JP6765855B2 - Anionic conductive membrane - Google Patents

Description

The present invention relates to anionic conductive membranes. More specifically, the present invention relates to an anionic conductive membrane that can be suitably used as a battery separator or the like.

In recent years, the importance of batteries has rapidly increased in many industries from small portable devices to large-scale applications such as automobiles, and new battery systems that have advantages mainly in terms of capacity, energy density, and secondary batteries. Has been developed and improved in various ways. For example, zinc negative electrodes using zinc type as the negative electrode active material have been studied for a long time with the spread of batteries, and in particular, air / zinc primary batteries, manganese / zinc primary batteries, and silver / zinc primary batteries have been put into practical use. Widely used in the world.
However, when zinc is used for the negative electrode of the storage battery, there is a problem that the positive electrode and the negative electrode are short-circuited by the dendrite formed on the surface of the negative electrode during charging, and the battery cannot be charged and discharged.

Many technological developments have been made to solve such problems. For example, a positive electrode, a negative electrode containing at least one of zinc and a zinc compound as a negative electrode active material, and ion exchange formed on the negative electrode or the negative electrode active material. At least one selected from the group consisting of the negative electrode, the coating, and the electrolyte having a coating containing a resin and an electrolyte containing an alkaline aqueous solution as an electrolytic solution is noble than the standard electrode potential of zinc and is of zinc. An alkaline secondary battery comprising a metal having a melting point lower than the melting point, an oxide containing the metal, a salt containing the metal, and at least one selected from the group consisting of an ion containing the metal is disclosed. (See, for example, Patent Document 1.). Then, a zinc negative electrode active material for a zinc alkaline secondary battery coated with a hydroxide that does not show substantial solubility in an alkaline aqueous solution and does not involve an oxidation / reduction reaction in the potential range of the charge / discharge reaction of the battery is disclosed. (See, for example, Patent Document 2). Further, a technique for suppressing dendrites by forming a separator with an anionic conductive material containing a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table is disclosed. (See, for example, Patent Document 3.).
A material containing a polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table, similar to the anionic conductive material, is used as a negative electrode mixture for a lithium ion secondary battery. The technique to be used is disclosed (see, for example, Patent Document 4).

Japanese Unexamined Patent Publication No. 2013-54877 Japanese Patent Application Laid-Open No. 5-144431 International Publication No. 2014/1196665 Japanese Unexamined Patent Publication No. 2013-134896

As described above, various methods have been developed for suppressing a short circuit between the positive electrode and the negative electrode due to the growth of dendrites of the battery using zinc type as the negative electrode active material and extending the life of the battery. There is a need for longer life, and there is a need to develop materials that can extend the life of batteries.

The present invention has been made in view of the above situation, and an object of the present invention is to provide a material capable of further extending the life of a battery using zinc type as a negative electrode active material.

The present inventors have studied various materials capable of further extending the life of a battery using zinc type as a negative electrode active material, and have selected a conjugated diene polymer, a (meth) acrylic polymer, and a specific inorganic compound. We focused on using an anionic conductive film containing and. In such an anionic conductive film, the particle portion of the inorganic compound selectively permeates hydroxide ions, and the conjugated diene polymer and the (meth) acrylic polymer are conventional such as polytetrafluoroethylene. It is possible to reduce the voids of the film as compared with the fibrous polymer of the above, and suppress the growth of dendrite. Furthermore, the present inventors have studied variously and formed an anionic conductive film having a liquid absorption rate of 25% or less, which contains a conjugated diene polymer or a (meth) acrylic polymer and a specific inorganic compound. did. When this anionic conductive film is used as a battery separator, the present inventors have found that the hydrophilic functional groups and low-fused portions of the conjugated diene polymer and the (meth) acrylic polymer, and the polymer. It was found that the life of the battery can be further extended because the short circuit between the positive electrode and the negative electrode can be prevented by suppressing the holding amount of the aqueous electrolyte solution derived from the additives and the like. We came up with the idea that it could be solved and arrived at the present invention.

That is, the present invention comprises a conjugated diene-based polymer and / or a (meth) acrylic-based polymer, and at least one inorganic compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides. It is an anionic conductive film containing 25% or less of liquid absorption.
The present invention will be described in detail below.
It should be noted that a combination of two or more of the individual preferred embodiments of the present invention described below is also a preferred embodiment of the present invention.

<Anionic conductive membrane>
The anionic conductive membrane of the present invention has a liquid absorption rate of 25% or less.

The liquid absorption rate is determined from the viewpoint of the hydrophilic functional group and the low-fused portion of the conjugated diene polymer or the (meth) acrylic polymer, and the amount of the aqueous electrolyte retained from the polymer additive or the like. It is preferably 22% or less, more preferably 20% or less, further preferably 18.5% or less, and particularly preferably 18% or less.
The lower limit of the liquid absorption rate is not particularly limited, but the liquid absorption rate should be 1% or more from the viewpoint of ensuring sufficient ionic conductivity for use as a separator in the anionic conductive membrane of the present invention. It is more preferably 5% or more, more preferably 9% or more, and particularly preferably 11% or more from the viewpoint of further improving the life performance of the anion conductive membrane.
If the liquid absorption rate is low, the life performance of the anionic conductive membrane tends to be low. It is considered that the reason is that when an anionic conductive membrane having a low liquid absorption rate is used as a battery separator, the battery performance deteriorates from the viewpoint of electrolyte retention and ionic conductivity.
The liquid absorption rate can be calculated by the following formula.
Liquid absorption rate [%] = {(M _{a −} M _b ) / M _b } * 100
M _a: anion conducting membrane weight after the electrolyte solution dipping [g]
M _b : Mass of anionic conductive membrane before immersion in electrolytic solution [g]
Note that the M _a, M _b can be prepared according to the procedure described for example, is measured.
Further, when preparing the anionic conductive film, the liquid absorption rate is heat-treated after the film formation, or the composition, emulsifier amount and type of the conjugated diene polymer or (meth) acrylic polymer are adjusted. It can be adjusted by.

In the anionic conductive membrane of the present invention, the average value of the liquid absorption rate calculated from each of the 10 test pieces in the method described in the examples may be within a predetermined range, but each is calculated from 10 test pieces. It is preferable that all of the liquid absorption rates are within a predetermined range.

Further, the anion conductive membrane of the present invention preferably has a swelling degree of 10% or less. As a result, the life of the battery can be extended as in the case of reducing the liquid absorption rate.

The degree of swelling is more preferably 9% or less, further preferably 8% or less, and particularly preferably 7% or less. The degree of swelling is preferably 0.5% or more, more preferably 1% or more, and further preferably 1.5% or more.
The degree of swelling can be calculated by the following formula.
Swelling degree [%] = {(T _a −T _b ) / T _b } * 100
T _a: thickness after the electrolyte solution dipping [[mu] m]
T _b : Film thickness [μm] before immersion in electrolytic solution
The T _a and T _b can be measured according to the method described in Examples.
The degree of swelling can be adjusted by the same method as the method for adjusting the liquid absorption rate.

The anion conductive membrane of the present invention may be calculated from 10 test pieces, although the average value of the swelling degree calculated from each of the 10 test pieces in the method described in the examples may be within a predetermined range. It is preferable that all of the swelling degrees are within a predetermined range.

The anionic conductive membrane of the present invention preferably has a value of X calculated by the formula (1) described in Examples of 200 or more. By satisfying such a value, it is possible to exert an effect of suppressing dendrite when the anionic conductive film is used in a battery using an electrode active material in which the growth of dendrite such as zinc is a problem.

In the anionic conductive film of the present invention, at least one inorganic compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides contained in the anionic conductive film is particulate. Is preferable. When the inorganic compound is in the form of particles, the effect of suppressing the permeation of zincate ions into the anion conductive membrane is enhanced, and the permeability of hydroxide ions is further improved.
The cross section of the anionic conductive film of the present invention includes the total area of at least one inorganic compound particle (compound particle) selected from the group consisting of oxides, hydroxides, and layered compound hydroxides, and the compound. The ratio of the total area of the compound particles to the sum of the total areas of the anionic conductive film-forming material components other than the above (compound particles / [compound particles + anionic conductive film-forming material components other than the compound]) is 30% or more. It is preferably 70% or less. With such an area ratio, the anion conductive film can exhibit better hydroxide ion conductivity while having sufficient strength.
The area of the compound particles and the area of the anionic conductive film-forming material component other than the compound can be measured according to the method described in Examples.

The anion conductive film of the present invention is the total area of compound particles with respect to the sum of the total area of the compound particles and the total area of the anion conductive film forming material components other than the compound in at least one cross section of the film. The ratio may be within the above-mentioned predetermined range, but from the viewpoint of the permeability of hydroxide ions, it is preferably within the above-mentioned predetermined range in any cross section, and also within the above-mentioned predetermined range on the surface of the film. More preferably.

The anionic conductive membrane of the present invention may partially contain independent voids. The area of the voids in the anion conductive membrane of the present invention is preferably 3% or less of the total area of the anion conductive membrane.
The ratio of the area of the voids can be measured by observing the cross section of the anion conductive membrane according to the method described in Examples.

The average cross-sectional particle size of the compound particles is preferably 0.1 to 1.0 μm. When the average value of the cross-sectional particle diameter is in such a range, the permeability of hydroxide ions becomes better.
The average value of the cross-sectional particle diameter can be measured according to the method described in Examples.
The above range description of "0.1 to 1.0 μm" means a range including the numerical values of the upper end and the lower end of the range. That is, "0.1 to 1.0 μm" has the same meaning as "0.1 μm or more and 1.0 μm or less".
Similarly, all the range descriptions using "~" described in the present invention mean a range including the numerical values of the upper end and the lower end of the range.

The anionic conductive membrane of the present invention preferably has a resistance value R of 0.01Ω or more. The resistance value R is more preferably 0.02Ω or more, further preferably 0.03Ω or more, further preferably 0.05Ω or more, and particularly preferably 0.1Ω or more.
The anionic conductive membrane of the present invention preferably has a resistance value R of 1.0 Ω or less. The resistance value R is more preferably 0.5 Ω or less, further preferably 0.3 Ω or less, and particularly preferably 0.25 Ω or less.
The resistance value R can be measured according to the method described in Examples.

The anionic conductive film of the present invention contains a conjugated diene polymer and / or a (meth) acrylic polymer.

<Conjugated diene polymer>
The conjugated diene-based polymer is not particularly limited as long as it has a monomer unit derived from the conjugated diene-based monomer, but the inorganic compound can be uniformly present in the anionic conductive film and the machine of the film. From the viewpoint of target strength, a conjugated diene-based copolymer further having a monomer unit derived from an aromatic vinyl monomer is preferable. The composition of the conjugated diene polymer shall be as shown below, for example, it shall contain a monomer unit derived from another unsaturated monomer having a functional group or an acid group or the like. Alternatively, the liquid absorption rate of the anionic conductive film of the present invention can be suitably adjusted by preparing it using a known emulsifier.

