WO2017033593A1 - Film polymère fonctionnel, module, et dispositif - Google Patents

Film polymère fonctionnel, module, et dispositif Download PDF

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Publication number
WO2017033593A1
WO2017033593A1 PCT/JP2016/070357 JP2016070357W WO2017033593A1 WO 2017033593 A1 WO2017033593 A1 WO 2017033593A1 JP 2016070357 W JP2016070357 W JP 2016070357W WO 2017033593 A1 WO2017033593 A1 WO 2017033593A1
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Prior art keywords
group
polyfunctional monomer
functional film
formula
polymer functional
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PCT/JP2016/070357
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English (en)
Japanese (ja)
Inventor
基 原田
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富士フイルム株式会社
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Priority claimed from JP2015241981A external-priority patent/JP2018167134A/ja
Application filed by 富士フイルム株式会社 filed Critical 富士フイルム株式会社
Publication of WO2017033593A1 publication Critical patent/WO2017033593A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J39/00—Cation exchange; Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/08—Use of material as cation exchangers; Treatment of material for improving the cation exchange properties
    • B01J39/16—Organic material
    • B01J39/18—Macromolecular compounds
    • B01J39/20—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
    • B01J41/12—Macromolecular compounds
    • B01J41/14—Macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • C08F20/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F20/56—Acrylamide; Methacrylamide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms

Definitions

  • the present invention relates to a polymer functional membrane, a module, and an apparatus.
  • ion exchange membranes 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.
  • 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.
  • conventional ion exchange membranes those described in Patent Document 1 or 2 are known.
  • the problems to be solved by the present invention include a polymer functional film having a low electrical resistance (hereinafter referred to as “membrane resistance”) and excellent pH resistance, and the polymer functional film. It is to provide modules and devices.
  • ⁇ 1> A polymer compound obtained by curing a composition containing a polyfunctional monomer, wherein the polyfunctional monomer has an ionic group and two or more ⁇ -alkylacryloylamino groups or ⁇ - When the ionic group is a cationic group, the ClogP value of the polyfunctional monomer is ⁇ 5.2 or more, and the ionic group is an anionic group, A polyfunctional monomer having a CLogP value of ⁇ 1.9 or more and a content of the polyfunctional monomer based on the total mass after drying of 500 ppm or more and 3,000 ppm or less, ⁇ 2> The polymer functional film according to ⁇ 1>, wherein the polyfunctional monomer includes a compound represented by the following formula PCL-I or formula II:
  • R A′1 and R A′2 each independently represents an alkyl group
  • R A′3 to R A′6 each independently represents an alkyl group or an aryl group
  • Z A ′ 1 and Z A′2 each independently represent —O— or —NRa—
  • Ra represents a hydrogen atom or an alkyl group
  • L A′1 and L A′2 each independently represent an alkylene group
  • R X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined
  • X A′1 and X A′2 each independently represent an organic or inorganic group Represents an anion
  • R 21 and R 22 each independently represents an alkyl group
  • R 23 , R 24 , R 25 and R 26 each independently represent a substituent
  • k 21 and k 24 each independently represent Represents an integer of 0 to 4
  • k 22 and k 23 each independently represents an alkyl
  • M 21 independently represents a hydrogen ion, an organic base ion or a metal ion
  • n 21 and n 22 each independently represents an integer of 1 to 4
  • m 21 and m 22 each independently Represents 0 or 1
  • J 1 represents a single bond, —O—, —S—, —SO 2 —, —CO—, —CR 28.
  • R 29 — represents an alkenylene group
  • R 28 and R 29 each independently represent a hydrogen atom, an alkyl group or a halogen atom
  • p 21 represents an integer of 1 or more
  • q 21 represents an integer of 1 or more.
  • ⁇ 3> The polymer functional film according to ⁇ 1> or ⁇ 2>, wherein the ⁇ -alkylacryloylamino group or the ⁇ -substituted alkyl group of the ⁇ -alkylacryloyloxy group is a methyl group
  • ⁇ 4> The polymer functional film according to any one of ⁇ 1> to ⁇ 3>, wherein the content of the polyfunctional monomer with respect to the total mass after drying is 1,000 ppm to 3,000 ppm
  • ⁇ 5> The polymer functional film according to any one of ⁇ 1> to ⁇ 4>, wherein the content of the polyfunctional monomer with respect to the total mass after drying is 1,000 ppm to 2,000 ppm.
  • ⁇ 6> The polymer functional film according to any one of ⁇ 1> to ⁇ 5>, wherein the composition further contains another monomer different from the polyfunctional monomer, ⁇ 7>
  • film, ⁇ 9> A module comprising the polymer functional film according to any one of ⁇ 1> to ⁇ 8>, ⁇ 10>
  • An apparatus comprising the polymer functional film according to any one of ⁇ 1> to ⁇ 8>.
  • 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.
  • “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.
  • the description which does not describe substitution and unsubstituted includes the thing which has a substituent with the thing which does not have a substituent.
  • 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).
  • 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.
  • the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
  • “(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 a resin copolymerized by 50% by mass or more. In the present invention, a combination of two or more preferred embodiments is a more preferred embodiment.
  • the polymer functional film of the present invention includes a polymer compound obtained by curing a composition containing a polyfunctional monomer.
  • the ClogP value of the polyfunctional monomer is ⁇ 5.2 or more and the ionic group is an anionic group
  • the polyfunctional monomer has a CLogP value of ⁇ 1.9 or more, and the polyfunctional monomer with respect to the total mass after drying.
  • the content of is not less than 500 ppm and not more than 3,000 ppm.
  • H + ions or OH ⁇ ions which are monovalent ions, have a smaller ion radius than, for example, the same monovalent ions Na + and Cl ⁇ , High density. That is, H + ions or OH ⁇ ions are considered to be more hydrophilic. Therefore, by using a polymer compound obtained by curing a monomer having a high CLogP value as the polymer compound constituting the film, the skeleton of the film becomes hydrophobic, and the affinity with H + ions or OH ⁇ ions decreases.
  • the chemical structure is not easily affected by the same ions, and the pH resistance is improved.
  • the polymer functional film contains a specific amount of monomer.
  • the polymer functional membrane of the present invention can be suitably used as a membrane for performing ion exchange, reverse osmosis, forward osmosis, gas separation and the like, and is preferably an ion exchange membrane.
  • the thickness of the polymeric functional membrane of the present invention is preferably 30 to 1,000 ⁇ m, more preferably 50 to 500 ⁇ m, even more preferably 100 to 400 ⁇ m, including the support, when the support has a support.
  • any electrically neutral and inactive group can be used without inhibiting the function of the polymer functional film. .
