JP2016137434A - Polymer functional film, and production method, laminate, and device thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polymer functional film which has high monovalent ion selective permeability and through which salt hardly leaks, to provide a production method of the polymer functional film, and to provide a laminate and a device each of which includes the polymer functional film.SOLUTION: The polymer functional film is: an anion exchange film containing an acrylic resin and/or a resin having a structural unit shown by the formula CL-1; or such a cation exchange film that a surface layer, which contains a polyamide resin having a cross-linked structure, is formed on the cation exchange film containing the acrylic resin. In the formula CL-1, Land Lare each an alkylene group or an alkenylene group independently, Rand Rare each an alkyl group or an aryl group independently or can be bonded to each other to form a ring, n1 and n2 are each an integer of 1-3 independently, and Xand Xare each an organic or inorganic anion independently.SELECTED DRAWING: None

Description

  The present invention relates to a polymer functional film, a production method thereof, a laminate, and an apparatus.

As membranes having various functions as polymer functional membranes, ion exchange membranes, reverse osmosis membranes, forward osmosis membranes, gas separation membranes and the like are known.
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 ion exchange membranes and electrical potentials to achieve ion 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.
As a conventional ion exchange membrane, the one described in Patent Document 1 is known.
Further, as a conventional composite semipermeable membrane, the one described in Patent Document 2 is known.

Japanese Patent Publication No. 36-15258 JP 2002-177750 A

  The problem to be solved by the present invention is a polymer functional membrane having a high monovalent ion selective permeability and less membrane salt leakage, a method for producing the same, and a laminate and an apparatus provided with the polymer functional membrane. Is to provide.

The above-described problems of the present invention have been solved by means described in the following <1>, <4> or <9> to <11>. It is described below together with <2>, <3> and <5> to <8> which are preferred embodiments.
<1> A polymer having a surface layer containing a polyamide resin having a crosslinked structure on an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the following formula CL-1. Functional membrane,

In Formula CL-1, L ¹ and L ² each independently represent an alkylene group or an alkenylene group, R ^a and R ^b each independently represent an alkyl group or an aryl group, and R ^a and R ^b are taken together, may form a ring, they are each n1 and n2 independently represent an integer of 1 to 3, X ₁ ^- and X ₂ ^- each independently represent an organic or inorganic anion.

  <2> The high resin according to <1>, wherein the acrylic resin and / or the resin having the structural unit represented by the formula CL-1 in the anion exchange membrane has a structural unit represented by the following formula IA. Molecular functional membrane,

In Formula IA, R ^A1 represents a hydrogen atom or an alkyl group, R ^{A2 to} R ^A4 each independently represents an alkyl group or an aryl group, and two or more of R ^{A2 to} R ^A4 are bonded to each other to form a ring. it may be ^{formed, Z A1} is -O- or -N ^{(R a)} - represents, ^{R a} represents hydrogen atom or an alkyl ^{group, L A1} represents an alkylene ^{group, X A1-} halide ion or Represents an aliphatic or aromatic carboxylate ion.

  <3> The resin having a structural unit represented by the above formula CL-1 and / or the acrylic resin in the anion exchange membrane has a structural unit represented by the following formula ICL, <1> or <2> A polymer functional membrane according to

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more.

  <4> The resin according to <2>, wherein the acrylic resin in the anion exchange membrane and / or the resin having a structural unit represented by the formula CL-1 has a structural unit represented by the following formula ICL-2. Polymer functional membrane,

In Formula ICL-2, R ^A′1 and R ^A′2 each independently represent a hydrogen atom or an alkyl group, R ^{A′3 to} R ^A′6 each independently represent an alkyl group or an aryl group, Z ^A′1 and Z ^A′2 each independently represent —O— or —NRa—, Ra represents a hydrogen atom or an alkyl group, and L ^A′1 and L ^A′2 each independently represent an alkylene group. R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined, and X ^A′1 and X ^A′2 each independently represent a halogen ^atom Represents a compound ion or an aliphatic or aromatic carboxylate ion.

<5> The polymer functional membrane according to <1>, wherein the anion exchange membrane has a structural unit represented by the formula CL-1.
<6> A polymer functional membrane comprising a surface layer containing a polyamide resin having a crosslinked structure on a cation exchange membrane containing an acrylic resin,
<7> The functional polymer membrane according to <6>, wherein the acrylic resin in the cation exchange membrane has a structural unit represented by the following formula IC:

In formula IC, R ^C1 represents a hydrogen atom or an alkyl group, L ^C1 represents an alkylene group or an arylene group, and X ^{C1 +} represents an inorganic or organic cation.

  <8> The polymer functional membrane according to <6> or <7>, wherein the cation exchange membrane has a structural unit represented by the following formula ICL:

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more.

  <9> The polymer functional membrane according to <6> or <7>, wherein the cation exchange membrane has a structural unit represented by the following formula ICL-3:

In Formula ICL-3, R ^B1 and R ^B2 each independently represent a hydrogen atom or an alkyl group, R ^{B3 to} R ^B6 each independently represent a substituent, and k1 to k4 each independently represent 0 to 4 If the an ^integer, presence of a plurality of at least one of ^{R B3 ~R B6, R B3 ~R} B6 may each be the same or different, may be bonded to each other to form a ring, ^{a 1} to a ⁴ each independently represent a single bond or a divalent linking group, M ¹ is a hydrogen atom, an organic base ion or a metal ion, it is nb1 and nb2 each independently represents an integer of 1 to 4, mb1 and mb2 represent 0 or 1, J ¹ represents a single bond, —O—, —S—, —SO ₂ —, —CO—, —CR ^B7 R ^B8 — or an alkenylene group, and R ^B7 and R ^B8. Each independently Atom, an alkyl group or a halogen atom, p is an integer of 1 or more, q represents 1 to 4 or more integer.

<10> Any one of <1> to <9>, wherein the polyamide resin is a polyamide resin comprising a polycondensation reaction between an aliphatic diamine and a divalent and / or trivalent aromatic carboxylic acid chloride. Functional polymer membrane according to
<11> The polymer functional film according to any one of <1> to <10>, wherein the surface layer has a thickness of 1 nm to 10 μm.
<12> An anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the above formula CL-1, or a cation exchange membrane containing an acrylic resin is impregnated or coated with an amine-containing aqueous solution. An amine treatment step, and a surface layer forming step of impregnating or applying an ion-exchange membrane impregnated or coated with an amine-containing aqueous solution with a carboxylic acid chloride-containing solution to form a surface layer containing a polyamide resin by a polycondensation reaction In this order, the method for producing a functional polymer film according to any one of <1> to <11>,
<13> A laminate comprising the polymer functional film according to any one of <1> to <11>,
<14> An apparatus comprising the polymer functional film according to any one of <1> to <11>.

  According to the present invention, a polymer functional membrane having high monovalent ion selective permeability and less membrane salt leakage, a method for producing the same, and a laminate and an apparatus provided with the polymer functional membrane are provided. I was able to.

It is a schematic diagram of the flow path of the apparatus for measuring the salt leakage rate of a membrane.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “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 the description of the group (atomic group) in this specification, the description which does not describe substitution and non-substitution includes what does not have a substituent and what has a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
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. Or a mixture thereof.
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In this specification, “(meth) acrylate” represents acrylate and methacrylate, “(meth) acryl” represents acryl and methacryl, “(meth) acryloyl” represents acryloyl and methacryloyl, “(meth) ) Acrylamide "refers to acrylamide and methacrylamide. The “acrylic resin” is a homopolymer or copolymer of a compound selected from the group consisting of a (meth) acrylate compound and a (meth) acrylamide compound. It is assumed that the resin is copolymerized by 50% by mass or more.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

(Polymer functional membrane)
The first embodiment of the polymer functional membrane of the present invention (hereinafter also simply referred to as “membrane”) is an anion containing an acrylic resin and / or a resin having a structural unit represented by the following formula CL-1. It has a surface layer containing a polyamide resin having a crosslinked structure on the exchange membrane.

In Formula CL-1, L ¹ and L ² each independently represent an alkylene group or an alkenylene group, R ^a and R ^b each independently represent an alkyl group or an aryl group, and R ^a and R ^b are taken together, may form a ring, they are each n1 and n2 independently represent an integer of 1 to 3, X ₁ ^- and X ₂ ^- each independently represent an organic or inorganic anion.

  The second embodiment of the polymer functional membrane of the present invention is characterized by having a surface layer containing a polyamide resin having a crosslinked structure on a cation exchange membrane containing an acrylic resin.

In recent years, an increase in nitrate ion concentration in groundwater has become a problem on a global scale, and a method for removing nitrate ions by electrodialysis using an ion exchange membrane has attracted attention. Preventing the precipitation (scaling) of sparingly soluble salts caused by sulfate ions or the like is an essential problem, and it is important to selectively permeate only nitrate ions (monovalent ions).
As a result of intensive studies, the present inventors have provided a surface layer containing a polyamide resin having a cross-linked structure on an ion exchange membrane containing a resin having a specific structure. It has been found that a polymer functional film with a small amount can be obtained.
Moreover, since it is a polymeric functional membrane with little salt leakage of a membrane, it is excellent in the desalination efficiency at the time of electrodialysis, Therefore It can use suitably for electrodialysis.
Hereinafter, the characteristics of the polymer functional film of the present invention and each component constituting the polymer functional film of the present invention will be described. Unless otherwise specified, the “polymer functional film of the present invention” simply includes the cases of both the first embodiment and the second embodiment.

