200951187 九、發明說明： 【發明所屬之技術領域】 本發明涉及喷墨印刷技術領域，特別涉及一種油墨及 ’利用該油墨製作導電線路之方法。 【先前技術】 利用喷墨列印技術製作導電線路於近年來受到了廣泛 關注，此方法只需將所需線路圖形直接由電腦給出，再藉 ®由控制器控制喷墨印刷系統之喷嘴，將油墨顆粒由喷嘴噴 出並逐點地形成線路圖形，製作線路圖形能夠精確控制線 路之位置及寬度，該方法屬非接觸式數碼圖案製程，可減 少不同印刷材料間相互污染。相較於傳統線路製作方法， 具有製作流程更加簡化、成本低及低污染之優點。請參見 文獻：Murata，K.; Matsumoto，J.; Tezuka，A.; Oyama，K·; Matsuba，Y.; Yokoyama, H.; Super fine wiring by inkjet printing Microprocesses and Nanotechnology Conference, 2004. Digest of Papers. 2004 InternationalOct. 27-29, 2004 Page(s):24-25。 先前技術中報導一種採用喷墨列印含有可溶性銀鹽之 墨水製造導電線路之方法。該方法係將可溶性銀離子溶液 製成可喷墨列印之墨水，於基材表面列印出含有銀離子線 路，然後於該線路表面列印含有還原劑如甲醛之墨水，藉 由氧化-還原反應將銀離子還原成為金屬銀，從而賦予線路 以導電性。上述方法原理上比較簡單，但實際操作並不容 200951187 =如需要大量實驗以配製氧化劑墨水與還原劑墨水；製 媳線路需要於基材表面同一位置反復列印，這樣存於印表 :之準確疋位問題；另外，所形成之銀線路於實際使用之 β程令還存於銀離子遷移，導致線路可靠度下降。 【發明内容】 、有鑑於此，提供一種油墨利用該油墨製作導電線路之 ❹方法實為必要，以避免於基材表面之同一位置反復列印， 使得製作之導電線路準確定位，並能夠提升線路之可靠度。 以下將以實施例說明一種油墨及利用該油 線路之方法。 表并导電 一種油墨，該油墨包括銀氨絡合物與還原劑。 :種利用該油墨製作導電線路之方法，將包括還原 、銀氛絡合物之油墨藉由嘴墨列印方式於基板表面形成線 路圖形；採用輻射照射線路圖形，使該線路圖形中之銀氨 ❹絡合物被還原劑還原為金屬銀粒子，從而獲得預製線路； 於该預製線路之軌跡鑛覆金屬，以形成導電線路。 與先前技術相比，該導電線路之製作方法避免了分別 配製氧化性油墨與還原性油墨再分別進行列印之問題 化了線路製作之工藝。 【實施方式】 下面將結合_及實施例對本技術方案實施例提供之 -種油墨及湘該油墨製料f線路方法作進—步詳細說 200951187 明。 本技術方案實施例提供之油墨，其包括還原劑與銀氨 絡合物。由於該油墨為水溶性，該銀氨絡合物完全溶解於 溶劑^ ’具有較好分散性。該油墨之配製具體如下： 首先配製/辰度為l(T4mol/L至5mol/L之銀鹽溶液， 向上述銀鹽溶液加入敏化劑，形成銀氨絡合物溶液。上述 溶液之溶劑可為水，也可為溶於水之有機溶劑如丙酮、乙 ❹醇等之水/合液，該可溶性銀鹽可為硝酸銀、碳酸銀、醋 銀及檸檬酸銀等，該敏化劑為氨水及有機胺類 可為甲胺、乙胺等一元與多元胺，也可為一級、二 級有機胺。該敏化劑與銀鹽之摩爾濃度比為1比；1至3比i 之間，配得溶液中之銀氨絡合物之濃度為ι〇_ν〇ι/1 5mol/L。 王 其次，向上述混合溶液中加入還原劑，還 ❹ 檬酸納或酒石酸㈣。該還原劑之濃度為ig_ = 5mol/L。 王 _再次：加入連接料、分散劑、保濕劑，表面活性劑等 該連接料可為聚氨醋、；:;醇=二_^ =基：略=聚乙稀醇等水溶性聚合物，該保濕劑可 \ 一醇醇_、二甘醇及甘油等高滞點_，該表 :活性劑可為陽離子表面活性劑、陰離子表面活性劑或兩 了 ^生劑。上述各助劑之加人量為體積比至娜 可加入防腐劑與殺菌劑等其他助劑。 疋 200951187 最後’充分攪拌上述混合溶液，使得全部助劑溶於溶 齊J中，得到配製完成之油墨。 . 該油墨還原劑具有較弱之還原性，沒有輻射照射之狀 態下’還原劑不與銀氨絡合物發生反應，該油墨可長時間 穩定存在。於輻射照射下’銀氨絡合物中之銀離子被還原 成單質銀。 請參閱圖1 ’本實施例提供之利用該油墨製作導電線路 之方法。 ❹ 第一步’將該油墨通過喷墨列印之方式印刷於基板100 表面以形成線路圖形。 如圖2所示，本實施例中，基板100為電路板製作過 程中需要進行線路製作之半成品。根據所要製作之電路板 之結構可選擇不同結構之基板100。例如，當待製作之電路 板為單層板時，該基板100為一層絕緣層；當待製作之電 路板為多層電路板時，該基板100為一由多層板與一絕緣 ©層壓合後所形成之結構，還可為矽基板或玻璃基板。本實 施例中，基板100為需要製作單面線路之單層板。該基板 100具有用於形成導電線路之表面110。當然，該基板100 也可用於製作雙面板，只要於基板100相對設置之兩個表 面上製作即可。 為增加形成之線路圖形200與基板100之表面110之 結合強度，於基板100形成線路圖形200之前，可藉由清 洗、微蝕等方法對基板110進行表面處理，以除去附著於 表面110之污物、氧化物、油脂等。 200951187 =圖3所示，分別於基板⑽之表面11〇藉由喷墨印 -"'形成線路圖形200。具體地，喷墨列印系統於控制器 〇控制下根據所需製作之導電線路之圖形，將該油墨自喷 圖灌到表面110’使沈積於表面11〇之油墨形成線路 路之圖形:墨形成之線路圖形2〇0與所需製作之導電線 ο 二步採用輻射照射線路圖形細，使該線路圖形 預製線絡合物被還原劑還原為金屬銀粒子，從而獲得 路圖^ 3及圖4所示，將形成於基板⑽表面110之線 圖形ί〇〇〇0之 1 變成預製線路3〇0。即，表面110上形成線路 合物中之銀Γ單=形合大物析與出該還原劑經化學反應，使銀氨絡 形成預製線路鳩。 從而於表面110上由銀單質 ❹ 應，==銀氨絡合物與該還原劑不發生化學反 與還原劑發生氧化田，…射，使侍銀氨絡合物 绩致應，析出銀單質，從而形成預製 線路該韓射可為紫外光、㈣或γ射線等。 外燈，將形成線路圖形細之基板⑽置於紫 光昭^0八^紫外切距離表面11G之距離約A 8厘米， 後料 取出紐100，對基材100進行水洗，铁 ^ 猎由上述過程，即可使得線路_ 200轉化為單 質銀之預製線路遍。實際操作中，可跟 … 對照射光之強度與照射時間進行調節。τ p之要， 200951187 ^ 一步·於預製線路之軌跡鍍覆金屬，以形成導 .電線路4〇〇。 •= 步驟中’包括還原劑與銀氨絡合物之油墨經喷墨 、統噴射至基板⑽之表面11G形成線路圖形200時， 該線路圖形2ΠΠ & \ y = 為为佈於表面110之還原劑與銀氨絡合物 3 =。該銀氨絡合物中金屬離子間可能沒有完全結合，其 面11^較差，使銀經反應生成之金屬銀粒子也為分佈於表 ❹之連續性較差之金屬銀粒子，從而降低由該金屬銀 &子形成之預製線路則之導電性，使整個預製線路耀 可月b無法達到良好之電性導通。 一因此，如圖5所示，於預製線路300之金屬銀粒子表 面經過電鑛或化學鑛之方法鑛覆金屬，使所艘覆金屬完全 匕裹於預製線路3〇〇之金屬銀粒子外並填充相鄰兩個金屬 銀粒子之間隙，從而形成連續之導電線路4〇〇。於鍍覆金屬 時，形成預製線路300之每個金屬銀粒子作為鍍覆反應之 ©催化中心，並以該每個金屬銀粒子為中心於其表面生長出 複數金屬粒子。該複數金屬粒子緻密排列於每個金屬銀粒 子之表面，使該每個金屬銀粒子完全被複數金屬粒子包 裹，同時沒有完全結合之相鄰兩個金屬銀粒子之表面分別 生長出之複數金屬粒子將該相鄰兩個金屬銀粒子電性連 接從而於基板之表面no形成具有良好之電性導通 之導電線路400。