TWI665270B - Latex primer composition and latex primed substrates - Google Patents

Abstract

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，從而黏著具有細線之圖案化材料。該第一聚合物乳膠包括第一聚合物及第一表面活性劑，使得該第一聚合物乳膠之乾燥塗層具有至少50%之表面極性。該第二聚合物乳膠包括第二聚合物及第二表面活性劑，使得該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。另外，該混合物之乾燥塗層具有至少15%且至多並包含50%之表面極性。打底基板可用於藉由將圖案化材料施加至基板上來製備直接在乾燥底漆層上具有導電細線之導電物件。該等物件可用作各種電子器件中之觸控螢幕顯示器。 The first polymer latex and the second polymer latex may be mixed to form a dry primer layer on the substrate, thereby adhering a patterned material having fine lines. The first polymer latex includes a first polymer and a first surfactant, so that the dry coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex includes a second polymer and a second surfactant, so that the dry coating of the second polymer latex has a surface polarity of less than or equal to 27%. In addition, the dry coating of the mixture has a surface polarity of at least 15% and at most 50%. The primer substrate can be used to prepare a conductive object having conductive thin wires directly on the dried primer layer by applying a patterning material to the substrate. These objects can be used as touch screen displays in various electronic devices.

Description

乳膠底漆組合物及經乳膠打底之基板 Latex primer composition and latex-primed substrate

本發明係關於一種塗層組合物及具有塗覆於載體(例如透明載體)上之塗層組合物之基板。此塗層組合物用作底漆層以將圖案化材料黏著至基板上，且包括兩種不同聚合物乳膠(各自含有聚合物顆粒及表面活性劑)之混合物。所得圖案化物件可用於各種目的且在圖案係導電材料時，圖案化物件可用作(例如)含有觸控螢幕之器件中之導電膜。 The present invention relates to a coating composition and a substrate having a coating composition coated on a carrier, such as a transparent carrier. This coating composition is used as a primer layer to adhere a patterning material to a substrate, and includes a mixture of two different polymer latexes (each containing polymer particles and a surfactant). The obtained patterned object can be used for various purposes and when the pattern is a conductive material, the patterned object can be used as, for example, a conductive film in a device containing a touch screen.

打底基板已用於許多工業中以更佳地黏著上覆層、圖案或文本。術語「打底」通常係指使用通常係乾燥聚合塗層之塗層，其對具有期望平滑度及組成之下伏基板及對上覆材料具有良好黏著。 Primer substrates have been used in many industries to better adhere overlays, patterns, or text. The term "priming" generally refers to the use of a coating, usually a dry polymeric coating, which has good adhesion to underlying substrates having a desired smoothness and composition and to overlying materials.

舉例而言，可圖案化材料可用於各種工業中以提供導電或非導電線、固體區、文本、柵格、電路或其他形狀之圖案。可使用凸版印刷部件將該等圖案施加至各種基板上，且可進一步處理所得圖案以提供用於電子器件、顯示器或能源工業中之導電性或其他性質。舉例而言，可在透明基板上設計及製備導電圖案以用於各種顯示器件中(例如用作觸控螢幕)。 For example, patternable materials can be used in various industries to provide patterns of conductive or non-conductive lines, solid areas, text, grids, circuits, or other shapes. These patterns can be applied to various substrates using letterpress printing components, and the resulting patterns can be further processed to provide conductivity or other properties for use in the electronic device, display, or energy industries. For example, a conductive pattern can be designed and prepared on a transparent substrate for use in various display devices (for example, as a touch screen).

數十年來，聚酯及其他聚合膜已熟知可用作施加塗層或圖案之基板。此類型聚合膜(或物件)通常因其強度、撓性及潛在透明性而更 適用於各種目的，包含印刷部件、成像元件及顯示器件。然而，端視擬施加材料，在試圖在聚合基板與上覆塗層或圖案之間產生及維持強黏著力之過程中，通常產生實際困難，此乃因聚合基板通常具有高疏水性且上覆塗層或圖案可具有較小疏水性。另一選擇為，聚合基板之疏水性可小於上覆塗層或圖案。 For decades, polyester and other polymeric films have been well known as substrates for applying coatings or patterns. This type of polymeric film (or object) is usually more robust due to its strength, flexibility, and potential transparency. Suitable for various purposes including printed parts, imaging elements and display devices. However, the end view intends to apply materials in the process of trying to generate and maintain strong adhesion between the polymer substrate and the overcoating layer or pattern, which usually causes practical difficulties, because the polymer substrate is usually highly hydrophobic and overlying. The coating or pattern may be less hydrophobic. Alternatively, the polymeric substrate may be less hydrophobic than the overcoat or pattern.

許多問題源自各種工業中之較差黏著。觸控敏感性面板或顯示器需要在預定圖案中具有極細線(寬度約小於20μm)以達成期望導電性同時具有高目測透明性(或高積分透射率)。 Many problems stem from poor adhesion in various industries. The touch-sensitive panel or display needs to have extremely thin lines (with a width of less than about 20 μm) in a predetermined pattern to achieve the desired conductivity while having high visual transparency (or high integrated transmittance).

在製造及使用導電材料(包含導電金屬或金屬前體)之細線期間不能達成或維持適當黏著時，不能達成期望導電性或電容。美國專利申請公開案2007/0170403(Conaghan等人)闡述該等黏著問題且提出一些藉由在基板上使用各種黏著劑或底漆層或將黏著促進化合物納入所施加導電「油墨」(組合物)中來達成之解決方案。 When proper adhesion cannot be achieved or maintained during the manufacture and use of thin wires of conductive materials (including conductive metals or metal precursors), the desired conductivity or capacitance cannot be achieved. U.S. Patent Application Publication 2007/0170403 (Conaghan et al.) Addresses these adhesion issues and proposes that by using various adhesives or primer layers on the substrate or incorporating adhesion promoting compounds into the applied conductive "ink" (composition) The solution reached in China.

舉例而言，可使用經施加以支撐聚合膜之表面之聚合底漆層來改良撓性及透明基板之黏著及各種表面性質。尤其在以均勻形式施加後續施加之材料時，期望更佳地黏著彼等材料。用於此目的之底漆層組合物之實例闡述於(例如)美國專利6,162,597(Bauer等人)及6,165,699(Bauer等人)中。 For example, a polymeric primer layer applied to support the surface of a polymeric film can be used to improve the adhesion and various surface properties of flexible and transparent substrates. Especially when subsequently applied materials are applied in a uniform form, it is desirable to better adhere to them. Examples of primer layer compositions used for this purpose are described, for example, in US Patents 6,162,597 (Bauer et al.) And 6,165,699 (Bauer et al.).

另外，美國專利申請公開案2013/0319275(Fohrenkamm等人)闡述藉由設計基板及印刷油墨具有獨特極性關係來改良柔性版印刷導電線之方式。 In addition, U.S. Patent Application Publication 2013/0319275 (Fohrenkamm et al.) Describes a way to improve the flexographic printing conductive wire by designing a substrate and a printing ink having a unique polarity relationship.

在輥-輥產生方法中於撓性及透明基板上使用沈積提供感測器功能性之導電圖案之「附加製程」產生觸控螢幕感測器及其他透明導電物件已成為最新工業研發之目標。尤其重要的是，應能夠產生在觸控螢幕感測器之可見部分(觸控區域)中具有期望電性能以及適當光學性質(透射率)之觸控螢幕感測器。為達成期望導電及光學性質，極為期 望導電柵格中之導電線之平均線寬小於10μm。 In the roll-to-roll production method, the use of the "additional process" of depositing conductive patterns that provide sensor functionality on flexible and transparent substrates to produce touch screen sensors and other transparent conductive objects has become the latest industrial research and development goal. It is particularly important to be able to produce a touch screen sensor with the desired electrical properties and appropriate optical properties (transmittance) in the visible portion (touch area) of the touch screen sensor. To achieve the desired conductive and optical properties, It is expected that the average line width of the conductive lines in the conductive grid is less than 10 μm.

該等製程中所使用之撓性及透明基板應為光學透明(高積分透射率)及無色且展現低濁度。使用附加製程施加導電圖案(例如柔性版印刷導電材料或晶種金屬組合物)需要撓性及透明基板具有與擬施加精細特徵(例如細線)之尺寸一致之適當表面能及粗糙度。在電子工業中作出大量努力來達成該等所需特徵。 The flexible and transparent substrates used in these processes should be optically transparent (high integrated transmittance), colorless, and exhibit low turbidity. The use of additional processes to apply conductive patterns (such as flexographic printing conductive materials or seed metal compositions) requires that the flexible and transparent substrate have the proper surface energy and roughness consistent with the dimensions of the fine features (such as thin lines) to be applied. Considerable efforts have been made in the electronics industry to achieve these desired characteristics.

WO 2013063188(Petcavich等人)闡述藉由以下過程產生包括介電基板之相互電容觸控感測器之方法：使用柔性版印刷製程利用至少第一母板及第一油墨將第一圖案印刷於介電基板之第一側上；及固化所印刷介電物件。可類似地施加第二油墨且固化以在基板之第二表面上形成第二圖案。然後可使用導電材料無電鍍敷兩個圖案。據闡述，所得介電物件具有1μm至1mm之厚度及20達因(Dyne)/cm至90達因/cm之較佳表面能。 WO 2013063188 (Petcavich et al.) Describes a method for generating a mutual capacitive touch sensor including a dielectric substrate by the following process: using a flexographic printing process to print a first pattern on a substrate using at least a first motherboard and a first ink On the first side of the electrical substrate; and curing the printed dielectric article. A second ink can be similarly applied and cured to form a second pattern on the second surface of the substrate. The two patterns can then be electrolessly plated using a conductive material. According to the description, the obtained dielectric article has a thickness of 1 μm to 1 mm and a preferable surface energy of 20 Dyne / cm to 90 dyne / cm.

始終努力探詢提供具有用於各種電子器件(例如觸控螢幕感測器及其他光學顯示器)之期望表面及光學性質之撓性及透明基板之成本有效方式。該等努力尤其旨在在基板經受各種化學及機械操作之高效輥-輥製造操作中製備及使用該等基板。 There is always an effort to explore cost-effective ways to provide flexible and transparent substrates with the desired surface and optical properties for various electronic devices such as touch screen sensors and other optical displays. These efforts are specifically aimed at preparing and using substrates in highly efficient roll-to-roll manufacturing operations where the substrates are subjected to various chemical and mechanical operations.

特定而言，業內需要如下撓性及透明基板：其展現低濁度、低顏色及表面均勻性且由此更適於黏著精細特徵(例如細線、文本或較小形狀)，且尤其適用於導電細線。亦期望對「印刷」圖案(例如彼等藉由柔性版印刷固有地或可進一步處理以變得導電之含金屬組合物所施加者)展現強黏著之撓性及透明基板。 In particular, there is a need in the industry for flexible and transparent substrates that exhibit low turbidity, low color, and surface uniformity and are therefore more suitable for adhering fine features (such as thin lines, text, or smaller shapes), and are particularly suitable for conductive Thin line. It is also desirable to exhibit strongly adherent flexible and transparent substrates to "printed" patterns (such as those applied by metal-containing compositions that are inherently or further processable by flexographic printing to become conductive).

本發明使用包括第一聚合物乳膠及第二聚合物乳膠之混合物之塗層組合物來解決業內所遇到之各種問題，其中第一聚合物乳膠包括第一聚合物及第一表面活性劑，使得 第一聚合物乳膠之乾燥塗層具有至少50%之表面極性，且其中第二聚合物乳膠包括第二聚合物及第二表面活性劑，使得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，且其中第一聚合物乳膠及第二聚合物乳膠之混合物之乾燥塗層具有至少15%且至多並包含50%之表面極性。 The present invention uses a coating composition including a mixture of a first polymer latex and a second polymer latex to solve various problems encountered in the industry. The first polymer latex includes a first polymer and a first surfactant. Make The dry coating of the first polymer latex has a surface polarity of at least 50%, and wherein the second polymer latex includes a second polymer and a second surfactant, so that the dry coating of the second polymer latex has a thickness less than or equal to 27% surface polarity, and the dry coating of the mixture of the first polymer latex and the second polymer latex has a surface polarity of at least 15% and up to and including 50%.

此外，本發明提供一種基板，其包括載體及佈置於載體之至少一個支撐表面上之乾燥底漆層，乾燥底漆層包括以下物質之混合物：第一聚合物乳膠，其包括第一聚合物及第一表面活性劑，使得第一聚合物乳膠之乾燥塗層具有至少50%之表面極性，及第二聚合物乳膠，其包括第二聚合物及不同於第一表面活性劑之第二表面活性劑，使得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，其中乾燥底漆層具有至少15%且至多並包含50%之表面極性。 In addition, the present invention provides a substrate including a carrier and a dry primer layer disposed on at least one supporting surface of the carrier. The dry primer layer includes a mixture of the following materials: a first polymer latex including a first polymer and The first surfactant enables the dry coating of the first polymer latex to have a surface polarity of at least 50%, and the second polymer latex includes the second polymer and a second surfactant different from the first surfactant Agent, such that the dry coating of the second polymer latex has a surface polarity of less than or equal to 27%, wherein the dry primer layer has a surface polarity of at least 15% and up to and including 50%.

在本發明之特定實施例中，透明聚合基板包括透明聚酯載體及直接佈置於透明聚酯載體之至少一個支撐表面上之乾燥底漆層，其中：(i)透明聚合基板具有至少88%之積分透射率；(ii)乾燥底漆層具有至少0.05μm且至多並包含0.2μm之平均厚度，且包括以下物質之混合物：第一聚合物乳膠，其包括第一聚合物及第一表面活性劑，其中基於第一聚合物總重量，第一聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，第一聚合物具有至少20℃且至多並包含75℃之玻璃轉變溫度，且第一表面活性劑係α-烯烴(C₁₄-C₁₆)磺酸鈉；第二聚合物乳膠，其包括第二聚合物及不同於第一表面活性劑 之第二表面活性劑，其中基於第二聚合物總重量，第二聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，第二聚合物具有至少25℃且至多並包含75℃之玻璃轉變溫度，且第二表面活性劑係硫酸化聚乙氧基壬基苯酚之銨鹽；(iii)乾燥底漆層具有至少28%且至多並包含50%之表面極性；(iv)第一聚合物乳膠對第二聚合物乳膠之重量比率為1：1且至並包含2.5：1；(v)基於總乾燥底漆重量，第一表面活性劑以至少1重量%且至多並包含3重量%之量存在於乾燥底漆層中；(vi)基於總乾燥底漆層，第二表面活性劑以至少0.35重量%且至多並包含1.1重量%之量存在於乾燥底漆層中；且(vii)基於總乾燥底漆層重量，乾燥底漆層中之第一及第二表面活性劑之總量小於3.35重量%。 In a specific embodiment of the present invention, the transparent polymer substrate includes a transparent polyester carrier and a dry primer layer disposed directly on at least one supporting surface of the transparent polyester carrier, wherein: (i) the transparent polymer substrate has at least 88% Integral transmittance; (ii) the dried primer layer has an average thickness of at least 0.05 μm and up to and including 0.2 μm, and includes a mixture of: a first polymer latex including a first polymer and a first surfactant Wherein the first polymer includes at least 75% by weight and up to and including 90% by weight of repeating units derived from glycidyl (meth) acrylate based on the total weight of the first polymer and at least 10% by weight and including up to 25% The weight% is derived from repeating units of n-butyl (meth) acrylate, the first polymer has a glass transition temperature of at least 20 ° C and at most and contains 75 ° C, and the first surfactant is an α-olefin (C _14- C ₁₆ ) sodium sulfonate; a second polymer latex comprising a second polymer and a second surfactant different from the first surfactant, wherein the second polymer includes at least 75 based on the total weight of the second polymer % By weight and up to and including 90% by weight of repeating units derived from glycidyl (meth) acrylate and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, The second polymer has a glass transition temperature of at least 25 ° C and up to and including 75 ° C, and the second surfactant is an ammonium salt of sulfated polyethoxynonylphenol; (iii) the dried primer layer has at least 28% And up to and including 50% of the surface polarity; (iv) the weight ratio of the first polymer latex to the second polymer latex is 1: 1 and up to and including 2.5: 1; (v) based on the total dry primer weight, One surfactant is present in the dry primer layer in an amount of at least 1% by weight and up to and including 3% by weight; (vi) based on the total dry primer layer, the second surfactant is at least 0.35% by weight and up to and including An amount of 1.1% by weight is present in the dry primer layer; and (vii) the total amount of the first and second surfactants in the dry primer layer is less than 3.35% by weight based on the total dry primer layer weight.

本發明之各種實施例提供諸多優點。最重要的是，本發明所提供之組合物及打底基板展現用於以含有精細特徵(包含但不限於平均線寬小於15μm或更可能小於15μm之線)之圖案施加及黏著各種組合物之期望表面特性。舉例而言，可使用含有金屬晶種顆粒之光可固化或熱可固化組合物提供該等圖案，且該等圖案可適於無電鍍覆以提供具有期望精細特徵之導電圖案。該等基板及含有其之物件展現低濁度、低顏色、期望表面均勻性(塗層外觀)及高積分透射率(至少88%)。藉由使用包括具有下文所闡述性質及組成之第一聚合物乳膠及第二聚合物乳膠之混合物之底漆組合物「打底」適宜載體材料(例如透明載體材料)來達成該等優點。 Various embodiments of the invention provide a number of advantages. Most importantly, the composition and the base substrate provided by the present invention are used to apply and adhere various compositions in a pattern containing fine features (including but not limited to lines with an average line width of less than 15 μm or more possibly less than 15 μm). Desirable surface characteristics. For example, the patterns may be provided using a photo-curable or heat-curable composition containing metal seed particles, and the patterns may be suitable for electroless plating to provide a conductive pattern with desired fine characteristics. These substrates and objects containing them exhibit low turbidity, low color, desired surface uniformity (coating appearance) and high integrated transmittance (at least 88%). These advantages are achieved by "priming" a suitable carrier material (eg, a transparent carrier material) with a primer composition including a mixture of a first polymer latex and a second polymer latex having the properties and composition described below.

100‧‧‧柔性版印刷系統 100‧‧‧ flexographic printing system

102‧‧‧供應輥 102‧‧‧Supply roller

104‧‧‧捲曲輥 104‧‧‧Curl roller

105‧‧‧輥至輥方向 105‧‧‧roll-to-roll direction

106‧‧‧輥 106‧‧‧roller

107‧‧‧輥 107‧‧‧roller

110‧‧‧印刷模組 110‧‧‧printing module

111‧‧‧板滾筒 111‧‧‧ plate roller

112‧‧‧柔性版印刷板(或柔性版印刷部件) 112‧‧‧Flexographic printing plate (or flexographic printing component)

113‧‧‧凸起特徵 113‧‧‧ raised features

114‧‧‧壓印滾筒 114‧‧‧Impression roller

115‧‧‧網紋輥 115‧‧‧ Anilox Roller

116‧‧‧紫外固化台 116‧‧‧UV curing station

120‧‧‧印刷模組 120‧‧‧Printing Module

121‧‧‧板滾筒 121‧‧‧ plate roller

122‧‧‧柔性版印刷板(或柔性版印刷部件) 122‧‧‧Flexographic printing plate (or flexographic printing component)

124‧‧‧壓印滾筒 124‧‧‧Impression roller

125‧‧‧網紋輥 125‧‧‧ Anilox Roller

126‧‧‧紫外固化台 126‧‧‧UV curing station

130‧‧‧印刷模組 130‧‧‧Printing Module

131‧‧‧板滾筒 131‧‧‧ plate roller

132‧‧‧柔性版印刷板(或柔性版印刷部件) 132‧‧‧Flexographic printing plate (or flexographic printing component)

134‧‧‧壓印滾筒 134‧‧‧Impression roller

135‧‧‧網紋輥 135‧‧‧ Anilox Roller

136‧‧‧紫外固化台 136‧‧‧UV curing station

140‧‧‧印刷模組 140‧‧‧printing module

141‧‧‧板滾筒 141‧‧‧plate roller

142‧‧‧柔性版印刷板(或柔性版印刷部件) 142‧‧‧Flexographic printing plate (or flexographic printing component)

144‧‧‧壓印滾筒 144‧‧‧Impression roller

145‧‧‧網紋輥 145‧‧‧ Anilox Roller

146‧‧‧紫外固化台 146‧‧‧UV curing station

150‧‧‧基板(或連續網片) 150‧‧‧ substrate (or continuous mesh)

151‧‧‧第一支撐側 151‧‧‧first support side

152‧‧‧第二(相對)支撐側 152‧‧‧second (relative) support side

300‧‧‧裝置(或器件) 300‧‧‧ device (or device)

310‧‧‧觸控螢幕 310‧‧‧Touch screen

320‧‧‧顯示器件 320‧‧‧ display device

330‧‧‧觸控感測器 330‧‧‧Touch Sensor

340‧‧‧透明基板 340‧‧‧Transparent substrate

341‧‧‧第一支撐側 341‧‧‧first support side

342‧‧‧第二支撐側 342‧‧‧Second support side

350‧‧‧第一導電圖案 350‧‧‧first conductive pattern

351‧‧‧細線 351‧‧‧thin line

352‧‧‧柵格 352‧‧‧Grid

353‧‧‧細線 353‧‧‧thin line

354‧‧‧通道墊 354‧‧‧channel pad

355‧‧‧柵格行 355‧‧‧Grid line

356‧‧‧互連線 356‧‧‧interconnect

358‧‧‧連結器墊 358‧‧‧Connector Pad

360‧‧‧第二導電圖案 360‧‧‧Second conductive pattern

361‧‧‧細線 361‧‧‧ thin line

362‧‧‧柵格 362‧‧‧Grid

363‧‧‧細線 363‧‧‧thin line

364‧‧‧通道墊 364‧‧‧Channel Pad

365‧‧‧柵格列 365‧‧‧Grid column

366‧‧‧互連線 366‧‧‧interconnect

368‧‧‧連結器墊 368‧‧‧Connector Pad

380‧‧‧控制器 380‧‧‧controller

圖1係在本發明基板之兩側上之可用於輥至輥印刷(或成像)之柔性版印刷系統之示意側視圖，其中使用本發明之光可固化組合物(圖案化材料)及方法。 Figure 1 is a schematic side view of a flexographic printing system that can be used for roll-to-roll printing (or imaging) on both sides of a substrate of the present invention, in which the photocurable composition (patterned material) and method of the present invention are used.

圖2係包括具有可使用本發明製備(印刷)之觸控感測器之觸控螢幕之裝置(器件)之高級系統圖表。 FIG. 2 is a high-level system diagram including a device (device) having a touch screen that can be prepared (printed) using the present invention.

圖3係圖2之觸控感測器之側視圖。 FIG. 3 is a side view of the touch sensor of FIG. 2.

圖4係已在圖3之觸控感測器中之基板之第一支撐側上形成之導電金屬圖案之俯視圖。 FIG. 4 is a top view of a conductive metal pattern that has been formed on a first support side of a substrate in the touch sensor of FIG. 3.

圖5係已在圖3之觸控感測器中之基板之第二(相對)側上印刷之導電金屬圖案之俯視圖。 FIG. 5 is a top view of a conductive metal pattern that has been printed on the second (opposite) side of the substrate in the touch sensor of FIG. 3.

下列論述係關於本發明之各種實施例且儘管一些實施例對於特定用途而言可能期望，但所揭示實施例不應詮釋或換言之視為限制如下文所主張之本發明範圍。此外，熟習此項技術者應理解，下列揭示內容具有廣泛於所明確闡述之應用的應用。 The following discussion pertains to various embodiments of the invention and although some embodiments may be desirable for a particular use, the disclosed embodiments should not be interpreted or otherwise viewed as limiting the scope of the invention as claimed below. In addition, those skilled in the art will understand that the following disclosure has applications that are broader than the applications specifically articulated.

定義definition

如本文中所使用，為定義底漆塗層組合物、乾燥底漆層、光可固化及熱可固化組合物及本文所闡述之其他組成特徵中之各種組份，除非另外指示，否則單數形式「一個(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)。 As used herein, the various components of the primer coating composition, the dry primer layer, the photo-curable and heat-curable composition, and other compositional features described herein are defined in the singular unless otherwise indicated "A" and "the" are intended to include one or more components (ie, include a plurality of indicators).

應理解，本申請案中未明確定義之每一術語具有熟習此項技術者通常接受之含義。若術語之構造使得其在其上下文中無意義或基本上無意義，則該術語之定義應自標準字典獲得。 It should be understood that each term not explicitly defined in this application has the meaning commonly accepted by those skilled in the art. If a term is constructed such that it is meaningless or essentially meaningless in its context, the definition of the term should be obtained from a standard dictionary.

除非另外明確指示相反，否則在本文所指定各個範圍中使用之數值應視為近似值，如同規定範圍之最小值及最大值二者前面均由詞語「約」修飾。以此方式，可使用高於或低於規定範圍之輕微改變以 達成實質上與範圍內之值相同的結果。此外，該等範圍之揭示內容意欲作為包含最小與最大值之間之每一值的連續範圍。 Unless expressly stated to the contrary, numerical values used in the ranges specified herein are to be regarded as approximations, as if the minimum and maximum of the stated range were both preceded by the word "about". In this way, slight changes above or below the specified range can be used to Achieve substantially the same results as the values in the range. In addition, the disclosure of these ranges is intended as a continuous range containing each value between the minimum and maximum values.

如本文中所使用，除非另外指示，否則分子量皆為重量平均分子量，若自文獻尚且未知該等值，則其可使用已知程序及設備來確定。 As used herein, unless otherwise indicated, molecular weights are weight average molecular weights, and if such values are not known from the literature, they can be determined using known procedures and equipment.

除非另外指示，否則術語「光可固化或熱可固化組合物」係指可用於實踐本發明之各種方法且可提供於本發明物件中之化學組合物。該等組合物具有可在某些條件下固化、聚合或交聯之所需化學性質。 Unless otherwise indicated, the term "photocurable or thermally curable composition" refers to a chemical composition that can be used to practice the methods of the present invention and can be provided in the articles of the present invention. These compositions have the required chemical properties that can be cured, polymerized, or crosslinked under certain conditions.

術語「固化」及「聚合」在本文中用於意指藉由(例如)共價鍵結在適宜觸媒或起始劑存在下組合大量較小分子(例如單體或寡聚物)以形成極大分子(亦即大分子或聚合物)。固化或聚合可形成直鏈大分子或三維大分子(其通常稱為交聯聚合物，包含具支鏈材料)，或可同時形成直鏈及交聯(或具支鏈)材料。可在本發明實踐中實施之一類聚合係酸催化(陽離子型)聚合。亦可在本發明實踐中實施自由基聚合。另一選擇為，在一些實施例中，可同時實施酸催化聚合及自由基聚合。 The terms "curing" and "polymerization" are used herein to mean that a large number of smaller molecules (e.g., monomers or oligomers) are combined to form, for example, by covalent bonding in the presence of a suitable catalyst or initiator. Very large molecules (ie macromolecules or polymers). Curing or polymerizing can form linear macromolecules or three-dimensional macromolecules (which are commonly referred to as crosslinked polymers, which include branched materials), or can form both linear and crosslinked (or branched) materials. One type of polymerization-based acid-catalyzed (cationic) polymerization can be carried out in the practice of the present invention. Free radical polymerization can also be carried out in the practice of the present invention. Alternatively, in some embodiments, acid-catalyzed polymerization and free-radical polymerization may be performed simultaneously.

術語「光可固化」及「可固化」用於定義將在適當光起始劑組合物存在下經適宜輻射輻照(例如經諸如紫外(UV)、可見或紅外輻射等輻射輻照)時聚合之材料(例如環氧樹脂材料)。 The terms "light-curable" and "curable" are used to define that when polymerized in the presence of a suitable photoinitiator composition, it is irradiated with a suitable radiation (e.g., radiation such as ultraviolet (UV), visible or infrared radiation) Materials (such as epoxy materials).

本文所闡述層之平均乾燥厚度可為(例如)使用電子顯微鏡或光學顯微鏡在乾燥層之不同位置中獲取之兩個或更多個單獨量測之平均值。在某些實施例中，可期望獲得2個以上單獨量測。 The average dry thickness of the layers described herein can be, for example, the average of two or more separate measurements taken at different locations of the dried layer using an electron microscope or an optical microscope. In some embodiments, it may be desirable to obtain more than 2 separate measurements.

類似地，本文所闡述之線、柵格線或其他圖案特徵之平均乾燥厚度或寬度可為(例如)使用電子顯微鏡獲取之兩個或更多個單獨量測之平均值。 Similarly, the average dry thickness or width of a line, grid line, or other pattern feature set forth herein may be the average of two or more separate measurements taken, for example, using an electron microscope.

術語「可聚合環氧樹脂材料」意欲包含具有一或多個能夠發生 聚合之環氧乙烷環之任一材料或化合物。此術語涵蓋含有環氧樹脂之單體、含有環氧樹脂之寡聚物及含有環氧樹脂之交聯劑。該術語之單數形式意欲包含該術語之複數形式。寡聚物及多官能環氧樹脂材料亦係有用之可聚合環氧樹脂材料。 The term "polymerizable epoxy material" is intended to include having one or more Any material or compound of a polymerized ethylene oxide ring. This term covers monomers containing epoxy resins, oligomers containing epoxy resins, and crosslinking agents containing epoxy resins. The singular form of the term is intended to include the plural form of the term. Oligomeric and polyfunctional epoxy materials are also useful polymerizable epoxy materials.

術語「電子供體光敏劑」意欲係指用於誘導光固化之光吸收化合物。在光激發後，電子供體光敏劑引起鎓鹽之單電子還原。 The term "electron donor photosensitizer" is intended to refer to a light absorbing compound used to induce light curing. After photoexcitation, the electron donor photosensitizer causes a single electron reduction of the onium salt.

術語「光起始劑」意欲係指在曝光於光時分解成自由基或化學片段以引發其他反應之任一化學化合物。在一些實施例中，光起始劑係「鎓鹽」或「鎓化合物」或其他能夠接受來自經激發電子供體光敏劑之電子(該過程使得鎓鹽發生斷裂以提供引發環氧樹脂材料之聚合之布氏酸(Brönsted acid))之光酸生成劑。在其他實施例中，光起始劑分解成引起乙烯基之固化、聚合或交聯之自由基。 The term "photoinitiator" is intended to mean any chemical compound that breaks down into free radicals or chemical fragments to initiate other reactions when exposed to light. In some embodiments, the photoinitiator is an "onium salt" or "onium compound" or other capable of accepting electrons from an excited electron donor photosensitizer (a process that breaks the onium salt to provide the material that triggers the epoxy material). Photo-acid generator for polymerized Brönsted acid. In other embodiments, the photoinitiator is broken down into free radicals that cause the vinyl to cure, polymerize, or crosslink.

「光化輻射」用於係指任一能夠產生本發明之光化學或光聚合作用且波長為至少150nm且至多並包含750nm或甚至至少190nm且至多並包含700nm之電磁輻射。術語「曝光輻射」亦係指該光化輻射。 "Actinic radiation" is used to mean any electromagnetic radiation capable of producing the photochemical or photopolymerization of the present invention and having a wavelength of at least 150 nm and up to and including 750 nm or even at least 190 nm and up to and including 700 nm. The term "exposure radiation" also refers to the actinic radiation.

術語「可見光」用於係指具有大於400nm至且至多並包含750奈米(nm)之波長(例如λ_max)之電磁輻射。 The term "visible light" is used to refer to electromagnetic radiation having a wavelength (eg, λ _max ) greater than 400 nm and up to and including 750 nanometers (nm).

術語「UV光」用於係指具有至少150nm且至多並包含400nm之波長(例如λ_max)之電磁輻射。 The term "UV light" is used to refer to electromagnetic radiation having a wavelength (eg, λ _max ) of at least 150 nm and up to and including 400 nm.

術語「近紅外」及「紅外」在本文中用於係指具有至少750nm及更高且通常至少750nm且至多並包含1400nm之波長(例如λ_max)之電磁輻射。 The terms "near infrared" and "infrared" are used herein to refer to electromagnetic radiation having a wavelength (eg, λ _max ) of at least 750 nm and higher and usually at least 750 nm and up to and including 1400 nm.

