WO2015151922A1 - 溶液製膜用支持フィルムおよびそれを用いた電解質膜の製造方法 - Google Patents
溶液製膜用支持フィルムおよびそれを用いた電解質膜の製造方法 Download PDFInfo
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- 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
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
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- 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
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/20—Manufacture of shaped structures of ion-exchange resins
- C08J5/22—Films, membranes or diaphragms
- C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
- C08J5/2218—Synthetic macromolecular compounds
- C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
- C08J5/2262—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation containing fluorine
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- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/126—Halogenation
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- 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
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- 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
- H01M8/1086—After-treatment of the membrane other than by polymerisation
- H01M8/1088—Chemical modification, e.g. sulfonation
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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
- C08J2300/00—Characterised by the use of unspecified polymers
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/04—Homopolymers or copolymers of ethene
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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
- C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2323/10—Homopolymers or copolymers of propene
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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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08J2371/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
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- 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
- H01M2008/1095—Fuel cells with polymeric electrolytes
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- 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
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- 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 support film for forming a solution having a specific surface state and a method for producing an electrolyte membrane using the support film for forming a solution.
- a fuel cell is a kind of power generation device that extracts electric energy by electrochemically oxidizing a fuel such as hydrogen or methanol, and has recently attracted attention as a clean energy supply source.
- the polymer electrolyte fuel cell has a standard operating temperature as low as around 100 ° C. and a high energy density, so that it is a relatively small-scale distributed power generation facility, a mobile power generator such as an automobile or a ship.
- a mobile power generator such as an automobile or a ship.
- secondary batteries such as nickel metal hydride batteries and lithium ion batteries.
- an anode electrode and a cathode electrode in which a reaction responsible for power generation occurs, and a polymer electrolyte membrane composed of a proton conductor between the anode and the cathode are sometimes abbreviated as a membrane electrode assembly (hereinafter referred to as MEA).
- MEA membrane electrode assembly
- a cell in which this MEA is sandwiched between separators is configured as a unit.
- the fuel gas reacts in the catalyst layer to generate protons and electrons, the electrons are sent to the external circuit through the electrodes, and the protons are conducted to the electrolyte membrane through the electrode electrolyte.
- the cathode electrode in the catalyst layer, the oxidizing gas, protons conducted from the electrolyte membrane, and electrons conducted from the external circuit react to generate water.
- the electrode structure is devised to increase the reaction active point of the electrode reaction, and an electrolyte polymer is also blended into the electrode catalyst layer so that hydrogen ions can move quickly.
- an electrolyte polymer is also blended into the electrode catalyst layer so that hydrogen ions can move quickly.
- the film thickness be as thin as possible.
- the solution casting method has an advantage that an electrolyte membrane excellent in flatness and smoothness can be produced as compared with the former film.
- a solution containing an organic compound as a raw material and a solvent is cast on a support film to form a cast film, and then dried by a drying means to form a film. If necessary, chemical treatment or cleaning treatment And finally the product film is peeled from the support film. It is widely used not only as an electrolyte membrane manufacturing method but also as a polymer film manufacturing method for optical applications.
- Patent Document 1 is characterized by including a step of applying and drying an organic polymer on a substrate and a step of liquid-treating the obtained organic polymer film without peeling off the substrate.
- a polyethylene terephthalate (PET) film is used as the support film.
- Patent Document 2 provides a method for producing a particularly thin polymer electrolyte membrane that is less prone to thickness unevenness, wrinkles, and unevenness.
- a PET film is used as the support film.
- Patent Document 3 proposes a base film in which a support film and a film having releasability are laminated on at least one side.
- the inventors When solution casting is selected as the method for manufacturing the electrolyte membrane, the inventors have focused on the requirements for the support film used, as follows: solvent resistance not affected by polymer solution, polymer solution of electrolyte membrane Good coatability when applied to the support film, heat resistance that can withstand the heat of the drying process, and unintentional peeling of the polymer film during the manufacturing process, especially during the wet process such as the acid treatment process and the water washing process, does not occur In addition, the film can be easily peeled when the polymer film is intentionally peeled from the support film, and the low contamination property that does not contaminate the polymer film.
- Patent Documents 1 and 2 a PET film is used.
- the PET film has high adhesion, that is, it is not easily peelable. Horizontal stripes and wrinkles easily enter the electrolyte membrane. Therefore, it has been difficult to obtain a high-quality electrolyte membrane in a high yield.
