200400526 玖、發明說明： ㈠發明所屬之技術領域 本發明係有關一種具有使用鉬等閥作用金屬與黏合劑樹 脂之成形體、及其製法，其中，有關附有基體之燒結用成 形體及其製法，特別是有關爲具有形成電解電容器陽極元 件用多孔質燒結體之燒結用成形體的附有基體之燒結用成 形體及其製法。 ㈡先前技術 由鉅、鈮等閥作用金屬所成的多孔質體，可藉由陽極氧 化控制在多孔質表面上形成由膜厚之氧化物所成的介電 體，利用該多孔質體之廣泛表面積，大爲使用作爲電解電 容器用陽極兀件。特別是鉬使用於耐熱性、耐腐鈾性高、 作爲燒結體之單紗材料或化學裝置之零件、人工骨等，大 多利用於電解電容器用途。 近年來，表面封裝顯示器之小型化技術飛躍進步，且對 攜帶型電話、電腦、圖示數據相機等電子機器之零件基板 的封裝技術高密度化。其中，於電子零件之電容器元件中， 對於要求小型化、薄型化、大容量化而言有各種的硏究。 現在一般使用的電容器元件中，特別是例如钽電解電容 器具有可小型大容量化之特長，盛行硏究著重於更小型 化、薄型化。 具有與鉅金屬相同特長之材料，即作爲閥作用金屬例如 鋁、鈮、鈦等金屬類材料，於耐熱性、介電體被膜形成性 而言鉬金屬可得局需求。 上述閥作用金屬粉末，例如使用鉅之電解電容器製法， 200400526 通常使用鉬作爲陽極金屬粉、且將擔任作爲黏合劑之效果 的樹脂與鉅金屬粉末投入模具’使此等加壓加工以製作晶 片化的陽極元件用成形體。 該製作的陽極元件用成形體中設置陽極端子所成的零 件（通常爲鉅導線）。該導線通常使植入模具內之鉅金屬粉 末藉由加壓成形固定。 藉由上述步驟所得元件’於真空中藉由高溫加熱處理、 經由蒸發除去元件中所不需的樹脂步驟。 藉由該步驟蒸發除去存在於鉅金屬粉末間之樹脂，且藉 由鉬金屬粉末間之接觸點下熔融’製得形成多孔質體形態 之鉅電解電容器用陽極元件。 如此所得的鉬電解電容器用陽極元件置於電解液槽 中，施加所定的直流電壓、進行化成處理，在鉬金屬粉末 表面上形成由氧化鉅所成的介電體被膜後，在該被膜上形 成二氧化錳、或功能性高分子之固體電解質被膜。 然後，另外施予碳、銀漿料陰極層處理予以樹脂外裝， 製得最終的鉅電解電容器。 近年來，對電解電容器之小型化、薄型化之要求而言， 進行使電容器之尺寸更小型化、薄型化的硏究。藉由該薄 型化，例如可埋入基板且積層化’可實現低等價直列電阻 (ESR)，且可提高高周波特性。然而，使用習知模具的方法， 對於有效地製作〇.5mm以下薄型電解電容器用陽極元素有 困難，且對於製作厚度1 mm者亦有困難。 薄型化的方法係於日本特開昭5 6- 8 3022號公報中揭 示，使閥作用金屬之粉末與由熱塑性樹脂所成的黏合劑與 200400526 有機溶劑混合、製作漿料，由該漿料形成片（薄膜狀成形 體）’使導線接合於該片上進行脫黏合劑處理後，燒結電解 電容器用陽極元件之製法。 然而，上述由使閥作用金屬粉末、黏合劑樹脂與有機溶 劑混合的漿料形成片時，會有下述的問題。 特別是使燒結體用成形體燒結、形成電解電容器用陽極 元件時，爲確保殘留碳量低、外漏電流小的良好電容器特 性時’以使黏合劑樹脂儘可能少量較佳，惟黏合劑樹脂之 配合量少時，片（成形體）之強度降低、且不易處理。例如 於加工處理途中，因自成形體之載體剝離時、或使載體剝 離後之部分成形體會崩壞，導致製品處理性降低。 換言之，閥作用金屬粉末之配合量多時，藉由黏合劑樹 脂之黏合效果減低，特別是薄型化時由於成形體容易被破 壞’故必須配合一定比例以上之黏合劑樹脂。 另外，爲確保強度時配合充分的黏合劑樹脂時，如上述 般因殘留碳量變多，會有電容器元件之電器特性降低問 題。 ㈢發明內容 本發明係有鑑於上述問題，以提供一種具有良好加工性 之成形體的附有基體之成形體及其製法，特別是附有基體 之燒結用成形體及其製法。另外，提供特別是可得電氣特 性良好的電容器元件、且加工性良好的電解電容器之多孔 質性陽極所使用的具有燒結用成形體之附有基體的燒結用 成形體爲目的， 爲解決上述課題時，本發明附有基體之成形體，其係於 200400526 具有片狀基體、與在該片狀基體上設有可剝離的成形體之 附有基體的成形體中，其特徵爲成形體具有保護層與多孔 質體形成層，且該保護層含有以樹脂作爲主成分，該多孔 質體形成層含有閥作用金屬粉末與黏合劑樹脂。 此外，本發明附有基體之成形體的製法，其特徵爲包含 在片狀基體上形成以樹脂爲主成分之保護層步驟、與在該 保護層上含有閥作用金屬粉末與黏合劑樹脂之多孔質體形 成層的步驟，該保護層與多孔質體形成層之黏合強度較該 基體與保護層之黏合強度爲大。 另外，本發明之另一附有基體的燒結用成形體之製法， 其特徵爲包含在片狀基體上塗覆含有閥作用金屬粉末與黏 合劑樹脂與溶劑之多孔質體形成用塗料以形成塗膜之步 驟，與在該塗膜中藉由閥作用金屬粉末沉澱、在塗膜之表 層上形成以樹脂爲主成分之保護層的步驟。 而且，本發明係提供一種電解電容器陽極元件用成形 體’其係於具備含有閥作用金屬粉末與黏合劑樹脂之閥作 用金屬層的電解電容器陽極元件用成形體中，其特徵爲該 成形體之至少一面表層上具有爲保護閥作用金屬層之以樹 脂爲主成分的領域。 本發明之成形體’由於爲保護含有上述閥作用金屬粉末 與黏合劑樹脂之多孔質體形成層、由於具有以樹脂爲主成 分之層狀領域（保護層），故在該領域可達成補強效果、且 可防止成形體崩壞等。 此外，爲保護上述多孔質體形成層、以樹脂爲主成分之 層狀領域（保護層），由於配置於如成形體之部分表層領 200400526 域’故可減低燒結體之殘留碳、使燒結體使用作爲電解電 容器用多孔質性陽極時，可確保電解電容器陽極元件之良 好電氣特性。 (四）實施方式 實施發明之最佳形態 (成形體之製造） 於下述中以數個實施例說明有關本發明附有基體之成 形體的製法。 而且’於本說明書中「成形體」係包含附有基體者、或 沒有基體者，進行燒結等步驟前之各種形態稱呼。於說明 書中特別是沒有產生懷疑對象時所使用的直接稱呼，惟明 示與基體之關係較佳時爲附記的「附有基體」「沒有基體」 等語句。 「成形體之元件」係爲在上述「沒有基體之成形體」上 裝附有導線者，表示製作電解電容器陽極元件時燒結前成 形體的形態。 而且’「陽極元件」係爲使「成形體元件」燒結後之形 態。 此外，於本說明書中上述「爲保護多孔質體形成層之以 樹脂爲主成分的保護層」包含儘可能保護多孔質體形成層 之濃度的樹脂，亦可以實質上不含閥作用金屬粉末者，亦 可以含有閥作用金屬粉末。 「以樹脂爲主成分之層」，由於視保護層之製法等相關 保護層之形態、或使用材料之特性等而不同，無法一起全 部規定’例如在閥作用金屬上使用鉅時，樹脂濃度最高部 •10- 200400526 分之樹肖曰？辰度爲1 〇質量％以上、較佳者爲1 5質量％以上， 以設定可充分發揮保護多孔質體形成層之功能較佳。 對此而言，有關以閥作用金屬粉末爲主成分、且於燒結 後形成多孔質體之多孔質體形成層，以下述較佳配合比規 定下、樹脂之濃度例如閥作用金屬爲Ta時較佳者爲9質量 %以下、更佳者爲5質量％以下。 此外’以樹脂爲主成分之保護層例如可以多孔質體形成 層個別以獨立層存在、亦可以另外形成積層於多孔質體形 成層。或者，在多孔質體形成層之表層（例如與多孔質體形 成層一體化、且實質上作爲多孔質體形成層之一部份存 在’且形成該多孔質體形成層之表面層）上，藉由樹脂之濃 度梯度等形成的樹脂濃度高層。 總之’以樹脂爲主成分之保護層，較佳者作爲多孔質體 形成層之表層形成，或作爲與多孔質體形成層相鄰的獨立 層（保護層）形成。 而且’使上述以樹脂爲主成分之保護層作爲上述表層形 成時’如下述使用爲形成多孔質體形成層之塗料，在多孔 質體形成層中可形成樹脂之濃度梯度。而且，爲形成多孔 質體形成層之塗料、與較此之樹脂濃度高的其他塗料，使 用與爲形成上述多孔質體形成層時之塗料具有相溶性者， 藉由形成2層構造之塗膜（積層體），且使由2種塗料形成 的層相互一體化，結果在該一體化層中形成樹脂之濃度梯 度，可行成以樹脂爲主成分之保護層。 而且，以樹脂爲主成分之保護層可以在成形體表層上形 成，亦可以在成形體之一面或兩面上形成，惟使用燒結體 -11- 200400526 作爲電解電容器用多孔質性陽極時’就殘留碳量降低而言 以設於成形體之一面上較佳。 •第1之實施形態例_ 第1之實施形態例係爲在基體上順序設置由爲形成以 樹脂爲主成分之保護層的塗料所成第1層、與由爲形成多 孔質體形成層之塗料所成第2層’ 且製造上述第1層與第2層之黏合強度較上述基體與第1 層之黏合強度爲大的成形體。 第1〜2圖係爲本實施形態例之附有基體的成形體之製 法者。 首先，在片狀基體1上較佳者爲塗覆含有樹脂與溶劑之 溶液並乾燥作爲保護層2 ’以及於其上塗覆含有閥作用金 屬粉末3 a與黏合劑樹脂3 b、及含有溶劑之金屬粉末分散 液，且乾燥以形成多孔質體形成層3。 而且，使用上述溶液或金屬粉末分散液，構成保護層2 或多孔質體形成層3之方法，除塗覆外亦可使用印刷等各 種方法。 另外，與第1、2圖所示相反時，亦可先在基體1上使 用上述金屬粉末分散液，形成多孔質體形成層3。 然而，此時例如在多孔質體形成層3上形成保護層2， 使上述溶液塗覆於多孔質體形成層3上，藉由材料之特性 等使該溶液浸透於多孔質體形成層，結果無法製得以樹脂. 爲主成分之保護層領域。因此，通常可容易在基體上形成 保護層者。 如此，與第1、2圖所示時相反地，在基體1上先設置 > 12- 200400526 多孔質體形成層3、且於其上形成保護層2時等，例如爲 形成保護層2時設定提高含有樹脂與溶劑之溶液的黏度， 且在多孔質體形成層3上塗覆該溶液時，該溶液無法過份 浸透於多孔質體形成層3上，故爲所企求。 或另外形成保護層且藉由複印積層於多孔質體形成層 上。 然後，剝離基體1時，由於保護層2與多孔質體形成層 3之黏合力較基體1與保護層2之黏合力爲大時，如第2 圖所示保護層2與多孔質體形成層3 —體化的狀態下自基 體1剝離，製得在多孔質體形成層3之一面、即成形體4 之表層上設置以樹脂爲主成分的保護層2之成形體4。 而且，構成多孔質體形成層3之黏合劑樹脂3b與構成 保護層2之樹脂具有相溶性時，多孔質形成層3之黏合劑 樹脂3 b與構成保護層2之樹脂的部分或全部（較佳者爲全 部）界面消失且一體化。結果，如第3圖所示自多孔質體形 成層3，形成與其一體化、朝向基體1側之保護層2的樹脂 濃度梯度，自該第2層3側朝向第1層2側徐徐地提高樹 脂濃度（有機化合物之濃度）。 然後，如此藉由使保護層2與多孔質體形成層3 —體 化’實質上爲多孔質體形成層5之部份，在該表層上使以 樹脂爲主成分之保護層6形成於成形體4表層上。結果， 藉由該保護層6可提高成形體4之機械強度。 而且，如如第2圖、第3圖所示，是否可剝離基體1與 保護層2(或6)之界面’係藉由電子探子X線微分析器（EpMA) 或SEM-EDS等微小分析成形體4之剝離面上碳原子存在量 200400526200400526 (1) Description of the invention: (1) Technical field to which the invention belongs The present invention relates to a molded body having a valve action metal such as molybdenum and a binder resin, and a method for manufacturing the same, wherein a sintered molded body with a substrate and a method for manufacturing the same In particular, the present invention relates to a sintered molded body with a base, which is a sintered molded body having a porous sintered body for forming an anode element for an electrolytic capacitor, and a method for producing the same. ㈡In the prior art, porous bodies made of valve-acting metals such as giant and niobium can be controlled by anodization to form a dielectric body made of a film thickness oxide on the porous surface. The surface area is largely used as an anode element for electrolytic capacitors. In particular, molybdenum is used for heat resistance and corrosion-resistant uranium resistance, as a single yarn material for sintered bodies, parts of chemical devices, artificial bones, etc., and is mostly used for electrolytic capacitor applications. In recent years, the miniaturization technology of surface-mounted displays has made rapid progress, and the packaging technology of component substrates for electronic devices such as mobile phones, computers, and graphic data cameras has become denser. Among them, various considerations are required for capacitor elements of electronic parts for miniaturization, thinning, and large capacity. Among conventionally used capacitor elements, tantalum electrolytic capacitors, in particular, have the feature of being able to be reduced in size and capacity, and have been predominantly focused on making them smaller and thinner. Materials that have the same characteristics as giant metals, that is, metal materials such as aluminum, niobium, and titanium, which are valve-acting metals, molybdenum metal can be in demand in terms of heat resistance and dielectric film formation. For the above valve-acting metal powder, for example, the giant electrolytic capacitor manufacturing method is used. 200400526 Molybdenum is usually used as the anode metal powder, and the resin and the giant metal powder serving as the binder are put into a mold. Body for anode element. The fabricated anode body molded part is provided with an anode terminal (usually a giant wire). The wire usually fixes the giant metal powder implanted in the mold by press forming. The element 'obtained by the above steps is subjected to a high-temperature heat treatment in a vacuum, and an unnecessary resin step in the element is removed by evaporation. In this step, the resin existing between the giant metal powders is removed by evaporation, and an anode element for a giant electrolytic capacitor in the form of a porous body is produced by melting at the contact point between the molybdenum metal powders. The thus obtained anode element for a molybdenum electrolytic capacitor was placed in an electrolytic solution tank, a predetermined DC voltage was applied, and a chemical conversion treatment was performed to form a dielectric film made of an oxide giant on the surface of the molybdenum metal powder, and then formed on the film Manganese dioxide or functional polymer solid electrolyte coating. Then, a cathode layer treatment of carbon and silver paste was separately applied to the resin exterior to obtain a final giant electrolytic capacitor. In recent years, in order to reduce the size and thickness of electrolytic capacitors, research has been conducted to reduce the size and thickness of capacitors. This reduction in thickness allows, for example, the substrate to be embedded and laminated, to achieve low equivalent in-line resistance (ESR) and improve high frequency characteristics. However, a method using a conventional mold is difficult to efficiently produce an anode element for a thin electrolytic capacitor of 0.5 mm or less, and it is also difficult to produce a thickness of 1 mm. The method for reducing the thickness is disclosed in Japanese Patent Application Laid-Open No. 5-6-83022. A powder made of a valve-acting metal and a binder made of a thermoplastic resin are mixed with an organic solvent of 200,400,526 to prepare a slurry. The slurry is formed from the slurry. Sheet (film-shaped molded body) A