201005763 魏. 六、發明說明： 【發明所屬之技術領域】 本發明係較透明塗層領域，更特定言之侧於由含有 導電性細粒之乳液形成之透明導電塗層，在塗覆至基板及 在液體載劑洛發之後，該等顆粒可自組合成開放單元式網 狀導電圖案。本發明之特定領域係關於用於在基板上形成 透明導電塗層賴？文良之方法（其包㈣基板之表面處 理）’及在塗布之前不需要特殊底塗層的乳液調配物。 本申清案根據35 USC § 119(e)主張2008年6月6曰申請之 美國臨時申請案第61/059,608號之優先權，其全部内容以 引用之方式併入本文中。 【先前技術】 用於形成透明導電塗層之材料及方法有益於電子器件之 開發及製造。此等塗層提供諸如電磁（EMI)屏蔽及靜電耗 散之若干功能，且此等塗層在多種應用中充當透光的導電 層及電極。該等應用包括（但不限於）有用的器件或器件之 部分’諸如，觸控螢幕、無線電子板、光伏打器件 (photovoltaic device)、導電紡織品及纖維、顯示器、 OLED，及諸如電子紙之電致發光結構。 使用如US200502 14480中所描述之乳液來製備透明導電 塗層（TCC)。已使用在由乳液塗布之前立即塗覆的底塗層 或預處理塗層來優先改變將由乳液塗布之基板的表面特 徵。 在上述US2005/0214480中，在玻璃及聚醯亞胺基板上塗 140855.doc 201005763 布TCC之方法包括初步塗布步冑，在此步驟中，在塗覆 TCC乳液之前將丙酮中之我化合物或其他界面活性劑塗 覆至基板表面。此等預處理塗層組合物被稱為「底塗 劑」。在塗布底塗劑且使其乾燥之後，塗覆TCC塗層。類 - 似地’在W02006/135735中，相對於未經處理之膜，用辛 基三乙氧矽烷底塗劑的己烷溶液處理過之PET膜改良了 TCC圖案。 • 包括用以在沈積TCC乳液之前立即塗覆該等底塗劑或其 他初步塗布層之單獨步驟的方法有若干缺點。沈積底塗劑 或初步塗布層且接著沈積TCC調配物之商業上可行的塗布 方法需要兩個塗布頭且因此需要2步方法。較佳的是，方 法藉由單-塗布頭且以單-步驟來操作。又’當在沈積底 塗層之後立即塗覆後續TCC層時，底塗層之非均勻性以及 乳液與底塗劑之交互作用可能導致後續Tcc層中之缺陪。 以丙酮為主之錢劑尤其具有額外缺點。丙酮具高度可 • 燃性；以丙酮為主之底塗劑的膜品質通常會影響TCC單元 尺寸之後續均勻性；且自以丙酮為主之底塗劑產生的底塗 冑層在中間處置步驟（例如’若在後續取塗布步驟之前被 輥軋或以其他方式被儲存）之後可能無法保持其特性。 因此存在對替代性TCC乳液調配物或表面處理之需要， 以在商業規模的塗布操作中消除當前底塗劑而不會不利地 影響圖案形成。 【發明内容】 描述用於在基板上形成TCC之各種經改良的方法，其中 140855.doc 201005763 兩種方法消除在塗布T C C乳液之前立即將底塗劑塗布至基 板上的需要且仍獲得可接受之TCC圖案。第三種方法在基 板上提供新的且更通用的初步處理塗層。此等方法對市售 "T撓性基板（包括使用大規模塗布設備之光學ΡΕτ基板）尤 其有用。 —種方法包括將UV固化組份併入至TCC乳液中及在TCC 形成期間應用UV固化步驟。 另種方法包括在由TCC乳液塗布之前對基板之uv活化 或其他物理活化。 另種方法包括藉由在基板上充分穩定的uv活化黏合 劑來預處理基板以允許在單遍塗布方法中儲存基板且稍後 藉由TCC乳液來塗布基板。 【實施方式】 當將 TCC乳液（諸如 US2005/214480及 WO2006/3 5735 中所 描述之彼等乳液，兩案皆以引用之方式併入本文中）塗布 至基板表面上之初步「預處理」塗布層或底塗層上時， TCC乳液提供具有相對均勻之單元尺寸分布的均勻圖案。 仁疋，如上文所提及，首先沈積初步塗布層或底塗層且接 著沈積TCC乳液之方法具有某些缺點（尤其是在商業規模的 塗布操作中）。在單步方法中沈積TCC乳液且形成具有所要 特性的塗層而無需在塗布TCC乳液之前立即塗覆之底塗劑 係獨特優點。 已開發出二種方法以改良在基板上塗布TTC乳液之方 法0 140855.doc 201005763 第一方法包括使用含有UV活化組份之TCC乳液組合物。 此等組合物允許1塗層方法而在沈積TCC乳液之前不會立 即需要底塗劑或預處理塗層。 TCC調配物内之UV活化組份至少包括（但不限於）寡聚物 組份、單體組份及光引發劑組份。每一組份可為單一材料 或若干材料之混合物。 寡聚物或「樹酯」組份可含有（但不限於）環氧丙缔酸 酯 '丙烤酸胺基曱酸酯、聚酯丙烯酸酯（P〇lyester acrylate)、聚醚丙稀酸醋（polyether acrylate)、不飽和丙稀 酸醋、丙烯酸丙稀酸g旨（acrylic acrylate)、乙婦驗、石夕氧 烷’或其組合。寡聚物之目的為提供可聚合材料之物理特 性’例如（但不限於）膜的形成、光澤、黏著力、剛性、風 化、抗化學腐敍性（chemical resistance)、抗刮性及抗磨 性。寡聚物之量相對於總的UV「黏合劑系統」組份（由寡 聚物、單體及光引發劑組成）而言較佳為40%至80%，更佳 為50%至70%，且最佳為55%至65%。 UV黏合劑系統之單體組份可含有（但不限於）：苯乙烯， 或多官能基丙稀酸g旨（其中諸如，異冰片丙浠酸.酉旨 (isobornyl acrylate)、己二醇二丙烯酸酯（HDDA)、二丙二 醇二丙烯酸酯（DPGDA)、三丙二酵二丙稀酸酯（TPGDA)、 三羥曱基丙烷三丙烯酸酯（TMPTA)、聚乙二醇二丙烯酸 酯、雙三羥甲基丙烷四丙浠酸酯（ditrimethylolpropane tetraacrylate)、雙異戊四醇六丙烯酸酯、寡聚三丙埽酸 酯）’及其組合。單體組份亦可稱為反應性稀釋劑。單體 140855.doc 201005763 係多官能基交連劑，其與寡聚物反應以產生聚合材料。單 體通常為單官能基的、雙官能基的或三官能基的，但亦存 在具有更高官能度之其他可用單體。 除了作為反應性稀釋劑之外，單體亦用以達成多種所要 特性，例如，用以改良黏著力、反應性、抗化學腐蝕性或 抗刮性。 單體之量相對於總的UV黏合劑系統組份而言較佳為25% 至45%，更佳為30%至40%，且最佳為32%至37%。 光引發劑組份可為自由基型或離子型。光引發劑類型包 括（但不限於）經基酮（hydroxyl-ketone)、胺基酮、安息香醚 (benzoin ether)、苯曱基二甲基縮酮（BDK)、苯乙酮衍生 物、醯基膦氧化物（例如BAPO)、茂金屬、二苯甲酮/胺、 二茂鈦及°塞π顿酮（thioxanthone)衍生物。光引發劑濃度通常 小於UV活化黏合劑組份之10重量％。 較佳的光引發劑為在處於240 nm至365 nm且更佳處於 25 0 nm至280 nm之範圍中的UV波長下予以活化之光引發 劑，諸如，2-經基-2-曱基-1 -苯丙酮（IGM Resins之Omnirad 7 3)及類似化合物（例如，如IGM Re sins所提供的）。 TTC乳液之剩餘成份係如US 2005/214480及WO/2006/135735 中所描述，且主要為導電性細粒及溶劑系統。 可塗布或不塗布TCC乳液中之導電性細粒，且其組合物 可包括金屬、金屬合金、金屬鹽或其他導電的非金屬組 份，及其混合物。在較佳實施例中，顆粒係銀、銀銅合 金、碳黑或石墨，或包括銀、銀銅合金、碳黑或石墨。顆 140855.doc 201005763 粒必:頁相對細微以便形成穩定分散液。可使用具有小於約 三微米之平均顆粒尺寸的顆粒。較佳地，顆粒在「奈米」 尺寸範圍中且具有小於約100奈米之平均顆粒尺寸。 ，冷劑系統可包括非極性有機溶劑及/或極性溶劑。通 常顆粒刀散於連續有機溶劑相中，且第二相或不連續相 為水相或極性溶劑相，以產生油包水乳液。然而，亦有可 =形成顆粒之水相分散液，將有機相添加至該分散液以製 φ 仔水包油礼液。對於最佳的圖案形成而言’希望：將顆粒 7散於連續相中’且形成乳液之連續相之溶劑系統比形成 乳液之不連續相的溶劑系統蒸發得快。 將顆粒與所要溶劑混合以形《分散液可冑由機械攪摔、 球磨機>、昆合或借助於均質機或超音波混合設備來實現。可 針對每一調配物使混合次序、次數及溫度最佳化。 在較佳實施例中，將uv活化組份添加至分散液中，然 後添加第二相（藉由該第二相形成乳液狀態 瞻 其他添加劑可存在於乳液調配物中。舉例而言，添加劑 可包括（但不限於）反應性稀釋劑或非反應性稀釋劑、去氧 劑、硬塗層組份、抑制劑、穩定劑、著色劑、顏料、況吸 附劑、界面活性劑 '潤濕劑、勻塗劑（leveling agent)、流 量控制劑、觸變改質劑或其他流變改質劑、光滑劑、分散 助劑、消泡劑及腐蝕抑制劑。額外的黏合劑或黏著組份亦 可存在於調配物中，例如，熱活化黏合劑或黏著促進劑。 在製備之後且在塗布於所選基板上之前，可儲存乳液， 直至塗布方法需要乳液為止。在使用之前可混合乳液且可 140855.doc 201005763 能加熱乳液以便在塗布之前立即使乳液特性最佳化。 分散液及乳液之特徵化可包括顆粒尺寸分布、金屬負 載、穩定性，及對諸如黏度之流變特性的判定（例如，藉 由贊恩（Zahn)杯法、黏度計及/或卡森（Cass〇n)曲線分析）。 TCC乳液所塗布至之基板可為剛性材料、可撓性材料、 聚合材料、紙質材料、陶瓷材料、玻璃材料或半導體材 料。可直接使用基板，或預處理基板（例如）以便清潔表面 或以其他方式藉由物理方法或化學方法將其改變。物理方 法包括（但不限於）電暈處理、電漿處理、uv曝露處理或火 焰處理。基板可具有塗層或表面處理以改良某些特性。舉 例而言，基板可具有經塗覆以便提供對刮傷及損害之機械 抗性的硬塗層。可將此處所描述之處理及方法應用於純基 板或應用於膜供應者已置放了底塗劑、初步塗層或以其他 方式預處理了將接收TCC乳液之表面的基板。 可藉由分批塗布設備或連續塗布設備以小型實驗室規模 或以較大工業規模來執行塗布，其包括捲軸式方法。塗布 裝置可為此項技術中已知之多種接觸式或非接觸式塗布機 中之任一者’諸如’缺角輪塗布機（comma coater)、模塗 機（die coater)、凹印式塗布機（gravure c〇ater)、逆輥式塗 布機、到刀式塗布機、棒式塗布機、擠壓塗布機、簾式塗 布機’或任何其他塗布器件或計量器件。 在藉由TCC乳液對基板的塗布之後，藉由蒸發（在室内 條件下乾燥或熱處理）來移除溶劑且接著為了聚合、固化 及固定而將其曝露至UV燈。較佳的uv燈源在處於240 nm 140855.doc 201005763 至365 nm、更佳處於25〇 11„1至28〇 nm之範圍中的波長下活 化。對處理而言較佳的條件包括輸送機系統。速度為光引 發劑的類型及濃度以及所選組份之官能度的函數。對於在 以下實例中所描述之工作而言，將配備服泡之台上型輸 • 送機系統（Fusion uv System公司的 LC6B型）與 〇mnirad 73 - 光引發劑一起使用。較佳的操作速度為0.5 m/min至4 m/min ’更佳的輸送機速度為1 m/min至3 。 • 可接著應用用於固化、燒結、黏著力或其他特性改良之 額外的塗布後處理步驟，例如，二次熱步驟、雷射步驟、 微波步驟、紫外步驟或化學曝露步驟。可應用洗務步驟， J用水及/或其他化學洗滌溶液（諸如（但不限於）酸性 溶液、丙酮）或有機溶劑洗滌步驟進行洗滌。 可藉由分批處理設備或連續塗布設備以小型實驗室規模 或乂較大工業規模來執行對塗層之後處理，其包括捲轴式 方法。 • 所得TCC膜之特徵於是可為以下方面：乾燥膜厚度、基 板上之塗層的均質性、平均丁叫元尺寸、單元尺于分 布、透光度、混濁度、薄層電阻、取單元之行高、tcc 行之厚度、表面能、塗層對基板之黏著力、麵屏蔽作 用，及對刮傷、摩擦、輥軋及按壓的抗性。 在不使用初步塗層或底塗層的情況下，將含有—活化 組份之TCC組合舶JΕ ΤΤΛλ m 勿曝路至UV固化條件，其給出小於丄2 〇—之電阻值’大於娜之透光度，小於5%之混濁卜 用於在不需要在線塗覆底塗劑的情況下改良塗布TCC乳 140855.doc 11 201005763 液之方法之第二方法包括在藉由Tcc乳液塗布之前對基板 的uv活化或其他物理活化。較佳藉由具有在24〇 1^1至365 nm、更佳250 nm至280 nm之範圍中之主要波長的uv源（例 如，如同Η燈泡的情形一樣）將表面曝露至uv活化。作為 替代或除了將UV活化成份併入乳液調配物中之外，可使 用該活化。 除了 UV活化之外，用以預處理基板之物理活化方法包 括藉由電漿、雷射、微波或化學曝露進行之處理。可在後 續塗布步驟之前立即離線或線上執行預處理步驟。