JP2002035607A - Anion exchange resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a heat resistant anion exchange resin improved in appearance, physical strengths, elution properties of impurities or the like. SOLUTION: The anion exchange resin is composed of a bridged copolymer containing, as a main constitutive unit, a constitutive unit expressed by general formula (2), wherein, A is a 3-8C alkylene group; R1 to R3 are each hydrogen atom, a 1-4C alkyl group or a 1-4C alkanol group; and X is a counterion coordinated to the ammonium group, with the proviso that R1 to R3 are not simultaneously hydrogen atom, and a constitutive unit expressed by general formula (1) and has the following characteristics. [1] The content of the constitutive unit expressed by general formula (1) is <0.5 wt.%. [2] The ratio of the resin having no crack is >=90%. [3] The crushing strength is >=200 g/particle. [4] When pure water of 25 deg.C is passed through the resin with the space velocity SV of 30, the concentration of alkylamines in pure water passed through the resin at 6 hours after the start of water supply is <=200 ppt.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an anion exchange resin having excellent heat resistance and a method for producing the same. The anion exchange resin of the present invention is suitable for producing high-purity water used in the electronic industry, such as ultrapure water for electronic materials, such as washing water used in the production process of an ultra LSI.

[0002]

2. Description of the Related Art Anion exchange resins include, for example, desalination of water for boilers, production of ultrapure water for semiconductor production, purification of sugar solution,
It is used as a water treatment and purification means in various industrial fields such as purification of amino acids and antibiotics, and is also used as a catalyst for chemical reactions. The most widely used anion exchange resin is a strong basic anion exchange resin in which an anion exchange group such as a trimethylammonium group is introduced into the benzene ring of a crosslinked polymer obtained by copolymerizing styrene and divinylbenzene via a methylene group. There is. However, such a strongly basic anion exchange resin, under high temperature conditions, decomposes the ammonium salt and causes the exchange group to be dropped, resulting in a significant decrease in performance.
The temperature was set to 80 ° C. for the Cl-type resin.

[0003] As a heat-resistant ion exchange resin which solves this drawback, Japanese Patent Application Laid-Open No. 4-34991 discloses a polymer in which a quaternary ammonium group is introduced into a benzene ring of a crosslinked polymer via a polymethylene group having 3 to 18 carbon atoms. Ion exchange resins have been proposed. As described above, an anion exchange resin having an alkylene group having 3 or more carbon atoms (referred to as a spacer) between the benzene ring and the anion exchange group of the crosslinked polymer is kept at 100 ° C. for a long time when the spacer is 4, for example. Even after this, sufficient ion exchange capacity remains and is expected as an anion exchange resin usable at high temperatures.

[0004] Anion exchange resins having the structure represented by the general formula (2) are also disclosed in JP-A-4-33491 and JP-A-10-24290 (Mitsubishi Chemical). JP-A-10-24290 discloses that the concentration of trimethylamine leaked from a resin is 20 ppb, at least several ppb.
Met. As a result, radical polymerization was not completed, and as a result, not only eluates from the resin increased, but also leakage of alkylamines such as trimethylamine increased by orders of magnitude.

[0005]

In order for an ion exchange resin to be used industrially, various properties other than heat resistance are required. As one index, there is a numerical value (hereinafter, referred to as “appearance”) representing the ratio of the resin having no crack in the ion-exchange resin particles as a percentage. Appearance is usually 90%
Higher numbers are required. If the appearance is low, the crack resin is large, the appearance is poor, the strength is poor, and the commercial value is undesirably reduced. According to the studies of the present inventors, an anion exchange resin having an industrially produced spacer is:
This "appearance" is not always sufficient.

The concentration of alkylamines in water is several
In high-purity pure water such as 0 ppt, impurities derived from the ion-exchange resin greatly affect water quality. That is, when the solution is passed through the ion exchange resin bed, impurities in 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. For this reason, the obtained water quality does not improve more than a certain degree.

[0007] As one of measures to reduce elution of impurities from the ion exchange resin, ultrapure water is passed through an ion exchange resin tower before use to remove elutes remaining in the resin. I have. However, this consumes a part of the product ultrapure water in the manufacturing process, which reduces the efficiency of the process. Therefore, in order to increase the amount of water with high quality, an ion-exchange resin that elutes from the resin quickly and has a small amount of elution is desired. On the other hand, it is said that the concentration of alkylamines in water is greatly related to the defective rate of products in semiconductor production.
In order to improve the yield rate of semiconductors, ultrapure water that minimizes leakage of alkylamines such as trimethylamine is desired.

An object of the present invention is to provide a heat-resistant anion exchange resin having improved appearance, physical strength, elution of impurities and the like.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies in order to achieve the above object, and have found that the content of the constituent units derived from impurities in the monomer used as a reaction raw material among the constituent units of the resin. Has been found to affect the generation of cracked resin, and by reducing the amount of such impurities, succeeded in obtaining a resin having excellent appearance, high physical strength, and little elution of impurities, and reached the present invention. did. That is, the first of the gist of the present invention is 1) an anion exchange resin comprising a crosslinked copolymer having a repeating unit represented by the following general formula (2) as a main constituent unit, wherein the crosslinked copolymer is Wherein the content of the structural unit represented by the following general formula (1) is less than 0.5% by weight.

[0010]

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In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms, and R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, an alkyl group having 4 or less carbon atoms, and an alkyl group having 4 carbon atoms. The following alkanol groups are shown, and X represents a counter ion coordinated to an ammonium group, but R ₁ , R ₂ and R ₃ are not simultaneously hydrogen atoms. 2) According to a preferred embodiment of the present invention, the crosslinked copolymer contains at least one type of a structural unit represented by the following general formula (3) or (4), and comprises a structural unit represented by the following general formula (1). The content is less than 1.5% by weight, the following general formula (4)
The anion exchange resin according to the above 1), wherein the content of the structural unit represented by is less than 2% by weight;

[0012]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 3) The crosslinked copolymer simultaneously contains the structural units represented by the general formulas (1), (3) and (4), and the content thereof is less than 0.5% by weight and less than 1.5% by weight, respectively. , And 2
The anion exchange resin according to the above 2), which is less than 1% by weight; 4) The content of the structural unit represented by the general formula (3) is less than 1% by weight; The content of the constituent unit is 1
An anion exchange resin according to the above 2), wherein the content of the structural unit represented by the general formula (1) is less than 0.07% by weight; ) Is 0.0
Above 1) to 4), which is less than 1% by weight.
6) In the general formula (2), A is a butylene group, wherein the anion exchange resin according to any one of the above 1) to 5); 7) In the general formula (2), R ₁ , R ₂ and R ₃ are a methyl group at the same time, and the anion exchange resin according to any one of the above 1) to 6) is provided. The second of the gist of the present invention is 8) a crosslinked copolymer containing a repeating unit represented by the following general formula (2) as a main constitutional unit and containing a constitutional unit represented by the following general formula (1). An anion exchange resin, wherein the proportion of crack-free resin in the anion exchange resin is 90% or more.

[0014]

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In the formula (2), A is an alkyl having 3 to 8 carbon atoms.
Represents a kylene group;₁, R_Two, And R _ThreeAre independently
Hydrogen atom, alkyl group having 4 or less carbon atoms and 4 or less carbon atoms
X is coordinated to an ammonium group.
The counter ion₁, R_Two, And R_ThreeIs hydrogen at the same time
9) In the crosslinked copolymer, the following general formulas (3) and (4)
Comprising at least one structural unit represented by the following general formula:
The content of the structural unit represented by (3) is not more than 1.5% by weight.
When the content of the structural unit represented by the following general formula (4) is 2
% By weight and containing a structural unit represented by the general formula (1).
Characterized in that the prevalence is less than 0.5% by weight
Anion exchange resin according to 8) above;

[0016]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms.) 10) The structure represented by the general formulas (1), (3) and (4) in the crosslinked copolymer Units at the same time, the content of each being less than 0.5% by weight, less than 1.5% by weight, and 2
The anion exchange resin according to the above 9), wherein the content is less than 1% by weight; the content of the structural unit represented by the general formula (3) is less than 1% by weight; The anion according to 9) above, wherein the content of the structural unit is less than 1% by weight, and the content of the structural unit represented by the general formula (1) is less than 0.07% by weight. Exchange resin; 12) the content of the structural unit represented by formula (1) is 0.1;
8) to 1), wherein the content is less than 01% by weight.
13) an anion exchange resin according to any one of the above 8) to 12), wherein in the general formula (2), A is a butylene group; 14) In the general formula (2), R ₁ , R ₂ and R ₃ are simultaneously a methyl group.
An anion exchange resin according to any one of the above. The third of the gist of the present invention is 15) a cross-linked copolymer containing a repeating unit represented by the following general formula (2) as a main constitutional unit and containing a constitutional unit represented by the following general formula (1). An ion exchange resin,
The crushing strength of the anion exchange resin is 200 g / particle or more.