- the present invention has good applicability of the polymer solution, that is, good wettability of the polymer solution, and there is no premature peeling of the polymer film during the drying process and the wet process such as the acid treatment process and the water washing process
- it has good releasability when the polymer film is intentionally peeled off from the support film, and it can be suitably used as a support film for electrolyte membranes because it does not contaminate the polymer film. It is intended to provide a support film.
- the inventors have prepared a solution film-forming support film that is compatible with the wettability of the polymer solution and the early peel resistance that does not peel off during the wetting process and the easy peelability that conflicts with them, and that does not contaminate the polymer film and that can be produced at low cost.
- a solution film-forming support film that is compatible with the wettability of the polymer solution and the early peel resistance that does not peel off during the wetting process and the easy peelability that conflicts with them, and that does not contaminate the polymer film and that can be produced at low cost.
- the present invention employs the following means in order to solve such problems. That is, polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide, polysulfone, polyetherketone, polyetheretherketone, polyimide, polyetherimide, polyamide, polyamideimide, polybenzimidazole, polycarbonate, polyarylate
- a support film for solution casting in which the ratio of the number of fluorine atoms / number of carbon atoms measured by X-ray photoelectron spectroscopy on the surface into which atoms are introduced, that is, the modified surface, is 0.02 or more and 0.8 or less. That.
- the support film for solution casting of the present invention has good polymer solution applicability (sometimes referred to as wettability) at the time of solution casting, and early peeling of the polymer film at the time of a wet process such as an acid treatment process or a water washing process. On the other hand, it has good releasability when the polymer film is intentionally peeled off from the support film for solution film formation, and the polymer film is not easily contaminated, so it is suitable for the production of a polymer film with high surface quality and few impurities. is there.
- a support film for production of various functional films such as electrolyte membranes and optical films, and microporous membranes having a wet coagulation process
- it can be used to make good use of good coatability, easy peelability, and low contamination.
- it is most suitable as a support film for solution membrane formation of an electrolyte membrane from the viewpoints of wettability, early peel resistance in a wet process, and excellent peelability when intentionally peeling a polymer film.
- the base film as the base of the support film for solution casting according to the present invention can introduce fluorine atoms and is inexpensive, so that polyethylene, polypropylene, polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyphenylene sulfide , Polysulfone, Polyetherketone, Polyetheretherketone, Polyimide, Polyetherimide, Polyamide, Polyamideimide, Polybenzimidazole, Polycarbonate, Polyarylate, Polyvinyl Chloride Use a good one.
- the film may be formed from two or more kinds of blend polymers, or a laminate in which layers formed from the respective polymers are laminated. From the viewpoint of cost, it is preferable to use a single layer film made of one kind of polymer.
- the support film for solution casting of the present invention is one in which fluorine atoms are introduced on at least one surface of the base film.
- the surface modification refers to replacing a part of hydrogen atoms bonded to carbon existing on the surface of the base film with fluorine atoms.
- introduction of a hydroxyl group, a carboxylic acid group, a sulfonic acid group, or the like may be further accompanied.
- Introduction of hydroxyl groups, carboxylic acid groups, and sulfonic acid groups can lower the contact angle of the surface of the base film, and the coating properties (wetting properties) of the polymer solution during film formation can be controlled by the composition and properties of the polymer solution. It becomes.
- the surface into which this fluorine atom is introduced is sometimes simply referred to as “modified surface”.
- the surface modification may be performed only on one side or both sides of the film, but it is preferable to modify only one side from the viewpoint of cost. Alternatively, it may be locally fluorinated only on the portion where the polymer solution for film formation is applied.
- the ratio of the number of fluorine atoms / number of carbon atoms measured by X-ray photoelectron spectroscopy on the modified surface into which fluorine atoms are introduced is 0.02 or more and 0.8 or less.
- the ratio of the number of fluorine atoms / the number of carbon atoms on the modified surface is 0.02 or more, the releasability when the film after film formation is intentionally peeled off from the modified surface is improved.
- the ratio of the number of fluorine atoms / the number of carbon atoms is 0.8 or less, even if the film manufacturing process includes a wet process such as an acid treatment process or a water washing process, the polymer film in these processes is in an early stage. Peeling can be prevented. In this case, it is not intended to be early peeling, and a part of the product film peels off or floats from the support film for solution casting during the manufacturing process, and the polymer film is wrinkled or damaged during the manufacturing process.
- the ratio of the number of fluorine atoms / number of carbon atoms on the modified surface is preferably 0.03 or more, and more preferably 0.04 or more. Moreover, it is preferable that it is 0.5 or less, and it is more preferable that it is 0.27 or less.
