200916235 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種具有優異傳導性及黏著力之傳導性無電鍍覆 粉之製造方法；特定而言，係關於一種以無電鍍覆法為基礎之突 起型傳導性鍍覆粉之製造方法，其中於鍍覆層上具有尺寸為0.3 至1.0微米之微型突起物且於無突起物之區域則經平滑地鍍覆，可 獲得優異電阻、鍍覆層與樹脂粉末之間的優異黏著力、及優異規 則性。 【先前技術】 已廣泛使用傳導性樹脂粉末以防止電器或其零件之靜電作用、 吸收電波、或形成電磁遮罩。最近，已使用鍍覆粉作為電子設備 微零件之電性連接的傳導性材料，例如LCD面板電極與LSI晶片 電路板之連接，及微間距（micro pitch )電極終端之間的連接等等。 傳統鍍覆粉之製造方法可大致例示如下：利用金屬顆粒之樹脂粉 末的物理塗層（日本專利申請案第1993-55263號）及於基材粉末 表面上鋪設金屬顆粒突起物之方法（日本專利申請案第 2002- 55952號）。然而，使用無電鍍覆法的鍍覆粉製造方法已成為 目前主要的選擇（日本專利申請案第2003-103494號、第 2003- 57391號、第2001-394798號等等）。自傳統方法所獲得之傳 導性鍍覆粉，例如金、銀及鎳，在連接微間距電極終端期間，有 著於低連接壓力下之高電阻的問題。隨著電子機械的快速進步及 開發，是需要低連接電阻的。 為降低連接電阻，已提出於表面上具有突起物之傳導性顆粒（曰 5 200916235 本專利公開案第2003-234020號）。舉例言之，在使用非傳導性顆 粒進行無電鎳鍍覆時，利用鎳鍍覆液的自我分解以藉由同時形成 微突起物及鎳薄膜而生產傳導性無電鍍覆粉。然而，根據此方法， 除了難以降低連接電阻（由於突起物所造成之不足夠之樹脂排斥 (resin exclusion)所致）以外，突起物會變為鎳塊且難以控制塊 體的尺寸、形狀及數量。 因此，業經報導其他可供選擇的傳導性微顆粒，其含有與最外 層傳導性金属層平行、尺寸為〇.〇2至〇 3微米之微突起物，且最 高為0.1微米之微突起物的比例為I少祕，以促進樹脂的排斥作 用且具有咼連接可#性（日本專利公開案第2〇〇4_296322號）。且 70至90%表面覆蓋有突起物的傳導性微顆粒亦經報導（日本專利 公開案第2__228474號同時’亦經報導—種製造傳導性顆粒 之方法，該傳導性齡係以在其傳導性層上具有如塊體顆粒之凝 聚物（⑽g—)的突起物為特徵，且突起物密度為每顆傳導性 顇粗具有25至50個突起物（日本專利公開案第·6_3〇2716號 根據上述方法之描述，至少80%微突起物具有Q.G2至Q 3微米的 尺寸。大部分微突起物之高度最高為Q3微米。當試著在輕重量 LCD板的電關導«’無法達成僅有微突起物連接之點接觸。 此外，儘管具有優異的連接穩定性，不充足的樹脂排斥會對可靠 電阻造成干擾。 韓國專利第0602726號描述—種鉦 ^ 裡無電傳導性鍍覆方法，其1 或鎳合金薄膜係藉由無電鍍覆而形放 成於球狀核心顆粒的表面 讀核心顆粒的平均直徑為1至20微牛，η 1木且0.05至4微米之微: 200916235 物係形成於薄膜的最外層上，且同時形成一包含該等微突起物之 連續薄膜及鎳薄膜。 尤其是，此方法係於非傳導性顆粒上進行無電鎳鍍覆，其係藉 由同時形成鎳微突起物及鎳薄膜，從而生產傳導性無電鍍覆粉， 該方法係以鎳鍍覆液的自我分解為基礎。然而，根據此方法，非 常難以控制突起物之形狀與數量且難以降低連接電阻，因為突起 物所造成之樹脂排斥並不足夠且無突起物之鍍覆層因具有所形成 之孔隙而相當粗糙且不規則。當不規則且多孔之鍍覆層藉由置換 金鐘覆（displacement gold plating)而將金鐘上時，該鏡覆層會有 剝離的傾向而造成不規則的金鍍覆層。因此，難以降低連接電阻。 隨著電子機械的快速進步及電子零件的微型化，例如在板上的 接線等會變得更微小。所以，具有高傳導性及於鍍覆層與樹脂粉 末之間具有優異黏著力的導電粉末係所需者。 因此，本案發明人經過研究以研發具有優異傳導性及黏著力之 傳導性無電鍍覆粉。結果，本案發明人藉由研發一種以無電鍍覆 法為基礎的傳導性鍍覆粉之製造方法，在無電鍍覆液中、於樹脂 粉末基材的表面上形成一金屬鍍覆層，其可促進於鍍覆層與樹脂 粉末之間具有優異黏著力及規則性以及優異電阻之傳導性鍍覆粉 的生產，該電阻係由於鍍覆層表面具有尺寸為0.3至1.0微米之微 突起物且無突起物之區域則經平滑鍍覆。 本發明之一目的在於提供一種傳導性無電鍍覆粉之製造方法， 該鍍覆粉具有優異的傳導性及黏著力，如此其可處理微接線的需 求，於連接期間提供令人滿意之突起物所造成之樹脂排斥，及提 7 200916235 供高傳導性。 本發明方法所製備之傳導性無電鑛覆粉具有優異傳導性及黏著 力’於其中之第-金屬鑛覆層係、含有尺寸為03至i G微米之微突 起物，且無突起物形成之剩餘區域係經平滑鍍覆。 本發明之另一目的在於以不同的金屬來艘覆第一金屬鍵覆層及 微突起物。 【發明内容】 為達成上述目的’本發明提供—種傳導性無電鍵覆粉之製造方 法03以下步驟.藉由在作為核心材料之樹脂粉末表面上進行 鑛覆而形成第-金屬财層；使用相同或不同金屬來形成微突起 物；以及藉由以相同或不同金屬來鍍覆微突起物與無突起物之第 —金屬鍍覆層的上部而形成第二金屬鍍覆層。 以不同金屬來鍵覆第-金屬鍍覆層及第二金屬鍍覆層係較佳 者0 如第1圖所示’本發明突起型料，時覆粉包含： 使用樹脂粉末之核心材料; 鍍覆於核心材料⑴表面上之第一無電金屬鍍覆層⑺； 形成於第-無電金屬鍍覆層（2)上之過渡金屬突起物 (3 );以及 上與第一無電金屬鍍覆層（2)上之 鍍覆於突起物（3 第二無電金屬鍍覆層（4)。 若有必要的話，突起型傳導性錄覆粉可額外包含形成於第二無 電金屬鍍覆層（4)上之金鍍覆層（5 ^ 200916235 本發明鑛覆粉的特徵在於，形成至少五個尺寸為〇3至1 〇 、, 之圓球狀突起物（3)在該鍍覆粉的1/2表面上， h〇微米 l牡無突起物开冬 成處形成平滑的錢覆層。 在下文中，將更詳細地描述本發明鍍覆粉之製造方法。 本發明提供-種突起型傳導性鍍覆粉之製造方法， Y弟~益 電金屬«層係根據無電鑛覆而形成於使用樹脂粉末之核心㈣ 的表面上Μ及過渡金屬突起物賴㈣時添加過渡金屬與還原 劑而形成於樹脂粉末的表面上。 、 於本發明令，過渡金屬突起物及第一無電金屬鑛覆層較佳係使 用不同金屬。 可包含-額外步驟，根據無電錢覆法，以與第—無電金屬鍵覆 層所用金屬相同或不同之金屬，形成_第二無電金屬鑛覆層於過 渡金屬突起物上及無突起物之第—無電金賴覆層上^且亦可包 含-額外步驟，於第二無電金屬錢覆層上形成金錢覆層。 為形成金錄覆層，將塗覆有第二無電金屬錢覆層之傳導性鑛覆 粉分散於置換金之Π夜巾，w丨發㈣金鍍f㈠丨响咖咖 g〇idplating);以及調整置換金鑛覆液為鹼性，並於其中添加還原 劑以於置換金鑛覆層上形成還原的金鍍覆層。如此-來，金鑛覆 層便可精確地且有規則地形成，且可防止第—無電金屬鑛覆層之 金屬被離析（elute)。於此，較佳的鹼性條件係指pH為1〇至μ。 在下文中，將更詳細地描述本發明所使用之成分。 如上文中所⑤明’本案發明人發現藉由無電锻覆而將金屬鍵覆 層形成於樹脂粉末表面上之方法，可製造具錢異規雜及在鑛 200916235 覆層與樹脂粉末之間具有優異黏著力之傳導性鍍 覆粉，因為鍍覆 粉具有尺寸為〇,3至1.〇微米之微突起物且在無突起物形成之區域 係經非$平滑地鍍覆。且發明人藉由證實本發明方法於電極的微 連接期間具有突起物所造成之充分的樹脂排斥及高傳導性的優 點’來進一步完成本發明。 於本發明中’用於無電鍍覆核心材料之樹脂並無限制。舉例言 之，較佳係一選自以下群組中之樹脂或至少二者之混合物：諸如 聚己稀、聚氣乙稀、聚丙烯、聚苯乙烯及聚異丁烯之聚烯烴；諸 如笨乙烯-丙烯腈共聚物及丙烯腈_丁二烯-苯乙烯三聚物之烯烴共 聚物，諸如聚丙烯酸酯、聚曱基丙烯酸甲酯及聚丙烯醯胺之丙烯 酸订生物，諸如聚乙酸乙烯酯及聚乙烯醇之聚乙烯化合物；諸如 水、％醛、聚乙二醇、聚丙二醇及環氧樹脂之醚聚合物，·諸如苯代 -聚氰胺、脲、硫腺、三聚氫胺、乙酿三聚氰胺、二氰胺及苯胺 之胺聚合物；諸如甲醛、鈀甲醛及乙醛之醛類；聚胺甲酸酯；以 及聚酯。 根據本發明’樹脂粉末之平均直徑為〇.5至⑻微米。若平均 直k不及0.5微米，傳導性粉末與電極的接觸會變得困難。若電極 有缝隙存在，則會觀察到連接失敗。若平均直徑超過1 〇⑼微 米微傳V性連接會變得困難。因此，平均直徑的範圍較佳為！ 至⑽微米’更佳為2至20微米，最佳為3至1〇微米。 土於本發明中’樹脂粉末之長寬&係、低於2，更佳係低於a，最 佳係低於1.G6。若長寬比大於2’顆粒直徑會變得不規則，意指當 傳夺性粉末被返與電極闕時，未接觸獅賴量會增加。因此， 200916235 長寬比較佳係限制在上述範_，且更佳係限制在丨至2的範圍 内0 控制顆粒（reinpartide)直徑之較佳變化係數（CO最高為3〇%， 較佳係最高為2G%，更佳係最高為·，最佳係丨至3Q%。若c 超過30%，顆粒直徑是不規則的，以至於傳導性粉末與電極的接 觸變付困難’意指未接觸顆粒的數量增加。因此，必須將Cv調整 至上述範圍内。於此，cv值係由以下數學式！所定義之： [數學式1]200916235 IX. Description of the Invention: [Technical Field] The present invention relates to a method for producing a conductive electroless plating powder having excellent conductivity and adhesion; in particular, based on an electroless plating method A method for producing a protrusion-type conductive plating powder, which has micro-protrusions having a size of 0.3 to 1.0 μm on a plating layer and is smoothly plated in a region without protrusions, thereby obtaining excellent resistance and plating Excellent adhesion between the layer and the resin powder, and excellent regularity. [Prior Art] Conductive resin powder has been widely used to prevent electrostatic action of an electric appliance or a part thereof, absorption of electric waves, or formation of an electromagnetic mask. Recently, plating powder has been used as a conductive material for electrical connection of electronic device micro-components, such as connection of an LCD panel electrode to an LSI chip circuit board, and connection between micro pitch electrode terminals and the like. The manufacturing method of the conventional plating powder can be roughly exemplified as follows: a physical coating using a resin powder of metal particles (Japanese Patent Application No. 1993-55263) and a method of laying metal particle protrusions on the surface of a base powder (Japanese Patent) Application No. 2002- 55952). However, a method of manufacturing a plating powder using an electroless plating method has been the main choice at present (Japanese Patent Application No. 2003-103494, No. 2003-57391, No. 