JP2002249742A - Adhesive porous membrane, polymeric gel electrolyte obtained therefrom and application thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a porous membrane having a combination of ionic conductivity with mechanical strength and having adhesivity in itself, and to provide a polymeric gel electrolyte obtained from the above porous membrane. SOLUTION: This adhesive porous membrane with ionic conductivity, which has a 180 deg. peel adhesive force of >=2N in itself at 20 mm width, is obtained by bearing a porous base film with an electrolyte salt and a polymer with the main chain of polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, polyethylene propylene oxide, polyphosphazene, polyvinyl ether or polysiloxane structure and the side chain of chain oligoalkylene oxide structure.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

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

For example, according to a battery using such a conventional solid electrolyte, the solid electrolyte has a significantly lower ionic conductivity than a liquid electrolyte. Discharge cannot be performed. If the shape of the electrode changes due to charging and discharging, the solid electrolyte cannot follow such a change in the shape of the electrode. It cannot be discharged.

Therefore, in recent years, in order to improve the ionic conductivity of such a solid electrolyte, for example, it has been proposed to mix an organic solvent such as propylene carbonate or γ-butyrolactone as a plasticizer with the solid electrolyte. .

[0005] For example, J. Electrochem. Soc., Vol.
7, 1657-1658 (1990) proposed a sheet-like polymer gel electrolyte obtained by gelling an organic electrolyte comprising a mixed solvent of propylene carbonate and ethylene carbonate in which lithium perchlorate was dissolved with polyacrylonitrile. ing. JP-A-11-16579 proposes a polymer gel electrolyte comprising polyacrylonitrile, an electrolyte salt and a non-aqueous solvent. Further, Japanese Patent Application Laid-Open No. 8-2981
No. 26 proposes a polymer gel electrolyte using polyethylene oxide or polypropylene oxide as a polymer component and using γ-butyrolactone as a solvent.

However, such a polymer gel electrolyte is
Since the strength is low, the thickness must be increased in order to form a film, and as a result, if the battery is assembled by providing electrodes with such a polymer gel electrolyte interposed, the distance between the electrodes is large, and the internal The resistance becomes high, and sufficient charging and discharging cannot be performed.

In order to solve the problem of strength in the conventional polymer gel electrolyte, Japanese Patent Laid-Open No.
No. -40128 discloses that 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. And
A method is described in which a porous membrane is stretched to be impregnated with an electrolyte solution and gelled to obtain a polymer gel electrolyte. JP-A-11-353935 discloses a gel-forming polymer which forms a gel together with a non-aqueous (organic) solvent for forming a non-aqueous electrolyte such as propylene carbonate, ethylene carbonate, dimethoxyethane and the like. Fibers, for example, polyacrylonitrile-methyl acrylate copolymer resin fibers, and a fiber having resistance to the above-mentioned solvent, for example, to form a fibrous structure composed of polyolefin fibers, and this 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 from the above-mentioned polyolefin resin or polyolefin fiber, which is a reinforcing material, has a relatively high strength even in a film shape. Therefore, the proportion of a polymer substance or a gel-forming polymer capable of holding an electrolyte solution must be relatively reduced. Therefore, in such a polymer gel electrolyte, these polymer substances and the gel-forming polymer tend to form an incomplete gel body, and as a result, there is an inherent advantage of the polymer gel electrolyte that there is no liquid leakage. In addition, there is a problem that the ionic conductivity of the obtained polymer gel electrolyte is reduced because the polymer gel electrolyte does not have complete integrity and continuity due to the presence of the reinforcing material. Of course, if the blending ratio of the polymer substance or the gel-forming polymer that holds the electrolyte solution is increased, the resulting polymer gel electrolyte has high ionic conductivity but low strength.

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

As described above, the polymer gel electrolyte is useful as a battery separator. Here, in order to prevent a short circuit due to direct contact between the positive electrode and the negative electrode and to secure ion permeability between the positive electrode and the negative electrode, a porous membrane having a large number of micropores is used for the battery separator. Have been. Various characteristics are required for the porous film used for such a battery separator in relation to the battery characteristics. Among them, in order to improve the battery characteristics, in particular, to reduce the thickness and increase the strength. Is desired.

Therefore, conventionally, a porous membrane for a battery separator has been manufactured by a method of stretching a molded sheet at a high magnification, as described in, for example, JP-A-9-12756. . Therefore, the battery separator made of such a porous membrane significantly shrinks in a high-temperature environment such as when the battery is abnormally heated due to an internal short circuit or the like, and in some cases, does not function as a partition between electrodes. There is a problem. Therefore, in order to improve the safety of the battery, it is important to reduce the heat shrinkage of the battery separator under such a high temperature environment. In this regard, in order to suppress thermal shrinkage of the battery separator in a high-temperature environment, Japanese Patent Application Laid-Open No. Hei 5-310899 discloses a method of manufacturing a porous film by a method that does not include a stretching treatment in a manufacturing process. On the other hand, the porous membrane thus obtained is not stretched,
There is a problem that the strength is not sufficient.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems in the conventional polymer gel electrolyte, and has both ionic conductivity and strength. It is an object of the present invention to provide an ion-conductive porous membrane having adhesiveness, a porous membrane therefor, and a polymer gel electrolyte obtained therefrom. In particular, an object of the present invention is to provide a polymer gel electrolyte in which a crosslinked polymer is supported as a polymer component (polymer matrix) on a porous base material membrane and has a small heat shrinkage even under a high temperature environment. And Another object of the present invention is to provide a battery or a capacitor using such a polymer gel electrolyte.

[0013]

According to the present invention, a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene,
It has a polyvinyl ether or polysiloxane structure and a polymer having a chain oligoalkylene oxide structure in a side chain supported on a porous base material film, and is itself peeled at 180 ° in a width of 20 mm. Adhesive strength is 2
An adhesive porous film having an adhesive property of N or more is provided.

Further, according to the present invention, polyacrylate, polymethacrylate, polyethylene oxide,
A polymer having a polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure and having a chain oligoalkylene oxide structure in a side chain and an electrolyte salt are supported on a porous base material membrane. The present invention provides an ion-conductive adhesive porous membrane having an adhesiveness of 180 ° peeling adhesion of 2 N or more in a width of 20 mm by itself.

Further, according to the present invention, there is provided a porous base material membrane,
A polymer having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain and a chain oligoalkylene oxide structure in the side chain. In addition, there is provided a polymer gel electrolyte comprising a polymer supported on the porous film of the base material and swollen with an organic solvent, and an electrolyte salt.

In particular, according to the present invention, the following polymers having a polyethylene oxide, polypropylene oxide or poly (ethylene oxide / propylene oxide) structure in the main chain and a chain oligoalkylene oxide structure in the side chain are used according to the present invention. A polymer gel electrolyte using an ether multi-component copolymer is provided.

That is, according to the present invention, a porous substrate membrane
As the monomer components, 1 to 99 mol% of the components of the following formula (1), 99 to 1 mol% of the components of the formula (2), and 0 to 20 of the reactive group-containing components represented by the formula (3) or (4). %, And the repeating structural units are represented by the formulas (5) and (6):
It is represented by any of the formulas (5), (6) and (7), and the formulas (5), (6) and (8), and has a weight average molecular weight of 10 ⁴
A polyether multicomponent copolymer in 10 ⁷ within the range of, along with being supported on the base porous film, a polyether multicomponent copolymers which are allowed to swell in an organic solvent, an electrolyte salt A polymer gel electrolyte characterized by comprising:

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(In the formulas (1) and (5), R and R ′ are each independently a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 12 carbon atoms, and 2 to 8 carbon atoms.
A alkenyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and the degree of polymerization k of an oxyalkylene unit serving as a side chain portion Is 1 to 12. In the formulas (2) and (6), R ′ is a hydrogen atom or a methyl group.
In the formulas (3) and (7), R ′ is a hydrogen atom or a methyl group, and R ₂ is a substituent containing an ethylenically unsaturated group, a reactive silicon-containing substituent, or an epoxy group. And (4) and (8), wherein R is
₃ represents a reactive silicon-containing substituent. (9) In the formula, A represents an organic residue. According to the invention, such polymer gel electrolytes have, in the main chain, polyacrylates, polymethacrylates, polyethylene oxides, polypropylene oxides, poly (ethylene oxide / propylene oxide),
Polyphosphazene, having a polyvinyl ether or polysiloxane structure, a polymer having a chain-like oligoalkylene oxide structure in the side chain is supported on the base porous film,
The adhesive porous membrane can be obtained by contacting the adhesive porous membrane with an electrolytic solution comprising an organic solvent that dissolves the electrolyte salt and swells the polymer and the electrolyte salt.

