JP6899634B2 - 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 used is disclosed (see, for example, Patent Document 4).

Japanese Unexamined Patent Publication No. 2013-54877 Japanese Unexamined Patent Publication 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 high 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 inventor has studied various materials capable of further extending the life of a battery using zinc type as a negative electrode active material, and is selected from conjugated diene compounds and groups 1 to 17 of the periodic table. Using a material for forming an anionic conductive film containing a compound containing at least one element (hereinafter, such a material before film formation is also referred to as an anionic conductive film forming material) is used in the periodic table. An anionic conductive film containing compound particles containing at least one element selected from Groups 1 to 17 and an anionic conductive film-forming material component other than the compound that covers between the compound particles. The total area of compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in the cross section of the film, and the total area of anionic conductive film-forming material components other than the compound. A film was formed in which the ratio of Then, it was found that when this anion conductive film is used as a separator, the growth of dendrites is effectively suppressed while having good selective permeability of hydroxide ions, and the battery can be extended in life. I came up with the idea that I could solve the problem brilliantly. The present inventor has further conceived that the same effect can be exhibited by using a (meth) acrylic polymer instead of the conjugated diene polymer, and the above problem can be solved brilliantly. It has reached the present invention.

That is, the present invention is an anionic conductive film formed by using an anionic conductive film-forming material, wherein the anionic conductive film-forming material is a conjugated diene-based polymer and / or a (meth) acrylic-based polymer. The cross section of the anion conductive film contains a compound containing at least one element selected from Groups 1 to 17 of the periodic table, and the cross section of the anion conductive film is at least 1 selected from Groups 1 to 17 of the periodic table. The ratio of the total area of the compound particles containing the seed element to the total area of the anionic conductive film-forming material component other than the compound (compound particle / component of the anionic conductive film-forming material other than the compound) is 70 /. It is an anion conductive film characterized by being 30 to 30/70.
The present invention will be described in detail below.
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 film of the present invention contains a conjugated diene polymer and / or a (meth) acrylic polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. It is characterized by being formed from an anionic conductive film-forming material. In conventional anionic conductive membranes, a polymer that is fiberized by kneading such as polytetrafluoroethylene has been often used as a component for holding the compound particles for the purpose of forming a membrane having high strength and excellent flexibility. .. According to the present inventor, when such a fibrous polymer is used as a main component, the obtained membrane has many fine voids, and zincate ions permeate into the voids having no ion selectivity. We have found that there is a new problem that the growth of dendrite in the membrane is promoted, and as a result, the life of the battery is shortened.
On the other hand, an anionic conductive film formation containing a conjugated diene-based polymer and / or a (meth) acrylic-based polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table is formed. The anion conductive film of the present invention formed from the material suppresses the permeation of zincate ions, has good selective permeability of hydroxide ions through which hydroxide ions permeate, and has few voids. Since it is a film, by using this film as a separator, the life of the battery can be extended as compared with the case where a conventional anionic conductive film is used. Further, since the anionic conductive film formed by using the conjugated diene polymer and / or the (meth) acrylic polymer has alkali resistance, it is suitably used as a material for a battery separator that comes into contact with an alkaline electrolytic solution. be able to. Further, the conjugated diene polymer and the (meth) acrylic polymer can have an appropriate affinity with the compound particles at the time of film formation, and when used as an anionic conductive film, a hydrophobic portion between the particles is provided. Can be formed, so that the compound particles are uniformly dispersed in the film, and an anionic conductive film in which the permeation of zincate ions is suppressed can be formed.

The anionic conductive film of the present invention is the total area of compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in the cross section of the film, and an anionic conductive film other than the compound. The ratio to the total area of the forming material components (compound particles / components of the anionic conductive film forming material other than the compound) is 70/30 to 30/70. In a battery having a zinc type as a negative electrode active material, in order to suppress the outflow of the electrode active material from the electrode, the separator does not allow the zincate ions generated in the electrode reaction to permeate, and the hydroxide ions required for the electrode reaction. Preferably has selective ion permeability to permeate. In the anion conductive film of the present invention, in the cross section of the film, the particle portion of the compound containing at least one element selected from Groups 1 to 17 of the periodic table has such selective ion permeability. By using a conjugated diene polymer and / or a (meth) acrylic polymer, the voids in the anionic conductive film-forming material component portion between the compound particles can be made into a conventional fibrous polymer. Since it is less than when used as a component of an anion conductive film-forming material, it suppresses the permeation of zincate ions into the film while maintaining good permeability of hydroxide ions, and promotes the growth of dendrites. Effectively suppress.
In the anionic conductive membrane of the present invention, the total area of compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table and the total area of compound particles other than the compound in at least one cross section of the membrane. The ratio to the total area of the anion conductive film-forming material components may be within the above-mentioned predetermined range, but from the viewpoint of the permeability of hydroxide ions, it may be within the above-mentioned predetermined range in any cross section. It is preferable that the surface of the film is also in the above-mentioned predetermined range.

In the anion conductive film of the present invention, the total area of compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in its cross section and the formation of an anion conductive film other than the compound. As long as the ratio to the total area of the material components is within the above range, some independent voids may be included. Air trapped during kneading of the anionic conductive film-forming material remains to form voids in the film, or compound particles containing at least one element selected from Group 1 to Group 17 aggregate and aggregate. Voids can occur between the particles.
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. It is more preferably 1% or less, further preferably 0.5% or less, and particularly preferably 0.2% or less.
The proportion of the area of the voids in the anion conductive membrane can be measured by observing the cross section of the anion conductive membrane with a scanning electron microscope (SEM) according to the method described in Examples.

As described above, in the anionic conductive film of the present invention, the total area of compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table and anionic conductivity other than the compound. The ratio to the total area of the film-forming material components (compound particles / anionic conductive film-forming material components other than the compound) is 70/30 to 30/70. With such an area ratio, the anion conductive film can exhibit better hydroxide ion conductivity while having sufficient strength. Preferably, (compound particles / components of anionic conductive film-forming material other than the compound) are 65/35 to 35/65, and more preferably 60/40 to 40/60.
The area of the compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in the cross section of the anion conductive film referred to here is the area of the cross section of the anion conductive film being scanned by a scanning electron microscope ( It is the white part of FIGS. 1 and 2 measured by SEM), and the area of the anion conductive film-forming material component other than the compound is the black part of FIGS. 1 and 2. These can be measured by observing the cross section of the anionic conductive membrane with a scanning electron microscope (SEM) according to the method described in Examples.
In the present invention, the anion conductive film-forming material component other than the compound containing at least one element selected from Group 1 to Group 17 of the periodic table is included in the periodic table. It means all components other than compounds containing at least one element selected from Groups 1 to 17 in the table.

The average cross-sectional particle size of the compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in the cross section of the anion conductive film shall be 0.1 to 1.0 μm. Is preferable. 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 is more preferably 0.2 to 0.7 μm, further preferably 0.3 to 0.5 μm, and particularly preferably 0.3 to 0.4 μm.
The average cross-sectional particle size of the compound particles containing at least one element selected from Groups 1 to 17 of the periodic table can be measured by 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 the range including the numerical values of the upper end and the lower end of the range.

The film thickness of the anionic conductive film of the present invention is preferably 10 to 1000 μm. More preferably, it is 20 to 500 μm. If it is thinner than 10 μm, many damages will occur during film formation, and if it is thicker than 1000 μm, it will be disadvantageous in terms of cost and the ability to permeate hydroxide ions will be reduced.
The film thickness of the anion conductive film can be measured according to the method described in Examples.

Further, the anionic conductive film of the present invention preferably has a liquid absorption rate of 1 to 25% from the viewpoint of preventing a short circuit between the positive electrode and the negative electrode and having good ionic conductivity. Further, the anion conductive membrane preferably has a swelling degree of 10% or less from the viewpoint of extending the life of the battery using the anion conductive membrane.
The liquid absorption rate and the degree of swelling of the anionic conductive membrane can be measured by the method described in Examples.