The conjugated diene-based monomer is preferably an aliphatic conjugated diene-based monomer. Examples of the aliphatic conjugated diene-based monomer include 1,3-butadiene, isoprene, 2-chloro-1,3-butadiene, chloroprene and the like, and 1,3-butadiene is preferable. The conjugated diene-based monomer may be used alone or in combination of two or more.
In addition, a functional group such as an ester group, a hydroxy group, and a carboxy group may be introduced into the conjugated diene polymer. By introducing these functional groups, the affinity between the conjugated diene polymer and the inorganic compound particles is increased, and the uniformity of the material is improved.

As the conjugated diene-based polymer, one or more homopolymers such as polybutadiene and polyisoprene, and copolymers can be used. As described above, for example, an aromatic vinyl monomer can be used. It is preferably a copolymer further having the derived monomer unit.

Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and o-. Methylstyrene, m-methoxystyrene, p-methoxystyrene, o-ethoxystyrene, m-ethoxystyrene, p-ethoxystyrene, o-fluorostyrene, m-fluorostyrene, p-fluorostyrene, o-chlorostyrene, m- Chlorostyrene, p-chlorostyrene, o-bromostyrene, m-bromostyrene, p-bromostyrene, o-acetoxystyrene, m-acetoxystyrene, p-acetoxystyrene, o-tert-butoxystyrene, m-tert-butoxy Examples thereof include styrene, p-tert-butoxystyrene, o-tert-butylstyrene, m-tert-butylstyrene, p-tert-butylstyrene, vinyltoluene and the like. Among these, styrene and α-methylstyrene are preferable because the heat resistance and mechanical strength of the anionic conductive membrane can be increased. Each of these aromatic vinyl monomers may be used alone, or two or more of them may be used in combination.

In the above-mentioned conjugated diene polymer, the mass ratio of the monomer unit derived from the aliphatic conjugated diene monomer and the monomer unit derived from the aromatic vinyl monomer is, for example, 1/9 or more, 9 / It is preferably 1 or less, more preferably 2/8 or more and 8/2 or less, and further preferably 3/7 or more and 7/3 or less.

As the conjugated diene polymer, one or more of styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer and the like are preferably used from the viewpoint of film moldability. Can be done. Among these, from the viewpoint of the fact that the inorganic compound can be uniformly present in the anionic conductive film and the mechanical strength of the film, both conjugated diene copolymers such as styrene-butadiene copolymer and acrylonitrile-butadiene copolymer The polymer is more preferable, and the styrene-butadiene copolymer is particularly preferable.

The conjugated diene polymer is a monomer derived from other unsaturated monomers other than the monomer unit derived from the aliphatic conjugated diene monomer and the monomer unit derived from the aromatic vinyl monomer. It may have a unit.

Other unsaturated monomers include acid group-containing vinyl monomers such as itaconic acid, acrylic acid, methacrylic acid, fumaric acid, maleic acid, acrylamide methylpropane sulfonic acid, and styrene sulfonate; (meth). Methyl acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, (Meta) acrylates such as hexyl (meth) acrylate, heptyl (meth) acrylate, octyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, etc. Alkyl ester monomer; hydroxyl group-containing vinyl monomer such as 2-hydroxyethyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; nitrile group-containing vinyl monomer such as (meth) acrylonitrile; (meth) ) (Meta) acrylamide-based monomers such as acrylamide, N-methylol (meth) acrylamide, N-ethylol (meth) acrylamide, dimethyl (meth) acrylamide, diethyl (meth) acrylamide; divinylbenzene, ethylene glycol dimethacrylate, iso Bifunctional vinyl monomer such as propylene glycol diacrylate and tetramethylene glycol dimethacrylate; containing an alkossisilane group such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxipropyltriethoxysilane A vinyl monomer can be mentioned.
By introducing a highly polar functional group such as an ester group, a hydroxy group, or a carboxy group into the conjugated diene-based polymer, the affinity between the conjugated diene-based polymer and the inorganic compound particles is improved, and the inorganic compound particles Dispersibility is improved, liquid absorption is controlled, and material uniformity is improved.

The mass ratio of the monomer unit derived from the other unsaturated monomer in 100% by mass of the conjugated diene polymer is preferably 40% by mass or less, more preferably 20% by mass or less, and 10% by mass. The following is more preferable, and 5% by mass or less is particularly preferable.
When the monomer unit derived from the (meth) acrylic acid alkyl ester monomer is contained as the monomer unit derived from the other unsaturated monomer, the (meth) acrylic acid alkyl in the conjugated diene-based polymer is included. The mass ratio of the monomer unit derived from the ester monomer is smaller than the mass ratio of the monomer unit derived from the conjugated diene-based monomer.

<(Meta) acrylic polymer>
The (meth) acrylic polymer in the present invention contains a monomer unit derived from the (meth) acrylic acid alkyl ester monomer as a main component. The inclusion of a monomer unit derived from a (meth) acrylic acid alkyl ester monomer as a main component is occupied by a monomer unit derived from a (meth) acrylic acid alkyl ester monomer in a (meth) acrylic polymer. It means that the mass ratio is larger than any of the mass ratios of the monomer units derived from each of the other unsaturated monomers described later.

Examples of the (meth) acrylic acid alkyl ester monomer include methyl (meth) acrylic acid, ethyl (meth) acrylic acid, n-propyl (meth) acrylic acid, isopropyl (meth) acrylic acid, and n (meth) acrylic acid. -Butyl, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, sec-butyl (meth) acrylate, amyl (meth) acrylate, cyclohexyl (meth) acrylate, heptyl (meth) acrylate, ( 2-Ethylhexyl acrylate, n-octyl acrylate, isooctyl acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, decyl (meth) acrylate A (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms such as dodecyl is preferable, and one or more of these can be used.

For example, in the anionic conductive film of the present invention, the (meth) acrylic polymer contains a monomer unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms as a main component. It is preferable to include as. A (meth) acrylic polymer containing a monomer unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms as a main component means an alkyl group having 1 to 12 carbon atoms. The mass ratio of the monomer unit derived from the (meth) acrylic acid alkyl ester monomer having is the mass ratio of the monomer unit derived from each of the other unsaturated monomers described later or the number of carbon atoms of 13 or more. It means that it is larger than any of the mass ratios of the monomer units derived from the (meth) acrylic acid alkyl ester monomer having an alkyl group.

The (meth) acrylic polymer may be composed only of the above (meth) acrylic acid alkyl ester monomer, but the main component is a monomer unit derived from the (meth) acrylic acid alkyl ester monomer. It is preferable that the (meth) acrylic copolymer contains a monomer unit derived from other unsaturated monomers. At that time, from the viewpoint of extending the life of the battery, the mass ratio of the monomer unit derived from the (meth) acrylic acid alkyl ester monomer is 50 mass of the entire monomer unit of the (meth) acrylic polymer. % Or more is preferable. The mass ratio of the monomer unit is more preferably 60% by mass or more, and further preferably 70% by mass or more. The upper limit of the mass ratio of the monomer unit is not particularly limited and is 100% by mass, but from the viewpoint of improving the mechanical strength of the film, for example, the mass ratio is preferably 99% by mass or less. , 98% by mass or less, more preferably 95% by mass or less.

Examples of the other unsaturated monomer include a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester monomer, an oxo group-containing monomer, a nitrogen atom-containing monomer, and a fluorine atom-containing simple substance. Monofunctional monomers such as mer, epoxy group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene-based monomer, (meth) acrylic acid aralkyl ester monomer, and polyfunctional Examples include, but the present invention is not limited to such embodiments. These unsaturated monomers may be used alone or in combination of two or more.

Examples of the carboxy group-containing monomer include (meth) acrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, maleic anhydride, maleic acid monomethyl ester, maleic acid monobutyl ester, and itaconic acid. Examples thereof include carboxy group-containing aliphatic monomers such as monomethyl ester, itaconic acid monobutyl ester, and vinyl benzoic acid, but the present invention is not limited to these examples. These carboxy group-containing monomers may be used alone or in combination of two or more. Among these carboxy group-containing monomers, acrylic acid, methacrylic acid, maleic acid, fumaric acid and itaconic acid are preferable, and acrylic acid, methacrylic acid and itaconic acid are more preferable from the viewpoint of improving the mechanical strength of the film. preferable. The carboxy group may be in the form of a metal salt of the carboxy group (alkali metal or the like) or a salt such as an ammonium salt.

Examples of the hydroxyl group-containing (meth) acrylic acid ester monomer include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, and (meth). Examples thereof include hydroxyl group-containing (meth) acrylic acid ester monomers having 1 to 18 carbon atoms in ester groups such as 2-hydroxybutyl acrylate and 4-hydroxybutyl (meth) acrylate. It is not limited to illustrations only. These hydroxyl group-containing (meth) acrylic acid ester monomers may be used alone or in combination of two or more.

Examples of the oxo group-containing monomer include (di) ethylene glycol (methoxy) such as ethylene glycol (meth) acrylate, ethylene glycol methoxy (meth) acrylate, diethylene glycol (meth) acrylate, and diethylene glycol methoxy (meth) acrylate. Meta) acrylate and the like can be mentioned, but the present invention is not limited to such examples. These oxo group-containing monomers may be used alone or in combination of two or more.

Examples of the nitrogen atom-containing monomer include (meth) acrylamide, N-monomethyl (meth) acrylamide, N-monoethyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N-n-propyl (meth). ) Acrylamide, N-isopropyl (meth) acrylamide, methylenebis (meth) acrylamide, N-methylol (meth) acrylamide, N-butoxymethyl (meth) acrylamide, dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropylacrylamide , Acrylamide compounds such as diacetoneacrylamide, nitrogen atom-containing (meth) acrylic acid ester monomers such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, (meth) acrylonitrile and the like. However, the present invention is not limited to such examples. These nitrogen atom-containing monomers may be used alone or in combination of two or more.

Examples of the fluorine atom-containing monomer include a fluorine atom having 2 to 6 carbon atoms in an ester group such as trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate, and octafluoropentyl (meth) acrylate. Alkyl (meth) acrylate and the like can be mentioned, but the present invention is not limited to such examples. These fluorine atom-containing monomers may be used alone or in combination of two or more.

Examples of the epoxy group-containing monomer include epoxy group-containing (meth) acrylates such as glycidyl (meth) acrylate, α-methylglycidyl (meth) acrylate, and glycidyl allyl ether. It is not limited to illustrations only. These epoxy group-containing monomers may be used alone or in combination of two or more.

Examples of the carbonyl group-containing monomer include achlorine, formylstyrene, vinyl ethyl ketone, (meth) acrylic oxyalkylpropenal, acetnyl (meth) acrylate, diacetone (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. Acetyl acetate, butanediol-1,4-acrylate acetyl acetate, 2- (acetoacetoxy) ethyl (meth) acrylate and the like can be mentioned, but the present invention is not limited to these examples. These carbonyl group-containing monomers may be used alone or in combination of two or more.

