JPH04184811A - Solid electrolyte film - Google Patents

Abstract

PURPOSE:To obtain a thermally/electrically stable solid electrolyte with an extremely high dielectric characteristic at a room temperature by including a matrix polymer made of a polymer of polymerizating vinyl monomer, a specific conductive polymer compound and specific soluble substance and the like. CONSTITUTION:A solid electrolyte film is prepared by including a matrix polymer made of polymer of polymerizing vinyl monomer, and conductive polymer compound obtained by the method of applying chemical oxydation polymerization to a monomer selected from the formula III or/and IV. A soluble substance made of salt in which ammonium ion as expressed by the formula I or/and II or quarternary phosphonium ion is a cation component while a conjugate base is an anion component, and an organic solvent are also included. In the formulae I and III, R<1>-R<4> may be the same or different, and denote alkyl group of 1-4 of hydrogen and carbon atoms or alkyl group of 6-10 of carbon atoms, R<5> represent aliphatic complex ring being coupled to N atom in the formula II.

Description

[Detailed description of the invention] [Background of the invention] Regarding solid electrolyte membranes.

More specifically, the present invention provides a thin film solid electrolyte that has extremely high conductivity at room temperature, is thermally and electrochemically stable, and is highly flexible, and is safe as an electrolyte for electrolytic capacitors. The present invention relates to a solid electrolyte membrane that can be suitably used for various purposes.

<Prior Art> Conventionally, ion conductive materials have been used in the form of a solution by dissolving an electrolyte in water or an organic solvent, which has caused a problem of leakage. By improving this leakage resistance, highly reliable equipment,
For example, for the development of solid electrolytic capacitors, solid electrolytes have high conductivity comparable to or higher than liquid organic electrolytes, are thermally and electrochemically stable, and are flexible and flexible. development is desired. Therefore,
In recent years, research on solidifying electrolytes has been actively conducted.

For example, organic solid electrolytes include a complex system of crown ether and an alkali metal halide, and a system in which an alkali metal salt is complexed with polyethylene oxide as a matrix (solid medium ionics (S
solid 5tate Ionlcs), 3/1.38
9 (1981)), polyacrylonitrile and LiC
Composite membrane of IO4 and ethylene carbonate (Journal of Polymer Science (J, Poly■, Sci.
, ), A 2.21.939 (1983)).

However, all of these solid electrolytes have electrical conductivities of 10' to 10-2S-am-' at room temperature, and are liquid organic electrolytes (hereinafter abbreviated as electrolytes).

Electrical conductivity: 10-10-2S extremely small compared to 10-2S-.

C. Summary of the Invention〕〈Problems to be Solved by the Invention〉 In particular, when applied to electrolytic capacitors, solid electrolytes are thermally and electrochemically stable, flexible, and have excellent safety. It has been demanded. Furthermore, as electronic devices become more sophisticated and smaller, there is a growing demand for high-performance electrolytic capacitors, such as higher frequency switching power supplies and smaller electrolytic capacitors. development is an important issue and challenge.

Means for Solving the Problems> The present invention has been made to solve the above problems, and provides a solid electrolyte membrane that can be suitably used as an electrolyte in an electrolytic capacitor.

That is, the solid electrolyte membrane according to the present invention comprises (a) a matrix polymer consisting of a polymer of polymerizable and nil monomers, and (b) the following general formula (m) or/and (mV).
(C) ammonium ion or quaternary compound represented by the following general formula (I) or/and (■); It is characterized in that it contains at least one kind of solute consisting of a salt having a phosphonium ion as a cation component and a conjugate base of an acid as an anion component, and (d) an organic solvent.

(In formulas (1) and (II), R1, R2, R3 and R4 may be the same or different and represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. represented, R5 has 3 to 3 carbon atoms which forms an aliphatic heterocycle or an aromatic heterocycle by bonding with the nitrogen atom in formula (II);
Represents 10 groups. ) (in formula (m) and formula (IV),
R6-R13 may be the same or different and represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and at least one of R6 and R7 is hydrogen. ), R12 and R13 may each have a cyclic structure. Also, X is oxygen, sulfur or NR
14, N is nitrogen, R14 is hydrogen, carbon number 1
-4 alkyl group or an aryl group having 6 to 10 carbon atoms. ) <Effects of the Invention> The solid electrolyte membrane according to the present invention exhibits extremely high conductivity at room temperature (e.g., 5 mS-cm-' or more), is electrochemically stable, flexible, and heat resistant. It is a solid electrolyte with excellent properties and safety, and is particularly suitable for use as an electrolyte in electrolytic capacitors.

[Detailed description of the invention]

Matrix Polymer (Component (a))> The matrix polymer forming the matrix or linking phase of the solid electrolyte membrane in the present invention is composed of a polymer of polymerizable vinyl monomers.

Here, the polymerizable and nil monomers are preferably C1 to
It means a monomer having a C2 alkyl group) which forms a polymer by addition polymerization of this monomer. Therefore, "vinyl monomer J" as used in the present invention has the same meaning as "ethylenic unsaturated monomer." and,
"Polymer of polymerizable vinyl monomers and vinyl monomers" means, in addition to homopolymers of polymerizable vinyl monomers and mutual copolymers, a predominant amount of polymerizable vinyl monomers and a smaller amount of copolymerizable monomers. It means a copolymer with a body.

