1235392 玖、發明說明： 【發明所屬之技術領域】 本發明係與固體電解電容器有 ，把陽極電極箔與陰極電極箔進：特別與經由分隔片 ，並在該捲繞元件内形成固態心纟製作捲繞70件 有關。 貝層之固態電解電容器 【先前技術】 上電下結構所構成者:在陽極電極之表面 出4 = 氧化皮膜層，並從該氧化皮膜層引 ;:;^極係由表面具有微細孔或敍刻坑之组 的引I二用金屬所形成者。此外’從氧化皮膜層之電極 的引出係猎由具有導電性之電解質層來進行。因此，在電 ^電谷益方面，電解質層係扮演真正的陰極。針對此且有 /、正陰極功能之電解質層，其與氧化皮膜層之密合性、敏 密性、均一性等是相當重要的。尤其，由於與陽極電極之 微細孔或钱刻坑内部之電解質的密合性，會對電性特性帶 來極大的影響，因此先前有許多電解質層的發明被提出。 近^來，隨著電子機器之數位化、高頻率化趨勢，小型 二大谷量，i在高頻率區域具有餘抗之電纟器成為市場 而求針對此一需求，捲繞型電解電容器被開發問世，且 、二為基礎，使得電解電容器得以達成小型大容量化；而1235392 发明 Description of the invention: [Technical field to which the invention belongs] The present invention relates to solid electrolytic capacitors, in which anode electrode foil and cathode electrode foil are fed: particularly through a separator and forming a solid core in the winding element. Related to winding 70 pieces. Solid-state electrolytic capacitors in the shell layer [Previous technology] Structure consisting of power-on and power-down: 4 = oxide film layer on the surface of the anode electrode, and lead from the oxide film layer ;: ^ pole is formed by the surface with fine holes or The pit group of primers is formed of metal. In addition, the extraction of the electrode from the oxide film layer is performed by an electrolyte layer having conductivity. Therefore, in terms of electricity, the electrolyte layer acts as a true cathode. In view of this, the electrolyte layer having the positive and negative electrode functions is very important for its adhesion, sensitivity, and uniformity to the oxide film layer. In particular, since the adhesion with the electrolyte inside the pores of the anode electrode or the nicks of the anode electrode can greatly affect the electrical characteristics, many previous inventions of the electrolyte layer have been proposed. Recently, with the trend of digitalization and high frequency of electronic equipment, small two large valleys, i with a reactor with high reactance in the high frequency region have become the market. In response to this demand, wound electrolytic capacitors have been developed. Advent, and based on, two, enabling electrolytic capacitors to achieve small size and large capacity; and
°亥捲繞型電解電容器係把捲繞元件收納於金屬盒中，以封 口橡膠實妳私L 、 4止者；而該捲繞元件係經由分隔片，把陽極 O:\89\89916.DOC 2 1235392 電極fi與陰極電極ϋ捲繞而成者。此外，針對低阻抗需求 ’電解質係可制固態電解f來因應，在此類@ ,態電解質 方面，以二氧化錳、7,7,8,8-四氟化四氰代二甲基苯（TCNQ) 絡合物為一般所熟知。然而，前述固態電解質之導電性低 ，故使用之的電解電容器難以具有充分之阻抗特性。 因此，為了解決此一問題，有人提議使用聚呲咯、聚噻 吩等具有高導電性之導電性高分子來作為I態電解質。此 外，取近，有人著眼於聚乙烯二羥基噻吩（PEDt)具有聚合 速度穩U與陽極電極之氧化皮膜層之密合性佳的特性， 可作為I態電解質（參考特開平2_15611號公報）使用，並提 出、如下固態電解電容器之製作方法(參考特開平10姻29 號公報）：使捲繞元件含浸乙烯塞吩（EDT)單體與氧 化劑’利用隨後穩定發生之與單體及氧化劑之化學聚合反 應，在捲繞it件内部形成固態電解f聚乙烯H塞^ 而該捲繞元件係經由分隔片，把陽極電極箔與陰極電極箱 捲繞而成者。 然而，在依照上述建議方法製作之固態電解電容器方面 ’以導電性高分子作為陰極材料所獲得之ESR(等價串炉兩 阻）降低效果有時並不如預期；而該固態電解電容ϋ係S 繞元件内部形成有固態電解質者。 【發明内容】 器中之上述問題點； 把陽極電極箔與陰極 並在該捲繞元件内形 本發明之目的為解決固態電解電容 而該固態電解電容器係經由分隔片， 電極箔進行捲繞，來製作捲繞元件， O:\89\89916.DOC2 1235392 成固態電解質層而成者。 本發明之發明者們，為了達成上述目的，經過審慎反覆 的研时，此次發現採取如下兩種方法，可獲得保有高固態 電解質保存量之固態電解電容器，而完成了本發明；方法 一 ··在形成固態電解質之前，先把捲繞元件實施溶劑浸潰 處理，使分隔片減量；而該捲繞元件係經由分隔片把陽極 电極箔與陰極電極箔捲繞而成者；或是，方法二··分隔片 係使用由熱分解溫度不同之至少2種構成成分所形成者，且 在形成固態電解質之前，先把捲繞元件實施分隔片之熱分 解處理，使分隔片減量。 V因此，本發明係提供一種固態電解電容器，其特徵為： 經由分隔片，把陽極電極箔與陰極電極箔進行捲繞，來製 作捲繞7G件，並在該捲繞元件内形成固態電解質層；且其 係以如下方法來達成分隔片之減量： (a) 在形成固態電解質之前，先把捲繞元件浸潰於溶劑 中（以下，稱為本發明之樣態（a));而該溶劑係可把分隔片 之構成成分中之至少一種進行溶解者；或 (b) 分隔片係使用由熱分解溫度不同之至少2種構成成分 所形成者’且在形成該固態電解質層之前，先把該捲繞元 件加熱到下述溫度，使低熱分解溫度成分之至少一部分分 解除去（以下，稱為本發明之樣態（b));而上述溫度係··高 於分隔片構成成分中之低熱分解溫度成分之熱分解溫度之 溫度。 【實施方式】 O:\89\89916.DOC 2 1235392 以下針對本發明之固態電解電容器作更詳細說明。 如圖1所示，基本上’本發明之固態電解電容器係具有如 下結構：經由分隔片（3)，把陽極電極箱⑴及陰極電極箱⑺ 進仃捲繞，形成捲繞元件（6);且讓此捲繞元件0)之分隔片 ⑺中保持著固態電解質。陽極電極箱⑴係由含銘、紐等閥 作用金屬所形成，在陽極電極箱⑴之表面通常係預先實施 :刻處理’使表面積擴大“匕外，藉由化成處理，譬如， 藉由在蝴酸銨等之水溶液中施加電壓，來形成介電體氧化 皮膜層。另-方面，與陽極電極箱⑴同樣，陰極電極箱⑺ 亦由銘等金屬所形成；其表面通常實施有㈣處理。 、在‘陽極電㈣⑴及陰極電㈣⑺上，係藉由跳焊、超音 焊接等a知之手段，而連接著陽極引出手段（4)及陰極引 出手段（5);而該陽極引出手段⑷及陰極引出手段（5)係用於 使各電極與外部連接者。前述電㈣出手段⑷、（5)係從捲 繞元件（6)之端面被導出。 般而s，捲繞元件（6)係採取把分隔片（3)捲繞於陽極電 極v白（1)及陰極電極荡（2)之間的方式來形成。兩極電極箱⑴ ⑺之尺寸並無特別限制，係根據目的之固態電解電容器 的規格等來決定；故分隔片（3)之尺寸亦依照兩極電極箔⑴ 、（2)，而設定成比其略大的尺寸。 本發明之樣態⑷中所使用之分隔片⑶，亦可採用在捲繞 里固悲包解私谷态之製作上先前所使用同樣之分隔片；其 構成素材言如有·芳香族聚醯胺纖維、聚自旨、聚硫化亞苯 PBI(聚苯并味<)、PBQ(聚對苯撑苯并雙。惡峻 O:\89\89916.DOC 2 1235392 )、聚醯亞胺、玻璃、％丙烯腈、氧化聚丙烯腈、碳或豆前 體:氧化銘、纖維素、殿粉、聚乙烯、聚丙稀、環氧:、聚 :烯醇等，在使用之際，可將前述素材以單獨方式，或組 。一種以上乃至組合更多種來使用。 岫述刀隔片之構成材料，係均依照後述溶劑浸潰處理中 所使用之溶劑種類而定，而可能成為溶解於該溶劑之成分 ;或相反地，實質上可能成為不溶性之成分。 