201217827 六、發明說明： 【發明所屬之技術領域】 本發明涉及一種塗料及其應用，特別是涉及一種抗指紋塗 料、具有抗指紋塗層的產品及該產品的製備方法。 【先前技術】 按’消費者對於手機、個人及工業電腦、pda、相機、ATM 等電子產品要求越來越高，除具有更多更強的功能之外，也要 求其更具便利性’觸控技術隨之廣泛應用。因此，不僅對電子 產品的外殼，而且電子產品的螢幕也提出了防指紋化 (anti-fingerprint)的要求。 人體手指上皮質所分泌的物質主要包括：約40°/。三酸甘油 酉曰（triglycerides)、約 25 % wax monoesters、約 15% free fatty acids、約12% squalene及約7%其他物質，以上物質皆為油酯 性’再加上手指表面也容易殘留水潰，不論是油酯或是水潰皆 非常容易附著於所接觸過的產品表面。 藉此，要使產品表面達到抗指紋的目的，必須使產品表面 具備疏水及疏油特性，產品表面的疏水及疏油特性的差別通常 取決於產〇〇表面與手指表面的表面能（surface energy )大小差 異。設定產品表面的表面能為㈧，液體的表面能為γ，當㈧^時 附著於手指表面的液體很容易附著於產品表面，而當時附 著於手指表面的液體不易附著於產品表面。水的表面能G)為 72mN/m，大部分油酯的表面能(γ)約為2〇4〇mN/m，大部分常 見的電子產品用材料’例如破璃、金屬、聚酯纖維（p〇lyest叶）、 聚乙烯（polyethylene)等的表面能皆大於2〇mN/m，因此水與 油醋容易附著於由這些材料製成的電子產品表面，從而間接殘 留指紋印。因此設計於玻璃、金屬、陶究、高分子基材表面塗 201217827 佈一表面能低於20mN/m的薄膜’以達到疏水、疏油抗指紋印 殘留的目的。而含氟的化合物普遍具備較低的表面能，聚四氟 乙烯（polytetrafluoroethylene )的表面能約為 20mN/m，氣氟 苯脲（cloflucarban，簡寫為-CF3 )分子的表面能約低於 10mN/m ’因此由含氟的化合物所形成的塗層能達到有效抗指 紋目的。 中華民國專利公開第200617419號，提出於電子產品表面 形成一’’表面抗指紋化塗層” ’即於電子產品表面形成一疏水性 奈米材料塗層、疏油性奈米材料塗層或超雙疏奈米材料塗層。 φ 其實質是於疏水性奈米材料塗層中含有各種聚合物奈米纖 維、各類有機矽烷化合物或含氟有機矽烷化合物等，或者於超 雙疏（疏油且疏水）奈米材料塗層中含有超雙疏陣列奈米碳管 膜’以使塗層具備疏水及疏油特性。 惟，上述的”表面抗指紋化塗層”的產品表面雖具有疏水性 或疏油性’但要達到疏水性及疏油性兩種特性皆有的超雙疏特 性塗層’則須形成上述的陣列奈米碳管膜。而陣列奈来碳管膜 的形成，一般須透過模板輔助生長碳管或須特殊的加工工藝來 φ 達到此一目的，不易大量生產，且其塗料配方主要適用的領域 為電子產品外殼的防指紋化。 有鑑於此，提供一種適用於電子產品外殼及螢幕表面處理 防指紋化’且製備簡單的塗層技術實為必要。 【發明内容】 本發明之目的係針對上述習知技術之不足提供一種抗指 紋塗料、具有抗指紋塗層的產品及該產品的製備方法，由該抗 指紋塗料製成具有抗指紋塗層的產品方法簡單，適合大量生 產0 5 201217827 一種抗指紋塗料，由以下步驟製成： (1) 將含氟高分子與溶劑混合得到含有氟高分子的塗料； (2) 將粒徑為5〜20nm的奈米粒子與溶劑混合，再加入含 氟偶合劑，並攪拌均勻，得到表面修飾有氟分子的奈米粒子溶 液； (3) 將步驟（1)得到的含有氟高分子的塗料與步驟（2) 得到的表面修飾有氟分子的奈米粒子溶液混合，並攪拌12〜24 小時後，即得到抗指紋塗料。 其中所述抗指紋塗料表面修飾氟分子的奈米粒子可以是 金屬氧化物、金屬或者高分子，再或者是碳球。 上述步驟（1)和步驟（2)中所述的溶劑為碳氟溶劑。 一種具有抗指紋塗層的產品，包括基材和覆蓋於基材表面 的抗指紋塗層，該抗指紋塗層係由如上所述之抗指紋塗料塗佈 於基材表面而製成。 一種具有抗指紋塗層的產品的製備方法，包括如下步驟： (1) 將抗指紋塗料塗佈於基材上，得到具有抗指紋塗層 的產品， (2) 將步驟（1)製備得到的具有抗指紋塗層的產品於溫 度80〜120°C下加熱0.5〜2小時，或者於室溫下自然乾燥24〜48 小時，從而於產品表面形成一厚度為10〜l〇〇nm的抗指紋塗層。 綜上所述，本發明係利用抗指紋塗層中含氟高分子及含氟 偶合劑的氟原子及奈米粒子表面所修飾的氟分子的低表面能 以及高度規則排列的奈米粒子所形成的立體屏障，有效使得手 指上的微小的油滴及水滴在接觸時不易吸附於產品表面，從而 使表面不會殘留指紋。且本發明具有抗指紋塗層的產品的製備 方法簡單，不需昂貴及特殊的反應設備，容易大量生產及降低 塗料生產成本，且電子產品的外殼及螢幕都適用。 201217827 【實施方式】 本發明之技術内容、構造特徵及其所達成之目的與功效， 以下詳予說明。 本發明抗指紋塗料由以下步驟製成： (1)將含氟高分子與碳氟溶劑混合得到含有氟高分子的 塗料。具體地，將0.1%〜0.5%的含氟高分子及99.5%〜99.9%的 含碳氟溶劑（methoxynonafluorobutane )混和得到含有氟高分 子的塗料；201217827 VI. Description of the Invention: [Technical Field] The present invention relates to a coating and an application thereof, and more particularly to an anti-fingerprint coating, a product having an anti-fingerprint coating, and a method of preparing the same. [Prior Art] According to 'consumers' demand for electronic products such as mobile phones, personal and industrial computers, pdas, cameras, ATMs, etc., in addition to having more and more powerful functions, it is also required to be more convenient. Control technology is widely used. Therefore, anti-fingerprint requirements have been imposed not only on the outer casing of electronic products but also on the screens of electronic products. The substances secreted by the cortex on the human finger mainly include: about 40 ° /. Triglycerides, about 25% wax monoesters, about 15% free fatty acids, about 12% squalene, and about 7% other substances, all of which are oily esters' plus the surface of the fingers are also prone to water Crush, whether it is oil ester or water collapse, is very easy to adhere to the surface of the product that has been touched. Therefore, in