JPWO2017038328A1 - Ion exchange polymer, curable composition, cured product, member, and apparatus - Google Patents

Abstract

The ion exchange polymer has a structure represented by the following formula 1 and a structure represented by the following formula 2. In Formula 1 and Formula 2, L1 and L2 each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R1, R2 and R3 each independently represent a hydrogen atom or an alkyl group. , R3 and L2 may combine with each other to form a ring, and n independently represents an integer of 0 or more.

Description

  The present invention relates to an ion exchange polymer, a curable composition, a cured product, a member, 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 conventional ion exchange membranes, those described in Patent Document 1 or 2 are known.

US Patent Application Publication No. 2003/0036574 U.S. Pat. No. 4,374,720

  Problems to be solved by the present invention are low water permeability, selective permeability, excellent pH resistance, ion exchange polymer having low membrane resistance when a membrane is formed, low water permeability, selective permeability, and A curable composition capable of obtaining a cured product having excellent pH resistance and low film resistance when a film is formed, a cured product formed by curing the curable composition, and the ion exchange polymer or the above It is providing the member and apparatus provided with hardened | cured material.

The above-described problems of the present invention have been solved by the means described in <1>, <8>, <12>, <14> or <15> below. It is described below together with <2> to <7>, <9> to <11> and <13> which are preferred embodiments.
<1> an ion exchange polymer having a structure represented by the following formula 1 and a structure represented by the following formula 2;

In Formula 1 and Formula 2, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ , R ² and R ³ each independently represent a hydrogen atom Or an alkyl group, R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.
<2> The ion exchange polymer according to <1>, wherein an ester density of the ion exchange polymer is 1.70 mmol / g or less,
<3> The ion exchange polymer according to <1> or <2>, wherein an ester density of the ion exchange polymer is 0.30 mmol / g or more,
<4> The structure represented by Formula 1 includes the structure represented by Formula 3 below, and the structure represented by Formula 2 includes the structure represented by Formula 4 below, <1> to <3> An ion exchange polymer according to any one of

In Formula 3 and Formula 4, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring,
<5> The structure represented by formula 1 includes the structure represented by formula 5 below, and the structure represented by formula 2 includes the structure represented by formula 6 below, <1> to <4> An ion exchange polymer according to any one of

In Formula 5 and Formula 6, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may bond to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion;
<6> The ion exchange polymer according to any one of <1> to <5>, wherein the charge density is 2.00 mmol / g or more and the cross-linking group density is 1.00 mmol / g or more,
<7> The ion exchange polymer according to any one of <1> to <6>, wherein the ion exchange capacity is 2.00 meq or more,
<8> For any one of <1> to <7>, which is for an ion exchange membrane, a proton conductive membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte and / or a water absorbent resin The ion exchange polymers described,
<9> A curable composition containing a polymerizable compound represented by the following formula 7 and a polymerizable compound represented by the following formula 8;

In Formula 7 and Formula 8, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ _, R ² and R ³ each independently represent a hydrogen atom Or an alkyl group, R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.
<10> The curable composition according to <9>, containing 0.1 to 30.0% by mass of the polymerizable compound represented by formula 7 with respect to the total mass of the polymerizable compound,
<11> The polymerizable compound represented by formula 7 includes a polymerizable compound represented by formula 9 below, and the polymerizable compound represented by formula 8 includes a polymerizable compound represented by formula 10 below. <9> or <10> curable composition as described above,

In Formula 9 and Formula 10, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring,
<12> The polymerizable compound represented by formula 7 includes a polymerizable compound represented by formula 11 below, and the polymerizable compound represented by formula 8 includes a polymerizable compound represented by formula 12 below. <9>-<11> any one of <11> curable composition,

In Formula 11 and Formula 12, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may bond to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion;
<13> A cured product formed by curing the curable composition according to any one of <9> to <12>,
<14> The cured product according to <13>, which is an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, and / or a water absorbent resin.
<15> It is formed by curing the ion-exchange polymer according to any one of <1> to <8> or the curable composition according to any one of <9> to <12>. A member provided with a cured product,
<16> It is formed by curing the ion-exchange polymer according to any one of <1> to <8> or the curable composition according to any one of <9> to <12>. A device provided with a cured product.

  According to the present invention, an ion exchange polymer having low water permeability, excellent permselectivity and pH resistance, low membrane resistance when a membrane is formed, low water permeability, excellent permselectivity and pH resistance. A curable composition capable of obtaining a cured product having low film resistance when a film is formed, a cured product formed by curing the curable composition, and the ion-exchange polymer or the cured product. Members and apparatus could be provided.

It is a schematic diagram of the flow path of the apparatus for measuring the water permeability of the film | membrane used in the Example.

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 present specification, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value.
In the notation of group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes the group which has a substituent with the thing which does not have 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 that is the substitution pattern of the double bond in each formula may be either E-form or Z-form, unless otherwise specified, even if one of the isomers is described for the convenience of display. 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.
In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.

(Ion exchange polymer)
The ion exchange polymer of the present invention has a structure represented by the following formula 1 and a structure represented by the following formula 2.
In the present invention, the ion exchange polymer refers to a polymer having an ionic group in the molecular structure.
The ion exchange polymer of the present invention is preferably an anion exchange polymer.
The use of the ion exchange polymer of the present invention is not particularly limited and can be used in various applications. For ion exchange membranes, proton conducting membranes, reverse osmosis membranes, forward osmosis membranes, polymer electrolytes and / or Or it is preferable for water-absorbent resins. Moreover, as an ion exchange membrane, an anion exchange membrane is preferable.
That is, the ion exchange membrane, the proton conducting membrane, the reverse osmosis membrane, the forward osmosis membrane, the polymer electrolyte, and the water absorbent resin preferably include the ion exchange polymer of the present invention.
Moreover, the ion exchange polymer of this invention can be manufactured by hardening | curing the curable composition of this invention mentioned later.

In Formula 1 and Formula 2, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ , R ² and R ³ each independently represent a hydrogen atom Alternatively, it represents an alkyl group, and R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.

In general, the performance required for ion exchange polymers includes low water permeability, high ion selectivity (selectivity), high durability against acids and alkalis (pH resistance), and high conductivity when a membrane is formed. (Low film resistance).
The present inventors consider that the higher the charge density of the ion exchange polymer, the lower the membrane resistance and the higher the selective permeability, and the higher the crosslinkable group density or hydrophobicity, the lower the water permeability. Moreover, in order to increase the crosslinkable group density and the charge density of the ion exchange polymer, it is considered necessary to increase the concentration of the monomer in the curable composition used for the production of the ion exchange polymer.
In the inventions described in Patent Documents 1 and 2, an ion exchange polymer is produced by crosslinking only one of a (meth) acrylamide monomer and a (meth) acrylate monomer.
When the (meth) acrylamide monomer is used alone in the curable composition used for the production of the ion exchange polymer and the monomer concentration in the curable composition is high, the amide of the (meth) acrylamide monomer The present inventors have found that since the site has hydrogen bonding properties, a monomer is precipitated during curing, and there is a problem that a defective site is generated in the ion exchange polymer and the performance is lowered.
In addition, when a (meth) acrylate monomer is used alone in the curable composition used for the production of an ion exchange polymer, the ester group in the structure derived from the (meth) acrylate monomer is derived from the (meth) acrylamide monomer. It was found that there is a problem that the pH resistance of the ion exchange polymer is poor because it is more easily hydrolyzed than the amide group in the structure.
Therefore, the present inventors have a specific structure including an ester group and a quaternary ammonium salt structure and a specific structure including an amide group and a quaternary ammonium salt structure, so that the water permeability is low and the selective permeability is low. The present inventors have found that an ion exchange polymer having a high pH, excellent pH resistance, and low membrane resistance when a membrane is formed can be obtained.
In addition, when an ion exchange polymer containing a combination of the above specific structures is produced using a curable composition containing a specific (meth) acrylate monomer and a specific (meth) acrylamide monomer, it is highly soluble. It is speculated that the monomer concentration in the curable composition can be increased by that the (meth) acrylate monomer serves as a solvent for the specific (meth) acrylamide monomer. Therefore, it is estimated that the charge density and crosslinking group density of the ion exchange polymer can be increased, resulting in a decrease in water permeability.
Furthermore, since the ester group is more easily hydrolyzed than the amide group, according to the embodiment of the present invention containing a specific structure containing an amide group and a specific structure containing an ester group, a (meth) acrylate monomer It is presumed that the pH resistance is improved as compared with an ion-exchange polymer having a specific structure containing an amide group, which is crosslinked alone.
In addition, the present inventors set the ester density in the ion exchange polymer to a value within a specific range, so that even if a structure containing an ester group is included, pH resistance uses only acrylamide as a monomer. It was found to be equivalent to an ion exchange polymer.

  The ion exchange polymer of the present invention preferably includes a structure represented by the following formula 3 as the structure represented by the formula 1, and a structure represented by the following formula 4 as the structure represented by the formula 2. More preferably, the structure represented by Formula 1 includes the structure represented by Formula 5 below, and the structure represented by Formula 2 includes the structure represented by Formula 6 below.

In Formula 3 and Formula 4, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring.

In Formula 5 and Formula 6, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may be bonded to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion.
Hereinafter, the details of the structures represented by Formulas 1 to 6 will be described.

<Structure represented by Formula 1>
The ion exchange polymer of the present invention contains a structure represented by Formula 1.
In Formula 1, L ¹ represents a (2 + n) -valent linking group having a quaternary ammonium salt structure, and a quaternary ammonium salt structure and a hydrocarbon having 2 or more and (2 + n) valence of 2 or more carbon atoms. A group in which at least one group selected from the group, —O—, —S— and —N (R ^N ) — is combined is preferable, and a plurality of quaternary ammonium salt structures and a plurality of divalent or more (2 + n) groups are preferred. ) A group in combination with a hydrocarbon group having 2 or less carbon atoms having a valence or less is more preferable. Here, ^RN 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.
As the quaternary ammonium salt structure, a structure represented by —N ⁺ R ¹¹ R ¹² — is preferable. R ¹¹ and R ¹² each independently represent a monovalent group or a divalent or higher valent group, each independently preferably an alkyl group, and preferably an alkyl group having 1 to 4 carbon atoms. R ¹¹ and / or R ¹² may be a bonding site with n structures in Formula 1 by representing a divalent or higher valent linking group. The divalent or higher linking group is preferably a divalent or higher valent hydrocarbon group, and more preferably an alkylene group.
When the divalent hydrocarbon group is a divalent hydrocarbon group having 2 or more (2 + n) valence or less, an arylene group, an alkylene group, an alkenylene group, or a group represented by a bond thereof is preferable. , An arylene group, an alkylene group, or a group represented by a bond thereof, more preferably a group represented by a bond between an arylene group and an alkylene group, and a bond between a phenylene group and an alkylene group having 1 to 8 carbon atoms. The groups represented are particularly preferred.
When the hydrocarbon group having 2 or more (2 + n) valence or less and having 2 or more carbon atoms represents a hydrocarbon group having 3 or more valences, a group obtained by removing 2 or more hydrogen atoms from an alkyl group, or 2 from an aryl group A group in which the above hydrogen atoms are removed is preferable, and a group in which 2 or more hydrogen atoms are removed from an alkyl group having 1 to 8 carbon atoms or a group in which 3 or more hydrogen atoms are removed from a benzene ring is more preferable. .