Also, the polymer gel electrolyte according to the present invention comprises:
A polymer having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain and a chain oligoalkylene oxide structure in the side chain; The first electrolyte salt is supported on the porous base material membrane to form an ion-conductive adhesive porous membrane, and the electrolyte comprises an organic solvent that swells the polymer and a second electrolyte salt that is dissolved in the organic solvent. It can also be obtained by bringing the liquid into contact with the ion-conductive adhesive porous membrane.

Further, the polymer gel electrolyte according to the present invention comprises:
A polymer having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain and a chain oligoalkylene oxide structure in the side chain; An electrolyte salt is supported on a porous base material membrane to form an ion-conductive adhesive porous membrane, and an organic solvent that dissolves the electrolyte salt and swells the polymer contacts the ion-conductive adhesive porous membrane. Can also be obtained.

Further, according to the present invention, in particular, the following polymer having a polyethylene oxide, polypropylene oxide or poly (ethylene oxide / propylene oxide) structure in the main chain and a chain oligoalkylene oxide structure in the side chain is used as the polymer. And a method for producing a polymer gel electrolyte using the polyether multi-component copolymer.

That is, first, as the monomer components, 1 to 99 mol% of the components of the following formula (1),
1 mol%, and 0 to 20 mol% of the reactive group-containing component represented by the formula (3) or (4), wherein the repeating structural units are represented by the formulas (5) and (6), (5) and (6) And (7),
(5) and (6) and a polyether multi-component copolymer having a weight average molecular weight in the range of 10 ⁴ to 10 ⁷ , which is represented by any of the formulas, is supported on the porous base material membrane, An adhesive porous membrane, wherein an electrolytic solution comprising an organic solvent that dissolves the electrolyte salt and swells the polyether multi-component copolymer and the electrolyte salt is brought into contact with the adhesive porous membrane. A method for producing a molecular gel electrolyte is provided.

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(In the formulas (1) and (5), R and R ′ are each independently a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 12 carbon atoms, and 2 to 8 carbon atoms.
A alkenyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and the degree of polymerization k of an oxyalkylene unit serving as a side chain portion Is 1 to 12. In the formulas (2) and (6), R ′ is a hydrogen atom or a methyl group.
In the formulas (3) and (7), R ′ is a hydrogen atom or a methyl group, and R ₂ is a substituent containing an ethylenically unsaturated group, a reactive silicon-containing substituent, or an epoxy group. And (4) and (8), wherein R is
₃ represents a reactive silicon-containing substituent. (9) In the formula, A represents an organic residue. Second, the polyether multi-component copolymer and the first electrolyte salt are supported on a porous base material membrane,
An electrolytic solution comprising an organic solvent for swelling the polyether copolymer and a second electrolyte salt dissolved in the organic solvent is brought into contact with the ion-conductive adhesive porous membrane as an ion-conductive adhesive porous membrane. The present invention provides a method for producing a polymer gel electrolyte.

Third, the polyether multicomponent copolymer and an electrolyte salt are supported on a porous base material film to form an ion-conductive adhesive porous film. The electrolyte salt is dissolved and the polyether multicomponent polymer is dissolved. A method for producing a polymer gel electrolyte is provided, wherein an organic solvent for swelling the copolymer is brought into contact with the ion-conductive adhesive porous membrane.

According to the present invention, there is further provided a polymer gel electrolyte comprising the above polyether multicomponent copolymer as a polymer component, wherein the polyether multicomponent copolymer is crosslinked. And a method of manufacturing the same.

In addition to the above, the present invention provides a battery or a capacitor using the above polymer gel electrolyte.

[0045]

BEST MODE FOR CARRYING OUT THE INVENTION The adhesive porous membrane according to the present invention comprises:
Polymers having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain and a chain oligoalkylene oxide structure in the side chain It is supported on a porous substrate membrane, and has an adhesiveness of 180 N peeling strength of 2N or more in a width of 20 mm by itself.

In the present invention, the 180 ° peel adhesive strength is measured using a stainless steel plate as an adherend according to JIS Z0237.

In the present invention, the porous base material has both strength and strength in consideration of using the polymer gel electrolyte finally obtained by using the same as the separator of a battery, a capacitor or the like according to the present invention. It does not dissolve in the electrolytic solution, as long as it has oxidation-reduction resistance, but is not particularly limited, for example, a polyolefin resin such as a polyethylene resin including an ultrahigh molecular weight polyethylene resin or a polypropylene resin, a fluororesin, or the like. It is preferably used.

Similarly, in the present invention, the porous base material film is particularly preferable in consideration of using the polymer gel electrolyte finally obtained by using the same as the separator of a battery, a capacitor or the like according to the present invention. Although not limited, the porosity is 30 to 95%, preferably 33 to 9
0%, particularly preferably in the range of 35-85%. When the porosity is too low, the ionic conduction path decreases,
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 substrate porous film is not sufficient in strength, and in order to obtain a substrate porous film having sufficient strength, it is necessary to increase the film thickness. As described above, when the obtained polymer gel electrolyte is used as a battery separator, the internal resistance is increased.

The porous substrate has a permeability of 15%.
00 sec / 100 mL or less, preferably 1000 sec / 1
It is preferably not more than 00 mL. When the air permeability is too high, the ionic conductivity of the obtained polymer gel electrolyte becomes low. For example, when the obtained polymer gel electrolyte is used as a battery separator, sufficient battery characteristics cannot be obtained. Further, the porous base material preferably has a needle penetration strength per 25 μm of 3 N or more. When the needle penetration strength is too small, when the resulting polymer gel electrolyte is used as a battery separator, the base porous film may break when surface pressure is applied between the electrodes, causing an internal short circuit. is there.

According to the present invention, a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane is added to such a substrate porous membrane in the main chain. By carrying a polymer having a structure and having a chain oligoalkylene oxide structure in a side chain, an adhesive porous membrane having an adhesive force by itself can be obtained.

In order to carry such a polymer on the porous base material membrane, for example, the polymer is dissolved in an appropriate solvent, usually an organic solvent, and the obtained coating liquid is applied to the porous base material membrane. Alternatively, the organic solvent may be removed by immersing the porous substrate film in a coating solution and then heating and drying the film.
Incidentally, in the present invention, the adhesive porous membrane is thus,
As a result of supporting the polymer on the porous base material membrane, it is assumed that the polymer is filled in all pores of the porous base material membrane.

In the present invention, the above-mentioned organic solvent dissolves the polymer having a chain-like oligoalkylene oxide structure in the side chain while dissolving the substrate porous membrane.
In particular, but not limited to, for example, methyl alcohol, ethyl alcohol, acetonitrile, propionitrile, benzene, toluene, dimethyl carbonate, diethyl carbonate, propylene carbonate,
Ethyl methyl carbonate, γ-butyrolactone, diethyl ether, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and the like, and an arbitrary mixed solvent thereof are preferably used.

According to the present invention, the amount of the polymer supported on the porous substrate membrane is usually per 1 cm ^{2 of the} porous substrate membrane,
The range is 0.01 to 5 mg, preferably 0.03 to 3 mg.
mg range.

According to the present invention, among the above polymers, polyether multi-components having a polyethylene oxide, polypropylene oxide or poly (ethylene oxide / propylene oxide) structure in the main chain and a chain oligoalkylene structure in the side chain are preferred. Polymers are preferably used.
In particular, according to the present invention, the main chain has a polyethylene oxide or poly (ethylene oxide / propylene oxide) structure, and the side chain has a chain oligoethylene structure, a chain oligopropylene structure or a chain oligoethylene propylene structure (particularly, A polyether multi-component copolymer having a chain oligoethylene structure or a chain oligopropylene structure, in particular, the former) is preferably used.

Such a polyether multi-component copolymer is as follows:
For example, JP-A-63-154736, JP-A-9-324114, and JP-A-10-130487 have already been described.
JP, JP-A-10-176105, JP-A-10-176105
Such a polyether multi-component copolymer, which is known as described in JP-A-204172 and the like, will be described below.

The polyether multi-component copolymer which can be preferably used in the present invention has, as a monomer component,
Component 1-99 mol% of the following formula (1), component 9 of the formula (2)
9 to 1 mol%, and 0 to 20 mol% of the reactive group-containing component represented by the formula (3) or (4), wherein the repeating structural units are (5) and (6). )formula,
It is represented by any of the formulas (5) and (6) and (7), and the formulas (5) and (6) and (8), and its weight average molecular weight is
In ^104-107 range.