作為線 上預處理之實例，在單一 1遍1塗層之連續方法中，可藉由 uv輻射來處理ΡΕΤ膜且接著立即藉由適當Tcc調配物來塗 布PET膜。 可將此處所描述之處理及方法應用於純基板或應用於膜 供應者已置放了底塗劑、初步塗層或以其他方式預處理了 將接收TCC乳液沈積之表面的基板。 可藉由分批處理設備或連績塗布設備以小型實驗室規模 或以較大工業規模來執行在塗覆TCC塗層之前對基板的該 物理處理，其包括捲軸式方法。 改良塗布tcc乳液之方法的另一種方法包括使用uv活化 黏合劑組合物來預處理基板。已發現該預處理會改良（尤 其是在諸如PET基板之可撓性基板上的）後續塗布之TCC圖 案且產生經均勻塗布且很好地黏附至基板的黏合劑層。 UV活化黏合劑組合物可至少包括（但不限於）寡聚物組 份、單體組份及光引發劑組份。每一組份可為單一材料或 140855.doc 12 201005763 可為若干材料之混合物。 寡聚物或「樹酯」組份可含有（但不限於）環氧丙烯酸 酯、丙烯酸胺基曱酸酯、聚酯丙烯酸酯、聚醚丙烯酸酯、 不飽和丙烯酸酯、丙烯酸丙烯酸酯、乙烯醚、矽氧烷，或 其組合。募聚物之量相對於總的υν活化組份（由募聚物、 單體及光引發劑組成）而言較佳為40%至80%，更佳為50% 至70%，最佳為55%至65%。 單體組份可含有（但不限於）苯乙烯，或多官能基丙烯酸 酯（其中諸如，異冰片丙稀酸酯、己二醇二丙稀睃酯 (HDDA)、二丙二醇二丙締酸酯（DPGDA)、三丙二酵二丙 稀酸醋（TPGDA)、三經甲基丙烧三丙烯酸g旨（ΤΜΡΤΑ)、聚 乙一醇二丙稀酸醋、雙三經甲基丙烧四丙稀酸醋、雙異戊 四醇六丙烯酸酯、寡聚三丙烯酸酯），及其組合。單體組 份亦可稱為反應性稀釋劑。單體通常為單官能基的、雙官 月&基的或二官能基的’但亦存在具有更高官能度之其他可 用單體。單體之量相對於黏合劑調配物中之總的UV活化 組份而言較佳為25%至45%，更佳為30%至40%，最佳為 32%至 37%。 光引發劑組份可為自由基型或離子型。其可包括（但不 限於）羥基酮、胺基酮、安息香醚、苯曱基二曱基縮酮 (BDK)、苯乙酮衍生物、醯基膦氧化物（例如BAp〇)、茂金 屬、二苯曱酮化合物、二笨曱酮/胺' 樟腦醌、二苯基乙 一輞、一戊鈦，及苐酮、蒽8¾ (anthraquinone)、氧雜蔥網 (xanthone)及/或噻噸酮衍生物。光引發劑濃度通常小於uv 140855.doc 13 201005763 活化組份之1〇重量％。較佳的光引發劑為在處於24〇 nm至 365 nm且更佳處於250 nm至280 nm之範圍中的Uv波長下 予以活化之光引發劑，諸如，2-羥基-2-甲基_1_苯丙酮 (IGM Resins之Omnirad 73)及類似化合物（例如，如IGM Resins所提供的）。 較佳地，UV活化黏合劑預處理組合物亦可包括能夠與 黏合劑調配物中之UV活化組份以化學方式交互作用的額 外組份，例如，界面活性劑。舉例而言，Maxemul 5〇11及 5〇l〇(Uniqema)為具有不飽和烯基之界面活性劑，其能夠 在u v起始聚合期間與黏合劑調配物中之u v活化組份以化201005763 Wei. VI. Description of the Invention: [Technical Field] The present invention is in the field of transparent coatings, more specifically on a transparent conductive coating formed of an emulsion containing conductive fine particles, applied to a substrate And after the liquid carrier is released, the particles can be self-assembled into an open unit mesh conductive pattern. The particular field of the invention relates to the formation of a transparent conductive coating on a substrate. Wenliang's method (its package (4) substrate surface treatment)' and an emulsion formulation that does not require a special primer layer prior to coating. This application is hereby incorporated by reference in its entirety by reference in its entirety in its entirety in the the the the the the the the the the the [Prior Art] Materials and methods for forming transparent conductive coatings are beneficial for the development and manufacture of electronic devices. These coatings provide several functions such as electromagnetic (EMI) shielding and static dissipation, and these coatings act as light transmissive conductive layers and electrodes in a variety of applications. Such applications include, but are not limited to, useful devices or portions of devices such as touch screens, wireless electronic boards, photovoltaic devices, conductive textiles and fibers, displays, OLEDs, and electronics such as electronic paper. Light-emitting structure. A transparent conductive coating (TCC) is prepared using an emulsion as described in US200502 14480. The undercoat or pretreatment coating applied immediately prior to coating by the emulsion has been used to preferentially modify the surface characteristics of the substrate to be coated by the emulsion. In the above-mentioned US 2005/0214480, the method of coating 140855.doc 201005763 cloth TCC on a glass and polyimide substrate comprises a preliminary coating step in which a compound or other interface in acetone is applied before the TCC emulsion is applied. The active agent is applied to the surface of the substrate. These pretreatment coating compositions are referred to as "primer". After the primer is applied and allowed to dry, the TCC coating is applied. In the case of WO2006/135735, the PET film treated with a hexane solution of an octyltriethoxysilane primer was modified to have a TCC pattern relative to the untreated film. • There are several disadvantages to including a separate step for applying the primer or other preliminary coating layer immediately prior to deposition of the TCC emulsion. A commercially viable coating method for depositing a primer or a preliminary coating layer and then depositing a TCC formulation requires two coating heads and thus requires a two-step process. Preferably, the method operates by a single-coating head and in a single-step process. Further, when the subsequent TCC layer is applied immediately after the deposition of the primer layer, the non-uniformity of the undercoat layer and the interaction of the emulsion with the primer may cause a lack of accompanying in the subsequent Tcc layer. Acetone-based money agents have additional disadvantages. Acetone is highly flammable; the film quality of the acetone-based primer usually affects the subsequent uniformity of the TCC unit size; and the primer layer produced by the acetone-based primer is in the intermediate disposal step. (For example, 'If it is rolled or otherwise stored before the subsequent coating step, it may not be able to maintain its characteristics. There is therefore a need for alternative TCC emulsion formulations or surface treatments to eliminate current primers in commercial scale coating operations without adversely affecting pattern formation. SUMMARY OF THE INVENTION Various improved methods for forming TCC on a substrate are described, wherein 140855.doc 201005763 both methods eliminate the need to apply a primer to a substrate immediately prior to coating the TCC emulsion and still obtain acceptable TCC pattern. A