在本發明中，一般而言，分隔片係採取由如下構成素材 之組合所形成者為佳；而該構成素材之組合係包含：在後 述溶劑浸潰處理所使用之溶劑中具有可溶性之至少一種構 成、素材；及在該溶劑中實質上呈不溶性之至少一種構成素 材0 如此一來，由上述構成素材所形成之分隔片譬如有，由 聚乙烯或聚丙烯般聚鏈烯烴系聚合物所形成之多孔質薄膜 (特開昭63-27365 1號公報）、聚乙烯或聚丙烯般聚鏈烯烴系 聚合物之纖維所形成之不織布（特開2〇〇1_11761號公報）、尼 龍纖維所形成之不織布（特開昭58_147956號公報）、由芳香 族聚醯胺纖維及芳香族聚醯胺纖條體之任一種或兩者之混 合物所形成之薄膜（特願2001-325540號明細書）等；而其中 係以藉由濕式抄造法，由芳香族聚醯胺纖維及芳香族聚醯 胺纖條體所形成之薄膜為佳。 又’在本發明之樣態（b)中所使用之分隔片（3)方面，係使 用由相對性熱分解溫度不同之至少二種構成成分所形成者 在低熱分解溫度成分方面，一般以2 0 〇〜5 0 0 °C，特別是 O:\89\89916.DOC 2 -9- 1235392 在250〜350°C範圍内之溫度進行分解者為佳。又，在高熱 分解溫度成分方面，一般以具有比上述低熱分解溫度成分 至少高l〇°C，特別是高50°C以上之高熱分解溫度者為佳。 在此，所謂「熱分解溫度」係指，當把某物質進行加熱 後，使該物質分解，變化為小質量之物的最低溫度；通常 係使用TGA(熱重量分析裝置），以一定之升溫溫度將物質加 熱後，測定物質之質量開始減少之溫度，來作為該溫度。 因此’在本發明之分隔片之構成成分中’南熱分解溫度 成分係譬如有：芳香族聚醯胺、聚酯、聚硫化亞苯、氟系 樹脂、PBI(聚苯并咪唑）、PBO(聚對苯撑苯并雙噁唑）、聚 醯、亞胺、玻璃、聚丙烯腈、氧化聚丙烯腈、碳或其前體、 氧化鋁等；另一方面，低熱分解溫度成分係譬如有：纖維 素、澱粉、聚乙烯、聚丙烯、環氧、尼龍、聚乙烯醇、芳 香族聚醯胺、聚酯、聚硫化亞苯、氟系樹脂、PBI(聚苯并 咪唑）、PBO(聚對苯撑苯并雙噁唑）、聚醯亞胺等；可從前 述各群中進行選擇，組合滿足上述熱分解溫度差條件者來 使用。其中，尤其以利用濕式抄造法，從芳香族聚醯胺纖 維、木材紙漿（纖維素）所形成之薄膜為佳。 高熱分解溫度成分及低熱分解溫度成分之構成比率，並 無嚴格限制；可根據各成分之種類及捲繞元件所需分隔片 之空隙率等來作變更；但一般而言，高熱分解溫度成分/低 熱分解溫度成分之重量比為1/99〜99/1 ;尤其以在10/90〜 90/10之範圍内為佳。 藉由在捲繞元件（6)内形成固態電解質層，可獲得固態電 O:\89\89916.DOC2 -10- 1235392 解電容器。在固態電解質層方面係譬如有：聚噻吩、聚呲 咯、聚苯胺、7,7,8,8-四氟化四氰代二甲基苯絡合物及前述 各者之誘導體等；尤其以使用聚乙烯二羥基噻吩（PEDT)為 佳，因為如使用之則可獲得具有大容量、低ESR特性之固 態電解電容器之故。此PEDT係可以如下方法獲得：讓單體 3,4-乙烯二羥基噻吩（EDT)與氧化劑p-甲苯磺酸第二鐵反應 ，進行聚合。固態電解質層之形成可採取如下方法：把EDT 或EDT溶液及氧化劑溶液（譬如丁醇溶液）分別注入捲繞元 件中，並譬如以150°C加熱約1小時，使EDT進行聚合；或 是，把預先調製之EDT及氧化劑之混合液注入捲繞元件中 ，v或把捲繞元件浸潰於該混合液中使之含浸，並譬如以150 °C加熱約1小時。 接著，把形成固態電解質層後之捲繞元件，收納於有底 筒狀之金屬盒中，並以封口橡膠（譬如，在丁基橡膠聚合物 中添加加硫劑烷基酚樹脂之橡膠；而該丁基橡膠聚合物係 由異丁烯及異戊二烯之共聚物所形成者）進行加壓封止，來 形成固態電解電容器。如此，譬如就可獲得額定4WV-330 μ F之固態電解電容器。 在本發明之樣態（a)方面，在讓捲繞元件形成前述固態電 解質層之前，先把捲繞元件浸潰於溶劑中，進行減量；而 該溶劑係可把分隔片之構成成分中之至少一種進行溶解者 。此溶劑浸潰處理係使減量後之分隔片部分之空隙率為 85%以上，尤其以維持在85〜95%之範圍内為佳。減量後之 分隔片部分之空隙率係利用下列之式（1)及式（2)中之任一 O:\89\89916.DOC2 -11 - 1235392 種計算所獲得之值·在 在本發明方面，以式〇)及 -種所算出之空隙率，如在85%以上即可 ）中之任 [空隙率](°，❶）= (a-b)/Ax100.·.式 在此， A—[構成分隔片之素材之密度](g/cm3) B=[減量後分隔片之鬆密度](g/cm3) [空隙率]W=C/(C + D)X100式⑺ 在此， C=[捲繞元件内之固體電解質之 質之密度](g/cm3) 、 ](g)/[固體電解 :D =[減量後分隔片之質量]_ 密度](g/cm3) 刀h片之素材之 用於捲繞元件之溶劑浸潰處理之溶劑，馨产 溶液、氳鹼溶液、有機溶媒 *虱乳 -鍤^3虱有機〉谷媒及前述各者之 -種或二種以上之混合物； ☆、八+ , 尔J杷分隔片之構成 刀中之至父一種進行溶解者。 p T根據用於捲繞元件之分 隔片之構成成分的種類，來 八 木4擇其中之適當者；孽如，如 Ν Ν二甲其r ☆ 、、、香矢來鯭胺時，則適合採用 ，乂 ^胺及•甲基1環。此㈣為溶劑。 盘用；』 的條件方面’譬如，可藉由 =於捲繞W同分W的輯片及所選擇之溶劑， 仃小規模實驗，從錯誤嘗試中選出正確者；如此 ’則可決定可讓該測試片之* 声及日士門玫灿 片之工陳率達85〇/〇以上時所需的溫 ⑽條件。捲繞元件之溶劑浸潰處理的溫度，依照分 0:\89\899l6.D〇C2 -12- 1235392 隔片之材質而定，亦可使用常溫；但通常可藉由加熱到所 用溶劑之沸點以下之適溫，來促進分隔片之減量化。又， 浸潰時間係極受處理溫度大幅度左右，但通常可設定為1 分至3小時左右。 又，在本發明之樣態（b)方面，在讓捲繞元件形成前述固 體電解質層之前，先把捲繞元件加熱到下述溫度，使低熱 分解溫度成分之至少一部分分解除去，進行分隔片的減量 ;而上述溫度係：高於分隔片構成成分中之低熱分解溫度 成分之熱分解溫度之溫度。此加熱分解處理係以使減量後 之分隔片部分之空隙率為85%以上，尤其以維持在85〜95% 之jr圍内為佳。減量後之分隔片部分之空隙率係利用下列 之式（3)及式（4)中之任一種計算所獲得之值；在本發明中， 以式（3)及式（4)中之任一種所算出之空隙率，如在85%以上 即可。 [空隙率](%) = (A - B) / A X 100 ·••式（3) 在此， A二[構成分隔片之素材之密度] (g/cm3) =[南熱分解溫度成分之素材密度](g/cm3) χ [焉熱分 解溫度成分在分隔片中所占體積百分比]+ [低熱分解溫度 成分之素材密度](g/cm3) X[低熱分解溫度成分在分隔片中 所占體積百分比] B =[減量後分隔片之鬆密度] (g/cm3) [空隙率](%) = C / (C + D) X 100 …式（4) 在此， O:\89\89916.DOC2 -13- 1235392 c =[捲繞元件内之固體電解質之質量](g)/[固體電解 質之密度](g/cm3)° He wound electrolytic capacitors contain winding elements in a metal box, and seal them with a rubber seal. The winding elements pass through separators, and the anode O: \ 89 \ 89916.DOC 2 1235392 The electrode fi is wound with the cathode electrode ϋ. In addition, for low impedance requirements, the electrolyte system can be prepared by solid-state electrolytic f. In this type of electrolyte, manganese dioxide, 7,7,8,8-tetracyanodimethylbenzene tetrafluoride ( TCNQ) complexes are generally well known. However, since the aforementioned solid electrolyte has low conductivity, it is difficult for the electrolytic capacitor used to have sufficient impedance characteristics. Therefore, in order to solve this problem, it has been proposed to use a conductive polymer such as polyfluorene or polythiophene as a state I electrolyte. In addition, some people have noticed that polyethylene dihydroxythiophene (PEDt) has the characteristics of stable polymerization rate U and excellent adhesion with the oxide film layer of the anode electrode, and can be used as an I-state electrolyte (see Japanese Patent Application Laid-Open No. 2_15611). And proposed the following method for manufacturing solid electrolytic capacitors (refer to Japanese Patent Application Laid-Open No. 29-29): impregnating a wound element with an ethylene thiophene (EDT) monomer