TW459255B - Solid electrolyte capacitor and the manufacturing method thereof - Google Patents

Abstract

The present invention relates to a solid electrolyte capacitor and the manufacturing method thereof which comprises a solid electrolyte containing layer and a conductor layer containing metal powder, or a conductive carbon layer and a conductor layer containing metal powder and formed thereon; in which, at least one of the solid electrolyte layer and the conductor layer is composed of rubber-like elastic material. The present invention also relates to the solid electrolyte used in the solid electrolyte capacitor and the manufacturing method for the solid electrolyte; and, relates to the conductive paste used in the solid electrolyte capacitor and the conductive carbon paste. The inventive solid electrolyte capacitor provides the features of such as miniaturization, high capacity, low impedance and having excellent external stress relaxation, productivity, heat-resistance and moisture-resistance.

Description

459255 A7 B7 V. Description of the invention (1) < Technical Field > The present invention relates to an electrolyte layer and an isoelectric layer (containing, conductive of gold tincture powder. The electrical layer or a conductive carbon calendar and the above) Conductive body made of gold 靥 powder 暦) At least one solid solid containing rubber-like elastic material i.. · Electrolytic 鼋 container and its manufacturing method. ; D In detail, it is a solid electrolytic capacitor that can be miniaturized, high capacity, and / or low impedance, and has excellent external stress and characteristics, productivity, resistance to humidity and humidity. And its manufacturing method. The present invention also relates to a solid electrolyte for a solid electrolytic capacitor, a metal powder-containing conductive paste, and a conductive carbon paste. < Background technology > · '. * The solid electrolytic capacitor is formed by an etching treatment on a metal substrate with a large specific surface area (an electrode substrate) to form an oxide coating layer of a dielectric (insulating medium), and forms an opposite surface on the outside thereof. The solid semiconducting body calendar of the electrode (K is referred to as the solid electrolytic layer), and it is further taken as a mold-forming body layer containing metal powder on the outside or a conductive carbon layer and the gold powder on it. The conductive element layer is formed, and it is connected to the lead wire to form a basic element of the capacitor, and then the entire element M is completely encapsulated with an insulating resin such as epoxy resin, and is widely used as an electrical container component in electrical products. With the digitization of electrical equipment and the speeding up of personal computers, the use of small-sized and large-capacity electric power is required for solid electrolytic capacitors used thereon.

I 'Container and capacitor with low impedance in high frequency range. In response to the requirements of these solid electrolytic capacitors, various solid 'electrolytes and conductors have been proposed heretofore. For Μ solid electrolytes, such as manganese dioxide and lead dioxide, etc., the Chinese paper standard (CMS) A4 specifications (2! 0 X 297 mm) are applicable to this paper. (Please read the precautions on the back before filling this page ) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China. 45925 5 Α7 Β7 V. Description of the invention (2) Organic semi-corporeal materials; there are also organic semiconductor materials, For example, TC »Q (tetracyanoquinodimethane) complex salt, or a truly conductive polymer having a conductivity in the range of 10-3 to 5X 10.3s / cb [Japanese Patent Application Laid-Open No. 1-1699 1 4 (US Patent Nos. 4,80 3, 5 9 6 or π-conjugated fluorene polybenzylamine (Japanese Patent Laid-Open No. 61-239 617), polypicine (Japanese Patent Laid-open No. 61-240625), and polythiophene derivatives Electrically conductive polymers such as Japanese Patent Application Laid-Open No. 2-15611 (US Patent No. 4,910,645), polyisothioindene (Japanese Patent Publication No. 62-118511) are used. ^ Capacitors using solid electrolytes of manganese dioxide , Not only during the thermal decomposition to form manganese nitrate, the medium oxygen previously formed in the anode foil In addition to the coating layer being damaged, it has the disadvantage of insufficient resistance. When using lead dioxide, 'there is also a concern about environmental problems.' In addition, capacitors using TCNQ complex salts lacking solid electrolytes have good Hot melt processability and electrical conductivity, but the TCNQ complex salt itself has the problem of heat resistance, and the reliability of the heat resistance is poor during welding. As for the capacitor using a solid electrolyte of a conductive polymer, although the dielectric coating may not be broken And has high impedance characteristics, but it has the problems of poor heat resistance, thermal shock resistance, and shock resistance. In the past, a solid electrolyte using a conductive polymer has been used as a valve with a fine void structure. A method for forming a dielectric surface on a metal surface by melting the above-mentioned conductive polymer (solid electrolyte) or a method for precipitating the above-mentioned galvanic polymer on a dielectric calendar is known. Specifically, for example, When a polymer of a five-membered heterocyclic compound such as pyrrole or thiophene is used as a solid electrolyte, the anode foil formed with a dielectric film is impregnated. -5- paper rule Applicable Chinese National Standard (CNS) A4 size (210 X 297 mm)

4 5 9 2 5 5 A7 ____B7_ V. Description of the invention (3) After the low alcohol and / or water solution of these heterocyclic compounds, then immersed in the aqueous solution in which the oxidant and electrolyte are dissolved to carry out the chemical polymerization of single amidine. The method of forming a conductive lip with a desired thickness (Japanese Patent Application Laid-Open No. 5-1.75082.); Coating 3,4-dioxyethylene thiophene monomer and oxidizing agent, preferably K solution »before or after the shape separately or together Method for forming conductive polymer layer on metal and oxidized coating layer [(Japanese Patent Application Laid-Open No. 2-15611 (US Patent

No. 4,91Q, 6 4 5) or JP 1Q- 3 2 1 4 5 (European Patent '', * Publication No. 8 2 0 Q 7 6) and others are known. Among the known oxidants are iron chloride (m), F e (C 1 0 *) 3 or organic acid iron (I), which are used in the polymerization of five-membered heterocyclic compounds such as thiophene and the like. , Inorganic acid iron (M), alkyl persulfate, ammonium persulfate. (M hereinafter referred to as APS), hydrogen peroxide, K2 Cr3 07, etc. [Japanese Unexamined Patent Publication No. 2-156U (US Patent No. 4,9 No. 10, No. 645)] or feed compounds, silver compounds, etc. [Japanese Unexamined Patent Publication No. 10- 3 2 1.4 (European Patent Publication No. 82 0 0 76 ')] »A method recently disclosed. It is K powder polyaniline As a conductive and raw material, it is added and dispersed in the rubber and / or thermoplastic resin of the base material ^ It is compounded into a polybenzylamine compound with organic strength and flexibility, and a special polybenzylamine compound Method (Japanese Patent Application Laid-Open No. 64- 6 9 6 6.2). In addition, there is also a poly * t aniline solution containing 1 to 25 weight X of polymer adhesive on the metal electrode of the capacitor electrode to form a composite coating, and then an isoelectric polymerization with an anion added to the polyaniline. Method for manufacturing capacitors characterized by physical layers (Japanese Patent Application Laid-Open No. 5-3138). According to the above method, since a conductive polymer layer is formed on the oxide coating of the insulator, a thin conductive layer must be formed in advance by chemical polymerization. At the same time, the paper dance scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (ttRead the notes on the back before filling in the flavor page) -------, | Order i, — III—line {" 3r | _1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 45925 5 A7 __._ B7_ V. Description of the invention (4) In order to make it suitable for various capacitors, the following problems are often encountered: (1) In the case of electrolytic polymerization: polymers with poor flexibility, if the viscosity is increased, the capacity will be caused The reduction of (capacity) is because the aluminum foil with the medium formed on the surface obtained by the engraving of the surface is immersed in the oxidant solution and dried. A highly viscous oxidant film is formed on the surface of the porous body, so it exists in the porous The orifices of fine pores on the body surface will be douced. In addition, a polymer is formed on the surface of the porous body due to contact with the monomer, so that no polymer is formed inside the fine pores, resulting in a decrease in capacity. (2) In the case of chemical polymerization: the amount of polymer that can be obtained by one polymerization is small, so it must be impregnated multiple times, so the productivity is low. (3) The adhesion between the dielectric film and the solid electrolyte must be good. If it is not good, it will cause the degradation of the product and the problem of uniformity, which affects the manufacturing yield and service life. In order to solve the above problem, most of them are produced by the depolymerization polymerization method or the chemical polymerization method. Conductive polymers such as polypica are used as the solid electrolyte for solid electrolytic capacitors, but the conductivity of the resulting capacitors is The uniformity of the polymer film, or the soldering heat resistance and impedance characteristics when making electrolytic capacitors are difficult to be ideal.

I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs | In addition, the conductivity of the cathode lead terminal and the solid electrolyte layer is bonded by M. r 'The physical history is usually a conductive material composed of a conductive filler and a synthetic resin as an adhesive' Sexual paste. The conductive filler is usually selected from metal powders or carbon powders such as gold, silver, copper, etc. Due to cost and performance, silver powder is generally preferred. Synthetic resins for adhesives are usually epoxy resins, resins, etc., and other resins such as polyhoned, polyimide, and fluorinated resins (Japanese Unexamined Patent Application No. 5-1.5 2 1 7 1) or -7- The scale is applicable to the national standard (CNS) A4 specification (210 X 297 mm) A7 459255 _B7_ V. Description of the invention (5> Polyacrylic resin < Japanese Patent Application Laid-Open No. 7-233298) is also known. Electro-pastes have been widely used as bonding agents for silicon M and lead frames, that is, they are used as die bonding materials. A conductive paste for crystal bonding using a fluorine-containing polymer as an adhesive has been disclosed (Chai Kaihei 2-53Q4). The conductive paste for die bonding must have high conductivity, high heat resistance, small shrinkage stress during die bonding, and low water absorption after bonding. In addition, it is necessary for the conductive paste to have a property capable of reducing the stress occurring between the sand crystal and the lead frame during thermal bonding. 'As for the silver paste used by M-like synthetic resin as an adhesive, it has a high modulus of elasticity and is prone to high stress during reflow, which increases leakage. J ·. · · Electricity or peeling of the bonding interface Cause of thermal degradation of impedance. In addition, the paste has a high water absorption rate, and has a problem that performance degradation easily occurs under high temperature and high humidity. In addition, there is silver tincture using K fluorine resin as an adhesive. This paste has the same high elasticity as the above, and it is easy to generate high stress during reflow, which affects the product properties. Furthermore, it is widely used as electrical conductivity. The silver of the material is superior in price and performance, but it is easy to cause migration. Therefore, the conductive paste printed by the solid electrolytic capacitors \ Ministry of Economics and Intellectual Property Bureau employee consumer cooperatives needs to be pre-coated for various occasions. After the carbon paste, conductive silver paste is used. There are many types of conductive materials, adhesives, and solvents used for conductive carbon paste. For example, the conductive material can be a combination of natural black lead (scaly thallium lead of 10-20wm) and carbon black (Japanese Patent Application Laid-Open No. 9-31402 ); Carbon particles with protrusions (Japanese Unexamined Patent Publication No. 5-7 ◦ 7 8); a combination of conductive materials and viscous, stubborn ^ 8 " This paper size applies to the Chinese solid standard (CNS > A4 specifications < 210 X 297 mm) 459255 A7 B7 V. Description of the invention (6) * {Please read the precautions on the back before filling this page) Carbon black and synthetic resin below 20wffi can be used (Japanese Patent Laid-Open No. 4-181607); scaly black Combination of lead powder and fine black lead powder (above aspect ratio 10, average particle size 10 «under) and epoxy resin (Japanese Patent Application Laid-Open No. 7-262822); black lead and fluorine-containing polymer, such as p TFE fine particles ( JP-A-Sho 6 1-6 98 5 3); In addition, carbon powder and glycidyl ethyl chain are used in combination of isoelectric materials and solvents (JP-A 4-177802); and it can be used as an adhesive. Synthetic resins include polyethylene, epoxy resin, and phenol resin. _ —Π * 二 But, using the conductive carbon paste of natural black tincture, because the natural black lead is in the shape of scales, the filling property is not good, and because of the large amount of impurities, the conductivity is significantly lower. The subsequent surface has fewer irregularities, and the interface has the disadvantages of easy peeling and thermal degradation of the impedance caused by the island. In addition, the conductive phosphorus paste using carbon black has extremely small powder particles and therefore cannot improve the filling property. As with natural black lead, it is difficult to improve the conductivity. Therefore, the conductive carbon paste using natural black lead and carbon black must be fully dispersed during the production of the paste, so that it is troublesome to handle.

U Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When K epoxy resin wax is used as an adhesive, although it has a lower cost and is easier to handle, due to the high rain, with the increase in the size of the chip, In the case of reflow, there is a problem of reducing the stress that occurs between the crystal core and the lead frame during heating, and problems such as low moisture resistance due to M and high water absorption islands. < Object of the invention> The object of the present invention is to provide a small, lightweight, high capacity, high

C-frequency characteristics, δ, leakage current, heat resistance (reflow resistance), thermal shock resistance, resistance to solid electrolytic capacitors, etc., especially M provides excellent paper size applicable to Chinese National Standard (CNS) A4 specifications (2.10 X 297 mm) 459 25 5 A7 B7 V. Description of the invention (7) The low-resistance characteristic, long-term resistance to spark voltage test, and heat-resistant solid electrolytic plutonium container that is compatible with external stress. Another object of the present invention is to provide a solid electrolytic capacitor that has low thermal stress during reflow, does not suffer from thermal degradation of impedance due to peeling of a bonding (paste) interface, and the like, and has excellent moisture resistance. A conductive paste and a solid electrolytic capacitor using the paste. Still another object of the present invention is to provide a conductive carbon halide for grain bonding or use in solid electrolytic capacitors, which is a high-conductivity shed with high filling density of various conductive materials, K, and can reduce heating due to heating. Conductive carbon paste that reduces the water absorption and improves the moisture resistance of the product due to the difference in the thermal expansion coefficient between the materials and the solid electrolytic capacitor using the paste. < Summary of the invention > The present invention relates to a solid electrolyte layer, a conductive layer containing gold rhenium powder, and a conductive carbon layer formed between the solid electrolyte and the conductive layer containing metal powder as described below. At least one layer is a solid electrolytic capacitor containing rubber: shaped elastic material and its manufacturing method; and a solid electrolyte for solid < bulk electrolytic capacitors; a conductive paste containing metal powder, and a conductive material. Carbon paste. 1. A solid electrolytic capacitor provided with a solid electrolyte and a galvanic body mill on a dielectric coating layer formed on the surface of a metal substrate, characterized in that at least one of the solid electrolyte layer and the conductive body contains elasticity Rubber material. : 2. The solid electrolytic capacitor according to item 1 above, wherein the conductive layer is a conductive layer containing metal powder, or a conductive carbon calendar and is disposed on the layer-10- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) ----- Order ----- V. -1 Line 3_ .. ¾ Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs r Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 device? | Rubber capacity W Electric surface breakout electricity% f Mass solid 5 5 -2 9 1 or ° ο 7-There are 6 content, system ^ 0 ^ quality The first solution is to power up the body. Solid 11 of the I bullet Teng Oak. As for the material, the electrical layer of the device assembly is electrically conductive, and the electrophoretic layer 11 or the upper film is like this. The material 12 is a springy rubber. Among them, > The combination of electrical colloidal rubber solidification and 12 rubber or rubber can be chosen freely from the sky. 13 Material properties: 4 5 9 2 b 5 A7 ___B7_ V. The description of the invention (8) contains the conductive powder layer containing metal powder. Make up. 3. The solid electrolytic capacitor according to item 1 or 2 above, wherein the solid r-- electrolyte layer contains a rubber-like elastic material. 4. The solid electrolytic capacitor of item 2 above, wherein the conductive carbon layer contains a rubber-like elastic material. 5. The solid electrolytic capacitor according to item 2 above, wherein the conductive layer containing the gold powder contains a rubber-like elastic material. 6. The solid electrolytic capacitor according to item 2 above, wherein the solid electrolyte layer and the conductive carbon layer both contain a rubber-like elastic material. 7. The solid electrolytic capacitor according to item _2 above, wherein the conductive layer of the solid electrolyte layer containing metal powder all contains a rubber-like elastic material. 8. The solid electrolytic capacitor according to item 2 above, wherein the conductive carbon layer and the conductive layer containing gold tincture powder each contain a rubber-like elastic material. 9. The solid electrolytic capacitor according to item 2 above, wherein the solid electrolytic layer, the conductive carbon layer, and the metal powder-containing conductive layer all contain rubber-like elastic rhenium. 10. The solid electrolytic capacitor according to any one of items 1 to 9 above, wherein the solid electrolyte layer of the solid electrolytic capacitor has a film-like or layered structure. This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 mm)

A7 459255 ___; __ B7____ 5. Description of the invention (9) The material of the shape is Tan rubber. < Please read the precautions on the back before filling this page) 14. The solid electrolytic capacitor of item 11 or 12 above, where the conductive polymer is pyrrole, thiophene, aniline or a divalent radical containing their derivatives It repeats at least one polymer of military element. > 1δ. The solid electrolytic capacitors as described in item 2, 5, 7, 8 or g above: wherein the conductive layer containing the gold powder contains a conductive filler composed of metal powder and a main component as a binder Fluorine rubber. 16_ The solid electrolytic capacitor of item 15 above, wherein 80 mass 5S Μ of the binder is a fluorine-based rubber. 17. The solid electrolytic capacitor according to item 15 above, wherein the conductive filled 80 mass X is silver powder from above. 18. The solid electrolytic capacitor according to item 15 or 17 above, wherein the average particle diameter of the electric fillers is 1 «βιM to 10jumM. • Wire. 19. The solid fugitive capacitor according to item 15, 17, or 18 above, wherein the conductive filler is 50 to 95 mass% and the binder is 5 to 50 mass%. .. 20. The solid electrolytic capacitor according to item 15 above, wherein the conductive powder of the metal powder is a layer formed of a conductive paste containing a galvanic filler, a binder, and an organic solvent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 21. —A capacitor element with a dielectric oxide film, a solid electrolyte layer, and a conductor layer formed on the surface of the anode body formed by the valve body. The state of the exposed portion of the terminal is a solid electrolytic capacitor composed of an insulating resin package. The solid electrolyte is characterized in that the solid electrolyte is a conductive polymer layer, and the conductive layer is contained in the above-mentioned item 15, 20, or 21. The conductive skull layer of gold tincture powder. -12- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Description of the invention (10) ^ 2. The solid electrolytic capacitor of item 21 above, where the conductor is calendared It is a layer formed by a galvanic carbon layer on the conductive polymer and a conductive layer containing metal powder as described in any one of the above 15 to 20 on the layer. 23. The solid electrolytic capacitor of item 21 or 22 above, wherein the conductive polymer layer is poly (3,4-ethoxythiophene) ° 24. The item of 2, 4, 6, 8, 3 or 22 above A solid electrolytic capacitor, in which the conductive history is a layer made of conductive carbon paste containing κ conductive material, a binder and a solvent as main components, and 80% of the conductive material X or more is artificial black lead. And the artificial black lead is a fixed carbon with 97 masses X K, an average particle diameter of 1 to 13 wm, an aspect ratio of less than 32 "® and a particle size of 12" or more and 12 masses of S: K. 25. As above No. 24 The solid electrolytic capacitor according to item 2, wherein the binder is a rubber elastic material which can be swelled or suspended in a solvent. 2 6. The solid electrolytic capacitor according to item 25 above, wherein the material having rubber elasticity is selected from isoprene. Metadiene rubber, butadiene rubber, styrene / butadiene rubber, eye rubber, isobutylene rubber, ethylene / propylene copolymers, acrylic rubber, polysulfide fluorene rubber, fluorine fluorene polymer, silicone rubber and At least one material of thermoplastic elastomer. 2 The solid as described in item 24 above. Electrolytic capacitors in which the conductive carbon paste has a solid content of 30 to 99 masses: Ϊ is a conductive material and 1 to 70 masses X is a binder. 28. — A dielectric film formed on the surface of a valve-acting metal is provided Method for manufacturing solid electrolytic capacitors with solid body electrolyte layer and conductor layer: Special 13- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm)

I Note Boxing staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative Cooperative. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative. 459 2b D A7 B7 V. Description of the invention (11) 戡 Includes: Orders of military solutions of electrical polymers At least one of the oxidant solution and the oxidant solution contains an oak-like elastic material; a valve-acting metal having a dielectric coating formed on the surface of the conductive polymer monomer solution and the oxidant solution interacting with the cells once or several times The medium is coated with a film or layer of a conductive polymer composition. 23. The method for manufacturing a solid electrolytic capacitor according to item 28 above, wherein the polymer composition contains 0.01 to 25 mass of a rubbery elastic branch. 30. The method for manufacturing a solid electrolytic capacitor as described in item 28 or 29 above, wherein the rubber-like elastic material in 萁 萁 is an air strip rubber. 31. —A method for producing a picture-type electrolytic capacitor with a solid electrolyte calendar and a conductive layer on a dielectric film formed on the surface of a valve-acting metal, which is characterized by the use of a binder / solvent containing a conductive material and a rubber elasticity The conductive paste forms a conductive calendar on a solid electrolyte. 32. The method for manufacturing a solid electrolytic capacitor according to item 31 above, wherein the conductive body is a metal-containing paste formed by using an electroconductive paste containing a metal powder-containing conductive filler, a rubber elastic binder, and a solvent. Powder isoelectric calendar. 33. The method for manufacturing a solid electrolytic capacitor as described in item 31 above, wherein the bender layer is made of a binder containing isoelectric material, rubber elasticity, and a conductive carbon paste of a solvent to form "electrical carbon". After that, a conductor layer containing gold and rhenium powder is formed. 34. The method for manufacturing a solid electrolytic capacitor according to item 31 above, wherein the conductive layer is made of a conductive material containing rubber and has a strong rubber viscosity. 14- ^ This paper is a national standard (CNS) A4 specification （210 X 297 公 ί） it-. 4 —--- rl — AJ ---. V_ '' .. (Please read the legal notices on the back before filling out this page) Order 丨 $ Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 4 59 25 5 A7 B7 V. Description of the Invention (12) After the conductive carbon paste of the agent and the solvent forms a conductive carbon calendar, a conductive filler filled with gold tincture powder is used to charge Agent, conductive adhesive with rubber knee elasticity, and conductive paste of solvent to form a galvanic layer containing gold tincture powder 35. The method for manufacturing a solid electrolytic capacitor according to any one of items 31 to 34 above, wherein the solid electrolyte is used in the past Conductive polymer monomer solution and at least one oxidant solution containing a rubbery elastic material. The conductive polymer monomer solution and oxidant are dissolved on the dielectric coating and alternately applied one or more times to form a conductive coating. Film of sexual polymer composition. 36. The method for manufacturing a solid electrolytic capacitor according to any one of items 31 to 35 above, wherein the solid electrolyte layer has a film-like or layered structure. 37. The method for manufacturing a solid electrolytic capacitor according to item 36 above, wherein the thickness of each of the membranes or layers of the solid electrolyte having a film-like or layered structure is in the range of about 0.1 to G < m. 38. A solid electrolyte composed of a conductive polymer composition 'containing a rubber elastic material of 0.01 to 25 mass 35, formed into a film or a layer. 39. The solid electrolyte according to item 38 above, wherein the rubber-like elastic material is at least one selected from natural rubber and synthetic rubber. 40. The solid electrolyte according to item 38 or 39 above, wherein the rubber-like elastic material is a fluorine-based rubber. f 41. The solid electrolyte according to item 38 above, wherein the conductive polymer is at least one polymer of pyrrole, thiophene, aniline, or a repeating unit containing a divalent group of a derivative thereof. 42. —A method for producing an object with a solid electrolyte, including: for the surface frost to form a body electrolyte composed of a conductive polymer composition ... ··· -15- This paper applies Chinese national standard (CNS) A4 specifications (210 X 297 public love) Read the note on the back

Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 45925 5 A7 _____B7__ V. Description of the Invention (13) The use of a conductive polymer army solution and an oxidant to dissolve at least one of the above solutions containing a rubber-like elastic material was carried out once. Or several times of repeated coating to forge a film-like or layer-like conductive polymer composition on the surface of the object. 43. The method for producing a solid-reading object according to item 42 above, wherein the coating is It is a cell by any method such as dipping, coating, coating, or solvent pouring. : 44. The method for manufacturing an object having a solid electrolyte as described in item 42 above, wherein the rubber-like elastic material is added to a conductive polymer monomer and / or a solution containing an oxidizing agent by dissolving or dispersing. 4 5. —A conductive paste for solid disintegrating capacitors, which is a conductive filler composed of metal powder. The material and the main component is a binder made of fluorine rubber. 46. The conductive paste for solid electrolytic capacitors according to item 45 above, wherein 80% by mass of the binder is fluorine-based rubber. 47. The conductive paste for solid electrolytic capacitors according to item 45 above, wherein the conductive filler has a silver powder on the basis of 80 mass and 35K. 48. The conductive paste for solid electrolytic capacitors according to item 45 or 47 above, wherein the average particle diameter of the electrical fillers is in the range of 1 to η. 49. The conductive paste for solid electrolytic capacitors according to item 45, 47, or 48 above, wherein the conductive filler 枓 accounts for 50 to 95% by mass and the binder 彳 accounts for 5 to 50% by mass 50. As described in items 45 to 49 above The conductive paste for a solid electrolytic capacitor according to any one, wherein the conductive paste contains an organic solvent. -16- This paper size applies to China National Standard (CNS) A4 (210 * 297 mm) J — — — II 1 i — — — — — — —'---— · (Please read the note on the back first Please fill in this page again for details) 459255 A7 ____ B7 _._____ V. Description of the invention (14) 51. — A conductive carbon paste for solid digestion capacitors, which is composed of conductive carbon materials, binders and solvents as the main components, of which Which of the conductive carbon materials? 〇 Mass S; M is artificial black chromium, and the fixed content of the artificial black lead is 97 mass χ κ, the average particle size, the aspect ratio is less than 10, and the particle size of 32 «ια Μ accounts for I2 mass Under the most%. 5 2. The conductive carbon paste for solid electrolytic capacitors according to item 51 above, wherein the binder is a rubbery material that can swell or suspend in a solvent. 53. The conductive carbon paste for solid electrolytic capacitors as described in item 52 above, the material having rubber elasticity in-'.. is selected from isoprene rubber, butadiene rubber, styrene / butadiene rubber , At least one of rubber, isobutylene rubber, ethylene / propylene copolymerization compound, acrylic rubber, polysulfide rubber, fluorene polymer, silicone rubber and thermoplastic elastomer. 54. The conductive carbon paste for solid electrolytic capacitors according to items 51 to 53 above, wherein 30 to 99% by mass of the solid content of the conductive carbon paste is a conductive material, and 1 to 7Q mass X is a binder. . <Detailed description of the invention> The solid P electrolytic capacitor of the invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics is a solid electrolyte layer and a metal powder-containing body formed on a dielectric film formed on a valve-acting metal. It is formed by forming an isoelectric carbon layer between the solid electrolyte layer and the metal powder-containing conductive layer as required, which is characterized in the solid electrolyte, the metal powder-containing conductive layer and the electrocarbon A rubbery elastic material is included in at least one of the layers. K indicates that (1) the rubber-like elasticity is contained in the solid electrolyte layer. -17- This paper applies the national standard (CNS) A4 specification (210 X 297 mm). 459255 A7 B7 The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 5. Description of the invention (15). / Material; (2) the rubber-like elastic material is contained in the conductive layer containing gold tincture powder; and (3) the embodiment in which the rubberized tincture is contained in the conductive carbon layer However, the present invention also includes an embodiment in which the rubber-like elastic cymbal is contained in any of the 2 or 3 layers of the solid electrolyte layer, the electrical body layer containing metal powder, and the conductive carbon layer. (1) When the solid electrolyte layer contains a rubber-like elastic material • I When the rubber-like elastic material is contained in the solid electrolyte layer, it is preferable to use a film-like rubber material containing 0.01 to 25 mass range Or a layered conductive polymer composition to form the solid electrolyte layer. When the rubber-like elastic material in the above range is contained in the conductive polymer composition, it is possible to reduce the number of coatings and also form an isoelectric polymer composition layer having heat resistance and a desired thickness on the dielectric layer ( Charge transfer complex). Due to the addition of 1 _ rubber-like elasticity, the formed solid electrolyte layer retains the stress .. The element is harmonious. As a result, a high-performance solid electrolyte layer with good low-impedance characteristics and durability during spark voltage tests and the like can be obtained. And solid electrolytic capacitors. The electropolymer which is suitable for use in the conductive polymer composition of the capacitor of the present invention is a polymer having a κ electron conjugate structure on the polymer main bond and a degree of polymerization of 2 Μ above 1Q0 k, preferably 5 Μ above 500. Of polymers'. Specific examples are poly five-membered heterocyclic polymers, polyaniline, polyparaphenylene, polyparaphenylene vinylene, polypyridine divinylidene, and substituted derivatives thereof. Only the above-mentioned polymer can be formed, and it can also be a copolymer produced by copolymerizing at least two or more monomers. A specific example of a preferable five-membered heterocyclic polymer is a 7T electron conjugated polymer containing a structural unit represented by the following general formula (1): -18-: -JIIII I --- M ~~ J -III — .. Vi.. (Please read the notes on the back before filling this page) Order ill