  • the polymer functional film of the present invention contains a polymer compound.
  • the above polymer compound is a polyfunctional monomer having an ionic group and two or more ⁇ -alkylacryloylamino groups or ⁇ -alkylacryloyloxy groups in one molecule (hereinafter referred to as “specific polyfunctional monomer”).
  • the ionic group is a cationic group
  • the ClogP value of the specific polyfunctional monomer is a polymer compound obtained by curing a composition containing the above (hereinafter also referred to as “specific composition”). Is ⁇ 5.2 or more, and when the ionic group is an anionic group, the ClogP value of the specific polyfunctional monomer is ⁇ 1.9 or more.
  • the polymer compound in the present invention is preferably an ion exchange resin. As long as it is an ion exchange resin, it may be an anion exchange resin or a cation exchange resin.
  • the polymer functional membrane of the present invention is preferably an anion exchange membrane.
  • the polymer functional membrane of the present invention is preferably a cation exchange membrane.
  • the content of the structural unit derived from the specific polyfunctional monomer in the polymer compound is preferably 20 to 90% by mass and more preferably 30 to 80% by mass with respect to the total mass of the polymer compound. Preferably, it is 40 to 80% by mass. Details of the components contained in the specific composition such as the specific polyfunctional monomer will be described later.
  • the polymer functional film in the present invention may have a 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.
  • the polymer functional film of the present invention is preferably a film having at least a part of the polymer compound of the present invention inside the porous support.
  • the said polymeric functional film is a film
  • the material forming the porous support in the present invention is, for example, polyethylene, polypropylene, polyacrylonitrile, polyvinyl chloride, polyester, polyamide and copolymers thereof, or polysulfone, polyethersulfone, polyphenylenesulfone, polyphenylenesulfide.
  • 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., Tapils Co., Ltd., and Freudenberg Filtration Technologies.
  • the porous support when performing a polymerization (curing) reaction by irradiation with actinic light, the porous support preferably does not block the wavelength region of actinic light, that is, allows the irradiation of the wavelength used for polymerization (curing) to pass.
  • the porous support is preferably capable of penetrating the specific composition forming the polymer compound in the present invention.
  • the porous support preferably has hydrophilicity.
  • general methods such as corona treatment, plasma treatment, fluorine gas treatment, ozone treatment, sulfuric acid treatment, and silane coupling agent treatment can be used.
  • the porous support in the present invention is preferably a non-woven fabric, and more preferably a non-woven fabric made of a composite fiber of polyethylene and polypropylene.
  • the fiber diameter of the composite fiber is preferably 0.5 to 15 ⁇ m, more preferably 1 to 13 ⁇ m, and particularly preferably 2 to 10 ⁇ m.
  • the thickness of the porous support in the present invention is preferably 20 to 200 ⁇ m, more preferably 30 to 150 ⁇ m, and particularly preferably 40 to 120 ⁇ m.
  • the content of the specific polyfunctional monomer with respect to the total mass after drying is preferably 500 ppm to 3,000 ppm, and preferably 1,000 ppm to 3,000 ppm. More preferably, it is 2,000 ppm or more and 2,000 ppm or less.
  • the drying is performed by storing the polymer functional membrane in a vacuum oven at 60 ° C. for 24 hours. In order to prevent moisture from being adsorbed in the air, the total mass after drying is determined by weighing the mass within one minute after removal from the oven.
  • the content of the specific polyfunctional monomer is determined by cutting the polymer functional membrane into 5 cm square, immersing it in 10 g of dimethyl sulfoxide, and performing extraction for 24 hours using a mix rotor.
  • the content (concentration) of was determined by quantification using HPLC (High Performance Liquid Chromatography).
  • content of the said specific polyfunctional monomer can be adjusted with the grade which wash
  • the specific composition used in the present invention is preferably a curable composition, and more preferably a photocurable composition.
  • the “curability” in the present invention is not particularly limited as long as a solid or gel-like object can be formed by some stimulus such as light or heat.
  • 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.
  • the “active light” is not particularly limited as long as it is an active light that can impart energy capable of generating an initiation species from a photopolymerization initiator described later by irradiation thereof, and is widely used for ⁇ rays, ⁇ Including X-rays, X-rays, ultraviolet rays (UV), visible rays, electron beams and the like. Among these, light containing at least ultraviolet rays is preferable.
  • each component which the specific composition used for this invention contains is demonstrated.
  • the specific polyfunctional monomer used in the present invention has an ionic group and two or more ⁇ -alkylacryloylamino groups or ⁇ -alkylacryloyloxy groups in one molecule.
  • the ⁇ -substituted alkyl group contained in the ⁇ -alkylacryloylamino group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.
  • the ⁇ -substituted alkyl group contained in the ⁇ -alkylacryloyloxy group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.
  • the specific polyfunctional monomer contains 2 or more ⁇ -alkylacryloylamino groups or ⁇ -alkylacryloyloxy groups, preferably 2 to 6, and preferably 2 to 4 in a molecule. More preferably, two are more preferable.
  • the ionic group possessed by the specific polyfunctional monomer used in the present invention may be an anionic group or a cationic group.
  • the polymer compound is preferably a cation exchange resin, and when the ionic group is a cationic group, the polymer compound is preferably an anion exchange resin.
  • a sulfo group, a phosphonic acid group, a phosphoric acid group, and a carboxy group are preferable, and a sulfo group is more preferable.
  • the anionic group may form a salt or a quaternary ammonium salt, an alkali metal salt, an alkaline earth metal salt, or the like.
  • the cationic group is not particularly limited and is preferably a group having an onium salt structure, and more preferably a group having a quaternary ammonium salt structure.
  • the cationic group may form a salt, and may form a carboxylate, a halogen salt, a sulfate, or the like.
  • the ClogP value of the specific polyfunctional monomer is ⁇ 5.2 or more, and preferably ⁇ 5.0 or more.
  • the upper limit is not particularly limited, and it is preferably 1 or less because the specific polyfunctional monomer can be cured in a state dissolved in water.
  • the specific multifunctional monomer has a CLogP value of ⁇ 1.9 or more, preferably ⁇ 1.7 or more.
  • the upper limit is not particularly limited, and it is preferably 1 or less because the specific polyfunctional monomer can be cured in a state dissolved in water.
  • the CLogP value is an estimated value of the water / octanol partition coefficient.
  • the ionized structure not containing a counter ion can be calculated using ChemDraw 14.0.
  • a compound having a sulfonic acid group is calculated for a structure in which the sulfonic acid group is replaced with —SO 3 — .
  • the specific polyfunctional monomer preferably includes a compound represented by the following formula PCL-I or formula II.