Further, in the anion conductive membrane of the present invention, the value of X calculated by the formula (1) described in the examples is preferably 5000 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 growth of dendrite such as zinc is a problem.

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 0.02 Ω or more, further preferably 0.03 Ω or more, further preferably 0.05 Ω or more, and particularly preferably 0.1 Ω 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 and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. The total area of the compound particles formed from the anionic conductive film-forming material and containing at least one element selected from Group 1 to Group 17 of the periodic table, and the components of the anionic conductive film-forming material other than the compound. The ratio (compound particles / components of anionic conductive film-forming material other than the compound) to the total area of is 70/30 to 30/70, and the first group to the first group of the periodic table in the cross section of the anionic conductive film. The average cross-sectional particle size of the compound particles containing at least one element selected from Group 17 is preferably 0.1 to 1.0 μm.
Further, in the anionic conductive film of the present invention, a compound containing a conjugated diene-based polymer and / or a (meth) acrylic-based polymer and at least one element selected from Groups 1 to 17 of the periodic table. The total area of compound particles formed from an anionic conductive film-forming material containing, and containing at least one element selected from Group 1 to Group 17 of the periodic table, and formation of an anionic conductive film other than the compound. It is preferable that the ratio to the total area of the material components (compound particles / components of the anionic conductive film-forming material other than the compound) is 70/30 to 30/70, and the liquid absorption rate is 1 to 25%.
Further, in the anionic conductive film of the present invention, a compound containing a conjugated diene-based polymer and / or a (meth) acrylic-based polymer and at least one element selected from Groups 1 to 17 of the periodic table. The total area of compound particles formed from an anionic conductive film-forming material containing, and containing at least one element selected from Group 1 to Group 17 of the periodic table, and formation of an anionic conductive film other than the compound. It is preferable that the ratio to the total area of the material components (compound particles / components of the anionic conductive film-forming material other than the compound) is 70/30 to 30/70, and the degree of swelling is 10% or less.
Further, in the anionic conductive film of the present invention, a compound containing a conjugated diene-based polymer and / or a (meth) acrylic-based polymer and at least one element selected from Groups 1 to 17 of the periodic table. The total area of compound particles formed from an anionic conductive film-forming material containing, and containing at least one element selected from Group 1 to Group 17 of the periodic table, and formation of an anionic conductive film other than the compound. The ratio to the total area of the material components (compound particles / components of the anionic conductive film-forming material other than the compound) is 70/30 to 30/70, and X calculated by the formula (1) described in the examples. The value of is preferably 5000 or more.
Further, in the anionic conductive film of the present invention, a compound containing a conjugated diene-based polymer and / or a (meth) acrylic-based polymer and at least one element selected from Groups 1 to 17 of the periodic table. The total area of compound particles formed from an anionic conductive film-forming material containing, and containing at least one element selected from Group 1 to Group 17 of the periodic table, and formation of an anionic conductive film other than the compound. The ratio to the total area of the material components (compound particles / component of anionic conductive film-forming material other than the compound) is 70/30 to 30/70, and the resistance value R is 0.01Ω or more and 1.0Ω or less. It is preferable to have.

The conjugated diene polymer or (meth) acrylic polymer used as a raw material for the anionic conductive film of the present invention preferably has a weight average molecular weight of 1000 to 7000000. Thereby, the ionic conductivity, flexibility and the like of the anionic conductive membrane can be adjusted. The weight average molecular weight is more preferably 20000 to 6500000, still more preferably 100000 to 5000000, and particularly preferably 100000 to 1000000.
The weight average molecular weight can be measured by gel permeation chromatography (GPC) as a polystyrene-equivalent weight average molecular weight.

The conjugated diene polymer and the (meth) acrylic polymer preferably have a glass transition temperature (Tg) of -20 to 50 ° C.
When the Tg of the conjugated diene polymer or the (meth) acrylic polymer is −20 ° C. or higher, the anionic conductive film has sufficient strength and can sufficiently exert the dendrite suppressing effect. Further, when the Tg is 50 ° C. or lower, the anion conductive film does not become too hard and brittle, and the anion conductive film does not become too hard and brittle, and the anion conductive film cracks or the like when the film is formed. It is possible to avoid a risk of deterioration in life performance. When the anion conductive film of the present invention contains at least one compound selected from the group consisting of oxides, hydroxides, and layered double hydroxides, the oxides and hydroxides are contained in the anion conductive film. In order to suppress the formation of voids due to the aggregation of at least one inorganic compound particles selected from the group consisting of the substance and the layered double hydroxide, the anionic conductive film-forming material is included. It is preferable to sufficiently knead the components to suppress the aggregation of the compound particles so that the compound particles and the components other than the compound particles are in a uniform state. When the Tg of the conjugated diene-based polymer or the (meth) acrylic-based polymer is -20 ° C or higher and 50 ° C or lower, the kneaded product at the time of kneading with the compound particles has appropriate fluidity, and agglomerates of the compound particles. It is possible to make the components contained in the crushed or anionic conductive film-forming material more uniform. The Tg of the conjugated diene polymer or the (meth) acrylic polymer is more preferably −15 ° C. or higher and 30 ° C. or lower, further preferably −10 ° C. or higher and 10 ° C. or lower, and particularly preferably. , -10 ° C or higher and 5 ° C or lower.
The Tg of the polymer can be measured by a differential scanning calorimeter according to the method described in Examples.

The mass ratio of the conjugated diene polymer or the (meth) acrylic polymer is 20% by mass or more with respect to 100% by mass of the anionic conductive film-forming material from the viewpoint of the strength and ionic conductivity of the anionic conductive film. It is preferably 25% by mass or more, and more preferably 25% by mass or more. More preferably, it is 30% by mass or more. The mass ratio is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% 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 "ratio of conjugated diene-based polymer or (meth) acrylic-based polymer" refers to the case where the anionic conductive film-forming material contains either a conjugated diene-based polymer or a (meth) acrylic-based polymer. Means the proportion of the polymer contained, and when the anionic conductive film-forming material contains both a conjugated diene polymer and a (meth) acrylic polymer, it means the total proportion of both.

<Conjugated diene polymer>
The conjugated diene polymer is not particularly limited as long as it has a monomer unit derived from a conjugated diene monomer, but it may have a monomer unit derived from an aromatic vinyl monomer. 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. Alternatively, the liquid absorption rate of the anionic conductive film of the present invention can be suitably adjusted by preparing 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.
The conjugated diene polymer may have a functional group such as an ester group, a hydroxy group, or a carboxy group introduced therein. 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 polymer, one or more homopolymers such as polybutadiene and polyisoprene and copolymers can be used. For example, a monomer derived from an aromatic vinyl monomer can be used. It is preferably a copolymer having more units.
Examples of the aromatic vinyl monomer include styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, and o-. Methoxystyrene, 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. These aromatic vinyl monomers may be used alone or in combination of two or more.

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.

The conjugated diene-based polymer is a monomer derived from other unsaturated monomers other than the monomer unit derived from the aliphatic conjugated diene-based 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.

The mass ratio of the monomer unit derived from other unsaturated monomers 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 alkyl (meth) acrylate 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.

As the conjugated diene polymer, one or more of styrene-butadiene copolymer, polybutadiene, polyisoprene, acrylonitrile-butadiene copolymer, isobutylene-isoprene copolymer and the like are preferably used. Can be done. Among these, a styrene-butadiene copolymer and an acrylonitrile-butadiene copolymer are preferable 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 anionic conductive film. In particular, a styrene-butadiene copolymer is preferable.

<(Meta) acrylic polymer>
The (meth) acrylic polymer in the present invention contains a monomer unit derived from a (meth) acrylic acid alkyl ester monomer as a main component. The term "containing a monomer unit derived from a (meth) acrylic acid alkyl ester monomer as a main component means that the (meth) acrylic polymer contains a monomer unit derived from a (meth) acrylic acid alkyl ester monomer. It means that the mass ratio occupies more 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, (meth) ) 2-Ethylhexyl acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate A (meth) acrylic acid alkyl ester monomer having an alkyl group having 1 to 12 carbon atoms such as the above is preferable, and one or more of these can be used.

