200914121 九、發明說明： 【發明所屬之技術領域】 本發明涉及-種導電溶液，特別涉及一種用於印製線 路板通孔金屬化工藝的黑孔化溶液及其製備方法。 【先前技術】 〜通孔金屬化係多層印製線路板製造過程中最關鍵的工 农衣節之’匕對後期線路的形成、上下線路的導通有重 大作用。通孔金屬化指各層印製導線在通孔中經過前處理 後用化學鑛和電鐘的方法使絕緣樹脂的孔壁上鑛上一層 導電金屬，從而使各層印製導線相連接的工藝。 曰 黑孔/職技術（請參見，印製祕板孔^化電鑛工 I電鑛與塗飾，61_65頁，12卷3期（1993))提供了一 if ί學方法實現通孔金屬化技術。採用黑孔增銅技術實 孔金屬化的工藝流程包括：提供-個印製 ί:!、=過鑽孔獲得通孔；對帶有通孔的印製線路板 處理; #_後的印製_板進行黑孔化 ,吏侍’，，、孔化洛液塗覆于通孔孔壁上；對黑孔彳卜卢 後的=線路板電鍍銅，從而實現印製線路板通孔金屬二匕。 則採用的黑孔化溶液，其成分包括：俨 =活性劑，驗性物質和適量的液體溶劑。其中，α = 材料—般採用細小的炭里啖畧斗 —电反 下，這此户里…；成石墨粒子。在分散劑的作用 靜電相定地分散于水中。它們經由 相互作用，被吸附至印製線路板上經整孔 孔中，形成一層導電層。 序後的通 然而，隨著人們對高密度印製線路板的追卞、 這要求 200914121 .印製線路板厚度不斷增加’通孔孔徑不斷縮小 ，]、孔電鑛又要求其在吸附較少黑孔化材料 黑η導電效果。❿目前採用的黑孔化材料炭黑或石 墨粒子，已經不能滿足上述要求。 f生碳材料的黑孔化溶 有鑒于此，提供一種含有高導電, 液及其製備方法實為必要。 【發明内容】BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a conductive solution, and more particularly to a black hole solution for a through-hole metallization process of a printed circuit board and a method of preparing the same. [Prior Art] ~ The most critical tooling of the through-hole metallization multi-layer printed circuit board manufacturing process has a major effect on the formation of the later lines and the conduction of the upper and lower lines. Through-hole metallization refers to a process in which the printed conductors of each layer are pretreated in a through-hole and then a layer of conductive metal is cast on the walls of the insulating resin by means of a chemical ore and an electric clock, thereby connecting the printed conductors of the layers.曰 black hole / job technology (please see, printing secret hole hole ^ chemical miner I electric mine and finishing, 61_65 pages, 12 volumes 3 (1993)) provides a method to achieve through-hole metallization . The process of solid metallization using black hole copper-increasing technology includes: providing - printing ί:!, = through-hole to obtain through-holes; processing of printed circuit boards with through-holes; printing after #_ _ plate for black hole, 吏 ' ',,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, dagger. The black pore solution used includes components: 俨 = active agent, test substance and appropriate amount of liquid solvent. Among them, α = material is generally used in a small charcoal bucket - electric reverse, this household ... ... into graphite particles. The role of the dispersant is electrostatically dispersed in water. They are adsorbed to the through-holes on the printed circuit board via interaction to form a conductive layer. However, as people follow up on high-density printed circuit boards, this requires 200914121. The thickness of printed circuit boards continues to increase, 'the aperture of the through-holes continues to shrink,' and the hole-electric mines require less adsorption. Black hole material black η conductive effect.黑 The currently used black hole material carbon black or graphite particles can no longer meet the above requirements. The black hole of the f-carbon material is dissolved. In view of the above, it is necessary to provide a method containing a high conductivity, a liquid, and a preparation method thereof. [Summary of the Invention]
