TW201630718A - Electrically-conductive articles with protective polymeric coatings - Google Patents

Abstract

An article comprises a transparent substrate having a first supporting side and an opposing second supporting side. An electrically-conductive pattern is disposed on at least the first supporting side. A dry outermost polymeric coating disposed over at least part but not all of the electrically-conductive pattern, the dry outermost polymeric coating having a dry thickness of less than 5 [mu]m, an integrated transmittance of at least 80%, and comprising a non-crosslinked thermoplastic polymer having a glass transition temperature (Tg) that is equal to or greater than 65 DEG C. Such articles can be prepared and incorporated into various electronic devices.

Description

具有保護性聚合物塗層之導電物件 Conductive article with protective polymer coating

本發明係關於導電物件，其包括一或多種通常包含一或多種導電金屬圖案之導電圖案。乾燥聚合物塗層通常佈置於用於各種保護性及著色特徵之至少一部分導電圖案上。可將該等導電物件納入各種電子器件中以(例如)提供觸控螢幕顯示器。 The present invention is directed to a conductive article that includes one or more conductive patterns that typically comprise one or more conductive metal patterns. The dried polymer coating is typically disposed on at least a portion of the conductive pattern for various protective and colored features. The electrically conductive articles can be incorporated into various electronic devices to, for example, provide a touch screen display.

各種電子器件正快速發展，尤其係用於各種通信、金融及檔案目的之顯示器件。對於諸如觸控螢幕板、電致變色器件、發光二極體、場效應電晶體及液晶顯示器等應用而言，導電膜極為重要且在工業中進行大量工作以改良彼等導電膜之性質且尤其改良金屬柵格或線導電性並在遮罩設計與所得使用者金屬圖案之間提供較大一致性。 Various electronic devices are rapidly evolving, especially for display devices for a variety of communication, financial, and archival purposes. For applications such as touch screen panels, electrochromic devices, light-emitting diodes, field effect transistors, and liquid crystal displays, conductive films are extremely important and work extensively in the industry to improve the properties of their conductive films and especially Improve metal grid or wire conductivity and provide greater consistency between the mask design and the resulting user metal pattern.

各種電子器件中所使用之導電物件(包含電子、光學、感覺及診斷器件(包含但不限於電話、計算器件及其他顯示器件)中之觸控螢幕)已經設計以對人類指尖或機械記錄針之觸控具有反應。通常，觸控螢幕技術納入使用構成顯示器之一部分之電阻性或電容性感測器層。 Conductive objects used in various electronic devices (including touch screens in electronic, optical, sensory, and diagnostic devices (including but not limited to telephones, computing devices, and other display devices) have been designed to be used with human fingertips or mechanical stylus The touch has a reaction. Typically, touch screen technology incorporates a resistive or capacitive sensor layer that forms part of the display.

通常，觸控螢幕技術納入使用構成顯示器之一部分之電阻性或電容性感測器層。需要提供含有改良導電膜元件之觸控螢幕感測器及顯示器。當前，該等電阻性及電容性觸控螢幕顯示器使用氧化銦錫(ITO)塗層來產生用於區分多個接觸點之陣列。在工業中正努力尋找 用於ITO塗層之有用替代者，包含使用各種其他導電金屬組合物。 Typically, touch screen technology incorporates a resistive or capacitive sensor layer that forms part of the display. There is a need to provide touch screen sensors and displays that include improved conductive film elements. Currently, such resistive and capacitive touch screen displays use an indium tin oxide (ITO) coating to create an array for distinguishing multiple contact points. Struggling in the industry A useful alternative for ITO coatings involves the use of various other conductive metal compositions.

如所論述，因顯示器使用者之直接接觸(觸控)程度有所增加或因環境中之水分或水，觸控螢幕通常易於損害。電阻性及電容性觸控感測器可包含佈置於顯示結構上之半透明(或接近透明)電絕緣覆蓋材料以保護觸控螢幕感測器免受環境條件(例如水分)、磨損、氧及任何有害化學劑影響且使其隔離。 As discussed, touch screens are often susceptible to damage due to increased levels of direct contact (touch) by the display user or due to moisture or water in the environment. The resistive and capacitive touch sensors can include a translucent (or nearly transparent) electrically insulating cover material disposed on the display structure to protect the touch screen sensor from environmental conditions (eg, moisture), wear, oxygen, and Any harmful chemicals affect and isolate them.

亦需要在製造及整合操作期間保護感測器之導電部分免受環境損害(例如水分)及環境與物理損害影響。 It is also desirable to protect the conductive portion of the sensor from environmental damage (eg, moisture) and environmental and physical damage during manufacturing and integration operations.

該等電絕緣覆蓋材料包含玻璃或聚酯層作為保護性覆蓋物。該等材料中之每一者具有一定優點及缺點。WO 2013/062630(Petcavich)及WO 2013/063051(Petcavich等人)皆闡述使用含有各種光起始劑及光固化材料之光可固化組合物在觸控感測器(及顯示螢幕)上形成交聯聚合物保護性層。 The electrically insulating cover material comprises a layer of glass or polyester as a protective covering. Each of these materials has certain advantages and disadvantages. WO 2013/062630 (Petcavich) and WO 2013/063051 (Petcavich et al.) all disclose the use of photocurable compositions containing various photoinitiators and photocurable materials to form intersections on touch sensors (and display screens). A polymeric protective layer.

美國專利7,569,250(Nelson)闡述將保護性塗層施加至在一個表面上具有導電跡線之撓曲電路上且藉由自包含保護性塗層之輥以逐圖案方式將保護性塗層以實質上液態施加至一個表面上之製程。撓曲電路之多個部分保持暴露(未塗覆)用於連結至電子器件(例如印刷頭總成)。可將保護性塗層施加至撓曲電路之表面上且然後進一步(例如)藉由交聯或熱固化進行處理。 U.S. Patent No. 7,569,250 (Nelson) teaches the application of a protective coating to a flex circuit having conductive traces on one surface and the protective coating in a pattern-by-pattern manner by means of a roll comprising a protective coating. A process in which a liquid is applied to a surface. Portions of the flex circuit remain exposed (uncoated) for attachment to an electronic device (eg, a printhead assembly). A protective coating can be applied to the surface of the flex circuit and then further processed, for example, by crosslinking or thermal curing.

儘管該等材料可在觸控感測器中提供保護性表面，但期望避免由所需其他處理程序所致之可交聯材料以及與光起始劑或其他可在最終保護性表面中保持化學反應性且可以殘餘物形式保留於保護性塗層中時引起黃化之交聯劑有關之潛在問題。 While such materials can provide a protective surface in a touch sensor, it is desirable to avoid crosslinkable materials resulting from other processing procedures as desired, as well as to maintain chemistry with the photoinitiator or other in the final protective surface. A potential problem associated with crosslinkers that cause yellowing when reactive and can remain in the protective coating.

另外，用於製備保護性塗層之光固化操作中所使用之殘餘光起始劑可引起黏著及收縮問題，此至少一部分地係由於其低分子量、高流動性及(同樣)高初始濃度，從而在光固化之後之殘餘濃度可高達最 終保護性覆層重量之15%。在使用印刷方法(例如柔版印刷術)以高固化及印刷速度施加至導電圖案之光可固化組合物中，該等問題可尤其明顯。 In addition, the residual photoinitiator used in the photocuring operation used to prepare the protective coating can cause adhesion and shrinkage problems, at least in part due to its low molecular weight, high flow, and (same) high initial concentration. Thus the residual concentration after photocuring can be as high as the most 15% of the final protective coating weight. These problems are particularly noticeable in photocurable compositions that are applied to the conductive pattern at high cure and printing speeds using printing methods such as flexography.

因此，需要改良導電圖案之保護(尤其在存在高濃度之光固化光起始劑時)，從而將黃化及其他問題最小化。 Therefore, there is a need to improve the protection of conductive patterns (especially in the presence of high concentrations of photocuring photoinitiators) to minimize yellowing and other problems.

本發明提供一種物件，其包括：透明基板，其具有第一支撐側及相對第二支撐側；佈置於至少第一支撐側上之導電圖案，及乾燥最外聚合物塗層，其佈置於至少一部分但非全部該導電圖案上，該乾燥最外聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The present invention provides an article comprising: a transparent substrate having a first support side and an opposite second support side; a conductive pattern disposed on at least the first support side, and a dry outermost polymer coating disposed at least The dry outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a non-crosslinked thermoplastic comprising a glass transition temperature (T _g ) equal to or greater than 65 ° C on a portion but not all of the conductive pattern. polymer.

在一些實施例中，本發明物件進一步包括：佈置於透明基板之相對第二支撐側上之導電圖案，及乾燥最外聚合物層，其佈置於透明基板中相對第二支撐側上之至少一部分但非全部該導電圖案上，此乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 In some embodiments, the article of the present invention further comprises: a conductive pattern disposed on the opposite second support side of the transparent substrate, and a dried outermost polymer layer disposed on at least a portion of the transparent substrate opposite the second support side But not all of the conductive patterns, the dry polymer coating has a dry thickness of less than 5 [mu]m, an integrated transmission of at least 80%, and a non-crosslinked thermoplastic polymer having a glass transition temperature ( _Tg ) equal to or greater than 65 °C.

舉例而言，作為導電物件之物件可具有係連續透明聚合物網片之透明基板，且該物件可包括佈置於連續透明聚合物網片中第一支撐側之至少第一部分及相對第二支撐側之至少第一部分上之相同或不同導電圖案。 For example, an article as a conductive article may have a transparent substrate that is a continuous transparent polymer mesh, and the article may include at least a first portion and a second support side disposed on a first support side of the continuous transparent polymer mesh. The same or different conductive patterns on at least the first portion.

此外，在本發明之一些其他實施例中，連續透明聚合物網片包括：位於第一支撐側上之多個部分及位於相對第二支撐側上之多個 部分；分別佈置於透明基板中第一支撐側及相對第二支撐側之多個部分上之相同或不同導電圖案；及乾燥最外聚合物塗層，其佈置於至少一部分但非全部每一導電圖案上。 Moreover, in some other embodiments of the invention, the continuous transparent polymer web comprises: a plurality of portions on the first support side and a plurality of portions on the opposite second support side a portion; the same or different conductive patterns respectively disposed on the first support side and the second support side of the transparent substrate; and a dry outermost polymer coating disposed at least a portion but not all of the conductive On the pattern.

本發明提供諸多優點。因乾燥最外聚合物塗層未交聯(或可交聯)，故乾燥最外聚合物塗層無需固化或後處理，由此減小了印刷裝置及製程之複雜性。另外，與光起始劑及其他交聯劑有關之問題(例如來自殘餘反應物之黃化)及其他與後固化化學反應有關之問題得以避免。另外，來自收縮及黏著之潛在問題亦得以避免，此乃因無需低分子量材料(例如光起始劑)。最後，乾燥最外聚合物層高度透明且可適當地用於覆蓋全部或僅一部分導電圖案，從而可在期望時達成適當電連結。 The present invention provides a number of advantages. Since the outermost polymer coating is not crosslinked (or crosslinkable), the outermost polymer coating does not require curing or post treatment, thereby reducing the complexity of the printing apparatus and process. In addition, problems associated with photoinitiators and other crosslinkers (e.g., yellowing from residual reactants) and other problems associated with post-cure chemical reactions are avoided. In addition, potential problems from shrinkage and adhesion are also avoided because no low molecular weight materials (such as photoinitiators) are required. Finally, the dried outermost polymer layer is highly transparent and can be suitably used to cover all or only a portion of the conductive pattern so that a suitable electrical bond can be achieved as desired.

定義definition

除非另外指示，否則如本文定義導電圖案及乾燥最外聚合物塗層之各種組份所用，單數形式「一(a、an)」及「該(the)」意欲包含一或多種組份(亦即包含複數個指示物)。 The singular forms "a", "an" and "the" are intended to include one or more components, as used herein, unless otherwise indicated. That is, it contains a plurality of indicators).

如本文中所使用，術語「光固化」意指使功能寡聚物及單體或甚至聚合物因應於該等材料之輻照(例如使用適宜波長之紫外(UV)、可見或紅外輻射之輻照)聚合成交聯聚合物網絡。 As used herein, the term "photocuring" means the irradiation of functional oligomers and monomers or even polymers in response to such materials (eg, irradiation with ultraviolet (UV), visible or infrared radiation of a suitable wavelength). ) Polymerization of a crosslinked polymer network.

術語「光固化」用於定義在適當環境中使用適宜輻射輻照(例如使用諸如紫外(UV)、可見或紅外輻射等輻射輻照)時發生聚合或交聯之材料(或組份)。 The term "photocuring" is used to define a material (or component) that polymerizes or crosslinks when suitable radiation exposure is used in a suitable environment (eg, using radiation exposure such as ultraviolet (UV), visible or infrared radiation).

「熱塑性聚合物」係指在個別聚合物大分子之間並無交聯位點且在高於具體溫度下變成液體、易曲折或可模製且然後在冷卻後返回固態之聚合物。在多種情況下，熱塑性聚合物亦可溶於適當有機溶劑介質中。 "Thermoplastic polymer" refers to a polymer that has no crosslinking sites between individual polymer macromolecules and that becomes liquid at a higher temperature, is tortuous or moldable, and then returns to a solid state upon cooling. In many cases, the thermoplastic polymer can also be dissolved in a suitable organic solvent medium.

本文所闡述非交聯熱塑性聚合物中之重複單元通常衍生自縮合或自由基聚合製程中所使用之可聚合單元，該等可聚合單元具有期望性質且有助於期望聚合物T_g。 The repeating units in the non-crosslinked thermoplastic polymers described herein are typically derived from polymerizable units used in a condensation or free radical polymerization process, which have desirable properties and contribute to the desired polymer _Tg .

本文所闡述層(例如乾燥最外聚合物塗層)之平均乾燥厚度可(例如)使用電子顯微術、光學顯微術或輪廓術自在乾燥層中所進行至少兩個單獨量測之平均值測得。 The average dry thickness of the layers described herein (eg, the dried outermost polymer coating) can be, for example, averaged using at least two separate measurements in the dried layer using electron microscopy, light microscopy, or profilometry. Measured.

類似地，本文所闡述線、柵格線或其他圖案特徵之平均乾燥厚度或寬度可為(例如)使用電子顯微術、光學顯微術或輪廓術進行之至少兩次單獨量測之平均值。 Similarly, the average dry thickness or width of a line, grid line or other pattern feature as set forth herein can be, for example, an average of at least two separate measurements using electron microscopy, optical microscopy, or profilometry. .

「光化輻射」用於係指能夠根據本發明產生光固化或光聚合作用且波長為至少200nm且至多並包含1400nm及通常至少200nm且至多並包含750nm或甚至至少300nm且至多並包含700nm之任一電磁輻射。術語「曝光輻射」亦係指該光化輻射。 "Activizing radiation" is used to mean any photocurable or photopolymerizable effect according to the invention and having a wavelength of at least 200 nm and up to and including 1400 nm and usually at least 200 nm and up to and including 750 nm or even at least 300 nm and up to 700 nm An electromagnetic radiation. The term "exposure radiation" also refers to the actinic radiation.

術語「UV輻射」在本文中用於係指具有至少200nm且至多並包含400nm之波長(λ_max)之電磁輻射。 The term "UV radiation" as used herein refers to electromagnetic radiation having a wavelength of at least 200 nm and up to and including 400 nm (λ _max ).

使用尺寸排除層析(SEC)測定重量平均分子量(M_w)。本文所報告之值係以聚(甲基丙烯酸甲酯)等效重量形式報告。 The weight average molecular weight (M _w ) was determined using size exclusion chromatography (SEC). The values reported herein are reported as poly(methyl methacrylate) equivalent weight.

可使用差示掃描量熱法(DSC)測定玻璃轉變溫度(T_g)且本文所報告之值係指銦標準。 The glass transition temperature ( _Tg ) can be determined using differential scanning calorimetry (DSC) and the values reported herein refer to the indium standard.

本文所使用提及基板、聚合物層(包含乾燥最外聚合物塗層)之術語「透明」及「透明性」係指積分透射率為至少80%及更可能至少90%之材料及結構。積分透射率係在電磁光譜(例如410nm至700nm) 之可見區中使用分光光度計及已知技術量測。 As used herein, the terms "transparent" and "transparent" as used in reference to a substrate, a polymeric layer (including a dry outermost polymeric coating), refer to materials and structures having an integrated transmission of at least 80% and more preferably at least 90%. The integrated transmittance is in the electromagnetic spectrum (eg 410nm to 700nm) A spectrophotometer and known techniques are used in the visible region.

如本文中所使用，術語「導電圖案」係指導電材料之具有攜載電流之功能之預定或隨機配置圖案。在大部分實施例中，該等導電圖案係導電金屬圖案，但可使用其他導電材料，舉例而言，可在其他實施例中使用導電聚合物、碳奈米管、石墨烯及其他導電碳結構。導電圖案可由多個區構成，一些區經設計位於納入導電物件之器件(例如觸控螢幕感測器)之「觸控」區內。導電圖案之其他區可位於「觸控」區外側且配置於邊界或電連結區內。該等區可由導電匯流排線、探針墊、電極及連結器組成。如針對本發明所定義之連結器或連結器墊係導電圖案之導電區，其連結至外部電子連結、檢測器、電路或其他外部組件。舉例而言，每一導電圖案可包括可佈置於「觸控」區中之「導電柵格」或「導電金屬柵格」。導電圖案亦可包括位於「觸控」區外側且為連結器墊之一部分之「導電連結器」或「導電金屬連結器」。其他區可包括提供器件組份內之電流路徑之其他導電線及互連。 As used herein, the term "conductive pattern" refers to a predetermined or randomly arranged pattern of electrical materials that have the function of carrying current. In most embodiments, the conductive patterns are conductive metal patterns, but other conductive materials may be used. For example, conductive polymers, carbon nanotubes, graphene, and other conductive carbon structures may be used in other embodiments. . The conductive pattern may be formed by a plurality of regions that are designed to be located within the "touch" region of a device (eg, a touch screen sensor) that is incorporated into the conductive article. Other regions of the conductive pattern may be located outside of the "touch" region and disposed within the boundary or electrical connection region. The zones may be comprised of a conductive bus bar, a probe pad, an electrode, and a connector. A connector or connector pad as defined in the present invention is a conductive region of a conductive pattern that is bonded to an external electronic link, detector, circuit or other external component. For example, each conductive pattern can include a "conductive grid" or a "conductive metal grid" that can be disposed in a "touch" region. The conductive pattern may also include a "conductive connector" or a "conductive metal connector" located outside the "touch" region and being part of the connector pad. Other zones may include other conductive lines and interconnects that provide current paths within the device components.

用途use

本發明物件可用於各種技術及器件中，包含但不限於觸控螢幕感測器、顯示器、積體電路組件、微晶片、薄膜電晶體組件及其他可用於諸多消費者、工業及商業產品中之顯示器或功能器件。可用於該等顯示器件中之影像器件可包含陰極射線管(CRS)、投影機、平板液晶顯示器(LCD)、LED系統、OLED系統、電漿系統、電致發光顯示器(ECD)及場發射顯示器(FED)。舉例而言，本發明可用於製備可納入具有觸控-敏感特徵之電子器件中之電容式觸控感測器以提供計算器件、電腦顯示器、可攜式媒體播放器(包含電子閱讀器、行動電話及其他可攜式通信器件)。 The inventive article can be used in various technologies and devices, including but not limited to touch screen sensors, displays, integrated circuit components, microchips, thin film transistor components, and others, which can be used in many consumer, industrial, and commercial products. Display or functional device. Imaging devices that can be used in such display devices can include cathode ray tubes (CRS), projectors, flat panel liquid crystal displays (LCDs), LED systems, OLED systems, plasma systems, electroluminescent displays (ECD), and field emission displays. (FED). For example, the present invention can be used to prepare a capacitive touch sensor that can be incorporated into an electronic device having touch-sensitive features to provide a computing device, a computer display, a portable media player (including an e-reader, an action) Telephones and other portable communication devices).

使用本發明以高容量捲對捲製造製程製作撓性及光學順應性觸 控感測器之系統及方法係可能的，其中可在單遍次中產生微導電特徵。可使用多個印刷部件(例如多個柔版印刷板)來自彼等多個印刷部件中所提供之預定設計或圖案形成多個高解析度導電圖案(或影像)。可如下文更詳細闡述將多個圖案印刷於透明基板之一側或兩側上。舉例而言，可將一個預定圖案形成於透明基板之一側上且可將不同預定圖案形成於透明基板之相對側上。可將本文所闡述之乾燥最外聚合物塗層納入或佈置於至少一部分但非全部之多個導電圖案中之每一者中。 Using the present invention to make flexible and optically compliant touches in a high volume roll-to-roll manufacturing process It is possible to control the system and method of the sensor in which micro-conducting features can be produced in a single pass. A plurality of high-resolution conductive patterns (or images) may be formed from predetermined designs or patterns provided in a plurality of printed components using a plurality of printed components (eg, a plurality of flexographic printing plates). Multiple patterns can be printed on one or both sides of the transparent substrate as explained in more detail below. For example, one predetermined pattern may be formed on one side of the transparent substrate and different predetermined patterns may be formed on opposite sides of the transparent substrate. The dry outermost polymer coatings described herein can be incorporated or disposed in each of at least a portion, but not all, of the plurality of conductive patterns.

最外聚合物塗層Outer polymer coating

本發明中所使用之最外聚合物塗層係源於混合一或多種非交聯熱塑性聚合物(若並不另外指示，則在下文中係「聚合物」)，每一聚合物或聚合物混合物具有等於或大於65℃之玻璃轉變溫度(T_g)。 The outermost polymeric coating used in the present invention is derived from the mixing of one or more non-crosslinked thermoplastic polymers (hereinafter "polymers" unless otherwise indicated), each polymer or polymer mixture It has a glass transition temperature (T _g ) equal to or greater than 65 ° C.

可使用有用非交聯熱塑性聚合物來提供如本文所定義具有上述積分透射率之透明膜。 A useful non-crosslinked thermoplastic polymer can be used to provide a transparent film having the above-described integral transmittance as defined herein.

該等非交聯熱塑性聚合物可無縮合聚合物，包含但不限於聚酯、聚醯胺、聚醯亞胺、聚碳酸酯、聚胺基甲酸酯、聚脲及聚碸。更可能的是，非交聯熱塑性聚合物係衍生自一或多種乙烯系不飽和可聚合單體之加成聚合物，該等聚合物包含但不限於聚乙烯縮醛、聚丙烯酸、聚丙烯醯胺、聚苯乙烯、聚烯烴、聚乙烯基鹵化物、聚亞乙烯基鹵化物、聚碸及聚乙烯基醚。亦可使用天然或合成纖維素。 The non-crosslinked thermoplastic polymers may be free of condensation polymers including, but not limited to, polyesters, polyamines, polyimines, polycarbonates, polyurethanes, polyureas, and polyfluorenes. More likely, the non-crosslinked thermoplastic polymer is derived from an addition polymer of one or more ethylenically unsaturated polymerizable monomers, including but not limited to polyvinyl acetal, polyacrylic acid, polypropylene hydrazine Amines, polystyrenes, polyolefins, polyvinyl halides, polyvinylidene halides, polyfluorenes and polyvinyl ethers. Natural or synthetic cellulose can also be used.

有用非交聯熱塑性聚合物可為線性、具支鏈、梳形或任一其他已知聚合物形態。亦有用者係含有各種形態之多個單體之嵌段、接枝或錐形共聚物或聚合物，只要達成本文所闡述之其他性質。 Useful non-crosslinked thermoplastic polymers can be linear, branched, combed, or any other known polymeric form. Also useful are block, graft or tapered copolymers or polymers containing a plurality of monomers in various forms as long as other properties as set forth herein are achieved.

尤其有用之非交聯熱塑性聚合物為「非芳香族」，此意味著在聚合物內並不特意納入碳環芳香族或雜環芳香族部分(或基團)。 Particularly useful non-crosslinked thermoplastic polymers are "non-aromatic", which means that no carbocyclic aromatic or heterocyclic aromatic moieties (or groups) are specifically incorporated into the polymer.