2001-394798, etc.). Conductive plating powders obtained by conventional methods, such as gold, silver, and nickel, have a problem of high electrical resistance at low connection pressures during the connection of the micro-pitch electrodes. With the rapid advancement and development of electronic machinery, low connection resistance is required. In order to reduce the connection resistance, conductive particles having protrusions on the surface have been proposed (曰 5 200916235 Patent Publication No. 2003-234020). For example, in the case of electroless nickel plating using non-conductive particles, self-decomposition of the nickel plating solution is utilized to produce a conductive electroless plating powder by simultaneously forming microprojections and a nickel film. However, according to this method, in addition to difficulty in lowering the connection resistance (due to insufficient resin exclusion caused by the protrusions), the protrusions become nickel blocks and it is difficult to control the size, shape, and number of the blocks. . Therefore, other alternative conductive microparticles have been reported which contain microprojections parallel to the outermost conductive metal layer and having a size of 〇.〇2 to 〇3 μm and microprojections of up to 0.1 μm. The ratio is less than I, in order to promote the repulsion of the resin and to have a ruthenium linkage (Japanese Patent Publication No. 2-296322). And 70 to 90% of the conductive microparticles having a surface covered with protrusions have also been reported (Japanese Patent Publication No. 2__228474] is also reported as a method for producing conductive particles in which the conductivity is based on conductivity. The layer has a protrusion such as agglomerates of the bulk particles ((10)g-), and the density of the protrusions has 25 to 50 protrusions per conductive upset (Japanese Patent Publication No. 6_3〇2716) According to the above method, at least 80% of the microprojections have a size of Q.G2 to Q3 micrometers. Most of the microprojections have a height of up to Q3 micrometers. When trying to control the light weight of the LCD panel, it cannot be achieved. In addition, although there is excellent contact stability, insufficient resin repelling may interfere with reliable resistance. Korean Patent No. 0602726 describes a method for electroless plating in a kind of ,^. The 1 or nickel alloy film is formed by electroless plating on the surface of the spherical core particles. The read core particles have an average diameter of 1 to 20 micro-N, η 1 wood and 0.05 to 4 μm: 200916235 form A continuous film and a nickel film comprising the microprojections are simultaneously formed on the outermost layer of the film. In particular, the method is performed on electroless nickel plating on non-conductive particles by simultaneously forming nickel microprotrusions. And nickel film to produce conductive electroless plating powder, which is based on self-decomposition of nickel plating solution. However, according to this method, it is very difficult to control the shape and number of protrusions and it is difficult to reduce the connection resistance because The resin repulsion caused by the protrusions is not sufficient and the plating layer without protrusions is rather rough and irregular due to the formed pores. When the irregular and porous coating layer is replaced by a gold platoon (displacement gold plating) When the Admiralty is applied, the mirror coating tends to peel off and cause an irregular gold plating layer. Therefore, it is difficult to reduce the connection resistance. With the rapid advancement of electronic machinery and the miniaturization of electronic components, for example, The wiring and the like on the board are made smaller. Therefore, it is required for a conductive powder having high conductivity and excellent adhesion between the plating layer and the resin powder. Therefore, the inventors of the present invention have studied to develop a conductive electroless plating powder having excellent conductivity and adhesion. As a result, the inventors of the present invention have developed a method for producing a conductive plating powder based on an electroless plating method. Forming a metal plating layer on the surface of the resin powder substrate in the electroless plating solution, which can promote the conductive plating powder having excellent adhesion and regularity between the plating layer and the resin powder and excellent electrical resistance. The production is based on the fact that the surface of the plating layer has microprojections having a size of 0.3 to 1.0 μm and the regions without protrusions are smoothly plated. One of the objects of the present invention is to provide a conductive electroless plating powder. By the method, the plated powder has excellent conductivity and adhesion, so that it can handle the need of microwiring, provide resin repulsion caused by satisfactory protrusions during the connection, and provide high conductivity for 200916235. The conductive electroless mineral powder prepared by the method of the invention has excellent conductivity and adhesion, and the first metal ore coating layer therein has microprojections having a size of 03 to i G micrometers, and no protrusions are formed. The remaining area is smooth plated. Another object of the invention is to coat the first metal bond coating and the microprojections with different metals. SUMMARY OF THE INVENTION In order to achieve the above object, the