- the ratio of the number of oxygen atoms / number of carbon atoms measured by X-ray photoelectron spectroscopy on the modified surface into which fluorine atoms have been introduced is preferably from 0.10 to 0.60.
- the ratio of the number of oxygen atoms / the number of carbon atoms is 0.10 or more, when used as a support film for solution casting, the coating property (wetting property) of the polymer solution on the modified surface becomes good.
- the ratio of the number of oxygen atoms / number of carbon atoms is 0.60 or less, the peelability when the film after film formation is intentionally peeled from the modified surface is improved.
- the ratio of the number of oxygen atoms / number of carbon atoms on the modified surface is preferably 0.40 or more and 0.50 or less from the viewpoint of the balance between wettability and peelability.
- X-ray photoelectron spectroscopy soft X-rays are irradiated on the surface of a sample placed in an ultra-high vacuum, and photoelectrons emitted from the surface are detected by an analyzer.
- photoelectrons are emitted from the surface into the vacuum due to the photoelectric effect.
- information on the elemental composition and chemical state of the surface can be obtained.
- E b h ⁇ E kin ⁇ sp (Formula 1)
- E b is the binding energy of bound electrons
- h ⁇ is the soft X-ray energy
- E kin is the kinetic energy of photoelectrons
- ⁇ is the work function of the spectrometer.
- the binding energy (E b ) of the bound electrons is intrinsic to the element. Therefore, by analyzing the energy spectrum of photoelectrons, it becomes possible to identify elements present on the surface of the material. Since the length (mean free path) that the photoelectron can travel through the substance is several nm, the detection depth in this analytical method is several nm.
- the ratio of the number of fluorine atoms / the number of carbon atoms and the ratio of the number of oxygen atoms / the number of carbon atoms on the modified surface are those of a depth of several nm from the surface.
- X-ray photoelectron spectroscopy surface atomic information is obtained from the binding energy value of bound electrons in a substance, and information on valence and bonding state is obtained from the energy shift of each peak. Furthermore, the ratio of the number of atoms can be obtained using the peak area ratio.
- the measurement conditions of the X-ray photoelectron spectroscopy used in the present invention are as follows.
- the modified surface preferably has a water contact angle ( ⁇ ) of 35 ° or more and 75 ° or less. If the contact angle is 35 ° or more, the peelability when the polymer film is intentionally peeled from the support film for solution casting becomes good. When the contact angle is 75 ° or less, a coating with a good surface quality can be obtained in which coating unevenness hardly occurs when a polymer solution or the like is applied. Contact angle is the most intuitive measure of wetting by a solid liquid. In the present invention, a value measured by a droplet method is adopted. Specifically, it was carried out in accordance with JIS R3257. Instead of glass, water is dropped on the modified surface of the support film for solution casting of the present invention, and the angle formed between the tangent of the droplet at the contact point between the modified surface and the formed droplet and the modified surface is determined. It was measured.
- ⁇ water contact angle
- the thickness of the support film for solution casting of the present invention can be appropriately determined depending on the thickness of the electrolyte membrane to be produced and the production apparatus, and is not particularly limited, but is preferably 5 ⁇ m to 500 ⁇ m from the viewpoint of handling. In addition, a thickness of 50 ⁇ m to 200 ⁇ m is more preferable from the viewpoint of productivity, cost, and reduction effects such as deformation during drying.
- the manufacturing method of the support film for solution casting of the present invention is not particularly limited, and various known methods can be used.
- various known methods can be used.
- direct fluorination reaction with fluorine gas fluorination with high-valent metal fluoride, indirect fluorination mainly using halogen exchange reaction, fluorination by electrolysis method, etc. (Organic Synthetic Chemistry, Vol. 31, Vol. 31) 6 (1973) pp. 441-454).
- direct fluorination reaction by bringing the base film into contact with fluorine gas can be preferably applied.
- Control of the amount of fluorine atoms introduced by the fluorine gas adjusts the fluorine gas concentration in the gas containing the fluorine gas, the temperature and pressure of the gas containing the fluorine gas, the conveyance speed of the film when continuously processing the film, etc.
- those skilled in the art can appropriately determine experimentally depending on the equipment and equipment to be used.
- FIG. 1 is a conceptual diagram showing an example of an apparatus for contacting a fluorine gas while continuously transporting a film.
- the surface modification is performed in the fluorine gas contact chamber 3 having the gas supply port 1 and the gas discharge port 2 while the film base 6 is continuously conveyed from the unwinding unit 4 to the winding unit 5.
- the support roll 7 is configured to minimize leakage of fluorine gas.
- temperature control in the fluorination reaction can be performed.