Such polymerizable vinyl monomers have polar groups,
Especially hydroxyl group or lower alkoxyl group (C1~
C4 or so), those having a carboxyl group, an amide group, or an amino group are preferred.

Specific examples of such monomers include alkoxyalkyl-(meth)acrylates, hydroxyalkyl-(
(meth)acrylic acid esters such as meth)acrylate, glycerol mono-, di- and tri-(meth)acrylate, alkylene glycol mono- and di(meth)acrylate, unsaturated nitriles such as (meth)acrylonitrile, styrene, etc. Examples include aromatic olefins, vinyl compounds such as vinyl chloride and vinyl acetate, N-vinyl lactams such as N-vinylpyrrolidone and N-vinylpiperidone, (meth)acrylic acid, and (meth)acrylamide. Among these, at least one selected from alkoxyalkyl-(meth)acrylates, hydroxyalkyl-(meth)acrylates, glycerol-mono-, di- and tri-(meth)acrylates, and alkylene glycol-mono- and di-(meth)acrylates. (meth)acrylic acid esters are preferably used.

Here, "(meth)acrylic acid" and "(meth)acrylate" mean both acrylic acid and methacrylic acid, and acrylate and methacrylate, respectively.

Now, a group of preferred (meth)acrylic esters for obtaining high electrical conductivity are alkoxyalkyl-(meth)acrylates. Each of the "alkoxyalkyl" groups is a lower one, especially one having about 1 to 4 carbon atoms, preferably about 1 to 3 carbon atoms for an "alkoxy" group, and about 2 to 3 carbon atoms for an "alkyl" group, is preferred.

Specific examples of such alkoxyalkyl-(meth)acrylates include methoxyethyl, ethoxyethyl and propoxyethyl esters of acrylic and methacrylic acids.

Another group of preferred (meth)acrylic esters are hydroxyalkylates. In this case, "the alkyl j group is also a lower one,
In particular, those having about 2 to 4 carbon atoms are preferred.

The "hydroxylalkyl" group preferably has 1 m of hydroxyl groups.

Specific examples of such hydroxyalkyl-(meth)acrylates include hydroxyethyl and hydroxypropyl esters of acrylic and methacrylic acids.

Another group of preferred (meth)acrylic esters are glycerol-(meth)acrylates. This (meth)acrylate is preferably one in which one or two of the three hydroxyl groups of glycerol are esterified.

Specific examples of such glycerol-covered (meth)acrylates include glycerol monomethacrylate, glycerol dimethacrylate, and glycerol acrylate methacrylate. Another group of preferred (meth)acrylic esters is alkylene glycol-(
meth)acrylate. "Alkylene" group is lower,
In particular, C2 to C3 are preferable, and "alkylene glycol" refers to oligoalkylene glycols, especially polymers ranging from di-, tri-, and tetra-alkylene glycols to polyalkylene glycols (molecular weight up to about 4,000) and their terminal hydroxyl groups ( (if any) alkoxylated derivatives (especially lower alkoxylated derivatives).

Specific examples of such alkylene glycol-acrylates include diethylene glycol-(meth)acrylate, triethylene glycol-(
meth)acrylate, polyethylene glycol-(meth)acrylate (average molecular weight about 200 to 2,000)
, dipropylene glycol (meth)acrylate, tripropylene glycol (meth)acrylate, polypropylene glycol (meth)acrylate (average molecular weight about 300 to 3.000), polyalkylene glycol (meth)acrylate (ethylene oxide/propylene) Oxide block copolymer, average molecular weight 20
0 to 3,000), methoxypolyethylene glycol-(meth)acrylate (average molecular weight 200 to 2,0
(about 00), ethoxypolyethylene glycol-(meth)acrylate (average molecular weight about 200 to 2,000)
, propoxypolyethylene glycol-(meth)acrylate (average molecular weight approximately 200 to 2,000), phenoxypolyethylene glycol-(meth)acrylate (
average molecular weight 300 to 2,000) methoxypolypropylene glycol-(meth)acrylate (average molecular weight 250 to 3,000) ethoxypolypropylene glycol-(meth)acrylate (average molecular weight 250 to 3
,000) and ethylene glycol (meth)acrylate. These esters are for some or all of a given hydroxyl group.

As mentioned above, the polymer of these polymerizable vinyl monomers may be a copolymer with a small amount of copolymerizable monomer, but specific examples of such comonomers include: (a) Monofunctional monomers, such as (meth)acrylic acid alkyl esters (the alkyl group has about 1 to 3 carbon atoms); (b) difunctional monomers, such as ethylene glycol di(meth)acrylate, Ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polybrobylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neobentyl glycol di(meth)acrylate, 2- Hydroxy-1,3-di(
(meth)acryloxypropane, 2-hydroxy-1-acryloxy-3-methacryloxypropane, etc.
There are trifunctional monomers such as trimethylolpropane tri(meth)acrylate, tetramethylolmethane tri(meth)acrylate, and the like.

By polymerizing these polymerizable vinyl monomers using a polymerization initiator, it is possible to obtain a matrix polymer of component (a) that is thermally stable, flexible, and has excellent flexibility.

Electrically conductive polymer compound (component (b)) It is a polymer compound obtained by oxidative polymerization.