present invention provides a method for producing a conductive electroless bond-free powder. The following steps: forming a first-metal metal layer by performing mineral coating on the surface of a resin powder as a core material; The same or different metals are used to form the microprojections; and the second metal plating layer is formed by plating the upper portions of the first and third metallization layers of the microprojections and the non-protrusions with the same or different metals. Preferably, the first metal plating layer and the second metal plating layer are bonded with different metals. As shown in FIG. 1 , the protruding material of the present invention comprises: a core material using a resin powder; a first electroless metal plating layer (7) overlying the surface of the core material (1); a transition metal protrusion (3) formed on the first electroless metal plating layer (2); and an upper and first electroless metal plating layer ( 2) plating on the protrusion (3 second electroless metal plating layer (4). If necessary, the protrusion type conductive recording powder may additionally be formed on the second electroless metal plating layer (4) Gold plating layer (5 ^ 200916235) The ore coating powder of the present invention is characterized in that at least five spheroidal protrusions (3) having a size of 〇3 to 1 形成 are formed on the 1/2 surface of the plating powder. Above, the h〇 micron l no protrusions form a smooth money coating at the winter opening. Hereinafter, the manufacturing method of the plating powder of the present invention will be described in more detail. The present invention provides a protuberance type conductive plating powder. The manufacturing method, Y Di ~ Yi Electric Metal « layer is formed on the core of the resin powder according to the electroless mineral coating (4) The surface of the transition metal protrusion and the transition metal protrusion (4) are added to the surface of the resin powder by adding a transition metal and a reducing agent. In the present invention, the transition metal protrusion and the first electroless metal ore coating are preferably used. Different metals may include - an additional step of forming a second electroless metal ore coating on the transition metal protrusions and no protrusions according to the electroless money coating method, with the same or different metal as the metal used for the first electroless metal bond coating The first element - the non-electrical gold coating on the coating ^ can also contain - an additional step to form a gold coating on the second electroless metal money coating. To form a gold coating, it will be coated with a second non-ferrous metal The layer of conductive ore-coated powder is dispersed in the replacement gold night towel, w hair (four) gold plating f (a) 丨 咖 咖 咖 咖 咖 ; ; ; ; ; ; ; ; ; ; ; ; ; 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整 调整Forming a reduced gold plating layer on the replacement gold deposit. Thus, the gold ore coating can be formed accurately and regularly, and the metal of the first-electroless metal ore coating can be prevented from being separated (elute) Here, the preferred alkaline strip The term refers to a pH of from 1 to μ. Hereinafter, the components used in the present invention will be described in more detail. As described above, the inventors have found that a metal bond coating is formed on a resin powder by electroless forging. On the surface, it can produce conductive coating powder with excellent adhesion and excellent adhesion between the coating of 200916235 and resin powder, because the plating powder has a size of 〇, 3 to 1. The microprojections are non-smoothly plated in areas where no protrusions are formed, and the inventors have demonstrated sufficient resin repelling and high conductivity caused by protrusions during micro-joining of the electrodes by the method of the present invention. Advantages 'to further complete the present invention. In the present invention, the resin used for the electroless plating core material is not limited. For example, it is preferably a resin selected from the following group or a mixture of at least two: such as Polyolefins, polyethylene, polypropylene, polystyrene and polyisobutylene; olefin copolymers such as stupid ethylene-acrylonitrile copolymers and acrylonitrile-butadiene-styrene trimers, such as poly Propylene Acrylic acid esters of acid esters, polymethyl methacrylates and polypropylene decylamines, such as polyethylene compounds of polyvinyl acetate and polyvinyl alcohol; such as water, % aldehyde, polyethylene glycol, polypropylene glycol and epoxy resin Ether polymer, amine polymers such as benzo-melamine, urea, sulfur gland, melamine, melamine, dicyanamide and aniline; aldehydes such as formaldehyde, palladium formaldehyde and acetaldehyde; polyamine Acid ester; and polyester. The average diameter of the resin powder according to the present invention is 〇.5 to (8) μm. If the average straight k is less than 0.5 μm, the contact of the conductive powder with the electrode becomes difficult. If there is a gap in the electrode, a connection failure will be observed. If the average diameter exceeds 1 〇 (9) micrometers, the micro-transmission V-connection will become difficult. Therefore, the range of the average diameter is preferably! It is more preferably from 2 to 20 μm, more preferably from 3 to 1 μm. In the present invention, the length and width of the resin powder are less than 2, more preferably less than