TW434602B - Solid electrolytic capacitor and method for preparing the same - Google Patents
Solid electrolytic capacitor and method for preparing the same Download PDFInfo
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434602 A 7 B7 經濟'哪中夬#準局員工消費合作'社印製 五、發明説明(1 ) 本發明關於固體電解電容器及其製造方法,更詳细地 說,係有翡在固體電解質中含有選自(1)烷氧基取代蔡一 磺酸陰離子、(2)雜環化合物之磺酸陰離子及(3)脂肪族 多環化合物的陰離子之至少一種有櫬陰離子作為摻雜物( dopant)之一種具有7T電子共軛構造之専電性聚合物之固 體電解電容器及該電容器之製造方法。 固髏電解電容器係於經蝕刻處理之金羼萡(陽搔基板) 上形成介質氧化被膜層及在其外側形成作為對向電極之固 艚半導電體層(M下簡稱為固體電解質),且更可取為進一 步形成有導電糊等之導電體層所成之元件。此元件之金屬 箔接於陰極引線端子而導電體層接於陽極引線端子,全體 Μ絕緣性樹脂完全封裝作為電容器组件而廣用於電氣製品。 上述之固體電解質之習知者例如包括·•二氧化錳或二 氧化鉛等無饑半等體材料;四氰基醌二甲烷(TCNQ)络鹽 或電導率10-2〜5x103s/cb範圍之真性導電性聚合物[特 開平1 - 16 99 1 4號公報(美國專利第4 , 80 3 , 5 96號)】或;! 共輛系之聚苯胺(特開昭61-239617號公報)、\聚毗咯(特 開昭6卜240 6 25號公報)、聚噻吩衍生物[特開平2-156 11 號公報{美國專利第4 9 1 G 6 4 5號)]、聚異硫茚(特開昭6 2 -1185U號)等。ft等由?I共轭系構造之反覆構造簞元形 成之導電性聚合物多Μ含有摻雜物(dopant}之组成物肜 態使用。最近除了添加摻雜物之外更有併用二氧化錳ί特 公平6 - 1 01 4 1 8號公報(美國專利第4,9 5 9 , 7 5 3號)或填充 料(特開平9-320901公報)之方案。 -4- 請电閱讀背面之注意事項再填ί 14頁) .- ! - - —II · 訂 線 張尺度適用中國國家標準(CNS ) A4.it格(210X 297公| ) 4346 〇 2 經濟部中央.標準局員工消費合作社印裂 A 7 B7五、發明説明(2 ) 有關固體電解質之形成方法,Μ往有例如於具有微细 的空隙構造之閥作用金臑表面之介質層上,藉融解如上述 之固體電解質而形成之方法或在介質層上產生上述之導電 性聚合物之方法等為人所知。具體而言,例如有使用吡咯 或睡吩等五節雜環化合物之聚合物時,將陽極箔浸清於該 等雜環化合物之低級酵/水系溶液之後,再浸潰於溶有氧 化劑及電解質之水溶液中進行化學聚合而形成導電性聚合 物之方法(持開平5 - 1 7 5 0 8 2號公報);將3 , 4 -二氧乙烯-睡 吩單體及氣化劑,最好Κ溶液形態前後分別或一起塗布於 金騸箔之氧化被膜層上而形成之方法[(特開平2-15611號 公報(美國專利第4,910,645號)或特開平10-32145號公 報(歐洲專利公開第8 2 0 0 7 6 Α2號 >】等為人所知。特別是在 特開平10-32145號公報中有揭示摻雜有分子搆瑄中具有 複數之磺酸基之芳香族聚磺酸(例如華二磺酸)之選自吡咯 、噻盼、峡喃、苯胺及由彼等之衍生物選出之聚合物,而 製造方法乃有揭示將上述之聚合性軍體及氧化劑之混合溶 液塗悔及乾燥,或導人氧化劑之後導入單體之聚合方法。 又,在特開平10-32145號公報中有揭示一種將芳香 族聚磺酸之摻雜物當作氧吼劑(亞_〇*)之構成成分利用之 製造方法,其中並有述及具備有該成分之固體電解電容器 表琨優異之附高溫性或防止靜電容量之低降之特徵。 另外,在特公平6 - 8 2 5利號公報(美國專利第4 9 5 9 7 5 號)中有揭示將被1個以上之烷基取代之烷基萘磺酸陰離 子作為摻雜物含存之固體電解電容器,並有逑及此電容器 (請先閔讀背面之注β事本頁) 本紙伕尺度適用中國國家標準(CNS ) Α4規格(210Χ 297公釐) 經濟部中央標準局員工消f合作社印製 A7 B7五、發明説明(3 ) 具有儍異之初期特性及漏電滾特性。 此等習知技術之聚合用氧化劑中被人热知者有例如唾 吩等五節雜環化合物之聚合時所用之氛化鐵(蛋)、Fe(Cl〇4)3 或有檄酸嫌(S )、無櫬酸嫌(fi )、烷基過硫酸强、過磙酸 銨(M下簡稱APS)、遇氧化g、1^(:1'2〇7等[特開平2-15611 號公報(美國專利第4 , 910, 645號)]或鋦化合物、銀化合 物等[特開平10-3214 5號公報(歃洲專利公開第820076八2 號)]0 但上述之使用二氧化錳之固體電解質之電容器在硝酸 錳之热分解時,氧化皮膜層有被破壊之鈇黠,而且阻抗特 性亦不夠理想。另外,使用二氧化鉛時,對環境有顧盧之 問題。 使用四氰基醌二甲烷(TCNQ>絡«之固體電解質之電 " 容器雖然具有P異之熱熔融加工性或導電性,但TCNQ络 隳本身卻有耐熱性問題,在焊接耐熱性上可靠性差。 為了改善上述問題,雖可藉電解聚合法或化學聚合法 將上述之聚吡咯等導電性聚合物作為介質表面之固體電解 質使用,但仍無法獲得滿意之皮膜均匀性、焊接酎熱性及 阻抗特性等〇 . 為此,在製造高性能之電容器上,對於固體電解質之 材料或其製造方法,熱安定性、皮膜之均匀性等之改進有 殷切之要求。 有鑑於上述之問題,本發明提供一棰輕又小型、高容 量、K及高頻特性、損失係數(tanS )、溏電流、耐熱性 -6 -本纸張尺度適用中國國家標隼(CNS ) A4規格(210X 297公煃) (請先叫讀tw面之注意事項再填寫本頁 » mt n^i n^l n I ϋ^— till tn V!J 、y5 泉 434602 A 7 B7 M濟部中央標準局員工消費合作社印製 五、發明説明(4 ) (回流性)等優異之固體電解電容器,尤其本發明提供具有 低阻抗特性而且對火花電壓試驗顯示優異之酎久性之酎熱 性固體電解電容器。 本發明等人為了解決上述之間題,對於導電性聚合物 中之摻雜物陰雄子之種類、組合W及含量等加W潛心探討 结果發琨在備有:對向一對電極而其一個電極係由閥作用 金靨箔表面之金雇氧化物形成之微细構造的介質(絕緣物) 層。及在該介質層上形成之由導電性聚合物形成之固體電 解質層之一種固體電解電容器中,將特定之有機陰離子作 為摻雜物,令其含存於上述固體電解質中,從而解決上逑 之間題。 即,本發明提供一種在固體電解質中含有選自:(1) 由碳原子數1〜12個(Ct-C12)之直鍵或支鍵之飽和或不飽 和羥基之至少一個Μ上取代之烷氧塞取代萘一磺酸陰維子 ;(2)具有5或6節之雜環之雜環化合物之磺酸陰離子( ? . 以下稱為雜環磺酸陰離子)及(3)脂族多環化合物之陰雔 子之至少一種作為有機陰維子為特激之小型又低阻抗且對 火花電壓試驗表琨耐久性之高性能固體電解電容器及其製 造方法。更具體而言,本發明涉及: [1]—種在介質氧化被膜上形成有含有7Τ電子共拥構 造之導電性聚合物姐成物層之固體電解電容器,其特徴乃 在該聚合物姐成物層中含有選自(1)由碳原子數1〜12((^ -C12)之直鍵或支鍵之飽和或不飽和烷氧基之至少一個以 上取代之垸氧基取代萦一磺酸陰維子;(2)具有5節或6 請 先 閱 讀 背 面 之 注 意 事 項 % 本 頁 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X 297公釐) 434602 A7 經濟部中央標準局員工消費合作社印11 B7 ____五、發明説明(5 ) 節之雜環之雜環化合物之磺酸陰離子(Μ下稱為雑環磺酸 陰難子);及(3)脂族多環化合物之陰離子之至少一種有 機陰糠子作為摻雜物(dopant)。 [2_】如上述[1]項所述之固賵霣解電容器,其中作為 摻雜物之該有機陰離子偽由碳原子数1〜12之直鏈或支鐽 之飽和或不飽和烷氧基之至少一個以上取代之烷氧基取代 蓊一磺酸陰麁子。 [31如上述[2】項所述之固體電解電容器,其中烷氧 基取代萘一磺酸之芳香族環氫原子係由選自鹵原子、硝基 、氟基及三鹵甲基中之至少一種取代基取代之烷氧基取代 萘磺酸。 [4]如上逑[1]項所述之固體電解電容器,其中作為 摻雜物之該有機陰離子為雜環磺酸陰離子。 [51如上述[4】項所述之固體電解電容器,其中該雜 環磺酸陰離子之雜環骨架係選自一棰含有嗎啉、皭唾、哌 嗪、味唑、呋哺、1,4-二噁烷、苯並咪唑、苯並噻唑硫、 苯並異噁唑、苯並三唑及苯並呋哺之化學構造之化合物。 [6】如上逑[4]項所述之固體電解電容器,其中該雜 環播酸陰離子係在其化學構造内含有一個以上之焼基碌酸 取代基。 [T]如上述丨1]項所述之固體電解電容器,其中作為 摻雜物Z該有機陰離子係脂昉族多環化合物之陰離子。 [8]如上述[II〜[7】,項所述之固體電解電容器,其 中該有機陰離子係對導電性聚合物之全反覆單元Μ 〇. 1〜 -8- 本纸張尺度適用中國國家標準(CN’S ) Α4規格(210 X 297公漦"Τ'"~~ ' VHI m g-lsi ^.nn i in ml —I*· If . - (請先閱讀背面之注意事項再1,:¾本頁) 訂 線 3 A 7 _B7 五、發明説明(6 ) 50其耳$範圍含存者。 [9】如上述【11〜[8】項所述之固體電解電容器,其 係除上述之有懺陰離子Μ外,尚含有具有摻雜物性能之氧 化劑的還原體陰雄子0 · 1〜萁耳X範圍。 [1G]如上述[9]項所述之固體電解電容器,其中該 氧化劑的遢原體陰離子係硫酸陰鐮子。 讀 I 先丨 閱 | 讀; 背· i 面 h 之 、注- 上逑[1】〜[10】項之任一項所述之在介 質氧化被膜上形成有導電性聚合物姐成物層之固胃胃$ 容器,其中該組成物之専電性聚合物係含有下β 1式(I)所 之反覆構造單元: 11] 種如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 電 示 頁 裝I electrical display
(I) 訂 式中:取代基R1及R2各獨立的代表由氧、P ^ L 1 _ C e之直 鏈或支鏟之飽和或不飽和烴基、或(:1-(:6直_命+ (^ _ 珥或支鐽之飽 和或不飽和烷氧基、羥基、鹵原子、硝基、^ m 叫S、二齒甲(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
