JP5907848B2 - Polymer functional membrane and method for producing the same - Google Patents

Description

  The present invention relates to a polymer functional membrane useful for an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, a gas separation membrane or the like, and a method for producing the same.

As a polymer functional membrane, an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, a gas separation membrane, or the like is known as a membrane having various functions.
For example, ion exchange membranes are used for electrodeionization (EDI), continuous electrodeionization (CEDI), electrodialysis (ED), reverse electrodialysis (EDR), and the like. .
Electrodesalting (EDI) is a water treatment process in which ions are removed from an aqueous liquid using thin films and electrical potentials to achieve ionic transport. Unlike other water purification techniques such as conventional ion exchange, it does not require the use of chemicals such as acid or caustic soda and can be used to produce ultrapure water. Electrodialysis (ED) and reverse electrodialysis (EDR) are electrochemical separation processes that remove ions and the like from water and other fluids.

  For ion exchange membranes, studies have been made on improving transport number and pH resistance (see, for example, Patent Documents 1 to 3). However, further improvement in performance as a polymer functional film is required, and improvement in the characteristics of other polymer functional films is also required.

International Publication No. 2011/073637 Pamphlet International Publication No. 2011/073638 Pamphlet International Publication No. 2011/025867 Pamphlet

  In the present inventors' research, the conventional polymer functional membrane has room for further improvement in, for example, pH resistance, and in order to remarkably enhance the use as a polymer functional membrane, It was found that it is important to further reduce the water permeability.

  It is an object of the present invention to provide a polymer functional membrane that can be used in a wide range of applications and has excellent water permeability suppression and pH resistance without reducing the transport number of various substances, and a method for producing the same. And Among them, in particular, the object of the present invention is to provide a polymer functional membrane as an ion exchange membrane excellent in water permeability suppression, ion transport number and pH resistance.

  In view of the above problems, the present inventors have intensively studied a polymerizable compound suitable for a polymer functional film. As a result, the polymer functional film using the polyfunctional polymerizable compound having the structure represented by the following general formula (1) not only exhibits good ion transport number and pH resistance, but also serves as an ion exchange film. It has been found that it exhibits good low water permeability when used. The present invention has been made based on these findings.

（一般式（１）中、Ｒ^１は水素原子またはメチル基を表す。Ｌ^１は炭素原子数２〜４の直鎖もしくは分岐のアルキレン基を表す。ただし、Ｌ^１において、Ｌ^１の両端に結合する酸素原子と窒素原子とがＬ^１の同一の炭素原子に結合した構造をとることはない。Ｌ^２は２価の連結基を表す。ｋは２または３を表す。ｘ、ｙおよびｚは、各々独立に０〜６の整数を表し、ｘ＋ｙ＋ｚは０〜１８を満たす。）
＜２＞前記（Ｂ）単官能重合性化合物が、解離基を有する前記＜１＞項に記載の高分子機能性膜。
＜３＞前記解離基が、スルホ基もしくその塩、カルボキシル基もしくはその塩、アンモニオ基およびピリジニオ基から選択される前記＜２＞項に記載の高分子機能性膜。
＜４＞前記（Ｂ）単官能重合性化合物が、（メタ）アクリレートまたは（メタ）アクリルアミドである前記＜１＞〜＜３＞項のいずれか１項に記載の高分子機能性膜。
＜５＞前記（Ｂ）単官能重合性化合物１００質量部に対して、前記（Ａ）一般式（１）で表される重合性化合物が、１〜４５質量部である前記＜１＞〜＜４＞項のいずれか１項に記載の高分子機能性膜。
＜６＞前記組成物が、さらに（Ｅ）溶媒を含む前記＜１＞〜＜５＞項のいずれか１項に記載の高分子機能性膜。
＜７＞前記（Ｅ）溶媒が、水および水溶性溶媒から選択される溶媒である前記＜６＞項に記載の高分子機能性膜。
＜８＞前記組成物中の前記（Ｅ）溶媒の含有量が、１０〜５０質量％である前記＜６＞又は＜７＞項に記載の高分子機能性膜。
＜９＞支持体を有する前記＜１＞〜＜８＞項のいずれか１項に記載の高分子機能性膜。
＜１０＞前記高分子機能性膜が、イオン交換膜、逆浸透膜、正浸透膜またはガス分離膜である前記＜１＞〜＜９＞項のいずれか１項に記載の高分子機能性膜。
＜１１＞支持体を有し、（Ａ）下記一般式（１）で表される重合性化合物、及び（Ｂ）単官能重合性化合物を含有する組成物を硬化反応させる高分子機能性膜の製造方法であって、
前記組成物を前記支持体に含浸させた後に硬化反応する高分子機能性膜の製造方法。

（一般式（１）中、Ｒ^１は水素原子またはメチル基を表す。Ｌ^１は炭素原子数２〜４の直鎖もしくは分岐のアルキレン基を表す。ただし、Ｌ^１において、Ｌ^１の両端に結合する酸素原子と窒素原子とがＬ^１の同一の炭素原子に結合した構造をとることはない。Ｌ^２は２価の連結基を表す。ｋは２または３を表す。ｘ、ｙおよびｚは、各々独立に０〜６の整数を表し、ｘ＋ｙ＋ｚは０〜１８を満たす。）
＜１２＞（Ａ）下記一般式（１）で表される重合性化合物、（Ｂ）単官能重合性化合物を含有する組成物をエネルギー線照射して重合する高分子機能性膜の製造方法。

（一般式（１）中、Ｒ^１は水素原子またはメチル基を表す。Ｌ^１は炭素原子数２〜４の直鎖もしくは分岐のアルキレン基を表す。ただし、Ｌ^１において、Ｌ^１の両端に結合する酸素原子と窒素原子とがＬ^１の同一の炭素原子に結合した構造をとることはない。Ｌ^２は２価の連結基を表す。ｋは２または３を表す。ｘ、ｙおよびｚは、各々独立に０〜６の整数を表し、ｘ＋ｙ＋ｚは０〜１８を満たす。）
That is, the said subject of this invention was solved by the following means.
<1> (A) A polymer functional film obtained by curing a composition containing a polymerizable compound represented by the following general formula (1) and (B) a monofunctional polymerizable compound.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.)
<2> The polymer functional film according to <1>, wherein the (B) monofunctional polymerizable compound has a dissociation group.
<3> The polymer functional membrane according to <2>, wherein the dissociating group is selected from a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an ammonio group, and a pyridinio group.
<4> The polymer functional film according to any one of <1> to <3>, wherein the (B) monofunctional polymerizable compound is (meth) acrylate or (meth) acrylamide.
<5> The <1> to <1> in which the polymerizable compound represented by the general formula (1) is 1 to 45 parts by mass with respect to 100 parts by mass of the (B) monofunctional polymerizable compound. Item 4> The polymer functional film according to any one of Items.
<6> The polymer functional film according to any one of <1> to <5>, wherein the composition further comprises (E) a solvent.
<7> The polymer functional film according to <6>, wherein the solvent (E) is a solvent selected from water and a water-soluble solvent.
<8> The polymer functional film according to <6> or <7>, wherein the content of the solvent (E) in the composition is 10 to 50% by mass.
<9> The polymer functional film according to any one of <1> to <8>, having a support.
< 10 > The polymer functional membrane according to any one of <1> to < 9 >, wherein the polymer functional membrane is an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, or a gas separation membrane. .
< 11 > A polymer functional film having a support and (A) a polymerizable compound represented by the following general formula (1) and (B) a composition containing a monofunctional polymerizable compound is cured. A manufacturing method comprising:
A method for producing a functional polymer film that undergoes a curing reaction after the support is impregnated with the composition.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.)
<12> (A) A method for producing a functional polymer film comprising polymerizing a composition containing a polymerizable compound represented by the following general formula (1) and (B) a monofunctional polymerizable compound by irradiation with energy rays.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.)