method for producing an anode element for an electrolytic capacitor by sintering a lead wire to the sheet and subjecting it to a debonding treatment. However, when the above-mentioned sheet is formed from a slurry in which a valve-acting metal powder, a binder resin, and an organic solvent are mixed, there are the following problems. In particular, when sintering a molded body for a sintered body to form an anode element for an electrolytic capacitor, in order to ensure good capacitor characteristics with a low residual carbon content and a small external leakage current, it is better to make the binder resin as small as possible, but the binder resin When the blending amount is small, the strength of the sheet (molded article) is reduced and it is difficult to handle. For example, during processing, when the carrier is peeled from the molded body, or a part of the molded body is broken after the carrier is peeled off, the product handleability is lowered. In other words, when the compounding amount of the valve-acting metal powder is large, the bonding effect by the binder resin is reduced, and especially when the thickness is reduced, since the formed body is easily damaged, a binder resin having a certain proportion or more must be blended. In addition, when a sufficient amount of the binder resin is blended in order to secure the strength, as described above, the amount of residual carbon increases, which may cause a reduction in the electrical characteristics of the capacitor element. ㈢ SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and provides a molded body with a base and a method for manufacturing the same, particularly a molded body with a base and a method for manufacturing the same. In addition, a purpose is to provide a sintered molded body with a sintered body having a sintered molded body for use in a porous anode for an electrolytic capacitor having a capacitor element having excellent electrical characteristics and excellent processability, in order to solve the above-mentioned problems. In the present invention, the formed body with a base body is formed from a 200400526 sheet-shaped base body, and a formed body with a base body provided with a peelable formed body on the sheet-shaped base body, which is characterized in that the formed body has protection. The layer and the porous body form a layer, and the protective layer contains a resin as a main component, and the porous body forming layer contains a valve action metal powder and a binder resin. In addition, the method for manufacturing a molded body with a substrate according to the present invention is characterized by including a step of forming a protective layer mainly composed of a resin on a sheet-like substrate, and a porous layer containing the valve action metal powder and the binder resin on the protective layer. In the step of forming a plastid, the adhesion strength between the protective layer and the porous body forming layer is greater than the adhesion strength between the substrate and the protective layer. In addition, another method for producing a sintered molded body with a substrate according to the present invention is characterized by comprising coating a sheet-like substrate with a coating material for forming a porous body containing a valve action metal powder, a binder resin, and a solvent to form a coating film. This step is a step of forming a protective layer mainly composed of a resin on the surface layer of the coating film by depositing metal powder in the coating film by a valve action. Furthermore, the present invention provides a molded body for an electrolytic capacitor anode element, which is a molded body for an electrolytic capacitor anode element provided with a valve-acting metal layer containing a valve-acting metal powder and a binder resin, and is characterized in that On at least one surface, there is an area mainly composed of resin, which is a metal layer for protecting a valve. The formed body of the present invention is formed to protect the porous body containing the valve-acting metal powder and the binder resin, and since it has a layered area (protective layer) mainly composed of resin, it can achieve a reinforcing effect in this area. Also, it can prevent collapse of the molded body. In addition, in order to protect the porous body forming layer and the layered area (protective layer) mainly composed of resin, it is arranged in a part of the surface layer of the formed body, such as the 200400526 domain. When used as a porous anode for electrolytic capacitors, good electrical characteristics of the anode element of electrolytic capacitors can be ensured. (4) Embodiment The best mode for carrying out the invention (manufacturing of formed body) In the following, several examples will be used to explain the method for producing the formed body with a substrate of the present invention. In the present specification, "formed body" refers to various forms before or after steps such as those with or without a substrate. In the explanation, it is used as a direct address when there is no doubt about the object. However, when the relationship with the base is better, it is the additional words such as “with base” and “no base”. The term "component of a molded body" refers to a case in which a lead is attached to the above-mentioned "molded body without a substrate", and indicates the shape of the molded body before sintering when an anode element for an electrolytic capacitor is manufactured. The "" anode element "is a sintered" formed element ". In addition, in the present specification, the above-mentioned "protective layer mainly composed of a resin for protecting the porous body-forming layer" includes a resin that protects the porous body-forming layer as much as possible, and may not substantially contain a valve-acting metal powder. , May also contain valve action metal powder. The "layer mainly composed of resin" cannot be specified together because it depends on the form of the protective layer such as the method of manufacturing the protective layer or the characteristics of the materials used. "For example, when the giant is used on a valve-acting metal, the resin concentration is the highest. Department • 10- 200400526 Xiao Zhi of the Tree? The degree is 10% by mass or more, and more preferably 15% by mass or more, and it is preferable to set a function that can sufficiently exert the function of protecting the porous body forming layer. In this regard, regarding the porous body forming layer that mainly contains valve action metal powder and forms a porous body after sintering, the resin concentration is determined under the following preferred mixing ratio, for example, when the valve action metal is Ta It is preferably 9% by mass or less, and more preferably 5% by mass or less. In addition, the protective layer mainly composed of a resin may be a porous body-forming layer, which may exist as an independent layer, or may be separately formed as a layer formed on the porous body. Alternatively, on the surface layer of the porous body forming layer (for example, a surface layer integrated with the porous body forming layer and substantially existing as a part of the porous body forming layer and forming the surface layer of the porous body forming layer), The resin concentration is formed by a resin concentration gradient or the like. In short, a protective layer mainly composed of a resin is preferably formed as the surface layer of the porous body forming layer or as an independent layer (protective layer) adjacent to the porous body forming layer. Further, "when the protective layer mainly composed of a resin is formed as the surface layer", a coating material for forming a porous body forming layer is used as described below, and a resin concentration gradient can be formed in the porous body forming layer. In addition, in order to form a coating for forming a porous body and other coatings having a higher concentration of the resin, those having a compatibility with the coating for forming the above-mentioned porous body forming layer are used, and a coating film having a two-layer structure is formed. (Layered body), and the layers formed of the two kinds of coating materials are integrated with each other. As a result, a concentration gradient of the resin is formed in the integrated layer, and it is possible to form a protective layer mainly composed of a resin. In addition, a protective layer containing a resin as a main component may be formed on the surface of the molded body, or may be formed on one or both sides of the molded body. However, when a sintered body is used as a porous anode for electrolytic capacitors, it remains' It is preferable that the carbon content be reduced to be provided on one surface of the molded body. • The first embodiment example_ The first embodiment example is that a first