order to achieve anti-fingerprint surface, the surface of the product must have hydrophobic and oleophobic properties. The difference in hydrophobic and oleophobic properties of the product surface usually depends on the surface energy of the calving surface and the finger surface. ) size difference. The surface energy of the surface of the product is set to (8), and the surface energy of the liquid is γ. When (8)^, the liquid attached to the surface of the finger is easily attached to the surface of the product, and the liquid attached to the surface of the finger is not easily attached to the surface of the product. The surface energy G of water is 72mN/m, and the surface energy (γ) of most oil esters is about 2〇4〇mN/m. Most common electronic products are used for materials such as glass, metal and polyester fiber. The surface energy of p〇lyest leaf, polyethylene, etc. is more than 2〇mN/m, so water and oil vinegar are easily attached to the surface of electronic products made of these materials, thereby indirectly leaving fingerprints. Therefore, it is designed to coat the surface of glass, metal, ceramics and polymer substrate with 201217827 cloth with a surface energy of less than 20mN/m to achieve hydrophobic, oleophobic and anti-fingerprint residue. The fluorine-containing compounds generally have a low surface energy, the surface energy of polytetrafluoroethylene is about 20 mN/m, and the surface energy of cloflucarban (-CF3) molecules is less than about 10 mN/ m 'The coating formed from the fluorine-containing compound thus achieves an effective anti-fingerprint effect. The Republic of China Patent Publication No. 200617419 proposes to form a ''surface anti-fingerprint coating' on the surface of an electronic product' to form a hydrophobic nanomaterial coating, an oleophobic nanomaterial coating or a super double on the surface of an electronic product. The coating of the nano-material is φ. The essence is that the hydrophobic nano-material coating contains various polymer nanofibers, various organic decane compounds or fluorine-containing organic decane compounds, or super-double s The hydrophobic) nano-material coating contains a super-double-sparing array of carbon nanotube film 'to make the coating hydrophobic and oleophobic. However, the surface of the above-mentioned "surface anti-fingerprint coating" is hydrophobic or The oleophobic 'but to achieve both hydrophobic and oleophobic properties, the super-double-difference coating' must form the above array of carbon nanotube membranes. The formation of the array of carbon nanotube membranes generally requires the formation of a template. Assisted growth of carbon tubes may require special processing techniques to achieve this goal, and it is not easy to mass produce, and the main application area of coating formulations is the anti-fingerprinting of electronic product casings. It is necessary to provide a coating technology suitable for electronic product casing and screen surface treatment for anti-fingerprinting and simple preparation. SUMMARY OF THE INVENTION The object of the present invention is to provide an anti-fingerprint coating with anti-fingerprint resistance against the above-mentioned deficiencies of the prior art. The product of the fingerprint coating and the preparation method of the product, the method for preparing the