TW459255B - Solid electrolyte capacitor and the manufacturing method thereof - Google Patents
Solid electrolyte capacitor and the manufacturing method thereof Download PDFInfo
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459255 A7 B7 五、發明説明(1 ) <技術領域> 本發明係關於一種在_體電解質層及等電體層(含有, 金羼粉末之導.電體層或由導電性碳曆及其上面之金靥粉末 構成之導電體暦)之至少一曆含有橡膠狀彈性材料之固體 i • . · 電解鼋容器及其製法。;d其詳细地說,係蹦於一種可小型 化、高容量化及/低阻抗化且備有優異之外應力廣和特性 、生產性、耐無性及耐濕性等之固體電解電容器及其製法。 本發明亦涉及固體電解電容器用固體電解質,含金屬 粉末導電性糊及導電性碳糊(carbon paste)。 <背景技術> · ' . * 固體電解電容器係於經蝕刻處理之比表面積大之金羼. 萡極基體)上形成介質(絕緣介質)之氧化被膜層及在其 外側彤成作為對向電極之固體半導轚體曆(K下簡稱固體 電解層),且更坷取為進一步在其外面彤成含金屬粉末之 導霉體層或由導.電性碳層及其上面之金靥粉末構成之導電 體層,而將其連接於引線製成電容器之基本元件,進而將 該元件全體Μ環氧樹脂等絕緣性樹脂完全封裝K供作為電' 容器組件廣範應用於電氣製品。 輓近隨著電氣機器之數位化及個人電腦之高速化,對 於其上使用之固體電解電容器要求使用小型而大容量之電459255 A7 B7 V. Description of the invention (1) < Technical Field > The present invention relates to an electrolyte layer and an isoelectric layer (containing, conductive of gold tincture powder. The electrical layer or a conductive carbon calendar and the above) Conductive body made of gold 靥 powder 暦) At least one solid solid containing rubber-like elastic material i.. · Electrolytic 鼋 container and its manufacturing method. ; D In detail, it is a solid electrolytic capacitor that can be miniaturized, high capacity, and / or low impedance, and has excellent external stress and characteristics, productivity, resistance to humidity and humidity. And its manufacturing method. The present invention also relates to a solid electrolyte for a solid electrolytic capacitor, a metal powder-containing conductive paste, and a conductive carbon paste. < Background technology > · '. * The solid electrolytic capacitor is formed by an etching treatment on a metal substrate with a large specific surface area (an electrode substrate) to form an oxide coating layer of a dielectric (insulating medium), and forms an opposite surface on the outside thereof. The solid semiconducting body calendar of the electrode (K is referred to as the solid electrolytic layer), and it is further taken as a mold-forming body layer containing metal powder on the outside or a conductive carbon layer and the gold powder on it. The conductive element layer is formed, and it is connected to the lead wire to form a basic element of the capacitor, and then the entire element M is completely encapsulated with an insulating resin such as epoxy resin, and is widely used as an electrical container component in electrical products. With the digitization of electrical equipment and the speeding up of personal computers, the use of small-sized and large-capacity electric power is required for solid electrolytic capacitors used thereon.
I '容器且在高頻領域具有低阻抗(impedance)之電容器。 因應此等固體電解電容器之要求,前此已有各種固體 '電解質及導電體等被提出。 Μ固體電解質而言,例如有二氧化錳及二氧化鉛等無 本紙張尺度適用中國國家標準(CMS ) A4規格(2! 0 X 297公釐} (請先閱讀背面之注意事項再填寫本頁) 訂 經濟部智慧財產局員工消費合作社印製 丄 經濟部智慧財產局員工消費合作杜印製 45925 5 Α7 Β7 五、發明說明(2 ) 機糸半専體材料;另外亦有有機糸半導體材料,例如TC»Q (四氰基醌二甲烷)絡鹽,或電導度1〇-3〜5X 1〇.3s/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 9 6號或π共轭糸之聚笨胺(特開昭61-239 617號公報)、聚吡喀(特開昭61-240625號公報)、聚噻 吩衍生物ί特開平2-15611號公報(美國專利第4,910,645 號)]、聚異硫茚(特開蹈62-118511啤公報)等導電性聚 合物被人使用。 ^ 使用二氧化錳之固體電解質之電容器,不但在熱分解 形成硝酸錳時,先前形成於陽極箔之介質氧化被膜層會受 破壊之外,有咀抗特性不夠之缺點。又使用二氧化鉛時‘, 更有對環倮有顧慮之問題。' 另外,使用TCNQ絡鹽乏固體電解質之電容器,雖然 具有良好之熱熔融加工性及導電性,但TCNQ絡鹽本身卻 有耐熱性問題,在焊接時,抗熱性之可靠性差。 至於使用導電性聚合物之固體電解質之電容器,雖然 介質被膜無被破壊之虞,且阻抗特性高,但卻有耐熱性、 / 附熱銜擊性及耐震性較差之問題。 使用導電性聚合物之固體電解質之彤成方法,以往有 例如於具有微细的空隙構造之閥作用金屬表面之介質曆上 ,藉融解如上述之導電性聚合物(固體電解質)而形成之方 法或在介質曆上析出上述之専電性聚合物之方法等為人所 知。具體而言,例如以吡咯或噻吩等五節雜環化合物之聚 合物作為固體電解質時,將形成有介質被膜之陽極箔浸潰 -5- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐)I 'Container and capacitor with low impedance in high frequency range. In response to the requirements of these solid electrolytic capacitors, various solid 'electrolytes and conductors have been proposed heretofore. For Μ solid electrolytes, such as manganese dioxide and lead dioxide, etc., the Chinese paper standard (CMS) A4 specifications (2! 0 X 297 mm) are applicable to this paper. (Please read the precautions on the back before filling this page ) Order printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs and printed by the Intellectual Property Bureau of the Ministry of Economic Affairs of the Ministry of Economic Affairs of the People's Republic of China. 45925 5 Α7 Β7 V. Description of the invention (2) Organic semi-corporeal materials; there are also organic semiconductor materials, For example, TC »Q (tetracyanoquinodimethane) complex salt, or a truly conductive polymer having a conductivity in the range of 10-3 to 5X 10.3s / cb [Japanese Patent Application Laid-Open No. 1-1699 1 4 (US Patent Nos. 4,80 3, 5 9 6 or π-conjugated fluorene polybenzylamine (Japanese Patent Laid-Open No. 61-239 617), polypicine (Japanese Patent Laid-open No. 61-240625), and polythiophene derivatives Electrically conductive polymers such as Japanese Patent Application Laid-Open No. 2-15611 (US Patent No. 4,910,645), polyisothioindene (Japanese Patent Publication No. 62-118511) are used. ^ Capacitors using solid electrolytes of manganese dioxide , Not only during the thermal decomposition to form manganese nitrate, the medium oxygen previously formed in the anode foil In addition to the coating layer being damaged, it has the disadvantage of insufficient resistance. When using lead dioxide, 'there is also a concern about environmental problems.' In addition, capacitors using TCNQ complex salts lacking solid electrolytes have good Hot melt processability and electrical conductivity, but the TCNQ complex salt itself has the problem of heat resistance, and the reliability of the heat resistance is poor during welding. As for the capacitor using a solid electrolyte of a conductive polymer, although the dielectric coating may not be broken And has high impedance characteristics, but it has the problems of poor heat resistance, thermal shock resistance, and shock resistance. In the past, a solid electrolyte using a conductive polymer has been used as a valve with a fine void structure. A method for forming a dielectric surface on a metal surface by melting the above-mentioned conductive polymer (solid electrolyte) or a method for precipitating the above-mentioned galvanic polymer on a dielectric calendar is known. Specifically, for example, When a polymer of a five-membered heterocyclic compound such as pyrrole or thiophene is used as a solid electrolyte, the anode foil formed with a dielectric film is impregnated. -5- paper rule Applicable Chinese National Standard (CNS) A4 size (210 X 297 mm)
4 5 9 2 5 5 A7 ____B7_ 五、發明說明(3 ) 於該等雜環化合物之低鈒醇及/或水糸溶液之後,再浸漬於 溶有氧化劑及電解質之水溶液中進行單遛之化學聚合而形 成所要厚度之導電性餐^物脣i方法(特開平5- 1.7 5082.號 公報);將3,4-二氧乙烯噻吩單體及氧化劑,最好K溶液 » 形態前後分別或一起塗布於金屬,搭之氧化被膜層上而形成 導電性聚合物層之方法[(特開平2-15611號公報(美國專4 5 9 2 5 5 A7 ____B7_ V. Description of the invention (3) After the low alcohol and / or water solution of these heterocyclic compounds, then immersed in the aqueous solution in which the oxidant and electrolyte are dissolved to carry out the chemical polymerization of single amidine. The method of forming a conductive lip with a desired thickness (Japanese Patent Application Laid-Open No. 5-1.75082.); Coating 3,4-dioxyethylene thiophene monomer and oxidizing agent, preferably K solution »before or after the shape separately or together Method for forming conductive polymer layer on metal and oxidized coating layer [(Japanese Patent Application Laid-Open No. 2-15611 (US Patent
. I 利第4,91Q, 6 4 5號)或特開平1Q- 3 2 1 4 5號公報(歐.洲專利' ' , * 公開第8 2 0 Q 7 6號)等為人#知。 此等習知技術之氧化劑中被人熟知者有例如噻吩等/五 節雜環化合物之聚合時所用之氯化鐵(m )、F e ( C 1 0 * ) 3或 有機酸鐵(I )、無機酸鐵(Μ )、烷基過硫酸鹽、過硫酸銨 .(M下簡稱APS)、過氧化氫、K2 Cr3〇7等[特開平2-156U號 公報(美_專利第4,9 1 0 , 645號)]或飼化合物、銀化合物 等[特開平10- 3 2 1.4 5號公報(歐洲専利公開第82 0 0 76'號)]» 最近公開的一種方法.是K粉末聚苯胺作為導電性•原料 ,將其添加、分散於基質原料之橡膠及/或熱塑性樹脂中^ 使其複合化成為具有機择強度及柔軟性之聚苹胺複合物為 特戡之聚笨胺複合物之製法(特開昭64- 6 9 6 6.2號公報)。 另外亦有使用含有1〜25重量X之高分子粘着劑之聚 * t 苯胺溶液於電容器電極之金屬氧化物上彤成複合被膜,進 而在其上面形成聚苯胺中添加有陰離子之等電性聚合物層 為特徵之電容器之製法(特開平5-3138號公報)。 依上述方法時,因在絕緣體之氧化被膜上形成導電性 聚合物層,故須藉化學聚合預先形成一曆薄導電層,同f時 本纸舞尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (tt先閱讀背面之注意事項再填寫味頁) -------,|訂 i, — III—線{"3r |_1 經濟部智慧財產局員工消費合作社印製 45925 5 A7 __._B7_ 五、發明說明(4 ) 為使其適用於各個電容器,常遭遇下逑之問題: (1) 電解聚合之場合:柔軟性不佳之聚合物,若是增 高粘性則勢引起容量(capacity)之降下,此乃因為將表 面鈾刻所得之表面形成有介質之鋁箔浸潰於氧化劑溶液並 經乾燥而.在多孔質體的表面形成高粘性之氧化劑辦膜,故 存在於多孔質體表面之微细孔之孔口會被杜塞。加之,在 該多孔質體的表面會因與單體接觸形成聚合物,_使微细 孔內部不形成聚合物,於是導致容.量之低落。 (2) 化學聚合之場合:一次之聚合所能得之聚合物的 附着量少,因此必須多次浸潰,故生產性偏低。 (3) 介質被膜與固體電解質之密着性必須良好,若不 好時,會導致製品之劣化.及均一性之問題,影響製造收率 且使用壽命。 為解決上逑之問題,時下多藉由罨解聚合法或化學聚 合法製造上,逑之聚吡喀等導電性聚合物作為固體電解電容 器之固艘電解質使用,但所得之電容器之導電性聚合物被 膜之均一性,或製作電解電容器時之焊接耐熱性及阻抗特 性等均難稱理想。No. 4,91Q, 6 4 5) or JP 1Q- 3 2 1 4 5 (European Patent '', * Publication No. 8 2 0 Q 7 6) and others are known. Among the known oxidants are iron chloride (m), F e (C 1 0 *) 3 or organic acid iron (I), which are used in the polymerization of five-membered heterocyclic compounds such as thiophene and the like. , Inorganic acid iron (M), alkyl persulfate, ammonium persulfate. (M hereinafter referred to as APS), hydrogen peroxide, K2 Cr3 07, etc. [Japanese Unexamined Patent Publication No. 2-156U (US Patent No. 4,9 No. 10, No. 645)] or feed compounds, silver compounds, etc. [Japanese Unexamined Patent Publication No. 10- 3 2 1.4 (European Patent Publication No. 82 0 0 76 ')] »A method recently disclosed. It is K powder polyaniline As a conductive and raw material, it is added and dispersed in the rubber and / or thermoplastic resin of the base material ^ It is compounded into a polybenzylamine compound with organic strength and flexibility, and a special polybenzylamine compound Method (Japanese Patent Application Laid-Open No. 64- 6 9 6 6.2). In addition, there is also a poly * t aniline solution containing 1 to 25 weight X of polymer adhesive on the metal electrode of the capacitor electrode to form a composite coating, and then an isoelectric polymerization with an anion added to the polyaniline. Method for manufacturing capacitors characterized by physical layers (Japanese Patent Application Laid-Open No. 5-3138). According to the above method, since a conductive polymer layer is formed on the oxide coating of the insulator, a thin conductive layer must be formed in advance by chemical polymerization. At the same time, the paper dance scale applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (ttRead the notes on the back before filling in the flavor page) -------, | Order i, — III—line {" 3r | _1 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 45925 5 A7 __._ B7_ V. Description of the invention (4) In order to make it suitable for various capacitors, the following problems are often encountered: (1) In the case of electrolytic polymerization: polymers with poor flexibility, if the viscosity is increased, the capacity will be caused The reduction of (capacity) is because the aluminum foil with the medium formed on the surface obtained by the engraving of the surface is immersed in the oxidant solution and dried. A highly viscous oxidant film is formed on the surface of the porous body, so it exists in the porous The orifices of fine pores on the body surface will be douced. In addition, a polymer is formed on the surface of the porous body due to contact with the monomer, so that no polymer is formed inside the fine pores, resulting in a decrease in capacity. (2) In the case of chemical polymerization: the amount of polymer that can be obtained by one polymerization is small, so it must be impregnated multiple times, so the productivity is low. (3) The adhesion between the dielectric film and the solid electrolyte must be good. If it is not good, it will cause the degradation of the product and the problem of uniformity, which affects the manufacturing yield and service life. In order to solve the above problem, most of them are produced by the depolymerization polymerization method or the chemical polymerization method. Conductive polymers such as polypica are used as the solid electrolyte for solid electrolytic capacitors, but the conductivity of the resulting capacitors is The uniformity of the polymer film, or the soldering heat resistance and impedance characteristics when making electrolytic capacitors are difficult to be ideal.
I 經濟部智慧財產局員工消費合作社印製 | 另外,用Μ接合陰極引線端子及固體電解質層之導電 . r ' 體曆,通常是使用由導電性填充料及作為粘劑之合成樹脂 組成之導電'性糊。導電性填充料通常選自金、銀、銅等之 '金屬粉末或碳粉末,由於成本及性能,一般喜用銀粉。粘 劑用之合成樹脂通常使用環氧樹脂、鼢樹脂等,及其他例 如聚醸磨、聚亞醯胺及氟糸樹脂(特開平5 - 1.5 2 1 7 1號)或 -7- ’ 本纸張尺度適用令國國家標準(CNS)A4規格(210 X 297公釐) A7 459255 _B7_ 五、發明說明(5〉 聚丙烯酸樹脂 < 特開平7-233298號公報)亦為已知。 専電性糊已廣作為矽晶Μ及引線框之接着劑,即亦.怍 為晶粒接合(die bonding)材料使用。將含氟素聚合物作 為粘劑之晶粒接合用導電性糊已被公開(铸開平2-53Q4號 公報)。晶粒接合用導電性糊必需具傲高導電性、高耐熱 性及晶粒接合時發生很小之收縮應力且接合後吸水率低等 特性。另外在加熱接合時,導電性糊必需具有能減低砂晶 片及'引線框之間發生之應力之性能。 ' 至於,Μ —般.的合成樹脂作為粘劑使用之銀糊,因:彈 性率高,回流(reflow)等時易發生高應力而成為增加漏 J · . · · 電或引起接合界面之剝離,導致阻抗之熱劣化之原因。加 之,此種糊因吸水率高,在高溫高濕下有易發生性能劣化 之.問題。 另外亦有K氟系樹脂作為粘劑使用之銀猢,此種糊、與 上述者同樣彈性率高,回流等時易發生高應力,影響製品 性.成0 再者,廣被用作導電性材料之銀,由於價棬及性能上 較優,但易引起移行(migration),故依固體電解電容器 \ 經濟部智慧財產局員工消費合作社印製 之導電性糊在多種場合需預先塗佈等電性碳糊後,再使用 導電性銀糊。 導電性碳糊所用之導電性材料、粘劑及溶媒種類頗多 ,舉例言之,導電性材料可併用天然黑鉛(10〜20wm之鱗 片狀黒鉛)與碳黑(特開平9-31402號公報);具有突起之 碳粒(特開平5 - 7 ◦ 7 8號公報);導電性材料與粘,誧乏組合 ^ 8 " 本紙張尺度適用中國固家標準(CNS>A4規格<210 X 297公釐) 459255 A7 B7 五、發明說明(6 ) * {請先閱讀背面之注意事項再填寫本頁) 可用20wffi以下之碳黑及合成樹脂(特開平4-181607號公 報);鱗片狀黑鉛粉及微细黑鉛粉(長寬比10以上,平均粒 徑10« 下)及環氧樹脂之組合(特開平7-262822號); 黑鉛與含氟系聚合物,例如p T F E微粒子(特開昭6 1 - 6 98 5 3 號公報);又,等電性材料與溶媒之組合使用碳粉末及縮 水甘油乙链(特開平4-177802號公報);而可作為粘劑之 .合成樹脂則有聚乙烯、環氧樹及酚系樹脂等。 _ —Π*二 但,.使用天然黑鍇之導電性碳糊,因天然黑鉛呈鱗Η 狀,故填充性不佳,且因含有多量之雜質,使導電性顯著 槭低,此外塗佈後之表面因凹凸少,界面有易起剝離且又 島引起阻抗之熱劣化等缺點。 另外,使用碳黑之導電性磷糊,因粉末粒子極小,故 無法提高填充性,與天然黑鉛同樣,難提高導電性。於是 ,使用天然黑鉛及碳黑之導電性碳糊,在製造糊(paste) 時必須充分實行分散處理,於是手缜較煩。I Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs | In addition, the conductivity of the cathode lead terminal and the solid electrolyte layer is bonded by M. r 'The physical history is usually a conductive material composed of a conductive filler and a synthetic resin as an adhesive' Sexual paste. The conductive filler is usually selected from metal powders or carbon powders such as gold, silver, copper, etc. Due to cost and performance, silver powder is generally preferred. Synthetic resins for adhesives are usually epoxy resins, resins, etc., and other resins such as polyhoned, polyimide, and fluorinated resins (Japanese Unexamined Patent Application No. 5-1.5 2 1 7 1) or -7- The scale is applicable to the national standard (CNS) A4 specification (210 X 297 mm) A7 459255 _B7_ V. Description of the invention (5> Polyacrylic resin < Japanese Patent Application Laid-Open No. 7-233298) is also known. Electro-pastes have been widely used as bonding agents for silicon M and lead frames, that is, they are used as die bonding materials. A conductive paste for crystal bonding using a fluorine-containing polymer as an adhesive has been disclosed (Chai Kaihei 2-53Q4). The conductive paste for die bonding must have high conductivity, high heat resistance, small shrinkage stress during die bonding, and low water absorption after bonding. In addition, it is necessary for the conductive paste to have a property capable of reducing the stress occurring between the sand crystal and the lead frame during thermal bonding. 'As for the silver paste used by M-like synthetic resin as an adhesive, it has a high modulus of elasticity and is prone to high stress during reflow, which increases leakage. J ·. · · Electricity or peeling of the bonding interface Cause of thermal degradation of impedance. In addition, the paste has a high water absorption rate, and has a problem that performance degradation easily occurs under high temperature and high humidity. In addition, there is silver tincture using K fluorine resin as an adhesive. This paste has the same high elasticity as the above, and it is easy to generate high stress during reflow, which affects the product properties. Furthermore, it is widely used as electrical conductivity. The silver of the material is superior in price and performance, but it is easy to cause migration. Therefore, the conductive paste printed by the solid electrolytic capacitors \ Ministry of Economics and Intellectual Property Bureau employee consumer cooperatives needs to be pre-coated for various occasions. After the carbon paste, conductive silver paste is used. There are many types of conductive materials, adhesives, and solvents used for conductive carbon paste. For example, the conductive material can be a combination of natural black lead (scaly thallium lead of 10-20wm) and carbon black (Japanese Patent Application Laid-Open No. 9-31402 ); Carbon particles with protrusions (Japanese Unexamined Patent Publication No. 5-7 ◦ 7 8); a combination of conductive materials and viscous, stubborn ^ 8 " This paper size applies to the Chinese solid standard (CNS > A4 specifications < 210 X 297 mm) 459255 A7 B7 V. Description of the invention (6) * {Please read the precautions on the back before filling this page) Carbon black and synthetic resin below 20wffi can be used (Japanese Patent Laid-Open No. 4-181607); scaly black Combination of lead powder and fine black lead powder (above aspect ratio 10, average particle size 10 «under) and epoxy resin (Japanese Patent Application Laid-Open No. 7-262822); black lead and fluorine-containing polymer, such as p TFE fine particles ( JP-A-Sho 6 1-6 98 5 3); In addition, carbon powder and glycidyl ethyl chain are used in combination of isoelectric materials and solvents (JP-A 4-177802); and it can be used as an adhesive. Synthetic resins include polyethylene, epoxy resin, and phenol resin. _ —Π * 二 But, using the conductive carbon paste of natural black tincture, because the natural black lead is in the shape of scales, the filling property is not good, and because of the large amount of impurities, the conductivity is significantly lower. The subsequent surface has fewer irregularities, and the interface has the disadvantages of easy peeling and thermal degradation of the impedance caused by the island. In addition, the conductive phosphorus paste using carbon black has extremely small powder particles and therefore cannot improve the filling property. As with natural black lead, it is difficult to improve the conductivity. Therefore, the conductive carbon paste using natural black lead and carbon black must be fully dispersed during the production of the paste, so that it is troublesome to handle.