layer made of a coating material for forming a protective layer mainly composed of a resin and a layer for forming a porous body are sequentially provided on a substrate. The second layer formed by the coating material, and a molded body having a higher bonding strength between the first layer and the second layer than that of the substrate and the first layer is manufactured. Figures 1 to 2 show the method of manufacturing a molded body with a base body according to this embodiment. First, the sheet-like substrate 1 is preferably coated with a solution containing a resin and a solvent and dried as a protective layer 2 ′, and coated thereon with a valve action metal powder 3 a and a binder resin 3 b and a solvent containing The metal powder dispersion liquid is dried to form a porous body forming layer 3. In addition, as the method of forming the protective layer 2 or the porous body forming layer 3 using the solution or the metal powder dispersion liquid, various methods other than coating may be used, such as printing. In addition, in contrast to those shown in Figs. 1 and 2, the porous body-forming layer 3 may be formed by using the above-mentioned metal powder dispersion liquid on the substrate 1 first. However, at this time, for example, a protective layer 2 is formed on the porous body forming layer 3, the above solution is coated on the porous body forming layer 3, and the solution is impregnated into the porous body forming layer by the characteristics of the material, etc. Can not make resin. Protective layer field with main ingredients. Therefore, it is usually easy to form a protective layer on the substrate. In this way, contrary to the time shown in FIGS. 1 and 2, when the porous body-forming layer 3 is first provided on the substrate 1 and a protective layer 2 is formed thereon, for example, when the protective layer 2 is formed It is desirable to increase the viscosity of a solution containing a resin and a solvent, and to apply the solution on the porous body forming layer 3, because the solution cannot excessively penetrate the porous body forming layer 3, so it is desirable. Alternatively, a protective layer is formed and laminated on the porous body forming layer by copying. Then, when the substrate 1 is peeled off, since the adhesion force between the protective layer 2 and the porous body forming layer 3 is larger than the adhesion force between the substrate 1 and the protective layer 2, as shown in FIG. 2, the protective layer 2 and the porous body forming layer are formed. 3—The body 1 is peeled from the base body 1 in a bulk state, and a molded body 4 provided with a protective layer 2 containing a resin as a main component on one surface of the porous body forming layer 3, that is, a surface layer of the molded body 4 is obtained. In addition, when the adhesive resin 3b constituting the porous body forming layer 3 and the resin constituting the protective layer 2 are compatible, part or all of the adhesive resin 3b constituting the porous forming layer 3 and the resin constituting the protective layer 2 (more than The best is all) The interface disappears and is integrated. As a result, as shown in FIG. 3, the layer 3 is formed from the porous body, and the resin concentration gradient of the protective layer 2 which is integrated with the protective layer 2 toward the substrate 1 side is gradually increased from the second layer 3 side toward the first layer 2 side. Resin concentration (concentration of organic compounds). Then, by forming the protective layer 2 and the porous body forming layer 3 as a unitary body, the portion of the porous body forming layer 5 is substantially formed, and a protective layer 6 mainly composed of a resin is formed on the surface layer in a molding process. Body 4 on the surface. As a result, the mechanical strength of the molded body 4 can be improved by the protective layer 6. As shown in Fig. 2 and Fig. 3, whether or not the interface between the substrate 1 and the protective layer 2 (or 6) is peelable is determined by microanalysis such as an electron probe X-ray microanalyzer (EpMA) or SEM-EDS. Existence of carbon atoms on the peeling surface of the molded body 4 400 400 526
Catm與閥作用金屬原子 X之存在量 Xatm的比値 C a tm/X atm，對應各特性X線之電子信號脈衝之計算比測定 求取。 換言之，形成保護層2或6時，保護層2或6爲由以樹 脂爲主成分之有機化合物時，於成形體4中基體1側之 Catm/Xatm較相反面爲大。 以樹脂爲主成分之保護層中Catm/Xatm以1.0以上較 佳、更佳者爲1.2以上、最佳者爲1.3以上。 而且，形成保護層2或6時，直至燒結步驟爲止之繼後 步驟中，由於可保持成形體4(多孔質體形成層5或多孔質 體形成層3與保護層2)之形狀、提高加工性，藉由提高實 施製造步驟試驗之加工適性，可確認保護層2或6之存在。 •第2實施形態例 第2實施形態例係爲在基體上使用含有閥作用金屬粉 末與黏合劑樹脂與溶劑之金屬粉末分散液以形成塗膜，且 於上述塗膜中藉由使閥作用金屬粉末沉澱，使樹脂偏在於 該塗膜表層（基體之相反側）上，形成以上述樹脂爲主成分 之保護層的成形體製法。 例如第4圖所示，在與第1圖所示基體1相同的基體！， 上塗覆含有閥作用金屬粉末3’a與黏合劑樹脂3’b之金屬粉 末分散液以形成塗膜3 ’，於該塗膜3 ’中使閥作用金屬粉末 3 ’ a沉澱於基體1 ’側，在塗膜3 ’之表層上形成以樹脂爲主 成分之保護層6 ’。而且，保護層6 ’下方係爲以閥作用金屬 粉末爲主成分之多孔質體形成層7 ’。 另外，上述塗膜3 ’除塗覆金屬粉末分散液外，可使用印 200400526 刷等各種方法形成。 此時，與第3圖所示時相同地在上述塗膜3 5中形成樹脂 ί辰度梯度。而且’形成黏合劑樹脂3 ’ b之ί辰度梯度’結果’ 形成以樹脂爲主成分之保護層6 ’。總之，實質上爲多孔質 體形成層5’之部分，在其表面上形成保護層6’。 因此，即使剝離基體1 ’時，於成形體4 ’中藉由多孔質 體形成層5 ’表層上所形成保護層5 ’之作用賦予適當的強 度、予以補強，故可得提高加工性之效果。 爲使該閥作用金屬沉澱、形成保護層6 ’時，以使上述金 屬粉末分散液之黏度爲5Pa · s以下較佳、更佳者爲IPa · s 以下。該黏度之測定可使用B型黏度計進行，測定溫度爲 作業時之溫度。使用該黏度低的金屬粉末分散液、以一般 方法形成多孔質體形.成層時，例如直至使金屬粉末分散液 塗覆•乾燥爲止間，徐徐地使閥作用金屬粉末沉澱，且形 成樹脂與閥作用金屬粉末之濃度梯度。 本實施形態例只要是多孔質體形成層5，所成的塗料即 可’藉由調整塗覆時之黏度，結果可形成保護層6，，且材 料種類或製造步驟較爲簡單，故爲企求。 而且，於第1或第2實施形態例中，例如皆如第2圖所 示在加工途中使基體剝離前，使第i圖所示的成形體4與 基體1同時以所定寬度狹縫化時，例如可顯著提高電解電 谷器用陽極兀件用成形體之繼後連續加工性，故較佳。此 外，由於於除去加工中不會產生稱爲耳朵之耗費部分，故 較佳。另外，於第1層2上塗覆金屬粉末分散液時，條狀 塗覆、乾燥、裁成塗覆的形狀。 -15- 200400526 於下述中’詳細說明有關上述製造槪要說明的附有基體 之成形體所使用的各構成與製造順序。 (基體之準備） 可使用作爲片狀基體之材料，例如聚乙烯薄膜、聚丙烯 薄膜、聚氯化乙烯基薄膜、聚氯化次乙烯基薄膜、聚對酞 酸乙二酸薄膜、聚乙烯醇薄膜、聚對酞酸乙二酯（PET)薄 膜、聚碳酸酯薄膜、耐龍薄膜、聚苯乙烯薄膜、乙烯醋酸 乙烯酯共聚物薄膜、乙烯乙烯基共聚物薄膜等所成的塑膠 薄膜或片；或鋁等金屬片；紙、含浸紙；由此等材料所成 的複合物。於此等之中，就考慮黏合性、剝離性而言，可 藉由組合構成基體上形成層之樹脂等爲更佳的使用。此等 以外之材料只要是具備必要的強度、可撓性、以及較佳的 剝離性等，沒有特別的限制。特別是就強度、耐溶劑性、 價格等而言，通常使用PET薄膜。 基體之厚度沒有特別的限制，例如5μιη〜5 00μιη、較佳 者爲 ΙΟμηι 〜ΙΟΟμιη。 上述基體在容易剝離基體與成形體之界面下，亦可使用 剝離性基體。剝離性基體例如構成基體之薄膜狀材料本身 具有剝離性者，或在上述薄膜狀材料表面上形成有剝離層 者。而且，成形體之基體側表面對基體而言具有剝離性時， 即使沒有使用剝離性基體仍可順利地進行處理。 如下所述，例如PET薄膜爲基體時，藉由在基體上形成 以丙烯酸樹脂、聚乙烯基縮醛樹脂等爲主成分之層作爲塗 覆的第1層，可使第1層與基體之剝離性良好。 (以樹脂爲主成分之保護層的形成） -16- 200400526 保護層所使用的樹脂視製造方法等不同，就與PET之剝 離性而言可使用聚乙烯醇樹脂、聚乙烯基縮醛、丁縮醛樹 脂、丙烯酸樹脂等。藉此以含有一種以上選自於此等之樹 脂者較佳。其中，就降低殘留碳量而言以丙烯酸樹脂更佳。 而且，如第4圖所示使用金屬粉末分散液，藉由閥作用 金屬粉末沉澱以形成以樹脂爲主成分的保護層時，藉由該 閥作用金屬粉末之黏合劑樹脂以形成該保護層之領域。此 時，以使用上述例示的樹脂作爲黏合劑樹脂較佳。 於此等樹脂中，尤其是丙烯酸樹脂與金屬粉倂存、燒結 時，會有完全燃燒的傾向，故容易形成殘留碳量少的多孔 質體金屬燒結物。 此外’在如上述片狀基體上順序設置上述作爲第i層之 保護層、與作爲第2層之多孔質體形成層，且上述保護層 與多孔質體形成層之黏合強度較上述片狀基體與保護層之 黏合強度大時，必須在滿足該條件下設定黏合強度。 該黏合強度由於使構成各層之樹脂種類（樹脂相溶 性）、塗覆速度等各種條件變化，以實際製造條件進行試 驗、評估，且選擇可滿足該較佳特性者較佳。 雖沒有特別限制，具體例如在基體上使用pET薄膜時， 如組合下述之樹脂。 組合第1層（保護層）：丙烯酸樹脂、第2層（多孔質體形 成層）：與第1層相同種類之丙烯酸樹脂，或組合第1層（保 護層）：聚乙烯基縮醛樹脂、與第2層（多孔質體形成層）： 丙烯酸樹脂。 而且，在多孔質體形成層上使用與保護層相同種類之樹 -17 - 200400526 脂時，藉由相溶性、如第3圖所示使保護層2與多孔質體 形成層3之界面消失，且形成樹脂之濃度梯度。 藉由該界面消失，使第1層與第2層一體化，層間不會 產生剝離情形，故爲企求。 惟形成多孔質體形成層所使用的塗覆液中之溶劑，溶解 以樹脂爲主成分之保護層中樹脂的程度愈大時，使以樹脂 爲主成分之保護層的厚度本身愈薄的可能性愈大。爲此所 使用的樹脂以含有分子量爲25萬以上之成分較佳，以含有 樹脂全體之30質量％以上的上述分子量25萬以上成分更 佳。 以樹脂爲主成分之保護層例如可第1優所示在片狀基 體1上使用各種方法形成。 塗覆方法例如習知輥塗物方法等，具體例如氣刮漿刀塗 覆法、刮刀塗覆法、批次塗覆法、押出塗覆法、氣刀塗覆 法、擠壓塗覆法、含浸塗覆法、可逆輥塗覆法、轉換輥塗 覆法、凹槽輥塗覆法、接觸塗覆法、鑄造塗覆法、噴霧塗 覆法等。 而且，此時可使用以適當濃度溶解適當樹脂之溶液。溶 劑可使用與下述構成金屬粉末分散液之溶劑等相同者等。 以樹脂爲主成分之保護層厚度由於保護層本身有各種 形態，不易明確規定，惟至少直至燒結開始爲止間不會使 成形體崩壞等、可維持形狀效果的領域即可，沒有特別的 限制。 例如，以1 μπι〜20μπι較佳，只要是在該程度即可，不 會使成形體中樹脂總量大幅增加，亦不會使燒結後之殘留 -18- 200400526 碳量增加。特別是1 μιτι〜1 〇 μπι範圍，對燒結後之殘留碳量 影響很小，可適當維持塗膜之強度，故較佳。 (多孔質體形成層之形成） 構成多孔質體形成層之金屬粉末分散液可使閥作用金屬 粉末、黏合劑、以及溶劑、與視其所需之添加劑混合、分 散作成。 •閥作用金屬粉末 閥作用金屬粉末可使用鉅、鋁、鈮、鈦等閥作用金屬之 粉末。此等之閥作用金屬中以鉅、鈮較佳，更佳者爲鉅。 於下述說明中爲鉬金屬粉末例。 鉬金屬粉末之純度以99.5 %以上者較佳，其平均1次粒 徑以0.01〜5.0μιη較佳、更佳者爲0.01〜2.0μιη。 _•黏合劑樹脂 黏合劑樹脂可使用溶劑可溶性黏合劑樹脂。適合黏合劑 樹脂例如聚乙烯醇樹脂、聚乙烯基縮醛樹脂、丁縮醛樹脂、 苯酚樹脂、丙烯酸樹脂、尿素樹脂、醋酸乙烯酯乳液、聚 胺甲酸酯樹脂、聚醋酸乙烯酯樹脂、環氧樹脂、蜜胺樹脂、 院氧化物樹脂、硝基纖維素樹脂、天然樹脂等。此等樹脂 可以單獨使用或2種以上混合使用。 此外，於上述樹脂中與以樹脂爲主成分之保護層時相同 地，可使用聚乙烯醇樹脂、聚乙烯基縮醛樹脂、丁縮醛樹 脂、丙烯酸樹脂等。 其中，丙烯酸樹脂在真空中之黏合劑處理時，由於幾乎 完全分解、且殘留碳量少，特別是由成形體製作電解電容 器用陽極元件時可以防止電解電容器之外漏電流情形增 -19- 200400526 加，故爲企求。 上述樹脂之玻璃轉移點以5 0 °C以下較佳、更佳者爲室 溫以下。右爲50C以下時’如第1、2圖所示由於可使多孔 質體形成層3具有可撓性、成形體不易崩壞，故可提高處 理性，爲所企求。 而且’黏合劑樹脂說明有關上述以樹脂爲主成分之保護 層’以滿足黏合強度之關係下適當選擇較佳。 上述黏合劑樹脂之使用量例如鉅金屬粉末時，以1 00質 量份爲基準0.01〜30質量份較佳、更佳者爲0.01〜15質量 份。 若黏合劑樹脂之配合量過多時，燒結後之殘留碳量增 加，例如自成形體製作電解電容器用陽極元件時，會產生 電容器特性降低等缺點。 •溶劑 溶劑例如水、或甲醇、2-丙醇（異丙醇）、二乙二醇等之 醇類；甲基溶纖劑等之溶纖劑類；丙酮、甲基乙酮、異佛 爾酮等酮類；N，N-二甲基甲醯胺等之醯胺類；醋酸乙酯等 之酯類；二噁烷等之醚類；氯化甲基等之氯系溶劑；甲苯、 二甲苯等之芳香族烴類；等。此等溶劑可以單獨使用或2 種以上混合使用。 溶劑之使用量係設定於可順利實施塗覆金屬粉末分散 液之步驟的範圍。 而且，所使用的金屬粉末分散液中除上述鉬金屬粉末、 黏合劑樹脂及溶劑外，以爲使該金屬粉末分散液塗覆或印 刷於基體表面時之較佳物性、且爲安定保持金屬粉末之分 -20 - 200400526 散或流動性等爲目的時，可以添加各種適當添加劑。 適當添加劑例如有對酞酸酯、磷酸酯、脂肪酸酯等分散 劑、醇類等之可塑劑、低沸點醇、聚矽氧烷矽或非聚矽氧 烷系等消泡劑、矽烷偶合劑、鈦偶合劑、四級銨鹽等之分 散劑等’視其所需適當使用。特別是藉由使用熔點爲3 (TC 以下之脂肪酸酯，提高由金屬粉末分散液形成的成形體加 工性’較不易發生加工時成形體部分崩壞或欠缺的情形。 此等添加劑之使用量，例如爲鉬時對1 〇〇質量份金屬粉末 而言以0.01〜5.0質量份較佳。 • __金屬粉末分散液之調整方法 上述之閥作用金屬粉末、溶劑、溶劑可溶性黏合劑樹 脂、及視其所需配合的添加劑，可同時或各順序投入，藉 由使用各種熔融•分散機予以分散製得。 捏合•分散可使用攪拌機、二條輥、三條輥等之輥型捏 合機、縱型捏合機、加壓捏合機、行星齒輪混合機等之葉 片型捏合機、球型回轉磨、砂磨等分散機、超音波分散機、 奈米分散機等。 ·___閥作用金屬粉末分散液之配合例 例示閥作用金屬粉末分散液之配合比例，例如對1 〇〇質 里份組金屬粉末而言黏合劑樹脂爲〇.〇1〜30質量份（較佳 者爲0.0 1〜1 5質量份）、溶劑爲5〜1 60質量份、添加劑爲0 〜5質量份。 而且’閥作用金屬粉末分散液之黏度爲1〜lOOOPa · s、 以5〜lOOPa · s較佳。