- the support film for solution casting of the present invention is Step 1: applying an electrolyte polymer solution to the modified surface of the support film; Step 2: removing the solvent from the electrolyte polymer solution applied in Step 1 to form an electrolyte polymer film on the modified surface; Step 3: bringing the electrolyte polymer film obtained in Step 2 into contact with one or more liquids selected from the group consisting of an acidic solution, a basic solution, water and an organic solvent together with the support film; Step 4: A step of peeling the electrolyte polymer film obtained in Step 3 from the support film; It can use suitably as a support film in the manufacturing method of the electrolyte membrane which has this.
- the “electrolyte polymer” includes an electrolyte precursor polymer that becomes an electrolyte by a subsequent treatment.
- the electrolyte polymer film peels off from the support film at an early stage, the electrolyte film is broken or wrinkles are generated.
- the support film for solution casting of the present invention is used as a support film, it can be produced without such early peeling.
- the above-described method for producing an electrolyte membrane is suitable for continuously producing an electrolyte membrane having an acidic group density of 1.0 mmol / g or more. This is because the film can be prevented from breaking due to swelling, wrinkles and surface defects during drying by being brought into contact with an acidic solution or the like without being peeled off from the support film.
- the above production method is particularly suitable when an electrolyte membrane having an acid group density of 1.5 mmol / g or more and 3.5 mmol / g or less is continuously produced.
- the method for manufacturing an electrolyte membrane regardless of the acid group density.
- the electrolyte polymer film alone reduces the mechanical strength during liquid swelling and easily breaks the film during production, and wrinkles occur during drying and surface defects are likely to occur, so after the electrolyte film is peeled off from the support film This is because, in the method of performing a wet process such as contact with an acidic solution, the transport system for preventing these phenomena tends to be expensive.
- the necessity of contact with an acidic solution without peeling off the electrolyte membrane or the electrolyte membrane precursor is particularly high, and the thickness of the electrolyte membrane is 20 ⁇ m or less. In some cases it is even higher.
- the electrolyte film is peeled off from the support film.
- a process is included. If the adhesion between the support film and the electrolyte membrane is too strong, it cannot be peeled off well, and wrinkles and membrane breakage may occur. However, when the solution film-forming support film of the present invention is used as a support film, the peelability at the time of peeling the electrolyte membrane is good, and defects such as wrinkles and film breakage can be reduced.
- Examples of the electrolyte membrane suitably produced by the production method as described above include ionic group-containing polyphenylene oxide, ionic group-containing polyether ketone, ionic group-containing polyether ether ketone, and ionic group-containing polyether sulfone.
- the ionic groups herein include a sulfonic acid group (—SO 2 (OH)), a sulfuric acid group (—OSO 2 (OH)), and a sulfonimide group (—SO 2 NHSO 2 R (R represents an organic group). ), A phosphonic acid group (—PO (OH) 2 ), a phosphoric acid group (—OPO (OH) 2 ), a carboxylic acid group (—CO (OH)), and a metal salt thereof. Can be preferably employed.
- a sulfonic acid group it is more preferable to have at least one of a sulfonic acid group, a sulfonimide group, a sulfuric acid group and a phosphonic acid group from the viewpoint of high proton conductivity, and most preferable to have at least a sulfonic acid group from the viewpoint of hydrolysis resistance. preferable.
- a metal salt can be substituted with a proton and converted into an ionic group.
- the metal that forms the metal salt may be any metal that can form a salt with the ionic group. From the viewpoint of price and environmental load, Li, Na, K, Rb, Cs, Mg, Ca, Sr, Ba, Ti, V, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, W, etc. are preferable. Among these, Li, Na, K, Ca, Sr, and Ba are more preferable, and Li, Na, and K are more preferable.
- the introduction of the ionic group into the electrolyte membrane may be performed by a method of introducing a metal salt or derivative of the ionic group into the polymer after polymerization, or after introducing the metal salt of the ionic group into the monomer, You may carry out by the method of superposing
- the electrolyte precursor polymer may contain a hydrolyzable group.
- the hydrolyzable group here refers to a substituent that is primarily introduced for the purpose of removing or modifying at least a part in a later step, for example, to inhibit crystallization in a solution film forming process.
- An embodiment in which a hydrolyzable group for enhancing solubility is introduced and the film is hydrolyzed after film formation is exemplified.
- an electrolyte membrane using an electrolyte precursor polymer containing a hydrolyzable group for example, the acetal or ketal site is protected at the ketone site of a crystalline polyether ketone, and the crystallinity is destroyed due to steric hindrance and used as a solvent. Solubilization is mentioned.
