WO2008029761A1 - Procédé de fabrication d'une membrane fonctionnelle - Google Patents

Procédé de fabrication d'une membrane fonctionnelle Download PDF

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Publication number
WO2008029761A1
WO2008029761A1 PCT/JP2007/067129 JP2007067129W WO2008029761A1 WO 2008029761 A1 WO2008029761 A1 WO 2008029761A1 JP 2007067129 W JP2007067129 W JP 2007067129W WO 2008029761 A1 WO2008029761 A1 WO 2008029761A1
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WIPO (PCT)
Prior art keywords
functional
porous substrate
pores
impregnated
functional polymer
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PCT/JP2007/067129
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English (en)
Japanese (ja)
Inventor
Hideki Hiraoka
Original Assignee
Toagosei Co., Ltd.
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Application filed by Toagosei Co., Ltd. filed Critical Toagosei Co., Ltd.
Priority to JP2008533145A priority Critical patent/JPWO2008029761A1/ja
Publication of WO2008029761A1 publication Critical patent/WO2008029761A1/fr

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
    • B29C44/34—Auxiliary operations
    • B29C44/56—After-treatment of articles, e.g. for altering the shape
    • B29C44/5618—Impregnating foam articles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1058—Polymeric electrolyte materials characterised by a porous support having no ion-conducting properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/02—Cellular or porous
    • B32B2305/026—Porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/18—Fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/08—Impregnating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a method of producing a functional film.
  • the above ion exchange membrane can suppress the permeation of fuel such as methanol and has ion conductivity, and in particular, is expected to be applied to direct methanol fuel cells (DMFCs). It is
  • JP-A-2005-76012 has a function having a step of immersing a porous resin sheet in a container containing a polymer precursor solution.
  • a method of producing a sex membrane is disclosed.
  • the porous substrate since the porous substrate is immersed in the solution, the solution is impregnated from both sides of the porous substrate into the pores.
  • the immersion time of the porous substrate is increased as one means for avoiding the entrapment of air in the pores.
  • the present invention has been made in view of the above problems, and the problem to be solved by the present invention is to provide a method for producing a functional film, in which the air in the hole is removed and the productivity is also better than before.
  • a method for producing a functional film according to the present invention is a method for producing a functional film in which a functional polymer is filled in pores of a porous substrate, and a porous group is provided.
  • the present invention is characterized by at least a second step of fixing the functional polymer in the pores by chemically reacting the precursor or the liquid thereof.
  • the chemical reaction in the second step is preferably one or more kinds of reactions selected from a polymerization reaction, a crosslinking reaction and a grafting reaction.
  • a polymerization reaction for polymerizing low molecular weight compounds such as monomers and oligomers a crosslinking reaction of a crosslinking agent added as necessary, a crosslinking reaction of a functional polymer precursor of high molecular weight having crosslinking reactivity, a function Reaction of the porous polymer precursor on the porous substrate, and the like.
  • the lamination in the first step may be performed by sandwiching the functional polymer precursor or a layer of the liquid between the porous substrate and the base substrate.
  • a cover base material is further provided on the porous base material surface opposite to the lamination side of the layer of the functional polymer precursor or the liquid between the first step and the second step. You may have the 3rd process of laminating.
  • the porous substrate may be previously subjected to a hydrophilic treatment.
  • the pore of the porous substrate may be impregnated beforehand with a volatile solvent having an affinity for the functional polymer precursor or the liquid thereof.
  • the functional polymer precursor or the solution thereof is impregnated into the pores from one surface of the porous substrate.
  • the method for producing a functional film according to the present invention air in the hole is more easily released than in the conventional production method.
  • the productivity is also good.
  • the layer of the functional polymer precursor or the liquid is sandwiched between the porous substrate and the base substrate in the first step, the impregnation of the substance to be impregnated into the pores is improved. It can be done.
  • the functional polymer precursor impregnated in the pores or the liquid thereof is subjected to a chemical reaction (polymerization reaction, crosslinking reaction, grafting reaction, etc.) to obtain a functional polymer in the pores. It is firmly held and fixed. Therefore, it is possible to obtain a functional film having good durability in which it is difficult for the functional polymer to drop out of the pores when using the functional film.
  • a chemical reaction polymerization reaction, crosslinking reaction, grafting reaction, etc.
  • the loss is large because a large amount of solution which has not been impregnated into the porous substrate finally remains.
  • the manufacturing method of the present invention since it has the first step! /, It is possible to use the material to be impregnated such as the solution only for the necessary amount, There is an advantage that the loss is reduced.
  • the to-be-immersed substance impregnated in the hole in the first step is shielded from air (outside air) by the cover base material. Therefore, when forming a functional polymer from a functional polymer precursor by polymerization etc., depending on the type of functional polymer precursor, the oxygen in the air may inhibit the polymerization, but it is easy to prevent this. . In addition, the flatness of the functional film to be obtained can be easily improved.
  • the porous substrate is rendered hydrophilic in advance.
  • the highly hydrophilic substance to be impregnated is easily impregnated into the pores. Therefore, it is easy to improve productivity.
  • the volatile solvent in the pores volatilizes to replace the impregnated substance. Ru.
  • the infiltration of the substance to be impregnated into the pores is improved, and the productivity can be further improved.
  • FIG. 1 is a view schematically showing an example of a method for continuously producing a functional film by using a die coater (coating a material to be impregnated on a base substrate).
  • FIG. 2 is a view schematically showing an example of a method for continuously producing a functional film using a comma coater.
  • FIG. 3 is a view schematically showing an example in the case where a porous solvent is impregnated in advance in the pores of the porous substrate in the manufacturing method of FIG.
  • FIG. 4 is a view schematically showing an example of a method for continuously producing a functional film by using a die coater (coating a substance to be impregnated on a porous substrate).
  • the present production method the method for producing a functional film according to the present embodiment (hereinafter sometimes referred to as “the present production method”) will be described in detail.