  • the polymer compound obtained by curing the specific composition is preferably an anion exchange resin.
  • R A′1 and R A′2 each independently represents an alkyl group
  • R A′3 to R A′6 each independently represents an alkyl group or an aryl group
  • Z A ′ 1 and Z A′2 each independently represent —O— or —NRa—
  • Ra represents a hydrogen atom or an alkyl group
  • L A′1 and L A′2 each independently represent an alkylene group
  • R X represents an alkylene group, an alkenylene group, an alkynylene group, an arylene group, —O— or a divalent linking group in which these are combined
  • X A′1 and X A′2 each independently represent an organic or inorganic group Represents an anion.
  • R 21 and R 22 each independently represents an alkyl group
  • R 23 , R 24 , R 25 and R 26 each independently represent a substituent
  • k 21 and k 24 each independently represent Represents an integer of 0 to 4
  • k 22 and k 23 each independently represents an integer of 0 to 3
  • R 23 , R 24 , R 25 and R 26 may be the same or different from each other and may be bonded to each other to form a ring
  • a 21 , A 22 , A 23 and A 24 are each independently a single bond or a divalent group.
  • M 21 independently represents a hydrogen ion, an organic base ion or a metal ion
  • n 21 and n 22 each independently represents an integer of 1 to 4
  • m 21 and m 22 each independently Represents 0 or 1
  • J 1 represents a single bond, —O—, —S—, —SO 2 —, —CO—, —CR 28.
  • R 29 — represents an alkenylene group
  • R 28 and R 29 each independently represent a hydrogen atom, an alkyl group or a halogen atom
  • p 21 represents an integer of 1 or more
  • q 21 represents an integer of 1 or more.
  • R A′1 and R A′2 each independently represent an alkyl group, preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and a methyl group Is more preferable.
  • R A′1 and R A′2 are preferably the same group.
  • Z A′1 and Z A′2 are preferably both —NRa— from the viewpoint of resistance of the ion exchange membrane after curing to acid and alkali.
  • R A′3 to R A′6 are preferably each independently an alkyl group.
  • R A′3 to R A′6 may be the same or different from each other, and are preferably the same.
  • the number of carbon atoms of the alkyl group in R A′3 to R A′6 is preferably 1 to 9, more preferably 1 to 3, further preferably 1 or 2, and particularly preferably 1.
  • the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a hexyl group, a pentyl group, an octyl group, and a nonyl group, and a methyl group, an ethyl group, a propyl group, or an isopropyl group is preferable, and a methyl group or an ethyl group Is more preferable, and a methyl group is still more preferable.
  • the alkyl group may have a branched structure or a ring structure.
  • X A′1 and X A′2 each independently represent an inorganic or organic anion, and there is no particular limitation as long as it is an anion that neutralizes the charge, even if it is a monovalent anion, It may be a polyvalent anion, preferably a monovalent anion, more preferably an aliphatic or aromatic sulfonate ion, an aliphatic or aromatic carboxylate ion, a halide ion, or a sulfate ion. More preferred are halide ions or aliphatic or aromatic carboxylate ions.
  • halide ion in X A′1 and X A′2 a chloride ion, a bromide ion or an iodide ion is preferable, and a chloride ion or a bromide ion is more preferable.
  • an acetate anion is preferable.
  • the number of carbon atoms of L A′1 and L A′2 is independently preferably 1 to 10, more preferably 2 to 10, still more preferably 2 to 6, particularly preferably 2 to 4, 3 is most preferred.
  • R X in the formula PCL-I is preferably an alkylene group, an arylene group or a divalent linking group obtained by combining these, more preferably an alkylene group or a group obtained by combining an alkylene group and an arylene group, and an alkylene group and an arylene group.
  • a group in combination with a group is more preferred.
  • the alkylene group preferably has 1 to 12 carbon atoms, preferably 1 to 9, more preferably 2 to 8, still more preferably 3 to 8, and particularly preferably 3 to 5. Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octamethylene group, and a nonamethylene group.
  • Examples of the arylene group include a phenylene group and a naphthylene group, and preferably have 6 to 12 carbon atoms.
  • Examples of the group in which the alkylene group and the arylene group are combined include an alkylene group-arylene group-alkylene group, and —CH 2 —C 6 H 4 —CH 2 — is preferable.
  • the molecular weight of the compound represented by the formula PCL-I is preferably 250 to 800, more preferably 250 to 700, and still more preferably 250 to 600.
  • the specific polyfunctional monomer may contain a compound represented by the formula PCL-I alone or in combination of two or more.
  • the content of the compound represented by the formula PCL-I in the specific composition is 10 to 70% by mass with respect to the total mass of the specific composition. It is preferably 20 to 60% by mass, more preferably 30 to 60% by mass.
  • the content of the structural unit derived from the compound represented by the formula PCL-I is 20 to 90% by mass with respect to the total mass of the polymer compound. It is preferably 30 to 80% by mass, more preferably 40 to 80% by mass.
  • the polymer compound obtained by curing the specific composition is preferably a cation exchange resin.
  • R 21 and R 22 each independently represents an alkyl group, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, More preferably, it is a methyl group.
  • R 21 and R 22 are preferably the same group.
  • R 23 , R 24 , R 25 and R 26 each independently represents a substituent, and the substituent includes an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, More preferably 1 to 4 carbon atoms), an aryl group (preferably 3 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), an alkenyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms). More preferably 2 to 4 carbon atoms), an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 4 carbon atoms), an alkoxy group (preferably 1 to 2 carbon atoms).
  • an alkyl group preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, More preferably 1 to 4 carbon atoms
  • an aryl group preferably 3 to 20 carbon atoms, more preferably 6 to 10 carbon atoms
  • aryloxy group (preferably 3 to 20 carbon atoms, more preferably 6 to 10 carbon atoms), halogen atom, acyl group (preferably Carbon number To 20, more preferably 2 to 12 carbon atoms, still more preferably 2 to 4 carbon atoms), acyloxy groups (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 4 carbon atoms). ), A cyano group.
  • the alkyl group may be linear, branched or cyclic.
  • the aryl group may be a heteroaryl group containing an N atom, an O atom, or an S atom as a hetero atom.
  • k 21 and k 24 each independently represents an integer of 0 to 4, preferably 0 or 1, and more preferably 0.
  • k 22 and k 23 each independently represents an integer of 0 to 3, preferably 0 or 1, and more preferably 0.
  • a 21 , A 22 , A 23 and A 24 each independently represents a single bond or a divalent linking group.
  • the divalent linking group include a linear, branched or cyclic alkylene group (preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 4 carbon atoms).
  • Examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, and a decylene group, and in the case of a cyclic alkylene group, that is, a cycloalkylene group, preferably 3 carbon atoms.
