200900531 九、發明說明： 【發明所屬之技術領域】 本發明關於一種製備具有優異導電性之經鍍覆粉末的無電方 法。更具體地，本發明關於一種製備導電粉末之方法，其係於作 為一核心的樹脂粉末上形成一導電之過渡金屬鍍覆層，接著實施 無電置換金鍍覆。其中，係於酸性狀態下藉由置換反應將過渡金 屬鍍覆粉末鍍覆金，接著於鹼性狀態下添加還原劑以實施沉積金 鍍覆以形成一微小且均質的金鍍覆層，同時抑制過量鎳之析離。 依據該方法，經連接至一微電路之導電球的顆粒具有絕佳導電 性、高可靠性、且顆粒間的電阻偏差很小。 【先前技術】 具備導電性的樹脂微粒材料廣泛地用作一防止電子裝置或其零 件之靜電力、電波之吸收、電波之屏蔽等等的輔助材料。近來， 經鍍覆的顆粒係用作電性連接電子儀器之微部件的導電材料，包 含液晶顯示面板的電極與操作用之LSI晶片之電路基板的連接， 及微間距中電極接頭間的連接。 製備經鍍覆粉末的傳統方法已包含一種於樹脂微粒之表面上物 理性地塗佈金屬顆粒的方法（日本專利第丨994_267328號申情 案）、一種於基礎微粒之表面上併入細粉末化金屬突出的方法（曰 本專利第2GG3-253465號中請案）等等。近來，較佳係使用藉由 無電鍍覆法以製備經鍍覆粉末的方法（日本專利第2〇〇4_238973〇 號、第2004-265731號、及第2003-197028號申請案等等）。 利用無電鍍覆法的傳統技術包含經由無電鍍覆法鍍覆鎳為具有 6 200900531 80奈米至120奈米厚度之薄膜的鎳鍍覆層（以下稱作「初級鍍覆 層」）；隨後利用置換鍍覆法進行金鍍覆^根據該方法，係使用一 錯合劑以促進鎳之分解反應並將經分解之鎳離子溶解於鍍覆液中 (日本專利第 2003-277942 號、第 2003-147542 號及第 2003-293147 號申請案）。然而，當該置換金鍍覆反應進行時，該薄初級鍍覆層 之金屬層可能會被完全或部分的過量析離破壞，或者會產生微小 的針孔，以至於該鍍覆層會容易自該樹脂粉末剝離，或於將該層 壓縮至一基材或一電極終端時，在該樹脂粉末及該鍵覆層之間發 生剝離，從而導致導電性降低之問題。 為了克服該問題’習知技術嘗試使用一析離抑制劑以便在酸性 PH範圍為4至6之置換鍍覆反應中，防止鎳鍍覆層之過量析離（日 本專利第 2005-307309 號、第 1993-222542 號及第 1993_331655 號 申請案）。當使用一析離抑制劑時，金鍍覆係被抑制以致不能輕易 地獲得所欲的厚度，且難以獲得一均勻的金鍍覆層。此外，因為 析離之抑制及過量析離之抑制，欲鍍覆金至一所欲厚度，所使用 的金量將會增加，從而增加生產成本。當連接至—微電路時，由 此所製備之作為導電粉末的導電球可能會引起高連接電阻或短 路。由於析離抑制劑包含還原劑，可能會產生如於長時間使用該 鍍覆液期間的穩疋性退化的缺點’以及在該初級錢覆層中抑制微 孔的困難。因此，在微電路的連接上，依據習知技術所製造的導 電球缺乏可靠性，且導電球之顆粒間具非常大的電阻偏差。 近來，隨著電子儀器及電子零件的小型化之急速進展，以及基 材上的微佈線等等，使得具有高度優異導電性的導電粉末是必須 7 200900531 的0 【發明内容】 [技術問題] 本發明人做了大量研究以開發具有優異導電性的導電粉末，而 結果他們發現一種方法，其中係在置換金鍍覆之早期階段，於酸 性狀態下藉由置換反應形成一金鑛覆層，且接著在驗性狀態下使 用一特定量之還原劑以進行金鍍覆，藉此形成一微小的金鍍覆層 同時抑制過量鎳之析離，以於連接至一微電路時，藉由個別的導 電球顆粒間之電阻偏差的降低而獲得高可靠性。本發明係基於此 發現而完成。 因此，本發明之目的係提供一種製備經鍍覆粉末的方法，其可 反應一微佈線且在連接時沒有電容量問題的情況下提供高導電性 效能。 為了達到上述目的，本發明提供一種將金鍍覆至金屬鍍覆粉末 上的無電方法，其中可藉由調整pH及添加—還原劑而抑制初級鑛 覆層之塗佈的破壞或微孔的產生。 [技術手段] +本發明關於—種洲置換錢覆溶賴覆金的方法。本發明係 藉由發現-種製備導電粉末的方法而完成，其係以無電形成一過 渡金屬《層於心之表面上’接著形成—金料層於該過渡金 屬鑛覆層之表面上，其中係藉由抑制金屬（用來作為上述過渡金 屬者）之析離㈣整該置換錢覆溶液之阳而形成—微小及均質 的金鑛覆層。 200900531 更具體地，本發明句冬—海:也丨， 、 種製備導電粉末方法，係在無電鍍覆 液中形成一金屬鍍覆層於—作 、 、 作為—核心之樹脂粉末上，盆句含下 列步驟： ^ U)形成-導電過渡金屬層於該核心之表面上； (b) 於置換金錢覆溶液中’藉由分散該導電粉末以實施置換金 鑛覆’其中該導電過渡金屬層業經形成於該導電粉末上；以及 (c) 。周整該置換金鑛覆溶液至驗性狀態，並添加—還原劑以於 該置換金鑛覆層上形成一還原金鍍覆層。 【實施方式】 [最佳模式] 本發明之方法中，欲用作-核心之樹脂粉末的型式並無特殊限 制。可使用之樹脂係選自下列群組之一種樹脂或二或多種樹脂的 混合物：聚烯烴如聚乙烯、聚氣乙烯、聚丙烯、聚苯乙烯及聚異 丁烯；烯烴共聚物如苯乙烯-丙烯腈共聚物及丙烯腈_丁二烯_苯乙 稀二元共聚物；丙烯酸衍生物如聚丙稀酸酯、聚甲基丙烯酸甲略 及聚丙烯醯胺；聚乙烯化合物如聚乙烯基乙酯及聚乙烯醇；越共 聚物如聚縮醛、聚乙二醇、聚丙二醇及環氧樹脂；胺基化合物如 苯基胍胺甲醛（benzoguanamine)、尿素、硫脲（thi〇urea)、二 聚氰胺、乙醯基胍胺甲醛（acetoguanamine)、二氰亞胺及笨胺. 醛樹脂如酚甲醛樹脂、鈀酚甲醛樹脂及乙醛樹脂；聚胺g旨樹脂· 及聚S旨。 根據本發明，樹脂粉末之平均顆粒直徑為0.5微米至1，00〇微 米。如果平均顆粒直徑小於〇.5微米，導電粉末可能不會接觸待連 200900531 接的電極表面，且當電極間有一間隙時會發生不良的接觸。另一 方面，如果直徑大於1，〇〇〇微米，則無法達到微小的導電連接。因 此將平均顆粒直徑限制於上述範圍内，且更佳為1微米至1〇〇微 米，尤佳為2微米至20微米，最佳為3微米至1〇微米。 根據本發明之樹脂粉末的長寬比係小於2，更佳為小於1 2，尤 佳為1.06。如果長寬比大於2,則由於顆粒直徑不是均勾的，因此 當導電微粒於電極之間接觸時，會出現大量未經接觸的顆粒。因 此將長寬比限制於上述範圍内。 該待使用的樹脂粉末具有不大於3〇%之變異係數（Cv)值，較 佳為不大於20%，更佳為不大於5%。如果Cv值超過3〇%，由於 顆粒直徑不均勻，當導電微粒於電極之間接觸時會出現大量未經 接觸的顆粒。因此將該係數限制於上述範圍内。 於本發明_，係藉由下列公式1定義變異係數（Cv): [公式1]200900531 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to an electroless method for preparing a plated powder having excellent conductivity. More specifically, the present invention relates to a method of producing a conductive powder by forming a conductive transition metal plating layer as a core resin powder, followed by electroless gold plating. Wherein, the transition metal plating powder is plated with gold in a acidic state by a displacement reaction, and then a reducing agent is added in an alkaline state to perform deposition gold plating to form a minute and homogeneous gold plating layer while suppressing Excessive nickel separation. According to this method, particles of a conductive ball connected to a microcircuit have excellent conductivity, high reliability, and little resistance variation between particles. [Prior Art] The resin fine particle material having conductivity is widely used as an auxiliary material for preventing electrostatic force of an electronic device or a component thereof, absorption of electric waves, shielding of electric waves, and the like. Recently, the plated particles are used as a conductive material for electrically connecting micro-components of an electronic device, and include a connection between an electrode of a liquid crystal display panel and a circuit substrate of an LSI chip for operation, and a connection between electrode terminals in a fine pitch. A conventional method of preparing a plated powder has included a method of physically coating a metal particle on the surface of a resin particle (Japanese Patent No. 994-267328), and incorporating fine powder on the surface of the base particle. A method of protruding metal (in the case of the patent No. 2GG3-253465) and the like. Recently, a method of preparing a plated powder by electroless plating is preferably used (Japanese Patent No. 2, 238, 973, No. 2004-265731, and No. 2003-197028, etc.). A conventional technique using an electroless plating method includes plating a nickel to a nickel plating layer having a thickness of 6 200900531 from 80 nm to 120 nm by electroless plating (hereinafter referred to as "primary plating layer"); Gold plating by displacement plating method according to the method, a dislocation agent is used to promote the decomposition reaction of nickel and dissolve the decomposed nickel ions in the plating solution (Japanese Patent No. 2003-277942, 2003-147542) No. 2003-293147). However, when the replacement gold plating reaction is carried out, the metal layer of the thin primary plating layer may be completely or partially destroyed by excessive precipitation, or minute pinholes may be generated, so that the plating layer is easy to self-deposit