TW434602B - Solid electrolytic capacitor and method for preparing the same - Google Patents

Abstract

Disclosed are a solid electrolytic capacitor and its preparation method that comprises forming an electrically conducting polymer composition layer on an oxide dielectric film layer, in which the electrically conducting polymer composition layer contains as a dopant at least one anion selected from (1) an alkoxy-substituted naphthalene monosulfonate anion, (2) a heterocyclic sulfonate anion, and (3) an anion of an aliphatic polycyclic compound or a combination thereof with another anion having a dopant ability and a method for producing such a solid electrolytic capacitor. The solid electrolytic capacitor of the invention is excellent in voltage resistance, high frequency property, tanδ, leakage current, heat resistance, etc.

Description

434602 A 7 B7 Printed by the economy “哪 中 夬 #Associate Bureau Consumer Consumption Cooperative” V. Description of the Invention (1) The present invention relates to solid electrolytic capacitors and their manufacturing methods. In more detail, Fei is in solid electrolyte. A dopant containing at least one fluorene anion selected from the group consisting of (1) an alkoxy-substituted Chaimonosulfonic acid anion, (2) a sulfonic acid anion of a heterocyclic compound, and (3) an aliphatic polycyclic compound anion. A solid electrolytic capacitor having a 7T electron conjugate structure of an electropolymer and a method for manufacturing the capacitor. The solid cross electrolytic capacitor is formed by forming a dielectric oxide coating layer on an etched gold substrate (impregnated substrate) and a solid semiconducting layer (referred to as a solid electrolyte hereinafter) as a counter electrode on the outside thereof, and more It may be an element formed by further forming a conductive layer such as a conductive paste. The metal foil of this element is connected to the cathode lead terminal and the conductor layer is connected to the anode lead terminal. The entire M insulating resin is completely encapsulated as a capacitor component and widely used in electrical products. Those skilled in the above solid electrolytes include, for example, manganese dioxide or lead dioxide and other hunger-free quasi-isomeric materials; tetracyanoquinodimethane (TCNQ) complex salts or electrical conductivity in the range of 10-2 to 5x103s / cb. True conductive polymer [Japanese Patent Application Laid-Open No. 1-16 99 1 4 (US Patent No. 4, 80 3, 5 96)] or;! Polyaniline (Japanese Patent Laid-Open No. 61-239617), Polypyrrol (Japanese Patent Laid-Open No. 6-240 240 25), polythiophene derivatives [Japanese Patent Laid-Open No. 2-156 11 {US Patent No. 4 9 1 G 6 4 5)], polyisothioindene (Japanese Patent Laid-Open No. 6 2 -1185U), etc. ft and so on? The conductive polymer formed by the repeated structure of the I conjugated structure is usually used as a composition containing a dopant. In addition to the addition of a dopant, manganese dioxide has been used in combination. 6 -Scheme of 1 01 4 1 8 (U.S. Patent No. 4, 9 59, 7 5 3) or filler (Japanese Unexamined Patent Publication No. 9-320901). -4- Please read the precautions on the back and fill in (14 pages) .-!--—II · The scale of the thread is applicable to the Chinese National Standard (CNS) A4.it (210X 297 male |) 4346 〇2 Central Ministry of Economic Affairs. Standards Bureau Employees Cooperative Cooperative A 7 B7 5 2. Description of the invention (2) Regarding the method for forming a solid electrolyte, there is a method of forming a solid electrolyte as described above on a dielectric layer having a fine void structure on the surface of a valve, and a method for forming the solid electrolyte, or on the dielectric layer. A method and the like for producing the above-mentioned conductive polymer are known. Specifically, for example, when using a polymer of a five-membered heterocyclic compound such as pyrrole or paclitaxel, the anode foil is immersed in a lower enzyme / aqueous solution of the heterocyclic compound, and then immersed in an oxidizing agent and an electrolyte. A method for chemically polymerizing an aqueous solution to form a conductive polymer (Kokukai Hei 5-1 7 5 0 8 2); a 3,4-dioxyethylene-phenylene monomer and a gasifying agent, preferably K A method of forming the solution on the oxidized coating layer of gold foil before or after the solution form, respectively or together [(Japanese Patent Publication No. 2-15611 (US Patent No. 4,910,645) or Japanese Patent Application Publication No. 10-32145 (European Patent Publication No. 8 2 0 0 7 6 A2 >] and others are known. In particular, Japanese Unexamined Patent Publication No. 10-32145 discloses an aromatic polysulfonic acid doped with a plurality of sulfonic acid groups in a molecular structure (for example, Huadisulfonic acid) is selected from the group consisting of pyrrole, thiopan, thiamine, aniline and polymers selected from their derivatives, and the manufacturing method has disclosed that a mixed solution of the polymerizable military and oxidant described above is applied and After drying or introducing oxidant into monomer In addition, Japanese Patent Application Laid-Open No. 10-32145 discloses a manufacturing method using a dopant of an aromatic polysulfonic acid as a constituent of an oxygen halide (Asia_〇 *). And it has the characteristics of solid electrolytic capacitors with this component, which is excellent in high temperature resistance or prevents a decrease in electrostatic capacity. In addition, it is disclosed in U.S. Patent No. 6-8 2 5 Lee (US Patent No. 4 9 5 9 7 5 A solid electrolytic capacitor containing an alkylnaphthalenesulfonic acid anion substituted with more than one alkyl group as a dopant is disclosed in (), and this capacitor is mentioned (please read the note on the back of this page first) The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210 × 297 mm). It is printed by the staff of the Central Bureau of Standards of the Ministry of Economic Affairs and printed by the cooperative. A7 B7 V. Invention Description (3) It has stupid initial characteristics and creepage characteristics. Among the known oxidants for polymerization, such as oxidized iron (egg), Fe (Cl〇4) 3, or acetic acid (S) ), Non-fluoric acid (fi), strong alkyl persulfate, ammonium persulfate M is abbreviated as APS), oxidized g, 1 ^ (: 1'2〇7, etc. [Japanese Unexamined Patent Publication No. 2-15611 (U.S. Patent No. 4,910,645)] or osmium compounds, silver compounds, etc. [Japanese Unexamined Patent Application] 10-3214 No. 5 (Weizhou Patent Publication No. 82007682)] 0 However, when the above-mentioned solid electrolyte capacitor using manganese dioxide is thermally decomposed by manganese nitrate, the oxide film layer is broken, and The impedance characteristics are also not ideal. In addition, when using lead dioxide, there are environmental concerns. Use of tetracyanoquinodimethane (TCNQ) solid electrolyte of a solid electrolyte " container although it has a P melting process Electrical conductivity or conductivity, but TCNQ network itself has heat resistance problems, poor reliability in soldering heat resistance. In order to improve the above problems, although the conductive polymer such as polypyrrole can be used as a solid electrolyte on the surface of the medium by electrolytic polymerization method or chemical polymerization method, satisfactory film uniformity, soldering heat resistance, and resistance characteristics cannot be obtained. 〇. For this reason, in the manufacture of high-performance capacitors, there is a strong demand for the improvement of the thermal stability and the uniformity of the film of the solid electrolyte material or its manufacturing method. In view of the above problems, the present invention provides a light and small, high-capacity, K and high frequency characteristics, loss coefficient (tanS), 耐热 current, heat resistance-6-This paper size applies Chinese National Standard (CNS) A4 specifications (210X 297 public 煃) (Please call for the precautions on tw before filling out this page »mt n ^ in ^ ln I ϋ ^ — till tn V! J, y5 Quan 434602 A 7 B7 M Central Standard of Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives. 5. Description of the Invention (4) (Reflowability) and other excellent solid electrolytic capacitors. In particular, the present invention provides thermal solid electrolytic capacitors with low impedance characteristics and excellent durability for spark voltage tests. In order to solve the above-mentioned problems, the present inventors made an intensive study on the type, combination, and content of the male and female dopants in the conductive polymer, and the results are as follows: a pair of electrodes is opposed to each other It is a solid electrolytic capacitor with a finely structured dielectric (insulator) layer formed of a gold oxide on the surface of a valve-operated gold foil and a solid electrolyte layer made of a conductive polymer formed on the dielectric layer. In the present invention, a specific organic anion is used as a dopant, so that it is contained in the solid electrolyte, so as to solve the above problem. That is, the present invention provides a solid electrolyte containing a selected from: (1) carbon atoms Number of 1 to 12 (Ct-C12) straight or branched saturated or unsaturated hydroxy groups substituted on at least one M substituted alkoxy plug substituted naphthalene monosulfonic anion; (2) 5 or 6 section At least one of the sulfonic acid anion of a cyclic heterocyclic compound (?. Hereinafter referred to as a heterocyclic sulfonic acid anion) and (3) an anisotropic compound of an aliphatic polycyclic compound is a small, low-impedance, and extremely excitable organic organic anion. High-performance solid electrolytic capacitor for durability against spark voltage test table and manufacturing method thereof. More specifically, the present invention relates to: [1]-a conductive polymer having a 7T electron shared structure formed on a dielectric oxide film The solid electrolytic capacitor of the material layer is characterized in that the polymer layer contains a saturated or branched straight or branched bond selected from (1) a carbon number of 1 to 12 ((^ -C12) or At least one substituted alkoxy group of unsaturated alkoxy group Substitute yin sulfonic acid; (2) 5 sections or 6 Please read the notes on the back.% The paper size on this page applies to the Chinese National Standard (CNS) Λ4 specification (210X 297 mm) 434602 A7 Central Standard of the Ministry of Economic Affairs Bureau Consumer Consumption Cooperative Seal 11 B7 __V. Description of the Invention (5) The sulfonic acid anion of the heterocyclic heterocyclic compound of Section 5 (hereinafter referred to as fluorene ring sulfonate) and (3) aliphatic polycyclic At least one organic anion of the compound is used as a dopant. [2_] The solid decomposition capacitor as described in the item [1] above, wherein the organic anion as the dopant is pseudo-numbered by the number of carbon atoms. 1 to 12 linear or branched fluorinated saturated or unsaturated alkoxy substituted at least one substituted alkoxy substituted fluorene-sulfonic anion. [31] The solid electrolytic capacitor according to the above [2], wherein the aromatic ring hydrogen atom of the alkoxy substituted naphthalene monosulfonic acid is at least one selected from a halogen atom, a nitro group, a fluoro group, and a trihalomethyl group. A substituted alkoxy substituted naphthalenesulfonic acid. [4] The solid electrolytic capacitor according to item [1] above, wherein the organic anion as a dopant is a heterocyclic sulfonic acid anion. [51] The solid electrolytic capacitor according to the above item [4], wherein the heterocyclic skeleton of the heterocyclic sulfonic acid anion is selected from the group consisting of morpholine, saliva, piperazine, wezod, furfur, 1,4 -Chemically constructed compounds of dioxane, benzimidazole, benzothiazole sulfur, benzoisoxazole, benzotriazole and benzofurazole. [6] The solid electrolytic capacitor according to item [4] above, wherein the heterocyclic sour anion system contains more than one fluorenyl acid substituent in its chemical structure. [T] The solid electrolytic capacitor according to the above-mentioned item [1], wherein the organic anion is an anion of the aliphatic polycyclic polycyclic compound as the dopant Z. [8] The solid electrolytic capacitor as described in [II ~ [7] above, wherein the organic anion is a full repeating unit of conductive polymer M 〇. 1 ~ -8- This paper size is applicable to Chinese national standards (CN'S) Α4 specification (210 X 297 male " Τ '" ~~' VHI m g-lsi ^ .nn i in ml —I * · If.-(Please read the precautions on the back first, then :: ¾ This page) Ordering line 3 A 7 _B7 V. Description of the invention (6) 50 The ear range is inclusive. [9] The solid electrolytic capacitor as described in the above [11 ~ [8], except for the above In addition to the plutonium anion M, there is also a reduced male masculine male in the range of 0.1 to 1 x X which contains an oxidant with a dopant property. [1G] The solid electrolytic capacitor according to the above item [9], wherein The protoan anion is sulphate yin sulphate. Read I first | Read | Read; on the back · i face h, note-on the upper surface [1] ~ [10] as described in any one of the formation on the dielectric oxide film A solid-stomach container with a conductive polymer layer, wherein the polymer of the composition contains a repeating structural unit represented by the following β 1 formula (I): 11] Such as

I electrical display

(I) In the formula: each of the substituents R1 and R2 independently represents a saturated or unsaturated hydrocarbon group of oxygen, a linear or branched chain of P ^ L1_Ce, or (: 1-(: 6 straight_life) + (^ _ 珥 or branched 鐽 saturated or unsaturated alkoxy, hydroxyl, halogen atom, nitro, ^ m is S, bidentate

Any one of the monovalent radicals selected from phenyl, phenyl and substituted phenyl; Y 乂, the substituents mentioned above! ^ And R2 can be combined with each other at any position to form at least 1 涸 monovalent bond to form at least one 5 to 7-membered ring saturation or ^% Α running and ring structure; X represents heteroatoms S, 0 , Se, Te, or MR3 _ * where R3S Cj -ce is a saturated or unsaturated hydrocarbon group with a straight or branched bond, phenyl, d is a straight or branched Ci-CB saturated or unsaturated alkoxy group; also the above b, R3 = $ This paper size applies Chinese National Standards (cns). μ size (m0x 297 mm) Central Government Bureau of Standards Bureau, Ministry of Economic Affairs, Consumer Cooperatives, India 4 3 4 6 0 2 A7 B7 V. Invention Note: The hydrazone of (7) group and alkoxy group may arbitrarily contain a carbonyl bond, an ether bond, a sulfonium group, a hydrazine bond, and an imino bond; and δ represents Q ~ 1. [12] As described above [11 The solid electric ramie capacitor as described in the above item, wherein the repeated structural unit of the formula (I) is shown by the following formula (II):

S -----;: I! An ······· shi n JJ-(Please read the precautions of Xiannian before <; this page ·) Printed by the Employees' Cooperatives of the Central Bureau of Standards, Ministry of Economic Affairs In the formula: each of the substituents ϋ4 and R5 independently represents a Ci-Cs straight or branched saturated or unsaturated hydrocarbon group, or a Ci-Ce hydrocarbon group is combined with each other at any position to form two gas atoms described in the formula 5 of at least one M? Substituents for the fluorene ring structure; the scope of forming the above ring structure includes chemical structures such as substituted vinylene groups or 0-phenylene groups; S represents 0 i 〇 [13] — as described in [1] above The method for manufacturing a solid electrolytic capacitor having a conductive polymer layer formed on a dielectric oxide film is a method for polymerizing a polymerizable monomer compound by an oxidant on the dielectric oxide film. The characteristics include: Polymerizable monozhao compound represented by formula (III): R1 R2

