WO2011081145A1 - モザイク荷電複層膜およびその製造方法 - Google Patents
モザイク荷電複層膜およびその製造方法 Download PDFInfo
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- WO2011081145A1 WO2011081145A1 PCT/JP2010/073589 JP2010073589W WO2011081145A1 WO 2011081145 A1 WO2011081145 A1 WO 2011081145A1 JP 2010073589 W JP2010073589 W JP 2010073589W WO 2011081145 A1 WO2011081145 A1 WO 2011081145A1
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- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- MOTZDAYCYVMXPC-UHFFFAOYSA-N dodecyl hydrogen sulfate Chemical compound CCCCCCCCCCCCOS(O)(=O)=O MOTZDAYCYVMXPC-UHFFFAOYSA-N 0.000 description 1
- 229940043264 dodecyl sulfate Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010556 emulsion polymerization method Methods 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- YCUBDDIKWLELPD-UHFFFAOYSA-N ethenyl 2,2-dimethylpropanoate Chemical compound CC(C)(C)C(=O)OC=C YCUBDDIKWLELPD-UHFFFAOYSA-N 0.000 description 1
- CMDXMIHZUJPRHG-UHFFFAOYSA-N ethenyl decanoate Chemical compound CCCCCCCCCC(=O)OC=C CMDXMIHZUJPRHG-UHFFFAOYSA-N 0.000 description 1
- GLVVKKSPKXTQRB-UHFFFAOYSA-N ethenyl dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC=C GLVVKKSPKXTQRB-UHFFFAOYSA-N 0.000 description 1
- GFJVXXWOPWLRNU-UHFFFAOYSA-N ethenyl formate Chemical compound C=COC=O GFJVXXWOPWLRNU-UHFFFAOYSA-N 0.000 description 1
- AFSIMBWBBOJPJG-UHFFFAOYSA-N ethenyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC=C AFSIMBWBBOJPJG-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 239000004088 foaming agent Substances 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
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- 238000007646 gravure printing Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- IBUDOENFVGHGFQ-UHFFFAOYSA-N hydroxy propyl carbonate Chemical compound CCCOC(=O)OO IBUDOENFVGHGFQ-UHFFFAOYSA-N 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 125000001841 imino group Chemical group [H]N=* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000003014 ion exchange membrane Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 125000005647 linker group Chemical group 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004957 naphthylene group Chemical group 0.000 description 1
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- 238000007645 offset printing Methods 0.000 description 1
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- 150000007524 organic acids Chemical class 0.000 description 1
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- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 125000005496 phosphonium group Chemical group 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
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- 230000001737 promoting effect Effects 0.000 description 1
- QYUMESOEHIJKHV-UHFFFAOYSA-M prop-2-enamide;trimethyl(propyl)azanium;chloride Chemical compound [Cl-].NC(=O)C=C.CCC[N+](C)(C)C QYUMESOEHIJKHV-UHFFFAOYSA-M 0.000 description 1
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 1
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- 239000013535 sea water Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- XFTALRAZSCGSKN-UHFFFAOYSA-M sodium;4-ethenylbenzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=C(C=C)C=C1 XFTALRAZSCGSKN-UHFFFAOYSA-M 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- NLVXSWCKKBEXTG-UHFFFAOYSA-N vinylsulfonic acid Chemical compound OS(=O)(=O)C=C NLVXSWCKKBEXTG-UHFFFAOYSA-N 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Images
Classifications
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- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/80—Block polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/12—Special parameters characterising the filtering material
- B01D2239/1233—Fibre diameter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D2325/38—Hydrophobic membranes
Definitions
- the present invention relates to a mosaic charged multilayer film and a method for producing the same.
- the mosaic charged membrane is a membrane having a charged structure in which cation exchange domains and anion exchange domains are alternately arranged and each domain is continuous from one side of the membrane to the other side. With such a charged structure, the mosaic charged membrane can promote the permeation of low molecular weight ions in the target solution without requiring an external current.
- the cation exchange domains and the anion exchange domains are alternately arranged, the electric charges of the domains are opposite to each other, so that an electric circuit is formed in which the salt solution portions on both sides of the membrane become resistance.
- the cation and the anion are transported through the cation exchange domain and the anion exchange domain, respectively, thereby generating a circulating current and promoting the transport of the salt.
- the mosaic charged membrane has a mechanism that causes ion transport in the membrane itself, unlike an ion exchange membrane having a single type of fixed charge that requires an external current.
- Patent Document 1 describes a method for desalting organic compounds using a mosaic charged membrane produced by utilizing the microphase separation phenomenon of a block copolymer.
- the method for producing a mosaic charged membrane using the microphase separation phenomenon of a block copolymer requires advanced techniques to obtain a block copolymer having a desired structure, and the operation is complicated. It is difficult to efficiently and inexpensively manufacture a large-area mosaic charged film that is expensive and industrially practical.
- it is difficult to form a structure in which the cation exchange domain and the anion exchange domain are continuous from one side of the membrane to the other side it is difficult to achieve high salt selective permeability.
- Patent Document 2 a film-forming polymer, a solvent capable of dissolving the film-forming polymer, a cation exchange resin and an anion exchange resin are mixed, and the cation exchange resin and the anion exchange resin are dispersed in the polymer solution to uniformly Preparing a suitable polymer dispersion; and applying and stretching the polymer dispersion on a substrate, drying and solidifying, then removing the solvent from the resulting film and washing.
- a method for manufacturing a mosaic charged film is described. It is described that the mosaic charged membrane obtained by this method increases the salt permeation amount as the pressure increases in the pressure dialysis experiment.
- Patent Document 3 discloses that an average particle size of 0.01 to 10 ⁇ m is present in a crosslinked continuous phase formed by any one of a cationic polymer and an anionic polymer.
- a method for producing a mosaic charged membrane composed of a cationic polymer domain and an anionic polymer domain dispersed as crosslinked particles at least a continuous phase is formed in a solution of any one of the ionic polymers forming the continuous phase of the membrane.
- a mosaic charged film characterized in that a film is formed using a dispersion in which spherical fine particles of a polymer having an ionicity opposite to the polymer are dispersed, at least a continuous phase in the film is crosslinked, and then immersed in water or an aqueous solution.
- the manufacturing method is described.
- the film produced by this method can be easily adjusted in domain size and film thickness, and the greatest advantage is that a film having a large area can be produced relatively easily.
- polymer fine particles having a small average particle diameter must be prepared, and there is a problem that a high level of technology and a long time are required.
- the resulting mosaic charged membrane is composed of a highly hydrous microgel, the pressure resistance is very low, and in particular, the adhesiveness between the membrane matrix and the positive and negative microgel interfaces is not perfect because of its structure. It is difficult to produce a mosaic charged membrane having electrolyte permeability, and the mechanical strength is not sufficient.
- Patent Document 4 discloses a mosaic charged membrane body comprising a cationic polymer, an anionic polymer, and a support, the support being an asymmetric porous body, and the support being filled with both polymers in a dialysis manner.
- a mosaic charged film body in which a support is filled with a polymer particle mixed dispersion obtained by mixing cationic and anionic spherical polymers is described. According to this, it is said that it is possible to provide a mosaic charged membrane having a large area that can improve pressure resistance and mechanical strength, and can separate an electrolyte and a non-electrolyte or can desalt a salt solution in a simple process. ing.
- the mosaic charged membrane obtained in this way has insufficient salt permselectivity performance, and the adhesion between the cationic polymer and the anionic polymer and the support may be insufficient. It was done.
- Non-Patent Document 1 describes a mosaic charged film manufactured by a lamination method.
- a lamination method a cation exchange membrane is produced from polyvinyl alcohol and a polyanion, an anion exchange membrane is produced from polyvinyl alcohol and a polycation, and a laminated charge block is produced by alternately laminating these with polyvinyl alcohol as an adhesive.
- the resulting block is cut with a lab cutter perpendicular to the laminated surface, and then subjected to a crosslinking treatment to produce a laminated mosaic charged film having a thickness of about 150 ⁇ m.
- the laminated mosaic charged membrane thus obtained has a KCl salt flux J KCl of 3.0 ⁇ 10 ⁇ 9 mol ⁇ cm ⁇ 2 ⁇ s ⁇ 1 and an electrolyte permselectivity ⁇ of 2300, which is a very high value. It is described to show. Although the tensile strength was 5.7 MPa in the direction parallel to the charged layer, it was 2.7 MPa in the vertical direction and can be used for diffusion dialysis. Need to increase.
- Non-Patent Document 2 describes a mosaic charged membrane produced by a polymer blend method using polyvinyl alcohol as a membrane matrix.
- an aqueous solution of a modified PVA polyanion containing 2 mol% of a vinyl compound containing polyvinyl alcohol and an itaconic acid group as a copolymer composition is used to suppress dissociation of hydrogen ions from the carboxyl group of the itaconic acid group.
- a polymer blend aqueous solution was prepared by mixing a solution acidified with hydrochloric acid and a polyvinyl alcohol and a polyallylamine hydrochloride aqueous solution.
- This solution is cast on a glass plate or the like to obtain a membrane, and then chemically crosslinked to obtain a mosaic charged membrane.
- the mosaic charged membrane thus obtained has a KCl salt flux J KCl of 1.7 ⁇ 10 ⁇ 8 mol ⁇ cm ⁇ 2 ⁇ s ⁇ 1 and an electrolyte permselectivity ⁇ of 48.
- higher electrolyte permselectivity is desired.
- the acidic solution has a problem that the salt selective permeability is lowered.
- JP 59-203613 A JP 2006-297338 A JP-A-8-155281 JP-A-8-276122 JP 59-187003 A JP 59-189113 A
- the present invention has been made in order to solve the above-described problems, and an object of the present invention is to provide a mosaic charged multilayer film having a large salt permeation flux and excellent mechanical strength.
- the above-mentioned problems include a porous support layer (A) made of fibers having an average fiber diameter of 1 ⁇ m or more and 100 ⁇ m or less, a porous intermediate layer (B) made of fibers having an average fiber diameter of 0.01 ⁇ m or more and less than 1 ⁇ m, and a cationic polymer.
- the porosity of the support layer (A) is large. This can be solved by providing a mosaic charged multilayer film in which the cationic polymer and / or the anionic polymer constituting the zyk charged layer (C) is polyvinyl alcohol having an ionic group.
- the hydrophilic fiber is preferably a polyvinyl alcohol fiber
- the porous support layer (A) preferably contains a hydrophobic polymer.
- the hydrophobic polymer is at least one selected from the group consisting of polyolefin, polyester and polyamide
- the porous support layer (A) is a fiber layer containing at least 50% by mass of the hydrophobic polymer.
- the porous intermediate layer (B) is preferably composed of a fiber layer containing at least 50% by mass of hydrophilic fibers.
- the cationic polymer and / or the anionic polymer constituting the mosaic charge layer (C) is a block copolymer containing a polymer block having an ionic group and a vinyl alcohol polymer block. is there.
- the mosaic charge layer (C) is formed by printing on the porous intermediate layer (B).
- a method for producing a charged multilayer film is a preferred embodiment of the present invention.
- the mosaic charged multilayer membrane of the present invention has a large salt flux and excellent mechanical strength. Thereby, separation of electrolyte and non-electrolyte, removal of electrolyte (desalting), etc. can be performed efficiently, and it can be used for both diffusion dialysis and pressure dialysis. Moreover, the dimensional stability in the surface direction is also enhanced by the porous support layer.
- the mosaic charged multilayer film of the present invention comprises a porous support layer (A), a porous intermediate layer (B), and a mosaic charged layer (C) composed of a cationic polymer domain and an anionic polymer domain. ), Wherein the porous support layer (A), the porous intermediate layer (B), and the mosaic charged layer (C) are arranged in this order, or within the porous intermediate layer (B) A mosaic charged layer (C) is formed.
- the porous support layer (A) and / or the porous intermediate layer (B) is composed of a fiber layer containing at least 50% by mass of hydrophilic fibers, and the mosaic charged layer (C) is provided.
- the constituent cationic polymer and / or anionic polymer is polyvinyl alcohol having an ionic group, and the porosity of the porous support layer (A) is larger than the porosity of the porous intermediate layer (B). It is characterized by. As a result, a mosaic charged multilayer film having a large salt flux and excellent mechanical strength can be obtained. That is, the present invention provides a cationic polymer in which the porous support layer (A) and the porous intermediate layer (B) are composed of a fiber layer containing at least 50% by mass of hydrophilic fibers and constitute the mosaic charged layer (C).
- the anionic polymer is polyvinyl alcohol having an ionic group
- the porous support layer (A) having a larger porosity than the porous intermediate layer (B) is used, so that the water treatment speed is not lowered.
- the mechanical strength of the mosaic charged multilayer film itself can be improved.
- the porous intermediate layer (B) having a porosity smaller than that of the porous support layer (A) and having a thickness of 0.1 to 100 ⁇ m the surface smoothness of the porous intermediate layer (B) is high. Therefore, the mosaic charge layer (C) is uniformly and firmly formed. As a result, the salt permeation flux can be increased.
- the cationic polymer used in the present invention is a polymer containing a cationic group in the molecular chain.
- the cationic group may be contained in any of the main chain, side chain, and terminal.
- Examples of the cationic group include an ammonium group, an iminium group, a sulfonium group, and a phosphonium group.
- an ammonium group is preferable from the viewpoint of industrial availability.
- ammonium group any of primary ammonium group (ammonium group), secondary ammonium group (alkyl ammonium group, etc.), tertiary ammonium group (dialkyl ammonium group, etc.), quaternary ammonium group (trialkyl ammonium group, etc.) can be used. Although it can be used, a quaternary ammonium group (such as a trialkylammonium group) is more preferable.
