WO2009119638A1 - ポリマー繊維体、その製造方法及び流体濾過用フィルタ - Google Patents
ポリマー繊維体、その製造方法及び流体濾過用フィルタ Download PDFInfo
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- WO2009119638A1 WO2009119638A1 PCT/JP2009/055901 JP2009055901W WO2009119638A1 WO 2009119638 A1 WO2009119638 A1 WO 2009119638A1 JP 2009055901 W JP2009055901 W JP 2009055901W WO 2009119638 A1 WO2009119638 A1 WO 2009119638A1
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
- D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
- B01D39/16—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres
- B01D39/1607—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous
- B01D39/1623—Other self-supporting filtering material ; Other filtering material of organic material, e.g. synthetic fibres the material being fibrous of synthetic origin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28023—Fibres or filaments
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J47/00—Ion-exchange processes in general; Apparatus therefor
- B01J47/12—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes
- B01J47/127—Ion-exchange processes in general; Apparatus therefor characterised by the use of ion-exchange material in the form of ribbons, filaments, fibres or sheets, e.g. membranes in the form of filaments or fibres
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- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/48—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polymers of halogenated hydrocarbons
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H3/00—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length
- D04H3/02—Non-woven fabrics formed wholly or mainly of yarns or like filamentary material of substantial length characterised by the method of forming fleeces or layers, e.g. reorientation of yarns or filaments
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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
- B01D2239/06—Filter cloth, e.g. knitted, woven non-woven; self-supported material
- B01D2239/0604—Arrangement of the fibres in the filtering material
- B01D2239/0631—Electro-spun
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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
- B01D2239/10—Filtering material manufacturing
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- 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
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/637—Including strand or fiber material which is a monofilament composed of two or more polymeric materials in physically distinct relationship [e.g., sheath-core, side-by-side, islands-in-sea, fibrils-in-matrix, etc.] or composed of physical blend of chemically different polymeric materials or a physical blend of a polymeric material and a filler material
Definitions
- the present invention relates to a hybrid polymer fiber body comprising a non-electrolyte polymer and an electrolyte polymer, and a method for producing the same. Moreover, this invention relates to the filter for fluid filtration which consists of this hybrid polymer fiber body.
- Pleated ion exchange filters are widely used for high purity treatment of ultrapure water used in semiconductor manufacturing processes.
- This pleated ion exchange filter is a flat membrane such as a nonwoven fabric or a porous membrane made into a pleated shape.
- the flow tends to be biased in the pleat folding portion, and a sufficient removal rate cannot be obtained in the extremely low concentration region as described above. Further, since the film thickness is thin, breakthrough is quick and the life is short. From the viewpoint of particle removal, as described above, long life and high removal performance are problems. If the film thickness is increased or the pores of the film are reduced in order to improve the ion removal rate, there is a problem that water permeability is sacrificed.
- An electrospinning method (electrostatic spinning method) is known as a method for producing ultrafine nanofibers having a fiber diameter of the order of nanometers (JP 2006-144138, JP 2007-92237).
- electrospinning method an electric field is formed between a nozzle and a target, and spinning is performed by discharging a liquid raw material from the nozzle in the form of fine fibers. The fine fibers are accumulated on the target to form a fibrous body.
- Non-electrolyte polymer and electrolyte polymer each have excellent features and disadvantages when made into fibers. The following points are mentioned as the characteristics of the non-electrolyte polymer and the characteristics of the electrolyte polymer.
- non-electrolyte polymers have high mechanical strength and chemical resistance, but are difficult to wet (low hydrophilicity) and have poor dyeability (low ionic substance adsorptivity).
- the electrolyte polymer has high hydrophilicity and high dyeability, but has a problem in terms of spinnability and mechanical strength.
- Polyvinylidene fluoride which has been conventionally used as a material for ion exchange filters, is a material having high heat resistance, but is hydrophobic and has to be subjected to a hydrophilic treatment with plasma or the like.
- An object of the present invention is to provide a hybrid polymer fiber body having both properties and advantages of both a non-electrolyte polymer and an electrolyte polymer, a method for producing the same, and a filter for fluid filtration comprising the fiber body.
- the method for producing a polymer fibrous body according to the present invention includes a non-electrolyte polymer in a mixed solvent containing at least a first solvent having a water concentration of 10% by weight or less in which the non-electrolyte polymer is soluble and a second solvent in which the electrolyte polymer is soluble And a raw material solution preparation step of preparing a raw material solution in which the electrolyte polymer is dissolved, and a step of electrospinning using the mixed solution.