and an oxidant 'using a chemical that is subsequently stably generated with the monomer and the oxidant In the polymerization reaction, a solid electrolytic f polyethylene H plug is formed inside the wound IT, and the wound element is obtained by winding the anode electrode foil and the cathode electrode box through a separator. However, in the case of solid electrolytic capacitors made in accordance with the above-mentioned suggested method, the ESR (Equivalent String Furnace Two Resistance) reduction effect obtained by using conductive polymers as cathode materials is sometimes not as expected; and the solid electrolytic capacitors are not S A solid electrolyte is formed around the inside of the element. [Summary] The above-mentioned problems in the device; the anode electrode foil and the cathode are formed in the winding element. The purpose of the present invention is to solve the solid electrolytic capacitor, which is wound through the separator and the electrode foil, To make a wound element, O: \ 89 \ 89916.DOC2 1235392 is made of a solid electrolyte layer. In order to achieve the above-mentioned object, the inventors of the present invention, after careful and repeated research, found that the following two methods can be adopted to obtain a solid electrolytic capacitor with a high solid electrolyte storage capacity, and completed the present invention; Method 1 · · Before forming a solid electrolyte, first perform a solvent immersion treatment on the wound element to reduce the amount of the separator; and the wound element is obtained by winding the anode electrode foil and the cathode electrode foil through the separator; or, Method two: The separator is formed by using at least two constituents having different thermal decomposition temperatures, and before forming a solid electrolyte, the thermal decomposition treatment of the separator is performed on the wound element to reduce the weight of the separator. Therefore, the present invention provides a solid electrolytic capacitor, which is characterized in that the anode electrode foil and the cathode electrode foil are wound through a separator to form a wound 7G piece, and a solid electrolyte layer is formed in the wound element. ; And it is to achieve the reduction of the separator by the following method: (a) before forming the solid electrolyte, the winding element is immersed in a solvent (hereinafter, referred to as the aspect (a) of the present invention); and the The solvent is capable of dissolving at least one of the constituents of the separator; or (b) the separator is formed by using at least two constituents having different thermal decomposition temperatures, and before forming the solid electrolyte layer, The winding element is heated to the following temperature to decompose and remove at least a part of the low-temperature decomposition temperature component (hereinafter, referred to as the aspect (b) of the present invention); and the above-mentioned temperature is higher than the constituent components of the separator The temperature of the thermal decomposition temperature of a low thermal decomposition temperature component. [Embodiment] O: \ 89 \ 89916.DOC 2 1235392 The solid electrolytic capacitor of the present invention is described in more detail below. As shown in Figure 1, basically 'the solid electrolytic capacitor of the present invention has the following structure: through the separator (3), the anode electrode box ⑴ and the cathode electrode box ⑺ are wound into 仃 to form a winding element (6); And the solid electrolyte is held in the separator ⑺ of the winding element 0). The anode electrode box ⑴ is formed of valve-acting metals such as inscriptions and buttons. The surface of the anode electrode box 通常 is usually implemented in advance: engraving treatment 'enlarges the surface area', and by chemical treatment, for example, by A voltage is applied to an aqueous solution of ammonium acid and the like to form a dielectric oxide film layer. On the other hand, like the anode electrode box ⑴, the cathode electrode box 由 is also formed of a metal such as Ming; its surface is usually treated with rhenium. On the anode anode and cathode cathode, the anode extraction means (4) and the cathode extraction means (5) are