-10- This paper size applies the Chinese National Standard (CNS) A4 grid (210X 297mm) 434602 Λ7 B7 V. Description of the invention (8) (where: the substituents R1, R * 6 and X are the same as above Formula (same as defined by Π). Substituted at least one alkoxy substituted naphthalene monoacid ion in at least one selected from (1) straight or branched and unsubstituted or unsaturated alkoxy; (2) ) A sulfonic acid anion of a heterocyclic compound having a heterocycle of 5 or &amp; sections (referred to as a heterocyclic sulfonic acid anion); (3) at least one compound that can provide an organic anion for the male and female of an aliphatic polycyclic compound The polymerization reaction is carried out in the presence of i- U 4]. The method for producing a solid electrolytic capacitor as described in the above item [1 3], wherein the polymerizable monomer compound of the formula (III) is represented by the following formula (IV) Shown compound: 'R40 OR5 \ /

S —V (IV), (please read the precautions on the back before widening. 4 'this page) Order the printed format of the Consumer Cooperatives of the Central Luzhun Bureau of the Ministry of Economic Affairs: R4 and Rs are defined by the above formula (II) The same. [15] The method for manufacturing a solid electrolytic capacitor as described in [13] or [U] above, further comprising: immersing the osmium-impregnated gold yangyang foil with a dielectric oxide coating layer formed in a solution containing a polymer military compound And a step of immersing in a solution containing an oxidizing agent and the above-mentioned organic anion. [16] The method for manufacturing a solid electrolytic capacitor as described in [13] or [14] above, further comprising: forming a dielectric oxide film layer; ^ valve action Jinyang anode must be immersed in a solution containing an oxidant Step · and -U- line

— / PLT This paper size applies the Chinese National Standard (CNS) A4 specification (210X'297 gong) ά Printed by the Consumers' Cooperative of the Central Procurement Bureau of the Ministry of Economic Affairs A 7 B7 V. Description of the invention (9) Impregnated with polymerizable 箪Of the compound and the sulfonium anion solution described above. [1 7] The method for manufacturing a solid electrolytic capacitor according to the item [1 3] or [1 4], further comprising: immersing a valve-acting metal anode foil having a dielectric oxide coating layer formed on the solution containing an oxidant , Soaked in the solution containing polymerizable military compounds and the above organic anions. [18] The method for manufacturing a solid electrolytic capacitor according to the above item [13] or [14], further comprising: immersing the valve-acting gold-alloy anode foil having a dielectric oxide film layer formed therein with a polymerizable monomer compound. The solution is immersed in a solution containing an oxidizing agent and the organic anion described above. [19] The method for manufacturing a solid electrolytic capacitor according to the item [13} or [14], further comprising: immersing the valve action gold 鼷 anode 形成 formed with the dielectric oxide film layer in an oxidizing agent and the organic Yin male The solution is then immersed in a solution containing a polymerizable carcass compound. [20] The method for manufacturing a solid electrolytic capacitor according to item [13] or [14] above, further comprising: immersing a valve-acting gold-alloy anode foil having a dielectric oxide film layer formed therein containing a polymerizable military compound and After the solution of the organic anion described above, it is immersed in a step of dissolving the oxidized cargo. [21] The method for manufacturing a solid electrolytic capacitor according to the above item [13] or [14], further comprising: immersing the anode gold foil having a dielectric effect coating layer formed thereon, and immersing the anode foil containing an oxidizing agent and an upper organic cathode. After the solution of vitamins, the step of immersing in a solution containing a polymerizable monomer compound is repeatedly performed. [22] The solid electrolytic capacitors described in [13] or [14] above -12- This paper size applies to China National Standard (CNS) A4 specifications (210 ', &lt; 2? 7 mm) ---- ----- install-(Please read the precautions on the back first, ¾ this page)

、 TT line 434602 A7 B7 Consumption cooperation with employees of the Central Standards Bureau of the Ministry of Economic Affairs. Printing 5. Production method of invention description (i〇), further comprising: immersing the valve action gold 羼 anode 形成 formed with the dielectric oxide coating layer. After the solution of the polymerizable monomer compound and the organic anion is coated, the step of immersing in the solution containing the oxidizing agent is repeatedly performed repeatedly. [23] 方法 The method for manufacturing a solid electrolytic 罨 container as described in the item [13] or [14] above, further comprising: immersing a valve-acting metal anode having a dielectric oxide coating layer 萡 in a solution of an oxidant, and immersing in The step of dissolving the polymerizable monomer compound and the organic anion described above is performed repeatedly. [24] The method for manufacturing a solid electrolytic plutonium container as described in the above item [13] or [14], further comprising: immersing the valve action Jinyang anode foil formed with a dielectric oxide film layer in a polymerizable military body After the solution of the compound, the step of immersing in the solution containing the oxidizing agent and the organic anions mentioned above is repeated several times. [251] The method for manufacturing a solid electrolytic capacitor as described in [13] or [14] above, further comprising: immersing a valve-acting metal anode foil having a dielectric gasification film layer formed therein containing an oxidizing agent and the organic Yin male After the solution is immersed, the steps of the solution containing the polymerizable military compound are repeatedly carried out, and then the steps of washing and drying are performed. [26] The method for manufacturing a solid electrolytic capacitor according to the above [13] or [14], further comprising: immersing a valve-acting metal anode foil having a dielectric oxide film layer formed therein containing a polymerizable monomer compound and After loading the solution of organic anions, the steps of immersion in a solution containing an oxidant are repeatedly performed, and then the steps of washing and drying are performed. -13- This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification (2 丨 0X 297 mm) (Please read the precautions on the back before &%; this page). Binding-Thread 434602 A7 B7 Through the center of the drop section Printed by the Standards Bureau Consumer Cooperatives V. Invention Description (11) [27] 50 The method for manufacturing a solid disintegrating capacitor as described in [13 1 or [14] above, further comprising forming a dielectric layer oxidized by an m layer The valve action gold foil anode foil is immersed in a solution containing oxidil. 9 The steps of immersing in a solution containing a polymerizable military compound and the above-mentioned organic male masculinity are repeatedly performed. 1 The steps of washing and drying are performed again. [28 ] The method for manufacturing a solid disintegrating capacitor as described in [1 3] or (1 4) above, further comprising: immersing a valve action gold yangyang foil with a dielectric oxide coating layer formed on a polymerizable monomer compound After the solution 9 is immersed in the gasifier and organic After the steps of the solution of the anion are repeatedly performed, the steps of washing and drying are carried out. [29] The method for manufacturing a solid electrolytic capacitor as described in [13] ~ [28 3 above, wherein the organic masculine male It is a monosulfonic acid anion substituted by at least one M of a straight or branched saturated or unsaturated alkoxy group of Cl -C 12. [30] The solid electrolytic capacitor described in [29] above. Production method 4 wherein the aromatic ring hydrogen atom of alkoxy substituted naphthalene monosulfonic acid is at least one kind of substituted alkoxy substituted naphthalene by m white halo atom, nitro group, cyano group> trihalomethyl group [31] The method for manufacturing a solid electrolytic capacitor according to the above [13] ^-I 28], wherein the anion-based heterocyclic sulfonic acid anion is [32] the above-mentioned [13, [31] Manufacturing of solid electric-jm capacitors Method, wherein the heterocyclic skeleton system of the heterocyclic sulfonic acid anion is selected from the group consisting of morpholine, piperidine, and piperazine imidazole \ furan Λ 1,4-dioxobenzobenzoylbenzothiazole sulfur, benzoiso Oxazole N Benzotriazole and benzofuran -14- The size of the paper of the wood is applicable to the Chinese national standard (CNS> A4 Regulations (2i0x2W mm) Please read the precautions before deteriorating the page Λ 7 Β7 Printed by the Consumers Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs of the People's Republic of China on the preparation of the five 'inventions (12). [s33] The method for producing a solid electrolytic rhenium container according to the above item [31], wherein the sulfonium sulfonic acid anion contains at least one alkylsulfonic acid substituent in a chemical structure. [34] The method for manufacturing a solid electrolytic capacitor according to the above [13] to [281], wherein the organic male male is a male male of an aliphatic polycyclic compound. [35] The solid electrolytic container according to any one of the above [13] to [34], wherein the oxidant is a persulfate. [361] The solid electrolytic capacitor according to the above [1], wherein at least a part of the solid electrolyte layer has a layered structure. [37] The solid electrolytic capacitor according to the above item [36], wherein the solid electrolytic calendar having at least a part of a layered structure is formed on the outer surface of the dielectric film or on the outer surface and the micropore portion. [38] The solid electrolytic capacitor according to the above [36] or [37], wherein at least a part of the interlayers of the stellate structure has a space portion. [39] The solid electrolytic capacitor according to the above item [36] or [37], wherein the thickness of each layer forming the solid electrolyte of the layered structure is in a range of 0.01 to 5 «B, and the total thickness of the solid electrolyte layer It is in the range of 1 ~ 200w 1Π. <Detailed description> 详细 Detailed description of the present invention is as follows: According to the present invention, since the conductive polymer sister layer contains at least a saturated or unsaturated alkoxy group having a straight or branched Ci-Ciat bond— The above substituted alkoxy substituted naphthalene monosulfonic anion, (2) has 5 sections or 6 -1 5-This paper size applies to Chinese National Standard (CNS) Λ4 specification (210 × 297 mm) (read the first Note on this page again) • Xi a / * τ Γ, ί, 4 ο 4 6 Ο 2 A7 B7 Central Standards of the Ministry of Economy 扃 Printed by Employee Consumer Cooperatives V. Miscellaneous Heterocyclic Rings of Invention Description (13) Sulfonic acid anion of the compound; and (3) at least one organic anion selected by an anion of an aliphatic polycyclic compound as a main anion having a dopant ability, so it can form a conductive polymer layer with good thermal properties (Charge-shifting complex). As a result, it can provide a high-performance solid electrolytic capacitor with a long-lasting resistance and a high-performance solid electrolytic capacitor that exhibits [different iW longevity in spark electric JE tests and the like. In addition, the present invention can further improve the above-mentioned properties by using other female chicks other than the male dopant M of the organic Yin male as a dopant, and is suitable as the conductive polymer layer of the capacitor of the present invention. The κ-electron conjugated polymer in the polymer is a polymer compound with a κ-electron conjugated structure in the main structure of the polymer. Its elegant examples are polybenzylamine, poly-p-phenylene, poly-p-phenylene vinylene, Polythienylene vinylene, polyheterocyclic polymers and their substituted derivatives. A specific example of a preferable polyheterocyclic polymer is an α-electron conjugated polymer having a structural unit represented by the above formula (I), and more preferably a π-electron conjugated polymer having a structural unit represented by the above formula (II) Thing. In the above formula (I) and formula (I), the substituents R1,! ? 2 and R3 represent straight or branched saturated or unsaturated hydrocarbon groups of h-Ce. Specific examples are methyl, ethyl, vinyl, propyl, allyl, isobutylene, butyl, and 1-butenyl. Specific examples of the straight- or branched-chain saturated or unsaturated alkoxy groups of Ci-Cs are methoxy, ethoxy, propoxy, isopropoxy, and butoxy. Specific examples of useful substituents other than the above-mentioned nicotinyl group or alkoxy group M are nitro, cyano, phenyl, and substituted phenyl (halogen-substituted phenyl such as Cl, Br, and F) ° R1, R2's alkynyl and alkoxyl chains can optionally contain truncated bonds, K 鐽, -16- (Please read the precautions on the back before writing this page) National Standard (CNS) Λ4 specification (210x297 mm) 4346 Ο 2 佟 正 Μα &quot; mmm A 7 B7 V. Description of the invention (14) Ester bond, fluorene amine and imino fluorene, a particularly useful example is formazan. Oxyethoxy and methoxyethoxyethoxy. Further, the above-mentioned substituents R1 and R2 may be combined with each other at any position to form a divalent group having a saturated or unsaturated cyclic structure of one or more 5 to 7-membered rings. Specific examples of such a divalent radical of formula (I) or formula (S) include 3,4-propene substituted fluorene (VI), 3,4-butane substituted structure (νΓΙ), 3,4 as shown below. -Butene substituted structure (? 111) and Cai Cong [2,3- &lt; ^] sickle compilation (IX): Please read back f, 1 1 I save I f

'X (V) Tintin

4346U2

V. Description of the invention (15

X (ΥΙΠ)

(IX) The printed bag of the Consumer Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs In the above formula: χ represents a heteroatom. Specific examples are s, 0, Se, Te, or NR3. X is the above-mentioned 3,4-butadiene-substituted substitution port of S. If it is a repeated unit structure of formula (I), it is commonly known as isothianaphthenylene structure. If it is a polymerizable carbohydrate compound of formula (S) Tectonic is commonly known as isothianaphthene structure. In addition, Tsai [2,3-c] combined substitution structure, if it is the formula. In the case of (I), it is a condensed [2,3-c] thiophene (thienylene) structural unit and a polymerizable monomer compound of the formula (I) is recommended. When constructed, 'thin is naphtho [2,3-c] thiophene. In the formula, δ represents the charge number of an iterative structural unit, which is a value in the range of 0 to 1. Examples of useful substituents of β * and R5 in formula (II) or formula (IV) are methyl, ethyl, propyl, isopropyl, vinyl and allyl. 8 * and again! {3%-% hydrocarbon groups can also be combined with each other at any position to form the above formula (11 (please read the precautions on the back first, and then-this page)

N c% T \

Ai 4 A

X

I A7 B7 V. Description of the invention (I6) or a substituent of a heterocyclic structure of a 5 to 7-membered ring containing at least 1 俚 or more of 2 oxygen as shown in Formula (IV); and specific examples of this substituent are preferable It is 1,2-ethylene, 1,2-propylene, 1,2-dimethyl-ethylene. In addition, R * and R5 can also be cyclic structures of unsaturated hydrocarbons such as vinylene or o-phenylene, which are combined with the above-mentioned Ct-Cs hydrocarbon groups to each other at any position. For example, 1,2- Ethylene (X), 1,2-propylene (XI), 2,3-butene-2- (XII)

V, 1,2-cyclohexene (XIII), methyl-O-phenylene (XIV), 1,2-dimethyl-0-phenylene (XV), and 2-yl-0-phenylene (XVI ): '(Please read the notes on the back first, then this page)

\ J- (XI order line--i Printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs

f y

I (XI

This paper scale it uses towels (CNS) A4a grid (21Qx297 Gongcheng) 4346 0 2 A7 B7 V. Description of the invention (l7

(Please read the notes on the back before I: this page)

ο 2 This paper size applies Chinese National Standard (CNS) Λ4 specification (210 X Μ? mm)-line A 7 B7 V. Description of invention (18)

