CN1723515A - Solid electrolytic capacitor and process for producing the same - Google Patents

Abstract

A cathode foil and an anode foil, with an oxidized film layer formed on the surface and a separator interposed therebetween, are wound together to form a capacitor element, and prior to subjecting the capacitor element to chemical repair the content of the binder in the separator is adjusted to 10 to 20% with respect to the total weight of the separator. After the chemical repair, the capacitor element is immersed in mixed liquid prepared by mixing a polymerizable monomer and an oxidizing agent together with a predetermined solvent, a polymerization reaction of the electroconductive polymer is induced in the capacitor element, and a solid electrolyte layer is formed. The capacitor element is then inserted in an outer case; sealing rubber is mounted in the open-end portion and sealed with a tightening operation; and the unit is thereafter aged to form a solid electrolytic capacitor.

Description

Solid electrolytic capacitor And Manufacturing approach

Technical field

The present invention relates to Solid electrolytic capacitor And Manufacturing approach, particularly a kind of Solid electrolytic capacitor And Manufacturing approach of being devoted to reduce ESR, improving electrostatic capacitance and raising proof voltage.In addition, also relate to and a kind ofly be devoted to improve proof voltage, suppress the Solid electrolytic capacitor And Manufacturing approach that the LC behind the anti-stream (reflow) changes.

Technical background

For using this electrolytic capacitors such as tantalum or aluminium with metal of valve action, make the shape that becomes sintered body or etched foil etc. as the valve metals of anode-side counter electrode, dielectric is expanded faceization, can realize small-sized thus and capacitor big electric capacity, therefore be widely used usually.Particularly use solid electrolyte to be used as electrolytical solid electrolytic capacitor, except aspects such as small-sized, big electric capacity, low equivalent series resistance, also have easy chipization, be suitable for characteristic such as mounted on surface, so it becomes miniaturization, multifunction, the indispensable element of cost degradation of realizing electronic equipments.

About this solid electrolytic capacitor, as purposes small-sized, big electric capacity, generally has following structures: between anode foils that forms by valve metals such as aluminium and Cathode Foil, insert division board, then with its surrounded formation capacitor element, driving electrolytic solution is impregnated in this capacitor element, capacitor element is contained in the metallic housing or synthetic resin system housing of aluminium etc., seals.In addition, as anode material, be representative with aluminium, can also use tantalum, niobium, titanium etc., cathode material uses the metal identical with anode material.

In addition, as the solid electrolyte that is used for solid electrolytic capacitor, known have manganese dioxide and 7,7,8,8-four cyano quinone bismethane (TCNQ) complex compound, in recent years, also occurred being conceived to reaction speed slowly and with the technology (spy opens flat 2-15611 communique) of the good poly-ethylidene dioxy thiophene electric conductive polymers such as (following note are made PEDT) of the adaptation of the oxidation film layer of anode electrode.

The such solid electrolytic capacitor that forms the solid electrolyte of being made up of electric conductive polymers such as PEDT in the circulating type capacitor element is made as shown in Figure 5.At first, the surface of the anode foils that is formed by valve metals such as aluminium makes its surface roughening by the electrochemical etch process in aqueous chloride solution, after forming a plurality of etch pits, in addition voltage forms as dielectric oxidation film layer (changing into) in the aqueous solution of ammonium borate etc.With anode foils similarly, cathodic coating is also formed by valve metals such as aluminium, but only etch processes is carried out on its surface.

So, formed the anode foils of oxidation film layer on the surface and only formed between the Cathode Foil of etch pit the surrounded formation capacitor element of insertion division board.Then, with 3,4-ethylidene dioxy thiophene polymerizable monomers such as (following note are made EDT) and oxidizing agent solution are ejected to respectively have been implemented to repair on the capacitor element that changes into, perhaps be immersed in the two the mixed liquor, promote the polymerization reaction in the capacitor element, generate the solid electrolyte layer that forms by electric conductive polymers such as PEDT.Then, this capacitor element is housed in the shell basket of bottom tube-like, makes solid electrolytic capacitor.

Summary of the invention

In addition, in recent years, above-mentioned this solid electrolytic capacitor also is used to vehicle-mounted purposes.Usually the driving voltage of vehicle mounted circuit is 12V, therefore needs the high withstand voltage of 25V for solid electrolytic capacitor.Yet when making the product of this high withstand voltage by above-mentioned this existing manufacture method, it is higher to have a probability that is short-circuited in etching work procedure, the shortcoming that productive rate is lower.

In addition, in recent years, owing to environmental problem is used dystectic leadless soft soldering, thereby the anti-temperature that flows of solder reaches 230～270 ℃ from 200～220 ℃ of further high temperatureization.Yet, if causing under this high temperature that solder is counter flows, have the shortcoming that proof voltage reduces, therefore, even wish to develop a kind of when the anti-stream of the soft pin weldering of high temperature, the solid electrolytic capacitor that voltage-resistent characteristic can variation yet.

In addition, this problem is not limited to EDT as the situation of polymerizable monomer, can take place too when the thiophene derivant that uses other, pyrroles, aniline etc.

The 1st purpose of the present invention provides a kind of Solid electrolytic capacitor And Manufacturing approach that can lower ESR and improve electrostatic capacitance.

The 2nd purpose of the present invention provides a kind of Solid electrolytic capacitor And Manufacturing approach that can lower ESR, improve electrostatic capacitance and raising proof voltage.

The 3rd purpose of the present invention provides a kind of can preventing because the deterioration of the voltage-resistent characteristic that causes of unleaded anti-stream, can improve the Solid electrolytic capacitor And Manufacturing approach of the productive rate when making the high withstand voltage product.

The 4th purpose of the present invention provides the Solid electrolytic capacitor And Manufacturing approach that a kind of LC that can realize improving after proof voltage, inhibition are instead flowed changes.

The present invention is directed to the solid electrolytic capacitor that uses the division board that contains compound,, can lower ESR and improve electrostatic capacitance by adjusting the content that contains vinyl compound contained in the division board aptly with vinyl.

In addition, the solid electrolytic capacitor that contains the division board of compound for use with vinyl, before closing oxidant at the impregnation polymerizable monomer, make capacitor element contain the coupling agent or the surfactant of ormal weight, ESR be can reduce, electrostatic capacitance and proof voltage improved.

And then, at the solid electrolytic capacitor that contains division board for use with vinyl compound, by additive solutions such as impregnation boronic acid compounds in capacitor element, the combination that generation is formed by additives such as compound that contains vinyl and boronic acid compounds, form the solid electrolyte layer of forming by electric conductive polymer then, can prevent like this because the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes improves the productive rate when making the high withstand voltage product.

In addition, contain the solid electrolytic capacitor of the division board of compound,, form the film that forms by compound that contains vinyl and polyimides silicon by being immersed in the capacitor element in the polyimides silicon solution with vinyl for use.Can improve proof voltage, the LC change after suppressing instead to flow.

Brief Description Of Drawings

Fig. 1 is the figure of the structural formula of expression thiophene derivant, Fig. 2～Fig. 4 is the flow chart of an example of the manufacturing process of expression solid electrolytic capacitor of the present invention, and Fig. 5 is the flow chart of an example of manufacturing process of the solid electrolytic capacitor of expression prior art.

Embodiment

(A) the 1st execution mode

Present inventors have carried out conscientious research in order to reach above-mentioned the 1st purpose, found that by constitute the adhesive of division board by the compound that contains vinyl, and its content is 10～20% of division board total weight, can improve electrostatic capacitance when lowering ESR.

That is to say, present inventors have made various changes to the content of the adhesive that formed by the compound that contains vinyl and have studied, and find that then ESR, electrostatic capacitance characteristic reduce if surpass above-mentioned scope, if not enough above-mentioned scope then has fixing characteristic.

(A-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 1st execution mode is as described below.Promptly formed between the anode foils and Cathode Foil of oxidation film layer on the surface, insertion contains the division board of the adhesive that is formed by the compound that contains vinyl, carry out around forming capacitor element, this capacitor element is implemented to repair change into before, the binder content in the division board is adjusted to make its total weight with respect to division board be 10～20%.

Then, after reparation changes into, this capacitor element is immersed in by in polymerizable monomer and oxidant and the specified solvent mixed together liquid mixture prepared, the polymerization reaction of electric conductive polymer takes place in capacitor element, form solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

(A-2) division board

Usually, the solid electrolytic capacitor division board based on synthetic fibers is to be made of synthetic fibers and the adhesive that engages.As this adhesive, can use this synthetic resin itself, or synthetic resin be made fibrous, in the manufacturing process of division board, make it fusion and engage with main fibre.

In the 1st execution mode, use has the compound of vinyl as adhesive, the content that made above-mentioned adhesive in the division board before reparation changes into is 10～20% with respect to the total weight of division board, more preferably 13～17%, and use such division board can obtain good result.

Wherein, as compound, can use polyvinyl alcohol (PVA), polyvinyl acetate, PVP, polyacrylamide etc., especially more preferably PVA with vinyl.In addition, as the main fibre of division board, the polyester fiber or the nylon fiber of preferred excellent heat resistance.On the other hand, therefore the division board that is formed by vinylon fiber is inappropriate owing to can not satisfy unleaded anti-properties of flow.

Then, the method that the binder content in the division board is adjusted to above-mentioned scope before reparation changes into is described.As the 1st kind of method, the adhesive that will be formed by the compound that contains vinyl and the main fibre mixed together of division board are the content of 10～20 weight % so that it reaches with respect to division board.

In addition,, the division board that contains the adhesive that is formed by the compound that contains vinyl more than 10% can be handled by warm water immersion, be made the adhesive dissolving in the division board, obtain and it is adjusted in the above-mentioned scope as the 2nd kind of method.

When warm water was handled dipping, warm water temperature was preferably 60～100 ℃ of solubilized PVA etc., and the warm water immersion time is 5～180 minutes, more preferably 20～60 minutes.In addition, if warm water immersion is handled the dissolution velocity of carrying out improving PVA etc. in the mode of flowing water, in addition can uniform dissolution, therefore preferred.

This warm water immersion is handled and is preferably carried out after capacitor element forms.Handle if before capacitor element forms, carry out warm water immersion because the intensity of division board reduces, then around the time reduce around the intensity of volume, the formation state variation of the electric conductive polymer in the capacitor element, characteristic reduces.

