WO2015098052A1 - Separator for aqueous electrolyte power storage device, production method for separator for aqueous electrolyte power storage device, and aqueous electrolyte power storage device using separator for aqueous electrolyte power storage device - Google Patents

Separator for aqueous electrolyte power storage device, production method for separator for aqueous electrolyte power storage device, and aqueous electrolyte power storage device using separator for aqueous electrolyte power storage device Download PDF

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Publication number
WO2015098052A1
WO2015098052A1 PCT/JP2014/006312 JP2014006312W WO2015098052A1 WO 2015098052 A1 WO2015098052 A1 WO 2015098052A1 JP 2014006312 W JP2014006312 W JP 2014006312W WO 2015098052 A1 WO2015098052 A1 WO 2015098052A1
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Prior art keywords
epoxy resin
separator
storage device
aqueous electrolyte
power storage
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PCT/JP2014/006312
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French (fr)
Japanese (ja)
Inventor
伊藤　聡
俊祐 能見
矢野　雅也
洋佑 山田
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日東電工株式会社
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Publication of WO2015098052A1 publication Critical patent/WO2015098052A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/52—Separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/10—Batteries in stationary systems, e.g. emergency power source in plant
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a separator for an aqueous electrolyte electricity storage device and an aqueous electrolyte electricity storage device, and more particularly to a separator suitable for an aqueous electrolyte electricity storage device represented by an electric double layer capacitor using an aqueous electrolyte and this kind of electricity storage device.
  • Known separators for water-based electrolyte electricity storage devices include, for example, fiber sheets made of inorganic fibers (for example, Patent Document 1) and porous membranes using a polyolefin-based resin (for example, Patent Document 2).
  • the separator for the aqueous electrolyte storage device is required to have high affinity with the aqueous electrolyte.
  • the present invention A separator for an aqueous electrolyte electricity storage device, A three-dimensional network skeleton composed of epoxy resin; Pores communicating so that ions can move between the front and back surfaces of the separator; The separator for water-system electrolyte electrical storage devices provided with this.
  • the present invention provides: Preparing an epoxy resin composition comprising an epoxy resin, a curing agent and a porogen; A step of molding the cured product of the epoxy resin composition into a sheet shape or curing the sheet-shaped molded product of the epoxy resin composition so as to obtain an epoxy resin sheet; Removing the porogen from the epoxy resin sheet; The manufacturing method of the separator for water-system electrolyte electrical storage devices containing this is provided.
  • the present invention provides: A positive electrode; A negative electrode, The separator of the present invention disposed between the positive electrode and the negative electrode; An aqueous electrolyte impregnated in the separator; A water-based electrolyte electricity storage device is provided.
  • Epoxy resin has a high affinity with aqueous electrolytes and is suitable for forming a microporous structure in which short-circuiting between electrodes is unlikely to occur.
  • ADVANTAGE OF THE INVENTION According to this invention, the separator for aqueous
  • FIG. 1 is a schematic cross-sectional view of an aqueous electrolyte electricity storage device according to an embodiment of the present invention. Schematic diagram of the cutting process
  • the water-based electrolyte power storage device refers to a power storage device using an aqueous electrolyte solution (aqueous electrolyte solution).
  • the water-based electrolyte electricity storage device 100 is a water-based electric double layer capacitor including a positive electrode 2, a negative electrode 3, and a separator 4.
  • the separator 4 is disposed between the positive electrode 2 and the negative electrode 3.
  • the positive electrode 2, the negative electrode 3, and the separator 4 are integrally wound to constitute the element body 10.
  • the positive electrode 2 and the negative electrode 3 are each configured by laminating a polarizable electrode, a collector electrode, and a polarizable electrode in this order.
  • the separator 4 includes a three-dimensional network skeleton made of an epoxy resin and holes that communicate with each other so that ions can move between the front surface and the back surface of the separator.
  • the element body 10 is accommodated in the cylindrical case 6. That is, the water-based electrolyte electricity storage device 100 has a cylindrical shape. However, the shape of the water-based electrolyte electricity storage device 100 is not particularly limited. The water-based electrolyte electricity storage device 100 may have a flat square shape, for example. The element body 10 does not necessarily have a winding structure. A plate-shaped element body may be formed by simply laminating the positive electrode 2, the separator 4, and the negative electrode 3.
  • the case 6 is made of a metal such as stainless steel or aluminum.
  • the water-based electrolyte electricity storage device 100 further includes a positive electrode terminal 2a and a negative electrode terminal 3a.
  • the positive electrode terminal 2 a and the negative electrode terminal 3 a protrude upward from the upper surface of the case 6.
  • the element body 10 is impregnated with an aqueous electrolyte.
  • the positive electrode 2, the negative electrode 3, and other members constituting the water-based electrolyte electricity storage device 100 those conventionally known can be used without particular limitation.
  • the water-based electric double layer capacitor is taken as an example, but the present invention is not limited to this, and can be applied to a water-based electrolyte electricity storage device using a water-based electrolyte and a separator.
  • the separator 4 is composed of a porous epoxy resin film having a three-dimensional network skeleton and pores. Adjacent holes may be in communication with each other so that ions can move between the front surface and the back surface of the separator 4, that is, ions can move between the positive electrode 2 and the negative electrode 3.
  • the separator 4 has a thickness in the range of 5 to 50 ⁇ m, for example. If the separator 4 is too thick, it becomes difficult to move ions between the positive electrode 2 and the negative electrode 3. Although it is not impossible to manufacture the separator 4 having a thickness of less than 5 ⁇ m, in order to ensure the reliability of the water-based electrolyte electricity storage device 100, a thickness of 5 ⁇ m or more, particularly 10 ⁇ m or more is preferable.
  • the separator 4 has, for example, a porosity of 20 to 80%, preferably 20 to 60%, and an average pore diameter of 0.02 to 1 ⁇ m. When the porosity and average pore diameter are adjusted to such ranges, the separator 4 can sufficiently exhibit the required functions.
  • the average pore diameter can be obtained by observing the cross section of the separator 4 with a scanning electron microscope. Specifically, image processing is performed for each of the holes existing in a range of a field width of 60 ⁇ m and a predetermined depth from the surface (for example, 1/5 to 1/100 of the thickness of the separator 4). Thus, the pore diameter can be obtained, and the average value thereof can be obtained as the average pore diameter.
  • Image processing can be performed using, for example, free software “Image J” or “Photoshop” manufactured by Adobe.
  • the separator 4 may have an air permeability (Gurley value) in the range of 1 to 1000 seconds / 100 cm 3 . Since the separator 4 has air permeability in such a range, ions can easily move inside the separator 4.
  • the air permeability can be measured according to a method defined in Japanese Industrial Standard (JIS) P8117.
  • the separator for an aqueous electrolyte electricity storage device (separator 4) of this embodiment includes an epoxy resin porous film having a microporous structure, and short-circuiting between electrodes is less likely to occur. Even when the film thickness is small, short-circuiting is unlikely to occur, so this separator is suitable for increasing the capacity of the aqueous electrolyte electricity storage device.
  • the separator for an aqueous electrolyte electricity storage device of this embodiment does not contain a filler. For this reason, it is suitable for weight reduction and thickness reduction of an electrical storage device.
  • the separator for an aqueous electrolyte electricity storage device of the present embodiment is easy for the electrolyte to penetrate.
  • the internal resistance in the electricity storage device can be suppressed, and the characteristics of the aqueous electrolyte electricity storage device can be improved.
  • the time until the separator is filled with the aqueous electrolytic solution can be shortened, so that the productivity of the aqueous electrolyte electrical storage device can be improved.
  • the epoxy resin porous membrane can be produced, for example, by any of the following methods (a), (b), and (c).
  • the methods (a) and (b) are common in that the curing step is performed after the epoxy resin composition is formed into a sheet.
  • the method (c) is characterized in that an epoxy resin block-shaped cured body is formed and the cured body is formed into a sheet shape.
  • Method (a) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied onto a substrate so that a sheet-like molded body of the epoxy resin composition is obtained. Thereafter, the sheet-like molded body of the epoxy resin composition is heated to three-dimensionally crosslink the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the porogen is removed by washing from the obtained epoxy resin sheet and dried to obtain an epoxy resin porous film having pores communicating with the three-dimensional network skeleton.
  • substrate is not specifically limited, A plastic substrate, a glass substrate, a metal plate, etc. can be used as a board
  • Method (b) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied on the substrate. Thereafter, another substrate is placed on the applied epoxy resin composition to produce a sandwich structure. Note that spacers (for example, double-sided tape) may be provided at the four corners of the substrate in order to ensure a certain distance between the substrates. Next, the sandwich structure is heated to cross-link the epoxy resin three-dimensionally. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the obtained epoxy resin sheet is taken out, the porogen is removed by washing, and dried to obtain an epoxy resin porous membrane having pores communicating with the three-dimensional network skeleton.
  • substrate is not restrict
  • Method (c) An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is filled into a mold having a predetermined shape. Thereafter, a cured product of the cylindrical or columnar epoxy resin composition is produced by three-dimensionally crosslinking the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Then, while rotating the hardening body of an epoxy resin composition centering on a cylinder axis
  • the method for producing the porous epoxy resin membrane will be described in more detail while taking the method (c) as an example.
  • the process of preparing an epoxy resin composition, the process of hardening an epoxy resin, the process of removing a porogen, etc. are common to each method.
  • the material which can be used is common to each method.
  • the epoxy resin porous membrane can be manufactured through the following main steps.
  • An epoxy resin composition is prepared.
  • a cured product of the epoxy resin composition is formed into a sheet.
  • the porogen is removed from the epoxy resin sheet.
  • an epoxy resin composition containing an epoxy resin, a curing agent and a porogen is prepared. Specifically, an epoxy resin and a curing agent are dissolved in a porogen to prepare a uniform solution.
  • an aromatic epoxy resin either an aromatic epoxy resin or a non-aromatic epoxy resin can be used.
  • the aromatic epoxy resin include a polyphenyl-based epoxy resin, an epoxy resin containing a fluorene ring, an epoxy resin containing triglycidyl isocyanurate, an epoxy resin containing a heteroaromatic ring (for example, a triazine ring), and the like.
  • Polyphenyl-based epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, stilbene type epoxy resins, biphenyl type epoxy resins, and bisphenol A novolak type epoxy resins.
  • Non-aromatic epoxy resins include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, alicyclic glycidyl amine type epoxy resins, and alicyclic glycidyl ester type epoxy resins. Etc. These may be used alone or in combination of two or more.
  • bisphenol A type epoxy resin brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin containing fluorene ring, triglycidyl isocyanurate
  • Preferred is at least one selected from the group consisting of an epoxy resin, an alicyclic glycidyl ether type epoxy resin, an alicyclic glycidyl amine type epoxy resin, and an alicyclic glycidyl ester type epoxy resin. What has an equivalent can be used conveniently.
  • these epoxy resins are used, a uniform three-dimensional network skeleton and uniform pores can be formed, and excellent chemical resistance and high strength can be imparted to the epoxy resin porous film.
  • the epoxy resin composition includes a glycidylamine type epoxy resin, such as a glycidylamine type epoxy resin and a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol.
  • AD type epoxy resin epoxy resin containing fluorene ring, epoxy resin containing triglycidyl isocyanurate, alicyclic glycidyl ether type epoxy resin, and at least one epoxy resin selected from the group consisting of alicyclic glycidyl ester type epoxy resins Including.