[0018]

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(In the formula (2), A is an alkyl having 3 to 8 carbon atoms.)
Represents a kylene group;₁, R_Two, And R _ThreeAre independently
Hydrogen atom, alkyl group having 4 or less carbon atoms and 4 or less carbon atoms
X is coordinated to an ammonium group.
The counter ion₁, R_Two, And R_ThreeIs hydrogen at the same time
16) In the crosslinked copolymer, the following general formulas (3) and (4)
Including at least one structural unit represented by the following general formula
The content of the structural unit represented by the formula (3) is less than 1.5% by weight.
When the content of the structural unit represented by the following general formula (4) is 2
% By weight and containing a structural unit represented by the general formula (1).
Characterized in that the prevalence is less than 0.5% by weight
Anion exchange resin according to 15) above;

[0020]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms.) 17) The structure represented by the general formulas (1), (3) and (4) in the crosslinked copolymer Units at the same time, the content of each being less than 0.5% by weight, less than 1.5% by weight, and 2
An anion exchange resin according to the above 16), which is less than 18% by weight; 18) a content of the structural unit represented by the general formula (3) is less than 1% by weight and represented by the general formula (4). The anion exchange resin according to the above item 16), wherein the content of the structural unit is less than 1% by weight and the content of the structural unit represented by the general formula (1) is less than 0.07% by weight. 19) the content of the structural unit represented by the general formula (1) is 0.1;
The anion exchange resin according to any one of the above 15) to 18), which is less than 01% by weight; 20) In the general formula (2), A is a butylene group. 21) The anion exchange resin according to any one of the above items 15) to 20), wherein in the general formula (2), R ₁ , R ₂ and R ₃ are simultaneously a methyl group.
The anion exchange resin according to any one of the above is provided. A fourth subject of the present invention is 22) a crosslinked copolymer containing a repeating unit represented by the following general formula (2) as a main constitutional unit and containing a constitutional unit represented by the following general formula (1). An ion exchange resin,
Space velocity SV30, water passing temperature 25
When pure water is passed under the condition of 0 ° C., the concentration of alkylamines in the passed pure water after 6 hours from the start of water passing is 2%.
An anion exchange resin characterized by being at most 00 ppt.

[0022]

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(In the formula (2), A represents an alkyl having 3 to 8 carbon atoms.)
Represents a kylene group;₁, R_Two, And R _ThreeAre independently
Hydrogen atom, alkyl group having 4 or less carbon atoms and 4 or less carbon atoms
X is coordinated to an ammonium group.
The counter ion₁, R_Two, And R_ThreeIs hydrogen at the same time
23) In the crosslinked copolymer, the following general formulas (3) and (4)
Including at least one structural unit represented by the following general formula
The content of the structural unit represented by the formula (3) is less than 1.5% by weight.
When the content of the structural unit represented by the following general formula (4) is 2
% By weight and containing a structural unit represented by the general formula (1).
Characterized in that the prevalence is less than 0.5% by weight
Anion exchange resin according to 22) above;

[0024]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms.) 24) The structure represented by the general formulas (1), (3) and (4) in the crosslinked copolymer Units at the same time, the content of each being less than 0.5% by weight, less than 1.5% by weight, and 2
25) the anion exchange resin according to the above 23), wherein the content of the structural unit represented by the general formula (3) is less than 1% by weight; The anion according to the above item 23), wherein the content of the structural unit is less than 1% by weight and the content of the structural unit represented by the general formula (1) is less than 0.07% by weight. Exchange resin; 26) when the content of the structural unit represented by the general formula (1) is 0.
The anion exchange resin according to any one of the above 22) to 25), wherein the content is less than 01% by weight; 27) the general formula (2), wherein A is a butylene group; 28) The anion exchange resin according to any one of the above items 22) to 26), wherein in the general formula (2), R ₁ , R ₂ and R ₃ are simultaneously a methyl group.
The anion exchange resin according to any one of 7) is provided.
A fifth aspect of the gist of the present invention is 29) a cross-linked copolymer containing a repeating unit represented by the following general formula (2) as a main constitutional unit and containing a constitutional unit represented by the following general formula (1). An ion exchange resin,
An anion exchange resin characterized in that the surface of the ion exchange resin is treated with a polymer electrolyte.

[0026]

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In the formula (2), A represents an alkyl having 3 to 8 carbon atoms.
Represents a kylene group;₁, R_Two, And R _ThreeAre independently
Hydrogen atom, alkyl group having 4 or less carbon atoms and 4 or less carbon atoms
X is coordinated to an ammonium group.
The counter ion₁, R_Two, And R_ThreeIs hydrogen at the same time
30) In the crosslinked copolymer, the following general formulas (3) and (4)
Including at least one structural unit represented by the following general formula
The content of the structural unit represented by the formula (3) is less than 1.5% by weight.
When the content of the structural unit represented by the following general formula (4) is 2
% By weight and containing a structural unit represented by the general formula (1).
Characterized in that the prevalence is less than 0.5% by weight
Anion exchange resin according to 29) above;

[0028]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms.) 31) The structure represented by the general formulas (1), (3) and (4) in the crosslinked copolymer Units at the same time, the content of each being less than 0.5% by weight, less than 1.5% by weight, and 2
The anion exchange resin according to the above item 30), wherein the content of the structural unit represented by the general formula (3) is less than 1% by weight; The anion according to the above item 30), wherein the content of the constituent unit is less than 1% by weight and the content of the constituent unit represented by the general formula (1) is less than 0.07% by weight. Exchange resin; 33) when the content of the structural unit represented by the general formula (1) is 0.
The anion exchange resin according to any one of the above 29) to 32), which is less than 01% by weight; 34) In the general formula (2), A is a butylene group. 35) The anion exchange resin according to any one of the above items 29) to 33), wherein in the general formula (2), R ₁ , R ₂ and R ₃ are simultaneously a methyl group.
4) The anion exchange resin according to any of 3); 36) the polymer electrolyte is polystyrenesulfonic acid, polyvinylbenzylsulfonic acid, poly (meth) acrylic acid,
The anion exchange resin according to any one of the above 29) to 35), which is selected from the group consisting of polymaleic acid, polyvinyl sulfonic acid, and salts thereof, is provided. Fifth of the gist of the present invention is 37) a crosslinked copolymer containing a repeating unit represented by the following general formula (2) as a main constitutional unit and containing a constitutional unit represented by the following general formula (1). An ion exchange resin,
Space velocity SV30, water passing temperature 25
An anion exchange resin characterized in that when pure water is passed under the condition of ° C., the number of fine particles in pure water passing therethrough after 12 hours from the start of water passing is 50 particles / ml or less.

[0030]

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In the formula (2), A represents an alkyl having 3 to 8 carbon atoms.
Represents a kylene group;₁, R_Two, And R _ThreeAre independently
Hydrogen atom, alkyl group having 4 or less carbon atoms and 4 or less carbon atoms
X is coordinated to an ammonium group.
The counter ion₁, R_Two, And R_ThreeIs hydrogen at the same time
It cannot be an atom). 38) In the crosslinked copolymer, the following general formulas (3) and (4)
Including at least one structural unit represented by the following general formula
The content of the structural unit represented by the formula (3) is less than 1.5% by weight.
When the content of the structural unit represented by the following general formula (4) is 2
% By weight and containing a structural unit represented by the general formula (1).
Characterized in that the prevalence is less than 0.5% by weight
Anion exchange resin according to 37) above;

[0032]

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(In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 39) The crosslinked copolymer simultaneously contains the structural units represented by the general formulas (1), (3) and (4), and the content thereof is less than 0.5% by weight and less than 1.5% by weight, respectively. , And 2
The anion exchange resin according to the above item 38), wherein the content of the structural unit represented by the general formula (3) is less than 1% by weight; 38. The anion according to the above item 38), wherein the content of the structural unit is less than 1% by weight and the content of the structural unit represented by the general formula (1) is less than 0.07% by weight. Exchange resin; 41) when the content of the structural unit represented by the general formula (1) is 0.
37 to 4 characterized by being less than 01% by weight.
42) The anion exchange resin according to any one of the above 37) to 41), wherein in the general formula (2), A is a butylene group; 43) In the above general formula (2), R ₁ , R ₂ and R ₃ are simultaneously a methyl group.
Anion exchange resin according to any of 2); 44) the following general formula (5):

