TW201631055A - Non-aqueous compositions of dispersed carbon-coated metal particles, articles, and uses - Google Patents

Abstract

A non-aqueous composition contains dispersed carbon-coated metal particles in an organic diluent in an amount of at least 10 weight %. The dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 [mu]m, and are dispersed using a particle dispersing agent that has a weight average molecular weight (Mw) of at least 2,000 and up to and including 100,000 and comprises nitrogen-containing units. The median diameter of the dispersed particles is determined using a dynamic light scattering method. Moreover, when the non-aqueous composition contains up to and including 25 weight % of the dispersed carbon-coated metal particles, it exhibits no visual settling when subjected to a settling test of at least 24 hours at 20 DEG C. Such non-aqueous compositions can include photocurable components and are useful to prepare photocurable and photocured electrically-conductive patterns and layers in various articles, including touch screen devices having touch screen displays.

Description

經分散之經碳塗覆的金屬顆粒的非水性組合物、物件及用途 Non-aqueous composition, article and use of dispersed carbon coated metal particles

本發明係關於含有經分散之經碳塗覆的金屬顆粒及經獨特選用之顆粒分散劑之非水性組合物。本發明亦關於含有此等經分散之經碳塗覆的金屬顆粒及顆粒分散劑之非水性可光固化組合物。可使用此等非水性可光固化組合物以提供用於經設計以提供導電材料之圖案之無電電鍍方法之晶種金屬觸媒。 This invention relates to non-aqueous compositions containing dispersed carbon coated metal particles and a uniquely selected particulate dispersant. The invention also relates to non-aqueous photocurable compositions comprising such dispersed carbon coated metal particles and particulate dispersing agents. These non-aqueous photocurable compositions can be used to provide a seed metal catalyst for an electroless plating process designed to provide a pattern of conductive material.

在用於各種通訊、財務及檔案目的之各種電子裝置(特別是顯示器裝置)上取得快速進步。就觸控螢幕面板、電致變色裝置、發光二極體、場效電晶體及液晶顯示器之此等用途而言，導電膜係必需的且在工業上極大程度地致力於改良此等導電膜之性能。 Rapid advances have been made in various electronic devices (especially display devices) for a variety of communication, financial and archival purposes. For such applications as touch screen panels, electrochromic devices, light-emitting diodes, field effect transistors, and liquid crystal displays, conductive films are essential and industrially highly committed to improving such conductive films. performance.

尤其需要提供裝納經改良之導電膜元件之觸控螢幕顯示器及裝置。目前，觸控螢幕顯示器使用氧化銦錫(ITO)塗層以建立用於區分多點接觸之電容區陣列。ITO塗層具有許多缺點。銦為昂貴稀土金屬及在全世界極少資源中可供量受到限制。ITO導電性相對地低及需要短線長度以達成足夠的反應速率。用於大型顯示器之觸控螢幕分解成更小的片段以減小導線長度達成可接受的電阻。此等更小的片段需要額外的驅動及感測電子裝置。此外，ITO為陶瓷材料，不易彎曲或撓曲，及需要利用高處理溫度真空沉積以製造導電層。 In particular, there is a need to provide touch screen displays and devices incorporating improved conductive film elements. Currently, touch screen displays use an indium tin oxide (ITO) coating to create an array of capacitor regions for distinguishing multiple contacts. ITO coatings have a number of disadvantages. Indium is an expensive rare earth metal and is limited in availability in very few resources around the world. ITO conductivity is relatively low and short line lengths are required to achieve a sufficient reaction rate. The touch screen for large displays is broken down into smaller segments to reduce the wire length to achieve acceptable resistance. These smaller segments require additional drive and sensing electronics. In addition, ITO is a ceramic material that is not easily bent or flexed, and requires high deposition temperature vacuum deposition to produce a conductive layer.

銀係一種具有比ITO大50至100倍的電導率之理想導體。銀用於許多商業應用中及可從許多來源獲得。極度期望使用銀作為導電源來製造導電膜元件，但需要大程度發展以獲得最佳特性。 Silver is an ideal conductor with a conductivity that is 50 to 100 times greater than ITO. Silver is used in many commercial applications and is available from many sources. It is highly desirable to use silver as a conductive source to fabricate a conductive film element, but it requires a large degree of development to obtain optimum characteristics.

