WO2012133805A1 - 複合膜 - Google Patents
複合膜 Download PDFInfo
- Publication number
- WO2012133805A1 WO2012133805A1 PCT/JP2012/058641 JP2012058641W WO2012133805A1 WO 2012133805 A1 WO2012133805 A1 WO 2012133805A1 JP 2012058641 W JP2012058641 W JP 2012058641W WO 2012133805 A1 WO2012133805 A1 WO 2012133805A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- moisture
- composite membrane
- membrane
- permeable resin
- porous membrane
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 257
- 239000002131 composite material Substances 0.000 title claims abstract description 102
- 239000011347 resin Substances 0.000 claims abstract description 139
- 229920005989 resin Polymers 0.000 claims abstract description 139
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 68
- 230000003014 reinforcing effect Effects 0.000 claims abstract description 40
- 238000010030 laminating Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 72
- 238000012360 testing method Methods 0.000 claims description 29
- 239000004745 nonwoven fabric Substances 0.000 claims description 19
- 239000012779 reinforcing material Substances 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 230000008961 swelling Effects 0.000 claims description 10
- 239000003456 ion exchange resin Substances 0.000 claims description 9
- 229920003303 ion-exchange polymer Polymers 0.000 claims description 9
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 7
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical group [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- 229920001577 copolymer Polymers 0.000 claims description 6
- 229920002635 polyurethane Polymers 0.000 claims description 4
- 239000004814 polyurethane Substances 0.000 claims description 4
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 claims description 3
- 229940005642 polystyrene sulfonic acid Drugs 0.000 claims description 3
- 239000002759 woven fabric Substances 0.000 claims description 3
- 230000035699 permeability Effects 0.000 abstract description 30
- 239000010410 layer Substances 0.000 description 63
- 239000011148 porous material Substances 0.000 description 28
- 238000000034 method Methods 0.000 description 21
- 239000007788 liquid Substances 0.000 description 15
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 14
- 239000000843 powder Substances 0.000 description 14
- 230000002787 reinforcement Effects 0.000 description 13
- 238000004821 distillation Methods 0.000 description 11
- 239000012530 fluid Substances 0.000 description 10
- 239000002346 layers by function Substances 0.000 description 10
- 239000002245 particle Substances 0.000 description 10
- 239000000047 product Substances 0.000 description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 7
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 7
- -1 etc.) Substances 0.000 description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 239000013535 sea water Substances 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000012466 permeate Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 229920000728 polyester Polymers 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 229920003935 Flemion® Polymers 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 2
- 229920000544 Gore-Tex Polymers 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005373 pervaporation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OIEWLITYBUYJOH-UHFFFAOYSA-N 2,3-bis(ethenyl)benzoic acid Chemical compound OC(=O)C1=CC=CC(C=C)=C1C=C OIEWLITYBUYJOH-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 1
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920001289 polyvinyl ether Polymers 0.000 description 1
- 229920002620 polyvinyl fluoride Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 229920002717 polyvinylpyridine Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000005846 sugar alcohols Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/36—Pervaporation; Membrane distillation; Liquid permeation
- B01D61/364—Membrane distillation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
- B01D63/08—Flat membrane modules
- B01D63/082—Flat membrane modules comprising a stack of flat membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D65/00—Accessories or auxiliary operations, in general, for separation processes or apparatus using semi-permeable membranes
- B01D65/10—Testing of membranes or membrane apparatus; Detecting or repairing leaks
-
- 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
-
- 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
-
- 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
-
- 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
- B01D69/122—Separate manufacturing of ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/04—Characteristic thickness
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/38—Hydrophobic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2305/00—Condition, form or state of the layers or laminate
- B32B2305/02—Cellular or porous
- B32B2305/026—Porous
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/724—Permeability to gases, adsorption
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/447—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by membrane distillation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Definitions
- the present invention relates to a novel composite membrane, and more specifically, a composite membrane obtained by laminating a moisture permeable resin layer on one surface of a hydrophobic porous membrane, the moisture permeable resin layer being included in the reinforcing porous membrane.
- the present invention relates to a composite membrane having a performance excellent in water vapor separation characteristics.
- the membrane distillation method is generally a membrane separation method utilizing the properties of a porous hydrophobic membrane (Patent Document 1). The mechanism of the membrane distillation method will be described with reference to FIG. When one side of this porous hydrophobic membrane is contacted with high temperature primary water (solution such as seawater) and the other side of this membrane is contacted with low temperature fresh water (pure water), the membrane is hydrophobic. Primary water is blocked at the membrane surface and the primary water cannot penetrate the membrane (as a liquid).
- the gas can permeate through the porous membrane, the water vapor evaporating from the high temperature primary water is allowed to permeate through the membrane, and the permeated water vapor is condensed at the low temperature portion, so that the primary water (solution It is possible to separate only water from That is, in the membrane distillation method, high temperature feed water is allowed to flow through one side of the membrane and a cooling surface is provided on the other side of the membrane, so that the vapor pressure difference based on the generated temperature difference becomes the driving force for vapor transmission.
- the non-volatile solute separation performance is extremely high, for example, the non-volatile salt content is mainly the solute.
- High purity fresh water can be obtained from seawater.
- the membrane distillation method is the same as the evaporation method in terms of the basic principle, but has various advantages over the evaporation method as follows. -The degree of freedom in the shape of the membrane is large, and the restrictions on the shape of the device are small. ⁇ By increasing the membrane filling rate, the device volume can be reduced. ⁇ Because it is based on the difference in vapor pressure, it can be used at relatively low temperatures below the boiling point. If exhaust heat can be used or water sources with different temperatures can be used, there are significant energy benefits. -Since the solution and the permeated water do not come into direct contact, there is little need to consider osmotic pressure as in the reverse osmosis method, and the power cost is very low.
- the biggest problem in the membrane distillation method is that when the membrane surface becomes dirty, not only does the evaporation surface of the water vapor become clogged but also the hydrophobicity of the membrane is lost, and finally the feed water becomes a porous hydrophobic membrane. There is an essential problem that there is a risk of intrusion and leakage to the cooling side (transmission side).
- Patent Document 2 a method of forming a composite film by placing a hydrophilic resin film on the surface of a porous hydrophobic film has been proposed.
- the hydrophilic resin film swells when it comes into contact with the primary water, so that the strength is reduced, the film is worn out by the flow rate of the primary water, the film is cracked, and pinholes are opened. is there.
