WO2019151271A1 - Membrane poreuse hydrophile - Google Patents

Membrane poreuse hydrophile Download PDF

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Publication number
WO2019151271A1
WO2019151271A1 PCT/JP2019/003048 JP2019003048W WO2019151271A1 WO 2019151271 A1 WO2019151271 A1 WO 2019151271A1 JP 2019003048 W JP2019003048 W JP 2019003048W WO 2019151271 A1 WO2019151271 A1 WO 2019151271A1
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Prior art keywords
porous membrane
hydrophilic
membrane
acrylic monomer
film
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PCT/JP2019/003048
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English (en)
Japanese (ja)
Inventor
陽大 石井
健志 梅原
勇也 元村
三ツ井　哲朗
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富士フイルム株式会社
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Publication of WO2019151271A1 publication Critical patent/WO2019151271A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment

Definitions

  • the present invention relates to a hydrophilic porous membrane.
  • Porous membranes made of various polymers such as polysulfone and polyolefin are used as filtration membranes in water purification and blood treatment. Since these materials are generally hydrophobic and difficult to wet with water, they are used after being hydrophilized depending on the application.
  • Patent Document 1 has a monomer (A) composed of one or more polyfunctional (meth) acrylates and a hydrocarbon residue having 5 to 20 carbon atoms on the surface of at least some of the pores of a polyolefin porous membrane.
  • A a monomer composed of one or more polyfunctional (meth) acrylates and a hydrocarbon residue having 5 to 20 carbon atoms on the surface of at least some of the pores of a polyolefin porous membrane.
  • a heat-resistant hydrophilized porous membrane in which a cross-linked copolymer with a monomer (B) composed of one or more types of monofunctional (meth) acrylate is retained, and further a hydrophilic polymer is retained thereon.
  • the heat resistant hydrophilized porous membrane described in Patent Document 1 has both heat resistance and hydrophilicity achieved simultaneously by a hydrophilization treatment using a crosslinked copolymer.
  • a hydrophilization treatment using a crosslinked copolymer there is room for further improvement in order to use as a filtration membrane applied to various uses such as a filtration membrane for uses requiring high-pressure steam sterilization.
  • the porous membrane is likely to be clogged by the hydrophilization treatment and the water permeability is lowered, in Patent Document 1, the examination of water permeability is not sufficient.
  • An object of the present invention is to provide a hydrophilic porous membrane that has high hydrophilicity and does not deteriorate water permeability and wettability even after high-pressure steam sterilization.
  • the present invention provides the following ⁇ 1> to ⁇ 9>.
  • ⁇ 1> a porous membrane and a hydrophilic coating that covers at least part of the outer surface of the porous membrane,
  • the hydrophilic coating is a cured product of a composition containing the first acrylic monomer,
  • the first acrylic monomer is a trifunctional to hexafunctional monomer,
  • ⁇ 2> The hydrophilic porous membrane according to ⁇ 1>, wherein the first acrylic monomer is a trifunctional to tetrafunctional monomer.
  • ⁇ 3> The hydrophilic porous membrane according to ⁇ 1> or ⁇ 2>, wherein the ClogP value of the first acrylic monomer is 0.0 or less.
  • ⁇ 4> The hydrophilic porous membrane according to any one of ⁇ 1> to ⁇ 3>, wherein the first acrylic monomer is (meth) acrylamide.
  • ⁇ 5> The hydrophilic porous membrane according to any one of ⁇ 1> to ⁇ 4>, wherein the composition contains a second acrylic monomer having 1 to 2 functions.
  • ⁇ 6> The hydrophilic porous membrane according to ⁇ 5>, wherein the mass ratio of the first acrylic monomer to the second acrylic monomer in the composition is 20:80 to 80:20.
  • ⁇ 7> The hydrophilic porous membrane according to ⁇ 5> or ⁇ 6>, wherein the second acrylic monomer is (meth) acrylamide.
  • ⁇ 8> The hydrophilic porous membrane according to any one of ⁇ 1> to ⁇ 7>, wherein the porous membrane contains polysulfone.
  • ⁇ 9> The hydrophilic porous membrane according to any one of ⁇ 1> to ⁇ 8>, wherein the porous membrane has a pore size distribution.
  • hydrophilic porous membrane that has high hydrophilicity and does not deteriorate water permeability and wettability even after high-pressure steam sterilization treatment.
  • (meth) acryloyl group means acryloyl group (H 2 C ⁇ CH—C ( ⁇ O) —) and methacryloyl group (H 2 C ⁇ C (CH 3 ) —C ( ⁇ O) —). Represents one or both of the above.
  • (meth) acrylamide represents one or both of acrylamide and methacrylamide.
  • the hydrophilic porous membrane means a membrane obtained by subjecting a porous membrane serving as a base material to a hydrophilic treatment.