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(In the formulas (1) and (5), R and R ′ are each independently a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 12 carbon atoms, and 2 to 8 carbon atoms.
A alkenyl group, a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and the degree of polymerization k of an oxyalkylene unit serving as a side chain portion Is 1 to 12. In the formulas (2) and (6), R ′ is a hydrogen atom or a methyl group.
In the formulas (3) and (7), R ′ is a hydrogen atom or a methyl group, and R ₂ is a substituent containing an ethylenically unsaturated group, a reactive silicon-containing substituent, or an epoxy group. And (4) and (8), wherein R is
₃ represents a reactive silicon-containing substituent. (9) In the formula, A represents an organic residue. Such polyether multi-component copolymers used in the present invention include, for example, a catalyst system mainly composed of organoaluminum, a catalyst system mainly composed of organic zinc, and an organic tin-phosphate ester condensate as a ring-opening polymerization catalyst. Using a catalyst system or the like, each monomer corresponding to the formula (3) or (4) is added to the monomers corresponding to the above formulas (1) and (2), if necessary, and the mixture is added in the presence of a solvent. Alternatively, it is obtained by reacting in the absence and at a reaction temperature of 10 to 80 ° C with stirring. Among them, an organic tin-phosphate ester condensate catalyst system is particularly preferably used as a catalyst from the viewpoint of the degree of polymerization and properties of the obtained polyether multi-component copolymer.

In the production of the above polyether multi-component copolymer, a monomer component represented by the formula (1) or (2)
The formula and the formula (3) or (4) are represented by (1)
Formula 1 to 99 mol%, (2) Formula 99 to 1 mol% and (3)
The formula (4) is used at a ratio of 0 to 20 mol%, preferably (1) 2 to 95 mol%, (2) 98 to 5 mol% and (3) or (4) formula 0 It is used in a proportion of 15 mol%.

In the production of the polyether multi-component copolymer used in the present invention, it is essential to use the monomer components represented by the formulas (1) and (2) as the above-mentioned monomer components. As will be described later, in order to obtain a crosslinked product of the polyether multi-component copolymer, in addition to the above-mentioned monomer components, as a reactive group-containing monomer component, a reaction selected from the monomer components (3) and (4) A polyether multi-component copolymer is produced by using a functional group-containing monomer component and copolymerizing them. Thus, a polyether multi-component copolymer having a reactive group-containing monomer component as a copolymer component unit, as described below, utilizing the reactive group, for example, if necessary, a crosslinking aid And by heating in the presence of a polymerization initiator to form a crosslinked product.

For example, as described above, a polyether multi-component copolymer having a reactive group-containing monomer component is supported on a porous membrane together with an electrolyte salt to form an ion-conductive adhesive porous membrane. After the polyether multi-component copolymer is swollen, the polyether multi-component copolymer can be cross-linked by further heating, and thus a cross-linked product of the polyether multi-component copolymer is obtained. Can be obtained as a polymer component (matrix).

In the production of the polyether multi-component copolymer, when the amount of the monomer component of the above formula (2) exceeds 99 mol%, the glass transition temperature is increased and the oxyethylene chain is crystallized, and as a result, the resulting product is obtained. This will significantly deteriorate the ionic conductivity of the polymer gel electrolyte. In general,
It is known that the ionic conductivity of the obtained polymer is improved by lowering the crystallinity of polyethylene oxide, but the polyether multi-component copolymer used in the present invention reduces the crystallinity of polyethylene oxide. The effect of improving the ionic conductivity is very large.

In the monomer component of the above formula (1),
R ′ represents a hydrogen atom or a methyl group;
In the oxyalkylene unit in the formula, R independently represents a hydrogen atom or a methyl group, all may be hydrogen atoms, all may be methyl groups, or some may be hydrogen atoms, and the remainder may be methyl groups. May be. Accordingly, the oxyalkylene unit may be an oxyethylene unit or an oxypropylene group unit, or may be an oxyethylene / oxypropylene unit, but is preferably an oxyethylene unit or an oxypropylene unit, and particularly preferably an oxyethylene unit. It is. Further, the degree of polymerization k of the oxyalkylene unit is preferably from 1 to 12. When the value of the degree of polymerization k exceeds 12, the ionic conductivity of the resulting polymer gel electrolyte decreases.

The polyether used in the present invention
The molecular weight of the multi-component copolymer depends on processability, moldability, and mechanical strength.
To obtain flexibility and flexibility, a weight average molecular weight of 10^Four~
10⁷, Preferably 10^Five~ 5x10⁶In the range
Is preferred. Weight average molecular weight of 10^FourLess than
, A sufficient mechanical strength cannot be obtained. On the other hand, 1
0 ⁷If it exceeds, a problem occurs in solubility.

Further, the glass transition temperature of the multi-component polyether copolymer is preferably -60 ° C. or lower, and the heat of fusion is 70 ° C.
J / g or less is preferable. The glass transition temperature and the heat of fusion are measured by a differential scanning calorimeter (DSC). Such a multi-component polyether copolymer used in the present invention may be any of a block copolymer and a random copolymer,
Random copolymers are preferred because they have a greater effect of lowering the crystallinity of the polymer main chain composed of polyethylene oxide.

Specific examples of the monomer component represented by the above formula (1) include diethylene glycol glycidyl methyl ether, dipropylene glycol glycidyl methyl ether and the like. According to the invention, a mixture of two or more of these may be used.

The monomer component represented by the formula (2) is
Specifically, it is ethylene oxide or propylene oxide. According to the invention, a mixture of two or more of these may be used.

Among the reactive group-containing monomer components represented by the formula (3), the ethylenically unsaturated group-containing monomer components include allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether and α-terpinyl glycidyl ether. , Cyclohexenylmethyl glycidyl ether, p-vinylbenzyl glycidyl ether, allylphenyl glycidyl ether, vinyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-1
-Pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-
1-vinylcyclohexene, 1,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate,
Glycidyl crotonate, glycidyl-4-hexenoate and the like (the above is a case where R ′ is a hydrogen atom),
3-epoxy-2-methylpropyl vinyl ether, 2,
3-epoxy-2-methylpropyl allyl ether, 3,
4-epoxy-3-methyl-1-butene, etc.
R 'is a methyl group. ) Etc. are used. According to the invention, a mixture of two or more of these may be used. According to the present invention, among these, in particular,
Allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate and the like are preferably used.

Among the reactive group-containing monomer components represented by the formula (3), specific examples of the silicon-containing monomer include the following formulas (10) and (11).

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Specific examples of the reactive silicon-containing monomer represented by the above formula (4) include, for example, the following (12)
Formulas can be mentioned.

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In the above formulas (10) to (12), R ′
Is a hydrogen atom or a methyl group; _Four, R_Five, R₆Is
Each may be the same or different, but few
At least one is an alkoxyl group and the rest is an alkyl group
It is. m represents 1 to 6.

Examples of the monomer represented by the above formula (10) include glycidoxymethyltrimethoxysilane,
Glycidoxymethylmethyldimethoxysilane, glycidoxyethyltrimethoxysilane, glycidoxyethylmethyldimethoxysilane, glycidoxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxybutylmethyldimethoxysilane, glycid Xybutylmethyltrimethoxysilane, glycidoxyhexylmethyldimethoxysilane, glycidoxyhexylmethyltrimethoxysilane, etc. (wherein R ′ is a hydrogen atom), 2,3-epoxy-2-methyl Propoxymethyltrimethoxysilane, 2,3-epoxy-2-methylpropoxymethylmethyldimethoxysilane, 2,3-epoxy-2-methylpropoxymethyldimethylmethoxysilane, etc. (above, R ′ is a methyl group. ) Can. According to the invention, a mixture of two or more of these may be used.

Examples of the monomer represented by the above formula (11) include 1,2-epoxypropyltrimethoxysilane, 1,2-epoxypropylmethyldimethoxysilane,
1,2-epoxypropyldimethylmethoxysilane, 1,2
-Epoxybutyltrimethoxysilane, 1,2-epoxybutylmethyldimethoxysilane, 1,2-epoxypentyltrimethoxysilane, 1,2-epoxypentylmethyldimethoxysilane, 1,2-epoxyhexyltrimethoxysilane, 1,2 -Epoxyhexylmethyldimethoxysilane and the like (the above is the case where R 'is a hydrogen atom);
2,3-epoxy-2-methylpropyltrimethoxysilane, 2,3-epoxy-2-methylpropylmethyldimethoxysilane, 2,3-epoxy-2-methylpropyldimethylmethoxysilane, etc. (where R 'is methyl Group).). According to the invention, a mixture of two or more of these may be used.

The monomer represented by the above formula (12) includes, for example, (3,4-epoxycyclohexyl)
-1-methyltrimethoxysilane, (3,4-epoxycyclohexyl) -1-methylmethyldimethoxysilane,
(3,4-epoxycyclohexyl) -1-ethyltrimethoxysilane, (3,4-epoxycyclohexyl) -1
-Ethylmethyldimethoxysilane, (3,4-epoxycyclohexyl) -1-propyltrimethoxysilane,
(3,4-epoxycyclohexyl) -1-propylmethyldimethoxysilane, (3,4-epoxycyclohexyl) -1-butyltrimethoxysilane, (3,4-epoxycyclohexyl) -1-butylmethyldimethoxysilane, and the like. be able to.