- Patent Document 3 a method in which a hydrophobic porous film is arranged on the surface of the hydrophilic resin film and the hydrophilic resin film is sandwiched between the hydrophobic porous films.
- the hydrophilic resin layer is not in direct contact with primary water, and the surface of the hydrophilic resin layer is also reinforced by the hydrophobic porous membrane, so that the durability of the composite membrane can be improved. Since the hydrophilic resin layer is not in direct contact with the raw water, there is a problem that the water vapor transmission rate may not be sufficient.
- the present invention has been made to solve the above-described problems, and an object thereof is to provide a composite film having excellent durability and moisture permeability.
- the present invention provides the following.
- the moisture-permeable resin has polystyrene sulfonic acid, polyvinyl alcohol, vinyl alcohol copolymer, fluorine ion exchange resin, a resin having a protic hydrophilic group in a repeating unit, and an aprotic hydrophilic group in a repeating unit.
- a breathable reinforcing material is laminated on a surface opposite to the surface of the hydrophobic porous membrane on which the moisture-permeable resin layer is laminated, (1) to (11) A composite membrane according to any one of the above.
- FIG. 2 is a schematic sectional view showing an example of the composite membrane of the present invention.
- a layer of moisture permeable resin (functional layer) is laminated on one side of the hydrophobic porous membrane, and the layer of moisture permeable resin is further included in the reinforcing porous membrane. It is.
- the composite membrane of the present invention is excellent in surface durability when it comes into contact with the outer member because the moisture-permeable resin layer is reinforced with a reinforcing porous membrane. Therefore, it is not worn out, cracked or pinholed. When wear, cracks, pinholes, etc. occur, the gas barrier properties decrease, and gas and liquid permeate there from. In order to prevent wear, cracks, pinholes, etc., and to secure gas barrier properties, the entire thickness of the moisture-permeable resin layer must be formed thickly, in which case the moisture permeability is reduced. However, since the composite membrane of the present invention is excellent in surface durability, the moisture-permeable resin layer can be made thin, and therefore the moisture permeability is high.
- the moisture-permeable resin layer can be exposed from the upper surface of the reinforcing porous membrane.
- the composite membrane is used as a separation membrane for selectively allowing water contained in gas or liquid (separation membrane for water content adjustment module), for example, a membrane for membrane distillation
- the moisture-permeable resin is primary. It can be in direct contact with water and can achieve excellent moisture permeability.
- Patent Document 3 proposes a method of sandwiching a resin film with a hydrophobic porous film and cannot directly contact raw water. In this respect, the moisture permeability of the composite membrane of the present invention is further improved than that of Patent Document 3.
- the moisture-permeable resin layer can be exposed from the lower surface of the reinforcing porous membrane.
- the exposed portion of the moisture permeable resin layer exists in contact with the reinforcing porous membrane and the hydrophobic porous membrane.
- a liquid reservoir of moisture-permeable resin liquid is formed at the boundary between the nonwoven fabric and the moisture-permeable resin. May be uniform. If this thickness is non-uniform, there is a concern that pinholes are likely to occur at relatively thin portions. In that case, in order to prevent pinholes, measures such as increasing the thickness of the moisture-permeable resin layer as a whole have been taken.
- the moisture-permeable resin is in contact with the porous membrane, and the unevenness (pore diameter) on the surface of the porous membrane is much smaller than the fiber diameter of the nonwoven fabric or the like. Can be prevented. Therefore, the moisture-permeable resin can exist with a uniform thickness, and the occurrence of pinholes can be prevented. As a result, it is not necessary to increase the thickness of the moisture-permeable resin layer, so that high moisture permeability can be realized.
- the layer of moisture-permeable resin may be formed on the surface without entering the hydrophobic porous membrane. Further, at least a part of the moisture-permeable resin layer may enter the inside of the hydrophobic porous membrane.
- the moisture-permeable resin layer enters the hydrophobic porous membrane, the anchor effect to the small holes in the hydrophobic porous membrane is exhibited and the durability is improved.
- the moisture-permeable resin layer that has entered the inside of the hydrophobic porous membrane is not exposed from the lower surface of the hydrophobic porous membrane. That is, the composite membrane of the present invention has a layered portion composed only of the hydrophobic porous membrane over the entire surface, and this portion prevents liquid from permeating.
- the composite membrane is preliminarily coated or impregnated with a liquid containing moisture-permeable resin on the reinforcing porous membrane, and the solvent is removed from the applied or impregnated solution by washing, drying, etc., and then thermocompression bonded with the hydrophobic porous membrane. It can be manufactured by the method to do.
- the composite membrane may have a breathable reinforcing material laminated on a surface opposite to the surface of the hydrophobic porous membrane on which the moisture-permeable resin layer is laminated. Further, the breathable reinforcing material may be laminated on a surface opposite to the surface on which the hydrophobic porous membrane of the reinforcing porous membrane is laminated. In this case, a breathable reinforcing material may be laminated via a hydrophilic resin layer exposed from the upper surface of the reinforcing porous membrane.
- the breathable reinforcing material can be laminated by adhering to one of a hydrophobic porous membrane, a reinforcing porous membrane, a hydrophilic resin layer, or a combination thereof by, for example, heat sealing.
- a breathable reinforcing material By laminating a breathable reinforcing material, the strength of the composite membrane can be increased.
- the average thickness of the moisture-permeable resin layer is 25 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less. By reducing the average thickness, water vapor permeability can be improved.
- the average thickness is preferably as thin as possible so long as no pinhole is generated, but the lower limit is, for example, 1 ⁇ m or more (particularly 2 ⁇ m or more).
- a preferable moisture-permeable resin is a water-resistant and water-permeable resin excellent in water resistance.
- durability high temperature and humidity resistance
- moisture permeability in a high temperature and high humidity environment is increased.
- the water resistance of the water and moisture permeable resin can be evaluated based on the degree of swelling obtained from the following water resistance test.
- the degree of swelling of the water-resistant moisture-permeable resin is, for example, 20 times or less, preferably 15 times or less, and more preferably 10 times or less.
- the lower limit of the degree of swelling is not particularly limited, but may be 2 times or more (particularly 5 times or more).
- moisture-permeable resin examples include polystyrene sulfonic acid, polyvinyl alcohol, urethane, vinyl alcohol copolymer (ethylene-vinyl alcohol copolymer, tetrafluoroethylene-vinyl alcohol copolymer), fluorine ion exchange resin (DuPont).