  • the present production method is a method for producing a functional film in which a functional polymer is filled in the pores of a porous substrate, and includes at least the following first and second steps. [0031] 1. First step
  • the first step is to laminate a layer of a functional polymer precursor or a liquid thereof (hereinafter sometimes referred to as “impregnated matter”) on one surface of a porous substrate, and to make the layer porous.
  • the functional polymer precursor or its solution is impregnated into the pores of the substrate.
  • the porous substrate mainly forms the framework of the functional membrane.
  • a planar shape such as a film shape, a sheet shape, or a plate shape can be exemplified as a suitable shape.
  • the porous substrate is impregnated with the substance to be impregnated, it has at least an open hole communicating with the outside.
  • open pores closed pores may be present.
  • the open pores are preferably through holes penetrating from one side to the other side of the porous substrate.
  • non-through holes may be present.
  • the through holes may penetrate, for example, substantially perpendicularly to the substrate surface, or may penetrate at an angle of less than 90 ° with respect to the substrate surface. . In addition, they may be penetrated at random, such as meandering or zigzag.
  • the cross-sectional shape of the open pores is not particularly limited, and any cross-sectional shape may be used as long as it can be impregnated with the substance to be impregnated.
  • the cross section of the open pores specifically, for example, a circular shape, an elliptical shape, a polygonal shape, a shape in which these are connected, and a combination thereof can be exemplified.
  • the porosity of the porous base material can be appropriately selected depending on the application of the functional film and the like, and it is preferable that the porosity is approximately in the range of 5 to 95%.
  • the upper limit of the porosity of the porous base material is preferably 90% or less, and more preferably 85% or less. % Or less is most preferable.
  • the lower limit of the porosity of the porous substrate is preferably 10% or more, more preferably 15% or more, and most preferably 20% or more.
  • the porosity is determined from the thickness and area of the porous substrate, the volume is measured, and the ratio of air occupied in the entire volume is calculated from the specific gravity of the material to be constructed.
  • % Porosity (thickness of porous substrate X area of porous substrate weight / configuration of porous substrate specific gravity of material) / (thickness of porous substrate X area of porous substrate) X 100
  • the pore diameter of the porous base material can also be appropriately selected S depending on the application of the functional film and the like. If the pore diameter is too small, it tends to be difficult to impregnate the material to be impregnated. On the other hand, if the diameter of the hole is too large, it will be difficult to retain the functional polymer in the hole, and it may fall off when the functional film is deformed. These should be kept in mind when selecting the hole diameter.
  • the upper limit of the hole diameter is preferably 50 m or less, more preferably 10 m or less, and more preferably l ⁇ m or less from the viewpoint of easily retaining the functional polymer filled in the hole. Most preferred.
  • the lower limit of the pore diameter is, for example, a force S of at least 0.101 m or more, preferably 0 ⁇ Ol m or more, from the viewpoint that the functional polymer precursor or the liquid is easily filled in the pores. .
  • the hole diameter is a value measured by mercury porosimetry.
  • the material of the porous substrate can be appropriately selected according to the application of the functional film, etc.
  • organic materials such as polymers, ceramics such as glass, alumina, mullite, etc.
  • inorganic materials such as mixes and metals (including alloys) and composite materials made by combining them.
  • the material of the porous base material a functional film excellent in flexibility and strength can be obtained, and from the viewpoint of deformation / defects and the like during continuous production from a hole! Polymers can be suitably used.
  • examples of the above-mentioned polymer include ethylene-based resins (resins mainly composed of ethylene such as polyethylene), olefin-based resins such as polypropylene and polymethylpentene, and chlorides such as polychlorinated bures.
  • ethylene-based resins resins mainly composed of ethylene such as polyethylene
  • olefin-based resins such as polypropylene and polymethylpentene
  • chlorides such as polychlorinated bures.
  • olefin resin etc. from the viewpoint of obtaining a functional film excellent in mechanical strength, chemical stability, chemical resistance, flexibility and the like. .
  • the thickness of the porous substrate may be appropriately selected according to the application of the functional film! For example, when using a functional membrane as an ion exchange membrane such as a fuel cell, if the thickness of the porous substrate is excessively thin, the membrane strength may be reduced, or the amount of permeation of fuel such as methanol may be large. There is a tendency to On the other hand, when the thickness of the porous substrate is excessively thick, the migration path of ions becomes long, the membrane resistance becomes large, and the tendency such that the ion conductivity decreases is observed. Therefore, these should be kept in mind in selecting the thickness of the porous substrate.
  • the thickness of the porous substrate may vary depending on the material thereof.
  • the upper limit of the thickness of the porous substrate may be, for example, an internal resistance in the case of an ion exchange membrane.
  • the force S is preferably 200 m or less, more preferably 150 m or less, and more preferably 100 m or less.
  • the lower limit of the thickness of the porous substrate is 1 m or more from the viewpoint of maintaining the membrane strength and making it difficult to cause defects such as breakage when joining the electrode or incorporating it into a fuel cell. Is preferably 5 m or more, more preferably 10 m or more.
  • the method for obtaining the porous substrate as described above is different in force depending on the material, for example, a method by stretching, coating a solution or a melt of the substrate material in which the pore forming material is dispersed in a planar shape.
  • a method of making the surface flat by removing the solvent by evaporation, cooling the molten base material, etc., and removing the pore forming material to form holes, for the flat surface formed base material Method of forming holes by using processing means such as punching, drilling, laser, chemical, physical etching, etc., Melt solution of base material such as polymer is poured into a mold that can transfer the holes. rear, By peeling off the flat substrate material, the method of transferring the hole to the substrate surface, etc. is exemplified.
  • the most common method is the method by stretching. That is, in this method, the material of the porous base material such as a polymer and the liquid or solid pore former are mixed by a method such as melt mixing, and the pore former is once finely dispersed, and this is used as a T die. It is stretched while being extruded from etc., and the pore forming material is removed by a method such as washing to make a porous substrate.
  • a stretching method there are methods such as uniaxial stretching and biaxial stretching.