The polymer functional membrane of the present invention is a membrane having monovalent ion selective permeability. More specifically, the polymer functional membrane of the present invention in the first embodiment is monovalent anion selective permeability. The polymer functional membrane of the present invention in the second embodiment is a membrane having monovalent cation selective permeability.
The polymer functional membrane of the present invention can be suitably used as a membrane for performing ion exchange, reverse osmosis, forward osmosis, gas separation and the like.
When it has a support body, the thickness of the polymeric functional film of this invention is 30-1,000 micrometers including a support body, 50-500 micrometers is more preferable, 100-400 micrometers is still more preferable.
In addition, as a substituent in each structural unit or component used in the present invention, an electrically neutral and inactive group can be used without inhibiting the function of the polymer functional film. is there.

<Surface layer>
The polymer functional membrane of the present invention is crosslinked on an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the formula CL-1, or a cation exchange membrane containing an acrylic resin. It has a surface layer containing a polyamide resin having a structure.
The polymer functional membrane of the present invention may have the surface layer on one side or both sides of the anion exchange membrane or the cation exchange membrane. It is preferable to have it on both sides from the viewpoint of the property and the salt leakage inhibiting property of the membrane.
The surface layer is a layer containing a polyamide resin having a cross-linked structure, and is preferably a layer made of a polyamide resin having a cross-linked structure from the viewpoints of monovalent ion selective permeability and suppression of salt leakage of the membrane.
The thickness of the surface layer is preferably 10 nm to 10 μm, more preferably 50 nm to 1 μm, and still more preferably 100 to 600 nm. Within the above range, the monovalent ion selective permeability and the salt leakage inhibiting property of the membrane are excellent, and an increase in the electrical resistance of the membrane can also be suppressed.

The polyamide resin having a crosslinked structure can be suitably synthesized by using a bifunctional or higher functional amine compound and a bifunctional and / or trifunctional or higher functional carboxylic acid compound as raw materials. It is more preferable to use an acid compound.
The polyfunctional carboxylic acid compound used for the synthesis of the polyamide resin may be a polyfunctional carboxylic acid, a polyfunctional carboxylic acid ester, or a polyfunctional carboxylic acid halide. From the viewpoint of cost, a polyfunctional carboxylic acid halide is preferable, and a polyfunctional carboxylic acid chloride is more preferable.

Examples of the polyfunctional amine compound used in the present invention include amine compounds having two or more primary or secondary amino groups.
Specific examples of the polyfunctional amine compound include, for example, phenylenediamine in which two primary amino groups (—NH ₂ ) are bonded to a benzene ring in the ortho, meta, or para positional relationship, 1, 3, 5 -Aromatic polyfunctional amine compounds such as triaminobenzene, 1,2,4-triaminobenzene, 3,5-diaminobenzoic acid and xylylenediamine, aliphatic polyfunctional amine compounds such as ethylenediamine and propylenediamine, Examples include alicyclic polyfunctional amine compounds such as 2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, and 4-aminomethylpiperazine. These polyfunctional amine compounds may be used individually by 1 type, and 2 or more types may be mixed and used for them. Moreover, the polyfunctional amine compound which has both a primary amino group and a secondary amino group may be sufficient.
Among these, an aliphatic polyfunctional amine compound and / or an alicyclic polyfunctional amine compound are preferable, and ethylenediamine and / or piperazine are more preferable.

The polyfunctional carboxylic acid halide used in the present invention is not particularly limited as long as it is a polyfunctional carboxylic acid halide having two or more carboxylic acid halide groups. For example, trimesine which is a trifunctional carboxylic acid halide. Acid trichloride, 1,3,5-cyclohexanetricarboxylic acid trichloride, 1,2,4-cyclobutanetricarboxylic acid trichloride, bifunctional polyfunctional carboxylic acid halide, for example, biphenyl dicarboxylic acid dichloride, biphenylene dicarboxylic acid dichloride , Aromatic bifunctional carboxylic acid halides such as azobenzene dicarboxylic acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, naphthalene dicarboxylic acid dichloride, adipoyl dichloride, sebacoyl dichloride, etc. Aliphatic difunctional carboxylic acid halide, cyclopentane dicarboxylic acid dichloride, cyclohexanedicarboxylic acid dichloride, alicyclic bifunctional carboxylic acid halides such as tetrahydrofuran dicarboxylic acid dichloride and the like. These polyfunctional carboxylic acid halides may be used alone or in a combination of two or more.
Among these, polyfunctional carboxylic acid chloride is preferable, trifunctional carboxylic acid chloride is more preferable, and trimesic acid trichloride is still more preferable.

  There is no restriction | limiting in particular as a formation method of a surface layer, Although a well-known method can be used, It is preferable to form by the manufacturing method of the polymeric functional film of this invention mentioned later.

<Anion exchange membrane>
The first embodiment of the polymer functional membrane of the present invention has an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the formula CL-1.
The anion exchange membrane includes a resin having an anion exchange group.
The anion exchange group is not particularly limited as long as it is a cationic group, but is preferably a group having a quaternary nitrogen atom. For example, a nitrogen atom in a nitrogen-containing heterocycle such as an ammonio group or a pyridinio group is a cation, or a quaternized nitrogen atom or a nitrogen atom in an aromatic heterocycle is substituted such as alkylation or arylation And those substituted with a group.
In addition, the resin having the structural unit represented by the formula CL-1 has two anion exchange groups in the structural unit represented by the formula CL-1.

<< Support >>
The anion exchange membrane may have a support, and the support is preferably a membrane having a porous support. By allowing the acrylic resin and / or the resin having the structural unit represented by the formula CL-1 to exist in the pores of the porous support, the porous support can be configured as a part of the membrane. .
The porous support as the reinforcing material is preferably a resin porous support, for example, a nonwoven fabric such as a synthetic woven fabric or a synthetic nonwoven fabric, a sponge film, or a film having fine through-holes. It is done.

The material forming the porous support in 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, polyetherimide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoro Examples include porous membranes based on propylene, polychlorotrifluoroethylene and copolymers thereof.
Commercially available porous supports are commercially available from, for example, Mitsubishi Paper Industries Co., Ltd., Nippon Kogyo Paper Industry Co., Ltd., Asahi Kasei Fibers Co., Ltd., Japan Vilene Co., Ltd., Tapirs Corporation, and Freudenberg Filtration Technologies.
In addition, when performing the polymerization hardening reaction by energy ray irradiation, the porous support body is required not to block the wavelength region of the energy ray, that is, to pass the irradiation of the wavelength used for the polymerization hardening.

The porous support is preferably one that can be penetrated by the polymerizable composition forming the structural unit represented by the acrylic resin and / or the formula CL-1.
The porous support preferably has hydrophilicity. In order to impart hydrophilicity to the support, general methods such as corona treatment, plasma treatment, fluorine gas treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.

The porous support in the present invention is preferably a non-woven fabric, and more preferably a non-woven fabric made of a composite fiber of polyethylene and polypropylene. The fiber diameter of the composite fiber is preferably 0.5 to 15 μm, more preferably 1 to 13 μm, and particularly preferably 2 to 10 μm.
The thickness of the porous support in the present invention is preferably 20 to 200 μm, more preferably 30 to 150 μm, and particularly preferably 40 to 120 μm.

<< Structural Unit Represented by Formula CL-1 >>
The anion exchange membrane preferably contains a resin having a structural unit represented by the following formula CL-1.

In Formula CL-1, L ¹ and L ² each independently represent an alkylene group or an alkenylene group, R ^a and R ^b each independently represent an alkyl group or an aryl group, and R ^a and R ^b are taken together, may form a ring, they are each n1 and n2 independently represent an integer of 1 to 3, X ₁ ^- and X ₂ ^- each independently represent an organic or inorganic anion.

L ¹ and L ² each independently represent an alkylene group or an alkenylene group, preferably an alkylene group.
The alkylene group and alkenylene group may be linear, may have a branch, or may have a ring structure.
The alkylene group in L ¹ and L ² preferably has 2 to 10 carbon atoms, more preferably 2 or 3 carbon atoms, 1,2-ethylene group, 1,3-propylene group, 1, A 2-propylene group is mentioned.
The alkenylene group in L ¹ and L ² preferably has 2 to 10 carbon atoms, more preferably 2 or 3 carbon atoms, and still more preferably an ethenylene group.