- a method for producing a polymer fiber body according to a first preferred embodiment includes at least a first solvent having a water concentration of 10% by weight or less in which a non-electrolyte polymer is soluble, and a second solvent in which an electrolyte polymer is soluble, Preparing a mixed solvent in which both are dissolved, preparing a mixed solution by dissolving the non-electrolyte polymer and the electrolyte polymer in the mixed solvent, and electrospinning using the mixed solution It is characterized by.
- the method for producing a polymer fiber body according to the second preferred embodiment comprises a step of preparing a first solution by dissolving a non-electrolyte polymer in a first solvent having a water concentration of 10% by weight or less, and dissolving the electrolyte polymer in a second solvent.
- a step of preparing a second solution a step of mixing the first solution and the second solution so that both the polymers maintain a dissolved state, and preparing a mixed solution, and using the mixed solution.
- a step of electrospinning is a step of electrospinning.
- a method for producing a polymer fiber body according to a third preferred embodiment is characterized in that, in the first or second embodiment, the non-electrolyte polymer and / or the electrolyte polymer is a fluoropolymer.
- the method for producing a polymer fiber body according to a fourth preferred embodiment is characterized in that, in any one of the first to third embodiments, the non-electrolytic polymer is polyvinylidene fluoride.
- the method for producing a polymer fiber body according to a fifth preferred embodiment is characterized in that, in any one of the first to fourth embodiments, the electrolyte polymer is a perfluorocarbon sulfonic acid type polymer.
- the solvent of the mixed solution contains at least alcohol and water, and the polymer concentration is 5 to 40% by weight. It is characterized by being.
- the solution in which the non-electrolyte polymer and the electrolyte polymer are dissolved is maintained at a high temperature by the gelation temperature to perform electrospinning. It is a feature.
- the method for producing a polymer fiber body according to an eighth preferred aspect is the method according to any one of the first to seventh aspects, wherein the second solvent is a solvent having a water concentration of 10% by weight or more and a solvent having a boiling point higher than that of water. And then dewatering by evaporation to reduce the concentration of water to 10% by weight or less.
- the second solvent is a solvent having a water concentration of 10% by weight or more and a solvent having a boiling point higher than that of water.
- the method for producing a polymer fiber body according to a ninth preferred embodiment is characterized in that, in the eighth embodiment, the evaporation is performed while decreasing the temperature of the solvent stepwise or continuously.
- the polymer fiber body of the present invention is produced by the above method.
- the polymer fiber body is preferably laminated on a planar or perforated hollow body.
- the polymer fiber body provided by the present invention is a hybrid polymer fiber body composed of a non-electrolyte polymer and an electrolyte polymer.
- This hybrid polymer fiber body can be used for various applications such as clothing, curtains, adsorbents, in addition to filters for fluid filtration. Since many non-electrolyte polymers are easily fiberized by electrospinning, a hybrid polymer fiber body containing an electrolyte polymer can be easily produced by electrospinning a mixed solution containing the non-electrolyte polymer and the electrolyte polymer. be able to.
- the filter of the present invention is composed of, for example, an electrospun hybrid polymer fiber nonwoven fabric. This filter has no drift like a pleated filter and has a long life. And permeation flux can be kept high over a long period of time.
- the mechanical strength, hydrophilicity, charge and other characteristics of the spun hybrid polymer fiber body can be controlled. Therefore, in the treatment of fluids such as air, organic gas, water, aqueous solution, organic solvent, or in the treatment of gas-liquid mixtures, a small amount of metals, organic substances, fine particles, etc. contained in the fluid to be treated are adsorbed and separated.
- fluids such as air, organic gas, water, aqueous solution, organic solvent, or in the treatment of gas-liquid mixtures.
- a small amount of metals, organic substances, fine particles, etc. contained in the fluid to be treated are adsorbed and separated.
- filters suitable for the above can be provided.
- this filter is used as an air filter, it is possible to separate charged substances such as amines.
- the filter of the present invention is suitable for use in the production of ultrapure water and the like, and can reduce the concentration of metal ions in ultrapure water to an extremely low concentration.
- it is sometimes required in the electronic component manufacturing process to treat high-temperature water at 50 ° C. or higher (eg, 60 to 100 ° C.).
- high-temperature water at 50 ° C. or higher (eg, 60 to 100 ° C.).
- 2 is a photomicrograph showing the product of Comparative Example 1.
- 2 is a photomicrograph of the fiber of Example 1.
- 2 is a photomicrograph of the fiber of Example 2.
- 6 is a photomicrograph showing a hydrophilicity test of a nonwoven fabric of Comparative Example 2.