一種黑孔化溶液，其成分包括：奈米碳管，表面活性 別’驗性物質和適量的液體溶劑。其中，採用單壁、雙辟 ^壁奈求碳管，經過功能化處理後，在分散劑的作 铋疋地分散于域水中形成。這些奈米碳管經由靜電相互作 用’被吸附至印製線路板經整孔m的通孔中，形成一 層導電網路。 進一步，該黑孔化溶液中還可以加入適量 如石夕膠或水溶性聚合物，讀高溶液㈣合性。^ —太、，種製備黑孔化溶液的方法，其具體步驟包括：提供 二米灰g原料’並對奈米碳管原料進行功能化處理；將 力此化的奈米碳管與—鹼性物質混合，將該混合物質加入 旦液體办剤中’得到一懸浮溶液；將該懸浮溶液中加入少 ^表面活性劑；機械攪拌該懸浮溶液，使奈米碳管均勻分 散，得到黑孔化溶液。 、相對于先前技術，所述的黑孔化溶液，採用奈米碳管 ^為^電唆材料。由於奈米碳管具有高的長徑比，故形成 、周路所乾的奈米碳管的量要小於傳統黑孔化溶液中所 200914121 採用的炭黑或石墨。而且，奈米碳管的導電性要 里 與石墨’故㈣上述黑孔化溶液處 厌… 較少黑孔化㈣㈣件下可《❹Η目同 奈米碳管的功能化方法簡單，所需的化t 另 功月b化後所產生的廢液易於處理。 ” 于 【實施方式】 黑孔= = = = =詳術方— 術方案提供—種黑孔化溶液，其成分包括：奈米 石反官’表面活性劑，鹼性物質和適量的液體溶劑。該里孔 二匕溶液中’奈米碳管的重量比，表面活性劑的重 量比為0.01-4%，鹼性物質的重量比為〇 〇1_1%。進一步， 該黑孔化溶液中還可以加入適量的優化劑，如：加入^量 比為0-0.5%的矽膠’重量比為〇_〇2%的水溶性聚合物，以 k南溶液的枯合性。 本技術方案實施例中，奈米礙管可以為通過電狐放電 法、鐳射蒸發法或者化學氣相沈積法所製備的單壁或多壁 的奈求碳管’奈米碳管的長徑比大於1〇〇(hl。奈米碳管均 勻分散在溶液t，在奈米碳管管壁上或端帽處引入親水性 的羧基（-COOH)或羥基（-OH)。該黑孔化溶液中，表面活性 劑選自陰離子表面活性劑（如：十二烷基硫酸鈉）和非離 子表面活性劑（如：聚山梨醇酯）中的一種或多種。表面 活性劑包裹在奈米碳管表面，使奈米碳管均勻分散在溶液 中。該黑孔化溶液中，所用的鹼性物質為氫氧化鈉 200914121 .(NaOH)、氫氧化鉀（κ (k2cxm i水（ΝΗ4〇Η)或碳酸鉀 溶液的mm性;^ _旨在提高黑孔化 入優化劑可以提高溶液的粘合 受攻刀 溶液處理印製線路板時，將於在制該黑孔化 板通孔表面。㈣孔n^，，、孔化讀塗覆在印製線路 選去離早匕孔化办液中，液體溶劑為水，其中，優 ^ 水。亥川、孔化溶液的PH值為8-11。 请參閱圖1’本技街方宏 法，其主要包括以=案一黑孔化溶液的製備方 功能ϋ提供—奈米碳f原料，並對奈㈣管原料進行 射·中’奈米碳管原料選自通過電弧放電法、错 者化學氣相沈積法所製備的單壁或多壁的奈米 二碳;生長的奈米碳管陣列。 、不/卡反5疋向排列而沒有相互纏繞， 管分散於溶液中。奈米碳管的長徑比大於 00.1。大的長徑比有利於奈米碳管形成導電網路。 、子上述不米石反官原料功能化處理分為兩個步驟： f先’提純上述奈米碳管原料。提純奈米碳管原料又 包括以下步驟： 將奈米碳管原料放於we的爐中’在空氣流中加熱2 小時以除去奈米碳管補巾殘留的無定型碳；將爐中剩餘 的奈求碳管原料浸泡在36%的濃鹽酸中，浸泡认，除去夺 米碳管原料中殘留的金屬催化劑；將鹽酸浸泡後的奈米碳 官原料進行離心分離；將分離所得的奈米碳管原料沈殿物 200914121 用去離子水反復洗滌；再將洗滌後的奈米碳管原料沈澱物 經由0.2mm孔徑的聚四氟乙烯膜過濾，得到提純的奈米碳 管原料。 μ 提純的目的在於除去奈米碳管原料中殘留的無定型碳 和金屬催化劑等雜質。通過提純，可以得到純淨的奈米碳 管原料。 其次’功能化處理。對奈米碳管原料功能化處理又包 括以下步驟：A black hole solution comprising: a carbon nanotube, a surface active substance, and an appropriate amount of a liquid solvent. Among them, a single-walled, double-walled carbon tube is used, and after functionalization, it is formed by dispersing the dispersant in the domain water. These carbon nanotubes are adsorbed to the printed circuit board through the through holes of the entire hole m via electrostatic interaction to form a layer of conductive network. Further, an appropriate amount of a gelatin or a water-soluble polymer may be added to the black pore solution to read the high solution (tetra). ^ - too, a method for preparing a black hole solution, the specific steps thereof include: providing a two-meter ash g raw material 'and functionalizing the carbon nanotube raw material; and the carbon nanotube and the alkali Mixing the substance, adding the mixture to the liquid solution to obtain a suspension solution; adding less surfactant to the suspension solution; mechanically stirring the suspension solution to uniformly disperse the carbon nanotubes to obtain black pores Solution. Compared with the prior art, the black hole solution is made of a carbon nanotube material. Since the carbon nanotubes have a high aspect ratio, the amount of carbon nanotubes formed and formed by the circumferential path is smaller than that of the carbon black or graphite used in the conventional black hole solution. Moreover, the conductivity of the carbon nanotubes is the same as that of the graphite. Therefore, the above-mentioned black hole solution is annoying... Less black hole (4) (4) The functionalization method of the carbon nanotubes is simple and required. The waste liquid produced after the other month is easy to handle. [Invention] Black hole = = = = = Detailed prescription - The program provides a black hole solution, the composition of which includes: nano stone anti-official surfactant, alkaline substance and appropriate amount of liquid solvent. The weight ratio of the carbon nanotubes in the lining solution is 0.01-4% by weight of the surfactant, and the weight ratio of the alkaline substance is 〇〇1_1%. Further, the black pore solution can also be used. Adding an appropriate amount of the optimizing agent, for example, adding a water-soluble polymer having a weight ratio of 0-0.5% to a weight ratio of 〇_〇2% to the dryness of the k-nan solution. In the embodiment of the present invention, The nano tube can be a single-walled or multi-walled carbon tube prepared by electric fox discharge method, laser evaporation method or chemical vapor deposition method. The aspect ratio of the carbon nanotubes is greater than 1 〇〇 (hl. The carbon nanotubes are uniformly dispersed in the solution t, and a hydrophilic carboxyl group (-COOH) or a hydroxyl group (-OH) is introduced on the wall of the carbon nanotube tube or at the end cap. In the black pore solution, the surfactant is selected from the group consisting of Anionic surfactants (eg sodium lauryl sulfate) and nonionic surfactants (eg polysorbates) One or more of the surfactants are coated on the surface of the carbon nanotubes to uniformly disperse the carbon nanotubes in the solution. In the black pore solution, the alkaline substance used is sodium hydroxide 200914121 (NaOH). Potassium hydroxide (k2cxm i water (ΝΗ4〇Η) or potassium carbonate solution mm; ^ _ designed to improve the black hole into the optimizer can improve the adhesion of the solution is affected by the tapping solution processing printed circuit board , the surface of the through hole of the black hole plate will be made. (4) The hole n^,, the hole is read and coated on the printed circuit, and the liquid solvent is water, wherein The pH value of the Haichuan and Konghua solution is 8-11. Please refer to Figure 1 'Benji Street Fanghong method, which mainly includes the preparation function of the black hole solution of the case - nano carbon f raw material, and The raw material of the naphthalene (four) tube is selected from the single-wall or multi-walled nano-carbon prepared by the arc discharge method and the chemical vapor deposition method; the grown carbon nanotube array , not / card reverse 5 排列 aligned without intertwining, the tube is dispersed in the solution. The aspect ratio of the carbon nanotube At 00.1, the large aspect ratio is beneficial to the formation of a conductive network of carbon nanotubes. The functionalization of the above-mentioned non-meterite anti-official raw materials is divided into two steps: f first 'purification of the above carbon nanotube raw materials. The carbon nanotube raw material further comprises the following steps: placing the carbon nanotube raw material in the furnace of the 'heating air stream for 2 hours to remove the amorphous carbon remaining in the carbon nanotube filling towel; The carbon tube raw material is immersed in 36% concentrated hydrochloric acid, immersed and recognized, and the metal catalyst remaining in the raw material of the rice carbon tube is removed; the