JP2003049133A - Adhesive porous film, polymer gel electrolyte obtained thereform and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an ionic conductive porous film having both ionic conductivity and strength and adhesiveness by itself and a polymer gel electrolyte obtained from the ionic conductive porous film. SOLUTION: This ionic conductive porous film is obtained by supporting a polymer crosslinked body made by polymerizing a polyfunctional monomer or the polyfunctional monomer and a monofunctional monomer in the presence or absence of a polymer and an electrolytic salt on a porous film substrate and has 180 deg. peeling adhesive strength in 20 mm width of >=0.2 N by itself. This polymer gel electrolyte comprises the porous film substrate, a polymer crosslinked body which is the polymer crosslinked body, supported on the porous film substrate and is swollen with an organic solvent and an electrolytic salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION In recent years, solid electrolytes widely used in electrochemical devices are substances having a high ionic conductivity in a solid state. Among them, polymer solid electrolytes using a polymer substance as a solid are Recently, as an electrolyte for a next-generation lithium-ion secondary battery, attention has been particularly paid, and research is being promoted worldwide. Such a polymer solid electrolyte has less risk of liquid leakage than conventional electrolyte solutions, and can be formed into a thin film.
Greater freedom.

However, conventionally known non-aqueous polymer solid electrolytes have a problem that their ionic conductivity is significantly lower than that of electrolyte solutions. For example, conventionally, a non-aqueous polymer solid electrolyte formed by complexing a polymer material such as a chain polymer such as polyethylene oxide or polypropylene oxide or a comb-shaped polymer such as polyphosphazene with an electrolyte salt is known. Conductivity is 10 at room temperature
^Nothing above ^-3 S / cm has been found.

For example, according to a battery using such a conventional solid electrolyte, since the solid electrolyte is significantly inferior in ionic conductivity to the liquid electrolyte, the battery has a high internal resistance and is practically charged. Cannot discharge. In addition, when the shape of the electrode changes due to charging / discharging, etc., the solid electrolyte cannot follow such a change in the shape of the electrode, resulting in insufficient contact between the electrode and the electrolyte. It becomes impossible to discharge.

Therefore, in order to improve the ionic conductivity of such a solid electrolyte, it has recently been proposed to blend an organic solvent such as propylene carbonate or γ-butyrolactone as a plasticizer into the solid electrolyte. .

For example, J. Electrochem. Soc., Vol. 13
7, 1657-1658 (1990), a sheet-shaped polymer gel electrolyte is proposed in which an organic electrolytic solution consisting of a mixed solvent of propylene carbonate and ethylene carbonate in which lithium perchlorate is dissolved is gelated with polyacrylonitrile to form a sheet. ing. Japanese Patent Application Laid-Open No. 11-16579 proposes a polymer gel electrolyte composed of polyacrylonitrile, an electrolyte salt and a non-aqueous solvent. In addition, JP-A-8-2981
Japanese Patent Laid-Open No. 26-26 proposes a polymer gel electrolyte containing polyethylene oxide or polypropylene oxide as a polymer component and γ-butyrolactone as a solvent.

However, such a polymer gel electrolyte is
Since the strength is low, it is unavoidable to increase the thickness in order to form a film.As a result, if an electrode is provided with such a polymer gel electrolyte sandwiched between them to assemble a battery, the distance between the electrodes will be large and Resistance becomes high, and sufficient charging / discharging cannot be performed.

Therefore, in order to solve the problem of strength in such a conventional polymer gel electrolyte, Japanese Unexamined Patent Application Publication No. HEI 11-1999
No. 40128, a polymer material capable of holding an electrolyte solution, for example, a mixture of a vinylidene fluoride-hexafluoropropylene copolymer and a resin such as a polyolefin resin is heated and kneaded to form a sheet. Then
A method is described in which a porous membrane is stretched, impregnated with an electrolyte solution, and gelled to obtain a polymer gel electrolyte. Further, JP-A No. 11-353935 discloses, for example, a gel-forming polymer which forms a gel with a non-aqueous (organic) solvent for forming a non-aqueous electrolyte such as propylene carbonate, ethylene carbonate and dimethoxyethane. Fiber, for example, polyacrylonitrile-methyl acrylate copolymer resin fiber, and a fiber having resistance to the solvent, for example, a fiber structure comprising a polyolefin fiber is formed, and the fiber structure is formed with the non-aqueous solvent. A method of forming a gel body and thus obtaining a polymer gel electrolyte is described.

In such a polymer gel electrolyte,
The polymer gel electrolyte obtained by the above-mentioned polyolefin resin or polyolefin fiber, which is, so to speak, has a relatively high strength even in a film shape, but in order to obtain a practical strength, these reinforcement materials are relatively Therefore, the blending ratio of the polymer substance and the gel-forming polymer capable of holding the electrolyte solution must be relatively reduced. Therefore, in such a polymer gel electrolyte, these polymer substances and gel-forming polymers are likely to form an incomplete gel body, and as a result, the inherent advantage of the polymer gel electrolyte that there is no liquid leakage is. In addition to this, the polymer gel electrolyte does not have perfect integrity and continuity due to the presence of the reinforcing material, so that there is a problem that the ion conductivity of the obtained polymer gel electrolyte becomes low. Of course, if the blending ratio of the polymer substance holding the electrolyte solution and the gel-forming polymer is increased, the obtained polymer gel electrolyte has high ionic conductivity, but its strength becomes weak.

Further, conventionally known polymer gel electrolytes generally have little adhesion to electrodes.
Therefore, when a conventional solid electrolyte is used in a battery having an electrode laminated type or an elliptical winding type cross section, for example, as a separator,
Since the surface pressure between the electrodes becomes non-uniform and low,
It may be difficult to keep the inter-electrode distance constant, and the inter-electrode distance may be partially increased. As described above, in the battery, when the distance between the electrodes is partially large, it is difficult to obtain excellent battery characteristics.

[0010]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in conventional polymer gel electrolytes, and has both ionic conductivity and strength, and itself. An object of the present invention is to provide an ion conductive porous membrane having adhesiveness, a porous membrane therefor, and a polymer gel electrolyte using them and a method for producing the same.

