201224082 、發明說明： 【發明所屬之技術領域】 本發明係關於一種抗菌塗層，特別是指一種透明 的抗菌塗層。 【先前技術】 近年來具有抗菌性的商品大量的被使用於生活用 品上，以減少細菌的孽生，以提升生活品質及環境衛 生。 市面上應用最廣的抗菌材料為銀系抗菌材料，例 如將銀奈米粒子分散於塑膠原料，製造具有抗菌性的 塑膠容器。然而，銀系的抗菌材料係藉由銀奈米粒子 或銀離子的釋出，破壞細菌的細胞壁，來達到抗菌的 效果，其抗菌效果的持續性有限。並且，銀為貴金屬， 價格昂貴。 此外，雖然將銀與透明塑膠等混合，可以製備具 有抗菌特性之透明容器等，但銀離子的分散步驟繁 雜，且容易著色，並且銀離子容易有被光還原，或與 氯離子反應而失去特性。一般為改善這些缺點，需要 將銀離子附載於矽膠、水溶性玻璃、或沸石等。 除了銀之外，銅與鋅亦為構成無機系抗菌性化合 物之重要金屬。但是由於銅對細菌之抗菌活性較弱， 大約只有銀的1/200，因此，利用銅或鋅的金屬離子 的抗菌材料通常並非主流。但是，不同金屬離子的抗 菌材料，對於黴菌等所產生的靜菌作用又和對細菌的 情況有所不同。針對黴菌而言，以銅離子、鎳離子、 201224082 钻離子較強，接著是鋅離子與銀離子。又，自古已知 在花瓶放入銅板，可抑制菌類或藻類的發生，而使花 較持久，現在亦有在下水道淨水場、船舶、潛水艇之 外殼，利用貼銅板的工法來防藻。又，自古即已使用 混合硫酸銅與生石灰的水溶液，來預防葡萄的露菌病。 銅的抗菌機構有兩種說法，其一係溶出之銅離子 與微生物一旦接觸，會與酵素或蛋白質結合而降低活 性，阻礙其代謝功能，銅離子的濃度達40ppb，50% 大腸菌的將無法生存，菌數的減少亦受到銅離子濃度 的影響。另一說法係藉由銅的觸媒作用將空氣或水中 的一部分氧變成活化氧，而將微生物中的有機物分解。 銅與銀同樣地可以附載於沸石或矽膠等的形式使 用，與銀相比，銅會因為光或氯之性能惡化較少，因 此其使用的自由度高，可以是金屬銅本身、合金、含 有銅的無機物、有機銅化合物、或以配位在纖維上等 方式使用。 銅系抗菌性化合物，與銀系化合物相同，可以用 於塑膠或纖維製品之抗菌防臭加工，除此之外，藉由 其優異的防黴、防生藻作用，可廣泛地應用於水處理 領域、漁網或水路的防污、木材的防腐、流理台週邊 產品的去黏濕或防黑黴、或加工成抗菌不銹鋼，並應 用於廚房或食品搬運車、調理用器具等。 由此可知，銅系抗菌材料可有相當廣的應用，然 而上述銅系抗菌材料均大部分是以銅金屬、銅合金、 氧化銅、氧化亞銅等，皆會吸收可見光，因此若將該 201224082 等材料塗層塗佈於基材表面，將會影響基材之外觀。 近年來，利用觸控面板等的資訊終端機，不僅被 應用在智慧型行動電話，也時見於便利商店、鐵路、 捷運等大眾運輸之購票系統，或是醫院、百貨公司等 的觸控式資訊系統。這些觸控面板不斷的被多數人所 觸摸，也無形中增加了病菌傳染的途徑。然而，現今 的抗菌塗層大多數具有顏色而無法應用於觸控面板， 如果能有透明的抗菌塗層，不僅可以應用在上述會被 多數人觸摸的終端機，亦可應用在玻璃底船、觀光潛 水艇的觀景玻璃防止微生物的附著，或是應用於水族 箱、一般窗戶抗菌防霉等，可有非常多方面的應用。 關於抗菌材料之無色透明性，日本專利特開平 9-40502號揭示，將特性粒徑之抗菌性溶解性玻璃， 添加於合成樹脂。但是，該抗菌材料的母材為塑膠， 一般而言塑膠的财磨性、对候性、而t光性均較差。因 此，另外開發一種透明且具有良好的抗菌效果之塗層 材料，為本發明欲解決之課題。 【發明内容】 有鑑於上述課題，本發明之目的在於提供一種透 明抗菌塗層，主要材料化合物為氧化銅锶（SrCu2〇2)或 以化學式AB〇2代表，為具有赤銅鐵礦結構的化合物， 具有良好的抗菌效果，其中，A選自銀(Ag)、或銅（Cu) 其中一種，B選自鋁(AI)、銃(Sc)、鉻(Cr)、釔(Y)、鐵 (Fe)、銦（In)、鎵(Ga)、鈷（Co)其中之一種。 其中，AB〇2之B金屬離子以二價離子進行摻雜。 201224082 且透明抗菌塗層化合物之能隙至少大於2_5 eV，厚度 大約5 nm至3GG nm。透明抗g塗層的可見光穿透率 需至少大於50%’並且’紫外線f透率低於1〇%。 本發明所提供的透明的抗菌塗層，可以保持被塗 層基材之外觀’且具有良好的抗菌特性。由於本發明 之抗菌塗層本身在可見光範圍透明，因此可廣泛地應 用於玻璃固、玻璃容器、竟磚、衛浴用品等，或應 々板、玻璃底船、觀光潛水艇之觀景窗。201224082, invention description: TECHNICAL FIELD The present invention relates to an antibacterial coating, and more particularly to a transparent antibacterial coating. [Prior Art] In recent years, a large amount of antibacterial products have been used in household products to reduce the growth of bacteria to improve the quality of life and environmental hygiene. The most widely used antibacterial material on the market is a silver-based antibacterial material, for example, a silver nanoparticle is dispersed in a plastic material to produce an antibacterial plastic container. However, silver-based antibacterial materials are produced by the release of silver nanoparticles or silver ions, which destroy the cell wall of bacteria to achieve an antibacterial effect, and the persistence of the antibacterial effect is limited. Also, silver is a precious metal and expensive. Further, although silver is mixed with a transparent plastic or the like, a transparent container having antibacterial properties or the like can be prepared, but the dispersion step of silver ions is complicated and easy to color, and silver ions are easily photoreduced or reacted with chloride ions to lose characteristics. . In order to improve these disadvantages, it is necessary to attach silver ions to silicone rubber, water-soluble glass, or zeolite. In addition to silver, copper and zinc are also important metals constituting inorganic antibacterial compounds. However, since copper has a weak antibacterial activity against bacteria, it is only about 1/200 of silver. Therefore, antibacterial materials using metal ions of copper or zinc are usually not mainstream. However, the antibacterial materials of different metal ions have different effects on the bacteria caused by molds and the like. For mold, copper ions, nickel ions, 201224082 drill ions are strong, followed by zinc ions and silver ions. Moreover, it has been known since ancient times that the use of copper plates in vases can inhibit the occurrence of fungi or algae, and the flowers are more durable. Now, there are also sewer water purification plants, ships and submarines, and the method of using copper plates is used to prevent algae. Also, since ancient times, an aqueous solution of mixed copper