a, and most preferably less than 1.G6. If the aspect ratio is larger than 2', the particle diameter will become irregular, meaning that when the submerged powder is returned to the electrode, the amount of untouched lion will increase. Therefore, the comparison of length and width of 200916235 is limited to the above-mentioned range, and it is better to limit the variation coefficient of the diameter of the control particle (reinpartide) within the range of 丨2 to 2 (CO is up to 3〇%, preferably the highest It is 2G%, the best is the highest, and the best is 3 to 3Q%. If c exceeds 30%, the particle diameter is irregular, so that the conductive powder and the electrode are difficult to contact with the 'meaning no contact with the particles. The number is increased. Therefore, Cv must be adjusted to the above range. Here, the cv value is defined by the following mathematical formula! [Math 1]
Cv ( %) = (σ/Dn) χ1〇〇 其中，σ係顆粒直徑的標準偏差，Dn係數量平均直徑 (number average mean diameter )。 標準偏差及數量平均直徑係由顆粒尺寸分析器（Accusizer m〇del 780-particle sizing systems, Inc)來計算的。 \ 根據本發明，第一金屬層係以無電鍍覆法而形成於樹脂粉末基 材的表面上，且將以還原劑還原的過渡金屬溶液加至其中以於第 一金屬鍍覆層上產生突起物。如此一來，過渡金屬便會於第—金 屬鍍覆層上還原。接著，第二無電鍍覆層係形成於還原的過渡金 屬突起物上及第一無電鎳鍍覆層上，以製造突起型傳導性球狀物。 特定言之，為形成第一鍍覆層，將樹脂基材顆粒添加至如〇丨2溶 液中，Sn+2離子藉此而黏著於樹脂基材的表面上。隨後，係藉 由使用PdC丨2溶液形成催化核（cataiyt：ic mic丨ei )而於抖於美材表 面上還原’從而形成第一鍍覆薄膜層。 電鍍覆之傳 用以形成第一鍍覆薄膜層之金屬可為任何適用於無 200916235 導性金屬，例如金、銀、钻、銅、錄、把、始及錫或其合金。亦 可形成二或多種不同金屬之雙層鍍覆層或多層鍍覆層。鎳薄膜層 係較佳的金屬薄膜層。鎳薄膜層與樹脂基材顆粒之間具有優異的 黏著力，且可形成具有優異抗剝離力之無電鍍覆薄膜層。可允許 的薄膜層厚度為10至100奈米，但並非總是限於此。 為於形成第一薄膜層之後產生突起物，較佳係使用與形成第一 薄膜層所用之金屬不同的金屬作為過渡金屬。舉例言之，過渡金 屬係選自由把、銅、釕、銘、銀、钻及其合金所組成之群組，可 用作第二無電鍍覆之催化核。亦可形成二或多種不同金屬之雙層 链·覆層或多層鑛覆層。 用於鍍覆之金屬溶液的濃度及所添加的量與突起物的尺寸及數 量有關。金屬溶液較佳係含有0.01至100公克/公升之過渡金屬。 若過渡金屬的含量過低，過渡金屬的析離（eduction)會變得困難 且突起物的尺寸會變得過小。若含量超過50公克/公升，突起物的 尺寸會變得過大且成本亦會增加。因此，較佳含量為〇.〇1至50 公克/公升，更佳含量為0.1至20公克/公升。 用於過渡金屬之還原劑並無限制，且可接受任何可還原過渡金 屬溶液的還原劑。舉例言之，可使用選自由異抗壞血酸（erythorbic acid)化合物、聯胺（hydrazine)化合物、對苯二紛化合物、蝴化 合物及填酸化合物或其鹽類所組成之群組的一或多種化合物作為 還原劑。 添加此類還原劑有助於以有利的析離速度產生具有優異穩定性 之過渡金屬突起物。 12 200916235 異抗壞血酸化合物的例子有左旋抗壞血酸鹽；聯胺化合物的例 子有對聯胺苯磺酸與硫酸聯胺衍生物；對苯二酚化合物的例子有 曱基對苯二酚、氯對苯二酚與甲氧基對苯二酚；硼化合物的例子 有硼氫化鈉與二甲基胺基溴化物；以及磷酸化合物的例子有次磷 酸納（sodium hyperphosphite)與焦亞鱗酸鹽（pyrophosphite)。 本發明之還原劑及還原劑衍生物係可個別的使用或以至少二化 合物的混合物使用。並未限制本發明鍍覆液中還原劑的含量。但 若還原劑的含量過低，過渡金屬的析離會變得困難且成本會增加 過多。因此，於總鍍覆液中還原劑的較佳含量為0.01至50公克/ 公升，更佳含量為0.1至20公克/公升。 由過渡金屬形成突起物的較佳溫度為至少40°C。然而，若溫度 過高，鍍覆液也許會降解且水會過度地蒸發，有可能會使鍍覆液 中的成分含量發生改變。因此，鍍覆液的溫度較佳係調整為20至 80°C。添加還原劑以調整鍍覆液的pH為3至14。若pH低於3， 金屬會從第一薄膜層中離析，此代表金屬層會被破壞，鑛覆會變 得不規則，突起物無法形成於樹脂粉末表面上、或因離析出的金 屬與過渡金屬的結合所產生之合金而使突起物的產生變得不規 則，因而提高連接電阻。反之，若pH高於14，pH調整劑的量必 須增加以降低影響。因此，pH較佳係調整為3至14，更佳係調整 為5至12。pH調整劑可為無機鹽類，例如氫氧化鈉、氯化銨等。 鍍覆液中pH調整劑的含量較佳為10至200公克/公升。 於在過渡金屬突起物及第一無電鍍覆層表面上形成第二無電鎳 鍍覆層的步驟中，鍍覆粉可作為基材以在鍍覆薄膜層上形成至少 13 200916235 二種金屬層。舉例言之，可輕易地於鎳薄膜層上形成金層，其有 助於與鍍覆薄膜層的連接性。鎳-金雙薄膜層可提供高於單薄膜層 的傳導性。單薄膜層的厚度為10至200奈米，雙薄膜層的厚度為 10至300奈米，但並非總是限於此。 由本發明方法所製備之傳導性鍍覆粉具有優異傳導性及鍍覆層 間之黏著力，可滿足微接線的需求，且該鍍覆粉係高品質及高價 值之鍍覆粉，於連接期間不會因電容而被限制。 如之前所說明，本發明突起型傳導性鍍覆粉的特徵在於具有規 則形狀及尺寸之突起物及於熱壓縮期間因異向性傳導性膜而對電 極有優異的樹脂排斥（因為突起物係規則的且無突起物形成區域 係經平滑地鍍覆），·對電極具有優異連接可靠性；以及精細鍍覆層 與樹脂粉末之間的優異黏著力及優異規則性。因此，本發明提供 高品質的傳導性無電鍍覆粉，其可滿足微接線的需求且於連接期 間不會被電容所限制。 【實施方式】 自以下較佳實施態樣之說明内容連同圖式可更全面瞭解本發明 之其他及另外之目的、特徵及優點。 在下文中，將更詳細地描述本發明具有優異傳導性及黏著力的 傳導性鍍覆粉之製造方法，但本發明精神及範圍並不限於以下實 施例。 製備實施例 樹脂粉末之預處理 使用丙烯酸系粉末（平均直徑·· 3.6微米，Cv: 5%，長寬比：1.06， 14 200916235 甲基丙烯酸：三乙二醇二甲基丙烯酸酯=20 : 80 (重量比例），重 量平均分子量：30,000)。將30公克粉末分散於含有10公克Cr03、 200公克硫酸及1000公克超優質水之混合溶液中，接著以超音波 清洗器處理30分鐘。 在超音波處理之後，將混合物放置於60°C下10分鐘，接著用 去離子水沖洗。在沖洗之後，將該混合物放置於SnCl2溶液（1.0 公克/公升）中3分鐘，隨後用冷去離子水沖洗。將其放置於PdCl2 溶液（0.1公克/公升）中3分鐘之後，用冷去離子水沖洗該混合物 數次以產生漿料。 第一無電鎳鍍覆 製備1公升之0.5M NaH2P02分散溶液。升溫至60°C，於該溶 液中邊攪拌邊添加30公克漿料。於其中緩慢添加50毫升之1M硫 酸鎳溶液及2M NaH2P04 (還原劑），係藉由使用微量化泵以3毫 升/分鐘的速度進行10分鐘。 在完成硫酸鎳及還原劑的添加之後，以高速攪拌該反應溶液直 至氫氣起泡停止為止。將溫度保持在60。(：且將pH保持在6.0以 進行無電錄鍍覆。鎳鍍覆層的厚度大約是15奈米。隨後產生過渡 金屬突起物。 實施例1 過渡金屬突起物的產生 將0.5克PdCI2 (過渡金屬）溶於500公克超純水中。將10公 克聯胺（還原劑）稀釋於500公克超純水中。將pH調整為6.0。 同時添加各該溶液200公克至第一鎳鍍覆分散溶液中，以於第一 15 200916235 無電鎳鍍覆粉上產生Pd突起物。Pd突起物的尺寸平均為1〇奈米。 第二無電鎳鍍覆 將表面上有Pd突起物之第一無電鎳鍍覆粉以無電鍍覆液 (Union440, Union Specialty)進行錢覆。 無電鍍覆液可分為A溶液（1M，硫酸鎳）及b溶液（還原劑， 2M，NaHJO4)，其係藉由使用微量化泵以3毫升/分鐘的速度歷 時80分鐘而緩慢添加的。在完成硫酸鎳及還原劑的添加之後，於 相同溫度下攪拌以形成第二無電鎳鍍覆層，直到氫氣起泡停止為 止。將所得錄鑛覆粉以醇沖洗數次，在8〇°C下真空乾燥以產生鎳 鍍覆粉。鎳鍍覆層的厚度大約是120奈米。 所得結果係如表1所示。第2圖所示為本發明實施例】所製備 之鍍覆粉表面的SEM照片（6,000倍數），證實突起物分佈的規則 性。第3圖說明了金屬顆粒的1/2表面上之突起物的尺寸及數量 (20,000倍數）。照片中所示為具有不規則黏附的pd之鎳球狀物 的表面，突起物的尺寸為280至400奈米且最大的突起物尺寸為 大約600奈米。無突起物產生之表面區域係經均勻地錄覆。測量 突起物的尺寸與數量及電阻值與黏著力，結果列於表丨中。 實施例2 以實施例1情粒相同方絲進行預處理程序，且第一及驾 一無電錄鑛覆亦係以上述相同方法來進行 T 不同處在於使用1 克HsPtCl6作為過渡金屬，其溶於5〇〇公岩 ,見赵純水中並使用實施令 1中之還原液作為還原劑以產生突起型傳缘 ♦性球狀物，其係藉由力 成Pt突起物於第一無電鎳鍍覆層上而產峰 9 王的。所得結果係如第 16 200916235 圖及第5圖所示。使用SEM照片（20,000倍數）來測量金屬顆粒 的1/2表面上之犬起物的尺寸及數量並測試電阻值及黏著力。所得 結果係如表1所示。 實施例3 將10克氰化金鉀（potassium gold cyanide)、150公克乙二胺四 乙酸及70公克檸檬酸铵（amm〇nium citrate)完全溶解於3公升 去離子水中以製備置換金之鍍覆液。在那時的pH為5.2。將鍍覆 液的溫度升至60。〇於其中添加20公克由上述鎳鍍覆程序中所製 得的鎳鍍覆粉，接著攪拌該鍍覆液10分鐘以分散鎳鍍覆粉。金鍍 覆層的厚度係調整為0.08微米。藉由使用量化栗添加10M NaOH 溶液從而將pH調整為13.0。添加10公克聯胺二水合物（98%) 作為還原劑，其係藉由使用微量化泵以1公克/分鐘的速度進行10 分鐘。使該反應持續35分鐘。 以去離子水沖洗所得鍍覆粉5次，接著改用醇以完全除去殘留 的水分。然後，將鍍覆粉於80°C下真空乾燥以產生金鍍覆粉。 以聚焦離子束（Focused Ion Beam，FIB )切割所得金鑛覆粉並 將其剖面置於SEM下觀察。金鍍覆層的厚度大約是20奈米。 將上述所製備之金锻覆層置於SEM下觀察其表面，並在6,〇〇〇 倍數及18,000倍數下拍攝照片，如第6圖及第7圖所示。測量經 金屬塗覆之鍍覆粉的1 /2表面上之突起物的尺寸及數量並測試電 阻值及黏著力。所得結果係如表1所示。 實施例4 以實施例3中所述之相同方法來進行金鍍覆，惟使用實施例2 17 200916235 中所製備之突起型鎳鍍覆粉。 所得鍍覆粉係如第8圖及第9圖所示。測量經金塗覆之鍍覆粉 的1/2表面上之突起物的尺寸及數量並測試電阻值及黏著力。所得 結果係如表1所示。 比較例1 从實施例1中所述之相同方法進行實驗；惟，以鎳鍍覆樹脂粉 面且無大起物形成在其表面上，並以實施例3中所述之同方 =所得軸覆粉均行㈣金鑛覆。 如第10圖所示，於比私 塗藉〜 、私例1中並未觀察到突起物。測量經金屬 之鍍覆粉的1/2表 及黏楚丄 由上之突起物的尺寸及數量並測試電阻值 比1者力°所得結果如^所示。 匕較例2 以實施例1中所述之 形成在預處理㈣所^法進行實驗；惟，Pd突起物係誘發 苐二鎳鍍覆。 之樹脂粉末上，且隨後接著進行第一及 如第11圖及第12圖所_ ^ 數量增加。