術語「積分透射率」係用於量測「透明性」之參數。因此，在載體、基板及物件提及為透明時，電磁光譜之可見區域(例如400nm至750nm)上之積分透射率為80%或更高或更可能至少88%或甚至93%或更高，如(例如)使用分光光度計及已知技術所量測。一般而言，導 電物件或膜中之觸控區域具有此高積分透射率。然而，電極連結器區域或BUS區域通常具有極小透明性且使用上述相同設備及程序可通常具有小於68%或小於50%或甚至小於40%之積分透射率。 The term "integrated transmittance" is a parameter used to measure "transparency". Therefore, when the carrier, substrate, and object are referred to as transparent, the integrated transmittance in the visible region of the electromagnetic spectrum (for example, 400 nm to 750 nm) is 80% or higher or possibly at least 88% or even 93% or higher, As measured, for example, using a spectrophotometer and known techniques. Generally speaking, the guide Touch areas in electrical objects or films have this high integrated transmittance. However, the electrode connector area or the BUS area usually has very little transparency and can generally have an integrated transmittance of less than 68% or less than 50% or even less than 40% using the same equipment and procedures described above.

另一選擇為，積分透射率可與透明物件、載體或基板區中未由觸控區域中之導電圖案覆蓋之計算百分比有關。 Alternatively, the integrated transmittance may be related to the calculated percentage of the transparent object, the carrier, or the substrate area that is not covered by the conductive pattern in the touch area.

在提及本文所闡述各種圖案或圖案化材料時之術語「平均線寬」係指使用熟習此項技術者已知之適當量測技術及設備自相同或不同線之不同位置中兩個或更多個單獨線量測所測得的尺寸。在某些實施例中，可期望2個以上之該等量測。 The term "average line width" when referring to the various patterns or patterned materials described herein refers to the use of appropriate measurement techniques and equipment known to those skilled in the art from two or more of the different locations of the same or different lines Dimensions measured by individual wires. In some embodiments, more than two such measurements may be desired.

導電表面、部分、膜或其他結構上之「觸控區域」係指具有圖案化材料之物件區域，該等導電圖案經設計用於接觸以操縱影像、「apps」或顯示器件中之其他數位資訊)。因此，觸控區域與「導電電極連結器區域」、「BUS線」及「BUS區域」不同。 "Touch areas" on conductive surfaces, sections, films, or other structures are areas of objects with patterned materials that are designed to contact to manipulate images, "apps" or other digital information in a display device ). Therefore, the touch area is different from the "conductive electrode connector area", "BUS line", and "BUS area".

如下文實例中所闡述來定義表面極性。 Surface polarity is defined as set forth in the examples below.

用途use

本文所闡述之塗層組合物、基板、物件及方法可用於各種目的，其中需要具有所述性質之基板來進一步施加材料或形成圖案。舉例而言，本文所闡述之(底漆)塗層組合物、基板及物件尤其可用於(例如)使用無電鍍覆程序提供具有精細特徵之導電金屬圖案，其可納入各種器件(包含但不限於觸控螢幕或其他可用於諸多工業及商業產品中之顯示器件)中。 The coating compositions, substrates, articles, and methods described herein can be used for a variety of purposes, where substrates having the properties described are needed to further apply materials or form patterns. For example, the (primer) coating compositions, substrates, and articles described herein are particularly useful, for example, to provide conductive metal patterns with fine features using electroless plating processes, which can be incorporated into a variety of devices, including but not limited to Touch screens or other display devices that can be used in many industrial and commercial products).

舉例而言，觸控螢幕技術可包括不同觸控感測器構形(包含電容式及電阻式觸控感測器)。電阻式觸控感測器包括若干層，該等層彼此面對且在毗鄰層之間存在間隙，該間隙可能藉由在製造期間形成之間隔件而留存。電阻式觸控螢幕面板可包括若干層，其包含兩個藉由可能藉由間隔件產生之間隙分開之薄金屬導電層。在諸如觸針、手掌 或指尖等物體於面板外表面上之點上向下按壓時，兩個金屬層接觸且形成連結從而使得電流發生改變。此接觸事件發送至控制器用於進一步處理。 For example, touch screen technology may include different touch sensor configurations (including capacitive and resistive touch sensors). The resistive touch sensor includes several layers that face each other with a gap between adjacent layers that may be retained by spacers formed during manufacturing. A resistive touch screen panel may include several layers including two thin metal conductive layers separated by a gap that may be created by a spacer. Such as stylus, palm When an object such as a fingertip is pressed down on a point on the outer surface of the panel, the two metal layers contact and form a connection so that the current changes. This contact event is sent to the controller for further processing.

電容式觸控感測器可用於具有接觸-敏感特徵之電子器件中。該等電子器件可包含但不限於可適於顯示影像(包含文本、圖形、視訊影像、電影、靜態影像及演示)之電視、監測器及投影機。可用於該等顯示器件之影像器件可包含陰極射線管(CRT)、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(ELD)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接觸-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、行動電話及其他通信或數位儲存器件)。 Capacitive touch sensors can be used in electronic devices with touch-sensitive features. Such electronic devices may include, but are not limited to, televisions, monitors, and projectors that are suitable for displaying images (including text, graphics, video images, movies, still images, and presentations). The imaging devices that can be used for these display devices can include cathode ray tubes (CRT), projectors, flat panel liquid crystal displays (LCD), LED systems, OLED systems, plasma systems, electroluminescence displays (ELD), and field emission displays ( FED). For example, the present invention can be used to prepare capacitive touch sensors that can be incorporated into electronic devices with touch-sensitive features to provide computing devices, computer monitors, and portable media players (including electronic readers, mobile phones). And other communication or digital storage devices).

使用本發明以高容量輥至輥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。光可固化或熱可固化組合物可與凸版印刷部件(例如柔性版印刷板)一起使用以自預定圖案設計形成多個高解析度導電影像。可如下文更詳細闡述將多個圖案印刷於發明性基板之一個或兩個支撐側上。舉例而言，可將一個預定圖案印刷於基板之一個支撐側上且可將不同預定圖案印刷於基板之相對支撐側上。然後可(例如)使用無電金屬鍍覆技術進一步處理光可固化或熱可固化組合物之印刷圖案以提供含有精細特徵之導電金屬圖案。 A system and method for manufacturing flexible and optically compliant touch sensors in a high-volume roll-to-roll manufacturing process using the present invention is possible, where micro-conductive features can be generated in a single pass. The photo-curable or heat-curable composition can be used with letterpress printing components, such as flexographic printing plates, to form multiple high-resolution conductive images from a predetermined pattern design. Printing multiple patterns on one or both support sides of the inventive substrate can be explained in more detail below. For example, one predetermined pattern may be printed on one supporting side of the substrate and different predetermined patterns may be printed on the opposite supporting side of the substrate. The printed pattern of the photo-curable or heat-curable composition can then be further processed, for example, using electroless metal plating techniques to provide a conductive metal pattern containing fine features.

聚合物乳膠Polymer latex

向本發明提供獨特組合物，可使用任一用於提供本發明優點之適宜方式將該組合物沈積於表面上。此一組合物亦可通常稱為「塗層組合物」、「底漆層組合物」或「底漆組合物」。此塗層組合物包括至少一種第一聚合物乳膠及至少一種第二聚合物乳膠之混合物。藉由 使用修飾語「第一」及「第二」，其並不意欲意指一種聚合物乳膠(或聚合物)在任一給定性質方面優於另一聚合物乳膠(或聚合物)，而是僅用於區分兩種不同聚合物乳膠組合物。其他聚合物乳膠可存在於混合物中(若期望)，只要獲得期望性質(闡述於本文中)。 Providing the present invention with a unique composition, the composition can be deposited on a surface using any suitable means for providing the advantages of the present invention. This composition may also be commonly referred to as a "coating composition," "primer layer composition," or "primer composition." The coating composition includes a mixture of at least one first polymer latex and at least one second polymer latex. By The use of the modifiers "first" and "second" is not intended to mean that one polymer latex (or polymer) is superior to another polymer latex (or polymer) in any given property, but only Used to distinguish between two different polymer latex compositions. Other polymer latexes may be present in the mixture, if desired, as long as the desired properties are obtained (explained herein).

第一及第二聚合物：First and second polymers:

第一及第二聚合物乳膠分別包括第一聚合物及第二聚合物。在呈乳膠形式或聚合分散液形式時，第一及第二聚合物通常以使用已知乳液聚合技術形成於膠束中之顆粒形式存在。儘管可分離第一及第二聚合物中之每一者，但其以第一及第二乳膠之混合物形式用於本發明中且由此分離可能使得更難以在塗層中使用其。 The first and second polymer latexes include a first polymer and a second polymer, respectively. When in the form of a latex or a polymeric dispersion, the first and second polymers are typically present in the form of particles formed in micelles using known emulsion polymerization techniques. Although each of the first and second polymers can be separated, it is used in the present invention in the form of a mixture of the first and second latex and thus the separation may make it more difficult to use it in a coating.

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，且在大部分實施例中，第一及第二聚合物中之每一者至少部分地衍生自(甲基)丙烯酸縮水甘油基酯。此外，第一聚合物及第二聚合物中之至少一者可交聯，且可(例如)在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)交聯。熟習此項技術者知曉如何藉由慎重選擇聚合物重複單元及反應性基團之設計來在給定聚合物中提供交聯能力。 At least one of the first and second polymers described herein includes containing at least partially derived from glycidyl (meth) acrylate (meaning glycidyl acrylate, glycidyl methacrylate, or both) ), And in most embodiments, each of the first and second polymers is at least partially derived from glycidyl (meth) acrylate. In addition, at least one of the first polymer and the second polymer may be crosslinked, and may be crosslinked, for example, after being coated on a suitable carrier (for example, during drying of the substrate or various heat treatments). Those skilled in the art know how to provide cross-linking capabilities in a given polymer by carefully selecting the design of the polymer repeat units and reactive groups.

本發明中所使用之第一聚合物乳膠包括一或多種第一聚合物及一或多種第一表面活性劑(闡述於下文中)，使得第一聚合物乳膠之乾燥塗層具有至少50%(50%或更高)或甚至至少55%(55%或更高)之表面極性。在大部分實施例中，第一聚合物乳膠基本上由兩種基本組份組成：一或多種第一聚合物及一或多種第一表面活性劑。 The first polymer latex used in the present invention includes one or more first polymers and one or more first surfactants (described below), so that the dry coating of the first polymer latex has at least 50% ( 50% or higher) or even at least 55% (55% or higher) surface polarity. In most embodiments, the first polymer latex consists essentially of two basic components: one or more first polymers and one or more first surfactants.

尤其有用之第一聚合物係至少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。術語「縮水甘油基」係指包括附接至具有1至4個碳原子之烷基(亦可進一步經取代之直鏈或具支鏈烷基，例如甲基、乙基、異丙基及第三丁基)之環氧乙烷環之基團。 A particularly useful first polymer is a vinyl polymer that is at least partially derived from one or more glycidyl-functional vinyl-based unsaturated polymerizable monomers, such as glycidyl acrylate and glycidyl methacrylate. . Therefore, the first polymer may be derived from Homopolymer of glycidyl (meth) acrylate, but more likely it is derived from a copolymer of glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers. The term "glycidyl" refers to a straight or branched alkyl group attached to an alkyl group having 1 to 4 carbon atoms (which may also be further substituted, such as methyl, ethyl, isopropyl, and Tributyl) ethylene oxide ring group.

舉例而言，基於第一聚合物之總重量，第一聚合物可以至少75重量%且至多並包含100重量%或至少75重量%且至多並包含90重量%之量包括衍生自(甲基)丙烯酸縮水甘油基酯之重複單元。尤其期望之第一聚合物由此衍生自(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(共單體)，該等其他乙烯系不飽和可聚合單體(共單體)實質上與(甲基)丙烯酸縮水甘油基酯單體共聚合而非在乳液聚合期間與縮水甘油基發生反應且將促進反應分散液內之所有乙烯系不飽和可聚合單體之乳液聚合。適宜乙烯基共單體包含但不限於丙烯酸烷基酯及甲基丙烯酸烷基酯，其中酯烷基具有1至4個碳原子；其他經取代丙烯酸烷基酯及甲基丙烯酸烷基酯；丙烯醯胺及甲基丙烯醯胺；乙烯基鹵化物，例如氯乙烯；亞乙烯基鹵化物，例如二氯亞乙烯；乙烯基吡咯啶酮；其他N-乙烯基醯胺；乙烯基吡啶；苯乙烯及苯乙烯衍生物，例如α-甲基苯乙烯；丁二烯；異戊二烯；丙烯腈；甲基丙烯腈；及其他為熟習此項技術者所易知者。若期望，則可使用共單體之混合物。熟習此項技術者能夠使用常規實驗確定提供本文所闡述之期望成膜性質及表面極性值之各種共單體之適當量。 For example, based on the total weight of the first polymer, the first polymer may be at least 75% by weight and up to and including 100% by weight or at least 75% by weight and up to and including 90% by weight, including derived from (methyl) Glycidyl acrylate repeat unit. A particularly desirable first polymer is thus derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers (comonomers) which are other ethylenically unsaturated polymerizable monomers. (Comonomer) Copolymerizes with glycidyl (meth) acrylate monomers substantially instead of reacting with glycidyl groups during emulsion polymerization and will promote all ethylenically unsaturated polymerizable monomers in the reaction dispersion Emulsion polymerization. Suitable vinyl comonomers include, but are not limited to, alkyl acrylates and alkyl methacrylates, where the ester alkyl group has 1 to 4 carbon atoms; other substituted alkyl acrylates and alkyl methacrylates; propylene Ammonium and methacrylamide; vinyl halides, such as vinyl chloride; vinylidene halides, such as dichlorovinylidene; vinyl pyrrolidone; other N-vinyl ammonium amines; vinyl pyridine; styrene And styrene derivatives, such as α-methylstyrene; butadiene; isoprene; acrylonitrile; methacrylonitrile; and others well known to those skilled in the art. If desired, mixtures of comonomers can be used. Those skilled in the art will be able to use routine experimentation to determine appropriate amounts of various co-monomers that provide the desired film-forming properties and surface polarity values described herein.

第一聚合物尤其係藉由共聚合一或多種(甲基)丙烯酸縮水甘油基酯與一或多種酯烷基具有含至少2個碳原子之(甲基)丙烯酸烷基酯來設計，該等(甲基)丙烯酸烷基酯包含但不限於丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁基酯、甲基丙烯酸正丁基酯、丙烯酸環己基酯、甲基丙烯酸環己基酯、丙烯酸月桂基酯、甲基丙烯酸月桂基酯、甲基 丙烯酸烯丙基酯、甲基丙烯酸羥乙基酯、丙烯酸羥乙基酯及其他為熟習此項技術者所易知者。尤其有用之共單體係酯烷基具有至少4個碳原子之(甲基)丙烯酸烷基酯，包含但不限於丙烯酸正丁基酯、甲基丙烯酸正丁基酯、丙烯酸正己基酯、甲基丙烯酸正己基酯及甲基丙烯酸環己基酯。 The first polymer is especially designed by copolymerizing one or more glycidyl (meth) acrylates with one or more alkyl esters having an alkyl (meth) acrylate having at least 2 carbon atoms, such that Alkyl (meth) acrylates include, but are not limited to, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate Ester, lauryl methacrylate, methyl Allyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and others are well known to those skilled in the art. Particularly useful co-monomer ester alkyl (meth) acrylic acid alkyl esters having at least 4 carbon atoms, including but not limited to n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, methyl N-hexyl acrylate and cyclohexyl methacrylate.

可用於本發明中之第二聚合物乳膠包括一或多種二聚合物及一或多種第二表面活性劑(闡述於下文中)，使得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。在大部分實施例中，第二聚合物乳膠基本上由以下兩種基本組份組成：一或多種第二聚合物及一或多種第二表面活性劑。 The second polymer latex that can be used in the present invention includes one or more dipolymers and one or more second surfactants (described below) so that the dry coating of the second polymer latex has less than or equal to 28% Or less than or equal to 27% of the surface polarity. In most embodiments, the second polymer latex consists essentially of two basic components: one or more second polymers and one or more second surfactants.

尤其有用之第二聚合物係至少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，如上文針對第一聚合物所闡述。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。術語「縮水甘油基」定義於上文中。 A particularly useful second polymer is at least partially derived from one or more glycidyl-functional ethylenically unsaturated polymerizable monomers (e.g., glycidyl (meth) acrylate, such as glycidyl acrylate and methyl Glycidyl acrylate) vinyl polymer, as explained above for the first polymer. Therefore, 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. Thing. The term "glycidyl" is defined above.

因此，基於第二聚合物之總重量，第二聚合物可以至少75重量%且至多並包含100重量%或至少75重量%且至多並包含90重量%之量包括衍生自(甲基)丙烯酸縮水甘油基酯之重複單元。尤其期望之第二聚合物由此衍生自(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(共單體)，該等其他乙烯系不飽和可聚合單體(共單體)實質上與(甲基)丙烯酸縮水甘油基酯單體共聚合而非在乳液聚合期間與縮水甘油基發生反應且將促進反應分散液內之所有乙烯系不飽和可聚合單體之乳液聚合。適宜乙烯基共單體包含但不限於丙烯酸烷基酯及甲基丙烯酸烷基酯，其中酯烷基具有1至4個碳原子；其他經取代 丙烯酸烷基酯及甲基丙烯酸烷基酯；丙烯醯胺及甲基丙烯醯胺；乙烯基鹵化物，例如氯乙烯；亞乙烯基鹵化物，例如二氯亞乙烯；乙烯基吡咯啶酮；其他N-乙烯基醯胺；乙烯基吡啶；苯乙烯及苯乙烯衍生物，例如α-甲基苯乙烯；丁二烯；異戊二烯；丙烯腈；甲基丙烯腈；及其他為熟習此項技術者所易知者。若期望，則可使用共單體之混合物。如同第一聚合物，熟習此項技術者能夠使用常規實驗確定提供本文所闡述用於第二聚合物乳膠之期望成膜性質及表面極性值之各種共單體之適當量。 Thus, based on the total weight of the second polymer, the second polymer may be at least 75% by weight and up to and including 100% by weight or at least 75% by weight and up to and including 90% by weight, including derived from (meth) acrylic shrink Glyceryl repeat unit. A particularly desirable second polymer is thus derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers (comonomers) which are other ethylenically unsaturated polymerizable monomers. (Comonomer) Copolymerizes with glycidyl (meth) acrylate monomers substantially instead of reacting with glycidyl groups during emulsion polymerization and will promote all ethylenically unsaturated polymerizable monomers in the reaction dispersion Emulsion polymerization. Suitable vinyl comonomers include, but are not limited to, alkyl acrylates and alkyl methacrylates, where the ester alkyl group has 1 to 4 carbon atoms; other substituted Alkyl acrylate and alkyl methacrylate; acrylamide and methacrylamide; vinyl halides, such as vinyl chloride; vinylidene halides, such as dichlorovinylidene; vinylpyrrolidone; others N-vinylpyridine; vinylpyridine; styrene and styrene derivatives, such as α-methylstyrene; butadiene; isoprene; acrylonitrile; methacrylonitrile; and others are familiar with this Known for techies. If desired, mixtures of comonomers can be used. As with the first polymer, those skilled in the art can use routine experimentation to determine the appropriate amount of various co-monomers that provide the desired film-forming properties and surface polarity values for the second polymer latex described herein.

第二聚合物尤其係藉由共聚合一或多種(甲基)丙烯酸縮水甘油基酯與一或多種共單體(例如一或多種酯烷基具有含至少2個碳原子之(甲基)丙烯酸烷基酯)來設計，該等(甲基)丙烯酸烷基酯包含但不限於丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁基酯、甲基丙烯酸正丁基酯、丙烯酸環己基酯、甲基丙烯酸環己基酯、丙烯酸月桂基酯、甲基丙烯酸月桂基酯、甲基丙烯酸烯丙基酯、甲基丙烯酸羥乙基酯、丙烯酸羥乙基酯及其他為熟習此項技術者所易知者。尤其有用之共單體係酯烷基具有至少4個碳原子之(甲基)丙烯酸烷基酯，例如丙烯酸正丁基酯、甲基丙烯酸正丁基酯、丙烯酸正己基酯、甲基丙烯酸正己基酯及甲基丙烯酸環己基酯。 The second polymer is, in particular, by copolymerizing one or more glycidyl (meth) acrylates with one or more comonomers (e.g., one or more ester alkyl groups having (meth) acrylic acid having at least 2 carbon atoms) Alkyl esters), such alkyl (meth) acrylates include, but are not limited to, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, Cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and others are easy for those skilled in the art. Knower. Especially useful are monoalkyl ester (meth) acrylates having at least 4 carbon atoms, such as n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate And cyclohexyl methacrylate.

如尤其在下文所闡述之本發明實例中所述，儘管第一及第二聚合物可為不同材料，但第一及第二聚合物可有益地具有相同組成(相同縮水甘油基-官能重複單元及來自共單體之重複單元)或具有類似或相同分子量。 As described in particular in the examples of the invention described below, although the first and second polymers may be different materials, the first and second polymers may advantageously have the same composition (same glycidyl-functional repeating units) And repeat units from comonomers) or have similar or identical molecular weights.

儘管第一及第二聚合物之分子量不能總是確切地測得(此乃因該等聚合物可具有自縮水甘油基獲得之橋接結構)，但一般而言，每一聚合物獨立地具有至少10,000或更可能至少50,000之分子量。 Although the molecular weights of the first and second polymers cannot always be determined exactly (because these polymers can have bridged structures obtained from glycidyl groups), in general, each polymer independently has at least A molecular weight of 10,000 or more, possibly at least 50,000.

此外，第一及第二聚合物中之每一者可獨立地具有至少25℃或 更通常至少40℃且至多並包含75℃之玻璃轉變溫度(T_g)，如藉由差示掃描熱量測定(DSC)所測定。 In addition, each of the first and second polymers may independently have a glass transition temperature (T _g ) of at least 25 ° C. or more typically at least 40 ° C. and up to and including 75 ° C., as determined by differential scanning calorimetry (DSC).

第一聚合物乳膠中第一聚合物之量及第二聚合物乳膠中第二聚合物之量可相同或不同。在大部分實施例中，基於全部第一聚合物乳膠固體，第一聚合物乳膠中之第一聚合物之量為至少10重量%且至多並包含40重量%；且基於全部第二聚合物乳膠固體，第二聚合物乳膠中之第二聚合物之量為至少20重量%且至多並包含30重量%。 The amount of the first polymer in the first polymer latex and the amount of the second polymer in the second polymer latex may be the same or different. In most embodiments, the amount of the first polymer in the first polymer latex is at least 10% by weight and up to and including 40% by weight based on the entire first polymer latex solid; and based on the entire second polymer latex The amount of the second polymer in the solid, second polymer latex is at least 20% by weight and up to and including 30% by weight.

第一及第二表面活性劑：First and second surfactants:

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⁺代表之化合物(其中R係C₁₀、C₁₁或C₁₂烴基團)或該等化合物(具有係C₁₀至C₁₂烴基團中之任一者之不同R基團)之混合物。一種含有第一表面活性劑之有用商業產品係Rhodacal^® A246L(可(例如)自Rhodia獲得)。若期望，則可使用該等第一表面活性劑之混合物。 The first polymer latex includes one or more first surfactants, each of which is a sodium alkylsulfonic acid salt, wherein the alkyl group has at least 10 carbon atoms. For example, the first surfactant may be an α-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate, or the first surfactant may be R-CH ₂ -CH = CH-CH ₂ -S (= O ) Compounds represented by ₂ O ^- Na ⁺ (wherein R is a C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon group) or these compounds (having different R groups that are any of C ₁₀ to C ₁₂ hydrocarbon groups) mixture. A useful commercial product containing a first surfactant is Rhodacal ^® A246L (available, for example, from Rhodia). If desired, mixtures of these first surfactants can be used.

調節第一聚合物乳膠中之一或多種第一表面活性劑之總量，使得在將第一聚合物乳膠及第二聚合物乳膠之混合物(闡述於下文中)施加至基板上且乾燥(作為底漆層)時，基於總乾燥底漆層重量，該乾燥底漆層中之一或多種第一表面活性劑之總量為至少1重量%且至多並包含3重量%或通常至少1.6重量%且至多並包含2.8重量%。熟習此項技術者已知將多少第一表面活性劑納入用於製備第一聚合物乳膠之乳液中以便考慮到第一聚合物乳膠及第二聚合物乳膠之混合重量比率所需量存在於乾燥底漆層中。 The total amount of the one or more first surfactants in the first polymer latex is adjusted so that a mixture of the first polymer latex and the second polymer latex (described below) is applied to the substrate and dried (as (Primer layer), based on the total dry primer layer weight, the total amount of one or more first surfactants in the dry primer layer is at least 1% by weight and up to and including 3% by weight or usually at least 1.6% by weight And up to and including 2.8% by weight. Those skilled in the art know how much of the first surfactant is incorporated into the emulsion used to prepare the first polymer latex in order to take into account the mixing weight ratio of the first polymer latex and the second polymer latex. The amount required is present in the dry In the primer layer.

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苯酚硫酸銨鹽。舉例而言，第二 表面活性劑可為聚乙氧基壬基苯酚之硫酸銨鹽，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為至少3且至多並包含10，或更可能n為至少3且至多並包含6。一種含有第二表面活性劑之有用商業產品係Rhodapex^® CO-436(可(例如)自Rhodia獲得)。若期望，則可使用該等第二表面活性劑之混合物。 The second polymer latex includes one or more second surfactants, each of which is an alkylphenol ammonium sulfate salt having at least 3 ethylene oxide units. For example, the second surfactant may be an ammonium sulfate salt of polyethoxynonylphenol, 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. A useful commercial product containing a second surfactant is Rhodapex ^® CO-436 (available, for example, from Rhodia). If desired, mixtures of these second surfactants can be used.

調節第二聚合物乳膠中之一或多種第二表面活性劑之總量，使得在將第一聚合物乳膠及第二聚合物乳膠之混合物(闡述於下文中)施加至基板上且乾燥(作為底漆層)時，基於總乾燥底漆層重量，該乾燥底漆層中之一或多種第二表面活性劑之總量為至少0.35重量%且至多並包含1.1重量%或通常至少0.45重量%且至多並包含0.9重量%。熟習此項技術者已知將多少第二表面活性劑納入製備第二聚合物乳膠之乳液中以便考慮到第一聚合物乳膠及第二聚合物乳膠之混合重量比率所需量存在於乾燥底漆層中。 The total amount of the one or more second surfactants in the second polymer latex is adjusted so that a mixture of the first polymer latex and the second polymer latex (described below) is applied to the substrate and dried (as (Primer layer), based on the total dry primer layer weight, the total amount of one or more second surfactants in the dry primer layer is at least 0.35 wt% and at most and includes 1.1 wt% or usually at least 0.45 wt% And up to and including 0.9% by weight. Those skilled in the art know how much second surfactant is included in the preparation of the second polymer latex in order to take into account the mixed weight ratio of the first polymer latex and the second polymer latex in the dry primer. Layer.

第一聚合物及第二聚合物通常以微細顆粒形式分散於分別包括第一及第二聚合物乳膠之個別水性分散液中。在根據本發明混合該等聚合物乳膠時，可以任一適宜方式將其以塗層調配物形式施加至適宜基板中。可使用水可混溶性有機溶劑(例如甲醇或丙酮)代替每一聚合物乳膠中之一些水。 The first polymer and the second polymer are usually dispersed as fine particles in individual aqueous dispersions including the first and second polymer latexes, respectively. When the polymer latexes are mixed according to the present invention, they can be applied to a suitable substrate in the form of a coating formulation in any suitable manner. A water-miscible organic solvent such as methanol or acetone may be used in place of some of the water in each polymer latex.

通常期望使用平均第一及第二聚合物粒徑分別且獨立地小於200μm、更可能小於150μm及甚至更期望小於100μm之第一及第二聚合物乳膠。為達成小及窄聚合物粒徑分佈，在乳液聚合中可能需要第一聚合物乳膠及第二聚合物乳膠中之任一者或兩者包含超過先前段落中所闡述量之第一及第二表面活性劑量。然而，可藉由使用透析去除過量第一及第二表面活性劑來將總第一及第二表面活性劑量減小至低於本發明所闡述之最高限值。 It is generally desirable to use first and second polymer latexes with average first and second polymer particle diameters of less than 200 μm, more likely less than 150 μm, and even more desirably less than 100 μm, respectively. In order to achieve small and narrow polymer particle size distributions, either or both of the first polymer latex and the second polymer latex may be required in the emulsion polymerization to contain first and second amounts in excess of those set forth in the previous paragraph. Surface active dose. However, the total first and second surfactant doses can be reduced below the maximum limits set forth in the present invention by using dialyzing to remove excess first and second surfactants.

第一聚合物乳膠及第二聚合物乳膠中之每一者可使用乳液聚合製得或以微粒乳液聚合物之水性分散液形式獲得。業內已知包含有用條件及反應物之乳液聚合程序且代表性細節提供於美國專利6,162,597(第5-7卷)中。上文所闡述之第一及第二表面活性劑分別(例如)以至少一種陰離子表面活性劑形式包含於第一聚合物乳膠及第二聚合物乳膠之製備中。然而，第一及第二聚合物乳膠之製備並不限於僅分別使用第一及第二表面活性劑。代表性製備方法提供於下文實例中。 Each of the first polymer latex and the second polymer latex can be made using emulsion polymerization or obtained as an aqueous dispersion of a particulate emulsion polymer. Emulsion polymerization procedures including useful conditions and reactants are known in the art and representative details are provided in US Patent 6,162,597 (Vols. 5-7). The first and second surfactants described above are included in the preparation of the first polymer latex and the second polymer latex, respectively, for example, in the form of at least one anionic surfactant. However, the preparation of the first and second polymer latex is not limited to using only the first and second surfactants, respectively. Representative preparation methods are provided in the examples below.

塗層組合物Coating composition

第一聚合物乳膠及第二聚合物乳膠中之每一者可獨立地包括一或多種水可混溶性有機溶劑(以至多且包含10重量%之量，基於總乳膠重量)；一或多種表面活性劑；一或多種無機消光劑(只要濁度並不顯著增加且透明性並不顯著減弱)；抗靜電劑；酸或鹼，用以調節pH；及緩衝劑。 Each of the first polymer latex and the second polymer latex may independently include one or more water-miscible organic solvents (in an amount up to and including 10% by weight based on the total latex weight); one or more surfaces Active agents; one or more inorganic matting agents (as long as turbidity does not increase significantly and transparency does not significantly decrease); antistatic agents; acids or bases to adjust pH; and buffering agents.

亦可期望以已知量納入一或多種交聯劑(在業內亦可稱為「硬化劑」)以在將聚合物乳膠顆粒施加至載體上且乾燥後進一步促進其交聯。有用交聯劑包含但不限於含醛化合物(例如甲醛及乙二醛)、含伸乙基亞胺化合物(例如四亞甲基-1,4-雙(伸乙基脲))、甲烷磺酸之酯(例如三亞甲基雙甲烷磺酸酯)、活性乙烯基化合物(例如雙丙烯醯基脲及亞甲基二乙烯基磺酸)、含縮水甘油基化合物(例如雙酚縮水甘油基醚)及異氰酸酯。 It may also be desirable to incorporate one or more crosslinking agents (also known as "hardeners" in the industry) in known amounts to further promote the crosslinking of the polymer latex particles after they are applied to the support and dried. Useful crosslinking agents include, but are not limited to, aldehyde-containing compounds (e.g., formaldehyde and glyoxal), ethyleneimine-containing compounds (e.g., tetramethylene-1,4-bis (ethyleneurea)), methanesulfonic acid Esters (such as trimethylene bismethane sulfonate), reactive vinyl compounds (such as bispropenyl urea and methylene divinyl sulfonic acid), glycidyl-containing compounds (such as bisphenol glycidyl ether) And isocyanates.

然而，最佳地，第一聚合物乳膠及第二聚合物乳膠皆不含顯著量之凝聚助劑(例如間苯二酚)及美國專利6,162,597第6卷第53列至第7卷第3列中所闡述用於此目的之其他化合物(如上所述)。在兩種聚合物乳膠係混合物且施加至載體上時，基於乾燥底漆層(闡述於下文中)之總重量，尤其期望第一及第二聚合物乳膠包括小於1重量%之該等凝聚助劑(例如間苯二酚)。 However, optimally, both the first polymer latex and the second polymer latex do not contain significant amounts of coacervation aids (such as resorcinol) and US Patent 6,162,597, Volume 6, Column 53 to Volume 7, Column 3 Other compounds described above for this purpose (as described above). When two polymer latex-based mixtures are applied to a carrier, it is particularly desirable that the first and second polymer latex include less than 1% by weight of these agglomeration aids based on the total weight of the dry primer layer (described below). Agents (such as resorcinol).