VK This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Description of the invention (κ)

In the formula, a saturated or unsaturated chain, a linear or branched unsaturated alkoxy group containing Ci-Cii, a hydroxyl group, a dentate, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a. Substituted phenyl to select a monovalent group; R1 and R2 can also be combined with each other at any position to form at least one divalent group with a saturated or unsaturated cyclic structure of 5-7 sections; X represents a heteroatom S, 〇, Se, Te, or .NE3, where R3 represents the true or branched saturated or unsaturated hydrocarbon group of H, CrCs, or a saturated or unbranched, linear or branched Ci-Ce, or Unsaturated alkoxy groups; and the above-mentioned alkyl groups of R1, R2 and R3, and alkoxy chains may optionally contain carbonyl groups, ether groups, ester groups, amido groups, and imino groups; 5 represents 0 ~ 1 Range. More preferably, it is a 7Γ electron conjugated polymer containing a fluorene unit represented by the following general formula (2): I: ------ 1 equipment ---------------------- -{Please read the notes on the back before taking this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs

2) In the formula: 1 ^ and [^ each independently represent Η or a straight or branched saturated or unsaturated hydrocarbon group of Ci-Cs, or the hydrocarbon groups are combined with each other at an arbitrary position to form the formula shown as containing 2 5-7 on at least one of the oxygen &quot; 19 * # This paper size applies to China National Standard (CNS) A4 (210x297 mm) Printed by the Consumer Support Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs' ^ 45925 5 A7_ _B7___; __V. Description of the invention (17) Substituents of heterocyclic ring structure of the ring; and the chemical structure such as substituted vinyl group or substituted 0-phenylene group is included in the range forming the upper structure; δ stands for 〇 The range is ~ 1. 'Supposedly represented by the substituents R1 to R3 and R3 of the general formula (1)', .. ·} · .. Examples of saturated or unsaturated hydrocarbon groups in the chain or branch are methyl, ethyl, and ethylene. Base, propylene, dipropyl'isopropylbutyl, 1 ~ butenyl. Examples of the straight-chain or branched-chain saturated or unsaturated alkoxy groups of Ci-CB are methoxy, ethoxy, propoxy, isopropoxy, butoxy, and the like. In addition, examples of the substituents other than the above-mentioned `` hydrocarbon-based alkoxy group K '' are nitro, cyano, phenyl, and substituted phenyl (halogen-substituted phenyl such as Ci, .Br, and F). The alkyl and alkoxy bonds of Ri and P may optionally contain a carboxyl group, an ether group, an ester group, an amido group, and an imino group. Among them, methoxyethoxy and methoxyethoxy are particularly useful. Oxyethoxy. · Also, an example of the general formula (1) of β1 and R2 which are mutually combined at any position to form a divalent group of a saturated or unsaturated green-like structure with a 5-7-membered ring on at least one M can be given. : 3,4-propene structure [General formula (3)]; 3,4-butene structure [General formula ((4)];. 3, 4- (2'-buteneene) structure [General formula (5 )]; 3, 4 · -butadiene structure [General formula (6)] and naphtho [2,3-C] condensation structure [General formula (7Π, etc.).

43) (4) (5) -2 0-. I. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back first, and pay attention to the details before writing this page) ) --- r '^ _-ΓΊ. · Γ IIIII 1 1111! (1.

'7-

-I 459255 a? B7 V. Description of the invention (is)

In the printed version of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, X stands for heteroatom S, 0, Se, Te or NR3. X represents s of the above-mentioned 3,4-butadiene structure [general formula (6)] is also referred to as an isothianaphthenyleae structure when it is a repeating structure _ unit of general formula (1). The condensed [2,3-c] condensed structure [general formula (7)] is called a naphtho [2, 3-c] thiophene structure in the case of general formula (1). In the formula, δ represents the number of charge of each repetitive structure military element, which is a value ranging from 0 to 1. Examples of the substituents of R4 and ^ in the general formula (2) are methyl, ethyl, propyl, isopropyl, vinyl, and allyl. In addition, R4 and Ci-Ce hydrocarbon groups may be combined with each other at any position to form a heterocyclic structure of 5 to 7 sections of at least 1 K containing 2 oxygen shown in the above general formula (2>). For example, 1,2-ethylene, 1,2-propylene, 1,2-dimethyl-ethylene. R4 and PiCi-Cs hydrocarbon groups are bonded to each other at any position to form a substituted vinyl group or a substituted 0, phenylene group. Specific examples of the cyclic structure of isounsaturated hydrocarbons are 1,2-ethylene [general formula (8)], 12-cyclohexene [general formula (9)], and 1,2-dimethyl-0-benzene Support [General formula (1 Q)]: -21- --- I ΙΊ--I ---- 装 -Lf--? (Please read the note f on the back page tk first)

Q This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 459 255 A7 __: ____ B7 V. Description of the invention (I9)

In the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs, Du printed the solid electrolytic capacitor of the present invention and the monomer compounds used in the preparation method. The monomer compounds such as thiopan, pyrrole or 3,4-ethylenedioxythiophene are 'It is common practice that oxidants for the polymerization of these monomer compounds are also known. 'Γ However, a capacitor provided with a solid electrolyte in which a rubber-like elastic material is added to the above isoelectric polymer composition has never been known. In the present invention, the rubber-like elastic material constituting the solid electrolyte is dissolved in a carcass polymer as a matrix and dispersed in a conductive polymer as a matrix. The amount of rubber-like elastic material to be added to the π-conjugated conductive polymer on the solid electrolyte constituting the 苳 solid electrolytic capacitor of the present invention is 0.001 to 2 5 mass X, preferably 〇.ι ~ 1 ()% by mass. A solid-decomposed electrolytic capacitor provided with a rubber-like elastic material is particularly suitable for a heat-resistant solid electrolytic capacitor that has excellent low-buck resistance, shows durability against spark voltage tests, and has external resistance to external forces. The addition amount of rubbery elastic concrete is less than 0.01 mass! At KK, the effect of adding rubber-like elastic material is not shown at all; on the contrary, if it exceeds 25 mass Si _, the conductivity of the solid electrolyte will be reduced, especially when the rubber-like elastic material is added -22-

Please read the precautions before f.] Page I The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 4592 ^ 5-RAS 4592 ^ 5- Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperative B7 V. Description of the invention (more than 20, the conductivity will decrease sharply when the matrix is reversed, so it must be limited to 25 mass: SK. For this reason, use the full mass of the solid electrolyte composition Q G1 ~ 2 5 mass Γ range, especially 0.1 ~ 10 mass X range. In this way, capacitors with excellent low impedance characteristics can be provided. Usually in the solid electrolytic capacitor manufacturing method, in order to improve the high-frequency characteristics of high capacity and Loss coefficient (tan5), leakage current, heat resistance (reflow), impedance characteristics and durability, etc. / The method of manufacturing (forming) the solid electrolyte described above is extremely important. For this reason, the isoelectricity of the solid electrolyte Π-electron conjugate structure of polymer, composition of electrical polymer composition such as rubber-like elastic material, conductive polymer composition, weaving The uniformity of the varistor is extremely important, among which the composition of the electropolymeric composition has a great influence on the characteristics of the capacitor. According to the method for producing the solid electrolyte of the present invention, due to the polymerization of the π-electron conjugated structure described above In addition, rubbery materials are added to the mash containing monomers and / or oxidants, so it can increase the adhesion amount of Shuning solution and reduce the number of necessary immersion times. In addition, because of the addition of rubber-like It can make the conductive polymer composition have stress and flexibility. It can increase the elasticity against external pressure such as heating or encapsulation. As a result, the leakage current of the initial characteristics is reduced, and the high temperature and high temperature are reduced. Characteristics of deterioration in capacity and loss coefficient when placed under wet conditions for a long period of time. A specific example is mixing a rubber-like elastic material solution or dispersion with a monomer compound-containing solution, and coating the solvent with a crushing valve. Acting on a metal anode foil with a fine pore dielectric coating, the monomer compound is oxidized and polymerized by the action of an oxidizing agent, and the resulting polymer composition is used as a solid 23- China National Standard (CNS) A4 Specification (210 X 297 mm) iill.l ------ 1¾ -------- ^ -------- &lt; Please read the note on the back first Matters written on this page) h. A7 459 2b5 _____ B7 _.___ V. Description of the invention (21) I · (Guess to read the notes on the back before filling this page) The body electrolyte is formed on the surface of the medium. The above process is applied to an anode The substrate is applied at least once, preferably 3 to 20 times, to easily form a dense solid electrolyte layer. One of the preferred processes is the immersion method. This method is performed when the above polymerization is performed. The valve action of the dielectric film The gold anode anode foil is immersed in a solution containing an oxidant (Solution 1), and then immersed in a mixed solution containing a monomer compound and a rubber-like elastic material (Solution 2). The above impregnation order can also be reversed, that is, the valve-acting metal anode foils are immersed in the above-mentioned solution 2. Then, they are immersed in the above-mentioned solution 1. • s In another embodiment, the anode foil is immersed in a solution (solution 3) containing an oxidizing agent and a rubber elastic material, and then immersed in a solution (solution 4) containing a military compound. The above impregnation order can also be reversed. The above-mentioned solutions 1 to 4 may be suspensions. In addition, the dipping method described above may be replaced by a coating method, a blow-by method, or a solution-casting method, so that a polymerization reaction is performed on the anode foil. The solvent for printing solutions 1 to 4 of the consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs may be the same, or they may be different solvents, and may be processed in solutions 1 and 2, or solutions 3 and 4 depending on the type of solvent. Add another drying step in between. In addition, after the conductive polymer coating film (solid electrolyte) is formed as described above and _ is a capacitor element, a step of washing with an organic solvent or washing with water may be added. The organic solvent for cleaning is preferably the solvent used in solution 1 to solution 4. This operation is relatively simple, but any other solvent that can dissolve monomer compounds and other compounds with an anion with dopant properties can also be used. . Where the above-mentioned oxidation polymerization is repeatedly carried out, welding can be easily generated ~ 2 4 ^ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 459255 Δ7 A / B7 V. Description of the invention (22, ) Connected with a solid electrolyte with excellent heat resistance (thermal stability). Capacitors using solid polyelectrolytes formed by conventional polypharyngeals and the like have large variations in capacitor characteristics and poor reliability at high temperatures and high humidity, but use the solid electrolyte formed by the conductive polymer composition of the present invention. The capacitor has excellent thermal stability and good stability in a dope-containing state. .This is because the conductive polymer composition with the above-mentioned rubber-like elastic vibration is not only on the surface of the medium but also deep inside the pores. The precipitation filling at the stage is on the surface of the medium and inside the pores, so Multiple layers of the polymer composition can be formed, such as a thin film and a laminated layer, so as to provide a capacitor having flexibility and good thermal stability without the dielectric film being damaged. The rubber-like elastic material applicable to the present invention is a substance having the unique elasticity of elastic rubber or a rubber-like substance, which has the property of returning the race shape to its original shape when deformed by an external force. Specific examples include: general rubber (such as natural rubber and urine rubber , Ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, butyl rubber, isoprene rubber rubber, *, silicone rubber and fluorine rubber Rubber) or thermoplastic elastomers (such as styrene-based, olefin-based, urethane-based, 1,2-polybutadiene-based and vinyl chloride-based, etc.). Fluoride rubber is a general term for synthetic rubber containing fluorine atoms in its molecules. It is used as a special rubber, which is different from rubber for i. Specific examples are polymers containing fluorinated fluorinated esters, fluorinated ethylene copolymers, ethylene tetrafluoride-perfluoromethyl vinyl acid Copolymers of olive oil, fluorine-containing phosphorus nitrogen strips, fluorine-containing silicone polymers, etc. These synthetic resins show different properties depending on the type, but have far superior heat resistance, chemical resistance, and weather resistance compared to commercially available rubbers / -25- 'paper ruler Degree applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the ί outfit on the back -------- * 'guang ·· ¾ and then fill out this page) Order ----- ---- Printed A7 B7 459255 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. The description of the invention (23) is also stupid. The above-mentioned silicone rubber is a kind of silicone rubber whose main chain is combined with siloxane and the side chain has a The rubber-like rubber compound formed by the linear polymers of substituents such as phenyl and phenyl groups bridges each other, which has good heat resistance and electrical insulation. These elastic materials are preferably conductive polymers that can be dissolved in organic polymers during the polymerization reaction. In the solvent. Suitable elastic materials include polyester urethane, polyether urethane, and fluorinated vinylidene-cyclohexene copolymers. The organic solvent used at this time is ketone strips such as MZ »methylmethylfluorene and acetone. Acetic acid esters such as isopropyl acetate, ethers such as dioxane, THF, and alcohols such as methanol are preferred. If using insoluble organic solvents, rubbers can be used with monomers or oxidants. The solvent of the solution is the same as the environment or the dispersion of the media that can be mixed with it. In particular, the solid should be electrolytic When the material has heat resistance, use high heat resistance. Fluorine rubber, silicone rubber, etc. The oxidant used in the present invention may be any oxidizing polymer suitable for pyrrole or phenanthrene, for example, JP 2-1 5 6 Ferric chloride (11),? 6 ((: 104) 3 or organic acid 戡 U), inorganic iron (M), alkyl persulfate, Ammonium sulfate, hydrogen peroxide, iUCra〇7, etc. The organic acid on the top of the organic acid) is, for example, methanesulfonic acid or dodecylbenzenesulfonic acid (^-(: 21) alkylsulfonic acid or. fat