(A-3) EDT and oxidant

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., wherein especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～58 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, specially suitable is ethanol.Think that ethanol is that the solvent that is particularly suitable as oxidant is because its steam forces down easy evaporation, so residual quantity is less.

(A-4) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into that changes into adipic acid classes such as liquid, ammonium adipate that changes into boric acid classes such as liquid, ammonium borate of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, wherein especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(A-5) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT, and can form the material of electric conductive polymer by certain oxidant oxidation polymerization, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(A-6) effect of the 1st execution mode, effect

As mentioned above, use and to contain the adhesive of the compound of vinyl as division board, the content by making adhesive before changing in reparation is 10～20% with respect to the total weight of division board, and it is as follows to do the reason that can obtain good result like this.That is to say that use the division board of content in this scope of adhesive to compare with the maintenance dose of the electric conductive polymers such as PEDT that use the division board formation that surpasses this scope, it is constant.On the other hand, when the division board of the content that uses adhesive in this scope, the characteristic of solid electrolytic capacitor improves, and when using the division board that surpasses this scope, the characteristic of solid electrolytic capacitor reduces.

Thus, think in the process that forms electric conductive polymers such as PEDT, a large amount of exist as adhesive ingredients contain the compound of vinyl the time, this compound can produce harmful effect to the formation of PEDT, and is in the state of original characteristic such as the electric conductive polymer that can not get PEDT (electrostatic capacitance, ESR).On the other hand, think, can obtain good result by suitably adjusting the amount that vinyl compound is arranged as adhesive ingredients.

(A-7) embodiment of the 1st execution mode

Then, according to the embodiment A 1～A5 and the Comparative examples A 1 of following manufacturing, the invention of the 1st execution mode is described in detail.

(embodiment A 1)

Use with the PET fiber as main fibre, contain the division board of 15% adhesive that forms by PVA, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil that the surface formed oxidation film layer, and surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 5 φ * 2.8L.Then, this capacitor element was flooded 20 minutes in 100 ℃ warm water, the binder content after warm water immersion is handled is adjusted to 13%.This capacitor element flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.

On the other hand, in the container of regulation, mix the ethanolic solution of the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, 120 ℃ of heating 60 minutes, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer.

Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 8.2V carries out 120 minutes etching, forms solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 6.3WV, rated capacity are 120 μ F.

(embodiment A 2)

Use contains the division board of 25% adhesive that is formed by PVA, after forming capacitor element in 100 ℃ warm water dipping 20 minutes, the binder content after warm water immersion handled is adjusted to 14%.Other condition is identical with embodiment A 1 with operation.

(embodiment A 3)

Use contains the division board of 30% adhesive that is formed by PVA, after forming capacitor element in 100 ℃ warm water dipping 10 minutes, the binder content after warm water immersion handled is adjusted to 20%.Other condition is identical with embodiment A 1 with operation.

(embodiment A 4)

Use contains the division board of 30% adhesive that is formed by PVA, after forming capacitor element in 100 ℃ warm water dipping 20 minutes, the binder content after warm water immersion handled is adjusted to 15%.Other condition is identical with embodiment A 1 with operation.

(embodiment A 5)

Use contains the division board of 15% adhesive that is formed by PVA, handles and repairs and change into without warm water immersion.Other condition is identical with embodiment A 1 with operation.

(Comparative examples A 1)

Use contains the division board of 30% adhesive that is formed by PVA, handles and repairs and change into without warm water immersion.Other condition is identical with embodiment A 1 with operation.

[comparative result]

Embodiment A 1～the A5 that obtains by said method and the initial stage characteristic of Comparative examples A 1 are studied, obtain result as shown in table 1.

[table 1]

	Binder content (%)	Dip time in the warm water (minute)	Binder content after the impregnation process (%)	The initial stage characteristic
						Cap (μF)	ESR (Ω/100kHz)
				Embodiment A 1	15			20	13	141	0.0185
Embodiment A 2	25	20	14			139	0.0185
				Embodiment A 3	30			10	20	130	0.0200
Embodiment A 4	30	20	15			138	0.0186
				Embodiment A 5	15			-	15	138	0.0187
Comparative examples A 1	30	-	30			120	0.0215

As can be seen from Table 1, use the embodiment A 1 of the division board contain 15% adhesive that is formed by PVA and embodiment A 5 relatively, the electrostatic capacitance, the ESR that carry out the embodiment A 1 of warm water immersion processing have obtained good result.

In addition, use contains the embodiment A 3 of division board of 30% adhesive that is formed by PVA and embodiment A 4 and Comparative examples A 1 relatively, and embodiment A 3 and embodiment A 4 are all obtaining better result than the Comparative examples A 1 of not carrying out the warm water immersion processing aspect electrostatic capacitance, the ESR.

And the electrostatic capacitance and the ESR of the embodiment A 4 that the warm water immersion time is long are good than embodiment A 3 results.

(B) the 2nd execution mode

Present inventors have carried out conscientious research in order to reach above-mentioned the 2nd purpose, found that to contain and contain the division board of vinyl compound more than the 10 weight % as adhesive by use, before impregnation polymerizable monomer and oxidant, by making the coupling agent that contains regulation in the capacitor element, obtain a kind of ESR that can realize lowering, improve the Solid electrolytic capacitor And Manufacturing approach of electrostatic capacitance and raising proof voltage.

(B-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 2nd execution mode is as described below.Promptly form between the anode foils and Cathode Foil of oxidation film layer on the surface, insertion contains and contains the division board of the compound of vinyl as adhesive more than the 10 weight %, carries out around forming capacitor element, this capacitor element is implemented to repair change into.Then, make its coupling agent that contains regulation after, this capacitor element is impregnated in the mixed liquor of polymerizable monomer and oxidant, the polymerization reaction of electric conductive polymer takes place in capacitor element, form solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

In addition, make before it contains coupling agent, be more preferably and make it contain boronic acid compounds earlier.

(B-2) division board

Usually, the solid electrolytic capacitor division board based on synthetic fibers is to be made of synthetic fibers and the adhesive that engages.As this adhesive, can use this synthetic resin itself, or synthetic resin be become fibrous, in the manufacturing process of division board, make it fusion and engage with main fibre.In the present invention, use will contain the division board of vinyl compound as adhesive.

Wherein, as compound, can use polyvinyl alcohol (PVA), polyvinyl acetate, PVP, polyacrylamide etc., especially more preferably PVA with vinyl.

In addition, as the main fibre of division board,, therefore preferred if synthetic fibers such as the polyester fiber of use excellent heat resistance or nylon fiber can improve thermal endurance.In addition, the content of the adhesive that forms by the compound that contains vinyl with respect to division board preferably more than 10 weight %.If less than 10 weight % then can not get effect of sufficient.

(B-3) coupling agent

As coupling agent, can use following silane coupler, as titanium coupling agent, aluminum coupling agent, can use to be selected from the wherein coupling agent more than a kind or 2 kinds.

In addition, as making the method that contains these coupling agents in the capacitor element, can be after reparation changes into, capacitor element was flooded several minutes in 0.1～5%, preferred 0.5～3% coupling agent aqueous solution, mention the back 50～100 ℃ of dry down methods.

As above-mentioned silane coupler, that can enumerate has a vinyl trichlorosilane, vinyl (β methoxy silane) vinyltriethoxysilane, vinyltrimethoxy silane, vinyl three (β methoxy ethoxy) silane, the rare acyloxy silane of γ-methyl-prop, the rare acyloxy propyl group of γ-methyl-prop methyl dimethoxysilane, the rare acyloxy propyl-triethoxysilicane of γ-methyl-prop, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrime,hoxysilane, γ-glycidoxy propyl group methyldiethoxysilane, N-β (aminoethyl) γ-aminopropyl methoxy silane, gamma-aminopropyl-triethoxy-silane, N-phenyl-γ-aminopropyl methoxy silane, γ-sulfydryl propyl group methoxy silane, γ-r-chloropropyl trimethoxyl silane.

In addition; as titanium coupling agent; what can enumerate is isopropyl three iso stearate base titanate esters; isopropyl three (dioctyl pyrophosphite) titanate esters; isopropyl three (N-aminoethyl-aminoethyl) titanate esters; isopropyl three decyl benzenesulfonyl titanate esters; four octyl groups two (double tridecyl phosphite ester) titanate esters; four (2,2-two allyloxy methyl isophthalic acid-butyl) two (two-tridecyl) phosphite ester titanate esters; two (dioctyl pyrophosphite) fluoroacetic acid ester titanate esters; two (dioctyl pyrophosphite) ethylidene titanate esters; isopropyl three caprylyl titanate esters; isopropyl dimethyl propylene acyl group iso stearate base titanate esters; isopropyl three cumyl phenyl titanium acid esters.

Further, as aluminum coupling agent, that can enumerate has an acetyl aluminum alkoxide diiso propoxide.

(B-4) boronic acid compounds

As boronic acid compounds, can use boric acid, borax, borates such as the ammonium salt of boric acid, slaine, borates such as triethyl borate especially preferably use boric acid.

In addition, as the solvent of these boronic acid compounds, can be the material of these compounds of solubilized, can mainly make water, glycerine etc.In addition, the concentration of boronic acid compounds solution is preferably 0.1 weight %～10 weight %, more preferably 3 weight %～7 weight %.When the concentration of boronic acid compounds solution was beyond this scope, effect reduced.Its reason is, if the concentration less than 0.1 weight % of boronic acid compounds solution, because the boronic acid compounds in the solution is less, the amount of the combination that forms is insufficient, on the other hand, if surpass 10 weight %, though agnogenio, supposition may be that ESR rises owing to remaining boric acid after forming combination produces harmful effect.

In addition,, can use capacitor element is immersed in method in the solution of boronic acid compounds, perhaps the solution of boronic acid compounds is ejected to the method on the capacitor element as making capacitor element contain the method for above-mentioned boronic acid compounds.

In addition, make capacitor element contain boronic acid compounds after, if heat treated can improve the initial stage characteristic.Its reason is that the compound stripping that contains vinyl contained in the division board by increasing the hydrophobicity of its end group, can improve the adaptation of oxide-film and solid electrolyte in capacitor element.In addition, this heating-up temperature is preferably 120～250 ℃, more preferably 150～200 ℃.When heating-up temperature was beyond this scope, effect reduced.Its reason is, when 120 ℃ of heating-up temperature less thaies, can not fully promote to contain the reaction of hydrophobization etc. of the end group of vinyl compound, on the other hand, if surpass 250 ℃, causes the thermal degradation when that contains vinyl compound and effect is reduced.