^ / ^ Η2ΟΗ3 〇 〇

s Please read the note on the back # Item ί. The consumer cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs printed the monomer compound of the above formula (1) used in the solid electrolytic capacitor of the present invention and its manufacturing method, for example, phenanthrene (1 ^ =! ^ = 11,] [= 8) or pyrrole (R ^ R ^ H, X = NH), or the 3,4-dioxyethylene-thiophene of the thiophenes represented by the above formula (IV) Polymeric military bodies are known, and oxidants that can polymerize these monomers are also known. However, it has never been known to manufacture a capacitor with a solid electrolyte by using the organic anion (1) to (3) as a dopant and the other anions as auxiliary dopants in the conductive composition. . That is, the conductive polymer composition for capacitors disclosed in Japanese Patent Application Laid-Open No. 10-32145 is an aromatic polysulfonic acid compound (for example, naphthalenedisulfonic acid) selected from the group consisting of doped sulfonic acid groups having a plurality of sulfonic acid groups. (A) Polymers such as pyrrole, phenanthrene, furan, benzene limb and its derivatives. It does not disclose any organic anions as described in (1) to (3) above, nor does it show any combined technology of erbium co-rib dopant anions and the enhancement effect obtainable by them. In addition, the preferred form of the dopants of the solid electrolyte constituting the solid electrolytic capacitor of the present invention is the opposite; the total repetition of the polymer is -2 1- The paper rule uses the Chinese national standard (CNsT ^ 4 specifications (210X297 public Jie) 1- this page) .rL --- installed ---- --- order. Line -----, ----- ^ ---; ---- ^ -

V. Description of the invention (IS) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs &gt; Yuan contains the above-mentioned (1) ~ (3) yin yin zizi 0 · 1 ~ 50 mol x and more preferably contains and contains the above organic Anions other than the anion K are 0.1 to 10 moles X. A capacitor provided with a solid electrolyte containing such inclusions can solve the above-mentioned problems, and also has excellent low impedance characteristics and a spark voltage test showing excellent durability. Such a solid electrolytic capacitor and its manufacturing method have never been known. In the capacitor of the present invention, the solid electrolyte of the capacitor which can provide a low impedance characteristic is an all-repeat unit of a π-conjugated fluorene polymer containing 1 to 30 moles; the above-mentioned organic anion. In addition, it is preferable that the content of the anions other than the organic anion M in the above-mentioned solid electrolyte in the solid electrolyte is 0.1 to 5% of the full repeat military element of the π-conjugated polymer. In the production method of the present invention, the other anions mentioned above are used in the polymerization of military compounds, so they can be contained in the anion heterozygous state of the oxidizing agent, so they need not be added separately, but they can also be added separately. This inclusive method is not particularly limited. In the manufacturing method of the capacitor, in order to improve the high-frequency characteristics of high capacity, leakage current, heat resistance (reflow property), impedance, and durability, the method for manufacturing (forming) the solid hip electrolyte is even important. For this reason, the 7! Electron conjugate structure and dopants of the solid electrolyte are combined, and K and the dense filling on the fine dielectric layer to form a conductive polymer layer to improve the uniformity of the conductive variable resistance are important measures. In particular, the composition of the conductive polymer has a great influence on the characteristics of the capacitor. One of the solid electrolytic capacitors of the present invention is a layered structure in which at least a part of the solid electrolyte layer is provided with thermal stress relaxation characteristics and the like. -2 2-This paper size is in accordance with Chinese National Standard (CNS) Λ4 specification. (210.X 297 gong) Wen M's tears binding page binding line 4346 〇2 A 7 B7 5. Description of the invention (2〇) solid The electrolyte layer is formed in the fine pore portion of the dielectric layer on the surface of the valve action metal and the outer surface thereof. The thickness of the outer surface layer is in the range of 1 to 200 w η, and preferably in the range of 1 to 100 w ία. In the present invention, the above-mentioned layered structure is mostly formed on the outer surface, but it is also preferably formed in the fine pore portion at the same time. The arrangement direction of the layers is mostly parallel to the valve surface. At the same time, a space portion is formed in at least a part of the adjacent layers. The thickness of each layer forming the layered structure is in the range of 0.01 to 5 w®, preferably in the range of 0.01 to 1 lua, and most preferably in the range of 0.1 to Q. 3 w η. The solid electrolyte manufacturing method of the present invention is characterized in that a combination of the above organic anions and other anions is used as a polymer dopant of the polymerizable monomer compound to polymerize into a solid electrolytic layer. Specifically, let the polymerizable military compound represented by the formula (Et) or the formula (IV) be coated with a microporous medium by the action of an oxidizing agent and in the presence of a compound that can be provided with a scrofula. The resulting polymer is oxidized and formed on the surface of the medium as a solid electrolyte. Furthermore, the aforementioned process is performed once for one anode substrate, preferably three to thirty times, to form a dense solid electrolyte layer as desired. For example, one of the more desirable processes is to include IU-ί-^ 丨 installation during the above polymerization reaction (please read the precautions on the back first to write this page.) The Ministry of Economic Affairs Central Standards Bureau is responsible for the work Consumption cooperation Du printed with gold immersion or liquid, the film of the step of dissolving the valve step} Yin is mechanized 2 aerobic (the quality of the liquid is described by the dissolution and the formation of the compound will oxidize , The body contains 2 liquids containing mono-yang in water stains, and the impregnating step dipping step foil contains extremely polar steps, which is the step or 1 2 liquids. The liquid solution after immersion is immersed on top of the immersion ii The liquid solution is immersed on top of the immersion or liquid immersion on the paper The scale of the paper is applicable to the Chinese National Standard (CNTS) ΑΦ specifications (210X 297 mm) 4 3 4 6 u '2 A7 Printed by the Consumer Standards Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs B7 V. Invention Description (21) Another embodiment includes the steps of dipping the anode foil in a solution (solution 3) containing an oxidant and the above-mentioned organic anion, and dipping Collapsed in solution containing polymerizable monomer compound (Solution 4), or impotence The step of immersing in the above solution 4 and then immersing in the above solution 3, or the step of immersing in the above solution 3 and then immersing in the above solution 4. The above solutions 1 to 4 can also be used in suspension respectively. In addition, the above immersion step can also be replaced by coating operation. The solvents of solutions 1 to 4 can be homogeneous or different solvents, and depending on the type of solvent, they can also be used in solution 1 and solution 2 or solution 3 and solution 4. A drying step is added between the steps. In addition, after the solid electrolyte is formed, a step of washing the element with a rhenium solvent or water can be added. The organic solvent for washing is preferably the same solvent used in solutions 1 to 4, but Any other solvent that can dissolve polymerizable military compounds or the above-mentioned fluorene anion compounds and other compounds with anionic properties of dopants can be used. After washing with the above solvents, fluorene anions are not added to the polymer The content of other male masculine males other than M will be reduced. However, as long as the organic male masculine male is contained, it will contribute to the characteristics of the solid electrolytic capacitor of the present invention. In the case of repeated implementation, solid electrolytes with excellent soldering heat resistance (thermal stability) can be easily produced. Capacitors using solid electrolytes made of conventional polypyrrole, etc., have large changes in capacitor characteristics at high temperatures and high humidity, which is reliable Poor performance, but the capacitor provided with the solid electrolyte of the conductive composition of the present invention has excellent thermal stability and good stability in the bark state of inclusions. The present invention contains the organic Yin male and the oxidant-derived The precipitation of the polymer phase of the dopant (anion) is -24- ---- MJ --- 1 .----------------------------------- (Please read the precautions on the back before writing this page) This paper size is applicable to the Chinese National Standard (CNS) Α4 size (210X 297 mm). The consumer cooperation of the Central Standards Bureau of the Ministry of Economic Affairs printed A 7 B7 5. Description of the invention (22), '. It is filled on the surface of the dielectric and inside the pores, so it can form a multilayer thin film stack of the polymer, so as to provide a capacitor with good thermal stability and the dielectric coating is not damaged by the polymer. In addition, the above-mentioned organic anions used in the present invention are better than conventional dopants (such as CIO *-, BF *-, Cl-, S0 «2 ·, benzenesulfonate anion, alkyl-substituted sulfonate anion, etc.) A dopant compound that exhibits excellent thermal stability and stability in the conductive state when a charge-transporting complex is formed with a π-co-fluorene polymer. Therefore, a low-impedance characteristic and excellent heat resistance to spark voltage tests can be obtained. Durable high-performance capacitors. That is, for example, in the organic anion heterocycle, when an alkoxy group is used instead of the Chai-sulfonic acid anion, the electron attraction and water solubility of the sulfonic acid group substituted by the aromatic ring due to the high aromaticity of the naphthalene skeleton In addition, the alkoxy group imparts electrons to Cai Huan, and provides a capacitor having the above characteristics. The organic anions used in the present invention are as follows: U) Alkoxy substituted naphthalene monosulfonic acid anion The alkoxy substituted naphthalene monosulfonic acid used in the present invention has an alkoxy group substituted with a sulfonic acid group on the naphthalene skeleton. Synonyms for substituted naphthalene monosulfonic acid compounds and other substituted tsai monosulfonic acid compounds. Preferred compounds are those in which the hydrogen atom of the naphthalene ring of naphthalene monosulfonic acid is substituted with at least one K of Cl-Cli, especially a straight or branched saturated or unsaturated alkoxy group of Ci-Cs. Specific examples of the compound capable of providing the above-mentioned alkoxy-substituted naphthalene monosulfonic acid anion are compounds having a skeleton of compounds such as naphthalene-1-sulfonic acid, fluorene-2-sulfonic acid and their sulfonium metal salts, ammonium salts, and organic quaternary amine salts. And the hydrogen atom of its naphthalene ring is alkoxy-2 5 ~ This paper size applies the Chinese National Standard (CNS) A4 specification (210'〆297 mm) (Please read the precautions on the back again: write this page- Binding _ order A7 B7 V. Description of the invention (23). A chemically-structured compound substituted on 1 K of λ. That is, C ί-C i 2 is linear or) branched saturated or unsaturated alkoxy Substituted compounds. Examples of useful substituents are methoxy, ethoxy, vinyloxy, propoxy, allyloxy, isopropoxy, butoxy, 1-butenyloxy, pentyloxy, hexyl Acyl, octyloxy, nonyloxy, decoxy and the like may also include alkoxy substituted with a cyclic hydrocarbon group such as cyclohexyloxy or phenoxy. In addition, for example, a sulfonic acid compound in which 2 to 8 positions of a 1-alkoxynaphthalene ring is substituted or a sulfonic compound in which 1 to 3 and 8 positions of a 2-alkoxyfluorene ring are substituted may be Effectively used as the alkoxy-substituted naphthalene monosulfonic acid compound. In addition, a hydrogen atom on the alkoxynaphthalene ring may be substituted with a halogen atom such as F, 01, 81 &gt;, 1, or 0? 3, a nitro group, a cyano group, or the like. U) The sulfonic anion of a sulfonium ring compound (heterocyclic sulfonic anion) The heterocyclic sulfonic acid anion used in the present invention has: a sulfonic acid group on M directly or indirectly through an alkylene group The general term for the female of the heterocyclic sulfonic acid compound with a chemical structure substituted on a heterocyclic ring. The preferable skeleton of the heterocyclic compound includes morpholine, piperidine, piperidine, imidazole, furan, 1,4- Dioxane, benzimidazole, benzothiazole sulfide, benzoisoxazole, benzotriazole and benzofuran substituted skeleton. Preferable examples printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs that can provide the above-mentioned indirect heterocyclic compounds substituted with sulfonic anions are morpholine skeleton compounds: for example, 1-morpholino methanesulfonic acid, 2-morpholinoethanesulfonic acid, 3-morpholinopropanesulfonic acid, 2-methyl-2-morpholinopropanesulfonic acid, 4-morpholinobutanesulfonic acid, 5-morpholinopentane Sulfonic acid, 6-morpholinohexanesulfonic acid, 7-morpholinoheptanesulfonic acid, 8-morpholinooctanesulfonic acid, 9--26- This paper size applies to China National Standard (CNS) Λ4 specifications (210X 297 mm) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (24) Morpholinononanesulfonic acid, 10-morpholinodecanesulfonic acid, 12-morpholinodecanesulfonic acid Acid etc. Piperidine skeleton compounds: For example, 1-pyridinomethanesulfonic acid, 2-piperidinoethaneethanesulfonic acid, 3-piperidinopropanesulfonic acid, 2-methyl-2-nickridinopropanesulfonic acid, 4-pipesialbutanesulfonic acid, 5-piperidinylpentanesulfonic acid, 6-piperidinylhexanesulfonic acid, 7-piperidineheptanesulfonic acid, 8-piperidineoctanesulfonic acid, 9-piperidinononanesulfonic acid, 10-piperidinodecanesulfonic acid, 12-piperidinododecanesulfonic acid, and the like. Piperazine skeleton compounds: for example, piperazine-1,4-bis (1-sulfomethyl), piperazine Sf-1,4-bis (2-sulfoethyl), piperazine M, 4-bis (3- Sulfopropyl), piperazine-1,4-bis (4-sulfobutyl), piperazine-1,4-bis (5-sulfopentyl), piperazine-1,4-bis (6-sulfohexyl) ), Piperazine-14-bis (7-sulfoheptyl), piperazine-1,4-bis (8-sulfoctyl), piperazine-fluorene, 4-bis (9-sulfonyl), piperazine -1,4-bis (10-sulfodecyl), piperazine-1,4-bis (12-sulfodedecyl) acid and the like. Oxazole skeleton compounds: for example, 1- (2-oxazolyl) methane acid, 2- (2-oxazolyl) ethanesulfonic acid, 3- (2-oxazolyl) propanesulfonic acid, 2-methyl 2- (2-imidazolyl) propanesulfonic acid, 4- (2-oxazolyl) butanesulfonic acid, 5- (2-oxazolyl &gt; pentanesulfonic acid, 6- (2-imidazolyl) Hexanesulfonic acid, 7- (2-oxazolyl) heptanesulfonic acid, 8- (2-oxazolyl) octanesulfonic acid, 9- (2-oxazolyl) nonanesulfonic acid, 10- ( 2-oxazolyl) decanesulfonic acid, 12- (2-oxazolyl) dodecanesulfonic acid, etc. Peptan skeleton compounds: For example, 1- (2-furyl) methanesulfonic acid, 2- ( 2-pyranyl) ethanesulfonic acid, 3- (2-furyl) propanesulfonic acid, 2-methyl-2- (2-furyl) propanesulfonic acid, 4- (2-furyl) butanesulfonic acid Acid, 5- (2-furanyl) pentanesulfonic acid, 6- (2-furanyl) hexanesulfonic acid, 7- (2-furanyl-27-) This paper is applicable to national standards (CN'S) Specification Λ4 (210X29? Mm) A 7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (25)) Heptanesulfonic acid, 8- (2-furanyl) octanesulfonic acid, 9- ( 2-furanyl) nonanesulfonic acid, 10- (2-furanyl) decane Sulfonic acid, 12- (2-furanyl) dodecanesulfonic acid, etc. 1,4-dioxane skeleton compounds: for example, 1- (1,4-dioxane-2-yl) methanesulfonic acid, 2- (1,4-dioxane-2-yl) ethanesulfonic acid, 3- (1,4-dioxane-2-yl) propanesulfonic acid, 2-methyl-2- (1,4 -Dioxane-2-yl) propanesulfonic acid, 4- (1,4-dioxane-2-yl) butanesulfonic acid, 5- (1,4-dioxane-2-yl) pentane Sulfonic acid, 6- (1,4-dioxane-2-yl) hexanesulfonic acid, 7- (1,4-dioxane-2-yl) heptanesulfonic acid, 8- (1,4- Dioxane-2-yl) octanesulfonic acid, 9- (1,4-dioxane-2-yl) nonanesulfonic acid, 10- (1,4-dioxane-2-yl) decane Sulfonic acid, 12- (1,4-dioxane-2-yl) dodecanesulfonic acid, etc. Benzoxazole skeleton compounds. · For example, 1-U-benzimidazolyl) methanesulfonic acid, 2 -U-benzoxazolyl) acetamidosulfonic acid, 3- (1-benzoxazolyl) propanesulfonic acid, 2-methyl-2-U-benzoxazolyl) propanesulfonic acid, 4- U-benzoxazolyl) butanesulfonic acid, 5-U-benzoxazolyl) pentanesulfonic acid, 6- (benzobenzoxazolyl) hexanesulfonic acid, 7- (benzophenazolyl) Wowyl) heptanesulfonic acid, 8- (bubenzimidazolyl) octanesulfonic acid, 9- (bu And imidazolyl) nonane acid, 1D- (1-imidazolyl) decanesulfonic acid, 12- (imidazol-1-yl) dodecanoic acid. Benzothiazole sulfur skeleton compounds: For example, 1- (2-benzothiazylthio) methanesulfonic acid, 2- (2-benzothiazolesulfonyl) ethanesulfonic acid, 3- (2-benzoxazole Thio) propanesulfonic acid, 2-methyl-2- (2-benzothiazolethio) propanesulfonic acid, 4- (2-benzoxazolylthio) butanesulfonic acid, 5- (2-benzene Benzothiazolyl) pentanesulfonic acid, 6- (2-benzothiazylthio) hexanesulfonic acid, 7- (2-benzothiazyl-28-) This paper size applies to Chinese National Standard (CNS) Λ4 specifications ( 210X297 mm) 434602 Μ B7 V. Description of the invention (26 azolethio group printed by the Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs) heptanesulfonic acid, 8- (2-phenylchlorothiazylthio) octanesulfonic acid, 9 -(2-benzoxazolium) nonanesulfonic acid, 10- (2-benzoxazolamine) decanesulfonic acid, 12- (2-benzoxazolium telluryl) dodecanesulfonic acid Etc. Benzoisoxazole skeleton compounds: For example, 1- (bubenzoisoxazolyl) methanesulfonic acid, 2- (1-benzoisooxazolyl) ethanesulfonic acid, 3- (bu Benzoisoxazolyl) propanesulfonic acid, 2-methyl-2-U-benzisoxazolyl) propanesulfonic acid, 4-U-benzoisoxazolyl) butanesulfonic acid, 5- (1-benzoisoxazolyl) pentanesulfonic acid, 6- (benzobenzoxazolyl) hexanesulfonic acid, 7-U-benzoisoxazolyl) heptanesulfonic acid, 8- ( 1-benzoisoxazolyl) octanesulfonic acid, 9- (bubenzoisoxazolyl) nonanesulfonic acid, 1G- (bubenzoisoxazolyl) decanesulfonic acid, 12- (1 -Benzoisoxazolyl) dodecanesulfonic acid and the like. Benzotriazole skeleton compounds: For example, 1- (2-benzotriazolyl) methanesulfonic acid, 2- (2-benzotriazolyl) &gt; ethanesulfonic acid, 3- (2-benzotriazole Oxazolyl) propanesulfonic acid, 2-methyl-2- (2-benzotriazolyl) propanesulfonic acid, 4- (2-benzotriazolyl) butanesulfonic acid, 5- (2-benzo Triazolyl) pentanesulfonic acid, 6- (2-benzotriazolyl) hexanesulfonic acid, 7- (2-benzotriazolyl) heptanesulfonic acid, δα-benzotriazolyl) octyl Alkanesulfonic acid, 9- (2-benzotriazolyl) nonanesulfonic acid, 10- (2-benzotriazolyl) decanesulfonic acid, 12- (2-benzotriazolyl) dodecane Lu acid and so on. Benzofuran-based compounds; for example, 1- (3-benzofuranyl) methanesulfonic acid, 2- (3-benzofuryl) ethanesulfonic acid, 3- (3-benzofuryl) propanesulfonic acid Acid, 2-methyl-2- (3-benzofuryl) propanesulfonic acid, 4- (3-benzofuryl) butanesulfonic acid, 5- (3-benzofuryl) pentanesulfonic acid , 6- (3-benzofuranyl) hexanesulfonic acid, 7- (3-benzofuranyl) heptanesulfonic acid, 8- &lt; 3- -29- (Please read the note 1 on the back first '-This page) This paper size applies to Chinese National Standards (CNS) A4 specifications (2ί〇' × 297 mm) A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention (27) Benzofuryl) Octanesulfonic acid, 9- (3-benzyfuranyl) nonanesulfonic acid, 10-ίδ-benzofuranyl) decanesulfonic acid, 12- (3-benzofuranyl) dodecanesulfonic acid, etc. . In addition, the above-mentioned quaternary nitrogen compounds such as sodium sulfide compounds such as sodium or calcium aluminium or ammonium salts can also be used as the above-mentioned compounds that provide anions. Furthermore, the above-mentioned sulfonic acid groups are directly in the heterocyclic ring. Preferred specific examples of heterocyclic compounds substituted on the backbone are 2-imidazolesulfonic acid, furan-2-sulfonic acid, furfur-3-sulfonic acid, 2-benzimidazolesulfonic acid, and benzofuran-3-sulfonic acid. Alkali gold salts, ammonium salts or quaternary ammonium salts such as sodium salts of acids and their compounds. In addition, the hydrogen atom on the heterocyclic skeleton is replaced by C t-C t 2, which is more preferably a derivative of one or more substituted C i-CB straight or branched saturated or unsaturated hydrocarbon groups or alkoxy groups. Used as the heterocyclic sulfonic acid ion. Specific examples of the substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, pentyl, hexyl, octyl, nonyl, dodecyl and the like Or unsaturated groups such as vinyl, allyl, 3-butenyl, 5-hexenyl, and methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, Octyloxy, nonyloxy and dodecyloxy. (3) Anion of aliphatic polycyclic compound The anion heterocycle of the aliphatic polycyclic compound used in the present invention has as many as two or more rings having a protonic acid group (Briinsted acid) such as sulfonic acid or carboxylic acid, phosphoric acid, and boric acid. The compound of the cycloaliphatic yin extract is preferably a sulfonic acid or carboxylic acid-substituted compound, and particularly preferably a sulfonic acid-substituted compound. Specific examples include: d-camphorsulfonic acid (formula X V11) (alias: 1) -Camphorsulfonic acid), 2 _ -30--This paper size is in accordance with the Chinese Standard (CNS) Λ4 specification (2 丨 0X297 mm) (Please read the precautions on the back before continuing on 1 'this page) -Packing— — Order --- r line