U 經濟部智慧財產局員工消費合作社印製 再者,K環氧樹腊作為粘劑使用時,雖然有成本較低 ,操持容易之利黠,但由於雨性高,隨晶片之大型化,在 回流等時,對加熱時在晶Η及引線框之間發生之應力之減 低欠具緩和能力,Μ及有吸水性高島發生耐濕性低降等問 題。 . <發明之目的〉 本發明之目的在於提供一種小型、輕量、高容躉、高U Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. When K epoxy resin wax is used as an adhesive, although it has a lower cost and is easier to handle, due to the high rain, with the increase in the size of the chip, In the case of reflow, there is a problem of reducing the stress that occurs between the crystal core and the lead frame during heating, and problems such as low moisture resistance due to M and high water absorption islands. < Object of the invention> The object of the present invention is to provide a small, lightweight, high capacity, high
C 頻特性、δ、漏電流、耐熱性(回流性)、耐熱衝擊性 、耐$性等優異之固體電解電容器,尤其Μ提供備有優異 本紙張尺度適用中國國家標準(CNS)A4規格(2.10 X 297公釐) 459 25 5 A7 B7 五、發明說明(7 ) 之低姐抗特性、對火花電壓試驗具有附久性以及對於外應 力具有鑀和性之耐熱性固體電解罨容器為目的。 本發明之另一目的為提供一種回流(reflow)時之熱 應力小,不畲因接合(糊曆)界面之剝離等引起阻抗之熱劣 > 化而且耐濕性亦極優之固體電解電容器用導電性糊及使用 該糊之固體電解電容器。 本發明之再一目的為提供一種晶粒接合用或可用於固 體電解電容器之導電性碳猢,其係~種導電性材料之填充 密度高之高導電性棚,K及具有可減低因加熱等時之材料 間之熱膨脹係數之差引起之應力及減低吸水性而增進製品 之耐濕性之導電性碳糊及使用該糊之固體電解電容器。 <發明之概要> 本發明係關於如下所述之固體電解質層、含金羼粉末 之導電體層,以及在上述固體電解質曆及含金屬粉末.之導 電體層之間·形成之導電性碳層之至少一層為含有橡膠:狀彈’ 性料為其特徵之固體電解電容器及··其製法;以及使用於固< 體電解電容器之固體電解質;含金屬粉末導電性糊、及導. 電性碳糊。 1. 一種於闕作用金靨表面上形成之介質被膜層上設 有固體電解質餍及専電體磨之固體電解電容器,其.特徵乃 在於該固體電解質層及·導電體廇之至少一層含有彈性狀橡 膠料。 :2. 如上第1項之固體電解電容器,其中該導電體層 係由含金屬粉末之導電體層,或導電性碳曆及設置在該層 -10- 本紙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) -----訂-----V. -1線3_ ..¾ 經濟部智慧財產局員工消費合作社印製r 經濟部智慧財產局員工消費合作社印製 狀 0 器 ?|橡 容W 電麵 解圍 電%f 體量 固質 之 5 a-2 9 1 或° ο 7 - 有 6 含 、 係 ^ 0 ^質 第解 上電 如體 . 固 11該 中 其 I 彈 狀 滕 橡 該 中 。 其 物 , 成器 組容 體電 聚解 性電 電體 導固 之之 狀項 層11 或第 狀上 膜如 之 . 料12 性 彈 躍 橡 該 中 其 ο > 種器 I 容 少電 至解 之電 膠體 橡固 成之 合項 及12 膠或 橡11 然第 天上 自如 選 . 係13 料 性 :4 5 9 2 b 5 A7 ___B7_ 五、發明說明(8 ) 上之含有金屬粉末之導電體層所構成。 3 . 如上第1或2項之固體電解電容器,其中該固體 r-- 電解質層含有橡膠狀彈性料。 4. 如上第2項之固體電解電容器,.其中該導電性碳 層含有橡膠狀彈性料。 5. 如上第2項之固體電解電容器,其中該含金靥粉 末之導電體層含有橡膠狀彈性料。 6. 如上第2項之固體電解電容器,其中該固體電解 質層及導電性碳層均含有橡膠狀彈性料。 7. 如上第_2項之固體電解電容器,其中該固體電解 質層友含金屬粉末之導電體層均含有橡膠狀彈性料。 8. 如上第2項之固體電解電容器,其中該導電性碳 層及含金靥粉末之導電體層均含有橡膠狀彈性料。 9. 如上第2項之固體電解電容器,其中該固體電解 質層、導電性碳層及含金屬粉末之導電體層均含有橡膠狀 彈性枓。 10. 如上第1〜9項之任一項之固體電解電容器,其中 該固體電解電容器之固體電解質層係具有膜狀或層狀構造。 本紙張尺度適用中國國家標準(CNS>A4規格(210 X 297公釐)C-frequency characteristics, δ, leakage current, heat resistance (reflow resistance), thermal shock resistance, resistance to solid electrolytic capacitors, etc., especially M provides excellent paper size applicable to Chinese National Standard (CNS) A4 specifications (2.10 X 297 mm) 459 25 5 A7 B7 V. Description of the invention (7) The low-resistance characteristic, long-term resistance to spark voltage test, and heat-resistant solid electrolytic plutonium container that is compatible with external stress. Another object of the present invention is to provide a solid electrolytic capacitor that has low thermal stress during reflow, does not suffer from thermal degradation of impedance due to peeling of a bonding (paste) interface, and the like, and has excellent moisture resistance. A conductive paste and a solid electrolytic capacitor using the paste. Still another object of the present invention is to provide a conductive carbon halide for grain bonding or use in solid electrolytic capacitors, which is a high-conductivity shed with high filling density of various conductive materials, K, and can reduce heating due to heating. Conductive carbon paste that reduces the water absorption and improves the moisture resistance of the product due to the difference in the thermal expansion coefficient between the materials and the solid electrolytic capacitor using the paste. < Summary of the invention > The present invention relates to a solid electrolyte layer, a conductive layer containing gold rhenium powder, and a conductive carbon layer formed between the solid electrolyte and the conductive layer containing metal powder as described below. At least one layer is a solid electrolytic capacitor containing rubber: shaped elastic material and its manufacturing method; and a solid electrolyte for solid < bulk electrolytic capacitors; a conductive paste containing metal powder, and a conductive material. Carbon paste. 1. A solid electrolytic capacitor provided with a solid electrolyte and a galvanic body mill on a dielectric coating layer formed on the surface of a metal substrate, characterized in that at least one of the solid electrolyte layer and the conductive body contains elasticity Rubber material. : 2. The solid electrolytic capacitor according to item 1 above, wherein the conductive layer is a conductive layer containing metal powder, or a conductive carbon calendar and is disposed on the layer-10- This paper standard applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) ----- Order ----- V. -1 Line 3_ .. ¾ Printed by the Employees' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs r Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 0 device? | Rubber capacity W Electric surface breakout electricity% f Mass solid 5 5 -2 9 1 or ° ο 7-There are 6 content, system ^ 0 ^ quality The first solution is to power up the body. Solid 11 of the I bullet Teng Oak. As for the material, the electrical layer of the device assembly is electrically conductive, and the electrophoretic layer 11 or the upper film is like this. The material 12 is a springy rubber. Among them, > The combination of electrical colloidal rubber solidification and 12 rubber or rubber can be chosen freely from the sky. 13 Material properties: 4 5 9 2 b 5 A7 ___B7_ V. The description of the invention (8) contains the conductive powder layer containing metal powder. Make up. 3. The solid electrolytic capacitor according to item 1 or 2 above, wherein the solid r-- electrolyte layer contains a rubber-like elastic material. 4. The solid electrolytic capacitor of item 2 above, wherein the conductive carbon layer contains a rubber-like elastic material. 5. The solid electrolytic capacitor according to item 2 above, wherein the conductive layer containing the gold powder contains a rubber-like elastic material. 6. The solid electrolytic capacitor according to item 2 above, wherein the solid electrolyte layer and the conductive carbon layer both contain a rubber-like elastic material. 7. The solid electrolytic capacitor according to item _2 above, wherein the conductive layer of the solid electrolyte layer containing metal powder all contains a rubber-like elastic material. 8. The solid electrolytic capacitor according to item 2 above, wherein the conductive carbon layer and the conductive layer containing gold tincture powder each contain a rubber-like elastic material. 9. The solid electrolytic capacitor according to item 2 above, wherein the solid electrolytic layer, the conductive carbon layer, and the metal powder-containing conductive layer all contain rubber-like elastic rhenium. 10. The solid electrolytic capacitor according to any one of items 1 to 9 above, wherein the solid electrolyte layer of the solid electrolytic capacitor has a film-like or layered structure. This paper size applies to Chinese national standards (CNS > A4 size (210 X 297 mm)
A7 459255 ___;__B7____ 五、發明說明(9 ) 狀弾性料為譚系橡膠。 <請先閲讀背面之注意事項再填寫本頁) 14.如上第11或12項之固體電解電容器,其中該導電 性聚體為吡咯、噻吩、苯胺或含有彼等之衍生物之二價基 之反覆軍元之至少一種聚合物。 > 1δ.,如上第2、5、7、8或g項之固體電解電容器,.. 其中該含金觴粉末之導電體層係含有金屬粉末構成之導電 性填充料及作為粘結劑之主成分之氟系橡膠。 16_如上第15項之固體電解電容器,其中該粘结劑之 80質量5S Μ上為氟系橡膠。 17. 如上第15項之固體電解電容器,其中該導電性填 充枓之80質量X从上為銀粉。 18. 如上第15或17項之固體電解電容器,其中該等電 性填充料之平均粒徑為1«βιΜ上lOjumM下。 •線. 19. 如上第15、17或18項之固體窜解電容器,其中該 導電性填充料為50〜95質量粘结劑為5〜50質量%。.. 20·如上第15項之固體電解電容器,其中該金屬粉末 之導電體廇係由含有骞電性填充料、粘结劑及有機溶劑之 導電性糊所形成之層。 經濟部智慧財產局員工消費合作社印製 21. —種將於閥作用金覊構成之陽極體的表面形成有 介質氧化被膜、固體電解質層及導電體層之電容器元件, Μ保留陽極引線端子及陰極引線端子之露出部之狀態使用 絕緣性樹脂封裝構成之固體電解電容器,其特徵乃在該固 體電解質曆為導電性聚合物層,而該導電體層為上逑第15 、20或21項所述之含有金觴粉末之導電髏層。 -12- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459255 A7 B7 五、發明說明(l〇 ) ^2.如上第21項之固體電解電容器,其中該導電體曆 為導電體聚合物曆上之専電性碳層及®置於該層上之由上 第15乃至2 0項之任一項所述之含有金属粉末之導電體層所 形成之層。 23. 如上第21或22項之固體電解電容器,其中該導電 性聚合物層為聚(3, 4-次乙氧基噻吩)° 24. 如上第2、4、6、8、3或22項之固體電解電容器 ,其中該導電性縯曆係Κ導電性材料、粘结劑及溶媒為主 成分之導電性碳糊所彤成之層,該導電性材料之80質垦X 以上為人造黑鉛,而該人造黑鉛為固定碳分97質量X Κ上 、平均粒徑1〜13wm、長寬比以下、粒徑32“®以上之 粒徑佔12質量S: K下。 25. 如上第24項之固體電解電容器,其中該粘结劑係 使用可膨潤或懸浮於溶劑之具有橡膠彈性之材料。 2 6.如上第25項之固體電解電容器,其中該具有橡膠 彈性之材料係選自異戊間二烯橡膠、丁二烯橡膠、苯乙烯 /丁二烯橡膠、睛橡膠、異丁烯橡膠、乙烯/丙烯共'聚合物 、丙烯酸類橡膠、多硫化糸橡膠、氟糸聚合物、矽酮橡膠 及熱塑性彈性料之至少一種材料。 2 如上第2 4項之固體電解電容器,其中該導電性碳 糊之固形份中3 0〜99質量:Ϊ為導電性材料、1〜70質量X 為粘结劑。 28. —種於閥作用金屬表面形成之介質被膜上設有固. 體電解質層及導電體層構成之固體電解電容器之製法,:特 13- 本紙張尺度適用中國國家標準(CNS)A4規袼(210 X 297公釐)A7 459255 ___; __ B7____ 5. Description of the invention (9) The material of the shape is Tan rubber. < Please read the precautions on the back before filling this page) 14. The solid electrolytic capacitor of item 11 or 12 above, where the conductive polymer is pyrrole, thiophene, aniline or a divalent radical containing their derivatives It repeats at least one polymer of military element. > 1δ. The solid electrolytic capacitors as described in item 2, 5, 7, 8 or g above: wherein the conductive layer containing the gold powder contains a conductive filler composed of metal powder and a main component as a binder Fluorine rubber. 16_ The solid electrolytic capacitor of item 15 above, wherein 80 mass 5S Μ of the binder is a fluorine-based rubber. 17. The solid electrolytic capacitor according to item 15 above, wherein the conductive filled 80 mass X is silver powder from above. 18. The solid electrolytic capacitor according to item 15 or 17 above, wherein the average particle diameter of the electric fillers is 1 «βιM to 10jumM. • Wire. 19. The solid fugitive capacitor according to item 15, 17, or 18 above, wherein the conductive filler is 50 to 95 mass% and the binder is 5 to 50 mass%. .. 20. The solid electrolytic capacitor according to item 15 above, wherein the conductive powder of the metal powder is a layer formed of a conductive paste containing a galvanic filler, a binder, and an organic solvent. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 21. —A capacitor element with a dielectric oxide film, a solid electrolyte layer, and a conductor layer formed on the surface of the anode body formed by the valve body. The state of the exposed portion of the terminal is a solid electrolytic capacitor composed of an insulating resin package. The solid electrolyte is characterized in that the solid electrolyte is a conductive polymer layer, and the conductive layer is contained in the above-mentioned item 15, 20, or 21. The conductive skull layer of gold tincture powder. -12- This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Description of the invention (10) ^ 2. The solid electrolytic capacitor of item 21 above, where the conductor is calendared It is a layer formed by a galvanic carbon layer on the conductive polymer and a conductive layer containing metal powder as described in any one of the above 15 to 20 on the layer. 23. The solid electrolytic capacitor of item 21 or 22 above, wherein the conductive polymer layer is poly (3,4-ethoxythiophene) ° 24. The item of 2, 4, 6, 8, 3 or 22 above A solid electrolytic capacitor, in which the conductive history is a layer made of conductive carbon paste containing κ conductive material, a binder and a solvent as main components, and 80% of the conductive material X or more is artificial black lead. And the artificial black lead is a fixed carbon with 97 masses X K, an average particle diameter of 1 to 13 wm, an aspect ratio of less than 32 "® and a particle size of 12" or more and 12 masses of S: K. 25. As above No. 24 The solid electrolytic capacitor according to item 2, wherein the binder is a rubber elastic material which can be swelled or suspended in a solvent. 2 6. The solid electrolytic capacitor according to item 25 above, wherein the material having rubber elasticity is selected from isoprene. Metadiene rubber, butadiene rubber, styrene / butadiene rubber, eye rubber, isobutylene rubber, ethylene / propylene copolymers, acrylic rubber, polysulfide fluorene rubber, fluorine fluorene polymer, silicone rubber and At least one material of thermoplastic elastomer. 2 The solid as described in item 24 above. Electrolytic capacitors in which the conductive carbon paste has a solid content of 30 to 99 masses: Ϊ is a conductive material and 1 to 70 masses X is a binder. 28. — A dielectric film formed on the surface of a valve-acting metal is provided Method for manufacturing solid electrolytic capacitors with solid body electrolyte layer and conductor layer: Special 13- This paper size is applicable to Chinese National Standard (CNS) A4 (210 X 297 mm)
I 注 拳 窝 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工.消費合作社印製 459 2b D A7 B7 五、發明說明(11) 戡包括: 令専電性聚合物之軍體溶液及氧化劑溶液之至少一者 含有橡藤狀彈性料; 使用該導電性聚合物之單體溶液及氧化劑溶液交互的 實胞一次或数次之反覆塗覆而在表面形成有介質被膜之閥 作用金屬之該介質被膜上彤成導電性聚體組成物之膜或層。 23.如上箄28項之固體電解電容器之製法,其中該専 電性聚體組成物中含有0.01〜25質量之橡膠狀彈性科。 30..如上第28或29項之固體電解電容器之製法,,'萁中 該橡膠狀彈性料為氣条橡膠。 31. —種於閥作用金屬表面形成之介質被膜上設有固 體電解質曆及導電體層之画體電解電容器之製法,其特徵 乃在使用含有導電性材料、具有橡膠彈性之粘结劑矣溶媒 之導電性糊,在固體電解質上形成導電體曆。 32. 如上第31項之固體電解電容器之製法,其中該導 甯體曆係使用一種含有金屬粉末構成之導電性填充劑、具 有橡膠彈性之粘结劑及溶媒之専電性糊所彤成之含金屬粉 末等電體曆。 33. 如上第3 1項之固體電解電容器之製法,其中該彎 電體層係使用一種含有等電性材料、具有橡膠彈性之粘结 劑及.溶媒之導電性碳糊彤成専電性碳廇之後,形成含有金 .羼粉末之導電體層。 34. 如上第31項之固體電解電容器之製法,其中該導 電體層係使用一種含有導電性材料、具有橡膠強性之粘多 -14- ^ 本紙張尺度S用令國國家標準(CNS)A4規格(210 X 297公ί ) it--.4 —---r l — AJ --- . v_''.. (請先閱讀背面之法意事現再填寫本頁) 訂丨 $ 經濟部智慧財產局員工消費合作社印製 4 59 25 5 A7 B7 五、發明說明(12) 劑及溶媒之導電性碳糊形成導電性碳曆之後,再使用一種 含有金靥粉末構‘成之導電性填'充劑、具有橡膝彈性之粘结 劑及溶媒之導電性糊形成含有金靥粉末之専電體層 35. 如上第31〜34項之任一項固體電解電容器之製 法,其中該固體電解質曆係使用導電性聚合物之單體溶液 及氧化劑溶液之至少一種含有橡膠狀彈性料之該導電性聚 合物之單體溶液及氧化劑溶疲在介質被膜上交互的實施一 次或數次之反覆塗覆形成導電性聚體組成物之被膜。 36. 如上第31〜35瑄之任一項固體電解電容器之製 法,其中該固體電解質層係膜狀或層狀構造。 37. 如上第36項之固體電解電容器之製法,其中該具 有膜狀或層狀構造之固體電解質之膜或每一層的厚度為約 0 . 1~ G . 3 " m範圍。 38. —種固體電解質,係由含有0.01〜25質量35之 掾膠彈性料之導電性聚體組成物'形成膜狀或層狀所構成者。 39. 如上第38項之固體電解質,其中該橡膠狀彈性料: 係選自天然橡膠及合成橡膠之至少一種。 40. 如上第38或39項之固體電解質,其中該橡膠狀彈 性料為氟系橡膠。 f 41. 如上第38項之固體電解質,其中該導電性聚體為 為吡咯、噻吩、苯胺或含有彼等之衍生物之二價基之反覆 單元之至少一種聚合物。 42. —種具有固體電解質之物體之製法,.包括:對表 面霜要形成由導電性聚體組成物構成之画體電解質之物體 .· ·. . -15- 本紙張尺度適用中國國家標學(CNS)A4規格(210 X 297公爱〉 閱 讀 背 面 之 注I Note Boxing staff of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative Cooperative. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative. 459 2b D A7 B7 V. Description of the invention (11) 戡 Includes: Orders of military solutions of electrical polymers At least one of the oxidant solution and the oxidant solution contains an oak-like elastic material; a valve-acting metal having a dielectric coating formed on the surface of the conductive polymer monomer solution and the oxidant solution interacting with the cells once or several times The medium is coated with a film or layer of a conductive polymer composition. 23. The method for manufacturing a solid electrolytic capacitor according to item 28 above, wherein the polymer composition contains 0.01 to 25 mass of a rubbery elastic branch. 30. The method for manufacturing a solid electrolytic capacitor as described in item 28 or 29 above, wherein the rubber-like elastic material in 萁 萁 is an air strip rubber. 31. —A method for producing a picture-type electrolytic capacitor with a solid electrolyte calendar and a conductive layer on a dielectric film formed on the surface of a valve-acting metal, which is characterized by the use of a binder / solvent containing a conductive material and a rubber elasticity The conductive paste forms a conductive calendar on a solid electrolyte. 32. The method for manufacturing a solid electrolytic capacitor according to item 31 above, wherein the conductive body is a metal-containing paste formed by using an electroconductive paste containing a metal powder-containing conductive filler, a rubber elastic binder, and a solvent. Powder isoelectric calendar. 33. The method for manufacturing a solid electrolytic capacitor as described in item 31 above, wherein the bender layer is made of a binder containing isoelectric material, rubber elasticity, and a conductive carbon paste of a solvent to form "electrical carbon". After that, a conductor layer containing gold and rhenium powder is formed. 34. The method for manufacturing a solid electrolytic capacitor according to item 31 above, wherein the conductive layer is made of a conductive material containing rubber and has a strong rubber viscosity. 14- ^ This paper is a national standard (CNS) A4 specification (210 X 297 公 ί) it-. 4 —--- rl — AJ ---. V_ '' .. (Please read the legal notices on the back before filling out this page) Order 丨 $ Intellectual Property of the Ministry of Economic Affairs Printed by the Bureau ’s Consumer Cooperatives 4 59 25 5 A7 B7 V. Description of the Invention (12) After the conductive carbon paste of the agent and the solvent forms a conductive carbon calendar, a conductive filler filled with gold tincture powder is used to charge Agent, conductive adhesive with rubber knee elasticity, and conductive paste of solvent to form a galvanic layer containing gold tincture powder 35. The method for manufacturing a solid electrolytic capacitor according to any one of items 31 to 34 above, wherein the solid electrolyte is used in the past Conductive polymer monomer solution and at least one oxidant solution containing a rubbery elastic material. The conductive polymer monomer solution and oxidant are dissolved on the dielectric coating and alternately applied one or more times to form a conductive coating. Film of sexual polymer composition. 36. The method for manufacturing a solid electrolytic capacitor according to any one of items 31 to 35 above, wherein the solid electrolyte layer has a film-like or layered structure. 37. The method for manufacturing a solid electrolytic capacitor according to item 36 above, wherein the thickness of each of the membranes or layers of the solid electrolyte having a film-like or layered structure is in the range of about 0.1 to G < m. 38. A solid electrolyte composed of a conductive polymer composition 'containing a rubber elastic material of 0.01 to 25 mass 35, formed into a film or a layer. 39. The solid electrolyte according to item 38 above, wherein the rubber-like elastic material is at least one selected from natural rubber and synthetic rubber. 40. The solid electrolyte according to item 38 or 39 above, wherein the rubber-like elastic material is a fluorine-based rubber. f 41. The solid electrolyte according to item 38 above, wherein the conductive polymer is at least one polymer of pyrrole, thiophene, aniline, or a repeating unit containing a divalent group of a derivative thereof. 42. —A method for producing an object with a solid electrolyte, including: for the surface frost to form a body electrolyte composed of a conductive polymer composition ... ··· -15- This paper applies Chinese national standard (CNS) A4 specifications (210 X 297 public love) Read the note on the back