- the cationic polymer may contain only one type of cationic group or may contain a plurality of types of cationic groups.
- the counter anion of the cation group is not particularly limited, and examples thereof include halide ions, hydroxide ions, phosphate ions, and carboxylate ions. Of these, halide ions are preferred and chloride ions are more preferred from the standpoint of availability.
- the cationic polymer may contain only one type of counter anion or may contain multiple types of counter anions.
- the cationic polymer used in the present invention may be a polymer composed only of the structural unit containing the cationic group or a polymer further containing a structural unit not containing the cationic group. Moreover, it is preferable that these polymers have a crosslinking property.
- the cationic polymer may be composed of only one type of polymer, or may include a plurality of types of cationic polymers. Moreover, you may be a mixture of these cationic polymers and another polymer.
- the polymer other than the cationic polymer is preferably not an anionic polymer.
- Examples of the cationic polymer include those having structural units of the following general formulas (1) to (8).
- R 1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
- R 2 , R 3 and R 4 each independently represent a hydrogen atom or an optionally substituted alkyl group, aryl group or aralkyl group having 1 to 18 carbon atoms.
- R 2 , R 3 and R 4 may be connected to each other to form a saturated or unsaturated cyclic structure.
- Z represents —O—, —NH—, or —N (CH 3 ) —, and Y represents a divalent linking group having 1 to 8 carbon atoms which may contain an oxygen, nitrogen, sulfur or phosphorus atom.
- X ⁇ represents an anion.
- Counter anion X in the general formula (1) - include a halide ion, hydroxide ion, phosphate ion, a carboxylic acid ion are exemplified.
- Examples of the cationic polymer containing the structural unit represented by the general formula (1) include 3- (meth) acrylamidepropyltrimethylammonium chloride, 3- (meth) acrylamide-3,3-dimethylpropyltrimethylammonium chloride, and the like. Examples include homopolymers or copolymers of-(meth) acrylamide-alkyltrialkylammonium salts.
- R 5 represents a hydrogen atom or a methyl group.
- R 2 , R 3 , R 4 , and X ⁇ are as defined in general formula (1).
- Examples of the cationic polymer containing the structural unit represented by the general formula (2) include homopolymers or copolymers of vinylbenzyltrialkylammonium salts such as vinylbenzyltrimethylammonium chloride.
- R 2 , R 3 , and X ⁇ are as defined in the general formula (1).
- R 2 , R 3 , and X ⁇ are as defined in the general formula (1).
- a homopolymer or copolymer obtained by cyclopolymerizing a diallyldialkylammonium salt such as diallyldimethylammonium chloride is exemplified.
- n 0 or 1; R 2 and R 3 have the same meaning as in the general formula (1).
- Examples of the cationic polymer containing the structural unit represented by the general formula (5) include allylamine homopolymers and copolymers.
- Examples of the cationic polymer containing the structural unit represented by the general formula (6) include homopolymers or copolymers of allyl ammonium salts such as allylamine hydrochloride.
- R 5 represents a hydrogen atom or a methyl group
- A represents —CH (OH) CH 2 —, —CH 2 CH (OH) —, —C (CH 3 ) (OH) CH 2 —, —CH 2 C (CH 3 ) (OH) —, —CH (OH) CH 2 CH 2 —, or —CH 2 CH 2 CH (OH) —
- E is -N (R 6) 2 or -N + (R 6) 3 ⁇ X - represents, R 6 represents a hydrogen atom or a methyl group.
- X ⁇ represents an anion.
- R 5 represents a hydrogen atom or a methyl group
- R 7 represents a hydrogen atom, a methyl group, an ethyl group, an n-propyl group or an i-propyl group
- R 8 represents a hydrogen atom, a methyl group or an ethyl group, respectively. .
- Cationic polymers containing the structural unit represented by the general formula (8) include (meth) acrylamide, N-methyl (meth) acrylamide, N-ethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, etc. Is exemplified.
- the anionic polymer used in the present invention is a polymer containing an anionic group in the molecular chain.
- the anionic group may be contained in any of the main chain, side chain, and terminal.
- Examples of the anion group include a sulfonate group, a carboxylate group, and a phosphonate group.
- functional groups that can be converted at least partially into sulfonate groups, carboxylate groups, and phosphonate groups in water, such as sulfonic acid groups, carboxyl groups, and phosphonic acid groups are also included in the anionic groups.
- a sulfonate group is preferred because of its large ion dissociation constant.
- the anionic polymer may contain only one type of anionic group or may contain a plurality of types of anionic groups.
- the counter cation of an anion group is not specifically limited, A hydrogen ion, an alkali metal ion, etc. are illustrated. Of these, alkali metal ions are preferred from the viewpoint of less equipment corrosion problems.
- the anionic polymer may contain only one type of counter cation or may contain a plurality of types of counter cation.
- the anionic polymer used in the present invention may be a polymer composed only of a structural unit containing the anionic group, or may be a polymer further containing a structural unit not containing the anionic group. Moreover, it is preferable that these polymers have a crosslinking property.
- An anionic polymer may consist of only one type of polymer, or may include a plurality of types of anionic polymers. Moreover, you may be a mixture of these anionic polymers and another polymer.
- the polymer other than the anionic polymer is preferably not a cationic polymer.
- anionic polymer examples include those having structural units of the following general formulas (9) and (10).
- R 5 represents a hydrogen atom or a methyl group.
- G represents —SO 3 H, —SO 3 ⁇ M + , —PO 3 H, —PO 3 ⁇ M + , —CO 2 H or —CO 2 ⁇ M + .
- M + represents an ammonium ion or an alkali metal ion.
- anionic polymer containing the structural unit represented by the general formula (9) examples include 2-acrylamido-2-methylpropanesulfonic acid homopolymer or copolymer.
- R 5 represents a hydrogen atom or a methyl group
- T represents a phenylene group or a naphthylene group in which the hydrogen atom may be substituted with a methyl group.
- G is synonymous with the general formula (9).
- anionic polymer containing the structural unit represented by the general formula (10) examples include homopolymers or copolymers of p-styrene sulfonate such as sodium p-styrene sulfonate.
- anionic polymer examples include homopolymers or copolymers of sulfonic acids such as vinyl sulfonic acid and (meth) allyl sulfonic acid or salts thereof, fumaric acid, maleic acid, itaconic acid, maleic anhydride, itaconic anhydride.
- G is preferably a sulfonate group, a sulfonic acid group, a phosphonate group, or a phosphonic acid group that gives a higher charge density.
- examples of the alkali metal ion represented by M + include sodium ion, potassium ion, lithium ion and the like.
- a vinyl alcohol component is preferable.
- a mixture of a polymer containing an ionic group selected from cationic groups or anionic groups and a polymer not containing an ionic group selected from cationic groups or anionic groups is used, Those having high affinity with the polymer containing an ionic group are preferably used.
- one selected from the group consisting of polyvinyl alcohol and polyacrylamide is preferably used.
- polyvinyl alcohol is more preferably used because of its high crosslinkability.
- the cationic polymer and the anionic polymer are preferably hydrophilic polymers, and this has the advantage of reducing pressure loss.
- that the cationic polymer and the anionic polymer are hydrophilic polymers means that the cationic polymer and the anionic polymer have hydrophilicity in a structure having no functional group necessary for the cationic polymer and the anionic polymer.
- the hydrophilic polymer is a water-soluble polymer
- the mosaic charged layer (C) can be formed by aqueous printing.
- the cationic polymer and the anionic polymer are hydrophilic polymers, a mosaic charged multilayer film having a high degree of hydrophilicity can be obtained, and the organic pollutant in the liquid to be treated can be converted into a mosaic charged multilayer film.
- the problem of adhering to the film and degrading the film performance can be reduced.
- the film strength is increased.
- hydrophilic cationic polymers examples include polyvinyl alcohols containing cationic groups, cellulose derivatives containing cationic groups, polyacrylamides containing cationic groups, polymers containing cationic groups, and polyvinyl alcohols containing no cationic groups. And a mixture of a polymer containing a cationic group and a cellulose derivative not containing a cationic group, a mixture of a polymer containing a cationic group and a polyacrylamide containing no cationic group, and the like. Among these, a polyvinyl alcohol containing a cationic group or a mixture of a polymer containing a cationic group and polyvinyl alcohol not containing a cationic group is preferable.
- a polymer having a polyvinyl alcohol unit from the viewpoint of the strength of the mosaic charged multilayer film, the flexibility of the mosaic charged layer (C), and the physical or chemical crosslinkability.
- a copolymer of methacrylamide alkyltrialkylammonium salt and polyvinyl alcohol component a copolymer of vinylbenzyltrialkylammonium salt and polyvinyl alcohol component, diallyldialkylammonium salt and polyvinyl alcohol from the point of availability.
- polyvinyl alcohol containing a cationic group or a mixture of a polymer containing a cationic group and a polyvinyl alcohol containing no cationic group the ratio of the number of vinyl alcohol units to the total number of monomer units in the cationic polymer However, it is preferable that it is 50 mol% or more, and it is more preferable that it is 70 mol% or more.
- the cationic polymer when it is a hydrophilic polymer, it may be one kind of hydrophilic polymer or a mixture of plural kinds of hydrophilic polymers. Moreover, the mixture of a hydrophilic polymer and a non-hydrophilic polymer may be sufficient. Further, it may contain a polymer other than a hydrophilic or non-hydrophilic cationic polymer. Here, the polymer other than the cationic polymer is preferably not an anionic polymer.
- hydrophilic anionic polymers examples include polyvinyl alcohols containing anionic groups, cellulose derivatives containing anionic groups, polyacrylamides containing anionic groups, polymers containing anionic groups, and polyvinyl alcohols containing no anionic groups. And a mixture of a polymer containing an anionic group and a cellulose derivative not containing an anionic group, a mixture of a polymer containing an anionic group and a polyacrylamide containing no anionic group, and the like. Among these, a polyvinyl alcohol containing an anionic group or a mixture of a polymer containing an anionic group and a polyvinyl alcohol not containing an anionic group is preferable.
- a polymer having a polyvinyl alcohol unit from the viewpoint of the strength of the mosaic charged multilayer film, the flexibility of the mosaic charged layer (C), and physical or chemical crosslinking.
- a copolymer of 2-acrylamido-2-methylpropane sulfonate component and vinyl alcohol component a copolymer of p-styrene sulfonate component and vinyl alcohol component, from the viewpoint of availability.
- Particularly preferred is a mixture of a polymer of acrylamide-2-methylpropane sulfonate and polyvinyl alcohol, or a mixture of a polymer of polystyrene sulfonate and polyvinyl alcohol.
- the ratio of the number of vinyl alcohol units to the total number of monomer units in the anionic polymer is 50 mol% or more, and it is more preferable that it is 70 mol% or more.
- the anionic polymer is a hydrophilic polymer, it may be one kind of hydrophilic polymer or a mixture of plural kinds of hydrophilic polymers.
- the mixture of a hydrophilic polymer and a non-hydrophilic polymer may be sufficient.
- it may contain a polymer other than a hydrophilic or non-hydrophilic cationic polymer.
- the polymer other than the anionic polymer is preferably not a cationic polymer.
- the cationic polymer and / or the anionic polymer constituting the mosaic charged layer (C) is polyvinyl alcohol having an ionic group.
- a block copolymer or graft copolymer containing a polymer component obtained by polymerizing an ionic monomer and a polyvinyl alcohol component is preferably used as the cationic polymer and / or anionic polymer.
- a block copolymer is more preferably used.
- the ionic polymer undergoes microphase separation, and the polyvinyl alcohol component responsible for the function of improving the strength of the entire mosaic charged multilayer film, suppressing the degree of swelling of the film, and maintaining the shape, and the cation or
- the role of the polymer component formed by polymerizing the ionic monomer having the function of allowing the anion to permeate can be shared, and both the swelling degree and the dimensional stability of the mosaic charged multilayer film can be achieved.
- the structural unit of the polymer component obtained by polymerizing the ionic monomer is not particularly limited, and examples thereof include those represented by the general formulas (1) to (10).
- a cationic polymer a block copolymer containing a polymer component obtained by polymerizing a methacrylamide alkyltrialkylammonium salt and a polyvinyl alcohol component, vinylbenzyltrialkyl, because it is easily available.
- a block copolymer containing a polymer component obtained by polymerizing a salt and a polyvinyl alcohol component, or a block copolymer containing a polymer component obtained by polymerizing a diallyldialkylammonium salt and a polyvinyl alcohol component is preferably used. It is done.
- the anionic polymer may be a block copolymer containing a polymer component obtained by polymerizing p-styrene sulfonate and a polyvinyl alcohol component, or 2-acrylamido-2-methylpropane sulfonate.
- a block copolymer containing a polymer component and a polyvinyl alcohol component is preferably used.
- the method for producing a block copolymer containing a polymer component obtained by polymerizing an ionic monomer used in the present invention and a polyvinyl alcohol component is roughly classified into the following two methods.
- one or more types of monomers are block copolymerized in the presence of polyvinyl alcohol having a mercapto group at the terminal, and then one or more types of polymer in the block copolymer are copolymerized.
- a block copolymer is produced by radical polymerization of at least one ionic monomer in the presence of polyvinyl alcohol having a mercapto group at the terminal.
- the method is preferable because of industrial ease.