Examples of the aziridinyl group-containing monomer include (meth) acryloyl aziridine, 2-aziridinyl ethyl (meth) acrylate, and the like, but the present invention is not limited to these examples. These aziridinyl group-containing monomers may be used alone or in combination of two or more.

Examples of the styrene-based monomer include styrene, α-methylstyrene, p-methylstyrene, tert-methylstyrene, chlorostyrene, vinyltoluene and the like, but the present invention is limited to such examples. It's not a thing. These styrene-based monomers may be used alone or in combination of two or more. The styrene-based monomer has an alkyl group such as a methyl group or a tert-butyl group, a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group, a functional group such as a halogen atom on the benzene ring. You may. Among the styrene-based monomers, styrene is preferable from the viewpoint of increasing the mechanical strength of the film.

Examples of the (meth) acrylic acid aralkyl ester monomer include benzyl (meth) acrylate, phenylethyl (meth) acrylate, methyl benzyl (meth) acrylate, and naphthylmethyl (meth) acrylate. Examples thereof include (meth) acrylic acid aralkyl ester monomers having 7 to 18 aralkyl groups, but the present invention is not limited to these examples. These (meth) acrylic acid aralkyl ester monomers may be used alone or in combination of two or more.

Among them, suitable monofunctional monomers include, for example, a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester monomer, an oxo group-containing monomer, a fluorine atom-containing monomer, and a nitrogen atom-containing monomer. Examples thereof include a monomer, an epoxy group-containing monomer, a styrene-based monomer, and the like, and these monomers may be used alone or in combination of two or more.

Examples of the polyfunctional monomer include ethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, and 1,4-butanediol di (meth) acrylate. , 1,6-hexanediol di (meth) acrylate, ethylene oxide-modified 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, propylene oxide-modified neopentyl glycol di (meth) acrylate , Di (meth) acrylate of polyhydric alcohol having 1 to 10 carbon atoms such as trimethylolpropylene di (meth) acrylate; Polyethylene glycol di (meth) acrylate having 2 to 50 additional moles of ethylene oxide, additional molar of propylene oxide Alkyldi (meth) acrylates having 2 to 50 molar additions of alkylene oxide groups having 2 to 4 carbon atoms, such as polypropylene glycol di (meth) acrylates having 2 to 50 numbers and tripropylene glycol di (meth) acrylates; ethoxy. Glycerin tri (meth) acrylate, propylene oxide-modified glycerol tri (meth) acrylate, ethylene oxide-modified trimethylolpropane tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol monohydroxytri (meth) acrylate, trimethylol Tri (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms such as propanetriethoxytri (meth) acrylate; pentaerythritol tetra (meth) acrylate, dipentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth). Tetra (meth) acrylate of polyvalent alcohol having 1 to 10 carbon atoms such as acrylate; Pentaerythritol Penta (meth) acrylate, dipentaerythritol (monohydroxy) Penta (meth) acrylate and other polyvalent alcohol having 1 to 10 carbon atoms Penta (meth) acrylate; hexa (meth) acrylate of a polyhydric alcohol having 1 to 10 carbon atoms such as pentaerythritol hexa (meth) acrylate; bisphenol A di (meth) acrylate, 2- (2'-vinyloxyethoxyethyl). ) Epoxy group-containing (meth) acrylates such as (meth) acrylates and epoxy (meth) acrylates; polyfunctional (meth) acrylates such as urethane (meth) acrylates; Examples thereof include the above-mentioned conjugated diene-based monomers, but the present invention is not limited to these examples. Each of these polyfunctional monomers may be used alone, or two or more kinds may be used in combination.

The mass ratio of the monomer unit derived from the other unsaturated monomer in the (meth) acrylic polymer is 50% by mass out of 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is preferably less than or equal to, more preferably 40% by mass or less, and further preferably 30% by mass or less. The lower limit of the mass ratio of the monomer unit derived from the other unsaturated monomer is not particularly limited and is 0% by mass, but the mass ratio is preferably 0.1% by mass or more.

When the (meth) acrylic polymer has a monomer unit derived from a carboxy group-containing monomer as a monomer unit derived from another unsaturated monomer, a single amount derived from the carboxy group-containing monomer. The mass ratio of the body unit is preferably 0.5% by mass or more based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer from the viewpoint of extending the life of the manufactured battery. It is more preferably 1% by mass or more, and further preferably 2% by mass or more. Further, the mass ratio of the monomer unit derived from the carboxy group-containing monomer is preferably 8% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably 4% by mass or less.

When the (meth) acrylic polymer has a styrene-based monomer-derived monomer unit as a monomer unit derived from other unsaturated monomers, the styrene-based monomer-derived monomer unit The mass ratio of is preferably 1% by mass or more, more preferably 5% by mass or more, and 10% by mass or more, based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. Is more preferable. Further, the mass ratio of the monomer unit derived from the styrene-based monomer is preferably 45% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer, which is 35. It is more preferably mass% or less, and further preferably 25 mass% or less.

When the (meth) acrylic polymer has a monomer unit derived from a polyfunctional monomer as a monomer unit derived from another unsaturated monomer, the monomer unit derived from the polyfunctional monomer The mass ratio of the above is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably 0.5% by mass or more. Further, the mass ratio of the monomer unit derived from the polyfunctional monomer is preferably 5% by mass or less based on 100% by mass of all the monomer units constituting the (meth) acrylic polymer. It is more preferably mass% or less.

<Physical properties and preparation method of conjugated diene polymer and (meth) acrylic polymer>
The conjugated diene polymer and the (meth) acrylic polymer preferably have a weight average molecular weight of 10,000 or more and 1,000,000 or less. The weight average molecular weight can be measured as a polystyrene-equivalent weight average molecular weight by gel permeation chromatography (GPC) under the following conditions.
Equipment: HCL-8220GPC manufactured by Tosoh Corporation
Column: TSKgel Super AWM-H
Eluent (LiBr · H ₂ O, NMP containing phosphoric acid): 0.01 mol / L

The conjugated diene-based polymer and the (meth) acrylic-based polymer preferably have a glass transition temperature (Tg) of −20 ° C. or higher and 50 ° C. or lower. This is because when the Tg of the conjugated diene polymer or the (meth) acrylic polymer is less than −20 ° C., the strength of the anion conductive film may be insufficient and the dendrite suppressing effect may be lowered. Further, when the Tg exceeds 50 ° C., the anion conductive film becomes too hard and brittle, and cracks or the like may occur in the anion conductive film when forming the battery, which may reduce the life performance of the battery. Because. In the anionic conductive film of the present invention, voids are formed due to the aggregation of at least one inorganic compound particles selected from the group consisting of oxides, hydroxides, and layered double hydroxides. In order to suppress the above, the components contained in the material for forming the anionic conductive film (hereinafter, such a material before film formation is also referred to as the anionic conductive film forming material) are sufficiently kneaded to form an inorganic compound. It is preferable to suppress the aggregation of the particles so that the inorganic compound particles and the components other than the inorganic compound particles are in a uniform state. When the Tg of the conjugated diene polymer or the (meth) acrylic polymer is -20 ° C or higher and 50 ° C or lower, the kneaded product at the time of kneading with the inorganic compound particles becomes appropriately fluid, and the inorganic compound particles have an appropriate fluidity. It is possible to crush the agglomerates and make the components contained in the anionic conductive film-forming material more uniform. The Tg of the conjugated diene-based polymer or the (meth) acrylic-based polymer is more preferably −15 ° C. or higher and 30 ° C. or lower, and further preferably −10 ° C. or higher and 20 ° C. or lower.
The Tg of the conjugated diene polymer or the (meth) acrylic polymer can be measured by a differential scanning calorimeter according to the method described in Examples.

The conjugated diene-based polymer and the (meth) acrylic-based polymer can be produced by polymerizing a monomer component that forms a structural unit contained in the above-mentioned polymer.
The polymerization method of the monomer component is not particularly limited, and examples thereof include methods such as an aqueous solution polymerization method, an emulsion polymerization method, a reverse phase suspension polymerization method, a suspension polymerization method, a solution polymerization method, and a bulk polymerization method. it can. Among these methods, it is preferable to use the emulsion polymerization method from the viewpoint of easy production.
When the emulsion polymerization method is used as the polymerization method of the above-mentioned monomer component, the emulsion polymerization may be carried out after mixing the monomer component, the surfactant and the dispersion medium containing water as the main components. The ingredients, surfactants and aqueous medium may be emulsified by stirring to prepare a preemulsion and then emulsion polymerization, or at least one of the monomeric components, surfactants and medium and the rest thereof. May be mixed with the pre-emulsion of the above to carry out emulsion polymerization. The monomer component, the surfactant and the medium may be added all at once, may be added separately, or may be continuously added dropwise.

Examples of the above-mentioned surfactant include anionic surfactants, nonionic surfactants, cationic surfactants, amphoteric surfactants and the like, and one or more of these surfactants are used. be able to.
The anionic surfactant is not particularly limited, and is, for example, an alkyl sulfate salt such as ammonium dodecyl sulfate or sodium dodecyl sulfate; an alkyl sulfonate salt such as ammonium dodecyl sulfonate, sodium dodecyl sulfonate, or sodium alkyl diphenyl ether disulfonate; dodecylbenzene sulfone. Alkylaryl sulfonate salts such as sodium dodecylbenzenesulfonate, sodium dodecylnaphthalene sulfonate, etc .; polyoxyethylene alkylphenyl ether sulfate salts; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryl Sulfate salt; dialkyl sulfosuccinate; aryl sulfonic acid-formalin condensate; fatty acid salts such as ammonium laurylate and sodium stearilate; bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfonate salt, propenyl-alkyl sulfosuccinate salt, Sulfate ester having an allyl group such as (meth) polyoxyethylene sulfonate salt of acrylate, polyoxyethylene phosphonate salt of (meth) acrylate, sulfonate salt of allyloxymethylalkyloxypolyoxyethylene, or a salt thereof; allyloxymethyl Examples thereof include a sulfate ester salt of alkoxyethylpolyoxyethylene.

The nonionic surfactant is not particularly limited, and is, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, condensate of polyethylene glycol and polypropylene glycol, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, fatty acid. Examples thereof include monoglyceride, a condensate of ethylene oxide and an aliphatic amine, allyloxymethylalkoxyethyl hydroxypolyoxyethylene, and polyoxyalkylene alkenyl ether.
The cationic surfactant is not particularly limited, and examples thereof include alkylammonium salts such as dodecylammonium chloride.
The amphoteric surfactant is not particularly limited, and examples thereof include betaine ester-type surfactants.