When the resin powder is peeled off or the layer is compressed to a substrate or an electrode terminal, peeling occurs between the resin powder and the key layer, resulting in a problem of lowering conductivity. In order to overcome this problem, the prior art attempts to use a separation inhibitor to prevent excessive deposition of the nickel plating layer in the displacement plating reaction having an acidic pH range of 4 to 6 (Japanese Patent No. 2005-307309, No. Applications 1993-222542 and 1993_331655). When a separation inhibitor is used, the gold plating is suppressed so that the desired thickness cannot be easily obtained, and it is difficult to obtain a uniform gold plating layer. In addition, because of the inhibition of separation and the suppression of excessive separation, it is necessary to plate gold to a desired thickness, and the amount of gold used will increase, thereby increasing production costs. When connected to a microcircuit, the conductive ball prepared as a conductive powder may cause high connection resistance or short circuit. Since the separation inhibitor contains a reducing agent, there may be a disadvantage of deterioration of stability during use of the plating solution for a long period of time and difficulty in suppressing micropores in the primary money coating. Therefore, on the connection of the microcircuit, the conductive ball manufactured according to the conventional technique lacks reliability, and the conductive ball has a very large resistance deviation between the particles. Recently, with the rapid advancement of miniaturization of electronic instruments and electronic components, and microwiring on substrates, etc., it is necessary to have a highly conductive conductive powder. [2009] The content of the invention [Technical Problem] The inventors have conducted extensive research to develop conductive powders having excellent electrical conductivity, and as a result, they have found a method in which a gold ore coating is formed by a displacement reaction in an acidic state in an early stage of replacement gold plating, and Then, a specific amount of reducing agent is used in the verification state to perform gold plating, thereby forming a tiny gold plating layer while suppressing excessive nickel separation, so as to be connected to a micro circuit by individual High reliability is obtained by lowering the resistance deviation between the conductive ball particles. The present invention has been completed based on this finding. Accordingly, it is an object of the present invention to provide a method of preparing a plated powder which is capable of reacting a micro-wiring and providing high conductivity performance without connection problems at the time of connection. In order to achieve the above object, the present invention provides an electroless method for plating gold onto a metal plating powder, wherein the coating of the primary mineral coating or the generation of micropores can be suppressed by adjusting the pH and adding a reducing agent. . [Technical means] + The present invention relates to a method for dissolving gold in a country. The present invention is accomplished by a method for preparing a conductive powder by forming a transition metal "on the surface of the core" without electricity to form a gold layer on the surface of the transition metal ore layer, wherein A small and homogeneous gold ore coating is formed by inhibiting the separation of the metal (used as the transition metal) and the replacement of the cation of the solution. 200900531 More specifically, the method of the present invention is also a method for preparing a conductive powder by forming a metal plating layer in an electroless plating solution on a resin powder as a core. The method comprises the steps of: ^) forming a conductive transition metal layer on the surface of the core; (b) forming a replacement gold deposit by dispersing the conductive powder in the replacement money coating solution, wherein the conductive transition metal layer is Formed on the conductive powder; and (c). The gold ore coating solution is replaced by a replacement state, and a reducing agent is added to form a reduced gold plating layer on the replacement gold ore coating. [Embodiment] [Best Mode] In the method of the present invention, the type of the resin powder to be used as the core is not particularly limited. The resin which can be used is selected from one of the following groups of resins or a mixture of two or more resins: polyolefins such as polyethylene, polyethylene, polypropylene, polystyrene and polyisobutylene; olefin copolymers such as styrene-acrylonitrile Copolymer and acrylonitrile-butadiene-styrene ethylene binary copolymer; acrylic acid derivatives such as polyacrylate, polymethyl methacrylate and polypropylene decylamine; polyethylene compounds such as polyvinyl ethyl ester and poly Vinyl alcohol; the more copolymers such as polyacetal, polyethylene glycol, polypropylene glycol and epoxy resin; the amine compounds such as benzoguanamine, urea, thiureure, melamine , acetoguanamine, dicyanimide and stupid amine. Aldehyde resins such as phenol formaldehyde resin, palladium phenol formaldehyde resin and acetaldehyde resin; polyamine g for resin · and poly S. According to the present invention, the resin powder has an average particle diameter of from 0.5 μm to 1,00 μm. If the average particle diameter is less than 〇.5 μm, the conductive powder may not contact the electrode surface to be connected to 