third method provides a new and more versatile preliminary treatment coating on the substrate. These methods are particularly useful for commercially available "T flexible substrates, including optical ΡΕτ substrates using large scale coating equipment. A method includes incorporating a UV curable component into a TCC emulsion and applying a UV curing step during TCC formation. Another method involves uv activation or other physical activation of the substrate prior to coating by the TCC emulsion. Another method involves pre-treating the substrate by a uv-activated binder that is sufficiently stable on the substrate to allow storage of the substrate in a single pass coating process and later coating the substrate with a TCC emulsion. [Embodiment] When a TCC emulsion (such as those described in US 2005/214480 and WO 2006/3 5735, both of which are incorporated herein by reference), is applied to the "pre-treatment" coating on the surface of the substrate. The TCC emulsion provides a uniform pattern with a relatively uniform cell size distribution on the layer or undercoat. Renmin, as mentioned above, the first method of depositing a preliminary coating or undercoat layer followed by deposition of a TCC emulsion has certain disadvantages (especially in commercial scale coating operations). It is a unique advantage to deposit the TCC emulsion in a single step process and form a coating having the desired characteristics without the need to apply the primer immediately prior to application of the TCC emulsion. Two methods have been developed to improve the method of coating a TTC emulsion on a substrate. 0 140855.doc 201005763 The first method involves the use of a TCC emulsion composition containing a UV activating component. These compositions allow for a one coat process without the need for a primer or pretreatment coating immediately prior to depositing the TCC emulsion. The UV-activated component of the TCC formulation includes, but is not limited to, an oligomer component, a monomer component, and a photoinitiator component. Each component can be a single material or a mixture of several materials. The oligomer or "tree ester" component may contain, but is not limited to, epoxidized propionate 'propanol phthalate, styrene acrylate, polyether acrylate vinegar (polyether acrylate), unsaturated acrylate vinegar, acrylic acrylate, acetaminophen, oxalate, or a combination thereof. The purpose of the oligomer is to provide physical properties of the polymerizable material such as, but not limited to, film formation, gloss, adhesion, rigidity, weathering, chemical resistance, scratch resistance and abrasion resistance. . The amount of oligomer is preferably from 40% to 80%, more preferably from 50% to 70%, relative to the total UV "binder system" component (composed of oligomers, monomers, and photoinitiators). And the best is 55% to 65%. The monomer component of the UV adhesive system may contain, but is not limited to, styrene, or polyfunctional acrylate acid (wherein, for example, isobornyl acrylate, hexanediol II) Acrylate (HDDA), dipropylene glycol diacrylate (DPGDA), tripropylene diacetate (TPGDA), trihydroxydecyl propane triacrylate (TMPTA), polyethylene glycol diacrylate, double three Ditrimethylolpropane tetraacrylate, diisoamyltetraol hexaacrylate, oligomeric tripropionate, and combinations thereof. The monomer component can also be referred to as a reactive diluent. Monomers 140855.doc 201005763 is a polyfunctional crosslinking agent that reacts with oligomers to produce a polymeric material. Monomers are typically monofunctional, difunctional or trifunctional, but other available monomers having higher functionality are also present. In addition to being a reactive diluent, the monomers are also used to achieve a variety of desirable properties, for example, to improve adhesion, reactivity, chemical resistance, or scratch resistance. The amount of monomer is preferably from 25% to 45%, more preferably from 30% to 40%, and most preferably from 32% to 37%, relative to the total UV binder system component. The photoinitiator component can be free radical or ionic. Types of photoinitiators include, but are not limited to, hydroxyl-ketone, aminoketone, benzoin ether, benzoyl dimethyl ketal (BDK), acetophenone derivatives, sulfhydryl groups Phosphonium oxides (e.g., BAPO), metallocenes, benzophenones/amines, titanocene, and thioxanthone derivatives. The photoinitiator concentration is typically less than 10% by weight of the UV activated binder component. Preferred photoinitiators are photoinitiators which are activated at UV wavelengths in the range of from 240 nm to 365 nm and more preferably from 25 nm to 280 nm, such as 2-amino-2-indenyl- 1-propiophenone (Imnirad 7 3 of IGM Resins) and similar compounds (for example, as provided by IGM Resins). The remaining components of the TTC emulsion are as described in US 2005/214480 and WO/2006/135735, and are primarily conductive fine particles and solvent systems. The conductive fine particles in the TCC emulsion may or may not be coated, and the composition may include a metal, a metal alloy, a metal salt or other conductive non-metal component, and a mixture thereof. In a preferred embodiment, the particles are silver, silver-copper alloy, carbon black or graphite, or include silver, silver-copper alloy, carbon black or graphite. 