R ^a and R ^b each independently represents an alkyl group or an aryl group, preferably an alkyl group, and R ^a and R ^b may be bonded to each other to form a ring. Among these, it is more preferable that R ^a and R ^b are bonded to each other to form a ring.
When R ^a and R ^b are bonded to each other to form a ring, the group in which R ^a and R ^b are bonded to each other is preferably an alkylene group, and is preferably an alkylene group having 2 to 4 carbon atoms. More preferred is an alkylene group having 2 or 3 carbon atoms, and particularly preferred is a 1,2-ethylene group.
In Formula CL-1, L ¹ and L ² and two nitrogen atoms preferably form a piperazine ring or a dihydropyrazine ring, and R ^a and R ^b are bonded to each other, together with L ¹ and L ² It is more preferable to form a triethylenediamine ring (1,4-diazabicyclo [2.2.2] octane ring). Further, the formed ring may have a substituent. As the substituent, an alkyl group is preferable.
R ^a and R ^b each independently preferably have 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and still more preferably 1 to 4 carbon atoms.
When R ^a and R ^b are not bonded to each other to form a ring, the alkyl group is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and 1 or 2 carbon atoms. Further preferred. Preferred examples of the alkyl group include a methyl group, an ethyl group, an isopropyl group, an n-butyl group, and a 2-ethylhexyl group.
The alkyl group may have a branch or a ring structure.
Moreover, as an aryl group, a C6-C10 aryl group is preferable and a phenyl group is more preferable.

n1 and n2 each independently represent an integer of 1 to 3, preferably 1 or 2, and more preferably 1.
From the viewpoint of synthesis, n1 and n2 are preferably the same.
X ₁ ^- and X ₂ ^- each independently represents an organic or inorganic anion, an inorganic anion is preferable. The organic or inorganic anion may be a monovalent anion or a divalent or higher anion. In the case of a divalent or higher anion, there is an amount that is electrically equivalent to a cation such as an ammonium group in formula CL-1. For example, X ₁ ⁻ and X ₂ ⁻ in the formula CL-1 may be one divalent anion, or a divalent or higher anion is a structural unit X ₁ ^{− of the} structural unit represented by the formula CL-1. And / or X ₂ ⁻ may be present.
Examples of the organic anion include an alkyl sulfonate anion, an aryl sulfonate anion, an alkyl or aryl carboxylate anion, and examples thereof include a methane sulfonate anion, a benzene sulfonate anion, a toluene sulfonate anion, and an acetate anion.
Examples of inorganic anions include halide ions, sulfate ions, and phosphate ions, and halide ions are preferred. Of the halide ions, chloride ions and bromide ions are preferable, and chloride ions are particularly preferable.

  The structural unit represented by the formula CL-1 is preferably a structural unit represented by any one of the following formulas CL-2 to CL-13, but the present invention is not limited thereto.

  The molecular weight of the structural unit represented by Formula CL-1 is preferably 300 to 600, more preferably 300 to 500, and still more preferably 300 to 450.

The resin may contain the structural unit represented by the formula CL-1 alone or in combination of two or more.
The content of the structural unit represented by the formula CL-1 is preferably 55 to 99% by mass, more preferably 70 to 99% by mass, and 75 to 99% by mass with respect to the total mass of the resin. % Is more preferable, 85 to 99% by mass is particularly preferable, and 90 to 99% by mass is most preferable. When the content of the structural unit represented by Formula CL-1 is in the above range, the physical strength of the formed film is excellent, and the film performance is excellent.

  The method for introducing the structural unit represented by the formula CL-1 is not particularly limited, but as a crosslinking agent, a method represented by the following formula CL-1 ′ or a styrene alkyl halide compound is polymerized. A method of preparing a resin and reacting an amine compound as a cross-linking agent by a polymer reaction may be mentioned.

^L 1 in Formula ^{CL-1 ', L 2,} R a, R b, n1, n2, X 1 - and _{X 2} ^- is, ^{L 1,} L ² in Formula ^{CL-1, R a, R} b, n1, n2, _{X 1} ^- and _{X 2} ^- and have the same meanings and preferred ranges are also the same.

<< Structural Unit Represented by Formula IA >>
The acrylic resin contained in the anion exchange membrane preferably has a structural unit represented by the formula IA.

In Formula IA, R ^A1 represents a hydrogen atom or an alkyl group, R ^{A2 to} R ^A4 each independently represents an alkyl group or an aryl group, and two or more of R ^{A2 to} R ^A4 are bonded to each other to form a ring. it may be ^{formed, Z A1} is -O- or -N ^{(R a)} - represents, ^{R a} represents hydrogen atom or an alkyl ^{group, L A1} represents an alkylene ^{group, X A1-} halide ion or Represents an aliphatic or aromatic carboxylate ion.

The alkyl group in R ^A1 , R ^{A2 to} R ^A4 and R ^a is preferably a linear or branched alkyl group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, and 1 to 4 carbon atoms. Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
6-16 are preferable, as for carbon number of the aryl group in R < ^A2 > -R < ^A4 >, 6-12 are more preferable, and 6-10 are still more preferable. Examples include phenyl and naphthyl.
As a ring formed by bonding two or more of R ^{A2 to} R ^A4 to each other, a 5- or 6-membered monocyclic or bridged ring is preferable, and the carbon number thereof is preferably 4 to 16, and preferably 4 to 10 More preferred. Examples include pyrrolidine ring, piperazine ring, piperidine ring, morpholine ring, thiomorpholine ring, indole ring, and quinuclidine ring.

The number of carbon atoms of L ^A1 is 1 to 10, more preferably from 2 to 10, more preferably 2 to 6, more particularly preferably 2 to 4, 3 being most preferred.
Examples of halide ions in X ^A1 include fluoride ions, chloride ions, bromide ions, and iodide ions.
The number of carbon atoms of the aliphatic carboxylic acid ions in X ^A1 is preferably from 1 to 20, more preferably from 2 to 10, more preferably 2 to 5, particularly preferably 2 or 3, and most preferably 2.
The aliphatic carboxylic acid in the aliphatic carboxylate ion may be either a carboxylic acid in which a carboxyl group is bonded to a saturated hydrocarbon or a carboxylic acid in which a carboxyl group is bonded to an unsaturated hydrocarbon, but the saturated hydrocarbon has a carboxyl group. A bound carboxylic acid is preferred.
The aromatic carboxylate ion in X ^A1 is preferably an aryl carboxylate ion or a heteroaryl carboxylate ion. Here, the heteroaryl group in the heteroaryl sulfonate ion is preferably a 5- or 6-membered ring, and the hetero atom constituting the hetero ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom. 1-17 are preferable, as for carbon number of aromatic carboxylate ion, 2-13 are more preferable, and 6-11 are still more preferable. For example, benzoate ion, naphthalenecarboxylate ion, nicotinate ion, and isonicotinic acid ion can be mentioned.

R ^A1 is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R ^{A2 to} R ^A4 are each independently preferably a methyl group or an ethyl group.
Z ^A1 is preferably —N (R ^a ) —.
R ^a is preferably ^a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
X ^A1- is preferably a halide ion.

  The structural unit represented by the formula IA is preferably a structural unit represented by any of the following formulas IA-1 to IA-26, but the present invention is not limited thereto.

  The molecular weight of the structural unit represented by Formula IA is preferably 150 to 350, more preferably 150 to 300, and still more preferably 150 to 270.

Two or more structural units represented by the formula IA may be used in combination in the film.
The content of the structural unit represented by the formula IA is preferably 1 to 90% by mass, more preferably 5 to 90% by mass, and still more preferably 10 to 90% by mass with respect to the total mass of the resin.

  A method for introducing the structural unit represented by the formula IA is not particularly limited, but a method of polymerizing a compound represented by the following formula IA 'is preferable.

^R A1 ^{to R} A4 in formula ^{IA ', Z A1, R a} , L A1 and ^{X A1-} are ^{R A1 ~R A4, Z A1,} R a, L A1 and ^{X A1-} and same meanings in Formula IA The preferable range is also the same.

<< Structural Unit Represented by Formula ICL >>
The resin having the structural unit represented by the acrylic resin and / or the formula CL-1 in the anion exchange membrane preferably has a structural unit represented by the following formula ICL.

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more.

R ^CL1 is preferably a hydrogen atom or a linear or branched alkyl group, and the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. Or 2 is particularly preferred, and 1 is most preferred.
R ^CL1 is more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
Z ^CL1 and Z ^CL2 are preferably each independently —N (R ^a ) —. R ^a is preferably ^a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
p1 is preferably an integer of 1 to 4, more preferably an integer of 1 to 3, further preferably 1 or 2, and particularly preferably 1.

L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, but a (p1 + 1) -valent hydrocarbon group having 2 or more carbon atoms, or a (p1 + 1) -valent group, -O-, -S- or A group having 2 or more carbon atoms in which —N (R ^a ) — and a hydrocarbon group are combined is preferable. Here, R ^a represents a hydrogen atom or an alkyl group. 1-20 are preferable and, as for carbon number of the said coupling group, 1-10 are more preferable.
When Z ^CL1 and Z ^CL2 are —N (R ^a ) —, L ^CL1 is preferably a (p1 + 1) -valent hydrocarbon group. 1-10 are preferable, as for carbon number of such a hydrocarbon group, 1-6 are more preferable, 1-3 are more preferable, and 1 or 2 is especially preferable.
When L ^CL1 is a divalent hydrocarbon group, for example, an ethylene group, a propylene group, a hexamethylene group, an octamethylene group, or a decamethylene group is preferably exemplified.
When Z ^CL1 and Z ^CL2 are —O—, L ^CL1 is a (p1 + 1) valence, and the number of carbons in which —O—, —S—, or —N (R ^a ) — and a hydrocarbon group are combined. Two or more groups are preferred. Among them, a (p1 + 1) -valent group having 2 or more carbon atoms in which —O— and a hydrocarbon group are combined is preferable, and an alkyleneoxyalkyl group or a polyalkyleneoxyalkyl group is more preferable.
When L ^CL1 is a divalent linking group, for example, an alkyleneoxyalkyl group (—L ^Al —O—L ^Al —, L ^Al represents an alkylene group), a polyalkyleneoxyalkyl group (— (L ^Al —O ) _N -L ^Al- , L ^Al represents an alkylene group, and n represents an integer of 2 or more.), Preferably an ethyleneoxyethyl group, a polyethyleneoxyethyl group, a propyleneoxypropyl group, or a polypropyleneoxypropyl group. . That is, the L ^Al is more preferably an ethylene group or a propylene group.

