JP2016154505A - Method of removing electrolyte in fruit juice-containing alcoholic solution - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for stably removing electrolytes for a long period of time by using an ion exchange membrane having sufficient ion exchange performance and durability, which can efficiently remove electrolytes in a fruit juice-containing alcoholic solution by electrodialysis treatment.SOLUTION: There is provided a method for removing inorganic electrolytes and/or organic electrolytes having a molecular weight of 1000 or less contained in a fruit juice-containing alcoholic solution by electrodialysis, wherein the electrodialysis is carried out by using an ion exchange membrane including a copolymer (P) comprising a vinyl alcohol-based polymer component (A), a vinylene-based polymer component (B) and a polymer component (C) having an ionic group as constituent components as a cation exchange membrane and/or an anion exchange membrane.SELECTED DRAWING: None

Description

  The present invention relates to a method for removing an electrolyte in a fruit juice-containing alcohol solution. More specifically, the present invention relates to a method for stably and efficiently desalting an electrolyte contained in a fruit juice-containing alcohol solution by electrodialysis.

  In general, when desalting by an ion exchange membrane electrodialysis from an aqueous solution of a salt containing an organic substance, in particular, a macromolecule that becomes charged by ionization or intramolecular polarization (hereinafter also referred to as giant organic ion, etc.) There arises a problem of organic contamination of the membrane, in which giant organic ions or the like in the liquid to be treated adhere to the ion exchange membrane and deteriorate the performance of the membrane. When organic contamination occurs, electrodialysis performance decreases due to an increase in electrical resistance of the membrane, a decrease in current efficiency, a change in solution pH, and the like.

  Conventionally, ion exchange membranes that easily transmit giant organic ions or the like as ion exchange membranes that suppress organic contamination, or ion exchange membranes that prevent penetration of giant organic ions into the membrane at the membrane surface layer have been proposed. Yes. As a method for facilitating membrane permeation of giant organic ions or the like, a method of loosening the membrane structure is known (Non-Patent Document 1). However, when the membrane structure is loosened, ion selectivity is inevitably lowered, and as a result, efficient desalting cannot be performed. On the other hand, ion exchange membranes that prevent the invasion of giant organic ions into the membrane include those in which a thin layer of neutral, amphoteric or opposite ion exchange groups is formed on the membrane surface, and the membrane structure is dense. The effect is more remarkable as the molecular weight of the larger organic ions and the larger the molecular weight. For example, an anion exchange membrane (Patent Document 2) in which an oppositely charged sulfonic acid group is introduced into the surface layer portion of a resin membrane having an anion exchange group to suppress the penetration of organic anions into the membrane has been reported. There has also been reported an ion exchange membrane in which organic contamination is suppressed by introducing hydrophilic polyether into the membrane surface or inside to make the membrane surface hydrophilic (Patent Document 3).

  Furthermore, in recent years, polyvinyl alcohol ion exchange membranes that are excellent in ion exchange ability and selective permeation ability, have excellent organic contamination resistance, have high processability, and are capable of reducing costs have been attracting attention (Patent Documents). 4 and 5).

JP 2011-135815 A Japanese Patent Publication No.51-40556 Japanese Patent No. 3981598 Japanese Patent No. 4767683 International Publication No. 2010/110333 Pamphlet

Desalination, 13, 105 (1973)

  However, although the ion exchange membrane disclosed in Patent Document 2 or 3 has a certain degree of organic contamination resistance, the resistance of the ion exchange membrane by the oppositely charged layer provided on the surface layer of the resin membrane ( (Hereinafter referred to as “membrane resistance”) has a drawback of significantly increasing. In addition, a film having a hydrophilic group introduced on the surface or inside thereof has a problem that the hydrophilic group portion modified in the vicinity of the surface is lost due to long-term use or brushing washing of the film, and the organic contamination resistance is lowered.

  In addition, as for ion exchange membranes using polyvinyl alcohol copolymers as described in Patent Documents 4 and 5, since hydrophilic polyvinyl alcohol is used as a base material, it is usually bifunctional like glutaraldehyde. Insolubilization treatment with a hydroxyl group modifier such as formaldehyde or formaldehyde such as formaldehyde is indispensable, and even after insolubilization treatment, the water content is high and dimensional stability may be poor. When an electrodialysis apparatus using such an ion exchange membrane is operated for a long period of time, the ion exchange membrane swells due to water content, so that sufficient dimensional stability cannot be obtained, and the durability of the ion exchange membrane is not sufficient. Therefore, it may be difficult to perform electrodialysis stably in the long term.

  Therefore, the present invention includes a fruit juice containing an ion exchange membrane having sufficient ion exchange performance and durability that can efficiently and stably remove the electrolyte contained in the fruit juice-containing alcohol solution by electrodialysis. It is an object of the present invention to provide a method for removing an electrolyte from an alcohol solution.

  In order to solve the above-mentioned problems, the present inventors have studied in detail an ion exchange membrane used in a method for removing an electrolyte from a fruit juice-containing alcohol solution, and have completed the present invention.

［式中、０．５０００≦（ｏ^１＋ｐ^１）／（ｎ^１＋ｏ^１＋ｐ^１）≦０．９９９９であり、０．１００≦ｐ^１／（ｎ^１＋ｏ^１＋ｐ^１）≦０．９９９であり、０．０１≦ｍ^１／（ｍ^１＋ｎ^１＋ｏ^１＋ｐ^１）≦０．５０であり、Ｍはイオン性基を有する単量体Ｍ’に由来する構成単位である。］
で示される共重合体（Ｐ１）である、前記〔１〕又は〔２〕に記載の電解質の除去方法。
〔４〕前記共重合体（Ｐ）は下記一般式（２）：

［式中、０．５０００≦（ｏ^２＋ｐ^２）／（ｎ^２＋ｏ^２＋ｐ^２）≦０．９９９９であり、０．１００≦ｐ^２／（ｎ^２＋ｏ^２＋ｐ^２）≦０．９９９であり、０．００１≦ｑ^２／（ｎ^２＋ｏ^２＋ｐ^２＋ｑ^２）≦０．０５０であり、０．０１≦ｑ^２ｍ^２／（ｑ^２ｍ^２＋ｎ^２＋ｏ^２＋ｐ^２）≦０．５０であり、Ｒ^１は、水素原子又はカルボキシル基であり、Ｒ^２は、水素原子、メチル基、カルボキシル基又はカルボキシメチル基であり、Ｌは、窒素原子及び／又は酸素原子を含んでいてもよい炭素数１〜２０の２価の脂肪族炭化水素基であり、Ｒ^１がカルボキシル基の場合やＲ^２がカルボキシル基又はカルボキシメチル基の場合は、隣接する水酸基と環を形成していてもよい。Ｍはイオン性基を有する単量体Ｍ’に由来する構成単位である。］
で示される共重合体（Ｐ２）である、前記〔１〕又は〔２〕に記載の電解質の除去方法。
〔５〕前記イオン性基がアニオン性基である共重合体（Ｐ）を含有するイオン交換膜をカチオン交換膜として用いる、前記〔１〕〜〔４〕のいずれかに記載の電解質の除去方法。
〔６〕前記イオン性基がカチオン性基である共重合体（Ｐ）を含有するイオン交換膜をアニオン交換膜として用いる、前記〔１〕〜〔４〕のいずれかに記載の電解質の除去方法。
〔７〕前記イオン性基がアニオン性基である共重合体（Ｐ）を含有するイオン交換膜をカチオン交換膜として用い、前記イオン性基がカチオン性基である共重合体（Ｐ）を含有するイオン交換膜をアニオン交換膜として用いる、前記〔１〕〜〔４〕のいずれかに記載の電解質の除去方法。
〔８〕前記共重合体（Ｐ）に架橋結合が導入されている、前記〔１〕〜〔７〕のいずれかに記載の電解質の除去方法。
〔９〕前記共重合体（Ｐ）を含有するイオン交換膜は補強材料を含む、前記〔１〕〜〔８〕のいずれかに記載の電解質の除去方法。
〔１０〕前記補強材料は多孔膜、メッシュ又は不織布からなる連続した支持体である、前記〔９〕に記載の電解質の除去方法。
〔１１〕前記不織布はポリビニルアルコール系短繊維の湿式不織布である、前記〔１０〕に記載の電解質の除去方法。
〔１２〕前記共重合体（Ｐ）を含有するイオン交換膜の膜抵抗は１０Ωｃｍ^２以下である、前記〔１〕〜〔１１〕のいずれかに記載の電解質の除去方法。
〔１３〕前記電気透析により除去される前記無機電解質は無機酸及び／又は無機塩である、前記〔１〕〜〔１２〕のいずれかに記載の電解質の除去方法。
〔１４〕前記無機塩は塩化ナトリウム及び／又は塩化カリウムである、前記〔１３〕に記載の電解質の除去方法。
〔１５〕前記電気透析により除去される前記有機電解質は分子量１０００以下の有機酸及び／又は有機塩である、前記〔１〕〜〔１２〕のいずれかに記載の電解質の除去方法。
〔１６〕前記有機酸は、クエン酸、グルコン酸、酒石酸、グリシン、アラニン及びシステインからなる群から選択される少なくとも１種である、前記〔１５〕に記載の電解質の除去方法。
〔１７〕果汁含有アルコール溶液は果汁含有アルコール飲料である、前記〔１〕〜〔１６〕のいずれかに記載の電解質の除去方法。
〔１８〕前記〔１〕〜〔１７〕のいずれかに記載の電解質の除去方法を用いる、電解質が除去された果汁含有アルコール溶液の製造方法。 That is, the present invention includes the following preferred embodiments.
[1] In a method for removing an inorganic and / or organic electrolyte having a molecular weight of 1000 or less contained in a fruit juice-containing alcohol solution by electrodialysis, the electrodialysis is performed using a vinyl alcohol polymer component (A) or a vinylene polymer component. Containing fruit juice containing an ion exchange membrane comprising (B) and a copolymer (P) comprising a polymer component (C) having an ionic group as a constituent component, as a cation exchange membrane and / or an anion exchange membrane A method for removing an electrolyte contained in an alcohol solution.
[2] The copolymer (P) comprises 0.05 to 89.1 mol% of a vinyl alcohol polymer component (A), 5 to 98, based on 100 mol% of all the structural units of the copolymer (P). The method for removing an electrolyte according to the above [1], comprising 901 mol% of a vinylene polymer component (B) and 1-50 mol% of a polymer component (C) having an ionic group.
[3] The copolymer (P) is represented by the following general formula (1):

[In the formula, 0.5000 ≦ (o ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) ≦ 0.9999, 0.100 ≦ p ¹ / (n ¹ + o ¹ + p ¹ ) ≦ 0.999 Yes, 0.01 ≦ m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) ≦ 0.50, and M is a structural unit derived from the monomer M ′ having an ionic group. ]
The method for removing an electrolyte according to the above [1] or [2], which is a copolymer (P1) represented by formula (1).
[4] The copolymer (P) is represented by the following general formula (2):

[In the formula, 0.5000 ≦ (o ² + p ² ) / (n ² + o ² + p ² ) ≦ 0.9999, and 0.100 ≦ p ² / (n ² + o ² + p ² ) ≦ 0.999. Yes, 0.001 ≦ q ² / (n ² + o ² + p ² + q ² ) ≦ 0.050, 0.01 ≦ q ² m ² / (q ² m ² + n ² + o ² + p ² ) ≦ 0. 50, R ¹ is a hydrogen atom or a carboxyl group, R ² is a hydrogen atom, a methyl group, a carboxyl group or a carboxymethyl group, and L may contain a nitrogen atom and / or an oxygen atom. It is a good divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when R ¹ is a carboxyl group or R ² is a carboxyl group or a carboxymethyl group, it may form a ring with an adjacent hydroxyl group Good. M is a structural unit derived from the monomer M ′ having an ionic group. ]
The method for removing an electrolyte according to the above [1] or [2], which is a copolymer (P2) represented by:
[5] The method for removing an electrolyte according to any one of [1] to [4], wherein an ion exchange membrane containing a copolymer (P) in which the ionic group is an anionic group is used as a cation exchange membrane. .
[6] The method for removing an electrolyte according to any one of [1] to [4], wherein an ion exchange membrane containing a copolymer (P) in which the ionic group is a cationic group is used as an anion exchange membrane. .
[7] An ion exchange membrane containing a copolymer (P) in which the ionic group is an anionic group is used as a cation exchange membrane, and the copolymer (P) in which the ionic group is a cationic group The method for removing an electrolyte according to any one of [1] to [4], wherein the ion exchange membrane is used as an anion exchange membrane.
[8] The method for removing an electrolyte according to any one of [1] to [7], wherein a crosslink is introduced into the copolymer (P).
[9] The method for removing an electrolyte according to any one of [1] to [8], wherein the ion exchange membrane containing the copolymer (P) contains a reinforcing material.
[10] The method for removing an electrolyte according to [9], wherein the reinforcing material is a continuous support made of a porous film, a mesh, or a nonwoven fabric.
[11] The method for removing an electrolyte according to [10], wherein the nonwoven fabric is a wet nonwoven fabric of polyvinyl alcohol-based short fibers.
[12] The method for removing an electrolyte according to any one of [1] to [11], wherein a membrane resistance of the ion exchange membrane containing the copolymer (P) is 10 Ωcm ² or less.
[13] The method for removing an electrolyte according to any one of [1] to [12], wherein the inorganic electrolyte removed by electrodialysis is an inorganic acid and / or an inorganic salt.
[14] The method for removing an electrolyte according to [13], wherein the inorganic salt is sodium chloride and / or potassium chloride.
[15] The method for removing an electrolyte according to any one of [1] to [12], wherein the organic electrolyte removed by the electrodialysis is an organic acid and / or an organic salt having a molecular weight of 1000 or less.
[16] The method for removing an electrolyte according to [15], wherein the organic acid is at least one selected from the group consisting of citric acid, gluconic acid, tartaric acid, glycine, alanine, and cysteine.
[17] The method for removing an electrolyte according to any one of [1] to [16], wherein the fruit juice-containing alcohol solution is a fruit juice-containing alcoholic beverage.
[18] A method for producing a fruit juice-containing alcohol solution from which an electrolyte has been removed, using the method for removing an electrolyte according to any one of [1] to [17].