200900531, and poor contact may occur when there is a gap between the electrodes. On the other hand, if the diameter is larger than 1, 〇〇〇 micron, a small conductive connection cannot be achieved. Therefore, the average particle diameter is limited to the above range, and more preferably from 1 μm to 1 μm, more preferably from 2 μm to 20 μm, most preferably from 3 μm to 1 μm. The resin powder according to the present invention has an aspect ratio of less than 2, more preferably less than 12, and particularly preferably 1.06. If the aspect ratio is greater than 2, since the particle diameter is not uniformly hooked, when the conductive particles are in contact with each other, a large amount of uncontacted particles appear. Therefore, the aspect ratio is limited to the above range. The resin powder to be used has a coefficient of variation (Cv) of not more than 3%, more preferably not more than 20%, more preferably not more than 5%. If the Cv value exceeds 3 %, since the particle diameter is not uniform, a large amount of uncontacted particles may appear when the conductive particles are in contact with each other. Therefore, the coefficient is limited to the above range. In the present invention, the coefficient of variation (Cv) is defined by the following formula 1: [Formula 1]
Cv (%) = (σ/Dn) x 1〇〇 其中，σ係該顆粒直徑之標準偏差，且Dn係數目平均粒徑 (number average particle diameter)。 可藉由利用—來自Particle Sizing System有限公司的&⑶dm 780型來計算該標準偏差及該數目平均粒徑。 在形成一過渡金屬鍍覆層於樹脂粉末之表面上的步驟中，可使 用一選自Au、Ag、Co、Cu、见、pd、pt及％、或其合金之導電 過渡金屬。可採用含有相同金屬或不同金屬之多層的鍍覆。較佳 地，鍍覆層係包含Ni4Ni_Au多層的鍍覆層。鎳鍍覆層具有與基 200900531 礎樹脂顆粒的緊密黏結，以形成一具有良好剝離抗力（peeiing resistence)的電解锻覆層。此外，以多層之方式將金鍍覆於一鎳 鍍覆層上，以確保與該經鍍覆層的穩定黏結係容易的。當形成一Cv (%) = (σ/Dn) x 1〇〇 where σ is the standard deviation of the particle diameter and Dn is the number average particle diameter. The standard deviation and the number average particle diameter can be calculated by using & (3) dm 780 type from Particle Sizing System Co., Ltd. In the step of forming a transition metal plating layer on the surface of the resin powder, a conductive transition metal selected from the group consisting of Au, Ag, Co, Cu, s, pd, pt and %, or an alloy thereof may be used. Plating with multiple layers of the same metal or different metals may be employed. Preferably, the plating layer comprises a plating layer of Ni4Ni_Au multilayer. The nickel plating layer has a close bond with the base resin particles of the base 200900531 to form an electrolytic forged coating layer having good peeling resistance. In addition, gold is plated on a nickel plating layer in multiple layers to ensure a stable bond to the plated layer. When forming one
Ni-Au多層時，相較於單層鍍覆層，其可進一步提高導電效能。於 鑛覆過渡金屬的方法中，於樹脂粉末之表面上可使用濕式鍵覆或 乾式鍍覆。 濕式鍍覆製程可區分為電鍍製程及無電鍍覆製程。電鍍製程係 將電極置於—含有金屬料的電鑛液體中，施加電流至其中， 從而在作為陰極的基材表面上，造成金屬離子之還原沉積以形成 金屬鍍覆層。無電锻覆製程係在沒有使用電力的情況下，將水 容液狀I、的金屬離子沉積，其可廣泛地應用到如非導電樹脂的基 材無電鑛覆製程又區分為置換鑛覆製程及還原鑛覆製程。 於置換鍍覆中，由於鍍覆溶液及基材間的電離趨勢（ionization endency)所造成之電子移動而提供鍍覆。但當反應進行而形成一 特定厚度之鍍覆層時該置換反應將終止，以至於無法再形成鍍覆 層。此亦使緊密黏結惡化。 還原鍍覆製程區分為非催化的化學還原鍍覆製程及自身催化的 予還原鑛復製私。因為前者不具有自身催化的特性，而於厚層 中的鍍覆上有所限制。再者，反應係同時地發生在基材及鍍覆溶 中 以至於溶液不能重複使用。後者係自身催化的無電鍍覆製 釦其廣泛地使用在目前的產業領域中，其係藉由還原劑的作用 將鍍覆溶液中的金屬還原地沉積。 相較於濕式鑛覆製程，乾式鑛覆製程廣泛地包含熱浸鐘塗佈、 11 200900531 熱喷鍍、及氣相沉積等等，但一般係指氣相沉積。氣相沉積製程 包含化學氣相沉積（CVD)及物理氣相沉積（PVD)，其係在真空 中將金屬或化合物氣相沉積。氣相沉積製程的優點在於可對大部 分之金屬或金屬化合物（包含在水溶液中無法經電沉積的Al、Ti 等等）進行沉積。過渡金屬鍍覆層係經由上述鍍覆製程而形成於 作為基材的樹脂粉末上，但本發明不限於此。於單層鍍覆層之情 況中，鍍覆層之厚度在10奈米至200奈米之範圍，於多層鍍覆層 之情況中係在10奈米至300奈米之範圍，但厚度並不限於此。 根據本發明之置換金鍍覆溶液包含一水溶性的金成分、一錯合 劑及一還原劑。現在開始描述根據本發明之置換金鍍覆溶液中所 含有的個別成份。 本發明之置換金鍍覆溶液中，在沒有具體限制的情況下可使用 任何金成分，只要其為水溶性的，以氰化金錯合鹽係尤佳。氰化 金錯合鹽之特定實例包含選自氰化金鉀及氰化金鈉之一者、或其 混合物。於根據本發明之置換金鍍覆液中，水溶性金成分之濃度 並無特殊限制。如果金成分之濃度太低，則金鍍覆之初始沉積速 率是緩慢的，且需要長時間以形成一特定厚度之金鍍覆層。另一 方面，如果金成分之濃度太高，則由於所使用的金量增加將提高 成本。鑑於這些情況，置換金鍍覆溶液中之水溶性金成分的濃度 較佳在0.01莫耳/升至1莫耳/升之範圍中，但不限於此。 自根據本發明之置換金鍍覆溶液中將金沉積係以二階段實施： 在反應之早期階段藉由金屬鍍覆層的置換反應；以及隨後藉由使 用一還原劑的還原作用。結果，當於具有導電之過鍍金屬鍍覆層 12 200900531 的粉末上實施金鍍覆時，金在早期反應階段係於過渡金屬相中被 還原而形成一金層，且初級鍍覆層之金屬係解離於鍍覆液體中。 與本發明之鍍覆液體混和的錯合劑係促進經鍍覆於該核心上的導 電過渡金屬之解離反應，且溶解電鍍液體中經解離的金屬離子。 於依據本發明之鍍覆液體中，可使用任何錯合劑，並無特殊限 制，只要其可穩定地溶解鍍覆液體中的金屬離子，以乙二胺衍生 物尤佳。可有效地用於本發明之乙二胺衍生物之特定實例包含於 乙二胺或二乙烯三胺之氮原子上具有三至五個取代基之衍生物的 鹼金屬鹽（如鈉鹽或鉀鹽）或胺鹽等等，該取代基係選自羥烷基、 羧烷基、磺酸基等等，例如N-羥乙基乙二胺、四羥乙基已二胺、 乙二胺四乙酸及乙二胺四亞甲基乙酸。根據本發明之方法中，可 使用選自以上錯合劑之任一者或其混合物。 如果錯合劑之濃度太低，則難以穩定地溶解經解離的金屬離 子。另一方面，如果濃度太高，將因鍍覆於核心上的過渡金屬過 度解離而引起剝離。錯合劑之濃度較佳為10克/升至1，〇〇〇克/升， 更佳為100克/升至600克/升。 本發明之方法中，還原劑係用於還原置換金鍍覆溶液中所含有 的水溶性金鹽。藉由還原劑的使用，可獲得一具有合適沉積速率 及優異穩定性的無電置換金鍍覆溶液。根據本發明，一選自以下 群組之化合物可用作還原劑：抗壞血酸化合物如L-抗壞血酸鹽、 聯胺化合物如對聯胺苯磺酸及硫酸聯胺、一對苯二酚化合物如曱 基對苯二紛、氯對苯二紛及甲氧基對苯二酌、或其混合物。 本發明之鍍覆液體中的還原劑濃度並無特殊限制。如果濃度太 13 200900531 低，難以將金沉積，當其太多時，則成本增加。由此觀點，以於 鑛覆液體中〇.5克/升之待還原的金離子計，還原劑之濃度較佳為 0.01克/升至50克/升，更佳為〇丨克/升至20克/升。 根據本發明之金鍍覆層起初係在酸性狀態下藉由與過渡金屬鍍 覆層的置換反應所形成，且於調整該置換鍍覆溶液之pH值至鹼性 狀態後，將還原劑合併至其中以藉由還原作用形成一金鍍覆層。 因此，初始的置換金鑛覆溶液之pH值係於例如3至8之酸性範 圍中，更佳為4至ό，接著加入還原劑之前將該液體之pH值調整 為9至14。 如果用於置換之鍍覆液體的pH值在早期反應階段時低於3，則 鍵覆液體中的氰離子將被排放至大氣中，鍍覆液體之穩定性將降 低，且導電過渡金屬將過量地析離而引起剝離。相反地，如果 值咼於7’則因為置換鑛覆之初始反應並不會發生而無法實施金鐘 覆。因此，適合的pH值為3至7，較佳為4至6。可用作pH值 控制劑者係有機酸（如摔樣酸、乙酸及草酸，但不限於此）、或 其鹽類（如鈉鹽或鉀鹽）。有機酸之濃度可依所期望達到之pH值 而疋，但以母公升之置換鍍覆液體計，較佳於丨〇克/升至克/ 升之範圍中。 接著’於添加還原劑前調整該液體之pH值為9至14。如果pH 值低於9’則由於置換鍍覆而自初級過渡金屬鍍覆層析離出來的金 屬離子將被還原劑還原，且鍍覆液體中的金離子亦被還原，進而 使鍍覆層不平坦。此外，初級鍍覆層之過渡金屬將形成一合金而 產生氧化薄膜’從而引起連接電阻之增加。另一方面，如果pH值 14 200900531 超過14亦非可取的，因為pH值控制劑含量的增加無法達到相應 的效果。因此’驗性狀態之pH值較佳為9至14,更佳為1〇至14。 可用作pH控制劑而獲得鹼性狀態者係無機鹽（如氫氧化鈉及氯化 銨），以每公升之置換鍍覆液體計，濃度較佳為1〇克/升至2〇〇 克/升。 無電置換金鍍覆溶液之較佳溫度係不低於4〇它。如果溫度太 高，則會輕易地發生鍍覆液體之分解，且因為水的劇烈蒸發將難 以維持鍍覆液體中所含成分之濃度。因此，電鍍液體之溫^較佳 為 20°C 至 80°C。 因此，根據本發明所製備之導電粉末具有優異的導電性及均句 且緊密黏結之鍍覆層，因此可應對較多微佈線，並提供—高品質 導電性無電置換金鑛覆溶液及於連接時不引起電容量問題的鍵覆 方法。 又 如上所述，根據本發明之方法可減少生產成本，其中藉著在置 換金鍍覆反應期間使用—牲宁旦 特疋里之還原劑，以於金鍍覆之早期階 段’藉由置換反應形成—且胜卞度β "特疋厚度之金鍍覆層，接著調整 以藉由還原劑之作用將全沉籍拍被—士 兮儿積。