[0011]

According to the present invention, a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence of a polymer or It is characterized in that a crosslinked polymer obtained by polymerization in the absence is supported on a porous film of a base material, and as such, has a 180 ° peeling adhesive strength of 0.2 N or more in a width of 20 mm. An adhesive porous membrane is provided.

Further, according to the present invention, a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer are present in the presence or absence of a polymer. A crosslinked polymer obtained by polymerization and an electrolyte salt are supported on a base material porous membrane, and by themselves, 180 ° peeling adhesive strength in a 20 mm width has an adhesiveness of 0.2 N or more. An adhesive porous membrane is provided.

Furthermore, according to the present invention, (a) a substrate porous membrane, (b) an organic solvent, (c) a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer. A crosslinked polymer obtained by polymerizing a monofunctional polymerizable monomer with a monofunctional polymerizable monomer in the presence or absence of a polymer, which is supported on the substrate porous membrane and swelled with the organic solvent. Provided is a polymer gel electrolyte comprising a polymer crosslinked body and a (d) electrolyte salt.

Further, according to the present invention, a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer are present in the presence or absence of a polymer. An electrolytic solution consisting of an organic solvent for swelling the polymer crosslinked body and an electrolyte salt dissolved in the organic solvent after the polymer crosslinked body formed by the polymerization is carried on a substrate porous membrane to form an adhesive porous membrane. And a method for producing a polymer gel electrolyte, which comprises contacting the adhesive porous membrane with the polymer gel electrolyte.

Alternatively, according to the present invention, a polyfunctional polymerizable monomer or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer may be used in the presence or absence of a polymer. An organic solvent for swelling the polymer crosslinked body after supporting the polymer crosslinked body obtained by polymerization in the presence and the first electrolyte salt on the base material porous membrane to form an ion conductive adhesive porous membrane There is provided a method for producing a polymer gel electrolyte, which comprises contacting an electrolyte solution containing a second electrolyte salt dissolved in this organic solvent with the ion conductive adhesive porous membrane.

As another method, according to the present invention,
A polyfunctional polymerizable monomer, or a polymer crosslinked product obtained by polymerizing a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer, and an electrolyte salt. Is carried on a substrate porous membrane to form an ion conductive adhesive porous membrane, and then an organic solvent for swelling the crosslinked polymer and dissolving the electrolyte salt is added to the ion conductive adhesive porous membrane. There is provided a method for producing a polymer gel electrolyte, which comprises contacting with

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive porous membrane according to the present invention comprises:
Porous base material is a polyfunctional polymerizable monomer or a polymer crosslinked product obtained by polymerizing a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. It is supported on a quality membrane, and has an adhesive property of itself having a 180 ° peeling adhesive strength of 0.2 N or more in a width of 20 mm.

In the present invention, the 180 ° peeling adhesive strength is measured according to JIS Z 0237 using a stainless steel plate as an adherend.

In the present invention, the substrate porous membrane has strength as well as strength, considering that the polymer gel electrolyte finally obtained by using the porous membrane according to the present invention is used as a separator for batteries, capacitors and the like. As long as it does not dissolve in the electrolytic solution and has redox resistance, it is not particularly limited, but for example, a polyolefin resin such as a polyethylene resin or a polypropylene resin containing an ultrahigh molecular weight polyethylene resin, a fluororesin, or the like may be used. It is preferably used.

Similarly, in the present invention, the substrate porous membrane is particularly preferable in consideration of using the polymer gel electrolyte finally obtained by using the porous membrane according to the present invention as a separator for batteries, capacitors and the like. The porosity is, but not limited to, 30 to 95%, preferably 33 to 9
0%, particularly preferably 35 to 85%. When the porosity is too low, there are few ionic conduction paths,
For example, when the obtained polymer gel electrolyte is used as a battery separator, sufficient battery characteristics cannot be obtained. However, when the porosity is too high, the strength of the base material porous film is not sufficient, and in order to obtain a base material porous film having sufficient strength, the film thickness must be increased. As described above, when the polymer gel electrolyte thus obtained is used as a battery separator, the internal resistance is increased.

The porous film of the substrate has an air permeability of 15
00 seconds / 100 mL or less, preferably 1000 seconds / 1
It is preferably 00 mL or less. If the air permeability is too high, the ion conductivity of the polymer gel electrolyte obtained will be low. For example, when the polymer gel electrolyte obtained is used as a battery separator, sufficient battery characteristics cannot be obtained. Furthermore, it is preferable that the porous film of the base material has a needle penetration strength of 3 N or more. When the needle penetration strength is too small, when the obtained polymer gel electrolyte is used as a battery separator, the base material porous membrane is ruptured when a surface pressure is applied between the electrodes, which may cause an internal short circuit. is there.

According to the present invention, a polyfunctional polymerizable monomer or a polymer of a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer is added to such a substrate porous membrane. In the presence or absence of the above, a crosslinked polymer is polymerized, and this is supported on the substrate porous membrane to obtain an adhesive porous membrane.

That is, (a) a polyfunctional polymerizable monomer,
(B) a mixture of a polyfunctional polymerizable monomer and a polymer,
(C) Mixture of polyfunctional polymerizable monomer and monofunctional polymerizable monomer, or (d) mixture of polyfunctional polymerizable monomer, monofunctional polymerizable monomer and polymer (Hereinafter, the above (a)
Each of (d) to (d) may be referred to as a polymer crosslinked raw material. ) Is supported on the base material porous membrane, and then the polyfunctional polymerizable monomer (and the monofunctional polymerizable monomer) (and the monofunctional polymerizable monomer) is prepared by an appropriate means such as heating or irradiation with an active energy ray. (Co) polymerization (in the presence or absence of a polymer) to form a crosslinked polymer, whereby the crosslinked polymer is supported on a porous membrane of a substrate, and the adhesive has an adhesive force by itself. A porous film can be obtained.