  According to the method for removing an electrolyte of the present invention in which an electrodialysis treatment is performed on a fruit juice-containing alcohol solution using an ion exchange membrane having sufficient ion exchange performance and durability, for example, inorganic and / or contained in the fruit juice-containing alcohol solution. Alternatively, an organic electrolyte having a molecular weight of 1000 or less (particularly inorganic acid, inorganic salt, organic acid or organic salt having a molecular weight of 1000 or less) can be efficiently and stably removed over a long period of time, and the fruit juice-containing alcohol from which the electrolyte has been removed The solution can be produced efficiently and stably over the long term.

It is explanatory drawing sectional drawing of the apparatus used for the measurement of the dynamic transport number of the ion exchange membrane used for the manufacturing method of this invention. It is explanatory sectional drawing of the apparatus used for the measurement of the membrane resistance of the ion exchange membrane used for the manufacturing method of this invention.

  The method of the present invention is a method for removing an electrolyte from a fruit juice-containing alcohol solution, in which the electrolyte is removed by subjecting the fruit juice-containing alcohol solution to electrodialysis. In the present invention, the electrodialysis treatment is a raw material in an electrodialysis tank constituted by alternately arranging a plurality of cation exchange membranes (cathode side) and anion exchange membranes (anode side) between an anode and a cathode. It means an operation of removing at least a part of the electrolyte contained in the fruit juice-containing alcohol solution by supplying an aqueous liquid containing food and energizing it. Examples of the electrolyte removed by the removing method of the present invention include inorganic and / or organic electrolytes having a molecular weight of 1000 or less, and particularly inorganic acids, inorganic salts, organic acids having a molecular weight of 1000 or less, and organic salts.

In the removal method of the present invention, as a cation exchange membrane and / or anion exchange membrane used in electrodialysis, a vinyl alcohol polymer component (A), a vinylene polymer component (B), and a polymer component having an ionic group An ion exchange membrane containing a copolymer (P) containing (C) as a constituent component is used.
In the removal method of the present invention,
(1) An ion exchange membrane comprising a copolymer (P) comprising a vinyl alcohol polymer component (A), a vinylene polymer component (B) and a polymer component (C) having an ionic group as constituent components May be used as a cation exchange membrane, and electrodialysis may be performed using an electrodialysis tank having a configuration in which the cation exchange membrane is arranged in combination with another anion exchange membrane different from the specific ion exchange membrane,
(2) An ion exchange membrane comprising a copolymer (P) comprising a vinyl alcohol polymer component (A), a vinylene polymer component (B) and a polymer component (C) having an ionic group as constituent components May be used as an anion exchange membrane, and electrodialysis may be performed using an electrodialysis tank having a configuration in which the anion exchange membrane is arranged in combination with another cation exchange membrane or the like different from the specific ion exchange membrane,
(3) An ion exchange membrane comprising a copolymer (P) comprising a vinyl alcohol polymer component (A), a vinylene polymer component (B) and a polymer component (C) having an ionic group as constituent components May be used as a cation exchange membrane and an anion exchange membrane, and electrodialysis may be performed using an electrodialysis tank having a configuration in which the cation exchange membrane and the anion exchange membrane are arranged.

[Ion exchange membrane]
The ion exchange membrane used in the removal method of the present invention is composed of a vinyl alcohol polymer component (A), a vinylene polymer component (B) and a polymer component (C) having an ionic group as constituent components. Contains coalescence (P).
Examples of the vinyl alcohol polymer component (A) include a polyvinyl alcohol component including a polyvinyl acetate component. Examples of the vinylene polymer component (B) include an oligoene component or a polyene component in which carbon-carbon single bonds and carbon-carbon double bonds are alternately connected. The ionic group contained in the polymer component (C) having an ionic group is an anionic group or a cationic group. Examples of such a polymer component (C) include poly (2-acrylamido-2-methyl). -1-propanesulfonic acid), poly (sodium parastyrene sulfonate) and poly (vinylbenzyltrimethylammonium chloride).

  The ion exchange membrane containing the copolymer (P) used in the removal method of the present invention is preferably 5% by mass or more, more preferably, based on the total amount of the ion exchange membrane, from the viewpoint of separation performance and strength. The copolymer (P) is contained in an amount of 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the content of the copolymer (P) based on the total amount of the ion exchange membrane may be 100% by mass. The ion exchange membrane used in the removal method of the present invention may be an ion exchange membrane containing only the copolymer (P), or an ion exchange membrane containing the copolymer (P) and a reinforcing material. Also good.

  When the ion exchange membrane used in the removal method of the present invention has an anionic group as an ionic group in the polymer component (C) having an ionic group, the ion exchange membrane can be used as a cation exchange membrane. . When the ion exchange membrane used in the removal method of the present invention has a cationic group as the ionic group in the polymer component (C) having an ionic group, the ion exchange membrane can be used as an anion exchange membrane. .

The copolymer (P) in the ion exchange membrane used in the removing method of the present invention is preferably 0.05 to 89.1 mol%, more preferably 100 mol% of all structural units of the copolymer (P), more preferably It contains 0.7 to 72.75 mol%, more preferably 3.75 to 47.5 mol% of vinyl alcohol polymer component (A). When the amount of the vinyl alcohol polymer component (A) is not more than the above upper limit, the water resistance of the ion exchange membrane is good, which is preferable. It is preferable that the amount of the vinyl alcohol polymer component (A) is not less than the above lower limit because the toughness of the ion exchange membrane is good.
The copolymer (P) in the ion exchange membrane used in the removal method of the present invention is preferably 5 to 98.901 mol%, more preferably 17.5 mol, based on 100 mol% of all structural units of the copolymer (P). 5 to 96.03 mol%, more preferably 37.5 to 90.25 mol% of vinylene polymer component (B) is contained. It is preferable that the amount of the vinylene polymer component (B) is not more than the above upper limit because the toughness of the ion exchange membrane is good. It is preferable that the amount of the vinylene polymer component (B) is not less than the above lower limit because the water resistance of the ion exchange membrane is good.
The copolymer (P) in the ion exchange membrane used in the removal method of the present invention is preferably 1 to 50 mol%, more preferably 3 to 30 mol, based on 100 mol% of all structural units of the copolymer (P). %, More preferably 5 to 25 mol% of the polymer component (C) having an ionic group. It is preferable for the amount of the polymer component (C) having an ionic group to be not more than the above upper limit because swelling of the ion exchange membrane can be satisfactorily suppressed. It is preferable for the amount of the polymer component (C) having an ionic group to be not less than the above lower limit because the ion conductivity is good and the ion exchange performance is easily improved.

［式中、０．５０００≦（ｏ^１＋ｐ^１）／（ｎ^１＋ｏ^１＋ｐ^１）≦０．９９９９であり、０．１００≦ｐ^１／（ｎ^１＋ｏ^１＋ｐ^１）≦０．９９９であり、０．０１≦ｍ^１／（ｍ^１＋ｎ^１＋ｏ^１＋ｐ^１）≦０．５０であり、Ｍはイオン性基を有する単量体Ｍ’に由来する構成単位である。］
で示されるブロック共重合体（以下において「共重合体（Ｐ１）」とも称する）である。 In a preferred embodiment of the present invention, the copolymer (P) is represented by the following general formula (1):

[In the formula, 0.5000 ≦ (o ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) ≦ 0.9999, 0.100 ≦ p ¹ / (n ¹ + o ¹ + p ¹ ) ≦ 0.999 Yes, 0.01 ≦ m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) ≦ 0.50, and M is a structural unit derived from the monomer M ′ having an ionic group. ]
(Hereinafter also referred to as “copolymer (P1)”).

［式中、０．５０００≦（ｏ^２＋ｐ^２）／（ｎ^２＋ｏ^２＋ｐ^２）≦０．９９９９であり、０．１００≦ｐ^２／（ｎ^２＋ｏ^２＋ｐ^２）≦０．９９９であり、０．００１≦ｑ^２／（ｎ^２＋ｏ^２＋ｐ^２＋ｑ^２）≦０．０５０であり、０．０１≦ｑ^２ｍ^２／（ｑ^２ｍ^２＋ｎ^２＋ｏ^２＋ｐ^２）≦０．５０であり、Ｒ^１は、水素原子又はカルボキシル基であり、Ｒ^２は、水素原子、メチル基、カルボキシル基又はカルボキシメチル基であり、Ｌは、窒素原子及び／又は酸素原子を含んでいてもよい炭素数１〜２０の２価の脂肪族炭化水素基であり、Ｒ^１がカルボキシル基の場合やＲ^２がカルボキシル基又はカルボキシメチル基の場合は、隣接する水酸基と環を形成していてもよい。Ｍはイオン性基を有する単量体Ｍ’に由来する構成単位である。］
で示されるグラフト共重合体（以下において「共重合体（Ｐ２）」とも称する）である。 In another preferred embodiment of the present invention, the copolymer (P) has the following general formula (2):

[In the formula, 0.5000 ≦ (o ² + p ² ) / (n ² + o ² + p ² ) ≦ 0.9999, and 0.100 ≦ p ² / (n ² + o ² + p ² ) ≦ 0.999. Yes, 0.001 ≦ q ² / (n ² + o ² + p ² + q ² ) ≦ 0.050, 0.01 ≦ q ² m ² / (q ² m ² + n ² + o ² + p ² ) ≦ 0. 50, R ¹ is a hydrogen atom or a carboxyl group, R ² is a hydrogen atom, a methyl group, a carboxyl group or a carboxymethyl group, and L may contain a nitrogen atom and / or an oxygen atom. It is a good divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when R ¹ is a carboxyl group or R ² is a carboxyl group or a carboxymethyl group, it may form a ring with an adjacent hydroxyl group Good. M is a structural unit derived from the monomer M ′ having an ionic group. ]
(Hereinafter also referred to as “copolymer (P2)”).

The symbols in the general formulas (1) and (2) will be described.
Formula in ^{(1) (o 1 + p} 1) / (n 1 + o 1 + p 1) is other than vinyl acetate units contained in the vinyl alcohol polymer component (A) and vinylene-based polymer component (B) Indicates the ratio. The lower limit of (o ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) is preferably 0.5000 or more, more preferably 0.7000 or more, and further preferably 0.8000 or more. The upper limit of (o ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) is preferably 0.9999 or less, more preferably 0.999 or less, and even more preferably 0.995 or less. (O ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) is preferably within the above range from the viewpoint of ease of production.

In the general formula (1), p ¹ / (n ¹ + o ¹ + p ¹ ) is the vinyl alcohol polymer component (A) and the vinylene polymer component (B) contained in the vinylene polymer component (B). Indicates the ratio. In this specification, this value is referred to as “polyene conversion rate”. The lower limit of the polyene conversion rate is preferably 0.100 or more, more preferably 0.250 or more, and further preferably 0.500 or more. The upper limit of the polyene conversion rate is preferably 0.999 or less, more preferably 0.99 or less, and still more preferably 0.95 or less. The polyene conversion rate is preferably not more than the above upper limit because the toughness of the ion exchange membrane is good, and is preferably not less than the above lower limit because the water resistance of the ion exchange membrane is good.

In the general formula (1), m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) represents a vinyl alcohol polymer component (A), a vinylene polymer component (B), and a polymer component having an ionic group (C ) Shows the ratio of the polymer component (C) having an ionic group contained therein. The lower limit of m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more. The upper limit of m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) is preferably 0.50 or less, more preferably 0.30 or less, and even more preferably 0.25 or less. When m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) is not more than the above upper limit, swelling of the ion exchange membrane can be favorably suppressed, and when it is not less than the above lower limit, ion conductivity is good. It is preferable because ion exchange performance is easily improved.