  • the porous substrate is formed of a hydrophobic polymer material
  • at least the surface of the porous substrate on the side in contact with the object to be impregnated is treated to be hydrophilic. It is good to be done.
  • the porous member is previously hydrophilized when impregnating the highly hydrophilic material into the pores, the highly hydrophilic material is rapidly impregnated into the pores, if the porous substrate is previously hydrophilized. It is because productivity can be improved.
  • hydrophilic treatment examples include surfactant treatment, corona treatment, sulfonation treatment, graft treatment of a hydrophilic polymer, and the like. One or more of these treatments may be used in combination.
  • the pores of the porous substrate are impregnated with a functional polymer precursor or its liquid (impregnated material).
  • the functional polymer precursor capable of producing a functional polymer when the functional polymer precursor capable of producing a functional polymer is impregnated, when the liquid containing the functional polymer precursor is impregnated, the functional polymer and the functional polymer precursor May be impregnated.
  • the functional polymer precursor is one that is polymerized in the second step to become a functional polymer, has a functional group that exhibits a function such as an ion exchange group, etc. /
  • a functional group that exhibits a function such as an ion exchange group, etc.
  • an environment using a membrane below is a mixture of a polymer that can not be fixed in the pores due to elution and a compound that has cross-linking reactivity, and the cross-linkable substance cross-links to solidify the polymer.
  • any of those which can become a functional polymer as a whole have a functional group capable of forming a chemical bond with a crosslinkable or functional group on the surface of a porous substrate, and have a function such as an ion exchange group
  • polymers which also have a functional group that expresses C. or O.sup.2, which is fixed as a functional polymer by crosslinking or formation of a chemical bond to the surface of the porous substrate (re, graft reaction).
  • Various types of functional polymers can be used as the above-mentioned functional polymer depending on the purpose, application and the like of the functional film.
  • cation exchange groups such as a sulfonic acid group, a carboxylic acid group, a phosphonic acid group, and a phosphonous acid group
  • Anion exchange groups such as ammonium group, an epoxy group And polymerizable groups such as an alkoxysilane group
  • amino groups such as an amino group, a mercapto group and an acid anhydride group, which can be reacted in combination with these polymerizable groups, such as polymerization and addition
  • hydrophilicity examples of polymers having functional functional groups such as hydrophilic groups such as ether groups, hydroxyl groups and pyrrolidone groups capable of absorbing and holding drugs, and lipophilic groups such as long chain alkyl groups capable of holding lipophilic drugs It is possible to do S.
  • These polymers may have one or more
  • various types of functional polymer precursors may be used depending on the purpose, application, etc. of the functional film.
  • a monomer having a functional functional group described above, a functional group that can be converted to the functional functional group before and after polymerization, and a monomer having a site to which the functional functional group can be introduced before and after polymerization hereinafter At least one or more functional monomers are included.
  • These functional monomers have one or more sites capable of introducing a functional group before or after polymerization, or a functional group that can be converted to the functional group, or the functional group described above! /, Even good!
  • the functional membrane when used as an ion exchange membrane such as a fuel cell, specifically as the functional monomer, for example, a monomer having an ion exchange group, a functional group capable of being converted to an ion exchange group It is preferable to use a monomer having the following formula, a monomer having a moiety capable of introducing an ion exchange group before and after polymerization, and the like. These may be used alone or in combination of two or more.
  • the monomer having an ion exchange group as described above is characterized by having an ion exchange with a polymerizable functional group in one molecule. It is a compound having a substituent and a substituent.
  • the monomer having an ion exchange group include, for example, 2- (meth) arylamido-2-methylpropanesulfonic acid, 2- (meth) acrylamide-2-methylpropanephosphonic acid, and styrenesulfonic acid. And (meth) aryl sulfonic acid, vinyl sulfonic acid, isoprene sulfonic acid, (meth) acrylic acid, maleic acid, crotonic acid, bulonic acid, acid phosphoric acid group-containing (meth) atalylate and the like.
  • (meth) acrylic means “acrylic and / or methacrylic
  • (meth) aryl means “aryl and / or methallyl
  • (meth) atarylate means “allarylate and / or metatalylate” Means the same (the same applies hereinafter).
  • the monomer having a functional group that can be converted to an ion exchange group before and after the polymerization can include, for example, salts, anhydrides, and esters of the above-mentioned compounds.
  • the acid residue of the monomer to be used is a derivative such as a salt, an anhydride, or an ester
  • proton conductivity can be imparted by converting it to a protonic acid type after polymerization.
  • the monomer having a site capable of introducing an ion exchange group before and after the above polymerization include, for example, monomers having a benzene ring such as styrene, ⁇ -methylstyrene, chloromethylstyrene and t-butylstyrene. It can be illustrated.
  • a method of introducing a cation exchange group to these specifically, for example, a method of sulfonation with a sulfonating agent such as chlorosulfonic acid, concentrated sulfuric acid, sulfur trioxide and the like can be mentioned.
  • a bule compound having a sulfonate group, a bule compound having a phosphate group, and the like are preferable, and a viewpoint such as having high polymerizability and the like is preferable.
  • 2- (meth) acrylamide-2-methylpropane sulfonic acid is preferable.
  • the functional polymer precursor may contain, in addition to the functional monomer, a crosslinking agent and the like.
  • a crosslinking point can be formed in the functional polymer formed by polymerization of the functional monomer, and the functional polymer can be a crosslinked product. Therefore, the insolubility and infusibility of the functional polymer filled in the pores of the functional film are improved, and there is an advantage that it becomes difficult to drop out of the pores.
  • the functional polymer precursor has a functional group that exhibits functionality or such a functional group. You may mix
  • the above-mentioned crosslinking agent is, for example, a compound having two or more polymerizable functional groups in one molecule, and is capable of performing a crosslinking reaction with a polymerizable double bond in one molecule.
  • examples thereof include compounds having a combination of functional groups. One or more of these may be contained.