基、苯基及取代苯基選出之任1個一價基;Y 乂,上述之取 代基!^及R2可在任意之位置互相结合形成至少 1涸一價鍵 用以形成至少1個以上之5〜7節環之飽和或^ % Α跑和之環 狀構造;X代表雜原子S、0、Se、Te或MR3 _ *其中R3S Cj -ce直鐽或支鍵之飽和或不飽和烴基、苯基、 d 驭Ci-CB之直 鐽或支鏈之飽和或不飽和烷氧基;又上述b、R3= $ 本纸張尺度適用中國國家標準(cns ) .μ規格(m〇x 297公釐 線 經濟部中央標隼局負工消費合作社印掣 4 3 4 6 0 2 A7 B7 五、發明説明(7 ) 基、烷氧基之鐽中亦可任意的含有羰基鍵、醚鍵、酷鐽、、 醸胺鍵及亞胺基鍵;而δ代表Q〜1。 [12】如上述[11】項所述之固體電麻電容器,其中式 (I)之反覆構造單元為如下式(II)所示: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······· 士 n J J -- (請先閲讀贤面之注意事項再< ;本頁·) 經濟部中央標隼局員工消費合作社印製 式中:取代基ϋ4及R5各獨立的代表Ci-Cs直鍵或支鐽 之飽和或不飽和烴基、或Ci-Ce之烴基在任意之位置互相 结合形成含有式中記載之二個氣原子之至少一個Μ上之5 〜?節之雑環構造之取代基;又形成上述環構造之範圍包 含取代乙烯撐基或取代0-苯撐基等之化學構造;S代表0 i 〇 [13] —種如上述[1】項所述之在介質氧化被膜上形 成有導電性聚合物姐成物層之固體電解電容器之製造方法 ,其係在介質氧化被膜上藉氧化劑將聚合性單體化合物聚 合之方法,其特徵包括:令下式(III)所示之聚合性單趙 化合物: R1 R2S -----;: 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- 本紙张尺度適用中國國家標準(CNS ) A4说格(210X 297公釐) 訂 線 434602 Λ7 B7 五、發明説明(8 ) (式中:取代基R1、R*6及X係與上式(Π所定義者同)。 在選自(1}由之直鐽或支鏈之餓和或不飽和烷 氧基之至少一個以上取代之烷氧基取代萘一戶酸瞎離子; (2)具有5節或&節之雜環之雜瑁化合物之磺酸陰離子( 稱為雜環磺酸陰離子);.(3)脂肪族多環化合物之陰雄子 之至少一種可提供有機陰離子之化合物之存在下進行該聚 合反懕。 i- U 4 ]·如上述[1 3 ]項所述之固體電解電容器之製造方 法,其中式(III)之聚合性單體化合物係下式(IV)所示 之化合物:‘ R40 OR5 \ /-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 & 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)、 (請先閲讀背面之注意事項再广.4'本頁) 訂 經濟部中央祿準局員工消費合作社印製 式中:R4及Rs係與上式(II)所定義者相同。 [15] 如上述[13]或[U】項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 闕作用金靥陽搔箔浸漬於含有聚合物軍體化合物之溶液中 之步驟;及浸潰於含有氧化劑及上述有機陰離子之溶液中 之步驟。 [16] 如上述[13]或[14]項所逑之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層;^ 閥作用金颺陽極須浸漬於含有氧化劑之溶液中之步驟·,及 -U- 線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 本紙張尺度適用中國國家標準(CNS ) A4規格(210X'297公浼) ά 經濟部中央樣準局員工消費合作社印製 A 7 B7 五、發明説明(9 ) 浸漬於含有聚合性簞體化合物及上述有櫬陰離子之溶液中 之步驟。 [1 7]如上述[1 3 ]或[1 4 ]項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金屬陽極箔浸漬於含有氧化劑之溶液之後,浸潰於 含有聚合性軍體化合物及上述有機陰離子之溶液之步嫌。 [18]如上述[13】或[14]項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金靥陽極箔浸漬於含有聚合性單體化合物之溶液後 ,浸漬於含有氧化劑及上述有機陰離子之溶液之步驟。 [19】如上述[13}或[14]項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金鼷陽極萡浸漬於含有氧化劑及上述有機陰雄子之 溶液後,浸潰於含有聚合性簞體化合物之溶液之步驟。 [20]如上述[13]或[14]項所逑之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金鼷陽極箔浸漬於含有聚合性軍體化合物及上述有 機陰離子之溶液後,浸潰於含有氧化货之溶疲之步驟。 [21】如上述〖13]或[14】項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 闕作用金靨陽極箔浸漬於含有氧化劑及上逑有機陰維子之 溶液後,浸漬於含有聚合性單體化合物之溶液之步驟多次 反覆實行之步驟。 [22]如上述[13】或[14]項所述之固體電解電容器 -12- 本紙张尺度適用中國國家標準(CNS ) A4規格(210',<2?7公釐) ---------裝-- (請先閲讀背面之注意事項再一,¾本頁)— / 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 ', < 2? 7 mm) ---- ----- install-(Please read the precautions on the back first, ¾ this page)
、tT 線 434602 A7 B7 經濟部中央標準局員工消費合作衽印製 五、發明説明(i〇) 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金羼陽極萡浸漬於含有聚合性單體化合物及上逑有 機陰離子之溶液後,浸潰於含有氧化劑之溶液之步驟多次 反覆實行之步睡。 [23]卯上述[13]或[14]項所述之固體電解罨容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金屬陽極萡浸漬於氧化劑之溶液後,浸漬於含有聚 合性單體化合物及上述有機陰離子之溶菝之步驟多次反覆 實行之步驟。 [24】如上述[13】或[14】項所述之固體電解霣容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金颺陽極箔浸潰於含有聚合性軍體化合物之溶液後 ,浸漬於含有氧化劑及上述有機陰維子之溶液之步驟多次 反覆實行之步驟。 [251如上述[13】或[14】項所述之固趙電解電容器 之製造方法,其進一步包括:將形成有介質氣化被膜層之 閥作用金屬陽極箔浸漬於含有氧化劑及上述有機陰雄子之 溶液後,浸潰、於含有聚合性軍體化合物之溶液之步驟多次 反覆實行之後,再實行洗淨及乾煉之步驟。 [26]如上述[13]或[14]項所述之固體電解電容器 之製造方法,其進一步包括:將形成有介質氧化被膜層之 閥作用金屬陽極箔浸潰於含有聚合性單體化合物及上逑有 機陰離子之溶液後,浸漬於含有氧化劑之溶液之步驟多次 反覆實行之後,再實行洗淨及乾燥之步驟。 -13- 本紙張尺度適用中國國家標準(CNS ) Λ4規格(2丨0X 297公釐) (請先閱讀背面之注意事項再"%本頁) .裝- 訂 線 434602 A7 B7 經滴部中央標準局員工消費合作社印製 五、發明説明 (11 ) [27] 50上述[ 13 1 或 [14] 項所述之固體罨解電容器 之 製 造方 法,其進 一 步 包 括 將 形 成 有 介 質 氧 化 被 m 層 之 閥 作 用金 羼陽極箔 浸 漬 於 含 有 氧 化 爾 之 溶 液 後 9 浸 漬 於 含 有 聚 合性 軍體化合 物 及 上 述 有 機 陰 雄 子 之 溶 液 之 步 驟 多 次 反 覆 實行 之後1再 實 行 洗 淨 及 乾 煉 之 步 驟 〇 [28] 如上述[ 1 3 ] 或 (1 4] 項所逑之固體霣解電容器 之 製 造方 法,其進 一 步 包 括 : 將 形 成 有 介 質 氧 化 被 膜 層 之 閥 作 用金 臛陽棰箔 浸 漬 於 含 有聚 合 性 單 體 化 合 物 之 溶 液 後 9 浸 漬於 含有氣化 劑 及 上 述 有 機 陰 離 子 之 溶 液 之 步 驟 多 次 反 覆 實行 之後,再 實 行 洗 淨 及 乾 燥 之 步 驊 0 [29] 如上述[ 13 ]〜[ 28 3 項 所 述 之 固 艚 電 解 電 容 器 之 製 造 方法 ,其中該 有 機 陰 雄 子 係 由 Cl -C 12 之 直 鐽 或 支鐽 之 飽 和 或不 飽和烷氧 基 之 至 少 一 個 Μ 上 取 代 之 院 氧 基 取 代 一 磺 酸陰 離子。 [30] 上述[29] 項 所 述 之 固 體 電 解 電 容 器 之 製 造 方 法 4 其 中烷 氧基取代 萘 一 磺 酸 之 芳 香 族 環 氫 原 子 係 由 m 白 鹵 原 子 、硝 基、氰基 > 三 鹵 甲 基 之 至 少 — 種 取 代 基 取 代 之 烷 氧 基 取代 萘磺酸。 [31] 上述[13 ]^ -I 28 ] 項 所 述 固 體 電 解 電 容 器 之 製 造 方 法, 其中有撻 陰 離 子 係 雜 環 磺 酸 陰 離 子 〇 [32] 上述[13 卜[ 31 ] 項 所 述 之 固 體 電 -jm 解 電 容 器 之 製 造 方 法, 其中該雜 環 磺 酸 陰 離 子 之 雜 環 骨 架 係 選 白 一 種 含 有 嗎 啉、 哌啶、哌 嗪 味 唑 \ 呋 喃 Λ 1, 4- 二 噁 烧 苯 並 眯 唾 苯並 噻唑硫、 苯 並 異 噁 唑 Ν 苯 並 三 唑 及 苯 並 呋 喃 之 化 -14- 訂 線 木紙張尺度適用中國國家標準(CNS〉A4規袼(2i〇x2W公釐) 請 先 閱 讀 背 ιέ 之 注 意 事 項 再 衰裝 頁 Λ 7 Β7 經濟部中央標準局員工消費合作社印製 五 '發明説明(12) 學構造之化合物。 [s33]上述[31]項所述之固體電解罨容器之製造方法 - ,其中該雑環磺酸陰離子係在化學構造中含有至少一個以 上之烷基磺酸取代基。 [34】上述[13]〜[281項所述之固體電解電容器之製 造方法,其中該有機陰雄子為脂肪族多環化合物之陰雄子。 [35]上述[13]〜[34]項之任一項所述之固體電解霄 容器,其中該氧化劑為過疎酸鹽。 [361上述[1】項所述之固體電解電容器,其中該固 體電解質層之至少一部分係呈層狀構造。 [37] 上述[36]項所述之固體電解電容器,其中該至 少一部分圼層狀構造之該固體電解曆曆,係形成於介質被 膜上之外部表面或形成於外部表面及微细孔部分内。 [38] 上述[36]或[37]項所述之固體電解電容器, 其中在該餍狀構造之層間之至少一部分係具有空間部。 [39】上述[36]或[37】項所述之固體電解電容器, 其中形成該層狀構造之固體電解質之各層的厚度係在0.01 〜5« Β之範圍,而該固體電解質層之總厚度係在1〜2〇〇 w 1Π之範圍。 〈詳细說明〉 爰詳细說明本發明於下: 依本發明,由於在導電性聚合物姐成物層中含有由 Ci-Ciat直鍵或支鍵之飽和或不飽和烷氧基之至少—傾以 上取代之烷氧基取代萘一磺酸陰離子、(2)具有5節或6 -1 5 - 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210Χ 297公釐) (精先閲讀背面之注意事項再一ic本頁) •Xi a/ *τ Γ ,ί, 4 ο 4 6 Ο 2 A7 B7 經濟部中央標準扃員工消費合作社印製 五、發明説明(13) 節之雜瑁之雜環化合物之磺酸陰離子;/及(3)脂肪族多環 化合物之陰難子選出之至少一種有機陰離子作為具有摻雜 物能力之主要陰離子,因此可Κ形成具有良好_熱性之導 電性聚合物層(電荷移動絡合物),结果能夠提供具有低姐 抗特性及在火花電JE試驗等顯示《[異iW久性之高性能固體 電解電容器及其製造方法。 另外,本發明可藉由併用上述有機陰雄子之摻雜物Μ 外之其他陰雛子作為摻雜物,Κ進一步提高上述之諸性能° 適合作為本發明之電容器之導電性聚合物姐成物層中 之κ電子共轭聚合物係在聚合物主鐽構造中具有κ電子共 軛構造之高分子化合物,其具雅例為聚笨胺、聚對-苯撐 、聚對-苯撐乙烯撐、聚噻聰撐乙烯撐、聚雜環聚合物及 其取代衍生物。 可取之聚雜環聚合物之具體例為具有上述式(I)所示 之構造單元之α電子共輛聚合物,更可取為具有上述式( II)所示之構造單元之π電子共轭聚合物。 上述式(I)及式(I)中,取代基R1、!?2及R3代表h-Ce之直鐽或支鍵飽和或不飽和烴基。具體例為甲基、乙基 、乙烯基、丙基、烯丙基、異丁烯、丁基、1-丁烯基。又 Ci-Cs之直鐽或支鐽飽和或不飽和之烷氧基之具體例為甲 氧基、乙氧基、丙氧基、異丙氧基、丁氧基。又,上述’煙 基或烷氧基Μ外之有用之取代基之具體例為硝基、氰基、 苯基及取代苯基(Cl、Br、F等鹵素取代苯基)°上述之R1 、R2之烧基及烧氧基中之鏈中可任意的含有截鍵、K鐽、 -16- (請先閱讀背面之注意事項再罐寫本頁) -装· 訂 旅 本纸張尺度適用中國國家標準(CNS ) Λ4規格(210x297公釐) 4346 Ο 2 佟正 Μα " mmm A 7 B7 五、發明説明(14 ) 酯键、豳胺鐽及亞胺基鐽,特別有用之例為甲.氧乙氧基及 甲氧乙氧乙氧基。 又,上述之取代基R1及R2亦可互相在任箄之位置结合 而彤成1個以上之5〜7節環之飽和或不飽和環狀構造之 二價基。此種式(I)或式(S)之二價基之具體例包括如 下所示之3,4-丙烯取代櫞造(VI)、3,4-丁稀取代構造(νΓΙ )、3,4-丁烯撐取代構造(?111)及蔡笼[2,3-<^】鎌合辑造 (IX): 請 閲 讀 背 f ,1 1 I 存 I f 装 本 I 育、 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 " 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- < ^] sickle compilation (IX): Please read back f, 1 1 I save I f