因此，在本文所闡述組合物之一些實施例中，組合物之乾燥底漆塗層具有至少28%且至多並包含50%之表面極性。此外，該等組合物可具有下列性質：基於第一聚合物總重量，第一聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，第一聚合物具有至少50℃且至多並包含70℃之玻璃轉變溫度，且第一表面活性劑係α-烯烴(C₁₄-C₁₆)磺酸鈉；基於第二聚合物總重量，第二聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，第二聚合物具有至少50℃且至多並包含70℃之玻璃轉變溫度，且第二表面活性劑係硫酸化聚乙氧基壬基苯酚之銨鹽；組合物之乾燥塗層具有至少28%且至多並包含50%之表面極性；混合物中之第一聚合物乳膠對第二聚合物乳膠之重量比率為1：1且至並包含2.5：1；基於乾燥塗層總重量，第一表面活性劑以至少1重量%且至多並包含3重量%之量存在於混合物之乾燥塗層中；基於乾燥塗層總重量，第二表面活性劑以至少0.35重量%且至多並包含1.1重量%之量存在於混合物之乾燥塗層中；且基於乾燥塗層總重量，混合物之乾燥塗層中之第一及第二表面活性劑之總量小於3.35重量%。 Therefore, in some embodiments of the compositions described herein, the dry primer coating of the composition has a surface polarity of at least 28% and at most and including 50%. In addition, the compositions may have the following properties: based on the total weight of the first polymer, the first polymer includes at least 75% by weight and up to and includes 90% by weight of repeating units derived from glycidyl (meth) acrylate and At least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, the first polymer has a glass transition temperature of at least 50 ° C and up to and including 70 ° C, and the first surface activity Agent is an alpha-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate; based on the total weight of the second polymer, the second polymer includes at least 75% by weight and up to and includes 90% by weight derived from glycidyl (meth) acrylate Ester repeating units and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, the second polymer having a glass transition temperature of at least 50 ° C and up to and including 70 ° C, And the second surfactant is an ammonium salt of sulfated polyethoxynonylphenol; the dry coating of the composition has a surface polarity of at least 28% and at most 50%; the first polymer latex in the mixture The weight of the second polymer latex The ratio is 1: 1 and up to and including 2.5: 1; based on the total weight of the dry coating, the first surfactant is present in the dry coating of the mixture in an amount of at least 1% and up to and including 3% by weight; based on drying The total weight of the coating, the second surfactant is present in the dry coating of the mixture in an amount of at least 0.35 wt% and up to and including 1.1 wt%; and based on the total weight of the dry coating, the first of the dry coatings of the mixture And the total amount of the second surfactant is less than 3.35% by weight.

基板Substrate

可以適宜方式將上文所闡述之組合物(「底漆」組合物)施加至任一適宜載體上進一步處理(processing或treatment)以用於給定工業目的，使得形成本發明基板。所得基板可為不透明、透明或半透明或其 組合(具有不透明部分及透明部分)。 The composition set forth above ("primer" composition) may be applied in any suitable manner to any suitable carrier for further processing or treatment for a given industrial purpose, such that a substrate of the present invention is formed. The resulting substrate can be opaque, transparent or translucent or Combination (with opaque part and transparent part).

舉例而言，乾燥底漆層可形成於任一適宜載體材料上，只要其並不抑制設計所得物件之目的。舉例而言，載體可自包含但不限於以下之材料形成：聚合膜、金屬、玻璃(未處理或(例如)使用四氟碳電漿、疏水性氟或矽氧烷防水材料處理)、矽或陶瓷晶圓、織物、紙及其組合(例如各種膜之壓層或紙及膜之壓層)。所得基板可為剛性或撓性的。尤其有用之載體材料係聚酯、聚碳酸酯、聚苯乙烯、聚醯亞胺、聚醯胺及其複合物。 For example, a dry primer layer can be formed on any suitable carrier material as long as it does not inhibit the purpose of designing the resulting article. For example, the carrier may be formed from a material that includes, but is not limited to, a polymeric film, metal, glass (untreated or (e.g., treated with a tetrafluorocarbon plasma, hydrophobic fluorine or silicone waterproof material), silicon, or Ceramic wafers, fabrics, paper, and combinations thereof (eg, lamination of various films or lamination of paper and films). The resulting substrate can be rigid or flexible. Particularly useful carrier materials are polyester, polycarbonate, polystyrene, polyimide, polyimide, and composites thereof.

基板中所使用之載體可具有通常至少50μm且至多並包含3,000μm之任一期望乾燥平均厚度。本發明中所使用之大部分連續網片具有取決於自其所形成物件之最終用途(例如其納入各種物件或光學或顯示器件中)之平均乾燥厚度(乾燥底漆層及載體)。舉例而言，基板乾燥厚度(包含乾燥底漆層、載體及任一可選層或塗層)可為至少50μm且至多並包含250μm，且尤其對於聚合膜而言，基板乾燥厚度可為至少80μm且至多並包含175μm或至少100μm且至多並包含125μm。 The carrier used in the substrate may have any desired dry average thickness that is usually at least 50 μm and up to and including 3,000 μm. Most of the continuous webs used in the present invention have an average dry thickness (dry primer layer and carrier) depending on the end use of the objects formed from them (for example, they are incorporated into various objects or optical or display devices). For example, the substrate dry thickness (including the dry primer layer, the carrier, and any optional layer or coating) can be at least 50 μm and at most 250 μm, and especially for polymeric films, the substrate dry thickness can be at least 80 μm And up to and including 175 μm or at least 100 μm and up to and including 125 μm.

本發明基板可以各種形式提供，例如呈任一大小或形狀之個別薄板及連續網片(例如適於輥至輥操作之透明基板(包含透明聚酯基板)之連續網片)。該等連續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圖案化材料圖案(闡述於下文中)。 The substrate of the present invention can be provided in various forms, such as individual sheets and continuous meshes of any size or shape (such as continuous meshes of transparent substrates (including transparent polyester substrates) suitable for roll-to-roll operations). The continuous webs can be divided or formed into individual first, second, and other portions, which can be used to form the same or different patterned material patterns (described below).

在乾燥底漆層形成於載體之一個或兩個支撐側上之前或之後，可以適宜方式處理載體材料(尤其對於聚合材料而言)以改良乾燥底漆組合物之黏著，減小基板在製造、塗覆或下文所闡述之其他操作期間之收縮。舉例而言，通常期望在形成乾燥底漆層之前或之後，聚酯或其他聚合載體在一或兩個平面方向(機器及橫向方向)上延伸。然而，在大部分實施例中，使用已知程序及條件在乾燥底漆層形成於載體之 一或兩個支撐側上之後實施橫向及機器方向拉伸。在該等拉伸程序之後於(例如)大於100℃且至多並包含150℃之溫度下熱處理(或熱鬆弛)數分鐘可提供足以凝聚乾燥底漆層中之第一及第二聚合物顆粒之熱能，使得形成相對均勻之乾燥底漆層膜且使第一及第二聚合物中之一或兩者發生交聯(若其具有所需可交聯基團)。 Before or after the dry primer layer is formed on one or both of the support sides of the carrier, the carrier material (especially for polymeric materials) may be treated in a suitable manner to improve the adhesion of the dry primer composition, reducing the Shrinkage during coating or other operations described below. For example, it is often desirable that the polyester or other polymeric support extends in one or two planar directions (machine and lateral direction) before or after the dry primer layer is formed. However, in most embodiments, the dry primer layer is formed on the carrier using known procedures and conditions. Lateral and machine-direction stretching is performed on one or both support sides. Heat treatment (or thermal relaxation) for a few minutes after these stretching procedures, for example, at a temperature greater than 100 ° C and up to and including 150 ° C can provide sufficient time to agglomerate the first and second polymer particles in the dry primer layer. The thermal energy makes it possible to form a relatively uniform dry primer layer film and to crosslink one or both of the first and second polymers (if they have the required crosslinkable groups).

其他有用載體處理包含電暈放電處理、火焰處理及各種清潔及洗滌程序。 Other useful carrier treatments include corona discharge treatment, flame treatment, and various cleaning and washing procedures.

通常以足以向本文所闡述乾燥底漆層提供期望乾燥厚度之覆蓋率(例如以至少30mg固體/m²且至多並包含300mg固體/m²之覆蓋率)使用本文所闡述之任一技術將上文所闡述之底漆組合物施加至本文所闡述適宜載體(例如包含連續聚酯網片之聚酯載體)上。塗層製程可發生於在製造本發明基板期間之任一時間，例如在如上文所闡述之雙軸拉伸之前或在機器方向拉伸之後且在橫向拉伸之前或在雙軸拉伸之後。 Typically the dried primer layer is sufficient to set forth herein to provide a desired thickness of the dried coverage (e.g. solid at least 30mg / m ² and up to and containing a solid 300mg / m ² of coverage) set forth herein using any of the techniques of the upper The primer composition described herein is applied to a suitable support (such as a polyester support comprising a continuous polyester mesh) as described herein. The coating process may occur at any time during the manufacture of the substrate of the present invention, for example, before biaxial stretching as described above or after machine direction stretching and before transverse stretching or after biaxial stretching.

熟習此項技術者亦應瞭解，可藉由本發明之相同或不同底漆組合物之多個塗層達成給定乾燥底漆層之期望乾燥厚度，使得最終乾燥底漆層可為多個具有相同或不同化學組成及乾燥厚度之子層之複合物。若形成多個層之此一複合物，則最終乾燥底漆層之表面極性係(藉由定義)複合乾燥底漆層之最外表面之評估。 Those skilled in the art should also understand that the desired dry thickness of a given dry primer layer can be achieved by multiple coatings of the same or different primer compositions of the present invention, so that the final dry primer layer can be multiple with the same Or a composite of sub-layers of different chemical composition and dry thickness. If such a composite of multiple layers is formed, the surface polarity of the final dry primer layer is (by definition) the evaluation of the outermost surface of the composite dry primer layer.

如上所述，尤其有用之基板包括上面可直接佈置有本文所闡述組合物構成之乾燥底漆層之載體(包括一或多種先前段落中所闡述之材料)。乾燥底漆層包括如上文所定義之第一聚合物乳膠及第二聚合物乳膠之混合物(例如凝聚混合物)。此外，乾燥底漆層具有至少15%且至多並包含50%或至少22%且至多並包含45%之表面極性。尤其期望載體由一或多種透明聚合材料(例如聚酯、聚酯混合物或聚酯及另一聚合物之混合物)構成，且所得基板可具有至少88%及更可能至少93%之積分透射率。舉例而言，尤其有用之透明載體材料可由聚(對 苯二甲酸乙二酯)及聚(萘二甲酸乙二酯)構成。 As mentioned above, particularly useful substrates include a carrier (including one or more of the materials set forth in the previous paragraph) on which a dry primer layer composed of the composition set forth herein can be directly arranged. The dry primer layer comprises a mixture (eg, a coacervate mixture) of a first polymer latex and a second polymer latex as defined above. In addition, the dry primer layer has a surface polarity of at least 15% and up to and including 50% or at least 22% and up to and including 45%. It is particularly desirable that the carrier be composed of one or more transparent polymeric materials, such as polyester, a polyester blend, or a mixture of polyester and another polymer, and the resulting substrate may have an integrated transmittance of at least 88% and more likely at least 93%. For example, a particularly useful transparent carrier material can be Ethylene phthalate) and poly (ethylene naphthalate).

儘管在大部分實施例中將乾燥底漆層直接佈置於載體上(意指在乾燥底漆層與載體之間並不特意形成或提供中間層)，但亦可使用一或多種不同底漆聚合物或聚合物混合物塗覆載體以使用照相技術中通常已知用於此目的之材料形成一或多個「中間底漆層」，且然後可將本發明之乾燥底漆層直接施加至一或多個中間底漆層上。該等中間底漆層可形成於載體之一或兩個支撐側上，且然後可將本發明之乾燥底漆層直接形成於載體之一或兩個支撐側上之中間底漆層上。 Although in most embodiments the dry primer layer is arranged directly on the carrier (meaning that no intermediate layer is intentionally formed or provided between the dry primer layer and the carrier), one or more different primers can also be used for polymerization The polymer or polymer mixture is used to coat a carrier to form one or more "middle primer layers" using materials commonly known in photography for this purpose, and the dry primer layer of the present invention can then be applied directly to one or more Multiple intermediate primer layers. The intermediate primer layers may be formed on one or both support sides of the carrier, and the dry primer layer of the present invention may then be formed directly on the intermediate primer layers on one or both support sides of the carrier.

可由此將乾燥底漆層佈置於載體之至少一個支撐側上，且在許多實施例中，可將相同或不同(在組成、厚度或表面極性)乾燥底漆層直接佈置於載體之兩個支撐側(亦即第一支撐側及第二相對支撐側)上。「支撐側」意欲係指載體之平面側而非載體材料之邊緣。舉例而言，可將本發明之乾燥底漆組合物佈置於載體之一個支撐側上，而可將其他(非發明性)聚合物(或底漆)層佈置於載體之相對支撐側上。 The dry primer layer can thus be arranged on at least one support side of the carrier, and in many embodiments, the same or different (in composition, thickness, or surface polarity) dry primer layer can be directly arranged on two supports of the carrier Side (ie, the first support side and the second opposite support side). "Support side" is intended to mean the planar side of the carrier and not the edge of the carrier material. For example, the dry primer composition of the present invention may be disposed on one support side of a carrier, and other (non-inventive) polymer (or primer) layers may be disposed on the opposite support side of the carrier.

可藉由使用任一適宜方式(例如浸塗、輥塗、漏斗塗覆、噴塗、旋塗或任一通常提供可以任一適宜方式(例如使用照相載體技術中已知之程序及設備)乾燥之均勻塗層之其他方法)施加上文所闡述乳膠混合物(組合物)來在載體之至少一個支撐側上形成乾燥底漆層。另一選擇為，可(例如)使用噴墨、光微影壓印、「柔性版」印刷(使用凸版印刷部件，例如柔性版印刷部件(例如柔性版印刷板及柔性版印刷套筒))、微影印刷(使用微影印刷板)及凹版或凹雕印刷(使用適當印刷部件)將圖案底漆組合物施加至載體上(或施加至其上之任一中間底漆層上)。 It can be made uniform using any suitable method (e.g., dip coating, roll coating, funnel coating, spray coating, spin coating, or any method that generally provides drying by any suitable method (e.g., using procedures and equipment known in photographic carrier technology). Other methods of coating) Apply the latex mixture (composition) set forth above to form a dry primer layer on at least one supporting side of the carrier. Alternatively, for example, inkjet, photolithographic printing, "flexographic" printing (using letterpress printing components such as flexographic printing components (such as flexographic printing plates and flexographic printing sleeves)), Lithographic printing (using a lithographic printing plate) and gravure or intaglio printing (using appropriate printed parts) apply the pattern primer composition to a carrier (or to any intermediate primer layer thereon).

佈置於載體上之乾燥底漆層可具有若干期望性質。舉例而言，乾燥底漆層中乾燥第一聚合物乳膠對乾燥第二聚合物乳膠之重量比率為1：3且至並包含3：1或1：1且至並包含2.5：1。 The dry primer layer disposed on the carrier may have several desirable properties. For example, the weight ratio of the dried first polymer latex to the dried second polymer latex in the dried primer layer is 1: 3 and up to and including 3: 1 or 1: 1 and up to and including 2.5: 1.

另外，基於乾燥底漆層總重量，第一表面活性劑(闡述於上文中)可以至少1重量%且至多並包含3重量%及更通常至少1.6重量%且至多並包含2.8重量%之量存在於乾燥底漆層中。 In addition, based on the total weight of the dry primer layer, the first surfactant (described above) may be present in an amount of at least 1% by weight and up to and including 3% by weight and more usually at least 1.6% by weight and up to and including 2.8% by weight In a dry primer layer.

此外，基於乾燥底漆層總重量，第二表面活性劑以至少0.35重量%且至多並包含1.1重量%或通常至少0.45重量%且至多並包含0.9重量%之量存在於乾燥底漆層中。 In addition, based on the total weight of the dry primer layer, the second surfactant is present in the dry primer layer in an amount of at least 0.35 wt% and up to and including 1.1 wt% or usually at least 0.45 wt% and up to and including 0.9 wt%.

基於乾燥底漆層總重量，乾燥底漆層中第一及第二表面活性劑之總量為至少1.35重量%且至多並包含3.35重量%。 Based on the total weight of the dry primer layer, the total amount of the first and second surfactants in the dry primer layer is at least 1.35 weight% and up to and including 3.35 weight%.

亦有用的是，乾燥底漆層(或如上文所闡述之子層之複合物)具有至少0.05μm且至多並包含0.4μm或通常至少0.05μm且至多並包含0.2μm或甚至至少0.07μm且至多並包含0.2μm之平均乾燥厚度。熟習此項技術者知曉如何測定根據本發明製得之特定底漆組合物之密度且然後計算經施加以達成所得乾燥底漆層之期望乾燥厚度之濕覆蓋率。 Also useful is a dry primer layer (or a composite of sublayers as set forth above) having at least 0.05 μm and at most and including 0.4 μm or usually at least 0.05 μm and at most and including 0.2 μm or even at least 0.07 μm and at most and Contains an average dry thickness of 0.2 μm. Those skilled in the art know how to determine the density of a particular primer composition made according to the present invention and then calculate the wet coverage that is applied to achieve the desired dry thickness of the resulting dry primer layer.

在將如上文所闡述包括第一及第二聚合物乳膠之混合物之塗層施加至適宜載體上且乾燥後，乳膠顆粒混合物通常「凝聚」以在施加其之整個支撐表面上形成通常具有均勻組成之聚合物膜。在許多實施例中，乳膠顆粒亦可自身交聯以提供更可抵抗有機溶劑降解之更耐久性表面。該等耐久性均勻乾燥底漆層塗層可然後提供更適於施加可固化組合物之表面。 After a coating comprising a mixture of first and second polymer latexes as described above is applied to a suitable support and dried, the latex particle mixture generally "agglomerates" to form a generally uniform composition over the entire supporting surface to which it is applied Polymer film. In many embodiments, the latex particles can also crosslink themselves to provide a more durable surface that is more resistant to degradation by organic solvents. These durable uniform dry primer layer coatings can then provide a surface more suitable for applying a curable composition.

物件object

可使用上文所闡述之基板來提供將圖案化材料直接佈置於乾燥底漆層上(其繼而直接佈置於(在大部分實施例中)載體(例如透明聚合載體)上)之物件。尤其有用的是，即使存在圖案化材料，物件亦可具有至少88%或通常至少95%之積分透射率。該等物件可包括具有上文針對基板所闡述之性質之乾燥底漆層，該等性質包含平均乾燥厚度、第一聚合物乳膠對第二聚合物乳膠之重量比率、乳膠中第一及第二乙 烯基聚合物之特定組成及玻璃轉變溫度及特定的第一及第二表面活性劑(及其量)。 The substrates set forth above can be used to provide an article having a patterning material disposed directly on a dry primer layer, which in turn is disposed directly on (in most embodiments) a carrier, such as a transparent polymeric carrier. It is particularly useful that an object can have an integrated transmittance of at least 88% or typically at least 95% even if a patterned material is present. The articles may include a dry primer layer having the properties described above for the substrate, the properties including the average dry thickness, the weight ratio of the first polymer latex to the second polymer latex, the first and second in the latex B The specific composition and glass transition temperature of the alkenyl polymer and the specific first and second surfactants (and their amounts).

亦期望該等物件中之該等乾燥底漆層實質上不含間苯二酚，例如基於乾燥底漆層總重量小於1重量%間苯二酚或甚至小於0.5重量%。 It is also desirable that the dry primer layers in the objects are substantially free of resorcinol, such as less than 1% by weight resorcinol or even less than 0.5% by weight based on the total weight of the dry primer layer.

可以任一適宜方式(例如使用上文所闡述用於形成乾燥底漆層之方式及技術，包含但不限於，使用柔性版印刷部件(例如柔性版印刷板、柔性版印刷圓筒及柔性版印刷套筒)、使用凹雕印刷及使用凹版印刷)將圖案化材料按一定圖案形式提供於本發明物件中。亦可使用噴墨印刷方法及設備將圖案化材料施加至基板上。在施加後，圖案化材料之至少一部分可包括平均線寬小於15μm或甚至小於10μm之細線。當然，圖案化材料無需完全由該等細線構成，此乃因其亦可包括較大區、文字及各種形狀(若期望)。然而，在大部分實施例中，圖案化材料之至少一部分主要包括細線以形成細線之柵格或圖案。在一些實施例中，乾燥底漆層上之整個圖案化材料由該等細線構成。 In any suitable manner (e.g., using the methods and techniques described above for forming a dry primer layer, including, but not limited to, the use of flexographic printing components (e.g., flexographic printing plates, flexographic printing cylinders, and flexographic printing) Sleeve), using intaglio printing and using intaglio printing) to provide the patterned material in the object of the present invention in a certain pattern. Patterned materials can also be applied to substrates using inkjet printing methods and equipment. After application, at least a portion of the patterned material may include fine lines with an average line width of less than 15 μm or even less than 10 μm. Of course, the patterned material need not be entirely composed of such thin lines, because it can also include larger areas, text, and various shapes (if desired). However, in most embodiments, at least a portion of the patterned material mainly includes thin lines to form a grid or pattern of thin lines. In some embodiments, the entire patterned material on the dry primer layer is composed of the thin lines.

有用圖案化材料通常包括任一可按一定圖案形式施加至基板上且可以此形式用於特定目的之適宜組合物或「油墨」。 Useful patterned materials typically include any suitable composition or "ink" that can be applied to a substrate in a patterned form and that can be used for a particular purpose in that form.

在一些實施例中，術語「圖案化材料」係導電或可進一步處理以變得導電之「導電印刷材料」。該等材料可為有機、無機材料或包括有機及無機組份。有用導電印刷材料通常至少因應於電位而展現預定活性，但該等材料亦可對其他刺激具有反應。導電印刷材料之實例包含但不限於導電有機或無機聚合物(或其複合物)、氧化銦錫顆粒、顆粒、薄片或金屬(例如金、銀、銅、鉑、鎳、鐵、鋁及鈀)之長絲、金屬錯合物顆粒、金屬合金及金屬前體及其組合。導電印刷材料另一選擇可為導電材料前體，例如金屬鹽(例如銀鹽，如銀鹵化物或有機銀鹽)或無電金屬化觸媒(例如鈀顆粒)。尤其有用之導電印刷材料包含 銀及銀鹽、金、銅、鈀、鉑、鎳、鐵、氧化銦錫、碳黑及其組合。 In some embodiments, the term "patterned material" is a "conductive printing material" that is conductive or can be further processed to become conductive. These materials may be organic or inorganic materials or include organic and inorganic components. Useful conductive printing materials typically exhibit a predetermined activity at least in response to a potential, but these materials can also respond to other stimuli. Examples of conductive printing materials include, but are not limited to, conductive organic or inorganic polymers (or composites thereof), indium tin oxide particles, particles, flakes, or metals (e.g., gold, silver, copper, platinum, nickel, iron, aluminum, and palladium) Filaments, metal complex particles, metal alloys and metal precursors, and combinations thereof. Another option for conductive printing material may be a conductive material precursor, such as a metal salt (such as a silver salt such as a silver halide or an organic silver salt) or an electroless metallization catalyst (such as palladium particles). Particularly useful conductive printing materials include Silver and silver salts, gold, copper, palladium, platinum, nickel, iron, indium tin oxide, carbon black, and combinations thereof.

另外，有用導電印刷材料可具有任一形式或組成，包含微粒(或任一期望形狀)、聚合材料或非聚合分子。舉例而言，有用微粒或成膜聚合導電印刷材料包含但不限於聚噻吩、聚苯胺、聚吡咯、聚咔唑、聚吲哚、聚氮呯、聚伸乙基二氧基噻吩、聚(3-烷基噻吩、聚(對-伸苯基伸乙烯基)、聚(對-伸苯基)、聚(苯乙烯磺酸)(PSS)、聚(對-伸苯基硫化物)、聚乙炔、聚(3,4-伸乙基二氧基噻吩)(PEDOT)及聚(苯乙烯磺酸)及聚(3,4-伸乙基二氧基噻吩)之混合物(PSS：PEDOT)。 Additionally, useful conductive printing materials can have any form or composition, including particulates (or any desired shape), polymeric materials, or non-polymeric molecules. For example, useful particulate or film-forming polymeric conductive printing materials include, but are not limited to, polythiophene, polyaniline, polypyrrole, polycarbazole, polyindole, polyazepine, polyethoxydioxythiophene, poly (3 -Alkylthiophene, poly (p-phenylenephenylene), poly (p-phenylene), poly (styrenesulfonic acid) (PSS), poly (p-phenylene sulfide), polyacetylene, Poly (3,4-ethylenedioxythiophene) (PEDOT) and a mixture of poly (styrenesulfonic acid) and poly (3,4-ethylenedioxythiophene) (PSS: PEDOT).

在一些實施例中，圖案化材料或導電印刷材料可包括導電材料奈米顆粒或完全由其構成，且由此其大小係以奈米(nm)形式量測，舉例而言，至少一個尺寸小於200nm且在一些實施例中平均直徑為至少3nm至且包含100nm。奈米顆粒可以簇形式提供或使用。奈米顆粒之形狀並無限制且包含奈米球、奈米棒及奈米杯。舉例而言，有用導電印刷材料可包含碳奈米顆粒，例如碳黑、碳奈米管、石墨及等效含碳材料。金屬奈米顆粒及金、銀、鈀、鉑及銅之分散液亦可用於圖案化材料中。 In some embodiments, the patterning material or the conductive printing material may include or consist entirely of nano particles of the conductive material, and thus its size is measured in the form of nanometers (nm), for example, at least one dimension is less than 200 nm and in some embodiments an average diameter of at least 3 nm to and including 100 nm. Nanoparticles can be provided or used in the form of clusters. The shape of the nano particles is not limited and includes nano balls, nano bars, and nano cups. For example, useful conductive printing materials may include carbon nano particles such as carbon black, carbon nanotubes, graphite, and equivalent carbon-containing materials. Metal nano particles and dispersions of gold, silver, palladium, platinum and copper can also be used in patterned materials.

更尤其而言，本發明中所使用之印刷材料包括導電金屬(或其前體)之顆粒(例如奈米顆粒)，例如銀、金、銅、鈀、鉑、鎳及鐵或其組合中之任一者之顆粒，該等金屬顆粒可分散於如下文所闡述之光可固化或熱可固化組合物內。亦可使用該等金屬之前體，例如金屬之鹽或金屬-配體錯合物。此外，可將氧化銦錫納入圖案化材料中。 More specifically, the printing materials used in the present invention include particles (e.g., nano particles) of conductive metals (or precursors thereof), such as silver, gold, copper, palladium, platinum, nickel, and iron, or combinations thereof. Particles of any one of the metal particles may be dispersed in a photo-curable or heat-curable composition as described below. Such metal precursors can also be used, such as metal salts or metal-ligand complexes. In addition, indium tin oxide can be incorporated into the patterning material.

一般而言，藉由以下方式來調配圖案化材料之固體材料：分散、溶解或懸浮於適宜載劑液體中，由此形成用於施加至如本文所闡述之基板之液體組合物(「油墨」)，且尤其使用如本文所闡述之柔性版印刷部件。用於此目的之載劑液體可包含有機溶劑及水，只要其與圖案化材料之固體組份相容且並不與其反應(惰性)。舉例而言，載劑 液體可為一或多種能夠將固體組份(例如金屬顆粒)分散或懸浮於足以實施本發明方法之溶液中之有機溶劑。在如下文所闡述之一些實施例中，載劑液體可為光可固化或熱可固化組合物中作為圖案化材料之一部分之反應性組份。 In general, solid materials of patterned materials are formulated by dispersing, dissolving, or suspending in a suitable carrier liquid, thereby forming a liquid composition ("ink") for application to a substrate as described herein ), And in particular flexographic printing parts as explained herein. The carrier liquid used for this purpose may include organic solvents and water as long as it is compatible with the solid components of the patterning material and does not react with it (inert). For example, a carrier The liquid may be one or more organic solvents capable of dispersing or suspending solid components (such as metal particles) in a solution sufficient to perform the method of the present invention. In some embodiments as described below, the carrier liquid may be a reactive component as part of a patterning material in a photo-curable or heat-curable composition.

可圖案化材料調配物應至少能夠至少潤濕柔性版印刷部件之最上凸版表面，此乃因此係在本發明方法期間將圖案化材料施加至基板之乾燥底漆層之期望方法。載劑液體可具有一定揮發性，且亦可在柔性版印刷部件中引起某一程度之膨脹，此取決於製備柔性版印刷部件之組合物類型。因此，可有利地使用並不侵襲柔性版印刷部件之彈性體凸版表面或不利地影響其穩定性及尺寸大小之載劑液體。業內充分教示用於特定圖案化材料之適宜載劑液體。代表性有用載劑液體溶劑包含但不限於醇(例如異丙醇、2-乙基己醇及α-萜烯醇)、乙酸酯(例如乙酸乙酯)、水、烴(例如甲苯及環己烷)及可混溶溶劑之組合。 The patternable material formulation should at least be able to wet at least the uppermost relief surface of the flexographic printing component, which is therefore the desired method of applying the patterning material to the dry primer layer of the substrate during the method of the invention. The carrier liquid may have some volatility and may also cause a certain degree of swelling in flexographic printing parts, depending on the type of composition used to prepare the flexographic printing parts. Therefore, it is advantageous to use a carrier liquid that does not attack the surface of the elastomeric relief of the flexographic printing member or adversely affects its stability and size. The industry is well taught about suitable carrier liquids for specific patterning materials. Representative useful carrier liquid solvents include, but are not limited to, alcohols (e.g., isopropanol, 2-ethylhexanol, and alpha-terpene alcohol), acetates (e.g., ethyl acetate), water, hydrocarbons (e.g., toluene and cyclic alcohols) Hexane) and a miscible solvent.

一般而言，在施加至基板上之前，圖案化材料通常具有至少1cp且至多並包含1500cp或通常至少100cp且至多並包含1000cp之黏度。若期望，則可使用較高黏度之圖案化材料。可使用習用方式及設備(例如布魯克菲爾德黏度計(Brookfield Viscometer)DV-II+Pro(Brookfield Engineering實驗室))量測黏度。 Generally, the patterned material generally has a viscosity of at least 1 cp and up to and including 1500 cp or usually at least 100 cp and up to and including 1000 cp before being applied to a substrate. If desired, higher viscosity patterning materials can be used. Viscosity can be measured using conventional methods and equipment, such as the Brookfield Viscometer DV-II + Pro (Brookfield Engineering Laboratory).

一些有用圖案化材料包含但不限於含有導電顆粒(例如金屬薄片或顆粒)之導電油墨。導電油墨包含導電含銀油墨(例如包括銀奈米顆粒之油墨)、含金油墨、含銅油墨、含碳油墨、含鈀油墨及其他含有用於電鍍或無電鍍覆之「晶種」材料之油墨。該等油墨中之一些可在商業上自諸如InkTec(California)、Flint Ink公司(Michigan)、Method Development公司(Chicago)及Novacentrix(Austin,Texas)等來源獲得。該等「油墨」中之一些可用作載劑液體，而其他油墨包括載劑液體及一或多種導電組份。 Some useful patterning materials include, but are not limited to, conductive inks containing conductive particles, such as metal flakes or particles. Conductive inks include conductive silver-containing inks (e.g., inks containing silver nanoparticles), gold-containing inks, copper-containing inks, carbon-containing inks, palladium-containing inks, and other materials that contain "seed" materials used for electroplating or electroless plating. Ink. Some of these inks are commercially available from sources such as InkTec (California), Flint Ink (Michigan), Method Development (Chicago), and Novacentrix (Austin, Texas). Some of these "inks" can be used as a carrier liquid, while others include a carrier liquid and one or more conductive components.

在一些實施例中，圖案化材料可進一步包括著色劑，包含但不限於染料、光學吸收劑、顏料、遮光劑及任一在本發明方法期間之任一時間改變圖案化材料之透射或反射性質之材料。 In some embodiments, the patterning material may further include a colorant, including but not limited to dyes, optical absorbers, pigments, opacifiers, and any one of the methods of changing the transmission or reflection properties of the patterning material Of materials.

如上所述，圖案化材料可為光可固化或熱可固化。「光可固化」係指組合物可在曝光於適宜光固化輻射後發生聚合或交聯。舉例而言，光固化可在使用(例如)λ_max為至少150nm且至多並包含750nm之適宜輻射或更可能使用λ_max為至少150nm且至多並包含400nm之輻射曝光包括適宜光可固化組份之圖案化材料後發生。可使用該等輻射之適宜來源實施曝光適宜時間以提供所需固化能量。熟習此項技術者將知曉如何最佳化用於達成期望聚合或交聯之條件。 As described above, the patterned material may be photo-curable or heat-curable. "Photocurable" means that the composition can polymerize or crosslink after exposure to suitable photocurable radiation. For example, photocuring can be performed using, for example, a suitable radiation having a λ _max of at least 150 nm and up to and including 750 nm or more likely using a radiation exposure with a λ _max of at least 150 nm and up to and including 400 nm including suitable photo-curable components. Occurs after patterning the material. A suitable source of such radiation can be used for a suitable exposure time to provide the desired curing energy. Those skilled in the art will know how to optimize the conditions used to achieve the desired polymerization or crosslinking.