- the kind and amount of each component of the polymer component obtained by polymerizing the polyvinyl alcohol component and the ionic monomer in the block copolymer can be easily controlled, the presence of polyvinyl alcohol having a mercapto group at the terminal
- a method of producing a block copolymer by radical polymerization of at least one ionic monomer is preferred.
- the block copolymer containing the polymer component obtained by polymerizing the ionic monomer thus obtained and the polyvinyl alcohol component may contain unreacted polyvinyl alcohol having a mercapto group at the terminal. Absent.
- the vinyl alcohol polymer having a mercapto group at the terminal used for the production of these block copolymers can be obtained, for example, by the method described in Patent Document 5 and the like. That is, a method of saponifying a vinyl ester polymer obtained by radical polymerization of a vinyl ester monomer such as vinyl acetate in the presence of thiolic acid can be mentioned. Examples of a method for obtaining a block copolymer using a polyvinyl alcohol having a mercapto group at the terminal thus obtained and an ionic monomer include the method described in Patent Document 6 and the like.
- a block copolymer can be obtained by radical polymerization of an ionic monomer in the presence of polyvinyl alcohol having a mercapto group at the terminal.
- This radical polymerization can be carried out by a known method such as bulk polymerization, solution polymerization, pearl polymerization, emulsion polymerization, etc., but mainly contains a solvent capable of dissolving polyvinyl alcohol containing a mercapto group at the terminal, such as water or dimethyl sulfoxide. It is preferable to carry out in the medium.
- any of a batch method, a semi-batch method, and a continuous method can be employed.
- the content of the ionic monomer unit in the ionic polymer is not particularly limited, but the content of the ionic monomer unit in the ionic polymer, that is, the total number of monomer units in the ionic polymer.
- the ratio of the number of ionic monomer units is preferably 0.1 mol% or more.
- the content of the ionic monomer unit is less than 0.1 mol%, the effective charge density in the mosaic charge layer (C) is lowered, and the electrolyte selective permeability may be lowered.
- the content is more preferably 0.5 mol% or more, and further preferably 1 mol% or more.
- it is preferable that content of an ionic monomer unit is 50 mol% or less.
- the content of the ionic monomer unit exceeds 50 mol%, the degree of swelling of the mosaic charged multilayer film is increased, and the permeation flux of the electrolyte may be decreased.
- the content of the ionic monomer unit is more preferably 30 mol% or less, and further preferably 20 mol% or less.
- Unit content refers to the ratio of the number of ionic monomer units to the total number of monomer units in the mixture.
- the structural unit other than the ionic group can be independently selected, but the cationic polymer and the anionic polymer are different from each other. , Preferably having the same structural unit. Thereby, since the affinity between domains becomes high, the mechanical strength of a mosaic charge layer (C) increases. It is preferable that both the cationic polymer and the anionic polymer have the same structural unit in an amount of 50 mol% or more, and more preferably 80 mol% or more.
- the domains can be chemically cross-linked by a cross-linking agent such as glutaraldehyde, so the mechanical strength of the mosaic charged multilayer film Can be further increased.
- the domain of the cationic polymer is a polyvinyl alcohol containing a cationic group, or a polymer containing a cationic group and a polyvinyl alcohol containing no cationic group. It is made of a mixture, and the domain of the anionic polymer may be a polyvinyl alcohol containing an anionic group, or a mixture of a polymer containing an anionic group and a polyvinyl alcohol containing no cationic group.
- the cationic polymer and / or the anionic polymer constituting the mosaic charge layer (C) is a block copolymer including a polymer block having an ionic group and a vinyl alcohol polymer block. This has the advantage that cross-linking is possible and the adhesion between the porous intermediate layer (B) and the mosaic charge layer (C) is good.
- the polyvinyl alcohol containing an ionic group selected from a cationic group or an anionic group is obtained by copolymerizing an ionic monomer and a vinyl ester monomer and saponifying this by a conventional method.
- the vinyl ester monomer can be used as long as it can be radically polymerized.
- vinyl formate, vinyl acetate, vinyl propionate, vinyl valenate, vinyl caprate, vinyl laurate, vinyl stearate, vinyl benzoate, vinyl pivalate, vinyl versatate and the like can be mentioned.
- vinyl acetate is preferable.
- Examples of the method of copolymerizing the ionic monomer and the vinyl ester monomer include known methods such as a bulk polymerization method, a solution polymerization method, a suspension polymerization method, and an emulsion polymerization method. Among these methods, a bulk polymerization method performed without a solvent or a solution polymerization method performed using a solvent such as alcohol is usually employed. When the copolymerization reaction is carried out using the solution polymerization method, examples of the alcohol used as the solvent include lower alcohols such as methyl alcohol, ethyl alcohol, and propyl alcohol.
- Examples of the initiator used in the copolymerization reaction include 2,2′-azobisisobutyronitrile (AIBN), 2,2′-azobis (2,4-dimethyl-valeronitrile), 1,1′-azobis.
- Azo initiators such as (cyclohexane-1-carbonitrile), 2,2′-azobis (N-butyl-2-methylpropionamide); peroxide initiators such as benzoyl peroxide and n-propyl peroxycarbonate
- known initiators such as an agent.
- the polymerization temperature for carrying out the copolymerization reaction is not particularly limited, but a range of 5 ° C. to 180 ° C. is appropriate.
- the vinyl ester polymer obtained by copolymerizing the ionic monomer and the vinyl ester monomer is then saponified in a solvent according to a known method to form polyvinyl alcohol containing an ionic group. It is guided.
- Alkaline substances are usually used as catalysts for saponification reactions of vinyl ester polymers.
- Examples thereof include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, and alkali metal alkoxides such as sodium methoxide. It is done.
- the saponification catalyst may be added all at once in the early stage of the saponification reaction, or a part thereof may be added in the early stage of the saponification reaction, and the rest may be added and added during the saponification reaction.
- the solvent used for the saponification reaction include methanol, methyl acetate, dimethyl sulfoxide, diethyl sulfoxide, dimethylformamide and the like. Of these solvents, methanol is preferred.
- the saponification reaction can be carried out by either a batch method or a continuous method. After completion of the saponification reaction, the remaining saponification catalyst may be neutralized as necessary, and usable neutralizing agents include organic acids such as acetic acid and lactic acid, and ester compounds such as methyl acetate. .
- the degree of saponification of polyvinyl alcohol containing ionic groups is not particularly limited, but is preferably 40 to 99.9 mol%. If the degree of saponification is less than 40 mol%, the crystallinity is lowered and the strength of the mosaic charge layer (C) may be insufficient.
- the saponification degree is more preferably 60 mol% or more, and further preferably 80 mol% or more. Usually, the saponification degree is 99.9 mol% or less.
- the saponification degree when the polyvinyl alcohol is a mixture of plural kinds of polyvinyl alcohols refers to the average saponification degree of the whole mixture.
- the saponification degree of polyvinyl alcohol is a value measured according to JIS K6726.
- the saponification degree of polyvinyl alcohol containing no ionic group used in the present invention is also preferably in the above range.
- the viscosity average degree of polymerization of the polyvinyl alcohol containing ionic groups (hereinafter sometimes simply referred to as the degree of polymerization) is not particularly limited, but is preferably 50 to 10,000. When the degree of polymerization is less than 50, there is a possibility that the mosaic charged layer (C) cannot maintain sufficient strength in practical use. More preferably, the degree of polymerization is 100 or more. If the degree of polymerization exceeds 10,000, the viscosity of the polymer solution used for printing may be too high to handle. The degree of polymerization is more preferably 8000 or less.
- the polymerization degree in the case where the polyvinyl alcohol is a mixture of plural kinds of polyvinyl alcohols means an average polymerization degree as the whole mixture.
- the viscosity average polymerization degree of polyvinyl alcohol is a value measured according to JIS K6726.
- the polymerization degree of polyvinyl alcohol containing no ionic group used in the present invention is also preferably within the above range.
- the porous support layer (A) used in the present invention is not particularly limited as long as it is made of a porous material.
- the resulting mosaic charged multilayer membrane has excellent mechanical strength and facilitates transport of the salt.
- the porous support layer (A) include non-woven fabrics, membranes, woven fabrics, and synthetic papers, and any conventionally known porous sheet can be used. Among these, a nonwoven fabric, a film, and synthetic paper are more preferable.
- a polyvinyl alcohol fiber aggregate is particularly preferably used, which has an advantage of high strength.
- the thickness of the porous support layer (A) used in the present invention is not particularly limited and is preferably 5 to 1000 ⁇ m. If the thickness of the porous support layer (A) is less than 5 ⁇ m, the strength of the mosaic charged multilayer film may be insufficient. The thickness is more preferably 10 ⁇ m or more, and further preferably 30 ⁇ m or more. If the thickness of the porous support layer (A) exceeds 1000 ⁇ m, it may be difficult to transport the salt. The thickness is more preferably 800 ⁇ m or less, and further preferably 300 ⁇ m or less.
- the basis weight of the porous support layer (A) used in the present invention is not particularly limited, and is preferably 1 to 100 g / m 2 .
- the basis weight is less than 1 g / m 2, the mechanical strength of the resulting mosaic charged multilayer film may be lowered, and it is more preferably 5 g / m 2 or more, and preferably 10 g / m 2 or more. Further preferred.
- the basis weight exceeds 100 g / m 2 , the transport resistance of the salt of the mosaic charged multilayer film is increased, and there is a possibility that sufficient transport may not be possible, and it is more preferably 80 g / m 2 or less, and 50 g / M 2 or less is more preferable.
- the porosity of the porous support layer (A) used in the present invention is not particularly limited as long as it is larger than the porosity of the porous intermediate layer (B) described later.
- the difference in porosity is preferably 5% or more, more preferably 10% or more, and further preferably 15% or more.
- Known means can be used as means for controlling the porosity of the porous support layer (A) and the porous intermediate layer (B) to a desired range.
- the porosity can be controlled by adjusting the basis weight of the resin and the thickness of the layer at the time of manufacture.
- the porosity can be controlled by adjusting the expansion ratio according to the type and amount of the foaming agent.
- the porous support layer (A) and / or the porous intermediate layer (B) is a fiber layer
- the porosity can be controlled by adjusting the entanglement density of the fibers. Further, by reducing the fiber diameter, it becomes easy to increase the entanglement density, and the porosity can be increased.
- the porosity of the porous support layer (A) is preferably 40 to 90%. When the porosity is in this range, the mechanical strength of the obtained mosaic charged multilayer film is excellent, and the air permeability can be kept in a certain range. When the porosity of the porous support layer (A) is less than 40%, the salt transport resistance may be increased, more preferably 50% or more, and even more preferably 55% or more. On the other hand, when the porosity of the porous support layer (A) exceeds 90%, the mechanical strength of the resulting mosaic charged multilayer film may be inferior, more preferably 80% or less, and 75% or less. More preferably it is.
- the porous support layer (A) is made of fibers having an average fiber diameter of 1 ⁇ m or more and 100 ⁇ m or less. Thereby, a mosaic charged multilayer film having excellent mechanical strength can be obtained.
- the average fiber diameter is less than 1 ⁇ m, the salt transport resistance may increase, and it is preferably 3 ⁇ m or more.
- the surface smoothness is inferior, and the porous intermediate layer (B) may not be provided uniformly, and is preferably 50 ⁇ m or less.
- the porous intermediate layer (B) used in the present invention is made of a porous material and is not particularly limited as long as the thickness of the porous intermediate layer (B) is 0.1 to 100 ⁇ m.
- the porous intermediate layer (B) include polyvinyl alcohol and polyacrylamide. Among them, polyvinyl alcohol is preferably used.
- the thickness of the porous intermediate layer (B) is less than 0.1 ⁇ m, pinholes may occur, and the thickness is preferably 0.5 ⁇ m or more, and more preferably 1 ⁇ m or more.
- the thickness of the porous intermediate layer (B) exceeds 100 ⁇ m, the salt transport resistance may increase, and it is preferably 70 ⁇ m or less, and more preferably 50 ⁇ m or less.
- the ratio (A / B) between the thickness of the porous support layer (A) and the thickness of the porous intermediate layer (B) is not particularly limited, and is preferably 2 or more and preferably 5 or more. Preferably, it is 10 or more.
- the thickness ratio (A / B) is usually 100 or less.
- the basis weight of the porous intermediate layer (B) used in the present invention is not particularly limited, and is preferably 0.1 to 10 g / m 2 . If the basis weight is less than 0.1 g / m 2 , pinholes may occur, more preferably 0.8 g / m 2 or more, and even more preferably 1 g / m 2 or more. On the other hand, when the basis weight exceeds 10 g / m 2 , the salt transport resistance may increase, and it is more preferably 5 g / m 2 or less.
- the ratio (A / B) between the basis weight of the porous support layer (A) and the basis weight of the porous intermediate layer (B) is not particularly limited, and is preferably 2 or more, and is 5 or more. It is more preferable. On the other hand, the basis weight ratio (A / B) is usually 100 or less.
- the porosity of the porous intermediate layer (B) used in the present invention is not particularly limited as long as it is smaller than the porosity of the porous support layer (A), and specifically 30 to 80%. Is preferred.
- the porosity is in this range, the smoothness of the surface of the porous intermediate layer (B) can be increased, so that the mosaic charge layer (C) is uniformly formed on the porous intermediate layer (B). .
- the permeation flux of the salt in the obtained mosaic charged multilayer membrane can be increased.
- the porosity of the porous intermediate layer (B) is less than 30%, the salt transport resistance may increase, and it is more preferably 35% or more.
- the porosity of the porous intermediate layer (B) exceeds 80%, it may be difficult to uniformly provide the mosaic charge layer (C), and it is more preferably 70% or less, and 65% More preferably, it is as follows.