connected by a known means such as jump welding and supersonic welding; and the anode extraction means and the cathode The lead-out means (5) is used to connect each electrode to the outside. The aforementioned electric extraction means (5) and (5) are derived from the end surface of the winding element (6). Generally, the winding element (6) is It is formed by winding the separator (3) between the anode electrode v white (1) and the cathode electrode (2). The size of the two-electrode box ⑴ ⑺ is not particularly limited, and it is a solid electrolytic capacitor according to the purpose To determine the specifications, etc .; The size of the separator (3) is also set to a slightly larger size in accordance with the bipolar electrode foils 、, (2). The separator ⑶ used in the aspect ⑷ of the present invention can also be used in the winding The same separator used in the production of sadness and deprivation of the valley state; its composition materials include, for example, aromatic polyamide fibers, polyether, polyphenylene sulfide, PBI (polybenzoyl odor <), PBQ (Poly-p-phenylene benzobis. Evil O: \ 89 \ 89916.DOC 2 1235392), polyimide, glass,% acrylonitrile, oxidized polyacrylonitrile, carbon or bean precursors: oxide oxide, cellulose , Dianfen, polyethylene, polypropylene, epoxy :, poly: enol, etc., when using, the aforementioned materials can be used individually or in groups. More than one or even more types can be used. The constituent materials of the tablet may depend on the type of solvent used in the solvent impregnation treatment described later, and may become a component dissolved in the solvent; or, conversely, may substantially become an insoluble component. In the present invention, generally In terms of separation, it is better to use a combination of the following constituent materials; and The combination of constituent materials includes: at least one constituent material and material that are soluble in a solvent used in the solvent impregnation process described later; and at least one constituent material that is substantially insoluble in the solvent. Examples of the separator to be formed include a porous film made of a polyethylene or polypropylene-based polyolefin-based polymer (Japanese Patent Application Laid-Open No. 63-27365 1), and a polyethylene or polypropylene-based polyolefin-based polymerization. Non-woven fabrics made of natural fibers (Japanese Laid-Open Patent Publication No. 2001-1761), non-woven fabrics made of nylon fibers (Japanese Patent Laid-Open Publication No. 58_147956), and aromatic polyamide fibers and aromatic polyamide fiber slivers. Films made of either one or a mixture of both (Special Application No. 2001-325540), etc .; and among them, the aromatic polyamide fiber and the aromatic polyamide fiber sliver are prepared by a wet papermaking method. The formed film is preferably. Also, in the aspect of the separator (3) used in the aspect (b) of the present invention, a low thermal decomposition temperature component is generally formed by using a component formed of at least two constituent components having different relative thermal decomposition temperatures. 0 〇 ～ 50 0 ° C, especially O: \ 89 \ 89916.DOC 2 -9-1235392 It is better to decompose at a temperature in the range of 250 ~ 350 ° C. As for the high thermal decomposition temperature component, it is generally preferred to have a high thermal decomposition temperature that is at least 10 ° C higher than the low thermal decomposition temperature component, and particularly higher than 50 ° C. Here, the "thermal decomposition temperature" refers to the lowest temperature at which a substance is decomposed and changed to a small mass when it is heated; usually, a TGA (thermogravimetric analysis device) is used to increase the temperature After the substance is heated, the temperature at which the mass of the substance starts to decrease is determined as the temperature. Therefore, among the constituents of the separator of the present invention, the thermal decomposition temperature components include, for example, aromatic polyamidoamine, polyester, polyphenylene sulfide, fluorine-based resin, PBI (polybenzimidazole), and PBO ( Poly (p-phenylene benzobisoxazole), polyfluorene, imine, glass, polyacrylonitrile, oxidized