'X (V) ΐ丁'X (V) Tintin
4346U24346U2
五、發明説明(15V. Description of the invention (15
X (ΥΙΠ)X (ΥΙΠ)
(IX) 經濟部中央標準局員工消費合作社印袋 上式中:·χ代表雜原子,具體例為s、0、Se、Te或 NR3。X為S之上述3,4 -丁二.輝取代構埠,若是式(I)之反 覆單元構造時,俗稱為異碇茚撐(isothianaphthenylene )構造,若是式(S)之聚合性罝體化合物構造時俗稱為 異硫雜(isothianaphthene)構造。又蔡並[2,3-c]结合取 代構造,若是式.(I)時為萦並[2,3-c]噻吩(thienylene) 構造單元而荐是式(I)之聚合性單體化合物構造時'薄為 萘並[2,3-c】噻吩。式中,δ代表一個反覆構造單元之荷 電數,係0〜1範圍之值。 式(II)或式(IV)中之β*及R5之有用之取代基之例為 甲基、乙基、丙基、異丙基、乙烯基及烯丙基。又8*及!{3 之%-%烴基亦可互相在任意之位置结合而形成上述式(11 (请先Μ讀背面之注意事項再一,-本頁)(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 \N c% T \
Ai 4 AAi 4 A
XX
I A7 B7 五、發明説明(I6 ) 或式(IV)中所示之含有2個氧之至少1俚以上之5〜7節 環之雜環構造之取代基;而此取代基之可取具體例為1,2-乙烯、1,2-丙烯、1,2-二甲基-乙烯。又R*及R5亦可為上 述之Ct-Cs烴基互相在任蕙之位置结合而形成取代乙烯撐 或取代鄰-苯撐等不飽和烴之環狀櫞造,例如下面所示之 1,2-乙烯撐(X)、1,2-丙烯撐(XI)、2,3-丁烯-2-撐(XII)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-環己烯撐(XIII}、甲基-〇-苯撐(XIV)、1,2-二甲基 -0-苯撐(XV)及2基-〇-苯撐(XVI): ’ (請先閱讀背面之注意事項再1,,¾本頁)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 訂 線--i 經濟部中央標準局員工消費合作社印裝\ J- (XI order line--i Printed by the staff consumer cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
f yf y
I (XII (XI
本纸張尺度it用巾關家轉(CNS) A4a格(21Qx297公澄) 4346 0 2 A7 B7 五、發明説明(l7This paper scale it uses towels (CNS) A4a grid (21Qx297 Gongcheng) 4346 0 2 A7 B7 V. Description of the invention (l7
(請先閱讀背面之注意事項再I :本頁) 裝. 訂 經濟部中央標準局員工消費合作杜印製(Please read the notes on the back before I: this page)
ο 2 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210 X Μ?公釐) -線 A 7 B7 五、發明説明(18 )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^ / ^ Η2ΟΗ3 〇 〇
s 請先閱讀背面之注意#.項ί . 經濟部中央標準局員工消費合作社印製 在本發明之固體電解電容器及其製造方法中使用之上 述式(1)之單體化合物中,例如嘍吩(1^=!^=11、][ = 8)或 吡咯(R^R^H、X = NH),或上述式(IV)代表之噻吩類中之 3,4-二氧乙烯-噻吩之聚合性軍體為習知,而可用Μ聚合 該等單體之氧化劑亦為習知。但,在導電性组成物中以上 述(1)〜(3)之有機陰離子作為摻雜物及Μ其他陰維子作 為輔助摻雑物含存而製造具有固體電解質之電容器為從未 被人所知。 即,特開平10-32145號公報所揭示之電容器用導電 性聚合物組成物為選自摻雜有分子構造中具有複數之磺酸 基之芳香族聚磺酸化合物(例如萘二磺酸陰雜子)之吡咯 、唪吩、呋喃、苯肢及其衍生物等聚合物。其中並無揭示 Μ如上述(1)〜(3)之有機陰離子,同時亦無掲示任何有 闞輔肋摻雜物陰離子之併用技術及由其可獲得之增進效果。 又,構成本發明之固體電解電容器之固體電解質之摻 雜物之較可取的形態係由對上逑;r共辆聚合物之全反覆簞 -2 1- 本紙張尺用中國國家標準(CNsT^4規格(210X297公婕) 1-本頁) .r.L--— 裝-------訂 .線------,-----^---;----^--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 -----, ----- ^ ---; ---- ^ -
五、發明説明(IS ) 經濟部中央標準局員工消費合作社印裝> 元含有上述(1)〜(3)之有櫬陰維子〇·1〜50莫耳χ及更 可取為併含有上述有機陰離子Κ外之其他摻雜物陰離子0.1 〜1〇莫耳X。具備含有此種接雜物之固體電解質之電容器 除可解決上述之問題之外,更具備優異之低阻抗特性及附 火花電壓試驗顯示優異之耐久性。此種固體電解電容器及 其製法是從未被人所知。 在本發明之電容器中,尤其可Μ提供低阻抗特性之電 容器之固體電解質為對π共軛糸聚合物之全反覆單元含有 1〜30莫耳;ί之上述有機陰離子。又,本潑明之上述固體 電解質中之有機陰離子Μ外之其他陰離子之含童最好為該 π共扼聚合物之全反覆軍元之0.1〜5冥耳%。上述之其他 陰離子,於本發明之製造方法中,由於在軍體化合物之聚 合時使用氧化爾,因此可以氧化劑之還原體陰雜子狀態含 存,故不需另外添加,但亦可另外添加。此種併含方法不 受特別之限制。 在電容器之製造方法中,為了改進高容量之高頻特性 及、漏電流、酎熱性(回流性)、阻抗及酎久性等,上 述之固髖電解質之製造(形成)方法乃至闞重要。為此,構 成固體電解質之7!電子共軛構造及摻雜物之姐合,K及在 微细之介質層上緻密的填充形成導電性聚合物層提高導電 變阻之均匀性係羼重要之擧,尤其導電性聚合物之構成對 電容器之特性有很大之影響。 本發明之固體電解電容器之一係為使具備熱應力緩和 特性等,將固體電解質層之至少一部分形成為層狀構造。 -2 2- 本紙張尺度適用中國國家標準(CNS ) Λ4規格.(210.X 297公菝) 聞 Μ 之 泣 項 衰裝 頁 訂 線 4346 〇2 A 7 B7 五、發明説明(2〇 ) 固體電解質層係形成於閥作用金屬表面之介質層上之 微细孔部分内及其外部表面。此外部表面層之厚度為1〜 2 0 0 w η範圍,最好為1〜100 w ία範圍。在本發明中,上述 之層狀構造係多形成於上述外部表面,但最好亦同時形成 於微细孔部分内。層之排列方向多與閥作用金鼷面大致成 平行。同時,相鄰接之層間至少一部分形成有空間部。形 成層狀構造之各個層之厚度為〇.〇1〜5 w®範圍,較佳為 0. 0 1〜lua範圍,最佳〇.1〜Q.3 w η範圍。 本發明之固體電解質製造方法之符徵乃在於以上逑之 有機陰離子及其他陰離子之組合作為上述聚合性單體化合 物之聚合物之摻雜物實行聚合彤成固體電解層。具體而言 ,令式(Et)或式(IV)所示之聚合性軍體化合物,藉氧化 劑之作用及於可提供上逑有櫬陰難子之化合物之存在下, 在微细孔之介質被膜上進行氧化的聚合而將生成之聚合物 作為固體電解質形成於介質表面。進而,將前述之製程對 1個陽極基板實行1次Μ上,最好反覆實行3〜30次,即 可如意的形成緻密之固體電解質層。 例如,較可取之製程之一為,在上述之聚合反應時包 — IU-ί--^丨裝-- (請先閱讀背面之注意事項iti寫本頁·) 經濟部中央標隼局負工消費合作杜印裝 金浸 用或液 作,溶 閥驟之 之步子 層之離 膜 } 陰 被Ϊ機化2有 氧(¾之 質液述 介溶上 有之及 成劑物 形化合 將氧化 ,有體 含含單 陽於 臛漬 2 液 溶 於性 , 漬合驟 浸聚步 箔有之 極含 極 陽驟驟 該步步 將之之 或 1 2 液 溶 述 上 於 漬 浸 先 箔 潰 浸 再 後 之 液 溶 述 上 潰 浸 再 後 之 ii 液 溶 述 上 於 漬 浸 先 或 液 溶 述 上 本紙浪尺度適用中國國家標準(CNTS ) ΑΦ規格(210X 297公釐) 4 3 4 6 u' 2 A7 經濟部中央標準局員工消費合作社印製 B7五、發明説明(21 ) 另一實施形態包括將上述陽極箔浸潰於含有氧化劑及 上述之有機陰離子之溶液(溶液3)之步驟及浸潰於含聚合 性單體化合物之溶液(溶液4),或將陽掻萡先浸潰於上述 溶液4後再浸潰於上述溶液3之步驟,或先浸漬於上述溶 液3後再浸潰於上述溶液4之步驟。上述溶液1〜溶液4 亦可分別在懸浮狀態使用。 另外,上述之浸漬步骒亦可由塗佈作業取代。溶液1 〜4之溶媒可為同系亦可為不同系溶媒,又依溶媒之種類 亦可在溶液1及溶液2或溶液3及溶液4之步驟之間加插 乾燥步驟。另外,在上述固體電解質形成後亦可加插利用 有櫬溶媒或水洗淨元件之步驟。洗淨用有機溶媒最好使用 溶液1〜4所用相同之溶媒,但其他任何可溶解聚合性軍 體化合物或上述有櫬陰離子化合物及具有摻雜物性能之陰 離子之其他化合物之溶媒皆可俾用。经過上述溶媒洗淨後 ,聚合物中之上逑有櫬陰離子Μ外之其他陰雄子之含量會 降低。但只要有上述之有機陰雄子含存,對於本發明之固 體電解電容器之特性有所貢獻。 蔣上述之氧化的聚合反覆實行之場合,可容易生成焊 接耐熱性(熱安定性)優異之固體電解質。使用習知之聚瞅 咯等所成之固體電解質之電容器,在高溫高濕度時,電容 器特性之變動大,可靠性差,但備有本發明所述之導電性 組成物之固體電解質之電容器具有優異之熱安定性且含接 雜物吠態之安定性良好。本發明由於使含有上述有機陰雄 子及來自氧化劑之摻雜物(陰離子)之聚合物階段的析出而 -24- ----MJ---1.