JP2003249421A - Polymer electrolytic complex for electrolytic-capacitor driving, electrolytic capacitor using the same, and manufacturing method of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer electrolyte for an electrolytic-capacitor driving having high ion conductivity in room temperature, superior heat-resistance, characteristics hard to react with electrode foil like aluminum foil, and superior formability in mold and a long life, and to provide an electrolytic capacitor with the electrolyte. <P>SOLUTION: The polymer electrolytic complex comprises acrylic polymer containing copolymer of acrylic derivative and electrolyte. The electrolyte is composed of polar solvent, and one or more of solute of inorganic acid, organic acid and salt thereof. The copolymer is polymer made of a first monomer out of mono-functional monomer group as an acrylic derivative having a hydroxyl group at an end and one polymeric unsaturated double bond, and a second monomer out of polymeric multi-functional monomer group having a plurality of unsaturated double bonds. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer electrolyte composite for driving an electrolytic capacitor, an electrolytic capacitor using the same, and a method for producing the same, and the electrolyte is an ion conductive type.

[0002]

2. Description of the Related Art An electrolytic capacitor has a structure in which an electrolyte is sandwiched between a cathode and an anode having a dielectric oxide film formed by chemical conversion. There are two types of electrolytes, liquid or solid and ionic conductive, and solid and electronically conductive. The liquid and ion conductive type uses an electrolytic solution as an electrolyte. In the case of electrolytic solution, a high repair voltage can be applied between the positive and negative electrodes even if a considerably deep defect occurs in the dielectric oxide film, that is, a high formation voltage for the purpose of reforming the oxide film is applied. Therefore, the defective portion can be easily repaired. The fact that a high restoration voltage can be applied means that no spark is generated even if a high voltage is applied, that is, the spark voltage is high.

However, in order to hold the electrolytic solution between the positive and negative electrodes, a separator that is sufficiently filled with the electrolytic solution and sufficiently separates the anode and the cathode is required. It is necessary to use paper or non-woven fabric having a sufficiently large basis weight, that is, the product of density and thickness, as a separator material that satisfies the condition. The electrolyte itself has a relatively high ionic conductivity, and the resistance (ESR: Equivalent Series Resistance) of the electrolyte itself is relatively small, but the separator / electrolyte composite has a large resistance due to the large basis weight of the separator. growing.
That is, of the resistance loss as the electrolytic capacitor, the resistance loss due to the electrolytic solution itself can be made relatively small, but the resistance loss as a whole becomes large because of the separator. Further, since a liquid is used in the first place, there are disadvantages in terms of liquid leakage, mounting on a device, workability, and the like.

Therefore, solidification of the electrolytic solution has been conventionally studied. The type using a solid electrolyte has no disadvantages because a liquid is used. Among them, one example of a solid and electronically conductive type is one in which, for example, polypyrrole is used as an electrolyte and a porous resin such as polypropylene or polyethylene is used as a separator, instead of the above-mentioned electrolytic solution. Since electron conduction is used, its resistance is small and the resistance loss as an electrolytic capacitor is small. However, in the case of this solid electron conductive type, even if the dielectric oxide film has a defect, it is difficult to sufficiently repair it by applying a high repair voltage. In the case of this type, a spark is generated even when a relatively low repair voltage is applied. That is,
It has almost no oxide film repair function.

On the other hand, solid and ion conductive types include inorganic type and polymer type. The inorganic type has the feature of high ionic conductivity, but has the disadvantages of being heavy, lacking in flexibility, and having poor moldability.
The solid polymer type, that is, the ion conductive polymer, has much lower ionic conductivity than the inorganic electrolyte, but is lightweight and excellent in mechanical properties such as flexibility and moldability. So it is drawing attention. A conventionally proposed ion-conducting polymer is, for example, a complex of polyethylene oxide (PEO) and a lithium salt (ionic conductivity: 1
At 00 ° C to ^{-10 -4} S / cm) {polymer, 14,586 (197
3)}, a diisocyanate cross-linked polymer of triol-type polyethylene oxide-metal salt complex (ionic conductivity:
10 ⁻⁵ S / cm at 30 ° C. {JP-A-62-48716}, counterion-fixed ion-conducting polymer of polymethacrylic acid oligooxyethylene-alkali metal salt of methacrylic acid (ionic conductivity: (10 ^-7 S / cm at room temperature)
{Polymer Re-prints Japan, 35,583 (1986)}, a mixture of monofunctional and polyfunctional acryloyl-modified polyalkylene oxides and alkali metal and / or alkaline earth metal salts (ionic conductivity: 10 ^-3 S / at 25 ° C) cm) {JP-A-8-295711} and the like are reported. Further, as an example of the ion conductive polymer actually applied to the electrolytic capacitor, a solvent and an electrolyte salt are added to a heat-modified polymer and / or a cellulose derivative, and the solvent has a molecular weight of 20.
An ion-conducting polymer (ionic conductivity: 1 at room temperature, containing 0 or less polyhydric alcohol compound, wherein the heat-modified polymer contains egg white protein and / or β-1,3-glucan.
0 ^-3 S / cm) {Hei 5-55088 Publication} have been reported.

However, some of these ion-conductive polymers have low ionic conductivity at room temperature, so that when applied to an electrolytic capacitor, resistance loss is large and sufficient characteristics cannot be obtained. And in another type,
Even if the polymer has the same ionic conductivity as the electrolytic solution, the heat resistance of the polymer may be low. Further, since the metal salt is used, there are disadvantages that a short circuit occurs in a high temperature environment and sufficient characteristics cannot be obtained.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned problems of the prior art, and has high ionic conductivity at room temperature and high heat resistance, and an electrode such as aluminum when an electrolytic capacitor is constructed. It is an object of the present invention to provide a polymer electrolyte composite for driving an electrolytic capacitor, which does not react with the foil and is excellent in moldability and long life. Another object of the present invention is to provide an electrolytic capacitor using the same polymer electrolyte composite.

[0008]

The polymer electrolyte composite for driving an electrolytic capacitor of the present invention is a composite comprising an electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative. The electrolyte comprises a polar solvent and at least one solute of an inorganic acid or an organic acid or a salt thereof. The copolymer is an acrylic derivative having a hydroxyl group at a terminal and at least one of a monofunctional monomer group having one polymerizable unsaturated double bond, and a first monomer which is polymerized with the acrylic derivative. It is a polymer with a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of unsaturated unsaturated double bonds. Here, the hydroxyl group at the terminal of the acrylic derivative includes not only a hydroxyl group in a narrow sense, but also a terminal hydroxyl group such as a carboxyl group, a phosphoric acid group, and a dihydroxyl group.

It is preferable that the acrylic derivative copolymer constitutes a copolymer matrix and the electrolyte is incorporated in the copolymer matrix. The acrylic derivative copolymer preferably contains a polyoxyalkylene group. Further, it is preferable that the solute does not contain a metal salt as a cation.
In particular, the solute preferably comprises at least one salt selected from the group consisting of ammonium salts, amine salts and amidine salts of the inorganic acids and the organic acids.