亦可藉由使用適宜熱源(例如熱板、紅外、紅外加熱(例如曝光至發射近紅外光或紅外光之雷射)或其他加熱裝置)將圖案化材料加熱至至少110℃且至多並包含150℃之溫度保持足以獲得期望聚合或交聯之時間(例如至少10分鐘且至多並包含30分鐘)來實施有用熱固化製程。熟習此項技術者可易於確定達成期望聚合或交聯所期望之最佳加熱溫度及時間條件。 The patterned material can also be heated to at least 110 ° C and up to and including 150 by using a suitable heat source (e.g., a hot plate, infrared, infrared heating (e.g., exposure to a laser emitting near-infrared or infrared light), or other heating means) The temperature of ° C is maintained for a time (e.g., at least 10 minutes and up to and including 30 minutes) to achieve the desired polymerization or crosslinking to perform a useful thermal curing process. Those skilled in the art can easily determine the optimal heating temperature and time conditions desired to achieve the desired polymerization or crosslinking.

更尤其而言，圖案化材料可為包括如上文所闡述金屬顆粒之光可固化組合物及自由基可固化組合物、酸催化可固化組合物或自由基可固化組合物及酸催化可固化組合物之混合物。 More particularly, the patterned material may be a photo-curable composition and a radical-curable composition including metal particles as described above, an acid-catalysable curable composition or a radical-curable composition, and an acid-catalysable curable composition A mixture of things.

自由基可固化組合物通常包括一或多種在曝光於適宜輻射後會生成繼而引起亦存在反應性單體、寡聚物或聚合物之聚合或交聯之自由基之材料。各種所需及可選組份通常攜載於一或多種溶劑(載劑溶劑)內，該等溶劑可為不同化學化合物或其亦可為對自由基(例如亦用作載劑溶劑之自由基反應性單體，例如丙烯酸酯)具有反應性之化合物。許多該等自由基可固化組合物闡述於期刊及專利文獻中。 Free radical curable compositions typically include one or more materials that, upon exposure to suitable radiation, will generate free radicals which in turn cause polymerization or cross-linking of reactive monomers, oligomers or polymers. Various required and optional components are usually carried in one or more solvents (carrier solvents). These solvents can be different chemical compounds or they can be free radicals (such as free radicals also used as carrier solvents). Reactive monomers such as acrylates) are reactive compounds. Many of these free radical curable compositions are described in journals and patent literature.

類似地，酸催化可固化組合物亦在業內已知且通常包括一或多 種在曝光於適宜輻射後生成酸部分(該酸部分然後催化設計用於該化學環境之適宜化學化合物之聚合或交聯)之化合物。 Similarly, acid-catalyzed curable compositions are also known in the art and often include one or more A compound that, upon exposure to suitable radiation, generates an acid moiety that then catalyzes the polymerization or crosslinking of a suitable chemical compound designed for the chemical environment.

在其他圖案化材料中，光可固化組合物可包含自由基可固化及酸催化可固化之化學物質之混合物。在使用兩種類型之固化化學物質時，所得交聯基質可構成包含交聯材料之互穿聚合物網絡(IPN)。此增加之交聯密度可進一步增加耐化學品性及硬度且向包括導電細線之最終導電金屬圖案提供優異性質。 Among other patterned materials, the photocurable composition may include a mixture of free radical curable and acid catalyzed curable chemicals. When using two types of curing chemistries, the resulting crosslinked matrix can constitute an interpenetrating polymer network (IPN) containing crosslinked materials. This increased crosslinking density can further increase chemical resistance and hardness and provide excellent properties to the final conductive metal pattern including conductive thin wires.

(a)光可聚合環氧樹脂材料(a) Photopolymerizable epoxy material

陽離子可聚合環氧樹脂材料(「環氧樹脂」)係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： A cationic polymerizable epoxy material ("epoxy resin") is an organic compound having at least one ethylene oxide ring, which is shown in the following formula:

其可藉由開環機制聚合。該等環氧樹脂材料亦稱為「環氧化物」，包含單體環氧樹脂化合物及聚合型環氧化物且可為脂肪族、環脂族、芳族或雜環的。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個且甚至至少約2個可聚合環氧基。聚合環氧樹脂材料包含具有末端環氧基之直鏈聚合物(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)。 It can be polymerized by a ring-opening mechanism. These epoxy materials are also referred to as "epoxides" and include monomeric epoxy compounds and polymeric epoxides and can be aliphatic, cycloaliphatic, aromatic, or heterocyclic. Such materials typically have an average of at least one polymerizable epoxy group per molecule, or typically have at least about 1.5 and even at least about 2 polymerizable epoxy groups per molecule. Polymeric epoxy materials include linear polymers with terminal epoxy groups (such as diglycidyl ethers of polyoxyalkylene glycols), polymers with backbone (backbone) ethylene oxide units (such as polybutadiene Ene polyepoxide) and polymers having side chain epoxy groups (such as glycidyl methacrylate polymer or copolymer).

可聚合環氧樹脂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樹脂材料之混合物。每分子中環氧基之「平均」數係藉由將環氧樹脂材料中環氧基之總數除以所存在之含有環氧樹脂之分子之總數來確定。 The polymerizable epoxy material may be a single compound or it may be a mixture of different epoxy materials containing one, two or more epoxy groups per molecule. The "average" number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy material by the total number of molecules containing epoxy resin present.

環氧樹脂材料可自低分子量單體材料至高分子量聚合物變化且 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過程之任一基團。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。環氧樹脂材料之分子量可為至少58且至多100,000並包含100,000或甚至更高。 Epoxy materials can vary from low molecular weight monomer materials to high molecular weight polymers and The nature of its main chain 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, siloxane groups, nitro groups, and phosphate groups. The molecular weight of the epoxy material can be at least 58 and up to 100,000 and include 100,000 or even higher.

有用環氧樹脂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樹脂材料之更詳細列表提供於美國專利3,117,099(Proops等人)中。其他有用環氧樹脂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]。 Useful epoxy materials include those containing epoxy cyclohexane groups, such as epoxy cyclohexane formate (e.g. 3,4-epoxycyclohexylmethyl-3,4-epoxy ring Hexane formate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexane formate) and adipic acid bis (3, 4-Epoxy-6-methylcyclohexylmethyl) ester. A more detailed list of useful epoxy materials having this property is provided in US Patent 3,117,099 (Proops et al.). Other useful epoxy resin materials include glycidyl ether monomers, which are glycidyl ethers of polyhydric phenols obtained by reacting polyhydric phenols with excess chlorohydrins (e.g., epichlorohydrin) [eg 2,2-bis- ( 2,3-epoxypropoxyphenol) -propane diglycidyl ether].

許多市售環氧樹脂材料係有用的，包含縮水甘油基醚，例如雙酚-A-二縮水甘油基醚(DGEBA)、雙酚S及雙酚F之縮水甘油基醚、丁二醇二縮水甘油基醚、雙酚-A-延伸之縮水甘油基醚、苯酚-甲醛縮水甘油基醚(環氧基酚醛清漆)及甲酚-甲醛縮水甘油基醚(環氧基甲酚酚醛清漆)；環氧化烯烴，例如1,2-環氧基辛烷、1,2,13,14-十四烷二環氧化物、1,2,7,8-辛烷二環氧化物、十八烯氧化物、表氯醇、苯乙烯氧化物、乙烯基環氧環己烷、環氧環己烷、縮水甘油、甲基丙烯酸縮水甘油基酯、雙酚A之二縮水甘油基醚(例如彼等以EPON商標購得者，例如來自Momentive之Epon^TM 828、Epon^TM 825、Epon^TM 1004及Epon^TM 1010，來自Dow Chemical公司之DER-331、DER-332及DER-334樹脂)、乙烯基環己烯二氧化物(例如來自Polyscience之ERL-4206樹脂)、3,4-環氧基環己基甲基-3,4-環氧基環己烯甲酸酯(例如來自Dow Chemical公司之ERL-4221、UVR 6110或UVR 6105樹脂)、3,4-環 氧基-6-甲基環己基甲基-3,4-環氧基-6-甲基-環己烯甲酸酯(例如來自Pfalz及Bauer)、己二酸雙(3,4-環氧基-6-甲基環己基甲基)酯、雙(2,3-環氧基-環戊基)醚、經聚丙二醇改質之脂肪族環氧樹脂、二戊烯二氧化物、環氧化聚丁二烯(例如來自FMC公司之Oxiron 2001樹脂)、含有環氧基官能基之聚矽氧樹脂、阻燃環氧樹脂(例如自Dow Chemical公司購得之DER-580樹脂，其係溴化雙酚型環氧樹脂)、苯酚甲醛清漆型酚醛樹脂之1,4-丁二醇二縮水甘油基醚(例如來自Dow Chemical公司之DEN-431及DEN-438樹脂)、雷鎖辛(resorcinol)二縮水甘油基醚(例如來自Dow Corning公司之CYRACURE^TM樹脂)、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間二噁烷、2-(3,4-環氧基環己基-5,5-螺-3,4-環氧基)環己烷-間二噁烷、乙烯基環己烯單氧化物、1,2-環氧基十六烷(例如來自Dow Corning公司之CYRACURE^TM樹脂)、烷基縮水甘油基醚(例如HELOXY^TM Modifier 7及HELOXY^TM Modifier 8(來自Momentive))、丁基縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 61)、甲苯酚基縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 62)、對第三丁基苯基縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 65)；多官能縮水甘油基醚，例如1,4-丁二醇之二縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 67)、新戊二醇之二縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 68)、環己烷二甲醇之二縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 107)、三羥甲基乙烷三縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 44)、三羥甲基丙烷三縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 48)、脂肪族多元醇之聚縮水甘油基醚(例如來自Momentive之HELOXY^TM Modifier 84)；聚二醇二環氧化物(例如來自Momentive之HELOXY^TM Modifier 32)；雙酚F環氧化物(例如來自Huntman Advanced Materials 之EPN-1138或GY-281樹脂)及9,9-雙[4-(2,3-環氧基丙氧基)-苯基]茀酮(例如來自Momentive之Epon^TM 1079樹脂)。 Many commercially available epoxy materials are useful and include glycidyl ethers, such as bisphenol-A-diglycidyl ether (DGEBA), glycidyl ethers of bisphenol S and bisphenol F, butanediol diglycidyl Glyceryl ether, bisphenol-A-extended glycidyl ether, phenol-formaldehyde glycidyl ether (epoxy novolac) and cresol-formaldehyde glycidyl ether (epoxy cresol novolac); Alkylene oxides such as 1,2-epoxy octane, 1,2,13,14-tetradecane diepoxide, 1,2,7,8-octane diepoxide, octadecene oxide , Epichlorohydrin, styrene oxide, vinyl epoxycyclohexane, epoxycyclohexane, glycidol, glycidyl methacrylate, diglycidyl ether of bisphenol A (such as EPON Trademark purchasers, such as Epon ^TM 828, Epon ^TM 825, Epon ^TM 1004, and Epon ^TM 1010 from Momentive, DER-331, DER-332, and DER-334 resins from Dow Chemical), vinylcyclohexene di Oxides (e.g. ERL-4206 resin from Polyscience), 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexene carbamate (e.g. from Dow Chemical) ERL-4221, UVR 6110 or UVR 6105 resin), 3,4-epoxy-6-methylcyclohexylmethyl-3,4-epoxy-6-methyl-cyclohexene carbamate (e.g. From Pfalz and Bauer), bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate, bis (2,3-epoxy-cyclopentyl) ether, modified by polypropylene glycol Quality aliphatic epoxy resin, dipentene dioxide, epoxidized polybutadiene (such as Oxiron 2001 resin from FMC), epoxy resin containing polysiloxane resin, flame retardant epoxy resin ( For example, DER-580 resin available from Dow Chemical, which is a brominated bisphenol epoxy resin, and 1,4-butanediol diglycidyl ether (for example, from Dow Chemical Company). DEN-431 and DEN-438 resins), resorcinol diglycidyl ether (e.g. CYRACURE ^TM resin from Dow Corning), 2- (3,4-epoxycyclohexyl-5,5 -Spiro-3,4-epoxy) cyclohexane-m-dioxane, 2- (3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy) cyclohexane M-dioxane, vinylcyclohexene monooxide, 1,2-epoxyhexadecane (e.g. CYRACUR from Dow Corning) E ^TM resin), alkyl glycidyl ether (such as HELOXY ^TM Modifier 7 and HELOXY ^TM Modifier 8 (from Momentive)), butyl glycidyl ether (such as HELOXY ^TM Modifier 61 from Momentive), cresol glycidyl Ether (such as HELOXY ^™ Modifier 62 from Momentive), p-tert-butylphenyl glycidyl ether (such as HELOXY ^™ Modifier 65 from Momentive); polyfunctional glycidyl ether, such as 1,4-butanediol Diglycidyl ether (such as HELOXY ^™ Modifier 67 from Momentive), diglycidyl ether of neopentyl glycol (such as HELOXY ^™ Modifier 68 from Momentive), diglycidyl ether of cyclohexanedimethanol ( For example, HELOXY ^TM Modifier 107 from Momentive, triglycidyl ether of trimethylolethane (for example, HELOXY ^TM Modifier 44 from Momentive), triglycidyl ether for trimethylolpropane (for example, HELOXY ^TM Modifier from Momentive ⁾ 48), the aliphatic polyhydric alcohol polyglycidyl ether (e.g. from Momentive of HELOXY ^TM Modifier 84); polyglycol diepoxide (e.g. from Momentive of HELOXY ^TM Modifier 32); Phenol F epoxide (e.g. EPN-1138 or GY-281 resin from Huntman Advanced Materials) and 9,9-bis [4- (2,3-epoxypropoxy) -phenyl] fluorenone (e.g. Epon ^™ 1079 resin from Momentive).

其他有用環氧樹脂材料係樹脂，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。其他有用環氧樹脂材料係表氯醇(例如表氯醇)、環氧烷(例如氧化丙烯及氧化苯乙烯)、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)。其他有用環氧樹脂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樹脂材料。該等環氧樹脂材料之商業實例包含自Momentive購得之UV 9300、UV 9315、UV 9400、UV 9425聚矽氧材料。 Other useful epoxy resin-based resins, such as those derived from the copolymerization of glycidyl acrylates (such as glycidyl acrylate and glycidyl methacrylate) with one or more ethylenically unsaturated polymerizable monomers Copolymer. Other useful epoxy materials are epichlorohydrin (such as epichlorohydrin), alkylene oxide (such as propylene oxide and styrene oxide), alkenyl oxide (such as butadiene oxide), and glycidyl ester (such as glycidyl Ethyl glycerate). Other useful epoxy materials are polysiloxanes with epoxy functional groups or groups such as cyclohexyl epoxy groups, especially their epoxy materials with a polysiloxane backbone. Commercial examples of these epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 polysiloxane materials available from Momentive.

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

光可聚合環氧樹脂材料可包括兩種或更多種不同環氧樹脂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樹脂材料，例如一或多種低分子量(低於200)環氧樹脂材料與一或多種中等分子量(200至10,000)光可聚合環氧樹脂材料或一或多種該等光可聚合環氧樹脂材料與一或多種較高分子量(高於10,000)環氧樹脂材料之摻合物。 The photopolymerizable epoxy material may include 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 weights (200 to 10,000) ) Photopolymerizable epoxy material or a blend of one or more such photopolymerizable epoxy materials with one or more higher molecular weight (greater than 10,000) epoxy materials.

可針對給定用途使用光可聚合環氧樹脂材料提供黏合劑功能(若期望)。另外，若需要，則出於此目的可包含非光可固化聚合物或樹脂。另一選擇為，可使用下文所闡述之光可固化丙烯酸酯提供黏合劑功能。 Adhesive functionality can be provided using a photopolymerizable epoxy material for a given application, if desired. In addition, if necessary, a non-photocurable polymer or resin may be included for this purpose. Alternatively, the photocurable acrylates described below can be used to provide the adhesive function.

光可聚合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聚合環氧樹脂材料。舉例而言，基於光可固化組合物中 (a)至(d)所有4種組份之總重量，一或多種光可聚合環氧樹脂材料係以至少10重量%且至多並包含95重量%之量存在。 The photopolymerizable composition includes one or more amounts of a photopolymerizable epoxy material suitable to provide the desired effective photocuring or photopolymerization. For example, in photo-curable compositions (a) to (d) the total weight of all four components, one or more photopolymerizable epoxy resin materials are present in an amount of at least 10% by weight and up to and including 95% by weight.

(b)光酸生成劑(b) Photoacid generator

可使用各種化合物來生成適宜酸以參與本文所闡述之光可聚合組合物之光固化。一些該等「光酸生成劑」為酸性且其他者為非離子性。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。可用作光酸生成劑之各種化合物可購自各種商業來源或使用已知合成方法及起始材料來製備。 Various compounds can be used to generate suitable acids to participate in the photocuring of the photopolymerizable composition described herein. Some of these "photoacid generators" are acidic and others are non-ionic. Those skilled in the art can readily understand other useful photoacid generators other than those described below based on the teachings provided herein. Various compounds useful as photoacid generators can be purchased from various commercial sources or prepared using known synthetic methods and starting materials.

(i)鎓鹽(i) Onium salts

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 onium hydrochloric acid generator includes, but is not limited to, a diazonium salt, a sulfonium, an iodonium, or a sulfonium salt, and includes a polyaryldiazonium, a sulfonium, an iodonium, and a sulfonium salt. Iodonium or sulfonium 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 arenesulfonate ). An onium salt may also be an oligomer or polymer compound having multiple onium salt moieties and a molecule having a single onium salt moiety.

有用芳族碘鎓鹽之實例包含但不限於四氟硼酸二苯基碘鎓；四氟硼酸二(4-甲基苯基)碘鎓；四氟硼酸苯基-4-甲基苯基碘鎓；四氟硼酸二(4-庚基苯基)碘鎓；六氟磷酸二(3-硝基苯基)碘鎓；六氟磷酸二(4-氯苯基)碘鎓；四氟硼酸二(萘基)碘鎓；四氟硼酸二(4-三氟甲基苯基)碘鎓；六氟磷酸二苯基碘鎓；六氟磷酸二(4-甲基苯基)碘鎓；六氟砷酸二苯基碘鎓；四氟硼酸二(4-苯氧基苯基)碘鎓；六氟磷酸苯基-2-噻吩基碘鎓；六氟磷酸3,5-二甲基吡唑基-4-苯基碘鎓；六氟銻酸二苯基碘鎓；2,2'-四氟硼酸二苯基碘鎓；六氟磷酸二(2,4-二氯苯基)碘鎓；六氟磷酸二(4-溴苯基)碘鎓；六氟磷酸二(4-甲氧基苯基)碘鎓；六氟磷酸二(3-羧基苯基)碘鎓；六氟磷酸二(3-甲氧基羰基苯基)碘鎓；六氟磷酸二(3-甲氧基磺醯基苯基)碘鎓；六氟磷酸二(4-乙醯胺基 苯基)碘鎓；六氟磷酸二(2-苯并噻吩基)碘鎓；及六氟銻酸二苯基碘鎓；及其混合物。該等化合物可藉由根據Beringer等人，J.Am.Chem.Soc.81,342(1959)之教示覆分解相應芳族碘鎓簡單鹽(例如二苯基碘鎓硫酸氫鹽)來製備。 Examples of useful aromatic iodonium salts include, but are not limited to, diphenyliodonium tetrafluoroborate; bis (4-methylphenyl) iodonium tetrafluoroborate; phenyl-4-methylphenyliodonium tetrafluoroborate ; Bis (4-heptylphenyl) iodonium tetrafluoroborate; bis (3-nitrophenyl) iodonium hexafluorophosphate; bis (4-chlorophenyl) iodonium hexafluorophosphate; bis (4-chlorophenyl) iodonium hexafluorophosphate Naphthyl) iodonium; bis (4-trifluoromethylphenyl) iodonium tetrafluoroborate; diphenyliodonium hexafluorophosphate; bis (4-methylphenyl) iodonium hexafluorophosphate; hexafluoroarsenic Acid diphenyliodonium; bis (4-phenoxyphenyl) iodonium tetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate; 3,5-dimethylpyrazolyl hexafluorophosphate- 4-phenyliodonium; diphenyliodonium hexafluoroantimonate; diphenyliodonium 2,2'-tetrafluoroborate; bis (2,4-dichlorophenyl) iodonium hexafluorophosphate; hexafluoro Bis (4-bromophenyl) iodonium phosphate; bis (4-methoxyphenyl) iodonium hexafluorophosphate; bis (3-carboxyphenyl) iodonium hexafluorophosphate; bis (3-methylhexafluorophosphate) Oxycarbonylphenyl) iodonium; bis (3-methoxysulfonylphenyl) iodonium hexafluorophosphate; bis (4-ethylamidophenyl) iodonium hexafluorophosphate; bis (hexafluorophosphate) 2-benzothienyl) iodine Onium; and diphenyliodonium hexafluoroantimonate; and mixtures thereof. These compounds can be prepared by overlying the corresponding simple aromatic iodonium salt (e.g., diphenyl iodonium hydrogen sulfate) according to the teachings of Beringer et al., J. Am . Chem . Soc . 81 , 342 (1959).

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，則可使用該等相同或不同種類碘鎓鹽中之任一者之混合物。 Useful iodonium salt may be a simple salt (e.g., containing an anion (e.g. chloride, bromide, iodide, or ^{_{C 4 H 5 SO 3 -)}} ) or a metal complex salt (e.g., containing ^{_{SbF 6 -, PF 6 -,}} BF ₄ ^-, tetrakis (perfluorophenyl) borate or ^{_{SbF 5 OH 31 AsF 6 -)}} . If desired, a mixture of any of these same or different iodonium salts may be used.

有用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(例如以SarCa^TM KI85自Sartomer公司購得)。 Useful sulfonium salts include, but are not limited to, triaryl substituted salts, such as mixed hexafluoroantimonate triarylsulfonium (for example, commercially available from Dow Chemical Company as UVI-6974), mixed hexafluorophosphate triarylsulfonium (for example, UVI- 6990 (available from Dow Chemical Co.) and arylfluorene hexafluorophosphate (for example, SarCa ^™ KI85 from Sartomer).

基於(a)至(d)所有4種組份之總重量，一或多種鎓鹽(例如碘鎓鹽或鋶鹽)通常以至少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%之量存在於光可聚合組合物中。 Based on the total weight of all four components (a) to (d), one or more onium salts (such as iodonium salts or sulfonium salts) are typically at least 0.05% by weight and up to and including 10% by weight or usually at least 0.1% by weight And is present in the photopolymerizable composition in an amount up to and including 10% by weight.

(ii)非離子光酸生成劑(ii) Nonionic photoacid generator

除上文所闡述之鎓鹽外，非離子光酸生成劑亦係有用的。該等化合物包含但不限於重氮甲烷衍生物，例如雙(苯磺醯基)-重氮甲烷、雙(對甲苯磺醯基)重氮甲烷、雙(二甲苯磺醯基)-重氮甲烷、雙(環己基磺醯基)-重氮甲烷、雙(環戊基磺醯基)重氮甲烷、雙(正丁基磺醯基)重氮甲烷、雙(異丁基磺醯基)-重氮甲烷、雙(第二丁基磺醯基)重氮甲烷、雙(正丙基磺醯基)重氮甲烷、雙(異丙基磺醯基)-重氮甲烷、雙(第三丁基磺醯基)重氮甲烷、雙(正戊基磺醯基)重氮甲烷、雙(異戊基磺醯基)-重氮甲烷、雙(第二戊基磺醯基)重氮甲烷、雙(第三戊基磺醯基)重氮甲烷、1-環己基磺醯基-1-(第三丁基磺醯基)重氮甲烷、1-環己基磺醯基-1-(第三戊基磺醯基)重氮甲烷及1-第三戊基磺醯基-1-(第 三丁基磺醯基)重氮甲烷。 In addition to the onium salts described above, non-ionic photoacid generators are also useful. These compounds include, but are not limited to, diazomethane derivatives, such as bis (benzenesulfonyl) -diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylylenesulfonyl) -diazomethane , Bis (cyclohexylsulfonyl) -diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl)- Diazomethane, bis (second butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) -diazomethane, bis (thirdbutyl) Sulfosulfanyl) diazomethane, bis (n-pentylsulfonyl) diazomethane, bis (isopentylsulfonyl) -diazomethane, bis (second pentylsulfonyl) diazomethane, Bis (third pentylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (third butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (third (Pentylsulfonyl) diazomethane and 1-third pentylsulfonyl-1- ( Tributylsulfonyl) diazomethane.

非離子光酸生成劑亦可包含乙二醛二肟衍生物，例如雙-鄰-(對甲苯磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(對甲苯磺醯基)-α-二苯基乙二醛二肟、雙-鄰-(對甲苯磺醯基)-α-二環己基-乙二醛二肟、雙-鄰-(對甲苯磺醯基)-2,3-戊烷二酮-乙二醛二肟、雙-鄰-(對甲苯磺醯基)-2-甲基-3,4-戊烷-二酮乙二醛二肟、雙-鄰-(正丁烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(正丁烷磺醯基)-α-二苯基乙二醛二肟、雙-鄰-(正丁烷磺醯基)-α-二環己基乙二醛二肟、雙-鄰-(正丁烷磺醯基)-2,3-戊烷二酮乙二醛二肟、雙-鄰-(正丁烷磺醯基)-2-甲基-3,4-戊烷二酮乙二醛二肟、雙-鄰-(甲烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(三氟甲烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(1,1,1-三氟乙烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(第三丁烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(全氟辛烷磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(環己烷-磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(苯磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(對氟苯磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(對第三丁基苯磺醯基)-α-二甲基乙二醛二肟、雙-鄰-(二甲苯磺醯基)-α-二甲基乙二醛二肟或雙-鄰-(樟腦磺醯基)-α-二甲基乙二醛二肟。 Nonionic photoacid generators may also include glyoxal dioxime derivatives, such as bis-o-o- (p-toluenesulfonyl) -α-dimethylglyoxal dioxime, bis-o-o- (p-toluenesulfonyl) ) -Α-diphenylglyoxal dioxime, bis-o- (p-toluenesulfonyl) -α-dicyclohexyl-glyoxal dioxime, bis-o- (p-toluenesulfonyl)- 2,3-pentanedione-glyoxal dioxime, bis-o- (p-toluenesulfonyl) -2-methyl-3,4-pentane-dione glyoxal dioxime, bis-o-ortho -(N-butanesulfonyl) -α-dimethylglyoxal dioxime, bis-o- (n-butanesulfonyl) -α-diphenylglyoxal dioxime, bis-o-o- ( N-butanesulfonyl) -α-dicyclohexylglyoxal dioxime, bis-o- (n-butanesulfonyl) -2,3-pentanedione glyoxal dioxime, bis-ortho- (N-butanesulfonyl) -2-methyl-3,4-pentanedione glyoxal dioxime, bis-o- (methanesulfonyl) -α-dimethylglyoxal dioxime, Bis-o- (trifluoromethanesulfonyl) -α-dimethylglyoxal dioxime, bis-o- (1,1,1-trifluoroethanesulfonyl) -α-dimethylethyl Dialdehyde dioxime, bis-o- (third-butanesulfonyl) -α-dimethylglyoxal dioxime, bis-o- (perfluorooctanesulfonyl) -α-dimethylethyl two Aldehydioxime, bis-o- (cyclohexane-sulfofluorenyl) -α-dimethylglyoxal dioxime, bis-o- (benzenesulfonyl) -α-dimethylglyoxal dioxime Bis-o- (p-fluorobenzenesulfonyl) -α-dimethylglyoxal dioxime, bis-o- (p-third butylbenzenesulfonyl) -α-dimethylglyoxal Oxime, bis-o- (xylylsulfonyl) -α-dimethylglyoxal dioxime or bis-o- (camphorsulfonyl) -α-dimethylglyoxal dioxime.

該等光酸生成劑進一步包含雙碸衍生物，例如雙萘基磺醯基甲烷、雙三氟甲基磺醯基甲烷、雙甲基磺醯基甲烷、雙乙基磺醯基甲烷、雙丙基磺醯基甲烷、雙異丙基-磺醯基甲烷、雙對甲苯磺醯基甲烷、雙苯磺醯基甲烷、2-環己基-羰基-2-(對甲苯磺醯基)丙烷(β-酮基碸衍生物)及2-異丙基-羰基-2-(對甲苯磺醯基)丙烷(β-酮基碸衍生物)。 The photoacid generators further include bisfluorene derivatives, such as bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropane Sulfosulfanylmethane, bisisopropyl-sulfonylmethane, bis-p-toluenesulfonylmethane, bisphenylsulfonylmethane, 2-cyclohexyl-carbonyl-2- (p-toluenesulfonyl) propane (β -Ketofluorene derivative) and 2-isopropyl-carbonyl-2- (p-toluenesulfonyl) propane (β-ketofluorene derivative).

其他種類之有用非離子光酸生成劑包含二磺基衍生物，例如二苯基二碸及二環己基二碸；磺酸硝基苄基酯衍生物，例如對甲苯磺酸2,6-二硝基苄基酯及對甲苯磺酸2,4-二硝基苄基酯；磺酸酯衍生物，例如1,2,3-叁(甲烷磺醯基氧基)苯、1,2,3-叁(三氟-甲烷磺醯基氧基)苯 及1,2,3-叁(對甲苯磺醯基氧基)苯；及N-羥基醯亞胺之磺酸酯，例如N-羥基琥珀醯亞胺甲烷磺酸酯、N-羥基琥珀醯亞胺三氟甲烷磺酸酯、N-羥基琥珀醯亞胺乙烷磺酸酯、N-羥基琥珀醯亞胺1-丙烷磺酸酯、N-羥基琥珀醯亞胺2-丙烷磺酸酯、N-羥基琥珀醯亞胺1-戊烷磺酸酯、N-羥基琥珀醯亞胺1-辛烷磺酸酯、N-羥基琥珀醯亞胺對甲苯磺酸酯、N-羥基琥珀醯亞胺對甲氧基苯磺酸酯、N-羥基琥珀醯亞胺2-氯乙烷磺酸酯、N-羥基琥珀醯亞胺苯磺酸酯、N-羥基琥珀醯亞胺2,4,6-三氟-苯磺酸酯、N-羥基琥珀醯亞胺2,4,6-三甲基-苯磺酸酯、N-羥基琥珀醯亞胺2,4,6-三氯-苯磺酸酯、N-羥基琥珀醯亞胺4-氰基-苯磺酸酯、N-羥基琥珀醯亞胺1-萘磺酸酯、N-羥基琥珀醯亞胺2-萘磺酸酯、N-羥基-2-苯基琥珀醯亞胺甲烷磺酸酯、N-羥基馬來醯亞胺甲烷磺酸酯、N-羥基馬來醯亞胺乙烷磺酸酯、N-羥基-2-苯基馬來醯亞胺甲烷磺酸酯、N-羥基戊二醯亞胺甲烷磺酸酯、N-羥基戊二醯亞胺苯磺酸酯、N-羥基鄰苯二甲醯亞胺甲烷磺酸酯、N-羥基鄰苯二甲醯亞胺苯磺酸酯、N-羥基鄰苯二甲醯亞胺三氟甲烷磺酸酯、N-羥基鄰苯二甲醯亞胺對甲苯磺酸酯、N-羥基萘二甲醯亞胺甲烷磺酸酯、N-羥基萘二甲醯亞胺苯磺酸酯、N-羥基-5-降莰烯-2,3-二羧基醯亞胺甲烷磺酸酯、N-羥基-5-降莰烯-2,3-二羧基醯亞胺三氟甲烷磺酸酯、N-羥基-5-降莰烯-2,3-二羧基醯亞胺對甲苯磺酸酯、N-羥基萘二甲醯亞胺三氟甲磺酸酯及N-羥基-5-降莰烯-2,3-二甲醯亞胺全氟-1-丁烷磺酸酯。 Other types of useful nonionic photoacid generators include disulfo derivatives such as diphenyl difluorene and dicyclohexyl difluorene; nitrobenzyl sulfonate derivatives such as p-toluenesulfonic acid 2,6-di Nitrobenzyl esters and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonate derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3 -Tris (trifluoro-methanesulfonyloxy) benzene And 1,2,3-tris (p-toluenesulfonyloxy) benzene; and sulfonates of N-hydroxystilbene imine, such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide Amine trifluoromethanesulfonate, N-hydroxysuccinimide ethane ethane sulfonate, N-hydroxysuccinimide 1-propane sulfonate, N-hydroxysuccinimide 2-propane sulfonate, N -Hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide Methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide benzenesulfonate, N-hydroxysuccinimide 2,4,6-tris Fluoro-benzenesulfonate, N-hydroxysuccinimide 2,4,6-trimethyl-benzenesulfonate, N-hydroxysuccinimide 2,4,6-trichloro-benzenesulfonate, N-Hydroxysuccinimide 4-cyano-benzenesulfonate, N-Hydroxysuccinimide 1-naphthalenesulfonate, N-Hydroxysuccinimide 2-naphthalenesulfonate, N-Hydroxy-2 -Phenylsuccinimide imine methane sulfonate, N-hydroxymaleimide imine methane sulfonate, N-hydroxymaleimide imine ethane sulfonate, N-hydroxy-2-phenylmethane Fluorenimethane methane sulfonate, N-hydroxypentamidine imine methane sulfonate, N-hydroxypentamidine imine benzene sulfonate, N-hydroxyphthalimide methane sulfonate, N -Hydroxyphthalimide benzenesulfonate, N-Hydroxyphthalimide trifluoromethanesulfonate, N-Hydroxyphthalimide p-toluenesulfonate, N-Hydroxy Naphthalene dimethyl imine methane sulfonate, N-hydroxynaphthalene dimethyl imine benzene sulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyfluorene imine methane sulfonate, N -Hydroxy-5-norbornene-2,3-dicarboxyfluorenimine trifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboxyfluorenimine p-toluenesulfonate, N-hydroxynaphthalenedimethylimine triflate and N-hydroxy-5-norbornene-2,3-dimethylformimine perfluoro-1-butanesulfonate.

