TW468189B - Solid electrolytic capacitor, its fabrication method and oxidizing agent solution for polymerizing an electrically conductive polymer - Google Patents

Abstract

The present invention relates to a solid electrolytic capacitor having a large capacitance and a higher resistance to heat and adapted as a surface-mount device and a method of producing the same. The followings are the features of the invention. (1) A layer containing an electroconductive polymer and a less conductive polymer is provided on a dielectric oxide film on the positive electrode foil. (2) A separator of a polyester resin based unwoven fabric made by span bonding and/or wet processing a resin material is sandwiched between the positive electrode foil and the negative electrode foil and rolled together to form a capacitor element which also include a solid electrolyte. (3) A separator is sandwiched between the positive electrode foil and the negative electrode foil coated with a dielectric oxide film exhibiting a withstand voltage of 0.8 to 10 V and rolled together to form a capacitor element which also include a solid electrolyte of an electrically conductive polymer. (4) The negative electrode foil is coated with a layer made of at least a metallic material selected from titanium, zirconium, hafnium, and its compound or of a carbon material. (5) The capacitor element has its content of water adjusted to not higher than 1% by weight and is enclosed in an outer case. (6-A) The solid electrolyte is a conductive polymer prepared by chemically polymerizing a heterocyclic monomer with the use of an oxidizing solution of which the weight ratio of bivalent iron to trivalent iron is not higher than 0.02. (6-B) The solid electrolyte is a conductive polymer prepared by chemically polymerizing a heterocyclic monomer with the use of an oxidizing solution of which the molar ratio of aliphatic and/or aromatic sulfonic acid to trivalent iron ranges from 3.0 to 3.5. (7) The solid electrolyte is a conductive polymer prepared by chemically polymerizing a heterocyclic monomer in which the remaining of a basic organic solvent is not higher than 0.8%.

Description

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 818 9 A7-B7 V. Description of the Invention (!) The present invention relates to a solid electrolytic capacitor and its manufacturing method, and an oxidant solution for conductive polymer polymerization, that is, there are A solid electrolytic capacitor having a winding structure using a conductive polymer as an electrolyte material and a method for manufacturing the solid electrolytic capacitor, and a polymer for conductive polymer for polymerizing the conductive polymer of the solid electrolytic capacitor Oxidant solution. With the increasing frequency of electronic equipment, the demand for electrolytic capacitors with excellent impedance characteristics and large capacity in the high-frequency field is gradually increasing. Recently, in order to reduce the impedance in the high-frequency field, research on solid electrolytic capacitors using tetracyanoquinodimethane salt (hereinafter abbreviated as TCNQ) having high electrical conductivity and conductive polymers as electrolytes has been ongoing. Also, for the requirement of large capacity, some people continue to propose the use of wound type solid electrolytic capacitors with TCNQ and conductive polymers as the electrolyte (the anode foil and the cathode foil are wound with an insulation layer wound). Compared with those in the electrode box, it is easier to increase the capacity. In this field of wound solid electrolytic capacitors, there have been many proposals on the method of forming conductive polymers so far. Generally, the heterocyclic monomer solution and the oxidant solution are alternately electrolytically polymerized or chemically polymerized to form a solid electrolyte layer. 'Or use a mixed solution of a monomer solution of a conductive polymer and an oxidant solution for electrolytic polymerization or chemical polymerization to form a solid electrolyte layer. Whereas the heterocyclic monofluorene proposed here is Neiming, stilbene, ethoxylated thiophene, aniline or its derivatives, and the oxidant solution is p-toluene acid, second iron, M 'undecylic acid and basic acid. The iron paper, second iron salt of cinnamic acid, second iron salt of triisopropylnaphthalenesulfonic acid, and long-chain aliphatic sulfonic acid, etc. The paper standards containing the second iron salt are applicable to China® Family Standard (CNS) A4 specifications (210 X 297 mm) f! ----- ^ — 1— equipment --- (Jing first read the precautions on the back before filling out this page) Order-• Line. -5--^. Guide.士 9, .ίβψ..μ · * '---.' 3 have * points Γ pay for the use of oxidized floc .. Detailed recommendations for the impact of liquid _ or ring-shaped generations. Pay next g The technology from various BSs is washed away. Agent: The concentration of seven agents of gas in the liquid container has been specified as a winding type capacitor structure, and it must be interposed between the anode foil and the cathode-an isolation layer to Avoid contact between the anode box and the cathode ^, and it is well-known that electrolytic capacitors that use conventional electrolytes as electrolytes use so-called electrolytic papers made of manila hemp or kraft paper as the insulation layer. Isolation for dead weight in wound solid electrolytic capacitors used as electrolytes | 'It is known to use 1 乂 glass fiber as the main component of non-woven fabric, Manila hemp J_ 乂 and electrolytic paper composed of kraft paper_ which is wound around capacitor elements Heat treatment is applied inside. Electrolytic paper (hereinafter referred to as carbonized paper) in a carbonized state after electrolytic carbonization is used as a separator. Further, as in the technology disclosed in Japanese Patent Laid-Open Publication No. 10-34〇829, in a solid electrolytic capacitor, an isolation layer is composed of a non-woven fabric mainly composed of synthetic fibers, and the non-woven fabric is recommended in the publication. Vinylon (Polyvinyl alcohol-based resin 丨 or mixed non-woven fabric with Vinylon as the main component and mixed with other resins. As for the manufacturing method of winding type electrolytic capacitors with TCNQ as the solid electrolyte, there are the following suggestions That is, first heat T (: NQ to a temperature above the melting point for a short time, so that the molten liquid TCNQ (the component that substantially contributes to conductivity is 100 ° /.) Penetrates into the capacitor element, and then It is cooled, and a TCNQ is formed between the anode foil and the cathode foil of the capacitor element. It is printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 6 8 18 9 A7 ___B7____ 5. Description of the invention (3) Solid electrolyte layer. There is also a proposal At this time, a dielectric oxide film of about 2 to 5 V is applied to the cathode foil to prevent the voltage from going backwards in the opposite direction of the capacitor. As the cathode foil of an aluminum electrolytic capacitor having an electrolytic solution as an electrolyte, for example, there are proposals of Japanese Patent Laid-Open Publication No. Sho 60—1826, Japanese Patent Laid-Open No. 1-304720, Japanese Patent Laid-Open No. 9-186054, and the like. Technologies such as titanium are used to increase the electrostatic capacity of the cathode foil, or to prevent leakage of the electrolyte due to an electrochemical reaction on the cathode side. Titanium and titanium nitride are formed on a cathode foil made of a conductive metal such as Ming. It is generally considered that solid electrolytic capacitors using a conductive polymer as a solid electrolyte are compared with capacitors using a liquid electrolyte (electrolyte) type having a vapor pressure because capacitor elements are not soldered by soldering. The components that evaporate under the high temperature environment (specifically 200 C or higher) when the electronic component women's clothing is on the surface of the printed circuit board, so when the surface is mounted, the pressure in the outer box will rarely increase. However, it is rare for the outer box to swell or damage the sealing component, and surface mounting will be easier. However, conductive polymers are used as solid electricity. Compared with the electrolytic capacitors of electrolytic capacitors, the research on the surface of high-quality solid electrolytic capacitors is still behind. In fact, the surface-mounting technology of capacitors using conductive polymers as solid electrolytes has not yet been established. In addition, when TCNQ, an electrically conductive solid electrolyte or conductive polymer, is used as the capacitor's electrolyte, the electrolyte does not have ionic conductivity, so I 111 ^ -----— II — — — — — —-: (Please (Read the precautions on the back before reading this page)

J Js' ^ Standing on the heating step towel and there is an easy short circuit Isolation method of ~~ ^^ is because the strong object when the coil is bent is more than that of the bending part _! *. And ^. _ I It is easy to be damaged due to the gasification of the plant and the leakage current of the capacitor B `` Besides the dagger, there is a short circuit prone problem during the heating step. Also, glass cutting, 隹 non-woven fabrics are cut and wound, because the needle-like glass fibers will be placed in the same direction. There is also a major problem for the working environment. Furthermore, for electrolytic paper in a carbonized state, if the capacitor element is not heated to more than 25frc i =, it is difficult to maintain TC'NQ and conductive polymer at 2. In the frequency domain, the carbonized state has a reduced impedance, and heating not only damages the dielectric film, increases the leakage current, but also oxidizes the plating layer of the lead wire of the electrolytic capacitor (such as tin-lead eutectic soldering). After the usual plating line is completed, the soldering wettability of the leading part of the product will be significantly reduced, so, Do not use strong high oxidation resistance of the silver plating of the wire or the like problems. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs.Because the tensile strength of non-woven fabrics composed of vinylon and mixed non-woven fabrics mainly composed of vinylon and mixed with other resins is weaker than that of electrolytic paper, capacitor elements are likely to be isolated during winding. When the layer is shredded, not only is the short-circuit occurrence rate high during aging, but it is also difficult to maintain the conductive polymer in the isolation layer due to the influence of the adhesive component used when the resin fiber is thinned. The problem of solid electrolytic capacitors with low impedance in the high frequency field. In addition, due to the lack of heat resistance of vinylon resin, high-temperature reflection is used when solid electrolytic capacitors are used for soldering and soldering at high temperatures. P This paper is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 8 18 9 A7 B7 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (5) In the case of" Vigny, the resin is easy to decompose, and the sealing part is damaged due to the rise of the internal pressure due to the occurrence of gas. " Electrical characteristics and other issues. It is also generally considered that solid electrolytic capacitors using TCNQ and conductive polymers as solid electrolytes are compared with capacitors that use liquid electrolytes (ie, electrolytes) with vapor pressure, because capacitor elements are not soldered by soldering. The components that will evaporate under the high temperature environment (specifically above 200 ° C) when the electronic component is mounted on the surface of the printed circuit board, so when the surface is mounted, the pressure in the outer box will rarely increase. As a result, problems such as swelling or damage to the sealing components of the outer packaging box are rarely caused, and surface mounting will be easier. However, in fact, because the solid electrolyte itself easily adsorbs moisture in the air, during the manufacturing process, the electronic component itself retains a large amount of moisture, and because the adsorbed moisture will vaporize under high temperature conditions during surface mounting, 'so' The inventors of the present case have found that it is difficult to achieve surface mounting equal to or more than those using an electrolyte type. That is, in the conventional structure, the glass fiber nonwoven fabric used as the insulation layer originally uses sand dioxide having high affinity with water as the main raw material. Therefore, when compared with the resin-made insulation layer, it absorbs air to make water It has a large capacity, so after the formation of the solid electrolyte, the moisture content of the capacitor element is still high, and it is not suitable for surface mounting. Also, "carbonized paper is originally made of cellulose with high affinity for water, so when compared with resin-made insulation layers, it has a higher ability to absorb moisture in the air." The retained moisture content is still high, and it is not suitable for surface mounting. This paper size applies to China National Standard (CNS) A4 specifications (210 X 297 public love) --1111 — III — I — — — — — — — I — — — — — — — — (Please read the Please fill in this page again) -9- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs * IJfi Another-Evening Knowledge >: se, .'1 FREE Sister Electrolyte. ¾ ^ leizhuji is best for begging iu Dagger, print ... one on one '_ "; one — K deposits the phenotype to carry on: Bu, m, p, in the shape of m. ^^ 一一 毛', Shengnancai + Keep it in Tzudouwei full + ., 4 sighs, 'I and glass fiber woven fabric. With polypropylene as the main body: >, ^ α 1 1, non-k cloth and _ thermal 4 force and other electrical polymer peel, resulting in K layer "Compared with the resistance" and increase the capacity extraction rate with the electrolyte as the electrolyte protection + + a 'Meng', so when compared to the capacitor ^, the average capacity of t is too large .. '' Each set & Ning You In the various types of solid-state electrolysis cells of the winding type, the extraction rate of the cathode capacity is very low compared to the static electricity of the anode hall. The phase extraction rate of the electrostatic capacity at the listening side is very low. Capacitance composition is based on the anode foil gamma bow + + u ~ Zhidian ^ The electrostatic capacitance drawn from the white side and the cathode box 出 are drawn together to form a capacitance, so the capacitance of the capacitor itself; the extraction rate usually only reaches 4 〇 side, the result is compared with the capacitor when using an electrolytic electrolyte, and there are ^ 10 problems, the size of f is too large n To address this problem, it is necessary to take the following countermeasures, that is, containing Heterocyclic monomers such as oxytelokine, and the second iron salt of p-methylbenzyl acid: Polymerization solutions of oxidants and solvents (alcohols such as water and n-butanol) penetrate into the capacitor element Θ, and are chemically polymerized on the electrode A large amount of conductive: macromolecules are formed near the surface of the museum. To achieve the above countermeasures, it is appropriate to use an insulation layer structure with a large amount of liquid retention and a very low density; however, once the density of the insulation layer decreases, the short circuit rate increases. And 'especially in solid electrolytic capacitors with a rated voltage of more than 16V', if the isolation layer is turned off to reduce the short-circuit rate and increase the withstand voltage, this paper will again apply the Chinese National Standard (CNS) A4 specification (210x297 mm) ) ----------------- Install --------- Order --------- Please read the back of the line :, i4 items before filling (This page) -10- ^ 8189