R ¹ each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
n represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.

Moreover, the structure represented by Formula 1 preferably contains an inorganic or organic anion as a counter anion with respect to the quaternary ammonium salt structure, and preferably contains an inorganic anion. The inorganic or organic anion is not particularly limited as long as it is an anion that neutralizes electric charge, and may be a monovalent anion or a polyvalent anion, but is preferably a monovalent anion.
Examples of the organic anion include alkane or arene sulfonate ions, alkyl or aryl carboxylate ions, and specific examples include methane sulfonate ions, benzene sulfonate ions, toluene sulfonate ions, and acetate ions.
Examples of the inorganic anion include halide ions, sulfate ions, nitrate ions, carbonate ions, and phosphate ions, and halide ions are preferable. As a halide ion, a chloride ion and a bromide ion are preferable, and a chloride ion is particularly preferable.
The organic or inorganic anion is preferably an alkane or arene sulfonate ion, an alkyl or aryl carboxylate ion, a halide ion, or a sulfate ion, and an alkane or arene sulfonate ion, a halide ion, or It is more preferably a sulfate ion, and further preferably a halide ion.

The structure represented by Formula 1 preferably includes the structure represented by Formula 3, and more preferably includes the structure represented by Formula 5.
The structure represented by Formula 1 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
The method for introducing the structure represented by Formula 1 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 7 (hereinafter also referred to as “compound represented by Formula 7”) is described. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 1 individually by 1 type, and may contain 2 or more types.
The ion exchange polymer of the present invention preferably contains 0.1 to 30% by mass, preferably 5 to 27% by mass of the structure represented by Formula 1 with respect to the total mass of the ion exchange polymer. It is more preferable to contain the mass%.

<Structure represented by Formula 2>
The ion exchange polymer of the present invention contains a structure represented by Formula 2.
In Formula 2, L ² represents a (2 + n) -valent linking group having a quaternary ammonium salt structure, and a quaternary ammonium salt structure and a hydrocarbon having 2 or more and (2 + n) valence of 2 or more carbon atoms. A group in which at least one group selected from the group, —O—, —S— and —N (R ^N ) — is combined is preferable, and a plurality of quaternary ammonium salt structures and a plurality of divalent or more (2 + n) groups are preferred. ) A group in combination with a hydrocarbon group having 2 or less carbon atoms having a valence or less is more preferable. Here, ^RN 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.
As the quaternary ammonium salt structure, a structure represented by —N ⁺ R ²¹ R ²² — is preferable. R ²¹ and R ²² each represent a monovalent group or a divalent or higher valent linking group, each independently preferably an alkyl group, and preferably an alkyl group having 1 to 4 carbon atoms. R ²¹ and / or R ²² may be a binding site with n structures in Formula 1 by representing a divalent or higher valent linking group. The divalent or higher linking group is preferably a divalent or higher valent hydrocarbon group, and more preferably an alkylene group. When R ³ and L ² are bonded to each other to form a ring, it is preferable that R ³ and R ²¹ and / or R ²² are bonded to form a ring.
When the divalent hydrocarbon group is a divalent hydrocarbon group having 2 or more (2 + n) valence or less, an arylene group, an alkylene group, an alkenylene group, or a group represented by a bond thereof is preferable. , An arylene group, an alkylene group, or a group represented by a bond thereof, more preferably a group represented by a bond between an arylene group and an alkylene group, and a bond between a phenylene group and an alkylene group having 1 to 8 carbon atoms. The groups represented are particularly preferred.
When the hydrocarbon group having 2 or more valences (2 + n) or less carbon number is 2 or more and represents a hydrocarbon group having 3 or more valences, it is a group obtained by removing 3 or more hydrogen atoms from an alkyl group, or 3 from an aryl group. A group in which the above hydrogen atom is removed is preferable, a group in which 3 or more hydrogen atoms are removed from an alkyl group having 1 to 8 carbon atoms, or a group in which 3 or more hydrogen atoms are removed from a benzene ring is more preferable. .

R ² each independently represents a hydrogen atom or an alkyl group, preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
R ³ represents a hydrogen atom or an alkyl group, preferably an alkyl group, and more preferably an alkyl group having 1 to 4 carbon atoms.
n represents an integer of 0 or more, preferably 0 to 4, more preferably 0 to 2, and still more preferably 0.

The structure represented by Formula 2 preferably contains an inorganic or organic anion as a counter anion with respect to the quaternary ammonium salt structure, and preferably contains an inorganic anion. The inorganic or organic anion is not particularly limited as long as it is an anion that neutralizes electric charge, and may be a monovalent anion or a polyvalent anion, but is preferably a monovalent anion.
Examples of the organic anion include alkane or arene sulfonate ions, alkyl or aryl carboxylate ions, and specific examples include methane sulfonate ions, benzene sulfonate ions, toluene sulfonate ions, and acetate ions.
Examples of the inorganic anion include halide ions, sulfate ions, nitrate ions, carbonate ions, and phosphate ions, and halide ions are preferable. As a halide ion, a chloride ion and a bromide ion are preferable, and a chloride ion is particularly preferable.
The organic or inorganic anion is preferably an alkane or arene sulfonate ion, an alkyl or aryl carboxylate ion, a halide ion, or a sulfate ion, and an alkane or arene sulfonate ion, a halide ion, or It is more preferably a sulfate ion, and further preferably a halide ion.

The structure represented by Formula 2 preferably includes a structure represented by Formula 4 described below, and more preferably includes a structure represented by Formula 6.
The structure represented by Formula 2 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
The method for introducing the structure represented by Formula 2 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 8 (hereinafter also referred to as “compound represented by Formula 8”) is described. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 2 individually by 1 type, and may contain 2 or more types.
Further, the ion exchange polymer of the present invention preferably contains 0.1 to 95% by mass, preferably 5 to 85% by mass of the structure represented by Formula 2 with respect to the total mass of the ion exchange polymer. It is more preferable to contain -80 mass%.

<Structure represented by Formula 3>
The ion exchange polymer of the present invention preferably has a structure represented by Formula 3.
In Formula 3, L ³ represents a divalent linking group having a quaternary ammonium salt structure, and includes a quaternary ammonium salt structure, a divalent hydrocarbon group having 2 or more carbon atoms, —O—, —S. -And -N ( ^RN )
-A group in which at least one group selected from the above is combined is preferable, and a group in which a plurality of quaternary ammonium salt structures and a plurality of divalent hydrocarbon groups having 2 or more carbon atoms are combined is more preferable- A group represented by A ³ B ³ C ³ B ³ A ³ — is more preferable. Here, A ³ and C ³ each independently represent a divalent hydrocarbon group having 2 or more carbon atoms, and B ³ each independently represents a quaternary ammonium salt structure.
^RN 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.
As the quaternary ammonium salt structure, a structure represented by —N ⁺ R ³¹ R ³² — is preferable. R ³¹ and R ³² each represent a monovalent group, each independently preferably an alkyl group, and preferably an alkyl group having 1 to 4 carbon atoms.
The divalent hydrocarbon group having 2 or more carbon atoms is preferably an arylene group, an alkylene group, an alkenylene group, or a group represented by a bond thereof, an arylene group, an alkylene group, or a group represented by a bond thereof. Are more preferable, a group represented by a bond of an arylene group and an alkylene group is still more preferable, and a group represented by a bond of a phenylene group and an alkylene group having 1 to 8 carbon atoms is particularly preferable.
R ⁴ in formula ³ has the same meaning as R ^{1 in} formula 1, and the preferred embodiment is also the same.

  Moreover, it is preferable that the structure represented by Formula 3 contains an inorganic or organic anion as a counter anion with respect to the quaternary ammonium salt structure. The anion is synonymous with the anion contained in the structure represented by Formula 1, and the preferred range is also the same.

The structure represented by Formula 3 preferably includes a structure represented by Formula 5 described below.
The structure represented by Formula 3 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
The method for introducing the structure represented by Formula 3 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 9 (hereinafter also referred to as “compound represented by Formula 9”) is described. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 3 individually by 1 type, and may contain 2 or more types.
The ion exchange polymer of the present invention preferably contains 0.1 to 30% by mass, preferably 5 to 27% by mass of the structure represented by Formula 3 with respect to the total mass of the ion exchange polymer. It is more preferable to contain the mass%.

<Structure represented by Formula 4>
The ion exchange polymer of the present invention preferably has a structure represented by Formula 4.
In Formula 4, L ⁴ represents a divalent linking group having a quaternary ammonium salt structure, and includes a quaternary ammonium salt structure, a divalent hydrocarbon group having 2 or more carbon atoms, —O—, —S. -And -N ( ^RN )
-A group in which at least one group selected from the above is combined is preferable, and a group in which a plurality of quaternary ammonium salt structures and a plurality of divalent hydrocarbon groups having 2 or more carbon atoms are combined is more preferable- A group represented by A ⁴ B ⁴ C ⁴ B ⁴ A ⁴ — is more preferable. Here, A ⁴ and C ⁴ each independently represent a divalent hydrocarbon group having 2 or more carbon atoms, and B ⁴ each independently represents a quaternary ammonium salt structure. Here, ^RN 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.
As the quaternary ammonium salt structure, a structure represented by —N ⁺ R ⁴¹ R ⁴² — is preferable. R ^4
1 and R ⁴² each represent a monovalent group, and are preferably each independently an alkyl group, and preferably an alkyl group having 1 to 4 carbon atoms. When R ⁶ and L ⁴ are bonded to each other to form a ring, it is preferable that R ⁶ and R ⁴¹ and / or R ⁴² are bonded to form a ring.
The divalent hydrocarbon group having 2 or more carbon atoms is preferably an arylene group, an alkylene group, an alkenylene group, or a group represented by a bond thereof, an arylene group, an alkylene group, or a group represented by a bond thereof. Are more preferable, a group represented by a bond of an arylene group and an alkylene group is still more preferable, and a group represented by a bond of a phenylene group and an alkylene group having 1 to 8 carbon atoms is particularly preferable.