- hydrolyzable group It becomes easy and an electrolyte membrane excellent in water resistance and solvent resistance can be obtained by hydrolyzing the hydrolyzable group by acid treatment and returning it to a ketone bond.
- the hydrolyzable group can also be removed by heating, electron beam or the like.
- a protecting group other than a hydrolyzable group may be employed in order to impart solubility.
- the hydrolyzable group is most preferable from the viewpoint of continuous productivity of the electrolyte membrane. Specific examples of the hydrolyzable group include those described in JP-A-2006-561103.
- the solvent used in the solution casting can be appropriately selected experimentally without particular limitation as long as the electrolyte polymer can be dissolved or dispersed.
- aprotic such as N, N-dimethylacetamide, N, N-dimethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, sulfolane, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphontriamide, etc.
- Polar solvents such as ⁇ -butyrolactone and butyl acetate, carbonate solvents such as ethylene carbonate and propylene carbonate, alkylene such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether and propylene glycol monoethyl ether Glycol monoalkyl ether is suitably used, and may be used alone or as a mixture of two or more.
- alcohol solvents such as methanol and isopropanol
- ketone solvents such as acetone and methyl ethyl ketone
- ester solvents such as ethyl acetate, butyl acetate and ethyl lactate
- hydrocarbon solvents such as hexane and cyclohexane
- Aromatic hydrocarbon solvents such as benzene, toluene and xylene
- halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane, dichloromethane, perchloroethylene, chlorobenzene and dichlorobenzene, diethyl ether, tetrahydrofuran,
- Various low boiling point solvents such as ether solvents such as 1,4-dioxane, nitrile solvents such as acetonitrile, nitrated hydrocarbon solvents such as
- a method for coating the electrolyte polymer solution known methods can be adopted, such as knife coating, direct roll coating (comma coating), gravure coating, spray coating, brush coating, dip coating, die coating, vacuum die coating, curtain coating, flow coating, Techniques such as spin coating, reverse coating, and screen printing can be applied, and continuous coating is preferably die coating or comma coating.
- a known method such as heating, hot air or infrared heater can be selected.
- the drying time, temperature, wind speed, and wind direction of the solvent can be determined experimentally as appropriate.
- the wet process includes a step of contacting an acidic solution and a polymer film composed of an electrolyte precursor polymer
- aqueous solutions of inorganic acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and nitric acid are preferable. It is.
- sulfuric acid is preferable from the viewpoint of productivity and workability.
- the concentration and temperature of the acidic solution can be appropriately determined experimentally, but from the viewpoint of workability and productivity, the concentration is preferably from 0.1% to 30%, more preferably from 1% to 20%.
- the temperature is preferably in the range of room temperature to 80 ° C. and 40 ° C. or more for shortening the treatment time.
- the acid solution and the polymer film can be brought into contact with each other by introducing the support film and the polymer film to the acidic solution tank while continuously peeling them, or by cutting into single sheets and fixing them to a dedicated frame and using a batch type acidic solution tank.
- the method of immersing in is mentioned.
- a method of blowing a gas such as compressed air, a method of absorbing droplets with a cloth, sponge roll or nonwoven fabric roll, or a method of sucking the roll by combining a decompression pump or the like are preferable.
- the drying process after removing the droplets is performed mainly for the purpose of controlling the water content of the electrolyte membrane, and the drying conditions and the like are appropriately determined experimentally according to the requirements of the subsequent processes. Conditions that do not cause wrinkles, warping, tearing, etc. are preferred.
- wrinkle prevention includes a method of fixing the film with a frame tension, a tenter, a suction roll, or the like, and can prevent the film from shrinking due to drying. In continuous processing, tenters and suction rolls are preferred.
- the present invention will be described in more detail with reference to examples of the support film for forming a solution using a polyethylene terephthalate film as a base material.
- the present invention is not limited to these.
- Surface modification can also be produced according to this example.
- the measurement conditions of each physical property are as follows.
- Ratio of fluorine atoms / carbon atoms on the film surface F / C ratio
- Table 1 shows the fluorine atom / carbon atom ratio, oxygen atom / carbon atom ratio, water contact angle, wettability, early peel resistance, and easy peelability of the treated surface of the support film A for solution casting.
- Examples 2, 3, 4, 5 and Comparative Example 1 The film was produced by changing the ratio of the fluorine / air mixed gas or the blowing time in Example 1 to obtain support films BF for solution casting. These ratios of the number of fluorine atoms / the number of carbon atoms, the ratio of the number of oxygen atoms / the number of carbon atoms, water contact angle and wettability, early peel resistance, and easy peelability are summarized in Table 1.