In the present invention, examples of the polyfunctional polymerizable monomer include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate and polypropylene glycol di (meth). Acrylate, polytetramethylene glycol di (meth) acrylate,
1,3-butylene glycol di (meth) acrylate,
(Poly) alkylene glycol poly (meth) acrylate such as 1,4-butylene glycol diacrylate,
Ethylene oxide modified trimethylolpropane tri (meth) acrylate, propylene oxide modified trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, 1,3-glycerol di (meth) acrylate, 1,1,1-trimethylol Ethanedi (meth) acrylate, 1,1,1-trimethylolpropane di (meth) acrylate, 1,2,
Examples thereof include aliphatic polyhydric alcohol poly (meth) acrylates such as 6-hexane triacrylate and sorbitol pentamethacrylate, triallyl isocyanurate, and triallyl cyanurate. These polyfunctional polymerizable monomers are used alone or as a mixture of two or more kinds.

In the present invention, (meth) acrylate means acrylate or methacrylate. Further, the (poly) alkylene glycol includes, in addition to alkylene glycol, oligoalkylene glycol such as dialkylene glycol and trialkylene glycol, polyalkylene glycol and the like. same as below.

In the present invention, examples of the monofunctional polymerizable monomer include methoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate and 3-methoxybutyl acrylate, methoxypolyethylene glycol acrylate and methoxydiacrylate. Methoxy (poly) alkylene glycol (meth) acrylates such as propylene glycol acrylate, 2-ethoxyalkyl (meth) acrylates such as 2-ethoxyethyl acrylate and 2-ethoxybutyl acrylate, and ethoxypolyalkylene glycols such as ethoxydiethylene glycol acrylate ( (Meth) acrylates, phenoxy polyethylene glycol acrylates, alkylphenoxy polyethylene glycol acrylates, hydroxyethyl (meth) Acrylates such as ethylene oxide modified alkyl phenyl allyl, N- vinylpyrrolidone, morpholinoethyl acrylate, methyl methacrylate,
(Meth) acrylic acid esters such as ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate and lauryl methacrylate, vinyl ethers such as butyl vinyl ether and isobutyl vinyl ether,
Examples thereof include vinyl acetates such as vinyl acetate and vinyl butyrate, and vinyl cyanide such as acrylonitrile and methacrylonitrile.

Furthermore, according to the present invention, as the polymer,
For example, poly (meth) acrylate such as polymethylmethacrylate, polyethylacrylate, polybutylacrylate, methylmethacrylate / ethoxyethylacrylate copolymer, polyalkylene oxide, polyvinyl ether, polyvinylidene fluoride, (meth) acrylonitrile copolymer, Examples thereof include polyester and polysiloxane. These polymers are used alone or as a mixture of two or more kinds.

According to the invention, these polymers are not particularly restricted in their molecular weight. Further, these polymers may have a polymerizable group such as a double bond, a chain transfer group, a silanol group, a reactive group such as an epoxy group in the molecule.

In the present invention, among the various polyfunctional polymerizable monomers described above, those having a polyalkylene oxide chain such as polyalkylene glycol dimethacrylates are particularly preferable, and monofunctional Among the polymerizable monomers, mono (meth) acrylates such as butyl acrylate and 2-methoxyethyl acrylate are preferred. The polymer is preferably poly (meth) acrylate such as polymethyl methacrylate, polyethyl acrylate, polybutyl acrylate, and methyl methacrylate / ethoxyethyl acrylate copolymer.

According to the present invention, when the crosslinked polymer raw material is loaded on the substrate porous membrane, when the mixture of the polyfunctional polymerizable monomer and the polymer is loaded, the polyfunctional polymerizable monomer is used. The monomer is used in the range of 1 to 99% by weight of the polymer crosslinked raw material. When the mixture of the polyfunctional polymerizable monomer and the monofunctional polymerizable monomer is supported on the substrate porous membrane, the polyfunctional polymerizable monomer is 1 to 99 of the polymer crosslinked raw material. Used in the range of wt%. Further, even when a mixture of a polyfunctional polymerizable monomer, a monofunctional polymerizable monomer and a polymer is carried on the substrate porous membrane, the polyfunctional polymerizable monomer is a polymer crosslinked raw material. It is used in the range of 1 to 99% by weight.

According to the present invention, as described above, the polyfunctional polymerizable monomer may be used alone as the raw material for the crosslinked polymer, however, the adhesive porous membrane and the ionic conductivity obtained are not used. In order to impart sufficient flexibility to the adhesive porous membrane or the polymer gel electrolyte, it is preferable to use a monofunctional polymerizable monomer or polymer together with the polyfunctional polymerizable monomer.

According to the present invention, after the above-mentioned polymer crosslinked raw material is supported on the substrate porous membrane, the polyfunctional material in the above polymer crosslinked raw material is heated by an appropriate means such as heating or irradiation with an active energy ray. Polymerizable monomer (and monofunctional polymerizable monomer) (in the presence or absence of polymer)
By (co) polymerizing to form a polymer crosslinked body, an adhesive porous membrane can be obtained in which the polymer crosslinked body is supported on the substrate porous membrane.

In this way, after the raw material of the polymer crosslinked body is supported on the porous membrane of the base material and crosslinked to form the polymer crosslinked body, for example, the above-mentioned raw material of the polymer crosslinked body is crosslinked as described below. Along with the auxiliaries or sensitization aids, they are dissolved in an appropriate solvent, usually an organic solvent, and the obtained coating liquid is applied to the base material porous film, or the base material porous film is immersed in the coating liquid. After that, the polyfunctional polymerizable monomer (and the monofunctional polymerizable monomer) in the raw material of the polymer crosslinked body (in the presence of the polymer or (In the absence) (co) polymerization to form a crosslinked polymer, and then the organic solvent is removed.

In the present invention, the adhesive porous membrane has such a structure that the polymer cross-linked body is carried on the substrate porous membrane as a result, and as a result, the polymer cross-linked body is present in all the pores of the substrate porous membrane. Including those filled with.

Further, according to the present invention, the substrate porous film is
After supporting the polymer crosslinked raw material and the electrolyte salt on the base material porous membrane, the polyfunctional polymerizable monomer in the polymer crosslinked raw material is heated by an appropriate means such as heating or irradiation with an active energy ray. (Co) polymerizing the monomer (and the monofunctional polymerizable monomer) (in the presence or absence of the polymer),
By forming the polymer crosslinked body, the polymer crosslinked body and the electrolyte salt are supported on the substrate porous membrane, and the ion conductive adhesive porous membrane having the adhesive force by itself can be obtained.

