JP3248205B2 - Ion exchange resin for ultrapure water production, method for producing the same, and method for producing ultrapure water using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to relates to ultrapure water production for using ion-exchange <br/> resins, pure water production process. In particular, the present invention is suitable very high purity deionized water, preparation of ultrapure water using a so-called ultrapure water production for ion-exchange resins for use in the washing water and electronic industry for use in ultra-LSI manufacturing process It is about.

[0002]

2. Description of the Related Art There are many known methods for producing pure water.
In a typical example, raw water is subjected to coagulation filtration to remove suspended matter, and then treated with an ion exchange resin to obtain deionized water in which most of the ionic substances present are removed. Deionized water is then irradiated with ultraviolet light to oxidatively decompose organic matter,
Steps of removing dissolved gases under reduced pressure, steps of removing ionic substances dissolved in a mixed bed of a strongly acidic cation exchange resin and a strongly basic anion exchange resin, steps of removing dissolved substances with a reverse osmosis membrane, etc. And purified water. The quality of the pure water obtained in this way is a good one having a specific resistance of 18 MΩ · cm.
As described above, the total organic carbon content has reached 10 ppb or less.

When this pure water is further purified, it becomes ultrapure water.
In a typical example, pure water is irradiated with short-wavelength ultraviolet rays to decompose organic substances contained therein into carbonic acid or carboxylic acid. Then, the pure water that has been subjected to the irradiation treatment is treated with a strongly basic anion exchange resin, and further treated with a mixed bed of a strongly acidic cation exchange resin and a strongly basic anion exchange resin. Is removed. Finally, the suspension is treated with an ultrafiltration membrane to remove a very small amount of a suspended substance such as a colloidal substance to obtain ultrapure water.

[0004]

In the production of high-purity pure water or ultrapure water having a total organic carbon content of 10 ppb or less, impurities mixed into the water from the material constituting the apparatus are required. It has a great effect on the quality of pure or ultrapure water that is finally obtained. In particular, the ion exchange resin is a particle having a small particle size, and the ion exchange resin bed has an extremely large resin surface area in comparison with its volume. Has a non-negligible effect on ultrapure water. That is, when water is passed through the ion-exchange resin bed, impurities in the water are adsorbed and removed by the ion-exchange resin, and at the same time, a small amount of impurities are eluted from the ion-exchange resin. It does not rise above that. As one of the measures to reduce the elution from the ion exchange resin, it has been carried out to remove the eluate in the resin by passing water through the ion exchange resin tower for a long time before use. Means that part of the product water is consumed in the manufacturing process, which reduces the efficiency of the process. Therefore, an ion exchange resin with less elution of impurities when passing water is desired.

In general, quaternary ammonium type anion exchange resins are more difficult to reduce elution by passing water than sulfonic acid type cation exchange resins. Resins are particularly desired. The present inventors have studied the ion-exchange resin based on a copolymer of a monovinyl aromatic compound and a polyvinyl compound as a base, and eluted when the ion-exchange resin was used as a regenerative type and shaken in warm water at 50 ° C. As a result, the eluate having a molecular weight of less than 3000 is easily adsorbed to an ion exchange resin having an opposite sign, that is, if it is eluted from a basic anion exchange resin, is easily adsorbed to a sulfonic acid type cation exchange resin. It was found that those having 3,000 or more were hardly adsorbed to the ion exchange resin having the opposite sign, and that this phenomenon was particularly remarkable in the eluate from the basic anion exchange resin. Therefore, when water is passed through a mixed-bed ion exchange column composed of a cation exchange resin and an anion exchange resin having substantially no eluate having a molecular weight of 3000 or more, ultrapure water with very little eluate can be obtained. In the production of ultrapure water, it is general that water is finally passed through a cartridge-type mixed-bed ion exchange tower, so this finding is that ion exchange resins for ultrapure water production, especially basic anion exchange resins, Even without thorough washing until the eluate disappears, the molecular weight is 3000
This means that washing may be performed until the above-mentioned eluate is substantially eliminated. Further, the washing may be performed by a washing method such that an elute having a molecular weight of 3000 or more is efficiently removed.