  • a hydrophilic porous membrane is a membrane having a plurality of pores. The hole can be confirmed by, for example, a scanning electron microscope (SEM) image or a transmission electron microscope (TEM) image of the film cross section.
  • the hydrophilic porous membrane of the present invention includes a porous membrane and a hydrophilic coating that covers at least a part of the outer surface of the porous membrane.
  • the outer surface of the porous membrane refers to the surface of the porous membrane (the front surface or the back surface of the membrane) and the surface of the porous membrane facing each pore inside the porous membrane (this book In the specification, it is sometimes referred to as “the surface of the pore”.
  • the surface of at least one of the porous membranes and the surface of the porous membrane facing at least some of the plurality of pores inside the porous membrane are hydrophilized It is preferable that it is covered with a coating, and it is more preferable that substantially all of the outer surface of the porous membrane is covered with a hydrophilic coating.
  • the porous membrane may be coated on either one of the membrane surfaces or on both membrane surfaces, but it is preferable that both membrane surfaces are coated. As described later, when any one of the porous membranes having a pore size distribution is coated, it is preferable that the membrane surface having a smaller pore size is coated.
  • the porous membrane is hydrophobic, the water permeability is particularly lowered at a site where the pore diameter is small due to the surface tension of water. Therefore, a decrease in water permeability can be efficiently suppressed by coating a highly crosslinked polymer with a hydrophilic coating at a site where the pore diameter is small.
  • the part is, for example, any one of the porous membranes It may be in the vicinity of the film surface.
  • the film surface at that time is preferably a coated film surface.
  • any one of the porous membranes having a pore size distribution is coated, it is preferable that the pores in the vicinity of the membrane surface having a smaller pore size are coated.
  • the surface of the porous membrane facing all the pores of the plurality of pores inside the porous membrane is covered.
  • the coating with the hydrophilic coating may be performed to such an extent that the hydrophilic porous membrane is not easily peeled off during storage or use.
  • the coating may be carried out by covalent bonding between the compound in the hydrophilic coating and the residue on the outer surface of the porous membrane, but the hydrophilic coating is formed on the membrane surface or by forming a cured product network described later. It is preferably in a state held in the pores.
  • the hydrophilic coating only needs to be applied to the porous film as the base material in an arbitrary mass in consideration of necessary wettability and water permeability. About 25 to 20% by mass, and preferably about 0.5 to 15% by mass.
  • a porous membrane refers to a membrane having a plurality of pores.
  • the pores can be confirmed by, for example, a scanning electron microscope (SEM) image or a transmission electron microscope (TEM) image of the film cross section.
  • SEM scanning electron microscope
  • TEM transmission electron microscope
  • the pore diameter of the pores of the porous membrane can be appropriately selected depending on the size of the object to be filtered, but may be 0.01 ⁇ m to 10 ⁇ m, more preferably 0.01 ⁇ m to 5 ⁇ m, and more preferably 0.01 ⁇ m. More preferably, it is ⁇ 2 ⁇ m. What is necessary is just to measure a hole diameter from the photograph of the film
  • the porous membrane is cut with a microtome or the like, and a photograph of the cross section of the porous membrane can be obtained as a slice of a thin film whose cross section can be observed.
  • the pore size of the pores of the hydrophilic porous membrane may be smaller than the pore size of the porous membrane of the base material as a result of the hydrophilization treatment, but usually approximated to be the same as the pore size of the porous membrane. it can.
  • the structure of the porous membrane may be either a structure having a pore size distribution in the thickness direction or a homogeneous structure having no pore size distribution in the thickness direction.
  • a structure having a pore size distribution in the thickness direction a structure (asymmetric structure) that is asymmetric in the thickness direction having a pore size distribution so that the pore size of the front surface and the back surface of the membrane are different is preferable.
  • asymmetric structures include a structure in which the pore diameter continuously increases in the thickness direction from one membrane surface to the other membrane surface, and has a layered dense portion in which the pore diameter is minimized.
  • the porous membrane has a layered dense portion in which the pore diameter is minimized, and the pore diameter continuously increases in the thickness direction from the dense portion toward at least one surface of the porous membrane.
  • a structure is preferred.
  • the SEM photograph of the film cross section is divided in the film thickness direction.
  • the number of divisions can be appropriately selected from the thickness of the film.
  • the number of divisions is at least 5 or more.
  • the size of the division width means the size of the width in the thickness direction of the film, and does not mean the width size in the photograph.
  • the pore diameter is compared as the average pore diameter of each section.
  • the average pore diameter of each section may be, for example, an average value of 50 holes in each section of the membrane cross-sectional view.
  • the film cross-sectional view in this case may be obtained, for example, with a width of 80 ⁇ m (a distance of 80 ⁇ m in a direction parallel to the surface).
  • the layered dense part having the smallest pore diameter refers to the layered part of the porous film corresponding to the section having the smallest average pore diameter among the sections of the membrane cross section. Even if the dense part consists of parts corresponding to one section, such as two, three, etc., from parts corresponding to a plurality of sections having an average pore diameter within 1.1 times that of the section having the smallest average pore diameter It may be.