- the porous intermediate layer (B) is composed of a fiber layer having an average fiber diameter of 0.01 ⁇ m or more and less than 1 ⁇ m. This makes it possible to further increase the smoothness of the surface of the porous intermediate layer (B), and the mosaic charge layer (C) is uniformly formed on the porous intermediate layer (B). Moreover, the porous intermediate layer (B) has a high density. As a result, there is an advantage that the permeation flux of the salt in the obtained mosaic charged multilayer membrane can be increased.
- the average fiber diameter is less than 0.01 ⁇ m, the strength of the fiber layer may be insufficient, and is preferably 0.05 ⁇ m or more, more preferably 0.1 ⁇ m or more.
- the average fiber diameter is 1 ⁇ m or more
- the smoothness of the fiber layer surface may be lowered, and it is preferably 0.8 ⁇ m or less, and more preferably 0.6 ⁇ m or less.
- the ratio (A / B) between the average fiber diameter of the porous support layer (A) and the average fiber diameter of the porous intermediate layer (B) is not particularly limited, but is preferably 2 or more, and 5 or more. It is more preferable that On the other hand, the average fiber diameter ratio (A / B) is usually 100 or less.
- the porous support layer (A) and / or the porous intermediate layer (B) is composed of a fiber layer containing at least 50% by mass of hydrophilic fibers. Since the porous intermediate layer (B) is composed of a fiber layer containing at least 50% by mass of hydrophilic fibers, there are advantages in that the pressure loss is low and the water treatment speed is high. Moreover, since affinity with a mosaic charged layer (C) becomes high, it has the advantage that the adhesiveness of a porous intermediate
- the porous support layer (A) and the porous intermediate layer (B) are composed of a fiber layer containing at least 50% by mass of hydrophilic fibers, in addition to the above effects, the porous support layer (A) and the porous layer there is an advantage that the adhesion between the layers of the quality intermediate layer (B) is also improved.
- the hydrophilic fiber is preferably a polyvinyl alcohol fiber. That is, the porous support layer (A) and / or the porous intermediate layer (B) is preferably composed of a fiber layer containing at least 50% by mass of polyvinyl alcohol fibers. This has the advantages of low pressure loss and high water treatment speed. Moreover, since affinity with a mosaic charged layer (C) becomes high, it also has the advantage that the adhesiveness of a porous intermediate
- the porous support layer (A) preferably contains a hydrophobic polymer.
- the resulting mosaic charged multilayer membrane has excellent strength in water, a large salt permeation flux, and excellent electrolyte selective permeability.
- a porous support layer (A) can suppress the swelling and deformation
- a porous intermediate layer (B) is formed on the porous support layer (A), and a mosaic charged layer (C) is formed by applying or printing a solution or dispersion on the porous intermediate layer (B).
- the dimensional stability is improved.
- the porous support layer (A) is made of hydrophilic fibers, the present inventors have a large air permeability of the obtained mosaic charged multilayer film due to the influence of the dimensional change of the porous support layer (A). Confirm that it will be.
- the hydrophobic polymer used for the porous support layer (A) is not particularly limited as long as it does not substantially have a protic functional group such as a hydroxyl group or a carboxyl group. From the polyolefin, polyester and polyamide It is preferably at least one selected from the group consisting of, and more preferably at least one selected from the group consisting of polyester and polyamide.
- the porous support layer (A) preferably contains 50% by mass or more of the hydrophobic polymer, more preferably 70% by mass or more, and still more preferably 90% by mass or more.
- the component other than the hydrophobic polymer contained in the porous support layer (A) is not particularly limited, and a polymer having high adhesion to the porous intermediate layer (B) may be used.
- the porous support layer (A) when the polymer forming the porous intermediate layer (B) is a vinyl alcohol resin, the porous support layer (A) also contains the vinyl alcohol resin or is coated on the fiber surface, thereby supporting the porous support.
- the adhesiveness between the layer (A) and the porous intermediate layer (B) can be enhanced.
- the thickness of the mosaic charge layer (C) used in the present invention is not particularly limited, and is preferably 0.1 to 80 ⁇ m from the viewpoint of increasing the salt flux.
- the thickness is more preferably 0.5 ⁇ m or more, further preferably 1 ⁇ m or more, and particularly preferably 2 ⁇ m or more.
- the salt permeation flux may be reduced.
- the thickness is more preferably 50 ⁇ m or less, further preferably 30 ⁇ m or less, and particularly preferably 10 ⁇ m or less.
- the thickness of the multilayer structure (D) obtained by forming the porous intermediate layer (B) on the porous support layer (A), and the thickness of the mosaic charged layer (C) The ratio (C / D) is not particularly limited, and is preferably 0.001 to 0.2. When the ratio (C / D) is less than 0.001, there is a possibility that defects will occur in the resulting mosaic charged layer (C). The ratio is more preferably 0.005 or more, and still more preferably 0.01 or more. If the ratio (C / D) exceeds 0.2, the salt permeation flux may be too small. The ratio is more preferably 0.15 or less, and further preferably 0.1 or less.
- the domain size (Wc) of the cationic polymer constituting the mosaic charged layer (C) is not particularly limited, but between the positively charged region and the negatively charged region in the mosaic charged multilayer film. Since the electrolyte selective permeability tends to increase as the distance becomes smaller, it is preferably 1000 ⁇ m or less.
- the domain size is more preferably 500 ⁇ m or less, further preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less. On the other hand, the domain size is usually 0.1 ⁇ m or more.
- the domain size of the cationic polymer means an average value of the diameters of circles inscribed in the domain, and is a value obtained by arithmetic average from the dimension of the horizontal domain observed with a microscope.
- the domain size (Wa) of the anionic polymer constituting the mosaic charged layer (C) is not particularly limited, but between the positively charged region and the negatively charged region in the mosaic charged multilayer film. Is preferably 1000 ⁇ m or less from the viewpoint of decreasing the distance and increasing the electrolyte selective permeability.
- the domain size is more preferably 500 ⁇ m or less, further preferably 300 ⁇ m or less, and particularly preferably 100 ⁇ m or less. On the other hand, the domain size is usually 0.1 ⁇ m or more.
- the domain size of an anionic polymer means the average value of the diameter of the circle
- the porous support layer (A), the porous intermediate layer (B), and the mosaic charged layer (C) described above are arranged in this order, or the porous intermediate layer
- the mosaic charge layer (C) is formed in (B).
- the porous support layer (A) and / or the porous intermediate layer (B) is composed of a fiber layer containing at least 50% by mass of hydrophilic fibers, and the mosaic charged layer (C) is provided.
- the constituent cationic polymer and / or anionic polymer is polyvinyl alcohol having an ionic group, and the porosity of the porous support layer (A) is larger than the porosity of the porous intermediate layer (B). It is characterized by.
- the method of arranging the porous support layer (A), the porous intermediate layer (B), and the mosaic charged layer (C) in this order is not particularly limited. After obtaining the multilayer structure (D) in which the porous intermediate layer (B) is formed on the porous support layer (A), mosaic charging is performed on the porous intermediate layer (B) in the multilayer structure (D). A method of forming the layer (C) is preferably employed.
- the smoothness is not particularly limited, and pulp test method No. of JAPAN TAPPI paper. 5 is preferably 10 seconds or more, more preferably 50 seconds or more, and still more preferably 200 seconds or more.
- the method for forming the mosaic charged layer (C) on the porous intermediate layer (B) is not particularly limited, but from the viewpoint that the mosaic charged layer (C) having a desired pattern can be easily formed, the porous intermediate layer is formed.
- a method of forming the mosaic charged layer (C) on the (B) by printing is preferably employed. By adopting the printing method, a mosaic charged layer (C) having a small thickness can be formed, so that a mosaic charged multilayer film having a large permeation flux can be obtained. Furthermore, the domain size of each of the cationic polymer and the anionic polymer can be reduced, and a mosaic charged multilayer film having excellent electrolyte selective permeability can be obtained.
- the pattern shape is not particularly limited, and examples thereof include a stripe shape, a checkered shape, a lattice shape, and a polka dot shape. Printing is usually performed using a printing apparatus.
- any conventionally known printing method can be applied as the printing method used in the present invention.
- the printing method include an inkjet printing method, a screen printing method, a transfer printing method, a dispenser printing method, a gravure printing method, and an offset printing method.
- the inkjet printing method, the screen printing method, the transfer printing method, and the dispenser printing method are particularly preferable from the viewpoint of simplicity of printing.
- the mosaic charged layer (C) may be formed only on the surface of the porous intermediate layer (B), and not only the surface of the porous intermediate layer (B) but also the porous
- the mosaic charge layer (C) may be formed inside the intermediate layer (B).
- the inventors of the present invention have a part of the mosaic charged layer (C) inside the porous intermediate layer (B) due to capillary action. Therefore, it has been confirmed that the mosaic charge layer (C) is formed not only on the surface of the porous intermediate layer (B) but also inside the porous intermediate layer (B).
- the mosaic charged layer (C) when the mosaic charged layer (C) is printed on the porous intermediate layer (B), and the entire mosaic charged layer (C) enters the inside of the porous intermediate layer (B) by capillary action.
- the mosaic charge layer (C) is not formed on the porous intermediate layer (B) but inside the porous intermediate layer (B).
- the mosaic charged multilayer film of the present invention has a mosaic charged layer (C) formed in the porous intermediate layer (B). In the mosaic charged layer multilayer film thus obtained, the mosaic charged layer (C) is not exposed on the surface of the porous intermediate layer (B).
- the method for producing a mosaic charged multilayer film of the present invention it is preferable to perform heat treatment after forming the mosaic charged layer (C).
- the degree of crystallinity is increased, so that physical cross-linking is increased, and the mechanical strength of the resulting mosaic charged multilayer film is increased.
- the cation groups and anion groups are concentrated in the amorphous part and a high-density ion exchange path is formed, the charge density is increased, so that the counter ion selectivity is improved and the salt flux is improved.
- the method of heat treatment is not particularly limited, and a hot air dryer or the like is generally used.
- the temperature of the heat treatment is not particularly limited, but in the case of polyvinyl alcohol, it is preferably 50 to 250 ° C. If the heat treatment temperature is less than 50 ° C., the mechanical strength of the resulting mosaic charged multilayer film may be insufficient.
- the temperature is more preferably 80 ° C. or higher, and further preferably 100 ° C. or higher. If the temperature of the heat treatment exceeds 250 ° C, polyvinyl alcohol may be thermally decomposed.
- the temperature is more preferably 230 ° C. or less, and further preferably 200 ° C. or less.
- the heat treatment time is usually about 1 minute to 10 hours.
- the heat treatment is desirably performed in an inert gas (eg, nitrogen gas, argon gas, etc.) atmosphere.
- the method for producing a mosaic charged multilayer film of the present invention it is preferable to perform hot pressing after forming the mosaic charged layer (C).
- the hot press treatment By performing the hot press treatment, the mosaic charged layer (C) provided by printing becomes dense, and the mechanical strength of the resulting mosaic charged layer (C) increases.
- the method of the heat press treatment is not particularly limited, and calendar equipment or the like is generally used.
- the temperature of the hot press treatment is not particularly limited, but in the case of polyvinyl alcohol, it is preferably 80 to 250 ° C. If the temperature of the hot press treatment is less than 80 ° C., the mechanical charge layer (C) obtained may have insufficient mechanical strength.
- the temperature is more preferably 100 ° C. or higher, and further preferably 130 ° C. or higher. If the temperature of the hot press treatment exceeds 250 ° C, the polyvinyl alcohol may be melted.
- the press temperature is more preferably 230 ° C. or lower, and further preferably 200 ° C. or lower.
- the method for producing a mosaic charged multilayer film of the present invention it is preferable to perform a crosslinking treatment after forming the mosaic charged layer (C).
- the method for the crosslinking treatment is not particularly limited as long as it is a method capable of bonding the molecular chains of the polymer by chemical bonding.
- a method of immersing the mosaic charged layer (C) in a solution containing a crosslinking agent is used.
- the crosslinking agent include glutaraldehyde, formaldehyde, glyoxal and the like.
- the concentration of the crosslinking agent is usually 0.001 to 1% by volume of the volume of the crosslinking agent with respect to the solution.
- all of heat treatment, hot press treatment and crosslinking treatment may be performed, two of them may be performed, or only one of them may be performed.
- the order of processing to be performed is not particularly limited. A plurality of processes may be performed simultaneously. It is preferable to perform a crosslinking treatment after the heat treatment or the heat press treatment.
- a cross-linking treatment particularly a chemical cross-linking treatment, the cross-linked portion and the non-cross-linked portion are mixed, thereby increasing the film strength. It is.
- the heat press treatment, the heat treatment, and the crosslinking treatment are performed in this order.
- the mosaic charge layer (C) is a water-soluble polymer
- the mosaic charge layer (C) is used when the mosaic charge multilayer film is used by performing the heat treatment, the heat press treatment, the crosslinking treatment, and the like. Can be prevented from eluting.
- the mosaic charged multilayer film of the present invention may contain various additives such as an inorganic filler as long as the object of the present invention is not impaired.
- the charge density of the mosaic charged multilayer film of the present invention is not particularly limited, but is preferably 0.1 to 20 mol ⁇ dm ⁇ 3 . If the charge density is less than 0.1 mol ⁇ dm ⁇ 3 , the counter ion selectivity of the membrane may be inferior. More preferably charge density of 0.3 mol ⁇ dm -3 or more, and more preferably 0.5 mol ⁇ dm -3 or more. If the charge density of the film exceeds 20 mol ⁇ dm ⁇ 3 , the film will swell significantly, resulting in poor dimensional stability and difficulty in handling. More preferably charge density of the membrane is 10 mol ⁇ dm -3 or less, more preferably 3 mol ⁇ dm -3 or less.