(In formula (m) and formula (IV), R6-R13 may be the same or different and represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. and at least one of R6 and R7 is hydrogen)
, R12 and R13 may each have a cyclic structure.

Further, X represents oxygen, sulfur or NR, N is nitrogen, and R14 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ) Here, "chemical oxidative polymerization" refers to the above general formula (III)
When a compound having an active hydrogen atom such as a heterocyclic compound represented by (IV) is reacted with an oxidizing agent, radicals are generated and polymerization is accompanied by dehydrogenation.

Specific examples of the monomer compound represented by formula (m) include aniline, 0-methylaniline, m-methylaniline, 0
Examples include alkylanilines such as -ethylaniline and m-ethylaniline and/or water-soluble salts thereof.

Specific examples of the monomeric compound represented by formula (IV) include:
Pyrrole, N-methylvirol, 3-methylvirol,
Examples include pyrrole compounds such as N-methyl-3-methylpyrrole and 3,4-dimethylpyrrole, thiophene compounds such as thiophene, 3-methylthiophene, 3-ethylthiophene, and inthianaphthene, and furan.

These monomers can be used alone or in combination. In addition, particularly preferred monomers for obtaining a highly conductive polymer compound are aniline and pyrrole.

In addition, there are no particular restrictions on the oxidizing agent used to cause the oxidative polymerization reaction of these monomers, but - for boat fishing, it is recommended to use an oxidizing agent with a standard electrode potential of 0.5 V or more. can. This standard electrode potential refers to the chemical reaction in which an oxidizing agent obtains electrons from an oxidized substance and is itself reduced, as a half-cell consisting of an electrode that receives and receives electrons from an external circuit. It refers to the magnitude of the electromotive force of a battery, and therefore, the oxidizing power can be quantified using this standard electrode potential. The value of such standard electrode potential is, for example, “
“Revised 4th Edition Electrochemistry Handbook” (edited by the Electrochemistry Association, Maruzen (1)
985))) etc.

Specifically, (a) iron chloride (■), ruthenium chloride (■
), molybdenum chloride (■), aluminum chloride (III
) Lewis acids such as (b) peroxides such as hydrogen peroxide and peracetic acid, (c) persulfates such as sodium persulfate, potassium persulfate, and ammonium persulfate, (d) sulfuric acid, nitric acid, fluorosulfuric acid, etc. protonic acids, (d) protonic acids such as sulfuric acid, nitric acid, and fluorosulfuric acid, (e) metal oxides such as cerium oxide (■), lead oxide (■), manganese dioxide, etc., (f) iodine, bromine, and iodide. Single halogens such as bromine and metal salts such as lead (tri)tetraacetate and cupric chloride can be used.

<Solute (component (c))> The solute of the component (c) used in the composition of the present invention is one that exhibits ionic conductivity when ionized into ions in the organic solvent of the component (d) described below. . As such a solute, a salt consisting of an ammonium ion or quaternary phosphonium ion represented by the following general formula (I) or/and (II) as a cation component and a conjugate base of an acid as an anion component is used. .

(In formulas (I) and (II), R1, R2, R3 and R4 may be the same or different, hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms ( (preferably phenyl or lower alkyl-substituted phenyl), and R5 is bonded to the nitrogen atom in formula (n) to form an aliphatic heterocycle (preferably a 5- to 7-membered aliphatic heterocycle) or an aromatic heterocycle having 3 to 3 carbon atoms. Represents 10 groups. ) The salt as the solute may be one type or a combination of two or more types.

Here, the conjugate base of an acid is defined as the conjugate base of an acid, as described in chemistry textbooks, etc., in the Brønsted-Lowry acid-base theory. H) means something that has lost.

Examples of ammonium ions as cationic components that form such salts include aliphatic ammonium ions, ammonium ions, and alicyclic ammonium ions represented by the above general formulas (I) and (II), as well as nitrogen-containing aromatic ammonium ions. There are ions.

Specifically, the ammonium ions represented by the formula (1) include (a) tetraethylammonium, tetrapropylammonium, tetrabutylammonium, methyltriethylammonium, methyltripropylammonium, methyltributylammonium, dimethyldiethylammonium, dimethyldipropylammonium , dimethyldibutylammonium, ethyltripropylammonium, ethyltributylammonium, diethyldipropylammonium, diethyldibutylammonium, triethylpropylammonium, triethylbutylammonium, etc., quaternary ammonium ions, such as (b)
Aliphatic ammonium ions such as triethylammonium, tripropylammonium, tributylammonium, methyldiethylammonium, methyldipropylammonium, methyldibutylammonium, dimethylethylammonium, dimethylpropylammonium, dimethylbutylammonium, ethyldipropylammonium, ethyldibutylammonium, Diethylpropylammonium, diethylbutylammonium, monomethylammonium, monoethylammonium, monopropylammonium, dimethylammonium, diethylammonium, dipropylammonium, dibutylammonium, methylethylammonium, etc., and (c)
An example is ammonium ion (NH'').