140855.doc 201005763 Grains: The pages are relatively fine to form a stable dispersion. Particles having an average particle size of less than about three microns can be used. Preferably, the particles are in the "nano" size range and have an average particle size of less than about 100 nanometers. The refrigerant system may include a non-polar organic solvent and/or a polar solvent. Typically the granules are dispersed in a continuous organic solvent phase and the second or discontinuous phase is an aqueous phase or a polar solvent phase to produce a water-in-oil emulsion. However, there is also an aqueous phase dispersion which forms particles, and an organic phase is added to the dispersion to prepare a φ water-in-water liqueur. For optimum pattern formation, it is desirable to disperse the particles 7 in the continuous phase and the solvent system that forms the continuous phase of the emulsion evaporates faster than the solvent system that forms the discontinuous phase of the emulsion. The granules are mixed with the desired solvent to form a dispersion which can be achieved by mechanical agitation, ball mills, kneading or by means of a homogenizer or ultrasonic mixing device. The mixing order, number of times, and temperature can be optimized for each formulation. In a preferred embodiment, the uv activating component is added to the dispersion and then the second phase is added (by the second phase forming an emulsion state, other additives may be present in the emulsion formulation. For example, the additive may Including, but not limited to, reactive diluents or non-reactive diluents, oxygen scavengers, hard coat components, inhibitors, stabilizers, colorants, pigments, sorbents, surfactants, wetting agents, Leveling agent, flow control agent, thixotropic modifier or other rheology modifier, smoothing agent, dispersing aid, antifoaming agent and corrosion inhibitor. Additional adhesive or adhesive component can also be used. In the formulation, for example, a heat activated adhesive or an adhesion promoter. The emulsion may be stored after preparation and before application to a selected substrate until the coating process requires an emulsion. The emulsion may be mixed prior to use and may be 140855 .doc 201005763 The emulsion can be heated to optimize emulsion characteristics immediately prior to coating. Characterization of dispersions and emulsions can include particle size distribution, metal loading, stability, and The determination of the rheological properties of the degree (for example, by Zahn cup method, viscometer and / or Cassin curve). The substrate to which the TCC emulsion is applied can be rigid material and flexible. Materials, polymeric materials, paper materials, ceramic materials, glass materials or semiconductor materials. The substrate can be used directly, or the substrate can be pretreated, for example, to clean the surface or otherwise altered by physical or chemical means. This includes, but is not limited to, corona treatment, plasma treatment, uv exposure treatment, or flame treatment. The substrate may have a coating or surface treatment to improve certain characteristics. For example, the substrate may be coated to provide scratch protection And mechanically resistant hard coatings that may be damaged. The treatments and methods described herein may be applied to a pure substrate or applied to a film supplier who has placed a primer, preliminary coating or otherwise pretreated to receive Substrate on the surface of the TCC emulsion. Coating can be performed on a small laboratory scale or on a larger industrial scale by batch coating equipment or continuous coating equipment, including roll-type The coating device can be any of a variety of contact or non-contact coaters known in the art, such as comma coaters, die coaters, gravure coatings. Machine (gravure c〇ater), reverse roll coater, to knife coater, bar coater, extrusion coater, curtain coater' or any other coating device or metering device. After coating of the substrate, the solvent is removed by evaporation (drying or heat treatment under room conditions) and then exposed to a UV lamp for polymerization, curing and fixing. A preferred uv source is at 240 nm 140855.doc 201005763 to 365 nm, more preferably activated at a wavelength in the range of 25 〇 11 „1 to 28 〇 nm. Preferred conditions for processing include conveyor systems. Speed is a function of the type and concentration of the photoinitiator and the functionality of the selected component. For the work described in the examples below, an on-board conveyor system (LC6B from Fusion uv System) equipped with a bubbling machine was used with 〇mnirad 73 - photoinitiator. The preferred operating speed is from 0.5 m/min to 4 m/min. The better conveyor speed is from 1 m/min to 3 . • Additional post-coating treatment steps for curing, sintering, adhesion or other property modification may be applied, for example, a secondary thermal step, a laser step, a microwave step, an ultraviolet step, or a chemical exposure step. A washing step can be applied, J washing with water and/or other chemical washing solution such as, but not limited to, an acidic solution, acetone, or an organic solvent washing step. The post-coating treatment can be performed on a small laboratory