---裝------訂---'·---—線 ΐ . 二 (請先閲讀背面之注意事項再螃寫本頁) 本紙張尺度適用中國國家標準(CNS ) Α4規格(210X 297公釐) 經濟部中央標準局員工消費合作杜印製 A 7 B7 五、發明説明(22 ) , ' . 填充於介質表面及细孔內部,因此可形成該聚合物之多層 薄膜叠合層,從而提供具有良好的热安定性且介質被膜不 受該聚合物之破壊之電容器。 又,由於本發明使用之上述有機陰離子,比習知之摻 雜物(例如CIO*-、BF*-、Cl-、S0«2·、苯磺酸陰離子、烷 基取代萦磺酸陰離子等)在與π共轆系聚合物形成電荷移 動络合物時顯示優異之熱安定性及導電狀態之安定性之摻 雜物化合物,因此可製得具有低阻抗特性及對火花電壓試 驗顯示優異耐熱性及耐久性之高性能電容器。 即,例如上述有機陰雜子中,使用烷氧基取代蔡一磺 酸陰離子時,由於萘骨架所具之高芳香族性及芳香族環取 代之磺酸基所具之電子吸引性及水溶性,進而烷氧基之對 蔡環之電子給予性,提供具有上述特性之電容器。 次說明使用於本發明之有機陰離子於下: U)烷氧基取代萘一磺酸陰離子 本發明使用之烷氧基取代萘一磺酸係有一個磺酸基在 萘骨架上取代之烷氧基取代萘一磺酸化合物及其他取代蔡 一磺酸化合物的緦稱。 較可取之化合物為萘一磺酸之萘環之氫原子被Cl-Cli ,尤其Ci-Cs之直鑣或支鰱之飽和或不飽和烷氧基之至少 一個K上取代之化合物。 能提供上述之烷氧基取代萘一磺酸陰離子之化合物之 具體例為具有萘-1-磺酸、萦-2-磺酸及其鹸金屬鹽、銨鹽 、有機四级胺鹽等化合物骨架且其萘環之氫原子被烷氧基 -2 5 ~ 本纸張尺度適用中國國家標準(CNS ) A4規格(210'〆297公釐) (請先閲讀背面之注意事項又:寫本頁 -裝_ 訂 A7 B7 五、發明説明(23 ) .λ 之1個K上取代之化學構造之化合物。即C ί - C i 2之直鏈或 ) 支鍵之飽和或不飽和之烷氧基的取代化合物。有用之取代 基之例子為甲氧基、乙氧基、乙烯氧基、丙氧基、烯丙氧 基、異丙氧基、丁氧基、1-丁烯氧基、戊氧基、己氣声、 辛氧基、壬氧基、癸氧基等,亦可包含被環己氧基或苯氧 基等環狀烴基取代之烷氧基。 又,例如1-烷氧基萘環之2位乃至8位被取代之一磺 酸化合物或2-烷氧基萦環之1位及3位乃至8位被取代之 一磺酸化合物陰雛子可有效的作為上述之烷氧基取代萘一 磺酸化合物使用。另外,烷氧基萘環上之氫原子亦可被F 、01、81>、1等鹵原子或0?3、硝基、氰基等取代。 U)雑環型化合物之磺酸陰雄子(雜環磺酸陰雜子) 本發明使用之雜環磺酸陰離子係具有:有一個Μ上之 磺酸基直接或經由烷撐基(alkylene)間接的在雜環上取 代之化學構造之雜環型磺酸化合物之陰雛子的總稱,較可 取之雜環化合物之骨架可例舉嗎啉、哌啶、哌嚎、咪唑、 呋喃、1,4-二噁烷、苯並咪唑、苯並噻唑硫、苯並異噁唑 、苯並三唑及苯並呋喃取代骨架。 經濟部中央標準局員工消費合作社印製 可提供上述間接的取代有磺酸陰離子之雜環化合物陰 雛子之較可取例為包括: 嗎啉骨架系化合物:例如,1-嗎啉代甲烷磺酸、2-嗎 啉代乙烷磺酸、3-嗎啉代丙烷磺酸、2 -甲基-2-嗎啉代丙 烷磺酸、4-嗎啉代丁烷磺酸、5-嗎啉代戊烷磺酸、6-嗎啉 代己烷磺酸、7-嗎啉代庚烷磺酸、8-嗎啉代辛烷磺酸、9- -26-本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X 297公釐) 經濟部中央標準局員工消費合作社印裝 五、發明説明(24) 嗎啉代壬烷磺酸、10-嗎啉代癸烷磺酸、12-嗎啉代十二烷 磺酸等。 哌啶骨架系化合物:例如,1-暱啶代甲烷磺酸、2-哌 啶代乙烷磺酸、3 -哌啶代丙烷磺酸、2 -甲基-2-暱啶代丙 烷磺酸、4-哌唾代丁烷磺酸、5-哌啶代戊烷磺酸、6-哌啶 代己烷磺酸、7-哌啶代庚烷磺酸、8-哌啶代辛烷磺酸、9-哌啶代壬烷磺酸、10 -哌啶代癸烷磺酸、12 -哌啶代十二烷 磺酸等。 哌唼骨架条化合物:例如,哌螓-1,4-雙(1-磺甲基) 、哌Sf-1,4-雙(2-磺乙基)、哌嗪Μ ,4-雙(3-磺丙基)、哌 嗪-1,4-雙(4-磺丁基)、哌嗪-1,4-雙(5-磺戊基)、哌螓-1 ,4-雙(6-磺己基)、哌嗪-14-雙(7-磺庚基)、暱螓-1,4-雙(8-磺辛基)、哌嗪- ΐ,4-雙(9-磺壬基)、哌矂-1,4-雙( 10-磺癸基)、哌嗪-1,4-雙(12-磺十二基)酸等。 唑唑骨架系化合物:例如1-(2-眯唑基)甲烷酸、2-(2 -眯唑基)乙烷磺酸、3 -(2-眯唑基)丙烷磺酸、2-甲基-2-( 2-咪唑基)丙烷磺酸、4-(2-眯唑基)丁烷磺酸、5-(2-眯唑 基> 戊烷磺酸、6-(2-咪唑基)己烷磺酸、7-(2-眯唑基)庚 烷磺酸、8-(2-眯唑基)辛烷磺酸、9-(2-眯唑基)壬烷磺酸 、10-(2-眯唑基)癸烷磺酸、12 -(2-眯唑基)十二烷磺酸等。 肤喃骨架系化合物:例如,1-(2 -呋喃基)甲烷磺酸、 2-(2-咲喃基)乙垸磺酸、3_(2_呋喃基)丙烷磺酸、2-甲基 -2-(2-呋喃基)丙烷磺酸、4-(2-呋喃基)丁烷磺酸、5-(2-呋喃基)戊烷磺酸、6-(2-呋喃基)己烷磺酸、7-(2-呋喃基 -27- 本纸張尺度適用中困國家標準(CN'S ) Λ4規格(210X29?公釐) 經濟部中央標準局員工消費合作社印製 A 7 B7五、發明説明(25 ) )庚烷磺酸、8-(2-呋喃基)辛焼磺酸、9-(2-呋喃基)壬烷 磺酸、10-(2-呋喃基)癸烷磺酸、12-(2-呋喃基)十二烷磺 酸等。 1,4-二噁烷骨架系化合物:例如,1-(1,4-二嗦烷-2-基)甲烷磺酸、2-(1,4-二噁烷-2-基)乙烷磺酸、3-(1,4-二噁烷-2-基)丙烷磺酸、2-甲基- 2-(1 ,4-二噁烷-2-基)丙 烷磺酸、4-(1,4-二噁烷-2-基)丁烷磺酸、5-(1,4-二噁烷 -2-基}戊烷磺酸、6-(1,4-二噁烷-2-基)己烷磺酸、7-(1, 4-二噁烷-2-基)庚烷磺酸、8-(1,4-二噁烷-2-基)辛烷磺 酸、9-(1,4-二噁烷-2-基)壬烷磺酸、10-(1,4-二噁烷- 2-基)癸烷磺酸、12-(1,4-二嗦烷-2-基)十二烷磺酸等。 苯並眯唑骨架系化合物.·例如,1-U-苯並咪唑基)甲 烷磺酸、2-U-苯並眯唑基)乙焼磺酸、3-(1-苯並眯唑基) 丙烷磺酸、2-甲基- 2-U-苯並眯唑基)丙烷磺酸、4-U-苯 並眯唑基)丁烷磺酸、5-U-苯並眯唑基)戊烷磺酸、6-(卜 苯並眯唑基)己烷磺酸、7-(卜笨並眯哇基)庚烷磺酸、8-( 卜苯並咪唑基)辛烷磺酸、9-(卜苯並咪唑基)壬烷磺酸、 1D-(1-苯並咪唑基)癸烷磺酸、12-(1-苯並咪唑基)十二烷 磺酸等。 苯並噻唑硫骨架系化合物:例如,1-(2 -苯並噻唑硫 基)甲烷磺酸、2-(2-笨並噻唑碕基)乙烷磺酸、3-(2-苯並 唾唑硫基)丙烷磺酸、2-甲基- 2-(2-苯並噻唑硫基)丙烷磺 酸、4-(2-苯並睡唑硫基)丁烷磺酸、5-(2-苯並噻唑疏基) 戊烷磺酸、6-(2-苯並噻唑硫基)己烷磺酸、7-(2-苯並噻 -28- 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210X297公釐) 434602 Μ Β7 五、發明説明(26 經濟部中央標聲局員工消費合作社印製 唑硫基)庚烷磺酸、8-(2-苯雏噻唑硫基)辛烷磺酸、9-(2-苯並瞜唑磙基)壬烧磺酸、10-(2-苯並睡唑疏華)癸烷磺酸 、12-(2-苯並睡唑碲基)十二烷磺酸等。 苯並異噁唑骨架系化合物:例如,1-(卜笨並異噁唑 基)甲焼磺酸、2-(1-苯並異噁唑基)乙烷磺酸、3-(卜苯並 異噁唑基)丙烷磺酸、2-甲基- 2-U-笨並異噁唑基)丙烷磺 酸、4-U-苯並異噁唑基)丁烷磺酸、5-(1-苯並異噁唑基) 戊烷磺酸、6-(卜苯並異噁唑基)己烷磺酸、7-U-苯並異 噁唑基)庚烷磺酸、8-(1-苯並異噁唑基)辛烷磺酸、9-(卜 苯並異噁唑基)壬烷磺酸、1G-(卜苯並異噁唑基)癸烷磺酸 、12-(1-苯並異噁唑基)十二烷磺酸等。 苯並三唑骨架系化合物:例如,1-(2-苯並三唑基)甲 烷磺酸、2-(2-笨並三唑基 > 乙烷磺酸、3-(2-苯並三唑基) 丙烷磺酸、2-甲基- 2-(2-苯並三唑基)丙烷磺酸、4-(2-苯 並三唑基)丁烷磺酸、5-(2-苯並三唑基)戊烷磺酸、6-(2-苯並三唑基)己烷磺酸、7-(2-苯並三唑基)庚烷磺酸、δα-苯並三唑基) 辛烷 磺酸、 9-(2-苯並三 唑基) 壬烷磺酸、 10-(2-苯並三唑基)癸烷磺酸、12-(2-苯並三唑基)十二烷 碌酸等。 苯並呋喃骨架系化合物;例如1-(3-苯並呋喃基}甲烷 磺酸、2-(3-苯並呋喃基)乙烷磺酸、3-(3-苯並呋哺基)丙 烷磺酸、2-甲基- 2-(3-苯並呋喃基)丙烷磺酸、4-(3-苯並 呋喃基)丁烷磺酸、5-(3-苯並呋喃基)戊烷磺酸、6-(3-苯 並呋喃基)己烷磺酸、7-(3-苯並呋哺基)庚烷磺酸、8-<3- -29- (請先閱讀背面之注意事項1'-本頁) 本紙張尺度適用中國國家標準(CNS ) Α4規格(2ί〇'Χ297公釐) A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(27 ) 苯並呋哺基)辛烷磺酸、9-(3-笨並呋喃基)壬烷磺酸、ΙΟ-ίδ-苯並呋 喃基) 癸烷 磺酸、 12-(3-苯並呋 喃基) 十 二烷磺 酸等。 又,上述之磺酸化合物之納或鈣翹等驗金靨或銨鹽等 四级氮系化合物鹽亦可作為上述之W提供陰離子之化合物 使用C 再者,上述之磺酸基直接於雜環骨架上取代之雜環化 合物之較可取之具體例為2-咪唑磺酸、呋喃-2-磺酸、呋 哺-3-磺酸、2-苯並咪唑磺酸、笨並呋喃-3-磺酸及其化合 物之鈉鹽等鹼金羼鹽、銨鹽或四级銨鹽。 又,雜環骨架上之氫原子被C t - C t 2,較可取為C i - C B 之直鐽或支鐽之飽和或不飽和之烴基或烷氧基之一個以上 取代之衍生物亦可作為上述之雜環磺酸離子使用。其取代 基之具體例包括:甲基、乙基、丙基、異丙基、丁基、異 丁基、第三丁基、戊基、己基、辛基、壬基、十二等等烷 基,或乙烯基、烯丙基、3-丁烯基、5-己烯基等不飽和基 ,及甲氧基、乙氧基、丙氧基、丁氧基、戊氧基、己氧基 、辛氧基、壬氧基及十二烷氧基等。 (3)脂肪族多環化合物之陰離子 本發明使用之脂肪多環化合物之陰雜子為具有:備有 磺酸或羧酸、磷酸、硼酸等質子酸基(Briinsted acid)之 二環以上之多環脂肪族陰雔子之化合物,較可取者為磺酸 或羧酸取代化合物,尤其可取者為磺酸取代化合物,其具 體例包括:d -樟腦磺酸(式X V11)(別名:1 〇 -樟腦磺酸)、2 _ -30- - 本紙張尺度適用中國因家標準(CNS ) Λ4規格(2丨0X297公釐) (請先閱讀背面之注意事項再續1'本頁) -裝—— 訂 ---r線V. Description of the invention (IS) Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs > 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 >, 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 > 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) > 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- < 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 一一 一 _ _ 五、發明説明(28 ) 撺腦磺酸(式XVIII)、3-撺腦磺酸、8-撺腦磺酸、d-樟腦 羧酸及其衍生物。在使用時,K其銨鹽或鐮金羼之形態使 用。 (XVII)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)