- 2 is a photomicrograph showing the hydrophilicity test of the nonwoven fabric of Example 1.
- the method for producing a polymer fiber body of the present invention includes a step of preparing a mixed solution containing a non-electrolyte polymer and an electrolyte polymer that can be independently electrospun, and electrospinning the mixed solution.
- an extremely thin fiber having an equivalent diameter of about 1 to 1000 nm, particularly about 10 to 700 nm is preferable.
- the length of the ultrafine fiber is preferably 1 ⁇ m or more.
- the length can be several tens of centimeters, and since continuous spinning is possible, the length can be increased without an upper limit.
- Non-electrolyte polymer and first solvent The non-electrolyte polymer is not particularly limited as long as predetermined water permeability and strength can be secured in the case of a fiber.
- Non-electrolyte polymers include polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyhydroxycarboxylic acid, PTFE, CTFE, PFA, fluororesins such as polyvinylidene fluoride (PVDF), polyvinyl chloride, etc.
- polyolefins such as polyethylene and polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyesters such as polyhydroxycarboxylic acid, PTFE, CTFE, PFA, fluororesins such as polyvinylidene fluoride (PVDF), polyvinyl chloride, etc.
- PVDF polyvinylidene fluoride
- Polyamide such as halogenated polyolefin, nylon-6, nylon-66, urea resin, phenol resin, melamine resin, polystyrene, cellulose, cellulose acetate, cellulose nitrate, polyether ketone, polyether ketone ketone, polyether ether ketone, polysulfone, Polyethersulfone, polyimide, polyetherimide, polyamideimide, polybenzimidazole, polycarbonate, polyphenylene resin Fido, polyacrylonitrile, polyether nitrile, and the material can be used, such as a copolymer thereof, it is not limited thereto. In particular, it is not limited to one kind of material, and various materials can be selected as necessary.
- a fluororesin having heat resistance is preferable, and PVDF is particularly preferable.
- Solvents (first solvent) for dissolving this non-electrolytic polymer include alcohols such as methanol, ethanol, propanol and isopropanol, ketones, ethers, N-methylpyrrolidone, dimethylformamide, dimethylacetamide (DMAc), formamide, dimethylsulfo It is preferable to select and use one in which the polymer is soluble from oxide (DMSO), chlorine-based solvent, fluorine-based solvent and the like.
- the water concentration in the polymer solution is preferably 10% by weight or less.
- the electrolyte polymer is preferably a polymer having an anionic or cationic functional group.
- the ionic functional group include a sulfo group, a carboxyl group, a phosphate group, and a primary to quaternary amino group.
- the base polymer of the electrolyte polymer include polymers of the above-mentioned non-electrolyte polymer. Among them, polyethylene, polystyrene, polysulfone, a polymer having a polyamide heterocyclic ring, a fluororesin, a polyamino acid, and the like are preferable.
- an electrolyte polymer having heat resistance an electrolyte polymer having fluorine is preferable, and for example, a fluororesin having a sulfo group is preferable.
- a fluororesin having a sulfo group introduced include commercially available Nafion (registered trademark). Nafion is mainly composed of perfluorosulfonic acid / polytetrafluoroethylene copolymer.
- the same solvents as described above can be used as the solvent for the electrolyte polymer (second solvent).
- a mixed solvent including a first solvent for dissolving the non-electrolyte polymer and a second solvent for dissolving the electrolyte polymer is prepared, and the electrolyte polymer and the non-electrolyte polymer are added to the mixed solvent. Dissolve.
- This mixed solvent may consist of only the first solvent and the second solvent, or may further include another third solvent.
- the third solvent include water, alcohol, chlorine-based solvent, and fluorine-based solvent.
- a first solution is prepared by dissolving a non-electrolyte polymer in a first solvent
- a second solution is prepared by dissolving an electrolyte polymer in a second solvent.
- the two solutions are mixed to prepare a mixed solution.
- the total polymer concentration of the non-electrolyte polymer and the electrolyte polymer in the mixed solution is preferably about 5 to 40% by weight.
- Solvent selection is based on solubility parameters.
- the solubility parameter of the solvent is divided into dispersion force ⁇ D, polarity ⁇ P, and hydrogen bond strength ⁇ H, and the solubility parameter when solvent A and B are mixed in the ratio of X: Y (weight ratio) is obtained by the following formula, and this value To determine the solvent mixing ratio. The same is true when the solvent has three or more components.
- ⁇ D has been described as an example, the same applies to ⁇ P and ⁇ H.
