WO2010047383A1 - 熱硬化性樹脂多孔シートの製造方法、熱硬化性樹脂多孔シート、及びそれを用いた複合半透膜 - Google Patents

熱硬化性樹脂多孔シートの製造方法、熱硬化性樹脂多孔シート、及びそれを用いた複合半透膜 Download PDF

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WO2010047383A1
WO2010047383A1 PCT/JP2009/068235 JP2009068235W WO2010047383A1 WO 2010047383 A1 WO2010047383 A1 WO 2010047383A1 JP 2009068235 W JP2009068235 W JP 2009068235W WO 2010047383 A1 WO2010047383 A1 WO 2010047383A1
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Prior art keywords
epoxy resin
thermosetting resin
porous sheet
semipermeable membrane
composite semipermeable
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PCT/JP2009/068235
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English (en)
French (fr)
Japanese (ja)
Inventor
原田　憲章
敦 廣
勝視 石井
川口　佳秀
敦子 水池
修 林
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Nitto Denko Corp
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Nitto Denko Corp
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Priority to CN200980142522.2A priority Critical patent/CN102197073B/zh
Priority to KR1020117011526A priority patent/KR101361873B1/ko
Priority to US13/125,639 priority patent/US9186633B2/en
Publication of WO2010047383A1 publication Critical patent/WO2010047383A1/ja
Anticipated expiration legal-status Critical
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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
    • C08J9/26—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a solid phase from a macromolecular composition or article, e.g. leaching out
    • 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
    • B01D71/56—Polyamides, e.g. polyester-amides
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/46—Epoxy resins
    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/15—Use of additives
    • B01D2323/18—Pore-control agents or pore formers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/219—Specific solvent system
    • B01D2323/225—Use of supercritical fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/42—Details of membrane preparation apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
    • B01D61/025—Reverse osmosis; Hyperfiltration
    • 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
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/046—Elimination of a polymeric phase
    • 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
    • C08J2300/00—Characterised by the use of unspecified polymers
    • C08J2300/24—Thermosetting resins
    • 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
    • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
    • 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
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • 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
    • C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
    • Y10T428/269—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension including synthetic resin or polymer layer or component

Definitions

  • the present invention relates to a thermosetting resin porous sheet and a method for producing the same.
  • the present invention also relates to a composite semipermeable membrane comprising a skin layer and a thermosetting resin porous sheet that supports the skin layer.
  • a thermosetting resin porous sheet is suitably used as a support for a separation membrane or a composite semipermeable membrane.
  • such a composite semipermeable membrane is suitable for the production of ultrapure water, desalination of brackish water or seawater, etc., and it is also included in the contamination due to pollution such as dyeing wastewater and electrodeposition paint wastewater. It can contribute to the closure of wastewater by removing and recovering contaminated sources or effective substances. Moreover, it can be used for advanced treatments such as concentration of active ingredients in food applications and removal of harmful components in water purification and sewage applications.
  • Patent Document 1 a composite semipermeable membrane has been proposed in which a skin layer made of polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional aromatic acid halide is formed on a porous support.
  • Patent Document 2 a skin layer made of polyamide obtained by interfacial polymerization of a polyfunctional aromatic amine and a polyfunctional alicyclic acid halide on a porous support.
  • porous support examples include those in which a microporous layer having a substantially separating function is formed on the surface of a substrate.
  • the substrate examples include woven fabrics, nonwoven fabrics, mesh nets, and foamed sintered sheets made of polyester, polypropylene, polyethylene, polyamide, and the like.
  • the material for forming the microporous layer include various materials such as polysulfone and polyarylethersulfone such as polyethersulfone, polyimide, and vinylidene fluoride, and are particularly chemically, mechanically, and thermally stable. Therefore, polysulfone and polyaryl ether sulfone are preferably used.
  • the composite semipermeable membrane has practical chemical resistance, it cannot be said that any composite semipermeable membrane has chemical resistance that can withstand long-term resistance to regular or intermittent chlorine sterilization. Therefore, development of a composite semipermeable membrane having higher chemical resistance and practical levels of water permeability and salt-blocking properties, particularly a porous support excellent in chemical resistance, is desired.
  • porous epoxy resin cured material that can selectively distinguish substances with a planar molecular structure such as dioxin and PCB (polychlorinated biphenyl), has a low back pressure, and can be processed in large quantities.
  • Patent Document 3 The cured epoxy resin porous body is a non-particle agglomerated porous body having a columnar three-dimensional branched structure, and has a porosity of 20 to 80% and an average pore diameter of 0.5 to 50 ⁇ m. It is characterized by that.
  • the cured epoxy resin porous body is prepared by dissolving an epoxy resin and a curing agent in a porogen (pore forming agent) to prepare a mixed solution. Produced by forming a three-dimensional branched structure and then removing the porogen. In the case of the production method, there is a problem that a resin film having no pores is easily formed on the surface of the porous body, and the resin film needs to be removed for use as a separation medium, and the production process becomes complicated.
  • Patent Document 4 For the purpose of providing a method capable of producing a modified PTFE film without deteriorating mechanical properties and requiring a large capital investment, a bulk molded product of polytetrafluoroethylene powder is modified. After that, a method for producing a modified polytetrafluoroethylene film which is cut into a long film has been proposed (Patent Document 4).