The amount of the surfactant used in the above emulsion polymerization method is polymerization stability with respect to 100% by mass of all the monomer components used as raw materials for the conjugated diene polymer and / or the (meth) acrylic polymer. From the viewpoint of improving the above, preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, and particularly preferably 1% by mass. % Or more. Further, from the viewpoint of extending the life of the battery, it is preferably 10% by mass or less, more preferably 7% by mass or less, and further preferably 5% by mass or less.

A polymerization initiator can be used for the polymerization of each of the above-mentioned monomer components. As the polymerization initiator, a commonly used one can be used, and is not particularly limited as long as it generates radical molecules by heat. Examples of the polymerization initiator include persulfates such as potassium persulfate, ammonium persulfate, and sodium persulfate; 2,2'-azobis [N- (2-carboxyethyl) -2-methylpropion amidine], 2,2. Water-soluble azo compounds such as'-azobis (2-amidinopropane) dihydrochloride, 4,4'-azobis (4-cyanopentanoic acid); thermal decomposition initiators such as hydrogen peroxide; hydrogen peroxide and ascorbic acid , T-Butylhydroperoxide and Longalit, Potassium Persulfate and Metal Salt, Ammonium Persulfate and Sodium Hydrogen Sulfite, and other redox-based initiators, and one or more of these can be used. ..

The amount of the polymerization initiator used is preferably 0.02% by mass or more and 2% by mass or less with respect to 100% by mass of the total amount of the monomer components to be subjected to the polymerization reaction. More preferably, it is 0.05% by mass or more and 1% by mass or less.

The temperature of the polymerization reaction for producing the conjugated diene polymer or the (meth) acrylic polymer is not particularly limited as long as the polymerization reaction proceeds, but it is preferably carried out at 20 ° C. or higher and 100 ° C. or lower. More preferably, it is 40 ° C. or higher and 90 ° C. or lower.
Further, the time of the polymerization reaction is not particularly limited, but in consideration of productivity, 0.5 hours or more and 10 hours or less are preferable. More preferably, it is 1 hour or more and 5 hours or less.

When the emulsion polymerization method using water as a medium is used as the polymerization method of the monomer component, the volume average of the conjugated diene polymer or the (meth) acrylic polymer obtained as latex particles in an aqueous dispersion. From the viewpoint of forming a uniform film, the particle size is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more, and the binder in the film (mainly a conjugated diene polymer or (meth)). From the viewpoint of suppressing the permeation of water and ions into the portion (component composed of the acrylic polymer), the thickness is preferably 5000 nm or less, more preferably 1000 nm or less, still more preferably 500 nm or less.
The volume average particle size can be measured using a particle size distribution measuring device according to the method described in Examples.

The mass ratio of the conjugated diene polymer or the (meth) acrylic polymer is 10% by mass or more in 100% by mass of the anion conductive film forming material from the viewpoint of the strength of the anionic conductive film and the ionic conductivity. It is more preferable, it is more preferably 15% by mass or more, further preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. The mass ratio is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less.
Here, the preferable mass ratios of the conjugated diene polymer and the (meth) acrylic polymer in the anionic conductive film-forming material have been described, but the conjugated diene polymer and the (meth) acrylic polymer in the anionic conductive film have been described. The same applies to the preferable mass ratio of the polymer.
Here, the "mass ratio of the conjugated diene polymer or the (meth) acrylic polymer" means whether the anionic conductive film-forming material or the anionic conductive film is the conjugated diene polymer or the (meth) acrylic polymer. When one of them is contained, it means the mass ratio of the contained polymer, and when the anionic conductive film forming material or the anionic conductive film contains both a conjugated diene polymer and a (meth) acrylic polymer. Means the total mass ratio of both.

<At least one inorganic compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides>
The anionic conductive membrane of the present invention contains at least one inorganic compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides.
The above-mentioned inorganic compound is at least one element selected from Li, Na, Mg, Al, K, Ca, transition metal elements of the 4th to 5th periods, Zn, In, Sn, Pb, and Bi as constituent elements. It is preferable that it is an inorganic compound containing.

Examples of the oxide include lithium oxide, sodium oxide, potassium oxide, calcium oxide, barium oxide, scandium oxide, yttrium oxide, lanthanoid oxide, zirconium oxide, niobium oxide, ruthenium oxide, nickel oxide, palladium oxide, copper oxide and oxidation. Those containing at least one compound selected from the group consisting of cadmium, boron oxide, gallium oxide, indium oxide, tallium oxide, silicon oxide, germanium oxide, tin oxide, lead oxide, phosphorus oxide, and bismuth oxide are preferable. More preferably, it is cerium oxide or zirconium oxide, and even more preferably, it is cerium oxide. Further, the cerium oxide may be, for example, a samarium oxide, gadolinium oxide, bismuth oxide or the like doped with a metal oxide, or a solid solution with a metal oxide such as zirconium oxide. It may have an oxygen defect.

Examples of the hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, barium hydroxide, scandium hydroxide, yttrium hydroxide, lanthanoid hydroxide, zirconium hydroxide, niobium hydroxide, and water. Luthenium oxide, nickel hydroxide, palladium hydroxide, copper hydroxide, cadmium hydroxide, boric acid, gallium hydroxide, indium hydroxide, tallium hydroxide, silicic acid, germanium hydroxide, tin hydroxide, lead hydroxide, phosphorus Those containing at least one compound selected from the group consisting of acid and bismuth hydroxide are preferable. More preferably, it is cerium hydroxide or zirconium hydride.

The layered double hydroxide is the following general formula:
^{_{[M 1 1-x M 2}} x (OH) 2] (A n-) x / n · mH 2 O
(M ¹ represents a divalent metal ion which is any one of Mg, Fe, Zn, Ca, Li, Ni, Co, Cu and Mn. M ² represents Al, Fe, Mn, Co, Cr and In. the ^.A n-representing a trivalent metal ion is any ^{_{one, OH -, Cl -, NO}} 3 -, CO 3 2-, COO - 1 or more valences such as, the .m representing a trivalent following anions 0 The above number, n is a number of 1 or more and 3 or less. X is a number of 0.20 or more and 0.40 or less). It is preferable that ^An− is a divalent or less anion.
Such layered double hydroxides are naturally occurring (eg, hydrotalcite, manaceite, motukoreaite, stichtite, sjogrenite, barbertite). , Pyroaurite, Iomaite, Chlormagalminite, Hydrocalmite, Green Last 1, Green Last 1, Berthierine, Tacoveite (Reevesite), Honesite, Eardlyite, Meixnerite, etc.), or artificially synthesized compounds, which may be artificially synthesized, by firing at 150 ° C. or higher and 900 ° C. or lower. It may be a dehydrated compound, a compound obtained by decomposing anions in layers, or a compound in which anions in layers are exchanged for hydroxide ions or the like.
Among these layered double hydroxides, Mg—Al-based layered double hydroxides such as hydrotalcite are preferable.

Among them, the inorganic compound is preferably a layered double hydroxide and / or an oxide, and more preferably a layered double hydroxide.

As described above, the inorganic compound is preferably in the form of particles from the viewpoint of suppressing the permeation of zincate ions into the film and the permeability of hydroxide ions, and the shape thereof is fine powder or powder. , Granular, granular, scaly, polyhedral, rod-like, curved surface-containing state and the like. For particles having an average particle size in the range described below, for example, a method of crushing the particles with a ball mill or the like, dispersing the obtained coarse particles in a dispersant to obtain a desired particle size, and then drying the particles. In addition to the method of selecting the particle size by sieving the coarse particles, the production can be performed by a method of optimizing the preparation conditions at the stage of producing the particles and obtaining (nano) particles having a desired particle size.

The inorganic compound preferably has an average particle size of 5 μm or less, more preferably 1 μm or less, still more preferably 0.5 μm or less, and particularly preferably 0.3 μm or less. On the other hand, the average particle size is preferably 0.001 μm or more, more preferably 0.01 μm or more. By using an inorganic compound having an average particle size in the above range, the permeability of hydroxide ions becomes better.
The average particle size can be measured by a laser diffraction method according to the method described in the method of the example.

The mass ratio of the inorganic compound is preferably 30% by mass or more in 100% by mass of the anion conductive film forming material from the viewpoint of improving the strength and ionic conductivity of the anion conductive film. The mass ratio is more preferably 40% by mass or more, further preferably 50% by mass or more, and particularly preferably 60% by mass or more. The mass ratio is preferably 90% by mass or less, more preferably 85% by mass or less, further preferably 80% by mass or less, and particularly preferably 75% by mass or less.
Here, the preferable mass ratio of the inorganic compound in the anionic conductive membrane-forming material has been described, but the preferable mass ratio of the inorganic compound in the anionic conductive membrane is also the same.

<Other ingredients>
The anion conductive film of the present invention is at least one selected from the group consisting of a conjugated diene polymer and / or a (meth) acrylic polymer and an oxide, a hydroxide, and a layered double hydroxide. Other components may be contained as long as they include an inorganic compound.
Among other components, the polymer is represented by a hydrocarbon site-containing polymer such as polyolefin such as polyethylene and polypropylene, an aryl group-containing polymer such as polystyrene; and polyalkylene glycol such as polyethylene oxide and polypropylene oxide. Ether group-containing polymer; hydroxyl group-containing weight of polyvinyl alcohol, poly (α-hydroxymethylacrylate), cellulose, methyl cellulose, hydroxyethyl methyl cellulose, hydroxypropyl methyl cellulose, hydroxyalkyl cellulose (for example, hydroxyethyl cellulose, hydroxypropyl cellulose, etc.) Combined; amide group-containing polymers such as polyamide, nylon, polyacrylamide, polyvinylpyrrolidone and N-substituted polyacrylamide; imide group-containing polymers such as polymaleimide and polyimide; poly (meth) acrylic acid (salt), polymaleic acid ( (Salt), polyitaconic acid (salt), polymethyleneglutaric acid (salt), carboxymethyl cellulose and other carboxy group-containing polymers (including carboxy group metal salts (alkali metals, etc.) and ammonium salts, etc.); Poly (meth) acrylic Carboxylate-containing polymers such as acid salts, polymaleates, polyitaconates, and polymethyleneglutarates; halogen atom-containing polymers such as polyvinyl chloride, polyvinylidene fluoride, and polytetrafluoroethylene; epoxys such as epoxy resins. Polycondensate of group-containing compound; sulfonic acid group-containing polymer; sulfonic acid (salt) -containing polymer; quaternary ammonium base-containing polymer; quaternary phosphonium base-containing polymer; used for cation / anion exchange membrane, etc. Ion-exchangeable polymers; sugars such as cellulose acetate, chitin, chitosan, alginic acid (salt); amino group-containing polymers such as polyethyleneimine; carbamate group-containing polymers; carbamide group-containing polymers; heterocycles and / or Examples thereof include conjugated diene-based polymers such as ionized heterocyclic substituent-containing polymers and polymers other than (meth) acrylic-based polymers, and one or more of these can be used.
By adding such other polymers, effects such as improving the strength of the film can be obtained.
In addition, these polymers may be crosslinked with a known organic cross-linking agent compound.
By adding a polymer other than such a conjugated diene-based polymer and a (meth) acrylic-based polymer, effects such as improving the uniformity of the film and the strength of the film can be obtained.