A7 B7 One by one _ _ V. Description of the invention (28) Benzenesulfonic acid (Formula XVIII), 3- Benzenesulfonic acid, 8- Benzenesulfonic acid, d-Camphoric acid and derivatives thereof. In use, K is used in the form of its ammonium salt or sickle tincture. (XVII)

(XII) Any oxidizing agent used in the present invention may be used as long as it is oxidatively polymerized with pyrrole or phenanthrenes, such as ferric chloride (H) and Fe (Cl〇4) described in JP-A No. 2-15611. 3 There are arsenic acid (ban), inorganic acid iron (®), alkyl persulfate, ammonium persulfonate, hydrogen peroxide, K2Craor and so on. The above-mentioned organic acid having iron osmate {B) is, for example, methanesulfonic acid or Ci-C21J alkane S sulfonic acid such as dodecylbenzenesulfonic acid or an aliphatic carboxylic acid. However, the use of the above-mentioned oxidant may be limited by the chemical structure of the monomer compound represented by the above formula (If), the oxidant M, and the reaction conditions. For example, the oxidation (polymerization) of thiophenes, according to the description of the Handbook of Conducting Polymers heterojunction (M arce 1 Dekker, Inc · issued, 1 987, pp. 9 9, F ig · 5), according to the substituents Kind of oxidation potential (an indicator of the ease of polymerization) -3 1- This paper size is applicable to the Chinese National Standard (CNS) Λ4 specification (2 丨 OX29 ·; mm) nn ^ — m »1 ^ 1 · *- -..1 ^ 1 -I In---- 1 ^ eJ .......-«-..... t- n ...... HM (Please read the notes on the back first .Zhuangguang ', this page) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 4 3 4 6 Ο 2 A7 B7 Printed by the Consumers' Cooperative of the Central Bureau of Standards of the Ministry of Economic Affairs 5. Printing of the Invention (29) Significant changes (oxidation The potential range is about 1.8 to about 2.7V), and the polymerization reaction is about left and right. Therefore, the combination of the polymerizable monomer compound, the oxidizing agent, and the reaction conditions is extremely important. In the present invention, the anions other than the organic masculine male M that are used as inclusions are the plasmodium male masculine males after the reaction of the above oxidizing agents, such as chlorine chicks, C10 «-, Ct-Cu aliphatic organic carboxylic acid anions, Sulfuric acid male, maleic acid male, Ci-Cu fatty organic phosphate anion, sun acid anion, etc. In addition, NO *, NO〆 salts (such as NOBF *, NOPFs, HOSbFe n NOAsFb 'NOCHs SOs' N 0 2 B F «&gt; NOaPFe' NOa CF3 S03) can also be used. In the manufacturing method of the solid electrolytic capacitor of the present invention, persulfate is most suitable for the chemical polymerization of the thiophenes represented by the above formula (IV). When using the rhenium (I) salt-based oxidant, there is a Residual problems affect the characteristics of capacitors. In addition, the caseinate which is applicable to the polymerizable military compound of the formula (IV) is not applicable to the aforementioned formula U), in which RhRkH and X = S are not applicable. Therefore, the use of an oxidant has its own limitations. Persulfates particularly suitable for chemical polymerization of thiophenes represented by the above formula (IV) are, for example, ammonium persulfate and potassium peracid. The following describes the preferable conditions for the formation (polymerization) reaction of the solid electrolyte: The concentration, oxidant, and the above-mentioned (1) of the polymerizable military compound of formula (H) or formula (IV) used in the method of manufacturing the capacitor of the present invention ) ~ (3) Although the concentration of each organic masculinity dopant varies depending on the type of compound and its substituents or the combination with the solvent, etc., it is usually lx 1 {)-* ~ 10 mol / liter The range is preferably in the range of IX 10-3 to 5 mol / liter. Reverse -32- (* Read the precautions on the back before transcripting this page) -Install the., Βτ line This paper size applies the Chinese National Standard (CNS) Λ4 specification (2i〇X 297)

