WO2015133364A1 - 複合微多孔質膜及びこれを用いたフィルター - Google Patents

複合微多孔質膜及びこれを用いたフィルター Download PDF

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Publication number
WO2015133364A1
WO2015133364A1 PCT/JP2015/055639 JP2015055639W WO2015133364A1 WO 2015133364 A1 WO2015133364 A1 WO 2015133364A1 JP 2015055639 W JP2015055639 W JP 2015055639W WO 2015133364 A1 WO2015133364 A1 WO 2015133364A1
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Prior art keywords
microporous membrane
composite microporous
polyvinylidene fluoride
layer
fluoride resin
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PCT/JP2015/055639
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English (en)
French (fr)
Japanese (ja)
Inventor
修 古嶋
直 長迫
山口　修
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Jnc株式会社
Jnc石油化学株式会社
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Priority to JP2016506449A priority Critical patent/JP6447623B2/ja
Publication of WO2015133364A1 publication Critical patent/WO2015133364A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • 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
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02832—1-10 nm
    • 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
    • B01D71/02—Inorganic material
    • B01D71/04—Glass
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • 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
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage

Definitions

  • the present invention relates to a microporous membrane suitable for water treatment applications such as a membrane separation activated sludge method (membrane bioreactor: MBR).
  • MBR membrane separation activated sludge method
  • PVDF polyvinylidene fluoride
  • the PVDF microporous membrane can be produced by a non-solvent induced phase separation method (by preparing a solution in which a polymer is dissolved in a good solvent and immersing this solution thinly on a glass plate or the like in a non-solvent. For example, a method of inducing phase separation to obtain a microporous membrane) (for example, Patent Document 1).
  • the PVDF microporous membrane Since the PVDF microporous membrane is hydrophobic, it needs to be subjected to a hydrophilization treatment by coating it with a hydrophilizing agent such as polyvinyl alcohol (PVA) or by replacing it with ethanol in order to use it for water treatment.
  • a hydrophilizing agent such as polyvinyl alcohol (PVA)
  • PVA polyvinyl alcohol
  • Patent Document 2 the hydrophilized microporous membrane obtained by this method has poor persistence of the hydrophilizing effect, and the hydrophilizing effect is lost when all of PVA and ethanol are eluted.
  • PVA polyvinyl alcohol
  • the object of the present invention is to provide a composite microporous membrane for water treatment that has no permanent clogging due to coating with a hydrophilizing agent and has permanent hydrophilicity, and a filter using the same. There is to do.
  • the composite microporous membrane according to the first aspect of the present invention is characterized in that a SiO 2 glass layer is coated on the surface of at least one side of a microporous membrane containing a polyvinylidene fluoride resin.
  • a SiO 2 glass layer is coated on the surface of at least one side of a microporous membrane containing a polyvinylidene fluoride resin.
  • the composite microporous membrane according to the second aspect of the present invention is the composite microporous membrane according to the first aspect of the invention, wherein the microporous membrane containing the polyvinylidene fluoride resin is a non-solvent induced phase. It is produced by a separation method. With this configuration, the skin layer in which the pore diameter changes in the thickness direction of the membrane (see the left side of FIG. 8), and the pores larger than the pores supporting the skin layer and the skin layer in which the pores are formed are formed. Since it has the structure provided with the formed support layer, the filtration accuracy is maintained by the skin layer, and the permeability can be secured by the support layer.
  • the composite microporous membrane according to the third aspect of the present invention is the composite microporous membrane according to the first or second aspect of the invention, wherein the microporous membrane containing a polyvinylidene fluoride resin is An asymmetric membrane, comprising a skin layer in which micropores are formed and a support layer in which pores larger than the micropores are formed to support the skin layer, the skin layer having a plurality of spherical bodies, A plurality of linear binders extend from each of the spherical bodies in a three-dimensional direction, and the adjacent spherical bodies are connected to each other by the linear binders, and a three-dimensional network having the spherical bodies as intersections. Form a structure.
  • FIG. 1 shows an example of a three-dimensional network structure according to the present invention.
  • FIG. 1 is a scanning electron microscope (SEM) photograph of the skin layer surface.
  • the “skin layer” refers to the layer from the surface to the macro void in the cross section of the microporous membrane containing the polyvinylidene fluoride resin
  • the “support layer” refers to the fine layer containing the polyvinylidene fluoride resin.
  • “Macrovoid” refers to a huge cavity that occurs in a support layer of a microporous membrane and has a minimum size of several ⁇ m and a maximum size approximately the same as the thickness of the support layer.
  • the “spherical body” is a sphere formed at the intersection of the three-dimensional network structure, and is not limited to a perfect sphere, but includes almost a sphere. With this configuration, the gap between the sphere and the sphere is partitioned by a linear binder, making it easy to form micropores of uniform shape and size, and a skin layer with excellent permeability. Can be formed. Since the linear binding material also serves to crosslink the spherical body, the spherical body does not fall off and the filtering medium itself can be prevented from being mixed into the filtrate. Furthermore, since a spherical body exists at the intersection of the three-dimensional network structure, the skin layer can be prevented from being crushed by pressure when used as a filtration membrane.