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (7) The volume density of the isolation layer will be increased, and the amount of polymer solution near the electrode tears cannot be fully ensured. Problems with solid electrolytes in sufficient quantities of conductive polymers. For this reason, it is known that it is generally difficult to uniformly and sufficiently penetrate the conductive polymer into the wound capacitor element, especially in the case of polyethylene oxide polymerized by ethylene oxide. In phenanthrene, due to various oxidation conditions (specifically, the difference between batches of oxidant solution and heterocyclic monomers) and the polymerization conditions, and after the oxidant solution is adjusted, the monomers of the conductive polymer are polymerized. High frequency range determined by the elapsed time, etc., of deviations in electrical characteristics (especially the deviation in capacitance due to the coverage on the dielectric oxide film of the conductive polymer and the filling rate of the conductive polymer) Internal impedance deviation). In order to solve these problems in the past, the purpose of the present invention is to provide a solid electrolytic capacitor having a small leakage current, a large capacity, and a high heat resistance, which is suitable for use as a surface mount component, and a method for manufacturing the same. One object is to provide an oxidant solution for conductive polymer polymerization which can stably produce a solid electrolytic capacitor having the aforementioned properties with a good yield. According to the foregoing object, the present invention includes: (1) providing a structure in which a dielectric oxide film of an anode body composed of a valve-acting metal is provided with a layer containing an electronic conductive polymer and a molecule lacking conductivity. (2) In order to obtain a solid electrolytic capacitor composed of the above structure and having a winding structure, there are the following manufacturing methods, that is, the Chinese national standard (CNS) A4 specification (210 X 297 mm) --------- install -------- order --------- line-. V * y (please read the precautions on the back before filling the vn copy (Page) -11-:: Delamination, immersion: · Responsibility 1. Conductivity 1ii high, body. ¾. Ί 犋 The victory of the stack benefits and Yin: ¾ between the branches to form a capacitor element. Capacitor π electric: Health high + lack of guidance, lightning high scores. Bu:.,: Then in the night, 'Hold this capacitor to make the former: the mysterious component of the mysterious liquid in the hair, and at least 柃A layer of the anode foil's electrical vaporizer is provided with a layer containing electrons & knives and polymers lacking conductivity. Furthermore, the capacitor element is immersed in a solution containing at least a conductive polymer polymerization oxidant. Or in a mixed solution with a heterocyclic monomer, or immersed the capacitor element in a solution containing a conductive polymer polymerization oxidant, and then immersed it in a solution containing a heterocyclic monomer After the capacitor element is immersed in a solution containing a hetero-type monomer, the capacitor element is immersed in a solution containing a conductive polymer polymerization oxidant to form between the anode foil and the cathode foil. A solid electrolyte composed of two molecules of conductive rhenium. In addition, (3) the solid capacitor includes a capacitor element and a solid electrolyte, the capacitor element is between an anode foil and a cathode 洎 formed with a dielectric oxide ytterbium, and the resin is used as the main body and the spunbond method and / or A separator made of a non-woven fabric obtained by a wet method, and then wound to form the electrolyte, and the electrolyte is provided between the cathode foil of the capacitor element and the cathode pig, and there is a V-electrolyte molecule: especially the separator The layer is made of non-woven polyester resin mainly composed of polyethylene terephthalate and its derivatives. In addition, the solid electrolytic capacitor can also include a capacitor element and a solid: electrolyte. The Shaw capacitor element is formed in an anode box formed with a dielectric osmium oxide and formed with a dielectric oxidant. 8 ~ 10V dielectric oxidation The paper of the film: i i. -If I I.!-Ti. 11¾ 1 ίΛ n -1 1 * 1 ^ 1 nb— i fl— i I in n II n I! Please read the back first; Please fill in this page again for the matter ') Printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 12 Printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 468189 A7 _ B7 V. Description of the invention (9) Insulation layer between the foils (the special system Non-woven insulation layer mainly composed of resins such as polyethylene terephthalate, etc.), and further formed by winding the solid electrolyte. The solid electrolyte is formed by containing a high conductivity between the anode foil and the cathode foil of the capacitor element. Made up of molecules. And / or (5) the solid electrolytic capacitor comprises a capacitor element and a solid electrolyte, the capacitor element is formed on an anode foil formed with a dielectric hafnium oxide film and at least one metal or a compound thereof formed of titanium, hafnium, or hafnium; or The solid electrolyte is formed by holding a separator (especially a non-woven separator composed mainly of a resin such as polyethylene terephthalate) as a covering layer between a cathode foil made of a carbon film material, and the solid electrolyte, It consists of a conductive polymer that is placed between the anode foil and the cathode foil of the capacitor element. In addition, (6) the solid electrolytic capacitor may include a capacitor element, an outer packaging box, and a sealing component. The capacitor element is formed by holding an insulation layer between an anode foil and a cathode foil formed with a dielectric oxide film, and further It is wound to form a 'solid electrolyte layer containing a conductive polymer' between the anode foil and the cathode foil, and the moisture content is based on the weight as i weight% or less. It is made of metal with a bottomed tube shape, and is used to accommodate the capacitor element, and the sealing component contains a polymer component and closes the opening of the outer packaging box. (7) The solid electrolytic capacitor may include a capacitor element, an outer packaging box, and a sealing component. The capacitor element is a holding insulating layer between an anode foil and a cathode foil formed with a dielectric oxide film layer. The outer packaging box is made of a metal with a bottomed 茼 shape. It is used to store the capacitor element, and the sealing component is made of oxygen paper. The Chinese standard (CNS) ) A4 size (210 X 297 Public Love > ------------------------ II ting ----- I-- line-.) / 1 (Please read the back first Note for re-filling t; this page) -13- Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs printed * ΙΛ chemical offenders. Brother 殳 .., or .1¾. Cats such as cutting edge _ _ "base rubber jump shirt $ 成 者 又 '+ 8) You should think about electrolytic thunder and cry for you — τ… 5 in _' will you 昉 斿, ¾ or fang 杳 sulfonic acid No.-: iron salt, the solution is in the chain: price ^% -The bath is a good gas, and the capacity is: Φ is less than the amount of trivalent iron, and the amount of iron is less than μμ, and the amount of oxidant solution is less than 0.02. (9) This solid electrolytic Capacitors' can be dissolved in a solution of 1 aliphatic and / or fragrant acid second iron salt in an alcoholic solvent, with an ear ratio of 3.0 to 3.5 relative to the amount of trivalent iron ㈣ aliphatic and / or ΗΜ 0 The nm agent n uses the conductive two molecules obtained by chemically oxidizing and polymerizing a heterocyclic military problem as a solid electrolyte, and M 1)), which constitutes the capacitor's lightning resistance. $ / V; & The composition of the oxidant solution is 1 in an oxidant solution prepared by dissolving an aliphatic and .. The ratio of the amount of divalent iron used is equal to or less than 0,02 by weight ... For the amount of trivalent iron, the ratio of the amount of aliphatic and / or aromatic sulfonium is in the range of Mohr ratio 3 [] to 3 5. Also, (1Π the solid electrolytic capacitor 'is a solid polymer that uses a conductive polymer obtained by chemically oxidizing and polymerizing a heterocyclic body containing impurities of a residual organic solvent of less than 0% .. Also, ( 12) The manufacturing method of the solid electrolytic capacitor is as follows: first, a capacitor element is formed between an anode foil having a dielectric oxide film formed thereon and an anode foil passing from a shaft to a negative foil, and an insulating layer (particularly based on Polyethylene to nail—! 5 :. :: 4 C with r-Γί >,: β Please open first. ¾ Read the back of i; fill in this page with the items of interest > ------- binding.- The linebook #m applies the Chinese National Standard (CNS) A4 specification “297 Public Love” -14- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 68189 A7 One B7 V. Description of the invention (11) Diacid and other resins Zhao Zhi non-woven insulation layer), and then wound it to form a capacitor, and then at least impregnated the capacitor element-the second iron salt of aliphatic and / or aromatic acids (especially the first Iron) is dissolved in an oxidant solution made of an alcoholic solvent. The ratio of the amount of iron is 0.02 or less by weight, and the ratio of the amount of aliphatic and / or aromatic sulfonic acid to the amount of trivalent iron is a molar ratio of 3.0 to 3 5 Heterocyclic monomers (especially ethylene dioxythiophene) with a miscellaneous mass of less than 0.8% of the solution and the residual alkaline organic solvent to form a conductive polymer (especially polyethylene oxide) between the anode foil and the cathode foil A solid electrolyte of thiophene), and further, it is used in combination with the constitution of the manufacturing method described in the above (2). According to the invention, a small leakage current, a large capacity, and high heat resistance can be obtained, which is suitable for use as a surface mount component. Solid electrolytic capacitors can also be used to produce solid Zhao electrolytic capacitors with excellent electrical characteristics and stable yields. They can also obtain oxidant solutions for conductive polymer polymerization and heterocyclic monomers for conductive polymers. [Figure Brief description] Figure 1: A perspective view of a section of a solid electrolytic capacitor in accordance with an embodiment of the present invention. Second circle: A conceptual diagram in which important parts of the same capacitor element are enlarged. The first aspect of the invention is a structure in which a dielectric layer is formed between the anode electrode and the cathode flute to support an isolation layer, and then it is wound to form a capacitor. This paper applies the China National Standard (CNS) A4 specification. < 210 X 297 mm) -15-— J'J Policy ----- Order! 1 · Wire {Please read the precautions on the back before filling out this page) A7 B7 V. Description of the invention (12) Device element ', and the capacitor element is provided with at least electronic conductivity on the dielectric oxide film of the anode box A layer of a polymer and a polymer lacking conductivity. According to this structure, an electronic conductive polymer having a low resistivity is disposed on a dielectric oxide film as an electrolyte, and the resistivity of a capacitor can be reduced. Reduce the impedance of the capacitor, and furthermore, because the dielectric oxide film is provided with a non-electronically conductive polymer that lacks electrical conductivity and has a very high resistivity (which can also be insulating depending on the occasion), even the dielectric Electrolytic disintegration) begins to occur in the damaged part of the damaged part, and when the leakage current is significantly increased, the electronic disintegration can be suppressed, and the phenomenon can be suppressed in the local area until the dielectric body is destroyed (short circuit ), It can constitute a solid electrolytic capacitor with small leakage current and not easy to short circuit during aging. * By providing a polymer lacking conductivity on the dielectric oxide film, the effect of improving the coverage of the electronic conductive polymer on the dielectric oxide film can be obtained. Big solid electrolytic capacitor. The number of copies printed by the Consumer Cooperatives of the Ministry of Intellectual Property Bureau — — — — — — — I! — ——.. I I I I I — I Order ·! 111! ^^ (Please read the note on the back before filling in this summer) In the second aspect of the present invention, in the first aspect, the electrons of the layer provided on the dielectric film of the anode body are conductive. The resistivity of the polymer component monomer is less than 1.0 × 1010 Ω / □, and the resistivity of the polymer component monomer lacking conductivity is more than 1.0 × 100 Ω / □. According to this structure, since the resistivity of the electronic conductive polymer is set to 1.0 × 1010Ω, □ or less, the impedance performance of the loss capacitor can be eliminated, and the resistivity of the polymer lacking conductivity is set to l. .〇xl01QQ / □ or more, so that the electronic disintegration phenomenon can be suppressed to a local range, so that the layer on the dielectric oxide film can have sufficient insulation properties, so that a leak can be obtained without damaging the impedance performance Low current, • 16 · This paper is scaled to Chinese Θ Standard (CNS) A4 (210 X 297 mm) 468189 Consumption cooperation between employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by A7 B7 V. Description of the invention (13) A solid electrolytic capacitor coil which is not prone to short circuit. In addition, if the resistivity of the electronic conductive polymer is more than 10 × 10, the resistivity of the electrolyte will be increased, and the impedance performance of the capacitor will be deteriorated. Therefore, it is inappropriate to set the value exceeding this value. If the resistivity of the polymer is below 1.0 × 100 Ω / □, it is difficult to suppress the phenomenon of electron disintegration to a local range so that the layer on the dielectric oxide film has sufficient insulation properties. So it is also not ideal. In the third aspect of the present invention, in any of the first or second aspects, the electronically conductive polymer of a layer provided on the dielectric oxide film of the anode body is selected from the group consisting of at least One of them is formed, the group is: polypyrrole, polyaniline, jinghua polyaniline, polythiophene, polyethylenedioxythiophene, polyethylene sulfonic acid and derivatives of these compounds; Structure, so the conductivity of the electronic conductive polymer is extremely high, so it is not only easy to set the resistivity of the electronic conductive polymer in the layer provided on the anode dielectric oxide film to 1.0 × 1010Ω / □ or less, and Compatibility with polymers that lack conductivity (described in the description of the fourth aspect of the present invention), such as cyclopropylpropyl modified polyester, sulfonic acid modified polyester, carboxylic acid modified polyester, etc. Very high, so by using these non-electroconductive polymers together, it can have the effect of improving the coverage of the dielectric oxide film by these electronic conductive polymers, so it can constitute a very small leakage current, and Short circuit is not easy to occur during aging, and the capacity extraction rate is large Large solid electrolytic capacitor. According to a fourth aspect of the present invention, in any of the first or second aspects, a component of a polymer lacking conductivity in a layer provided on a dielectric oxide film of an anode body is selected from the following: For at least one of the polymers or copolymers, the paper size applies to the Chinese National Standard (CNS) A4 (210 X 297 mm) --------!-Packed!! | Order (Please read first (Note on the back of this item is again on this page) -17- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs-Invented TD ..; Public, 3 rhetoric: Section ¾ is enoate polyts:! * 哞 Polyurethane, 聚 is polyene ^^ .. w. Packing isoΛdiene. Polyether polyester. Ethylene glycol, polymer / dicarboxylic acid, two bromide, polyamine, polyimide. 'Lower aldehyde resin, silicon j > street fat. Di.-polymelamine resin, alkyd street fat' cellulose , Nitrocellulose. Sewing off: \ -type epoxy resin .. Double-type F-type epoxy resin .. Alicyclic epoxy resin, resin, and a group consisting of its derivatives; Those who make up these polymers or copolymers that lack conductivity: and It is easy to set the resistivity to 1.0 01 ΰ Ω ..._: "above" so it can constitute a layer on the dielectric gasification board that suppresses the electron disintegration phenomenon to a local range and has sufficient insulation properties. • Therefore, it can constitute a solid electrolytic capacitor with extremely small leakage current and less prone to short circuit during aging. Also, although nylon is a polymer that lacks conductivity, its water absorption rate is high. Therefore, it is not ideal because of the influence of the moisture absorbed when the electron disintegration phenomenon occurs, and the prevention rate of the electron disintegration phenomenon is low. In the fifth aspect of the present invention, in the fourth aspect, the polymer lacking conductivity in the layer provided on the dielectric gasification film of the anode body contains at least one of the following polymers or copolymers The 'property' is a group consisting of epoxy propyl modified polyester, sulfonic acid modified polyester, and carboxylic acid modified polyester; according to this structure, such polymers or copolymers lack high electrical conductivity. It is easy to set the resistivity to 1.0 × 1 〇π) Ω / □ or more, so it can not only constitute a dielectric body that suppresses the electron disintegration phenomenon to a local range and has sufficient insulation properties. In addition to the layer on the oxide film, it can also depend on the effect of the substituent of the variant, which has the effect of improving the coverage of the dielectric conductive film by the electronic conductive polymer. The paper size is applicable to China National Standard (CNS) A4 (210 X 297g t)-丨 丨 i 1ί. 丨 丨 丨 丨 丨 '丨! — 丨 丨-_ 1] Read the precautions on the back before filling out this page) -18-468189 A7 ____B7____ V. Description of the Invention (I5) As a result, it can constitute a very small leakage current, and it is not easy to short-circuit during aging. , And a large-capacity solid electrolytic capacitor with a very high capacity extraction rate. (Please read the precautions on the back before refurbishing this page.) The sixth to eighth aspects of the present invention include a capacitor element and a solid electrolyte. The Valley II element is based on an anode pig with a dielectric oxide film. It is formed by splicing and / or wet-laid non-woven separators based on reading grease (special materials such as polyethylene terephthalate) with the cathode m and then winding it to form The solid electrolyte is composed of a conductive polymer provided between the anode foil and the cathode foil of the capacitor element. According to this structure, a solid electrolyte composed of a conductive polymer obtained by chemically polymerizing a heterocyclic monomer representing polyethylenedioxyphene and a resin as a main body, and a spunbond method and / or a wet method are used. Adhesion and adhesion of non-woven fabrics (such as polyester fibers, nylon fibers, fluorene fibers, trimethylpentene fibers, polystyrene sulfide fibers, celluloid [or nitrated fibers] fibers) Excellent performance, can further reduce the impedance in the high frequency area. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the non-woven fabric obtained by the spunbond method is different from the synthetic resin non-woven fabric made by other methods, because it does not use adhesives and resin when thin plates are used, and can be glued by heat. The method and the method of mechanically arranging a thin plate make it difficult for chemical polymerization to be inhibited and peeled off due to the influence of the components of the adhesive. Therefore, it is possible to easily hold chemically polymerized conductive polymers such as polyethylene dioxyphene on the isolation layer. According to this, a solid electrolytic capacitor with low impedance in the high-frequency field can be formed. Furthermore, the non-woven fabric obtained by the spunbond method is compared with the non-woven fabric manufactured by the dry melt blowing method of the same dry method because the length of one fiber is -19- This paper standard applies to China National Standard (CNS) A4 Specifications (210 X 297 mm) The same thickness. The same amount # 3 trough device t with rolls, body s ~ ... Manichi: '' .π _ layer W 峄;: ..S details Zhong :.. ㈣Happened: " Drop ⑤ So reasonable: ¾ ...... ~ 'and using polyester resin as its body and drinking thirsty by using thirsty method ^, tr ... body and drinking Farr: look different .Although θ 'm has a strong body 1 If the same thickness is used, the same T will be compared.' Because of the tensile strength + the strength of the father, the frequency of the shredder when the capacitor element is wound is reduced [short circuit occurs The rate is also reduced ^, non-woven fabric obtained by wet method refers to resin with I s resin. , Xiben—Ethylene formate resin or polyethylene terephthalate resin or polyethylene terephthalate resin or polybutylene terephthalate resin and nylon fiber, snail purple fiber , Polyvinyl ethoxylates, Poly-coated fibers, 隹 dimethyl n fibers, Polypropylene vulcanized m borosilicate (or sulfonated "fibers" fibers and fibers represented by horse & ramie fibers, etc. One of them is a mixed nonwoven fabric prepared by a wet method; and the content of the polyester resin and its derivative in the nonwoven fabric is preferably 50 wt. I / 0 or more, and particularly 80 wt.% or more. The content ratio of medium and polyester resins and their derivatives is 50% by weight. /. In the following, due to the low adhesion and adhesion between the non-woven fabric and the solid electrolyte, it will be difficult to maintain the impedance at a low level in the high-frequency region. In particular, the polyethylene terephthalate in the polyester resin is also It is very close to the compatibility parameter of polyethylene oxide which is a solid electrolyte and it is easy to be compatible with each other. Therefore, the adhesion and adhesion between the nonwoven fabric and the solid electrolyte are extremely strong. Compared with other synthetic resin insulation layers, it can further reduce the fullness of high-frequency collar paper. Applicable to China National Standard (CNS) A4 (21CU 297 mm) • i —i (ii JJ is ini D nni-I It. FteJ · Nnnni ... ^ Read the notes on the back before filling out this page) Printed by the consumer cooperation of the Intellectual Property Bureau of the Sub-Ministry-20- 46 8 1 8 9 A7 ______B7___ V. Explanation of the invention (17) Impedance within the rate "In the sixth aspect of the present invention, 'in the sixth aspect, the thickness of the insulation layer composed of non-woven fabric is less than 80 mm, and the scale is 1 mm. The range of ~ 60 g / m2; The composition 'because it can ensure that its tensile strength is suitable to prevent the capacitor element from being shredded when it is wound, so even a capacitor element with a small diameter' has a large average unit volume, and the anode foil and the cathode foil are large. The resistance becomes smaller, so a solid electrolytic capacitor with low impedance in the high-frequency area can be obtained. In addition, if the scale of the isolation layer is 10 g / m2 or less, it is not ideal because the insulation layer is often shredded during winding, and if the scale is 60 g / m2 or more, the impedance in the high frequency range will increase. So it is also not ideal. The constitution of the tenth aspect of the present invention includes a capacitor element and a solid electrolyte. The capacitor element is composed of an anode foil formed with a dielectric oxide film and a cathode foil formed with a dielectric oxide film having a withstand voltage of 0.8 to 10 V. The solid electrolyte is formed by holding an isolation layer and then winding it, and the solid electrolyte is composed of a conductive polymer that is provided between an anode foil and a cathode foil of the capacitor element. According to this structure, the dielectric oxide film formed on the cathode foil can have good moisture permeability with a polymerization solution (specifically, it contains a large amount of a solvent having an argon-binding property such as water and alcohol). The amount of the polymerization solution existing near the cathode foil is the same as that of a known person. The coverage of the cathode foil of the solid electrolyte produced by the conductive polymer will also be significantly improved, so the capacitance extraction rate will be higher, which will cause it to be extracted from the anode foil. The combined series capacity of the electrostatic capacity also becomes large, so a solid electrolytic capacitor with a large capacity can be obtained. Also, if the withstand voltage of the cathode foil is ίον or more, because the average unit size of the paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) ------------ order- -------- line (please read the first item on the back and fill in the S page) -21- Member of the Intellectual Property Bureau of the Ministry of Economic Affairs X Consumer Cooperative Co., Ltd. Printed% 台 ： ¾ 冬 _ 寺 ㈣ Capacitance 丨 Low-grade Ling-level " .If the electric repair is __ due to miscellaneous shape .. By mistake, it is related to f, capacity: to avoid violation of deterioration. Can not make the static capacitor # 七出 基提 and therefore The overdose of the Yin gasification film is G8 ... 丨 0 '., Which means ..... It is surrounded by ...… the heart is 隹' ';; the yin foil of aluminum electrolytic capacitors used in ^ know also has a degree of 0H5V The electric resistance is strong. But because it is composed of a thermal vaporization film and a natural oxide film, it is an uneven film. It also contains water leeches, which is inconsistent with the purpose of the present invention. The dielectric oxide film used in the present invention is suitable for the oxide film formed by the anode vaporization method. Because the dielectric oxide film formed by the anodization method is both fine and uniform, the surface of the cathode hall has good moisture permeability. In addition, the electrostatic capacity extraction rate can also be improved. X, the internal resistance of the cathode interface can be reduced, so that the impedance in the high frequency area is reduced. The constitution of the first aspect of the present invention includes a capacitor element and a solid electrolyte capacitor element, which are formed in an anode box formed with a dielectric oxide film and formed with at least one kind of metal or a compound thereof or a carbon-based material. The solid electrolyte is composed of a conductive polymer between the anode foil and the cathode of the capacitor element. According to this structure, the covering layer formed on the cathode foil can improve the moisture permeability with the polymerization solution (specifically, it contains a large amount of water-soluble alcohol and other hydrogen-binding solvents) and can be cleanly penetrated into the separation layer. The amount of polymerization solution can be more than those of other insulation materials. T-click .. ¾.?, Iv: Hook first and read the back; 1 Note the matter and then fill out this page} Installation-thread paper size applies Chinese National Standards (CNS) A4 specification (21 × x297 mm) -22- ^ 8189 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 V. Description of the invention (I9) Although the amount of the polymer solution existing near the cathode foil is the same as that of a conventional person, However, the coverage of the cathode foil of the conductive polymer solid electrolyte produced is significantly improved1, resulting in a higher capacitance extraction rate. Therefore, the combined series capacity of the capacitance with the capacitance extracted from the anode foil also becomes larger. Large-capacity solid electrolytic capacitor. Further, the compounds of titanium, tungsten, and hafnium are composed of oxides, carbides, and nitrides', and carbon-based materials include carbon, graphite, glassy carbon, and the like. In the twelfth aspect of the present invention, in the tenth or tenth aspect, the separation layer is a non-woven fabric with uneven density in the thickness direction, and has a winding structure with the low-density side of the non-woven fabric facing the cathode foil side. According to this structure, although it is necessary to form a solid electrolyte of a conductive polymer in order to draw the electrostatic capacity from the cathode box, a sufficient amount of a polymerization solution can be present near the cathode foil (the low-density side of the isolation layer), and it can be simultaneously Preventing sparks on the anode side due to short circuit and ensuring sufficient inter-electrode isolation (high-density side of the isolation layer). Therefore, despite its large capacity, short circuits are less likely to occur during aging during manufacturing. Also, the method of adjusting the density in the thickness direction of the insulation layer is preferably: a method of heat-sealing two nonwoven fabrics with different densities, a method of pressing, a method of using heat, melting, and pressing together, or A method of 'differing thickness densities in the thickness direction by adjusting temperature on the surface of a nonwoven fabric prepared in advance, and depositing and joining resin fibers in a softened or semi-fused state of the resin fibers ^ Adhesive agent followed by two isolation layers The method of adjustment will obviously reduce the impedance performance when forming the capacitor, so it is not ideal. The structure of the thirteenth aspect of the present invention includes a capacitor element, an outer box, and a sealing assembly. The capacitor element is formed by dielectric oxidation — — — — — — — — —. — — — — — Β, — II — — — — — (Please read the precautions on the back before this page ) -23- 唭 之 阳: ¾ and the solid electric alcohol f 1 柽 · 柽 该 a1 -f *-cathode-based female f printed by the Economic and Intellectual Property Bureau employee consumer cooperatives挦 之 # Wrap around and form ...-Contains conductive reference material; Weight ~. The box is made of metal phenol with a bottomed tube. It is a sealed component system containing container components and contains high The sheet component and the opening of the outer box are closed. According to this structure, in the manufacturing step, a body-shaped electrolyte and a wound capacitor element are inserted into a metal outer packaging box and the opening of the metal outer packaging box is used. The inside of the sealed metal packaging box (there is a wound capacitor element. 丨, only the moisture contained in the wound container element is vaporized (specifically, it is more insulating than the solid electrolyte and contains the moisture in the second gas) The judgement coefficient of the retained moisture is large because it is a metal that seals The internal pressure of the outer box is increased. Therefore, by limiting the amount of water held by the capacitor element, the internal pressure of the outer box is difficult to withstand even under high temperature conditions at the time of surface mounting, and stable surface mounting performance can be exerted. , Aluminum and aluminum alloy and other metal outer packaging boxes. Because it rarely plastically deforms due to pressure rise, it is combined with the aforementioned effects. 'Even under high temperature conditions during surface mounting, the outer packaging box is difficult to deform, and can be more Stable surface mounting performance. Furthermore, in the step of sealing a metal outer packaging box, when the outer opening portion is hardened, a high-quality sealing member containing an elastomer is used to obtain a stable sealing performance. In combination with the foregoing, even under high temperature conditions during surface mounting, the sealing surface is difficult to deform, and it can exert a more stable surface-mounting structure (1, 2), which can be installed in a solid state. (Electricity is easy to absorb outside the base). · Above the watch, it ’s in the box. I it. I i 1 ί i 1 I iii I ·. ^ 1--nn I- ^ OJ «J1 nnli 璜 Read the back first; 1 Please fill in this page again for the matters needing attention) This paper is again applicable to China National Standard (CNS) A4 specification (210 x 297 public love) -24- Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 46 8 1 8 9 A7 ___B7_____ V. Invention Explanation (21) The structure of the fourteenth aspect of the present invention includes a capacitor element, an outer packaging box, and a sealing assembly. The capacitor element is a holding insulating layer between an anode foil and a cathode foil formed with a dielectric oxide film layer. Then, it is wound to form 'the outer packaging box is made of a bottomed cylindrical metal and accommodates the capacitor element', and the sealed component is subjected to oxide sulfur and / or resin sulfur at 250 Formed by butyl rubber having an elastic modulus of 450 N / cm2 or higher at a temperature of 'C', and sealing the opening of the aforementioned outer box. According to this structure, since the butyl rubber subjected to oxide vulcanization and / or resin vulcanization has high heat resistance, even if extreme heat stress is added during installation, the sealing performance is not reduced, and the interior of the solid electrolytic capacitor is reduced. After a period of time, the solid electrolyte is not easily deteriorated due to the infiltration of water over a period of time, which can constitute a highly reliable solid electrolytic capacitor. In addition, the temperature of the solid electrolytic capacitor is usually in the range of 200 ~ 250 ° C. Therefore, the sealing rubber of the solid electrolytic capacitor is set at about 250 ° C with an elastic modulus of 450N / cra2 or more to make the installation When the internal pressure of the capacitor element rises due to moisture vaporization, the mechanical strength at that temperature is large when the internal pressure of the outer box rises, so the deformation rate due to the internal pressure is small. Deformation and stable surface mount performance. According to the constitution of the fifteenth aspect of the present invention, in the thirteenth aspect, peroxide-sulfurization and / or resin-sulfurization are performed on a sealing component containing a polymer component, and the temperature is 450N / cra2 or more at 250 ° C. The elastic modulus of butyl rubber, and the fifteenth aspect has the same effect as that obtained in the fourteenth aspect. The constitution of the sixteenth aspect of the present invention is to apply the Chinese National Standard (CNS) A4 specification (210 x 2 mm) to the standard of aliphatic and / or aromatic paper. • 25 · ------- ^ ---.--- ^ Order --------- line (please read the notes on the back before filling out this page) Dissolved in _ i: i name Xi Xiluo dissolves at night P phase heart. The amount of valence iron makes the car of free divalent iron amount tf A n,; 2 p ,: The monomer is subjected to oxidative polymerization and is used for the purpose of oxidation polymerization. The polymer is used as a perimeter electrolyte: it is formed in this way. The yield is good. The constitution of the 17th aspect is' in a solution obtained by dissolving an aliphatic and / or aromatic square yasulfonic acid second iron salt in an alcoholic solvent, and using an aliphatic and / or aromatic relative to the amount of trivalent iron. The ratio of the group sulfonic acid is an oxidant solution with a molar ratio of 0 to 0.5, and chemically vaporizes and polymerizes the heterocyclic monomer 5 and uses the obtained conductive polymer as a solid electrolyte. According to this structure, ° Get a good rate A conductive polymer having a high conductivity and a small amount of damage to the dielectric substance due to the free sulfonic acid component can reduce the leakage current. Relative to the amount of trivalent iron, if the ratio of aliphatic and / or aromatic sulfonic acid is equal to or less than 3.0, the amount of sulfonic acid component acting as a dopant is small, resulting in low conductivity of the conductive erbium molecule. , And the impedance performance deteriorates, so it is not ideal. In addition, if the ratio of the aliphatic and / or aromatic sulfonic acid with respect to the amount of divalent iron is 3.3 or more, the excess sulfonic acid will become chemically active in the solution relative to the amount that can act as a dopant. Free sulfonic acid, and damage the dielectric oxide film, resulting in large leakage current, so it is not ideal. From the reasons mentioned above, it can be known that the inventors of the present case used analytical methods (qualitative and titrimetric methods of trivalent iron and divalent iron), and oxidized oxidant solutions (especially alcohols having a fluorenyl group). (Solvent solvents) The paper size of the coat is in accordance with the Chinese National Standard (CNS) A4 specification (2) 0X 297. Jing first read the iit on the reverse side and then scolded this page.) Binding. --Line-26- Bureau of Intellectual Property, Ministry of Economic Affairs Printed by the employee consumer cooperative 468189 A7 _____B7 --------- V. Description of the invention (23) The fact that the divalent iron changes into divalent iron, and when it is found that there are more divalent iron, it is polymerized by chemical oxidation. A conductive polymer is available, but it will have a very significant impact. It has also been found that, especially in the alcoholic solution of the second iron of p-benzenesulfonic acid, doped with a lot of impurities of divalent iron, when it is adjusted by the oxidant solution, the elapsed time is very long, and the oxidant solution itself or after the blending When the storage temperature of the solution is very high, the amount of divalent iron will increase significantly, and the polymerization yield of the conductive polymer will decrease. This is because with the chemical oxidation and polymerization of heterocyclic monomers, the trivalent iron of the oxidant will be reduced to divalent iron. Therefore, if the impurities of the divalent iron exist in the oxidant solution in advance, the reduction reaction speed of the trivalent iron will be reduced. Decrease, even the chemical oxidative polymerization of heterocyclic monomer is hindered, resulting in low polymerization yield. Furthermore, the inventors used an analytical method (quantitative method of trivalent iron and sulfonic acid representing p-benzoic acid) and found a phenomenon that an oxidant solution (especially an alcoholic solvent having a hydroxyl group) is used as a dopant When the acting sulfonic acid component is relatively less than the trivalent iron, the doping rate of the chemical oxidation polymerization of the heterocyclic monomer by the trivalent iron desulfurization cannot reach a sufficient value, although the polymerization yield is not low 'but However, conductive polymers with low conductivity are preferentially formed. According to the present invention, by limiting the ratio of (A) the amount of divalent iron to the amount of trivalent iron and (B) the ratio of aliphatic and / or aromatic sulfonic acid to the amount of trivalent iron in the oxidant solution during polymerization, It has the effect of reducing the deviation of electrostatic capacity and impedance characteristics. According to the eighteenth aspect of the present invention, in the sixteenth or seventeenth aspect, the composition of the oxidant solution is an alcohol solution for the second iron salt of mebenzylsulfonic acid, which has a particularly significant effect. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 male *) ----------- I .--- Kang-! ----- Order *! 1 line '( (Please read the precautions on the back before filling out this page) -27- The ratio of the amount of fatty Egyptian or aromatic siblings is Moore :: bu. < J u red®, which constitutes the fourth or the first r-like state. The stable solid electrolytic capacitor-the 20th aspect of the present invention will contain N-II from 0-8% or less Heterocyclic monomers of impurities remaining in the basic organic solvent formed by methyl ethyl alcohol are used as the solid electrolyte for the conductive polymer obtained by chemical oxidation polymerization: according to this structure, 'the amount of residual basic organic solvents is limited Below the weight basis of {) _8%, the conductive polymer having a high conductivity is good in yield, and the resistance performance is lower and stable. The amount of residual organic solvents in the heterocyclic monomer should be 0.6. % In the following, the 21st aspect of the present invention is "in the 20th aspect, using polyethylenedioxophene as a heterocyclic monomer" and chemically polymerized by using at least an oxidant component and a dopant component The latter conductive polymer is used as the solid electrolyte of the capacitor. According to this structure, the amount of N.N-dimethylethylamine used as a reaction solvent is limited to the synthesis of polyethylene terephthalene ( Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Impurity Economy When combined, a high conductive polymer yield is good. In addition, for the reasons described above, the following can be known: solid electrolytic capacitors that generally use conductive polymers, and the method for forming conductive polymers is to chemically polymerize heterocyclic monomers In order to make the high-conductivity high-conductivity polymer yield good, in the acidic polymerization environment, this paper scale applies the Chinese national standard specifications (210 X i > 97 issued) -28- 468189 Employees of the Intellectual Property Office of the Ministry of Economy Cooperative printed A7 V. Description of Invention (25). This is because the yield and conductivity of the conductive polymer produced will decrease as the polymerization environment becomes more alkaline. The method of keeping the polymerization environment acidic can of course use the method of adding various inorganic and organic acids to a polymerization solution (such as a solution formed from a polymerizable heterocyclic monomer, an oxidant, a dopant, and a polymerization solution). However, depending on the type of acid added, when the conductive polymer is formed, a competitive doping reaction between the dopant and the added acid will occur, which will cause the inhibition of polymerization (specifically, the yield will be low). And the conductivity of the formed conductive polymer is low), therefore, the polymerization agent used in the polymerization solution itself should be limited to water and alcohols (methanol, ethanol, isopropyl alcohol, etc.) Propanol, n-propanol, n-butanol, ethylene glycol, etc.). In this example, n-butanol, ethylene glycol, and the like are used as the polymerization solution in the chemical polymerization of ethoxylated diphenone, which is one of the heterocyclic monomers. The inventors of the present case used an analytical method (gas chromatography-mass spectrometry), and found that, in particular, ethylenedioxane, which is one of the heterocyclic monomers, is mixed with impurities to make it exhibit alkali. The substance of sex. It was also found that the substance was N, N-dimethylacetamide. One of the reaction solvents used in the N, N-dimethylacetamidine polymerization of ethylenedioxyphene is also one of the most likely alkaline substances remaining in ethylenedioxophene. And it is known that the residual amount of N, N-dimethylacetamide has a very significant influence on the preparation of conductive polymers by chemical oxidation polymerization. According to the present invention, a solid electrolytic capacitor with a small deviation in capacitance and impedance characteristics can be obtained by limiting the amount of residual alkaline organic solvents. The paper size is suitable for the National Standard (CNS) A4 specification (21G X 297). _ ------ '! Τ1-' ^ 1--Order- --- J! -Line (please read the precautions on the back first: this page) • 29 ·