(B-5) EDT and hydrogenant agent

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～65 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, suitable is ethanol.Think that ethanol is that the solvent that is suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(B-6) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, wherein preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(B-7) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivatives beyond the EDT, and can form the material of electric conductive polymer by certain oxidant oxidation polymerization, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(B-8) effect of the 2nd execution mode, effect

Formation with above-mentioned the 2nd execution mode can realize that the reason that lowers ESR, raising electrostatic capacitance and improve proof voltage is, the PVA of dissolving was attached on the dielectric film during reparation changed into, after making it contain coupling agent then, form PEDT, increase the adhesiveness of PVA and PEDT, improve electrostatic capacitance and ESR.

Further, PVA dissolves from division board in reparation changes into, and the space of division board increases, and the maintenance dose of the PEDT of division board increases thus, and ESR lowers.In addition, attached to the PVA on the dielectric film invasion and attack of the dielectric film that residues in the oxidant among the PEDT are weakened, proof voltage improves.

Further, think, form the combination with boric acid on the surface of PVA, further increased adherence with PEDT by synergy with coupling agent if make it contain boric acid.In addition, if PVA contain quantity not sufficient 10 weight % then these effects lower.

(R-9) related embodiment of the 2nd execution mode

Then, according to the embodiment and the existing example of following manufacturing, the invention of present embodiment is described in detail.

(Embodiment B 1)

Use with the PET fiber as main fibre, contain more than the 10 weight % division board as the PVA of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil that the surface formed oxidation film layer, surrounded after inserting above-mentioned division board between two electrode foils, form capacitor element.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element after 100 ℃ of following dryings, was flooded several minutes in 5 weight % boric acid aqueous solutions at normal temperatures, drying is 1 hour under 150 ℃.In addition, flooded at normal temperatures 1 minute in 1 weight %N-β (aminoethyl) γ-aminopropyl methoxy silane aqueous solution, drying is 1 hour under 80 ℃.

On the other hand, in the container of regulation, mix the ethanolic solution of the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, 120 ℃ of heating 60 minutes, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer.Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 5.2V carries out 120 minutes etching, forms solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 2.5WV, rated capacity are 180 μ F.

(Embodiment B 2)

Except not carrying out the dipping in the boric acid aqueous solution, other condition is identical with Embodiment B 1 with operation.

(comparative example B1)

Except do not carry out in boric acid aqueous solution and coupling agent in dipping, other condition and operation and

Embodiment B 1 is identical.

[comparative result]

Initial stage characteristic to the Embodiment B 1, Embodiment B 2 and the comparative example B1 that obtain by said method is studied, and obtains result as shown in table 2.

[table 2]

	The boric acid dipping	The silane coupler dipping	The initial stage characteristic
					Cap (μF)	ESR (Ω/100kHz)
			Embodiment B 1	Have			Have	152	0.021
Embodiment B 2	Do not have	Have			143	0.021
			Comparative example B1	Do not have			Do not have	132	0.023

As can be seen from Table 2, to all not have to flood in boric acid, and compare with comparative example B1 but impregnated in aspect the coupling agent different Embodiment B 2 whether, the Embodiment B 2 that contains coupling agent be compared with comparative example B1, electrostatic capacitance is increased to about 1.08 times, and ESR is reduced to about 91%.Further, making its Embodiment B that contains boric acid 1 compare electrostatic capacitance with Embodiment B 2 further increases.

In addition, will not contain relatively the short-circuit voltage 20V that risen as the division board of the PVA of adhesive and the situation of using it.

(C) the 3rd execution mode

Present inventors have carried out conscientious research repeatedly in order to reach above-mentioned the 2nd purpose, found that to contain and contain the division board of vinyl compound more than the 10 weight % as adhesive by use, before impregnation polymerizable monomer and oxidant, contain a kind or 2 kinds that is selected from ethinylation glycol, the cacodyl oxide base bay alkylamine in the capacitor element by making, can obtain a kind of ESR that can realize lowering, improve the Solid electrolytic capacitor And Manufacturing approach of electrostatic capacitance and raising proof voltage.

(C-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 3rd execution mode is as described below.Promptly formed between the anode foils and Cathode Foil of oxidation film layer on the surface, insertion contains and contains the division board of the compound of vinyl as adhesive more than the 10 weight %, carries out around forming capacitor element, this capacitor element is implemented to repair change into.Then, make contain a kind or 2 kinds that is selected from ethinylation glycol, the dimethyl lauryl amine oxide in the capacitor element after, this capacitor element is impregnated in the mixed liquor of polymerizable monomer and oxidant, the polymerization reaction of electric conductive polymer takes place in capacitor element, forms solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

(C-2) division board

Usually, the solid electrolytic capacitor division board based on synthetic fibers is to be made of synthetic fibers and the adhesive that engages.As this adhesive, can use synthetic resin itself, or synthetic resin be become fibrous, in the manufacturing process of division board, make it fusion and engage with main fibre.In the present invention, use will contain the division board of vinyl compound as adhesive.

Wherein, as compound, can use polyvinyl alcohol (PVA), polyvinyl acetate, PVP, polyacrylamide etc., especially more preferably PVA with vinyl.

In addition, as the main fibre of division board,, therefore preferred if synthetic fibers such as the polyester fiber of use excellent heat resistance or nylon fiber can improve thermal endurance.In addition, the content of the adhesive that forms by the compound that contains vinyl with respect to division board preferably more than 10 weight %.If less than 10 weight % then can not get effect of sufficient.

(C-3) additive

As additive, find to use in ethinylation glycol, the dimethyl lauryl amine oxide a kind or 2 kinds of being selected from as surfactant, it is contained in the capacitor element, can improve electrostatic capacitance, lower ESR.Think that its reason is the adhesive increase between PVA and the PEDT.

In addition, as making the method that contains these additives in the capacitor element, preferably after reparation changes into, at normal temperatures capacitor element is immersed in 0.1～10%, in preferred 0.5～2% the aqueous solution, after 50～90 ℃ of following dryings, 150～200 ℃ of following methods of heating treatment.Think by heating, improved the cross-linked state of PVA, PEDT, surfactant, increased adaptation.

(C-4) EDT and oxidant

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～65 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, suitable is ethanol.Think that solvent that ethanol is suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(C-5) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(C-6) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT can form the material of electric conductive polymer by certain oxidant oxidation polymerization, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(C-7) effect of the 3rd execution mode, effect

Formation with above-mentioned the 3rd execution mode can realize that the reason that lowers ESR, raising electrostatic capacitance and improve proof voltage is, the PVA of dissolving was attached on the dielectric film during reparation changed into, after making it contain coupling agent then, form PEDT, increase the adhesiveness of PVA and PEDT, improve electrostatic capacitance and ESR.

Further, PVA dissolves from division board in reparation changes into, and the space of division board increases, and the maintenance dose of the PEDT of division board increases thus, and ESR lowers.In addition, attached to the PVA on the dielectric film invasion and attack of the dielectric film that residues in the oxidant among the PEDT are weakened, proof voltage improves.In addition, if PVA contain quantity not sufficient 10 weight %, then these effects reduce.

(C-8) related embodiment of the 3rd execution mode

Then, according to the embodiment and the existing example of following manufacturing, the invention of the 3rd execution mode is described in detail.

(Embodiment C 1)

Use with the PET fiber as main fibre, contain more than the 10 weight % division board as the PVA of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil that the surface formed oxidation film layer, surrounded after inserting above-mentioned division board between two electrode foils, form capacitor element.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element after 100 ℃ of following dryings, was flooded 3 minutes in the 1 weight % aqueous solution of ethinylation glycol, after 60 ℃ of following dryings, 170 ℃ of heating at normal temperatures.

On the other hand, in the container of regulation, mix the ethanolic solution of the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, kept 60 minutes at 120 ℃, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer.Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 5.2V carries out 120 minutes etching, forms solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 4WV, rated capacity are 180 μ F.

(Embodiment C 2)

After reparation changes into, this capacitor element after 100 ℃ of following dryings, was flooded 3 minutes in the 1 weight % aqueous solution of dimethyl lauryl amine oxide, after 60 ℃ of following dryings, 170 ℃ of heating at normal temperatures.Its condition is identical with Embodiment C 1 with operation.

(comparative example C1)

Except not adding additive, other condition is identical with Embodiment C 1 with operation, makes solid electrolytic capacitor.

[comparative result]

Initial stage characteristic to the Embodiment C 1, Embodiment C 2 and the comparative example C1 that obtain by said method is studied, and obtains result as shown in table 3.

[table 3]

	Additive	The initial stage characteristic
				Cap (μF)	ESR (mΩ/100kHz)
		Embodiment C 1	The ethinylation glycol			80	18.5
Embodiment C 2	The dimethyl lauryl amine oxide			75	19.0
		Comparative example C1	Do not have			71	20.5

As can be seen from Table 3, the Embodiment C 1 of use additive is compared electrostatic capacitance with Embodiment C 2 with comparative example C1 and is all increased, and ESR lowers.

Contain relatively the short-circuit voltage 20V that risen in addition and not as the situation of the division board of the PVA of adhesive.

(D) the 4th execution mode

Present inventors are in order to reach above-mentioned the 3rd purpose, and to when making the product of high withstand voltage, the reason that the ratio that is short-circuited in etching work procedure raises has been carried out various research, drawn following conclusion.That is to say, think common in having formed the capacitor element behind the electric conductive polymer, except electric conductive polymer, also exist and irrelevant monomer or oxidant and other reaction residue of polymerization reaction.Thereby because the proof voltage of the material beyond these electric conductive polymers is lower than the proof voltage of electric conductive polymer, so these materials reduce the proof voltage of solid electrolytic capacitor.

Therefore, even present inventors are in order to realize having these reaction residue, the proof voltage of solid electrolytic capacitor is improved, can prevent simultaneously because the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes, carried out research repeatedly, found that the division board formation capacitor element that contains vinyl compound by use, make in this capacitor element and contain boronic acid compounds, can improve the proof voltage of solid electrolytic capacitor.