[0006]

The present invention SUMMARY OF] has been achieved based on these findings, it is an object of the present invention a method of producing ultra pure water had use of ion exchange resin for ultrapure water production.

An object of the present invention is to provide a method for producing pure water or ultrapure water which is less contaminated by leaching from the ion exchange resin used. Another object of the present invention is to provide a method for producing pure water or ultrapure water having a remarkably low total organic carbon content. Still another object of the present invention is to provide a method for producing pure water or ultrapure water using a mixed bed having extremely low contamination of water by the eluate from the ion exchange resin.

According to the present invention, there is provided a strongly basic anion exchange resin based on a copolymer of a monovinyl aromatic compound and a polyvinyl compound, which may contain a monovinyl aliphatic compound, and comprising a hot water at 50 ° C. When immersed in water for 7 days, organic compounds having a molecular weight of less than 3000 elute, but organic compounds having a molecular weight of 3000 or more do not substantially elute, and water is passed through a mixed bed with a strongly acidic cation exchange resin. By removing a small amount of ionic impurities dissolved in water by adsorption, pure water or ultrapure water of extremely high purity can be obtained.

Preferably, both the strongly basic anion exchange resin and the strongly acidic cation exchange resin constituting the mixed bed are copolymers of a monovinyl aromatic compound and a polyvinyl compound which may contain a monovinyl aliphatic compound. The organic compound having a molecular weight of less than 3000 elutes when immersed in warm water at 50 ° C. for 7 days, but the organic compound having a molecular weight of 3000 or more is not substantially eluted. More preferably, a strongly basic anion exchange resin or a strongly basic anion exchange resin and a strongly acidic cation exchange resin constituting the mixed bed, in which an organic compound having a molecular weight of 2,000 or more does not substantially elute, is used. .

The ion-exchange resin for producing ultrapure water used in the present invention is an ion-exchange resin having a copolymer of a monovinyl aromatic compound and a polyvinyl compound as a base material.
Organic compounds having a molecular weight of less than 3000 elute when immersed in warm water at a temperature of ℃, but organic compounds having a molecular weight of 3000 or more are not substantially eluted. Here, it is more preferable that the organic compound having a molecular weight of 2,000 or more does not substantially elute.

[0011] The ion exchange resin for producing ultrapure water used in the present invention may contain an eluate having a molecular weight of less than 3000. However, even if such an eluate is used in a large amount, the water quality deteriorates. The amount is preferably 300 ppm or less as organic carbon as measured by a method for measuring an eluted material described below. Considering the washing efficiency when removing the eluted material, the eluted material is 300 ppm or less as organic carbon, particularly 1 ppm.
It is preferably in the range of 00 ppm or less. The eluate preferably has a medium molecular weight, and 90% of the eluate
The molecular weight is preferably less than 2,000, particularly preferably in the range of 100 to 1,000.

The ion exchange resin for producing ultrapure water used in the present invention is obtained by copolymerizing a monovinyl aromatic compound and a polyvinyl compound according to a known method, introducing an ion exchange group into the copolymer, and finally swelling more than water and water. After washing with a strong organic solvent, the molecular weight is 3000 or more, preferably 20
It can be produced by removing substantially all of the eluate of 00 or more.

Examples of the monovinyl aromatic compound include monovinyl aromatic compounds which may have, as a substituent, 1 to 3 alkyl groups or halogen atoms in an aromatic ring, and generally, styrene, α-methylstyrene, Other aromatic compounds such as ethylstyrene, chlorostyrene, vinyltoluene, vinylxylene and vinylnaphthalene can be used, but styrene is preferred. Also,
If desired, these may be used in combination with a small amount of a monovinyl aliphatic compound.