The content of the polymer other than the conjugated diene polymer and the (meth) acrylic polymer is 20% by mass or less with respect to 100% by mass of the anionic conductive film from the viewpoint of material uniformity and film moldability. It is preferably, more preferably 10% by mass or less.
When two or more kinds of polymers other than the conjugated diene polymer and the (meth) acrylic polymer are contained, the above content is the total amount of the polymers other than the conjugated diene polymer.

These polymers may be crosslinked with known organic cross-linking agent compounds.

Other components that may be contained in the anionic conductive film of the present invention include polymers other than conjugated diene-based polymers and (meth) acrylic-based polymers, as well as, for example, conductive carbon and conductive ceramics. Other inorganic components can be mentioned.

The content ratio of other inorganic components in the anion conductive membrane of the present invention is preferably 1% by mass or less, more preferably 0.5% by mass, based on 100% by mass of the anion conductive membrane from the viewpoint of film strength. It is less than or equal to, more preferably 0.2% by mass or less.

<Method for producing anionic conductive membrane of the present invention>
As a method for producing an anion conductive film of the present invention, a step of preparing a material for forming an anion conductive film (hereinafter, such a material before film formation is also referred to as an anion conductive film forming material). In addition, the step of molding the obtained anion conductive film-forming material into a film shape is included.
Examples of the method for preparing the anion conductive film-forming material in the present invention include the following methods.
If necessary, other components are mixed together with the conjugated diene-based polymer and / or the (meth) acrylic-based polymer, and the inorganic compound. For mixing, a mixer, a blender, a kneader, a bead mill, a ready mill, a roll mill, a ball mill and the like can be used. At the time of mixing, water, an organic solvent such as methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran, N-methylpyrrolidone, or a mixed solvent of water and an organic solvent may be added as a medium.

The content ratio of the medium in the anionic conductive film-forming material of the present invention is 20% by mass or more and 60% by mass or less in 100% by mass of the anionic conductive film-forming material from the viewpoint of suppressing film shrinkage during molding. preferable. The content ratio is more preferably 30% by mass or more and 50% by mass or less. By adjusting the content ratio of the medium in this way, the liquid absorption rate of the anionic conductive membrane of the present invention can be suitably adjusted.
The medium also includes a dispersion medium in which the polymer is dispersed or a solvent in which the polymer is dissolved, in which the polymer contained in the anionic conductive film-forming material is in the form of a dispersion or a solution.

The method for producing an anionic conductive film from an anionic conductive film-forming material is not particularly limited as long as the film is formed, and a method of rolling an anionic conductive film-forming material with a roll to form a film, a flat plate press, etc. A method of forming into a film by rolling with, or a method of forming into a film such as an injection molding method, an extrusion molding method, or a casting method can be used. These molding methods may be used alone or in combination of two or more methods.
A method for producing an anionic conductive film in this manner, that is, selected from the group consisting of a conjugated diene polymer and / or a (meth) acrylic polymer and an oxide, a hydroxide, and a layered double hydroxide. A method for producing an anionic conductive film, which comprises a step of forming an anionic conductive film-forming material containing at least one inorganic compound to be formed into a film, is also one of the present inventions. As the anion conductive film forming material used in this production method, the above-mentioned one is preferable, and the anion conductive film to be produced is also preferably the above-mentioned anion conductive film of the present invention.

The above-mentioned production method preferably includes a step of heating the film after the step of forming the anion conductive film-forming material into a film shape. Thereby, the liquid absorption rate of the anion conductive membrane can be appropriately reduced.
In the heat treatment after the film formation, the heating temperature may be appropriately set, and can be, for example, 60 ° C. or higher and 180 ° C. or lower. The heating temperature is preferably 160 ° C. or lower, more preferably 150 ° C. or lower. Moreover, the heating temperature may be changed stepwise. By setting the temperature in such a range, the life performance of the anion conductive membrane can be further improved.

<Separator>
The anionic conductive film of the present invention can be suitably used as a battery separator, and the battery can be extended in life by using such a separator.
Such a separator configured including the anionic conductive film of the present invention is also one of the present inventions.

<Battery>
A battery configured using the separator of the present invention is also one of the present inventions.
In the battery of the present invention, the anionic conductive film exerts the function of a separator, but another separator may be laminated on the anionic conductive film of the present invention.
Such separators include non-woven fabrics, filter papers, polyolefin resins such as polyethylene and polypropylene, fluorine atom-containing resins such as polytetrafluoroethylene and polyvinylidene fluoride, cellulose, fibrillated cellulose, biscous rayon, cellulose acetate, and hydroxyalkyl cellulose. , Carboxymethyl cellulose, polyvinyl alcohol, aryl group-containing resin such as polystyrene, polyacrylonitrile resin, polyacrylamide resin, polyamide resin, polyimide resin, (meth) acrylic resin, hydroxyl group-containing resin such as polyisoprenol and poly (meth) allyl alcohol. , Polycarbonate resin, polyester resin, polyurethane resin, agar, organic-inorganic composite resin, ion exchange resin, sulfonate-containing resin, quaternary ammonium salt-containing resin, quaternary phosphonium salt-containing resin, cycloolefin polymer, inorganic substances such as ceramics, etc. A membrane composed of. One kind or two or more kinds of these separators may be used.
The laminated structure in which the anion conductive film of the present invention and another separator are laminated may be an integrated laminated structure or a laminated structure in which they are independently laminated. When the films are in close contact with each other, the laminated structure may have a clear interface, or the laminated structure may have a mixed layer in which these components are mixed.

As the positive electrode active material constituting the battery of the present invention, a material usually used as a positive electrode active material of a primary battery or a secondary battery can be used, and is not particularly limited, but for example, oxygen (oxygen is a positive electrode active material). If so, the positive electrode contains perovskite-type compounds, cobalt-containing compounds, iron-containing compounds, copper-containing compounds, manganese-containing compounds, vanadium-containing compounds, nickel-containing compounds, iridium-containing compounds, and platinum-containing compounds that can reduce oxygen and oxidize water. Compound; Palladium-containing compound; Gold-containing compound; Silver-containing compound; Air electrode composed of carbon-containing compound, etc.); Nickel-containing compound such as nickel oxyhydroxide, nickel hydroxide, cobalt-containing nickel hydroxide, etc .; Manganese dioxide Manganese-containing compounds such as; silver oxide; lithium-containing compounds such as lithium cobalt oxide; iron-containing compounds; zinc species such as metallic zinc and zinc oxide.
Among these, it is one of the preferred embodiments of the present invention that the positive electrode active material is a nickel-containing compound or a zinc species.
Further, it is also one of the preferred embodiments of the present invention that the positive electrode active material such as an air battery or a fuel cell is oxygen.

As the negative electrode active material constituting the battery of the present invention, carbon, lithium, sodium, magnesium, zinc, nickel, tin, cadmium, hydrogen storage alloy, silicon-containing material, etc., which are usually used as the negative electrode active material of the battery, are used. Can be used. Among these, from the viewpoint of demonstrating the characteristics of the anionic conductive membrane of the present invention, dendrites may be generated due to electrode reactions such as lithium, magnesium, zinc, nickel, and cadmium. In particular, it can be preferably used as it is.

The electrodes constituting the battery of the present invention can be manufactured by forming an active material layer on a current collector.
The current collectors that make up the electrodes include (electrolytic) copper foil, copper mesh (expanded metal), foamed copper, punching copper, copper alloys such as brass, brass foil, brass mesh (expanded metal), foamed brass, and punching brass. , Nickel foil, Corrosion resistant nickel, Nickel mesh (expanded metal), Punching nickel, Metallic zinc, Corrosion resistant metallic zinc, Zinc foil, Zinc mesh (Expanded metal), (Punching) Steel plate, Non-woven fabric with conductivity; Ni ・ Zn ・(Electrolytic) copper foil with added Sn, Pb, Hg, Bi, In, Tl, brass, etc. (electrolytic) Copper foil, copper mesh (expanded metal), foamed copper, punching copper, copper alloys such as brass, brass foil, brass mesh (expanded metal) ) ・ Foamed brass ・ Punching brass ・ Nickel foil ・ Corrosion resistant nickel ・ Nickel mesh (expanded metal) ・ Punching nickel ・ Metallic zinc ・ Corrosion resistant metal zinc ・ Zinc foil ・ Zinc mesh (expanded metal) ・ (Punching) steel plate ・ Non-woven fabric; Ni ・(Electrolytic) copper foil, copper mesh (expanded metal) plated with Zn, Sn, Pb, Hg, Bi, In, Tl, brass, etc., copper foam, punching copper, copper alloy such as brass, brass foil, brass mesh (Expanded metal), foamed copper, punching brass, nickel foil, corrosion-resistant nickel, nickel mesh (expanded metal), punching nickel, metallic zinc, corrosion-resistant metal zinc, zinc foil, zinc mesh (expanded metal), (punching) steel plate, non-woven fabric ; Silver; Materials used as current collectors and containers for alkaline (storage) batteries and air-zinc batteries.

The anionic conductive membrane of the present invention can be used not only as a solid electrolyte but also as an ion exchange membrane. When the anion conductive membrane of the present invention is used as an ion exchange membrane, an electrolyte solution or a gel electrolyte can be separately used as an electrolyte material. The electrolytic solution constituting the battery of the present invention is not particularly limited as long as it is usually used as the electrolytic solution of the battery, and examples thereof include a water-containing electrolytic solution, an organic solvent-based electrolytic solution, and the like. Is preferable. The water-containing electrolytic solution refers to an electrolytic solution (aqueous electrolytic solution) that uses only water as an electrolytic solution raw material, or an electrolytic solution that uses a solution obtained by adding an organic solvent to water as an electrolytic solution raw material. Further, the anionic conductive membrane of the present invention can also exhibit anionic conductivity under humidifying conditions, heating conditions, and conditions in the absence of the above-mentioned electrolytic solution or solvent.

As the water-based electrolytic solution, an alkaline electrolytic solution is preferable. Examples of the alkaline electrolytic solution include potassium hydroxide aqueous solution, sodium hydroxide aqueous solution, lithium hydroxide aqueous solution, zinc sulfate aqueous solution, zinc nitrate aqueous solution, zinc phosphate aqueous solution, zinc acetate aqueous solution and the like. The above-mentioned aqueous electrolytic solution can be used alone or in combination of two or more.