  • cycloalkylene group having 3 to 8 carbon atoms, and still more preferably 3 to 6 carbon atoms
  • a linear, branched or cyclic alkynylene group preferably having 2 to 30 carbon atoms, more preferably An alkenylene group having 2 to 12 carbon atoms, more preferably 2 to 4 carbon atoms, and examples thereof include an ethenylene group and a propenylene group.
  • the cyclic alkenylene group is preferably a 5- or 6-membered cycloalkenylene group), an alkyleneoxy group (preferably an alkylene group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, and still more preferably 1 to 4 carbon atoms).
  • An oxy group such as a methyleneoxy group, an ethyleneoxy group, a propyleneoxy group, a butyleneoxy group, a pentyleneoxy group, a hexyleneoxy group, an octyleneoxy group, and a decyleneoxy group
  • an aralkylene group preferably Aralkylene groups having 7 to 30 carbon atoms, more preferably 7 to 13 carbon atoms, such as benzylidene groups and cinnamylidene groups, and arylene groups (preferably having 6 to 30 carbon atoms, more preferably having 6 to 6 carbon atoms).
  • arylene groups for example, phenylene group, cumenylene group, mesitylene group .
  • the further substituent is preferably a hydroxy group or a halogen atom.
  • M 21 each independently represents a hydrogen ion, an organic base ion or a metal ion.
  • Organic base ions include ammonium ions (eg, ammonium, methylammonium, dimethylammonium, trimethylammonium, diethylammonium, triethylammonium, dibenzylammonium), organic heterocyclic ions (nitrogen-containing heterocyclic ions are preferred,
  • the heterocycle in the nitrogen heterocycle ion is preferably a 5- or 6-membered ring, which may be an aromatic ring or a mere heterocycle, and may be condensed with another ring such as a benzene ring, Spiro ring and bridged ring may be formed, for example, pyridinium, N-methylimidazolium, N-methylmorpholinium, 1,8-diazabicyclo [5.4.0] -7-undecanium, 1,8 -Diazabicyclo [4.3.0] -7-nonenium, gu
  • the metal ions include metal ions selected from alkali metal ions (for example, lithium ions, sodium ions, potassium ions) and alkaline earth metal ions (for example, beryllium ions, magnesium ions, calcium ions), Alkali metal ions are preferred.
  • alkali metal ions for example, lithium ions, sodium ions, potassium ions
  • alkaline earth metal ions for example, beryllium ions, magnesium ions, calcium ions
  • Alkali metal ions are preferred.
  • the plurality of M 21 may be the same as or different from each other.
  • M 21 is preferably a hydrogen ion, an organic base ion or an alkali metal ion, more preferably a hydrogen ion, an organic heterocyclic ion, a lithium ion, a sodium ion or a potassium ion, and a hydrogen ion, pyridinium, N-alkylmorpholinium ( Particularly preferred are N-methylmorpholinium), N-alkylimidazolium (preferably N-methylimidazolium), lithium ion or sodium ion.
  • n 21 and n 22 each independently represents an integer of 1 to 4, and m 21 and m 22 each independently represents 0 or 1.
  • n 21 and n 22 are each independently preferably 1 to 3, more preferably 1 or 2, and particularly preferably 1.
  • m 21 and m 22 are preferably 0.
  • J 1 represents a single bond, —O—, —S—, —SO 2 —, —CO—, —CR 28 R 29 —, or an alkenylene group
  • R 28 and R 29 are each independently a hydrogen atom Represents an alkyl group or a halogen atom.
  • J 1 represents a single bond, -O -, - SO 2 - , - CO -, - CR 28 R 29 -, or (preferably ethylene group) alkenylene group is preferably a single bond, -SO 2 —, —CR 28 R 29 — or an alkenylene group is more preferable, and a single bond is particularly preferable.
  • R 28 and R 29 are each independently preferably an alkyl group or a halogen atom, more preferably a methyl group or a fluorine atom.
  • p 21 represents an integer of 1 or more, preferably 1-5, more preferably 1-3, 1 being particularly preferred.
  • q 21 represents an integer of 1 or more, preferably 1 to 4, more preferably 1 to 2, and still more preferably 1.
  • the compound represented by the above formula II is preferably a compound represented by the following formula III.
  • R 21, R 22, R 23, R 24, R 25, R 26, k 21, k 22, k 23, k 24, A 21, A 22, A 23, A 24, M 21, m 21 , m 22 , n 21 , n 22 are R 21 , R 22 , R 23 , R 24 , R 25 , R 26 , k 21 , k 22 , k 23 , k 24 , A 21 in the above formula II, respectively.
  • a 22 , A 23 , A 24 , M 21 , m 21 , m 22 , n 21 , n 22 , and the preferred range is also the same.
  • the molecular weight of the compound represented by Formula II is preferably 250 to 800, more preferably 250 to 700, and still more preferably 250 to 600.
  • the specific polyfunctional monomer may contain the compound represented by Formula II alone or in combination of two or more.
  • the content of the compound represented by Formula II in the specific composition is 10 to 70% by mass with respect to the total mass of the specific composition. It is preferably 20 to 60% by mass, more preferably 25 to 50% by mass.
  • the polymer functional membrane of the present invention is a cation exchange membrane
  • the content of the structural unit derived from the compound represented by Formula II is 20 to 90% by mass with respect to the total mass of the polymer compound. It is preferably 30 to 80% by mass, more preferably 40 to 80% by mass.
  • the specific composition in the present invention may contain a monofunctional monomer as another monomer different from the specific polyfunctional monomer.
  • the monofunctional monomer is not particularly limited, and a compound represented by the following formula IA is preferably used.
  • the compound represented by the formula IA is preferably contained in the specific composition when the polymer compound is an anion exchange resin.
  • 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
  • two or more of R A2 to R A4 are bonded to each other to form a ring.
  • 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
  • the alkyl group in R A1 , R A2 to R A4 and R N is preferably a linear or branched alkyl group, and preferably has 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. Is more preferable, 1 or 2 is particularly preferable, and 1 is most preferable.
  • the carbon number of the aryl group in R A2 to R A4 is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 10. For example, a phenyl group and a naphthyl group are mentioned.
  • 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 preferably 1 to 10, more preferably 2 to 10, still more preferably 2 to 6, particularly preferably 2 to 4, and most preferably 3.
  • X A1- is preferably a halide ion or an aliphatic or aromatic carboxylate ion. Examples of the halide ion in X A1- include fluoride ion, chloride ion, bromide ion, and iodide ion.