Specifically, the ammonium ion represented by the formula (II) includes (a) an alicyclic ammonium ion, such as N,
N-dimethylpyrrolidinium, N+N-dimethylpiperidinium, N-methyl-N-ethylpyrrolidinium, N
-Methyl-N-ethylpiperidinium, N,N-tetramethylenepyrrolidinium, N,N-pentamethylenepiperidinium, N-methylpiperidinium, N-methylpyrrolidinium, etc., (b) Nitrogen-containing Aromatic ammonium ions such as N-ethylpyridinium%N+N-dimethylimidazolium, pyridinium, N-methylimidazolium, etc. can be exemplified.

Similarly, quaternary phosphonium ions as cationic components include (a) aliphatic four-ball phosphonium ions, such as tetramethylphosphonium, tetraethylphosphonium, tetrapropylphosphonium, tetrabutylphosphonium, methyltriethylphosphonium, methyltripropylphosphonium, methyltributylphosphonium; Dimethyldiethylphosphonium, dimethyldipropylphosphonium, dimethyldibutylphosphonium, trimethylethylphosphonium, trimethylpropylphosphonium, trimethylbutylphosphonium, ethyltripropylphosphonium, ethyltributylphosphonium, diethyldipropylphosphonium, diethyldibutylphosphonium, triethylpropylphosphonium, triethylbutylphosphonium , propyltributylphosphonium, dipropyldibutylphosphonium, tripropylbutylphosphonium, etc. (b) Alicyclic quaternary phosphonium ions, such as 1.1-dimethylphosphoranium, 1-methyl-
1-ethylphosphoranium, 1,1-diethylphosphoranium, 1,1-diethylphosphoranium, 1-methyl-1-ethylpiperidinium, 1.1-diethylphosphoranium, 1.1-benta Examples include methylenephosphorinium.

On the other hand, as the anion component of the solute, a conjugate base of an acid selected from the following five groups is preferably used.

(1) Carboxylic acids and phenols (2) Boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, silicic acid and their derivatives (3) Picric acid and sulfonic acid (4) Nitric acid, sulfuric acid, sulfite , thiocyanic acid and their derivatives (5) Anion which is a conjugate base of an acid selected from the group of strong acids (1) and (2) containing a halogen atom is a good film-forming anion, and it is used. The solid electrolyte membrane of the present invention can be used not only for low voltage capacitors but also for medium and high voltage capacitors.

Those selected from groups (3), (4), and (5) also have the ability to form an oxide film, but they are highly acidic and easily corrode the oxide film, so solid electrolyte membranes are used in low-voltage capacitors of 100V or less. Only available. In particular, anions selected from group (5) liberate halide ions that are unfavorable to aluminum;
Can only be used with low voltage capacitors below 0V. Depending on the purpose of the capacitor used in this way, the above (1)
) to (5), a suitable one can be selected and used as appropriate.

The carboxylic acid of group (1) has a total carbon number of 1 to
30, preferably 2 to 20, aliphatic and aromatic 1
Preferred are monocarboxylic or polyhydric carboxylic acids.

Specifically, (a) aliphatic monocarboxylic acids, such as formic acid, acetic acid, propionic acid, butyric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, uralic acid, vaccenic acid, and gadoleic acid. , methacrylic acid, 3-methylcrotonic acid, tiglic acid, methylpentenoic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, etc., (b) Aliphatic dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid , pimelic acid, superric acid, azelaic acid, sebacic acid, undecanoic acid, dodecanoic acid, tridecanoic acid, tetradecandioic acid, pentadecanedioic acid, hexadecanedioic acid,
Heptadecanniic acid, octadecanniic acid, nonadecannic acid, eicosanniic acid, methylmalonic acid, ethylmalonic acid,
Propylmalonic acid, butylmalonic acid, pentylmalonic acid, hexylmalonic acid, dimethylmalonic acid, methylethylmalonic acid, diethylmalonic acid, methylpropylmalonic acid, methylbutylmalonic acid, ethylpropylmalonic acid, dipropylmalonic acid, ethyl Butylmalonic acid, propylbutylmalonic acid, dibutylmalonic acid, methylsuccinic acid, ethylsuccinic acid, 2゜2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid, 3-methyl -3-ethylglutaric acid, 3.3
-diethylglutaric acid, maleic acid, citraconic acid, 1
．． 5-octanedicarboxylic acid, 5.6-decanedicarboxylic acid, 1,7-decanedicarboxylic acid 1, 4,6-dimethyl-4-nonene-1,2-dicarboxylic acid, 4,6-dimethyl-1,2-nonanedicarboxylic acid acid, 1,7-dodecanedicarboxylic acid, 5-ethyl-1,10-decanedicarboxylic acid, 6-methyl-6-dodecene-1,12-dicarboxylic acid, 6-methyl-1,12-dodecanedicarboxylic acid, 6 -ethylene-1,12-dodecanedicarboxylic acid, 6
-ethyl-1,12-dodecanedicarboxylic acid, 7-methyl-7-tetradecene-1,14-dicarboxylic acid, 7-
Methyl-1,14-tetradecanedicarboxylic acid, 3-hexyl-4-decene-1゜2-dicarboxylic acid, 3-hexyl-1,2-decanedicarboxylic acid, 6-nitylene-9
-Hexadecene-1,16-dicarboxylic acid, 6-nityl-1゜16-hexadecanedicarboxylic acid, 6-phenyl-1,12-dodecanedicarboxylic acid, 7,12-dimethyl-7,11-octadecadiene-1゜18-dicarboxylic acid, 7,12-dimethyl-1°18-octadecanedicarboxylic acid, 6,8-diphenyl-1,14-tetradecanedicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid , 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 4-cyclohexene-1,2-dicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, etc., (iii) aromatic monocarboxylic acid (o , m.