The monofunctional monomer group is represented by the formula (1) described below.
To the acrylic derivative represented by the formula (4), and the polyfunctional monomer group preferably comprises the acrylic derivative represented by the formulas (5) to (16) described below. Furthermore, the weight ratio of the first monomer to the second monomer is preferably in the range of 100: 3 to 3: 100. More preferably, the range is 100: 10 to 10: 100. Further, the content of the solute and the acrylic derivative in the total weight of the copolymer is 5 to 50 w.
It is preferably in the range of t%.

The electrolytic capacitor of the present invention comprises an anode foil, a cathode foil, and a separator sandwiched between the anode foil and the cathode foil and containing a polymer electrolyte composite for driving an electrolytic capacitor. The polymer electrolyte composite for driving an electrolytic capacitor comprises an electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative, and the electrolyte is a polar solvent and an inorganic acid or an organic acid or a salt thereof. At least one of a monofunctional monomer group having a hydroxyl group at a terminal and having one polymerizable unsaturated double bond, which is an acrylic derivative. And a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of polymerizable unsaturated double bonds, which is an acrylic derivative. It has been. The basis weight of the separator of the electrolytic capacitor is preferably in the range of 0.01 to 55 g / m ² . Further, the material of the separator is preferably a porous resin film or a non-woven fabric. Further, the porosity of the separator is 10 to 90.
It is preferably in the range of%.

The method for producing an electrolytic capacitor of the present invention comprises a step of forming a capacitor precursor comprising an anode foil, a cathode foil and a separator sandwiched therebetween, and a polymer electrolyte composite stock solution is added to the capacitor precursor. The method includes a production step of producing an electrolytic capacitor raw element by impregnation, and a curing step of curing the polymer electrolyte complex undiluted solution in the electrolytic capacitor original element, wherein the polymer electrolyte complex undiluted solution is a polar solvent. A group of monofunctional monomers having an electrolyte solution containing a solute composed of at least one of an inorganic acid or an organic acid or a salt thereof, and an acrylic derivative having a hydroxyl group at the terminal and one polymerizable unsaturated double bond At least one of a polyfunctional monomer group having a plurality of unsaturated double bonds polymerizable with an acrylic derivative Is a mixed solution containing a second monomer consisting of two, wherein the curing step copolymerizes the first monomer and the second monomer to form a copolymer matrix, and the electrolyte solution is substantially gelled. The electrolytic matrix driving electrolyte is incorporated into the copolymer matrix.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to the drawings and more specifically with reference to Examples, but the present invention is limited to the contents described above. Not a thing. FIG. 1 is a perspective view showing main components of an electrolytic capacitor according to an embodiment of the present invention. As shown in FIG. 1, an anode foil 1 made of, for example, aluminum as an anode and a cathode foil 2 also made of, for example, aluminum as a cathode sandwich a separator 3a, 3b containing a polymer electrolyte composite described later. The basic structure of the capacitor element is that it is wound so as to face each other. Lead-out leads 4a and 4b are connected to the anode foil 1 and the cathode foil 2, respectively.

A method of manufacturing this capacitor element will be specifically described. First, the capacitor precursor is formed by sandwiching the separators 3a and 3b between the anode foil 1 and the cathode foil 2 and winding them so as to face each other. The capacitor precursor is impregnated with a polymer electrolyte composite stock solution containing an electrolyte solution and a liquid polymer material described below to prepare an electrolytic capacitor stock element. After that, although not shown, the original electrolytic capacitor element is enclosed in a case made of aluminum, for example, and then the case is sealed with a sealing material such as rubber or phenol resin. Before and after the sealing step, the stock solution for polymer electrolyte complex is cured by heating or the like. Through these steps, the electrolytic capacitor according to the embodiment of the present invention is manufactured. Now, the polymer electrolyte composite stock solution for driving the electrolytic capacitor is a mixed solution of an electrolyte solution and a liquid polymer material described later. By the curing step, the polymer material is cured to form a polymer matrix, and the electrolyte solution becomes a gel electrolyte and is taken into the polymer matrix.

Now, the embodiment of the polymer-electrolyte composite, that is, the composite of a polymer and an electrolyte, which is the greatest point of the present invention, will be described in detail below. The polymer electrolyte composite for driving an electrolytic capacitor of the present invention is a composite composed of an electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative. In the present invention, the following expression is an acrylic _{derivative: H 2 C = C (R} ) C (= O) - ( wherein, R is H or an alkyl group having 1 to 5 carbon atoms) a group represented by It is a derivative of the compound having.

The electrolyte comprises a polar solvent and at least one solute of an inorganic acid or an organic acid or a salt thereof. The copolymer is an acrylic derivative having a hydroxyl group at a terminal and at least one of a monofunctional monomer group having one polymerizable unsaturated double bond, and a first monomer which is polymerized with the acrylic derivative. It is a polymer with a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of unsaturated unsaturated double bonds.

The monofunctional monomer group is an acrylic derivative group represented by the following formulas (1) to (4),
Examples of the polyfunctional monomer group include formulas (5) to (16)
It is suitable to use the acrylic derivative group represented by.

[0018]

[Chemical 17]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms, AO ¹ is an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 200.

[0020]

[Chemical 18]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 200.

[0022]

[Chemical 19]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 200.

[0024]

[Chemical 20]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 200.

[0026]

[Chemical 21]

R ³ is H or an alkyl group having 1 to 5 carbon atoms, AO ² is an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 200.

[0028]

[Chemical formula 22]

R ³ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 200.

[0030]

[Chemical formula 23]

R ¹ and R ² are H or an alkyl group having 1 to 5 carbon atoms, and they may be the same or different.

[0032]

[Chemical formula 24]

R ¹ and R ² are H or an alkyl group having 1 to 5 carbon atoms, and they may be the same or different.
l, m and n are 1 to 200.

[0034]

[Chemical 25]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms.

[0036]

[Chemical formula 26]

R1 is H or an alkyl group having 1 to 5 carbon atoms.

[0038]

[Chemical 27]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms.

[0040]

[Chemical 28]

[0041]

[Chemical 29]

[0042]

[Chemical 30]

[0043]

[Chemical 31]

[0044]

[Chemical 32]

R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is a natural number of 1 to 9.

The monofunctional monomers of the formulas (1) to (4) have a hydroxyl group at the terminal and have a polymerizable unsaturated double bond of 1
I have one. Here, the expression "hydroxyl group" is used not only in a narrow sense of hydroxyl group but also in the meaning including carboxyl group, phosphoric acid group, dihydroxyl group and the like having a hydroxyl group at the terminal. Further, the polyfunctional monomers of formulas (5) to (16) have a plurality of polymerizable unsaturated double bonds.