nano carbon official material after the hydrochloric acid immersion is centrifuged; the obtained carbon nanotube raw material is separated. Shen Dianwu 200914121 was repeatedly washed with deionized water; the washed carbon nanotube raw material precipitate was filtered through a 0.2 mm pore size polytetrafluoroethylene membrane to obtain a purified carbon nanotube raw material. The purpose of μ purification is to remove impurities such as amorphous carbon and metal catalyst remaining in the carbon nanotube raw material. Pure carbon nanotube raw materials can be obtained by purification. Secondly, functional processing. The functionalization of the carbon nanotube raw materials further includes the following steps:
將初步提純過的奈米碳管原料在硝酸中回流加熱48小 夺在笞壁上或端帽處引入親水性的叛基（_c〇〇h)或經基 (ΟΗ)，然後將回流加熱後的奈米石炭管原料經由孔徑 的過濾膜過濾，得到奈米碳管固體；用去離子水反復洗滌 該奈米碳管固體至濾液的PH值為7。 功能化處理的旨在使奈米碳管表面帶有負電荷。在應 用—該黑孔化溶液處理印製線路板時，帶有負電荷的奈米碳 官通過靜電相互作用可以吸附在印製線路板通孔表面。請 參閱圖2 ’按上述功能化方法處理後的奈米碳管11，在管壁 上或端帽處引入親水性的羧基（ _COOH)或羥基（ 〇H)。 按上述功能化方法處理後的奈米碳管11，長度方面與 未處理鈾相似，而奈米碳管n表面由於氧化的原因，其粗 糖度有所增加。表明以上的處理方法只是在奈米碟管原有 ，缺陷處發生了氧化反應’並沒有在奈米碳管表面引入更 夕的缺陷，這樣對奈米碳管原有的電學性能影響不大。 (一）將功能化的奈米碳管與一驗性物質混合，將混 合物加入至一液體溶劑中，得到一懸浮溶液。 匕 11 200914121 本實施例中，上述鹼性物質可以為氳氧化鈉 (NaOH)、氫氧化鉀（K〇H)、氨水（而4加）或破酸卸 (K2C03)等鹼性物質。其中’鹼性物質旨在用來調節溶 液的PH值。通過調節驗性物質的重量&，使得到的懸浮液 PH值在8-11之間。考慮到成本和使用方便，溶劑選用水， 而且優L去離子水，旨在以後的電鑛工序中減少 離 的污染。該懸浮液中，奈米碳管的重量比小於3%。 (二）將該懸浮溶液中加入少量表面活性劑。 本實施例中，加入表面活性劑旨在增進奈米碳管的表 面潤濕性能，使相互纏繞的奈米碳管容易分散。所用表面 活性劑選自陰離子表面活性劑（如：十二燒基硫酸納）及 非離子表面活性劑（如：聚山梨醇醋）中的—種或多種。 (四）機械攪拌該懸浮溶液得到黑孔化溶液。 本實施例中，在室溫下機械攪拌混合溶液，時間為 20-50分鐘。得到黑孔化溶液。機械攪拌的過程中，表面活 裹在奈米碳管表面，從而使奈米碳管均勾的分散在 溶液裏。 本實施例中，在上述黑孔化溶液中，可以進_步加入 優化劑。優化劑為矽膠或水溶性聚合物，如. (PVA)、聚維飼（PVP)。其中，石夕膠的ΡΗ值為㈣，水 合物分子量為麵侧。在上述黑孔化溶液中加人 :塗:溶液_合性’有利於黑孔化溶液更好 的塗覆在印製線路板通孔表面。 ,t實施财，進—步提供—種應用上述方法製備的里 孔化浴液實現印製線路板通孔金屬化的方法，其具體包括 12 200914121 以下步驟： (一） 提供一個印製線路板，並通過鑽孔獲得通孔。 印製線路板為覆銅層壓板。 (二） 清洗帶有通孔的印製線路板’清除線路板通孔 中的油污和其他雜質，中和樹脂表面的電荷，以利於黑孔 化溶液在孔壁上完全吸附。 (二）將清洗後印製線路板置入上述黑孔化溶液中浸 潰，製得黑孔化板。 又 本實施例中，將清洗後的印製線路板浸入黑孔化溶液 中，溫度保持在15_4(rc。浸潰㈣分鐘。黑孔化溶液均 勻地塗覆在印製線路板通孔孔壁上，並與絕緣基層良好接 觸，得到黑孔化線路板。黑孔化溶液中的奈米碳管由於靜 電相互作用，被吸附至孔中形成導電網路。由於奈米碳管 具有高的長徑比，故形成導電網路所需的奈米碳管的量要 小於傳統黑孔化溶液中所採用的炭黑或石墨。而且，奈米 石f管的導電性要好于炭黑與石墨，故採用上述黑孔化i液 處理印製線路板，在吸附較少黑孔化材料的條件下可以達 =相同的導電效果。該黑孔化溶液可以應用於對更厚的印 製線路板的孔徑更小的通孔進行金屬化的工藝中。 、（四）乾燥黑孔化板，塗覆在印製線路板表面的軍 化溶液形成一黑色薄膜。 … (五）進行去膜處理，將銅層表面的黑色薄膜除去。 (/、）對上述黑孔化板進行電鍵銅。 本實施例中，以吸附了奈米碳管的印製線路板作為陰 °進仃電鍍作業，電鍍作業在常規酸性電鍍槽中進行。二 13 200914121 .果為通孔被金屬化’得到金屬化印製線路板。由於奈米碳 管優異的導電性，電鍍銅時獲得相同的鍍層厚度所用的時 間少於採用傳統黑孔/鍍銅技術所用的時間。 實施例 將奈米碳管原料放在350 °C的爐中，在空氣流中加熱2 小時以除去奈米竣管原料中的無定型碳。然後將爐中剰餘 的奈米碳官原料浸泡在36%的濃鹽酸中丄天后離心分離，所 得的沈澱用去離子水反復洗滌。經由〇2mm孔徑的聚四氟 乙烯膜過濾得到提純的奈米碳管原料。將提純過的奈米碳 管原料80mg在2.6M的硝酸中回流加熱48小時後，經由 lOOnrn孔徑的過濾膜過濾後，得到奈米碳管固體。用去離 子水反復洗滌至濾液的PH值為7。稱量一定量的上述功能 化後的奈米碳管和一定量的碳酸鉀。將上述碳酸鉀和功能 化後的奈米碳管混合，加入到一定量的去離子水中，再加 入少里十一烷基硫酸鈉。控制溶液中奈米碳管的重量比為 1%。通過調節碳酸鉀的重量比，控制溶液的pH值為。 在室溫下，機械攪拌30分鐘得到黑孔化溶液。 提供一個印製線路板，並通過鑽孔獲得通孔。將鑽孔 後。的印製線路板放入減洗槽中浸泡5分鐘，減洗槽溫度為 40 C。取出後用水沖洗，再放入離子水槽中浸泡，並立即 取出放入馱洗槽中浸潰2分鐘。酸洗槽溫度為室溫。取出後 用水沖洗，再放入離子水槽中浸泡，並立即取出放入上述 黑孔化溶液，在室溫下浸潰4分鐘後製得黑孔化板。取出該 黑孔化板，用烘乾箱將其烘乾，烘乾温度為1〇5。匚。將烘乾 後的線路板冷卻到室溫後，用濃度為〇5%的硫酸弱腐蝕液 200914121 浸泡50秒，黑孔化板表面的黑色薄膜成片脫落。取出並用 水沖洗後即可進行電鍍作業。將去膜後的黑孔化板放入電 鍍槽中作為陰極電鍍銅。電鍍時，電流密度為8A/dm2，電 鍍時間保持在5分鐘，鍍層厚度為1〇〇# m。 綜上所述，本發明確已符合發明專利之要件，遂依法 提出專利申請。惟，以上所述者僅為本發明之較佳實施例， 自不能以此限制本案之申請專利範圍。舉凡熟悉本案技藝 之人士挺依本發明之精神所作之等效修飾或變化，皆應涵 蓋於以下申請專利範圍内。 