p-including each isomer), such as benzoic acid, toluic acid, ethylbenzoic acid, propylbenzoic acid, isopropylbenzoic acid, butylbenzoic acid, isobutylbenzoic acid, nibutylbenzoic acid, tertiary-butylbenzoic acid, hydroxybenzoic acid , anisic acid, ethoxybenzoic acid, propoxybenzoic acid, isopropoxybenzoic acid, butoxybenzoic acid, isobutoxybenzoic acid, sec-butoxybenzoic acid, tertiary-butoxybenzoic acid, aminobenzoic acid, N-methylaminobenzoic acid, N- Ethylaminobenzoic acid, N-propylaminobenzoic acid, N-isopropylaminobenzoic acid, N-butylaminobenzoic acid, N-isobutylaminobenzoic acid, N-sec-butylaminobenzoic acid, N-tert-butylaminobenzoic acid , N,N-dimethylaminobenzoic acid, N,N-diethylaminobenzoic acid, nitrobenzoic acid, resorcinic acid, etc.
(d) Aromatic polycarboxylic acids, such as phthalic acid, isophthalic acid, terephthalic acid, 3-nitrophthalic acid, 4-nitrophthalic acid, trimellitic acid, hemimellitic acid, trimesic acid, pyromellitic acid, etc. I can do it.

Specifically, the phenols include phenol, catechol, resorcinol, hydroquinone, phloroglucinol, pyroganol, 1. 2.4-trihydroxybenzene, 0-nitrophenol, m-nitrophenol, p-nitrophenol, 2,4-dinitrophenol, 2. Examples include 5-dinitrophenol, 2,6-dinitrophenol, 3,4-dinitrophenol, 4-nitrocatechol and 2-nitroresorcinol.

Those belonging to group (2) include boric acid, the following general formula (
Boric acid derivatives represented by V), phosphoric acid, and the following general formula (V
Phosphoric acid ester represented by I), phosphorous acid, phosphorous acid derivative represented by the following general formula (■), hypophosphorous acid, hypophosphorous acid derivative represented by the following general formula (■), carbonic acid, the following These are carbonic acid monoester represented by general formula (IX) and silicic acid.

C formula (V) ~ (in DO, R6-R9 each have 1 to 1 carbon number
10 alkyl group (preferably about 1 to 6 carbon atoms) or aryl group (preferably phenyl or lower alkyl-substituted phenyl). However, one of R or R8 may be a hydrogen atom. ] Specific examples of the boric acid derivative represented by formula (V) include methylboric acid, ethylboric acid, phenylboric acid, and the like.

Specific examples of the phosphoric acid ester represented by formula (Vl) include monomethyl phosphoric acid, dimethyl phosphoric acid, phenyl phosphoric acid, and the like.

Specific examples of the phosphorous acid derivative represented by formula (■) include phosphorous acid monomethyl ester, methylphosphonic acid, and methylphosphonic acid methyl ester.

Specific examples of the hypophosphorous acid derivative represented by formula (■) include methylphosphinic acid, dimethylphosphinic acid, phenylphosphinic acid, and the like.

Specific examples of the carbonate monoester represented by formula (IX) include carbonate monomethyl ester, carbonate monophenyl ester, and the like.

Belonging to group (3) are picric acid and sulfonic acid. Sulfonic acid has a total carbon number of 1 to 30
, preferably 1 to 20, aliphatic and aromatic mono- or polyhydric sulfonic acids.

Specifically, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, hexanesulfonic acid, heptanesulfonic acid, octanesulfonic acid, nonanesulfonic acid, decanesulfonic acid, vinylsulfonic acid, allyl Sulfonic acid, 1,2-ethanedisulfonic acid, 1,4-butanedisulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 1-ethylbenzenesulfonic acid, xylene sulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, nitrobenzenesulfonic acid , 2,4-dinitrobenzenesulfonic acid, picrylsulfonic acid, pyridine-3-sulfonic acid, m-benzenesulfonic acid, toluene-3,4-disulfonic acid, and the like.

Those belonging to group (4) are nitric acid, sulfuric acid, sulfuric acid monoester represented by the following general formula (X), sulfurous acid, sulfite monoester represented by the following general formula (xl), and thiocyanic acid.

[Formula (X) to (XI), R10 has 1 to 10 carbon atoms
represents an alkyl group (preferably one or more carbon atoms) or an aryl group. ] Those belonging to group (5) are acids that exhibit strong acidity because they contain halogen atoms with high electronegativity.

Specifically, HBF HPF6, HA s F 6
．． 4ゝHSbF CF So H, CF3COH.

6ゝ33C4F9S03H1C4F9COOH1HCI04 etc. can be exemplified.

Organic Solvent (Component (d))> The component (d) used in the composition of the present invention is an organic solvent. This organic solvent is for dissolving the solute of component (c) described above to form an ion-conductive electrolyte.