該鍍覆之金屬可為銅或鎳等，鍍覆金屬可 採用電鑛或化學鍵之方式。 本實施例中，對包括金屬銀粒子之預製線路300進行 11 200951187 化學鍍銅，於基板100之表面110形成導電線路400。具體 地，將形成預製線路300之基板100置於化學鍍銅溶液中， 於50攝氏度之溫度下進行化學鍍銅2分鐘，即可使預製線 路300形成完全電連通之導電線路400。導電線路400中之 銅粒子之粒徑為50至150奈米。該鍍液還可包括銅化合 物、還原劑與絡合劑。銅化合物可為硫酸銅、氣化銅等； 還原劑可為曱醛、乙醛酸等；絡合劑可為乙烯二胺四乙酸 二鈉鹽、酒石酸鉀鈉等絡合物。當然，還可於渡液中加入 穩定劑、光亮劑等，以滿足化學鍍之需要。具體地，該鍍 銅溶液之組分為：硫酸銅10g/L、酒石酸鉀鈉22g/L、乙烯 二胺四乙酸二鈉鹽50g/L、甲醛15mL/L及曱醇10mL/L。 其中，固體採用品質體積比，即，單位體積溶液中含該固 體之品質，單位g/L ;液體採用體積體積比，即，單位體積 溶液中含該液體之體積，單位mL/L。 由此完成基板100之表面110具有較高導電性及均勻 ❹性之導電線路300之製作，以供後續加工使用。該製作方 法採用同時含有氧化劑銀氨絡合物與弱還原劑之油墨，該 銀氨絡合物與弱還原劑於常溫狀態下穩定存於，於高能量 光之照射下，迅速發生化學反應。這樣避免了分別配製氧 化性油墨與還原性油墨再分別進行列印之問題，於保證了 線路品質之情況下，簡化了線路製作之工藝。本製作方法 中之油墨之主要成分易溶於水，不必考慮分散穩定之問 題。本方法中銀氨絡合物與弱還原劑之反應於輻射照射條 件下進行，所需設備簡單，而且方便進行控制。此外，鍍 12 200951187 覆金屬提n 了線路之導電性，並對銀線路進行了保護，避 兔了銀離子遷移之問題。 、练上所述，本發明確已符合發明專利之要件，遂依法 提出專射。惟，以上料者料本發明之較佳實施方 式’自不能以此限制本案之中請專利範圍。舉凡熟悉本案 技藝之人士援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係本技術方案提供之製作導電線路方法之流程圖。 圖2係本技術方案實施例提供之基板之結構示意圖。 圖3係圖2中基板形成線路圖形之結構示意圖。 圖4係圖2中基板形成預製線路之結構示意圖。 圖5係圖2中基板形成導電線路之結構示意圖。 【主要元件符號說明】 基板 100 表面 110 線路圖形 200 預制線路 300 導電線路 400 13BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the field of ink jet printing technology, and more particularly to an ink and a method of making a conductive line using the ink. [Prior Art] The use of ink jet printing technology to fabricate conductive lines has received much attention in recent years. This method only requires the required line pattern to be directly given by the computer, and then the controller controls the nozzle of the inkjet printing system. The ink particles are ejected from the nozzles to form a line pattern point by point, and the line pattern can be precisely controlled to control the position and width of the line. The method is a non-contact digital pattern process, which can reduce mutual contamination between different printing materials. Compared with the traditional circuit manufacturing method, it has the advantages of more simplified production process, low cost and low pollution. See literature: Murata, K.; Matsumoto, J.; Tezuka, A.; Oyama, K.; Matsuba, Y.; Yokoyama, H.; Super fine wiring by inkjet printing Microprocesses and Nanotechnology Conference, 2004. Digest of Papers 2004 InternationalOct. 27-29, 2004 Page(s): 24-25. A method of fabricating a conductive line by ink jet printing of an ink containing a soluble silver salt has been reported in the prior art. In the method, the soluble silver ion solution is made into an inkjet printable ink, and a silver ion line is printed on the surface of the substrate, and then an ink containing a reducing agent such as formaldehyde is printed on the surface of the circuit by oxidation-reduction. The reaction reduces the silver ions to metallic silver, giving the line conductivity. The above method is simple in principle, but the actual operation does not allow 200951187 = If a large number of experiments are required to prepare the oxidant ink and the reducing agent ink; the sputum line needs to be repeatedly printed at the same position on the surface of the substrate, so that it is stored in the printing table: In addition, the formed silver line is still in the silver ion migration in the actual use of the β-cycle, resulting in a decrease in