  • the pressure resistance is high. Furthermore, the three-dimensional network structure as shown in FIG. 1 using a spherical body and a linear binder makes the skin layer voids smaller than conventional microporous membranes containing a polyvinylidene fluoride resin having the same pore size. Therefore, the passage is maintained, and the voids are more uniformly and three-dimensionally arranged.
  • the composite microporous membrane according to the fourth aspect of the present invention is the composite microporous membrane according to the third aspect of the present invention, wherein the spherical particles have a width within ⁇ 10% of the average particle size. In the range of 50% or more. If comprised in this way, the spherical body which a skin layer has will become the thing with the equal particle size. Therefore, a void having a uniform pore diameter is easily formed between the spherical body and the spherical body.
  • the composite microporous membrane according to the fifth aspect of the present invention is the composite microporous membrane according to the third aspect or the fourth aspect of the present invention, wherein the length of the binder is ⁇ the average length. It has a frequency distribution of 50% or more in a range of 30% width. If comprised in this way, the spherical body which a skin layer has will be disperse
  • the composite microporous membrane according to the sixth aspect of the present invention is the composite microporous membrane according to any one of the third to fifth aspects of the present invention, wherein the spherical body is 0 0.05 to 0.5 ⁇ m average particle size. If comprised in this way, a micropore will be easily formed between a spherical body and a spherical body with the spherical body which has the average particle diameter in the said range, and the linear binding material which connects a spherical body.
  • the composite microporous membrane according to the seventh aspect of the present invention is the composite microporous membrane according to any one of the third to sixth aspects of the present invention, wherein the thickness of the skin layer is 0.5 to 5 ⁇ m, and the thickness of the support layer is 20 to 500 ⁇ m.
  • the skin layer is a layer (functional layer) that removes impurities in the asymmetric membrane, the thinner it is within the range that does not hinder the formation of the three-dimensional network structure with the spherical body as an intersection, the lower the filtration resistance. Since it can be made small, it is preferable.
  • the support layer occupying most of the microporous membrane hardly contributes to the removal of impurities, but can be avoided by a support layer that is sufficiently thicker than the skin layer because it can be broken only by an extremely thin skin layer. it can.
  • the composite microporous membrane according to the eighth aspect of the present invention is the composite microporous membrane according to any one of the third to seventh aspects of the present invention, wherein the substrate supporting the support layer is provided.
  • a material layer is provided. If comprised in this way, a base material layer will become a reinforcing material and will be able to endure a higher filtration pressure.
  • a part of the support layer is mixed with the base material layer, and the boundary between them is not so clear. When there are too few mixed parts of a support layer and a base material layer, a support layer may become easy to peel from a base material layer.
  • the composite microporous membrane according to the ninth aspect of the present invention is the composite microporous membrane according to the first to eighth aspects of the present invention, wherein the weight average molecular weight (Mw) of the polyvinylidene fluoride-based resin is the same. ) Is between 600,000 and 1 million.
  • Mw weight average molecular weight
  • the polyvinylidene fluoride resin having the weight average molecular weight includes a skin layer having a three-dimensional network structure in which the spherical bodies and the spherical bodies formed by a linear binder that cross-links the spherical bodies are crossed.
  • a microporous film containing a polyvinylidene fluoride resin can be easily formed.
  • the composite microporous membrane according to the tenth aspect of the present invention is the composite microporous membrane according to any one of the first to ninth aspects of the present invention, the average flow pore diameter of which is 5 ⁇ 500 nm. If the average flow hole diameter is 5 nm or more, an increase in pressure loss due to clogging during filtration can be minimized, and if it is 500 nm or less, transmission of coarse impurity particles can be suppressed. The filtration performance is shown.
  • the composite microporous membrane according to the eleventh aspect of the present invention shows the shape of a flat membrane in the composite microporous membrane according to any one of the first to tenth aspects of the present invention. .
  • impurities are less likely to accumulate between the membranes, and an increase in pressure loss can be suppressed. Excellent filtration performance.
  • the filter according to the twelfth aspect of the present invention is a filter characterized by using the composite microporous membrane according to any one of the first to eleventh aspects of the present invention. If comprised in this way, the composite microporous film excellent in hydrophilic property and permeability
  • the method for producing a composite microporous membrane according to the thirteenth aspect of the present invention is the method for producing a composite microporous membrane according to any one of the first to eleventh aspects of the present invention.
  • Te after forming the coating film of the silica precursor on at least one side of the microporous film containing polyvinylidene fluoride resin, by the conversion of the silica precursor to SiO 2 glass, to form a SiO 2 glass layer , A production method for obtaining a microporous film containing a polyvinylidene fluoride resin at least one side coated with SiO 2 glass.
  • the method for producing a composite microporous membrane according to the fourteenth aspect of the present invention is the method for producing a composite microporous membrane according to the thirteenth aspect of the present invention, wherein the silica precursor is polysilazane. This is a method for producing a microporous membrane. When configured in this manner, it is possible to proceed with the conversion to SiO 2 glass layer having a dense structure with ease.
  • the method for producing a composite microporous membrane according to the fifteenth aspect of the present invention is the method for producing a composite microporous membrane according to the eighth aspect of the present invention, wherein the polyvinylidene fluoride resin is used as a good solvent.