  • the carbon number of the aliphatic carboxylate ion in X A1- is preferably 1 to 20, more preferably 2 to 10, still 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, and the carboxyl group is bonded to a saturated hydrocarbon.
  • the aromatic carboxylate ion in X A1- is preferably an arylcarboxylate ion or a heteroarylcarboxylate ion.
  • the heteroaryl group in the heteroarylcarboxylate ion is preferably a 5- or 6-membered ring.
  • the hetero atom constituting the heterocyclic ring is preferably a nitrogen atom, an oxygen atom or a sulfur atom, and more preferably a nitrogen atom.
  • the aromatic carboxylate ion has preferably 1 to 17 carbon atoms, more preferably 2 to 13 carbon atoms, and still more preferably 6 to 11 carbon atoms.
  • 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 compound represented by the formula IA is preferably a compound represented by any one of the following formulas IA-1 to IA-26, but the present invention is not limited thereto.
  • the molecular weight of the compound represented by the formula IA is preferably 150 to 350, more preferably 150 to 300, and still more preferably 150 to 270.
  • the compounds represented by the formula IA may be used singly or in combination of two or more. Further, the content of the compound represented by the formula IA in the specific composition is preferably 1 to 40% by mass, more preferably 5 to 30% by mass with respect to the total mass of the specific composition. More preferably, it is 10 to 25% by mass.
  • IC-Compound represented by Formula IC- As the monofunctional monomer, a compound represented by the following formula IC is also preferably used.
  • the compound represented by the formula IC is preferably contained in the specific composition when the polymer compound is a cation exchange resin.
  • R C1 represents a hydrogen atom or an alkyl group
  • L C1 represents an alkylene group or an arylene group
  • X C1 + represents an inorganic or organic cation.
  • R C1 is preferably a hydrogen atom or a linear or branched alkyl group, more preferably a hydrogen atom or a methyl group, and still more preferably a hydrogen atom.
  • the number of carbon atoms of the alkyl group is preferably 1 to 10, more preferably 1 to 6, still more preferably 1 to 4, particularly preferably 1 or 2, and most preferably 1.
  • the alkylene group of L C1 preferably has 1 to 10 carbon atoms, more preferably 2 to 8 carbon atoms, and still more preferably 3 to 8 carbon atoms.
  • Examples thereof include an ethylene group, a propylene group, a 1-methylmethylene group, a 1,1-dimethylmethylene group, a 1,1-dimethylethylene group, a butylene group, a hexamethylene group, and an octamethylene group.
  • the carbon number of the arylene group of L C1 is preferably 6 to 16, more preferably 6 to 12, and still more preferably 6 to 10. Examples thereof include a phenylene group and a naphthylene group.
  • the alkylene group and arylene group of L C1 may have a substituent.
  • the type of the substituent is not particularly limited, and preferred examples include a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, and an aryl group.
  • the inorganic cation in X C1 + is preferably a proton or an alkali metal ion, more preferably a proton, a lithium ion, a sodium ion or a potassium ion.
  • Examples of the organic cation in X C1 + include a quaternary ammonium cation and a cation obtained by alkylating a nitrogen atom of an aromatic nitrogen-containing heterocycle.
  • Examples of the quaternary ammonium cation include a tetramethylammonium cation, a tetraethylammonium cation, and a dimethylbenzylammonium cation.
  • Examples of the cation obtained by alkylating the nitrogen atom of the aromatic nitrogen-containing heterocycle include a pyridinium cation.
  • X C1 + is preferably a proton, an alkali metal ion, a quaternary ammonium cation or a pyridinium cation.
  • —SO 3 — and X C1 + may form a covalent bond, an ionic bond, or X C1 + may be free.
  • the molecular weight of the compound represented by the formula IC is preferably 150 to 350, more preferably 150 to 300, and still more preferably 150 to 270.
  • the compounds represented by the formula IC may be used singly or in combination of two or more. Further, the content of the compound represented by the formula IC in the specific composition is preferably 1 to 40% by mass, more preferably 10 to 40% by mass with respect to the total mass of the specific composition, More preferably, it is contained at 40% by mass.
  • the specific composition used in the present invention preferably further contains another polyfunctional monomer different from the specific polyfunctional monomer.
  • another polyfunctional monomer different from the specific polyfunctional monomer a monomer having two or more acrylamide groups or a monomer having two or more acryloyloxy groups is preferable.
  • a compound represented by the following formula PCL-I ′ is preferable.
  • the compound represented by the formula PCL-I ′ is preferably included in the specific composition when the polymer compound is an anion exchange resin.
  • R A′3 to R A′6 , Z A′1 , Z A′2 , L A′1 , L A′2 , R x , X A′1 and X A′2 are R A′3 to R A′6 , Z A′1 , Z A′2 , L A′1 , L A′2 , R x , X A′1 and X A′2 in the above formula PCL-I, respectively.
  • the preferred range is also the same.
  • the molecular weight of the compound represented by the formula PCL-I ′ is preferably 250 to 800, more preferably 250 to 700, and still more preferably 250 to 600.
  • the specific composition may contain one compound or two or more compounds represented by the formula PCL-I ′.
  • the content of the compound represented by the formula PCL-I ′ in the specific composition is preferably 10 to 70% by mass and more preferably 20 to 60% by mass with respect to the total mass of the specific composition. Preferably, it is 30 to 60% by mass.
  • a compound represented by the following formula II ′ is preferable as another polyfunctional monomer different from the specific polyfunctional monomer.
  • the compound represented by the formula II ′ is preferably contained in the specific composition when the polymer compound is a cation exchange resin.
  • R 23 , R 24 , R 25 , R 26 , k 21 , k 22 , k 23 , k 24 , A 21 , A 22 , A 23 , A 24 , M 21 , m 21 , m 22 , n 21 , n 22 , J 1 , p 21 and q 21 are respectively R 23 , R 24 , R 25 , R 26 , k 21 , k 22 , k 23 , k 24 , A 21 , A in the above formula II. 22 , A 23 , A 24 , M 21 , m 21 , m 22 , n 21 , n 22 , J 1 , p 21 and q 21 have the same meaning, and the preferred range is also the same.
  • the molecular weight of the compound represented by Formula II ′ is preferably 250 to 800, more preferably 250 to 700, and still more preferably 250 to 600.
  • the specific composition may contain the compound represented by Formula II ′ alone or in combination of two or more.
  • the content of the compound represented by formula II ′ in the specific composition is preferably 10 to 70% by mass, more preferably 20 to 60% by mass, based on the total mass of the specific composition, More preferably, it is 25 to 50% by mass.
  • the specific composition may contain a polyfunctional monomer having no ionic group as another polyfunctional monomer different from the specific polyfunctional monomer.