此類有用非交聯熱塑性聚合物包含衍生自至少一或多種丙烯酸 酯或甲基丙烯酸酯乙烯系不飽和可聚合單體之丙烯酸聚合物。使用該等單體在(共)聚合物中提供至少5mol%或至少10mol%且至多並包含100mol%之「丙烯酸」重複單元(基於總重複單元)。若「丙烯酸」重複單元佔小於100mol%，則剩餘重複單元可衍生自一或多種熟習此項技術者所熟知之乙烯系不飽和可聚合單體，只要該等重複單元並不包括能夠發生變色反應之碳環芳香族或雜環芳香族部分或其他官能基。因此，有用丙烯酸聚合物可為均聚物或包括兩個或更多個衍生自兩種或更多種不同乙烯系不飽和可聚合單體之不同重複單元之共聚物。 Such useful non-crosslinked thermoplastic polymers comprise derived from at least one or more acrylics An acrylic polymer of an ester or methacrylate ethylenically unsaturated polymerizable monomer. The monomers are used to provide at least 5 mol% or at least 10 mol% and up to and including 100 mol% of "acrylic" repeating units (based on total repeat units) in the (co)polymer. If the "acrylic" repeating unit is less than 100 mol%, the remaining repeating unit may be derived from one or more ethylenically unsaturated polymerizable monomers well known to those skilled in the art, as long as the repeating units do not include a color change reaction. A carbocyclic aromatic or heterocyclic aromatic moiety or other functional group. Thus, useful acrylic polymers can be homopolymers or copolymers comprising two or more different repeating units derived from two or more different ethylenically unsaturated polymerizable monomers.

因此，丙烯酸酯或甲基丙烯酸酯乙烯系不飽和可聚合單體可包括可未經取代或經一或多個烷氧基、羥基烷氧基、烷氧基烷氧基或鹵代烷氧基取代之適宜酯烷基。舉例而言，該等有用乙烯系不飽和可聚合單體包含羥基烷基甲基丙烯酸酯(例如甲基丙烯酸羥甲基酯)、甲基丙烯酸甲酯、甲基丙烯酸乙酯、丙烯酸甲酯、丙烯酸乙酯、丙烯酸正丁基酯、甲基丙烯酸正丁基酯、甲基丙烯酸異丁基酯、丙烯酸第三丁基酯、甲基丙烯酸第三丁基酯、甲基丙烯酸正己基酯、丙烯酸正十二烷基酯、甲基丙烯酸2-乙基己基酯、丙烯酸2-乙基己基酯、甲基丙烯酸環己基酯、丙烯酸環己基酯、甲基丙烯酸縮水甘油基酯、丙烯酸縮水甘油基酯、丙烯酸氯甲基酯或羥基烷基丙烯酸酯(例如丙烯酸羥乙基酯或丙烯酸羥丙基酯)。 Thus, the acrylate or methacrylate ethylenically unsaturated polymerizable monomer can include unsubstituted or substituted with one or more alkoxy, hydroxyalkoxy, alkoxyalkoxy or haloalkoxy groups. Suitable ester alkyl groups. For example, the useful ethylenically unsaturated polymerizable monomers comprise a hydroxyalkyl methacrylate (eg, hydroxymethyl methacrylate), methyl methacrylate, ethyl methacrylate, methyl acrylate, Ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl acrylate, t-butyl methacrylate, n-hexyl methacrylate, acrylic acid N-dodecyl ester, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, glycidyl methacrylate, glycidyl acrylate , chloromethyl acrylate or hydroxyalkyl acrylate (such as hydroxyethyl acrylate or hydroxypropyl acrylate).

在許多實施例中，非交聯熱塑性聚合物係共聚物(包含三元聚合物)，其各自包括衍生自(甲基)丙烯酸甲酯(意指丙烯酸甲酯或甲基丙烯酸甲酯)之重複單元及衍生自(甲基)丙烯酸烷基酯(其中烷基具有至少1個碳原子且至多並包含18個碳原子)之重複單元，其中衍生自(甲基)丙烯酸烷基酯之重複單元佔總共聚物重複單元之至少5mol%且至多並包含25mol%，且衍生自甲基丙烯酸甲酯之重複單元構成其餘共 聚物。有用乙烯系不飽和可聚合單體闡述於上文中且其他者為熟習此項技術者易於明瞭。 In many embodiments, non-crosslinked thermoplastic polymer-based copolymers (including terpolymers) each comprising a repeat derived from methyl (meth)acrylate (meaning methyl acrylate or methyl methacrylate) a unit and a repeating unit derived from an alkyl (meth) acrylate (wherein the alkyl group has at least 1 carbon atom and up to 18 carbon atoms), wherein the repeating unit derived from the alkyl (meth) acrylate comprises At least 5 mol% and at most 25 mol% of the total copolymer repeating unit, and repeating units derived from methyl methacrylate constitute the remaining Polymer. The use of ethylenically unsaturated polymerizable monomers is set forth above and others will be readily apparent to those skilled in the art.

其他可用於提供共聚物中之重複單元之有用乙烯系不飽和可聚合單體包含但不限於丙烯醯胺、甲基丙烯醯胺、丙烯酸酸、甲基丙烯酸、丙烯腈、乙酸乙烯酯、氯乙烯及二氯亞乙烯或任一能夠與(甲基)丙烯酸酯共聚合之其他乙烯系不飽和單-芳香族可聚合單體。 Other useful ethylenically unsaturated polymerizable monomers that can be used to provide repeating units in the copolymer include, but are not limited to, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, vinyl chloride And dichloroethylene or any other ethylenically unsaturated mono-aromatic polymerizable monomer copolymerizable with the (meth) acrylate.

可製備具有一或多個不同類型衍生自一或多種上述乙烯系不飽和可聚合單體之重複單元之非交聯熱塑性聚合物，且該等重複單元可以任一期望順序(例如隨機、交替、嵌段或熟習聚合物化學技術者明瞭之其他配置)配置於聚合物內。 Non-crosslinked thermoplastic polymers having one or more different types of repeating units derived from one or more of the above ethylenically unsaturated polymerizable monomers can be prepared, and the repeating units can be in any desired order (eg, random, alternating, The block or other configuration known to those skilled in the art of polymer chemistry is disposed within the polymer.

本文針對所闡述聚合物定義之各種重複單元之mol%量意欲係指存在於聚合物中之實際莫耳量。熟習此項技術者應理解，實際mol%值可不同於源自聚合程序中所使用乙烯系不飽和可聚合單體之量之彼等理論可能值。然而，在大部分達成所有乙烯系不飽和可聚合單體之高聚合物產率及最佳反應之聚合條件下，每一乙烯系不飽和可聚合單體之實際mol%通常在理論量±15mol%內。 The amount of mol% of various repeating units defined herein for the polymers described is intended to mean the actual amount of morth present in the polymer. Those skilled in the art will appreciate that the actual mol% value may differ from the theoretically possible values derived from the amount of ethylenically unsaturated polymerizable monomer used in the polymerization procedure. However, the actual mol% of each ethylenically unsaturated polymerizable monomer is typically at a theoretical amount of ±15 mol% under most polymerization conditions which achieve high polymer yields and optimum reaction of all ethylenically unsaturated polymerizable monomers. Inside.

一些代表性非交聯熱塑性聚合物包含但不限於下列聚合物，其中莫耳比率係基於聚合製程中所使用乙烯系不飽和可聚合單體之實際莫耳比之理論(標稱)量。若聚合反應並未實施完全，則重複單元之實際莫耳量可不同於乙烯系不飽和可聚合單體之理論(標稱)量。 Some representative non-crosslinked thermoplastic polymers include, but are not limited to, the following polymers, wherein the molar ratio is based on the theoretical (nominal) amount of the actual molar ratio of the ethylenically unsaturated polymerizable monomer used in the polymerization process. If the polymerization is not carried out completely, the actual molar amount of the repeating unit may be different from the theoretical (nominal) amount of the ethylenically unsaturated polymerizable monomer.

聚(甲基丙烯酸甲酯-共-甲基丙烯酸正丁基酯)90：10莫耳比；聚(甲基丙烯酸甲酯-共-甲基丙烯酸正丁基酯)75：25莫耳比；聚(甲基丙烯酸甲酯-共-甲基丙烯酸正丁基酯-共-甲基丙烯酸)85：15：5莫耳比；聚(甲基丙烯酸甲酯-共-甲基丙烯酸己酯)90：10莫耳比；聚(甲基丙烯酸甲酯-共-甲基丙烯酸辛酯)90：10莫耳比； 聚(甲基丙烯酸甲酯-共-甲基丙烯酸月桂基酯)90：10莫耳比；聚(甲基丙烯酸乙酯-共-甲基丙烯酸正丁基酯-共-甲基丙烯酸)80：15：5莫耳比；及聚(甲基丙烯酸乙酯-共-甲基丙烯酸)90：10莫耳比。 Poly(methyl methacrylate-co-n-butyl methacrylate) 90:10 molar ratio; poly(methyl methacrylate-co-n-butyl methacrylate) 75:25 molar ratio; Poly(methyl methacrylate-co-n-butyl methacrylate-co-methacrylic acid) 85:15:5 molar ratio; poly(methyl methacrylate-co-hexyl methacrylate) 90 : 10 molar ratio; poly(methyl methacrylate-co-octyl methacrylate) 90:10 molar ratio; Poly(methyl methacrylate-co-methyl methacrylate) 90:10 molar ratio; poly(ethyl methacrylate-co-n-butyl methacrylate-co-methacrylic acid) 80: 15:5 molar ratio; and poly(ethyl methacrylate-co-methacrylic acid) 90:10 molar ratio.

有用非交聯熱塑性共聚物及三元聚合物市面有售。舉例而言，聚(甲基丙烯酸甲酯-共-甲基丙烯酸正丁基酯)係以ELVACITE^® 4028形式獲得；聚(甲基丙烯酸甲酯-共-甲基丙烯酸正丁基酯-共-甲基丙烯酸)係以ELVACITE^® 2614形式獲得；且聚(甲基丙烯酸甲酯-共-甲基丙烯酸月桂基酯)係以ELVACITE^® 2552形式自Lucite International獲得。 Useful non-crosslinked thermoplastic copolymers and terpolymers are commercially available. For example, poly (methyl methacrylate - co - n-butyl methacrylate) -based obtained in the form of ELVACITE ^® 4028; Poly (methyl methacrylate - co - methacrylate, n-butyl acrylate - co - Methacrylic acid) was obtained in the form of ELVACITE ^® 2614; and poly(methyl methacrylate-co-methyl methacrylate) was obtained from Lucite International in the form of ELVACITE ^® 2552.

具有乾燥最外聚合物塗層之物件之製備Preparation of articles with dried outermost polymer coating

一般而言，藉由首先提供具有第一支撐側及相對第二支撐側(與邊緣相對之相對平面側)之適宜透明基板來製備本發明物件。適宜透明基板可由各種材料構成。 In general, articles of the invention are prepared by first providing a suitable transparent substrate having a first support side and an opposite second support side (opposite planar sides opposite the edges). Suitable transparent substrates can be constructed from a variety of materials.

適宜透明基板包含但不限於玻璃(包含撓性玻璃)、玻璃增強之環氧壓層、三乙酸纖維素、丙烯酸酯、聚碳酸酯、黏著劑塗覆之聚合物透明基板、聚酯膜及透明複合材料。用作透明聚合物基板之適宜透明聚合物包含但不限於聚乙烯及其他聚烯烴、聚酯(例如聚對苯二甲酸乙二酯(PET)、聚萘二甲酸乙二酯(PEN)、聚-對苯二甲酸1,4-環己烷二亞甲基酯、聚(對苯二甲酸伸丁基酯)及其共聚物)、聚丙烯、聚乙酸乙烯酯、聚胺基甲酸酯、聚醯胺、聚醯亞胺、聚碸、聚碳酸酯、聚(甲基丙烯酸甲酯)及熟習此項技術者易於明瞭之其他材料。其他有用透明基板可由纖維素衍生物(例如纖維素酯、三乙酸纖維素、二乙酸纖維素、乙酸丙酸纖維素、乙酸丁酸纖維素、聚丙烯酸酯、聚醚亞醯胺及其混合物)構成。 Suitable transparent substrates include, but are not limited to, glass (including flexible glass), glass reinforced epoxy laminate, cellulose triacetate, acrylate, polycarbonate, adhesive coated polymer transparent substrate, polyester film, and transparent Composite material. Suitable transparent polymers for use as transparent polymer substrates include, but are not limited to, polyethylene and other polyolefins, polyesters (eg, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), poly - 1,4-cyclohexanedimethylene terephthalate, poly(butylene terephthalate) and copolymers thereof, polypropylene, polyvinyl acetate, polyurethane, Polyamides, polyimines, polyfluorenes, polycarbonates, poly(methyl methacrylate), and other materials that are readily apparent to those skilled in the art. Other useful transparent substrates may be cellulose derivatives (eg, cellulose esters, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, polyacrylates, polyether amides, and mixtures thereof) Composition.

在表現為具有一層時，雙軸定向薄片亦可提供有其他可用於改變雙軸定向薄片之光學或其他性質之層。該等層可含有著色劑、抗靜 電或導電材料或滑動劑，只要維持期望積分透射率。 When present as having one layer, the biaxially oriented sheet can also be provided with other layers that can be used to alter the optical or other properties of the biaxially oriented sheet. The layers may contain colorants and antistatic Electrical or electrically conductive material or slip agent as long as the desired integral transmission is maintained.

使用撓性透明基板來製造撓性電子器件或觸控螢幕組件會促進快速捲對捲製造。ESTAR^®聚(對苯二甲酸乙二酯)膜、MELLINEX^®聚(對苯二甲酸乙二酯)膜及三乙酸纖維素膜係用於製造撓性透明基板(包含連續基板網片)之尤其有用材料。 The use of flexible transparent substrates to fabricate flexible electronic devices or touch screen assemblies facilitates rapid roll-to-roll manufacturing. ESTAR ^® poly(ethylene terephthalate) film, MELLINEX ^® poly(ethylene terephthalate) film and cellulose triacetate film are used to make flexible transparent substrates (including continuous substrate mesh). Useful materials.

透明基板可具有至少20μm且至多並包含300μm或通常至少75μm且至多並包含200μm之厚度。若期望，則可以適宜量將抗氧化劑、抗靜電或導電劑、塑化劑及其他有用添加劑納入透明基板中。 The transparent substrate may have a thickness of at least 20 μm and up to and including 300 μm or usually at least 75 μm and up to and including 200 μm. If desired, an antioxidant, an antistatic or conductive agent, a plasticizer, and other useful additives may be incorporated into the transparent substrate in an appropriate amount.

可使用任一期望方式(存在業內已知之若干技術)將導電圖案(例如導電金屬圖案，其可包含導電柵格(例如導電金屬柵格)及導電連結器(例如導電金屬連結器))佈置於透明基板中第一支撐側及相對第二支撐側中之一者或兩者上。 Conductive patterns (eg, conductive metal patterns, which may include conductive grids (eg, conductive metal grids) and conductive connectors (eg, conductive metal connectors)) may be disposed in any desired manner (there are several techniques known in the art) One or both of the first support side and the opposite second support side in the transparent substrate.

一些導電圖案可自一或多種導電聚合物(許多為業內已知)構成。舉例而言，該等導電聚合物可選自經取代或未經取代之含吡咯聚合物[如(例如)在美國專利5,665,498(Savage等人)及5,674,654(Zumbalyadis等人)中所闡述]；經取代或未經取代之含噻吩聚合物[如(例如)在美國專利5,300,575(Joans等人)、5,312,681(Muys等人)、5,354,613(Quinters等人)、5,370,981(Krafft等人)、5,372,924(Quinters等人)、5,391,472(Muys等人)、5,403,467(Jonas等人)、5,443,944(Azoulay)、4,987,042(Jonas等人)及4,731,408(Jasne)中所闡述]；及經取代或未經取代之含苯胺聚合物[如(例如)在美國專利5,716,550(Gardner等人)、5,093,439(Epstein等人)及4,070,189(Kelley等人)中所闡述]。 Some conductive patterns can be constructed from one or more conductive polymers (many known in the art). For example, the conductive polymers may be selected from substituted or unsubstituted pyrrole-containing polymers [as described, for example, in U.S. Patent Nos. 5,665,498 (Savage et al.) and 5,674,654 (Zumbalyadis et al.); Substituted or unsubstituted thiophene-containing polymers [for example, in U.S. Patent Nos. 5,300,575 (Joans et al.), 5,312,681 (Muys et al.), 5,354,613 (Quinters et al.), 5,370,981 (Krafft et al.), 5,372,924 (Quinters et al. Human), 5, 391, 472 (Muys et al), 5, 403, 467 (Jonas et al), 5, 443, 944 (Azoulay), 4, 987, 042 (Jonas et al) and 4, 731, 408 (Jasne); and substituted or unsubstituted aniline-containing polymers [, for example, as described in U.S. Patent Nos. 5,716,550 (Gardner et al.), 5,093,439 (Epstein et al.) and 4,070,189 (Kelley et al.).

一些導電圖案可由一或多種導電碳結構構成，許多為業內已知，包含(例如)導電碳黑、碳奈米管、石墨、石墨烯或其組合。 Some of the conductive patterns may be comprised of one or more conductive carbon structures, many of which are known in the art, including, for example, conductive carbon black, carbon nanotubes, graphite, graphene, or combinations thereof.

在其他實施例中，導電圖案經設計以具有金屬特徵。舉例而言，光敏性鹵化銀技術可用於此目的以在透明基板之一或兩個支撐側 上提供導電銀圖案，例如如美國專利申請公開案2011/0289771(Kuriki)及2011/0308846(Ichiki)中所闡述。用於此目的之其他鹵化銀技術亦闡述於共同申請且共同讓與之美國專利臨時申請案第14/468,626號(2014年8月26日由Lushington提出申請)。在該技術中，可將鹵化銀乳液設計於透明基板之一或兩個支撐側上，經由適宜遮罩暴露，且然後可處理藉由此暴露形成之圖案以形成銀金屬圖案且適宜地去除非暴露鹵化銀乳液。可使用具有相應圖案之預定遮罩元件設計各種導電銀圖案以具有期望圖案。 In other embodiments, the conductive pattern is designed to have metallic features. For example, a photosensitive silver halide technique can be used for this purpose on one or both of the support sides of a transparent substrate A conductive silver pattern is provided, for example, as described in U.S. Patent Application Publication No. 2011/0289771 (Kuriki) and 2011/0308846 (Ichiki). Other silver halide technologies for this purpose are also described in co-pending and commonly assigned U.S. Patent Provisional Application Serial No. 14/468,626 (filed on August 26, 2014 by Lushington). In this technique, a silver halide emulsion can be designed on one or both of the support sides of the transparent substrate, exposed through a suitable mask, and then the pattern formed by the exposure can be processed to form a silver metal pattern and suitably removed. Expose the silver halide emulsion. Various conductive silver patterns can be designed using a predetermined masking element having a corresponding pattern to have a desired pattern.

在其他實施例中，可使用可提供用於無電電鍍製程之晶種金屬觸媒之光可固化組合物在透明基板之一或兩個支撐側上形成導電圖案(例如導電金屬圖案)。舉例而言，光可固化組合物可包括酸催化光可固化化學物質、自由基光可固化化學物質或此兩類化學物質，其實例闡述於下文中，但本發明並不限於所闡述光可固化化學物質且可使用任一可進一步包括適於無電金屬電鍍製程之晶種金屬觸媒之已知光可固化組合物來實施。 In other embodiments, a conductive pattern (eg, a conductive metal pattern) can be formed on one or both of the support sides of the transparent substrate using a photocurable composition that provides a seed metal catalyst for the electroless plating process. For example, the photocurable composition may include an acid catalyzed photocurable chemical, a free radical photocurable chemical, or both, examples of which are set forth below, but the invention is not limited to the illustrated light The chemistry is cured and can be carried out using any known photocurable composition that can further include a seed metal catalyst suitable for electroless metal plating processes.

酸催化光可固化化學物質：Acid catalyzed photocurable chemicals:

在一些實施例中，有用光可固化組合物包括一或多種UV可固化組份，其中之至少一者係酸催化光可固化組份。該等光可固化組合物可進一步包括參與生成酸自由基以引起光可固化組份之光固化之光酸生成劑。 In some embodiments, the useful photocurable composition comprises one or more UV curable components, at least one of which is an acid catalyzed photocurable component. The photocurable compositions can further comprise a photoacid generator that participates in the formation of acid free radicals to cause photocuring of the photocurable component.

一些有用酸催化光可固化組份係光可固化環氧材料。陽離子型光可固化環氧材料可為具有至少一個環氧乙烷環之有機化合物，該環氧乙烷環展示於下式中： Some useful acid catalyzed photocurable components are photocurable epoxy materials. The cationic photocurable epoxy material can be an organic compound having at least one oxirane ring, which is shown in the following formula:

其可藉由開環機制聚合(光固化)。該等環氧材料包含單體環氧化合物及聚合物類型之環氧化物且可為脂肪族、環脂族、芳香族或雜環的。該等材料通常每分子具有平均至少一個可聚合環氧基，或通常每分子具有至少約1.5個或甚至至少約2個可聚合環氧基。聚合物環氧材料包含具有末端環氧基之線性聚合物(例如聚氧化烯二醇之二縮水甘油基醚)、具有骨架(主鏈)環氧乙烷單元之聚合物(例如聚丁二烯聚環氧化物)及具有側鏈環氧基之聚合物(例如甲基丙烯酸縮水甘油基酯聚合物或共聚物)。光可固化環氧材料可為單一化合物或其可為每分子含有一個、兩個或更多個環氧基之不同環氧材料之混合物。 It can be polymerized (photocured) by an open loop mechanism. The epoxy materials comprise monomeric epoxy compounds and polymer type epoxides and may be aliphatic, cycloaliphatic, aromatic or heterocyclic. The materials typically have an average of at least one polymerizable epoxy group per molecule, or typically have at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule. The polymer epoxy material comprises a linear polymer having a terminal epoxy group (for example, a diglycidyl ether of a polyoxyalkylene glycol), a polymer having a skeleton (backbone) ethylene oxide unit (for example, polybutadiene). Polyepoxides) and polymers having pendant epoxy groups (for example, glycidyl methacrylate polymers or copolymers). The photocurable epoxy material can be a single compound or it can be a mixture of different epoxy materials containing one, two or more epoxy groups per molecule.

環氧材料可自低分子量單體材料至高分子量聚合物有所變化且其主鏈及取代基(或側鏈)基團之性質可大不相同。舉例而言，主鏈可為任一類型且其上之取代基可為在室溫下實質上不干擾期望之陽離子光固化製程之任一基團。所闡釋之容許取代基包含但不限於鹵素、酯基團、醚、磺酸酯基團、矽氧烷基團、硝基及磷酸酯基團。 Epoxy materials can vary from low molecular weight monomer materials to high molecular weight polymers and the properties of their backbone and substituent (or side chain) groups can vary widely. For example, the backbone can be of any type and the substituents thereon can be any group that does not substantially interfere with the desired cationic photocuring process at room temperature. The permissible substituents illustrated include, but are not limited to, halogens, ester groups, ethers, sulfonate groups, oxoalkyl groups, nitro groups, and phosphate groups.

有用之光環氧材料包含彼等含有環氧環己烷基團者，例如環氧基環己烷甲酸酯(例如3,4-環氧基環己基甲基-3,4-環氧基環己烷甲酸酯、3,4-環氧基-2-甲基環己基甲基-3,4-環氧基-2-甲基環己烷甲酸酯)及己二酸雙(3,4-環氧基-6-甲基環己基甲基)酯。具有此性質之有用環氧材料之更詳細列表提供於美國專利3,117,099(Proops等人)中。 Useful optical epoxy materials include those containing an epoxycyclohexane group, such as an epoxycyclohexanecarboxylate (eg, 3,4-epoxycyclohexylmethyl-3,4-epoxy) Cyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate) and adipic acid bis (3) , 4-epoxy-6-methylcyclohexylmethyl) ester. A more detailed list of useful epoxy materials of this nature is provided in U.S. Patent 3,117,099 (Proops et al.).

其他有用之環氧材料包含縮水甘油基醚單體，其為藉由使多元酚與過量氯醇(例如表氯醇)反應獲得之多元酚之縮水甘油基醚[例如2,2-雙-(2,3-環氧基丙氧基苯酚)-丙烷之二縮水甘油基醚]。此類環氧材料之其他實例闡述於美國專利3,018,262(Schroeder)及Lee及Neville之「Handbook of Epoxy Resins」,McGraw-Hill Book公司，New York(1967)中。 Other useful epoxy materials comprise a glycidyl ether monomer which is a glycidyl ether of a polyhydric phenol obtained by reacting a polyhydric phenol with an excess of a chlorohydrin such as epichlorohydrin [eg 2,2-bis-( 2,3-epoxypropoxyphenol)-propane diglycidyl ether]. Other examples of such epoxy materials are described in U.S. Patent 3,018,262 (Schroeder) and Lee & Neville, "Handbook of Epoxy Resins", McGraw-Hill Book Company, New York (1967).