[0034]

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(Wherein, A represents an alkylene group having 3 to 8 carbon atoms, and Z represents a halogen atom), and a crosslinking agent is reacted with a crosslinking agent in the presence of a polymerization initiator.
The crosslinked polymer obtained by copolymerization and the following general formula (6)

[0036]

Embedded image R ₁ R ₂ R ₃ N (6) (wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
An alkyl group having 4 or less carbon atoms and an alkanol group having 4 or less carbon atoms are shown, but R ₁ , R ₂ , and R ₃ are not hydrogen atoms at the same time. )), Wherein the haloalkylstyrene contains at least one compound selected from the group consisting of divinylbiphenyl, bis (vinylphenyl) alkane, and vinylphenol. 45) a process for producing an anion exchange resin, wherein the content of vinylphenol is less than 0.5% by weight; 45) the haloalkylstyrene of the general formula (5) is divinylbiphenyl, bis (vinylphenyl) alkane , And vinylphenol, and the content thereof is less than 1.5% by weight, less than 2% by weight, and less than 0.5% by weight, respectively, 46). Divinylbiphenyl, bis (vinylphenyl) alkane in haloalkylstyrenes of general formula (5), and The content of alkenyl phenol, respectively less than 1% by weight,
The production method according to the above item 45), wherein the production method is less than 1% by weight and less than 0.07% by weight.

There are several known methods for producing a crosslinked polymer having the structural unit represented by the general formula (2) as a main component, but the most industrially advantageous production method is the general formula (5)
And a cross-linking agent such as divinylbenzene is copolymerized, and the obtained cross-linked copolymer is reacted with an amine such as trimethylamine to introduce an anion exchange group.

As the monomer represented by the general formula (5),
For example, chloropropyl styrene, bromopropyl styrene, chlorobutyl styrene, bromobutyl styrene, bromopentyl styrene, bromohexyl styrene and the like are preferable, and a haloalkyl styrene in which a haloalkylene group is substituted at the para-position of a vinyl group is particularly preferable. These haloalkylstyrenes can be obtained, for example, by reacting chlorostyrene with 1, ω-dihalogenoalkane by the Grignard method.

The monomer represented by the general formula (5) contains various impurities derived from side reactions in the synthesis process or raw materials or impurities in the raw materials. Such impurities include, for example, styrene, bis (vinylphenyl) alkane, divinylbiphenyl, vinylphenol, chlorostyrene, bromostyrene, dihalogenoalkane, and the like. These impurities are contained to a considerable extent in the monomer. I have.

Among these trace impurities, particularly those having one or more vinyl groups are those represented by the general formula (5)
Is polymerized with a vinyl monomer or a cross-linking agent, and is taken into the ion exchange resin produced. Heretofore, it has been considered that various vinyl compounds derived from impurities in these monomers do not substantially affect properties such as the weight and exchange capacity of the ion-exchange resin because of their small amounts. The present inventors have found that some of these impurities have a large effect on the formation of cracked (cracked) resins, and by reducing the content of components derived from these impurities in the ion exchange resin, the content of the cracked resin is reduced. A heat-resistant anion exchange resin having excellent physical strength was obtained.

[0041]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The anion exchange resin according to the present invention is an anion exchange resin comprising a crosslinked copolymer having a repeating unit represented by the general formula (2) as a main constituent unit. The content of the structural unit represented by the formula (1) is less than 0.5% by weight, preferably 0.07% by weight.
, More preferably less than 0.01% by weight, particularly preferably 0.0001 to less than 0.01% by weight. In the general formula (2), A represents an alkylene group having 3 to 8 carbon atoms (the alkylene group represents a linear or branched bonding group having a carbon chain; for example, a propylene group, a butylene group, and a hexylene group. Octylene group etc.), R ₁ ,
R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group having 4 or less carbon atoms and an alkanol group having 4 or less carbon atoms, and X represents a counter ion coordinated to an ammonium group,
R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time. Further, the crosslinked polymer contains at least one structural unit represented by the general formulas (3) and (4), and the structural unit represented by the general formula (3) is less than 1.5% by weight, preferably 1% by weight. Is less than 0.001 to 1% by weight, and the structural unit of the general formula (4) is less than 2% by weight, preferably less than 1% by weight, and more preferably 0.0001 to less than 1% by weight. The cross-linked polymer may contain the structural units of the general formulas (1), (3) and (4) at the same time.

The method for reducing the content of impurities in the ion exchange resin to the above range is not particularly limited. For example, as a monomer of the general formula (5) as a raw material, an impurity producing the above structural unit may be used. That is, the amounts of divinylbiphenyl which forms the structural unit of the general formula (3), bis (vinylphenyl) alkane which forms the structural unit of the general formula (4), and vinylphenol which generates the structural unit of the general formula (1) It is preferred to use a reduced one.

The method of reducing the impurities is not particularly limited, but a method of suppressing the generation of these impurities during the synthesis or the purification of the product to reduce the impurities in the general formula (5) Achieved by a reducing method. That is, the monomer of the general formula (5) is usually produced by reacting a dihalogenoalkane with a Grignard reagent of chlorostyrene. At the time of Grignard reagent preparation, for example, by replacing the nitrogen gas and controlling the amount of oxygen in the reaction system,
The amount of generation of impurities can be reduced.

Examples of the method for purifying the monomer of the general formula (5) include distillation (thin film purification), adsorption (adsorbent: alumina and silica gel), chromatographic separation, crystallization, and fractional precipitation. Can be adopted. The amount of impurities allowed in the monomer of the general formula (5) for obtaining the anion exchange resin of the present invention is used for the amount of a cross-linking agent and other copolymer components, and for introducing an ion exchange group. The amount of divinyl biphenyl is at least less than 1.5% by weight, preferably less than 1% by weight, more preferably less than 1% by weight. 0.
0001 to less than 1% by weight, and bis (vinylphenyl)
Less than 2% by weight of alkane, preferably less than 1% by weight, more preferably less than 0.001 to 1% by weight, and less than 0.2% by weight of vinylphenol, preferably less than 0.07% by weight, More preferably 0.0001 to
Less than 0.07% by weight.

The monomer of the general formula (5) in which impurities are reduced is copolymerized with a crosslinking agent and, if necessary, other vinyl monomers in the presence of a polymerization initiator by a known method. As a crosslinking agent, a monomer having two or more unsaturated double bonds, specifically, polyvinyl benzene such as divinyl benzene and trivinyl benzene, alkyl divinyl benzene such as divinyl toluene, ethylene glycol di (meth) acrylate And (meth) acrylate derivatives such as diethylene glycol di (meth) acrylate. Of these, divinylbenzene is preferred. Although divinylbenzene for industrial use contains about 20 to 50% by weight of impurities such as ethylstyrene, the presence of ethylstyrene is not particularly problematic. For example, when divinylbenzene is used, the amount of the crosslinking agent used is 0 to
It is 50% by weight, preferably 0 to 20% by weight, more preferably 0.2 to 8% by weight. The amount of divinylbenzene is 0
Even in the case of weight%, divinyldiphenyl or bis (vinylphenyl) alkane is contained as an impurity in the monomer of the general formula (5), so that the obtained copolymer is slightly crosslinked. .

Examples of other vinyl monomers used as required include styrenes such as styrene, methylstyrene and chlorostyrene, and (meth) acrylates such as methyl (meth) acrylate. The amount used is 0 to 20% by weight. Examples of the polymerization initiator include peroxide initiators such as benzoyl peroxide (BPO), lauroyl peroxide, and t-butyl hydroperoxide, azobisisobutyronitrile (AIBN), 2,2-azobis (2, An azo-based polymerization initiator such as 4-dimethylvaleronitrile) is used. The amount used is 0.05 to 3% by weight based on all monomers.

The polymerization temperature varies depending on the half-life temperature of the polymerization initiator used, the amount used, the polymerizability of the monomer and the like.
To 150 ° C, preferably 50 to 100 ° C. The polymerization time is selected from a wide range, and is usually about 1 to 30 hours, preferably 3 to 18 hours. Although the polymerization method is not particularly limited, for example, when producing the most general-purpose granular resin, it is preferable to carry out the polymerization in a suspension medium. As the suspension medium, an aqueous medium, usually water, is used, and it is desirable that the aqueous medium contains a dispersion stabilizer such as xanthan gum, polyacrylate, or polyvinyl alcohol. Also, p
Various salts such as alkali and borate may be contained in order to maintain H properly.