【圖式簡單說明】 圖1係本技術方案實施例中黑孔化溶液的製備方法的 流程圖 圖2係本技術方案實施例中功能化處理後的奈米碳管 的示意圖 【主要元件符號說明】 奈米碳管 11 15The initially purified carbon nanotube raw material is heated under reflux in nitric acid for 48 hours to introduce a hydrophilic thiol (_c〇〇h) or a transbasic (ΟΗ) at the wall or at the end cap, and then heated under reflux. The nano-carboniferous material is filtered through a pore size filter membrane to obtain a carbon nanotube solid; the carbon nanotube solid is repeatedly washed with deionized water until the pH of the filtrate is 7. The functionalization is designed to impart a negative charge to the surface of the carbon nanotubes. When the printed circuit board is treated with the black hole solution, the negatively charged nanocarbon can be adsorbed on the surface of the through hole of the printed circuit board by electrostatic interaction. Referring to Figure 2, the carbon nanotubes 11 treated according to the above functionalization method introduce a hydrophilic carboxyl group (_COOH) or a hydroxyl group (〇H) on the tube wall or at the end cap. The carbon nanotubes 11 treated according to the above functionalization method are similar in length to untreated uranium, and the surface of the carbon nanotube n has an increased sugar content due to oxidation. It shows that the above treatment method is only in the original of the nano-disc tube, and the oxidation reaction occurs at the defect. The defect is not introduced on the surface of the carbon nanotube, which has little effect on the original electrical properties of the carbon nanotube. (1) The functionalized carbon nanotube is mixed with a test substance, and the mixture is added to a liquid solvent to obtain a suspension solution.匕 11 200914121 In the present embodiment, the alkaline substance may be an alkaline substance such as sodium hydride (NaOH), potassium hydroxide (K〇H), ammonia (and 4) or acid-depleted (K2C03). The 'basic substance' is intended to adjust the pH of the solution. By adjusting the weight & of the test substance, the resulting pH of the suspension is between 8 and 11. Considering the cost and ease of use, the solvent is water, and the L-deionized water is designed to reduce the pollution in the subsequent electric ore process. In the suspension, the weight ratio of the carbon nanotubes is less than 3%. (2) adding a small amount of a surfactant to the suspension solution. In this embodiment, the addition of a surfactant is intended to enhance the surface wetting property of the carbon nanotubes, so that the intertwined carbon nanotubes are easily dispersed. The surfactant used is selected from the group consisting of anionic surfactants (e.g., sodium dodecyl sulfate) and nonionic surfactants (e.g., polysorbate). (4) Mechanically stirring the suspension solution to obtain a black pore solution. In this example, the mixed solution was mechanically stirred at room temperature for a period of 20 to 50 minutes. A black pore solution was obtained. During mechanical agitation, the surface is wrapped around the surface of the carbon nanotubes so that the carbon nanotubes are dispersed in the solution. In the present embodiment, in the above-mentioned black hole solution, the optimizer may be added in a stepwise manner. The optimizer is silicone or water soluble