  • the glycidyl amine type epoxy resin is an epoxy resin having a structure in which the hydrogen atom of the amino group of the amine compound is substituted with a glycidyl group, and the glycidyl amine type epoxy resin has two or more diglycidyl from the viewpoint of particularly high crosslinkability. It preferably has an amino group.
  • a specific example of such a glycidylamine type epoxy resin is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (commercially available from Mitsubishi Gas Chemical Company under the trade name “TETRAD®-C”).
  • N, N, N ′, N′-tetraglycidyl-m-xylenediamine (commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name “TETRAD (registered trademark) -X”)
  • an epoxy resin having a diglycidylamino group (commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name “TETRAD (registered trademark) -X”)
  • an epoxy resin having a diglycidylamino group When using glycidylamine type epoxy resin, uniform three-dimensional network skeleton and uniform pores can be formed, crosslink density after curing is improved, and epoxy resin porous film has high strength, heat resistance and chemical resistance. Can be granted.
  • a glycidylamine type epoxy resin may be used independently and may use 2 or more types together.
  • Aromatic curing agents include aromatic amines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (eg, phthalic anhydride, trimellitic anhydride) , Pyromellitic anhydride), phenol resins, phenol novolac resins, amines containing heteroaromatic rings (for example, amines containing triazine rings), and the like.
  • Non-aromatic curing agents include aliphatic amines (eg, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane.
  • aliphatic amines eg, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane.
  • Alicyclic amines eg, isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane adduct, Bis (4-amino-3-methyl Kurohekishiru) methane, bis (4-aminocyclohexyl) methane, these modified products
  • aliphatic polyamide amines containing a polyamine and a dimer acid may be used alone or in combination of two or more.
  • a curing agent having two or more primary amines in the molecule can be suitably used.
  • 1,6-hexanediamine is preferred because of the high crosslink density of the resulting epoxy resin porous membrane, higher chemical stability, and ease of availability and handling.
  • a combination of an epoxy resin and a curing agent a combination of an aromatic epoxy resin and an aliphatic amine curing agent, a combination of an aromatic epoxy resin and an alicyclic amine curing agent, or an alicyclic epoxy resin and an aromatic amine A combination with a curing agent is preferred.
  • excellent heat resistance can be imparted to the porous epoxy resin membrane.
  • the porogen may be a solvent that can dissolve the epoxy resin and the curing agent. Porogens are also used as solvents that can cause reaction-induced phase separation after the epoxy resin and curing agent are polymerized. Specifically, cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol and polypropylene glycol, polyoxyethylene monomethyl ether and polyoxyethylene Ethers such as dimethyl ether can be used as the porogen. These may be used alone or in combination of two or more.
  • at least one selected from the group consisting of polyethylene glycol having a molecular weight of 200 or less, polypropylene glycol having a molecular weight of 500 or less, polyoxyethylene monomethyl ether, and propylene glycol monomethyl ether acetate can be preferably used.
  • these porogens are used, a uniform three-dimensional network skeleton and uniform pores can be formed. These may be used alone or in combination of two or more.
  • a solvent in which a reaction product of the epoxy resin and the curing agent is soluble can be used as a porogen.
  • porogen include brominated bisphenol A type epoxy resin (“Epicoat 5058” manufactured by Japan Epoxy Resin Co., Ltd.).
  • the porosity, average pore size, and pore size distribution of the epoxy resin porous membrane vary depending on the type of raw material, the mixing ratio of the raw material, and the reaction conditions (for example, heating temperature and heating time during reaction-induced phase separation). Therefore, it is preferable to select optimum conditions in order to obtain the target porosity, average pore diameter, and pore diameter distribution.
  • the reaction conditions for example, heating temperature and heating time during reaction-induced phase separation. Therefore, it is preferable to select optimum conditions in order to obtain the target porosity, average pore diameter, and pore diameter distribution.
  • the co-continuous structure of the crosslinked epoxy resin and porogen is fixed in a specific state and stable. A porous structure can be obtained.
  • the blending ratio of the curing agent to the epoxy resin is, for example, 0.6 to 1.5 in terms of the curing agent equivalent to 1 equivalent of epoxy group.
  • Appropriate curing agent equivalent contributes to improvement of properties such as heat resistance, chemical durability and mechanical properties of the epoxy resin porous membrane.
  • a curing accelerator may be added to the solution in order to obtain the desired porous structure.
  • the curing accelerator include tertiary amines such as triethylamine and tributylamine, and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4,5-dihydroxyimidazole. It is done.
  • porogen 40 to 80% by weight of porogen can be used with respect to the total weight of epoxy resin, curing agent and porogen.
  • an epoxy resin porous film having a desired porosity, average pore diameter, and air permeability can be formed.
  • the average pore diameter of the epoxy resin porous membrane As one method for adjusting the average pore diameter of the epoxy resin porous membrane to a desired range, there is a method of using a mixture of two or more epoxy resins having different epoxy equivalents.
  • the difference in epoxy equivalent is preferably 100 or more, and there are cases where an epoxy resin that is liquid at normal temperature and an epoxy resin that is solid at normal temperature are mixed and used.
  • a cured product of the epoxy resin composition is prepared from a solution containing an epoxy resin, a curing agent and a porogen. Specifically, the solution is filled in a mold and heated as necessary. A cured body having a predetermined shape is obtained by three-dimensionally crosslinking the epoxy resin. In that case, a co-continuous structure is formed by phase-separation of a crosslinked epoxy resin and a porogen.
  • the shape of the cured body is not particularly limited. If a columnar or cylindrical mold is used, a cured body having a cylindrical or columnar shape can be obtained. When the cured body has a cylindrical or columnar shape, it is easy to carry out a cutting step (see FIG. 2) described later.
  • the temperature and time required for curing the epoxy resin composition are not particularly limited because they vary depending on the type of epoxy resin and curing agent.
  • a curing treatment can be performed at room temperature.
  • the temperature is about 20 to 40 ° C., and the time is about 3 to 100 hours, preferably about 20 to 50 hours.
  • the temperature is about 40 to 120 ° C., preferably about 60 to 100 ° C., and the time is about 10 to 300 minutes, preferably about 30 to 180 minutes.
  • post-cure post-treatment
  • post-curing conditions are not particularly limited, but the temperature is room temperature or about 50 to 160 ° C., and the time is about 2 to 48 hours.
  • the dimensions of the cured body are not particularly limited.
  • the diameter of the cured body is, for example, 20 cm or more, preferably 30 to 150 cm, from the viewpoint of manufacturing efficiency of the epoxy resin porous film.
  • the length (axial direction) of the cured body can also be appropriately set in consideration of the dimensions of the epoxy resin porous film to be obtained.
  • the length of the cured body is, for example, 20 to 200 cm, preferably 20 to 150 cm, and more preferably 20 to 120 cm from the viewpoint of ease of handling.
  • the cured body is formed into a sheet.
  • the cured body having a cylindrical or columnar shape can be formed into a sheet shape by the following method. Specifically, the cured body 12 is attached to the shaft 14 as shown in FIG.
  • the surface layer portion of the cured body 12 is cut (sliced) at a predetermined thickness using a cutting blade 18 (slicer) so that an epoxy resin sheet 16 having a long shape is obtained.
  • the surface layer portion of the cured body 12 is cut while rotating the cured body 12 relative to the cutting blade 18 around the cylindrical axis O (or columnar axis) of the cured body 12. According to this method, the epoxy resin sheet 16 can be produced efficiently.
  • the line speed when cutting the cured body 12 is in the range of 2 to 70 m / min, for example.
  • the thickness of the epoxy resin sheet 16 is determined according to the target thickness (10 to 50 ⁇ m) of the epoxy resin porous film. Since the thickness slightly decreases when the porogen is removed and dried, the epoxy resin sheet 16 is usually slightly thicker than the target thickness of the epoxy resin porous film.
  • the length of the epoxy resin sheet 16 is not specifically limited, From a viewpoint of the production efficiency of the epoxy resin sheet 16, it is 100 m or more, for example, Preferably it is 1000 m or more.
  • the porogen is extracted from the epoxy resin sheet 16 and removed.
  • the porogen can be removed from the epoxy resin sheet 16 by immersing the epoxy resin sheet 16 in a solvent.
  • the solvent is preferably a halogen-free solvent that does not have a large environmental load.
  • the halogen-free solvent for removing the porogen from the epoxy resin sheet 16 at least one selected from the group consisting of water, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), and THF (tetrahydrofuran) is used as the porogen. It can be used depending on the type. Also, supercritical fluids such as water and carbon dioxide can be used as a solvent for removing porogen. In order to positively remove the porogen from the epoxy resin sheet 16, ultrasonic cleaning may be performed, or the solvent may be heated and used.
  • the cleaning device for removing the porogen is not particularly limited, and a known cleaning device can be used.
  • a multistage cleaning apparatus having a plurality of cleaning tanks can be suitably used.
  • the number of cleaning stages is more preferably 3 or more.
  • the temperature of the solvent may be changed or the type of the solvent may be changed in the cleaning of each stage.
  • the epoxy resin porous film is dried.
  • the drying conditions are not particularly limited, and the temperature is usually about 40 to 120 ° C., preferably about 50 to 100 ° C., and the drying time is about 10 seconds to 5 minutes.
  • a drying apparatus employing a known sheet drying method such as a tenter method, a floating method, a roll method, or a belt method can be used. A plurality of drying methods may be combined.
  • an epoxy resin porous film having a microporous structure that can be used as the separator 4 can be manufactured very easily. Since the process required at the time of manufacture of a polyolefin porous membrane, for example, an extending process, can be omitted, an epoxy resin porous membrane can be manufactured with high productivity.
  • the separator 4 may be comprised only by the epoxy resin porous film, and may be comprised by the laminated body of an epoxy resin porous film and another porous material.
  • porous materials include polyolefin porous films such as polyethylene porous films and polypropylene porous films, cellulose porous films, and fluororesin porous films.
  • Other porous materials may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
  • the separator 4 may be composed of a laminate of an epoxy resin porous film and a reinforcing material.
  • the reinforcing material include woven fabric and non-woven fabric.
  • the reinforcing material may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
  • RO water means pure water obtained by processing using a reverse osmosis membrane.
  • the short circuit rate was measured by the following method. An aluminum foil having a thickness of 20 ⁇ m was cut into a 30 mm square. Next, the separator was cut into a 40 mm square. This separator was immersed in a 0.5 mol / L sulfuric acid aqueous solution as an electrolytic solution, and then sandwiched between the aluminum foils to prepare an electrode group. Next, a square aluminum plate having a thickness of 5 mm and a 35 mm square, and an electrode group was sandwiched from both sides using an aluminum plate having a terminal connection portion prepared on the end face.
  • interposed this electrode group was inserted
  • the test electrode group obtained as described above was placed in a pressure device.
  • An AC resistance measuring machine manufactured by Hioki Electric Co., Ltd.
  • Pressure was applied until a surface pressure of 0.2 MPa was applied to the test electrode group, and the resistance value was measured. When the resistance value decreased, it was determined that a short circuit occurred. This measurement was carried out 10 times in total for each example, and the short circuit rate was X / 10 (of 10 measurements, the number of short circuits was X times).
  • Example 1 In a 3 L cylindrical plastic container, jER (registered trademark) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq.) And TETRAD (registered trademark) -C (glycidylamine) Type epoxy resin, Mitsubishi Gas Chemical Co., Ltd., epoxy equivalent 95-110 g / eq.) 25.0 parts by weight is dissolved in polypropylene glycol (ADEKA Co., Ltd., Adeka Polyether P-400) 211.9 parts by weight, An epoxy resin / polypropylene glycol solution was prepared.