Such an ion-conductive adhesive porous membrane is also 20 m in itself as in the above-mentioned adhesive porous membrane.
180 degree peeling adhesive strength in m width has adhesiveness of 0.2 N or more.

As described above, in order to support the polymer crosslinked material raw material and the electrolyte salt on the substrate porous membrane, for example, a polymerization initiator or a sensitization aid is appropriately added together with the polymer crosslinked material raw material and the electrolyte salt. Dissolved in a solvent, usually an organic solvent,
The polymer cross-linked raw material described above is applied by such means as applying the obtained coating liquid to a substrate porous film, or immersing the substrate porous film in the coating liquid, then heating or irradiating with radiation. By (co) polymerizing the above polyfunctional polymerizable monomer (and monofunctional polymerizable monomer) (in the presence or absence of a polymer) to form a crosslinked polymer. Then, a crosslinked product is obtained, and then the organic solvent is removed.

The polymer gel electrolyte according to the present invention comprises (a)
Presence of a polymer comprising a substrate porous membrane, (b) an organic solvent, and (c) a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer. A polymer cross-linked product obtained by polymerizing under or absent, which is carried on the above-mentioned substrate porous membrane and swollen with the above organic solvent, and (d) an electrolyte salt. Consists of.

According to the present invention, the polymer gel electrolyte according to the present invention can be obtained by various methods using the above-mentioned adhesive porous membrane or ion conductive adhesive porous membrane. Here, according to the present invention, the electrolyte salt,
At least a part thereof is preferably dissolved in the organic solvent.

According to the present invention, as a first method, a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence of a polymer or After supporting a polymer cross-linked product obtained by polymerization in the absence of the porous film on a substrate to form an adhesive porous film, an organic solvent for swelling the polymer cross-linked product and an electrolyte salt dissolved in the organic solvent It can be obtained by contacting the above-mentioned adhesive porous membrane with an electrolytic solution consisting of.

That is, according to the first method, as described above, after the crosslinked polymer is supported on the substrate porous membrane (that is, after the adhesive porous membrane is obtained), the electrolyte salt is dissolved. At the same time, the polymer gel electrolyte can be obtained by contacting the adhesive porous membrane with an electrolytic solution containing an organic solvent for swelling the crosslinked polymer and the electrolyte salt.

In the second method, the polyfunctional polymerizable monomer or the polyfunctional polymerizable monomer and the monofunctional polymerizable monomer are added in the presence or absence of the polymer. After the crosslinked polymer obtained by polymerization and the first electrolytic solution salt are supported on the base material porous membrane to form an ion conductive adhesive porous membrane,
It is also possible to obtain a polymer gel electrolyte by contacting an electrolyte solution composed of an organic solvent for swelling the crosslinked polymer and a second electrolyte salt dissolved in the organic solvent with the ion conductive adhesive porous membrane. it can.

According to the second method, after the crosslinked polymer and the first electrolyte salt are supported on the base material porous membrane (that is, after the ion conductive adhesive porous membrane is obtained). A polymer gel electrolyte can be obtained by contacting an electrolytic solution composed of an organic solvent for swelling the crosslinked polymer and a second electrolyte salt dissolved in the organic solvent with the ion conductive adhesive porous membrane. it can.

In obtaining the polymer gel electrolyte according to the present invention by the above-mentioned first or second method, the electrolyte salt used for preparing the above-mentioned electrolytic solution is not particularly limited, and the above-mentioned ion conductive adhesive is used. In order to obtain a porous porous film, it may be appropriately selected from those supported on the substrate porous film.

In the second method, the base electrolyte membrane is loaded with the first electrolyte salt to form an ion-conductive adhesive porous membrane, and then the electrolyte solution containing the second electrolyte salt is used. A second electrolyte salt is supported on the ion-conductive adhesive porous membrane, and the first electrolyte salt and the second electrolyte salt are added here.
The electrolyte salt is not particularly limited, and may be appropriately selected from, for example, those supported on the base material porous membrane in order to obtain the above-mentioned ion conductive adhesive porous membrane. Further, the first and second electrolyte salts may be the same as or different from each other.

Further, as a third method, a polyfunctional polymerizable monomer or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer is added in the presence or absence of a polymer. After the polymer cross-linked product obtained by polymerization and the electrolyte salt are supported on the base material porous membrane to form the ion conductive adhesive porous membrane, the polymer cross-linked body is swollen, and the electrolyte salt is dissolved in the organic material. A polymer gel electrolyte can be obtained by bringing a solvent into contact with the ion conductive adhesive porous membrane.

According to the third method, after the crosslinked polymer and the electrolyte salt are supported on the base material porous membrane (that is, after the ion conductive adhesive porous membrane is obtained), the electrolyte salt is added. An organic solvent that swells the polymer cross-linked body while dissolving the polymer is contacted with the ion conductive adhesive porous membrane to swell the polymer cross-linked body, preferably, at least a part of the electrolyte salt A polymer gel electrolyte can be obtained by dissolving it in a solvent.

That is, in the third method, instead of the electrolytic solution used in the second method, only the organic solvent for the electrolytic solution is brought into contact with the ion conductive adhesive porous membrane, and the electrolytic salt is used. First, in order to obtain the ion conductive adhesive porous membrane, only the one supported on the porous membrane of the substrate is used. Therefore, the organic solvent used in the third method is preferably the same as the organic solvent used for preparing the electrolytic solution in the first or second method.

As described above, according to the present invention, using the above-mentioned adhesive porous membrane or ion conductive adhesive porous membrane,
Although the polymer gel electrolyte can be obtained by various methods, in particular, according to the present invention, the polymer gel electrolyte having high ion conductivity can be easily obtained in a short time by the second method. .

According to the present invention, in the preparation of the adhesive porous membrane, the ion conductive adhesive porous membrane or the polymer gel electrolyte, the loading amount of the polymer on the substrate porous membrane is
It is usually in the range of 0.01 to 5 mg, and preferably in the range of 0.03 to 3 mg, per 1 cm ^{2 of the} substrate porous membrane.