scale or on a larger industrial scale by a batch processing apparatus or a continuous coating apparatus, including a roll-to-roll method. • The characteristics of the resulting TCC film can then be as follows: dry film thickness, uniformity of the coating on the substrate, average butyl size, unit size distribution, transmittance, turbidity, sheet resistance, unit Row height, thickness of tcc row, surface energy, adhesion of the coating to the substrate, surface shielding, and resistance to scratching, rubbing, rolling and pressing. In the case where the preliminary coating or the undercoat layer is not used, the TCC combination containing the -active component is not exposed to the UV curing condition, which gives a resistance value less than 丄2 〇 - greater than Na Transmittance, less than 5% turbidity The second method for improving the method of coating TCC milk 140855.doc 11 201005763 without the need for in-line coating of the primer includes the substrate before coating by Tcc emulsion Uv activation or other physical activation. Preferably, the surface is exposed to uv activation by a uv source having a dominant wavelength in the range of 24 〇 1^1 to 365 nm, more preferably 250 nm to 280 nm (e.g., as in the case of a xenon bulb). This activation can be used in place of or in addition to incorporating the UV activating component into the emulsion formulation. In addition to UV activation, the physical activation method used to pretreat the substrate includes treatment by plasma, laser, microwave or chemical exposure. The pre-treatment step can be performed offline or online immediately prior to the subsequent coating step. As an example of on-line pretreatment, in a continuous process of a single pass 1 coating, the ruthenium film can be treated by uv radiation and then the PET film can be applied immediately by a suitable Tcc formulation. The processes and methods described herein can be applied to a pure substrate or applied to a film. The substrate has been primed, preliminarily coated, or otherwise pretreated with a substrate that will receive the surface deposited by the TCC emulsion. This physical treatment of the substrate prior to application of the TCC coating can be performed on a small laboratory scale or on a larger industrial scale by batch processing equipment or continuous coating equipment, including a roll-to-roll method. Another method of improving the method of coating a tcc emulsion involves pretreating the substrate using a uv activated adhesive composition. This pretreatment has been found to improve (e.g., on a flexible substrate such as a PET substrate) a subsequently coated TCC pattern and produce a layer of adhesive that is uniformly coated and adheres well to the substrate. The UV-activated binder composition can include, but is not limited to, an oligomer component, a monomer component, and a photoinitiator component. Each component can be a single material or 140855.doc 12 201005763 can be a mixture of several materials. The oligomer or "tree ester" component may contain, but is not limited to, epoxy acrylate, urethane acrylate, polyester acrylate, polyether acrylate, unsaturated acrylate, acrylic acrylate, vinyl ether , a siloxane, or a combination thereof. The amount of the polymer is preferably from 40% to 80%, more preferably from 50% to 70%, more preferably from 50% to 70%, based on the total υν activating component (composed of a polymer, a monomer, and a photoinitiator). 55% to 65%. The monomer component may contain, but is not limited to, styrene, or a polyfunctional acrylate (such as, for example, isobornyl acrylate, hexanediol diisopropyl ester (HDDA), dipropylene glycol dipropionate) (DPGDA), tripropylene glycol diacetate (TPGDA), trimethyl methacrylate triacrylate g (ΤΜΡΤΑ), polyethyl propylene glycol diacetate, bis trimethyl methacrylate Sour vinegar, diisoamyltetraol hexaacrylate, oligomeric triacrylate), and combinations thereof. The monomer component can also be referred to as a reactive diluent. The monomers are typically monofunctional, bis-monthly & amply or difunctional' but other available monomers having higher functionality are also present. The amount of monomer is preferably from 25% to 45%, more preferably from 30% to 40%, most preferably from 32% to 37%, relative to the total UV-activated component of the adhesive formulation. The photoinitiator component can be free radical or ionic. It may include, but is not limited to, hydroxyketones, aminoketones, benzoin ethers, benzoguanidinyl ketal (BDK), acetophenone derivatives, mercaptophosphine oxides (eg, BAp), metallocenes, Diphenyl fluorenone compound, diclofenac/amine ' camphor quinone, diphenyl ethane oxime, monopenta titanium, and anthraquinone, anthraquinone, xanthone and/or thioxanthone Things. The photoinitiator concentration is typically less than 1% by weight of the uv 140855.doc 13 201005763 activating component. Preferred photoinitiators are photoinitiators which are activated at Uv wavelengths in the range of from 24 Å to 365 nm and more preferably from 250 nm to 280 nm, such as 2-hydroxy-2-methyl_1 Benzylacetone (Imnirad 73 from IGM Resins) and similar compounds (for example, as provided by IGM Resins). Preferably, the UV-activated binder pretreatment composition can also include additional components that are capable of chemically interacting with the UV-activated component of the binder formulation, for example, a surfactant. For example, Maxemul 5〇11 and 5〇l〇(Uniqema) are surfactants having an unsaturated alkenyl group capable of reacting with the v-v activation component in the binder formulation during the initial polymerization of u v