  • the polypropylene glycol was removed by immersion in water for 12 hours. Then, it dried for 2 hours in 80 degreeC atmosphere, and obtained the epoxy resin porous membrane (separator) which has a thickness of 48 micrometers.
  • Example 2 The same procedure as in Example 1 was carried out except that a continuous lathe was sliced with a thickness of 22 ⁇ m using a cutting lathe device to obtain an epoxy resin porous film (separator) having a thickness of 21 ⁇ m.
  • Table 1 shows the evaluation results for the examples.
  • Example 1 As shown in Table 1, in Example 1, no short circuit between the electrodes occurred. Also in Example 2 in which the film thickness was made thinner than Example 1, no short circuit occurred between the electrodes. Moreover, these epoxy resin porous membranes (separator) showed favorable liquid absorptivity, and it turned out that it has high affinity with the sulfuric acid aqueous solution which is aqueous electrolyte solution.
  • the separator provided by the present invention can be suitably used for water-based electrolyte electricity storage devices such as electric double layer capacitors, and is particularly required for vehicles, motorcycles, ships, construction machinery, industrial machinery, residential electricity storage systems, and the like. It can be suitably used for a capacitor having a capacity.

Abstract

Provided is a separator for an aqueous electrolyte power storage device. The separator is highly compatible with an aqueous electrolyte battery and is suited to preventing short circuits between electrodes. A separator for an aqueous electrolyte power storage device, the separator being provided with a three-dimensional network structure that is constituted by an epoxy resin, and with pores that communicate so as to allow ions to move between front and rear surfaces of the separator. The thickness of the separator is in the range of, for example, 5-50 μm. This separator can be produced, for example, by removing porogens from an epoxy resin sheet.

Description

水系電解質蓄電デバイス用セパレータとその製造方法、及びそれを用いた水系電解質蓄電デバイスSeparator for aqueous electrolyte electricity storage device, method for producing the same, and aqueous electrolyte electricity storage device using the same
　本発明は、水系電解質蓄電デバイス用セパレータ及び水系電解質蓄電デバイスに関し、詳しくは、水系の電解液を用いる電気二重層コンデンサに代表される水系電解質蓄電デバイスに適したセパレータ及びこの種の蓄電デバイスに関する。 The present invention relates to a separator for an aqueous electrolyte electricity storage device and an aqueous electrolyte electricity storage device, and more particularly to a separator suitable for an aqueous electrolyte electricity storage device represented by an electric double layer capacitor using an aqueous electrolyte and this kind of electricity storage device.
　水系電解質蓄電デバイス用セパレータとしては、例えば、無機繊維からなる繊維シート（例えば、特許文献１）やポリオレフィン系樹脂を用いた多孔膜（例えば、特許文献２）が知られている。 Known separators for water-based electrolyte electricity storage devices include, for example, fiber sheets made of inorganic fibers (for example, Patent Document 1) and porous membranes using a polyolefin-based resin (for example, Patent Document 2).
特開２００５－３２７９３５号公報JP 2005-327935 A 特開２００５－１０９２４４号公報JP 2005-109244 A
　水系電解質蓄電デバイス用セパレータには、水系電解質蓄電デバイスの内部抵抗を小さくする観点から、水系電解液との高い親和性が求められる。また、内部抵抗を低くするため、セパレータの厚みを薄くしたときに、電極間の短絡が生じないことも求められる。 From the viewpoint of reducing the internal resistance of the aqueous electrolyte storage device, the separator for the aqueous electrolyte storage device is required to have high affinity with the aqueous electrolyte. In addition, in order to reduce the internal resistance, it is also required that no short circuit occurs between the electrodes when the thickness of the separator is reduced.
　本発明は、水系電解液との親和性が高く、電極間の短絡の防止に適した、水系電解質蓄電デバイス用セパレータを提供することを目的とする。本発明の別の目的は、このようなセパレータの製造に適した方法を提供することにある。本発明の更に別の目的は、このようなセパレータの優れた特性を活かした水系電解質蓄電デバイスを提供することにある。 An object of the present invention is to provide a separator for an aqueous electrolyte storage device that has a high affinity with an aqueous electrolyte and is suitable for prevention of a short circuit between electrodes. Another object of the present invention is to provide a method suitable for manufacturing such a separator. Still another object of the present invention is to provide a water-based electrolyte electricity storage device utilizing the excellent characteristics of such a separator.
　すなわち、本発明は、
　水系電解質蓄電デバイス用セパレータであって、
　エポキシ樹脂で構成された三次元網目状骨格と、
　前記セパレータの表面と裏面との間でイオンが移動できるように連通している空孔と、
を備えた、水系電解質蓄電デバイス用セパレータ、を提供する。 That is, the present invention
A separator for an aqueous electrolyte electricity storage device,
A three-dimensional network skeleton composed of epoxy resin;
Pores communicating so that ions can move between the front and back surfaces of the separator;
The separator for water-system electrolyte electrical storage devices provided with this.
　別の側面において、本発明は、
　エポキシ樹脂、硬化剤及びポロゲンを含むエポキシ樹脂組成物を調製する工程と、
　エポキシ樹脂シートが得られるように、前記エポキシ樹脂組成物の硬化体をシート状に成形する又は前記エポキシ樹脂組成物のシート状成形体を硬化させる工程と、
　前記エポキシ樹脂シートから前記ポロゲンを除去する工程と、
を含む、水系電解質蓄電デバイス用セパレータの製造方法、を提供する。 In another aspect, the present invention provides:
Preparing an epoxy resin composition comprising an epoxy resin, a curing agent and a porogen;
A step of molding the cured product of the epoxy resin composition into a sheet shape or curing the sheet-shaped molded product of the epoxy resin composition so as to obtain an epoxy resin sheet;
Removing the porogen from the epoxy resin sheet;
The manufacturing method of the separator for water-system electrolyte electrical storage devices containing this is provided.
　別の側面において、本発明は、
　正極と、
　負極と、
　前記正極と前記負極との間に配置された、本発明のセパレータと、
　前記セパレータに含浸した水系電解液と、
を備えた、水系電解質蓄電デバイス、を提供する。 In another aspect, the present invention provides:
A positive electrode;
A negative electrode,
The separator of the present invention disposed between the positive electrode and the negative electrode;
An aqueous electrolyte impregnated in the separator;
A water-based electrolyte electricity storage device is provided.
　エポキシ樹脂は、水系電解液との親和性が高く、電極間の短絡が生じにくい微多孔構造の形成にも適している。本発明によれば、水系電解液との親和性が高く、電極間の短絡が生じにくい水系電解質蓄電デバイス用セパレータが得られる。また、このセパレータの優れた特性を活かした水系電解質蓄電デバイスを得ることができる。 Epoxy resin has a high affinity with aqueous electrolytes and is suitable for forming a microporous structure in which short-circuiting between electrodes is unlikely to occur. ADVANTAGE OF THE INVENTION According to this invention, the separator for aqueous | water-based electrolyte electrical storage devices with high affinity with aqueous | water-based electrolyte solution and being hard to produce the short circuit between electrodes is obtained. Moreover, the water-system electrolyte electrical storage device which utilized the outstanding characteristic of this separator can be obtained.
本発明の一実施形態に係る水系電解質蓄電デバイスの概略断面図1 is a schematic cross-sectional view of an aqueous electrolyte electricity storage device according to an embodiment of the present invention. 切削工程の概略図Schematic diagram of the cutting process
　以下、添付の図面を参照しつつ、本発明の一実施形態を説明する。なお、本明細書において、水系電解質蓄電デバイスとは、水溶液系の電解液（水系電解液）を用いる蓄電デバイスを示す。 Hereinafter, an embodiment of the present invention will be described with reference to the accompanying drawings. In the present specification, the water-based electrolyte power storage device refers to a power storage device using an aqueous electrolyte solution (aqueous electrolyte solution).
　本実施形態に係る水系電解質蓄電デバイス１００は、正極２、負極３、及びセパレータ４を備えた水系電気二重層コンデンサである。セパレータ４は、正極２と負極３との間に配置されている。正極２、負極３及びセパレータ４は、一体的に巻回されて素子本体１０を構成している。正極２及び負極３は、それぞれ分極性電極、集電極、分極性電極がこの順に積層されて構成されている。セパレータ４は、エポキシ樹脂で構成された三次元網目状骨格と、セパレータの表面と裏面との間でイオンが移動できるように連通している空孔と、を備えている。 The water-based electrolyte electricity storage device 100 according to the present embodiment is a water-based electric double layer capacitor including a positive electrode 2, a negative electrode 3, and a separator 4. The separator 4 is disposed between the positive electrode 2 and the negative electrode 3. The positive electrode 2, the negative electrode 3, and the separator 4 are integrally wound to constitute the element body 10. The positive electrode 2 and the negative electrode 3 are each configured by laminating a polarizable electrode, a collector electrode, and a polarizable electrode in this order. The separator 4 includes a three-dimensional network skeleton made of an epoxy resin and holes that communicate with each other so that ions can move between the front surface and the back surface of the separator.
　本実施形態において、素子本体１０は円筒形のケース６に収容されている。すなわち、水系電解質蓄電デバイス１００は円筒の形状を有している。しかし、水系電解質蓄電デバイス１００の形状は特に限定されない。水系電解質蓄電デバイス１００は、例えば、扁平な角型の形状を有していてもよい。また、素子本体１０は巻回構造を必須としない。正極２、セパレータ４及び負極３が単に積層されることによって、板状の素子本体が形成されていてもよい。ケース６は、ステンレス、アルミニウム等の金属で作られている。 In the present embodiment, the element body 10 is accommodated in the cylindrical case 6. That is, the water-based electrolyte electricity storage device 100 has a cylindrical shape. However, the shape of the water-based electrolyte electricity storage device 100 is not particularly limited. The water-based electrolyte electricity storage device 100 may have a flat square shape, for example. The element body 10 does not necessarily have a winding structure. A plate-shaped element body may be formed by simply laminating the positive electrode 2, the separator 4, and the negative electrode 3. The case 6 is made of a metal such as stainless steel or aluminum.
　水系電解質蓄電デバイス１００は、さらに、正極端子２ａ及び負極端子３ａを備えている。正極端子２ａ及び負極端子３ａは、ケース６の上面から上方に突出している。素子本体１０には、水系電解液が含浸されている。 The water-based electrolyte electricity storage device 100 further includes a positive electrode terminal 2a and a negative electrode terminal 3a. The positive electrode terminal 2 a and the negative electrode terminal 3 a protrude upward from the upper surface of the case 6. The element body 10 is impregnated with an aqueous electrolyte.
　水系電解質蓄電デバイス１００を構成する正極２、負極３及びその他の部材は、従来から知られていたものを特に制限することなく使用することができる。 As the positive electrode 2, the negative electrode 3, and other members constituting the water-based electrolyte electricity storage device 100, those conventionally known can be used without particular limitation.
　上記では、水系電気二重層コンデンサを例に挙げたが、本発明は、これに限らず、水系電解液とセパレータとを用いる水系電解質蓄電デバイスに適用できる。 In the above, the water-based electric double layer capacitor is taken as an example, but the present invention is not limited to this, and can be applied to a water-based electrolyte electricity storage device using a water-based electrolyte and a separator.
　次に、セパレータ４について詳しく説明する。 Next, the separator 4 will be described in detail.