- ⁇ D (X ⁇ DA + Y ⁇ DB) / (X + Y)
- Nafion (product number 527122) is soluble in water and 1-propanol. Since Nafion has a charge, the value of ⁇ H affects the solubility. There is the following relationship between the concentration of Nafion and ⁇ H required to maintain a dissolved state at that concentration. [When Nafion concentration is 16% by weight, ⁇ H> 7 When 8% by weight, ⁇ H> 5.5]
- PVDF polyvinylidene fluoride
- Nafion is dissolved in the following mixed solvents up to a concentration of 8% and PVDF is dissolved up to a concentration of 10% by weight.
- ⁇ H of the solution in which Nafion dissolves it is possible to lower ⁇ H of the solution in which Nafion dissolves than the above value. That is, as the second solvent, a solvent having a slightly higher water content and a water concentration of 10% by weight or more can be used, but a solvent having a boiling point higher than that of water (such as DMAc) is added to this solvent. Then, by performing dehydration by evaporation, the concentration of water in the solvent can be reduced to 10% by weight or less, whereby ⁇ H of the solvent can be lowered.
- a solvent having a slightly higher water content and a water concentration of 10% by weight or more can be used, but a solvent having a boiling point higher than that of water (such as DMAc) is added to this solvent. Then, by performing dehydration by evaporation, the concentration of water in the solvent can be reduced to 10% by weight or less, whereby ⁇ H of the solvent can be lowered.
- the polymer precipitates when it is rapidly evaporated and dehydrated, so after roughing water at a high temperature, the temperature of the solvent is lowered stepwise or continuously and gradually evaporated at a low temperature. It is preferable to perform dehydration.
- the polymer mixed solution becomes below a certain temperature, it may gel and interfere with polymer discharge in electrospinning. In that case, it is necessary to heat the electrospinning so that it does not gel and maintain it at a temperature higher than the gelling temperature.
- liquidity of a solution improves by making it high temperature, and it is advantageous to polymer discharge.
- FIG. 1 is a schematic perspective view for explaining this manufacturing method.
- a voltage is applied between the discharge port 1 and the target (opposite surface portion) 3 so that the discharge port 1 side is positive and the target 3 side is negative.
- the mixed solution of the non-electrolyte polymer is discharged toward the target 3, and the electrolyte polymer and the non-electrolyte polymer are accumulated (deposited) on the target 3 to manufacture the hybrid polymer fiber body 2.
- the distance between the discharge port 1 and the target 3 is preferably about 50 to 500 mm, particularly about 70 to 300 mm. It is preferable that the applied voltage between the two has a potential gradient of about 1 to 20 kV / cm.
- the fiber discharged from the discharge port 1 and flying toward the target 3 is heated to promote the evaporation of the solvent in the fiber. Good.
- the atmosphere of the fiber flying zone may be heated, and infrared rays may be irradiated toward the flying zone.
- the evaporation of the solvent may be promoted by heating the fibers deposited on the target 3 or the hybrid polymer fiber taken out from the target 3.
- a thin film is placed on the target for spinning, and after spinning, the thin film is peeled off to obtain a self-supporting hybrid polymer fiber body.
- polyolefin such as polyethylene, polyester, polysulfone, aluminum foil and the like can be used.
- a base material-integrated hybrid polymer fiber body can be obtained by placing a porous body on the target and spinning to integrate the porous body as a base material.
- a porous body a nonwoven fabric, a sintered body, a separation membrane, or the like can be selected.
- polyolefin such as polyethylene and polypropylene
- polyester, polysulfone, cellulose derivative and the like can be used.
- a material of the sintered body a polymer such as polyolefin, a metal such as stainless steel, glass, or the like can be used.
- As a material for the separation membrane polyolefin, polyester, polysulfone, cellulose derivative, polyamide, or the like can be used.
- the filter for fluid filtration is produced using the hybrid polymer fiber body obtained as described above, the filter for fluid filtration is produced by laminating the hybrid polymer fiber body in a planar shape or on a porous hollow body. can do.
- this filter is used, fluid is circulated through the filter in the deposition direction on the target 3 (perpendicular to the surface of the target 3).
- the thickness of the filter is preferably about 0.05 to 50 mm, and the bulk density is preferably about 0.2 to 0.5 g / cm 3 . Further, the water flow SV is preferably about 500 to 15000 hr ⁇ 1 .
- the filter of the present invention is suitable for use when ultrapure water having a metal ion concentration of 0.5 to 5 ng / L is filtered to reduce the metal ion concentration to about 0.1 ng / L or less.
- the filter of the present invention can also be used for processing liquids other than water.
