JP2011202186A - Method for producing polymer gel electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polymer gel electrolyte using an ionically conductive porous film having both ionic conductivity and strength, and also adhesion for itself.SOLUTION: The method for producing the polymer gel electrolyte includes the steps of: supporting a polymer having a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide/propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in a main chain and a chain oligoalkylene oxide structure in a side chain with a substrate porous film; then, crosslinking this polymer to obtain an adhesive porous film as a crosslinked product; and next bringing an electrolyte comprising an organic solvent for swelling the crosslinked product of the polymer and an electrolyte salt dissolved in this organic solvent in contact with the adhesive porous film.

Description

The present invention relates to a method for producing a polymer gel electrolyte.

In recent years, solid electrolytes widely used in electrochemical devices are substances having high ion conductivity in the solid state. Among them, polymer solid electrolytes using polymer substances as solids have recently been used as next-generation lithium ions. In particular, it is attracting attention as an electrolyte for secondary batteries, and research is being promoted worldwide. Such a polymer solid electrolyte has a high degree of freedom in its shape, such as no risk of liquid leakage and can be made into a thin film, as compared with a conventional electrolyte solution.

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 formed by combining 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. Nothing has been found with a conductivity above 10 ⁻³ S / cm at room temperature.

For example, according to a battery using such a conventional solid electrolyte, since the solid electrolyte has significantly lower ionic conductivity than the liquid electrolyte, the battery has a high internal resistance and performs practical charge / discharge. I can't. In addition, when the shape of the electrode changes due to charge / discharge, etc., the solid electrolyte cannot follow the change in the shape of the electrode, resulting in insufficient contact between the electrode and the electrolyte. It becomes impossible to discharge.

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

For example, a polymer gel electrolyte in which an organic electrolytic solution made of a mixed solvent of propylene carbonate and ethylene carbonate in which lithium perchlorate is dissolved is gelled with polyacrylonitrile to form a sheet has been proposed (see Non-Patent Document 1). . A polymer gel electrolyte composed of polyacrylonitrile, an electrolyte salt, and a nonaqueous solvent has been proposed (see Patent Document 1). Further, a polymer gel electrolyte using polyethylene oxide or polypropylene oxide as a polymer component and γ-butyrolactone as a solvent has been proposed (see Patent Document 2).

However, since such a polymer gel electrolyte has low strength, in order to form a film, the thickness has to be increased, and as a result, an electrode is provided with such a polymer gel electrolyte in between to provide a battery. If the assembly is assembled, the distance between the electrodes is large, the internal resistance becomes high, and sufficient charge / discharge cannot be performed.

Therefore, in order to solve the strength problem in such a conventional polymer gel electrolyte, a polymer substance capable of holding an electrolyte solution, such as a vinylidene fluoride-hexafluoropropylene copolymer and a polyolefin resin, can be used. A method is described in which a mixture with such a resin is heated, kneaded, formed into a sheet, stretched to form a porous membrane, impregnated with an electrolyte solution, and gelled to obtain a polymer gel electrolyte. (See Patent Document 3). Also, for example, fibers made of a gel-forming polymer that forms a gel with a non-aqueous (organic) solvent for forming a non-aqueous electrolyte such as propylene carbonate, ethylene carbonate, dimethoxyethane, etc., for example, polyacrylonitrile-acrylic acid A fiber structure composed of a methyl copolymer resin fiber and a fiber having resistance to the solvent, for example, a polyolefin fiber, is formed, and this is formed into a gel body with the non-aqueous solvent. A method for obtaining a gel electrolyte is described (see Patent Document 4).

In such a polymer gel electrolyte, the polymer gel electrolyte obtained by the polyolefin resin or polyolefin fiber, which is a so-called reinforcing material, has a relatively high strength even in a film shape, but obtains a practical strength. Therefore, it is necessary to use a relatively large amount of these reinforcing materials, and as a result, it is necessary to relatively reduce the blending ratio of the polymer substance or gel-forming polymer capable of holding the electrolyte solution. Therefore, in such a polymer gel electrolyte, these polymer substances and gel-forming polymers tend to form imperfect gel bodies, and as a result, there is an inherent advantage of the polymer gel electrolyte that there is no liquid leakage. In addition, the polymer gel electrolyte does not have complete integrity and continuity due to the presence of the reinforcing material, so that there is a problem that the ionic conductivity of the obtained polymer gel electrolyte is lowered. Of course, if the blending ratio of the polymer substance or gel-forming polymer that holds the electrolyte solution is increased, the resulting polymer gel electrolyte has high ionic conductivity, but the strength is weakened.

Furthermore, 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 stack type or an elliptical cross-section wound type, for example, as a separator, the surface pressure between the electrodes becomes non-uniform and the distance between the electrodes is constant. It may be difficult to maintain the distance between the electrodes, and the distance between the electrodes may be partially increased. Thus, in a battery, when the distance between electrodes is partially large, it is difficult to obtain excellent battery characteristics.

Japanese Patent Laid-Open No. 11-16579 Japanese Patent Laid-Open No. 08-298126 Japanese Patent Laid-Open No. 11-40128 JP 11-353935 A

J. Electrochem. Soc., Vol. 137, 1657-1658 (1990)

The present invention has been made in order to solve the above-described problems in conventional polymer gel electrolytes, and has both ion conductivity and strength, and itself has an ion conductivity porous property. It is an object of the present invention to provide a method for producing a polymer membrane, a porous membrane therefor, and a polymer gel electrolyte using them.

According to the present invention, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and the side chain has a chain oligoalkylene. Adhesive characterized in that a crosslinked polymer of a polymer having an oxide structure is supported on a porous substrate, and itself has an adhesive strength of 180 N peel-off at a width of 20 mm and an adhesive strength of 0.2 N or more. A porous membrane is provided.

Further, according to the present invention, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and the side chain has a chain shape. A cross-linked polymer having an oligoalkylene oxide structure and an electrolyte salt are supported on a porous substrate, and as such, has a 20 mm width 180 ° peeling adhesive strength of 0.2 N or more. An ion conductive adhesive porous membrane is provided.

Furthermore, according to the present invention, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and the side chain is a chain. After supporting the polymer having an oligoalkylene oxide structure on the base porous membrane, the polymer is cross-linked to obtain an adhesive porous membrane as a cross-linked body, and then an organic solvent that swells the cross-linked body of the polymer There is provided a method for producing a polymer gel electrolyte, characterized in that an electrolytic solution comprising an electrolyte salt dissolved in an organic solvent is brought into contact with the adhesive porous membrane.

Further, according to the present invention, as another method, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, After the polymer having the chain oligoalkylene oxide structure in the side chain and the first electrolyte salt are supported on the base porous membrane, the polymer is cross-linked to form an ion conductive adhesive porous membrane as a cross-linked body. And then contacting the ion conductive adhesive porous membrane with an electrolytic solution comprising an organic solvent for swelling the crosslinked polymer and a second electrolyte salt dissolved in the organic solvent. A method for producing a molecular gel electrolyte is provided.