一或多種非離子光酸生成劑可以如下量存在於光可聚合組合物中：基於(a)至(d)所有4種組份之總重量，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%。 One or more non-ionic photoacid generators may be present in the photopolymerizable composition in an amount of at least 0.05% by weight and up to and including 10% by weight or based on the total weight of all four components (a) to (d) Usually at least 0.1% by weight and up to and including 10% by weight.

(c)電子供體光敏劑(c) Electron donor photosensitizer

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過程之官能基，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。 Useful electron donor photosensitizers should be soluble in the photocurable composition, contain no functional groups that substantially interfere with the cationic photocuring process, and can absorb (sensitivity) at least 150nm and Includes at most wavelengths in the 1000 nm range.

適宜電子供體光敏劑引發鎓鹽(或其他光酸生成劑)因應於自輻照吸收之光子之化學轉換。在電子供體光敏劑吸收光(亦即光誘導電子轉移)之後，電子供體光敏劑亦應能夠還原光酸生成劑。因此，電子供體光敏劑在自輻照吸收光子後通常能夠向光酸生成劑供給電子。 Suitable electron-donor photosensitizers initiate the chemical conversion of onium salts (or other photoacid generators) in response to photons absorbed by irradiation. After the electron donor photosensitizer absorbs light (ie, light-induced electron transfer), the electron donor photosensitizer should also be able to reduce the photoacid generator. Therefore, the electron donor photosensitizer is usually capable of supplying electrons to the photoacid generator after absorbing photons from irradiation.

對於期望極迅速固化(例如固化所施加之組合物薄膜)之光可固化組合物之使用而言，電子供體光敏劑在使用光固化過程之期望輻照波長下可具有至少1000公升-莫耳^-1cm^-1且通常至少50,000公升-莫耳^-1cm^-1之消光係數。 For the use of photocurable compositions that are expected to cure very quickly (e.g., to cure a thin film of the applied composition), the electron donor photosensitizer may have at least 1000 liters-Mole at the desired irradiation wavelength using the photocuring process. Extinction coefficient of ^-1 cm ^-1 and usually at least 50,000 liters-Mole ^-1 cm ^-1 .

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(相對於SCE(飽和甘汞電極))或更通常至少0.8V且至多並包含2V(相對於SCE)之氧化電位。 For example, each electron donor photosensitizer typically has an oxidation of at least 0.4V and up to and including 3V (relative to SCE (saturated calomel electrode)) or more often at least 0.8V and up to and including 2V (relative to SCE) oxidation Potential.

一般而言，可使用許多不同種類之化合物作為用於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。 In general, many different kinds of compounds can be used 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, pyrene, phenanthrene, benzo [c ] Phenanthrene and fluoranthene.

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。 Other useful electron donor photosensitizers involving triplet excited states are carbonyl compounds such as thioxanthone and xanthone. Ketones (including aromatic ketones (e.g. fluorenone)) and coumarin dyes (e.g. ketocoumarin) (e.g. those with a strong electron donating moiety (e.g. dialkylamino)) can also be used as electron donors Body photosensitizer. It is believed that other suitable electron donor photosensitizers include xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, amine ketone dye, porphyrin, aromatic polycyclic hydrocarbon, para-substitution Amine styryl ketone compounds, amine triarylmethanes, merocyanin, squaraine dyes and pyridinium dyes.

亦可使用選自相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 can also be used.

各種有用之電子供體光敏劑係自各種商業來源購得且可易於發 現以用於本發明中。 A variety of useful electron donor photosensitizers are commercially available and readily available Now used in the present invention.

基於組份(a)至(d)之總重量，一或多種電子供體光敏劑可以至少0.0001重量%且至多並包含5重量%及通常至少0.001重量%且至多並包含2重量%之量存在於光可固化組合物中。在一些實施例中，電子供體光敏劑係芘、苯并芘、苝或苯并苝，其基於組份(a)、(b)及(d)之總重量以至少0.05重量%且至多並包含2重量%之量存在。 Based on the total weight of components (a) to (d), one or more electron donor photosensitizers may be present in an amount of at least 0.0001% by weight and up to and including 5% by weight and usually at least 0.001% by weight and up to and including 2% by weight In a photocurable composition. In some embodiments, the electron donor photosensitizer is pyrene, benzopyrene, pyrene or benzopyrene, which is at least 0.05% by weight and at most 0.05% by weight based on the total weight of components (a), (b), and (d). Contained in an amount of 2% by weight.

(d)金屬顆粒(d) Metal particles

光可固化組合物中存在金屬顆粒。通常，僅使用一種類型之金屬顆粒，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。 Metal particles are present in the photocurable composition. Generally, only one type of metal particles is used, but a mixture of metal particles from the same or different kinds of metals that do not interfere with each other can also be included. The metal particles typically have a net neutral charge.

有用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。有用貴金屬顆粒包含但不限於金、銀、鈀、鉑、銠、銥、錸、汞、釕及鋨之顆粒。有用半貴金屬顆粒包含但不限於鐵、鈷、鎳、銅、碳、鋁、鋅及鎢之顆粒。有用第IV族金屬顆粒包含但不限於錫、鈦及鍺之顆粒。貴金屬顆粒(例如金、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族金屬類別中尤其有用。在許多實施例中，在光可固化組合物中使用銀或銅顆粒作為無電鍍覆方法之「晶種」金屬顆粒。 Useful metal particles may be selected from one or more kinds of precious metals, semi-precious metals, Group IV metals, or combinations thereof. Useful precious metal particles include, but are not limited to, particles of gold, silver, palladium, platinum, rhodium, iridium, osmium, mercury, ruthenium, and osmium. Useful semi-precious metal particles include, but are not limited to, particles of iron, cobalt, nickel, copper, carbon, aluminum, zinc, and tungsten. Useful Group IV metal particles include, but are not limited to, particles of tin, titanium, and germanium. Precious metal particles (such as particles of gold, silver, palladium, and platinum) are particularly useful, as are semi-precious particles of nickel and copper. Tin particles are particularly useful in the Group IV metal category. In many embodiments, silver or copper particles are used as the "seed" metal particles in the electroless plating method in the photocurable 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。用於塗覆金屬顆粒之碳可具有非晶型、sp2雜化或類石墨烯性質。該碳可用於防止金屬顆粒之聚集且提供改良之於光可固化組合物中之分散性。 Surfactants, polymers or carbon can be used to coat metal particles that can be used in the present invention. The carbon used to coat the metal particles may have amorphous, sp2-hybrid, or graphene-like properties. The carbon can be used to prevent the aggregation of metal particles and provide improved dispersibility in the photocurable composition.

金屬顆粒可分散於各種有機溶劑中且在光可固化組合物之其他基本組份(例如多官能聚合環氧樹脂材料)存在下或在下文所闡述之可選組份(例如多官能丙烯酸酯樹脂)存在下可具有改良之分散性。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。 Metal particles can be dispersed in various organic solvents and in the presence of other basic components of the photocurable composition (such as a polyfunctional polymeric epoxy resin material) or optional components (such as a polyfunctional acrylate resin) as described below ) Can have improved dispersibility in the presence. Methods for dispersing metal particles include, but are not limited to, ball milling, magnetic stirring, high-speed homogenization, and high pressure Homogenization and ultrasonic processing.

金屬顆粒可作為個別顆粒存在於光可聚合組合物中，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凝聚物存在。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。個別及凝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別限制，但最佳益處可使用平均粒徑為至少0.02μm且至多並包含10μm之個別顆粒或凝聚物形式之金屬顆粒來達成。粒徑分佈合意地窄，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 may be present in the photopolymerizable composition as individual particles, but in many embodiments, the metal particles are present as agglomerates of two or more metal particles. These metal particles can exist in any geometric shape, including but not limited to spherical, rod-shaped, prism-shaped, cubic, cone-shaped, pyramid-shaped, wire-shaped, lamellar, platelet-shaped, 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 can vary from at least 0.01 μm and up to and including 25 μm or more likely 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 in the form of individual particles or agglomerates having an average particle size of at least 0.02 μm and up to and including 10 μm. The particle size distribution is desirably narrow, as defined by a particle size in which more than 50% or usually at least 75% of the particles is 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 for the equipment Diameter distribution.

可自各種商業來源獲得有用之金屬顆粒，或其可源自各種金屬鹽或錯合物及已知之還原及分離過程，之後用於實踐本發明中。一些商業金屬顆粒可自(例如)Novacentrix獲得。 Useful metal particles can be obtained from a variety of commercial sources, or they can be derived from various metal salts or complexes and known reduction and separation processes before being used in the practice of the present invention. Some commercial metal particles are available from, for example, Novacentrix.

基於組份(a)至(d)之總重量，金屬顆粒通常以至少0.1重量%且至多並包含50重量%或更高通常至少1重量%且至多並包含30重量%之量存在於光可固化組合物中。 Based on the total weight of components (a) to (d), the metal particles are generally present in the photopolymer in an amount of at least 0.1% by weight and up to and including 50% by weight or higher, usually at least 1% by weight and up to and including 30% by weight. In the cured composition.

(e)自由基可聚合化合物(e) Free radical polymerizable compounds

光可固化組合物亦可含有一或多種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且其可包括兩個或更多個能夠發生加成(或自由基)聚合之該等不飽和部分。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，包含但不限於甲基丙烯酸酯、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至並包含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。若期望，則可使用兩種或更多種該等自由基可聚合材料之混合物。 The photocurable composition may also contain one or more free radical polymerizable compounds to provide free radical polymerizable functional groups, including ethylenically unsaturated polymerizable monomers, oligomers, or polymers (e.g., monofunctional or polyfunctional acrylates). ) (Also includes methacrylate). The radical polymerizable compounds include at least one ethylenically unsaturated polymerizable bond and it may include two or more such unsaturated moieties capable of undergoing addition (or radical) polymerization. Those freedoms Polymerizable materials include mono-, di- or polyacrylates and methacrylates, including but not limited to methacrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate Ester, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, new Pentylene glycol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, neopentyl tetraol Triacrylate, neopentaerythritol tetraacrylate, neopentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, bis [1- (2-propenyloxy)] -P-ethoxyphenyldimethylmethane, bis [1- (3-propenyloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane and Trihydroxyethyl isocyanurate trimethacrylate; diacrylates and bismethacrylates of polyethylene glycol having a molecular weight of 200 to and including 500; copolymerizable mixtures of acrylate monomers, for example In U.S. Patent No. 4,652,274 (Boettcher et al.); And acrylate oligomers such as those described in U.S. Patent No. 4,642,126 (Zader et al.); And vinyl compounds such as styrene and styrene derivatives, o-phthalene Diallyl formate, divinyl succinate, divinyl adipate and divinyl phthalate. If desired, a mixture of two or more of these radically polymerizable materials can be used.

該等材料可購自大量商業來源或使用已知合成方法及起始材料來製備。 These materials can be purchased from a number of commercial sources or prepared using known synthetic methods and starting materials.

儘管該一或多種自由基可聚合材料之量並無特別限制，但其可以基於光可固化組合物之所有組份之總重量至少20重量%且至多並包含75重量%或通常至少40重量%且至多並包含60重量%之量存在於光可聚合組合物中，且其可基於組合物溶解性之期望性質及光固化組合物之機械強度進行最佳化。 Although the amount of the one or more radical polymerizable materials is not particularly limited, it may be at least 20% by weight and up to and including 75% by weight or generally at least 40% by weight based on the total weight of all components of the photocurable composition. It is present in the photopolymerizable composition in an amount of up to and including 60% by weight, and it can be optimized based on the desired properties of the solubility of the composition and the mechanical strength of the photocurable composition.

(f)自由基光起始劑(f) Free radical photoinitiator

若存在(e)組份，則光可固化組合物中亦存在一或多種自由基光起始劑以在自由基可聚合化合物存在下生成自由基。該等自由基光起始劑包含能夠在曝光於實踐本發明中所使用之光聚合輻射(例如紫外或可見輻射)後生成自由基之任一化合物。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、重氮化合物及聯咪唑化合物及熟習此項技術者可易於明瞭之其他化合物。該等化合物之混合物可選自相同或不同種類。 If component (e) is present, one or more free radical photoinitiators are also present in the photocurable composition to generate free radicals in the presence of a free radical polymerizable compound. The free radical photoinitiators include any compound capable of generating free radicals upon exposure to photopolymerizable radiation (such as ultraviolet or visible radiation) used in the practice of the present invention. For example, the radical photoinitiator can be selected from triazine compounds, thioxanthone compounds, benzoin compounds, carbazole compounds, dione compounds, sulfonium borate compounds, diazo compounds, and biimidazole compounds, and are familiar with the technology The other compounds can be easily understood. The mixture of these compounds may be selected from the same or different species.

亦有用者係二苯甲酮化合物，例如二苯甲酮、苯甲酸苯甲醯基酯、苯甲酸甲基苯甲醯基酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯醯化二苯甲酮、4,4'-雙(二甲基胺基)二苯甲酮及4,4'-雙(二乙基胺基)二苯甲酮；蒽醌化合物；及苯乙酮化合物，例如2,2'-二乙氧基苯乙酮、2,2'-二丁氧基苯乙酮、2-羥基-2-甲基丙醯苯、對第三丁基三氯苯乙酮、對第三丁基二氯苯乙酮、二苯甲酮、4-氯苯乙酮、4,4'-二甲基胺基二苯甲酮、4,4'-二氯二苯甲酮、3,3'-二甲基-2-甲氧基二苯甲酮、2,2'-二氯-4-苯氧基苯乙酮、2-甲基-1-(4-(甲基硫基)苯基)-2-嗎啉基丙-1-酮及2-苄基-2-二甲基胺基-1-(4-嗎啉基苯基)-丁烷-1-酮。此類型之其他有用化合物闡述於(例如)美國專利7,875,416(Park等人)中。 Also useful are benzophenone compounds, such as benzophenone, benzophenone benzoate, methylbenzophenate benzoate, 4-phenylbenzophenone, hydroxybenzophenone, propylene Tritiated benzophenone, 4,4'-bis (dimethylamino) benzophenone and 4,4'-bis (diethylamino) benzophenone; anthraquinone compounds; and acetophenone Ketone compounds, such as 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropanone, p-tert-butyltrichlorobenzene Ethyl ketone, p-third butyl dichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorodiphenyl Methanone, 3,3'-dimethyl-2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- ( Methylthio) phenyl) -2-morpholinylpropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1- ketone. Other useful compounds of this type are described, for example, in U.S. Patent 7,875,416 (Park et al.).

許多該等自由基光起始劑可自各種商業來源獲得。 Many of these free radical photoinitiators are available from a variety of commercial sources.

該等自由基光起始劑通常以如下量存在於光可固化組合物中：基於光可固化組合物之所有組份之總重量，至少0.1重量%且至多並包含10重量%或通常至少1重量%且至多並包含5重量%。 The free radical photoinitiators are generally present in the photocurable composition in an amount of at least 0.1% by weight and up to and including 10% by weight or usually at least 1 based on the total weight of all components of the photocurable composition. % By weight and up to and including 5% by weight.

亦可包含導電奈米氧化物及導電奈米碳材料，例如奈米管、奈米石墨烯及巴氏球(bucky ball)。導電奈米氧化物包含但不限於氧化銦錫、氧化銻、氧化銻錫、氧化銦、氧化鋅、氧化鋅鋁及其混合物。 It may also contain conductive nano-oxides and conductive nano-carbon materials, such as nano-tubes, nano-graphene, and bucky balls. Conductive nano-oxides include, but are not limited to, indium tin oxide, antimony oxide, antimony tin oxide, indium oxide, zinc oxide, zinc aluminum oxide, and mixtures thereof.

可有用地在光可固化組合物中包含一或多種含有羥基之材料(包含多元醇)作為電荷轉移劑以輔助光聚合過程。術語「多元醇」係指分子中具有兩個或更多個一級或二級脂肪族羥基之有機化合物。含有羥基之材料中之每一羥基(hydroxy或hydroxyl)直接鍵結至分子中之非芳族碳原子。在使用時，含有羥基之材料可呈液體或固體形式且具有有機性質。任一羥基可位於末端或懸垂於均聚物或共聚物主鏈。 It may be useful to include one or more hydroxyl-containing materials (including polyols) as charge transfer agents in the photocurable composition to assist the photopolymerization process. The term "polyol" refers to an organic compound having two or more primary or secondary aliphatic hydroxyl groups in a molecule. Each hydroxy or hydroxyl in a hydroxy-containing material is directly bonded to a non-aromatic carbon atom in the molecule. In use, hydroxyl-containing materials can be in liquid or solid form and have organic properties. Either the hydroxyl group may be terminal or dangling from the homopolymer or copolymer backbone.

亦可期望將乙烯基醚化合物作為鏈轉移劑添加至光可固化組合物中以進一步增加光聚合速率或確保於最終光固化圖案化材料中之期望物理性質。有用乙烯基醚化合物之實例包含但不限於Rapi-Cure^TMDVE-3(三乙二醇二乙烯基醚)、Rapi-Cure^TM CHVE(1,4-環己烷二甲醇二乙烯基醚)及Rapi-Cure^TM HBVE(丁二醇單乙烯基醚)，皆購自Ashland公司。 It may also be desirable to add a vinyl ether compound as a chain transfer agent to the photocurable composition to further increase the rate of photopolymerization or to ensure the desired physical properties in the final photocurable patterned material. Examples of useful vinyl ether compounds include, but are not limited to, Rapi-Cure ^TM DVE-3 (triethylene glycol divinyl ether), Rapi-Cure ^TM CHVE (1,4-cyclohexanedimethanol divinyl ether), and Rapi-Cure ^™ HBVE (butanediol monovinyl ether) was purchased from Ashland.

光可固化組合物亦可含有適宜佐劑(或添加劑)，例如加速劑、抑制劑、吸收劑、穩定劑、顏料、染料、UV吸收劑、黏度改質劑、流動改良劑、表面張力降低劑及潤濕助劑、抗氧化劑、表面活性劑及彼等熟習此項技術者熟知之其他成份。 The photocurable composition may also contain suitable adjuvants (or additives), such as accelerators, inhibitors, absorbers, stabilizers, pigments, dyes, UV absorbers, viscosity modifiers, flow improvers, surface tension reducers And wetting auxiliaries, antioxidants, surfactants and other ingredients well known to those skilled in the art.

通常製備光可固化組合物以作為圖案化材料藉由簡單混合在「安全光」條件下於並不與其中所納入任一組份輕微反應之適宜惰性有機溶劑內塗覆、印刷或以其他方式施加至本發明基板上。適宜惰性溶劑之實例包含但不限於丙酮、二氯甲烷、異丙醇、Dowanol PM、1-甲氧基-2-丙醇、乙二醇及其混合物。在一或多種擬使用組份呈液體形式時，彼等組份可用作光可固化組合物之「溶劑」，或與一或多種惰性有機溶劑組合使用。可藉由使用或不使用用於促進溶解或分散之適度加熱進行簡單溶解、分散並混合基本組份(a)至(d)及任何可選組份來製備無溶劑之光可固化組合物。 Photocurable compositions are usually prepared as patterning materials by simple mixing under "safe light" conditions, coating, printing, or otherwise in a suitable inert organic solvent that does not slightly react with any of the components included therein. Apply to the substrate of the present invention. Examples of suitable inert solvents include, but are not limited to, acetone, dichloromethane, isopropanol, Dowanol PM, 1-methoxy-2-propanol, ethylene glycol, and mixtures thereof. When one or more of the components to be used are in liquid form, their components can be used as a "solvent" for the photocurable composition, or used in combination with one or more inert organic solvents. Solvent-free photocurable compositions can be prepared by simply dissolving, dispersing, and mixing the basic components (a) to (d) and any optional components with or without the use of moderate heating for promoting dissolution or dispersion.

在使用惰性有機溶劑時，其可基於上文所闡述之組份(a)至(d)之 總重量以如下量存在：至少1重量%且至多並包含70重量%或至少20重量%且至多並包含50重量%。 When an inert organic solvent is used, it may be based on the components (a) to (d) described above. The total weight is present in an amount of at least 1% by weight and up to and including 70% by weight or at least 20% by weight and up to and including 50% by weight.

在適宜光固化或熱固化條件下，上文所闡述之物件可包括含有導電金屬及光固化或熱固化組合物(其皆按一定圖案形式佈置於基板之乾燥底漆層上)之圖案化材料。圖案化材料之至少一部分圖案可包括平均線寬小於15μm之線。該等圖案化材料由此可包括分散於衍生自相應光可固化或熱可固化組合物之光固化或熱固化組合物內之金、銀、銅、鈀或鉑之顆粒。 Under conditions suitable for photo-curing or heat-curing, the objects described above may include patterning materials containing conductive metals and photo-curing or heat-curing compositions, which are all arranged in a certain pattern on the dry primer layer of the substrate. . At least a portion of the pattern of the patterned material may include lines having an average line width of less than 15 μm. The patterned materials may thus include particles of gold, silver, copper, palladium, or platinum dispersed in a photo-curable or heat-curable composition derived from a corresponding photo-curable or heat-curable composition.

製備包含導電圖案之圖案之方法Method for preparing pattern including conductive pattern

使用第一方法來提供具有圖案化材料之打底物件，該方法包含：提供包括透明聚合物載體(如上文所闡述)及乾燥底漆層(如上文所闡述)之透明聚合基板，且然後直接在乾燥底漆層上提供可圖案化材料(如上文所闡述)之圖案。如上所述，可藉由使乾燥底漆層與如本文所闡述之凸版印刷部件(例如柔性版印刷部件)直接接觸來提供此圖案，該凸版印刷部件在通常形成於彈性體材料之凸版影像之上表面上攜載圖案化材料。凹版印刷及凹雕印刷係用於將可圖案化材料圖案施加至乾燥底漆層上之其他方式。 A first method is used to provide a primer article having a patterned material, the method comprising: providing a transparent polymeric substrate including a transparent polymer carrier (as explained above) and a dry primer layer (as explained above), and then directly A pattern of a patternable material (as explained above) is provided on the dry primer layer. As described above, this pattern can be provided by directly contacting the dry primer layer with a relief printing component (such as a flexographic printing component) as set forth herein, which is typically formed on a relief image of an elastomeric material. A patterned material is carried on the upper surface. Intaglio printing and intaglio printing are other methods used to apply a patternable material pattern to a dry primer layer.

另外，期望由此提供之圖案化材料之至少一部分圖案包括平均線寬為小於15μm之線，且該部分圖案化材料將以最終作為打底物件之觸控螢幕區域(與電極區域或BUS區域相對)之形式存在。該圖案化材料可包括如上文所闡述之導電金屬或導電金屬前體，且圖案化材料可包括光可固化或熱可固化組合物，其中之任一者包括導電金屬或導電金屬前體。 In addition, it is expected that at least a part of the pattern of the patterned material thus provided includes a line having an average line width of less than 15 μm, and the part of the patterned material will be a touch screen region (as opposed to an electrode region or a BUS region) that is ultimately used as a substrate ). The patterned material may include a conductive metal or a conductive metal precursor as set forth above, and the patterned material may include a photo-curable or heat-curable composition, any of which includes a conductive metal or a conductive metal precursor.

自下文所闡述特定製造實施例之闡述尤其亦應理解，可將相同或不同圖案化材料施加至基板之相對支撐側上，尤其在基板於載體之兩個支撐側上包括乾燥底漆層時。該等打底及圖案化物件可視為「雙 重構造(duplex)」，此乃因其在載體(包含透明聚合物載體)之兩側上皆具有乾燥底漆層及圖案材料。 It should also be understood from the following description of specific manufacturing embodiments that the same or different patterning materials may be applied to the opposite support sides of the substrate, especially when the substrate includes a dry primer layer on the two support sides of the carrier. These primers and patterned objects can be regarded as "double "Duplex" because it has a dry primer layer and pattern material on both sides of the carrier (including the transparent polymer carrier).

在圖案化材料包括光可固化或熱可固化組合物之尤其期望之實施例中，然後使圖案化材料在基板之一側或兩側經受固化條件及裝置。 In particularly desirable embodiments where the patterning material includes a photo-curable or heat-curable composition, the patterning material is then subjected to curing conditions and devices on one or both sides of the substrate.

舉例而言，可藉由使用如上文所闡述之輻射能(例如紫外光)輻照圖案化材料來達成光固化。可使用波長為至少184.5nm至且包含700nm且強度為至少1mJ/cm²且至多並包含1000mJ/cm²或更通常至少1mJ/cm²且至多並包含800mJ/cm²之UV或可見輻照來達成期望光固化。 For example, light curing can be achieved by irradiating a patterned material with radiant energy (such as ultraviolet light) as set forth above. UV or visible radiation having a wavelength of at least 184.5 nm to and including 700 nm and an intensity of at least 1 mJ / cm ² and up to and including 1000 mJ / cm ² or more typically at least 1 mJ / cm ² and up to and including 800 mJ / cm ² may be used Achieve desired photocuring.

圖案化材料(例如前體導電材料)之至少一部分所得固化圖案可包括平均在該部分中線寬小於15μm之固化材料細線。在許多實施例中，整個圖案以此方式發生固化。 The resulting cured pattern of at least a portion of a patterned material (such as a precursor conductive material) may include thin lines of cured material having a line width less than 15 μm on average in the portion. In many embodiments, the entire pattern is cured in this manner.

可將前體導電材料之至少一部分及通常所有固化圖案轉化成包括如上文所闡述之導電細線之導電材料圖案。「前體導電材料」係指可以化學方式、以物理方式或以電方式處理以致使材料導電之組合物。該等「前體」材料之一些實施例係包括下文所闡述「晶種」金屬之組合物。 At least a portion of the precursor conductive material and generally all of the cured patterns may be converted into a conductive material pattern including conductive thin wires as set forth above. "Precursor conductive material" means a composition that can be chemically, physically, or electrically treated to render the material conductive. Some examples of such "precursor" materials include compositions of "seed" metals as described below.

在該等實施例中之圖案化材料包括導電金屬或導電金屬前體時(舉例而言，其中導電金屬包括晶種金屬顆粒)，可使用業內已知之條件及無電鍍覆試劑無電金屬鍍覆基板上圖案化材料之圖案中之晶種金屬顆粒，其中之一些細節闡述於下文中。可以此方式產生含有晶種金屬顆粒之多個圖案，尤其在含有乾燥底漆層之透明聚合基板係連續網片時，如下文所闡釋及圖1中所展示。 When the patterned material in these embodiments includes a conductive metal or a conductive metal precursor (for example, where the conductive metal includes seed metal particles), conditions known in the industry and electroless plating agents can be used to electrolessly plate the substrate. Some details of the seed metal particles in the pattern of the above patterned material are described below. Multiple patterns containing seed metal particles can be produced in this way, especially when the transparent polymeric substrate containing the dry primer layer is a continuous mesh, as explained below and shown in FIG. 1.

在該等實施例中，以連續網片形式將光可固化或熱可固化組合物之多個個別圖案提供於透明聚合基板上，該光可固化或熱可固化組 合物係含有晶種金屬顆粒之前體導電材料，其係直接施加於連續網片之多個個別部分中之乾燥底漆層上。該連續網片可具有至少88%或至少95%的積分透射率，且在可為透明聚酯載體之透明聚合物載體(如上文所闡述)上包括乾燥底漆(如上文所闡述)。 In these embodiments, a plurality of individual patterns of the photo-curable or heat-curable composition are provided on a transparent polymer substrate in the form of a continuous mesh. The photo-curable or heat-curable group The composition contains a seed metal particle precursor conductive material, which is applied directly to the dried primer layer in a plurality of individual parts of the continuous mesh. The continuous mesh may have an integrated transmittance of at least 88% or at least 95% and include a dry primer (as described above) on a transparent polymer support (as described above), which may be a transparent polyester support.

以此方式，可製備本文所闡述之多個前體物件以在產生之後立即使用或隨後使用。舉例而言，可在本發明之打底基板之連續網片(以捲形式提供)上形成多個前體物件，且然後以含有第一、第二及多個其他可選固化圖案之形式捲繞。如上所述來固化圖案化材料中光可固化或熱可固化組合物之複數個個別圖案中之每一者以在連續網片上之複數個個別部分中形成多個個別固化圖案，該等個別固化圖案含有晶種金屬顆粒。 In this manner, a plurality of precursor articles set forth herein can be prepared for immediate use or subsequent use after production. For example, a plurality of precursor objects may be formed on a continuous mesh (provided in a roll form) of the base substrate of the present invention, and then rolled in a form containing first, second, and multiple other optional curing patterns Around. Each of the plurality of individual patterns of the photo-curable or heat-curable composition in the patterned material is cured as described above to form a plurality of individual curing patterns in a plurality of individual portions on a continuous web, the individual curing The pattern contains seed metal particles.

然後可如下文所闡述在固化之後立即或隨後且視情況在不同位置處使用相同或不同無電鍍覆浴及條件無電鍍覆該複數個個別固化圖案。 The plurality of individual curing patterns may then be plated using the same or different electroless plating baths and conditional electroless plating at different locations, as described below, immediately or subsequently and optionally at different locations.

所得產品物件在基板一側或兩側含有一或多個導電圖案，該等導電圖案可包括平均線寬小於15μm之細線，且可配置於導電物件或顯示器件之觸控區域中。尤其有用之此類器件包括積分透射率至少為88%之透明導電膜且將基板之乾燥底漆層(如上文所闡述)直接佈置於透明聚合物載體(例如聚酯載體)上。 The obtained product object contains one or more conductive patterns on one or both sides of the substrate. The conductive patterns may include thin lines with an average line width of less than 15 μm, and may be arranged in the touch area of the conductive object or display device. Particularly useful devices of this type include a transparent conductive film with an integrated transmittance of at least 88% and a dry primer layer (as explained above) of the substrate is disposed directly on a transparent polymer carrier (such as a polyester carrier).

現在考慮關於大規模製造及使用打底物件以提供導電物件及器件之更多細節。 Consider now more details about mass manufacturing and use of primers to provide conductive objects and devices.

本發明之打底物件可個別地用作單一元件，或用作直接在乾燥底漆層上(在基板之一或兩個支撐側上)佈置有圖案化材料圖案之多個部分之連續網片(例如用於輥-輥製程)。可處理該連續網片以在塗覆台中施加圖案化材料且然後行經曝光(固化)台，或可使曝光(固化)器件通過連續網片之圖案化材料之多個圖案上方。可於基板之支撐側上之 圖案化材料(例如印刷材料)中使用相同或不同光可固化組合物，無論其呈單一元件抑或連續網片形式。在許多實施例中，在基板(或連續網片)之相對支撐側上形成不同導電金屬圖案。 The primer article of the present invention can be used individually as a single element or as a continuous mesh in which multiple portions of a patterned material pattern are arranged directly on a dry primer layer (on one or both support sides of a substrate). (Eg for roll-to-roll processes). The continuous web may be processed to apply a patterning material in a coating station and then run through an exposure (curing) station, or an exposure (curing) device may be passed over multiple patterns of the patterning material of the continuous web. Available on the support side of the substrate The same or different photo-curable compositions are used in patterned materials, such as printed materials, whether they are in the form of a single element or a continuous mesh. In many embodiments, different conductive metal patterns are formed on opposite support sides of a substrate (or continuous mesh).