line reliability. SUMMARY OF THE INVENTION In view of the above, it is necessary to provide a method for making an ink using the ink to make a conductive line, thereby avoiding repeated printing at the same position on the surface of the substrate, so that the fabricated conductive line is accurately positioned and the line can be lifted. Reliability. An ink and a method of using the same will be described below by way of examples. The sheet is electrically conductive and comprises an ink comprising a silver ammonia complex and a reducing agent. : a method for making a conductive line by using the ink, forming a line pattern on the surface of the substrate by using a method of printing the ink of the silver complex by using a nozzle ink printing method; using a radiation irradiation circuit pattern to make the silver ammonia in the line pattern The ruthenium complex is reduced to metallic silver particles by a reducing agent to obtain a prefabricated line; the trajectory of the prefabricated line is coated with a metal to form a conductive line. Compared with the prior art, the manufacturing method of the conductive line avoids the problem of separately preparing the oxidizing ink and the reducing ink separately for printing, and the process of making the line. [Embodiment] Hereinafter, a method for providing an ink and a method for preparing an ink material f line provided by an embodiment of the present technical solution will be described in conjunction with the embodiment and the embodiment. An ink provided by an embodiment of the present technical solution includes a reducing agent and a silver ammonia complex. Since the ink is water-soluble, the silver-ammonium complex is completely soluble in the solvent to have good dispersibility. The preparation of the ink is as follows: Firstly, a silver salt solution of 1 (T4mol/L to 5mol/L) is prepared, and a sensitizer is added to the silver salt solution to form a silver ammonia complex solution. The solvent of the above solution can be It may be water or a water/liquid mixture of an organic solvent soluble in water such as acetone or acetol. The soluble silver salt may be silver nitrate, silver carbonate, silver vinegar or silver citrate, and the sensitizer is ammonia water. And the organic amines may be monoamines and polyamines such as methylamine and ethylamine, or may be primary and secondary organic amines. The molar concentration ratio of the sensitizer to the silver salt is 1 ratio; between 1 and 3 ratios, The concentration of the silver ammonia complex in the solution is ι〇_ν〇ι/1 5 mol/L. Wang Qiji, adding a reducing agent to the above mixed solution, or sodium citrate or tartaric acid (IV). The concentration is ig_ = 5mol/L. Wang _ again: adding the binder, dispersant, moisturizer, surfactant, etc. The binder can be polyurethane,;:; alcohol = two _^ = base: slightly = poly a water-soluble polymer such as a dilute alcohol, the humectant may have a high hysteresis point such as alcoholic alcohol, diethylene glycol and glycerol, and the active agent may be a cation. Surfactant, anionic surfactant or two bio-agents. The above-mentioned additives are added in a volume ratio to the other additives such as preservatives and fungicides. 