The polyvinyl compound is selected from di- or trivinyl aromatic compounds or di- or trivinyl aliphatic compounds, and is preferably divinylbenzene, trivinylbenzene, divinyltoluene, divinylxylene, divinylnaphthalene, ethylene glycol di (meth ) Acrylate, divinyl ketone, divinyl sulfone, diallyl phthalate, diallyl fumarate, diallyl adipate and the like are used. Particularly preferred is divinylbenzene.

The polyvinyl compound may be a small amount of 2% (by weight) of the whole vinyl compound, but is usually 4% or more.
Preferably, it is used so as to be at least 6%. As is well known, as the ratio of the polyvinyl compound increases, the formed ion exchange resin hardly swells in water, and thus it becomes difficult to remove the eluted material by washing. Further, since the polyvinyl compound constitutes a hydrophobic part in the ion exchange resin to be produced, if the amount of the ion exchange group, which is a hydrophilic part, is constant, the larger the amount of the polyvinyl compound is, the more the organic solvent is generally used rather than water. Swells easily.

The production of a copolymer from a monovinyl aromatic compound and a polyvinyl compound is generally carried out by a suspension polymerization method, and is carried out in an aqueous medium or in a solvent in which the mono and polyvinyl compounds are dissolved but the copolymer is not dissolved. It is copolymerized in the presence of an initiator. Thereby, a bead-like copolymer which is the most preferable shape for use is obtained. Generally, a gel-shaped resin is obtained in the former aqueous medium, and a porous resin is obtained in the latter solvent. As the polymerization catalyst,
Benzoyl peroxide, tertiary butyl peroxide, lauroyl peroxide, azobisisobutyronitrile and the like are used. The temperature of the polymerization reaction is usually in the range of 50 to 100 ° C., though it depends on the type of the catalyst.

An ion exchange group such as a sulfonic acid group or an amino group is introduced into the obtained copolymer by a known method. In introducing an amino group, first, a haloalkylating agent is allowed to act on the copolymer by a known method to obtain a haloalkylated copolymer. As the haloalkylating agent, chloromethyl methyl ether, chloroethyl methyl ether, chloromethyl ethyl ether, bromomethyl methyl ether, bromoethyl methyl ether, bromomethyl ethyl ether and the like are used. As a catalyst for haloalkylation, zinc chloride, anhydrous aluminum chloride, tin chloride, iron chloride and the like are used. The catalyst is 1 to 100 (weight) based on the copolymer.
%, And for the same copolymer, the degree of haloalkylation can be controlled by increasing or decreasing the use ratio. Further, in order to achieve the same haloalkylation ratio, the amount of the catalyst used increases as the copolymer has a higher ratio of the polyvinyl compound.

Alternatively, a chlorine-containing reagent selected from hydrochloric acid, methanol, chlorosulfuric acid, sulfuryl chloride, thionyl chloride, acyl chloride, phosphorus trichloride, phosphorus pentachloride, aluminum chloride and the like, and formalin or paraformaldehyde, trioxane, etc. Haloalkylation can also be performed using a solution consisting of a substance that produces formalin during the reaction.

The reaction is usually carried out in the presence of an organic solvent which swells the copolymer, for example, ethylene dichloride, propylene dichloride, benzene, toluene, etc.
A large amount of haloalkylating agent can be used as a swelling solvent. The reaction is usually carried out at a temperature of 40 to 60 ° C for several hours to one day. By reacting the haloalkylated copolymer with various amines such as trimethylamine and dimethylethanolamine, a basic anion exchange resin having characteristics according to the type of amine can be obtained.

