JP2002324735A - Method for manufacturing gelled electrolyte - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing gelled electrolyte for an aluminum electrolytic capacitor wherein ion conductivity is high since content of electrolytic solution to polymer component in the gelled electrolyte is large, thermal resistance form stability is ensured, and further manufacturing of an aluminum electrolytic capacitor is enabled by using the conventional manufacturing process almost as it is. SOLUTION: This method for manufacturing gelled electrolyte is provided with an electrode manufacturing process, an assembling process, an impregnation process wherein impregnation of gelled electrolyte forming composition is performed, and a heating process. The impregnation process is arranged after the electrode manufacturing process or the assembling process. In the heating process, heating is performed at 50-170 deg.C. The gelled electrolyte forming composition contains polymerizable monomer, electrolytic solution and radical polymerization initiator, and forms gelled electrolyte by gelation in the heating process. The polymerizable monomer contains monovinyl monomer and polyvinyl monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a gel electrolyte for an aluminum electrolytic capacitor.

[0002]

2. Description of the Related Art Conventionally manufactured aluminum electrolytic capacitors use an electrolytic solution in which an electrolyte is dissolved in an organic solvent, and use a sealing material such as a rubber sealing material in a metal case. Was enclosed.

However, during use, a voltage higher than the rated voltage may be applied to the aluminum electrolytic capacitor.
In such a case, the temperature of the condenser increases, the vapor pressure of the organic solvent constituting the electrolytic solution increases, and hydrogen gas is also generated by the electrochemical reaction, so that the internal pressure of the condenser increases. As a result, when the internal pressure of the condenser exceeds the withstand pressure limit of the case or the seal, there is a problem that the organic solvent is gasified and ejected together with the hydrogen gas.

[0004] Liquid electrolytes do not have shape retention properties,
Special consideration was also required for the liquid leakage resistance of the product, and improvement was required.

[0005] As a technique for improving the liquid leakage resistance and maintaining the degree of freedom of processing, there is a method corresponding to the above-mentioned demand by making the electrolyte non-fluidized, and the cross-linked vinyl polymer and the electrolyte are mixed. A technique for forming a gel electrolyte is disclosed in Japanese Patent Application Laid-Open No. 5-325.
No. 986.

[0006]

SUMMARY OF THE INVENTION The gel electrolyte disclosed in the above publication is obtained by synthesizing a polymer, purifying and drying the polymer,
Thereafter, the electrolytic solution is mixed. This technology is
It has the following problems. (1) The retention rate of the electrolytic solution in the gel electrolyte is limited to 6 to 7 times the polymer component, and the ratio of the polymer component having a high specific resistance is high. It is not satisfactory as a gel electrolyte. (2) Since the electrolytic solution is mixed after the production of the polymer, the production steps for producing the gel electrolyte are many and complicated, and when applied to an aluminum electrolytic capacitor, the size of each depends on the type. The degree of freedom in responding to the size variation of the capacitor is small, such as the need to manufacture different types.

[0007] In the manufacturing and processing steps of the capacitor, it is possible to arbitrarily cope with the manufacture of capacitors having different sizes and shapes, and since there is a high degree of freedom in processing, electrodes and separators are arranged in a case in a predetermined configuration. After that, a capacitor is manufactured by pouring an electrolyte solution into a predetermined gap and sealing it. Even when a gel electrolyte is used, a similar high degree of workability is required. However, the technique described in Japanese Patent Application Laid-Open No. 5-325986 cannot meet such a demand.

[0008] An object of the present invention is to provide a high content of an electrolytic solution with respect to a polymer component in a gel electrolyte, that is, a high electrolytic solution retention rate, and therefore, a high ionic conductivity, a heat-resistant shape stability, and a conventional type. Provided is a method for producing a gel electrolyte for an aluminum electrolytic capacitor, which is capable of producing an aluminum electrolytic capacitor using the production process almost as it is.

[0009]

SUMMARY OF THE INVENTION A method for producing a gel electrolyte for an aluminum electrolytic capacitor according to the present invention is a process for producing an electrode by processing an aluminum foil and forming the electrode into an electrode shape to form an electrode. An assembly step of disposing at least the electrode in a case, an impregnation step of impregnating a gel electrolyte forming composition, and a heating step, wherein the impregnation step is performed after the electrode manufacturing step or after the assembly step. The heating step is performed at 50 ° C. to 170 ° C., wherein the gel electrolyte forming composition contains a polymerizable monomer, an electrolytic solution, and a radical polymerization initiator. Wherein the polymerizable monomer contains a monovinyl monomer and a polyvinyl monomer, and the monovinyl monomer is an alkyl mono ( (T) acrylate or alkyl mono (meth) acrylate and polyethylene glycol mono (meth) acrylate as main components, the polyvinyl monomer contains polyethylene glycol di (meth) acrylate as main component, and the alkyl mono (meth) acrylate is It is characterized in that an alkyl mono (meth) acrylate having an alkyl group having 3 or more carbon atoms is a main component.