Formula in ^{(2) (o 2 + p} 2) / (n 2 + o 2 + p 2) is other than vinyl acetate units contained in the vinyl alcohol polymer component (A) and vinylene-based polymer component (B) Indicates the ratio. The lower limit of (o ² + p ² ) / (n ² + o ² + p ² ) is preferably 0.5000 or more, more preferably 0.7000 or more, and further preferably 0.8000 or more. The upper limit of (o ² + p ² ) / (n ² + o ² + p ² ) is preferably 0.9999 or less, more preferably 0.999 or less, and even more preferably 0.995 or less. (O ² + p ² ) / (n ² + o ² + p ² ) is preferably within the above range from the viewpoint of ease of production.

^{P 2 / (n 2 + o} 2 + p 2) in the general formula (2), vinylene-based polymer component contained in the vinyl alcohol polymer component (A) and vinylene-based polymer component (B) of (B) Indicates the ratio. In this specification, this value is also referred to as “polyene conversion rate”. The lower limit of the polyene conversion rate is preferably 0.100 or more, more preferably 0.250 or more, and further preferably 0.500 or more. The upper limit of the polyene conversion rate is preferably 0.999 or less, more preferably 0.99 or less, and still more preferably 0.95 or less. The polyene conversion rate is preferably not more than the above upper limit because the toughness of the ion exchange membrane is good, and is preferably not less than the above lower limit because the water resistance of the ion exchange membrane is good.

Q ² / (n ² + o ² + p ² + q ² ) in the general formula (2) represents a ratio of structural units having a branched structure contained in the compound represented by the general formula (2). The lower limit of q ² / (n ² + o ² + p ² + q ² ) is preferably 0.001 or more, more preferably 0.002 or more, and further preferably 0.003 or more. The upper limit of q ² / (n ² + o ² + p ² + q ² ) is preferably 0.050 or less, more preferably 0.02 or less, and still more preferably 0.01 or less. q ² / (n ² + o ² + p ² + q ² ) is preferably within the above range from the viewpoint of easy control of the copolymerization reaction.

Formula ^q 2 ^m 2 ^/ in ^{(2) (q 2 m 2} + n 2 + o 2 + p 2) a heavy having a vinyl alcohol polymer component (A), vinylene-based polymer component (B) and ionic groups The ratio of the polymer component (C) having an ionic group contained in the combined component (C) is shown. The lower limit of q ² m ² / (q ² m ² + n ² + o ² + p ² ) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more. The upper limit of q ² m ² / (q ² m ² + n ² + o ² + p ² ) is preferably 0.50 or less, more preferably 0.30 or less, and even more preferably 0.25 or less. When q ² m ² / (q ² m ² + n ² + o ² + p ² ) is not more than the above upper limit, it is preferable because swelling of the ion exchange membrane can be satisfactorily suppressed, and when it is not less than the above lower limit, ion conductivity is achieved. Is preferable, and ion exchange performance is easily improved.

In the general formulas (1) and (2), n ¹ , o ¹ , p ¹ , n ² , o ² , p ² and q ² represent the number of each repeating unit, and are independently of each other, preferably 1 10000, more preferably 5 to 9000, and even more preferably 10 to 8000. The general formulas (1) and (2) do not mean that the repeating units in parentheses are arranged as shown, but simply indicate that each repeating unit is present. The repeating units are usually arranged randomly at each other, but the same repeating units may be arranged continuously.

R ¹ in the general formula (2) is a hydrogen atom or a carboxyl group, and R ² is a hydrogen atom, a methyl group, a carboxyl group, or a carboxymethyl group. R ¹ and R ² are selected independently of each other at each occurrence.

  L in General formula (2) is a C1-C20 bivalent aliphatic hydrocarbon group which may contain a nitrogen atom and / or an oxygen atom. The number of nitrogen atoms and / or oxygen atoms contained in L is not particularly limited. The aliphatic hydrocarbon group may be linear, branched or cyclic, and is preferably linear or branched. When the aliphatic hydrocarbon group is branched, the number of carbon atoms at the site branched from the main chain of the aliphatic hydrocarbon group (a chain in which atoms are continuous between a sulfur atom and a nitrogen atom) is 1 to 5. Preferably there is. Examples of the case where L contains a nitrogen atom and / or an oxygen atom include, for example, a carbonyl bond in which the aliphatic hydrocarbon group has a nitrogen atom and / or an oxygen atom inserted into the aliphatic hydrocarbon group ( -CO-), ether bond (-O-), amino bond [-NR- (R is a hydrogen atom or a group containing carbon bonded to N)], amide bond (-CONH-), etc. The aliphatic hydrocarbon group may contain a nitrogen atom and / or an oxygen atom as a carboxyl group (—COOH), a hydroxyl group (—OH), or the like that replaces the aliphatic hydrocarbon group. From the viewpoint of raw material availability and ease of synthesis, L is preferably a linear or branched alkylene group having a total carbon number of 1 to 20 and optionally having a carboxyl group. Is preferably a linear or branched alkylene group having 2 to 15 and optionally having a carboxyl group, and having a total carbon number of 2 to 10 and optionally having a carboxyl group. More preferably, it is a chain or branched alkylene group.

  M in the general formulas (1) and (2) is a structural unit derived from a monomer having an ionic group (hereinafter also referred to as “monomer M ′”). Monomer M ′ includes a monomer composed of at least one ionic group and at least one ethylenically unsaturated monomer.

  Examples of the ionic group include an anionic group and a cationic group. When the ionic group is an anionic group, the ion exchange membrane can be used as a cation exchange membrane in the removal method of the present invention. When the ionic group is a cationic group, the ion exchange membrane can be used as an anion exchange membrane in the removal method of the present invention.

Examples of the anionic group in the monomer M ′ include a sulfonic acid group, a phosphoric acid group, a carboxylic acid group, a boronic acid group, and a sulfonylimide group. Although it does not specifically limit as a cation of a counter, Monovalent cations, such as an alkali metal ion, H ^<+> , quaternary ammonium ion, are preferable.

As the cationic group in the monomer M ′, an amino group such as an unsubstituted amino group, an N-alkylamino group or an N-dialkylamino group, a nitrogen-containing heterocyclic ring such as a pyridyl group or an imidazolyl group, or an N-trialkyl Quaternary ammonium groups such as an ammonium group, an N-alkylpyridinium group, an N-alkylimidazolium group, a thiouronium group, and an isothiouronium group can be given. The anion of the quaternary ammonium group counter is not particularly limited, but a halogenated anion of a group 5B element such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ^−, a halogenated anion of a group 3B element such as BF ₄ ⁻ , I ^{_{- (I 3 -), Br}} -, Cl - and a halogen anion, ClO ₄ ^- halogen anion such ^{_{as, AlCl 4 -, FeCl 4 -}} , SnCl 5 - represented by ^- metal halide anions such as, NO ₃ Nitrate anion, p-toluenesulfonate anion, naphthalenesulfonate anion, organic sulfonate anions such as CH ₃ SO ₃ ⁻ and CF ₃ SO ₃ ^— , carboxylate anions such as CF ₃ COO ⁻ and C ₆ H ₅ COO ⁻ , OH ^- 1 monovalent anion, and the like are preferable.

  Examples of the ethylenically unsaturated monomer in the monomer M ′ include α-olefins such as ethylene, propylene, n-butene and isobutylene; styrenes such as styrene and α-methylstyrene; acrylic acid and methyl acrylate. Acrylic acid such as ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, i-butyl acrylate, t-butyl acrylate, etc .; methacrylic acid, methyl methacrylate, Methacrylic acid or esters thereof such as ethyl methacrylate, n-propyl methacrylate, i-propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, t-butyl methacrylate; acrylamide, N-methylacrylamide, N -Ethylacrylamide, N, N-dimethylacrylic Acrylamides such as amide and diacetone acrylamide; methacrylamides such as methacrylamide, N-methyl methacrylamide, N-ethyl methacrylamide, methacrylamide propyl dimethylamine; methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, i-propyl Vinyl ethers such as vinyl ether, n-butyl vinyl ether, i-butyl vinyl ether, t-butyl vinyl ether, dodecyl vinyl ether, stearyl vinyl ether, 2,3-diacetoxy-1-vinyloxypropane; allyl acetate, 2,3-diacetoxy-1- Examples include allyl compounds such as allyloxypropane and allyl chloride; unsaturated dicarboxylic acids such as maleic acid, itaconic acid and fumaric acid, and esters thereof.

  Examples of the monomer M composed of an anionic group and an ethylenically unsaturated monomer include compounds represented by the following general formulas (3) to (9).

［式中、Ｒ^３は水素原子又はアルカリ金属原子である。］

[Wherein R ³ represents a hydrogen atom or an alkali metal atom. ]

［式中、Ｒ^３は前記と同義である。］

[Wherein R ³ has the same meaning as described above. ]

［式中、Ｒ^３は前記と同義である。］

[Wherein R ³ has the same meaning as described above. ]

［式中、Ｒ^３は前記と同義である。］

[Wherein R ³ has the same meaning as described above. ]

［式中、Ｒ^３は前記と同義である。］

[Wherein R ³ has the same meaning as described above. ]

［式中、Ｒ^３は前記と同義であり、Ｒ^４は水素原子又はメチル基である。］

[Wherein, R ³ has the same meaning as described above, and R ⁴ represents a hydrogen atom or a methyl group. ]

［式中、Ｒ^３とＲ^４は前記と同義である。］

[Wherein, R ³ and R ⁴ are as defined above. ]

  As an example of the monomer M comprised from a cationic group and an ethylenically unsaturated monomer, the compound shown by following General formula (10)-(19) is mentioned, for example.

［式中、Ｘ⁻は、ＰＦ_６ ⁻、ＳｂＦ_６ ⁻、ＡｓＦ_６ ⁻等の５Ｂ族元素のハロゲン化アニオン、ＢＦ_４ ⁻等の３Ｂ族元素のハロゲン化アニオン、Ｉ⁻（Ｉ_３ ⁻）、Ｂｒ⁻、Ｃｌ⁻等のハロゲンアニオン、ＣｌＯ_４ ⁻等のハロゲン酸アニオン、ＡｌＣｌ_４ ⁻、ＦｅＣｌ_４ ⁻、ＳｎＣｌ_５ ⁻等の金属ハロゲン化物アニオン、ＮＯ_３ ⁻で示される硝酸アニオン、ｐ−トルエンスルホン酸アニオン、ナフタレンスルホン酸アニオン、ＣＨ_３ＳＯ_３ ⁻、ＣＦ_３ＳＯ_３ ⁻等の有機スルホン酸アニオン、ＣＦ_３ＣＯＯ⁻、Ｃ_６Ｈ_５ＣＯＯ⁻等のカルボン酸アニオン、ＯＨ⁻等の１価のアニオンであり、Ｒ^４は前記と同義である。］

[Wherein, X ⁻ represents a halogenated anion of a group 5B element such as PF ₆ ⁻ , SbF ₆ ⁻ , AsF ₆ ^−, a halogenated anion of a group 3B element such as BF ₄ ⁻ , I ⁻ (I ₃ ⁻ ), Halogen anions such as Br ⁻ and Cl ⁻ , halogen acid anions such as ClO ₄ ⁻ , metal halide anions such as AlCl ₄ ⁻ , FeCl ₄ ⁻ and SnCl ₅ ⁻ , nitrate anions represented by NO ₃ ⁻ , p-toluenesulfone Monovalent cation such as acid anion, naphthalene sulfonate anion, organic sulfonate anion such as CH ₃ SO ₃ ⁻ and CF ₃ SO ₃ ^— , carboxylic acid anion such as CF ₃ COO ⁻ and C ₆ H ₅ COO ⁻ , and OH ⁻ An anion, and R ⁴ is as defined above. ]

［式中、Ｘ⁻は前記と同義である。］

[Wherein, X ⁻ has the same meaning as described above. ]

［式中、Ｘ⁻は前記と同義である。］

[Wherein, X ⁻ has the same meaning as described above. ]

［式中、Ｘ⁻は前記と同義である。］

[Wherein, X ⁻ has the same meaning as described above. ]

［式中、Ｘ⁻は前記と同義である。］

[Wherein, X ⁻ has the same meaning as described above. ]

［式中、Ｒ^４は前記と同義であり、相互に同一であっても異なっていてもよい。］

[Wherein, R ⁴ has the same meaning as described above and may be the same as or different from each other. ]

［式中、Ｒ^４は前記と同義である。］

[Wherein, R ⁴ has the same meaning as described above. ]

[Production of ion exchange membranes]
The ion exchange membrane used in the removal method of the present invention contains a copolymer (P). The ion exchange membrane containing the copolymer (P) is usually a copolymer (P ′) comprising a vinyl alcohol polymer component (A ′) and a polymer component (C) having an ionic group as constituent components. Containing a copolymer (P) by a dehydration polyene reaction, and a step I for preparing an intermediate (precursor) containing a step I, a step II for producing a film-like molded body by imparting a desired form to the intermediate The ion exchange membrane to be manufactured can be manufactured by a manufacturing method including Step III.