此外，使用在基體上塗覆閥作用金 屬分散液、且使閥作用金屬沉澱，在多孔質體形成層之表 - 21- 200400526 層上形成以樹脂爲主成分之保護層的製法時，閥作用金屬 粉末分散液之黏度以5 P a · s以下較佳、更佳者爲1 P a ·以 下。黏度測定方法藉由B型黏度計進行者，測定溫度爲作 業時之溫度。 •陽極形成層之形成 使如此所得的閥作用金屬粉末分散液視使用的製法而 定塗覆於基體上等。例如，第1圖即上述所示片狀基體1 上形成保護層2後，於該保護層2上使該金屬粉末分散液 塗覆、乾燥時，可製得多孔質體形成層3。然後，結果可 製得由多孔質體形成層3與以樹脂爲主成分之保護層2所 成的成形體4。 閥作用金屬粉末分散液之塗覆方法與上述剝離層相同 地可使用各種塗覆方法。 閥作用金屬粉末分散液之乾燥以使用40〜12(TC之熱風 較佳，可使分散液中之溶劑揮發。使該溶劑揮發後，可使 成形體與基體捲取成捲軸狀。換言之，爲使具有作爲保護 層功能之第1層存在時，即使捲成捲軸狀，該成形體破壞、 無法製基體脫落。因此，可以塗覆完成之成形體作爲基體 且捲取，藉由連續的塗覆步驟可在基體上形成成形體。 成形體4之厚度可是當地設定，惟使用該燒結體形成電 解電容器用多孔質性陽極時，可藉由作爲電解電容器要求 的靜電容量與以適當設定，直至乾燥前金屬粉末分散液之 塗覆物厚度（濕時厚度）爲數μιτι〜300μιη爲止予以薄膜化。 通常，爲製作對應薄型電解電容器之電解電容器陽極元 件時，多孔質體形成層之乾燥厚度以〇.5mm以下膜厚更 -22- 200400526 佳。另外，乾燥厚度以〇.4mm以下自六杜 _ ^ ^ ^ μ卜較佳、更佳者爲〇 . 3〜 0.05mm、最佳者爲 0.2 〜0.05mm。 (狹縫化操作） •狹縫化方法 然後，例如第1圖所示成形體4，較佳者與片狀基體1 共同以所定寬度狹縫化。 狹k化方式例如雷射切割方式、刀與輥之間運動利用切 變作用的共同切割方式等、可利用習知方法中任何方法。 切割精度可以爲共同切割者，使厚者切斷時亦可以同時切 割者。而且，亦可使用具有各片刀之滾動切割予以狹縫化。 此外，可使上述金屬分散液在如第1圖所示第丨層2上 條狀塗覆、乾燥、裁成塗覆形狀後，捲成捲軸狀。塗覆成 條狀時’乾燥後必須狹縫化成塗覆形狀。狹縫化可以與上 述相同方法進行。 如此所得的成形體係爲在基體上均勻形成者，膜厚分布 狹窄、可撓性、柔軟性優異。因此，不會引起位置脫離情 形，可容易捲成片狀基體與捲軸狀。於該狹縫化後，捲繞 成捲軸狀之燒結體用成形體，保存性、搬送性優異。 (電解電容器陽極元件之製作） 使用藉由上述方法製作的本發明成形體，可製造電解電 容器陽極元件。其具體方法如下述所示。 使用本發明成形體之電解電容器用陽極元件，例如可如 下述製作。 首先，使成形體自基體剝離且切斷成企求長度後，如第 5圖所示於其上放置導線或較佳的扁平導線1 3之扁平部分 -23- 200400526 1 3 a，另與其他成形體1 4重疊，視其所需施加適 處理，藉由使2張成形體12，14與扁平導線13 成電解電容器陽極元件用成形體元件15(以下倂 元件1 5之簡略形）。 該狹縫寬度夾住導線，藉由與加壓處理製作的 器陽極元件之寬度一致下預先調整，狹縫化後不 體切斷成一定長度，且可製得企求尺寸的電解電 元件用成形體。該方法與由寬度同寬的片狀成形 求尺寸的成形體方法相比時，由於不會使不需的 形體生成’故可以良好生產效率且大量生產。 本發明之成形體爲具有保護多孔質體形成層之 主成分的保護層時，上述狹縫、或狹縫後捲繞時 會破壞、自基體脫離，且夾住導線之加壓處理中 易破壞成形體。 上述扁平導線由閥作用金屬（例如由鉅）所成、 陽極元件之部份或全體以扁平形成。該扁平導線 至少部分鉅線加壓成形予以扁平化所製作者。扁 扁平部分的厚度與寬度係考慮製作的陽極元件厚 強度等而言予以適當設定，較佳者扁平化成成形 爲5〜70 %之厚度。 _•燒結步驟 然後，使上述電解電容器陽極元件用成形體3 其所需適當乾燥，且在真空中藉由約300〜600°C 步驟進行除去有機物質（黏合劑），另進行約1 0〜 約 1 200〜1 600 t：之高溫加熱處理（燒結），藉由使 當的加壓 密接，形 用成形體 電解電容 僅使成形 容器陽極 體形成企 部分在成 以樹脂爲 成形體不 仍不會容 至少埋入 例如藉由 平導線之 度、導線 體之厚度 5件1 5視 之熱處理 3 0分鐘、 組金屬粉 200400526 末間及鉅金屬粉末與導線（較佳者爲扁平導線1 3)熔融，可 製得如第6圖所示在薄型正方形鉅多孔質燒結體1 7內埋入 導線13(較佳者扁平導線之扁平部分13a)構造之钽電解電 容器用陽極元件1 8。如此所得的鉅電解電容器用陽極元件 1 8爲鉅多孔質燒結體與導線1 3堅固地黏接狀態。 (電解電容器之製作） 使用上述鉅電解電容器用陽極元件1 8，於製造鉬電解 電容器時使該陽極元件置於電解液槽中，對該陽極元件施 加所定直流電壓以實施化成處理，在該陽極元件1 8表面上 形成氧化鉬之介電體被膜。 然後，形成氧化被膜後，另於其上形成二氧化錳被膜、 或功能性高分子被膜之固體電解質。 如上述所得的形成氧化钽被膜·二氧化錳被膜或機能 性高分子被膜的電容器元件3 1，形成碳（石墨）層、銀漿料 層’例如第7圖所示在電容器元件3丨表面上以焊料34接 合陰極端子3 2之一側，使扁平導線丨3之前端部分以點熔 接（以符號35表示熔接部）接合於陽極元件33後，例如藉由 樹脂成形加工、或浸漬於樹脂溶液中形成等實施樹脂外裝 3 6以形成鉅電解電容器。 本發明之製法亦可使用於製造積層型電解電容器。該積 層型電解電容器係使用本發明製法所製造的積層極爲薄型 電解電容器，藉由連接它形成。 實施例 於下述中以實施例詳細說明本發明。 (鉬金屬粉末分散液之調整） -25- 200400526 使下述二種配合物加入100cc聚瓶中混合，使用振動機 精練1小時，製得鉬金屬粉末分散液A、及B。 分散液A : •平均一次粒徑〇.5μιη之鉬金屬粉末50g， •作爲黏合劑樹脂之丙烯酸樹脂「NCB-166」（大日本油墨 化學工業（股）製）6.0g(2.5g)(()內爲固成分量）， •作爲溶劑之環己酮與甲苯之混合溶劑5.5 g，及 • 3mm之鋼球50g 分散液B : •平均一次粒徑0.5μιη之鉅金屬粉末50g， •作爲黏合劑樹脂之丙烯酸樹脂「NCB-166」（大日本油墨 化學工業（股）製）6.02(2.5£)(()內爲固成分量）， •作爲溶劑之環己酮與甲苯之混合溶劑1 2.9g，及 • 3 m m之鋼球5 0 g (電解電容器陽極元件用成形體之製作） (實施例1) 在作爲基體之厚度50μιηΡΕΤ薄膜上使丙烯酸樹脂「IB-30 」 （藤 倉化成 （股）製 構成成 分：甲 基丙烯 酸異丁 酯重量 平均酚子量：20萬〜30萬）、固成分比20質量％之甲苯溶 液以#16滑動片展色，且設置厚度4μιη之保護層。 然後，在該第1層上使鉅金屬粉末分散液Α以45 Ομιη 深度之塗覆器展色，製得厚度2 00μιη之鉬金屬粉末分散液 Α之乾燥塗膜（多孔質體形成層）。 使所得電解電容器陽極元件用之附有基體的成形體截 面影像如第8圖所示。 -26- 200400526 由該影像可知，由於含有多孔質體形成層之黏合劑樹脂 與保護層中所使用的樹脂具有相溶性，部分保護層與多孔 質體形成層沒有界面，且可得形成樹脂濃度高的以樹脂爲 主成分之保護層的電解電容器陽極元件用成形體之截面。 此外’該碳原子與鉅原子之圖示數據各如第9a圖、第 9B圖所示。而且，圖示數據係爲以SEM-EDS測定的碳數K 線、鉅L線。檢測器係使用EDX公司製者且Time constant 外之測定條件係以EDX公司之標準測定條件進行。 而且，以SEM-EDS測定電解電容器陽極元件用成形體 之基體側（形成以樹脂爲主成分之保護層側）的鉅原子存在 量Taatm與碳原子存在量之原子數比Catm/Taatm，及相反 側之原子數比Catm/Taatm時，各爲1.49〜3.50與0.65〜 0.73。 (實施例2) 除使用以75質量％與「IB-30」相同構成成分之重量平 均分子量爲23〜29萬丙烯酸樹脂、與25質量％「IB-30」 相同構成成分之分子量爲7〜9萬之丙烯酸樹脂作爲第1層 所使用的丙烯酸樹脂外，與實施例1相同地測定基體側與 基體與相反側之成形體表面Catm/Taatm時，各爲1.25〜 1 .41、0.64〜0·74。 (實施例3) 除使用以50質量％與「ΙΒ-30」相同構成成分之重量平 均分子量爲23〜29萬丙烯酸樹脂、與50質量％「ΙΒ-30」 相同構成成分之分子量爲7〜9萬之丙烯酸樹脂作爲第1層 所使用的丙烯酸樹脂外，與實施例1相同地測定基體側與 -27- 200400526 基體與相反側之成形體表面Catm/Taatm時’各爲1·〇8〜 1 .28、0.37 〜0.42。 (實施例4) 在作爲基體之厚度5 0 μιη之PET薄膜上使鉅金屬粉末分 散液B以45 0μιη深度之塗覆器展色，製得厚度2 0 0μιη之鉅 金屬粉末分散液Β之乾燥塗膜。 使所得電解電容器陽極元件用之附有基體的成形體截 面影像如第1 0圖所示。 由該影像可知，由於含有多孔質體形成層之黏合劑樹脂 與保護層中所使用的樹脂具有相溶性，部分保護層與多孔 質體形成層沒有界面，且可得形成樹脂濃度高的以樹脂爲 主成分之保護層的電解電容器陽極元件用成形體之截面。 此外，該碳原子之圖示數據如第11圖所示。而且，圖 示數據之作成以與實施例1相同的測定條件進行。 而且，電解電容器陽極元件用成形體之基體側的鉬原子 存在量Taatm與碳原子存在量之原子數比Catm/Taatm，及 相反側（形成·以樹脂爲主成分之保護層側）之原子數比 Cat m/ Taatm 時，各爲 0.46 〜0.69 與 1.29 〜3.50。 (比較例1) 除沒有形成以樹脂爲主成分之保護層外，與實施例1相 同地製得厚度200 μιη之鉬金屬粉末分散液A的乾燥塗膜（多 孔質體形成層）。 使所使所得電解電容器陽極元件用之附有基體的成形 體截面影像如第8圖所示。 此外，該碳原子與鉅原子之圖示數據如第13A、13B圖 -28- 200400526 所示。而且，圖示數據之作成以與實施例1相同的測定條 件進行。 而且，電解電容器陽極元件用成形體之基體側的鉬原子 存在量Taatm與碳原子存在量之原子數比Catm/Taatm，及 相反側之原子數比Catm/Taatm時皆爲0.60〜0.75。 (電解電容器陽極元件之製作） (實施例5) 使用上述實施例1、2所得附有基體之成形體，如下所 述製造電解電容器陽極元件。 換言之，使成形體與PET(基體）使用狹縫器狹縫化成寬 度3.6 m m，捲繞成捲軸狀。 然後，使捲成捲軸狀之成形體自PET剝離伸長成直線狀 後，裁成3.6 X 4.4mm大小之晶片狀。另外，使直徑0.2mm 導線之前端部分加壓，夾住扁平化的扁平導線之扁平部分 重疊，製作如第5圖所示形狀之電解電容器陽極元件用成 形體元件1 5。 其次，使電解電容器陽極元件用成形體元件1 5在6.6 X l〇-3Pa(5xlCr5Torr)真空中昇溫至350 °C，加熱處理 90分 鐘，進行有機物質（黏合劑）之分解•除去，另在1 3 00 °C下 進行燒結處理20分鐘，製得如第6圖所示在薄型直方體形 狀鉅多孔質體燒結體1 7內埋入扁平導線1 3之扁平部分1 3 a 構造的鉬電解電容器用陽極元件1 8。 爲使藉由該以樹脂爲主成分之保護層賦予較強的強 度，電解電容器陽極元件用成形體進行狹縫化，使基體剝 離、且拉伸成直線狀裁斷，另在使導線以夾子加壓等之加 -29- 200400526 工步驟中纏繞、且賦予於切斷時之衝擊，即使施予與導線 一體化時之壓力時，仍維持捲軸狀或晶片狀之形狀，加工 性極佳。而且，由於可連續由捲軸狀成形體製作電解電容 器陽極元件用成形體元件，電解電容器陽極元件用成形體 元件及電解電容器陽極元件之生產效率極佳。 (比較例2) 使用以上述比較例1所得的電解電容器陽極元件用成 形體’與上述實施例2相同地製造電解電容器陽極元件。 然而，使PET剝離後，成形體之形狀變形、無法加工。 藉由此等結果可知，與比較例相比可確知，本發明之實 施例中金屬粉末分散液中使用的黏合劑樹脂量很少，燒結 後之殘留碳量減少，電解電容器陽極元件用成形體之加工 性極佳，生產性提高。 產業上之利用價値 於本發明中藉由以樹脂爲主成分之保護層賦予強度，故 多孔質體形成層中所含的黏合劑樹脂量減少，燒結後之殘 留碳量降低，可提供加工性極佳的成形體。 而且，爲保護上述閥作用金屬之以樹脂爲主成分的保護 層，由於配置於成形體表層，於燒結時可容易地除去碳。 因此，使用於電解電容器用陽極元件時’可製作加工性佳 且外漏電流情形少的具有良好電氣特性之電解電容器陽 極元件。 ㈤圖式簡單說明 第1圖係爲本發明附有基體之成形體的製法例，爲在基 體上設有保護層、多孔質體形成層狀態之截面圖。 -30- 200400526 第2圖係爲於第1圖所示附有基體之成形體中，在基體 與保護層（以樹脂爲主成分的層狀領域）之界面上引出剝離 時狀態的截面圖。 第3圖係爲於本發明附有基體之成形體中，於含有保護 層與多孔質體形成層具有相溶性之樹脂例中，表示此等一 體化狀態之截面圖。 第4圖係爲在與多孔質體形成層之基體相反面上形成 保護層例的附有基體之成形體截面圖。 第5圖係爲說明本發明電解電容器陽極元件之製法例 圖，在2張片間夾住扁平導線所得的成形體元件之斜視 圖。 第6圖係爲使電解電容器陽極元件用成形體元件燒，結 所得的電解電容器陽極元件之斜視圖。 第7圖係爲使用本發明電解電容器陽極元件所得的電 解電容器之簡略圖。 第8圖係爲實施例1之附有基體的成形體截面之SEM 影像。 第9A、9B圖係各爲第8圖所示截面之碳原子與鉅原子 之圖示數據圖。 第10圖係爲實施例2之附有基體的成形體截面之SEM 影像。 第11圖係爲第10圖所示截面之碳原子圖示數據圖。 第12圖係爲比較例1之附有基體的成形體截面之SEM 影像。 第13A、13B圖係各爲第12圖所示截面之碳原子與鉅原 子之圖不數據圖。 -31 - 200400526 元件符號簡單說明·_ 1,1’…基體 2…保護層 3，3’…多孔質體形成層 3 a，3a’…閥作用金屬粉末 3b,3b’…黏合劑樹脂 4,4’…成形體 5，5’…多孔質體形成層 6,6,…保護層 ® 7,7’…多孔質體形成層 12…成形體 13…扁平導線 13a···扁平部分 14…成形體 15…成形體元件 17…鉅多孔質燒結體 1 8…陽極元件 β 30…鉅電解電容器 31…電容器元件 32…陰極元件 33…陽極端子 34…焊料 35…熔接部 36…樹脂外裝 -32-The ratio of the presence of Catm to the valve-acting metal atom X, Xatm, a C a tm / X atm, is determined by calculating the calculation ratio of the electronic signal pulse corresponding to each characteristic X-ray. In other words, when the protective layer 2 or 6 is formed, and when the protective layer 2 or 6 is an organic compound mainly composed of a resin, the Catm / Xatm on the substrate 1 side in the molded body 4 is larger than the opposite surface. Catm / Xatm in the protective layer mainly composed of resin is preferably 1.0 or more, more preferably 1.2 or more, and most preferably 1.3 or more. In addition, when the protective layer 2 or 6 is formed, the shape of the molded body 4 (the porous body forming layer 5 or the porous body forming layer 3 and the protective layer 2) can be maintained in the subsequent steps up to the sintering step, and the processing can be improved. It is possible to confirm the existence of the protective layer 2 or 6 by improving the processing suitability of the manufacturing step test. • Second Embodiment Example The second embodiment example uses a metal powder dispersion liquid containing a valve action metal powder, a binder resin, and a solvent on a substrate to form a coating film, and the valve action metal is used in the coating film. A powder forming method in which the resin is deposited on the surface of the coating film (on the opposite side of the substrate) to form a protective layer containing the resin as a main component. For example, as shown in Fig. 4, the same base body as the base body 1 shown in Fig. 1 is shown! The metal powder dispersion liquid containing the valve action metal powder 3'a and the binder resin 3'b is coated to form a coating film 3 ', and the valve action metal powder 3'a is precipitated in the substrate 1' in the coating film 3 '. On the other hand, a protective layer 6 ′ containing a resin as a main component is formed on the surface layer of the coating film 3 ′. Below the protective layer 6 'is a porous body forming layer 7' containing a valve action metal powder as a main component. In addition, the coating film 3 'can be formed using various methods such as a stamp 200400526, in addition to coating the metal powder dispersion liquid. At this time, a resin gradient is formed in the coating film 35 as in the case shown in FIG. 3. In addition, the "gradient gradient of the formation of the binder resin 3" b "results in the formation of a protective layer 6" containing a resin as a main component. In short, the porous body forming layer 5 'is substantially a portion, and a protective layer 6' is formed on the surface. Therefore, even when the substrate 1 ′ is peeled off, the protective body 5 ′ formed on the surface layer of the porous body forming layer 5 ′ in the molded body 4 ′ imparts appropriate strength and reinforcement, so that the effect of improving workability can be obtained. . In order to precipitate the valve action metal to form the protective layer 6 ', it is preferable that the viscosity of the metal powder dispersion is 5 Pa · s or less, and more preferably IPa · s or less. The viscosity can be measured using a B-type viscometer, and the measurement temperature is the temperature during operation. This low viscosity metal powder dispersion is used to form a porous body by a general method. During the layer formation, for example, until the metal powder dispersion is applied and dried, the valve action metal powder is gradually precipitated, and a resin and a valve action are formed. Metal powder concentration gradient. As long as the porous body-forming layer 5 is used in this embodiment, the coating material can be formed. 