  • a method for producing a chip seal for a scroll compressor comprising a step of molding a resin composition containing a fluororesin as a main component into a columnar or cylindrical molded body, and molding the molded body into a sheet-like body by skiving.
  • Patent Document 5 a method for producing a chip seal for a scroll compressor, comprising a step of molding a resin composition containing a fluororesin as a main component into a columnar or cylindrical molded body, and molding the molded body into a sheet-like body by skiving.
  • a polytetrafluoroethylene powder is compression molded to produce a cylindrical pre-compression molded body, the pre-compression molded body is horizontally suspended by a mandrel and fired to produce a fired porous molded body,
  • a method for producing a fired polytetrafluoroethylene porous sheet by cutting the fired porous molded body has been proposed (Patent Document 6).
  • An object of the present invention is to provide a method for easily producing a long thermosetting resin porous sheet having no resin film on the surface, and a thermosetting resin porous sheet produced by the method.
  • Another object of the present invention is to provide a composite semipermeable membrane having excellent chemical resistance and practical water permeability and salt blocking properties.
  • the present inventors have found that the target porous support can be easily produced by the following method, and have completed the present invention.
  • the present invention includes a step of producing a cylindrical or columnar resin block comprising a cured body of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a porogen, and the surface of the resin block is cut to a predetermined thickness.
  • the present invention relates to a method for producing a thermosetting resin porous sheet including a step of producing a long thermosetting resin sheet and a step of removing porogen in the thermosetting resin sheet.
  • thermosetting resin porous sheet can be easily produced without a resin film on the surface.
  • thermosetting resin sheet It is necessary to remove the porogen after producing the thermosetting resin sheet. Thereby, a smooth and continuous thermosetting resin porous sheet can be obtained.
  • the method of cutting after removing the porogen from the resin block is difficult to obtain a smooth and continuous thermosetting resin porous sheet because the resin block becomes brittle and a defect may occur in the hole during cutting.
  • the epoxy resin porous sheet is excellent in chemical resistance because it is made of a crosslinked epoxy resin, and has high strength (high pressure resistance) despite having a high porosity due to a continuous three-dimensional network skeleton.
  • polyethylene glycol As the porogen, it is preferable to use polyethylene glycol as the porogen.
  • thermosetting resin porous sheet obtained by the production method of the present invention has pores that communicate with each other.
  • the average pore diameter of the thermosetting resin porous sheet is preferably 0.01 to 0.4 ⁇ m from the viewpoints of water permeability, salt-inhibiting property, and formation of a uniform skin layer on the sheet surface.
  • the present invention also relates to a composite semipermeable membrane in which a skin layer is formed on the surface of the thermosetting resin porous sheet.
  • the skin layer is preferably formed of a material containing a polyamide-based resin in order to obtain practical water permeability and salt blocking property.
  • the method for producing a thermosetting resin porous sheet of the present invention comprises a step of producing a cylindrical or columnar resin block comprising a cured body of a thermosetting resin composition containing a thermosetting resin, a curing agent, and a porogen, It includes a step of cutting the surface of the resin block with a predetermined thickness to produce a long thermosetting resin sheet, and a step of removing porogen in the thermosetting resin sheet.
  • thermosetting resin examples include those that can form a porous body using a curing agent and a porogen. Examples include epoxy resins, phenol resins, melamine resins, urea resins (urea resins), alkyd resins, unsaturated polyester resins, polyurethanes, thermosetting polyimides, silicone resins, and diallyl phthalate resins. Epoxy resins are particularly preferred. Can be used.
  • thermosetting resin is an epoxy resin.
  • epoxy resin examples include bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, stilbene type epoxy resin, biphenyl type epoxy resin, bisphenol A novolak type epoxy resin, Contains cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, polyphenyl base epoxy resin such as tetrakis (hydroxyphenyl) ethane base, fluorene-containing epoxy resin, triglycidyl isocyanurate, heteroaromatic ring (eg triazine ring) Aromatic epoxy resins such as epoxy resins; aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl Ether type epoxy resin, aromatic epoxy resins such as alicyclic glycidyl ester type epoxy resins. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin brominated bisphenol A type epoxy resin, bisphenol F are used to form a uniform three-dimensional network skeleton and uniform pores, and to ensure chemical resistance and film strength.
  • a bisphenol A type epoxy resin from the group consisting of a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol AD type epoxy resin, a fluorene-containing epoxy resin, and a triglycidyl isocyanurate having an epoxy equivalent of 6000 or less and a melting point of 170 ° C. or less.
  • At least one aromatic epoxy resin selected selected from the group consisting of an alicyclic glycidyl ether type epoxy resin having an epoxy equivalent of 6000 or less and a melting point of 170 ° C. or less, and an alicyclic glycidyl ester type epoxy resin It is preferable to use at least one alicyclic epoxy resin.
  • curing agent examples include aromatic amines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (eg, phthalic anhydride, trimellitic anhydride).