Particularly when a tertiary amine is reacted, a strongly basic resin can be obtained. The tertiary amine is selected from trialkylamines comprising an alkyl group having 1 to 4 carbon atoms or alkanol groups, and dialkyl- (mono) alkanolamines. The basic anion exchange resin thus obtained is thoroughly washed with water after removing the remaining amine, and then further washed with an aqueous sodium hydroxide solution as a regeneration type. The ion-exchange resin swells when it is of the regenerative type, but the anion-exchange resin used in the present invention usually has a volume of 110% or more of the Cl-type anion-exchange resin.
An ion exchange resin having a volume of 120% or more is more preferable for the regeneration type. The ion-exchange resin that has been washed with water as a regeneration type is then washed with an organic solvent to have a molecular weight of 3
Eluents of 000 or more, preferably 2000 or more are substantially completely removed. In order to efficiently perform washing with an organic solvent, it is preferable that the ion exchange resin swells more largely in methanol than in water in the regeneration type.

As an organic solvent, methanol is preferably used. If desired, alcohols such as ethanol, propanol and butanol, ketones such as acetone and methyl ethyl ketone, acetonitrile, N, N-dimethylformamide and the like may be used. . These organic solvents are preferably used as an aqueous solution having a concentration of at least 60% (by weight) or more. More preferably 80% or more, especially 90%
It is more preferable to use the above concentration. In any case, it is necessary that the organic solvent used for washing gives the regenerated ion exchange resin greater swelling than in water. In particular, it is preferable to wash the regenerated ion exchange resin with an organic solvent that gives a volume 4% or more larger than the volume in water.

The swelling of the ion-exchange resin in water and in an organic solvent varies depending on the type and amount of the polyvinyl compound, the amount of ion-exchange groups introduced, and the like. Is preferred. On the other hand, in order to make the ion exchange resin easy to wash with an organic solvent, it is necessary to consider increasing the ratio of the polyvinyl compound in the matrix or increasing the hydrophobicity by limiting the amount of ion exchange groups introduced. is there. For example, the amount of ion-exchange groups introduced is preferably set to 4.0 meg / g or less as an exchange capacity. Washing is preferably performed by filling the column with an ion exchange resin, passing an organic solvent through the column in a downward or upward flow, and then passing ultrapure water through the column. The amount of the organic solvent used is at least one time the volume of the regenerative ion exchange resin. Usually, it is used in an amount of 2 times or more, preferably 4 times or more.
Ultrapure water is passed until the organic solvent is completely removed. The column temperature at the time of washing is determined in consideration of the danger and the washing efficiency depending on the type of the organic solvent, and the washing efficiency is often higher when the temperature is as high as possible.

Washing is carried out according to a measuring method described later, with a molecular weight of 30.
The process is performed until no more than 00, preferably no more than 2000 organic compounds are substantially not detected. In the present specification, "substantially not detected" means that an organic compound is eluted according to a method described later, and when the eluted amount and its molecular weight distribution are measured, it is 3 ppm or less as organic carbon, preferably 1 ppm or less. means. In the calculation, the ratio of carbon in the molecule is fixed regardless of the molecular weight. Some organic compounds having a molecular weight of less than 3000 may be left. In order to completely remove this, the washing must be repeated excessively, which is not efficient, and even if some remains, the adverse effect on water quality is small. Usually, the amount of organic carbon dissolved is 300 ppm or less, particularly 1
It is preferable to carry out the washing until the concentration becomes 00 ppm or less.

In the present invention, a mixed bed is formed by combining the anion exchange resin, whose impurities have been reduced as described above, with the cation exchange resin. The cation exchange resin is also preferably one having reduced impurities as described above, but a resin having more impurities can also be used. The reason is that the organic compounds having a molecular weight of 3000 or more eluted from the cation exchange resin are mainly those produced by sulfonating oligomers produced when the base of the ion exchange resin is produced, and are captured by the coexisting anion exchange resin. This is because it is easy to be done.