　本実施形態において、セパレータ４は、三次元網目状骨格と、空孔とを備えたエポキシ樹脂多孔膜で構成されている。セパレータ４の表面と裏面との間でイオンが移動できるように、つまり、正極２と負極３との間をイオンが移動できるように、隣り合う空孔は互いに連通していてもよい。セパレータ４は、例えば、５～５０μｍの範囲の厚さを有する。セパレータ４が厚すぎると、正極２と負極３との間のイオンの移動が困難となる。５μｍ未満の厚さのセパレータ４を製造することは不可能ではないが、水系電解質蓄電デバイス１００の信頼性を確保するうえで、５μｍ以上、特に１０μｍ以上の厚さが好ましい。 In this embodiment, the separator 4 is composed of a porous epoxy resin film having a three-dimensional network skeleton and pores. Adjacent holes may be in communication with each other so that ions can move between the front surface and the back surface of the separator 4, that is, ions can move between the positive electrode 2 and the negative electrode 3. The separator 4 has a thickness in the range of 5 to 50 μm, for example. If the separator 4 is too thick, it becomes difficult to move ions between the positive electrode 2 and the negative electrode 3. Although it is not impossible to manufacture the separator 4 having a thickness of less than 5 μm, in order to ensure the reliability of the water-based electrolyte electricity storage device 100, a thickness of 5 μm or more, particularly 10 μm or more is preferable.
　セパレータ４は、例えば、２０～８０％、好ましくは２０～６０％の範囲の空孔率を有し、０．０２～１μｍの範囲の平均孔径を有する。空孔率及び平均孔径がこのような範囲に調節されていると、セパレータ４は、必要とされる機能を十分に発揮しうる。 The separator 4 has, for example, a porosity of 20 to 80%, preferably 20 to 60%, and an average pore diameter of 0.02 to 1 μm. When the porosity and average pore diameter are adjusted to such ranges, the separator 4 can sufficiently exhibit the required functions.
　空孔率は、以下の方法で測定できる。まず、測定対象を一定の寸法（例えば、直径６ｃｍの円形）に切断し、その体積及び重量を求める。得られた結果を次式に代入して空孔率を算出する。
　　空孔率（％）＝１００×（Ｖ－（Ｗ／Ｄ））／Ｖ
　　　Ｖ：体積（ｃｍ3）
　　　Ｗ：重量（ｇ）
　　　Ｄ：構成成分の平均密度（ｇ／ｃｍ3） The porosity can be measured by the following method. First, a measurement object is cut into a certain dimension (for example, a circle having a diameter of 6 cm), and its volume and weight are obtained. The porosity is calculated by substituting the obtained result into the following equation.
Porosity (%) = 100 × (V− (W / D)) / V
V: Volume (cm 3 )
W: Weight (g)
D: Average density of components (g / cm 3 )
　平均孔径は、走査型電子顕微鏡でセパレータ４の断面を観察して求めることができる。具体的には、視野幅６０μｍ、かつ表面から所定の深さ（例えば、セパレータ４の厚さの１／５～１／１００）までの範囲内に存在する空孔のそれぞれについて、画像処理を行って孔径を求め、それらの平均値を平均孔径として求めることができる。画像処理は、例えば、フリーソフト「Image J」又はAdobe社製「Photoshop」を使用して行える。 The average pore diameter can be obtained by observing the cross section of the separator 4 with a scanning electron microscope. Specifically, image processing is performed for each of the holes existing in a range of a field width of 60 μm and a predetermined depth from the surface (for example, 1/5 to 1/100 of the thickness of the separator 4). Thus, the pore diameter can be obtained, and the average value thereof can be obtained as the average pore diameter. Image processing can be performed using, for example, free software “Image J” or “Photoshop” manufactured by Adobe.
　また、セパレータ４は、１～１０００秒／１００ｃｍ3の範囲の通気度（ガーレー値）を有していてもよい。セパレータ４がこのような範囲に通気度を有していることにより、セパレータ４の内部をイオンが容易に移動しうる。通気度は、日本工業規格（ＪＩＳ）Ｐ８１１７に規定された方法に従って測定できる。 The separator 4 may have an air permeability (Gurley value) in the range of 1 to 1000 seconds / 100 cm 3 . Since the separator 4 has air permeability in such a range, ions can easily move inside the separator 4. The air permeability can be measured according to a method defined in Japanese Industrial Standard (JIS) P8117.
　本実施形態の水系電解質蓄電デバイス用セパレータ（セパレータ４）は、微多孔構造を有するエポキシ樹脂多孔膜を備えており、電極間における短絡が生じにくい。膜厚が薄い場合であっても短絡が生じにくいため、このセパレータは水系電解質蓄電デバイスの高容量化に適している。 The separator for an aqueous electrolyte electricity storage device (separator 4) of this embodiment includes an epoxy resin porous film having a microporous structure, and short-circuiting between electrodes is less likely to occur. Even when the film thickness is small, short-circuiting is unlikely to occur, so this separator is suitable for increasing the capacity of the aqueous electrolyte electricity storage device.
　本実施形態の水系電解質蓄電デバイス用セパレータはフィラーを含んでいない。このため、蓄電デバイスの軽量化及び薄型化に適している。 The separator for an aqueous electrolyte electricity storage device of this embodiment does not contain a filler. For this reason, it is suitable for weight reduction and thickness reduction of an electrical storage device.
　また、本実施形態の水系電解質蓄電デバイス用セパレータは、電解液が浸透しやすい。その結果、蓄電デバイス中での内部抵抗を抑制して、水系電解質蓄電デバイスの特性を向上できる。さらに、セパレータに電解液を含浸させる工程において、セパレータ中に水系電解液が満たされるまでの時間を短縮できるため、水系電解質蓄電デバイスの生産性を向上できる。 Moreover, the separator for an aqueous electrolyte electricity storage device of the present embodiment is easy for the electrolyte to penetrate. As a result, the internal resistance in the electricity storage device can be suppressed, and the characteristics of the aqueous electrolyte electricity storage device can be improved. Furthermore, in the step of impregnating the separator with the electrolytic solution, the time until the separator is filled with the aqueous electrolytic solution can be shortened, so that the productivity of the aqueous electrolyte electrical storage device can be improved.
　次に、セパレータ４に使用されたエポキシ樹脂多孔膜の製造方法を説明する。 Next, the manufacturing method of the epoxy resin porous film used for the separator 4 will be described.
　エポキシ樹脂多孔膜は、例えば、下記（ａ）（ｂ）及び（ｃ）のいずれかの方法で製造することができる。方法（ａ）及び（ｂ）は、エポキシ樹脂組成物をシート状に成形した後で硬化工程を実施する点で共通している。方法（ｃ）は、エポキシ樹脂のブロック状の硬化体を作り、その硬化体をシート状に成形することを特徴としている。 The epoxy resin porous membrane can be produced, for example, by any of the following methods (a), (b), and (c). The methods (a) and (b) are common in that the curing step is performed after the epoxy resin composition is formed into a sheet. The method (c) is characterized in that an epoxy resin block-shaped cured body is formed and the cured body is formed into a sheet shape.
　方法（ａ）
　エポキシ樹脂組成物のシート状成形体が得られるように、エポキシ樹脂、硬化剤及びポロゲンを含むエポキシ樹脂組成物を基板上に塗布する。その後、エポキシ樹脂組成物のシート状成形体を加熱してエポキシ樹脂を三次元架橋させる。その際、エポキシ樹脂架橋体とポロゲンとの相分離により共連続構造が形成される。その後、得られたエポキシ樹脂シートからポロゲンを洗浄によって除去し、乾燥させることにより、三次元網目状骨格と連通する空孔とを有するエポキシ樹脂多孔膜が得られる。基板の種類は特に限定されず、プラスチック基板、ガラス基板、金属板等を基板として使用できる。 Method (a)
An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied onto a substrate so that a sheet-like molded body of the epoxy resin composition is obtained. Thereafter, the sheet-like molded body of the epoxy resin composition is heated to three-dimensionally crosslink the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the porogen is removed by washing from the obtained epoxy resin sheet and dried to obtain an epoxy resin porous film having pores communicating with the three-dimensional network skeleton. The kind of board | substrate is not specifically limited, A plastic substrate, a glass substrate, a metal plate, etc. can be used as a board | substrate.
　方法（ｂ）
　エポキシ樹脂、硬化剤及びポロゲンを含むエポキシ樹脂組成物を基板上に塗布する。その後、塗布したエポキシ樹脂組成物の上に別の基板を被せてサンドイッチ構造体を作製する。なお、基板と基板との間に一定の間隔を確保するために、基板の四隅にスペーサー（例えば、両面テープ）を設けてもよい。次に、サンドイッチ構造体を加熱してエポキシ樹脂を三次元架橋させる。その際、エポキシ樹脂架橋体とポロゲンとの相分離により共連続構造が形成される。その後、得られたエポキシ樹脂シートを取り出し、ポロゲンを洗浄によって除去し、乾燥させることにより、三次元網目状骨格と連通する空孔とを有するエポキシ樹脂多孔膜が得られる。基板の種類は特に制限されず、プラスチック基板、ガラス基板、金属板等を基板として使用できる。特に、ガラス基板を好適に使用できる。 Method (b)
An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is applied on the substrate. Thereafter, another substrate is placed on the applied epoxy resin composition to produce a sandwich structure. Note that spacers (for example, double-sided tape) may be provided at the four corners of the substrate in order to ensure a certain distance between the substrates. Next, the sandwich structure is heated to cross-link the epoxy resin three-dimensionally. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Thereafter, the obtained epoxy resin sheet is taken out, the porogen is removed by washing, and dried to obtain an epoxy resin porous membrane having pores communicating with the three-dimensional network skeleton. The kind of board | substrate is not restrict | limited in particular, A plastic substrate, a glass substrate, a metal plate etc. can be used as a board | substrate. In particular, a glass substrate can be suitably used.
　方法（ｃ）
　エポキシ樹脂、硬化剤及びポロゲンを含むエポキシ樹脂組成物を所定形状の金型内に充填する。その後、エポキシ樹脂を三次元架橋させることによって、円筒状又は円柱状のエポキシ樹脂組成物の硬化体を作製する。その際、エポキシ樹脂架橋体とポロゲンとの相分離により共連続構造が形成される。その後、エポキシ樹脂組成物の硬化体を円筒軸又は円柱軸を中心に回転させながら、硬化体の表層部を所定の厚さに切削して長尺状のエポキシ樹脂シートを作製する。そして、エポキシ樹脂シートに含まれたポロゲンを洗浄によって除去し、乾燥させることにより、三次元網目状骨格と連通する空孔とを有するエポキシ樹脂多孔膜が得られる。 Method (c)
An epoxy resin composition containing an epoxy resin, a curing agent and a porogen is filled into a mold having a predetermined shape. Thereafter, a cured product of the cylindrical or columnar epoxy resin composition is produced by three-dimensionally crosslinking the epoxy resin. At that time, a co-continuous structure is formed by phase separation of the crosslinked epoxy resin and the porogen. Then, while rotating the hardening body of an epoxy resin composition centering on a cylinder axis | shaft or a cylinder axis | shaft, the surface layer part of a hardening body is cut to predetermined thickness, and a long-shaped epoxy resin sheet is produced. Then, the porogen contained in the epoxy resin sheet is removed by washing and dried to obtain an epoxy resin porous film having pores communicating with the three-dimensional network skeleton.