The ratio between the monomer and the suspension medium is usually from 1/15 to 1/2 by volume. When the amount of the suspending medium is small, the suspension state becomes unstable, and when the amount is large, the productivity is lowered. The obtained crosslinked polymer is reacted with an amine represented by the following general formula (6) to introduce an anion exchange group according to a known method.

[0049]

NR ₁ R ₂ R ₃ (6) (wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
An alkyl group and having 4 or less of alkanol group having a carbon number of 4 or less carbon atoms (e.g., dimethyl ethanolamine, dimethyl propanolamine, and the like) is, R _1,
R ₂ and R ₃ are not hydrogen atoms at the same time. A) The reaction conditions for amination vary depending on the type of amine, but are usually in the range of room temperature to 100 ° C, and the reaction time is 1 to 24 hours. When a typical trimethylamine is used at a reaction condition of usually 50 ° C. for 10 hours, most of the substituent X can be converted to an amino group. In addition to this, even when dimethylethanolamine is reacted, it is possible to completely introduce the amine by reacting at 80 ° C. for 12 hours. Specific examples of the amine represented by the general formula (6) include, for example, trimethylamine, triethylamine, dimethylamine, diethylamine, dimethylethanolamine and the like.

The anion exchange resin of the present invention thus obtained has few cracks, has an appearance (proportion of resin without cracks) of 90% or more, has excellent physical strength, and has excellent heat resistance. The physical strength of the anion exchange resin of the present invention was evaluated by the crushing strength of the OH type ion exchange resin. The crushing strength is determined using OH using 600 μm particles.
Measured by mold. The crushing strength is 200 g / grain or more, preferably 300 g / grain or more, and more preferably 400 g / grain to 2000 g / grain. If the crushing strength is less than 200 g / particle, the anion exchange resin may be crushed or deformed in a state where the column is filled with water, which is not preferable. The preparation was performed by placing a preparation on a stage of a crushing strength measuring instrument (TCD-200 manufactured by Shachiron Co., Ltd.). A single ion-exchange resin (particle size: 600 μm, OH type) containing water was placed on the preparation. A load was applied to the ion exchange resin, and the strength at which the resin was crushed was measured. This operation was repeated 100 times, and the average value was defined as the crushing strength (g / particle) of the resin.

The average particle size in terms of the volume of the granular resin is usually in the range of 0.1 μm to 2 mm. More preferably, it is in the range of 0.1 mm to 1 mm. The eluted components from the strongly basic ion exchange resin are roughly divided into two. One is an eluate (unpolymerized monomer, oligomer, etc.) derived from the decomposition of anion exchange groups in the ion exchange resin resin or (oxidation) deterioration of the resin skeleton, and the other is styrene derivative or These are residues derived from the reaction products and eluates derived from the raw materials and solvents used in the reaction. The eluate from these resins can be reduced by washing in each manufacturing process.

In the stage before the reaction with the amine, for example, after polymerization, it is effective to wash the polymer with benzene, toluene, xylene, dichloroethane, methylene chloride, chloroform, THF, and isopropyl alcohol which are good solvents for the polymer. It is. It is preferable that the resin is brought into contact with the organic solvent in the range of 1.0 to 10 volumes. As a method for contacting with an organic solvent, a method of stirring in a suspended state or a method of filling a resin into a column and passing the solution through the column is used.

As a method for reducing the amount of elution at the stage of the anion exchange resin, the water-soluble organic solvent may be a loaded type (Cl type or Br type, hydrogen carbonate ion) or a regenerated type (OH type).
If washing is performed several times to about 10 volumes of the resin volume, the elution amount from the resin becomes extremely small. Preferably, the ion exchange resin is in contact with the washing solution in the regeneration type which swells most.

Another method includes washing in the presence of an alkaline solution. When treating with an alkaline solution, the type of the solution does not matter. Usually, using a solution of caustic alkali, alkali carbonate, alkali hydrogen carbonate, alcohol alkali, etc., at a pH of 12 or more, at a temperature of 50 ° C. or more, more preferably at a reflux condition of the solution or at 120 ° C. or less, for at least 30 minutes or more. Washing is preferred.

Alkylamines such as trimethylamine and dimethylamine and ammonia are said to have a correlation with the defective product rate in semiconductor production, and it is considered that reducing the amount of alkylamines will greatly increase the yield of non-defective semiconductors. ing. For this reason, an ion exchange resin with less leakage (elution) of alkylamines is required.

The concentration of the alkylamines at the outlet of the column greatly varies depending on the liquid passing speed (space velocity) and the liquid passing temperature. Here, the space velocity is a parameter indicating how many times the volume of the resin flows in one hour. Generally, when producing ultrapure water, the water flow rate of the resin tower is determined by the space velocity SV.
The value ranges from 10 (a solution having a volume of 10 times the resin volume per hour is passed) to SV300 (a solution having a volume of 300 times the resin volume is passed per hour). More preferably, the space velocity SV30
SV150. It is known that the alkylamine concentration increases as the passing water temperature increases, but ultrapure water is generally produced at 50 ° C. or lower. At space velocity SV30,
When ultrapure water was passed at a water passing temperature of 25 ° C., the concentration of alkylamines 6 hours after the start of water passing was defined as a standard condition in the present invention.

Here, it is assumed that the ultrapure water used in the present invention is highly purified water. The quality of ultrapure water used in the present invention generally has a specific resistance of 18.24M.
Ω · cm, TOC (total organic carbon) 0.5 ppb, 0.
The number of fine particles having a size of 05 μm or more is 1 / mL or less, the concentration of trialkylamines is 5 ppt, and the concentration of dialkylamines is 1 ppt. Here, the ultrapure water used as raw water is manufactured using the existing anion exchange resin, and the raw water also contains alkylamines. For this reason, the difference between the concentration of alkylamines and the concentration of amines in raw water was defined as the concentration of amines eluted from the resin. Alkylamines such as trimethylamine and dimethylamine in water, and ammonia were measured by ion chromatography after column concentration.

The anion exchange resin of the present invention can be treated in a single bed with SV.
When water is passed at 30, 25 ° C., the concentration of alkylamines (elution concentration of alkylamines) in the outlet water measured 6 hours after the start of water supply is 200 ppt or less, as measured by the above method. When the space velocity is increased to SV100, the eluted alkylamines are diluted with pure water, and the concentration of the alkylamines decreases to 100 ppt or less.

As described above, the elution concentration of alkylamines of the anion exchange resin of the present invention is 10 under standard conditions.
0 ppt or less. Further, the elution concentration of alkylamines under the above standard conditions is preferably 50 ppt or less. This is because the trimethylamine concentration is 1/100 to 1/1000 as compared with JP-A-10-24290.
To be reduced.

[0060] Anion-exchange resins are sometimes used alone, it includes cation exchange resins (strongly acidic cation exchange resin, for example, Diaion ^R SK1BH, etc. Diaion ^R SKT10 DIAION ^R PK208 is These cation exchange resins are used in a regenerated form). Usually, it is empirically known that simply mixing both ion-exchange resins causes the charged resin to become bulky due to electrostatic interaction of surface charges and to cause drift. As a method for preventing this, the charge on the surface of the anion exchange resin may be neutralized with a polymer electrolyte having the opposite charge. When treating an anion exchange resin with a water-soluble polymer electrolyte,
Examples of the polymer electrolyte include polystyrene sulfonic acid, polyvinyl benzyl sulfonic acid, poly (meth) acrylic acid, polymaleic acid, polyvinyl sulfonic acid, and salts thereof. Examples of the salt include Na salt and Ca salt.
Salts, among which Na salts are preferred. The addition amount is from 0.02 meq / L resin to 0.50 meq / L.
L resin range, further 0.05 meq / L resin to 0.3
0 meq / L resin, and further 0.10 meq / L resin
0.20 meq / L resin.

When the amount of the polymer electrolyte added is small,
Both ion-exchange resins aggregate, causing the polymer on the resin surface to peel off, causing fine particles to be generated. Conversely, when the amount of the polymer electrolyte added is large, the electrolyte does not easily diffuse into the resin, so that ion exchange tends to be inhibited. The amount of the polymer electrolyte added is 0.02 meq / L resin or less.
0.50 meq / L resin range, further 0.05 meq
/ L resin to 0.30 meq / L resin, further 0.10 m
eq / L resin to 0.20 meq / L resin.