Further, the water-containing electrolytic solution may contain an organic solvent used in the organic solvent-based electrolytic solution. Examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, γ-butyrolactone, dimethoxymethane, diethoxymethane, dimethoxyethane, tetrahydrofuran, methyl tetrahydrofuran, diethoxyethane, dimethyl sulfoxide, sulfolane, acetonitrile, and the like. Examples thereof include benzonitrile, ionic liquid, fluorine-containing carbonates, fluorine-containing ethers, polyethylene glycols, fluorine-containing polyethylene glycols and the like. The above-mentioned organic solvent-based electrolytic solution can be used alone or in combination of two or more. The electrolyte of the organic solvent-based electrolyte is not particularly limited, but LiPF ₆ , LiBF ₄ , LiB (CN) ₄ , lithium bis (fluorosulfonyl) imide (LiFSI), lithium bis (trifluoromethylsulfonyl) imide ( LiTFSI) and the like are preferable.
In the case of a water-containing electrolytic solution containing an organic solvent-based electrolytic solution, the content of the aqueous electrolytic solution is preferably 10% by mass or more, 99.9% with respect to the total of 100% by mass of the water-based electrolytic solution and the organic solvent-based electrolytic solution. It is mass% or less, more preferably 20 mass% or more, and 99.9 mass% or less.

The gel electrolyte constituting the battery of the present invention is not particularly limited as long as it can be used as the electrolyte of the battery. For example, a solid electrolyte containing a compound similar to the above separator or a gel crosslinked by a cross-linking agent is used. Examples include electrolytes.

The form of the battery of the present invention is a primary battery; a rechargeable secondary battery (storage battery); utilization of mechanical culture (mechanical replacement of zinc negative electrode); utilization of a third pole (electrode suitable for charging as a positive electrode). It may be in any form, such as an electrode suitable for discharging), a fuel cell, etc., but a secondary battery or a fuel cell is preferable.
The type of battery of the present invention is not particularly limited, but is a battery that uses an alkaline electrolyte, such as an alkaline dry battery, a nickel-hydrogen battery, a nickel-cadmium battery, a manganese-zinc battery, a nickel-zinc battery, a fuel cell, and an air battery. It is preferable to have.

The anion conductive film of the present invention has the above-mentioned structure, has selective permeability of hydroxide ions, and can effectively suppress the growth of dendrites, so that the electrode activity that produces dendrites is active. It can be suitably used as a separator for a battery using a substance, especially a zinc type, and can extend the life of the battery.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples. Unless otherwise specified, "part" means "part by weight" and "%" means "mass%".

Various measurements in the examples were carried out by the following methods.
<Charge / discharge test>
・ Number of charged cells: 5 cells (list the average value)
-Cell constituent action electrode: Zinc oxide powder / PTFE (polytetrafluoroethylene) mixture attached to a tin-plated punched steel plate current collector Counter electrode: Zinc oxide / PTFE mixture welded with zinc metal reference electrode that was attached to the collector: a mercury electrode-electrolyte: KOH aqueous solution, the charge and discharge conditions the charge-discharge current value of 6.7 mol / L concentration saturated with zinc ^oxide: 60mA / cm 2 ^-10min

<Liquid absorption rate>
On specimens 10 sheets cut from any location 25 mm × 25 mm square of the anion conducting membrane, the mass of each dry _{(M b)} and, KOH aqueous solution 6.7 mol / L concentration saturated with zinc oxide was liquid absorption rate by respectively calculated from the mass when immersed overnight (M _a), obtain their average values as two significant figures on.

<Swelling degree>
Ten test pieces cut into 25 mm × 25 mm squares from any location of the anionic conductive membrane were immersed overnight in a dry film thickness (T _b ) and a 6.7 mol / L concentration KOH aqueous solution. respectively calculated from the thickness (T _a) of the time was, and swelling degree by obtaining an average value as two significant figures.

<Resistance value>
The resistance value R (Ω) was measured under the following conditions.
・ Number of charged cells: 5 cells (list the average value)
-Cell composition Working electrode: Ni plate counter electrode: Ni plate Electrolyte: 6.7 mol / L concentration KOH aqueous solution saturated with zinc oxide Measurement sample: Immerse in the above electrolyte overnight Effective area: φ15 mm
・ Measure AC impedance. After allowing to stand in a constant temperature bath at 25 ° C. for 30 minutes, the measurement was carried out under the following conditions.
Applied voltage: 10 mV vs. Open circuit voltage frequency range: 100kHz to 100Hz
The resistance value (R) was calculated from the intercept component (Ra) obtained by impedance and the intercept component (Rb) when the measurement sample was not included by the following formula.
R = (Ra-Rb)

<Air permeability value>
In the embodiment, the air permeability value T (s) is measured by the Oken type air permeability smoothness measuring device KY-55 (manufactured by Asahi Seiko Co., Ltd.) according to the JIS P8117 (2009) Oken type testing machine method. It was measured and the average value of the measured values was calculated. The upper limit of the measurement time was set to 30,000 s, and when the upper limit of the measurement was exceeded, the air permeability value was set to 30,000 s. That is, in the embodiment, the air permeability value of 30,000 s means that it is at least 30,000 s, and the X value obtained from this means the value of the X value when it is estimated to be the least.

<Puncture strength>
The puncture strength F (N) was measured with a digital force gauge ZTA-50N (manufactured by Imada) according to JIS Z1707 (1997). The test piece was fixed, and a semicircular needle-shaped jig with a diameter of 1.0 mm and a tip shape radius of 0.5 mm was pierced at a speed of 50 ± 5 mm per minute, and the maximum stress until the tip of the jig penetrated was measured. .. The number of test pieces was 5 or more, and the average value was calculated.

<Density>
The density ρ (g / cm ³ ) was calculated by measuring the mass and volume of the test piece of the anionic conductive membrane and dividing the mass by the volume. The volume of the test piece was calculated by measuring the length in the vertical direction and the length in the horizontal direction of the test piece using a caliper, and measuring the film thickness based on the following film thickness measuring method. The mass of the test piece was measured using a precision balance having four decimal places for the test piece whose volume was measured.

<Film thickness>
The film thickness L (μm) of the anion conductive film was measured using a digital micrometer 543-394 (manufactured by Mitutoyo Co., Ltd.). Arbitrary 10 points of the membrane were measured, and the average value was taken as the film thickness of the anionic conductive membrane.

<Calculation of X value>
The X value is the following formula (1) using the air permeability value T (s), the puncture strength F (N), the density ρ (g / cm ³ ), and the film thickness L (μm) calculated by the above measurement method. Obtained by.

<Average particle size of inorganic compound particles>
The average particle size of the inorganic compound particles is determined by a laser diffraction method (device name: laser diffraction / scattering type particle size distribution measuring device LA-950 manufactured by HORIBA) using a dispersion liquid in which the inorganic compound particles are dispersed in the following dispersion medium. , Dispersion medium: 0.2 mass% sodium hexametaphosphate-containing ion-exchanged water), and the obtained 50% volume average particle size was obtained as the average particle size.
<Volume average particle size of polymer aqueous dispersion>
The volume average particle size of the polymer water dispersion is determined by diluting the polymer water dispersion with distilled water, collecting about 10 mL of the obtained diluent in a glass cell, and measuring this by a dynamic light scattering method. The measurement was performed using [Particle Size Systems, Inc., trade name: NICOMP Model 380], and a 50% volume average particle size was obtained as the average particle size.

<Glass transition temperature>
The glass transition temperature of the polymer is such that the polymer is applied to a glass plate and dried at 120 ° C. for 1 hour to form a polymer film, and the obtained polymer film is subjected to a differential scanning calorimeter (device name:: It was measured using a thermal analyzer DSC3100S, BRVKER).

<Area ratio of compound particles to anionic conductive film-forming material components other than compounds>
The area ratio is the cross section of the membrane obtained by cutting the anionic conductive membrane perpendicular to the surface of the membrane (the cross section of the membrane was prepared using a range of 10 mm × 10 mm at the center of the short side of the anionic conductive membrane). Using a scanning electron microscope, 10,000-fold magnified photographs were taken at five locations at arbitrary locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film-forming material portion was extracted, and the material portion was converted into a black-and-white display. In such an image, the portion other than the inorganic compound particles is displayed in black, and the portion of the inorganic compound particles is displayed in white. Using image analysis software manufactured by Image matrix Co., Ltd., the ratio of the total area of the inorganic compound particle portion to the total area of the portion other than the inorganic compound particle in the obtained image was determined. At the time of treatment, the contrast between the black part and the white part was clarified so that the particles could be clearly separated.

<Ratio of voids>
Similar to the above area ratio, the membrane cross section obtained by cutting the anionic conductive membrane perpendicularly to the surface of the membrane (the membrane cross section is prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). With a scanning electron microscope, 10,000-fold magnified photographs were taken at five locations at arbitrary locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film-forming material portion was extracted, and the material portion was converted into a black-and-white display. In such an image, the void portion is displayed in black, and the other component portions are displayed in white. The ratio of the void portion to the image was determined by using image analysis software manufactured by Image metrology for the obtained image. At the time of treatment, the contrast between the black portion and the white portion was clarified so that the void portion could be clearly separated.

<Cross-sectional particle size of inorganic compound particles in the membrane>
Similar to the above area ratio, the membrane cross section obtained by cutting the anionic conductive membrane perpendicularly to the surface of the membrane (the membrane cross section is prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). A scanning electron microscope was used to take 10,000-fold magnified photographs of any five locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. At this time, the contrast was adjusted and stored so that only the inorganic compound particle portion could be displayed in white by the following image processing. A region of 8 μm in the thickness direction × 12 μm in the plane direction in the obtained enlarged cross-sectional photograph was developed by Microsoft's image creation software, Paint Ver. It was taken up in 5.1, and the region of the anion conductive film-forming material portion was extracted, and the material portion was converted into a black-and-white display. In the image, the inorganic compound particle portion was displayed in white, and the size of the white portion in the image was determined as the particle diameter of the inorganic compound particle using image analysis software manufactured by Image matrix Co., Ltd. for the obtained image. At the time of treatment, the contrast between the black part and the white part was clarified so that the particles could be clearly separated. The measurement was performed on 100 particles, and the average value was taken as the cross-sectional particle diameter. When the observed particles are elliptical particles, 100 particles are measured on each of the major axis side and the minor axis side, and the average value of the respective average values is the cross-sectional particle diameter of the particles in the film. And said.

<Evaluation of ease of film formation>
The ease of film formation was evaluated as follows.
0. The film could not be formed.
1. 1. The film was formed, but a part of the sheet was torn due to adhesion to the roll.
2. There is little cracking and damage, but there is a lot of unevenness.
3. 3. I was able to form a film firmly.

<Preparation example of (meth) acrylic polymer>
[Preparation Example 1]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 26 parts by mass of deionized water, 4 parts by mass of 10% aqueous sodium dodecylbenzene sulfonate solution, 1.5 parts by mass of 1,6-hexanediol dimethacrylate, 46.5 parts by mass of methyl methacrylate, and methacrylic acid were added to the dropping funnel. A pre-emulsion consisting of 50 parts by mass of dodecyl and 2 parts by mass of acrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.2% and the pH to about 8. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle size of 190 nm was obtained at 7.8.