經濟部智慧財產局員工消費合作社印製 45925 5 A7 _____B7__ 五、發明說明(13) ,使用導電性聚合物之軍髒溶液及氧化劑溶疲之至少一種 含有橡膠狀彈性料之上述溶液交互的實施一次或數次之反 覆塗覆而在該物體的表面锻成膜狀或層狀之導電性聚體組 成物〇 . 43. 如上第4 2項之具有固體讀解質之物體之製法,其 中該被覆係藉浸漬、塗佈、嗔塗或溶疲澆鏑法之任方法 實胞。: 44. 如上第42項乏具有固體電解質之物體之製法,其 中該橡膠狀彈性料像藉溶解或分散添加於導電性聚合物之 單體及/或含氧化劑之溶液中。 4 5. —種固體罨解電容器用導電性糊,其係由金屬粉 末構成之導電性填充.料及主成份為氟糸橡膠之粘结劑所構 成。 46. 如上第45項之固體電解電容器用導電性糊,其中 該粘結劑之80質量% Μ上為氟系橡膠。 47. 如上第45項之固體電解電容器用導電性糊,其中 該導電性填充料之80質量35 Κ上為銀粉。 48. 如上第45或47項之固體電解電容器用導電性糊, 其中該等電性填充料之平均粒徑為1〜η範圍。 49 .如上第45、47或48項之固體電解電容器用導電 性糊,其中該導電性填充枓佔50〜95質量%,粘结劑彳占5〜 50質量〇 50.如上第45〜49之任一項之固體電解電容器用導 電性糊,其中該導電性糊含有有機溶劑。 -16- 本紙張尺度適用中國國家標準(CNS)A4規格(210 * 297公釐) J — — — I I 1 i — — — — — — --'---—· (請先閱讀背面之注意事項再填寫本頁) 459255 A7 ____B7_._____ 五、發明說明(14 ) 51. —種固體鼋解電容器用導電性碳糊,係由導電性 碳材料、粘结劑及溶媒為主成份組成,其中該導罨性碳材 料之?〇質量S; Μ上為人造黑鉻,而該人造黑鉛之固定蟫份 為97質量χ κ上、平均粒徑、長寬比1〇以下及粒 徑32«ια Μ上之粒子佔I2質.最%以下。 5 2.如上第51項之固體電解電容器用導電性碳糊,其 中該粘结劑係使用一種可膨潤或懸浮於溶劑之具有橡膠彌 性之材料。 53. 如上第52項之固體電解電容器用導電性碳糊,其 - ' .. 中具有橡膠彈性之材料係選自異戊間二烯橡膠、,丁二稀橡 膠、苯乙烯/丁二烯橡膠、睛橡膠、異丁烯橡膠、乙烯/丙 烯共聚.合物、丙烯酸類橡膠、多硫糸橡膠、氟糸聚合物、 矽酮橡膠及熱塑性彈性料之至少一種材料。 54. 如上第51〜53項之固體電解電容器用導電性碳 糊,其中該導電性碳糊之固形份中30〜99質量%為導電 性材料、1~7Q質量X為粘结劑。 .〈發明之詳细說明> 經濟部智慧財產局員工消費合作社印製 本發明之固P電解電容器係於閥作用金屬上肜成之介 質被膜上形成固體電解質層及含金屬粉末之専零體餍及依 需要於上述固體電解質層及含金屬粉末之導電體層之間再 胗成等電性碳層所構成者,其特徵乃在該固體電解質曆, 含金屬粉末之導電體層及専電性碳層之至少一曆中含有橡 膠狀彈性料。 K下分別說明(1)在固體電解質層中含有橡膠狀彈性 -17- 本紙張尺度適用令國國家標準(CNS)A4規格(210 X 297公釐) 459255 A7 B7 經濟部智慧財產局員工消費合作杜印製 五、發明說明(15 ) . / 料;(2)在含金靥粉末之導電體層中含有橡膠狀彈性料; 及(3)在導電性碳層中含有橡膠性弾性料之實施形態,但 本發明亦包含在上述固體電解質層、含金屬粉末之等電體 層及導電性碳層之任意2餍或3層中皆含有橡膠狀彈性枓 之實施形態。 (1)固體電解質層含有橡膠狀彈性料之場合 • I 使在固體電解質層中含有橡膠狀彈性料時,最好係以 含有0·01〜25質量範圔之掾膠狀彈性料之膜狀或層狀 之導電性聚體組成物.形成該固體電解質層。 使導電性聚體組成物中含存上述範圍之橡膠狀彈性料 時,g卩使減少塗覆次數亦可在介質層上形成所需厚度之具 有耐熱性之等電性聚體組成物層(電荷移動絡合物)。由於 , 1 _ 添加橡膠狀彈性科,使得形成之固體電解質層保有應力..媛 和性,·結果可獲得具有良好之低阻抗特性,在火花電壓弒 驗等顯現耐久性之高性能固體電解質層及固體電解電容器。 適用於本發明之電容器之導電性聚體組成物中之専電 性聚合物係於聚合物主鍵備有κ電子共軛構造而聚合度2 Μ上1Q0O k下,較可取為5 Μ上500以下之聚合物'。具 體之例為聚五節雜環聚合物、聚苯胺、聚對次苯基、聚對 次苯基次亞乙烯基、聚瞜吡二胺次亞乙烯基及其取代衍生 物。.只生成上述聚合物亦可為使用至少2種以上之單體共 聚合生成之共聚合物。 可取之聚五節雜環聚合物之具體例,乃含有如下通式 (1)所示構造單元之7Τ電子共酾聚合物: -18- : -J I I I I I--— Μ ~~ J -III — . . Vi. . (請先閱讀背面之注意事項再填寫本頁) 訂 illPrinted by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 45925 5 A7 _____B7__ V. Description of the Invention (13) The use of a conductive polymer army solution and an oxidant to dissolve at least one of the above solutions containing a rubber-like elastic material was carried out once. Or several times of repeated coating to forge a film-like or layer-like conductive polymer composition on the surface of the object. 43. The method for producing a solid-reading object according to item 42 above, wherein the coating is It is a cell by any method such as dipping, coating, coating, or solvent pouring. : 44. The method for manufacturing an object having a solid electrolyte as described in item 42 above, wherein the rubber-like elastic material is added to a conductive polymer monomer and / or a solution containing an oxidizing agent by dissolving or dispersing. 4 5. —A conductive paste for solid disintegrating capacitors, which is a conductive filler composed of metal powder. The material and the main component is a binder made of fluorine rubber. 46. The conductive paste for solid electrolytic capacitors according to item 45 above, wherein 80% by mass of the binder is fluorine-based rubber. 47. The conductive paste for solid electrolytic capacitors according to item 45 above, wherein the conductive filler has a silver powder on the basis of 80 mass and 35K. 48. The conductive paste for solid electrolytic capacitors according to item 45 or 47 above, wherein the average particle diameter of the electrical fillers is in the range of 1 to η. 49. The conductive paste for solid electrolytic capacitors according to item 45, 47, or 48 above, wherein the conductive filler 枓 accounts for 50 to 95% by mass and the binder 彳 accounts for 5 to 50% by mass 50. As described in items 45 to 49 above The conductive paste for a solid electrolytic capacitor according to any one, wherein the conductive paste contains an organic solvent. -16- This paper size applies to China National Standard (CNS) A4 (210 * 297 mm) J — — — II 1 i — — — — — — —'---— · (Please read the note on the back first Please fill in this page again for details) 459255 A7 ____ B7 _._____ V. Description of the invention (14) 51. — A conductive carbon paste for solid digestion capacitors, which is composed of conductive carbon materials, binders and solvents as the main components, of which Which of the conductive carbon materials? 〇 Mass S; M is artificial black chromium, and the fixed content of the artificial black lead is 97 mass χ κ, the average particle size, the aspect ratio is less than 10, and the particle size of 32 «ια Μ accounts for I2 mass Under the most%. 5 2. The conductive carbon paste for solid electrolytic capacitors according to item 51 above, wherein the binder is a rubbery material that can swell or suspend in a solvent. 53. The conductive carbon paste for solid electrolytic capacitors as described in item 52 above, the material having rubber elasticity in-'.. is selected from isoprene rubber, butadiene rubber, styrene / butadiene rubber , At least one of rubber, isobutylene rubber, ethylene / propylene copolymerization compound, acrylic rubber, polysulfide rubber, fluorene polymer, silicone rubber and thermoplastic elastomer. 54. The conductive carbon paste for solid electrolytic capacitors according to items 51 to 53 above, wherein 30 to 99% by mass of the solid content of the conductive carbon paste is a conductive material, and 1 to 7Q mass X is a binder. . <Detailed description of the invention> The solid P electrolytic capacitor of the invention printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics is a solid electrolyte layer and a metal powder-containing body formed on a dielectric film formed on a valve-acting metal. It is formed by forming an isoelectric carbon layer between the solid electrolyte layer and the metal powder-containing conductive layer as required, which is characterized in the solid electrolyte, the metal powder-containing conductive layer and the electrocarbon A rubbery elastic material is included in at least one of the layers. K indicates that (1) the rubber-like elasticity is contained in the solid electrolyte layer. -17- This paper applies the national standard (CNS) A4 specification (210 X 297 mm). 459255 A7 B7 The consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs Du printed 5. Description of the invention (15). / Material; (2) the rubber-like elastic material is contained in the conductive layer containing gold tincture powder; and (3) the embodiment in which the rubberized tincture is contained in the conductive carbon layer However, the present invention also includes an embodiment in which the rubber-like elastic cymbal is contained in any of the 2 or 3 layers of the solid electrolyte layer, the electrical body layer containing metal powder, and the conductive carbon layer. (1) When the solid electrolyte layer contains a rubber-like elastic material • I When the rubber-like elastic material is contained in the solid electrolyte layer, it is preferable to use a film-like rubber material containing 0.01 to 25 mass range Or a layered conductive polymer composition to form the solid electrolyte layer. When the rubber-like elastic material in the above range is contained in the conductive polymer composition, it is possible to reduce the number of coatings and also form an isoelectric polymer composition layer having heat resistance and a desired thickness on the dielectric layer ( Charge transfer complex). Due to the addition of 1 _ rubber-like elasticity, the formed solid electrolyte layer retains the stress .. The element is harmonious. As a result, a high-performance solid electrolyte layer with good low-impedance characteristics and durability during spark voltage tests and the like can be obtained. And solid electrolytic capacitors. The electropolymer which is suitable for use in the conductive polymer composition of the capacitor of the present invention is a polymer having a κ electron conjugate structure on the polymer main bond and a degree of polymerization of 2 Μ above 1Q0 k, preferably 5 Μ above 500. Of polymers'. Specific examples are poly five-membered heterocyclic polymers, polyaniline, polyparaphenylene, polyparaphenylene vinylene, polypyridine divinylidene, and substituted derivatives thereof. Only the above-mentioned polymer can be formed, and it can also be a copolymer produced by copolymerizing at least two or more monomers. A specific example of a preferable five-membered heterocyclic polymer is a 7T electron conjugated polymer containing a structural unit represented by the following general formula (1): -18-: -JIIII I --- M ~~ J -III — .. Vi.. (Please read the notes on the back before filling this page) Order ill
VK 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459255 A7 B7 五、發明說明(κ)VK This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Description of the invention (κ)
式中 鏈的飽和或不飽和®基、含Ci-Cii之直鏈或支鏈的不飽和 烷氧基、羥基、齒原字、硝基、氰基、三鹵甲基、苯基、、 . 取代苯基選出之一價基;R1及R2亦可互相的在任意之位置 结合而形成至少一個以上之具有5-7節的飽和或不飽和環 狀構造之二價基;X代表一雜原子S、〇、Se、Te或.NE3 , • · 其中R3代表H、CrCs之真鐽或支鏈的飽·和或不飽和烴基、 苯基、或Ci-Ce之直鏈或支鐽的飽和或不飽和烷氧基;而上 述之R1、R2及R3之烷基、烷氧基之鏈中亦可任意的含有羰 基、醚基、酯基、醢胺基及亞胺基;5代表0〜1之範圍。 更可取者為含有如下通式(2)所示構瑄單元之7Γ電子 共轆聚合物: I : ------1 裝-------„—訂 ------- {請先閱讀背面之注意事項再取寫本頁) 經濟部智慧財產局員工消費合作社印製In the formula, a saturated or unsaturated chain, a linear or branched unsaturated alkoxy group containing Ci-Cii, a hydroxyl group, a dentate, a nitro group, a cyano group, a trihalomethyl group, a phenyl group, a. Substituted phenyl to select a monovalent group; R1 and R2 can also be combined with each other at any position to form at least one divalent group with a saturated or unsaturated cyclic structure of 5-7 sections; X represents a heteroatom S, 〇, Se, Te, or .NE3, where R3 represents the true or branched saturated or unsaturated hydrocarbon group of H, CrCs, or a saturated or unbranched, linear or branched Ci-Ce, or Unsaturated alkoxy groups; and the above-mentioned alkyl groups of R1, R2 and R3, and alkoxy chains may optionally contain carbonyl groups, ether groups, ester groups, amido groups, and imino groups; 5 represents 0 ~ 1 Range. More preferably, it is a 7Γ electron conjugated polymer containing a fluorene unit represented by the following general formula (2): I: ------ 1 equipment ---------------------- -{Please read the notes on the back before taking this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs
2) 式中:1^及[^各獨立的代表Η或Ci-Cs之直鐽或支鏈 的飽和或不飽和烴基、或之烴基互相在任意的位置 结合而形成式中所示之含有2個氧之至少一個K上之5-7 "19* # 本紙張尺度適用中國國家標準(CNS)A4規格(210x297公釐) 經濟部智慧財產局員工消費支作社印製 '^ 45925 5 A7_;_B7___;__五、發明說明(17) 節環之雜環構造之取代基;而形成上逑瑗狀構造之範圍中 含有取代乙烯基或取代〇 -苯撐基等化學構造;δ代表〇〜1 之範圍。' 上逑通式(1)之取代基R1飞R3及R3代表之 ' ,..·} ·.. 鏈或支鐽的飽和或不飽和烴基之例子為甲基、乙基、乙烯 r . ' 基、丙烯、,稀丙基' 異丙基丁基、1~ 丁烯基。又,Ci-CB 之直鏈或支鏈的飽和.或不飽和之烷氧基之例子為甲氧基、 乙氧基、丙氧基、異丙氧基、丁氧基等,。 另外,上述烴基產''糕氧基K外之取代基之例子為硝基 、氰基、苯基及取代苯基(Ci、.Br、F等之鹵取代苯基)。 在上述Ri、P之烷基及烷氧基之鍵中亦可任意的含有羧基 、醚基、酯基、醸胺基及亞胺基,其中特別有用者為甲氧 乙氧基及甲氧乙氧乙氧基。· — 又,β1、R2互栢的在任意之位置結合形成至少一個Μ 上之具有5-7節環的飽和或不飽和之翠狀構造之二價基之 通式(1)之例子可舉: 3 ,4-丙烯構造[通式(3) ]; 3,4-丁烯構造[通式.(4)〗;. 3, 4-(2’-丁烯撐)構造[通式(5)】;3, 4·-丁二烯撐構造[通 式(6)】及萘並[2,3-C]縮合構造[通式(7Π等。2) In the formula: 1 ^ and [^ each independently represent Η or a straight or branched saturated or unsaturated hydrocarbon group of Ci-Cs, or the hydrocarbon groups are combined with each other at an arbitrary position to form the formula shown as containing 2 5-7 on at least one of the oxygen " 19 * # This paper size applies to China National Standard (CNS) A4 (210x297 mm) Printed by the Consumer Support Bureau of the Intellectual Property Bureau of the Ministry of Economic Affairs' ^ 45925 5 A7_ _B7___; __V. Description of the invention (17) Substituents of heterocyclic ring structure of the ring; and the chemical structure such as substituted vinyl group or substituted 0-phenylene group is included in the range forming the upper structure; δ stands for 〇 The range is ~ 1. 'Supposedly represented by the substituents R1 to R3 and R3 of the general formula (1)', .. ·} · .. Examples of saturated or unsaturated hydrocarbon groups in the chain or branch are methyl, ethyl, and ethylene. Base, propylene, dipropyl'isopropylbutyl, 1 ~ butenyl. Examples of the straight-chain or branched-chain saturated or unsaturated alkoxy groups of Ci-CB are methoxy, ethoxy, propoxy, isopropoxy, butoxy, and the like. In addition, examples of the substituents other than the above-mentioned `` hydrocarbon-based alkoxy group K '' are nitro, cyano, phenyl, and substituted phenyl (halogen-substituted phenyl such as Ci, .Br, and F). The alkyl and alkoxy bonds of Ri and P may optionally contain a carboxyl group, an ether group, an ester group, an amido group, and an imino group. Among them, methoxyethoxy and methoxyethoxy are particularly useful. Oxyethoxy. · Also, an example of the general formula (1) of β1 and R2 which are mutually combined at any position to form a divalent group of a saturated or unsaturated green-like structure with a 5-7-membered ring on at least one M can be given. : 3,4-propene structure [General formula (3)]; 3,4-butene structure [General formula ((4)];. 3, 4- (2'-buteneene) structure [General formula (5 )]; 3, 4 · -butadiene structure [General formula (6)] and naphtho [2,3-C] condensation structure [General formula (7Π, etc.).
43) (4) (5) -2 0 - . 一· 本紙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,面之注意事碩再來寫本頁) ---r'^_ - ΓΊ. · Γ I I I I I 1 1111![1.43) (4) (5) -2 0-. I. This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the back first, and pay attention to the details before writing this page) ) --- r '^ _-ΓΊ. · Γ IIIII 1 1111! (1.
'7-'7-
-I 459255 a? B7 五、發明說明(is )-I 459255 a? B7 V. Description of the invention (is)
經濟部智慧財產局員工消費合作社印製 式中X代表雜原子S、0、Se、Te或NR3。X代表s之 上述3,4-丁二烯撐構造[通式(6)]在通式(1)之反覆構造 _單元時亦稱為異硫ίί撐(isothianaphthenyleae)構造。 又,蒹並[2,3-c]縮合構造[通式(7)]在通式(1)之場合稱 為萘並[2, 3-c】噻吩撐構造。式中,δ代表每一反覆構造 軍元之荷電數,係〇〜1範圍之值。 通式(2)中之R4及]^之取代基為例$0甲基、乙基、·丙 基、異丙基、乙烯基及烯丙基。又R4及之C.i-Ce烴基亦 可互相在任意之位蓳结合而形成上述通式(2>中所示之含 2個氧之至少1個K上之5 - 7節之雜環構造苳取代基,為 例如1,2-乙烯、1,2-丙烯、1,2-二甲基-乙烯。 又R4及PiCi-Cs烴基互相在任意之位置结合形成取 代乙烯基或取代0,苯撐基等不飽和烴之環狀構埴之具體例 為1,2-乙烯[通式(8)]、12-環己烯[通式(9)]及1,2-二甲 基-0 -苯撐[通式(1 Q )]: -21- ---I ΙΊ--I----裝-Lf - - ? (請先閱讀背面之注f項tk本頁)In the printed version of the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, X stands for heteroatom S, 0, Se, Te or NR3. X represents s of the above-mentioned 3,4-butadiene structure [general formula (6)] is also referred to as an isothianaphthenyleae structure when it is a repeating structure _ unit of general formula (1). The condensed [2,3-c] condensed structure [general formula (7)] is called a naphtho [2, 3-c] thiophene structure in the case of general formula (1). In the formula, δ represents the number of charge of each repetitive structure military element, which is a value ranging from 0 to 1. Examples of the substituents of R4 and ^ in the general formula (2) are methyl, ethyl, propyl, isopropyl, vinyl, and allyl. In addition, R4 and Ci-Ce hydrocarbon groups may be combined with each other at any position to form a heterocyclic structure of 5 to 7 sections of at least 1 K containing 2 oxygen shown in the above general formula (2>). For example, 1,2-ethylene, 1,2-propylene, 1,2-dimethyl-ethylene. R4 and PiCi-Cs hydrocarbon groups are bonded to each other at any position to form a substituted vinyl group or a substituted 0, phenylene group. Specific examples of the cyclic structure of isounsaturated hydrocarbons are 1,2-ethylene [general formula (8)], 12-cyclohexene [general formula (9)], and 1,2-dimethyl-0-benzene Support [General formula (1 Q)]: -21- --- I ΙΊ--I ---- 装 -Lf--? (Please read the note f on the back page tk first)
Q 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459 255 A7 __:____ B7 五、發明說明(I9 )Q This paper size is applicable to China National Standard (CNS) A4 specification (210 X 297 mm) 459 255 A7 __: ____ B7 V. Description of the invention (I9)
經濟部智慧財產局員工消費合作杜印製 本發明之固體電解電容盏及其製法所使用之單體化合 物中,洌如噻盼、吡咯或3 ,4-乙二氧撐噻吩之單體化合物 為'習知,此等單體化合物之聚合用氧化劑亦多為習.知。 ' Γ 但,備有於上述之等電性聚體組成物中加有橡膠狀彈 性料之固體電解質之電容器為從未被人所知。 於本發明中,構成固體電解質之橡膠狀彈性料經推考 係溶解於専體性聚合物中作為基質(matrix)分散於導電 性聚合物中。 對構成本發明苳固體電解電容器之固體電解質之上逑 π共軛系導電性聚合物所需添加之橡膠狀彈性料量·為〇.01· 〜2 5質量X,最好為〇.ι〜1()質量%。備有橡膠‘狀彈性料之 固體_解質之電解電容器,尤其可成具有優異之低胆抗特 性,及對火花電壓試驗顯示耐久性而且對外臛力具有鑀和 性之耐熱性固體電解電容器。 橡膠狀彈性枓之添加量未滿0.01質量!Κ時,完全不 顯出添加橡膠狀彈性料之效果;反之超過25質量Si _,則 會降低固體電解質之導電性,尤其當橡膠狀彈性料之添加 -22-In the consumer cooperation of the Intellectual Property Bureau of the Ministry of Economic Affairs, Du printed the solid electrolytic capacitor of the present invention and the monomer compounds used in the preparation method. The monomer compounds such as thiopan, pyrrole or 3,4-ethylenedioxythiophene are 'It is common practice that oxidants for the polymerization of these monomer compounds are also known. 'Γ However, a capacitor provided with a solid electrolyte in which a rubber-like elastic material is added to the above isoelectric polymer composition has never been known. In the present invention, the rubber-like elastic material constituting the solid electrolyte is dissolved in a carcass polymer as a matrix and dispersed in a conductive polymer as a matrix. The amount of rubber-like elastic material to be added to the π-conjugated conductive polymer on the solid electrolyte constituting the 苳 solid electrolytic capacitor of the present invention is 0.001 to 2 5 mass X, preferably 〇.ι ~ 1 ()% by mass. A solid-decomposed electrolytic capacitor provided with a rubber-like elastic material is particularly suitable for a heat-resistant solid electrolytic capacitor that has excellent low-buck resistance, shows durability against spark voltage tests, and has external resistance to external forces. The addition amount of rubbery elastic concrete is less than 0.01 mass! At KK, the effect of adding rubber-like elastic material is not shown at all; on the contrary, if it exceeds 25 mass Si _, the conductivity of the solid electrolyte will be reduced, especially when the rubber-like elastic material is added -22-