根據§亥方法，將抑制過量的 離同時形成一微小及均勺的厶版费a + , ” 的金鍍覆層，使得當導電粉末經When the Ni-Au multilayer is used, it can further improve the electrical conductivity compared to the single-layer plating layer. In the method of coating a transition metal, wet or dry plating may be used on the surface of the resin powder. The wet plating process can be divided into an electroplating process and an electroless plating process. The electroplating process places an electrode in an electro-mineral liquid containing a metal material, and applies an electric current thereto, thereby causing reduction deposition of metal ions on the surface of the substrate as a cathode to form a metal plating layer. The electroless forging process deposits the metal ions of the water-containing liquid I without using electric power, and can be widely applied to the non-electrical coating process of the non-conductive resin, and is also divided into the replacement ore-removing process and Restore the ore-covering process. In displacement plating, plating is provided due to electron movement caused by ionization endency between the plating solution and the substrate. However, when the reaction proceeds to form a plating layer of a specific thickness, the displacement reaction is terminated, so that the plating layer can no longer be formed. This also worsens the tight adhesion. The reduction plating process is divided into a non-catalytic chemical reduction plating process and a self-catalyzed pre-reduction mineral copying process. Because the former does not have its own catalytic properties, it is limited in plating in thick layers. Furthermore, the reaction occurs simultaneously in the substrate and in the plating solution so that the solution cannot be reused. The latter is a self-catalyzed electroless plating which is widely used in the current industrial field by the reductive deposition of metals in the plating solution by the action of a reducing agent. Compared to the wet ore coating process, the dry ore coating process widely includes hot dip coating, 11 200900531 thermal spraying, vapor deposition, etc., but generally refers to vapor deposition. Vapor deposition processes include chemical vapor deposition (CVD) and physical vapor deposition (PVD), which vapor deposit metals or compounds in a vacuum. The vapor deposition process has the advantage that most of the metal or metal compound (including Al, Ti, etc. which cannot be electrodeposited in an aqueous solution) can be deposited. The transition metal plating layer is formed on the resin powder as a substrate via the above plating process, but the present invention is not limited thereto. In the case of a single-layer plating layer, the thickness of the plating layer is in the range of 10 nm to 200 nm, and in the case of the multi-layer plating layer, it is in the range of 10 nm to 300 nm, but the thickness is not Limited to this. The gold-plated plating solution according to the present invention comprises a water-soluble gold component, a compounding agent and a reducing agent. The individual components contained in the replacement gold plating solution according to the present invention will now be described. In the gold-plated plating solution of the present invention, any gold component can be used without particular limitation, and as long as it is water-soluble, a gold-substituted gold cyanide salt is preferred. Specific examples of the gold cyanide mixed salt include one selected from the group consisting of potassium gold cyanide and sodium gold cyanide, or a mixture thereof. In the replacement gold plating solution according to the present invention, the concentration of the water-soluble gold component is not particularly limited. If the concentration of the gold component is too low, the initial deposition rate of the gold plating is slow, and it takes a long time to form a gold plating layer of a specific thickness. On the other hand, if the concentration of the gold component is too high, the cost will increase due to the increased amount of gold used. In view of these circumstances, the concentration of the water-soluble gold component in the replacement gold plating solution is preferably in the range of 0.01 mol/liter to 1 mol/liter, but is not limited thereto. The gold deposition is carried out in two stages from the replacement gold plating solution according to the present invention: a displacement reaction by a metal plating layer in the early stage of the reaction; and then a reduction by using a reducing agent. As a result, when gold plating is performed on the powder having the conductive overplated metal plating layer 12 200900531, gold is reduced in the transition metal phase in the early reaction stage to form a gold layer, and the metal of the primary plating layer Dissociated in the plating liquid. The complexing agent mixed with the plating liquid of the present invention promotes the dissociation reaction of the conductive transition metal plated on the core and dissolves the dissociated metal ions in the plating liquid. In the plating liquid according to the present invention, any compounding agent can be used without particular limitation as long as it can stably dissolve the metal ions in the plating liquid, and it is particularly preferable to use an ethylenediamine derivative. Specific examples of the ethylenediamine derivative which can be effectively used in the present invention include an alkali metal salt (for example, sodium salt or potassium) having