In the present invention, among the reactive group-containing monomer components, particularly, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 1,2-epoxybutyltrimethoxysilane , 1,2-epoxypentyltrimethoxysilane,
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and the like are preferred.

In the epoxy group-containing monomer having the substituent (9) represented by the formula (3), the organic residue A is not particularly limited in its structure. And (poly) methylene groups, and hydrocarbon groups having an ether bond in the group.

Accordingly, examples of the epoxy group-containing monomer having the substituent (9) represented by the formula (3) include compounds represented by the following formulas (13) to (15). it can.

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In the above formula (13), R ₇ and R
₈ is each independently a hydrogen atom or a methyl group,
N in the formulas (13) and (14) is an integer in the range of 0 to 12.

Examples of the monomer represented by the above formula (13) include, for example, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, ethylene glycol-2,3-epoxypropyl- 2 ', 3'-epoxy-2'-methylpropyl ether, diethylene glycol-2,3-
Epoxypropyl-2 ', 3'-epoxy-2'-methylpropylether and the like can be mentioned.

Examples of the monomer represented by the above formula (14) include 2-methyl-1,2,3,4-diepoxybutane, 2-methyl-1,2,4,5-diepoxypentane, 2-
Methyl-1,2,5,6-diepoxyhexane and the like can be mentioned.

The monomer represented by the above formula (15) includes, for example, hydroquinone-2,3-epoxypropyl-
2 ', 3'-epoxy-2'-methylpropyl ether, catechol-2,3-epoxypropyl-2', 3'-epoxy-
2'-methylpropyl ether and the like can be mentioned.

Among the above epoxy group-containing monomers,
In particular, 2,3-epoxypropyl-2 ', 3'-epoxy-2'
-Methylpropyl ether, ethylene glycol-2,3
-Epoxypropyl-2 ', 3'-epoxy-2'-methylpropylether and the like are preferred.

In the production of the multi-component polyether copolymer, as the monomer components, those represented by the formulas (3) or (4) as well as those represented by the formulas (1) and (2) are used. Thereby, a polyether multi-component copolymer having a reactive group in a molecule can be obtained, and such a polyether multi-component copolymer is formed into a crosslinked product by utilizing the reactivity of the reactive group. be able to.
When obtaining such a crosslinked product, if necessary, a polyfunctional crosslinking auxiliary having a reactive group can be used in combination,
By using such a crosslinking aid, a crosslinking reaction of a polyether multi-component copolymer having a reactive group-containing monomer component unit in a molecule, that is, the formation of a cross-linked product of a polyether multi-component copolymer is promoted. Can be.

The adhesive porous membrane according to the present invention has an adhesive property by itself, and has a thickness of 180 mm at a width of 20 mm.
° Peel adhesion is 2N or more. In the present invention, the upper limit of the adhesive force of the adhesive porous film is not particularly limited, but is 180 ° at the above-mentioned 20 mm width.
The peel strength is usually 20N.

Accordingly, after laminating or winding such an adhesive porous membrane with an electrode to form a porous membrane-electrode structure in which the electrode is adhered to the porous membrane, the porous membrane-electrode structure is formed on a battery or a capacitor. When assembling batteries and the like, as described later, an electrolyte solution obtained by dissolving an electrolyte salt in an organic solvent is brought into contact therewith to swell the polymer and form a polymer gel electrolyte, as described later. Since the surface pressure between the electrodes can be increased uniformly, the distance between the electrodes can be easily maintained constant, and thus a battery or the like having excellent characteristics can be obtained.

The ion-conductive adhesive porous membrane according to the present invention comprises the above-mentioned polymer, preferably the above-mentioned polyether multi-component copolymer, and an electrolyte salt supported on the above-mentioned porous membrane. As in the case of the adhesive porous membrane, the adhesive itself has a 180 ° peeling adhesive strength of 2 N or more in a width of 20 mm.

Such an ion-conductive adhesive porous membrane is preferably prepared by dissolving an electrolyte salt together with the above-mentioned polymer in an appropriate solvent, usually an organic solvent, and applying the obtained coating solution to a substrate porous membrane. It can be obtained by coating or immersing the substrate porous membrane in a coating liquid, followed by heating and drying to remove the organic solvent.

In the present invention, the organic solvent is not particularly limited as long as it dissolves the electrolyte salt together with the polymer and does not dissolve the porous substrate membrane.
For example, methyl alcohol, ethyl alcohol, acetonitrile, propionitrile, benzene, toluene, dimethyl carbonate, diethyl carbonate, propylene carbonate, ethyl methyl carbonate, γ-butyrolactone, diethyl ether, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, N- Methyl-2-pyrrolidone and the like, and an arbitrary mixed solvent thereof are preferably used.

According to the present invention, the amount of the electrolyte salt to be supported on the porous base material membrane is usually preferably 1 to 100 parts by weight based on 100 parts by weight of the polymer. 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 supported electrolyte salt is the above-mentioned polymer 100.
Usually, the ratio is preferably 1 to 100 parts by weight with respect to parts by weight.

In the present invention, in order to obtain an ion-conductive adhesive porous membrane, the electrolyte salt supported on the substrate porous membrane is not particularly limited. It may be appropriately selected depending on the required properties and applications of the polymer gel electrolyte according to the present invention obtained from the membrane. For example, alkali metals such as hydrogen, lithium, sodium and potassium; alkaline earth metals such as calcium and strontium; A quaternary or quaternary ammonium salt as a cationic component, and an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, borofluoric acid, hydrofluoric acid, hexafluorophosphoric acid, perchloric acid, or a carboxylic acid, or an organic sulfone Examples thereof include salts containing an acid or an organic acid such as a fluorine-substituted organic sulfonic acid as an anion component.

In the present invention, among the above-mentioned electrolyte salts, the electrolyte salt containing an alkali metal ion as a cation component and an inorganic acid or an organic acid, particularly, trifluoroacetic acid or an organic sulfonic acid as an anion component, is used as the electrolyte salt. Is preferred. As such an electrolyte salt, for example, lithium perchlorate, sodium perchlorate, alkali metal perchlorate such as potassium perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, potassium tetrafluoroborate and the like Alkali metal tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate, alkali metal hexafluorophosphate such as potassium hexafluorophosphate, alkali metal trifluoroacetate such as lithium trifluoroacetate, lithium trifluoromethanesulfonate And alkali metal trifluoromethanesulfonate.

Since the ion-conductive adhesive porous membrane according to the present invention also has an adhesive property by itself, it is laminated or wound with an electrode to form a porous membrane having the electrode adhered to the porous membrane. After forming the electrode structure, as described above, by incorporating this into a work-in-progress such as a battery and a capacitor to form a polymer gel electrolyte, the same as described for the adhesive porous membrane is excellent. A battery or the like having excellent characteristics can be obtained.

The polymer gel electrolyte according to the present invention comprises a porous base material,
It is composed of the polymer swollen with an organic solvent, and the electrolyte salt supported on the substrate porous membrane together with the polymer, and at least a part of the electrolyte salt is dissolved in the organic solvent. Is preferred. In particular, according to the present invention, the polymer preferably has a crosslinked structure, that is, a crosslinked product.

According to the present invention, such a polymer gel electrolyte can be obtained from the above-mentioned adhesive porous membrane or ion-conductive adhesive porous membrane by various methods.

That is, according to the first method, after the polymer is supported on the porous base material membrane (that is, after the adhesive porous membrane is obtained), the electrolyte salt is dissolved and the polymer is swollen. A polymer gel electrolyte can be obtained by bringing an electrolytic solution comprising the organic solvent to be made and the electrolyte salt into contact with the adhesive porous membrane.

According to a second method, the polymer and the first
After the electrolyte salt is supported on the porous base material membrane (that is, after the ion-conductive adhesive porous membrane is obtained), the organic solvent that swells the polymer and the second electrolyte that dissolves in the organic solvent A polymer gel electrolyte can be obtained by bringing the salt-containing electrolytic solution into contact with the ion-conductive adhesive porous membrane.

In obtaining the polymer gel electrolyte according to the present invention by the first or second method, the electrolyte salt used for preparing the electrolyte is not particularly limited. What is necessary is just to select suitably from what is carried by a base material porous membrane in order to obtain a porous membrane.

Further, according to the first or second method,
In obtaining the polymer gel electrolyte according to the present invention, the organic solvent used for the preparation of the electrolytic solution dissolves the electrolyte salt used and can swell the polymer used. Aprotic organic solvents are preferred, and specific examples include, for example, ethylene carbonate, propylene carbonate, butylene carbonate, cyclic esters such as γ-butyrolactone,
Tetrahydrofuran, ethers such as dimethoxyethane, dimethyl carbonate, chain esters such as diethyl carbonate can be mentioned, and these alone,
Alternatively, it is used as a mixture of two or more.