　以下、方法（ｃ）を例として取り上げつつ、エポキシ樹脂多孔膜の製造方法についてさらに詳細に説明する。なお、エポキシ樹脂組成物を調製する工程、エポキシ樹脂を硬化させる工程、ポロゲンを除去する工程等は、各方法に共通している。また、使用できる材料も各方法に共通である。 Hereinafter, the method for producing the porous epoxy resin membrane will be described in more detail while taking the method (c) as an example. In addition, the process of preparing an epoxy resin composition, the process of hardening an epoxy resin, the process of removing a porogen, etc. are common to each method. Moreover, the material which can be used is common to each method.
　方法（ｃ）によれば、エポキシ樹脂多孔膜は、以下の主要な工程を経て製造されうる。
（i）エポキシ樹脂組成物を調製する。
（ii）エポキシ樹脂組成物の硬化体をシート状に成形する。
（iii）エポキシ樹脂シートからポロゲンを除去する。 According to the method (c), the epoxy resin porous membrane can be manufactured through the following main steps.
(I) An epoxy resin composition is prepared.
(Ii) A cured product of the epoxy resin composition is formed into a sheet.
(Iii) The porogen is removed from the epoxy resin sheet.
　まず、エポキシ樹脂、硬化剤及びポロゲン（細孔形成剤）を含むエポキシ樹脂組成物を調製する。具体的には、エポキシ樹脂及び硬化剤をポロゲンに溶解させて均一な溶液を調製する。 First, an epoxy resin composition containing an epoxy resin, a curing agent and a porogen (pore forming agent) is prepared. Specifically, an epoxy resin and a curing agent are dissolved in a porogen to prepare a uniform solution.
　エポキシ樹脂としては、芳香族エポキシ樹脂及び非芳香族エポキシ樹脂のいずれも使用可能である。芳香族エポキシ樹脂としては、ポリフェニルベースエポキシ樹脂、フルオレン環を含むエポキシ樹脂、トリグリシジルイソシアヌレートを含むエポキシ樹脂、複素芳香環（例えば、トリアジン環）を含むエポキシ樹脂等が挙げられる。ポリフェニルベースエポキシ樹脂としては、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、スチルベン型エポキシ樹脂、ビフェニル型エポキシ樹脂、ビスフェノールＡノボラック型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、ジアミノジフェニルメタン型エポキシ樹脂、テトラキス（ヒドロキシフェニル）エタンベースエポキシ樹脂等が挙げられる。非芳香族エポキシ樹脂としては、脂肪族グリシジルエーテル型エポキシ樹脂、脂肪族グリシジルエステル型エポキシ樹脂、脂環族グリシジルエーテル型エポキシ樹脂、脂環族グリシジルアミン型エポキシ樹脂、脂環族グリシジルエステル型エポキシ樹脂等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 As the epoxy resin, either an aromatic epoxy resin or a non-aromatic epoxy resin can be used. Examples of the aromatic epoxy resin include a polyphenyl-based epoxy resin, an epoxy resin containing a fluorene ring, an epoxy resin containing triglycidyl isocyanurate, an epoxy resin containing a heteroaromatic ring (for example, a triazine ring), and the like. Polyphenyl-based epoxy resins include bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD type epoxy resins, stilbene type epoxy resins, biphenyl type epoxy resins, and bisphenol A novolak type epoxy resins. , Cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, tetrakis (hydroxyphenyl) ethane base epoxy resin, and the like. Non-aromatic epoxy resins include aliphatic glycidyl ether type epoxy resins, aliphatic glycidyl ester type epoxy resins, alicyclic glycidyl ether type epoxy resins, alicyclic glycidyl amine type epoxy resins, and alicyclic glycidyl ester type epoxy resins. Etc. These may be used alone or in combination of two or more.
　これらの中でも、ビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、芳香族グリシジルアミン型エポキシ樹脂、フルオレン環を含むエポキシ樹脂、トリグリシジルイソシアヌレートを含むエポキシ樹脂、脂環族グリシジルエーテル型エポキシ樹脂、脂環族グリシジルアミン型エポキシ樹脂及び脂環族グリシジルエステル型エポキシ樹脂からなる群より選ばれる少なくとも１つが好適であり、これらの中でも６０００以下のエポキシ当量を有するものを好適に使用できる。これらのエポキシ樹脂を使用すると、均一な三次元網目状骨格及び均一な空孔を形成できるとともに、エポキシ樹脂多孔膜に優れた耐薬品性及び高い強度を付与できる。 Among these, bisphenol A type epoxy resin, brominated bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, aromatic glycidylamine type epoxy resin, epoxy resin containing fluorene ring, triglycidyl isocyanurate Preferred is at least one selected from the group consisting of an epoxy resin, an alicyclic glycidyl ether type epoxy resin, an alicyclic glycidyl amine type epoxy resin, and an alicyclic glycidyl ester type epoxy resin. What has an equivalent can be used conveniently. When these epoxy resins are used, a uniform three-dimensional network skeleton and uniform pores can be formed, and excellent chemical resistance and high strength can be imparted to the epoxy resin porous film.
　本発明の一実施形態では、エポキシ樹脂組成物は、グリシジルアミン型エポキシ樹脂を含み、例えばグリシジルアミン型エポキシ樹脂とビスフェノールＡ型エポキシ樹脂、臭素化ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、フルオレン環を含むエポキシ樹脂、トリグリシジルイソシアヌレートを含むエポキシ樹脂、脂環族グリシジルエーテル型エポキシ樹脂、及び脂環族グリシジルエステル型エポキシ樹脂からなる群より選ばれる少なくとも１つのエポキシ樹脂とを含む。 In one embodiment of the present invention, the epoxy resin composition includes a glycidylamine type epoxy resin, such as a glycidylamine type epoxy resin and a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol. AD type epoxy resin, epoxy resin containing fluorene ring, epoxy resin containing triglycidyl isocyanurate, alicyclic glycidyl ether type epoxy resin, and at least one epoxy resin selected from the group consisting of alicyclic glycidyl ester type epoxy resins Including.
　グリシジルアミン型エポキシ樹脂は、アミン化合物のアミノ基の水素原子がグリシジル基で置換された構造を有するエポキシ樹脂であり、グリシジルアミン型エポキシ樹脂は、特に高い架橋性の観点から２個以上のジグリシジルアミノ基を有することが好ましい。このようなグリシジルアミン型エポキシ樹脂の具体例としては、１，３－ビス（Ｎ，Ｎ－ジグリシジルアミノメチル）シクロヘキサン（三菱ガス化学株式会社から商品名「ＴＥＴＲＡＤ（登録商標）－Ｃ」として市販されている）、Ｎ，Ｎ，Ｎ’，Ｎ’－テトラグリシジル－ｍ－キシレンジアミン（三菱ガス化学株式会社から商品名「ＴＥＴＲＡＤ（登録商標）－Ｘ」として市販されている）等の２個のジグリシジルアミノ基を有するエポキシ樹脂等が挙げられる。グリシジルアミン型エポキシ樹脂を使用すると、均一な三次元網目状骨格及び均一な空孔を形成できるとともに、硬化後の架橋密度が向上し、エポキシ樹脂多孔膜に高い強度と耐熱性及び耐薬品性を付与できる。グリシジルアミン型エポキシ樹脂は単独で用いてもよく、２種以上を併用してもよい。 The glycidyl amine type epoxy resin is an epoxy resin having a structure in which the hydrogen atom of the amino group of the amine compound is substituted with a glycidyl group, and the glycidyl amine type epoxy resin has two or more diglycidyl from the viewpoint of particularly high crosslinkability. It preferably has an amino group. A specific example of such a glycidylamine type epoxy resin is 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane (commercially available from Mitsubishi Gas Chemical Company under the trade name “TETRAD®-C”). N, N, N ′, N′-tetraglycidyl-m-xylenediamine (commercially available from Mitsubishi Gas Chemical Co., Ltd. under the trade name “TETRAD (registered trademark) -X”) And an epoxy resin having a diglycidylamino group. When using glycidylamine type epoxy resin, uniform three-dimensional network skeleton and uniform pores can be formed, crosslink density after curing is improved, and epoxy resin porous film has high strength, heat resistance and chemical resistance. Can be granted. A glycidylamine type epoxy resin may be used independently and may use 2 or more types together.
　硬化剤としては、芳香族硬化剤及び非芳香族硬化剤のいずれも使用可能である。芳香族硬化剤としては、芳香族アミン（例えば、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ベンジルジメチルアミン、ジメチルアミノメチルベンゼン）、芳香族酸無水物（例えば、無水フタル酸、無水トリメリット酸、無水ピロメリット酸）、フェノール樹脂、フェノールノボラック樹脂、複素芳香環を含むアミン（例えば、トリアジン環を含むアミン）等が挙げられる。非芳香族硬化剤としては、脂肪族アミン類（例えば、エチレンジアミン、１，４－ブチレンジアミン、１，５－ペンタンジアミン、１，６－ヘキサンジアミン、１，７－ヘプタンジアミン、１，８－オクタンジアミン、ジエチレントリアミン、トリエチレンテトラミン、テトラエチレンペンタミン、イミノビスプロピルアミン、ビス（ヘキサメチレン）トリアミン、１，３，６－トリスアミノメチルヘキサン、ポリメチレンジアミン、トリメチルヘキサメチレンジアミン、ポリエーテルジアミン）、脂環族アミン類（例えば、イソホロンジアミン、メンタンジアミン、Ｎ－アミノエチルピペラジン、３，９－ビス（３－アミノプロピル）２，４，８，１０－テトラオキサスピロ（５，５）ウンデカンアダクト、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、ビス（４－アミノシクロヘキシル）メタン、これらの変性品）、ポリアミン類とダイマー酸とを含む脂肪族ポリアミドアミン等が挙げられる。これらは単独で用いてもよく、２種以上を併用してもよい。 As the curing agent, either an aromatic curing agent or a non-aromatic curing agent can be used. Aromatic curing agents include aromatic amines (eg, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene), aromatic acid anhydrides (eg, phthalic anhydride, trimellitic anhydride) , Pyromellitic anhydride), phenol resins, phenol novolac resins, amines containing heteroaromatic rings (for example, amines containing triazine rings), and the like. Non-aromatic curing agents include aliphatic amines (eg, ethylenediamine, 1,4-butylenediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octane. Diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine, polyetherdiamine) Alicyclic amines (eg, isophoronediamine, menthanediamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane adduct, Bis (4-amino-3-methyl Kurohekishiru) methane, bis (4-aminocyclohexyl) methane, these modified products), aliphatic polyamide amines containing a polyamine and a dimer acid. These may be used alone or in combination of two or more.
　これらの中でも、分子内に一級アミンを２つ以上有する硬化剤を好適に使用できる。具体的には、メタフェニレンジアミン、ジアミノジフェニルメタン、ジアミノジフェニルスルホン、ポリメチレンジアミン、ビス（４－アミノ－３－メチルシクロヘキシル）メタン、ビス（４－アミノシクロヘキシル）メタン、１，４－ブチレンジアミン、１，５－ペンタンジアミン、１，６－ヘキサンジアミン、１，７－ヘプタンジアミン、１，８－オクタンジアミン、ジエチレントリアミン、トリエチレンテトラミン、及びテトラエチレンペンタミンからなる群より選ばれる少なくとも１つを好適に使用できる。これらの硬化剤を使用すると、均一な三次元網目状骨格及び均一な空孔を形成できるとともに、エポキシ樹脂多孔膜に高い強度及び適切な弾性を付与できる。得られるエポキシ樹脂多孔膜の架橋密度の高さ、より高い化学的安定性、並びに入手及び取り扱いの容易さから１，６－ヘキサンジアミンが好ましい。 Among these, a curing agent having two or more primary amines in the molecule can be suitably used. Specifically, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, polymethylenediamine, bis (4-amino-3-methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, 1,4-butylenediamine, 1 And at least one selected from the group consisting of 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine. Can be used. When these curing agents are used, a uniform three-dimensional network skeleton and uniform pores can be formed, and high strength and appropriate elasticity can be imparted to the epoxy resin porous membrane. 1,6-hexanediamine is preferred because of the high crosslink density of the resulting epoxy resin porous membrane, higher chemical stability, and ease of availability and handling.