無突起㈣/ 例2中之微突起物及突起物的 孔性且有許多齡未被=區域係呈残則的《，意指其為多 比教例3 Ί <吏用比較例2令所穿 i^相同方法來進行實^⑽4__粉’以實施例3中所 如第13圖及第丨4圖 覆<後顯著地減少，心表面上㈣起㈣《在置換金鍍 且麵覆層之間的黏著力降低。表i中所列之 18 200916235 物理特性係以下列方式來測量： 1) 鍍覆規則性 以SEM( 6,000倍數）拍攝鍍覆粉表面來觀察鍍覆粉及突起物的 規則性。 2) 連接電阻 將傳導性顆粒以250,000顆粒/平方毫米的密度摻入環氧樹脂黏 合劑，將其放置於具有200x100微米連接線圖案的彈性印刷電路 板之間。於190%下、60N壓縮氣壓下進行連接20秒鐘。接著測 量電阻值。 3) 突起物之尺寸及數量 以SEM ( 20,000倍數）拍攝鍍覆粉表面以觀察形成於金屬顆粒 的1/2表面區域上之突起物的尺寸及數量。 4) 黏著力 將上述所得之1公克鍍覆粉及直徑為5毫米之10公克氧化鉛珠 加入100毫升玻璃瓶中，於其中加入10毫升甲苯，接著以400轉 、/分鐘攪拌10分鐘。在攪拌完成之後，將氧化锆珠分離出來並將鍍 覆層置於光學顯微鏡下觀察。 該層之條件係以下列方式來評估： 〇:未觀察到鍍覆薄膜層的剝離。 A:有觀察到部分鍍覆薄膜層膜的剝離。 X :有觀察到鍍覆薄膜層的剝離。 表1 19 200916235Cv ( %) = (σ/Dn) χ1〇〇 where, the standard deviation of the diameter of the σ-based particle, and the number average mean diameter of the Dn coefficient. The standard deviation and the number average diameter were calculated by a particle size analyzer (Accusizer m〇del 780-particle sizing systems, Inc). According to the present invention, the first metal layer is formed on the surface of the resin powder substrate by electroless plating, and a transition metal solution reduced with a reducing agent is added thereto to cause protrusion on the first metal plating layer. Things. As a result, the transition metal will be reduced on the first metal plating layer. Next, a second electroless plating layer is formed on the reduced transition metal protrusions and the first electroless nickel plating layer to produce a protruding conductive ball. Specifically, in order to form the first plating layer, the resin substrate particles are added to a solution such as ruthenium 2, and Sn+2 ions are thereby adhered to the surface of the resin substrate. Subsequently, a first plating film layer was formed by forming a catalytic core (cataiyt: ic mic丨ei) using a PdC 2 solution and reducing it on the surface of the substrate. The metal used to form the first plated film layer can be any suitable for use with non-200916235 conductive metals such as gold, silver, diamond, copper, ruthenium, palladium, tin and alloys thereof. It is also possible to form a two-layer plating layer or a multi-layer plating layer of two or more different metals. The nickel film layer is a preferred metal film layer. The nickel film layer has excellent adhesion to the resin substrate particles, and can form an electroless plating film layer having excellent peeling resistance. The allowable film layer thickness is from 10 to 100 nm, but is not always limited thereto. In order to produce a protrusion after forming the first film layer, it is preferred to use a metal different from the metal used to form the first film layer as a transition metal. For example, the transition metal is selected from the group consisting of copper, copper, ruthenium, silver, diamond, and alloys thereof, and can be used as a second electroless plating nucleus. It is also possible to form a double layer chain coating or a plurality of mineral coating layers of two or more different metals. The concentration of the metal solution used for plating and the amount added are related to the size and number of the protrusions. The metal solution preferably contains from 0.01 to 100 g/l of transition metal. If the content of the transition metal is too low, the transition of the transition metal becomes difficult and the size of the projections becomes too small. If the content exceeds 50 g/liter, the size of the projections becomes too large and the cost increases. Therefore, the preferred content is from 至1 to 50 g/liter, more preferably from 0.1 to 20 g/liter. The reducing agent for the transition metal is not limited and can accept any reducing agent for the reducible transition metal solution. For example, one or more compounds selected from the group consisting of an erythorbic acid compound, a hydrazine compound, a p-benzoic compound, a butterfly compound, and an acid-filling compound or a salt thereof can be used as reducing agent. The addition of such a reducing agent helps to produce transition metal protrusions having excellent stability at an advantageous separation rate. 12 200916235 Examples of erythorbic acid compounds are L-ascorbate; examples of hydrazine compounds are bis-aminobenzenesulfonic acid and hydrazine sulfate derivatives; examples of hydroquinone compounds are decyl hydroquinone and chlorohydroquinone With methoxy hydroquinone; examples of the boron compound are sodium borohydride and dimethylamino bromide; and examples of the phosphoric acid compound are sodium hyperphosphite and pyrophosphite. The reducing agent and reducing agent derivative of the present invention may be used singly or as a mixture of at least two compounds. The content of the reducing agent in the plating solution of the present invention is not limited. However, if the content of the reducing agent is too low, the precipitation of the transition metal becomes difficult and the cost is excessively increased. Therefore, the preferred amount of the reducing agent in the total plating solution is from 0.01 to 50 g/liter, more preferably from 0.1 to 20 g/liter. The preferred temperature for forming the protrusions from the transition metal is at least 40 °C. However, if the temperature is too high, the plating solution may degrade and the water may evaporate excessively, which may change the content of the components in the plating solution. Therefore, the temperature of the plating solution is preferably adjusted to 20 to 80 °C. A reducing agent is added to adjust the pH of the plating solution to 3 to 14. If the pH is lower than 3, the metal will be separated from the