sulfate and quicklime has been used to prevent the bacterial disease of grapes. The antibacterial mechanism of copper has two kinds of sayings. The copper ions dissolved in the first phase will contact with the enzyme or protein to reduce the activity and hinder its metabolic function. The concentration of copper ions reaches 40ppb, and 50% of the coliform bacteria will not survive. The decrease in the number of bacteria is also affected by the concentration of copper ions. Another theory is to decompose organic matter in microorganisms by converting a part of oxygen in air or water into activated oxygen by the catalytic action of copper. Copper can be used in the form of zeolite or silicone, as in silver. Compared with silver, copper has less deterioration due to the performance of light or chlorine. Therefore, it has high degree of freedom in use, and it can be metal copper itself, alloy, or An inorganic substance of copper, an organic copper compound, or a method of coordinating on a fiber or the like. Copper-based antibacterial compound, similar to silver-based compounds, can be used for antibacterial and deodorant processing of plastics or fiber products. In addition, it can be widely used in water treatment by its excellent anti-mildew and anti-algae action. Anti-fouling of fishing nets or waterways, anti-corrosion of wood, de-wetting or anti-black mold of products around the flow table, or processing into antibacterial stainless steel, and applied to kitchens, food handling vehicles, conditioning equipment, etc. It can be seen that the copper-based antibacterial material can be widely used. However, most of the copper-based antibacterial materials are copper metal, copper alloy, copper oxide, cuprous oxide, etc., and all absorb visible light, so if the 201224082 Coating of the material on the surface of the substrate will affect the appearance of the substrate. In recent years, information terminals such as touch panels have been used not only in smart mobile phones, but also in ticketing systems for mass transit such as convenience stores, railways, and MRT, or touches in hospitals, department stores, and the like. Information system. These touch panels are constantly being touched by most people, and they also virtually increase the path of infection. However, most of today's antibacterial coatings have color and cannot be applied to touch panels. If transparent antibacterial coatings are available, they can be applied not only to the above-mentioned terminals that are touched by most people, but also to glass bottom boats. The viewing glass of the sightseeing submarine can prevent the adhesion of microorganisms, or it can be applied to aquariums, general windows, antibacterial and mildewproof, etc., and can be used in many aspects. Regarding the colorless transparency of the antibacterial material, Japanese Patent Publication No. Hei 9-40502 discloses that an antimicrobially soluble glass having a characteristic particle diameter is added to a synthetic resin. However, the base material of the antibacterial material is plastic, and in general, the plastic has poor grindability, weatherability, and t-lightness. Therefore, the development of a coating material which is transparent and has a good antibacterial effect is a subject to be solved by the present invention. SUMMARY OF THE INVENTION In view of the above problems, an object of the present invention is to provide a transparent antibacterial coating, the main material compound being copper cerium oxide (SrCu 2 〇 2) or represented by the chemical formula AB 〇 2, which is a compound having a cherobite structure. Has a good antibacterial effect, wherein A is selected from silver (Ag), or copper (Cu), B is selected from aluminum (AI), strontium (Sc), chromium (Cr), strontium (Y), iron (Fe) ), one of indium (In), gallium (Ga), and cobalt (Co). Among them, the B metal ion of AB〇2 is doped with divalent ions. 201224082 The transparent antibacterial coating compound has a gap of at least 2_5 eV and a thickness of about 5 nm to 3 GG nm. The visible anti-g coating has a visible light transmission of at least greater than 50% ' and the 'ultraviolet f transmittance is less than 1%. The transparent antibacterial coating provided by the present invention can maintain the appearance of the coated substrate and has good antibacterial properties. Since the antibacterial coating of the present invention itself is transparent in the visible light range, it can be widely applied to glass solids, glass containers, bricks, sanitary articles, etc., or to viewing windows of slabs, glass bottom boats, and sightseeing submarines.