The polymer electrolyte used here has a molecular weight of 1,000 to 1,000,000, preferably 5,000.
0 to 500,000, more preferably 5,000 to 10
It is 0,000. If the molecular weight is small, the electrolyte tends to diffuse into the polymer and inhibit desalting.
Conversely, even when the molecular weight is large, ions are difficult to diffuse, and desalination is inhibited. The polyelectrolyte must be present at least on the surface of the ion exchange resin so as to offset the charge between the particles. The polymer electrolyte may be diffused into the particles of the ion exchange resin and the charge may be neutralized. However, since the ion exchange capacity is reduced, the ion exchange group is not treated more than necessary with the polymer electrolyte.

The addition amount of the polymer electrolyte varies depending on the molecular weight. The higher the molecular weight, the smaller the addition amount of the polymer electrolyte. When the anion exchange resin is treated with, for example, polystyrene sulfonic acid, if the molecular weight is 10,000, 0.02 mm
The optimum range is from ol / L resin to 0.5 mmol / L resin. The treatment of the polymer electrolyte with the ion-exchange resin has an effect of reducing fine particles generated from the resin, in addition to suppressing aggregation of the resin due to charges of both ion-exchange resin resins.

The fine particles referred to here have a particle diameter of 0.05 μm.
m or more. The components of the fine particles are presumed to be mainly fragments of the ion exchange resin resin and aggregates from the eluted material, but the process of generating the fine particles is not clear. The generation of fine particles from the resin is not a problem with ordinary demineralized water, but the fine particles from the resin are an important problem in ultrapure water for cleaning semiconductors. Depending on the production process of ultrapure water, there is a step of capturing fine particles generated from the ion-exchange resin in a post-step of the mixed-bed ion-exchange resin, so that it may not be a fatal problem. However, it is desirable that the number of fine particles from the resin be as small as possible. When the number of fine particles having a particle size of 0.05 μm or more is passed through pure water under the conditions of space velocity SV30 and water passing temperature of 25 ° C. After 12 hours, the number of fine particles in the passing pure water is 50 particles / mL or less, preferably 10 particles / mL. As described above, in the anion exchange resin of the present invention, the eluate in the polymer is reduced by reducing impurities in the monomer, and the elution of alkylamines is reduced to an extreme by a combination of washing of the polymer. It has been reduced. Ultrapure water produced using the anion exchange resin of the present invention having such characteristics is considered to be essential as washing water when producing a semiconductor having an integration degree of 1 giga or more.

[0065]

As described above, in the monomer represented by the general formula (5) used as a reaction raw material, various impurities derived from side reactions in the synthesis process or raw materials or impurities in the raw materials are contained. Is mixed. Such impurities include, for example, styrene, bis (vinylphenyl) alkane, divinylbiphenyl, vinylphenol, chlorostyrene, dihalogenoalkane, etc. These impurities are contained to a considerable extent in the monomer.

Among these trace impurities, particularly those having one or more vinyl groups are those represented by the general formula (5)
Is polymerized with a vinyl monomer or a cross-linking agent, and is taken into the ion exchange resin produced. Heretofore, it has been considered that various vinyl compounds derived from impurities in these monomers do not substantially affect properties such as the weight and exchange capacity of the ion-exchange resin because of their small amounts. The present inventors have found that some of these impurities have a large effect on the formation of cracked (cracked) resins, and by reducing the content of components derived from these impurities in the ion exchange resin, the content of the cracked resin is reduced. A heat-resistant anion-exchange resin having excellent physical strength was obtained.

The anion exchange resin of the present invention thus obtained has a high content of crack-free resin, a high physical strength,
The product value is also excellent. By treating the surface of the anion exchange resin of the invention with a polymer electrolyte, it has become possible to suppress the generation of fine particles from the resin. Furthermore, by using the anion exchange resin of the present invention, it is possible to reduce the concentration of alkylamines in pure water to the utmost limit, and to use ultrapure water produced using the same as washing water in semiconductor production. It is expected that the use will greatly improve the product yield. The anion exchange resin of the present invention,
It is particularly useful as a semiconductor manufacturing application that requires high quality pure water.

[0068]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which should not be construed as limiting the scope of the invention. In the following examples, “%” means “% by weight” unless otherwise specified. Production Example-1 Production of 4- (4-bromobutyl) styrene (1) Nitrogen gas introduction pipe, Dimro cooling pipe, equal pressure dropping funnel with branch pipe, mercury thermometer, jacket 3 equipped with stirring blade
136.1 g of metallic magnesium in an L (liter) reactor
{5.60 gram atom, 1.40 equivalents / 4-chlorostyrene} was added, the atmosphere was sufficiently replaced with nitrogen gas, and the jacket temperature was set at 20 ° C. On the other hand, 808 g (2.8 equivalents / PCST) of dry tetrahydrofuran (THF) and 737 g (2.0 equivalents / P
CST), dry 4-chlorostyrene (PCST) 554
g (4.0 mol) of solution was prepared. First, dry THF
40 ml of the PCST THF-toluene solution 30
ml, and 1,2-dibromoethane was added thereto in an amount of 0.3 ml.
When the ml was dropped, the solution foamed and ethylene was generated, and at the same time, the internal temperature was temporarily increased to 38 ° C. After a few minutes, the solution became light gray-green and after 10 minutes became a dark green solution. The solution was dropped continuously for 3 hours so that the temperature of the solution became 28 ° C, and the jacket temperature was adjusted so that the internal temperature became 28 ° C. After dropping and aging for 3 hours, the PCST of the raw material is 0.3.
% (HPLC analysis). The prepared Grignard reagent was cooled to 10 ° C. and subjected to the next step Grignard reaction.

For a Grignard reaction, a dry nitrogen vessel was used to replace a jacketed 5 L reactor equipped with a nitrogen gas inlet tube, a Dimro cooling tube, a mercury thermometer, a stirring blade, and a Grignard solution dropping tube. On the other hand, THF 58 g (0.2 equivalent / PCS
T), 8.1 g of catalyst CuCl ₂ (0.06 mol, 1.5 mol% / PCST) and 5.0 g of LiCl (0.12 mol,
(3.0 mol% / PCST) and dissolved. Furthermore, 1,4
3454 g (16.0 mol, 4.0 equivalents / PCST) of dibromobutane was added, and the mixture was cooled to 10 ° C. About 20 ml of the above-prepared Grignard reagent is first added dropwise over 3 hours so that the internal temperature does not exceed 15 ° C., and the solution turns from an orange transparent solution to a dark (black) green transparent solution through a colorless transparent solution. It became a solution. After dropwise addition of all Grignard reagents, the mixture was stirred at 15 ° C. for 2 hours to complete the reaction. After aging,
19.2 g of methanol was dropped into the solution to stop the reaction. The yield of the desired product, 4- (4-bromobutyl) styrene, was 86%. Other components are 0.24% of 4,4′-divinylbiphenyl, 1,4-bis (vinylphenyl)
Butane 6.9%, styrene 2.4%, vinylphenol 0.3%. Deionized water was added to the above reaction solution, the mixture was allowed to stand for separation, and the aqueous phase was removed. Under reduced pressure, the solvent THF and toluene, and styrene partially generated in the reaction were removed. After removing the 1,4-dibromobutane used in a large excess, finally, the objective substance, 4- (4-bromobutyl) styrene (slightly yellowish transparent solution, boiling point: 105 ° C./40P)
a) was obtained. The purity of the obtained 4- (4-bromobutyl) styrene (BBS) is 97%, and the impurities are 1,4-bis (vinylphenyl) butane 0.7%, 4,4′-divinylbiphenyl 0.2%, 4-vinylphenol 0.08
% And 1,4-dibromobutane 1.8%.

The purified monomer was passed through silica gel (7% charged to the monomer) packed in the column to remove 4-vinylphenol. The content of 4-vinylphenol in the obtained 4- (4-bromobutyl) styrene was 0.001% (10 ppm). Table 1 shows the results. The analysis conditions are as follows. HPLC analysis; ODS column: Inertsil OD
S-2, Eluent 80% methanol aqueous solution, flow rate:
2.00 ml / min, detector: UV 254 nm, column temperature: 25 ° C., and eluent 60% MeOH aqueous solution GC analysis; GC column HP-1 (Hewlett-Packard) or DB-1 (J & W) (ID 0.25 mm × 25 m), 50 ℃ (3mi
n hold) → (temperature rise 10 ° C / min) → 280 ° C (hold 3min), detector: FID, flow rate 2.0ml / min, split ratio: 1/50, constant flow rate program Production Example-2 4- (3- Production of bromopropyl) styrene In place of 1,4-dibromobutane used in Production Example-1, 4038 g of 1,3-dibromopropane (5.0 equivalent / P
The reaction was carried out in the same manner as in Production Example 1 except that CST) was used. The yield of the desired product, 4- (3-bromopropyl) styrene, in the reaction product solution was 88%. The impurities are 4,
0.21% of 4'-divinylbiphenyl, 4.7% of 1,3-bis (vinylphenyl) propane and 2.7% of styrene.