請 先 閱 讀 背 之 注 意 事 項, 再f .】 頁 I 訂 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 4592^5-垃 4592^5-垃 經濟部智慧財產局員工消費合作社印製 B7 五、發明說明(2〇 量多到基質逆轉時會使導電性急激下降,因此務須限制在 2 5質量:S K下。為此,對固體電解質之組成物的全質量使 用Q.G1〜2 5質量Γ範圍,尤其0.1〜10質量X範.圍,如此. 便可提供具有低阻抗特性優異之電容器。 通常在固體電解電容器之製法上,為改善高容量之高 頻特性及損失係數(tan5>、漏電流、耐熱性(回流性)、 阻抗特性及耐久性等/上述之固體電解質之.製造(形成)方 法乃極關重要。為此,構成固驩電解質之丨等電性聚合物之 π電子共軛構造、摻配橡膠狀彈性料之等電性聚體組成物 之構成、,導電性聚體組成撖餍織«充於微细的表面 構造之介質曆上K提高導電變阻之均一性為極重要,其中 専電性聚體組成物之構成對電容器之特性影響特別大。. 依本發明之固體電解質之製法,因於彤成具有上述π 電子共軛構造之聚合物時,於含有單體及/或氧化劑之滓 液中添加橡膠狀彍性料,故具有可增趣#述寧液之附著量 ,減少必要之浸潰次數之特徵。又,因添加橡膠狀彌性料 ,故可使導電性聚體組成物具有應力媛和性,對於因热化 或封裝等之外壓力可增高彈性力,结果顯現諸如降低初期 特性之漏電流、減小在高溫、高濕下長期間放置時之容量 及損失'係數等之劣化之特徵。 具體的例子為將橡膠狀彈性料之溶液或分散液混合於 含有單體化合物之溶释中,將此溶疲被覆碎閥作用金屬陽 極箔之具有微细孔之介電質被膜上,利用氧化劑之作用使 單體化合物進行氧化的聚合而將生成之聚體組成物作為固 -23- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) iill.l------1¾--------^-------- <請先閱讀背面之注意事項寫本頁) h. A7 459 2b5 _____B7_.___ 五、發明說明(21 ) I · (猜先閲讀背面之注意事項再填寫本頁) 體電解質形成於介質表面上。將上述之製程對一個陽極基 板至少賁施一次,最好反覆的實施3〜20次,即可輕易的 形成緻密之固體電解質層。 較可取之製程之一為浸漬法,此方法係在進行上述之 聚合時,先將形成有介質被膜之閥作用金靥陽極箔浸漬於 含有氧化劑之溶液(溶液1)中,然後再浸漬於含有單體化 合物及橡膠狀彈性料之混合溶液(溶疲2)中。上述之浸潰 順序亦可顛倒,即將閥作用金屬陽極箔眾浸漬於上述之溶. 液2之後,再浸漬於上逑之溶液1中。 •s 另一實施形態為將該陽極箔浸漬於含有氧化劑及橡膠 彈性料之溶疲(溶液3)後,再浸漬於含有軍體化合物之溶 液(溶液4)中。上述之浸潰順序亦可顛倒。又,上述之溶 液1〜溶液4亦可為懸浮 '液。 另外,上述之浸濱法亦可由塗佈法、嗔吹法或溶液澆 鏞法替代,使在陽極箔上進行聚合反應。 經濟部智慧財產局員工消費合作社印製 溶液1〜溶液4之溶媒可為同条,或可為不同系溶媒, 且可依溶媒之種類在溶液1及溶液2,或溶液3及溶液4 之製程之間另加乾燥步驟。另外,於形成上述之,導電性聚 合物被膜(固體電解質)而_為電容器元件之後,亦可加一 利用有機溶媒洗淨或水洗淨之步驟。洗淨用有機溶媒最好 為溶液1〜溶液4所使用之溶媒,如此作業較簡便,但其 他任何可溶解單體化合物及具有摻雜物(dopant)性能之 陰離子之其他化合物之溶媒亦可使用。 將上述之氧化的聚合反覆實行之場合,可容易生成焊 ~ 2 4 ^ 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459255 Δ7 A/ B7 五、發明說明(22,) 接抗熱性(热安定性)優異之固體電解質。使用習知之聚咽 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,但捷用本發明之由導電性聚 體組成物溝成之固體電解質ά電容器具有優異之熱安定性 且含摻雜物(dope)狀態之安定性良好。 .此艿因為加有上述橡膠狀彈性抖之導電性聚體組成物. 不但可在介質表面且可深入至细孔内部.而階段的析出填充 ·*· , 於介質表面及细孔内部,因此可形成該聚體組成物之多'層 薄..膜曼合層,從而提供具有柔軟性及良好的熱安定性且介 質被膜不受破壞之電容器。 本發明適用之橡膠狀彈性料係具有彈性橡膠或橡膠類 似物質之獨特彈性而受到外力變形時有使赛形回復原狀之 性質之物質,其具體例包括:一般橡膠(例如天然橡膠及 尿焼橡膠、乙烯-丙烯共聚合物、乙烯-丙烯-二烯共聚合 物、苯乙烯-丁二烯掾膠、丁基橡膠、異戊間二烯橡醪、 * , 矽酮橡膠及氟糸橡膠等合成橡膠)或熱塑性彈性枓(例如 苯乙烯系、烯烴系、尿烷糸、1,2 -聚丁二烯系及氯乙烯系 等}。 氟系橡膠惠分子中含有氟原子之合成橡膠的總稱,係 作為特殊橡膠使用,與i用橡膠有區別。其具體例為含氟 西輝酸酯之聚合物、氟化亞乙嫌系共聚合物、四氟化乙稀 -全氟代甲基乙烯酸共聚合橄、含氟磷氮条及含氟矽酮系 聚合物等。這些合成樹脂依種類顯示不同性質,但比一般 市售之橡膠具有遠為優異之耐熱性而且附藥品性及耐候性 / -25-' 本纸張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閲讀背面之ί Ί裝------ *' 广·· ¾再1填寫本頁) 訂---------線 經濟部智慧財產局員工消費合作社印製 A7 B7 459255 五、發明說明(23 ) 亦儍異。上述之矽酮橡膠係一種其主鏈由矽氧烷鐽结合而 側鏈具有甲基、苯基等取代基之線型聚合物互相橋接所成 之橡膠狀弾性料,具有良好之耐熱性及電絕緣性。此等彈 性料最好為導電性聚合物之聚合反應時可溶解於有機溶媒 中。適用之彈性料可舉聚酯尿烷、聚醚尿烷及氟化亞乙烯 -環己丙烯共聚合物等。此時使用之有機溶媒Μ Ζ»基甲基 鬭、丙酮等酮条、乙酸異丙酯等乙酸酯糸、二噁烷、THF 等醚系、甲醇等醇系較為可取。若是使用不溶於'有機溶屬. ,之橡膠時,可使用與含有單體或氧化劑之溶液之溶媒栢同 之境蹕或可與其混合之繪媒之分散液。 特別要使固體電解質具有耐熱性時,使用高耐熱性之 .氟糸橡膠及矽酮橡膠等。 本發明中使用之氧化劑,只要其適合吡咯或睡吩類之 氧化聚合者均可,例如特開平2 - 1 5 6 11號公報(美國專利 第4,910,645號)所述之氯化鐵(11)、?6((:104)3或有機 酸戡U )、無機酸鐵(Μ )、烷基過硫酸盥、過硫酸銨、過 氧化氫、iUCra〇7等。上逑之有機酸鐵)之有機酸為例 如甲烷磺酸或例如十二烷基苯磺酸等(^-(:21)烷基磺酸或.脂Please read the precautions before f.] Page I The size of the paper is applicable to the Chinese National Standard (CNS) A4 (210 X 297 mm) 4592 ^ 5-RAS 4592 ^ 5- Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by Consumer Cooperative B7 V. Description of the invention (more than 20, the conductivity will decrease sharply when the matrix is reversed, so it must be limited to 25 mass: SK. For this reason, use the full mass of the solid electrolyte composition Q G1 ~ 2 5 mass Γ range, especially 0.1 ~ 10 mass X range. In this way, capacitors with excellent low impedance characteristics can be provided. Usually in the solid electrolytic capacitor manufacturing method, in order to improve the high-frequency characteristics of high capacity and Loss coefficient (tan5), leakage current, heat resistance (reflow), impedance characteristics and durability, etc. / The method of manufacturing (forming) the solid electrolyte described above is extremely important. For this reason, the isoelectricity of the solid electrolyte Π-electron conjugate structure of polymer, composition of electrical polymer composition such as rubber-like elastic material, conductive polymer composition, weaving The uniformity of the varistor is extremely important, among which the composition of the electropolymeric composition has a great influence on the characteristics of the capacitor. According to the method for producing the solid electrolyte of the present invention, due to the polymerization of the π-electron conjugated structure described above In addition, rubbery materials are added to the mash containing monomers and / or oxidants, so it can increase the adhesion amount of Shuning solution and reduce the number of necessary immersion times. In addition, because of the addition of rubber-like It can make the conductive polymer composition have stress and flexibility. It can increase the elasticity against external pressure such as heating or encapsulation. As a result, the leakage current of the initial characteristics is reduced, and the high temperature and high temperature are reduced. Characteristics of deterioration in capacity and loss coefficient when placed under wet conditions for a long period of time. A specific example is mixing a rubber-like elastic material solution or dispersion with a monomer compound-containing solution, and coating the solvent with a crushing valve. Acting on a metal anode foil with a fine pore dielectric coating, the monomer compound is oxidized and polymerized by the action of an oxidizing agent, and the resulting polymer composition is used as a solid 23- China National Standard (CNS) A4 Specification (210 X 297 mm) iill.l ------ 1¾ -------- ^ -------- < Please read the note on the back first Matters written on this page) h. A7 459 2b5 _____ B7 _.___ V. Description of the invention (21) I · (Guess to read the notes on the back before filling this page) The body electrolyte is formed on the surface of the medium. The above process is applied to an anode The substrate is applied at least once, preferably 3 to 20 times, to easily form a dense solid electrolyte layer. One of the preferred processes is the immersion method. This method is performed when the above polymerization is performed. The valve action of the dielectric film The gold anode anode foil is immersed in a solution containing an oxidant (Solution 1), and then immersed in a mixed solution containing a monomer compound and a rubber-like elastic material (Solution 2). The above impregnation order can also be reversed, that is, the valve-acting metal anode foils are immersed in the above-mentioned solution 2. Then, they are immersed in the above-mentioned solution 1. • s In another embodiment, the anode foil is immersed in a solution (solution 3) containing an oxidizing agent and a rubber elastic material, and then immersed in a solution (solution 4) containing a military compound. The above impregnation order can also be reversed. The above-mentioned solutions 1 to 4 may be suspensions. In addition, the dipping method described above may be replaced by a coating method, a blow-by method, or a solution-casting method, so that a polymerization reaction is performed on the anode foil. The solvent for printing solutions 1 to 4 of the consumer cooperative of employees of the Intellectual Property Bureau of the Ministry of Economic Affairs may be the same, or they may be different solvents, and may be processed in solutions 1 and 2, or solutions 3 and 4 depending on the type of solvent. Add another drying step in between. In addition, after the conductive polymer coating film (solid electrolyte) is formed as described above and _ is a capacitor element, a step of washing with an organic solvent or washing with water may be added. The organic solvent for cleaning is preferably the solvent used in solution 1 to solution 4. This operation is relatively simple, but any other solvent that can dissolve monomer compounds and other compounds with an anion with dopant properties can also be used. . Where the above-mentioned oxidation polymerization is repeatedly carried out, welding can be easily generated ~ 2 4 ^ This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 459255 Δ7 A / B7 V. Description of the invention (22, ) Connected with a solid electrolyte with excellent heat resistance (thermal stability). Capacitors using solid polyelectrolytes formed by conventional polypharyngeals and the like have large variations in capacitor characteristics and poor reliability at high temperatures and high humidity, but use the solid electrolyte formed by the conductive polymer composition of the present invention. The capacitor has excellent thermal stability and good stability in a dope-containing state. .This is because the conductive polymer composition with the above-mentioned rubber-like elastic vibration is not only on the surface of the medium but also deep inside the pores. The precipitation filling at the stage is on the surface of the medium and inside the pores, so Multiple layers of the polymer composition can be formed, such as a thin film and a laminated layer, so as to provide a capacitor having flexibility and good thermal stability without the dielectric film being damaged. The rubber-like elastic material applicable to the present invention is a substance having the unique elasticity of elastic rubber or a rubber-like substance, which has the property of returning the race shape to its original shape when deformed by an external force. Specific examples include: general rubber (such as natural rubber and urine rubber , Ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene-butadiene rubber, butyl rubber, isoprene rubber rubber, *, silicone rubber and fluorine rubber Rubber) or thermoplastic elastomers (such as styrene-based, olefin-based, urethane-based, 1,2-polybutadiene-based and vinyl chloride-based, etc.). Fluoride rubber is a general term for synthetic rubber containing fluorine atoms in its molecules. It is used as a special rubber, which is different from rubber for i. Specific examples are polymers containing fluorinated fluorinated esters, fluorinated ethylene copolymers, ethylene tetrafluoride-perfluoromethyl vinyl acid Copolymers of olive oil, fluorine-containing phosphorus nitrogen strips, fluorine-containing silicone polymers, etc. These synthetic resins show different properties depending on the type, but have far superior heat resistance, chemical resistance, and weather resistance compared to commercially available rubbers / -25- 'paper ruler Degree applies to China National Standard (CNS) A4 specification (210 X 297 mm) (Please read the ί outfit on the back -------- * 'guang ·· ¾ and then fill out this page) Order ----- ---- Printed A7 B7 459255 by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. The description of the invention (23) is also stupid. The above-mentioned silicone rubber is a kind of silicone rubber whose main chain is combined with siloxane and the side chain has a The rubber-like rubber compound formed by the linear polymers of substituents such as phenyl and phenyl groups bridges each other, which has good heat resistance and electrical insulation. These elastic materials are preferably conductive polymers that can be dissolved in organic polymers during the polymerization reaction. In the solvent. Suitable elastic materials include polyester urethane, polyether urethane, and fluorinated vinylidene-cyclohexene copolymers. The organic solvent used at this time is ketone strips such as MZ »methylmethylfluorene and acetone. Acetic acid esters such as isopropyl acetate, ethers such as dioxane, THF, and alcohols such as methanol are preferred. If using insoluble organic solvents, rubbers can be used with monomers or oxidants. The solvent of the solution is the same as the environment or the dispersion of the media that can be mixed with it. In particular, the solid should be electrolytic When the material has heat resistance, use high heat resistance. Fluorine rubber, silicone rubber, etc. The oxidant used in the present invention may be any oxidizing polymer suitable for pyrrole or phenanthrene, for example, JP 2-1 5 6 Ferric chloride (11),? 6 ((: 104) 3 or organic acid 戡 U), inorganic iron (M), alkyl persulfate, Ammonium sulfate, hydrogen peroxide, iUCra〇7, etc. The organic acid on the top of the organic acid) is, for example, methanesulfonic acid or dodecylbenzenesulfonic acid (^-(: 21) alkylsulfonic acid or. fat
I 肪族羧酸。但,上述氧化劑之使用範圍間或會受軍體化合 物之化學構造、氧化劑Μ及反應條件等之限例如,噬 吩類之氧化(聚合),依 Handbook of Conducting Polymers 雜誌(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,. Ϊ1 i g . 5 ) 之說明,依取代基之種類氧·化電位(衾示聚合容易度之指 標)大幅改變(氧化電位之範園為約1.8〜約2.7 V).,而左 - 2 6 - ^氏張尺度^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) r 經濟部智慧財產局員工消費合作社印製 Λ A7 B7 五、發明說明(24) 右聚合反應。因此,使用之軍體化合物與氧化劑有特定之 組合。本發明係在此種限制範圍內找出可改良電容器特性 之製法上之组合,從而解決了上述之課題° 在本發明之導電性聚合物之製造中,視需要共存之具 有摻雜物性能之陰離子乃可使甩對於上逑氧化劑產生之氧 化劑陰離子ί氧化劑之遨原體)具配葑離子之電解質化合物 或其他陰離子系罨解質。其具體的例子為氯離子、 、h-Cu之腊肪族有機羧酸陰離子、硫酸陰離子、磷酸陰 離子、Ci-Cu之脂肪族有櫬磷酸陰離子、硼酸陰離子等。 另外亦可使用 M0+、NOa* 鹽(例如 NOBFi、NOPFb、NOSbFc、 NOAsFs、NOCH3S〇3、N0sBF4、fiOaPFs、N〇zCF3S03)之電 子受容體摻雜物。 又,由於本發明使用之上述陰雜子與習知之分子陰雄 子(例如CIO*-、Βί·*·1等)具有不同之摻雜物性能(電荷移 動络合物之安定性、導電性等)及化學性質且又與單獨使 用上述之習知分子陰離子之糸相比可顗示較優之效果。即 ,以製作多數之電容器元件時之電容器栓能作比較之場合 ,特別可顯現優異效果之化合物為芳香族化合物(磺基醌 、葸一磺酸、取代萘~磺酸、取代笨磺酸)或雜環磺酸。 於本發明中使用之所謂碌基醌係^分子内具有1個Κ 上之磺酸基及酮構造之化合物的總稱,其具有能Μ磺基餛 陰離子形態充當摻雜物有效的作用之化學構造者即可。碌 基醌之基本骨架之具體例有對-苯匯、鄰-苯醌、1,2-案围 、.1,4-萘醞、2, 6-萘醌、9, 10-蒽醌(Μ下簡稱蒽醌)、i,4 -27- 本紙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,歡寫本頁) tr----------線一 經 濟 部 智 ,慧 財 產 局 員 工 消 費 合 作 社 印 製I aliphatic carboxylic acid. However, the range of use of the above-mentioned oxidants may be limited by the chemical structure of the military compound, the oxidant M, and the reaction conditions. For example, the oxidation (polymerization) of phenophanes, according to the Handbook of Conducting Polymers (M arce 1 Dekker, I nc .Issued, 1 8 7, pp. 9 9, Ϊ1 ig. 5), depending on the type of substituent, the oxygenation potential (an indicator of the ease of polymerization) is greatly changed (the model garden of oxidation potential) (Approximately 1.8 to approximately 2.7 V). The left-2 6-^ 's Zhang scale ^ uses the Chinese National Standard (CNS) A4 specification (210 X 297 mm)' (Please read the precautions on the back before filling this page ) r Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Λ A7 B7 V. Description of the invention (24) Right polymerization reaction. Therefore, there are specific combinations of military compounds and oxidants. The present invention is to find a combination of manufacturing methods that can improve the characteristics of capacitors within such a limited range, thereby solving the above-mentioned problems. In the production of the conductive polymer of the present invention, the coexistence of dopant The anion is an electrolyte compound or other anionic system that can dissociate the oxidant anion produced by the above oxidant (an oxidant anion). Specific examples thereof include chloride ion, an aliphatic organic carboxylic acid anion of h-Cu, sulfuric acid anion, phosphate anion, and Ci-Cu aliphatic ammonium phosphate anion and boric acid anion. In addition, electron acceptor dopants of M0 +, NOa * salts (such as NOBFi, NOPFb, NOSbFc, NOAsFs, NOCH3S〇3, NosBF4, fiOaPFs, NozCF3S03) can also be used. In addition, since the aforementioned yin heterozygotes used in the present invention and the conventional molecular yin male (eg, CIO *-, Β ··· 1, etc.) have different dopant properties (the stability of the charge transfer complex, the conductivity, etc.) ) And chemical properties, and compared with the conventional use of the conventional molecular anions of fluorene can show better results. That is, when the capacitor plugs used in the production of most capacitor elements can be compared, the compounds that exhibit particularly excellent effects are aromatic compounds (sulfoquinone, pyrenesulfonic acid, substituted naphthalene ~ sulfonic acid, and substituted sulfonic acid) Or heterocyclic sulfonic acid. The so-called quinone quinone series used in the present invention is a general term for compounds having a sulfonic acid group and a ketone structure on a K in the molecule. It has a chemical structure that can effectively act as a dopant when the sulfonium anion form is used. That's all. Specific examples of the basic skeleton of quinone are p-benzene sink, o-benzoquinone, 1,2-case, .1,4-naphthalene, 2, 6-naphthoquinone, 9, 10-anthraquinone (M (Hereinafter referred to as anthraquinone), i, 4 -27- This paper size applies to Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page) tr --- ------- Printed by Zhiyi, Ministry of Economic Affairs, Consumer Cooperatives of Hui Property Bureau
-I I —i Λν I A7 B7 459255 五、發明說明(25 ) _恵醒、1.2 -惠醒、1,4-鹿醌.、5,6 -鹿醒'、6, ,12 -窟醒、览 並醌、茛醌、莰醌、2 , 3-莰二醌、9 ,10-菲醌、及2 , 7-芘 醒0 另外,上述磺基醌之磺酸基係含有上述醌化合物之氫 原子之1個Μ上被磺酸基取代之芳香族磺酸構造,或介着 Ci-Cui飽和或不飽和烴基之2價基由磺烷撐基取代之脂 肪族磺酸構造。又,亦可為上逑之磺基醌之氫之1個W上 被Ct-c6之飽和或不飽和烴基或烷氧基或選自F、Cl、Br之 取代基取代之化學構造。其中,在本發明中最哥取之磺基 醌為使用具有蒽癘、1,4-蔡醌、2 ,6-萘醌之骨架之磺基醒 ;例如蒽醌類時為蒽餛Μ-磺'酸、蒽醗-2-碼酸、蒽醌-1,5 ψ -二磺酸、蒽醌-1,4-二磺酸、蒽醌-1 ,3-二磺酸、蒽錕-1, 6-二磺酸、葸匯-1,7-二磺酸、蒽_-1,8-二磺酸、葸醒-2 ,二磺酸、:ί圜-2 ,3-二磺酸、蒽圈-2,7-二磺酸、蒽匯-1,4,5-三磺酸、蒽輥、-2,3,6,7-四磺1酸、及其鹼釜靥鹽 及銨鹽。 、 經濟部智慧財產局員工消費·合作社印製 若是1,4-萘醌類時可使用1,4-萘醌-5-磺酸、ι,4-萘 酲-8-磺酸、1,4-萘醌-5,7-二磺酸、1,4-萘醌-5,8-二磺 酸及其鹼金靥盥及銨鹽。 2,8-萘醌頰時可使用2,6-萘醒4-磺酸、2,6-蔡圈-3-磺酸、2,6-萘醌-4-磺酸、2,1萘醗-3,7-二磺酸、2,6-萘 醗-4, ,8-二磺酸及其鹼金靥鹽及銨鹽。 另外,上述之磺基醌亦可從工業用染料Ψ選用,例如 :蒽醌藍R、蒽醌紫RN-3RN,這些染料亦可作為磺基輥系摻 " -2 8 - 本紙張尺度適用中國國家標準(CNS)A4規绛(210 X 297公釐) 459255 A7 B7 五、發明說明(26 ) 雜物K上述之盥彤態使用。 本發明使用之磺基醌,依化合物有些會參與單體化合 物之聚合反應而充當氧化的脫氫化劑作用,结果磺基醌被 遢原而Μ醒構造體之質子附加體,即氫醌或Μ原來之圃氫 •醌(quinhydrone)彤態作為摻雜物含存於固體電解質,内亦 可。 本發明使用之蒽單磺酸係其1個磺酸基由蒽骨架取代 之蒽單磺酸化合物之總稱,較可取之化合物為例如未取代 之Μ磺酸,或蒽磺酸之蒽環之氫由(h-Cu晕好Ct-C8之直 鏈或支耦之飽和或不飽和趣基或烷氧基之至少一個取代之 取代化合物。 可提供上述之未取代窻一磺酸陰離子之化合物為例如 蒽-1-磺酸、蒽-2-磺酸、蒽-9-磺酸及其鹼金屬鹽及銨_鹽 。又,上述之蒽環之氫進一步被取代之Μ單磺酸取代化合 物之該取代基乃例如_基、乙基、丙基、異丙基、丁基、 |> 異丁基、第三丁基、戊基、己基、辛,基、癸基、+二基等. 烷基、或乙烯基、稀丙基、3-丁烯基、έ-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、辛氧等、癸氧基及十二烷氧基等。 本發明使用之取代蔡一磺酸係有一個磺酸基在萘骨架 上取代之萘一磺酸化合物及烷氧基取代蔡一磺酸化合物的 缌稱。 較可取之化合物為萘一磺酸之萘環之氫原子被 ,尤其Ci-Cei直鏈或'支鏈之飽和或不飽和烷氧基之至少 -29- 本紙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#/填寫本頁) -----訂---.1-----線、 經濟部智慧財產局員工消費合作社印製 經濟部智慧財產局員工消費合作社印製 459 255 A7 _ __B7_;_ 五、發明說明(27 ) 一個Μ上取代之化合物。 能提供上述之取代萊一磺酸陰離.子之化合物之具體.例 為具有萘-1-磺酸、策-2-磺酸及其鹼金釋鹽、銨鹽、有襪 四鈒胺鹽等化合物费架且其萘環之氫原子被烷氧基之1個 以上取代之化學構造之化合物。 本發明使用之取代苯磺酸係有一個Μ上之磺齒基在苯 核骨架上取代之苯磺酸及烷基取代苯碩酸之總稱。 較可取之化合物為未取代之苯磺酸或苯磺酸之苯環之 氫原子被^-。》,尤其Ci-Cis之直键或支鐽之飽和或不飽 和烴基之一個K上取代之化合物。 本發明使用之雜環磺酸陰難子係具有有一個Μ上之 磺酸基直接或經由烷撐基(aUylene)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離子的總稱,較可 取之雜環化合物之骨架可例舉嗎啉、哌啶、哌嗪、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***及苯並呋喃骨架。 可提供上述雜環磺酸陰離子之化合物之具體例為2-眯 唑磺酸、4-嗎啉丙烷磺酸、.呋喃-3-磺酸、2-苯並咪唑磺 酸、2-苯並眯唑丙烷磺酸、4-甲基-4-哌嗪甲烷磺酸、2,3 -苯並呋喃-3-磺酸及該等化合物之納鹽等鹼金羼鹽、銨鹽 或季銨鹽。 其中較可取者為芳番族系磺酸化合物包括:十二烷基 苯磺酸鈉、萘磺酸鈉、蒽醌-2-磺酸鈉、蒽囿-2,6-二磺酸 銨、1,4-萘醞-2-磺酸納、3-甲基-2-蒽醌.甲垸磺酸鈉、蒽 ,3 0 -. 本紙張尺度適用中國國家標準(CNS>A4規格(210 X 297公釐〉 i Ji I I,----I I I ^---ul^ilmln (請先閱讀背面之注$項#,篆寫本頁) 、 A7 459 255 ______B7_;_ 五、發明說明(28) -2-磺酸納、9,10-二甲氧葸-2-磺酸四丁銨鹽、9,10-二己 基蒽-2-磺酸四丁銨鹽、2-丙氧蔡-6-磺酸鈉、2-丙氧蔡-6 -磺酸四丁銨盥、2-甲氧萘-6-磺酸鈉、2,3-二甲氧萘- 6-磺酸四丁銨鹽等;及雜環型磺酸包括:4 -嗎啉丙烷磺酸鈉 、2-苯难眯唑代丙烷磺酸鈉、4-甲基-卜哌嗪甲烷磺酸納 、2,3-苯並呋哺-3-磺酸納等。 在本發明中,為形成固體電解質而在噻吩及吡咯類之 單體化合物之化學聚合時,最好K適硫酸鹽作為氧化劑使 用。在噻吩類之化學聚合時最適合之過硫酸鹽為過硫酸銨 及過硫酸鉀;對此使用鐵(31)鹽糸氧化劑時,無法避免有 鏃元素殘留於導電性聚體組.成物中而影響電容器之特性之 問題。 次說明固體電解質(等電性聚體組成物)之形成(聚合 反應)之條件於下ί 聚>反應所用之單體化合物、氧化劑、有機陰離子摻 雜物及橡膠狀彈性料之各個使用濃度雖依單體化合物、氧 化劑、摻雜物f彈性料之種類(包括取代基之種類)或其與 溶媒等之組合而%同,但單體之濃度通常為IX 10 - 4〜10 冥耳/公升範圍,最佳為1Χ10-3〜5莫耳/公升範圍。反 應溫度則依反應物之種類及反應方法而改變3故難加以界 — 定,但通常為- 70¾〜2 50¾ ,較可取為0D〜15〇υ,特別可 取為1 5〜1 0 範圍。 上述聚合反應適用之溶液或聚合後之洗淨用溶媒之較 可取者為例如四氫呋喃(THF)或二噁烷、二***等醚類、 -31- 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) Λ- ' — — — If--» I I I I I I I . 經濟部智慧財產局員工消費合作社印製 459255 : 經濟部智慧財產局員工消費合作社印製 五、發明說明(29 ) 或丙围、甲基乙基酮等酮類;二甲基甲醢胺(DMP)或乙睛 、苄睛、S-甲基吡咯醌(NMP)、二甲基亞硯(DMSq)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 甲烷等非芳香族糸氯化烴溶媒;硝基甲烷或硝基乙烷、硝 基苯等硝基化合物;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 酸酐)、水或彼等之混合溶媒。較可取者為水、酵類、_ 類、乙酸酯類及/或其混合糸。 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: 本發明之一方之電極(陽極U係使用鋁、鈦、钽、鈮 或Μ其為基質之合金系等具有閥作用之金屬萡、棒或K其 為主成分形成之燒锫體等習知材料,並為了彤成介質層及 增大比表面積目的,依習知方法對該等金屬電搔之表面實 施蝕刻或化學.(化成)處理,以在金屬箔上彤成該金龎糸氧 化被膜層3 〇 . 固體電解質(導電性聚體11成物)4之胗成,宜採用在 閥作電極箔之介質層上聚合上述單體化合物之方法 ,尤其使用可使本發明之含橡膠狀彈性料之耐熱性及耐衝 擊性優異之導電性聚趙姐成物在具有细孔或空隙構造之介 質層上化學的析出之方法。另外,為了提高罨接觸,最好 在上述之方法形成之導電性聚體組成物曆上進一步設置其 他導霄體層,即例如塗佈導電糊或利用電鍍、蒸鍍、導電 樹腊膜等肜成導電體曆5。 -32- (請先閱讀背面之注意事項再填寫本頁) 致 ----訂---- ,·線、 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459255 A7 經濟部智慧財產局員工消費合作社印製 _____B7_五、發明說明(30 ) 對依本發明之上述製造方法製造之固體電解電容器, 再在其導電體曆5上模覆樹脂或配裝樹脂或金屬製之外裝 殼,或藉浸潰樹脂等方式設置包封體6,進而配設接续端 子7即可製得適合各種用途之固體電解電容器製品。 (II)於含金屬粉末導電體曆含有橡膠狀彈性料之場合· 使在含有金屬粉末之導電體層中含有橡膠狀彈性料時 ,使用由金属粉末構成之導電體填充料及以橡膠狀彈 作為粘结劑之主成分之金屬粉末.導電性糊。 適用之橡膠狀强性料為一般之掾膠(天然橡膠,尿烷 橡膠、乙烯-丙烯共聚合物、乙烯-丙烯-二烯共聚合物、 苯乙烯-丁二烯橡膠、丁基橡膠、異戊間二烯橡膠、矽酮 系橡膠及氟系橡膠等合成橡膠)或熱塑性彈性料(苯乙烯系 、烯烴系、尿烷系、1,2-聚丁二烯系及氯乙烯系等)◊ 上述之中,K具有耐熱性優異之氟系橡膠及矽酹条橡 膠較為可取。 氟糸橡膠為分子中含有氟原子之合成橡膠之總稱,係 作為特殊橡膠使用,與通用之橡膠有所區別。其具體例為 含氟丙滕襁酯之聚合物、氟化亞乙烯系共聚合物、四氟化 乙烯-全氟代甲基乙烯酸共聚合物、含氟磷氮糸及含氟矽 嗣系聚合物等。這些合成樹脂依種類具有不同性質,但在 市售之橡膠中具有超群之附熱性,且具優晷之耐藥品性及 耐候性。 調製等電性糊之溶媒可為一般習用之等電性糊用溶媒 ,例如可使用N-甲基-2-吡咯烷酮、N , 二甲基乙酿基醯 -33- 本紙張尺度適角中國國家標準(CNS)A4規格(210 X 297公釐) <請先閱後背面之注意事項#,餐寫本頁) J 裝 i I.