The Intellectual Property Bureau of the Ministry of Economic Affairs P 'Industry and Consumer Cooperatives printed the 22nd evil sea K made of this invention. Smoke: Yu Cheng Cheng You. Η. Electron membrane and foil: ¾ between holding. Translation Li. 罾. And to be continued, 乂 奴 奴 slave electrical appliances 再 再 .. This capacitor is immersed in 4. ping so far. Right. Ρ No. 9 sorrowful high conductivity score. . Polymerization oxidant solution and as follows:丨 Mixing of heterocyclic monomers in a state: in a liquid container. Or, dispersing the capacitor into a capacitor containing a gasification agent for conductive polymer polymerization as in the 9th state. Immerse in a solution containing a heterocyclic monomer as in the 20th or 21st state, or 'dip this capacitor element in a heterocyclic monomer solution containing the sensation as in 20th or 2nd Then, it is immersed in a solution containing an oxidant for conductive polymer polymerization as in the first () state, and a solid electrolyte composed of a conductive polymer is formed between the anode foil and the cathode foil. According to the composition and manufacturing method of the oxidant solution, it is possible to stably manufacture a solid electrolytic capacitor with a small deviation in capacitance and impedance characteristics. The present invention is a manufacturing method of a solid electrolytic capacitor, that is, a dielectric is formed The anode layer and the cathode foil of the bulk oxide film hold an insulation layer 'and are wound to form a capacitor element. The capacitor element is immersed in a conductive polymer containing at least the third aspect and the fourth or fifth aspect. In a solution of a plutonium molecule lacking conductivity, the capacitor is heated to evaporate the solvent component of the solution, and at least an electroconductive polymer containing electrons and a lack of conductivity are provided on the dielectric oxide film of the anode foil. The polymer layer. Then the capacitor element is immersed in a mixed solution containing at least a conductive polymer polymerization oxidant bath and a heterocyclic monomer, or 'this valley device is immersed in a conductive polymer After polymerization, the oxidant solution is then > collapsed into a solution containing a heterocyclic monomer, or the capacitor is applied to the national standard (C NS) A4 specification (2i〇x 297 public love) l: ci—tf J1 ·.?. If ts SI 1 i = LI, i —r · n IF i ^-· · nf i-t I 4 Back-Note: Please fill in this I > -30- ^ 68189 Printed by B7, Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs V. Description of Invention (27) After the element is immersed in the solution containing heterocyclic monomer, It is immersed in a solution containing a conductive polymer polymerization oxidant, and a solid electrolyte composed of a conductive polymer is formed between the anode foil and the cathode foil. According to this method, a solid electrolytic capacitor which is excellent in reducing leakage current and has a large capacity can be stably manufactured. The manufacturing method of the twenty-fourth aspect of the present invention is, in the twenty-third aspect, a solution containing a conductive polymer and a polymer lacking conductivity contains at least an aqueous solvent; according to this method, especially with the aforementioned synthetic resin (Polyethylene terephthalate) as the main isolation layer combination (because most synthetic resins are hydrophobic), by allowing water to exist in the solution to dry the solvent components in the solution, and the dielectric When a layer containing electronically conductive polymers and 1¾ molecules lacking conductivity is formed on the bulk oxide film, the layer can be distributed on the hydrophilic dielectric instead of being distributed on the fibers of the hydrophobic spacer because of the distribution control. On the bulk oxide film, the coverage of the electronic conductive polymer and the polymer lacking the electronic conductivity of the dielectric oxide film can be further improved, because it can take out the electrostatic capacity more efficiently than the dielectric oxide film. Therefore, it is particularly ideal for the production of large-capacity solid electrolytic capacitors. The water content in the solution containing the electronic conductive polymer and the non-conductive polymer is preferably 1% by weight or more, and more preferably 0% by weight or more. When the water content in the solution is 1% by weight or less, it is difficult to control the distribution. The manufacturing method of the twenty-fifth aspect of the present invention is that, in the twenty-third or twenty-fourth aspect, the guide paper used when forming a solid electrolyte composed of a conductive polymer is applicable to the national paper standard + national standard (CNS) A4 specification ( 210 X 297 mm) -31-1 I ---- install -------- order --------- line (please read item iii on the back of the page first, then click this page) High-molecular-weight oxygen-containing elixirs, the conductive state of the Rongguang method: the oxygen γ two-K combined milk solution, and the #ring type system system or the gas phase heterocyclic type. According to this method, the body sound of the rat is removed from the 3rd or the 3rd aspect of the 'ΐApple; 1 There are still the following from the invention of borrowing wood contained in the 2nd aspect.' Embodiment 1-Figure 1 and Figure 2 are partial cross-sectional views showing the structure of the solid electrolytic capacitor of the present invention and a conceptual diagram in which the same element is enlarged, as shown in the figure. After the surface is bond-bonded, a dielectric gasification film 1 1 is formed by the ablative treatment. The aluminum foil is used as the anode body. That is, the field electrode is extremely etched. The aluminum foil is etched and used as the cathode body. 2 while in anode foil 1 and female Foil 2 holds one. Isolation layer 3, and then it is wound to make a capacitor το 12 'and a layer 4 containing an electron conductive molecule and a polymer lacking conductivity is formed on the dielectric oxide film 1]: In addition, a capacitor 5 is formed between the anode foil 1 and the cathode poise 2 (connected to the layer 4 containing the electronically conductive polymer and the molecule lacking conductivity) to form a capacitor. Element 12 t_ The surface of the cathode oil 2 can be provided with a dielectric oxide film with a withstand voltage of 0 ~ 1ϋν (not shown in the heat map). Also, the surface of the cathode foil 2 can also be provided with titanium '鍅 to a medium; a metal or Its compound or a covering layer made of carbon film material (not shown) / The separation layer 3 is mainly composed of polyester resins such as polyethylene terephthalate, and the density of the isolation layer may be approximately the thickness direction. The uniform non-woven towel may be an isolation layer having different density in the thickness direction. I also use the insulation layer Risi with different density in the direction of drought. It is advisable to close the low-level paper towel of the insulation layer " read the urgent matters on the back before filling in this I) t. Consumption Cooperative Prints 297 mm) -32- A7