Examples of such organic solvents include (a) amide solvents such as N-methylformamide, N-ethylformamide, N,N'-dimethylformamide, N,
N-diethylformamide, N-methylacetamide,
N-ethylacetamide, N,N-dimethylacetamide, N,N-diethylacetamide, N-methylpyrrolidinone, etc., (b) carbamate solvents, such as N-methylo, xazolidinone, etc., (c) urea solvents, such as N,N' -dimethylimidazolidinone, etc., (di)lactone solvents, such as γ-butyrolactone, γ-valerolactone, etc., (e)carbonate solvents, such as ethylene carbonate, propylene carbonate, butylene carbonate, etc., (h)alcohol solvents, such as ethylene glycol , methyl cellosolve, etc., (t)sulfolane solvents, such as sulfolane, 3-methylsulfolane, etc.
(h) Nitrile solvents, such as acetonitrile, 3-methoxypropionitrile, (h) phosphate solvents,
For example, trimethyl phosphate, etc., (nu)ether solvents such as 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane, etc., and (li)hydrocarbon solvents such as hexane, benzene, toluene, etc. alone or in combination. I can give an example. Also,
A mixed solvent of the above organic solvent and water can also be used.

Among these, electrolytic solutions containing γ-butyrolactone, ethylene glycol, etc. as main solvents are preferred because they have a wide usable temperature range, low toxicity, and strong halogen resistance.

Reinforcing material> The porous membrane and/or nonwoven fabric used in combination with the matrix polymer of component (a) to improve the mechanical and physical strength of the solid electrolyte membrane of the present invention include polyethylene, polypropylene, Microporous films and/or nonwoven fabrics made of resins such as polytetrafluoroethylene, polyester, and polyacrylonitrile, natural papers for electrolytic capacitors made of cellulose fibers such as kraft paper and Manila paper, and nonwoven fabrics made of cellulose fibers. can be used. Among these, it is preferable to use a nonwoven fabric with high porosity in order to have excellent mechanical strength, high heat resistance, and to reduce internal resistance while being thinner.

Blending ratio> In the present invention, in order to obtain a solid electrolyte membrane that has high conductivity, is thermally and electrochemically stable, is soft and flexible, and has excellent safety, (a The polymer used in component ) is 2% to 35% by weight, preferably 2.5% by weight, based on the total amount of components (a) to (d)
It is preferable to adjust the proportion to include 25% by weight.

In addition, when the component polymer (a) is a copolymer of monofunctional and/or polyfunctional monomers, monofunctional and/or polyfunctional monomers may be added to the polymerizable monomers. It is preferable to contain it in a range of 1 to 10% by weight, preferably 3 to 6% by weight based on the total amount, for the purpose of obtaining a matrix polymer with high conductivity, softness, and excellent flexibility.

In addition, the polymer compound used for component (b) has a
It is preferable to adjust the proportion to contain 0.1 to 50% by weight, preferably 1 to 40% by weight.

In addition, the content of the solute of component (c) is the solid electrolyte ((a
(based on the total amount of components (a) to (d)), the concentration is below the saturation concentration for boat fishing, preferably 0.1 to 30% by weight. More preferably, the proportion is adjusted to 5 to 25% by weight for low voltage capacitors, and 1 to 20% by weight for medium and high voltage capacitors.

Manufacture of Solid Electrolyte Membrane> The solid electrolyte membrane of the present invention can be manufactured by any suitable method, including the use of a reinforcing material if necessary. Specifically, for example, a matrix polymer (
Synthesize the film-like material of a), and add a conductive polymer (
b) A solid electrolyte membrane is formed by impregnating the forming monomer and an oxidizing agent, carrying out chemical oxidative polymerization to contain and integrate a conductive polymer compound, and adding and mixing a solute and an organic solvent into the membrane-like material. There is a way to get it.

That is, a polymerizable vinyl monomer (precursor of component (a)) is dissolved in an organic solvent (component (d)), and a radical polymerization initiator such as peroxide or an azo compound or light (UV ) A homogeneous solution containing a polymerization initiator is formed into a film by a casting method or a casting method,
Or, if necessary, cast on a reinforcing material such as non-woven fabric, and
Polymerization is performed under heating at 90° C. or by irradiation with light (UV) to synthesize a film-like matrix polymer. Next, a film-like material of the matrix polymer is added to a conductive polymer monomer (precursor of component (b)) solution (monomer concentration 0.01 to 2).
．． About 0iol/liter, preferably 0.01~
1.0 intestines/liter) for 5 minutes to 24 hours. Next, the oxidizing agent solution (oxidizing agent concentration 0.01-3
．． About 0 sol/liter, preferably 0.1 to 2
．． 0 sol/liter) at a temperature of about -10 to 60° C. for about 1 minute to about 6 hours to carry out chemical oxidative polymerization in the matrix polymer to form a conductive polymer compound. In addition, at this time, there is no problem even if the immersion procedure of the monomer and the oxidizing agent is reversed. Next, a solid electrolyte membrane can be manufactured by immersing the conductive polymer compound-containing membrane in an organic solvent in which a solute (component (C)) is dissolved.

Furthermore, the film-like material containing the conductive polymer compound described above is placed between an anode foil and a cathode foil having a dielectric oxide film, and is wound to form an electrolytic capacitor element. A solid electrolyte membrane can also be formed integrally with a capacitor element by immersing or impregnating it in an organic solvent.