According to the above-described production method, the content of the electrolytic solution with respect to the polymer component in the gel electrolyte, that is, the electrolytic solution holding ratio is high, and therefore the ionic conductivity is high, the heat-resistant shape stability is obtained, and the conventional The gel electrolyte constituting the aluminum electrolytic capacitor can be formed using the manufacturing process almost as it is.

In particular, when the alkyl mono (meth) acrylate is mainly composed of an alkyl mono (meth) acrylate having an alkyl group having 3 or more carbon atoms, the hydrophobicity of the resin constituting the gel increases, and the alkyl mono (meth) acrylate becomes Compared to the case where methyl acrylate or methyl methacrylate is used as the meth) acrylate, a gel electrolyte having excellent hydrolysis resistance is formed even when the electrolyte is heated at a high temperature for a long time in the presence of water. Is done.

In the above invention, the content of the polyethylene glycol di (meth) acrylate is preferably from 5 to 70 mol% based on all the monomers.

When the content of the polyethylene glycol di (meth) acrylate is less than 5 mol%, the high temperature durability is insufficient, and when it exceeds 70 mol%, the retention of the electrolyte may be insufficient.

In the above invention, the monovinyl monomer has an alkyl mono (meth) acrylate / polyethylene glycol mono (meth) acrylate ratio of:
It is preferably from 100/0 to 5/95 (molar ratio).

The monovinyl monomer may be composed of only alkyl mono (meth) acrylate, but the combined use of polyethylene glycol mono (meth) acrylate increases the electrolyte retention. However, when the ratio of alkyl mono (meth) acrylate / polyethylene glycol mono (meth) acrylate is more than 5/95 (molar ratio), if the amount of polyethylene glycol mono (meth) acrylate is higher than that in the presence of water in the electrolytic solution, it will be longer at high temperatures. When heated for a period of time, the case where hydrolysis resistance becomes insufficient occurs.

The (meth) acrylate means at least one of acrylate and methacrylate, and either or both of them can be used.

Further, another method for producing a gel electrolyte for an aluminum electrolytic capacitor according to the present invention is a method for producing an electrode material by processing an aluminum foil and forming the electrode material into an electrode shape to form an electrode. An assembling step of disposing the electrode in the case, an impregnating step of impregnating the gel electrolyte forming composition, and a heating step, wherein the impregnating step is provided after the electrode manufacturing step or after the assembling step. The heating step is to heat at 50 ° C. to 170 ° C., and the gel electrolyte-forming composition contains a polymerizable monomer, an electrolytic solution, and a radical polymerization initiator. Wherein the polymerizable monomer contains a monovinyl monomer and a polyvinyl monomer, and the monovinyl monomer is a hydroxyl group-containing mono (meth) Acrylate comprises at least one carboxyl group-containing mono (meth) acrylate as a main component, wherein the polyvinyl monomer is characterized by containing two or more functional the (meth) acrylate as a main component.

According to the above-mentioned production method, the content of the electrolytic solution with respect to the polymer component in the gel electrolyte, that is, the electrolytic solution holding ratio is high, and thus the ionic conductivity is high, and the heat-resistant shape stability is obtained. The gel electrolyte constituting the aluminum electrolytic capacitor can be formed using the conventional manufacturing process almost as it is.

In particular, by using at least one of a hydroxyl group-containing mono (meth) acrylate and a carboxyl group-containing mono (meth) acrylate as a main component, a lactone-based organic solvent or a lactone-based organic solvent and an alcohol-based organic solvent can be used. It is possible to form a gel electrolyte having a high retention rate of an electrolytic solution using an electrolytic solution using a mixed solvent and having excellent high-temperature durability.

In the above-mentioned gel electrolyte forming composition, the bifunctional or higher functional (meth) acrylate is selected from polyethylene glycol di (meth) acrylate, glycerin di (meth) acrylate, and trimethylolpropane tri (meth) acrylate. It is preferable that the content of the bifunctional or higher functional (meth) acrylate is 1 to 50 mol% of all monomers.