- Example 6 Continuous fluorine surface treatment apparatus having a roll-shaped film unwinding section capable of controlling the conveyance speed and a winding section, and having a contact chamber for fluorine gas provided with fluorine and air gas supply ports and exhaust ports therebetween.
- Table 1 shows the fluorine atom / carbon atom ratio, oxygen atom / carbon atom ratio, water contact angle, wettability, early peel resistance, and easy peelability of the treated surface of the support film G for solution casting.
- Example 2 The same procedure as in Example 6 was performed except that the PET film (“Lumirror” (registered trademark) -T60, thickness 125 ⁇ m, manufactured by Toray Industries, Inc.) was changed to a polytetrafluoroethylene film.
- Table 1 summarizes the ratio of the number of fluorine atoms / the number of carbon atoms, the ratio of the number of oxygen atoms / the number of carbon atoms, the contact angle of water and wettability, early peel resistance, and easy peelability.
- Table 1 summarizes the ratio and contact angle of water, wettability, early peel resistance, and easy peelability.
- a polymer solution comprising 20% by weight of a sulfonated polyetherketone precursor (see Japanese Patent Application Laid-Open No. 2006-561103) and N-methyl-2-pyrrolidone (NMP) is continuously formed into a solution by a slit die coater.
- the support film G was cast on the surface-modified surface, the solvent was removed in a hot air drying oven at 150 ° C., and a sulfonated polyetherketone precursor film having a thickness of 12 ⁇ m was formed on the support film G for solution casting. Formed on top. At this time, the wettability of the polymer solution was good and there was no defect such as repelling, and no early peeling of the sulfonated polyetherketone precursor film was observed during drying.
- the sulfonated polyetherketone precursor film is continuously immersed in a 10% by weight sulfuric acid aqueous solution at 60 ° C. for 30 minutes together with the support film G for solution casting, and repeatedly washed with pure water until the cleaning liquid becomes neutral. And dried at 80 ° C. for 10 minutes. At this time, the sulfonated polyetherketone film did not peel early from the solution-forming support film G, and had good surface quality with no wrinkles or membrane damage.
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Abstract
Description
