WO2022215685A1 - 中空糸膜の製造方法 - Google Patents
中空糸膜の製造方法 Download PDFInfo
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- WO2022215685A1 WO2022215685A1 PCT/JP2022/017059 JP2022017059W WO2022215685A1 WO 2022215685 A1 WO2022215685 A1 WO 2022215685A1 JP 2022017059 W JP2022017059 W JP 2022017059W WO 2022215685 A1 WO2022215685 A1 WO 2022215685A1
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- fiber membrane
- hollow fiber
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- 239000012528 membrane Substances 0.000 title claims abstract description 116
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 103
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 20
- 238000000034 method Methods 0.000 title abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 133
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 24
- 239000011347 resin Substances 0.000 claims abstract description 24
- 229920005989 resin Polymers 0.000 claims abstract description 24
- 238000009987 spinning Methods 0.000 claims abstract description 24
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims description 85
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 12
- 238000000578 dry spinning Methods 0.000 claims 1
- 238000002166 wet spinning Methods 0.000 claims 1
- 239000011550 stock solution Substances 0.000 abstract description 12
- 238000001891 gel spinning Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 abstract description 3
- 238000005259 measurement Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 16
- 238000011156 evaluation Methods 0.000 description 15
- 230000035699 permeability Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000010828 elution Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000005191 phase separation Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000005345 coagulation Methods 0.000 description 3
- 230000015271 coagulation Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 229920006393 polyether sulfone Polymers 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000002145 thermally induced phase separation Methods 0.000 description 2
- 229930185605 Bisphenol Natural products 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229920000491 Polyphenylsulfone Polymers 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 229920000110 poly(aryl ether sulfone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- -1 that is Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
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Classifications
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- 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
- D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
- D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
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- B01D69/087—Details relating to the spinning process
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- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
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- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
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- D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
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- 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
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- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
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- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4391—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres
- D04H1/43914—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece characterised by the shape of the fibres hollow fibres
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- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
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- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06C—FINISHING, DRESSING, TENTERING OR STRETCHING TEXTILE FABRICS
- D06C7/00—Heating or cooling textile fabrics
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Definitions
- the present invention relates to a method for manufacturing hollow fiber membranes.
- porous membranes such as microfiltration membranes and ultrafiltration membranes
- porous membranes used in the water purification field are applied not only to sterilization of clean water but also to sterilization and turbidity removal in the sewage field.
- polysulfone-based porous membranes such as polysulfone and polyethersulfone, which are excellent in heat resistance, chemical resistance, mechanical properties and moldability, are widely used.
- Water permeability and separation performance are required as filtration performance of porous membranes used in the water purification field. These water permeability and separation performance are determined by the surface structure and internal structure of the membrane, and greatly depend on the manufacturing method of the porous membrane. For example, Patent Document 1 discloses that both virus removal performance and water permeability performance are achieved by controlling the short diameter and long diameter of the pores on the surface of the hollow fiber membrane within a desired range.
- a method that uses phase separation is widely known as a method for manufacturing membranes with excellent water permeability and separation performance.
- methods using liquid phase separation such as the non-solvent induced phase separation method described in Patent Document 2 and the thermally induced phase separation method described in Patent Document 3 are known.
- a hydrophobic resin that is a raw material of the hollow fiber membrane, a hydrophilic polymer substance that imparts hydrophilicity to the resin, and a water solution that dissolves them are used.
- a spinning dope containing mainly a organic solvent is discharged into a coagulation bath through a double ring nozzle together with a core liquid, and then washed to produce a hollow fiber membrane.
- the used organic solvent may remain in the hollow fiber membrane after membrane formation.
- a polysulfone-based resin is used as the resin, it is difficult to completely remove the organic solvent contained in the skeleton of the polysulfone only by washing with water or the like.
- Patent Documents 1 to 3 disclose properties such as permeation performance of the obtained hollow fiber membranes, they do not mention organic solvent components remaining in the hollow fiber membranes. Therefore, it is desired to develop a hollow fiber membrane that can further reduce the concentration of the organic solvent remaining in the hollow fiber membrane and ensure a high level of safety.