Another manufacturing method is to polymerize a polymerizable vinyl monomer in the presence of a solute and an organic solvent to synthesize a membrane-like solid electrolyte, and then add a conductive polymer monomer and an oxidizing agent to the membrane. A solid electrolyte membrane containing a conductive polymer compound can also be produced by impregnation and chemical oxidative polymerization.

Specifically, a polymerizable vinyl monomer is added and mixed into a homogeneous solution in which a solute is dissolved in an organic solvent, and an ordinary radical polymerization initiator or a photo (UV) polymerization initiator is further added to the homogeneous solution. The material is formed into a film-like material by a casting method or a casting method, or if necessary, it is cast onto a reinforcing material such as nonwoven fabric, and heated at 60 to 90°C or exposed to light (UV
) Polymerize by irradiation to synthesize a solid electrolyte membrane.

Next, the film-like material is sequentially immersed in a monomer solution of a conductive polymer and an oxidizing agent solution, and chemical oxidative polymerization is performed in the film to form an integrated solid electrolyte membrane containing a conductive polymer compound. Obtainable.

Note that the component ratio in the solid electrolyte was determined by the method shown below.

1> Polymerizable vinyl hexamer is polymerized in the presence of an organic solvent to obtain a matrix polymer film. This 2
Cut into 5×25 pieces, vacuum dry at 70° C. for 24 hours, and measure the weight of the membrane. Hereinafter, this weight will be referred to as "dry matrix polymer membrane weight (A)."

2) The above dried film (A) is immersed in a monomer solution of a conductive polymer compound/or an oxidizing agent solution for 1 hour, and then immersed in an oxidizing agent solution/or a monomer solution to remove the conductive polymer. An integrated film containing the compound is obtained. After washing this membrane,
Vacuum dry at 70° C. for 24 hours and measure the weight of the film. Hereinafter, this weight will be referred to as "dry conductive polymer compound-containing layer weight 1 (
B) It's called J.

3) The dried membrane (B) is immersed for 4 hours in a homogeneous electrolytic solution in which a solute is dissolved in an organic solvent to obtain a solid electrolyte membrane of the present invention. Wipe off the liquid adhering to the surface with a filter paper and measure the weight of the membrane. Hereinafter, this weight will be referred to as "solid electrolyte membrane weight (C)"
That's what it means.

4) The film-like material (C) is vacuum-dried at 70° C. for 24 hours and the weight of the film is measured. Hereinafter, this weight will be referred to as "dry solid electrolyte membrane weight (D)".

(% by weight) (C) (From the above, AD in the above formula is as follows.

A- (a) component B- (a) + (b) component C- (a) to (d) component D- (a) + (b) 10 (c) component) [Implementation
Examples] The following examples are provided to further specifically explain the present invention. These examples do not limit the scope of the invention.

Measuring method of conductivity The conductivity was measured by the following method.

After measuring the thickness of the solid electrolyte membrane of the sample with a micrometer, circular stainless steel electrodes with a diameter of 10+U were closely attached to both sides of the solid electrolyte membrane, and the whole was placed in a nitrogen atmosphere with a temperature controlled at 25°C. A multi-φ frequency LCR meter (manufactured by Yokogawa Hewlett-Packard, 4274A) was installed inside the chamber.

4275A), an alternating current of 102 to 106 H2 was applied, and the conductivity was measured by the complex impedance method.

Example 1 To 10 g of γ-butyrolactone solvent (GBL), 10 g of 2-hydroxyethyl methacrylate (HEMA) as a polymerizable monomer was added and mixed, and as a polymerization initiator, "Barbutyl OJ (PBO1 manufactured by Nippon Yuko) 20" was added. was added to make a homogeneous solution.

A portion of the above prepared solution was prepared using a polyester film and a glass plate.
The matrix polymer (a) was injected into a cell having a space of A film-like substance was obtained.

Next, the above film-like material was cut into a size of 25×25-■, and placed in a 1 OL/liter aqueous sulfuric acid solution containing 0.1 L of aniline hydrochloride as a monomer of the conductive compound (b) for 1 hour. After soaking, ammonium persulfate 1s
The sample was immersed in OL/L for 10 minutes under water cooling to cause oxidative polymerization of aniline, thereby obtaining a film containing an integrated conductive polymer compound. After washing this membrane with pure water, it was heated at 70℃ for 24 hours.
Vacuum dried for hours.

Next, the dried film was mixed with GB in which monotetramethylammonium phthalate (25% by weight) was dissolved as the solute (c).
L (d) A solid electrolyte membrane was obtained by immersing it in an electrolytic solution for 4 hours. The characteristics of the obtained solid electrolyte membrane, such as conductivity, appearance, and properties, were measured and the results are shown in Table 1.

Example 2 In Example 1, 6 g of ethoxyethyl methacrylate (EEMA) and 4 g of 2-hydroxyethyl methacrylate (HEMA) were used as the polymerizable vinyl monomer for the matrix polymer (a), and as the conductive polymer compound (b).
Aniline hydrochloride as a monomer for 0. 2sol/liter aqueous solution was used as a reinforcing material for the matrix polymer, and a long fiber cellulose nonwoven fabric with a thickness of 50 μm was installed in the cell to prepare a matrix polymer membrane with the nonwoven fabric integrated. A solid electrolyte membrane was obtained in the same manner as in 1. The properties of the obtained film were as shown in Table 1.