In addition, according to the present invention, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and the side chain has a chain. After the polymer having an oligoalkylene oxide structure and an electrolyte salt are supported on the base porous membrane, the polymer is cross-linked to obtain an ion conductive adhesive porous membrane as a cross-linked body. There is provided a method for producing a polymer gel electrolyte, wherein an organic solvent that swells a crosslinked body is brought into contact with the ion-conductive adhesive porous membrane.

According to the present invention, in the adhesive porous membrane, the ion conductive adhesive porous membrane, and the polymer gel electrolyte as described above, according to the present invention, the polymer is, in particular, a repeat represented by the formula (1). 1 to 99 mol% of structural units, 99 to 1 mol% of repeating structural units represented by formula (2), and at least one kind selected from repeating structural units represented by formulas (3) and (4) It is preferably a polyether multi-component copolymer comprising 0 to 20 mol% of repeating structural units for crosslinking and having a weight average molecular weight in the range of 10 ⁴ to 10 ⁷ .

(In the above formula, in formula (1), R and R ′ each independently represent a hydrogen atom or a methyl group, and R ₁ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a carbon number. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, the degree of polymerization k of the side chain oxyalkylene unit is 1 to 12, and in formula (2) , R ′ represents a hydrogen atom or a methyl group, and in formula (3), R ′ represents a hydrogen atom or a methyl group, R ₂ represents an ethylenically unsaturated group, a reactive silicon-containing substituent, In the formula (4), R ₃ represents a reactive silicon-containing substituent, and in the formula (5), A represents an organic residue. .)

The adhesive porous membrane according to the present invention is obtained by supporting a crosslinked polymer of a selected polymer on a substrate porous membrane, having adhesive strength by itself, and dissolving an electrolyte salt in an organic solvent. The polymer gel electrolyte can be obtained by contacting the electrolyte solution to swell the crosslinked polymer, and the ion-conductive adhesive porous membrane according to the present invention is a crosslinked polymer of the selected polymer. And an electrolyte salt are carried on a porous membrane, and have an adhesive force by themselves. By contacting this with a solvent for dissolving the electrolyte salt or an electrolyte solution containing the electrolyte salt, A polymer gel electrolyte can be obtained.

In particular, according to the present invention, a polyether multi-component copolymer having a crosslinkable reactive group in the molecule is used as the polymer, and the polyether multi-component copolymer is crosslinked using the reactive group. By using a crosslinked body, a high-performance polymer gel electrolyte having such a crosslinked body as a polymer component can be obtained.

Here, the above-mentioned adhesive porous membrane and ion-conductive adhesive porous membrane according to the present invention have an adhesive force per se, and thus, for example, in the manufacture of batteries, capacitors, etc., they are laminated or wound with electrodes. Then, after the electrodes are adhered to these porous membranes to form a porous membrane-electrode structure, a polymer gel electrolyte is used to uniformly increase the surface pressure between the electrodes, thereby reducing the distance between the electrodes. Thus, a battery or the like having excellent characteristics can be obtained.

The adhesive porous membrane according to the present invention has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain and in the side chain. A crosslinked polymer of a polymer having a chain oligoalkylene oxide structure is supported on a porous substrate, and as such, it has an adhesive strength of 180 N with a 20 mm width and an adhesive strength of 0.2 N or more.

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

In the present invention, the substrate porous membrane has strength and electrolyte solution in consideration of using the polymer gel electrolyte finally obtained by using the porous membrane as a separator for batteries, capacitors and the like according to the present invention. In particular, polyolefin resins such as polyethylene resins and polypropylene resins including ultra high molecular weight polyethylene resins, and fluororesins are preferably used. .

Similarly, in the present invention, the substrate porous membrane is particularly limited in consideration of using the polymer gel electrolyte finally obtained by using it as a separator for a battery, a capacitor, etc. according to the present invention. Although not intended, the porosity is in the range of 30 to 95%, preferably 33 to 90%, particularly preferably 35 to 85%. When the porosity is too low, ion conduction paths are reduced. 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 membrane is not sufficient in strength, and in order to obtain a substrate porous membrane having sufficient strength, the film thickness must be increased. If the polymer gel electrolyte obtained is used as a battery separator, as described above, the internal resistance is increased.

Further, the base porous membrane has an air permeability of 1500 seconds / 100 mL or less, preferably 1000 seconds / 100 mL or less. When the air permeability is too high, the ionic conductivity of the obtained polymer gel electrolyte is lowered. For example, when the obtained polymer gel electrolyte is used as a battery separator, sufficient battery characteristics cannot be obtained. Furthermore, the base porous membrane preferably has a needle penetration strength of 3N or more. When the needle penetration strength is too low, when the resulting polymer gel electrolyte is used as a battery separator, the substrate porous membrane may break when an interfacial pressure is applied between the electrodes, causing an internal short circuit. is there.

According to the present invention, such a base porous membrane has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain. Then, after supporting a polymer having a chain oligoalkylene oxide structure in the side chain, the polymer is crosslinked by an appropriate means such as heating or irradiation with active energy rays to form a crosslinked product, whereby the polymer The cross-linked body is supported on the base porous membrane, and an adhesive porous membrane having adhesive strength by itself can be obtained.

Thus, in order to support the crosslinked polymer of the polymer on the substrate porous membrane, for example, the polymer is dissolved in an appropriate solvent, usually an organic solvent, together with a crosslinking assistant and a polymerization initiator as described later. The obtained coating solution is applied to the substrate porous membrane, or after immersing the substrate porous membrane in the coating solution, the polymer is crosslinked by means such as heating or irradiation with radiation. Thus, a crosslinked product is obtained, and then the organic solvent is removed.

According to the present invention, in order to form a crosslinked product of the polymer, an ethylenically unsaturated group, a reactive silicon-containing substituent, an epoxy group, Provide a crosslinkable reactive group containing a halogen atom, etc., and use a crosslinking assistant composed of a polyfunctional polymerizable monomer to bond the polymer chains to each other using such a crosslinkable reactive group. Thus, a crosslinked product is preferable.

However, according to the present invention, in the presence of the polymer, by polymerizing a crosslinking aid composed of a monofunctional polymerizable monomer, the polymer is graft-polymerized, or by polymerization of the crosslinking aid. A polymer chain is generated, and a structure in which the polymer chain from the crosslinking aid and the polymer chain penetrate each other can be obtained. According to the present invention, using the monofunctional crosslinking aid to make the polymer into such a structure is also included in the production of the crosslinked polymer.

Therefore, according to the present invention, even when the polymer does not have a crosslinkable reactive group in the molecule, the polymer chain is similarly formed from a crosslinking aid composed of a monofunctional polymerizable monomer. Thus, a structure in which the polymer chain from the crosslinking aid and the polymer chain are mutually penetrated can be formed, and three-dimensionality can be obtained by polymerization of the crosslinking aid comprising a polyfunctional polymerizable monomer. A network structure is generated, and the polymer chain is incorporated into the three-dimensional network structure, whereby a structure in which these two polymer chains penetrate each other can be obtained. According to the present invention, when the polymer forms such a structure, it is included in the production of the crosslinked body.