anti-fingerprint coating by the anti-fingerprint coating is simple, and is suitable for mass production 0 5 201217827 An anti-fingerprint coating is prepared by the following steps: (1) The fluoropolymer is mixed with a solvent to obtain a coating containing a fluoropolymer; (2) a nanoparticle having a particle diameter of 5 to 20 nm is mixed with a solvent, and then a fluorinated coupling agent is added and stirred uniformly to obtain a surface-modified fluorine molecule. (3) mixing the fluoropolymer-containing coating obtained in the step (1) with the nanoparticle solution having the fluorine-modified molecular surface obtained in the step (2), and stirring for 12 to 24 hours, that is, An anti-fingerprint coating is obtained. The nanoparticle of the anti-fingerprint coating surface modified fluorine molecule may be a metal oxide, a metal or a polymer, or a carbon sphere. The solvent described in the step (1) and the step (2) is a fluorocarbon solvent. A product having an anti-fingerprint coating, comprising a substrate and an anti-fingerprint coating covering the surface of the substrate, the anti-fingerprint coating system The anti-fingerprint coating is applied to the surface of the substrate as described above. The preparation method of the product with anti-fingerprint coating comprises the following steps: (1) applying an anti-fingerprint coating to the substrate to obtain Anti-fingerprint coated products, (2) The anti-fingerprint coating product prepared in step (1) is heated at a temperature of 80 to 120 ° C for 0.5 to 2 hours, or naturally dried at room temperature for 24 to 48 hours. Thus, an anti-fingerprint coating having a thickness of 10 to 1 〇〇 nm is formed on the surface of the product. In summary, the present invention utilizes fluorine atoms and nanoparticles of a fluorine-containing polymer and a fluorine-containing coupling agent in an anti-fingerprint coating. The low surface energy of the fluorine molecules modified on the surface of the particles and the three-dimensional barrier formed by the highly regularly arranged nano particles effectively make the tiny oil droplets and water droplets on the fingers not easily adsorb on the surface of the product when contacted, so that the surface does not Residual fingerprints. Moreover, the method for preparing the anti-fingerprint coating of the invention is simple, does not require expensive and special reaction equipment, is easy to mass-produce and reduces the production cost of the coating, and is applicable to the outer casing and the screen of the electronic product. 201217827 [Embodiment] The technical contents, structural features, and the objects and effects achieved by the present invention are described in detail below. The anti-fingerprint coating of the present invention is produced by the following steps: (1) A fluoropolymer is mixed with a fluorocarbon solvent to obtain a coating containing a fluoropolymer. Specifically, 0.1% to 0.5% of a fluorine-containing polymer and 99.5% to 99.9% of a fluorononafluorobutane are mixed to obtain a coating material containing fluorine molecules;