The first monomer, ie, the monofunctional monomer, and the polyfunctional monomer, ie, the second monomer, are heated or irradiated with ultraviolet rays (UV) or electron beams (EB) to cause radical polymerization reaction. It can be aged, cross-linked and copolymerized to form a copolymer matrix. At the same time, an electrolyte comprising a solute of one or more of inorganic or organic acids or salts thereof and a polar solvent can be incorporated into the copolymer matrix. As a result, it is possible to obtain a material having a high ionic conductivity at room temperature. In addition, when the acrylic derivative of the polyfunctional monomer is a compound having a diacrylic acid ester, it becomes easy to form a three-dimensional cross-linking structure, and compared with the homopolymerization of only the acrylic acid ester of the monofunctional monomer, The skeleton of the polymer matrix can be maintained more stably. As a result, the electrolyte provided with the polar solvent in which one or more solutes of inorganic acids or organic acids or salts thereof are dissolved can be more stably retained in the copolymer matrix.

By using an acrylic acid ester having a hydrophilic group at the end of the molecule like the acrylic acid ester of the monofunctional monomer, the affinity with a solvent is improved, and the inorganic acid or It facilitates the incorporation of a polar solvent in which one or more solutes of organic acids or salts thereof are dissolved. Further, by having a crosslinked structure having a functional group such as an acrylic derivative of the polyfunctional monomer, or having a multichain type crosslinked structure, affinity with a solvent and crosslink density can be increased, and the content of the electrolyte can be increased. Can be improved. Further, by using a cross-linked acrylic derivative having a phosphoric acid group, the adsorption of the copolymer matrix on the anode foil and cathode foil of the electrolytic capacitor is promoted, and the driving electrolyte containing the acrylic derivative copolymer matrix is used. The adhesiveness can be enhanced and the contact resistance with the foil can be reduced. As a result, higher ionic conductivity can be realized, and since the copolymer matrix maintains the physical distance between electrodes, it exhibits excellent characteristics that it is difficult to cause a short circuit when applied to an electrolytic capacitor.

In the structures represented by the formulas (1) and (5), AO is an oxyalkylene group having 2 to 4 carbon atoms. As the oxyalkylene group having 2 to 4 carbon atoms, an oxyethylene group (hereinafter referred to as EO), an oxypropylene group (hereinafter referred to as PO), an oxybutylene group (hereinafter referred to as BO), an oxytetramethylene group ( Hereinafter, TMO) and the like can be used. The polyoxyalkylene group may be a homopolymer of one kind or a copolymer of two or more kinds of these oxyalkylene groups, as long as a matrix of polyoxyalkylene groups as a crosslinked product is formed. Among these, from the viewpoint of incorporating a larger amount of electrolytic solution components into the matrix, depending on the type of polar solvent or solute in the components of the electrolytic solution used, the affinity between the electrolytic solution components and the matrix is high. The oxyalkylene group to be polymerized may be selected so that The polyoxyalkylene group containing two or more kinds of oxyalkylene groups may be added in a block shape or randomly added, and is not particularly limited.

The state of the driving electrolyte containing a polar solvent in which at least one solute of an inorganic acid or an organic acid or a salt thereof is dissolved in a copolymerization matrix is basically substantially the same. It becomes a gel. Here, the meaning of "substantially gel-like" means that at least a considerable portion is in a gel state, and it is possible that a part thereof is in the state of a solid or a highly viscous liquid, etc., and the whole is completely The present invention is not limited to gelled ones.
That is, in the present embodiment, the substantially gel electrolyte is basically retained by the polymer, that is, the copolymer matrix. Therefore, the separator used when manufacturing the electrolytic capacitor does not need to have a function of directly holding an electrolyte such as an electrolytic solution that does not have a self-holding function. Therefore, the function required of the separator is basically the function of separating the anode and the cathode. In other words, the material of the separator does not have to be limited to the paper or non-woven fabric conventionally used for holding the electrolytic solution, but a material having a smaller basis weight, that is, a lower resistance can be used. Therefore, the polymer electrolyte composite-separator configuration of the present embodiment, considering the resistance of only the electrolyte, the electrolytic solution in the conventional electrolyte-separator configuration has a high ionic conductivity and low resistance, but the separator Considering this, it is possible to reduce the resistance as a whole. Furthermore, as compared with the case of a conventional solid electrolyte such as polypyrrole, since the electrolyte is substantially gel-like, a higher formation voltage is applied to repair the anodic oxide film than that of the conventional solid electrolyte. be able to.

As the polar solvent, ethylene glycol, propylene glycol, 1,4-butanediol,
Glycerin, water, polyoxyalkylene polyols,
Amides, alcohols, ethers, nitriles, furans, sulfolanes, carbonates, lactones,
One or two or more of imidazolidinones and pyrrolidones can be used in combination and used as a polar solvent. Specific examples of the solvents described above as a class are described below. Examples of the polyoxyalkylene polyols include polyethylene oxide having a molecular weight of 200 or less, polypropylene oxide, polyoxyethylene / oxypropylene glycol, and a combination of two or more thereof. As the amides, N-methylformamide,
There are N, N-dimethylformamide, N-methylacetamide, N-methylpyrrolidinone and the like.

Examples of alcohols include methanol and ethanol. As ethers, methylal,
There are 1,2-dimethoxytaene, 1-ethoxy-2-methoxyethane, 1,2-diethoxyethane and the like. Examples of nitriles include acetonitrile and 3-methoxypropionitrile. Examples of furans include 2,5-dimethoxytetrahydrofuran. Examples of the sulfolane include sulfolane, 3-methylsulfolane, 2,4-dimethylsulfolane and the like.

Examples of carbonates include propylene carbonate, ethylene carbonate, diethyl carbonate, styrene carbonate, dimethyl carbonate, and methyl ethyl carbonate. Lactones include γ-butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1,3-oxaziridine-.
2-one, 3-ethyl-1,3-oxazolidine-2-
There is ON etc. As the imidazolidinones, 1,3-
Examples include dimethyl-2-imidazolidinone.

Among the above polar solvents, ethylene glycol, propylene glycol, diethylene glycol, water, lactones, alcohols, carbonates,
Ethers, nitrites and furans are preferred. As the above-mentioned inorganic acid and organic acid, polycarboxylic acids (2 to 4 valent) and monocarboxylic acids can be used, and further, boric acid, phosphoric acid, silicotungstic acid, silicomolybdic acid, phosphotungstic acid, phosphoric acid. Molybdic acid or the like can also be used. Among them, the polycarboxylic acids include aliphatic polycarboxylic acids, aromatic polycarboxylic acids, alicyclic polycarboxylic acids, alkyl (having 1 to 3 carbon atoms) or nitro substitution products of these polycarboxylic acids, for example, citraconic acid, Dimethyl maleic acid and nitrophthalic acid (3-nitrophthalic acid, 4-nitrophthalic acid) can be used, and further sulfur-containing polycarboxylic acids such as thiopropionic acid can be used.