如上所述，可按一定圖案方式使用任一適宜施加方式來施加圖案化材料，但使用柔性版印刷部件之柔性版印刷尤其有用。 As described above, the patterned material may be applied in a certain pattern using any suitable application method, but flexographic printing using a flexographic printing member is particularly useful.

在將圖案化材料施加至基板上之後，可藉由不會不利地影響剩餘組份或過早引起聚合之乾燥或預烘培程序去除任何惰性有機溶劑。有用之乾燥條件可端視製造製程低至室溫並保持短至5秒且至多若干小時且包含若干小時。在下文所闡述之大多數製程(例如輥至輥製程)中，乾燥條件可處於足夠高之溫度下以在至少1秒內去除至少90%之惰性有機溶劑。 After the patterning material is applied to the substrate, any inert organic solvents can be removed by a drying or pre-baking process that does not adversely affect the remaining components or cause polymerization prematurely. Useful drying conditions may depend on the manufacturing process as low as room temperature and held as short as 5 seconds and up to several hours inclusive. In most processes described below, such as roll-to-roll processes, the drying conditions can be at a temperature high enough to remove at least 90% of the inert organic solvent in at least 1 second.

任一所施加之圖案化材料圖案可包括平均厚度(或寬度)為至少0.2μm且至多並包含20μm或通常至少2μm且至多並包含15μm之線柵格(或其他形狀(包含圓形或不規則網狀物))，且最佳乾燥厚度(或寬度)可針對所得均勻光固化層之預期用途來調節，其通常具有與非光固化圖案化材料之柵格線大約相同之乾燥厚度(或寬度)。 Any of the applied patterned material patterns may include a line grid (or other shape (including circular or irregular) having an average thickness (or width) of at least 0.2 μm and at most and including 20 μm or usually at least 2 μm and at most and including 15 μm Mesh)), and the optimal dry thickness (or width) can be adjusted for the intended use of the resulting uniform photo-curable layer, which typically has a dry thickness (or width) approximately the same as the grid lines of the non-photo-curable patterned material ).

因此，本發明提供包括基板及圖案化材料圖案之物件，其中可認為該等物件係「前體」物件，此意味著其係用於提供導電物件之方法中產生之第一物件。 Accordingly, the present invention provides an article including a substrate and a pattern of a patterned material, wherein the articles can be considered to be "precursor" articles, which means that they are the first articles produced in a method for providing a conductive article.

在一些實施例中，可以適宜方式將相同或不同光可固化或熱可固化組合物施加於基板之兩個支撐側上以在「雙重構造」或雙側前體物件上形成用於每一可固化圖案之各種特徵，且多個固化圖案可具有相同或不同晶種金屬顆粒(其係金顆粒、銀顆粒、銅顆粒、鈀顆粒或鉑顆粒)。 In some embodiments, the same or different photo-curable or heat-curable compositions may be applied on both support sides of the substrate in a suitable manner to form a "dual construction" or double-sided precursor article for each Various characteristics of the curing pattern, and the plurality of curing patterns may have the same or different seed metal particles (which are gold particles, silver particles, copper particles, palladium particles, or platinum particles).

在許多實施例中，使用凸版印刷部件(例如源於柔性版印刷板前體之彈性凸版部件)將光可固化或熱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)之一個或兩個(相對)支撐側上，許多該等凸版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柔版板購自Eastman Kodak公司。 In many embodiments, a pattern of a photocurable or heat-curable composition is applied to a substrate (e.g., as a roll-to-roll continuous web) using a relief printing member (e.g., an elastic letterpress member derived from a flexographic printing plate precursor). On one or two (opposite) support sides, many of these letterpress printed components are known in the industry and some are purchased, for example, from ^Cyrel® flexographic photopolymer plates from DuPont and Flexcel SR and NX flexographic plates from Eastman Kodak Company.

尤其有用之凸版印刷部件源於柔性版印刷板前體及柔性版印刷套筒前體，其每一者可適當地成像(及處理(若需要))以提供凸版影響用於「印刷」或施加適宜圖案。 Particularly useful letterpress printing components are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be appropriately imaged (and processed (if needed)) to provide letterpress effects for "printing" or to apply suitable pattern.

舉例而言，有用柔性版印刷部件前體闡述於美國專利7,799,504(Zwadlo等人)及8,142,987(Ali等人)及美國專利申請公開案2012/0237871(Zwadlo)中。凸版影像層可印刷不同以向基板之相同或相對支撐側提供圖案化材料之不同圖案。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)雷射可雕刻彈性體凸版元件前體提供彈性體凸版元件，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)。 For example, useful flexographic printing component precursors are described in US Patents 7,799,504 (Zwadlo et al.) And 8,142,987 (Ali et al.) And US Patent Application Publication 2012/0237871 (Zwadlo). The relief image layer can be printed differently to provide different patterns of patterned material to the same or opposite support side of the substrate. In other embodiments, the elastomeric relief element is provided from a direct (or ablated) laser engravable elastomeric relief element precursor with or without the use of 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 et al.), 8,153,347 (Veres et al.), 8,187,793 (Regan et al.) And U.S. Patent Application Publication 2002/0136969 (Hiller et al.), 2003/0129530 (Leinenback et al.), 2003/0136285 (Telser et al.) ), 2003/0180636 (Kanga et al.) And 2012/0240802 (Landry-Coltrain et al.).

在本發明中使用所述彈性體凸版元件時，可以適宜方式將圖案化材料施加至凸版印刷部件中之最上凸版表面(凸起之表面)。可使用若干適宜方式實現施加且期望儘可能少地塗覆至凸版凹陷之側(斜坡)或凹部。因此，期望將儘可能多的圖案化材料僅施加至最上凸版表面。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圖案化材料至最上 凸版表面上之最佳計量。 When the elastomeric relief element is used in the present invention, a patterning material can be applied to the uppermost relief surface (convex surface) in a relief printing member in a suitable manner. Application can be achieved using several suitable means and it is desirable to apply as little as possible to the sides (slopes) or recesses of the relief of the relief. Therefore, it is desirable to apply as much patterning material as possible only to the uppermost relief surface. Anilox roll systems or other roll application systems can be used, especially low capacity anilox rolls (less than 2.5 billion cubic micrometers per square inch (6.35 billion cubic micrometers per square centimeter)) and related abrasive knives. Patterned materials can be achieved by controlling viscosity or thickness or selecting appropriate application methods Best metering on letterpress surfaces.

可自網紋輥或其他輥式上墨系統以量測量供給圖案化材料以用於每一印刷圖案。在一實施例中，可使用第一輥將圖案化材料自「油墨」盤或計量系統轉移至計量輥或網紋輥。圖案化材料在自網紋輥轉移至印刷板滾筒時通常經計量至均勻厚度。在經由輥至輥處置系統將基板(例如連續網片)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，使得將影像自凸版印刷部件轉移至基板。 The patterning material can be supplied in metered quantities from an anilox roll or other roll inking system for each printed pattern. In one embodiment, the first roll can be used to transfer the patterned material from an "ink" tray or metering system to a metering roll or anilox roll. The patterned material is typically metered to a uniform thickness as it is transferred from the anilox roll to the printing plate cylinder. When a substrate (such as a continuous web) is moved from a printing plate cylinder to an impression cylinder via a roll-to-roll processing system, the impression cylinder applies pressure to the printing plate cylinder so that the image is transferred from the letterpress printing component to the substrate.

在已將圖案化材料施加至凸版印刷部件之最上凸版表面(或凸起之表面)之後，可有用地去除包含於圖案化材料中之任何惰性有機溶劑之至少25重量%，以在凸版影像之最上凸版表面上形成更大黏性沈積物。惰性有機溶劑之此去除可以任一方式來達成，例如使用熱空氣噴射、在室溫下蒸發或在烘箱中在升高之溫度下加熱或業內已知用於去除溶劑之其他方式。 After the patterning material has been applied to the uppermost relief surface (or raised surface) of the letterpress printing part, it is useful to remove at least 25% by weight of any inert organic solvent contained in the patterning material, in Larger sticky deposits form on the uppermost relief surface. This removal of the inert organic solvent can be achieved in any manner, such as using hot air spray, evaporation at room temperature, or heating in an oven at elevated temperatures or other methods known in the industry for removing solvents.

在將一或多種圖案佈置於基板(例如呈連續網片形式)之乾燥底漆層上後，可立即(例如)藉由使用如上文所闡述來自適宜來源(例如螢光燈或LED)之適宜輻射進行輻照來固化所得前體物件中之圖案化材料以在基板上提供一或多個固化圖案。用於生成適宜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)。該等燈可包含能夠透射波長為至少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。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)上之輻照通量可為至少0.01瓦特/英吋²(0.00155瓦特/cm²)以使所施加圖案化材料以連續方式(例如以輥至 輥操作)在1秒至20秒內實現足夠迅速之光固化。 Immediately after placing one or more patterns on a dry primer layer of a substrate (e.g., in the form of a continuous mesh), such as by using a suitable source from a suitable source (e.g., a fluorescent lamp or LED) as explained above The radiation is irradiated to cure the patterned material in the resulting precursor article to provide one or more cured patterns on the substrate. Irradiation systems for generating suitable radiation may consist of one or more ultraviolet lamps in the form of, for example, 1 to 50 discharge lamps, such as xenon, metal halides, metal arcs (for example, having pressures from a few millimeters to about 10 atmospheres) Low pressure, medium pressure or high pressure mercury vapor discharge lamp with the desired operating pressure). Such lamps may include a shell capable of transmitting light having a wavelength of at least 190 nm and up to and including 700 nm or typically at least 240 nm and up to and including 450 nm. Typical lamps that can be used to provide UV radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and Hanovia 450W arc lamps. Light curing can be implemented using a combination of various lamps, and some or all of these lamps can be operated in an inert atmosphere. When using a UV lamp, the radiation flux impinging on the substrate (or the applied layer or pattern) may be at least 0.01 watts / inch ² (0.00155 watts / cm ² ) so that the applied patterning material is in a continuous manner (E.g., roll-to-roll operation) sufficiently fast light curing within 1 to 20 seconds.

擬用於光固化台中之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 irradiating device intended for use in a photo-curing station may have an emission peak wavelength of 350 nm or more. The LED device may include 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 more and having an ultraviolet light emitting diode (UV-LED) is NCCU-033 from Nichia Corporation.

前體物件之該輻照會得到中間物件，其包括基板(例如個別薄板或連續網片)且在基板之一或兩個支撐側具有一或多個固化圖案(舉例而言，各自含有適宜晶種金屬顆粒)。在前體物件之一些實施例中，可使用相同光可固化或熱可固化組合物形成多種可固化圖案及固化圖案。該光可固化組合物可包括自由基可固化組合物、酸催化組合物或自由基可固化組合物及酸催化可固化組合物二者，其皆如上文所闡述。 This irradiation of the precursor object results in an intermediate object that includes a substrate (e.g., individual sheets or continuous mesh) and has one or more curing patterns on one or both supporting sides of the substrate (for example, each containing a suitable crystal) Metal particles). In some embodiments of the precursor article, a plurality of curable patterns and cured patterns may be formed using the same photo-curable or heat-curable composition. The photocurable composition may include a radical curable composition, an acid-catalyzed composition, or both a radical-curable composition and an acid-catalytic curable composition, all of which are as described above.

所得中間物件可以此形式用於一些應用中，但在大部分實施例中，將其進一步處理以在一或多種(多種)固化圖案(其中之每一者可包含用於無電金屬鍍覆程序之晶種金屬顆粒)上納入導電金屬。舉例而言，晶種金屬顆粒可為在上文鑑別為組份(d)之金屬顆粒，例如金顆粒、銀顆粒、銅顆粒、鈀顆粒、或鉑顆粒或其混合物。 The resulting intermediate article may be used in this form for some applications, but in most embodiments, it is further processed to cure one or more (multiple) curing patterns (each of which may include an electroless metal plating process). Seed metal particles) incorporate conductive metal. For example, the seed metal particles may be metal particles identified as component (d) above, such as gold particles, silver particles, copper particles, palladium particles, or platinum particles or a mixture thereof.

本發明之一種有用方法在印刷台中使用多個柔性版印刷板(舉例而言，如上文所闡述製得)之堆疊，其中每一堆疊具有其自身印刷板滾筒，使得使用每一柔性版印刷板在基板上印刷圖案化材料之個別部分，例如使用印刷板堆疊在基板網片(例如聚合連續網片)之一或兩個支撐側上之多個部分中印刷圖案化材料之圖案。可使用多個柔性版印刷板將相同或不同光可聚合組合物「印刷」或施加至基板上之該多個部分中。 A useful method of the present invention uses a stack of multiple flexographic printing plates (for example, made as set forth above) in a printing station, where each stack has its own printing plate cylinder such that each flexographic printing plate is used Individual portions of the patterned material are printed on the substrate, for example, a pattern of the patterned material is printed in multiple portions on one or both support sides of a substrate mesh (eg, a polymeric continuous mesh) using a printing plate. Multiple flexographic printing plates can be used to "print" or apply the same or different photopolymerizable compositions to the multiple portions on a substrate.

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。隨著基板進入印刷機框架中，其與壓印滾筒接觸且使用圖案化材料(例如光可固化組合物)印刷適當圖案。另一選擇為，可利用線上柔性版印刷製程，其中印刷站係配置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可在業內獲得之資訊易於確定設備及站之其他有用構形。例如於WO 2013/063084(Jin等人)中闡述全方位(in-the-round)成像製程。 In other embodiments, it can be combined with a single impression cylinder mounted on the printing press frame. Use the center impression cylinder. As the substrate enters the printer frame, it is in contact with the impression cylinder and a suitable pattern is printed using a patterning material, such as a photocurable composition. Alternatively, an on-line flexographic printing process may be utilized, in which the printing stations are configured as horizontal lines and driven by common spools. Printing stations can be coupled to exposure stations, cutting stations, folding machines and other post-processing equipment. Those skilled in the art can use information available in the industry to easily determine other useful configurations of equipment and stations. For example, an in-the-round imaging process is described in WO 2013/063084 (Jin et al.).

可將在此階段所製得含有一或多種含有晶種金屬顆粒之固化圖案(或部分)之中間物件立即浸漬於基於水性之無電金屬鍍覆浴或溶液中，或可僅在隨後使用固化圖案時儲存中間物件。 The intermediate article containing one or more solidified patterns (or portions) containing seed metal particles can be immediately immersed in a water-based electroless metal plating bath or solution, or the solidified pattern can be used only later Intermediate objects are stored at all times.

可使中間物件與跟相應晶種金屬顆粒(上文所闡述之金屬顆粒)相同或不同之無電鍍覆金屬接觸。在大部分實施例中，無電鍍覆金屬係與相應晶種金屬顆粒不同之金屬。 The intermediate object may be brought into contact with an electroless plated metal that is the same as or different from the corresponding seed metal particles (the metal particles described above). In most embodiments, the electroless plated metal is a metal different from the corresponding seed metal particles.

此時可使用將可能無電「鍍覆」於相應晶種金屬顆粒之固化圖案上之任一金屬，但在大部分實施例中，無電鍍覆金屬可為(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)係尤其有用之無電鍍覆金屬。 At this time, any metal that may be "plated" on the solidified pattern of the corresponding seed metal particles may be electrolessly used, but in most embodiments, the electroless plated 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 plated metals.

基於水性之無電鍍覆浴或溶液中可存在一或多種無電鍍覆金屬，其量基於總溶液重量為至少0.01重量%且至多並包含20重量%。 One or more electroless plated metals may be present in the water-based electroless plating bath or solution in an amount of at least 0.01% by weight and up to and including 20% by weight based on the total solution weight.

無電鍍覆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鍍覆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鍍覆厚度或金屬無電鍍覆沈積速率。 Electroless plating can be performed using known temperature and time conditions because these conditions are well known in various textbooks and scientific literature. It is also known to include various additives such as metal complexing agents or stabilizers in aqueous-based electroless plating solutions. Changes in time and temperature can be used to change the metal electroless plating thickness or metal electroless plating deposition rate.

有用之基於水性之無電鍍覆溶液或浴係無電銅(II)鍍覆浴，其含有甲醛作為還原劑。乙二胺四乙酸(EDTA)或其鹽可存在作為銅錯合劑。舉例而言，銅無電鍍覆可端視期望沈積速率及電鍍速率及電鍍金 屬厚度而在室溫下實施若干秒且至多若干小時。 Useful are aqueous based electroless plating solutions or bath-based electroless copper (II) plating baths which contain formaldehyde as a reducing agent. Ethylenediaminetetraacetic acid (EDTA) or a salt thereof may be present as a copper complexing agent. For example, copper electroless plating can depend on the desired deposition rate and plating rate and electroplated gold Depending on the thickness, it is carried out at room temperature for several seconds and at most several hours.

其他有用之基於水性之無電鍍覆溶液或浴包括銀(I)與EDTA及酒石酸鈉、銀(I)與氨及葡萄糖、銅(II)與EDTA及二甲基胺硼烷、銅(II)與檸檬酸鹽及次磷酸鹽、鎳(II)與乳酸、乙酸及次磷酸鹽，及其他工業標準之基於水性之無電浴或溶液，例如彼等由Mallory等人在Electroless Plating：Fundamentals and Applications 1990中所闡述者。 Other useful water-based electroless plating solutions or baths include silver (I) and EDTA and sodium tartrate, silver (I) and ammonia and glucose, copper (II) and EDTA and dimethylamine borane, and copper (II) With citrate and hypophosphite, nickel (II) with lactic acid, acetic acid and hypophosphite, and other industry-standard water-based electroless baths or solutions, such as those by Mallory et al. In Electroless Plating: Fundamentals and Applications 1990 Explained in.

在用於在基板(例如以連續網片形式)之一個或相對支撐側之一或多個固化部分上提供導電金屬圖案之無電鍍覆程序之後，自基於水性之無電鍍覆浴或溶液去除所得產品物件且可使用蒸餾水或去離子水或另一基於水性之溶液再次洗滌以去除任何殘餘無電鍍覆化學品。此時，無電鍍覆金屬通常較為穩定且可用於其預期目的。 After electroless plating procedures for providing a conductive metal pattern on one or more cured portions of one or more supporting sides of a substrate (e.g., in a continuous mesh form), the resulting solution is removed from a water-based electroless plating bath or solution Product items can be washed again with distilled or deionized water or another aqueous-based solution to remove any residual electroless plating chemicals. At this time, electroless plated metal is generally relatively stable and can be used for its intended purpose.

在一些實施例中，所得產品物件可如(例如)WO 2013/063183(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 may use water at room temperature as described in, for example, [0048] of WO 2013/063183 (Petcavich) or in [0027] of WO 2013/169345 (Ramakrishnan et al.) Rinse or rinse with deionized water at temperatures less than 70 ° C.

因此，此方法提供如下產品物件：其包括如上文所闡述包括乾燥底漆層之基板且在基板之一或兩個支撐側上佈置有包括至少一些平均線寬小於15μm之細線之導電圖案。 Therefore, this method provides a product object that includes a substrate including a dry primer layer as described above and a conductive pattern including at least some fine lines with an average line width of less than 15 μm arranged on one or both of the supporting sides of the substrate.

為出於視覺或耐久性原因改變無電鍍覆金屬之表面，可採用各種後處理，包含在無電鍍覆金屬上表面再電鍍至少另一(第三或更多)金屬(例如鎳、鈀或銀)(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鍍覆(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。端視該方法之各覆蓋程序中所使用之金屬，可利用基於水性之晶種金屬觸媒溶液中之另一晶種金屬觸媒合意地處理無電鍍覆金屬以促進其他金屬之沈積。 To modify the surface of an electroless metal for visual or durability reasons, various post-treatments can be used, including replating at least another (third or more) metal (such as nickel, palladium, or silver) on the upper surface of the electroless metal ) (This procedure is sometimes referred to as "covering"), or to produce a layer of metal oxide, metal sulfide, or metal selenide sufficient to change the surface color and scattering properties without reducing the conductivity of the electroless (second) metal. Depending on the metal used in each overlay procedure of this method, another seed metal catalyst in an aqueous-based seed metal catalyst solution can be used to desirably treat the electroless plated metal to promote the deposition of other metals.

另外，可使用相同或不同條件依序實施利用基於水性之無電金屬電鍍溶液之多個處理。若適當，則亦可在室溫下或小於70℃之溫度下實施依序洗滌或沖洗步驟。 In addition, multiple treatments using an aqueous-based electroless metal plating solution may be sequentially performed using the same or different conditions. If appropriate, the sequential washing or rinsing steps can also be performed at room temperature or at a temperature of less than 70 ° C.

另外，可使用相同或不同之無電鍍覆金屬及相同或不同之無電鍍覆條件將無電鍍覆程序依序實施多次。 In addition, the same or different electroless plating metals and the same or different electroless plating conditions may be used to sequentially perform the electroless plating process multiple times.

因此，在用於提供本發明產品物件之方法之一些實施例中，該方法包括：提供上文所闡述任一實施例之透明聚合基板之連續網片，使用如上文所闡述之光可固化或熱可固化組合物(例如)使用柔性版印刷部件在連續網片之至少第一部分上(直接在乾燥底漆層上)形成光可固化或熱可固化圖案，以適宜方式(如上文所闡述)固化光可固化或熱可固化圖案以在第一部分上形成光固化或熱固化圖案，及使用上文所闡述之無電鍍覆程序利用導電金屬於第一部分上無電鍍覆光固化或熱固化圖案。 Therefore, in some embodiments of the method for providing a product object of the present invention, the method includes: providing a continuous mesh of the transparent polymeric substrate of any of the embodiments described above, using a photo-curable or The heat-curable composition (for example) uses a flexographic printing member to form a photo-curable or heat-curable pattern on at least a first portion of the continuous web (directly on the dried primer layer), in a suitable manner (as explained above) The photo-curable or heat-curable pattern is cured to form a photo-curable or heat-curable pattern on the first part, and the electro-less plating process is used to electrolessly photo-cure or heat-cure the pattern on the first part using the electroless plating process described above.

可在基板之單一支撐側上或在基板之相對支撐側上實施此方法之實施例以提供相同或不同之導電圖案。 Embodiments of this method can be implemented on a single support side of a substrate or on an opposite support side of a substrate to provide the same or different conductive patterns.

在其他實施例中，可使用本發明方法來提供複數個導電金屬圖案，其包括：提供在各別部分中包括多個光固化圖案之本發明連續網片，每一光固化圖案係藉由輻照如上文所闡述之光可固化或熱可固化組合物提供，利用無電金屬鍍覆溶液處理包括多個光固化或熱固化圖案之該連續網片以在該連續網片上在該等各別部分中提供多個無電鍍覆金屬圖案，及視情況，利用覆蓋金屬進一步處理該多個無電鍍覆金屬圖案以 在該連續網片上提供多個覆蓋導電圖案。 In other embodiments, the method of the present invention may be used to provide a plurality of conductive metal patterns, including: providing a continuous mesh of the present invention including a plurality of light-cured patterns in respective portions, each light-cured pattern is Provided as a light-curable or heat-curable composition as set forth above, the continuous web including a plurality of light-cured or heat-cured patterns is treated with an electroless metal plating solution to form the respective parts on the continuous web. To provide multiple electroless plated metal patterns, and optionally use cover metal to further process the multiple electroless plated metal patterns to A plurality of overlay conductive patterns are provided on the continuous mesh.

此方法可藉由以下進一步實施：自包括多個覆蓋導電圖案之該連續網片形成個別導電物件，及將該等個別導電物件組裝成相同或不同之個別器件，例如具有觸控螢幕顯示器之顯示器件。 This method can be further implemented by forming individual conductive objects from the continuous mesh covering a plurality of conductive patterns, and assembling the individual conductive objects into the same or different individual devices, such as a display with a touch screen display Device.

可使用相同或不同之光可固化或熱可固化組合物在基板之兩個支撐側上實施該等方法實施例。 These method embodiments can be implemented on the two support sides of a substrate using the same or different light-curable or heat-curable compositions.

可將根據本發明製得之有用之產品物件尤其制定為包括適宜導電柵格線、電極(或BUS區域)、電引線及電連結器之電容式觸控螢幕感測器。舉例而言，可藉由印刷圖案材料及無電鍍覆經印刷圖案來形成電極及尾部。 Useful product objects made in accordance with the present invention can be specifically formulated as capacitive touch screen sensors including suitable conductive grid lines, electrodes (or BUS areas), electrical leads, and electrical connectors. For example, electrodes and tails can be formed by printing pattern materials and electroless plated printed patterns.

用於實施本發明之有用之方法及裝置之一些細節闡述於(例如)WO 2013/063183(Petcavich)、WO 2013/169345(Ramakrishnan等人)中。在PCT/US/062366(由Petcavich及Jin於2012年10月29日提出申請)中提供用於尤其以輥至輥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 devices for implementing the present invention are described in, for example, WO 2013/063183 (Petcavich), WO 2013/169345 (Ramakrishnan et al.). Further details of a useful manufacturing system for the preparation of conductive articles, especially in a roll-to-roll manner, are provided in PCT / US / 062366 (filed by Petcavich and Jin on October 29, 2012).

可用於實施本發明之設備及步驟特徵之其他系統闡述於美國專利第14/146,867號(由Shifley在2014年1月3日提出申請)中。 Other systems that can be used to implement the features of the apparatus and steps of the present invention are described in U.S. Patent No. 14 / 146,867 (filed by Shifley on January 3, 2014).

參照圖1，其展示可用於本發明方法實施例之柔性版印刷系統100之示意性側視圖，該柔性版印刷系統用於在基板150(可包括直接佈置於載體上之乾燥底漆層)之兩個(相對)支撐側上輥-輥印刷光可固化或熱可固化組合物。在整個柔性版印刷系統100中，基板150係以連續網片形式自供應輥102供給至捲曲輥104。基板150將具有第一支撐側151及第二支撐側152。 Referring to FIG. 1, there is shown a schematic side view of a flexographic printing system 100 that can be used in an embodiment of the method of the present invention. The flexographic printing system is used for Two (opposite) support side upper roll-to-roll prints of light curable or heat curable compositions. In the entire flexographic printing system 100, the substrate 150 is supplied from the supply roller 102 to the curling roller 104 in the form of a continuous web. The substrate 150 will have a first support side 151 and a second support side 152.

柔性版印刷系統100包含兩個印刷模組120及140，其經構形以在基板150之第一支撐側151上印刷；以及兩個印刷模組110及130，其經 構形以在基板150之第二(相對)支撐側152上印刷。基板150之連續網片總體在輥至輥方向105(圖1中左至右)上行進。然而，使用各個輥106及107以視需要局部改變基板之連續網片之方向用於調節網張力、提供緩衝區及使支撐側翻轉用於印刷。特定而言，印刷模組120輥107用以逆轉基板150之連續網片之局部方向，使得使得其實質上以自右至左之方向移動。 The flexographic printing system 100 includes two printing modules 120 and 140 that are configured to print on the first support side 151 of the substrate 150; and two printing modules 110 and 130 that are It is configured to be printed on the second (opposite) support side 152 of the substrate 150. The continuous web of the substrate 150 generally travels in a roll-to-roll direction 105 (left to right in FIG. 1). However, each of the rollers 106 and 107 is used to locally change the direction of the continuous web of the substrate as needed for adjusting the web tension, providing a buffer zone, and flipping the support side for printing. Specifically, the printing module 120 roller 107 is used to reverse the local direction of the continuous web of the substrate 150 so that it is substantially moved from right to left.

印刷模組110、120、130、140中之每一者可包含一些類似裝置組件，包含各別板滾筒111、121、131、141，其上分別安裝各別柔性版印刷板112、122、132、142。每一柔性版印刷部件(柔性版印刷板)112、122、132、142具有界定擬印刷於基板150上之影像圖案之凸起特徵113。每一印刷模組110、120、130、140亦包含各別壓印滾筒114、124、134、144，其經構形以迫使基板150之支撐側與相應柔性版印刷部件112、122、132、142接觸。 Each of the printing modules 110, 120, 130, 140 may include some similar device components, including respective plate rollers 111, 121, 131, 141, on which respective flexographic printing plates 112, 122, 132 are respectively mounted. , 142. Each flexographic printing component (flexographic printing plate) 112, 122, 132, 142 has a raised feature 113 defining an image pattern to be printed on the substrate 150. Each printing module 110, 120, 130, 140 also includes a respective impression cylinder 114, 124, 134, 144, which is configured to force the supporting side of the substrate 150 and the corresponding flexographic printing component 112, 122, 132, 142 contacts.

在提及印刷模組110、120、130、140之不同組件之旋轉方向時，應注意在圖1中展示之視圖中印刷模組120及140(用於在基板150之第一側151上印刷)之壓印滾筒124及144逆時針旋轉，而在此視圖中印刷模組110及130(用於在基板150之第二側152上印刷)之壓印滾筒114及134順時針旋轉。 When referring to the rotation directions of the different components of the printing modules 110, 120, 130, 140, it should be noted that the printing modules 120 and 140 (for printing on the first side 151 of the substrate 150) are shown in the view shown in FIG. ), The impression cylinders 124 and 144 rotate counterclockwise, and in this view the impression cylinders 114 and 134 of the printing modules 110 and 130 (for printing on the second side 152 of the substrate 150) rotate clockwise.

每一印刷模組110、120、130、140亦包含各別網紋輥115、125、135、145，其用於將圖案化材料提供至相應柔性版印刷部件(柔性版印刷板)112、122、132、142。如印刷工業中眾所周知，網紋輥係硬滾筒，其通常由鋼或鋁核心構築而成，其具有含有數百萬極細微坑(稱為小室)之外表面。使用網紋輥將可易於轉移圖案化材料。在一些實施例中，印刷模組110、120、130、140中之一部分或全部亦包含各別UV固化台116、126、136、146，其用於將所印刷圖案化材料固化至基板150上。 Each printing module 110, 120, 130, 140 also includes a respective anilox roller 115, 125, 135, 145, which is used to provide a patterned material to a corresponding flexographic printing component (flexographic printing plate) 112, 122 , 132, 142. As is well known in the printing industry, anilox rollers are hard cylinders, which are usually constructed of a steel or aluminum core, and have an outer surface containing millions of extremely fine pits (called cells). Using an anilox roller will make it easy to transfer the patterned material. In some embodiments, one or all of the printing modules 110, 120, 130, 140 also include respective UV curing stations 116, 126, 136, 146 for curing the printed patterning material onto the substrate 150. .

圖2至5中展示可藉由本發明實施例製備之產品物件及器件之一些實施例。 Some embodiments of product objects and devices that can be prepared by embodiments of the present invention are shown in FIGS. 2 to 5.

圖2展示具有包含顯示器件320及覆蓋顯示器件320之可視區域之至少一部分之觸控感測器330之觸控螢幕310之裝置(或器件)300之高級系統圖表。觸控感測器330感測接觸且對應於所感測接觸將電信號(與(例如)電容值相關)傳達至控制器380。觸控感測器330係可藉由包含納入上文所闡述之柔性版印刷(上墨)系統之實施例之印刷模組之柔性版印刷系統100在兩個支撐側上印刷之物件的實例。 FIG. 2 shows a high-level system diagram of a device (or device) 300 having a touch screen 310 including a display device 320 and a touch sensor 330 covering at least a portion of a visible area of the display device 320. The touch sensor 330 senses a contact and communicates an electrical signal (related to, for example, a capacitance value) to the controller 380 corresponding to the sensed contact. The touch sensor 330 is an example of an article that can be printed on two support sides by a flexographic printing system 100 including a printing module incorporating an embodiment of the flexographic printing (inking) system described above.

圖3展示觸控感測器330之示意性側視圖。本發明透明基板340(例如透明聚酯(例如透明聚(對苯二甲酸乙二酯)))具有印刷於第一支撐側341上之第一導電圖案350及印刷於第二(相對)支撐側342上之第二導電圖案360。自捲取輥104(圖1)切割之透明基板340之長度及寬度不大於柔性版印刷系統100(圖1)之柔性版印刷板(或柔性版印刷部件)112、122、132、142，但其可能小於柔性版印刷板(或柔性版印刷部件)112、122、132、142。視情況，可在柔性版印刷及固化圖案或圖案化材料後針對改良導電率使用鍍覆製程鍍覆第一導電圖案350及第二導電圖案360。可使用圖案化材料提供本發明方法之所述導電圖案350及360。 FIG. 3 shows a schematic side view of the touch sensor 330. The transparent substrate 340 (such as a transparent polyester (such as transparent poly (ethylene terephthalate)) of the present invention has a first conductive pattern 350 printed on the first support side 341 and a second (opposite) support side. The second conductive pattern 360 on 342. The length and width of the transparent substrate 340 cut by the self-winding roller 104 (Fig. 1) are not larger than the flexographic printing plates (or flexographic printing parts) 112, 122, 132, 142 of the flexographic printing system 100 (Fig. 1), but It may be smaller than flexographic printing plates (or flexographic printing components) 112, 122, 132, 142. Optionally, the first conductive pattern 350 and the second conductive pattern 360 may be plated using a plating process for improved conductivity after the flexographic printing and curing of the pattern or patterning material. The patterned material may be used to provide the conductive patterns 350 and 360 of the method of the present invention.