(2) 將l〇g粒徑為5〜20nm的二氧化矽奈米粒子與l〇〇mi 碳敗溶劑混合’再加入〇·〇5〜0.2g的含氟偶合劑，並於室溫下 攪拌24小時，此時二氧化矽奈米粒子表面會修飾一層含氟分 子，即得到表面修飾有氟分子的二氧化矽奈米粒子溶液； (3) 將900ml步驟（1)得到的含有氟高分子的塗料與 100ml步驟（2)得到的表面修飾有氟分子的奈米粒子溶液混 合，並於室溫下攪拌12〜24小時後，即可得到抗指紋塗料。 其中奈米粒子可以是金屬氧化物，例如：二氧化鈦(Ti〇2)、 二氧化石夕(Si02)、1氧化二銘(A12〇3)、二氧化錯(Zr〇2)等；或 是金屬’例如：金、銀、銅等；或是高分子例如：ps、PM· 等；或是碳球。 本發明具有抗指紋塗層的產品的製備方法，包括如 驟： 得到具有抗指 (1)將上述之抗指紋塗料塗佈於基材上 紋塗層的產品； 本步驟中’塗佈時利用浸塗的方法，將抗指紋塗料塗佈於 產品表面，產品表面所形成的塗層中所包含 氣偶合劑可根據塗佈產品的材料種類不同優選適當官能基，以 201217827 確保會與基材形成化學鍵結。其中所包含的粒徑5-20 nm的奈 米粒子會自己形成一連續性且高規則排列的立體結構。 (2)將步驟（1)製備得到的具有抗指紋塗層的產品於溫 度80〜120°C下加熱0.5〜2小時，或者於室溫下自然乾燥24〜48 小時，此時，抗指紋塗料中奈米粒子表面的含氟高分子及含敗 偶合劑的上官能基會與產品表面的基材進行鍵接反應，從而於 產品表面形成一厚度為10~100nm的抗指紋塗層。 請參閱第一圖，為本發明具有抗指紋塗層的產品的抗指紋 塗層的示意圖。本發明具有抗指紋塗層的產品，藉由上述具有 抗指紋塗層的產品的製備方法製備而得，其包括基材3和覆蓋 於基材3表面的抗指紋塗層。該抗指紋塗層係由抗指紋塗料塗 佈於基材表面而製成，該抗指紋塗層中含有奈米粒子1、奈米 粒子1表面所修飾的含氟高分子4及含氣化合物2。 本發明具有抗指紋塗層的產品的抗指紋塗層中，奈米粒子 (本實施例中採用二氧化矽奈米粒子）自己形成高規則排列的 立體結構。由此，塗佈後產品的外殼及螢幕表面所形成的塗 層，利用奈米粒子本身規則排列的立體結構，有效達到雙重的 抗指紋效果；再加上抗指紋塗層中含氟高分子及含氟偶合劑的 氟原子及奈米粒子表面所修飾的氟分子的低表面能，使其具備 良好的疏水疏油特性，藉此使產品達到抗指紋效果。 其中產品可以是電子產品外殼及螢幕，例如手機螢幕、電 腦螢幕、PDA螢幕、工業電腦螢幕、相機螢幕、ATM螢幕等 需要使用觸控操作的物件。 塗佈產品的基材可以是玻璃、金屬、陶瓷、高分子中的一 種。 綜上所述，本發明係利用抗指紋塗層中含氟高分子及含氟 偶合劑的氟原子及奈米粒子表面所修飾的氟分子的低表面能 201217827 以及高度規則排列的奈米粒子所形成的立體屏障，有效使得手 指上的微小的油滴及水滴在接觸時不易吸附於產品表面，從而 使產品表面不會殘留指紋。且本發明具有抗指紋塗層的產品的 製備方法簡單，不需昂貴及特殊的反應設備，容易大量生產及 降低塗料生產成本，且電子產品的外殼及螢幕都適用。藉此， 本發明之「具有抗指紋塗層的產品及其塗佈方法」由上述揭露 之方法，可以達到所述之功效，且本發明之申請合乎專利之要 件，故依法提出申請。 【圖式簡單說明】 • 第一圖係本發明具有抗指紋塗層的產品的抗指紋塗層的 示意圖。 【主要元件符號說明】 奈米粒子 1 氟化合物 2 產品表面 3 氟分子 4(2) mixing cerium oxide nanoparticles having a particle diameter of 5 to 20 nm with a l〇〇mi carbonaceous solvent, and then adding a fluorinated coupling agent of 〜·〇5 to 0.2 g at room temperature. Stirring for 24 hours, at this time, the surface of the cerium oxide nanoparticles will modify a layer of fluorine-containing molecules, that is, a solution of cerium oxide nanoparticles having a surface modified with fluorine molecules; (3) high fluoride content obtained by the step (1) of 900 ml The molecular coating is mixed with 100 ml of the nanoparticle solution having the surface modified with fluorine molecules obtained in the step (2), and stirred at room temperature for 12 to 24 hours to obtain an anti-fingerprint coating. The nanoparticle may be a metal oxide such as: titanium dioxide (Ti〇2), dioxide dioxide (SiO 2 ), oxidized Erming (A12〇3), dioxin (Zr〇2), etc.; or metal 'Example: gold, silver, copper, etc.; or polymers such as: ps, PM·, etc.; or carbon spheres. The invention relates to a method for preparing a product with anti-fingerprint coating, comprising the steps of: obtaining a product having an anti-fingerprint coating coated on a substrate with an anti-finger coating; (1) utilizing in the step of coating The dip coating method applies an anti-fingerprint coating to the surface of the product, and the gas coupling agent contained in the coating formed on the surface of the product may be appropriately functionalized according to the kind of the material of the coated product, and is ensured to form a substrate with the 201217827. Chemical bonding. The nanoparticles having a particle size of 5-20 nm contained therein form a continuous and highly regular three-dimensional structure. (2) The product having the anti-fingerprint coating prepared in the step (1) is heated at a temperature of 80 to 120 ° C for 0.5 to 2 hours, or naturally dried at room temperature for 24 to 48 hours, at this time, the anti-fingerprint coating The fluorine-containing polymer on the surface of the nano-particles and the upper functional group of the stagnation coupling agent are bonded to the substrate on the surface of the product to form an anti-fingerprint