本発明の溶液製膜用支持フィルムのベースとなるベースフィルムは、フッ素原子の導入が可能であり、かつ安価であることから、ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリフェニレンスルフィド、ポリスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリイミド、ポリエーテルイミド、ポリアミド、ポリアミドイミド、ポリベンズイミダゾール、ポリカーボネート、ポリアリレート、ポリ塩化ビニルから選択される単独または2種以上のポリマーから形成されるものを用いるとよい。2種以上のポリマーからフィルムを形成する場合には、2種以上のブレンドポリマーからフィルムを形成してもよく、また各ポリマーから形成した層を積層した積層体としてもよい。コストの点からは1種のポリマーからなる単層フィルムを用いることが好ましい。
Eb=hν-Ekin-φsp(式1)
式1のEbは束縛電子の結合エネルギー、hνは軟X線のエネルギー、Ekinは光電子の運動エネルギー、φは分光器の仕事関数となる。ここで束縛電子の結合エネルギー(Eb)は元素固有のものとなる。よって光電子のエネルギースペクトルを解析すれば、物質表面に存在する元素の同定が可能となる。光電子が物質中を進むことができる長さ(平均自由行程)が数nmであることから、本分析手法における検出深さは数nmとなる。すなわち、本発明において、改質表面のフッ素原子数/炭素原子数の比および酸素原子数/炭素原子数の比は表面より数nmの深さの原子数比である。
励起X 線:monochromatic Al Kα1,2 線(1486.6 eV)
X 線径:100μm(分析領域:100μmφ)
光電子脱出角度:45 °(試料表面に対する検出器の傾き)
スムージング:9 points smoothing
横軸補正:C1s ピークメインピークを284.6 eV に合わせた。
本発明の溶液製膜用支持フィルムの製造方法は特に限定されず、公知の様々な方法を用いることができる。例えば、フッ素ガスによる直接フッ素化反応のほか、高原子価金属フッ化物によるフッ素化、ハロゲン交換反応を主体とした間接フッ素化、電解法によるフッ素化などが挙げられる(有機合成化学 第31巻 第6号(1973)441頁~454頁)。これらの中でも、量産性、導入量の制御性の観点から、ベースフィルムをフッ素ガスと接触させることによる直接フッ素化反応が好ましく適用できる。
以下、本発明の溶液製膜用支持フィルムを用いた電解質膜の製造方法について説明する。本発明の溶液製膜用支持フィルムは、
工程1:電解質ポリマー溶液を支持フィルムの改質表面に塗布する工程;
工程2:工程1で塗布した電解質ポリマー溶液から溶媒を除去し、電解質ポリマー皮膜を改質表面上に形成する工程;
工程3:工程2で得た電解質ポリマー皮膜を、支持フィルムごと酸性溶液、塩基性溶液、水および有機溶媒からなる群より選択される一種以上の液体に接触させる工程;
工程4:支持フィルムから工程3で得た電解質ポリマー皮膜を剥離する工程;
を有する電解質膜の製造方法における支持フィルムとして好適に用いることができる。ここで、「電解質ポリマー」には、後の処理により電解質となる電解質前駆体ポリマーも含まれるものとする。
本発明では、X線光電子分光法で測定した値を採用する。光電子が物質中を進むことができる長さ(平均自由行程)が数nm であることから、本分析手法における検出深さは数nm となり、本発明のフッ素原子数/炭素原子数の比は表面より数nmの深さの原子比であり、炭素原子基準で(C/C=1)表した。X線光電子分光法の測定条件の一例を下記する。なお、酸素原子数/炭素原子数の比(O/C比)も同方法で取得できる。
励起X 線:monochromatic Al Kα1,2 線(1486.6 eV)
X 線径:100μm(分析領域:100μmφ)
光電子脱出角度:45 °(試料表面に対する検出器の傾き)
スムージング:9 points smoothing
横軸補正:C1s ピークメインピークを284.6 eV に合わせた。
水に対する接触角は、JIS-R3257(1999)に準拠した方法で測定した。
20重量%のスルホン化ポリエーテルケトンの前駆体(特開2006-561103号公報等参考)とN-メチル-2-ピロリドン(NMP)からなるポリマー溶液を溶液製膜用支持フィルム上に流延塗布し乾燥前の塗布膜の表面品位を目視観察で評価した。
上記の濡れ性を評価後、100℃で乾燥し、湿潤工程として60℃の10重量%硫酸水溶液に10分間浸漬し、ついで純水に30分浸漬し、溶液製膜用支持フィルム上からポリマー皮膜の剥離の有無を目視観察で評価した。
上記耐早期剥離性を評価後、80℃で水分を乾燥し、溶液製膜用支持フィルム上からポリマー皮膜を手動で剥離し、はぎ取ったポリマー皮膜の皺の状態を目視観察で評価した。
PETフィルム (東レ株式会社製“ルミラー”(登録商標)-T60、厚み125μm)をフッ素ガスおよび空気供給口と排気口を備えた20Lのステンレス製圧力容器に入れ、窒素ガスを流速100ml/minで吹き込んで1時間パージした後、フッ素/ 空気=10/90(体積比)混合ガスを流速10ml/ m i nで吹き込み10分間反応させた。引き続き窒素ガスを流速100ml/minで吹き込んで1時間パージしてから容器を開封し、溶液製膜用支持フィルムAを得た。
実施例1の、フッ素/ 空気混合ガスの比率または吹き込み時間を変えて製造し、溶液製膜用支持フィルムB~Fを得た。これらのフッ素原子数/炭素原子数の比、酸素原子数/炭素原子数の比と水の接触角および濡れ性、耐早期剥離性、易剥離性を表1にまとめた。
搬送速度制御が可能なロール状のフィルムの巻出し部と、巻き取り部を有し、その間にフッ素および空気ガス供給口と排気口を備えたフッ素ガスとの接触室を有する連続フッ素表面処理装置を用い、搬送速度1m/minでフッ素ガスとの接触室にフッ素/空気=30/70(体積比)混合ガス10ml/minで吹き込みながら連続的にPETフィルム (東レ株式会社製“ルミラー”(登録商標)-T60、厚み125μm)の表面改質を実施し、溶液製膜用支持フィルムGの連続処理膜を得た。溶液製膜用支持フィルムGの処理面のフッ素原子数/炭素原子数の比、酸素原子数/炭素原子数の比と水の接触角および濡れ性、耐早期剥離性、易剥離性を表1にまとめた。