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Second, the capacitor element 12 is housed in a bottomed cylindrical box 9 and the open end of the box 9 is sealed by a rubber sealing material 8 but sealed by the anode. W and cathode 2 are externally led anode leads and cathode leads 7 through the sealing material 8 respectively. After that, a seat plate ⑺ can be further configured, and the anode lead 6 and the cathode lead 7 pass through the seat plate 10, and at least the anode lead 6 and the outer lead portion of the cathode lead 7 are folded back into a flat shape to constitute a surface mount. Type of solid electrolytic capacitor. The layer 4 containing an electronic conductive polymer and a polymer lacking conductivity may be formed at least on the dielectric oxide film η 'or may be formed on the surfaces of the cathode foil 2 and the isolation layer 3 at the same time. Next, specific embodiments of the present invention will be described; however, it should be understood that the present invention is not limited thereto. Also, all parts hereinafter are expressed by weight. First, implementation modes in the first to fifth and 23rd to 25th aspects will be described. (Embodiment 1) A spunbond nonwoven fabric insulation layer (thickness 50 // m, weighing 25g / m2) made of polyethylene terephthalate was held between the anode foil and the cathode foil, and wound. , To make a wound capacitor element (this capacitor element is impregnated with a 10% by weight ethylene glycol solution of amine adipate, and the electrostatic capacity at a frequency of 120 Hz is 670 // F). Second, the capacitor element was immersed in polyethylene dioxythiophene polystyrene sulfonic acid (a highly conductive electronically conductive polymer) at a concentration of 1.0% by weight, and the epoxy propylene modified polyester (lacking The concentration of conductive polymer) is 3.0. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -33-I ί -----— — — — — — (Please first Read the notes on the reverse side and fill in this page) ί. Inventions say two tft r- .¼ \ rc., :: licensed it ^: 1..p 1 Xi .; Cheng: meaning t — 〇tt. It is called broad basis. Λ) Φ 涘 after taking out. W 丨 5〇τ — Management, > Bell 'and Yttrium less e:'.;, Electricity Oxygen Chess Board ... ¾. *, Printed by the Consumer Cooperative of the Smart Financial Investigation Bureau of the Ministry of Economics and High Scores. Oxygen-containing poly (ethylene) tellurium bases and high-level electrical properties f. High-quality epoxy epoxy-based polyesters; side; a glass film with a thickness of 1 0 " m of polyethylene gas After supporting 3 layers of polybenzenesulfonic acid layer, the measured resistivity was 1, 〇χ 丨 〇4 八 Ώ / n.L ~ J.- and a ring with a film thickness of 10 pm was formed on the glass plate. After the oxypropyl A complex polyester layer is measured, its resistivity exceeds the rigid limit of the resistivity measuring device, which is 1.0 × 10Ι () Ω / □. Next, this capacitor element is immersed in A solution of 1 part of cyclic mono-ethylenedioxythiophene, p-toluenesulfonate as an oxidant-2 parts of non-iron, and 4 parts of n-butanol as a polymerization solution (hereinafter this solution is called Qingren Ye A ), After taking out the thorium, place it at 85t for 60 minutes to form a chemically polymerizable electronically conductive polymer, namely polyethylenedioxysigmathiophene, between the electrodes. Next, this capacitor element is washed with water ... After drying, it is sealed with resin and vulcanized butyl rubber sealing material (consisting of 30 parts of butyl rubber polymer, 20 parts of carbon, 50 parts of inorganic filler, hardness of the sealing body : 7〇Irhd [International Rubber Hardness Unit]) After being packed into an aluminum outer box together, the openings are sealed by hardening, so that the two lead terminals derived from the anode foil and the cathode foil pass through the polystyrene sulfur An ether-based seat plate is manufactured by bending a lead wire to manufacture a surface-mounted solid electrolytic capacitor (size: diameter 丨 〇Tnm X height 10 mm) ^ (Embodiment Mode 2) This paper is suitable for national standards in fiscal countries (CNS) A4 size d) • 34-, I read the Wen Yin on the back first? Please fill in this page again) 468189 Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (31) In this embodiment, one part of the heterocyclic single system uses ethylenedioxyphene, and the oxidant system uses 1 part of the second iron of naphthalenesulfonic acid and i part of the second iron of triisopropylnaphthalenesulfonic acid, and 4 parts of ethanol is used as the polymerization solvent; this replaces the polymerization solution A in Embodiment 1. Also, the spunbonded non-woven insulation layer made of polyethylene terephthalate in Embodiment 1 is a non-woven insulation layer (thickness 50; um) made of polyethylene terephthalate resin by a wet method. , Seed amount 25g / m2) instead; the rest are made entirely according to Embodiment 1. (Embodiment 3) In this embodiment, the heterocyclic mono-zhao system uses 1 part of Luoluo, the oxidant system uses 2 parts of persulfuric acid, and the polymerization solvent uses 1 part of methanol and 3 parts of water. This replaces the polymerization solution A in the first embodiment. The rest are completely manufactured according to the first embodiment. (Embodiment 4) Except that the insulation layer in Embodiment 1 is made of a polybutene terephthalate resin prepared by a wet method (thickness: 50 ren m, weighing capacity: 22.5 g / m2), the rest is completely Fabrication according to Embodiment 1 (Embodiment 5) Except for using the non-woven fabric containing glass fiber (thickness 80 卩 m 'weighing 10g / m2) as the isolation layer in Embodiment 1, the rest is made according to the embodiment] . (Embodiment 6) In addition to holding an electrolytic paper composed of Manila hemp between anode cadmium and cathode foil, the size of the paper is applicable to China National Standard (CNS) A4 (210 X 297 male «) ---- ---- ----- ---I-I—— — — —— — — — (Please read the precautions on the back before clicking this page) -35-

Jin Qiao · Production (Implementation Form Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs except for the implementation form 丨 the base liquid A in the electronic conductive polymer sulfonated polybenzyl i concentration 丨 .0 weight 1%; and propylene oxide Base variant polyester; an aqueous solution with a concentration of! (:! Wt%) (in total solution > solid content concentration of 4.0 wt%) is replaced. The rest is made entirely according to the embodiment 丨 this is formed on a glass plate to form a film thickness After 10 m of sulfonated polybenzylamine.f, the measured 'resistivity is + + 0xi 0 s,. &Quot; Ω / □' (Embodiment 8) except that the base liquid A in Embodiment 1 Ethylenedioxythiophene polybenzyl sulfonic acid (concentration) .0 weight, polymer sulfonic acid variant polyester lacking conductivity (: concentration 〖0.5% by weight) and polymer carboxylic acid variant lacking conductivity The concentration of the ester was 1.5% by weight) in water solution (the total concentration of the solid content in the solution was 4.0% by weight) instead of the rest. The rest was made entirely according to Embodiment 1: A film thickness of 1 〇 / ″ · m was formed on a glass plate. After the sulfonic acid-modified polyester layer is measured, its resistivity exceeds that of the resistivity measuring device The limit value is i.〇x 1 (J μ Ω; the value of □ is 'measured' after forming a carboxylic acid modified polyester layer with a film thickness of 10 μm on a glass plate, and its resistivity exceeds that of the resistivity measuring device. The measurement limit is the value of 1.0 × 101ϋΩ / □. (Embodiment 9) Except the polymerization solution A in Embodiment 1, it is assumed that the ethylene dioxygen 4 of the heterocyclic monomer is firstly read the matter on the back and then fill out this. page)

HQR I J2 n I 1 I Binding · -line. Unprinted paper again applies Chinese National Standard (CNS) A4 (210 X 297 mm) -36- 16 8 1 8 9

Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (33) 1 part of stilbene, 2 parts of p-methyl benzoate second iron as oxidant, 4 parts of polymer n-butanol and Glycidyl variants of the lacking conductive polymer (same composition as the base liquid A) were replaced by 0.5 parts of the solution, and the rest were made entirely according to the implementation form. (Comparative Example 1) Except that the base liquid A in Embodiment 1 was replaced with an aqueous solution of an electronically conductive polymer polyoxyethylene thiophene polybenzyl acetic acid (wavelength 4.0% by weight), the rest It is made entirely according to the first embodiment. (Comparative Example 2) Except that the base liquid A in Embodiment 1 was replaced with an aqueous solution of an epoxy-propyl-modified polyester (concentration 4.0% by weight) which is a polymer lacking conductivity, the rest was completely in accordance with the embodiment. 1 Make it. For the solid electrolytic capacitors according to Embodiments 1 to 9 and Comparative Examples 2 of the present invention, the capacitance (measurement frequency number 120 Hz), impedance (measurement frequency number 100 kHz), and leakage current (applied 6) · 3ν (value after 2 minutes of rated voltage), and after a short circuit (poor quality) occurs during curing, the results are shown in Table 1. In addition, the number of experiments in any experiment is 50, and the capacitance, impedance, and leakage current are shown by the average value of samples other than those in which a short circuit occurs. [Table 1] This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) -37- (Please read the precautions on the back before filling in this page ℴ Order: .Line. Ί Description iA .

Γ i 2 G! .. Bu,-" T " '": 〇 _______________________ ______ This embodiment f of the present invention 1; 603. This embodiment of the present invention 2 600 .... This embodiment of the present invention 3 601-this Inventive Mode 4 590 Inventive Mode 5 59 1 Inventive Mode 6 600 i_ Inventive Mode 7 602-Inventive Mode S | 602: ―Innovative Mode 9 I 630 495 1W

^ Example 1 " ^ tTfe ^ TT

To ΓΓ IT To ~ 10 " IF 'IT'

29 TIT-~ Bu.-

If ΤΓ • ~ v .- — „> 2 ·· —r——. 3 8

34 Tso ~ IT o " '〇 " ΤΓ Printed by the Consumer Consumption Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs] It can be seen that' as a result of the embodiment of the present invention 丨 to 9 ^^-^ 一 m— the composition is composed of valve action metal A layer containing an electrically conductive polymer and a polymer lacking conductivity is provided on the dielectric oxide film of the anode body. Therefore, the low-resistance electronic conductive polymer provided on the dielectric oxide film is used as the electrolyte. , Can make the capacitor's resistivity (impedance 丨 lowered and because the dielectric rolling is added with a highly resistive non-electronically conductive polymer, so even the damaged part of the dielectric gasification film When the electronic disintegration phenomenon starts to occur and the leakage current significantly increases, the electronic disintegration phenomenon can also be suppressed at the X β position, and the phenomenon can be suppressed to a local range until "electric body destruction (short circuit)", Compared with the solid electrolytic capacitor of Comparative Example], "It is available-small leakage current. Solid electrolytic capacitor that is not easy to short-circuit during maturation = further" The lack of conductivity by the epoxy propylene modified polyester, etc. Polymer The effect of sighing on the dielectric oxide film will increase the coverage of the electronic conductive polymer to "electricity gasification". Therefore, compared with Comparative Example 1, it is a sentence * A large capacity with high electrostatic capacity Solid electrolytic capacitors — On the other hand, the solid electrolytic capacitors of Comparative Example 2 are

(2i〇κ 297 mm) -... H ϊί f-; .Lt- il 111 n! T KII t— i II i n- ϋ- ^ OJ. N n- n > I (Please fill in this page for Bihui matters)