Deionized water was added to the reaction solution to carry out liquid separation, and the aqueous phase was removed. This operation was repeated three times. TH under reduced pressure
F, toluene, and styrene partially generated in the reaction were removed. After removing the 1,3-dibromopropane used in a large excess, 4- (3-bromopropyl) styrene (a slightly yellowish transparent solution, boiling point 92 ° C./60 Pa)
I got The purity of the obtained 4- (3-bromopropyl) styrene (BPS) is 97%, and impurities are 0.2% of 4,4′-divinylbiphenyl and 0.5% of 1,3-bis (vinylphenyl) propane. , 4-vinylphenol 0.12
% And 1,3-dibromopropane 1.2%.

The purified monomer was passed through silica gel (5% loaded on the monomer) packed in a column to remove 4-vinylphenol. The obtained 4-
The vinylphenol content in (3-bromopropyl) styrene was 0.001% (10 ppm). Table 1 shows the results. Production Example-3 Production of 4- (6-bromohexyl) styrene Instead of 1,4-dibromobutane used in Production Example-1, 4880 g of 1,6-dibromohexane (5 equivalents / PCS)
The reaction was carried out in the same manner as in Production Example 1 except that T) was used. The yield of the desired product, 4- (6-bromohexyl) styrene, was 78%.

After treating in the same manner as in Production Example 1 to remove the 1,6-dibromohexane used in large excess, 4- (6-
Bromohexyl) styrene (pale yellow transparent solution, boiling point 12)
3 ° C./30 Pa). The purity of the obtained 4- (6-bromohexyl) styrene is 96.5%,
6-bis (vinylphenyl) hexane 0.7%, 4,
It was 0.2% of 4'-divinylbiphenyl, 0.06% of 4-vinylphenol, and 1.6% of 1,6-dibromohexane. Table 1 shows the results. Production Example-4 Production of 4- (4-bromobutyl) styrene (2) In the preparation of the Grignard reagent and the Grignard reaction of Production Example-1, after replacing the reactor with dry air without substituting with nitrogen, the reactor was sealed. In the same manner as in Production Example-1, 4- (4-bromobutyl) styrene was synthesized. 4- (4-
The yield of (bromobutyl) styrene was 81%. The other components were 1.24% of 4,4′-divinylbiphenyl,
5.7% of 4-bis (vinylphenyl) butane and 3.7% of styrene.

By treating in the same manner as in Production Example 1, a large excess of 1,
4-Dibromobutane was removed to obtain 4- (4-bromobutyl) styrene. The purity of the obtained 4- (4-bromobutyl) styrene is 94.4%, and the impurity is 4,4′-.
0.75% of divinylbiphenyl, 0.88% of 1,4-bis (vinylphenyl) butane, 1.23% of 4-vinylphenol, and 2.4% of 1,4-dibromobutane. Table 1 shows the results. Production Example-5 Production of 4- (4-bromobutyl) styrene (3) Instead of replacing the jacket with nitrogen gas, nitrogen gas 9
A Grignard reagent was prepared in the same manner as in Production Example 1 while flowing a mixed gas of 9% and dry air at 1% at a flow rate of 20 ml / min. Thereafter, 4- (4-bromobutyl) styrene was synthesized by the same operation as in Production Example-1.

The yield of the desired product, 4- (4-bromobutyl) styrene, was 67%. The other components were 4.3% 4,4'-divinylbiphenyl, 3.9% 1,4-bis (vinylphenyl) butane, and 3.9% styrene. A large excess of 1,4-dibromobutane was removed to obtain 4- (4-bromobutyl) styrene. The obtained 4- (4-bromobutyl) styrene has a purity of 94.8% and an impurity of 4,
2.32% of 4'-divinylbiphenyl, 0.88% of 1,4-bis (vinylphenyl) butane, 1.23% of 4-vinylphenol and 1.4% of 1,4-dibromobutane. Table 1 shows the results. Example-1 200 ml of demineralized water and 50 ml of a 2% aqueous polyvinyl alcohol solution were added to a 500 ml four-necked flask equipped with a nitrogen gas inlet tube and a cooling tube, and nitrogen was introduced. On the other hand, 54.0 g of 4-bromobutylstyrene obtained in Production Example-1
(0.226 mol), divinylbenzene (DVB) 1.5
5 g (0.00952 mol) (content 80%) and 0.37 g benzoyl peroxide (BPO) (content 75%)
Was dissolved to prepare a monomer solution. The monomer solution was placed in the flask and stirred at 220 rpm to form a suspension. After stirring at room temperature for 30 minutes, the temperature was raised to 80 ° C., and polymerization was carried out for 12 hours to obtain a crosslinked polymer with a polymerization yield of 93%.

Then, 30 g of the above resin was placed in a 500 ml four-necked flask equipped with a cooling tube, and 30 ml of toluene was added.
was added, 100 ml of a 30% aqueous solution of trimethylamine was added, and the mixture was stirred at 50 ° C. for 5 hours. After the reaction, the polymer was taken out and washed with water. A 4% aqueous solution of sodium chloride was passed 10 times the amount of the resin to convert the counter ion from the Br form to the Cl form. The amount of impurities in the obtained Cl-type resin was measured by pyrolysis gas chromatography. The structural unit of the general formula (1) was below the detection limit, and the structural unit of the general formula (2) was 0.1%.
7%, and the structural unit of the general formula (3) was 0.2%. Table 2 shows the results.

The neutral salt decomposition capacity and water content of this Cl type resin were measured. The measurement method is "Diaion: Ion Exchange Resin Manual" (Mitsubishi Kasei Kogyo Co., Ltd., published in 1976)
Followed. In addition, a certain amount of resin was observed, and the percentage of the number of crack-free resins to the total number of particles was defined as the appearance. Further, the obtained CL-type resin was regenerated into an OH-type resin, and the crushing strength of the resin was measured as follows. First, a 5% aqueous solution of sodium chloride was passed through 20 times the amount of the resin, and then 5 volumes of ultrapure water were passed through. Further, a 50% aqueous solution of 5% sodium hydrogen carbonate was passed through the resin, and 10 volumes of ultrapure water were passed through. Further, 2N-sodium hydroxide aqueous solution was passed 50 times by volume at SV5, 10 volumes of ultrapure water were passed, and it was confirmed that the pH at the outlet of the column was neutral.

Next, a crushing strength measuring instrument (TCD-20)
0 Shachiron) prepared slides on the stage,
Prepare the above OH-type resin containing water (prepared with a particle size of 60
0 μm). A load was applied to the resin, and the strength at which the resin was crushed was measured. This operation was repeated 100 times, and the average value was defined as the crushing strength (g / particle) of the resin. The results are shown in Table 1. Examples-2 and 3 and Comparative Examples-1 and 2 Using 4- (bromoalkyl) styrene obtained in Production Examples-2 to -5, the molar fraction of the crosslinking agent (divinylbenzene) was measured in Examples. In the same manner as in Example 1, an anion exchange resin was produced in the same manner as in Example 1, and converted into Cl type and OH type in the same manner, and the impurity content and performance thereof were measured. Table 1 shows the results
And Table 2.

[0079]

[Table 1]

[0080]

[Table 2]

Example 4 Into a 3 L baffled polymerization vessel were placed ₂ L of a 20% CaCl ₂ aqueous solution and a solution prepared by adjusting polyvinyl alcohol to a 0.7% aqueous solution. To this solution, a monomer solution was prepared by adding 465 g of 4- (4-bromobutyl) styrene purified by silica gel in Production Example-1, 35 g of divinylbenzene (purity: 80%), and 2.3 g of benzoyl peroxide. Use an anchor type stirring blade at room temperature for 12 hours.
After stirring at 0 rpm for 1 hour, the temperature was raised to 80 ° C. in 1 hour. After stirring at 80 rpm at 100 rpm for 8 hours, the solution was cooled. A part of the obtained polymer was taken out and dried, and the polymerization yield was measured.