- ion exchange resins such as divinylbenzene sulfonic acid copolymer and divinylbenzene carboxylic acid copolymer
- ion exchange resins such as divinylbenzene sulfonic acid copolymer and divinylbenzene carboxylic acid copolymer
- Resin having a protic hydrophilic group protic hydrophilic resin
- a resin having an aprotic hydrophilic group in a repeating unit such as polyethylene oxide, polyvinyl pyridine, polyvinyl ether, polyvinyl pyrrolidone, pyrrolidone (aprotic hydrophilic resin) Etc. That.
- the moisture-permeable resin may form a three-dimensional crosslinked structure.
- the three-dimensional crosslinked moisture-permeable resin include a crosslinked product of the protic hydrophilic resin and a crosslinked product of the aprotic hydrophilic resin.
- the three-dimensional crosslinked moisture-permeable resin is excellent in water resistance.
- the moisture-permeable resin (including a three-dimensional crosslinked moisture-permeable resin) can be used alone or in combination of two or more.
- Preferred moisture-permeable resins include polyvinyl alcohol cross-linked products (for example, cross-linked products of a mixture of glutaraldehyde and HCl, cross-linked products of formaldehyde, cross-linked products of blocked isocyanate, etc.), polyurethane cross-linked products (for example, at both ends).
- the cross-linked polyvinyl alcohol is not only excellent in water resistance but also easy to apply and can easily achieve a thin moisture-permeable resin layer.
- the crosslinked polyurethane is not only excellent in water resistance but also excellent in abrasion resistance, oxidation resistance, oil resistance, and aging resistance.
- Fluorine ion exchange resins have excellent heat resistance and chemical resistance, so they are highly durable in high temperatures, high humidity, and systems where acids and alkalis exist, making them suitable for use in harsh environments. Yes.
- the layer of moisture-permeable resin is included in the reinforcing porous membrane and is reinforced thereby.
- An example of a composite film provided with such a layer of moisture-permeable resin is shown in FIG.
- FIG. 3A is a schematic cross-sectional view of a layer of moisture-permeable resin reinforced with a reinforcing porous membrane
- FIG. 3B is a schematic cross-sectional view of a composite membrane provided with the layer of moisture-permeable resin. It is.
- the reinforcing porous membrane may be the same as the hydrophobic porous membrane described later.
- the thickness of the reinforcing porous membrane can be appropriately adjusted so that a desired uniform moisture-permeable resin layer thickness can be obtained.
- the hydrophobic porous membrane constitutes a part of the composite membrane and maintains air permeability while bringing hydrophobicity to the composite membrane.
- the type of resin constituting the hydrophobic porous membrane is not particularly limited as long as the hydrophobic porous membrane has hydrophobicity and air permeability. Specifically, those having heat resistance and corrosion resistance are preferable.
- Polyolefins such as polyethylene and polypropylene; polycarbonate; polystyrene; polyvinyl chloride; polyvinylidene chloride; polyester; polytetrafluoroethylene, tetrafluoroethylene / hexafluoro Fluorine resins such as propylene copolymer, polyvinyl fluoride, and polyvinylidene fluoride can be used.
- a preferred hydrophobic porous membrane is a fluororesin porous membrane.
- the fluororesin is excellent in heat resistance and corrosion resistance, and has extremely low critical surface tension, that is, high hydrophobicity (water repellency).
- a particularly preferred hydrophobic porous membrane is a stretched porous membrane made of polytetrafluoroethylene (PTFE) (hereinafter sometimes referred to as “ePTFE membrane”, “stretched porous PTFE membrane”, etc.). Since the ePTFE membrane can form extremely fine pores and can improve the smoothness of the surface, the moisture-permeable resin layer can be formed easily and uniformly. In addition, the ePTFE membrane can increase the porosity, and can increase the moisture permeability of the resulting composite membrane. Furthermore, the ePTFE membrane has extremely excellent hydrophobicity, so that the resulting composite membrane can reliably prevent liquid penetration.
- the layers When laminating a hydrophobic porous membrane and a layer of moisture-permeable resin, the layers may be laminated by thermal fusion. However, if the heat resistance of the hydrophobic porous membrane is lower than the heat resistance of the moisture-permeable resin, the layer is melted. The dressing process becomes difficult. Therefore, if a material excellent in heat resistance is used for the hydrophobic porous membrane, it is easy to fuse with the moisture-permeable resin layer, and the degree of freedom in selecting the material of the moisture-permeable resin is increased.
- the ePTFE membrane is obtained by molding a paste obtained by mixing PTFE fine powder with a molding aid, removing the molding aid from the molded body, stretching at a high temperature and high speed, and further firing if necessary. Is obtained. The details are described in, for example, Japanese Patent Publication No. 51-18991.
- the stretching may be uniaxial stretching or biaxial stretching.
- the uniaxially stretched porous PTFE film there are micro island-like nodes (folded crystals) that are substantially perpendicular to the stretching direction in a microscopic manner, and interdigital fibrils (the folded crystals are stretched by stretching). It is characterized in that the linear molecular bundles (melted and drawn) are oriented in the stretching direction.
- the biaxially stretched porous PTFE film has a cobweb-like fibrous structure in which fibrils spread radially, nodes connecting the fibrils are scattered in islands, and there are many spaces divided by the fibrils and nodes. There is a micro feature in the point.
- the biaxially stretched porous PTFE film is particularly suitable because it is easier to widen than the uniaxially stretched porous PTFE film, has an excellent balance of physical properties in the vertical and horizontal directions, and lowers the production cost per unit area. Used.
- the maximum pore size of the hydrophobic porous membrane is, for example, 15 ⁇ m or less, preferably 10 ⁇ m or less, and more preferably 5 ⁇ m or less. If the maximum pore size is too large, the moisture permeable resin will easily enter the pores of the hydrophobic porous membrane when a mixed solution containing the moisture permeable resin is applied or impregnated during the production of the composite membrane. Formation of the resin layer may be difficult. As the maximum hole diameter decreases, the moisture-permeable resin layer becomes easier to uniform, and the generation of pinholes can be suppressed.
- the maximum pore diameter of the ePTFE membrane can be appropriately controlled by the draw ratio or the like.
- the maximum pore diameter can be determined by the following formula by obtaining the bubble point value according to the bubble point method (JISK3832) using isopropanol.
- the average pore diameter of the hydrophobic porous membrane is, for example, 0.05 ⁇ m or more, preferably 0.1 ⁇ m or more, and more preferably 0.2 ⁇ m or more.