學方式反應。界面活性劑增加基板之可濕性。藉由與黏1 劑調配物t之可聚合組份反應，界面活性劑變得固^至: 面且在塗覆之後不會隨著時間的推移而在基板上遷移。Learning method response. The surfactant increases the wettability of the substrate. By reacting with the polymerizable component of the adhesive formulation t, the surfactant becomes solidified to the surface and does not migrate over the substrate over time after coating.
可將黏合劑組份可分散或稀釋⑨溶劑中，㈣分散或奉 釋，以水為主或以乙醇為主之溶劑或稀釋劑中。總的固患 3 $較佳小於2G重量％。黏合劑組合物亦可包括額外添办 劑’例如，反純雜_敍應性賴#卜敎劑、去 氧劑、、硬塗層組份、抑制劑、著色劑、顏料、m吸附劑、 ::活性劑、潤濕劑、勻塗劑、&量控制劑、觸變改質劑 二劑他二：改質劑、光滑劑、分散助劑、消泡劑及腐韻抑 夕黏合劑或黏著組份亦可存在於調配物中，例 ，…、活化黏合劑或黏著促進劑。 混：:：劑組合物之組份的現合可藉由機械授掉、球磨機 S 3助於均質機或超音波混合設備來實現。可針對每 140855.doc -14- 201005763 一調配物使混合次序、次數及溫度最佳化。黏合劑調配物 之特徵化可包括對黏度的判定（例如，藉由黏度計或諸如 贊恩（Zahn)杯方法的其他方法）。 可將黏合劑預處理應用於純基板或應用於膜供應者已置 放了底塗劑、初步塗層或以其他方式預處理了將接收1^€ 乳液之表面的基板。The binder component can be dispersed or diluted in a solvent, (iv) dispersed or decontaminated, in a water-based or ethanol-based solvent or diluent. The total solids 3 $ is preferably less than 2 G weight percent. The binder composition may also include additional additives 'eg, anti-pure _ _ _ _ _ _ 敎 敎 、 去 去 去 去 去 去 去 去 去 去 去 去 、 、 、 硬 硬 硬 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ::Active agent, wetting agent, leveling agent, & amount control agent, thixotropic modifier two agents: modifier, smoothing agent, dispersing aid, defoaming agent and stagnation adhesive Or the adhesive component may also be present in the formulation, for example, an activated binder or an adhesion promoter. The mixing of the components of the ::: composition can be achieved by mechanical transfer, ball mill S 3 assisted by a homogenizer or ultrasonic mixing device. The mixing order, number of times and temperature can be optimized for each formulation of 140855.doc -14- 201005763. Characterization of the adhesive formulation can include a determination of viscosity (e.g., by a viscometer or other method such as the Zahn cup method). Adhesive pretreatment can be applied to a pure substrate or applied to a film supplier where a primer has been placed, a preliminary coating, or otherwise pretreated with a substrate that will receive the surface of the emulsion.
可應用於具有硬塗層之HF1C21 PET膜（Teijin Dupont)的 UV可聚合黏合劑預處理之實例（例如，用於觸控螢幕應用） 為在乙酸乙酯或乙醇中以重量計1:2〇之比率經稀釋2LUv_ PET-004黏合劑（T〇(jay,s suntech有限公司）。 可藉由分批處理設備或連續塗布設備以小型實驗室規模 或、較大工業規模來執行在基板上對黏合劑組合物的塗 布，其包括捲軸式方法。塗布裝置可為此項技術中已知之 多種接觸式或非接觸式塗布機中之任一者，諸如缺角輪塗 布機杈塗機、凹印式塗布機、逆輥式塗布機、刮刀式塗 布機 '棒式塗布機、擠壓塗布機、簾式塗布機，或任何其 他塗布器件或計量器件。 黏合劑層之濕潤厚度通常小於3〇微米，較佳小於職 :’且最佳小於12微米。在藉由黏合劑組合物對基板的塗 布之後，藉由基發（例 '' (]如，精由在至内條件下乾燥或藉由 如在洪箱中之敎處 ”，、 ）來移除溶劑且接著為了聚合、固化 及固疋而將經參亦 堂布之膜曝露至UV燈（通常在24〇 ηπ^365 nm的範圍中）。 "著將萄外處理步驟應用於黏合劑預處理塗層，以便 I40855.doc 201005763 在藉由TCC乳液調配物塗布之前改良黏著力或添加圖案化 或其他特性。 在應用黏合劑預處理塗層及可選的塗布後處理之後，可 輥軋、捲繞、堆疊、按壓及儲存該等膜，直至在將來的時 間藉由TCC乳液調配物進行的後續塗布為止。 乾燥後之點合劑層及經塗布之基板的特徵可為以下方 面.乾燥膜厚度、表面上之塗層的均質性、黏著力、透射 率、混濁度、表面能、接觸角及關於時間之穩定性。 實例1 : 執仃1步、1遍之TCC沈積方法，其中將11乂可聚合組份併 入TCC乳液調配物内。製備uv固化募聚物' 單體及光引發 劑組份的乙酸乙酯溶液（「s_uv」）。單體為HDDA(1,6己 二醇二丙烯酸酯）’寡聚物為脂族丙烯酸胺基甲酸酯（臺灣 Eternal Chem· Co 的 Etercure 6161_100)，且光引發劑為 Omnirad 73(荷蘭 Waalwjik 之 IGM Resins)» 募聚物：單體： 光引發劑之比率為以重量計6〇:35:5，且此等材料與乙酸乙 酯溶劑之比例為以重量計40:60。接著將此uv添加劑溶液 以1重量％之含量添加至TCC分散液。接著添加水相溶液以 產生如表1中所展示之最終TCC乳液。 140855.doc -16· 201005763 成份 % Byk410 0.1 Byk 106 0.02 2-胺基-1-丁醇 0.2 曱苯中之5%磺琥珀酸鈉二辛酯(AOT) 0.3 苯胺 0.5 環己酮 2.9 甲苯 44.4 S-UV 1 Span 60 0.1 甲環己烷 9.9 P204銀奈米粉體 3.7 BS16 (Wacker) 0.4 水中之0.02%的1-辛烷-硫酸鈉鹽 36.5 總計 100 接著將TCC乳液塗布於用於EMI屏蔽應用的商用 Lumirror U46 PET膜（Toray)上。在約 22°C 及約 50% 的濕度 下使用配備梅爾（Meyer)塗布棒之K202 K控制塗布機（英國 RK Print)將該乳液塗覆至膜表面。在沈積乳液之前未藉由 底塗劑或初步塗布層來塗布該膜。乳液之濕潤厚度為30微 米。在藉由乳液塗布之後，在150°C下加熱該膜歷時12 秒，且接著使其以2 m/min之速度通過UV腔室（Fusion UV System公司的LC6B台上型輸送機），該UV腔室在離取樣 表面53.3 mm距離處具有120 W/cm的Η燈泡。在UV曝露之 後，藉由接連浸潰於丙酮中歷時30秒，然後浸潰於1Μ HCI溶液中歷時1分鐘，且接著在去離子水中沖洗歷時30秒 來處理該膜。接著在封閉烘箱中在150t下加熱該膜歷時2 分鐘® 140855.doc -17- 201005763 如藉由配備ESP型探針之Loresta GP電阻儀所判定，TCC 塗層之電阻為6 ohm/sq至9 ohm/sq。藉由Haze Gard Plus (Byk-Gardner)混濁度儀（hazemeter)測得之平均透射率及混 濁度分別為82%及4.6%。在圖1中展示所得TCC塗層之顯微 圖（如藉由Nikon SMZ800立體顯微鏡在4X放大率下所獲 得）。 實例2 : 藉由以在1.5 m/min至2.7 m/min的範圍中之各種輸送機 速度通過LC6B台上型輸送機腔室（Fusion UV System公 司），將具有硬塗層表面之光學級HF1C21 PET膜（日本的 Teijin DuPont)在非硬塗層側上曝露至UV處理。然後，以 40微米之濕潤厚度在非硬塗層側上將如下表2中所描述之 TCC乳液塗布至該等膜上。在沈積TCC乳液之前不塗覆底 塗劑或初步塗布材料。在塗布步驟之後，在1 50°C下加熱 該膜歷時3分鐘且隨後用丙酮洗滌該膜歷時30秒至40秒且 接著在空氣中使其乾燥。所得TCC塗層具有200 ohm/sq至 300 ohm/sq之薄層電阻、85%以上的透光度及約4%之混濁 度’且適合於觸控螢幕應用。如在對圖案表面應用並移除 膠帶（Permacel P-99)之後藉由薄層電阻的重複量測所判 定’ TCC對基板之黏著力良好。圖2展示在以1.5 m/min之 輸送機速度予以UV處理的該膜上獲得之TCC圖案。 140855.doc -18- 201005763 表2 : TCC乳液、組份 成份 重量(％) Cymel 1168 0.1 K flex 307 xm 0.1 Nacure 2501 0.1 Byk410 0.2 Span 60 0.2 苯胺 0.1 Byk 106 0.1 2胺基丁醇 0.2 環己烷 8.0 環己酮 4.1 甲苯 53.9 P204銀奈米粉體 1.0 水中之0.04%的十二烷基硫酸鈉(SDS) 31.9 總計 100 相對於上文描述之HF1C21膜，另一商用硬塗層PET膜 (Toyobo A4300)需要較高之UV曝露以便在隨後在非硬塗層 側上藉由TCC乳液對該等膜進行塗布時導致良好TCC圖 案。藉由以1 · 1 m/min之速度兩次通過UV腔室（當其後以40 • 微米之濕潤厚度來塗布TCC乳液時）獲得良好結果。藉由以 上針對HF1C21膜給出之相同條件對膜進行後處理。 以1 m/min及2 m/min之輸送機速率在與以上相同之設備 上對 PET 膜 Skyrol SH34 PET 膜（SKC)及 Lumirror U46 PET 膜（Toray)(兩者皆不具有硬塗層表面）進行UV處理。當隨後 藉由如表3中所描述之TCC乳液進行塗布時，獲得如圖3中 之網狀圖案。 