(D-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 4th execution mode is as described below.Promptly formed between the anode foils and Cathode Foil of oxidation film layer, inserted the division board of the compound that contains vinyl, carried out this capacitor element being implemented reparation changing into around forming capacitor element on the surface.Then, the solution of impregnation boronic acid compounds in this capacitor element, generation is by containing the combination that vinyl compound and boronic acid compounds form, afterwards, this capacitor element is immersed in by in the formulated mixed liquor of polymerizable monomer and oxidant and certain solvent, the polymerization reaction of electric conductive polymer takes place in capacitor element, forms solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

(D-2) division board

Usually, the solid electrolytic capacitor division board based on synthetic fibers is to be made of synthetic fibers and the adhesive that engages.As this adhesive, can use synthetic resin itself, or synthetic resin be become fibrous, in the manufacturing process of division board, make it fusion and engage with main fibre.In the present invention, by will containing main fibre or the adhesive that vinyl compound is used for this division board, and use this division board, obtained good result.

In addition, the necessary amount that contains vinyl compound contained in the main fibre of division board or the adhesive is got final product for trace, even but increase its effect and also can not lower.Its reason is, because can reach effect of the present invention contained containing after the vinyl compound stripping attached on the oxide-film in the division board.Thereby, also can as the vinylon division board, form by 100% vinylon fiber.At this moment, for fear of in manufacturing process, the intensity of division board being reduced, can control stripping quantity owing to containing the excessive stripping of vinyl compound.In addition, in typical case of the present invention, be that at this moment, for the intensity that obtains stipulating, its content is preferably 10～20 weight % with the division board of PVA as adhesive.

Wherein, as compound, can use polyvinyl alcohol (following note is made PVA), polyvinyl acetate, PVP, polyacrylamide etc., especially more preferably PVA with vinyl.Specifically, the vinylon of PVA fiber (vinylon) or not stretching can be used for the main fibre of division board, also PVA polymer or the vinylon that does not stretch can be used for adhesive.For example, can adopt with fibre diameter be the vinylon fiber of 3.0～12.0 μ m as short fiber with regulation Cutting Length, will use the adhesive of regulation, form the material of nonwoven fabrics by means arbitrarily.

In addition, as making the method that contains vinyl compound in the division board, except aforesaid by containing method that vinyl compound constitutes main fibre or adhesive (in other words, be to make to contain the method that vinyl compound contains as the constituent of division board) in addition, can also use division board is immersed in method in the solution that contains vinyl compound, coating contains the method for vinyl compound.

(D-3) boronic acid compounds

As boronic acid compounds, can use boric acid, borax, borates such as borates such as the ammonium salt of boric acid, slaine, triethyl borate especially preferably use boric acid.

In addition, as the solvent of these boronic acid compounds, can be the material of these compounds of dissolving, can mainly make water, glycerine etc.In addition, the concentration of boronic acid compounds solution is preferably 0.1 weight %～10 weight %, more preferably 3 weight %～7 weight %.When the concentration of boronic acid compounds solution was beyond this scope, effect reduced.Its reason is, if the concentration less than 0.1 weight % of boronic acid compounds solution, because the boronic acid compounds in the solution is less, so the amount of the combination that forms is insufficient, on the other hand, if surpass 10 weight %, though agnogenio, supposition may be that ESR rises owing to remaining boric acid after forming combination produces harmful effect.

(D-4) make capacitor element contain the method for boronic acid compounds

As making capacitor element contain the method for above-mentioned boronic acid compounds, can use capacitor element is immersed in method in the solution of boronic acid compounds, perhaps the solution of boronic acid compounds is ejected to the method on the capacitor element.

In addition, make capacitor element contain boronic acid compounds after, if heat treated can improve the initial stage characteristic.Its reason is that the compound stripping that contains vinyl contained in the division board by increasing the hydrophobicity of its end group, can improve the adaptation of oxide-film and solid electrolyte in capacitor element.In addition, this heating-up temperature is preferably 120～250 ℃, more preferably 150～200 ℃.When heating-up temperature was beyond this scope, effect reduced.Its reason is, when 120 ℃ of heating-up temperature less thaies, can not fully promote to contain the reaction of hydrophobization etc. of the end group of vinyl compound, on the other hand, if surpass 250 ℃, causes the thermal degradation when that contains vinyl compound and effect is reduced.

(D-5) make capacitor element contain the period of boronic acid compounds

Further, present inventors are to having carried out various researchs the period that makes capacitor element contain above-mentioned boronic acid compounds.The stage before the operation that forms electric conductive polymer found that, so long as can be in any stage.That is to say that as mentioned above, can also can be attached on the electrode foil this period, for example can consider the method for following (1)～(3) before forming capacitor element before reparation changes into.In addition, the method for (1) is equivalent to the manufacture method shown in (D-1).

In addition, in the method for following (1)～(3), the method of (1) most preferably, promptly between anode foils and Cathode Foil, insertion contains the division board of the compound of vinyl, carry out around forming capacitor element, to this capacitor element implement to repair change into after, the solution of impregnation boronic acid compounds in this capacitor element, generation is by containing the combination that vinyl compound and boronic acid compounds form, afterwards, the polymerization reaction of electric conductive polymer taking place in this capacitor element, can form the method for solid electrolyte layer.In addition, even do not carry out resin-sealedly in the following method, can not change effect of the present invention yet.

(1) after reparation changes into ... with reference to Fig. 2

Change into → use the division board that contains vinyl compound form capacitor element → reparation and change into → dipping → impregnation polymerizable monomer and oxidant → polymerization in boronic acid compounds solution → be inserted into be in the shell framework → resin-sealed → etching

(2) before capacitor element forms back～reparation and changes into ... with reference to Fig. 3

Change into → use the division board that contains vinyl compound form the dipping → reparation of capacitor element → in boronic acid compounds solution and change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

(3) before capacitor element forms ... with reference to Fig. 4

Change into → at least one side in the electrode foil of the two poles of the earth be impregnated in the boronic acid compounds (or after the coating, dried) → use the division board that contains vinyl compound to form capacitor element → reparation to change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

Concentration, temperature, impregnation time, baking temperature, drying time that need to prove the boronic acid compounds solution in these methods etc. is identical with above-mentioned condition.

(D-6) EDT and oxidant

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～57 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, specially suitable is ethanol.Think that solvent that ethanol is suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(D-7) decompression

More preferably in polymerization process, reduce pressure.Its reason is, if reduce pressure when heated polymerizable, can make the residue evaporation in polymerization.In addition, the degree of decompression preferably reaches the decompression state about 10～360mmHg.

(D-8) dipping operation

The time that capacitor element be impregnated in the mixed liquor determines according to the size of capacitor element, be preferably more than 5 seconds for the capacitor element about φ 5 * 3L, be preferably more than 10 seconds minimum must the dipping for 5 seconds for the capacitor element about φ 9 * 5L.In addition, even long-time dipping can not produce harmful effect to characteristic yet.

In addition, so behind the dipping, preferably remain on decompression state.Think that its reason is that the residual quantity that is volatile solvent reduces.The condition of decompression and the reduced pressure of above-mentioned polymerization process are same.

(D-9) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(D-10) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT can form electric conductive polymer by certain oxidant oxidation polymerization, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(D-11) effect of the 4th execution mode, effect

As mentioned above, when use contains the division board formation capacitor element of vinyl compound, in the period of regulation, by making capacitor element contain boronic acid compounds, the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes can prevent owing to can also significantly lower the ratio that is short-circuited simultaneously in etching work procedure.

The reason that can access this effect is: the contained compound that contains vinyl stripping in manufacturing process in the division board, in capacitor element, form combination by boronic acid compounds and hydrogen bond etc., this combination is attached to cambium layer on the oxide-film of electrode foil, can improve the adaptation of solid electrolyte and oxide-film thus, further, can improve the proof voltage of capacitor thus owing to the proof voltage height of this layer.

In addition, compared with the compound that after forming at capacitor element element is contained to have vinyl, the combination that the method for the compound stripping that contains vinyl contained in the division board is had make itself and boronic acid compounds is equably attached to the advantage on the oxide-film.

Particularly under the situation of using PVA and boric acid, form the combination that is formed by ester compounds, this ester compounds can not be penetrated in the dielectric film, but attached to forming good layer on the film surface, therefore can obtain good characteristic.

Thereby, as mentioned above, think make it contain boronic acid compounds after, carry out heat treated, the adherence of the end group that contains vinyl compound of stripping and dielectric oxide film and electric conductive polymer improves from division board, obtains the effect that initial stage characteristic, particularly electrostatic capacitance and ESR characteristic improve.

(D-12) related embodiment of the 4th execution mode

Then, according to embodiment, comparative example and the existing example of following manufacturing, the invention of the 4th execution mode is described in detail.

(embodiment D1)

Contain 49 weight %PET fibers in the main consuming body fiber, with the PVA polymer as the division board of adhesive, the following solid electrolytic capacitor of making like that.The electrode means of drawing are connected on the anode foils and Cathode Foil that the surface formed oxidation film layer, and surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 5 φ * 2.8L.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element is immersed in the 5 weight % boric acid aqueous solutions, 175 ℃ of following heat treated.

On the other hand, in the container of regulation, the ethanolic solution that mixes the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, remain on the decompression state about 250mmHg, under identical condition, heated 60 minutes then, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer at 120 ℃.

Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 33V carries out 120 minutes etching, forms solid electrolytic capacitor.The rated voltage of this solid electrolytic capacitor is that 25WV, rated capacity are 15 μ F.

(Comparative Example D 1)

After reparation changes into, in boric acid aqueous solution, do not flood, form electric conductive polymer.Other condition is identical with embodiment D1 with operation.

(Comparative Example D 2)

Contain 49 weight %PET fibers in the main consuming body fiber, with pet polymer as the division board of adhesive, other condition is identical with embodiment D1 with operation.

(Comparative Example D 3)

After reparation changes into, this capacitor element is immersed in the 5 weight % boric acid aqueous solutions, and does not carry out heat treated.Other condition is identical with embodiment D1 with operation.

[comparative result]

Short circuit number during respectively to the initial stage characteristic of the solid electrolytic capacitor of 50 embodiment that obtain by said method and comparative example and etching is studied, and obtains result as shown in table 4.In addition, for the excellent product that is not short-circuited, carrying out peak temperature is 250 ℃, after keeping the unleaded anti-stream in 30 seconds more than 230 ℃, under 125 ℃, carry out the impact that discharges and recharges (surge) test of 1000 32.5V, measure short-circuit voltage, obtain result as shown in table 4.