疋200951187 Finally 'satisfy the above mixed solution, So that all the auxiliaries are dissolved in the solvent J to obtain a finished ink. The ink reducing agent has a weak reducing property, and the reducing agent does not react with the silver ammonia complex in the absence of radiation irradiation. It can be stably existed for a long time. Under the irradiation of radiation, the silver ions in the silver-ammonia complex are reduced to elemental silver. Please refer to Fig. 1 'The method for making conductive lines using the ink provided in this embodiment. ❹ First step' The ink is printed on the surface of the substrate 100 by inkjet printing to form a line pattern. As shown in FIG. 2, in the embodiment, the substrate 100 is a semi-finished product that needs to be fabricated during the circuit board manufacturing process. The structure of the circuit board can be selected from different structures of the substrate 100. For example, when the circuit board to be fabricated is a single layer board, the substrate 100 is an insulating layer; When the circuit board is a multi-layer circuit board, the substrate 100 is a structure formed by laminating a multi-layer board and an insulating layer, and may also be a germanium substrate or a glass substrate. In this embodiment, the substrate 100 needs to be fabricated on one side. The substrate 100 has a surface 110 for forming a conductive line. Of course, the substrate 100 can also be used to fabricate a double panel, as long as it is formed on the opposite surfaces of the substrate 100. The bonding strength between the circuit pattern 200 and the surface 110 of the substrate 100 can be surface-treated by a method such as cleaning or micro-etching to remove dirt and oxide adhering to the surface 110 before the substrate 100 forms the wiring pattern 200. , grease, etc. 200951187 = As shown in FIG. 3, the wiring pattern 200 is formed by inkjet printing on the surface 11 of the substrate (10). Specifically, the inkjet printing system, under the control of the controller 根据, according to the pattern of the conductive lines to be fabricated, the ink is poured from the spray pattern onto the surface 110' to form a pattern of ink deposited on the surface 11〇: ink The formed circuit pattern 2〇0 and the conductive line to be fabricated ο the second step is to use the radiation irradiation line pattern to make the line pattern prefabricated line complex reduced to metal silver particles by the reducing agent, thereby obtaining the road map ^ 3 and As shown in Fig. 4, the line pattern ί〇〇〇0 of the surface 110 formed on the substrate (10) is changed to the prefabricated line 3〇0. That is, the silver ruthenium formed in the wiring composition on the surface 110 is deformed and chemically reacted with the reducing agent to form a pre-fabricated crucible. Therefore, on the surface 110, the silver element is ❹, == the silver-ammonium complex and the reducing agent do not chemically react with the reducing agent to form an oxidized field, ..., so that the silver-ammonia complex is caused to react, and the silver element is precipitated. To form a prefabricated line, the Korean shot can be ultraviolet light, (four) or gamma rays, and the like. The outer lamp, the