　エポキシ樹脂と硬化剤との組み合わせとしては、芳香族エポキシ樹脂と脂肪族アミン硬化剤との組み合わせ、芳香族エポキシ樹脂と脂環族アミン硬化剤との組み合わせ、又は脂環族エポキシ樹脂と芳香族アミン硬化剤との組み合わせが好ましい。これらの組み合わせにより、エポキシ樹脂多孔膜に優れた耐熱性を付与できる。 As a combination of an epoxy resin and a curing agent, a combination of an aromatic epoxy resin and an aliphatic amine curing agent, a combination of an aromatic epoxy resin and an alicyclic amine curing agent, or an alicyclic epoxy resin and an aromatic amine A combination with a curing agent is preferred. By these combinations, excellent heat resistance can be imparted to the porous epoxy resin membrane.
　ポロゲンは、エポキシ樹脂及び硬化剤を溶かすことができる溶剤でありうる。ポロゲンは、また、エポキシ樹脂と硬化剤とが重合した後、反応誘起相分離を生じさせることができる溶剤として使用される。具体的には、メチルセロソルブ、エチルセロソルブ等のセロソルブ類、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート等のエステル類、ポリエチレングリコール、ポリプロピレングリコール等のグリコール類、ポリオキシエチレンモノメチルエーテル、ポリオキシエチレンジメチルエーテル等のエーテル類をポロゲンとして使用できる。これらは単独で用いてもよく、２種以上を併用してもよい。 The porogen may be a solvent that can dissolve the epoxy resin and the curing agent. Porogens are also used as solvents that can cause reaction-induced phase separation after the epoxy resin and curing agent are polymerized. Specifically, cellosolves such as methyl cellosolve and ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol and polypropylene glycol, polyoxyethylene monomethyl ether and polyoxyethylene Ethers such as dimethyl ether can be used as the porogen. These may be used alone or in combination of two or more.
　これらの中でも、メチルセロソルブ、エチルセロソルブ、分子量６００以下のポリエチレングリコール、エチレングリコールモノメチルエーテルアセテート、プロピレングリコールモノメチルエーテルアセテート、ポリプロピレングリコール、ポリオキシエチレンモノメチルエーテル及びポリオキシエチレンジメチルエーテルからなる群より選ばれる少なくとも１つを好適に使用できる。特に、分子量２００以下のポリエチレングリコール、分子量５００以下のポリプロピレングリコール、ポリオキシエチレンモノメチルエーテル及びプロピレングリコールモノメチルエーテルアセテートからなる群より選ばれる少なくとも１つを好適に使用できる。これらのポロゲンを使用すると、均一な三次元網目状骨格及び均一な空孔を形成できる。これらは単独で用いてもよく、２種以上を併用してもよい。 Among these, at least one selected from the group consisting of methyl cellosolve, ethyl cellosolve, polyethylene glycol having a molecular weight of 600 or less, ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, polypropylene glycol, polyoxyethylene monomethyl ether, and polyoxyethylene dimethyl ether. Can be preferably used. In particular, at least one selected from the group consisting of polyethylene glycol having a molecular weight of 200 or less, polypropylene glycol having a molecular weight of 500 or less, polyoxyethylene monomethyl ether, and propylene glycol monomethyl ether acetate can be preferably used. When these porogens are used, a uniform three-dimensional network skeleton and uniform pores can be formed. These may be used alone or in combination of two or more.
　また、個々のエポキシ樹脂又は硬化剤と常温で不溶又は難溶であっても、エポキシ樹脂と硬化剤との反応物が可溶となる溶剤についてはポロゲンとして使用可能である。このようなポロゲンとしては、例えば、臭素化ビスフェノールＡ型エポキシ樹脂（ジャパンエポキシレジン株式会社製「エピコート５０５８」）が挙げられる。 Moreover, even if it is insoluble or hardly soluble at room temperature with an individual epoxy resin or curing agent, a solvent in which a reaction product of the epoxy resin and the curing agent is soluble can be used as a porogen. Examples of such porogen include brominated bisphenol A type epoxy resin (“Epicoat 5058” manufactured by Japan Epoxy Resin Co., Ltd.).
　エポキシ樹脂多孔膜の空孔率、平均孔径及び孔径分布は、原料の種類、原料の配合比率及び反応条件（例えば、反応誘起相分離時における加熱温度及び加熱時間）に応じて変化する。そのため、目的とする空孔率、平均孔径、孔径分布を得るために、最適な条件を選択することが好ましい。また、相分離時におけるエポキシ樹脂架橋体の分子量、分子量分布、溶液の粘度、架橋反応速度等を制御することにより、エポキシ樹脂架橋体とポロゲンとの共連続構造を特定の状態で固定し、安定した多孔質構造を得ることができる。 The porosity, average pore size, and pore size distribution of the epoxy resin porous membrane vary depending on the type of raw material, the mixing ratio of the raw material, and the reaction conditions (for example, heating temperature and heating time during reaction-induced phase separation). Therefore, it is preferable to select optimum conditions in order to obtain the target porosity, average pore diameter, and pore diameter distribution. In addition, by controlling the molecular weight, molecular weight distribution, solution viscosity, crosslinking reaction rate, etc. of the crosslinked epoxy resin during phase separation, the co-continuous structure of the crosslinked epoxy resin and porogen is fixed in a specific state and stable. A porous structure can be obtained.
　エポキシ樹脂に対する硬化剤の配合比率は、例えば、エポキシ基１当量に対して硬化剤当量が０．６～１．５である。適切な硬化剤当量は、エポキシ樹脂多孔膜の耐熱性、化学的耐久性、力学特性等の特性の向上に寄与する。 The blending ratio of the curing agent to the epoxy resin is, for example, 0.6 to 1.5 in terms of the curing agent equivalent to 1 equivalent of epoxy group. Appropriate curing agent equivalent contributes to improvement of properties such as heat resistance, chemical durability and mechanical properties of the epoxy resin porous membrane.
　硬化剤の他に、目的とする多孔質構造を得るために、溶液中に硬化促進剤を添加してもよい。硬化促進剤としては、トリエチルアミン、トリブチルアミン等の三級アミン、２－フェノール－４－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－フェノール－４，５－ジヒドロキシイミダゾール等のイミダゾール類が挙げられる。 In addition to the curing agent, a curing accelerator may be added to the solution in order to obtain the desired porous structure. Examples of the curing accelerator include tertiary amines such as triethylamine and tributylamine, and imidazoles such as 2-phenol-4-methylimidazole, 2-ethyl-4-methylimidazole, and 2-phenol-4,5-dihydroxyimidazole. It is done.
　エポキシ樹脂、硬化剤及びポロゲンの総重量に対して、例えば４０～８０重量％のポロゲンを使用できる。適切な量のポロゲンを使用することにより、所望の空孔率、平均孔径及び通気度を有するエポキシ樹脂多孔膜を形成しうる。 For example, 40 to 80% by weight of porogen can be used with respect to the total weight of epoxy resin, curing agent and porogen. By using an appropriate amount of porogen, an epoxy resin porous film having a desired porosity, average pore diameter, and air permeability can be formed.
　エポキシ樹脂多孔膜の平均孔径を所望の範囲に調節する方法の１つとして、エポキシ当量の異なる２種以上のエポキシ樹脂を混合して用いる方法が挙げられる。その際、エポキシ当量の差は１００以上であることが好ましく、常温で液状のエポキシ樹脂と常温で固形のエポキシ樹脂とを混合して用いる場合もある。 As one method for adjusting the average pore diameter of the epoxy resin porous membrane to a desired range, there is a method of using a mixture of two or more epoxy resins having different epoxy equivalents. In this case, the difference in epoxy equivalent is preferably 100 or more, and there are cases where an epoxy resin that is liquid at normal temperature and an epoxy resin that is solid at normal temperature are mixed and used.
　次に、エポキシ樹脂、硬化剤及びポロゲンを含む溶液からエポキシ樹脂組成物の硬化体を作製する。具体的には、溶液を金型に充填し、必要に応じて加熱する。エポキシ樹脂を三次元架橋させることによって、所定の形状を有する硬化体が得られる。その際、エポキシ樹脂架橋体とポロゲンとが相分離することにより、共連続構造が形成される。 Next, a cured product of the epoxy resin composition is prepared from a solution containing an epoxy resin, a curing agent and a porogen. Specifically, the solution is filled in a mold and heated as necessary. A cured body having a predetermined shape is obtained by three-dimensionally crosslinking the epoxy resin. In that case, a co-continuous structure is formed by phase-separation of a crosslinked epoxy resin and a porogen.
　硬化体の形状は特に限定されない。円柱状又は円筒状の金型を使用すれば、円筒又は円柱の形状を有する硬化体を得ることができる。硬化体が円筒又は円柱の形状を有していると、後述する切削工程（図２参照）を実施しやすい。 The shape of the cured body is not particularly limited. If a columnar or cylindrical mold is used, a cured body having a cylindrical or columnar shape can be obtained. When the cured body has a cylindrical or columnar shape, it is easy to carry out a cutting step (see FIG. 2) described later.
　エポキシ樹脂組成物を硬化させるために必要な温度及び時間は、エポキシ樹脂及び硬化剤の種類に応じて変化するので特に限定されない。均一な分布及び均一な孔径を持った空孔を有するエポキシ樹脂多孔膜を得るために、室温にて硬化処理を実施することができる。室温硬化の場合、温度は２０～４０℃程度であり、時間は３～１００時間程度、好ましくは２０～５０時間程度である。加熱硬化の場合、温度は４０～１２０℃程度、好ましくは６０～１００℃程度であり、時間は１０～３００分程度、好ましくは３０～１８０分程度である。硬化処理後、エポキシ樹脂架橋体の架橋度を高めるためにポストキュア（後処理）を行ってもよい。ポストキュアの条件は特に制限されないが、温度は室温又は５０～１６０℃程度であり、時間は２～４８時間程度である。 The temperature and time required for curing the epoxy resin composition are not particularly limited because they vary depending on the type of epoxy resin and curing agent. In order to obtain an epoxy resin porous film having pores having a uniform distribution and a uniform pore size, a curing treatment can be performed at room temperature. In the case of room temperature curing, the temperature is about 20 to 40 ° C., and the time is about 3 to 100 hours, preferably about 20 to 50 hours. In the case of heat curing, the temperature is about 40 to 120 ° C., preferably about 60 to 100 ° C., and the time is about 10 to 300 minutes, preferably about 30 to 180 minutes. After the curing treatment, post-cure (post-treatment) may be performed to increase the degree of crosslinking of the crosslinked epoxy resin. The post-curing conditions are not particularly limited, but the temperature is room temperature or about 50 to 160 ° C., and the time is about 2 to 48 hours.