Further, in the above first or second method,
The concentration of the electrolyte salt in the electrolytic solution is not particularly limited, but is usually in the range of 0.05 to 3 mol / L, preferably in the range of 0.1 to 2 mol / L.

In the second method, the first electrolyte salt is supported on the porous base material membrane 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 carried on the ion-conductive adhesive porous membrane. Here, the first electrolyte salt and the second electrolyte salt are supported.
The electrolyte salt is not particularly limited. For example, in order to obtain the above-described ion-conductive adhesive porous membrane, the electrolyte salt may be appropriately selected from those supported on the substrate porous membrane. Further, the first and second electrolyte salts may be the same or different.

According to the third method, after the polymer and the electrolyte salt are supported on the porous base material membrane (that is, after the ion-conductive adhesive porous membrane is obtained), the electrolyte salt is dissolved. Contacting the organic solvent that swells the polymer with the ion-conductive adhesive porous membrane to swell the polymer, and preferably dissolves at least a portion of the electrolyte salt in the organic solvent. By
A polymer gel electrolyte can be obtained.

That is, in the third method, only the organic solvent for this electrolyte is brought into contact with the ion-conductive adhesive porous membrane instead of the electrolyte used in the second method, and the electrolyte salt is used as the electrolyte salt. First, in order to obtain an ion-conductive adhesive porous membrane, only the one supported on the base porous membrane 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, 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. According to the second method,
A polymer gel electrolyte having high ionic conductivity can be easily obtained in a short time.

Furthermore, a preferred polymer gel electrolyte according to the present invention is a porous base material membrane and the polyether multi-component copolymer supported on the base material porous membrane and swelled with an organic solvent. And the electrolyte salt supported on the substrate porous membrane together with the crosslinked product of the polyether multi-component copolymer, and at least a part of the electrolyte salt is contained in the organic solvent. Preferably, it is dissolved.

As described above, such a crosslinked product of a multi-component polyether copolymer is represented by the formula (3) or (4) together with the monomer component represented by the formula (1) or (2). The reactive group-containing monomer component thus obtained is copolymerized. Thus, a polyether copolymer having the formulas (5) and (6) as the repeating structural units and the formula (7) or the formula (8) is used. A polymer was obtained, and this formula (7) or (8)
It can be obtained by cross-linking a polyether multi-component copolymer using a substituent containing an ethylenically unsaturated group, a reactive silicon-containing substituent, or an epoxy group in the repeating structural unit of the formula.

Thus, according to the present invention, by imparting a cross-linked structure to the polyether multi-component copolymer supported on the porous base material membrane, the mechanical strength of the obtained polymer gel electrolyte is further improved. In addition, the resulting polymer gel electrolyte has an area heat shrinkage reduced by 10% or more as compared with the porous substrate membrane itself. Specifically, although it depends on the amount of the polyether multi-component copolymer with respect to the organic solvent used for producing the polymer gel electrolyte, the area heat shrinkage is usually 10 to 7 as compared with the base porous film itself.
It is reduced in the range of 0%.

The production of a crosslinked product of a polyether multi-component copolymer will be described below.

First, when the ethylenically unsaturated group is used to obtain a crosslinked product of a polyether multi-component copolymer, a thermal polymerization using a radical polymerization initiator selected from organic peroxides, azo compounds and the like is used. Polymerization or photopolymerization using active energy rays such as ultraviolet rays and electron beams can be used.

As the organic peroxide, conventionally known ones such as ketone peroxide, peroxyketal, hydroperoxide, dialkyl peroxide, diacyl peroxide and peroxyester are 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-butylcumyl 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-butylperoxyisopropyl carbonate and the like. Such organic peroxides
Although it depends on the type, it is usually used in the range of 0.01 to 10% by weight of the polyether multi-component copolymer.

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'-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'-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-cyano Herbic acid), 2,2′-azobis [2-hydroxymethyl) propionitrile] and the like.

Such azo compounds are usually from 0.01 to 10 of a polyether multi-component copolymer, though depending on the kind thereof.
It is used in the range of weight%.

In the production of a crosslinked product utilizing an unsaturated group possessed by the polyether multi-component copolymer, when irradiating with active energy rays such as ultraviolet rays, as a sensitizing 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-propyl) ketone, 2,2-dimethoxy-1,2-
Acetophenones such as diphenylethane-1-one, 1-hydroxycyclohexylphenyl 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]
Benzophenones such as benzenemethanaminium bromide and (4-benzoylbenzyl) trimethylammonium chloride; thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone and 2,4-dichlorothioxanthone; Azidopyrene, 3-sulfonylazidebenzoic acid, 4
-Sulfonyl azidobenzoic acid, 2,6-bis (4'-azidobenzal) cyclohexanone-2,2'-disulfonic acid (sodium salt), p-azidobenzaldehyde, p-azidoacetophenone, p-azidobenzoic acid, p-azido Benzalacetophenone, 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 , 1,3
Azides such as -bis (4'-azidocinnasiliden) -2-propanone and the like are appropriately used.

As monomer components suitable for crosslinking by irradiation with active energy rays such as ultraviolet rays, for example, glycidyl ether acrylate, glycidyl ether methacrylate, glycidyl ether cinnamate and the like are particularly preferable.

As described above, in order to obtain a crosslinked product of the polyether multicomponent copolymer, the ethylenically unsaturated group itself may be crosslinked, and if necessary, a crosslinking aid may be used. The polyether multi-component copolymer may be crosslinked.

Examples of the crosslinking aid include ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, oligopropylene glycol diacrylate, Oligopropylene glycol dimethacrylate, 1,3-butylene glycol diacrylate, 1,4
-Butylene glycol diacrylate, 1,3-glycerol dimethacrylate, 1,1,1-trimethylolpropane dimethacrylate, 1,1,1-trimethylolethanediacrylate, pentaerythritol trimethacrylate, 1,2,6-hexane Triacrylate, sorbitol pentamethacrylate, methylenebisacrylamide,
Methylenebismethacrylamide divinylbenzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, triallyl cyanyl sulfide, divinyl ether, divinyl sulfo ether, diallyl phthalate, glycerol trivinyl ether, allyl methacrylate, allyl ac Rate, diallyl maleate, diallyl fumarate, diallyl itaconate, methyl methacrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, ethylene glycol acrylate, triallyl isocyanurate, maleimide, phenylmaleimide, p-quinone dioxime , Maleic anhydride, itaconic acid and the like can be optionally used.

In order to obtain a crosslinked product of the polyether multi-component copolymer by utilizing the reactive silicon-containing group of the polyether multi-component copolymer, a reaction between the reactive silicon group and water may be used. In order to enhance the reactivity of the reactive silicon-containing group, tin compounds such as dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, tin octylate, dibutyltin acetylacetonate, tetrabutyl titanate, tetrapropyl titanate, etc. Titanium compound, aluminum trisacetylacetonate,
Organometallic compounds such as aluminum compounds such as aluminum trisethyl acetoacetate and diisopropoxyaluminum ethyl acetoacetate, or butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine And amine compounds such as cyclohexylamine, benzylamine, diethylaminopropylamine, guanine, diphenylguanine and the like may be used as catalysts.

When a crosslinked product of a polyether multi-component copolymer is obtained by utilizing an epoxy group of the polyether multi-component copolymer, polyamines, acid anhydrides and the like are used.

Examples of polyamines include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine, N-aminoethylpiperazine, bis (amino Propylpiperazine), aliphatic polyamines such as trimethylhexamethylenediamine, isophthalic dihydrazide, 4,4-diaminodiphenyl ether, diaminodiphenylsulfone, m
-Phenylenediamine, 2,4-toluylenediamine, m
-Aromatic polyamines such as -toluylenediamine, o-toluylenediamine and xylylenediamine.

Such polyamines are usually from 0.01 to 1 of polyether multi-component copolymer, though depending on the kind.
It is used in the range of 0% by weight.

Examples of the acid anhydrides include maleic anhydride, dodecenyl succinic anhydride, chlorendexic anhydride, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, Examples thereof include tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and trimellitic anhydride.

Such acid anhydrides are usually from 0.01 to 10 of the polyether multi-component copolymer, though depending on the kind thereof.
It is used in the range of weight%.

According to the present invention, a cross-linking accelerator may be used in obtaining a cross-linked polyether multi-component copolymer. As an accelerator in the crosslinking reaction of polyamines,
For example, phenol, cresol, resorcinol, pyrogallol, nonylphenol, 2,4,6-tris (dimethylaminomethyl) phenol and the like can be mentioned. Accelerators for the crosslinking reaction of acid anhydrides include, for example, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminoethyl) phenol, dimethylaniline, 2-ethyl- 4
-Methylimidazole and the like. Such an accelerator is usually used as a crosslinking agent, although it depends on its type.
It is used in the range of 01 to 10% by weight.