- the average pore diameter is a value obtained from the pore distribution (volume distribution with respect to the pore diameter). That is, the pore distribution was measured on the assumption that all the pores of the porous membrane were cylindrical, and the pore diameter corresponding to the intermediate value of the pore volume was determined as the average pore diameter.
- the average pore diameter of the hydrophobic porous membrane was determined using a Coulter Porometer manufactured by Coulter Electronics.
- the porosity of the hydrophobic porous membrane can be appropriately set according to the average pore diameter, and is, for example, 40% or more (preferably 50% or more).
- the porosity is, for example, about 98% or less (preferably 90% or less). Note that the porosity of the ePTFE membrane can be adjusted as appropriate by the draw ratio and the like, as with the average pore diameter.
- the thickness of the hydrophobic porous membrane when calculating the volume V was measured with a dial thickness gauge (measured in a state where a load other than the main body spring load was applied using “SM-1201” manufactured by Teclock Corporation). Depending on the average thickness.
- Porosity (%) [1- (D / D standard )] ⁇ 100
- the air permeability (JISP 8117: 1998) of the hydrophobic porous membrane is, for example, 500 sec or less, preferably 10 sec or less.
- the value of the air permeability is too large, the moisture permeability of the composite membrane becomes low, and the moisture permeability of the resulting composite membrane becomes insufficient. Further, when the composite membrane is used as a heat exchange membrane or a membrane for membrane distillation, the heat exchange capacity and the separation efficiency are lowered.
- Air permeability means the Gurley number.
- the Gurley number is the time required for 100 cm 3 of air to flow over an area per square inch (642 mm 2 ). In this specification, unless otherwise specified, the air permeability is measured using an Oken type air permeability measuring device “KG1 (trade name)” manufactured by Asahi Seiko Co., Ltd.
- the thickness of the hydrophobic porous membrane is not particularly limited, but is, for example, 100 ⁇ m or less, preferably 50 ⁇ m or less, and more preferably 25 ⁇ m or less. If it is too thick, the moisture permeability of the composite membrane is lowered, and when used as a membrane for membrane distillation, the heat exchange capability and the separation efficiency are lowered. However, if the film is too thin, the gas barrier properties are lowered, and liquids and salts can permeate, and workability can be impaired. Therefore, the thickness of the hydrophobic porous membrane is, for example, 5 ⁇ m or more, preferably 10 ⁇ m or more, and more preferably 20 ⁇ m or more.
- the hydrophobic porous membrane and the moisture permeable resin layer reinforced by the reinforcing porous membrane are combined.
- the unevenness (pore diameter) on the surface of the porous membrane is much smaller than the fiber diameter of the nonwoven fabric, and it is possible to prevent the moisture-permeable resin liquid from collecting.
- the layer of the moisture-permeable resin is made thin and uniform, and as a result, highly durable.
- the hydrophobic porous membrane itself reinforces the entire composite membrane.
- the breathable reinforcing material is usually made of a fibrous resin.
- a fibrous resin By using a fibrous resin, a reinforcing material having both air permeability and strength can be easily produced.
- the breathable reinforcing material formed by the fibrous resin may be any of a woven fabric, a knitted fabric, a non-woven fabric (for example, a non-woven fabric formed by a manufacturing method such as a thermal bond method or a spun bond method), or a net.
- a particularly preferable breathable reinforcing material is a nonwoven fabric.
- the composite membrane of the present invention has high gas barrier properties and high moisture permeability. Therefore, it can be advantageously used as a separation membrane (separation membrane for moisture amount adjustment module) for selectively permeating water vapor contained in gas or liquid, for example, pervaporation membrane [eg seawater desalination or water and other liquids It can be used as a membrane for separating (alcohol such as ethanol), a dehumidifying membrane, a humidifying membrane or the like.
- the fluid (including the fluid to be dehydrated) is supplied to the surface of the composite membrane on the layer side of the water-permeable resin, and water is supplied to the other surface of the composite membrane.
- the receiving side fluid (including the dehydrating side fluid) is flowed, and the flow path is controlled so that the water supply side fluid and the water receiving side fluid are not mixed.
- a preferable moisture amount adjustment module is a flat membrane stack type module, and the water supply side fluid and the water reception side fluid are caused to flow in the counterflow direction.
- composite membranes are stacked, and the stacked composite membranes are separated at a predetermined interval by a spacer or the like.
- a spacer or the like For example, as shown in FIG. 4, there is a mode in which the composite film 10 and the corrugated spacer 50 are laminated.
- this gap can be used as a fluid flow path, and moisture can be adjusted by exchanging moisture between the fluids on both sides.
- the composite membrane of the present invention can improve gas barrier properties and moisture permeability even under high temperature and high humidity by using a water-resistant moisture-permeable resin as the moisture-permeable resin. Therefore, a gas for selectively supplying water vapor to a fuel electrode or an air electrode (especially a fuel electrode) contained in a separation membrane (for example, exhaust gas of a fuel cell electrode (especially exhaust gas on the air electrode side)) for selectively permeating water vapor from a hot and humid gas. It can also be advantageously used as a humidifying film for use in humidification of water.
- Example 1 As a porous membrane for reinforcement, ePTFE membrane (manufactured by Japan Gore-Tex Co., Ltd., average thickness 4 ⁇ m, average pore diameter 0.3 ⁇ m, maximum pore diameter 0.5 ⁇ m, porosity 80%, Gurley number 0.9 seconds, tensile strength MD1 .0N, TD1.2N). As a hydrophobic porous membrane, ePTFE membrane (manufactured by Japan Gore-Tex Co., Ltd., average thickness 40 ⁇ m, average pore size 0.2 ⁇ m, maximum pore size 0.4 ⁇ m, porosity 86%, Gurley number 5.4 seconds, tensile strength MD1 .2N, TD1.8N).
- ePTFE membrane manufactured by Japan Gore-Tex Co., Ltd., average thickness 4 ⁇ m, average pore diameter 0.3 ⁇ m, maximum pore diameter 0.5 ⁇ m, porosity 80%, Gurley number 0.9 seconds, tensile strength MD1 .0N,
- a thermal bond nonwoven fabric (“9820F (trade name)” manufactured by Shinwa Co., Ltd.) using polyester fibers (“Melty (trade name)” manufactured by Unitika Fiber Co., Ltd., 2.2 dtex) was prepared.
- the breathable reinforcing material was thermally fused to the surface opposite to the surface coated with the moisture-permeable resin of the hydrophobic porous membrane (3 minutes at 150 ° C. while applying a load of 500 kPa), and the composite with nonwoven fabric of Example 1 A film was formed.