Step I is a step of preparing an intermediate. Step I is either of the following methods (Ia) or (Ib).
(Ia) A method of producing an intermediate containing a copolymer (P ′) by producing a vinyl alcohol polymer and then binding an ionic group to the vinyl alcohol polymer, or (Ib) vinyl A method for producing an intermediate containing a copolymer (P ′) by polymerizing an alcohol polymer and at least one monomer having an ionic group.

  As the method of (Ia), in the presence of a vinyl alcohol polymer, one or more hydroxyl group modifiers (for example, butyraldehyde sulfonic acid or its alkali metal salt, benzaldehyde sulfonic acid or its alkali metal salt, cationic ammonium aldehyde, etc.) ) Is reacted to introduce an ionic group into the vinyl alcohol polymer to produce an intermediate containing the copolymer (P ′) from the viewpoint of industrial ease. As the method of (Ib), the copolymer (P ′) is contained by radical polymerization of at least one monomer containing an ionic group in the presence of a vinyl alcohol polymer containing a mercapto group. The production of the intermediate is preferable from the viewpoint of industrial ease. Since the type and amount of each component can be easily controlled, the method (Ib) is more preferable.

［式中、０．５０００≦ｏ^３／（ｎ^３＋ｏ^３）≦０．９９９９であり、０．０１≦ｍ^３／（ｍ^３＋ｎ^３＋ｏ^３）≦０．５０であり、Ｍは前記と同義である。］
で示されるブロック共重合体（以下において「共重合体（Ｐ１’）」とも称する）、又は一般式（２１）：

［式中、０．５０００≦ｏ^４／（ｎ^４＋ｏ^４）≦０．９９９９であり、０．００１≦ｑ^４／（ｎ^４＋ｏ^４＋ｑ^４）≦０．０５であり、０．０１≦ｑ^４ｍ^４／（ｑ^４ｍ^４＋ｎ^４＋ｏ^４）≦０．５０であり、Ｒ^１、Ｒ^２、Ｌ及びＭは前記と同義である。］
で示されるグラフト共重合体（以下において「共重合体（Ｐ２’）」とも称する）が挙げられる。 As a preferable structure of the copolymer (P ′), a general formula (20);

[Wherein, 0.5000 ≦ o ³ / (n ³ + o ³ ) ≦ 0.9999, 0.01 ≦ m ³ / (m ³ + n ³ + o ³ ) ≦ 0.50, and M is It is synonymous. ]
(Hereinafter also referred to as “copolymer (P1 ′)”), or a general formula (21):

[In the formula, 0.5000 ≦ o ⁴ / (n ⁴ + o ⁴ ) ≦ 0.9999, 0.001 ≦ q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) ≦ 0.05, and 0.01 ≦ q ⁴ m ⁴ / (q ⁴ m ⁴ + n ⁴ + o ⁴ ) ≦ 0.50, and R ¹ , R ² , L and M are as defined above. ]
(Hereinafter also referred to as “copolymer (P2 ′)”).

The symbols in the general formulas (20) and (21) will be described.
In the general formula (20), o ³ / (n ³ + o ³ ) represents a ratio other than vinyl acetate units contained in the vinyl alcohol polymer component (A ′). The lower limit of o ³ / (n ³ + o ³ ) is preferably 0.5000 or more, more preferably 0.7000 or more, and further preferably 0.8000 or more. The upper limit of o ³ / (n ³ + o ³ ) is preferably 0.9999 or less, more preferably 0.999 or less, and further preferably 0.995 or less. It is preferable from the viewpoint of ease of production that o ³ / (n ³ + o ³ ) is within the above range.

M ³ / (m ³ + n ³ + o ³ ) in the general formula (20) has an ionic group contained in the vinyl alcohol polymer component (A ′) and the polymer component (C) having an ionic group. The ratio of the polymer component (C) is shown. The lower limit of m ³ / (m ³ + n ³ + o ³ ) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more. The upper limit of m ³ / (m ³ + n ³ + o ³ ) is preferably 0.50 or less, more preferably 0.30 or less, and even more preferably 0.25 or less. When m ³ / (m ³ + n ³ + o ³ ) is not more than the above upper limit, swelling of the ion exchange membrane can be favorably suppressed, and when it is not less than the above lower limit, ion conductivity is good, It is preferable because the exchange performance is easily improved.

By dehydrating the compound represented by the general formula (20), the vinyl alcohol polymer component (A ′) is converted into the vinyl alcohol polymer component (A) and the vinylene polymer component (B). . Therefore, when the block copolymer (P1 ′) represented by the general formula (20) is used as an intermediate, o ³ / (n ³ + o ³ ) in the general formula (20) is represented by the general formula (1). (O ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) Further, m ³ / (m ³ + n ³ + o ³ ) in the general formula (20) is equivalent to m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) in the general formula (1).

In the general formula (21), o ⁴ / (n ⁴ + o ⁴ ) represents a ratio other than vinyl acetate units contained in the vinyl alcohol polymer component (A ′). The lower limit of o ⁴ / (n ⁴ + o ⁴ ) is preferably 0.5000 or more, more preferably 0.7000 or more, and further preferably 0.8000 or more. The upper limit of o ⁴ / (n ⁴ + o ⁴ ) is preferably 0.9999 or less, more preferably 0.999 or less, and even more preferably 0.995 or less. o ⁴ / (n ⁴ + o ⁴ ) is preferably within the above range from the viewpoint of ease of production.

In the general formula (21), q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) represents a ratio of structural units having a branched structure contained in the compound represented by the general formula (21). The lower limit of q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) is preferably 0.001 or more, more preferably 0.002 or more, and further preferably 0.003 or more. The upper limit of q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) is preferably 0.05 or less, more preferably 0.02 or less, and still more preferably 0.01 or less. It is preferable that q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) is within the above range from the viewpoint of easy control of the copolymerization reaction.

Q ⁴ m ⁴ / (q ⁴ m ⁴ + o ⁴ + n ⁴ ) in the general formula (21) is an ionicity contained in the vinyl alcohol polymer component (A ′) and the polymer component (C) having an ionic group. The ratio of the polymer component (C) having a group is shown. The lower limit of q ⁴ m ⁴ / (q ⁴ m ⁴ + o ⁴ + n ⁴ ) is preferably 0.01 or more, more preferably 0.03 or more, and further preferably 0.05 or more. The upper limit of q ⁴ m ⁴ / (q ⁴ m ⁴ + o ⁴ + n ⁴ ) is preferably 0.50 or less, more preferably 0.30 or less, and even more preferably 0.25 or less. When q ⁴ m ⁴ / (q ⁴ m ⁴ + o ⁴ + n ⁴ ) is not more than the above upper limit, swelling of the ion exchange membrane can be satisfactorily suppressed, and when it is not less than the above lower limit, ion conductivity is good. It is preferable because it is easy to improve the ion exchange performance.

By dehydrating the compound represented by the general formula (21), the vinyl alcohol polymer component (A ′) is converted to the vinyl alcohol polymer component (A) and the vinylene polymer component (B). . Therefore, when the block copolymer (P2 ′) represented by the general formula (21) is used as an intermediate, o ⁴ / (n ⁴ + o ⁴ ) in the general formula (21) is the same as that in the general formula (2). It is equivalent to (o ² + p ² ) / (n ² + o ² + p ² ). Q ⁴ / (n ⁴ + o ⁴ + q ⁴ ) in the general formula (21) is equivalent to q ² / (n ² + o ² + p ² + q ² ) in the general formula (2). Further, q ⁴ m ⁴ / (q ⁴ m ⁴ + o ⁴ + n ⁴ ) in the general formula (21) is q ² m ² / (q ² m ² + n ² + o ² + p ² ) in the general formula (2). It is equivalent.

In the general formulas (20) and (21), n ³ , n ⁴ , o ³ , o ⁴ and q ⁴ represent the number of each repeating unit, and are independently of each other, preferably 1 to 10,000, more preferably It may be 5 to 9000, more preferably 10 to 8000. The general formulas (20) and (21) do not mean that the repeating units in parentheses are arranged as shown, but simply indicate that each repeating unit is present. The repeating units are usually arranged randomly at each other, but the same repeating units may be arranged continuously.

  The copolymer (P1 ′) is described in, for example, Patent Document 3 and Patent Document 4 using a terminal mercapto group-containing vinyl alcohol polymer and an ionic group-containing monomer (M). Can be produced by the polymerization method.

  The content rate of the vinyl alcohol unit in the above-mentioned terminal mercapto group-containing vinyl alcohol polymer (that is, the degree of saponification of the terminal mercapto group-containing vinyl alcohol polymer) is not particularly limited, but 100 mol of all the structural units in the polymer. % Is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 80 mol% or more. The upper limit of the content of the vinyl alcohol unit is preferably 99.99 mol% or less, more preferably 99.9 mol% or less, and even more preferably 99 mol%, based on 100 mol% of all structural units in the polymer. .5 mol% or less.

  The viscosity average polymerization degree measured in accordance with JIS K6726 of the above-mentioned terminal mercapto group-containing vinyl alcohol polymer is not particularly limited, and is preferably 100 to 5,000, more preferably 200 to 4,000. . The viscosity average degree of polymerization is preferably at least the above lower limit from the viewpoint of the mechanical strength of the derived copolymer. It is preferable that the viscosity average degree of polymerization is not more than the above upper limit because a vinyl alcohol polymer is easily produced industrially.

［式中、Ｒ^１、Ｒ^２及びＬは前記と同義である。］
で示される構成単位及びビニルアルコール系構成単位から構成される、一般式（２３）：

［式中、ｎ^４、ｏ^４、ｑ、Ｌ、Ｒ^１及びＲ^２は前記と同義である。］
で示される側鎖メルカプト基含有ビニルアルコール系重合体と、イオン性基を有する単量体（Ｍ）とを用いて、例えば前記特許文献３や前記特許文献４等に記載された重合方法で製造することができる。 The copolymer (P2 ′) is, for example, the general formula (22):

[Wherein, R ¹ , R ² and L are as defined above. ]
General formula (23) comprised from the structural unit shown by and vinyl alcohol type structural unit:

[Wherein, n ⁴ , o ⁴ , q, L, R ¹ and R ² are as defined above. ]
Produced by the polymerization method described in, for example, Patent Document 3 and Patent Document 4 using a side chain mercapto group-containing vinyl alcohol polymer represented by the formula (I) and a monomer (M) having an ionic group. can do.

［式中、Ｒ^１ａ及びＲ^１ｂは、水素原子又はカルボキシル基であり、但しＲ^１ａ及びＲ^１ｂの少なくとも一方は水素原子であり、Ｒ^３はメチル基であるか、Ｌに含まれる特定の炭素原子と共有結合して環状構造を形成し、Ｒ^２及びＬは前記と同義である。］
で示される不飽和二重結合を有するチオエステル系単量体から誘導することができる。 The structural unit represented by the general formula (22) can be derived from an unsaturated monomer that can be converted into the structural unit, and preferably the general formula (24):

[Wherein, R ^1a and R ^1b are a hydrogen atom or a carboxyl group, provided that at least one of R ^1a and R ^1b is a hydrogen atom, and R ³ is a methyl group or a specific carbon contained in L A cyclic structure is formed by covalent bonding with an atom, and R ² and L are as defined above. ]
It can derive from the thioester type monomer which has an unsaturated double bond shown by these.

  The thioester monomer having an unsaturated double bond represented by the general formula (24) can be produced according to a known method.

  Preferred specific examples of the thioester monomer having an unsaturated double bond represented by the general formula (24) include, for example, thioacetic acid S- (3-methyl-3-buten-1-yl) ester, thioacetic acid S-17-octadecene-1-yl ester, thioacetic acid S-15-hexadecene-1-yl ester, thioacetic acid S-14-pentadecene-1-yl ester, thioacetic acid S-13-tetradecene-1-yl ester, Thioacetic acid S-12-tridecen-1-yl ester, thioacetic acid S-11-dodecen-1-yl ester, thioacetic acid S-10-undecen-1-yl ester, thioacetic acid S-9-decene-1-yl Esters, thioacetic acid S-8-nonen-1-yl ester, thioacetic acid S-7-octen-1-yl ester, thioacetic acid S-6-hepten-1-yl ester Thioacetic acid S-5-hexen-1-yl ester, thioacetic acid S-4-penten-1-yl ester, thioacetic acid S-3-buten-1-yl ester, thioacetic acid S-2-propene-1 -Yl ester, thioacetic acid S- [1- (2-propen-1-yl) hexyl] ester, thioacetic acid S- (2,3-dimethyl-3-buten-1-yl) ester, thioacetic acid S- ( 1-ethenylbutyl) ester, thioacetic acid S- (2-hydroxy-5-hexen-1-yl) ester, thioacetic acid S- (2-hydroxy-3-buten-1-yl) ester, thioacetic acid S- (1 , 1-dimethyl-2-propen-1-yl) ester, 2-[(acetylthio) methyl] -4-pentenoic acid, thioacetic acid S- (2-methyl-2-propen-1-yl) ester, and the like, and The following chemical formula Compounds represented by a-1) ~ (a-30) can be mentioned.