In the present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. In addition, the “dissociable group” refers to a group that can be reversibly decomposed into its component atoms, ions, atomic groups, and the like.
In the present invention, the description such as “(meth) acryl” means —C (═O) CH═CH ₂ and / or —C (═O) C (CH ₃ ) ═CH _2. “(Meth) acrylamide” represents acrylamide and / or methacrylamide, and “(meth) acrylate” represents acrylate and / or methacrylate.
In each general formula, unless otherwise specified, when there are a plurality of groups having the same sign, these may be the same or different from each other, and similarly, when there are repetitions of a plurality of partial structures, These repetitions mean both the same repetition and a mixture of different repetitions within the specified range.
Furthermore, the geometrical isomer which is the substitution mode of the double bond in each general formula is not limited to the E-form or the Z-form unless otherwise specified, even if one of the isomers is described for convenience of display. Or a mixture thereof.

  ADVANTAGE OF THE INVENTION According to this invention, the polymeric functional film excellent in suppression of water permeability and pH tolerance can be provided. Furthermore, according to the present invention, it is possible to provide a polymer functional membrane that is excellent in all of the main properties as an ion exchange membrane, such as suppression of water permeability, ion transport number, and pH resistance.

FIG. 1 is a chart of ¹ H-NMR spectrum of the polymerizable compound 1 below. FIG. 2 schematically shows the flow path of the apparatus for measuring the water permeability of the membrane.

  The polymer functional film of the present invention (hereinafter sometimes simply referred to as “film”) includes (A) a polymerizable compound represented by the general formula (1), and (B) a monofunctional polymerizable compound. It is contained as an essential component, and is formed by a curing reaction of a composition containing (C) a polymerization initiator, (D) a polymerization inhibitor, and (E) a solvent as necessary.

  The polymer functional membrane of the present invention can be used for ion exchange, reverse osmosis, forward osmosis, gas separation and the like. Hereinafter, a preferred embodiment of the present invention will be described by taking as an example the case where the polymer functional membrane has a function as an ion exchange membrane.

The polymer functional membrane of the present invention is an anion exchange membrane or a cation exchange membrane.
The thickness of the membrane including the support is preferably less than 1000 μm, more preferably 10 to 300 μm, and most preferably 20 to 200 μm.

  The polymeric functional membrane of the present invention comprises a membrane and any porous support that remains in contact with the resulting membrane, the porous support contained within the membrane, and the total drying of any porous reinforcing material. Based on the mass, the ion exchange capacity is preferably 0.3 meq / g or more, more preferably 0.5 meq / g or more, and particularly preferably 1.0 meq / g or more. The ion exchange capacity can be measured by titration as described in the examples below.

The permselectivity of the functional polymer membrane (anion exchange membrane) of the present invention with respect to anions such as Cl- is preferably more than 75%, more preferably more than 80%, particularly preferably more than 85%, most preferably. Exceeds 90%. The permselectivity of the polymer functional membrane (cation exchange membrane) of the present invention with respect to cations such as Na + is preferably more than 75%, more preferably more than 80%, particularly preferably more than 85%, most preferably. Over 90%.

The electrical resistance of the polymer functional film of the present invention (film resistor) is preferably less than 10 [Omega · cm ^2, more preferably less than 5 [Omega · cm ^2, and most preferably less than 3Ω · cm ^2. Although there is no restriction | limiting in particular in the minimum of electrical resistance, it is practical that it is 0.1 ohm * cm < ² > or more.

The water absorption of the polymer functional membrane of the present invention is preferably less than 70%, more preferably less than 50%, and particularly preferably less than 30% based on the mass of the dry membrane.
Electrical resistance and permselectivity can be measured by the methods described in Membrane Science, 319, 217 to 218 (2008).

The water permeability of the polymer functional membrane of the present invention is preferably 20 × 10 ⁻⁵ ml / (m ² · Pa · hr) or less, preferably 15 × 10 ⁻⁵ ml / (m ² · Pa · hr). More preferably, it is more preferably 10 × 10 ⁻⁵ ml / (m ² · Pa · hr) or less.

  Typically, the polymeric functional membrane of the present invention is substantially non-porous, for example, the pores are smaller than the detection limit of a standard scanning electron microscope (SEM). Therefore, when Jeol JSM-6335F field emission SEM is used (acceleration voltage of 2 kV is applied, working distance is 4 mm, aperture 4, sample is coated with 1.5 nm thick Pt, magnification is × 100,000 times, field of view With an inclination of 3 °), the average pore size is generally smaller than 5 nm.

  Next, each component of the composition for producing the polymer functional film of the present invention will be described.

<Ingredients>
(A) Polymerizable compound represented by general formula (1) The polymer functional film of the present invention is obtained by curing a composition containing a polymerizable compound represented by the following general formula (1).
The polymerizable compound represented by the general formula (1) has four acrylamide groups and / or methacrylamide groups as polymerizable groups in the molecule, has high polymerization ability and curing ability, and has high pH resistance and mechanical strength. Also excellent. In addition, for example, by applying active energy rays such as α rays, γ rays, X rays, ultraviolet rays, visible rays, infrared rays, electron rays, or energy such as heat, the polymer is easily polymerized to obtain a polymer film. be able to. Further, the compound represented by the general formula (1) exhibits water solubility and dissolves well in water-soluble organic solvents such as water and alcohol.

In general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ^1, the oxygen atom and the nitrogen atom bonded to both ends of the L ¹ does not take a structure bound to the same carbon atom of L ^1. L ² represents a divalent linking group. k represents 2 or 3. x, y, and z each independently represent an integer of 0-6, and x + y + z satisfies 0-18.

R ¹ represents a hydrogen atom or a methyl group. Several R < ¹ > may mutually be same or different. R ¹ is preferably a hydrogen atom.