  • the former crosslinking agent examples include N, N′-methylenebis (meth) acrylylamide, N, N, -butylenebis (meth) acrylamide, polyethylene glycol di (meth) arylates, polypropylene glycol Di (meth) atalylate, trimethylol propane, dilinolee tenole, pentaerythritole tri alinolee tenole, divininole benzene, bisphenol di (meth) atalylate, isocyanuric acid di (meth) atalylate, tetraaryl
  • crosslinkable monomers such as oxetane, triallylamine and dihydroxyacetate can be given.
  • crosslinking agent specifically, a crosslinkable monomer such as N methylol acrylamide, N methoxymethyl acrylamide, N-butoxymethyl acrylamide and the like can be exemplified. These can be heated to conduct a condensation reaction or the like after radical polymerization of the polymerizable double bond, to cause a condensation reaction, etc., and to carry out a similar crosslinking reaction by heating simultaneously with the radical polymerization.
  • crosslinking agent is not limited to a compound having a carbon-carbon double bond, and although the polymerization reaction rate is slightly small, a compound having a bifunctional or higher epoxy compound, a phenyl group having a hydroxymethyl group, etc. Etc. can also be used.
  • crosslinking is carried out by reacting with an acid such as a carboxyl group contained in the polymer. Bridge points are formed.
  • the functional polymer precursor may contain a monomer copolymerizable with the functional monomer and / or the crosslinking agent.
  • a monomer copolymerizable with the functional monomer and / or the crosslinking agent include, for example, (meth) acrylic esters, (meth) acrylamides, maleimides, styrenes, organic acid buries, aryl compounds, methallyl compounds and the like. Can. These are included one or two or more!
  • the functional polymer precursor described above is not particularly limited in the polymerization method at the time of force that will polymerize the monomer in a later step, and irradiation of active energy rays such as ultraviolet rays, electron beams, etc. Various methods such as heating can be used.
  • the functional polymer precursor may contain a polymerization initiator.
  • radical initiator for thermally initiated polymerization and redox initiated polymerization include, for example, azo compounds such as 2,2′-azobis (2-amidinopropane) dihydrochloride, and persulfates Peroxides such as monium, potassium persulfate, sodium persulfate, hydrogen peroxide, benzene peroxide, cumene hydroperoxide, dibutyl peroxide, the above peroxides, sulfites, bisulfites, thiosulfates Redox initiator combined with a reducing agent such as salt, formamidine sulfinic acid, askorbinic acid, etc.
  • Azo based radical polymerization initiator such as 2, 2'-azobis mono (2- amidino propane) dihydrochloride, azobis cyanovaleric acid It is possible to illustrate S etc. One or more of these may be contained.
  • photopolymerization initiator examples include, for example, benzophenone type, thioxantone type, thioataridon type, benzoin type, benzyl type, acetophenone type, and derivatives thereof. Can. One or more of these may be included.
  • examples of the benzophenone-based initiator include, for example, methyl o benzylbenzoate, 4 phenylbenzophenone, 4 benzoyl 4′-methyldiphenyl Phenized, 3,3 ', 4,4'-tetra (t-butylperoxycarboquinone) benzophenone, 2,4,6-trimethylbenzophenone, 4-benzoyl N, N dimethyl-N- [2 (1 (1) Oxy 2 propenyloxy) ethyl] benzenemetanamimbide, (4 benzeneyl) trimethylammonium chloride, 4,4'-dimethylaminobenzophenone, 4,4'-diethylaminobenzophenone and the like can be exemplified.
  • thioxanthone initiator examples include, for example, thioxanthone, 2-chlorothioxanthone, 2,4 jettythioxanthone, 2-acetylthioxanthone, etc.
  • thioacridone initiator examples include, for example, thioathalidone and the like.
  • benzoin initiator may include benzoin, benzoin methyl ethenole, benzoin isopropinoleate tenole, bennin ethinolee tenole, benzoin isobutyl ether, and the like.
  • acetophenone-based initiator examples include, for example, acetophenone, propiophenone, diethoxyacetophenone, 2, 2-dimethoxy 1, 2-diphenenoleethane 1-on, 1 -hydroxycyclohexyl.
  • benzyl-based initiator examples include, for example, benzyl and the like.
  • the upper limit of the content of these photopolymerization initiators is contained in the functional polymer precursor from the viewpoint of the stability of the functional polymer precursor or the liquid thereof, and the maintenance of the degree of polymerization of the obtained polymer. 10% by weight or less is preferable, and 5% by weight or less is more preferable, and 2% by weight or less is most preferable.
  • the lower limit of the content of these photopolymerization initiators is preferably at least 0.01% by mass with respect to the total mass of the monomers contained in the functional polymer precursor from the viewpoint of maintaining the polymerizability and the like. 0. 01% by mass or more The force is preferably 0.1% by mass or more.
  • the functional polymer precursor may optionally contain one or more of various additives such as an antioxidant, a chelating agent, a UV absorber, and a plasticizer! Also good!
  • the functional polymer precursor including a mixture of a crosslinking agent and a polymerization initiator, etc.
  • the functional polymer precursor including a mixture of a crosslinking agent and a polymerization initiator, etc.
  • the pores can be impregnated.
  • the preferable viscosity is about 1-1 OOOOmPa ⁇ s at 25 ° C.
  • the functional polymer precursor itself is a liquid
  • it is a liquid monomer having an acidic group, such as vinyl sulfonic acid, acrylic acid, acrylamido-N-phosphoric acid or a mixture of styrene and dibenzene.
  • an acidic group such as vinyl sulfonic acid, acrylic acid, acrylamido-N-phosphoric acid or a mixture of styrene and dibenzene.
  • a precursor that can be converted to a functional polymer through a chemical reaction such as sulfonation after polymerization can be exemplified.
  • the preferred viscosity is about 1 to about 100 mPa's at 25 ° C.
  • the above viscosity is a value measured by a B-type viscometer.
  • solvent and dispersion medium examples include aromatic organic solvents such as toluene, xylene and benzene, aliphatic organic solvents such as hexane and heptane, cromoform and dichloroethane, etc.