The (meth) acrylic polymer may be composed of only the monomer unit derived from the (meth) acrylic acid alkyl ester monomer, but the monomer unit derived from other unsaturated monomers. May include. In that case, 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 the total monomer unit constituting the (meth) acrylic polymer. It is preferably 50% by mass or more.

Examples of the other unsaturated monomer include a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester compound, an oxo group-containing monomer, a nitrogen atom-containing monomer, and a fluorine atom-containing monomer. , Epoxy group-containing monomer, carbonyl group-containing monomer, aziridinyl group-containing monomer, styrene-based monomer, (meth) acrylic acid aralkyl ester compound, and other monofunctional and polyfunctional monomers However, the present invention is not limited to such an example. 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 compound include 2-hydroxyethyl (meth) acrylic acid, 2-hydroxypropyl (meth) acrylic acid, 3-hydroxypropyl (meth) acrylic acid, and (meth) acrylic acid. Examples thereof include hydroxyl group-containing (meth) acrylic acid ester compounds having 1 to 18 carbon atoms in ester groups such as 2-hydroxybutyl and 4-hydroxybutyl (meth) acrylate, but the present invention is limited to such examples. It is not something that is done. These hydroxyl group-containing (meth) acrylic acid ester compounds 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 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 these examples. These fluorine atom-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 compounds such as dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate, N-vinylpyrrolidone, (meth) acrylonitrile and the like. , 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 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 and 2-aziridinyl ethyl (meth) acrylate, 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 functional group such as a nitro group, a nitrile group, an alkoxyl group, an acyl group, a sulfone group, a hydroxyl group or 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 compound include benzyl (meth) acrylate, phenylethyl (meth) acrylate, methyl benzyl (meth) acrylate, and naphthylmethyl (meth) acrylate, which have 7 carbon atoms. Examples thereof include (meth) acrylic acid aralkyl ester compounds having ~ 18 aralkyl groups, but the present invention is not limited to these examples. These (meth) acrylic acid aralkyl ester compounds may be used alone or in combination of two or more.

Among the above, suitable monofunctional monomers include, for example, a carboxy group-containing monomer, a hydroxyl group-containing (meth) acrylic acid ester compound, an oxo group-containing monomer, a fluorine atom-containing monomer, and a nitrogen atom-containing monomer. Examples thereof include monomers, epoxy group-containing monomers, and styrene-based monomers, 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) acrylates of polyhydric alcohols 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. ) Acrylate and the like, but the present invention is not limited to such examples. These polyfunctional monomers may be used alone or in combination of two or more.

The mass ratio of the monomer units derived from other unsaturated monomers 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.
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 monomer unit derived from a styrene-based monomer as a monomer unit derived from another unsaturated monomer, a monomer unit derived from a styrene-based monomer 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, a monomer unit derived from the polyfunctional monomer 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.

The conjugated diene-based polymer and the (meth) acrylic-based polymer can be produced by polymerizing the monomer components that form the structural units contained in the above-mentioned polymers.
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 a main component, and the monomer may be carried out. The ingredients, surfactants and aqueous medium may be emulsified by stirring to prepare a pre-emulsion and then emulsified and polymerized, or at least one of the monomeric components, surfactants and mediums and the rest thereof. May be mixed with the pre-emulsion of the above to carry out emulsification 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 dodecylbenzene sulfonate, sodium dodecylnaphthalene sulfonate; polyoxyethylene alkylphenyl ether sulfates; polyoxyethylene alkyl sulfonate salts; polyoxyethylene alkyl sulfate salts; polyoxyethylene alkyl aryls 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, (meth) polyoxyethylene phosphonate salt, allyloxymethylalkyloxypolyoxyethylene sulfonate salt, or a salt thereof; allyloxymethyl Examples thereof include a sulfate ester salt of alkoxyethylpolyoxyethylene.

The nonionic surfactant is not particularly limited, and 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, and the like. Examples thereof include fatty acid 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 tenside agent is not particularly limited, and examples thereof include betaine ester type surfactants and the like.

As for the amount of the surfactant used in the above emulsion polymerization method, the polymerization stability is improved with respect to 100% by mass of all the monomer components used as the raw materials of the conjugated diene polymer and the (meth) acrylic polymer. From the viewpoint of making it, it is preferably 0.01% by mass or more, more preferably 0.5% by mass or more, and further 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 Persulfate 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. The time of the polymerization reaction is also not particularly limited, but in consideration of productivity, it is preferably 0.5 hours or more and 10 hours or less. 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. The particle size is preferably 20 nm or more, more preferably 50 nm or more, still more preferably 80 nm or more from the viewpoint of forming a uniform film, and from the viewpoint of suppressing the permeation of water or ions into the binder portion in the film. Therefore, it is preferably 5000 nm or less, more preferably 1000 nm or less, and further preferably 500 nm or less.
The volume average particle size is determined by diluting an aqueous dispersion of a conjugated diene polymer or a (meth) acrylic polymer with distilled water, collecting about 10 mL of the obtained diluent in a glass cell, and collecting this in a glass cell with dynamic light. It can be measured by using a particle size distribution measuring device by a scattering method [manufactured by Particle Sizing Systems, trade name: NICOM Polymer 380].

<Compounds containing at least one element selected from Groups 1 to 17 of the Periodic Table>
The anionic conductive membrane of the present invention contains a compound containing at least one element selected from Groups 1 to 17 of the periodic table.
As at least one element selected from Group 1 to Group 17 of the periodic table, alkali metal, alkaline earth metal, Mg, Sc, Y, lanthanoid, Ti, Zr, Hf, V, Nb, Ta, Cr , Mo, W, Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P , Sb, Bi, S, Se, Te, F, Cl, and Br, preferably at least one element selected from the group. Among them, at least one element selected from Group 1 to Group 15 of the periodic table is preferable, and Li, Na, K, Cs, Mg, Ca, Ba, Sc, Y, lanthanoid, Ti, Zr, Nb, Cr , Mn, Fe, Ru, Co, Ni, Pd, Cu, Ag, Au, Zn, Cd, B, Al, Ga, In, Tl, C, Si, Ge, Sn, Pb, N, P, Sb, and , At least one element selected from the group consisting of Bi is more preferred. More preferably, Li, Mg, Ca, Ba, Sc, Y, lanthanoids, Ti, Zr, Nb, Cr, Mn, Fe, Ru, Co, Ni, Pd, Cu, Zn, Cd, B, Al, Ga, It is at least one element selected from the group consisting of In and Tl.

Examples of the compound containing at least one element selected from Groups 1 to 17 of the periodic table include oxides; composite oxides; layered compound hydroxides; hydroxides; clay compounds; solid solutions; Alloys; zeolites; halides; carboxylate compounds; carbonate compounds; hydrogen carbonate compounds; nitrate compounds; sulfuric acid compounds; sulfonic acid compounds; phosphoric acid compounds such as hydroxyapatite; phosphite compounds; hypophosphite compounds, boric acid compounds; Examples thereof include silicic acid compounds; aluminic acid compounds; sulfides; onium compounds; salts and the like. Preferably, oxide; composite oxide; layered double hydroxide such as hydrotalcite; hydroxide; clay compound; solid solution; zeolite; fluoride; phosphoric acid compound; boric acid compound; silicic acid compound; aluminic acid compound. ; Salt is mentioned.
Among these, compounds containing at least one element selected from Groups 1 to 17 of the periodic table are from the group consisting of oxides, hydroxides, layered compound hydroxides, and phosphoric acid compounds. It is preferably at least one compound of choice. More preferably, it is a layered double hydroxide and / or an oxide.

As the oxide, for example, cerium oxide and zirconium oxide are preferable. More preferably, it is cerium oxide. Further, the cerium oxide may be a solid solution with a metal oxide such as samarium oxide, gadolinium oxide, bismuth oxide or zirconium oxide. It may have an oxygen defect.