The linking group in ^LCL1 may have a substituent.
The type of the substituent is not particularly limited, and examples thereof include the substituent X described below.
Preferred examples of the substituent X include a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, and an aryl group.

  Specific examples of the structural unit represented by the formula ICL include the following structural units, but the present invention is not limited to these. In the following, q1 represents an integer of 1 to 6, q2 represents an integer of 1 to 4, q3 and q4 each independently represents 2 or 3, q5 to q8 each independently represents 1 to 3 Represents an integer.

  The method for introducing the structural unit represented by the formula ICL is not particularly limited, but a method of polymerizing a compound represented by the following formula ICL ′ is preferable.

^R CL1 in Formula ^{ICL ', Z CL1, Z CL2} , R a, L CL1 and p1 are, ^R CL1 in Formula ^{ICL, Z CL1, Z CL2,} R a, have the same meanings as ^{L CL1} and p1, preferable range It is the same.

  The acrylic resin and / or the resin having a structural unit represented by the formula CL-1 in the anion exchange membrane of the present invention preferably has a structural unit represented by the following formula ICL-2.

In Formula ICL-2, R ^A′1 and R ^A′2 each independently represent a hydrogen atom or an alkyl group, R ^{A′3 to} R ^A′6 each independently represent an alkyl group or an aryl group, Z ^A′1 and Z ^A′2 each independently represent —O— or —NRa—, Ra represents a hydrogen atom or an alkyl group, and L ^A′1 and L ^A′2 each independently represent an alkylene group. R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined, and X ^A′1 and X ^A′2 each independently represent a halogen ^atom Represents a compound ion or an aliphatic or aromatic carboxylate ion.

R ^A′1 and R ^A′2 are each independently preferably a hydrogen atom or a methyl group, and preferably a hydrogen atom. R ^A′1 and R ^A′2 are preferably the same group.
Z ^A′1 and Z ^A′2 are preferably both —NRa— from the viewpoint of resistance to the acid and alkali of the ion exchange membrane after curing.
R ^{A′3 to} R ^A′6 are preferably each independently an alkyl group. R ^{A′3 to} R ^A′6 may be the same as or different from each other, but are preferably the same.
1-9 are preferable, as for carbon number of the alkyl group in ^{RA'3- RA'6} , 1-3 are more preferable, 1 or 2 is still more preferable, and 1 is especially preferable. Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, a pentyl group, an octyl group, and a nonyl group, and a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferable, and a methyl group or an ethyl group Is more preferable, and a methyl group is still more preferable.
The alkyl group may have a branch or a ring structure.

The halide ions in X ^A′1 and X ^A′2 are preferably chloride ions, bromide ions, or iodide ions, and more preferably chloride ions or bromide ions.
As the aliphatic or aromatic carboxylate ion in X ^A′1 and X ^A′2 , an acetate anion is preferable.
The number of carbon atoms of L ^A′1 and L ^A′2 is preferably 1 to 10, preferably 2 to 10, more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 3.
R ^X is preferably an alkylene group, an arylene group or a divalent linking group obtained by combining these, more preferably an alkylene group or a group obtained by combining an alkylene group and an arylene group, and further preferably an alkylene group.
1-9 are preferable, as for carbon number of an alkylene group, 2-8 are more preferable, 3-8 are still more preferable, and 3-5 are especially preferable. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octamethylene group, and a nonamethylene group.
Examples of the arylene group include phenylene and naphthylene, and the number of carbon atoms is preferably 6 to 12.
Examples of the group in which an alkylene group and an arylene group are combined include an alkylene-arylene-alkylene group, and —CH ₂ —C ₆ H ₄ —CH ₂ — is preferable.

  The acrylic resin and the resin having the structural unit represented by the formula CL-1 are structural units other than the structural unit, for example, a known (meth) acrylate compound, a known (meth) acrylamide compound, a known You may have the structural unit derived from monofunctional and / or polyfunctional ethylenically unsaturated compounds, such as a styrene compound. The polyfunctional ethylenically unsaturated compound functions as a crosslinking agent.

<Cation exchange membrane>
The second embodiment of the polymer functional membrane of the present invention has a cation exchange membrane containing an acrylic resin.
The cation exchange membrane includes a resin having a cation exchange group.
The cation exchange group is not particularly limited as long as it is an anionic group, but an acid group or a salt of an acid group is preferable, and a sulfonic acid group or a salt of a sulfonic acid group is more preferable.
The cation exchange membrane may have a support, and the support is preferably a membrane having a porous support.
Examples of the porous support include those described above.

<< Structural Unit Represented by Formula IC >>
The acrylic resin in the cation exchange membrane preferably has a structural unit represented by the following formula IC.

In formula IC, R ^C1 represents a hydrogen atom or an alkyl group, L ^C1 represents an alkylene group or an arylene group, and X ^{C1 +} represents an inorganic or organic cation.

R ^C1 is preferably a hydrogen atom or a linear or branched alkyl group, and the alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 4 carbon atoms. Or 2 is particularly preferred, and 1 is most preferred.
R ^C1 is more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
The alkylene group of L ^C1 is 1 to 10, more preferably from 2 to 8, 3 to 8 is more preferable. Examples thereof include an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a butylene group, a hexamethylene group, and an octamethylene group.
The number of carbon atoms of the arylene group L ^C1 is preferably 6 to 16, more preferably 6 to 12, 6 to 10 is more preferable. Examples thereof include a phenylene group and a naphthylene group.
The alkylene group and arylene group of L ^C1 may have a substituent. Although the kind of substituent is not particularly limited, the substituent X is exemplified.

As an inorganic cation in ^{XC1 +} , a proton or an alkali metal ion is preferable, and a proton, a lithium ion, a sodium ion, or a potassium ion is more preferable.
^Examples of the organic cation in X ^{C1 +} include a quaternary ammonium cation and a cation obtained by alkylating a nitrogen atom of an aromatic nitrogen-containing heterocycle.
Examples of the quaternary ammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, and a dimethylbenzylammonium cation. Examples of the cation obtained by alkylating the nitrogen atom of the aromatic nitrogen-containing heterocycle include a pyridinium cation.
Among them, X ^{C1 +} is preferably a proton, an alkali metal ion, a quaternary ammonium cation or a pyridinium cation.
In Formula IC, —SO ₃ ^— and X ^{C1 +} may form a covalent bond, an ionic bond, or X ^{C1 +} may be free.

  Specific examples of the structural unit represented by the formula IC are shown below, but the present invention is not limited thereto.

  The method for introducing the structural unit represented by the formula IC is not particularly limited, but a method of polymerizing a compound represented by the following formula IC 'is preferable.

^R C1 in formula IC ^{', L C1} and ^{X C1 +} is ^{R C1, L C1} and ^{X C1 +} and same meanings in Formula IC, the preferred range is also the same.

<< Structural Unit Represented by Formula ICL >>
The resin having a structural unit represented by the acrylic resin in the cation exchange membrane preferably has a structural unit represented by the following formula ICL.

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more.

<< Structural Unit Represented by Formula ICL-3 >>
The resin having a structural unit represented by the acrylic resin in the cation exchange membrane preferably has a structural unit represented by the following formula ICL-3.

In Formula ICL-3, R ^B1 and R ^B2 each independently represent a hydrogen atom or an alkyl group, R ^{B3 to} R ^B6 each independently represent a substituent, and k1 to k4 each independently represent 0 to 4 If the an ^integer, presence of a plurality of at least one of ^{R B3 ~R B6, R B3 ~R} B6 may each be the same or different, may be bonded to each other to form a ring, ^{a 1} to a ⁴ each independently represent a single bond or a divalent linking group, M ¹ is a hydrogen atom, an organic base ion or a metal ion, it is nb1 and nb2 each independently represents an integer of 1 to 4, mb1 and mb2 represent 0 or 1, J ¹ represents a single bond, —O—, —S—, —SO ₂ —, —CO—, —CR ^B7 R ^B8 — or an alkenylene group, and R ^B7 and R ^B8. Each independently Atom, an alkyl group or a halogen atom, p is an integer of 1 or more, q represents 1 to 4 or more integer.

The ^type of the substituent in R ^{B3 to} R ^B6 is not particularly limited, but preferred examples include a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, and an aryl group.