- the mosaic charged multilayer film of the present invention can be used for various applications.
- the mosaic charged multilayer membrane of the present invention has a large salt permeation flux and excellent electrolyte permselectivity, so that it can purify water, desalinate food and pharmaceutical raw materials, demineralize brine and seawater, and desalinate. Suitable for doing.
- the mosaic charged multilayer membrane of the present invention is particularly suitable for performing pressure dialysis because of its excellent mechanical strength. According to the method for producing a mosaic charged multilayer film of the present invention, a large-area film can be easily produced at low cost.
- the obtained data was subjected to image analysis using “NIS-Elements.D.2.30” manufactured by Nikon Corporation. Thus, the thickness of the mosaic charged layer (C) was calculated. Similarly, the thicknesses of the porous support layer (A) and the porous intermediate layer (B) were calculated. In addition, the value of the thickness obtained here is a value at the time of drying.
- Porosity (%) ⁇ 1- [basis weight (g / m 2 ) / thickness ( ⁇ m)] / resin density (g / cm 3 ) ⁇ ⁇ 100
- the density of polyethylene terephthalate and polyvinyl alcohol was 1.3 (g / cm 3 )
- the density of polyamide-9T was 1.1 (g / cm 3 ).
- the NaCl flux J S was calculated by the following equation.
- J S V I ⁇ ⁇ C I S / (S ⁇ ⁇ t) ⁇ 1000
- the water flux Jw was calculated by the following equation.
- J W ⁇ M I / (S ⁇ ⁇ t)
- J S NaCl component flux [mol ⁇ m ⁇ 2 ⁇ s ⁇ 1 ]
- V I Amount of ion-exchanged water in cell I [m 3 ]
- S Effective membrane area of the mosaic charged multilayer film [m 2 ]
- ⁇ ⁇ C I S initial concentration change of NaCl component in the cell I [mol / L]
- ⁇ t Transmission time [s]
- ⁇ M I change in initial number of moles of NaCl aqueous solution in cell I [mol]
- the gelled product is taken out from the reaction system and pulverized, and then acetic acid is added to the pulverized product after 1 hour has passed since the gelled product was formed. Neutralization was performed to obtain a swollen solid content. After adding 6 times the amount of methanol (6 times bath ratio) to the solid content and washing under reflux for 1 hour, the solid content recovered by filtration was dried at 65 ° C. for 16 hours, and then poly (vinyl A cationic polymer P-1 which is a random copolymer of (alcohol-methacrylamidopropyltrimethylammonium chloride) was obtained.
- the obtained cationic polymer P-1 was dissolved in heavy water and subjected to 1 H-NMR measurement at 400 MHz.
- the content of the cationic monomer in the cationic polymer, ie, in the polymer was 2 mol%.
- the degree of polymerization was 2400, and the degree of saponification was 98.5 mol%.
- Table 1 shows the polymerization conditions and saponification reaction conditions such as vinyl acetate, methanol (MeOH), the type and initial charge amount of an anionic monomer, the use amount of a polymerization initiator (AIBN), the sequential addition amount of an anionic monomer.
- the anionic polymer P-2 was obtained in the same manner as the cationic polymer P-1, except that the amount was changed as shown in FIG. Table 1 shows the physical properties of the obtained polymer.
- aqueous solution of a cationic polymer P-3 which is a block copolymer of polyvinyl alcohol-polyvinylbenzyltrimethylammonium chloride having a solid content concentration of 18%. It was.
- Table 2 shows the polymerization conditions such as the type and amount of polyvinyl alcohol having a mercapto group at the end, the type and amount of cationic monomer, the amount of water, the amount of polymerization initiator (potassium persulfate), etc. Except for the change, cationic polymers P-4 and P-5, which are block copolymers, were synthesized in the same manner as the cationic polymer P-3. Table 2 shows the physical properties of the obtained cationic polymers P-4 and P-5.
- Table 3 shows the polymerization conditions such as the type and amount of polyvinyl alcohol having a mercapto group at the end, the type and amount of anionic monomer, the amount of water, and the amount of polymerization initiator (potassium persulfate).
- Anionic polymers P-6 and P-7 which are block copolymers, were obtained in the same manner as for the cationic polymer P-3 except that the amount was changed.
- Table 3 shows the physical properties of the obtained anionic polymers P-6 and P-7.
- PVA main fiber (“VPB102 ⁇ 5” manufactured by Kuraray Co., Ltd .; 1.1 dtex ⁇ 5 mm) and 80% by mass of PVA binder fiber (“VPB105-1 manufactured by Kuraray Co., Ltd.); 1.1 dtex (equivalent to yen) (Diameter 10 ⁇ m) ⁇ 3 mm, water dissolution temperature 70 ° C.) 20% by mass and mixed to obtain a raw material, which is made with a long paper machine and dried with a Yankee type dryer, and has a basis weight of 30.0 g.
- a porous support layer (A) composed of a wet nonwoven fabric substrate having a thickness of / m 2 and a thickness of 76 ⁇ m was obtained.
- PVA124 manufactured by Kuraray Co., Ltd .; polymerization degree 2400, saponification degree 98.5 mol%) was added to water so as to be 10% by mass, and then stirred and dissolved at 90 ° C. A spinning dope was obtained upon cooling.
- a nanofiber electrospinning unit Kato Tech Co., Ltd. on the porous support layer (A) obtained in (1) above, needle inner diameter: 0.9 mm, distance between electrodes:
- a structure (D) was obtained.
- the basis weight of the porous intermediate layer (B) was 2 g / m 2 and the average fiber diameter was 300 nm.
- the thickness of the porous support layer (A) was 76 ⁇ m
- the thickness of the porous intermediate layer (B) was 3.7 ⁇ m.
- the properties of the obtained substrate-1 are shown in Table 4.
- the porous support layer (A) and the porous intermediate layer (B) were produced in the same manner as for the substrate-1.
- the multilayer structure (D) in which the porous intermediate layer (B) is formed on the porous support layer (A) is hot-pressed for 1 minute with a hot press machine at a temperature of 80 ° C. and a pressure of 10 kgf / cm 2.
- a base material-2 was obtained.
- the thickness of the porous support layer (A) was 65 ⁇ m
- the thickness of the porous intermediate layer (B) was 3 ⁇ m. Table 4 shows the properties of the obtained base material-2.
- the porous support layer (A) and the porous intermediate layer (B) were produced in the same manner as for the substrate-1.
- the multilayer structure (D) in which the porous intermediate layer (B) is formed on the porous support layer (A) is hot-pressed with a hot press machine at a temperature of 140 ° C. and a pressure of 10 kgf / cm 2 for 1 minute.
- a base material-3 was obtained.
- the thickness of the porous support layer (A) was 58 ⁇ m
- the thickness of the porous intermediate layer (B) was 2.4 ⁇ m.
- Table 4 shows the properties of the obtained base material-3.
- PVA main fiber (“VPB102 ⁇ 5” manufactured by Kuraray Co., Ltd .; 1.1 dtex ⁇ 5 mm) and 80% by mass of PVA binder fiber (“VPB105-1 manufactured by Kuraray Co., Ltd.); 1.1 dtex (equivalent to yen) (Diameter 10 ⁇ m) ⁇ 3 mm, water dissolution temperature 70 ° C.) 20% by mass and mixed to obtain a raw material, which is made with a long paper machine and dried with a Yankee type dryer, and has a basis weight of 30.0 g.
- N-methylmorpholine-N-oxide hydrate solution heated to 90 ° C. is 0.25% by weight gallic acid-n-propyl as a solution stabilizer with respect to the pulp and lauryl sulfate as a surfactant.
- Sodium was added at a ratio of 0.25% by mass to prepare a solution with stirring and dissolution.
- a nanofiber electrospinning unit Kato Tech Co., Ltd. on the porous support layer (A) obtained in (1) above, needle inner diameter: 0.9 mm, distance between electrodes:
- a structure (D) was obtained.
- the basis weight of the porous intermediate layer (B) was 2 g / m 2 and the average fiber diameter was 250 nm.
- the thickness of the porous support layer (A) was 54 ⁇ m
- the thickness of the porous intermediate layer (B) was 2.5 ⁇ m.
- Table 4 shows the properties of the obtained base material-4.
- the porous support layer (A) was produced in the same manner as the substrate-1. Further, the hot pressing treatment of the porous support layer (A) in the substrate-6 was performed under the conditions shown in Table 4, and the porous intermediate layer (B) was not formed. At this time, the thickness of the porous support layer (A) in the substrate-5 was 76 ⁇ m, and the thickness of the porous support layer (A) in the substrate-6 was 13 ⁇ m. Table 4 shows the properties of the obtained base material-5 and base material-6.
- PVA124 manufactured by Kuraray Co., Ltd .; polymerization degree 2400, saponification degree 98.5 mol%) was added to water so as to be 10% by mass, and then stirred and dissolved at 90 ° C. A spinning dope was obtained upon cooling.
- a nanofiber electrospinning unit Kato Tech Co., Ltd.
- needle inner diameter 0.9 mm
- distance between electrodes A multilayer in which a porous intermediate layer (B) comprising a fiber layer is formed on a porous support layer (A) by performing electrostatic spinning under conditions of 8 cm, conveyor speed: 0.1 m / min, and applied voltage: 20 kV
- a structure (D) was obtained.
- the basis weight of the porous intermediate layer (B) was 3 g / m 2 and the average fiber diameter was 300 nm.
- the obtained multilayer structure (D) was hot-pressed with a hot press machine at a temperature of 100 ° C. and a pressure of 10 kgf / cm 2 for 1 minute. Table 5 shows the properties of the obtained base material-7.
- the porous support layer (A) was produced in the same manner as for the base material-7. Next, a toluene / methyl ethyl ketone equivalent mixed solution in which 10 parts by mass of catalyst CAT-10 (manufactured by Toyo Morton) was blended with 100 parts by mass of anchor coating agent AD335AE (manufactured by Toyo Morton) was prepared to a concentration of 10 wt%. This solution was applied to the surface of the porous support layer (A) with a wire bar and dried in a hot air dryer at 80 ° C. for 1 minute. The application amount of the adhesive layer was 0.3 g / m 2 .
- PVA124 manufactured by Kuraray Co., Ltd .; polymerization degree 2400, saponification degree 98.5 mol%) was added to water so as to be 10% by mass, and then stirred and dissolved at 90 ° C. A spinning dope was obtained upon cooling.
- a nanofiber electrospinning unit Kato Tech Co., Ltd.
- needle inner diameter 0.9 mm
- distance between electrodes A multilayer in which a porous intermediate layer (B) comprising a fiber layer is formed on a porous support layer (A) by performing electrostatic spinning under conditions of 8 cm, conveyor speed: 0.1 m / min, and applied voltage: 20 kV
- a structure (D) was obtained.
- the basis weight of the porous intermediate layer (B) was 3 g / m 2 and the average fiber diameter was 300 nm.
- the obtained multilayer structure (D) was hot-pressed with a hot press machine at a temperature of 100 ° C. and a pressure of 10 kgf / cm 2 for 1 minute. Table 5 shows the properties of the obtained base material-8.
- the porous support layer (A) having the adhesive layer and the porous intermediate layer (B) were produced in the same manner as for the substrate-8.
- the obtained multilayer structure (D) was hot-pressed with a hot press machine at a temperature of 200 ° C. and a pressure of 10 kgf / cm 2 for 1 minute.
- Table 5 shows the properties of the obtained base material-9.
- the basis weight of the porous intermediate layer (B) was 3 g / m 2 and the average fiber diameter was 250 nm.
- the obtained multilayer structure (D) was hot-pressed with a hot press machine at a temperature of 180 ° C. and a pressure of 10 kgf / cm 2 for 1 minute.
- the properties of the obtained base material-10 are shown in Table 5.
- Example 1 Melt-Coupled polymer aqueous solution having a concentration of 17%. The viscosity was 87,000 mPa ⁇ s (20 ° C.).
- the obtained printed matter was dried in a hot air dryer at 50 ° C. for 10 minutes. Thereafter, the aqueous anionic polymer P-2 solution was similarly printed on the Wa portion shown in FIG. 2 using a screen printing apparatus, and the obtained printed matter was dried in a hot air dryer at 50 ° C. for 10 minutes.
- the thickness of the mosaic charged layer (C) 10 in the mosaic charged multilayer film 3 obtained in this way was measured with a shape measuring laser microscope VK-970 (Keyence Co., Ltd.) and found to be 4.5 ⁇ m.
- the thickness of the porous support layer (A) 8 was 76 ⁇ m, and the thickness of the porous intermediate layer (B) 9 was 3.7 ⁇ m.
- the air permeability of the obtained mosaic charged multilayer film 3 was 100,000 seconds or more and ⁇ or less.
- “below ⁇ ” indicates a measurement limit or less.
- the mosaic charged multilayer film thus obtained was heat-treated at 170 ° C. for 30 minutes using a hot air dryer to cause physical crosslinking.
- the membrane was immersed in an aqueous electrolyte solution of 2 mol / L sodium sulfate for 24 hours.
- Concentrated sulfuric acid was added to the aqueous solution so that the pH was 1, and then the membrane was immersed in a 0.05% by volume glutaraldehyde aqueous solution and stirred with a stirrer at 25 ° C. for 24 hours for crosslinking treatment. .