- Comparative Example 1 A composite membrane was formed in the same manner as in Example 1 except that the reinforcing porous membrane was not used.
- Example 1 The composite membranes of Example 1 and Comparative Example 1 were evaluated for moisture permeability, mechanical strength, and durability. Below, each evaluation method and evaluation result are explained in full detail.
- the mechanical strength of the reinforcing porous membrane is improved under high temperature and high humidity conditions.
- a moisture amount adjusting module for example, a dehumidifying membrane, a humidifying membrane, or a pervaporation membrane
- the mechanical strength of the composite membrane of the present invention is high under high temperature and high humidity conditions close to actual use conditions.
- the composition of the test powder, SiO 2 is 95%, Fe 2 O 3, Al 2 O 3, TiO 2 and MgO ignition loss was 5% or less.
- the particle density of the test powder was 2.6-2.7 g / cm 3 .
- the particle size distribution is as shown in Table 3, and the oversize (%) in the table is a powder having a particle size larger than the indicated particle size (%) with respect to the total powder (particles). The ratio of particles). For example, the proportion of powder having a particle size larger than 45 ⁇ m is 100% and the proportion of powder having a particle size larger than 75 ⁇ m is approximately 90% with respect to the total powder.
- the proportion of 45-75 ⁇ m powder is approximately 10% (100-90).
- the proportion of powder having a particle size larger than 106 ⁇ m is approximately 80%, and therefore the proportion of powder having a particle size of 75 to 106 ⁇ m is approximately 10% (90-80).
- the composite membrane with nonwoven fabric was subjected to FT-IR analysis before and after the durability test.
- the composite membrane with a nonwoven fabric the one with the reinforcing layer of Example 1 and the one without the reinforcing layer of Comparative Example 1 were used.
- a change in peak height was observed on the FT-IR chart before and after durability.
- changes such as a valley near 500 cm ⁇ 1 increased after endurance and a valley near 1000 cm ⁇ 1 decreased.
- there was almost no change in peak on the FT-IR before and after durability That is, it is considered that the surface of the composite membrane without reinforcement changed before and after the endurance, but the surface of the composite membrane with reinforcement hardly changed before and after the endurance.
- the composite membrane without reinforcement and the FT-IR chart of ePTFE alone were compared.
- the composite membrane without reinforcement had a large valley near 500 cm ⁇ 1 after endurance. This was very similar to the valley around 500 cm ⁇ 1 of ePTFE. From this, it is considered that the unreinforced functional layer (moisture-permeable resin layer) was worn out by the durability test, and the hydrophobic porous membrane (ePTFE membrane) under the functional layer was exposed. Further, the unreinforced composite membrane had a small valley near 1000 cm ⁇ 1 after durability. ePTFE shows a flat chart around 1000 cm ⁇ 1 and no peak. From this, the valley seen near 1000 cm ⁇ 1 is considered to be caused by the material of the functional layer (moisture-permeable resin layer), and it is worn out by the durability test, and the valley seen near 1000 cm ⁇ 1 It seems that it has become smaller.
- the functional layer (moisture permeable resin layer) of the composite membrane without reinforcement was depleted by the durability test, and the hydrophobic porous membrane (ePTFE membrane) under the functional layer was exposed.
- the composite film with reinforcement hardly changed the surface components even after the durability test, that is, the functional layer (moisture-permeable resin layer) did not wear out and maintained a healthy state.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
・膜の形状に自由度が大きく、装置の形の制限が小さい。
・膜の充填率を高くすることにより、装置体積の小型化が可能。
・蒸気圧差に基づくため、沸点以下の比較的低温での利用の可能性があり、排熱を利用したり、温度の異なる水源を利用したりすることができれば、エネルギー的なメリットが大きい。
・溶液と透過水が直接接触しないので、逆浸透法のような浸透圧を考慮する必要が少なく、動力費は非常に低い。
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
耐水性試験:温度120℃、水蒸気圧0.23MPaの環境下に樹脂を24時間放置し、次いで温度25℃の水に15分間浸漬すること、
を特徴とする、(1)~(7)のいずれか1つに記載の複合膜。
以下、図を参照しつつ、本発明の複合膜について詳細に説明する。
透湿性樹脂の層の平均厚さは、25μm以下、好ましくは10μm以下、さらに好ましくは5μm以下である。平均厚さを薄くすることで、水蒸気の透過性を向上できる。平均厚さは、ピンホールが発生しない限り薄いほど好ましいが、その下限は、例えば、1μm以上(特に2μm以上)である。