The above aliphatic polycarboxylic acids include: saturated polycarboxylic acids such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,6-decane. Dicarboxylic acid, 5,6-decanedicarboxylic acid, 1,7-octanedicarboxylic acid, 7-methyl-7-methoxycarbonyl-1,9-decanedicarboxylic acid, 7,9-dimethyl-
7,9-dimethoxycarbonyl-1,11-dodecanedicarboxylic acid, 7,8-dimethyl-7,8-dimethoxycarbonyl-1,14-tetradecanedicarboxylic acid; and unsaturated polycarboxylic acids such as maleic acid, fumaric acid, Itaconic acid can be used. Examples of the aromatic polycarboxylic acids that can be used include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, and pyromellitic acid.

Examples of the alicyclic polycarboxylic acids include tetrahydrophthalic acid (cyclohexane-1,2-
Dicarboxylic acid, etc.) and hexahydrophthalic acid can be used. Aliphatic monocarboxylic acids (having 1 to 30 carbon atoms), aromatic monocarboxylic acids, and oxycarboxylic acids can be used as the above monocarboxylic acids. The aliphatic monocarboxylic acids include: saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, lauric acid, myristic acid, stearic acid. , Behenic acid, malic acid, tartaric acid; unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, oleic acid can be used. Examples of the aromatic monocarboxylic acids include benzoic acid, o-nitrobenzoic acid, p-nitrobenzoic acid,
Cinnamic acid and naphthoic acid can be used. As the oxycarboxylic acids, for example, salicylic acid, mandelic acid, resorcinic acid and the like can be used.

Next, ammonium salts, amine salts or amidine salts are suitable as the above-mentioned inorganic or organic acid salts. Of these, examples of ammonium salts are omitted here. As amines constituting amine salts, primary amines (methylamine, ethylamine, propylamine, butylamine, ethylenediamine, etc.), secondary amines (dimethylamine, diethylamine, dipropylamine, methylethylamine, diphenylamine, diethanolamine, etc.), 3 Primary amines (trimethylamine,
Triethylamine, tripropylamine, triphenylamine, triethanamine, etc.) and quaternary amines (tetramethylamine, tetraethylamine, tetrapropylamine, etc.) can be used. As amidine salt,
A compound having an alkyl-substituted amidine group and a quaternary compound of the same can be used. For example, carbon number 1
An imidazole compound quaternized with an alkyl group or an arylalkyl group of 11, a benzimidazole compound,
Alicyclic amidine compounds can be used. Specifically, the quaternized compound having an alkyl-substituted amidine group includes 1-methyl 1,8-diazabicyclo [5,4,0].
Undecene-7,1-methyl-1,5-diazabicyclo [4,3,0] nonene-5,1,2,3-trimethylimidazolinium, 1,2,3,4-tetramethylimidazolinium, 1 , 2-Dimethyl-3-ethyl-imidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethyl-2-heptylimidazolinium, 1,3-dimethyl-2- ( -3'heptyl)
Imidazolinium, 1,3-dimethyl-2-dodecylimidazolinium, 1,2,3-trimethyl-1,4
5,6-tetrahydropyrimidinium, 1,3-dimethylimidazolium, 1-methyl-3-ethyl-imidazolinium, 1,3-dimethylbenzimidazolinium and the like, and one or more selected from these Can be used. Since these materials do not use a metal salt as a cation, when applied to an electrolytic capacitor, high ionic conductivity can be obtained while improving short-circuit resistance, that is, making short-circuiting less likely to occur. The effect is obtained.

Next, the mixing ratio of the first monomer and the second monomer is preferably 100: 3 to 3: 100 by weight. If the weight ratio exceeds the upper and lower limits, it becomes difficult to form a copolymer matrix. Further, it is preferably 100: 10 to 10: 100. Thereby, the skeleton of the matrix is more stably maintained, and the effect that the effect can be more efficiently obtained can be obtained. Further, the content of the acrylic derivative copolymer is preferably 5 to 50 wt% in the total weight of the solute and the acrylic derivative copolymer. If the content of the copolymer is less than 5 wt%, the matrix of the cross-linked product cannot be formed and curing cannot be performed. Further, when the content is 50 wt% or more, the absolute amount of the electrolytic solution taken in the matrix decreases,
This is because the ionic conductivity is significantly reduced and sufficient characteristics cannot be obtained.

An electrolytic capacitor produced by sandwiching a separator containing the polymer electrolyte composite according to the present embodiment as an element for driving an electrolytic capacitor between an anode foil and a cathode foil is long in an environment of high temperature. It is possible to maintain stable performance over time. The polymer electrolyte composite does not react with, for example, an aluminum or carbon electrode foil, and can provide a capacitor excellent in moldability and long life. In the electrolytic capacitor according to this embodiment, the basis weight of the separator is preferably in the range of 0.01 to 55 g / m ² . In the conventional electrolytic solution or ion conductive polymer, when these low-basis weight separators are used, short circuit is caused and stable characteristics cannot be maintained, whereas the polymer electrolyte composite for driving the electrolytic capacitor of the present embodiment is not maintained. When the body is used, the polymer matrix is stretched around the separator in a mesh shape, so that the distance between the electrodes of the capacitor can be physically maintained. Further, for this reason, the stability of the withstand voltage is improved, and it is possible to use a separator having a low basis weight even for a medium to high voltage capacitor which could not be conventionally applied, and it is possible to bring out good characteristics. If the basis weight of the separator is outside the above-mentioned preferred range, a short circuit is likely to occur or the dielectric loss (tan δ) becomes too large.

Here, examples of materials that can be used as the separator include manila paper, kraft paper, and Hemp.
There are papers, non-woven fabrics, and mixed paper materials thereof. Further preferred separator materials are porous resin films and non-woven fabrics. This is because it is easy to control the porosity.
The porosity of the separator is preferably in the range of 10 to 90%. In particular, the effect is remarkable when a porous resin film or a nonwoven fabric is used as the material of the separator. That is, in the conventional electrolytic solution or ion conductive polymer, a short circuit was caused within the range of 10 to 90% depending on the type of the porous resin film or the non-woven fabric. When a molecular electrolyte complex is used, the polymer matrix is stretched around the porous resin film or non-woven fabric in a mesh shape and contains the gel of the polar solvent in which the solute is dissolved. Can be physically maintained. Therefore, the breakdown voltage can be kept stable, and good characteristics can be obtained. Incidentally, if the porosity of the separator is outside the preferred range, it is easy to cause a short circuit,
The dielectric loss (tan δ) becomes too large. In particular,
By using these materials, it is possible to greatly reduce the resistance component occupied by the separator in the capacitor, and therefore it is very effective in lowering ESR (equivalent series resistance) and lowering impedance.