[Preparation Example 2]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, a preemulsion consisting of 26 parts by mass of deionized water, 4 parts by mass of a 10% sodium dodecylbenzene sulfonate aqueous solution, 54 parts by mass of methyl methacrylate, 44 parts by mass of dodecyl methacrylate, and 2 parts by mass of acrylic acid was prepared in the dropping funnel. did. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 47.8% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 7.6 nm was obtained.

[Preparation Example 3]
63 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 21 parts by mass of deionized water, 10 parts by mass of a 25% aqueous solution of Hytenol LA-10, 1.5 parts by mass of 1,6-hexanediol dimethacrylate, 21 parts by mass of methyl methacrylate, and 2 parts by mass of methacrylic acid were added to the dropping funnel. A pre-emulsion consisting of 76 parts by mass of ethylhexyl and 1.5 parts by mass of acrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Next, 124.5 parts by mass, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 47.7% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 7.9 and a volume average particle diameter of 200 nm was obtained.

[Preparation Example 4]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 26 parts by mass of deionized water, 4 parts by mass of 10% aqueous sodium dodecylbenzene sulfonate solution, 1.5 parts by mass of 1,6-hexanediol dimethacrylate, 56.5 parts by mass of methyl methacrylate, and methacrylic acid were added to the dropping funnel. A pre-emulsion consisting of 41 parts by mass of dodecyl and 1 part by mass of methacrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.0% and the pH. 8.1, an aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 220 nm was obtained.

[Preparation Example 5]
59 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, in the dropping funnel, 10.5 parts by mass of deionized water, 6 parts by mass of a 25% aqueous solution of Hytenol NF-08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 18 parts by mass of 2-ethylhexyl acrylate, and n-butyl methacrylate. A pre-emulsion (1) consisting of 31 parts by mass and 1 part by mass of acrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion (1) into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 1 part by mass of a 5% ammonium persulfate aqueous solution was added. Polymerization was started. Then, 60 parts by mass of the balance of the preemulsion (1), 3 parts by mass of 5% ammonium persulfate, and 3 parts by mass of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 2 hours.
After completion of the dropping, the temperature was further maintained at 80 ° C. for 1 hour, followed by 10.5 parts by mass of deionized water, 6 parts by mass of a 25% aqueous solution of Hytenol NF-08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), and 2-acrylic acid. 2 parts by mass of a preemulsion (2) consisting of 18 parts by mass of ethylhexyl, 30 parts by mass of n-butyl methacrylate and 2 parts by mass of acrylic acid, 3 parts by mass of a 5% ammonium persulfate aqueous solution and 3 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution. Dropped evenly over time.
After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.1% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 7.6 and a volume average particle diameter of 180 nm was obtained.

[Preparation Example 6]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 21 parts by mass of deionized water, 10 parts by mass of a 25% aqueous solution of Hytenol LA-10, 1.5 parts by mass of 1,6-hexanediol dimethacrylate, 53 parts by mass of methyl methacrylate, and 2 parts by mass of acrylic acid were added to the dropping funnel. A pre-emulsion consisting of 44 parts by mass of ethylhexyl and 1.5 parts by mass of acrylic acid was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Next, 124.5 parts by mass, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.3% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 190 nm was obtained at 7.8.

[Preparation Example 7]
59 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, in the dropping funnel, 10.5 parts by mass of deionized water, 6 parts by mass of a 25% aqueous solution of Hytenol NF-08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1 part by mass of 1,6-hexanediol dimethacrylate, and methacrylic acid. A preemulsion (1) consisting of 10 parts by mass of methyl, 23 parts by mass of dodecyl methacrylate, 5 parts by mass of styrene, 10 parts by mass of n-butyl methacrylate and 1 part by mass of acrylate was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion (1) into the flask, the temperature was raised to 80 ° C. while gently blowing nitrogen gas, and 1 part by mass of a 5% ammonium persulfate aqueous solution was added. Polymerization was started. Then, 60 parts by mass of the balance of the preemulsion (1), 3 parts by mass of 5% ammonium persulfate, and 3 parts by mass of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 2 hours.
After completion of the dropping, the mixture was further maintained at 80 ° C. for 1 hour, followed by 10.5 parts by mass of deionized water, 6 parts by mass of a 25% aqueous solution of Hytenol NF-08 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.), 1,6-. With the pre-aqueous solution (2) consisting of 0.5 parts by mass of hexanediol dimethacrylate, 10 parts by mass of methyl methacrylate, 23 parts by mass of dodecyl methacrylate, 15 parts by mass of styrene, 1 part by mass of itaconic acid and 0.5 parts by mass of acrylic acid. 3 parts by mass of a 5% aqueous ammonium persulfate solution and 3 parts by mass of a 2.5% aqueous sodium hydrogen sulfite solution were uniformly added dropwise over 2 hours.
After completion of the dropping, the mixture was further maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.1% and the pH. An aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 785 nm was obtained at 7.7.

[Preparation Example 8]
64 parts by mass of deionized water was charged in a flask equipped with a dropping funnel, a stirrer, a nitrogen gas introduction pipe, a thermometer and a reflux condenser. On the other hand, 26 parts by mass of deionized water, 4 parts by mass of 10% aqueous sodium dodecylbenzene sulfonate solution, 24 parts by mass of methyl methacrylate, 43.5 parts by mass of dodecyl methacrylate, 30 parts by mass of styrene, and 1 part by mass of itaconic acid were added to the dropping funnel. A pre-emulsion consisting of 1.5 parts by mass of acrylic acid and 1.5 parts by mass was prepared. Next, after adding 6.5 parts by mass of the prepared preemulsion into the flask, the temperature was raised to 80 ° C. with stirring while gently blowing nitrogen gas into the flask, and 2 parts by mass of a 5% ammonium persulfate aqueous solution was added. Was added to initiate polymerization. Then, 123.5 parts by mass of the remainder of the prepared preemulsion, 6 parts by mass of a 5% ammonium persulfate aqueous solution, and 6 parts by mass of a 2.5% sodium hydrogen sulfite aqueous solution were uniformly added dropwise to the flask over 2 hours. After completion of the dropping, the mixture was maintained at 80 ° C. for 2 hours, 25% aqueous ammonia was added so that the pH became about 8, and then the reaction solution was cooled to room temperature to increase the non-volatile content to 48.2% and the pH to about 8. 7.6, an aqueous dispersion of a (meth) acrylic polymer having a volume average particle diameter of 185 nm was obtained.

(Example 1)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, Tg = -2) (° C., solid content 48%) and pure water are kneaded with a kneader at a mass ratio of 100: 100: 20, and roll-rolled to obtain a thickness of 100 μm. An anionic conductive film was prepared by heat-treating for 1 hour. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.5 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 237,825.
The liquid absorption rate of the obtained anionic conductive membrane was 18%, and the swelling degree was 7%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 54/46, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.38 μm.
The resistance value (R) of the obtained anion conductive film was 0.23Ω, and when charge / discharge evaluation was performed, 450 cycles were achieved.

(Example 2)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, Tg = -2) (° C., solid content 48%) and pure water are kneaded with a kneader at a mass ratio of 100: 100: 35 and rolled to a thickness of 100 μm, and this film is made at 80 ° C. for 1 hour and further at 160 ° C. An anionic conductive film was prepared by heat-treating for 1 hour. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.5 N, the density (ρ) is 1.49 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 234,675.
The liquid absorption rate of the obtained anionic conductive membrane was 12%, and the swelling degree was 8%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 53/47, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.38 μm.
The resistance value (R) of the obtained anion conductive film was 0.24 Ω, and when charge / discharge evaluation was performed, 380 cycles were achieved.

(Example 3)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD102A, manufactured by JSR, Tg = -5) (° C., solid content 48%) and pure water are kneaded with a kneader at a mass ratio of 100: 100: 5, and roll rolling is performed to obtain a thickness of 100 μm. An anionic conductive film was prepared by heat-treating for 1 hour. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.4 N, the density (ρ) is 1.54 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 235,620.
The liquid absorption rate of the obtained anionic conductive membrane was 11%, and the swelling degree was 1%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.35 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.21Ω, and when charge / discharge evaluation was performed, 330 cycles were achieved.

(Example 4)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: SR-152, manufactured by Nippon A & L Inc., solid) The volume of 48%) and pure water are kneaded with a kneader at a mass ratio of 100: 100: 20, and roll rolling is performed to obtain a thickness of 100 μm. An anionic conductive film was prepared by heat treatment. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.2 N, the density (ρ) is 1.52 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 218,880.
The liquid absorption rate of the obtained anionic conductive membrane was 4%, and the swelling degree was 5%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 54/46, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.35 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.23Ω, and when charge / discharge evaluation was performed, 305 cycles were achieved.

(Example 5)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, solid content 48%) ) And pure water in a mass ratio of 100: 50: 5, kneaded with a kneader and rolled to obtain a thickness of 100 μm, and this film is heat-treated at 80 ° C. for 12 hours to obtain an anionic conductive film. It was created. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.4 N, the density (ρ) is 1.52 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 232,560.
The liquid absorption rate of the obtained anionic conductive membrane was 8%, and the swelling degree was 6%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.35 μm.
The resistance value (R) of the obtained anion conductive film was 0.21Ω, and when charge / discharge evaluation was performed, 320 cycles were achieved.

(Example 6)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: SR-152, manufactured by Nippon A & L Inc., solid) (Amount 48%) and pure water are kneaded at a mass ratio of 100: 100: 20 and rolled to a thickness of 100 μm, and this film is heat-treated at 80 ° C. for 1 hour to obtain anions. A conductive film was prepared. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.1 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 100 μm. , The X values calculated from these were 210,645.
The liquid absorption rate of the obtained anionic conductive membrane was 19%, and the swelling degree was 8%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.38 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and when charge / discharge evaluation was performed, 315 cycles were achieved.

(Example 7)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD-2001, manufactured by JSR, solid content) 48%) and pure water are kneaded at a mass ratio of 100: 100: 20 and rolled to a thickness of 100 μm, and this film is heat-treated at 80 ° C. for 1 hour to conduct anion conduction. A sex membrane was created. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.3 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 224,235.
The liquid absorption rate of the obtained anionic conductive membrane was 21%, and the swelling degree was 9%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 53/47, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.36 μm.
The resistance value (R) of the obtained anion conductive film was 0.21Ω, and when charge / discharge evaluation was performed, 310 cycles were achieved.

(Example 8)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and carboxymethyl cellulose (trade name: Daicel), an aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1. 1380, manufactured by Daicel Fine Chem Ltd.) and pure water were measured at a ratio of 100: 100: 3:10, kneaded using a kneader until a uniform state was obtained, and then the obtained kneaded product was thickened. An anionic conductive film was obtained by roll-pressing until the thickness reached 100 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability value (T) was 30,000 s, the puncture strength (F) was 1.9 N, the density (ρ) was 1.50 g / cm ³ , and the film thickness (L) was 99 μm. The X value calculated from was 129,545.
The liquid absorption rate of the obtained anionic conductive membrane was 11%, and the swelling degree was 4%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 54/46, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.37 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and 400 cycles were achieved for charge / discharge evaluation.