平均厚さt=面積A/長さL
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
d=4γIPAcosθ1/PB
(式中、dは最大孔径、γIPAはイソプロパノールの表面張力、θ1はイソプロパノールと疎水性多孔質膜の接触角(但し、疎水性多孔質膜がIPAで濡れている場合は、cosθ1=1)、PBはバブルポイント値を示す)
空孔率(%)=[1-(D/Dstandard)]×100
補強用多孔質膜として、ePTFE膜(ジャパンゴアテックス株式会社製、平均厚さ4μm、平均孔径0.3μm、最大孔径0.5μm、空孔率80%、ガーレー数0.9秒、引張強度MD1.0N、TD1.2N)を用意した。
疎水性多孔質膜として、ePTFE膜(ジャパンゴアテックス株式会社製、平均厚さ40μm、平均孔径0.2μm、最大孔径0.4μm、空孔率86%、ガーレー数5.4秒、引張強度MD1.2N、TD1.8N)を用意した。
透湿性樹脂溶液として、フッ素系イオン交換樹脂(旭硝子株式会社製「フレミオン(商品名)」、固形分9%エタノール溶媒(EtOH/H2O=50/50))を用意した。
透湿性樹脂を、補強用多孔質膜の両面から、含浸させた。含浸と同時に、疎水性多孔質膜を、補強用多孔質膜の片面に載せ貼り合わせた。塗布した透湿性樹脂を130℃で1分間乾燥させた。
通気性補強材として、ポリエステル繊維(ユニチカファイバー株式会社製「メルティ(商品名)」、2.2dtex)を用いたサーマルボンド不織布(シンワ株式会社製「9820F(商品名)」)を用意した。通気性補強材を疎水性多孔質膜の透湿性樹脂を塗布した面とは反対の面に熱融着し(500kPaの荷重をかけながら150°Cで3分間)、実施例1の不織布付複合膜を形成した。
補強用多孔質膜を使用しなかったことを除いて、実施例1と同様にして複合膜を形成した。
実施例1および比較例1の複合膜の、透湿度、機械的強度、ならびに耐久性について評価を行った。以下に、それぞれの評価方法および評価結果について詳述する。
得られた不織布付複合膜の室温透湿性(JISL1099B-1法に依る)を測定した。測定結果を表1に示す。
補強用多孔質膜の有無が透湿性樹脂の層(機能層)の機械的強度に与える影響を評価した。疎水性多孔質膜、通気性補強材による機械的強度向上の影響を除くために、実施例1および比較例1の不織布付複合膜から、疎水性多孔質膜、通気性補強材を除いたものを試料として用意した。引っ張り試験機にて、常温条件での環境温湿度(23℃、50%RH)又は高温多湿条件での環境温湿度(60℃、100%RH)において、初期チャック間距離:80mm、試験片形状:10mm幅矩形、引張速度200mm/minにて測定を行った。引っ張り強度が最大になった時点での強度及び試料が破断した時点での伸度を求めた。また、弾性率は伸度が2%の時点での値を用いた。結果を表2に示す。
図5に示す耐久試験装置を用いて、実施例1および比較例1の不織布付複合膜の耐久性を試験した。耐久試験装置において、不織布付複合膜を配置し、水を注入し、そして試験用粉体を10wt%で水中に分散させた。耐久試験装置は、Airをバブリングすることができ、これにより試験用粉体を14日間攪拌させた。攪拌された試験用粉体は、耐久試験装置に配置した不織布付複合膜と接触した。耐久試験前後の不織布付複合膜について、フーリエ変換型赤外分光(FT-IR)による分析を行った。(FT-IRの測定装置:PerkinElmer社製Spectrum100、測定条件(ATR法により4000-400cm-1範囲で測定を実施。))
なお、試験用粉体の組成は、SiO2が95%であり、Fe2O3、Al2O3、TiO2およびMgOの強熱減量が5%以下であった。試験用粉体の粒子密度は、2.6-2.7g/cm3であった。粒径分布は、表3に示したとおりであり、表中のオーバーサイズ(%)とは、全粉体(粒子)に対して、指示されている粒径よりも大きな粒径の粉体(粒子)の割合を意味する。例えば、全粉体に対して、粒径が45μmより大きな粉体の割合は100%であり、粒径が75μmより大きな粉体の割合はおよそ90%である。したがって、45~75μmの粉体の割合は、およそ10%(100-90)である。また、粒径が106μmより大きな粉体の割合はおよそ80%であり、したがって粒径が75~106μmの粉体の割合は、およそ10%(90-80)である。
50 スペーサー
Claims (14)
- 疎水性多孔質膜の片面に透湿性樹脂の層を積層してなる複合膜であって、該透湿性樹脂の層は補強用多孔質膜に含まれることを特徴とする、複合膜。
- 該透湿性樹脂の層が該補強用多孔質膜の上表面から露出していることを特徴とする、請求項1に記載の複合膜。
- 該透湿性樹脂の層が該補強用多孔質膜の下面から露出していることを特徴とする、請求項1または2に記載の複合膜。
- 該補強用多孔質膜の下面から露出した該透湿性樹脂の層の少なくとも一部が、該疎水性多孔質膜内に入り込んでいるが、該疎水性多孔質膜の下面から露出していないことを特徴とする、請求項3に記載の複合膜。
- 該透湿性樹脂の層の厚みが25μm以下であることを特徴とする、請求項1~4のいずれか1項に記載の複合膜。
- 該透湿性樹脂の層の厚みが10μm以下であることを特徴とする、請求項1~5のいずれか1項に記載の複合膜。
- 該透湿性樹脂の層の厚みが5μm以下であることを特徴とする、請求項1~6のいずれか1項に記載の複合膜。
- 該透湿性樹脂が、以下の耐水性試験前後の樹脂の体積変化から求まる膨潤度が2倍以上且つ20倍以下の膨潤性を示し、
膨潤度=耐水性試験後の樹脂の体積/耐水性試験前の樹脂の体積
耐水性試験:温度120℃、水蒸気圧0.23MPaの環境下に樹脂を24時間放置し、次いで温度25℃の水に15分間浸漬すること、
を特徴とする、請求項1~7のいずれか1項に記載の複合膜。 - 該透湿性樹脂がポリスチレンスルホン酸、ポリビニルアルコール、ビニルアルコール共重合体、フッ素系イオン交換樹脂、繰り返し単位にプロトン性親水性基を有する樹脂、繰り返し単位に非プロトン性親水性基を有する樹脂のいずれかであることを特徴とする、請求項1~8のいずれか1項に記載の複合膜。
- 該透湿性樹脂がフッ素系イオン交換樹脂、ポリビニルアルコール、ポリウレタンのいずれかであることを特徴とする、請求項1~9のいずれか1項に記載の複合膜。
- 該補強用多孔質膜が、延伸PTFE膜であることを特徴とする、請求項1~10のいずれか1項に記載の複合膜。
- 通気性補強材を、該疎水性多孔質膜の該透湿性樹脂の層が積層されている面と逆の面に積層していることを特徴とする、請求項1~11のいずれか1項に記載の複合膜。
- 該通気性補強材が織布、不織布、ネットのいずれかであることを特徴とする、請求項12に記載の複合膜。
- 水蒸気分離膜として使用することを特徴とする、請求項1~13のいずれか1項に記載の複合膜。
Priority Applications (7)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020137024870A KR101570916B1 (ko) | 2011-03-30 | 2012-03-30 | 복합막 |
AU2012233249A AU2012233249A1 (en) | 2011-03-30 | 2012-03-30 | Composite membrane |
CA2831772A CA2831772C (en) | 2011-03-30 | 2012-03-30 | Composition membrane comprising moisture-permeable resin and reinforcing porous membrane |
US14/008,584 US9358507B2 (en) | 2011-03-30 | 2012-03-30 | Composite membrane |
EP12765268.3A EP2692421B1 (en) | 2011-03-30 | 2012-03-30 | Composite membrane |
CN201280016576.6A CN103459005B (zh) | 2011-03-30 | 2012-03-30 | 复合膜 |
AU2016200400A AU2016200400B2 (en) | 2011-03-30 | 2016-01-22 | Composite membrane |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2011075382A JP2012206062A (ja) | 2011-03-30 | 2011-03-30 | 複合膜 |
JP2011-075382 | 2011-03-30 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2012133805A1 true WO2012133805A1 (ja) | 2012-10-04 |
Family
ID=46931499
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2012/058641 WO2012133805A1 (ja) | 2011-03-30 | 2012-03-30 | 複合膜 |
Country Status (8)
Country | Link |
---|---|
US (1) | US9358507B2 (ja) |
EP (1) | EP2692421B1 (ja) |
JP (1) | JP2012206062A (ja) |
KR (1) | KR101570916B1 (ja) |
CN (1) | CN103459005B (ja) |
AU (2) | AU2012233249A1 (ja) |
CA (1) | CA2831772C (ja) |
WO (1) | WO2012133805A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109855377A (zh) * | 2017-11-30 | 2019-06-07 | 青岛海尔股份有限公司 | 冷藏冷冻装置及其储物容器 |