- the present invention reduces the organic solvent remaining in the hollow fiber membrane and provides a method for manufacturing a highly safe hollow fiber membrane.
- a method for producing a hollow fiber membrane according to an embodiment of the present invention comprises 10% by mass or more and 40% by mass or less of a polysulfone-based resin, 1% by mass or more and 30% by mass or less of polyvinylpyrrolidone, and 1% by mass or more and 80% by mass or less of A spinning stock solution containing N,N-dimethylformamide is discharged from a double ring nozzle together with a core liquid to prepare a hollow fiber membrane by dry-wet spinning. Dry heat treatment is performed for 48 hours or more and 168 hours or less.
- the core liquid contains 30% by mass or more and 100% by mass or less of N,N-dimethylformamide.
- the polysulfone-based resin is a polysulfone resin.
- the concentration of N,N-dimethylformamide remaining in the hollow fiber membrane after the dry heat treatment is 10 ppm or less.
- the concentration of N,N-dimethylformamide eluted from the hollow fiber membrane immersed in water after the dry heat treatment is 90 ppb or less.
- the spun hollow fiber membrane is washed with warm water before the dry heat treatment.
- the present invention it is possible to reduce the organic solvent remaining in the hollow fiber membrane and provide a method for manufacturing a highly safe hollow fiber membrane.
- FIG. 1 is a graph showing the relationship between the drying time and the concentration of N,N-dimethylformamide remaining in the hollow fiber membrane for each sample prepared in Examples.
- FIG. 2 is a graph showing the vapor pressure curve of N,N-dimethylformamide.
- FIG. 3 is a graph showing the relationship between the washing time with water and the concentration of N,N-dimethylformamide eluted from the hollow fiber membrane.
- FIG. 4 is a graph showing the concentration of N,N-dimethylformamide eluted from hollow fiber membranes when dry heat treatment was not performed and when dry heat treatment was performed.
- a spinning stock solution containing predetermined amounts of a polysulfone-based resin, polyvinylpyrrolidone and N,N-dimethylformamide (hereinafter also referred to as “DMF”) is prepared together with a core liquid.
- DMF N,N-dimethylformamide
- the hollow fiber membrane in this state is subjected to a dry heat treatment at a temperature equal to or higher than the inflection point of the vapor pressure curve of the water-soluble organic solvent used, so that the hollow fiber membrane remains in the hollow fiber membrane and furthermore, can remove the concentration of the water-soluble organic solvent, that is, DMF, contained in the skeleton of , to the order of ppb.
- the concentration of the organic solvent remaining in the hollow fiber membrane is extremely low, and a highly safe hollow fiber membrane can be produced.
- polysulfone-based resins examples include polysulfone resins, polyphenylsulfone resins, polyethersulfone resins, polyarylethersulfone resins, bisphenol A-type polysulfone resins, etc. Polysulfone resins are preferably used.
- polysulfone resin For the polysulfone resin, commercially available products such as the Udel (registered trademark) series manufactured by Solvay Specialty Polymers and the Ultrason (registered trademark) S series manufactured by BASF can be used.
- the content of the polysulfone-based resin contained in the spinning stock solution is 10% by mass or more and 40% by mass or less, preferably 12% by mass or more and 25% by mass or less.
- the blending ratio of the polysulfone-based resin is 10% by mass or more, the decrease in the strength of the hollow fiber membrane during spinning is suppressed, and further, the formation of the hollow fiber membrane is facilitated, and the spinning is performed more reliably. can be done.
- the blending ratio of the polysulfone-based resin is 40% by mass or less, holes are easily formed in the hollow fiber membrane, so that deterioration of water permeability can be suppressed.
- the spinning dope containing polysulfone as a spinning (film-forming) component further contains polyvinylpyrrolidone and DMF.
- Polyvinylpyrrolidone is added as a hydrophilic polymeric substance.
- the weight average molecular weight (Mw) of polyvinylpyrrolidone is preferably 1,000 or more and 1,200,000 or less, more preferably 10,000 or more and 120,000 or less.
- Examples of such polyvinylpyrrolidone include commercially available products such as "PVP K-30" manufactured by BASF.