(ΧΥΉΙ) 本發明中使用之氧化劑,只要其逋合吡咯或睡吩類之 氧化聚合者均可,例如特開平2-15611號公報所述之氯化 鐵(H )、Fe(Cl〇4)3或有櫬酸_(班)、無機酸鐵(® )、烷 基過硫酸鹽、過磺酸銨、過氧化氫、K2Cra〇r等。上述之 有櫬酸鐵{B)之有機酸為例如甲烷磺酸或例如十二烷基 苯磺酸等Ci -C21J烷S磺酸或脂肪族羧酸。但,上述氧化劑 之使用範圃間或會受上述式(If)所示之單體化合物之化 學構造、氧化劑Μ及反應條件等之限制。例如,噻吩類之 氧化(聚合),依 Handbook of Conducting Polymers 雜結 (M a r c e 1 D e k k e r , I n c ·發行,1 9 8 7,p p . 9 9 , F i g · 5 )之 說明,依取代基之種類氧化電位(表示聚合容易度之指標) -3 1- 本紙張尺度適用中國國家標率(CNS ) Λ4規格(2丨OX29·;公釐) n n^— m» 1^1 ·*--- ..1^1 -I In - ---1^eJ....... --« -..... t- n ...... HM (請先閲讀背面之注意事項.再广',本頁) 一 經濟部中央標準局員工消費合作社印裝 4 3 4 6 Ο 2 A7 B7 經濟部中央橾準局員工消費合作杜印製 五、發明説明(29 ) 大幅改變(氧化電位之範圃為約1.8〜約2.7V),而左右聚 合反應。因此,使用之聚合性單體化合物與氧化劑、反應 條件之組合乃極為重要。 本發明中上逑有機陰雄子Μ外之其他作為接雜物之陰 離子為上述氧化劑之反應後之邋原體陰雄子,例如氯雛子 、C10«-、Ct-Cu之脂肪族有機羧酸陰離子、疏酸陰雄子 、璘酸陰雄子、Ci-Cu之脂肪族有機磷酸陰離子、晒酸陰 離子等。另外亦可使用NO*、NO〆鹽(例如NOBF*、NOPFs、 HOSbFe n NOAsFb ' NOCHs SOs ' N 0 2 B F« > NOaPFe ' NOa CF3 S03 )之電子受容體接雜物。 在本發明之固體電解電容器之製造方法中,上逑式 (IV)所示噻吩類之化學聚合時,以過硫酸鹽作為氧化爾 最為適合,使用锇(I)鹽系氧化劑時有锇元素之殘存問題 ,影響電容器之特性。又,對上述式(IV)之聚合性軍體化 合物適用之遇磙酸鹽對前述式U)中,其RhRkH及X = S 之睡吩並不適用,因此氧化劑之使用自有其限制。於上述 式(IV)所示之噻吩類之化學聚合特別適用之過硫酸鹽為 例如過硫酸銨及過確酸鉀。 次說明固體電解質之形成(聚合)反應的可取條件於下: 使用於本發明之電容器之製造方法之式(H)或式(IV) 之聚合性軍賭化合物之,濃度、氧化劑以及上述(1)〜(3)之 有機陰雄子摻雜物之各使用濃度雖然依化合物及其取代基 之種類或其與溶媒等之組合而不同,但通常為lx 1{)-*〜 10莫耳/公升範圍,最佳為IX 1〇-3〜5莫耳/公升範圍。反 -32- (*先閱讀背面之注意事項再楨寫本頁) -裝. 、βτ 線 本紙張尺度適用中國國家標準(CNS ) Λ4規格(2i〇X 297公後)(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 «> 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、發明説明(30 ) 請 閲 讀 背 之 注 意 事 項 I袭 頁 應溫度則依反應古法而不同,故難加K界定,但通常為-70 t:〜25〇υ ,較可取為otl〜1501C ,特別可取為15〜lflflt: 範琴。 訂 本發明製造方法逋用之溶液或聚合後之洙淨用溶媒之 . 較可取考為例如四氣呋哺(ΤΗΠ或二噁烷、二乙醚等酸類 、或丙酮、二甲基乙酮等飼類,二甲基甲釀胺(DMF)或乙 睛、苄睛、N-甲基吡咯醌(SMP)、二甲基亞碘(DMSO)等非 質子性極性溶媒,乙酸乙酯或乙酸丁酯等酯類,.氛仿或二 氯甲烷等非芳香族之氛糸溶媒,硝基甲烷或硝基乙烷、硝 基笨等硝基化合物,或例如甲醇、乙醇、丙醇等醇類,另 外如甲酸或乙酸、丙酸等有機酸或該有機酸之酸酐(如乙 _酐)、水或披等之混合溶媒。較可取者為水、酵類、萌 類及/或其混合系。 茲參照第1圖說明本發明固體電解電容器之構成之概 要於次: 線 經濟部中央標舉局—工消费合作社印製- 本發明之一方之電極(陽極)1係使用鋁、钛、組、鈮 或Μ其為基質之合金系等具有閥作用之金靨萡、棒或Μ其 為主成分形成之燒结體等習知材料,並為了形成介質層及 增大比表面積目的,依習知方法對該等金羼電極之表面實 腌蝕刻或化學(化成)處理,Μ在金鼷箔上形成該金靥系氧 化被膜層3。 固體電解質(導電性聚合物組成物)4之形成,宜採用 在介質層上聚合上述聚合性軍體化合物之方法,尤其使用 本發明之酎熱性優異之専電性聚合物組成物在具有细孔或 -33- 本紙张尺度適用中國國家標隼(CNS ) Λ4^格(2iOX297公釐) 434602 Α7 Β7 五 發明説明(31 ) 經濟部中央標準局員工消費合作社印製 空隙構造之介質層上化學的析出之方法。另外,為了提高 電接觸,最好在上述之方法形成之導電性聚合物狙成物層 上進一步設置其他導電體層,即例如塗佈等電糊或利用電 鍍、蒸鍍、赛電樹腊膜等形成導電體層5。 對依本發明之上述製造方法製造之固體電解電容器, 再在其導電體層5上模覆樹胞或配裝樹脂或金屬製之外装 毅,或藉浸漬(dipping)樹脂等方式設置包封體6,進而 配設接縯端子?即可製得適合各種用途之固體電解電容器 製品。 次配合實施例、比較例及參考例說明本發明之最佳霣 施形態於下<= 實施例1 使用10重量!K之己二酸铵水溶液及施加13V之電壓對 切成所規定之大小面積之蝕刻處理過之鋁箔(基板)進行化 學(化成)處理使在該鋁箔表面形介質層(即形成介質氣化 被膜),繼之將其浸漬於含有20重量3:之璏磙酸铵(以下稱 為APS)及0.3重量:ί之2-丙氧萘-6-磺酸納之水溶液(3Γ 中,使介質層表面含浸該水溶液後,再浸漬於溶有5克之 3,4-二氧乙烯-噻吩之1.2莫耳/公升的異丙酵(以下稱ΙΡΑ )溶液(溶液4 )中之後取出,並在6 0 1C之環境下放置1 0分 鐘實行氧化聚合。聚合完成後Μ水洗淨。將此聚合反應處 理及洗淨步驟各反覆實施10次。随後,將上述形成之導電 性聚合物層(固賭電解質層)置於水/ ΙΡΑ溶媒中行肼還原 並小心的萃取及利用鑼子色層分析求得聚合物中之碕酸離 -34- 本紙張尺度適用中國國家標準(CNS ) Α4規格(210Χ 297公:t ) 經濟部中央標隼局員工消費合作社印製 A7 B7 五、發明説明(32 ) 子及2-丙氧萘-6-磺酸離子之含量,结果K聚合物之每一 全反覆構造單元計,碲酸雄子含量為1.6莫耳3;,2-丙氧 萘-6-磺酸離子含1為13.6莫耳3!。固體電解質層之電専 度為 75s/ca。 繼之,將上述之形成有噻吩聚合物之鋁箔(基板)置於 10重董X之己二酸銨水溶鞔中處理後,檢測其火花霣壓。 為了確切比較試樣元件特性,增加元件數目(Μ下之霣施 例亦同)。即,在sot:環境下及電流密度10 B A/c·2之條件 * 下,對元件各實行5次5;结果如下表i所示。 然後,於上述鋁箔之肜成有導電性聚合物層之部分塗 上碳糊(carbon paste)及銀糊後接陰極引線端子,同時 在未ϋ成有導電性聚合物層之鋁芯部焊接陽極引線蝙子, i 最後利用環氧樹脂封止而製取電容器元件。將此電容器元 件置於125TC下經過2小時之熟化後,測定其初期特性, 其结果示於下表2。此表中之初期特性之C代表容量,DF 代表損失角之正切(tanS )(亦即損失係數)。此等值皆在 12 0Hz測定者。Z代表諧振頻率時之姐抗值,而LC代表施 加額定電壓1分鐘測定之漏電流值。各測定值皆為3 0個電 容器元件之平均值。又,LC係Kl« A以上者視為不良品, ΙΟμΑΜ上者以短路品表示。 霣施例2 將依實胨例1所述方法製備之具有介質層之鋁萡(基 板),浸漬於含有20重量3:之ASP之水溶液(溶液1)中,使 介質表面含浸該水溶液後,再浸漬於溶有5克之3,4-二氧 -35- 尺度適用中國國家標隼(CNS ) Λ4規格(2IOX29V公;隻) 1^1, HH ! - i I —Hr «^^1 If In In i-! Ml - ! i - — —I-eJ......I II: 匿 m - - * (請先閱讀背面之注意事項4?本頁) ~ A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(33 ) 乙烯-睡盼之1 . 2其耳/公升,之IPA溶液中添加有2-丙氧萘 -6-磺酸四丁銨鹽而將此鹽之濃度調成0. 1重量%所得之 IPA/水混合溶获(溶液2)中。 此時使用之上述2-丙氧萘-6-磺酸四丁銨鹽係由2-丙 氧菜-6-磺酸納與四丁基銨化溴混合反應後再结晶製取者。 然後,混合溶液(溶液2)取出,並在60¾之環境下 放置10分鐘進行氧化聚合,聚合完成後K水洗淨。將此聚 合反應處理及洗淨步驟各反覆實施1β次後,依實施例1所 述方法評估结果如表1及表2所示,即聚合物中之硫酸離 子含量為2.2莫耳%, 2-丙氧萘-6-磺酸雜子含量為7.5莫 耳3!,固趙電解質層之電導度為58s/cb。 實施例3 將依賁廉例1所述方法製備之具有介質層之鋁萡(基 板),浸濱於溶有5克之3,4-二氧乙烯-睡吩之1.2其耳/ 公升的IPA溶液(溶液4)後,再浸潰於APS濃度2 0重量 及2-甲氧萘-6-磺酸納濃度0.1重量X之水溶液(溶液3)中 。随後取出並在8〇υ之環境下放置1〇分鐘進行氧化聚合, 聚合完成後K水洗淨。將此聚合反應處理及洙淨步驟各反 覆實施10次後,依賁施例1所述方法評估结果如表1及表 2所示,即聚合物中之硫酸雄子含量為1.8冥耳55,2-甲氧 蔡-6-磺酸離子含量為〇 . 8莫耳5!,固體電解質層之電導度 為 6.0s/cn〇 實ife例4 將依實施例1所述方法製備之具有介質層之鋁箔(基 -36- 本紙張尺度適用中國國家標準(CNS } A4.C格(2!GX297公釐) (請先閱讀背面之注意事項再铲%本頁) .裝--1 4° 經濟部中央標舉局員工消費合作杜印製 Α7 Β7 五、發明説明(34 ) 板),浸漬於含有過碲酸鉀10重最%及2 -甲氧萘-6-磺酸納 fl.l重量X之溶液(溶液3)後,再浸潰於溶有5克之3,4-二氧乙烯-睡吩之1.2其耳/公升的IPA溶液(溶液4)中。 陲後取出該基板並在60t:之環境下放置1Q分鐘逍行氧化聚 合。將上述之浸潰步》及聚合反應處理各反覆實腌10次後 Κ水洗淨。然後依寶施例1所述方法評估,结果為表1及 表2所示,即聚合物中之碇酸雄子含量為5.9莫耳X、2-甲氧萘-6-磺酸離子含量為15.5莫耳Ϊ,固通電解質層之 ' 電導度為73s/cb。 實施例5 將依實施例1所述方法製備之具有介質層之鋁萡(基 板),浸漬於含有APS濃度3 5重量X之水溶液(溶液u後, 再浸湏於溶有5克之3,4-二氧乙烯-噻吩之1.2其耳/公升 之ΙΡΑ溶液中添加有2,3-二甲氧苯-6-磺酸四丁銨鹽(湄度 0.04重量X)之ΙΡΑ/水混合溶液(溶液γ)。此時,使用之 上述2,3-二甲氧萘-6-確酸四丁銨盥係由2,3-二甲氧蔡- 6-磺酸納與四丁基銨溴反應後予以再结晶製得者。 遒之,由上述溶液2取出該基板,並在60t:環境下放 置1Q分鐘進行氧化聚合。將上述之浸漬步驟及聚合反應處 理各反覆實施10次後Μ水洗淨及乾烽。然後依實施例1所 逑方法評估,结果如表1及表2所示,即聚合物中之磙酸 離子含最5.2莫耳X, 2,3-二甲氧萘-6-磺酸離子含量為7. 