As the porous resin film or nonwoven fabric, polyethylene resin, polypropylene resin,
Fluorine resin, polyester resin, polyamide resin, polyurethane resin, styrene resin, polyethylene terephthalate resin, vinyl chloride resin, vinylcarbazole resin,
Vinylidene chloride resin, vinyl acetate resin, methacrylic resin, polycarbonate resin, polyacetal resin, cellulose resin, phenol resin, urea resin, melamine resin, guanamine resin, aniline resin, epoxy resin, unsaturated polyester resin, allyl resin, xylene resin, silicon Resin or furan resin can be used.
Hereinafter, examples in which the present embodiment is embodied will be described using examples, and some comparative examples will be specifically described in order to compare them.

[0062]

EXAMPLES Specific examples will be described in detail below. << Example 1 group >> [I-1. Composition of Electrolytes of Examples 1 to 17 and Their Properties]
As an example based on the present embodiment, 17 kinds of polymer electrolyte composite samples, two kinds of solid electrolyte samples (Comparative Examples 1 and 2) for comparison, and a total of 19 kinds of electrolyte samples were prepared. Tables 1 to 3 show the measurement results of the constituent materials, compositions and properties thereof. There are various types of acrylic derivatives of the formulas (1) and (5). They are illustrated in Table 4 and Table 5. As the examples, as shown in Tables 1 to 3, predetermined ones were used. The electrolyte samples of Examples 1 to 17 and Comparative Examples 1 and 2 were prepared as follows.

First, the first embodiment will be described. Table 1
4 materials shown in the column of the constituent material of Example 1 in 3 to 3 were prepared. That is, ethylene glycol as a polar solvent, ammonium benzoate as a solute, a compound of formula (1) as the first monomer (however, No. 1 in Table 4), and a compound of formula (5) as the second monomer. (However, in Table 5, No. 11). These four materials were similarly mixed at the compounding ratios shown in the column of composition in Tables 1 to 3 to prepare an electrolyte sample stock solution. 20 g of this electrolyte sample stock solution was put in a petri dish, the lid was covered, and then the electrolyte sample of Example 1 was produced by heating and curing at a predetermined temperature and time. The water content in the electrolyte sample after heat curing was adjusted to be 2 wt%. The ionic conductivity of the electrolyte sample of Example 1 thus produced was measured using an impedance analyzer. As a result of the measurement, the ionic conductivity is 2.2 mS / cm.
Met.

Further, the spark generation voltage of the same electrolyte sample of Example 1 was measured as follows. That is, first, a predetermined amount of an electrolyte sample stock solution was prepared by the same method as described above, and put into a closed bottle. In the electrolyte sample stock solution, an aluminum anode foil and an aluminum cathode foil having a size of 2 cm × 5 cm and having a predetermined thickness are immersed with a 1 cm interval, and the sealed bottle is fixed with both electrode foils fixed. Sealed. The electrolyte sample stock solution was cured by heating the closed bottle at a predetermined temperature and for a predetermined time. In that state, a voltage was applied between both electrode foils, and the voltage was gradually increased to measure the spark generation voltage, that is, the voltage at which sparks started to be generated between both electrodes. The anode foil is an aluminum foil, which is subjected to an etching treatment in an acidic aqueous solution, and then anodized in a boric acid aqueous solution under application of a predetermined voltage to form an aluminum oxide dielectric film having a predetermined thickness on both front and back surfaces. It was prepared by forming a body film. As a result of the measurement, the spark generation voltage was 580V.

Electrolyte samples of Examples 2 to 17 and Comparative Examples 1 and 2 were also prepared by the same method as the method of preparing the electrolyte sample of Example 1 above. That is, 20 g of each electrolyte sample stock solution having the constituent materials and compositions shown in Tables 1 to 3 is heat-cured in the same manner as above to prepare an electrolyte sample, and the water content in each electrolyte sample after heat-curing is 2 wt.
Adjusted to be%. The ionic conductivity of each of these electrolyte samples was measured by an impedance analyzer as described above. The measurement results are shown in Tables 1 to 3. Furthermore, the spark generation voltage for the electrolyte samples of the same Examples 2 to 17 and Comparative Examples 1 and 2 was measured by the spark generation voltage measurement method using the same sealed bottle as above. Tables 1 to 3 show the measurement results of those spark generation voltages.

[0066]

[Table 1]

[0067]

[Table 2]

[0068]

[Table 3]

[0069]

[Table 4]

[0070]

[Table 5]

From the results shown in Tables 1 to 3, Examples 1 to 1
It can be seen that in the electrolyte sample of No. 17, as compared with Comparative Examples 1 and 2, the ionic conductivity is slightly reduced, but the spark generation voltage is improved. That is, a short-circuit improving effect of making short-circuiting difficult is recognized.

Next, based on Example 1, in order to investigate the influence of the weight ratio of the first monomer and the second monomer on the formation of the copolymer matrix, the ionic conductivity and the spark voltage, the electrolyte sample of Example 1 was examined. The same manufacturing method as that of Example 1 except that the weight ratio of the first monomer to the second monomer is 10
As shown in Table 6, Example 1 was varied in the range of 0: 1 to 1: 100 (the weight ratio in which the larger one is 100 parts by weight).
In addition to the above, eight electrolyte samples were prepared. For these electrolyte samples, it was confirmed whether or not a matrix was formed, and the ionic conductivity and the spark voltage were measured as in Tables 1 to 3. The results are also shown in Table 6. In the case of Example 1, the ratio of 8 wt% and 2 wt%, which are the respective weight percentages shown in Tables 1 to 3, that is, 8: 2 is 100: 25 when converted into a weight ratio with the larger one being 100 parts by weight. Is.

[0073]

[Table 6]

From Table 6, when the weight ratio of the first monomer to the second monomer is less than 100: 3 or more than 3: 100, the matrix is not formed, and the ionic conductivity and the spark voltage are comprehensively evaluated. Then, even if the weight ratio is 100: 3 to 3: 100, further 100: 10.
It turns out that the range of 10: 100 is more preferable.

[I-2. Characteristics of Electrolytic Capacitors Using Electrolytes of the Above Examples] Next, among the constituent materials of the electrolytes shown in Tables 1 to 3, those having the same Example number in Table 7, that is, Examples 1, 4, 5, 7 , 8, 9, 12, 14 and 15, and 20 aluminum electrolytic capacitor samples were prepared for each electrolyte using the constituent materials of Comparative Examples 1 and 2, and initial characteristics were measured and a life test was performed. Example 1
The method of producing the electrolytic capacitor sample and the like will be described below by taking the case of using the electrolyte of 1. as an example. First, an electrolyte sample stock solution based on Example 1 was prepared in advance by the same method as described in [I-1]. On the other hand, an aluminum foil having a thickness of 100 μm was prepared, and after etching treatment in an acidic aqueous solution, anodization was performed in a boric acid aqueous solution under application of a voltage of 600 V. A dielectric oxide film was formed. Through this step, an anode foil having a dielectric film having a predetermined thickness was formed. Anode foil prepared in this way and 2
60 μm thick kraft paper as a separator (basis weight is 35 g / m 2) between a 2 μm thick aluminum cathode foil.
² ) was sandwiched and wound a predetermined number of times so that both electrode foils face each other, and leads were electrically connected to the anode foil and the cathode foil, respectively. Thus, a capacitor precursor was produced.