  • the spherical bodies included in the skin layer are cross-linked with each other by a linear binder to form a three-dimensional network structure with the spherical bodies as intersections. Since the spherical bodies are more uniformly dispersed in a uniform size, the pores of the skin layer are uniformly dispersed and have excellent permeability.
  • a method for producing a composite microporous membrane according to a sixteenth aspect of the present invention is a method for producing a composite microporous membrane according to the ninth aspect of the present invention, wherein the polyvinylidene fluoride resin is used as a good solvent.
  • An application step of applying the dissolved raw material liquid onto a base material layer or a support and an immersion step of immersing the base material layer and the applied raw material liquid in a non-solvent after the application step are provided.
  • the composite microporous membrane of the present invention is a composite microporous membrane comprising a microporous membrane containing a polyvinylidene fluoride resin having a regular three-dimensional network structure whose surface is coated with a SiO 2 glass layer. Therefore, it has excellent heat resistance and chemical resistance, and has high porosity and permanent hydrophilicity.
  • FIG. 1 is a photograph of the surface of a skin layer of a microporous film containing a polyvinylidene fluoride resin in the present invention.
  • FIG. 2 is a photograph of a conventional filtration membrane made of polyvinylidene fluoride.
  • FIG. 3 is a flowchart showing a method for producing a composite microporous membrane according to the present invention.
  • 4 is a photograph of the surface of the skin layer of the composite microporous membrane of Example 1.
  • FIG. FIG. 5 is a photograph of the surface of the skin layer that the microporous membrane of Comparative Example 1 has.
  • 6A is a cross-sectional photograph of the composite microporous membrane of Example 1.
  • FIG. 6B is an enlarged photograph of a cross-sectional portion of the skin layer.
  • FIG. 7 is a photograph of the surface of the skin layer of the composite microporous membrane of Example 1, and is a photograph used to measure the particle size of the spherical body and the length of the linear binder.
  • FIG. 8 is a schematic diagram showing a cross-sectional view (left) of the asymmetric membrane and a cross-sectional view (right) of the symmetric membrane. (Source: JPO Homepage / 2005 Standard Technology Collection, Water Treatment Technology / 1-6-2-1 Symmetric Membrane and Asymmetric Membrane)
  • the composite microporous membrane in the present invention will be described.
  • the composite microporous membrane of the present invention has a structure in which the surface of a microporous membrane containing a polyvinylidene fluoride resin is covered with a SiO 2 glass layer, and the SiO 2 glass layer contains a hydrophobic polyvinylidene fluoride resin. It serves to impart hydrophilicity to the microporous membrane.
  • the SiO 2 glass layer is preferably formed by impregnating and coating the silica precursor solution over the entire pores of the microporous membrane containing the polyvinylidene fluoride resin, but the air permeability required for the composite microporous membrane
  • the polyvinylidene fluoride resin is contained so that at least one side of the surface of the microporous film containing the polyvinylidene fluoride resin is covered with the SiO 2 glass layer.
  • a SiO 2 glass layer may be formed on at least one side of the microporous film.
  • polyvinylidene fluoride resin used in the present invention examples include resins containing a vinylidene fluoride homopolymer and / or a vinylidene fluoride copolymer.
  • a polyvinylidene fluoride resin a plurality of types of vinylidene fluoride homopolymers having different physical properties (viscosity, molecular weight, etc.) may be contained. Alternatively, a plurality of types of vinylidene fluoride copolymers may be included.
  • the vinylidene fluoride copolymer is not particularly limited as long as it is a polymer having a vinylidene fluoride residue structure, and is typically a copolymer of a vinylidene fluoride monomer and other fluorine-based monomers. And a copolymer of one or more fluorine-based monomers selected from vinyl fluoride, ethylene tetrafluoride, propylene hexafluoride, and ethylene trifluoride chloride and vinylidene fluoride. Particularly preferred is a vinylidene fluoride homopolymer (polyvinylidene fluoride).
  • the microporous film containing the polyvinylidene fluoride resin used in the present invention can be constituted by using the above-mentioned polyvinylidene fluoride resin, but may further contain other components. Further, the microporous film containing the polyvinylidene fluoride resin used in the present invention may be a microporous film made of a polyvinylidene fluoride resin. In this case, other components may be included as long as the effects of the present invention are not hindered. Examples of other components include polymers other than polyvinylidene fluoride resins and additives such as antibacterial agents for imparting other characteristics.
  • the composite microporous membrane of the present invention has an asymmetric structure in which the pore diameter changes in the thickness direction of the membrane (see the left side of FIG. 8), the pore diameter of the layer (skin layer) near the surface of the membrane is the smallest, and goes to the back surface. As the hole diameter increases.
  • the skin layer has a pore size necessary for separation characteristics and functions as a functional layer.
  • the remaining portion is a layer that functions as a support layer, has a large pore size and a small permeation resistance, and maintains the flow path and membrane strength.
  • the thickness of the skin layer is preferably 0.5 to 5 ⁇ m, and the thickness of the support layer is preferably 20 to 500 ⁇ m.
  • FIG. 1 is a part of a photograph of the surface (skin layer side) of the composite microporous membrane of the present invention taken with a scanning electron microscope (SEM).