  • the dense part may have a thickness of 0.5 ⁇ m to 50 ⁇ m, and preferably 0.5 ⁇ m to 30 ⁇ m. In this specification, the average pore size of the dense part is defined as the minimum pore size of the porous membrane.
  • the minimum pore size of the porous membrane is preferably 0.01 ⁇ m or more, more preferably 0.02 ⁇ m or more, more preferably 10 ⁇ m or less, and even more preferably 5 ⁇ m or less. This is because at least normal cell permeation can be prevented with such a minimum pore size of the porous membrane.
  • the average pore diameter of the dense part is measured by ASTM F316-80.
  • the porous membrane preferably has a dense portion inside. “Inside” means not in contact with the surface of the film, and “having a dense part inside” means that the dense part is not the closest segment to any surface of the film.
  • the dense part is biased to one of the surface sides with respect to the central part of the thickness of the porous film.
  • the dense part is preferably at a distance within one third of the thickness of the porous film from one of the surfaces of the porous film, and more preferably at a distance within two fifths. More preferably, the distance is within a quarter. This distance may be determined in the above-mentioned film cross-sectional photograph.
  • the surface of the porous membrane closer to the dense part is referred to as “surface X”.
  • the pore diameter continuously increases in the thickness direction from the dense part toward at least one of the surfaces.
  • the pore diameter may continuously increase in the thickness direction from the dense portion toward the surface X, and the pore diameter continuously increases in the thickness direction from the dense portion toward the surface opposite to the surface X.
  • the pore diameter may be continuously increased from the dense part to any surface of the porous membrane in the thickness direction.
  • the pore diameter is continuously increased in the thickness direction from at least the dense portion toward the surface opposite to the surface X, and when moving from the dense portion to any surface of the porous film in the thickness direction. More preferably, the pore diameter continuously increases.
  • the pore diameter increases continuously in the thickness direction means that the average pore diameter difference between adjacent sections in the thickness direction is 50% or less of the difference between the maximum average pore diameter (maximum pore diameter) and the minimum average pore diameter (minimum pore diameter). , Preferably 40% or less, more preferably 30% or less. “Successively increasing” essentially means that there is no decrease and that the increase is uniform, but a decreasing site may occur accidentally. For example, when two sections are combined from the surface, the average value of the combination increases uniformly (decreases uniformly when going from the surface to the dense part). It can be determined that the pore diameter continuously increases in the thickness direction.
  • the maximum pore size of the porous membrane is preferably more than 0.1 ⁇ m, more preferably more than 0.1 ⁇ m, further preferably more than 1.5 ⁇ m, more preferably not more than 25 ⁇ m, and 23 ⁇ m Or less, more preferably 21 ⁇ m or less.
  • the average pore diameter of the section having the maximum average pore diameter among the sections of the membrane cross section is defined as the maximum pore diameter of the porous film.
  • Ratio of the average pore size of the dense part to the maximum pore size of the porous membrane (the ratio of the minimum pore size of the porous membrane to the maximum pore size, the value obtained by dividing the maximum pore size by the minimum pore size, Is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more. This is to increase the average pore size other than the dense part and increase the material permeability of the porous membrane.
  • the anisotropy ratio is preferably 25 or less, and more preferably 20 or less. This is because the effect such as the above-described multi-stage filtration is efficiently obtained when the anisotropy ratio is 25 or less.
  • the section having the largest average pore diameter is preferably a section closest to any surface of the membrane or a section in contact with the section.
  • the average pore size is preferably more than 0.05 ⁇ m and 25 ⁇ m or less, more preferably more than 0.08 ⁇ m and 23 ⁇ m or less, and more than 0.1 ⁇ m and 21 ⁇ m or less. Is more preferable.
  • the ratio of the average pore diameter of the section closest to any surface of the membrane to the average pore diameter of the dense portion is preferably 1.2 or more and 20 or less, more preferably 1.5 or more and 15 or less. More preferably, it is 2 or more and 13 or less.
  • the thickness of the porous membrane is not particularly limited, but it may be 10 ⁇ m to 1000 ⁇ m from the viewpoint of membrane strength, handleability, and filtration performance, preferably 10 ⁇ m to 500 ⁇ m, more preferably 30 ⁇ m to 300 ⁇ m. preferable.
  • the thickness of the hydrophilic porous film may be larger than the thickness of the porous film of the base material as a result of the hydrophilization treatment, it is usually almost the same as the thickness of the porous film.
  • the porous membrane includes a polymer.
  • the porous membrane is preferably composed essentially of a polymer.
  • the polymer preferably has a number average molecular weight (Mn) of 1,000 to 10,000,000, more preferably 5,000 to 1,000,000.