其他有用之環氧材料係樹脂，例如衍生自與縮水甘油反應之丙 烯酸酯(例如丙烯酸縮水甘油基酯及甲基丙烯酸縮水甘油基酯)與一或多種乙烯系不飽和可聚合單體共聚合之共聚物。其他有用之環氧材料係表氯醇、環氧烷(例如環氧丙烷及氧化苯乙烯)、烯基氧化物(例如丁二烯氧化物)及縮水甘油基酯(例如縮水甘油酸乙酯)。其他有用之環氧材料係具有環氧基官能基或諸如環己基環氧基等基團之聚矽氧，尤其係彼等具有聚矽氧主鏈之環氧材料。該等環氧材料之商業實例包含可自Momentive獲得之UV 9300、UV 9315、UV 9400、UV 9425聚矽氧材料。 Other useful epoxy material resins, such as those derived from the reaction with glycidol A copolymer of an enoate such as glycidyl acrylate and glycidyl methacrylate copolymerized with one or more ethylenically unsaturated polymerizable monomers. Other useful epoxy materials are epichlorohydrin, alkylene oxides (such as propylene oxide and styrene oxide), alkenyl oxides (such as butadiene oxide), and glycidyl esters (such as ethyl glycidate). . Other useful epoxy materials are polyoxyxides having epoxy functional groups or groups such as cyclohexyl epoxy groups, especially those having a polyfluorene backbone. Commercial examples of such epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 polyoxyl materials available from Momentive.

聚合環氧材料可視情況含有在室溫下實質上不干擾光可固化組合物之陽離子光固化之其他官能基。舉例而言，光可聚合環氧材料亦可包含自由基可聚合功能性。 The polymeric epoxy material may optionally contain other functional groups that do not substantially interfere with cationic photocuring of the photocurable composition at room temperature. For example, the photopolymerizable epoxy material may also comprise free radical polymerizable functionality.

光可聚合環氧材料可包括兩種或更多種不同環氧材料之摻合物或混合物。該等摻合物之實例包含兩個或更多個分子量分佈之光可聚合環氧材料，例如一或多種低分子量(低於200)環氧材料與一或多種中等分子量(200至10,000)光可聚合環氧材料或一或多種該等光可聚合環氧材料與一或多種較高分子量(高於10,000)環氧材料之摻合物。另一選擇為或另外，光可聚合環氧材料可包括具有不同化學性質(例如脂肪族及芳香族性質或不同官能基(例如極性及非極性性質))之環氧材料之摻合物。 The photopolymerizable epoxy material can comprise a blend or mixture of two or more different epoxy materials. Examples of such blends include two or more molecular weight distribution photopolymerizable epoxy materials, such as one or more low molecular weight (less than 200) epoxy materials and one or more medium molecular weight (200 to 10,000) light. A blend of a polymerizable epoxy material or one or more of such photopolymerizable epoxy materials with one or more higher molecular weight (greater than 10,000) epoxy materials. Alternatively or additionally, the photopolymerizable epoxy material can include blends of epoxy materials having different chemical properties, such as aliphatic and aromatic properties or different functional groups (eg, polar and non-polar properties).

光可固化組合物中包含一或多種量適於提供期望有效光固化(或光聚合)之光可固化環氧材料。舉例而言，基於光可固化組合物之總重量，一或多種光可聚合環氧材料可以至少5重量%且至多並包含50重量%或通常至少10重量%且至多並包含40重量%之量存在。 The photocurable composition comprises one or more amounts of a photocurable epoxy material suitable for providing a desired effective photocuring (or photopolymerization). For example, one or more photopolymerizable epoxy materials may be at least 5% by weight and up to and including 50% by weight or typically at least 10% by weight and up to and including 40% by weight, based on the total weight of the photocurable composition. presence.

可使用各種化合物作為光酸生成劑來生成適宜酸以參與環氧材料中之光固化。一些該等「光酸生成劑」為酸性且其他為非離子性。熟習此項技術者根據本文所提供之教示可易於明瞭除彼等於下文所闡 述者外之其他有用之光酸生成劑。 Various compounds can be used as photoacid generators to form suitable acids to participate in photocuring in epoxy materials. Some of these "photoacid generators" are acidic and others are nonionic. Those skilled in the art will be readily ascertained by the teachings provided herein. Other useful photoacid generators other than those described.

可在本發明實踐中用作光酸生成劑之鎓鹽酸生成劑包含但不限於重氮之鹽、鏻、碘鎓或鋶鹽，包含聚芳基重氮、鏻、碘鎓及鋶鹽。碘鎓或鋶鹽包含但不限於二芳基碘鎓及三芳基鋶鹽。有用之抗衡陰離子包含但不限於錯合物金屬鹵化物，例如四氟硼酸鹽、六氟銻酸鹽、三氟甲烷磺酸鹽、六氟砷酸鹽、六氟磷酸鹽及芳烴磺酸鹽(arenesulfonate)。鎓鹽亦可為具有多個鎓鹽部分之寡聚物或聚合物化合物以及具有單一鎓鹽部分之分子。 The hydrazine hydrochloride generating agent which can be used as a photoacid generator in the practice of the present invention includes, but is not limited to, a salt of diazonium, hydrazine, iodonium or sulfonium, and contains polyaryldiazo, hydrazine, iodonium and sulfonium salts. Iodine or phosphonium salts include, but are not limited to, diaryl iodonium and triarylsulfonium salts. Useful counter anions include, but are not limited to, complex metal halides such as tetrafluoroborate, hexafluoroantimonate, trifluoromethanesulfonate, hexafluoroarsenate, hexafluorophosphate, and arene sulfonates ( Arenesulfonate). The onium salt may also be an oligomer or polymer compound having a plurality of onium salt moieties and a molecule having a single onium salt moiety.

有用碘鎓鹽可為簡單鹽(例如含有陰離子(例如氯離子、溴離子、碘離子或C₄H₅SO₃ ^-))或金屬錯合物鹽(例如含有SbF₆ ^-、PF₆ ^-、BF₄ ^-、四(全氟苯基)硼酸鹽或SbF₅OH₃₁ AsF₆ ^-)。若期望，可使用該等相同或不同種類碘鎓鹽中之任一者之混合物。鋶鹽之使用係合意的且其應溶於任一惰性有機溶劑(如下文所闡述)中且其亦應儲架穩定，此意味著其在曝光於適宜輻射前與其他組份(尤其電子受體光敏劑及電子供體共起始劑)混合時並不自發地促進聚合。尤其有用之鋶鹽包含但不限於三芳基取代之鹽，例如混合型六氟銻酸三芳基鋶(例如以UVI-6974自Dow化學公司購得)、混合型六氟磷酸三芳基鋶(例如以UVI-6990自Dow化學公司購得)及六氟磷酸芳基鋶(例如自Sartomer公司購得)。 Useful iodonium salts can be simple salts (eg containing anions such as chloride, bromide, iodide or C ₄ H ₅ SO ₃ ^- ) or metal complex salts (eg containing SbF ₆ ^- , PF ₆ ^- , BF) ₄ ^- , tetra (perfluorophenyl) borate or SbF ₅ OH ₃₁ AsF ₆ ^- ). Mixtures of any of the same or different types of iodonium salts can be used if desired. The use of cerium salts is desirable and should be soluble in any inert organic solvent (as set forth below) and should also be stable to the shelf, which means that it is associated with other components prior to exposure to suitable radiation (especially electronically The bulk photosensitizer and the electron donor co-initiator do not spontaneously promote polymerization when mixed. Particularly useful sulfonium salts include, but are not limited to, triaryl substituted salts, such as mixed hexafluoroantimonate triaryl sulfonium (e.g., commercially available from Dow Chemical Company as UVI-6974), mixed triaryl sulfonium hexafluorophosphate (e.g., UVI-6990 is available from Dow Chemical Company) and aryl sulfonium hexafluorophosphate (e.g., available from Sartomer Corporation).

基於光可固化組合物之總重量，一或多種鎓鹽(例如碘鎓鹽或鋶鹽)通常可以至少0.05重量%且至多並包含10重量%或通常至少0.1重量%且至多並包含10重量%或甚至至少0.5重量%且至多並包含5重量%之量存在於光可固化組合物中。 One or more onium salts (eg, iodonium or phosphonium salts) may generally be at least 0.05% by weight and up to and including 10% by weight or typically at least 0.1% by weight and up to and including 10% by weight, based on the total weight of the photocurable composition. Or in an amount of at least 0.5% by weight and up to 5% by weight in the photocurable composition.

非離子型光酸生成劑亦可用於本發明中，該等化合物包含但不限於重氮甲烷衍生物。非離子型光酸生成劑亦可包含乙二肟衍生物。有用光酸生成劑亦可包含雙碸衍生物。其他種類之有用非離子型光酸 生成劑包含二磺基衍生物。 Nonionic photoacid generators can also be used in the present invention, including but not limited to diazomethane derivatives. The nonionic photoacid generator may also comprise a ethylenediazine derivative. Useful photoacid generators may also contain biguanide derivatives. Other types of useful nonionic photoacids The generating agent comprises a disulfo derivative.

基於光可固化組合物之總重量，一或多種非離子型光酸生成劑可以至少0.05重量%且至多並包含10重量%或通常至少0.1重量%且至多並包含10重量%或甚至至少0.5重量%且至多並包含5重量%之量存在於光可固化組合物中。 The one or more nonionic photoacid generators may be at least 0.05% by weight and up to and including 10% by weight or typically at least 0.1% by weight and up to and including 10% by weight or even at least 0.5 weight, based on the total weight of the photocurable composition. % and up to and in an amount of 5% by weight are present in the photocurable composition.

本文所闡述之一些光可固化組合物、尤其彼等含有光可聚合環氧材料及光酸生成劑者可含有一或多種電子供體光敏劑以改良光固化效率。有用之電子供體光敏劑應溶於光可固化組合物中，不含實質上干擾陽離子光固化製程之官能基，且能夠吸收(敏感度)至少150nm且至多並包含1000nm範圍內之波長之光。 Some photocurable compositions, particularly those containing photopolymerizable epoxy materials and photoacid generators, as described herein, may contain one or more electron donor photosensitizers to improve photocuring efficiency. Useful electron donor photosensitizers should be soluble in the photocurable composition, free of functional groups that substantially interfere with the cationic photocuring process, and capable of absorbing (sensitivity) light of at least 150 nm and up to and including wavelengths in the range of 1000 nm. .

適宜電子供體光敏劑因應於自輻照吸收之光子來引發鎓鹽(或其他光酸生成劑)之化學轉變。在電子供體光敏劑吸收光之後，電子供體光敏劑亦應能夠還原光酸生成劑(亦即光誘導電子轉移)。因此，電子供體光敏劑在自輻照吸收光子後通常能夠將電子供予光酸生成劑。 Suitable electron donor photosensitizers initiate chemical transformation of the onium salt (or other photoacid generator) in response to photons absorbed by the radiation. After the electron donor photosensitizer absorbs light, the electron donor photosensitizer should also be capable of reducing the photoacid generator (i.e., photoinduced electron transfer). Therefore, the electron donor photosensitizer is generally capable of supplying electrons to the photoacid generator after self-irradiation absorption of photons.

在期望極快速固化(例如固化所施加之光可固化組合物薄膜)時，電子供體光敏劑在使用光固化製程之期望輻照波長下可具有至少1000公升-莫耳^-1 cm^-1且通常至少50,000公升-莫耳^-1 cm^-1之消光係數。舉例而言，每一電子供體光敏劑通常具有至少0.4V且至多並包含3V之氧化電位(相對於SCE)。 The electron donor photosensitizer can have at least 1000 liters-mole ^-1 cm" ¹ at a desired irradiation wavelength using a photocuring process when extreme fast curing (e.g., curing of the applied photocurable composition film) is desired. Usually an extinction coefficient of at least 50,000 liters-mole ^-1 cm ^-1 . For example, each electron donor photosensitizer typically has an oxidation potential (relative to SCE) of at least 0.4 V and up to and including 3V.

一般而言，許多不同種類之化合物可用作各種反應物之電子供體光敏劑。有用電子供體光敏劑包含但不限於芳香族化合物，例如萘、1-甲基萘、蒽、9,10-二甲氧基蒽、苯并[a]蒽、芘、菲、苯并[c]菲及螢蒽。其他涉及三重激發態之有用電子供體光敏劑係羰基化合物，例如噻噸酮及呫噸酮。酮(包含芳香族酮(例如茀酮))及香豆素染料(例如酮基香豆素)(例如彼等具有強供電子部分者(例如二烷基胺基))亦可用作電子供體光敏劑。據信，其他適宜電子供體光敏劑包含 呫噸染料、吖啶染料、噻唑染料、噻嗪染料、噁嗪染料、吖嗪染料、胺基酮染料、卟啉、芳香族多環烴、對取代之胺基苯乙烯基酮化合物、胺基三芳基甲烷、部花青素、方酸菁染料及吡啶鎓染料。 In general, many different types of compounds are useful as electron donor photosensitizers for various reactants. Useful electron donor photosensitizers include, but are not limited to, aromatic compounds such as naphthalene, 1-methylnaphthalene, anthracene, 9,10-dimethoxyanthracene, benzo[a]anthracene, anthracene, phenanthrene, benzo[c ] Philippine and Firefly. Other useful electron donor photosensitizers involving triplet excited states are carbonyl compounds such as thioxanthone and xanthone. Ketones (including aromatic ketones (such as fluorenone)) and coumarin dyes (such as keto coumarin) (such as those with strong electron donating moiety (such as dialkylamino)) can also be used as electrons Body photosensitizer. It is believed that other suitable electron donor photosensitizers contain Xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, porphyrin, aromatic polycyclic hydrocarbon, substituted aminostyryl ketone compound, amine group Triarylmethane, merocyanine, squaraine dye and pyridinium dye.

亦可使用選自同或不同種類材料之電子供體光敏劑之混合物。 Mixtures of electron donor photosensitizers selected from the same or different types of materials may also be used.

基於光可固化組合物之總重量，一或多種電子供體光敏劑可以至少0.000001重量%且至多並包含5重量%及通常至少0.0001重量%且至多並包含2重量%之量存在於光可固化組合物中。 One or more electron donor photosensitizers may be present in the photocurable amount based on the total weight of the photocurable composition, at least 0.000001% by weight and up to and including 5% by weight and typically at least 0.0001% by weight and up to and including 2% by weight. In the composition.

在一些實施例中，電子供體光敏劑係芘、苯并芘、苝或苯并苝，其基於光可固化組合物之總重量以至少0.0001重量%且至多並包含2重量%之量存在。 In some embodiments, the electron donor photosensitizer is ruthenium, benzoxanthene, anthracene or benzopyrene, which is present in an amount of at least 0.0001% by weight and up to and including 2% by weight, based on the total weight of the photocurable composition.

在其他實施例中，可使用一或多種電子受體光敏劑及一或多種電子供體共起始劑之組合來代替電子供體光敏劑。 In other embodiments, a combination of one or more electron acceptor photosensitizers and one or more electron donor co-initiators can be used in place of the electron donor photosensitizer.

適宜電子受體光敏劑因應於自輻照吸收之光子引發鎓鹽之化學轉換。電子受體光敏劑亦應能夠在電子受體光敏劑吸收光之後將電子供體共起始劑(如下文所闡述)氧化為自由基陽離子(亦即光誘導之電子轉移)。因此，電子受體光敏劑在自輻照吸收光子後通常能夠自電子供體共起始劑接受電子。 Suitable electron acceptor photosensitizers are chemically converted by the photon induced by self-irradiation. The electron acceptor photosensitizer should also be capable of oxidizing the electron donor co-initiator (as set forth below) to a free radical cation (i.e., photoinduced electron transfer) after the electron acceptor photosensitizer absorbs light. Thus, electron acceptor photosensitizers are typically capable of accepting electrons from an electron donor co-initiator after self-irradiation absorption of photons.

在期望極快速固化(例如固化所施加之組合物薄膜)時，電子受體光敏劑在使用光固化製程之期望輻照波長下可具有至少1000公升-莫耳^-1 cm^-1且通常至少10,000公升-莫耳^-1 cm^-1之消光係數。 The electron acceptor photosensitizer may have at least 1000 liters-mole ^-1 cm" ¹ and typically at least 10,000 at a desired irradiation wavelength using a photocuring process when extreme fast curing (e.g., curing of the applied composition film) is desired. The extinction coefficient of liter-mole ^-1 cm ^-1 .

一般而言，可使用許多不同種類之化合物作為電子受體光敏劑用於各種反應物，前提係滿足上文所論述之能量需求。有用電子受體光敏劑包含但不限於氰基芳香族化合物、芳香族酸酐及亞醯胺及縮合吡啶鎓鹽。其他涉及三重激發態之有用電子受體光敏劑係羰基化合物，例如醌。酮(包含芳香族酮(例如茀酮))及香豆素染料(例如酮基香豆素)(例如具有強吸電子部分者(例如吡啶鎓))亦可用作電子受體光敏 劑。據信，其他適宜電子受體光敏劑包含呫噸染料、吖啶染料、噻唑染料、噻嗪染料、噁嗪染料、吖嗪染料、胺基酮染料、卟啉、芳香族多環烴、對取代之胺基苯乙烯基酮化合物、胺基三芳基甲烷、部花青素、方酸菁染料及吡啶鎓染料。二芳基酮及其他芳香族酮(例如茀酮)係有用之電子受體光敏劑。 In general, many different classes of compounds can be used as electron acceptor photosensitizers for various reactants, provided that the energy requirements discussed above are met. Useful electron acceptor photosensitizers include, but are not limited to, cyano aromatic compounds, aromatic acid anhydrides, and sulfoxides and condensed pyridinium salts. Other useful electron acceptor photosensitizers involving triplet excited states are carbonyl compounds such as hydrazine. Ketones (including aromatic ketones (such as fluorenone)) and coumarin dyes (such as ketocoumarin) (such as those with strong electron-withdrawing moiety (such as pyridinium) can also be used as electron acceptor Agent. It is believed that other suitable electron acceptor photosensitizers include xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, and pairs of substitutions. An aminostyryl ketone compound, an aminotriarylmethane, a merocyanine, a squarylium dye, and a pyridinium dye. Diaryl ketones and other aromatic ketones (e.g., fluorenone) are useful electron acceptor photosensitizers.

基於光可固化組合物之總重量，一或多種電子受體光敏劑可以至少0.000001重量%且至多並包含5重量%及通常至少0.0001重量%且至多並包含2重量%之量存在於光可固化組合物中。 One or more electron acceptor photosensitizers may be present in the photocurable amount based on the total weight of the photocurable composition, at least 0.000001% by weight and up to and including 5% by weight and typically at least 0.0001% by weight and up to and including 2% by weight. In the composition.

藉由在光可固化組合物中包含一或多種電子供體共起始劑，電子受體光敏劑之使用高度有效，每一電子供體共起始劑具有至少0.1V且至多並包含3V之氧化電位(相對於SCE)。該等電子供體共起始劑應可溶於光可固化組合物中。 The use of an electron acceptor photosensitizer is highly effective by including one or more electron donor co-initiators in the photocurable composition, each electron donor co-starter having at least 0.1 V and up to 3 V Oxidation potential (relative to SCE). The electron donor co-initiators should be soluble in the photocurable composition.

有用之電子供體共起始劑係烷基芳香族聚醚、芳基經一或多個吸電子基團(包含但不限於羧酸、羧酸酯、酮、醛、磺酸、磺酸酯及腈基團)取代之芳基烷基胺基化合物。舉例而言，芳基二烷基二胺基化合物係有用的，其中芳基係經取代或未經取代之苯基或萘基(例如具有一或多個如上所述之吸電子基團之苯基或萘基)，且兩個烷基獨立地包括1至6個碳原子。 Useful electron donor co-initiators are alkyl aromatic polyethers, aryl groups via one or more electron withdrawing groups (including but not limited to carboxylic acids, carboxylic acid esters, ketones, aldehydes, sulfonic acids, sulfonates) And a nitrile group-substituted arylalkylamine based compound. For example, aryldialkyldiamine compounds are useful wherein the aryl group is substituted or unsubstituted phenyl or naphthyl (eg, benzene having one or more electron withdrawing groups as described above) Or naphthyl), and the two alkyl groups independently comprise from 1 to 6 carbon atoms.

一般而言，基於光可固化組合物之總重量，一或多種電子供體共起始劑可以至少0.001重量%且至多並包含10重量%或更通常至少0.005重量%且至多並包含5重量%或甚至至少0.01重量%且至多並包含2重量%之量存在。 In general, the one or more electron donor co-initiators may be at least 0.001% by weight and up to and including 10% by weight or more typically at least 0.005% by weight and up to and including 5% by weight, based on the total weight of the photocurable composition. Or present in an amount of at least 0.01% by weight and up to and including 2% by weight.

如上所述，所有含有各種基本及可選組份之光可固化組合物可基於光可固化組合物之總重量進一步以至少0.5重量%且至多並包含20重量%或至少1重量%且至多並包含10重量%之量包括經分散碳黑。 As noted above, all photocurable compositions containing various basic and optional components can be further at least 0.5% by weight and up to and including 20% by weight or at least 1% by weight and at most based on the total weight of the photocurable composition. The amount of 10% by weight includes dispersed carbon black.

自由基光可固化化學物質：Free radical photocurable chemicals:

在其他實施例中，光可固化組合物可包括一或多種UV可固化組份，其中之至少一者係自由基光可固化組份且光可固化組合物可進一步包括自由基光起始劑以在光固化期間提供自由基。 In other embodiments, the photocurable composition can include one or more UV curable components, at least one of which is a free radical photocurable component and the photocurable composition can further comprise a free radical photoinitiator To provide free radicals during photocuring.

可存在一或多自由基可聚合化合物以提供自由基可聚合官能基，包含乙烯系不飽和可聚合單體、寡聚物或聚合物(例如單官能或多官能丙烯酸酯)(亦包含甲基丙烯酸酯)。該等自由基可聚合化合物包括至少一個乙烯系不飽和可聚合鍵(部分)且在許多實施例中其可包括該等不飽和部分中之兩者或更多者。此類適宜材料含有至少一個乙烯系不飽和可聚合鍵且能夠發生加成(或自由基)聚合。該等自由基可聚合材料包含單-、二-或聚丙烯酸酯及甲基丙烯酸酯，包含但不限於丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸異丙基酯、丙烯酸正己基酯、丙烯酸硬脂基酯、丙烯酸烯丙基酯、甘油二丙烯酸酯、甘油三丙烯酸酯、乙二醇二丙烯酸酯、二乙二醇二丙烯酸酯、三乙二醇二甲基丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,3-丙二醇二甲基丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、新戊二醇二丙烯酸酯、新戊二醇二甲基丙烯酸酯、三羥甲基丙烷三丙烯酸酯、1,2,4-丁烷三醇三甲基丙烯酸酯、1,4-環己二醇二丙烯酸酯、新戊四醇三丙烯酸酯、新戊四醇四丙烯酸酯、新戊四醇四甲基丙烯酸酯、二新戊四醇六丙烯酸酯、山梨醇六丙烯酸酯、雙[1-(2-丙烯醯氧基)]-對乙氧基苯基二甲基甲烷、雙[1-(3-丙烯醯氧基-2-羥基)]-對丙氧基苯基二甲基甲烷及異氰尿酸三羥乙基酯三甲基丙烯酸酯；具有200至500且包含500之分子量之聚乙二醇之雙丙烯酸酯及雙甲基丙烯酸酯；丙烯酸酯單體之可共聚合混合物，例如闡述於美國專利4,652,274(Boettcher等人)中者；及丙烯酸酯寡聚物，例如闡述於美國專利4,642,126(Zader等人)中者；及乙烯基化合物，例如苯乙烯及苯乙烯衍生物、鄰苯二甲酸二烯丙基酯、琥珀酸二乙烯基酯、己二酸二乙烯 基酯及鄰苯二甲酸二乙烯基酯。 One or more free-radically polymerizable compounds may be present to provide free-radically polymerizable functional groups, including ethylenically unsaturated polymerizable monomers, oligomers or polymers (eg, monofunctional or polyfunctional acrylates) (also including methyl groups) Acrylate). The radically polymerizable compounds include at least one ethylenically unsaturated polymerizable bond (partially) and in many embodiments it can include two or more of the unsaturated moieties. Such suitable materials contain at least one ethylenically unsaturated polymerizable bond and are capable of undergoing addition (or free radical) polymerization. The free radical polymerizable materials comprise mono-, di- or polyacrylates and methacrylates, including but not limited to methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, acrylic acid N-hexyl ester, stearyl acrylate, allyl acrylate, glycerin diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate , 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate , neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butane triol trimethacrylate, 1,4-cyclohexanediol diacrylate, neopentyl Tetraol triacrylate, neopentyl alcohol tetraacrylate, neopentyl alcohol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, bis[1-(2-propenyloxy) )]-p-ethoxyphenyldimethylmethane, bis[1-(3-propenyloxy-2-hydroxy)]-p-propoxyphenyl dimethyl Methane and trishydroxyethyl methacrylate trimethacrylate; diacrylate and dimethacrylate having polyethylene glycol having a molecular weight of 200 to 500 and comprising 500; copolymerizable mixture of acrylate monomers , for example, in U.S. Patent 4,652,274 (Boettcher et al.); and acrylate oligomers such as those described in U.S. Patent 4,642,126 (Zader et al.); and vinyl compounds such as styrene and styrene derivatives, Diallyl phthalate, divinyl succinate, diethylene adipate Base ester and divinyl phthalate.