The layered double hydroxide is represented by the following 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 ^{_{either, OH -, Cl -, NO}} 3 -, CO 3 2-, COO - .m representing a 1-3-valent anion such as 0 or more N is a number from 1 to 3. x is a number from 0.25 to 0.40). ^{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 may be used, and the compounds may be dehydrated by firing at 150 ° C to 900 ° C. It may be a compound obtained by decomposing anions in the layers, a compound in which anions in the layers are exchanged with hydroxide ions, or the like. Among these layered double hydroxides, Mg—Al-based layered double hydroxides such as hydrotalcite are preferable. A compound having a functional group such as a hydroxyl group, an amino group, a carboxyl group, or a silanol group may be coordinated with the layered double hydroxide.

As the hydroxide, for example, cerium hydroxide and zirconium hydride are preferable.

As the phosphoric acid compound, for example, hydroxyapatite is preferable.
The above-mentioned hydroxyapatite is _{a compound typified by Ca 10} (PO ₄ ) ₆ (OH) ₂ , and a compound in which the amount of Ca is reduced depending on the conditions at the time of preparation, a hydroxyapatite compound in which an element other than Ca is introduced, and the like. May be used as the above-mentioned inorganic compound.

The compound containing at least one element selected from Groups 1 to 17 of the periodic table preferably has an average particle size of 5 μm or less, more preferably 1 μm or less, and even more preferably. It is 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, it is 0.01 μm or more.
The average particle size can be measured by a laser diffraction method.
The shape of the particles of the compound containing at least one element selected from Group 1 to Group 17 of the above periodic table is fine powder, powder, granular, granular, scaly, polyhedral, rod-like, and so on. Examples include curved surface content. For particles having an average particle size in the above range, for example, a method in which the particles are crushed by a ball mill or the like, the obtained coarse particles are dispersed in a dispersant to obtain a desired particle size, and then dried. 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 ratio of the compound containing at least one element selected from Groups 1 to 17 of the periodic table is preferably 25% by mass or more with respect to 100% by mass of the anion conductive film-forming material. More preferably, it is 35% by mass or more, and further preferably 40% by mass or more. Further, it is preferably 65% by mass or less. More preferably, it is 55% by mass or less, and further preferably 50% by mass or less.

<Other ingredients>
The anionic conductive film of the present invention contains a conjugated diene polymer and / or a (meth) acrylic polymer and a compound containing at least one element selected from Groups 1 to 17 of the periodic table. As long as it may contain other components.
Other components include hydrocarbon site-containing polymers typified by polyolefins such as polyethylene and polypropylene, aromatic group-containing polymers typified by polystyrene and the like; ether groups typified by alkylene glycols such as polyethylene oxide and polypropylene oxide. Containing polymer: Containing hydroxyl groups typified by polyvinyl alcohol, poly (α-hydroxymethylacrylate), cellulose, methylcellulose, hydroxyethylmethylcellulose, hydroxypropylmethylcellulose, hydroxyalkylcellulose (for example, hydroxyethylcellulose, hydroxypropylcellulose, etc.), etc. Polymers; amide bond-containing polymers typified by polyamide, nylon, polyacrylamide, polyvinylpyrrolidone, N-substituted polyacrylamide, etc .; imide bond-containing polymers typified by polymaleimide, polyimide, etc .; 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) Halogen atom-containing polymers such as polyvinyl chloride, polyvinylidene fluoride, and polytetrafluoroethylene; polymers bonded by opening an epoxy group such as epoxy resin; sulfonic acid (salt) site-containing polymer; AR ¹ R ² R ³ B (A represents N or P. B represents an anion such as ^{a halogen anion or OH −. R 1} , R ² , and R ³ are alkyl groups having 1 to 7 carbon atoms, which are the same or different. It represents a hydroxyalkyl group, an alkylcarboxyl group, and an aromatic ring group. R ¹ , R ² , and R ³ may be bonded to form a ring structure), and is represented by a polymer to which a group represented by the group is bonded. Polymers containing quaternary ammonium salts and quaternary phosphonium salts; ion-exchangeable polymers used for cation / anion exchange membranes, etc .; saccharides typified by cellulose acetate, chitin, chitosan, alginic acid (salt), etc.; polyethylene Amino group-containing polymer represented by imine; Carbamate group site-containing polymer; Carbamide group site-containing polymer; Epoxy group site-containing polymer; Heterocycle and / or ionized heterocyclic site-containing polymer; Polymer alloy; Heteroatom-containing polymer ; Poly other than conjugated diene-based polymers such as low molecular weight surfactants Examples thereof include those that do not correspond to the conjugated diene polymer or the (meth) acrylic polymer in the present invention, and one or more of these can be used. By adding a polymer other than the conjugated diene polymer or the (meth) acrylic polymer in the present invention, the effect of improving the strength of the film can be obtained.
In addition, these polymers may be crosslinked with a known organic cross-linking agent compound.

Among the polymers other than the conjugated diene polymer and the (meth) acrylic polymer in the present invention, halogen atom-containing polymers, carboxy group-containing polymers, and hydroxyl group-containing polymers are preferable.
That is, in the present invention, the anion conductive film-forming material preferably further contains at least one selected from the group consisting of a halogen atom-containing polymer, a carboxy group-containing polymer, and a hydroxyl group-containing polymer. More preferably, it contains at least one selected from the group consisting of a fluorine-containing polymer, poly (meth) acrylic acid (salt), carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose.

The content of the polymer other than the conjugated diene polymer and the (meth) acrylic polymer in the present invention is based on 100% by mass of the anionic conductive film-forming material from the viewpoint of material uniformity and film moldability. It is preferably 1 to 20% by mass. More preferably, it is 2 to 10% by mass.
When two or more kinds of polymers other than the conjugated diene-based polymer and the (meth) acrylic-based polymer in the present invention are contained, it is the total amount of the two or more kinds of polymers.

The weight average molecular weight of the polymers other than the conjugated diene polymer and the (meth) acrylic polymer in the present invention is the same as the weight average molecular weight of the conjugated diene polymer and the (meth) acrylic polymer in the present invention described above. The method for measuring the weight average molecular weight is also the same.

The conjugated diene polymer, the (meth) acrylic polymer, and other polymers in the present invention have radical polymerization, radical (alternate) copolymerization, anion polymerization, and anion (alternate) from the monomer corresponding to the constituent unit thereof. ) Copolymerization, cationic polymerization, cationic (alternate) copolymerization, graft polymerization, graft (alternate) copolymerization, living polymerization, living (alternate) copolymerization, dispersion polymerization, emulsification polymerization, suspension polymerization, ring-opening polymerization, cyclization It can be obtained by polymerization, polymerization by light, ultraviolet rays or electron beam irradiation, metathesis polymerization, electrolytic polymerization and the like. When these polymers have a functional group, they may have it in the main chain and / or the side chain, and may exist as a binding site with a cross-linking agent. One type of these polymers may be used, or two or more types may be used.
These polymers are composed of an organic cross-linking agent compound other than a compound containing at least one element selected from Groups 1 to 17, such as ester bond, amide bond, ionic bond, van der Waals bond, and agostic interaction. Hydrogen bond, acetal bond, ketal bond, ether bond, peroxide bond, carbon-carbon bond, carbon-nitrogen bond, carbon-oxygen bond, carbon-sulfur bond, carbamate bond, thiocarbamate bond, carbamide bond, thiocarbamide bond, oxazoline It may be crosslinked via a site-containing bond, a triazine bond, or the like.

Other components that may be contained in the anionic conductive film-forming material in the present invention include polymers other than conjugated diene-based polymers and (meth) acrylic-based polymers, for example, alumina, silica, and conductive carbon. Examples thereof include other inorganic components such as conductive ceramics and solvents.

The average particle size of the other inorganic components is preferably 5 μm or less. The average particle size is preferably 1 μm or less, more preferably 0.5 μm or less, still more preferably 0.1 μm or less. On the other hand, the average particle size is preferably 0.001 μm or more. The average particle size is more preferably 0.01 μm or more.
The average particle size of the other inorganic components can be measured by the same method as the average particle size of the compound containing at least one element selected from the above-mentioned Groups 1 to 17.