'By adjusting the viscosity at the time of coating, a protective layer 6 can be formed as a result, and the type of materials or manufacturing steps are relatively simple. . In the first or second embodiment, for example, as shown in FIG. 2, before the base is peeled off during processing, the molded body 4 shown in FIG. I and the base 1 are slit into a predetermined width at the same time. For example, it can significantly improve the subsequent continuous processability of the formed body for the anode element for the electrolytic valley device, so it is preferable. In addition, it is preferable because no wasted part called ear is generated during the removal process. In addition, when the metal powder dispersion is applied to the first layer 2, it is applied in a strip shape, dried, and cut into a coated shape. -15- 200400526 In the following, 'the structure and manufacturing sequence used for the molded body with a base to be described in the above-mentioned manufacturing process will be described in detail. (Preparation of substrate) Materials that can be used as sheet substrates, such as polyethylene film, polypropylene film, polyvinyl chloride vinyl film, polyvinyl chloride vinyl film, polyethylene terephthalate film, polyvinyl alcohol Plastic film or sheet made of film, polyethylene terephthalate (PET) film, polycarbonate film, nylon film, polystyrene film, ethylene vinyl acetate copolymer film, ethylene vinyl copolymer film, etc. Or metal sheets such as aluminum; paper, impregnated paper; composites of these materials. Among these, in consideration of adhesiveness and releasability, it is more preferable to use a combination of a resin or the like for forming a layer on a substrate. Materials other than these are not particularly limited as long as they have the necessary strength, flexibility, and good peelability. Particularly in terms of strength, solvent resistance, price, etc., PET films are generally used. The thickness of the substrate is not particularly limited, for example, 5 μm to 500 μm, and more preferably 10 μm to 100 μm. The substrate may be a peelable substrate when the interface between the substrate and the molded body is easily peeled. The peelable substrate is, for example, one in which the film-like material constituting the substrate has peelability itself, or one in which a release layer is formed on the surface of the film-like material. Moreover, when the side surface of the base body of the molded body is peelable from the base body, it can be processed smoothly without using a peelable base body. As described below, for example, when a PET film is used as a substrate, the first layer can be peeled off from the substrate by forming a first layer coated with an acrylic resin, a polyvinyl acetal resin, or the like as a main component on the substrate. Sex is good. (Formation of a protective layer containing a resin as a main component) -16- 200400526 The resin used for the protective layer depends on the manufacturing method and the like. In terms of releasability from PET, polyvinyl alcohol resin, polyvinyl acetal, and butadiene can be used. Acetal resin, acrylic resin, etc. It is therefore preferable to include one or more resins selected from these. Among them, acrylic resin is more preferable in terms of reducing the amount of residual carbon. In addition, when a metal powder dispersion is used as shown in FIG. 4, when the valve action metal powder is precipitated to form a resin-based protective layer, the valve action metal powder is used as a binder resin to form the protective layer. field. In this case, it is preferable to use the resin exemplified above as the binder resin. Among these resins, especially when an acrylic resin and metal powder are stored and sintered, they tend to be completely burned, and therefore a porous metal sintered body having a small amount of residual carbon is easily formed. In addition, 'the protective layer as the i-th layer and the porous body forming layer as the second layer are sequentially provided on the sheet-like substrate as described above, and the adhesion strength between the protective layer and the porous body-forming layer is higher than that of the sheet-like substrate. When the adhesive strength with the protective layer is large, the adhesive strength must be set under such conditions. The adhesion strength is changed by various conditions such as the resin type (resin compatibility) and coating speed of each layer. It is tested and evaluated under actual manufacturing conditions, and it is better to select those that can satisfy the better characteristics. Although not particularly limited, for example, when using a pET film on a substrate, the following resins may be combined. Combine the first layer (protective layer): acrylic resin, the second layer (porous body-forming layer): the same kind of acrylic resin as the first layer, or the combined first layer (protective layer): polyvinyl acetal resin, With the second layer (porous body-forming layer): acrylic resin. Furthermore, when using the same kind of tree-17-200400526 grease as the protective layer on the porous body forming layer, the interface between the protective layer 2 and the porous body forming layer 3 disappears due to compatibility, as shown in FIG. 3, And the concentration gradient of the resin is formed. Since the interface disappears, the first layer and the second layer are integrated, and no peeling occurs between the layers, so it is desirable. However, as the solvent in the coating liquid used to form the porous body forming layer dissolves the resin in the resin-based protective layer, the greater the possibility that the thickness of the resin-based protective layer itself becomes thinner. The greater the sex. The resin used for this purpose preferably contains a component having a molecular weight of 250,000 or more, and more preferably contains the above-mentioned component having a molecular weight of 250,000 or more in an amount of 30% by mass or more of the entire resin. The protective layer containing a resin as a main component can be formed on the sheet-like substrate 1 using various methods, as shown in the first example. The coating method is, for example, a conventional roll coating method, and specifically, for example, an air doctor blade coating method, a doctor blade coating method, a batch coating method, an extrusion coating method, an air knife coating method, an extrusion coating method, Impregnation coating method, reversible roll coating method, conversion roll coating method, groove roll coating method, contact coating method, casting coating method, spray coating method, and the like. Moreover, a solution in which an appropriate resin is dissolved at an appropriate concentration can be used at this time. As the solvent, the same solvents as the solvents and the like constituting the metal powder dispersion liquid described below can be used. The thickness of the protective layer containing a resin as a main component is difficult to specify because the protective layer itself has various forms. However, it is not required to limit the area of the molded body until the sintering starts, and the shape can be maintained. . For example, 1 μm to 20 μm is preferred, as long as it is within this range, it will not increase the total amount of resin in the molded body, nor will it increase the amount of carbon remaining after sintering. In particular, the range of 1 μm to 10 μm has a small effect on the amount of residual carbon after sintering, and the strength of the coating film can be appropriately maintained, so it is preferable. (Formation of porous body forming layer) The metal powder dispersion liquid constituting the porous body forming layer can be made by mixing and dispersing the valve action metal powder, the binder, and the solvent with additives as necessary. • Valve-acting metal powder The valve-acting metal powder can be powder of