In the present invention, in the production of the adhesive porous membrane, the ion conductive adhesive porous membrane or the polymer gel electrolyte, the polymer crosslinked raw material is optionally combined with an electrolyte salt to form a base material. The organic solvent used for supporting the material on the porous film dissolves the polymer crosslinked raw material,
Furthermore, when an electrolyte salt is used, it is dissolved, but is not particularly limited as long as it does not dissolve the substrate porous membrane, for example, methyl alcohol, ethyl alcohol, acetonitrile, propionitrile. , Benzene, toluene, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylmethyl carbonate, γ-butyrolactone, diethyl ether, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and any of these. The mixed solvent of is preferably used.

On the other hand, after supporting the above-mentioned crosslinked polymer (if necessary, together with an electrolyte salt) on the substrate porous membrane,
The organic solvent used for obtaining the polymer gel electrolyte by swelling the polymer crosslinked body (and optionally supporting an electrolyte salt) can swell the polymer crosslinked body, and further, the electrolyte When using salt,
Although not particularly limited, a non-aqueous solvent, particularly an aprotic organic solvent is preferably used as long as it can be dissolved and the substrate porous membrane to be used is not dissolved. As a specific example of such a non-aqueous organic solvent,
For example, cyclic esters such as ethylene carbonate, propylene carbonate, butylene carbonate, γ-butyrolactone, ethers such as tetrahydrofuran and dimethoxyethane, chain esters such as dimethyl carbonate and diethyl carbonate, and these can be used alone. Or a mixture of two or more kinds.
When the electrolyte salt is dissolved in the above organic solvent and used as the electrolyte solution, the concentration of the electrolyte salt in the electrolyte solution is not particularly limited, but is usually in the range of 0.05 to 3 mol / L. Yes, and preferably in the range of 0.1 to 2 mol / L.

According to the present invention, in the ion conductive adhesive porous membrane, the amount of the electrolyte salt supported on the substrate porous membrane is usually 1 to 100 parts by weight based on 100 parts by weight of the polymer. It is preferable. As will be described later, even in the polymer gel electrolyte obtained from the adhesive porous membrane or the ion conductive adhesive porous membrane according to the present invention, the amount of the electrolyte salt carried is 100 parts by weight of the polymer,
Generally, it is preferable to set the ratio to 1 to 100 parts by weight.

In the present invention, in order to obtain the ion conductive adhesive porous membrane or the polymer gel electrolyte, the above-mentioned electrolyte salt to be supported on the base material porous membrane is not particularly limited, and the ion conductive The adhesive porous film and the polymer gel electrolyte obtained therefrom may be appropriately selected depending on the required properties and applications, for example, hydrogen, lithium, sodium,
An alkali metal such as potassium, an alkaline earth metal such as calcium or strontium, or a tertiary or quaternary ammonium salt is used as a cation component, and hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, borofluoric acid, hydrofluoric acid, hexafluoride is used. Illustrative are salts having anionic components of inorganic acids such as phosphoric acid and perchloric acid, or organic acids such as carboxylic acids, organic sulfonic acids, and fluorine-substituted organic sulfonic acids.

In the present invention, the electrolyte salt is an electrolyte salt containing an alkali metal ion as a cation component and an inorganic acid or an organic acid, and in the latter case, particularly, trifluoroacetic acid or an organic sulfonic acid as an anion component, among others. Is preferred. As such an electrolyte salt, for example, lithium perchlorate, sodium perchlorate, alkali metal perchlorates such as potassium perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate, etc. Alkali metal tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate, potassium hexafluorophosphate, etc., alkali metal trifluoroacetate, such as lithium trifluoroacetate, lithium trifluoromethanesulfonate Examples thereof include alkali metal trifluoromethanesulfonate and the like.

Since the adhesive porous membrane or the ion conductive adhesive porous membrane according to the present invention has adhesiveness by itself,
It can be advantageously used for manufacturing batteries, capacitors and the like.

That is, for example, after the adhesive porous membrane or the ion conductive adhesive porous membrane according to the present invention is laminated with electrodes, or this laminate is wound, and the electrodes are adhered to these porous membranes. , Such a porous membrane-electrode structure is impregnated with the above organic solvent or electrolytic solution to produce a work-in-process product such as a battery or a capacitor, which is then incorporated into an appropriate outer package and sealed, or the porous film After the porous membrane-electrode structure is incorporated into an appropriate exterior body, the organic solvent or the electrolytic solution is injected into the exterior body, and a method of sealing, for example, forms a polymer gel electrolyte on the spot. Thus, a battery, a capacitor or the like using the polymer gel electrolyte according to the present invention can be obtained.

Also, for example, when assembling a battery or the like in this way, the surface pressure between the electrodes can be increased uniformly, so that the distance between the electrodes can be easily kept constant, and thus excellent. A battery or the like having characteristics can be obtained.

According to the present invention, in order to support the crosslinked polymer on the substrate porous membrane, the raw material of the crosslinked polymer is a polymerization initiator such as an organic peroxide or an azo compound, or After being dissolved in an appropriate organic solvent together with a sensitization aid, etc., a coating solution is applied to or impregnated into the porous film of the base material, then thermal polymerization, active energy such as ultraviolet rays, electron beams, etc. As described above, the polyfunctional polymerizable monomer (and the monofunctional polymerizable monomer) is (co) polymerized (in the presence or absence of the polymer) by photopolymerization with a line to obtain a polymer. A crosslinked product may be formed, and then the above organic solvent may be removed.

In the present invention, the crosslinked polymer means
Thus, it means a three-dimensional network formed by (co) polymerization of polyfunctional polymerizable monomers (and monofunctional polymerizable monomers). When (co) polymerizing a monomer (and a monofunctional polymerizable monomer), it means a structure in which a polymer chain of the polymer is incorporated in the three-dimensional network. However, a part of the above-mentioned polymer may be bonded to a cross-linked polymer formed by the polyfunctional polymerizable monomer (and the monofunctional polymerizable monomer) by a covalent bond.