The content ratio of the other inorganic components is preferably 1% by mass or less with respect to 100% by mass of the anionic conductive film-forming material from the viewpoint of film strength. More preferably, it is 0.5% by mass or less, and further preferably 0.2% by mass or less.

Examples of the solvent include one or more of organic solvents such as water, methanol, ethanol, propanol, isopropanol, butanol, hexanol, tetrahydrofuran and N-methylpyrrolidone.

The content ratio of the solvent is preferably 20 to 40% by mass with respect to 100% by mass of the anionic conductive film-forming material from the viewpoint of suppressing film shrinkage during molding. More preferably, it is 30 to 35% by mass.
When the polymer contained in the anionic conductive film-forming material is in the form of an emulsion, the dispersion medium in which the emulsion polymer is dispersed is also included in the solvent.

Examples of the method for preparing the anion conductive film-forming material in the present invention include the following methods.
If necessary, the above-mentioned other components are mixed together with the polymer, a compound containing at least one element selected from Groups 1 to 17 of the periodic table, and the like. A mixer, blender, kneader, bead mill, ready mill, ball mill or the like can be used for mixing. 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.
The form of the anion conductive film-forming material in the present invention is not limited as long as it can form a film, and may be in any form such as clay-like, paste-like, and slurry-like. ..

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, a conjugated diene polymer and / or a (meth) acrylic polymer and at least one element selected from Groups 1 to 17 of the periodic table. A method for producing an anionic conductive film, which comprises a step of forming an anionic conductive film-forming material containing a compound contained therein 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 may include a step of drying the film in addition to the step of forming the anion conductive film-forming material into a film shape. The drying temperature may be appropriately set, but it can be set at 60 ° C to 160 ° C.

<Battery>
The anionic conductive membrane 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 composed of the anionic conductive film of the present invention is also one of the present inventions, and a battery constructed by 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, hydrocarbon site-containing polymers such as polyethylene and polypropylene, polytetrafluoroethylene site-containing polymers, polyfluorinated vinylidene site-containing polymers, cellulose, fibrillated cellulose, biscous rayon, cellulose acetate, etc. Aromatic ring site-containing polymers such as hydroxyalkyl cellulose, carboxymethyl cellulose, polyvinyl alcohol-containing polymer, cellophane, polystyrene, etc., polyacrylonitrile site-containing polymer, polyacrylamide site-containing polymer, polyhalogenated vinyl site-containing polymer, polyamide site-containing polymer, polyimide site Containing polymer, ester site-containing polymer such as nylon, poly (meth) acrylic acid site-containing polymer, poly (meth) acrylate site-containing polymer, hydroxyl group-containing polymer such as polyisoprenor and poly (meth) allyl alcohol, polycarbonate, etc. Carbonate group-containing polymer, ester group-containing polymer such as polyester, carbamate or carbamide group site-containing polymer such as polyurethane, agar, gel compound, organic-inorganic hybrid (composite) compound, ion-exchange film polymer, cyclized polymer, sulfonic acid Examples thereof include a film made of a salt-containing polymer, a quaternary ammonium salt-containing polymer, a quaternary phosphonium salt polymer, a cyclic hydrocarbon group-containing polymer, an ether group-containing polymer, an inorganic substance such as ceramics, and the like. 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 laminated independently of each other. When the films are in close contact with each other, the laminated structure may have a clear interface, or may form a laminated structure having a mixed layer in which these components are mixed.

As the positive electrode active material constituting the battery of the present invention, a substance 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 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, etc. Manganese-containing compounds; silver oxide; lithium-containing compounds such as lithium cobalt oxide; iron-containing compounds; zinc species such as metallic zinc and zinc oxide.
Among these, one of the preferred embodiments of the present invention is 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, materials usually used as the negative electrode active material of the battery, such as carbon, lithium, sodium, magnesium, zinc, nickel, tin, and silicon-containing materials, can be used. Among these, from the viewpoint of exhibiting the characteristics of the anionic conductive film of the present invention, it is particularly preferably used as it is for an active material such as zinc, lithium, nickel, etc., which may generate dendrites due to an electrode reaction. be able to.

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, Metal zinc, Corrosion resistant metal Zinc, Zinc foil, Zinc mesh (Expanded metal), (Punching) steel plate, Non-woven fabric with conductivity; (Electrolytic) copper foil with added Sn, Pb, Hg, Bi, In, Tl, brass, etc., copper mesh (expanded metal), foamed copper, punched copper, copper alloy such as brass, brass foil, brass mesh (expanded metal) ) ・ Foamed brass ・ Punching brass ・ Nickel foil ・ Corrosion resistant nickel ・ Nickel mesh (expanded metal) ・ Punching nickel ・ Metal zinc ・ Corrosion resistant metal zinc ・ Zinc foil ・ Zinc mesh (expanded metal) ・ (Punching) steel plate ・ Non-woven fabric; Ni ・(Electrolytic) copper foil plated with Zn, Sn, Pb, Hg, Bi, In, Tl, brass, etc., copper mesh (expanded metal), foamed copper, punched copper, copper alloy 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 ; 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 aqueous 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 electrolyte 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 to 99.9% by mass, based on 100% by mass of the total of the aqueous electrolytic solution and the organic solvent-based electrolytic solution. More preferably, it is 20 to 99.9% by mass.

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, but for example, a solid electrolyte containing a compound similar to the above separator or a gel crosslinked by a cross-linking agent. 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); a third pole (for example, charging) different from the positive electrode and the negative electrode. Any form may be used, such as the use of an electrode that removes oxygen and hydrogen generated during discharge, a fuel cell, and the like, but a secondary battery or a fuel cell is preferable.
The type of the battery of the present invention is not particularly limited, but is a battery using 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 substance, especially a separator for a battery using a zinc type.

It is a figure which showed the result of having observed the cross section of the anion conductive film of 100 μm thickness produced in Example 1 with a scanning electron microscope. It is a figure which showed the result of having observed the cross section of the anion conductive film of 100 μm thickness produced in Comparative Example 1 with a scanning electron microscope. It is a figure which showed the result of charge / discharge evaluation of Example 1 and Comparative Examples 1 and 2.

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.
<Air permeability>
In the examples, the air permeability (s) was measured by Asahi Seiko Co., Ltd. Oken type air permeability smoothness measuring device KY-55 according to JIS P8117 Oken type testing machine method, 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 was set to 30,000 s. That is, in the embodiment, the air permeability of 30,000 s means that the air permeability 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 (N) was measured using a digital force gauge ZTA-50N (manufactured by Imada Co., Ltd.) 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 (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 (μm) of the anionic conductive film and the film of the insulating substance was measured with a film thickness meter (trade name: Digimatic Indicator 543-394, manufactured by Mitutoyo Co., Ltd.) and calculated as an average of three measurement points. ..
<Calculation of X value>
The X value is determined by the following formula, where the air permeability obtained by the above measurement method is T (s), the puncture strength is F (N), the density is ρ (g / cm ³ ), and the film thickness is L (μm). Obtained according to 1).