[table 4]

	The initial stage characteristic		Short circuit frequency after the etching	Short-circuit voltage after the shock test (V)
					Cap (μF)	ESR (Ω/100kHz)
	Embodiment D1	15.3					0.045	0	52.5
Comparative Example D 1			15.0	0.050	6	51.0
	Comparative Example D 2	14.2					0.055	7	51.0
Comparative Example D 3			15.1	0.047	4	51.2

As can be seen from Table 4, contain the division board of PVA polymer in use, make among the embodiment D1 that contains boric acid aqueous solution in the capacitor element short circuit number after initial stage characteristic, the etching, short circuit number after the impact, any one in the short-circuit voltage after the impact all is better than Comparative Example D 1～D3.

Relative therewith, the characteristic of the Comparative Example D 2 of do not carry out Comparative Example D 1 that boric acid handles, using the division board that does not contain vinyl compound is not as embodiment D1.In addition, though do not carry out the result that the Comparative Example D 3 of heat treated obtains being better than Comparative Example D 1 or Comparative Example D 2, to compare its effect lower with embodiment D1.

(E) the 5th execution mode

Present embodiment is the variation of above-mentioned the 4th execution mode, the division board that use contains vinyl compound forms capacitor element, in this capacitor element, add DBSA (DBS) as additive, in this case, find also can obtain effect, the effect same with above-mentioned the 4th execution mode.

(E-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 5th execution mode is as described below.Promptly formed between the anode foils and Cathode Foil of oxidation film layer, inserted the division board of the compound that contains vinyl, carried out this capacitor element being implemented reparation changing into around forming capacitor element on the surface.Then, impregnation dodecylbenzenesulfonic acid solution in this capacitor element, generation is by containing the combination that vinyl compound and DBSA form, afterwards, this capacitor element is immersed in the mixed liquor that is formed by polymerizable monomer and oxidant and specified solvent mixed preparing, the polymerization reaction of electric conductive polymer takes place in capacitor element, forms solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

(E-2) division board

As division board used in the present embodiment, same division board shown in (D-2) division board item of preferred use and the 4th execution mode.

(E-3) DBSA (DBS)

As the solvent of DBSA used among the present invention, preferably make water, alcohol etc.In addition, the concentration of dodecylbenzenesulfonic acid solution is preferably 0.1 weight %～5 weight %, more preferably 0.2 weight %～2 weight %.If the concentration of dodecylbenzenesulfonic acid solution is less than this scope, because the layer of the combination of DBS and PVA is thinner, electrostatic capacitance, ESR characteristic are improved, proof voltage improves, and LC suppresses effect and reduces.On the other hand, if surpass this scope, because the layer of the combination of DBS and PVA is blocked up, because the conductivity of this layer reduces, so electrostatic capacitance, ESR characteristic reduce.

(E-4) make capacitor element contain the method for DBS

As making capacitor element contain the method for above-mentioned DBSA, with execution mode 4 similarly, can use capacitor element is immersed in method in the dodecylbenzenesulfonic acid solution, perhaps dodecylbenzenesulfonic acid solution is ejected to the method on the capacitor element.

In addition, after finding to make capacitor element contain DBSA, if heat treated can improve the initial stage characteristic.Its reason is that the compound stripping that contains vinyl contained in the division board by increasing the hydrophobicity of its end group, can improve the adaptation of oxide-film and solid electrolyte in capacitor element.In addition, this heating-up temperature is preferably 120～250 ℃, more preferably 150～200 ℃.When heating-up temperature was beyond this scope, effect reduced.Its reason is, when 120 ℃ of heating-up temperature less thaies, the reaction of hydrophobization etc. that contains the end group of vinyl compound can not fully be carried out, and on the other hand, if surpass 250 ℃, then causes the thermal degradation when that contains vinyl compound and effect is reduced.

(E-5) make capacitor element contain the period of DBS

Further, present inventors have been to having carried out various researchs the period that makes capacitor element contain DBSA, found that and above-mentioned the 4th execution mode similarly, so long as the stage before the operation that forms electric conductive polymer can be in any stage.That is to say that as mentioned above, can be attached on the electrode foil this period, for example can consider the method for following (1)～(3) before forming capacitor element before reparation changes into.In addition, the method for (1) is equivalent to above-mentioned manufacture method.

In addition, in the method for following (1)～(3), the method of (1) most preferably, promptly between anode foils and Cathode Foil, insertion contains the division board of vinyl compound, carry out around forming capacitor element, to this capacitor element implement to repair change into after, impregnation dodecylbenzenesulfonic acid solution in this capacitor element, generation is by containing the combination that vinyl compound and DBSA form, afterwards, the polymerization reaction of electric conductive polymer taking place in capacitor element, can form the method for solid electrolyte layer.

In addition, following each method can replace with dodecylbenzenesulfonic acid solution with the boronic acid compounds solution of Fig. 2～Fig. 4 shown in above-mentioned the 4th execution mode and be suitable for.

(1) after reparation changes into ... with reference to Fig. 2

Change into → use the division board that contains vinyl compound form capacitor element → reparation and change into → dipping → impregnation polymerizable monomer and oxidant → polymerization in dodecylbenzenesulfonic acid solution → be inserted into be in the shell framework → resin-sealed → etching

(2) before capacitor element forms back～reparation and changes into ... with reference to Fig. 3

Change into → use the division board that contains vinyl compound form the dipping → reparation of capacitor element → in dodecylbenzenesulfonic acid solution and change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

(3) before capacitor element forms ... with reference to Fig. 4

Change into → at least one side in the electrode foil of the two poles of the earth be impregnated in the dodecylbenzenesulfonic acid solution (or after the coating, dried) → use the division board that contains vinyl compound to form capacitor element → reparation to change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

The concentration of the dodecylbenzenesulfonic acid solution in these methods, temperature, impregnation time, baking temperature, drying time etc. are identical with above-mentioned condition.

(E-6) EDT and oxidant

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～57 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, suitable is ethanol.Think that solvent that ethanol is suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(E-7) decompression

More preferably in polymerization process, reduce pressure.Its reason is, if reduce pressure when heated polymerizable, can make the residue evaporation in polymerization.In addition, the degree of decompression preferably reaches the decompression state about 10～360mmHg.

(E-8) dipping operation

The time that capacitor element be impregnated in the mixed liquor determines according to the size of capacitor element, be preferably more than 5 seconds for the capacitor element about φ 5 * 3L, be preferably more than 10 seconds minimum must the dipping for 5 seconds for the capacitor element about φ 9 * 5L.In addition, even long-time dipping can not produce harmful effect to characteristic yet.

In addition, so behind the dipping, preferably remain on decompression state.Think that its reason is that the residual quantity that is volatile solvent reduces.The condition of decompression and the reduced pressure of above-mentioned polymerization process are same.

(E-9) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(E-10) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT can form electric conductive polymer by the oxidant oxidation polymerization of regulation, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(E-11) effect of the 5th execution mode, effect

As mentioned above, when use contains the division board formation capacitor element of vinyl compound, in the period of regulation, by making capacitor element contain DBSA, the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes can prevent owing to can also significantly lower the ratio that is short-circuited simultaneously in etching work procedure.

The reason that can access this effect is: the contained compound that contains vinyl stripping in manufacturing process in the division board, in capacitor element, form combination by DBSA and hydrogen bond etc., this combination is attached to cambium layer on the oxide-film of electrode foil, can improve the adaptation of solid electrolyte and oxide-film thus, further, can improve the proof voltage of capacitor owing to the proof voltage height of layer.

In addition, compared with the compound that after forming at capacitor element element is contained to have vinyl, the combination that the method for the compound stripping that contains vinyl contained in the division board is had make this compound that contains vinyl and DBSA is equably attached to the advantage on the oxide-film.

Particularly under the situation of using PVA and DBSA, form the combination that is formed by ester compounds, this ester compounds can not be penetrated in the dielectric film, but attached to the film that forms the blocking-up electronics on the film surface, therefore can obtain good characteristic.

Thereby, as mentioned above, after making it contain DBSA, carry out heat treated, the adherence of the end group that contains vinyl compound of stripping and dielectric oxide film and electric conductive polymer improves from division board, obtains the effect that initial stage characteristic, particularly electrostatic capacitance and ESR characteristic improve, proof voltage improves, LC lowers.

(E-12) related embodiment of the 5th execution mode ... it is 1 years old

Then, according to embodiment E 1～E4, the Comparative Example E 1 of following manufacturing, the invention of the 5th execution mode is described in detail.

(embodiment E 1)

Contain 49 weight %PET fibers in the main consuming body fiber, with the PVA polymer as the division board of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil of surface formation oxidation film layer, surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 7 φ * 5L.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element after 100 ℃ of following dryings, is immersed in this capacitor element in the DBSA aqueous solution of 0.1 weight %, 150 ℃ of following heat treated.

On the other hand, in the container of regulation, the ethanolic solution that mixes the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, remain on the decompression state about 250mmHg, under identical condition, heated 60 minutes then, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer at 120 ℃.

Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 33V carries out 120 minutes etching, forms solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 25WV, rated capacity are 22 μ F.

(embodiment E 2)

Make the concentration of dodecylbenzenesulfonic acid solution become 0.5 weight %.Other is identical with embodiment E 1, makes solid electrolytic capacitor.

(embodiment E 3)

Make the concentration of dodecylbenzenesulfonic acid solution become 2.0 weight %.Other is identical with embodiment E 1, makes solid electrolytic capacitor.

(embodiment E 4)

Make the concentration of dodecylbenzenesulfonic acid solution become 5.0 weight %.Other is identical with embodiment E 1, makes solid electrolytic capacitor.

(Comparative Example E 1)

After reparation changes into, in dodecylbenzenesulfonic acid solution, do not flood, form electric conductive polymer.Other condition is identical with embodiment E 1 with operation.

[comparative result]

Initial stage characteristic and anti-properties of flow to each solid electrolytic capacitor of the embodiment E 1～E4 that obtains by said method and Comparative Example E 1 are studied, and obtain result as shown in table 5.It should be noted that, in the anti-stream test, obtain that to carry out peak temperature be 250 ℃, the leakage current behind the unleaded anti-stream that kept for 30 seconds more than 230 ℃.