  • Chlorinated solvents such as jetyl ether, ketones such as methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, dimethyl formamide, Amide-based solvents such as dimethylacetoamide, N-methyl-2-pyrrolidone, water, alcohol and the like can be exemplified. One or more of these may be contained. Among these, preferably, it is preferable to mainly contain water. They are excellent in handling and economy.
  • the concentration of the solution or dispersion can be appropriately adjusted in consideration of the viscosity, the impregnating ability to the pores, the impregnation amount of the functional polymer precursor component to be impregnated into the pores, and the like.
  • the liquid concentration is excessively low, the amount of the functional polymer precursor component to be impregnated into the pores may be reduced, and the function of the functional film may be degraded.
  • the liquid concentration becomes excessively high There is a tendency that the viscosity becomes high, the impregnation property is lowered and the productivity is deteriorated. Therefore, these should be kept in mind when selecting the liquid concentration.
  • the concentration of the above solution or dispersion As the lower limit of the concentration of the above solution or dispersion, if the concentration is too low, it is necessary to repeat the impregnation step, and from the viewpoint of decreasing productivity etc., 5% by mass or more is preferable. 20% by weight or more is most preferred, with% by weight being more preferred.
  • the component constituting the precursor may contain a low molecular weight component such as a monomer or an oligomer, or a molecule Precursors composed of relatively low molecular weight polymers of 10,000 or less can be suitably used.
  • the concentration is lowered to improve the impregnation property immediately, the loading amount of the functional polymer is difficult to increase and the impregnation defect tends to occur.
  • the functional polymer precursor as in the present invention when used, the viscosity can be reduced, the impregnation property is excellent immediately, and the air in the pores can be easily expelled.
  • high concentration is also suitable for filling many functional polymers into pores.
  • the functional polymer precursor component impregnated in the pores is polymerized and cross-linked later to form a functional polymer, whereby the functional film is used in an environment in contact with a liquid such as water. It is because it becomes difficult for the functional polymer to drop out of the hole even in the case of
  • the functional membrane when used as an ion exchange membrane for a fuel cell or the like, it is possible to suitably use a functional polymer precursor or a liquid (solution, dispersion) thereof as the substance to be impregnated.
  • PEFC sometimes humidifies fuel because it needs water for proton transfer, and DMFC contains water in fuel.
  • DMFC contains water in fuel.
  • water is produced by the cell reaction. Therefore, when the ion conductive polymer (in this case, the proton conductive polymer 1) is directly impregnated into the pores and filled, the water inside the battery causes the ion conductive polymer to flow through the pores of the ion exchange membrane. May fall out.
  • such problems are less likely to occur if the functional polymer precursor or its solution is used.
  • a layer of the object to be impregnated is laminated on one surface of the porous substrate.
  • the laminating method is not particularly limited. Specifically, for example, a method of applying the to-be-impregnated material to one surface of the porous base material (a base base material described later is not used) Method), the method of sandwiching the material to be impregnated, etc., between the porous substrate and the base substrate can be used.
  • this method for example, a method of coating an impregnated material on one surface of a base substrate, and superposing a porous substrate on the coated layer, one surface of a porous substrate
  • the force S can be exemplified by the method of overlapping the coated layers.
  • a method can be suitably used in which the to-be-impregnated material is coated on one surface of the base substrate, and the porous substrate is superposed on the coated layer. It is because the air in the hole is easy to escape.
  • the above-mentioned lamination may be laminated from the lower side in the order of the base substrate, the object to be impregnated and the porous substrate, or the porous substrate, the object to be impregnated and the base substrate may be laminated in order. It is good. Preferably, it is the former. This is because the substance to be impregnated penetrates into the pores from the lower side of the porous substrate, and air tends to naturally escape upward. In addition, since it is in a state of receiving the to-be-impregnated material by the base substrate, it is also excellent in continuous productivity which makes it difficult to drip the to-be-impregnated material.
  • the coating method is not particularly limited, and may be appropriately selected in consideration of the viscosity, layer thickness, continuous productivity, and the like of the impregnated material to be coated.
  • Specific examples of the coating method include roll coating, bar coating, reverse coating, die coating, comma coating, gravure coating, microgravure coating, knife coating, spin coating, and the like.
  • various coating methods such as a brush coating method can be exemplified. These may be used alone or in combination of two or more.
  • the shape of the above-mentioned base material is, for example, a film, a sheet, etc.
  • the planar shape such as a shape or a plate shape can be exemplified as a suitable shape.
  • the base substrate does not have to be as porous as a porous substrate.
  • the material of the above-mentioned base material may be any of an organic material such as a polymer, a glass, a ceramic, and an inorganic material such as a metal (including an alloy). In addition, it may be a composite material in which these are combined.
  • a polymer can be suitably used from the viewpoint of being relatively inexpensive, flexible, and available in many cases as a roll body.
  • polystyrene resins such as polyethylene terephthalate and polybutylen terephthalate, olefin resins such as polyethylene, polypropylene and polymethylpentene, and polyamide resins such as nylon 6 and nylon 66.
  • polychlorinated burls and other chlorinated resins cellulose, polycarbonate, polycarbonate sulfide, etc. One or more of these may be contained.
  • two or more kinds of polymers may be laminated.
  • the thickness of the above-mentioned base material is not particularly limited as long as the object to be impregnated can be sandwiched between the base material and the porous substrate and the purpose such as supporting the porous substrate can be achieved. is not.
  • the thickness of the above-mentioned base material becomes excessively thin, wrinkles will occur and mechanical strength will decrease.
  • the thickness of the above-mentioned base substrate becomes excessively thick, the base substrate is partially absorbed during the polymerization, which is difficult to absorb slight strain etc. generated during continuous feeding to the apparatus by film elongation etc. It floats up and tends to cause filling defects.
  • active energy rays such as ultraviolet rays
  • the amount of absorption of ultraviolet rays by the base material increases, so that it becomes difficult to polymerize, and it is necessary to increase the amount of energy. Therefore, these should be kept in mind when selecting the thickness of the base substrate.