L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. The plurality of L ¹ may be the same as or different from each other. The number of carbon atoms of the alkylene group represented by L ¹ is preferably 3 or 4, more preferably 3, and among these, a linear alkylene group having 3 carbon atoms is particularly preferable. The alkylene group of L ¹ may further have a substituent, and examples of the substituent include an aryl group and an alkoxy group.
However, in L ^1, the oxygen atom and the nitrogen atom bonded to both ends of the L ¹ does not take a structure bound to the same carbon atom of L ^1. L ¹ is a linear or branched alkylene group linking an oxygen atom and a nitrogen atom of a (meth) acrylamide group. When the alkylene group has a branched structure, oxygen atoms at both ends and the nitrogen of the (meth) acrylamide group It is also conceivable to take an —O—C—N— structure (hemaminal structure) in which an atom is bonded to the same carbon atom in an alkylene group. However, the polymerizable compound represented by the general formula (1) used in the present invention does not include a compound having such a structure. When the molecule has an —O—C—N— structure, decomposition is likely to occur at the position of the carbon atom. In particular, such a compound is easily decomposed during storage, and the decomposition is accelerated in the presence of water and moisture, thereby reducing the storage stability of the cured composition.

Examples of the divalent linking group in L ² include an alkylene group, an arylene group, a divalent heterocyclic group, or a group composed of a combination thereof, and an alkylene group is preferable. When the divalent linking group includes an alkylene group, the alkylene group may further include at least one group selected from -O-, -S-, and -N (Ra)-. . Here, Ra represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
The term “-O— contained in the alkylene group” means that the alkylene group of the linking group of the linking group is linked via the heteroatom as in, for example, -alkylene-O-alkylene-.
Specific examples of the alkylene group containing —O— include —C ₂ H ₄ —O—C ₂ H ₄ —, —C ₃ H ₆ —O—C ₃ H ₆ — and the like.

When L ² contains an alkylene group, examples of the alkylene group include methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octyne, nonylene and the like. L number of carbon atoms in the alkylene group of ² to 6 is preferred, more preferably 1 to 3, 1 is particularly preferred. The alkylene group may further have a substituent, and examples of the substituent include an aryl group and an alkoxy group.

When L ² contains an arylene group, examples of the arylene group include phenylene and naphthylene. 6-14 are preferable, as for carbon number of an arylene group, 6-10 are more preferable, and 6 is especially preferable. The arylene group may further have a substituent, and examples of the substituent include an alkyl group and an alkoxy group.

When L ² contains a divalent heterocyclic group, this heterocyclic ring is preferably a 5-membered or 6-membered ring and may be condensed. Further, it may be an aromatic heterocyclic ring or a non-aromatic heterocyclic ring. The heterocyclic ring of the divalent heterocyclic group includes pyridine, pyrazine, pyrimidine, pyridazine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene, benzothiophene, pyrazole, imidazole, Examples include benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline and the like. Of these, aromatic heterocycles are preferable, and pyridine, pyrazine, pyrimidine, pyridazine, triazine, pyrazole, imidazole, benzimidazole, triazole, thiazole, benzothiazole, isothiazole, benzisothiazole, and thiadiazole are preferable.

The position of the two bonds of the heterocycle of the divalent heterocyclic group is not particularly limited. For example, in the case of pyridine, substitution at the 2-position, 3-position, and 4-position is possible. The bond may be in any position.
Moreover, the heterocyclic ring of a bivalent heterocyclic group may further have a substituent, and examples of the substituent include an alkyl group, an aryl group, and an alkoxy group.

k represents 2 or 3, and a plurality of k may be the same as or different from each other. C _k H _2k may have a linear structure or a branched structure.

  x, y, and z each independently represent an integer of 0 to 6, preferably an integer of 0 to 5, and more preferably an integer of 0 to 3. Although x + y + z satisfies 0-18, 0-15 are preferable and 0-9 are more preferable.

  Specific examples of the polymerizable compound represented by the general formula (1) are shown below, but the present invention is not limited thereto.

  The polymerizable compound represented by the general formula (1) can be produced, for example, according to the following scheme 1 or scheme 2. In the polymer functional film of this embodiment, two or more compounds represented by the general formula (1) may be used in combination.

Scheme 1
(First step) A step of obtaining a polycyano compound by a reaction of acrylonitrile and trishydroxymethylaminomethane. The reaction in this step is preferably performed at 3 to 60 ° C. for 2 to 8 hours.
(Second step) A step of reacting a polycyano compound with hydrogen in the presence of a catalyst to obtain a polyamine compound by a reduction reaction. The reaction in this step is preferably performed at 20 to 60 ° C. for 5 to 16 hours.
(Third step) A step of obtaining a polyfunctional acrylamide compound by an acylation reaction between a polyamine compound and acrylic acid chloride or methacrylic acid chloride. The reaction in this step is preferably performed at 3 to 25 ° C. for 1 to 5 hours. The acylating agent may be diacrylic anhydride or dimethacrylic anhydride instead of acid chloride. In addition, by using both acrylic acid chloride and methacrylic acid chloride in the acylation step, a compound having an acrylamide group and a methacrylamide group in the same molecule can be obtained as the final product.

  Bz represents a benzyl group.

Scheme 2
(First step) A step of obtaining a nitrogen-protected aminoalcohol compound by a protecting group introduction reaction with a benzyl group, a benzyloxycarbonyl group or the like on the nitrogen atom of the aminoalcohol. The reaction in this step is preferably performed at 3 to 25 ° C. for 3 to 5 hours.
(2nd process) The process of introduce | transducing leaving groups, such as a methanesulfonyl group and p-toluenesulfonyl group, into OH group of a nitrogen protection amino alcohol compound, and obtaining a sulfonyl compound. The reaction in this step is preferably performed at 3 to 25 ° C. for 2 to 5 hours.
(Third step) A step of obtaining an amino alcohol addition compound by S _N 2 reaction between a sulfonyl compound and trishydroxymethylnitromethane. The reaction in this step is preferably performed at 3 to 70 ° C. for 5 to 10 hours.
(Fourth step) A step of reacting an amino alcohol addition compound with hydrogen in the presence of a catalyst to obtain a polyamine compound by hydrogenation reaction. The reaction in this step is preferably performed at 20 to 60 ° C. for 5 to 16 hours.
(Fifth step) A step of obtaining a polyfunctional acrylamide compound by an acylation reaction between a polyamine compound and acrylic acid chloride or methacrylic acid chloride. The reaction in this step is preferably performed at 3 to 25 ° C. for 1 to 5 hours. The acylating agent may be diacrylic anhydride or dimethacrylic anhydride instead of acid chloride. In addition, by using both acrylic acid chloride and methacrylic acid chloride in the acylation step, a compound having an acrylamide group and a methacrylamide group in the same molecule can be obtained as the final product.

  The compound obtained by the above steps can be purified from the reaction product solution by a conventional method. For example, it can be purified by liquid separation extraction using an organic solvent, crystallization using a poor solvent, column chromatography using silica gel, and the like.