coating having a thickness of 10 to 100 nm on the surface of the product. Please refer to the first figure for a schematic view of an anti-fingerprint coating of an anti-fingerprint coated product of the present invention. The anti-fingerprint coating product of the present invention is prepared by the above-described method for preparing a product having an anti-fingerprint coating comprising a substrate 3 and an anti-fingerprint coating covering the surface of the substrate 3. The anti-fingerprint coating is prepared by coating an anti-fingerprint coating on a surface of a substrate, wherein the anti-fingerprint coating comprises a nanoparticle, a fluorine-containing polymer 4 modified on the surface of the nanoparticle 1, and a gas-containing compound 2 . In the anti-fingerprint coating of the product having the anti-fingerprint coating of the present invention, the nanoparticle (in the present embodiment, the cerium oxide nanoparticle is used) forms a highly regular three-dimensional structure. Therefore, the coating formed on the outer shell of the product and the surface of the screen can effectively achieve the double anti-fingerprint effect by using the three-dimensional structure of the regular arrangement of the nano particles themselves; and the fluorine-containing polymer in the anti-fingerprint coating and The fluorine atom of the fluorine-containing coupling agent and the low surface energy of the fluorine molecule modified on the surface of the nanoparticle have good hydrophobic and oleophobic properties, thereby achieving an anti-fingerprint effect. The product can be an electronic product casing and a screen, such as a mobile phone screen, a computer screen, a PDA screen, an industrial computer screen, a camera screen, an ATM screen, and the like that require touch operation. The substrate of the coated product may be one of glass, metal, ceramic, and polymer. In summary, the present invention utilizes the fluorine atom of the fluorine-containing polymer and the fluorine-containing coupling agent in the anti-fingerprint coating and the low surface energy of the fluorine molecule modified by the surface of the nanoparticle 201217827 and the highly regularly arranged nanoparticle. The formed three-dimensional barrier effectively prevents tiny oil droplets and water droplets on the finger from being easily adsorbed on the surface of the product when contacted, so that no fingerprint remains on the surface of the product. Moreover, the method for preparing the anti-fingerprint coating of the invention is simple, does not require expensive and special reaction equipment, is easy to mass-produce and reduces the production cost of the coating, and is applicable to the outer casing and the screen of the electronic product. Accordingly, the "anti-fingerprint-coated product and its coating method" of the present invention can achieve the above-mentioned effects by the method disclosed above, and the application of the present invention meets the requirements of the patent, so the application is made according to law. BRIEF DESCRIPTION OF THE DRAWINGS • The first figure is a schematic view of an anti-fingerprint coating of a product having an anti-fingerprint coating of the present invention. [Main component symbol description] Nanoparticles 1 Fluorine compound 2 Product surface 3 Fluorine molecule 4