In the present invention, the means and method for crosslinking the polyether multi-component copolymer are not limited to those exemplified above. According to the present invention, the polymer gel electrolyte described above can be obtained, for example, as follows.

For example, in the first, second or third method described above, the polyether multi-component copolymer (and the electrolyte salt) may be used.
In addition, if necessary, a crosslinking aid or a sensitizing aid is carried on the porous film, and the obtained adhesive porous film or ion-conductive adhesive porous film is treated with an organic solvent or an electrolytic solution as described above. And after swelling the polyether multi-component copolymer, further heating, or irradiating an active energy ray, etc., performing necessary treatments according to the desired crosslinking method,
By crosslinking this polyether multicomponent copolymer, a polymer gel electrolyte containing a crosslinked product of the polyether multicomponent copolymer as a polymer component can be obtained.

As another method, a polyether multi-component copolymer (and an electrolyte salt) is supported on a porous membrane to obtain an adhesive porous membrane or an ion-conductive adhesive porous membrane.
To this, if necessary, an organic solvent or an electrolytic solution in which a crosslinking aid or a sensitizing aid is dissolved is brought into contact, and after swelling the polyether multi-component copolymer, it is further heated or activated. By subjecting the polyether multi-copolymer to cross-linking by performing necessary treatments such as irradiation with energy rays according to the desired cross-linking method, a cross-linked polyether multi-copolymer can be used as a polymer component. A molecular gel electrolyte can be obtained.

The adhesive porous membrane having adhesiveness by itself or the ion-conductive adhesive porous membrane according to the present invention can be used for batteries,
It can be advantageously used for manufacturing 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 on an electrode, or the laminate is wound, and the electrode is adhered to the porous membrane. After impregnating such a porous membrane-electrode structure with the organic solvent or the electrolytic solution to produce a work-in-progress such as a battery and a capacitor, and incorporating the same into an appropriate exterior body and sealing the same, After assembling the membrane-electrode structure into an appropriate exterior body, the organic solvent or the electrolytic solution is injected into the exterior body, and the polymer gel electrolyte is formed on the spot, in other words, by a method such as sealing. Thus, a battery, a capacitor and the like using the polymer gel electrolyte according to the present invention can be obtained.

[0142]

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

(Thickness) The thickness was determined based on a 1 / 10,000 mm thickness gauge measurement and a 10000-fold scanning electron micrograph of the cross section of the porous substrate film.

(Porosity) The unit area S (c) of the porous substrate film
The weight W (g) per m ² ), the average thickness t (cm), and the density d (g / cm ³ ) of the resin constituting the porous base material membrane were calculated by the following formula. Porosity (%) = (1− (100 W / S / t / d)) × 1
00

(Air permeability) Measured in accordance with JIS P 8117.

(Piercing Strength) A piercing test was performed 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 piercing strength per 25 μm of the film thickness was determined. The needle is 1.
0mm, the radius of curvature of the tip is 0.5mm, 2cm
Per second.

(Analysis of Polyether Multicomponent Copolymer) The analysis of the polyether multicomponent copolymer was carried out as follows.

The glass transition temperature and the heat of fusion were measured using a differential scanning calorimeter (DSC8230B, manufactured by Rigaku Corporation) in a nitrogen atmosphere, in a temperature range of -100 to 80 ° C., and at a heating rate of 10 ° C.
/ Min.

The monomer-converted composition of the polyether multi-component copolymer was determined from the proton NMR spectrum.

The molecular weight of the polyether multi-component copolymer was measured by gel permeation chromatography.
The weight average molecular weight was calculated by standard polystyrene conversion. Gel permeation chromatography measurement
Using a measuring device RID-6A manufactured by Shimadzu Corporation, column "Showdex" KD-80 manufactured by Showa Denko KK
7, KD-806, KD-806M and KD-803,
Performed at 60 ° C. using the solvent dimethylformamide.

(Measurement of Conductivity) The conductivities of the polymer gel electrolytes produced in the examples and the porous membranes immersed in the electrolyte in the comparative examples were determined by sandwiching them between platinum electrodes and measuring the voltage at a temperature of 25 ° C. It was calculated by the complex impedance method using an AC method of 0.5 V and a frequency range of 5 Hz to 1 MHz.

(Measurement of Area Heat Shrinkage) The area heat shrinkage of the polymer gel electrolyte was measured as follows. First, a polyether multi-component copolymer, a cross-linking agent, a polymerization initiator and an electrolyte salt are dissolved in an organic solvent so that they have the same composition ratio as those supported on the base porous film in each example. A polyether multi-component copolymer solution was prepared. Next, on the glass plate, the same substrate porous membrane used in each example was placed in an enclosure surrounded by a spacer having a thickness of 50 μm, and the polyether multi-component copolymer solution was placed in the enclosure. After the injection, another glass plate was put on the spacer, and the porous substrate was dipped in the polyether multi-component copolymer solution between the two glass plates. In this state, the mixture was heated at 100 ° C. for 3 hours to crosslink the polyether multi-component copolymer, and then heat-treated at 120 ° C. for 1 hour. The area S of the polymer gel electrolyte after the heat treatment is compared with the area S ₀ before the heat treatment, and the area heat shrinkage R of the polymer gel electrolyte R = ((S−S ₀ ) / S ₀ ) × 100.
(%) Was determined.

Separately, an electrolyte salt is dissolved in an organic solvent,
Prepare an electrolytic solution having the same composition ratio as used in each example.
Was. Next, on a glass plate, surround with a 50 μm thick spacer.
The same substrate porosity as used in each example
After placing the electrolyte membrane and injecting the electrolyte into the enclosure,
A glass plate is placed on the spacer, and these two
Immerse the substrate porous membrane between the glass plates in the above electrolyte, and
Was heated at 120 ° C. for 1 hour. This heat treatment
Area A of the base material porous membrane after and area A before the heat treatment ₀And
In comparison, the area heat shrinkage r of the substrate porous membrane r = ((A-A
₀) / A₀) × 100 (%).

The thermal contraction rate suppression rate G of the polymer gel electrolyte is
G = ((r−R) / r) × 100, based on the shrinkage ratio r of the above-mentioned porous film of the base material alone and the heat shrinkage ratio R of the polymer gel electrolyte.
(%).

Reference Example 1 (Production Example of Catalyst) 10 g of tributyltin chloride and 35 g of tributyl phosphate were placed in a three-necked flask equipped with a stirrer, a thermometer and a distillation apparatus, and stirred at 250 ° C. under a nitrogen stream at 20 ° C. After heating for 1 minute, the distillate was distilled off to obtain a solid condensed substance as a residue. In the following, this organotin-phosphate ester condensate was used as a catalyst.

(Production of Polyether Multi-Polymer) The inside of a 3 L glass four-necked flask was purged with nitrogen, and the organotin-phosphate ester condensate was used as a catalyst.
The following formula (16) adjusted to 0.3 g and water 10 ppm or less.

[0157]

Embedded image

Glycidyl ether compound 30 represented by the following formula:
0 g, allyl glycidyl ether 15 g and solvent n-hexane 2000 g, and ethylene oxide 75
g of the glycidyl ether compound was sequentially added while monitoring the polymerization rate of the glycidyl ether compound by gas chromatography. The polymerization reaction was stopped with methanol. After completion of the polymerization reaction, the resulting polymer was taken out by decantation, and then dried under normal pressure at 40 ° C. for 24 hours, and further under reduced pressure at 45 ° C. for 10 hours to obtain an allyl glycidyl ether component as a reactive monomer component. 340 g of a polymer having the same were obtained. The polyether multi-component copolymer thus obtained had a glass transition temperature of -70 ° C. and a weight average molecular weight of 1.25 × 10 ^{6 as} measured by gel permeation chromatography. There was no heat of fusion. Also, proton NMR
The monomer-converted composition of this polyether multi-component copolymer in the spectrum is the above-mentioned glycidyl ether compound (1
6): ethylene oxide: allyl glycidyl ether =
49: 51: 1 mol%.

Example 1 The above polyether multi-component copolymer 2.0 prepared in Reference Example 1
g and 0.110 g of a crosslinking agent diethylene glycol dimethacrylate (Blenmer PDE-100 manufactured by NOF CORPORATION) and 0.020 g of a polymerization initiator benzoyl peroxide were dissolved in 17.9 g of toluene to prepare a coating solution.