(B) Monofunctional polymerizable compound The functional polymer film of the present invention polymerizes (cures) the polymerizable compound represented by (A) the general formula (1) and (B) the monofunctional polymerizable compound. Can be obtained.
Examples of such monofunctional polymerizable compounds include (meth) acrylate compounds, (meth) acrylamide compounds, vinyl ether compounds, aromatic vinyl compounds, N-vinyl compounds (polymerizable monomers having an amide bond), allyl compounds, and the like. It is done.
Among these, from the stability and pH resistance of the obtained functional polymer film, those having no ester bond, (meth) acrylamide compounds, vinyl ether compounds, aromatic vinyl compounds, N-vinyl compounds (amide bonds) Polymerizable monomers) and allyl compounds are preferred, and (meth) acrylamide compounds are particularly preferred.
Examples of the monofunctional polymerizable compound include compounds described in JP-A-2008-208190 and JP-A-2008-266561.
These monofunctional polymerizable compounds are preferably those having a dissociating group, as described later, for imparting the function of the polymer film.
For example, in the (meth) acrylate compound, those having a substituent in the alcohol part of the ester (preferable substituents include those described below), particularly those having a dissociating group in the alkyl part of the alcohol are preferable.

  As the monofunctional polymerizable compound having a (meth) acrylamide structure used in the present invention, a compound represented by the following general formula (2) is preferable.

In general formula (2), R ¹⁰ represents a hydrogen atom or a methyl group. R ¹¹ represents a hydrogen atom or a substituted or unsubstituted alkyl group, and R ¹² represents a substituted or unsubstituted alkyl group. Here, R ¹¹ and R ¹² may be bonded to each other to form a ring.

R ¹⁰ is preferably a hydrogen atom.
The alkyl group in R ¹¹ and ^{R 12,} carbon atoms preferably 1 to 18, more preferably 1-12, even more preferably 1-6. Examples include methyl, ethyl , n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, n-hexyl, n-octyl, t-octyl, n-decyl and n-octadecyl.

These alkyl groups are preferably linear or branched alkyl groups and may have a substituent.
Alkyl group substituents include hydroxyl groups, sulfo groups or salts thereof, carboxyl groups or salts thereof, onio groups (ammonio groups, pyridinio groups, sulfonio groups, etc.), halogen atoms, alkyl groups, aryl groups, heterocyclic groups, alkoxy groups. Group, aryloxy group, alkylthio group, arylthio group, amino group (including amino group, alkylamino group, arylamino group, heterocyclic amino group), amide group, sulfonamido group, carbamoyl group, sulfamoyl group, acyl group, And a cyano group.

In the present invention, in order to impart the function of the polymer membrane, it is preferable to impart the function with a substituent of the alkyl group. For this reason, among the above substituents, a dissociating group and a polar substituent are preferable, and a dissociating group is particularly preferable.
The dissociating group is preferably a hydroxyl group (particularly a phenolic or enolic hydroxyl group), a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an onio group (such as an ammonio group, a pyridinio group, or a sulfonio group), and a sulfo group. More preferably a group or a salt thereof, a carboxyl group or a salt thereof, or an onio group.

  Here, as a salt in a sulfo group or a carboxyl group, a cation of an alkali metal atom, for example, a lithium cation, a potassium cation, or a sodium cation is preferable.

  The onio group is preferably a group represented by the following general formula (a) or (b).

General formula (a) General formula (b)
_{^{-N (Rb) 3 + X -}} -S (Rb) 2 + X -

In general formulas (a) and (b), Rb represents an alkyl group or an aryl group. A plurality of Rb may be the same or different from each other, and two Rb may be bonded to each other to form a ring.
X ⁻ represents an anion.

The alkyl group for Rb preferably has 1 to 18 carbon atoms, more preferably 1 to 12, and still more preferably 1 to 6. The alkyl group may have a substituent, and examples of such a substituent include a substituent that the alkyl group in R ¹¹ and R ¹² may have. Of these, an aryl group is preferred. Of the alkyl groups substituted by the aryl group in Rb, a benzyl group is preferred.

6-18 are preferable and, as for the aryl group in Rb, 6-12 are more preferable.
The aryl group in Rb may have a substituent, and examples of such a substituent include the substituent that the alkyl group in R ¹¹ and R ¹² may have.
The ring formed by bonding two Rb to each other is preferably a 5- or 6-membered ring.
As such a ring, in general formula (a), a nitrogen-containing aromatic ring is preferable, and a pyridine ring is particularly preferable.

X ^- is the anion, a halogen ion, carboxylate ion (e.g., acetate ion, benzoate ion), sulfate ion, organic acid ion (e.g., methanesulfonic acid ion, benzenesulfonate ion, p- toluenesulfonate ion) , OH ^{− and the} like.

Examples of the group represented by the general formula (a) include trimethylammonio, triethylammonio, tributylammonio, dimethylbenzylammonio, dimethylphenylammonio, dimethylcetylammonio, and pyridinio.
Examples of the group represented by the general formula (b) include dimethylsulfonio, methylbenzylsulfonio, and methylphenylsulfonio.
Of the groups represented by the general formulas (a) and (b), the group represented by the general formula (a) is preferable.

Of the substituents that the alkyl group in R ¹¹ and R ¹² may have, a polar group is preferred, an acyl group and an amino group are preferred, and an amino group is particularly preferred, other than the dissociating group. The amino group is preferably a tertiary amino group, and is preferably a group represented by the following general formula (c).

Formula (c)
-N (Rb) ₂

  In general formula (c), Rb has the same meaning as Rb in general formula (a), and the preferred range is also the same.

  Examples of the group represented by the general formula (c) include dimethylamino and diethylamino.

Of the substituents that the alkyl group in R ¹¹ and R ¹² may have, the acyl group may be either an alkylcarbonyl group or an arylcarbonyl group, but is preferably an alkylcarbonyl group. The alkylcarbonyl group preferably has 2 to 12 carbon atoms, and the arylcarbonyl group preferably has 7 to 12 carbon atoms. Examples of the acyl group include acetyl, propionyl, pivaloyl, and benzoyl.

When the alkyl group in R < ¹¹ > and R < ¹² > has a substituent, 1-6 are preferable and, as for carbon number of an alkyl group part, 1-3 are preferable.

Examples of the ring and R ¹¹ and R ¹² are bonded to each other to form, Ri Ah with hetero ring, such heteroaryl ring, R ¹¹ and R ¹² are other than nitrogen atom bonded ring-constituting atom is an oxygen atom, A nitrogen atom or a sulfur atom is preferable.
The ring formed by combining R ¹¹ and R ¹² with each other is preferably a 5- or 6-membered ring.
These rings, for example, pin Perijin ring, morpholine ring, piperazine ring, and etc. pin roll ring.

In the general formula (2), one of R ¹¹ and R ¹² is preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  Specific examples of the monofunctional polymerizable compound having a (meth) acrylamide structure represented by the general formula (2) include the following exemplary compounds (B-1) to (B-23). It is not limited to.