  • polystyrene-acrylonitrile copolymer examples include polysulfone, sulfonated polysulfone, polyethersulfone (PES), sulfonated polyethersulfone, cellulose acylate, nitrocellulose, polyacrylonitrile, styrene-acrylonitrile copolymer, styrene-butadiene copolymer, ethylene- Saponified vinyl acetate copolymer, polyvinyl alcohol, polycarbonate, organosiloxane-polycarbonate copolymer, polyester carbonate, organopolysiloxane, polyphenylene oxide, polyamide, polyimide, polyamideimide, polybenzimidazole, ethylene vinyl alcohol copolymer, polytetrafluoroethylene (PTFE), polyethylene, polypropylene, polyfluoroethylene, polyethylene Terephthalate, polyamide, polyimide, 6,6-nylon, polyvinylidene fluor fluor fluor
  • polysulfone, polyethersulfone, PVDF, sulfonated polysulfone, sulfonated polyethersulfone, 6,6-nylon, and cellulose acylate are preferable, and polysulfone is more preferable.
  • the porous membrane may contain components other than the polymer as additives.
  • the additives include metal salts of inorganic acids such as sodium chloride, lithium chloride, sodium nitrate, potassium nitrate, sodium sulfate and zinc chloride, metal salts of organic acids such as sodium acetate and sodium formate, polyethylene glycol, polyvinyl pyrrolidone and the like.
  • examples include molecules, polymer electrolytes such as sodium polystyrene sulfonate and polyvinylbenzyltrimethylammonium chloride, and ionic surfactants such as sodium dioctylsulfosuccinate and sodium alkylmethyl taurate.
  • the additive may act as a swelling agent for the porous structure.
  • the porous membrane preferably further contains polyvinylpyrrolidone.
  • the polyvinylpyrrolidone may be held in the porous film.
  • Hydrophobic polysulfone or polyethersulfone is highly hydrophilic by containing polyvinylpyrrolidone. That is, the porous membrane which is the base material of the hydrophilic porous membrane of the present invention may already have a certain degree of hydrophilicity before the hydrophilization treatment.
  • Polyvinyl pyrrolidone is added as a pore-forming agent in a polysulfone membrane or a polyethersulfone membrane forming stock solution as described in, for example, JP-A No. 64-34403. Most of the polyvinylpyrrolidone in the film-forming stock solution is dissolved and removed in the coagulated water during the film-forming process, but a part remains on the film surface.
  • the porous film is preferably a film formed from one composition as a single layer, and preferably not a multi-layer laminated structure.
  • the method for producing the porous membrane reference can be made to JP-A-4-349927, JP-B-4-68966, JP-A-4-351645, JP-A-2010-235808, and the like.
  • a commercially available product may be used as the porous membrane.
  • Sumilite FS-1300 manufactured by Sumitomo Bakelite Co., Ltd.
  • Micro PES 1FPH manufactured by Membrana Co., Ltd.
  • PSEUH20 polysulfone membrane, manufactured by Fuji Film Co., Ltd.
  • Durapore PVDF membrane, manufactured by Merck Millipore
  • 15406 PES membrane, manufactured by Sartorius
  • the hydrophilic coating in the hydrophilic porous membrane of the present invention comprises a cured product of a composition containing a predetermined acrylic monomer described as “first acrylic monomer” in the present specification.
  • acrylic monomer means a monomer having a (meth) acryloyl group.
  • examples of the “acrylic monomer” include (meth) acrylate and (meth) acrylamide.
  • the composition may contain a predetermined acrylic monomer described as a “second acrylic monomer” in the present specification, other monomers, a polymerization initiator, and the like. It is preferable that the composition is prepared as a hydrophilizing liquid further containing a solvent, and is cured by the procedure described later to form a hydrophilizing coating.
  • first acrylic monomer an acrylic monomer having 3 to 6 functional ClogP values of 2.0 or less is used.
  • the first acrylic monomer is preferably trifunctional or higher and tetrafunctional or lower.
  • the functional number of an acrylic monomer shows the number of (meth) acryloyl groups.
  • the ClogP value is a value obtained by calculating the common logarithm logP of the distribution coefficient P to 1-octanol and water.
  • the ClogP value is a hydrophilicity index. Any known method or software may be used to calculate the ClogP value. In the present invention, unless otherwise specified, a ClogP program incorporated in ChemBioDraw Ultra 13.0 of Cambridge software is used. To do.
  • the ClogP value of the first acrylic monomer is 2.0 or less, more preferably 1.0 or less, and further preferably 0.0 or less. The lower limit is preferably ⁇ 6.0, more preferably ⁇ 2.0, and even more preferably ⁇ 1.0.
  • the ClogP value of the first acrylic monomer is, for example, preferably from ⁇ 6.0 to 2.0, more preferably from ⁇ 2.0 to 1.0, and from ⁇ 1.0 to 0 More preferably, it is 0.0 or less.