first film layer, which means that the metal layer will be destroyed, the ore cover will become irregular, the protrusions cannot be formed on the surface of the resin powder, or the metal and transition due to separation The alloy produced by the combination of the metals causes the generation of the projections to become irregular, thereby increasing the connection resistance. Conversely, if the pH is above 14, the amount of pH adjusting agent must be increased to reduce the effect. Therefore, the pH is preferably adjusted to 3 to 14, and more preferably to 5 to 12. The pH adjuster may be an inorganic salt such as sodium hydroxide, ammonium chloride or the like. The content of the pH adjuster in the plating solution is preferably from 10 to 200 g/liter. In the step of forming a second electroless nickel plating layer on the surface of the transition metal protrusion and the first electroless plating layer, the plating powder may be used as a substrate to form at least 13 200916235 two metal layers on the plating film layer. For example, a gold layer can be easily formed on the nickel film layer, which contributes to the connectivity to the plated film layer. The nickel-gold double film layer provides conductivity above the single film layer. The thickness of the single film layer is 10 to 200 nm, and the thickness of the double film layer is 10 to 300 nm, but is not always limited thereto. The conductive plating powder prepared by the method of the invention has excellent conductivity and adhesion between the plating layers, and can meet the requirements of the micro-wiring, and the plating powder is high-quality and high-value plating powder, and is not connected during the connection. It will be limited by the capacitance. As described above, the protrusion type conductive plating powder of the present invention is characterized by protrusions having a regular shape and size and excellent resin repelling to the electrodes due to the anisotropic conductive film during thermal compression (because the protrusion system The regular and non-protrusion-forming regions are smoothly plated, the electrodes have excellent connection reliability, and the excellent adhesion between the fine plating layer and the resin powder and excellent regularity. Accordingly, the present invention provides a high quality conductive electroless plating powder which satisfies the requirements of microwiring and is not limited by capacitance during connection. Other and other objects, features and advantages of the present invention will become more fully understood from Hereinafter, the method for producing a conductive plating powder having excellent conductivity and adhesion of the present invention will be described in more detail, but the spirit and scope of the present invention are not limited to the following examples. Preparation Example Resin powder was pretreated using acrylic powder (average diameter · 3.6 μm, Cv: 5%, aspect ratio: 1.06, 14 200916235 methacrylic acid: triethylene glycol dimethacrylate = 20: 80 (weight ratio), weight average molecular weight: 30,000). 30 g of the powder was dispersed in a mixed solution containing 10 g of Cr03, 200 g of sulfuric acid, and 1000 g of ultra-premium water, followed by treatment with an ultrasonic cleaner for 30 minutes. After the ultrasonic treatment, the mixture was placed at 60 ° C for 10 minutes, followed by rinsing with deionized water. After rinsing, the mixture was placed in a SnCl 2 solution (1.0 g/L) for 3 minutes, followed by rinsing with cold deionized water. After placing it in a PdCl 2 solution (0.1 g/L) for 3 minutes, the mixture was rinsed several times with cold deionized water to produce a slurry. First electroless nickel plating A 1 liter 0.5 M NaH2P02 dispersion solution was prepared. The temperature was raised to 60 ° C, and 30 g of the slurry was added while stirring in the solution. 50 ml of 1 M nickel sulfate solution and 2 M NaH2P04 (reducing agent) were slowly added thereto by using a micro-pumping pump at a rate of 3 ml/min for 10 minutes. After completion of the addition of nickel sulfate and a reducing agent, the reaction solution was stirred at a high speed until the hydrogen foaming stopped. Keep the temperature at 60. (: and maintaining the pH at 6.0 for electroless plating. The thickness of the nickel plating layer is approximately 15 nm. Subsequently, transition metal protrusions are produced. Example 1 Generation of transition metal protrusions 0.5 g PdCI2 (transition metal) Soluble in 500 grams of ultrapure water. Dilute 10 grams of hydrazine (reducing agent) in 500 grams of ultrapure water. Adjust pH to 6.0. Add 200 grams of each solution to the first nickel plating dispersion. For the first 15 200916235 electroless nickel plating powder to produce Pd protrusions. The size of the Pd protrusions is 1 nanometer on average. The second electroless nickel plating will be the first electroless nickel plating with Pd protrusions on the surface. The powder is covered with an electroless plating solution (Union 440, Union Specialty). The electroless plating solution can be divided into A solution (1M, nickel sulfate) and b solution (reducing agent, 2M, NaHJO4), which is used by using micronization. The pump was slowly added at a rate of 3 ml/min for 80 minutes. After the addition of nickel sulfate and the reducing agent was completed, the mixture was stirred at the same temperature to form a second electroless nickel plating layer until the hydrogen foaming ceased. The obtained