As the above-mentioned organic peroxide, for example, conventionally known ones such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide, and peroxy ester can be appropriately used. . As a specific example, for example,
Methyl ethyl ketone peroxide, cyclohexanone peroxide, 1,1-bis (t-butylperoxy)
-3,3,5-Trimethylcyclohexane, 2,2-bis (t
-Butylperoxy) octane, n-butyl-4,4-bis (t-butylperoxy) valerate, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydro Peroxide, di-t-butyl peroxide, t-butyl cumyl peroxide, dicumyl peroxide, α,
α'-bis (t-butylperoxy m-isopropyl)
Benzene, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, benzoyl peroxide, t-butylper Examples thereof include oxyisopropyl carbonate. Such an organic peroxide is usually used in a range of 0.01 to 10% by weight based on the total amount of the polyfunctional and monofunctional polymerizable monomers, depending on its type.

Examples of the azo compound include azonitrile compounds, azoamide compounds, azoamidine compounds and the like.
A conventionally known one is appropriately used. Specific examples include, for example, 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,
2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 1,1'-azobis (cyclohexane-1-carbonitrile), 2 -(Carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2-azobis (2-methyl-N-
Phenylpropionamidine) dihydrochloride, 2,2'-azobis [N- (4-chlorophenyl) -2-methylpropionamidine] dihydrochloride, 2,2'-azobis [N-hydroxyphenyl) -2-methylpropion Amidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (2-propenyl) propionamidine ] Dihydrochloride, 2,2'-azobis (2-methylpropionamidine) dihydrochloride, 2,2'-azobis [N- (2-hydroxyethyl) -2-methylpropionamidine] dihydrochloride, 2, 2'-azobis [2- (5-methyl-2-imidazolin-2-yl) propane] dihydrochloride, 2,2'-azobis [2- (2-imidazolin-2-yl) propane]
Dihydrochloride, 2,2'-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepin-2-yl) propane]
Dihydrochloride, 2,2'-azobis [2- (3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,2 '
-Azobis [2- (5-hydroxy-3,4,5,6-tetrahydropyrimidin-2-yl) propane] dihydrochloride, 2,
2'-azobis {2- [1- (2-hydroxyethyl)-
2-Imidazolin-2-yl] propane} dihydrochloride, 2,
2'-azobis [2- (2-imidazolin-2-yl) propane], 2,2'-azobis {2-methyl-N- [1,1-
Bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, 2,2'-azobis {2-methyl-N-
[1,1-bis (hydroxymethyl) ethyl] propionamide}, 2,2′-azobis [2-methyl-N- (2-hydroxyethyl) propionamide], 2,2′-azobis (2-methylpropion Amide) dihydrate, 2,2 '
-Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis (4-cyanoyoshi) Herb acid), 2,2′-azobis [2-hydroxymethyl) propionitrile] and the like.

Such an azo compound is usually used in an amount of 0.01 to 10% by weight based on the total amount of the polyfunctional and monofunctional polymerizable monomers, depending on its type.

When the polymerization is carried out by irradiation with active energy rays such as ultraviolet rays, as a sensitization aid, for example, diethoxyacetophenone, 2-hydroxy-2-methyl-1-
Phenylpropan-1-one, benzyldimethylketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2- Acetophenones such as propyl) ketone, 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one , Benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether,
Benzoin ethers such as benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate,
4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenylsulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone,
4-benzoyl-N, N-dimethyl-N- [2- (1-
Oxo-2-propenyloxy) ethyl] benzenemethanaminium bromide, benzophenones such as (4-benzoylbenzyl) trimethylammonium choroid, 2
-Thioxanthones such as isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, and 2,4-dichlorothioxanthone, azidopyrene, 3-sulfonylazidobenzoic acid, 4-sulfonylazidobenzoic acid, 2,6-bis (4'-azidobenzal) cyclohexanone-2,2'-disulfonic acid (sodium salt),
p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azidobenzalacetophenone, p-azidobenzalacetone, 4,4'-diazidochalcone, 1,3-bis (4'-azidobenzal) Acetone, 2,6-bis (4'-azidobenzal) cyclohexanone, 2,6-bis (4-azidobenzal) -4-methylcyclohexanone, 4,4'-diazidostilbene-2,2'-
Disulfonic acid, 1,3-bis (4'-azidobenzal) -2
-Propanone-2'-sulfonic acid, azides such as 1,3-bis (4'-azidocinnaylidene) -2-propanone and the like are appropriately used.

Such a sensitization aid is usually used in a range of 0.01 to 10% by weight based on the total amount of the polyfunctional and monofunctional polymerizable monomers, although it depends on the kind.

[0066]

EXAMPLES The present invention will be described below with reference to examples and reference examples, but the present invention is not limited to these examples. In the following, the physical properties of the substrate porous membrane used were evaluated as follows.

(Thickness) It was determined based on the measurement with a 1/10000 mm thickness gauge and a scanning electron micrograph of a cross section of the porous film substrate at 10000 times.

(Porosity) Unit area S (c
It was calculated by the following formula from the weight W (g) per m ² ), the average thickness t (cm), and the density d (g / cm ³ ) of the resin that constitutes the substrate porous film. Porosity (%) = (1- (100 W / S / t / d)) × 1
00

(Air permeability) The air permeability was measured according to JIS P 8117.

(Puncture Strength) A puncture test was carried out using a compression tester KES-G5 manufactured by Kato Tech Co., Ltd. The maximum load was read from the obtained load displacement curve and the puncture strength per film thickness of 25 μm was determined. Needle diameter 1.
0mm, radius of curvature 0.5mm at the tip, 2cm
/ Sec.

Example 1 20 parts by weight of trimethylolpropane trimethacrylate, 80 parts by weight of 2-methoxyethyl acrylate and 2,
2-azobis- (2,4-dimethylvaleronitrile) 0.
A coating solution was prepared by dissolving 3 parts by weight of toluene in 1900 parts by weight.