  • the skin layer has a plurality of spherical bodies 1, and a plurality of linear binders 2 extend from each spherical body 1 in a three-dimensional direction. They are connected by a linear binder 2 to form a three-dimensional network structure with the spherical body 1 as an intersection, and the generated voids are holes. Therefore, a hole is easily formed in the skin layer, and the hole is not easily deformed.
  • an asymmetric membrane has a dense thin layer called a skin layer, and this layer generally has few pores, so it is extremely effective to improve permeability by opening many holes that are difficult to deform in this layer. It is.
  • the permeability is greatly improved by the spherical body 1 included in the skin layer and the linear bonding material 2 connecting them. Therefore, it can have higher permeability than the conventional microporous membrane having the same average flow pore diameter.
  • the “average flow pore size” is a value obtained by ASTM F316-86, and when a composite microporous membrane is used as a filtration membrane, its inhibition particle size is greatly affected.
  • the average flow pore size of the composite microporous membrane is preferably 5 to 500 nm, more preferably 5 to 450 nm, and most preferably 10 to 400 nm. If the average pore size of the composite microporous membrane is 5 nm or more, an increase in pressure loss due to clogging during filtration can be minimized, and if it is 500 nm or less, transmission of coarse impurity particles is suppressed. Is preferable. Furthermore, as shown in FIG. 1, the spherical bodies 1 are almost uniform in size and are dispersed almost uniformly. Therefore, a skin layer is formed in which the shape and size of the gap formed between the spherical body 1 and the spherical body 1 are uniform.
  • the space between the spheres 1 is delimited by a linear binder 2 that bridges the adjacent spheres 1, and the resulting holes are egg-shaped or almost egg-shaped with no dents on the outer periphery curve.
  • a microporous membrane having a uniform pore shape is obtained.
  • FIG. 2 is a scanning electron micrograph of a conventional polyvinylidene fluoride filtration membrane having such a structure as an example.
  • the average particle diameter of the spherical body of the skin layer of the composite microporous membrane of the present invention is preferably 0.05 to 0.5 ⁇ m. More preferably, it is 0.1 to 0.4 ⁇ m, and still more preferably 0.2 to 0.3 ⁇ m. Most of the spherical particles have a value close to the average particle size and have a uniform size. Further, the average particle diameter varies depending on the produced microporous membrane, and the value has a range as described above. Therefore, various microporous membranes having different pore sizes formed in the skin layer and different average flow pore diameters can be obtained.
  • the particle size of the spherical body As for the particle size of the spherical body, at least 50 arbitrary spherical bodies were photographed using a scanning electron microscope (SEM) or the like at such a magnification that the spherical body could be clearly confirmed on the skin layer side surface of the composite microporous membrane. It can be obtained by measuring the particle size and averaging the number. Specifically, it is as described in the examples. As shown in FIG. 7, the “particle diameter” is the diameter of a perfect circle when the outer periphery of the spherical body is surrounded by a perfect circle having the maximum diameter that does not include the surrounding holes. In order to make the shape of the pores of the skin layer more uniform, the shape of each spherical body is preferably close to a perfect sphere, and the size of the spherical body is preferably small in variation.
  • SEM scanning electron microscope
  • the particle diameter of the spherical body preferably has a frequency distribution of 50% or more in the range of ⁇ 10% width of the average particle diameter in the frequency distribution. More preferably, it is 55% or more, More preferably, it is 60% or more.
  • the frequency of 50% or more is distributed in the range of the width of ⁇ 10% of the average particle diameter
  • the spherical body of the skin layer has a more uniform shape and size, and the pore size between the spherical body and the spherical body Can form uniform (aligned) voids.
  • the average length of the linear binding material of the skin layer of the composite microporous membrane of the present invention is preferably 0.05 to 0.5 ⁇ m. More preferably, it is 0.1 to 0.4 ⁇ m, and still more preferably 0.2 to 0.3 ⁇ m. Most of the lengths of the linear binders are close to the average length, and the length is uniform. Further, the average length varies depending on the produced microporous membrane, and the value has a width as described above. Therefore, various composite microporous membranes having different pore sizes formed in the skin layer and different average flow pore diameters can be obtained.
  • the average length of the linear binder is at least 100 by taking a photograph using a scanning electron microscope (SEM) or the like at a magnification at which the linear binder can clearly confirm the skin-side surface of the composite microporous membrane. It can be obtained by measuring the length of an arbitrary linear binding material of a book and averaging the number. Specifically, it is as described in the examples. As shown in FIG. 7, the “length of the linear binding material” is the distance between the perfect circles when the outer periphery of the spherical body is surrounded by a perfect circle having the maximum diameter so as not to include the surrounding holes. is there.
  • the length of the linear binder preferably has a frequency distribution of 50% or more in the range of ⁇ 30% of the average length in the frequency distribution. More preferably, it is 55% or more, More preferably, it is 60% or more.
  • the frequency of 50% or more is distributed in the range of the average length ⁇ 30%, the spherical bodies of the skin layer are more uniformly dispersed, and voids with a uniform or uniform pore diameter are formed between the spherical bodies and the spherical bodies. Can be formed.
  • the ratio of the average particle diameter of the spherical body to the average length of the linear binder is preferably between 3: 1 and 1: 3.