recorded ore powder is washed with alcohol Then, it was vacuum dried at 8 ° C to produce a nickel plating powder. The thickness of the nickel plating layer was about 120 nm. The results obtained are shown in Table 1. Fig. 2 shows an example of the present invention. The SEM photograph (6,000 magnifications) of the prepared plating powder surface confirmed the regularity of the projection distribution. Fig. 3 illustrates the size and number (20,000 times) of the projections on the 1/2 surface of the metal particles. Shown as the surface of a nickel sphere with irregularly adhered pd, the size of the protrusions is 280 to 400 nm and the largest protrusion size is about 600 nm. The surface area without protrusions is evenly recorded. The measurement measures the size and quantity of the protrusions and the resistance value and adhesion. The results are shown in the table. Example 2 The pretreatment procedure was carried out with the same square wire of the example 1 and the first and the first The same method is used to carry out T. The difference is that 1 gram of HsPtCl6 is used as a transition metal, which is dissolved in 5 〇〇 public rock, see Zhao pure water and the reducing solution in the implementation of the first embodiment is used as a reducing agent to produce a protuberance. ♦ Spherical spheroid The Pt protrusions were produced on the first electroless nickel plating layer and the peaks were obtained. The results obtained are shown in Figures 16 200916235 and Figure 5. SEM photographs (20,000 magnifications) were used to measure the 1/2 surface of the metal particles. The size and number of the dogs were tested and the resistance and adhesion were tested. The results are shown in Table 1. Example 3 10 g of potassium gold cyanide, 150 g of ethylenediaminetetraacetic acid and 70 g of ammonium citrate (amm〇nium citrate) was completely dissolved in 3 liters of deionized water to prepare a replacement gold plating solution. The pH at that time was 5.2. Increase the temperature of the plating solution to 60. 20 g of the nickel plating powder prepared by the above nickel plating procedure was added thereto, and then the plating solution was stirred for 10 minutes to disperse the nickel plating powder. The thickness of the gold plating layer was adjusted to 0.08 μm. The pH was adjusted to 13.0 by adding a 10 M NaOH solution using a quantitative pump. 10 g of hydrazine dihydrate (98%) was added as a reducing agent by using a micro-pumping pump at a rate of 1 g/min for 10 minutes. The reaction was allowed to continue for 35 minutes. The resulting plating powder was rinsed 5 times with deionized water, followed by switching to alcohol to completely remove residual moisture. Then, the plating powder was vacuum dried at 80 ° C to produce a gold plating powder. The obtained gold ore was cut with a Focused Ion Beam (FIB) and its profile was observed under SEM. The thickness of the gold plating layer is approximately 20 nm. The gold forging layer prepared above was placed under SEM to observe the surface, and photographs were taken at 6, 〇〇〇 multiple and 18,000 times, as shown in Figs. 6 and 7. The size and number of protrusions on the 1 /2 surface of the metal coated plating powder were measured and the resistance and adhesion were tested. The results obtained are shown in Table 1. Example 4 Gold plating was carried out in the same manner as described in Example 3 except that the protrusion type nickel plating powder prepared in Example 2 17 200916235 was used. The obtained plating powder is as shown in Figs. 8 and 9. The size and number of protrusions on the 1/2 surface of the gold-coated plating powder were measured and the resistance value and adhesion were tested. The results obtained are shown in Table 1. Comparative Example 1 An experiment was conducted in the same manner as described in Example 1 except that the surface of the resin powder was plated with nickel and no large objects were formed on the surface thereof, and the same direction as described in Example 3 was used. Powder average (4) gold ore cover. As shown in Fig. 10, no protrusions were observed in the private case 1. The 1/2 gauge of the metal-plated powder and the size and number of the protrusions on the metal were measured and the resistance value was measured as compared with the force of one.匕Comparative Example 2 The experiment was carried out in the pretreatment (4) as described in Example 1; however, the Pd projections induced Niobium nickel plating. On the resin powder, and then proceeding to the first and as shown in Figures 11 and 12, the number is increased. No protrusions (4) / Porosity of the microprojections and protrusions in Example 2 and many years of age = "The area is residual", meaning it is more than the teaching example 3 Ί < 吏Comparative Example 2 The same method is used to perform the actual ^(10)4__powder', as shown in Fig. 13 and Fig. 4, in Fig. 3, the thickness is significantly reduced, and the surface of the heart is (4) (4). The adhesion between the coatings is reduced. The physical properties listed in Table i are measured in the following manner: 1) Plating regularity The surface of the plating powder is photographed by SEM (6,000 magnification) to observe the regularity of the plating powder and the projections. 2) Connecting resistance The conductive particles were incorporated into the epoxy resin adhesive at a density of 250,000 particles/mm 2 and placed between elastic printed circuit boards having a 200 x 100 μm connecting line pattern. The connection was carried out for 20 seconds at 190% under a compression pressure of 60 N. Then measure the resistance value. 