  Although the specific example of the monomer used for formation of the structural unit represented by Formula ICL-3 below is shown, this invention is not limited to these.

  The content of the structural unit represented by the formula ICL-3 in the resin having the structural unit represented by the acrylic resin is preferably 1 to 95% by mass, more preferably 10 to 60% by mass with respect to the total mass of the resin. 15-50 mass% is still more preferable. When it is in the above range, the desired curability, pH resistance, mechanical strength, and flexibility are excellent.

  The acrylic resin in the cation exchange membrane may be a monofunctional and / or a structural unit other than the structural unit, for example, a known (meth) acrylate compound, a known (meth) acrylamide compound, a known styrene compound, etc. You may have the structural unit derived from a polyfunctional ethylenically unsaturated compound. The polyfunctional ethylenically unsaturated compound functions as a crosslinking agent.

The anion exchange membrane is preferably a membrane having the acrylic resin and / or a resin having a structural unit represented by the formula CL-1 on the surface and / or inside of the porous support.
The cation exchange membrane is preferably a membrane having the acrylic resin on the surface and / or inside the porous support.
The anion exchange membrane and the cation exchange membrane are preferably membranes containing water, and the resin having the amino group and the structural unit represented by Formula 1 contains water and becomes a gel. More preferably, it is a film.

  The anion exchange membrane and the cation exchange membrane may contain known additives as other components, such as a polymer compound, a polymer dispersant, an anti-crater agent, a plasticizer, a viscosity. It may contain preparation agents, antioxidants, and / or preservatives, and also includes surfactants used before and during film formation, and / or additives such as polymerization inhibitors. You may go out. Moreover, you may contain the polymerization initiator used at the time of superposition | polymerization, the catalyst itself, these residues, etc.

In addition to the resin, various polymer compounds may be added to the anion exchange membrane and the cation exchange membrane in order to adjust membrane properties.
High molecular compounds include acrylic polymers, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinyl butyral resins, polyvinyl formal resins, shellac, vinyl resins, acrylic resins, rubber resins. Waxes and other natural resins can be used. Moreover, these may be used individually by 1 type, or may use 2 or more types together.
The anion exchange membrane and the cation exchange membrane may contain a polymer dispersant.
Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide.

Anti-crater agent is also called surface conditioner, leveling agent or slip agent, and prevents unevenness on the film surface. For example, organic modified polysiloxane (mixture of polyether siloxane and polyether), polyether modified poly Examples thereof include compounds having a structure of siloxane copolymer or silicone-modified copolymer.
Examples of commercially available products include, for example, Tego Glide 432, 110, 130, 406, 410, 411, 415, 420, 435, 440, 450, 482, and 480 manufactured by Evonik Industries. A115, B1484, and ZG400 (all are trade names).
The crater inhibitor is preferably 0 to 10 parts by mass, more preferably 0 to 5 parts by mass, and still more preferably 1 to 2 parts by mass with respect to 100 parts by mass of the total mass of the ion exchange membrane.

The anion exchange membrane and the cation exchange membrane are surfactants such as nonionic surfactants, cationic surfactants, and organic fluoro compounds for adjusting the liquid properties of the coating liquid when forming the membrane. May be contained.
Specific examples of the surfactant include alkylbenzene sulfonate, alkylnaphthalene sulfonate, higher fatty acid salt, sulfonate of higher fatty acid ester, sulfate ester of higher alcohol ether, sulfonate of higher alcohol ether, higher alkyl Anionic surfactants such as alkyl carboxylates of sulfonamides, alkyl phosphates, polyoxyethylene alkyl ethers, polyoxyethylene alkyl phenyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, ethylene oxide adducts of acetylene glycol, Nonionic surfactants such as ethylene oxide adducts of glycerin and polyoxyethylene sorbitan fatty acid esters, and other amphoteric interfaces such as alkyl betaines and amide betaines Sexual agents, silicone-based surfactants, including such as a fluorine-based surfactant, can be appropriately selected from surfactants and derivatives thereof are known.

It is also preferable that the anion exchange membrane and the cation exchange membrane contain a polymerization inhibitor in order to impart stability to the coating solution when forming the membrane.
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 phenol (phenol having a t-butyl group at the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenol. . Specific examples of the hydroquinone compound include monomethyl ether hydroquinone. Specific examples of the amine compound include N-nitroso-N-phenylhydroxylamine, N, N-diethylhydroxylamine and the like. In addition, you may use these polymerization inhibitors individually by 1 type or in combination of 2 or more types.
The content of the polymerization inhibitor is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 1 part by mass, and 0.01 to 0.5 parts by mass with respect to 100 parts by mass of the total mass in the ion exchange membrane. Part is more preferred.

  The thickness of the anion exchange membrane and the cation exchange membrane is preferably 30 to 500 μm, more preferably 50 to 300 μm, still more preferably 50 to 250 μm, and particularly preferably 100 to 160 μm.

<Composition for forming ion exchange membrane>
The ion exchange membrane composition for forming the anion exchange membrane and the cation exchange membrane comprises the polymerizable compound that forms the anion exchange membrane and the cation exchange membrane with respect to the total solid content of the composition. The content is preferably 20 to 90% by mass, more preferably 35 to 85% by mass, and still more preferably 30 to 80% by mass.
It is preferable to contain 1-90 mass% of crosslinking agents, such as a polyfunctional ethylenic compound, with respect to the total solid of a composition, and it is more preferable to contain 10-85 mass%.

<< Polymerization initiator >>
The ion exchange membrane composition preferably contains a polymerization initiator in order to perform polymerization and curing.
Among the polymerization initiators, in the present invention, a photopolymerization initiator is preferable, and a photopolymerization initiator that can be polymerized by ultraviolet irradiation is more preferable.
As photopolymerization initiators, aromatic ketones, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, 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.
The polymerization initiator is not limited to the photopolymerization initiator as long as it can be dissolved in the above components and the solvent used during the reaction.
Examples of this polymerization initiator include oil-soluble peroxide-based thermal polymerization initiators such as benzoyl peroxide (BPO), oil-soluble azo-based thermal polymerization initiators such as azobisisobutyronitrile (AIBN), azobiscyano Examples thereof include water-soluble azo-based thermal polymerization initiators such as herbal acid (ACVA).
In addition, when the water ratio in the solvent for solution polymerization is large, water-soluble peroxide thermal polymerization initiators such as ammonium persulfate and potassium persulfate, hydrogen peroxide water, and the like can also be used. Furthermore, combinations of redox agents such as ferrocene and amines are possible.

  Preferable examples of aromatic ketones, acylphosphine oxide compounds, and thio compounds include “RADIATION CURING IN POLYMER SCIENCE AND TECHNOLOGY”, pp. 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: 1989), etc. can be mentioned.

As the polymerization initiator, a water-soluble polymerization initiator is preferable.
Here, that the polymerization initiator is water-soluble means that it is dissolved in distilled water at 25 ° C. in an amount of 0.1% by mass or more. The water-soluble polymerization initiator is more preferably dissolved by 1% by mass or more in distilled water at 25 ° C., particularly preferably 3% by mass or more.

  In this invention, it is preferable that content of a polymerization initiator is 0.1-10 mass% with respect to the total solid in the composition for ion exchange membrane formation, and it is 0.1-5 mass%. Is more preferable, and it is still more preferable that it is 0.3-2 mass%.

<< Polymerization inhibitor >>
The ion exchange membrane forming composition preferably contains a polymerization inhibitor.
As the polymerization inhibitor, any polymerization inhibitor can be used, and the above-mentioned polymerization inhibitors are preferred.
In addition, 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% by mass, more preferably 0.01 to 1% by mass, based on the total solid content in the composition for forming an ion exchange membrane. More preferably, it is 0.01-0.5 mass%.

<< solvent >>
The composition for forming an ion exchange membrane may contain a solvent.
It is preferable that content of the solvent in the composition for ion exchange membrane formation is 1-60 mass% with respect to the total mass of a composition, It is more preferable that it is 5-50 mass%, 10-40 mass % Is more preferable.
By including the solvent, the curing (polymerization) reaction proceeds uniformly and smoothly. Further, when the porous support is impregnated with the composition for forming an ion exchange membrane, the impregnation proceeds smoothly.

As the solvent, water or a mixed liquid of a solvent having a solubility in water and water of 5% by mass or more is preferably used. Moreover, as said solvent, what is freely mixed with water is preferable. For this reason, the solvent selected from water and a water-soluble solvent is preferable.
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, hexamethylphosphoramide, hexamethylphosphorotriamide, Pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, γ-butyrolactone and the like are mentioned as preferred solvents. Of these, dimethyl sulfoxide, N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferable. These can be used alone or in combination of two or more.

<< Catalyst >>
The composition for forming an ion exchange membrane preferably contains a catalyst from the viewpoint of improving the solubility of the polymerizable compound to be used and / or improving the polymerization rate.
Preferred examples of the catalyst include alkali metal compounds.
As the alkali metal compound, lithium, sodium, potassium hydroxide salt, chloride salt, nitrate salt and the like are preferable. Among these, lithium compounds are more preferable.
Specific examples of lithium compounds include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoroborate, lithium hexa Examples include fluorophosphate and lithium hexafluoroarsenate.
Moreover, it is also preferable to use the said alkali metal compound in order to neutralize the composition for ion exchange membrane formation.
These alkali metal compounds may be hydrates.
Moreover, a catalyst can be used individually by 1 type or in combination of 2 or more types.
The addition amount of the catalyst is preferably 0.1 to 35% by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 30 parts by mass with respect to the total solid content of the composition for forming an ion exchange membrane.