  • the average particle size of the spherical body is smaller than three times the average length of the linear binder, the opening on the skin layer surface of the composite microporous membrane becomes large, and a high permeation amount can be obtained more remarkably.
  • the average particle size of the spheres is larger than one third of the average length of the binder, the number of binders that can be connected to one sphere increases, so there is little dropout of the filter media and high pressure resistance. Features can be obtained more prominently.
  • the weight average molecular weight (Mw) of the polyvinylidene fluoride resin is preferably 600,000 to 1,000,000. More preferably, it is 700,000-950,000, and more preferably 790,000-900,000.
  • Mw weight average molecular weight
  • the selection range of a good solvent and a poor solvent, which will be described later, is widened, and it becomes easier to further increase the permeability and film strength of the microporous film containing the polyvinylidene fluoride resin.
  • the viscosity of the raw material liquid can be suppressed by making the weight average molecular weight (Mw) not much higher than 1 million, it becomes easy to apply uniformly, and the support layer and the base material layer This is preferable because a mixed portion is more easily formed.
  • a polyvinylidene fluoride resin having a weight average molecular weight (Mw) outside this range may be mixed.
  • the good solvent is a liquid capable of dissolving a necessary amount of the polyvinylidene fluoride resin under a temperature condition for applying the raw material liquid.
  • the non-solvent is a solvent that does not dissolve or swell the polyvinylidene fluoride-based resin under temperature conditions that replace the good solvent in the coating film with a non-solvent.
  • the poor solvent is a solvent that cannot dissolve the required amount of the polyvinylidene fluoride resin, but can dissolve or swell less than that amount.
  • Good solvents include N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide, N, N-dimethylacetamide (DMAc), N, N-dimethylformamide (DMF), methyl ethyl ketone, acetone, tetrahydrofuran, tetramethylurea, phosphorus Examples include lower alkyl ketones such as trimethyl acid, esters, amides, and the like. These good solvents may be used as a mixture, and may contain a poor solvent and a non-solvent as long as the effects of the present invention are not impaired. When film formation is performed at room temperature, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, and N, N-dimethylformamide are preferable.
  • Non-solvents include water, hexane, pentane, benzene, toluene, methanol, ethanol, carbon tetrachloride, o-dichlorobenzene, trichloroethylene, low molecular weight polyethylene glycol and other aliphatic hydrocarbons, aromatic hydrocarbons, chlorine Chlorinated hydrocarbons or other chlorinated organic liquids.
  • the non-solvent needs to be dissolved in a good solvent and is preferably mixed with the good solvent in a free ratio.
  • a good solvent or a poor solvent may be intentionally added to the non-solvent. Since the substitution rate of the good solvent and the non-solvent affects the expression of the three-dimensional network structure in the present invention, the combination thereof is also important.
  • NMP / water, DMAc / water, DMF / water, and the like are preferable from the viewpoint of easy expression of a three-dimensional network structure, and a combination of DMAc / water is particularly preferable.
  • a porosifying agent for promoting porosity to the raw material solution for film formation.
  • the porous agent is not limited as long as it does not inhibit the dissolution of the polyvinylidene fluoride resin in a good solvent, dissolves in a non-solvent, and promotes the microporous membrane to become porous. Absent.
  • Examples include organic high-molecular substances or low-molecular substances, such as water-soluble polymers such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, and polyacrylic acid, and sorbitan fatty acid esters.
  • water-soluble polymers such as polyethylene glycol, polypropylene glycol, polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, and polyacrylic acid, and sorbitan fatty acid esters.
  • Low ethylene oxide such as ester of polyhydric alcohol such as (mono, triester, etc.), ethylene oxide low molar adduct of sorbitan fatty acid ester, ethylene oxide low molar adduct of nonylphenol, pluronic ethylene oxide low molar adduct Mole adducts, polyoxyethylene alkyl esters, alkylamine salts, surfactants such as sodium polyacrylate, polyhydric alcohols such as glycerin, tetraethylene glycol, triethylene glycol, etc. Mention may be made of the recall class. These may be used alone or in a mixture of two or more.
  • porous agents preferably have a weight average molecular weight (Mw) of 50,000 or less, more preferably 30,000 or less, and still more preferably 10,000 or less. If the weight average molecular weight of the porosifying agent is within the above range, it is preferable because it is uniformly dissolved in the polyvinylidene fluoride resin solution. This porous agent is considered to remain in the microporous membrane containing the polyvinylidene fluoride resin for a relatively long time as compared with the good solvent when the good solvent is extracted in the non-solvent and the structural aggregation occurs. As the porous agent when water is used as the non-solvent, polyethylene glycol is particularly preferable because it can easily exhibit these functions, and those having a weight average molecular weight of 200 to 1000 are more preferable.
  • Mw weight average molecular weight
  • the obtained porous resin containing the polyvinylidene fluoride resin has porosity. Get higher.
  • the resulting structure depends on the type of porous agent, molecular weight, added amount, and the like.
  • the porosifying agent is preferably added in an amount of 0.1 to 2 times, more preferably 0.5 to 1.5 times the weight of the polyvinylidene fluoride resin. If the addition amount of the porosifying agent is within the above range, it is preferable that macrovoids generated in the support layer do not become too large and the film strength does not decrease.