L貝施方式】 為使本發明之上述目的、特徵和優點能更明顯易 ’下文依本發明所提供的透明抗g塗層及塗料的製 備方法’特舉較佳實施例’並配合所附相關圖式，作 詳細說明如下。 本發明實施例所提供的透明抗菌塗層，包含具有 ，鐵鑛結構的化合物。化合物可以是氧化銅錯 2〇2)或以刀子S AB〇2表示，所述的赤銅鐵礦結 =圖1所示。其中，A金屬.離子選自銀(Ag)、或銅(Cu) 八一種，B金屬離子選自鋁(A|)、銃（Sc)、鉻(Cr)、 紀(Y)、鐵(Fe)、銦⑽、鎵(Ga)、銘(c〇)其中之一種。 本發明之抗菌塗層之厚度，大約在5nm至3〇〇 nrT^為佳’膜厚低於5 nm ’則抗菌效果難以長期維持， 膜厚超過300 nm則降低抗菌膜層之光穿透率，而影響 被塗層物之外觀。 由於本發明之抗菌塗層能隙至少大於2.5 eV，選 擇不同肖b隙的材料時，再配合塗層厚度控制，使本發 ，之抗菌塗層之可見光穿透率，至少大於50%，最佳 是大於80%。使本發明抗菌塗層應用於透明基材上 201224082 時，對於透明基材之可見光穿透率不至於有太大的影 響，而應用於非透明之基材上時，則可保持基材之外 觀。因此，本發明之抗菌塗層可廣泛地應用於觸控面 板、玻璃底船、觀光潛水艇之觀景窗、玻璃窗、玻璃 容器、瓷磚、衛浴用品等。 本發明所提供的透明抗菌塗層塗佈於基材時，可 以選擇使用熱蒸鍍、電子束蒸鍍法、分子束磊晶、脈 衝雷射蒸鍍法、濺鍍法、電漿喷塗法、氣凝膠法等真 空物理鍍膜法，化學氣相沉積法等化學鍍膜法，或是 化學溶液法、喷灑熱裂解法、凝膠-熔膠法等濕式化學 法。不論使用何種方法將塗層形成於基材上，只要能 使塗層化合物形成赤銅鐵礦結構即可。 其中，濕式法或化學氣相沉積法可形成梯度覆蓋 性良好的薄膜，因此，不論基材表面形狀如何，將本 發明之抗菌塗層以該等方式形成於基材上時，可形成 均勻的塗層。因此，如欲將本發明之透明抗菌塗層塗 佈於形狀不規則的人工瓷牙或磁器，使用上述方法較 佳。 在本發明其中一實施例中，是使用化學溶液法製 備透明抗菌塗層。以金屬鹽類作為原料，並以適當溶 劑溶解配製前驅溶液後，再以濕式法將塗料塗佈於基 材。所述的金屬鹽類即為含B金屬離子之化合物。比 如：銅鹽、鉻鹽、鋁鹽、銃鹽、銦鹽、銥鹽、鎵鹽、 鈷鹽等。 其中，所述的銅鹽，只要是含銅金屬離子之化合 物，並無特別限定，例如：醋酸銅、硝酸銅、硫酸銅、 201224082 氣化銅、氯化亞銅等，或雙乙醯丙酮基銅、β-二酮基 銅，雙六氟化乙醯丙酮基銅等有機金屬化合物。 所述的鉻鹽，可選擇使用醋酸鉻、硝酸鉻、硫酸 鉻、乳酸鉻、草酸鉻或氯化鉻等；鋁鹽可選擇使用醋 酸鋁或硝酸鋁；銃鹽可選擇使用醋酸銳或硝酸銃；鐵 鹽可選擇使用醋酸鐵、硝酸鐵、氯化鐵、硫酸鐵、乳 酸鐵。其它如製備銥鹽、銦鹽、鎵鹽、鈷鹽的金屬鹽 類，同樣只要分別含銥、銦、鎵、鈷的金屬離子即可， 並無特別限定。 前述用來均勻溶解上述金屬鹽類所使用之溶劑， 可選擇水、曱醇、乙醇、丙醇、丁醇、乙醚、曱乙醚、 曱基丁基醚、乙二醇曱醚、丙二醇曱醚、四氫呋喃等。 若是考慮塗層與基材之沾濕性，則選擇乙二醇曱醚、 乙醇、丙醇為佳，本發明實施例中，選用乙二醇甲醚 具有最佳效果。若考慮安全性及成本，則以水、乙醇 為佳。 此外，為了提升金屬離子在前驅溶液中的穩定 性，亦可添加增黏劑、螯合劑、酸鹼度調整劑等添加 劑。 前驅溶液製備完成後，欲使用濕式法於基材上形 成塗層時，可以選擇旋轉塗佈，浸潰塗佈、喷灑塗佈、 網印塗佈，刷毛塗佈等方式，並無特別限定。其中， 以旋轉塗佈將抗菌塗料塗佈於基材上，可以使塗層具 有較佳的均勻性。 使用濕式法塗佈將塗層塗佈於基材後，須依序進 行乾燥，熱裂解，反應結晶化的步驟。 201224082 其中，乾燥步驟，係將基材放置於加熱盤上或烘 箱内進行，乾燥溫度的範圍自80°C至300°C為佳， 但最好控制在120°C至250°C可以得到更佳的效果。 因為乾燥溫度過低，會使乾燥時間過長，且溶液的沾 濕性不佳時，會使塗層不均勻（請貴方確認），乾燥溫 度過高，則容易使塗層產生裂痕。 接著進行的熱裂解步驟，同樣可將基材放置於加 熱盤上或烘箱内進行，熱裂解溫度範圍在250°C至 500°C為佳，本發明實施例中，將熱裂解溫度控制在 300°C至450°C的範圍内更佳。熱裂解溫度低於250°C 時會有裂解反應不完全的情況發生，而再次於其上塗 佈前驅物溶液時，前驅溶液之溶劑會將前次塗佈層中 未完全裂解之化合物溶出，而使膜質惡化。 最後進行結晶化步驟，將基材放置於加熱盤，管 狀高溫爐，或快速退火爐等加熱裝置内進行。結晶化 溫度視塗層之組成及反應氣氛而定，例如：在空氣中 氧化鋁銅（CuAI〇2)的結晶化溫度需要達到至少 900°C，方可得到純相的赤銅鐵礦結構，而氧化鉻銅 (CuCr〇2)則只需要達到700°C即可得到純相的赤銅鐵 礦結構。然而，若在鈍氣氣氛中，或是在還原氣氛中 加熱，則可以在較低的溫度使氧化鋁銅（CuAI02)及氧 化鉻銅（CuCr02)結晶。但結晶化溫度範圍控制在大約 450°C至1000°C為佳，但最好控制在大約500°至 800°C，更進一步的將溫度範圍控制在600°C至700°C 最佳。 本發明利用化學溶液法製備透明抗菌塗層的方 201224082 法’以下列實施例具體說明。 首先，調製氧化鋁銅（CuA丨ο。或氧化鉻銅 (CuCr〇2)的前驅溶液。將醋酸鋼：硝酸鋁（或醋酸鉻）： 乙醇胺=2 : 1 : 4的莫耳比例量秤。調配時，先將醋 酸銅及乙醇胺溶於乙二醇曱謎，加熱搜拌2小時，再 加入硝酸鋁（或醋酸鉻），混合攪拌12小時後，加入溶 劑至特定量，調製成氧化鋁銅（CuA丨〇2)或氧化鉻銅 (CuCr02)的前驅溶液。 接著，利用旋轉塗佈機將氧化紹銅（Cuai〇2)或氧 •化鉻銅（CuCr〇2)塗佈於一玻璃基材或一氧化鋁基材。 以轉速每分鐘4000轉，在玻璃基板上旋塗15秒。每 旋轉塗佈一層後’就將玻璃基材放置於加熱板上，升 溫至大約150 °C乾燥4分鐘，再放入管狀爐中預退 火進行熱裂解，係先將玻璃基材加熱至大約40CTC， 持溫5分鐘後，再冷卻3分鐘。在另一實施例中，係 使用浸潰塗佈法將氧化鋁銅（CuAI〇2)或氧化鉻銅 (CuCr〇2)塗佈於基材上。 • 將塗佈、乾燥、熱裂解的步驟重覆進行五次後， 將玻璃基材放置於管狀爐以進行結晶化步驟，本發明 實施例中，在空氣氣氛下，是以900。〇進行退火30 分鐘’得氧化鋁銅（CuAI02)薄膜，以700 °C進行退火 30分鐘’得氧化鉻銅（Cucr〇2)薄膜。 若選擇使用熱蒸鍍、電子束蒸鍍法、分子束蠢晶、 脈衝雷射蒸鍍法、濺鍍法等物理氣相沉積法，將本發 明之透明抗菌塗層形成於基材上時，玎使用具有赤銅 鐵礦構造之化合物AB〇2燒結體作為靶材’或者使用 201224082 多個純金屬靶或氧化物靶，進行多源蒸鍍，並通入適 當的氣體，以形成本發明之透明抗菌塗層。以物理真 空法所製備之塗層，亦可進一步在各種氣氛進行退 火，以提升抗菌塗層之結晶性、附著性、透明性等特 性。 在本發明一較佳實施例中，將氧化銅粉末與三氧 化二鉻或三氧化二鋁粉末以莫耳比2:1之劑量混合配 製，接著，與高純度酒精及直徑1 mm之紀安定化氧 化鍅磨球於PE塑膠罐中混合，其固含量約為30 wt.%，再以行星運動式混合機進行濕式球磨24小時。 球磨後的粉末在烘箱中以70 °C乾燥36小時，乾 燥後之粉末再使用高緻密瑪瑙研体研磨，研磨後將粉 末置入氧化鋁坩鍋内，放入高溫爐中以1200 °C煆燒6 小時。之後將粉末再研磨並過篩，所得粉末以手動成 形機壓製成直徑2吋的圓錠，再將之放入高溫爐中以 1250 °C燒結8小時，即為氧化鉻銅（CuCr02)或氧化 I呂銅（CuAI〇2)或之2 p寸把材。 將靶材及一玻璃基板或一氧化鋁基板放入濺鍍 機，以氧氬混合氣體，進行射頻磁控濺鍍，於玻璃基 板或氧化鋁基板上形成氧化鉻銅（CuCr〇2)或氧化鋁 銅（CuAI〇2)薄膜。 為了測試本發明之透明抗菌塗層之抗菌能力及對 於基材之附著性，發明人並以濺鍍方式於玻璃基材上 製備銅膜，以化學溶液法，在玻璃基板上製備氧化銅 (Cu〇）薄膜作為比較例。其中，以化學溶液法在在玻璃 基板上製備氧化銅（CuO)薄膜時，仍以醋酸銅：乙醇胺 201224082 =1 : 4的比例量秤，將醋酸銅及乙醇胺溶於乙二醇甲 醚’加熱授拌12小時後，加入溶劑至特定量，調製 CuO的前驅溶液。旋轉塗佈、乾燥及熱裂解步驟的條 件皆和製備氧化鉻銅（CuCr〇2)或氧化銘銅（cuai〇2)塗 層相同。最後將基材放置於管狀爐中結晶化時，是以 600 °C進行退火30分鐘，得Cu〇薄膜。 另外’並將厚度0.3 mm商用抗菌不銹鋼、純銅 片，以及被塗層基材之玻璃基板本身裁切成長2cmx 寬2cm，與本發明之實施例同樣地進行各種測試比 較。 