<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 respectively calculated from the mass (M _a) when immersed overnight in, and the liquid absorption rate by obtaining an average value thereof.
<Swelling degree>
Ten test pieces cut into 25 mm × 25 mm squares from any location of the anion 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.
<Resistance value>
The resistance value (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: Immersed 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 the impedance and the intercept component (Rb) when the measurement sample was not included by the following formula.
R = (Ra-Rb)

<Charge / discharge test>
Zinc oxide powder (manufactured by Mitsui Metal Mining Co., Ltd.), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) and carbon powder (trade name: Ketjen Black EC600JD, Lion Specialty Co., Ltd.) A zinc electrode negative electrode was prepared by placing an active material kneaded with (manufactured by Chemicals) at a mass ratio of 59: 5: 4 on punching nickel, and a positive electrode was prepared by attaching a zinc plate and the above-mentioned active material to punching nickel. Then, this single-layer anion conductive film was placed between the two poles to charge and discharge. Using a mercury electrode as a reference electrode ^{, charging / discharging was performed at a charging / discharging current of 60 mA / cm 2} for 10 minutes, and the charging / discharging characteristics of the anionic conductive film were confirmed.
・ Number of charged cells: 5 cells (list the average value)
-Reference electrode: Mercury electrode-Electrolyte: 6.7 mol / L concentration KOH aqueous solution saturated with zinc oxide <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% by mass of 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 aqueous dispersion is determined by diluting the polymer aqueous dispersion with distilled water, collecting about 10 mL of the obtained diluent in a glass cell, and measuring the particle size distribution by a dynamic light scattering method. The measurement was performed using [Particle Sizing Systems, Inc., trade name: NICOMP Model 380], and a 50% volume average particle size was obtained as the volume average particle size.
<Glass transition temperature of polymer>
For the glass transition temperature, a polymer film was formed by applying the polymer to a glass plate and drying at 120 ° C. for 1 hour, and the obtained polymer film was subjected to a differential scanning calorimeter (device name: thermal analyzer). DSC3100S, BRVKER) was used for measurement.

<Area ratio of compound particles to anionic conductive film-forming material components other than compounds>
The area ratio is the membrane cross section obtained by cutting the anionic conductive membrane perpendicular to the surface of the membrane (the membrane cross section was prepared using a range of 10 mm × 10 mm at the center of the short side of the anion conductive membrane). Using a scanning electron microscope, 10,000-fold magnified photographs were taken at any five locations so that 70% or more of the cross section was the anionic conductive film-forming material portion. In the obtained enlarged cross-sectional photograph, a region of 8 μm in the thickness direction × 12 μm in the plane direction is covered by 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. The obtained image was analyzed using image analysis software manufactured by Image technology, and 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 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). 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. In the obtained enlarged cross-sectional photograph, a region of 8 μm in the thickness direction × 12 μm in the plane direction is covered by 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 obtained image was analyzed using image analysis software manufactured by Image metrology, and the ratio of the void portion to the image was determined. 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. In the obtained enlarged cross-sectional photograph, a region of 8 μm in the thickness direction × 12 μm in the plane direction is covered by 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 obtained image was analyzed using image analysis software manufactured by Image technology, and the size of the white portion in the image was determined as the particle diameter of the inorganic compound particle. .. 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.

<Charge / discharge evaluation>
Zinc oxide powder (manufactured by Mitsui Metal Mining Co., Ltd.), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) and carbon powder (trade name: Ketjen Black EC600JD, Lion Specialty Co., Ltd.) A zinc electrode negative electrode was prepared by placing an active material kneaded with (manufactured by Chemicals) at a mass ratio of 59: 5: 4 on punching nickel, and a positive electrode was prepared by attaching a zinc plate and the above-mentioned active material to punching nickel. Then, this single-layer anion conductive film was placed between the two poles to charge and discharge. Using a mercury electrode as a reference electrode ^{, charging / discharging was performed at a charging / discharging current of 60 mA / cm 2} for 10 minutes, and the charging / discharging characteristics of the anionic conductive film were confirmed.
<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 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 so that the non-volatile content was 48.2% and the pH was adjusted to 48.2%. An aqueous dispersion of a (meth) acrylic copolymer having a volume average particle diameter of 7.8 and a volume average particle diameter of 190 nm was obtained.

[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 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 copolymer 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 to initiate polymerization. Then, 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 copolymer 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 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 copolymer 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, 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 were added to the dropping funnel. 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 remainder of the pre-emulsion (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 pre-emulsion (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 copolymer 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 to initiate polymerization. Then, 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 copolymer having a volume average particle diameter of 7.8 and a volume average particle diameter of 190 nm was obtained.

[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 pre-aqueous solution (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 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 remainder of the pre-emulsion (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 copolymer 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 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 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 so that the non-volatile content was 48.2% and the pH was adjusted to 48.2%. An aqueous dispersion of a (meth) acrylic copolymer having a volume average particle diameter of 8.6 nm was obtained.

Example 1
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: Polyflon D210C, manufactured by Daikin Industries, Ltd., solid content 60%) and carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem). Pure water and pure water were kneaded with a kneader at a mass ratio of 100: 100: 5: 3: 15 and roll-rolled to prepare 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 (T) was 30,000 s, the puncture strength (F) was 3.3 N, the density (ρ) was 1.54 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 228,690.
The liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 9%.
The results of observing the cross section of the obtained anion conductive film with a scanning electron microscope are shown in FIG. 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 0.00%. The cross-sectional particle size 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 0.23 Ω, and when charge / discharge evaluation was performed, 310 cycles of charge / discharge could be achieved. The charge / discharge evaluation results are shown in FIG.

Example 2
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 100: 100: 5: 3: 15 and roll-rolled to prepare an anionic conductive film having a thickness of 300 μm. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 4.3 N, the density (ρ) was 1.51 g / cm ³ , and the film thickness (L) was 300 μm. The calculated X value was 97,395.
The liquid absorption rate of the obtained anionic conductive film was 20%, and the swelling degree was 11%.
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 55/45, 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 0.39 μm.
The resistance value (R) of the obtained anion conductive film was 0.64Ω, and when charge / discharge evaluation was performed, 700 cycles of charge / discharge could be achieved.

Example 3
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 65: 135: 5: 3: 15 and roll-rolled to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 3.1 N, the density (ρ) was 1.35 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 188,325.
The liquid absorption rate of the obtained anionic conductive film was 17%, and the swelling degree was 11%.
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 33/67, and the ratio of voids was 0%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.42 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and 250 cycles of charge / discharge could be achieved by performing charge / discharge evaluation.

Example 4
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 135: 65: 5: 3: 15 and roll-rolled to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.7 N, the density (ρ) was 1.68 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 204,120.
The liquid absorption rate of the obtained anionic conductive membrane was 15%, 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 69/31, and the ratio of voids was 0.5%. The cross-sectional particle size of the hydrotalcite particles in the anion conductive film at this time was 0.30 μm.
The resistance value (R) of the obtained anion conductive film was 0.20 Ω, and when charge / discharge evaluation was performed, 260 cycles of charge / discharge could be achieved.

Example 5
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD102A, manufactured by JSR Corporation, Tg = -5 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 100: 100: 5: 3: 15 and roll-rolled to prepare 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 (T) was 30,000 s, the puncture strength (F) was 2.7 N, the density (ρ) was 1.51 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 183,465.
The liquid absorption rate of the obtained anionic conductive film was 16%, 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 52/48, and the ratio of voids was 0.1%. The cross-sectional particle size 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 when charge / discharge evaluation was performed, 300 cycles of charge / discharge could be achieved.

Example 6
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD104A, manufactured by JSR Corporation, Tg = 7 ° C., solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure water. And kneaded with a kneader at a mass ratio of 100: 100: 5: 3: 20 and roll-rolled to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.8 N, the density (ρ) was 1.49 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 187,740.
The liquid absorption rate of the obtained anionic conductive membrane was 15%, 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 0.37 μm.
The resistance value (R) of the obtained anion conductive film was 0.2Ω, and when charge / discharge evaluation was performed, 300 cycles of charge / discharge could be achieved.

Example 7
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, Tg = -2 ° C., solid content 48%) was kneaded with a kneader at a mass ratio of 100: 100, and roll rolling was carried out to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 3.2 N, the density (ρ) was 1.53 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 220,320.
The liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 11%.
In the obtained anion conductive film cross section, the ratio of the total area of hydrotalcite particles to the total area of other components was 54/46, and the ratio of the area of voids to the entire cross section of the film was 0.2%. there were. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.39 μm.
The resistance value (R) of the obtained anion conductive film was 0.25Ω, and when charge / discharge evaluation was performed, 290 cycles of charge / discharge could be achieved.

Example 8
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD1002, manufactured by JSR Corporation, Tg = -20 ° C, solid content 50%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 100: 100: 5: 3: 15 and roll-rolled to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 3.1 N, the density (ρ) was 1.52 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 212,040.
The liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 11%.
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 52/48, 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 0.39 μm.
The resistance value (R) of the obtained anion conductive film was 0.20 Ω, and when charge / discharge evaluation was performed, 300 cycles of charge / discharge could be achieved.