-----訂·---^------II —i Λν I A7 B7 459255 V. Description of the invention (25) _ Xing Xing, 1.2-Hui Xing, 1, 4-deerquinone., 5, 6-Lu Xing ', 6,, 12-Cave Xing, overview Benzoquinone, butter quinone, perylene quinone, 2, 3-perylene diquinone, 9, 10-phenanthrene quinone, and 2, 7-perylene, and the sulfonic acid group of the sulfoquinone contains a hydrogen atom of the quinone compound The structure of an aromatic sulfonic acid substituted with a sulfonic acid group on one M or an aliphatic sulfonic acid substituted with a sulfoalkylene group in the divalent group of a saturated or unsaturated Ci-Cui hydrocarbon group. Alternatively, it may be a chemical structure in which one of the hydrogens of the sulfoquinone in the above structure is substituted with a saturated or unsaturated hydrocarbon group or alkoxy group of Ct-c6 or a substituent selected from F, Cl, and Br. Among them, the most preferred sulfoquinone in the present invention is the use of sulfo groups with anthracene, 1,4-caequinone, and 2,6-naphthoquinone; for example, anthraquinone M-sulfone 'Acid, anthracene-2-code acid, anthraquinone-1,5 ψ-disulfonic acid, anthraquinone-1,4-disulfonic acid, anthraquinone-1,3-disulfonic acid, anthracene-1, 6-disulfonic acid, fluorene-1,7-disulfonic acid, anthracene-1,8-disulfonic acid, hydrazone-2, disulfonic acid, fluorene-2,3-disulfonic acid, anthracene Circle-2,7-disulfonic acid, anthracene-1,4,5-trisulfonic acid, anthracene roll, -2,3,6,7-tetrasulfonic acid 1 and its alkali ketones and ammonium salts. 1. Employees of the Intellectual Property Bureau of the Ministry of Economic Affairs and Cooperatives can use 1,4-naphthoquinone-5-sulfonic acid, ι, 4-naphthoquinone-8-sulfonic acid, 1,4 if it is 1,4-naphthoquinones. -Naphthoquinone-5,7-disulfonic acid, 1,4-naphthoquinone-5,8-disulfonic acid and its alkali metal ammonium salts and ammonium salts. For 2,8-naphthoquinone, 2,6-naphthoquinone 4-sulfonic acid, 2,6-naphthoquinone-3-sulfonic acid, 2,6-naphthoquinone-4-sulfonic acid, and 2,1 naphthalene -3,7-disulfonic acid, 2,6-naphthalene-4,, 8-disulfonic acid and its alkali gold phosphonium salts and ammonium salts. In addition, the above sulfoquinones can also be selected from industrial dyes, such as: anthraquinone blue R, anthraquinone violet RN-3RN, these dyes can also be used as sulfo rolls. Chinese National Standard (CNS) A4 Regulations (210 X 297 mm) 459255 A7 B7 V. Description of the Invention (26) Miscellaneous objects K are used in the above state. The sulfoquinone used in the present invention acts as an oxidative dehydrogenating agent depending on the fact that some of the compounds will participate in the polymerization reaction of the monomer compound. As a result, the sulfoquinone is protonated by the proton and the structure of the M, ie, the hydroquinone or M The original hydroquinone (quinhydrone) state is contained in the solid electrolyte as a dopant, and may also be contained therein. The anthracene monosulfonic acid used in the present invention is a general term for an anthracene monosulfonic acid compound in which one sulfonic acid group is substituted by an anthracene skeleton. The preferred compound is, for example, unsubstituted M sulfonic acid, or hydrogen of anthracene ring of anthracene sulfonic acid. Substituted compounds substituted by at least one of (h-Cu halo Ct-C8 linear or branched saturated or unsaturated saturated or unsaturated dialkyl or alkoxy groups. Compounds that can provide the above-mentioned unsubstituted sulfonium monosulfonic anions are, for example, Anthracene-1-sulfonic acid, anthracene-2-sulfonic acid, anthracene-9-sulfonic acid, and alkali metal salts and ammonium salts thereof. Furthermore, the above-mentioned anthracene ring hydrogen is further substituted by the M monosulfonic acid-substituted compound. Substituents are, for example, _yl, ethyl, propyl, isopropyl, butyl, > isobutyl, third butyl, pentyl, hexyl, octyl, decyl, + diyl, etc. Or unsaturated groups such as vinyl, dilute propyl, 3-butenyl, and hexa-hexenyl; and methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy , Octyloxy, etc., decyloxy and dodecyloxy, etc. The substituted naphthalenesulfonic acid used in the present invention is a naphthalenemonosulfonic acid compound and an alkoxy group having a sulfonic acid group substituted on the naphthalene skeleton. Substitute the nickname of Tsai monosulfonic acid compound. A more preferred compound is the hydrogen atom of the naphthalene ring of naphthalene monosulfonic acid, especially Ci-Cei linear or 'branched saturated or unsaturated alkoxy group of at least -29- This paper size applies to the Chinese National Standard < CNS) A4 specification (210 X 297 mm) ------ (Please read the precautions on the back # / fill out this page first) ----- Order ---. 1 ----- line, printed by the Consumer Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs, printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, printed by 459 255 A7 _ __B7 _; _ 5. Description of the invention (27) A compound substituted on M. Can provide the above-mentioned anionic compounds of substituted lysine sulfonic acid. Specific examples of the compounds are naphthalene-1-sulfonic acid, cer-2-sulfonic acid and its alkali gold-release salts, ammonium salts, and hosiotetraamine salts. A chemically structured compound such as a compound that has a hydrogen atom in its naphthalene ring replaced by one or more alkoxy groups. The substituted benzenesulfonic acid used in the present invention is a general term for a benzenesulfonic acid group substituted with a sulfonic acid group on the benzene core skeleton and an alkyl-substituted benzenesulfonic acid. The preferred compound is unsubstituted benzenesulfonic acid or the hydrogen atom of the benzene ring of benzenesulfonic acid. 》, Especially compounds substituted on a K of Ci-Cis straight or branched saturated or unsaturated hydrocarbon groups. The heterocyclic sulfonic acid anisodote used in the present invention has an anion of a heterocyclic sulfonic acid compound having a chemical structure substituted on a heterocyclic ring directly or indirectly through an alkylene group (aUylene). In general, the skeleton of the preferred heterocyclic compound may be morpholine, piperidine, piperazine, imidazole, furan, 1,4-dioxane, benzimidazole, benzothiazole sulfur, benzoisoxazole, benzene Benzotriazole and benzofuran skeleton. Specific examples of the compound capable of providing the above heterocyclic sulfonic acid anion are 2-oxazolesulfonic acid, 4-morpholinepropanesulfonic acid, furan-3-sulfonic acid, 2-benzimidazolesulfonic acid, 2-benzopyrene Alkali gold sulfonium salts, ammonium salts or quaternary ammonium salts such as zopropanesulfonic acid, 4-methyl-4-piperazinemethanesulfonic acid, 2,3-benzofuran-3-sulfonic acid and sodium salts of these compounds. Among them, aromatic sulfonate compounds are preferred: sodium dodecylbenzenesulfonate, sodium naphthalenesulfonate, sodium anthraquinone-2-sulfonate, ammonium anthracene-2,6-disulfonate, 1 , 4-naphthyl naphthalene-2-sulfonate, 3-methyl-2-anthraquinone. Sodium methosulfonate, anthracene, 3 0-. This paper size applies to Chinese national standard (CNS > A4 specification (210 X 297 Mm> i Ji II, ---- III ^ --- ul ^ ilmln (please read the note on the back of the item #, write this page first), A7 459 255 ______B7_; _ 5. Description of the invention (28)- Sodium 2-sulfonic acid, 9,10-dimethoxyfluoren-2-sulfonic acid tetrabutylammonium salt, 9,10-dihexylanthracene-2-sulfonic acid tetrabutylammonium salt, 2-propoxycae-6-sulfonic acid Sodium, propionite-6-tetrabutylammonium sulfonate, sodium 2-methoxynaphthalene-6-sulfonate, 2,3-dimethoxynaphthalene-6-sulfonic acid tetrabutylammonium salt, etc .; and Heterocyclic type sulfonic acids include: sodium 4-morpholine propane sulfonate, sodium 2-benzodoxazolyl propane sulfonate, sodium 4-methyl-piperazine methane sulfonate, 2,3-benzofuran- 3-Sodium sulfonate, etc. In the present invention, in the case of chemical polymerization of thiophene and pyrrole monomer compounds in order to form a solid electrolyte, it is preferable to use K-sulphate as an oxidant. The most suitable persulfate at the time is ammonium persulfate and potassium persulfate; when iron (31) salt is used as the osmium oxidant, it is impossible to avoid the presence of europium elements in the conductive polymer group. The composition will affect the characteristics of the capacitor. The conditions for the formation (polymerization reaction) of solid electrolyte (isoelectric polymer composition) are described below. The conditions of the monomers, oxidants, organic anion dopants, and rubbery elastic materials used in the polymerization are described below. Each use concentration is the same depending on the type of monomer compound, oxidant, dopant f elastic material (including types of substituents) or its combination with the solvent, etc., but the concentration of the monomer is usually IX 10-4 ~ 10 The range of ears / litres is preferably 1 × 10-3 ~ 5 moles / litres. The reaction temperature varies depending on the type of reactant and the reaction method. Therefore, it is difficult to define, but it is usually -70¾ ~ 2 50¾, 0D ~ 15〇υ is more preferable, and the range of 15 ~ 10 is particularly preferable. The solution or polymerization solvent suitable for the polymerization reaction is preferably tetrahydrofuran (THF) or dioxane or diethyl ether. Isoethers, -31- Paper size applies to China National Standard (CNS) A4 (210 X 297 mm) (Please read the notes on the back before filling out this page) Λ- '— — — If-- »IIIIIII. Employees of Intellectual Property Bureau, Ministry of Economic Affairs Printed by the Consumer Cooperative 459255: Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. 5. Description of the Invention (29) or ketones such as propionate, methyl ethyl ketone; dimethylformamide (DMP) or acetonitrile, benzyl Non-protonic polar solvents such as eye, S-methylpyrroloquinone (NMP), dimethyl sulfene (DMSq); esters such as ethyl acetate or butyl acetate; non-aromatic ammonium chloride such as chloroform or dichloromethane Hydrocarbon solvents; nitro compounds such as nitromethane or nitroethane, nitrobenzene; or alcohols such as methanol, ethanol, propanol, and other organic acids, such as formic acid or acetic acid, propionic acid, or the organic acid. Acid anhydride (such as acetic anhydride), water or their mixed solvents. Preferable are water, yeast, _, acetate, and / or mixed mash. The outline of the structure of the solid electrolytic capacitor of the present invention is described below with reference to FIG. 1: The electrode of one of the present invention (the anode U is made of aluminum, titanium, tantalum, niobium, or an alloy of which the matrix is used as a matrix, and has a valve function. Rhenium, rod, or K is a conventional material such as sintered carcass, and for the purpose of forming a dielectric layer and increasing the specific surface area, the surface of these metal electrodes is etched or chemically treated according to conventional methods. Chemical conversion) treatment to form the gold oxide coating layer 3 on the metal foil. 0. Solid electrolyte (conducting polymer 11 product) 4 formation, it is suitable to polymerize the above on the dielectric layer of the valve as the electrode foil As a method for a monomer compound, in particular, a method for chemically precipitating an electrically conductive poly-zhaocheng product having excellent heat resistance and impact resistance of the rubber-containing elastic material of the present invention on a medium layer having a pore or void structure In addition, in order to improve the contact of rhenium, it is best to further provide another conductive layer on the conductive polymer composition formed by the method described above, such as coating a conductive paste or using electroplating, evaporation, and a conductive wax film. Wait until it becomes a conductive calendar 5. -32- (Please read the precautions on the back before filling out this page) To ---- order ----, · The line, this paper size applies to China National Standard (CNS) A4 specifications (210 X 297 mm) 459255 A7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs _____B7_V. Description of the invention (30) For solid electrolytic capacitors manufactured according to the above-mentioned manufacturing method of the present invention, A solid electrolytic capacitor product suitable for various uses can be prepared by covering the upper mold with a resin or a matching resin or a metal outer case, or by providing the encapsulation body 6 by impregnating the resin, and then providing the connection terminal 7. (II ) Where metal powder-containing electrical conductors contain rubber-like elastic materials · When rubber-like elastic materials are included in a conductor layer containing metal powder, use a conductive filler made of metal powder and use rubber-like elastics as a binder The main ingredient is metal powder. Conductive paste. Suitable rubber-like strength materials are general rubber (natural rubber, urethane rubber, ethylene-propylene copolymer, ethylene-propylene-diene copolymer, styrene -Butadiene rubber , Synthetic rubber such as butyl rubber, isoprene rubber, silicone rubber and fluorine rubber) or thermoplastic elastomers (styrene, olefin, urethane, 1,2-polybutadiene and (Vinyl chloride, etc.) 之中 Among the above, fluorine-based rubber and silicone rubber with excellent heat resistance are preferred. Fluorine rubber is a general term for synthetic rubber containing fluorine atoms in the molecule. It is used as a special rubber and is used in general The rubbers are different. Specific examples are polymers containing fluorinated propenyl esters, fluorinated vinylidene copolymers, ethylene tetrafluoride-perfluoromethyl vinyl acid copolymers, and fluorinated phosphorus nitrogen And fluorosilicone-based polymers, etc. These synthetic resins have different properties depending on the type, but they have excellent heat resistance among commercially available rubbers, and have excellent chemical resistance and weather resistance. The solvent used to prepare the isoelectric paste can be the commonly used isoelectric paste. For example, N-methyl-2-pyrrolidone, N, dimethyl ethyl hydrazone-33- This paper is suitable for China. Standard (CNS) A4 specification (210 X 297 mm) < Please read the precautions on the back #, write this page) J Pack i .----- Order · --- ^ ---- -
A7 B7 459255 五、發明說明(31 ) 胺、二甲基甲醯胺、乙酸丁酯等溶媒或其混合物。摻配於 導電性糊之溶媒量,雖依導電性糊之使用目的及要求之粘 度而不同,但一般為糊之固形.份之等童乃至10倍量。 適合作為導電性糊之導電性填充料之例子為銀粉或其 他金或銅等金屬粉末及碳粉末等。較可取者為銀粉,尤其 含銀粉量80質暈3: Μ上之填充料最佳。粉末之粒度以平均 粒徑1〜lQi/ ϊβ者較佳。平均粒徑1W m从下時視密度太小, 將增大糊之體積,不利於導電層之形成。反之,平均粒徑 超過lDwra時,粒度過粗,易發生與陰極引線端子接鱭不 良之問題。 - 玆說明較可取之粘结劑之氟系橡膠之使用情形於下: 可取之粘结劑為含有8 G〜1 0 Q質量%之氟系橡膠所構 成,其餘成分可混合習知之樹脂等。氟条橡膠具有良好之 橡膠彈性,受變形時有將該變彤復原之性質,與不能使變 形復原之氟糸橡膠有所區別^此種氟条橡膠包括習知之氟 化亞乙烯系共聚體橡膠、6-氟化丙烯糸共聚體橡膠、4-氟 化乙烯糸共聚體橡膠、含氟两烯酸酯橡膠及含氟矽酮祿膠 等。這些橡膠為未加碲者,其玻璃轉移點(Tg)低於室溫, 因此由此點即可與氟樹脂明顯的區別。 上述導電性填充料及粘结劑之混合比例為導電性填充 料50〜95質量%及粘结劑5〜50質量$較佳。導電性填 充料低於50質量%畤降低導電性,超過35質量%時降低粘 結劑之结合力,難Μ如期形成.専電體層。 為使上述之導電性填充料及粘结劑之混合物(固形份) -3 4 - 本紙張尺度適用令國國家標準(CNS)A4規格(210 X 297公釐) <請先閱讀背面之注意事項年填寫本頁)A7 B7 459255 V. Description of the invention (31) Solvents such as amine, dimethylformamide, butyl acetate or mixtures thereof. Although the amount of the solvent blended in the conductive paste varies depending on the purpose and required viscosity of the conductive paste, it is generally equal to 10 times the solid content of the paste. Examples of the conductive filler suitable as the conductive paste are silver powder, metal powder such as gold or copper, carbon powder, and the like. The preferred powder is silver powder, especially the silver powder containing 80 mass halo 3: the best filling material. The particle size of the powder is preferably from 1 to lQi / ϊβ. The apparent particle density of the average particle diameter of 1 W m is too small from below, which will increase the volume of the paste, which is not conducive to the formation of the conductive layer. Conversely, when the average particle size exceeds 1 Dwra, the particle size is too coarse, and the problem of poor connection with the cathode lead terminal easily occurs. -The use of fluorine-based rubber, which is a more preferable binder, is described below. The preferable binder is a fluorine-based rubber containing 8 G to 10 Q% by mass, and the remaining ingredients can be mixed with conventional resins. Fluorine strip rubber has good rubber elasticity, and has the property of recovering the deformation when deformed. It is different from fluorinated rubber which cannot recover the deformation. ^ This fluororubber includes the conventional fluorinated vinylidene copolymer rubber. , 6-fluorinated propylene fluorene copolymer rubber, 4-fluorinated ethylene fluorene copolymer rubber, fluorine-containing diacrylate rubber, and fluorine-containing silicone rubber. These rubbers are those with no tellurium added, and their glass transition point (Tg) is lower than room temperature, so this point can be clearly distinguished from fluororesin. The mixing ratio of the conductive filler and the binder is preferably 50 to 95% by mass of the conductive filler and 5 to 50% by mass of the binder. If the conductive filler is less than 50% by mass, the conductivity will be reduced, and if it is more than 35% by mass, the binding force of the binder will be reduced, and it will be difficult to form the electrostrip layer as expected. In order to make the above-mentioned mixture of conductive fillers and binders (solid content) -3 4-This paper size applies the national standard (CNS) A4 specification (210 X 297 mm) < Please read the precautions on the back first (Fill out this year)