R ⁵ and R ⁶ in Formula 4 have the same meanings as R ² and R ^{3 in} Formula 2, respectively, and the preferred embodiments are also the same.

  Moreover, it is preferable that the structure represented by Formula 4 contains an inorganic or organic anion as a counter anion with respect to a quaternary ammonium salt structure. The anion is synonymous with the anion contained in the structure represented by Formula 2, and the preferred range is also the same.

The structure represented by Formula 4 preferably includes a structure represented by Formula 6 described below.
The structure represented by Formula 4 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
A method for introducing the structure represented by Formula 4 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 10 (hereinafter also referred to as “compound represented by Formula 10”) is described below. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 4 individually by 1 type, and may contain 2 or more types.
The ion exchange polymer of the present invention preferably contains 0.1 to 95% by mass, preferably 5 to 85% by mass of the structure represented by Formula 4 with respect to the total mass of the ion exchange polymer. It is more preferable to contain -80 mass%.

<Structure represented by Formula 5>
The ion exchange polymer of the present invention preferably has a structure represented by Formula 5.
In Formula 5, each R ^a is independently an alkylene group or a combination of one or more alkylene groups and one or more linking groups selected from the group consisting of arylene groups, —O— and —NR ^N —. And preferably an alkylene group. R ^N represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
L ⁵ represents a divalent linking group, and is an alkylene group or a combination of one or more alkylene groups and one or more linking groups selected from the group consisting of an arylene group, —O— and —NR ^N —. An alkylene-arylene-alkylene group, more preferably —CH ₂ —C ₆ H ₄ —CH ₂ —, and —CH ₂ —p—C ₆ H _4. Particularly preferred is —CH ₂ —. The number of carbon atoms of the divalent linking group for L ⁵ represents, preferably 1-20, more preferably 2 to 20, more preferably 8 to 20. R ^N represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
R ^b and R ^c each independently represents an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group or an aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms.
R ⁷ has the same meaning as R ^{1 in} Formula 1, and the preferred embodiment is also the same.
Xa each independently represents an inorganic or organic anion, and is not particularly limited as long as it is an anion that neutralizes charge, and may be a monovalent anion or a polyvalent anion. Preferably, it is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ⁻ , more preferably Cl ⁻ or Br ⁻ , and particularly preferably Cl ⁻ .

The structure represented by Formula 5 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
A method for introducing the structure represented by Formula 5 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 11 (hereinafter, also referred to as “compound represented by Formula 11”) is described below. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 5 individually by 1 type, and may contain 2 or more types.
The ion exchange polymer of the present invention preferably contains 0.1 to 30% by mass, preferably 5 to 27% by mass of the structure represented by Formula 5 with respect to the total mass of the ion exchange polymer. It is more preferable to contain the mass%.

<Structure represented by Formula 6>
In formula 6, each R ^d independently represents an alkylene group or one or more alkylene groups and one or more linking groups selected from the group consisting of an arylene group, —O— and —NR ^N —. And preferably an alkylene group. R ^N represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
L ⁶ represents a divalent linking group, and is an alkylene group or a combination of one or more alkylene groups and one or more linking groups selected from the group consisting of an arylene group, —O— and —NR ^N —. An alkylene-arylene-alkylene group, more preferably —CH ₂ —C ₆ H ₄ —CH ₂ —, and —CH ₂ —p—C ₆ H _4. Particularly preferred is —CH ₂ —. The number of carbon atoms of the divalent linking group for L ⁶ is preferably 1 to 20, more preferably 2 to 20, more preferably 8 to 20. R ^N represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 8 carbon atoms, and more preferably a methyl group.
R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group, preferably an alkyl group or an aryl group, and more preferably an alkyl group having 1 to 8 carbon atoms.
R ⁸ and R ⁹ are the same as R ² and R ^{3 in} Formula 2, respectively, and the preferred embodiments are also the same.
Xb each independently represents an inorganic or organic anion, and is not particularly limited as long as it is an anion that neutralizes charge, and may be a monovalent anion or a polyvalent anion. Preferably, it is Cl ⁻ , Br ⁻ , I ⁻ or CH ₃ COO ⁻ , more preferably Cl ⁻ or Br ⁻ , and particularly preferably Cl ⁻ .

The structure represented by Formula 6 is preferably a constituent unit of an ion exchange polymer, and more preferably a monomer unit.
The method for introducing the structure represented by Formula 6 into the ion exchange polymer is not particularly limited, but a polymerizable compound represented by Formula 12 (hereinafter also referred to as “compound represented by Formula 12”) is described below. A preferred method is polymerization.

The ion exchange polymer of this invention may contain the structure represented by Formula 6 individually by 1 type, and may contain 2 or more types.
The ion exchange polymer of the present invention preferably contains 0.1 to 95% by mass, preferably 5 to 85% by mass of the structure represented by formula 6 with respect to the total mass of the ion exchange polymer. It is more preferable to contain -80 mass%.

  Although the specific example of the structure represented by Formula 1 is shown below, this invention is not limited to these. In the following specific examples, Rs independently represents a hydrogen atom or a methyl group. In the following specific examples, the hydrogen atoms in the hydrocarbon structure are omitted.

  Moreover, although the specific example of the structure represented by Formula 2 is shown below, this invention is not limited to these. In the following specific examples, Rs independently represents a hydrogen atom or a methyl group. In the following specific examples, the hydrogen atoms in the hydrocarbon structure are omitted.

<Other structures>
[Crosslinked structure without ionic groups]
The ion exchange polymer of the present invention may have a crosslinked structure having no ionic group as another structure.
As the crosslinked structure having no ionic group, a structure represented by the following formula ICL is preferable.

Wherein ICL, R ^CL1 represents a hydrogen atom or an alkyl group, are each Z ^CL1 and Z ^CL2 independently, -O- or -N (R ^N) - represents, R ^N 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 ^N ) —. ^RN 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, and (p1 + 1) -valent hydrocarbon group having 2 or more carbon atoms, or (p1 + 1) -valent, -O-, -S- or A group having 2 or more carbon atoms in which —N (R ^N ) — and a hydrocarbon group are combined is preferable. Here, ^RN 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 ^N ) —, 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 has a (p1 + 1) valence and has 2 carbon atoms in combination of —O—, —S— or —N (R ^N ) —, and a hydrocarbon group. The above groups are preferred. Among these, 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 L ^CL1 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.

The structure represented by the formula ICL is preferably a structural unit, and more preferably a monomer unit.
The method of introducing the structure represented by the formula ICL into the ion exchange polymer is not particularly limited, but a method of polymerizing a compound represented by the formula ICL ′ described below is preferable.

The ion exchange polymer of the present invention may contain one type of structure represented by the formula ICL, or may contain two or more types.
Moreover, it is preferable that the ion exchange polymer of this invention contains 0-30 mass% of structures represented by Formula ICL with respect to the total mass of an ion exchange polymer from a viewpoint of the charge density of an ion exchange polymer, and 0-20 It is preferably contained, more preferably 0 to 10% by mass, and still more preferably not contained.

  Specific examples of the structure represented by the formula ICL can preferably include the following structures, 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.

[Structures having other ionic groups]
The ion exchange polymer of the present invention may have a structure having other ionic groups as another structure.
Examples of the structure having other ionic groups include structures represented by the following 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 N)} - represents, ^{R N} represents a 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 ~R ^A4 and ^{R N} is preferably a linear or branched alkyl group, its carbon number is 1 to 10, more preferably 1 to 6, 1 to 4 Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
R ^A2 to R number of carbon atoms of the aryl group in ^A4 is preferably from 6 to 16, more preferably 6 to 12, 6 to 10 is more preferable. Examples include phenyl and naphthyl.
The ring formed by bonding two or more of R ^{A2 to} R ^A4 to each other is preferably a 5- or 6-membered monocyclic or bridged ring, and preferably has 4 to 16 carbon atoms, preferably 4 to 10 carbon atoms. 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 preferably each independently a methyl group or an ethyl group.
Z ^A1 is preferably —N (R ^N ) —.
R ^N is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.
X ^A1- is preferably a halide ion.

  The structure represented by the formula IA is preferably a structure 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 structure represented by Formula IA is preferably 150 to 350, more preferably 150 to 300, and still more preferably 150 to 270.

The structure represented by the formula IA is preferably a structural unit, and more preferably a monomer unit.
A method for introducing the structure represented by the formula IA into the ion exchange polymer is not particularly limited, but a method for polymerizing a compound represented by the formula IA ′ described below is preferable.

In the ion exchange polymer, the structure represented by the formula IA may be used singly or in combination of two or more.
Moreover, it is preferable that the ion exchange polymer of this invention contains 0-30 mass% of structures represented by Formula IA with respect to the total mass of an ion exchange polymer from a viewpoint of the crosslinking group density of an ion exchange polymer. The content is preferably 20% by mass, more preferably 0 to 15% by mass, and even more preferably not.

<Physical properties of ion exchange polymer>
[Ester density]
The ester density of the ion exchange polymer of the present invention is preferably 1.70 mmol / g or less, more preferably 1.50 mmol / g or less, and particularly preferably 1.30 mmol / g or less.
Further, the ester density of the ion exchange polymer of the present invention is preferably 0.30 mmol / g or more, more preferably 0.50 mmol / g or more, and further preferably 0.70 mmol / g or more. .
If the ester density is 1.70 mmol / g or less, the pH resistance of the ion exchange polymer is further excellent, and if it is 0.30 mmol / g or more, the ion exchange polymer has a low water permeability, which is preferable.
The ester density in the unit structure can be calculated by the following formula, where Es is the number of ester groups contained in the unit structure and M is the molecular weight excluding the ions of the unit structure.
(Es-1) / M × 1,000 [mmol / g]
The ester density of the ion exchange polymer can be calculated by the following formula.
Σ [(Es _i −1) / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, Es _i and M _i are the number of ester groups of monomer i and the molecular weight of the unit structure, respectively.