  These compounds are commercially available from Kojin Co., Ltd., Kyowa Hakko Chemical Co., Ltd., Fluka Co., Ltd., aldrich Co., Ltd., and Toa Gosei Co., Ltd., or can be easily synthesized by known methods.

The content ratio of the polymerizable compound represented by (A) the general formula (1) and the (B) monofunctional polymerizable compound is based on 100 parts by mass of the (B) monofunctional polymerizable compound. (A) As for the polymeric compound represented by General formula (1), 1-50 mass parts is preferable, 10-50 mass parts is more preferable, and 10-40 mass parts is further more preferable.
Within the above preferred ranges, the desired curability, pH resistance, mechanical strength and flexibility are excellent.

(C) Polymerization initiator The composition of the present invention preferably contains a polymerization initiator.
Among the polymerization initiators, in the present invention, a photopolymerization initiator that can be polymerized by irradiation with energy rays is preferable.
As photopolymerization initiators, aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic oxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borate compounds, azinium compounds, metallocene compounds, Examples thereof include active ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.

  Preferred examples of aromatic ketones, acylphosphine oxide compounds, and thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, p. 77-117 (1993), and the compounds having a benzophenone skeleton or a thioxanthone skeleton. More preferable examples include α-thiobenzophenone compounds described in JP-B-47-6416, benzoin ether compounds described in JP-B-47-3981, and α-substituted benzoins described in JP-B-47-22326. Compounds, benzoin derivatives described in JP-B-47-23664, aroylphosphonic acid esters described in JP-A-57-30704, dialkoxybenzophenones described in JP-B-60-26483, JP-B-60- 26403, benzoin ethers described in JP-A-62-81345, JP-B-1-34242, US Pat. No. 4,318,791, and European Patent Application Publication No. 0284561A1 α-Aminobenzophenones, p-di (described in JP-A-2-211452) Methylaminobenzoyl) benzene, thio-substituted aromatic ketone described in JP-A-61-194062, acylphosphine sulfide described in JP-B-2-9597, acylphosphine described in JP-B-2-9596, Examples thereof include thioxanthones described in JP-B 63-61950, and coumarins described in JP-B 59-42864. Moreover, the polymerization initiators described in JP 2008-105379 A and JP 2009-114290 A are also preferable. Moreover, the polymerization initiator etc. which are described in 65th-148th pages of "An ultraviolet curing system" written by Kiyosuke Kato (the General Technology Center Co., Ltd. issue: Heisei 1st year) can be mentioned.

In the present invention, a water-soluble polymerization initiator is preferred.
Here, that the polymerization initiator is water-soluble means that it is dissolved in distilled water at 0.1% by mass or more at 25 ° C. The water-soluble photopolymerization initiator is more preferably dissolved by 0.5% by mass or more in distilled water at 25 ° C., and particularly preferably by 1% by mass or more.

  Among these, a suitable photopolymerization initiator for the curable composition in the present embodiment is an aromatic ketone (particularly an α-hydroxy-substituted benzoin compound) or an acylphosphine oxide compound. In particular, p-phenylbenzophenone (manufactured by Wako Pure Chemical Industries), bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide (Irgacure 819, manufactured by BASF Japan), 2,4,6-trimethylbenzoyldiphenylphosphine Oxide (Darocur TPO, manufactured by BASF Japan), 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1 (Irgacure 369, manufactured by BASF Japan), 2-methyl-1 -(4-Methylthiophenyl) -2-morpholinopropan-1-one (Irgacure 907, manufactured by BASF Japan Ltd.), 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl -1-propan-1-one (Irgac re 2959, manufactured by BASF Japan Ltd.), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Darocur 1173, manufactured by Ciba Specialty Chemicals Co., Ltd.) is preferable, from the viewpoint of water solubility and hydrolysis resistance. Irgacure 2959 (manufactured by BASF Japan) and Darocur 1173 (manufactured by Ciba Specialty Chemicals) are most preferable.

In this invention, 0.1-10 mass parts is preferable with respect to 100 mass parts of total solid content in a composition, as for content of a polymerization initiator, 0.1-5 mass parts is more preferable, 0.3 More preferably, ˜2 parts by mass.

(D) Polymerization inhibitor In this invention, it is also preferable that a polymerization inhibitor is included.
As the polymerization inhibitor, a known polymerization inhibitor can be used, and examples thereof include a phenol compound, a hydroquinone compound, an amine compound, and a mercapto compound.
Examples of the phenol compound include hindered phenols (phenols having a t-butyl group in the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenols. Specific examples of the hydroquinone compound include monomethyl ether hydroquinone. Specific examples of the amine compound include N-nitroso-N-phenylhydroxylamine and N, N-diethylhydroxylamine.
These polymerization inhibitors may be used alone or in combination of two or more.
The content of the polymerization inhibitor is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass, and more preferably 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total solid content in the composition. Part by mass is more preferable.

(E) Solvent The composition of the present invention may contain (E) a solvent. The content of the solvent (E) in the composition is preferably 5 to 50% by mass, more preferably 10 to 50% by mass, and still more preferably 10 to 40% by mass with respect to the total composition.
By including the solvent, the curing (polymerization) reaction proceeds uniformly and smoothly. Further, when the porous support is impregnated with the composition, the impregnation proceeds smoothly.

(E) As the solvent, a solvent having a solubility in water of 5% by mass or more is preferably used, and a solvent that is freely mixed with water is preferable. For this reason, a solvent selected from water and a water-soluble solvent is preferred.
As the water-soluble solvent, alcohol solvents, ether solvents that are aprotic polar solvents, amide solvents, ketone solvents, sulfoxide solvents, sulfone solvents, nitrile solvents, and organic phosphorus solvents are particularly preferable. .
Examples of the alcohol solvent include methanol, ethanol, isopropanol, n-butanol, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol and the like. These can be used alone or in combination of two or more.
Examples of aprotic polar solvents include dimethyl sulfoxide, dimethyl imidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylurea, hexamethylphosphorotriamide, pyridine, propionitrile, Preferred examples of the solvent include butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, and γ-butyrolactone. Among them, dimethylsulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferable. preferable. These can be used alone or in combination of two or more.

(F) Alkali Metal Compound The curable composition in the present embodiment may contain (F) an alkali metal compound in order to improve the solubility of the compound having the (meth) acrylamide structure. As the alkali metal compound, lithium, sodium, potassium hydroxide salt, chloride salt, nitrate salt and the like are preferable. Among them, lithium compounds are more preferable, and specific examples thereof include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoro Examples thereof include borate, lithium hexafluorophosphate, and lithium hexafluoroarsenate.
Here, it is also preferable to use the alkali metal compound in order to neutralize the composition and the composition solution mixture.
These alkali metal compounds may be hydrates. Moreover, it can be used individually by 1 type or in combination of 2 or more types.
0.1-20 mass parts is preferable with respect to 100 mass parts of total solid content in a composition, as for the addition amount in the case of adding an alkali metal compound, 1-20 mass parts is more preferable, 5-20 mass parts Is more preferable.