  • FIG. 3 shows a rough flow of the manufacturing method.
  • a raw material liquid is normally used after returning to normal temperature.
  • the polyvinylidene fluoride resin include Arkema's polyvinylidene fluoride “Kyner HSV900”, “Kyner HSV800”, “Kyner 761A”, Solvay “Solef6020”, and Kureha “W # 7200”.
  • the coating is preferably performed so that the thickness after film formation is 10 to 500 ⁇ m.
  • the entire support is immersed in a non-solvent for polyvinylidene fluoride resin for 3 minutes to 12 hours.
  • a standing time after coating it is preferably about 5 to 60 seconds. If the standing time is taken longer, the average flow hole diameter becomes larger, but if it is taken too long, pinholes are generated and the effects of the present invention may not be sufficiently obtained.
  • a good solvent and a non-solvent are mixed, and the solubility of the polymer in the good solvent is reduced due to the mixing of the non-solvent, so that the polymer is precipitated and porous.
  • a polyester nonwoven fabric is placed on a glass plate and a raw material solution is applied.
  • a baker applicator, a bar coater, a T die, or the like can be used.
  • the glass plate as a support is removed to obtain a microporous membrane.
  • DMAc is less likely to evaporate than water, and therefore incomplete cleaning may cause the solvent (DMAc) to concentrate and the resulting pore structure to dissolve again, so multiple cleanings are preferred.
  • warm water may be used for washing, or an ultrasonic washing machine may be used.
  • the microporous membrane may be dried. Drying may be natural drying, a hot air drier or far-infrared drier may be used to increase the drying speed, and a pin tenter type to prevent shrinkage and undulation of the microporous membrane during drying. A dryer may be used.
  • SiO 2 glass layer forming step (S04) Finally, a SiO 2 glass layer is formed on the surface of the microporous film containing the polyvinylidene fluoride resin obtained in the cleaning / drying step (S03).
  • the method for forming the SiO 2 glass layer include a sol-gel method in which polyorganosiloxane is infiltrated and adhered to a microporous film containing a polyvinylidene fluoride resin and converted by a method such as heating. it can.
  • a solution in which a hydrolyzable silicon-containing organic compound is partially gelled by reacting with water is applied to the surface of a microporous film containing a polyvinylidene fluoride resin by a technique such as coating or spraying.
  • a method of obtaining a composite microporous membrane by reacting with water to completely gel and further drying by heating at a suitable temperature usually in the range of 25 to 120 ° C. can be mentioned.
  • a solution mainly composed of a polysilazane compound having a structural unit represented by the following formula (A) is attached to a microporous film containing a polyvinylidene fluoride resin by a technique such as coating or spraying.
  • a technique such as coating or spraying.
  • examples thereof include a polysilazane method in which a composite microporous film is obtained by being converted into a SiO 2 glass layer through treatment with air heating, hot water, water vapor or the like.
  • each R independently represents hydrogen or alkyl having 1 to 22 carbon atoms.
  • the polysilazane method using polysilazane as the silica precursor is most preferable.
  • the polysilazane method is easy to obtain a high-strength composite microporous membrane by relatively easy conversion to a SiO 2 glass layer having a dense structure, and there is little elution of impurities derived from crosslinking agents, catalyst residues, etc. preferable.
  • the polysilazane used in the present invention is preferably a polysilazane that can be converted into SiO 2 glass at a low temperature.
  • examples of such polysilazane include a solution containing polysilazane having a Si—H bond described in JP-A-2004-155835, a silicon alkoxide-added polysilazane described in JP-A-5-238827, and the like. And glycidol-added polysilazane described in JP-A-6-122852, and acetylacetonato complex-added polysilazane described in Japanese Patent No. 3307471.
  • the polysilazane solution can be obtained, for example, as “AQUAMICA” manufactured by AZ Electronic Materials Co., Ltd.
  • the method for applying the polysilazane solution to the microporous film is not particularly limited, and examples thereof include known methods such as roll coating, gravure coating, blade coating, spin coating, bar coating, and spray coating.
  • the polysilazane solution is applied to and adhered to the microporous film, and then the solvent is evaporated by pre-drying to produce a polysilazane layer.
  • the polysilazane layer is converted into a SiO 2 glass layer by a method such as heating, hot water immersion, or steam exposure to form a microporous film.
  • after winding in a state of forming a polysilazane layer it may be converted to SiO 2 glass layer is subjected to processing such as winding body for each heating or steam exposure.
  • a base material layer may be provided during film formation.
  • the raw material liquid can be prevented from inadvertently flowing out during the application of the raw material liquid.
  • the base material layer functions as a reinforcing material during filtration, and the membrane can withstand the filtration pressure.
  • the base material layer non-woven fabrics, woven fabrics, porous plates and the like obtained by papermaking, a spunbond method, a melt blow method, and the like can be used. Polyester, polyolefin, ceramic, and the like can be used as the material.
  • the basis weight is preferably in the range of 15 to 150 g / m 2 , more preferably in the range of 30 to 90 g / m 2 .
  • the basis weight exceeds 15 g / m 2 , the effect of providing the base material layer is sufficiently obtained.
  • the basis weight is less than 150 g / m 2 , post-processing such as bending and heat bonding becomes easy.