valve-acting metal such as giant, aluminum, niobium, and titanium. Of these valve-acting metals, giants and niobium are preferred, and those that are more preferred are giants. Examples of molybdenum metal powder are described below. The purity of the molybdenum metal powder is preferably 99.5% or more, and the average primary particle diameter is preferably 0.01 to 5.0 μm, and more preferably 0.01 to 2.0 μm. _ • Binder Resin A solvent-soluble binder resin can be used as the binder resin. Suitable for binder resins such as polyvinyl alcohol resin, polyvinyl acetal resin, butyral resin, phenol resin, acrylic resin, urea resin, vinyl acetate emulsion, polyurethane resin, polyvinyl acetate resin, ring Oxygen resin, melamine resin, oxide resin, nitrocellulose resin, natural resin, etc. These resins can be used alone or in combination of two or more. In addition, in the above resin, as in the case of the protective layer mainly comprising a resin, a polyvinyl alcohol resin, a polyvinyl acetal resin, a butyral resin, an acrylic resin, or the like can be used. Among them, when the acrylic resin is treated with a binder in a vacuum, it is almost completely decomposed, and the amount of residual carbon is small. In particular, when an anode element for an electrolytic capacitor is manufactured from a molded body, the leakage current outside the electrolytic capacitor can be prevented from increasing. 19- 200400526 Plus, so it's an aspiration. The glass transition point of the above resin is preferably below 50 ° C, and more preferably below room temperature. When the right is 50C or lower ', as shown in Figs. 1 and 2, since the porous body forming layer 3 can be made flexible and the formed body is not easily broken, it is desirable to improve the processing. In addition, the description of the "adhesive resin" means that the above-mentioned resin-based protective layer is appropriately selected in order to satisfy the relationship of adhesive strength. When the amount of the binder resin used is, for example, giant metal powder, it is preferably 0.01 to 30 parts by mass based on 100 parts by mass, and more preferably 0.01 to 15 parts by mass. If the amount of the binder resin is too large, the residual carbon content after sintering increases. For example, when an anode element for an electrolytic capacitor is manufactured from a molded body, disadvantages such as a decrease in capacitor characteristics may occur. • Solvent solvents such as water, or alcohols such as methanol, 2-propanol (isopropanol), diethylene glycol, etc .; Cellosolvents such as methyl cellosolve; acetone, methyl ethyl ketone, isophor Ketones, such as ketones; Ammoniums, such as N, N-dimethylformamide; Esters, such as ethyl acetate; Ethers, such as dioxane; Chlorine solvents, such as methyl chloride; Toluene, two Aromatic hydrocarbons such as toluene; etc. These solvents can be used alone or in combination of two or more. The amount of the solvent used is set within a range in which the step of applying the metal powder dispersion liquid can be smoothly performed. In addition, in addition to the above-mentioned molybdenum metal powder, binder resin, and solvent, the metal powder dispersion used has the best physical properties when the metal powder dispersion is coated or printed on the surface of the substrate, and the metal powder is stably maintained. For the purpose of -20-200400526 powder or fluidity, you can add various appropriate additives. Suitable additives include, for example, dispersants such as paraphthalates, phosphates, and fatty acid esters, plasticizers such as alcohols, low boiling point alcohols, defoamers such as polysiloxanes and non-polysiloxanes, and silane coupling agents. , Titanium coupling agents, dispersants such as quaternary ammonium salts, etc. In particular, by using fatty acid esters having a melting point of 3 ° C or less, the workability of the formed body formed from the metal powder dispersion liquid is improved, so that the part of the formed body is not easily broken or lacking during processing. The amount of these additives used For example, in the case of molybdenum, 0.01 to 5.0 parts by mass is preferable for 100 parts by mass of metal powder. __Method for adjusting metal powder dispersion liquid The above-mentioned valve action metal powder, solvent, solvent-soluble binder resin, and Depending on the additives to be blended, they can be added simultaneously or sequentially, and dispersed by using various melting and dispersing machines. Kneading and dispersing can be carried out using roller type kneaders, vertical kneaders such as mixers, two rolls, and three rolls. Machine, pressure kneader, planetary gear mixer, etc. blade type kneader, ball type rotary mill, sand mill and other dispersers, ultrasonic dispersers, nano-dispersers, etc. The mixing example illustrates the mixing ratio of the valve-acting metal powder dispersion liquid. For example, the binder resin is 0.01 to 30 parts by mass (preferably for 100 parts by mass of metal powder). It is 0.0 1 to 15 parts by mass), the solvent is 5 to 160 parts by mass, and the additive is 0 to 5 parts by mass. In addition, the viscosity of the valve-acting metal powder dispersion is 1 to 100 OPa · s, and 5 to 100 Pa · s In addition, when the valve-acting metal dispersion is coated on the substrate and the valve-acting metal is precipitated, a protective layer containing a resin as a main component is formed on the surface of the porous body forming layer-21- 200400526. The viscosity of the valve action metal powder dispersion is preferably 5 P a · s or less, and more preferably 1 P a · or less. The viscosity measurement method is performed by a B-type viscometer, and the measurement temperature is the temperature during operation. • Anode The formation of the formation layer is such that the thus-obtained valve-acting metal powder dispersion is applied to the substrate depending on the method used. For example, as shown in FIG. 1, a protective layer 2 is formed on the sheet-like substrate 1 shown above, and then the protective When the metal powder dispersion is coated and dried on the layer 2, a porous body forming layer 3 can be obtained. As a result, a porous body forming layer 3 and a protective layer 2 mainly containing a resin can be obtained as a result.的 shaped body 4. Valve action metal powder The coating method of the dispersion liquid can be variously applied in the same manner as the above-mentioned peeling layer. The valve action metal powder dispersion liquid is dried to use 40 ~ 12 (hot air of TC is preferred, and the solvent in the dispersion liquid can be volatilized. After the solvent is volatilized, the formed body and the substrate can be wound into a roll shape. In other words, when the first layer having a function as a protective layer exists, the formed body is broken and the substrate cannot fall off even if it is rolled into a roll shape. Therefore, The coated molded body can be used as a substrate and rolled up, and a molded body can be formed on the substrate by a continuous coating step. The thickness of the molded body 4 can be set locally, but the sintered body is used to form a porous anode for electrolytic capacitors. At this time, the electrostatic capacity required as an electrolytic capacitor can be appropriately set until the thickness of the coating material (thickness when wet) of the metal powder dispersion before drying is several μm to 300 μm. Generally, in order to produce an electrolytic capacitor anode element corresponding to a thin electrolytic capacitor, the dry thickness of the porous body-forming layer is preferably less than 0.5 mm and a film thickness of -22-200400526. In addition, a dry thickness of 0.4 mm or less is preferred from Liu Du ^ ^ ^ ^ μ, more preferably 0.3 to 0.05 mm, and most preferably 0.2 to 0.05 mm. (Slit formation operation) • Slit formation method Then, for example, the formed body 4 shown in FIG. 1 is preferably slit with the sheet-like base body 1 to a predetermined width. The narrowing method, such as a laser cutting method, a common cutting method in which the movement between a knife and a roller uses a shearing action, and the like, may be any method known in the art. The cutting accuracy can be a common cutter, so that when the thicker is cut, the cutter can be cut at the same time. In addition, slitting can also be performed using rolling cutting with each blade. In addition, the above-mentioned metal dispersion liquid may be coated in a strip shape on the second layer 2 as shown in Fig. 1, dried, cut into a coated shape, and then rolled into a roll shape. In the case of coating in a strip shape, the slit must be formed into a coating shape after drying. The slitting can be performed in the same manner as described above. The molding system obtained in this manner is formed uniformly on the substrate, and has a narrow film thickness