-i ! I 訂--------V 經 濟 部. 智 慧 財 產 局 員 工 消 費 合 作 社 印 製 i:r^4S9 2 〇〇 A7 B7 經濟部智慧財產局員工消費合作松印製 適量之有機溶媒。使用 使用例如乙酸丁海、_乙 用量為對固形份100質 狀彈性料之導電性糊之 解電容器之一實施例。 属箔(陽極),在其表面 被膜3及细孔2。茌暘 子7a » 4為形成於氧化 固體電解質層雖然亦可 發明之導電性糊時,導 質。 面(I)項之「在電醇質 分詳加說明過,但可使 咯及聚苯肢等,尤其聚吡 取。於此導電性聚合物. 醌磺酸、烷基蒽醌磺酸 Μ磺酸、烷氧基蒽磺酸 磺酸、苯磺酸、烷基苯 上述有機磺酸陰離子之 物之任意的可结合位置 烷基或烷氧基之上述化 意的可结合位置上.結合 五、發明說明(32 ) 彤成具適當粘性之糊,通常需添加 之溶媒宜可溶解氟糸橡膠者,即可 酸戊酿及乙酸丙酯等。有機溶媒之 ^量份通常使用4 0〜1 0 0質量份。 次說明使用本發明之含有橡膠 固體電解電容器聆下: 第2圖所示為本發明之固體電 圃中1為鋁或鉅等之閥作用金 藉電解陽極氧化等彤成有介質氧化 極1上藉焊接等連结有陽極引線端 被膜3上之固體電解質層(陰極)? 使用無機半導體化合物,但使用本 電性聚合物特別適合作為固體電解 有關導電性聚合物,雖已在前 層中含有橡膠狀彈性料之場合」部 用聚(3,4-次乙二氧基噻吩)、聚吡 咯或聚(3,4-次乙二氧基噻吩)較可 中使含有作為摻雜物(dopant)之蒽 、烷氧基葸醌磺酸、蒽磺酸、烷基 、萘磺酸、烷基萘磺酸、烷氧基薬 磺酸、烷氧基苯磺酸等之陰離子。 磺酸取代基,只要具有在骨架化合 上结合之化學構造者即可;又具有 合物,係具有在其骨架化合'物之任 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 閱 讀 背 面 之 >主 項 再: 填 窝 本 頁 459255 A7 B7 五、發明說明(33 ) 有Ci-thei烷基或烷氧基之化學構造。 等電性聚合物之彤成方法可採用例如使甩氣化劑(聚 合引發劑)使形成上述聚合物之單體化學聚合、或電解聚 合或其併用等一般習知方法。舉例而言,將氧化被膜曆浸 漬於單體溶液後,再浸漬於氧化劑溶液,然後加溫進行化 學聚合,並將此操作反覆數次。依此反覆聚合可使導電性 聚合杨層成為多_壘合構造,利用外裝樹脂封裝時顯示優 異之耐,熱應力性。 又,固體電解質層亦可為由含上述橡膠狀彈性料之導 電性聚體組成物構成者。 以氟糸橡膠粘结劑作為導電性糊使用時可發揮下,述之 作用效畢。雖然導電性聚合物層具有多層叠合構造而顯示 優異之耐熱應力性,對其塗敷加有瓌氧樹脂等熱收縮性大 之粘结劑之導電性糊時,可侵入導電性聚合物之表曆。此 導電性糊在加熱時發生較大應力使導電性聚合物層之多曆 彤狀受影響。但,使用氟糸橡膠粘结劑時,浸入導電性聚 合物表層之糊之發生應力小,可Μ保持生成之導電性聚合 锪曆之形狀,於是,可增進電容器之耐熱性。 化學聚合時使用之氧化劑為過硫酸銨、有機磺酸鐵( 1 )、氯化鐵U )等無機酸鐵、Fe(Cl〇4)3、有機酸鐵(I ) 、過硫酸鹽、烷基過硫酸鹽、過硫化氫、K2Cr207等。 在固體電解質層4之表面形成有導電體層5。此導電 體曆5係與固體電解質層密着接合,充當陰極作用之同時 成為接合陰極引線端子7b之接着.劑作用。導電體層5之厚 、 ^ -36- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閲靖背面之沒意事項再填寫本頁) 裝!— 訂· — 4 經濟部智慧財產局員工消費合作社印φ1取 459 255 . A7 ____B7 五、發明說明(34 ) 度一般為10〜5〇wm左右。 ..導電體層5雖然可單獨ίΐΤ使用本發明之導電性糊形成 ,但最好為如下詳述,於導電性聚合物餍(即固體電解質 層)4.上形成碳糊形成之層,進而在其上設置利用本發明 之導電性糊形成之層。 ^ 碳糊可使用在黑鉛粉末中加有粘结鋪之樹脂及溶媒之 一紐習用碳糊,但最好Κ氟糸橡)Τ作為粘结齊j之樹脂。碳 糊層.之厚度只有' 1〜2 μ m即可。 於導電體層5之外表面接合陰極引線端子7b,然後保 留該陰揮引線端子7b及陽極引線端子7a之露出部·,利用絕 緣性樹脂6封裝。絕緣性樹脂主要使用環氧樹脂。封裝時 i 亦可藉壓鐮法實行〇 _ (S)等電性碳層含有橡膠狀彈性料之埸合 導電性碳層係使用由導電性材料、粘结劑及溶媒為主 成物之導電性碳糊形成。上述導電性材料最好由80質量3! Μ上之人造黑鉛粉組成。人造黑鉛粉以使用固定碳99質量 3ί Κ上、平均粒徑1〜3/iBi、長寬比10Μ下而粒徑32wmM 上之粒子佔12質量;SM下者為宜。 鱗片狀或葉片狀之天然黑鉛之長寬比為10K上,因此 與本發明使用之導電性材料不同。由於人造黑鉛之長寬比 愈高,其作為導電^性碳糊之填充性會降低而增加糊之柢抗 性,故人造黑鉛粉之長寘比必須10以下。此種人劈黑鉛之 純度逭比天然黑鉛或碳黑高,可提高填充率,具有因熱而 劣化之程度極小之特性。 . -3 7- 本紙張尺度適用中國國家標<(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 i ! -----線.^*31 經濟部智慧財產局員工消費合作社印製 4 59 255 A7 __B7___ 五、發明說明(35 ) 另外,該黑鉛粉之固定碳份亦同樣會影饗糊之抵抗性 ,人造黑鉛粉之固定碳份愈高愈可使抵坪性降低。因此, 為達成本發明之目的必須使用固舍碳份9 7質量% K上之人 (............... ......·.·..· 造黑鉛粉。在此所諝之固定碳份係指含碳量之指操之值, V . . 有JIS法(JISK 2 4 2 5 )、碳素協會法、ASTM法及BS ΐ等。 為獲得導電性碳糊之等旬塗布性,該黑鉛粉之平均粒 徑最好在1〜13w in範圍。即使使用人造黑铅粉,如果使用 平均粒徑13/ίΐιΜ上之粉末時,有時亦無法獲得均匀之糊 層,使用於固體電解電容器時,會使電容器特性之tan δ * · .. j 及等值串聯電阻(ESR) f之惡化。又,即使平均粒徑在該 範圍内,若含有粗粒子時亦會妨箐塗押之巧勻性,但將粒 徑32W mK上之粒子之含有虽控麗奔12@最1篇工里,可 避免上逑之問題。 作為専電性材料使用之本發明導電性碳糊必須使用含 上述人造黑鉛粉至少80質量%以上之材料。將夫然黑鉛及 碳黒併合使用且上述人造黑鉛粉末满.80声量X靖,所調製 之導電性碳糊無法確保充分之導電度。人造黑鉛粉之使用 須95質量K上,最好為100質量35。専電性材料之其餘 v ...... ..................... 經濟部智慧財產局員工消費合作社印製 部份為銀、金及錮等金屬粉以琴碳黑、天缚黒鉛及其他赞 末狀導電性物質。 本發明之固體電解電容器係使用主含有人造黑鉛粉80 質量χ μ上之導電性材料、粘结劑及溶.見名麈.麗..生.碳,.糊 雖然在此使用人造黒鉛粉不限定具備上述之固定碳份、平 . 均粒徑及長寬比者,但最好是使用如上所界定之人造黑鉛 - -. .... " """' 〜 -3 8 *-r 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 459255 A7 B7 五、發明說明(36 ) 之.糊。’ 導電性碳糊適用之粘结劑為.一種具有橡膠弾性而受變 形時有回復原形之性質之材料,而且最好在寅施形態中可 被溶劑膨潤或可懸浮之材料,同時在製造電容器時之回流 處理時顯規優異之耐熱性之橡膠狀彈性料。具有上述特性 之彈性料包括輿戊間二烯橡膠、丁二烯橡膠、笨乙烯/丁 二烯橡膠、睛橡膠、乙烯/丙烯共聚合物(EPM、EPDM等) 、丙烯酸類橡膠、多硫化系橡膠、氟系聚合物、矽酮橡膠 及其他熟塑性彈性聚合物等。其中較可取者為EPM、EPDM 及氟糸聚合物。氟糸聚合物只要是含有氟素之聚合物即可 ,並無持別限制。此等橡膠性聚合物比一般作為導電性碳 糊使用之環氧樹脂吸水性及彈性率低,及在接合部具有鑀 和應力之效果。 上逑氟条聚合物包括:例如聚四氟乙烯、聚(氛三氟 乙烯)、氟化亞乙烯(VDF)及六氟丙烯(HFP)之二元共聚 合物、含有四氟乙烯之共聚合物、四氟乙烯/丙烯共聚合 物、聚氟化距乙烯、聚氟化乙烯、含氟丙烯酸酯橡膠及含 氟矽嗣橡膠等。 __ 導電性碳糊中之導電性材料與粘结劑之混合比例>乂全 固彫份質量言,導電性材料為30〜99質量%,50〜90質 量客較佳,粘結劑為1〜70質量S:。導電性材料低於3Q質 量%時,導電性碳櫬之導電性過低,超過3 9質畺t時喪失 導電性碳糊之接着性及應力媛和性能。 専電性碳糊中使用之溶媒係與一般導電性碳糊所用者 -39- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 一 ·1 1 K · 1 n < .· N}- ^ . f (請先聞讀背面之注意事t填寫本頁) t5J· 經濟部智慧財產局員工消費合作社印製 ^ 4 5 9 2^〇 45925^ B7 五、發明說明(37) 相同,例如N-甲基-2-吡咯、Ν,Ν-二甲基乙醯醯胺 '二 甲基甲醢胺、乙酸丁醅等溶媒之軍獨或混合物。添加於導 電性碳糊中之溶媒量办依使甩目的所要求之粘度加Μ決定 ,通常為葑糊之固彤份使用等量乃至10倍量。 使用本發明之導電性碳糊製作固體電解電容器時,其 陽搔係使用具有閥作用之鋁、钽、鈮、鈦、结等之單體金 屬或彼等之合金且經過蝕刻處理之金臛箔,或亦可為微粉 燒结體等表Β積經增大者。 I 、. 對此等金靥表面實行化學處理等形成介質層後,於其-i! I Order -------- V Ministry of Economy. Intellectual Property Bureau employee consumer cooperative prints i: r ^ 4S9 2 〇〇A7 B7 The Ministry of Economic Affairs ’Intellectual Property Bureau employee consumer cooperation loosely prints an appropriate amount of organic solvent . An example of an electrolytic capacitor is a conductive paste using, for example, Dinghai Acetate and B as a conductive paste with a solid content of 100 mass. It is a foil (anode) and has a film 3 and pores 2 on its surface. Rhenium 7a »4 is conductive when it is formed on an oxidized solid electrolyte layer, although a conductive paste can be invented. The above (I) item "is described in detail in the alcohol content, but it can be used for polyphenylene, especially polypyridine. Here is the conductive polymer. Quinone sulfonic acid, alkyl anthraquinone sulfonic acid M Sulfuric acid, alkoxyanthracenesulfonic acid, benzenesulfonic acid, alkylbenzene, any of the above-mentioned organic sulfonic acid anions of the organic sulfonic acid anion can be bonded to any of the alkyl or alkoxy in the above-mentioned intended binding position. 2. Description of the invention (32) Tongcheng has a paste with proper viscosity. Usually, the solvent that needs to be added is suitable for dissolving fluororubber, that is, succinic acid, propyl acetate, etc. The amount of organic solvent is usually 40 ~ 1. 0 0 parts by mass. Using the rubber-containing solid electrolytic capacitor of the present invention: Figure 2 shows the solid electric garden of the present invention. 1 is aluminum or giant valve action gold by electrolytic anodization, etc. A solid electrolyte layer (cathode) connected to the anode lead end film 3 by welding or the like on the dielectric oxidizing electrode 1? An inorganic semiconductor compound is used, but the use of this electrical polymer is particularly suitable as a conductive polymer for solid electrolysis. Contains rubber-like elastic material in the front layer Occasionally, poly (3,4-ethylenedioxythiophene), polypyrrole, or poly (3,4-ethylenedioxythiophene) may contain anthracene and alkane as dopants. Anions of oxyfluorenone sulfonic acid, anthracenesulfonic acid, alkyl, naphthalenesulfonic acid, alkylnaphthalenesulfonic acid, alkoxyfluorenesulfonic acid, alkoxybenzenesulfonic acid, and the like. The sulfonic acid substituent is only required if it has a chemical structure bonded to the skeleton compound; it also has a compound, which has any of its skeleton compounds. The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Read the main item on the reverse side: Fill in this page 459255 A7 B7 5. Description of the invention (33) There is a chemical structure of Ci-thei alkyl or alkoxy group. The isoelectric polymer can be formed by a conventionally known method such as chemically polymerizing a monomer forming the polymer with a gasification agent (polymerization initiator), electrolytic polymerization, or a combination thereof. For example, after immersing the oxide film in the monomer solution, immersing it in the oxidant solution, and then heating it for chemical polymerization, this operation is repeated several times. Repeated polymerization according to this can make the conductive polymerized poplar layer into a multi-barrier structure, which exhibits excellent resistance and thermal stress when encapsulated with an exterior resin. The solid electrolyte layer may be composed of a conductive polymer composition containing the rubber-like elastic material. When a fluorinated rubber adhesive is used as a conductive paste, the following effects can be exhibited. Although the conductive polymer layer has a multi-layered structure and exhibits excellent thermal stress resistance, when a conductive paste coated with a highly heat-shrinkable adhesive such as fluorene resin is applied thereto, it can penetrate the conductive polymer layer. Table calendar. This conductive paste undergoes a large stress upon heating, which affects the multi-layered shape of the conductive polymer layer. However, when a fluorene rubber adhesive is used, the stress caused by the paste immersed in the surface layer of the conductive polymer is small, and the shape of the resulting conductive polymer calendar can be maintained. Therefore, the heat resistance of the capacitor can be improved. The oxidants used in chemical polymerization are inorganic acid iron such as ammonium persulfate, organic iron sulfonate (1), iron chloride U), Fe (Cl04) 3, organic acid iron (I), persulfate, alkyl Persulfate, hydrogen persulfide, K2Cr207, etc. A conductor layer 5 is formed on the surface of the solid electrolyte layer 4. This conductor 5 is in close contact with the solid electrolyte layer, and acts as a cathode and at the same time as a bonding agent for joining the cathode lead terminal 7b. The thickness of the conductor layer 5 ^ -36- This paper size applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (please read the unintentional matter on the back of Jing before filling this page) Install! — Order · — 4 Employee Cooperative Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs φ1 take 459 255. A7 ____B7 V. Description of the invention (34) The degree is generally about 10 ~ 50wm. .. The conductor layer 5 can be formed by using the conductive paste of the present invention alone, but it is preferable to form a layer of carbon paste on the conductive polymer (ie, solid electrolyte layer) 4. A layer formed using the conductive paste of the present invention is provided thereon. ^ The carbon paste can be a conventional carbon paste in which a resin and a solvent are added to the black lead powder. However, it is preferable to use fluorocarbon as the resin. The thickness of the carbon paste layer is only 1 ~ 2 μm. The cathode lead terminal 7b is bonded to the outer surface of the conductor layer 5, and the exposed portions of the female lead terminal 7b and the anode lead terminal 7a are retained, and sealed with an insulating resin 6. As the insulating resin, epoxy resin is mainly used. At the time of encapsulation, i can also be implemented by pressing the sickle method. _ (S) and other electrical carbon layers contain rubber-like elastic materials. The conductive conductive carbon layer uses conductive materials composed of conductive materials, binders and solvents. Sexual carbon paste is formed. The conductive material is preferably composed of artificial black lead powder of 80 mass 3 μM. For artificial black lead powder, the fixed carbon 99 mass 3 ί, average particle size 1 ~ 3 / iBi, aspect ratio 10M and particle size 32wmM account for 12 masses; the lower SM is preferred. The scale-like or leaf-like natural black lead has an aspect ratio of 10K, and is therefore different from the conductive material used in the present invention. As the length-to-width ratio of artificial black lead is higher, its filling property as a conductive carbon paste will decrease and increase the resistance of the paste. Therefore, the length ratio of artificial black lead powder must be 10 or less. This kind of human black lead has higher purity than natural black lead or carbon black, can increase the filling rate, and has the characteristics of minimal degradation due to heat. -3 7- This paper size applies to China National Standard < (CNS) A4 Specification (210 X 297 mm) (Please read the precautions on the back before filling this page.) / Installation ---- Order i!- ---- Line. ^ * 31 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 4 59 255 A7 __B7___ V. Description of the Invention (35) In addition, the fixed carbon content of the black lead powder will also affect the resistance of the paste. The higher the fixed carbon content of artificial black lead powder, the lower the flatness. Therefore, in order to achieve the purpose of the invention, it is necessary to use a person with a carbon content of 97.7% by mass on K (..................... Black lead powder. The fixed carbon content here refers to the value of carbon content. V... There are JIS method (JISK 2 4 2 5), Carbon Association method, ASTM method and BS ΐ. In order to obtain the equal coatability of conductive carbon paste, the average particle diameter of the black lead powder is preferably in the range of 1 to 13 in. Even if artificial black lead powder is used, if the powder with an average particle size of 13 / ίΐΜ is used, It is not possible to obtain a uniform paste layer, and when used in solid electrolytic capacitors, tan δ * · .. j and equivalent series resistance (ESR) f of the capacitor characteristics are deteriorated. Even if the average particle diameter is within this range If the coarse particles are contained, the uniformity of the coating may be affected, but the particle content on the particle size 32W mK can be controlled by Liben 12 @ 最 一 工 工, which can avoid the problem of the upper part. The conductive carbon paste of the present invention used as a material must be made of a material containing at least 80% by mass of the above-mentioned artificial black lead powder. A combination of black black lead and carbon tritium is used and the above-mentioned artificial black lead powder is used. Full .80 sound volume X Jing, the modulation of the conductive carbon paste can not ensure sufficient conductivity. The use of artificial black lead powder must be 95 mass K, preferably 100 mass 35. The rest of the electrical materials v ... ........... Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs are silver, gold and osmium metal powder with carbon black, Sky-bound lead and other Zanzi-like conductive substances. The solid electrolytic capacitor of the present invention uses conductive materials, binders, and solvents containing 80 mass x μ of artificial black lead powder as the main ingredient. Carbon, paste Although the use of artificial rhenium lead powder is not limited to those with the above-mentioned fixed carbon content, average particle size and aspect ratio, it is best to use artificial black lead as defined above--... " " " " '~ ~ 3 8 * -r This paper size applies to China National Standard (CNS) A4 (210 X 297 mm) 459255 A7 B7 V. Paste of the description of the invention (36). '' The conductive carbon paste is suitable as a binder. It is a material that is rubbery and has the property of returning to its original shape when deformed, and it is best to be swollen by solvents in the form Suspended material and rubber-like elastic material with excellent heat resistance during reflow treatment during capacitor manufacturing. Elastic materials with the above characteristics include pentadiene rubber, butadiene rubber, styrene / butadiene Ethylene rubber, eye rubber, ethylene / propylene copolymers (EPM, EPDM, etc.), acrylic rubber, polysulfide rubber, fluoropolymer, silicone rubber, and other mature plastic elastic polymers, etc. Among them, the more preferable ones are EPM, EPDM and fluorene polymers. The fluorofluorene polymer is not limited as long as it is a polymer containing fluorine. These rubbery polymers have lower water absorption and modulus of elasticity than epoxy resins generally used as conductive carbon paste, and have the effects of stress and stress at the joints. Fluoropolymers on the top include: binary copolymers of polytetrafluoroethylene, poly (trifluoroethylene), vinylidene fluoride (VDF) and hexafluoropropylene (HFP), and copolymers containing tetrafluoroethylene Polymers, tetrafluoroethylene / propylene copolymers, polyvinylidene fluoride, polyvinylidene fluoride, fluorinated acrylate rubber, and fluorinated silicone rubber. __ The mixing ratio of the conductive material and the binder in the conductive carbon paste > 乂 Full solid content, the conductive material is 30 to 99% by mass, preferably 50 to 90% by mass, and the binder is 1 ~ 70 mass S :. When the conductive material is less than 3% by mass, the conductivity of the conductive carbon is too low, and when it exceeds 39% by mass, the adhesiveness and stress properties of the conductive carbon paste are lost.之 The solvent used in electric carbon paste and those used in general conductive carbon paste-39- This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)-· 1 1 K · 1 n < . · N}-^. F (Please read the notes on the back t to fill out this page) t5J · Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs ^ 4 5 9 2 ^ 〇45925 ^ B7 V. Description of Invention (37 ) Identical, such as N-methyl-2-pyrrole, N, N-dimethylacetamide, dimethylformamide, butyl acetate and other solvents. The amount of the solvent to be added to the conductive carbon paste is determined according to the viscosity required for the purpose of the addition plus M, which is usually equal to or even 10 times the solid content of the paste. When using the conductive carbon paste of the present invention to make a solid electrolytic capacitor, the impregnation is a gold-plated foil made of a single metal or an alloy of aluminum, tantalum, niobium, titanium, and a junction that have a valve function, and an etching treatment Or, it can also be an increase in the surface B product such as a fine powder sintered body. I. After chemical treatment is applied to the surface of these gold tinctures to form a dielectric layer,
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V 外表面設置固體之半導電ii層(最好為上述導電性聚合物 , 構成之固體電解質層),進面在其外表面形成本發明之導 電性碳糊層後,再在其表面形成含金屬導電體層(最好為 含有上述橡膠性彈性料之'含金屬導電體層),然後配装引 線製成^體電解電容器。 使用本發明之讀電性碳糊製成之固體電解電容器具有 耐熱性高,等值串聯電阻(ESR)及阻抗低,阻抗之熱劣化 小及耐濕性優等多種特性。 〈實施本發明最佳之形態〉 次配合實施例、比較例及參考例說明本發明之蕞佳黄 施形態於下。 _ —---- .---------------------- 踅施例1 使用1Q重量3!之己二酸銨水溶液及施加13V之電壓對 切成所規定之大小面積之蝕刻處理過之鋁萡(基板)進行-化,-學(化成)處理使在該鋁箔表面彤成介質層(即形成介質氧 , -40' 本紙張尺度適用中國國家標準(CNS)A4規格(210^ 297公釐) (請先閱請背面之注意事項再填寫本頁) 裝------訂-------' 經濟部智慧財產局員工消費合作社印製 459255 A7 B7 經濟部智慧財產局員工消費合作社印制π 五、發明說明(33) 化被膜),繼之將其浸漬於溶有5克之3 ,4-次乙二氧基噻 吩之1.2其耳/公升的乙基甲基酮溶疲中溶解有聚酯尿焼 .橡膠0·05克之溶液(溶液〇中,然後再浸潰於含有20質 童X之過硫酸銨(Κ下稱為APS)及0.125質量!S之2-蒽醌 磺酸鈉(東京化成社製)之水溶液(溶液3)中,使介質層表 面含浸該水溶液後取出,並在6Gtr之環境下放置1Q分鐘實 行氣化聚合。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1(]次。隨後,利用電子顯微鏡照片觀 察结果確認形成之導電性聚合物層(固體電解質曆)係里層 狀構造。 呙外,將上述聚合處理後之基板置於水/異丙醇(IPA) 溶媒中進行胼遷原並小心的萃取及利用離子色曆分析求得 等電性聚體組成物中之硫酸離子及2-蒽醌磺酸離子之含量 ,结果以導電性聚體組成物中之聚合物之每一反覆構造單 元計,硫酸離子之含量為1.5莫耳X,2-蒽醒磺酸離子之 含量為14.0冥耳%。該基板之附著質量(固體電解質)増加 15¾。該固體電解質層之導電度為73 s/cm。 繼之,將上述之彤成有3,4 -次乙二氧基曄吩聚合物之 鋁萡(基板)置於10重量%之己二酸銨水溶液中處理後,檢 測其火花電壓。為了確切比較試樣元件特性,增加元件數 目(以下之實施例亦同)。卽,在50¾環境下及電流密度ί0 mA/ca^之條件下,對元件各實行5次n = 5 ;结果如下表i 所示。 然後,於上逑鋁箔之形成有等電性聚合物層之部分塗 -4 1- 本紙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赛寫本頁) ,裝 !1訂.! 線 ΓΤ· 459255 A7 B7 五、發明說明(39 ) 上碳糊及銀糊後接陰極引線端子,同時在未形成有導電性 聚合物層之鋁芯部焊接陽搔引線端芋,最後利用環氧樹脂 封裝而製取電容器元件。將此電容器元件置於125t!下經 過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代表損失角之正切1 ( tanS )(亦即損失係数)。此等值皆在120Hz測定者。Z代 表諧振頻率時之胆抗值,而LC代表腌加額定電壓1分鐘後 測定之漏電流值。各測定值皆為30個電容器元件之平均值 。又,LC係Μ 1 w AM上者視為不良品;^ 0以AM上者視為短 .路品表示,並將其剔除求出LC值之平均。 比較例1 ' .1 除不添加聚醑尿烷橡膠之外,其餘悉依實_例1實行 ,並與實施例.1同樣評估所得之電容器元件,结果如表1 及表2所示。 另外,依實施例1所逑方法求得聚體組成物中之硫酸· 果 结 量· 含 之 子 衛 酸 磺 醒 蒽 - 2 及S5f 子耳 離莫 為 量 含 子 雛 酸 磺 醌 葸 - 2 - 質 &解 ?* 鶯體 含免 ?-固 離 % 酸耳 硫莫 .(請先閲讀背面之注意事項再灰寫本頁) /裝----- -6Ji---V. A solid semi-conducting ii layer (preferably a solid polymer layer composed of the above-mentioned conductive polymer) is provided on the outer surface, and the conductive carbon paste layer of the present invention is formed on the outer surface, and then formed on the surface. A metal-containing electric conductor layer (preferably a 'metal-containing electric conductor layer containing the above-mentioned rubber elastic material), and then equipped with leads to form a bulk electrolytic capacitor. The solid electrolytic capacitor made of the electric-reading carbon paste of the present invention has various characteristics such as high heat resistance, low equivalent series resistance (ESR) and low impedance, low thermal degradation of impedance, and excellent humidity resistance. <The best form for carrying out the present invention> The following examples, comparative examples, and reference examples will be used to explain the best form of the present invention. _ —---- .