a derivative of three to five substituents on the nitrogen atom of ethylenediamine or diethylenetriamine. a salt or an amine salt or the like, the substituent being selected from the group consisting of a hydroxyalkyl group, a carboxyalkyl group, a sulfonic acid group and the like, such as N-hydroxyethylethylenediamine, tetrahydroxyethylhexamethylenediamine, ethylenediaminetetra Acetic acid and ethylenediaminetetramethyleneacetic acid. In the method according to the present invention, any one selected from the above complexing agents or a mixture thereof can be used. If the concentration of the binder is too low, it is difficult to stably dissolve the dissociated metal ions. On the other hand, if the concentration is too high, peeling will occur due to excessive dissociation of the transition metal plated on the core. The concentration of the complexing agent is preferably from 10 g/liter to 1, gram/liter, more preferably from 100 g/liter to 600 g/liter. In the method of the present invention, the reducing agent is used for the reduction of the water-soluble gold salt contained in the gold plating solution. By using a reducing agent, an electroless gold plating solution having a suitable deposition rate and excellent stability can be obtained. According to the present invention, a compound selected from the group consisting of ascorbic acid compounds such as L-ascorbate, hydrazine compounds such as p-diaminobenzenesulfonic acid and hydrazine sulfate, and a resorcinol compound such as thiol pair Benzophenone, chloro-p-benzoic acid and methoxy-p-benzene, or a mixture thereof. The concentration of the reducing agent in the plating liquid of the present invention is not particularly limited. If the concentration is too low, 200900531, it is difficult to deposit gold, and when it is too much, the cost increases. From this point of view, the concentration of the reducing agent is preferably from 0.01 g/liter to 50 g/liter, more preferably gram/liter to the gold ion to be reduced in the ore-covering liquid. 20 g / liter. The gold plating layer according to the present invention is initially formed by a displacement reaction with a transition metal plating layer in an acidic state, and after adjusting the pH of the displacement plating solution to an alkaline state, the reducing agent is combined to Wherein a gold plating layer is formed by reduction. Therefore, the pH of the initial displacement gold ore coating solution is, for example, in the acid range of 3 to 8, more preferably 4 to ό, and the pH of the liquid is adjusted to 9 to 14 before the addition of the reducing agent. If the pH of the plating liquid used for the replacement is less than 3 in the early reaction stage, the cyanide ions in the keying liquid will be discharged to the atmosphere, the stability of the plating liquid will be lowered, and the conductive transition metal will be excessive. The ground is separated to cause peeling. Conversely, if the value is at 7', the gold bell cannot be implemented because the initial reaction of the replacement ore does not occur. Therefore, a suitable pH is from 3 to 7, preferably from 4 to 6. As the pH controlling agent, organic acids (such as, but not limited to, sulphuric acid, acetic acid, and oxalic acid), or salts thereof (such as sodium or potassium salts) may be used. The concentration of the organic acid may be enthalpy depending on the desired pH value, but it is preferably in the range of gram/liter to gram per liter in terms of the mother plating liter of the displacement plating liquid. The pH of the liquid was then adjusted to 9 to 14 prior to the addition of the reducing agent. If the pH value is lower than 9', the metal ions separated from the primary transition metal plating chromatography due to displacement plating will be reduced by the reducing agent, and the gold ions in the plating liquid are also reduced, so that the plating layer is not flat. Further, the transition metal of the primary plating layer will form an alloy to produce an oxidized film', thereby causing an increase in the connection resistance. On the other hand, it is not preferable if the pH value 14 200900531 exceeds 14 because the increase in the pH control agent content cannot achieve the corresponding effect. Therefore, the pH of the "acceptable state" is preferably from 9 to 14, more preferably from 1 to 14. It can be used as a pH control agent to obtain an alkaline state (for example, sodium hydroxide and ammonium chloride), and the concentration is preferably 1 gram per liter to 2 gram per liter of displacement plating liquid. /Rise. The preferred temperature of the electroless gold plating solution is not less than 4 Å. If the temperature is too high, decomposition of the plating liquid easily occurs, and it is difficult to maintain the concentration of the components contained in the plating liquid because of the vigorous evaporation of water. Therefore, the temperature of the plating liquid is preferably from 20 ° C to 80 ° C. Therefore, the conductive powder prepared according to the present invention has excellent conductivity and a uniform and tightly bonded plating layer, so that it can cope with more micro-wiring and provide high-quality conductive electroless replacement gold ore coating solution and connection. A key overlay method that does not cause a capacitance problem. Further, as described above, the production method according to the present invention can reduce the production cost by using a reducing agent during the replacement gold plating reaction to reduce the reaction in the early stage of gold plating. Forming a gold plating layer that is superior to the thickness of β ", and then adjusting to shoot the entire sunken by the action of the reducing agent. According to the § Hai method, the excessive separation will be inhibited while forming a small and even spoon of the gold plated layer of a + , "", so that when the conductive powder