[Charge density]
The ion exchange polymer of the present invention preferably has a charge density of 2.00 mmol / g or more, preferably 3.50 to 10.00 mmol / g, more preferably 3.80 to 10.00 mmol / g. More preferably, it is 3.95 to 10.00 mmol / g.
If the charge density is within the above range, the charge density in the unit structure is expressed by the following formula, where N is the number of ionic groups (ammonium groups) contained in the unit structure, and M is the molecular weight excluding the counter ion of the unit structure. It can be calculated.
N / M × 1,000 [mmol / g]
The charge density of the ion exchange polymer can be calculated by the following formula.
Σ [(N _i / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, Ni and Mi represent the number of ionic groups of monomer i and the molecular weight of the unit structure, respectively.

[Crosslinking group density]
The ion exchange polymer of the present invention preferably has a crosslinking group density of 1.00 mmol / g or more, preferably 1.50 to 10.00 mmol / g, more preferably 1.80 to 10.00 mmol / g. 2.00 to 10.00 mmol / g is more preferable.
The crosslinkable group density in the unit structure can be calculated by the following formula, where E is the number of polymerizable ethylene groups contained in the unit structure and M is the molecular weight excluding ions of the unit structure.
(E-1) / M × 1,000 [mmol / g]
The crosslinkable group density of the ion exchange polymer can be calculated by the following formula.
Σ [(E _i −1) / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, E _i and M _i are the number of polymerizable ethylene groups of the monomer i and the molecular weight of the unit structure, respectively.

[Ion exchange capacity (meq)]
The ion exchange polymer of the present invention preferably has an ion exchange capacity of 2.00 meq / g or more, more preferably 3.50 to 10.00 meq, and even more preferably 3.80 to 5.00 meq.
The ion exchange capacity of the ion exchange polymer refers to the amount (mmol) of ammonium groups per dry mass (g) of the ion exchange polymer.
Ion exchange capacity of ion exchange polymer (meq) = (Amount of ammonium group of ion exchange polymer [mmol]) / (Dry mass of ion exchange polymer (g))
The ion exchange capacity of the ion exchange polymer can be measured directly from the ion exchange polymer or can be measured from the anion exchange membrane.

-Measurement from ion exchange polymer-
Ion exchange capacity of ion exchange polymer (meq) = (Amount of ammonium group of ion exchange polymer [mmol]) / (Dry mass of ion exchange polymer (g))
The ammonium group amount [mmol] of the ion exchange polymer can be measured as follows.
The ion exchange polymer is immersed in a 2.0 mol / l NaNO ₃ aqueous solution at room temperature for 30 minutes, washed with water, and then immersed in a 2.0 mol / l NaCl aqueous solution for 6 hours or more while changing the solution. The ion exchange polymer completely converted to the Cl type is sufficiently washed with a 0.1 mol / l AgNO ₃ aqueous solution until the washing solution does not become cloudy, and immersed in about 30 mL of a 2 mol / l NaNO ₃ aqueous solution. Replace the solution twice every hour (30 mL each). Finally, after immersion for 6 hours or more, take out the ion-exchange polymer and wash thoroughly with 0.1 mol / l AgNO ₃ aqueous solution until it does not become cloudy. The liquids are combined and the amount of Cl ⁻ ions extracted from the ion exchange polymer is quantified using ion chromatography.
The dry mass (g) of the ion exchange polymer is measured by the following method.
The ion exchange polymer is dried by storing in a vacuum oven at 60 ° C. for 24 hours. In order to prevent moisture from being adsorbed in the air, a dry mass is defined as a weight measured within one minute after removal from the oven.

-Measurement from anion exchange membrane-
Ion exchange capacity of ion exchange polymer (meq) = (ion exchange capacity per dry mass of anion exchange membrane (meq)) / 0.7
Ion exchange capacity per dry mass of anion exchange membrane (meq) = Amount of ammonium group of anion exchange membrane [mmol]) / (Dry mass of anion exchange membrane (g))
Measurement of the amount of ammonium groups in the anion exchange membrane is carried out by the following method.
The anion exchange membrane is immersed in a 2.0 mol / l NaNO ₃ aqueous solution at room temperature for 30 minutes, then washed with water, and immersed in a 2.0 mol / l NaCl aqueous solution for 6 hours or more while changing the solution. The anion exchange membrane completely converted to the Cl type is thoroughly washed with a 0.1 mol / l AgNO ₃ aqueous solution until it does not become cloudy, and is immersed in about 30 mL of a 2 mol / l NaNO ₃ aqueous solution. Replace the solution twice every hour (30 mL each). Finally, after immersion for 6 hours or more, take out the anion exchange membrane and thoroughly wash it with 0.1 mol / l AgNO ₃ aqueous solution until it does not become cloudy. The liquids are combined, and the amount of Cl ⁻ ions extracted from the anion exchange membrane is quantified using ion chromatography.
The dry mass (g) of the anion exchange membrane is measured by the following method.
The anion exchange membrane is dried by storing it in a vacuum oven at 60 ° C. for 24 hours. In order to prevent moisture from being adsorbed in the air, a dry mass is defined as a weight measured within one minute after removal from the oven.
The ion exchange capacity per dry mass of the ion exchange polymer excluding the support is calculated by dividing by 0.7, considering that the porosity of the support is 70%.

(Curable composition)
The curable composition of the present invention (hereinafter also simply referred to as “composition”) contains a compound represented by the following formula 7 and a compound represented by the following formula 8.
Moreover, it is preferable that the curable composition of this invention is a photocurable composition.
The “photocurability” in the present invention is not particularly limited as long as a solid or gel-like material can be formed by irradiation with actinic rays.
In addition, the “active light” is not particularly limited as long as it is an active energy ray that can impart energy capable of generating an initiation species from a photopolymerization initiator described later by irradiation thereof, and is widely α-ray, It includes γ rays, X rays, ultraviolet rays (UV), visible rays, electron beams, and the like. Among these, light containing at least ultraviolet rays is preferable.
The curable composition of the present invention is preferably used for an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte and / or a water absorbent resin. Moreover, as an ion exchange membrane, an anion exchange membrane is preferable.

In Formula 7 and Formula 8, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ _, R ² and R ³ each independently represent a hydrogen atom Alternatively, it represents an alkyl group, and R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.

  The curable composition of the present invention includes a compound represented by the following formula 9 as the compound represented by the formula 7, and a compound represented by the following formula 10 as the compound represented by the formula 8. Preferably, the compound represented by the formula 7 includes a compound represented by the following formula 11, and the compound represented by the formula 8 more preferably includes a compound represented by the following formula 12.

In Formula 9 and Formula 10, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring.

In Formula 11 and Formula 12, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may be bonded to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion.
Hereinafter, details of the compounds represented by Formula 7 to Formula 12 will be described.

<Compound represented by Formula 7>
The curable composition of the present invention contains a compound represented by Formula 7.
In the formula 7, L ^1, R ^1, and, n represents, L ^1, R ¹ in Formula 1, and has the same meaning as n, preferred embodiment is also the same.
Moreover, it is preferable that the compound represented by Formula 7 contains an inorganic or organic anion as a counter anion with respect to a quaternary ammonium salt structure. The anion is synonymous with the anion contained in the structure represented by Formula 1, and the preferred range is also the same.

  The compound represented by Formula 7 preferably includes the compound represented by Formula 9, and more preferably includes the compound represented by Formula 11.

The curable composition of this invention may contain the compound represented by Formula 7 individually by 1 type, and may contain 2 or more types.
It is preferable that the curable composition of this invention contains 0.1-30 mass% of compounds represented by Formula 7 with respect to the total mass of a polymeric compound, and it is preferable that 5-27 mass% is included. It is more preferable to contain -25 mass%.

<Compound represented by Formula 8>
The curable composition of the present invention contains a compound represented by Formula 8.
In the formula 8, L ^2, R ^2, R ^3, and, n represents, L ² in Formula 2, R ^2, R ^3, and has the same meaning as n, preferred embodiment is also the same.
Moreover, it is preferable that the compound represented by Formula 8 contains an inorganic or organic anion as a counter anion with respect to a quaternary ammonium salt structure. The anion is synonymous with the anion contained in the structure represented by Formula 2, and the preferred range is also the same.

  The compound represented by Formula 8 preferably includes the compound represented by Formula 10, and more preferably includes the compound represented by Formula 12.

The curable composition of this invention may contain the compound represented by Formula 8 individually by 1 type, and may contain 2 or more types.
Further, the curable composition of the present invention preferably contains 0.1 to 95% by mass, preferably 5 to 85% by mass, of the compound represented by Formula 8 with respect to the total mass of the polymerizable compound. It is more preferable to contain 8-80 mass%.

<Compound represented by Formula 9>
It is preferable that the curable composition of this invention contains the compound represented by Formula 9 as a compound represented by Formula 7.
In the formula 9, L ³ and, R ⁴ is, L ³ in Formula 3, and has the same meaning as R ^4, preferable embodiments thereof are also the same.
Moreover, it is preferable that the compound represented by Formula 9 contains an inorganic or organic anion as a counter anion with respect to a quaternary ammonium salt structure. The anion is synonymous with the anion contained in the structure represented by Formula 3, and the preferred range is also the same.

The curable composition of this invention may contain the compound represented by Formula 9 individually by 1 type, and may contain 2 or more types.
Moreover, it is preferable that the curable composition of this invention contains 0.1-30 mass% of compounds represented by Formula 9 with respect to the total mass of a polymeric compound, and it is preferable that 5-27 mass% is included. 10 to 25% by mass is more preferable.

<Compound represented by Formula 10>
It is preferable that the curable composition of this invention contains the compound represented by Formula 10 as a compound represented by Formula 8.
In Formula 10, L ^4, R ^5, and, R ⁶ is, L ^4, R ⁵ in the formula 4, and have the same meanings as R ^6, preferable embodiments thereof are also the same.
Moreover, it is preferable that the compound represented by Formula 10 contains an inorganic or organic anion as a counter anion with respect to a quaternary ammonium salt structure. The anion is synonymous with the anion included in the structure represented by Formula 4, and the preferred range is also the same.

The curable composition of this invention may contain the compound represented by Formula 10 individually by 1 type, and may contain 2 or more types.
Moreover, the curable composition of the present invention preferably contains 0.1 to 95% by mass of the compound represented by Formula 10 with respect to the total mass of the polymerizable compound, and preferably 5 to 85% by mass, It is more preferable to contain 8-80 mass%.

<Compound represented by Formula 11>
It is preferable that the curable composition of this invention contains the compound represented by Formula 11 as a compound represented by Formula 7.
In Formula ^{11, L 5, R a,} R b, R c, R 7 and, Xa is, L ⁵ in formula ^{5, R a, R b,} R c, R 7, and, located in Xa synonymous The preferred embodiment is also the same.