  • aromatic amines eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene
  • aromatic acid anhydrides eg, phthalic anhydride, trimellitic anhydride
  • Non-aromatic curing agents such as adducts, bis (4-amino-3-methylcyclohexyl), phenolic resins, phenol novolac resins, heteroaromatic ring-containing amines (eg, triazine ring-containing amines), etc .; aliphatic amines (eg, ethylenediamine, diethylenetriamine, triethylene) Tetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine, polyester Terdiamine, etc.), alicyclic amines (isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane
  • Non-aromatic curing agents such as
  • metaphenylenediamine having two or more primary amines in the molecule, diaminodiphenylmethane, And at least one aromatic amine curing agent selected from the group consisting of diaminodiphenylsulfone; bis (4-amino-3-methylcyclohexyl) methane having two or more primary amines in the molecule, and bis (4-amino) It is preferred to use at least one alicyclic amine curing agent selected from the group consisting of (cyclohexyl) methane.
  • the combination of the epoxy resin and the curing agent is preferably a combination of an aromatic epoxy resin and an alicyclic amine curing agent, or a combination of an alicyclic epoxy resin and an aromatic amine curing agent. These combinations increase the heat resistance of the resulting epoxy resin porous sheet and are suitably used as a porous support for a composite semipermeable membrane.
  • a porogen is a solvent that can dissolve an epoxy resin and a curing agent, and can cause reaction-induced phase separation after the epoxy resin and the curing agent are polymerized, such as methyl cellosolve and ethyl cellosolve.
  • Examples thereof include cellosolves, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol and polypropylene glycol, and ethers such as polyoxyethylene monomethyl ether and polyoxyethylene dimethyl ether. These may be used alone or in combination of two or more.
  • polyethylene glycol having a molecular weight of 200 or less, polypropylene glycol having a molecular weight of 500 or less, polyoxyethylene monomethyl ether, and propylene glycol monomethyl ether acetate are preferably used. These may be used alone or in combination of two or more.
  • a solvent in which a reaction product of the epoxy resin and the curing agent is soluble can be used as a porogen.
  • porogen include brominated bisphenol A type epoxy resin (“Epicoat 5058” manufactured by Japan Epoxy Resin Co., Ltd.).
  • the porosity, average pore size, pore size distribution, etc. of the epoxy resin porous sheet are based on the type and compounding ratio of raw materials such as epoxy resin, curing agent, porogen, etc., and reaction such as heating temperature and heating time during reaction-induced phase separation. Since it varies depending on the conditions, it is preferable to create a phase diagram of the system and select the optimum conditions in order to obtain the desired porosity, average pore diameter, and pore diameter distribution. In addition, by controlling the molecular weight, molecular weight distribution, system viscosity, crosslinking reaction rate, etc. of the crosslinked epoxy resin during phase separation, the co-continuous structure of the crosslinked epoxy resin and porogen is fixed in a specific state and stable. A porous structure can be obtained.
  • the type and blending ratio of the epoxy resin and the curing agent may be determined so that the ratio of carbon atoms derived from the aromatic ring to the total carbon atoms constituting the epoxy resin porous sheet is in the range of 0.1 to 0.65. preferable.
  • the recognizability of the planar structure of the separation medium which is a characteristic of the epoxy resin porous sheet, tends to decrease.
  • it exceeds 0.65 it becomes difficult to form a uniform three-dimensional network skeleton.
  • the blending ratio of the curing agent to the epoxy resin is preferably such that the curing agent equivalent is 0.6 to 1.5 with respect to 1 equivalent of the epoxy group.
  • the curing agent equivalent is less than 0.6, the crosslinking density of the cured product is lowered, and the heat resistance, solvent resistance and the like tend to be lowered. On the other hand, if it exceeds 1.5, unreacted curing agent remains or tends to hinder the improvement of the crosslinking density.
  • a curing accelerator may be added to the solution in order to obtain the desired porous structure.
  • known ones can be used.
  • tertiary amines such as triethylamine and tributylamine, 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenol- Examples thereof include imidazoles such as 4,5-dihydroxyimidazole.
  • the average pore diameter of the epoxy resin porous sheet is more preferably 0.05 to 0.2 ⁇ m.
  • a method for adjusting the average pore diameter of the epoxy resin porous sheet to 0.01 to 0.4 ⁇ m a method in which two or more epoxy resins having different epoxy equivalents are mixed and used is also suitable.
  • the difference of epoxy equivalent is 100 or more, and it is preferable to mix and use a liquid epoxy resin and a solid epoxy resin at normal temperature.
  • the average pore diameter of the epoxy resin porous sheet can be adjusted to a desired range by appropriately setting various conditions such as the total epoxy equivalent and the porogen ratio and the curing temperature.
  • the cylindrical or columnar resin block can be produced, for example, by filling the epoxy resin composition into a cylindrical or columnar mold and then heating the epoxy resin three-dimensionally as necessary. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen.
  • a columnar resin block may be produced using a columnar mold, and then the central portion may be punched to produce a cylindrical resin block.
  • the temperature and time for curing the epoxy resin composition vary depending on the type of the epoxy resin and the curing agent, but the normal temperature is about 15 to 150 ° C., and the time is about 10 minutes to 72 hours.
  • curing is preferably performed at room temperature, the initial curing temperature is preferably about 20 to 40 ° C., and the curing time is preferably 1 to 48 hours.
  • post-cure post-treatment
  • the post-curing conditions are not particularly limited, but the temperature is room temperature or about 50 to 160 ° C., and the time is about 2 to 48 hours.