[table 5]

	DBS concentration (%)	The initial stage characteristic		Anti-properties of flow
					Proof voltage (V)	LC(μA)	LC(μA)
		Embodiment E 1	0.1	58				0.3	20
Embodiment E 2	0.5				59	0.7	9
		Embodiment E 3	2.0	58				1.0	20
Embodiment E 4	5.0				55	1.5	20
		Comparative Example E 1	0	54				2.0	30

As can be seen from Table 5, contain the division board of PVA polymer in use, the proof voltage that makes the embodiment E 1～E4 that contains dodecylbenzenesulfonic acid solution in the capacitor element is 55～59V, and the proof voltage (54V) of any one and Comparative Example E 1 is compared all raising.Particularly DBS concentration is that proof voltage demonstrates the higher value of 58～59V among embodiment E 1～E3 of 0.1～2.0%.

In addition, the leakage current behind its initial stage and the anti-stream is reduced to 0.3～1.5 μ A, 9～20 μ A respectively with respect to 2 μ A in the Comparative Example E 1,30 μ A.

(E-13) related embodiment of the 5th execution mode ... they are 2 years old

Then, according to embodiment E 5, the Comparative Example E 2 of following manufacturing, the invention of the 5th execution mode is described in detail.

(embodiment E 5)

Contain 49 weight %PET fibers in the main consuming body fiber, with the PVA polymer as the division board of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil of surface formation oxidation film layer, surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 5 φ * 3L.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element after 100 ℃ of following dryings, is immersed in this capacitor element in the DBSA aqueous solution of 0.5 weight %, 150 ℃ of following heat treated.

On the other hand, in the container of regulation, the ethanolic solution that mixes the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, remain on the decompression state about 250mmHg, under identical condition, heated 60 minutes then, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer at 120 ℃.

Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then, carry out etching, form solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 6.3WV, rated capacity are 180 μ F.

(Comparative Example E 2)

After reparation changes into, in dodecylbenzenesulfonic acid solution, do not flood, form electric conductive polymer.Other condition is identical with embodiment E 5 with operation.

[comparative result]

The embodiment E 5 that obtains by said method and each solid electrolytic capacitor of Comparative Example E 2 are carried out the initial stage The Characteristic Study, obtain result as shown in table 6.

[table 6]

	DBS concentration (%)	The initial stage characteristic
				Cap (μF)	ESR (Ω/100kHz)
		Embodiment E 5	0.5			185	0.013
Comparative Example E 2	0			180	0.015

As can be seen from Table 6, use the division board contain the PVA polymer, the embodiment E 5 that contains dodecylbenzenesulfonic acid solution in the capacitor element is compared with Comparative Example E 2, obtained good result.

(F) the 6th execution mode

Present embodiment is the variation of above-mentioned the 4th execution mode, the division board that use contains vinyl compound forms capacitor element, in this capacitor element, add sodium naphthalene sulfonate (NPS) as additive, in this case, find also can obtain effect, the effect same with above-mentioned the 4th execution mode.

(F-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 6th execution mode is as described below.Promptly form between the anode foils and Cathode Foil of oxidation film layer, insert the division board of the compound that contains vinyl, carry out this capacitor element being implemented reparation changing into around forming capacitor element on the surface.Then, impregnation sodium naphthalene sulfonate solution in this capacitor element, generation is by containing the combination that vinyl compound and sodium naphthalene sulfonate form, afterwards, this capacitor element is immersed in the mixed liquor that is formed by polymerizable monomer and oxidant and specified solvent mixed preparing, the polymerization reaction of electric conductive polymer takes place in capacitor element, forms solid electrolyte layer.Then, this capacitor element is inserted in the shell framework, installs at open end and seal rubber, after securing member processing sealing, carry out etching, form solid electrolytic capacitor.

(F-2) division board

As division board used in the present embodiment, same division board shown in (D-2) division board item of preferred use and the 4th execution mode.

(F-3) sodium naphthalene sulfonate (NPS)

As the solvent of sodium naphthalene sulfonate used among the present invention, preferably make water, alcohol etc.In addition, the concentration of sodium naphthalene sulfonate solution is preferably 0.1 weight %～5 weight %, more preferably 0.2 weight %～2 weight %.If the concentration of sodium naphthalene sulfonate solution is less than this scope, because the layer of the combination of NPS and PVA is thin, electrostatic capacitance, ESR characteristic are improved, proof voltage improves, LC suppresses effect and reduces.If surpass this scope, because the layer of the combination of NPS and PVA is blocked up, because the conductivity of this layer reduces, so voltage-resistent characteristic, electrostatic capacitance, ESR characteristic reduce.

(F-4) make capacitor element contain the method for NPS

As making capacitor element contain the method for above-mentioned sodium naphthalene sulfonate, with shown in above-mentioned execution mode 4 and the execution mode 5 similarly, can use capacitor element is immersed in method in the sodium naphthalene sulfonate solution, perhaps sodium naphthalene sulfonate solution is ejected to the method on the capacitor element.

In addition, after finding to make capacitor element contain sodium naphthalene sulfonate, if heat treated can improve the initial stage characteristic.Its reason is that the compound stripping that contains vinyl contained in the division board by increasing the hydrophobicity of its end group, can improve the adaptation of oxide-film and solid electrolyte in capacitor element.In addition, this heating-up temperature is preferably 120～250 ℃, more preferably 150～200 ℃.When heating-up temperature was beyond this scope, effect reduced.Its reason is, when 120 ℃ of heating-up temperature less thaies, the reaction of hydrophobization etc. that contains the end group of vinyl compound can not fully be carried out, and on the other hand, if surpass 250 ℃, causes the thermal degradation when that contains vinyl compound and effect is reduced.

(F-5) make capacitor element contain the period of NPS

Further, present inventors have been to having carried out various researchs the period that makes capacitor element contain above-mentioned sodium naphthalene sulfonate, found that and above-mentioned the 4th execution mode similarly, so long as the stage before the operation that forms electric conductive polymer can be in any stage.That is to say that as mentioned above, can be attached on the electrode foil this period, for example can consider the method for following (1)～(3) before forming capacitor element before reparation changes into.In addition, the method for (1) is equivalent to above-mentioned manufacture method.

In addition, in the method for following (1)～(3), the method of (1) most preferably, promptly between anode foils and Cathode Foil, insertion contains the division board of vinyl compound, carry out around forming capacitor element, to this capacitor element implement to repair change into after, impregnation sodium naphthalene sulfonate solution in this capacitor element, generation is by containing the combination that vinyl compound and sodium naphthalene sulfonate form, afterwards, the polymerization reaction of electric conductive polymer taking place in this capacitor element, can form solid electrolyte layer.

In addition, following each method can replace with sodium naphthalene sulfonate solution with the boronic acid compounds solution of Fig. 2～Fig. 4 shown in above-mentioned the 4th execution mode and be suitable for.

(1) after reparation changes into ... with reference to Fig. 2

Change into → use the division board that contains vinyl compound form capacitor element → reparation and change into → dipping → impregnation polymerizable monomer and oxidant → polymerization in sodium naphthalene sulfonate solution → be inserted into be in the shell framework → resin-sealed → etching

(2) before capacitor element forms back～reparation and changes into ... with reference to Fig. 3

Change into → use the division board that contains vinyl compound form the dipping → reparation of capacitor element → in sodium naphthalene sulfonate solution and change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

(3) before capacitor element forms ... with reference to Fig. 4

Change into → at least one side in the electrode foil of the two poles of the earth be impregnated in the sodium naphthalene sulfonate (or after the coating, dried) → use the division board that contains vinyl compound to form capacitor element → reparation to change into → impregnation polymerizable monomer and oxidant → polymerization → be inserted into be in the shell framework → resin-sealed → etching

Concentration, temperature, impregnation time, drying time that need to prove the sodium naphthalene sulfonate solution in these methods etc. is identical with above-mentioned condition.

(F-6) EDT and oxidant

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., wherein particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～57 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, specially suitable is ethanol.Think that solvent that ethanol is particularly suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(F-7) decompression

More preferably in polymerization process, reduce pressure.Its reason is, if reduce pressure when heated polymerizable, can make the residue evaporation in polymerization.In addition, the degree of decompression preferably reaches the decompression state about 10～360mmHg.

(F-8) dipping operation

The time that capacitor element be impregnated in the mixed liquor determines according to the size of capacitor element, be preferably more than 5 seconds for the capacitor element about φ 5 * 3L, be preferably more than 10 seconds minimum must the dipping for 5 seconds for the capacitor element about φ 9 * 5L.In addition, even long-time dipping can not produce harmful effect to characteristic yet.

In addition, so behind the dipping, preferably remain on decompression state.Think that its reason is that the residual quantity that is volatile solvent reduces.The condition of decompression and the reduced pressure of above-mentioned polymerization process are same.

(F-9) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(F-10) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT can form electric conductive polymer by the oxidant oxidation polymerization of regulation, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(F-11) effect of the 6th execution mode, effect

As mentioned above, when use contains the division board formation capacitor element of vinyl compound, in the period of regulation, by making capacitor element contain sodium naphthalene sulfonate, the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes can prevent owing to can also significantly lower the ratio that is short-circuited simultaneously in etching work procedure.

The reason that can access this effect is: the contained compound that contains vinyl stripping in manufacturing process in the division board, in capacitor element, form combination by sodium naphthalene sulfonate and hydrogen bond etc., this combination is attached to cambium layer on the oxide-film of electrode foil, can improve the adaptation of solid electrolyte and oxide-film thus, further, can improve the proof voltage of capacitor because the proof voltage of this layer is higher.

In addition, compared with the compound that after forming at capacitor element element is contained to have vinyl, the combination that the method for the compound stripping that contains vinyl contained in the division board is had make this compound that contains vinyl and sodium naphthalene sulfonate is equably attached to the advantage on the oxide-film.

Particularly under the situation of using PVA and sodium naphthalene sulfonate, form the combination that is formed by ester compounds, this ester compounds can not be penetrated in the dielectric film, but attached to the film that forms the blocking-up electronics on the film surface, therefore can obtain good characteristic.

Thereby, as mentioned above, think make it contain sodium naphthalene sulfonate after, carry out heat treated, the adherence of the end group that contains vinyl compound of stripping and dielectric oxide film and even electric conductive polymer improves from division board, obtains the effect that initial stage characteristic, particularly electrostatic capacitance and ESR characteristic improve, proof voltage improves, LC lowers.

(F-12) related embodiment of the 6th execution mode

Then, according to embodiment F 1～F4, the Comparative Example F 1 of following manufacturing, the present invention will be described in more detail.