　硬化体の寸法は特に限定されない。硬化体が円筒又は円柱の形状を有している場合、エポキシ樹脂多孔膜の製造効率の観点から、硬化体の直径は、例えば２０ｃｍ以上であり、好ましくは３０～１５０ｃｍである。硬化体の長さ（軸方向）も、得るべきエポキシ樹脂多孔膜の寸法を考慮して適宜設定することができる。硬化体の長さは、例えば２０～２００ｃｍであり、取扱いやすさの観点から２０～１５０ｃｍであることが好ましく、２０～１２０ｃｍであることがより好ましい。 The dimensions of the cured body are not particularly limited. When the cured body has a cylindrical or columnar shape, the diameter of the cured body is, for example, 20 cm or more, preferably 30 to 150 cm, from the viewpoint of manufacturing efficiency of the epoxy resin porous film. The length (axial direction) of the cured body can also be appropriately set in consideration of the dimensions of the epoxy resin porous film to be obtained. The length of the cured body is, for example, 20 to 200 cm, preferably 20 to 150 cm, and more preferably 20 to 120 cm from the viewpoint of ease of handling.
　次に、硬化体をシート状に成形する。円筒又は円柱の形状を有する硬化体は、以下の方法でシート状に成形されうる。具体的には、図２に示すように、硬化体１２をシャフト１４に取り付ける。長尺の形状を有するエポキシ樹脂シート１６が得られるように、切削刃１８（スライサー）を用いて、硬化体１２の表層部を所定の厚さで切削（スライス）する。詳細には、硬化体１２の円筒軸Ｏ（又は円柱軸）を中心として、切削刃１８に対して硬化体１２を相対的に回転させながら硬化体１２の表層部を切削する。この方法によれば、効率的にエポキシ樹脂シート１６を作製することができる。 Next, the cured body is formed into a sheet. The cured body having a cylindrical or columnar shape can be formed into a sheet shape by the following method. Specifically, the cured body 12 is attached to the shaft 14 as shown in FIG. The surface layer portion of the cured body 12 is cut (sliced) at a predetermined thickness using a cutting blade 18 (slicer) so that an epoxy resin sheet 16 having a long shape is obtained. Specifically, the surface layer portion of the cured body 12 is cut while rotating the cured body 12 relative to the cutting blade 18 around the cylindrical axis O (or columnar axis) of the cured body 12. According to this method, the epoxy resin sheet 16 can be produced efficiently.
　硬化体１２を切削するときのライン速度は、例えば２～７０ｍ／ｍｉｎの範囲にある。エポキシ樹脂シート１６の厚さは、エポキシ樹脂多孔膜の目標厚さ（１０～５０μｍ）に応じて決定される。ポロゲンを除去して乾燥させると厚さが若干減少するので、エポキシ樹脂シート１６は、通常、エポキシ樹脂多孔膜の目標厚さよりも若干厚い。エポキシ樹脂シート１６の長さは特に限定されないが、エポキシ樹脂シート１６の製造効率の観点から、例えば１００ｍ以上であり、好ましくは１０００ｍ以上である。 The line speed when cutting the cured body 12 is in the range of 2 to 70 m / min, for example. The thickness of the epoxy resin sheet 16 is determined according to the target thickness (10 to 50 μm) of the epoxy resin porous film. Since the thickness slightly decreases when the porogen is removed and dried, the epoxy resin sheet 16 is usually slightly thicker than the target thickness of the epoxy resin porous film. Although the length of the epoxy resin sheet 16 is not specifically limited, From a viewpoint of the production efficiency of the epoxy resin sheet 16, it is 100 m or more, for example, Preferably it is 1000 m or more.
　最後に、エポキシ樹脂シート１６からポロゲンを抽出し、除去する。具体的には、溶剤にエポキシ樹脂シート１６を浸漬することによって、エポキシ樹脂シート１６からポロゲンを除去することができる。これにより、セパレータ４として利用できるエポキシ樹脂多孔膜が得られる。溶剤としては、環境に対する負荷が大きくないハロゲンフリーの溶剤が好ましい。 Finally, the porogen is extracted from the epoxy resin sheet 16 and removed. Specifically, the porogen can be removed from the epoxy resin sheet 16 by immersing the epoxy resin sheet 16 in a solvent. Thereby, the epoxy resin porous film which can be utilized as the separator 4 is obtained. The solvent is preferably a halogen-free solvent that does not have a large environmental load.
　エポキシ樹脂シート１６からポロゲンを除去するためのハロゲンフリーの溶剤として、水、ＤＭＦ（Ｎ，Ｎ－ジメチルホルムアミド）、ＤＭＳＯ（ジメチルスルホキシド）及びＴＨＦ（テトラヒドロフラン）からなる群より選ばれる少なくとも１つをポロゲンの種類に応じて使用できる。また、水、二酸化炭素等の超臨界流体もポロゲンを除去するための溶剤として使用できる。エポキシ樹脂シート１６からポロゲンを積極的に除去するために、超音波洗浄を行ってもよく、また、溶剤を加熱して用いてもよい。 As the halogen-free solvent for removing the porogen from the epoxy resin sheet 16, at least one selected from the group consisting of water, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), and THF (tetrahydrofuran) is used as the porogen. It can be used depending on the type. Also, supercritical fluids such as water and carbon dioxide can be used as a solvent for removing porogen. In order to positively remove the porogen from the epoxy resin sheet 16, ultrasonic cleaning may be performed, or the solvent may be heated and used.
　ポロゲンを除去するための洗浄装置も特に限定されず、公知の洗浄装置を使用できる。エポキシ樹脂シート１６を溶剤に浸漬することによってポロゲンを除去する場合には、洗浄槽を複数備えた多段洗浄装置を好適に使用できる。洗浄の段数としては、３段以上がより好ましい。また、カウンターフローを利用することによって、実質的に多段洗浄を行ってもよい。さらに、各段の洗浄で、溶剤の温度を変えたり、溶剤の種類を変えたりしてもよい。 The cleaning device for removing the porogen is not particularly limited, and a known cleaning device can be used. When removing the porogen by immersing the epoxy resin sheet 16 in a solvent, a multistage cleaning apparatus having a plurality of cleaning tanks can be suitably used. The number of cleaning stages is more preferably 3 or more. Moreover, you may perform multistage washing | cleaning substantially by utilizing a counterflow. Furthermore, the temperature of the solvent may be changed or the type of the solvent may be changed in the cleaning of each stage.
　ポロゲンを除去した後、エポキシ樹脂多孔膜の乾燥処理を行う。乾燥条件は特に限定されず、温度は通常４０～１２０℃程度であり、５０～１００℃程度が好ましく、乾燥時間は１０秒～５分程度である。乾燥処理には、テンター方式、フローティング方式、ロール方式、ベルト方式等の公知のシート乾燥方法を採用した乾燥装置を使用できる。複数の乾燥方法を組み合わせてもよい。 After removing the porogen, the epoxy resin porous film is dried. The drying conditions are not particularly limited, and the temperature is usually about 40 to 120 ° C., preferably about 50 to 100 ° C., and the drying time is about 10 seconds to 5 minutes. For the drying treatment, a drying apparatus employing a known sheet drying method such as a tenter method, a floating method, a roll method, or a belt method can be used. A plurality of drying methods may be combined.
　本実施形態の方法によれば、セパレータ４として使用できる微多孔構造を有するエポキシ樹脂多孔膜を極めて簡単に製造できる。ポリオレフィン多孔膜の製造時に必要である工程、例えば延伸工程を省略できるため、高い生産性でエポキシ樹脂多孔膜を製造できる。 According to the method of this embodiment, an epoxy resin porous film having a microporous structure that can be used as the separator 4 can be manufactured very easily. Since the process required at the time of manufacture of a polyolefin porous membrane, for example, an extending process, can be omitted, an epoxy resin porous membrane can be manufactured with high productivity.
　なお、セパレータ４は、エポキシ樹脂多孔膜のみで構成されていてもよいし、エポキシ樹脂多孔膜と他の多孔質材料との積層体で構成されていてもよい。他の多孔質材料としては、ポリエチレン多孔膜、ポリプロピレン多孔膜等のポリオレフィン多孔膜、セルロース多孔膜、フッ素樹脂多孔膜等が挙げられる。他の多孔質材料は、エポキシ樹脂多孔膜の片面にのみ設けられていてもよいし、両面に設けられていてもよい。 In addition, the separator 4 may be comprised only by the epoxy resin porous film, and may be comprised by the laminated body of an epoxy resin porous film and another porous material. Examples of other porous materials include polyolefin porous films such as polyethylene porous films and polypropylene porous films, cellulose porous films, and fluororesin porous films. Other porous materials may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
　同様に、セパレータ４は、エポキシ樹脂多孔膜と補強材との積層体で構成されていてもよい。補強材としては、織布、不織布等が挙げられる。補強材は、エポキシ樹脂多孔膜の片面にのみ設けられていてもよいし、両面に設けられていてもよい。 Similarly, the separator 4 may be composed of a laminate of an epoxy resin porous film and a reinforcing material. Examples of the reinforcing material include woven fabric and non-woven fabric. The reinforcing material may be provided only on one side of the epoxy resin porous membrane, or may be provided on both sides.
　以下、実施例を挙げて本発明をより詳細に説明するが、本発明は、これら実施例に限定されるものではない。なお、以下において、ＲＯ水は逆浸透膜を用いて処理して得た純水を意味する。 Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to these examples. In the following, RO water means pure water obtained by processing using a reverse osmosis membrane.
　実施例における物性は以下の方法を用いて測定した。 The physical properties in the examples were measured using the following methods.
（空孔率）
　空孔率は、以下の方法で測定した。まず、測定対象を一定の寸法（例えば、直径６ｃｍの円形）に切断し、その体積及び重量を求める。得られた結果を次式に代入して空孔率を算出する。
　　空孔率（％）＝１００×（Ｖ－（Ｗ／Ｄ））／Ｖ
　　　Ｖ：体積（ｃｍ3）
　　　Ｗ：重量（ｇ）
　　　Ｄ：構成成分の平均密度（ｇ／ｃｍ3） (Porosity)
The porosity was measured by the following method. First, a measurement object is cut into a certain dimension (for example, a circle having a diameter of 6 cm), and its volume and weight are obtained. The porosity is calculated by substituting the obtained result into the following equation.
Porosity (%) = 100 × (V− (W / D)) / V
V: Volume (cm 3 )
W: Weight (g)
D: Average density of components (g / cm 3 )
（短絡率）
　短絡率は以下の方法で測定した。厚さ２０μｍのアルミニウム箔を３０ｍｍ角の正方形に切り出した。次いで、セパレータを４０ｍｍ角の正方形に切り出した。このセパレータを電解液である０．５ｍｏｌ／Ｌの硫酸水溶液に浸漬後、上記アルミニウム箔に挟み込み、電極群を作製した。次いで、厚さ５ｍｍ、３５ｍｍ角の正方形のアルミニウム板であって、端面に端子接続部の準備されたアルミニウム板を用いて電極群を両側から挟み込んだ。さらにこの電極群を挟んだアルミニウム板を、シリコーンゴムシートを用いて両側から挟み込み、試験用電極群を得た。上記のように得られた試験用電極群を加圧装置に設置した。上記２か所の端子接続部に交流抵抗測定機（日置電気株式会社製）を接続し、加圧した。面圧０．２ＭＰａが試験用電極群にかかるまで加圧し、抵抗値を測定した。抵抗値が低下すると短絡が生じたと判断した。この測定を、各実施例につき計１０回実施し、短絡率Ｘ／１０（１０回の測定のうち、短絡した回数Ｘ回）とした。 (Short-circuit rate)
The short circuit rate was measured by the following method. An aluminum foil having a thickness of 20 μm was cut into a 30 mm square. Next, the separator was cut into a 40 mm square. This separator was immersed in a 0.5 mol / L sulfuric acid aqueous solution as an electrolytic solution, and then sandwiched between the aluminum foils to prepare an electrode group. Next, a square aluminum plate having a thickness of 5 mm and a 35 mm square, and an electrode group was sandwiched from both sides using an aluminum plate having a terminal connection portion prepared on the end face. Furthermore, the aluminum plate which pinched | interposed this electrode group was inserted | pinched from the both sides using the silicone rubber sheet, and the electrode group for a test was obtained. The test electrode group obtained as described above was placed in a pressure device. An AC resistance measuring machine (manufactured by Hioki Electric Co., Ltd.) was connected to the two terminal connection portions and pressurized. Pressure was applied until a surface pressure of 0.2 MPa was applied to the test electrode group, and the resistance value was measured. When the resistance value decreased, it was determined that a short circuit occurred. This measurement was carried out 10 times in total for each example, and the short circuit rate was X / 10 (of 10 measurements, the number of short circuits was X times).