- the solvent is partially evaporated by adding another solvent of the first solvent or the second solvent to the solution in which the non-electrolyte polymer or the electrolyte polymer is dissolved, and then heating the solution.
- the composition may be changed.
- FIG. 2 is a photograph of platinum (Pt) deposited on a sample and photographed with an electron microscope at a magnification of 1000 times.
- a fiber of 500 nm could be spun, and a polymer fiber body having a thickness of 50 ⁇ m made of this fiber could be produced. Moreover, the nonwoven fabric flat film of thickness 2mm was able to be produced by laminating
- Example 1 A solution containing 10% by weight of PVDF, 8.3% by weight of Nafion, 4.2% by weight of water, 4.2% by weight of 1-propanol and 73.3% by weight of DMAc was prepared as a solution containing a non-electrolyte polymer and an electrolyte polymer.
- This solution was easily gelled, it was heated during spinning and maintained at about 45 ° C.
- FIG. 3 is a photograph taken with an electron microscope with platinum deposited on the obtained fiber and magnification of 1000 times.
- a 200 nm fiber could be spun and a 50 ⁇ m thick hybrid polymer fiber body comprising this fiber could be produced.
- the nonwoven fabric flat film of thickness 2mm was able to be produced by laminating
- Example 2 A solution containing 15% by weight of PVDF, 4.2% by weight of Nafion, 2.1% by weight of water, 2.1% by weight of 1-propanol, and 76.6% by weight of DMAc was prepared as a solution containing a non-electrolyte polymer and an electrolyte polymer.
- This solution was easily gelled, it was heated during spinning and maintained at about 45 ° C.
- FIG. 4 is a photograph taken with an electron microscope at a magnification of 1000 with platinum deposited on the obtained fiber.
- the concentration of each metal can be reduced to 0.1 ng / L or less.
- Example 3 DMAc 40 mL as a solvent having a boiling point higher than that of water was added to 50 mL of an electrolyte polymer solution of Nafion 20 wt%, 1-propanol 40 wt%, and water 40 wt%, and the temperature was 100 ° C. for 1 hour, and the temperature was 80 ° C. for 2 hours. Hold for 8 hours at a temperature of 60 ° C., gradually evaporate water and 1-propanol having a boiling point lower than that of DMAc, 20% by weight of Nafion, 79 to 80% by weight of DMAc, and 1% by weight of 1-propanol and water are less than 1% by weight.
- An electrolyte polymer solution (second solution) was prepared. At this time, ⁇ H was 5.0.
- This second solution was mixed with a non-electrolyte polymer solution (first solution) of 20% by weight of PVDF and 80% by weight of DMAc at a weight ratio of 5: 5.
- a mixed solution of 10 wt% and DMAc 79-80 wt% was prepared.
- Example 4 In the same manner as in Example 3, an electrolyte polymer solution (second solution) containing 20% by weight of Nafion, 79 to 80% by weight of DMAc, and 1% by weight or less of 1-propanol and water was prepared.
- the second solution and the first solution were mixed at a weight ratio of 7: 3 to prepare a mixed solution of 6% by weight of PVDF, 14% by weight of Nafion, and 79 to 80% by weight of DMAc as a solution containing the non-electrolyte polymer and the electrolyte polymer. . *
- Example 5 DMSO 40 mL as a solvent having a boiling point higher than that of water was added to 50 mL of an electrolyte polymer solution of Nafion 20 wt%, 1-propanol 40 wt%, and water 40 wt%, and the temperature was 100 ° C. for 1 hour, and the temperature was 80 ° C. for 2 hours. Hold for 8 hours at a temperature of 60 ° C., gradually evaporate water and 1-propanol having a boiling point lower than that of DMSO, Nafion 20 wt%, DMSO 79 to 80 wt%, 1-propanol and water are 1 wt% or less.
- An electrolyte polymer solution (second solution) was prepared.
- This second solution was mixed with a non-electrolyte polymer solution (first solution) of 20% by weight PVDF and 80% by weight DMSO at a weight ratio of 5: 5, and a solution containing the non-electrolyte polymer and the electrolyte polymer was 10% by weight PVDF, Nafion A mixed solution of 10% by weight and DMSO 79-80% by weight was prepared.
- first solution 20% by weight PVDF and 80% by weight DMSO at a weight ratio of 5: 5
- a solution containing the non-electrolyte polymer and the electrolyte polymer was 10% by weight PVDF
- Nafion A mixed solution of 10% by weight and DMSO 79-80% by weight was prepared.