圖4展示可使用一或多個印刷模組(例如柔性版印刷系統(圖1)之印刷模組120及140)印刷於基板340(圖3)之第一支撐側341(圖3)上之導電圖案350之實例。導電圖案350包含柵格352，其包含相交細線351及353之柵格行355，該等柵格行與通道墊354之陣列連結。互連線356將通道墊354連結至與控制器380(圖2)連結之連結器墊358。在一些實施例中，可藉由單一印刷模組120印刷導電圖案350。然而，由於用於細線351及353(例如具有大約4μm至8μm之線寬)之最佳印刷條件通常與用於印刷較寬通道墊354、連結器墊358及互連線356不同，故可 有利地使用一個印刷模組120用於印刷細線351及353及第二印刷模組140用於印刷較寬特徵。另外，為使細線351及353清晰相交，可進一步有利地使用一個印刷模組120印刷並固化一組細線351，且使用第二印刷模組140印刷並固化第二組細線353，且使用經構形類似於印刷模組120及140之第三印刷模組(圖1中未展示)印刷較寬特徵。 Figure 4 shows that one or more printing modules (e.g., printing modules 120 and 140 of a flexographic printing system (Figure 1)) can be printed on a first support side 341 (Figure 3) of a substrate 340 (Figure 3). An example of the conductive pattern 350. The conductive pattern 350 includes a grid 352 including grid lines 355 that intersect thin lines 351 and 353, and the grid lines are connected to an array of channel pads 354. The interconnect line 356 connects the channel pad 354 to a connector pad 358 connected to the controller 380 (FIG. 2). In some embodiments, the conductive pattern 350 may be printed by a single printing module 120. However, since the optimal printing conditions for fine lines 351 and 353 (for example, having a line width of about 4 μm to 8 μm) are usually different from those used for printing wider channel pads 354, connector pads 358, and interconnect lines 356, it is possible to It is advantageous to use one printing module 120 for printing thin lines 351 and 353 and a second printing module 140 for printing wider features. In addition, in order to make the thin lines 351 and 353 clearly intersect, a set of thin lines 351 may be further printed and cured using a printing module 120, and a second set of thin lines 353 may be printed and cured using a second printing module 140, and A third printing module (not shown in Fig. 1) having a shape similar to the printing modules 120 and 140 prints wider features.

圖5展示可使用一或多個印刷模組(例如柔性版印刷系統100(圖1)之印刷模組110及130)印刷於基板340(圖3)之第二支撐側342(圖3)上之導電圖案360之實例。導電圖案360包含柵格362，其包含相交細線361及363之柵格列365，該等柵格列與通道墊364之陣列連結。互連線366將通道墊364連結至與控制器380(圖2)連結之連結器墊368。在一些實施例中，可藉由單一印刷模組110(圖1)印刷導電圖案360。然而，由於用於細線361及363(例如具有大約4μm至8μm之線寬)之最佳印刷條件通常與用於較寬通道墊364、連結器墊368及互連線366不同，故可有利地使用一個印刷模組110(圖1)用於印刷細線361及363及第二印刷模組130(圖1)用於印刷較寬特徵。另外，為使細線361及363清晰相交，可進一步有利地使用一個印刷模組110(圖1)印刷並固化一組細線361，且使用第二印刷模組130(圖1)印刷並固化第二組細線363，且使用經構形類似於印刷模組110及130(圖1)之第三印刷模組(圖1中未展示)印刷較寬特徵。 Fig. 5 shows that one or more printing modules (e.g., printing modules 110 and 130 of the flexographic printing system 100 (Fig. 1)) can be printed on the second support side 342 (Fig. 3) of the substrate 340 (Fig. 3). Examples of conductive patterns 360. The conductive pattern 360 includes a grid 362 including grid lines 365 of intersecting thin lines 361 and 363, which are connected to an array of channel pads 364. The interconnect line 366 connects the channel pad 364 to a connector pad 368 connected to the controller 380 (FIG. 2). In some embodiments, the conductive pattern 360 may be printed by a single printing module 110 (FIG. 1). However, since the optimal printing conditions for fine lines 361 and 363 (for example, having a line width of about 4 μm to 8 μm) are generally different from those used for wider channel pads 364, connector pads 368, and interconnect lines 366, it may be advantageous One printing module 110 (FIG. 1) is used for printing thin lines 361 and 363 and a second printing module 130 (FIG. 1) is used for printing wider features. In addition, in order to make the fine lines 361 and 363 intersect clearly, a set of fine lines 361 may be further printed and cured using one printing module 110 (FIG. 1), and the second printing module 130 (FIG. 1) may be used to print and cure the second Set of thin lines 363, and print a wider feature using a third printing module (not shown in Figure 1) that is similar in configuration to printing modules 110 and 130 (Figure 1).

另一選擇為，在一些實施例中，可使用一或多個如印刷模組110及130(圖1)構形之印刷模組印刷導電圖案350(圖4)，且可使用一或多個如印刷模組120及140(圖1)構形之印刷模組印刷導電圖案360(圖5)。 Alternatively, in some embodiments, the conductive pattern 350 (FIG. 4) may be printed using one or more printed modules configured as the printing modules 110 and 130 (FIG. 1), and one or more may be used For example, a printed module configured by printing modules 120 and 140 (Figure 1) prints a conductive pattern 360 (Figure 5).

參照圖2至5，在觸控螢幕310之操作中，控制器380可經由連結器墊358依序電驅動柵格行355且可經由連結器墊368依序感測柵格列365上之電信號。在其他實施例中，可逆轉對柵格行355及柵格列365 之驅動及感測作用。 Referring to FIGS. 2 to 5, in the operation of the touch screen 310, the controller 380 may sequentially drive the grid rows 355 via the connector pads 358 and sequentially sense the power on the grid rows 365 via the connector pads 368. signal. In other embodiments, the grid rows 355 and grid columns 365 can be reversed. Driving and sensing functions.

本發明提供至少下列實施例及其組合，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 those skilled in the art will appreciate from the teachings disclosed herein since then:

1.一種組合物，其包括第一聚合物乳膠及第二聚合物乳膠之混合物，其中該第一聚合物乳膠包括第一聚合物及第一表面活性劑，使得該第一聚合物乳膠之乾燥塗層具有至少50%之表面極性，且其中該第二聚合物乳膠包括第二聚合物及第二表面活性劑，使得該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，且其中該組合物之乾燥塗層具有至少15%且至多並包含50%之表面極性。 A composition comprising a mixture of a first polymer latex and a second polymer latex, wherein the first polymer latex includes a first polymer and a first surfactant, so that the first polymer latex is dried The coating has a surface polarity of at least 50%, and wherein the second polymer latex includes a second polymer and a second surfactant, so that the dry coating of the second polymer latex has a surface polarity of less than or equal to 27% And wherein the dry coating of the composition has a surface polarity of at least 15% and at most 50%.

2.如實施例1之組合物，其中該組合物之乾燥塗層具有至少28%且至多並包含50%之表面極性。 2. The composition of embodiment 1, wherein the dry coating of the composition has a surface polarity of at least 28% and at most and including 50%.

3.如實施例1或2之組合物，其中：基於第一聚合物總重量，該第一聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，該第一聚合物具有至少25℃且至多並包含75℃之玻璃轉變溫度，且該第一表面活性劑係α-烯烴(C₁₄-C₁₆)磺酸鈉；基於第二聚合物總重量，該第二聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，該第二聚合物具有至少25℃且至多並包含75℃之玻璃轉變溫度，且該第二表面活性劑係硫酸化聚乙氧基壬基苯酚之銨鹽；該混合物中之該第一聚合物乳膠對該第二聚合物乳膠之重量比率為1：1且至並包含2.5：1； 基於乾燥塗層總重量，該第一表面活性劑以至少1重量%且至多並包含3重量%之量存在於該混合物之乾燥塗層中；基於乾燥塗層總重量，該第二表面活性劑以至少0.35重量%且至多並包含1.1重量%之量存在於該混合物之乾燥塗層中；且基於乾燥塗層總重量，該混合物之乾燥塗層中之該等第一及第二表面活性劑之總量為至多且包含3.35重量%。 3. The composition according to embodiment 1 or 2, wherein: the first polymer comprises at least 75% by weight and at most 90% by weight based on glycidyl (meth) acrylate, based on the total weight of the first polymer Repeating units and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, the first polymer has a glass transition temperature of at least 25 ° C and up to and including 75 ° C, And the first surfactant is an α-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate; based on the total weight of the second polymer, the second polymer includes at least 75% by weight and at most and includes 90% by weight derived from ( Repeating units of glycidyl methacrylate and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, the second polymer has at least 25 ° C and at most Contains a glass transition temperature of 75 ° C, and the second surfactant is an ammonium salt of sulfated polyethoxynonylphenol; the weight ratio of the first polymer latex to the second polymer latex in the mixture is 1: 1 and up to and including 2.5: 1; based on dry coating The total weight of the first surfactant is present in the dry coating of the mixture in an amount of at least 1% and up to and including 3% by weight; based on the total weight of the dry coating, the second surfactant is at least 0.35 weight % And up to and including 1.1% by weight is present in the dry coating of the mixture; and based on the total weight of the dry coating, the total amount of the first and second surfactants in the dry coating of the mixture is Up to and including 3.35% by weight.

4.如實施例1至3中任一項之組合物，其中該第一表面活性劑係由R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺代表之化合物，其中R係C₁₀、C₁₁或C₁₂烴基團；或具有係C₁₀至C₁₂烴基團中之任一者之不同R基團之該等化合物之混合物；且該第二表面活性劑係由R’-苯基-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺代表，其中R’係C₈至C₁₂烴基團，且n為3至10。 4. The composition according to any one of embodiments 1 to 3, wherein the first surfactant is a compound represented by R-CH ₂ -CH = CH-CH ₂ -S (= O) ₂ O ^- Na ⁺ Wherein R is a C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon group; or a mixture of these compounds having different R groups that are any one of C ₁₀ to C ₁₂ hydrocarbon groups; and the second surfactant is a R'- phenyl _{- (O-CH 2 CH 2} ) n -S (= O) O 2 - NH 4 + representatives, where R 'based C ₈ to C ₁₂ hydrocarbon group, and n is 3-10.

5.如實施例1至4中任一項之組合物，其中該第一聚合物乳膠及該第二聚合物乳膠中之至少一者包括乙烯基聚合物，該乙烯基聚合物進一步包括衍生自具有含至少2個碳原子之酯烷基之(甲基)丙烯酸烷基酯之重複單元。 5. The composition of any one of embodiments 1 to 4, wherein at least one of the first polymer latex and the second polymer latex includes a vinyl polymer, and the vinyl polymer further includes a derivative derived from Repeating unit of an alkyl (meth) acrylate having an ester alkyl group containing at least 2 carbon atoms.

6.如實施例1至5中任一項之組合物，其中該第一聚合物及該第二聚合物中之至少一者經交聯。 6. The composition according to any one of embodiments 1 to 5, wherein at least one of the first polymer and the second polymer is crosslinked.

7.一種基板，其包括載體及佈置於該載體之至少一個支撐表面上之乾燥底漆層，該乾燥底漆層包括如實施例1至6中任一項之組合物。 7. A substrate comprising a carrier and a dry primer layer disposed on at least one supporting surface of the carrier, the dry primer layer comprising the composition as in any one of embodiments 1 to 6.

8.如實施例7之基板，其具有至少88%之積分透射率。 8. The substrate of embodiment 7 having an integrated transmittance of at least 88%.

9.如實施例7或8之基板，其包括透明聚合載體且直接在上面佈置有乾燥底漆層。 9. The substrate according to embodiment 7 or 8, which comprises a transparent polymeric carrier and a dry primer layer is arranged directly on it.

10. 如實施例7至9中任一項之基板，其中該乾燥底漆層中之該第一聚合物乳膠對該第二聚合物乳膠之重量比率為1：3且至並包含3：1。 10. The substrate according to any one of embodiments 7 to 9, wherein the weight ratio of the first polymer latex to the second polymer latex in the dry primer layer is 1: 3 and up to and including 3: 1 .

11. 如實施例7至10中任一項之基板，其中該乾燥底漆層具有至 少0.05μm且至多並包含0.4μm之平均厚度。 11. The substrate according to any one of embodiments 7 to 10, wherein the dry primer layer has It is at least 0.05 μm and at most and includes an average thickness of 0.4 μm.

12. 如實施例7至11中任一項之基板，其包括聚(對苯二甲酸乙二酯)或聚(萘二甲酸乙二酯)載體。 12. The substrate according to any one of embodiments 7 to 11, comprising a poly (ethylene terephthalate) or a poly (ethylene naphthalate) carrier.

13. 如實施例7至12中任一項之基板，其係連續撓性基板。 13. The substrate according to any one of Examples 7 to 12, which is a continuous flexible substrate.

14. 一種物件，其包括如實施例7至13中任一項之基板，且包括：透明聚合載體及佈置於該透明載體之至少一個支撐表面上之乾燥底漆層，及包括平均線寬小於15μm之線之圖案化材料，該圖案化材料直接佈置於該乾燥底漆層上。 14. An article comprising the substrate according to any one of embodiments 7 to 13, and comprising: a transparent polymeric carrier and a dry primer layer disposed on at least one supporting surface of the transparent carrier, and including an average line width less than The patterning material of the 15 μm line is directly arranged on the dry primer layer.

15. 如實施例14之物件，其中該圖案化材料包括選自由金、銀、銅、鈀、鉑、鎳及其前體組成之群之導電金屬或其前體。 15. The article of embodiment 14, wherein the patterned material comprises a conductive metal or a precursor thereof selected from the group consisting of gold, silver, copper, palladium, platinum, nickel, and precursors thereof.

16. 如實施例14或15之物件，其中該圖案化材料包括自由基可固化組合物、酸催化可固化組合物或自由基可固化組合物及酸催化可固化組合物之混合物。 16. The article of embodiment 14 or 15, wherein the patterning material comprises a free radical curable composition, an acid catalysable curable composition or a mixture of a free radical curable composition and an acid catalysable curable composition.

17. 如實施例14或15之物件，其中該圖案化材料包括分散於光固化或熱固化組合物內之金屬顆粒。 17. The article of embodiment 14 or 15, wherein the patterned material comprises metal particles dispersed in a photo-curable or heat-curable composition.

18. 如實施例14、15及17中任一項之物件，其中該圖案化材料包括分散於衍生自自由基可固化組合物及酸催化可固化組合物之光固化或熱固化組合物內之金、銀、銅、鈀或鉑之顆粒。 18. The article as in any one of embodiments 14, 15, and 17, wherein the patterned material comprises a light- or thermal-curable composition dispersed in a free-radical curable composition and an acid-catalyzed curable composition. Particles of gold, silver, copper, palladium or platinum.

19. 一種提供如實施例14至18中任一項之物件之方法，該方法包括：提供如實施例7至13中任一項之基板，及直接在該乾燥底漆層上提供圖案化材料之圖案。 19. A method of providing an article as in any of Examples 14 to 18, the method comprising: providing a substrate as in any of Examples 7 to 13, and providing a patterned material directly on the dried primer layer Of the pattern.

20. 如實施例19之方法，其中圖案化材料之該圖案之至少一部分包括平均線寬小於15μm之線。 20. The method of embodiment 19, wherein at least a portion of the pattern of the patterned material includes lines having an average line width of less than 15 μm.

21. 如實施例19或20之方法，其中圖案化材料之該圖案之至少一部分存在於該打底物件之觸控螢幕區域中。 21. The method of embodiment 19 or 20, wherein at least a portion of the pattern of the patterned material is present in a touch screen area of the base object.

22. 如實施例19至21中任一項之方法，其包括：藉由使該乾燥底漆層與攜載該圖案化材料之凸版印刷部件直接接觸來直接在該乾燥底漆層上提供該圖案化材料。 22. The method of any one of embodiments 19 to 21, comprising: providing the dry primer layer directly on the dry primer layer by directly contacting the dry primer layer with a letterpress printing member carrying the patterned material. Patterned material.

23. 如實施例19至22中任一項之方法，其中該圖案化材料包括導電金屬或其前體。 23. The method of any one of embodiments 19 to 22, wherein the patterned material comprises a conductive metal or a precursor thereof.

24. 如實施例19至23中任一項之方法，其進一步包括：固化該圖案化材料中之光可固化或熱可固化組合物。 24. The method of any one of embodiments 19 to 23, further comprising: curing the photo-curable or heat-curable composition in the patterned material.

25. 如實施例19至24中任一項之方法，其中該圖案化材料包括金屬顆粒且該方法進一步包括：無電金屬鍍覆圖案化材料之該圖案。 25. The method of any one of embodiments 19 to 24, wherein the patterning material comprises metal particles and the method further comprises: electroless metal plating the pattern of the patterning material.

26. 一種自如實施例19至25中任一項之方法獲得之產品物件，其中該產品物件包括導電材料之至少一種圖案，其中導電材料之該圖案之至少一部分包括平均線寬小於15μm之導電線，導電材料之該圖案之該部分直接佈置於該透明聚合基板之該乾燥底漆層上。 26. A product article obtained by the method of any one of embodiments 19 to 25, wherein the product article includes at least one pattern of a conductive material, wherein at least a portion of the pattern of the conductive material includes conductive lines having an average line width of less than 15 μm The portion of the pattern of the conductive material is directly disposed on the dry primer layer of the transparent polymer substrate.

27. 如實施例19至25中任一項之方法，其包括：提供呈連續網片形式之透明聚合基板，直接在該連續網片之一或多個個別部分中之該乾燥底漆層上分別提供作為前體導電材料之光可固化或熱可固化組合物之一或多個個別圖案，該光可固化或熱可固化組合物包括金屬晶種顆粒，藉由固化來轉化光可固化或熱可固化組合物之該一或多個個別圖案中之每一者以在該一或多個個別部分中形成一或多個個別固化圖案，該一或多個個別固化圖案中之每一者包括該等金屬晶種顆粒，及無電鍍覆該一或多個個別固化圖案中之每一者中之該等金屬晶種顆粒以提供一或多個個別導電圖案。 27. The method of any one of embodiments 19 to 25, comprising: providing a transparent polymeric substrate in the form of a continuous mesh directly on the dry primer layer in one or more individual portions of the continuous mesh. One or more individual patterns of a light-curable or heat-curable composition are provided as precursor conductive materials, respectively. The light-curable or heat-curable composition includes metal seed particles, and the light-curable or Each of the one or more individual patterns of the heat-curable composition to form one or more individual cured patterns in the one or more individual portions, each of the one or more individual cured patterns Including the metal seed particles, and electroless plating the metal seed particles in each of the one or more individual cured patterns to provide one or more individual conductive patterns.

28. 一種提供複數個物件之方法，該方法包括：提供如實施例7至13中任一項之基板， 直接在該連續網片之第一部分中之乾燥底漆層上形成第一可固化圖案，該第一可固化圖案包括含有晶種金屬顆粒之光可固化或熱可固化組合物，此係藉由使該連續網片之該第一部分中之該乾燥底漆層與攜載該光可固化或熱可固化組合物之柔性版印刷部件直接接觸來達成，使包括含有該第一可固化圖案之該第一部分之該連續網片行進至鄰近固化台且固化該第一可固化圖案，由此在該第一部分上形成第一固化圖案，該第一固化圖案包括晶種金屬顆粒，直接在該連續網片之第二部分中之乾燥底漆層上形成第二可固化圖案，該第二可固化圖案包括含有相同或不同之晶種金屬顆粒之相同或不同光可固化或熱可固化組合物，此係藉由與攜載該相同或不同之光可固化或熱可固化組合物之柔性版印刷部件直接接觸來達成，使包括含有該第二可固化圖案之該第二部分之該連續網片行進至鄰近固化台且固化該第二可固化圖案，由此在該第二部分上形成第二固化圖案，該第二固化圖案包括相同或不同之晶種金屬顆粒，視情況，使用相同或不同之可固化或熱可固化組合物及相同或不同之柔性版印刷部件針對該連續網片之其他各別部分將形成及行進特徵實施一或多次，以在該等其他各別部分上形成其他固化圖案，及捲繞包括第一、第二及其他可選固化圖案之該連續網片以提供多個前體物件的捲材。 28. A method for providing a plurality of objects, the method comprising: providing a substrate as in any one of embodiments 7 to 13, A first curable pattern is formed directly on the dried primer layer in the first part of the continuous mesh, and the first curable pattern includes a photo-curable or heat-curable composition containing seed metal particles by This is achieved by directly contacting the dry primer layer in the first part of the continuous web with a flexographic printing member carrying the photo-curable or heat-curable composition, such that the The continuous mesh in the first part travels to the adjacent curing table and cures the first curable pattern, thereby forming a first curing pattern on the first part, the first curing pattern including seed metal particles directly on the continuous mesh. A second curable pattern is formed on the dried primer layer in the second part of the sheet, and the second curable pattern includes the same or different photo-curable or heat-curable composition containing the same or different seed metal particles. This is achieved by direct contact with a flexographic printing part carrying the same or different photo-curable or heat-curable composition, such that the second part including the second curable pattern is included The continuous mesh advances to a neighboring curing station and cures the second curable pattern, thereby forming a second curing pattern on the second portion, the second curing pattern including the same or different seed metal particles, as appropriate, Using the same or different curable or heat-curable compositions and the same or different flexographic printing parts will implement one or more features for the other individual parts of the continuous web to form one or more times in these other individual parts Other cured patterns are partially formed, and the continuous web including the first, second, and other optional cured patterns is wound to provide a web of multiple precursor objects.

29. 如實施例28之方法，其中該等相同晶種金屬顆粒存在於該多個固化圖案中之每一者中，該等晶種金屬顆粒係金顆粒、銀顆粒、銅顆粒、鈀顆粒或鉑顆粒。 29. The method of embodiment 28, wherein the same seed metal particles are present in each of the plurality of curing patterns, and the seed metal particles are gold particles, silver particles, copper particles, palladium particles, or Platinum particles.

30. 如實施例28或29之方法，其中將該相同光可固化或熱可固化組合物用於每一可固化圖案之每一形成特徵中。 30. The method of embodiment 28 or 29, wherein the same photo-curable or heat-curable composition is used in each forming feature of each curable pattern.

31. 如實施例28至30中任一項之方法，其中將該相同光可固化 組合物用於每一可固化圖案之每一形成特徵中，該光可固化組合物包括自由基可固化組合物、酸催化可固化組合物或自由基可固化組合物及酸催化可固化組合物二者。 31. The method of any one of embodiments 28 to 30, wherein the same photocurable The composition is used in each forming feature of each curable pattern, and the photocurable composition includes a radical curable composition, an acid-catalysable curable composition or a radical-curable composition, and an acid-catalysable curable composition. both.

32. 一種器件，其包括如實施例14至18及26中任一項之物件，該物件包括一或多種直接佈置於該乾燥底漆層上之導電金屬圖案，其中該一或多種導電金屬圖案中之每一者包括含有平均線寬小於15μm之導電線之觸控區域。 32. A device comprising the article as in any one of embodiments 14 to 18 and 26, the article comprising one or more conductive metal patterns arranged directly on the dry primer layer, wherein the one or more conductive metal patterns Each of them includes a touch area including conductive lines having an average line width of less than 15 μm.

33. 如實施例32之器件，其係觸控螢幕器件。 33. The device of embodiment 32, which is a touch screen device.

提供下列實例以闡釋本發明之實踐且不欲以任何方式進行限制。 The following examples are provided to illustrate the practice of the invention and are not intended to be limiting in any way.

實例1：組合物-聚合物乳膠混合物之製備Example 1: Preparation of a composition-polymer latex mixture 第一聚合物乳膠(乳膠A)之製備：Preparation of the first polymer latex (latex A):

藉由向2公升玻璃反應器中添加652g去礦質水來合成聚(甲基丙烯酸縮水甘油基酯-共-丁基丙烯酸酯)。向2公升玻璃原料罐中再添加651g去礦質水。將兩個器皿中之攪動器設定於150RPM。在系統中確立氮氣氛，且向每一器皿中添加30.9g Rhodacal^® A246L陰離子表面活性劑(「第一表面活性劑」)。將反應器內容物溫度升至60℃，且向原料罐中添加526g甲基丙烯酸縮水甘油基酯及92.3g丙烯酸正丙基酯。在原料罐中製得單體乳液且溫度為60℃時，向反應器中添加6.16g偶氮雙(4-氰基)戊酸(75%)。將原料罐之內容物經240分鐘計量至反應器中且將反應器內容物在60℃下攪拌兩小時，隨後添加0.48g溶於9g水中之異抗壞血酸。然後，以逐滴方式向反應器中添加1.35g溶於47g水中之30重量%過氧化氫。然後將反應器內容物在60℃下再攪拌一小時。然後將所得第一聚合物乳膠冷卻至25℃並經由30μm毛布過濾。此製備得到1900g含有32%固體之經過濾第一聚合物乳膠。藉由UPA測得第一聚合物中值粒徑為53.1nm。 Poly (glycidyl methacrylate-co-butyl acrylate) was synthesized by adding 652 g of demineralized water to a 2 liter glass reactor. Add 651 g of demineralized water to the 2 liter glass raw material tank. Set the agitator in both vessels to 150 RPM. A nitrogen atmosphere was established in the system, and 30.9 g of Rhodacal ^® A246L anionic surfactant ("first surfactant") was added to each vessel. The temperature of the reactor contents was raised to 60 ° C, and 526 g of glycidyl methacrylate and 92.3 g of n-propyl acrylate were added to the raw material tank. When a monomer emulsion was prepared in a raw material tank and the temperature was 60 ° C., 6.16 g of azobis (4-cyano) valeric acid (75%) was added to the reactor. The contents of the raw material tank were metered into the reactor over 240 minutes and the reactor contents were stirred at 60 ° C for two hours, and then 0.48 g of erythorbic acid dissolved in 9 g of water was added. Then, 1.35 g of 30% by weight hydrogen peroxide dissolved in 47 g of water was added to the reactor in a dropwise manner. The reactor contents were then stirred for an additional hour at 60 ° C. The resulting first polymer latex was then cooled to 25 ° C and filtered through a 30 μm felt. This preparation yielded 1900 g of filtered first polymer latex containing 32% solids. The median particle size of the first polymer measured by UPA was 53.1 nm.

第二聚合物乳膠(乳膠B)之製備：Preparation of the second polymer latex (latex B):

藉由向2公升玻璃反應器中添加675.2g去礦質水來合成聚(甲基丙烯酸縮水甘油基酯-共-丁基丙烯酸酯)。向2公升玻璃原料罐中添加674g去礦質水。將兩個器皿中之攪動器設定於150RPM。在系統中確立氮氣氛，且向每一器皿中添加7.72g Rhodapex^® CO-436陰離子表面活性劑(「第二表面活性劑」)。將反應器內容物溫度升至60℃，且向原料罐中添加526g甲基丙烯酸縮水甘油基酯及92.3g丙烯酸正丙基酯。在原料罐中製得單體乳液且反應器內容物溫度為60℃時，向反應器中添加6.16g偶氮雙(4-氰基)戊酸(75%)及2.66g28%氨水溶液。將原料罐之內容物經240分鐘計量至反應器中且將反應器內容物在60℃下攪拌兩小時，隨後添加0.48g溶於9g水中之異抗壞血酸。然後，以逐滴方式向反應器中添加1.35g溶於47g水中之30重量%過氧化氫。將反應器內容物在60℃下再攪拌一小時。然後將所得第一聚合物乳膠冷卻至25℃並經由30μm毛布過濾。此製備得到1900g含有30.6%固體之經過濾第一聚合物乳膠。藉由UPA測得第一聚合物中值粒徑為87.1nm。 Poly (glycidyl methacrylate-co-butyl acrylate) was synthesized by adding 675.2 g of demineralized water to a 2 liter glass reactor. Add 674 g of demineralized water to a 2 liter glass raw material tank. Set the agitator in both vessels to 150 RPM. A nitrogen atmosphere was established in the system, and 7.72 g of Rhodapex ^® CO-436 anionic surfactant ("second surfactant") was added to each vessel. The temperature of the reactor contents was raised to 60 ° C, and 526 g of glycidyl methacrylate and 92.3 g of n-propyl acrylate were added to the raw material tank. When a monomer emulsion was prepared in the raw material tank and the temperature of the reactor content was 60 ° C., 6.16 g of azobis (4-cyano) valeric acid (75%) and 2.66 g of a 28% aqueous ammonia solution were added to the reactor. The contents of the raw material tank were metered into the reactor over 240 minutes and the reactor contents were stirred at 60 ° C. for two hours, and then 0.48 g of erythorbic acid dissolved in 9 g of water was added. Then, 1.35 g of 30% by weight hydrogen peroxide dissolved in 47 g of water was added to the reactor in a dropwise manner. The reactor contents were stirred for an additional hour at 60 ° C. The resulting first polymer latex was then cooled to 25 ° C and filtered through a 30 μm felt. This preparation yielded 1900 g of filtered first polymer latex containing 30.6% solids. The median particle size of the first polymer measured by UPA was 87.1 nm.

所獲得使用如上文所闡述乳液聚合獲得之各種聚合物之玻璃轉變溫度及不同單體重量比率如下： The glass transition temperatures and different monomer weight ratios of the various polymers obtained using the emulsion polymerization as described above are as follows:

實例2：基板及物件之製備Example 2: Preparation of substrates and objects

以下列方式製備打底聚(對苯二甲酸乙二酯)基板。 A primer poly (ethylene terephthalate) substrate was prepared in the following manner.

藉由擠出且澆注至適於在機器及橫向方向上拉伸之後得到125μm厚雙軸定向膜之厚度來形成透明聚(對苯二甲酸乙二酯)(PET)膜(或 載體)之試樣。在拉伸操作之前，施加底漆組合物且乾燥以在PET載體之兩個相對支撐側上提供乾燥底漆層。所測試底漆組合物含有上文所闡述乳膠A及乳膠B中之一者或兩者。然後如本文所述拉伸包括透明載體及乾燥底漆層之所得打底基板以減小收縮及濁度。各種所得打底基板A至N及所得乾燥底漆層之平均乾燥厚度闡述於下表II中。 Form a transparent poly (ethylene terephthalate) (PET) film by extruding and casting to a thickness suitable for obtaining a 125 μm thick biaxially oriented film after stretching in the machine and transverse direction Carrier). Prior to the stretching operation, the primer composition is applied and dried to provide a dry primer layer on two opposite support sides of the PET carrier. The primer composition tested contained one or both of latex A and latex B as described above. The resulting base substrate including a transparent support and a dried primer layer is then stretched as described herein to reduce shrinkage and turbidity. The average dry thickness of each of the resulting base substrates A to N and the resulting dry primer layer is described in Table II below.

以20%總乳膠聚合物之濃度使用等量第一聚合物乳膠(乳膠A)及第二聚合物乳膠(乳膠B)、0.2重量%皂苷(以50重量%溶液)及0.033重量% Aerodisp^® W7512S發煙二氧化矽顆粒(平均大小為0.1μm)來製備表II中所闡述鑑別為試樣B之打底基板。以類似形式使用如表II中所述加以變化之量之第一聚合物乳膠及第二聚合物乳膠來製備鑑別為試樣A、C及D至N之打底基板。鑑別為試樣D之打底基板亦含有1重量%之間苯二酚。以與鑑別為試樣A之底漆組合物相同之方式來製備鑑別為試樣N之打底基板，只是以相對於乳膠B中之第二聚合物總重量2重量%之量向分散液中添加Rhodacal^® A246L陰離子表面活性劑(「第一表面活性劑」)(因此，納入第一表面活性劑及第二表面活性劑，但第一表面活性劑並非納入作為不同聚合物乳膠之一部分)。 Use the same amount of first polymer latex (latex A) and second polymer latex (latex B), 0.2% by weight saponin (in 50% by weight solution), and 0.033% by weight Aerodisp ^® W7512S at a concentration of 20% total latex polymer Fuming silica particles (average size 0.1 μm) were used to prepare the base substrate identified as Sample B as set forth in Table II. Primer substrates identified as samples A, C, and D to N were prepared in a similar manner using the first polymer latex and the second polymer latex in varying amounts as described in Table II. The base substrate identified as Sample D also contained 1% by weight resorcinol. A primer substrate identified as Sample N was prepared in the same manner as the primer composition identified as Sample A, except that it was added to the dispersion in an amount of 2% by weight relative to the total weight of the second polymer in Latex B. Add Rhodacal ^® A246L anionic surfactant ("first surfactant") (therefore, the first surfactant and the second surfactant are included, but the first surfactant is not included as part of different polymer latex).