莫取Χ,固體電解質層之電導度為4 0 s / c Β。 -37- 本紙浪尺度適用中國國家標率(CNS〉Α4規格(2ΐϋΧ 297公釐) 4“,、 經濟部中央標準局員工消費合作社印製 A7 ,_^_B7 五、發明説明(35 ) 實施例6 將實豳例1所述方法製備之具有介質層之鋁萡(基板) I ,浸潰於依特開平2 -2 4 2 316號公報記載方法合成及昇華 所得之5, 6-二甲氧基異硫茚的1.2莫耳/公升瀠度之脫氣 , 二 IPA溶液(溶液4)後,再浸漬於20重量χ濃度之APS水溶 液中添加有0.1重量X之2-丙氧蔡-6-磺酸鈉之水t瘩液(溶 硖3) 〇 繼之,由上洋溶蔌3取出該基板,並在60Ό環境下放 置10分鐘進行氧化聚合。將上述之浸漬步驟及聚合反應處 、 I 理各反覆實施10次後K水洗淨及乾燥。然後依實施例1所 述方法評估,结果如表1及表2所示,即聚合物中之硫酸' « 離子含、董0.7莫耳:ϊ,2 -丙氧蔡-6-磺酸離子含量為6·0莫 取!Ϊ,固體電解質層之電専虔為33s/cm。 , 實施例7 ‘ . 除了替代ΐ施例1之3,4-二氧乙烯-睡吩便用吡咯-N-甲基_之同濃度溶液之外,其餘悉依實施例1所述方法實 行及評估,结果如表1及表2所示,卽聚合物中之硫酸雄 子含量為7.8莫耳X, 2-甲氧萘-6-磺酸離子含量為12.3莫 耳尤,固體電解質層之電導度為7S/CB。 實施例8 將實施例1製備之鋁箔(基板)浸漬於含有2-甲氧萘-6 -磺酸納濃度0.1軎量X及3, 4-二氧乙烯-噻吩1.2其耳/, 公升濃度之30¾ DMF(二甲基甲豳胺)-IPA溶液(溶液2)後 / ’ ,再浸漬於20重量$之APS水溶液(溶液1)。取出該基板 _ 3 8 - (請先閱讀背面之注^一^項再"寫本頁) -裝. 訂 線 本紙張尺度適用中國國家標準(CNS ) A4規格(21ϋΧ 297公| ) Λ Α7 Β7 五、發明説明(36 ) 經濟部中夹標隼局員工消費合作社印製 後,在60¾環境下放置ΙΟ公鐘進行氧化聚合。將此浸湏步 驟及聚合反應處理各反覆1〇次後水洗及乾燥。繼之,依實 施例1所述方法評估结果如表1及表2所示,即硫^酸離子 含量為1.5冥耳X, 2-甲氧萦-6-磺酸離子含量為3.2冥耳 X,固體電解質層之電導度為7 1 s / c m。 實施例9 ^ 除了使用12重量55以替代2〇M量%之APS之外,其餘 悉依實施例1實施。評估结果以表1及表2所示。聚合物 中之疏酸離子含量為0.2莫耳X,2丨甲氧磺酸離子含 量為20莫耳$,固體電解質層之電導度為28s/cm。 ^ 實施例10 將實施例1製備之鋁箔(基板)浸漬於含有2-甲氧萘-6 -磺酸鐵(III)之12¾ IPA溶液後,再浸漬於溶有5克之 3 , 4-二氧乙烯-噻吩之1 · 2其耳/公升濃度之IPA溶液。取 出該基板後,在瑁境下放置10公鐘進行氧化聚合後水 洙淨。將上述之聚合反應處理及洗淨步驟反覆實施10次後 ,依實施例1所同樣方法評估结果如表1及表2所示。聚 合物中之2-甲氧萘-6-磺酸離子含量為17萁耳!Ϊ,固體電解 質層之電導度為30s/cb〇 參考例1 除了以硫酸鐵10重1¾以替代APS及使用2 -甲氧萘-6 -磺酸納之0.1重量3;溶疲之外,其餘悉依實施例1實行, 结果如表1及表2所示。聚合物中之硫酸離子含量為24. 5其耳5;、2-甲氧萘-6-磺酸雜子含最為33.8耳χ,但,由 -39- 本紙乐尺度適用中國國家標準(CNS ) Λ4規格(2!0X29?公漦) '(閱讀背面之注意事項:本頁) -裝 ,?τ 線· 434602 A7 B7 五、發明説明(37i. 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
經濟部中央標準局員工消費合作杜印I 於有鐵離子8萁耳χ存在Μ及碕酸雄子含量超過ίο莫耳ί, 因此電容器之特性不良。 參考例2 除將實施例1使用之3,4-二氧乙烯-噻朌改為噻吩, Μ10重量Ϊ之氧化‘替代APS及使用2-甲氧萘-6 =磺酸納 0.1重量X之溶液之外,其餘悉依實施例1實行,结果如' 表1及表2所示。聚合物中之2-甲氧萦-6-磺酸離子含量 為3.1莫耳X。由於不含硫酸離子,故電容器之4性不良。 參考例3 π . 除將實豳例1使用之3, 4-二氧乙烯-噻吩改為睡吩之* 外,其餘悉依實.施例1實行,但完全不生成黑青色之聚睡 吩即APS之作用無法使噻吩起聚合反應。即,依APS之ΐέ 吩類之氧化聚令僅對3, 4-二氧基取代之噻吩類特異的發生。 參考例4 ' 除將實施例1使用之2-丙氧萘-6-磺酸納改為2-羥基 萘-6-磺酸納之外,其餘悉依實施例1實行',结果如表1 及表2所示。聚合物中之硫酸離子含量為4.3萁耳X, 2-羥基萘-6-磺酸離子含量/為12.1其耳χ,固體電解質層之 電導度為iOs/cm。 由表中所示可知,實施例1〜9在火花電壓試驗中幾 乎無電壓之下降,此證明介質被膜層無發生任何損傷。又 簧陁例10之使用有機系鐵鹽之電容器,在火花電壓試驗中 並無電壓之下降,但使用無機糸鐵鹽之參考例1、2均有 電壓之明顯下降,K致在規定次數终了前均無法保持電壓 -40- (請先閱讀背面之注意事項再4 ,Α本頁 本紙張尺度適用中國國家標準(CNS ) Λ4規格(210 X 公釐)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)
.-r w . C Λ7 B7 五、發明説明(38 之漬 % 浸。 耳之用 冥次實 8 數合 有經不 於即 , 由 ,傷 ,大損 合極生 場下發 之降層 鐵之質 酸壓介 硫電果 用花结 使火 , 之果下 1 结降 例,顯 考存 參殘 其子、電 尤離花 ,鐵火 asl ^ 表 位 單 /IV 壓 電 花 火 數 件 元 聚合操作次数 1 2 3 4 ‘· 5 6 8 10 實施例1 實施例2 實施例3 實施例4 實施例5 實施例6 實施例7 實施例8 實施例9 實施例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 18 19 19 19 19 19 19 19 19 19 17 19 19 19 19 19 19 19 19 19 16 19 19 19 19 19 19 19 19 19 15 19 19 19 19 19 19 19 19 19 11 19 19 19 19 19 19 參考例1 參考例2 參考例4 19 18 19 16 16 18 14 10 15 7 3 11 3 9 3 I --·- 1-1*!. -* —-批衣--- (請先閲讀背面之注意事項>1 ,,寫本頁) 訂 線 經濟部中央標準局員工消費合作社印製 4 Λ Nsc. 準 標 一家 -國 I國 I中 用, 一適 尺 張 紙 it 公 97 2 434602 Α7 Β7 五、發明説明(39 ) 表2 初 期 特性 C DF Ζ LC 不良數/試樣數 短路 U F % οΩ u k 個/個 實施例1 8.1 0.8 60 0.02 0/30 0 實賍例2 8.0 0.8 60 0.02 0/30 0 實旛例3 7.6 0.8 60 0.02 0/30 0 賁施例4 7.0 0.8 60 0.04 1/30 0 賁施例5 6.8 0.9 60 0 .05 1/30 0 賁胨例6 6.8 0.8 60 0.05 1/3» 0 實施例7 4.0 1.3 60 0.11 1/30 0 實施例8 8.2 0.7 60 0.02 0/30 ,0 實施例S 6.9 0.7 60 0.10 1/30 0 賁施例 6.9 1.0 60 0.10 1/30 0 參考例1 8.1 3.2 83 0.41 15/30 10 參考锊2 5.S η 0 . U 87 0.40 27/30 16 參考例4 5.0 1.2 60 0 . 10 3/30 0 (請先閲讀背面之注意事項再疗寫本育) 裝---- 經濟部中央標準局員工消費合作社印製 實施例11 將依實旅例1製備之表面形成有介電質層之寧箔(基 板)浸漬於含有APS 20重量χ 、4-嗎啉丙烷磺酸納(東京 化成公司製)0.125重量5S之水溶液(溶液3)後,再浸潰 > 於溶有5克之3 ,4-二氧乙辦噻盼之1.2莫耳/公升ΐρΑ溶 液(溶液4)。取出該基板後,在6〇t:環境下放置1〇分鐘進 行氧化聚合。聚合完成後Μ水洗淨該基板。將上述之聚合 反應處理及洗淨步驟各反覆實行10次。 導電性聚合物中之硫酸離子及4-嗎啉丙烷磺酸離子、之 含量,係藉將上逑所得之基板置於水/ΙΡΑ溶媒中,利用 阱遨_原後,小心的萃取而依.離子色層分析法求得聚合物中 之硫酸雜子及4-嗎啉丙烷磺酸.離之含量,结果以聚合物之 -4 2 - ^ I _ 1 If···· 1 線 本紙張尺度適用中國國家標準(CNS ) A4规格(210X29'?公釐) 434602 經濟部中来標準局負工消費合作社印a* A7 ' B7五、發明説明(4〇 ) 全反覆構造軍元計,硫酸離子含量為1·5冥耳5:, 4-嗎啉 丙烷磺酸雄子含量14、0冥耳5S,固體電解質層之電導度73 S / C 1 ° * 黴之,將上述之形成有3,4-二f乙烯-嗶吩聚合物之 鋁箔基板置於ifl重量ίί之己二酸銨i溶液中處理後,檢測 其火花電壓,為了硫切比較試漾元件之特性,增加元件數 目(以下之實施例亦同)。即,在50Ό環'境及電流密度11) πΑ/cm2之條件下,對元件數π = 5實行(即對5涸元件實行) ,结果如表3所示。 ' ' 然後,於上逑箔之形成有導電性聚合物靨之部分塗上 碳糊(carbon paste).及銀槌後,接陰極引線端子,同時在 未形成有導電性聚合物層之鋁芯部焊接陽極引線端子,最 後利用環氧樹脂封止而製取電容器元件。將此電容器元件 置於1 2 5 υ下經遴2小時之热化後,測定其初期特性,其 结果示於下表2。此表中之初期特性之C代表容量,DF代 V ♦ 表損失角之正切UaaS )(亦即損失係數)。此等值皆在120 Η z測定者。Z代表諧振頻率時之姐抗值,而L C代表廉加額 定電壓1分鐘測定之漏電流值。各澉值比為30個電容器元 件之平均测值。又,LC係M i«AK上者視為不良品,10 AM上者Μ短路品表示。 實施例1 2 將實陁例11所述方法製備之表面形成有介質層之鋁箔 (基板)浸漬於APS濃度20重量X之水溶液(溶液1)後,再 浸潰於溶有5克之3, 4-二氧乙烯-噻吩之1 . 2莫耳/公升之 -43- 請 閱 讀 背 之 注 意 事 項 再- 1/ k 本 頁 本紙伕尺度適用中國國家標準(CN’S > Λ4規格(2!〇>+ 297公釐〉 ,Η . / 經濟'邓中央樣準馬員工消费合作·杜印袋 ·*1-♦ 4.-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 > 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 > Λ4 specifications (2! 〇 > + 297 mm>, Η. / Economy 'Deng Zhongyang likes Malaysian consumer consumption cooperation · Du India bags · * 1- ♦ 4