468189 V. Description of the invention (35) A large resistivity polymer lacking conductivity is provided on the oxide film, so the effect of suppressing the electronic disintegration phenomenon is large, and the number of short-circuit occurrences is 0, but on the other hand, it is combined with the Compared with the embodiments of the present invention where the conductive polymer with electrons lacks conductivity, the resistance is not only significantly higher, but the capacity extraction rate on the dielectric oxide film is also worse. Next, the embodiments in the sixth to ninth aspects will be described. (Embodiment 10) After the surface of the aluminum foil is saccharified by engraving, an anode oxidation process is performed to form a dielectric oxide film, and an anode foil composed of the aluminum foil is interposed with a cathode foil that is also engraved with Shao Ming , Holding an isolating layer (thickness of 45 to m 'weighing 25g / m2) composed of a non-woven fabric obtained by spunbonding of polyethylene terephthalate resin, and winding it to obtain a capacitor element (this After the capacitor element was impregnated with a 10% by weight ethylene glycol solution of adipic acid amine, the capacitance at a frequency of 120 Hz was 670 // F). Next, this capacitor element was impregnated with 1 part of ethylenedioxophenone which is a heterocyclic monomer, 2 parts of p-toluenesulfonic acid second iron as an oxidant, and 4 parts of n-butanol as a polymerization solvent. Remove the solution from the solution and place at 85 ° C. (: Place it underneath for 60 minutes to form a solid electrolyte of polyethylene dioxythiophene which is a chemically polymerizable conductive polymer between the anode foil and the cathode foil. Next, the capacitor element is washed with water, dried, and sulfurized with the resin. Butyl rubber sealing material (consisting of 30 parts of butyl rubber polymer, 20 parts of carbon, and 50 parts of inorganic filler, sealing hardness: [International Rubber Hardness Unit]) Packed into an aluminum outer box with a bottom barrel shape together Later, by hardening, the format of the paper will be applicable _ National Standard (CNS) A4 (210 X 297 mm) II I -------_ II 1111111 · 1111111 {Please read the precautions on the back first (Reprinted on this page) Printed by the Employees ’Cooperative of the Intellectual Property Bureau of the Ministry of Hydrocarbons-39 · m Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Industrial and Consumer Cooperatives" Ice Seal: Lien. :. + Introduced t ΐ to consolidate the H cloth bismuth .. Rebellion: and then install the wire 钚, .. ^ ^ ^ R surface installation 翌: t, ® bulk electrolytic capacitors to greedy .: ; jl 'Again! 5 * m】 rTi 'Solid morphology 丨 丨） From this embodiment, a solid of polyethylene gas-supported thiazide is formed. "Then, the capacitor element is first immersed in polyethylene thiophene-polyethylene stele 1 U) 〇 / 〇 Aqueous solution, after taking out 诶, drying at a temperature of 50: c / min, on the dielectric oxide film, the cathode is knitted with the isolation layer fiber t to form polyethylene dioxythiophene Polybenzyl sulfonate layer. The rest is complete. Production is performed in Embodiment 10. 1 ('Embodiment 12) In this embodiment, Tc ~ Q is melt-impregnated at a temperature of 200 t or more. It is left to cool at room temperature so that the capacitor element forms a TCNQ conductive layer that is a solid electrolyte. This replaces the polyoxyethylene thiophene as a solid electrolyte in the embodiment, and the rest is completely according to the embodiment} ( (Embodiment 13) In this embodiment, '1 part of heterocyclic single system is used with pyrrole, 2 parts of gasification agent is used for saccharic acid, and 1 part of methanol is used for polymerization solution, and 3 parts of water are used as polymerization solution. The resulting mixed solvent 'the rest is made entirely in accordance with Embodiment 10. (Embodiment 14) Except for implementation The isolation layer in state 10 uses a mixed resin of polyethylene terephthalate (20% by weight) and polypropylene (80% by weight): ¾ Read the back first; -i (This page) ------ Chu · Line! This paper ruler applies to the National Standard of China (CNS) A4 (210 x 297 mm). 40-46 8 1 8 9 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs Printed A7 B7 V. Description of the invention (37 > Isolation layer (thickness 50 " m, weighing 25g / m2) composed of non-woven fabric obtained by spunbonding, the rest are made entirely according to Embodiment 10. (Implementation Form 15) Except that the isolating layer in Embodiment 10 uses an isolating layer (thickness 50 at m 'and weighing 25g / m2) composed of a non-woven fabric obtained by wet-type method using polyethylene terephthalate resin. Fabrication was carried out according to Embodiment 10. (Embodiment 16) Except for the isolating layer in Embodiment 10, polyethylene terephthalate (80% by weight), polypropylene resin (10% by weight), Manila hemp fiber (5% by weight), sulfate pulp fiber (% by weight) 4%), and the insulation layer (thickness 50 // m, weighing 25g / m2) composed of mixed nonwoven fabrics obtained by wet method with vinylon fiber (1% by weight), etc., and the rest are completely according to Embodiment 10 (Comparative Example 3) The spunbond insulation layer in Embodiment 10 was replaced with a glass fiber nonwoven fabric (thickness 80 " m, weighing 10 g / m2), and the rest were produced entirely in accordance with Embodiment 10. Comparative Example 4) The spunbond release layer in Embodiment 10 was replaced with a melt-dissolved nonwoven fabric (thickness: 50 kernels m, seed amount: 25 g / m2) composed of polypropylene, and the rest was made entirely according to Embodiment 10. (Comparative Example 5) Except in Embodiment 10, an electrolytic paper (thickness: 45 em) made of Manila hemp was held between the anode foil and the cathode foil, and the capacitor was wound. ----!-&Quot; ------ Order ί— it — · — · Line (Please read the precautions on the back before filling out this page} ， 41 _

In 'Hanging pole .: ¾ and Lou Ji method% solution ¥' s thinning, modern structure. ¾ electricity 3.¾ # 余 # 完 t ι'Λ. Actual translation 'Zhu Hen A Jin, — 袈 4 ί Comparison Example 6) Obtained by the spunbond method in the embodiment u): m is separated from the layer, u is a non-woven fabric made of polypropylene resin by the wet method. Thickness 50 μm 'Weigh ZSg / mh and take the rest It is made entirely according to the embodiment 10. The embodiment of the present invention made on the above! The solid electrolytic capacitors of 0 to 丨 6 and Comparative Examples 3 to 6 · Compared with the capacitance (measured frequency number! 2 OHz impedance (measured frequency number 1 () 0k.H z) ...: trailing leakage current ί applied 6.3 Value of V rated voltage after 2 minutes :), the number of short circuits (poor quality) during curing, and the impedance after reflection treatment (condition: maximum exposure temperature 2501, 2 () 0 t exposure for 45 seconds) (Measurement frequency is 100 kHz), and the results are shown in Table 2. Also, the number of experiments in any experiment is 50. The capacitance, impedance, leakage current, and capacitance after reflection treatment are Read the value on the back of the sample as the average value of the samples other than the short-circuited ones; 1) Please fill in this page) ------ --- 6i, the paper size of the thread applies to the Chinese national standard (CNSM4 specification (21〇 χ 297 mm) -42- 468 彳 89 A7 B7 V. Description of the invention (39) Capacitance (F. 1 20Hz | Impedance (mfi, 100kHz) Leakage current (μ. A, 2mi η) Short circuit occurrence (number of occurrences) Impedance after reflection processing (ηιΩ, 100kHz) Embodiment 10 of the present invention 10 603 9 38 0 ία Implementation of the present invention Aspect 11 600 10 37 0 15 Embodiment 12 of the present invention 12 602 10 36 0 10 Embodiment of the present invention 13 602 15 34 0 14 Embodiment of the present invention 14 601 14 34 0 14 Embodiment of the present invention 15 600 13 34 0 14 Implementation of the present invention Form 16 601 13 35 0 15 Comparative Example 3 430 40 55 7 SO Comparative Example 4 600 11 58 8 12 Comparative Example 5 430 45 60 10 88 Comparative Example 6 429 44 60 10 88 As shown in Table 2, 'Embodiment 1 of the present invention. To 16 solid electrolytic capacitors (please read the precautions on the back before filling this page). Use the resin as the isolation layer obtained by spinning and drying method, or the non-woven fabric obtained by wet method containing polyester resin. Since the solid electrolyte has excellent adhesion and adhesion with these separators, other separator materials are used as shown in Comparative Example 3, Comparative Example 5, and Comparative Example 6 (Comparative Example 3 is a glass fiber nonwoven fabric) (Comparative example 5 is carbonized electrolytic paper, and comparative example 6 is polypropylene wet type non-woven fabric). Compared with this, it is the one that can lower the impedance in the high frequency range. Also, because it can be a solid electrolyte polyethylene oxide Thiophene etc. adheres closely and follows Because of the isolation layer, the impedance change after reflection processing is small, and the reliability as a surface-mounted solid electrolytic capacitor is also high. It is printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and 'if using the isolation layers of Comparative Examples 3 to 6 ( (Comparative Example 3 is a glass fiber non-woven fabric, Comparative Example 4 is a melt-melted non-woven fabric, Comparative Example 5 is a carbonized electrolytic paper, and Comparative Example 6 is a polypropylene non-woven fabric.) Contact with the cathode foil will result in a high incidence of short circuits in the curing process. Next, embodiments of the tenth and twelfth aspects will be described. (Embodiment Mode 17) -43- This paper size applies the Chinese National Standard (CNS > A4 specification (210 X 297 mm) 4: 'ί: jr, m ^ Etching process will roughen the .ss foil. Surface * m. Ten-electrode gasification 犋. 屮 into 砀 殛 foil: Division '. ,,, with a ton of electricity of 0.8 \ ECG oxygen η: series of anode metal foil and cathode made of Wc Foil-in-a-middle-Yu-Yu-Fu-Di-Mei-Ya ... No ... ~ She. One-yfi clothing ~ 'f W + So: and the interval between attacks M i-cycle-wound capacitor element. This capacitor' : Denier. ,, β 7-e _ mono-acid amine 10 weight + +-after the mussel solution, the static electricity at the frequency of 1 20 Hz θ The amount of electricity is ㈣

B.I Next, this capacitor element was immersed in polyethylene 4 3 塞 1.0 /. In the aqueous solution, take out i 5 0 ′. Observe the surface treatment for 5 minutes to form a polyethylene oxide plug on the dielectric gasification between the anode foil and the cathode foil and on the fibers of the insulation layer. Second, the capacitor element is immersed in a component containing heterocyclic 53 monomer: 1 part of dioxophenone, 2 parts of p-sulfonium and 2nd iron as oxidant, In a solution of 4 parts of n-butyrate as a polymerization solvent, after removing it, it was left for 60 minutes to form a chemically polymerizable conductive polymer of polyethylene dioxythiophene between the anode foil and the cathode foil. This capacitor element is washed with water—after drying, the resin is sealed with butyl rubber sealing material (composed of 30 parts carbon of butyl rubber and 20 parts of inorganic filler: > 0 parts. Sealing hardness: 70IRHD [International Rubber Hardness Unit ”) After being packed together in an aluminum outer packaging box, the-opening is sealed by hardening, so that the two lead terminals led out by the anode 洎 and the cathode foil are passed through a polystyrene sulfide ether seat plate, and then borrowed. Manufactured by bending the lead part

This paper size applies to China National Standard (C.NS) A4 specifications (210 X 297 public love * J * ---- ί! Ι ·--· ιί 1 ·· ί— lt- &1; 1 i I. * n 1 n UK n gy. J_. ^ 1 .1 · —i JII ^ Please read the notes on the back before filling out this page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation * 44- Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs Printed by the consumer cooperative d 6 8 1 8 9 A7 _ B? V. Description of the invention (41) Surface-mounted solid electrolytic capacitors (size: diameter 10mm x height 10mm, rated voltage 6V). (Embodiment 18) In this embodiment, 'apart from the cathode 阳极 which is formed by using an anodic oxidation method to form dielectric oxide films with different breakdown voltages of 0-5V, 1V, 5V, 7V, 10V, and 12v, instead of Embodiment 17, A cathode foil having a dielectric oxide film with a withstand voltage of 0.8 V was formed by the anodizing method, and the rest were made entirely in accordance with Embodiment 17. (Embodiment 19) Except for the separation layer in Embodiment 17, a non-woven fabric composed of polyethylene terephthalate (having a thickness of 50 // m in total, wherein The thickness of 30 ohms is divided into a density of 0.8g / m3, and the remaining 20 #m points connected thereto have a density of 0.2g / m3), and the lower density side is rolled toward the cathode foil, The rest are made entirely in accordance with Embodiment 17. (Embodiment 20) Except for using a mixed non-woven insulation layer (thickness 50 " m, weighing 25g / m2 'density 0.5g / cm3) containing nylon and glass fiber as the insulation layer in embodiment 17, the rest is completely according to the embodiment 17 to make. (Embodiment 21) Except for using the polypropylene nonwoven fabric (thickness 50 μm, weighing 25g / m2 'density 0.5g / cm3) obtained by spunbonding as the isolation layer in embodiment 17, the rest is completely according to embodiment 17 Production 6 (Embodiment 22) This paper size is in accordance with Chinese national standard (CNS> A4 specification (210 X 297 male «)) 45_ I I--i II ^ -------- Order · --- --- line (please read the notes on the back side and fill in the κ this W) | -t # ίίί rfi3 | -t # ίίί rfi3 .¾ 'SI side bowl 醆 press 2 rely on the agent to take alcohol gluten η. 4 The rest: 乇 f 泫 t peak H electrolytic capacitors !: Comparative Example 7) Use a cathode foil without a dielectric oxide film (this female cup has a natural emulsified film, withstand voltage of 0 3 νΊ instead of borrowing The anode foil method is used to form a cathode foil with a withstand voltage of 0.8, and the rest of the cathode foil is completely made in accordance with Embodiment 丨 7. The above-mentioned embodiments of the present invention 丨 7 to 22 and the mouth of Comparative Example 7 The volume electrolytic valley device 'compares its electrostatic capacity (measurement frequency 1 20Hz), impedance (measurement frequency 100kHz), leakage current (rated voltage) 6V after printing ), And the number of short-circuit occurrences during the heating process are shown in Table 3. The number of experiments in the experiment was 50, and the electrostatic capacity, impedance, and Δ leakage current were used to eliminate maturation. The average value of samples other than those short-circuited is shown as' f · ft ft tf. Hi I i I i I ϋ I-II n III i ^ -OJ n ft I n I- f I t. {Please read the back; Please fill in this page again if necessary)) Printed by the Economic and Intellectual Property Bureau Staff Consumer Cooperatives' 46- This paper is fully applicable to China National Standard (CNS) A4 (210 X 297 Gongchu) 468189 A7 B7 Intellectual Property Bureau, Ministry of Economic Affairs Man Ming instructions printed by employee consumer cooperatives (43) Capacitance-(HF, 120Hz) Impedance (n \ Q, 300kHz) Leakage current (with A. 2 points) Short circuit occurrence (number of occurrences) .. Cathode foil resistance Voltage Embodiment 17 of the invention 17 0.8V 150 18 100 0 Embodiment 18 of the invention 18 0,5V 125-35 105 0 IV 155 22 102 0 5 V 154 21 103 0 7V 148 23 101 0 ϊον 146, 25 Ϊ05 0 12V 136 π 32 110 0 Embodiment 19 180, 12 100 0 Embodiment 20 146 20 210 2 _ This invention ★ Embodiment 21 145 20 102 0 Embodiment 22 of the present invention 22 151 18 101 0 Comparative Example 7 —94-(-51- 102 0 The solid electrolytic capacitor of Example 7 has a dielectric withstand voltage of 10 V or less because it is formed on the cathode foil. The electrical oxide film has a high capacitance extraction rate and excellent impedance characteristics. Also, in Embodiment 18, if the withstand voltage of the dielectric oxide film of the cathode foil is 10V or more, the capacitance extraction rate will be low, and the impedance characteristics will be inferior, and "the solid electrolytic capacitor with a withstand voltage of 0.5 V or less" It is also similar to the result of Comparative Example 7 that the pair voltage of the dielectric oxide film of the cathode junction is preferably in the range of 0.8V to 10V. In the solid electrolytic capacitor of Embodiment 19, an insulation layer having a different thickness in the thickness direction is held between the anode foil and the cathode pig, and the arrangement is such that the low-density side of the insulation layer faces the cathode foil during winding. The solid capacitor of Embodiment 17 in which an equal isolation layer is wound and wound is large in capacitance and excellent in impedance performance. In the comparison between Embodiment 17 and Embodiments 20 and 21, from the point of view of the separation layer consisting of a non-woven fabric containing a resin and the use of a dielectric oxide film having a withstand voltage on a cathode ridge, Of course, they have a total of — — — — — — — — — — — — — — II I-- 丨 Order. — — — — — 111 V .. (please first) «Read the notes on the back side and then fill in this page ) I store a piece of one $ -47 · Printed borders by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Structure, however. Real shape 2 丨:, and 2 丨 Xingshi & deduction valley. Shao Tan still has another form of real bell 丨 7 ^ ^ ^ his own 4 ^ ^ · fc, .. 2, 2, {?, S ,,. Leaving the doctor: Erji's' Because it is compared with the use of gadolinium and polypropylene and other gadolinium as the insulating layer material, J ~ Embodiments 20 and 21 can better exert the effect of the present invention. In the embodiment 20 of the mixed fiber insulation layer, "the leakage current is slightly larger due to the shadow of the glass fiber f." Furthermore, although the number of M-channels is small, it still occurs. 3 The solid electricity of embodiment 22 Although slightly so that the capacitor substituted Bi Bi embodiment ethylenedioxy morphology of support used Π woven thiophene 'but still obtain the same embodiment Shu characteristic = 7 Next, the first 11 and the second! The embodiment in the second aspect is mainly described (Embodiment 23) After an aluminum foil surface is roughened by an etching process, a dielectric hafnium oxide is formed thereon by anodization to form an anode foil, and at the same time an Aluminum a is etched, and its surface is covered with metal titanium by vacuum precipitation method, and the structure = .- cathode foil, the anode foil and cathode foil thus produced are held between the poly-p-dibenzoic acid and the per-point method Isolation layer made of non-woven cloth made of ethylene glycol (thickness of 50 " m '25g / mI :, density of 0.5g / cm;). It is rolled into a wound capacitor element (this capacitor element After being impregnated with an ethylene glycol solution of 0%-* 1 -'- stilbamine, the capacitance at a frequency of 120 Hz was 700 pF). Next, this capacitor element was immersed in polyethylene oxide.伟 嗔 芬 聚 策 不 'Ji η Please read the precautions on the back before filling out this page) .t · I didn 1] --- -0J. 丨 Line · Degree Applies to Chinese National Standard (CNS) A4 Specification (210 X 297 mm) ^ 48- 468189 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs (45) alkenyl-sulfonic acid 1.0% aqueous Ming, after once taken out,! A drying treatment was performed at a temperature of 50 ° C for 5 minutes to form a layer of polyethylenedioxythiophene polystyrenesulfonic acid on the dielectric oxide film of the anode foil and the cathode foil and on the fibers of the separator. Next, this capacitor element was immersed in a solution containing 1 part of ethylenedioxophenone as a heterocyclic monomer, 2 parts of p-toluenesulfonic acid second iron as an oxidizing agent, and 4 parts of n-butanol a polymerization solvent. After the cymbals were taken out, they were left at 85 ° C for 60 minutes to form a polyethylene polymer of a chemically polymerizable conductive polymer between the anode foil and the cathode foil. Next, the capacitor element was washed with water and dried, and then the resin was added with a sulfur-butyl rubber sealing material (consisting of 30 parts of butyl rubber polymer, 20 parts of carbon, and 50 parts of inorganic filler. Sealing hardness: 70IRHD [International Rubber Hardness Unit]) After being put into an aluminum outer box together, the opening is sealed by hardening treatment, and then the two lead terminals respectively derived from the anode foil and the cathode foil are passed through a seat plate made of polysulfide. 'Furthermore, the lead part was folded to produce a solid-state electrolytic capacitor (size: diameter 10 mrn X height 10 mm, rated voltage 10 V). (Embodiment 24) Except that the cathode foil covered with metal titanium by the vacuum precipitation method is replaced by the cathode foil covered with iridium nitride by the vacuum sinking method in Embodiment 23, the rest are completely surface-mounted according to Embodiment 23. Production of solid electrolytic capacitors. (Embodiment 25) Except that the cathode foil covered with metal titanium by the vacuum precipitation method in Embodiment 23 is replaced by the cathode foil covered with zirconium nitride by the vacuum precipitation method, the rest of this paper applies the Chinese standard (CNS) ) A4 size (210 X 297 mm) -49-: I—! Packing -------- Order ------- Line (Please read the > i notice on the back before filling in the book Page) • rn Consumer cooperation of Du Intellectual Property Office of Intellectual Property Bureau of the Ministry of Economic Affairs: “儿,;…; charge dad. ¾ implementation of flat state: Π facet t type 疋: i: body electricity than electricity gt. Pieces,- The actual form 2 6: Except for the method 2J +, the metal foil is covered by the vacuum precipitation method f, and the cathode foil is covered with the vacuum foil by the vacuum precipitation method. The rest is completely surface-mounted according to the embodiment 23. Manufacture of solid electrolytic capacitors. ^ Except Form 2 " ^ Except that in Embodiment 23, the cathode foil covered with metal titanium by vacuum precipitation method is replaced by the cathode foil covered with vaporized titanium by vacuum precipitation method. Embodiment 23 manufactures a surface-mounted solid electrolytic capacitor. (Embodiment 28) Except for vacuum deposition in Embodiments 2 and 3 The cathode foil covered with metal titanium is replaced by a cathode foil covered with titanium carbide by a vacuum precipitation method, and the rest is entirely manufactured in accordance with Embodiment 23 for a surface-mounted solid electrolytic capacitor. (Embodiment 29) Except for Embodiment 23, Covering the cathodic diarrhea of metal titanium by vacuum precipitation method Replace the outside with cathode foil covered with carbon by vacuum precipitation method 'The rest is made entirely according to Embodiment 23 Surface-mounted solid electrolytic capacitors (Embodiment 30) Embodiment 2 In 3 of 1 except that the non-woven fabric made of polyethylene terephthalate obtained by spunbonding with different density in the thickness direction of the insulation layer is used (the entire paper is also applicable to the National Standard (CNS) A4) (2i0 X 297 mm)! I n ri, is JJJ ί 1 i Jt I _ I d n__ 一-^ un II u I (¾Read the precautions on the back before filling this page) -50- 4BS1 A7- ---- B7___ V. Description of the invention (47) The thickness of the body is 50 em, of which the thickness 30 is divided into m with a density of 0.8 g / m3, and the density of the remaining 20 / im is 0.2 g / m3) And make the lower density side face out of the cathode foil during winding. Embodiment 23 produces a surface-mounted solid electrolytic capacitor. (Comparative Example 8) In addition to the foregoing embodiment 23, the cathode ball of metal titanium is covered by a vacuum precipitation method to etch only the aluminum foil (the surface of the foil). In addition to the thermal oxidation film with a withstand voltage of 0.6 V), the rest is made entirely according to the embodiment 23 of the surface-mounted solid electrolytic capacitor. The solids of the embodiments 23 to 30 of the present invention and the solid of the comparative example 8 are manufactured as described above. Electrolytic capacitors, after comparing their capacitance (measurement frequency i 20Hz), impedance (measurement frequency 100kHz), leakage current (value of 丨 6V rated voltage for 2 minutes), and the number of short-circuits during aging, compare The results are shown in Table 4. In any of the experiments, the number of experiments is 50. The capacitance, impedance, and leakage current are shown by the average value of the samples among the 50 experiments, except for those who short-circuited during aging. -------: ---.--- install -------- order- {Please read the note on the back first and then fill this page ¾) Cooperate with the shellfish of the Intellectual Property Bureau of the Ministry of Economic Affairs Du Print Tabulation -51- This paper size 剌 + @g 家 standard (CNS) A4 specifications < 210 X 297 is clear. A product electric Λ ☆ II. Η, invention implementation form 2 3 6 6 8 ........... Λ iS Embodiment 24 of the present invention: 679! Fly 2 0 indicates Embodiment 2 5 677 9 11 Embodiment 2 6 of the present invention; 676 9 X > υ Embodiment 2 of the present invention 67 1 12 3 9! Ί} Embodiment 2S 065 1 13 4 0 i) of the present invention, embodiment 29 of the wood invention; 6 69; 11 4 I υ Embodiment 3 of the invention of wood () 1 670! 1 1 12: 3 8 〇 Comparative Example 8; 555; 30: 102:. 可 As can be seen from Table 4, the solid electrolytic capacitors of the embodiments 23 to 29 are compared with the solid electrolytic capacitor of the comparative example 8 'because of the metal titanium formed on the cathode foil' I titanium = nitrogen Zirconium hafnium nitride, hafnium nitride, titanium carbide, titanium carbide, and carbon coatings-so high capacitance extraction rate and excellent impedance characteristics. Among them, the excellent capacitance of the nitride-covered capacitors leads to the extremely high capacitance and low resistance. "The solid electrolytic capacitor of Embodiment 30" holds a thickness density difference between the anode foil and the cathode foil. When winding, the low-density side of the insulation layer is arranged toward the cathode foil side when winding 1 so that its electrostatic capacity is greater than that of an insulation layer with uniform density in the thickness direction, and the solid electrolytic capacitor in Embodiment 23 is wound. Capacitance-and excellent impedance characteristics. Next, the description will be given mainly on the implementation forms of the 13th to t5th aspects. (1) (Embodiment 3 1) A spunbond made of polyethylene terephthalate is supported between the anode foil and the cathode foil. 5 倍 的 聚 笨 聚聚 氢 乙 the isolating layer (thickness 50 / im. Weighing 2 5 g, trT), and it is wound 'and by the outer periphery of the capacitor element, the winding length is 1.5 times the poly-pumene sulfide Substrate adhesive tape 'to form a wound capacitor element (this capacitor element is immersed in this paper containing 10% by weight of adipic acid amine, this paper size is applicable to China National Standard (CNS) A4 specification (21ϋ X 297 mm)谪 Please read the back of the first; fill in the I items and fill in this I > equipment-printed by the Ministry of Economic Affairs Intellectual Property Bureau employee consumer cooperative 468189