140855.doc •19· 201005763 表3 : TCC乳液、組份 成份 重量(％) Byk410 0.2 Span 60 0.2 苯胺 0.2 Byk 106 0.4 2胺基丁醇 0.1 曱苯中之5%的續琥珀酸鈉二辛酯(AOT) 0.1 環己酮 4.1 環己烷 —--- 28.1 Cymel 303 0.2 K flex 307xm 0.1 Nacure 2501 0.2 -- 30.1 油酸 0.1 曱苯中之0.08%的Bykl06 0.2 P 204 1.2 水中之1).04%的十二烷基硫酸鈉(SDS) 34.5 總計 100 實例3 對於觸控螢幕應用而言，針對HF1C21光學PET膜（Teijin Dupont)開發出具有uv可聚合黏合劑預處理之2步、2遍方 法。製備包含0.3 g具有雙鍵之反應性界面活性劑（Maxemul 5011)、4.0 g LUV-PET-004(Today，s Suntech有限公司）及 45.7 g乙醇的黏合劑調配物。LUV-PET-004為用於PET之市 售UV固化硬塗層樹脂。其化學性專屬於供應者，但包括 丙烯酸型募聚物、單體及光引發劑。將此黏合劑組合物以 12微米之濕潤厚度塗布於HF1C21膜上，且接著在室溫下 將其乾燥歷時1分鐘。接著在150°C下熱處理該黏合劑塗層 歷時1分鐘，且接著以2m/min在LC6B輸送機上將其曝露至 140855.doc •20· 201005763 輕射’ S^LC6B輸送機在離取樣表面53.3 mm距離處具 有120/W/cm的Η燈泡。在乾燥及uV聚合之後，乾燥厚度為 約〇·5微米。相對於未處理之膜而言，未不利地影響透射 率及屈w蜀度特性。認為雙鍵界面活性劑能夠與LUV_pET_ 004材料中之可固化丙烯酸硬塗層組份聚合或鍵結至該等 組伤。所得的所塗布黏合劑層為均貲的（如藉由視覺及顯 微鏡檢驗所判定）且很好地固定在基板表面上。 如以上在表1中所描述之TCC乳液在被塗覆於此黏合劑 預處理層上時給出具有大於80%之透光度的良好圖案。在 被塗布於基板上之後，黏合劑層在高達18天之測試中關於 時間穩定°此外，當藉由黏合劑組合物來塗布基板且接著 在20 kg重量之壓力下將基板保持於膜堆疊中歷時18天 時’隨後以上文所描述之方式塗布於該基板上面的TCC塗 層給出可接受之薄層電阻及大於8〇%的透光度。 【圖式簡單說明】 圖1為由含有UV活化組份之乳液形成之透明導電塗層的 顯微照片； 圖2為形成於在塗覆TCC乳液之前已予以UV處理的基板 上之透明導電塗層的顯微照片；及 圖3為形成於在塗覆TCC乳液之前亦已予以UV處理的基 板上之透明導電塗層的顯微照片。 140855.doc -21-An example of UV polymerizable adhesive pretreatment that can be applied to HF1C21 PET film (Teijin Dupont) with hard coat (for example, for touch screen applications) is 1:2 by weight in ethyl acetate or ethanol The ratio is diluted with 2LUv_PET-004 adhesive (T〇 (jay, s suntech Co., Ltd.). It can be performed on a substrate on a small laboratory scale or on a larger industrial scale by batch processing equipment or continuous coating equipment. Coating of the adhesive composition, including a roll-to-roll method. The coating device can be any of a variety of contact or non-contact coaters known in the art, such as a slant coater, gravure, gravure Coating machine, reverse roll coater, knife coater 'bar coater, extrusion coater, curtain coater, or any other coating device or metering device. The wet thickness of the adhesive layer is usually less than 3 μm Preferably, less than: 'and optimally less than 12 micrometers. After coating the substrate by the binder composition, by base hair (eg, '[], for example, by drying under internal conditions or by As in the floodgates , , ) to remove the solvent and then expose the film of the ginseng to the UV lamp for polymerization, solidification and solidification (usually in the range of 24 〇 π π 365 nm). The procedure is applied to the binder pretreatment coating so that I40855.doc 201005763 improves the adhesion or adds patterning or other properties prior to coating by the TCC emulsion formulation. Applying the binder pretreatment coating and optional post-coating treatment Thereafter, the films can be rolled, wound, stacked, pressed, and stored until subsequent coating by the TCC emulsion formulation at a later time. The dried dot layer and the coated substrate can be characterized The following aspects: dry film thickness, coating homogeneity, adhesion, transmittance, turbidity, surface energy, contact angle and stability with respect to time. Example 1: TCC deposition of 1 step, 1 pass A method in which a 11 Å polymerizable component is incorporated into a TCC emulsion formulation. An acetified solution of a uv-cured merging polymer monomer and a photoinitiator component ("s_uv") is prepared. The monomer is HDDA (1) 6 hexanediol dipropylene The acid ester) is an aliphatic urethane urethane (Etercure 6161_100 from Eternal Chem. Co., Taiwan), and the photoinitiator is Omnirad 73 (IGM Resins, Waalwjik, Netherlands). Concentrate: Monomer: Light The ratio of initiator is 6 〇:35:5 by weight, and the ratio of these materials to ethyl acetate solvent is 40:60 by weight. This uv additive solution is then added to the TCC dispersion at a content of 1% by weight. The aqueous phase solution was then added to produce the final TCC emulsion as shown in Table 1. 140855.doc -16· 201005763 Ingredient% Byk410 0.1 Byk 106 0.02 2-Amino-1-butanol 0.2 5% sodium sulfosuccinate dioctyl ester (AOT) 0.3 Aniline 0.5 Cyclohexanone 2.9 Toluene 44.4 S -UV 1 Span 60 0.1 Cyclohexane 9.9 P204 Silver Nano Powder 3.7 BS16 (Wacker) 0.4 0.02% 1-octane-sodium sulfate salt in water 36.5 Total 100 Next TCC emulsion is applied to EMI shielding applications Commercial Lumirror U46 PET film (Toray). The emulsion was applied to the surface of the film using a K202 K controlled coater (UK RK Print) equipped with a Meyer coating bar at about 22 ° C and about 50% humidity. The film was not coated by a primer or a preliminary coating layer prior to depositing the emulsion. The wet thickness of the emulsion is 30 microns. After coating by emulsion, the film was heated at 150 ° C for 12 seconds and then passed through a UV chamber (Fusion UV System LC6B overhead conveyor) at a rate of 2 m/min. The chamber has a 120 W/cm xenon bulb at a distance of 53.3 mm from the sampling surface. After UV exposure, the film was treated by successively immersing in acetone for 30 seconds, then dipping in 1 Torr of HCI solution for 1 minute, and then rinsing in deionized water for 30 seconds. The film was then heated in a closed oven at 150 t for 2 minutes. ® 140855.doc -17- 201005763 The resistance of the TCC coating was 6 ohm/sq to 9 as determined by a Loresta GP resistor equipped with an ESP probe. Ohm/sq. The average transmittance and turbidity measured by Haze Gard Plus (Byk-Gardner) hazemeter were 82% and 4.6%, respectively. A micrograph of