substrate (10) forming the fine line pattern is placed at a distance of about 8 cm from the surface of the ultraviolet light-cutting surface 11G, and the material 100 is taken out, and the substrate 100 is washed with water, and the iron is hunted by the above process. , the line _ 200 can be converted into a pre-made line of elemental silver. In actual operation, the intensity of the illumination and the illumination time can be adjusted. τ p要要, 200951187 ^ One step · plating the metal on the track of the prefabricated line to form the conductive line 4〇〇. • In the step, when the ink including the reducing agent and the silver ammonia complex is sprayed onto the surface 11G of the substrate (10) to form the wiring pattern 200, the wiring pattern 2ΠΠ & \ y = is disposed on the surface 110. Reducing agent and silver ammonia complex 3 =. The silver-ammonium complex may not have complete bonding between the metal ions, and the surface thereof is relatively poor, so that the metal silver particles formed by the reaction of the silver are also metallic silver particles which are poorly distributed in the surface of the surface, thereby reducing the metal. The pre-fabrication of the silver & sub-forms is electrically conductive, so that the entire prefabricated circuit can not achieve good electrical conduction. Therefore, as shown in FIG. 5, the surface of the metal silver particles on the prefabricated line 300 is coated with metal by means of electric ore or chemical ore, so that the coated metal is completely wrapped around the metal silver particles of the prefabricated line 3 and The gap between adjacent two metallic silver particles is filled to form a continuous conductive line 4〇〇. When metal is plated, each of the metal silver particles of the prefabricated line 300 is formed as a © catalytic center of the plating reaction, and a plurality of metal particles are grown on the surface of the metal silver particles. The plurality of metal particles are densely arranged on the surface of each of the metallic silver particles, so that each of the metallic silver particles is completely surrounded by the plurality of metal particles, and the plurality of metal particles respectively grown on the surfaces of the adjacent two metallic silver particles are not completely combined The two adjacent metal silver particles are electrically connected to form a conductive line 400 having good electrical conduction on the surface no of the substrate. The plated metal may be copper or nickel, and the plated metal may be in the form of electric ore or chemical bonds. In the present embodiment, the copper plating is performed on the prefabricated line 300 including the metallic silver particles, and the conductive wiring 400 is formed on the surface 110 of the substrate 100. Specifically, the substrate 100 forming the prefabricated line 300 is placed in an electroless copper plating solution, and electroless copper plating is performed at a temperature of 50 ° C for 2 minutes to form the electrically conductive line 400 in which the prefabricated wiring 300 is completely electrically connected. The copper particles in the conductive line 400 have a particle diameter of 50 to 150 nm. The bath may also include