---------------------- 踅 Example 1 Using 1Q weight 3! Ammonium adipate aqueous solution and applying a voltage of 13V to The etched aluminum alloy (substrate) cut into a prescribed size and area is subjected to chemical conversion, chemical conversion (chemical conversion) treatment to form a dielectric layer on the surface of the aluminum foil (that is, to form dielectric oxygen, -40 '. This paper is applicable to China National Standard (CNS) A4 Specification (210 ^ 297 mm) (Please read the notes on the back before filling out this page) Packing -------- Order ------- 'Intellectual Property Bureau Staff, Ministry of Economic Affairs Printed by the Consumer Cooperative 459255 A7 B7 Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs π 5. Description of the invention (33) Chemical film), and then immersed in 5 grams of 3,4-ethylenedioxythiophene 1.2 In its ear / litre of ethyl methyl ketone, polyester urethane was dissolved. A solution of 0.05 g of rubber (in solution 0, and then immersed in ammonium persulfate containing 20 mass children X (hereinafter referred to as "K" APS) and 0.125 mass! S of 2-anthraquinone sulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.) in an aqueous solution (solution 3), the surface of the dielectric layer was impregnated with the aqueous solution, and the solution was placed in a 6 Gtr environment for 1 Q minutes Gasification polymerization is performed. After completion of polymerization, K water is washed. This polymerization reaction treatment and washing steps are repeatedly performed 1 () times. Subsequently, the results of electron microscope photographs are used to confirm the formation of the conductive polymer layer (solid electrolyte calendar). ) Is a layered structure. In addition, the substrate after the above polymerization treatment is placed in a water / isopropanol (IPA) solvent for migration and careful extraction, and the isoelectric polymer is obtained by ion color history analysis. The content of sulfate ion and 2-anthraquinone sulfonate ion in the composition. As a result, based on each repeated structural unit of the polymer in the conductive polymer composition, the content of sulfate ion was 1.5 mol X, 2-anthracene. The content of sulfonic acid ions is 14.0 mole%. The adhesion mass of the substrate (solid electrolyte) is increased by 15¾. The electrical conductivity of the solid electrolyte layer is 73 s / cm. Then, the above-mentioned Tongcheng has 3,4- After processing the aluminum rhenium (substrate) of ethylenedioxyphene polymer in a 10% by weight aqueous solution of ammonium adipate, the spark voltage is measured. In order to accurately compare the characteristics of the sample elements, increase the number of elements (the following implementation Example is the same). In the environment of 50¾ and the current density of 0 mA / ca ^, the components were implemented 5 times each n = 5; the results are shown in Table i below. Then, an isoelectric polymer layer was formed on the aluminum foil. Partially coated-4 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page), and install! 1 order.! Line ΓΤ · 459255 A7 B7 V. Description of the invention (39) After the carbon paste and silver paste are applied, the cathode lead terminals are connected, and the impregnated lead terminals are welded on the aluminum core portion without the conductive polymer layer. Take the capacitor element. This capacitor element was heated at 125 t! For 2 hours, and its initial characteristics were measured. The results are shown in Table 2 below. C in the initial characteristics in this table represents capacity, and DF represents the tangent 1 (tanS) of the loss angle (that is, the loss coefficient). These values are measured at 120Hz. Z represents the choke resistance value at the resonance frequency, and LC represents the leakage current value measured 1 minute after the rated voltage is marinated. Each measurement value is an average of 30 capacitor elements. In addition, LC above M 1 w AM is regarded as a defective product; ^ 0 is represented by AM above as a short circuit product, and the average value is calculated by excluding it. Comparative Example 1 '.1 Except that polyureaurethane rubber was not added, the rest was implemented in accordance with Example 1 and the capacitor element obtained in the same evaluation as in Example .1 was shown in Tables 1 and 2. In addition, according to the method described in Example 1, the sulfuric acid, the fruit yield, and the sulfonanthrene sulphanthracene-2 and S5f contained in the polymer composition were determined according to the method described in Example 1. 2- Quality & Solution? * The body of the warbler contains free-solid% sulfide. (Please read the precautions on the back before graying this page) / Installation ----- -6Ji ---
n H ϋ I 經濟部智慧財產局員工消費合作社印製 實/ 依件 悉元 他器 其容 ,電 Λ 外之 之得 次所 . 7 恬 .為評 改樣 次同 ο 由例 。 數跑 CIn次實 S/之與 70.合並 為 聚 , 度 化行 電 2 氧實 導例除 1 之胨 例 層實 施 及 子 離 酸 硫1. 之為 中量 物含 成子 組灕 體斷+ 聚硫 .得, 求果 。 法结 示方量 所述含 2 所之 表 1 子 及例雛 1 施酸 表實磺 如依酿 果 蒽 结2- 耳 莫 本紙張尺度適用中國國家標準'(CNS)A4規格(210 X 297公釐) 4 5 9 2 55 A7 B7 五、發明說明(40) - 2-蒽酲磺酸離子含量為13*0其耳基板上之附着質量與 不添加聚酷尿稗.橡膨而實行10次氧化聚合之·場.合大致相同 。固體電解質層之導.電度為70s/cm。 實施例3 除Μ四氟乙烯/丙烯共聚合物之同濃度丙嗣溶液.替代 實腌例1所使用之聚醋尿烷橡膠溶液之外-,其餘悉依實施 例1實行,並與實施例1同樣評估所得之電容器元件,结 * . 果如表1及表2所示。 另外,依實晦例1所述方法求得聚體組成物中之硫酸 離子及2-BS磺酸雛子之含量,结果硫酸離子含量為1*8 冥耳X,蒽醒磺酸雜子含量為15 _ 8莫耳Γ。基板上之附 着質量增加25¾ ◊固體電解質層之導電度為65s/cni。 實疵例4 ’ 除Μ十二烷基苯磺酸鈉之同濃度溶液替代實施例1所 I 使用之2-蒽醒磺酸納液之外,其餘悉依寅睢例1簧行,並 與實施例1同樣評估所得之電容器元件,結果如表1及表 酸 硫 之 中 物 成 組 .體 聚 得 求 法 方 逑 所 IX 例0 實 依 。 外 示另 所 (請先閱讀背面之注意事項再,#寫本頁> ii------訂·n H ϋ I Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs / according to the original knowledge of other contents, electricity Λ other than the best place. 7 Tian. For the evaluation and modification, the same is the same ο by example. The number of CIn times S / and 70. Combined into a polymerization, the degree of electric power 2 The implementation of the example of oxygen and the separation of the acid and sulfur 1. The medium is composed of the adult group and the body is broken. Sulfur. Get it. The formula shown in Table 1 contains 2 Table 1 seeds and cases. 1 Sulfuric acid, Sulfuric acid, anthracene knot 2-ear Mo. This paper size is applicable to China National Standard (CNS) A4 (210 X 297). (Centi) 4 5 9 2 55 A7 B7 V. Description of the invention (40)-2-Anthracenesulfonic acid ion content is 13 * 0. The adhesion quality on the ear substrate and the addition of polyurethane are not performed. The field of oxidation polymerization is almost the same. The conductivity of the solid electrolyte layer was 70 s / cm. Example 3 Except for the same concentration of acrylonitrile solution of M tetrafluoroethylene / propylene copolymer, instead of the polyurethane urethane rubber solution used in actual pickling example 1, the rest is carried out in accordance with example 1, and is the same as the example 1The capacitor element obtained by the same evaluation, the results are shown in Tables 1 and 2. In addition, the content of sulfate ions and 2-BS sulfonic acid in the polymer composition was determined according to the method described in Example 1. As a result, the content of sulfate ions was 1 * 8 gluteal X, and the content of heteroanthracene sulfonate was 15 _ 8 Mol Γ. The conductivity of the 25 ◊ 增加 solid electrolyte layer on the substrate increased by 65 s / cni. Defective example 4 'Except that the solution of the same concentration of sodium dodecylbenzenesulfonate was used instead of the 2-anthracene sodium sulfonic acid sodium solution used in Example 1, the other Xiyiyin Example 1 was performed, and The capacitor element obtained in Example 1 was similarly evaluated. The results are shown in Table 1 and Table Sulfur and the intermediates were grouped. (Please read the notes on the back before, #write this page > ii ------ order
-flf I n n I 線、 經濟部智慧財產局員工消費合作社印製 翔 上 為板 量基 含 子 0 酸 碕5 果14 结為 ,量 量含 含子 之雛 子酸 離磺 酸苯20 磺基20 苯烷加 基二增 烷十量 二,質 十Μ着 I 耳 f ¾莫# 子31之 ο · % 6 耳為 莫度 5 電 4導 L之 層 質 解 電 體 固 fr 夕 之 液 溶 烯膠 乙橡 亞烷 化尿 氟酯 mM聚 例除代 施 替 實 液 溶 嗣 丙 度 濃 同 之 物 合 聚 共0 丙 氟 六 行 實 1 例 施 實 依 悉 餘 其 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 459255 A7 __B7_ 五、發明說明(41) 並與賁施例1同樣評估所得之電容器元件,结果如表1及 表2所示。 另外,嵌實施例1 ·所逑方法求得聚體組成物中之硫酸 雛子及2-蒽醍磺酸鞲子吝含最,结果硫酸離子含量為1.4 莫耳%,卜恵醌礎酸雜子含童:為1 4 . 2..莫耳%。基板上之附 着質量增加24¾。齒體電解質曆之導電度為73s/cm。併用 氧瓶燃燒法及離子色餍分析法測定含氟量结果為0.5質量 %,因此可知聚體組成物中所含有之氟系橡膠相當於約1 質量% 〇 實施例6 除K吡咯之同濃度溶寐替代3,4 -次乙二氧基噻吩溶液 以及將氧化聚合溫度改為5¾之外,其餘:悉依實施例1實 行,並與實施例1同樣評估所得之電容器元件,结果如表 1及表2所示。 另外,依實胞例1所述方法求得聚體組成'+物中之硫酸 離子及2-蒽醌磺酸離子之含量,结巣硫酸離子含量為1.7 冥耳Si, 2-蒽醌磺酸解子含蠆為15.9其耳X。基板上之附 着質量增加213:。固體電解質曆之導電度為SOs/cih。 參考例1 Μ 4 -甲基噻吩替代3,4-次乙二氧基噻吩之外,其餘悉 依實施例1實行結果完全未生成黑青色之聚4-甲基_吩之 聚合物,顯示4-甲基〇§吩並不因過硫酸鞍(APS)之:作用而 進行聚合反應。 -44 Μ氏張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閲讀背面之注意事項再故寫本頁)-flf I nn I, printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs on the board as a base with a base of 0, acid and 5 fruit 14 The result is that the amount of a young child with an acid is benzene sulfonate 20 sulfo 20 Benzane plus dioxane, ten ounces, ten ounces, two ounces, ¾, ¾ Mo # 子 31 之 ·% 6 ounces are in degrees 5 electrical 4 conductance L layer electrolytes solid fr xi liquid soluble olefin Gum, ethylene, rubber, alkylene, urethane, mM, poly, except for the replacement of the actual solution, the concentration of the same degree of concentration, the same thing together, a total of 0, six examples of propylene fluoride, according to Shi Xiyu, the paper size is applicable to Chinese national standards (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 459255 A7 __B7_ V. Description of the invention (41) The capacitor element obtained by the same evaluation as in Example 1 is shown in Table 1 and Table 2 shows. In addition, in Example 1, the sulfuric acid broth and 2-anthrenesulfonic acid gardenia contained in the polymer composition were determined by the method described above. As a result, the content of sulfate ion was 1.4 mol%, and the benzoquinone basic acid heterozygous With children: for 1 4. 2 .. Mohr%. The mass of the attachment on the substrate is increased by 24¾. The conductivity of the tooth electrolyte was 73 s / cm. The oxygen content was measured by the oxygen cylinder combustion method and the ionic color spectrometry method, and the fluorine content was 0.5% by mass. Therefore, it can be seen that the fluorine-based rubber contained in the polymer composition is equivalent to about 1% by mass. Example 6 The same concentration except Kpyrrole Solvent substitution instead of 3,4-ethylenedioxythiophene solution and change of oxidative polymerization temperature to 5¾, the rest: It is implemented according to Example 1, and the capacitor element obtained in the same evaluation as in Example 1 is shown in Table 1 And Table 2. In addition, the content of sulfate ions and 2-anthraquinone sulfonate in the polymer composition '+ was determined according to the method described in Example 1. The content of sulfate ions was 1.7. The solution contains 15.9 of its ear X. The attached mass on the substrate is increased by 213 :. The solid electrolyte has a conductivity of SOs / cih. Reference Example 1 Except for the replacement of 3,4-ethylenedioxythiophene with M 4-methylthiophene, the rest of the implementation according to Example 1 did not result in the formation of a black-cyan poly 4-methyl-phene polymer at all, showing 4 -Methylphene does not undergo polymerization due to the action of saddle persulfate (APS). -44 MM scale is applicable to China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before writing this page)
459 255 A7 B7 五、發明說明(42 表1火花電腔(單位:v,n=:5) 實施例1 實施例2 實施例3 實施例4 實施例5 賁施例δ 比較例1 19 19 19 19 19 19 19 19 19 19 19 19 19 19 聚合處理次數 .3 4 5 6 19 19 19 19 19 19 19 19 19 19 19 19 18 18 18 18 19 19 19 19 19 19 19 19 19 19 19 19 8 10 19 19 19 19 19 19 18 18 19 19 19 19 19 19 (請先閱讀.背面之注意事項#,填窝本頁) 表2 初期特.性459 255 A7 B7 V. Description of the invention (42 Table 1 Spark electric cavity (unit: v, n =: 5) Example 1 Example 2 Example 3 Example 4 Example 5 贲 Example δ Comparative Example 1 19 19 19 19 19 19 19 19 19 19 19 19 19 19 19 Number of polymerization treatments. 3 4 5 6 19 19 19 19 19 19 19 19 19 19 19 19 19 18 18 18 18 18 19 19 19 19 19 19 19 19 19 19 19 19 8 10 19 19 19 19 19 19 18 18 19 19 19 19 19 19 19 (Please read first. Note on the back #, fill in this page) Table 2 Initial characteristics
不良數/試料數 個/傾Number of defectives / number of samples / tilt
例例例例例例Μ 施腌施施施施較 實實實實實實比 0 8 8 7 7 7 8 6 6 6 8 7 6 6 ooooooo 6 6 6 6 6 6 6 3 3 2 5 2 3 6 ooooooo ooooooo 3 3 3 3 3 / / / / / ο ο 3 3 ο ο y.·裝------ί 訂----1----Example Example Example Example M Pickling Application The application ratio is more actual than the actual ratio 0 8 8 7 7 7 8 6 6 6 8 7 6 6 ooooooo 6 6 6 6 6 6 6 3 3 2 5 2 3 6 ooooooo ooooooo 3 3 3 3 3 / / / / / ο ο 3 3 ο ο y. · 装 -------- ί Order ---- 1 ----
經濟部智慧財產局員工消費合作社印製 對實Jfe例1〜6製得之電容器元件測定初期特性(如表 2)後,曝露於高溫高濕下50D小時,然後再度測定在120 Hz之容量(C)及損失係數(DF%)。结果如表3所示對比較 例1 (不添加聚醅尿烷橡膠)製得之電容器元件亦在同條件 下作同漾之測定,结果併列於表3。由表'3數據顯示,實 -45- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公莩) r 459255 A7 B7 五、發明說明(43) 施例1〜6之電容器元件之壽命加速試驗後之特性之變化 (容最變化率X及損突係數3;)均比比較例為小。由此可知 ,本發明之電容器元件對外應力具有緵和性,壽命長,性 能較高。 表3 初期特性 、85¾ 13V 50Q 時間後 容量U 〇 損失(%) 容量變化率(%) 損失U) 賁施例1 8.0 、 0.6 5.3 3.5 實施例2 8.0 0.6 7.1 4.5 實施例3 8.0 ύ、6 5.2 3.4 實施例4 7.2 0.8 5.7 3.7 實施例5 7.8 0.7 5.1 3.4 實施例6 7.8 0.6 5.2 3.3 比較例1 8.0 0.6 10.5 5.3 (請先閱讀背面之注意事項再填寫本頁) 裝-------訂----- 經濟部智慧財產局員工消費合作社印製 實施例7:導電性糊之調製 使用平均粒徑5.5μ m之銀粉作為導電性填充料及氟系 橡膠之Vi ton橡膠(氟化亞Z烯“氟化乙烯-6氟化丙烯共 聚合物)作為粘结劑。將錕粉8 5質量5S RViton橡膠粉末 15質量Si混合作為糊之固形份,然後添加乙酸丁酷作為溶 媒,混捏製取固彤份60質量S:之粘稠銀糊β -4 6 一 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) 經濟部智慧財產局員工消費合作社印製 459255 A7 ... B7 五、發明說明(44 ) 實施例8;固體電解電容器之製作 .將蝕刻處理及陽極氧化後之具化學變化護膜之鋁箔( 稱化成箔)切成寬度Sum之帶狀,然後K 10mm之長度裁 斷後利用13V之電壓對切口部之未化成部分實行處理,使 在鋁箔之全面胗成介質桌化被膜。將此化成箔之長度方向 之約50¾部分浸漬於3,4-次乙二氧基噻吩之1萁耳/公升 濃度之乙醇溶液中,然後再浸漬於作為氧化劑(聚含引發 劑)之過硫酸銨1.5萁耳/公升及·作為摻雜物(d〇E»ant)之 I · .萘-2-磺酸鈉!3. 12萁耳/公升濃度之水溶液中,保持40¾ 進行聚合反應。將上述之浸漬及聚合操作反覆實胞20次, 使在鋁箔之氧化被膜上形成由3, 4-碑乙二氧基噻吩構成吝 等電性聚合物層。經過20次之反覆聚合形成之等電性聚合 物層之掃猫電子顯微鏡的放大(5000倍)照片如第3圖所 示,係呈層狀構*(第3圖中,上部為廇狀構造之導電性' 聚合物層)〇 次將該具有等電性聚合物層之部分浸漬於碳糊中,在 lQQt;下熱處理30分鐘彤成碳糊層_。所用之碳糊為由混合 ' ' <· 平均粒徑3 w mi黑鉛粉末6 0質量X及氟糸橡膠40質量%,. 添加乙酸丁鹿(作爲溶媒)混捏而成之具有固形份1 6質童% * · » 之粘稠碳糊。 繼之,將形成有上述碳糊層之部分浸漬於貿施例7 士 銀.糊中形成.導電體層而製成電容器元件。將此電容器元件 之未被覆有導電體層之鋁箔部分切斷,然後將其蠱合.4片 ,利用上述之銀糊互相接合後,再接合於引線框(銅合金) -47- ' 本紙張尺度適用_國國家標準(CNS)A4規格(210 X 297公釐)After printing the initial characteristics (as shown in Table 2) of the capacitor elements made by the Jfe cases 1 to 6 by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, the capacitors were exposed to high temperature and humidity for 50D hours, and then the capacity was measured again at 120 Hz ( C) and loss factor (DF%). The results are shown in Table 3. The capacitor elements obtained in Comparative Example 1 (without the addition of polyurethane rubber) were also subjected to the same measurement under the same conditions. The results are shown in Table 3. According to the data in Table '3, the actual -45- size of this paper is applicable to the Chinese National Standard (CNS) A4 specification (210 X 297 cm) r 459255 A7 B7 V. Description of the invention (43) The capacitor elements of Examples 1 to 6 The changes in characteristics after the accelerated life test (capacity change rate X and damage coefficient 3;) were smaller than those in the comparative example. From this, it can be seen that the capacitor element of the present invention has a mild external stress, long life and high performance. Table 3 Initial characteristics, capacity U after 85¾ 13V 50Q time 〇 Loss (%) Capacity change rate (%) Loss U) 贲 Example 1 8.0, 0.6 5.3 3.5 Example 2 8.0 0.6 7.1 4.5 Example 3 8.0, 6 5.2 3.4 Example 4 7.2 0.8 5.7 3.7 Example 5 7.8 0.7 5.1 3.4 Example 6 7.8 0.6 5.2 3.3 Comparative Example 1 8.0 0.6 10.5 5.3 (Please read the precautions on the back before filling this page) Installation ----- Order ----- Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs Example 7: Modulation of conductive pastes Use silver powder with an average particle size of 5.5 μm as a conductive filler and Vi ton rubber (fluorinated rubber) Zene "fluorinated ethylene-6 fluorinated propylene copolymer" was used as a binder. Blend powder 8 5 mass 5S RViton rubber powder 15 mass Si was mixed as a solid content of the paste, then butyl acetate was added as a solvent, and kneaded Take a solid part of 60 mass S: thick viscous silver paste β -4 6 A paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economy 459255 A7. .. B7 V. Description of the Invention (44) Embodiment 8; Production of electrolytic capacitors. After etching and anodizing, the aluminum foil (weighed into foil) with a chemical change protective film is cut into a strip with a width of Sum, and then cut to a length of K 10mm. The voltage of 13V is applied to the unformed portion. Part of the treatment is carried out to form a film covering the entire surface of the aluminum foil. About 50¾ of the length of the formed foil is immersed in a 1-ear / liter concentration of ethanol solution of 3,4-ethylenedioxythiophene. , And then immersed in ammonium persulfate as a oxidant (poly initiator-containing) 1.5 萁 per liter / liters and · as a dopant (d〇E »ant) I ·. Sodium naphthalene-2-sulfonate! 3. 12 In an aqueous solution of mol / liter concentration, maintain 40¾ for polymerization reaction. The above-mentioned immersion and polymerization operations were repeated for 20 times to form an aluminum oxide coating on the aluminum foil. Electrical polymer layer. A magnified (5000x) photo of a scanning electron microscope of an isoelectric polymer layer formed by 20 iterative polymerizations, as shown in Figure 3, shows a layered structure * (Figure 3 , The top is a conductive polymer layer with a 廇 -shaped structure) 0 times The part with the isoelectric polymer layer was immersed in a carbon paste, and heat-treated at 1QQt for 30 minutes to form a carbon paste layer. The carbon paste used was made by mixing '' < · average particle diameter of 3 w mi black lead Powder 60 mass X and 40% by mass of fluorene rubber, a thick carbon paste with solid content of 16 mass% * * »mixed with butyl deer acetate (as solvent) and kneaded. Next, a portion where the carbon paste layer was formed was immersed in the silver paste of Example 7 to form a conductive layer to form a capacitor element. Cut off the aluminum foil part of this capacitor element that is not covered with a conductive layer, and then bond them. 4 pieces are bonded to each other with the silver paste described above, and then bonded to the lead frame (copper alloy) -47- 'This paper size Applicable_China National Standard (CNS) A4 Specification (210 X 297 mm)