（吸液性）
　広口瓶に０．５ｍｏｌ／Ｌの硫酸水溶液を、深さ１０ｍｍまで入れた。セパレータを幅１０ｍｍに切断し、セパレータの最下部に重石としてＳＵＳ（ステンレス鋼）製クリップを取り付けた。このセパレータを、広口瓶の底面に対し垂直方向に浸漬させた。浸漬開始後３分経過後に取出し、硫酸水溶液の液面部位からの吸液高さを測定した。 (Liquid absorption)
A 0.5 mol / L sulfuric acid aqueous solution was put in a wide-mouth bottle up to a depth of 10 mm. The separator was cut into a width of 10 mm, and a SUS (stainless steel) clip was attached as a weight at the bottom of the separator. This separator was immersed in a direction perpendicular to the bottom surface of the wide-mouth bottle. The sample was taken out 3 minutes after the start of immersion, and the liquid absorption height from the liquid surface portion of the sulfuric acid aqueous solution was measured.
（実施例１）
　３Ｌの円筒形のポリ容器にｊＥＲ（登録商標）８２８（ビスフェノールＡ型エポキシ樹脂、三菱化学株式会社製、エポキシ当量１８４～１９４ｇ/ｅｑ．）１００重量部とＴＥＴＲＡＤ（登録商標）－Ｃ（グリシジルアミン型エポキシ樹脂、三菱ガス化学株式会社製、エポキシ当量９５～１１０ｇ/ｅｑ．）２５．０重量部をポリプロピレングリコール（株式会社ＡＤＥＫＡ製、アデカポリエーテルＰ－４００）２１１．９重量部に溶解させ、エポキシ樹脂／ポリプロピレングリコール溶液を調製した。その後、このポリ容器に１，６－ヘキサンジアミン２２．３重量部を添加し、エポキシ樹脂／アミン／ポリプロピレングリコール溶液を調製した。その後、遊星撹拌装置（株式会社シンキー製、商品名「あわとり練太郎（登録商標）」）を用い、約０．７ｋＰａで真空脱泡すると同時に自／公転比率３／４の条件下、公転８００ｒｐｍの比率で１０分間撹拌する手順を２回繰り返した。
　その後、数日間自然冷却させ、ポリ容器からエポキシ樹脂ブロックを取り出し、切削旋盤装置を用いて５０μｍの厚みで連続的にスライスしてエポキシ樹脂シートを得た。このエポキシ樹脂シートをＲＯ水とＤＭＦとの混合溶媒（体積比でＲＯ水／ＤＭＦ＝１／１）中で１０分間超音波洗浄した後、ＲＯ水のみを用いて１０分間超音波洗浄し、ＲＯ水に１２時間浸漬させて、ポリプロピレングリコールを除去した。その後、８０℃雰囲気下で２時間乾燥させ、４８μｍの厚みを有するエポキシ樹脂多孔膜（セパレータ）を得た。 Example 1
In a 3 L cylindrical plastic container, jER (registered trademark) 828 (bisphenol A type epoxy resin, manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of 184 to 194 g / eq.) And TETRAD (registered trademark) -C (glycidylamine) Type epoxy resin, Mitsubishi Gas Chemical Co., Ltd., epoxy equivalent 95-110 g / eq.) 25.0 parts by weight is dissolved in polypropylene glycol (ADEKA Co., Ltd., Adeka Polyether P-400) 211.9 parts by weight, An epoxy resin / polypropylene glycol solution was prepared. Thereafter, 22.3 parts by weight of 1,6-hexanediamine was added to the polycontainer to prepare an epoxy resin / amine / polypropylene glycol solution. After that, using a planetary agitator (trade name “Awatori Nertaro (registered trademark)” manufactured by Shinky Co., Ltd.), vacuum defoaming was performed at about 0.7 kPa, and at the same time, revolution 800 rpm under the condition of self / revolution ratio 3/4. The procedure of stirring at a ratio of 10 minutes was repeated twice.
Thereafter, it was naturally cooled for several days, the epoxy resin block was taken out from the plastic container, and continuously sliced with a thickness of 50 μm using a cutting lathe device to obtain an epoxy resin sheet. This epoxy resin sheet was subjected to ultrasonic cleaning for 10 minutes in a mixed solvent of RO water and DMF (volume ratio of RO water / DMF = 1/1), and then ultrasonically cleaned using only RO water for 10 minutes. The polypropylene glycol was removed by immersion in water for 12 hours. Then, it dried for 2 hours in 80 degreeC atmosphere, and obtained the epoxy resin porous membrane (separator) which has a thickness of 48 micrometers.
（実施例２）
　切削旋盤装置を用いて２２μｍの厚みで連続的にスライスした以外は実施例１と同様に実施し、２１μｍの厚みを有するエポキシ樹脂多孔膜（セパレータ）を得た。 (Example 2)
The same procedure as in Example 1 was carried out except that a continuous lathe was sliced with a thickness of 22 μm using a cutting lathe device to obtain an epoxy resin porous film (separator) having a thickness of 21 μm.
　実施例についての評価結果を表１に示す。 Table 1 shows the evaluation results for the examples.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、実施例１では電極間の短絡が生じなかった。実施例１よりも膜厚を薄くした実施例２においても、電極間の短絡が生じなかった。また、これらのエポキシ樹脂多孔膜（セパレータ）は良好な吸液性を示し、水系電解液である硫酸水溶液との高い親和性を有することがわかった。 As shown in Table 1, in Example 1, no short circuit between the electrodes occurred. Also in Example 2 in which the film thickness was made thinner than Example 1, no short circuit occurred between the electrodes. Moreover, these epoxy resin porous membranes (separator) showed favorable liquid absorptivity, and it turned out that it has high affinity with the sulfuric acid aqueous solution which is aqueous electrolyte solution.
　本発明によって提供されたセパレータは、電気二重層キャパシタ等の水系電解質蓄電デバイスに好適に使用でき、特に、車両、オートバイ、船舶、建設機械、産業機械、住宅用蓄電システム等に必要とされる大容量のキャパシタに好適に使用できる。 The separator provided by the present invention can be suitably used for water-based electrolyte electricity storage devices such as electric double layer capacitors, and is particularly required for vehicles, motorcycles, ships, construction machinery, industrial machinery, residential electricity storage systems, and the like. It can be suitably used for a capacitor having a capacity.

Claims (5)

  1. 　水系電解質蓄電デバイス用セパレータであって、
    　エポキシ樹脂で構成された三次元網目状骨格と、
    　前記セパレータの表面と裏面との間でイオンが移動できるように連通している空孔と、
    を備えた、水系電解質蓄電デバイス用セパレータ。     A separator for an aqueous electrolyte electricity storage device,
    A three-dimensional network skeleton composed of epoxy resin;
    Pores communicating so that ions can move between the front and back surfaces of the separator;
    A separator for a water-based electrolyte electricity storage device.
  2. 　前記セパレータの厚さが５～５０μｍの範囲にある、
    請求項１に記載の水系電解質蓄電デバイス用セパレータ。     The thickness of the separator is in the range of 5 to 50 μm;
    The separator for aqueous electrolyte electricity storage devices according to claim 1.
  3. 　エポキシ樹脂、硬化剤及びポロゲンを含むエポキシ樹脂組成物を調製する工程と、
    　エポキシ樹脂シートが得られるように、前記エポキシ樹脂組成物の硬化体をシート状に成形する又は前記エポキシ樹脂組成物のシート状成形体を硬化させる工程と、
    　前記エポキシ樹脂シートから前記ポロゲンを除去する工程と、
    を含む、水系電解質蓄電デバイス用セパレータの製造方法。     Preparing an epoxy resin composition comprising an epoxy resin, a curing agent and a porogen;
    A step of molding the cured product of the epoxy resin composition into a sheet shape or curing the sheet-shaped molded product of the epoxy resin composition so as to obtain an epoxy resin sheet;
    Removing the porogen from the epoxy resin sheet;
    The manufacturing method of the separator for water-system electrolyte electrical storage devices containing this.
  4. 　正極と、
    　負極と、
    　前記正極と前記負極との間に配置された、請求項１に記載のセパレータと、
    　前記セパレータに含浸した水系電解液と、
    を備えた、水系電解質蓄電デバイス。     A positive electrode;
    A negative electrode,
    The separator according to claim 1 disposed between the positive electrode and the negative electrode;
    An aqueous electrolyte impregnated in the separator;
    A water-based electrolyte electricity storage device comprising:
  5. 　電気二重層キャパシタである、請求項４に記載の水系電解質蓄電デバイス。 The water-based electrolyte electricity storage device according to claim 4, which is an electric double layer capacitor.
PCT/JP2014/006312 2013-12-25 2014-12-17 Separator for aqueous electrolyte power storage device, production method for separator for aqueous electrolyte power storage device, and aqueous electrolyte power storage device using separator for aqueous electrolyte power storage device WO2015098052A1 (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013672A (en) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology Composite material containing cured epoxy resin porous material and fiber
JP2010077358A (en) * 2008-09-29 2010-04-08 Nitto Denko Corp Porous epoxy resin membrane and method for producing the same
WO2010047383A1 (en) * 2008-10-23 2010-04-29 日東電工株式会社 Method for producing porous thermosetting resin sheet, porous thermosetting resin sheet and composite semipermeable membrane using same
JP2011103430A (en) * 2009-11-11 2011-05-26 Taiwan Textile Research Inst Aqueous electrolyte for electric double layer capacitor, and electric double layer capacitor employing the same
JP2013004210A (en) * 2011-06-13 2013-01-07 Nitto Denko Corp Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device and manufacturing method therefor

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013672A (en) * 2006-07-06 2008-01-24 Kyoto Institute Of Technology Composite material containing cured epoxy resin porous material and fiber
JP2010077358A (en) * 2008-09-29 2010-04-08 Nitto Denko Corp Porous epoxy resin membrane and method for producing the same
WO2010047383A1 (en) * 2008-10-23 2010-04-29 日東電工株式会社 Method for producing porous thermosetting resin sheet, porous thermosetting resin sheet and composite semipermeable membrane using same
JP2011103430A (en) * 2009-11-11 2011-05-26 Taiwan Textile Research Inst Aqueous electrolyte for electric double layer capacitor, and electric double layer capacitor employing the same
JP2013004210A (en) * 2011-06-13 2013-01-07 Nitto Denko Corp Separator for nonaqueous electrolyte power storage device, nonaqueous electrolyte power storage device and manufacturing method therefor

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