  In addition to the alkali metal compound, if necessary, for example, a surfactant, a viscosity improver, a surface tension modifier, and a preservative may be contained.

Next, the manufacturing method of the polymeric functional film of this embodiment is demonstrated.
The polymer functional membrane of the present embodiment can be prepared batchwise using a fixed support, but the membrane can also be prepared continuously using a moving support. The support may be in the form of a roll that is continuously rewound. In addition, when preparing a film | membrane by a continuous type, a support body can be mounted on the belt moved continuously, and a film | membrane can be prepared (or combination of these methods). Using such techniques, the composition of the present invention can be applied to the support in a continuous manner, or it can be applied in a large batch.
In addition, you may use a temporary support body (it peels a film | membrane from a temporary support body after completion | finish of hardening reaction) until a hardening reaction is completed by immersing a composition in a porous support body separately from a support body.
Such a temporary support does not need to consider material permeation, and may be any material as long as it can be fixed for film formation including a metal plate such as a PET film or an aluminum plate. .
Alternatively, the composition can be immersed in a porous support and cured without using a support other than the porous support.

  The composition can be applied by any suitable method such as curtain coating, extrusion coating, air knife coating, slide coating, nip roll coating, forward roll coating, reverse roll coating, dip coating, kiss coating, rod bar coating or spray coating. It can be applied to the porous support layer. Multi-layer coating can be performed simultaneously or sequentially. For multilayer simultaneous coating, curtain coating, slide coating, slot die coating and extrusion coating are preferred.

  Accordingly, in a preferred method, the composition of the present invention is continuously applied to a moving support, more preferably a curable composition application station, an irradiation source for curing the composition, and a film collection. Application is by a production unit comprising a station and means for moving the support from the curable composition application station to the irradiation source and the film collection station.

  In this production example, (i) the curable composition is applied to the porous support, (ii) the composition is cured by light irradiation, and (iii) the film is removed from the support as desired. The polymer functional film of this embodiment is created.

The curable composition application station can be located upstream from the irradiation source, and the irradiation source is located upstream from the composite film collection station.
In order to have sufficient fluidity for application by a high speed coating machine, the composition of the present invention is preferably 4000 mPa.s measured at 35 ° C. s, more preferably 1 to 1000 mPa.s measured at 35 ° C. having a viscosity of s. The viscosity of the curable composition is 1 to 500 mPa.s measured at 35 ° C. Most preferably, it is s. For coating methods such as slide bead coating, the preferred viscosity is 1-100 mPa.s measured at 35 ° C. s.

  With suitable coating techniques, the composition of the invention can be applied to a support moving at speeds greater than 15 m / min, such as greater than 20 m / min, or even higher speeds, such as 60 m. / Min, 120 m / min, or up to 400 m / min.

  Prior to applying the composition of the present invention to the surface of the support, particularly if the support is intended to leave the membrane in the membrane, the support is treated with, for example, the wettability and adhesion of the support. In order to improve, it may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like.

  During the curing reaction, (A) the polymerizable compound represented by the general formula (1) and (B) the monofunctional polymerizable compound are polymerized to form a polymer. The curing reaction can be carried out by light irradiation under the condition that curing occurs quickly enough to form a film within 30 seconds.

Curing of the composition of the present invention begins preferably within 60 seconds, more preferably within 15 seconds, especially within 5 seconds, and most preferably within 3 seconds after the composition is applied to the support layer.
Curing is achieved by irradiating the composition with light for preferably less than 10 seconds, more preferably less than 5 seconds, particularly preferably less than 3 seconds and most preferably less than 2 seconds. In the continuous method, the irradiation is continuously performed, and the speed at which the composition moves through the irradiation beam mainly determines the duration of the curing reaction time.

  When high intensity UV light is used for the curing reaction, a significant amount of heat can be generated. Thus, cooling air may be applied to the lamp and / or support / membrane to prevent overheating. Often, a significant dose of IR light is irradiated along with the UV beam. In one aspect, curing is performed by irradiation with UV light filtered through an IR reflective quartz plate.

  It is preferable to use ultraviolet rays for curing. Suitable wavelengths are for example UV-A (400 to> 320 nm), UV-B (320 to> 280 nm), provided that the wavelength and wavelength of any photoinitiator included in the composition are compatible. UV-C (280-200 nm).

  Suitable UV sources include mercury arc lamps, carbon arc lamps, low pressure mercury lamps, medium pressure mercury lamps, high pressure mercury lamps, swirling plasma arc lamps, metal halide lamps, xenon lamps, tungsten lamps, halogen lamps, lasers and UV light emitting diodes. is there. Medium pressure or high pressure mercury vapor type UV lamps are particularly preferred. In addition, additives such as metal halides may be present to modify the emission spectrum of the lamp. In most cases, lamps having an emission maximum between 200 and 450 nm are particularly suitable.

The energy output of the irradiation source is preferably 20 to 1000 W / cm, preferably 40 to 500 W / cm, but can be higher or lower if the desired exposure dose can be achieved. The exposure intensity is one of the parameters that can be used to control the degree of cure that affects the final structure of the film. Exposure dose is High
Preferably at least 40 mJ / cm ² , more preferably 40-1000 mJ / cm ² , as measured by the Energy UV Radiometer (UV Power Pack ^™ from EIT-Instrument Markets) in the UV-B range indicated by the device, Most preferably, it is 50-500 mJ / cm < ² >. The exposure time can be chosen freely but is preferably short, typically less than 2 seconds.

  In order to reach the desired dose at high coating speeds, more than one UV lamp may be required so that the curable composition is exposed to more than one lamp. When more than one lamp is applied, all lamps can provide an equivalent dose, or each lamp can have an individual setting. For example, the first lamp can provide a higher dose than the second or subsequent lamp, or the exposure intensity of the first lamp may be lower.

Many techniques can be used to provide the membrane of this embodiment having particularly good mechanical strength. For example, a support can be used as the membrane reinforcing material, and a porous support can be preferably used. This porous support can constitute a part of the membrane by being impregnated with the composition and then subjected to a curing reaction.
Examples of the porous support as the reinforcing material include a synthetic woven fabric or synthetic nonwoven fabric, a sponge film, a film having fine through holes, and the like. The material forming the porous support of the present invention is, for example, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or, for example, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylene. Sulfide, polyimide, polyetheramide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, poly It can be a porous membrane based on hexafluoropropylene, polychlorotrifluoroethylene and their copolymers. Commercially available porous supports and reinforcing materials are, for example, Japan Vilene and Freudenberg.
Commercially available from Filtration Technologies (Novatexx material) and Separ AG. In an embodiment in which the porous reinforcing material is applied to the curable composition before curing, the porous reinforcing material is capable of passing irradiation of the wavelength used for curing and / or the curable composition is It is preferred that it is able to penetrate the porous reinforcing material so that it is cured in step (iii).