the resulting TCC coating is shown in Figure 1 (as obtained by a Nikon SMZ800 stereomicroscope at 4X magnification). Example 2: Optical grade HF1C21 with hard coated surface by passing through an LC6B overhead conveyor chamber (Fusion UV System) at various conveyor speeds in the range of 1.5 m/min to 2.7 m/min The PET film (Teijin DuPont, Japan) was exposed to UV treatment on the non-hard coating side. Then, the TCC emulsions described in Table 2 below were applied to the films on the non-hard coat side with a wet thickness of 40 μm. No primer or preliminary coating material is applied prior to depositing the TCC emulsion. After the coating step, the film was heated at 150 ° C for 3 minutes and then the film was washed with acetone for 30 seconds to 40 seconds and then allowed to dry in air. The resulting TCC coating has a sheet resistance of 200 ohm/sq to 300 ohm/sq, a transmittance of more than 85%, and a haze of about 4% and is suitable for touch screen applications. The adhesion of the TCC to the substrate was judged by repeated measurement of the sheet resistance after applying and removing the tape (Permacel P-99) to the surface of the pattern. Figure 2 shows the TCC pattern obtained on the film which was UV treated at a conveyor speed of 1.5 m/min. 140855.doc -18- 201005763 Table 2: TCC Emulsion, Component Ingredient Weight (%) Cymel 1168 0.1 K flex 307 xm 0.1 Nacure 2501 0.1 Byk410 0.2 Span 60 0.2 Aniline 0.1 Byk 106 0.1 2 Aminobutanol 0.2 Cyclohexane 8.0 cyclohexanone 4.1 toluene 53.9 P204 silver nanopowder 1.0 0.04% sodium dodecyl sulfate (SDS) in water 31.9 total 100 compared to the HF1C21 membrane described above, another commercial hardcoat PET film (Toyobo A4300 A higher UV exposure is required to result in a good TCC pattern upon subsequent coating of the films by TCC emulsion on the non-hardcoat side. Good results were obtained by passing the UV chamber twice at a speed of 1 · 1 m/min (when the TCC emulsion was subsequently applied at a wet thickness of 40 μm). The film was post-treated by the same conditions as given above for the HF1C21 film. PET film Skyrol SH34 PET film (SKC) and Lumirror U46 PET film (Toray) at both conveyor rates of 1 m/min and 2 m/min on the same equipment as above (both have no hard coat surface) Perform UV treatment. When subsequently coated by the TCC emulsion as described in Table 3, a mesh pattern as in Fig. 3 was obtained. 140855.doc •19· 201005763 Table 3: TCC Emulsion, Component Ingredient Weight (%) Byk410 0.2 Span 60 0.2 Aniline 0.2 Byk 106 0.4 2 Aminobutanol 0.1 5% of phenylbenzene succinate (AOT) 0.1 Cyclohexanone 4.1 Cyclohexane---- 28.1 Cymel 303 0.2 K flex 307xm 0.1 Nacure 2501 0.2 -- 30.1 Oleic acid 0.1 0.08% of the benzene in the benzoyl group Bykl06 0.2 P 204 1.2 in the water 1).04 % sodium dodecyl sulfate (SDS) 34.5 Total 100 Example 3 For touch screen applications, a 2-step, 2-pass method with uv polymerizable adhesive pretreatment was developed for HF1C21 optical PET film (Teijin Dupont) . An adhesive formulation comprising 0.3 g of a reactive surfactant having a double bond (Maxemul 5011), 4.0 g of LUV-PET-004 (Today, s Suntech Co., Ltd.), and 45.7 g of ethanol was prepared. LUV-PET-004 is a commercially available UV-cured hard coat resin for PET. Its chemistry is exclusively for suppliers, but it includes acrylic acid polymers, monomers and photoinitiators. This adhesive composition was applied to the HF1C21 film at a wet thickness of 12 μm, and then dried at room temperature for 1 minute. The adhesive coating was then heat treated at 150 ° C for 1 minute and then exposed to an LC 6B conveyor at 2 m/min to 140855.doc • 20· 201005763 Light shot 'S^LC6B conveyor off the sampling surface A 120/W/cm xenon bulb is available at a distance of 53.3 mm. After drying and uV polymerization, the dried thickness was about 〇·5 μm. Transmittance and flexural properties were not adversely affected relative to the untreated film. The double bond surfactant is believed to be capable of polymerizing or bonding to the curable acrylic hardcoat component of the LUV_pET_ 004 material to the group of wounds. The resulting applied adhesive layer was uniform (as judged by visual and microscopic inspection) and was well fixed to the surface of the substrate. The TCC emulsion as described above in Table 1 gave a good pattern with a transmittance of greater than 80% when applied to the binder pretreatment layer. After being applied to the substrate, the adhesive layer is stable with respect to time in tests up to 18 days. Furthermore, when the substrate is coated by the adhesive composition and then the substrate is held in the film stack under a pressure of 20 kg weight The TCC coating applied to the substrate in the manner described above, at 18 days, gave acceptable sheet resistance and greater than 8% transmittance. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photomicrograph of a transparent conductive coating formed from an emulsion containing a UV-activated component; Figure 2 is a transparent conductive coating formed on a substrate that has been UV-treated prior to coating a TCC emulsion. A photomicrograph of the layer; and Figure 3 is a photomicrograph of a transparent conductive coating formed on a substrate that has also been UV treated prior to application of the TCC emulsion. 140855.doc -21-