  • the thickness of the cylindrical resin block is not particularly limited, but is preferably 5 cm or more, more preferably 10 cm or more from the viewpoint of production efficiency of the epoxy resin porous sheet.
  • the diameter of the columnar resin block is not particularly limited, but is preferably 30 cm or more, more preferably 40 to 150 cm from the viewpoint of production efficiency of the epoxy resin porous sheet.
  • the width of the block (length in the axial direction) can be appropriately set in consideration of the size of the target epoxy resin porous sheet, but is usually 20 to 200 cm, and is 30 from the viewpoint of ease of handling. It is preferably ⁇ 150 cm, more preferably 50 to 120 cm.
  • the surface of the block is cut at a predetermined thickness to produce a long epoxy resin sheet.
  • FIG. 1 is a schematic view showing a process of slicing a cylindrical resin block 1 using a slicer 2.
  • the line speed during slicing is, for example, about 2 to 50 m / min.
  • the thickness of the epoxy resin sheet 4 is not particularly limited, but is preferably 50 to 500 ⁇ m, more preferably 100 to 200 ⁇ m from the viewpoint of strength and ease of handling.
  • the length of the epoxy resin sheet 4 is not particularly limited, but is preferably 100 m or more, more preferably 1000 m or more from the viewpoint of production efficiency of the epoxy resin porous sheet.
  • porogen in the epoxy resin sheet is removed to form a porous epoxy resin sheet having pores communicating therewith.
  • Examples of the solvent used for removing the porogen from the epoxy resin sheet include water, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), THF (tetrahydrofuran), and a mixed solvent thereof. Depending on the type of porogen, it is appropriately selected. Also, a supercritical fluid such as water or carbon dioxide can be preferably used.
  • the epoxy resin porous sheet may be dried.
  • the drying conditions are not particularly limited, but the temperature is usually about 40 to 120 ° C., preferably about 50 to 80 ° C., and the drying time is about 3 minutes to 3 hours.
  • a composite semipermeable membrane by forming a skin layer on the surface of the epoxy resin porous sheet, before forming the skin layer on the surface of the epoxy resin porous sheet, on the surface side where the skin layer of the epoxy resin porous body is formed.
  • An atmospheric pressure plasma treatment or an alcohol treatment may be applied.
  • the surface is modified (for example, improved hydrophilicity, increased surface roughness, etc.)
  • the adhesion between the epoxy resin porous sheet and the skin layer is improved, and the skin layer does not easily float (the phenomenon that the skin layer swells in a semicircular shape due to water entering between the epoxy resin porous sheet and the skin layer).
  • a semipermeable membrane can be produced.
  • the atmospheric pressure plasma treatment is preferably performed at a discharge intensity of about 0.1 to 5 Wsec / cm 2 in the presence of nitrogen gas, ammonia gas, or a rare gas such as helium or argon.
  • the alcohol treatment may be performed by applying an aqueous solution containing 0.1 to 90% by weight of a monohydric alcohol such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, or t-butyl alcohol, or in the aqueous solution. It is preferable to immerse in
  • the thickness of the epoxy resin porous sheet is not particularly limited, but is about 20 to 1000 ⁇ m from the viewpoint of strength, and when used as a porous support of a composite semipermeable membrane, practical water permeability and salt blocking property are not included. From the viewpoint, it is preferably about 50 to 250 ⁇ m, more preferably 80 to 150 ⁇ m. Further, the back surface of the epoxy resin porous sheet may be reinforced with a woven fabric or a nonwoven fabric.
  • the average pore diameter by mercury intrusion method is preferably 0.01 to 0.4 ⁇ m, more preferably 0.05 to 0.00. 2 ⁇ m. If the average pore diameter is too large, it is difficult to form a uniform skin layer, and if it is too small, the performance of the composite semipermeable membrane tends to be impaired. Further, the porosity is preferably 20 to 80%, more preferably 30 to 60%.
  • the material for forming the skin layer is not particularly limited, and examples thereof include cellulose acetate, ethyl cellulose, polyether, polyester, and polyamide.
  • a skin layer containing a polyamide-based resin obtained by polymerizing a polyfunctional amine component and a polyfunctional acid halogen component can be preferably used.
  • the polyfunctional amine component is a polyfunctional amine having two or more reactive amino groups, and examples thereof include aromatic, aliphatic, and alicyclic polyfunctional amines.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • aromatic polyfunctional amines include m-phenylenediamine, p-phenylenediamine, o-phenylenediamine, 1,3,5-triaminobenzene, 1,2,4-triaminobenzene, and 3,5-diamino.
  • examples include benzoic acid, 2,4-diaminotoluene, 2,6-diaminotoluene, N, N′-dimethyl-m-phenylenediamine, 2,4-diaminoanisole, amidole, xylylenediamine and the like.
  • Examples of the aliphatic polyfunctional amine include ethylenediamine, propylenediamine, tris (2-aminoethyl) amine, and n-phenyl-ethylenediamine.
  • Examples of the alicyclic polyfunctional amine include 1,3-diaminocyclohexane, 1,2-diaminocyclohexane, 1,4-diaminocyclohexane, piperazine, 2,5-dimethylpiperazine, 4-aminomethylpiperazine, and the like.