  The porous support preferably has hydrophilicity. As a method for imparting hydrophilicity to the support, general methods such as corona treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.

  The polymer functional membrane of this embodiment is mainly intended for use in ion exchange. However, it is considered that the polymer functional membrane of the present invention is not limited to ion exchange and can be suitably used for reverse osmosis and gas separation.

  EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited to these Examples. Unless otherwise specified, “part” and “%” are based on mass.

(Example 1)
(Synthesis of polyfunctional polymerizable compounds)
-Synthesis of polymerizable compound 1-
The polymerizable compound 1 exemplified above was synthesized according to the following scheme.

(First step)
To a 1 L three-necked flask equipped with a stir bar, 121 g (1 equivalent) of tris (hydroxymethyl) aminomethane (manufactured by Tokyo Chemical Industry Co., Ltd.), 84 ml of a 50% aqueous potassium hydroxide solution and 423 ml of toluene were added and stirred, The reaction system was maintained at 20 to 25 ° C., and 397.5 g (7.5 equivalents) of acrylonitrile was added dropwise over 2 hours. After dripping, after stirring for 1.5 hours, 540 ml of toluene was added to the reaction system, the reaction mixture was transferred to a separatory funnel, and the aqueous layer was removed. The remaining organic layer was dried over magnesium sulfate, filtered through celite, and the solvent was distilled off under reduced pressure to obtain an acrylonitrile adduct. The results of analysis of the obtained substance by ¹ H NMR and MS showed a good agreement with the known substance, and thus it was used for the next reduction reaction without further purification.

(Second step)
In a 1 L autoclave, 24 g of the previously obtained acrylonitrile adduct, 48 g of Ni catalyst (Raney nickel 2400, manufactured by WR Grace & Co.), and 600 ml of 25% aqueous ammonia: methanol = 1: 1 solution were suspended and reacted. The container was sealed. 10 Mpa of hydrogen was introduced into the reaction vessel and reacted at a reaction temperature of 25 ° C. for 16 hours.
The disappearance of the raw materials was confirmed by ¹ H NMR, the reaction mixture was filtered through celite, and the celite was washed several times with methanol. The filtrate was evaporated under reduced pressure to obtain a polyamine compound. The obtained material was used in the next reaction without further purification.

(Third process)
To a 2 L three-necked flask equipped with a stirrer was added 30 g of the polyamine obtained above, 120 g of NaHCO ₃ (14 equivalents), 1 L of dichloromethane, and 50 ml of water, and 92.8 g (10 equivalents) of acrylic acid chloride in an ice bath. Was added dropwise over 3 hours and then stirred at room temperature for 3 hours. After confirming the disappearance of the raw materials by ¹ H NMR, the reaction mixture was evaporated under reduced pressure, the reaction mixture was dried over magnesium sulfate, filtered through celite, and the solvent was evaporated under reduced pressure. Finally, it was purified by column chromatography (ethyl acetate / methanol = 4: 1) to obtain a white solid (yield 40%) at room temperature. The total yield of the above three steps was 40%.

¹ H-NMR was measured for the obtained white solid under the following measurement conditions. A chart of ¹ H-NMR spectrum is shown in FIG.
¹ H-NMR Solvent: deuterated chloroform, internal standard: TMS

From the ¹ H-NMR data shown in FIG. 1, the integration ratio of the single hydrogen peak derived from acrylic at around 5.6 ppm is 6 to the integral ratio of singlet peak at 3.75 ppm (peak derived from the mother skeleton). Since it was 4, it turned out that the said compound has four acrylamide groups. From these results, it was confirmed that the white solid had a structure represented by the polymerizable compound 1.

(Creation of anion exchange membrane)
A coating solution of the composition shown in Table 1 below was manually applied to an aluminum plate at a speed of about 5 m / min using a 150 μm wire winding rod, followed by a non-woven fabric (FO-2223 manufactured by Freudenberg). -10) was impregnated with the coating solution. Excess coating solution was removed using a rod around which no wire was wound. The temperature of the coating solution at the time of coating was about 50 ° C. An anion exchange membrane was prepared by curing reaction of the coating liquid-impregnated support using a UV exposure machine (Fusion UV Systems, Model Light Hammer LH6, D-bulb, speed 15 m / min, 100% strength). did. The exposure amount was 750 mJ / cm ² in the UV-A region. The resulting membrane was removed from the aluminum plate and stored in 0.1 M NaCl solution for at least 12 hours. The thickness of the obtained film was 131 μm.

(Cation exchange membrane creation)
A cation exchange membrane was prepared in the same manner as the anion exchange membrane, except that the composition of the composition was changed to the composition shown in Table 1 in the preparation of the anion exchange membrane. The thickness of the obtained film was 135 μm.

(Example 2)
In the preparation of the anion exchange membrane and the cation exchange membrane of Example 1, the anion exchange membrane and the cation exchange membrane of Example 2 were respectively the same as Example 1 except that the composition was changed to the composition described in Table 1 below. It was created. The thicknesses of the obtained anion exchange membrane and cation exchange membrane were 138 μm and 140 μm, respectively.

(Example 3)
In the preparation of the anion exchange membrane and the cation exchange membrane of Example 1, the anion exchange membrane and the cation exchange membrane of Example 3 were respectively the same as Example 1 except that the composition was changed to the composition described in Table 1 below. It was created. The thicknesses of the obtained anion exchange membrane and cation exchange membrane were 140 μm and 143 μm, respectively.

(Comparative example)
With reference to International Publication No. 2011/025867 pamphlet, a non-woven fabric (FO-2223-10 manufactured by Freudenberg) is impregnated with a coating solution of the composition described in Table 1 below, and 1 at 80 ° C. in a nitrogen atmosphere. The anion exchange membrane and the cation exchange membrane of the comparative example were created by time thermal polymerization. The thicknesses of the obtained anion exchange membrane and cation exchange membrane were 118 μm and 120 μm, respectively.

[Description of Abbreviations in Table 1]
PW: pure water IPA: isopropyl alcohol NMP: N-methylpyrrolidone DPG: dipropylene glycol 1-PA: 1-propyl alcohol MEHQ: monomethyl ether hydroquinone DMAPAA-Q: dimethylaminopropylacrylamide methyl chloride quaternary salt
(3-acrylamidopropyltrimethylammonium chloride)
TMAEMC: Trimethylammonium ethyl methacryl chloride
(2-methacrylamidoethyltrimethylammonium chloride)
AMPS: 2-acrylamido-2-methylpropanesulfonic acid 2-SEM: 2-sulfoethyl methacrylate HEAA: hydroxyethyl acrylamide EGDM: ethylene glycol dimethacrylate AIBN: azobisisobutyronitrile

  The following items were evaluated for the anion exchange membrane and the cation exchange membrane prepared in Examples 1 to 3 and Comparative Example. The results are shown in Table 2 below.