i. Description of the invention (30) Please read the notes on the back. The temperature of the page should be different according to the ancient method of reaction, so it is difficult to define K, but it is usually -70 t: ~ 25〇υ, more preferably otl ~ 1501C. It is particularly preferable to be 15 ~ lflflt: Fan Qin. The solution used in the manufacturing method of the present invention or the solvent used after polymerization is more preferred. For example, it can be considered to be acid such as tetrakifuramine (ΤΗΠ or dioxane, diethyl ether, etc.), or acetone, dimethyl ethyl ketone, etc. Type, aprotic polar solvents such as dimethyl methylamine (DMF) or acetonitrile, benzyl, N-methylpyrroloquinone (SMP), dimethyl iodide (DMSO), ethyl acetate or butyl acetate Ester esters, non-aromatic atmosphere solvents such as dichloromethane or dichloromethane, nitro compounds such as nitromethane or nitroethane, nitrobenzene, or alcohols such as methanol, ethanol, propanol, etc. Such as formic acid, acetic acid, propionic acid and other organic acids, or mixed solvents of the organic acid anhydride (such as acetic anhydride), water or acetic acid, etc. It is more preferable to use water, yeasts, sprouts and / or their mixed systems. The outline of the structure of the solid electrolytic capacitor of the present invention will be described with reference to FIG. 1 as follows: Printed by the Central Bureau of the Ministry of Economic Affairs—printed by the Industrial and Consumer Cooperatives-The electrode (anode) 1 of the present invention uses aluminum, titanium, group, and niobium Or alloys with a matrix function such as gold alloys, rods or alloys with a matrix as the main component For the purpose of forming a sintered body and other conventional materials, and for the purpose of forming a dielectric layer and increasing the specific surface area, the surface of the gold electrode is subjected to pickling etching or chemical (chemical) treatment according to conventional methods. The gold-based oxide coating layer 3 is formed. For the formation of the solid electrolyte (conductive polymer composition) 4, the method of polymerizing the above-mentioned polymerizable military compound on the dielectric layer should be adopted, and in particular, the one having excellent thermal properties of the present invention is used. The electropolymer composition has fine pores or -33- This paper size is applicable to the Chinese National Standard (CNS) Λ4 ^ grid (2iOX297 mm) 434602 Α7 Β7 Five invention descriptions (31) Staff Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs A method for printing chemical precipitation on the dielectric layer of the void structure. In addition, in order to improve electrical contact, it is best to further provide another conductive layer on the conductive polymer layer formed by the above method, that is, for example, coating and other electrical layers Paste or use electroplating, vapor deposition, Selenium wax film, etc. to form the conductive layer 5. For the solid electrolytic capacitor manufactured according to the above-mentioned manufacturing method of the present invention, 5The upper mold is covered with tree cells or equipped with resin or metal exterior, or the encapsulation body 6 is provided by dipping resin, etc., and then equipped with connection terminals? You can produce solid electrolytic capacitors suitable for various uses. The following examples, comparative examples, and reference examples are used to illustrate the best application form of the present invention. <= Example 1 A 10 weight! K ammonium adipate aqueous solution was used and a voltage of 13 V was applied to cut into the prescribed A large area of aluminum foil (substrate) that has been etched is subjected to a chemical (chemical) treatment so that a dielectric layer is formed on the surface of the aluminum foil (that is, a medium gasification film is formed), and then it is immersed in a solution containing 20 wt. Ammonium (hereinafter referred to as APS) and 0.3 weight: aqueous solution of 2-propoxynaphthalene-6-sodium sulfonate (3Γ), the surface of the medium layer is impregnated with the aqueous solution, and then immersed in 5 g of 3,4- Dioxethylene-thiophene was removed from a 1.2 mol / liter isopropion (hereinafter referred to as IPA) solution (solution 4), and was left for 10 minutes in an environment of 60 1C to carry out oxidative polymerization. After the polymerization was completed, the M was washed with water. This polymerization reaction treatment and washing steps were repeated 10 times each. Subsequently, the conductive polymer layer (solid electrolyte layer) formed in the above was placed in water / IPA solvent for hydrazine reduction and careful extraction. The gallium ion-34- This paper size applies to Chinese National Standard (CNS) A4 specifications (210 × 297 male: t) Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs A7 B7 5. Description of the invention (32) and 2-propoxynaphthalene-6-sulfonate The content of acid ions, as a result of each fully repeating structural unit of the K polymer, the maleic tellurate content was 1.6 mol 3; the 2-propoxynaphthalene-6-sulfonic acid ion contained 1 was 13.6 mol 3 !. The electrical conductivity of the solid electrolyte layer was 75 s / ca. Next, the aluminum foil (substrate) having the above-mentioned thiophene polymer formed was treated in a 10 wt% T X ammonium adipate solution, and its spark pressure was measured. In order to accurately compare the characteristics of the sample components, the number of components is increased (the same is true for the examples below M). That is, under the conditions of sot: environment and a current density of 10 B A / c · 2, 5 times were performed on each of the elements 5; the results are shown in Table i below. Then, the carbon foil and silver paste were coated on the part of the aluminum foil where the conductive polymer layer was formed, and then the cathode lead terminals were connected. At the same time, the anode was welded on the aluminum core portion where the conductive polymer layer was not formed. The lead bat, i is finally sealed with epoxy resin to make a capacitor element. This capacitor element was aged at 125TC for 2 hours, and its initial characteristics were measured. The results are shown in Table 2 below. The C in the initial characteristics in this table represents the capacity, and DF represents the tangent of the loss angle (tanS) (that is, the loss coefficient). These values were measured at 120 Hz. Z represents the sister reactance value at the resonance frequency, and LC represents the leakage current value measured for 1 minute after applying the rated voltage. Each measurement value is an average of 30 capacitor elements. In addition, those of LC series K1 «A or higher are regarded as defective products, and those above 10μΑΜ are represented by short-circuit products. (Example 2) An aluminum alloy (substrate) having a dielectric layer prepared according to the method described in Example 1 was immersed in an aqueous solution (solution 1) containing 20% by weight of ASP, and the surface of the medium was impregnated with the aqueous solution. Re-immersed in 3,4-dioxo-35- with 5 grams dissolved. Applicable to Chinese National Standard (CNS) Λ4 specification (2IOX29V male; only) 1 ^ 1, HH!-I I —Hr «^^ 1 If In In i-! Ml-! I-— —I-eJ ...... I II: mm--* (Please read the note on the back 4? This page) ~ A7 B7 Staff of the Central Bureau of Standards, Ministry of Economic Affairs Printed by a consumer cooperative V. Description of the invention (33) Ethylene-Wanpan 1.2 ears / litre, 2-propoxynaphthalene-6-sulfonic acid tetrabutylammonium salt was added to the IPA solution and the concentration of this salt Adjusted to 0.1% by weight of the obtained IPA / water mixed solution (solution 2). The 2-propoxynaphthalene-6-sulfonic acid tetrabutylammonium salt used at this time is prepared by mixing 2-propoxycaline-6-sulfonic acid sodium and tetrabutylammonium bromide and then crystallizing. Then, the mixed solution (Solution 2) was taken out, and it was left to stand for 10 minutes in an environment of 60¾ for oxidative polymerization. After the polymerization was completed, it was washed with K water. After repeatedly performing this polymerization treatment and washing step for 1 β times, the evaluation results according to the method described in Example 1 are shown in Table 1 and Table 2, that is, the sulfuric acid ion content in the polymer is 2.2 mole%, 2- The content of heteroproton-6-sulfonic acid was 7.5 moles 3, and the conductivity of Gu Zhao electrolyte layer was 58 s / cb. Example 3 An aluminum alloy (substrate) having a dielectric layer prepared according to the method described in Example 1 was immersed in an IPA solution (solution of 1.2 ears / liter of 5 g of 3,4-dioxyethylene-sleepin) in solution. 4) Then, it is immersed in an aqueous solution (solution 3) having an APS concentration of 20 weight and a 2-methoxynaphthalene-6-sulfonic acid concentration of 0.1 weight X. Subsequently, it was taken out and left to stand for 10 minutes in an environment of 80 ° to carry out the oxidative polymerization. After the polymerization was completed, it was washed with K water. After performing this polymerization reaction treatment and cleaning step repeatedly for 10 times, the evaluation results according to the method described in Example 1 are shown in Table 1 and Table 2, that is, the content of male sulfate in the polymer is 1.8 -Methocae-6-sulfonic acid ion content is 0.8 mol 5 !, and the conductivity of the solid electrolyte layer is 6.0s / cn. Example 4 A dielectric layer having a dielectric layer will be prepared according to the method described in Example 1. Aluminum Foil (Base-36- This paper size applies to Chinese National Standards (CNS) A4.C (2! GX297 mm) (Please read the precautions on the back before shoveling on this page).)-1 4 ° Ministry of Economy Consumption cooperation by employees of the Central Bureau of Standards Du printed A7 B7 5. Invention description (34) board), impregnated with potassium per tellurate 10% by weight and 2-methoxynaphthalene-6-sulfonic acid sodium fl.l weight X After the solution (Solution 3), it was immersed in an IPA solution (Solution 4) in which 5 grams of 3,4-dioxyethylene-sleepin 1.2 were dissolved per ear (liter 4). After that, the substrate was taken out and at 60t: Place in the environment for 1Q minutes for free radical oxidative polymerization. After the above immersion step and the polymerization reaction treatment are repeatedly marinated for 10 times, rinse with water. Then evaluate according to the method described in Example 1. The results are shown in Tables 1 and 2. That is, the maleic acid content in the polymer is 5.9 moles X, and the content of 2-methoxynaphthalene-6-sulfonic acid ion is 15.5 moles. The degree is 73s / cb. Example 5 The aluminum alloy (substrate) with a dielectric layer prepared according to the method described in Example 1 was immersed in an aqueous solution containing an APS concentration of 3 to 5 weight X (solution u, and then immersed in a solvent). There are 5 grams of 3,4-dioxyethylene-thiophene 1.2 ears / liter of IPA solution added with 2,3-dimethoxybenzene-6-sulfonic acid tetrabutylammonium salt (Mao 0.04 weight X) of IPA / Water mixed solution (solution γ). At this time, the above-mentioned 2,3-dimethoxynaphthalene-6-tetrabutylammonium tetrabutylammonium was prepared from 2,3-dimethoxycae-6-sulfonic acid sodium and four The butylammonium bromide was recrystallized after being reacted. That is, the substrate was taken out from the above solution 2 and left to stand for 1Q minutes at 60t: environment for oxidative polymerization. Each of the above-mentioned immersion step and polymerization reaction treatment was repeated 10 times. It was washed with water and dried after the second time, and then evaluated according to the method described in Example 1. The results are shown in Tables 1 and 2. The acetic acid ion in the polymer contained the most 5.2 mole X, 2,3- Methoxide -6- The sulfonic acid ion content is 7. Mo takes X, and the conductivity of the solid electrolyte layer is 40 s / c Β. -37- The standard of this paper is applicable to China's national standard (CNS> Α4 specification (2ΐϋ × 297 mm) 4 ", A7 printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs, _ ^ _ B7 V. Description of the Invention (35) Example 6 The aluminum alloy (substrate) I with a dielectric layer prepared by the method described in Example 1 will be used, Impregnated with 1.2 Molars / liter of deaeration of 5, 6-dimethoxyisothioindane obtained by the synthesis and sublimation of the method described in JP-A-Heisei 2-2 4 2 316, a solution of two IPA (solution 4 ), And then immersed in a 20 wt.% APS aqueous solution to which 0.1 wt. X of 2-propoxycae-6-sulfonic acid sodium t-solution (Solution 3) was added. Then, Shanghai Ocean Solvent Co., Ltd. 3 Take out the substrate and leave it for 60 minutes in an environment of 60 ° F to carry out oxidative polymerization. The above-mentioned immersion step, the polymerization reaction place, and the iris were repeatedly performed 10 times, and then washed with K water and dried. It was then evaluated according to the method described in Example 1. The results are shown in Tables 1 and 2. That is, the sulfuric acid in the polymer '«ion content, Dong 0.7 mol: ϊ, 2-propoxycae-6-sulfonic acid ion content Take it for 6.0! Alas, the electrical conductivity of the solid electrolyte layer is 33 s / cm. Example 7 '. Except replacing the 3,4-dioxyethylene-sleep phene solution of Example 1 with the same concentration solution of pyrrole-N-methyl-, the rest is implemented according to the method described in Example 1 and The evaluation results are shown in Tables 1 and 2. The content of androgenic sulfate in the amidine polymer was 7.8 moles. The content of 2-methoxynaphthalene-6-sulfonic acid ion was 12.3 moles. The conductivity of the solid electrolyte layer For 7S / CB. Example 8 The aluminum foil (substrate) prepared in Example 1 was immersed in a solution containing 2-methoxynaphthalene-6-sulfonic acid at a concentration of 0.1% by weight X and 3,4-dioxyethylene-thiophene at 1.2 liters / liter. After 30¾ DMF (dimethylformamide) -IPA solution (Solution 2) / ', and then immersed in a 20 wt% APS aqueous solution (Solution 1). Take out the substrate _ 3 8-(please read the note ^ a ^ item on the back before writing this page)-binding. The paper size of the binding thread is applicable to the Chinese National Standard (CNS) A4 specification (21ϋΧ 297 公 |) Λ Α7 Β7 V. Description of the invention (36) After printed by the Consumers' Cooperative of the Ministry of Economic Affairs, the Ministry of Economic Affairs placed 10 minutes in a 60¾ environment for oxidative polymerization. This dipping step and the polymerization reaction were repeated 10 times each, and then washed and dried. Next, the evaluation results according to the method described in Example 1 are shown in Tables 1 and 2. That is, the content of sulfuric acid ion is 1.5 and the content of 2-methoxyfluorene-6-sulfonic acid ion is 3.2. The electrical conductivity of the solid electrolyte layer is 7 1 s / cm. Example 9 ^ Except that 12 weight 55 was used instead of 20% by weight of APS, the rest was implemented according to Example 1. The evaluation results are shown in Tables 1 and 2. The content of sparse acid ions in the polymer was 0.2 mol X, the content of 2 methoxysulfonic acid ions was 20 mol, and the conductivity of the solid electrolyte layer was 28 s / cm. ^ Example 10 The aluminum foil (substrate) prepared in Example 1 was immersed in a 12¾ IPA solution containing 2-methoxynaphthalene-6-iron (III) sulfonate, and then immersed in 5 g of 3, 4-dioxane. Ethylene-thiophene IPA solution at 1-2 ear / liter concentration. After the substrate was taken out, it was left to stand for 10 minutes in an environment to carry out the oxidative polymerization, and then it was decanted. After repeatedly performing the above-mentioned polymerization treatment and washing steps 10 times, the evaluation results are shown in Table 1 and Table 2 in the same manner as in Example 1. The content of 2-methoxynaphthalene-6-sulfonic acid ion in the polymer is 17 萁! A: The electrical conductivity of the solid electrolyte layer is 30s / cb. Reference Example 1 Except for the use of iron sulfate 10 weight 1¾ instead of APS and the use of 2-methoxynaphthalene-6-sodium sulfonate 0.1 weight 3; It is implemented according to Example 1, and the results are shown in Tables 1 and 2. The content of sulfuric acid ion in the polymer is 24.5 and its ear 5; 2-methoxynaphthalene-6-sulfonic acid heterozygote contains the most 33.8 ear χ, but, from -39- the paper scale is applicable to the Chinese National Standard (CNS) Λ4 specification (2! 0X29? Male) "(Read the note on the back: this page)-installed,? Τ line · 434602 A7 B7 V. Description of the invention (37

Du Yin I, the consumer cooperation of the Central Bureau of Standards of the Ministry of Economic Affairs, has 8 iron ions in the presence of iron ions, and maleic acid content in the maleic acid exceeds ίο Mo Er, so the characteristics of the capacitor are poor. Reference Example 2 Except changing the 3,4-dioxyethylene-thiofluorene used in Example 1 to thiophene, the oxidation of M10 weight Ϊ was used in place of APS and a solution of 2-methoxynaphthalene-6 = sodium sulfonate 0.1 weight X Except that, the rest is implemented according to Example 1, and the results are shown in Tables 1 and 2. The 2-methoxyfluorene-6-sulfonic acid ion content in the polymer was 3.1 Molar X. Because it does not contain sulfate ions, the capacitors have poor properties. Reference Example 3 π. Except that 3,4-dioxyethylene-thiophene used in Example 1 was changed to Phenylphenone *, the rest is true. Example 1 was implemented, but no black-cyan polyacetin was generated at all. That is, the effect of APS cannot make thiophene polymerize. That is, the oxidative polycondensation of phenols according to APS only occurs specifically for 3,4-dioxy-substituted thiophenes. Reference Example 4 'Except that the 2-propoxynaphthalene-6-sulfonic acid sodium used in Example 1 was changed to 2-hydroxynaphthalene-6-sulfonic acid sodium, the rest were implemented according to Example 1', and the results are shown in Table 1 And Table 2. The content of sulfate ion in the polymer was 4.3 moles X, the content of 2-hydroxynaphthalene-6-sulfonic acid ion was 12.1 ears χ, and the conductivity of the solid electrolyte layer was iOs / cm. As can be seen from the table, Examples 1 to 9 showed almost no voltage drop in the spark voltage test, which proves that no damage occurred to the dielectric coating layer. In the case of capacitor 10 using organic iron salt, there is no voltage drop in the spark voltage test, but the reference examples 1 and 2 using inorganic iron salt have a significant drop in voltage, and K ends at the specified number of times. The voltage cannot be maintained before -40- (please read the precautions on the back before 4), the paper size on this page applies the Chinese National Standard (CNS) Λ4 specification (210 X mm)