When the content of the bifunctional or higher (meth) acrylate is less than 1 mol%, the high-temperature durability may be insufficient, and when it exceeds 50 mol%, the electrolyte retention may not be sufficient. There is.

The hydroxyl group-containing mono (meth) acrylate preferably contains at least 20 mol% of hydroxyl group-terminated polyethylene glycol mono (meth) acrylate in the monovinyl monomer. More preferably, all of the hydroxyl group-containing mono (meth) acrylate is a hydroxyl-terminated polyethylene glycol mono (meth) acrylate.

When the content of the hydroxyl group-containing mono (meth) acrylate is less than 20 mol%, the retention of the electrolyte may not be sufficient.

In the above-mentioned method for producing a gel electrolyte for an aluminum electrolytic capacitor, the impregnating step preferably involves a decompression step.

By providing the depressurizing step, a necessary portion of the electrolyte, such as between the electrodes inside the capacitor, can be filled with the gel electrolyte forming composition while excluding air.

It is preferable that the polymerizable monomer and the electrolytic solution are blended at an electrolytic solution / polymerizable monomer ratio of 6/1 to 15/1.

After the formation of the gel electrolyte, the ratio of the electrolytic solution to the polymer component is high, and practical ion conductivity can be obtained. When the amount of the polymerizable monomer is increased to the extent that the electrolyte / polymerizable monomer ratio is less than 6/1, the ionic conductivity of the gel electrolyte is reduced. Problems such as leakage may occur.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION Raw materials used in the present invention will be described. As a polymerizable component constituting the gel electrolyte of the present invention, an acrylic monovinyl monomer and an acrylic polyvinyl monomer are used. From the viewpoint that the retention rate of the electrolyte solution can be increased, it is preferable that the monovinyl monomer and the polyvinyl monomer each use a compound exemplified below as a main component. (Meth) acrylate means that either acrylate or methacrylate may be used.

[A] Examples of acrylic monovinyl monomers include mono (meth) acrylates of polyoxyalkylene polyols such as alkyl (meth) acrylate, alkoxypolyethylene glycol mono (meth) acrylate, and acylpolyethylene glycol mono (meth) acrylate. Are exemplified as suitable compounds.

As the alkyl group constituting the alkyl (meth) acrylate, specifically, methyl, ethyl, n
-Propyl, i-propyl, n-butyl, i-butyl,
t-butyl, n-, i- and neo-pentyl, n
And alkyl groups such as -hexyl, cyclohexyl, n-octyl, 2-ethylhexyl, lauryl and stearyl.

When a hydrophobic gel is formed, the alkyl mono (meth) acrylate has an alkyl group having 3 carbon atoms.
It is preferable that the above-mentioned alkyl mono (meth) acrylate is a main component.

When a gel having a high solvent affinity is formed, the monovinyl monomer contains at least one of a hydroxyl group-containing mono (meth) acrylate and a carboxyl group-containing mono (meth) acrylate as a main component, and the polyvinyl monomer has two or more functional groups. (Meth) acrylate as a main component.

Whether to use a hydrophobic gel or a gel having a high solvent affinity is appropriately selected depending on the use and the like.

As the hydroxyl group-containing mono (meth) acrylate, hydroxyalkyl (meth) acrylate, specifically, hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxybutyl acrylate,
Hydroxybutyl methacrylate is exemplified, and the use of hydroxyl-terminated polyethylene glycol mono (meth) acrylate having a structure obtained by ring-opening addition of ethylene oxide to hydroxyalkyl (meth) acrylate has a high affinity with the organic solvent used. This is preferable in that a gel electrolyte having a high electrolyte retention rate can be obtained.

As the carboxyl group-containing mono (meth) acrylate, at least one of acrylic acid and methacrylic acid is used.

As the polyethylene glycol (PEG) constituting the alkoxy polyethylene glycol (meth) acrylate, those having a repeating unit of ethylene oxide of 1 to 70 are used. If the molecular weight is too large, the gel strength will decrease.

[B] As the acrylic polyvinyl monomer, a polyfunctional (meth) acrylate having a polyoxyethylene unit such as polyethylene glycol di (meth) acrylate or urethane group-containing polyethylene glycol (meth) acrylate is mainly used. use.

The urethane group-containing di (meth) acrylate is a polyisocyanate compound such as a diisocyanate compound, a (meth) acrylate having an active hydrogen group, and if necessary, a polyhydroxy compound having an average molecular weight of 400 to 4000, preferably It is manufactured by the following exemplary method using PEG.