The curable composition of this invention may contain the compound represented by Formula 11 individually by 1 type, and may contain 2 or more types.
Moreover, it is preferable that the curable composition of this invention contains 0.1-30 mass% of compounds represented by Formula 11 with respect to the total mass of a polymeric compound, and it is preferable that 5-27 mass% is included. 10 to 25% by mass is more preferable.

<Compound represented by Formula 12>
It is preferable that the curable composition of this invention contains the compound represented by Formula 12 as a compound represented by Formula 8.
In the formula 12, L ⁶ , R ^d , R ^e , R ^f , R ⁸ , R ⁹ , and Xb are L ⁶ , R ^d , R ^e , R ^f , R ⁸ , R ⁹ , and , Xb, and the preferred embodiments are also the same.

The curable composition of this invention may contain the compound represented by Formula 12 individually by 1 type, and may contain 2 or more types.
Further, the curable composition of the present invention preferably contains 0.1 to 95% by mass of the compound represented by Formula 12 with respect to the total mass of the polymerizable compound, preferably 5 to 85% by mass, It is more preferable to contain 8-80 mass%.

  Specific examples of the compound represented by Formula 7 are shown below, but the present invention is not limited to these. In the following specific examples, Rs independently represents a hydrogen atom or a methyl group. In the following specific examples, the hydrogen atoms in the hydrocarbon structure are omitted.

  Specific examples of the compound represented by Formula 8 are shown below, but the present invention is not limited thereto. In the following specific examples, Rs independently represents a hydrogen atom or a methyl group. In the following specific examples, the hydrogen atoms in the hydrocarbon structure are omitted.

<Other polymerizable compounds>
[Polymerizable compound having no ionic group]
The curable composition of the present invention may contain a polymerizable compound having no ionic group as the other polymerizable compound.
As the polymerizable compound having no ionic group, a compound represented by the following formula ICL ′ is preferable.

^{R CL1, Z CL1, Z CL2} , L CL1 and p1 in formula ICL 'are each a ^{R CL1, Z CL1, Z CL2} , L CL1 and p1 synonymous in Formula ICL, the preferred range is also the same.

The curable composition of the present invention may contain one compound represented by the formula ICL ′ alone, or may contain two or more compounds.
Moreover, it is preferable that the curable composition of this invention contains 0-30 mass% of compounds represented by Formula ICL 'with respect to the total mass of a polymeric compound from a viewpoint of the charge density of the hardened | cured material after hardening. 0 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably not contained.

[Other compounds having an ionic group]
The ion exchange polymer of this invention may have the compound which has another ionic group as another polymeric compound.
Examples of other compounds having an ionic group include compounds represented by the following formula IA ′.

^{R A1 ~R A4, Z A1,} L A1 and X ^A1- in Formula IA ', R ^A1 ~R ^A4 in formula IA,
Z ^A1 , L ^A1 and X ^A1- have the same ^meanings, and preferred ranges are also the same.

The curable composition of the present invention may contain one compound represented by the formula IA ′ alone, or may contain two or more compounds.
Moreover, the curable composition of this invention contains 0-30 mass% of compounds represented by Formula IA 'with respect to the total mass of a polymeric compound from a viewpoint of the crosslinking group density of the ion exchange polymer after hardening. It is preferable to contain 0 to 20% by mass, more preferably 0 to 15% by mass, and still more preferably not contained.

In the curable composition of the present invention, the total mass of the polymerizable compound is preferably 30% by mass or more, more preferably 60% by mass or more, and 65% by mass with respect to the total mass of the curable composition. % Or more is more preferable, and 70% by mass or more is particularly preferable.
Moreover, it is preferable that the total mass of a polymeric compound is 95 mass% or less with respect to the total mass of a curable composition, and, as for the curable composition of this invention, it is more preferable that it is 90 mass% or less.
If the total mass of the polymerizable compound is 30% by mass or more with respect to the total mass of the curable composition, the strength of the cured product is excellent, and if it is 60% by mass or more, the water permeability of the cured product is reduced. Excellent.
Moreover, if the total mass of a polymeric compound is 95 mass% or less with respect to the total mass of a curable composition, it will be excellent in the physical property of a composition and will be easy to handle.

<Polymerization initiator>
The curable composition of the present invention preferably contains a polymerization initiator, and more preferably contains a photopolymerization initiator in order to cure by light.
The photopolymerization initiator that can be used in the present invention is a compound that can initiate and accelerate the polymerization of a polymerizable compound such as a compound having an ethylenically unsaturated group by actinic rays.
The photopolymerization initiator is preferably a radical photopolymerization initiator.
Moreover, as a photoinitiator, a water-soluble photoinitiator is preferable.
Here, the fact that the photopolymerization initiator is water-soluble means that it dissolves in distilled water at 0.1% by mass or more at 25 ° C. The water-soluble photopolymerization initiator is more preferably dissolved by 1% by mass or more in distilled water at 25 ° C., particularly preferably 3% by mass or more.
As photopolymerization initiators, aromatic ketone compounds, acylphosphine compounds, aromatic onium salt compounds, oxime ester compounds, organic peroxide compounds, thio compounds, hexaarylbiimidazole compounds, borate compounds, azinium compounds, metallocene compounds, activity Examples thereof include ester compounds, compounds having a carbon halogen bond, and alkylamine compounds.
Especially, an aromatic ketone compound or an acylphosphine compound is mentioned preferably, and the compound represented by the following formula PPI-1 or formula PPI-2 is mentioned more preferably.

In Formula PPI-1 and Formula PPI-2, R ^P1 and R ^P2 each independently represent a hydrogen atom, an alkyl group, an alkoxy group, or an aryloxy group, and R ^P3 represents an alkyl group, an alkoxy group, or an aryloxy group. , L represents an integer of 0 to 5, R ^P4 represents an alkyl group, an aryl group, an alkylthio group or an arylthio group, R ^P5 represents an alkyl group, an aryl group, an alkylthio group, an arylthio group or an acyl group, and R ^P6 Represents an alkyl group or an aryl group. Here, R ^P1 and R ^P2 , or R ^P4 and R ^P5 may be bonded to each other to form a ring.

R ^P1 and R ^P2 are each independently preferably an alkyl group, an alkoxy group or an aryloxy group, more preferably an alkyl group having 1 to 8 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, or an aryl group having 6 to 10 carbon atoms. An alkyl group is more preferable, and a methyl group is particularly preferable.
The ring formed by combining R ^P1 and R ^P2 with each other is preferably a 5- or 6-membered ring, and more preferably a cyclopentane ring or a cyclohexane ring.
R ^P3 is preferably an alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and the alkyl group, alkoxy group, or aryloxy group may have a substituent. . Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
The aryl group is preferably a phenyl group.
R ^P3 is more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a hydroxyethyl group.
Further, the bonding position of R ^P3 on the aromatic ring is not particularly limited, and may be any position other than the position where the carbonyl group is bonded.
L represents an integer of 0 to 5, an integer of 0 to 3 is preferable, and 0 or 1 is more preferable.

The alkyl group in R ^{P4 to} R ^P6 is preferably an alkyl group having 1 to 8 carbon atoms, and the aryl group in R ^{P4 to} R ^P6 is preferably an aryl group having 6 to 16 carbon atoms, and the aryl group has a substituent. You may have. Examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
The alkylthio group or arylthio group in R ^P4 and R ^P5 is preferably an alkylthio group having 1 to 12 carbon atoms or an arylthio group having 6 to 12 carbon atoms.
The acyl group in R ^P5 is preferably an alkylcarbonyl group or an arylcarbonyl group, more preferably an alkylcarbonyl group having 2 to 12 carbon atoms or an arylcarbonyl group having 7 to 17 carbon atoms.
R ^P5 is more preferably an arylcarbonyl group, particularly preferably an optionally substituted phenylcarbonyl group. The acyl group may have a substituent, and examples of the substituent include a halogen atom, an alkyl group, an aryl group, an alkoxy group, and a hydroxy group.
R ^P6 is preferably an aryl group, more preferably a phenyl group which may have a substituent.

As the photopolymerization initiator, a compound represented by the formula PPI-1 is particularly preferable to a compound represented by the formula PPI-2.
Specific examples of the compound represented by Formula PPI-1 or Formula PPI-2 are shown below, but the present invention is not limited thereto.

The curable composition of this invention may contain the polymerization initiator individually by 1 type, and may contain 2 or more types.
In the curable composition of the present invention, the content of the polymerization initiator is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the composition. 0.5 to 5 parts by mass is particularly preferable. The total solid content in the curable composition of the present invention represents an amount excluding volatile components such as a solvent.

<Solvent>
The curable composition of the present invention may contain a solvent.
The solvent may be included singly or in combination of two or more.
It is preferable that content of the solvent in a composition is 1-60 mass% with respect to the total mass of a composition, It is more preferable that it is 5-50 mass%, It is 10-45 mass%. Further preferred is 20 to 40% by mass. Within the above range, the water permeability of the cured product obtained is excellent, the film resistance is reduced, and the handleability is also excellent.
By including the solvent, the curing (polymerization) reaction proceeds uniformly and smoothly. Further, when the porous support is impregnated with the curable composition of the present invention, 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. Among 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.

Among them, the solvent preferably includes water, more preferably water or a mixed solvent of water and an alcohol solvent, and particularly preferably a mixed solvent of water and an alcohol solvent.
As a mixed solvent of water and an alcohol solvent, a mixed solvent of water and isopropanol is particularly preferable.
Further, the mixing ratio of the mixed solvent of water and alcohol solvent is preferably a mass ratio of water: alcohol solvent = 20: 1 to 3: 1, and water: alcohol solvent = 10: 1 to 4: 1 is more preferable.

<Polymerization inhibitor>
The curable composition of the present invention may contain a polymerization inhibitor.
As a polymerization inhibitor, a well-known polymerization inhibitor can be used, and a phenol compound, a hydroquinone compound, an amine compound, a mercapto compound, etc. are mentioned.
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, these polymerization inhibitors may be used alone or in combination of two or more.
The content of the polymerization inhibitor is preferably 0.01 to 5 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the total solid content in the curable composition. More preferably, it is 0.01-0.5 mass part.

<Catalyst>
The curable composition of the present invention preferably contains a catalyst from the viewpoint of improving the solubility of the polymerizable compound 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 the lithium compound include lithium hydroxide, lithium chloride, lithium bromide, lithium nitrate, lithium iodide, lithium chlorate, lithium thiocyanate, lithium perchlorate, lithium tetrafluoroborate, lithium hexafluorophosphate, And lithium hexafluoroarsenate.
Moreover, it is also preferable to use the said alkali metal compound in order to neutralize a curable composition.
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 parts by mass, more preferably 1 to 30 parts by mass, and still more preferably 5 to 30 parts by mass with respect to 100 parts by mass of the total solid content of the curable composition.