  • polyfunctional amines may be used alone or in combination of two or more. In order to obtain a skin layer having a high salt inhibition performance, it is preferable to use an aromatic polyfunctional amine.
  • the polyfunctional acid halide component is a polyfunctional acid halide having two or more reactive carbonyl groups.
  • polyfunctional acid halide examples include aromatic, aliphatic, and alicyclic polyfunctional acid halides.
  • aromatic polyfunctional acid halides include trimesic acid trichloride, terephthalic acid dichloride, isophthalic acid dichloride, biphenyldicarboxylic acid dichloride, naphthalene dicarboxylic acid dichloride, benzenetrisulfonic acid trichloride, benzenedisulfonic acid dichloride, chlorosulfonylbenzene dicarboxylic acid.
  • An acid dichloride etc. are mentioned.
  • Examples of the aliphatic polyfunctional acid halide include propanedicarboxylic acid dichloride, butanedicarboxylic acid dichloride, pentanedicarboxylic acid dichloride, propanetricarboxylic acid trichloride, butanetricarboxylic acid trichloride, pentanetricarboxylic acid trichloride, glutaryl halide, adipoid Examples include luhalides.
  • Examples of the alicyclic polyfunctional acid halide include cyclopropanetricarboxylic acid trichloride, cyclobutanetetracarboxylic acid tetrachloride, cyclopentanetricarboxylic acid trichloride, cyclopentanetetracarboxylic acid tetrachloride, cyclohexanetricarboxylic acid trichloride, and tetrahydrofuran.
  • Examples thereof include tetracarboxylic acid tetrachloride, cyclopentane dicarboxylic acid dichloride, cyclobutane dicarboxylic acid dichloride, cyclohexane dicarboxylic acid dichloride, and tetrahydrofurandicarboxylic acid dichloride.
  • polyfunctional acid halides may be used alone or in combination of two or more.
  • an aromatic polyfunctional acid halide it is preferable to use an aromatic polyfunctional acid halide.
  • a polymer such as polyvinyl alcohol, polyvinyl pyrrolidone or polyacrylic acid, a polyhydric alcohol such as sorbitol or glycerin may be copolymerized.
  • the method for forming the skin layer containing the polyamide resin on the surface of the epoxy resin porous sheet is not particularly limited, and any known method can be used. Examples thereof include an interfacial polymerization method, a phase separation method, and a thin film coating method.
  • the interfacial polymerization method is a method in which a skin layer is formed by interfacial polymerization by bringing an amine aqueous solution containing a polyfunctional amine component into contact with an organic solution containing a polyfunctional acid halide component.
  • Is a method in which a skin layer made of a polyamide-based resin is directly formed on the epoxy resin porous sheet by the interfacial polymerization on the epoxy resin porous sheet. Details of the conditions of such interfacial polymerization method are described in JP-A-58-24303, JP-A-1-180208, etc., and those known techniques can be appropriately employed.
  • an aqueous solution coating layer comprising an aqueous amine solution containing a polyfunctional amine component is formed on a porous support, and then an organic solution containing the polyfunctional acid halide component is contacted with the aqueous solution coating layer to perform interfacial polymerization.
  • the method of forming a skin layer by making it preferable is preferable.
  • the concentration of the polyfunctional amine component in the aqueous amine solution is not particularly limited, but is preferably 0.1 to 5% by weight, more preferably 1 to 4% by weight. If the concentration of the polyfunctional amine component is too low, defects such as pinholes are likely to occur in the skin layer, and the salt blocking performance tends to be reduced. On the other hand, when the concentration of the polyfunctional amine component is too high, the film thickness becomes too thick, the permeation resistance increases, and the permeation flux tends to decrease.
  • the concentration of the polyfunctional acid halide component in the organic solution is not particularly limited, but is preferably 0.01 to 5% by weight, more preferably 0.05 to 3% by weight. If the concentration of the polyfunctional acid halide component is less than 0.01% by weight, the unreacted polyfunctional amine component tends to remain, or defects such as pinholes are likely to occur in the skin layer, resulting in a decrease in salt blocking performance. Tend to. On the other hand, when the concentration of the polyfunctional acid halide component exceeds 5% by weight, the unreacted polyfunctional acid halide component tends to remain, or the film thickness becomes too thick to increase the permeation resistance, thereby increasing the permeation flux. It tends to decrease.
  • the organic solvent used in the organic solution is not particularly limited as long as it has low solubility in water, does not deteriorate the porous support, and dissolves the polyfunctional acid halide component.
  • cyclohexane, heptane, octane And saturated hydrocarbons such as nonane, and halogen-substituted hydrocarbons such as 1,1,2-trichlorotrifluoroethane is preferred.
  • a saturated hydrocarbon having a boiling point of 300 ° C. or lower, more preferably a boiling point of 200 ° C. or lower.
  • additives can be added to the aqueous amine solution and the organic solution for the purpose of facilitating film formation and improving the performance of the resulting composite semipermeable membrane.
  • the additive include surfactants such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate, sodium hydroxide that removes hydrogen halide generated by polymerization, trisodium phosphate, and triethylamine.
  • surfactants such as sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and sodium lauryl sulfate
  • sodium hydroxide that removes hydrogen halide generated by polymerization
  • trisodium phosphate triethylamine.