進行机函測试時，對實施例及比較例所得之抗菌 塗層，進行塗層之抗菌能力、密著性（膠帶試驗）及光 穿透率三方面的測試。 1.抗菌測試 本發明中根據JIS Z 2801抗菌測試方法，將測定 之抗菌特性示於表1。其中，抗菌率（R)=(對照組_樣 品組)/對照組x100 %，以作用12小時之抗菌率作為評 估基準’抗菌率大於90%者評估為〇,抗菌率低於 90%，高於50%者評估為△，抗菌率低於5〇%者評估 為X。於第2圖表示塗盤試驗計數時之照片。於第3圖 表示實施例及比較例之抗菌能力之圖。 請參照圖4,表示本發明之一實施形態之氧化鋁 銅（CuAI〇2)、氧化鉻銅（CuCr〇2)抗菌塗層塗佈於玻璃 基板、氧化鋁基板之照片。本發明實施例1〜4及比較 例1〜2放置於背景30上’可以明顯比較出本發明實施 例1及2將氧化鋁銅（CuAI〇2)、氧化鉻銅（CuCr〇2)抗 12 201224082 菌塗層塗佈於玻璃基板上之透光率仍然很高，證明本 發明之透明抗菌塗層除了抗菌能力不亞於習知使用的 銅塗層之外，也可以保持被塗層基材之外觀。 2. 密著性的測定（膠帶試驗） 針對密著性的測定（膠帶試驗），是對實施例及比較 例所得之抗菌塗層，以3M scotch膠帶黏貼1 cmX1 cm 試片表面靜置1分鐘後，撕下觀察是否有抗菌塗層之 剝落，判定塗層與其材之密著性，完全沒有剝落者判 定為〇,可以肉眼觀察到有剝落者判定為X。將結果示 於表1。 3. 光穿透率測試 將實施例及比較例所得之抗菌塗層，以玻璃基材 作為空白試片，以UV-Vis光譜儀（JASCO V630)測定， 並將550nm之光穿透率結果示於表1。將測定穿透率 示於表1。 201224082 [表1]In order to make the above objects, features and advantages of the present invention more apparent, the following is a preferred embodiment of the transparent anti-g coating and coating provided by the present invention. The relevant drawings are described in detail below. The transparent antibacterial coating provided by the embodiment of the present invention comprises a compound having an iron ore structure. The compound may be copper oxide 2 〇 2) or represented by a knife S AB 〇 2, which is shown in Figure 1. Wherein, the A metal ion is selected from the group consisting of silver (Ag) or copper (Cu), and the B metal ion is selected from the group consisting of aluminum (A|), strontium (Sc), chromium (Cr), ge (Y), and iron ( One of Fe), indium (10), gallium (Ga), and Ming (c〇). The thickness of the antibacterial coating of the present invention is about 5 nm to 3 〇〇 nr T ^ is good, and the film thickness is less than 5 nm. The antibacterial effect is difficult to maintain for a long time, and the film thickness exceeding 300 nm reduces the light transmittance of the antibacterial film layer. And affect the appearance of the coated object. Since the antibacterial coating of the present invention has an energy gap of at least more than 2.5 eV, when a material having a different Schiff b gap is selected, and the thickness of the coating is controlled, the visible light transmittance of the antibacterial coating of the present invention is at least 50%, most Good is greater than 80%. When the antibacterial coating of the present invention is applied to a transparent substrate on 201224082, the visible light transmittance of the transparent substrate is not greatly affected, and when applied to a non-transparent substrate, the appearance of the substrate can be maintained. . Therefore, the antibacterial coating of the present invention can be widely applied to a touch panel, a glass bottom boat, a viewing window of a sightseeing submarine, a glass window, a glass container, a tile, a bathroom, and the like. When the transparent antibacterial coating provided by the invention is applied to a substrate, thermal evaporation, electron beam evaporation, molecular beam epitaxy, pulsed laser evaporation, sputtering, plasma spraying may be selected. , such as the vacuum physical coating method such as the aerogel method, the chemical vapor deposition method, or the wet chemical method such as the chemical solution method, the spray pyrolysis method, or the gel-melting method. Regardless of the method used to form the coating on the substrate, it is sufficient that the coating compound forms a cuprite structure. Among them, the wet method or the chemical vapor deposition method can form a film having a good gradient coverage, and therefore, the antibacterial coating of the present invention can be formed uniformly on the substrate in such a manner regardless of the surface shape of the substrate. Coating. Therefore, if the transparent antibacterial coating of the present invention is to be applied to an irregularly shaped artificial porcelain tooth or a magnet, the above method is preferably used. In one embodiment of the invention, a transparent antimicrobial coating is prepared using a chemical solution process. The metal salt is used as a raw material, and the precursor solution is dissolved in a suitable solvent, and then the coating is applied to the substrate by a wet