.-rw. C Λ7 B7 V. Description of the invention (38% dip in immersion. The number of ears used in the ears is 8 and the number has no effect. The damage caused by the damage is greatly reduced. The acid-pressed sulphur electric fruit uses a flower knot to make the fire, and the result will be reduced to 1 example. It is obvious that there are some children, electric flowers, and iron fire asl ^ epitope / IV piezoelectric flower fire. Number of times 1 2 3 4 '· 5 6 8 10 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 18 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 16 19 19 19 19 19 19 19 19 19 19 15 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 Reference example 1 Reference example 2 Reference example 4 19 18 19 16 16 18 14 10 15 7 3 11 3 9 3 I ----- 1-1 * !.-* —-Batch clothing --- (Please read the precautions on the back &gt; 1 ,, write this page) Printed by the Consumers Cooperative of the Central Standards Bureau, Ministry of Economic Affairs 4 Λ Nsc. Standard One-country I-country I, one Rule paper it public 97 2 434602 Α7 Β7 V. Description of the invention (39) Table 2 Initial characteristics C DF Zn LC Number of defectives / Number of samples Short-circuit UF% οΩ uk Example 1 8.1 0.8 60 0.02 0/30 0 Example 2 8.0 0.8 60 0.02 0/30 0 Example 3 7.6 0.8 60 0.02 0/30 0 Example 4 7.0 0.8 60 0.04 1/30 0 Example 5 6.8 0.9 60 0 .05 1/30 0 Example 6 6.8 0.8 60 0.05 1/3 »0 Example 7 4.0 1.3 60 0.11 1/30 0 Example 8 8.2 0.7 60 0.02 0/30, 0 Example S 6.9 0.7 60 0.10 1/30 0 贲 Example 6.9 1.0 60 0.10 1/30 0 Reference example 1 8.1 3.2 83 0.41 15/30 10 Reference example 2 5.S η 0. U 87 0.40 27/30 16 Reference example 4 5.0 1.2 60 0. 10 3/30 0 (Please read first Remarks on the back of the book (Re-treatment of the textbook) Packing ---- Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs Example 11 The Ning foil (substrate) with a dielectric layer formed on the surface prepared according to Example 1 was immersed in Contain APS 20 weight χ, 4-morpholine propane sulfonate sodium (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.125 wt. 5S aqueous solution (solution 3), and then immersed in 5 g of 3,4-dioxane Hope of 1.2 mole / liter ΐρΑ solution (solution 4). After the substrate was taken out, it was left to stand for 10 minutes in a 60 t: environment for oxidative polymerization. After the polymerization was completed, the substrate was washed with M water. The above polymerization reaction treatment and washing steps were repeated 10 times each. The content of sulfate ion and 4-morpholine propane sulfonic acid ion in the conductive polymer is obtained by placing the substrate obtained by the above-mentioned substrate in a water / IPA solvent, and using careful extraction. Ion chromatographic analysis was used to obtain the heterosulfate sulfate and 4-morpholine propanesulfonic acid in the polymer. The content of the polymer was -4 2-^ I _ 1 If ... Applicable to China National Standard (CNS) A4 specification (210X29 '? Mm) 434602 Printed by the China National Standards Bureau of the Ministry of Economic Affairs, Consumer Cooperative Cooperative Association a * A7' B7 V. Description of the invention (4〇) Fully repeated construction military meter, sulfate ion The content is 1.5 moles, 5: 4-morpholine propane sulfonate, and male moles, 14, 0 moles, 5S, and the conductivity of the solid electrolyte layer is 73 S / C 1 ° * mold, the above is formed into 3,4 -Diethylene glycol-Aluminum polymer substrate is placed in an ifl weight of ammonium adipate solution, and its spark voltage is measured. In order to compare the characteristics of the test element for sulfur cutting, increase the number of elements (the following implementation Example is the same). That is, under the conditions of a 50Ό environment and a current density of 11) πΑ / cm2, the number of components π = 5 is implemented (that is, the 5 涸 components are implemented), and the results are shown in Table 3. '' Then apply carbon paste to the portion of the upper foil where the conductive polymer is formed. After the silver mallet, connect the cathode lead terminal, and at the same time, the aluminum core without the conductive polymer layer is formed. The anode lead terminals were soldered to the outside, and finally sealed with epoxy resin to obtain a capacitor element. This capacitor element was heated at 1 2 5 υ for 2 hours, and its initial characteristics were measured. The results are shown in Table 2 below. The initial characteristic C in this table represents capacity, and DF V represents the tangent UaaS of the loss angle (that is, the loss coefficient). These values are measured at 120 Η z. Z represents the sister reactance value at the resonance frequency, and L C represents the leakage current value measured at a nominal voltage for 1 minute. Each threshold value is an average measurement of 30 capacitor elements. In addition, the LC system M i «AK is regarded as a defective product, and the 10 AM above M short circuit product is indicated. Example 1 2 An aluminum foil (substrate) having a dielectric layer formed on its surface prepared by the method described in Example 11 was immersed in an aqueous solution (solution 1) having an APS concentration of 20% by weight, and then immersed in 3, 4 with 5 g -Dioxyethylene-thiophene 1.2 Molars / litre-43- Please read the precautions on the back again-1 / k The paper's dimensions on this page apply to Chinese national standards (CN'S &gt; Λ4 specifications (2! 〇 &gt; + 297 mm>, Η. / Economy 'Deng Zhongyang likes Malaysian consumer consumption cooperation · Du India bags · * 1- ♦ 4

B7__ 5. Description of the invention (41) Add 4-morpholine propane sulfonate tetrabutylammonium sulfonium (M hereinafter referred to as M OP STB salt) to the IPA solution and adjust its degree to 0.1 wt. 2 IPA / water mixed solution (Solution 2) . The above-mentioned MOPSTB salt was obtained by recrystallization by using 4-morpholine propane sulfonate (manufactured by Tokyo Kasei Co., Ltd.) and tetrabutylammonium bromide in a mixed reaction. After taking out the substrate, it was left to stand for 1 G minutes in a 60 ° environment for oxidative polymerization, and then washed with water. The above polymerization reaction treatment and washing steps were performed 1G times each, and the capacitor element was evaluated according to the method described in Example 11. The results are shown in Table 3 and Table 4. The sulfuric acid ion in the polymer is 1.6 and its ear X The content of the 4-exhaustline propanesulfonic acid ion was S.1 mole, and the conductivity of Guya electrolyte was 5 6 s / c ffl. _Example 1 3 The aluminum rhenium substrate (substrate) prepared in the same manner as in Example 11 was immersed in a solution of 5 grams of 3,4-dioxyethylene-thiophene 1.2 ears / liter of IPA solution (Solution 4) Then, it was immersed in an aqueous solution (solution 3) having a concentration of 20% by weight of APS) and a fl.l% by weight of 4-morpholine propanesulfonic acid. After taking out this substrate, it was allowed to stand in a 60C environment for 10 minutes for oxidative polymerization, and then washed with water. The above polymerization reaction treatment and washing steps were repeated 10 times each, and the resulting capacitor element was evaluated according to the method described in Example 11. The results are shown in Tables 3 and 4. The content of sulfate ion in the polymer was 2.0 moles: the content of U, 4-morpholine propanesulfonic acid ion was 0.8 mole%, and the electrical conductivity of the solid electrolyte layer was 60 s / cia. Example i 4 I The aluminum foil (substrate) prepared in the same manner as in Example 11 was immersed in an IPA solution (-44- present) in which 5 g of 3,4-dioxyethylene-thiophene 1.2 was dissolved. The paper size applies the Chinese National Standard (CMS) Λ4 specification (2: 0: &lt; 297 mm) (please read the note on the back Ϋ-for refilling. ¾ this page) — ^ ϋ 1 ^ 1 m UK In leJ I ----- —I— 1 line --- 43460 a Α7 Β7 .The consumption cooperation of staff of the Central Economic Standards Bureau Du printed five. Description of the invention (42) Solution 4), then immersed in APS concentration 20 Weight: 1 and an aqueous solution of 4-morpholineethanesulfonic acid with a concentration of 0.3 weight X (solution 3). After taking out the substrate, it was left to stand in a 60 ° environment for oxidative polymerization, and then washed with M water. The above polymerization reaction treatment and washing steps were repeated 10 times each, and the resulting capacitor element was evaluated according to the method described in Example 11, and the results are shown in Tables 3 and 4. The content of sulfate ion in the polymer was 2.1 mole J; the content of 4-morpholine acetamidine sulfonic acid ion was 0.8 mole X, and the conductivity of the solid electrolyte layer was 60S / CB ». Example 15-The aluminum foil (substrate) prepared in the same manner as in Example was immersed in a solution containing 10% by weight of potassium persulfate and sodium 4-morpholine propanesulfonate (manufactured by Tokyo Chemical Industry Co.). Solution 3), and then immersed in a 1.2 mol / liter IPA solution (solution 4) in which 5 g of 3,4-dioxyethylene-oxaphene was dissolved (solution 4). After taking out the substrate, place it in 6 01: environment After 10 minutes of oxidative polymerization, M was washed with water. The impregnation and polymerization treatments described above were repeated 10 times each, followed by washing and drying with water, and evaluation of the resulting electric and container components according to the method of Example 11. The results are shown in Tables 3 and 4. The polymer had a sulfate ion content of 6.2 mol X, 4-morpholine propane sulfonic acid ion content of 15 mol X, and the electrical conductivity of the solid electrolyte layer was 74 s / cb. Example 16 An aluminum foil (substrate) prepared in the same manner as in Example 11 was immersed in 5, 6-dimethoxy-isoprepared and synthesized by the method described in Japanese Patent Application Laid-Open No. 2-2 4 28 16 and sublimated. Sulfide of 1.2 Molars / liter degassing concentration I ρ Αsolve * 45 ~ m HI. Λ 1 m ~ I — tmt (Please read the precautions on the back before ^-this page) Applicable to paper size China National Standard (C1SS) Λ4 specification (· 2 丨 0) &lt; 297 seats) A7 B7 printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs (5) Invention Description (43) Liquid 4), and then immersed in 20 X. The concentration of the aqueous solution of APS contains 0.1% by weight of 3; the degree of morpholine propane sulfonate solution (solution). The substrate was taken out and left to stand for 10 minutes in a 60 ° F environment for oxidative polymerization. After repeatedly performing the impregnation and polymerization reaction treatment of the upper loop 10 times, K was washed and dried, and the obtained capacitor element was evaluated according to the method of Example 11. The results are shown in Tables 3 and 4. The gallate ion content in the polymer was 0.8 mol 35, and the heteromorphic content of 4-morpholinpropanesulfonate was 5.7 and its ear J; the conductivity of the solid electrolyte layer was 31 s / cb. Example 17 Except that M-pyrrole-N-formamidine was substituted for 3,4-dioxyethylene-thiophene, the rest was carried out according to Example 11, and the evaluation results of the obtained capacitor elements are shown in Tables 3 and 4. The content of sulfate ion in the polymer was 6.8 mol 3: and the content of 4-morphopropane acetic acid ion was 16 · 8 mol 3: and the conductivity of the solid electrolyte layer was 7s / cib. The aluminum foil (substrate) prepared in the same manner as in Example 11 was impregnated with sodium 4-morpholine propane sulfonate at a concentration of 0.1% by weight 5: and 3,4-dioxyethylene-thiophene at a concentration of 30% DMF-IPA (LMF After solution 2), it was immersed in 20% by weight APS aqueous solution (solution 1). After taking out the substrate, it was placed in a 60Ό environment for 10 minutes for oxidative polymerization. The above-mentioned immersion and polymerization reactions were performed repeatedly. After 10 times washing and drying, and evaluating the capacitor element obtained according to the method of Example 11, the results are shown in Table 3 and Table 4. The content of sulfate ion in the polymer was 1.7 mole%, and 4-morpholine propanesulfonic acid The dimensional content is 32, and the solid electrolyte layer of the ear is -46- ---- J --------- installation ------ order ------- line 1— &lt; · ί (Please Please read the precautions on the back before you read this. Write this page) This paper size applies to China National Standard (CNS) A4 (2 丨 OXM: 7mm) Printed by the Intellectual Property Bureau Staff Consumer Cooperatives . * 1 * · A7 B7 V. Description of the invention () The electrical conductivity of j is 75s / c in. Example 19 Except the 20 weight used in Example 1 5 5! APS changed to 12 weight XAPS 9 rest It is implemented according to Example 11. The evaluation results of the obtained capacitor element are shown in Tables 3 and 4. 0 The polymer has a sulfate ion content of 0.16 mol% and a 4-morpholine propanesulfonic acid ion content of 25 mol. X, the electric conductivity of the solid electrolyte layer is 34 s / cm. Example 20 Except replacing 4-soline sodium morpholine propane sulfonate with 2-benzoxazole propane sulfonate, the procedure was carried out in accordance with Example 11. The evaluation results of the capacitor element are shown in Tables 3 and 4. The content of sulfate ion in the polymer ^ 1.8 mole%, the content of 2-benzimidazolepropanesulfonic acid ion was 14.5 mole%, and the conductivity of the solid electrolyte layer was 70 s / c curse. Example 21 Except that M4-methyl-1-piperazine methanesulfonate replaces sodium 4-morpholine propanesulfonate, the rest are carried out according to Example 11. Evaluation of the capacitor element produced The results are shown in Table 3 and Table 4. As shown, the content of sulfuric acid ions in the polymer was 20% by mole, the content of 4-methyl-1-piperidinesulfonic acid ion was 16.5% by mole, and the conductivity of the solid electrolyte layer was 65s / cm. Example 22 is implemented in accordance with Example 11 except that M 2, 3-benzofuran-3-sulfonate is used instead of sodium 4-morpholine propane sulfonate). The evaluation results of the obtained capacitor components are shown in Tables 3 and 4. The content of sulfuric acid ion in the polymer is 1.9 mole%, 2,3-benzo benzoate-the content of 3-sulfonic acid ion is 15.8 mole%, solid-47- (Please read the note on the back first Please fill in this page again for this matter) This paper size is applicable to China National Standard (CNS) A4 specifications &quot; (210 χ 297 mm) 4346 0 2

Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (45) The conductivity of the body electrolyte layer is 61s / cm. Comparative Example 1 Except that K thiophene was substituted for 3,4-dioxyethylene-thiophene as a monomer compound and a chlorinated block of M 1Π weight X was used instead of APS, and sodium 4-morpholine propane sulfonate 0.1 weight X Except for preparing the aqueous solution, the rest are carried out in accordance with Example '11. The evaluation results of the obtained capacitor elements are shown in Tables 3 and 4. The content of 4-morpholine propanesulfonic acid ion in the polymer was 2.5 moles; Since no sulfate ion is used in combination, the defective rate of the capacitor is high. Comparative Example 2 The aluminum ig (substrate) prepared in the same manner as in Example 11 was immersed in a 12X IPA solution of 4-morpholinpropanesulfonic acid (III), and then immersed in 5 g of 3,4-diamine. Oxyethylene-Phenan 1.2 in its ear / liter IPA solution. After taking out the substrate, it was left to stand in a PC environment for 6 minutes for oxidative polymerization, and then washed with water. The above polymerization reaction and cleaning steps were repeated 10 times each. The content of 4-morpholine propanesulfonic acid ions in the polymer is based on The above polymer was placed in a water / IPA solvent, and the hydrazine primordial gold was carefully extracted and determined by _ raccoon chromatographic analysis. The result 4-acid acetonide acid ions content was 15 based on the polymer's total repeating structural unit. The electrical conductivity of the Mohr solid electrolyte layer was 35 S / CB. The capacitor element was fabricated using the aluminum foil with the conductive polymer layer formed as described above, and the spark voltage and other capacitor characteristics were measured according to the method of Example 11. The results are shown in Table 3. The results are shown in Table 4. Comparative Example 3 Except that 10% by weight of K ferric sulfate was used instead of 20% by weight of APS and 0.1% by weight of 4-morpholine propane sulfonate was used. 48- The size of this paper applies Chinese National Standard (CNS) Λ4 specification (2 丨 GX 297 mm) C Please read the legal notice on the back 1 / ¾ Ben Guan-installation line 4 3 4 A7 B7 Five 'invention description (46 ) The evaluation results of the obtained capacitor components are shown in Table 3. The results are shown in Table 4. The content of sulfate ion and 4-morpholine propionatesulfonic acid ion in the polymer was calculated according to the method described in Example 11. The content of sulfate ion was I9.6 Moore X, 4-morpholine. The content of propane sulfonate is 3 u Moore X. However, because of the presence of 8 Moore X in iron ions, and the presence of uric acid heterodons exceeding 10 Moore, the failure rate of the capacitor is high. 0 The spark voltage test of Examples 11 to 22 There was almost no voltage drop, and the spark voltage at the end of the reaction was all 19 V Μ. Therefore, in the case of using iron sulfate in Comparative Example 3, 8 moles of iron impurities remained, so the spark voltage dropped. The spark voltage drops before the end of the prescribed reaction, so that the solid electrolyte cannot be filled sufficiently. Reference Example 5 Except replacing 3,4-dioxyethylene-thiophene with thiophene, the rest is carried out according to Example 11 Capacitor element, but no black-cyan polythiophene polymer at all, shows that the polymerization of thiophene does not occur due to the action of APS. That is, the oxidative polymerization of sialones of APS is only for 3,4-dioxy Substituted thiophenes are specific. ~ ---- ^-^ --- Γ 装------ Order ----.----- line- »(Please read the notes on the back before` `· this page ''. Printed by the China Ministry of Economic Affairs and China Standards Bureau Shoulder Workers Cooperatives- 49- The paper scale is applicable to China's National Standard (CN'S) A4 (210 X 297 mm) 7 Β V. Description of the invention (47) Epidemic list / 1% Press Β Lease firework 5 II η Number of element response times 1 2 3 4 5 6 8 10 Example U Example 1 2 Example 13 Example 14 Example 15 Example 16 Example 1 7 Example 18 Example 1S Example 20 Example 21 Example ME 22 19 19 19 19 19 19 19 19 19 19 19 1 9 19 19 19 19 19 19 19 19 13 19 1 9 19 19 19 19 19 19 19 9 19 19 19 19 19 19 19 19 19. 19 18 19 19 19 19 19 19 1 9 19 19 19 19 17 19 19 19 19 19 19. 19 19 19 19 19 19 14 19 19 19 19 19 19 19 19 19 19 19 12 19 19 19 19 19 19 19 19 19 19 19 10 10 19 19 19 19 19 19 19 19 Comparative Example 41 Comparative Example 2 Comparative Example 3 18 19 19 14 16 16 10 i2 12 3 5 3 2 4 Please refer to the table I first I read I read: back I surface j- 1 {Item I reprint% Initial characteristics of Standard Bureau employee consumer cooperatives C DF Zn LC Defective number / Number of samples short-circuited u F 96 βΩ UA ^ / one Example 11 8.0 0.6 60 0.02 0/30 0 Example 12 8.2 0.7 60 0.02 0/30 0 Example 13 7.9 0.8 60 0.03 0 / 30 0 Example 14 7.2 0.8 60 0.03 0/30 0 Example 15 7.0 '0.9 60 0.05 1/30 0 Example 16 7.0 0.9 60 0.05 1/30 0 Example Π 4.0 1.3 60 0.09 1/30 0 Example 18 7.9, 0.8 60 0.03 1/30 0 Example 19 7.0 0.7 60 0.08 1/30 0 Example 20 7.9 0.6 60 0.03 0/30 0 Example 21 7.9 0.7 60 0.03 0/30 0 Example 22 7.8 0.8 60 0.02 0/30 0 Comparative Example 1 5.8 3.2 90 0.44 27/30 19 Comparative Example 2 7.1 1.2 60 0.16 11/30 9 Comparative Example 3 6.0 3.2 83 0.40 14/30 10 ο 5 The paper size applies to the Chinese National Standard (CNS) Eight 4 specifications (210 × 297 male cliff) line 4346 0

A7 B7 V. Description of the invention (Example) 23 An etched aluminum foil of a predetermined size is placed in a 10% by weight aqueous solution of ammonium adipate, and a voltage of 13V is applied to form a dielectric layer on the surface. Zhanzhi, the aluminum foil was immersed in an aqueous solution (solution 1) containing 20 weight of APS and 0.2 weight of sodium d-camphorsulfonic acid (solution 1), and then immersed in 5 g (1.2 mol) of 3,4-dioxyethylene-thiophene / L) isopropionase (IPA) solution (Solution 2), remove it, place it in 6010 environment for 1Q minutes to carry out oxidative polymerization, and then wash with .M water. The polymerization reaction treatment and the washing treatment of the upper loop were repeated 10 times each. '' The above polymer was placed in a water / IP A solvent, and the hydrazine proton was extracted and extracted. The ion chromatographic method was used to determine the sulfate ion and d-camphorsulfonic acid ion in the polymer. The unit-based sulfate ion content was 1.5% by weight, and the d-camphorsulfonic acid ion content was 17% by weight X. The conductivity of the solid electrolyte layer was 7 Qs / cm. In addition, the aluminum core for anode current collection is welded to the positive (+) side lead terminal, and the negative (-) side lead terminal for cathode current collection is connected via carbon paste and silver paste, and finally sealed with epoxy resin. Preparation of capacitor components. This capacitor element was subjected to 125 t: aging treatment for 2 hours, and its initial characteristics were measured. The results are shown in Table 5. The capacity and loss coefficient (tan 5) of the initial characteristics in Table 5 are both measured by 1 2 0 Η z. The impedance is measured at M. Resonant frequency. Leakage current (LC) is the value measured after one minute of curing and rated voltage. Each measurement value is an average of 30 试样. Leakage current K exceeding 1w Α is regarded as defective (short circuit), and defective products are eliminated to obtain the average tC value. The results of the moisture resistance test are shown in Table 6. In this Table 6, except that the LC value 10w AM is regarded as a short-circuit (defective) product, the other values are the same as the initial value -5. China National Standard (CNS) A4 specification (210 X 297 mm) ------- l · I --- K --- 1-'clothing -------- order ·, 1 --- ---- J (Please read the note on the back? Matters before filling out this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs? Take A7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Sample of Invention (49). This humidity resistance test is a real defect of 500 hours under high temperature and high humidity of 85Ό ^ 85 RHX. The reflow test (also referred to as "welding heat resistance test") is evaluated according to the following method. That is, 30 capacitor elements (samples) are allowed to pass through at 30 ° C for 30 seconds, and the rated voltage is measured. A component with a rolling leakage value after minutes, which has a measured value of 0.04 CVUA or more, is regarded as a defective product. The number of defective components and the presence or absence of a short circuit were investigated for 30 components, and the results are shown in Table 6. 贲 例 24 Except M Except 2-camphor-ammonium sulfonate instead of d-camphorammonium sulfonate, the rest is implemented according to Example 2 3. The evaluation results of the capacitor element obtained are shown in Table 5 and Table 6. Sulfate ion in the polymer The content is I.9 and its 9 35,2_ camphor sulfonate content is 14 mol%, and the conductance of the solid electrolyte layer is 45 S / C BI. Example 25 In addition to Md-camphor carboxylate sodium replacing d-camphorsulfonic acid Except for ammonium, the rest is implemented in accordance with Example 2 3. The evaluation results of the capacitor elements obtained are shown in Table 5 and Table 6. The content of sulfate ion in the polymer is 4.7 glutamate 3; The male content was 4.3, and the conductivity of the solid electrolyte layer was 1 〇s / ci 〇 Example 26. Except Except that potassium persulfate replaces APS and KN-methylpyrrole replaces 3,4-dioxyethylene-salene, the rest is implemented according to Example 23. The evaluation results of the capacitor elements obtained are shown in Table 5 and Table 6. The content of sulfate ion in the polymer is 6.8 moles: the content of K, d-brainsulfonic acid males is 11 moles 2, and the conductivity of the solid electrolyte layer is 2 0 s / cb. HH —ϋ »ί an--HI n ^ i ^ mi · {1 i mi 一-· (mn ^ —----i m- &lt; _ US. Ί 麦 (Please read the notes on the back before lii. this page) A paper scale Applicable to China National Standard (CNS) A4 specification (2 丨 0 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 V. Description of the invention () Example 27 Except for the preparation of conductive polymers according to the following method In addition, the rest are implemented according to actual implementation 23, and the capacitor element was evaluated according to the same method as in Example 23. The results are shown in Table 5 and Table 6. _ Dipping the aluminum alloy (substrate) with a dielectric film on the surface After 3-dichloro-5, -6 dicyanobenzoquinone (hereinafter referred to as DDQ) 10% by weight and d-camphorammonium sulfonate 0.1% by weight dioxane solution (solution 1) Then immerse it in an IPA solution (Solution 2) in which 5 g of isothiosulfate (1.2 hare / liter) was dissolved. Then, take out the substrate and place it in the environment for 30 minutes for oxidative polymerization, and then wash the M dioxane and water in order. The polymerization reaction treatment and washing steps were repeated 10 times respectively. The d-camphorsulfonic acid ion content in the polymer was 11-5 moles, and the electrical conductivity of the solid electrolyte layer was 18 s / cm. Example 28 The procedure was carried out in accordance with Example 23 except that 10% by weight of M ferric sulfate was used instead of the APS preparation solution. The evaluation results of the obtained capacitor elements are shown in Tables 5 and 6. The polymer had a sulfate ion content of 23 mole% and a d-camphorsulfonic acid ion content of 14 mole%. However, since 11% by weight of iron is present, the capacitor characteristics are not satisfactory. Example 29 Except the use of 10 weight of ferric chloride instead of APS to prepare an aqueous solution of 0.1 d of sodium d-camphorsulfonate, the rest was carried out in accordance with Example 23. The evaluation results of the obtained capacitor elements are shown in Tables 5 and 6. The d-camphorsulfonic acid ion content in the polymer was 2.3 萁. Since no sulfate ion is contained, the capacitor characteristics are not ideal. -5 3-This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) ------ Line coffee 5. Description of the invention (si A 7 B7 Table initial characteristics C (u F) DF (96) Z (Ω) LC (u A) Defective rate defective number / trial kneading number short circuit Example 23 5.2 0.8 26 0.04! 0/30 0 Example 24 5.3 0.9 24 0.04 0/30 0 Example 25 5.0 1.0 32 0.05 1/30 0 Example 26 4.8 1.1 40 0.06 2/30 0 Example 27 4.7 1.2 50 0.08 2/30 0 Example 28 5.4 0.6 25 0.08 1/30 0 Example 29 4.5 1.4 52 0.05 2/30 0 Table 6 Reflow test Wetting test defect rate number of short-circuit defects / number of samples LC defect rate short-circuit UA) Number of defectives / number of samples 3 4 5 6 7 8 9 2 2 2 2 2 2 2 Examples Example Example Example Example Application Example Pickle Application Example Mι ρι Λί — tl rtn 8 9 8 2 2 2 2 2 /////// 0 0 0 2 12 2 ο ο 3 3 ο ο ο ο ο 4 6 0 5 0 5 4 112 2 3 3 8 ooooooo 0 0 9 6 7 7 6 3 3 2 2 2 2 2 / / / / / / / 0 0 0 110 2 0 0 0 0 10 2 Example 30 An aluminum box with a solid electrolyte layer formed by the method of Examples 1 to 10, Examples 11 to 22, and Examples 23 to 29 was investigated using a scanning electron microscope M5,000 magnification. As a result of cross-section, almost all of the surfaces inside the fine pores of the dielectric body of the aluminum foil were covered with the layered structure of the conductive polymer, and it was confirmed that there was space between the layers of the layered conductive polymer -5 4------ : --- *-, j T National Standards (CNS) Λ4 is now available (2 丨 0 X 297 mm)-{Please read the precautions on the back before you get to know? 'This page)

434602 A 7 B7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. The invention description (52) Department exists. For example, as shown in Figure 2, the foil cross-section photograph of Example 1 shows that the thickness of the conductive polymer layer formed on the outer surface of the microporous structure is 5 W η, and the thickness of each layer forming the layered structure is about 0. · 1 ~ 0.5 win range. In addition, it can be seen from the above-mentioned enlarged bet of the fine pore portion of the aluminum foil that although the electroactive polymer completely covers the surface inside the fine pore, there is still a space portion in this portion. As described above, since the solid electrolytic capacitor and the manufacturing method of the present invention are such that the solid electrolyte of a conductive polymer having a ττ electron conjugated structure contains an anion selected from (1) an alkoxy-substituted naphthalenesulfonic acid anion, (2 &gt; It is characterized by at least one organic anion of a heterocyclic sulfonic acid anion and (3) an anion of an aliphatic anti-cyclic polycyclic compound as a dopant, and containing other anisotropic compounds with the properties of a dopant, so it can provide Small, high-performance solid electrolyte capacitors with low impedance and / or excellent spark voltage resistance. In addition, the solid electrolytic capacitor of the present invention uses a specific polyfluorene ring compound as the solid electrolyte, and in particular, it is replaced by a dioxetyl group. Electrolytic-Polythiophene-type, so it has the effect of greatly improving the voltage characteristics (spark voltage test), high frequency characteristics, tanS, anti-resistance characteristics, leakage current, heat resistance (reflow) or durability. Especially in The above-mentioned conductive polymer contains the above-mentioned organic anion in the range of 0.1 to 50 mole X, and also contains the sulfate ion in the range of 0.1 to 10 mole%. We provide solid electrolytic capacitors with high-performance capacitors. 5 5-(Please read the precautions on the back and then this page)

Dongyou 7 long scale applies Chinese National Standard (CNS) Λ4 is present (210X297 mm) 4346 02 A7 B7 V. Description of the invention (53) _ simple explanation of the formula Figure 1 shows the invention using the valve action gold foil A longitudinal cut-away view of a representative capacitor; FIG. 2 is a scanning electron microscope photograph of the aluminum foil surface with a fine structure formed with a conductive polymer layer prepared in Example 29 (5,000 times). 1 ·. ·. Etching metal hafnium (anode) 2 — pores 3 — — oxidation coating layer (dielectric layer) • 4 — solid electrolyte (conductive polymer) 5 — — conductive layer S — encapsulation 7——Connection terminal (please read the precautions on the back before filling it out. ¾ 'This page-installation — printed by the staff consumer cooperative of the Central Bureau of Standards of the Ministry of Economics-56- This paper size applies to Chinese national standards (CNS ), 44¾ grid (2I0X297 mm)

Claims (1)