This electrolytic capacitor precursor was impregnated with a predetermined amount of the above-prepared electrolyte sample stock solution to prepare an electrolytic capacitor original element. The original element was placed in a predetermined aluminum case, and the case was sealed with a sealing member. After that, the case having this original element was heated to cure the electrolyte stock solution inside the original element. Two electrolytic capacitor samples based on Example 1 were prepared by this manufacturing method.
0 pieces were produced. In producing these samples, the number of windings of the foil-separator and the like were adjusted so that all 20 had a rating of 400 WV and 470 μF. These samples were aged for 1 hour under a voltage of 425V. In the same manner as the electrolytic capacitor sample manufacturing method based on the above-mentioned Example 1, Examples 4, 5, 7,
Electrolyte samples for 8, 9, 12, 14, 15 and Comparative Examples 1 and 2 were also made. That is, each electrolyte sample stock solution having the composition of each of those Examples shown in Tables 1 to 3,
The same method as described in [I-1] was prepared in advance, and the electrolytic capacitor samples based on the respective Examples and Comparative Examples were respectively prepared by the same method as described at the beginning of [I-2]. 20 pieces were produced.

With respect to the electrolytic capacitor samples thus produced, their initial characteristics and characteristics at the time of 5000 hours by the 105 ° C. ripple superimposed DC load test were measured. Where tan δ (dielectric loss), LC
(Leakage current) and capacity are JIS-C-5102 of Japanese Industrial Standards.
The measurement method is based on. In addition, as a method of the ripple load test, a ripple current of 60 Hz is superimposed on the DC voltage, the DC voltage is set so as to be a rated voltage, and the characteristic changes at a predetermined temperature (here, 105 ° C.). The method of investigation was used. The measurement results of those characteristics are shown in Table 7, and the numerical values are the average values of 20 samples. For example, for 20 electrolytic capacitor samples according to Example 1, the initial tan δ (dielectric loss) is 4.6.
%, LC (leakage current) is 20 μA, 105 ° C ripple load test At the time of 5000 hours, ΔC (rate of change in capacity)
Was −0.6%, tan δ was 6.8%, LC was 11 μA, and no abnormal appearance of the sample was observed in any of the 20 samples.

[0078]

[Table 7]

From the results shown in Table 7, for each of the 20 samples of Comparative Examples 1 and 2 using the solid electrolyte, a short circuit occurred during aging, and a normal electrolytic capacitor could not be manufactured. On the other hand, Example 1 and Examples 4, 5, 7, 8, 9, 12,
It can be seen that the electrolytic capacitors of Nos. 14 and 15 have stable initial characteristics and have no short circuit and valve opening problems even after 5000 hours of the 105 ° C. ripple load test. From this, it is understood that the polymer electrolyte composite for driving an electrolytic capacitor including the copolymer matrix made of the acrylic derivative of the present embodiment has a great effect on heat resistance.

Example 2 Group [II-1. Compositions of Electrolytes of Examples 18 to 30 and Their Properties] As examples based on the present embodiment, samples of 13 kinds of polymer electrolyte composites, and samples of solid electrolytes for comparison (Comparative Example 3) and electrolytic solutions were prepared. (Comparative Examples 4 and 5), a total of 16 kinds of electrolyte samples were prepared. Tables 8 and 9 show the measurement results of the constituent materials, compositions, and characteristics. As in the case of the above [I-1], among the compounds shown in Table 4 and Table 5 as examples of the acrylic derivative of the formulas (1) and (5), the present [II-1]
Tables 8 and 9 show examples used as a part of the above.

The electrolyte samples of Examples 18 to 30 and Comparative Examples 3, 4 and 5 are the same as described in [I-1] above, and the columns of the constituent materials of Examples in Tables 8 and 9 are the same. Similarly, the materials shown in Table 1 were mixed at the compounding ratios shown in the columns of composition in Tables 8 and 9 to prepare an electrolyte sample stock solution, 20 g of the electrolyte sample stock solution was placed in a Petri dish, and the lid was closed. Each electrolyte sample was prepared by curing over time. In addition, in Examples 18 to 25 and Comparative Example 3, as in the case of [I-1], the water content in each electrolyte sample after heat curing was adjusted to be 2 wt%. On the other hand, Examples 26 to 30 containing a boric acid-based material
Further, in Comparative Examples 4 and 5, the water content in each electrolyte sample was adjusted to 25 wt%. The ionic conductivity of the 16 electrolyte samples thus produced was measured using an impedance analyzer. further,
The spark generation voltage of the same 16 electrolyte samples was measured by the spark generation voltage measurement method using the same closed bottle as used in Example Group I. The measurement results of those characteristics are shown in Tables 8 and 9. For example, in the case of the electrolyte sample of Example 18, the ionic conductivity was 1.2 mS / cm and the spark generation voltage was 550V.

[0082]

[Table 8]

[0083]

[Table 9]

From the results shown in Tables 8 and 9, in the electrolyte samples of Examples 18 to 30, Comparative Examples 3 and 4 were obtained.
It can be seen that the spark generation voltage is significantly improved in comparison with Comparative Examples 5 and 5 as compared with Comparative Examples using the same solvent and the same solute.

[II-2. Characteristics of Electrolytic Capacitors Using Electrolytes of the Above Examples] Next, among the electrolytes shown in Table 1, Table 8 and Table 9, those shown by the same Example numbers in Tables 10 and 11 were used for aluminum electrolysis. Twenty capacitor samples were prepared for each electrolyte, and initial characteristics were measured and a life test was performed. Among them, as to the method for producing each electrolytic capacitor sample shown in Table 10,
The constituent material of the electrolyte is the same as the embodiment number in Table 10, the embodiment numbers in Table 1, Table 8 and Table 9, that is, the constituent materials in Examples 4, 18, 19, 22 and 24 and Comparative Example 3. Was used, Manila paper was used as the separator instead of kraft paper, and the basis weight was changed, and the applied voltage for anodic oxidation was changed to 30 V instead of 600 V.
It was produced by the same production method as the method described in [I-2] above, except that the electrolytic capacitor sample was set to 0 V, and correspondingly, the rating of each electrolytic capacitor sample was set to 160 WV330 μF instead of 400 WV470 μF. The basis weight is the product of density and thickness.