459255 A7 B7 五、發明說明(45 ) 上,及在1GQ°C下乾燥30分鐘。然後將未被覆有導電體層 之鋁箔部分溶接於引線框(铜合金)。最後使該等框之一端 露出,使用環氧樹脂(住友Bakelite公司製,商品名ΕΜΓ-?3'20Α),藉轉送模製法封裝製成肩片邀電容器。此電容器 之特性如表4所示。 比較例2 唪將銀糊之粘结劑改為環氧樹脂(油化She 11-Epoxy公 • , ·> * 司製,商品名Epic oat 8 28型)之外,其餘悉依實施例8 實行‘,製取之晶片型固體電解電容器之特性如表4所示。 (請^^讀背面之注^^項再填寫本頁) 裝 iyill-Λ 表 ESR(mQ ) 回流前後之 ESR增加(m£2 ) 回流不良率 耐濕不良率 實施例8 20 2 0/30 0/30 比較例 25 20 6/30 12/30 ---1 .訂·! 11 ^―yl ϋι 表4中: ESR (於100KHZ之等值串聯電阻‘)為試樣30個之平均 97 2 X ο 2 /V 格 規 4 )A s) N (c 準 標 國 國 中 用 適 度 尺 張 紙 -本 經濟部智慧財產局員工消費合作社印製 值。 固流(耐熱性)不良率及耐濕不良率為依下述方法測定 之試漾30個中之不良品數。 回流(亦即耐熱)不良率:通過回流瀘(2301C、30秒) 後,施加額定電壓(13V),經過1分鐘後測定漏電流值。 -48" 經濟部智慧財產局員工消費合作社印製 4 5 9 2 55 A7___;_B7 ___五、發明說明(46)· 灞電流值UyAM下者為合格品(良品),12«ΑΜ_Η者為不 良品。 ·、 耐濕不良率:將試樣、電容器)茸於溫度60ΐ!、相對濕 度90S;下,100(3小時後.取出,施加額定電壓,經過1分 鐘後測定漏電流值。漏電流值12 « AM下者為合格品,12 M AK 土者為不良品。 實施例9 ' Κ長寬比3〜1 . 5、平均粒徑3 w m、粒徑32 μ 上之 粒子佔2質量3ί Μ下.、固定碳分3 9質重;Ϊ之人造黒鉛粉末 (昭和電工公司製,茼品名UFG-5)作為導電性材料,於其 中添加充當粘结劑之乙烯/丙烯/二烯三元共聚合物(EPDM) 之乙酸丁酯懸浮液(懸浮液中之EPD.M 7質量X),使該樹脂 (三元共聚合物)之固彤份為人造黒鉛粉末1〇〇質量份之80 質量3ί,然後授拌2 4小時製得導電性碳湖。 遒之切取大小3 X 1 0 ra m之蝕刻處理過之紹萡,利用 寬lmia之聚醯亞胺膠帶在其兩面貼附,Μ劃分出4«及5mm 之二部分。然後將該鋁箔之3 MX 4 mra部分浸潰於10質量JS 之己二酸銨水溶液中施加13v電壓進行化學(化成)處理 形成介質氧化被膜。繼之,將i鋁箔之3 mm X4 min都分浸 漬於含有20質量3£ 3, 4-次乙二氧基噻吩之異丙酵溶疲(溶 液1)後取出並在室溫下乾燥。然後再將此鋁箔之3 mm X4 tain 部分(形成有介質氧化皮膜之部分)浸漬於含有3(3質董%過 硫酸銨(APS)及1質量3;葸醞-2-磺酸鈉之水溶液(溶液2) 之後取出,並在6Q°C氣氛中放置10分鐘實行氧化聚合。然 -49- • n I n I n ·1 n n n 1 . I 1 - - (請先閱讀背面之注項#-填寫本頁) 訂-· 0!- --線 本紙張尺度適用中國國家標準CCNS)A4規格(210 X 297公釐) r*459255 A7 _ B7 五、,發明說明(47) 後再度浸濱於溶液1中後賁行上述同樣之處理。將上述之 浸潰於溶液1至氧化聚合之操作反覆實行2 5次後,利用5 dt c之溫水洗淨10分鐘,最後在實行乾燥30分鐘,形成 _ 導電性聚合物層(固體電餘.質曆)。觀察如此製得之形成有 導電性聚合物層之鋁箔的斷面之掃描電子顯微鏡照片( 2 , 0 0 Q倍)確認導電性聚合物成曆狀構造完全包覆金靥鋁 上之介質(氧化鋁>之微细孔内的表面旦曆狀導電性聚合物 層間有空陳部存在。經査在微细孔構造之外部表面形成之 導電性聚合物層之厚度為約5W fa,而形成層狀構造之各層 之厚度為約Q . 1〜0 3 u m之範圍。然後,於上述鋁箔之彤 成有導電性聚合物層之部分塗上述方法調製之導電性碳輝 後,在ΙΟΕΙΊΟ下熱處理3D分鐘,在上.述導電性聚合物上形 成碳糊導電曆。 然後,於上述鋁箔之彤成有導電性聚合物層之部分塗 上銀糊接績陰極引線端子,同時在未形成有導電性聚合物 '•層之部分則利用環氧樹脂封裝藉焊接接缠有陽極引線端子 之元件之後,於125¾施加額定電壓進行2小時之熟化, 製取總共30個之電容器。 對此3D個之電容器,依習知方法測定等值串聯電阻( ESR)並實行回流處理。.然後再度測定回流處理後之ESR, 並評估回流處理前後之E S R的變化。同時對所有之電容器 分別實行後述之耐濕不良率的試驗,结果如表5所示。 實施例10 除將實施例9所述之EPDM之乙酸丁酷懸浮液改為氟 -50- 本紙張尺度埤用中國國家標準(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) 袭 \· 11—訂 --------線''y· 經濟部智慧財產局員工消費合作杜印製 1:^45 9 2 b5 a7 — _ B7 _ 五、發明說明(4.8 ). Ί· \ 糸聚合物ί氟化亞乙烯-六氟丙烯-四氟乙烯共聚合物)之乙 酸丁酯鼪浮液,Μ及將EPDM固形分對人造黑鉛粉末100質 量份之80質蠆X改為7 0質量X之外,其餘悉依實施例9所 述方法實施,製取3Q個之電容器,並依實施例9評估電容 器之特性,结果併,示於表5中。 - \ · 比較例3 ' , 除將等電性枯料之人造黑船·^粉末改用平均粒徑4Ϊ a、 粒徑32 wW上之粒子佔2質量!ϊ议下、固定碳4 98 . 5質 > · ·· 量X、長寬比明顯10Κ上之鱗片狀天然黒鉛,Μ及將粘结 劑之SPDM改用環氧樹脂之外,其餘悉依實施例9實跑, 製得30個之電容器。此等電容器之特性評估结果示於表5 中。 .' 比較例4 . > 將導電性材料之人造黑鉛粉末改用平均粒徑4yiii、粒 徑32« bK上之粒子佔2質量Χ’Κ下、固定碳分98.5質畺 %、長寬比明顯1 〇 Μ ±之鱗片天然黒鉛之外,其餘悉依實 施例Ifl實梅,製得30個之電容器。此等電容器之特性評估 结果示於表5中。 經濟部智慧財產局員工消費合作社印製 上逑實施例劣、1 tr及比較例3、4所實施之各種評估 試驗傜依下述之測定方法及條件實行。 〈測定方法> 1.回流(耐_性)不良·率 使製柞之3 0個固體霄解電容器通過高峰溫度230¾之 回流爐3 0秒後施加額定電壓(6 . 3 V ),1分鐘後測定漏電流 -5 1- 本纸張尺度適用中國國家標準(CNS)A4規格(210 Χ 297公釐) 459255 A7 VR7 五、發明說明(49) 1 j 。漏電流值未滿3 w A者視為合格品(良品.),超過者.辑為不 良品。 2.附濕不良率 將回流試驗之合格品置於溫度6DT:、相對濕度90¾之 .氣氛中,1000小時後取出,施加額定電壓6 . 3V) , _ 1分 . I 鐘後測定漏電流,漏電流值未滿12W Α者視為合格品。 表5 ESR ΙΟΟΚΗζ (m Ω ). 回流爵後之 E S E之變化 (m Ω ) 回流不 良率* 1 酎濕不 良率* 1 實施例S 20 5 0/30 2/30 實施例3 20 0 0/30 0/3 0 實施例10 50 50 ' 5/3 0 12/25 比較例4 40 20 ' 2/30 3/28 *1:不合格數/試樣數 <請先閱讀背面之注意事項再填寫本頁) ----ml 線 經濟部智慧財產局員工消費合作社印製 〈產業上之利用性〉 .,, 本發明提供一種由固體電解質層及含金靥粉末之導電 體層,或導電性碳層及在該層上設有含金靥粉末之導電體 層構成之至少一層中含有橡膠狀彈性料之固體電解罨容器 及其製法,K及使用於該固體電解電容器之固體電解質, 固體電解質之製法,固體電解電容器用導電性糊,及固體 電解電容器用導電性碳糊。 一 5 2 _ .本紙張尺度適用中國國家標準(CNS)A4規格(210 χ 297公釐) A7 459255 __B7__.__ 五、發明說明(50 ) 本發明之固體電解電容器由於在其形成固體電解質之 導電性聚體組成物中含有橡膠狀彈性料,因此可大幅減少 浸漬及聚合次數,提高生產性,從而苛提供小型、低阻抗 、高性能且對外應力具有緩和性之固體f觫電容器及其製 法。 另外,由於M.特定之聚雜環化合物,尤其導電性聚噻 吩作為π電子共軛聚合物,充當固體電解質使用,因此可 獲得耐電壓特性(火花電壓試驗〉、高頻持性、損失係數( t a n S )、阻抗特性、漏:電流、耐熱性(回流性)等大幅增進 之效果。 尤其,在上述導電性聚體k成物中,對於具‘有71電子459255 A7 B7 V. Description of the invention (45) and drying at 1GQ ° C for 30 minutes. Then, a part of the aluminum foil not covered with the conductor layer was dissolved in the lead frame (copper alloy). Finally, one end of these frames was exposed, and an epoxy resin (manufactured by Sumitomo Bakelite Corporation, trade name ΕΓΓ-? 3'20A) was used to package the shoulder capacitor by a transfer molding method. The characteristics of this capacitor are shown in Table 4. Comparative Example 2 之外 The adhesive of silver paste was changed to epoxy resin (oiled She 11-Epoxy company, * &*; * made by the company, trade name Epic oat 8 28 type), the rest is described in Example 8 If implemented, the characteristics of the obtained wafer-type solid electrolytic capacitor are shown in Table 4. (Please ^^ read the note on the back ^^ and fill in this page again) Install iyill-Λ Table ESR (mQ) ESR increase before and after reflow (m £ 2) Poor reflow rate Moisture poor rate Example 8 20 2 0/30 0/30 Comparative Example 25 20 6/30 12/30 --- 1. Order! 11 ^ ―yl ϋι In Table 4: ESR (equal series resistance at 100KHZ ') is the average of 30 samples 97 2 X ο 2 / V Gage 4) A s) N (c Appropriate standard in the country Rule paper-Printed values from the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Solid flow (heat resistance) defect rate and moisture resistance defect rate are the number of defective products in 30 samples tested according to the following method. That is, heat resistance) Defective rate: After reflow (2301C, 30 seconds), the rated voltage (13V) is applied, and the leakage current value is measured after 1 minute. -48 " Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and Consumer Cooperatives 4 5 9 2 55 A7___; _B7 ___ V. Description of the invention (46) · 下 The current value under UyAM is a qualified product (good product), and 12 «ΑΜ_Η is a defective product. Temperature 60ΐ !, relative humidity 90S; under 100 (after 3 hours. Take out, apply the rated voltage, and measure the leakage current value after 1 minute. The leakage current value 12 «AM is the qualified product, 12 M AK soil is not Good product. Example 9 'KK aspect ratio 3 ~ 1.5, average particle size 3 wm, particle size 32 μ The particles occupy 2 masses, 3 masses, and fixed carbon content of 3 to 9 masses; artificial rhenium lead powder (manufactured by Showa Denko Corporation, trade name UFG-5) is used as a conductive material, and ethylene / propylene is used as a binder. / Diene terpolymer (EPDM) in butyl acetate suspension (EPD.M 7 mass X in suspension), so that the solid content of the resin (terpolymer) is artificial rhenium lead powder 1〇 〇80 parts by mass of 3 liters, and then mixed for 2 4 hours to obtain a conductive carbon lake. The shovel was etched by etching with a size of 3 X 10 mm, and a polyimide tape with a wide lmia was used on it. The two sides are attached, and M is divided into two parts of 4 «and 5mm. Then, the 3 MX 4 mra part of the aluminum foil is immersed in a 10 mass JS ammonium adipate aqueous solution and a voltage of 13v is applied for chemical (chemical) treatment to form a medium for oxidation. Film. Next, immerse 3 mm x 4 min of aluminum foil in isopropylase (solution 1) containing 20 mass of 3 £ 3,4-ethylenedioxythiophene, and take it out and dry it at room temperature. ... then the 3 mm X4 tain part of the aluminum foil (the part where the dielectric oxide film is formed) is dipped in a solution containing 3 (3 Dong% ammonium persulfate (APS) and 1 mass 3; simmer the sodium sulfonate aqueous solution (Solution 2) and take it out, and place it in an atmosphere of 6Q ° C for 10 minutes to perform oxidative polymerization. -49- • n I n I n · 1 nnn 1. I 1--(Please read the note on the back # -Fill this page first) Order-· 0!---The size of the paper is applicable to the Chinese national standard CCNS) A4 size (210 X 297 mm) r * 459255 A7 _ B7 V. Description of the invention (47) After immersing in solution 1 again, perform the same treatment as above. The above operation of immersing in solution 1 to oxidative polymerization was repeatedly performed 25 times, and then washed with warm water of 5 dt c for 10 minutes, and finally dried for 30 minutes to form a conductive polymer layer (solid battery .Quality Calendar). A scanning electron microscope photograph (2, 0 0 Q times) of the cross-section of the aluminum foil with the conductive polymer layer thus prepared was observed to confirm that the conductive polymer had a history-like structure that completely covered the dielectric (oxidized) on the aluminum alloy. Aluminium > has voids between the denier-like conductive polymer layers on the surface of the micropores. The thickness of the conductive polymer layer formed on the outer surface of the micropore structure is about 5W fa, which forms a layer. The thickness of each layer of the structure is in the range of about Q. 1 ~ 0 3 um. Then, the conductive carbon glow prepared by the above method is coated on the part of the aluminum foil with a conductive polymer layer, and then heat-treated for 3D minutes at 10 ΙΙΊΟ. A carbon paste conductive calendar is formed on the above-mentioned conductive polymer. Then, a portion of the aluminum foil formed with a conductive polymer layer is coated with a silver paste to connect the cathode lead terminal, and at the same time, no conductive polymerization is formed. The part of the material layer is made of epoxy resin, and the components with anode lead terminals are wrapped by soldering. The rated voltage is applied at 125¾ for 2 hours, and a total of 30 capacitors are made. For this 3D capacitors For capacitors, the equivalent series resistance (ESR) is measured according to conventional methods and reflow treatment is performed. Then the ESR after reflow treatment is measured again and the ESR changes before and after reflow treatment are evaluated. At the same time, all capacitors are subjected to the resistance described below. The results of the test of the wet failure rate are shown in Table 5. Example 10 Except that the EPDM butyl acetate suspension described in Example 9 was changed to fluorine-50-This paper uses Chinese National Standard (CNS) A4 specifications (210 X 297 mm) (Please read the notes on the back before filling out this page) \ 11—Order -------- line `` y · Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs for consumer cooperation 1: ^ 45 9 2 b5 a7 — _ B7 _ V. Description of the invention (4.8). Ί · \ 糸 Polymer fluorinated vinylene-hexafluoropropylene-tetrafluoroethylene copolymer) Butyl acetate 鼪 float solution , M and change the solid content of EPDM to 80 parts by mass of 100 parts by mass of artificial black lead powder. X is changed to 70 parts by mass X. The rest is implemented according to the method described in Example 9 to make 3Q capacitors. Example 9 evaluated the characteristics of the capacitor, and the results are shown in Table 5. -\ Comparative Example 3 ', except that the artificial black ship of isoelectric dead material is used instead of powder with an average particle size of 4Ϊa, and particles with a particle size of 32 wW occupy 2 masses! Inferred, fixed carbon 4 98 .5 quality > ··· flake-shaped natural thallium lead on an amount of X, obvious aspect ratio of 10K, M and the SPDM of the adhesive changed to epoxy resin, and the rest Example 9 was run to obtain 30 capacitors. The evaluation results of the characteristics of these capacitors are shown in Table 5. 'Comparative Example 4. > The artificial black lead powder of conductive material was changed to an average particle diameter of 4yiii, the particle size of 32 «bK accounted for 2 mass X'K, fixed carbon content of 98.5 mass%, length and width Than the obvious 10M ± scales of natural thallium lead, the rest are made according to Example Ifl, and 30 capacitors were made. The results of the characteristics evaluation of these capacitors are shown in Table 5. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs The various evaluation tests performed in the previous example, 1 tr, and comparative examples 3 and 4 were performed according to the following measurement methods and conditions. <Measurement method> 1. Reflow (resistance) defect • The rate of passing 30 solid electrolytic capacitors through a reflow furnace with a peak temperature of 230¾ for 30 seconds and applying the rated voltage (6.3 V) for 1 minute. Post-measurement leakage current-5 1- This paper size is in accordance with Chinese National Standard (CNS) A4 (210 x 297 mm) 459255 A7 VR7 V. Description of the invention (49) 1 j. Those whose leakage current value is less than 3 w A are regarded as qualified products (good products), and those that exceed them are regarded as defective products. 2. Poor moisture adhesion rate The qualified products for the reflow test are placed at a temperature of 6DT: and a relative humidity of 90¾. In an atmosphere, take out after 1000 hours, apply a rated voltage of 6. 3V), _ 1 minute, and measure the leakage current after 1 minute. Those whose leakage current value is less than 12W Α are regarded as qualified products. Table 5 ESR ΙΟΟΚΗζ (m Ω). Changes in ESE after reflow (m Ω) Poor reflow rate * 1 Poor wetting rate * 1 Example S 20 5 0/30 2/30 Example 3 20 0 0/30 0/3 0 Example 10 50 50 '5/3 0 12/25 Comparative Example 4 40 20' 2/30 3/28 * 1: Number of non-conformities / Number of samples < Please read the notes on the back before filling (This page) ---- Printed by the Consumers' Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, <Utilization in Industry>., The present invention provides a solid electrolyte layer and a conductive layer containing gold tincture powder, or conductive carbon. Layer and a solid electrolytic container containing rubber-like elastic material in at least one layer composed of a conductive layer containing gold tin powder on the layer and a method for preparing the same, K and a solid electrolyte used in the solid electrolytic capacitor, and a method for manufacturing the solid electrolyte , Conductive paste for solid electrolytic capacitors, and conductive carbon paste for solid electrolytic capacitors. A 5 2 _. This paper size applies the Chinese National Standard (CNS) A4 specification (210 x 297 mm) A7 459255 __B7 __.__ V. Description of the invention (50) The solid electrolytic capacitor of the present invention is conductive due to the formation of a solid electrolyte in it The polymer composition contains a rubber-like elastic material, so it can greatly reduce the number of impregnations and polymerizations, and improve productivity, so as to provide small-sized, low-impedance, high-performance solid f 觫 capacitors with ease of external stress and its manufacturing method. In addition, since M. specific polyheterocyclic compounds, especially conductive polythiophenes, are used as π-electron conjugated polymers and used as solid electrolytes, voltage withstand characteristics (spark voltage test>, high-frequency durability, loss coefficient ( tan S), impedance characteristics, leakage: current, heat resistance (reflow resistance), etc. greatly improved effects. In particular, in the above-mentioned conductive polymer k product, there are 71 electrons
V 共輒辑造之聚合物反覆單^元,橡膠狀彈·性料之含星在Q.01 〜2 5質最%範圍,且硫酸離子含量在1〜10荑耳%範圍.莳 ,即可製成具有更高性能電容器特性之.固體電解電容器。 經濟部智藉財產局員工消費合作社印製 , 又,若本發明之固體電解電容器在導電體層(含有金 屬粉末之導電體層、或導電性碳廇,及在其上設有含金屬粉 末之導電體曆)含有橡膠狀彈性料時,可獲得下述之效果ία) 本發 明之導電性糊 ,其粘结劑 # 氟· 系橡膨 ,故彈 性率低且具優異之耐熱性及耐濕性。 ' (2)使用該導電性湖於導電體層之固體電解電容器,_ » 在回流等時發生之熱應力小.,因此不會在等電體層界面發 生剝雛。 ' (3 )结果,回流前後之等值串聯電阻(E S R)之變彳b小 ,同時不發生回流不良及耐濕不良之效果。 -53- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297.公釐) 459255 A7 _ B7 五 '發明說明(51 ) 更有進者,本發明之固體電解電容器在等電性碳層使 用橡膠狀彈性料,尤其氟糸橡膠狀彈性料時,具有優異之 附濕性(撥水性),而於導電性碳層使用待定之導電性材料 (人造黑鉛粉)時,更可增高填充密度而表現優異之専電性 及耐熱性。 / ί , 因此,將以其作為導電性碳糊f得之固體電解電容器 具fESR (在lOGKHz時之等值串聯電阻)低,回流前後之 ESS的變化小,及耐濕不良率低之效果。 . · · . .· ’圖式之簡單說明 第I圖為本發明固體電解電容器之一例之斷面圖; 第2圖為本發明固體電解電容器之另一例之斷面甌〜; 第3圃為本發明之等電性聚合物曆之電子親微鏡照片 (倍率:5 fl 0 0倍)。 ’ 符號說明 1 1 1----閥作用金屬 2·..·细孔 3____介質被膜 4----固體電解質曆 5----導電體層 S----舛裝體 7....接缜用端子 7a··.陽極端子 7b...陰極端子. -54- 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) - — If I.--------/rn.襄 (請先閲讀背面之注意事^再填寫本頁〕 ---- 訂-------I . 經濟部智慧財產局員工消費合作社印反The polymer is composed of V repeating units, the rubber-like elastic material contains the star in the range of Q.01 to 25%, and the sulfate ion content is in the range of 1 to 10 mole%. Can be made into capacitors with higher performance. Solid electrolytic capacitors. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs, and if the solid electrolytic capacitor of the present invention is provided on a conductive layer (conductor layer containing metal powder or conductive carbon), and a conductive body containing metal powder is provided thereon (Calendar) When the rubber-like elastic material is contained, the following effects can be obtained. Αα) The conductive paste of the present invention has a binder #fluorine, which is a rubber expansion, so it has low elasticity and excellent heat resistance and moisture resistance. '(2) The solid electrolytic capacitor using this conductive lake in the conductor layer has a small thermal stress during reflow, so it does not peel off at the interface of the isoelectric layer. '(3) As a result, the change in the equivalent series resistance (ESR) before and after reflow is small, and the effects of poor reflow and poor moisture resistance do not occur. -53- This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297. mm) 459255 A7 _ B7 Five 'invention description (51) Even more advanced, the solid electrolytic capacitor of the present invention is in isoelectric carbon When using a rubber-like elastic material for the layer, especially fluorinated rubber-like elastic material, it has excellent hygroscopicity (water repellency). When the conductive carbon layer uses a conductive material to be determined (artificial black lead powder), it can be even higher. Packing density and excellent electro-electricity and heat resistance. / ί, therefore, the solid electrolytic capacitor obtained by using it as a conductive carbon paste f has low fESR (equivalent series resistance at 10 GKHz), low ESS change before and after reflow, and low humidity resistance. ······ A brief description of the drawing Figure I is a sectional view of an example of a solid electrolytic capacitor of the present invention; Figure 2 is a sectional view of another example of a solid electrolytic capacitor of the present invention; Electron microphotograph (magnification: 5 fl 0 0 times) of the isoelectric polymer of the present invention. 'Symbol description 1 1 1 ---- Valve action metal 2 ... · pores 3____ Dielectric coating 4 ---- Solid electrolyte calendar 5 ---- Conductor layer S ---- Outfit body 7. .. Terminal 7a ··. Anode terminal 7b ... Cathode terminal. -54- This paper size applies to China National Standard (CNS) A4 (210 X 297 mm)-— If I .---- ---- / rn.Xiang (Please read the notes on the back ^ before filling out this page) ---- Order ------- I. Printed by the Consumers ’Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs
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US8630084B2 (en) | 2009-12-22 | 2014-01-14 | Murata Manufacturing Co., Ltd. | Solid electrolytic capacitor and method for producing solid electrolytic capacitor |
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WO2009051297A1 (en) * | 2007-10-19 | 2009-04-23 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
WO2009051296A1 (en) * | 2007-10-19 | 2009-04-23 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
WO2009051294A1 (en) * | 2007-10-19 | 2009-04-23 | Young Joo Oh | Metal capacitor and manufacturing method thereof |
CN102649893A (en) * | 2011-02-23 | 2012-08-29 | 爱博斯迪科化学(上海)有限公司 | Conductive coating for capacitor and related capacitor |
CN103560007B (en) * | 2013-10-18 | 2016-03-09 | 中国振华(集团)新云电子元器件有限责任公司 | There is the preparation method of the solid electrolyte capacitators of high conductivity |
CN105931863B (en) * | 2016-05-10 | 2019-04-19 | 湖南艾华集团股份有限公司 | A kind of metal-containing polymer, production method and the forming method on capacitor element |
CN111771254B (en) * | 2018-02-28 | 2022-11-18 | 松下知识产权经营株式会社 | Electrolytic capacitor and method for manufacturing the same |
KR102617851B1 (en) | 2018-06-21 | 2023-12-27 | 교세라 에이브이엑스 컴포넌츠 코포레이션 | Solid electrolyte capacitor with stable electrical properties at high temperatures |
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JPS58161315A (en) * | 1982-03-18 | 1983-09-24 | 日本電気ホームエレクトロニクス株式会社 | Electronic part |
JP3123772B2 (en) * | 1991-06-11 | 2001-01-15 | 三洋電機株式会社 | Organic semiconductor solid electrolytic capacitors |
JP2950670B2 (en) * | 1991-12-10 | 1999-09-20 | マルコン電子株式会社 | Solid electrolytic capacitors |
JPH0620877A (en) * | 1992-03-02 | 1994-01-28 | Du Pont Japan Ltd | Tantalum solid electrolytic capacitor |
JP3296727B2 (en) * | 1996-08-22 | 2002-07-02 | 三洋電機株式会社 | Method for manufacturing solid electrolytic capacitor |
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US8630084B2 (en) | 2009-12-22 | 2014-01-14 | Murata Manufacturing Co., Ltd. | Solid electrolytic capacitor and method for producing solid electrolytic capacitor |
US8945240B2 (en) | 2009-12-22 | 2015-02-03 | Murato Manufacturing Co., Ltd. | Solid electrolytic capacitor and method for producing solid electrolytic capacitor |
TWI488203B (en) * | 2009-12-22 | 2015-06-11 | 村田製作所股份有限公司 | Solid electrolytic capacitor and method for producing solid electrolytic capacitor |
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