- Spinning was performed under the same conditions as in Comparative Example 1, and fibers of about 400 nm could be spun.
- Example 6 Except for using quaternary ammoniumated polysulfone instead of Nafion, quaternary ammoniumated polysulfone 20% by weight, DMAc 79-80% by weight, 1-propanol and water were 1% by weight or less in the same manner as in Example 1. An electrolyte polymer solution (second solution) was prepared.
- This second solution is mixed with a non-electrolytic polymer solution (first solution) of 20% by weight PVDF and 80% by weight of DMAc at a weight ratio of 5: 5 to obtain a quaternary ammonium-modified polysulfone as a solution containing the non-electrolytic polymer and the electrolyte polymer.
- first solution 20% by weight PVDF and 80% by weight of DMAc at a weight ratio of 5: 5
- a mixed solution of 10% by weight, PVDF 10% by weight, and DMAc 79-80% by weight was prepared.
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Abstract
Description
単独で電界紡糸することが容易なものがある。
電界紡糸後、繊維同士の反発がないため、成膜し易い。
疎水性のもの、親水性のものを選択できる。
疎水性のものは耐水性を有するが、水を通しにくい。
単独で電界紡糸することが難しい。
電界紡糸出来ても繊維同士の反発により、かさ(嵩)が高くなって収まりが悪くなり(即ち、嵩密度が低くなり)、成膜に適さない。
親水性を有する。
イオン性物質の吸着性を有する。
水への溶解性を有するものもある。
非電解質ポリマーは、繊維とした場合に所定の透水性、強度を確保できるものであれば特に限定されない。
電解質ポリマーは、アニオン性又はカチオン性の官能基を有するポリマーが好適である。このイオン性の官能基としてはスルホ基、カルボキシル基、リン酸基、1~4級のアミノ基などが例示される。電解質ポリマーのベースポリマーとしては、上記非電解質ポリマーのポリマーが例示され、中でもポリエチレン、ポリスチレン、ポリスルホン、ポリアミド複素環を有するポリマー、フッ素樹脂、ポリアミノ酸などが好ましい。耐熱性を有する電解質ポリマーとしては、フッ素を有する電解質ポリマーが好適であり、例えばスルホ基を有するフッ素樹脂が好適である。スルホ基を導入したフッ素樹脂としては、市販のナフィオン(Nafion、登録商標)などが例示される。ナフィオンはパーフルオロスルホン酸/ポリテトラフロロエチレン共重合体を主成分とする。
本発明の一態様では、上記非電解質ポリマーを溶解するための第1溶媒と、電解質ポリマーを溶解するための第2溶媒とを含む混合溶媒を調製し、この混合溶媒に電解質ポリマー及び非電解質ポリマーを溶解させる。
δD=(XδDA+YδDB)/(X+Y)
[ナフィオン濃度16重量%のとき、δH>7 8重量%のとき、δH>5.5]
[PVDF濃度20重量%のとき、δH<5.5 10重量%のとき、δH<6.1]
即ち、水の濃度が低いほどPVDFが溶けやすいため、水の濃度は低い方が好ましく、相関するδHも低い方が好ましい。
水:1-プロパノール:ジメチルアセトアミド=2:2:35.2、δD=8.15、δP=5.59、δH=5.98
以下、この電解質ポリマー及び非電解質ポリマーを溶解させた混合溶液を電界紡糸してハイブリッドポリマー繊維体を製造する方法について、図面を参照して説明する。
<紡糸条件>
シリンジ径30Gのシリンジにナフィオン20重量%、1-プロパノール40重量%、水40重量%の電解質ポリマー溶液を入れ、シリンジ側をプラス、繊維を捕集するターゲット側にマイナスの35kVの電圧(4kV/cmの電位勾配)をかけることにより、ナフィオン繊維の紡糸を試みた。
第2図に示すように、ナフィオンは粒径1~3μmの粒子状となってしまい、不織布を作製することはできなかった。第2図は、試料に白金(Pt)を蒸着させ、電子顕微鏡にて倍率1000倍にて撮影した写真である。
ポリフッ化ビニリデン(PVDF)を20重量%含む、ジメチルアセトアミド(DMAc)の非電解質ポリマー溶液を調製し、これを比較例1と同様の条件で紡糸を試みた。