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the invention (49) After the solution of ethylene glycol, the electrostatic capacity at a frequency of 120 Hz is 67 ° F. Next, 'dilute this capacitor element to a solution containing 2 parts of p-toluenesulfonic acid, 2 parts of iron, and 4 parts of n-butanol, which is a polymerization solvent, containing 1 part of ethylene oxide as a heterocyclic monomer. After removing the middle, 俟 at 85. It was left for 60 minutes at 0 ° 'to form a polyethylenedioxythiophene which is a chemically polymerizable conductive polymer between the electrodes. Secondly, the capacitor element was washed with water-dried, and then dried at 12 ° C for 30 minutes. Next, this capacitor element was immediately moved to a glove box filled with dry air (Gloveve 0x; The glove is inserted into the box in which the glove is put into operation), and the resin is added with sulfur-butyl rubber sealing material (made of butyl rubber polymer) in a dry air environment and dried at 120 C for 1 hour to reduce the moisture content. 30 parts of carbon, 20 parts of carbon, 50 parts of inorganic filler, sealing hardness: 70Irhd [International Rubber Hardness Unit], 250 C elastic modulus is 450N / cm2)-Put it into the outer packaging box Then, the opening is sealed by "hardening treatment", and then the two lead terminals respectively led out by the anode foil and the cathode drop are passed through a seat made of polystyrene sulfide, and then the lead portion is processed to produce a surface-mount type Solid electrolytic capacitors (size: diameter 10mmx height 10.2mm). Dry air-filled glove box used when assembling the solid electrolytic capacitors thus produced. Decompose and remove the capacitor elements so as not to prevent With moisture in the air ', the moisture content held by this capacitor element was measured by an I gas introduction Fischer titration method with a moisture vaporization heating device, and the result was' relative to the anode foil portion, cathode foil portion, and isolation of the capacitor element. The total weight of the layer, solid electrolyte, and rolled tape (that is, the size of the paper without the anode is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -------: 11! _Pack- ----- 丨 Order -------- line (please read the precautions on the back before filling this page) -53- + Man broken and shaded green power. ¾: 器 '件The amount is "w: means: according to this: then the water content of the fixed electricity is determined] and the bird detects such unavailable content, the rate of k; then please change the capacitor element removed to remove the anode 'cathode two wires, Dry this Ίχ! _R at 1 妾 its weight is less than the weight before dryness. Hang the dry, edit the weight of the weight divided by this value, the percentage change in weight (it can be inferred that it is equivalent to the moisture absorption of the capacitor element) Weight percentage, the following. With w: said according to this test method. The moisture content in it) is 0.8% from this result. t It is indeed possible to grasp the moisture content with very high accuracy: (Embodiment 32) In addition to the application of Form 3, the oxidant system uses 1 part of naphthoic acid second iron and 1 part of triisopropylnaphthalenesulfonic acid second iron The polymerization solvent is 4 parts of ethanol. The rest is made entirely according to Embodiment 31. The water content of this embodiment is W9 is 0.89% and w2 is 0.89% (Embodiment 33). Bureau member M Consumer Cooperative Co., Ltd. f Except for Embodiment 31, the heterocyclic single system uses pyridinium, oxidant, 2 parts ammonium persulfate, and polymerization solvent, 1 part methanol and 3 parts polymer solution. Then, β is produced in accordance with Embodiment 31. The water content of this embodiment is W 1 is 0.8% and W 2 is 0.8 8% (Embodiment 34) Except that the insulation layer in Embodiment 31 is made of polypropylene. Spunbond non-woven fabrics (thickness 50 " m, weighing 25g / m2), the rest are made entirely according to the embodiment 3 1 "The moisture content of this embodiment, W1 is 0.94%, and W2 is 0.94%. The reverse of this paper applies Chinese national standards (CNSM4 specification (210 X 297 mm) • 54-468189 A7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs --------- 5. Description of the invention (51) ( Embodiment 35) Except for the isolating layer in Embodiment 31, which uses nitrate * acidified cellulose fiber paper obtained by nitrifying Manila hemp electrolytic paper, the rest is made entirely according to Embodiment 31. , W 1 is 0.97% 'W2 is 0.96%. (Embodiment 36) Except that the insulation layer in Embodiment 31 is made of glass fiber non-woven fabric (thickness 80 # m' weighing weight 10g / m2), the rest are completely according to The third embodiment is produced. The water content in this embodiment is 0 97% and 2 is 0 97%. (Embodiment 37) In Embodiment 31, the moisture content is held between the anode foil and the cathode foil. An electrolytic paper (thickness: 50V m) composed of Manila hemp is wound. The capacitor element is placed in a nitrogen environment and heated at a temperature of 275 ° C for 2 hours. Carbonization, and after forming the capacitor element, additional steps are added to this capacitor. Solid content of polyethylene dioxythiophene polystyrene sulfonic acid immersed in a polystyrene sulfonic acid derivative, a 3% aqueous solution, and a sulfonic acid modified poly-p-phenylene as an adhesive component for reducing water absorption The suspension solution (5.0% solids in water) of di-f-acid acid is in a mixed solution with a ratio of 丨:. After removing it, dry it at 15 ° C for 10 minutes, and then Immerse in a solution containing 1 part of ethylenedithiophene as a heterocyclic monomer, 2 parts of p-toluenesulfonic acid second iron as an oxidizing agent, 4 parts of n-butanol as a polymerization solvent, remove the thorium, and S5t: It is left for 60 minutes to form a chemically polymerizable conductive polymer of polyethylene dioxythiophene between the electrode foils, and the rest is made entirely according to Embodiment 31. Water in this embodiment {please read the back first Note for refilling. ¾ This page)-Installation magic---- line. This paper size is applicable to China National Tomb Standard (CNS) A4 specification ⑵Qx297 issued) -55- Printed and invented by the Consumers ’Cooperative of Intellectual Property Bureau of Ministry of Hydrocarbons Explanation ;; + Ί… * vv; island w ″: ¾ = t turtle form 3 S) Divide Form 31 4… Sealing the group of pi is to add the ancient flavor 丨 Jff_ .η 丨 ″ π with peroxy i, two different and two stupid peroxides and Luding 蟓 蟓 wins to become .v ', ... . For u: inch, made of 32 parts of butyl rubber polymer. 20 parts of carbon inorganic filling, a ,, r, i 嚷 ¢ (sealing hardness: 6SIRHD; international rubber hard 哽 unit h is% 4- The elasticity modulus in the 802 Oil C is 4 0 N / cm2). The rest is based on the water content of this embodiment completely according to the embodiment V1, W1 is 0.79%, W2 is 0-78%, (Embodiment 39) Except in Embodiment 3 1 Φ. Do not move the capacitor element to a dry air glove box ', and perform the combination in an environment with a temperature of 30 ° C and a relative humidity of RH60% (the capacitor element starts immediately after drying, until the combination, the time required is 1 '0 hours)' The rest are made entirely according to the actual form 31-the moisture content of the actual form, W 1 is 1.2%, W2 is 1.1% (Embodiment 40) Except for Embodiment 31, Heterocyclic monomer uses ethylene dioxophenone, oxidant uses 2 parts of p-toluenesulfonic acid second iron, and polymerization solvent uses 4 parts of n-butanol solution. Carboxylic acid poly (ethylene terephthalate) suspension solution (aqueous solution with a solid concentration of 30%) is used as an adhesive component to reduce its water absorption, and the rest is completely in accordance with embodiment 3! Make it. In the water content of this embodiment, W1 is 0.1% and W2 is 0.73% (Embodiment 41) Except that the insulation layer in Embodiment 3 丨 uses polyethylene terephthalate fiber and its derivative fibers and borrows moisture The non-woven insulation layer made by the method (thick paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -56- i — *-i 3 i — IIIII _-i I. III i! 6J · nnn! N 1 II Please read the notes on tt back * before filling out this page) A7 d68189 B7_ V. Description of the invention (53) (Please read the notes on the back before filling out this page > Degree 50 / zm, weighing 22.5g / m2), the rest are made entirely in accordance with Embodiment 31. The water content of this embodiment is W0 of 0.90% and W2 of 0.9 1%. (Comparative Example 9) A spunbond nonwoven fabric insulation layer (thickness 50 " m, weighing 25g / m2) made of polyethylene terephthalate was held between the anode foil and the cathode foil, and wound to make it. A wound capacitor element (this capacitor element is immersed in an ethylene glycol solution of 10% by weight of adipic acid, and its capacitance at a frequency of 120Hz is 670 // F). Next, this capacitor element was immersed in a solution containing 1 part of ethylenedioxythiophene as a heterocyclic monomer, 2 parts of p-toluenesulfonic acid, 2 parts of iron, and 4 parts of n-butanol as a polymerization solvent. After removing the middle, 俟 at 85. It was allowed to stand for 60 minutes at 0 ° 'to form a chemically polymerizable conductive polymer of polyethylenedioxythiophene between the electrode foils. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. Then ‘wash this capacitor element with water and dry it, and then dry it for 30 minutes at a temperature of 1201 or higher than the boiling point of n-butanol as a polymerization solvent. This step is followed by 'this capacitor element in an environment with a temperature of 30t-relative fishery RH60%, with resin and sulfur butyl rubber sealing material (32 parts of butyl rubber polymer, 20 parts of carbon' inorganic filler Consisting of 48 parts, the hardness of the sealing body: 68IRHD [International Rubber Hardness Unit], elastic modulus 400N / cm2 in 250 t)-After being packed in an aluminum alloy outer packaging box, the opening is sealed by hardening treatment ' Further, the two lead terminals respectively derived from the anode foil and the cathode foil were passed through a polyphenylene sulfide-made base plate, and then the lead portion was bent to manufacture a surface-mounted solid electrolytic capacitor (size: diameter 10 mm). X height 10.2mm). The moisture content of this comparative example, wi is i'2y〇, from 2 to ^ paper size applies Chinese National Standard (CNS) A4 specification 〇〇297297 Chu --------_ Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The embodiment of the present invention based on the above-made edges: 丨 丨 to 4 small and compared, q-body S-body electrolytic container €. Leaner static electricity: 嚷 嚷 Leading number: π Η / 丨 m pit i measurement frequency KK) kH.z). Reflective treatment on the contaminated surface Ampex® Yu (provided that the maximum temperature is 250 (', 20 ("(: above exposure for 45 seconds, expansion of the sealing surface of the solid electrolytic capacitor after expansion) The results are shown in the following table after the number of occurrences of poor soldering quality due to the floating of the sealing surface when the wire floats during surface mounting, and the results are shown in the table. == Also, the number of experiments in any experiment is 50. Capacitance and the expansion of the sealing surface of solid electrolytic capacitors are shown as an average of 50: _ [Table 5] Capacitance ί-F. 1 2 0 Η ζ) Impedance ^ ΙΓ.; J, 3 0 0 l · Η 2) The number of poor soldering quality after reflection The amount of expansion of the sealing surface after reflection (mm) Embodiment 3 3 603 9 〇0 1 0 Embodiment 3 of the present invention 2 2 600 10 〇0.12 Embodiment of the present invention 33 595 11 0 0.13 Embodiment of the present invention 34 602 14 〇.15. ^ Embodiment 3 of the present invention 3 5 602 12 〇0.15 Embodiment 3 of the present invention 6 6 600 12 0 0. S 6 Embodiment 3 of the present invention 3 7 596] 2 ο 0,] 6 Embodiment of the present invention 3 8 602 10 0 0.19 ^ Embodiment 3 of the present invention 3 9 602 10 0 0.19 Embodiment 40 of the present invention 40 599 10 0 ϋ 3 The actual form of the present invention 4 1 602 11 0 0.14 Comparative Example 9 599 i0 1 3 0.4 2 As can be seen from Table 5, the solid electrolytic capacitors according to Embodiments 3 1 to 38 and Embodiments 40 and 41 of the present invention ' Because of its structure, 'the moisture content of the capacitor element is specified to be 1% by weight or less based on the weight of the capacitor element, and the capacitor element is housed in an outer box, and the opening of the outer box is sealed.' Chinese National Standard < CNS) / U Regulation (2i〇x 297 mm) -5S-, ~~ i! F. ≪ 1F 'ί — ili — — · (—r. I i I! N II ni III "-" Read the notes on the back and fill out this page) A7