  • the polyfunctional monomer having no ionic group is not particularly limited, and a known monomer can be used, alkylene bisacrylamide is preferable, and methylene bisacrylamide is more preferable.
  • the total mass of the monomers is preferably 30% by mass or more, more preferably 50% by mass or more, and 60% by mass or more with respect to the total mass of the specific composition. Is more preferable, and it is especially preferable that it is 70 mass% or more. Moreover, it is preferable that the total mass of a monomer is 80 mass% or less with respect to the total mass of a specific composition, and, as for the specific composition in this invention, it is more preferable that it is 75 mass% or less. When the total mass of the monomer is 30% by mass or more with respect to the total mass of the specific composition, the strength of the cured product is excellent, and when the total mass is 60% by mass or more, the water permeability of the cured product is excellent. Moreover, if the total mass of a monomer is 80 mass% or less with respect to the total mass of a specific composition, it will be excellent in the physical property of a specific composition and will be easy to handle.
  • the specific composition used in the present invention preferably further contains (i) another monomer different from the specific polyfunctional monomer.
  • the other monomer different from the specific polyfunctional monomer includes the monofunctional monomer and / or another polyfunctional monomer different from the specific polyfunctional monomer.
  • the specific composition used in the present invention preferably contains (ii) the specific polyfunctional monomer and another polyfunctional monomer different from the specific polyfunctional monomer, and (iii) the specific polyfunctional monomer. It is more preferable to contain other polyfunctional monomers different from the specific polyfunctional monomer and the monofunctional monomer. According to the above aspect, the ionic group density in the specific composition can be increased, and a polymer functional film having low film resistance can be obtained.
  • (ii) As an embodiment containing the specific polyfunctional monomer and another polyfunctional monomer different from the specific polyfunctional monomer, (ii-1) a compound represented by the formula PCL-I, a formula PCL- More preferably, it contains a compound represented by I ′ or a compound represented by Formula II and a compound represented by Formula II ′.
  • An embodiment containing the specific polyfunctional monomer, another polyfunctional monomer different from the specific polyfunctional monomer, and the monofunctional monomer is represented by (iii-1) Formula PCL-I Containing a compound, a compound represented by formula PCL-I ′, and a compound represented by formula IA, or (iii-2) a compound represented by formula II and a compound represented by formula II ′ And a compound represented by the formula IC.
  • the specific composition preferably includes a polymerization initiator, and more preferably includes a photopolymerization initiator in order to perform curing with light.
  • the photopolymerization initiator that can be used in the present invention is a compound capable of initiating and promoting polymerization of a monomer such as a compound having an ethylenically unsaturated group by actinic rays.
  • the photopolymerization initiator is preferably a radical photopolymerization initiator.
  • a water-soluble photoinitiator is preferable as a photoinitiator.
  • the water-soluble photopolymerization initiator means a photopolymerization initiator that is dissolved in distilled water at 25 ° C.
  • the water-soluble photopolymerization initiator is more preferably a photopolymerization initiator that dissolves 1% by mass or more in distilled water at 25 ° C., and particularly preferably a photopolymerization initiator that dissolves 3% by mass or more.
  • 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. Among these, an aromatic ketone compound or an acylphosphine compound is preferable, and a compound represented by the following formula PPI-1 or formula PPI-2 is more preferable.
  • R P1 and R P2 each independently represents a hydrogen atom, an alkyl group, an alkoxy group or an aryloxy group
  • R P3 represents an alkyl group, an alkoxy group or an aryloxy group
  • L is 0 to Represents an integer of 5.
  • R P4 represents an alkyl group, aryl group, alkylthio group or arylthio group
  • R P5 represents an alkyl group, aryl group, alkylthio group, arylthio group or acyl group
  • R P6 represents an alkyl group or aryl group Represents a group.
  • 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 having 1 to 8 carbon atoms 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.
  • the alkyl group, alkoxy group, and 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 or an alkoxy group having 1 to 4 carbon atoms, and particularly preferably a hydroxyethoxy group.
  • 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, preferably an integer of 0 to 3, and more preferably 0 or 1.
  • the alkyl group in R P4 to R P6 is preferably an alkyl group having 1 to 8 carbon atoms.
  • the aryl group in R P4 to R P6 is preferably an aryl group having 6 to 16 carbon atoms.
  • the aryl 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 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.
  • a compound represented by the formula PPI-1 is particularly preferred over 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 specific composition in this invention may contain the polymerization initiator individually by 1 type, and may contain 2 or more types.
  • the content of the polymerization initiator is preferably 0.05 to 20 parts by mass, more preferably 0.05 to 10 parts by mass with respect to 100 parts by mass of the total solid content in the specific composition. 0.1 to 5 parts by mass is particularly preferable.
  • the total solid content in the specific composition in the present invention represents an amount excluding volatile components such as a solvent.
  • the specific composition in the present invention may contain a solvent.
  • the solvent may be included singly or in combination of two or more.
  • the content of the solvent in the specific composition is preferably 1 to 60% by mass, more preferably 5 to 50% by mass, and more preferably 10 to 45% by mass with respect to the total mass of the specific composition. More preferably, the content is 15 to 40% by mass.
  • the water permeability of the obtained cured product is more excellent, the film resistance is reduced, and the handleability is also excellent.
  • the curing (polymerization) reaction proceeds uniformly and smoothly. Further, when the porous support is impregnated with the specific composition of the present invention, the impregnation proceeds smoothly.
  • the solvent water or a mixed solution of water and a solvent having a solubility in 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.
  • the water-soluble solvent alcohol solvents, aprotic polar solvents, ether solvents, amide solvents, ketone solvents, sulfoxide solvents, sulfone solvents, nitrile solvents, and organic phosphorus solvents are particularly preferable. .
  • alcohol solvent examples 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.
  • aprotic polar solvent examples include dimethyl sulfoxide, dimethylimidazolidinone, sulfolane, N-methylpyrrolidone, dimethylformamide, acetonitrile, acetone, dioxane, tetramethylurea, hexamethylphosphoramide, hexamethylphosphorotriamide, Pyridine, propionitrile, butanone, cyclohexanone, tetrahydrofuran, tetrahydropyran, ethylene glycol diacetate, ⁇ -butyrolactone and the like are mentioned as preferred solvents.
  • dimethyl sulfoxide N-methylpyrrolidone, dimethylformamide, dimethylimidazolidinone, sulfolane, acetone or acetonitrile, and tetrahydrofuran are preferred. These can be used alone or in combination of two or more.
  • 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.
  • a mixed solvent of water and an alcohol solvent a mixed solvent of water and isopropanol is particularly preferable.
  • the specific composition in the present invention may contain a polymerization inhibitor.