  • the thickness of the above-mentioned base substrate varies depending on the material.
  • the upper limit of the thickness of the above-mentioned base substrate is 200 m or less and S preferably 150 ⁇ m or less. Even more preferred is 100 m or less which is more preferred.
  • the lower limit of the thickness of the above-mentioned base material 5 m or more is preferable 10 m or more is more preferable 20 m or more Force S is further more preferable.
  • the substance to be impregnated is impregnated in the pores of the porous substrate.
  • the to-be-impregnated material penetrates into the pores from one side of the porous substrate, that is, the side of the surface of the porous substrate in contact with the layer to be impregnated.
  • the material to be impregnated is the pores of the porous substrate. Almost all of the parts are uniformly impregnated! /, That force S preferred.
  • the substance to be impregnated may not be necessary for the substance to be impregnated to be impregnated in substantially all of the pores of the porous substrate. In such a case, there may be a portion where the impregnated material is not impregnated or a portion where the impregnation of the impregnated material is insufficient, within a range that does not impair the function of the functional film. Absent.
  • a volatile solvent having an affinity for the substance to be impregnated is preliminarily contained in the pores of the porous substrate.
  • the method of impregnation may be exemplified as a preferred method.
  • the impregnability can be enhanced without hydrophilizing the porous substrate in advance.
  • hydrophilic treatment may be used in combination.
  • affinity means that at least the substance to be impregnated can be dissolved.
  • volatile solvent examples include aromatic organic solvents such as toluene, xylene and benzene, aliphatic organic solvents such as hexane and heptane, and chlorine such as chloroform and dichloroethane.
  • Solvents ethers such as jetyl ether, ketones such as methyl ethyl ketone and cyclohexanone, esters such as ethyl acetate and butyl acetate
  • Examples include cyclic ethers such as 1,4-dioxane and tetrahydrofuran, amide solvents such as dimethylformamide, dimethylacetoamide, N-methyl-2-pyrrolidone, alcohols, and the like. One or more of these may be contained.
  • a method of impregnating the volatile solvent in the pores of the porous substrate specifically, for example, a method of immersing the porous substrate in the volatile solvent, the method of impregnating the porous substrate in the porous substrate
  • the method of applying a volatile substrate, the method of spraying the above-mentioned volatile substrate on a porous substrate, etc. can be exemplified. These methods may be used alone or in combination of two or more.
  • the second step is a step of fixing the functional polymer in the pores of the porous substrate.
  • Various fixing methods can be selected as the fixing method according to the type of the substance to be impregnated used in the first step.
  • the same polymer contained in the pores can be crosslinked.
  • the functional polymer is fixed in the hole.
  • the functional polymer When a liquid containing a functional polymer is used as the substance to be impregnated, the functional polymer is fixed in the pores if the solvent or dispersion medium contained in the pores is volatilized. Furthermore, the functional polymer in the pores may be crosslinked.
  • a monomer or a crosslinking agent may be used together. It is good.
  • the solvent or dispersion medium contained in the pores is volatilized, and then the functional polymer precursor is polymerized to form a machine. If functional polymer is generated, the functional polymer is fixed in the pores. Alternatively, after the functional polymer precursor contained in the pores is polymerized to form a functional polymer, the solvent or dispersion medium may be volatilized to fix the functional polymer in the pores. In addition, functional polymer precursors may be cross-linked to the functional polymer produced!
  • the functional polymer in the pore reacts with the pore surface of the porous substrate to chemically bond it. It will be fixed, etc. to produce etc!
  • the polymerization and crosslinking of the functional polymer precursor and the crosslinking of the functional polymer may be carried out by irradiation of active energy rays such as ultraviolet rays and electron beams, heating, and a combination of these methods. it can.
  • active energy rays such as ultraviolet rays and electron beams
  • heating and a combination of these methods.
  • at least ultraviolet irradiation is included, from the viewpoint that the functional film can be obtained with good productivity in a relatively simple process that controls the polymerization and crosslinking reaction.
  • Irradiation of the active energy ray may be carried out by irradiating from the porous substrate side, or by irradiation from the base substrate side. In addition, irradiation may be performed from both the porous substrate side and the base substrate side.
  • conditions for irradiation of active energy rays, heating conditions, etc. may be selected by appropriately selecting optimum conditions in consideration of the type of functional polymer and functional polymer precursor impregnated in the pores. There is no particular limitation.
  • the present manufacturing method may have the following third step between the first step and the second step, and the force S having at least the first step and the second step.
  • the third step is a step of laminating a cover substrate on the surface of the porous substrate opposite to the lamination side of the layer to be impregnated.
  • the base substrate and the opposite surface of the porous substrate are still in contact with air (open air).
  • the substance to be impregnated impregnated in the hole is surely shielded from air by the cover base material. Therefore, when the substance to be impregnated contains a functional polymer precursor, and in particular, when the functional polymer precursor is radically polymerizable, the cover substrate blocks oxygen in the air that inhibits radical polymerization. And the polymerizability can be improved.
  • the shape, material, thickness and the like of the cover base material are not particularly limited. The same shape, material, and thickness as the above-mentioned base material can be used.
  • the functional polymer precursor is contained in the substance to be impregnated, polymerization is carried out in the second step. Therefore, as a material of the cover substrate, it is possible to transmit active energy rays such as ultraviolet rays immediately or for thermal polymerization.
  • a polyester resin, an olefene resin, etc. can be illustrated as a suitable thing from a viewpoint of being hard to deteriorate by heating etc. at the time of the occasion.
  • the cover substrate is at least subjected to release treatment with a release agent on the surface side in contact with the porous substrate! /, May be.
  • the above-mentioned release agent depends on the material of the porous substrate, but specifically, for example, various types such as silicon-based release agent, fluorine-based release agent, higher aliphatic-based release agent, etc.
  • a mold release agent can be exemplified. These may be used alone or in combination of two or more.
  • the present manufacturing method may have the following fourth step after the second step.