method. The metal salt is a compound containing a B metal ion. For example, copper salts, chromium salts, aluminum salts, barium salts, indium salts, barium salts, gallium salts, cobalt salts, and the like. The copper salt is not particularly limited as long as it is a compound containing a copper metal ion, and is, for example, copper acetate, copper nitrate, copper sulfate, 201224082 vaporized copper, cuprous chloride, or the like. An organic metal compound such as copper, β-diketone copper or bishexafluoroacetic acid acetonyl copper. The chromium salt may be selected from the group consisting of chromium acetate, chromium nitrate, chromium sulfate, chromium lactate, chromium oxalate or chromium chloride; the aluminum salt may be selected from aluminum acetate or aluminum nitrate; the barium salt may be selected from acetic acid or barium nitrate. Iron salt can be selected from iron acetate, iron nitrate, iron chloride, iron sulfate, and iron lactate. Other metal salts such as a sulfonium salt, an indium salt, a gallium salt or a cobalt salt are not particularly limited as long as they respectively contain metal ions of cerium, indium, gallium or cobalt. The solvent used for uniformly dissolving the above metal salt may be selected from water, decyl alcohol, ethanol, propanol, butanol, diethyl ether, decyl ether, decyl butyl ether, ethylene glycol oxime ether, propylene glycol oxime ether, Tetrahydrofuran and the like. In view of the wettability of the coating and the substrate, ethylene glycol oxime ether, ethanol, and propanol are preferred. In the examples of the present invention, the use of ethylene glycol methyl ether has the best effect. When considering safety and cost, water and ethanol are preferred. Further, in order to improve the stability of the metal ion in the precursor solution, an additive such as a tackifier, a chelating agent, or a pH adjuster may be added. After the preparation of the precursor solution, if a wet method is used to form a coating on the substrate, spin coating, dip coating, spray coating, screen printing, brush coating, etc. may be selected, and there is no special limited. Among them, the antibacterial coating is applied to the substrate by spin coating, so that the coating has better uniformity. After the coating is applied to the substrate by wet coating, the steps of drying, thermal cracking, and reaction crystallization are sequentially performed. 201224082 wherein the drying step is performed by placing the substrate on a heating plate or in an oven, and the drying temperature is preferably from 80 ° C to 300 ° C, but it is preferably controlled at 120 ° C to 250 ° C to obtain more. Good results. If the drying temperature is too low, the drying time will be too long, and if the wettability of the solution is not good, the coating will be uneven (please confirm it). If the drying temperature is too high, the coating will be cracked easily. In the subsequent thermal cracking step, the substrate can also be placed on a heating plate or in an oven, and the thermal cracking temperature is preferably in the range of 250 ° C to 500 ° C. In the embodiment of the present invention, the thermal cracking temperature is controlled at 300. More preferably in the range of °C to 450 °C. When the thermal cracking temperature is lower than 250 ° C, the cracking reaction is incomplete, and when the precursor solution is applied again, the solvent of the precursor solution dissolves the compound which is not completely cracked in the previous coating layer. The film quality deteriorates. Finally, the crystallization step is carried out, and the substrate is placed in a heating device such as a heating plate, a tubular high-temperature furnace, or a rapid annealing furnace. The crystallization temperature depends on the composition of the coating layer and the reaction atmosphere. For example, in the air, the crystallization temperature of the aluminum oxide copper (CuAI〇2) needs to reach at least 900 ° C to obtain a pure phase of the copper-copper iron ore structure. The chromium oxide copper (CuCr〇2) only needs to reach 700 °C to obtain a pure phase of the