Water, which has been purified in advance and most of the impurities have been removed, is circulated through the mixed bed thus constituted to make pure water or ultrapure water. If desired, the pure or ultrapure water may be passed through a membrane purification means such as an ultrafiltration membrane. In the present invention, the water that has passed through the above-mentioned mixed bed is carried to the point of use without being further treated with the ion exchange resin. That is, the ion exchange resin containing only a trace amount of the eluate used in the present invention is used in the final stage of the production of pure water or ultrapure water, and is usually a cartridge type in which the ion exchange resin is not regenerated on site. Used as an ion exchange resin bed. Therefore, most of the impurities must be removed beforehand from the water flowing through the resin bed. Usually, water purified to a specific resistance of 12 MΩ · cm or more or a total organic carbon content of 30 ppb or less is treated with this ion exchange resin bed.

For example, in a typical example of the present invention, a specific resistance of 12 MΩ · cm or more and a total organic carbon content of 30 through treatments such as ion exchange resin treatment, degassing under reduced pressure, and reverse osmosis membrane treatment.
Pure water purified to ppb or less is passed through a mixed bed composed of the strongly basic anion exchange resin according to the present invention, and the microorganisms are further sterilized by irradiation with ultraviolet light and then suspended by a membrane separation device such as an ultrafiltration membrane. Remove turbid matter to make ultrapure water. In another typical example, the above-mentioned pure water is irradiated with short-wavelength ultraviolet rays, for example, ultraviolet rays of 185 nm, to decompose organic substances contained therein into carboxylic acids or carbonic acids, and then decompose the strongly basic acid according to the present invention. The mixed bed composed of an anion exchange resin is circulated to make ultrapure water. It is further preferred that the water is passed through a bed of the strongly basic anion exchange resin according to the present invention before the mixed bed, or the water passed through the mixed bed is treated with an ultrafiltration membrane.

[0027]

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited at all by these examples. In the present invention, the swelling volume of the ion exchange resin, the amount of organic carbon eluted during immersion in warm water, and the molecular weight thereof were measured by the following methods.

Measurement method of swelling volume A Cl-type resin is placed in a 10 ml measuring cylinder pre-filled with water, and is precisely adjusted to 10.0 volume.
Measure ml. This was put into a column, and a 1N aqueous solution of sodium hydroxide was passed at SV = 5 for 1 hour, and then sufficiently washed with demineralized water to obtain a regeneration type. 25 ml of this resin
Put in a measuring cylinder and measure the volume to obtain the swelling volume of the reclaimable resin. Further, the regenerated resin obtained above is put into a column, and methanol is passed through at SV = 1 for 4 hours. The resin is then placed in a 25 ml graduated cylinder and its volume measured to give the swelling volume in methanol. The measurement is performed in exactly the same manner for other organic solvents.

Elution amount of organic carbon: 100 ml of regenerated ion exchange resin sufficiently swollen in pure water together with water
Pour into a graduated cylinder of 100m
Match with the marked line of l. After filtration to remove water between the resin particles, the resin is transferred to a 500 ml flask, and 100 ml of pure water is added. The flask is immersed in a water bath at 50 ° C. and shaken at a shaking frequency of 100 / min for 7 days, that is, for 168 hours. After completion of the shaking, the ion exchange resin is filtered off using a 0.45 μm Teflon filter manufactured by Millipore.

20 μl of the filtrate is injected into a total organic carbon analyzer TOC-10B manufactured by Shimadzu Corporation, the height of the detection peak is measured, and the result is converted into the total organic carbon concentration in the filtrate and displayed. The calibration curve for conversion was obtained by using potassium hydrogen phthalate as a standard substance and carbon concentrations of 40 ppm, 100 ppm, and 200 pp.
Make based on m and 400 ppm solution. Molecular weight of eluate: The filtrate obtained above is analyzed by gel permeation chromatography (GPC) under the following conditions.