50 g of the obtained polymer was placed in a flask, 300 g of toluene was added, and the mixture was stirred at room temperature for 2 hours.
After completion, the toluene solution was filtered on a Nutsche, then returned to the flask, 200 g of toluene was added, and the mixture was stirred at room temperature for 2 hours. This operation was repeated two more times to extract unpolymerized monomers and impurities. Finally, the toluene was filtered on a Nutsche.

In a 500 ml four-necked flask equipped with a cooling tube, 50 g of the above resin, 50 ml of toluene, and 200 ml of a 30% aqueous solution of trimethylamine were added.
The temperature was raised to 50 ° C., and the mixture was stirred for 5 hours. After the reaction, the polymer was taken out and washed with water. The polymer was packed in a column, 5 volumes of MeOH were passed through SV1, and demineralized water was further added to 5 BV
Water passed. In the same manner as in Example 1, conversion was sequentially made to Cl type, HCO ₃ type and OH type, and their impurity content and performance were measured. The results are shown in Tables 1 and 2.

Further, the OH type resin is further washed with ultrapure water,
An ultrapure water specification anion exchange resin was used. The neutral salt decomposition capacity of this resin was 1.03 meq / mL (OH type), and the water content was 61% (OH type). 350 mL of this OH type anion exchange resin and strongly acidic cation exchange resin
Slowly mixed Diaion ^R SKT10L 150mL, was prepared mixed bed resin. Test Example 1 Evaluation of Leakage Concentration of Alkylamines The OH-type anion exchange resin produced in Example-4 was used as a resin for ultrapure water. This resin is 30mm inside diameter
(Column length: about 78 cm), and ultrapure water (TOC 0.5 ppb) at 25 ° C. was added to SV30 and SV1.
Water was passed through at 00. The concentration of alkylamines in the outlet water of the column was determined by ion chromatography. The results are shown in Table 3 (SV
30) and Table 4 (SV100).

The analysis of alkylamines was carried out as follows. An ion chromatography apparatus was installed in a class 1000 clean room, and the measurement was performed in an online environment where ultrapure water did not come into contact with the outside air. After trapping various ions in ultrapure water of column outlet water with ion exchange resin and concentrating,
The sample was eluted with an eluent and measured with an electric conductivity detector. Table 3
And, “empty time” in Table 4 indicates the amine concentration of outlet water when ultrapure water was passed through a column not packed with resin. The unit of the numbers in Tables 2 and 3 is ppt.

[0086]

[Table 3]

[0087]

[Table 4]

TMA represents trimethylamine, and DMA represents dimesylamine. Example-5 Polymer Electrolyte Treatment 5 L of ultrapure water was placed in a beaker, and 1 L of the anion exchange resin of Example-4 was added thereto, and the resin was slowly stirred. Into this, 0.15 polystyrene sulfonic acid having a molecular weight of 50,000 was added.
The mmol / L resin was added and stirred for 1 hour. After stirring,
Transfer the resin to a glass column and add ultrapure water with SV5 for 10
L was passed through to remove excess polystyrenesulfonic acid.
The obtained resin was taken out.

The polymer electrolyte-treated anion exchange resin (350 mL) and the strongly acidic cation exchange resin Diaion
150 mL of ^R SKT10L was slowly mixed to prepare a mixed bed resin. Test Example-2 Evaluation of the number of fine particles in ultrapure water The number of fine particles in ultrapure water was evaluated. Example 4 and -5 of Example-4 and -5 were applied to a column having an inner diameter of 30 mm (column length of about 100 cm).
A mixed bed resin (500 mL) of an H-type anion exchange resin and a strongly acidic cation exchange resin was filled, and ultrapure water was added at 25 ° C. (water quality at the time of an empty column was TOC 0.50 ppb,
Specific resistance 18.25 MΩ · cm, number of fine particles 1 or less / m
L) was passed through the SV 30 and the specific resistance, TOC, and the number of fine particles (> 0.05) of the column outlet water when the steady state was reached.
μm) was measured. The quality of the outlet water was evaluated using the following analytical equipment. The fine particle meter is HORIBA PLCA-3
10. Anatel A-1000XP was used for the TOC meter, and DKK AQ11 was used for the resistivity meter.

[0090]

[Table 5]

Continuing from the front page (72) Inventor Hirohisa Kubota 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki Office (72) Inventor Tsutomu Yonemori 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki In-house (72) Inventor Masao Tate 1-1 Kurosaki Castle Stone, Yawatanishi-ku, Kitakyushu City Inside Mitsubishi Chemical Kurosaki Office (72) Inventor Toyoka Sugawara 1-1 Kurosaki Castle Stone, Yawata-nishi-ku, Kitakyushu City Mitsubishi Chemical Corporation Kurosaki Office F-term (reference) 4F071 AA22X AA32 AA36 AA39 FA10 FB01 FD04 4J100 AB07P AB15Q AB16Q BA03 BA32 BA32H BB00 CA01 CA04 CA05 CA31 HA61 HC45 JA16

Claims (46)