500nmの繊維を紡糸でき、この繊維からなる厚さ50μmのポリマー繊維体を作製することができた。また、このポリマー繊維体を平面状に積層することにより厚さ2mmの不織布平膜を作製することができた。
非電解質ポリマーと電解質ポリマーとを含む溶液としてPVDF10重量%、ナフィオン8.3重量%、水4.2重量%、1-プロパノール4.2重量%、DMAc73.3重量%の溶液を調製し、これを比較例1と同様の条件で紡糸を試みた。なお、この溶液はゲル化しやすいため、紡糸の際加温して45℃程度に保持した。第3図は、得られた繊維に白金を蒸着させ、倍率1000倍にて電子顕微鏡で撮影した写真である。
第3図の通り、200nmの繊維を紡糸でき、この繊維からなる厚さ50μmのハイブリッドポリマー繊維体を作製することができた。また、このハイブリッドポリマー繊維体を平面状に積層することにより、厚さ2mmの不織布平膜を作製することができた。
非電解質ポリマーと電解質ポリマーとを含む溶液としてPVDF15重量%、ナフィオン4.2重量%、水2.1重量%、1-プロパノール2.1重量%、DMAc76.6重量%の溶液を調製し、これを比較例1と同様の条件で紡糸を試みた。なお、この溶液はゲル化しやすいため、紡糸の際加温して45℃程度に保持した。第4図は、得られた繊維に白金を蒸着させ、倍率1000倍にて電子顕微鏡で撮影した写真である。
第4図の通り、400nmの繊維を紡糸することができ、この繊維からなる厚さ50μmのハイブリッドポリマー繊維体を作製することができた。また、このハイブリッドポリマー繊維体を平面状に積層することにより、厚さ2mmの不織布平膜を作製することができた。
比較例2及び実施例1で作製した不織布平膜からなるフィルタを5重量%の塩酸で十分に洗浄した後、超純水で塩酸を洗い流した。膜面積13cm2のフィルタホルダーに設置し、被処理水の金属(Na,Mg,Al,K,Ca,Cr,Fe,Cu,Zn)濃度がそれぞれ10ng/Lになるように原子吸光用標準液を超純水に添加して原水を調製した。この原水をフィルタに濾過差圧30kPaで通水処理し、20L処理した時点の水質と透過流束を測定した。測定はサンプリング水を濃縮してから、ICPMS(横河アナリティカルシステムズAgilent-4500)で分析した。なお、比較例2では、超純水による上記洗浄後にフィルタをアルコールで親水化した。
比較例2で作製した不織布平膜を、1%メチレンブルーで染色しようとしたが、染色できなかった。一方、実施例1,2で作製した不織布平膜は青色に染まった。従って、本発明のハイブリッドポリマー繊維体はイオン性物質(ここでは色素成分)の吸着性能を有することが分かった。
比較例2及び実施例1で作製した不織布平膜にそれぞれ10μLの水滴を滴下した結果、比較例2では第5図のように不織布平膜に浸透せず球状の水滴ができたが、実施例1では第6図のように不織布平膜は水に濡れ、接触角が90度以下になった。従って本発明のハイブリッドポリマー繊維体からなる不織布平膜は親水性能を有することが分かった。
ナフィオン20重量%、1-プロパノール40重量%、水40重量%の電解質ポリマー溶液50mLに水よりも高沸点の溶媒としてDMAc40mLを添加して、温度100℃で1時間、温度80℃で2時間、温度60℃で8時間、順次保持し、DMAcよりも低沸点の水と1-プロパノールを徐々に蒸発させ、ナフィオン20重量%、DMAc79~80重量%、1-プロパノールと水は1重量%以下の電解質ポリマー溶液(第2溶液)を調製した。このときのδHは5.0であった。
実施例3と同様の方法で、ナフィオン20重量%、DMAc79~80重量%、1-プロパノールと水は1重量%以下の電解質ポリマー溶液(第2溶液)を調製した。
ナフィオン20重量%、1-プロパノール40重量%、水40重量%の電解質ポリマー溶液50mLに水よりも高沸点の溶媒としてDMSO40mLを添加して、温度100℃で1時間、温度80℃で2時間、温度60℃で8時間、順次保持し、DMSOよりも低沸点の水と1-プロパノールを徐々に蒸発させ、ナフィオン20重量%、DMSO79~80重量%、1-プロパノールと水は1重量%以下の電解質ポリマー溶液(第2溶液)を調製した。
ナフィオンの代りに4級アンモニウム化ポリスルホンを使用したこと以外は実施例1と同様の方法により、4級アンモニウム化ポリスルホン20重量%、DMAc79~80重量%、1-プロパノールと水は1重量%以下の電解質ポリマー溶液(第2溶液)を調製した。
Claims (12)
- 非電解質ポリマーが可溶な水濃度10重量%以下の第1溶媒と、電解質ポリマーが可溶な第2溶媒とを少なくとも含む混合溶媒に前記非電解質ポリマーと電解質ポリマーとが溶解した原料溶液を作製する原料溶液作製工程と、
該混合溶液を用いて電界紡糸する工程と
を有することを特徴とするポリマー繊維体の製造方法。 - 請求項1において、前記原料溶液作製工程は、前記第1溶媒と、前記第2溶媒とを少なくとも含み、前記両ポリマーが共に溶解する混合溶媒を調製する工程と、
該混合溶媒に前記非電解質ポリマーと電解質ポリマーとを溶解させて原料溶液を作製する工程と