  • 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.
  • the phenol compound include hindered phenols (phenols having a t-butyl group at the ortho position, typically 2,6-di-t-butyl-4-methylphenol) and bisphenols. It is done.
  • a monomethyl ether hydroquinone is mentioned as a hydroquinone compound.
  • the amine compound include N-nitroso-N-phenylhydroxylamine and N, N-diethylhydroxylamine.
  • 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 specific composition. More preferably, the content is 0.01 to 0.5 parts by mass.
  • the specific composition in the present invention may contain a neutralizing agent for counterion exchange of the ionic group of the monomer used.
  • a neutralizing agent for counterion exchange of the ionic group of the monomer used.
  • an alkali metal compound is preferably exemplified.
  • the alkali metal compound lithium, sodium, potassium hydroxide salts, halide salts, nitrates and the like are preferable. Of these, sodium and lithium compounds are more preferable.
  • a neutralizing agent can be used individually by 1 type or in combination of 2 or more types. The addition amount of the neutralizing agent 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 specific composition.
  • composition in the present invention may contain known additives other than those described above as necessary.
  • additives for example, surfactants, viscosity improvers, polymer compounds, polymer dispersants, crater inhibitors. , Plasticizers, viscosity modifiers, antioxidants, and / or preservatives.
  • the specific composition in the present invention may contain various polymer compounds 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.
  • the specific composition in 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 one that reduces irregularities on the film surface.
  • the anti-crater agent is also called a surface tension adjusting agent, a surface adjusting agent, a leveling agent or a slip agent.
  • a surface tension adjusting agent for example, an organic modified polysiloxane (mixture of polyether siloxane and polyether), polyether modified polysiloxane copolymer, silicone modified copolymer Compounds of the structure.
  • 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 specific composition.
  • the specific composition in the present invention may contain 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.
  • 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.
  • 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
  • Method for producing polymer functional membrane There is no restriction
  • the method for producing a polymer functional film in the present invention preferably includes a coating step of coating and / or impregnating a specific composition on a support.
  • the polymer functional membrane of the present invention may be prepared in a batch system using a fixed support (batch system), or may be prepared in a continuous system using a moving support system (continuous system). May be.
  • the support may be in the form of a roll that is continuously rewound.
  • the step of placing a support on a belt that is continuously moved and polymerizing with a continuous application of a coating solution that is a specific composition to form a film can be performed continuously. However, only one of the coating process and the film forming process may be performed continuously.
  • a temporary support it peels a film
  • a temporary support does not need to consider material permeation, and may be any material as long as it can be fixed for film formation, including a metal plate such as an aluminum plate.
  • the porous support can be impregnated with the composition, and polymerization can be performed without using a support other than the porous support.
  • compositions 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, slot die coating or spray coating.
  • the porous support can be applied or impregnated. Multiple layers can be applied simultaneously or sequentially.
  • curtain coating, slide coating, slot die coating and extrusion coating are preferred.
  • the production of the functional polymer film in a continuous manner is carried out by continuously applying the specific composition to the moving support, more preferably by applying the specific composition application portion and irradiation for polymerizing the specific composition. It is manufactured by a manufacturing unit including a source, a film winding unit, and a means for moving the support from the specific composition coating unit to the irradiation source and the film winding unit.
  • the polymer functional membrane of the present invention is produced through a process of removing the membrane from the support.
  • the specific composition coating part can be placed upstream of the active light irradiation source, and the irradiation source is placed upstream of the composite film winding part.
  • the viscosity of the specific composition at 50 ° C. is 4,000 mPa.s. less than s, preferably 1 to 1,000 mPa.s. s is more preferable, and 1 to 500 mPa.s is preferable. s is most preferred.
  • the viscosity at 50 ° C. is 1 to 100 mPa.s. s is preferred.
  • the specific composition can be applied to the moving support at a speed exceeding 15 m / min, and can be applied at a speed exceeding 400 m / min at the maximum.
  • a support when using a support to increase the mechanical strength of the membrane, before applying the specific composition to the surface of the support, to improve the wettability and adhesion of the support, for example, corona discharge treatment Further, it may be subjected to glow discharge treatment, flame treatment, ultraviolet irradiation treatment and the like.
  • the hardening process in the manufacturing method of the polymeric functional film in this invention is a process of irradiating a specific composition with an actinic ray and polymerizing.
  • the polymerization is preferably carried out by light irradiation under conditions where the polymerization occurs rapidly enough to form a film within 30 seconds.
  • the start of the polymerization is preferably within 60 seconds, more preferably within 15 seconds, particularly preferably within 5 seconds, and most preferably within 3 seconds after applying the specific composition to the support.
  • the time for irradiating the specific composition with light 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.
  • irradiation is performed continuously, and the polymerization time is determined by the speed at which the specific composition moves through the irradiation beam.
  • UV light ultraviolet ray
  • IR light infrared light
  • the active light is preferably ultraviolet light.
  • the irradiation wavelength is preferably compatible with the absorption wavelength of any photoinitiator included in the specific composition, for example, UV-A (400 to 320 nm), UV-B (320 to 280 nm), 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 UV lamps are particularly preferred.
  • additives such as metal halides may be present to modify the emission spectrum of the lamp. In most cases, lamps having an emission maximum between 200 and 450 nm are particularly suitable.
  • the energy output of the actinic radiation source is preferably 20 to 1,000 W / cm, more preferably 40 to 500 W / cm, but higher if this can achieve the desired exposure dose. It does n’t matter if it ’s low.
  • the degree of curing of the film can be adjusted by changing the exposure intensity.
  • the exposure dose is high energy UV radiometer (UV Power Puck TM manufactured by EIT-Instrument Markets). Preferably at least 40 mJ / cm 2 or more, more preferably from 100 to 2,000 mJ / cm 2 , even more preferably from 150 to 1,500 mJ / cm 2 , measured in the UV-B range indicated by the above apparatus. is there.
  • 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.
  • the manufacturing method of the polymeric functional film in this invention may also include the washing
  • the cleaning method is not particularly limited, and the film can be cleaned by immersing the cured film in a solvent.
  • a known solvent can be used without particular limitation, and dimethyl sulfoxide and methanol are preferable.
  • the immersion time may be appropriately set according to the target value of the content of the specific polyfunctional monomer contained in the polymer functional film, preferably 1 to 10 minutes, and more preferably 1 to 5 minutes. What is necessary is just to set the temperature at the time of immersion suitably, 10-60 degreeC is preferable and 20-50 degreeC is more preferable.
  • the polymeric functional membrane of the present invention is particularly intended for use in ion exchange.
  • the polymer functional membrane of the present invention is not limited to ion exchange applications, and can be suitably used for reverse osmosis and gas separation.