I aliphatic carboxylic acid. However, the range of use of the above-mentioned oxidants may be limited by the chemical structure of the military compound, the oxidant M, and the reaction conditions. For example, the oxidation (polymerization) of phenophanes, according to the Handbook of Conducting Polymers (M arce 1 Dekker, I nc .Issued, 1 8 7, pp. 9 9, Ϊ1 ig. 5), depending on the type of substituent, the oxygenation potential (an indicator of the ease of polymerization) is greatly changed (the model garden of oxidation potential) (Approximately 1.8 to approximately 2.7 V). The left-2 6-^ 's Zhang scale ^ uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm)' (Please read the precautions on the back before filling this page ) r Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Λ A7 B7 V. Description of the invention (24) Right polymerization reaction. Therefore, there are specific combinations of military compounds and oxidants. The present invention is to find a combination of manufacturing methods that can improve the characteristics of capacitors within such a limited range, thereby solving the above-mentioned problems. In the production of the conductive polymer of the present invention, the coexistence of dopant The anion is an electrolyte compound or other anionic system that can dissociate the oxidant anion produced by the above oxidant (an oxidant anion). Specific examples thereof include chloride ion, an aliphatic organic carboxylic acid anion of h-Cu, sulfuric acid anion, phosphate anion, and Ci-Cu aliphatic ammonium phosphate anion and boric acid anion. In addition, electron acceptor dopants of M0 +, NOa * salts (such as NOBFi, NOPFb, NOSbFc, NOAsFs, NOCH3S〇3, NosBF4, fiOaPFs, NozCF3S03) can also be used. In addition, since the aforementioned yin heterozygotes used in the present invention and the conventional molecular yin male (eg, CIO *-, Β ··· 1, etc.) have different dopant properties (the stability of the charge transfer complex, the conductivity, etc.) ) And chemical properties, and compared with the conventional use of the conventional molecular anions of fluorene can show better results. That is, when the capacitor plugs used in the production of most capacitor elements can be compared, the compounds that exhibit particularly excellent effects are aromatic compounds (sulfoquinone, pyrenesulfonic acid, substituted naphthalene ~ sulfonic acid, and substituted sulfonic acid) Or heterocyclic sulfonic acid. The so-called quinone quinone series used in the present invention is a general term for compounds having a sulfonic acid group and a ketone structure on a K in the molecule. It has a chemical structure that can effectively act as a dopant when the sulfonium anion form is used. That's all. Specific examples of the basic skeleton of quinone are p-benzene sink, o-benzoquinone, 1,2-case, .1,4-naphthalene, 2, 6-naphthoquinone, 9, 10-anthraquinone (M (Hereinafter referred to as anthraquinone), i, 4 -27- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page) tr --- ------- Printed by Zhiyi, Ministry of Economic Affairs, Consumer Cooperatives of Hui Property Bureau

-II —i Λν I A7 B7 459255 V. Description of the invention (25) _ Xing Xing, 1.2-Hui Xing, 1, 4-deerquinone., 5, 6-Lu Xing ', 6,, 12-Cave Xing, overview Benzoquinone, butter quinone, perylene quinone, 2, 3-perylene diquinone, 9, 10-phenanthrene quinone, and 2, 7-perylene, and the sulfonic acid group of the sulfoquinone contains a hydrogen atom of the quinone compound The structure of an aromatic sulfonic acid substituted with a sulfonic acid group on one M or an aliphatic sulfonic acid substituted with a sulfoalkylene group in the divalent group of a saturated or unsaturated Ci-Cui hydrocarbon group. Alternatively, it may be a chemical structure in which one of the hydrogens of the sulfoquinone in the above structure is substituted with a saturated or unsaturated hydrocarbon group or alkoxy group of Ct-c6 or a substituent selected from F, Cl, and Br. Among them, the most preferred sulfoquinone in the present invention is the use of sulfo groups with anthracene, 1,4-caequinone, and 2,6-naphthoquinone; for example, anthraquinone M-sulfone 'Acid, anthracene-2-code acid, anthraquinone-1,5 ψ-disulfonic acid, anthraquinone-1,4-disulfonic acid, anthraquinone-1,3-disulfonic acid, anthracene-1, 6-disulfonic acid, fluorene-1,7-disulfonic acid, anthracene-1,8-disulfonic acid, hydrazone-2, disulfonic acid, fluorene-2,3-disulfonic acid, anthracene Circle-2,7-disulfonic acid, anthracene-1,4,5-trisulfonic acid, anthracene roll, -2,3,6,7-tetrasulfonic acid 1 and its alkali ketones and ammonium salts. 1. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and Cooperatives can use 1,4-naphthoquinone-5-sulfonic acid, ι, 4-naphthoquinone-8-sulfonic acid, 1,4 if it is 1,4-naphthoquinones. -Naphthoquinone-5,7-disulfonic acid, 1,4-naphthoquinone-5,8-disulfonic acid and its alkali metal ammonium salts and ammonium salts. For 2,8-naphthoquinone, 2,6-naphthoquinone 4-sulfonic acid, 2,6-naphthoquinone-3-sulfonic acid, 2,6-naphthoquinone-4-sulfonic acid, and 2,1 naphthalene -3,7-disulfonic acid, 2,6-naphthalene-4,, 8-disulfonic acid and its alkali gold phosphonium salts and ammonium salts. In addition, the above sulfoquinones can also be selected from industrial dyes, such as: anthraquinone blue R, anthraquinone violet RN-3RN, these dyes can also be used as sulfo rolls. Chinese National Standard (CNS) A4 Regulations (210 X 297 mm) 459255 A7 B7 V. Description of the Invention (26) Miscellaneous objects K are used in the above state. The sulfoquinone used in the present invention acts as an oxidative dehydrogenating agent depending on the fact that some of the compounds will participate in the polymerization reaction of the monomer compound. As a result, the sulfoquinone is protonated by the proton and the structure of the M, ie, the hydroquinone or M The original hydroquinone (quinhydrone) state is contained in the solid electrolyte as a dopant, and may also be contained therein. The anthracene monosulfonic acid used in the present invention is a general term for an anthracene monosulfonic acid compound in which one sulfonic acid group is substituted by an anthracene skeleton. The preferred compound is, for example, unsubstituted M sulfonic acid, or hydrogen of anthracene ring of anthracene sulfonic acid. Substituted compounds substituted by at least one of (h-Cu halo Ct-C8 linear or branched saturated or unsaturated saturated or unsaturated dialkyl or alkoxy groups. Compounds that can provide the above-mentioned unsubstituted sulfonium monosulfonic anions are, for example, Anthracene-1-sulfonic acid, anthracene-2-sulfonic acid, anthracene-9-sulfonic acid, and alkali metal salts and ammonium salts thereof. Furthermore, the above-mentioned anthracene ring hydrogen is further substituted by the M monosulfonic acid-substituted compound. Substituents are, for example, _yl, ethyl, propyl, isopropyl, butyl, &gt; isobutyl, third butyl, pentyl, hexyl, octyl, decyl, + diyl, etc. Or unsaturated groups such as vinyl, dilute propyl, 3-butenyl, and hexa-hexenyl; and methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy , Octyloxy, etc., decyloxy and dodecyloxy, etc. The substituted naphthalenesulfonic acid used in the present invention is a naphthalenemonosulfonic acid compound and an alkoxy group having a sulfonic acid group substituted on the naphthalene skeleton. Substitute the nickname of Tsai monosulfonic acid compound. A more preferred compound is the hydrogen atom of the naphthalene ring of naphthalene monosulfonic acid, especially Ci-Cei linear or 'branched saturated or unsaturated alkoxy group of at least -29- This paper size applies to the Chinese National Standard &lt; CNS) A4 specification (210 X 297 mm) ------ (Please read the precautions on the back # / fill out this page first) ----- Order ---. 1 ----- line, printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by 459 255 A7 _ __B7 _; _ 5. Description of the invention (27) A compound substituted on M. Can provide the above-mentioned anionic compounds of substituted lysine sulfonic acid. Specific examples of the compounds are naphthalene-1-sulfonic acid, cer-2-sulfonic acid and its alkali gold-release salts, ammonium salts, and hosiotetraamine salts. A chemically structured compound such as a compound that has a hydrogen atom in its naphthalene ring replaced by one or more alkoxy groups. The substituted benzenesulfonic acid used in the present invention is a general term for a benzenesulfonic acid group substituted with a sulfonic acid group on the benzene core skeleton and an alkyl-substituted benzenesulfonic acid. The preferred compound is unsubstituted benzenesulfonic acid or the hydrogen atom of the benzene ring of benzenesulfonic acid. 》, Especially compounds substituted on a K of Ci-Cis straight or branched saturated or unsaturated hydrocarbon groups. The heterocyclic sulfonic acid anisodote used in the present invention has an anion of a heterocyclic sulfonic acid compound having a chemical structure substituted on a heterocyclic ring directly or indirectly through an alkylene group (aUylene). In general, the skeleton of the preferred heterocyclic compound may be morpholine, piperidine, piperazine, imidazole, furan, 1,4-dioxane, benzimidazole, benzothiazole sulfur, benzoisoxazole, benzene Benzotriazole and benzofuran skeleton. Specific examples of the compound capable of providing the above heterocyclic sulfonic acid anion are 2-oxazolesulfonic acid, 4-morpholinepropanesulfonic acid, furan-3-sulfonic acid, 2-benzimidazolesulfonic acid, 2-benzopyrene Alkali gold sulfonium salts, ammonium salts or quaternary ammonium salts such as zopropanesulfonic acid, 4-methyl-4-piperazinemethanesulfonic acid, 2,3-benzofuran-3-sulfonic acid and sodium salts of these compounds. Among them, aromatic sulfonate compounds are preferred: sodium dodecylbenzenesulfonate, sodium naphthalenesulfonate, sodium anthraquinone-2-sulfonate, ammonium anthracene-2,6-disulfonate, 1 , 4-naphthyl naphthalene-2-sulfonate, 3-methyl-2-anthraquinone. Sodium methosulfonate, anthracene, 3 0-. This paper size applies to Chinese national standard (CNS &gt; A4 specification (210 X 297 Mm> i Ji II, ---- III ^ --- ul ^ ilmln (please read the note on the back of the item #, write this page first), A7 459 255 ______B7_; _ 5. Description of the invention (28)- Sodium 2-sulfonic acid, 9,10-dimethoxyfluoren-2-sulfonic acid tetrabutylammonium salt, 9,10-dihexylanthracene-2-sulfonic acid tetrabutylammonium salt, 2-propoxycae-6-sulfonic acid Sodium, propionite-6-tetrabutylammonium sulfonate, sodium 2-methoxynaphthalene-6-sulfonate, 2,3-dimethoxynaphthalene-6-sulfonic acid tetrabutylammonium salt, etc .; and Heterocyclic type sulfonic acids include: sodium 4-morpholine propane sulfonate, sodium 2-benzodoxazolyl propane sulfonate, sodium 4-methyl-piperazine methane sulfonate, 2,3-benzofuran- 3-Sodium sulfonate, etc. In the present invention, in the case of chemical polymerization of thiophene and pyrrole monomer compounds in order to form a solid electrolyte, it is preferable to use K-sulphate as an oxidant. The most suitable persulfate at the time is ammonium persulfate and potassium persulfate; when iron (31) salt is used as the osmium oxidant, it is impossible to avoid the presence of europium elements in the conductive polymer group. The composition will affect the characteristics of the capacitor. The conditions for the formation (polymerization reaction) of solid electrolyte (isoelectric polymer composition) are described below. The conditions of the monomers, oxidants, organic anion dopants, and rubbery elastic materials used in the polymerization are described below. Each use concentration is the same depending on the type of monomer compound, oxidant, dopant f elastic material (including types of substituents) or its combination with the solvent, etc., but the concentration of the monomer is usually IX 10-4 ~ 10 The range of ears / litres is preferably 1 × 10-3 ~ 5 moles / litres. The reaction temperature varies depending on the type of reactant and the reaction method. Therefore, it is difficult to define, but it is usually -70¾ ~ 2 50¾, 0D ~ 15〇υ is more preferable, and the range of 15 ~ 10 is particularly preferable. The solution or polymerization solvent suitable for the polymerization reaction is preferably tetrahydrofuran (THF) or dioxane or diethyl ether. Isoethers, -31- Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) Λ- '— — — If-- »IIIIIII. Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 459255: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (29) or ketones such as propionate, methyl ethyl ketone; dimethylformamide (DMP) or acetonitrile, benzyl Non-protonic polar solvents such as eye, S-methylpyrroloquinone (NMP), dimethyl sulfene (DMSq); esters such as ethyl acetate or butyl acetate; non-aromatic ammonium chloride such as chloroform or dichloromethane Hydrocarbon solvents; nitro compounds such as nitromethane or nitroethane, nitrobenzene; or alcohols such as methanol, ethanol, propanol, and other organic acids, such as formic acid or acetic acid, propionic acid, or the organic acid. Acid anhydride (such as acetic anhydride), water or their mixed solvents. Preferable are water, yeast, _, acetate, and / or mixed mash. The outline of the structure of the solid electrolytic capacitor of the present invention is described below with reference to FIG. 1: The electrode of one of the present invention (the anode U is made of aluminum, titanium, tantalum, niobium, or an alloy of which the matrix is used as a matrix, and has a valve function. Rhenium, rod, or K is a conventional material such as sintered carcass, and for the purpose of forming a dielectric layer and increasing the specific surface area, the surface of these metal electrodes is etched or chemically treated according to conventional methods. Chemical conversion) treatment to form the gold oxide coating layer 3 on the metal foil. 0. Solid electrolyte (conducting polymer 11 product) 4 formation, it is suitable to polymerize the above on the dielectric layer of the valve as the electrode foil As a method for a monomer compound, in particular, a method for chemically precipitating an electrically conductive poly-zhaocheng product having excellent heat resistance and impact resistance of the rubber-containing elastic material of the present invention on a medium layer having a pore or void structure In addition, in order to improve the contact of rhenium, it is best to further provide another conductive layer on the conductive polymer composition formed by the method described above, such as coating a conductive paste or using electroplating, evaporation, and a conductive wax film. Wait until it becomes a conductive calendar 5. -32- (Please read the precautions on the back before filling out this page) To ---- order ----, · The line, this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 459255 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs _____B7_V. Description of the invention (30) For solid electrolytic capacitors manufactured according to the above-mentioned manufacturing method of the present invention, A solid electrolytic capacitor product suitable for various uses can be prepared by covering the upper mold with a resin or a matching resin or a metal outer case, or by providing the encapsulation body 6 by impregnating the resin, and then providing the connection terminal 7. (II ) Where metal powder-containing electrical conductors contain rubber-like elastic materials · When rubber-like elastic materials are included in a conductor layer containing metal powder, use a conductive filler made of metal powder and use rubber-like elastics as a binder The main ingredient is metal powder. Conductive paste. Suitable rubber-like strength materials are general rubber (natural rubber, urethane rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene -Butadiene rubber , Synthetic rubber such as butyl rubber, isoprene rubber, silicone rubber and fluorine rubber) or thermoplastic elastomers (styrene, olefin, urethane, 1,2-polybutadiene and (Vinyl chloride, etc.) 之中 Among the above, fluorine-based rubber and silicone rubber with excellent heat resistance are preferred. Fluorine rubber is a general term for synthetic rubber containing fluorine atoms in the molecule. It is used as a special rubber and is used in general The rubbers are different. Specific examples are polymers containing fluorinated propenyl esters, fluorinated vinylidene copolymers, ethylene tetrafluoride-perfluoromethyl vinyl acid copolymers, and fluorinated phosphorus nitrogen And fluorosilicone-based polymers, etc. These synthetic resins have different properties depending on the type, but they have excellent heat resistance among commercially available rubbers, and have excellent chemical resistance and weather resistance. The solvent used to prepare the isoelectric paste can be the commonly used isoelectric paste. For example, N-methyl-2-pyrrolidone, N, dimethyl ethyl hydrazone-33- This paper is suitable for China. Standard (CNS) A4 specification (210 X 297 mm) &lt; Please read the precautions on the back #, write this page) J Pack i .----- Order · --- ^ ---- -