儘管一或多種自由基可聚合材料之量並無特定限制，其可基於光可固化組合物之總重量以至少30重量%且至多並包含90重量%或通常至少40重量%且至多並包含85重量%之量存在於光可固化組合物中。 Although the amount of the one or more radically polymerizable materials is not particularly limited, it may be at least 30% by weight and up to and including 90% by weight or usually at least 40% by weight and up to and including 85 based on the total weight of the photocurable composition. The amount by weight is present in the photocurable composition.

一或多種自由基光起始劑亦可存在於光可固化組合物中以生成自由基。該等自由基光起始劑包含任一能夠在曝光於光固化輻射(例如紫外或可見輻射)後生成自由基之化合物。舉例而言，自由基光起始劑可選自三嗪化合物、噻噸酮化合物、安息香化合物、咔唑化合物、二酮化合物、鋶硼酸鹽化合物、重氮化合物、二苯甲酮化合物及聯咪唑化合物及熟習此項技術者易於明瞭之其他化合物。 One or more free radical photoinitiators may also be present in the photocurable composition to generate free radicals. The free radical photoinitiators comprise any compound capable of generating free radicals upon exposure to photocuring radiation, such as ultraviolet or visible radiation. For example, the radical photoinitiator may be selected from the group consisting of a triazine compound, a thioxanthone compound, a benzoin compound, a carbazole compound, a diketone compound, a bismuth borate compound, a diazo compound, a benzophenone compound, and a biimidazole. The compounds and other compounds which are readily apparent to those skilled in the art.

基於光可固化組合物之總重量，一或多種自由基光起始劑可以至少0.3重量%且至多並包含10重量%或通常至少0.4重量%且至多並包含10重量%或甚至至少0.5重量%且至多並包含5重量%之量存在於光可固化組合物中。 The one or more free radical photoinitiators may be at least 0.3% by weight and up to and including 10% by weight or typically at least 0.4% by weight and up to and including 10% by weight or even at least 0.5% by weight, based on the total weight of the photocurable composition. And present in the photocurable composition in an amount up to and including 5% by weight.

本文所闡述之光可固化組合物(酸催化化學物質或自由基化學物質)通常包含可用作用於無電電鍍製程之晶種金屬催化位點之適宜金屬顆粒。通常，僅使用一類金屬顆粒，但亦可包含來自相同或不同種類金屬且彼此不干擾之金屬顆粒之混合物。該等金屬顆粒通常具有淨中性電荷。 The photocurable compositions (acid catalyzed chemistries or free radical chemistries) set forth herein typically comprise suitable metal particles useful as seed metal catalytic sites for electroless plating processes. Typically, only one type of metal particle is used, but a mixture of metal particles from the same or different types of metals that do not interfere with each other may also be included. The metal particles typically have a net neutral charge.

有用之金屬顆粒可選自一或多種種類之貴金屬、半貴金屬、第IV族金屬或其組合。有用之金屬顆粒包含但不限於金、銀、鈀、鉑、銠、銥、錸、汞、釕、鋨、鐵、鈷、鎳、銅、鋁、鋅及鎢之顆粒。有用之第IV族金屬顆粒包含但不限於錫、鈦及鍺之顆粒。貴金屬顆粒(例如銀、鈀及鉑之顆粒)尤其有用，且鎳及銅之半貴顆粒亦尤其有用。錫顆粒在第IV族金屬種類中尤其有用。在許多實施例中，光可固 化組合物中使用銀顆粒或銅顆粒。 Useful metal particles can be selected from one or more of the noble metals, semi-precious metals, Group IV metals, or combinations thereof. Useful metal particles include, but are not limited to, particles of gold, silver, palladium, platinum, rhodium, ruthenium, iridium, mercury, osmium, iridium, iron, cobalt, nickel, copper, aluminum, zinc, and tungsten. Useful Group IV metal particles include, but are not limited to, particles of tin, titanium, and antimony. Precious metal particles such as particles of silver, palladium and platinum are especially useful, and semi-precious particles of nickel and copper are also particularly useful. Tin particles are especially useful in Group IV metal species. In many embodiments, the light can be solid Silver particles or copper particles are used in the composition.

可使用表面活性劑、聚合物或碳塗覆可用於本發明中之金屬顆粒且使其彼此分離。碳塗覆金屬顆粒上之碳可具有非晶形、sp2混成或類石墨烯性質。該碳可用於防止金屬顆粒之聚集且提供改良之於光可聚合組合物中之分散性。有用碳塗覆金屬顆粒包含碳塗覆銀顆粒及碳塗覆銅顆粒或碳塗覆銀顆粒及碳塗覆銅顆粒之混合物。 The metal particles usable in the present invention may be coated with a surfactant, a polymer or carbon and separated from each other. The carbon on the carbon coated metal particles can have amorphous, sp2 mixed or graphene-like properties. The carbon can be used to prevent aggregation of metal particles and to provide improved dispersion in the photopolymerizable composition. The useful carbon coated metal particles comprise carbon coated silver particles and carbon coated copper particles or a mixture of carbon coated silver particles and carbon coated copper particles.

可用於光可固化組合物中之金屬顆粒可分散於各種有機溶劑中且可在光可固化組合物之其他組份(例如多官能聚合物環氧材料)存在下或在可選組份(例如下文所闡述之多官能丙烯酸酯樹脂)存在下具有改良分散性。有用分散劑為業內已知且亦可存在(若期望)。用於分散金屬顆粒之方法包含但不限於球磨、磁攪拌、高速均質化、高壓均質化及超音波處理。 The metal particles useful in the photocurable composition can be dispersed in various organic solvents and can be present in the presence of other components of the photocurable composition (eg, a multifunctional polymeric epoxy material) or in optional components (eg, The polyfunctional acrylate resin described below has improved dispersibility in the presence of the polyfunctional acrylate resin. Useful dispersing agents are known in the art and may also be present if desired. Methods for dispersing metal particles include, but are not limited to, ball milling, magnetic stirring, high speed homogenization, high pressure homogenization, and ultrasonic processing.

可用於該等實施例中之金屬顆粒可作為個別顆粒存在於光可固化組合物中，但在許多實施例中，金屬顆粒係作為兩種或更多種金屬顆粒之團聚物存在。該等金屬顆粒可以任一幾何形狀存在，包含但不限於球形、桿形、棱柱形、立方形、圓錐形、棱錐形、絲線形、薄片形、小板形及其組合，且其形狀及大小可為均勻或非均勻的。個別及團聚金屬顆粒之平均粒徑可自至少0.01μm且至多並包含25μm或更可能至少0.02μm且至多並包含5μm變化。儘管金屬顆粒之大小並無特定限制，但最佳益處可使用平均粒徑為至少0.02μm且至多並包含10μm之個別顆粒或團聚物形式之金屬顆粒來達成。粒徑分佈合意地較窄，如其中大於50%或通常至少75%之顆粒之粒徑在平均粒徑之0.2倍至2倍範圍內所定義。平均粒徑(average particle size)(與平均粒徑(mean particle size)相同)可自可使用任一適宜程序及設備(包含購自Coulter或Horiba者)及該設備使用之適當數學計算確定之粒徑分佈來確定。 The metal particles useful in the embodiments can be present as individual particles in the photocurable composition, but in many embodiments, the metal particles are present as agglomerates of two or more metal particles. The metal particles may exist in any geometric shape, including but not limited to spheres, rods, prisms, cubes, cones, pyramids, filaments, flakes, platelets, and combinations thereof, and their shapes and sizes It can be uniform or non-uniform. The average particle size of the individual and agglomerated metal particles may vary from at least 0.01 μm and up to and including 25 μm or more possibly at least 0.02 μm and up to and including 5 μm. Although the size of the metal particles is not particularly limited, the best benefit can be achieved using metal particles having an average particle diameter of at least 0.02 μm and up to and including 10 μm of individual particles or agglomerates. The particle size distribution is desirably narrow, as is the particle size of more than 50% or typically at least 75% of the particles being defined in the range of 0.2 to 2 times the average particle size. The average particle size (same as the mean particle size) can be determined from any suitable procedure and equipment (including those purchased from Coulter or Horiba) and the appropriate mathematical calculations used in the equipment. The diameter distribution is determined.

在使用碳塗覆金屬顆粒時，其可經設計以具有等於或小於0.6μm或小於0.2μm或更可能小於0.1μm之中值顆粒直徑。該等碳塗覆金屬顆粒通常具有0.005μm之最小中值直徑。可使用動態光散射方法測定中值顆粒直徑[Dv(50%)]。舉例而言，可使用可在商業上自Malvern Instruments有限公司獲得之Malvern Zetasizer Nano ZS實施此一方法。 When carbon coated metal particles are used, they may be designed to have a median particle diameter equal to or less than 0.6 μm or less than 0.2 μm or more preferably less than 0.1 μm. The carbon coated metal particles typically have a minimum median diameter of 0.005 μm. The median particle diameter [Dv (50%)] can be determined using a dynamic light scattering method. For example, such a method can be carried out using a Malvern Zetasizer Nano ZS commercially available from Malvern Instruments, Inc.

光可固化組合物通常提供於用作溶解或分散光可固化組合物之組份之非水性(有機)溶劑或溶劑組合之適宜有機稀釋劑中。在許多實施例中，有機稀釋劑係有機溶劑介質，其包含一或多種惰性有機溶劑，例如2-乙氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、1-甲氧基-2-丙醇(DOWANOL^TM PM有機溶劑)、4-庚酮、3-庚酮、2-庚酮、環戊酮、環己酮、碳酸二乙酯、乙酸2-乙氧基乙基酯、丁酸正丁基酯、丙酮、二氯甲烷、異丙醇、乙二醇及乳酸甲酯。「惰性」意指有機溶劑並不明顯參與任一化學反應。 The photocurable composition is typically provided in a suitable organic diluent for use as a non-aqueous (organic) solvent or combination of solvents to dissolve or disperse the components of the photocurable composition. In many embodiments, the organic diluent is an organic solvent medium comprising one or more inert organic solvents such as 2-ethoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2- ethoxyethoxy) ethanol, 1-methoxy-2-propanol (DOWANOL ^TM PM organic solvent), 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, Diethyl carbonate, 2-ethoxyethyl acetate, n-butyl butyrate, acetone, dichloromethane, isopropanol, ethylene glycol and methyl lactate. "Inert" means that the organic solvent is not significantly involved in any chemical reaction.

基於光可固化組合物之總重量，有機稀釋劑(例如有機溶劑介質)可佔至多並包含1重量%或至多至少70重量%或至少10重量%且至多並包含30重量%。有機稀釋劑通常包含極少或不含水(通常小於總光可固化組合物重量之5重量%)，從而光可固化組合物可視為「光可固化組合物」。 The organic diluent (e.g., organic solvent medium) may comprise up to and comprise 1% by weight or at most 70% by weight or at least 10% by weight and up to and including 30% by weight, based on the total weight of the photocurable composition. The organic diluent typically contains little or no water (typically less than 5% by weight of the total photocurable composition) such that the photocurable composition can be considered a "photocurable composition."

在一或多種光可固化組份(如上文所闡述)以液體有機化合物形式存在時，彼等一或多種光可固化組份可用作有機稀釋劑且可無需單獨惰性有機溶劑。在該等情況下，有機稀釋劑可視為「反應性」稀釋劑。另一選擇為，一或多種反應性稀釋劑可與一或多種惰性有機溶劑組合使用以形成適宜有機稀釋劑。 When one or more photocurable components (as set forth above) are present as a liquid organic compound, one or more of the photocurable components may be used as an organic diluent and may not require a separate inert organic solvent. In such cases, the organic diluent can be considered a "reactive" diluent. Alternatively, one or more reactive diluents can be used in combination with one or more inert organic solvents to form a suitable organic diluent.

物件object

可如上文所闡述來調配上文所闡述之光可固化組合物且使用任 一適宜方式施加至任一適宜基板(闡述於下文中)之一或兩個支撐側(平面側)以形成「前體物件」。舉例而言，可使用(例如)浸塗、輥塗、料斗塗覆、噴塗、旋塗、噴墨、光微影壓印、使用柔版印刷部件(例如柔版印刷板及柔版印刷套筒))之柔版印刷、使用微影印刷板之微影印刷及使用適當印刷部件之凹版(gravure或intaglio)印刷以均勻或逐圖案方式將光可固化組合物施加至一或兩個支撐側。使用柔版印刷部件之柔版印刷可用於將相同或不同光可固化組合物之多個圖案提供於基板之一或兩個支撐側及基板任一支撐側之一或多個部分中(例如在其係連續透明聚合物網片時)。 The photocurable composition as set forth above can be formulated as described above and used A suitable means is applied to one or both of the support sides (planar side) to form a "precursor article". For example, dip coating, roll coating, hopper coating, spray coating, spin coating, ink jet, photolithography, use of flexographic printing components (eg flexographic printing plates and flexographic printing sleeves) can be used. Flexographic printing, lithographic printing using lithographic printing plates, and gravure or intaglio printing using suitable printing components to apply the photocurable composition to one or both of the support sides in a uniform or pattern-by-pattern manner. Flexographic printing using flexographic printing components can be used to provide multiple patterns of the same or different photocurable compositions on one or both of the support sides and one or more of the support sides of the substrate (eg, It is a continuous transparent polymer mesh).

所施加光可固化組合物可形成及乾燥為均勻層或乾燥為預定圖案。所得物件可視為在如下文所闡述實施光固化之前之「前體」物件。 The applied photocurable composition can be formed and dried into a uniform layer or dried to a predetermined pattern. The resulting article can be considered a "precursor" article prior to the photocuring as described below.

如下文更詳細所述，用於該等物件之基板可由任一有用材料構成且可為具有任一適宜大小及形狀之個別膜或薄片(例如由金屬材料、玻璃、紙料(任一類型之纖維素材料)或陶瓷構成)，或其可為材料連續網片(例如連續透明聚合物網片，例如連續聚(對苯二甲酸乙二酯)網片)。 As described in more detail below, the substrates for the articles can be constructed of any useful material and can be individual films or sheets of any suitable size and shape (eg, from metallic materials, glass, paper stock (of either type) The cellulosic material or ceramic composition), or it may be a continuous web of material (eg, a continuous transparent polymer web, such as a continuous poly(ethylene terephthalate) web).

在乾燥光可固化組合物中，金屬顆粒(例如碳塗覆金屬顆粒)可以至少10重量%且至多並包含90重量%之量存在，顆粒分散劑可以至少1重量%且至多並包含30重量%之量存在，個別碳顆粒可以至多並包含20重量%之量存在，且光可固化組份(闡述於上文中，在固化之前)可以至多並包含90重量%之量存在。 In the dried photocurable composition, the metal particles (eg, carbon coated metal particles) may be present in an amount of at least 10% by weight and up to and including 90% by weight, and the particulate dispersant may be at least 1% by weight and up to and including 30% by weight The amount may be present, individual carbon particles may be present in an amount up to 20% by weight, and the photocurable component (described above, prior to curing) may be present in an amount up to and including 90% by weight.

在以適宜方式(例如以逐圖案方式)將光可固化組合物施加於透明基板之一或兩個支撐側上後，可以適宜方式處理所得中間物件從而以適宜圖案光固化光可固化組合物以提供具有晶種金屬觸媒之導電圖案。 After the photocurable composition is applied to one or both of the support substrates in a suitable manner (e.g., in a pattern-by-pattern), the resulting intermediate article can be treated in a suitable manner to photocuring the photocurable composition in a suitable pattern. A conductive pattern having a seed metal catalyst is provided.

可將適宜乾燥最外聚合物塗層佈置於每一導電金屬圖案之整個表面上，但在大部分實施例中，其係僅佈置於導電金屬圖案之一部分上。舉例而言，可使用如上文所闡述之非交聯熱塑性聚合物將其佈置於整個導電金屬柵格上，但僅佈置於導電金屬連結器之一部分上。乾燥最外聚合物層之此配置可佈置於第一支撐側及相對第二支撐側中之僅一者上，或佈置於該等支撐側中之二者上。 A suitable dry outermost polymer coating can be disposed over the entire surface of each conductive metal pattern, but in most embodiments it is disposed only on one portion of the conductive metal pattern. For example, a non-crosslinked thermoplastic polymer as set forth above can be used to place it over the entire conductive metal grid, but only on one portion of the conductive metal bond. This configuration of the dried outermost polymer layer may be disposed on only one of the first support side and the opposite second support side, or on both of the support sides.

乾燥最外聚合物塗層可具有小於5μm或更可能小於3μm或甚至小於1μm之乾燥厚度。最大乾燥厚度並無限制，但出於實踐目的，最大乾燥厚度為最大20μm。乾燥最外聚合物塗層亦具有至少80%或更可能至少90%之積分透射率(如使用上文所闡述之技術所量測)及至少65℃(如上文所闡述)之玻璃轉變溫度。在一些實施例中，乾燥最外聚合物塗層具有小於3μm之乾燥厚度及大於90%之積分透射率，且非交聯熱塑性聚合物係為非交聯熱塑性丙烯酸聚合物之非交聯熱塑性非芳香族聚合物。 The dried outermost polymer coating may have a dry thickness of less than 5 [mu]m or more preferably less than 3 [mu]m or even less than 1 [mu]m. The maximum dry thickness is not limited, but for practical purposes, the maximum dry thickness is at most 20 μm. The dried outermost polymer coating also has an integrated transmission of at least 80% or more than at least 90% (as measured using the techniques set forth above) and a glass transition temperature of at least 65 °C (as set forth above). In some embodiments, the dried outermost polymer coating has a dry thickness of less than 3 μm and an integrated transmittance of greater than 90%, and the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic non-crosslinked thermoplastic acrylic polymer. Aromatic polymer.

在一些尤其有用之實施例中，該等物件在透明基板之第一支撐側及相對第二支撐側中之一者或兩者上包括導電圖案(例如導電金屬圖案)，其包括導電金屬圖案，例如由金屬線構成，該等金屬線係由銀、銅、鈀或鉑及尤其銅或銀構成。另外，可藉由無電電鍍碳塗覆金屬顆粒(例如碳塗覆銀顆粒)及視情況與碳塗覆金屬顆粒混合之個別碳顆粒來獲得該等導電金屬圖案。在導電金屬圖案具有導電金屬柵格及導電金屬連結器之情形下，導電金屬連結器可具有類似構成，只是其可實質上不包括個別碳顆粒(此意味著存在小於5重量%之個別碳顆粒)。 In some particularly useful embodiments, the articles include a conductive pattern (eg, a conductive metal pattern) on one or both of the first support side and the opposite second support side of the transparent substrate, including a conductive metal pattern, For example, it consists of metal wires which are composed of silver, copper, palladium or platinum and in particular copper or silver. Alternatively, the conductive metal patterns can be obtained by coating the metal particles (e.g., carbon coated silver particles) with electroless plating carbon and optionally carbon particles mixed with the carbon coated metal particles. In the case where the conductive metal pattern has a conductive metal grid and a conductive metal bond, the conductive metal bonder may have a similar configuration except that it may not substantially include individual carbon particles (this means that less than 5% by weight of individual carbon particles are present) ).

因此，在使中間物件經受用於光固化佈置於透明基板之支撐側上之光可固化組合物之條件且使用下文所闡述的程序及設備形成乾燥最外聚合物塗層後，可將所得產品物件納入需要導電圖案之觸控螢幕 或其他器件中。 Accordingly, the resulting product can be obtained after subjecting the intermediate article to the conditions for photocuring the photocurable composition disposed on the support side of the transparent substrate and using the procedures and apparatus set forth below to form the dried outermost polymer coating. The object is incorporated into a touch screen that requires a conductive pattern Or in other devices.

光可固化組合物之用途Use of photocurable composition

在提供乾燥最外聚合物塗層後，可使用適宜輻射(包含紫外光或可見光化光或二者)光固化(或光聚合)本文所闡述之光可固化組合物。可使用一或多種適宜光源用於曝光過程。可個別地以單一元件形式暴露每一前體物件，或在下文所闡述之替代實施例中，在使連續聚合物網片通過暴露站時，或在使暴露器件以期望路徑通過連續透明聚合物網片上方時，可個別地或共同暴露連續網片(例如捲對捲連續透明聚合物網片，其在連續透明聚合物網片之一或兩個支撐側之多個部分中包括多個前體物件(包括多個光可固化圖案))。可於基板之兩個支撐側上施加(例如使用柔版印刷術及柔版印刷部件印刷)相同或不同光可固化組合物，無論基板呈單一元件抑或連續透明聚合物網片形式。在許多實施例中，可使用本文所闡述之光可固化組合物在基板(或連續聚合物網片)之相對支撐側形成不同導電圖案。 After providing the dry outermost polymer coating, the photocurable composition described herein can be photocured (or photopolymerized) using suitable radiation, including ultraviolet or visible light or both. One or more suitable light sources can be used for the exposure process. Each precursor article may be individually exposed as a single component, or in an alternate embodiment set forth below, while passing the continuous polymer web through the exposure station, or passing the exposed device through the continuous transparent polymer in a desired path When over the web, the continuous web may be individually or collectively exposed (eg, a roll-to-roll continuous transparent polymer web comprising multiple fronts in one or both of the continuous transparent polymer webs) Body object (including multiple photocurable patterns)). The same or different photocurable compositions can be applied (e.g., printed using flexographic printing and flexographic printing components) on both support sides of the substrate, whether the substrate is in the form of a single component or a continuous transparent polymeric web. In many embodiments, different conductive patterns can be formed on the opposite support sides of the substrate (or continuous polymer mesh) using the photocurable compositions set forth herein.

在將光可固化組合物均勻施加至適宜基板時，可使用曝光輻射經由具有期望圖案之適宜光遮罩(遮蔽元件)使所得均勻乾燥層「成像」或選擇性曝光(或圖案化)，且然後使用溶解或以其他方式去除非光固化材料之適宜「顯影劑」溶液適當去除非交聯(非固化)光可固化組合物。該等特徵或步驟可在基板之兩個(相對)支撐側上實施。若期望，則可使用相同或不同光遮罩在乾燥層中形成多個導電及光固化圖案。 When the photocurable composition is uniformly applied to a suitable substrate, the resulting uniform dried layer can be "imaged" or selectively exposed (or patterned) using exposure radiation through a suitable light mask (shielding element) having a desired pattern, and The non-crosslinked (non-cured) photocurable composition is then suitably removed using a suitable "developer" solution that dissolves or otherwise removes the non-photocurable material. These features or steps can be implemented on two (relative) support sides of the substrate. If desired, multiple conductive and photocurable patterns can be formed in the dried layer using the same or different light masks.

更可能的是，可在適宜基板上使用如下文所闡述之方法形成一或多種光可固化組合物之預定圖案。 More likely, a predetermined pattern of one or more photocurable compositions can be formed on a suitable substrate using methods as set forth below.