  • the concentration of the polysilazane solution is preferably in the range of 0.1 to 20 parts by weight, and more preferably in the range of 0.5 to 10 parts by weight.
  • the polysilazane concentration exceeds 0.1 parts by weight, a sufficient hydrophilic effect can be obtained.
  • the polysilazane concentration is less than 20 parts by weight, the SiO 2 glass layer does not block pores, so that sufficient permeability can be secured.
  • the filter performance can be further improved by adding an appropriate filler to the polysilazane solution as long as the chemical resistance and heat distortion resistance of the microporous membrane are not hindered. Can do.
  • fillers include fine particles such as zinc oxide, titanium dioxide, barium titanate, barium carbonate, barium sulfate, zirconium oxide, zirconium silicate, alumina, magnesium oxide and silica, as well as silicon carbide, silicon nitride and carbon.
  • the carbon includes fine particles composed of activated carbon, carbon nanotubes and the like in addition to graphite carbon fine particles. At least one of these fillers adheres to the microporous membrane together with the polysilazane and is firmly fixed in the SiO 2 glass layer, whereby a composite porous membrane that does not fall off can be obtained.
  • the concentration of the filler in the polysilazane solution is usually 0 to 20% by weight, preferably 0 to 10% by weight. In such a concentration range, the performance as a filter can be further improved.
  • the composite microporous membrane of the present invention has a high hydrophilicity because the surface layer is coated with the SiO 2 glass layer, and the microporous membrane contains a polyvinylidene fluoride resin based on the SiO 2 glass layer. Since there is no blockage of micropores in the membrane, it is possible to maintain high permeability. Further, since the polyvinylidene fluoride resin is used as the film material, it can have excellent chemical resistance and high heat resistance (up to 120 ° C.).
  • the skin layer has a three-dimensional network structure composed of a homogeneous spherical body and a linear binder, the pore size and the pore diameter of the skin layer are uniform, and high permeability (for example, high water permeability and high liquid permeability) is achieved.
  • high permeability for example, high water permeability and high liquid permeability
  • it is a microporous film having the above three-dimensional network structure, it is easy to apply the polysilazane solution uniformly to the entire film, and the hydrophilic effect of the SiO 2 glass layer can be effectively exhibited.
  • the composite microporous membrane of the present invention can be used for applications such as a chemical solution holding material used for adhesive bandages, a sanitary material surface material, a battery separator, etc., in addition to a filter application such as a filtration membrane.
  • the length until the macro voids exist was defined as “skin layer thickness”, and the value obtained by subtracting the skin layer thickness from the total thickness of the composite microporous membrane was defined as “support layer thickness”. 3) Average flow hole diameter The average flow hole diameter was determined according to ASTM F316-86 using “Capillary Flow Porometer CFP-1200AEX” manufactured by PMI. 4) Flux The obtained composite microporous membrane is cut to a diameter of 25 mm, and is set in a filter sheet holder having an effective filtration area of 3.5 cm 2 for each of the case where the composite microporous membrane is immersed in an appropriate amount of ethanol and the case where it is not immersed.
  • the outer periphery of the spherical body is surrounded by a perfect circle with the maximum diameter so that the surrounding holes are not included.
  • the diameter of the perfect circle was taken as the particle size of the spherical body.
  • the number of the linear binding materials to be connected is 3 or less is difficult to distinguish from the linear binding materials, it was not regarded as a spherical body.
  • region was made into the average particle diameter.
  • the number distribution of particles within a range of ⁇ 10% of the average particle diameter was counted from all the spherical bodies, and the number was divided by the total number of particles of the spherical body to obtain a frequency distribution.
  • the frequency distribution was calculated
  • Example 1 [Preparation process of raw material liquid]
  • the total amount of the raw material liquid is 100 parts by weight, 86 parts by weight of dimethylacetamide, 7 parts by weight of polyvinylidene fluoride “Kyner HSV900 (weight average molecular weight 800,000)”, 7 parts by weight of polyethylene glycol, these are mixed, Dissolved at ° C. It was returned to room temperature to obtain a raw material solution.
  • [Porosification process] A polyester nonwoven fabric was placed on a glass plate, and the raw material liquid was applied thereon with a thickness of 250 ⁇ m using a Baker applicator. Immediately after application, the film was made porous to make it porous.
  • microporous membrane containing a polyvinylidene fluoride resin was taken out of the water and dried to obtain a microporous membrane containing a polyvinylidene fluoride resin.
  • SiO 2 glass layer forming step As the polysilazane solution, “AQUAMICA (registered trademark) model number NAX121-01 (polysilazane concentration: 1.0 part by weight)” manufactured by AZ Electronic Materials, Inc. After dipping and removing the membrane, it is allowed to stand in a fume hood for about 30 minutes until the solvent completely evaporates, placed in an oven maintained at 130 ° C., heat-treated for 1 hour, and then allowed to stand at room temperature for 1 week. And a composite microporous membrane was obtained.
  • AQUAMICA registered trademark model number NAX121-01 (polysilazane concentration: 1.0 part by weight)
  • Example 1 A single-layer microporous film was obtained in the same manner as in Example 1 except that the SiO 2 glass layer forming step was omitted.