A7 B7 459255 V. Description of the invention (31) Solvents such as amine, dimethylformamide, butyl acetate or mixtures thereof. Although the amount of the solvent blended in the conductive paste varies depending on the purpose and required viscosity of the conductive paste, it is generally equal to 10 times the solid content of the paste. Examples of the conductive filler suitable as the conductive paste are silver powder, metal powder such as gold or copper, carbon powder, and the like. The preferred powder is silver powder, especially the silver powder containing 80 mass halo 3: the best filling material. The particle size of the powder is preferably from 1 to lQi / ϊβ. The apparent particle density of the average particle diameter of 1 W m is too small from below, which will increase the volume of the paste, which is not conducive to the formation of the conductive layer. Conversely, when the average particle size exceeds 1 Dwra, the particle size is too coarse, and the problem of poor connection with the cathode lead terminal easily occurs. -The use of fluorine-based rubber, which is a more preferable binder, is described below. The preferable binder is a fluorine-based rubber containing 8 G to 10 Q% by mass, and the remaining ingredients can be mixed with conventional resins. Fluorine strip rubber has good rubber elasticity, and has the property of recovering the deformation when deformed. It is different from fluorinated rubber which cannot recover the deformation. ^ This fluororubber includes the conventional fluorinated vinylidene copolymer rubber. , 6-fluorinated propylene fluorene copolymer rubber, 4-fluorinated ethylene fluorene copolymer rubber, fluorine-containing diacrylate rubber, and fluorine-containing silicone rubber. These rubbers are those with no tellurium added, and their glass transition point (Tg) is lower than room temperature, so this point can be clearly distinguished from fluororesin. The mixing ratio of the conductive filler and the binder is preferably 50 to 95% by mass of the conductive filler and 5 to 50% by mass of the binder. If the conductive filler is less than 50% by mass, the conductivity will be reduced, and if it is more than 35% by mass, the binding force of the binder will be reduced, and it will be difficult to form the electrostrip layer as expected. In order to make the above-mentioned mixture of conductive fillers and binders (solid content) -3 4-This paper size applies the national standard (CNS) A4 specification (210 X 297 mm) &lt; Please read the precautions on the back first (Fill out this year)

-i! I Order -------- V Ministry of Economy. Intellectual Property Bureau employee consumer cooperative prints i: r ^ 4S9 2 〇〇A7 B7 The Ministry of Economic Affairs ’Intellectual Property Bureau employee consumer cooperation loosely prints an appropriate amount of organic solvent . An example of an electrolytic capacitor is a conductive paste using, for example, Dinghai Acetate and B as a conductive paste with a solid content of 100 mass. It is a foil (anode) and has a film 3 and pores 2 on its surface. Rhenium 7a »4 is conductive when it is formed on an oxidized solid electrolyte layer, although a conductive paste can be invented. The above (I) item "is described in detail in the alcohol content, but it can be used for polyphenylene, especially polypyridine. Here is the conductive polymer. Quinone sulfonic acid, alkyl anthraquinone sulfonic acid M Sulfuric acid, alkoxyanthracenesulfonic acid, benzenesulfonic acid, alkylbenzene, any of the above-mentioned organic sulfonic acid anions of the organic sulfonic acid anion can be bonded to any of the alkyl or alkoxy in the above-mentioned intended binding position. 2. Description of the invention (32) Tongcheng has a paste with proper viscosity. Usually, the solvent that needs to be added is suitable for dissolving fluororubber, that is, succinic acid, propyl acetate, etc. The amount of organic solvent is usually 40 ~ 1. 0 0 parts by mass. Using the rubber-containing solid electrolytic capacitor of the present invention: Figure 2 shows the solid electric garden of the present invention. 1 is aluminum or giant valve action gold by electrolytic anodization, etc. A solid electrolyte layer (cathode) connected to the anode lead end film 3 by welding or the like on the dielectric oxidizing electrode 1? An inorganic semiconductor compound is used, but the use of this electrical polymer is particularly suitable as a conductive polymer for solid electrolysis. Contains rubber-like elastic material in the front layer Occasionally, poly (3,4-ethylenedioxythiophene), polypyrrole, or poly (3,4-ethylenedioxythiophene) may contain anthracene and alkane as dopants. Anions of oxyfluorenone sulfonic acid, anthracenesulfonic acid, alkyl, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, alkoxyfluorenesulfonic acid, alkoxybenzenesulfonic acid, and the like. The sulfonic acid substituent is only required if it has a chemical structure bonded to the skeleton compound; it also has a compound, which has any of its skeleton compounds. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Read the main item on the reverse side: Fill in this page 459255 A7 B7 5. Description of the invention (33) There is a chemical structure of Ci-thei alkyl or alkoxy group. The isoelectric polymer can be formed by a conventionally known method such as chemically polymerizing a monomer forming the polymer with a gasification agent (polymerization initiator), electrolytic polymerization, or a combination thereof. For example, after immersing the oxide film in the monomer solution, immersing it in the oxidant solution, and then heating it for chemical polymerization, this operation is repeated several times. Repeated polymerization according to this can make the conductive polymerized poplar layer into a multi-barrier structure, which exhibits excellent resistance and thermal stress when encapsulated with an exterior resin. The solid electrolyte layer may be composed of a conductive polymer composition containing the rubber-like elastic material. When a fluorinated rubber adhesive is used as a conductive paste, the following effects can be exhibited. Although the conductive polymer layer has a multi-layered structure and exhibits excellent thermal stress resistance, when a conductive paste coated with a highly heat-shrinkable adhesive such as fluorene resin is applied thereto, it can penetrate the conductive polymer layer. Table calendar. This conductive paste undergoes a large stress upon heating, which affects the multi-layered shape of the conductive polymer layer. However, when a fluorene rubber adhesive is used, the stress caused by the paste immersed in the surface layer of the conductive polymer is small, and the shape of the resulting conductive polymer calendar can be maintained. Therefore, the heat resistance of the capacitor can be improved. The oxidants used in chemical polymerization are inorganic acid iron such as ammonium persulfate, organic iron sulfonate (1), iron chloride U), Fe (Cl04) 3, organic acid iron (I), persulfate, alkyl Persulfate, hydrogen persulfide, K2Cr207, etc. A conductor layer 5 is formed on the surface of the solid electrolyte layer 4. This conductor 5 is in close contact with the solid electrolyte layer, and acts as a cathode and at the same time as a bonding agent for joining the cathode lead terminal 7b. The thickness of the conductor layer 5 ^ -36- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the unintentional matter on the back of Jing before filling this page) Install! — Order · — 4 Employee Cooperative Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs φ1 take 459 255. A7 ____B7 V. Description of the invention (34) The degree is generally about 10 ~ 50wm. .. The conductor layer 5 can be formed by using the conductive paste of the present invention alone, but it is preferable to form a layer of carbon paste on the conductive polymer (ie, solid electrolyte layer) 4. A layer formed using the conductive paste of the present invention is provided thereon. ^ The carbon paste can be a conventional carbon paste in which a resin and a solvent are added to the black lead powder. However, it is preferable to use fluorocarbon as the resin. The thickness of the carbon paste layer is only 1 ~ 2 μm. The cathode lead terminal 7b is bonded to the outer surface of the conductor layer 5, and the exposed portions of the female lead terminal 7b and the anode lead terminal 7a are retained, and sealed with an insulating resin 6. As the insulating resin, epoxy resin is mainly used. At the time of encapsulation, i can also be implemented by pressing the sickle method. _ (S) and other electrical carbon layers contain rubber-like elastic materials. The conductive conductive carbon layer uses conductive materials composed of conductive materials, binders and solvents. Sexual carbon paste is formed. The conductive material is preferably composed of artificial black lead powder of 80 mass 3 μM. For artificial black lead powder, the fixed carbon 99 mass 3 ί, average particle size 1 ~ 3 / iBi, aspect ratio 10M and particle size 32wmM account for 12 masses; the lower SM is preferred. The scale-like or leaf-like natural black lead has an aspect ratio of 10K, and is therefore different from the conductive material used in the present invention. As the length-to-width ratio of artificial black lead is higher, its filling property as a conductive carbon paste will decrease and increase the resistance of the paste. Therefore, the length ratio of artificial black lead powder must be 10 or less. This kind of human black lead has higher purity than natural black lead or carbon black, can increase the filling rate, and has the characteristics of minimal degradation due to heat. -3 7- This paper size applies to China National Standard &lt; (CNS) A4 Specification (210 X 297 mm) (Please read the precautions on the back before filling this page.) / Installation ---- Order i!- ---- Line. ^ * 31 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 59 255 A7 __B7___ V. Description of the Invention (35) In addition, the fixed carbon content of the black lead powder will also affect the resistance of the paste. The higher the fixed carbon content of artificial black lead powder, the lower the flatness. Therefore, in order to achieve the purpose of the invention, it is necessary to use a person with a carbon content of 97.7% by mass on K (..................... Black lead powder. The fixed carbon content here refers to the value of carbon content. V... There are JIS method (JISK 2 4 2 5), Carbon Association method, ASTM method and BS ΐ. In order to obtain the equal coatability of conductive carbon paste, the average particle diameter of the black lead powder is preferably in the range of 1 to 13 in. Even if artificial black lead powder is used, if the powder with an average particle size of 13 / ίΐΜ is used, It is not possible to obtain a uniform paste layer, and when used in solid electrolytic capacitors, tan δ * · .. j and equivalent series resistance (ESR) f of the capacitor characteristics are deteriorated. Even if the average particle diameter is within this range If the coarse particles are contained, the uniformity of the coating may be affected, but the particle content on the particle size 32W mK can be controlled by Liben 12 @ 最 一 工 工, which can avoid the problem of the upper part. The conductive carbon paste of the present invention used as a material must be made of a material containing at least 80% by mass of the above-mentioned artificial black lead powder. A combination of black black lead and carbon tritium is used and the above-mentioned artificial black lead powder is used. Full .80 sound volume X Jing, the modulation of the conductive carbon paste can not ensure sufficient conductivity. The use of artificial black lead powder must be 95 mass K, preferably 100 mass 35. The rest of the electrical materials v ... ........... Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are silver, gold and osmium metal powder with carbon black, Sky-bound lead and other Zanzi-like conductive substances. The solid electrolytic capacitor of the present invention uses conductive materials, binders, and solvents containing 80 mass x μ of artificial black lead powder as the main ingredient. Carbon, paste Although the use of artificial rhenium lead powder is not limited to those with the above-mentioned fixed carbon content, average particle size and aspect ratio, it is best to use artificial black lead as defined above--... &quot; &quot; &quot; &quot; '~ ~ 3 8 * -r This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Paste of the description of the invention (36). '' The conductive carbon paste is suitable as a binder. It is a material that is rubbery and has the property of returning to its original shape when deformed, and it is best to be swollen by solvents in the form Suspended material and rubber-like elastic material with excellent heat resistance during reflow treatment during capacitor manufacturing. Elastic materials with the above characteristics include pentadiene rubber, butadiene rubber, styrene / butadiene Ethylene rubber, eye rubber, ethylene / propylene copolymers (EPM, EPDM, etc.), acrylic rubber, polysulfide rubber, fluoropolymer, silicone rubber, and other mature plastic elastic polymers, etc. Among them, the more preferable ones are EPM, EPDM and fluorene polymers. The fluorofluorene polymer is not limited as long as it is a polymer containing fluorine. These rubbery polymers have lower water absorption and modulus of elasticity than epoxy resins generally used as conductive carbon paste, and have the effects of stress and stress at the joints. Fluoropolymers on the top include: binary copolymers of polytetrafluoroethylene, poly (trifluoroethylene), vinylidene fluoride (VDF) and hexafluoropropylene (HFP), and copolymers containing tetrafluoroethylene Polymers, tetrafluoroethylene / propylene copolymers, polyvinylidene fluoride, polyvinylidene fluoride, fluorinated acrylate rubber, and fluorinated silicone rubber. __ The mixing ratio of the conductive material and the binder in the conductive carbon paste &gt; 乂 Full solid content, the conductive material is 30 to 99% by mass, preferably 50 to 90% by mass, and the binder is 1 ~ 70 mass S :. When the conductive material is less than 3% by mass, the conductivity of the conductive carbon is too low, and when it exceeds 39% by mass, the adhesiveness and stress properties of the conductive carbon paste are lost.之 The solvent used in electric carbon paste and those used in general conductive carbon paste-39- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)-· 1 1 K · 1 n &lt; . · N}-^. F (Please read the notes on the back t to fill out this page) t5J · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 4 5 9 2 ^ 〇45925 ^ B7 V. Description of Invention (37 ) Identical, such as N-methyl-2-pyrrole, N, N-dimethylacetamide, dimethylformamide, butyl acetate and other solvents. The amount of the solvent to be added to the conductive carbon paste is determined according to the viscosity required for the purpose of the addition plus M, which is usually equal to or even 10 times the solid content of the paste. When using the conductive carbon paste of the present invention to make a solid electrolytic capacitor, the impregnation is a gold-plated foil made of a single metal or an alloy of aluminum, tantalum, niobium, titanium, and a junction that have a valve function, and an etching treatment Or, it can also be an increase in the surface B product such as a fine powder sintered body. I. After chemical treatment is applied to the surface of these gold tinctures to form a dielectric layer,