In the present invention, in the adhesive porous membrane, as a result of supporting the crosslinked polymer in the base porous membrane in this way, all the pores of the porous substrate membrane are filled with the crosslinked polymer. Shall also be included.

Further, according to the present invention, the base porous membrane has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure in the main chain. After supporting the polymer having an oligoalkylene oxide structure in the side chain and an electrolyte salt, the polymer is cross-linked by an appropriate means such as heating or irradiation with active energy rays to obtain a cross-linked product. The cross-linked polymer and the electrolyte salt are supported on the base porous membrane, and an ion-conductive adhesive porous membrane having adhesive strength by itself can be obtained.
Such an ion conductive adhesive porous membrane itself has an adhesive strength of 180 N peel-off at a width of 20 mm and 0.2 N or more, like the adhesive porous membrane.

Thus, in order to support the crosslinked body of the polymer and the electrolyte salt on the base porous membrane, for example, the polymer, the electrolyte salt, the crosslinking assistant, and the polymerization initiator are combined with an appropriate solvent, usually an organic solvent. The polymer is dissolved in the coating liquid, applied to the porous substrate film, or immersed in the coating liquid, and then heated or irradiated with radiation, etc. Is crosslinked to form a crosslinked product, and then the organic solvent is removed.

Furthermore, according to the present invention, in this way, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, After supporting a polymer having a chain oligoalkylene oxide structure in the side chain on the base porous membrane, this polymer is crosslinked to obtain an adhesive porous membrane as a crosslinked product, and then the crosslinked product of this polymer is obtained. A polymer gel electrolyte can be obtained by bringing an electrolytic solution composed of an organic solvent to be swollen and an electrolyte salt dissolved in the organic solvent into contact with the adhesive porous membrane.

In addition, it has 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. After the polymer is supported on the substrate porous membrane together with the first electrolyte salt, the polymer is crosslinked to obtain an ion conductive adhesive porous membrane as a crosslinked body, and then an organic solvent for swelling the polymer The polymer gel electrolyte can also be obtained by bringing the electrolytic solution composed of the second electrolyte salt dissolved in the organic solvent into contact with the ion conductive adhesive porous membrane.

Further, as another method, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and a side chain has a chain oligo After the polymer having an alkylene oxide structure is supported on the substrate porous membrane together with the electrolyte salt, the polymer is cross-linked to obtain an ion conductive adhesive porous membrane as a cross-linked body, and then the organic that swells the polymer. A polymer gel electrolyte can be obtained by bringing a solvent into contact with the ion conductive adhesive porous membrane.

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

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 is supported on the substrate porous membrane together with an electrolyte salt as necessary. The organic solvent used for dissolving the above polymer is not particularly limited as long as it dissolves the above polymer and further dissolves the electrolyte salt, while not dissolving 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, dimethyl sulfoxide, N -Methyl-2-pyrrolidone And, also, any mixture of these solvents are preferably used.

On the other hand, after the crosslinked polymer is supported on the substrate porous membrane (along with an electrolyte salt, if necessary), the crosslinked polymer is swelled (if necessary, an electrolyte salt is further added). The organic solvent used for obtaining the polymer gel electrolyte by being supported can swell the crosslinked polymer, and can dissolve the electrolyte salt when it is used. If the porous membrane is not dissolved, it is not particularly limited, but a non-aqueous solvent, particularly an aprotic organic solvent is preferably used. Specific examples of such non-aqueous organic solvents include, for example, cyclic esters such as ethylene carbonate, propylene carbonate, butylene carbonate, and γ-butyrolactone, ethers such as tetrahydrofuran and dimethoxyethane, and chain structures such as dimethyl carbonate and diethyl carbonate. An ester can be mentioned, These are used individually or as a mixture of 2 or more types.

When the electrolyte salt is dissolved in the organic solvent and used as an electrolyte, the concentration of the electrolyte salt in the electrolyte is not particularly limited, but is usually in the range of 0.05 to 3 mol / L. Yes, preferably in the range of 0.1 to 2 mol / L.

According to the present invention, in the ion conductive adhesive porous membrane, the electrolyte salt to be supported on the base porous membrane is usually preferably in a ratio of 1 to 100 parts by weight with respect to 100 parts by weight of the polymer. . As will be described later, 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 supported is usually 100 parts by weight of the polymer. The ratio is preferably 1 to 100 parts by weight.

In the present invention, in order to obtain an ion conductive adhesive porous membrane or a polymer gel electrolyte, the electrolyte salt supported on the base porous membrane is not particularly limited, and the ion conductive adhesive porous It may be appropriately selected depending on the required properties and applications of the membrane or the polymer gel electrolyte obtained therefrom. For example, alkali metals such as hydrogen, lithium, sodium and potassium, alkaline earth metals such as calcium and strontium, or tertiary Alternatively, a quaternary ammonium salt or the like as a cation component, and an inorganic acid such as hydrochloric acid, nitric acid, phosphoric acid, sulfuric acid, borofluoric acid, hydrofluoric acid, hexafluorophosphoric acid, perchloric acid, carboxylic acid, or organic sulfonic acid And salts containing an organic acid such as a fluorine-substituted organic sulfonic acid as an anionic component.

In the present invention, among the above-mentioned electrolyte salts, an electrolyte salt having an alkali metal ion as a cation component and an inorganic acid or an organic acid, and the latter having trifluoroacetic acid or an organic sulfonic acid as an anion component is particularly preferable. Examples of such electrolyte salts include alkali metal perchlorates such as lithium perchlorate, sodium perchlorate, and potassium perchlorate, lithium tetrafluoroborate, sodium tetrafluoroborate, and potassium tetrafluoroborate. Alkali metal tetrafluoroborate, lithium hexafluorophosphate, sodium hexafluorophosphate such as sodium hexafluorophosphate, alkali metal trifluoroacetate such as lithium trifluoroacetate, lithium trifluoromethanesulfonate Examples thereof include alkali metals such as trifluoromethanesulfonic acid.

According to the present invention, the main chain has a polyacrylate, polymethacrylate, polyethylene oxide, polypropylene oxide, poly (ethylene oxide / propylene oxide), polyphosphazene, polyvinyl ether or polysiloxane structure, and a side chain has a chain oligo Among polymers having an alkylene oxide structure, a polyether multi-component copolymer 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 is preferably used. It is done. 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 oligoethylenepropylene structure (in particular, A polyether multi-component copolymer having a chain oligoethylene structure or a chain oligopropylene structure, particularly the former) is preferably used.

Such polyether multi-component copolymers have already been disclosed in, for example, JP-A-63-154736, JP-A-9-324114, JP-A-10-130487, JP-A-10-176105, JP-A-10-176105. It is known as described in JP-A-10-204172.

The polyether multi-component copolymer that can be preferably used in the present invention is 1 to 99 mol% of the repeating structural unit represented by the formula (1) and 99 to 1 mol% of the repeating structural unit represented by the formula (2). And at least one repeating structural unit for crosslinking selected from the repeating structural units represented by the formulas (3) and (4) in a range of 10 ⁴ to 10 ^{7 in} weight average molecular weight. It is what is inside.