(Example 9)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 2. To obtain an anionic conductive film. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.7 N, the density (ρ) is 1.53 g / cm ³ , and the film thickness (L) is 102 μm. , The X value calculated from these was 182,250.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 3%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.34 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and 400 cycles were achieved for charge / discharge evaluation.

(Example 10)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 3. To obtain an anionic conductive film. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.5 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 103 μm. , The X value calculated from these was 164,927.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 4%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 56/44, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.34 μm.
The resistance value (R) of the obtained anion conductive film was 0.21Ω, and 350 cycles were achieved for charge / discharge evaluation.

(Example 11)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 4. To obtain an anionic conductive film. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 1.7 N, the density (ρ) is 1.50 g / cm ³ , and the film thickness (L) is 98 μm. , The X value calculated from these was 117,092.
The liquid absorption rate of the obtained anionic conductive membrane was 12%, and the swelling degree was 3%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 56/44, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.34 μm.
The resistance value (R) of the obtained anion conductive film was 0.23Ω, and 360 cycles were achieved for charge / discharge evaluation.

(Example 12)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 5. To obtain an anionic conductive film. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 1.9 N, the density (ρ) is 1.52 g / cm ³ , and the film thickness (L) is 99 μm. , The X value calculated from these was 131,273.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 5%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.37 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.21Ω, and 330 cycles were achieved for charge / discharge evaluation.

(Example 13)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 6. To obtain an anionic conductive film. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 1.9 N, the density (ρ) is 1.5 g / cm ³ , and the film thickness (L) is 103 μm. , The X value calculated from these was 124,515.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 5%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.33 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.21Ω, and 330 cycles were achieved for charge / discharge evaluation.

(Example 14)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 7. To obtain an anionic conductive film. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.8 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 101 μm. , The X value calculated from these was 188,376.
The liquid absorption rate of the obtained anionic conductive membrane was 12%, and the swelling degree was 3%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.35 μm.
The resistance value (R) of the obtained anion conductive film was 0.23Ω, and 380 cycles were achieved for charge / discharge evaluation.

(Example 15)
In Example 8, the same as in Example 8 except that the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic polymer prepared in Preparation Example 8. To obtain an anionic conductive film. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.5 N, the density (ρ) is 1.49 g / cm ³ , and the film thickness (L) is 99 μm. , The X value calculated from these was 169,318.
The liquid absorption rate of the obtained anionic conductive membrane was 16%, and the swelling degree was 7%. The ratio of the total area of the hydrotalcite particles to the total area of the other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.38 μm.
The resistance value (R) of the obtained anion conductive film was 0.20 Ω, and 400 cycles were achieved for charge / discharge evaluation.

(Example 16)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle diameter 0.20 μm) 135 parts by mass, 65 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 1, carboxy Weigh 3 parts by mass of methyl cellulose (trade name: Daicel 1380, manufactured by Daicel Fine Chem Ltd.) and 15 parts by mass of pure water, knead them with a kneader until they become uniform, and then use the obtained kneaded product. An anionic conductive film was obtained by roll pressing until the thickness became 100 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 1.5 N, the density (ρ) is 1.67 g / cm ³ , and the film thickness (L) is 103 μm. , The X value calculated from these was 109,442.
The liquid absorption rate of the obtained anionic conductive membrane was 11%, and the swelling degree was 5%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 65/35, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.37 μm.
The resistance value (R) of the obtained anion conductive film was 0.20 Ω, and 400 cycles were achieved for charge / discharge evaluation.

(Example 17)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Kagaku Kogyo Co., Ltd., average particle size 0.20 μm) 65 parts by mass, 135 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 1, carboxy Weigh 3 parts by mass of methyl cellulose (trade name: Daicel 1380, manufactured by Daicel Fine Chem Ltd.) and 2 parts by mass of pure water, knead with a kneader until uniform, and then use the obtained kneaded product. An anionic conductive film was obtained by roll pressing until the thickness became 100 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.2 N, the density (ρ) is 1.34 g / cm ³ , and the film thickness (L) is 102 μm. , The X value calculated from these was 130,059.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 4%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 34/66, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.38 μm.
The resistance value (R) of the obtained anion conductive film was 0.20 Ω, and 360 cycles were achieved for charge / discharge evaluation.

(Example 18)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industries, Ltd., average particle size 0.20 μm) 100 parts by mass, 100 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 2, carboxy Weigh 3 parts by mass of methyl cellulose (trade name: Daicel 1380, manufactured by Daicel Fine Chem Ltd.) and 10 parts by mass of pure water, knead them with a kneader until they become uniform, and then use the obtained kneaded product. An anionic conductive film was obtained by roll pressing until the thickness became 50 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 1.8 N, the density (ρ) is 1.54 g / cm ³ , and the film thickness (L) is 52 μm. , The X value calculated from these was 239,885.
The liquid absorption rate of the obtained anionic conductive membrane was 13%, and the swelling degree was 4%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.34 μm.
The resistance value (R) of the obtained anion conductive film was 0.10 Ω, and 380 cycles were achieved for charge / discharge evaluation.

(Example 19)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industries, Ltd., average particle size 0.20 μm) 100 parts by mass, 100 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 2, carboxy Weigh 3 parts by mass of methyl cellulose (trade name: Daicel 1380, manufactured by Daicel Fine Chem Ltd.) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then obtain the kneaded product. An anionic conductive film was obtained by roll pressing until the thickness became 100 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.2 N, the density (ρ) is 1.52 g / cm ³ , and the film thickness (L) is 153 μm. , The X value calculated from these was 143,059.
The liquid absorption rate of the obtained anionic conductive membrane was 14%, and the swelling degree was 3%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 55/45, and the ratio of voids was 0.2%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.35 μm.
The resistance value (R) of the obtained anion conductive film was 0.31Ω, and 410 cycles were achieved for charge / discharge evaluation.

(Example 20)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 100 parts by mass, 100 parts by mass of aqueous dispersion of (meth) acrylic polymer prepared in Preparation Example 3, methylcellulose (Product name: SM1500, manufactured by Shin-Etsu Chemical Co., Ltd.) Weigh 3 parts by mass and 10 parts by mass of pure water, knead with a kneader until uniform, and then thicken the obtained kneaded product. An anionic conductive film was obtained by roll pressing to 100 μm and further heat-treating at 120 ° C. for 10 minutes. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 2.2 N, the density (ρ) is 1.52 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 150,480.
The liquid absorption rate of the obtained anionic conductive membrane was 11%, and the swelling degree was 3%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 56/44, and the ratio of voids was 0.3%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.34 μm.
The resistance value (R) of the obtained anion conductive film was 0.26 Ω, and 400 cycles were achieved for charge / discharge evaluation.

(Example 21)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Kagaku Kogyo Co., Ltd., average particle size 0.20 μm) 100 parts by mass, aqueous dispersion of acrylonitrile-butadiene copolymer (product name: NA-13, Nippon A & L Co., Ltd.) Made by, solid content 47%) 100 parts by mass, polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) 5 parts by mass and carboxymethyl cellulose (trade name: Daicel 1380, Daicel Finechem Ltd.) (Manufactured by) 3 parts by mass and 15 parts by mass of pure water are weighed and kneaded using a kneader until a uniform state is obtained. A conductive film was obtained. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive film, the air permeability value (T) was 30,000 s, the puncture strength (F) was 2.6 N, the density (ρ) was 1.52 g / cm ³ , and the film thickness (L) was 100 μm. The X value calculated from was 177,840.
The liquid absorption rate of the obtained anionic conductive membrane was 19%, and the swelling degree was 11%. The ratio of the total area of the hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 52/48, and the ratio of voids was 0.3%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.36 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and 340 cycles were achieved for charge / discharge evaluation.

(Comparative Example 1)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, Tg = -2) An anion conductive film having a thickness of 100 μm was prepared by kneading kneaded with pure water at a mass ratio of 100: 100: 35 (° C., solid content 48%) and rolling. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 30,000 s, the puncture strength (F) is 3.1 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 100 μm. , The X values calculated from these were 210,645.
The liquid absorption rate of the obtained anionic conductive membrane was 28%, and the swelling degree was 31%. The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the obtained anion conductive film was 53/47, and the ratio of voids was 0.2% or less. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.37 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.21Ω, and when charge / discharge evaluation was performed, 240 cycles were achieved.

(Comparative Example 2)
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) and polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) and pure Water and water were kneaded with a kneader at a mass ratio of 100: 120: 50 and rolled to produce an anionic conductive film having a thickness of 100 μm. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability value (T) is 1500 s, the puncture strength (F) is 0.7 N, the density (ρ) is 1.3 g / cm ³ , and the film thickness (L) is 100 μm. , The X value calculated from these was 102.
The liquid absorption rate of the obtained anionic conductive membrane was 26%, and the swelling degree was 12%. In the cross section of the obtained anion conductive film, only hydrotalcite particles and voids were observed, no anion conductive film-forming material components other than the compound particles could be confirmed, and the ratio of the void area was 5.2%. It was. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.41 μm.
The resistance value (R) of the obtained anion conductive membrane was 0.20 Ω, and when charge / discharge evaluation was performed, 180 cycles were achieved.

As described above, the anionic conductive film-forming material containing the conjugated diene polymer and / or the (meth) acrylic polymer and the inorganic compound particles such as hydrotalcite is used, and the liquid absorption rate is 25% or less. By forming a certain anion conductive film and forming a battery using the obtained anion conductive film, a battery having a long life and excellent long-term use was obtained.

Claims (5)

Containing conjugated diene-based polymers and / or (meth) acrylic-based polymers and at least one inorganic compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides.
An anionic conductive membrane having a liquid absorption rate of 1% or more and 25% or less .
The glass transition temperature of the conjugated diene polymer and / or the (meth) acrylic polymer is −20 ° C. or higher and 50 ° C. or lower.
The mass ratio of the inorganic compound is 30% by mass or more and 90% by mass or less in 100% by mass of the anionic conductive film.
The conjugated diene-based polymer is a styrene-butadiene-based copolymer, and is
The (meth) acrylic polymer is characterized by containing a monomer unit derived from a (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms as a main component. Anionic conductive film. The anionic conductive membrane according to claim 1, wherein the anionic conductive membrane further contains at least one selected from the group consisting of carboxymethyl cellulose, methyl cellulose, and polytetrafluoroethylene. The anionic conductive film according to claim 1 or 2, wherein the inorganic compound is a layered double hydroxide. A separator comprising the anionic conductive film according to any one of claims 1 to 3 . A battery characterized by being configured by using the separator according to claim 4 .