V. A solid semi-conducting ii layer (preferably a solid polymer layer composed of the above-mentioned conductive polymer) is provided on the outer surface, and the conductive carbon paste layer of the present invention is formed on the outer surface, and then formed on the surface. A metal-containing electric conductor layer (preferably a 'metal-containing electric conductor layer containing the above-mentioned rubber elastic material), and then equipped with leads to form a bulk electrolytic capacitor. The solid electrolytic capacitor made of the electric-reading carbon paste of the present invention has various characteristics such as high heat resistance, low equivalent series resistance (ESR) and low impedance, low thermal degradation of impedance, and excellent humidity resistance. <The best form for carrying out the present invention> The following examples, comparative examples, and reference examples will be used to explain the best form of the present invention. _ —---- .---------------------- 踅 Example 1 Using 1Q weight 3! Ammonium adipate aqueous solution and applying a voltage of 13V to The etched aluminum alloy (substrate) cut into a prescribed size and area is subjected to chemical conversion, chemical conversion (chemical conversion) treatment to form a dielectric layer on the surface of the aluminum foil (that is, to form dielectric oxygen, -40 '. This paper is applicable to China National Standard (CNS) A4 Specification (210 ^ 297 mm) (Please read the notes on the back before filling out this page) Packing -------- Order ------- 'Intellectual Property Bureau Staff, Ministry of Economic Affairs Printed by the Consumer Cooperative 459255 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs π 5. Description of the invention (33) Chemical film), and then immersed in 5 grams of 3,4-ethylenedioxythiophene 1.2 In its ear / litre of ethyl methyl ketone, polyester urethane was dissolved. A solution of 0.05 g of rubber (in solution 0, and then immersed in ammonium persulfate containing 20 mass children X (hereinafter referred to as "K" APS) and 0.125 mass! S of 2-anthraquinone sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in an aqueous solution (solution 3), the surface of the dielectric layer was impregnated with the aqueous solution, and the solution was placed in a 6 Gtr environment for 1 Q minutes Gasification polymerization is performed. After completion of polymerization, K water is washed. This polymerization reaction treatment and washing steps are repeatedly performed 1 () times. Subsequently, the results of electron microscope photographs are used to confirm the formation of the conductive polymer layer (solid electrolyte calendar). ) Is a layered structure. In addition, the substrate after the above polymerization treatment is placed in a water / isopropanol (IPA) solvent for migration and careful extraction, and the isoelectric polymer is obtained by ion color history analysis. The content of sulfate ion and 2-anthraquinone sulfonate ion in the composition. As a result, based on each repeated structural unit of the polymer in the conductive polymer composition, the content of sulfate ion was 1.5 mol X, 2-anthracene. The content of sulfonic acid ions is 14.0 mole%. The adhesion mass of the substrate (solid electrolyte) is increased by 15¾. The electrical conductivity of the solid electrolyte layer is 73 s / cm. Then, the above-mentioned Tongcheng has 3,4- After processing the aluminum rhenium (substrate) of ethylenedioxyphene polymer in a 10% by weight aqueous solution of ammonium adipate, the spark voltage is measured. In order to accurately compare the characteristics of the sample elements, increase the number of elements (the following implementation Example is the same). In the environment of 50¾ and the current density of 0 mA / ca ^, the components were implemented 5 times each n = 5; the results are shown in Table i below. Then, an isoelectric polymer layer was formed on the aluminum foil. Partially coated-4 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page), and install! 1 order.! Line ΓΤ · 459255 A7 B7 V. Description of the invention (39) After the carbon paste and silver paste are applied, the cathode lead terminals are connected, and the impregnated lead terminals are welded on the aluminum core portion without the conductive polymer layer. Take the capacitor element. This capacitor element was heated at 125 t! For 2 hours, and its initial characteristics were measured. The results are shown in Table 2 below. C in the initial characteristics in this table represents capacity, and DF represents the tangent 1 (tanS) of the loss angle (that is, the loss coefficient). These values are measured at 120Hz. Z represents the choke resistance value at the resonance frequency, and LC represents the leakage current value measured 1 minute after the rated voltage is marinated. Each measurement value is an average of 30 capacitor elements. In addition, LC above M 1 w AM is regarded as a defective product; ^ 0 is represented by AM above as a short circuit product, and the average value is calculated by excluding it. Comparative Example 1 '.1 Except that polyureaurethane rubber was not added, the rest was implemented in accordance with Example 1 and the capacitor element obtained in the same evaluation as in Example .1 was shown in Tables 1 and 2. In addition, according to the method described in Example 1, the sulfuric acid, the fruit yield, and the sulfonanthrene sulphanthracene-2 and S5f contained in the polymer composition were determined according to the method described in Example 1. 2- Quality &amp; Solution? * The body of the warbler contains free-solid% sulfide. (Please read the precautions on the back before graying this page) / Installation ----- -6Ji ---

n H ϋ I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs / according to the original knowledge of other contents, electricity Λ other than the best place. 7 Tian. For the evaluation and modification, the same is the same ο by example. The number of CIn times S / and 70. Combined into a polymerization, the degree of electric power 2 The implementation of the example of oxygen and the separation of the acid and sulfur 1. The medium is composed of the adult group and the body is broken. Sulfur. Get it. The formula shown in Table 1 contains 2 Table 1 seeds and cases. 1 Sulfuric acid, Sulfuric acid, anthracene knot 2-ear Mo. This paper size is applicable to China National Standard (CNS) A4 (210 X 297). (Centi) 4 5 9 2 55 A7 B7 V. Description of the invention (40)-2-Anthracenesulfonic acid ion content is 13 * 0. The adhesion quality on the ear substrate and the addition of polyurethane are not performed. The field of oxidation polymerization is almost the same. The conductivity of the solid electrolyte layer was 70 s / cm. Example 3 Except for the same concentration of acrylonitrile solution of M tetrafluoroethylene / propylene copolymer, instead of the polyurethane urethane rubber solution used in actual pickling example 1, the rest is carried out in accordance with example 1, and is the same as the example 1The capacitor element obtained by the same evaluation, the results are shown in Tables 1 and 2. In addition, the content of sulfate ions and 2-BS sulfonic acid in the polymer composition was determined according to the method described in Example 1. As a result, the content of sulfate ions was 1 * 8 gluteal X, and the content of heteroanthracene sulfonate was 15 _ 8 Mol Γ. The conductivity of the 25 ◊ 增加 solid electrolyte layer on the substrate increased by 65 s / cni. Defective example 4 'Except that the solution of the same concentration of sodium dodecylbenzenesulfonate was used instead of the 2-anthracene sodium sulfonic acid sodium solution used in Example 1, the other Xiyiyin Example 1 was performed, and The capacitor element obtained in Example 1 was similarly evaluated. The results are shown in Table 1 and Table Sulfur and the intermediates were grouped. (Please read the notes on the back before, #write this page &gt; ii ------ order

-flf I nn I, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the board as a base with a base of 0, acid and 5 fruit 14 The result is that the amount of a young child with an acid is benzene sulfonate 20 sulfo 20 Benzane plus dioxane, ten ounces, ten ounces, two ounces, ¾, ¾ Mo # 子 31 之 ·% 6 ounces are in degrees 5 electrical 4 conductance L layer electrolytes solid fr xi liquid soluble olefin Gum, ethylene, rubber, alkylene, urethane, mM, poly, except for the replacement of the actual solution, the concentration of the same degree of concentration, the same thing together, a total of 0, six examples of propylene fluoride, according to Shi Xiyu, the paper size is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 459255 A7 __B7_ V. Description of the invention (41) The capacitor element obtained by the same evaluation as in Example 1 is shown in Table 1 and Table 2 shows. In addition, in Example 1, the sulfuric acid broth and 2-anthrenesulfonic acid gardenia contained in the polymer composition were determined by the method described above. As a result, the content of sulfate ion was 1.4 mol%, and the benzoquinone basic acid heterozygous With children: for 1 4. 2 .. Mohr%. The mass of the attachment on the substrate is increased by 24¾. The conductivity of the tooth electrolyte was 73 s / cm. The oxygen content was measured by the oxygen cylinder combustion method and the ionic color spectrometry method, and the fluorine content was 0.5% by mass. Therefore, it can be seen that the fluorine-based rubber contained in the polymer composition is equivalent to about 1% by mass. Example 6 The same concentration except Kpyrrole Solvent substitution instead of 3,4-ethylenedioxythiophene solution and change of oxidative polymerization temperature to 5¾, the rest: It is implemented according to Example 1, and the capacitor element obtained in the same evaluation as in Example 1 is shown in Table 1 And Table 2. In addition, the content of sulfate ions and 2-anthraquinone sulfonate in the polymer composition '+ was determined according to the method described in Example 1. The content of sulfate ions was 1.7. The solution contains 15.9 of its ear X. The attached mass on the substrate is increased by 213 :. The solid electrolyte has a conductivity of SOs / cih. Reference Example 1 Except for the replacement of 3,4-ethylenedioxythiophene with M 4-methylthiophene, the rest of the implementation according to Example 1 did not result in the formation of a black-cyan poly 4-methyl-phene polymer at all, showing 4 -Methylphene does not undergo polymerization due to the action of saddle persulfate (APS). -44 MM scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page)

459 255 A7 B7 V. Description of the invention (42 Table 1 Spark electric cavity (unit: v, n =: 5) Example 1 Example 2 Example 3 Example 4 Example 5 贲 Example δ Comparative Example 1 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 Number of polymerization treatments. 3 4 5 6 19 19 19 19 19 19 19 19 19 19 19 19 19 18 18 18 18 18 19 19 19 19 19 19 19 19 19 19 19 19 8 10 19 19 19 19 19 19 18 18 19 19 19 19 19 19 19 (Please read first. Note on the back #, fill in this page) Table 2 Initial characteristics

Number of defectives / number of samples / tilt

Example Example Example Example M Pickling Application The application ratio is more actual than the actual ratio 0 8 8 7 7 7 8 6 6 6 8 7 6 6 ooooooo 6 6 6 6 6 6 6 3 3 2 5 2 3 6 ooooooo ooooooo 3 3 3 3 3 / / / / / ο ο 3 3 ο ο y. · 装 -------- ί Order ---- 1 ----