  Among the above compound groups, thioacetic acid S-7-octen-1-yl ester, chemical formulas (a-6), (a-7), and (a-9) from the viewpoint of raw material availability and ease of synthesis , (A-10), (a-11), (a-12), (a-14), (a-15), (a-16), (a-17), (a-19), ( a-20), (a-21), (a-22), (a-24), (a-25), (a-26), (a-27), (a-29), (a- 30) is preferred.

  The content of the structural unit represented by the general formula (22) in the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) is not particularly limited, but the total structural unit in the polymer is 100 mol%. As for this, Preferably it is 0.1-5 mol%, More preferably, it is 0.2-2 mol%, More preferably, it is 0.3-1 mol%.

  The side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) can have one or more structural units represented by the formula (22). When it has 2 or more types of the said structural unit, it is preferable that the sum total of the content rate of these 2 or more types of structural units exists in the said range.

  The content of vinyl alcohol units in the side-chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) (that is, the degree of saponification of the side-chain mercapto group-containing vinyl alcohol polymer) is not particularly limited. The total constituent unit in the content is 100 mol%, preferably 50 mol% or more, more preferably 70 mol% or more, and further preferably 80 mol% or more. The upper limit of the content of the vinyl alcohol unit is preferably 99.99 mol% or less, more preferably 99.9 mol% or less, and even more preferably 99 mol%, based on 100 mol% of all structural units in the polymer. .5 mol% or less.

  The vinyl alcohol unit in the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) can be derived from the vinyl ester unit by hydrolysis, alcoholysis or the like. Although it does not specifically limit as vinyl ester of the vinyl ester unit converted into a vinyl alcohol unit, Vinyl acetate is preferable from an industrial viewpoint.

  As long as the effects of the present invention are obtained, the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) is a structural unit other than the structural unit represented by the formula (22), the vinyl alcohol unit, and the vinyl ester unit. Can further be included. The structural unit includes, for example, an unsaturated monomer that can be copolymerized with a vinyl ester and can be converted into a structural unit represented by the formula (22), and an ethylenically unsaturated monomer that can be copolymerized with a vinyl ester. It is a derived structural unit. The ethylenically unsaturated monomer is synonymous with the ethylenically unsaturated monomer described for the monomer M '.

  The arrangement order of the structural unit represented by the formula (22), the vinyl alcohol unit, and other arbitrary structural units in the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) is not particularly limited. , Block, alternating, etc.

  The viscosity average polymerization degree measured according to JIS K6726 of the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) is not particularly limited, and is preferably 100 to 5,000, more preferably. 200 to 4,000. The viscosity average degree of polymerization is preferably at least the above lower limit from the viewpoint of the mechanical strength of the derived copolymer. It is preferable that the viscosity average degree of polymerization is not more than the above upper limit because a vinyl alcohol polymer is easily produced industrially.

  The method for producing the side chain mercapto group-containing vinyl alcohol polymer represented by the general formula (23) is not particularly limited as long as the target side chain mercapto group-containing vinyl alcohol polymer can be produced. For example, such a production method includes copolymerization of a vinyl ester and an unsaturated monomer that can be copolymerized with the vinyl ester and can be converted into a structural unit represented by the general formula (22). Derived from an unsaturated monomer that can be converted into a vinyl alcohol unit by solvolysis, while converting the vinyl ester unit of the resulting copolymer and the copolymer to a constituent unit represented by the general formula (22) And a conversion step of converting the structural unit into the structural unit represented by the general formula (22).

  In particular, it was obtained by copolymerizing a vinyl ester and a thioester monomer having an unsaturated double bond represented by the general formula (24) (hereinafter referred to as “thioester monomer (24)”). The ester bond of the vinyl ester unit of the copolymer and the thioester bond of the structural unit derived from the thioester monomer (24) are hydrolyzed or alcoholically decomposed to give a vinyl alcohol unit and a general formula (22), respectively. The method of converting to the structural unit shown is simple and preferably used.

In the above preferred production method of the polymer represented by the general formula (23), the copolymerization of the vinyl ester and the thioester monomer (24) employs a known method and conditions for homopolymerizing the vinyl ester. Can be done. In the copolymerization, a monomer copolymerizable with the vinyl ester and thioester monomer (24) may be further copolymerized. The copolymerizable monomer is the same as the ethylenically unsaturated monomer described for the monomer M ′.
The ester bond of the vinyl ester unit of the obtained copolymer and the thioester bond of the structural unit derived from the thioester monomer (24) can be hydrolyzed or alcoholically decomposed under substantially the same conditions. Accordingly, hydrolysis or alcoholysis of the ester bond of the vinyl ester unit of the obtained copolymer and the thioester bond of the structural unit derived from the thioester monomer (24) is used to saponify the vinyl ester homopolymer. The known methods and conditions can be employed.

  Step II is a step in which a desired form is imparted to the intermediate containing the copolymer (P ′) obtained in Step I to produce a film-like molded body.

  Although it does not specifically limit as a form of the intermediate body at the time of producing a film-shaped molded object, From a viewpoint of workability, a film-shaped molded object is produced using the solution of the intermediate body containing a copolymer (P '). It is preferable. The solvent is not particularly limited, but water, methanol, ethanol, isopropanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, acetone, methyl ethyl ketone, N-methylpyrrolidone, N, N-dimethylformamide, dimethyl sulfoxide, methyl ethyl Examples thereof include polar solvents such as sulfoxide and diethyl sulfoxide, or mixed solvents thereof. From the viewpoint of the solubility of the copolymer (P ′), it is preferable to use water as a solvent. Although the density | concentration of a solution is not specifically limited, It is preferable that the quantity of the copolymer (P ') with respect to 100 mass parts of said solvent is 0.1-50 mass parts, and it is more preferable that it is 5-30 mass parts. preferable.

In the intermediate solution containing the copolymer (P ′), in addition to the copolymer (P ′) and the solvent, optional additives may be added as necessary, and the order of addition is also arbitrary. You can choose. The additive can be appropriately selected from known additives, for example, metal fine particles, inorganic fine particles, inorganic salts, ultraviolet absorbers, antioxidants, deterioration inhibitors, dispersants, surfactants, Examples thereof include polymerization inhibitors, thickeners, conductive assistants, surface modifiers, antiseptics, antifungal agents, antibacterial agents, antifoaming agents, and plasticizers. These 1 type may be used independently and may use 2 or more types together.
In the solution of the intermediate containing the copolymer (P ′), in addition to the copolymer (P ′) and the solvent, polyvinyl alcohol is appropriately added for the purpose of improving the strength of the copolymer molded product. Also good. The viscosity average polymerization degree of the polyvinyl alcohol is not particularly limited, and is preferably 500 to 8,000, more preferably 1000 to 7,000, as measured according to JIS K6726.

  The pH of the intermediate solution is preferably less than 3.0, and more preferably less than 2.0, from the viewpoint of facilitating introduction of the vinylene polymer component in the subsequent Step III. The method for adjusting the pH of the intermediate solution is not particularly limited. For example, the pH is adjusted to an acidic compound such as sulfuric acid, hydrochloric acid, acetic acid, or ammonium chloride, or a basic such as sodium hydroxide, potassium hydroxide, ammonia, or sodium acetate. The compound may be adjusted by adding it to the intermediate solution, may be adjusted using an ion exchange resin such as an anion exchange resin or a cation exchange resin, or may be adjusted by electrodialysis.

  A method for producing a polyvinyl alcohol film-like molded article by imparting a desired form to the intermediate is not particularly limited. For example, the polyvinyl alcohol polymer is heated to plasticize the polymer and molded. After forming the melt molding method (for example, extrusion molding method, injection molding method, inflation molding method, press molding method, blow molding method) or casting the solution into a film shape, the solvent is removed by drying to form the film shape. And solvent casting method. By these molding methods, a film-shaped molded article having a desired thickness such as a film or a sheet can be obtained.

  When the melt molding method is used, an arbitrary thermoplastic resin may be added to the intermediate solution as necessary, and the order of addition may be arbitrarily selected. The thermoplastic resin is not particularly limited, and a general thermoplastic resin can be used.

  When using the solvent casting method, a casting machine, a film applicator, or the like can be used, but it is not particularly limited thereto. A film-shaped molded product may be laminated on a polymer film such as a polyethylene terephthalate film, nylon film, or polypropylene, on a metal foil such as a copper foil or an aluminum foil, or on an inorganic substrate such as a glass substrate or a silicon substrate. The film-shaped molded body may have a multilayer structure. In addition, the membrane-like molded product may be composited with a porous material such as a porous film, mesh, nonwoven fabric, porous ceramics and zeolite, or molding of a three-dimensionally processed polymer, metal, ceramics, glass, etc. It may be formed on the surface of the body.

  The film thickness of the ion exchange membrane used in the removal method of the present invention is preferably about 30 to 1000 μm, from 40 to 500 μm, from the viewpoints of performance required as an electrolyte membrane for electrodialysis, mechanical strength, handling properties, and the like. More preferably, it is more preferably 50 to 300 μm. It is preferable from a viewpoint of the mechanical strength of the film | membrane obtained that a film thickness is more than said lower limit. The film thickness is preferably not more than the above upper limit from the viewpoint of reducing the membrane resistance and enhancing the ion exchange property. In the step II, it is preferable to form a film-shaped formed body having a film thickness in the above preferable range. The film thickness can be measured with a micrometer.

In step II, the film-shaped molded article can be reinforced by adding a reinforcing material made of an inorganic material, an organic material, or an organic-inorganic hybrid material in combination with the above-described production method. The reinforcing material may be a fibrous material, a particulate material, or a flaky material. Further, a continuous support such as a porous film, a mesh, and a nonwoven fabric may be used. By adding a reinforcing material, the mechanical strength and dimensional stability of the finally obtained ion exchange membrane can be further improved. In particular, it is preferable to use a fibrous material or the above-mentioned continuous support as a reinforcing material because the mechanical strength and dimensional stability of the finally obtained ion exchange membrane are easily improved. Moreover, what laminated | stacked the layer which does not reinforce and the layer which carried out the said reinforcement layer in the multilayer form by arbitrary methods is also preferable.
When processing the reinforcing material into a film-like molded body, the reinforcing material may be added to and mixed with an intermediate solution containing a copolymer (P ′), or the reinforcing material may be a copolymer ( An intermediate solution containing P ′) may be impregnated, or a reinforcing material and a film-like molded body after film formation may be laminated.

  The reinforcing material is preferably a continuous support made of a porous film, a mesh or a nonwoven fabric, more preferably a nonwoven fabric, from the viewpoint of strength and processability. As a nonwoven fabric, the wet nonwoven fabric formed from a short fiber (fiber length: 1-30 mm) is preferable. The polymer that forms the nonwoven fabric (or the constituent polymer of the main fiber) is not particularly limited, and examples thereof include polyester (PET, PTT, etc.), polyvinyl alcohol, and the like, and polyvinyl alcohol is particularly preferable. A particularly preferable nonwoven fabric sheet includes a wet nonwoven fabric mainly composed of polyvinyl alcohol short fibers. Here, the wet non-woven fabric is made by dispersing the main fibers and a small amount of binder fibers for bonding between the main fibers in water and making the slurry uniform with gentle stirring. A sheet can be formed and manufactured using an apparatus for papermaking having at least one of wires such as a formula.

  In one embodiment of the present invention in which a nonwoven fabric is used as the reinforcing material, it is preferable that the polyvinyl alcohol-based main fiber does not dissolve in water at 90 ° C. or less and has a saponification degree of 99.9 mol% or more. Moreover, the polyvinyl alcohol main fiber in which the acetalization process is performed is also preferable. The degree of acetalization is preferably 15 to 40 mol%, and more preferably 25 to 35 mol%. The polymerization degree of polyvinyl alcohol constituting the polyvinyl alcohol-based main fiber is preferably 1000 to 2500. A known method can be adopted as a method for producing the polyvinyl alcohol-based main fiber, and any one of a wet spinning method, a dry wet spinning method, and a dry spinning method may be adopted. Since the polyvinyl alcohol-based main fiber used in this embodiment is used as a wet nonwoven fabric, its fineness is preferably 0.3 to 10 dtex, more preferably 0.5 to 5 dtex.