A base material porous film (film thickness: 25) made of an ultra high molecular weight polyethylene resin (weight average molecular weight 2.0 × 10 ⁶ ).
μm, porosity 40%, average pore size 0.05 μm, air permeability 5
00 seconds / 100 mL, needle penetration strength 7.0 N) was immersed in the above coating solution, sandwiched between two glass plates, and heated at 50 ° C. for 3 hours in an inert gas atmosphere to obtain the above trimethylolpropane trimethacrylate. And 2-methoxyethyl acrylate were copolymerized to form a polymer crosslinked body, and thus the swollen gel of the polymer crosslinked body was supported on the base material porous membrane. This was dried and toluene was removed to obtain an adhesive porous membrane carrying the crosslinked polymer. This adhesive porous membrane has adhesiveness by itself,
The 180 ° peeling adhesive strength was 1.8 N / 20 mm width.

Next, the adhesive porous membrane was immersed in a mixture of ethylene carbonate / ethyl methyl carbonate (volume ratio 1/2) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 3 hours to crosslink the polymer. The body was swollen to obtain a polymer gel electrolyte containing the crosslinked polymer as a polymer component. Its conductivity is 9.5 x 1 at 25 ° C.
It was 0 ⁻⁴ S / cm.

Example 2 A coating liquid was prepared in the same manner as in Example 1 except that acetonitrile was used as a solvent instead of toluene. Lithium perchlorate was added to this coating solution at a total weight ratio of trimethylolpropane trimethacrylate and 2-methoxyethyl acrylate / lithium perchlorate weight ratio of 100/15.
And a coating liquid were prepared.

The substrate porous membrane made of the same ultrahigh molecular weight polyethylene resin as in Example 1 was dipped in the above coating solution and then 2
Sandwiched between two glass plates, in an inert gas atmosphere, 50 ° C
By heating for 3 hours to react the above polymer crosslinked raw material,
Thus, a porous membrane supporting a swollen gel of a crosslinked polymer was obtained. This was dried and acetonitrile was removed to obtain an ion-conductive adhesive porous membrane supporting the crosslinked polymer and lithium perchlorate. The ion conductive adhesive porous membrane has adhesiveness by itself,
The 0 ° peeling adhesive strength was 2.1 N / 20 mm width.

Next, the ion conductive adhesive porous membrane was immersed for 3 hours in an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2) in which lithium perchlorate was dissolved at a concentration of 1 mol / L, The crosslinked polymer was swollen, and a polymer gel electrolyte containing the crosslinked polymer as a polymer component was thus obtained. Its conductivity is 25 ° C
Was 1.1 × 10 ⁻³ S / cm.

Example 3 In Example 1, as the base material porous film, a porous film made of polytetrafluoroethylene resin (film thickness 20 μm,
Porosity 70%, average pore size 1.0 μm, air permeability 200 seconds / 1
Example 1 except that 00 mL, needle penetration strength 3 N) was used.
In the same manner as above, an adhesive porous membrane supporting a crosslinked polymer was obtained. This adhesive porous film has adhesiveness by itself and has a 180 ° peeling adhesive force of 2.4 N / 20 m.
It was m width.

Then, the adhesive porous membrane was immersed in a mixture of ethylene carbonate / ethyl methyl carbonate (volume ratio: 1/2) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 3 hours to crosslink the polymer. The body was swollen, and thus a polymer gel electrolyte containing the polymer cross-linked body as a polymer component was obtained. Its conductivity at 25 ° C is
It was 1.4 × 10 ⁻³ S / cm.

Example 4 45 parts by weight of polyethylene glycol dimethacrylate,
Dissolve 50 parts by weight of ethoxydiethylene glycol acrylate, 5 parts by weight of methyl methacrylate / ethoxyethyl acrylate (1/2) copolymer, 1 part by weight of 1-hydroxycyclohexyl phenyl ketone and 1 part by weight of benzyl dimethyl ketal in 1900 parts by weight of methanol. A coating liquid was prepared.

A substrate porous film (thickness: 25) made of an ultra high molecular weight polyethylene resin (weight average molecular weight 2.0 × 10 ⁶ ).
μm, porosity 40%, average pore size 0.05 μm, air permeability 5
00 sec / 100 mL, needle penetration strength 7.0 N) was immersed in the above coating solution, sandwiched between two glass plates, and then irradiated with ultraviolet rays of 3 J / cm ² in an inert gas atmosphere to obtain the above polyethylene glycol dimethacrylate. And ethoxydiethylene glycol acrylate were copolymerized in the presence of a methyl methacrylate / ethoxyethyl acrylate copolymer to form a polymer crosslinked product, and thus the swollen gel of the polymer crosslinked product was supported on the substrate porous membrane. This was dried and methanol was removed to obtain an adhesive porous membrane supporting the crosslinked polymer. This adhesive porous film had adhesiveness by itself, and had a 180 ° peeling adhesive force of 2.2 N / 20 mm width.

Next, the adhesive porous membrane was immersed in a mixture of ethylene carbonate / ethyl methyl carbonate (volume ratio 1/2) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 3 hours to crosslink the polymer. The body was swollen to obtain a polymer gel electrolyte containing the crosslinked polymer as a polymer component. Its conductivity is 8.3 x 1 at 25 ° C.
It was 0 ⁻⁴ S / cm.

Comparative Example 1 15 parts by weight of an ultrahigh molecular weight polyethylene resin having a weight average molecular weight of 2.0 × 10 ⁶ and 85 parts by weight of liquid paraffin (kinematic viscosity 59 cst at 40 ° C.) were mixed to form a uniform slurry, which was made into a small size. Charge in a kneader and set the temperature to 160 ° C for 1
It was heated, melted and kneaded for a time. The obtained kneaded product is 0
It was sandwiched between metal plates cooled to ℃ and rapidly cooled to obtain a 5 mm thick gel-like sheet. This sheet was rolled by a heat press at a temperature of 120 ° C. to a thickness of 0.8 mm and simultaneously biaxially stretched at a temperature of 125 ° C. in the length and width of 3.5 × 3.5 to obtain a rolled stretched film. Then, the liquid paraffin was extracted and removed to obtain a porous film. This porous film was heat-treated at 130 ° C. for 20 minutes. The total draw ratio was 77 times. The porous film thus obtained has no adhesive property by itself and has a thickness of 20 mm.
The 180 ° C peeling adhesive strength across the width was zero.