  • Examples of the first acrylic monomer include (meth) acrylate and (meth) acrylamide, with (meth) acrylamide being preferred and acrylamide being more preferred.
  • first acrylic monomer Preferred examples of the first acrylic monomer are shown below, but the first acrylic monomer is not limited to the following examples.
  • the value in parentheses is the ClogP value of each monomer.
  • FAM-401 and FAM-301 are product names. FAM-401 and FAM-301 are available from FUJIFILM Corporation. ATM-35E is a product name. ATM-35E is available from Shin-Nakamura Chemical Co., Ltd.
  • the composition for forming a hydrophilic coating preferably contains a second acrylic monomer.
  • the second acrylic monomer is an acrylic monomer having 1 to 2 functional groups.
  • the ClogP value of the second acrylic monomer is not particularly limited, but is preferably from -6.0 to 2.0, more preferably from -2.0 to 1.0, and -1. More preferably, it is 0 or more and 0.0 or less.
  • Examples of the second acrylic monomer include (meth) acrylate, (meth) acrylamide and the like, (meth) acrylamide is preferable, and acrylamide is more preferable.
  • FAM-201 and FAM-101 are product names.
  • FAM-201 and FAM-101 are available from FUJIFILM Corporation.
  • N, N-methylenebisacrylamide is available from, for example, Tokyo Chemical Industry Co., Ltd.
  • the mass ratio of the first acrylic monomer to the second acrylic monomer in the composition for forming a hydrophilic coating is preferably 20:80 to 80:20, and 30:70 to 70:30. More preferably.
  • the composition for forming a hydrophilic coating is prepared as a hydrophilic liquid containing a solvent
  • the total mass of the first acrylic monomer and the second acrylic monomer is 0 with respect to the total mass of the hydrophilic liquid. It is desirable that the content be 0.05 to 10% by mass.
  • a hydrophilic component can fully be fixed to a film
  • it can prevent that there are too many hydrophilic components to fix
  • the composition for forming the hydrophilic coating preferably contains a polymerization initiator.
  • the polymerization initiator is not particularly limited, but is preferably soluble in a mixed solvent of water and a polar organic solvent. Moreover, what has absorption in the wavelength of 300 nm or more is preferable.
  • Preferable examples of the polymerization initiator include FAI-101L (manufactured by FUJIFILM Corporation), Irg2959 (manufactured by BASF), TPO-L (manufactured by BASF), L0290 (manufactured by Tokyo Chemical Industry Co., Ltd.), H1361 (Tokyo Chemical Industry).
  • the addition amount of the polymerization initiator is desirably 0.01 to 0.5% by mass with respect to the total mass of the hydrophilizing liquid.
  • composition for forming the hydrophilic coating is preferably prepared as a hydrophilic liquid containing a solvent. Any solvent may be used as long as it has a lower boiling point than any monomer contained in the composition, can wet the porous membrane, and can dissolve the monomer used. When adding a polymerization initiator etc., it is preferable that these can also be dissolved.
  • solvents examples include water, alcohols such as methanol, ethanol, n-propanol, and isopropanol, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, ethyl acetate, chloroform, and the like. Any two or more mixed solvents can be mentioned.
  • a mixed solvent of water and a polar organic solvent is particularly preferable.
  • the amount of the polar organic solvent is preferably 10 to 60% by mass, more preferably 20 to 55% by mass, and further preferably 30 to 50% by mass with respect to the total mass of the mixed solvent. preferable.
  • the hydrophilic porous membrane which water permeability and wettability do not fall after high-pressure-steam sterilization processing can be manufactured.
  • the amount of the polar organic solvent may be less than 10% by mass or more than 60% by mass with respect to the total mass of the mixed solvent. By setting this range, it is possible to produce a hydrophilic porous membrane that is less prone to clogging.
  • the polar organic solvent may be an organic solvent having a property of being miscible with water.
  • the polar organic solvent preferably contains at least one or more lower alcohols, and more preferably consists of lower alcohols.
  • the lower alcohol include alcohols having 5 or less carbon atoms such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, propylene glycol, and glycerin.
  • methanol, ethanol and isopropanol are particularly preferable, and ethanol is more preferable.
  • the hydrophilic porous membrane can be produced by performing a hydrophilization treatment for forming a hydrophilic coating on the porous membrane as a base material.
  • the hydrophilic coating can be formed by curing the composition containing the first acrylic monomer on at least a part of the outer surface of the porous membrane.
  • a hydrophilic coating can be formed by impregnating the composition prepared as the above-mentioned hydrophilization liquid into the porous membrane, and then subjecting the porous membrane impregnated with the hydrophilization liquid to a curing reaction. You may perform a washing process, a sterilization process, etc. further to the porous membrane in which the hydrophilic coating was formed.
  • the method for penetrating the hydrophilic liquid into the porous membrane is not particularly limited, and examples thereof include a dipping method, a coating method, a transfer method, and a spray method.