polymer, such as (PVA), polyvitamin (PVP). Among them, the ΡΗ value of Shixi gum is (4), and the molecular weight of the hydrate is the surface side. Adding a solution to the above-mentioned black hole solution: coating: solution-compatibility is advantageous for better coating of the black hole solution on the surface of the through-hole of the printed wiring board. , t implements the financial, further provides a method for applying the boring bath prepared by the above method to realize the through-hole metallization of the printed circuit board, which specifically includes 12 200914121. The following steps: (1) providing a printed circuit board And through holes to obtain through holes. The printed wiring board is a copper clad laminate. (2) Cleaning the printed circuit board with through holes 'clearing oil and other impurities in the through holes of the circuit board, neutralizing the charge on the surface of the resin to facilitate complete adsorption of the black hole solution on the hole walls. (2) The printed circuit board after the cleaning is placed in the black hole solution to be immersed to obtain a black hole plate. In this embodiment, the cleaned printed wiring board is immersed in the black hole solution, and the temperature is maintained at 15_4 (rc. immersion (four) minutes. The black hole solution is uniformly coated on the through-hole hole wall of the printed circuit board. Above, and in good contact with the insulating base layer, a black-pore circuit board is obtained. The carbon nanotubes in the black hole solution are adsorbed into the holes to form a conductive network due to electrostatic interaction. Since the carbon nanotubes have a high length The ratio of the diameter of the carbon nanotubes required to form the conductive network is smaller than that of the conventional black hole solution. Moreover, the conductivity of the nanotubes is better than that of carbon black and graphite. Therefore, the printed circuit board is treated by the above black hole i liquid, and the same conductive effect can be achieved under the condition of adsorbing less black hole material. The black hole solution can be applied to a thicker printed circuit board. The through hole of the smaller aperture is metallized. (4) The blackened plate is dried, and the military solution coated on the surface of the printed circuit board forms a black film. (5) The film is removed, The black film on the surface of the copper layer is removed. (/,) The black hole plate is made of a copper bond. In this embodiment, a printed circuit board on which a carbon nanotube is adsorbed is used as a negative electrode plating operation, and the plating operation is performed in a conventional acid plating bath. 2 13 200914121 . The vias are metallized' to obtain a metallized printed wiring board. Due to the excellent electrical conductivity of the carbon nanotubes, the time required to obtain the same plating thickness when electroplating copper is less than the time taken by conventional black hole/copper plating techniques. For example, the carbon nanotube raw material is placed in a furnace at 350 ° C, and heated in an air stream for 2 hours to remove amorphous carbon in the raw material of the nano tube. Then, the remaining carbon carbon raw material in the furnace is soaked in the furnace. 