一微電路時，個別導電M ^球間的電阻偏差小，帶來高可靠性。因此， 其在產業領域中的高效用係可預期的。 實施例 ’但本發明並不限於此。 以下實施觸㈣確描述本發明 [實施例1] 15 200900531 鎳鑛覆之預處理製程 使用甲基丙稀酸所交聯的丙婦酸粉末以及三乙二醇二甲基丙稀 _旨’其中該⑽_末具有3.6微米之平均直徑、5%之Cv及 之長寬比。將1〇克該粉末分餘刚克之混合溶液中，該混 合溶液係由以1，GGG克超純水中含！ 〇克CK)3及克硫酸之方式 所製備’接著將該混合物以超音波洗蘇器處理3G分鐘。經該處理 之後’將該粉末置於贼下歷時1G分鐘，接著时離子水洗蘇。 接著，將其置於- SnCl2之水溶液（1.〇克/升）中歷時3分鐘，並 以冷的去離子水洗滌。經置於一 Pdcl2之水溶液（〇1克/升）中歷 時3分鐘後，以冷的去離子水將其洗滌數次以獲得漿料。 初級的無電鎳鍍覆製程 製備次磷酸鹽（NaHJO2)水溶液（〇.5 μ)作為1公升之分散 物。於加熱該分散物至6(TC之後，以攪拌方式將前段所獲得的該 漿料（10克）倒入其中。使用一微量泵以丨毫升/分鐘之速率緩慢 添加硫酸鎳溶液（1 Μ，50毫升）及作為一還原劑的亞磷酸_ (NaH2P〇4 ’ 2Μ，50毫升）至所得之溶液中。 於完全混合硫酸鎳及該還原劑之後，大力地攪拌該混合物直至 氣之發泡終止。接著進行無電鎳鍍覆同時維持溫度於⑹^且pH 值為6.0。 以1公升之超純水洗;條由此所獲得的錄鍵覆粉末三次，接著_ 由100毫升醇之置換完全地去除殘餘的水。於80。(：下真空乾燥以 獲得鎳鍍覆粉末。由此所製備的鎳鍍覆層之厚度約為120奈米。 金鑛覆製程 16 200900531 將氰化金鉀（10.0克）、乙二胺四乙酸（150克）及檸檬酸銨（70 克）完全地溶解於3公升之去離子水中，以製備一置換金鍍覆溶 液。該溶液具有5.2之pH值。加熱由此所製備之鑛覆液體至60 °C，並添加由鎳鍍覆所獲得的鎳鍍覆粉末（20克）至其中。將所 得之混合物於攪拌及分散10分鐘的情況下反應以獲得約0.08微米 之金厚度。當使用一定量泵滴加氫氧化鈉（NaOH)水溶液（10 M) 至其中而調整其pH值至13.0時，藉著使用一微量泵以1克/分鐘 之速率添加作為還原劑的聯胺二水合物（98%，10克）10分鐘。 接著進行反應35分鐘，且鎳含量及金含量對金鍍覆時間之變化係 顯示於第1圖。 以1公升之去離子水洗滌由此所獲得的鑛覆粉末五次，且藉由 醇之置換完全地去除殘餘的水。於80°C下真空乾燥以產生金鍍覆 粉末。 藉由使用聚焦離子束（focused ion beam，FIB )切下由此所製備 的金鍍覆粉末之剖面，且藉由使用掃描電子顯微鏡（scanning electron microscope，SEM )測量該剖面。結果，該金鑛覆層之厚 度約為20奈米。對由此所製得的鍍覆粉末進行如下測試。微小性 (minuteness )及緊密黏結係顯示於表1。藉由隨反應時間的滴定， 分析使用鎳鍍覆粉末之金鍍覆過程期間，鎳含量及金含量之變 化，其結果係顯示於第1圖。第2圖、第3圖及第4圖為經放大 之該表面的SEM相片（2 : 1，000倍；3 : 20,000倍；4 : 40,000倍） 以決定實施例1所製備的鍍覆粉末之表面均勻性。第5圖顯示在 個別的壓縮壓力下十個導電顆粒對於依據該方法所製得之導電微 17 200900531 粒之接觸電阻的測量’以測量其導電性，如以下所述。 [實施例2] 藉由使用實施例1所製備的鎳鍍覆粉末，實施置換金鍍覆1〇分 鐘。當使用一定量泵滴加氫氧化鈉水溶液（1〇 M)至其中而調整 pH值至13.0時，藉由使用—微量泵以丨毫升/分鐘之速率添加溶 解於100毫升超純水的L-抗壞血酸（2〇克）作為還原劑，以進行 金鍍覆35分鐘。以1公升之去離子水洗滌由此所獲得的鍍覆粉末 五-入，且藉由醇之置換完全地去除殘餘的水。於下真空乾燥 以獲得金鑛覆粉末。 藉由使用聚焦離子束（FIB )切下由此所製得之金鑛覆粉末的剖 面，且藉由掃描電子顯微鏡（SEM)測量該剖面。結果，該金鍍 覆層之厚度約為22奈米。對由此所製備的經鍍覆粉末測量其導電 性、微小性及緊密黏結，並顯示於表丨。第6圖顯示該表面之sem 相片（40,〇〇〇倍）以決定由此所製備的鍍覆粉末之表面均勻性。 [比較例1] 依據如實施例1的相同程序實施置換金鍍覆，但於金鍍覆製程 期間不使用還原劑，且該反應之PH值維持在5.2歷時45分鐘。 兩此所獲得之鍍覆粉末的導電性、微小性及緊密黏結係顯示於 表1。第7圖顯示SEm相片以判定鍍覆之均勻性。藉由隨反應時 間的滴定，分析於使用鎳鍍覆粉末的金鍍覆過程期間之鎳含量及 金含量的變化，其結果顯示於第丨圖。第8圖顯示，在個別的壓 縮壓力下十個導電顆粒對於依據該方法所製得之導電微粒之接觸 電阻的測量，以測量比較例丨所獲得之金鍍覆粉末的導電性。 18 200900531 [比較例2] 藉由使用如實施例1之相同的置換金鍍覆溶液，使用1 〇 Μ氫氧 化鈉（NaOH)水溶液調整ΡΗ值至13.0。使用一微量泵以1克/ 分鐘之速率添加聯胺脫水物（98%，Wako化學有限公司）（10克） 歷時45分鐘。 以1公升之去離子水洗滌由此所獲得的鍍覆粉末五次，且藉由 醇之置換完全地去除殘餘的水。於80°C下真空乾燥以產生金錢覆 粉末。 根據以下方法測量表1之物理性質： (1) 鍍覆之均勻性 利用SEM放大所獲得之鍍覆粉末的表面以確認該粉末之鍍覆層 均勻性。 (2) 導電性之測量 藉由一微粒壓縮電阻計（Fischer，H100C )，在10毫牛頓 (milliNewtons，mN)下，實施一顆粒之電阻測量總共1〇次，且 計算平均及標準偏差。 (3) 鍍覆層之微小性 利用SEM將該鍍覆粉末之鍍覆表面放大5〇,〇〇〇倍，測量金屬顆 粒之尺寸，進而檢測該鍍層之微小性。該金屬顆粒愈小，則獲得 愈微小的鍍覆層。 (4) 緊密黏結之測量 將所獲得的«粉末（1_0克）及具有5毫米直徑的氧化錯微珠 (10克）倒入一 100毫升玻璃瓶中。添加10毫升之甲苯後，以每 19 200900531 分鐘400轉攪拌該混合物1〇分鐘 刀起。接者，分離該氧化锆微珠，並 使用一光學顯微鏡評估該鍍覆層之 说價<狀態。結果顯示於下。 表1When a microcircuit is used, the resistance deviation between individual conductive M^ balls is small, resulting in high reliability. Therefore, its efficient use in the industrial field can be expected. EXAMPLES 'But the invention is not limited thereto. The following embodiment (4) does describe the present invention [Example 1] 15 200900531 The nickel ore coating pretreatment process uses methyl acetoic acid to crosslink the propylene glycol powder and triethylene glycol dimethyl propylene. The (10)-end has an average diameter of 3.6 microns, a Cv of 5%, and an aspect ratio. 1 gram of the powder is mixed in a mixture solution of the mixture, and the mixed solution is contained in 1, GGG grams of ultrapure water! Prepare by the method of CK) 3 and gram of sulfuric acid. The mixture was then treated with an ultrasonic washer for 3 G minutes. After this treatment, the powder was placed under a thief for 1 G minutes, followed by ion water washing. Next, it was placed in an aqueous solution of -SnCl2 (1 g/l) for 3 minutes and washed with cold deionized water. After being placed in an aqueous solution of PdCl 2 (〇1 g/L) for 3 minutes, it was washed several times with cold deionized water to obtain a slurry. Primary electroless nickel plating process An aqueous solution of hypophosphite (NaHJO2) (〇.5 μ) was prepared as a 1 liter dispersion. After heating the dispersion to 6 (TC, the slurry obtained in the previous stage (10 g) was poured into it by stirring. A nickel pump solution (1 Μ, was slowly added at a rate of 丨ml/min using a micro pump. 50 ml) and phosphite _ (NaH 2 P 〇 4 ' 2 Μ, 50 ml) as a reducing agent to the obtained solution. After completely mixing the nickel sulphate and the reducing agent, vigorously stir the mixture until the gas foaming is terminated. Then, electroless nickel plating was carried out while maintaining the temperature at (6) and the pH was 6.0. Washed with 1 liter of ultrapure water; the thus obtained bond-bonded powder was obtained three times, and then _ completely removed by replacement of 100 ml of alcohol. Residual water at 80. (: vacuum drying to obtain nickel-plated powder. The thickness of the nickel plating layer thus prepared is about 120 nm. Gold ore coating process 16 200900531 Potassium cyanide (10.0 g) Ethylenediaminetetraacetic acid (150 g) and ammonium citrate (70 g) were completely dissolved in 3 liters of deionized water to prepare a replacement gold plating solution having a pH of 5.2. The prepared ore liquid