  • a dipping method or a coating method is preferable, and a dipping method is more preferable.
  • the permeation is preferably performed so that the hydrophilized liquid permeates the entire thickness direction of the porous membrane at least at a site subjected to light irradiation described later.
  • the porous film is impregnated with the hydrophilizing liquid by immersing the porous film in the hydrophilizing liquid. What is necessary is just to remove an excess hydrophilization liquid by raising a porous membrane from a hydrophilization liquid after immersion. Immersion may be performed under pressure.
  • the hydrophilization liquid can be efficiently injected into each pore of the porous membrane by pressurization.
  • the dipping time or press-fitting time in the dipping treatment or press-fitting treatment is not particularly limited, but is generally about 0.5 seconds to 30 minutes, and preferably about 0.5 seconds to 10 minutes.
  • the immersion time can be shortened by selecting a solvent or the like.
  • the porous membrane may be dried after the permeation of the hydrophilizing liquid into the porous membrane and before the curing reaction. By drying and removing at least a part of the solvent in the hydrophilized liquid by drying, the pores of the porous membrane are not blocked, and the composition can easily adhere uniformly over the entire pore surface of the porous membrane. Become. Drying may be semi-dry. In the present specification, semi-drying means that the solvent is volatilized and removed to the extent that the solvent that can volatilize remains. Examples of drying means include heating, wind, reduced pressure, and the like, and are not particularly limited. However, air drying and warm drying are preferable and air drying is more preferable because of the simplicity of the manufacturing process. Drying may be achieved simply by leaving it to stand.
  • the curing reaction is achieved by monomer polymerization.
  • the polymerization may be photopolymerization, radiation polymerization, or thermal polymerization, but photopolymerization is preferred, and photopolymerization using ultraviolet rays is particularly preferred.
  • a light source that emits light having a wavelength with which the polymerization initiator reacts can be arbitrarily selected.
  • a halogen xenon lamp, a metal halide lamp, a low pressure mercury lamp, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a sterilization lamp, a xenon lamp, an LED (Light Emitting Diode) light source lamp, or the like can be used.
  • the light irradiation may be performed from at least one surface of the porous film, but is preferably performed from both surfaces.
  • the curing reaction proceeds sufficiently in the entire porous film, and a hydrophilic porous film having higher water permeability can be obtained.
  • the curing reaction is performed using a porous film having a pore size distribution as a base material, it is preferable that at least the film surface having a smaller pore size is irradiated with light. Hydrophobic coating using a highly cross-linked polymer that facilitates the curing reaction on the membrane surface with a small pore diameter that is most difficult to permeate water due to the surface tension of water. It is for suppressing the fall of water permeability.
  • the atmosphere at the time of light irradiation is preferably air or an inert gas replacement atmosphere, and more preferably an atmosphere in which air is replaced with nitrogen until the oxygen concentration becomes 1% or less.
  • Irradiation energy when irradiated with ultraviolet rays as the light irradiation is preferably 20mJ / cm 2 ⁇ 50J / cm 2, 50mJ / cm 2 ⁇ 1500mJ / cm 2 is more preferable.
  • the illuminance is preferably 10mW / cm 2 ⁇ 2000mW / cm 2, more preferably 20mW / cm 2 ⁇ 1500mW / cm 2, further preferably 40mW / cm 2 ⁇ 1000mW / cm 2.
  • crosslinking occurs simultaneously with polymerization, and a network of crosslinked polymers is formed on at least a part of the outer surface of the porous membrane.
  • the degree of polymerization of the cross-linked polymer in the hydrophilic coating is not particularly limited.
  • the curing reaction may be performed after drying, may be performed simultaneously with drying (that is, semi-drying), or may be performed at a stage where drying is not performed.
  • the porous film retains the hydrophilic liquid, so that the mass of the porous film is constant from the mass of the porous film before the hydrophilic film has permeated.
  • the curing reaction may be performed when the amount is larger than the amount. Specifically, light irradiation is performed on a portion of the porous membrane in which the hydrophilizing liquid has permeated throughout the thickness direction and the mass is 3 to 16 times the mass before the hydrophilizing liquid is permeated.
  • a curing reaction is preferred. From the viewpoint of handleability, the mass is more preferably 3 to 12 times, and further preferably 3 to 8 times.
  • the part irradiated with light can be appropriately set according to the production conditions, and may be a part or the whole of the entire area of the porous membrane.
  • the entire area of the porous membrane may be subjected to the curing reaction by performing multiple times of light irradiation satisfying the above-mentioned mass conditions at different sites.
  • the entire region in the TD (transverse direction) direction within a certain distance range in the MD (machine direction) direction of the roll-like porous membrane is defined as the above-mentioned site.
  • the light may be sequentially irradiated in the MD direction.
  • the above-described permeation process and drying process, as well as a washing process and a sterilization process described later, can also be sequentially performed in the MD direction.