(In the above formula, in formula (1), R and R ′ each independently represent a hydrogen atom or a methyl group, and R ₁ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a carbon number. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, the degree of polymerization k of the side chain oxyalkylene unit is 1 to 12, and in formula (2) , R ′ represents a hydrogen atom or a methyl group, and in formula (3), R ′ represents a hydrogen atom or a methyl group, R ₂ represents an ethylenically unsaturated group, a reactive silicon-containing substituent, In the formula (4), R ₃ represents a reactive silicon-containing substituent, and in the formula (5), A represents an organic residue. .)

According to the present invention, such a polyether multi-component copolymer includes 1 to 98 mol% of the repeating structural unit (1) represented by the formula (1) and the repeating structural unit 98 represented by the formula (2). It is preferable to comprise 1 to 20 mol% of at least one repeating structural unit for crosslinking selected from repeating structural units represented by formula (3) and formula (4) together with ˜1 mol%. It is represented by Formula (3) and Formula (4) together with 2 to 95 mol% of the repeating structural unit (1) represented by 1) and 95 to 2 mol% of the repeating structural unit represented by Formula (2). It is preferably composed of 3 to 15 mol% of at least one repeating structural unit for crosslinking selected from repeating structural units.

In such a polyether multi-component copolymer, in the repeating structural unit represented by the above formula (1), R ′ represents a hydrogen atom or a methyl group, and in the oxyalkylene unit, each R is independently a hydrogen atom. Alternatively, each represents a methyl group, and each may be a hydrogen atom, all may be a methyl group, or some may be a hydrogen atom with the remainder being a methyl group. Therefore, the oxyalkylene unit may be an oxyethylene unit, an oxypropylene group unit, or an oxyethylenepropylene unit, but is preferably an oxyethylene unit or an oxypropylene unit, particularly an oxyethylene unit. . Furthermore, the degree of polymerization k of the oxyalkylene unit is preferably 1-12. When the value of the degree of polymerization k exceeds 12, the ionic conductivity of the resulting polymer gel electrolyte is lowered.

The molecular weight of the polyether multi-component copolymer used in the present invention is 10 ⁴ to 10 ⁷ , preferably 10 ⁵ to 10 in order to obtain processability, moldability, mechanical strength, and flexibility. It is preferably in the range of 5 × 10 ⁶ . If the weight average molecular weight is less than 10 ⁴ , sufficient ionic conductivity cannot be obtained. On the other hand, when it exceeds 10 ⁷ , a problem occurs in solubility. Furthermore, the glass transition temperature of the polyether multi-component copolymer is preferably −60 ° C. or lower.

Such a multi-component polyether copolymer used in the present invention may be either a block copolymer or a random copolymer, but reduces the crystallinity of a polymer main chain composed of polyalkylene oxide, preferably polyethylene oxide. Random copolymers are preferred because they are more effective.

Thus, according to the present invention, such a polyether multi-component copolymer is dissolved in an appropriate organic solvent as described above together with a crosslinking assistant and a polymerization initiator, and the resulting solution is formed into a substrate porous membrane. After contacting, heating or irradiating with radiation, the polyether multi-component copolymer is cross-linked to form a cross-linked product, and then the solvent is removed to cross-link the polyether multi-component copolymer. An adhesive porous membrane carrying the body can be obtained.

Such an adhesive porous membrane itself has adhesiveness, and the 180 ° peeling adhesive strength with a width of 20 mm is 0.2 N or more. In the present invention, the upper limit of the adhesive strength of the adhesive porous membrane is not particularly limited, but is usually 20 N in the 180 ° peeling adhesive strength with the 20 mm width.

Further, according to the present invention, the polyether multi-component copolymer is dissolved in an appropriate organic solvent as described above together with the electrolyte salt, the crosslinking aid and the polymerization initiator, and the resulting solution is formed into the base porous membrane. After contacting, heated or irradiated with radiation, the polyether multi-component copolymer is cross-linked to form a cross-linked product, and then the solvent is removed to support the cross-linked polyether multi-component copolymer An ion-conductive adhesive porous membrane can be obtained.

Such an ion conductive adhesive porous membrane itself has an adhesive strength of 180 N peel-off at a width of 20 mm and 0.2 N or more, like the adhesive porous membrane.

Since the adhesive porous membrane or the ion-conductive adhesive porous membrane according to the present invention has adhesiveness per se, it can be advantageously used in the production of batteries, capacitors and the like.

That is, for example, after laminating the adhesive porous membrane or the ion conductive adhesive porous membrane according to the present invention with the electrode, or winding the laminate to adhere the electrode to the porous membrane, Porous membrane-After impregnating the above-mentioned organic solvent or electrolyte into the electrode structure to produce a work-in-process product such as a battery or a capacitor, it is incorporated into a suitable exterior body and sealed, or the porous membrane- After the electrode structure is incorporated into a suitable outer package, the organic solvent or electrolyte is injected into the outer package and sealed, so that a polymer gel electrolyte is formed on the spot. A battery, a capacitor and the like using the polymer gel electrolyte according to the present invention can be obtained.

Further, 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 has excellent characteristics. A battery or the like can be obtained.

According to the present invention, the polymer gel electrolyte, that is, the substrate porous membrane, and the substrate porous membrane are obtained by various methods using the above-mentioned adhesive porous membrane and ion conductive adhesive porous membrane. A crosslinked product of the polyether multi-component copolymer supported on a membrane and swollen with an organic solvent, and the electrolyte supported on a substrate porous membrane together with the crosslinked product of the polyether multi-component copolymer A polymer gel electrolyte comprising a salt can be obtained. Here, according to the present invention, it is preferable that at least a part of the electrolyte salt is dissolved in the organic solvent.

That is, according to the first method, as described above, after supporting the crosslinked body of the polyether multi-component copolymer on the base porous membrane (that is, after obtaining the adhesive porous membrane), the electrolyte It is possible to obtain a polymer gel electrolyte by contacting an electrolyte solution composed of an organic solvent that dissolves a salt and swells a crosslinked product of the polyether multi-component copolymer and the electrolyte salt with the adhesive porous membrane. it can.

According to the second method, after the crosslinked body of the polyether multi-component copolymer and the first electrolyte salt are supported on the base porous membrane (that is, an ion conductive adhesive porous membrane is obtained). After), by contacting an electrolytic solution composed of an organic solvent that swells the crosslinked product of the polyether multi-component copolymer and a second electrolyte salt dissolved in the organic solvent, with the ion-conductive adhesive porous membrane A polymer gel electrolyte can be obtained.

In obtaining the polymer gel electrolyte according to the present invention by the first or second method, the electrolyte salt used for preparing the electrolytic solution is not particularly limited, and the ion conductive adhesive porous material described above is used. What is necessary is just to select suitably from what is carry | supported to a base-material porous film | membrane in order to obtain a film | membrane.