(1) An NCO / H ^* equivalent ratio of (meth) acrylate having an active hydrogen group (H ^* ) such as 2-hydroxyethyl methacrylate and a diisocyanate compound = 2
To synthesize an isocyanate group-containing intermediate, and react this isocyanate group-containing intermediate with a polyhydroxy compound at an NCO / OH equivalent ratio = 1. (2) NCO / OH equivalent ratio of polyethylene glycol mono (meth) acrylate and polyisocyanate compound =
React at 1.

The gel electrolyte-forming composition of the present invention may be produced by synthesizing a urethane group-containing di (meth) acrylate and then mixing it with a monovinyl monomer. Acrylates may be synthesized.

The polyethylene glycol used for the polyethylene glycol di (meth) acrylate or the polyethylene glycol mono (meth) acrylate used as the polyvinyl monomer has an average molecular weight of 400-4.
000 are used. If the molecular weight is too large, the gel strength will decrease.

As one component of the gel electrolyte forming composition of the present invention, if necessary, other vinyl monomers may be used in combination as long as the properties of the gel electrolyte of the present invention are not significantly impaired. This increases the degree of freedom in adjusting the characteristics of the gel electrolyte, which is preferable. As such a monomer, known compounds can be used without particular limitation. Specifically, styrene-based monomers such as styrene and α-methylstyrene, vinyl halides such as vinyl chloride, vinyl ethers, and vinyl acetate and the like Bifunctional or higher functional monomers such as alcohol derivatives, trimethylolpropane triacrylate, and divinylbenzene are exemplified. These vinyl monomers may be used alone or in combination of two or more.

The gel electrolyte for an aluminum electrolytic capacitor of the present invention is formed by heating a gel electrolyte forming composition. The radical polymerization initiator contained in the gel electrolyte composition preferably has a 10-hour half-life temperature of 70C to 150C.

By using the above-mentioned composition of the gel electrolyte forming composition, it can be handled in the same manner as the conventional electrolytic solution in the production process of the aluminum electrolytic capacitor, and can be used in the production of the aluminum electrolytic capacitor in the range of 50 to 17 times.
A gel electrolyte can be formed by heating at 0 ° C, generally 80 to 130 ° C.

If the 10-hour half-life temperature of the radical polymerization initiator is less than 50 ° C., if the liquid temperature rises during the distribution process in summer or the like, a polymerization reaction may take place, which may cause an increase in viscosity or gelation. In addition, it is necessary to review the heat resistance of members constituting the condenser and to change the heating process, which is not preferable.

The 10-hour half-life temperature of the radical polymerization initiator is more preferably from 80 to 130 ° C. from the viewpoint of the balance between the storage stability of the gel electrolyte-forming composition and the speed of gelation.

10 hour half-life temperature of radical polymerization initiator
Means that the radical polymerization initiator is heated and held at a certain temperature.
Temperature at which the amount is reduced by half in 10 hours.
Actual measurement is also possible (Nippon Oil & Fats Co., Ltd.,
Log) is the formula t representing the half-life _1/2 = (1 / k_d ) Ln
2 and Arrhenius equation, using the polymer data
The decomposition rate constant of the initiator described in the Handbook (Baifukan)
It can be calculated using the data.

Examples of the radical polymerization initiator having a 10-hour half-life temperature of 50 to 170 ° C. include benzoyl peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, dicumyl peroxide, di-t
Peroxide-based polymerization initiators such as -butyl peroxide, t-butyl hydroperoxide, t-butyl peroxybenzoate, and the like, 2,2'-azobis (2-isobutyronitrile), 2,2'-azobis Isobutyronitrile,
Azo-based polymerization initiators such as 2,2'-azobis (2,4-dimethylvaleronitrile) and 1,1'-azobis (cyclohexane-1-carbonitrile) can be used. These radical polymerization initiators may be used alone,
More than one species may be used in combination.

The amount of the thermal polymerization initiator to be added is not limited as long as a gel electrolyte can be obtained. ~ 5% by weight.

The radical polymerization initiator may be added to the gel electrolyte-forming composition from the beginning or may be added before use.

As the organic solvent constituting the electrolytic solution, one that can dissolve the electrolyte to a required concentration is used. Specifically, organic solvents having a high polarity, preferably liquid at room temperature, such as carbonate solvents, lactone solvents, and alcohol solvents are used.

Examples of the carbonate-based solvent include ethylene carbonate and propylene carbonate.

As the lactone solvent, specifically, γ-
Examples include butyrolactone, γ-valerolactone, δ-valerolactone, 3-methyl-1,3-oxazolidine-2-one, 3-ethyl-1,3-oxazolidine-2-one, and the like.