實例3：Example 3:

使用上文所闡述第一及第二聚合物乳膠之混合物及各種打底基板以下列方式來提供圖案化材料之印刷圖案(包含導電圖案)。 Using the mixture of the first and second polymer latexes described above and various base substrates to provide printed patterns (including conductive patterns) of patterned materials in the following manner.

表面極性%：Surface polarity%:

基於已知福克斯能量法(Fowkes energy method)，藉由首先量測一滴水及一滴二碘甲烷中之每一者在給定乾燥表面上之2分鐘接觸角(θ)來測定給定乾燥表面(例如聚合物乳膠之乾燥底漆層或乾燥層)之表面極性百分比。在知曉每一流體之液體表面張力(γ_L)之色散(γ^d _L)及極性(γ^p _L)分量(參見下表I)下，使用下文所展示之方程式1計算給定乾燥表面之極性及色散分量。然後使用下文及表I中所展示之方程式2計算 表面極性百分比。 Based on the known Fowkes energy method, a given dry surface is measured by first measuring the 2-minute contact angle (θ) of each of a drop of water and a drop of diiodomethane on a given dry surface ( (Eg, dry primer layer or dry layer of polymer latex). Knowing the dispersion (γ ^d _L ) and polarity (γ ^p _L ) components of the liquid surface tension (γ _L ) of each fluid (see Table I below), use Equation 1 shown below to calculate the polarity of a given dry surface And dispersion components. The surface polarity percentage is then calculated using Equation 2 shown below and in Table I.

γ_L(1+cosθ)=2[(γ^d _L γ^p _L)^½+(γ^d _S γ^p _S)^½] 方程式1 γ _L (1 + cosθ) = 2 [(γ ^d _L γ ^p _L ) ^½ + (γ ^d _S γ ^p _S ) ^½ ] Equation 1

表面極性%=100[γ^p _S/(γ^d _S+γ^p _S)] 方程式2 Surface polarity% = 100 [γ ^p _S / (γ ^d _S + γ ^p _S )] Equation 2

光可固化組合物(「油墨」)Photocurable composition (`` ink '')

光可固化組合物1(油墨1)： Photocurable composition 1 (ink 1):

此光可固化組合物(或圖案化材料)類似於在美國專利第14/174,879號之發明實例1(闡述於上文中)及美國專利第14/197,293號之發明實例1(亦闡述於上文中)中所闡述者，且至少包括形成為100g等分試樣之下列組份： 14.4g環氧樹脂丙烯酸酯(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異戊四醇四丙烯酸酯(Sigma-Aldrich)、0.8g混合於50%碳酸丙二酯中之三芳基鋶鹽六氟磷酸鹽(Sigma-Aldrich)、0.8g混合於50%碳酸丙二酯中之三芳基鋶鹽六氟銻酸鹽(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銀奈米顆粒(Novacentrix，20-25nm平均粒徑，Ag-25-ST3)、1.1g碳奈米顆粒(來自US Nano之US1074)、0.001g 9-茀酮(Sigma-Aldrich)及35g 1-甲氧基異丙醇(Sigma-Aldrich)溶劑。 This photocurable composition (or patterned material) is similar to Invention Example 1 (described above) in US Patent No. 14 / 174,879 and Invention Example 1 (also described above in US Patent No. 14 / 197,293) ) And at least the following components formed into 100 g aliquots: 14.4 g epoxy resin acrylate (CN 153 from Sartomer), 9.9 g poly (ethylene glycol) diacrylate (M _n 258, Sigma-Aldrich), 2.1 g poly (ethylene glycol) diacrylate (575 _n , Sigma-Aldrich), 10.8 g isopentaerythritol tetraacrylate (Sigma-Aldrich), 0.8 g mixed in 50 Triarylsulfonium hexafluorophosphate (Sigma-Aldrich) in% propylene carbonate, 0.8g Triarylsulfonium hexafluoroantimonate (Sigma-Aldrich) in 2.4% of propylene carbonate, 2.4g Free radical photo starter hydroxycyclohexylphenyl ketone (Sigma-Aldrich), 1.2 g of free radical photo starter methyl-4 '-(methylthio) -2-morpholinyl phenylacetone (Sigma-Aldrich) , 19.5g silver nanoparticle (Novacentrix, 20-25nm average particle size, Ag-25-ST3), 1.1g carbon nanoparticle (US1074 from US Nano), 0.001g 9-fluorenone (Sigma-Aldrich), and 35g 1-methoxyisopropanol (Sigm a-Aldrich) solvent.

光可固化組合物2(油墨2)： Photocurable composition 2 (ink 2):

類似於油墨1來製備此光可固化組合物(或圖案化材料)，但其並不含有9-茀酮。 This photocurable composition (or patterning material) was prepared similarly to ink 1, but it did not contain 9-fluorenone.

印刷光可固化組合物：Printing light curable composition:

使用來自IGT測試Systems公司，Arlington Heights,IL之臺式測試印刷機「IGT F1適印性測試儀」以柔性版墨水獲得各種打底PET基板上之上文所闡述光可固化組合物之印刷圖案的試樣。用於向柔性版印刷板施加光可固化組合物之網紋輥系統具有1.3BCMI及1803lpi之值，如由IGT所指定。在環境溫度下使用20N之網紋力、10N之印刷力及0.20m/s之印刷速度來製備印刷圖案。 Using the desktop test printing press "IGT F1 Printability Tester" from IGT Test Systems, Arlington Heights, IL to obtain the printing patterns of the photocurable composition described above on various primer PET substrates with flexographic inks Of the sample. The anilox roller system for applying a photocurable composition to a flexographic printing plate has values of 1.3BCMI and 1803 lpi, as specified by IGT. A printing pattern was prepared at ambient temperature using an anilox force of 20 N, a printing force of 10 N, and a printing speed of 0.20 m / s.

用於印刷光可固化組合物之柔性板係市售Kodak Flexcel NX光聚合物板前體(Eastman Kodak公司)之試樣，其已使用具有使用Kodak Square Spot雷射技術在12,800dpi之解析度下書寫之預定圖案之遮罩進行成像。對曝光柔性板前體實施UV曝光且使用由製造商建議用於該等凸版印刷部件之已知條件處理(顯影)。所得柔性版印刷板各為1.14mm厚(包含PET)。用於將柔性板安裝至印刷形式滾筒之背襯膠帶為來自3M公司之1120Beige膠帶，其為20密耳(0.051cm)厚且具有55之蕭氏A(Shore A)。柔性版印刷板中之凸版影像設計包含具有頂凸版表面寬度為7μm之細線之柵格圖案。自使用所述柵格圖案印刷之圖案獲得下文所展示打底PET基板上之印刷平均線寬。 The flexible board used to print the photocurable composition is a sample of a commercially available Kodak Flexcel NX photopolymer board precursor (Eastman Kodak Corporation), which has been written using a Kodak Square Spot laser technology at a resolution of 12,800 dpi A mask of a predetermined pattern is imaged. The exposed flexible plate precursor was subjected to UV exposure and treated (developed) using known conditions recommended by the manufacturer for such letterpress printing components. The resulting flexographic printing plates were each 1.14 mm thick (including PET). The backing tape used to mount the flexible board to the printed form cylinder was 1120 Beige tape from 3M Company, which was 20 mils (0.051 cm) thick and had a Shore A of 55. The relief image design in a flexographic printing plate includes a grid pattern with fine lines with a top relief surface width of 7 μm. The printed average line width on the primer PET substrate shown below was obtained from the pattern printed using the grid pattern.

在印刷之後，利用UV輻射使用Fusion 300 WPI中壓汞燈(其提供介於190-1500nm之間之輻照波長)利用298mJ/cm²之近似曝光來輻照光可固化組合物之每一印刷圖案以固化圖案化材料之每一印刷圖案。以透射及反射模式使用Olympus BH-2光學顯微鏡量測固化圖案之印刷平均線寬。 After printing, each print of the light curable composition was irradiated with UV radiation using a Fusion 300 WPI medium pressure mercury lamp (which provides an irradiation wavelength between 190-1500 nm) with an approximate exposure of 298 mJ / cm ² The pattern is to cure each printed pattern of the patterned material. Measure the printed average line width of the cured pattern in transmission and reflection mode using an Olympus BH-2 optical microscope.

無電金屬鍍覆：Electroless metal plating:

藉由以下方式來無電銅鍍覆各種打底基板上包括固化圖案之中間物件：將具有固化圖案之中間物件在45℃下於含有Enplate Cu-406無電鍍覆溶液(Enthone)之燒杯中浸漬7分鐘，隨後使用蒸餾水沖洗且 使用氮乾燥，使得形成在打底基板上佈置有導電圖案之產品物件。 Electroless copper was used to plate intermediate objects including cured patterns on various substrates by electroless copper by immersing the intermediate objects with cured patterns in a beaker containing Enplate Cu-406 electroless plating solution (Enthone) at 45 ° C. 7 Minutes, followed by rinsing with distilled water and Using nitrogen drying, a product object having a conductive pattern arranged on a base substrate is formed.

黏著測試(「膠帶去除測試」)：Adhesion Test ("Tape Removal Test"):

在無電鍍覆之後，立即將一片來自3M公司之Scotch^® 810 Magic Tape黏著膠帶施加至每一產品物件中之無電鍍覆圖案上且然後撕去產品物件之表面。記錄藉由此操作去除之銅量以指示無電鍍覆圖案與打底PET基板之黏著性。結果展示於下表II中。 Immediately after electroless plating, a piece of Scotch ^® 810 Magic Tape adhesive tape from 3M Company was applied to the electroless plated pattern in each product object and then the surface of the product object was peeled off. The amount of copper removed by this operation was recorded to indicate the adhesion between the electroless plated pattern and the underlying PET substrate. The results are shown in Table II below.

以0至5等級之量表評價每一基板之塗層外觀，其中「0」等級指示表面均勻性並無可見差異，「1」等級指示具有極少可觀察表面不均勻性，「2」等級指示具有較小但可觀察之表面不均勻性，「3」等級指示具有明顯可觀察之表面不均勻性，「4」等級指示具有顯著表面不均勻性(包含高濁度及虹彩)，且「5」等級指示具有嚴重表面不均勻性(包含高濁度及虹彩)。 The coating appearance of each substrate was evaluated on a scale of 0 to 5. A "0" grade indicates that there is no visible difference in surface uniformity, a "1" grade indicates that there is very little observable surface unevenness, and a "2" grade indicates Has a small but observable surface unevenness, a "3" grade indicates a noticeable surface unevenness, a "4" grade indicates a significant surface unevenness (including high turbidity and iridescence), and a "5" "The grade indicates severe surface unevenness (including high turbidity and iridescence).

另外，在下表II中，使用Hazegard Plus濁度計(BYK Gardner)量測濁度(%)及「%T」，其中「濁度」係穿過基板之光散射之量度，其中較高數值影響其澄清度；且「T%」係穿過基板之積分透射率之量度，其中較高數值指示較高透明性。 In addition, in Table II below, a Hazegard Plus turbidimeter (BYK Gardner) is used to measure turbidity (%) and "% T", where "turbidity" is a measure of light scattering through the substrate, and the higher value affects Its clarity; and "T%" is a measure of the integrated transmittance through the substrate, where higher values indicate higher transparency.

使用Ultrascan XE色度計(Hunter)量測每一基板之色度值且以標準CIELAB命名報告結果，其中表II中之b*代表藍-黃色軸上之基板顏色且較大正b*值指示基板中之較大黃色外觀。 Use the Ultrascan XE colorimeter (Hunter) to measure the colorimetric value of each substrate and report the results under the standard CIELAB nomenclature, where b * in Table II represents the color of the substrate on the blue-yellow axis and a larger positive b * value indicates the substrate Medium yellow appearance.

在表II中，「YI」代表黃色指數(E313標準)，其係納入CIELAB量測之計算值，使得增加之YI值指示基板外觀更黃。 In Table II, "YI" stands for the yellow index (E313 standard), which is included in the calculated value measured by CIELAB, so that the increased YI value indicates that the appearance of the substrate is more yellow.

在基板之兩個支撐側上實施柵格線評估。據觀察，兩個支撐側之線寬結果基本相同。 A grid line evaluation is performed on both support sides of the substrate. It is observed that the line width results of the two support sides are basically the same.

在表II中，「油墨」係指如上文所鑑別之油墨1或油墨2。 In Table II, "ink" means Ink 1 or Ink 2 as identified above.

鑑別為對比實例A、C及D之印刷物件展現類似總表面能，但展現不同表面極性%，使得使得圖案化材料之印刷具有差異。對比實例A得到平均線寬大於使用鑑別為發明實例B及E至M之印刷物件獲得之平均線寬之印刷導電線。鑑別為對比實例C及D之印刷物件展現較差印刷線品質。 The printed articles identified as Comparative Examples A, C, and D exhibited similar total surface energy, but exhibited different surface polarities%, making the printing of the patterned materials different. Comparative Example A resulted in printed conductive wires having an average line width greater than the average line width obtained using printed articles identified as Invention Examples B and E to M. The printed articles identified as Comparative Examples C and D exhibited poor print line quality.

鑑別為發明實例B及E至M之印刷物件(使用本發明之乾燥底漆層(第一及第二聚合物乳膠之混合物)製得以提供介於19與44之間之表面極性%)產生平均線寬小於10μm且具有良好品質之導電線，且顯示無電鍍覆銅對打底基板之良好無電鍍覆性能及黏著性。鑑別為發明實例E-G及I-L之印刷物件展現尤其良好之塗層外觀、低濁度及低顏色。 Printed articles identified as Invention Examples B and E to M (made using the dry primer layer (mixture of the first and second polymer latex) of the present invention to provide a surface polarity% between 19 and 44) yielded an average The line width is less than 10 μm and has good quality conductive wires, and shows the good electroless plating performance and adhesion of the electroless copper plating to the base substrate. The printed articles identified as Invention Examples E-G and I-L exhibited particularly good coating appearance, low turbidity, and low color.

鑑別為對比實例N之印刷物件顯示，僅向單一聚合物乳膠(「第二」聚合物乳膠或乳膠B)中添加其他表面活性劑(「第一表面活性劑」)不足以提供所需塗層均勻性。而是，根據本發明，需要藉助個別第一及第二聚合物乳膠向乾燥底漆層中提供第一及第二表面活性劑。 The printed article identified as Comparative Example N showed that the addition of other surfactants ("first surfactants") to a single polymer latex ("second" polymer latex or latex B) was not sufficient to provide the required coating Uniformity. Instead, according to the present invention, the first and second surfactants need to be provided into the dry primer layer by means of individual first and second polymer latexes.

鑑別為發明實例H之印刷物件並不展現最佳塗層外觀，但具有期望導電線品質。 The printed article identified as Invention Example H did not exhibit the best coating appearance, but had the desired conductive wire quality.

實例4：Example 4:

使用類似於實例1中使用Mark-Andy壓機以20ft/m(6.06m/min)所闡述之光可固化組合物及類似於圖1中所闡述用於在PET載體之兩個支撐側上提供窄線形式之光可固化組合物圖案之製程來形成含有打底基板的前體物件。 A photocurable composition similar to that illustrated in Example 1 using a Mark-Andy press at 20 ft / m (6.06 m / min) and similar to that illustrated in Figure 1 for providing on two support sides of a PET carrier were used. The process of patterning the light curable composition in the form of a narrow line to form a precursor object containing a primer substrate.

Claims (33)

一種組合物，其包括第一聚合物乳膠及第二聚合物乳膠之混合物，其中該第一聚合物乳膠包括第一聚合物及第一表面活性劑，使得該第一聚合物乳膠之乾燥塗層具有至少50%之表面極性，且其中該第二聚合物乳膠包括第二聚合物及第二表面活性劑，使得該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，且其中該組合物之乾燥塗層具有至少15%且至多並包含50%之表面極性，且其中基於第一聚合物總重量，該第一聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，該第一聚合物具有至少25℃且至多並包含75℃之玻璃轉變溫度，且該第一表面活性劑係α-烯烴(C₁₄-C₁₆)磺酸鈉；基於第二聚合物總重量，該第二聚合物包括至少75重量%且至多並包含90重量%衍生自(甲基)丙烯酸縮水甘油基酯之重複單元及至少10重量%且至多並包含25重量%衍生自(甲基)丙烯酸正丁基酯之重複單元，該第二聚合物具有至少25℃且至多並包含75℃之玻璃轉變溫度，且該第二表面活性劑係硫酸化聚乙氧基壬基苯酚之銨鹽；該混合物中之該第一聚合物乳膠對該第二聚合物乳膠之重量比率為1：1且至並包含2.5：1；基於乾燥塗層總重量，該第一表面活性劑係以至少1重量%且至多並包含3重量%之量存在於該混合物之乾燥塗層中；基於乾燥塗層總重量，該第二表面活性劑係以至少0.35重量%且至多並包含1.1重量%之量存在於該混合物之乾燥塗層中；且基於乾燥塗層總重量，該混合物之乾燥塗層中之該等第一及第二表面活性劑之總量為至多且包含3.35重量%。A composition comprising a mixture of a first polymer latex and a second polymer latex, wherein the first polymer latex includes a first polymer and a first surfactant such that the first polymer latex is a dry coating Have a surface polarity of at least 50%, and wherein the second polymer latex includes a second polymer and a second surfactant, so that the dry coating of the second polymer latex has a surface polarity of less than or equal to 27%, and Wherein the dry coating of the composition has a surface polarity of at least 15% and up to and including 50%, and wherein the first polymer includes at least 75% by weight and up to and including 90% by weight of the derivative based on the total weight of the first polymer From the repeating units of glycidyl (meth) acrylate and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate, the first polymer has at least 25 ° C and Up to and including a glass transition temperature of 75 ° C., and the first surfactant is an α-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate; based on the total weight of the second polymer, the second polymer includes at least 75% by weight And at most The second polymer containing 90% by weight of repeating units derived from glycidyl (meth) acrylate and at least 10% by weight and up to and including 25% by weight of repeating units derived from n-butyl (meth) acrylate Has a glass transition temperature of at least 25 ° C and at most and contains 75 ° C, and the second surfactant is an ammonium salt of sulfated polyethoxynonylphenol; the first polymer latex in the mixture is opposite to the second The weight ratio of the polymer latex is 1: 1 and up to and including 2.5: 1; the first surfactant is present in the mixture in an amount of at least 1% by weight and up to and including 3% by weight based on the total weight of the dry coating. In the dry coating; based on the total weight of the dry coating, the second surfactant is present in the dry coating of the mixture in an amount of at least 0.35 wt% and up to and including 1.1 wt%; and based on the total weight of the dry coating By weight, the total amount of the first and second surfactants in the dry coating of the mixture is up to and including 3.35% by weight. 如請求項1之組合物，其中該組合物之乾燥塗層具有至少28%且至多並包含50%之表面極性。The composition of claim 1, wherein the dry coating of the composition has a surface polarity of at least 28% and at most and including 50%. 如請求項1或2之組合物，其中該第一表面活性劑係由R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺代表之化合物，其中R係C₁₀、C₁₁或C₁₂烴基團；或具有係C₁₀至C₁₂烴基團中之任一者之不同R基團之該等化合物之混合物；且該第二表面活性劑係由R’-苯基-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺代表，其中R’係C₈至C₁₂烴基團，且n為3至10。The composition according to claim 1 or 2, wherein the first surfactant is a compound represented by R-CH ₂ -CH = CH-CH ₂ -S (= O) ₂ O ^- Na ⁺ , wherein R is C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon groups; or a mixture of these compounds having different R groups that are any of C ₁₀ to C ₁₂ hydrocarbon groups; and the second surfactant is R'-phenyl _{- (O-CH 2 CH 2} ) n -S (= O) O 2 - NH 4 + representatives, where R 'based C ₈ to C ₁₂ hydrocarbon group, and n is 3-10. 如請求項1或2之組合物，其中該第一聚合物乳膠及該第二聚合物乳膠中之至少一者包括乙烯基聚合物，該乙烯基聚合物進一步包括衍生自具有含至少2個碳原子之酯烷基之(甲基)丙烯酸烷基酯之重複單元。The composition of claim 1 or 2, wherein at least one of the first polymer latex and the second polymer latex includes a vinyl polymer, and the vinyl polymer further includes a derivative derived from a polymer having at least 2 carbons. Atomic ester alkyl Repeating unit of alkyl (meth) acrylate. 如請求項1或2之組合物，其中該第一聚合物及該第二聚合物中之至少一者經交聯。The composition of claim 1 or 2, wherein at least one of the first polymer and the second polymer is crosslinked. 一種基板，其包括載體及佈置於該載體之至少一個支撐表面上之乾燥底漆層，該乾燥底漆層包括如請求項1至5中任一項之組合物。A substrate comprising a carrier and a dry primer layer disposed on at least one supporting surface of the carrier, the dry primer layer comprising the composition as claimed in any one of claims 1 to 5. 如請求項6之基板，其具有至少88%之積分透射率。The substrate as claimed in claim 6, which has an integrated transmittance of at least 88%. 如請求項6或7之基板，其包括透明聚合載體且該乾燥底漆層直接佈置在該載體上。If the substrate of claim 6 or 7, it comprises a transparent polymeric carrier and the dried primer layer is arranged directly on the carrier. 如請求項6或7之基板，其中該乾燥底漆層中之該第一聚合物乳膠對該第二聚合物乳膠之重量比率為1：3且至並包含3：1。The substrate of claim 6 or 7, wherein the weight ratio of the first polymer latex to the second polymer latex in the dry primer layer is 1: 3 and up to and including 3: 1. 如請求項6或7之基板，其中該乾燥底漆層具有至少0.05μm且至多並包含0.4μm之平均厚度。The substrate of claim 6 or 7, wherein the dry primer layer has an average thickness of at least 0.05 μm and at most and including 0.4 μm. 如請求項6或7之基板，其包括聚(對苯二甲酸乙二酯)或聚(萘二甲酸乙二酯)載體。If the substrate of claim 6 or 7 comprises a poly (ethylene terephthalate) or poly (ethylene naphthalate) carrier. 如請求項6或7之基板，其係連續撓性基板。If the substrate of claim 6 or 7, it is a continuous flexible substrate. 一種物件，其包括如請求項6至12中任一項之基板，且包括：透明聚合載體及佈置於該透明載體之至少一個支撐表面上之乾燥底漆層，及包括平均線寬小於15μm之線之圖案化材料，該圖案化材料係直接佈置於該乾燥底漆層上。An article comprising a substrate as claimed in any one of claims 6 to 12 and comprising: a transparent polymeric carrier and a dry primer layer disposed on at least one supporting surface of the transparent carrier, and including an average line width of less than 15 μm The patterned material of the line is directly arranged on the dry primer layer. 如請求項13之物件，其中該圖案化材料包括選自由金、銀、銅、鈀、鉑、鎳及其前體組成之群之導電金屬或其前體。The article of claim 13, wherein the patterned material comprises a conductive metal or a precursor thereof selected from the group consisting of gold, silver, copper, palladium, platinum, nickel, and precursors thereof. 如請求項13或14之物件，其中該圖案化材料包括自由基可固化組合物、酸催化可固化組合物或自由基可固化組合物及酸催化可固化組合物兩者之混合物。The article of claim 13 or 14, wherein the patterning material comprises a free radical curable composition, an acid catalysable curable composition or a mixture of both a free radical curable composition and an acid catalysable curable composition. 如請求項13或14之物件，其中該圖案化材料包括分散於光固化或熱固化組合物內之金屬顆粒。The article of claim 13 or 14, wherein the patterned material comprises metal particles dispersed in a photo-curable or heat-curable composition. 如請求項13或14之物件，其中該圖案化材料包括分散於衍生自自由基可固化組合物及酸催化可固化組合物之光固化或熱固化組合物內之金、銀、銅、鈀或鉑之顆粒。The article of claim 13 or 14, wherein the patterning material comprises gold, silver, copper, palladium, or a light-curing or heat-curing composition derived from a radical curable composition and an acid-catalyzed curable composition, or Particles of platinum. 一種提供如請求項13至17中任一項之物件之方法，該方法包括：提供如請求項6至12中任一項之基板，及直接在乾燥底漆層上提供圖案化材料之圖案。A method of providing an article as in any of claims 13 to 17, the method comprising: providing a substrate as in any of claims 6 to 12, and providing a pattern of a patterned material directly on the dried primer layer. 如請求項18之方法，其中圖案化材料之該圖案之至少一部分包括平均線寬小於15μm之線。The method of claim 18, wherein at least a portion of the pattern of the patterned material includes lines having an average line width of less than 15 μm. 如請求項18或19之方法，其中圖案化材料之該圖案之該至少一部分係存在於該物件之觸控螢幕區域中。The method of claim 18 or 19, wherein the at least a portion of the pattern of the patterned material is present in a touch screen area of the object. 如請求項18或19之方法，其包括：藉由使該乾燥底漆層與攜載該圖案化材料之凸版印刷部件直接接觸而直接在該乾燥底漆層上提供該圖案化材料。The method of claim 18 or 19, comprising: directly providing the patterned material on the dried primer layer by directly contacting the dried primer layer with a relief printing member carrying the patterned material. 如請求項18或19之方法，其中該圖案化材料包括導電金屬或其前體。The method of claim 18 or 19, wherein the patterned material comprises a conductive metal or a precursor thereof. 如請求項18或19之方法，其進一步包括：固化該圖案化材料中之光可固化或熱可固化組合物。The method of claim 18 or 19, further comprising: curing the photo-curable or heat-curable composition in the patterned material. 如請求項18或19之方法，其中該圖案化材料包括金屬顆粒且該方法進一步包括：無電金屬鍍覆圖案化材料之該圖案。The method of claim 18 or 19, wherein the patterned material comprises metal particles and the method further comprises: electroless metal plating the pattern of the patterned material. 如請求項18或19之方法，其包括：提供呈連續網片形式之透明聚合基板，直接在該連續網片之一或多個個別部分中之該乾燥底漆層上分別提供作為前體導電材料之光可固化或熱可固化組合物之一或多個個別圖案，該光可固化或熱可固化組合物包括金屬晶種顆粒，藉由固化來轉化光可固化或熱可固化組合物之該一或多個個別圖案中之每一者以在該一或多個個別部分中形成一或多個個別固化圖案，該一或多個個別固化圖案中之每一者包括該等金屬晶種顆粒，及無電鍍覆該一或多個個別固化圖案中之每一者中之該等金屬晶種顆粒以提供一或多個個別導電圖案。A method as claimed in item 18 or 19, comprising: providing a transparent polymeric substrate in the form of a continuous mesh, directly providing conductive conduction as a precursor on the dry primer layer in one or more individual portions of the continuous mesh, respectively. One or more individual patterns of the light-curable or heat-curable composition of the material, the light-curable or heat-curable composition including metal seed particles, and the light-curable or heat-curable composition is converted by curing Each of the one or more individual patterns to form one or more individual cured patterns in the one or more individual portions, each of the one or more individual patterns includes the metal seed Particles, and the metal seed particles in each of the one or more individual cured patterns are electrolessly plated to provide one or more individual conductive patterns. 一種自如請求項18至24中任一項之方法獲得之產品物件，其中該產品物件包括導電材料之至少一種圖案，其中導電材料之該圖案之至少一部分包括平均線寬小於15μm之導電線，導電材料之該圖案之該部分係直接佈置於該透明聚合基板之該乾燥底漆層上。A product object obtained by the method of any one of claims 18 to 24, wherein the product object includes at least one pattern of a conductive material, wherein at least a portion of the pattern of the conductive material includes a conductive line having an average line width of less than 15 μm, conductive The portion of the pattern of the material is arranged directly on the dry primer layer of the transparent polymer substrate. 一種提供複數個物件之方法，該方法包括：提供呈連續網片形式之如請求項6至12中任一項之基板，直接在該連續網片之第一部分中之乾燥底漆層上形成第一可固化圖案，該第一可固化圖案包括含有晶種金屬顆粒之光可固化或熱可固化組合物，此係藉由使該連續網片之該第一部分中之該乾燥底漆層與攜載該光可固化或熱可固化組合物之柔性版印刷部件直接接觸來達成，使包括含有該第一可固化圖案之該第一部分之該連續網片行進至鄰近固化台且固化該第一可固化圖案，由此在該第一部分上形成第一固化圖案，該第一固化圖案包括該等晶種金屬顆粒，直接在該連續網片之第二部分中之乾燥底漆層上形成第二可固化圖案，該第二可固化圖案包括含有相同或不同晶種金屬顆粒之相同或不同光可固化或熱可固化組合物，此係藉由與攜載該相同或不同之光可固化或熱可固化組合物之柔性版印刷部件直接接觸來達成，使包括含有該第二可固化圖案之該第二部分之該連續網片行進至鄰近固化台且固化該第二可固化圖案，由此在該第二部分上形成第二固化圖案，該第二固化圖案包括該等相同或不同之晶種金屬顆粒。A method of providing a plurality of objects, the method comprising: providing a substrate in the form of a continuous mesh as in any of claims 6 to 12, forming a first layer directly on the dried primer layer in the first part of the continuous mesh; A curable pattern. The first curable pattern includes a photo-curable or heat-curable composition containing seed metal particles. This is achieved by combining the dry primer layer and the carrier in the first portion of the continuous mesh. The flexographic printing member carrying the photo-curable or heat-curable composition is brought into direct contact to achieve that the continuous web including the first portion containing the first curable pattern is advanced to an adjacent curing table and the first curable Curing pattern, thereby forming a first curing pattern on the first portion, the first curing pattern including the seed metal particles, forming a second coatable layer directly on the dried primer layer in the second portion of the continuous mesh. Curing pattern, the second curable pattern includes the same or different photo-curable or heat-curable composition containing the same or different seed metal particles, which is cured by carrying the same or different light-curable Or the direct contact of the flexographic printing parts of the heat-curable composition, so that the continuous web including the second part containing the second curable pattern is advanced to the adjacent curing table and the second curable pattern is cured, This forms a second cured pattern on the second portion, the second cured pattern including the same or different seed metal particles. 如請求項27之方法，其中該方法進一步包括使用相同或不同之可固化或熱可固化組合物及相同或不同之柔性版印刷部件針對該連續網片之其他各別部分將該等形成及行進特徵實施一或多次，以在該等其他各別部分上形成其他固化圖案，及捲繞包括第一及第二固化圖案之該連續網片或包括第一、第二及其他固化圖案之該連續網片以提供複數個前體物件的捲材。The method of claim 27, wherein the method further comprises using the same or different curable or heat-curable composition and the same or different flexographic printing parts to form and travel the other portions of the continuous web Features are implemented one or more times to form other cured patterns on these other respective parts, and to roll the continuous mesh including the first and second cured patterns or the first, second, and other cured patterns. Continuous webs to provide a web of precursor articles. 如請求項27或28之方法，其中該等相同晶種金屬顆粒存在於該多個固化圖案中之每一者中，該等晶種金屬顆粒係金顆粒、銀顆粒、銅顆粒、鈀顆粒或鉑顆粒。The method of claim 27 or 28, wherein the same seed metal particles are present in each of the plurality of solidified patterns, and the seed metal particles are gold particles, silver particles, copper particles, palladium particles, or Platinum particles. 如請求項27或28之方法，其中在每一可固化圖案之每一形成特徵中使用該相同光可固化或熱可固化組合物。The method of claim 27 or 28, wherein the same photo-curable or heat-curable composition is used in each forming feature of each curable pattern. 如請求項27或28之方法，其中在每一可固化圖案之每一形成特徵中使用該相同光可固化組合物，該光可固化組合物包括自由基可固化組合物、酸催化可固化組合物或自由基可固化組合物及酸催化可固化組合物二者。The method of claim 27 or 28, wherein the same photo-curable composition is used in each forming feature of each curable pattern, the photo-curable composition including a radical curable composition, an acid-catalyzed curable combination Or a free radical curable composition and an acid-catalyzed curable composition. 一種器件，其包括如請求項13至17及26中任一項之物件，該物件包括一或多個直接佈置於該乾燥底漆層上之導電金屬圖案，其中該一或多個導電金屬圖案中之每一者包括含有平均線寬小於15μm之導電線之觸控區域。A device comprising the article as claimed in any one of claims 13 to 17 and 26, the article comprising one or more conductive metal patterns arranged directly on the dry primer layer, wherein the one or more conductive metal patterns Each of them includes a touch area including conductive lines having an average line width of less than 15 μm. 如請求項32之器件，其係觸控螢幕器件。The device of claim 32 is a touch screen device.