B7__ 五、發明説明(41 ) IPA溶液中添加4-嗎啉丙烷磺酸四丁銨醱(M下簡稱M OP STB 鹽)而將其澹度調為0.1重量2IPA/水混合溶液(溶液2 )。炜時,上述之MOPSTB鹽係使用4-嗎啉丙烷磺酸納(東 京化成公司製)與四丁基溴化銨混合反應而經再结晶製得 者。取出該基板後在6〇υ環境下放置1G分鐘進行氧化聚合 ,然後以水洗淨。將上述之聚合反應處理及洗淨步驟各反 琿實行1G次,並依賁施例11所述方法評估電容器元件,结 果如表3及表4所示聚合物中之硫酸離子為1.6其耳X,4 -竭啉丙烷磺酸離子含量為S.1莫耳$,固涯電解質曆之電 導度為5 6 s / c ffl。 _實施例1 3 將實施例11之同樣方法製備之鋁萡(基板 >浸渍於溶有.. 5克之3, 4-二氧乙烯-噻吩之1.2其耳/公升的IPA溶液( 溶液4)後,再浸漬於APS濃度20重量)及4-嗎啉丙烷磺 酸納濃度fl.l重量%之水溶液(溶液3)。取出該基板後, 在60C環境下放實10分鐘進行氧化聚合後以水洗淨。 將上述聚合反應處理及洗淨步驟各反覆實行10次,並 依實施例11所述方法評估所得之電容器元件,结果如表3 及表4所示。聚合物中之硫酸離子含量為2,0莫耳:U、4-嗎啉丙烷磺酸離子含量為0.8萁耳%,固體電解質層之電 丨' 導度為60s/cia。 !施例i 4 I 將實施例11之同樣方法製備之鋁箔(基板)浸漬於溶有 5克之3 , 4-二氧乙烯-噻吩之1 . 2莫耳/公升的IPA溶液( -44- 本纸張尺度適用中國國家標準(CMS ) Λ4規格(2:〇:<297公釐) (請先閱讀背面之注意Ϋ-作再填.¾本頁) —^ϋ 1^1 m UK In leJ. I ----- —I— 1 線--- 43460 a Α7 Β7 .經濟中央標率局員工消費合作杜印製 五、發明説明(42) 溶液4)後,再浸潰於APS濃度20重量:ί及4-嗎啉乙烷磺 酸纳濃度0.3重量X之水溶液(溶液3)。取出該基板後, 在6〇υ環境下放置分鐘進行氧化聚合後Μ水洗淨。 將上述聚合反應處理及洗淨步驟各反覆實行10次,並 依實施例11所逑方法評估所得之電容器元件,结果如表3 及表4所示。聚合物中之硫酸離子含量為2.1莫耳J;、4-嗎啉乙焼磺酸離子含量為〇 . 8冥耳X,固體電解質層之電 導度為60S/CB»。 實施例15 - 將實施例之同樣方法製備之鋁箔(基板)浸潰於含有 過硫酸鉀10重量%、4-嗎啉丙烷磺酸納(東京化成公司製) 〇 . 1重量X之水溶疲(溶液3)後,再浸潰於溶有5克之3, 4-二氧乙烯-嗪吩之1 . 2莫耳/公升的ΙΡΑ溶液(溶液4)取 出該基板後,在6 01:環境下放置1 〇分鐘進行氧化聚合後Μ 水洗淨。 將上述浸漬及聚合反應處理各反覆實行10次後,水洗 及乾燥,並依實施例11之方法評估所得之電.容器元件,结 果如表3及表4所示。聚合物中之硫酸離子含量為6.2莫 耳X、4-嗎啉丙烷磺酸離子含量為15莫耳X,固體電解質 層之電導度為74s/cb。 實施例16 將實施例11之同樣方法製備之鋁箔(基板)浸漬於依日 本特開平2 - 2 4 28 1 6號公報記載之方法合成及昇華製得之 5 , 6 -二甲氧基-異硫茚之1 . 2莫耳/公升濃度之脫氣I ρ Α溶 *45~ m HI. Λ 1 m ~ I — tmt (請先閱讀背面之注意事項再^-本頁) 尽纸張尺度適用中國國家標準(C1SS ) Λ4規格(·2丨0)< 297公座) 經濟部中央標準局員工消費合作社印製 A7 B7五、發明説明(43 ) 液4)後,再浸漬於20重最X.濃度之APS水溶液中含有〇 . 1 重量3;溻度之嗎啉丙烷磺酸納之氺溶液(溶液)。取出 該基板在60Ό環境下放置10分鐘進行氧化聚合。 將上逑之浸漬及聚合反應處理各反覆實行10次後,K 水洗淨及乾煉,並依實施例11之方法評估所得之電容器元 件,结果如表3及表4所示。聚合物中之碇酸離子含量為 〇 . 8莫耳35、4-嗎琳丙烷磺酸雜子含量為5 . 7其耳J;,固體 電解質層之電導度為31s/cb。 實施例17 除了 Μ吡咯-N-甲醮替代3,4-二氧乙烯-噻吩以外,其 餘悉依實施例11實行,所得之電容器元件評估结果如表3 及表4所示。聚合物中之硫酸離子含量為6.8莫耳3:、4-嗎咻丙烷碕酸離子含量為1 6 · 8萁耳3:,固體電解質層之電 導度為7s/cib〇 實施例IS 將實陁例11之同樣方法製備之鋁箔(基板)浸潰於4-嗎 啉丙烷磺酸納濃度0.1重量5:及3,4-二氧乙烯-噻吩1.2莫 耳/公升濃度之30% DMF-IPA(溶液2)後,再浸濱於20重量 %濃度之APS水溶液(溶液1}。取出該基板後置於60Ό環 境下放置10分鐘進行氧化聚合。 將上述之浸潰及聚合反懕處理各反覆實行10次後水洗 及乾燥,並依實施例11之方法評估所得之電容器元件,结 果如表3及表4所示。聚合物中之硫酸離子含量為1.7莫 耳%,4-嗎啉丙烷磺酸維子含量為32其耳固體電解質層 -46- ----J---------裝------訂-------線1— <· ί (請先閱讀背面之注意事項再.績.寫本頁) 本纸張尺度適用中國國家標隼(CNS ) A4规格(2丨OXM:7公釐) 經濟部智慧財產局員工消費合作社印製 .* 1 *· A7 B7 五、發明說明() j 之電 導 度為75s/c in 〇 實施 例 19 除 將實施例1 1中使 用之2 0重量5! APS改為 12重量XAPS 之 外 9 其餘悉依實施例 11實行。製得之電容器 元件之評估 結 果 如 表3及表4 所示 0 聚合物之硫酸離子 含量0 . 16莫耳%,4-嗎 啉丙烷磺酸 離 子 含 量為25莫耳X,固體電解質層之電導度為34s/cm。 實 施 例 20 除 以2-苯並畔 唑丙 烷磺酸納替代4-嗎啉丙 烷磺酸納之 外 其 餘悉依實施 例11 實行。製得之電容器元 件之評估结 果 如 表 3及表4所 示。 聚合物中之硫酸離子含 量^ 1.8莫 耳 %, 2 -苯並咪唑丙烷磺酸離子含量為14.5冥 耳%,固體 電 解 質 層之電導度 為70 s / c 诅 〇 實 施 例 21 除 M4-甲基-1-哌嗪甲烷磺酸納替代4-嗎啉丙烷磺酸 納 之 外 ,其餘悉依 實施 例11實行。製得之電容 器元件之評 估 结 果 如表3及表 4所 示。聚合物中之硫酸離 子含量為 2 0 冥 耳%,4 -甲基-1- 哌晓甲烷磺酸離子含量 為16 . 5莫 耳 %, 固體電解質層之電導度為65s/cm。 實 施 例 22 除 Μ 2 , 3-苯並 呋喃 -3-磺酸鈉替代4-嗎啉丙烷磺酸納 之 外 ) 其餘悉依實 施例 11實行。製得之電容器 元件之評估 结 果 如 表3及表4 所示 。聚合物中之硫酸離子 含量為1 . 9 莫 耳 %, 2 , 3-苯並Β 夫哺- 3-磺酸離子含量為15 . 8 莫耳%,固 -47- (請先閱讀背面之注意事項再填寫本頁) 本紙張尺度適用中國國家標準(CNS)A4規格"(210 χ 297公釐) 4346 0 2B7__ 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: < 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) < 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— < · 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 " (210 χ 297 mm) 4346 0 2
經濟部中央標準局員工消費合作社印製 五、發明説明(45 ) 體電解質層之電導度為61s/cm。 .比較例1 除了 K噻吩替代3,4-二氧乙烯-噻吩作為單體化·合物 及Μ 1Π重量X之氯化截替代APS而與4-嗎啉丙烷磺酸钠 〇.1重量X調製水溶液之外,其餘悉依實施例'11實行。製 得之電容器元件之評估结果如表3及表4所示。聚合物中 之4-嗎啉丙烷磺酸離子含量為2.5莫耳5;。由於未併用硫 酸離子,故電容器之不良率高。 比較例2 將1施例11之同樣方法製備之鋁ig (基板)浸漬於4-嗎 琳丙烷磺酸截(III)之12X IPA溶液後,再浸潰於繪有5 克之3,4-二氧乙烯-睡吩之1 .2其耳/公升濃度IPA溶液。 取出該基板後在6(PC環境下放置10分鐘進行氧化聚合後以 水洗,。將上述聚合反應及冼淨步驟各反覆實行10次。聚 合物中之4-嗎啉丙烷磺酸離子之含量係將上述聚合物置於 水/ I P A溶媒中實行肼遢原金小心萃取而_雔子色層分析 法求出,结果4-嗎琳丙院擴酸離子含量以聚合物之全反覆 構造單元計為15莫耳固體電解質層之電導度為35 S/CB。 使用上述製得之形成有導電性聚合物層之鋁箔製作電 容器元件,並依實施例11方法檢測火花電壓及其他電容器 特性,结果如表3及表4所示。 比較例3 除了 K硫酸鐵1 0重量X替代A P S 2 0重量%及使用4 _嗎 啉丙烷磺酸納0.1重量%之外,其餘悉依實豳例丨丨實行。 -48- 本紙張尺度適用中國國家標準(CNS ) Λ4規格(2丨GX 297公釐) C請先閲讀背面之法意事項1/¾本貫 -装 線 4 3 4 A7 B7 五 '發明説明(46 ) 製得之電容器元件之評估结果如表3及表4所示。聚合物 中之硫酸離子及4-嗎啉丙焼磺酸離子之含量,依實施例11 記載之方法算出结果,硫酸離子含量為I9.6莫耳X,4-嗎 啉丙烷磺含量為3 u莫耳X。但,由於鐵離子有8莫耳X 存在,且醗酸雜子含畺超遇10莫耳玫電容器之不良率 高0 實施例11〜22之火花電壓試驗均幾乎無電壓降下,反 應终了時之火花電壓均在1 9 V Μ下。對此,比較例3之使 用硫酸鐵之場合,甶於有8莫耳之鐵雜子殘存,因此火花 電壓之降下大,在規定之反應终了前火花電壓即降下,致 使固體電解質無法充份的填充。 參考例5 ,除了以噻吩替代3,4-二氧乙烯-噻吩之外,其餘悉依 實施例11實行製造電容器元件,但完全不生成黑青色之聚 噻吩聚合物.,,顯示噻吩之聚合反應未因APS之作用而發生 。即,利用APS之唾吩類之氧化聚合僅對3 ,4-二氧基取代 之噻吩類特異的發生。 ~ ----^--^---Γ 裝------訂----.-----線 -» (請先閱讀背面之注意事項再''·本頁) . 一 經濟部中夫標準局肩工消費合作社印製 -49- 本纸乐尺度適用中國國家標準(CN’S ) A4规格(210 X 297公釐) 7 Β 五、發明説明(47 ) 表 位 單 /1% 壓 Β 賃 花 火 5 II η 數 件 元 反 應 次 數 1 2 3 4 5 6 8 10 實施例U 實施例1 2 實施例13 實施例14 實施例15 實施例16 實施例1 7 實施例18 實施例1S 實施例20 實施例21 實ME例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 ί9 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 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 19 19 19 19 19 19 19 19 比較例41 比較例2 比較例3 18 19 19 14 16 16 10 i2 12 3 5 3 2 4 表 請 I 先I 閱 I 讀: 背I 面 j- 之 1 { 項I 再卜 % 裝本十 頁 訂 經濟部中央標準局員工消費合作社印製 初 期 特性 C DF Ζ LC 不良數/試樣數 短路 u F 96 βΩ U A ^ 個/個 實施例11 8.0 0.6 60 0.02 0/30 0 實施例12 8.2 0.7 60 0.02 0/30 0 實施例13 7.9 0.8 60 0.03 0/30 0 實施例14 7.2 0.8 60 0.03 0/30 0 實施例15 7.0 '0.9 60 0.05 1/30 0 實施例16 7.0 0.9 60 0.05 1/30 0 實施例Π 4.0 1.3 60 0.09 1/30 0 實施例18 7.9 ,0.8 60 0.03 1/30 0 實施例19 7.0 0.7 60 0.08 1/30 0 實施例20 7.9 0.6 60 0.03 0/30 0 實施例21 7.9 0.7 60 0.03 0/30 0 實施例22 7.8 0.8 60 0.02 0/30 0 比較例1 5.8 3.2 90 0.44 27/30 19 比較例2 7.1 1.2 60 0.16 11/30 9 比較例3 6.0 3.2 83 0.40 14/30 10 ο 5 本紙張尺廋適用中國國家標準(CNS )八4規格(210Χ 297公崖) 線 4346 0Printed 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 五、發明說明() 實施例23 將所定大小之蝕刻鋁箔置於含10重量%乏己二酸銨水 溶液中,施加13V之電壓處理而在其表面形成介質層。