  • the skin layer of the composite microporous membrane of Example 1 has a three-dimensional network structure composed of a spherical body and a linear binder. Even when compared with the skin layer of the single-layer microporous film of Comparative Example 1, it can be seen that the micropores are not blocked by the SiO 2 glass layer. As shown in Table 1, it can also be seen that the inside of the microporous membrane is not clogged from the fact that the average flow pore diameter also shows the same value. Moreover, since Example 1 shows a very high flux even without ethanol treatment compared with Comparative Example 1, it can be seen that the hydrophilicity is very high due to the formation of the SiO 2 glass layer.
  • Tables 2 to 3 show the particle diameters (true circle diameters) of the spherical bodies 1 obtained from scanning electron micrographs of the composite microporous membrane of Example 1.
  • Table 4 shows the particle size characteristics of the spherical bodies of Example 1.
  • the skin layer of the composite microporous membrane of Example 1 has a spherical average particle size of 0.190 ⁇ m. Further, 112 spheres corresponding to 62% of the spheres have a particle diameter within a range of ⁇ 10% of the average particle diameter.
  • Table 5 shows a frequency distribution table of the particle size of the spherical body.
  • the particle size is concentrated within a width of 0.05 ⁇ m (0.15 to 0.20 ⁇ m), and it can be seen that the spherical body has a uniform particle size.
  • Tables 6 to 10 show the length of the linear binding material 2 (length between perfect circles) obtained from the scanning electron micrograph of the composite microporous membrane of Example 1.
  • Table 11 shows the characteristics of the linear binder of Example 1.
  • the average length of the linear binder is 0.219 ⁇ m.
  • the length of 259 binders, which is 61% of the binder is in the range of ⁇ 30% of the average length.
  • Table 12 shows a frequency distribution table of the lengths of linear binders. The frequency distribution increases and decreases so that the range of 0.20 to 0.25 ⁇ m peaks, and it can be seen that the length of the binder is concentrated in a specific range.
  • the composite microporous membrane of the present invention exhibits high water permeability without hydrophilic treatment such as alcohol substitution, it is possible to produce a filter having excellent chemical resistance and heat resistance possessed by a polyvinylidene fluoride resin. .
  • the membrane bioreactor, the water purification membrane, the medicine for which the high temperature sterilization process is essential, and the use for the food use can be used particularly effectively.

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WO2017159457A1 (ja) * 2016-03-16 2017-09-21 住友電工ファインポリマー株式会社 積層体の製造方法及び積層体
JP2017170418A (ja) * 2016-03-16 2017-09-28 住友電工ファインポリマー株式会社 積層体の製造方法及び積層体
CN108499363A (zh) * 2018-04-28 2018-09-07 广西民族大学 原位合成纳米二氧化硅改性pvdf疏水微孔膜的方法
CN109698300A (zh) * 2017-10-24 2019-04-30 住友化学株式会社 非水电解液二次电池用多孔层
WO2020138065A1 (ja) * 2018-12-26 2020-07-02 東レ株式会社 多孔質膜、複合膜及び多孔質膜の製造方法
CN111760470A (zh) * 2020-07-06 2020-10-13 中国海诚工程科技股份有限公司 一种膜转移涂布mbr膜及其制备方法
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EP4159304A4 (en) * 2020-05-29 2024-06-05 Toray Industries, Inc. POROUS FILM AND COMPOSITE FILM
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JP2017170418A (ja) * 2016-03-16 2017-09-28 住友電工ファインポリマー株式会社 積層体の製造方法及び積層体
CN105797591A (zh) * 2016-03-28 2016-07-27 上海应用技术学院 一种超疏水性聚偏氟乙烯微孔膜的制备方法
CN105797591B (zh) * 2016-03-28 2019-01-18 上海应用技术学院 一种超疏水性聚偏氟乙烯微孔膜的制备方法
CN109698300A (zh) * 2017-10-24 2019-04-30 住友化学株式会社 非水电解液二次电池用多孔层
CN108499363A (zh) * 2018-04-28 2018-09-07 广西民族大学 原位合成纳米二氧化硅改性pvdf疏水微孔膜的方法
WO2020138065A1 (ja) * 2018-12-26 2020-07-02 東レ株式会社 多孔質膜、複合膜及び多孔質膜の製造方法
JP7435438B2 (ja) 2018-12-26 2024-02-21 東レ株式会社 多孔質膜、複合膜及び多孔質膜の製造方法
US12097470B2 (en) 2018-12-26 2024-09-24 Toray Industries, Inc. Porous membrane, composite membrane, and method for producing porous membrane
EP4159304A4 (en) * 2020-05-29 2024-06-05 Toray Industries, Inc. POROUS FILM AND COMPOSITE FILM
CN111760470A (zh) * 2020-07-06 2020-10-13 中国海诚工程科技股份有限公司 一种膜转移涂布mbr膜及其制备方法
US20230045239A1 (en) * 2021-08-04 2023-02-09 ExxonMobil Technology and Engineering Company Floating Photobioreactors for Algae Biofuel Production and Devices and Methods Related Thereto
US11827861B2 (en) * 2021-08-04 2023-11-28 ExxonMobil Technology and Engineering Company Floating photobioreactors for algae biofuel production and devices and methods related thereto

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