3) Size and number of projections The surface of the plating powder was photographed by SEM (20,000 magnification) to observe the size and number of projections formed on the 1/2 surface area of the metal particles. 4) Adhesion A 1 g of the plating powder obtained above and 10 g of lead oxide beads having a diameter of 5 mm were placed in a 100 ml glass bottle, and 10 ml of toluene was added thereto, followed by stirring at 400 rpm for 10 minutes. After the stirring was completed, the zirconia beads were separated and the plated layer was observed under an optical microscope. The conditions of this layer were evaluated in the following manner: 〇: No peeling of the plating film layer was observed. A: Peeling of a partially plated film layer was observed. X: Peeling of the plated film layer was observed. Table 1 19 200916235
突起物的平均 突起物的平均尺 ------π 傳導性 — 黏著力 數量 寸（奈米） (Ω) 實施例1 25 310 11 ----- -------- 實施例2 11 〇 420 ~ 1 — 12 ---------- 〇 實施例3 15 452 —----- 1 ----— π 實施例4 19 522 1 r\ 比較例1 - «_ 25 比較例2 120 91 61 比較例3 25 82 一丨一— 45 X -------1 X 如表i及第2圖至第14圖所示，本發明方法提供具有優異電降 值之傳導性粉末（因其形成較大且規則的突起物，而無突起物开 叙&域餘平滑且均勻崎覆且具有精細鍍覆層）、於鑛覆層途 樹脂粉末之間有優異規祕及㈣力（與先前技術相比）。” 办如上文中所說明，以本發明方法所製得之含有較大且較規則的 犬起物之突起型傳導性鍍覆粉’其於熱壓縮期間因異向性傳導性 膜=電極有優異的樹脂排斥，因為無突起物形成之表面區域亦 滑地鑛覆；對電極具有優異的連接可靠性；以及於 ==覆層與樹脂粉末之間的優異黏著力及優異的規則性。因 需求且：、Γ供南品質的傳導性無電鑛覆粉，其可滿足微接線的 :連接期間不會被電容所限制。 【圖式簡單說明】 第1圓所㈣本發明料性無㈣覆粉之實施敵到面圖； 20 200916235 第2圖所示為本發明實施例1所製備之鍍覆粉表面的SEM照片 ( 6,000 倍數）； 第3圖所示為本發明實施例1所製備之鍍覆粉表面的SEM照片 (20,000 倍數）； 第4圖所示為本發明實施例2所製備之鍍覆粉表面的SEM照片 (6,000 倍數）； 第5圖所示為本發明實施例2所製備之鍍覆粉表面的SEM照片 (10,000 倍數）； 第6圖所示為本發明實施例3所製備之鑛覆粉表面的SEM照片 (6,000 倍數）； 第7圖所示為本發明實施例3所製備之鍍覆粉表面的sem照片 (18,000 倍數）； 第8圖所示為本發明實施例4所製備之艘覆粉表面的sem照片 (6,000 倍數）； 第9圖所示為本發明實施例4所製備之鐘覆粉表面的SEM照片 ( 20,000 倍數）； 第10圖所示為本發明比較例1所製備之鑛覆粉表面的Sem照 片（10,000倍數）； 第11圖所示為本發明比較例2所製備之鍍覆粉表面的SEM照 片（20,000倍數）； 第12圖所示為本發明比較例2所製備之鍍覆粉表面的SEM照 片（8,000倍數）； 第13圖所示為本發明比較例3所製備之鍍覆粉表面的SEM照 21 200916235 片（6,000倍數）；以及 第14圖所示為本發明比較例3所製備之鍍覆粉表面的SEM照 片（20,000倍數）。 【主要元件符號說明】 1 核心材料 2 第一無電金屬鍍覆層 3 過渡金屬突起物 4第二無電金屬鍍覆層 5 金鍍覆層 22The average size of the average protrusion of the protrusion ------ π conductivity - the number of adhesions (nano) (Ω) Example 1 25 310 11 ----- -------- Implementation Example 2 11 〇420 ~ 1 - 12 ---------- 〇 Example 3 15 452 —----- 1 ----— π Example 4 19 522 1 r\ Comparative Example 1 - «_ 25 Comparative Example 2 120 91 61 Comparative Example 3 25 82 One-one - 45 X -------1 X As shown in Table i and Figures 2 to 14, the method of the present invention provides excellent electrical power. Degraded conductive powder (due to the formation of large and regular protrusions without protrusions & the smooth and uniform coverage of the domain and with fine plating), between the resin coatings There are excellent rules and (four) forces (compared to prior art). As described above, the protrusion-type conductive plating powder containing the larger and more regular canines produced by the method of the present invention is excellent in anisotropic conductive film=electrode during thermal compression. The resin is repelled because the surface area where no protrusions are formed is also slip-coated; the electrode has excellent connection reliability; and the excellent adhesion between the coating and the resin powder and the excellent regularity. And: Γ 南 南 南 南 品质 品质 品质 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南 南The implementation of the enemy map; 20 200916235 Figure 2 shows the SEM photograph (6,000 times) of the surface of the plating powder prepared in Example 1 of the present invention; Figure 3 shows the plating prepared in Example 1 of the present invention. SEM photograph (20,000-fold) of the surface of the powder coating; Figure 4 is a SEM photograph (6,000 times) of the surface of the plating powder prepared in Example 2 of the present invention; and Figure 5 is a preparation of Example 2 of the present invention. SEM photograph of the surface of the plated powder (10,000 multiples) Fig. 6 is a SEM photograph (6,000 multiples) of the surface of the coated powder prepared in Example 3 of the present invention; Fig. 7 is a sem photograph of the surface of the coated powder prepared in Example 3 of the present invention ( Fig. 8 is a sem photograph (6,000 times) of the surface of the powder coating powder prepared in Example 4 of the present invention; Fig. 9 is a SEM of the surface of the bell powder prepared in Example 4 of the present invention. Photograph (20,000 multiple); Fig. 10 is a photograph of a Sem (10,000 magnification) of the surface of the ore-coated powder prepared in Comparative Example 1 of the present invention; and Figure 11 is a surface of the plating powder prepared in Comparative Example 2 of the present invention. SEM photograph (20,000 magnifications); Fig. 12 is a SEM photograph (8,000 magnifications) of the surface of the plating powder prepared in Comparative Example 2 of the present invention; and Fig. 13 is a plating preparation prepared in Comparative Example 3 of the present invention. The SEM photograph of the surface of the powder 21 200916235 (6,000 times); and Fig. 14 shows the SEM photograph (20,000 times) of the surface of the plating powder prepared in Comparative Example 3 of the present invention. [Description of main components] 1 Core material 2 First electroless metal plating layer 3 transition metal protrusion 4 Two electroless metal plating layer 5 of gold plating layer 22