- the content of polyvinylpyrrolidone contained in the spinning stock solution is 1% by mass or more and 30% by mass or less, preferably 5% by mass or more and 20% by mass or less.
- the blending ratio of polyvinylpyrrolidone is 1% by mass or more, it is possible to impart sufficient hydrophilicity to the hollow fiber membrane, prevent the pore size of the hollow fiber membrane from becoming small, and reduce the water permeability. can be suppressed. Moreover, since the mixing ratio of polyvinylpyrrolidone is 30% by mass or less, the spinning stock solution is stable, so clouding can be suppressed and spinning can be performed more reliably.
- DMF is added as a water-soluble organic solvent that dissolves the polysulfone resin.
- the content of DMF contained in the spinning stock solution is not particularly limited, but is preferably 1% by mass or more and 80% by mass or less, more preferably 50% by mass or more and 75% by mass.
- the spinning stock solution may further contain water as necessary, and may contain 1% by mass or less, preferably 0.3% by mass or more and 1% by mass or less of water.
- the production of the hollow fiber membrane is carried out by dry-wet spinning by discharging the spinning dope containing the above components from a double ring nozzle together with the core liquid.
- the core liquid preferably contains 30% by mass or more and 100% by mass or less of DMF.
- the core liquid is used as a solution, it is used as an aqueous solution containing water.
- DMF with a concentration of 30% by mass or more and 100% by mass or less as the core liquid, it is possible to improve the water permeability of the hollow fiber membrane.
- the discharged spinning dope is coagulated in a coagulation bath such as water and then washed in a washing bath such as water.
- the obtained hollow fiber membrane is subjected to dry heat treatment at a temperature of 80°C or higher and 100°C or lower for 48 hours or longer and 168 hours or shorter.
- Dry heat treatment can be performed using, for example, a precision thermostat.
- the heating temperature in the dry heat treatment is in the range of 80° C. or more and 100° C. or less, and the heating time is 48 hours or more and 168 hours or less, so that DMF remaining in the hollow fiber membrane can be significantly reduced and safe. It is possible to provide a method for producing a hollow fiber membrane with high toughness.
- the spun hollow fiber membrane may be washed with warm water before the dry heat treatment. In this case, washing is performed in pressurized water at a temperature of 121° C. or more and 125° C. or less for 1 hour or more and 2 hours or less using an autoclave or the like. do.
- the concentration of DMF remaining in the hollow fiber membrane after dry heat treatment is preferably 10 ppm or less, and the concentration of DMF eluted from the hollow fiber membrane immersed in water after dry heat treatment is preferably 90 ppb or less. is preferred.
- the lower limit of the heating temperature in dry heat treatment depends on the temperature at the inflection point of the vapor pressure curve of DMF contained in the spinning dope.
- FIG. 2 is a graph representing the vapor pressure curve of DMF, showing that the temperature at the inflection point is about 70°C.
- the heating temperature in the dry heat treatment is 80° C. or higher, it is higher than the temperature of the inflection point in the vapor pressure curve of DMF, so that DMF is easily volatilized and can be reduced to the desired concentration.
- the heating temperature in the dry heat treatment is 100°C or less, crosslinking of polyvinylpyrrolidone used as a hydrophilic polymer substance is prevented, and the characteristics of the hollow fiber membrane such as separation performance and water permeability performance are greatly changed. It is possible to suppress Moreover, since the heating time in the dry heat treatment is 48 hours or longer, the DMF can be more reliably reduced to the desired concentration at a temperature above the inflection point in the vapor pressure curve of DMF. On the other hand, even if the heating time in the dry heat treatment exceeds 168 hours, the concentration of the remaining DMF is constant, so from the viewpoint of efficiency, the upper limit of the heating time in the dry heat treatment is 168 hours or less. When the heating temperature in the dry heat treatment is 100° C., the DMF can be reduced to the desired concentration even if the heating time is 24 hours or more.
- the average pore size of the hollow fiber membrane is not particularly limited, it is, for example, 20 nm or more and 200 nm or less.