  • the fourth step is a step of removing the functional polymer layer to expose the surface of the substrate.
  • a functional polymer layer is formed on the surface of a porous substrate! /,
  • a functional film is used as an ion exchange film of a fuel cell
  • the bondability between the film surface and the electrode May decrease.
  • the rolls in which the functional film is wound up and the functional film cut out are stacked and stored, the films may stick to each other to deteriorate the workability. Therefore, having the fourth step is advantageous in that the above problem can be easily avoided.
  • examples of the above-mentioned removal method include a method of rubbing with a brush or the like, a method of rubbing with a brush or the like, a method of scraping with a scraper or the like, and the like.
  • the above method may be carried out after moistening with water or while washing. These methods may be used alone or in combination of two or more.
  • the method of manufacturing the functional film according to the present embodiment has been described above.
  • the present production method can be suitably used when producing a functional film continuously in a line system. Of course, it can also be used in batch production of functional membranes.
  • the method of continuously producing a functional film by applying the present production method is particularly limited. Specifically, for example, the following methods can be exemplified.
  • FIG. 1 shows an example of a method for continuously producing a functional film using a die coater. That is, on the upper surface of the base substrate 2 continuously supplied from the base substrate supply source 1, an immersion material 4 such as a functional polymer precursor solution is applied from the coater head 3 of the die coater.
  • the porous substrate 6 continuously supplied from the porous substrate source 5 is superposed on the layer of the to-be-impregnated material 4.
  • the base substrate 2 and the porous substrate 6 are laminated via the layer of the object 4 to be impregnated.
  • the to-be-impregnated material 4 is impregnated in the pore part of the porous base material 6.
  • the cover substrate 8 continuously supplied from the cover substrate supply source 7 is laminated on the porous substrate 6 impregnated with the to-be-impregnated substance 4 by the next roll. Overlap. Then, the laminated body 10 in which the porous base material 6 is held between the base base material 2 and the cover base material 8 is continuously placed in the irradiation device 11 of active energy rays such as ultraviolet rays in this state. Supply to
  • the functional polymer precursor contained in the pore is polymerized and the functional polymer is fixed in the pore to become a functional film.
  • the base substrate 2 is wound by the base substrate winding device 12 and the cover substrate 6 is wound by the cover substrate winding device 13 to form the functional film 14 to the base substrate 2, the cover substrate Separate material 6
  • the functional film 14 may be wound with the base substrate 2 and / or the cover substrate 6 laminated, in order to protect 4 and the like.
  • the porous substrate 6 is immersed in the volatile solvent tank 16 to previously impregnate the volatile solvent 17 in the pores, and this is used as a layer of the to-be-impregnated substance 4. You may stack it on top.
  • a layer of the to-be-impregnated substance 4 is formed on the surface of the porous substrate 6,
  • the base substrate 2 may be overlaid under this layer.
  • the functional film obtained by the present production method is not particularly limited, and it can be applied to various uses.
  • an electrolyte membrane for a fuel cell when the functional polymer filled in the pores is an ion conductive polymer, an electrolyte membrane for a fuel cell, a diaphragm of an electrolytic device, a separation membrane of a concentrator, or the like may be used as an ion exchange membrane.
  • the functional polymer filled in the hole is a hydrophilic polymer, it can be applied as a humidity control film to a humidifier, an air conditioner or the like.
  • a drug etc. is infiltrated into a functional polymer, it can be applied to a cup material etc.
  • porous base material As a porous base material, a roll of porous polyethylene film (thickness: 30 111, porosity: 35%, average pore diameter: about 0 ⁇ 06 ⁇ m) was prepared for 50 m in length.
  • the porous substrate immersed in the above-mentioned suspension tank is dried through a hot air drying oven at about 50 ° C., and wound up, thereby pre-treating the surfactant-treated porous substrate. Prepared.
  • the polymer precursor solution was applied from the coater head of a die coater onto the upper surface of the base substrate supplied continuously to form a coating layer.
  • the same film as the base substrate was laminated as a cover substrate on the porous substrate in which the polymer precursor solution was impregnated in the pores.
  • ultraviolet rays are irradiated from the both sides of the above-mentioned laminated film with an irradiation amount of 1000 mj / cm 2 to polymerize the polymer precursor contained in the pores, and fix the ion conductive polymer in the pores.
  • the base substrate and the cover substrate were peeled and removed to obtain a functional membrane applicable as an ion exchange membrane (electrolyte membrane) for a fuel cell.
  • porous substrate As a porous substrate, the same porous polyethylene film roll as in Example 1 is prepared, and the porous substrate is broken from this roll, and a solution of chlorosulfonic acid: concentrated sulfuric acid in a mass ratio of 1: 1 is prepared.
  • the mixture was stirred while being immersed for 3 hours.
  • porous substrate was washed with a 50% sulfuric acid solution, washed with water, and stirred while immersed in a 2 mol / l aqueous sodium hydroxide solution for 2 hours.
  • this porous substrate is immersed in 3.5% hydrochloric acid for 1 hour, washed with water and then dried.
  • Example 2 the polymer precursor solution prepared in Example 1 was coated from the top of the same base substrate as Example 1 with a comma coater head to form a coated layer.
  • the porous substrate pre-sulfonated was continuously drawn out and superposed.
  • the polymer precursor solution permeated into the pores of the porous substrate to give a transparent appearance as a whole.
  • the ion conductive polymer was fixed in the pores to obtain a functional membrane applicable as an ion exchange membrane (electrolyte membrane) for a fuel cell.
  • Example 2 In the same manner as in Example 1 using the apparatus shown in FIG. 3, a coated layer consisting of a polymer precursor solution was formed on the upper surface of the base substrate.
  • Example 2 the same porous substrate as in Example 1 (not previously subjected to hydrophilic treatment) was immersed in a tank of volatile solvent in which isopropyl alcohol and n-butyl alcohol were mixed at 1: 1: The volatile solvent was previously impregnated in the part.
  • the porous substrate impregnated with the volatile solvent was continuously drawn out and superposed on the coated layer.