As the alcohol solvent, alcohols which are liquid at ordinary temperature can be used without limitation, and monoalcohols such as n-butanol, i-butanol and methyl cellosolve, and polyhydric alcohols such as ethylene glycol, propylene glycol and diethylene glycol are used. Are exemplified.

As a gel electrolyte for an aluminum electrolytic capacitor, use of a lactone solvent such as γ-butyrolactone or an alcohol solvent such as ethylene glycol is particularly preferred. When two or more organic solvents are used in combination,
It is also preferred that the mixture is liquid at room temperature.

If necessary, other organic solvents may be added to the above-mentioned solvents as long as their properties are not impaired. Examples of such organic solvents include pyrrolidone solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-
Amide solvents such as dimethylacetamide, ether solvents such as tetrahydrofuran, dioxane, 1,2-dimethoxyethane, dibutyl ether, acetonitrile, 3
A nitrile solvent such as -methoxypropionitrile,
Examples thereof include imidazolidinone solvents such as 3-dimethyl-2-imidazolidinone and sulfolane solvents such as sulfolane and 3-methylsulfolane. These may be used alone or in combination of two or more.
Of these non-aqueous solvents, the use of carbonate solvents, ether solvents and cyclic ether solvents is particularly preferred.

The gel electrolyte forming composition of the present invention and the electrolyte which is a component of the gel electrolyte may be an alkali metal salt, a quaternary ammonium salt, an alkaline earth metal salt, or the like, depending on the use of the obtained gel electrolyte. Is appropriately selected without limitation from the known electrolytes.

Specifically, examples of the alkali metal salt include:
For example, LiClO_Four , LiSCN, LiBF_Four , LiA
sF₆ , LiCF_Three SO_Three , NaI, NaSCN, Na
ClO_Four , NaBF_Four , NaAsF₆ , KSCN, etc.
I can do it. As the quaternary ammonium salt, (CH_Three )
_Four NBF_Four , (C_Two H_Five )_Four NBF_Four , (N-C_Four H
₉ )_Four NBF_Four , (C_Two H_Five )_Four NBr, (C_Two H_Five )
_Four NCLO_Four , (N-C _Four H₉ )_Four NCLO_Four Etc.
Can be Further, as the alkaline earth metal salt, for example,
Mg (ClO_Four )_Two , Ca (ClO_Four )_Two , Mg (BF
_Four )_Two , Ca (BF_Four )_Two , Imidazolium phthalate
Salts, quaternary polybasic acids such as quaternary ammonium phthalate
Ammonium salts. These electrolytes are used alone
May be used, or two or more kinds may be used in combination.

The amount of the electrolyte to be added to the organic solvent is not particularly limited as long as it functions as an electrolyte, and depends on the solubility of the electrolyte in the solvent.
２2 mol / L, preferably 0.7-1.5 mol
1 / L.

Examples of the manufacturing process of the aluminum electrolytic capacitor are shown in FIGS. FIG. 1 shows a process of fixing a terminal 13 connected to a lead wire 12 to an aluminum foil 11 to form an electrode material. The aluminum foil of the anode is
Usually, high-purity aluminum is used, and the surface is etched to form an oxide film. The aluminum foil of the cathode does not require high purity as required for the anode, and it is preferable to form an oxide film on the aluminum foil.

FIG. 2 shows an electrode manufacturing process in which the electrode materials 11A and 11C are wound around the separator 15 and formed into an electrode shape. FIG. 3 shows the resulting electrode 16.
This is an example.

In the case of using the gel electrolyte of the present invention, if a member for maintaining the interval between the electrodes is used, after gelation, the gel electrolyte also functions as a separator. You may.

When a separator is used, the impregnating step may not be a single step but may be an impregnating step of separately impregnating the separator with the gel electrolyte forming composition.

FIG. 4 shows a process in which the electrode 16 having the lead wire 12 is accommodated in the case 19 and covered with the rubber seal material 18.

The impregnating step is performed after the electrode 16 is formed and before it is housed in the case, after FIG. 3, or after the electrode is housed in the case and before the heating step.

The heating step is performed at a temperature in the range of 50 to 170 ° C., generally about 80 to 130 ° C., for about one hour. In the gel electrolyte forming composition, it is preferable to select a radical polymerization initiator, adjust the amount added, and the like so that the polymerization reaction is completed during this time.

The aluminum electrolytic capacitor 20 is the case 1
9 is formed by caulking (FIG. 5).