copper-copper structure. However, if it is heated in a passive atmosphere or in a reducing atmosphere, alumina copper (CuAI2) and copper (CuCr02) can be crystallized at a relatively low temperature. However, it is preferred that the crystallization temperature range is controlled to be about 450 ° C to 1000 ° C, but it is preferably controlled at about 500 ° C to 800 ° C, and further preferably the temperature range is controlled from 600 ° C to 700 ° C. The method of preparing a transparent antibacterial coating by the chemical solution method of the present invention 201224082 is specifically described in the following examples. First, a precursor solution of alumina copper (CuA丨ο. or chromium chrome copper (CuCr〇2)) is prepared. The acetic acid steel: aluminum nitrate (or chromium acetate): ethanolamine = 2: 1 : 4 molar ratio scale. In the preparation, first dissolve copper acetate and ethanolamine in ethylene glycol 曱 mystery, heat and mix for 2 hours, then add aluminum nitrate (or chromium acetate), mix and stir for 12 hours, add solvent to a specific amount, prepare into aluminum oxide copper a precursor solution of (CuA丨〇2) or chromium chrome copper (CuCrO 2 ). Next, a copper coating (Cuai 2 ) or copper chrome ( CuCr 〇 2 ) is applied to a glass base by a spin coater. Or an alumina substrate. Spin-coated on a glass substrate for 15 seconds at 4,000 rpm. After each spin coating, place the glass substrate on a hot plate and heat to about 150 °C. Minutes, then pre-annealed in a tubular furnace for thermal cracking, first heating the glass substrate to about 40 CTC, holding the temperature for 5 minutes, and then cooling for another 3 minutes. In another embodiment, using the dip coating method Alumina copper (CuAI〇2) or chromium oxide copper (CuCr〇2) is coated on the substrate. After the steps of coating, drying, and thermal cracking are repeated five times, the glass substrate is placed in a tubular furnace to perform a crystallization step. In the embodiment of the present invention, annealing is performed at 900 Torr for 30 minutes in an air atmosphere. 'Aluminum oxide copper (CuAI02) film, annealed at 700 °C for 30 minutes' to obtain a chromium oxide copper (Cucr〇2) film. If you choose to use thermal evaporation, electron beam evaporation, molecular beam, crystal pulse When a transparent antibacterial coating layer of the present invention is formed on a substrate by a physical vapor deposition method such as a vapor deposition method or a sputtering method, a sintered body of a compound AB〇2 having a cherobite structure is used as a target 'or 201224082 Multiple pure metal targets or oxide targets, multi-source evaporation, and a suitable gas to form the transparent antibacterial coating of the present invention. The coating prepared by the physical vacuum method can be further in various atmospheres. Annealing is performed to enhance the properties of the antibacterial coating such as crystallinity, adhesion, transparency, etc. In a preferred embodiment of the present invention, the copper oxide powder and the chromium oxide or aluminum oxide powder are in molar ratio 2 :1 agent The mixture is prepared by mixing with high-purity alcohol and a 1 mm diameter oxidized cerium ball in a PE plastic tank with a solid content of about 30 wt.%, followed by wet ball milling with a planetary motion mixer. The ball-milled powder is dried in an oven at 70 ° C for 36 hours. The dried powder is then ground using a high-density agate mortar. After grinding, the powder is placed in an alumina crucible and placed in a high-temperature furnace at 1200 °. C 煆 6 hours. After that, the powder was reground and sieved, and the obtained powder was pressed into a round ingot of 2 直径 in diameter by a manual forming machine, and then placed in a high temperature furnace and sintered at 1250 ° C for 8 hours, which was chromium oxide. Copper (CuCr02) or oxidized Ilu copper (CuAI〇2) or 2 p inch. The target material and a glass substrate or an alumina substrate are placed in a sputtering machine, and an oxygen-argon mixed gas is used for RF magnetron sputtering to form chromium oxide copper (CuCr〇2) or oxidized on a glass substrate or an alumina substrate. Aluminum copper (CuAI〇2) film. In order to test the antibacterial ability of the transparent antibacterial coating of the present invention and adhesion to a substrate, the inventors prepared a copper film on a glass substrate by sputtering, and prepared copper oxide (Cu) on a glass substrate by a chemical solution method. 