可用於提供前體基板之適宜基板(亦在業內稱為「接收器元件」)可由任一適宜材料構成，只要其不抑制光可固化組合物之目的。舉例而言，有用基板可自包含但不限於以下之材料形成：聚合物膜、金 屬、紙料、剛性或柔性玻璃(未經處理或經(例如)四氟碳電漿、疏水氟或矽氧烷防水材料處理)、矽或陶瓷晶圓、織物及其組合(例如各種膜之壓層或紙與膜之壓層)，前提係可以適宜方式在該基板上形成光可固化組合物之均勻層或圖案且隨後輻照而在其至少一個接收(支撐)表面上形成均勻的光固化層或一或多種光固化圖案。基板可為透明的、半透明或不透明的及剛性的或撓性的。許多有用基板係透明的且具有至少90%之積分透射率，且該等透明基板亦可為撓性連續透明聚合物網片。 Suitable substrates (also referred to in the art as "receiver elements") that can be used to provide a precursor substrate can be constructed of any suitable material as long as it does not inhibit the photocurable composition. For example, a useful substrate can be formed from materials including, but not limited to, a polymer film, gold Genus, paper stock, rigid or flexible glass (untreated or treated with, for example, tetrafluorocarbon plasma, hydrophobic fluorine or decane waterproofing materials), tantalum or ceramic wafers, fabrics, and combinations thereof (eg, various films) a laminate or a laminate of paper and film, provided that a uniform layer or pattern of the photocurable composition is formed on the substrate in a suitable manner and subsequently irradiated to form a uniform light on at least one of its receiving (supporting) surfaces A cured layer or one or more photocurable patterns. The substrate can be transparent, translucent or opaque and rigid or flexible. Many useful substrates are transparent and have an integrated transmission of at least 90%, and the transparent substrates can also be flexible continuous transparent polymer webs.

在一些實施例中，基板可包括單獨接收層作為佈置於基板上之接收表面，該接收層及基板可由諸如高度接收光可固化組合物之適宜聚合物材料等材料構成。該等接收層之乾燥厚度在25℃下量測時可為至少0.05μm且至多並包含10μm，或通常至少0.05μm且至多並包含3μm。 In some embodiments, the substrate can include a separate receiving layer as a receiving surface disposed on the substrate, the receiving layer and substrate being comprised of a material such as a suitable polymeric material that highly receives the photocurable composition. The dry thickness of the receiving layers can be at least 0.05 μm and up to and including 10 μm, or typically at least 0.05 μm and up to and including 3 μm when measured at 25 °C.

更尤其地，用於形成連續透明聚合物網片形式之前體物件之適宜基板材料包含但不限於金屬膜或箔、位於聚合物上之金屬膜(例如使用導電聚合物膜上之金屬膜)、撓性玻璃、半導電有機或無機膜、有機或無機介電膜或該等材料之兩個或更多個層之壓層。舉例而言，有用連續透明聚合物網片基板可包含聚合膜(例如聚(對苯二甲酸乙二酯)膜、聚(萘二甲酸乙二酯)膜、聚醯亞胺膜、聚碳酸酯膜、聚丙烯酸酯膜、聚苯乙烯膜、聚烯烴膜及聚醯胺膜)、金屬箔(例如鋁箔)、纖維素紙或樹脂塗覆或玻璃塗覆紙、紙板網片及金屬化聚合物膜。 More particularly, suitable substrate materials for forming a body member in the form of a continuous transparent polymer web include, but are not limited to, a metal film or foil, a metal film on the polymer (eg, a metal film on a conductive polymer film), A flexible glass, semiconductive organic or inorganic film, organic or inorganic dielectric film or a laminate of two or more layers of such materials. For example, a continuous transparent polymer mesh substrate may comprise a polymeric film (eg, a poly(ethylene terephthalate) film, a poly(ethylene naphthalate) film, a polyimide film, a polycarbonate. Film, polyacrylate film, polystyrene film, polyolefin film and polyamide film), metal foil (such as aluminum foil), cellulose paper or resin coated or glass coated paper, cardboard mesh and metallized polymer membrane.

尤其有用之基板係如上文所闡述具有大於90%之積分透射率之透明聚酯膜。 Particularly useful substrates are clear polyester films having an integrated transmission of greater than 90% as set forth above.

在一些實施例中，可混合第一聚合物乳膠及第二聚合物乳膠以在基板上形成乾燥底漆層，從而黏附具有使用光可固化組合物形成之精細導電線之圖案化材料。第一聚合物乳膠可包括第一聚合物及第一 表面活性劑，從而第一聚合物乳膠之乾燥塗層具有至少50%之表面極性。第二聚合物乳膠可包括第二聚合物及第二表面活性劑，從而第二聚合物乳膠之乾燥塗層具有小於或等於27%之表面極性。 In some embodiments, the first polymer latex and the second polymer latex can be mixed to form a dry primer layer on the substrate to adhere the patterned material having the fine conductive lines formed using the photocurable composition. The first polymer latex may include a first polymer and a first The surfactant, such that the dried coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex can include a second polymer and a second surfactant such that the dried coating of the second polymer latex has a surface polarity of less than or equal to 27%.

本文所闡述第一及第二聚合物中之至少一者包括含有至少一部分地衍生自(甲基)丙烯酸縮水甘油基酯(意指丙烯酸縮水甘油基酯、甲基丙烯酸縮水甘油基酯或二者)之重複單元之乙烯基聚合物。另外，第一聚合物及第二聚合物中之至少一者係可交聯的，該聚合物可(例如)在將聚合物混合物塗覆於適宜載體上之後(例如在基板之乾燥或各種熱處理期間)發生交聯。 At least one of the first and second polymers recited herein includes at least a portion derived from glycidyl (meth)acrylate (meaning glycidyl acrylate, glycidyl methacrylate, or both) a repeating unit of a vinyl polymer. Additionally, at least one of the first polymer and the second polymer is crosslinkable, for example, after the polymer mixture is applied to a suitable support (eg, drying of the substrate or various heat treatments) Cross-linking occurred during the period.

第一聚合物可為衍生自(甲基)丙烯酸縮水甘油基酯之均聚物，但更可能地，其係衍生自(甲基)丙烯酸縮水甘油基酯及一或多種其他乙烯系不飽和可聚合單體之共聚物。 The first polymer may be a homopolymer derived from glycidyl (meth)acrylate, but more likely it is derived from glycidyl (meth)acrylate and one or more other ethylenically unsaturated A copolymer of polymerized monomers.

第二聚合物乳膠可包括一或多種第二聚合物及一或多種第二表面活性劑(闡述於下文中)，從而第二聚合物乳膠之乾燥塗層具有小於或等於28%或小於或等於27%之表面極性。如上文針對第一聚合物所闡述，尤其有用之第二聚合物係至少一部分地衍生自一或多種縮水甘油基官能乙烯系不飽和可聚合單體(例如(甲基)丙烯酸縮水甘油基酯，例如丙烯酸縮水甘油基酯及甲基丙烯酸縮水甘油基酯)之乙烯基聚合物。因此，第二聚合物可為衍生自(甲基)丙烯酸縮水甘油基酯之均聚物或衍生自(甲基)丙烯酸縮水甘油基酯及一或多種其他乙烯系不飽和可聚合單體之共聚物。 The second polymer latex can include one or more second polymers and one or more second surfactants (described below) such that the dried coating of the second polymer latex has less than or equal to 28% or less than or equal to 27% of the surface polarity. As explained above for the first polymer, a particularly useful second polymer is derived at least in part from one or more glycidyl functional ethylenically unsaturated polymerizable monomers (eg, glycidyl (meth)acrylate, For example, a vinyl polymer of glycidyl acrylate and glycidyl methacrylate. Thus, the second polymer may be a homopolymer derived from glycidyl (meth)acrylate or a copolymer derived from glycidyl (meth)acrylate and one or more other ethylenically unsaturated polymerizable monomers. Things.

第一聚合物乳膠包括一或多種第一表面活性劑，其中之每一者係烷基磺酸鈉鹽，其中烷基具有至少10個碳原子。舉例而言，第一表面活性劑可為α-烯烴(C₁₄-C₁₆)磺酸鈉，或第一表面活性劑可為由R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺(其中R係C₁₀、C₁₁或C₁₂烴基團)代表之化合物或該等化合物之混合物(其中不同R基團係C₁₀至C₁₂烴基團中之 任一者)。 The first polymeric latex comprises one or more first surfactants, each of which is a sodium alkyl sulfonate wherein the alkyl group has at least 10 carbon atoms. For example, the first surfactant can be an alpha-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate, or the first surfactant can be from R-CH ₂ -CH=CH-CH ₂ -S (=O a compound represented by ₂ O ^- Na ⁺ (wherein R is a C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon group) or a mixture of such compounds (wherein different R groups are any one of C ₁₀ to C ₁₂ hydrocarbon groups) .

第二聚合物乳膠包括一或多種第二表面活性劑，其中之每一者係具有至少3個環氧乙烷單元之烷基酚硫酸銨。舉例而言，第二表面活性劑可為聚乙氧基壬基酚硫酸銨鹽，或第二表面活性劑可由R’-苯基-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺代表，其中R’係C₈至C₁₂烴基團且n至少為3且至多並包含10，或更可能地n至少為3且至多並包含6。 The second polymeric latex comprises one or more second surfactants, each of which is an alkylphenol ammonium sulfate having at least 3 ethylene oxide units. For example, the second surfactant may be a polyethoxylated nonylphenol ammonium sulfate salt, or the second surfactant may be R'-phenyl-(O-CH ₂ CH ₂ ) _n -S(=O) O ₂ ^- NH ₄ ⁺ representatives, where R 'based C ₈ to C ₁₂ hydrocarbyl group and n is at least 3 and up to 10, and comprising, or more likely, n is at least 3 and up to 6, and comprising.

用於製備本文所闡述物件之基板可以各種形式提供，例如呈任一大小或形狀之個別薄片及連續網片(例如適於捲至捲操作之連續透明聚合物網片(包含連續透明聚酯網片)之連續網)。該等連續聚合物網片可分成或形成個別之第一、第二及其他部分，該等部分可用於形成相同或不同之光固化導電圖案。 The substrates used to prepare the articles described herein can be provided in a variety of forms, such as individual sheets and continuous webs of any size or shape (e.g., continuous transparent polymeric webs suitable for roll-to-roll operation (including continuous transparent polyester mesh) Slice) continuous network). The continuous polymeric webs can be divided or formed into individual first, second, and other portions that can be used to form the same or different photocurable conductive patterns.

在逐圖案施加光可固化組合物之後，可藉由蒸發(例如並不不利地影響剩餘組份或過早引起光固化之乾燥或預烘焙程序)去除任何剩餘有機溶劑。在下文所闡述之大部分製程(例如捲至捲製程)中，乾燥條件可處於足夠高之溫度及適宜乾燥設備下以在至少5秒內去除所有惰性有機溶劑之至少90%。舉例而言，可藉由使用熱空氣噴射、在室溫下蒸發或在升高溫度下於烘箱中加熱來達成惰性有機溶劑之適宜去除。 After application of the photocurable composition in a pattern-by-pattern, any remaining organic solvent can be removed by evaporation (eg, drying or pre-baking procedures that do not adversely affect the remaining components or prematurely cause photocuring). In most of the processes set forth below (e.g., roll-to-roll process), the drying conditions can be at a temperature high enough and under suitable drying equipment to remove at least 90% of all inert organic solvents in at least 5 seconds. For example, suitable removal of the inert organic solvent can be achieved by using hot air sparging, evaporation at room temperature, or heating in an oven at elevated temperatures.

任一所施加之均勻的光可固化組合物層之乾燥厚度可為至少0.1μm且至多並包含10μm或通常至少0.2μm且至多並包含1μm，且最佳乾燥厚度可針對所得均勻光固化層之預期應用來調節，其通常具有與均勻之非光固化光可固化組合物層大約相同之乾燥厚度。 The uniform thickness of any applied uniform photocurable composition layer can be at least 0.1 μm and up to and including 10 μm or typically at least 0.2 μm and up to and including 1 μm, and the optimum dry thickness can be for the resulting uniform photocurable layer. The application is intended to be adjusted, which typically has about the same dry thickness as the uniform non-photocurable photocurable composition layer.

任一所施加之光可固化組合物圖案可包括平均乾燥寬度為至少0.2μm且至多並包含100μm或通常至少5μm且至多並包含10μm線柵格(或其他形狀(包含圓、菱形或橢圓形或不規則網絡)之圖案)，且最佳乾燥寬度可針對所得均勻光固化層之預期用途來調節，該所得均勻 光固化層通常具有尺寸基本上與非光固化導電金屬線相同之光固化及導電金屬線。 Any applied photocurable composition pattern can include an average dry width of at least 0.2 μm and up to and including 100 μm or typically at least 5 μm and up to and including a 10 μm line grid (or other shape (including circles, diamonds or ellipses or Irregular network), and the optimum drying width can be adjusted for the intended use of the resulting uniform photocurable layer, which is evenly obtained The photocurable layer typically has photocurable and electrically conductive metal wires that are substantially the same size as the non-photocurable conductive metal wires.

在一些實施例中，可以適宜方式將相同或不同之光可固化組合物施加於基板之兩個支撐側(平面表面)上以形成「雙向」或雙側之前體物件，且每一所施加光可固化組合物可呈相同或不同之均勻層或預定圖案之形式。 In some embodiments, the same or different photocurable compositions can be applied to the two support sides (planar surfaces) of the substrate in a suitable manner to form a "two-way" or two-sided precursor article, and each applied light The curable composition can be in the form of a uniform layer or a predetermined pattern of the same or different.

在許多實施例中，使用任一已知印刷方法(例如噴墨印刷、凹版印刷或柔版印刷(其中凸版元件(例如彈性凸版元件(柔版印刷部件))源於柔版印刷板前體))將光可固化組合物之圖案施加於基板(例如作為輥至輥連續網片)之一或兩個(相對)支撐側上，許多該等印刷部件已為業內所知且一些以(例如)CYREL^®柔版光聚合物板購自DuPont及以Flexcel SR及NX柔版板及Flexcel直接柔版板購自Eastman Kodak公司。 In many embodiments, any known printing method is used (eg, inkjet printing, gravure printing, or flexographic printing (where a relief element (eg, an elastic relief element (flexographic printing component)) is derived from a flexographic printing plate precursor)) Applying a pattern of photocurable composition to one or both (opposite) support sides of a substrate (eg, as a roll-to-roll continuous web), many of which are known in the art and some (eg) CYREL ^® Flexographic photopolymer plates were purchased from DuPont and purchased from Eastman Kodak with Flexcel SR and NX flexo plates and Flexcel direct flexo plates.

尤其有用之彈性凸版元件源於柔版印刷板前體及柔版印刷套筒前體，其中之每一者可適當地成像(及處理(若需要))以提供凸版元件用於「印刷」或施加光可固化組合物之適宜圖案。 Particularly useful elastic relief elements are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be suitably imaged (and processed if desired) to provide relief elements for "printing" or application. A suitable pattern of the photocurable composition.

在其他實施例中，在利用或不利用整體遮罩之情形下自直接(或剝蝕)雷射可雕刻彈性凸版元件前體提供彈性凸版元件，如以下專利中所闡述：例如美國專利5,719,009(Fan)、5,798,202(Cushner等人)、5,804,353(Cushner等人)、6,090,529(Gelbart)、6,159,659(Gelbart)、6,511,784(Hiller等人)、7,811,744(Figov)、7,947,426(Figov等人)、8,114,572(Landry-Coltrain等人)、8,153,347(Veres等人)、8,187,793(Regan等人)及美國專利申請公開案2002/0136969(Hiller等人)、2003/0129530(Leinenback等人)、2003/0136285(Telser等人)、2003/0180636(Kanga等人)及2012/0240802(Landry-Coltrain等人)。 In other embodiments, the elastic relief element is provided from a direct (or ablated) laser-engravable elastic relief element precursor with or without an integral mask, as set forth in the following patents: for example, U.S. Patent 5,719,009 (Fan ), 5, 798, 202 (Cushner et al), 5, 804, 353 (Cushner et al), 6, 090, 529 (Gelbart), 6, 159, 659 (Gelbart), 6, 511, 784 (Hiller et al), 7, 811, 744 (Figov), 7, 947, 426 (Figov et al), 8, 114, 572 (Landry-Coltrain) </ RTI> </ RTI> <RTIgt; 2003/0180636 (Kanga et al.) and 2012/0240802 (Landry-Coltrain et al.).

在使用彈性凸版元件時，可以適宜方式將光可固化組合物施加至彈性凸版元件中之最上凸版表面(凸起表面)上。可使用適宜方式實 現該施加且期望儘可能少地塗覆至凸版凹陷之側(斜坡)或凹部。可使用網紋輥系統或其他輥施加系統、尤其低容量網紋輥(低於25億立方微米/平方英吋(63.5億立方微米/平方公分))及相關研磨刀。可藉由控制黏度或厚度或選擇適當施加方式來達成光可固化組合物至最上凸版表面上之最佳計量。舉例而言，光可固化組合物可經調配以具有用於該等應用之至少1cps(厘泊)且至多並包含5000cps之黏度。凸版影像上之光可固化組合物之厚度通常限於在施加期間可易於轉移至基板但不會太多以致於在凹部中之彈性凸版元件之邊緣上流動之足夠量。 When an elastic relief element is used, the photocurable composition can be applied to the uppermost relief surface (raised surface) in the elastic relief element in a suitable manner. Can be used in a suitable way It is now desirable and desirable to apply as little as possible to the side (slope) or recess of the relief depression. An anilox roll system or other roll application system, particularly a low volume anilox roll (less than 2.5 billion cubic microns per square inch (6.35 billion cubic microns per square centimeter)) and associated grinding knives can be used. The optimum metering of the photocurable composition onto the uppermost relief surface can be achieved by controlling the viscosity or thickness or by selecting an appropriate application. For example, the photocurable composition can be formulated to have a viscosity of at least 1 cps (centipoise) and up to 5000 cps for such applications. The thickness of the photocurable composition on the relief image is typically limited to a sufficient amount that can be easily transferred to the substrate during application but not so much as to flow over the edges of the elastic relief elements in the recess.

因此，可自網紋或其他輥噴墨系統以用於每一印刷前體物件(以均勻層或圖案形式)之量測量來供給光可固化組合物。在一實施例中，可使用第一輥將光可固化組合物自「油墨」盤或計量系統轉移至計量輥或網紋輥。光可固化組合物在其自網紋輥轉移至印刷板滾筒時通常計量至均勻厚度。在以連續網片形式經由捲至捲處置系統將基板自印刷板滾筒移動至壓印滾筒時，壓印滾筒將壓力施加至印刷板滾筒，從而將光可固化組合物之影像自彈性凸版元件轉移至基板。 Thus, the photocurable composition can be supplied from a web or other roll inkjet system in an amount measured for each printed precursor article (in a uniform layer or pattern). In one embodiment, the first roll can be used to transfer the photocurable composition from an "ink" tray or metering system to a metering roll or anilox roll. The photocurable composition is typically metered to a uniform thickness as it is transferred from the anilox roll to the printing plate cylinder. When the substrate is moved from the printing plate cylinder to the impression cylinder via a roll-to-roll handling system in the form of a continuous web, the impression cylinder applies pressure to the printing plate cylinder, thereby transferring the image of the photocurable composition from the elastic relief element To the substrate.

在基板上後，在柵格線或其他形狀之均勻層或預定圖案中(在基板之一或兩個相對側上)，可利用如上文所闡述來自適宜來源(例如螢光燈或LED)之適宜輻射輻照前體物件中之光可固化組合物以在基板上提供光固化層或一或多種光固化圖案。舉例而言，光固化可藉由使用波長(λ_max)為至少190nm且至多並包含700nm且強度為至少1,000微瓦特(microwatt)/cm²且至多並包含80,000微瓦特/cm²之UV-可見輻照來達成。用於生成該輻射之輻照系統可由一或多個(例如)呈1至50個放電燈形式之紫外燈組成，例如氙、金屬鹵化物、金屬弧(例如具有自數毫米至約10個大氣壓之期望操作壓力之低壓、中壓或高壓汞蒸氣放電燈)。該等燈可包含能夠傳送波長為至少190nm且至多並包含700nm或通常至少240nm且至多並包含450nm之光之殼。燈殼可由石英 (例如光譜純石英(spectrocil)或派熱克斯玻璃(Pyrex))組成。可用於提供紫外輻射之典型燈係(例如)中壓汞弧，例如GE H3T7弧及Hanovia 450W弧燈。光固化可使用各種燈之組合來實施，一些或所有該等燈可在惰性氣氛中操作。在使用UV燈時，碰撞在基板(或所施加之層或圖案)上之輻照通量可經設計以足以使所施加光可固化組合物以連續方式(例如以捲至捲操作)在1秒至20秒內實現足夠迅速之光固化。 After being on the substrate, in a uniform layer or predetermined pattern of grid lines or other shapes (on one or both opposite sides of the substrate), from a suitable source (such as a fluorescent lamp or LED) as explained above. The photocurable composition of the precursor article is suitably irradiated to provide a photocurable layer or one or more photocurable patterns on the substrate. For example, photocuring can be achieved by using a wavelength (λ _max ) of at least 190 nm and up to and including 700 nm and an intensity of at least 1,000 microwatts/cm ² and up to and including 80,000 microwatts/cm ² of UV-visible Irradiation is achieved. The irradiation system for generating the radiation may consist of one or more ultraviolet lamps in the form of, for example, 1 to 50 discharge lamps, such as helium, metal halides, metal arcs (eg having from a few millimeters to about 10 atmospheres) Low, medium or high pressure mercury vapor discharge lamps of the desired operating pressure). The lamps may comprise a shell capable of transmitting light having a wavelength of at least 190 nm and up to and comprising 700 nm or typically at least 240 nm and up to and including 450 nm. The lamp envelope may be composed of quartz (for example, spectrocil or Pyrex). Typical lamp systems that can be used to provide ultraviolet radiation, such as medium pressure mercury arcs, such as GE H3T7 arcs and Hanovia 450W arc lamps. Photocuring can be carried out using a combination of various lamps, some or all of which can be operated in an inert atmosphere. When a UV lamp is used, the irradiance flux impinging on the substrate (or applied layer or pattern) can be designed to be sufficient for the applied photocurable composition to be in a continuous manner (eg, in a roll-to-roll operation) Fast enough light curing in seconds to 20 seconds.

欲用於光固化中之LED輻照器件可具有350nm或更大之發射峰波長。LED器件可包含兩種或更多種類型之具有大於或等於350nm之不同發射峰波長之元件。具有350nm或更大之發射峰波長且具有紫外光發射二極體(UV-LED)之LED器件之商業實例係購自Nichia公司之NCCU-033。 The LED irradiation device to be used in photocuring may have an emission peak wavelength of 350 nm or more. The LED device can comprise two or more types of elements having different emission peak wavelengths greater than or equal to 350 nm. A commercial example of an LED device having an emission peak wavelength of 350 nm or greater and having an ultraviolet light emitting diode (UV-LED) is commercially available from Nichia Corporation NCCU-033.

前體物件之該輻照會得到包括基板(例如個別薄片或連續網片)且其上具有衍生自基板上一或兩個支撐側上之光可固化組合物之光固化層或一或多種光固化圖案之中間物件。每一光固化圖案通常含有可如下文所闡述無電電鍍之「晶種」金屬顆粒。 This irradiation of the precursor article results in a photocured layer or one or more lights comprising a substrate (e.g., individual sheets or continuous webs) having thereon a photocurable composition derived from one or both of the support sides of the substrate. The intermediate piece of the cured pattern. Each photocurable pattern typically contains "seed" metal particles that can be electrolessly plated as described below.

可進一步處理所得中間物件以在均勻光固化層或光固化圖案(其中之每一者包含金屬顆粒作為用於進一步(例如)使用無電金屬電鍍程序施加導電金屬之「晶種」材料)上納入導電金屬。舉例而言，如上文所闡述之無電「晶種」金屬顆粒可包含銀、鈀或鉑顆粒或其混合物以及上文所闡述之碳塗覆金屬顆粒，其可如下文所闡述使用銀、銅、鉑、鈀或其他金屬進行無電電鍍。 The resulting intermediate article can be further processed to incorporate conductive in a uniform photocurable layer or photocurable pattern, each of which comprises metal particles as a "seed" material for further application of a conductive metal, for example, using an electroless metal plating process) metal. For example, the electroless "seed" metal particles as set forth above may comprise silver, palladium or platinum particles or mixtures thereof and the carbon coated metal particles set forth above, which may be as described below using silver, copper, Electroless plating of platinum, palladium or other metals.