Families Citing this family (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2012206062A (ja) * | 2011-03-30 | 2012-10-25 | Nihon Gore Kk | 複合膜 |
JP6453537B2 (ja) * | 2013-12-27 | 2019-01-16 | 日東電工株式会社 | 透湿性濾材 |
US9695066B2 (en) | 2014-01-31 | 2017-07-04 | Paragon Space Development Corporation | Ionomer-membrane water processing apparatus |
US9399195B2 (en) * | 2014-01-31 | 2016-07-26 | Paragon Space Development Corporation | Ionomer-membrane water processing apparatus |
KR101625274B1 (ko) * | 2014-02-06 | 2016-06-08 | 한양대학교 에리카산학협력단 | 막 증발 모듈, 및 이를 이용한 담수화 시스템 |
CN104191680B (zh) * | 2014-09-03 | 2016-11-02 | 青岛志腾工贸有限公司 | 适用于固体废弃物堆肥发酵过程使用的覆盖膜材料 |
WO2016081541A1 (en) * | 2014-11-19 | 2016-05-26 | The Research Foundation For The State University Of New York | Nanostructured fibrous membranes for membrane distillation |
WO2017132409A1 (en) * | 2016-01-27 | 2017-08-03 | W. L. Gore & Associates, Inc. | Insulating structures |
JP6739834B2 (ja) * | 2016-05-30 | 2020-08-12 | 新江州株式会社 | 積層シートおよびその製造方法 |
US11168013B2 (en) | 2016-09-16 | 2021-11-09 | Paragon Space Development Corporation | In-situ resource utilization-derived water purification and hydrogen and oxygen production |
US10752523B2 (en) | 2016-09-16 | 2020-08-25 | Paragon Space Development Corporation | Systems and methods for recovery of purified water and concentrated brine |
CN112512679B (zh) | 2018-05-31 | 2023-04-21 | 斯攀气凝胶公司 | 火类增强的气凝胶组成物 |
CN109107399B (zh) * | 2018-07-30 | 2021-04-23 | 绍兴百立盛新材料科技有限公司 | 一种水分子渗透膜及其制备方法和应用 |
CN109280165A (zh) * | 2018-11-08 | 2019-01-29 | 济南大学 | 一种可逆光控亲水性的偶氮苯类pdo3改性膜及其制备方法 |
DE102018131922A1 (de) | 2018-12-12 | 2020-06-18 | Carl Freudenberg Kg | Membran für den selektiven Stofftransport |
CN111545069A (zh) * | 2019-02-12 | 2020-08-18 | 日立化成株式会社 | 层叠物 |
CN112172292A (zh) * | 2019-07-03 | 2021-01-05 | 滁州英诺信电器有限公司 | 一种显控面贴保护层结构 |
CN110749014B (zh) * | 2019-11-27 | 2023-09-29 | 广东美的制冷设备有限公司 | 用于空气调节设备的加湿膜及制备方法、空气调节设备 |
CN113150333A (zh) * | 2021-02-07 | 2021-07-23 | 浙江汉丞科技有限公司 | 高透湿含氟超疏油微孔膜的制备方法 |
CN112980118A (zh) * | 2021-02-07 | 2021-06-18 | 浙江汉丞科技有限公司 | 用于高透湿超透气微孔膜的含氟高分子混合料及其应用 |
CN112848572A (zh) * | 2021-02-07 | 2021-05-28 | 际华集团股份有限公司系统工程中心 | 超强防水多功能复合面料及其制作方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59203602A (ja) | 1983-05-02 | 1984-11-17 | Asahi Chem Ind Co Ltd | 複合膜 |
JPS6157205A (ja) | 1984-08-27 | 1986-03-24 | Nitto Electric Ind Co Ltd | サ−モパ−ベ−パレ−シヨン法による水溶液の処理方法 |
JPH01199625A (ja) * | 1988-02-04 | 1989-08-11 | Asahi Glass Co Ltd | 改良された除湿膜 |
JPH02135118A (ja) * | 1988-11-15 | 1990-05-24 | Asahi Glass Co Ltd | 低湿度空気の製造方法 |
JP2000350918A (ja) * | 1999-06-10 | 2000-12-19 | Japan Science & Technology Corp | 除湿方法およびその装置 |
JP2006150323A (ja) * | 2004-11-01 | 2006-06-15 | Japan Gore Tex Inc | 隔膜およびその製法、並びに該隔膜を備えた熱交換器 |
JP2009072701A (ja) * | 2007-09-20 | 2009-04-09 | Agc Engineering Co Ltd | 凝集水除去器 |
JP2010005515A (ja) | 2008-06-25 | 2010-01-14 | Japan Gore Tex Inc | 複合膜及びそれを用いた水分量調整モジュール |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4802988A (en) * | 1987-09-17 | 1989-02-07 | Texaco Inc. | Dehydration of glycols |
US5004861A (en) * | 1988-07-05 | 1991-04-02 | Texaco Inc. | Process for pervaporization using membrane separating means |
US4971699A (en) * | 1990-01-02 | 1990-11-20 | Texaco Inc. | Separation of compositions containing water and organic oxygenates |
US5938928A (en) * | 1991-08-01 | 1999-08-17 | Nonap Pty. Ltd. | Osmotic distillation process using a membrane laminate |
US5141649A (en) * | 1991-10-07 | 1992-08-25 | Texaco Inc. | Novel membrane and method of separation |
US5418054A (en) | 1993-03-16 | 1995-05-23 | W. L. Gore & Associates, Inc. | Flame-retardant, waterproof and breathable expanded PTFE laminate |
US5681433A (en) * | 1994-09-14 | 1997-10-28 | Bend Research, Inc. | Membrane dehydration of vaporous feeds by countercurrent condensable sweep |
US5547551A (en) * | 1995-03-15 | 1996-08-20 | W. L. Gore & Associates, Inc. | Ultra-thin integral composite membrane |
US5599614A (en) * | 1995-03-15 | 1997-02-04 | W. L. Gore & Associates, Inc. | Integral composite membrane |
US6062866A (en) * | 1998-03-27 | 2000-05-16 | Prom; James M. | Medical angioplasty model |
US20030034304A1 (en) * | 2001-08-17 | 2003-02-20 | Huang Robert Y.M. | N-acetylated chitosan membranes |
US6755975B2 (en) * | 2002-06-12 | 2004-06-29 | Membrane Technology And Research, Inc. | Separation process using pervaporation and dephlegmation |