〇) Film as a comparative example. Wherein, when a copper oxide (CuO) film is prepared on a glass substrate by a chemical solution method, copper acetate and ethanolamine are dissolved in the amount of ethylene glycol methyl ether by heating in a ratio of copper acetate: ethanolamine 201224082 = 1:4. After 12 hours of mixing, the solvent was added to a specific amount to prepare a precursor solution of CuO. The conditions of the spin coating, drying and thermal cracking steps are the same as for the preparation of chrome-platinum copper (CuCr〇2) or oxidized copper (cuai〇2) coatings. Finally, when the substrate was placed in a tubular furnace for crystallization, it was annealed at 600 ° C for 30 minutes to obtain a Cu ruthenium film. Further, the commercially available antibacterial stainless steel having a thickness of 0.3 mm, the pure copper sheet, and the glass substrate of the substrate to be coated were cut to a length of 2 cmx and a width of 2 cm, and various tests were carried out in the same manner as in the examples of the present invention. In the case of the machine function test, the antibacterial coatings obtained in the examples and the comparative examples were tested for the antibacterial ability, the adhesion (tape test) and the light transmittance of the coating. 1. Antibacterial test In the present invention, the measured antibacterial properties are shown in Table 1 according to the JIS Z 2801 antibacterial test method. Among them, the antibacterial rate (R) = (control group - sample group) / control group x 100%, with the antibacterial rate of 12 hours as the evaluation standard 'antibacterial rate is greater than 90%, the antibacterial rate is less than 90%, high 50% were evaluated as △, and those with an antibacterial rate lower than 5% were evaluated as X. Fig. 2 shows a photograph when the plate test is counted. Fig. 3 is a view showing the antimicrobial ability of the examples and comparative examples. Referring to Fig. 4, there is shown a photograph of an aluminum oxide (CuAI〇2) or chromium oxide copper (CuCr〇2) antibacterial coating applied to a glass substrate or an alumina substrate according to an embodiment of the present invention. The inventive examples 1 to 4 and the comparative examples 1 to 2 are placed on the background 30'. It can be clearly compared that the first embodiment and the second embodiment of the present invention have aluminum oxide (CuAI〇2) and copper chromium (CuCr〇2) anti-12. 201224082 The transmittance of the bacterial coating on the glass substrate is still high, which proves that the transparent antibacterial coating of the present invention can maintain the coated substrate in addition to the antibacterial ability as well as the conventional copper coating. The appearance. 2. Measurement of adhesion (tape test) For the measurement of adhesion (tape test), the antibacterial coating obtained in the examples and the comparative examples was adhered to the surface of a 1 cm×1 cm test piece with 3M scotch tape for 1 minute. After that, it was peeled off to observe whether or not the antibacterial coating was peeled off, and the adhesion of the coating to the material was judged. The flaw was judged to be flawless at all, and it was judged by the naked eye that the peeled person was judged as X. The results are shown in Table 1. 3. Light transmittance test The antibacterial coatings obtained in the examples and the comparative examples were measured with a glass substrate as a blank test piece by a UV-Vis spectrometer (JASCO V630), and the light transmittance at 550 nm was shown. Table 1. The measured penetration rate is shown in Table 1. 201224082 [Table 1]