- the hollow fiber membrane according to the present embodiment has a significantly low concentration of DMF remaining in the hollow fiber membrane and is highly safe. It is suitable for application to
- Example 1 A spinning stock solution containing 19% by weight of polysulfone (“Ultrason® S3010”, manufactured by BASF), 9% by weight of polyvinylpyrrolidone (“PVP K-30”, manufactured by BASF) and 72% by weight of DMF was prepared at room temperature. .
- a hollow fiber membrane was obtained by discharging the resulting spinning stock solution from a double annular nozzle into a water coagulation bath by a dry-wet spinning method using a core liquid containing 60% by mass of DMF and 40% by mass of water. After that, the obtained hollow fiber membrane was subjected to dry heat treatment at 80° C. for 48 hours in a precision thermostat (“DFS810”, manufactured by Yamato Scientific Co., Ltd.).
- Example 2 A hollow fiber membrane was produced in the same manner as in Example 1, except that in the dry heat treatment, the heating time was changed to 72 hours, and the above measurements and evaluations were performed. The results are shown in FIG. Note that the corresponding plots in FIG. 1 are also duplicated, as the results of the DMF measurements were the same for both runs.
- Example 3 A hollow fiber membrane was produced in the same manner as in Example 1, except that the heating time was changed to 96 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 4 A hollow fiber membrane was produced in the same manner as in Example 1, except that in the dry heat treatment, the heating time was changed to 168 hours, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 5 A hollow fiber membrane was produced in the same manner as in Example 1, except that the heating temperature was changed to 100° C. in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 6 A hollow fiber membrane was produced in the same manner as in Example 5, except that the heating time was changed to 72 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 7 A hollow fiber membrane was produced in the same manner as in Example 5, except that in the dry heat treatment, the heating time was changed to 96 hours, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 8 A hollow fiber membrane was produced in the same manner as in Example 5, except that the heating time was changed to 120 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 1 A hollow fiber membrane was produced in the same manner as in Example 1, except that in the dry heat treatment, the heating temperature was 70° C. and the heating time was 24 hours, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 2 A hollow fiber membrane was produced in the same manner as in Example 1, except that in the dry heat treatment, the heating temperature was set to 70° C. and the heating time was set to 48 hours, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 3 A hollow fiber membrane was produced in the same manner as in Example 1 except that in the dry heat treatment, the heating temperature was set to 70° C. and the heating time was set to 72 hours, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 4 A hollow fiber membrane was produced in the same manner as in Example 1, except that the heating temperature was set to 70° C. and the heating time was set to 96 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 5 A hollow fiber membrane was produced in the same manner as in Example 1, except that the heating temperature was set to 70° C. and the heating time was set to 120 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- Example 6 A hollow fiber membrane was produced in the same manner as in Example 1, except that the heating temperature was set to 70° C. and the heating time was set to 168 hours in the dry heat treatment, and the above measurements and evaluations were performed. The results are shown in FIG.
- FIG. 1 shows the DMF concentration when each heating temperature (70° C., 80° C., 100° C.) is 0 hours.
- a hollow fiber membrane produced using a spinning stock solution containing a predetermined component is subjected to a dry heat treatment at a temperature of 80° C. or higher and 100° C. or lower for 48 hours or more and 168 hours or less.
- the concentration of residual DMF was reduced to less than 10 ppm. Therefore, by the production methods in Examples 1 to 8, the organic solvent remaining in the hollow fiber membrane was reduced, and a highly safe hollow fiber membrane could be produced. In particular, it was confirmed that the higher the dry heat temperature, the higher the DMF removal effect.
- the hollow fiber membrane was applied to a hollow fiber membrane module for water purifiers, and the concentration of DMF eluted from the hollow fiber membrane module was measured. Since the elution standard value of DMF in NSF certification is stipulated to be 90 ppb or less, if the DMF concentration eluted from the hollow fiber membrane is 90 ppb or less, it can be said that a highly safe hollow fiber membrane has been obtained. evaluated.
- the DMF concentration was measured when the hollow fiber membrane was subjected to a washing treatment in which water was passed through for a certain period of time (flow rate: 3 L/min) instead of performing a dry heat treatment.