8 1 8 9 V. Description of the invention (55) This' even under high temperature conditions at the time of surface mounting, the internal pressure of the outer box is not easy to rise. As a result, compared with Comparative Example 9, The expansion of the sealing surface (the plastic deformation of the sealing surface due to the increase of the internal pressure) is small. Any one can control the inappropriateness of the surface mounting at the beginning of the expansion (= 0.20mm) or less. This effect can make the sealing surface bulge or the surface of the wire floating during soldering, such as poor solder joint failure will not occur, and a stable solid electrolytic capacitor with high temperature surface mounting performance. The solid electrolytic capacitors according to the 31st to 37th and 39th to 41st aspects of the present invention are used for 250. (: Peroxide and sulfurized butyl rubber sealing material with a medium elastic modulus of 450N / cm2 or more is used to seal the opening of the outer box 'so', even at the temperature (245 ° c) at the time of surface mounting) As a result of ensuring the mechanical strength of the sealing surface, as compared with Comparative Example 9, the expansion amount of the sealing surface of the solid electrolytic capacitor (the sealing surface is plastically deformed due to an increase in internal pressure) is smaller. Appropriately controlled below the initial swelling volume (= 0.20mm). Also according to this effect, it can prevent the soldering and welding defects such as the expansion of the sealing surface or the floating of the wire during surface mounting, and a stable high temperature Surface-mounted solid electrolytic capacitors. In addition to the solid electrolytic capacitors according to Embodiments 37 and 40 of the present invention, in addition to the aforementioned effects, 'the solid electrolyte contains an adhesive component to reduce water absorption' and it is one of polyesters. The modified poly-p-phenylenedicarboxylic acid is based on the diester tree, so the moisture content of the capacitor element can be controlled to a minimum. As a result, the amount of expansion of the sealing surface during surface mounting will be reduced. The lowest, can get this paper size correction _ house standard (CNS) A4 specifications d view public love ----- II 1 ----- installation---- I-order · -----!- Line (please read the precautions on the back before ^, ¾ this page) Stamp printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs • 59- £ Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs-there is a fixed W y ... . ± ........— .. The energy-generating body electrolytic electricity & Yiyi according to the present invention. Dingde ... rent_ '^: sad and safe: ΐ, ~, female noodle The installation performance of the surface-mounted gas S electric power &capacitor;, the temperature of the famous works with pen 丨 0 to 1 () form: Pan 2 2 form φ 卞 also mainly explain ~ ^-% 1 (Embodiment 42) A dielectric anode with a dielectric oxide film is formed on the anode collar, and it is held between the shaft engraving and the electrode foil. (When the thickness is 50, the volume is 25, and it is wound with two non-woven fabrics. The electrolytic capacitor i element (the capacitor element is broken into a volume of 10% by weight of ethylene glycol-capacitor), at 45 t ― Amine

After the W liquid, the frequency is 120HZT 670 «F) ^ The energized amount is then impregnated. This capacitor element is immersed in a component containing a heterocyclic grass called dioxethiene and a second oxidant p-toluenesulfonic acid. Iron II: 6 parts of n-butanol under the oxidant solution, this is called the oxidation of this combination; grain liquid (relative to the iron content of ferric iron: ferrous iron ratio of ferrous iron (b) 0.005; and, relative The ratio of methanesulfonic acid to trivalent iron is mol ratio. After being removed, it is placed for 6 minutes at 85t. For 1 minute in the electrode box: = polyethylenedioxythiophene, a chemically polymerizable conductive polymer / Secondly, after this capacitor element is washed with water and dried, it is sealed with resin and sulfur-butyl rubber sealing material (consisting of 30 parts of butyl rubber polymer, 20 parts of carbon, 50 parts of inorganic filler, sealing hardness: 7). Irhd [After the international rubber hardness unit is put together in an aluminum box, the opening is sealed by hardening, and then the two lead terminals of the anode box and the cathode foil are respectively passed through the polystyrene sulfide] This paper size is applicable to China Standard (CNS) A4 size (21ϋ x 297 cm) • 60- ------! ------- ---- Γ I ί ί ». ---- I--I -------- II (碛 Please read the notes on the back before filling out this page) 4681 89 Employee Consumer Cooperatives, Intellectual Property Bureau, Ministry of Economic Affairs A7 is printed. 5. The seat plate of the description of the invention (57) is made of a surface-mounted solid IS electrolytic capacitor by bending the lead portion (size: diameter 10 mm x height 10 mm). (Embodiment 43) In this embodiment, an oxidant solution in which the oxidant solution A is placed in a 40 t environment for 60 days is used (relative to the amount of trivalent iron, the ratio of the amount of divalent iron is 0.01 by weight; and also relative to the amount of trivalent iron The molar ratio of p-toluene acid is Mohr's ratio 3.3), instead of the oxidant solution A in Embodiment 42, and the rest are made entirely in accordance with Embodiment 42. (Embodiment 44) In this embodiment, 'use will The oxidant solution A was placed in a 40 t environment and the oxidant solution was placed for 90 days (the ratio of the amount of divalent iron with respect to the amount of trivalent iron is 0,02 by weight. Also, the amount of p-toluene is relative to the amount of trivalent iron. The ratio is Morr ratio 3.0) 'This is used instead of the oxidant solution VIII in Embodiment 42, and the rest Manufactured entirely in accordance with Embodiment 42. (Embodiment 45) In this embodiment, an oxidant solution in which oxidant solution A is placed in a 400 ° C environment for 120 days is used (relative to the amount of ferric iron and the amount of ferrous iron). The ratio is 0.03 by weight; and the ratio of methanesulfonic acid to the amount of trivalent iron is mol ratio 2.9). This is to replace the oxidant solution A ′ in Embodiment 42 and the rest is completely performed in accordance with Embodiment 42. (Embodiment 46) In this embodiment, the oxidant solution A is completely dried at a temperature of 120 C (by evaporation of the solvent n-butanol, the solid component in the oxidant solution A is precipitated as p-toluenesulfonic acid second iron. (Salt) for a short period of time to take out the benzene sulfonic acid: ---.-- come ------- order --------- (please read the notes on the back before filling in this (Page) -61-Hair; 1?-Crystal. And instead of reality: ¾ Form 4. Drum. Seven singularities, except for using this crystalline component to muffle it again; the solution is tested in Wang i alcohol sales! Weaving; 'and Jiang Yan — "alcohol: capacity liquid Φ ,. 4% by weight of the completion of the '!' The rest of the Yuanjin Huiguanyuan Sheng i-state 42 is produced _ adjusted gasification agent solution relative to the amount of ferric iron, ferrous iron f ratio island weight ratio 〇 !! In addition, the ratio of trivalent iron to methanesulfonic acid is a mole ratio of 2.5. For the solid electrolytic capacitors according to Embodiments 42 to -46 of the present invention manufactured above, the electrostatic capacity (measurement frequency) is compared. Number 1 20Hz) 'Impedance (measurement frequency number 00kHz)' and the deviation range of the Tsui reactance, the results are shown in the table ("Also, the number of experiments in any experiment is 50, electrostatic capacity, impedance system It is shown by the average of 50-one by one ___ [表 ύ] !:; ^ ΐ S ~ lT ai £ τ—the maximum and minimum impedance II (^ F. | 2〇μ2) | ιη; „.3〇〇tit2! I (mil .lOOkHz) i (1 _ ί 丨 the maximum value and the minimum value deviation Embodiment 4 2 584 10 12 1 8 4 Embodiment 43 of the invention 43 ^ 580 18 20] 4 6 This issue Embodiment 44 578 1 19 24 17 7 Embodiment 45 of the present invention 5 51 ~~~ 1 30 55 17 ″ 3 8 ¥ Difficult implementation of the invention 4 6 ~ Τ97 45 J 05 25 70… From Table 6, it can be seen that 'the embodiment of the present invention The solid aluminum electrolytic capacitors of 42 to 44 are compared with the embodiments 45 and 46. Not only the electrostatic capacitance is high and the impedance is low, the deviation range is also small, so a solid electrolytic capacitor with less deviation in electrical characteristics can be obtained. Furthermore, the present invention runs The impedance tendency shown in patterns 42 to 46 can be seen. In the oxidant solution, it is relative to the amount of trivalent iron. The amount of divalent iron + its amount is less than 0.02. '4 should be the standard outline of heavy paper _ _ 家 群 （CiNS ) A4 specification (? Κ) χ 29Γ public meal) Please read the details on the back before filling in this butter}-^ * • Printed by Xiao Gong Consumer Cooperative, Intellectual Property Bureau, Ministry of Economic Affairs -62 · 468188 Member of Intellectual Property Bureau, Ministry of Economic Affairs ΗConsumer Cooperation Du Yinfa B7 V. Description of the Invention (59) In the oxidant solution, if the ratio of the amount of divalent iron to the amount of trivalent iron exceeds about 0.02, the impedance value will become extremely large, which is not ideal. It can be seen that in the oxidant solution, relative to the amount of trivalent iron, the amount of divalent iron The ratio is preferably equal to or higher than 3.0 Mohr ratio. In addition, if the ratio of the amount of ferrous iron to the amount of ferric iron in the oxidant solution is lower than or equal to about 30 Molar ratio, the impedance value will be extremely large, which is not ideal. "Paraformic acid (commercial product: reagent grade 1) is added to the oxidant solution a used in Embodiment 42 of the present invention, so that the ratio of the p-toluene acid to the amount of divalent iron in the oxidant solution relative to the amount of divalent iron The molar ratio was adjusted to 3.6, and the same experiment was performed using this oxidant solution. As a result, the leakage current value increased significantly (in the range of 100 to 1000 / ZA). Compared with the solid electrolytic capacitors tested in Embodiments 42 to 46 of the present invention) The leakage current value is only 10 or less than A. It can be seen that the amount of p-toluene in the oxidant solution is relative to the amount of trivalent iron. If the ratio exceeds the Mohr's ratio of 3.5, the leakage current will be significantly larger, which is not ideal. Considering the tendency of the aforementioned impedance values together, the most suitable range of the ratio of p-toluenesulfonic acid with respect to the amount of trivalent iron in the amidine solution is a range of 3.0 to 3.5. In addition, by using the oxidizing agent solution and method for producing a conductive polymer of the present invention, a solid electrolytic capacitor with less variation in electrical characteristics can be produced stably. Next, the embodiments in the 20th to 22nd aspects will be mainly described. (Embodiment Mode 47) For anode foils composed of aluminum foil with a dielectric oxide film formed, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) -63-:-Kang- ----- -Order -------- • Line ί Please read the notes on the back before filling in the poor page) Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs 0 * Industrial Cooperatives ί # tv m .. .. .. [Table:] •, .......... Static electricity_1 ......; η Η-*: ¾.?; Implementation Department ^; 47 ~ .........— ..............; ... 600 1 ............ .... ....... -... 「Ο ......... .Earth inventions are shaped, they are all out ... 'oTT… 7 ϊτ ........ ....., / .. "" V .... The above invention implements the shape bear 49 * -......—_ 615… '— —To " One — ......—-- -----------1 .......... Left invention implementation shaped bear 5 (factory-.- a filT ... .... ......... nr ..............: —… — .. …… τι .......... Comparative Example 丨0 —— one: — * one one 598 22 4.2 It can be seen from Table 7 that the solid aluminum electrolytic capacitors according to the embodiments 47 to 50 of the present invention have a benefit compared to Comparative Example 10. Not only static electricity In addition to high capacity and low impedance, the standard deviation is also small, so it can be obtained-solid electrolytic capacitors with small deviations in electrical characteristics are also shown in the impedances shown in Embodiments 47 to 50 of the present invention and Comparative Examples]. The lower the residual amount of N, N-dimethylethylamine in dioxofluorene, the better, and the upper limit value is 0.8%. The residual amount of N, N-diethylacetamide is more than 0.8. Starting from the vicinity of%, the impedance value will become extremely large, so it is not ideal. Also, by using the manufacturing method of the present invention, a solid electrolytic capacitor with little variation in electrical characteristics can be manufactured stably. Although the foregoing embodiments of the present invention are only described, The winding type solid electrolytic capacitor is not limited to this. The solid electrolytic capacitor in which a dielectric polymer film, a dielectric polymer layer and a cathode layer are formed in this order on a valve-acting metal box is also used. The present invention can be effectively learned from the above embodiments: (1) Because a layer containing an electrically conductive polymer and a polymer lacking conductivity is provided on a dielectric oxide film of an anode body composed of a valve-acting metal, Low electrical resistivity The conductive polymer is set on the dielectric. The paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) -66-ft II id ~. I * i Γϊ 1 I n IE · II n D nt— I. O. I n II iii Read the back of the page first; I will fill in this page before the matter) i) Printed by Ai B7 Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention (61) Production according to Embodiment 47 "(Implementation Aspect 49) Except for Embodiment 47, the monomer A was further distilled under reduced pressure to adjust it to the result of gas chromatography analysis as an impurity N, N-dimethylacetamidine in ethylenedioxythiophene. Except for the residual amount of amine of 0.4%, the remainder was prepared entirely in accordance with Embodiment 47. (Embodiment 50) Except for Embodiment 47, the monomer A was further repeatedly distilled under reduced pressure, and adjusted to the result of gas chromatography analysis as an impurity N, N-dimethyl in ethylenedioxythiophene. Except for the residual amount of acetamide, which is 0-3%, the rest is made entirely according to Embodiment 47. (Comparative Example 10) Except for using ethylene dioxin without performing vacuum distillation in Embodiment 47, the rest of the production was performed in accordance with Embodiment 47. In addition, based on the results of gas chromatography analysis of this comparative example, the residual amount of the impurity N, N-dimethylethylamine in ethylenedioxyphene was adjusted to be! 〇〇 / 〇. As for the solid electrolytic capacitors of the present invention in the application forms 47 to 50 and Comparative Example 10, the capacitance (measurement frequency: 120 Hz) was compared with the impedance (measurement frequency: 100 kHz), and the leakage current (applied rating The value after 2 minutes of voltage 16V) and the standard deviation of impedance are shown in Table 7. In addition, the number of experiments in any experiment is 50, and the capacitance and impedance are shown by the average value of 50. This paper size applies to China National Standard (CNS) A4 specification (210 X 297 mm) • 65- UIIIIJIH- --- i 11 order ---- 111 i (谙 read the ii meanings on the back side before * this page) Economics-Ministry of Wisdom. Property Cooperation between Industrial and Consumer Affairs Du printed A7 B7 V. Description of Invention (62) [Table 7] Capacitance (β FJ20HZ) Impedance (τηΏ, 100kHz) Standard Deviation of Impedance (mQ, 100kHz) The present invention Embodiment 47 600 14 1.9 Embodiment 48 of the invention 48 611 12 1.8 Embodiment 49 of the invention 49 615 10 1.5 Embodiment 50 of the invention 50 614 10 1.5 Comparative Example 10 598 22 4'2 As can be seen from Table 7, Embodiments 47 to 50 of the invention Compared with Comparative Example 10, the solid aluminum electrolytic capacitor has a high electrostatic capacity and low impedance, and the standard deviation is small. Therefore, a solid electrolytic capacitor with less variation in electrical characteristics can be obtained. It is also known from the impedance trends shown in Embodiments 47 to 50 of the present invention and Comparative Example 10 that the lower the residual amount of N, N-dimethylacetamide in ethylenedioxophene is, the better, and the upper limit is The limit is 0.8%. Since the residual amount of N, N-dimethylacetamide exceeds 0.8%, the resistance value will become extremely large, which is not desirable. Furthermore, by using the manufacturing method of the present invention, a solid electrolytic capacitor with little variation in electrical characteristics can be manufactured stably. "Although the aforementioned embodiments of the present invention only describe winding type solid electrolytic capacitors", the present invention is not limited to this. For a valve-acting metal foil, a dielectric oxide film and a dielectric polymer are sequentially formed. A solid electrolytic capacitor having a wide range of layers and cathodes is also effective. The present invention can be known from the above embodiments: (1) Because a layer containing an electronic conductive polymer and a polymer lacking conductivity is provided on a dielectric oxide film of an anode body composed of a valve-acting metal, it can be Set the low-resistance electronic conductive polymer on the dielectric. The paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 male *) I 1IIIIIIIIII — -HI — — — ^ 111! 11 (please first Read the precautions on the back and fill in this page> -66- A7 _______ B7 ^ _ 5. Description of the invention (") on the oxide film and use this as an electrolyte to reduce the resistivity (impedance) of the capacitor. The electrical oxide film is combined with a non-electronically conductive polymer with a very high resistivity. Therefore, even if the electronic disintegration starts from the damaged part of the dielectric oxide film, and the leakage current is significantly large, it can be used in This part suppresses the phenomenon of electron disintegration. * Since this phenomenon can be suppressed in a local area until the dielectric body is destroyed (short-circuited), it can constitute a solid electrolytic capacitor with a small leakage current and a short circuit that is unlikely to occur during aging. (2) Between the anode foil and the cathode foil on which the dielectric oxide film is formed, an insulating layer composed of a nonwoven fabric obtained by using a resin as a main body and obtained by a spunbond method, or a polyester resin obtained by a wet method is held. A separator composed of a non-woven fabric is 'wound and wound' to form a capacitor element, and a solid electrolyte is provided between the anode foil and the cathode foil of the capacitor element, thereby constituting, due to the adhesion and adhesion of the solid electrolyte to these insulation layers. The resistance is excellent, so it can reduce the impedance in the high-frequency area. Also, because the isolating layer can fully ensure the strength, the short-circuit occurrence rate and leakage current in the curing process can be suppressed, and an impedance characteristic and leakage can be obtained. Solid electrolytic capacitors with excellent current. (3) Between the anode ball formed with the dielectric oxide film and the dielectric oxide film and the cathode foil with a withstand voltage of 0.8V, an isolation layer is held, and then it is rolled. A capacitor element is wound to form a solid electrolyte of a conductive polymer between the anode foil and the cathode foil of the capacitor element. The dielectric oxide film and the polymer solution have good moisture permeability. Therefore, the conductive polymer solid electrical paper produced near the cathode foil has a K degree suitable for Zhongguanweibiao iMCNS) A4 specification ⑽X 297 public love) --- ----—— ———— Install—— ί Please read the precautions on the back before jealous of this page) Order--Line · Printed by the Employee Consumer Cooperative of the Smart Finance and Economics Bureau of the Ministry of Economic Affairs-67 · Send a separate note ,. ....; Die. Gaikechun. Static electricity. Tamping. In the field of frequency bands: .t: ίτ; g of large capacity f; fresh electricity s and (4) formed on the surface of the cathode foil At least one of titanium, hafnium, and hafnium—a gold field or a hafnium compound or a carbon halide material: Based on this structure, the permeability of the hafnium layer and the polymerization solution formed by the shading can be improved, and it can also be used on the cathode. The coverage of the solid electrolyte of the conductive polymer that was recently produced is significantly different. Therefore, a solid electrolytic capacitor with a low impedance in the high frequency range and a large capacitance extraction rate can be obtained ( 5) A solid electrolytic layer and a fe electrode lead-out portion are provided on the anode electrode on which a dielectric film is formed. The quantity is limited to the weight basis 丨% by weight or less. The outer package component covers the capacitor element 1 according to this structure. It is a surface-mounted solid electrolytic capacitor with a high-temperature surface-mounting performance. ) Use a conductive polymer obtained by chemically oxidizing and polymerizing a heterocyclic monomer with a ratio of the amount of divalent iron to a weight of 0.02 or less of 0.02 iron oxide as a solid electrolyte, and (6 — B) Use a dry oxidant with a ratio of aliphatic and aromatic sulfonic acid relative to the amount of trivalent iron, or a molar ratio of 乂 0 ~ 3 ″, and chemically oxidize the heterocyclic monomers to polymerize γ. Conductive molecules are used as solid electrolytes. According to this structure, in chemical vaporization polymerization, a conductive polymer with high conductivity can be obtained in a good yield, so it can provide a solid electrolytic capacitor with small deviations in capacitance and impedance characteristics. And its manufacturing method. (7) Heterocyclic formula 468189 A7 with residual basic organic solvent content of 0.8% or less -------- B7 V. Description of the invention (65) Conductivity obtained by chemical polymerization of monomers As a solid electrolyte, a polymer is used, 'a conductive polymer having a high conductivity can be obtained with good yield during chemical polymerization', so a solid electrolytic capacitor with a small variation in capacitance and impedance characteristics and a method for manufacturing the same can be provided. The invention can obtain a solid electrolytic capacitor having a small leakage current, a large capacity, and high heat resistance, which is suitable as a surface mount component, and a manufacturing method thereof. Furthermore, it is possible to provide an amidine solution for conductive polymer polymerization and conductivity. The composition conditions of heterocyclic monomers for polymers are used in the manufacture of solid electrolytic capacitors with such performance for stable performance with low performance deviation, and have reported their industrial value. [Comparison Table of Component Numbers] 1 ... Anode Foil 2 ... Cathode Foil 3. Isolation Layer 7 ... Cathode Wire 9 ... Aluminum Outer Box 11 ... Dielectric Oxide Film 4 ... Contains Electronic Conductive Polymer and Layer 5 of polymer lacking conductivity ... Layer 6 containing chemically polymerizable electronic conductive polymer 6 ... Anode wire 8 ... Sealing material 1 〇 ... Seat plate 12 ... Capacitor element -69- (Please read the precautions on the back first (Fill in this page) This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