A base porous film (25 μm thick) made of ultra high molecular weight polyethylene resin (weight average molecular weight 2.0 × 10 ⁶ )
m, porosity 40%, average pore size 0.05 μm, air permeability 500
A needle penetration strength of 7.0 N per second / 100 mL, 25 μm) was fixed on a glass plate, and the above-mentioned coating solution was applied to the substrate porous membrane with a doctor blade, and then heated to 80 ° C. The solvent toluene was removed to obtain an adhesive porous membrane carrying the polyether multi-component copolymer. This adhesive porous membrane had adhesiveness by itself, and had a 180 ° peeling adhesive strength of 10 N / 20 mm width.

The above-mentioned adhesive porous membrane was immersed in a mixture of ethylene carbonate / ethyl methyl carbonate (volume ratio: 1/2, hereinafter referred to as electrolyte) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 5 minutes. Then, after swelling the polyether multi-component copolymer, sandwiched between two glass plates, heated in an inert gas atmosphere at 100 ° C. for 3 hours to cross-link the polyether multi-component copolymer, and thus, A polymer gel electrolyte containing a crosslinked product of a polyether multi-component copolymer as a polymer component was obtained. The conductivity of the polymer gel electrolyte was 8.0 × 10 ⁻⁴ S / cm at 25 ° C.

In the polymer gel electrolyte, the amount of the polyether multi-component copolymer supported on the porous base material film was 2.
0 mg / cm ² , and the carrying amount of the electrolyte was 17.5 m
was g / cm ^2. The weight ratio of the electrolyte solution in the polymer gel electrolyte excluding the porous substrate membrane was 89.7%.

Therefore, the same polyether multi-component copolymer, cross-linking agent and polymerization initiator as described above were added in a weight ratio of 2 / 0.1 / 0.02.
The above solution was dissolved in the above electrolyte solution to prepare a polyether multi-component copolymer solution having a weight ratio of the electrolyte solution of 89.7%. The area heat shrinkage of the polymer gel electrolyte according to the example was 13%. Separately, the area thermal shrinkage of the porous substrate film was measured using the same electrolytic solution as described above and found to be 20%. Therefore, the heat shrinkage suppression rate of the polymer gel electrolyte of this example was 35%.

Example 2 The polyether multi-component copolymer 2.0 prepared in Reference Example 1 was prepared.
g and a crosslinking agent diethylene glycol dimethacrylate (Nippon Oil & Fats Co., Ltd. Blenmer PDE-100) 0.10 g and a polymerization initiator benzoyl peroxide 0.020 g were dissolved in acetonitrile 17.9 g to prepare a coating solution. Then, lithium perchlorate was added to this coating solution so that the weight ratio of polyether multi-component copolymer / lithium perchlorate was 100/15.

A porous base film made of the same ultrahigh molecular weight polyethylene resin as in Example 1 was fixed on a glass plate, and the coating liquid was applied to the porous base material film with a doctor blade. The mixture was heated to ℃ and the solvent acetonitrile was removed to obtain an ion-conductive adhesive porous membrane supporting the polyether multi-component copolymer and lithium perchlorate.
This ion-conductive adhesive porous membrane has adhesiveness by itself, and has a 180 ° peeling adhesive strength of 7.0 N / 20 mm.
It was width.

Next, the ion-conductive adhesive porous material was mixed with an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2, hereinafter referred to as an electrolyte) in which lithium perchlorate was dissolved at a concentration of 1 mol / L. After dipping the membrane for 5 minutes to swell the polyether multi-component copolymer,
Sandwiched between two glass plates, in an inert gas atmosphere, 100
The mixture was heated at 3 ° C. for 3 hours to crosslink the polyether multi-component copolymer, thus obtaining a polymer gel electrolyte containing a cross-linked polyether multi-component copolymer as a polymer component. The conductivity of this polymer gel electrolyte was 8.8 × 1 at 25 ° C.
It was 0 ^-4 S / cm.

In this polymer gel electrolyte, the polyether multi-component copolymer and the electrolyte salt carried on the porous base material membrane were 2.5 mg / cm ² , and the electrolyte solution carried on the porous membrane was 1.8. It was 1 mg / cm ² . The weight ratio of the electrolyte solution in the polymer gel electrolyte excluding the base material porous membrane was 87.9%.

Therefore, the same polyether multi-component copolymer, cross-linking agent and polymerization initiator as described above were used in a weight ratio of 2 / 0.1 / 0.02.
To prepare a polyether multi-component copolymer solution in which the weight ratio of this electrolyte solution is 87.9%, and using this solution, this embodiment was determined as described above. The area thermal shrinkage of the polymer gel electrolyte according to the example was 12%. Separately, the area thermal shrinkage of the porous substrate film was measured using the same electrolytic solution as described above and found to be 20%. Accordingly, the thermal shrinkage suppression rate of the polymer gel electrolyte of this example was 40%.

Example 3 In Example 1, a porous film made of polytetrafluoroethylene resin (film thickness: 20 μm,
Porosity 70%, average pore diameter 1.0 μm, air permeability 200 sec / 1
Example 1 except that 00 mL and a needle penetration strength of 3 N) were used.
In the same manner as in, an adhesive porous film having adhesiveness by itself and peeling at 180 ° and having an adhesive force of 6.0 N / 20 mm width was obtained.

The above-mentioned adhesive porous membrane was immersed in a mixture of ethylene carbonate / ethyl methyl carbonate (volume ratio 1/2, hereinafter referred to as electrolyte) in which lithium perchlorate was dissolved at a concentration of 1 mol / L for 5 minutes. After swelling the polyether multi-component copolymer supported on the base porous membrane,
Sandwiched between two glass plates, in an inert gas atmosphere, 100
The mixture was heated at 3 ° C. for 3 hours to crosslink the polyether multi-component copolymer, thus obtaining a polymer gel electrolyte containing a cross-linked polyether multi-component copolymer as a polymer component. The conductivity of this polymer gel electrolyte was 2.0 × 1 at 25 ° C.
It was 0 ^-3 S / cm.

In the polymer gel electrolyte, the amount of the polyether multi-component copolymer supported on the porous base material film was 2.
3 mg / cm ² , and the carrying amount of the electrolyte was 18.5 m
was g / cm ^2. The weight ratio of the electrolytic solution in the polymer gel electrolyte excluding the porous substrate membrane was 88.9%.

Therefore, the same polyether multi-component copolymer, cross-linking agent and polymerization initiator as described above were used in a weight ratio of 2 / 0.1 / 0.02.
And dissolved in the above-mentioned electrolyte solution to prepare a polyether multi-component copolymer solution having a weight ratio of the electrolyte solution of 88.9%. The area thermal shrinkage of the polymer gel electrolyte according to the example was 6%. Separately, the area thermal shrinkage of the porous substrate film was measured using the same electrolytic solution as described above, and was found to be 8%. Therefore, the thermal shrinkage suppression rate of the polymer gel electrolyte of this example was 25%.

Comparative Example 1 A uniform slurry was prepared by mixing 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 at 40 ° C .: 59 cst). The mixture was charged in a kneader, heated and dissolved at a temperature of 160 ° C. for 1 hour, and kneaded. The obtained kneaded material is cooled to 0 ° C.
And rapidly cooled to obtain a 5 mm thick gel-like sheet. This sheet was rolled to a thickness of 0.8 mm at a temperature of 120 ° C by a heat press, and then vertically and horizontally at a temperature of 125 ° C.
The film was simultaneously biaxially stretched 5 × 3.5 times to obtain a rolled stretched film, which was immersed in heptane to extract and remove the liquid paraffin to obtain a porous film. This porous film was heat-treated at 130 ° C. for 20 minutes. The total stretching ratio was 77 times. The porous film thus obtained has no adhesiveness by itself and has a width of 1 mm at a width of 20 mm.
The peel strength at 80 ° C. was 0.

After the porous film 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 5 minutes, the conductivity was measured. At 25 ° C. was 9.3 × 10 ⁻⁴ S / cm.

[0175]

As described above, the adhesive porous membrane according to the present invention comprises a polymer selected from the group consisting of a substrate and a porous polymer, which has an adhesive force by itself and an electrolyte salt. By contacting an electrolytic solution dissolved in an organic solvent and swelling the polymer, a polymer gel electrolyte can be obtained, and the ion-conductive adhesive porous membrane according to the present invention is particularly selected. A polymer and an electrolyte salt are carried on a porous membrane, which has an adhesive force by itself, and a solvent that dissolves the electrolyte salt or an electrolyte solution containing the electrolyte salt is brought into contact with the polymer and the electrolyte. Then, a polymer gel electrolyte can be obtained.

Further, according to the present invention, a polyether multi-component copolymer having a monomer component having a reactive group is used as the polymer, and the polyether multi-component copolymer is utilized by utilizing the reactive group. By crosslinking,
A high-performance polymer gel electrolyte using this crosslinked product as a polymer component (matrix) can be obtained.