  • the entire porous film (sheet type not in a roll shape) having an area that can be irradiated with light once may be irradiated with light as the portion.
  • the porous membrane When the porous membrane is in the form of a roll, it may be difficult to compare the masses of specific parts.
  • a part of the porous membrane to be used may be sampled, and the semi-drying conditions for obtaining the above-mentioned mass after permeation of the used hydrophilizing solution may be confirmed in advance.
  • the light irradiation satisfying the above-mentioned mass condition can be performed.
  • a hydrophilic porous film having higher water permeability and higher wettability can be obtained.
  • the first light irradiation may be started when the part is in the above mass range. In any light irradiation, it is preferable that the same part is in the above mass range.
  • the hydrophilization liquid has penetrated into the porous membrane (for example, when it is pulled up after immersion), the mass of the porous membrane has already become 3 to 16 times the total mass of the porous membrane before the hydrophilization liquid has penetrated. If it is, it can be subjected to a curing reaction without further removing the solvent by volatilization. When it exceeds 16 times, it can be semi-dried until it reaches 3 to 16 times the total mass of the porous membrane before the permeation of the hydrophilizing liquid, and subjected to a curing reaction.
  • the cleaning method is not particularly limited, but the cleaning solvent may be permeated into the membrane surface and the pore surface of the hydrophilic porous membrane by dipping or press-fitting, and then removed.
  • the cleaning solvent include the solvents exemplified as the solvent for the hydrophilizing liquid.
  • the washing solvent may be permeated and removed two or more times. At this time, the washing solvent may be the same or different in two or more washings, but is preferably different.
  • the washing solvent used at the end of washing is preferably water. It is particularly preferable to immerse in water. This is to remove organic solvent components such as alcohol.
  • the hydrophilic porous membrane of the present invention is hydrophilized with a hydrophilic coating formed from a polyfunctional acrylic monomer having a functionality of 3 to 6, so that wettability and Water permeability is difficult to decrease.
  • high-pressure steam sterilization treatment for plastic is performed by pressurizing with saturated steam for 10 to 30 minutes in an environment of about 110 to 140 ° C.
  • Examples of the autoclave used for sterilization include SS325 manufactured by Tommy Seiko Co., Ltd.
  • the hydrophilic porous membrane of the present invention can be processed into a shape according to the application and used for various applications.
  • Examples of the shape of the hydrophilic porous membrane include a flat membrane shape, a tubular shape, a hollow fiber shape, a pleated shape, a fiber shape, a spherical particle shape, a crushed particle shape, and a massive continuous body shape. It may be processed into a shape according to the application before the hydrophilic treatment of the porous membrane, or may be processed into a shape according to the application after the hydrophilic treatment of the porous membrane.
  • the hydrophilic porous membrane may be mounted on a cartridge that can be easily removed in an apparatus used for various applications.
  • the hydrophilic porous membrane is preferably held in a form that can function as a filtration membrane.
  • a cartridge holding a hydrophilic porous membrane can be produced in the same manner as a known porous membrane cartridge, and for example, refer to WO2005 / 037413 and JP2012-045524A.
  • the hydrophilic porous membrane of the present invention can be used in various applications as a filtration membrane.
  • Filtration membranes are applied to the separation, purification, recovery, concentration, etc. of liquids containing or suspending various polymers, microorganisms, yeasts, and fine particles, especially from liquids containing fine fine particles that require filtration. It can be applied when it is necessary to separate.
  • a filtration membrane can be used when separating fine particles from various suspensions containing fine particles, a fermentation broth, a culture solution, or the like, or a pigment suspension.
  • the hydrophilic porous membrane of the present invention is required for the production of drugs in the pharmaceutical industry, the production of alcoholic beverages such as beer in the food industry, the fine processing in the electronics industry, the production of purified water, and the like. It can be used as a microfiltration membrane.
  • polysulfone membrane PSEUH20 manufactured by FUJIFILM Corporation was used. This polysulfone membrane has an asymmetric structure with a pore diameter of 0.2 ⁇ m and a thickness of 130 ⁇ m. As Comparative Example 6, this polysulfone membrane was used as it was. Durapore made by Merck Millipore was used as the PVDF membrane. This PVDF membrane has a homogeneous structure with a pore diameter of 0.22 ⁇ m and a thickness of 125 ⁇ m. As the PES film, 15406 made by Sartorius was used. This PES film has a homogeneous structure with a pore diameter of 0.45 ⁇ m and a thickness of 150 ⁇ m.
  • the hydrophilic porous film after UV exposure is heated to 70 ° C. with an IPA 75% aqueous solution (IPA (isopropyl alcohol) and water mixed at a mass ratio of 3: 1) at 70 ° C. for 10 minutes or ethanol After immersing in a 50% aqueous solution for 16 hours, it was dried at room temperature. Further, it was immersed in water for 5 minutes, and then the pulled up hydrophilic porous membrane was sandwiched between papers and dried naturally.