polyacrylonitrile, carbon or its precursor, alumina, etc. On the other hand, the low thermal decomposition temperature components include, for example: Cellulose, starch, polyethylene, polypropylene, epoxy, nylon, polyvinyl alcohol, aromatic polyamide, polyester, polyphenylene sulfide, fluororesin, PBI (polybenzimidazole), PBO (polyparaben) Phenylene benzobisoxazole), polyfluorene, and the like; they can be selected from the aforementioned groups and used in combination with those that satisfy the above-mentioned thermal decomposition temperature difference conditions. Among them, a film formed from aromatic polyamide fibers and wood pulp (cellulose) by a wet papermaking method is particularly preferred. The composition ratio of the high thermal decomposition temperature component and the low thermal decomposition temperature component is not strictly limited; it can be changed according to the type of each component and the void ratio of the separator required for the wound element; but generally, the high thermal decomposition temperature component / The weight ratio of the low thermal decomposition temperature component is 1/99 to 99/1; it is particularly preferably within a range of 10/90 to 90/10. By forming a solid electrolyte layer in the wound element (6), a solid-state electric O: \ 89 \ 89916.DOC2 -10- 1235392 capacitor can be obtained. Examples of the solid electrolyte layer include: polythiophene, polypyrrole, polyaniline, 7,7,8,8-tetrafluorotetradimethylbenzene complex, and inducers of each of the foregoing; especially It is preferable to use polyethylene dihydroxythiophene (PEDT), because if used, a solid electrolytic capacitor with large capacity and low ESR characteristics can be obtained. This PEDT system can be obtained by reacting the monomer 3,4-ethylenedihydroxythiophene (EDT) with the oxidizing agent p-toluenesulfonic acid second iron to perform polymerization. The solid electrolyte layer can be formed by injecting EDT or an EDT solution and an oxidant solution (such as a butanol solution) into the winding element and heating them at 150 ° C for about 1 hour to polymerize the EDT; or, A pre-prepared mixed solution of EDT and oxidant is injected into the winding element, or the winding element is immersed in the mixed solution to impregnate it, and heated at 150 ° C for about 1 hour, for example. Next, the wound element after forming the solid electrolyte layer is housed in a bottomed cylindrical metal box with a sealing rubber (for example, a rubber added with a sulfurizing agent alkylphenol resin in a butyl rubber polymer; and The butyl rubber polymer is formed of a copolymer of isobutylene and isoprene) under pressure to form a solid electrolytic capacitor. In this way, for example, a solid electrolytic capacitor rated 4WV-330 μ F can be obtained. In aspect (a) of the present invention, before the wound element is formed into the aforementioned solid electrolyte layer, the wound element is immersed in a solvent to reduce the amount; and the solvent can be used to separate the constituents of the separator. At least one performing dissolution. In this solvent impregnation treatment, the porosity of the separator portion after the reduction is 85% or more, and it is particularly preferable to maintain the range of 85 to 95%. The porosity of the reduced portion of the separator is a value obtained by using any one of the following formulas (1) and (2): \ 89 \ 89916.DOC2 -11-1235392. In terms of the present invention, , The porosity calculated according to formula 0) and-one, if it is more than 85%, any [void ratio] (°, ❶) = (ab) /Ax100.·. Here the formula, A— [ Density of the material constituting the separator] (g / cm3) B = [Loose density of the separator after reduction] (g / cm3) [Voidage] W = C / (C + D) X100 Formula ⑺ Here, C = [Density of solid electrolyte in the winding element] (g / cm3),] (g) / [Solid electrolysis: D = [mass of separator after weight reduction] _density] (g / cm3) Solvent-impregnated solvents for materials used in coils, solvent-producing solution, scopolamine solution, organic solvent * lice milk-锸 ^ 3 lice organic> cereal medium and a mixture of one or more of the foregoing ; ☆, eight +, er J 杷 The composition of the separator is the one of the knife to the father who