In the second method, the base electrolyte membrane is loaded with the first electrolyte salt to form an ion conductive adhesive porous membrane, and this ion conduction is then performed by the electrolytic solution containing the second electrolyte salt. The second electrolyte salt is supported on the adhesive adhesive porous membrane. Here, the first electrolyte salt and the second electrolyte salt are not particularly limited. For example, the ion conductivity described above is used. What is necessary is just to select suitably from what is carry | supported to a base-material porous membrane, in order to obtain an adhesive porous membrane. Further, the first and second electrolyte salts may be the same or different from each other.

According to the third method, after the polymer and the electrolyte salt are supported on the base porous membrane (that is, after obtaining the ion conductive adhesive porous membrane), the electrolyte salt is dissolved and the electrolyte salt is dissolved. An organic solvent that swells the polymer is brought into contact with the ion conductive adhesive porous membrane to swell the polymer, and preferably, by dissolving at least a part of the electrolyte salt in the organic solvent. A molecular gel electrolyte can be obtained.

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

Thus, according to the present invention, a polymer gel electrolyte 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.

Next, the production of the polyether multi-component copolymer and its crosslinked product used in the present invention will be described in detail.

The polyether multi-component copolymer used in the present invention includes, for example, a catalyst system mainly composed of organoaluminum as a catalyst for ring-opening polymerization, a catalyst system mainly composed of organic zinc, and an organotin-phosphate ester condensate catalyst system. Selected from the repeating structural unit represented by the formula (1), the repeating structural unit represented by the formula (2), and the repeating structural unit represented by the formulas (3) and (4). Corresponding to at least one repeating structural unit for crosslinking, 1 to 99 mol% of the monomer represented by the formula (6), 99 to 1 mol% of the monomer represented by the formula (7), 8) and at least one monomer selected from the monomers represented by formula (9), 0 to 20 mol%, are reacted in the presence or absence of a solvent at a reaction temperature of 10 to 80 ° C. with stirring. Can be obtained by: Among these, an organotin-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 above formula, in formula (6), R and R ′ each independently represent a hydrogen atom or a methyl group, R ₁ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a carbon number. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, the degree of polymerization k of the side chain oxyalkylene unit is 1 to 12, and in the formula (7) , R ′ represents a hydrogen atom or a methyl group, and in formula (8), R ′ represents a hydrogen atom or a methyl group, R ₂ represents an ethylenically unsaturated group, a reactive silicon-containing substituent, and the formula (5) And an alkyl group containing a halogen atom, and in formula (9), R ₃ represents a reactive silicon-containing substituent.

In particular, according to a preferred embodiment of the present invention, the monomer represented by the formula (6) is 1 to 98 mol%, preferably 2 to 95 mol%, and the monomer represented by the formula (7) is 98 to 1 mol%. Preferably, together with 95 to 2 mol%, at least one monomer selected from the monomers represented by formula (8) and formula (9) is used in an amount of 1 to 20 mol%, preferably 3 to 15 mol%. .

In the production of the polyether multi-component copolymer using the above monomer, the monomers represented by the formulas (8) and (9) have a crosslinkable reactive group in the molecule. By copolymerizing with the monomer represented by (7), a polyether multi-component copolymer having the crosslinkable reactive group in the molecule can be obtained. Thus, as described above, the polyether multi-component copolymer is obtained. For example, if necessary, by heating in the presence of a crosslinking aid and a polymerization initiator, the crosslinkable reactive group is used to crosslink the polyether multicomponent copolymer, and thus the polyether multicomponent A crosslinked product of the copolymer can be obtained.

In the monomer represented by the above formula (6), R ′ represents a hydrogen atom or a methyl group, and in the oxyalkylene unit in this monomer, each R independently represents a hydrogen atom or a methyl group, A hydrogen atom may be sufficient, all may be a methyl group, a part may be a hydrogen atom, and the remainder may be a methyl group. Therefore, the oxyalkylene unit may be an oxyethylene unit, an oxypropylene group unit, or an oxyethylenepropylene unit, but is preferably an oxyethylene unit or an oxypropylene unit, particularly an oxyethylene unit. . Furthermore, the degree of polymerization k of the oxyalkylene unit is preferably 1-12. When the value of the degree of polymerization k exceeds 12, the ionic conductivity of the resulting polymer gel electrolyte is lowered.

Specific examples of the monomer represented by the above formula (6) include diethylene glycol glycidyl methyl ether and dipropylene glycol glycidyl methyl ether. According to the invention, a mixture of two or more of these may be used. Moreover, the monomer represented by the formula (7) is specifically ethylene oxide or propylene oxide. According to this invention, the monomer represented by Formula (6) or Formula (7) may use 2 or more types of mixtures, respectively.

The monomer represented by the above formula (8) is one of the above-mentioned crosslinkable monomers having a crosslinkable reactive group. Examples of the crosslinkable reactive group include an ethylenically unsaturated group, a reactive silicon-containing substituent, Examples thereof include a substituent containing an epoxy group or an alkyl group containing a halogen atom.
Accordingly, among the crosslinkable monomers represented by the above formula (8), those having an ethylenically unsaturated group as the crosslinkable reactive group include, for example, allyl glycidyl ether, 4-vinylcyclohexyl glycidyl ether, α-terpi Nyl glycidyl ether, cyclohexenyl methyl 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, glycotonic acid Cisidyl, glycidyl-4-hexenoate, etc. (in the above, R 'is a hydrogen atom), 2,3-epoxy-2-methylpropyl vinyl ether, 2,3-epoxy-2-methylpropyl allyl ether, 3,4-epoxy-3-methyl-1-butene or the like (in the above, R ′ is a methyl group) or the like is used. According to the invention, a mixture of two or more of these may be used. Moreover, according to the present invention, among these, allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and the like are particularly preferably used.

Moreover, as a specific example of the monomer having a reactive silicon-containing substituent among the crosslinkable monomers represented by the above formula (8), for example, those represented by the following formula (10) or formula (11): Can be mentioned.

Specific examples of the crosslinkable monomer having a reactive silicon-containing substituent represented by the above formula (9) include those represented by the following formula (12).

In the crosslinkable monomer represented by the above formulas (10) to (12), R ′ is a hydrogen atom or a methyl group, and R ₄ , R ₅ and R ₆ are the same or different. However, at least one is an alkoxyl group and the remainder is an alkyl group. m represents 1-6.

Examples of the crosslinkable monomer represented by the above formula (10) include glycidoxymethyltrimethoxysilane, glycidoxymethylmethyldimethoxysilane, glycidoxyethyltrimethoxysilane, glycidoxyethylmethyldimethoxysilane, and glycidoxymethyltrimethoxysilane. Cidoxypropylmethyldimethoxysilane, glycidoxypropyltrimethoxysilane, glycidoxybutylmethyldimethoxysilane, glycidoxybutylmethyltrimethoxysilane, glycidoxyhexylmethyldimethoxysilane, glycidoxyhexylmethyltrimethoxysilane, etc. ( In the above, R 'is a hydrogen atom.), 2,3-epoxy-2-methylpropoxymethyltrimethoxysilane, 2,3-epoxy-2-methylpropoxymethylmethyldimethoxysilane, 2,3- Epoxy-2- Chill propoxymethyl dimethyl methoxy silane (above, R 'is of the methyl group.) Can be exemplified. According to the invention, a mixture of two or more of these may be used.