Claims (1)

468189 A8 B8 C8 D8 Patent application scope Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs l A solid electrolytic capacitor whose capacitor element is formed by holding an insulation layer between an anode foil and a cathode foil formed with a dielectric oxide film, and further It is formed by winding, and the capacitor element is provided at least on the dielectric oxide film of the anode foil. A layer containing an electron conductive polymer and a south molecule lacking conductivity. 2_ If the solid electrolytic capacitor according to item 1 of the scope of patent application, the resistivity of the electronic conductive polymer component monomer provided on the layer on the dielectric oxide film of the anode body is less than 1.0x1 / □, and it is lacking The resistivity of the conductive polymer component monomer is more than 1.0 ×× 10 × 10Ω / 匚]. 3. If the solid electrolytic capacitor of the scope of the application for the item 1 or 2 of the patent application, wherein the electronic conductive polymer of the layer provided on the dielectric oxide film of the anode body is selected from at least one of the following, namely: Poly Bila, polybenzyl amine, sulfonated polyaniline, polyphenanthrene, polyethylene dioxythiophene, polybenzyl sulfonic acid, and a group consisting of derivatives of these compounds. 4. If the solid electrolytic capacitor of item 1 or item 2 of the patent application scope, wherein the component of the polymer lacking conductivity in the layer provided on the dielectric oxide film of the anode body contains at least one selected from the following One or more polymers or copolymers, namely: polyvinyl alcohol 'polyvinyl acetate, polycarbonate, polyacrylate' polyfluorene acrylate, polystyrene, polyurethane, polyacrylonitrile, polybutadiene , Polyisoprene, polyether, polyester, polyethylene terephthalate, polybutylene terephthalate, polyamide, polyimide, butyraldehyde resin, silicone resin, Melamine resin, alkyd resin, cellulose, nitrocellulose, bisphenol A type epoxy resin, bisphenol F type epoxy resin, alicyclic epoxy resin, and derivatives thereof and the like. Circle national standard (CNS) A4 specification (210 X 297 public love) • 70--. ^ 1 I v ^ i. ^ 1 I ^ 』Λ (Please read the precautions on the back before filling this page) SJ. Line. Study of Lang's Formation For example, the solid electrolytic capacitor in item 4 of Shenqing Patent. Among them, the lack of conductivity of the layer on the dielectric oxide film of the carboxylamine body is selected from the group containing at least its umbrella. Molecule or copolymer 'one kind', that is, a group consisting of cyclopropyl propyl modified polyester sulfonic acid modified polyester modified polyester = 6 — solid electrolytic capacitors, including: a capacitor element, which is An insulation layer composed of a non-woven fabric obtained by a spunbond method or a wet method with resin as a main body is held between a male pig and a cathode with a dielectric film formed thereon, and then formed by winding it; And a solid electrolyte 'is composed of a conductive polymer containing a conductive polymer provided between the anode case and the cathode of the capacitor element. C 7' A solid electrolytic capacitor such as the scope of patent application No. 6, wherein the insulation formed by a non-woven fabric The layer is a non-woven fabric containing polyester resin. 8. The solid electrolytic capacitor according to item 6 of the patent application, wherein the insulating layer formed of a non-woven fabric is a non-woven fabric containing polyethylene terephthalate resin and its derivatives. 9. The solid electrolytic capacitor according to item 6 of the patent application, wherein the thickness of the isolation layer formed by the non-woven fabric is 80 m or less, and the weighing range is 10 to 60 g / m2. 10. A solid electrolytic capacitor, comprising:-a capacitor element, which is formed between an anode 4 having a dielectric oxide film formed thereon and a cathode foil having a dielectric oxide film having a withstand voltage 0.8 to 10 V; National Standard (CNS) A4 specification (2i0X 297 mm) Α8 Β8 CS D8 Sixth Intellectual Property Bureau of the Ministry of Economic Affairs printed by employee consumer cooperatives 46 818 9, the patent application scope 'holds the isolation layer, and then rolls it to form And a solid electrolyte 'are composed of a conductive polymer containing a conductive polymer disposed between the anode element and the cathode foil of the capacitor element. 11. A solid electrolytic capacitor, comprising: a capacitor element, which is formed on an anode foil with a dielectric oxide film formed thereon and a coating layer made of at least one metal of titanium, cobalt, and thorium or a compound thereof or a carbon film material Between the cathode foils, an insulation layer is held and wound, and a solid electrolyte is composed of a conductive polymer that is provided between the anode box and the cathode foil of the capacitor element. 12. For a solid electrolytic capacitor with the scope of application for item 10 or item η, the insulation layer is a non-woven fabric with uneven density in the thickness direction, and the low-density side of the non-woven fabric is wound toward the cathode foil side. 13. A solid electrolytic capacitor, comprising: a capacitor element, which is formed by holding an insulation layer between an anode foil and a cathode foil on which a dielectric oxide film is formed, and then winding it to form the anode foil; A solid electrolyte layer containing a conductive polymer is formed between the cathode foil and the moisture content based on the weight of the solid electrolyte layer is less than 1% by weight; an outer packaging box is made of a bottomed cylindrical metal, which is used for The capacitor element is housed; and a sealing unit is a unit that contains a polymer component and closes the opening of the outer packaging box. 14. A solid electrolytic capacitor, comprising: This paper size applies to China National Standard (CNS) A4 (210 X 297 public love) nn n. N * I ϋ u Ft n I ϋ —i ϋ ϋ ϋ a. n 1 i n. (Please read the precautions on the back before filling out this page) '72 ·. 乂 ”” Battery 《I. it decadent- ^ It is separated from the masculine, and then the round box is provided by you The base made of metal 1 is used to ㈣ the capacitor companion, and-the sealed component 'It is made of oxide and thinned " or resin ", and at 250 c' T has a modulus of elasticity above 450N / O112. Comment on the number of chopsticks ~ T base rubber opened ft into 'and sealed the outer box of the aforementioned α part t U. For example, the solid electrolytic capacitor of item 3 of the patent application, wherein the sealed component containing the shoulder polymer component is A butyl rubber that has a modulus of elasticity of 450N / cni 2 or more at 25 kt after vulcanization and / or resin vulcanization is used. Κ A solid electrolytic capacitor, which is based on the _ The second iron salt of acid is dissolved in an alcoholic solvent, and the ratio of the amount of divalent iron to trivalent iron I is the weight. 〇2 The oxidant ghost liquid 1 heterocyclic monomer is chemically oxidized and polymerized, and the obtained conductive polymer is used as a solid electrolyte. The Ministry of Economic Affairs Intellectual Property Bureau staff consumer cooperatives printed # ,, a solid electrolytic capacitor, Based on—A solution in which the second iron salt of an aliphatic and / or aromatic domain acid is dissolved in an alcoholic solvent, and the ratio of the aliphatic and / or aromatic sulfonic acid to the amount of trivalent iron is the molar ratio The oxidant solution in the range of 2.0 ~ 3,5 is used for chemically oxidizing and polymerizing heterocyclic monomers, and using the obtained conductive polymer as a solid electrolyte: is the solid electrolysis such as the 16th or 17th in the scope of patent application Capacitor, wherein the oxidant solution is an alcohol solution of the second iron salt of methanesulfonic acid; 19. An oxidant solution for conductive polymer polymerization, which is based on a fat-73-46 8 1 8 9 A8 B8 C8 _________ D8 6. The scope of the patent application and / or the second iron salt of aromatic sulfonic acid is dissolved in an oxidant solution made of an alcoholic solvent, and the ratio of the amount of divalent iron to the amount of trivalent iron is 0 to 02 by weight, and For ferric iron, aliphatic and / or aromatic ratio continued to acid molar ratio in the range of those of 3.〇~35. 2． · A solid electrolytic capacitor, which has high conductivity by chemically oxidizing and polymerizing heterocyclic monomers containing impurities of a basic organic solvent remaining from 0.8% or less of NH. Molecules act as solid electrolytes. 21. For example, the solid electrolytic capacitor of the scope of application for patent No. 20, wherein the heterocyclic monoethylene oxydiphene is chemically oxidized and polymerized by using at least an oxidant component and a dopant component. , And the obtained conductive polymer is used as a solid electrolyte. 22. —A method for manufacturing a solid electrolytic capacitor is to form a solid electrolyte composed of a conductive polymer between the anode 4 and the cathode 借 by the following method. The method is: forming a dielectric oxide film An insulation layer is held between the anode foil and the cathode foil, and then it is wound to form a capacitor element, and the capacitor element is immersed in a solution containing at least the conductive polymer polymerization oxidant such as the item 19 of the patent application scope and the patent application The mixed solution of the heterocyclic monomer of the scope item or item 21, or the capacitor element is immersed in a solution containing the conductive polymer polymerization oxidant such as the scope of the patent application scope item 19, and then immersed The capacitor element is immersed in a solution containing a heterocyclic monomer such as the scope of patent application No. 20 or 21, or the capacitor element is immersed in a solution containing the scope of patent application No. 20 or 21 Read. Conductivity of item 9 in the rat range. High score + 't ^ β Aqueous rolling agent is dissolved; night π is 23, the manufacturer of a solid electrolytic capacitor """ swimming column _F column; 5 Method in field ^ between foil and cathode Formed by Qi Lei. ★,., 'The solid solid group formed by Dian 1 Master Qiaozi is degraded, this method is: · In the formation of a dielectric gasification film', ~ anode · metallurgy and cathode The foil's common insulation layer 'is then wound into s to form a lightning strike. _ Take the I and steal the components, and then immerse the capacitor I element at least contains the same as the application ~' τ 1 patent dry enclosure No. 3 For the conductivity of the molecule, please contact the solution of the polymer with a lack of conductivity as described in item 4 or item 5 of the patent application. Then, heat A φ ^ to heat the electric valley IS to make the solvent The solvent component printed by the employee's consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs evaporates, and a layer containing the above-mentioned electronic conductive polymer and a shoulder molecule lacking conductivity is provided at least on the dielectric oxidation port of the foregoing anode 羯. The capacitor element is immersed in a mixed solution containing at least an oxidant solution for polymer polymerization of a galvanic polymer and a heterocyclic monomer, or the capacitor element is immersed in the solution containing the oxidant solution for the conductive high-S polymerization. And then immersed in the single In the solution, or immersing the capacitor element in the solution containing the aforementioned _ ring monomer, and then immersing the capacitor element in the solution containing the aforementioned conductive high-dose polymerization oxidizing agent. The manufacturing method of the solid electrolytic capacitor according to item 23, wherein the ocean liquid containing the conductive polymer and the polymer lacking conductivity is at least an aqueous solvent. 25, such as the solid electrolytic application of the 23rd or 24th in the scope of the patent application The manufacturing method of capacitors, which are sold in the form of solids composed of conductive polymers. • The paper size is applicable to China National Standard (CNS) Al specifications (210 X 297 mm) 468189 6. When applying for a patent, the conductive polymer polymerization oxidant solution used is the conductive polymer polymerization oxidant solution as described in item 19 of the patent, and the heterocyclic single system is as described in the scope of patent application. Item 20 or item 21 Heterocyclic monomer. — — II I ϋ n * 1 ϋ I n I 甘. * * I (Please read the precautions on the back before filling out this page > Order --------- Economics Department Intellectual Property Bureau employee consumption cooperation Du Yin-76- This paper size is applicable to the national standard (CNS) A4 specification (210 X 297 cm)