  The inorganic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect. For example, glass fiber, carbon fiber, cellulose fiber, kaolin clay, kaolinite, halloysite, pyrophyllite, talc, montmorillonite, sericite, mica Amesite, bentonite, asbestos, zeolite, calcium carbonate, calcium silicate, diatomaceous earth, silica sand, iron ferrite, aluminum hydroxide, aluminum oxide, magnesium oxide, titanium oxide, zirconium oxide, graphite, fullerene, carbon nanotube, And carbon nanohorns. The organic material used as the reinforcing material is not particularly limited as long as it has a reinforcing effect. For example, polyvinyl alcohol, polyphenylene sulfide, polyphenylene ether, polysulfone, polyether sulfone, polyether ether sulfone, polyether ketone, polyether ether ketone , Polythioether sulfone, polythioether ether sulfone, polythioether ketone, polythioether ether ketone, polybenzimidazole, polybenzoxazole, polyoxadiazole, polybenzoxazinone, polyxylylene, polyphenylene, polythiophene, polypyrrole, polyaniline, polyacene, polycyanogen , Polynaphthyridine, polyphenylene sulfide sulfone, polyphenylene sulfone, polyimide, poly Etherimide, polyesterimide, polyamideimide, polyamide, aromatic polyamide, polystyrene, acrylonitrile-styrene resin, polystyrene-hydrogenated polybutadiene-polystyrene block copolymer, acrylonitrile-butadiene-styrene resin, polyester, polyarylate, liquid crystal polyester , Polycarbonate, polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl chloride, polyvinylidene chloride, vinylon fiber, methacrylic resin, epoxy resin, phenol resin, melamine resin, urethane resin, cellulose, polyketone, polyacetal, polypropylene and polyethylene, etc. It is done. An organic-inorganic hybrid material can also be used as a reinforcing material, and examples thereof include an organic silicon polymer compound having a silsesquioxane structure or a siloxane structure such as POSS (Polyhedral Oligomeric Silsesquioxanes) or silicone rubber.

  Step III is a film-shaped molding containing a copolymer (P ′) comprising the vinyl alcohol polymer component (A ′) obtained in Step II and a polymer component (C) having an ionic group as constituent components. A copolymer (P) containing a vinyl alcohol polymer component (A), a vinylene polymer component (B) and a polymer component (C) having an ionic group as constituents Is a step of producing an ion exchange membrane containing

  As a method for performing the dehydration polyene conversion reaction, heat treatment of the film-shaped formed body can be mentioned. The heat treatment method may be appropriately selected depending on the type and form of the film-shaped molded body, and generally known methods can be used. The heat treatment can be performed using, for example, a hot air dryer, a hot press, a hot plate, an infrared heater, a roller heater, or the like. When performing heat treatment of a large area, a planar heating means is preferable, and a hot press, a hot plate, an infrared heater, a roller heater, and the like are more preferable. The conditions for the heat treatment are not particularly limited, and are preferably 100 to 250 ° C., more preferably 140 to 200 ° C., preferably 5 seconds in the air, in an inert gas atmosphere such as nitrogen, or in a reduced pressure. The heat treatment may be performed for a heating time of ˜4 hours, more preferably 1 minute to 2 hours. The heat treatment may be performed in a plurality of times.

  The ion exchange membrane used in the removal method of the present invention may be subjected to a crosslinking treatment as necessary. It is preferable to introduce a cross-linking bond by performing a cross-linking treatment because the electrodialysis performance is easily further improved and the mechanical strength of the ion exchange membrane is easily increased. The method for the crosslinking treatment is not particularly limited as long as it is a method capable of bonding the molecular chains of the polymer by chemical bonding. Usually, a method of immersing an ion exchange membrane in a solution containing a crosslinking agent is used. Examples of the crosslinking agent include formaldehyde or dialdehyde compounds such as glyoxal and glutaraldehyde.

  As a method for performing the crosslinking treatment, a film-like molded product is produced in Step II using an intermediate solution in which the crosslinking agent is mixed in advance, and the crosslinking treatment is conducted simultaneously with polyeneization in Step III, and Step III. After polyeneization by heat treatment in step 1, the obtained ion exchange membrane is subjected to crosslinking treatment by immersing it in a solution in which a dialdehyde compound is dissolved in water, alcohol or a mixed solvent thereof under acidic conditions. A method is mentioned. In consideration of process passability, it is preferable to perform the crosslinking treatment by the latter method. When performing the crosslinking treatment by the latter method, a solution having a volume concentration of the crosslinking treatment agent with respect to the solution of 0.001 to 10% by volume is usually used.

Membrane resistance of the ion-exchange membrane containing the copolymer to be used (P) in the method for removing the present invention obtained as described above, from the viewpoint of power costs, it is preferably 10 .OMEGA.cm ² or less, 5Omucm ² below It is more preferable that Membrane resistance of the ion exchange membrane may be any 0Omucm ² or more, usually at least about 0.1? Cm ^2.

In the removal method of the present invention, (1) the specific ion exchange membrane as a cation exchange membrane may be arranged in combination with another anion exchange membrane different from the specific ion exchange membrane in the electrodialysis tank. (2) The specific ion exchange membrane as an anion exchange membrane may be arranged in combination with another cation exchange membrane or the like different from the specific ion exchange membrane, and (3) a cation exchange membrane. Further, the specific ion exchange membrane as an anion exchange membrane may be arranged.
Other anion exchange membranes different from the specific ion exchange membrane used in combination with the cation exchange membrane in the aspect (1) are not particularly limited, and strongly basic groups such as quaternary ammonium groups are used. A film made of a polymer having a weak basic functional group such as a primary amino group, a secondary amino group, or a tertiary amino group can be appropriately selected and used.
Other cation exchange membranes different from the specific ion exchange membrane used in combination with the anion exchange membrane in the aspect (2) are not particularly limited, and strongly acidic functionalities such as sulfonic acid groups and sulfonylimide groups. A film made of a polymer having a group and a film made of a polymer having a weak acid acidic functional group such as a phosphate group, a carboxylic acid group, and a boronic acid group can be appropriately selected and used.

[Fruit juice-containing alcohol solution]
In the present invention, the fruit juice used in the fruit juice-containing alcohol solution is not particularly limited as long as it is a fruit juice. For example, citrus fruit (orange, mandarin orange, lemon, grapefruit, lime, mandarin, yuzu, tangerine, Fruit juice obtained from apple, grape, peach, pineapple, guava, banana, mango, acerola, papaya, passion fruit, ume, pear, apricot, plums and the like.

  In the present invention, the alcohol solution, preferably an alcoholic beverage, is not particularly limited as long as it is alcohol for beverages. For example, alcohol for brewing, spirits (rum, vodka, gin, etc.), liqueurs, whiskey, wine, brandy or shochu can be exemplified. Moreover, not only when mixing alcohol with fruit juice, you may ferment fruit juice alcohol and prepare a fruit juice containing alcohol solution.

  In the present invention, the liquid forming the fruit juice-containing alcohol solution may be soy milk or milk in addition to water.

  In the present invention, examples of the inorganic electrolyte and / or organic electrolyte having a molecular weight of 1000 or less contained in the fruit juice-containing alcohol solution include inorganic salts such as sodium chloride, potassium chloride, calcium salts, and magnesium salts, and sulfurous acid contained in grapes. Organic acids such as inorganic acids, citric acid, gluconic acid, tartaric acid, glycine, alanine, or cysteine, or salts thereof.

  On the other hand, a high molecular weight organic compound having a molecular weight exceeding 1000 means a useful component that is desired to remain in the liquid to be treated or a component that does not need to be removed. Such high molecular weight organic compounds include sugars such as glucose, sucrose, fructose, maltose, xylose, saccharose, raffinose, and other oligosaccharides; alcohols such as methanol, ethanol, propanol, and glycerin; glycols Organic acids such as gluconic acid and humic acid or salts thereof; amino acids or salts thereof such as glutamic acid and glycine; vitamins; extracts such as pulp and seafood; polyphenols and various proteins and nucleic acids Natural polymers such as enzymes; oligopeptides; antibiotics; coenzymes; surfactants such as dodecylbenzenesulfonic acid; water-soluble synthetic polymers such as polyvinyl alcohol and polyvinylpyrrolidone .

The fruit juice-containing alcohol solution to which the electrodialysis treatment according to the present invention is applied not only contains the above-described inorganic electrolyte and / or organic electrolyte having a molecular weight of 1000 or less, but also includes organic electrolytes and organic compounds having a molecular weight exceeding 1000 (high molecular weight). In the present invention, an organic electrolyte having a molecular weight of 1000 or less can be removed from a solution containing such a high molecular weight organic compound.
In addition, from the viewpoint of production efficiency, the content of the organic electrolyte having a molecular weight of 1000 or less and the high molecular weight organic compound having a molecular weight of more than 1000 in the liquid to be treated is 1 to 100,000 ppm (weight basis, the same applies hereinafter) and It is preferably 1 to 500,000 ppm, particularly 100 to 10,000 ppm and 100 to 100,000 ppm, respectively.

  Such a liquid to be treated contains 100 to 10,000 ppm of an organic acid or the like as an organic electrolyte having a molecular weight of 1000 or less, and a total of 1,000 to 50 polyphenols or sugars as a high molecular weight organic compound having a molecular weight exceeding 1000. Undistilled liquor containing 1,000 ppm (for example, wine etc.), fruit juice, etc .; glucose containing 100 to 10,000 ppm of inorganic salts, and a total of 1,000 to 100,000 ppm of polysaccharides as high molecular weight organic compounds Examples include molasses such as fructose. That is, the method of the present invention can be suitably used particularly in a synthesis process or a purification process for foods, pharmaceuticals, agricultural chemicals, etc., a desalting process of brine or waste water, or a drinking water manufacturing process.

[Electrodialysis]
The electrodialysis tank used in the removal method of the present invention has a basic structure constituted by arranging a cation exchange membrane and an anion exchange membrane between an anode and a cathode, and the cation exchange membrane and / or anion exchange If the membrane is the specific ion exchange membrane described above, a known electrodialysis tank can be used without particular limitation. For example, an anion exchange membrane and a cation exchange membrane are alternately arranged, such as a filter press type or a unit cell type constituted by a basic structure in which a desalination chamber and a concentration chamber are formed by these ion exchange membranes and a chamber frame. Such an electrodialysis tank can be preferably used. Note that the number of membranes used in the electrodialysis tank or the channel interval (membrane interval) between the desalting chamber and the concentrating chamber may be appropriately selected depending on the type of organic matter to be processed and the amount of processing. When the high molecular weight organic compound is positively charged, the ion exchange membrane of the present invention is preferably used as the cation exchange membrane.

  The method of the present invention for removing the inorganic electrolyte and / or the organic electrolyte having a molecular weight of 1000 or less from the fruit juice-containing alcohol solution, which is the liquid to be treated, using such an electrodialysis tank, The liquid to be treated was supplied by passing a direct current between the anode and the cathode while supplying the electrolyte solution to the concentration chamber and further supplying the electrode solution made of the electrolyte solution to the cathode chamber and the anode chamber. Is done. By energizing in this manner, the inorganic electrolyte and / or the organic electrolyte having a molecular weight of 1000 or less in the fruit juice-containing alcohol solution supplied into the desalting chamber is dissociated into anions and cations, which are respectively anion exchange membrane and cation. Since it passes through the exchange membrane and is discharged to the concentration chamber side, these electrolytes can be removed from the liquid to be treated over time. In such electrodialysis, the voltage, current density, and treatment time applied to the electrodialysis tank may be appropriately determined depending on the type and concentration of the inorganic electrolyte to be removed and / or the organic electrolyte having a molecular weight of 1000 or less.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited to these Examples.

(Measurement of dynamic transportation)
The dynamic transport number of the ion exchange membrane is such that the ion exchange membrane is sandwiched in a two-chamber cell having a platinum black electrode plate shown in FIG. Went. Using ion chromatography, the change in the amount of ions before and after dialysis was calculated and substituted into the following equation to calculate the dynamic transport number t _d ⁺ .
t _d ⁺ = Δm / Ea
t _d ⁺ : dynamic transport number Ea: theoretical equivalent = I · t / F
Δm: moving equivalent F: Faraday constant

(Measurement of membrane resistance)
The membrane resistance was determined by sandwiching an ion exchange membrane in a two-chamber cell having a platinum black electrode plate shown in FIG. 2, filling a 0.5 mol / L-NaCl solution on both sides of the membrane, and an AC bridge (frequency 1000 cycles / second). Then, the resistance between the electrodes at 25 ° C. was measured, and the resistance was calculated from the difference between the resistance between the electrodes and the resistance between the electrodes when no ion exchange membrane was installed. The membrane used for the above measurement was previously equilibrated in a 0.5 mol / L-NaCl solution.

[Measurement of polyene conversion rate]
Weight after film formation after drying at 80 ° C. for 30 minutes using a hot air dryer is [weight before polyeneization], and then heat treatment is performed at 160 ° C. for 30 minutes using a high temperature heat treatment machine Is [weight after polyeneization], and all the above weight reductions ([weight before polyeneization]-[weight after polyeneization]) are all vinyl alcohol polymer components (44.05 g / mol) contained in the copolymer. ) Was dehydrated by heat treatment and converted into a vinylene polymer component (26.04 g / mol), the conversion rate was defined as the polyene conversion rate. For the material containing the reinforcing material, the weight of the copolymer was obtained by subtracting the weight of the reinforcing material from the total weight of the membrane.

Synthesis Example 1: Synthesis of terminal mercapto group-containing polyvinyl alcohol Polyvinyl alcohol having a mercapto group at its terminal by the method described in JP-A-59-187003 (polyvinyl alcohol polymer having a mercapto group at its terminal and its method) Alcohol (PVA-1, -2, -3) was synthesized. The viscosity average polymerization degree of the obtained PVA-1 measured according to JIS K6726 was 1500, and the saponification degree was 99.9 mol%. The viscosity average polymerization degree of the obtained PVA-2 measured in accordance with JIS K6726 was 1500, and the saponification degree was 97.4 mol%. The viscosity average polymerization degree of the obtained PVA-3 measured according to JIS K6726 was 500, and the saponification degree was 99.8 mol%.