WO2007019350A2 (en) * | 2005-08-03 | 2007-02-15 | Donaldson Company, Inc. | Microporous membrane for flash distillation |
US8293112B2 (en) * | 2006-10-27 | 2012-10-23 | Cms Technologies Holdings, Inc. | Removal of water and methanol from fluids |
PL2145916T3 (pl) | 2008-07-17 | 2013-11-29 | Gore W L & Ass Gmbh | Powłoka substratu zawierająca kompleks jonowego fluoropolimeru i powierzchniowo naładowanych nanocząstek |
SG160281A1 (en) * | 2008-10-02 | 2010-04-29 | Sulzer Chemtech Gmbh | Composite membrane for the separation of water and method for its manufacture |
US9346021B2 (en) * | 2008-12-02 | 2016-05-24 | Membrane Distillation Desalination Ltd., Co. | Composite membranes for membrane distillation and related methods of manufacture |
JP2012206062A (ja) * | 2011-03-30 | 2012-10-25 | Nihon Gore Kk | 複合膜 |
-
2011
- 2011-03-30 JP JP2011075382A patent/JP2012206062A/ja active Pending
-
2012
- 2012-03-30 CA CA2831772A patent/CA2831772C/en active Active
- 2012-03-30 WO PCT/JP2012/058641 patent/WO2012133805A1/ja active Application Filing
- 2012-03-30 AU AU2012233249A patent/AU2012233249A1/en not_active Abandoned
- 2012-03-30 KR KR1020137024870A patent/KR101570916B1/ko active IP Right Grant
- 2012-03-30 CN CN201280016576.6A patent/CN103459005B/zh active Active
- 2012-03-30 US US14/008,584 patent/US9358507B2/en active Active
- 2012-03-30 EP EP12765268.3A patent/EP2692421B1/en active Active
-
2016
- 2016-01-22 AU AU2016200400A patent/AU2016200400B2/en active Active
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS59203602A (ja) | 1983-05-02 | 1984-11-17 | Asahi Chem Ind Co Ltd | 複合膜 |
JPS6157205A (ja) | 1984-08-27 | 1986-03-24 | Nitto Electric Ind Co Ltd | サ−モパ−ベ−パレ−シヨン法による水溶液の処理方法 |
JPH01199625A (ja) * | 1988-02-04 | 1989-08-11 | Asahi Glass Co Ltd | 改良された除湿膜 |
JPH02135118A (ja) * | 1988-11-15 | 1990-05-24 | Asahi Glass Co Ltd | 低湿度空気の製造方法 |
JP2000350918A (ja) * | 1999-06-10 | 2000-12-19 | Japan Science & Technology Corp | 除湿方法およびその装置 |
JP2006150323A (ja) * | 2004-11-01 | 2006-06-15 | Japan Gore Tex Inc | 隔膜およびその製法、並びに該隔膜を備えた熱交換器 |
JP2009072701A (ja) * | 2007-09-20 | 2009-04-09 | Agc Engineering Co Ltd | 凝集水除去器 |
JP2010005515A (ja) | 2008-06-25 | 2010-01-14 | Japan Gore Tex Inc | 複合膜及びそれを用いた水分量調整モジュール |
Non-Patent Citations (1)
Title |
---|
See also references of EP2692421A4 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109855377A (zh) * | 2017-11-30 | 2019-06-07 | 青岛海尔股份有限公司 | 冷藏冷冻装置及其储物容器 |
CN109855377B (zh) * | 2017-11-30 | 2020-10-30 | 青岛海尔股份有限公司 | 冷藏冷冻装置及其储物容器 |
Also Published As
Publication number | Publication date |
---|---|
AU2012233249A1 (en) | 2013-10-24 |
KR101570916B1 (ko) | 2015-11-20 |
AU2016200400B2 (en) | 2017-06-15 |
EP2692421B1 (en) | 2022-07-06 |
EP2692421A1 (en) | 2014-02-05 |
CA2831772C (en) | 2017-10-24 |
JP2012206062A (ja) | 2012-10-25 |
US9358507B2 (en) | 2016-06-07 |
US20140110332A1 (en) | 2014-04-24 |
CA2831772A1 (en) | 2012-10-04 |
CN103459005B (zh) | 2015-12-09 |
EP2692421A4 (en) | 2014-09-03 |
AU2016200400A1 (en) | 2016-02-11 |
CN103459005A (zh) | 2013-12-18 |
KR20130137208A (ko) | 2013-12-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
WO2012133805A1 (ja) | 複合膜 | |
JP5156504B2 (ja) | 複合膜及びそれを用いた水分量調整モジュール | |
KR101900241B1 (ko) | 이축배향 다공막, 복합체, 및 제조방법 및 용도 | |
KR101989901B1 (ko) | 필터여재, 이의 제조방법 및 이를 포함하는 필터모듈 | |
US20070151447A1 (en) | Gas separation membranes and processes for controlled environmental management | |
JP6667603B2 (ja) | 複合膜 | |
WO2012018089A1 (ja) | 隔膜およびこれを用いた熱交換器 | |
KR101572660B1 (ko) | 나노섬유웹층을 포함하는 역삼투막 및 그 제조방법 | |
Zhu et al. | Novel poly (vinylidene fluoride)/thermoplastic polyester elastomer composite membrane prepared by the electrospinning of nanofibers onto a dense membrane substrate for protective textiles | |
JP2016155129A (ja) | 複合膜 | |
JP2006179273A (ja) | 複合水蒸気透過膜 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 12765268 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 20137024870 Country of ref document: KR Kind code of ref document: A |
|
ENP | Entry into the national phase |
Ref document number: 2831772 Country of ref document: CA |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2012765268 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2012233249 Country of ref document: AU Date of ref document: 20120330 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14008584 Country of ref document: US |