本發明之一種有用方法在印刷站中使用呈堆疊形式之多個柔版印刷板(例如如上文所闡述製得)，其中每一堆疊其本身具有印刷板滾筒，從而使用每一柔版印刷板來印刷個別基板，或可使用印刷板之堆疊來印刷連續透明聚合物網片(在一或兩個支撐側上)中之多個部分。可使用多個柔版印刷板將相同或不同的光可固化組合物「印刷」或施 加至此一基板(在相同或相對支撐側上)。 One useful method of the present invention uses a plurality of flexographic printing plates in a stacked form (e.g., as described above) in a printing station, wherein each stack itself has a printing plate cylinder to use each flexographic printing plate The individual substrates are printed, or a stack of printing plates can be used to print portions of the continuous transparent polymer web (on one or both support sides). The same or different photocurable compositions can be "printed" or applied using a plurality of flexographic printing plates Add to this substrate (on the same or opposite support side).

在其他實施例中，可與安裝於印刷機框架上之單一壓印滾筒一起使用中心壓印滾筒。在基板(或接收器元件)進入印刷機框架時，使其與壓印滾筒接觸且利用光可固化組合物印刷適當圖案。另一選擇為，可利用線上柔版印刷製程，其中印刷站係排列成水平線且由常見線軸驅動。印刷站可耦合至曝光站、切割站、摺疊機及其他後處理設備。熟習此項技術者可使用業內可獲得之資訊容易地確定設備及站之其他有用構形。舉例而言，於WO 2013/063084(Jin等人)中闡述全方位(in-the-round)製程。 In other embodiments, a central impression cylinder can be used with a single impression cylinder mounted on the frame of the printer. As the substrate (or receiver element) enters the printer frame, it is brought into contact with the impression cylinder and the appropriate pattern is printed with the photocurable composition. Alternatively, an online flexographic process can be utilized in which the printing stations are arranged in a horizontal line and driven by a common spool. The printing station can be coupled to an exposure station, a cutting station, a folding machine, and other aftertreatment equipment. Those skilled in the art can readily determine other useful configurations of the device and station using information available in the industry. For example, an in-the-round process is described in WO 2013/063084 (Jin et al.).

可將本文所闡述具有含有金屬顆粒之所闡述光固化導電圖案之中間物件立即浸沒於基於水性之無電金屬電鍍浴或溶液中，或可儲存僅具有光固化圖案之中間物件(例如以捲起之連續網片形式)供隨後使用。 The intermediate article having the illustrated photocurable conductive pattern containing the metal particles described herein may be immediately immersed in an aqueous electroless metal plating bath or solution, or an intermediate article having only a photocurable pattern may be stored (eg, rolled up) Continuous mesh form) for subsequent use.

舉例而言，可使每一中間物件與光固化圖案內所納入金屬顆粒內之金屬相同或不同之無電電鍍金屬接觸。在大部分實施例中，然而，無電電鍍金屬係不同於分散於光固化圖案內之金屬顆粒中所使用之金屬的金屬。 For example, each of the intermediate articles may be contacted with an electroless plated metal that is the same or different from the metal contained in the metal particles within the photocurable pattern. In most embodiments, however, the electroless plating metal is different from the metal of the metal used in the metal particles dispersed in the photocuring pattern.

此時可使用將可能無電「電鍍」於金屬顆粒上之任一金屬，但在大部分實施例中，無電電鍍金屬可為(例如)銅(II)、銀(I)、金(IV)、鈀(II)、鉑(II)、鎳(II)、鉻(II)及其組合。銅(II)、銀(I)及鎳(II)係用於銀、銅、鉑或鈀晶種金屬觸媒之尤其有用之無電電鍍金屬。在一些實施例中，所得導電金屬圖案係由呈晶種金屬觸媒或電鍍金屬或二者之形式之銀、銅、鈀或鉑或其組合構成。 At this point, any metal that may be "electroplated" onto the metal particles may be used, but in most embodiments, the electroless plating metal may be, for example, copper (II), silver (I), gold (IV), Palladium (II), platinum (II), nickel (II), chromium (II), and combinations thereof. Copper (II), silver (I) and nickel (II) are particularly useful electroless plating metals for silver, copper, platinum or palladium seed metal catalysts. In some embodiments, the resulting conductive metal pattern is comprised of silver, copper, palladium, or platinum, or a combination thereof, in the form of a seed metal catalyst or a plated metal or both.

無電電鍍可使用已知溫度及時間條件來實施，此乃因該等條件在各種教科書及科學文獻中眾所周知。亦已知基於水性之無電電鍍溶液中包含各種添加劑，例如金屬錯合劑或穩定劑。時間及溫度之變化 可用於改變金屬無電電鍍厚度或金屬無電電鍍沈積速率。 Electroless plating can be carried out using known temperature and time conditions, as these conditions are well known in various textbooks and scientific literature. It is also known that aqueous based electroless plating solutions contain various additives such as metal complexing agents or stabilizers. Time and temperature changes It can be used to change the thickness of metal electroless plating or the rate of metal electroless plating deposition.

在用於在基板之一或兩個支撐側之一或多個部分上提供導電圖案之無電電鍍程序之後，可自基於水性之無電電鍍浴或溶液取出所得產品物件且使用蒸餾水或去離子水或另一基於水性之溶液洗滌以去除任何殘餘無電電鍍化學物質。此時，無電電鍍金屬通常較為穩定且可用於其預期目的以形成具有期望導電金屬圖案之各種導電物件。 After the electroless plating process for providing a conductive pattern on one or both of the support sides, the resulting product article may be taken from an aqueous electroless plating bath or solution and distilled or deionized water or Another aqueous based solution wash removes any residual electroless plating chemistry. At this time, the electroless plating metal is generally relatively stable and can be used for its intended purpose to form various conductive articles having a desired conductive metal pattern.

在一些實施例中，所得產品物件可如(例如)US 2014/0071356(Petcavich)之[0048]中所闡述在室溫下使用水或如WO 2013/169345(Ramakrishnan等人)之[0027]中所闡述在小於70℃之溫度下使用去離子水來沖洗或清洗。 In some embodiments, the resulting product article can be used at room temperature as set forth in [0048], for example, in US 2014/0071356 (Petcavich) or as in WO 2013/169345 (Ramakrishnan et al.) [0027] Deionized water is used for rinsing or washing at temperatures less than 70 °C.

為出於視覺或耐久性原因改變無電電鍍金屬之表面，可採用各種後處理，包含在無電電鍍金屬上表面電鍍再至少另一(第三或更多)金屬(例如鎳或銀)(此程序有時稱為「覆蓋」)，或產生足以改變表面色彩及散射性質而不降低無電電鍍(第二)金屬之導電率之金屬氧化物、金屬硫化物或金屬硒化物層。 In order to change the surface of an electroless plated metal for visual or durability reasons, various post-treatments may be employed, including plating on the surface of the electroless plated metal and then at least another (third or more) metal (such as nickel or silver) (this procedure) Sometimes referred to as "covering", or a metal oxide, metal sulfide or metal selenide layer that is sufficient to alter the surface color and scattering properties without reducing the conductivity of the electrolessly plated (second) metal.

用於實施本發明一些實施例之有用方法及裝置之一些細節闡述於(例如)US 2014/0071356(闡述於上文中)及WO 2013/169345(闡述於上文中)。由Petcavich及Jin於2012年10月29日提出申請之PCT/US/062366中提供用於尤其以捲至捲方式製備導電物件之有用之製造系統之其他細節。 Some details of useful methods and apparatus for practicing some embodiments of the invention are set forth, for example, in US 2014/0071356 (described above) and WO 2013/169345 (described above). Further details of a useful manufacturing system for preparing conductive articles, particularly in a roll-to-roll manner, are provided in PCT/US/062366, filed on Oct. 29, 2012.

可用於實施本發明之設備及步驟特徵之額外系統闡述於美國專利第14/146,867號(2014年1月3日由Shifley提出申請)中。 An additional system that can be used to implement the apparatus and step features of the present invention is described in U.S. Patent No. 14/146,867, filed on Jan. 3, 2014, by Shifley.

本文所闡述之光可固化組合物可用於提供一或多種導電物件之方法中。此方法包括提供連續透明聚合物網片[例如由聚(對苯二甲酸乙二酯)構成]。 The photocurable compositions set forth herein can be used in a method of providing one or more electrically conductive articles. This method comprises providing a continuous transparent polymer web [for example composed of poly(ethylene terephthalate)].

在至少透明基板之連續網片之第一部分上，方法亦包含形成包 括如上文所闡述之光可固化組份及分散金屬顆粒之光可固化組合物(如本文所闡述)之光可固化圖案。然後光固化光可固化圖案以在連續網片之第一部分上形成光固化圖案，該光固化圖案包括分散金屬顆粒(闡述於上文中)作為晶種金屬觸媒位點。然後可使用導電金屬(如上文所闡述)該光固化圖案無電電鍍於連續網片之第一部分上。 The method also includes forming a package on the first portion of the continuous web of at least the transparent substrate A photocurable composition of a photocurable composition as described above and a photocurable composition of dispersed metal particles (as set forth herein). The photocurable pattern is then photocured to form a photocured pattern on the first portion of the continuous web comprising dispersed metal particles (described above) as a seed metal catalyst site. The photocurable pattern can then be electrolessly electroplated onto the first portion of the continuous web using a conductive metal (as set forth above).

此方法可進一步包括：在連續網片中一或多個不同於第一部分之其他部分上使用相同或不同光可固化組合物再實施上文所闡述之形成、光固化及無電電鍍特徵一或多次。以該方式，可在基板之相同或不同支撐側上形成多個光固化及無電電鍍圖案。所得導電圖案可具有相同組成、圖案或導電性，或其可在任一或所有該等特徵中皆不同(如自消費者需要預先確定)。該多個無電板圖案可在透明聚合物網片中一或兩個支撐側上之多個部分中之每一者上分別形成為多個導電柵格及連結至其之多個導電連結器。如下文更詳細所述，可在多個部分中之任一者中於至少一部分但非全部每一導電圖案上形成乾燥最外聚合物塗層。以此方式在透明基板中第一支撐側及相對第二支撐側中之一者或二者上形成之導電金屬圖案可包括導電金屬線，其包括銀、銅、鈀或鉑或該等金屬中之兩者或更多者。 The method can further comprise: performing one or more of the forming, photocuring, and electroless plating features set forth above using the same or different photocurable compositions on one or more other portions of the continuous web that are different from the first portion Times. In this manner, a plurality of photocurable and electroless plating patterns can be formed on the same or different support sides of the substrate. The resulting conductive pattern can have the same composition, pattern, or conductivity, or it can be different in any or all of the features (e.g., as predetermined by the consumer). The plurality of electroless plate patterns may be formed as a plurality of electrically conductive grids and a plurality of electrically conductive connectors coupled thereto, respectively, on each of the plurality of portions on one or both of the support sides of the transparent polymer web. As described in more detail below, the dried outermost polymer coating can be formed on at least a portion, but not all, of each of the conductive patterns in any of a plurality of portions. The conductive metal pattern formed on one or both of the first support side and the opposite second support side in the transparent substrate in this manner may include a conductive metal wire including silver, copper, palladium or platinum or the like Two or more.

因此，本發明方法可用於提供複數個前體物件，其包括：藉由使用柔版印刷部件將光可固化組合物施加至連續透明聚合物網片之第一部分上來在該第一部分上形成第一光可固化圖案，使包括第一光可固化圖案之連續透明聚合物網片前進以接近曝光輻射，且由此在第一部分上形成第一光固化圖案，藉由使用柔版印刷部件將相同或不同之光可固化組合物施加至連續透明聚合物網片之第二部分來在該第二部分上形成第二光可固化圖案， 使包括第二光可固化圖案之連續透明聚合物網片前進以接近曝光輻射，且由此在第二部分上形成第二光固化圖案，視情況，以類似方式使用相同或不同之光可固化組合物及相同或不同之柔版印刷部件在連續透明聚合物網片之一或多個其他各別部分上形成一或多個其他光固化圖案，及捲繞包括多個光固化圖案之連續透明聚合物網片，或將連續網片立即用於進一步處理(例如無電電鍍)且在組裝成電子器件之前提供乾燥最外聚合物塗層。 Accordingly, the method of the present invention can be used to provide a plurality of precursor articles comprising: forming a first on the first portion by applying a photocurable composition to the first portion of the continuous transparent polymer web using a flexographic printing member a photocurable pattern that advances the continuous transparent polymer web comprising the first photocurable pattern to approximate exposure radiation, and thereby forming a first photocured pattern on the first portion, using the flexographic printing component to be the same or A different photocurable composition is applied to the second portion of the continuous transparent polymer web to form a second photocurable pattern on the second portion, The continuous transparent polymer web comprising the second photo-curable pattern is advanced to approximate exposure radiation, and thereby forming a second photo-curing pattern on the second portion, optionally using the same or different light in a similar manner The composition and the same or different flexographic printing members form one or more other photocurable patterns on one or more of the other discrete portions of the continuous transparent polymeric web, and are wound into a continuous transparent comprising a plurality of photocurable patterns The polymer web, or the continuous web, is immediately used for further processing (e.g., electroless plating) and provides a dry outermost polymer coating prior to assembly into an electronic device.

因此，該方法可進一步包括：自包括多個光固化圖案之連續透明聚合物網片形成多個導電物件，在多個光固化圖案中之每一者之至少一部分但非全部部分上形成乾燥最外聚合物塗層(如本文所闡述)，及將個別導電物件組裝成相同或不同之個別電子器件(例如相同或不同之觸控螢幕顯示器或器件)。 Accordingly, the method can further include forming a plurality of electrically conductive articles from the continuous transparent polymer web comprising the plurality of photocurable patterns, forming a dry most on at least a portion but not all of the plurality of photocurable patterns The outer polymer coating (as set forth herein), and the individual conductive articles are assembled into the same or different individual electronic devices (eg, the same or different touch screen displays or devices).

該方法亦可包括：無電電鍍連續透明聚合物網片中之多個光固化導電圖案中之每一者以形成多個導電物件，且形成期望乾燥最外聚合物塗層，且可藉由相同或不同之使用者將所得導電物件組裝成相同或不同之個別電子器件。該等器件可為觸控螢幕或其他顯示器件，其亦包含適宜控制器、外殼及軟體以用於經由網際網路進行之任一類型之期望通信。另一選擇為，器件可為該等觸控螢幕或其他顯示器件之子組件。在一些實施例中，由本發明提供之器件係觸控螢幕，其各自具有至少1cm²且至多並包含100m²之觀看面積。觸控螢幕之大小及形狀可端視預期用途而有所變化。 The method can also include electrolessly plating each of the plurality of photocurable conductive patterns in the continuous transparent polymer web to form a plurality of electrically conductive articles and forming a desired outermost outermost polymer coating, and by the same Or different users assemble the resulting conductive articles into the same or different individual electronic devices. The devices can be touch screens or other display devices that also include suitable controllers, housings, and software for any type of desired communication over the Internet. Alternatively, the device can be a sub-component of the touch screen or other display device. In some embodiments, the device-based touch screens provided by the present invention each have a viewing area of at least 1 cm ² and up to and including 100 m ² . The size and shape of the touch screen can vary depending on the intended use.

在一些實施例中，本發明方法可用於製備包括觸控螢幕之電子 器件，該方法包括：將一或多個個別導電物件組裝成器件外殼以形成觸控螢幕區，一或多個個別導電物件中之每一者包括含有導電金屬(無電電鍍於衍生自本文所闡述光可固化組合物之光固化導電圖案上)之導電圖案，且將乾燥最外聚合物塗層佈置於至少一部分但非全部導電金屬圖案上。 In some embodiments, the method of the present invention can be used to prepare an electronic device including a touch screen The device includes: assembling one or more individual conductive articles into a device housing to form a touch screen region, each of the one or more individual conductive members comprising a conductive metal (electroless plating is derived from the description herein) A conductive pattern on the photocurable conductive pattern of the photocurable composition, and the dried outermost polymer coating is disposed on at least a portion but not all of the conductive metal pattern.

可藉由以下方式來製備本文所闡述之乾燥最外聚合物塗層：首先將一或多種適宜非交聯熱塑性聚合物溶於適當溶劑(或其混合物)中，隨後將所得最外聚合物塗層調配物印刷或施加於導電圖案之一部分上。適宜非交聯熱塑性聚合物包含彼等詳細闡述於上文中者。 The dried outermost polymer coatings described herein can be prepared by first dissolving one or more suitable non-crosslinked thermoplastic polymers in a suitable solvent (or mixture thereof), followed by coating the resulting outermost polymer. The layer formulation is printed or applied to a portion of the conductive pattern. Suitable non-crosslinked thermoplastic polymers include those detailed above.

用於非交聯熱塑性聚合物之適當溶劑包含但不限於醇、醚及二醇醚，例如二丙二醇甲醚、1-甲氧基-2-丙醇及乙酸2-甲氧基-1-甲基乙基酯。可將其他材料添加至最外聚合物塗層調配物中以賦予其期望性質，且該等材料可用於控制黏度或其可為用於修改表面張力之表面活性劑。 Suitable solvents for the non-crosslinked thermoplastic polymer include, but are not limited to, alcohols, ethers and glycol ethers such as dipropylene glycol methyl ether, 1-methoxy-2-propanol and 2-methoxy-1-methyl acetate Ethyl ethyl ester. Other materials may be added to the outermost polymer coating formulation to impart their desired properties, and such materials may be used to control viscosity or it may be a surfactant used to modify surface tension.

根據本發明，可使用業內已知之各種沈積或印刷技術將最外聚合物塗層調配物佈置於基板中一或兩個支撐側上之至少一部分導電圖案上。該等技術包含但不限於柔版印刷、網版印刷、凹版印刷、噴墨印刷及狹縫沈積。可使用沈積方法將最外聚合物塗層調配物一次性施加於一個導電圖案中(例如間歇式製程)或以連續捲對捲製程施加於多個導電圖案中。 In accordance with the present invention, the outermost polymer coating formulation can be disposed on at least a portion of the conductive pattern on one or both of the support sides of the substrate using various deposition or printing techniques known in the art. Such techniques include, but are not limited to, flexographic printing, screen printing, gravure printing, ink jet printing, and slit deposition. The outermost polymer coating formulation can be applied to one conductive pattern (eg, a batch process) or a continuous roll-to-roll process to a plurality of conductive patterns using a deposition process.

可將根據本發明製得之有用產品物件調配成包括導電金屬圖案之適宜圖案及發明性乾燥最外聚合物塗層之電容性觸控螢幕感測器。舉例而言，可藉由以下方式在導電圖案中形成導電金屬柵格及導電金屬連結器：以預定圖案印刷光可固化組合物，隨後使用如上文所闡述之適宜金屬無電電鍍印刷圖案。亦可使用如上文所闡述之柔版印刷將 乾燥最外聚合物塗層調配物僅施加於導電金屬圖案上。 The useful product articles made in accordance with the present invention can be formulated into a capacitive touch screen sensor comprising a suitable pattern of conductive metal patterns and an inventive dry outermost polymer coating. For example, a conductive metal grid and a conductive metal bonder can be formed in the conductive pattern by printing the photocurable composition in a predetermined pattern, followed by printing the pattern using a suitable metal electroless plating as set forth above. Can also use flexo printing as explained above The dried outermost polymer coating formulation is applied only to the conductive metal pattern.

本發明提供至少以下實施例及其組合，但特徵之其他組合被視為在本發明內，如熟習此項技術者自此揭示內容之教示將瞭解： The present invention provides at least the following embodiments and combinations thereof, but other combinations of features are considered to be within the present invention, as will be appreciated by those skilled in the art from this disclosure.

1.一種導電物件，其包括：透明基板，其具有第一支撐側及相對第二支撐側；佈置於至少該第一支撐側上之導電圖案，及乾燥最外聚合物塗層，其佈置於至少一部分但非全部該導電圖案上，該乾燥最外聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 What is claimed is: 1. A conductive article comprising: a transparent substrate having a first support side and an opposite second support side; a conductive pattern disposed on at least the first support side, and a dry outermost polymer coating disposed on The dry outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a non-crosslinking comprising a glass transition temperature (T _g ) equal to or greater than 65 ° C on at least a portion but not all of the conductive pattern. Thermoplastic polymer.

2.如實施例1之導電物件，其中該導電圖案至少包括：導電柵格；及導電連結器，其連結至該導電柵格。 2. The electrically conductive article of embodiment 1, wherein the electrically conductive pattern comprises at least: a conductive grid; and a conductive connector coupled to the electrically conductive grid.

3.如實施例2之導電物件，其中該乾燥最外聚合物塗層佈置於100%或以下之該導電柵格上，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上。 3. The electrically conductive article of embodiment 2, wherein the dried outermost polymer coating is disposed on the electrically conductive grid of 100% or less, but the dried outermost polymer coating is disposed at less than 100% of the electrically conductive link On the device.

4.如實施例2或3之導電物件，其中該導電柵格係導電金屬柵格且該導電連結器係連結至其之導電金屬連結器。 4. The electrically conductive article of embodiment 2 or 3, wherein the electrically conductive grid is a conductive metal grid and the electrically conductive connector is coupled to a conductive metal bond therewith.

5.如實施例1至4中任一項之導電物件，其進一步包括：佈置於該透明基板之相對第二支撐側上之導電圖案，及乾燥最外聚合物層，其佈置於該透明基板中該相對第二支撐側上之至少一部分但非全部該導電圖案上，此乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 5. The electrically conductive article of any of embodiments 1 to 4, further comprising: a conductive pattern disposed on the opposite second support side of the transparent substrate, and a dried outermost polymer layer disposed on the transparent substrate The dry polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or at least a portion, but not all, of the conductive pattern on the second support side. Non-crosslinked thermoplastic polymer greater than 65 °C.

6.如實施例5之導電物件，其中該導電圖案至少包括：導電柵格，及 導電連結器，其連結至該導電柵格。 6. The conductive article of embodiment 5, wherein the conductive pattern comprises at least: a conductive grid, and A conductive connector coupled to the conductive grid.

7.如實施例6之導電物件，其中該乾燥最外聚合物塗層佈置於100%或以下之該導電柵格上，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上，其皆位於該透明基板之該相對第二支撐側上。 7. The electrically conductive article of embodiment 6, wherein the dried outermost polymer coating is disposed on the electrically conductive grid of 100% or less, but the dried outermost polymer coating is disposed at less than 100% of the electrically conductive link The devices are all located on the opposite second support side of the transparent substrate.

8.如實施例1至7中任一項之導電物件，其中該非交聯熱塑性聚合物係非交聯、非芳香族熱塑性聚合物。 The electrically conductive article of any of embodiments 1 to 7, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked, non-aromatic thermoplastic polymer.

9.如實施例1至8中任一項之導電物件，其中該乾燥最外聚合物塗層具有小於3μm之乾燥厚度。 9. The electrically conductive article of any of embodiments 1 to 8, wherein the dried outermost polymeric coating has a dry thickness of less than 3 [mu]m.

10.如實施例1至9中任一項之導電物件，其中該非交聯熱塑性聚合物係非交聯熱塑性丙烯酸聚合物。 10. The electrically conductive article of any of embodiments 1 to 9, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic acrylic polymer.

11.如實施例1至10中任一項之導電物件，其中該非交聯熱塑性聚合物包括至少衍生自(甲基)丙烯酸甲酯之重複單元及衍生自(甲基)丙烯酸烷基酯之重複單元，其中該烷基具有1至18個碳原子，其中衍生自(甲基)丙烯酸烷基酯之該等重複單元佔總聚合物重複單元之至少5mol%且至多並包含25mol%。 The conductive article of any one of embodiments 1 to 10, wherein the non-crosslinked thermoplastic polymer comprises at least a repeating unit derived from methyl (meth) acrylate and a repeat derived from an alkyl (meth) acrylate a unit wherein the alkyl group has 1 to 18 carbon atoms, wherein the repeating units derived from the alkyl (meth) acrylate account for at least 5 mol% and at most 25 mol% of the total polymer repeating unit.

12.如實施例1至11中任一項之導電物件，其中至少佈置於該透明基板之該第一支撐側上之該導電圖案包括由至少銀、銅、鈀或鉑構成之導電金屬線。 12. The electrically conductive article of any of embodiments 1 to 11, wherein the electrically conductive pattern disposed on at least the first support side of the transparent substrate comprises a conductive metal wire comprised of at least silver, copper, palladium or platinum.