Examples of the crosslinkable 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 (in the above, R 'is a hydrogen atom), 2,3-epoxy-2-methylpropyltrimethoxysilane, 2,3-epoxy-2-methylpropylmethyldimethoxy Silane, 2,3-epoxy-2-methylpropyldimethylmethoxysilane, etc. 'Can be mentioned is.) Those methyl groups. According to the invention, a mixture of two or more of these may be used.

Examples of the crosslinkable monomer represented by the above formula (12) include (3,4-epoxycyclohexyl) -1-methyltrimethoxysilane and (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, etc. Can do.

In the present invention, among the crosslinkable monomers, in particular, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldimethoxysilane, 1,2-epoxybutyltrimethoxysilane, 1,2-epoxy Pentyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like are preferable.

Further, in the crosslinkable monomer having a substituent of the formula (5) and represented by the formula (8), the organic residue A is not particularly limited in its structure. Examples include (poly) alkylene groups such as (poly) methylene groups, hydrocarbon groups having an ether bond in the group, and the like.

Therefore, examples of the crosslinkable monomer (8) having a substituent of formula (5) include compounds represented by the following formulas (13) to (15).

In the crosslinkable monomer represented by the formula (13), R ₇ and R ₈ are each independently a hydrogen atom or a methyl group, and in the formula (13) and the formula (14), n is 0-12. An integer in the range.

Examples of the crosslinkable monomer represented by the above formula (13) include 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, ethylene glycol-2,3-epoxypropyl-2. Examples include ', 3'-epoxy-2'-methylpropyl ether and diethylene glycol-2,3-epoxypropyl-2', 3'-epoxy-2'-methylpropyl ether.

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

Examples of the crosslinkable monomer represented by the above formula (15) include hydroquinone-2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, catechol-2,3-epoxypropyl- And 2 ', 3'-epoxy-2'-methylpropyl ether.

Among such crosslinkable monomers containing an epoxy group, in particular, 2,3-epoxypropyl-2 ′, 3′-epoxy-2′-methylpropyl ether, ethylene glycol-2,3-epoxypropyl-2 ′ 3,3′-epoxy-2′-methylpropyl ether and the like are preferable.

By using what is represented by said Formula (8) or Formula (9) with the thing represented by said Formula (6) and Formula (7) as a monomer in manufacture of a multi-component polyether copolymer. A polyether multi-component copolymer having a crosslinkable reactive group in the molecule can be obtained, and such a polyether multi-component copolymer can be obtained by utilizing the reactivity of the crosslinkable reactive group, can do. In obtaining such a crosslinked product, a crosslinking aid having reactivity with the crosslinking reactive group can be used as necessary. By using such a crosslinking aid, the crosslinking reaction of the polyether multi-component copolymer having the crosslinking reactive group in the molecule can be effectively performed. Thus, the mechanical strength of the resulting polymer gel electrolyte can be further improved by providing the polyether multi-component copolymer with a crosslinked structure.

Next, in order to obtain a crosslinked product of the polyether multi-component copolymer, when using the ethylenically unsaturated group, thermal polymerization using a radical polymerization initiator selected from organic peroxides, azo compounds, etc. Photopolymerization with active energy rays such as ultraviolet rays and electron beams can be used.

As said organic peroxide, conventionally well-known things, such as a ketone peroxide, a peroxy ketal, a hydroperoxide, a dialkyl peroxide, a diacyl peroxide, peroxy ester, are used suitably, for example. Specific examples include, 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-dihydroperoxide, di-t- Butyl peroxide, t-butylcumyl peroxide, dicumyl peroxide, α, α'-bis (t-butylperoxy-m-isopropyl) benzene, 2,5-dimethyl-2,5-di (t-butyl Peroxy) hexane, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, benzoyl peroxide, t And butyl peroxy isopropyl carbonate. Such an organic peroxide is usually used in an amount of 0.01 to 10% by weight of the polyether multi-component copolymer, although it depends on the type.

As the azo compound, conventionally known compounds such as an azonitrile compound, an azoamide compound, and an azoamidine compound are appropriately used. Specific examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethyl). Valeronitrile), 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-methyl Propionamidine] dihydrochloride, 2,2′-azobis [N-hydroxyphenyl) -2-methylpropionamidine] dihydrochloride, 2,2′-azobis [2-methyl-N- (phenylmethyl) propionamidine] two Hydrochloride, 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 2,2′-azobis [2- (2-imidazolin-2-yl) propane] dihydrochloride, 2,2′-azobis [2- (4,5,6,7-tetrahydro-1H-1,3-diazepine) -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-methylpropionamide) dihydrate, 2,2 '-Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methylpropane), dimethyl-2,2'-azobisisobutyrate, 4,4'-azobis (4-cyano Valeric acid), 2,2'-azobis [2-hydroxymethyl) pro Onitoriru] and the like can be mentioned.

Such an azo compound is usually used in an amount of 0.01 to 10% by weight of the polyether multi-component copolymer, although it depends on the type.

In the production of a crosslinked product using an unsaturated group of a polyether multi-element copolymer, when active energy ray irradiation such as ultraviolet rays is used, as a sensitizing aid, for example, diethoxyacetophenone, 2-hydroxy-2- Methyl-1-phenylpropan-1-one, benzyldimethyl ketal, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-hydroxyethoxy) phenyl- (2- Hydroxy-2-propyl) ketone, 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-2-morpholino (4-thiomethylphenyl) propane-1- Acetophenones such as ON, benzoin, benzoin methyl ether, benzoin ethyl ether, Benzoin ethers such as benzoin isopropyl ether and benzoin isobutyl ether, benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, alkylated benzophenone, 3,3 ', 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4-benzoyl-N, N-dimethyl-N- [2- (1-oxo-2-propenyloxy) ethyl] benzenemethananium bromide Benzophenones such as (4-benzoylbenzyl) trimethylammonium croid, thioxanthones such as 2-isopropylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, azide Len, 3-sulfonyl azidobenzoic 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-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) Azides such as 2-propanone-2′-sulfonic acid and 1,3-bis (4′-azidocinnalidene) -2-propanone are used as appropriate.

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

Thus, in order to obtain a crosslinked product of a polyether multi-component copolymer, the ethylenically unsaturated group itself may be cross-linked, and if necessary, a polyether multi-component may be used using a cross-linking aid. The copolymer may be cross-linked.

As described above, according to the present invention, a polyfunctional polymerizable monomer is preferably used as the crosslinking aid. However, a monocyclic polymerizable monomer is also effective as the crosslinking aid. Can be used.