  The composition for forming an ion exchange membrane may contain, for example, a surfactant, a viscosity improver, a surface tension adjuster, and / or a preservative, if necessary.

(Method for producing polymer functional membrane)
The method for producing the functional polymer membrane of the present invention is not particularly limited, but an acrylic resin and / or an anion exchange membrane containing a resin having a structural unit represented by the formula CL-1 or an acrylic resin is used. An amine treatment step in which the cation exchange membrane is impregnated or coated with an amine-containing aqueous solution, and the ion-exchange membrane impregnated or coated with the amine-containing aqueous solution is impregnated with or coated with a carboxylate chloride-containing solution It is preferable to include a surface layer forming step of forming a surface layer containing a polyamide resin by a condensation reaction in this order.

<Amine treatment process>
The method for producing a polymer functional membrane of the present invention is applied to an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the formula CL-1, or a cation exchange membrane containing an acrylic resin. It is preferable to include an amine treatment step of impregnating or applying an amine-containing aqueous solution.
As the amine compound in the amine-containing aqueous solution, the amine compound used for forming the polyamide resin in the surface layer described above is preferably exemplified.
The content of the amine compound in the amine-containing aqueous solution depends on the water solubility of the amine compound, but is preferably 0.1 to 20% by mass, and preferably 0.1 to 10% by mass with respect to the total mass of the aqueous solution. % Is more preferable, and 0.1 to 5% by mass is even more preferable.
Although there is no restriction | limiting in particular as water to be used, Pure water and ion-exchange water are mentioned preferably.

When an anion exchange membrane or a cation exchange membrane is impregnated with an amine-containing aqueous solution, the liquid temperature at the time of impregnation is preferably 0 ° C to 40 ° C, and more preferably 10 ° C to 35 ° C.
Moreover, the process of removing the excess amine containing aqueous solution may be included as needed after the impregnation. There is no restriction | limiting in particular as a removal method, It can remove by well-known methods, such as a rubber roller, an air blow, and wiping off.
Moreover, when impregnating or apply | coating an amine containing aqueous solution to an anion exchange membrane or a cation exchange membrane, after that, the process of removing excess water | moisture may be included as needed. There is no restriction | limiting in particular as a removal method of a water | moisture content, It can remove by a well-known method.

What is necessary is just to produce the anion exchange membrane or cation exchange membrane used for an amine treatment process with reference to a well-known method or a well-known method.
A preferred embodiment of the anion exchange membrane or the cation exchange membrane is as described above.
The anion exchange membrane or cation exchange membrane is preferably formed by impregnating or applying the above-mentioned composition for forming an ion exchange membrane on a porous support and carrying out a polymerization curing reaction.
Specifically, for example, it can be prepared using a temporary support (peeled off from the film after completion of the curing reaction). However, in the present invention, since a porous support that is a part of the polymer functional membrane is used, the ion exchange membrane should be prepared using this porous support without using a temporary support. Is preferred.
Further, the ion exchange membrane can be prepared in a batch system (batch system) using a fixed support, or can be prepared in a continuous system (continuous system) using a moving support.
In the case of using a temporary support, the temporary support does not need to be considered for material permeation. It does n’t matter.
What was mentioned above can be used conveniently for the composition for ion exchange membrane formation.

  The composition for forming an ion exchange membrane can be applied in various ways, for example, 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. Thus, the porous support can be applied or impregnated. Multiple layers can be applied simultaneously or sequentially. For simultaneous multi-layer application, curtain coating, slide coating, slot die coating and extrusion coating are preferred.

  In the continuous production of the ion exchange membrane, it is preferable to continuously produce the ion exchange membrane forming composition on the moving support, the ion exchange membrane forming composition application unit, and the ion exchange membrane. An irradiation source for polymerizing and curing the forming composition, a film winding unit for collecting the formed film, and a support are moved from the ion exchange film forming composition coating unit to the irradiation source and the film winding unit. It is more preferable to manufacture by a manufacturing unit including means for

  As a method for producing an ion exchange membrane, a step of applying or impregnating a porous support with an ion exchange membrane forming composition, and light irradiation of the applied or impregnated ion exchange membrane forming composition, if necessary, In addition to this, it is preferable that the method further includes a step of polymerizing and curing reaction by heating.

In the production unit, the ion exchange membrane-forming composition application unit is provided at a position upstream of the irradiation source, and the irradiation source is positioned upstream of the collection unit.
In order to have sufficient fluidity when applied with a high-speed coater, the viscosity at 35 ° C. of the ion exchange membrane forming composition is preferably less than 4,000 mPa · s, more preferably 1 to 1,000 mPa · s. Preferably, 1 to 500 mPa.s. s is more preferable. In the case of slide bead coating, the viscosity at 35 ° C. is preferably 1 to 100 mPa · s.
In a high-speed coating machine, the composition for forming an ion exchange membrane can be applied to a moving support at a speed exceeding 15 m / min, and can also be applied at a speed exceeding 20 m / min.
In particular, when using a support to increase the mechanical strength, before applying the ion exchange membrane forming composition to the surface of the support, the support is improved, for example, to improve the wettability and adhesion of the support. Therefore, it may be subjected to corona discharge treatment, glow discharge treatment, flame treatment, ultraviolet irradiation treatment, and the like.

Polymerization and curing of the ion exchange membrane forming composition is preferably performed within 60 seconds, more preferably within 15 seconds, particularly preferably within 5 seconds, most preferably, by applying or impregnating the ion exchange membrane forming composition to a support. Start within 3 seconds.
The light irradiation for polymerization curing is 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, irradiation is continuously performed, and the polymerization curing reaction time is determined in consideration of the speed at which the ion exchange membrane forming composition moves through the irradiation beam.
When high intensity ultraviolet rays (UV light) are used in the polymerization curing reaction, a considerable amount of heat is generated, and therefore the lamp of the light source and / or the support / film is cooled with cooling air or the like to prevent overheating. Is preferred. When a significant dose of infrared (IR light) is irradiated with the UV beam, the UV light is irradiated using an IR reflective quartz plate as a filter.
The energy ray is preferably ultraviolet light. The irradiation wavelength is preferably matched with the absorption wavelength and wavelength of any photopolymerization initiator included in the composition for forming an ion exchange membrane. For example, UV-A (400 to 320 nm), UV-B (320 to 280 nm), UV-C (280-200 nm).

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

The energy output of the irradiation source is preferably 20 to 1,000 W / cm, more preferably 40 to 500 W / cm, but it can be higher or lower if the desired exposure dose can be achieved. I do not care. The polymerization hardening of the film is adjusted according to the exposure strength. The exposure dose is preferably at least 40 mJ / cm ² or more, more preferably 100 to more than 100 mJ / cm ² , as measured by the High Energy UV Radiometer (UV Power Pack ^™ manufactured by EIT-Instrument Markets) in the UV-A range indicated by the apparatus. 2,000 mJ / cm ² , most preferably 150 to 1,500 mJ / cm ² . The exposure time can be chosen freely, but is preferably short and most preferably less than 2 seconds.

  When the application speed is high, a plurality of light sources may be used to obtain a necessary exposure dose. In this case, the plurality of light sources may have the same or different exposure intensity.

<Surface layer forming step>
In the method for producing a polymer functional membrane of the present invention, after the amine treatment step, a polycondensation reaction is performed by impregnating or applying an ion-exchange membrane impregnated with an amine-containing aqueous solution or impregnating a coated ion-exchange membrane with a solution containing a carboxylate chloride It is preferable to include a surface layer forming step of forming a surface layer containing a polyamide resin.
Preferred examples of the carboxylic acid chloride in the carboxylic acid chloride-containing solution include the carboxylic acid chlorides used for forming the polyamide resin in the surface layer described above.
The solvent in the carboxylic acid chloride-containing solution is preferably a hydrocarbon solvent, more preferably an aliphatic hydrocarbon solvent, and further preferably an aliphatic saturated hydrocarbon having 5 to 8 carbon atoms. Heptane and / or hexane is particularly preferable.
The said solvent may be used individually by 1 type, or may use 2 or more types together.
The content of the carboxylic acid chloride in the carboxylic acid chloride-containing solution is 0.01 to 5% by mass with respect to the total mass of the solution, although it depends on the solubility of the carboxylic acid chloride in the solvent. It is preferable that it is 0.02-1 mass%, and it is still more preferable that it is 0.05-0.5 mass%.

When the ion exchange membrane impregnated with the amine-containing aqueous solution or impregnated with the carboxylate chloride-containing solution, the liquid temperature during the impregnation is preferably 0 ° C to 40 ° C, and preferably 10 ° C to 35 ° C. It is more preferable.
Moreover, when impregnating or apply | coating the carboxylic acid chloride containing solution to the ion exchange membrane which impregnated or apply | coated the amine containing aqueous solution, the process of removing a solvent may be included as needed. There is no restriction | limiting in particular as a removal method of a solvent, It can remove by a well-known method.