The permselectivity was calculated by measuring the membrane potential (V) by static membrane potential measurement. The two electrolytic cells (cells) are separated by the membrane to be measured. Prior to measurement, the membrane was equilibrated in 0.05 M NaCl aqueous solution for about 16 hours. Thereafter, NaCl aqueous solutions having different concentrations were respectively poured into the cells on the opposite side of the film to be measured.
100 mL of 0.05 M NaCl aqueous solution was poured into one cell. Moreover, 100 mL of 0.5M NaCl aqueous solution was poured into the other cell.
After the temperature of the NaCl aqueous solution in the cell is stabilized at 25 ° C. by a constant temperature water bath, both electrolytic cells and an Ag / AgCl reference electrode (manufactured by Metrohm, Switzerland) The membrane potential (V) was measured by connecting with a bridge, and the transport number t was calculated by the following formula (a).
The effective area of the film was 1 cm ² .

t = (a + b) / 2b Formula (a)

Details of each symbol in the formula (a) are shown below.
a: Membrane potential (V)
b: 0.5915 log (f ₁ c ₁ / f ₂ c ₂ ) (V)
f ₁ , f ₂ : NaCl activity coefficient of both cells c ₁ , c ₂ : NaCl concentration (M) of both cells

[Water permeability (ml / (m ² · Pa · hr)]
The water permeability of the membrane was measured by an apparatus having a flow path 10 shown in FIG. In FIG. 2, reference numeral 1 represents a membrane, and reference numerals 3 and 4 represent flow paths for a feed solution (pure water) and a draw solution (3M NaCl), respectively. The arrow 2 indicates the flow of water separated from the feed solution.
400 mL of the feed solution and 400 mL of the draw solution were brought into contact with each other through the membrane (membrane contact area 18 cm ² ), and each solution was flowed at a flow rate of 8 cm / sec in the direction of the arrow 5 by using a peristaltic pump. The rate at which the water in the feed solution penetrates the draw solution through the membrane was analyzed by measuring the mass of the feed solution and the draw solution in real time, and the water permeability was determined.

[Electrical resistance of membrane (Ω · cm ² )]
Wipe both sides of the membrane immersed in 0.5 M NaCl aqueous solution for about 2 hours with dry filter paper, 2-chamber cell (effective membrane area 1 cm ² , Ag / AgCl reference electrode for electrodes (made by Metrohm, Switzerland)) Both chambers are filled with 100 mL of 0.5 M NaCl, placed in a constant temperature water bath at 25 ° C. and left to reach equilibrium, and after the liquid temperature in the cell reaches 25 ° C. correctly, an AC bridge (frequency 1 , 000 Hz), the electrical resistance r ₁ was measured.
Next, the film was removed, and the electric resistance r ₂ between the _two electrodes was measured using only a 0.5 M NaCl aqueous solution, and the electric resistance r of the film was determined as r ₁ -r ₂ .

  In Table 2 below, “electrical resistance of the membrane” is abbreviated as “membrane resistance”.

[PH tolerance]
The membrane was immersed in an aqueous hydrochloric acid solution having a pH of 1 and an aqueous sodium hydroxide solution having a pH of 14, respectively, and kept at 40 ° C. for 3 hours. The ratio (retention rate (%)) of the water permeability of the film after immersion to the water permeability of the film before immersion was calculated.
In any of the aqueous solution of hydrochloric acid at pH 1 and the aqueous solution of sodium hydroxide at pH 14, the retention rate of the water permeability of the membrane before and after immersion is 90% or more, “good”, the retention rate of the membrane in any solution Was evaluated as “bad”.

  As is clear from Table 2, the anion exchange membranes and cation exchange membranes of Examples 1 to 3 using the polymerizable compound 1 represented by the general formula (1) of the present invention are both transport number and water permeability. Good results were shown for all of the rates, membrane resistance and pH tolerance. On the other hand, the comparative anion exchange membrane and cation exchange membrane using a crosslinking agent that is a conventionally known polymerizable compound have a water permeability and pH resistance of the anion exchange membrane and cation exchange membrane of Examples 1 and 2. Inferior.

DESCRIPTION OF SYMBOLS 1 Membrane 2 The arrow which shows that the water in a feed solution osmose | permeates a draw solution through a film | membrane 3 The flow path of a feed solution 4 The flow path of a draw solution 10 The flow direction of a liquid 10 The flow path of a water permeability measuring apparatus

Claims (12)

(A) A polymer functional film obtained by curing a composition containing a polymerizable compound represented by the following general formula (1) and (B) a monofunctional polymerizable compound.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.)   The polymer functional film according to claim 1, wherein the (B) monofunctional polymerizable compound has a dissociation group.   The polymer functional membrane according to claim 2, wherein the dissociating group is selected from a sulfo group or a salt thereof, a carboxyl group or a salt thereof, an ammonio group and a pyridinio group.   The polymer functional film according to claim 1, wherein the (B) monofunctional polymerizable compound is (meth) acrylate or (meth) acrylamide.   The polymerizable compound represented by (A) the general formula (1) is 1 to 45 parts by mass with respect to 100 parts by mass of the (B) monofunctional polymerizable compound. The polymer functional film according to Item.   The polymer functional film according to any one of claims 1 to 5, wherein the composition further comprises (E) a solvent.   The polymer functional film according to claim 6, wherein the solvent (E) is a solvent selected from water and a water-soluble solvent.   The polymer functional film according to claim 6 or 7, wherein the content of the solvent (E) in the composition is 10 to 50% by mass.   The polymeric functional film of any one of Claims 1-8 which has a support body. The polymer functional membrane according to any one of claims 1 to 9 , wherein the polymer functional membrane is an ion exchange membrane, a reverse osmosis membrane, a forward osmosis membrane, or a gas separation membrane. A method for producing a polymer functional film comprising a support, wherein (A) a polymerizable compound represented by the following general formula (1) and (B) a composition containing a monofunctional polymerizable compound are subjected to a curing reaction. There,
A method for producing a functional polymer film that undergoes a curing reaction after the support is impregnated with the composition.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.) (A) A method for producing a polymer functional film, wherein a composition containing a polymerizable compound represented by the following general formula (1) and (B) a monofunctional polymerizable compound is polymerized by irradiation with energy rays.

(In the general formula (1), R ¹ represents a hydrogen atom or a methyl group. L ¹ represents a linear or branched alkylene group having 2 to 4 carbon atoms. However, in L ¹ , at both ends of L ¹ There is no structure in which an oxygen atom and a nitrogen atom to be bonded are bonded to the same carbon atom of L ^1. L ² represents a divalent linking group, k represents 2 or 3, x, y and z Each independently represents an integer of 0-6, and x + y + z satisfies 0-18.)

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