36% concentrated hydrochloric acid was centrifuged in the day, and the resulting precipitate was washed repeatedly with deionized water. The purified carbon nanotube raw material was obtained by filtration through a PTFE membrane with a pore size of 2 mm. The purified carbon nanotube raw material was purified. 80 mg was heated under reflux in 2.6 M nitric acid for 48 hours, and then filtered through a filtration membrane of 100 nrn pore size to obtain a carbon nanotube solid. The washing was repeated with deionized water until the pH of the filtrate was 7. Weigh a certain amount of the above functions.After the carbon nanotubes and a certain amount of potassium carbonate, the above potassium carbonate and the functionalized carbon nanotubes are mixed, added to a certain amount of deionized water, and then added sodium lauryl sulfate. The weight ratio of the medium carbon nanotubes is 1%. The pH of the solution is controlled by adjusting the weight ratio of potassium carbonate. The black hole solution is obtained by mechanical stirring at room temperature for 30 minutes. A printed circuit board is provided, and The through hole is obtained by drilling. The printed circuit board after drilling is placed in the rinsing tank for 5 minutes, and the temperature of the rinsing tank is 40 C. After taking out, rinse with water, then put it into the ion sink to soak, and immediately Take out and put in the rinsing tank for 2 minutes. The temperature of the pickling tank is room temperature. After taking out, rinse with water, then put it into the ion sink and soak it, and immediately take it out and put it into the above black hole solution, soak it at room temperature. A black hole plate was prepared after 4 minutes. The black plate was taken out and dried in a drying oven at a drying temperature of 1〇5. Hey. After the dried circuit board was cooled to room temperature, it was immersed for 50 seconds with a sulfuric acid weak etching solution of 5% 5%, and the black film on the surface of the black hole plate was peeled off. The plating operation can be carried out after taking out and rinsing with water. The blackened plate after the film removal was placed in an electroplating bath as a cathode electroplated copper. At the time of electroplating, the current density was 8 A/dm 2 , the plating time was maintained at 5 minutes, and the plating thickness was 1 〇〇 # m. In summary, the present invention has indeed met the requirements of the invention patent, and has filed a patent application according to law. However, the above description is only a preferred embodiment of the present invention, and it is not possible to limit the scope of the patent application in this case. Equivalent modifications or variations made by those skilled in the art in light of the spirit of the present invention are intended to be included in the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for preparing a black hole solution in an embodiment of the present technical solution. FIG. 2 is a schematic view of a carbon nanotube after functionalization in an embodiment of the present technical solution. 】 Carbon nanotubes 11 15