- the glutaraldehyde aqueous solution a product obtained by diluting “glutaraldehyde” (25% by volume) manufactured by Ishizu Pharmaceutical Co., Ltd. with water was used. After the crosslinking treatment, the membrane was immersed in deionized water, and the membrane was immersed in the deionized water several times in the middle until the membrane reached a swelling equilibrium.
- the above manufacturing method is shown in Table 6.
- Example 2 In Example 1, the types of the cationic polymer and anionic polymer to be used, the concentrations of the aqueous cationic polymer solution and the anionic polymer aqueous solution to be prepared, the base material type, and the temperature of the heat treatment were changed as shown in Table 6. Except for the above, a mosaic charged multilayer film was prepared and evaluated in the same manner as in Example 1. The production methods are shown in Table 6, and the results obtained are shown in Table 7.
- Example 6 In Example 4, instead of using the cationic polymer P-3, a cationic polymer aqueous solution having a concentration of 5% of the cationic polymer P-5 was prepared, and instead of using the anionic polymer P-6, A mosaic charged multilayer film was prepared in the same manner as in Example 4 except that an anionic polymer aqueous solution having a concentration of 5% of the anionic polymer P-6 was prepared and an inkjet printing apparatus was used instead of the screen printing apparatus. Fabricated and evaluated. The production methods are shown in Table 6, and the results obtained are shown in Table 7.
- the ink jet printing apparatus an ink jet printing apparatus “NanoPrinter 1100D” manufactured by Microjet Co., Ltd. was used.
- the viscosity of the cationic polymer aqueous solution was 12 mPa ⁇ s (20 ° C.), and the viscosity of the anionic polymer aqueous solution was 12 mPa ⁇ s (20 ° C.).
- Example 7 In Example 4, the concentration of the aqueous cationic polymer solution and the aqueous anionic polymer solution to be prepared was changed as shown in Table 6, and a dispenser type printing device was used instead of the screen printing device. In the same manner, a mosaic charged multilayer film was prepared and evaluated. The production methods are shown in Table 6, and the results obtained are shown in Table 7.
- a dispenser type printing apparatus a dispenser type printing apparatus “SHOTMASTER500” manufactured by Musashi Engineering Co., Ltd. was used.
- the viscosity of the 15% aqueous solution of the cationic polymer P-3 was 3000 mPa ⁇ s (20 ° C.), and the viscosity of the 15% aqueous solution of the anionic polymer P-6 was 3000 mPa ⁇ s (20 ° C.).
- Comparative Examples 1 to 3 In Example 2, a mosaic charged film was prepared and evaluated in the same manner as in Example 2 except that the base material used for screen printing was changed to the base material shown in Table 6. The manufacturing method is shown in Table 6. The obtained results are shown in Table 7, respectively.
- Comparative Examples 1 and 3 the test liquid leaked from the pressure side to the low pressure side during the pressure dialysis test, and the membrane characteristics could not be evaluated.
- the porous intermediate layer (B) is provided on the porous support layer (A), and further contains polyvinyl alcohol containing a cationic group, or a polymer containing a cationic group and a cationic group. And a mixture of polyvinyl alcohol containing an anionic group or a polymer containing an anionic group and a polyvinyl alcohol containing no anionic group. It can be seen that by printing on the porous intermediate layer (B), the salt permeation flux in the resulting mosaic charged multilayer membrane is large, and the electrolyte permselectivity is excellent (Examples 1 to 8).
- a mosaic charged layer (C) is printed using a high-viscosity ink using a substrate that has been subjected to a hot press treatment after the porous intermediate layer (B) has been provided, defects such as microvoids in the printed layer Therefore, it becomes a multi-layered membrane, and a pressure dialysis test at higher pressure is possible. Further, it can be seen that the permeation flux of the salt is increased and the electrolyte permselectivity is excellent (Examples 4 to 5 and 7 to 8).
- Example 9 Melaic charge multilayer film production
- a 200 mL Erlenmeyer flask add 90 mL of deionized water, add 22.5 g of the cationic polymer P-1, and then heat and stir in a 95 ° C. water bath to dissolve the polymer P-1. It was. Thereafter, deionized water was added to prepare a cationic polymer aqueous solution having a concentration of 17%. The viscosity was 87,000 mPa ⁇ s (20 ° C.).
- the thickness of the porous support layer (A) was 65 ⁇ m, and the thickness of the porous intermediate layer (B) was 3 ⁇ m.
- an air permeability measurement test was performed according to the above method. Table 9 shows the obtained results.
- the mosaic charged multilayer film thus obtained was heat-treated at 170 ° C. for 30 minutes using a hot air dryer to cause physical crosslinking.
- the membrane was immersed in an aqueous electrolyte solution of 2 mol / L sodium sulfate for 24 hours.
- Concentrated sulfuric acid was added to the aqueous solution so that the pH was 1, and then the membrane was immersed in a 0.1% by volume glutaraldehyde aqueous solution and stirred with a stirrer at 25 ° C. for 24 hours for crosslinking treatment.
- glutaraldehyde aqueous solution a product obtained by diluting “glutaraldehyde” (25% by volume) manufactured by Ishizu Pharmaceutical Co., Ltd. with water was used.
- the membrane was immersed in deionized water, and the membrane was immersed in the deionized water several times in the middle until the membrane reached a swelling equilibrium.
- Table 8 shows the above manufacturing method.
- the mosaic charged multilayer film thus prepared was cut into a desired size to prepare a measurement sample. Using the obtained measurement sample, an underwater strength test and a pressure dialysis test were performed according to the above-described methods. Table 9 shows the obtained results.
- Example 9 except that the types of the cationic polymer and anionic polymer used, the concentrations of the aqueous cationic polymer solution and the aqueous anionic polymer to be prepared, the substrate type, and the domain size were changed as shown in Table 8.
- Example 15 In Example 9, instead of using the cationic polymer P-1, an aqueous cationic polymer solution having a concentration of 5% of the cationic polymer P-5 was prepared, and instead of using the anionic polymer P-2, An anionic polymer aqueous solution having a concentration of 5% of the anionic polymer P-7 was prepared, and a mosaic charged multilayer film was formed in the same manner as in Example 9 except that an inkjet printing apparatus was used instead of the screen printing apparatus. Fabricated and evaluated. The production methods are shown in Table 8, and the results obtained are shown in Table 9, respectively.
- the ink jet printing apparatus an ink jet printing apparatus “NanoPrinter 1100D” manufactured by Microjet Co., Ltd. was used.
- the viscosity of the cationic polymer aqueous solution was 12 mPa ⁇ s (20 ° C.), and the viscosity of the anionic polymer aqueous solution was 12 mPa ⁇ s (20 ° C.).
- Example 16 In Example 9, instead of using the cationic polymer P-1, an aqueous cationic polymer solution having a concentration of 15% of the cationic polymer P-3 was prepared, and instead of using the anionic polymer P-2, A mosaic charged multilayer film was prepared in the same manner as in Example 9 except that an anionic polymer aqueous solution having a concentration of 15% of the anionic polymer P-6 was prepared and a dispenser type printing apparatus was used instead of the screen printing apparatus. Were prepared and evaluated. The production methods are shown in Table 8, and the results obtained are shown in Table 9, respectively.
- the dispenser type printing apparatus a dispenser type printing apparatus “SHOTMASTER500” manufactured by Musashi Engineering Co., Ltd. was used.