dissolves. p T is based on the type of the constituents of the separator used for the winding element, and Yagi 4 chooses the appropriate one. For example, if Ν Ν 二甲 其 r ☆ ,,, and selenium amine, it is suitable to use. , 乂 amine and • methyl 1 ring. This is a solvent. In terms of the conditions of "disc use", for example, you can choose the correct one from the wrong attempts through small-scale experiments by using the compilation film and the selected solvent in the winding W; The sound of the test piece and the temperature and temperature conditions required when the working rate of the Japanese Shimen Meichan film is above 85/0. The temperature of the solvent immersion treatment of the wound element depends on the material of the separator 0: \ 89 \ 899l6.D〇C2 -12-1235392. It can also be used at room temperature; but it can usually be heated to the boiling point of the solvent used. The following temperature is appropriate to promote the reduction of the separator. In addition, the immersion time is greatly affected by the treatment temperature, but it can usually be set to about 1 minute to 3 hours. In the aspect (b) of the present invention, before the winding element is formed into the solid electrolyte layer, the winding element is heated to the following temperature to decompose and remove at least a part of the low thermal decomposition temperature component, and then perform a separator. The above temperature is: a temperature higher than the thermal decomposition temperature of the low thermal decomposition temperature component of the constituents of the separator. This thermal decomposition treatment is performed so that the porosity of the separator portion after the reduction is 85% or more, and it is particularly preferable to maintain the jr range of 85 to 95%. The porosity of the reduced portion of the separator is a value obtained by calculation using any one of the following formulae (3) and (4); in the present invention, any one of the formulae (3) and (4) is used. One kind of calculated porosity may be 85% or more. [Voidage] (%) = (A-B) / AX 100 · •• Formula (3) Here, A 2 [density of material constituting separator] (g / cm3) = [of the thermal decomposition temperature component of the south Material density] (g / cm3) χ [焉 Volume percentage of thermal decomposition temperature component in separator] + [Material density of low thermal decomposition temperature component] (g / cm3) X [Low thermal decomposition temperature component in separator Percent by volume] B = [Loose density of separator after reduction] (g / cm3) [Voidage] (%) = C / (C + D) X 100… Formula (4) Here, O: \ 89 \ 89916.DOC2 -13- 1235392 c = [mass of solid electrolyte in wound element] (g) / [density of solid electrolyte] (g / cm3)
D =[減量後分隔片之質量](g)/A 加熱分解處理可以如下方法進行··藉由把捲繞元件以下 述溫度進行數分至數小時的加熱，來把分隔片構成成分中 之低熱分解溫度成分之一部分或實質上全部，進行分解除 去；而上述溫度係：高於該捲繞元件中之分隔片構成成分 中之低熱分解溫度成分之熱分解溫度；通常為比該熱分解 溫度至少高10°C之溫度，且係比高熱分解溫度成分之熱分 解溫度至少低20°C之溫度。進行加熱處理時之周圍環境並 無^特別限制，只要能夠迅速進行低熱分解溫度成分之熱分 解，無論是在氣體中、真空中、液體中之任何一種均可； 但一般而言，加熱分解處理係以在空氣中進行為佳。 在捲繞元件之加熱分解處理的適當條件方面，譬如，可 藉由與用於捲繞元件相同之分隔片的測試片，先進行小規 模實驗，從錯誤嘗試中選出正確者；如此一來，則容易決 定可讓該測試片之空隙率達85%以上時所需的溫度及時間 條件。 因此，本發明可提供一種固態電解電容器，其係穩定含 有並維持大量之固體電解質，且具有ESR降低效果等優秀 電性特性之固態電解電容器。 實施例 接著，利用實施例針對本發明作更具體說明。 實施例1 O:\89\89916.DOC2 -14- 1235392 利用濕式抄造法，把m_料族㈣胺纖維（把杜邦公 製「NOMEX」（註冊商標）切斷為6疆者）及芳香族聚 胺纖條體（其係把採用濕式沉澱機之方法所製造出來之 物，以叩解機進行處理，並把加拿大標準據水度調節^ 100 ml者，·而該濕式沉澱機係特公昭52_l5i624號公報記 載之由定子及轉子之組合所構成者）製作出成形為薄= 狀之芳香族聚醯胺紙，來將之作為分隔片。 、 經由上述製作出之芳香族聚醯胺紙，把陽極電極落及 陰極電極箔進行捲繞，製作2個捲繞元件；並把其中一個 浸潰於85t：之N·甲基n此㈣中2個小時。而'在該陽 、'極.電極箔方面，其表面係預先實施蝕刻處理，並實施化 成處理’且係由鋁箔所形成者，而該鋁箔表面係形成有 包含氧化鋁之氧化皮膜層者。 從此捲繞元件之質量的減少量，計算分隔片之密度、 空隙率；其結果係如下述表1所示。&，芳香族聚醯胺之 素材密度係以1 · 3 5 g/cm3進行計算。 