13.如實施例5至12中任一項之導電物件，其中佈置於該透明基板之該相對第二支撐側上之該導電圖案包括至少由銀、銅、鈀或鉑構成之導電金屬線。 The conductive article of any one of embodiments 5 to 12, wherein the conductive pattern disposed on the opposite second support side of the transparent substrate comprises a conductive metal wire composed of at least silver, copper, palladium or platinum.

14.如實施例1至13中任一項之導電物件，其中該透明基板係連續透明聚合物網片，且該物件包括相同或不同之佈置於上該連續透明聚合物網片中該第一支撐側之至少第一部分及該相對第二支撐側之至少第一部分上的導電圖案。 The conductive article of any one of embodiments 1 to 13, wherein the transparent substrate is a continuous transparent polymer mesh, and the article comprises the same or different ones disposed in the continuous transparent polymer mesh. a conductive pattern on at least a first portion of the support side and at least a first portion of the opposite second support side.

15.如實施例14之導電物件，其中該連續透明聚合物網片包括：位於該第一支撐側上之多個部分及位於該相對第二支撐側上之多個部分；分別佈置於該透明基板中該第一支撐側及該相對第二支撐側上之該多個部分上之相同或不同之導電圖案；及乾燥最外聚合物塗層，其佈置於至少一部分但非全部每一導電圖案上。 15. The conductive article of embodiment 14, wherein the continuous transparent polymer mesh comprises: a plurality of portions on the first support side and a plurality of portions on the opposite second support side; respectively disposed on the transparent a conductive pattern of the same or different on the first support side and the opposite second support side of the substrate; and a dry outermost polymer coating disposed on at least a portion but not all of the conductive patterns on.

16.一種電子器件，其包括作為觸控螢幕之如實施例1至15中任一項之導電物件。 16. An electronic device comprising a conductive article as in any one of embodiments 1 to 15 as a touch screen.

17.如實施例16之電子器件，其中該觸控螢幕具有至少1cm²且至多並包含100m²之觀看面積。 17. The electronic device of embodiment 16, wherein the touch screen has a viewing area of at least 1 cm ² and at most and 100 m ² .

18.一種提供如實施例1至15中任一項之導電物件之方法，該方法包括：在透明基板之第一支撐側上形成導電圖案，該透明基板亦包括相對第二支撐側；及在至少一部分但非全部該導電圖案上形成乾燥最外聚合物塗層，該乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 18. A method of providing a conductive article according to any one of embodiments 1 to 15, the method comprising: forming a conductive pattern on a first support side of the transparent substrate, the transparent substrate also including a second support side; Forming a dry outermost polymer coating on at least a portion but not all of the conductive pattern, the dried polymer coating having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and including a glass transition temperature (T _g ) equal to or greater than Non-crosslinked thermoplastic polymer at 65 °C.

19.如實施例18之方法，其中該導電圖案至少包括：導電柵格，及導電連結器，其連結至該導電柵格。 19. The method of embodiment 18, wherein the conductive pattern comprises at least: a conductive grid, and a conductive connector coupled to the conductive grid.

20.如實施例19之方法，其包括在100%或以下之該導電柵格上形成該乾燥最外聚合物塗層，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上。 20. The method of embodiment 19, comprising forming the dried outermost polymer coating on the electrically conductive grid of 100% or less, but the dried outermost polymer coating is disposed at less than 100% of the electrically conductive linkage On the device.

21.如實施例19之方法，其中該導電柵格係導電金屬柵格且該導電連結器係連結至其之導電金屬連結器。 21. The method of embodiment 19 wherein the electrically conductive grid is a conductive metal grid and the electrically conductive connector is coupled to a conductive metal bond therewith.

22.如實施例18至21中任一項之方法，其進一步包括：在該透明基板之該相對第二支撐側上形成導電圖案，及在該透明基板中該相對第二支撐側上之至少一部分但非全部該導電圖案上形成乾燥最外聚合物塗層，此乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The method of any one of embodiments 18 to 21, further comprising: forming a conductive pattern on the opposite second support side of the transparent substrate, and at least on the opposite second support side in the transparent substrate A portion, but not all, of the conductive pattern forms a dry outermost polymer coating having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or greater than 65 Non-crosslinked thermoplastic polymer at °C.

23.如實施例22之方法，其中該相對第二支撐側上之該導電圖案包括導電柵格及連結至該導電柵格之導電連結器。 23. The method of embodiment 22, wherein the conductive pattern on the opposite second support side comprises a conductive grid and a conductive bond coupled to the conductive grid.

24.如實施例22或23中任一項之方法，其包括在100%或以下之該導電柵格上形成該乾燥最外聚合物塗層，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上，其皆位於該透明基板之該相對第二支撐側上。 The method of any one of embodiments 22 or 23, comprising forming the dried outermost polymer coating on the conductive grid of 100% or less, but the dried outermost polymer coating is disposed less than 100% of the conductive connectors are located on the opposite second support side of the transparent substrate.

25.如實施例18至24中任一項之方法，其包括使用柔版印刷部件在該第一支撐側上形成該最外聚合物塗層。 The method of any one of embodiments 18 to 24, comprising forming the outermost polymer coating on the first support side using a flexographic printing member.

26.如實施例18至25中任一項之方法，其包括在係連續透明聚合物網片之該基板之第一部分上形成該導電圖案。 The method of any of embodiments 18 to 25, comprising forming the conductive pattern on a first portion of the substrate that is a continuous transparent polymer web.

27.如實施例18至26中任一項之方法，其包括：在係連續透明聚合物網片之該基板之該第一支撐側上之各別多個部分上形成多個導電圖案，及在該多個部分中之該等導電圖案中之每一者之至少一部分但非全部部分上形成乾燥最外聚合物塗層，該乾燥最外聚合物塗層佈置於該多個導電圖案中之每一者上且具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 27. The method of any one of embodiments 18 to 26, comprising: forming a plurality of conductive patterns on respective portions of the first support side of the substrate of the continuous transparent polymer web, and Forming a dry outermost polymer coating on at least a portion but not all portions of each of the plurality of portions of the conductive patterns, the dried outermost polymer coating being disposed in the plurality of conductive patterns Each has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a non-crosslinked thermoplastic polymer having a glass transition temperature (T _g ) equal to or greater than 65 °C.

28.一種提供如實施例1至15中任一項之導電物件之方法，該方法包括：(i)提供呈連續透明聚合物網片形式之基板；(ii)使用包括金屬顆粒之光可固化組合物在該連續透明聚合物網片之第一支撐側上之至少第一部分上形成第一光可固化圖案；(iii)將該光可固化圖案曝光於光固化輻射以在該第一支撐側之該第一部分上形成光固化圖案；(iv)使用導電金屬無電電鍍該第一支撐側之該第一部分上之該光固化圖案以在該第一支撐側之該第一部分上形成導電金屬圖案；及(v)在該第一支撐側之該第一部分中之至少一部分但非全部導電圖案上形成乾燥最外聚合物塗層。 28. A method of providing a conductive article according to any of embodiments 1 to 15, the method comprising: (i) providing a substrate in the form of a continuous transparent polymer web; (ii) curing using light comprising metal particles Forming a first photocurable pattern on at least a first portion of the continuous support web of the continuous transparent polymer web; (iii) exposing the photocurable pattern to photocuring radiation on the first support side Forming a photocuring pattern on the first portion; (iv) electrolessly plating the photocuring pattern on the first portion of the first support side using a conductive metal to form a conductive metal pattern on the first portion of the first support side; And (v) forming a dry outermost polymer coating on at least a portion but not all of the conductive patterns of the first portion of the first support side.

29.如實施例28之方法，其進一步包括：使用相同或不同之光可固化組合物及相同或不同之乾燥最外聚合物塗層，在該連續透明聚合物網片之該第一支撐側上一或多個不同於該第一部分之其他部分上重複特徵(ii)至(v)。 29. The method of embodiment 28, further comprising: using the same or different photocurable compositions and the same or different dry outermost polymer coatings on the first support side of the continuous transparent polymer web Features (ii) through (v) are repeated on one or more other portions than the first portion.

30.如實施例28或29之方法，其包括：藉由使用第一柔版印刷部件將該光可固化組合物施加至該連續透明聚合物網片之該第一支撐側上之第一部分上來在該第一部分上形成該第一光可固化圖案，使包括含有該第一光可固化圖案之該第一部分之該連續透明聚合物網片前進以接近曝光輻射，且由此在該第一部分上形成第一光固化圖案，藉由使用相同或不同之柔版印刷部件將相同或不同之光可固化組合物施加至該連續透明聚合物網片之該第一支撐側上之第二部分來同時或依序在該第二部分上形成第二光可固化圖案；使包括含有該第二光可固化圖案之該第一支撐側上之該第二部 分之該連續透明聚合物網片前進以接近曝光輻射，且由此在該第一支撐側之該第二部分上形成第二光固化圖案；視情況使用相同或不同之光可固化組合物及相同或不同之柔版印刷部件在該連續透明聚合物網片中該第一支撐側上之一或多個其他部分上同時或依序形成一或多個其他光固化圖案；無電電鍍該第一支撐側上之該等光固化圖案中之每一者以形成多個導電金屬圖案；及在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外聚合物塗層。 30. The method of embodiment 28 or 29, comprising: applying the photocurable composition to the first portion of the continuous transparent polymer web on the first support side by using a first flexographic printing member Forming the first photocurable pattern on the first portion, advancing the continuous transparent polymer web including the first portion containing the first photocurable pattern to approximate exposure radiation, and thereby on the first portion Forming a first photocurable pattern by applying the same or different photocurable composition to the second portion of the continuous transparent polymer web on the first support side by using the same or different flexographic printing members Or forming a second photocurable pattern on the second portion in sequence; including the second portion on the first support side including the second photocurable pattern Dividing the continuous transparent polymer web forward to approximate exposure radiation, and thereby forming a second photocurable pattern on the second portion of the first support side; using the same or different photocurable compositions as appropriate The same or different flexographic printing members form one or more other photo-curing patterns simultaneously or sequentially on one or more other portions of the first support side of the continuous transparent polymer web; electroless plating Each of the photocurable patterns on the support side to form a plurality of conductive metal patterns; and forming the dried outermost polymer on at least a portion but not all of each of the plurality of conductive metal patterns coating.

31.如實施例30之方法，其進一步包括在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外塗層之後：捲繞該連續聚合物網片。 31. The method of embodiment 30, further comprising, after forming the dried outermost coating on at least a portion but not all of the plurality of electrically conductive metal patterns: winding the continuous polymeric web.

32.如實施例28至30中任一項之方法，其進一步包括在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外塗層之後：將來自該連續透明聚合物網片之該等個別導電金屬圖案以個別物件形式組裝成相同或不同之個別器件。 The method of any one of embodiments 28 to 30, further comprising after forming the dried outermost coating on at least a portion but not all of the plurality of conductive metal patterns: from The individual conductive metal patterns of the continuous transparent polymer web are assembled in the form of individual articles into the same or different individual devices.

33.根據實施例28至32中任一項之方法，其進一步包括：使用包括金屬顆粒之光可固化組合物在該連續透明聚合物網片之相對第二支撐側之至少第一部分上形成光可固化圖案；將該光可固化圖案曝光於輻射以在該相對第二支撐側之該第一部分上形成光固化圖案；使用導電金屬無電電鍍該相對第二支撐側之該第一部分上之該光固化圖案以在該相對第二支撐側之該第一部分上形成導電金屬圖案；及在至少一部分但非全部該導電金屬圖案上形成乾燥最外聚合物 塗層，該乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The method of any one of embodiments 28 to 32, further comprising: forming light on at least a first portion of the opposite second support side of the continuous transparent polymer web using a photocurable composition comprising metal particles a curable pattern; exposing the photocurable pattern to radiation to form a photocurable pattern on the first portion of the opposite second support side; electroless plating the light on the first portion of the opposite second support side using a conductive metal Forming a conductive metal pattern on the first portion of the opposite second support side; and forming a dry outermost polymer coating on at least a portion but not all of the conductive metal pattern, the dried polymer coating having less than 5 μm The dry thickness, the integrated transmittance of at least 80%, and the non-crosslinked thermoplastic polymer having a glass transition temperature ( _Tg ) equal to or greater than 65 °C.

34.如實施例33之方法，其進一步包括：使用相同或不同之光可固化組合物及相同或不同之乾燥最外聚合物塗層，在該連續透明聚合物網片中不同於該相對第二支撐側上之該第一部分之該相對第二支撐側上之一或多個其他部分上，重複形成光可固化圖案、曝光、無電電鍍及形成乾燥最外聚合物塗層特徵。提供下列實例以闡釋本發明之實踐且不意欲以任何方式進行限制。代表性光可固化組合物1：此代表性光可固化組合物至少包括下列組份(形成為100g等分試樣)：14.4g環氧丙烯酸酯(來自Sartomer之CN 153)、9.9g聚(乙二醇)二丙烯酸酯(M_n為258，Sigma-Aldrich)、2.1g聚(乙二醇)二丙烯酸酯(M_n為575，Sigma-Aldrich)、10.8g新戊四醇四丙烯酸酯(Sigma-Aldrich)、0.8g混合於50%碳酸丙二酯中之六氟磷酸三芳基鋶鹽(Sigma-Aldrich)、0.8g混合於50%碳酸丙二酯中之六氟銻酸三芳基鋶鹽(Sigma-Aldrich)、2.4g自由基光起始劑羥基環己基苯基酮(Sigma-Aldrich)、1.2g自由基光起始劑甲基-4'-(甲硫基)-2-嗎啉基苯丙酮(Sigma-Aldrich)、19.5g「晶種」銀顆粒(來自NovaCentrix，20-25nm平均粒徑，Ag-25-ST3)、1.1g碳顆粒(US1074，來自US Nano)、0.001g 9-茀酮(Sigma-Aldrich)及35g 1-甲氧基異丙醇(Sigma-Aldrich)溶劑。 34. The method of embodiment 33, further comprising: using the same or different photocurable compositions and the same or different dry outermost polymer coatings, different from the relative number in the continuous transparent polymer web On one or more other portions of the first portion of the first support portion on the second support side, a photocurable pattern, an exposure, an electroless plating, and a dry outermost polymer coating feature are repeatedly formed. The following examples are provided to illustrate the practice of the invention and are not intended to be limiting in any way. Representative Photocurable Composition 1: This representative photocurable composition comprises at least the following components (formed as a 100 g aliquot): 14.4 g epoxy acrylate (CN 153 from Sartomer), 9.9 g poly ( ethylene glycol) diacrylate (M _n of 258, Sigma-Aldrich), 2.1g poly (ethylene glycol) diacrylate (M _n of 575, Sigma-Aldrich), 10.8g new pentaerythritol tetraacrylate ( Sigma-Aldrich), 0.8 g of triarylsulfonium hexafluorophosphate mixed with 50% propylene carbonate (Sigma-Aldrich), 0.8 g of triarylsulfonium hexafluoroantimonate mixed in 50% propylene carbonate (Sigma-Aldrich), 2.4 g of free radical photoinitiator hydroxycyclohexyl phenyl ketone (Sigma-Aldrich), 1.2 g of free radical photoinitiator methyl-4'-(methylthio)-2-morpholine Phenylpropiophenone (Sigma-Aldrich), 19.5 g "seed" silver particles (from NovaCentrix, 20-25 nm average particle size, Ag-25-ST3), 1.1 g carbon particles (US 1074, from US Nano), 0.001 g 9 - Anthrone (Sigma-Aldrich) and 35 g of 1-methoxyisopropanol (Sigma-Aldrich) solvent.

印刷光可固化組合物：Printing photocurable composition:

使用臺式測試印刷機「IGT F1印刷性測試儀」(來自IGT Testing Systems公司，Arlington Heights,IL)以柔版模式獲得位於各種塗底層聚(對苯二甲酸乙二酯)PET基板(MELLINEX^® 561，可自DuPont Teijin Films獲得)上之上文所闡述光可固化組合物之印刷圖案試樣。用於將光可固化組合物施加至柔版印刷板上之網紋輥系統具有1.3BCMI及1803lpi之值，如由IGT指定。在環境溫度下使用20N之網紋力、10N之印刷力及0.20m/sec之印刷速度形成印刷圖案。 Using a benchtop test press "IGT F1 Printability Tester" (from IGT Testing Systems, Inc., Arlington Heights, IL) to obtain a variety of undercoated poly(ethylene terephthalate) PET substrates (MELLINEX ^® ) in flexo mode 561, available from DuPont Teijin Films), a printed pattern sample of the photocurable composition described above. The anilox roll system for applying the photocurable composition to a flexographic printing plate has a value of 1.3 BCMI and 1803 lpi, as specified by IGT. A printed pattern was formed using a 20 N mesh force, a printing force of 10 N, and a printing speed of 0.20 m/sec at ambient temperature.

用於印刷光可固化組合物之柔版印刷板係市售KODAK^® Flexcel NX光聚合物板(來自Eastman Kodak公司)之試樣，其已使用遮罩進行UV輻射成像，該遮罩具有使用KODAK^® SQUARE SPOT雷射技術在12,800dpi之解析度下書寫之預定圖案。使用由製造商提出之已知條件處理(顯影)經曝光柔版光聚合物板。所得柔版印刷板(或部件)各自為1.14mm厚(包含PET)。用於將每一柔版印刷板安裝至印刷形式滾筒上之背襯膠帶為來自3M公司之1120米色膠帶，其為20密耳(0.051cm)厚且蕭氏A(Shore A)值為55。柔版印刷板中之凸版影像設計包含具有在頂部凸版表面上之寬度為7μm之精細線之柵格圖案。所得相應印刷光可固化組合物圖案具有佈置於塗底層PET基板上之平均線寬度。 A flexographic printing plate for printing a photocurable composition is a sample of a commercially available KODAK ^® Flexcel NX photopolymer plate (from Eastman Kodak Co., Ltd.) which has been subjected to UV radiation imaging using a mask having KODAK ^® SQUARE SPOT laser technology writes a predetermined pattern at a resolution of 12,800 dpi. The exposed flexographic photopolymer plate is treated (developed) using known conditions as proposed by the manufacturer. The resulting flexographic printing plates (or parts) were each 1.14 mm thick (including PET). The backing tape used to mount each flexographic printing plate to the printing form cylinder was a 1120 meter color tape from 3M Company, which was 20 mils (0.051 cm) thick and had a Shore A value of 55. The relief image design in flexographic printing plates comprises a grid pattern having fine lines of 7 [mu]m width on the top relief surface. The resulting corresponding printed photocurable composition pattern has an average line width disposed on the undercoated PET substrate.

在施加至基板上之後，利用UV輻射使用Fusion 300 WPI中壓汞燈(提供介於190-1500nm之間之輻照波長)利用298mJ/cm²之近似暴露輻照光可固化組合物之每一印刷圖案(亦即印刷圖案)以光固化每一印刷圖案。以透射及反射模式使用Olympus BH-2光學顯微鏡量測所得前體物件中之所得光固化圖案之印刷平均線寬度。 After application to the substrate, a Fusion 300 WPI medium pressure mercury lamp (providing an irradiation wavelength between 190 and 1500 nm) was used to approximate the exposure of the irradiated light curable composition with 298 mJ/cm ² using UV radiation. The printed pattern (ie, the printed pattern) is photocured with each printed pattern. The printed average line width of the resulting photocured pattern in the resulting precursor article was measured in a transmission and reflection mode using an Olympus BH-2 optical microscope.

無電金屬電鍍：Electroless metal plating:

藉由將具有固化圖案之前體物件在45℃下於含有Enplate Cu-406無電電鍍溶液(ENTHONE^®公司)的燒杯中浸沒7分鐘來無電銅電鍍包括位於各種塗底層基板上之光固化圖案之前體物件，隨後使用蒸餾水沖洗且使用氮乾燥以形成具有佈置於基板上之導電圖案之物件。 By previously having the cured pattern body object at 45 ℃ containing Enplate Cu-406 beakers electroless plating solution (ENTHONE ^® Corporation) was immersed for 7 minutes in an electroless copper plating includes a variety of light on the primed substrate cured pattern before the body The article is then rinsed with distilled water and dried using nitrogen to form an article having a conductive pattern disposed on the substrate.

最外聚合物塗層調配物：The outermost polymer coating formulation:

製備具有10重量%存於1-甲氧基-2-丙醇(DOWANOL^® PM有機溶劑)中之ELVACITE^® 4028樹脂(Lucite International)之最外聚合物塗層調配物。調配物較為澄清且在22℃下具有25cps之黏度。 Preparing a 10% by weight present in the 1-methoxy-2-propanol (DOWANOL ^® PM organic solvent) of ELVACITE ^® 4028 resin (Lucite International) the most outer polymeric coating formulations. The formulation was clear and had a viscosity of 25 cps at 22 °C.

印刷最外聚合物塗層調配物：Printing the outermost polymer coating formulation:

根據本發明藉由使用柔版印刷壓機(Performance Series P7，可自Mark Andy公司獲得)以連續捲對捲操作且使用單一柔版站來提供乾燥最外聚合物塗層。此柔版站包括塔盤(其裝填有300克最外聚合物塗層調配物)、彈性計量輥(硬度大約為30蕭氏A)、陶瓷網紋輥(具有鋼醫用刮刀)及柔版板輥。在此製程中，藉由彈性計量輥將最外聚合物塗層調配物自塔盤遞送至網紋輥中。藉由鋼醫用刮刀自網紋輥去除過量最外聚合物塗層調配物。網紋輥系統具有2.0 BCMI(十億μm³/in²)之值，其等效於0.31十億μm³/cm²。 The dry outermost polymer coating is provided in accordance with the present invention by using a flexographic printing press (Performance Series P7, available from Mark Andy) in a continuous roll-to-roll operation and using a single flexographic station. This flexo station consists of a tray (filled with 300 grams of the outermost polymer coating formulation), an elastic metering roll (hardness of approximately 30 Shore A), a ceramic anilox roll (with a steel medical blade) and a flexo Plate roll. In this process, the outermost polymer coating formulation is delivered from the tray to the anilox roll by an elastic metering roll. Excess outermost polymer coating formulations were removed from the anilox roll by a steel medical doctor blade. The anilox roll system has a value of 2.0 BCMI (billion μm ³ /in ² ) which is equivalent to 0.31 billion μm ³ /cm ² .

然後將最外聚合物塗層調配物轉移至如下文所闡述獲得之柔版印刷板中且然後轉移至含有上文在連續網片製程中所闡述無電金屬電鍍導電圖案之移動網片中。在18℃及50%相對濕度下在0.10m/sec之線速度下實施所有印刷、乾燥及捲繞操作。最終乾燥導電物件具有佈置於至少一部分但非全部每一導電圖案上之乾燥最外聚合物塗層，該乾燥塗層厚0.3μm。 The outermost polymer coating formulation is then transferred to a flexographic printing plate as set forth below and then transferred to a moving web containing the electroless metal plated conductive pattern set forth above in the continuous web process. All printing, drying and winding operations were carried out at 18 ° C and 50% relative humidity at a line speed of 0.10 m/sec. The final dried conductive article has a dried outermost polymer coating disposed on at least a portion but not all of the conductive patterns, the dried coating having a thickness of 0.3 [mu]m.

自已使用遮罩(具有使用KODAK^® SQUARE SPOT雷射技術在12,800dpi之解析度下書寫之預定圖案)成像之市售KODAK^® Flexcel NX光聚合物板(Eastman Kodak公司)形成用於施加(印刷)最外聚合物塗層調配物之柔版印刷板。使用由製造商提出之已知條件處理(顯影)UV曝光柔版光聚合物板。所得柔版印刷板大約為1mm厚。除標記為導電圖案最外部分之區中之矩形凸版區(2×35mm)外，柔版印刷板之表面保持平滑(亦即按接收狀態)。此凸版區並不接收(或傳輸)最外聚 合物塗層調配物且因此在所得導電物件中每一導電圖案之較小部分保持為「開放」(未塗覆)。此未塗覆區對應於印刷導電連結器之區。 Self-contained KODAK ^® Flexcel NX Photopolymer Sheet (Eastman Kodak Co., Ltd.) imaged using a mask (with a predetermined pattern written using KODAK ^® SQUARE SPOT laser technology at a resolution of 12,800 dpi) for application (printing) A flexographic printing plate of the outermost polymer coating formulation. The UV-exposed flexographic photopolymer plate was treated (developed) using known conditions as proposed by the manufacturer. The resulting flexographic printing plate was approximately 1 mm thick. The surface of the flexographic printing plate remains smooth (i.e., in a receiving state) except for the rectangular relief region (2 x 35 mm) in the region marked as the outermost portion of the conductive pattern. This relief region does not receive (or transport) the outermost polymer coating formulation and thus maintains a relatively "open" (uncoated) portion of each conductive pattern in the resulting conductive article. This uncoated area corresponds to the area where the conductive connector is printed.