- flow rate 3 L/min
- FIG. 3 even if water washing was performed for 240 minutes (4 hours) or more, the DMF elution standard value (90 ppb or less) in NSF certification could not be satisfied.
- the hollow fiber membranes were subjected to dry heat treatment at 80°C for 120 hours and at 100°C for 72 hours, respectively, each hollow fiber membrane after the dry heat treatment was immersed in the extraction test filtrate, and the concentration of DMF recovered from the filtrate was measured. did.
- a hollow fiber membrane as it was without dry heat treatment was also immersed in the extraction test filtrate, and the concentration of DMF recovered from the filtrate was measured.
- the results are shown in FIG. As shown in FIG. 4, by subjecting the hollow fiber membrane to a dry heat treatment, the eluted DMF concentration achieved less than the DMF elution standard value (90 ppb) certified by the NSF.
- the manufacturing method of the present invention even in the NSF certification, which is a very strict standard as a safety standard in the field of water purifiers, it is possible to produce a hollow fiber membrane with less than the elution standard value. It is useful for application to a highly safe and reliable hollow fiber membrane module for water purifiers.
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Abstract
Description
ポリスルホン(「Ultrason(登録商標)S3010」、BASF社製)19質量%、ポリビニルピロリドン(「PVP K-30」、BASF社製)9質量%およびDMF72質量%を含む紡糸原液を室温にて調製した。
GC-MS(島津製作所社製)を用いて、中空糸膜中に残存するDMFを測定した。中空糸膜中のDMF濃度が10ppm以下であれば、作業環境測定基準における管理濃度を満たすため、安全性の高い中空糸膜が得られていると評価した。
乾熱処理において、加熱時間を72時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。なお、DMF測定の結果が2回とも同じであったため、図1において対応するプロットも重複している。
乾熱処理において、加熱時間を96時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱時間を168時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を100℃とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱時間を72時間とした以外は、実施例5と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱時間を96時間とした以外は、実施例5と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱時間を120時間とした以外は、実施例5と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を24時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を48時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を72時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を96時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を120時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理において、加熱温度を70℃とし、かつ加熱時間を168時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
乾熱処理を行わず、紡糸後の中空糸膜に対して上記の測定および評価を行った。その結果を図1に示す。なお、便宜上、図1では各加熱温度(70℃、80℃、100℃)が0時間である場合におけるDMF濃度を示す。
乾熱処理において、加熱温度を100℃とし、かつ加熱時間を24時間とした以外は、実施例1と同様にして中空糸膜を作製して、上記の測定および評価を行った。その結果を図1に示す。
Claims (6)
- 10質量%以上40質量%以下のポリスルホン系樹脂、1質量%以上30質量%以下のポリビニルピロリドン、および1質量%以上80質量%以下のN,N-ジメチルホルムアミドを含有する紡糸原液を、芯液と共に二重環ノズルより吐出し、乾湿式紡糸により中空糸膜を作製した後、前記中空糸膜を80℃以上100℃以下の温度で48時間以上168時間以下乾熱処理することを特徴とする中空糸膜の製造方法。
- 前記芯液が、30質量%以上100質量%以下のN,N-ジメチルホルムアミドを含有する、請求項1に記載の中空糸膜の製造方法。
- 前記ポリスルホン系樹脂が、ポリスルホン樹脂である請求項1または2に記載の中空糸膜の製造方法。
- 前記乾熱処理後に中空糸膜中に残存するN,N-ジメチルホルムアミドの濃度が、10ppm以下である請求項1または2に記載の中空糸膜の製造方法。
- 前記乾熱処理後に水中に浸漬した中空糸膜から溶出されるN,N-ジメチルホルムアミドの濃度が、90ppb以下である請求項1または2に記載の中空糸膜の製造方法。
- 前記乾熱処理前に、紡糸した中空糸膜を温水で洗浄する請求項1または2に記載の中空糸膜の製造方法。
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JP2002045662A (ja) * | 2000-08-07 | 2002-02-12 | Toyobo Co Ltd | 選択透過性中空糸膜 |
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WO2020004212A1 (ja) * | 2018-06-26 | 2020-01-02 | Nok株式会社 | 加湿用多孔質中空糸膜の製造法 |
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