Further, in order to improve the adhesion between the ion exchange membrane and the surface layer, the step of roughening the surface of the ion exchange membrane with sandpaper or the like, or performing corona, plasma treatment or the like before the amine treatment step. May be included.
Moreover, the manufacturing method of the polymeric functional film of this invention may include arbitrary well-known processes other than the said process as needed.

<Uses of polymer functional membrane>
The polymer functional membrane of the present invention is mainly intended for use in particular 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.
As described above, the polymer functional membrane of the present invention is useful as an ion-exchange membrane that selectively permeates only monovalent ions. Electrodesalination, continuous electrodesalination, electrodialysis, polarity switching system It can be used for electrodialysis, reverse electrodialysis and the like, and can be used not only for general purposes but also for medical purposes, and recently it can also be used for solid polymer electrolyte fuel cells.

(Laminated body and device)
The laminate (also referred to as “stack”) of the present invention is a laminate comprising the polymer functional membrane of the present invention, and an anion exchange membrane and a cation exchange membrane are alternately arranged between a pair of electrodes. Preferably, the module is a module that includes at least the polymer functional membrane of the present invention as the anion exchange membrane and / or cation exchange membrane.
The device of the present invention is a device provided with the polymer functional film of the present invention, and is preferably a device used for the above-mentioned use.
Further, in the laminate of the present invention and the apparatus of the present invention, when the electrode pair is used and the polymer functional film of the first embodiment of the present invention is used, the polymer of the first embodiment of the present invention is used. It is preferable to provide the functional layer so that the surface layer is at least on the cathode side. In addition, when the electrode pair is used and the polymer functional film of the second embodiment of the present invention is used, the surface layer in the polymer functional film of the second embodiment of the present invention is at least on the anode side. It is preferable to provide it.

  The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.

<Preparation of coating solution for ion exchange membrane forming composition>
Preparation of anion exchange membrane forming compositions a-1 to a-5 and cation exchange membrane forming compositions c-1 and c-2 with the compositions (units: parts by mass) shown in Table 1 below, respectively. did.
In addition, "-" in Table 1 represents not containing.

<Description of Abbreviations in Table 1>
Monomer DMAPAA-Q: dimethylaminopropylacrylamide methyl chloride quaternary salt (3-acrylamidopropyltrimethylammonium chloride) (manufactured by Kojin Co., Ltd.)
VBTMAC: Vinylbenzyltrimethylammonium chloride (trade name: (vinylbenzyl) trimethylammonium chloride, manufactured by Sigma-Aldrich)
AMPS (registered trademark): 2-acrylamido-2-methylpropanesulfonic acid (manufactured by Lubrizol)
・ Crosslinking agent MBA: Methylenebisacrylamide (manufactured by Tokyo Chemical Industry Co., Ltd.)
SR-259: Polyethylene glycol 200 diacrylate (manufactured by Sartomer)
Polymerizable compounds 1 to 4: The compounds having structures shown on the right side described in Table 2 below and the schemes shown in Table 2 below were respectively synthesized.
Photopolymerization initiator Darocur (registered trademark) 1173: Trade name, manufactured by BASF Japan Ltd. Polymerization inhibitor MEHQ: Monomethyl ether hydroquinone (manufactured by Sigma Aldrich)
Genorad 16: trade name, manufactured by Rahn AG, catalyst LiNO ₃ : lithium nitrate (manufactured by Chemetall)
LiOH.H ₂ O: lithium hydroxide monohydrate (manufactured by Chemetall)
・ Neutralizer: Sodium hydroxide (manufactured by Tokyo Chemical Industry Co., Ltd.)
・ Solvent IPA: Isopropyl alcohol (Wako Pure Chemical Industries, Ltd.)
Non-woven fabric FO-2223-10: manufactured by Freudenberg, thickness 100 μm, polypropylene / polyethylene FO-2226-14: manufactured by Freudenberg, thickness 160 μm, polypropylene / polyethylene

<Preparation of surface layer forming composition>
Each composition for surface layer formation (a set of an amine aqueous solution and an acid chloride solution) was prepared with the composition (unit: parts by mass) shown in Table 3 below.
In addition, "-" in Table 3 represents not containing.

<Description of Abbreviations in Table 3>
EDA: Ethylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.)
TMC: trimesic acid chloride (1,3,5-benzenetricarbonyl trichloride, manufactured by Sigma-Aldrich)
Isophthaloyl dichloride: (manufactured by Tokyo Chemical Industry Co., Ltd.)

Example 1
Composition A-1 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 nonwoven fabric (FO-2223-10 manufactured by Freudenberg, thickness 100 μm). Was impregnated with composition a-1. Excess composition a-1 was removed using a rod not wound with wire. The temperature of the composition a-1 at the time of application | coating was about 25 degreeC (room temperature). By using a UV exposure machine (Fusion UV Systems, Model Light Hammer 10, D-bulb, conveyor speed 9.5 m / min, 100% strength), the composition a-1 impregnated nonwoven fabric is polymerized and cured. Composition a-1 was cured to form an anion exchange membrane. The exposure amount was 1,000 mJ / cm ² in the UV-A region. This was removed from the aluminum plate and stored in a 0.1 M NaCl solution for at least 12 hours to produce an anion exchange membrane a-1 having a thickness of 135 μm supported on a nonwoven fabric.

After the ion exchange membrane a-1 was immersed in an aqueous amine solution of SL-1 shown in Table 3 for 1 minute, the membrane was taken out and the excess aqueous amine solution on the surface was wiped off. Then, by immersing in the acid chloride solution of SL-1 shown in Table 3 for 1 minute, a surface layer made of a polyamide resin was formed on both surfaces of the ion exchange membrane a-1 by a polymerization reaction. A polymer functional membrane was obtained.
In addition, the thickness of each formed surface layer was about 200 nm when observed with the scanning electron microscope (SEM).

(Examples 2-8 and Comparative Examples 1-4)
As shown in Table 4 below, Examples 2 to 8 were performed in the same manner as Example 1 except that the thickness of the layer was changed by changing the ion exchange membrane, the composition forming the surface layer and / or the nonwoven fabric. And the polymeric functional film of Comparative Examples 1-4 was produced, respectively.
AMX: Astom Co., Ltd. Neoceptor standard membrane AMX was used. In Comparative Example 3, a membrane used in Comparative Example 3 was produced in the same manner as in Example 1 except that the ion exchange membrane was changed to AMX.
ACS: Neoceptor special membrane ACS manufactured by Astom Co., Ltd. was used as it was in Comparative Example 4.

Example 9
After the ion exchange membrane a-1 was immersed in an aqueous amine solution of SL-1 shown in Table 3 for 1 minute, the membrane was taken out and the excess aqueous amine solution on the surface was wiped off. Then, the surface layer is formed on one surface of the ion exchange membrane a-1 by a polymerization reaction by applying the acid chloride solution of SL-1 shown in Table 3 to only one surface of the ion exchange membrane a-1. Thus, a polymer functional film of Example 9 was obtained.

  The following items were evaluated for the polymer functional membranes of Examples 1 to 9 and Comparative Examples 1 to 4. The results obtained are summarized in Table 4 below.

<Film thickness>
At the stage where the ion exchange membrane and the surface layer to be measured are provided, a sample in a state before being provided and a sample after being provided are prepared, and these are immersed in a 0.1 M NaCl aqueous solution at a temperature of 25 ° C. for 12 hours. After removing the film and wiping off the water on the surface, the film thickness of each sample was measured with a micrometer. The film thickness of the provided layer was determined from the difference in film thickness before and after the provision.

<Neurability between amine solution and ion exchange membrane>
Place the ion-exchange membrane between Kim Towel and remove the moisture on the surface, then place it horizontally. The degree of spreading of the amine solution when the amine solution for forming the surface layer prepared according to Table 3 was dropped on this film was evaluated as a wettability and visually evaluated.
At this time, the evaluation was made with A as the case where the amine solution spreads in a film shape, B as the case where the spread was slightly observed, and C as the case where the spread was hardly observed.

<Electrical resistance ER (Ω · cm ² ) of membrane>
Wipe both sides of the membrane immersed in 0.5M NaCl aqueous solution for about 2 hours with dry filter paper and use a two-chamber cell (effective membrane area 1 cm ² , use Ag / AgCl reference electrode (made by Metrohm) as electrode) I caught it. Both chambers are filled with 100 mL of NaCl solution of the same concentration, placed in a constant temperature water bath at 25 ° C. and left to reach equilibrium, and after the liquid temperature in the cell has reached 25 ° C. correctly, an AC bridge (frequency 1,000 Hz) the electrical resistance r ₁ was measured by. 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 . This was taken as the electrical resistance ER (0.5 M NaCl) of the membrane.
In Table 4 below, the electrical resistance ER of the film was omitted and indicated as “ER”.