No. 88 1 0 8 2 3 Patent application of the Republic of China ^^ year "on January 21 amended the scope of the application patent 1 ·-a kind of π electron conjugated structure formed on the dielectric oxide film. Electrical polymer composition The physical layer of the solid electrolytic capacitor is characterized in that the polymer composition layer contains at least one K selected from (1) a saturated or unsaturated alkoxy group having a linear or branched chain of 1 to 12 carbon atoms. The substituted alkoxy substituted naphthalene monosulfonic anion; (2) a sulfonic anion of a heterocyclic compound having a 5- or 6-membered heterocyclic ring (hereinafter referred to as a heterocyclic sulfonic acid anion); and (3) At least one organic anion of the anion of an aliphatic polycyclic compound is used as a dopant. ---- 丨:-~ Equipment | (Please read the precautions on the back before drawing), Straightener capacity 2 0 7 Solution 1 ~ The electrical description of Guyuan's carbon is from the item $ 1 Ning Di Yin Wei Fan Fan The application of this application is mixed with 2 as the alkane in the replacement of M 1 as low as the basic oxygen Alkane and zeolite are not shaded or acid and sulfonium are replaced by naphthalene chain or radical oxygen, original halogen capacity is selected by electricity The solution is produced by the electric system, Guyuan's hydrogen ring, the family Xiangxiang 2 fragrant acid vansulfuric acid, a special naphthalene, please apply for it on behalf of the basic oxygen 3 burned J printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Substitute alkane for is. Substitute for is species 1 as low as middle methyl halides. Basic acid cyanosulfur, 0 basic nitrate, basic oxygen container capacity 0 '. Electron dissociation of anion and acid. As the item 1 is away from the shade of the fan, it is beneficial for the applicant to apply for miscellaneous materials. If it is mixed with 4, the paper size of the paper is in accordance with the Chinese National Standard (CNS) Α4 size (210 X 297 mm) Ε6 F6 434602 5 The solid electrolytic capacitor according to item 4 of the scope of the patent application, wherein the heterocyclic skeleton of the heterocyclic sulfonic acid anion is selected from the group consisting of?, Piperidine, morphazine, wezodazole, furan, and 1,4-diamine. Chemical compounds of the chemical structures of oxane, benzimidazole, benzothiazole sulfur, benzoisoidazole, benzotriazole and benzofuran. 6. Solid electrolytic capacitors as described in item 4 of the scope of patent application, wherein The heterocyclic sulfonic acid anion is in its chemical structure Contains more than one alkylsulfonic acid substituent. 7. The solid electrolytic capacitor according to item 1 of the scope of the patent application, wherein the organic anion-based aliphatic bicyclic polycyclic compound is used as a dopant. 8. Such as The solid electrolytic capacitor according to item 1 of the scope of the patent application, wherein the organic anion is contained in the range of 0.1 to 50 mol χ to the full repeat of the conductive polymer. — 9. If the scope of the patent application is item 8 1〜10 莫耳 S: Range. The solid electrolytic capacitor, in addition to the organic anion K described above, also contains a prionite anion with an oxidant having a dopant property of 0.1 to 10 mol S: range. 10. The solid electrolytic capacitor according to item 9 of the scope of the patent application, wherein the reducing anion of the oxidant is a sulfate anion. -2- This paper size is applicable to China National Standard (CNS) Α4 specification (210X 297 mm) --------- Ί—r .— ^ 装 J ----- 1r ---- ^ --- Line 丨-^ (Please read the precautions on the back to save and print) Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 4346 0 2 E6 F6 11. Solid Electrolysis as described in Item 1 of the patent application park The capacitor, wherein the conductive polymer of the conductive polymer composition layer contains a repeating structural unit represented by the following formula (I): In the printed format of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, each of the independent groups R1 and R2 is represented by hydrogen, (U-Cb linear or branched saturated or unsaturated hydrocarbon group, or (h-Cs straight or Any one of the branched saturated or unsaturated alkoxy, hydroxyl, halogen, nitro, cyano, trihalomethyl, phenyl, and substituted phenyl groups; and the above-mentioned substituents R1 and R2 can be combined with each other at any position to form at least one divalent chain to form a saturated or unsaturated ring of 5 to 7-membered ring on at least one M. like structure; X represents heteroatoms S, 0, Se, Te or NR3, where 1 ^ is G-Ce straight or branched saturated or unsaturated hydrocarbon group, phenyl, or (h-Ce straight or branched chain saturated or unsaturated alkoxy group; and Rt The alkyl and alkoxy groups of R2, R3 and R3 may optionally contain a carbonyl bond, an ether bond, an ester bond, a hydrazine bond, and an imino bond; and 3 represents 0 to 1. 12. As for the scope of patent application The solid electrolytic capacitor in item 11, in which the repeated structural unit of formula (I) is as shown in the following formula (II): (Please read the precautions on the back before drawing) This paper applies 1T-scale Chinese National Standard (CNS &gt; Α4 specifications (210Χ297 mm) 43460 2 E6 F6 OR5 (II) In the formula: each of the substituents R4 and Rs independently represents a linear or branched saturated or unsaturated hydrocarbon group of C i-C e or a hydrocarbon group of L-Cb mutually at any position. Combined to form a substituent having a heterocyclic structure of 5 to 7 sections on at least one μM of two oxygen atoms described in the formula; and the range of forming the above-mentioned ring structure includes substitution of vinylene group or substitution of 0-phenylene group, etc. Chemical structure; S stands for 0 ~ 1 0 ′ 1 3 · —A solid of conductive polymer composition layer containing #contained on the dielectric oxide film as described in item 1 of the scope of patent application; r electron conjugated structure The manufacturing method of an electrolytic capacitor is a method of polymerizing a polymerizable monomer compound by an oxidizing agent on a P-oxide film, and includes the following features: making the polymerizable monomer compound represented by the following formula (III): (III) (formula : Medium: The substituents Ri, R2, and X are the same as those defined in the above formula (I)) -4-This paper uses the Chinese National Standard (CNS) A4 specification (21 × 297 mm) _;. Straight 1. Thread-J (Please read the precautions on the back before making the system) Intellectual Property of the Ministry of Economic Affairs Bureau Consumer Consumption Du printed R1 R2 X 434602 ABCD is selected from the basic oxygen radicals —- / 1Α rnK alkane; and the sub-packages are not shaded or the acid and sulfonated I naphthalene chain branched or the base chain oxygen straight alkane is substituted: -C On C1, there are M ring ions and sulphonic acids combined with ring 3) Miscellaneous ί;); node 6 hindering or acetic acid 5 sulfonated ring with hetero}} (2 Multi-family fats and fats can be provided for the children who are combined under the condition of the march. It can be provided for it--it kind of i ο less should be the opposite and the combination of V) device (I capacitive electric system is an electric object. The solid form of the monograph and the 13th item in the 13th paragraph} Fan II Lee {I Special. Please enter: apply the things, such as, and legalize the 14 parties to make a place / Λ / (Please read the precautions on the back before binding) -Installation _ * 1T_ Chinese style is SR and the same phase is the Ministry of Economic Affairs, the Ministry of Economic Affairs, Xi'an Anthony Property Bureau employee consumer cooperatives printed the capacitive layer fatigue. Electrical film Dissolve the electrified object by oxygenation and solidification. The mediator has a single item that is formed into 14 pieces. Poly OR: There are 13 pieces containing the first step in the step, the second step is to dip the dip into the foil. Yang Shenfa, such as Fang Jin • The liquid-soluble son of the valve device made with 15 is described above and the dosed oxygen is contained in the dipping and ·, ο step by step in the middle-layer electric film The description of the solution of the electrified body oxygen and solid matter has a form of 14 will or: 1'3 brackets Fan Yili enters the special request, apply the law as the rule. Create a 16-made device [paper CN / | \ | Quasi-one standard, one country, one country, one country, one country, one k rule | centimeter 7 9 2 434602 A9 B9 C9 D9; Something is contained in the chemical staining body, soaked in a single foil. It is used to perform the immersion of the step valve, and the description of the oxygen storage of the electrified body in the mesophilic layer. The description of the oxygen solid matter is 4 1 or or: 3 1 The application method is as follows: 7. Make a device immersion step of 1 system, after that, the solution of the solution, the ionizer, anionizer, and oxygen of the solution are described in the above. The combination of the valve and the membrane is included in the description of the oxygenated solid of the electrified body. The description of the oxygen-solid substance is 4- 1 or OR: 3, 丨 1 including Bao Yuanbu Fan Yili's special request, apply Farufang. Make 8 play 1 twilight device fluid 0 solution step of the liquid liquefaction solution of the single-clutch yin polymerization machine is described in the stains and infusion foils polarized oxygen is a gold-containing Use the stain as the immersion valve, and then the dielectric film of the coating layer will be decomposed by the oxygen-solid medium of the electrified body. 4 1 will or: 3-丨 1 Including the enclosing step Fan Yili, please apply, apply law such as Fang. Make a 19-piece container. The liquid-state dissolving solution of the step-negative step machine is combined with the chemical compound. The oxygen compound has a single content, is impregnated with poly-impregnated foil, and contains extremely impregnated gold. After use, it is used as a liquid valve to dissolve it (please First, please read the precautions on the back of the product, and then go to the margin.) -Equipment-Order The printed description of the capacitor film printed by the Ministry of Economic Affairs, the Intellectual Property Bureau, the staff consumer cooperative, and the solution of the oxygen and solid matter of the electrified body. 14 will or: 13 including the enclosing step Fan Yili enters into his own request, applying the law as a rule. Making 2 systems. The single-dose chemical oxygenation solution of the combined liquid and liquid solution of the previous step and step contains the gold contained in the impregnated immersion solution, and the polar liquid cation-soluble gold after the foil is used as a negative valve machine. The paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) A9 B9 C9 D9 4346 〇 I The description of the dielectric layer of the capacitor layer is described in terms of oxygen and solid matter. 14 will or: If you want to make a profit, please apply for it. If you apply it, please make it. The 21-made device is a multi-step yin step machine. The liquid solution is dissolved and the chemical compound has a single content. With. Extremely sun-stained step is immersed in gold. After use, it is used as a liquid coating valve to dissolve it. On the other hand, it describes the dissolution on the electrical membrane and the oxygenated and solidified mediator of the electrochemical object. Combine 14 or OR: There are 13 included in the first step of Bin Fan Yi dip into the foil, please refer to it, Yang Shen method is like square gold. 22 valve valves made of many steps of the solution The dosage of oxygen is contained after the impregnation 9. The child of the liquid rapid dissolution step is separated from the solid shade coating machine. 23. The manufacturing method of the solid electrolytic capacitor as described in the application scope of item 13 or 14, further includes: a valve function of forming a dielectric oxide coating layer. After immersing the gold anode anode in the solution of the oxidant, the step of dipping the polymer containing the polymerizable military compound and the organic anion described above is repeatedly performed repeatedly. ------—— t—-.. (Please read the precautions on the back before drawing). Printed by the Consumer Cooperatives of the Intellectual Property Office of the Ministry of Economic Affairs. 24. If the scope of patent application is 13 or 14 The method for manufacturing a solid electrolytic capacitor further comprises: immersing a valve-acting metal anode foil having a dielectric oxide film layer in a solution containing a polymerizable monomer compound, and then immersing in a solution containing an oxidizing agent and the organic anion. The steps are repeated repeatedly. This paper size applies to China's National Standards (CNS) A4 specification (210 X 25 &gt; 7 mm) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 25. The solid electrolytic capacitors described in item 13 or 14 of the scope of patent application The manufacturing method further comprises: immersing the valve action gold anode anode foil having a dielectric oxide film layer in a solution containing an oxidizing agent and the above-mentioned organic anion, and immersing it in a solution containing a polymerizable monomer compound for several times. After repeated lapping, the steps of washing and drying are carried out. 26. The method for manufacturing a solid electrolytic capacitor according to item 13 or 14 of the scope of patent application, further comprising: immersing a valve-acting metal anode foil having a dielectric oxide film layer formed thereon containing a polymerizable monomer compound and the above organic After the solution of the female chick is immersed in the solution containing the oxidant repeatedly, the steps of washing and drying are performed again. 27. The method for manufacturing a solid electrolytic capacitor according to item 13 or 14 of the scope of the patent application, further comprising: immersing the valve action gold anode anode foil formed with the dielectric oxide film layer in a solution containing an oxidant, and immersing in After the steps of the solution containing the polymerizable monomer compound and the above-mentioned organic anion are repeatedly performed, the steps of washing and drying are performed again. 28. The method for manufacturing a solid electrolytic capacitor according to item 13 or 14 of the scope of the patent application, further comprising: immersing the valve-acting metal anode foil having the dielectric oxide film layer formed thereon after dissolution of the polymerizable monomer compound. After the steps of immersing in a solution containing an oxidant and the above-mentioned organic anion are repeatedly performed, the steps of washing and drying are performed. -8- (Please read the precautions on the back before drawing) This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 434602 A9 B9 C9 D9 Printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs 29. The method for manufacturing a solid electrolytic capacitor according to item 13 of the scope of patent application, wherein the organic anion is substituted with at least one of the Ci-Cl22 straight or branched saturated or unsaturated alkoxy groups substituted from above Naphthalene monosulfonic acid anion. 30. The method for manufacturing a solid electrolytic capacitor according to item 29 of the scope of the patent application, wherein the aromatic ring hydrogen atom of the alkoxy substituted naphthalene monosulfonic acid is selected from the group consisting of a halogen atom, a nitro group, and a fluoro group. An alkoxy substituted naphthalenesulfonic acid substituted with at least one substituent of a trihalomethyl group. 31. The method for manufacturing a solid electrolytic capacitor according to item 13 of the scope of the patent application, wherein the organic anion is a heterocyclic sulfonic acid anion. 32. The method for manufacturing a solid electrolytic capacitor according to item 31 of the scope of the application for a patent, wherein the heterocyclic skeleton of the heterocyclic sulfonic acid anion is selected from the group consisting of molybdenum, peridine, piperazine, azole, furan, 1 Chemical compounds of 4,4-dioxane, benzimidazole, benzoxazole, benzoisoxazole, benzotriazole and benzofuran. 33. The method for manufacturing a solid electrolytic capacitor according to item 31 of the scope of the patent application, wherein the heterocyclic sulfonic acid anion contains at least one alkylsulfonic acid substituent on K in the chemical structure. 34. As described in item 13 of the scope of patent application for solid electrolytic capacitors -9- (please read the precautions on the back before drawing) The paper size of this edition applies to China National Standard (CNS) A4 (210 X 297 mm) ) .3 .. Printed by the Intellectual Property of the Ministry of Economic Affairs / gjM Industrial Cooperative Cooperative, «L,, 4 9 9 9 9 ABCD Made. System The description of the device capacity and the structure of the solid layer of the electrical structure is the subdivision of the 11th division to the profit layer of the fan specialization. Please apply for the electricity. The 36 of the 36. Such as the 36th scope of the patent application The solid electrolytic capacitor described in the above item, wherein the solid electrolytic layer having at least a part of a layered structure is formed on the outer surface of the dielectric film or formed on the outer surface and the fine pore portion. The solid electrolytic capacitor according to item 36 or 37, wherein at least a part of the layer between the layers has a space portion. 39. The solid electrolytic capacitor according to item 36 or 37 of the scope of patent application, wherein the thickness of each layer of the solid electrolyte forming the layered structure is in the range of ~ 5wm, and the total thickness of the solid electrolyte layer is in the range of 1 ~ 2 〇0 wm range 〇-10- This paper size applies to Zhongqingjia County (CNS) A4 ^ (21QX 297 public director) ---- Ϊ m I. In I In An m (Please read the note on the back first Matter remarriage system)