を有することを特徴とするポリマー繊維体の製造方法。 - 請求項1において、前記原料溶液作製工程は、非電解質ポリマーを前記第1溶媒に溶解させて第1溶液を調製する工程と、
電解質ポリマーを前記第2溶媒に溶解させて第2溶液を調製する工程と、
前記第1溶液と第2溶液とを、前記両ポリマーが共に溶解状態を維持するように混合して原料溶液を調製する工程と
を有することを特徴とするポリマー繊維体の製造方法。 - 請求項1において、非電解質ポリマー及び/又は電解質ポリマーがフッ素系重合体であることを特徴とするポリマー繊維体の製造方法。
- 請求項1において、非電解質ポリマーがポリフッ化ビニリデンであることを特徴とするポリマー繊維体の製造方法。
- 請求項1において、電解質ポリマーがパーフルオロカーボンスルフォン酸型重合体であることを特徴とするポリマー繊維体の製造方法。
- 請求項1において、前記原料溶液の溶媒が少なくともアルコール及び水を含むものであり、ポリマー濃度が5~40重量%であることを特徴とするポリマー繊維体の製造方法。
- 請求項1において、前記原料溶液をゲル化温度よりも高温に保持して電界紡糸することを特徴とするポリマー繊維体の製造方法。
- 請求項1において、前記第2溶媒は、水の濃度が10重量%以上の溶媒に、水よりも高沸点の溶媒を添加し、次いで蒸発による脱水を行うことにより水の濃度を10重量%以下に低減して調製したものであることを特徴とするポリマー繊維体の製造方法。
- 請求項9において、前記蒸発は、段階的又は連続的に溶媒の温度を低下させながら行われることを特徴とするポリマー繊維体の製造方法。
- 請求項1乃至10のいずれか1項に記載の方法によって製造されたポリマー繊維体。
- 請求項11に記載のポリマー繊維体を有する流体濾過用フィルタ。
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JP2011201289A (ja) * | 2010-03-03 | 2011-10-13 | Kurita Water Ind Ltd | 複層シート |
JP2012127008A (ja) * | 2010-12-13 | 2012-07-05 | Kurita Water Ind Ltd | ナノファイバー不織布の製造方法及び装置 |
JP2016120490A (ja) * | 2011-04-01 | 2016-07-07 | イー・エム・デイー・ミリポア・コーポレイシヨン | ナノファイバー含有複合材構造体 |
JP2018108582A (ja) * | 2011-04-01 | 2018-07-12 | イー・エム・デイー・ミリポア・コーポレイシヨン | ナノファイバー含有複合材構造体 |
US11154821B2 (en) | 2011-04-01 | 2021-10-26 | Emd Millipore Corporation | Nanofiber containing composite membrane structures |
JP2013237942A (ja) * | 2012-05-14 | 2013-11-28 | Tokyo Metropolitan Univ | ナノファイバー、複合膜、高分子電解質膜、燃料電池用触媒層及び燃料電池 |
US12059644B2 (en) | 2014-06-26 | 2024-08-13 | Emd Millipore Corporation | Filter structure with enhanced dirt holding capacity |
US10675588B2 (en) | 2015-04-17 | 2020-06-09 | Emd Millipore Corporation | Method of purifying a biological material of interest in a sample using nanofiber ultrafiltration membranes operated in tangential flow filtration mode |
Also Published As
Publication number | Publication date |
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KR101217070B1 (ko) | 2012-12-31 |
CN101981242A (zh) | 2011-02-23 |
CN101981242B (zh) | 2012-08-08 |
JPWO2009119638A1 (ja) | 2011-07-28 |
TW201006975A (en) | 2010-02-16 |
EP2258896A4 (en) | 2012-06-20 |
JP5206787B2 (ja) | 2013-06-12 |
EP2258896A1 (en) | 2010-12-08 |
US20110011792A1 (en) | 2011-01-20 |
TWI381073B (zh) | 2013-01-01 |
KR20100113167A (ko) | 2010-10-20 |
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