Synthesis Example 2: Synthesis of thioester monomer-modified polyvinyl acetate (preceding stage of synthesis of side chain mercapto group-containing polyvinyl alcohol)
In a reactor equipped with a stirrer, a reflux condenser, an argon inlet, a comonomer addition port and a polymerization initiator addition port, 450 parts by mass of vinyl acetate, and the thioester monomer represented by the chemical formula (a-11) as a comonomer 0.64 parts by mass and 330 parts by mass of methanol were charged, and the system was purged with argon for 30 minutes while carrying out argon bubbling. Separately, a methanol solution (concentration 4% by mass) of the thioester monomer (a-11) was prepared as a comonomer sequential addition solution (hereinafter referred to as a delay solution), and argon was bubbled for 30 minutes. The temperature of the reactor was increased, and when the internal temperature reached 60 ° C., 0.1 part by mass of 2,2′-azobisisobutyronitrile was added to initiate polymerization. During the polymerization reaction, the prepared delay solution was dropped into the system so that the monomer composition in the polymerization solution (molar ratio of vinyl acetate and thioester monomer (a-11)) became constant. . After polymerization at 60 ° C. for 210 minutes, the polymerization was stopped by cooling. The polymerization rate when the polymerization was stopped was 40%. Next, unreacted vinyl acetate monomer was distilled off while adding methanol under reduced pressure at 30 ° C. to obtain a methanol solution of modified polyvinyl acetate into which the thioester monomer (a-11) was introduced.

で表される構成単位の含有量（変性量）は１．０ｍоｌ％であった。また、ＪＩＳ Ｋ６７２６に準拠して測定した粘度平均重合度は１０００、けん化度は９７．９モル％であった。 Synthesis Example 3 Synthesis of Side Chain Mercapto Group-Containing Polyvinyl Alcohol Methanol was added to a methanol solution of polyvinyl acetate into which the thioester monomer (a-11) obtained in Synthesis Example 2 was introduced, and sodium hydroxide methanol The solution (concentration 12.8%) was added, and saponification was carried out at 40 ° C. (the concentration of polyvinyl acetate into which the thioester monomer (a-11) of the saponification solution was introduced, 30%, thioester monomer) The molar ratio of sodium hydroxide to vinyl acetate units in the polyvinyl acetate introduced with (a-11) is 0.040). A gelled product was formed about 8 minutes after the addition of the sodium hydroxide methanol solution. This was pulverized by a pulverizer and further allowed to stand at 40 ° C. for 52 minutes to allow saponification to proceed. After adding the methyl acetate to this and neutralizing the remaining alkali, it wash | cleans thoroughly with methanol, By drying for 12 hours at 40 degreeC in a vacuum dryer, side chain mercapto group containing PVA (PVA-4) was obtained. . Moreover, the chemical shift value obtained by < ¹ > H-NMR measurement is shown below. Formula (I) determined by ¹ H-NMR measurement:

The content (modified amount) of the structural unit represented by 1.0 was 1.0 mol%. Moreover, the viscosity average degree of polymerization measured according to JIS K6726 was 1000, and the degree of saponification was 97.9 mol%.

¹ H-NMR (270 MHz, D ₂ O (DSS-containing), 60 ° C.) δ (ppm): 1.3-1.9 (—CH ₂ CH (OH) —), 2.0-2.2 (— _{CH 2 CH (OCOCH 3) -} ), 2.5-2.6 (CONHCH 2 CH 2 SH), 3.5-4.2 (-CH 2 CH (OH) -, - CH (COOH) CH-, CONHCH ₂ CH ₂ SH)

Synthesis Example 4: Aqueous solution P-1 (Aqueous solution of block copolymer PVA-b-AMPS)
In a 500 mL four-neck separable flask equipped with a reflux condenser and a stirring blade, 115 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , Purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 90 ° C. with stirring and dissolved while bubbling nitrogen. After nitrogen substitution, 5.6 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and 2-acrylamido-2-methylpropanesulfonic acid. An aqueous solution P-1 of the block copolymer PVA-b-AMPS was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-1 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 5 mol%.

Synthesis Example 5: Aqueous solution P-2 (Aqueous solution of block copolymer PVA-b-AMPS)
In a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 136 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , Purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was charged and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 11.9 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and 2-acrylamido-2-methylpropanesulfonic acid. An aqueous solution P-2 of the block copolymer PVA-b-AMPS was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-2 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 10 mol%.

Synthesis Example 6: Aqueous solution P-3 (Aqueous solution of block copolymer PVA-b-AMPS)
In a 500 mL four-neck separable flask equipped with a reflux condenser and a stirring blade, 154 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing terminal mercapto group and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , Purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was charged and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 17.4 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and 2-acrylamido-2-methylpropanesulfonic acid. An aqueous solution P-3 of the block copolymer PVA-b-AMPS was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-3 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of AMPS units was 14 mol%.

Synthesis Example 7: Aqueous solution P-4 (Aqueous solution of block copolymer PVA-b-AMPS)
In a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 185 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , Purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was charged and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 26.8 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and 2-acrylamido-2-methylpropanesulfonic acid. An aqueous solution P-4 of the block copolymer PVA-b-AMPS was prepared. The pH of the aqueous solution was 0.8. A part of the aqueous solution P-4 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 20 mol%.

Synthesis Example 8: Aqueous solution P-5 (Aqueous solution of block copolymer PVA-b-AMPS)
In a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 247 g of water, 25.0 g of terminal mercapto group-containing polyvinyl alcohol (PVA-1) and 2-acrylamido-2-methylpropanesulfonic acid (AMPS) , Purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 90 ° C. with stirring and dissolved while bubbling nitrogen. After nitrogen substitution, 45.9 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and 2-acrylamido-2-methylpropanesulfonic acid. An aqueous solution P-5 of the block copolymer PVA-b-AMPS was prepared. The pH of the aqueous solution was 0.8. A part of the aqueous solution P-5 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 30 mol%.

Synthesis Example 9: Aqueous solution P-6 (Aqueous solution of block copolymer PVA-b-AMPS)
The same procedure was performed except that the terminal mercapto group-containing polyvinyl alcohol (PVA-2) was used instead of the terminal mercapto group-containing polyvinyl alcohol (PVA-1) of Synthesis Example 3, and the block copolymer PVA-b-AMPS was An aqueous solution P-6 was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-6 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the modified amount of AMPS units was 14 mol%.

Synthesis Example 10: Aqueous solution P-7 (Aqueous solution of block copolymer PVA-b-AMPS)
The same procedure was performed except that the terminal mercapto group-containing polyvinyl alcohol (PVA-3) was used instead of the terminal mercapto group-containing polyvinyl alcohol (PVA-1) of Synthesis Example 3, and the block copolymer PVA-b-AMPS was An aqueous solution P-7 was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-7 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 14 mol%.

Synthesis example 11: aqueous solution P-8 (aqueous solution of graft copolymer PVA-g-AMPS)
The graft copolymer PVA-g-AMPS was performed in the same manner as in Synthesis Example 1 except that the side chain mercapto group-containing polyvinyl alcohol (PVA-4) was used instead of the terminal mercapto group-containing polyvinyl alcohol (PVA-1). An aqueous solution P-8 was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-8 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the AMPS unit was 14 mol%.

Synthesis Example 12: Aqueous solution P-9 (Aqueous solution of block copolymer PVA-b-VSA)
In a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 117 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and vinyl sulfonic acid (VSA, purity 95%: Asahi Kasei Finechem) 7.0 g) was heated to 90 ° C. with stirring and dissolved while bubbling nitrogen. After nitrogen substitution, 6.2 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 24 hours to allow the polymerization to proceed further, followed by cooling to block copolymer PVA- of polyvinyl alcohol and vinyl sulfonic acid. An aqueous solution P-9 of b-VSA was prepared. The pH of the aqueous solution was 0.9. A part of the aqueous solution P-9 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the VSA unit was 10 mol%.

Synthesis Example 13: Aqueous solution P-10 (Aqueous solution of block copolymer PVA-b-PSS)
In a 300 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 136 g of water and 25.0 g of PVA-1 as a polyvinyl alcohol having a mercapto group at the end and sodium parastyrenesulfonate (purity 90%: Tosoh Corporation) 14.0 g of organic chemistry) was charged and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 11.8 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started by adding to the polymer, and then allowed to proceed. Then, the system temperature is maintained at 90 ° C. for 4 hours to further promote the polymerization, followed by cooling, and a block copolymer of polyvinyl alcohol and sodium parastyrenesulfonate An aqueous solution P-10 of PVA-b-PSS was prepared. The pH of the aqueous solution was 7.0. A part of the aqueous solution P-10 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the PSS unit was 10 mol%.

Synthesis Example 14: Aqueous solution P-11 (Aqueous solution of block copolymer PVA-b-MAPTAC)
A 300 mL four-necked separable flask equipped with a reflux condenser and a stirring blade was charged with 138 g of water and 25.0 g of PVA-1 as a polyvinyl alcohol having a mercapto group at the end and (3-acrylamidopropyl) trimethylammonium chloride (MAPTAC). , Purity 96%: manufactured by Tokyo Chemical Industry Co., Ltd.) was heated to 90 ° C. with stirring and dissolved while bubbling nitrogen. After nitrogen substitution, 12.7 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. Polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 4 hours to allow further polymerization to proceed, followed by cooling to obtain polyvinyl alcohol and (3-acrylamidopropyl) trimethylammonium chloride. An aqueous solution P-11 of a block copolymer PVA-b-MAPTAC was prepared. The pH of the aqueous solution was 9.3. A part of the aqueous solution P-11 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the MAPTAC unit was 10 mol%.

Synthesis Example 15: Aqueous solution P-12 (Aqueous solution of block copolymer PVA-b-DAPMA)
In a 300 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 138 g of water and 25.0 g of PVA-1 as a polyvinyl alcohol having a mercapto group at the end and N- [3- (dimethylamino) propyl] 10.7 g of methacrylamide (DAPMA, purity 97%: manufactured by Wako Pure Chemical Industries, Ltd.) was added and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 9.8 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization was started and allowed to proceed, and then the system temperature was maintained at 90 ° C. for 4 hours to allow the polymerization to proceed further, followed by cooling to obtain polyvinyl alcohol and N- [3- (dimethylamino) propyl. An aqueous solution P-12 of a methacrylamide block copolymer PVA-b-DAPMA was prepared. The pH of the aqueous solution was 10.3. A part of the aqueous solution P-12 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of the DAPMA unit was 10 mol%.

Synthesis Example 16: aqueous solution P-13 (an aqueous solution of a block copolymer PVA-b-VBTAC)
To a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 137 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and vinylbenzyltrimethylammonium chloride (VBTAC, purity 97%: 13.4 g of AGC Seimi Chemical Co., Ltd.) was added and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 12.2 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 24 hours to proceed further, followed by cooling to block copolymer of polyvinyl alcohol and vinylbenzyltrimethylammonium chloride. An aqueous solution P-13 of PVA-b-VBTAC was prepared. The pH of the aqueous solution was 8.0. A part of the aqueous solution P-13 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of VBTAC units was 10 mol%.

Synthesis Example 17: Aqueous solution P-14 (an aqueous solution of a block copolymer PVA-b-VBTAC)
In a 500 mL four-necked separable flask equipped with a reflux condenser and a stirring blade, 155 g of water, 25.0 g of polyvinyl alcohol (PVA-1) containing a terminal mercapto group and vinylbenzyltrimethylammonium chloride (VBTAC, purity 97%: 19.6 g of AGC Seimi Chemical Co., Ltd.) was charged and heated to 90 ° C. with stirring to dissolve nitrogen while bubbling. After nitrogen substitution, 17.8 mL of a 2.0% aqueous solution of 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) -2-propionamide] was sequentially added to the above aqueous solution over 1.5 hours. The polymerization is started and allowed to proceed, and then the system temperature is maintained at 90 ° C. for 24 hours to proceed further, followed by cooling to block copolymer of polyvinyl alcohol and vinylbenzyltrimethylammonium chloride. An aqueous solution P-14 of PVA-b-VBTAC was prepared. The pH of the aqueous solution was 8.8. A part of the aqueous solution P-14 was dried, dissolved in heavy water, and subjected to ¹ H-NMR measurement at 500 MHz. As a result, the amount of modification of VBTAC units was 14 mol%.

Production Example 1: Production of Cation Exchange Membranes Q-1 to Q-9 Using the applicator bar on the PET film, the aqueous solutions P-1 to P-9 obtained in Synthesis Examples 4 to 12 were not adjusted to pH. After coating with a gap of 500 μm, it was dried at 80 ° C. for 30 minutes with a hot air dryer. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain cation exchange membranes Q-1 to Q-9 containing a polyene polymer component. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 1.