実施例6においてPETフィルム (東レ株式会社製“ルミラー”(登録商標)-T60、厚み125μm)をポリテトラフルオロエチレンフィルムに変更した以外は同様に実施した。フッ素原子数/炭素原子数の比、酸素原子数/炭素原子数の比と水の接触角および濡れ性、耐早期剥離性、易剥離性を表1にまとめた。の比と水の接触角および濡れ性、耐早期剥離性、易剥離性を表1にまとめた。
20重量%のスルホン化ポリエーテルケトンの前駆体(特開2006-561103号公報等参考)とN-メチル-2-ピロリドン(NMP)からなるポリマー溶液をスリットダイコーターで連続的に溶液製膜用支持フィルムGの表面改質面上に流延塗布し、150℃の熱風乾燥炉で溶媒を除去して、厚み12μmのスルホン化ポリエーテルケトンの前駆体の皮膜を溶液製膜用支持フィルムGの上に形成した。このときポリマー溶液の濡れ性は良好ではじき等の欠陥がなく、乾燥時にスルホン化ポリエーテルケトンの前駆体の皮膜の早期剥離も見られなかった。
2 ガス排出口
3 フッ素ガス接触室
4 フィルム巻出し部
5 フィルム巻き取り部
6 フィルム基材
7 支持ロール
Claims (6)
- ポリエチレン、ポリプロピレン、ポリエチレンテレフタレート、ポリブチレンテレフタレート、ポリエチレンナフタレート、ポリフェニレンスルフィド、ポリスルホン、ポリエーテルケトン、ポリエーテルエーテルケトン、ポリイミド、ポリエーテルイミド、ポリアミド、ポリアミドイミド、ポリベンズイミダゾール、ポリカーボネート、ポリアリレート、ポリ塩化ビニルからなる群より選択される1種または2種以上のポリマーから形成されたベースフィルムの少なくとも一方の表面にフッ素原子が導入されてなる溶液製膜用支持フィルムであって、該フッ素原子を導入した表面、すなわち改質表面の、X線光電子分光法で測定したフッ素原子数/炭素原子数の比が、0.02以上、0.8以下である溶液製膜用支持フィルム。
- 前記改質表面における水の接触角が、35°以上、70°以下である、請求項1に記載の溶液製膜用支持フィルム。
- 前記フッ素原子の導入は、前記ベースフィルムをフッ素ガスと接触させることにより行われたものである、請求項1または2に記載の溶液製膜用支持フィルム。
- 前記改質表面の、X線光電子分光法で測定した酸素原子数/炭素原子数の比が、0.10以上、0.60以下である、請求項1~3のいずれかに記載の溶液製膜用支持フィルム。
- 電解質膜の溶液製膜に用いられる、請求項1~4のいずれかに記載の溶液製膜用支持フィルム。
- 工程1:電解質ポリマー溶液を支持フィルムの改質表面に塗布する工程;
工程2:工程1で塗布した電解質ポリマー溶液から溶媒を除去し、電解質ポリマー皮膜を前記改質表面上に形成する工程;
工程3:工程2で得た電解質ポリマー皮膜を、前記支持フィルムごと酸性溶液、塩基性溶液、水および有機溶媒からなる群より選択される一種以上の液体に接触させる工程;
工程4:工程3で得た電解質ポリマー皮膜を前記支持フィルムから剥離する工程;
を有する電解質膜の製造方法であって、前記支持フィルムとして請求項1~4のいずれかに記載の溶液製膜用支持フィルムを用いることを特徴とする電解質膜の製造方法。
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- 2015-03-24 WO PCT/JP2015/058856 patent/WO2015151922A1/ja active Application Filing
- 2015-03-24 US US15/122,707 patent/US20170077540A1/en not_active Abandoned
- 2015-03-24 CN CN201580016541.6A patent/CN106133037B/zh active Active
- 2015-03-24 CA CA2941573A patent/CA2941573C/en active Active
- 2015-03-24 EP EP15773259.5A patent/EP3127946B1/en active Active
- 2015-03-24 JP JP2015516926A patent/JP6555124B2/ja active Active
- 2015-03-24 KR KR1020167028613A patent/KR102308396B1/ko active IP Right Grant
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Also Published As
Publication number | Publication date |
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CA2941573C (en) | 2021-12-07 |
TWI659984B (zh) | 2019-05-21 |
JPWO2015151922A1 (ja) | 2017-04-13 |
EP3127946A1 (en) | 2017-02-08 |
CN106133037B (zh) | 2019-01-18 |
KR102308396B1 (ko) | 2021-10-06 |
CA2941573A1 (en) | 2015-10-08 |
US20170077540A1 (en) | 2017-03-16 |
EP3127946B1 (en) | 2018-10-03 |
CN106133037A (zh) | 2016-11-16 |
EP3127946A4 (en) | 2017-11-29 |
KR20160140734A (ko) | 2016-12-07 |
JP6555124B2 (ja) | 2019-08-07 |
TW201542632A (zh) | 2015-11-16 |
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