distribution, excellent flexibility, and flexibility. Therefore, it can be easily rolled into a sheet-like substrate and a reel-like shape without causing positional separation. After forming the slit, the formed body for a sintered body wound into a roll shape is excellent in storage properties and transportability. (Production of electrolytic capacitor anode element) Using the formed body of the present invention produced by the above method, an electrolytic capacitor anode element can be manufactured. The specific method is shown below. The anode element for an electrolytic capacitor using the formed body of the present invention can be produced, for example, as follows. First, after the formed body is peeled from the substrate and cut to a desired length, a flat part of a wire or a preferred flat wire 13 is placed thereon as shown in Fig. 5-23- 200400526 1 3 a, and other parts are formed. The bodies 14 are overlapped, and appropriate processing is applied as necessary, and the two shaped bodies 12, 14 and the flat lead 13 are formed into a shaped body element 15 for an anode element of an electrolytic capacitor (a simplified form of the element 15 below). The slit width sandwiches the lead wire, and is adjusted in advance in accordance with the width of the anode element produced by the pressure treatment. After the slit is formed, the body is not cut to a certain length, and a desired size of the electrolytic element can be obtained. body. When this method is compared with a method of forming a molded body from a sheet having the same width as a sheet, it is possible to mass-produce good production efficiency because no unnecessary shape is formed. When the molded article of the present invention is a protective layer having a main component for protecting the porous body forming layer, the above-mentioned slits or the slits are damaged when wound up and detached from the substrate, and are liable to be broken during the pressurization process by sandwiching the wires. Shaped body. The flat wire is formed of a valve-acting metal (for example, a giant), and a part or the whole of the anode element is formed in a flat shape. The flat conductor is produced by press-forming and flattening at least a part of the giant wire. The thickness and width of the flat portion are appropriately set in consideration of the thickness and strength of the anode element to be manufactured, and the flat portion is preferably formed into a thickness of 5 to 70%. _ • Sintering step Then, the above-mentioned molded body for electrolytic capacitor anode element 3 is appropriately dried, and the organic matter (binder) is removed in a vacuum at about 300 ~ 600 ° C, and another about 10 ~ Approx. 1 200 ~ 1 600 t: High-temperature heat treatment (sintering). By using proper pressure and close contact, the electrolytic capacitor of the shaped body can only form the anode body of the forming container into a resin body. Will be embedded at least by, for example, the degree of flat wire, the thickness of the wire body 5 pieces 15 heat treatment for 30 minutes, the group of metal powder 200400526 and the giant metal powder and the wire (preferably flat wire 1 3) By melting, a tantalum electrolytic capacitor anode element 18 having a structure in which a lead 13 (preferably a flat portion 13a of a flat lead) is embedded in a thin square giant porous sintered body 17 as shown in FIG. 6 can be obtained. The anode element 18 for a giant electrolytic capacitor thus obtained is in a state in which the giant porous sintered body and the lead wire 13 are firmly bonded. (Production of Electrolytic Capacitor) The anode element 18 for the giant electrolytic capacitor is used. When the molybdenum electrolytic capacitor is manufactured, the anode element is placed in an electrolyte tank, and a predetermined DC voltage is applied to the anode element to perform chemical conversion treatment. A dielectric film of molybdenum oxide is formed on the surface of the element 18. After the oxide film is formed, a solid electrolyte including a manganese dioxide film or a functional polymer film is formed thereon. The capacitor element 31, which forms a tantalum oxide film, a manganese dioxide film, or a functional polymer film, is formed as described above, and a carbon (graphite) layer and a silver paste layer are formed. For example, as shown in FIG. 7, on the surface of the capacitor element 3, One side of the cathode terminal 32 is joined with the solder 34, and the front end portion of the flat wire 丨 3 is joined to the anode element 33 by spot welding (denoted by the symbol 35), for example, by resin molding or immersion in a resin solution Medium forming and the like are carried out with a resin case 36 to form a giant electrolytic capacitor. The manufacturing method of the present invention can also be used for manufacturing a multilayer electrolytic capacitor. This multilayer electrolytic capacitor is an extremely thin multilayer electrolytic capacitor manufactured by the method of the present invention, and is formed by connecting it. Examples The present invention will be described in detail in the following examples. (Adjustment of Molybdenum Metal Powder Dispersion Liquid) -25- 200400526 The following two kinds of complexes were added to a 100cc poly bottle and mixed, and the mixture was refined for 1 hour using a shaker to obtain Molybdenum Metal Powder Dispersions A and B. Dispersion A: • 50 g of molybdenum metal powder having an average primary particle size of 0.5 μm, • 6.0 g (2.5 g) of acrylic resin "NCB-166" (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) as a binder resin (( ) Is the solid content), • 5.5 g of mixed solvent of cyclohexanone and toluene as the solvent, and 50 g of a 3 mm steel ball Dispersion B: • 50 g of giant metal powder with an average primary particle diameter of 0.5 μm, • as a binder Acrylic resin "NCB-166" (manufactured by Dainippon Ink Chemical Industry Co., Ltd.) 6.02 (2.5 £) (solid content in ()), • mixed solvent of cyclohexanone and toluene as a solvent 1 2.9 g and 50 mm steel balls (production of a molded body for an anode element of an electrolytic capacitor) (Example 1) An acrylic resin "IB-30" (Fujikura Kasei Co., Ltd.) was made on a 50 μm thick PET film as a substrate. System components: isobutyl methacrylate weight average phenol content: 200,000 to 300,000), toluene solution with a solid content ratio of 20% by mass is developed with # 16 sliding sheet, and a protective layer with a thickness of 4 μm is provided. Then, the giant metal powder dispersion liquid A was developed on the first layer with a coater having a depth of 45 μm to prepare a dry coating film (porous body-forming layer) of the molybdenum metal powder dispersion A having a thickness of 200 μm. A cross-sectional image of the obtained molded body with a substrate for an anode element of an electrolytic capacitor is shown in Fig. 8. -26- 200400526 It can be seen from this image that because the binder resin containing the porous body forming layer and the resin used in the protective layer are compatible, part of the protective layer and the porous body forming layer have no interface, and the resin concentration can be obtained. A cross section of a molded body for an anode element of an electrolytic capacitor having a high protective layer containing a resin as a main component. In addition, the graph data of the carbon atom and the giant atom are shown in Figs. 9a and 9B, respectively. The data shown in the figure are the carbon number K-line and giant L-line measured by SEM-EDS. The detector is made by EDX and measurement conditions other than Time constant are performed by EDX's standard measurement conditions. Furthermore, the ratio of the number of atomic atoms Taatm to the amount of carbon atoms present in the matrix side (formed with a resin-based protective layer) of the formed body of the electrolytic capacitor anode element was measured by SEM-EDS, and the reverse was Catm / Taatm and vice versa When the atomic ratios on the sides are Catm / Taatm, they are 1.49 to 3.50 and 0.65 to 0.73, respectively. (Example 2) Except the use of an acrylic resin having a weight average molecular weight of 23 to 290,000 with 75 mass% of the same constituents as "IB-30" and a molecular weight of 7 to 9 with the same constituents as 25 mass% of "IB-30" Except for the acrylic resin used as the first layer of Wanzhi acrylic resin, the surface Catm / Taatm of the base body side and the base body and the opposite side of the formed body were measured in the same manner as in Example 1, and each was 1.25 to 1.41, 0.64 to 0 · 74. (Example 3) Except the use of 50% by weight of the same constituent components as "IB-30", the weight average molecular weight was 230,000 to 290,000 acrylic resins, and the molecular weight of the same constituent components as 50% by weight "IB-30" was 7 to 9 Except