After printing the initial characteristics (as shown in Table 2) of the capacitor elements made by the Jfe cases 1 to 6 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the capacitors were exposed to high temperature and humidity for 50D hours, and then the capacity was measured again at 120 Hz ( C) and loss factor (DF%). The results are shown in Table 3. The capacitor elements obtained in Comparative Example 1 (without the addition of polyurethane rubber) were also subjected to the same measurement under the same conditions. The results are shown in Table 3. According to the data in Table '3, the actual -45- size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 cm) r 459255 A7 B7 V. Description of the invention (43) The capacitor elements of Examples 1 to 6 The changes in characteristics after the accelerated life test (capacity change rate X and damage coefficient 3;) were smaller than those in the comparative example. From this, it can be seen that the capacitor element of the present invention has a mild external stress, long life and high performance. Table 3 Initial characteristics, capacity U after 85¾ 13V 50Q time 〇 Loss (%) Capacity change rate (%) Loss U) 贲 Example 1 8.0, 0.6 5.3 3.5 Example 2 8.0 0.6 7.1 4.5 Example 3 8.0, 6 5.2 3.4 Example 4 7.2 0.8 5.7 3.7 Example 5 7.8 0.7 5.1 3.4 Example 6 7.8 0.6 5.2 3.3 Comparative Example 1 8.0 0.6 10.5 5.3 (Please read the precautions on the back before filling this page) Installation ----- Order ----- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 7: Modulation of conductive pastes Use silver powder with an average particle size of 5.5 μm as a conductive filler and Vi ton rubber (fluorinated rubber) Zene "fluorinated ethylene-6 fluorinated propylene copolymer" was used as a binder. Blend powder 8 5 mass 5S RViton rubber powder 15 mass Si was mixed as a solid content of the paste, then butyl acetate was added as a solvent, and kneaded Take a solid part of 60 mass S: thick viscous silver paste β -4 6 A paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 459255 A7. .. B7 V. Description of the Invention (44) Embodiment 8; Production of electrolytic capacitors. After etching and anodizing, the aluminum foil (weighed into foil) with a chemical change protective film is cut into a strip with a width of Sum, and then cut to a length of K 10mm. The voltage of 13V is applied to the unformed portion. Part of the treatment is carried out to form a film covering the entire surface of the aluminum foil. About 50¾ of the length of the formed foil is immersed in a 1-ear / liter concentration of ethanol solution of 3,4-ethylenedioxythiophene. , And then immersed in ammonium persulfate as a oxidant (poly initiator-containing) 1.5 萁 per liter / liters and · as a dopant (d〇E »ant) I ·. Sodium naphthalene-2-sulfonate! 3. 12 In an aqueous solution of mol / liter concentration, maintain 40¾ for polymerization reaction. The above-mentioned immersion and polymerization operations were repeated for 20 times to form an aluminum oxide coating on the aluminum foil. Electrical polymer layer. A magnified (5000x) photo of a scanning electron microscope of an isoelectric polymer layer formed by 20 iterative polymerizations, as shown in Figure 3, shows a layered structure * (Figure 3 , The top is a conductive polymer layer with a 廇 -shaped structure) 0 times The part with the isoelectric polymer layer was immersed in a carbon paste, and heat-treated at 1QQt for 30 minutes to form a carbon paste layer. The carbon paste used was made by mixing '' &lt; · average particle diameter of 3 w mi black lead Powder 60 mass X and 40% by mass of fluorene rubber, a thick carbon paste with solid content of 16 mass% * * »mixed with butyl deer acetate (as solvent) and kneaded. Next, a portion where the carbon paste layer was formed was immersed in the silver paste of Example 7 to form a conductive layer to form a capacitor element. Cut off the aluminum foil part of this capacitor element that is not covered with a conductive layer, and then bond them. 4 pieces are bonded to each other with the silver paste described above, and then bonded to the lead frame (copper alloy) -47- 'This paper size Applicable_China National Standard (CNS) A4 Specification (210 X 297 mm)

459255 A7 B7 V. Description of the invention (45) and drying at 1GQ ° C for 30 minutes. Then, a part of the aluminum foil not covered with the conductor layer was dissolved in the lead frame (copper alloy). Finally, one end of these frames was exposed, and an epoxy resin (manufactured by Sumitomo Bakelite Corporation, trade name ΕΓΓ-? 3'20A) was used to package the shoulder capacitor by a transfer molding method. The characteristics of this capacitor are shown in Table 4. Comparative Example 2 之外 The adhesive of silver paste was changed to epoxy resin (oiled She 11-Epoxy company, * &*; * made by the company, trade name Epic oat 8 28 type), the rest is described in Example 8 If implemented, the characteristics of the obtained wafer-type solid electrolytic capacitor are shown in Table 4. (Please ^^ read the note on the back ^^ and fill in this page again) Install iyill-Λ Table ESR (mQ) ESR increase before and after reflow (m £ 2) Poor reflow rate Moisture poor rate Example 8 20 2 0/30 0/30 Comparative Example 25 20 6/30 12/30 --- 1. Order! 11 ^ ―yl ϋι In Table 4: ESR (equal series resistance at 100KHZ ') is the average of 30 samples 97 2 X ο 2 / V Gage 4) A s) N (c Appropriate standard in the country Rule paper-Printed values from the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Solid flow (heat resistance) defect rate and moisture resistance defect rate are the number of defective products in 30 samples tested according to the following method. That is, heat resistance) Defective rate: After reflow (2301C, 30 seconds), the rated voltage (13V) is applied, and the leakage current value is measured after 1 minute. -48 &quot; Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 4 5 9 2 55 A7___; _B7 ___ V. Description of the invention (46) · 下 The current value under UyAM is a qualified product (good product), and 12 «ΑΜ_Η is a defective product. Temperature 60ΐ !, relative humidity 90S; under 100 (after 3 hours. Take out, apply the rated voltage, and measure the leakage current value after 1 minute. The leakage current value 12 «AM is the qualified product, 12 M AK soil is not Good product. Example 9 'KK aspect ratio 3 ~ 1.5, average particle size 3 wm, particle size 32 μ The particles occupy 2 masses, 3 masses, and fixed carbon content of 3 to 9 masses; artificial rhenium lead powder (manufactured by Showa Denko Corporation, trade name UFG-5) is used as a conductive material, and ethylene / propylene is used as a binder. / Diene terpolymer (EPDM) in butyl acetate suspension (EPD.M 7 mass X in suspension), so that the solid content of the resin (terpolymer) is artificial rhenium lead powder 1〇 〇80 parts by mass of 3 liters, and then mixed for 2 4 hours to obtain a conductive carbon lake. The shovel was etched by etching with a size of 3 X 10 mm, and a polyimide tape with a wide lmia was used on it. The two sides are attached, and M is divided into two parts of 4 «and 5mm. Then, the 3 MX 4 mra part of the aluminum foil is immersed in a 10 mass JS ammonium adipate aqueous solution and a voltage of 13v is applied for chemical (chemical) treatment to form a medium for oxidation. Film. Next, immerse 3 mm x 4 min of aluminum foil in isopropylase (solution 1) containing 20 mass of 3 £ 3,4-ethylenedioxythiophene, and take it out and dry it at room temperature. ... then the 3 mm X4 tain part of the aluminum foil (the part where the dielectric oxide film is formed) is dipped in a solution containing 3 (3 Dong% ammonium persulfate (APS) and 1 mass 3; simmer the sodium sulfonate aqueous solution (Solution 2) and take it out, and place it in an atmosphere of 6Q ° C for 10 minutes to perform oxidative polymerization. -49- • n I n I n · 1 nnn 1. I 1--(Please read the note on the back # -Fill this page first) Order-· 0!---The size of the paper is applicable to the Chinese national standard CCNS) A4 size (210 X 297 mm) r * 459255 A7 _ B7 V. Description of the invention (47) After immersing in solution 1 again, perform the same treatment as above. The above operation of immersing in solution 1 to oxidative polymerization was repeatedly performed 25 times, and then washed with warm water of 5 dt c for 10 minutes, and finally dried for 30 minutes to form a conductive polymer layer (solid battery .Quality Calendar). A scanning electron microscope photograph (2, 0 0 Q times) of the cross-section of the aluminum foil with the conductive polymer layer thus prepared was observed to confirm that the conductive polymer had a history-like structure that completely covered the dielectric (oxidized) on the aluminum alloy. Aluminium &gt; has voids between the denier-like conductive polymer layers on the surface of the micropores. The thickness of the conductive polymer layer formed on the outer surface of the micropore structure is about 5W fa, which forms a layer. The thickness of each layer of the structure is in the range of about Q. 1 ~ 0 3 um. Then, the conductive carbon glow prepared by the above method is coated on the part of the aluminum foil with a conductive polymer layer, and then heat-treated for 3D minutes at 10 ΙΙΊΟ. A carbon paste conductive calendar is formed on the above-mentioned conductive polymer. Then, a portion of the aluminum foil formed with a conductive polymer layer is coated with a silver paste to connect the cathode lead terminal, and at the same time, no conductive polymerization is formed. The part of the material layer is made of epoxy resin, and the components with anode lead terminals are wrapped by soldering. The rated voltage is applied at 125¾ for 2 hours, and a total of 30 capacitors are made. For this 3D capacitors For capacitors, the equivalent series resistance (ESR) is measured according to conventional methods and reflow treatment is performed. Then the ESR after reflow treatment is measured again and the ESR changes before and after reflow treatment are evaluated. At the same time, all capacitors are subjected to the resistance described below. The results of the test of the wet failure rate are shown in Table 5. Example 10 Except that the EPDM butyl acetate suspension described in Example 9 was changed to fluorine-50-This paper uses Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) \ 11—Order -------- line `` y · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation 1: ^ 45 9 2 b5 a7 — _ B7 _ V. Description of the invention (4.8). Ί · \ 糸 Polymer fluorinated vinylene-hexafluoropropylene-tetrafluoroethylene copolymer) Butyl acetate 鼪 float solution ， M and change the solid content of EPDM to 80 parts by mass of 100 parts by mass of artificial black lead powder. X is changed to 70 parts by mass X. The rest is implemented according to the method described in Example 9 to make 3Q capacitors. Example 9 evaluated the characteristics of the capacitor, and the results are shown in Table 5. -\ Comparative Example 3 ', except that the artificial black ship of isoelectric dead material is used instead of powder with an average particle size of 4Ϊa, and particles with a particle size of 32 wW occupy 2 masses! Inferred, fixed carbon 4 98 .5 quality &gt; ··· flake-shaped natural thallium lead on an amount of X, obvious aspect ratio of 10K, M and the SPDM of the adhesive changed to epoxy resin, and the rest Example 9 was run to obtain 30 capacitors. The evaluation results of the characteristics of these capacitors are shown in Table 5. 'Comparative Example 4. &gt; The artificial black lead powder of conductive material was changed to an average particle diameter of 4yiii, the particle size of 32 «bK accounted for 2 mass X'K, fixed carbon content of 98.5 mass%, length and width Than the obvious 10M ± scales of natural thallium lead, the rest are made according to Example Ifl, and 30 capacitors were made. The results of the characteristics evaluation of these capacitors are shown in Table 5. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The various evaluation tests performed in the previous example, 1 tr, and comparative examples 3 and 4 were performed according to the following measurement methods and conditions. <Measurement method> 1. Reflow (resistance) defect • The rate of passing 30 solid electrolytic capacitors through a reflow furnace with a peak temperature of 230¾ for 30 seconds and applying the rated voltage (6.3 V) for 1 minute. Post-measurement leakage current-5 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 459255 A7 VR7 V. Description of the invention (49) 1 j. Those whose leakage current value is less than 3 w A are regarded as qualified products (good products), and those that exceed them are regarded as defective products. 2. Poor moisture adhesion rate The qualified products for the reflow test are placed at a temperature of 6DT: and a relative humidity of 90¾. In an atmosphere, take out after 1000 hours, apply a rated voltage of 6. 3V), _ 1 minute, and measure the leakage current after 1 minute. Those whose leakage current value is less than 12W Α are regarded as qualified products. Table 5 ESR ΙΟΟΚΗζ (m Ω). Changes in ESE after reflow (m Ω) Poor reflow rate * 1 Poor wetting rate * 1 Example S 20 5 0/30 2/30 Example 3 20 0 0/30 0/3 0 Example 10 50 50 '5/3 0 12/25 Comparative Example 4 40 20' 2/30 3/28 * 1: Number of non-conformities / Number of samples &lt; Please read the notes on the back before filling (This page) ---- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, <Utilization in Industry>., The present invention provides a solid electrolyte layer and a conductive layer containing gold tincture powder, or conductive carbon. Layer and a solid electrolytic container containing rubber-like elastic material in at least one layer composed of a conductive layer containing gold tin powder on the layer and a method for preparing the same, K and a solid electrolyte used in the solid electrolytic capacitor, and a method for manufacturing the solid electrolyte , Conductive paste for solid electrolytic capacitors, and conductive carbon paste for solid electrolytic capacitors. A 5 2 _. This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) A7 459255 __B7 __.__ V. Description of the invention (50) The solid electrolytic capacitor of the present invention is conductive due to the formation of a solid electrolyte in it The polymer composition contains a rubber-like elastic material, so it can greatly reduce the number of impregnations and polymerizations, and improve productivity, so as to provide small-sized, low-impedance, high-performance solid f 觫 capacitors with ease of external stress and its manufacturing method. In addition, since M. specific polyheterocyclic compounds, especially conductive polythiophenes, are used as π-electron conjugated polymers and used as solid electrolytes, voltage withstand characteristics (spark voltage test>, high-frequency durability, loss coefficient ( tan S), impedance characteristics, leakage: current, heat resistance (reflow resistance), etc. greatly improved effects. In particular, in the above-mentioned conductive polymer k product, there are 71 electrons

The polymer is composed of V repeating units, the rubber-like elastic material contains the star in the range of Q.01 to 25%, and the sulfate ion content is in the range of 1 to 10 mole%. Can be made into capacitors with higher performance. Solid electrolytic capacitors. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and if the solid electrolytic capacitor of the present invention is provided on a conductive layer (conductor layer containing metal powder or conductive carbon), and a conductive body containing metal powder is provided thereon (Calendar) When the rubber-like elastic material is contained, the following effects can be obtained. Αα) The conductive paste of the present invention has a binder #fluorine, which is a rubber expansion, so it has low elasticity and excellent heat resistance and moisture resistance. '(2) The solid electrolytic capacitor using this conductive lake in the conductor layer has a small thermal stress during reflow, so it does not peel off at the interface of the isoelectric layer. '(3) As a result, the change in the equivalent series resistance (ESR) before and after reflow is small, and the effects of poor reflow and poor moisture resistance do not occur. -53- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297. mm) 459255 A7 _ B7 Five 'invention description (51) Even more advanced, the solid electrolytic capacitor of the present invention is in isoelectric carbon When using a rubber-like elastic material for the layer, especially fluorinated rubber-like elastic material, it has excellent hygroscopicity (water repellency). When the conductive carbon layer uses a conductive material to be determined (artificial black lead powder), it can be even higher. Packing density and excellent electro-electricity and heat resistance. / ί, therefore, the solid electrolytic capacitor obtained by using it as a conductive carbon paste f has low fESR (equivalent series resistance at 10 GKHz), low ESS change before and after reflow, and low humidity resistance. ······ A brief description of the drawing Figure I is a sectional view of an example of a solid electrolytic capacitor of the present invention; Figure 2 is a sectional view of another example of a solid electrolytic capacitor of the present invention; Electron microphotograph (magnification: 5 fl 0 0 times) of the isoelectric polymer of the present invention. 'Symbol description 1 1 1 ---- Valve action metal 2 ... · pores 3____ Dielectric coating 4 ---- Solid electrolyte calendar 5 ---- Conductor layer S ---- Outfit body 7. .. Terminal 7a ··. Anode terminal 7b ... Cathode terminal. -54- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-— If I .---- ---- / rn.Xiang (Please read the notes on the back ^ before filling out this page) ---- Order ------- I. Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs

Claims (1)

459255 E6 F6 Repair / Implication &gt; £ · / Supplement No. 8 9 1 0 2 7 9 Q Patent Application Amends the scope of patent application (please read the precautions on the back before loading) 1. A kind of broad effect A solid electrolytic capacitor provided with a solid electrolyte layer and a conductor layer on a dielectric coating layer formed on the surface of Jin Guang is characterized in that the solid electrolyte layer and at least one of the conductor layers contain an elastic rubber material. 2. The solid electrolytic capacitor according to item 1 of the patent application chart, wherein the conductor layer is composed of a conductor layer containing metal powder, or a conductive carbon calendar and a conductor layer containing gold tincture powder provided on the layer . 3 v The solid electrolytic capacitor according to item 1 of the Shenhe patent, wherein the solid electrolyte layer contains a rubber-like elastic material. 4. The solid electrolytic capacitor according to item 2 of the patent application, wherein the conductive carbon layer contains a rubber-like elastic material. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. If the solid electrolytic concrete container of item 2 of the patent application scope, the conductive layer containing metal powder contains a rubber-like elastic material. 6. If you apply for a patent, the solid electrolytic capacitors around item 2, where the solid electrolyte layer and the conductive carbon layer both contain rubber-like elastic material ° This paper size applies to China National Standard (CNS) A4 (210X297 mm) ) 459 255 6 6 EF shot in the shape, the rubber container has electricity and solution, all obtained electricity, obtained the picture of the electricity. Guide 2 of the last fan Wei belongs to Fan Jinli, and please apply for qualification, such as electricity 7 .body. The solid material is neutral and its elasticity, and the rubber container of the container has the electrical conductivity of the solid layer which contains the electric homogeneous layer. The 2nd powder of the second powder is Lijin exclusive and please apply the carbon conductivity of the carbon layer. There are all layers in this material. The body capacitor conducts electricity. The powder is a solid component and 2 layers of carbon bacteria. Special, material, please apply the layered application bullets like solution gel 9. The body rubber inherently contains {Please read the precautions on the back before drawing) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. The solid electrolytic capacitor according to any one of items 1 to 9, wherein a solid electrolyte layer of the solid electrolytic capacitor has a film-like or layered structure. 11. For example, the solid electrolytic capacitor of item 1, 3, 6, 7, or 9 of the patent application park, wherein the solid electrolyte is a film or layer of rubber-like elastic material containing Q.0 1 ~ 25 mass range. Conductive polymer composition. 12. The solid electrolytic capacitor according to item 11 of the application, wherein the rubber-like elastic material is at least one selected from natural rubber and synthetic rubber. 13. For solid electrolytic capacitors under the scope of patent application No. 11, the paper size is applicable to China National Standard (CNS_) A4 specification (210X297 mm) 459255 E6 F6 The rubber-like elasticity printed by the staff consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The material is fluorine rubber. 14. The solid electrolytic capacitor according to item 11 of the application, wherein the conductive polymer is at least one polymer of whipping, thiophene, aniline, or a repeating unit containing a divalent group of their derivatives. 15_If the electrolytic capacitors with the scope of patent application No. 2, 5, 7, 8 or s, the metal powder-containing conductor is a conductive filler containing metal powder and as a main component of a binder Fluorine rubber. 16. For example, the solid cross electrolytic capacitor of the scope of application for item I5, wherein the binder is fluorinated rubber with a mass of 30 to 30. 17. The solid electrolytic capacitor according to item 15 of the application, wherein 80% by mass of the conductive filler is silver powder. 18. The solid-state lightning capacitor according to item 15 of the patent application, wherein the average particle diameter of the conductive filler is 1ϋϋΐK to 10jumM. -I 1 19. The solid cross electrolytic capacitor according to item 15 of the scope of patent application, wherein the conductive filler is 50 to 95% by mass and the binder is 5 to 50% by mass 3; 2 0. The solid electrolytic capacitor according to item 15 of the scope of patent application, wherein the conductive layer of the metal powder is composed of a conductive filler, a binder, and -3- This paper is applicable to the Chinese National Standard (CNS) A4 specification ( 210 × 297 mm) (Please read the precautions on the back before drawing) E6 F6 459255 A layer formed by a conductive paste of an organic solvent. 21. —A capacitor element in which a dielectric oxide film, a solid electrolyte layer, and a conductor layer are formed on the surface of an anode body made of a valve-acting metal, in order to maintain the insulation state of the exposed portions of the anode lead terminal and the cathode lead terminal. A solid electrolytic capacitor composed of a wax package is characterized in that the solid electrolyte is a conductive polymer calendar, and the conductive calendar is a conductive layer containing metal powder as described in item 15 or 2 Q of the above-mentioned patent application. . 22. For example, the solid electrolytic capacitor of the scope of application for the patent No. 21, wherein the conductor layer is a conductive carbon layer on the conductor polymer layer and any one of the items of the patent application No. 15 to 20 is superposed on the layer A layer formed by a conductor layer containing metal powder. 23. For example, the solid electrolytic capacitor of item 21 in the scope of patent application, wherein the conductive polymer is poly (3,4-ethoxythiophene) ° 24. For example, in the scope of patent application scope 2, 4, 6, 8 Item 9 of the solid electrolytic capacitor, wherein the conductive carbon is a K conductive material, a layer formed by a conductive carbon paste containing MS solvent as the main component, and the conductive material is $ 80. The upper is artificial black lead, and the artificial black lead is a fixed carbon component of 97-black or more, an average particle diameter of 1 to 13W1B, an aspect ratio of 1GK, and a particle diameter on the particle diameter M of 12% by mass. ™ 4 — This paper size applies to China National Standards (CNS) Α4 size (210 X 297 mm) (Please read the precautions on the back before making the green system) Order printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Consumer Cooperative F6 F6 ^ 4592 ^ 5 25. For example, the solid electrolytic capacitor of item 24 of the scope of patent application, wherein the binder is a rubber elastic material that can be swelled or suspended in a solvent _ 0 (Please read the precautions on the back before (Line drawing) 26. For example, the solid electrolytic capacitor of item 25 of the application, wherein the material having rubber elasticity is selected from isoprene rubber, butadiene rubber, styrene / butadiene rubber, eye rubber, At least one material of isobutylene rubber, ethylene / propylene copolymer, acrylic rubber, polysulfide fluorene rubber, fluorine fluorene polymer, silicon rubber, and thermoplastic elastomer. 27. The solid electrolytic capacitor according to item 24 of the application, wherein 30 to 99% by mass of the solid content of the conductive carbon paste is a conductive material and 1 to 7D by mass is a binder. 28. —A method for producing a solid electrolytic capacitor composed of a solid electrolyte and a conductor layer on a dielectric film formed on the surface of a valve-acting metal, including: &gt; Making a monomer solution of conductive polymer and an oxidant solution At least one of them contains a rubber-like elastic material; the consumer cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs prints a monomer solution using the conductive polymer and an oxidant solution alternately and repeatedly coats one or more times to form a dielectric film on the surface The medium of the gull acting metal is coated with a film or layer of a conductive polymer composition. 29. For example, the manufacturing method of solid electrolytic capacitors under the scope of patent application No. 28-This paper uses Chinese National Standard (CNS) A4 specification (2 丨 0X297 mm) E6 F6 459255, where the conductive polymer composition It contains 01 to 25% by mass of the edge gelatinous elastic material. 30. The method for manufacturing a solid electrolytic capacitor according to item 28 or 29 of the application, wherein the rubber-like elastic material is rubber. 31. — A method for manufacturing a solid electrolytic capacitor with a solid electrolyte layer and a conductive calendar on a dielectric film formed on the surface of a valve-acting metal, which is characterized by using a conductive material with a rubber and rubber elastic binder and The conductive paste of the solvent forms and forms a conductor layer on the solid electrolyte. 32. The method for manufacturing a solid electrolytic capacitor according to item 31 of the application, wherein the conductor layer is formed by using a conductive paste containing a metal powder. An electrically conductive paste, a rubbery binder, and a conductive paste of a solvent Metal powder-containing electrical conductor calendar. (Please read the precautions on the back before drawing)-, 1T Via Wisconsin A Consumer Cooperative 33. For example, the method for manufacturing solid electrolytic capacitors under the scope of patent application No. 31, in which these electrical layers are made of a conductive material After the conductive carbon paste with a rubber elastic binder and a solvent forms a conductive carbon layer, a conductive layer containing metal powder is formed. 34. If the solid electrolytic capacitor is manufactured according to item 31 of the scope of patent application, wherein the electrical layers are formed by using a conductive carbon paste containing a conductive material, a rubber elastic binder and a solvent to form a conductive carbon layer 1 6 _ French rubber paper size applicable to China National Standards (CNS) A4 specifications (llOXW7 mm) E6 F6 459255 A conductive filler containing metal powder, a rubber elastic binder and the conductivity of the solvent The conductive paste contains conductive and physical metal powder. (Please read the cautions on the back before drawing) 35. For example, the method for manufacturing a solid electrolytic capacitor according to any of the items 31 ~ 34 in the patent application, where the solid electrolyte layer is made of a conductive polymer. ^ Solution and oxidant dissolve at least one military solution of the conductive polymer containing a rubber-like elastic material and the oxidant are dissolved on the dielectric coating, and one or more repeated coatings are performed to form a conductive polymer. 36. The method for manufacturing a solid electrolytic capacitor according to any one of claims 31 to 34, wherein the solid electrolyte layer has a film-like or layered structure. 37. The method for manufacturing a solid electrolytic capacitor according to item 36 of the application for a patent, wherein the thickness of each of the membranes or layers of the solid electrolyte having a film-like or layered structure is in the range of about 0.1 to 0.3 Wia. 38. A kind of solid electrolyte, which is composed of conductive polymer composition of rubber elastic material printed by the consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs of 0.01 to 25 mass 55. 39. The solid electrolyte according to item 38 of the application, wherein the rubber-like elastic material is at least one selected from natural rubber and synthetic rubber. The size of this paper is in accordance with China National Standards (CNS) A4 specifications (2) 0 &gt; &lt; 297 mm) r 459 2 〇5 E6 F6 40. If you apply for a solid electrolyte in the scope of items 38 or 39, where The rubber-like elastic material is fluorine rubber. {Please read the precautions on the back before drawing) 41. For example, the digging electrolyte in item 38 of the patent application scope, in which the conductive polymer is pyrrole, sleep phen, aniline, or the derivative containing them. At least one polymer of valence-based repeating units. 42. — A method for producing an object having a solid electrolyte, including: · For an object requiring a solid electrolyte composed of a conductive polymer composition on its surface, using at least one of a conductive polymer monomer solution and an oxidant to dissolve The cells containing the above-mentioned solutions of the rubber-like elastic branch are repeatedly coated once or several times to form a film-like or layer-like conductive polymer composition on the surface of the object. 43. The method for manufacturing an object with a solid electrolyte, such as in item 42 of the scope of the patent application, wherein the coating is performed by any method such as dipping, coating, spraying, or solution pouring. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 44. For example, a method for manufacturing an object with a solid electrolyte, such as in item 42 of the patent application, in which the rubbery material is a monomer added to the conductive polymer by dissolving or dispersing And / or in oxidant-containing solutions. 45. A conductive paste for solid electrolytic capacitors, which is composed of a conductive filler composed of metal powder and a binder containing fluororubber as the main component ~ 8 ~ This paper size applies to China National Standard (CNS) A4 specifications (2 丨 0X297mm) 0 (please read the precautions on the back before drawing) 46. If you apply for the conductive paste for solid electrolytic concrete container with the scope of patent application No. 45, 80% of the adhesive SM is fluorine rubber. 47. For example, the conductive paste for solid electrolytic capacitors in the scope of application for patent No. 45, wherein the conductive filler is 80 pounds and more than 3 pounds of silver powder. 48. For example, the conductive paste for solid electrolytic capacitors in the scope of application for patent No. 45 or 47, wherein the average particle diameter of the conductive filler is in the range of 1 to 10 Win. 49. For example, the conductive paste for solid electrolytic capacitors in the scope of application patent No. 45 or 47, wherein the conductive filler accounts for 50 to 95% by mass, and the binder accounts for 5 to 50% by mass. 50. The solid electrolytic capacitor according to claim 45 of the application claims a conductive paste, wherein the conductive paste contains an organic solvent. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 5 1 · A kind of conductive carbon paste for solid electrolytic capacitors, which is composed of conductive carbon materials, binders and solvents. Among them, 80% of the conductive carbon material % Or more is artificial rhenium lead, and the fixed carbon content of the artificial erbium lead is 97% by mass or more, the average particle diameter is 1 to 3 Å, the aspect ratio is 10M, and the particles on the diameter of 32 «m Μ account for 12% by mass. -9- The size of this paper is applicable to the national standard (CMS) A4 specification (2〗 0X297 mm); m459 2 b5 E6 F6 52. For example, the conductive carbon paste for solid electrolytic capacitors in the 51st patent application park Among them, the drilling agent is a kind of rubber elastic material which can be swelled or suspended in a solvent. 53. For example, the conductive carbon paste for solid electrolytic capacitors according to the scope of application for patent No. 52, wherein the material having rubbery properties is selected from isoprene rubber, butadiene rubber, styrene / butadiene, and diene. At least one material of rubber, eye rubber, isobutylene rubber, ethylene / propylene copolymer, acrylic rubber, polysulfide rubber, fluorine polymer, silicone rubber and thermoplastic elastomer. 54. For example, the conductive carbon paste for solid electrolytic capacitors according to any one of items 51 to 53 in the scope of application, wherein the solid content of the conductive carbon paste is 30 to 99 mass. 8: is a conductive material, 1 to 70 The mass% is a binder. (Please read the precautions on the back before drawing) -Order --II 1 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by Consumer Cooperatives -10- This paper size applies to China National Standard (CMS) Α4 specification (210 × 297 mm)-