The above-mentioned porous film was immersed in an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 3 hours, and its conductivity was measured. At 25 ° C., it was 6.0 × 10 ⁻⁴ S / cm.

[0084]

INDUSTRIAL APPLICABILITY As described above, the adhesive porous membrane according to the present invention comprises a cross-linked polymer supported on a substrate porous membrane and has an adhesive force by itself, and an electrolyte salt is added to the organic porous membrane. A polymer gel electrolyte can be obtained by bringing an electrolyte solution dissolved in a solvent into contact with the polymer to swell the crosslinked body of the polymer, and the ion conductive adhesive porous membrane according to the present invention is a polymer. A crosslinked body and an electrolyte salt are supported on a porous membrane, which has an adhesive force by itself, and a solvent that dissolves the electrolyte salt therein, or by contacting an electrolytic solution containing the electrolyte salt, Similarly, a polymer gel electrolyte can be obtained.

Since the adhesive porous membrane or the ion conductive adhesive porous membrane according to the present invention has an adhesive force by itself, for example, in the production of batteries, capacitors, etc., it is laminated with electrodes, Alternatively, by winding and adhering the electrodes to these porous membranes to form a porous membrane-electrode structure,
By using a polymer gel electrolyte, the surface pressure between the electrodes can be increased uniformly and the distance between the electrodes can be kept constant.
Thus, a battery or the like having excellent characteristics can be obtained.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁷ Identification code FI theme code (reference) H01G 9/02 301 H01G 9/02 301 9/028 H01M 10/40 B 9/035 H01G 9/02 311 H01M 10/40 331G (72) Inventor Yoshihiro Uetani 1-2, Shimohozumi, Ibaraki City, Osaka Prefecture F-term within Nitto Denko Corporation (reference) 4J004 AA17 CA04 FA05 4J040 DF021 EE001 JA09 5G301 CA30 CD01 5H029 AJ01 AJ06 AJ14 AM00 AM02 AM03 AM04 AM05 AM07 AM16 CJ00 CJ08 CJ11 DJ04 DJ09 DJ13 EJ12 HJ04 HJ09 HJ14 HJ20

Claims (16)

[Claims] 1. A polymer crosslink obtained by polymerizing a polyfunctional polymerizable monomer or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. An adhesive porous membrane, which is obtained by supporting a body on a substrate porous membrane, and has an adhesive property of itself having a 180 ° peeling adhesive strength of 0.2 N or more in a width of 20 mm. 2. A polyfunctional polymerizable monomer, or a polymer crosslink obtained by polymerizing a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. The body and the electrolyte salt are supported on the base material porous membrane, and by itself,
An ion conductive adhesive porous membrane having an adhesiveness of 180 ° peeling adhesive strength of 0.2 N or more in a width of 20 mm. 3. The polyfunctional polymerizable monomer is (poly) alkylene glycol poly (meth) acrylate.
Or the adhesive porous membrane according to 2. 4. The adhesive porous membrane according to claim 1, wherein the monofunctional polymerizable monomer is mono (meth) acrylate. 5. The adhesive property according to any one of claims 1 to 4, wherein the substrate porous film has a porosity of 30 to 95%, an air permeability of 1500 seconds / 100 mL or less, and a needle penetration strength of 3N or more. Porous membrane. 6. (a) a substrate porous membrane, (b) an organic solvent, (c) a polyfunctional polymerizable monomer, or a polyfunctional polymerizable monomer and a monofunctional polymerizable A polymer cross-linked product obtained by polymerizing a monomer and a polymer in the presence or absence of a polymer, which is supported on the substrate porous membrane and swollen with the organic solvent. A polymer gel electrolyte comprising a body and (d) an electrolyte salt. 7. The polyfunctional polymerizable monomer is (poly) alkylene glycol poly (meth) acrylate.
The polymer gel electrolyte according to 1. 8. The polymer gel electrolyte according to claim 6, wherein the monofunctional polymerizable monomer is mono (meth) acrylate. 9. The polymer according to claim 6, wherein the porous film of the substrate has a porosity of 30 to 95%, an air permeability of 1500 seconds / 100 mL or less, and a needle penetration strength of 3N or more. Gel electrolyte. 10. The polymer gel electrolyte according to claim 6, which has an ionic conductivity of 1 × 10 ⁻⁴ S / cm or more. 11. A polyfunctional polymerizable monomer, or a polymer crosslink obtained by polymerizing a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. After the body is supported on the substrate porous membrane to form an adhesive porous membrane, an electrolytic solution comprising an organic solvent for swelling the polymer crosslinked body and an electrolyte salt dissolved in the organic solvent is added to the adhesive porous membrane. A method for producing a polymer gel electrolyte, which comprises contacting with a membrane. 12. A polyfunctional polymerizable monomer, or a polymer crosslink obtained by polymerizing a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. Body and the first electrolyte salt are carried on the base material porous membrane to form an ion conductive adhesive porous membrane, and then an organic solvent for swelling the polymer crosslinked body and a second solvent soluble in the organic solvent A method for producing a polymer gel electrolyte, which comprises bringing an electrolytic solution containing an electrolyte salt into contact with the ion conductive adhesive porous membrane. 13. A polymer crosslink obtained by polymerizing a polyfunctional polymerizable monomer or a polyfunctional polymerizable monomer and a monofunctional polymerizable monomer in the presence or absence of a polymer. Body and electrolyte salt are supported on a substrate porous membrane to form an ion-conductive adhesive porous membrane, and then the polymer crosslinked body is swollen, and an organic solvent for dissolving the electrolyte salt is added to the ion-conductive layer. A method for producing a polymer gel electrolyte, which comprises contacting with an adhesive porous membrane. 14. The method for producing a polymer gel electrolyte according to claim 11, wherein the polyfunctional polymerizable monomer is (poly) alkylene glycol poly (meth) acrylate. 15. The method for producing a polymer gel electrolyte according to claim 11, wherein the monofunctional polymerizable monomer is mono (meth) acrylate. 16. The polymer according to claim 11, wherein the porous membrane has a porosity of 30 to 95%, an air permeability of 1500 seconds / 100 mL or less, and a needle penetration strength of 3N or more. Method for producing gel electrolyte.