<Other additives>
The curable composition of the present invention may contain known additives other than those described above, if necessary, for example, surfactants, viscosity improvers, polymer compounds, polymer dispersants, crater inhibitors. , Plasticizers, viscosity modifiers, antioxidants, and / or preservatives.

In the curable composition of the present invention, various polymer compounds can be added in order to adjust film physical properties.
High molecular compounds include acrylic resin, polyurethane resin, polyamide resin, polyester resin, epoxy resin, phenol resin, polycarbonate resin, polyvinyl butyral resin, polyvinyl formal resin, shellac, vinyl resin, rubbers, waxes, and other natural resins. Etc. can be used. Moreover, these may be used individually by 1 type, or may use 2 or more types together.
Moreover, the curable composition of this invention may contain the polymer dispersing agent.
Specific examples of the polymer dispersant include polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl methyl ether, polyethylene oxide, polyethylene glycol, polypropylene glycol, and polyacrylamide.

An anti-crater agent is also called a surface tension adjusting agent, a surface adjusting agent, a leveling agent or a slip agent, and prevents irregularities on the film surface. For example, organic modified polysiloxane (mixture of polyether siloxane and polyether) , A compound having a structure of a polyether-modified polysiloxane copolymer and a 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 0.5 to 2 parts by mass with respect to 100 parts by mass of the total solid content of the curable composition.

The curable composition of the present invention contains a surfactant such as a nonionic surfactant, a cationic surfactant, or an organic fluoro compound in order to adjust the liquid properties of the coating liquid when forming a film. May be.
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.
The content of the surfactant is preferably 0.0001 to 5 parts by mass, more preferably 0.001 to 2 parts by mass, and 0.01 to 1 part by mass with respect to 100 parts by mass of the total solid content of the curable composition. Is more preferable.

(Cured product)
The cured product of the present invention is a cured product formed by curing the curable composition of the present invention.
The use of the cured product of the present invention is not particularly limited and can be used for various applications. Since the cured product of the present invention has a quaternary ammonium salt structure, an ion exchange resin (preferably anion exchange resin) is used. It also functions as a resin.
For example, the cured product of the present invention can be suitably used for an ion exchange membrane (preferably an anion exchange membrane), a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte, or a water absorbent resin.
The shape of the cured product of the present invention is not particularly limited and may be any desired shape, for example, a polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane and a forward osmosis membrane, or The polymer electrolyte used in a solid polymer electrolyte fuel cell or the like is preferably in the form of a film, and the water absorbent resin is preferably in the form of a film, a sphere or a bead.
In the case of the polymer functional membrane such as an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, and a forward osmosis membrane, the thickness of the polymer functional membrane includes the support when it has a support described later. 30 to 1,000 μm is preferable, 50 to 500 μm is more preferable, and 50 to 400 μm is still more preferable.

<Support>
In applications where the cured product of the present invention such as the ion exchange membrane is formed as a film, the cured product of the present invention may be formed on the support and / or inside the support. The support is preferably a porous support.
The porous support as the reinforcing material is preferably a resin porous support, and examples thereof include non-woven fabrics such as synthetic woven fabrics and synthetic non-woven fabrics, sponge-like films, and films having fine through holes. .
In the case of using a porous support, the film is preferably a film having at least a part of the cured product of the present invention inside the porous support.
Moreover, it is preferable that the said film | membrane is a film | membrane which has the hardened | cured material of this invention in the surface and / or inside of a porous support body.

The material forming the porous support is, for example, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or, for example, polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide, Polyimide, polyetherimide, polyamide, polyamideimide, polyacrylonitrile, polycarbonate, polyacrylate, cellulose acetate, polypropylene, poly (4-methyl-1-pentene), polyvinylidene fluoride, polytetrafluoroethylene, polyhexafluoropropylene, poly Examples include porous membranes based on chlorotrifluoroethylene and their copolymers.
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 curing reaction by energy beam irradiation, the porous support is required not to block the wavelength region of the energy beam, that is, to pass the irradiation of the wavelength used for curing.

The porous support is preferably one that can be penetrated by the curable composition of the present invention.
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 that can be used in the present invention is preferably a nonwoven fabric, and more preferably a nonwoven 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 that can be used in the present invention is preferably 20 to 200 μm, more preferably 30 to 150 μm, and particularly preferably 40 to 120 μm.

<Method for producing cured product>
There is no restriction | limiting in particular in the manufacturing method of the hardened | cured material of this invention, A well-known method can be used.
For example, the curable composition of the present invention may be applied onto a substrate and polymerized, or the curable composition of the present invention is cured in an arbitrary shape to obtain a cured product, and then the obtained cured product is used. Furthermore, you may process into a desired shape.
Further, for example, when a porous support is used, a film can be suitably produced by impregnating or coating the porous support with the curable composition of the present invention and performing photopolymerization. Alternatively, the film may be formed using a temporary support (attached to one or both surfaces of the porous support and peeled off from the film after completion of the curing reaction).
In addition, when the cured product of the present invention, particularly when the cured product of the present invention is formed into a film, it can be prepared in a batch system using a fixed support, or using a moving support. It can also be prepared in a continuous manner (continuous manner).
In the case of using a temporary support, the temporary support does not need to consider material permeation. For example, any temporary support can be used as long as it can be fixed for film formation, including a metal plate such as an aluminum plate. It does n’t matter.

  The curable composition of the present invention can be applied in various ways, such as curtain coating, extrusion coating, air knife coating, slide coating, nip roll coating, forward roll coating, reverse roll coating, dip coating, kiss coating, rod bar coating or spray coating. 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.

  The production of the film obtained by curing the curable composition of the present invention in a continuous system is preferably carried out by continuously applying the curable composition of the present invention to a moving support. Also, an application part for applying the curable composition of the present invention, an irradiation source for curing the curable composition of the present invention, a film winding part for collecting the formed film, and a support are applied as described above. It is more preferable to manufacture by a manufacturing unit including means for moving the irradiation source to the irradiation source and the film winding unit.

  As a method for producing a film obtained by curing the curable composition of the present invention, a step of applying or impregnating a porous support with the curable composition of the present invention, and a method of applying light to the curable composition coated or impregnated. It is preferable that the method includes a step of irradiation and, if necessary, a curing reaction by heating.

In the manufacturing unit, the 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 curable composition of the present invention 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 curable composition of the present invention 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.
Especially when using a support to increase the mechanical strength, before applying the curable composition of the present invention 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.

The curable composition of the present invention is cured by applying or impregnating the curable composition of the present invention to a support, preferably within 60 seconds, more preferably within 15 seconds, particularly preferably within 5 seconds, most preferably. Starts within 3 seconds.
The light irradiation for 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 performed continuously, and the curing reaction time is determined in consideration of the speed at which the curable composition of the present invention moves through the irradiation beam.
When a high-intensity ultraviolet ray (UV light) is used for the curing reaction, a considerable amount of heat is generated. Therefore, in order to prevent overheating, the lamp of the light source and / or the support / film may be cooled with cooling air or the like. preferable. When a significant dose of infrared (IR light) is irradiated along 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 contained in the curable composition of the present invention. For example, UV-A (400 to 320 nm), UV-B (320 to 280 nm) and UV-C (280 to 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 degree of cure of the film can be adjusted by the exposure strength. Exposure dose, the High Energy UV Radiometer (EIT-Instrument Markets , Inc. of UV Power Puck ^TM), as measured by UV-A range indicated by the apparatus, preferably at least 40 mJ / cm ² or more, more preferably 100 ˜2,000 mJ / cm ² , particularly 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.
Moreover, the manufacturing method of the hardened | cured material of this invention may include arbitrary well-known processes other than the said process as needed.

(Members and devices)
The member of this invention is a member provided with the hardened | cured material formed by hardening | curing the ion exchange polymer of this invention, or the curable composition of this invention.
Moreover, the apparatus of this invention is an apparatus provided with the hardened | cured material formed by hardening | curing the ion exchange polymer of this invention, or the curable composition of this invention.
The apparatus of the present invention is not particularly limited as long as it includes the ion exchange polymer of the present invention or a cured product formed by curing the curable composition of the present invention. Examples include a salt device, a pure water production device, a concentration device, a dialysis device, a purification device, and a combustion battery.
The member of the present invention is not particularly limited as long as it includes the ion exchange polymer of the present invention or a cured product formed by curing the curable composition of the present invention. Materials and the like. Specifically, for example, a module in which an anion exchange membrane and a cation exchange membrane formed by curing the curable composition of the present invention between a pair of electrodes are alternately arranged, the curable composition of the present invention Water-absorbing material containing a water-absorbing resin formed by curing, both electrodes in a fuel cell, a cell comprising a film and a separator formed by curing the curable composition of the present invention, a stack in which the cells are laminated, and the like Is mentioned.

  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.

(Example)
<Calculation method of ester density>
The ester density of the ion exchange polymer was calculated by the following formula.
Σ [(Es _i −1) / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, Es _i and M _i are the number of ester groups of monomer i and the molecular weight of the unit structure, respectively.

<Calculation method of charge density>
The charge density of the ion exchange polymer was calculated by the following formula.
Σ [(N _i / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, Ni and Mi represent the number of ionic groups (ammonium groups) of the monomer i and the molecular weight of the unit structure, respectively.

<Calculation method of crosslinking group density>
The charge density of the ion exchange polymer was calculated by the following formula.
Σ [(E _i −1) / M _i × 1,000) × (mass of monomer i / total monomer mass)] [mmol / g]
Here, E _i and M _i are the number of polymerizable ethylene groups of the monomer i and the molecular weight of the unit structure, respectively.