Example 9
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 50%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) and pure water in a mass ratio of 100: 100: 5: 15 kneader By kneading and rolling, an anionic conductive film having a thickness of 100 μm was produced. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 3.0 N, the density (ρ) was 1.53 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 206,550.
The obtained anionic conductive membrane had a liquid absorption rate of 17% and a swelling degree of 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 55/45, and the ratio of voids was 0.5%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.42 μm.
The resistance value (R) of the obtained anion conductive film was 0.21Ω, and when charge / discharge evaluation was performed, 280 cycles of charge / discharge could be achieved.

Example 10
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 50%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure water are kneaded with a kneader at a mass ratio of 100: 100: 3: 15 and rolled. , An anion conductive film having a thickness of 100 μm was prepared. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.7 N, the density (ρ) was 1.53 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 185,895.
The liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 10%.
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 51/49, and the ratio of voids was 0.7%. The cross-sectional particle size of the hydrotalcite particles in the anion conductive film at this time was 0.40 μm.
The resistance value (R) of the obtained anion conductive film was 0.22Ω, and when charge / discharge evaluation was performed, 270 cycles of charge / discharge could be achieved.

Example 11
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 an aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 membrane, the air permeability (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 calculated X value 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 12
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 2. In the same manner as above, an anion conductive film was obtained. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.7 N, the density (ρ) was 1.53 g / cm ³ , and the film thickness (L) was 102 μm. The X value calculated from 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 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 0.1%. The cross-sectional particle size 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 13
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 3. In the same manner as above, an anion conductive film was obtained. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (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 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 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 0.1%. The cross-sectional particle size 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 14
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 4. In the same manner as above, an anion conductive film was obtained. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 1.7 N, the density (ρ) was 1.50 g / cm ³ , and the film thickness (L) was 98 μm. The X value calculated from was 117,092.
The liquid absorption rate of the obtained anionic conductive film was 12%, 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 0.1%. The cross-sectional particle size 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 15
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 5. In the same manner as above, an anion 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 (T) was 30,000 s, the puncture strength (F) was 1.9 N, the density (ρ) was 1.52 g / cm ³ , and the film thickness (L) was 99 μm. The X value calculated from 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 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 film was 0.21Ω, and 330 cycles were achieved for charge / discharge evaluation.

Example 16
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 6. In the same manner as above, an anion conductive film was obtained. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 1.9 N, the density (ρ) was 1.5 g / cm ³ , and the film thickness (L) was 103 μm. The X value calculated from 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 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 size 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 film was 0.21Ω, and 330 cycles were achieved for charge / discharge evaluation.

Example 17
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 7. In the same manner as above, an anion conductive film was obtained. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.8 N, the density (ρ) was 1.51 g / cm ³ , and the film thickness (L) was 101 μm. The X value calculated from was 188,376.
The liquid absorption rate of the obtained anionic conductive film was 12%, 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 55/45, and the ratio of voids was 0.2%. The cross-sectional particle size 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 18
Example 11 except that the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1 was changed to the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 8. In the same manner as above, an anion 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 (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 was 169,318.
The liquid absorption rate of the obtained anionic conductive film was 16%, and the swelling degree was 7%.
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 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 19
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 135 parts by mass, 65 parts by mass of aqueous dispersion of (meth) acrylic copolymer prepared in Preparation Example 1. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 15 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 one of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (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 was 109,442.
The liquid absorption rate of the obtained anionic conductive film 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 20
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 65 parts by mass, 135 parts by mass of aqueous dispersion of (meth) acrylic copolymer prepared in Preparation Example 1. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 2 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 one of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.2 N, the density (ρ) was 1.34 g / cm ³ , and the film thickness (L) was 102 μm. The X value calculated from 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 21
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 an aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 2. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead 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 film, the air permeability (T) was 30,000 s, the puncture strength (F) was 1.8 N, the density (ρ) was 1.54 g / cm ³ , and the film thickness (L) was 52 μm. The X value calculated from 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 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 size 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 22
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 an aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 2. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (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 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 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 size 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 23
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 an aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 3. Weigh 3 parts by mass of methyl cellulose (trade name: SM1500, manufactured by Shin-Etsu Chemical Co., Ltd.) and 10 parts by mass of pure water, knead with a kneader until uniform, and then add the thickness of 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 film, the air permeability (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 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 size 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 24
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 100 parts by mass, aqueous dispersion of acrylonitrile-butadiene copolymer (product name: NA-13, manufactured by A & L) , 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, manufactured by Daicel FineChem) ) Weigh 3 parts by mass and 15 parts by mass of pure water, knead them with a kneader until they are in a uniform state, and then roll press the obtained kneaded product to a thickness of 100 μm to achieve anion conductivity. A film was obtained. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (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 calculated X value was 177,840.
The liquid absorption rate of the obtained anionic conductive film was 19%, and the swelling degree was 11%.
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 52/48, and the ratio of voids was 0.3%. The cross-sectional particle size 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.

Example 25
In Example 13, except that 3 parts by mass of carboxymethyl cellulose was changed to 5 parts by mass of polyacrylate (trade name: Aquaric DL522, manufactured by Nippon Shokubai Co., Ltd.) and 10 parts by mass of pure water was changed to 5 parts by mass. An anion conductive film was obtained in the same manner as in 13. The ease of film formation was 2 of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) is 30,000 s, the puncture strength (F) is 2.1 N, the density (ρ) is 1.51 g / cm ³ , and the film thickness (L) is 100 μm. The X value calculated from was 142,695.
The liquid absorption rate of the obtained anionic conductive film was 18%, and the swelling degree was 12%.
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 size 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 0.19Ω, and 350 cycles were achieved for charge / discharge evaluation.

Example 26
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) 50 parts by mass, 50 parts by mass of the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1. Anionic conductive film by measuring 1 part by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 60 parts by mass of pure water and kneading with a homodisper until a uniform state is obtained. An aqueous slurry of the forming material was obtained. The obtained aqueous slurry was applied to the silicone-treated side of a polyethylene terephthalate (PET) film (release film) whose one side was silicone-treated with an applicator, dried at 120 ° C. for 30 minutes, and then the obtained anion was obtained. An anionic conductive film was obtained by peeling the coating film made of the conductive forming material from the release film. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.5 N, the density (ρ) was 1.53 g / cm ³ , and the film thickness (L) was 98 μm. The calculated X value was 175,638.
The liquid absorption rate of the obtained anionic conductive membrane was 12%, and the swelling degree was 5%.
In the obtained anion conductive film cross section, the ratio of the total area of hydrotalcite particles to the total area of other components was 52/48, and the ratio of the area of voids to the entire cross section of the film was 0%. .. The cross-sectional particle size 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 420 cycles were achieved for charge / discharge evaluation.

Example 27
The aqueous dispersion of the (meth) acrylic copolymer of Example 26 was used as an aqueous dispersion of a styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C., solid content 50%). An anionic conductive film was obtained in the same manner as in Example 26 except for the modification. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (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 calculated X value was 177,840.
The liquid absorption rate of the obtained anionic conductive membrane was 16%, and the swelling degree was 9.5%.
In the obtained anion conductive film cross section, the ratio of the total area of hydrotalcite particles to the total area of other components was 52/48, and the ratio of the area of voids to the entire cross section of the film was 0%. .. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.39 μm.
The resistance value (R) of the obtained anion conductive film was 0.21Ω, and 320 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 is 0.20 μm) and polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) And pure water were kneaded with a kneader at a mass ratio of 100: 120: 50 and rolled to prepare an anionic conductive film having a thickness of 100 μm. The results of observing the cross section of the prepared film with a scanning electron microscope are shown in FIG. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 1000 s, the puncture strength (F) was 0.6 N, the density (ρ) was 1.27 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 38.
The liquid absorption rate of the obtained anionic conductive film was 25%, and the swelling degree was 11%. Furthermore, the percentage of voids was 4.5%. The cross-sectional particle size of the hydrotalcite particles in the anion conductive film at this time was 0.40 μm.
The resistance value (R) of this anionic conductive film was 0.19 Ω, and when charge / discharge evaluation was performed in the same manner as in Example 1, the positive electrode and the negative electrode were short-circuited due to the growth of dendrites in 85 cycles of charge / discharge. The charge / discharge evaluation results are shown in FIG.