  • the volatile solvent was volatilized from the pores of the porous substrate, and the polymer precursor solution permeated into the pores, resulting in an overall transparent appearance.
  • the ion conductive polymer was fixed in the hole to obtain a functional membrane applicable as an ion exchange membrane (electrolyte membrane) for a fuel cell.
  • a precursor solution of humidity control polymer was prepared by stirring and mixing 475 g of acrylic acid, 25 g of triallylamine, 0.05 g of ultraviolet radical polymerization initiator and 100 g of water until they became homogeneous solutions.
  • the viscosity of this solution was measured with a Brookfield viscometer, it was 5 mPa's (25 degreeC).
  • Example 4 ⁇ Production of Functional Film According to Example 4> Next, using the apparatus shown in FIG. 1, the above-prepared polymer precursor solution was applied from the coater head of a die coater on the same base substrate as in Example 1 to form a coating layer.
  • Example 1 the same porous substrate as that of Example 1 (not previously subjected to hydrophilic treatment) was continuously drawn out and superposed on this coated layer. As a result, the polymer precursor solution penetrated into the pores of the porous substrate, and the overall appearance became transparent.
  • the same film as the base substrate was laminated as a cover substrate on the porous substrate in which the polymer precursor solution was impregnated in the pores.
  • ultraviolet rays are irradiated from the both sides of the laminated film with an irradiation dose of 5000 mj / cm 2 to polymerize the polymer precursor contained in the pores, and fix the humidity control polymer in the pores.
  • the base substrate and the cover substrate were peeled and removed to obtain a functional film applicable as a humidity control film.
  • the apparatus shown in FIG. 4 is used 1 /, the polymer precursor prepared in Example 4 from the coater head of the die coater on the top of the same porous substrate as in Example 1 (previously hydrophilized! / Not). The solution was applied to form a coated layer.
  • Example 2 the same base substrate as in Example 1 was continuously fed out and superposed on the coated layer.
  • the polymer precursor solution permeated into the pores of the porous substrate, and the overall appearance became transparent.
  • Example 4 Thereafter, in the same manner as in Example 4, the humidity control polymer was fixed in the hole, and a functional film applicable as a humidity control film was obtained.
  • Example 1 350 g of 2-acrylamido-2-methylpropane sulfonic acid used in Example 1, N, A precursor solution of an ion conductive polymer was prepared by stirring and mixing 150 g of N'-ethylenebisacrylamide, 0.55 g of ultraviolet radical polymerization initiator, 0.55 g of a surfactant and 0.05 g of water until a uniform solution was obtained. . In addition, when the viscosity of this solution was measured with a Brookfield viscometer, it was 19 mPa's (25 degreeC).
  • Example 2 While the same porous substrate (not prehydrophilized) as in Example 1 was unrolled from the roll, it was introduced into a tank containing the above polymer-precursor solution at the same line speed as in Example 1. While it was tried to immerse the polymer precursor solution into the pores of the porous substrate after soaking for a minute, residual air was generated in the pores and places where the transparent appearance was not observed were observed.
  • Example 1 Thereafter, the same base substrate as in Example 1 is laminated on one side of the obtained porous substrate, and the same cover base as in Example 1 is laminated on the other side.
  • the polymerization of the monomer components in the parts was advanced to obtain a functional membrane applicable as an ion exchange membrane (electrolyte membrane) for fuel cells.
  • Example 1 Using the ion exchange membrane produced in Example 1 and the ion exchange membrane produced in Comparative Example 1, the membrane performances of both of them were evaluated by the following evaluation methods.
  • the ion exchange membrane was sandwiched between glass cells, a 10% by mass methanol aqueous solution was placed in one cell, and pure water was placed in the other cell. Then, the amount of methanol permeating the pure water side was measured over time by gas chromatography analysis, and the permeation coefficient and permeation flux of methanol at the steady state were measured.
  • the permeation coefficient is a numerical value standardized by the film thickness, methanol is more difficult to permeate in the ion exchange membrane as a material, as the permeation coefficient is lower!
  • the permeation flux indicates the permeability of methanol in the membrane itself, and the smaller the permeation flux, the more suitable it is, for example, for direct methanol fuel cell applications.
  • the air in the pores is immediately released or the porous substrate is removed. Since it is necessary to extend the immersion time, it is possible to confirm that the productivity is excellent!

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Abstract

L'invention concerne un procédé de fabrication d'une membrane fonctionnelle, dans laquelle l'air peut s'échapper plus facilement à partir des pores que dans l'état antérieur de la technique et une productivité élevée est assurée. Dans la fabrication d'une membrane fonctionnelle ayant un matériau de base poreux dont les pores sont remplis d'un polymère fonctionnel, la production est effectuée par au moins la première étape de superposition d'une couche de précurseur de polymère fonctionnel ou de liquide de celui-ci sur une surface majeure du matériau de base poreux, de telle sorte que les pores du matériau de base poreux sont imprégnés par le précurseur de polymère fonctionnel ou par le liquide de celui-ci, et la seconde étape d'opération d'une réaction chimique du précurseur de polymère fonctionnel ou du liquide de celui-ci pour fixer de cette façon le polymère fonctionnel dans les pores du matériau de base poreux.
PCT/JP2007/067129 2006-09-04 2007-09-03 Procédé de fabrication d'une membrane fonctionnelle WO2008029761A1 (fr)

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JP2016124925A (ja) * 2014-12-26 2016-07-11 トヨタ自動車株式会社 単官能光重合性単量体、光重合性組成物、非水電解質二次電池用のセパレータとその製造方法、および非水電解質二次電池
CN108391454A (zh) * 2015-12-11 2018-08-10 日东电工株式会社 电解质膜及其制造方法、以及具备电解质膜的燃料电池用膜-电极组件

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JP2016124925A (ja) * 2014-12-26 2016-07-11 トヨタ自動車株式会社 単官能光重合性単量体、光重合性組成物、非水電解質二次電池用のセパレータとその製造方法、および非水電解質二次電池
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