is added to 60 ° C and added A nickel plated powder (20 g) obtained by nickel plating was added thereto. The resulting mixture was reacted while stirring and dispersing for 10 minutes to obtain a gold thickness of about 0.08 μm. When a certain amount of pump was used, hydrogen peroxide was added dropwise. When a sodium (NaOH) aqueous solution (10 M) was added thereto and the pH was adjusted to 13.0, hydrazine dihydrate (98%, 10 g) as a reducing agent was added at a rate of 1 g/min using a micro pump. 10 minutes. The reaction was then carried out for 35 minutes, and the change in nickel content and gold content with respect to the gold plating time is shown in Fig. 1. The obtained ore-coated powder was washed five times with 1 liter of deionized water, and borrowed. The residual water was completely removed by displacement of alcohol, and dried under vacuum at 80 ° C to produce a gold-plated powder. The gold-plated powder thus prepared was cut by using a focused ion beam (FIB). The cross section was measured by using a scanning electron microscope (SEM). As a result, the thickness of the gold ore coating was about 20 nm. The plating powder thus obtained was tested as follows. Sex (minuteness) and The dense bonding system is shown in Table 1. The change in nickel content and gold content during the gold plating process using the nickel plating powder was analyzed by titration with reaction time, and the results are shown in Fig. 1. Fig. 2 Fig. 3 and Fig. 4 are SEM photographs of the enlarged surface (2: 1,000 times; 3: 20,000 times; 4: 40,000 times) to determine the surface uniformity of the plated powder prepared in Example 1. Figure 5 shows the measurement of the contact resistance of ten conductive particles for the conductive micro 17 200900531 pellets produced according to the method under individual compression pressures to measure its conductivity, as described below. [Example 2] By using the nickel plating powder prepared in Example 1, replacement gold plating was carried out for 1 〇 minutes. When a certain amount of pump was added dropwise to the aqueous sodium hydroxide solution (1 〇M) to adjust the pH to 13.0, L- dissolved in 100 ml of ultrapure water was added at a rate of 丨ml/min using a micro-pump. Ascorbic acid (2 g) was used as a reducing agent for gold plating for 35 minutes. The thus obtained plating powder was washed with 1 liter of deionized water, and the residual water was completely removed by displacement of alcohol. Dry under vacuum to obtain gold ore-coated powder. The cross section of the gold ore-coated powder thus obtained was cut by using a focused ion beam (FIB), and the cross section was measured by a scanning electron microscope (SEM). As a result, the thickness of the gold plating layer was about 22 nm. The electroplated powder thus prepared was measured for its conductivity, minuteness, and tight adhesion, and was shown in the surface. Figure 6 shows a sem print of the surface (40, 〇〇〇) to determine the surface uniformity of the plated powder thus prepared. [Comparative Example 1] Replacement gold plating was carried out in accordance with the same procedure as in Example 1, except that no reducing agent was used during the gold plating process, and the pH of the reaction was maintained at 5.2 for 45 minutes. The conductivity, minuteness, and tight adhesion of the plated powder obtained herein are shown in Table 1. Figure 7 shows the SEm photo to determine the uniformity of the plating. The change in nickel content and gold content during the gold plating process using the nickel-plated powder was analyzed by titration with the reaction time, and the results are shown in the figure. Fig. 8 shows the measurement of the contact resistance of the conductive particles prepared by the method under the respective compression pressures to measure the electrical conductivity of the gold-plated powder obtained in Comparative Example. 18 200900531 [Comparative Example 2] By using the same replacement gold plating solution as in Example 1, the enthalpy value was adjusted to 13.0 using a 1 Torr sodium hydroxide (NaOH) aqueous solution. A hydrazine dehydrate (98%, Wako Chemical Co., Ltd.) (10 g) was added at a rate of 1 g/min using a micropump for 45 minutes. The thus obtained plating powder was washed five times with 1 liter of deionized water, and the residual water was completely removed by displacement of alcohol. It was vacuum dried at 80 ° C to produce a money-coated powder. The physical properties of Table 1 were measured according to the following methods: (1) Uniformity of plating The surface of the obtained plating powder was enlarged by SEM to confirm the uniformity of the plating layer of the powder. (2) Measurement of conductivity A resistance measurement of a particle was performed for 1 time in total by a particle compression resistance meter (Fischer, H100C) at 10 millinewtons (mN), and the average and standard deviation were calculated. (3) Tinyness of the plating layer The surface of the plating powder was magnified by SEM by 5 times, and the size of the metal particles was measured, and the minuteness of the plating layer was examined. The smaller the metal particles, the finer the plating layer is obtained. (4) Measurement of tight adhesion The obtained «powder (1_0 g) and oxidized microbeads (10 g) having a diameter of 5 mm were poured into a 100 ml glass bottle. After adding 10 ml of toluene, the mixture was stirred at 400 rpm for every 19 200900531 minutes for 1 minute. Next, the zirconia microbeads were separated, and the price of the plating layer was evaluated using an optical microscope. The results are shown below. Table 1