Further, since the adhesive porous membrane and the ion-conductive adhesive porous membrane according to the present invention have an adhesive force by themselves, for example, in the production of batteries, capacitors and the like, they are laminated with electrodes, or After winding and bonding 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 uniformly increased, and the distance between the electrodes can be kept constant.
Thus, a battery or the like having excellent characteristics can be obtained.

In particular, as described above, according to the present invention,
A polymer gel electrolyte in which a crosslinked product of a polyether multi-component copolymer is supported as a polymer component on a porous substrate membrane,
In addition to excellent strength, even in a high-temperature environment, the area heat shrinkage is reduced by at least 10% as compared with the porous base film, and is small, so that it can be advantageously used, for example, as a battery separator. .

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C09J 183/12 C09J 183/12 201/00 201/00 H01B 1/06 H01B 1/06 A 13/00 13 / 00 Z H01G 9/02 H01G 9/02 301 301 H01M 10/40 B 9/035 C08L 101: 00 9/038 H01G 9/02 311 H01M 10/40 9/00 301D // C08L 101: 00 301C (72 ) Inventor Yoshihiro Uetani 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Keisuke Kiti 1-2-1, Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Takashi Yamamura 1-1-2 Shimohozumi, Ibaraki-shi, Osaka Nitto Denko Corporation (72) Inventor Seiji Nakamura 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka Daiso Corporation (72) Inventor Masato Tabuchi 1-10-8 Edobori, Nishi-ku, Osaka-shi, Osaka F-term (reference) 4F074 AA16 AA17 AA24 AA38 CE16 CE43 CE56 CE66 DA02 DA08 DA09 DA10 DA22 DA49 4J004 AA10 AA11 CC07 4J040 DF021 EE1 EK031 EL041 JA09 LA09 NA19 5G301 CD01 5H029 AJ06 AJ11 AM02 AM03 AM05 AM07 AM16 CJ08 DJ04 EJ12 HJ00 HJ01 HJ02 HJ04 HJ09 HJ20

Claims (19)

[Claims] 1. A polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide),
A polymer having a polyphosphazene, polyvinyl ether or polysiloxane structure and having a chain oligoalkylene oxide structure in a side chain is supported on a porous base material film, and as such, 180 ° peeling at a width of 20 mm is performed. An adhesive porous membrane having an adhesive strength of 2N or more. 2. A polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide),
Polyphosphazene, having a polyvinyl ether or polysiloxane structure, a polymer having a chain oligoalkylene oxide structure in a side chain and an electrolyte salt are supported on a base porous film, and as such, in a 20 mm width, 180 °
An ion-conductive adhesive porous membrane having an adhesive strength with a peeling strength of 2N or more. 3. A polymer comprising polyethylene oxide in the main chain,
Polypropylene oxide or poly (ethylene oxide /
The adhesive porous membrane according to claim 1, which is a polyether having a (propylene oxide) structure and a chain oligoalkylene oxide structure in a side chain. 4. The adhesive material according to claim 1, wherein the 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 3 N or more per 25 μm. Porous membrane. 5. A porous base film having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain. A polymer having a chain oligoalkylene oxide structure in a chain, comprising a polymer supported on the above-described porous substrate and swelled with an organic solvent, and an electrolyte salt. Molecular gel electrolyte. 6. A porous substrate film, and as a monomer component, 1 to 99% by mole of a component represented by the following formula (1) and a component 99 represented by the following formula (2):
-1 mol%, and 0-20 mol% of the reactive group-containing component represented by the formula (3) or (4), and the repeating structural units are represented by the formulas (5) and (6), (5) and (6). ) And (7)
A polyether multi-component copolymer represented by any of the formulas (5), (6) and (8) and having a weight average molecular weight in the range of 10 ⁴ to 10 ⁷ , A polymer gel electrolyte comprising a polyether multi-component copolymer supported on a membrane and swollen with an organic solvent, and an electrolyte salt. Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image Embedded image (In the formulas (1) and (5), R and R '
Are each independently a hydrogen atom or a methyl group, R ₁ is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms,
It is a group selected from a cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms and an aralkyl group having 7 to 12 carbon atoms, and the degree of polymerization k of the oxyalkylene unit serving as a side chain portion is 1 to 12. It is. In the formulas (2) and (6), R ′
Is a hydrogen atom or a methyl group. In the formulas (3) and (7), R ′ is a hydrogen atom or a methyl group, and R ₂ is a substituent containing an ethylenically unsaturated group, a reactive silicon-containing substituent, or an epoxy group. Wherein R ₃ represents a reactive silicon-containing substituent in the formulas (4) and (8). (9) In the formula, A represents an organic residue. ) 7. The polymer gel electrolyte according to claim 6, wherein in the formula (1), R ₁ is a group selected from an alkyl group having 1 to 6 carbon atoms and an alkenyl group having 2 to 6 carbon atoms. 8. Among the reactive group-containing components represented by the formula (3), the ethylenically unsaturated group-containing monomer component is allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpinyl glycidyl ether, Hexenylmethyl glycidyl ether, p-vinylbenzyl glycidyl ether, allylphenyl glycidyl ether, vinyl glycidyl ether, 3,4-epoxy-
1-butene, 3,4-epoxy-1-pentene, 4,5-epoxy-2-pentene, 1,2-epoxy-5,9-cyclododecadiene, 3,4-epoxy-1-vinylcyclohexene, 1 The polymer according to claim 6, which is a monomer selected from 2,2-epoxy-5-cyclooctene, glycidyl acrylate, glycidyl methacrylate, glycidyl sorbate, glycidyl cinnamate, glycidyl crotonate, and glycidyl-4-hexenoate. Gel electrolyte. 9. An ionic conductivity at 25 ° C. of 1 × 10 ^-4
The polymer gel electrolyte according to any one of claims 5 to 8, which is at least S / cm. 10. A battery comprising the polymer gel electrolyte according to claim 5. 11. A capacitor using the polymer gel electrolyte according to claim 5. 12. A polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide),
Polyphosphazene, having a polyvinyl ether or polysiloxane structure, a polymer having a chain-like oligoalkylene oxide structure in the side chain is supported on the base porous film,
Producing a polymer gel electrolyte comprising an adhesive porous membrane, and contacting the adhesive porous membrane with an electrolytic solution comprising an organic solvent which dissolves the electrolyte salt and swells the polymer and the electrolyte salt. Method. 13. A polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide),
A polymer having a polyphosphazene, polyvinyl ether or polysiloxane structure and having a chain oligoalkylene oxide structure in a side chain and a first electrolyte salt are supported on a porous base material film to form an ion-conductive adhesive porous film. Membrane,
A method for producing a polymer gel electrolyte, comprising contacting an electrolytic solution comprising an organic solvent for swelling the polymer and a second electrolyte salt dissolved in the organic solvent with the ion-conductive adhesive porous membrane. 14. A polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide),
A polymer having a polyphosphazene, polyvinyl ether or polysiloxane structure, and a polymer having a chain oligoalkylene oxide structure in a side chain and an electrolyte salt are supported on a porous base material to form an ion-conductive adhesive porous membrane. A method for producing a polymer gel electrolyte, comprising contacting an organic solvent that dissolves the electrolyte salt and swells the polymer with the ion-conductive adhesive porous membrane. 15. The method for producing a polymer gel electrolyte according to claim 6, wherein the polyether multi-component copolymer is supported on a porous base material to form an adhesive porous film, and the electrolyte salt is dissolved therein. A method for producing a polymer gel electrolyte, comprising contacting an electrolytic solution comprising an organic solvent for swelling the polyether multicomponent copolymer and the electrolyte salt with the adhesive porous membrane. 16. The method for producing a polymer gel electrolyte according to claim 6, wherein the polyether multi-component copolymer and the first electrolyte salt are supported on a porous base material film to form an ion-conductive adhesive porous material. And contacting an electrolyte comprising an organic solvent for swelling the polyether multi-component copolymer and a second electrolyte salt dissolved in the organic solvent with the ion-conductive adhesive porous membrane. Of producing a high molecular gel electrolyte. 17. The method for producing a polymer gel electrolyte according to claim 6, wherein the polyether multicomponent copolymer and the electrolyte salt are supported on a porous base material film to form an ion-conductive adhesive porous film. A method for producing a polymer gel electrolyte, comprising contacting an organic solvent that dissolves the electrolyte salt and swells the polyether multicomponent copolymer with the ion-conductive adhesive porous membrane. 18. The polymer gel electrolyte according to claim 6, wherein the polyether multi-component copolymer is represented by the formula (7) or (8) as a repeating unit together with the formulas (5) and (6). A polymer gel electrolyte having any one of the formulas and being crosslinked. 19. The method according to claim 18, wherein the area heat shrinkage is reduced by 10% or more as compared with the porous film of the base material.
The polymer gel electrolyte according to item 1.