  • the time from applying the amine aqueous solution on the epoxy resin porous sheet to applying the organic solution is 180 seconds or less, although it depends on the composition of the aqueous amine solution, the viscosity, and the pore diameter of the surface of the epoxy resin porous sheet. Preferably, it is 120 seconds or less.
  • the application interval of the solution is too long, the aqueous amine solution may penetrate and diffuse deep inside the porous epoxy resin sheet, and a large amount of unreacted polyfunctional amine component may remain in the porous epoxy resin sheet.
  • the unreacted polyfunctional amine component that has penetrated deep inside the epoxy resin porous sheet tends to be difficult to remove even in the subsequent film cleaning treatment.
  • covering the said amine aqueous solution on an epoxy resin porous sheet you may remove excess amine aqueous solution.
  • the heating temperature is more preferably 70 to 200 ° C., particularly preferably 80 to 130 ° C.
  • the heating time is preferably about 30 seconds to 10 minutes, more preferably about 40 seconds to 7 minutes.
  • the thickness of the skin layer formed on the epoxy resin porous sheet is not particularly limited, but is usually about 0.05 to 2 ⁇ m, preferably 0.1 to 1 ⁇ m.
  • the composite semipermeable membrane of the present invention is not limited in its shape. That is, any conceivable membrane shape such as a flat membrane shape or a spiral element shape is possible. Moreover, in order to improve the salt-blocking property, water permeability, oxidation resistance, etc. of the composite semipermeable membrane, various conventionally known treatments may be performed.
  • the salt rejection of the composite semipermeable membrane having a skin layer containing a polyamide-based resin is preferably 98% or more, and more preferably 99% or more. Moreover, a permeation
  • a dry type composite semipermeable membrane may be used from the viewpoint of excellent workability and storage stability.
  • a semipermeable membrane does not receive a restriction
  • the semipermeable membrane may be processed into a spiral shape to produce a membrane unit, and the membrane unit may be dried to produce a dry spiral element.
  • the produced flat membrane-like composite semipermeable membrane is cut into a predetermined shape and size and set in a cell for flat membrane evaluation.
  • An aqueous solution containing about 1500 mg / L NaCl and adjusted to pH 6.5 to 7.5 with NaOH is brought into contact with the membrane at 25 ° C. by applying a differential pressure of 1.5 MPa between the supply side and the permeation side of the membrane.
  • the permeation rate and conductivity of the permeated water obtained by this operation were measured, and the permeation flux (m 3 / m 2 ⁇ d) and the salt rejection (%) were calculated.
  • Salt rejection was calculated in advance using a correlation (calibration curve) between NaCl concentration and aqueous solution conductivity in advance.
  • Salt rejection (%) ⁇ 1 ⁇ (NaCl concentration in the permeate [mg / L]) / (NaCl concentration in the feed liquid [mg / L]) ⁇ ⁇ 100
  • Example 1 (Production of epoxy resin porous sheet) 139 parts by weight of bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 828), 93.2 parts by weight of bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd., Epicoat 1010), bis (4-aminocyclohexyl) methane 52 parts by weight and 500 parts by weight of polyethylene glycol 200 (Sanyo Chemical Co., Ltd.) were placed in a container and stirred at 400 rpm for 15 minutes using a three-one motor to obtain an epoxy resin composition.
  • the prepared epoxy resin composition is filled in a cylindrical mold (outer diameter 35 cm, inner diameter 10.5 cm) to a height of 30 cm, cured at room temperature for 12 hours at 25 ° C., and further cured by reaction for 18 hours at 130 ° C. to form a cylindrical shape.
  • a resin block was produced. Thereafter, the surface is continuously sliced with a thickness of 150 ⁇ m using a cutting device (manufactured by TOSHIBA MACHINERY CO., LTD.) While rotating the block around the cylindrical axis, and a long epoxy resin sheet (length: 150 m) is obtained. ) And the epoxy resin sheet was immersed in water for 12 hours, polyethylene glycol was removed, and the epoxy resin porous sheet was obtained.
  • the epoxy resin porous sheet was dried in a dryer at 50 ° C. for about 4 hours.
  • the thickness of the epoxy resin porous sheet after drying was 145 ⁇ m, the porosity was 45%, and the average pore diameter was 0.106 ⁇ m.
  • Example 2 An epoxy resin porous sheet was produced in the same manner as in Example 1 except that a cylindrical resin block was produced by reaction curing at 60 ° C. for 3 hours and then reaction curing at 130 ° C. for 15 hours. The thickness of the epoxy resin porous sheet after drying was 148 ⁇ m, the porosity was 48%, and the average pore diameter was 0.08 ⁇ m. A composite semipermeable membrane was prepared in the same manner as in Example 1 except that the epoxy resin porous sheet was used, and the above permeation test was performed. As a result of the permeation test, the salt rejection and permeation flux were the same as in Example 1.
  • Example 3 A porous epoxy resin sheet was prepared in the same manner as in Example 1 except that a cylindrical resin block was prepared by reaction curing at 60 ° C. for 3 hours, then reaction curing at 130 ° C. for 13 hours, and further reaction curing at 160 ° C. for 2 hours. Was made. The thickness of the epoxy resin porous sheet after drying was 141 ⁇ m, the porosity was 42%, and the average pore diameter was 0.09 ⁇ m.