(embodiment F 1)

Contain 49 weight %PET fibers in the main consuming body fiber, with the PVA polymer as the division board of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil that the surface formed oxidation film layer, and surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 7 φ * 5L.Then, this capacitor element is flooded to repair in 40 minutes in ammonium dihydrogen phosphate aqueous solution change into.After reparation changes into, this capacitor element after 100 ℃ of following dryings, is immersed in this capacitor element in the sodium naphthalene sulfonate aqueous solution of 0.1 weight %, 150 ℃ of following heat treated.

On the other hand, in the container of regulation, the ethanolic solution that mixes the p-methyl benzenesulfonic acid iron of EDT and 45%, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, remain on the decompression state about 250mmHg, under identical condition, heated 60 minutes then, the polymerization reaction of PEDT takes place in capacitor element, form solid electrolyte layer at 120 ℃.

Then, this capacitor element is inserted in the shell framework of bottom tube-like, installs at open end and seal rubber, by securing member processing sealing.Then under 150 ℃, in addition the voltage of 33V carries out 120 minutes etching, forms solid electrolytic capacitor.In addition, the rated voltage of this solid electrolytic capacitor is that 25WV, rated capacity are 22 μ F.

(embodiment F 2)

The concentration that makes sodium naphthalene sulfonate solution is 0.5 weight %.Other is identical with embodiment F 1, makes solid electrolytic capacitor.

(embodiment F 3)

The concentration that makes sodium naphthalene sulfonate solution is 2.0 weight %.Other is identical with embodiment F 1, makes solid electrolytic capacitor.

(embodiment F 4)

The concentration that makes sodium naphthalene sulfonate solution is 5.0 weight %.Other is identical with embodiment F 1, makes solid electrolytic capacitor.

(Comparative Example F 1)

After reparation changes into, in sodium naphthalene sulfonate solution, do not flood, form electric conductive polymer.Other condition is identical with embodiment F 1 with operation.

[comparative result]

Initial stage characteristic and anti-properties of flow to each solid electrolytic capacitor of the embodiment F 1～F4 that obtains by said method and Comparative Example F 1 are studied, and obtain result as shown in table 7.In addition, in the anti-stream test, obtain that to carry out peak temperature be 250 ℃, the leakage current behind the unleaded anti-stream that kept for 30 seconds more than 230 ℃.

[table 7]

	DBS concentration (%)	The initial stage characteristic		Anti-properties of flow
					Proof voltage (V)	LC(μA)	LC(μA)
		Embodiment F 1	0.1	57				0.2	20
Embodiment F 2	0.5				57	0.3	10
		Embodiment F 3	2.0	57				0.5	10
Embodiment F 4	5.0				55	0.1	8
		Comparative Example F 1	0	54				2.0	30

As can be seen from Table 7, using the division board contain the PVA polymer, making the proof voltage of the embodiment F 1～F4 that contains sodium naphthalene sulfonate solution in the capacitor element is 55～57V, and the proof voltage (54V) of any one and Comparative Example F 1 is compared all raising.Particularly NPS concentration is that proof voltage demonstrates the high value of 57V among embodiment F 1～F3 of 0.1～2.0%.

In addition, the leakage current behind its initial stage and the anti-stream is reduced to 0.1～0.5 μ A, 8～20 μ A respectively with respect to 2 μ A in the Comparative Example F 1,30 μ A.

(G) the 7th execution mode

Present inventors are in order to reach above-mentioned the 4th purpose, and research has repeatedly been carried out in the inhibition that the LC behind the raising of the proof voltage of realization solid electrolytic capacitor and the anti-stream changes, and has finished the invention shown in the 7th execution mode.Be that present inventors are conceived to conductive mechanism, the conduction of solid electrolytes such as electric conductive polymer is studied.

Usually, electronics emission is divided into these 2 kinds of the transition (not relying on the transition of electronics of the breakage of film) of the tunneling electron and the current potential barrier of electronics, think that the leakage current of solid electrolytic capacitor is not because short-circuit condition, but since the transition of current potential barrier cause.

In addition, as the reason that anti-stream back LC rises, think because mechanical stress (physical stress) and the chemical stress (invasion and attack of oxidant or the transition of electronics etc.) in the anti-stream that gas causes.

That is to say that for the high withstand voltageization of solid electrolytic capacitor, electronics increases in short circuit, become breakdown conditions, become tunnel state, for the rising of the LC in the anti-stream, not owing to insulation breakdown, but because the transition of electronics, both are electronics at common part.Therefore, think, suppressed the transition of current potential barrier, can realize high withstand voltageization, suppress the rising of the LC that anti-stream causes by the blocking-up electronics.

Based on these discoveries, present inventors have carried out various researchs repeatedly to the method for the transition that can prevent the current potential barrier, discovery is by making the compound that contains vinyl in the division board, and use this division board to form capacitor element, make this capacitor element contain polyimides silicon, can improve the proof voltage of product, the LC after suppressing instead to flow rises.

(G-1) manufacture method of solid electrolytic capacitor

The manufacture method of the solid electrolytic capacitor in the 7th execution mode is as described below.Promptly form between the anode foils and Cathode Foil of oxidation film layer, insert the division board of the compound that contains vinyl, carry out this capacitor element being implemented reparation changing into around forming capacitor element on the surface.Then, this capacitor element is immersed in dissolved below the 10 weight %, be preferably 1.5～9 weight %, more preferably in the ketone solution of the polyimides silicon of 5～8 weight %, after mentioning, at 40～100 ℃ of following evaporating solvents, under 150～200 ℃, heat-treat then.

Then, this capacitor element is immersed in the mixed liquor of polymerizable monomer and oxidant, the polymerization reaction of electric conductive polymer takes place in capacitor element, form solid electrolyte layer.Then, this capacitor element is accommodated to the shell framework, with sealing rubber seal, form solid electrolytic capacitor at open end.

(G-2) polyimides silicon

As the solvent of dissolving polyimides silicon, the ketones solvent of the favorable solubility of preferred polyimides silicon can use cyclohexanone, acetone, methylethylketone etc.

In addition, the concentration of polyimides silicon is below 10 weight %, preferably at 1.5～9 weight %, more preferably at 5～8 weight %.If not enough this scope of concentration, then proof voltage is not enough, if surpass the then electrostatic capacitance reduction of this scope.

(G-3) division board

As division board used in the present embodiment, same division board shown in (D-2) division board item of preferred use and the 4th execution mode.

(G-4) EDT and hydrogenant agent

When during as polymerizable monomer,, using the EDT monomer, also can use the monomer solution that EDT and volatile solvent are mixed with 1: 0～1: 3 volume ratio as containing the EDT that is dipped in the capacitor element with EDT.

As aforementioned volatile solvent, can use nitrogen compounds such as alcohols such as ketones such as ester class, acetone, methyl alcohol, acetonitrile such as ethers such as hydro carbons, oxolane, Ethyl formate such as pentane etc., especially particular methanol, ethanol, acetone etc.

In addition, as oxidant, can use the aqueous solution of the p-methyl benzenesulfonic acid iron, periodic acid or the acid iodide that are dissolved in ethanol, oxidant is preferably 40～65 weight % with respect to the concentration of solvent, more preferably 45～57 weight %.Oxidant is high more with respect to the concentration of solvent, and ESR lowers more.In addition, as the solvent of oxidant, can use employed volatile solvent in the above-mentioned monomer solution, specially suitable is ethanol.Think that ethanol is that the solvent that is particularly suitable as oxidant is because the low evaporation easily of its vapour pressure, so residual quantity is less.

(G-5) repair the liquid that changes into that changes into

Change into liquid as what reparation changed into, can use the liquid that changes into of phosphoric acid classes such as ammonium dihydrogen phosphate, diammonium hydrogen phosphate, boric acid classes such as ammonium borate change into liquid, adipic acid classes such as ammonium adipate change into liquid, especially preferably use ammonium dihydrogen phosphate.In addition, dip time is preferably 5～120 minutes.

(G-6) other polymerizable monomer

As polymerizable monomer used among the present invention, except above-mentioned EDT, if thiophene derivant, aniline, pyrroles, furans, acetylene or their derivative beyond the EDT can form electric conductive polymer by the oxidant oxidation polymerization of regulation, then can be suitable for.In addition, as thiophene derivant, can use material with structural formula shown in Figure 1.

(G-7) effect of the 7th execution mode, effect

With formation of the present invention, can be improved proof voltage and suppress anti-stream after the effect that changes of LC, think owing to due to the following reason.

That is to say, think,, form by PVA and these 2 layers film that prevents above-mentioned electron transition (hereinafter referred to as electron blocking layers) that forms of polyimides silicon on the oxide-film surface by after reparation changes into, capacitor element being immersed in the polyimides silicon solution.

And because this electron blocking layers, proof voltage rises, and can prevent the invasion and attack of oxidant to paper tinsel, lowers the LC at initial stage.In addition, carry out Block コ-ト again, can be prevented because the effect that the LC that anti-stream causes rises.Further, also be difficult to electrostatic capacitance, ESR are exerted an influence, control, can also control proof voltage by thickness to this electron blocking layers.In addition owing to can reduce the VF of now used paper tinsel, can give play to solid electrolytic capacitor miniaturization, improve the effect of electric capacity etc.

(G-8) related embodiment of the 7th execution mode

Then, according to the embodiment and the existing example of following manufacturing, the present invention will be described in more detail.

(embodiment G1)

Contain 49 weight %PET fibers in the main consuming body fiber, with the PVA polymer as the division board of adhesive, the following solid electrolytic capacitor of making.The electrode means of drawing are connected on the anode foils and Cathode Foil of surface formation oxidation film layer, surrounded after inserting above-mentioned division board between two electrode foils, the formation component shape is the capacitor element of 7 φ * 5L.Then, this capacitor element was flooded in ammonium dihydrogen phosphate aqueous solution 40 minutes, repair and change into.Afterwards, this capacitor element is immersed in the cyclohexanone solution of polyimides silicon of 2 weight %, after mentioning, 170 ℃ of following heat treated 1 hour.

Then, in the container of regulation, inject 40 weight % butanol solutions of EDT and p-methyl benzenesulfonic acid iron and prepare mixed liquor so that its weight ratio becomes 1: 3, capacitor element was flooded for 10 seconds in above-mentioned mixed liquor, EDT and oxidant are contained be dipped in the capacitor element, then, this capacitor element was placed 1 hour in 120 ℃ thermostat, the polymerization reaction of PEDT takes place in capacitor element, forms solid electrolyte layer.Then, this capacitor element is accommodated to the aluminium framework that bottom tube-like is arranged,, form solid electrolytic capacitor with sealing rubber seal.