材料 成膜方法 基材 抗菌測試 膠帶測試 可見光 穿透率 (%) 20(實施例1) 氧化鉻銅 (CuCr〇2) 溶液法 玻璃 〇 〇 74.60% 21 (實施例2) 氧化鋁銅 (CuAI02) 浸潰法 玻璃 〇 〇 86.70% 22(實施例3) 氧化鋁銅 (CuAI02) 溶液法 氧化鋁 〇 〇 — 23(實施例4) 氧化鉻銅 (CuCr02) 浸潰法 玻璃 〇 〇 — 24(實施例5) 氧化鉻銅 (CuCr02) 濺鍍法 玻璃 〇 〇 89.49% 25(實施例6) 氧化鋁銅 (CuAI02) 濺鍍法 玻璃 〇 〇 89.65% 26(實施例7) 氧化鋁銅 (CuAI02) 濺鍍法 氧化鋁 〇 〇 84.68% 27(比較例1) 玻璃基板 - 玻璃 〇 100% 28(比較例2) 銅 濺鍍法 玻璃 〇 X 4.8% 29(比較例3) 氧化銅 溶液法 玻璃 〇 X 40% 比較例4 銅板 - - 〇 〇 74.60% 14 201224082 由表1之結果可知’本發明所提供之透明抗菌塗 層’不僅具有良好的抗菌特性，且透光率高。根據膠 ▼附耆丨生5式驗’可知本發明之塗層於玻璃基板的附者 性’相較於習知技術中所使用的氧化銅及銅來說更 好。因此’可廣泛地使用於各種面板，尤其是觸控面 ，、觀光潛水艇及玻璃底船之觀景窗、一般玻璃的抗 菌防霉、水族箱、花瓶、或各種陶瓷。Material film formation method Substrate antibacterial test tape Test visible light transmittance (%) 20 (Example 1) Chromium oxide copper (CuCr〇2) Solution method Glass crucible 74.60% 21 (Example 2) Alumina copper (CuAI02) Dipping method glass crucible 86.70% 22 (Example 3) Alumina oxide copper (CuAI02) Solution method Alumina crucible - 23 (Example 4) Chromium oxide copper (CuCr02) Dipping glass crucible - 24 (Example 5) Chromium Oxide Copper (CuCrO 2 ) Sputtering Glass crucible 89.49% 25 (Example 6) Alumina Oxide (CuAI02) Sputtering Glass crucible 89.65% 26 (Example 7) Alumina Oxide (CuAI02) Sputtering Method Alumina 〇〇 84.68% 27 (Comparative Example 1) Glass substrate - Glass 〇 100% 28 (Comparative Example 2) Copper sputtering method Glass 〇 X 4.8% 29 (Comparative Example 3) Copper oxide solution method Glass 〇 X 40% Comparative Example 4 Copper plate - - 74.60% 14 201224082 It is understood from the results of Table 1 that the transparent antibacterial coating provided by the present invention not only has good antibacterial properties, but also has high light transmittance. According to the glue test, it is understood that the coating of the present invention on the glass substrate is better than that of the copper oxide and copper used in the prior art. Therefore, it can be widely used in various panels, especially touch surfaces, viewing windows for sightseeing submarines and glass bottom boats, antibacterial and mildewproof for general glass, aquariums, vases, or various ceramics.
此外本發明之抗菌塗層由於其能隙在3.1eV左 右，=外線穿透率低於！〇%，具有抗紫外線（UV c(jt) 、°另―方面，由於本發明之透明抗菌塗層本身 :可藉*連接1極’ Ή彡成除霧破續。因 光率之透明抗8塗層，可使玻璃同時具有高透 …、良好的抗菌性、紫外線遮蔽性及防霧特性。 ^本發明雖以較佳實例闡明如上，然其並非用。 ，㈣精神與發明實體僅止於上述實施例。 產：f術者’當可輕易了解並利用其它元件或方 效。是以’在不脫離本發明之精神ii 可内所作之修改’均應包含在下述之申請專利範申圍内乾 201224082 【圖式簡單說明】 圖1係關於本發明之赤銅鐵礦型抗菌化合物之結構示 意圖； 圖2係表示本發明之實施例與比較例之抗菌測試之結 果之照片； 圖3係表示本發明之實施例與比較例之抗菌性能圖； 及 圖4係表示本發明之一實施形態之氧化鋁銅 籲 （CuAI〇2)、氧化絡銅（CuCr〇2)抗菌塗層塗佈於玻璃基 板、氧化鋁基板之照片。 【主要元件符號說明】 A、B:金屬離子 0:氧離子 20〜26 :實施例1〜實施例7 27〜29 :比較例1〜3 200 :細菌Further, the antibacterial coating of the present invention has an outer gap of less than 3.1 eV because of its energy gap! 〇%, with UV resistance (UV c(jt), ° other aspects, due to the transparent antibacterial coating itself of the present invention: can be connected by 1 pole' into a defogging break. Due to the transparency of light rate 8 The coating can make the glass have high permeability, good antibacterial property, ultraviolet shielding property and anti-fog property at the same time. The present invention is exemplified by the preferred examples as above, but it is not used. (4) The spirit and the invention entity only stop at The above embodiments. Production: The operator's can easily understand and utilize other components or effects. The modifications made in the spirit of ii without departing from the spirit of the invention should be included in the following patent application. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing the structure of a cuprous iron type antibacterial compound of the present invention; Fig. 2 is a photograph showing the results of an antibacterial test of an embodiment of the present invention and a comparative example; The antibacterial performance chart of the examples and comparative examples of the present invention; and FIG. 4 shows that the aluminum oxide copper (CuAI〇2) and copper oxide (CuCr〇2) antibacterial coatings of one embodiment of the present invention are applied to the glass. Substrate, alumina substrate . The main sheet member REFERENCE NUMERALS A, B: 0 a metal ion: oxygen ions 20~26: Example 1 ~ Example 7 27~29: 1~3 Comparative Example 200: Bacterial
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