  • the polymer functional membrane of the present invention is useful as an ion exchange membrane, and can be used for electrodesalting, continuous electrodesalting, electrodialysis, polarity switching electrodialysis, reverse electrodialysis, and the like. Moreover, it can be used not only for general purposes but also for medical purposes, and recently it can also be used for solid polymer electrolyte fuel cells.
  • the module of the present invention (also referred to as “stack”) includes the polymer functional film of the present invention.
  • anion exchange membranes and cation exchange membranes are alternately arranged between a pair of electrodes, and the anion exchange membrane and / or cation exchange membrane is preferably the polymer functional membrane of the present invention.
  • modules include spiral, hollow fiber, pleated, tubular, plate & frame, and stack types.
  • the apparatus of the present invention includes the polymer functional film of the present invention. The apparatus is preferably used for the above-mentioned use.
  • Benzidine-2,2′-disulfonic acid was added to 288.3 g of sodium hydrogen carbonate (3.43 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and 1,343 mL of ion-exchanged water and stirred at room temperature.
  • 268.6 g (0.78 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little.
  • the mixture was cooled under ice cooling and stirring was continued.
  • 138.7 mL (1.53 mol, manufactured by Wako Pure Chemical Industries, Ltd.) of acryloyl chloride was added dropwise little by little so that the inside of the system was kept at 10 ° C. or lower while stirring under ice cooling.
  • Benzidine-2,2′-disulfonic acid was added to 288.3 g of sodium hydrogen carbonate (3.43 mol, manufactured by Wako Pure Chemical Industries, Ltd.) and 1,343 mL of ion-exchanged water and stirred at room temperature. 268.6 g (0.78 mol, manufactured by Tokyo Chemical Industry Co., Ltd.) was added little by little. After stirring at room temperature for 30 minutes, the mixture was cooled under ice cooling and stirring was continued. 160 mL of methacryloyl chloride (1.53 mol, manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise little by little so that the system was kept at 10 ° C. or lower while stirring under ice cooling.
  • DMAPAA-Q dimethylaminopropylacrylamide methyl chloride quaternary salt (3-acrylamidopropyltrimethylammonium chloride), manufactured by Kojin Film & Chemicals Co., Ltd., the following compounds: AMPS: AMPS (registered trademark), 2-acrylamide-2 -Methylpropanesulfonic acid, manufactured by Lubrizol Co., Ltd., the following compound.
  • the specific composition-impregnated support obtained as described above was subjected to a curing reaction using a UV exposure machine (manufactured by Fusion UV Systems, Model Light Hammer LH6, D-bulb, speed 15 m / min, 100% strength).
  • a UV exposure machine manufactured by Fusion UV Systems, Model Light Hammer LH6, D-bulb, speed 15 m / min, 100% strength.
  • an ion exchange membrane (polymer functional membrane) was produced.
  • the curing time was 0.8 seconds.
  • the exposure time was 0.47 seconds.
  • the obtained film was removed from the aluminum plate and immersed in methanol for the time described in Table 1 or Table 2. Subsequently, it was stored in a 0.1 mol / L NaCl aqueous solution for at least 12 hours. The thickness of the obtained film was 134 ⁇ m.
  • the membrane is cut into 5 cm square, immersed in 10 g of dimethyl sulfoxide, extracted for 24 hours using a mix rotor, and the content (concentration) of unreacted specific polyfunctional monomer in the extraction solution. was quantified using HPLC.
  • the measurement results are shown in Table 3.
  • the ion exchange membrane in the example described as “A” in the column of the exchange membrane type is an anion exchange membrane
  • the ion exchange membrane in the example described as “C” is a cation exchange membrane.
  • AA film resistance 2 [Omega ⁇ cm 2 below
  • A membrane resistance 2 [Omega ⁇ cm 2 or more 3 [Omega] ⁇ cm 2 less
  • B less than electrode resistance 3 [Omega] ⁇ cm 2 or more 4 ⁇ ⁇ cm 2
  • C membrane resistance 4ohm ⁇ cm 2 or more
  • the breaking stress change value is less than 2 MPa.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un film polymère fonctionnel, et un module ainsi qu'un dispositif équipé de celui-ci. Ledit film polymère fonctionnel contient un composé polymère obtenu par durcissement d'une composition comprenant un monomère polyfonctionnel. Ledit monomère polyfonctionnel possède un groupe ionique, et des groupes α－alkylacryloylamino ou des groupes α－alkylacryloyloxy à raison d'au moins deux groupes par molécule. Dans le cas où ledit groupe ionique consiste en un groupe cationique, une valeur LogP dudit monomère polyfonctionnel est supérieure ou égale à -5,2. Dans le cas où ledit groupe ionique consiste en un groupe anionique, la valeur LogP dudit monomère polyfonctionnel est supérieure ou égale à -1,9. La teneur en monomère polyfonctionnel par rapport à la masse totale après séchage, est supérieure ou égale à 500ppm et inférieure ou égale à 3000ppm.
PCT/JP2016/070357 2015-08-24 2016-07-11 Film polymère fonctionnel, module, et dispositif WO2017033593A1 (fr)

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JP2015164955 2015-08-24
JP2015-164955 2015-08-24
JP2015241981A JP2018167134A (ja) 2015-08-24 2015-12-11 高分子機能性膜、モジュール、及び、装置
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014171951A (ja) * 2013-03-07 2014-09-22 Fujifilm Corp 機能性複合膜及びその製造方法、並びに機能性複合膜を具備したイオン交換膜及びプロトン伝導膜
JP2014176840A (ja) * 2013-02-15 2014-09-25 Fujifilm Corp 高分子機能性膜及びその製造方法
JP2014526959A (ja) * 2011-07-19 2014-10-09 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 硬化性組成物および膜
JP2016137434A (ja) * 2015-01-27 2016-08-04 富士フイルム株式会社 高分子機能性膜及びその製造方法、積層体、並びに、装置

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2014526959A (ja) * 2011-07-19 2014-10-09 フジフィルム・マニュファクチュアリング・ヨーロッパ・ベスローテン・フエンノートシャップ 硬化性組成物および膜
JP2014176840A (ja) * 2013-02-15 2014-09-25 Fujifilm Corp 高分子機能性膜及びその製造方法
JP2014171951A (ja) * 2013-03-07 2014-09-22 Fujifilm Corp 機能性複合膜及びその製造方法、並びに機能性複合膜を具備したイオン交換膜及びプロトン伝導膜
JP2016137434A (ja) * 2015-01-27 2016-08-04 富士フイルム株式会社 高分子機能性膜及びその製造方法、積層体、並びに、装置

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