing the provided boron selective adsorption resin with alcohol; And
(3) treating the boron selective adsorption resin washed with alcohol with an alkali metal hydroxide;
Method for producing a boron-selective adsorption resin comprising a. The method of claim 1, wherein the alcohol is any one selected from the group consisting of methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, or combinations thereof. The method according to claim 1, wherein the boron selective adsorption resin is washed at a temperature of 50° C. or higher by using an aqueous alcohol solution having an alcohol content of 50 to 100% by weight in step (2). The method of claim 1, wherein the alkali metal hydroxide is any one aqueous solution selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, or a combination thereof. According to claim 1, Step (3) is a method for producing a boron-selective adsorption resin, which is treated at a temperature of 60° C. or higher using an alkali metal hydroxide aqueous solution having an alkali metal hydroxide content of 1 to 10% by weight. The method of claim 1, wherein the step (1) provides a boron selective adsorption resin by a method comprising the following steps:
(a) glycidyl methacrylate; Preparing a mixture by dissolving a trifunctional or higher polyfunctional vinyl monomer and a polymerization initiator in an organic solvent;
(b) dispersing the prepared mixture in water to prepare porous polymer particles by suspension polymerization; And
(c) reacting the prepared porous polymer particle with a compound having at least one amino group and two or more hydroxyl groups in the molecule to introduce a chelating group into the polymer particle. The compound according to claim 6, wherein the compound having one amino group and two or more hydroxyl groups is N-methyl-D-glucamine, 2-amino-2-(hydroxymethyl)-1,3-propanediol, 2- Amino-2-methyl-1,3-propanediol, 2-amino-1,3-propanediol, 3-amino-1,2-propanediol, 3-dimethylamino-1,2-propanediol, 3-di A method for producing a boron selective adsorption resin, which is selected from the group consisting of ethyl amino-1,2-propanediol or a combination thereof. Ultrapure water prepared using a boron selective adsorption resin prepared according to the method of claim 1. The ultrapure water according to claim 8, wherein the total organic carbon (TOC) is 1 μg/liter (ppb) or less, the specific resistance is 18 MΩ·cm or more, and the boron concentration is 10 ng/liter (ppt) or less.