湛 之,將該鋁箔浸漬於含APS 20重量及d-樟腦磺酸納0.2 重量X之水溶液(溶液1),然後再浸漬於溶有3,4-二氧乙 烯-噻吩5克(1.2莫耳/公升)之異丙酵(IPA)溶液(溶液2 )後取出,放置於6010環境下1Q分鐘實行氧化聚合,然後 .Μ水洗淨。將上逑之聚合反應處理及洗淨處理各反覆實行 10次。 ’ 將上述聚合物置於水/IP Α溶媒中,藉肼遢原並萃取, 利用離子色層分析法測定聚合物所含之硫酸離子及d-樟腦 磺酸離子,结果Μ聚合物之全反覆構造單元計硫酸離子含 量為1.5重量%, d-樟腦磺酸離子含量為17重量X。固體電 解質層之電導度為7Qs/cm。 另外將陽極集電用之鋁芯部焊接於正(+ )側引線端子 而將·陰極集電用之負(-)側引線端子經由碳糊及銀糊接缅 ,最後利用環氧樹脂封止製取電容器元件。對此電容器元 件實行125 t: X2小時之熟化處理後測定其初期特性,结 果如表5所示。表5中之初期特性之容量及損失係數(tan 5 ),皆1 2 0 Η z測定者。阻抗係Μ.諧振頻率時之測值表示 。漏電流(LC)為腌加額定電壓一分鐘後測定之值。各測 定值為試樣數30涸之平均值。漏電流Κ超過lw Α者視為不 良品(短路),將不良品剔除求出tC值之平均。 耐濕性能試驗之結果如表6所示,在此表6中除將LC 值l〇w AM上者視為短路(不良)品之外,其他與初期值同 -5 Ϊ - 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -------l· I —-K---1 -‘衣--------訂·,1-------J (請先閱讀背面之注音?事項再填寫本頁) 經濟部智慧財產局員工消費合作社印?取 A7 B7 經濟部中央標準局員工消費合作社印製 五、發明説明(49) 、 樣。此耐濕性能試驗係在85Ό ^85 RHX之高溫高濕下放置 500小時實疵。回流試驗(reflowtest,亦稱為”焊接耐 熱性試驗)係依下述方法評估。即令30個之電容器元件( 試樣)在23〇υ之溫度下通遇30秒鐘,測定庵加額定電壓一 分鐘後之漏電滾值,Μ該測定值0.04CVUA)以上之元件 視為不良品。對30個之元件調査其不良數及有無短路,而 將其结果示於表6。 賁施例24 除了 Μ 2-樟腦-磺酸铵替代d-樟腦磺酸銨之外,其餘 悉依實施例2 3實施。製得之電容器元件之評估茏果如表5 及表6所示。聚合物中之硫酸離子含量為I.9其9 35,2_ 樟腦磺酸雄子含量為14莫耳%,固體電解質層之電導為45 S / C BI 〇 實Ife例25 除了 Md-樟腦羧酸納替代d-樟腦磺酸銨之外,其餘悉 依實施例2 3實施。製得之電容器元件之評估结果如表5及 表6所示。聚合物中之硫酸離子含量為4.7冥耳3;,d-撺 腦羧酸雄子含量為4.3冥耳3;,固體電解質層之電導為1 〇 s/ci 〇 實施例26 . 除了以過硫酸鉀替代APS及KN-甲基吡咯替代3,4-二 氧乙烯-唾吩之外,其餘悉依簧施例23實施。製得之電容 器元件之評估结果如表5及表6所示。聚合物中之硫酸離 子含量為6.8莫耳:K, d-槔腦磺酸雄子含量為11莫耳2,固 體電解質層之電導為2 0 s / c b。 HH —ϋ» ί a n - -HI n^i ^ m i ·{1 i mi 一 -·(m n^— - -- - -i m- < _ US. Ί 麥 (請先閱讀背面之注意事項再lii.本頁) 一 本紙乐尺度適用中國國家標準(CNS ) A4規格(2丨0 X 297公釐) 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明() 實施例27 除了依下述方法製備導電性聚合物之外,其餘悉依實 實施2 3實施,並依實施例23同樣方法評估電容器元件,结 果如表5及表6所示。 _ 將表面形成有介質被膜之鋁萡(基板)浸漬於含有2,3-二氯-5,-6二氰基苯醌(K下簡稱DDQ) 10重量%及d-樟腦磺 酸銨0.1重量%之二噁烷溶液(溶液1)後,再浸漬於溶有 異硫甜5克(1.2冥耳/公升)之IPA溶液(溶液2)。然後取 出基板放置於環境下30分鐘進行氧化聚合後Μ二噁烷 及水依次洗淨。 將上述之聚合反應處理及洗淨步驟分別反覆10次。聚 合物中之d -樟腦磺酸離子含量為11_5莫耳,固體電解質 層之電導度為18s/cm。 實施例28 除了 Μ硫酸鐵10重量%替代APS調製溶液之外,其餘 悉依實施例23實施。製得之電容器元件之評估结果如表5 及表6所示。聚合物中之硫酸離子含量為23莫耳%,d-樟 腦磺酸離子含量為14萁耳%。但,由於有鐵元素11重量%存 在,故電容器特性不甚理想。 實施例29 除了使用氯化鐵10重量替代APS調製d-樟腦磺酸鈉 0.1重量X之水溶液之外,其餘悉依實施例2 3實施。製得 之電容器元件之評估结果如表5及表6所示。聚合物中之 d -樟腦磺酸離子含量為2.3萁耳ϋ:。由於不含有硫酸離子, 故電容器特性不理想。 -5 3 - 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 裝--------訂---------線咖 五、發明説明(si A 7 B7 表 初期 特性 C (u F) DF (96) Z (Ω) LC (u A) 不良率 不良數/試揉數 短路 實施例23 5.2 0.8 26 0.04 ! 0/30 0 實雎例24 5.3 0.9 24 0.04 0/30 0 實施例25 5.0 1.0 32 0.05 1/30 0 實胨例26 4.8 1.1 40 0.06 2/30 0 實施例27 4.7 1.2 50 0.08 2/30 0 實晦例28 5.4 0.6 25 0.08 1/30 0 實施例29 4.5 1.4 52 0.05 2/30 0 表6 回流試驗 酎濕試驗 不良率 短路 不良數/試樣数 LC 不良率 短路 UA)不良數/試樣數 3 4 5 6 7 8 9 2 2 2 2 2 2 2 例例例例例例例 施施施腌施施施 Μι ρι Λί — ί tl rtn 實霣實實實實實 9 8 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 經濟部中夾標隼局員工消費合作社印製 實施例30 利用掃描電子顯微鏡M5, 000倍之放大率調査上述實 施例1〜10,實施例11〜22及實_例23〜29方法形成之具 有専電性聚合物層之固體電解質的鋁箱斷面,結果幾乎全 部之鋁箔之介質體之微细孔內之表面由導電性聚合物之層 狀構造所被覆,同時確認在層狀導電性聚合物層間有空間 -5 4 - -----:---*- 、j T国國家標準(CNS ) Λ4現格(2丨0 X 297公釐) - {請先閱讀背面之注意事項再緣?'本頁)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- < _ 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 經濟部中央標準局員工消費合作社印製 五、發明説明(52) 部存在。例如,實施例1之箔斷面照片如第2圖所示,其 形成於微细孔構造之外部表面之導電性聚合物層之厚度為 5W η,形成層狀構造之每一層的厚度為約〇·1〜〇.5 win範 圍。另外,由上述之鋁箔之微细孔部份之放大赌片可知, 専電性聚合物雖完全被覆微细孔內之表面,但在該部分仍 有空間部存在。 如上面所述,由於本發明之固體電解電容器及製造方 法係使具有ττ電子共軛構造之導電性聚合物之固體電解質 中含有選自(1)烷氧基取代萘磺酸陰離子、(2>雜環型磺 酸陰離子及(3)脂防族多環化合物之陰離子之至少一種有 機陰離子作為摻雑物(dopant),及併含有其他具有摻雜物 性能之陰難子為特徵,因此可提供小型且具有低阻抗及/ 或耐火花電壓特性優異之高性能固體電解質電容器。 另外,本發明之固體電解電容器,其固體電解質因使 用特定之聚雑環化合物,尤其是使用二氧甲撐基取代専電 - 性聚噻盼類,因而具有大幅增進酎電壓特性(火花電壓試 驗)、高頻特性、tanS、姐抗特性、漏電滾、耐熱性(回 流性)或酎久性等效果。特別在上述之導電性聚合物中含 有上述之有機陰離子0.1〜50冥耳X範圍,且兼含有硫酸 離子0.1〜10莫耳%範圍者,更可提供具備有高性能之電 容器特性之固體電解電容器。 一 5 5 - (請先閱讀背面之注意事項再一本頁)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 > 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)
冬你7長尺度適用中國國家標準(CNS ) Λ4現格(210X297公釐) 4346 02 A7 B7 五、發明説明(53) _式之簡單說明 第1圖為使用閥作用金靨箔之本發明的代表性電容器 之縱除面圖; 第2圖為實施例29所製備之具有形成有導電性聚合物 層之微细構造之鋁箔躕面之掃描電子顯微鏡照邊"(5,000倍 )〇 符號說明 , 1 · . ·.蝕刻處理金屬萡(陽極) 2— —细孔 3— —氧化被膜層(介質層) · 4— —固體電解質(導電性聚合物) 5— —導電體層 S——包封體 7——接續端子 (請先間讀背面之注意事項再填.¾'本頁 -裝— 訂 線 經濟部中央標隼局員工消费合作社印製 -56- 本纸張尺度適用中國國家標準(CNS ) ,44¾格(2I0X297公釐)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)
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TWI412553B (en) * | 2010-10-27 | 2013-10-21 | Ind Tech Res Inst | Oxidant for fabricating solid capacitor, electrolyte composition employing the same, solid capacitor and method for manufacturing the same |
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1999
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TWI412553B (en) * | 2010-10-27 | 2013-10-21 | Ind Tech Res Inst | Oxidant for fabricating solid capacitor, electrolyte composition employing the same, solid capacitor and method for manufacturing the same |
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