[0068]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiments and the like specifically showing the configuration and effects of the present invention will be described below. (Example 1) Methoxy polyethylene glycol monomethacrylate (trade name: Light ester 130MA, degree of polymerization of polyethylene glycol = 9, manufactured by Kyoeisha Chemical)
25 g, n-butyl methacrylate (manufactured by Nakarai)
Then, 0.5 g of polyethylene glycol dimethacrylate (trade name: Light Ester 9EG, polymerization degree of polyethylene glycol = 9, manufactured by Kyoeisha Chemical Co., Ltd.) was mixed at room temperature to obtain a monomer composition A as a polymerizable component. In 0.82 g of the polymerizable component A, 7 g of an electrolytic solution obtained by dissolving imidazolium phthalate as an electrolyte in γ-butyrolactone (GBL) at a concentration of 1 mol / L (weight ratio of electrolytic solution / polymerizable monomer = 8. 5/1), and 0.02 g of t-butyl peroxybenzoate (trade name: Perbutyl Z, manufactured by NOF Corporation) was added using radical polymerization as an initiator to obtain a gel electrolyte-forming composition (a). The obtained gel electrolyte forming composition (a) was to form a gel electrolyte by heating at 100 ° C. for 1 hour. The obtained gel electrolyte had an ionic conductivity of 5.2.
× 10 ⁻³ S / cm (20 ° C.), indicating good ionic conductivity. The gel electrolyte was heated at 125 ° C. and 10 ° C.
When the heat resistance test was performed for 00 hours, the gel shape was maintained even after the test, and high heat shape stability was exhibited.

Example 2 Methoxy polyethylene glycol monomethacrylate (trade name: Blemmer PME-
400, degree of polymerization of polyethylene glycol = 9, 0.25 g of Nippon Yushi, 0.07 g of n-butyl methacrylate (manufactured by Nakarai), polyethylene glycol dimethacrylate (trade name: Blenmer PDE-400, degree of polymerization of polyethylene glycol = 9) (Manufactured by NOF Corporation) at room temperature to obtain a monomer composition B as a polymerizable component. 7 g of an electrolyte obtained by dissolving imidazolium phthalate as an electrolyte in GBL at a concentration of 1 mol / L in 0.82 g of the polymerizable component B (electrolyte solution / polymerizable monomer weight ratio = 8.5 / 1); 0.02 g of perbutyl Z was added as a radical polymerization initiator to obtain a gel electrolyte forming composition (b). The obtained gel electrolyte forming composition (b) was to form a gel electrolyte by heating at 100 ° C. for 1 hour. The ion conductivity of the obtained gel electrolyte is 5.3 × 10 ⁻³ S / cm (20
° C), and showed good ionic conductivity. The gel electrolyte was subjected to a heat resistance test at 125 ° C. for 1000 hours. As a result, the gel shape was maintained even after the test, indicating high heat-resistant shape stability.

When the gel electrolyte forming composition of the present example was poured into the void formed without using the separator in the condenser and heated and cured, the ionic conductivity was as follows:
It improved to 9.3 × 10 ⁻³ S / cm (20 ° C.).

Example 3 0.91 g of polyethylene glycol monomethacrylate (trade name: Blemmer PE-200, manufactured by NOF Corporation) and 0.09 g of polyethylene glycol dimethacrylate (trade name: Light Ester 9EG, manufactured by Kyoeisha Chemical) were mixed. Thus, a monomer composition C as a polymerizable component was obtained. An electrolytic solution 7 in which 1 g of the polymerizable component C is dissolved in ethylene glycol so that a quaternary ammonium phthalate is dissolved at a concentration of 1 mol / L as an electrolyte.
g (electrolyte solution / polymerizable monomer weight ratio = 7/1) and 0.02 g of t-butyl peroxybenzoate (trade name: Perbutyl Z, manufactured by NOF Corporation) as a radical polymerization initiator were added to form a gel electrolyte-forming composition. A product (c) was obtained. The obtained gel electrolyte forming composition (c) was to form a gel electrolyte by heating at 125 ° C. for 1 hour. The ionic conductivity of the obtained gel electrolyte was 9.2.
× 10 ⁻⁴ S / cm (20 ° C.), indicating good ionic conductivity. The gel electrolyte was heated at 125 ° C. and 10 ° C.
When the heat resistance test was performed for 00 hours, the gel shape was maintained even after the test, and high heat shape stability was exhibited.