For the method for producing each electrolytic capacitor sample shown in Table 11, the constituent materials of the electrolyte are shown in Table 1.
Example No. 1 in Table 9 which is the same as that of Example 1, that is, the constituent materials of Examples 26, 27, 28, 29 and 30 and Comparative Examples 4 and 5, and kraft paper as a separator Instead, a porous resin film having a thickness of 40 μm and different porosity and type was used, and the rating of each electrolytic capacitor sample was 400 WV47.
It was manufactured by the same manufacturing method as the method described in [I-2] above except that 400 WV was 330 μF instead of 0 μF. Here, the porosity is [1- (density of separator / true density of separator material)] × 100 (%)
It is defined by the value of.

With respect to the electrolytic capacitor samples thus produced, their initial characteristics and characteristics at the time of 5000 hours by the DC load test were measured.
Here, tan δ (dielectric loss), LC (leakage current) and capacity were measured by the measuring method based on JIS-C-5102 of Japanese Industrial Standards. The DC load test in Table 10 was set to a temperature of 125 ° C., the DC load test in Table 11 was set to a temperature of 95 ° C., and the same method as the 105 ° C. ripple superimposed DC load test was used. However, a load test was conducted in which a rated DC voltage was applied without superimposing ripples. The measurement results of those characteristics are shown in Tables 10 and 11, respectively, and the numerical values are the average values of 20 samples. Table 1
0, for example, the grammage of Example 18 is 12.0 g /
In the case of 20 electrolytic capacitor samples using a separator having a density of 0.3 g / cm ³ at m ² , the initial tan δ (dielectric loss) was 2.9%, and the LC (leakage current) was 30 μA, 12
5 ° C DC load test At the time of 5000 hours, ΔC
(Capacity change rate) is -0.8%, tan δ is 6.1%, L
C was 13 μA, and no abnormal appearance of the sample was observed in any of the 20 samples. Further, as shown in Table 11, for example, in the case of 20 electrolytic capacitor samples using a separator of a polyethylene resin film having a porosity of 40% based on Example 26, the initial tan δ (dielectric loss) was 24. 0.1%, LC (leakage current) is 24 μA, 9
5 ° C DC load test At the time of 5000 hours, ΔC
The (volume change rate) was −0.6%, tan δ was 6.7%, LC was 9 μA, and no abnormal appearance of the sample was observed in any of the 20 samples.

[0088]

[Table 10]

[0089]

[Table 11]

From the results shown in Tables 10 and 11, the aluminum electrolytic capacitors of Examples 18 to 30 of the present embodiment had the same electrical characteristics of the electrolytic capacitor driving electrolyte as compared with the comparative examples. In a DC load test at high temperature, all of the short circuits occurred in Comparative Example 3 in which a separator having a small basis weight was combined with a solid electrolyte and Comparative Example 4 in which a porous resin separator having a porosity of 25% was combined with an electrolytic solution. On the other hand, it can be seen that the examples of the present embodiment are very stable, and there are clear differences. In addition, the porosity is 25
% In Comparative Example 5 in which the kraft paper separator and the electrolytic solution are combined does not cause a short circuit, but the characteristic change rate before and after the load test is remarkably large, while each Example of the present embodiment is stable even after the test. It is shown to retain its properties.

[0091] Further, from Table 10, in the range separator basis weight of 0.01~55g / m ^2, the characteristic exhibits favorable values, 0.01 g / m ² less than or 55 g /
It can be seen that when the value exceeds m ² , the electrolytic capacitor sample is short-circuited or the value of tan δ becomes too large. Further, similarly from Table 11, when the porosity of the separator using the porous resin film is in the range of 10 to 90%, each characteristic shows a preferable numerical value, but when the porosity is less than 10% or more than 90%, the electrolytic capacitor is It can be seen that the sample is short-circuited or the value of tanδ becomes too large. Although not shown here as a specific sample, even when a non-woven fabric is used instead of the porous resin film, the porosity is in the range of 10 to 90% as in the case of the porous resin film. It was confirmed that each characteristic shows a preferable numerical value.

From these results, the first monomer having at least one compound having a hydroxyl group at the terminal of the acrylic derivative represented by the formulas (1) to (4) and the formula (5) to
A driving electrolyte containing a copolymer matrix composed of a second monomer having at least one acrylic derivative compound represented by the formula (16) has a lower ionic conductivity than conventional electrolytic solutions, The use of low volume separators and high porosity separators
δ, ESR and impedance can be made sufficiently low.

In order to make the effects shown in Tables 10 and 11 more clear, Examples 1 and 4 in Table 7, Example 18 in Table 10, and Example 26 in Table 11 were obtained.
(Third line: using a polyethylene resin separator having a porosity of 40%) and the aluminum electrolytic capacitor sample of Comparative Example 5 were disassembled after the above test, and the capacity and appearance of the cathode foil were examined. The results are shown in Table 12.

[0094]

[Table 12]

As is clear from Table 12, in the cathode foil after the test of Comparative Example 5, the initial capacity ratio was reduced to 1/2 or less, and the surface was discolored to black, while With the cathode foils of Examples 1, 4, 18 and 26, almost no change in capacity was observed and no discoloration was observed.

As described above, it was confirmed that the electrolyte for driving an electrolytic capacitor according to the present embodiment has the property of protecting the surface of the cathode foil even in a high temperature environment, and the aluminum electrolytic having a long life stability at high temperature. Capacitors can be supplied.

Finally, the driving electrolyte of this embodiment (see Table 7).
Example 1, Example 4 and Example 5, and Example 18) of Table 10 and the electrolytic capacitor samples of Comparative Example (Comparative Example 4) were compared for their ability to be formed into electrode foils. For comparison of the chemical conversion ability, a constant current voltage of ² mA / 10 cm ² was applied between the positive and negative electrodes of each electrolytic capacitor sample. By applying the voltage, formation of the anode foil started, and while the formation continued, the voltage between the positive and negative electrodes, that is, the repair voltage increased, and the repair voltage increased to the breakdown voltage of the dielectric oxide film. After that, the voltage began to fluctuate when sparks began to occur. The result is shown in FIG. It can be seen that when the driving electrolyte of the present embodiment is used, it has a high repair voltage of 100 V or more, that is, a high chemical conversion capacity, as compared with the comparative example. This means that the short-circuit resistance can be improved even in a higher temperature environment, and it can be seen that excellent life characteristics can be realized even if a separator having a low basis weight or a porous resin film is used.

Although not shown in the above examples, even when the driving electrolyte of the present embodiment is used in the electrolytic capacitor having a rating of 4 to 100 WV, the same effects as those obtained in the above various examples are obtained. It was also confirmed that an effect can be expected.