Column: Column for aqueous GPC (using Asahi Pack G310 and G510 of Asahi Kasei Kogyo Co., Ltd. connected in series) Developing solution: 0.01N-HCl Flow rate: 0.5 ml / min Temperature: 25 ° C. Detection: UV 240 nm Injection volume: 200 μl

Comparative Example 1 Styrene 94.6 (weight)
Parts, 5.4 parts by weight of divinylbenzene (purity 55.8%) and 0.5 parts by weight of dibenzoyl peroxide were mixed well, and this was mixed with water in which 0.5 parts by weight of polyvinyl alcohol was dissolved. 300 parts by weight. 8
The suspension polymerization was carried out with stirring at 0 ° C. for 10 hours, followed by washing with water and drying to obtain a granular copolymer. The polymerization yield was 95 (by weight)% based on the starting monomer.

To 100 parts by weight of the copolymer, 500 parts by weight of chloromethyl methyl ether was added, and the mixture was stirred at room temperature for 1 hour. Then, 10 parts by weight of zinc chloride was added thereto. The reaction was performed to effect chloromethylation. After completion of the reaction, the reaction product was cooled and water was added to decompose the remaining reagent. The obtained chloromethylated copolymer is thoroughly washed with water and then trimethylamine 10
(Weight)
And aminated for 10 hours.

After completion of the amination, the remaining trimethylamine was removed by vaporization by heating, and further thoroughly washed with water to obtain a basic anion exchange resin (I). This anion exchange resin was packed in a column, and a 5 volume-fold 1N aqueous solution of NaOH was passed through at SV = 5, followed by washing with deionized water to obtain a regenerated anion exchange resin (A). Was.

Example 1 The basic anion-exchange resin (I) obtained in Comparative Example 1 was packed in a column, and 5 times the volume of 1N-N
After passing an aOH aqueous solution at SV = 5 and then washing by passing demineralized water at a temperature of 25 ° C., pass 4% by volume of 100% methanol at SV = 1 and wash thoroughly with demineralized water. Thus, a regeneration type anion exchange resin (B) was obtained.

Example 2 87.4 styrene (weight)
Parts, 12.6 parts by weight of divinylbenzene (purity: 55.6%) and 0.5 parts by weight of dibenzoyl peroxide were used in the same manner as in Comparative Example 1 and Example 1, except that An anion exchange resin (C) was obtained.

Example 3 Styrene 85.6 (weight)
Parts, 14.4 parts by weight of divinylbenzene (purity 55.6%), 70 parts by weight of isooctane, and 1 part by weight of dibenzoyl peroxide were mixed well. The above mixture was added to 400 parts by weight of water in which 0.7 parts by weight of polyvinyl alcohol was dissolved, and 1 part of the mixture was stirred at 80 ° C. while stirring.
The suspension polymerization was performed for 0 hours.

After the completion of the reaction, isooctane and water were removed by azeotropic distillation, followed by washing and drying to obtain a granular copolymer. The polymerization yield was 92% by weight based on the starting monomer. 100 parts by weight of copolymer, 200 parts by weight of ethylene dichloride, chloromethyl methyl ether 3
Then, 00 (part by weight) was added, and the mixture was stirred at room temperature for 1 hour. Then, 50 (part by weight) of zinc chloride was added, and the mixture was reacted at 50 ° C. for 10 hours to perform chloromethylation.

After completion of the reaction, the reaction product was cooled and water was added to decompose the remaining reagent. The obtained chloromethylated copolymer was thoroughly washed with water, and then charged into 400 parts (by weight) of a 10% (by weight) aqueous solution of trimethylamine to obtain 5%.
Amination was carried out at 0 ° C. for 10 hours. After completion of the amination, the remaining trimethylamine was removed by vaporization by heating, and further thoroughly washed with water to obtain a basic anion exchange resin.