Example 4 0.96 g of polyethylene glycol monomethacrylate (trade name: Blemmer PE-200, manufactured by NOF Corporation) and 0.04 g of glycerin dimethacrylate (trade name: light ester G-101P, manufactured by Kyoeisha Chemical Co., Ltd.) By mixing, a monomer composition D as a polymerizable component was obtained. 7 g of an electrolytic solution obtained by dissolving a quaternary ammonium phthalate salt as an electrolyte in ethylene glycol at a concentration of 1 mol / L in 1 g of the polymerizable component D.
(Electrolyte solution / polymerizable monomer weight ratio = 7/1) and 0.02 g of perbutyl Z as a radical polymerization initiator were added to obtain a gel electrolyte-forming composition (d). The obtained gel electrolyte forming composition (d) was to form a gel electrolyte by heating at 125 ° C. for 1 hour.
The ionic conductivity of the obtained gel electrolyte was 9.5 × 10
⁻⁴ S / cm (20 ° C.), indicating good ionic conductivity. The gel electrolyte was heated at 125 ° C., 1
When a heat resistance test was performed for 000 hours, the gel shape was maintained even after the test, and high heat shape stability was exhibited.

Example 5 0.92 g of Blemmer PE
-200, trimethylolpropane trimethacrylate (trade name: Light Ester TMP, manufactured by Kyoeisha Chemical)
The polymerizable monomer composition E was obtained by mixing 0.08 g. 7 g of an electrolytic solution obtained by dissolving a quaternary ammonium phthalate salt as an electrolyte in ethylene glycol at a concentration of 1 mol / L in 1 g of the above polymerizable monomer composition E (electrolyte solution / polymerizable monomer weight ratio = 7/1) Then, 0.02 g of perbutyl Z was added as a radical polymerization initiator to obtain a gel electrolyte forming composition (e). The obtained gel electrolyte-forming composition (e) formed a gel electrolyte by heating and heating at 125 ° C. for 1 hour. The ionic conductivity of the obtained gel electrolyte was 9.3 × 10 ^−4.
S / cm (20 ° C.), indicating good ionic conductivity. The gel electrolyte was subjected to a heat resistance test at 125 ° C. for 1000 hours. As a result, the gel shape was maintained even after the test, indicating high heat-resistant shape stability.

Example 6 0.76 g of methacrylic acid and 0.24 g of polyethylene glycol dimethacrylate (trade name: Light Ester 9EG, manufactured by Kyoeisha Chemical Co., Ltd.) were mixed to obtain a polymerizable monomer composition F as a polymerizable component. Obtained. To 1 g of the polymerizable component F, 1 mol of quaternary ammonium phthalate was used as an electrolyte in ethylene glycol.
1 / L of an electrolyte solution dissolved to a concentration of 1 / L (weight ratio of electrolyte solution / polymerizable monomer = 7/1), and 0.02 g of perbutyl Z as a radical polymerization initiator were added thereto to form a gel electrolyte-forming composition ( f) was obtained. The obtained gel electrolyte forming composition (f) was to form a gel electrolyte by heating at 125 ° C. for 1 hour. The ionic conductivity of the obtained gel electrolyte is 9.7 × 10 ⁻⁴ S / cm.
(20 ° C.), showing good ionic conductivity. The gel electrolyte was subjected to a heat resistance test at 125 ° C. for 1000 hours. As a result, the gel shape was maintained even after the test, indicating high heat-resistant shape stability.

Example 7 Polyethylene glycol monomethacrylate (trade name: Blemmer PE-200, degree of polymerization of polyethylene glycol = 9, manufactured by NOF Corporation)
9 g and 0.1 g of polyethylene glycol dimethacrylate (trade name: Blenmer PDE-400, degree of polymerization of polyethylene glycol = 9, manufactured by NOF Corporation)
A monomer composition H as a polymerizable component was obtained. 8 g of an electrolytic solution prepared by dissolving imidazolium phthalate salt as an electrolyte in GBL at a concentration of 1 mol / L in 1 g of the polymerizable component H (electrolyte solution / polymerizable monomer weight ratio = 8/1), a radical polymerization initiator As a result, a gel electrolyte forming composition (h) was obtained by adding 0.02 g of benzoyl peroxide. The obtained gel electrolyte forming composition (h) was heated at 90 ° C.
For 1 hour to form a gel electrolyte. The ionic conductivity of the obtained gel electrolyte was 5.1 × 10 ⁻³ S / cm (20 ° C.), indicating good ionic conductivity. The gel electrolyte was subjected to a heat resistance test at 125 ° C. for 1000 hours. As a result, the gel shape was maintained even after the test, indicating high heat-resistant shape stability.