<Calculation method of ion exchange capacity>
The ion exchange capacity of the ion exchange polymer was calculated by the following formula.
Ion exchange capacity of ion exchange polymer (meq) = (ion exchange capacity per dry mass of anion exchange membrane (meq)) / 0.7
Ion exchange capacity per dry mass of anion exchange membrane (meq) = (Ammonium group amount [mmol] of anion exchange membrane) / (Dry mass of anion exchange membrane (g))
The ammonium group content of the anion exchange membrane was measured by the following method.
The anion exchange membrane was immersed in a 2.0 mol / l NaNO ₃ aqueous solution at room temperature for 30 minutes, washed with water, and then immersed in a 2.0 mol / l NaCl aqueous solution for 6 hours or more while changing the solution. The anion exchange membrane completely converted to the Cl type was sufficiently washed with a 0.1 mol / l AgNO ₃ aqueous solution until the washing solution did not become cloudy, and immersed in about 30 mL of a 2 mol / l NaNO ₃ aqueous solution. Replace the solution twice every hour (30 mL each). Finally, after immersion for 6 hours or more, take out the anion exchange membrane and thoroughly wash it with 0.1 mol / l AgNO ₃ aqueous solution until it does not become cloudy. The liquids were combined, and the amount of Cl ⁻ ions extracted from the anion exchange membrane was quantified using ion chromatography.
The dry mass (g) of the anion exchange membrane was measured by the following method.
The anion exchange membrane was dried by storing it in a vacuum oven at 60 ° C. for 24 hours. In order to prevent adsorption of moisture in the air, the dry mass was determined by weighing the mass within one minute after removal from the oven.

(Synthesis example)
<Synthesis of Compound M-1>
Compound M-1 was synthesized according to the following synthesis scheme.

p-Xylene dichloride 796.5 g (4.55 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), ultrapure water 1,364 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 180 mg (Tokyo Kasei) N- [3- (dimethylaminopropyl) acrylamide] 1,428.8 g (9.15 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added to the mixed solution of Kogyo Kogyo Co., Ltd. at 60 ^° C. Stir for 6 hours. The solution after stirring was filtered to obtain 3,565 g of an aqueous solution of M-1 (water content 38%, yield 99%).

<Synthesis of Compound M-2>
Compound M-2 was synthesized according to the following synthesis scheme.

p-xylene dichloride 796.5 g (4.55 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), ultrapure water 1,442.6 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 180 mg ( to a mixed solution of Tokyo Kasei Kogyo Co., Ltd.), N- and [3- (dimethylaminopropyl) methacrylamide] 1,557.8g (9.15mol, Tokyo Chemical industry Co., Ltd.) was added, 60 ^o Stir at C for 6 hours. The solution after stirring was filtered to obtain 3,758 g of M-2 aqueous solution (water content 38%, yield 99%).

<Synthesis of Compound M-3>
Compound M-3 was synthesized according to the following synthesis scheme.

p-xylene dichloride 796.5 g (4.55 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), ultrapure water 1,291 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 180 mg (Tokyo Kasei) To the mixed solution of Kogyo Kogyo Co., Ltd., 1,309.5 g (9.15 mol, Tokyo Kasei Kogyo Co., Ltd.) of 2- (dimethylaminoethyl) acrylate was added and stirred at 60 ^° C. for 6 hours. . The solution after stirring was filtered to obtain 3,363 g of M-3 aqueous solution (water content 38%, yield 99%).

<Synthesis of Compound M-4>
Compound M-4 was synthesized according to the following synthesis scheme.

p-xylene dichloride 796.5 g (4.55 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), ultrapure water 1,370 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 180 mg (Tokyo Kasei) To the mixed solution of Kogyo Kogyo Co., Ltd., 2- (dimethylaminoethyl) acrylate 1,437.8 g (9.15 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added and stirred at 60 ^° C. for 6 hours. . The solution after stirring was filtered to obtain 3,568 g of M-4 aqueous solution (water content 38%, yield 99%).

<Synthesis of Compound M-7>
Compound M-7 was synthesized according to the following synthesis scheme.

1,3,5-tris (chloromethyl) -2,4,6-trimethylbenzene 1.99 g (7.49 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-methoxyhydroquinone 14 mg (manufactured by Tokyo Chemical Industry Co., Ltd.) ), N- [3- (dimethylaminopropyl) methacrylamide 4.09 g (26.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) is added, and acetonitrile (7 mL, manufactured by Wako Pure Chemical Industries, Ltd.) is added. ), Methanol (7 mL, manufactured by Wako Pure Chemical Industries, Ltd.) at 50 ^° C. for 7 hours, and then acetone (100 mL, manufactured by Wako Pure Chemical Industries, Ltd.) was added thereto. M-7 was filtered by filtering the obtained crystals to obtain M-7 (3.30 g, yield 60%). This was diluted with a desired amount of water to obtain an aqueous solution of M-7 (water content: 38%).

<Synthesis of Compound M-8>
Compound M-8 was synthesized according to the following synthesis scheme.

Pentaerythrityl tetrachloride 955.2 g (4.55 mol, manufactured by Tokyo Chemical Industry Co., Ltd.), ultrapure water 1,461 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 180 mg (Tokyo) to a mixed solution of Chemical industry Co., Ltd.), N- [3- (dimethylamino propyl) acrylamide] 1,428.8g (9.15mol, Tokyo Chemical industry Co., Ltd.) was added, to 60 ^o C And stirred for 6 hours. The solution after stirring was filtered to obtain 3,807.0 g of M-1 aqueous solution (water content 38%, yield 99%).

<Synthesis of Compound M-9>
Compound M-9 was synthesized according to the following synthesis scheme.

1,3-dibromopropane 16.2 g (80.2 mmol, manufactured by Wako Pure Chemical Industries, Ltd.), ultrapure water 11.0 g, 4-hydroxy-2,2,6,6-tetramethylpiperazine 1-oxyl 210 mg 25.1 g of N- [3- (dimethylamino) propyl] acrylamide (160 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) with respect to the mixed solution (manufactured by Tokyo Chemical Industry Co., Ltd.)
And stirred at 50 ° C. for 9 hours. The solution after stirring was filtered to obtain 47.9 g of an aqueous solution of Compound M-9 (water content 20.0%, yield 92%).

<Synthesis of Compound M-10>
Compound M-10 was synthesized according to the following synthesis scheme.

1,3,5-tris (chloromethyl) -2,4,6-trimethylbenzene 1.99 g (7.49 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), p-methoxyhydroquinone 14 mg (manufactured by Tokyo Chemical Industry Co., Ltd.) ) Was added 3.75 g of 2- (dimethylaminoethyl) acrylate (26.2 mol, manufactured by Tokyo Chemical Industry Co., Ltd.). Next, acetonitrile (7 mL, manufactured by Wako Pure Chemical Industries, Ltd.) and methanol (7 mL, manufactured by Wako Pure Chemical Industries, Ltd.) were added thereto, and the mixture was stirred at 50 ^° C. for 7 hours. Acetone (100 mL, manufactured by Wako Pure Chemical Industries, Ltd.) was added to the stirred solution. M-10 was filtered by filtering the obtained crystals to obtain M-10 (3.12 g, yield 60%). This was diluted with a desired amount of water to obtain an aqueous solution of M-10 (water content 38%).

(Examples 1-17 and Comparative Examples 1-3)
<Preparation of curable composition>
The polymerizable compounds M-1 to M-10 described in Tables 1 to 3, the solvent, the initiator, and the additive were mixed and stirred to obtain a uniform solution. Stirring was performed at room temperature (25 ° C.).
In Tables 1 to 3, the numerical value represents the content (part by mass) of the corresponding component, “−” represents that the corresponding component is not contained, and “total mass part of the polymerizable compound” The total mass part of the polymerizable compound is represented, and “total (mass part)” represents the total mass part of all the components in the composition.

Details of the compounds described in Tables 1 to 3 are as follows.
(Polymerizable compound)
M-1: synthetic product according to the above synthesis example M-2: synthetic product according to the above synthesis example M-3: synthetic product according to the above synthesis example M-4: synthetic product according to the above synthesis example M-5: 3 -Acrylamidepropyltrimethylammonium chloride (dimethylaminopropylacrylamide methyl chloride quaternary salt), manufactured by Kojin Co., Ltd., the following compound: M-6: Methylenebisacrylamide, the following compound: M-7: Synthetic product according to the above synthesis example -8: Synthetic product according to the above synthesis example M-9: Synthetic product according to the above synthesis example M-10: Synthetic product according to the above synthesis example [solvent]
・ Pure water: Wako Pure Chemical Industries, Ltd. [Polymerization initiator]
Darocur 1173: photopolymerization initiator, manufactured by BASF, the following compound Irgacure 184: photopolymerization initiator, manufactured by BASF, the following compound [crater inhibitor]
-Tego Glide 432: Evonik industries

<Preparation of ion exchange membrane>
In each of the examples and comparative examples, the prepared curable composition was manually applied to an aluminum plate at a speed of about 5 m / min using a rod wound with a wire of 150 μm, followed by a nonwoven fabric (Freudenberg Company). Manufactured, FO-2223-10 (thickness: 100 μm)) was impregnated with the curable composition. The excess curable composition was removed using a rod with no wire wound around it. The temperature of the curable composition at the time of application was about 50 ° C. The curable composition-impregnated support obtained as described above is subjected to a curing reaction using a UV exposure machine (Fusion UV Systems, Model Light Hammer LH6, D-bulb, speed 15 m / min, 100% strength). Thus, an anion exchange membrane was prepared. The curing time was 0.8 seconds. The exposure time was 0.47 seconds.
The resulting membrane was removed from the aluminum plate and stored in a 0.1 mol / L NaCl aqueous solution for at least 12 hours. The thickness of the obtained film was 134 μm.

<Evaluation of solubility>
In each of the examples and comparative examples, the curable compositions having the compositions shown in Tables 1 to 3 were stirred at 40 ° C. for 24 hours. The evaluation is shown in Table 4 or Table 5.
In Table 4 or Table 5, the numerical values described in the columns of “charge density”, “crosslinking group density”, and “ester density” represent the respective values calculated by the above method. The description of “impossible to measure” indicates that measurement of the corresponding evaluation item was impossible because a solid was deposited on the curable composition in the evaluation of solubility.