a copper compound, a reducing agent, and a complexing agent. The copper compound may be copper sulfate, vaporized copper or the like; the reducing agent may be furfural or glyoxylic acid; and the complexing agent may be a complex such as ethylene diamine tetraacetic acid disodium salt or sodium potassium tartrate. Of course, stabilizers, brighteners, etc. can also be added to the liquid to meet the needs of electroless plating. Specifically, the composition of the copper plating solution is: copper sulfate 10 g/L, potassium sodium tartrate 22 g/L, ethylene diamine tetraacetic acid disodium salt 50 g/L, formaldehyde 15 mL/L, and decyl alcohol 10 mL/L. Among them, the solid uses a mass-to-volume ratio, that is, the mass per unit volume of the solid, in units of g/L; the liquid uses a volume-to-volume ratio, that is, the volume of the liquid per unit volume of the solution, in units of mL/L. Thus, the fabrication of the conductive trace 300 having a high conductivity and uniform enthalpy on the surface 110 of the substrate 100 is completed for subsequent processing. The production method employs an ink containing both an oxidant silver ammonia complex and a weak reducing agent, and the silver ammonia complex and the weak reducing agent are stably stored at a normal temperature, and a chemical reaction rapidly occurs under irradiation of high energy light. This avoids the problem of separately preparing the oxidizing ink and the reducing ink separately for printing, and simplifies the circuit manufacturing process while ensuring the quality of the line. The main component of the ink in the production method is easily soluble in water, and it is not necessary to consider the problem of dispersion stability. In the method, the reaction of the silver ammonia complex with the weak reducing agent is carried out under irradiation conditions, and the required equipment is simple and convenient for control. In addition, the plating 12 200951187 metal coated n the conductivity of the line, and the silver line is protected, avoiding the problem of silver ion migration. As described above, the present invention has indeed met the requirements of the invention patent, and has proposed a special shot according to law. However, the above preferred embodiments of the present invention are intended to limit the scope of the patent application in this case. Equivalent modifications or variations made by persons skilled in the art in light of the present invention are intended to be included within the scope of the following claims. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart of a method for fabricating a conductive line provided by the present technical solution. FIG. 2 is a schematic structural diagram of a substrate provided by an embodiment of the present technical solution. FIG. 3 is a schematic structural view of a circuit pattern formed by the substrate in FIG. 2. FIG. FIG. 4 is a schematic structural view of the substrate forming the prefabricated circuit in FIG. 2. FIG. FIG. 5 is a schematic structural view of a substrate forming a conductive line in FIG. 2. FIG. [Main component symbol description] Substrate 100 Surface 110 Line pattern 200 Prefabricated circuit 300 Conductive line 400 13