- the viscosity of the 15% aqueous solution of the cationic polymer P-3 was 3000 mPa ⁇ s (20 ° C.), and the viscosity of the 15% aqueous solution of the anionic polymer P-6 was 3000 mPa ⁇ s (20 ° C.).
- the porous intermediate layer is formed on the porous support layer (A) by providing the porous intermediate layer (B) on the porous support layer (A). It can be seen that the smoothness is improved while the air permeability of the multilayer structure (D) obtained by forming (B) is kept low. In particular, it can be seen that higher smoothness can be achieved by performing hot pressing (base material-7 to base material-10). It can also be seen that the porous support layer (A) is made of hydrophobic fibers, so that the shrinkage ratio after being dipped in water and dried is reduced, and the dimensional stability is improved (Base-7 to Base-10). ).
- a porous intermediate layer (B) is provided on a porous support layer (A) made of hydrophobic fibers, and further a polyvinyl alcohol containing a cationic group or a polymer containing a cationic group And a mixture of polyvinyl alcohol not containing a cationic group is printed on the porous intermediate layer (B), and a polyvinyl alcohol containing an anionic group, or a polymer containing an anionic group and a polyvinyl alcohol containing no anionic group
- the mosaic charged multilayer membrane obtained by printing the mixture with the porous intermediate layer (B) has excellent strength in water, a large salt permeation flux, and excellent electrolyte selective permeability.
- Examples 9 to 16 As can be seen (Examples 9 to 16). In particular, it can be seen that when the domain size is small, the salt permeation flux becomes larger and the electrolyte selective permeability is excellent (Examples 13 to 14). It can also be seen that an air permeability of 500,000 seconds or more can be obtained even when the domain size is less than 100 ⁇ m (Examples 9 to 16). In particular, when a mosaic charged layer (C) is printed using a high-viscosity ink using a base material provided with a porous intermediate layer (B), it becomes a multilayer film with few defects such as microvoids in the printed layer, It can be seen that high air permeability can be obtained (Examples 9 to 14, 16).
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Abstract
Description
モザイク荷電複層膜を25℃のイオン交換水中に5日以上浸漬させ、膨潤平衡状態としたのち、手術用ナイフで断面を切り出した後、イオン交換水にメチルバイオレットを濃度5×10-5mol/Lで溶解した水溶液に30分間浸漬してカチオン性重合体のドメインの部分を着色して測定試料を作製した。こうして得られた測定試料を乾燥させてから株式会社ニコン製光学顕微鏡「OPTIPHOT-2」で断面観察し、得られたデータを株式会社ニコン製「NIS-Elements.D.2.30」で画像解析することでモザイク荷電層(C)の厚みを算出した。また、同様にして多孔質支持層(A)および多孔質中間層(B)の厚みを算出した。なお、ここで得られた厚みの値は、乾燥時における値である。
下記計算式により空隙率を求めた。
空隙率(%)={1-[坪量(g/m2)/厚み(μm)]/樹脂密度(g/cm3)}×100
ここで、ポリエチレンテレフタレートおよびポリビニルアルコールの密度は1.3(g/cm3)、ポリアミド-9Tの密度は1.1(g/cm3)として計算した。
多孔性支持層(A)、多層構造体(D)に関しては、JIS P8117に従い、ガーレーデンソメーターを用いて100mlの空気の透過時間を測定した。また、モザイク荷電複層膜に関しては、JAPAN TAPPI紙のパルプ試験法No.5による王研式透気度試験に従って測定した。
王研式透気度平滑度試験機No.2040-C(熊谷理機工業(株))を用いて、JAPAN TAPPI紙のパルプ試験法No.5による王研式平滑度試験に従って測定した。
多孔質支持層(A)上に多孔質中間層(B)が形成された多層構造体(D)を、マグネトロンスパッタ装置「MPS-1S」(株式会社真空デバイス製)にてAu蒸着処理した。続いて、多孔質中間層(B)におけるナノファイバー表面を電子顕微鏡「VE-7800」(株式会社キーエンス製)にて観察し、表面観察画像を得た。得られた画像について、三谷商事株式会社製画像処理ソフト「WINROOF」を用いて画像処理を行い、多孔質中間層(B)の平均繊維径を求めた。測定個所は、ランダムに100個所を多孔質中間層(B)から選んで平均繊維径を算出した。
多層構造体(D)を35cm角に切り出して、MD方向に正確に30cmの2点を刻印した。次いで、25℃のイオン交換水中に10秒間浸漬させた後、熱風乾燥機中で105℃、2時間乾燥した。得られた膜の刻印間の距離を測定し、下記の式により、収縮率を計算した。得られた結果から収縮率を下記の三段階で評価した。
A:収縮率が0.5%未満であった。
B:収縮率が0.5%以上、2%未満であった。
C:収縮率が2%以上であった。
収縮率(%)=(水浸漬前の刻印2点間の距離-水浸漬・乾燥後の刻印2点間の距離)/水浸漬前の刻印2点間の距離×100
モザイク荷電複層膜をMD方向に幅15mmの短冊状に切り出した。次いで、引っ張り試験機AGS-100G(株式会社島津製作所製)を用いて、25℃の水中にて引っ張り速度20mm/分で引っ張り試験を行った。
圧透析試験は図1に示す装置で行った。フォルダに挟んだモザイク荷電複層膜3の測定試料を2つのセルの間に挟み、株式会社堀場製作所製導電率電極「3552-10D」を挿入したセルI6に所定濃度のNaCl水溶液を30mL入れ、セルII7にはセルI6と同濃度のNaCl水溶液を30mL入れた。続いて、両セル内の水溶液を攪拌子4で撹拌させながら、窒素ガスボンベ1からセルII7側に窒素ガスを加え、一定圧力に維持した。その際、導電率計5を用いてセルI6中の導電率を25℃の一定温度下で測定した。試験終了後、直ちにセルI6中のNaCl水溶液の質量を測定した。
JS=VI×ΔCI S/(S×Δt)×1000
水の流束Jwは、次式により算出した。
JW=ΔMI/(S×Δt)
・JS:NaCl成分の流束[mol・m-2・s-1]
・VI:セルI内のイオン交換水量[m3]
・S:モザイク荷電複層膜の膜有効面積[m2]
・ΔCI S:セルI内のNaCl成分の初期濃度変化[mol/L]
・Δt:透過時間[s]
・ΔMI:セルI内のNaCl水溶液の初期モル数変化[mol]
α=JW/JS
攪拌機、温度センサー、滴下漏斗および還流冷却管を備え付けた6Lのセパラブルフラスコに、酢酸ビニル2975g、メタノール525g、およびメタクリルアミドプロピルトリメチルアンモニウムクロライドを20質量%含有するメタノール溶液83.9gを仕込み、攪拌下に系内を窒素置換した後、かかる混合液の内温を60℃まで上げた。該混合液中に2,2’-アゾビスイソブチロニトリル(AIBN)を0.8g含有するメタノール20gを添加し、重合反応を開始した。重合開始時点よりメタクリルアミドプロピルトリメチルアンモニウムクロライドを20質量%含有するメタノール溶液222gを反応液中に添加しながら、4時間重合反応を行った後、重合反応を停止した。重合反応を停止した時点における反応液中の固形分濃度、すなわち、反応液全体に対する不揮発分の含有率は21.5質量%であった。ついで、系内にメタノール蒸気を導入することにより、未反応の酢酸ビニル単量体を追い出し、ビニルエステル共重合体を55質量%含有するメタノール溶液を得た。
酢酸ビニル、メタノール(MeOH)、アニオン性単量体の種類と初期仕込み量、重合開始剤(AIBN)の使用量、アニオン性単量体の逐次添加量などの重合条件、けん化反応条件を表1に示すように変化させた以外はカチオン性重合体P-1と同様の方法により、アニオン性重合体P-2を得た。得られた重合体の物性を表1に示す。
特許文献5に記載された方法(末端にメルカプト基を有するポリビニルアルコール系重合体およびその方法)によって、末端にメルカプト基を有するポリビニルアルコールPVA-1を合成した。得られたPVA-1の重合度は1550、けん化度は98.5モル%であった。また、同様の方法により、末端にメルカプト基を有するポリビニルアルコールPVA-2を合成した。得られたPVA-2の重合度は550、けん化度は98.5モル%であった。
還流冷却管、攪拌翼を備え付けた5Lの四つ口セパラブルフラスコに、水1900g、末端にメルカプト基を有するポリビニルアルコールとしてPVA-1を344g仕込み、攪拌下95℃まで加熱して該ポリビニルアルコールを溶解した後、室温まで冷却した。該水溶液に1/2規定の硫酸を添加してpHを3.0に調製した。別に、ビニルベンジルトリメチルアンモニウムクロライド179gを水300gに溶解し、これを先に調製した水溶液に攪拌下添加した後、該水溶液中に窒素をバブリングしつつ70℃まで加温し、さらに70℃で30分間窒素のバブリングを続けることで、窒素置換した。窒素置換後、上記水溶液に過硫酸カリウム(KPS)の2.5%水溶液121mLを1.5時間かけて逐次的に添加してブロック共重合を開始させ、進行させた後、系内温度を75℃に1時間維持して重合をさらに進行させ、ついで冷却して、固形分濃度18%のポリビニルアルコール-ポリビニルベンジルトリメチルアンモニウムクロライドのブロック共重合体であるカチオン性重合体P-3の水溶液を得た。得られた水溶液の一部を乾燥した後、重水に溶解し、400MHzでの1H-NMR測定を行ったところ、該ブロック共重合体中のカチオン性単量体含有量、すなわち、該重合体中の単量体単位の総数に対するビニルベンジルトリメチルアンモニウムクロライド単量体単位の数の割合は10モル%であった。
末端にメルカプト基を有するポリビニルアルコールの種類と仕込み量、カチオン性単量体の種類と仕込み量、水の量、重合開始剤(過硫酸カリウム)の量などの重合条件を表2に示すように変えた以外は、カチオン性重合体P-3と同様の方法によってブロック共重合体であるカチオン性重合体P-4、P-5を合成した。得られたカチオン性重合体P-4、P-5の物性を表2に示す。
末端にメルカプト基を有するポリビニルアルコールの種類と仕込み量、アニオン性単量体の種類と仕込み量、水の量、重合開始剤(過硫酸カリウム)の量などの重合条件を表3に示すように変化させた以外はカチオン性重合体P-3と同様の方法により、ブロック共重合体であるアニオン性重合体P-6、P-7を得た。得られたアニオン性重合体P-6、P-7の物性を表3に示す。
(1)PVA系主体繊維(株式会社クラレ製「VPB102×5」;1.1dtex×5mm)80質量%と、PVA系バインダー繊維(株式会社クラレ製「VPB105-1」;1.1dtex(円相当径10μm)×3mm、水中溶解温度70℃)20質量%とを加えて混合して原料とし、これを長網抄紙機にて抄紙し、ヤンキー型乾燥機にて乾燥して坪量30.0g/m2、厚さ76μmの湿式不織布基材からなる多孔質支持層(A)を得た。
(2)PVA124(株式会社クラレ製;重合度2400、ケン化度98.5モル%)を10質量%となるように水に投入後、90℃で攪拌溶解し、完全溶解したものを常温まで冷却して紡糸原液を得た。得られた紡糸原液を用い、ナノファイバーエレクトロスピニングユニット(カトーテック株式会社)にて、上記(1)で得た多孔質支持層(A)上に、ニードル内径:0.9mm、極間距離:8cm、コンベア速度:0.1m/分、印加電圧:20kVの条件で静電紡糸を行って、多孔質支持層(A)上に繊維層からなる多孔質中間層(B)が形成された多層構造体(D)を得た。得られた多層構造体(D)において、多孔質中間層(B)の坪量は2g/m2であり、平均繊維径は300nmであった。また、このとき、多層構造体(D)において、多孔質支持層(A)の厚みは76μmであり、多孔質中間層(B)の厚みは3.7μmであった。得られた基材-1の特性を表4に示す。
多孔質支持層(A)および多孔質中間層(B)の作製は基材-1と同様に行った。多孔質支持層(A)上に多孔質中間層(B)が形成された多層構造体(D)を熱プレス機で温度80℃、圧力10kgf/cm2の条件で、1分間熱プレスを行って基材-2を得た。このとき、多層構造体(D)において、多孔質支持層(A)の厚みは65μmであり、多孔質中間層(B)の厚みは3μmであった。得られた基材-2の特性を表4に示す。
多孔質支持層(A)および多孔質中間層(B)の作製は基材-1と同様に行った。多孔質支持層(A)上に多孔質中間層(B)が形成された多層構造体(D)を熱プレス機で温度140℃、圧力10kgf/cm2の条件で、1分間熱プレスを行って基材-3を得た。このとき、多層構造体(D)において、多孔質支持層(A)の厚みは58μmであり、多孔質中間層(B)の厚みは2.4μmであった。得られた基材-3の特性を表4に示す。
(1)PVA系主体繊維(株式会社クラレ製「VPB102×5」;1.1dtex×5mm)80質量%と、PVA系バインダー繊維(株式会社クラレ製「VPB105-1」;1.1dtex(円相当径10μm)×3mm、水中溶解温度70℃)20質量%とを加えて混合して原料とし、これを長網抄紙機にて抄紙し、ヤンキー型乾燥機にて乾燥して坪量30.0g/m2、厚さ54μmの湿式不織布基材からなる多孔質支持層(A)を得た。
(2)溶解槽にあらかじめ開繊したパルプ(ウエスタンパルプ、重合度DP=621、ALICELL社製)を入れ、80℃に加熱して1時間放置した。またこれとは別に90℃に加熱したN-メチルモルホリン-N-オキサイド水和物液に溶液安定剤として没食子酸-n-プロピルをパルプに対して0.25質量%および界面活性剤としてラウリル硫酸ナトリウムを0.25質量%となる割合で添加し、攪拌溶解した溶液を調製した。次いで該溶液を上記溶解槽内の加熱されたパルプに振りかけ、溶解槽の蓋をして窒素置換を行い、30分間放置してパルプを十分に膨潤させ、溶解槽設置の攪拌機で1時間攪拌してパルプを完全に溶解させた。その後溶解槽の温度を100℃に昇温し、攪拌を停止して4時間放置して十分に脱泡を行い、紡糸原液を作成した。得られた紡糸原液を用い、ナノファイバーエレクトロスピニングユニット(カトーテック株式会社)にて、上記(1)で得た多孔質支持層(A)上に、ニードル内径:0.9mm、極間距離:8cm、コンベア速度:0.1m/分、印加電圧:20kVの条件で静電紡糸を行って、多孔質支持層(A)上に繊維層からなる多孔質中間層(B)が形成された多層構造体(D)を得た。得られた多層構造体(D)において、多孔質中間層(B)の坪量は2g/m2であり、平均繊維径は250nmであった。また、このとき、多層構造体(D)において、多孔質支持層(A)の厚みは54μmであり、多孔質中間層(B)の厚みは2.5μmであった。得られた基材-4の特性を表4に示す。
基材-5および基材-6の作製において、多孔質支持層(A)の作製は基材-1と同様に行った。また、基材-6における多孔質支持層(A)の熱プレス処理は、表4に示す条件で行い、多孔質中間層(B)を形成しなかった。このとき、基材-5における多孔質支持層(A)の厚みは76μmであり、基材-6における多孔質支持層(A)の厚みは13μmであった。得られた基材-5および基材-6の特性を表4に示す。
(1)ポリエチレンテレフタレート繊維(商品名:EP053×5(EM)、クラレ製(0.84dtex×5mm))60質量%と、ポリエチレンテレフタレート複合バインダー繊維(商品名:EP101×5(EM)、クラレ製(1.1dtex(円相当径10μm)×5mm))40質量%とを加えて混合して原料とし、これを長網抄紙機にて抄紙し、ヤンキー型乾燥機にて乾燥して坪量30g/m2、厚さ65μmの湿式不織布基材からなる多孔質支持層(A)を得た。