  • IPA 75% aqueous solution IPA (isopropyl alcohol) and water mixed at a mass ratio of 3: 1
  • IPA isopropyl alcohol
  • the sterilization was performed by autoclaving the hydrophilic porous membrane after washing at 121 ° C. for 30 minutes using an autoclave (SS-325 manufactured by Tommy Seiko Co., Ltd.).
  • the primary surface and the secondary surface indicate a membrane surface having a large pore diameter and a membrane surface having a small pore diameter, respectively.
  • an arbitrary surface was designated as a primary surface, and its back surface was designated as a secondary surface.
  • Water permeability was evaluated by passing water through the hydrophilic porous membrane under pressure and measuring the water flow rate for 30 seconds.
  • the hydrophilic porous membrane was cut into a 47 mm diameter circle, and set at the bottom of a container (manufactured by Merck Millipore, stainless pressure filter holder XX4004700). At this time, it set so that the said primary surface of a hydrophilic porous membrane might turn into a container upper part side. Water was introduced from the upper part of the container, and the pressure was increased until a pressure of 100 kpa was applied to the hydrophilic porous membrane. In this state, the water flow rate of water passing through the porous membrane was evaluated.
  • the water flow rate [ml / cm 2 / min] per unit area was determined from the mass of the water discharged in 30 seconds after starting to collect water. If the flow rate is 50 [ml / cm 2 / min] or more, it can be determined that the surface is sufficiently hydrophilic. The results are shown in Table 1.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

La présente invention concerne une membrane poreuse hydrophile comprenant : une membrane poreuse et un revêtement hydrophilisé qui est appliqué sur au moins une partie de la surface extérieure de la membrane poreuse. Ce revêtement hydrophilisé est un matériau durci constitué d'une composition qui contient un premier monomère acrylique, le premier monomère acrylique étant un monomère trifonctionnel à hexafonctionnel, et la valeur de Clog P du premier monomère acrylique n'étant pas supérieure à 2,0. La membrane poreuse hydrophile selon la présente invention présente un caractère hydrophile élevé, et sa perméabilité à l'eau ou sa mouillabilité ne diminuent pas même après un traitement de stérilisation à la vapeur sous haute pression.
PCT/JP2019/003048 2018-01-31 2019-01-30 Membrane poreuse hydrophile WO2019151271A1 (fr)

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JP2005523146A (ja) * 2002-04-16 2005-08-04 ポール コーポレイション 中空ファイバ
WO2009041376A1 (fr) * 2007-09-27 2009-04-02 Fujifilm Corporation Procédé de production d'une structure poreuse
WO2013054889A1 (fr) * 2011-10-13 2013-04-18 特種東海製紙株式会社 Membrane microporeuse et son procédé de production
JP2015514012A (ja) * 2012-04-12 2015-05-18 フジフィルム マニュファクチャリング ユーロプ ビー．ブイ． 硬化性組成物および膜
WO2015141477A1 (fr) * 2014-03-18 2015-09-24 積水化学工業株式会社 Film microporeux de résine synthétique résistant à la chaleur ainsi que son procédé de fabrication, séparateur d'accumulateur à électrolyte non aqueux et accumulateur à électrolyte non aqueux
JP2017191777A (ja) * 2016-04-14 2017-10-19 三星エスディアイ株式会社Samsung SDI Co., Ltd. 多孔性耐熱層組成物、多孔性耐熱層を含む分離膜、および該分離膜を用いた電気化学電池

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JP2005523146A (ja) * 2002-04-16 2005-08-04 ポール コーポレイション 中空ファイバ
WO2009041376A1 (fr) * 2007-09-27 2009-04-02 Fujifilm Corporation Procédé de production d'une structure poreuse
WO2013054889A1 (fr) * 2011-10-13 2013-04-18 特種東海製紙株式会社 Membrane microporeuse et son procédé de production
JP2015514012A (ja) * 2012-04-12 2015-05-18 フジフィルム マニュファクチャリング ユーロプ ビー．ブイ． 硬化性組成物および膜
WO2015141477A1 (fr) * 2014-03-18 2015-09-24 積水化学工業株式会社 Film microporeux de résine synthétique résistant à la chaleur ainsi que son procédé de fabrication, séparateur d'accumulateur à électrolyte non aqueux et accumulateur à électrolyte non aqueux
JP2017191777A (ja) * 2016-04-14 2017-10-19 三星エスディアイ株式会社Samsung SDI Co., Ltd. 多孔性耐熱層組成物、多孔性耐熱層を含む分離膜、および該分離膜を用いた電気化学電池

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2020075710A1 (fr) * 2018-10-09 2020-04-16 Jnc株式会社 Composition de revêtement pour la fabrication d'une membrane microporeuse hydrophile, et membrane microporeuse hydrophile

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