減量前 減量後D = [mass of the separator after weight reduction] (g) / A The thermal decomposition treatment can be performed as follows: By heating the winding element at the following temperature for several minutes to several hours, A part or substantially all of the low thermal decomposition temperature component is decomposed and removed; and the above temperature is higher than the thermal decomposition temperature of the low thermal decomposition temperature component of the constituents of the separator in the wound element; usually it is higher than the thermal decomposition temperature A temperature of at least 10 ° C and a temperature at least 20 ° C lower than the thermal decomposition temperature of the high thermal decomposition temperature component. There is no particular limitation on the surrounding environment when performing the heat treatment, as long as the thermal decomposition of the low-temperature decomposition temperature component can be performed quickly, whether in a gas, a vacuum, or a liquid; but in general, the heat decomposition treatment It is better to carry out in the air. In terms of appropriate conditions for the thermal decomposition treatment of the wound element, for example, a test piece with the same separator as that used for the wound element can be firstly subjected to a small-scale experiment to select the correct one from wrong attempts; as a result, Then it is easy to determine the temperature and time conditions required when the void ratio of the test piece can reach 85% or more. Therefore, the present invention can provide a solid electrolytic capacitor, which is a solid electrolytic capacitor which stably contains and maintains a large amount of solid electrolyte and has excellent electrical characteristics such as an ESR reduction effect. Examples Next, the present invention will be described more specifically with reference to examples. Example 1 O: \ 89 \ 89916.DOC2 -14-1235392 Using wet copying method, m_ material family amine fiber (cutting DuPont metric "NOMEX" (registered trademark) to 6 Xinjiang) and fragrance Group of polyamine fibrids (which are made by using a wet precipitation machine, processed with a decomposing machine, and adjusted to the Canadian standard according to the water content ^ 100 ml, and the wet precipitation machine JP 52-l5i624 (composed of a combination of a stator and a rotor) is made of an aromatic polyamide paper formed in a thin shape to be used as a separator. 2. Through the aromatic polyamide paper prepared above, the anode electrode and the cathode electrode foil are wound to make two winding elements; and one of them is immersed in 85 t: N · methyl n. 2 hours. In the anode electrode foil, the surface is pre-etched and chemically treated, and formed of aluminum foil, and the surface of the aluminum foil is formed with an oxide film layer containing alumina. From the reduction in the mass of the wound element, the density and porosity of the separator were calculated; the results are shown in Table 1 below. & The material density of the aromatic polyamidamine was calculated at 1.35 g / cm3. Before reduction After reduction
芳香族聚醯 胺纖維/芳香 族聚酿胺纖 條體 — 芳香族?ϋ 胺纖維/芳香 族聚酿胺纖 條體 85/15 坪量 (g/cm2) 10 6.6 飞度 (㈣ (g/m3) --~~~—土 — 空隙率 (%) 35 0.29 --- 79 35 0.19 ---——. 86Aromatic Polyamide Fiber / Aromatic Polyvinyl Ammonium Cellulose — Aromatic Polyamide Fiber / Aromatic Polyvinyl Ammonium Cellulite 85/15 Aperture (g / cm2) 10 6.6 Fit (㈣ (g / m3 )-~~~ --soil- void ratio (%) 35 0.29 --- 79 35 0.19 -------. 86
O:\89\89916.DOC -15- 1235392 接著，把實施過溶劑浸潰處理之捲繞元件（本發明品、 及未作任何溶劑浸潰處理之捲繞元件（比較品），分別浸潰 於乙烯二羥基噻吩與苯磺酸第二鐵之丁醇溶液中， 使捲繞元件内充分含浸該溶液後，把捲繞元件從該溶液 中取出，以150°C加熱1小時，使乙烯二羥基噻吩聚合， 在捲繞元件内形成聚乙烯二羥基噻吩之固態電解質。其 結果顯不：與比較品相較，隨著空隙率的增加，本發明 產品之固態電解質之保存率亦跟著增加。 實施例2 利用濕式抄造法，把m_芳香族聚醯胺纖維（把杜邦公司 '製‘「NOMEX」（註冊商標）切斷為6 mm者）及纖維素（把木 材紙漿以叩解機進行處理，並把加拿大標準濾、水度調節 為300 ml者），製作出成形為薄膜狀之紙，來作為實施例 用之分隔片。又，利用濕式抄造法，把m料族聚醯胺 纖維/把杜邦公司製「NOMEX」（註冊商標）切斷為6mm者 )及方香族聚醯胺纖條體（其係把採用濕式沉澱機之方法 所製造出來之物，以叩解機進行處理，並把加拿大標準 濾水度調節為105 ml者；而該濕式沉澱機係特公昭 ^ 1624號公報記載之由定子及轉子之組合所構成者） ‘乍出成形為薄膜狀之芳香族聚醯胺紙，來作為比較例 用之分隔片。 、、二由上述製作出之芳香族聚醯胺紙，把陽極電極箔及 去極私極、名進行捲繞，製作2個捲繞元件；而在該陽極電 極箔方面，本二β 八衣面係預先實施蝕刻處理，並實施化成處 O:\89\89916.DOC 2 -16- 1235392 理，且係由鋁箔所形成者，而該鋁箔表面係形成有包含 氧化紹之氧化皮膜層者。 把此2種捲繞元件置入恆溫加熱爐中，以350°C加熱2 小時。 從各捲繞元件之質量的減少量，計算分隔片之密度、 空隙率；其結果係如下述表2所示。又，芳香族聚醯胺之 素材密度係以1.35 g/cm3、纖維素之素材密度係以1.55 g/cm3進行計算。 表2 V, 狀態 、.組成 重量 比 坪量 (g/cm2) 厚度 (μπι) 密度 (g/cm3) 空 隙 率 (%) 實施 例2 加熱處 理前 芳香族聚醯胺 纖維/纖維素 50/50 10 40 0.25 83 加熱處 理後 芳香族聚醯胺 纖維/纖維素 100/0 5 37 0.14 90 比較 例1 加熱處 理前 芳香族聚醯胺 纖維/芳香族 聚醯胺纖條體 80/20 10 40 0.25 81 加熱處 理後 芳香族聚醯胺 纖維/芳香族 聚醯胺纖條體 80/20 10 40 0.25 81 接著，把實施例2及比較例1之各捲繞元件，分別浸潰於 乙烯二羥基噻吩與P-曱苯磺酸第二鐵之丁醇溶液中，使捲 繞元件内充分含浸該溶液後，把捲繞元件從該溶液中取出 ，以15(TC加熱1小時，使乙烯二羥基噻吩聚合，在捲繞元 件内形成聚乙烯二羥基噻吩之固體電解質。其結果顯示： 與比較例1之捲繞元件相較，在實施例2之捲繞元件方面， O:\89\89916.DOC2 -17- 1235392 隨著空隙率的增加，其固體電解質之保存率亦跟著增加。 【圖式簡單說明】 圖1係在本發明中所使用之捲繞元件之分解立體圖。 