(2)PVA124(株式会社クラレ製;重合度2400、ケン化度98.5モル%)を10質量%となるように水に投入後、90℃で攪拌溶解し、完全溶解したものを常温まで冷却して紡糸原液を得た。得られた紡糸原液を用い、ナノファイバーエレクトロスピニングユニット(カトーテック株式会社)にて、上記(1)で得た多孔質支持層(A)上に、ニードル内径:0.9mm、極間距離:8cm、コンベア速度:0.1m/分、印加電圧:20kVの条件で静電紡糸を行って、多孔質支持層(A)上に繊維層からなる多孔質中間層(B)が形成された多層構造体(D)を得た。得られた多層構造体(D)において、多孔質中間層(B)の坪量は3g/m2であり、平均繊維径は300nmであった。得られた多層構造体(D)を熱プレス機で温度100℃、圧力10kgf/cm2の条件で、1分間熱プレスを行った。得られた基材-7の特性を表5に示す。
(1)多孔質支持層(A)の作製は基材-7と同様に行った。次いで、アンカーコート剤AD335AE(東洋モートン製)100質量部に対して触媒CAT-10(東洋モートン製)を10質量部配合したトルエン/メチルエチルケトン等量混合溶液を濃度10wt%に調製した。この溶液を、ワイヤーバーにて多孔質支持層(A)の表面に塗布し、熱風乾燥機中で80℃、1分間乾燥した。接着剤層の塗布量は0.3g/m2であった。
(2)PVA124(株式会社クラレ製;重合度2400、ケン化度98.5モル%)を10質量%となるように水に投入後、90℃で攪拌溶解し、完全溶解したものを常温まで冷却して紡糸原液を得た。得られた紡糸原液を用い、ナノファイバーエレクトロスピニングユニット(カトーテック株式会社)にて、上記(1)で得た多孔質支持層(A)上に、ニードル内径:0.9mm、極間距離:8cm、コンベア速度:0.1m/分、印加電圧:20kVの条件で静電紡糸を行って、多孔質支持層(A)上に繊維層からなる多孔質中間層(B)が形成された多層構造体(D)を得た。得られた多層構造体(D)において、多孔質中間層(B)の坪量は3g/m2であり、平均繊維径は300nmであった。得られた多層構造体(D)を熱プレス機で温度100℃、圧力10kgf/cm2の条件で、1分間熱プレスを行った。得られた基材-8の特性を表5に示す。
接着剤層を有する多孔質支持層(A)、および多孔質中間層(B)の作製は基材-8と同様に行った。得られた多層構造体(D)を熱プレス機で温度200℃、圧力10kgf/cm2の条件で、1分間熱プレスを行った。得られた基材-9の特性を表5に示す。
(1)ポリアミド-9T繊維(商品名:A590、クラレ製(0.8dtex×5mm))70質量%と、ポリエチレンテレフタレート複合バインダー繊維(EP101×5(EM)、クラレ製(1.1dtex(円相当径10μm)×5mm))30質量%とを加えて混合して原料とし、これを長網抄紙機にて抄紙し、ヤンキー型乾燥機にて乾燥して坪量30g/m2、厚さ70μmの湿式不織布基材からなる多孔質支持層(A)を得た。
(2)エチレンビニルアルコール共重合体(エチレン変性量32モル%)を10質量%となるようにジメチルスルホキシドに投入後、90℃で攪拌溶解し、完全溶解したものを常温まで冷却して紡糸原液を得た。得られた紡糸原液を用い、ナノファイバーエレクトロスピニングユニット(カトーテック株式会社)にて、上記(1)で得た多孔質支持層(A)上に、ニードル内径:0.9mm、極間距離:8cm、コンベア速度:0.1m/分、印加電圧:20kVの条件で静電紡糸を行って、多孔質支持層(A)上に繊維層からなる多孔質中間層(B)が形成された多層構造体(D)を得た。得られた多層構造体(D)において、多孔質中間層(B)の坪量は3g/m2であり、平均繊維径は250nmであった。得られた多層構造体(D)を熱プレス機で温度180℃、圧力10kgf/cm2の条件で、1分間熱プレスを行った。得られた基材-10の特性を表5に示す。
(モザイク荷電複層膜の作製)
200mLの三角フラスコに、90mLの脱イオン水を入れ、カチオン性重合体P-1を22.5g加えてから、95℃のウォーターバスの中で加熱撹拌し、該重合体P-1を溶解させた。その後、脱イオン水を加えて濃度17%のカチオン性重合体水溶液を調製した。粘度は8.7万mPa・s(20℃)であった。また、200mLの三角フラスコに、90mLの脱イオン水を入れ、アニオン性重合体P-2を22.5g加えてから、95℃のウォーターバスの中で加熱撹拌し、該重合体P-2を溶解させた。その後、脱イオン水を加えて濃度17%のアニオン性重合体水溶液を調製した。粘度は8.5万mPa・s(20℃)であった。まず、カチオン性重合体P-1水溶液をスクリーン印刷装置LS-34TV(ニューロング精密工業株式会社製)を用いて、基材-1上に図2に示すストライプ状印刷物のWc部分の印刷を行い、得られた印刷物を熱風乾燥機中で50℃、10分間乾燥した。その後、同様にしてアニオン性重合体P-2水溶液を、スクリーン印刷装置を用いて図2に示すWa部分の印刷を行い、得られた印刷物を熱風乾燥機中で50℃、10分間乾燥した。こうして得られたモザイク荷電複層膜3におけるモザイク荷電層(C)10の厚みを、形状測定レーザー顕微鏡VK-970(株式会社キーエンス)で測定した結果、4.5μmであった。このとき、多孔質支持層(A)8の厚みは76μmであり、多孔質中間層(B)9の厚みは3.7μmであった。さらに、得られたモザイク荷電複層膜3の透気度は10万秒以上∞以下の値であった。ここで、透気度の測定において、∞以下とは測定限界以下を示す。
このようにして作製したモザイク荷電複層膜を、所望の大きさに裁断し、測定試料を作製した。得られた測定試料を用い、上記方法にしたがって、圧透析試験を行った。得られた結果を表7に示す。
実施例1において、用いるカチオン性重合体およびアニオン性重合体の種類、調製するカチオン性重合体水溶液およびアニオン性重合体水溶液の濃度、基材種類、熱処理の温度を表6に示すように変えた以外は実施例1と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表6に、得られた結果を表7にそれぞれ示す。
実施例4において、カチオン性重合体P-3を用いる代わりに、カチオン性重合体P-5の濃度5%のカチオン性重合体水溶液を調製し、アニオン性重合体P-6を用いる代わりに、アニオン性重合体P-6の濃度5%のアニオン性重合体水溶液を調製し、スクリーン印刷装置の代わりに、インクジェット印刷装置を用いた以外は、実施例4と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表6に、得られた結果を表7にそれぞれ示す。ここで、インクジェット印刷装置としては、マイクロジェット社製インクジェット印刷装置「NanoPrinter1100D」を用いた。カチオン性重合体水溶液の粘度は12mPa・s(20℃)、アニオン性重合体水溶液の粘度は12mPa・s(20℃)であった。
実施例4において、調製するカチオン性重合体水溶液およびアニオン性重合体水溶液の濃度を表6に示すように変えて、スクリーン印刷装置の代わりに、ディスペンサー式印刷装置を用いた以外は、実施例4と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表6に、得られた結果を表7にそれぞれ示す。ここで、ディスペンサー式印刷装置としては、武蔵エンジニアリング株式会社製ディスペンサー式印刷装置「SHOTMASTER500」を用いた。カチオン性重合体P-3の濃度15%水溶液の粘度は3000mPa・s(20℃)、アニオン性重合体P-6の濃度15%水溶液の粘度は3000mPa・s(20℃)であった。
実施例2において、スクリーン印刷に使用する基材を表6に示す基材に変更した以外は、実施例2と同様にしてモザイク荷電膜を作製し、評価を行った。製造方法を表6に示す。得られた結果を表7にそれぞれ示す。ここで、比較例1と3では、圧透析試験時に加圧側から試験液が低圧側に漏洩し、膜特性の評価ができなかった。
(モザイク荷電複層膜の作製)
200mLの三角フラスコに、90mLの脱イオン水を入れ、カチオン性重合体P-1を22.5g加えてから、95℃のウォーターバスの中で加熱撹拌し、該重合体P-1を溶解させた。その後、脱イオン水を加えて濃度17%のカチオン性重合体水溶液を調整した。粘度は8.7万mPa・s(20℃)であった。また、200mLの三角フラスコに、90mLの脱イオン水を入れ、アニオン性重合体P-2を22.5g加えてから、95℃のウォーターバスの中で加熱撹拌し、該重合体P-2を溶解させた。その後、脱イオン水を加えて濃度17%のアニオン性重合体水溶液を調整した。粘度は8.5万mPa・s(20℃)であった。まず、カチオン性重合体P-1水溶液をスクリーン印刷装置LS-34TV(ニューロング精密工業株式会社製)を用いて、基材-7上に図2に示すストライプ状印刷物のWc部分の印刷を行った(印刷面積10cm×10cm)。得られた印刷物を熱風乾燥機中で50℃、10分間乾燥した。その後、同様にしてアニオン性重合体P-2水溶液を、スクリーン印刷装置を用いて図2に示すWa部分の印刷を行い、得られた印刷物を熱風乾燥機中で50℃、10分間乾燥した。こうして得られたモザイク荷電複層膜におけるモザイク荷電層(C)の厚みを形状測定レーザー顕微鏡VK-970(株式会社キーエンス)で測定した結果、6μmであった。このとき、多孔質支持層(A)の厚みは65μm、多孔質中間層(B)の厚みは3μmであった。得られた測定試料を用い、上記方法にしたがって透気度測定試験を行った。得られた結果を表9に示す。
このようにして作製したモザイク荷電複層膜を、所望の大きさに裁断し、測定試料を作製した。得られた測定試料を用い、上記方法にしたがって、水中強度試験、圧透析試験を行った。得られた結果を表9に示す。
実施例9において、用いるカチオン性重合体およびアニオン性重合体の種類、調製するカチオン性重合体水溶液およびアニオン性重合体水溶液の濃度、基材種類、ドメインサイズを表8に示すように変えた以外は実施例9と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表8に、得られた結果を表9にそれぞれ示す。
実施例9において、カチオン性重合体P-1を用いる代わりに、カチオン性重合体P-5の濃度5%のカチオン性重合体水溶液を調製し、アニオン性重合体P-2を用いる代わりに、アニオン性重合体P-7の濃度5%のアニオン性重合体水溶液を調製し、スクリーン印刷装置の代わりに、インクジェット印刷装置を用いた以外は、実施例9と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表8に、得られた結果を表9にそれぞれ示す。ここで、インクジェット印刷装置としては、マイクロジェット社製インクジェット印刷装置「NanoPrinter1100D」を用いた。カチオン性重合体水溶液の粘度は12mPa・s(20℃)、アニオン性重合体水溶液の粘度は12mPa・s(20℃)であった。
実施例9において、カチオン性重合体P-1を用いる代わりに、カチオン性重合体P-3の濃度15%のカチオン性重合体水溶液を調製し、アニオン性重合体P-2を用いる代わりに、アニオン性重合体P-6の濃度15%のアニオン性重合体水溶液を調製し、スクリーン印刷装置の代わりに、ディスペンサー式印刷装置を用いた以外は、実施例9と同様にしてモザイク荷電複層膜を作製し、評価を行った。製造方法を表8に、得られた結果を表9にそれぞれ示す。ここで、ディスペンサー式印刷装置としては、武蔵エンジニアリング株式会社製ディスペンサー式印刷装置「SHOTMASTER500」を用いた。カチオン性重合体P-3の濃度15%水溶液の粘度は3000mPa・s(20℃)、アニオン性重合体P-6の濃度15%水溶液の粘度は3000mPa・s(20℃)であった。
2 圧力計
3 モザイク荷電複層膜
4 攪拌子
5 導電率計
6 セルI
7 セルII
8 多孔質支持層(A)
9 多孔質中間層(B)
10 モザイク荷電層(C)
Wc カチオン性重合体のドメインサイズ
Wa アニオン性重合体のドメインサイズ
Claims (8)
- 平均繊維径1μm以上100μm以下の繊維からなる多孔質支持層(A)、平均繊維径0.01μm以上1μm未満の繊維からなる多孔質中間層(B)、およびカチオン性重合体のドメインとアニオン性重合体のドメインとから構成されるモザイク荷電層(C)を有するモザイク荷電複層膜であって、
多孔質支持層(A)、多孔質中間層(B)、およびモザイク荷電層(C)がこの順番で配置されるか、または多孔質中間層(B)内にモザイク荷電層(C)が形成されてなり、
多孔質支持層(A)および/または多孔質中間層(B)が、親水性繊維を少なくとも50質量%含む繊維層からなり、
多孔質中間層(B)の厚さが0.1~100μmであり、
多孔質中間層(B)の空隙率よりも多孔質支持層(A)の空隙率が大きく、
モザイク荷電層(C)を構成するカチオン性重合体および/またはアニオン性重合体が、イオン基を有するポリビニルアルコールであることを特徴とするモザイク荷電複層膜。 - 前記親水性繊維がポリビニルアルコール繊維である請求項1記載のモザイク荷電複層膜。
- 多孔質支持層(A)が、疎水性重合体を含む請求項1または2記載のモザイク荷電複層膜。
- 前記疎水性重合体がポリオレフィン、ポリエステルおよびポリアミドからなる群から選択される少なくとも1種である請求項3記載のモザイク荷電複層膜。
- 多孔質支持層(A)が疎水性重合体を少なくとも50質量%含む繊維層からなり、多孔質中間層(B)が親水性繊維を少なくとも50質量%含む繊維層からなる請求項1~4のいずれか記載のモザイク荷電複層膜。
- モザイク荷電層(C)を構成するカチオン性重合体および/またはアニオン性重合体が、イオン基を有する重合体ブロックとビニルアルコール重合体ブロックとを含むブロック共重合体である請求項1~5のいずれか記載のモザイク荷電複層膜。
- 請求項1~6のいずれか記載のモザイク荷電複層膜の製造方法であって、
多孔質支持層(A)上に多孔質中間層(B)を形成した後に、該多孔質中間層(B)上に印刷することによってモザイク荷電層(C)を形成することを特徴とするモザイク荷電複層膜の製造方法。 - 前記多孔質中間層(B)上にモザイク荷電層(C)を印刷によって形成した後に熱処理および/または架橋処理を行う請求項7記載のモザイク荷電複層膜の製造方法。
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CN103087452A (zh) * | 2011-11-03 | 2013-05-08 | 三星电子株式会社 | 离子交换膜填充组合物、其制法、离子交换膜和电池 |
EP2590250A1 (en) * | 2011-11-03 | 2013-05-08 | Samsung Electronics Co., Ltd. | Ion exchange membrane filling composition, method of preparing ion exchange membrane, ion exchange membrane, and redox flow battery |
JP2013095918A (ja) * | 2011-11-03 | 2013-05-20 | Samsung Electronics Co Ltd | イオン交換膜充電用組成物、イオン交換膜の製造方法、イオン交換膜及びレドックスフロー電池 |
US9728792B2 (en) | 2011-11-03 | 2017-08-08 | Samsung Electronics Co., Ltd. | Ion exchange membrane filling composition, method of preparing ion exchange membrane, ion exchange membrane, and redox flow battery |
KR101890747B1 (ko) | 2011-11-03 | 2018-10-01 | 삼성전자주식회사 | 이온 교환막 충전용 조성물, 이온 교환막의 제조방법, 이온 교환막 및 레독스 플로우 전지 |
WO2014103819A1 (ja) * | 2012-12-25 | 2014-07-03 | 株式会社クラレ | イオン交換膜およびその製造方法ならびに電気透析装置 |
JPWO2014103819A1 (ja) * | 2012-12-25 | 2017-01-12 | 株式会社クラレ | イオン交換膜およびその製造方法ならびに電気透析装置 |
US10125036B2 (en) | 2012-12-25 | 2018-11-13 | Kuraray Co., Ltd. | Ion exchange membrane, method for producing same, and electrodialyzer |
JP2018012084A (ja) * | 2016-07-22 | 2018-01-25 | 国立大学法人山口大学 | モザイク荷電膜の製造方法及びモザイク荷電膜 |
WO2018056242A1 (ja) * | 2016-09-20 | 2018-03-29 | 栗田工業株式会社 | 逆浸透膜の阻止率向上剤及び阻止率向上方法 |
JP7439237B2 (ja) | 2019-08-16 | 2024-02-27 | トーレ・アドバンスド・マテリアルズ・コリア・インコーポレーテッド | 一価陰イオン選択性イオン交換膜 |
Also Published As
Publication number | Publication date |
---|---|
EP2520357A4 (en) | 2015-07-15 |
CN102770197B (zh) | 2015-07-01 |
KR20120106878A (ko) | 2012-09-26 |
US20120285881A1 (en) | 2012-11-15 |
KR101768434B1 (ko) | 2017-08-16 |
US9346020B2 (en) | 2016-05-24 |
JPWO2011081145A1 (ja) | 2013-05-13 |
CN102770197A (zh) | 2012-11-07 |
JP5669047B2 (ja) | 2015-02-12 |
EP2520357A1 (en) | 2012-11-07 |
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