(embodiment G2)

Capacitor element is immersed in the cyclohexanone solution of polyimides silicon of 6 weight %, after mentioning, 170 ℃ of following heat treatments 1 hour.Other condition is identical with embodiment G1 with operation, makes solid electrolytic capacitor.

(embodiment G3)

Capacitor element is immersed in the cyclohexane solution of polyimides silicon of 10 weight %, after mentioning, 170 ℃ of following heat treatments 1 hour.Other condition is identical with embodiment G1 with operation, makes solid electrolytic capacitor.

(existing example G1)

Capacitor element is not immersed in the cyclohexanone solution of polyimides silicon, other condition is identical with embodiment G1 with operation, makes solid electrolytic capacitor.

[comparative result]

Embodiment G1～the G3 that obtains by said method and the electrology characteristic of existing example G1 are studied, obtain result as shown in table 8.In addition, the slip of initial stage electric capacity (Δ Cap) is to represent with respect to the percentage of blank (existing example).

[table 8]

	Addition (weight %)	The initial stage characteristic			LC(μA)
							Proof voltage (V)	ESR(mΩ)	ΔCap(％)	Initial stage	Behind the anti-stream
		Embodiment G1	2.0	66	25.0	0						0.1	5
Embodiment G2	6.0						74	26.0	-18	0.1	0.9
		Embodiment G3	10.0	75	26.5	-30						0.1	0.9
Comparative example G1	-						58	25.0	0	0.5	150

As can be seen from Table 8, for the embodiment G1～G3 that after reparation changes into, capacitor element is immersed in the polyimides silicon solution, its any one compare proof voltage with existing example G1 and improve, the LC behind the anti-stream significantly lowers.

According to the invention shown in the 1st execution mode, can provide a kind of Solid electrolytic capacitor And Manufacturing approach that can lower ESR and improve electrostatic capacitance.

In addition, according to the invention shown in the 2nd execution mode, as division board, use contains the above division board that contains vinyl compound as adhesive of 10 weight %, before impregnation polymerizable monomer and oxidant, by making capacitor element contain the coupling agent of regulation, can provide a kind of Solid electrolytic capacitor And Manufacturing approach that can realize lowering ESR, improve electrostatic capacitance and raising proof voltage.

In addition, according to the invention shown in the 3rd execution mode, as division board, use contains the above division board that contains vinyl compound as adhesive of 10 weight %, before impregnation polymerizable monomer and oxidant, by capacitor element being contained be selected from a kind or 2 kinds in ethinylation glycol, the dimethyl lauryl amine oxide, can provide a kind of and can realize lowering ESR, improve electrostatic capacitance and improve the Solid electrolytic capacitor And Manufacturing approach of proof voltage.

In addition, according to the invention shown in the 4th～the 6th execution mode, can provide a kind of and can prevent because the deterioration of the voltage-resistent characteristic that unleaded anti-stream causes improves the productive rate when making the high withstand voltage product, and then the also good Solid electrolytic capacitor And Manufacturing approach of initial stage characteristic.

In addition, according to the invention shown in the 7th execution mode, can provide a kind of and can improve proof voltage and suppress the Solid electrolytic capacitor And Manufacturing approach that anti-stream back LC changes.

Claims (28)

1. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, after reparation changes into, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: the adhesive of aforementioned division board is to be made of the compound that contains vinyl, and the content of adhesive is 10～20% with respect to the total weight of division board in the division board before aforementioned reparation changes into.

2. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: aforementioned division board contains the above compound that contains vinyl as adhesive of 10 weight %, before aforementioned polymerizable monomer of impregnation and oxidant, makes capacitor element contain the coupling agent of regulation.

3. the solid electrolytic capacitor of putting down in writing as claim 2 is characterized in that: capacitor element is contained before the aforementioned coupling agent, make capacitor element contain boronic acid compounds.

4. as claim 2 or 3 solid electrolytic capacitors of being put down in writing, it is characterized in that: aforementioned coupling agent is the coupling agent more than a kind or 2 kinds that is selected from silane coupler, titanium coupling agent, the aluminum coupling agent.

5. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: aforementioned division board contains the above compound that contains vinyl as adhesive of 10 weight %, before impregnation polymerizable monomer and oxidant, capacitor element is contained be selected from a kind or 2 kinds in ethinylation glycol, the dimethyl lauryl amine oxide.

6. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, make and contain the combination that forms by compound that contains vinyl and boronic acid compounds in the aforementioned capacitor element.

7. the solid electrolytic capacitor of putting down in writing as claim 6, it is characterized in that: aforementioned boronic acid compounds is boric acid or borax.

8. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, make and contain the combination that forms by compound that contains vinyl and DBSA in the aforementioned capacitor element.

9. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, make and contain the combination that forms by compound that contains vinyl and sodium naphthalene sulfonate in the aforementioned capacitor element.

10. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, with using this division board to carry out being immersed in the polyimides silicon solution, form by containing the film that vinyl compound and polyimides silicon form on the surface of oxide-film around the capacitor element that forms.

11. solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, the solid electrolyte layer that the formation of impregnation polymerizable monomer and oxidant is formed by electric conductive polymer in this capacitor element constitutes

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, to use this division board to carry out being immersed in the polyimides silicon solution, form on the surface of oxide-film by 2 tunics that form by polyimides silicon that contain vinyl compound and further form in the above around the capacitor element that forms.

12. as each solid electrolytic capacitor of putting down in writing in the claim 1 to 11, it is characterized in that: the aforementioned vinyl compound that contains is a polyvinyl alcohol.

13. as each solid electrolytic capacitor of putting down in writing in the claim 1 to 12, it is characterized in that: aforementioned polymerizable monomer is a thiophene derivant.

14. the solid electrolytic capacitor as claim 13 is put down in writing is characterized in that: aforementioned thiophene derivant is 3,4-ethylidene dioxy thiophene.

15. the manufacture method of a solid electrolytic capacitor, it is by inserting division board between anode foils and Cathode Foil, carrying out around forming capacitor element, after reparation changes into, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer

It is characterized in that: the adhesive of aforementioned division board is to be made of the compound that contains vinyl, and the content of above-mentioned adhesive is 10～20% with respect to the total weight of division board in the division board before aforementioned reparation changes into.

16. the manufacture method of a solid electrolytic capacitor, it is by inserting division board between anode foils and Cathode Foil, carrying out around forming capacitor element, after reparation changes into, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer

It is characterized in that: the adhesive of aforementioned division board is to be made of the compound that contains vinyl, by before aforementioned reparation changes into, the aforementioned capacitor element being immersed in 60～100 ℃ the warm water, before aforementioned reparation changes into division board in the content of above-mentioned adhesive be adjusted to that to make its total weight with respect to division board be 10～20%.

17. the manufacture method of a solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer in this capacitor element

It is characterized in that: as aforementioned division board, use the division board contain the above compound that contains vinyl as adhesive of 10 weight %, before aforementioned polymerizable monomer of impregnation and oxidant, make capacitor element contain the coupling agent of regulation.

18. the manufacture method of the solid electrolytic capacitor of putting down in writing as claim 17 is characterized in that: capacitor element is contained before the aforementioned coupling agent, make capacitor element contain boronic acid compounds.

19. the manufacture method as claim 17 or 18 solid electrolytic capacitors of being put down in writing is characterized in that: aforementioned coupling agent is the coupling agent more than a kind or 2 kinds that is selected from silane coupler, titanium coupling agent, the aluminum coupling agent.

20. the manufacture method of a solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer in this capacitor element

It is characterized in that: as aforementioned division board, use contains the division board of the above compound that contains vinyl as adhesive of 10 weight %, before injecting polymerizable monomer and oxidant, capacitor element is contained be selected from a kind or 2 kinds in ethinylation glycol, the dimethyl lauryl amine oxide.

21. the manufacture method of a solid electrolytic capacitor, it is characterized in that: by between anode foils and Cathode Foil, inserting the division board of the compound that contains vinyl, carry out around forming capacitor element, the solution of impregnation boronic acid compounds in this capacitor element, generation forms the solid electrolyte layer that is formed by electric conductive polymer afterwards by the combination that compound that contains vinyl and boronic acid compounds form.

22. the manufacture method of a solid electrolytic capacitor, it is characterized in that: by between anode foils and Cathode Foil, inserting the division board of the compound that contains vinyl, carry out around forming capacitor element, the solution of impregnation DBSA in this capacitor element, generation forms the solid electrolyte layer that is formed by electric conductive polymer afterwards by the combination that compound that contains vinyl and DBSA form.

23. the manufacture method of a solid electrolytic capacitor, it is characterized in that: by between anode foils and Cathode Foil, inserting the division board of the compound that contains vinyl, carry out around forming capacitor element, the solution of impregnation sodium naphthalene sulfonate in this capacitor element, generation forms the solid electrolyte layer that is formed by electric conductive polymer afterwards by the combination that compound that contains vinyl and sodium naphthalene sulfonate form.

24. the manufacture method of a solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer in this capacitor element

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, to use this division board to carry out being immersed in the polyimides silicon solution around the capacitor element that forms, surface at oxide-film forms by containing the film that vinyl compound and polyimides silicon form, and forms the solid electrolyte layer that is formed by aforementioned electric conductive polymer afterwards.

25. the manufacture method of a solid electrolytic capacitor, it is by insert division board between anode foils and Cathode Foil, carry out around forming capacitor element, impregnation polymerizable monomer and oxidant form the solid electrolyte layer that is formed by electric conductive polymer in this capacitor element

It is characterized in that: make the compound that contains vinyl in the aforementioned division board, to use this division board to carry out being immersed in the polyimides silicon solution around the capacitor element that forms, surface at oxide-film forms by the 2 layers of film that forms by polyimides silicon that contain vinyl compound, further form in the above, forms the solid electrolyte layer that is formed by aforementioned electric conductive polymer afterwards.

26. as the manufacture method of each solid electrolytic capacitor of putting down in writing in the claim 15 to 25, it is characterized in that: the aforementioned vinyl compound that contains is a polyvinyl alcohol.

27. as the manufacture method of each solid electrolytic capacitor of putting down in writing in the claim 15 to 26, it is characterized in that: aforementioned polymerizable monomer is a thiophene derivant.

28. the manufacture method of the solid electrolytic capacitor of putting down in writing as claim 27, it is characterized in that: aforementioned thiophene derivant is 3,4-ethylidene dioxy thiophene.

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