<Evaluation of water permeability (ml / (m ² · Pa · hr))>
The water permeability of the membrane was measured using an apparatus having the flow channel 10 shown in FIG.
A feed solution (pure water) 400 mL and a draw solution (3M NaCl aqueous solution) 400 mL are brought into contact with each other through the membrane 1 by flowing through the feed solution channel 3 and the draw solution channel 4 (membrane contact area 18 cm). ² ) Each liquid was flowed at a flow rate of 8 cm / sec in the direction of the liquid traveling direction 5 in the flow path 10 using a peristaltic pump. Analyzing the rate at which the pure water in the feed solution penetrates the draw solution through the membrane in the direction of the water stream 2 separated from the feed solution by measuring the mass of the feed solution and the draw solution in real time; The water permeability was determined.
Based on the obtained values, the evaluation was made in five stages according to the following criteria.
The evaluation results are shown in Table 4 or Table 5. If evaluation is A, B, or C, it can be used practically without a problem, A or B is preferable and A is more preferable.
A: Less than 7.6 × 10 ⁻⁵ ml / (m ² · Pa · hr) B: 7.6 × 10 ⁻⁵ ml / (m ² · Pa · hr) or more 9.0 × 10 ⁻⁵ ml / ( Less than m ² · Pa · hr) C: 9.0 × 10 ⁻⁵ ml / (m ² · Pa · hr) or more and less than 10.0 × 10 ⁻⁵ ml / (m ² · Pa · hr) D: 10. 0 × 10 ⁻⁵ ml / (m ² · Pa · hr) or more and less than 11.0 × 10 ⁻⁵ ml / (m ² · Pa · hr) E: 11.0 × 10 ⁻⁵ ml / (m ² · Pa・ Hr) or more

<Evaluation of electrical resistance of membrane (membrane resistance, Ω · cm ² )>
About 2 hours, both surfaces of the membrane immersed in 0.5 mol / L NaCl aqueous solution were wiped with dry filter paper, and sandwiched between two-chamber cells (effective membrane area 1 cm ² , platinum electrode used for electrodes). Both chambers were filled with 20 mL of 0.5 mol / L NaCl aqueous solution, and a two-chamber cell was placed in a constant temperature water bath at 25 ° C. until it reached equilibrium. After confirming that the liquid temperature in the cell was correctly 25 ° C., the electric resistance r ₁ of the ion exchange membrane was measured by an AC bridge (frequency: 1,000 Hz).
Next, the membrane was removed from the two-chamber cell, and the electrical resistance r ₂ was measured when there was only 0.5 mol / L NaCl aqueous solution between the _two electrodes. The electric resistance R (Ω · cm ² ) of the film was determined by r ₁ -r ₂ .
Based on the obtained value, it evaluated in five steps by the following criteria.
The evaluation results are shown in Table 4 or Table 5. If evaluation is A, B, C, or D, it can be used practically without a problem, A, B, or C is preferable, A or B is more preferable, and A is still more preferable.
A: Less than 1.95Ω · cm ² B: 1.95Ω · cm ² or more and less than 2.00Ω · cm ² C: 2.00Ω · cm ² or more and less than 2.80Ω · cm ² D: 2.80Ω · cm ² or more Less than 4.00 Ω · cm ² E: 4.00 Ω · cm ² or more

<Evaluation of selective permeability>
The permselectivity was evaluated by measuring the membrane potential (V) by static membrane potential measurement. For the measurement of the membrane potential, a two-chamber cell in which two electrolytic cells (cells) are separated by the membrane to be measured was used. Prior to measurement, the membrane was equilibrated in 0.05 mol / L NaCl aqueous solution for about 16 hours. Thereafter, NaCl aqueous solutions of different concentrations were respectively poured into the electrolytic cells on the opposite side of the film to be measured.
One cell was poured with 100 mL of 0.05 mol / L NaCl aqueous solution. Moreover, 100 mL of 0.5 mol / L NaCl aqueous solution was poured into the other cell. After the temperature of the NaCl aqueous solution in the cell is stabilized at 25 ° C. by a constant temperature water bath, both electrolytic cells and an Ag / AgCl reference electrode (manufactured by Metrohm, Switzerland) The membrane potential (V) was measured by connecting with a bridge. The selective permeability was evaluated based on the value calculated by the following formula (a).
The effective area of the film was 1 cm ² .
t = (a + b) / 2b Formula (a)
Details of each symbol in the formula (a) are shown below.
a: Membrane potential (V)
b: 0.5915 log (f ₁ c ₁ / f ₂ c ₂ ) (V)
f ₁ , f ₂ : NaCl activity coefficient of both cells c ₁ , c ₂ : NaCl concentration (mol / L) of both cells
Based on the obtained value, it evaluated in five steps by the following criteria.
The evaluation results are shown in Table 4 or Table 5. If evaluation is A, B, or C, it can be used practically without a problem, A or B is preferable and A is more preferable.
A: It exceeds 0.96 and is 1.00 or less.
B: It exceeds 0.95 and is 0.96 or less.
C: It exceeds 0.93 and is 0.95 or less.
D: It exceeds 0.90 and is 0.93 or less.
E: 0.90 or less.

<Evaluation of pH tolerance>
As evaluation of pH tolerance, a durability test at pH 2 (acid durability test) and a durability test at pH 12 (alkali durability test) were performed as follows.
(1) Acid durability test at pH 2 1 mol / L hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) and citric acid, trisodium citrate dihydrate as buffering agents (both manufactured by Wako Pure Chemical Industries, Ltd.) PH 2 aqueous hydrochloric acid solution was prepared using a solution obtained by diluting ()) with pure water.
The anion exchange membranes produced in Examples 1 to 15 and Comparative Examples 1 to 3 were immersed in the hydrochloric acid aqueous solution whose concentration was adjusted as described above for 24 hours, and then the anion exchange membrane was taken out and the water permeability was measured.
The method for measuring the water permeability was the same as the method for measuring the water permeability in the evaluation of the water permeability.
(2) Alkali durability test at pH 12 Sodium hydroxide granule (manufactured by Wako Pure Chemical Industries, Ltd.) and sodium dihydrogen phosphate dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) as a buffering agent The solution was diluted with pure water to prepare a pH 12 sodium hydroxide aqueous solution.
The anion exchange membranes prepared in Examples 1 to 15 and Comparative Examples 1 to 3 were immersed in the sodium hydroxide aqueous solution whose concentration was adjusted as described above for 24 hours, and then the anion exchange membrane was taken out and the water permeability was measured.
[Evaluation]
In the acid durability test and alkali durability test, the degree of decrease in water permeability was determined as (water permeability after immersion) − (water permeability before immersion in each aqueous solution).
Evaluation was made in five stages according to the degree of change in water permeability after the acid / alkali immersion test.
The evaluation results are shown in Table 4 or Table 5. If evaluation is A, B, C, or D, it can be used practically without problem, A, B, or C is more preferable, A or B is still more preferable, and A is especially preferable.
A: The water permeability is less than 1 ml / (m ² · Pa · hr).
B: Water permeability is 1 ml / (m ² · Pa · hr) or more and less than 2 ml / (m ² · Pa · hr).
C: The water permeability is 2 ml / (m ² · Pa · hr) or more and less than 3 ml / (m ² · Pa · hr).
D: The water permeability is 3 ml / (m ² · Pa · hr) or more and less than 4 ml / (m ² · Pa · hr).
E: Water permeability is 4 ml / (m ² · Pa · hr) or more.

1: membrane 2: flow of water separated from feed solution 3: feed solution channel 4: draw solution channel 5: liquid traveling direction 10: channel

Claims (16)

A structure represented by the following formula 1, and
An ion exchange polymer having a structure represented by the following formula 2.

In Formula 1 and Formula 2, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ , R ² and R ³ each independently represent a hydrogen atom Alternatively, it represents an alkyl group, and R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.   The ion exchange polymer of Claim 1 whose ester density of the said ion exchange polymer is 1.70 mmol / g or less.   The ion exchange polymer of Claim 1 or 2 whose ester density of the said ion exchange polymer is 0.30 mmol / g or more. The structure represented by Formula 1 includes a structure represented by Formula 3 below, and the structure represented by Formula 2 includes a structure represented by Formula 4 below. The ion exchange polymer described in 1.

In Formula 3 and Formula 4, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring. The structure represented by Formula 1 includes a structure represented by Formula 5 below, and the structure represented by Formula 2 includes a structure represented by Formula 6 below. The ion exchange polymer described in 1.

In Formula 5 and Formula 6, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may be bonded to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion.   The ion exchange polymer according to any one of claims 1 to 5, wherein the charge density is 2.00 mmol / g or more and the cross-linking group density is 1.00 mmol / g or more.   The ion exchange polymer according to any one of claims 1 to 6, wherein the ion exchange capacity is 2.00 meq or more.   The ion exchange polymer according to any one of claims 1 to 7, which is used for an ion exchange membrane, a proton conductive membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte and / or a water absorbent resin. . A curable composition containing a polymerizable compound represented by the following formula 7 and a polymerizable compound represented by the following formula 8.

In Formula 7 and Formula 8, L ¹ and L ² each independently represent a (2 + n) -valent linking group having a quaternary ammonium salt structure, and R ¹ _, R ² and R ³ each independently represent a hydrogen atom Alternatively, it represents an alkyl group, and R ³ and L ² may be bonded to each other to form a ring, and n independently represents an integer of 0 or more.   The curable composition of Claim 9 which contains 0.1-30.0 mass% of polymeric compounds represented by Formula 7 with respect to the total mass of a polymeric compound. The polymerizable compound represented by formula 7 includes a polymerizable compound represented by formula 9 below, and the polymerizable compound represented by formula 8 includes a polymerizable compound represented by formula 10 below. The curable composition according to 9 or 10.

In Formula 9 and Formula 10, L ³ and L ⁴ each independently represent a divalent linking group having a quaternary ammonium salt structure, and R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom or an alkyl Represents a group, and R ⁶ and L ⁴ may be bonded to each other to form a ring. The polymerizable compound represented by formula 7 includes a polymerizable compound represented by formula 11 below, and the polymerizable compound represented by formula 8 includes a polymerizable compound represented by formula 12 below. The curable composition of any one of 9-11.

In Formula 11 and Formula 12, R ^a and R ^d each independently represent an alkylene group, L ⁵ and L ⁶ each independently represent a divalent linking group, R ^b , R ^c , R ^e and R ^f each independently represents an alkyl group, an alkenyl group or an aryl group; R ⁷ , R ⁸ and R ⁹ each independently represents a hydrogen atom or an alkyl group; and R ⁹ and R ^e and / or R ⁹ and R ^{9 f} may be bonded to each other to form a ring, and Xa and Xb each independently represent an inorganic or organic anion. Hardened | cured material formed by hardening | curing the curable composition of any one of Claims 9-12.   The cured product according to claim 13, which is an ion exchange membrane, a proton conducting membrane, a reverse osmosis membrane, a forward osmosis membrane, a polymer electrolyte and / or a water absorbent resin. A member provided with the ion exchange polymer of any one of Claims 1-8, or the hardened | cured material formed by hardening | curing the curable composition of any one of Claims 9-12. An apparatus comprising: the ion exchange polymer according to any one of claims 1 to 8; or a cured product formed by curing the curable composition according to any one of claims 9 to 12.