<Salt leakage rate (ml / m ² / Pa / hr)>
The salt leakage rate of the membrane was measured by an apparatus having a flow path 10 shown in FIG. In FIG. 1, 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 electric conductivity of the feed solution after the measurement was measured by the measurement method using the above apparatus, and the concentration of NaCl was calculated. The salt leakage rate (NaCl permeation rate) was calculated from the NaCl concentration.
The salt leakage rate is defined as a value obtained by converting the amount (number of moles) of NaCl calculated from electric conductivity per unit time, per unit area, and per unit osmotic pressure.

<Ion selective permeability evaluation (electrodialysis): anion exchange membrane>
Electrodialysis evaluation was performed using a cartridge holder that can fix the cartridge “AC-220” (trade name, manufactured by Astom Co., Ltd.) for the micro acylator S1. As the electrode, titanium having a platinum plating of 0.2 μm was used for the anode, and platinum was used for the cathode side.
A solution prepared by mixing equal volumes of 0.05 M NaCl aqueous solution, 0.05 M NaNO ₃ aqueous solution and 0.025 M Na ₂ SO ₄ aqueous solution was used. The ion exchange membrane to be evaluated sufficiently immersed in the obtained mixed solution was prepared from the anode side using a cation exchange membrane (CMX manufactured by Astom Co., Ltd.), an anion exchange membrane (in Examples and Comparative Examples). The produced functional polymer membrane was used.), And the cation exchange membranes were stacked alternately with the spacers sandwiched in that order, and stored in a cartridge.
The electrode solution is 50 mL of 0.5 M sodium sulfate aqueous solution, the concentration side and electrolysis solution for electrodialysis is 20 mL of the above mixed solution, and electrodialysis is performed while circulating each at a flow rate of 6 mL / min. It was. The voltage was controlled so that the treatment current was a constant current of 30 mA.
Electrodialysis is performed for a predetermined time (30 minutes), and the ion concentration C _i of NO ₃ ^- and SO ₄ ^2- is quantified by ion chromatography on the diluted solution, and the solution is removed by comparing with the initial concentration C _{i, 0.} The salt rate was calculated. The ratio of the desalting rate between NO ₃ ⁻ and SO ₄ ²⁻ was defined as ion selective permeability.
In addition, the film | membrane which formed the surface layer of Example 7 on one side evaluated on the conditions which faced the surface layer formation surface to the cathode side.

<Ion selective permeability evaluation (electrodialysis): cation exchange membrane>
Electrodialysis evaluation was performed using a cartridge holder that can fix the cartridge “AC-220” (trade name, manufactured by Astom Co., Ltd.) for the micro acylator S1. As the electrode, titanium having a platinum plating of 0.2 μm was used for the anode, and platinum was used for the cathode side.
A solution prepared by mixing equal volumes of 0.05 M NaCl aqueous solution and 0.025 M MgCl ₂ aqueous solution was used. The ion exchange membrane to be evaluated sufficiently immersed in the obtained mixed solution was prepared from the anode side by using an anion exchange membrane (AMX manufactured by Astom Co., Ltd.), an anion exchange membrane (highly produced in Examples). Molecular functional membranes were used.), Anion-exchange membranes were stacked alternately with spacers in the order, and stored in cartridges.
The electrode solution is 50 mL of 0.5 M sodium sulfate aqueous solution, the concentration side and electrolysis solution for electrodialysis is 20 mL of the above mixed solution, and electrodialysis is performed while circulating each at a flow rate of 6 mL / min. It was. The voltage was controlled so that the treatment current was a constant current of 30 mA.
Electrodialysis was performed for a predetermined time (30 minutes), the ion concentration of Na ⁺ and Mg ²⁺ was quantified by ion chromatography on the diluted solution, and the desalination rate was calculated by comparing with the initial concentration. The ratio of the desalting rate was defined as ion selective permeability.

1: Membrane 2: Arrow indicating that water in the feed solution permeates the draw solution through the membrane 3: Feed solution channel 4: Draw solution channel 5: Liquid traveling direction 10: Salt leakage rate measurement Equipment flow path

Claims (14)

On an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the following formula CL-1,
A polymer functional film comprising a surface layer containing a polyamide resin having a crosslinked structure.

In Formula CL-1, L ¹ and L ² each independently represent an alkylene group or an alkenylene group, R ^a and R ^b each independently represent an alkyl group or an aryl group, and R ^a and R ^b are taken together, may form a ring, they are each n1 and n2 independently represent an integer of 1 to 3, X ₁ ^- and X ₂ ^- each independently represent an organic or inorganic anion. The polymer functionality according to claim 1, wherein the acrylic resin and / or the resin having a structural unit represented by the formula CL-1 in the anion exchange membrane has a structural unit represented by the following formula IA. film.

In Formula IA, R ^A1 represents a hydrogen atom or an alkyl group, R ^{A2 to} R ^A4 each independently represents an alkyl group or an aryl group, and two or more of R ^{A2 to} R ^A4 are bonded to each other to form a ring. it may be ^{formed, Z A1} is -O- or -N ^{(R a)} - represents, ^{R a} represents hydrogen atom or an alkyl ^{group, L A1} represents an alkylene ^{group, X A1-} halide ion or Represents an aliphatic or aromatic carboxylate ion. The polymer functionality according to claim 2, wherein the acrylic resin and / or the resin having a structural unit represented by the formula CL-1 in the anion exchange membrane has a structural unit represented by the following formula ICL. film.

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more. The polymer according to claim 2, wherein the acrylic resin and / or the resin having a structural unit represented by the formula CL-1 in the anion exchange membrane has a structural unit represented by the following formula ICL-2. Functional membrane.

In Formula ICL-2, R ^A′1 and R ^A′2 each independently represent a hydrogen atom or an alkyl group, R ^{A′3 to} R ^A′6 each independently represent an alkyl group or an aryl group, Z ^A′1 and Z ^A′2 each independently represent —O— or —NRa—, Ra represents a hydrogen atom or an alkyl group, and L ^A′1 and L ^A′2 each independently represent an alkylene group. R ^X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined, and X ^A′1 and X ^A′2 each independently represent a halogen ^atom Represents a compound ion or an aliphatic or aromatic carboxylate ion.   The polymer functional membrane according to claim 1, wherein the anion exchange membrane has a structural unit represented by the formula CL-1. On the cation exchange membrane containing acrylic resin,
A polymer functional film comprising a surface layer containing a polyamide resin having a crosslinked structure. The polymer functional membrane according to claim 6, wherein the acrylic resin in the cation exchange membrane has a structural unit represented by the following formula IC.

In formula IC, R ^C1 represents a hydrogen atom or an alkyl group, L ^C1 represents an alkylene group or an arylene group, and X ^{C1 +} represents an inorganic or organic cation. The polymer functional membrane according to claim 6 or 7, wherein the cation exchange membrane has a structural unit represented by the following formula ICL.

In the formula ICL, R ^CL1 represents a hydrogen atom or an alkyl group, Z ^CL1 and Z ^CL2 each independently represent —O— or —N (R ^a ) —, R ^a represents ^a hydrogen atom or an alkyl group, L ^CL1 represents a (p1 + 1) -valent linking group having 2 or more carbon atoms, and p1 represents an integer of 1 or more. The polymer functional membrane according to claim 6 or 7, wherein the cation exchange membrane has a structural unit represented by the following formula ICL-3.

In Formula ICL-3, R ^B1 and R ^B2 each independently represent a hydrogen atom or an alkyl group, R ^{B3 to} R ^B6 each independently represent a substituent, and k1 to k4 each independently represent 0 to 4 If the an ^integer, presence of a plurality of at least one of ^{R B3 ~R B6, R B3 ~R} B6 may each be the same or different, may be bonded to each other to form a ring, ^{a 1} to a ⁴ each independently represent a single bond or a divalent linking group, M ¹ is a hydrogen atom, an organic base ion or a metal ion, it is nb1 and nb2 each independently represents an integer of 1 to 4, mb1 and mb2 represent 0 or 1, J ¹ represents a single bond, —O—, —S—, —SO ₂ —, —CO—, —CR ^B7 R ^B8 — or an alkenylene group, and R ^B7 and R ^B8. Each independently Atom, an alkyl group or a halogen atom, p is an integer of 1 or more, q represents 1 to 4 or more integer.   The high polyamide according to any one of claims 1 to 9, wherein the polyamide resin is a polyamide resin comprising a polycondensation reaction between an aliphatic diamine and a divalent and / or trivalent aromatic carboxylic acid chloride. Molecular functional membrane.   The polymeric functional film of any one of Claims 1-10 whose thickness of the said surface layer is 1 nm or more and 10 micrometers or less. An amine treatment step in which an anion exchange membrane containing an acrylic resin and / or a resin having a structural unit represented by the formula CL-1 or a cation exchange membrane containing an acrylic resin is impregnated with or coated with an amine-containing aqueous solution. As well as
A surface layer forming step of impregnating or applying an ion-exchange membrane impregnated with an amine-containing aqueous solution or applying a solution containing a carboxylic acid chloride to form a surface layer containing a polyamide resin by a polycondensation reaction in this order;
The manufacturing method of the polymeric functional film of any one of Claims 1-11.   The laminated body provided with the polymeric functional film of any one of Claims 1-11.   The apparatus provided with the polymeric functional film of any one of Claims 1-11.

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