Therefore, according to the present invention, as the crosslinking aid, for example, ethylene glycol diacrylate, ethylene glycol dimethacrylate, oligoethylene glycol diacrylate, oligoethylene glycol dimethacrylate, propylene glycol diacrylate, propylene glycol dimethacrylate, oligo Propylene 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-trimethylolethane diacrylate, pentaerythritol trimethacrylate, 1,2,6-hexanetriacrylate, sorbitol pentamethacrylate Rate, methylene bisacrylamide, methylene bismethacrylamide divinyl benzene, vinyl methacrylate, vinyl crotonate, vinyl acrylate, vinyl acetylene, trivinyl benzene, triallyl cyanyl sulfide, divinyl ether, divinyl sulfoether, diallyl phthalate, glycerol trivinyl ether, Allyl metal acrylate, allyl acrylate, diallyl malate, diallyl fumarate, diallyl itaconate, methyl methacrylate, butyl acrylate, ethyl acrylate, 2-ethylhexyl acrylate, lauryl methacrylate, ethylene glycol acrylate, triallyl isocyanurate, maleimide, phenyl maleimide P-quinonedioxime, maleic anhydride, itaconic acid, etc. Can be mentioned.

In order to obtain a crosslinked product of a polyether multi-component copolymer by using the reactive silicon-containing group of the polyether multi-component copolymer, the reaction may be performed by reacting the reactive silicon group with water. In order to increase the reactivity of the silicon-containing group, tin compounds such as dibutyltin dilaurate, dibutyltin malate, dibutyltin diacetate, tin octylate, dibutyltin acetylacetonate, titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, Organometallic compounds such as aluminum compounds such as aluminum trisacetylacetonate, aluminum trisethylacetoacetate, diisopropoxyaluminum ethylacetoacetate, or butylamine, octylamine, laurylamine, dibutylamine, monoethanolamine, diethano Triethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, cyclohexylamine, benzylamine, diethylaminopropylamine, guanine, an amine compound such as diphenyl guanine may be used as a catalyst.

Moreover, when obtaining the crosslinked body of a polyether multi-component copolymer using the epoxy group which a polyether multi-component copolymer has, polyamines, acid anhydrides, etc. are used.

Polyamines include diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, hexamethylenediamine, N-aminoethylpiperazine, bis (aminopropylpiperazine) Aliphatic polyamines such as trimethylhexamethylenediamine and isophthalic acid dihydrazide, 4,4-diaminodiphenyl ether, diaminodiphenylsulfone, m-phenylenediamine, 2,4-toluylenediamine, m-toluylenediamine, o-toluylenediamine And aromatic polyamines such as xylylenediamine.

Such polyamines are usually used in an amount of 0.01 to 10% by weight of the polyether multi-component copolymer, although depending on the type.

Acid anhydrides include maleic anhydride, dodecenyl succinic anhydride, chlorendec anhydride, phthalic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride And acid, methyltetrahydrophthalic anhydride, trimellitic anhydride and the like.

Such acid anhydrides are usually used in an amount of 0.01 to 10% by weight of the polyether multi-component copolymer, although depending on the type.

According to the present invention, a crosslinking accelerator may be used in obtaining a crosslinked product of a polyether multi-component copolymer. Examples of the accelerator in the crosslinking reaction of polyamines include phenol, cresol, resorcinol, pyrogallol, nonylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, and the like. Examples of the accelerator for the crosslinking reaction of the acid anhydride include benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 2- (dimethylaminoethyl) phenol, dimethylaniline, 2-ethyl- 4-methylimidazole and the like can be mentioned. Such an accelerator is usually used in the range of 0.01 to 10% by weight of the crosslinking aid, although it depends on the type.

Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples. Below, the physical property of the used base-material porous membrane was evaluated as follows.

(Thickness)
It was determined based on a measurement with a 1/10000 mm thickness gauge and a 10,000 times scanning electron micrograph of the cross section of the porous substrate membrane.

(Porosity)
From the weight W (g) per unit area S (cm ² ) of the substrate porous membrane, the average thickness t (cm), and the density d (g / cm ³ ) of the resin constituting the substrate porous membrane, Calculated.
Porosity (%) = (1− (100 W / S / t / d)) × 100

(Air permeability)
Measurement was performed according to JIS P 8117.

(Puncture 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 thickness was determined. A needle having a diameter of 1.0 mm and a radius of curvature of the tip of 0.5 mm was used at a speed of 2 cm / second.

(Analysis of polyether multi-component copolymer)
The analysis of the polyether multi-component copolymer was performed as follows. The glass transition temperature and the heat of fusion were measured using a differential scanning calorimeter DSC8230B manufactured by Rigaku Denki Co., Ltd. in a nitrogen atmosphere at a temperature range of −100 to 80 ° C. and a temperature increase rate of 10 ° C./min. The monomer equivalent composition of the polyether multi-component copolymer was determined from a proton NMR spectrum.

The molecular weight of the polyether multi-component copolymer was measured by gel permeation chromatography, and the weight average molecular weight was calculated in terms of standard polystyrene. The gel permeation chromatography measurement uses a measuring device RID-6A manufactured by Shimadzu Corporation, and columns “Showex” KD-807, KD-806, KD-806M and KD-803 manufactured by Showa Denko K.K. Performed at 60 ° C. using the solvent dimethylformamide.

(Measurement of conductivity)
The conductivity of the polymer gel electrolyte produced in the example and the porous membrane immersed in the electrolyte solution in the comparative example are sandwiched between platinum electrodes, and at a temperature of 25 ° C., the voltage is 0.5 V, and the frequency range is 5 Hz to 1 MHz. It calculated by the complex impedance method using the alternating current method.

Reference example 1
(Catalyst production example)
A three-necked flask equipped with a stirrer, a thermometer and a distillation apparatus was charged with 10 g of tributyltin chloride and 35 g of tributyl phosphate, and heated at 250 ° C. for 20 minutes with stirring under a nitrogen stream to distill off the distillate. A solid condensate was obtained as a residue. In the following, this organotin-phosphate ester condensate was used as a catalyst.

(Manufacture of polyether multi-component copolymer)
The inside of a 3 L glass four-necked flask was purged with nitrogen, and the following formula (16) adjusted to 0.3 g of the organotin-phosphate ester condensate and water content of 10 ppm or less as a catalyst.

300 g of glycidyl ether compound, 27 g of allyl glycidyl ether, and 2000 g of solvent n-hexane were charged, and 320 g of ethylene oxide 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 produced 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. 595 g of polymer having was obtained.

The polyether multicomponent copolymer thus obtained had a glass transition temperature of -70 ° C. and a weight average molecular weight of 1.0 × 10 ^{6 as} measured by gel permeation chromatography. There was no heat of fusion. Moreover, the monomer conversion composition of this polyether multicomponent copolymer by proton NMR spectrum was the said glycidyl ether compound (16): ethylene oxide: allyl glycidyl ether = 20: 80: 2 mol%.

Example 1
Toluene was added 2.0 g of the above polyether multi-component copolymer prepared in Reference Example 1, 0.4 g of a crosslinking aid diethylene glycol dimethacrylate (Blenmer PDE-100 manufactured by NOF Corporation) and 0.02 g of a polymerization initiator benzoyl peroxide. A coating solution was prepared by dissolving in 21.6 g.