Comparative Example 2
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%) And pure water were kneaded with a kneader at a mass ratio of 100: 120: 50 and rolled to prepare an anionic conductive film having a thickness of 300 μm. The ease of film formation was 3 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 1600 s, the puncture strength (F) was 1.3 N, the density (ρ) was 1.29 g / cm ³ , and the film thickness (L) was 300 μm. The calculated X value was 72.
The liquid absorption rate of the obtained anionic conductive film was 23%, and the swelling degree was 15%. Furthermore, the percentage of voids was 5.1%. The cross-sectional particle diameter of the hydrotalcite particles in the anion conductive film at this time was 0.39 μm.
The resistance value (R) of this anionic conductive film was 0.57Ω, and when charge / discharge evaluation was performed in the same manner as in Example 1, the positive electrode and the negative electrode were short-circuited due to the growth of dendrites in 165 cycles of charge / discharge. The charge / discharge evaluation results are shown in FIG.

Comparative Example 3
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and an aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR Corporation, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure Water and water were kneaded with a kneader at a mass ratio of 150: 50: 5: 3: 30, and roll-rolled to prepare an anionic conductive film having a thickness of 100 μm. The ease of film formation was one of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 3800 s, the puncture strength (F) was 1.4 N, the density (ρ) was 1.59 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 1607.
The obtained anionic conductive membrane had a liquid absorption rate of 17% and a swelling degree of 11%.
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 74/26, and the ratio of voids was 1.4%. 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, the positive electrode and the negative electrode were short-circuited due to the growth of dendrites in 120 cycles of charge / discharge.

Comparative Example 4
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Co., Ltd., average particle size is 0.20 μm) and aqueous dispersion of styrene-butadiene copolymer (product name: TRD2001, manufactured by JSR, Tg = -2 ° C, solid content 48%), polytetrafluoroethylene aqueous dispersion (trade name: D210C, manufactured by Daikin Industries, Ltd., solid content 60%), carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and pure The kneader was kneaded with water at a mass ratio of 50: 150: 5: 3: 15, but the fluidity was high and film formation could not be performed. The ease of film formation was 0 of the above evaluation criteria.

Comparative Example 5
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size is 0.20 μm) and 50% polyolefin dispersion (product name: Chemipal, Mitsui Chemicals, Inc.) with a mass ratio of 100: 100. Although the kneader was kneaded in a ratio, it was not possible to sufficiently bind the mixture, and it was difficult to prepare a film. The ease of film formation was 0 of the above evaluation criteria.

Comparative Example 6
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 145 parts by mass, 55 parts by mass of the aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 2 of the above evaluation criteria.
In the obtained anion conductive membrane, the air permeability (T) was 4000 s, the puncture strength (F) was 1.9 N, the density (ρ) was 1.67 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 2538.
The liquid absorption rate of the obtained anionic conductive film was 16%, and the swelling degree was 11%.
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 74/26, and the ratio of voids was 1.3%. 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 0.18Ω, and 120 cycles were achieved for charge / discharge evaluation.

Comparative Example 7
Hydrotalcite (trade name: DHT-6, manufactured by Kyowa Chemical Industry Co., Ltd., average particle size 0.20 μm) 55 parts by mass, 145 parts by mass of an aqueous dispersion of the (meth) acrylic copolymer prepared in Preparation Example 1. Weigh 3 parts by mass of carboxymethyl cellulose (trade name: Daicel 1380, manufactured by Daicel FineChem) and 10 parts by mass of pure water, knead with a kneader until a uniform state is obtained, and then knead the obtained kneaded product. 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 one of the above evaluation criteria.
In the obtained anion conductive film, the air permeability (T) was 30,000 s, the puncture strength (F) was 2.3 N, the density (ρ) was 1.33 g / cm ³ , and the film thickness (L) was 100 μm. The calculated X value was 137,655.
The liquid absorption rate of the obtained anionic conductive film was 15%, and the swelling degree was 11%.
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 27/73, 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 0.37 μm.
The resistance value (R) of the obtained anion conductive film was 0.26 Ω, and 110 cycles were achieved for charge / discharge evaluation.

Example 28
An aqueous slurry of an anion conductive film-forming material was obtained in the same manner as in Example 27. The obtained aqueous slurry is applied onto a non-woven fabric (trade name: H-8007, manufactured by Japan Vilene) at ^{a coating amount of 1 g / cm 2} using an applicator, and dried at 120 ° C. for 30 minutes to obtain a non-woven fabric. An anion conductive membrane laminate in which an anion conductive membrane was integrated was obtained.
In the obtained anion conductive membrane laminate, the air permeability (T) was 30,000 s, the puncture strength (F) was 4.7 N, the density (ρ) was 1.23 g / cm ³ , and the film thickness (L) was 185 μm. The X values calculated from these were 140,619.
The liquid absorption rate of the obtained anion conductive membrane laminate was 11%, and the swelling degree was 0.8%.
The ratio of the total area of hydrotalcite particles to the total area of other components in the cross section of the anion conductive film portion of the obtained anion conductive film laminate is 53/47, and the ratio of voids to the entire film cross section is 53/47. The area ratio was 0%. 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 laminate was 0.14 Ω, and when charge / discharge evaluation was performed using the obtained anion conductive membrane laminate as a separator, 360 cycles were achieved.

Example 29
The anionic conductive film obtained in Example 1 was laminated on a non-woven fabric (trade name: H-8007, manufactured by Japan Vilene Company, Inc.) and bonded using a roll-type laminator, and the anionic conductive film was formed on the non-woven fabric. An anion conductive film laminate in which the above was integrated was obtained. When charge / discharge evaluation was performed using the obtained anion conductive membrane laminate as a separator, 340 cycles were achieved.

Example 30
The anionic conductive film obtained in Example 22 was laminated on a non-woven fabric (trade name: H-8007, manufactured by Japan Vilene Company, Inc.) and bonded using a roll-type laminator, and the anionic conductive film was formed on the non-woven fabric. An anion conductive film laminate in which the above was integrated was obtained. When charge / discharge evaluation was performed using the obtained anion conductive membrane laminate as a separator, 450 cycles were achieved.

As described above, using 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, the total area of the inorganic compound compound particles is combined with the total area of the inorganic compound compound particles. By forming an anionic conductive film having a ratio of 70/30 to 30/70 to the total area of other components and forming a battery using the obtained anionic conductive film, the life is long and long. A battery excellent in use for a period of time was obtained.

Claims (5)

An anion conductive film formed using an anion conductive film forming material.
The anionic conductive film-forming material includes a conjugated diene polymer and / or a (meth) acrylic polymer, a compound containing at least one element selected from Groups 1 to 17 of the periodic table, and further. As the polymer other than the conjugated diene polymer and the (meth) acrylic polymer, at least one selected from the group consisting of a halogen atom-containing polymer, a carboxy group-containing polymer, and a hydroxyl group-containing polymer is included.
The cross section of the anion conductive film is the total area of the compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table, and the components of the anion conductive film forming material other than the compound. An anionic conductive film characterized in that the ratio to the total area (compound particles / components of an anionic conductive film-forming material other than the compound) is 70/30 to 51/49. The average cross-sectional particle size of the compound particles containing at least one element selected from Group 1 to Group 17 of the periodic table in the cross section of the anion conductive film is 0.1 to 1.0 μm. The anionic conductive film according to claim 1. The compound containing at least one element selected from Groups 1 to 17 of the periodic table is at least selected from the group consisting of oxides, hydroxides, layered compound hydroxides, and phosphoric acid compounds. The anionic conductive film according to claim 1 or 2, characterized in that it is one compound. 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.

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