This anion exchange resin is packed in a column,
Washing was carried out by passing a 1-fold volume of 1N-NaOH aqueous solution at SV = 5 and subsequently passing demineralized water. 100 times that of twice the capacity
% Ethanol was passed at SV = 1, and then sufficiently washed with deionized water to obtain a regenerated anion exchange resin (D). Table 1 shows the ion exchange capacity, the swelling volume in 100% methanol and 100% ethanol in water, and the total amount of eluted organic carbon of the anion exchange resin thus obtained. In addition, the molecular weight distribution of the eluate measured by GPC after passing ultrapure water through the ion exchange resins produced in these comparative examples and Examples 1 to 3 is shown in FIGS. 1 to 4, respectively.

[0041]

[Table 1]

Test Example 1 A regenerated cation exchange resin for nuclear power, SKNUPA, which is obtained by sulfonating a styrene-divinylbenzene copolymer and then sufficiently washing it to reduce the amount of eluted material extremely (Diaion is Mitsubishi 370 ml of a registered trademark of Kasei Co., Ltd. and 630 ml of each of the anion exchange resins A to D obtained in Comparative Example 1 and Examples 1 to 3 as anion exchange resins were mixed well and packed into a column having an inner diameter of 50 mm. A mixed bed was formed. Ultrapure water (total organic carbon: 3 ppb) at 25 ° C. was added to the mixed bed by SV = 3.
Water was passed at 0, and the electric conductivity and total organic carbon content of the column effluent were measured. The results are shown in FIGS.

Example 4 In Example 2, instead of flowing the regenerated anion exchange resin at 4 times the amount of methanol at SV = 1, the aqueous methanol solution having the following concentration was quadrupled at SV = 1. The volume was passed. In addition, all column temperatures during the passage of the liquid were kept at 40 ° C. At each methanol concentration, the resulting resins were designated as Samples EI as described below. A sample of the resin not treated with methanol was designated as J.

[0044]

Table 2 Regeneration in methanol solvent Methanol concentration Resin volume in sample type (ml) 100% E 10.80% F 10.6 60% G 10.5 40% H 10.4 20% I 10.2 Unprocessed J 10.0

Test Example 2 A water flow test was performed in the same manner as in Test Example 1, except that Samples E, F, G, H, I, and J were used. FIG. 7 shows the result of measuring the total amount of organic carbon.

[0046]

According to the present invention, an ion exchange resin for producing ultrapure water can be easily produced, and ultrapure water can be produced easily using the ion exchange resin.

[Brief description of the drawings]

FIG. 1 is a graph showing a molecular weight distribution of an eluate of an anion exchange resin B produced in Example 1.

FIG. 2 is a graph showing a molecular weight distribution of an eluate of an anion exchange resin C produced in Example 2.

FIG. 3 is a graph showing a molecular weight distribution of an eluate of an anion exchange resin D produced in Example 3.

FIG. 4 is a graph showing the molecular weight distribution of the eluate of the anion exchange resin (A) produced in Comparative Example 1.

FIG. 5 shows the flow rate and effluent when ultrapure water is passed through a mixed bed composed of the anion exchange resin and Diaion (registered trademark) SKNUPA produced in Comparative Example 1 and Examples 1 to 3. It is a graph which shows the relationship with specific resistance.

FIG. 6 shows the amount of water flow and the amount of effluent water when ultrapure water is passed through a mixed bed composed of the anion exchange resin and Diaion (registered trademark) SKNUPA produced in Comparative Example 1 and Examples 1 to 3. It is a graph which shows the relationship with the total organic carbon concentration.