Example 3 4 g of ethoxyethyl methacrylate (EEMA) and 6&- of 2-hydroxyethyl methacrylate (HEMA) were used as polymerizable vinyl monomers, and 0.0 g of aniline hydrochloride was used as a monomer for a conductive polymer compound. A solid electrolyte membrane was obtained in the same manner as in Example 2 except that 3io+/liter aqueous solution was used. The properties of the obtained membrane were as shown in Table 1.

Example 4 A solid electrolyte membrane was obtained in the same manner as in Example 3, except that 10 g of glycerol methacrylate (GLMA) was used as the polymerizable monomer and monotriethylmethylammonium phthalate (25% by weight) was used as the solute.

The properties of the obtained membrane were as shown in Table 1.

Example 5 A solid electrolyte membrane was obtained in the same manner as in Example 3 except that monotriethylmethylammonium maleate (25% by weight) was used as the solute. The properties of the obtained membrane were as shown in Table 1.

Example 6 In Example 3, virol 0.0. A solid electrolyte membrane was obtained in the same manner as in Example 3, except that an aqueous solution of p-toluenesulfonic acid 0.1 o1/liter containing 3io+/liter was prepared and used. The properties of the obtained membrane were as shown in Table 2.

Example 7 Hydroxypropyl methacrylate (HPMA) as polymerizable vinyl methacrylate (HPMA) 10. A solid electrolyte membrane was obtained in the same manner as in Example 6 except that triethylmethylammonium benzoate (25% by weight) was used as the solute. The properties of the obtained membrane were as shown in Table 2.

Example 8 6 g of 2-hydroxyethyl acrylate (HEA) and methoxypolyethylene glycol methacrylate (MPEGM CCn-23) as polymerizable vinyl monomers
)4 as a monomer for conductive polymer compounds.
．． 0.5io+/liter. A solid electrolyte membrane was obtained in the same manner as in Example 2, except that a 5io+/liter sulfuric acid aqueous solution and monotetraethylphosphonium phthalate (25% by weight) were used as the solute. The properties of the obtained membrane were as shown in Table 2.

Example 9 Using 4.3 g of 2-hydroxyethyl methacrylate (HEMA) as a polymerizable monomer and 12 μg of "Perbutyl O" (PBO) as a polymerization initiator,
Ammonium azelate (10% by weight) as electrolyte
A solid electrolyte membrane was obtained in the same manner as in Example 6 except that an ethylene glycol (EG) solvent in which EG was dissolved was used. The properties of the obtained membrane were as shown in Table 2.

Example 10 In Example 2, aniline hydrochloride was used as the monomer of the conductive compound. A 5 sol/liter aqueous solution was mixed with triethylammonium maleate (25% by weight) as a solute.
) were used, respectively, and a solid electrolyte membrane was obtained in the same manner as in Example 2. The properties of the obtained membrane were as shown in Table 2.

Example 11 Example except that hydroxypropyl methacrylate (HPMA) was used as the polymerizable vinyl monomer and an ethylene glycol/water (80/20) mixed solvent in which ammonium adipate (10% by weight) was dissolved was used as the electrolyte. A solid electrolyte membrane was obtained in the same manner as in Example 10. The properties of the obtained membrane were as shown in Table 2.

Claims (4)

[Claims] 1. (a) A matrix polymer consisting of a polymer of polymerizable vinyl monomers and (b) At least one monomer selected from the following general formula (III) and/or (IV) obtained by chemical oxidation polymerization. and (c) a salt having an ammonium ion or quaternary phosphonium ion represented by the following general formula (I) or/and (II) as a cation component and a conjugate base of an acid as an anion component. (d) an organic solvent; and (d) an organic solvent. ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼(II) (In formulas (I) and (II), R^1, R^2, R^3
and R^4 may be the same or different and represent hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms, and R^5 is a nitrogen atom in formula (II). represents a group having 3 to 10 carbon atoms that forms an aliphatic heterocycle or aromatic heterocycle by bonding with. ) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (III) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (IV) (In formula (III) and formula (IV), R^6 to R^13 are the same. may be different, hydrogen, carbon number 1-4
represents an alkyl group or an aryl group having 6 to 10 carbon atoms (at least one of R^6 and R^7 is hydrogen), and R^1^2 and R^1^3 each have a cyclic structure. may be taken. Also, X is oxygen, sulfur or NR^1
^4, N is nitrogen, and R^1^4 represents hydrogen, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 10 carbon atoms. ) 2. The polymerizable vinyl monomer is at least one type of (meth)acrylic ester selected from alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, glycerol (meth)acrylate, and alkylene glycol (meth)acrylate,
The solid electrolyte membrane according to claim 1. 3. Anionic components of solutes include carboxylic acid, phenols, boric acid, phosphoric acid, phosphorous acid, hypophosphorous acid, carbonic acid, silicic acid, picric acid, sulfonic acid, nitric acid, sulfuric acid, sulfite, thiocyanic acid, and halogen atoms. The solid electrolyte membrane according to claim 1 or 2, wherein the solid electrolyte membrane is a conjugate base of at least one acid selected from strong acids containing strong acids and derivatives thereof. 4. The solid electrolyte membrane according to claim 1, 2 or 3, which is integrated with a porous membrane or/and a nonwoven fabric.