在10毫牛頓之壓縮下一顆粒之電阻 〇：未自該鍍覆層剝離。 △:部份自該鍍覆層剝離。 X:自該鍍覆層剝離。 自表1及第1至8圖所顯示的結果可清楚地領會，在該置換金 鍍覆之早期階段’藉由置換形成—金鑛覆層，且接著使用_還原 劑將金沉積’以形成-微小及均質的金鑛覆層，同時抑制過量錄 之析離。藉由還原劑將金還原以形成一均勻的金層，且將該鍍覆 液體中至少99%之金離子還原地沉積，以至於生產成本可有 降低。 [產業可利用性] 具備導電性的樹脂微粒材料廣泛地用作一防止雷 屯丁衣置或其零 件之靜電力、電波之吸收、電波之屏蔽等等的輔助材料。近來， 20 200900531 經鍍覆的顆粒係用作電性連接電子儀器之微部件的導電材料，其 包含液晶顯不面板的電極與為了操作用之液晶顯示面板的電極至 LSI晶片之電路基板的連接，以及微間距中電極接頭端之間的連接 依據傳統技術所製備的導電球由於經連接至一微電路時，各球 間具非常大的電阻偏差，因此具有可靠性上的近來，隨著 電子儀器及電子零件的小型化U速進展、以及基材上的微佈線 等等，使得具有高度優異導電性的導電粉末是必須的。 本發明關於一種製備具有優異導電性的經鍍覆粉末之無電方 法。更具體地，本發明關於一種製備導電粉末之方法，其係於作 為一核心的樹脂粉末上形成一導電之過渡金屬鍍覆層，接著實施 無電置換金鍍覆。其中，係於酸性狀態下藉由置換反應將過渡金 屬鑛覆粉末錢覆金，接著於驗性狀態下添加還原劑以實施沉積金 鍍覆以形成-微小及均質的金鐘覆層，同時抑制過量鎳之析離。 依據該方法，於經連接至―微電路之導電球的顆粒具有絕佳的導 電性、高可靠性、且顆粒間的電阻偏差小。附匕，其在產業領域 中的高效用係可預期的。 【圖式簡單說明】 第1圖係顯示在實施例i及比較例丨的金鍍覆製程期間改變鎳 έ 1及金3 £之結果，其係隨著時間的進行藉由滴定來分析； 第2圖係依據本發明實施例丨所製造之鍍覆粉末之表面的相片 (1，〇〇〇倍）’其係由一掃描電子顯微鏡（SEM)所拍攝； 第3圖係依據本發明實施例1所製造之鍍覆粉末之表面的相片 (20,000 L ) ’其係由一掃描電子顯微鏡（SEM )所拍攝； 21 200900531 第4圖係依據本發明實施例1所製造之鍍覆粉末之表面的相片 (40,000倍），其係由一掃描電子顯微鏡（SEM)所拍攝； 第5圖顯示對於個別的壓縮壓力，依據本發明實施例1所製造 之十個導電微粒之接觸電阻的測量； 第6圖係依據本發明實施例2所製造的鍍覆粉末之表面的放大 相片，其係由一掃描電子顯微鏡（SEM)所拍攝； 第7圖係依據本發明比較例2所製造之鍍覆粉末表面的放大相 片，其係由一掃描電子顯微鏡（SEM)所拍攝；以及 第8圖顯示對於個別的壓縮壓力，依據本發明實施例1所製造 的十個導電微粒之接觸電阻之測量。 【主要元件符號說明】 (無） 22The resistance of the next pellet at 10 millinewtons 〇: not peeled off from the plating layer. △: Partially peeled off from the plating layer. X: peeled off from the plating layer. The results shown in Table 1 and Figures 1 through 8 are clearly understood to form a gold deposit by displacement in the early stages of the gold plating, and then deposit gold using a reducing agent to form - Tiny and homogeneous gold deposits, while inhibiting excessive separation. The gold is reduced by a reducing agent to form a uniform gold layer, and at least 99% of the gold ions in the plating liquid are reductively deposited, so that the production cost can be lowered. [Industrial Applicability] The resin fine particle material having conductivity is widely used as an auxiliary material for preventing electrostatic force, absorption of electric waves, shielding of electric waves, and the like of the reticle coating or its parts. Recently, 20 200900531, the plated particles are used as a conductive material for electrically connecting the micro-components of the electronic device, and the connection between the electrode of the liquid crystal display panel and the electrode of the liquid crystal display panel for operation to the circuit substrate of the LSI chip. And the connection between the electrode joint ends in the micro pitch, the conductive ball prepared according to the conventional technology has a very large resistance deviation between the balls when connected to a micro circuit, and thus has a reliability recent, along with the electron The miniaturization of the U-speed of the instrument and electronic parts, and the micro-wiring on the substrate, etc., make it necessary to have a highly conductive conductive powder. The present invention relates to an electroless process for preparing a plated powder having excellent electrical conductivity. More specifically, the present invention relates to a method of producing a conductive powder by forming a conductive transition metal plating layer as a core resin powder, followed by electroless gold plating. Wherein, in the acidic state, the transition metal ore coating powder is covered with gold by a displacement reaction, and then a reducing agent is added under an inertial state to perform deposition gold plating to form a minute and homogeneous gold bell coating while suppressing Excessive nickel separation. According to this method, the particles connected to the conductive balls of the "microcircuit" have excellent conductivity, high reliability, and small resistance deviation between particles. Affinity, its efficient use in the industrial field can be expected. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 shows the results of changing nickel έ 1 and gold 3 £ during the gold plating process of Example i and Comparative Example, which are analyzed by titration over time; 2 is a photograph (1, 〇〇〇) of a surface of a plated powder manufactured according to an embodiment of the present invention, which is taken by a scanning electron microscope (SEM); FIG. 3 is an embodiment according to the present invention. Photograph of the surface of a plated powder produced (20,000 L) 'taken by a scanning electron microscope (SEM); 21 200900531 4 is a surface of a plated powder manufactured according to Example 1 of the present invention Photographs (40,000 times) taken by a scanning electron microscope (SEM); Figure 5 shows the measurement of the contact resistance of ten conductive particles produced according to Example 1 of the present invention for individual compression pressures; The photograph is an enlarged photograph of the surface of the plated powder produced according to Example 2 of the present invention, which is taken by a scanning electron microscope (SEM); and FIG. 7 is a surface of the coated powder produced according to Comparative Example 2 of the present invention. Enlarged photo, its Taken by a scanning electron microscope (SEM); and FIG. 8 shows that for an individual compression pressure, measured ten contacts of the conductive fine particles produced in Example 1 according to the present invention, the resistance of the embodiment. [Main component symbol description] (none) 22