【圖式代表符號說明】 1 陽極電極箔 2 陰極電極箔 3 分隔片 4 陽極引出手段 5 陰極引出手段 6 捲繞元件 O:\89\89916.DOC 2 -18-O: \ 89 \ 89916.DOC -15- 1235392 Next, the wound elements (the product of the present invention and the wound elements (comparative products) without any solvent impregnation treatment) which have been subjected to a solvent impregnation treatment are immersed separately. After the winding element is sufficiently impregnated with the solution of ethylene dihydroxythiophene and second iron benzenesulfonic acid in the butanol solution, the winding element is taken out of the solution, and heated at 150 ° C for 1 hour to make ethylene Hydroxythiophene polymerizes to form a solid electrolyte of polyethylene dihydroxythiophene in the winding element. The result is not as clear: Compared with the comparative product, as the porosity increases, the preservation rate of the solid electrolyte of the product of the present invention also increases. Example 2 Using wet papermaking, m_aromatic polyamide fibers (those cut from "Nomex" (registered trademark) made by DuPont Corporation to 6 mm) and cellulose (wood pulp was processed with a decomposing machine) Processed, and adjusted the Canadian standard filter and the water content to 300 ml) to produce a paper formed into a film shape as a separator for the example. In addition, the wet-type papermaking method was used to prepare the m-type polyamine. Fiber / made by DuPont `` NO "MEX" (registered trademark is cut to 6mm) and fragrant polyamidofibrids (which are made by using a wet precipitation machine method, processed with a decomposing machine, and Canadian standard filtration Those whose water content is adjusted to 105 ml; and this wet sedimentation machine is composed of a combination of a stator and a rotor described in Japanese Patent Publication No. 1624) 'Aromatic polyurethane paper formed into a thin film shape as the first Separator for Comparative Example. The two aromatic polyamide papers produced from the above are wound with the anode electrode foil and the depolarized private electrode and name to make two winding elements. In terms of the anode electrode foil, this two beta Yaki The surface is etched in advance and chemically processed at O: \ 89 \ 89916.DOC 2 -16-1235392. The surface is formed of aluminum foil, and the surface of the aluminum foil is formed with an oxide film layer containing oxide. The two types of winding elements were placed in a constant temperature heating furnace and heated at 350 ° C for 2 hours. The density and porosity of the separator were calculated from the decrease in the mass of each wound element; the results are shown in Table 2 below. The material density of the aromatic polyamine was calculated at 1.35 g / cm3, and the material density of the cellulose was calculated at 1.55 g / cm3. Table 2 V, state, composition weight ratio (g / cm2) thickness (μπι) density (g / cm3) porosity (%) Example 2 Aromatic polyamide fiber / cellulose 50/50 before heat treatment 10 40 0.25 83 Aromatic polyamide fiber / cellulose after heat treatment 100/0 5 37 0.14 90 Comparative Example 1 Aromatic polyamide fiber / aromatic polyamide fiber sliver before heat treatment 80/20 10 40 0.25 81 Aromatic Polyamide Fibers / Aromatic Polyamide Fiber Slivers 80/20 10 40 0.25 81 After Heat Treatment Next, each of the winding elements of Example 2 and Comparative Example 1 was immersed in ethylene dihydroxythiophene. In the butanol solution of the second iron with P-toluenesulfonic acid, the winding element is sufficiently impregnated with the solution, and then the winding element is taken out of the solution and heated at 15 ° C for 1 hour to make ethylene dihydroxythiophene. Polymerization to form a solid electrolyte of polyethylene dihydroxythiophene in the wound element. The results show that, compared with the wound element of Comparative Example 1, in the wound element of Example 2, O: \ 89 \ 89916.DOC2 -17- 1235392 As the porosity increases, the retention rate of its solid electrolyte also follows [Simplified illustration of the drawing] Fig. 1 is an exploded perspective view of the winding element used in the present invention. [Description of the representative symbols of the drawing] 1 anode electrode foil 2 cathode electrode foil 3 separator 4 anode extraction means 5 cathode extraction Means 6 winding element O: \ 89 \ 89916.DOC 2 -18-