Production Example 2: Production of Cation Exchange Membrane Q-10 and Anion Exchange Membranes Q-11 to Q-14 To the aqueous solutions P-10 to P-14 obtained in Synthesis Examples 13 to 17, concentrated sulfuric acid was added to adjust the pH. After adjusting to 1.0, it was applied on a PET film with an applicator bar at a gap of 500 μm, and then dried at 80 ° C. for 30 minutes with a hot air dryer. Thereafter, the PET film is peeled off, and heat treatment is performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine, and the cation exchange membrane Q-10 and the anion exchange membranes Q-11 to Q containing the polyene polymer component are used. -14 was obtained. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 1.

Production Example 3: Production of Cation Exchange Membranes Q-15 and Q-16 Concentrated sulfuric acid was added to the aqueous solution P-3 obtained in Synthesis Example 6 and the aqueous solution P-10 obtained in Synthesis Example 13 to adjust the pH to 1. After applying the aqueous solution adjusted to 0.0 on a PET film with an applicator bar at a gap of 500 μm, the vinylon nonwoven fabric BNF No. 2 (made by Kuraray Co., Ltd.) was bonded and dried at 80 ° C. for 30 minutes using a hot air dryer. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes with a high-temperature heat treatment machine to obtain cation exchange membranes Q-15 and Q-16 containing a polyene polymer component. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 1.

Comparative Production Example 1: Production of ion exchange membranes R-1 to R-9 To the aqueous solutions P-1 to P-9 obtained in Synthesis Examples 4 to 12, 1.0 M sodium hydroxide was added to adjust the pH to 7 After adjusting to 0.0, it was applied on a PET film with a gap of 500 μm using an applicator bar, and then dried at 80 ° C. for 30 minutes with a hot air dryer. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain ion exchange membranes R-1 to R-9. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 2. The resulting ion exchange membrane was so leached into water that membrane resistance and dynamic transport number could not be measured.

Comparative production example 2: Production of ion exchange membranes R-10 to R-14 Using the applicator bar on the PET film, the aqueous solutions P-10 to P-14 obtained in Synthesis Examples 13 to 17 were not adjusted in pH. After coating with a gap of 500 μm, it was dried with a hot air dryer at 80 ° C. for 30 minutes. Thereafter, the PET film was peeled off, and heat treatment was performed at 160 ° C. for 30 minutes using a high-temperature heat treatment machine to obtain ion exchange membranes R-10 to R-14. The polyene conversion rate, membrane resistance, and dynamic transport number of the obtained ion exchange membrane were measured. The results are shown in Table 2. The resulting ion exchange membrane was so leached into water that membrane resistance and dynamic transport number could not be measured.

  As shown in Table 1, the ion exchange membrane used in the removal method of the present invention obtained by introducing a vinylene polymer component by polyene reaction is imparted with water resistance without being subjected to crosslinking treatment. It turns out that the performance as an ion exchange membrane is expressing (manufacture examples 1-3). On the other hand, as shown in Table 2, when the polyene reaction was not performed, the water resistance of the ion exchange membrane was inferior (Comparative Production Examples 1 and 2).

Example 1
Q-1 was used as the cation exchange membrane, and “AMX” manufactured by Astom Co., Ltd. was used as the anion exchange membrane. Desalination test of organic compounds using a small electrodialysis machine ("Micro Acylizer S3" manufactured by Astom Co., Ltd.) in which cation exchange membranes and anion exchange membranes are alternately arranged and clamped between the cathode and the anode. Carried out. At this time, the membrane to be used was washed and immersed in 0.4 mol / l saline for 1 hour for conditioning. Next, 1 L of an aqueous solution containing 1 mol / L of sucrose, 0.3 mol / L of ethanol, 0.4 mol / L of potassium chloride and 0.1 mol / L of benzethonium chloride was placed in each of the concentration tank and the dilution tank, and the current density was 10 mA at 25 ° C. Electrodialysis was performed at / cm ^{2 for} 1 hour. The desalting rate after 1 hour and the leak rate of sucrose and ethanol were measured.

  The desalination rate was measured by measuring the electrical conductivity of the fruit juice-containing alcohol solution before electrodialysis and the desalted fruit juice-containing alcohol solution after electrodialysis with an electrical conductivity meter ("ES-51" manufactured by Horiba, Ltd.). 100− (electric conductivity of desalted fruit juice-containing alcohol solution after electrodialysis treatment / electric conductivity of fruit juice-containing alcohol solution before electrodialysis treatment) × 100 (%). The sucrose leak rate is measured by a high performance liquid chromatograph (“LC-10A” manufactured by Shimadzu Corporation) of the sucrose content of the fruit juice-containing alcohol solution before electrodialysis and the desalted fruit juice-containing alcohol solution after electrodialysis. 100- (sucrose content of desalted fruit juice-containing alcohol solution after electrodialysis treatment / sucrose content of fruit juice-containing alcohol solution before electrodialysis treatment) × 100 (%). The ethanol leak rate is determined by measuring the ethanol content of the fruit juice-containing alcohol solution before electrodialysis and the desalted fruit juice-containing alcohol solution after electrodialysis with a gas chromatograph ("GC-2014" manufactured by Shimadzu Corporation) 100− (ethanol content of desalted fruit juice-containing alcohol solution after electrodialysis treatment / ethanol content of fruit juice-containing alcohol solution before electrodialysis treatment) × 100 (%). Table 3 shows the measurement results.

Examples 2-12
Table 3 shows the results measured under the same conditions as in Example 1 except that the cation exchange membrane was changed to the cation exchange membrane shown in Table 3.

Examples 13-16
Results obtained under the same conditions as in Example 1 except that the cation exchange membrane was changed to a commercially available cation exchange membrane ("CMX" manufactured by Astom Co., Ltd.) and the anion exchange membrane was changed to the anion exchange membrane shown in Table 3. Is shown in Table 3.

Examples 17-18
Table 3 shows the results measured under the same conditions as in Example 1 except that the cation exchange membrane was changed to the cation exchange membrane shown in Table 3 and the anion exchange membrane was changed to the anion exchange membrane shown in Table 3.

Comparative Examples 1-16
Table 3 shows the results measured under the same conditions as in Example 1 except that the cation exchange membrane was changed to the cation exchange membrane shown in Table 3 and the anion exchange membrane was changed to the anion exchange membrane shown in Table 3.

From the results of Table 3, the ion exchange membranes used in Examples 1 to 18 have sufficient ion exchange performance and durability as compared with Comparative Examples 1 to 16, and therefore, from the fruit juice-containing alcohol solution, It can be seen that the electrolyte can be stably removed over a long period of time, and the ion exchange performance is hardly lowered even when the electrodialysis apparatus is operated for a long time.
A copolymer (P) comprising a vinyl alcohol polymer component (A), a vinylene polymer component (B), and a polymer component (C) having an ionic group, which are used in the treatment method of the present invention, as constituent components. The ion exchange membrane to be contained becomes an ion exchange membrane having a low water content and high water resistance when the ion exchange membrane contains a vinylene polymer component. Therefore, swelling due to the water content of the ion exchange membrane is suppressed, and the ion exchange membrane is excellent in dimensional stability. According to the method of the present invention in which electrodialysis is performed using such an ion exchange membrane as a cation exchange membrane and / or an anion exchange membrane, long-term stable electrodialysis is possible, from a fruit juice-containing alcohol solution, The electrolyte can be removed efficiently and stably over the long term.

  According to the method for removing an electrolyte of the present invention in which an electrodialysis treatment is performed on a fruit juice-containing alcohol solution using an ion exchange membrane containing the copolymer (P), for example, inorganic and / or contained in the fruit juice-containing alcohol solution. An organic electrolyte having a molecular weight of 1000 or less can be efficiently and stably removed for a long time, and a fruit juice-containing alcohol solution from which the electrolyte has been removed can be produced efficiently and stably for a long time. Therefore, the method for removing an electrolyte of the present invention can be suitably used for removing an electrolyte contained in a solution such as liquors such as wine, fruit juices such as juice, and electrodialysis for liquid foods.

  While the preferred embodiments of the present invention have been described above by way of example, those skilled in the art can make various modifications, additions and substitutions without departing from the scope and spirit of the present invention disclosed in the claims. It will be understandable.

A ion exchange membrane B platinum electrode C NaCl aqueous solution D water bath E LCR meter

Claims (18)

  In the method of removing inorganic and / or organic electrolytes having a molecular weight of 1000 or less contained in a fruit juice-containing alcohol solution by electrodialysis, the electrodialysis is carried out using a vinyl alcohol polymer component (A) or a vinylene polymer component (B). And a fruit juice-containing alcohol solution using an ion exchange membrane containing a copolymer (P) containing a polymer component (C) having an ionic group as a constituent component as a cation exchange membrane and / or an anion exchange membrane A method for removing contained electrolytes.   The copolymer (P) is 0.05 to 89.1 mol% of vinyl alcohol polymer component (A), 5 to 98.901 mol, with 100 mol% of all the structural units of the copolymer (P). 2. The method for removing an electrolyte according to claim 1, comprising: 1% vinylene polymer component (B) and 1-50 mol% polymer component (C) having an ionic group. The copolymer (P) has the following general formula (1):

[In the formula, 0.5000 ≦ (o ¹ + p ¹ ) / (n ¹ + o ¹ + p ¹ ) ≦ 0.9999, 0.100 ≦ p ¹ / (n ¹ + o ¹ + p ¹ ) ≦ 0.999 Yes, 0.01 ≦ m ¹ / (m ¹ + n ¹ + o ¹ + p ¹ ) ≦ 0.50, and M is a structural unit derived from the monomer M ′ having an ionic group. ]
The removal method of the electrolyte of Claim 1 or 2 which is a copolymer (P1) shown by these. The copolymer (P) has the following general formula (2):

[In the formula, 0.5000 ≦ (o ² + p ² ) / (n ² + o ² + p ² ) ≦ 0.9999, and 0.100 ≦ p ² / (n ² + o ² + p ² ) ≦ 0.999. Yes, 0.001 ≦ q ² / (n ² + o ² + p ² + q ² ) ≦ 0.050, 0.01 ≦ q ² m ² / (q ² m ² + n ² + o ² + p ² ) ≦ 0. 50, R ¹ is a hydrogen atom or a carboxyl group, R ² is a hydrogen atom, a methyl group, a carboxyl group or a carboxymethyl group, and L may contain a nitrogen atom and / or an oxygen atom. It is a good divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and when R ¹ is a carboxyl group or R ² is a carboxyl group or a carboxymethyl group, it may form a ring with an adjacent hydroxyl group Good. M is a structural unit derived from the monomer M ′ having an ionic group. ]
The removal method of the electrolyte of Claim 1 or 2 which is a copolymer (P2) shown by these.   The method for removing an electrolyte according to any one of claims 1 to 4, wherein an ion exchange membrane containing a copolymer (P) in which the ionic group is an anionic group is used as a cation exchange membrane.   The method for removing an electrolyte according to any one of claims 1 to 4, wherein an ion exchange membrane containing a copolymer (P) in which the ionic group is a cationic group is used as an anion exchange membrane.   An ion exchange membrane containing a copolymer (P) in which the ionic group is an anionic group is used as a cation exchange membrane, and an ion exchange containing a copolymer (P) in which the ionic group is a cationic group The method for removing an electrolyte according to any one of claims 1 to 4, wherein the membrane is used as an anion exchange membrane.   The method for removing an electrolyte according to claim 1, wherein a crosslink is introduced into the copolymer (P).   The method for removing an electrolyte according to any one of claims 1 to 8, wherein the ion exchange membrane containing the copolymer (P) contains a reinforcing material.   The method for removing an electrolyte according to claim 9, wherein the reinforcing material is a continuous support made of a porous film, a mesh, or a nonwoven fabric.   The method for removing an electrolyte according to claim 10, wherein the nonwoven fabric is a wet nonwoven fabric of polyvinyl alcohol short fibers. The method for removing an electrolyte according to any one of claims 1 to 11, wherein a membrane resistance of the ion exchange membrane containing the copolymer (P) is 10 Ωcm ² or less.   The method for removing an electrolyte according to claim 1, wherein the inorganic electrolyte removed by electrodialysis is an inorganic acid and / or an inorganic salt.   The method for removing an electrolyte according to claim 13, wherein the inorganic salt is sodium chloride and / or potassium chloride.   The method for removing an electrolyte according to claim 1, wherein the organic electrolyte removed by electrodialysis is an organic acid and / or an organic salt having a molecular weight of 1000 or less.   The method for removing an electrolyte according to claim 15, wherein the organic acid is at least one selected from the group consisting of citric acid, gluconic acid, tartaric acid, glycine, alanine, and cysteine.   The method for removing an electrolyte according to any one of claims 1 to 16, wherein the fruit juice-containing alcohol solution is a fruit juice-containing alcoholic beverage.   The manufacturing method of the fruit juice containing alcohol solution from which the electrolyte was removed using the removal method of the electrolyte in any one of Claims 1-17.

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