Base material porous membrane (film thickness 25 μm, porosity 40%, average pore diameter 0.05 μm, air permeability 500 seconds / 100 mL, needle penetration strength made of ultra high molecular weight polyethylene resin (weight average molecular weight 2.0 × 10 ⁶ ) 7.0N) is immersed in the coating solution, sandwiched between two glass plates, heated in an inert gas atmosphere at 85 ° C. for 2 hours to crosslink the polyether multi-component copolymer, A swelling gel of a crosslinked product of an ether multi-component copolymer was supported on the porous substrate membrane. This was dried, toluene was removed, and an adhesive porous membrane formed by supporting a crosslinked product of a polyether multi-component copolymer was obtained. This adhesive porous membrane had adhesiveness by itself, and was peeled off 180 °, and the adhesive strength was 2 N / 20 mm width.

Next, the adhesive porous membrane is immersed for 3 hours in an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2) in which lithium perchlorate is dissolved at a concentration of 1 mol / L, and the polyether multicomponent A polymer gel electrolyte having a polymer cross-linked product as a polymer component was obtained. The conductivity was 6.0 × 10 ⁻⁴ S / cm at 25 ° C.

Example 2
2.0 g of the polyether multi-component copolymer prepared in Reference Example 1, 0.4 g of a crosslinking aid diethylene glycol dimethacrylate (Blenmer PDE-100 manufactured by NOF Corporation) and a polymerization initiator 2,2-azobis (2, 4-dimethylvaleronitrile) 0.01 g is dissolved in 21.6 g of ethyl acetate, and lithium perchlorate is added thereto so that the weight ratio of polyether multi-component copolymer / lithium perchlorate is 100/15. Thus, a coating solution was prepared.

A substrate porous membrane made of the same ultrahigh molecular weight polyethylene resin as in Example 1 was immersed in the coating solution, sandwiched between two glass plates, heated in an inert gas atmosphere at 50 ° C. for 2 hours, The polyether multi-component copolymer was cross-linked, and thus a porous membrane carrying a crosslinked gel of the polyether multi-component copolymer was obtained. This was dried, ethyl acetate was removed, and an ion conductive adhesive porous membrane carrying a crosslinked product of the polyether multi-component copolymer and lithium perchlorate was obtained. This ion conductive adhesive porous film had adhesiveness by itself, and peeled off 180 ° and had an adhesive force of 1.5 N / 20 mm width.

Next, the ion conductive adhesive porous membrane is immersed in an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2) in which lithium perchlorate is dissolved at a concentration of 1 mol / L for 3 hours, and the polyether A crosslinked polymer of the multi-component copolymer was swollen, and thus a polymer gel electrolyte having the crosslinked polymer of the polyether multi-component copolymer as a polymer component was obtained. Its conductivity was 6.4 × 10 ⁻⁴ S / cm at 25 ° C.

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 seconds / 100 mL, needle penetration strength 3N as the porous substrate film in Example 1 ) Was used in the same manner as in Example 1 to obtain an adhesive porous membrane carrying a cross-linked polyether multi-component copolymer. This adhesive porous membrane had adhesiveness by itself, and peeled off 180 ° and had an adhesive force of 1.2 N / 20 mm width.

Next, the adhesive porous membrane is immersed for 3 hours in an ethylene carbonate / ethyl methyl carbonate mixture (volume ratio 1/2) in which lithium perchlorate is dissolved at a concentration of 1 mol / L, and the polyether multicomponent copolymer A crosslinked polymer product was swollen, and thus a polymer gel electrolyte containing a crosslinked polymer of a polyether multi-component copolymer as a polymer component was obtained. Its conductivity was 1.7 × 10 ⁻³ S / cm at 25 ° C.

Comparative Example 1
15 parts by weight of ultra high 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) are mixed to form a uniform slurry, which is charged into a small kneader and heated to a temperature of 160 The mixture was heated, dissolved, and kneaded at 1 ° C. for 1 hour. The obtained kneaded material was sandwiched between metal plates cooled to 0 ° C. and rapidly cooled to obtain a gel-like sheet having a thickness of 5 mm. This sheet was rolled to a thickness of 0.8 mm at a temperature of 120 ° C. with a heat press, and simultaneously biaxially stretched 3.5 × 3.5 times in length and width at a temperature of 125 ° C. to obtain a rolled stretched film. And 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 was not adhesive by itself, and the peel strength at 180 ° C. with a width of 20 mm was 0.

The 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 the conductivity was measured. 9.3 × 10 ⁻⁴ S / cm.

Claims (4)

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 After the polymer is supported on the base porous membrane, the polymer is crosslinked to obtain an adhesive porous membrane as a crosslinked body, and then an organic solvent that swells the crosslinked body of the polymer and an electrolyte salt that dissolves in the organic solvent A method for producing a polymer gel electrolyte, comprising contacting the above-mentioned electrolytic porous film with the adhesive porous 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; After the first electrolyte salt is supported on the base porous membrane, the polymer is cross-linked to obtain an ion conductive adhesive porous membrane as a cross-linked body, and then an organic that swells the cross-linked body of the polymer. A method for producing a polymer gel electrolyte, comprising bringing an electrolyte solution comprising a solvent and a second electrolyte salt dissolved in the organic solvent into contact with the ion conductive adhesive porous 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; After supporting the electrolyte salt on the substrate porous membrane, the polymer is crosslinked to obtain an ion conductive adhesive porous membrane as a crosslinked body, and then an organic solvent for swelling the crosslinked body of the polymer is A method for producing a polymer gel electrolyte, comprising contacting with an ion conductive adhesive porous membrane. The method for producing a polymer gel electrolyte according to any one of claims 1 to 3, wherein the polymer is 1 to 99 mol% of a repeating structural unit represented by the formula (1) and a repeating structure represented by the formula (2). It consists of 99 to 1 mol% of units and 0 to 20 mol% of at least one repeating structural unit for crosslinking selected from repeating structural units represented by the formulas (3) and (4), and has a weight average molecular weight of 10 ^A method for producing a polymer gel electrolyte, which is a polyether multi-component copolymer in the range of ⁴ to 10 ⁷ .

(In the above formula, in formula (1), R and R ′ each independently represent a hydrogen atom or a methyl group, and R ₁ represents an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 8 carbon atoms, or a carbon number. A cycloalkyl group having 3 to 8 carbon atoms, an aryl group having 6 to 14 carbon atoms or an aralkyl group having 7 to 12 carbon atoms, the degree of polymerization k of the side chain oxyalkylene unit is 1 to 12, and in formula (2) , R ′ represents a hydrogen atom or a methyl group, and in formula (3), R ′ represents a hydrogen atom or a methyl group, R ₂ represents an ethylenically unsaturated group, a reactive silicon-containing substituent, In the formula (4), R ₃ represents a reactive silicon-containing substituent, and in the formula (5), A represents an organic residue. .)