  • a composite semipermeable membrane was prepared in the same manner as in Example 1 except that the epoxy resin porous sheet was used, and the above permeation test was performed. As a result of the permeation test, the salt rejection and permeation flux were the same as in Example 1.
  • Example 4 (Production of epoxy resin porous sheet) A release agent (manufactured by Nagase ChemteX, QZ-13) was thinly applied to the inside of a 5 L stainless steel container, and the stainless steel container was dried in a dryer set at 40 to 100 ° C.
  • the epoxy resin block was taken out from the stainless steel container and sliced with a thickness of 100 to 150 ⁇ m using a cutting lathe device (manufactured by Toshiba Machine Co., Ltd.) to obtain an epoxy resin sheet.
  • the epoxy resin sheet was washed with pure water to remove polyethylene glycol, and then dried at 70 ° C. for 2 minutes, 80 ° C. for 1 minute, and 90 ° C. for 1 minute to produce an epoxy resin porous sheet. Then, the produced epoxy resin porous sheet was immersed in an aqueous solution of 20% by weight of isopropyl alcohol for 10 minutes for hydrophilization treatment.
  • a composite semipermeable membrane was produced in the same manner as in Example 1 using a porous epoxy resin sheet subjected to a hydrophilic treatment.
  • a permeation test was performed using the prepared composite semipermeable membrane.
  • the salt rejection was 99.5 (%)
  • the permeation flux was 0.9 (m 3 / m 2 ⁇ d).
  • SEM scanning electron microscope
  • Example 5 Implemented except using 3355.7 g of polypropylene glycol (trade name “D-250” manufactured by NOF Corporation) instead of 3087.2 g of polyethylene glycol (trade name “PEG200” manufactured by Sanyo Chemical Co., Ltd.)
  • An epoxy resin porous sheet subjected to a hydrophilization treatment in the same manner as in Example 4 was produced.
  • a composite semipermeable membrane was produced in the same manner as in Example 1 using a porous epoxy resin sheet subjected to a hydrophilic treatment.
  • a permeation test was performed using the prepared composite semipermeable membrane. As a result of the permeation test, the salt rejection was 99.3 (%), and the permeation flux was 0.9 (m 3 / m 2 ⁇ d).
  • FIGS. 3-1 and 3-2 Further, scanning electron microscope (SEM) photographs (800 times and 4000 times) of the cross section of the composite semipermeable membrane after the permeation test are shown in FIGS. 3-1 and 3-2. It can be seen that the skin layer is formed without defects on the epoxy resin porous sheet.
  • thermosetting resin porous sheet of the present invention is used as a support for a separation membrane or a composite semipermeable membrane.
  • the composite semipermeable membrane of the present invention is used for the production of ultrapure water, desalination of brackish water or seawater, etc., and also from dirt that causes pollution such as dyed wastewater and electrodeposition paint wastewater. Used to remove and recover contained pollutants or effective substances and close waste water. Moreover, it is used for the concentration of active ingredients for food use and the like, removal of harmful components for water purification, and the like.

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PCT/JP2009/068235 2008-10-23 2009-10-23 熱硬化性樹脂多孔シートの製造方法、熱硬化性樹脂多孔シート、及びそれを用いた複合半透膜 Ceased WO2010047383A1 (ja)

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011046145A1 (ja) * 2009-10-16 2011-04-21 日東電工株式会社 複合半透膜の製造方法
WO2012077636A1 (ja) * 2010-12-06 2012-06-14 日東電工株式会社 エポキシ樹脂多孔シートの製造方法
CN102832364A (zh) * 2011-06-13 2012-12-19 日东电工株式会社 非水电解质蓄电装置用隔板、非水电解质蓄电装置以及它们的制造方法和制造系统
WO2012172790A1 (ja) * 2011-06-13 2012-12-20 日東電工株式会社 熱硬化性樹脂多孔質シートの製造方法および製造装置、ならびに熱硬化性樹脂多孔質シートおよびシートロール
US20130098830A1 (en) * 2010-06-30 2013-04-25 Nitto Denko Corporation Method for producing porous thermosetting resin sheet and composite separation membrane using same
US20130330591A1 (en) * 2011-06-13 2013-12-12 Nitto Denko Corporation Porous epoxy resin membrane, separator for nonaqueous electrolyte electricity storage devices, nonaqueous electrolyte electricity storage device, composite semipermeable membrane, and production methods thereof
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CN103620816A (zh) * 2011-06-13 2014-03-05 日东电工株式会社 非水电解质蓄电装置及其制造方法
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WO2015098053A1 (ja) * 2013-12-25 2015-07-02 日東電工株式会社 電解コンデンサ用セパレータ、その製造方法、及びそれを用いた電解コンデンサ
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JP2012072255A (ja) * 2010-09-28 2012-04-12 Nitto Denko Corp エポキシ樹脂多孔シート及びその製造方法
JP2012217871A (ja) * 2011-04-04 2012-11-12 Nitto Denko Corp 複合半透膜及びその製造方法
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JP2014001373A (ja) * 2012-05-22 2014-01-09 Nitto Denko Corp 非水電解質蓄電デバイス用セパレータの製造方法、及びエポキシ樹脂多孔質膜の製造方法
US10464055B2 (en) * 2014-03-11 2019-11-05 Nitto Denko Corporation Photocatalytic element
KR101430717B1 (ko) * 2014-03-25 2014-08-14 홍순승 합성수지시트 제조장치 및 제조방법
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WO2019065493A1 (ja) * 2017-09-29 2019-04-04 住友化学株式会社 スパイラル型ガス分離膜エレメント、ガス分離膜モジュール、及びガス分離装置

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0494726A (ja) * 1990-08-09 1992-03-26 Toray Ind Inc 複合半透膜およびその製造方法および高純度水の製造方法
JP2003096229A (ja) * 2001-09-20 2003-04-03 Mitsui Chemicals Inc 多孔質（共）重合体フィルムの製造方法およびそれにより得られる多孔質（共）重合体フィルム
WO2006073173A1 (ja) * 2005-01-07 2006-07-13 Asahi Kasei Kabushiki Kaisha エポキシ樹脂硬化物多孔体
JP2008013672A (ja) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology エポキシ樹脂硬化物多孔体と繊維を含んでなる複合材料

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4277344A (en) 1979-02-22 1981-07-07 Filmtec Corporation Interfacially synthesized reverse osmosis membrane
CH660852A5 (de) 1982-11-23 1987-05-29 Aligena Ag Dynamische membranen, die sich als duenne polymerschichten auf poroesen, polymeren traegermaterialien befinden.