[0099]

As described above, the present invention comprises an electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative, the electrolyte being a polar solvent and an inorganic acid or organic acid or a salt thereof. At least one of a monofunctional monomer group having a hydroxyl group at a terminal and having one polymerizable unsaturated double bond, which is an acrylic derivative. A capacitor containing a copolymer matrix, which is a polymer of a first monomer consisting of 2) and a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of polymerizable unsaturated double bonds which is an acrylic derivative. By adopting a structure that uses a driving electrolyte, it has better characteristics in terms of leakage and heat resistance than conventional driving electrolyte solutions, and it has a metal-based structure compared to conventional driving ion-conducting polymers. Salt Such as by not are those showing a significant improvement in short-circuit resistance is made large industrial value.

[Brief description of drawings]

FIG. 1 is a perspective view showing main components of an electrolytic capacitor according to an embodiment of the present invention.

FIG. 2 is a graph showing a difference in chemical conversion ability for repairing an electrode foil when using a polymer electrolyte composite for driving an electrolytic capacitor according to an example of the present invention and a comparative example.

[Explanation of symbols]

1 Anode foil 2 cathode foil 3a, 3b Separator 4a, 4b lead

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Junji Ozaki             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. (72) Inventor Yuichiro Tsubaki             1006 Kadoma, Kadoma-shi, Osaka Matsushita Electric             Sangyo Co., Ltd. F-term (reference) 4J100 AL08P AL66Q BA02Q BA03P                       BA03Q BA04Q BA08P BA08Q                       BA12P BA16P BA38Q BA64P                       BA64Q BC04Q BC43Q CA04                       DA55 DA56 JA43

Claims (13)

[Claims] 1. An electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative, wherein the electrolyte is a polar solvent and a solute comprising at least one of an inorganic acid or an organic acid or a salt thereof. And the copolymer is
Acrylic derivative having a hydroxyl group at the terminal and at least one first monomer selected from the group of monofunctional monomers having one polymerizable unsaturated double bond, and an acrylic derivative polymerizable unsaturated double bond A polymer electrolyte composite for driving an electrolytic capacitor, which is a polymer with a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of bonds. 2. The polymer electrolyte composite for driving a capacitor according to claim 1, wherein the copolymer of the acrylic derivative constitutes a copolymer matrix, and the electrolyte is incorporated in the copolymer matrix. 3. The polymer electrolyte composite for driving a capacitor according to claim 1, wherein the acrylic derivative copolymer contains a polyoxyalkylene group. 4. The polymer electrolyte composite for driving a capacitor according to claim 1, wherein the solute does not contain a metal salt as a cation. 5. The polymer electrolyte composite for driving a capacitor according to claim 4, wherein the solute is at least one salt selected from the group consisting of ammonium salts, amine salts and amidine salts of the inorganic acids and the organic acids. . 6. The monofunctional monomer group is represented by the following formula (1):
To the acrylic derivative represented by the formula (4), and the polyfunctional monomer group comprises an acrylic derivative represented by the following formulas (5) to (16). Polyelectrolyte complex. [Chemical 1] R ¹ is H or an alkyl group having 1 to 5 carbon atoms, AO ¹ is an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 200. [Chemical 2] R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 2
00. [Chemical 3] R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 2
00. [Chemical 4] R ¹ is H or an alkyl group having 1 to 5 carbon atoms, and n is 1 to 2
00. [Chemical 5] R ³ is H or an alkyl group having 1 to 5 carbon atoms, AO ² is an oxyalkylene group having 2 to 4 carbon atoms, and n is 1 to 200. [Chemical 6] R ³ is H or an alkyl group having 1 to 5 carbon atoms, n is 1 to 2
00. [Chemical 7] R ¹ and R ² are H or an alkyl group having 1 to 5 carbon atoms, and both may be the same or different. [Chemical 8] R ¹ and R ² are H or an alkyl group having 1 to 5 carbon atoms, and both may be the same or different. l, m and n
Is 1 to 200. [Chemical 9] R ¹ is H or an alkyl group having 1 to 5 carbon atoms. [Chemical 10] R ¹ is H or an alkyl group having 1 to 5 carbon atoms. [Chemical 11] R ¹ is H or an alkyl group having 1 to 5 carbon atoms. [Chemical 12] [Chemical 13] [Chemical 14] [Chemical 15] [Chemical 16] R ¹ is H or an alkyl group having 1 to 5 carbon atoms, n is 1 to 9
Is a natural number of. 7. The polymer electrolyte composite for driving a capacitor according to claim 1, wherein the weight ratio of the first monomer to the second monomer is in the range of 100: 3 to 3: 100. 8. The content of the solute and the acrylic derivative is 5 to 50 wt% in the total weight of the copolymer.
The polymer electrolyte composite for driving a capacitor according to claim 1, which is in the range of%. 9. An electrolytic capacitor comprising an anode foil, a cathode foil, and a separator sandwiched between the anode foil and the cathode foil, the separator including a polymer electrolyte composite for driving an electrolytic capacitor, the electrolytic capacitor comprising: The capacitor-driving polymer-electrolyte complex comprises an electrolyte and an acrylic polymer containing a copolymer of an acrylic derivative, and the electrolyte is a polar solvent and at least an inorganic acid or an organic acid or a salt thereof. The copolymer is composed of one solute, and is at least one member selected from the group consisting of an acrylic derivative having a hydroxyl group at the terminal and having one polymerizable unsaturated double bond.
An electrolytic capacitor, which is a polymer of a first monomer consisting of two and a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of polymerizable unsaturated double bonds which is an acrylic derivative. 10. The basis weight of the separator is 0.01-5.
The electrolytic capacitor according to claim 9, which is in a range of 5 g / m ² . 11. The electrolytic capacitor according to claim 9, wherein the separator is a porous resin film or a nonwoven fabric. 12. The separator has a porosity of 10 to 90.
The electrolytic capacitor according to claim 9, which is in the range of%. 13. A forming step of forming a capacitor precursor comprising an anode foil, a cathode foil and an insulating separator sandwiched therebetween, and impregnating the capacitor precursor with a polymer electrolyte composite stock solution for driving an electrolytic capacitor. A method of manufacturing an electrolytic capacitor, comprising: a manufacturing step of manufacturing a raw electrolytic capacitor element; and a curing step of hardening the polymer electrolyte composite stock solution for electrolytic capacitor in the raw electrolytic capacitor element. The polyelectrolyte complex stock solution for driving contains an electrolyte solution composed of a polar solvent and a solute composed of at least one of an inorganic acid or an organic acid or a salt thereof, and an acrylic derivative having a hydroxyl group at the terminal, which is not polymerizable. Polymerizable with the first derivative consisting of at least one monofunctional monomer having one saturated double bond and an acrylic derivative Is a mixed liquid containing a second monomer consisting of at least one of a polyfunctional monomer group having a plurality of unsaturated double bonds, wherein the first monomer and the second monomer are copolymerized by the curing step. A method for producing an electrolytic capacitor, wherein a copolymer matrix is formed and the electrolyte solution becomes a gel electrolyte for driving an electrolytic capacitor and is taken into the copolymer matrix.