[Brief description of the drawings]

FIG. 1 shows a process of fixing a terminal to an aluminum foil to form an electrode material.

FIG. 2 is a diagram showing an electrode manufacturing process in which an electrode material is wound around a separator and formed into an electrode shape.

FIG. 3 shows an example of an electrode.

FIG. 4 is a view showing a process of accommodating an electrode having a lead wire in a case and covering with a rubber sealing material.

FIG. 5 is a diagram showing a configuration of an aluminum electrolytic capacitor.

 ────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Kimihiro Watanabe 1-17-18 Edobori, Nishi-ku, Osaka-shi, Osaka F-term in Toyo Tire & Rubber Co., Ltd. 4J002 BG041 BG051 BG071 BQ001 DD086 DE196 DK006 EY016 FD206 HA09 4J011 PA06 PA07 PA14 PA48

Claims (8)

[Claims] 1. An aluminum foil is processed into an electrode material.
An electrode manufacturing step of forming the electrode material into an electrode shape to form an electrode, an assembling step of disposing at least the electrode in a case, an impregnating step of impregnating a gel electrolyte forming composition, and a heating step, The impregnating step is provided after the electrode manufacturing step or after the assembling step.
Heating at 0 ° C., wherein the gel electrolyte forming composition contains a polymerizable monomer, an electrolytic solution, and a radical polymerization initiator, and forms a gel electrolyte by gelling in the heating step. Wherein the polymerizable monomer contains a monovinyl monomer and a polyvinyl monomer, and the monovinyl monomer contains an alkyl mono (meth) acrylate or an alkyl mono (meth) acrylate and a polyethylene glycol mono (meth) acrylate as main components, The polyvinyl monomer contains polyethylene glycol di (meth) acrylate as a main component, and the alkyl mono (meth)
A method for producing a gel electrolyte for an aluminum electrolytic capacitor, wherein the acrylate is mainly composed of an alkyl mono (meth) acrylate having an alkyl group having 3 or more carbon atoms. 2. The polyethylene glycol di (meth)
Acrylate content is 5 to 70 mol% of all monomers
The method for producing a gel electrolyte for an aluminum electrolytic capacitor according to claim 1, wherein 3. The aluminum electrolytic according to claim 1, wherein the monovinyl monomer has an alkyl mono (meth) acrylate / polyethylene glycol mono (meth) acrylate ratio of 100/0 to 5/95 (molar ratio). A method for producing a gel electrolyte for a capacitor. 4. An aluminum foil is processed into an electrode material.
An electrode manufacturing step of forming the electrode material into an electrode shape to form an electrode, an assembling step of disposing at least the electrode in a case, an impregnating step of impregnating a gel electrolyte forming composition, and a heating step, The impregnating step is provided after the electrode manufacturing step or after the assembling step.
Heating at 0 ° C., wherein the gel electrolyte forming composition contains a polymerizable monomer, an electrolytic solution, and a radical polymerization initiator, and forms a gel electrolyte by gelling in the heating step. Wherein the polymerizable monomer contains a monovinyl monomer and a polyvinyl monomer, and the monovinyl monomer contains, as a main component, at least one of a hydroxyl group-containing mono (meth) acrylate and a carboxyl group-containing mono (meth) acrylate. Is bifunctional or more (meta)
A method for producing a gel electrolyte for an aluminum electrolytic capacitor, comprising acrylate as a main component. 5. The bifunctional or higher functional (meth) acrylate is polyethylene glycol di (meth) acrylate,
It is at least one selected from glycerin di (meth) acrylate and trimethylolpropane tri (meth) acrylate, and the content of the bifunctional or higher-functional (meth) acrylate is 1 to 50 mol% in all monomers. Item 5. The method for producing a gel electrolyte for an aluminum electrolytic capacitor according to Item 4. 6. The hydroxyl-containing mono (meth) acrylate is a hydroxyl-terminated polyethylene glycol mono (meth).
20 mol% of acrylate in the monovinyl monomer
The method for producing a gel electrolyte for an aluminum electrolytic capacitor according to claim 4 or 5, which contains the above. 7. The method for producing a gel electrolyte for an aluminum electrolytic capacitor according to claim 1, wherein the impregnation step involves a pressure reduction step. 8. The aluminum electrolytic capacitor according to claim 1, wherein said polymerizable monomer and said electrolytic solution are blended in an electrolytic solution / polymerizable monomer ratio of 6/1 to 15/1. Method for producing gel electrolyte for use.