US4520044A (en) 1984-07-30 1985-05-28 E. I. Du Pont De Nemours And Company Production of composite membranes
US4529646A (en) 1984-07-30 1985-07-16 E. I. Du Pont De Nemours And Company Production of composite membranes
US4761234A (en) 1985-08-05 1988-08-02 Toray Industries, Inc. Interfacially synthesized reverse osmosis membrane
JPS62121603A (ja) 1985-08-05 1987-06-02 Toray Ind Inc 複合半透膜及びその製造方法
JPS63218208A (ja) 1987-03-05 1988-09-12 Toray Ind Inc 複合半透膜およびその製造方法
US4948507A (en) 1988-09-28 1990-08-14 Hydranautics Corporation Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same
US4872984A (en) 1988-09-28 1989-10-10 Hydranautics Corporation Interfacially synthesized reverse osmosis membrane containing an amine salt and processes for preparing the same
JP4028120B2 (ja) 1999-02-23 2007-12-26 Ｎｔｎ株式会社 スクロール型圧縮機用チップシールの製造方法
JP3556551B2 (ja) 1999-12-27 2004-08-18 エスケー化研株式会社 連通多孔体の形成方法
JP2001341138A (ja) 2000-06-06 2001-12-11 Daikin Ind Ltd ポリテトラフルオロエチレン成形体およびその製造法
US7081202B2 (en) 2001-03-19 2006-07-25 Nitto Denko Corporation Composite semipermeable membrane, production method thereof, and water treatment method using the same
EP1800735B1 (en) 2001-03-19 2012-05-23 Nitto Denko Corporation Method for producing composite semipermeable membrane
JP2003088730A (ja) * 2001-09-20 2003-03-25 Nitto Denko Corp 逆浸透膜エレメントの処理方法、および逆浸透膜モジュール
US20030036085A1 (en) * 2002-08-19 2003-02-20 Salinaro Richard F Membranes
JP4500002B2 (ja) 2003-05-06 2010-07-14 日東電工株式会社 複合半透膜及びその製造方法
JP2004338208A (ja) 2003-05-15 2004-12-02 Nitto Denko Corp 改質ポリテトラフルオロエチレンの製造方法
US8025960B2 (en) 2004-02-02 2011-09-27 Nanosys, Inc. Porous substrates, articles, systems and compositions comprising nanofibers and methods of their use and production
CA2583469C (en) 2004-10-06 2013-03-19 Research Foundation Of State University Of New York High flux and low fouling filtration media
US8758887B2 (en) * 2004-12-22 2014-06-24 Entegris, Inc. Multilayer porous membrane and process
US8231013B2 (en) 2006-12-05 2012-07-31 The Research Foundation Of State University Of New York Articles comprising a fibrous support

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0494726A (ja) * 1990-08-09 1992-03-26 Toray Ind Inc 複合半透膜およびその製造方法および高純度水の製造方法
JP2003096229A (ja) * 2001-09-20 2003-04-03 Mitsui Chemicals Inc 多孔質（共）重合体フィルムの製造方法およびそれにより得られる多孔質（共）重合体フィルム
WO2006073173A1 (ja) * 2005-01-07 2006-07-13 Asahi Kasei Kabushiki Kaisha エポキシ樹脂硬化物多孔体
JP2008013672A (ja) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology エポキシ樹脂硬化物多孔体と繊維を含んでなる複合材料

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011046145A1 (ja) * 2009-10-16 2011-04-21 日東電工株式会社 複合半透膜の製造方法
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WO2015098052A1 (ja) * 2013-12-25 2015-07-02 日東電工株式会社 水系電解質蓄電デバイス用セパレータとその製造方法、及びそれを用いた水系電解質蓄電デバイス
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US9186633B2 (en) 2015-11-17
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