[Claims] 1. An anion exchange resin comprising a crosslinked copolymer having a repeating unit represented by the following general formula (2) as a main constituent unit, wherein the anion exchange resin has the following general formula (1): An anion exchange resin characterized in that the content of the structural unit represented is less than 0.5% by weight. (In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms, and R ₁ , R ₂ , and R ₃ each independently represent a hydrogen atom, an alkyl group having 4 or less carbon atoms, and an alkanol having 4 or less carbon atoms. X represents a counter ion coordinated to an ammonium group, but R ₁ , R ₂ and R ₃ are not hydrogen atoms at the same time). 2. The crosslinked copolymer contains at least one structural unit represented by the following general formulas (3) and (4), and the content of the structural unit represented by the following general formula (3) is 1 2. The anion exchange resin according to claim 1, wherein the content of the structural unit represented by the following general formula (4) is less than 2% by weight. (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 3. The cross-linked copolymer contains a compound represented by the general formula (1) or (3):
3. The composition according to claim 2, wherein the constituent units represented by (4) and (4) are simultaneously contained, and their contents are less than 0.5% by weight, less than 1.5% by weight and less than 2% by weight, respectively. Anion exchange resin. 4. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) 3. The anion exchange resin according to claim 2, wherein the content of the structural unit represented by the formula (1) is less than 0.07% by weight. 5. The method according to claim 1, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight.
5. The anion exchange resin according to any one of items 1 to 4. 6. The anion exchange resin according to claim 1, wherein in the general formula (2), A is a butylene group. 7. In the general formula (2), R ₁ , R ₂ and R ₃
Is a methyl group at the same time, the anion exchange resin according to any one of claims 1 to 6, wherein 8. A repeating unit represented by the following general formula (2)
Is the main structural unit, and the structural unit represented by the following general formula (1)
Exchange resin consisting of a cross-linked copolymer containing
Thus, the proportion of crack-free resin in the anion exchange resin is
Anion exchange resin characterized by being 90% or more(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms.
Then R₁, R_Two, And R _ThreeAre each independently a hydrogen atom or charcoal
An alkyl group having a prime number of 4 or less and an alkano having a carbon number of 4 or less
X represents a counter ion coordinated to an ammonium group.
Shows that R₁, R_Two, And R_ThreeAre simultaneously hydrogen atoms
And not). 9. The crosslinked copolymer contains at least one structural unit represented by the following general formulas (3) and (4), and the content of the structural unit represented by the following general formula (3) is 1 Less than 0.5% by weight, the content of the structural unit represented by the following general formula (4) is less than 2% by weight, and the content of the structural unit represented by the general formula (1) is less than 0.5% by weight. The anion exchange resin according to claim 8, wherein (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 10. The cross-linked copolymer has the general formula (1):
The structural unit represented by (3) and (4) is simultaneously contained, and its content is less than 0.5% by weight, less than 1.5% by weight, and less than 2% by weight, respectively. 9
Anion exchange resin as described. 11. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) The anion exchange resin according to claim 9, wherein the content of the structural unit represented by the formula (1) is less than 0.07% by weight. 12. The anion exchange resin according to claim 8, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight. 13. The anion exchange resin according to claim 8, wherein in the general formula (2), A is a butylene group. 14. In the general formula (2), R ₁ , R ₂ and R
14. The anion exchange resin according to claim 8, wherein ₃ is a methyl group at the same time. 15. A repeating unit represented by the following general formula (2):
Is a structure represented by the following general formula (1), where
An ion exchange resin consisting of a cross-linked copolymer containing units
And the crushing strength in the anion exchange resin is 200
g / particle or more. Embedded image(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms.
Then R₁, R_Two, And R _ThreeAre each independently a hydrogen atom or charcoal
An alkyl group having a prime number of 4 or less and an alkano having a carbon number of 4 or less
X represents a counter ion coordinated to an ammonium group.
Shows that R₁, R_Two, And R_ThreeAre simultaneously hydrogen atoms
And not). 16. The crosslinked copolymer contains at least one structural unit represented by the following general formulas (3) and (4),
When the content of the structural unit represented by the following general formula (3) is 1.5
Less than 2% by weight of the structural unit represented by the following general formula (4), and less than 0.5% by weight of the structural unit represented by the general formula (1). The anion exchange resin according to claim 15, characterized in that: (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 17. The compound represented by the general formula (1):
The structural unit represented by (3) and (4) is simultaneously contained, and its content is less than 0.5% by weight, less than 1.5% by weight, and less than 2% by weight, respectively. 1
6. The anion exchange resin according to 6. 18. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) 17. The anion exchange resin according to claim 16, wherein the content of the structural unit represented by the formula (1) is less than 0.07% by weight. 19. The anion exchange resin according to claim 15, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight. 20. The anion exchange resin according to claim 15, wherein in the general formula (2), A is a butylene group. 21. In the general formula (2), R ₁ , R ₂ and R
16. A compound according to claim 15, wherein ₃ is simultaneously a methyl group.
21. The anion exchange resin according to any one of the above items. 22. A repeating unit represented by the following general formula (2):
Is a structure represented by the following general formula (1), where
An ion exchange resin consisting of a cross-linked copolymer containing units
Space velocity SV30, water flow through the anion exchange resin
When pure water is passed under the condition of a temperature of 25 ° C.,
6 hours later, the concentration of alkylamines in the passing pure water
A degree of not more than 200 ppt
Exchange resin. Embedded image(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms.
Then R₁, R_Two, And R _ThreeAre each independently a hydrogen atom or charcoal
An alkyl group having a prime number of 4 or less and an alkano having a carbon number of 4 or less
X represents a counter ion coordinated to an ammonium group.
Shows that R₁, R_Two, And R_ThreeAre simultaneously hydrogen atoms
And not). 23. A crosslinked copolymer comprising at least one structural unit represented by the following general formulas (3) and (4):
When the content of the structural unit represented by the following general formula (3) is 1.5
Less than 2% by weight of the structural unit represented by the following general formula (4), and less than 0.5% by weight of the structural unit represented by the general formula (1). The anion exchange resin according to claim 22, characterized in that: (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 24. A cross-linked copolymer having the general formula (1):
The structural unit represented by (3) and (4) is simultaneously contained, and its content is less than 0.5% by weight, less than 1.5% by weight, and less than 2% by weight, respectively. 2
3. The anion exchange resin according to 3. 25. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) The anion exchange resin according to claim 23, wherein the content of the structural unit represented by the formula (1) is less than 0.07% by weight. 26. The anion exchange resin according to claim 22, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight. 27. The anion exchange resin according to claim 22, wherein in the general formula (2), A is a butylene group. 28. In the general formula (2), R ₁ , R ₂ and R
23. ₃ is a methyl group at the same time.
28. The anion exchange resin according to any one of to 27. 29. A repeating unit represented by the following general formula (2)
Is a structure represented by the following general formula (1), where
An ion exchange resin consisting of a cross-linked copolymer containing units
And the surface of the ion exchange resin is treated with a polymer electrolyte.
Anion-exchange tree characterized by the following:
Fat(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms.
Then R₁, R_Two, And R _ThreeAre each independently a hydrogen atom or charcoal
An alkyl group having a prime number of 4 or less and an alkano having a carbon number of 4 or less
X represents a counter ion coordinated to an ammonium group.
Shows that R₁, R_Two, And R_ThreeAre simultaneously hydrogen atoms
And not). 30. The crosslinked copolymer contains at least one structural unit represented by the following general formulas (3) and (4),
When the content of the structural unit represented by the following general formula (3) is 1.5
Less than 2% by weight of the structural unit represented by the following general formula (4), and less than 0.5% by weight of the structural unit represented by the general formula (1). The anion exchange resin according to claim 29, characterized by the following: (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 31. A cross-linked copolymer having the general formula (1):
The structural unit represented by (3) and (4) is simultaneously contained, and its content is less than 0.5% by weight, less than 1.5% by weight, and less than 2% by weight, respectively. 3
The anion exchange resin according to 0. 32. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) 31. The anion exchange resin according to claim 30, wherein the content of the structural unit represented by the formula) is less than 0.07% by weight. 33. The anion exchange resin according to claim 29, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight. 34. The anion exchange resin according to claim 29, wherein in the general formula (2), A is a butylene group. 35. In the general formula (2), R ₁ , R ₂ and R
30. ₃ is a methyl group at the same time.
35. The anion exchange resin according to any one of items 34 to 34. 36. The polymer electrolyte according to claim 29, wherein the polymer electrolyte is selected from the group consisting of polystyrenesulfonic acid, polyvinylbenzylsulfonic acid, poly (meth) acrylic acid, polymaleic acid, polyvinylsulfonic acid, and salts thereof. The anion exchange resin according to any one of the above. 37. A repeating unit represented by the following general formula (2):
Is a structure represented by the following general formula (1), where
An ion exchange resin consisting of a cross-linked copolymer containing units
Space velocity SV30, water flow through the anion exchange resin
When pure water is passed under the condition of a temperature of 25 ° C.,
12 hours later, 50 particles /
An anion exchange resin characterized in that the amount is not more than 0.1 ml. Embedded image(In the formula (2), A represents an alkylene group having 3 to 8 carbon atoms.
Then R₁, R_Two, And R _ThreeAre each independently a hydrogen atom or charcoal
An alkyl group having a prime number of 4 or less and an alkano having a carbon number of 4 or less
X represents a counter ion coordinated to an ammonium group.
Shows that R₁, R_Two, And R_ThreeAre simultaneously hydrogen atoms
And not). 38. The crosslinked copolymer contains at least one structural unit represented by the following general formulas (3) and (4):
When the content of the structural unit represented by the following general formula (3) is 1.5
Less than 2% by weight of the structural unit represented by the following general formula (4), and less than 0.5% by weight of the structural unit represented by the general formula (1). An anion exchange resin according to claim 37, characterized by the following: (In the formula (4), A represents an alkylene group having 3 to 8 carbon atoms). 39. The cross-linked copolymer has the general formula (1):
The structural unit represented by (3) and (4) is simultaneously contained, and its content is less than 0.5% by weight, less than 1.5% by weight, and less than 2% by weight, respectively. 3
9. The anion exchange resin according to 8. 40. The content of the structural unit represented by the general formula (3) is less than 1% by weight, the content of the structural unit represented by the general formula (4) is less than 1% by weight, and the general formula (1) 39. The anion exchange resin according to claim 38, wherein the content of the structural unit represented by the formula) is less than 0.07% by weight. 41. The anion exchange resin according to claim 37, wherein the content of the structural unit represented by the general formula (1) is less than 0.01% by weight. 42. The anion exchange resin according to claim 37, wherein in the general formula (2), A is a butylene group. 43. In the general formula (2), R ₁ , R ₂ and R
38. The combination of claim 37, wherein ₃ is simultaneously a methyl group.
45. The anion exchange resin according to any one of to 42. 44. The following general formula (5): (Wherein A represents an alkylene group having 3 to 8 carbon atoms;
Represents a halogen atom. ) And a cross-linking agent are copolymerized in the presence of a polymerization initiator, and the obtained cross-linked polymer is combined with the following general formula (6): R ₁ R ₂ R ₃ N (6 Wherein R ₁ , R ₂ and R ₃ are each independently a hydrogen atom,
An alkyl group having 4 or less carbon atoms and an alkanol group having 4 or less carbon atoms are shown, but R ₁ , R ₂ , and R ₃ are not hydrogen atoms at the same time. )), Wherein the haloalkylstyrene contains at least one compound selected from the group consisting of divinylbiphenyl, bis (vinylphenyl) alkane, and vinylphenol. And a vinylphenol content of less than 0.5% by weight. 45. The haloalkylstyrene of the general formula (5) contains divinylbiphenyl, bis (vinylphenyl) alkane and vinylphenol, and their contents are each less than 1.5% by weight, less than 2% by weight, And 0.
The method according to claim 44, wherein the amount is less than 5% by weight. 46. The content of divinylbiphenyl, bis (vinylphenyl) alkane and vinylphenol in the haloalkylstyrene of the general formula (5) is less than 1% by weight, less than 1% by weight and 0.07% by weight, respectively. 46. The method of claim 45, wherein