FIG. 7 shows the flow rate when ultrapure water is passed through a mixed bed composed of the anion exchange resin samples E to I produced in Example 4 and Sample J for comparison and Diaion (registered trademark) SKNUPA. 4 is a graph showing the relationship between the concentration of the organic solvent and the total organic carbon concentration in the effluent.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁷ Identification symbol FI C08J 5/20 C08J 5/20 (56) References JP-A-63-291645 (JP, A) JP-A-60-102950 (JP) , A) Japanese Patent Publication No. 2-15258 (JP, B2) (58) Field surveyed (Int. Cl. ⁷ , DB name) C02F 1/42 B01J 39/00-49/02

Claims (10)

(57) [Claims] 1. An ion-exchange resin based on a copolymer of a monovinyl aromatic compound and a polyvinyl compound which may contain a monovinyl aliphatic compound, which is immersed in warm water at 50 ° C. for 7 days. the organic compound having a molecular weight of less than 3000 elutes but a molecular weight of 3,000 or more organic compounds substantially eluted such have basic anion exchange resin,
Mix with cation exchange resin to mix in ultrapure water production process
Production of ultrapure water characterized by use in a bed ion exchange column
Construction method. 2. A basic anion exchange resin, the eluate when immersed for 7 days in a 5 0 ° C. hot water, as organic carbon, Ru 10~300ppm der ultrapure of claim 1
Water production method. 3. A basic anion exchange resin, area by the near 90% by weight or more of molecular weight less than 2000 of the organic compound to elute, the preparation of pure water according to claim 1 or 2. 4. The basic anion exchange resin, after haloalkylated mother body, Ru der made aminated, wherein
Item 4. The method for producing ultrapure water according to any one of Items 1 to 3. 5. The method according to claim 1, wherein the basic anion exchange resin is C
When the volume of the l-type resin is 100%, the volume of the regenerated resin in water is 110% or more, and the volume of the regenerated resin in methanol is smaller than the volume of the regenerated resin in water. /> is a large cast, ultra according to any one of claims 1 to 4
Pure water production method. 6. anion exchange resin, motor Nobiniru aliphatic compound include good monovinyl aromatic optionally compound copolymer of a polyvinyl compound and a basic anion exchange resin regeneration type as a matrix, which water washed with a large organic solvent swelling power than, then washed with water is obtained by Rukoto be removed <br/> the organic solvent, claims 1-5 Neu
The method for producing ultrapure water described in any of the above. Relative 7. A playback type anion exchange resin, than in water, in the wash with an organic solvent to express a large volume of 4% or more, the preparation of ultra-pure water according to claim 6. 8. Prior to passing through the mixed bed ion exchange column,
Good monovinyl also include monovinyl aliphatic of compound
A copolymer of an aromatic compound and a polyvinyl compound is used as a base.
Ion-exchange resin that is kept in warm water at 50 ° C for 7 days
Organic compounds with a molecular weight of less than 3000 when immersed
However, organic compounds having a molecular weight of 3000 or more are substantially
Passing through a bed of non-eluting basic anion exchange resin,
The method for producing ultrapure water according to claim 1. 9. A system comprising at least a primary system and a secondary system,
In a method for producing ultrapure water, in which pure water obtained in the primary system is further purified in the secondary system and thereafter to ultrapure water, a monovinyl aliphatic
Monovinyl aromatic compounds which may contain
Ion-exchange tree based on a copolymer with a vinyl compound
Fat, when soaked in warm water at 50 ° C for 7 days
Organic compounds having a molecular weight of less than 3000 are eluted,
3000 or more organic compounds substantially eluted without salt group anion exchange resin, production of ultrapure water, which comprises using at least one secondary system and subsequent anion exchange column, or mixed bed ion exchange column Law. 10. A method for producing ultrapure water from which impurities including inorganic salts, organic substances, fine particles, and microorganisms are removed by performing a treatment including ion exchange, wherein at least the mixed bed ion exchange treatment of the ion exchange treatment is performed. The ion exchange resin to be used may be a resin which may contain a monovinyl aliphatic compound.
Copolymer of novinyl aromatic compound and polyvinyl compound
Is an ion exchange resin whose base is
Of molecular weight less than 3000 when immersed in water for 7 days
The compound elutes, but organic compounds with a molecular weight of 3000 or more
A method for producing ultrapure water, which is a basic anion exchange resin that does not substantially elute .