試樣之環境暴露：Environmental exposure of the sample:

將所有如上文所闡述製得之導電物件在維持於65℃及90% RH(相對濕度)之環境室中培育4週。導電物件垂直懸掛於環境室中且以不同時間間隔取出以用於評價電性質。 All of the electrically conductive articles prepared as described above were incubated for 4 weeks in an environmental chamber maintained at 65 ° C and 90% RH (relative humidity). Conductive articles are suspended vertically in the environmental chamber and taken out at different time intervals for evaluation of electrical properties.

電連續性之量測：Measurement of electrical continuity:

此導電物件之導電圖案包含多個導電柵格網絡，其中每一導電柵格網絡之終點連結至兩個探針墊，一個探針墊(近探針墊)連結至BUS導電線，其繼而可連結至「連結器」接合墊(其連結至外部電路)。「連結器」可包括多個連結器接合墊。第二探針墊(遠探針墊)連結至電路徑中距「連結器」接合墊最遠之點處之導電柵格。對於本實例而言，連結器接合墊未經最外聚合物塗層調配物塗覆以提供可用於量測電阻之連結器。 The conductive pattern of the conductive article comprises a plurality of conductive grid networks, wherein the end of each conductive grid network is connected to two probe pads, and one probe pad (near probe pad) is coupled to the BUS conductive line, which in turn Connect to the "connector" bond pad (which is connected to an external circuit). A "connector" can include a plurality of connector bond pads. The second probe pad (distal probe pad) is coupled to the conductive grid at the point farthest from the "connector" bond pad in the electrical path. For the present example, the bond pads were not coated with the outermost polymer coating formulation to provide a connector that could be used to measure resistance.

藉由向每一導電圖案中之每一導電連結器施加脈衝電壓(25伏特，DC)且量測連結器接合墊與相應末端探針墊之間的電流來測試上文所闡述經培育導電物件之電連續性。因此，電流路徑係自外部電路至連結器接合墊，其穿過BUS線、穿過近探針墊、穿過導電柵格網絡(長度大約300mm)並到達末端探針墊。然後使用歐姆定律(Ohm’s Law)測定電阻。此路徑中大於1000歐姆之電阻視為失敗且視為「斷路」。對於該等實例中所使用之每一導電物件而言，存在34個接合墊位點及34個晶格列網絡。因此，每一導電物件(且由此每一導電圖案)中可能「斷路」結果之最大數量為34。 The incubated conductive article described above is tested by applying a pulse voltage (25 volts, DC) to each of the conductive connectors and measuring the current between the bond pads and the respective end probe pads. Electrical continuity. Thus, the current path is from the external circuit to the connector bond pad, which passes through the BUS line, through the proximity probe pad, through the conductive grid network (about 300 mm in length), and to the end probe pad. The resistance was then measured using Ohm's Law. A resistance greater than 1000 ohms in this path is considered a failure and is considered an "open circuit." For each of the conductive articles used in these examples, there are 34 bond pad sites and 34 lattice column networks. Thus, the maximum number of possible "break" results in each conductive article (and thus each conductive pattern) is 34.

透明性之量測：Measurement of transparency:

藉由如上文所闡述量測在550nm下輻射之積分透射率來評估每一導電物件之透明性。 The transparency of each conductive article was evaluated by measuring the integrated transmittance of radiation at 550 nm as described above.

對比實例：Comparison example:

將如上文所闡述製得之導電物件發送至所述柔版印刷壓機上且並不施加最外聚合物塗層調配物。所得對比性導電物件由此在導電圖案上並不包括乾燥最外聚合物塗層。隨後如上文所闡述測試每一對比性導電物件之初始電連續性。三個對比性導電物件中之每一者之初始平均積分透射率為84%。 Conductive articles made as described above were sent to the flexographic printing press and the outermost polymer coating formulation was not applied. The resulting comparative conductive article thus does not include a dry outermost polymer coating on the conductive pattern. The initial electrical continuity of each of the comparative electrically conductive articles was then tested as set forth above. The initial average integrated transmission of each of the three contrast conductive articles was 84%.

然後如上文針對本發明導電物件所闡述，在環境室中培育對比性物件且週期性取出以評估電連續性。下表I展示對比性物件之「斷路」評估之數量之增加。如表I中所展示，在4週培育時段中，每一導電物件中「斷路」評估之平均數量漸進地增加5。 The contrast articles were then grown in an environmental chamber as described above for the conductive article of the present invention and periodically removed for evaluation of electrical continuity. Table I below shows the increase in the number of "open circuit" assessments of comparative objects. As shown in Table I, the average number of "open circuit" evaluations in each conductive article was progressively increased by 5 during the 4-week incubation period.

本發明實例：An example of the invention:

將9個如上文所闡述製得之導電物件發送至所述柔版印刷壓機中，該柔版印刷壓機與含有最外聚合物塗層調配物之印刷站充分嚙合。因此，除導電圖案之較小矩形區(2mm×35mm)外，該等本發明導電物件中之每一者包括施加於包含導電金屬柵格之導電圖案上之乾燥最外聚合物塗層。最外保護性塗層之乾燥厚度為0.3μm。所有9個導電物件之初始積分透射率經測定為84%。 Electrically conductive articles prepared as described above were sent to the flexographic printing press, which was fully meshed with the printing station containing the outermost polymer coating formulation. Thus, in addition to the smaller rectangular area of the conductive pattern (2 mm x 35 mm), each of the electrically conductive articles of the present invention comprises a dried outermost polymeric coating applied to a conductive pattern comprising a conductive metal grid. The outermost protective coating has a dry thickness of 0.3 μm. The initial integrated transmittance of all nine conductive articles was determined to be 84%.

如上文所闡述，在環境室中培育本發明物件且週期性取出評估電連續性。下表I展示本發明導電物件之「斷路」評估之數量之增加。如表I中所展示，在4週培育時段中，「斷路」評估之平均數量並不增加。因此，經測定，每一導電物件中佈置於上至少一部分但非全部導電圖案上之乾燥最外聚合物塗層會良好地保護導電圖案免受污染物(例如水及氧)影響，即使在苛刻環境條件下。 As explained above, the inventive article is incubated in an environmental chamber and periodically extracted to assess electrical continuity. Table I below shows the increase in the number of "open circuit" evaluations of the electrically conductive articles of the present invention. As shown in Table I, the average number of "open circuit" assessments did not increase during the 4-week incubation period. Thus, it has been determined that the dried outermost polymer coating disposed on at least a portion but not all of the conductive patterns in each of the electrically conductive articles will well protect the electrically conductive pattern from contaminants (eg, water and oxygen), even in harsh conditions. Under environmental conditions.

Claims (34)

一種導電物件，其包括：透明基板，其具有第一支撐側及相對第二支撐側；佈置於至少該第一支撐側上之導電圖案，及乾燥最外聚合物塗層，其佈置於至少一部分但非全部該導電圖案上，該乾燥最外聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 A conductive article comprising: a transparent substrate having a first support side and an opposite second support side; a conductive pattern disposed on at least the first support side, and a dry outermost polymer coating disposed at least in part But not all of the conductive patterns, the dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a non-crosslinked thermoplastic polymerization comprising a glass transition temperature (T _g ) equal to or greater than 65 ° C. Things. 如請求項1之導電物件，其中該導電圖案至少包括：導電柵格；及導電連結器，其連結至該導電柵格。 The conductive article of claim 1, wherein the conductive pattern comprises at least: a conductive grid; and a conductive connector coupled to the conductive grid. 如請求項2之導電物件，其中該乾燥最外聚合物塗層佈置於100%或以下之該導電柵格上，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上。 The conductive article of claim 2, wherein the dried outermost polymer coating is disposed on the conductive grid of 100% or less, but the dried outermost polymer coating is disposed on the conductive connector of less than 100% . 如請求項2或3之導電物件，其中該導電柵格係導電金屬柵格且該導電連結器係連結至其之導電金屬連結器。 The conductive article of claim 2 or 3, wherein the conductive grid is a conductive metal grid and the conductive connector is coupled to the conductive metal bond. 如請求項1至4中任一項之導電物件，其進一步包括：佈置於該透明基板之相對第二支撐側上之導電圖案，及乾燥最外聚合物層，其佈置於該透明基板之該相對第二支撐側上之至少一部分但非全部該導電圖案上，此乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The conductive article of any one of claims 1 to 4, further comprising: a conductive pattern disposed on the opposite second support side of the transparent substrate, and a dry outermost polymer layer disposed on the transparent substrate The dry polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or greater than 65 on at least a portion but not all of the conductive pattern on the second support side. Non-crosslinked thermoplastic polymer at °C. 如請求項5之導電物件，其中該導電圖案至少包括：導電柵格，及導電連結器，其連結至該導電柵格。 The conductive article of claim 5, wherein the conductive pattern comprises at least: a conductive grid, and a conductive connector coupled to the conductive grid. 如請求項6之導電物件，其中該乾燥最外聚合物塗層佈置於100%或以下之該導電柵格上，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上，所有皆位於該透明基板之該相對第二支撐側上。 The conductive article of claim 6, wherein the dry outermost polymer coating is disposed on the conductive grid of 100% or less, but the dry outermost polymer coating is disposed on the conductive connector of less than 100% All are located on the opposite second support side of the transparent substrate. 如請求項1至7中任一項之導電物件，其中該非交聯熱塑性聚合物係非交聯、非芳香族熱塑性聚合物。 The electrically conductive article of any one of claims 1 to 7, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked, non-aromatic thermoplastic polymer. 如請求項1至8中任一項之導電物件，其中該乾燥最外聚合物塗層具有小於3μm之乾燥厚度。 The electrically conductive article of any one of claims 1 to 8, wherein the dried outermost polymer coating has a dry thickness of less than 3 μm. 如請求項1至9中任一項之導電物件，其中該非交聯熱塑性聚合物係非交聯熱塑性丙烯酸聚合物。 The electrically conductive article of any one of claims 1 to 9, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic acrylic polymer. 如請求項1至10中任一項之導電物件，其中該非交聯熱塑性聚合物包括至少衍生自(甲基)丙烯酸甲酯之重複單元及衍生自(甲基)丙烯酸烷基酯之重複單元，其中該烷基具有1至18個碳原子，其中衍生自(甲基)丙烯酸烷基酯之該等重複單元佔總聚合物重複單元之至少5mol%且至多並包含25mol%。 The conductive article of any one of claims 1 to 10, wherein the non-crosslinked thermoplastic polymer comprises at least a repeating unit derived from methyl (meth) acrylate and a repeating unit derived from an alkyl (meth) acrylate. Wherein the alkyl group has from 1 to 18 carbon atoms, wherein the repeating units derived from the alkyl (meth) acrylate comprise at least 5 mol% and up to and including 25 mol% of the total polymer repeating unit. 如請求項1至11中任一項之導電物件，其中至少佈置於該透明基板之該第一支撐側上之該導電圖案包括由至少銀、銅、鈀或鉑構成之導電金屬線。 The conductive article of any one of claims 1 to 11, wherein the conductive pattern disposed on at least the first support side of the transparent substrate comprises a conductive metal wire composed of at least silver, copper, palladium or platinum. 如請求項5至12中任一項之導電物件，其中佈置於該透明基板之該相對第二支撐側上之該導電圖案包括至少由銀、銅、鈀或鉑構成之導電金屬線。 The conductive article of any one of claims 5 to 12, wherein the conductive pattern disposed on the opposite second support side of the transparent substrate comprises a conductive metal wire composed of at least silver, copper, palladium or platinum. 如請求項1至13中任一項之導電物件，其中該透明基板係連續透明聚合物網片，且該物件包括相同或不同之佈置於該連續透明聚合物網片之該第一支撐側之至少第一部分及該相對第二支撐側之至少第一部分上的導電圖案。 The conductive article of any one of claims 1 to 13, wherein the transparent substrate is a continuous transparent polymer mesh, and the article comprises the same or different ones disposed on the first support side of the continuous transparent polymer mesh. a conductive pattern on at least the first portion and at least the first portion of the opposite second support side. 如請求項14之導電物件，其中該連續透明聚合物網片包括： 位於該第一支撐側上之多個部分及位於該相對第二支撐側上之多個部分；分別佈置於該透明基板之該第一支撐側及該相對第二支撐側上之該多個部分上之相同或不同之導電圖案；及乾燥最外聚合物塗層，其佈置於至少一部分但非全部之每一導電圖案上。 The conductive article of claim 14, wherein the continuous transparent polymer mesh comprises: a plurality of portions on the first support side and a plurality of portions on the opposite second support side; the plurality of portions respectively disposed on the first support side and the opposite second support side of the transparent substrate And the same or different conductive patterns; and a dry outermost polymer coating disposed on at least a portion but not all of the conductive patterns. 一種電子器件，其包括作為觸控螢幕之如請求項1至15中任一項之導電物件。 An electronic device comprising a conductive object as any one of claims 1 to 15 as a touch screen. 如請求項16之電子器件，其中該觸控螢幕具有至少1cm²且至多並包含100m²之觀看面積。 The electronic device of claim 16, wherein the touch screen has a viewing area of at least 1 cm ² and at most and 100 m ² . 一種提供如請求項1至15中任一項之導電物件之方法，該方法包括：在透明基板之第一支撐側上形成導電圖案，該透明基板亦包括相對第二支撐側；及在至少一部分但非全部該導電圖案上形成乾燥最外聚合物塗層，該乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 A method of providing a conductive article according to any one of claims 1 to 15, the method comprising: forming a conductive pattern on a first support side of the transparent substrate, the transparent substrate also including a second support side; and at least a portion However, not all of the conductive patterns form a dry outermost polymer coating having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or greater than 65 ° C. Non-crosslinked thermoplastic polymer. 如請求項18之方法，其中該導電圖案至少包括：導電柵格，及導電連結器，其連結至該導電柵格。 The method of claim 18, wherein the conductive pattern comprises at least: a conductive grid, and a conductive connector coupled to the conductive grid. 如請求項19之方法，其包括在100%或以下之該導電柵格上形成該乾燥最外聚合物塗層，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上。 The method of claim 19, comprising forming the dried outermost polymer coating on the conductive grid of 100% or less, but the dry outermost polymer coating is disposed on the conductive connector of less than 100% . 如請求項19之方法，其中該導電柵格係導電金屬柵格且該導電連結器係連結至其之導電金屬連結器。 The method of claim 19, wherein the conductive grid is a conductive metal grid and the conductive connector is coupled to a conductive metal bond. 如請求項18至21中任一項之方法，其進一步包括：在該透明基板之該相對第二支撐側上形成導電圖案，及在該透明基板之該相對第二支撐側上之至少一部分但非全部該導電圖案上形成乾燥最外聚合物塗層，此乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The method of any one of claims 18 to 21, further comprising: forming a conductive pattern on the opposite second support side of the transparent substrate, and at least a portion of the opposite second support side of the transparent substrate A dry outermost polymer coating is formed on all of the conductive patterns, the dry polymer coating having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or greater than 65 ° C. Non-crosslinked thermoplastic polymer. 如請求項22之方法，其中該相對第二支撐側上之該導電圖案包括導電柵格及連結至該導電柵格之導電連結器。 The method of claim 22, wherein the conductive pattern on the opposite second support side comprises a conductive grid and a conductive connector coupled to the conductive grid. 如請求項22或23中任一項之方法，其包括在100%或以下之該導電柵格上形成該乾燥最外聚合物塗層，但該乾燥最外聚合物塗層佈置於小於100%之該導電連結器上，所有皆位於該透明基板之該相對第二支撐側上。 The method of any one of claims 22 or 23, comprising forming the dried outermost polymer coating on the conductive grid of 100% or less, but the dry outermost polymer coating is disposed at less than 100% All of the conductive connectors are located on the opposite second support side of the transparent substrate. 如請求項18至24中任一項之方法，其包括使用柔版印刷部件在該第一支撐側上形成該最外聚合物塗層。 The method of any one of claims 18 to 24, comprising forming the outermost polymer coating on the first support side using a flexographic printing member. 如請求項18至25中任一項之方法，其包括在係連續透明聚合物網片之該基板之第一部分上形成該導電圖案。 The method of any one of claims 18 to 25, comprising forming the conductive pattern on a first portion of the substrate that is a continuous transparent polymer web. 如請求項18至26中任一項之方法，其包括：在係連續透明聚合物網片之該基板之該第一支撐側上之各別多個部分上形成多個導電圖案，及在該多個部分中之該等導電圖案中之每一者之至少一部分但非全部部分上形成乾燥最外聚合物塗層，該乾燥最外聚合物塗層佈置於該多個導電圖案中之每一者上且具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The method of any one of claims 18 to 26, comprising: forming a plurality of conductive patterns on respective portions of the first support side of the substrate of the continuous transparent polymer web, and Forming a dry outermost polymer coating on at least a portion but not all of each of the plurality of portions of the conductive patterns, the dry outermost polymer coating being disposed in each of the plurality of conductive patterns And having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a non-crosslinked thermoplastic polymer having a glass transition temperature (T _g ) equal to or greater than 65 ° C. 一種提供如請求項1至15中任一項之導電物件之方法，該方法包括： (i)提供呈連續透明聚合物網片形式之基板；(ii)使用包括金屬顆粒之光可固化組合物在該連續透明聚合物網片之第一支撐側上之至少第一部分上形成第一光可固化圖案；(iii)將該光可固化圖案曝光於光固化輻射以在該第一支撐側之該第一部分上形成光固化圖案；(iv)使用導電金屬無電電鍍該第一支撐側之該第一部分上之該光固化圖案以在該第一支撐側之該第一部分上形成導電金屬圖案；及(v)在該第一支撐側之該第一部分中之至少一部分但非全部導電圖案上形成乾燥最外聚合物塗層。 A method of providing a conductive article according to any one of claims 1 to 15, the method comprising: (i) providing a substrate in the form of a continuous transparent polymer web; (ii) forming a first on at least a first portion of the first support side of the continuous transparent polymer web using a photocurable composition comprising metal particles a photocurable pattern; (iii) exposing the photocurable pattern to photocuring radiation to form a photocurable pattern on the first portion of the first support side; (iv) electroless plating the first support side using a conductive metal The photocuring pattern on the first portion forms a conductive metal pattern on the first portion of the first support side; and (v) at least a portion but not all of the conductive patterns on the first portion of the first support side A dry outermost polymer coating is formed. 如請求項28之方法，其進一步包括：使用相同或不同之光可固化組合物及相同或不同之乾燥最外聚合物塗層，在該連續透明聚合物網片之該第一支撐側上之一或多個不同於該第一部分之其他部分上重複特徵(ii)至(v)。 The method of claim 28, further comprising: using the same or different photocurable composition and the same or different dry outermost polymer coating on the first support side of the continuous transparent polymer web Features (ii) through (v) are repeated on one or more other portions than the first portion. 如請求項28或29之方法，其包括：藉由使用第一柔版印刷部件將該光可固化組合物施加至該連續透明聚合物網片之該第一支撐側上之第一部分上來在該第一部分上形成該第一光可固化圖案；使包括含有該第一光可固化圖案之該第一部分之該連續透明聚合物網片前進以接近曝光輻射，且由此在該第一部分上形成第一光固化圖案；藉由使用相同或不同之柔版印刷部件將相同或不同之光可固化組合物施加至該連續透明聚合物網片之該第一支撐側上之第二部分來同時或依序在該第二部分上形成第二光可固化圖案；使包括含有該第二光可固化圖案之該第一支撐側上之該第二 部分之該連續透明聚合物網片前進以接近曝光輻射，且由此在該第一支撐側之該第二部分上形成第二光固化圖案；視情況使用相同或不同之光可固化組合物及相同或不同之柔版印刷部件在該連續透明聚合物網片中該第一支撐側上之一或多個其他部分上同時或依序形成一或多個其他光固化圖案；無電電鍍該第一支撐側上之該等光固化圖案中之每一者以形成多個導電金屬圖案；及在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外聚合物塗層。 The method of claim 28 or 29, comprising: applying the photocurable composition to the first portion of the continuous transparent polymer web on the first support side by using a first flexographic printing member Forming the first photocurable pattern on the first portion; advancing the continuous transparent polymer web including the first portion containing the first photocurable pattern to approximate exposure radiation, and thereby forming a first portion on the first portion a photocurable pattern; applying the same or different photocurable composition to the second portion of the first support side of the continuous transparent polymer web by using the same or different flexographic printing members simultaneously or Forming a second photocurable pattern on the second portion; causing the second surface on the first support side to include the second photocurable pattern Part of the continuous transparent polymer web advances to approximate exposure radiation, and thereby forming a second photocurable pattern on the second portion of the first support side; using the same or different photocurable compositions as appropriate The same or different flexographic printing members form one or more other photo-curing patterns simultaneously or sequentially on one or more other portions of the first support side of the continuous transparent polymer web; electroless plating Each of the photocurable patterns on the support side to form a plurality of conductive metal patterns; and forming the dried outermost polymer on at least a portion but not all of each of the plurality of conductive metal patterns coating. 如請求項30之方法，其進一步包括在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外塗層之後：捲繞該連續聚合物網片。 The method of claim 30, further comprising, after forming the dried outermost coating on at least a portion but not all of the plurality of electrically conductive metal patterns: winding the continuous polymeric web. 如請求項28至30中任一項之方法，其進一步包括在該多個導電金屬圖案中之每一者之至少一部分但非全部部分上形成該乾燥最外塗層之後：將來自該連續透明聚合物網片之該等個別導電金屬圖案作為個別物件組裝成相同或不同之個別器件。 The method of any one of claims 28 to 30, further comprising after forming the dried outermost coating on at least a portion but not all of the plurality of conductive metal patterns: from the continuous transparent The individual conductive metal patterns of the polymer web are assembled as individual items into the same or different individual devices. 如請求項28至32中任一項之方法，其進一步包括：使用包括金屬顆粒之光可固化組合物在該連續透明聚合物網片之相對第二支撐側之至少第一部分上形成光可固化圖案；將該光可固化圖案曝光於輻射以在該相對第二支撐側之該第一部分上形成光固化圖案；使用導電金屬無電電鍍該相對第二支撐側之該第一部分上之該光固化圖案以在該相對第二支撐側之該第一部分上形成導電金屬圖案；及 在至少一部分但非全部之該導電金屬圖案上形成乾燥最外聚合物塗層，該乾燥聚合物塗層具有小於5μm之乾燥厚度、至少80%之積分透射率且包括玻璃轉變溫度(T_g)等於或大於65℃之非交聯熱塑性聚合物。 The method of any one of claims 28 to 32, further comprising: forming a photocurable on at least a first portion of the opposite second support side of the continuous transparent polymer web using a photocurable composition comprising metal particles a pattern; exposing the photocurable pattern to radiation to form a photocurable pattern on the first portion of the opposite second support side; electroless plating the photocuring pattern on the first portion of the opposite second support side using a conductive metal Forming a conductive metal pattern on the first portion of the opposite second support side; and forming a dry outermost polymer coating on at least a portion but not all of the conductive metal pattern, the dried polymer coating having less than 5 μm Dry thickness, at least 80% integrated transmittance and including a non-crosslinked thermoplastic polymer having a glass transition temperature ( _Tg ) equal to or greater than 65 °C. 如請求項33之方法，其進一步包括：使用相同或不同之光可固化組合物及相同或不同之乾燥最外聚合物塗層，在該連續透明聚合物網片之該相對第二支撐側上之不同於該相對第二支撐側上之該第一部分之一或多個其他部分上，重複形成光可固化圖案、曝光、無電電鍍及形成乾燥最外聚合物塗層特徵。 The method of claim 33, further comprising: using the same or different photocurable compositions and the same or different dry outermost polymer coatings on the opposite second support side of the continuous transparent polymer web On one or more other portions of the first portion on the opposite second support side, a photocurable pattern, exposure, electroless plating, and formation of a dry outermost polymer coating feature are repeatedly formed.