for the acrylic resin used as the first layer of Wanzhi acrylic resin, when measuring the Catm / Taatm on the surface of the substrate and -27- 200400526 on the substrate and the opposite side in the same manner as in Example 1, each was 1.08 ~ 1. .28, 0.37 to 0.42. (Example 4) On a PET film having a thickness of 50 μm as a substrate, the giant metal powder dispersion liquid B was developed with an applicator having a depth of 45 μm to obtain a dried giant metal powder dispersion B having a thickness of 200 μm. Coating film. A cross-sectional image of the obtained molded body with a substrate for an electrolytic capacitor anode element is shown in Fig. 10. From this image, it can be seen that since the binder resin containing the porous body forming layer and the resin used in the protective layer are compatible, part of the protective layer has no interface with the porous body forming layer, and a resin having a high resin concentration can be obtained. Cross section of a molded body for an anode element of an electrolytic capacitor with a protective layer as a main component. In addition, the graph data of this carbon atom is shown in FIG. The graph data was created under the same measurement conditions as in Example 1. In addition, the ratio of the number of molybdenum atoms Taatm to carbon atoms present on the substrate side of the molded body for electrolytic capacitor anode elements is Catm / Taatm, and the number of atoms on the opposite side (the side of the protective layer containing resin as the main component) The ratios of Cat m / Taatm are 0.46 to 0.69 and 1.29 to 3.50 respectively. (Comparative Example 1) A dry coating film (porous body-forming layer) of a molybdenum metal powder dispersion liquid A having a thickness of 200 µm was prepared in the same manner as in Example 1 except that a protective layer mainly composed of a resin was not formed. A cross-sectional image of the molded body with a substrate for the obtained electrolytic capacitor anode element is shown in Fig. 8. In addition, the graphic data of the carbon atoms and giant atoms are shown in Figures 13A and 13B in Figure -28- 200400526. The graph data was created under the same measurement conditions as in Example 1. Furthermore, the ratio of the number of atoms of molybdenum Taatm to the amount of carbon atoms present on the substrate side of the formed body for electrolytic capacitor anode elements is Catm / Taatm, and the ratio of the number of atoms on the opposite side is Catm / Taatm is 0.60 to 0.75. (Production of anode element for electrolytic capacitor) (Embodiment 5) An anode element for electrolytic capacitor was produced as described below by using the molded body with a substrate obtained in Examples 1 and 2 above. In other words, the molded article and PET (substrate) were slit into a width of 3.6 mm using a slitter and wound into a roll shape. Then, the formed article rolled into a reel shape was peeled from PET and stretched into a linear shape, and then cut into a wafer shape having a size of 3.6 × 4.4 mm. In addition, the front end portion of the 0.2 mm diameter wire was pressurized, and the flat portions of the flattened flat wire were sandwiched to overlap to produce a shaped body element 15 for an electrolytic capacitor anode element having a shape as shown in FIG. 5. Next, raise the temperature of the molded body element 15 for electrolytic capacitor anode elements to 350 ° C in a 6.6 X 10-3 Pa (5xlCr5Torr) vacuum, and heat treatment for 90 minutes to decompose and remove organic substances (binders). The sintering treatment was performed at 1 3 00 ° C for 20 minutes to obtain a molybdenum electrolysis with a flattened portion 1 3 of a flat wire 1 3 embedded in a thin rectangular parallelepiped sintered body 17 as shown in FIG. 6. Anode element for capacitor 18. In order to provide a strong strength with the resin-based protective layer, the molded body for the anode element of the electrolytic capacitor is slit, the substrate is peeled off and stretched into a linear shape, and the lead wire is clamped. The addition of pressure is -29- 200400526. It is wound in the process and is given an impact at the time of cutting. Even when pressure is applied when it is integrated with the wire, it still maintains the shape of a reel or wafer, which has excellent processability. Furthermore, since a molded body element for an electrolytic capacitor anode element can be continuously produced from a rolled shaped body, the production efficiency of a molded body element for an electrolytic capacitor anode element and an electrolytic capacitor anode element is excellent. (Comparative Example 2) An electrolytic capacitor anode element was produced in the same manner as in Example 2 above using the formed body for an electrolytic capacitor anode element obtained in Comparative Example 1 above. However, after the PET is peeled off, the shape of the formed body is deformed and cannot be processed. From these results, it can be confirmed that compared with the comparative example, the amount of the binder resin used in the metal powder dispersion liquid in the examples of the present invention is small, the amount of residual carbon after sintering is reduced, and the molded body for electrolytic capacitor anode elements Excellent processability and improved productivity. The industrial utilization value in the present invention is to provide strength with the protective layer mainly composed of resin, so the amount of the binder resin contained in the porous body forming layer is reduced, the amount of residual carbon after sintering is reduced, and processability can be provided. Excellent shaped body. Further, in order to protect the above-mentioned valve-acting metal with a resin-based protective layer, since it is arranged on the surface layer of the molded body, carbon can be easily removed during sintering. Therefore, when used in an anode element for an electrolytic capacitor, an electrolytic capacitor anode element having good electrical characteristics with good processability and less external leakage current can be produced. ㈤ Brief Description of Drawings Fig. 1 is a cross-sectional view showing a method for manufacturing a molded body with a substrate of the present invention, and a state in which a protective layer and a porous body-forming layer are provided on the substrate. -30- 200400526 Figure 2 is a cross-sectional view showing the state when the substrate is peeled off from the interface between the substrate and the protective layer (the layered area mainly composed of resin) in the molded body with the substrate shown in Figure 1. Fig. 3 is a cross-sectional view showing such an integrated state in an example of a resin having a compatibility between a protective layer and a porous body-forming layer in a molded body with a substrate of the present invention. Fig. 4 is a cross-sectional view of a molded body with a substrate in which a protective layer is formed on the surface opposite to the substrate of the porous body forming layer. Fig. 5 is a perspective view illustrating a method for manufacturing an anode element of an electrolytic capacitor according to the present invention, and a perspective view of a molded body element obtained by sandwiching a flat wire between two sheets. Fig. 6 is a perspective view of an electrolytic capacitor anode element obtained by firing a molded body element for an electrolytic capacitor anode element. Fig. 7 is a schematic diagram of an electrolytic capacitor obtained by using the anode element of the electrolytic capacitor of the present invention. FIG. 8 is a SEM image of the cross section of the molded body with a substrate in Example 1. FIG. Figures 9A and 9B are diagrammatic data diagrams of carbon atoms and giant atoms each in the cross section shown in Figure 8. FIG. 10 is a SEM image of the cross section of the molded body with a substrate in Example 2. FIG. Fig. 11 is a graph showing carbon atom data of the cross section shown in Fig. 10. FIG. 12 is a SEM image of a cross section of a molded body with a substrate in Comparative Example 1. FIG. Figures 13A and 13B are each a graph of carbon atoms and giant atoms with cross sections shown in Figure 12 and are not data figures. -31-200400526 Simple explanation of component symbols · _ 1,1 '... substrate 2 ... protective layer 3,3' ... porous body forming layer 3a, 3a '... valve action metal powder 3b, 3b' ... adhesive resin 4, 4 '... formed body 5,5' ... porous body forming layer 6,6, ... protective layer® 7,7 '... porous body forming layer 12 ... formed body 13 ... flat wire 13a ... flat part 14 ... formed Body 15 ... formed body element 17 ... giant porous sintered body 1 8 ... anode element β 30 ... giant electrolytic capacitor 31 ... capacitor element 32 ... cathode element 33 ... anode terminal 34 ... solder 35 ... welding portion 36 ... resin case -32 -