依捲繞式生產方法使用沉積導電圖案使得感測器具有功能性之「加法製程」在可撓且透明之基材上生產觸控螢幕感測器及其他透明導電物件係此工業中最新發展之標的。生產在觸控螢幕感測器之可見部分(觸控區)中同時具有所需電性能及適宜光學性質(透射率)之觸控螢幕感測器之能力尤其重要。為達成所需導電及光學性質，強烈要求導電格網中導電線之平均線寬度小於10μm。 The use of a roll-to-roll production method to produce a touch screen sensor and other transparent conductive articles on a flexible and transparent substrate using a conductive process that deposits the conductive pattern to make the sensor functional is the latest development in the industry. Subject. It is especially important to produce a touch screen sensor that has both desired electrical properties and suitable optical properties (transmittance) in the visible portion (touch region) of the touch screen sensor. In order to achieve the desired electrical and optical properties, it is strongly required that the average line width of the conductive lines in the conductive grid is less than 10 μm.

用於此等製程中之可撓且透明之基材應光學清透(高積合透射率)且無色並展現低濁度。使用添加製程(諸如，導電材料或晶種金屬組合物之柔版印刷)施覆導電圖案需要可撓且透明之基材具有適宜之表面能及與意欲施加的精細特徵(例如，精細線)之標度一致之粗糙度。在電子裝置工業中作出相當大的努力以獲得此等所需特徵。 The flexible and transparent substrate used in such processes should be optically clear (highly integrated transmittance) and colorless and exhibit low haze. Applying a conductive pattern using an additive process, such as flexographic printing of a conductive material or a seed metal composition, requires a flexible and transparent substrate having suitable surface energy and fine features (eg, fine lines) intended to be applied. Roughness with consistent scale. Considerable efforts have been made in the electronics industry to achieve these desirable features.

WO 2013/063188(Petcavich等人)描述一種藉由使用用至少第一主板及第一油墨(「可印刷組合物」)之柔版印刷製程印刷介電基材第一側上之第一圖案；及固化經印刷之介電物件生產包含介電基材之互電容型觸控感測器之方法。可類似地施覆第二油墨且固化以在基材之第二表面上形成第二圖案。兩圖案可含有可接著無電電鍍導電材料之晶種金屬觸媒。描述所得介電物件具有1μm至1mm之厚度及20達因/cm至90達因/cm之較佳表面能。用於此等方法中之油墨一般為非水性且含有各種可光固化組分及經分散之金屬顆粒。 WO 2013/063188 (Petcavich et al.) describes a first pattern printed on a first side of a dielectric substrate by using a flexographic printing process using at least a first motherboard and a first ink ("printable composition"); And a method of producing a mutual capacitance type touch sensor comprising a dielectric substrate by curing the printed dielectric article. The second ink can be similarly applied and cured to form a second pattern on the second surface of the substrate. The two patterns may contain a seed metal catalyst that can then be electrolessly plated with a conductive material. The resulting dielectric article is described as having a thickness of from 1 μm to 1 mm and a preferred surface energy of from 20 dynes/cm to 90 dynes/cm. The inks used in such processes are generally non-aqueous and contain various photocurable components and dispersed metal particles.

已知使用各種材料以使金屬顆粒分散於水性或非水性組合物中。例如，美國專利8,506,849(Li等人)描述包含金屬奈米顆粒及不同聚合物分散劑之可固化導電油墨。美國專利8,597,420(Iftime等人)中描述包含經分散之磁性奈米顆粒及聚合物分散劑之磁性噴墨印刷油 墨。在其他技術中，金屬奈米顆粒之外表面經修飾併入疏水性尾來增進在有機溶劑中之可分散性以用於如例如美國專利申請公開案2008/0090082(Shim等人)中所述之噴墨印刷。 It is known to use various materials to disperse metal particles in an aqueous or non-aqueous composition. For example, U.S. Patent No. 8,506,849 (Li et al.) describes a curable conductive ink comprising metal nanoparticles and different polymeric dispersants. Magnetic inkjet printing oils comprising dispersed magnetic nanoparticles and polymeric dispersants are described in U.S. Patent No. 8,597,420 (bytime et al.). ink. In other techniques, the outer surface of the metal nanoparticle is modified to incorporate a hydrophobic tail to enhance dispersibility in an organic solvent for use in, for example, U.S. Patent Application Publication No. 2008/0090082 (Shim et al.). Inkjet printing.

需要經改良之包含用於無電電鍍之晶種金屬觸媒之可印刷組合物(亦稱為油墨)。希望施覆(例如，印刷)此等經改良之組合物呈具有光學效應所需要之著色、針對於成功製造之穩定性及無電印刷性能之導電線圖案。 There is a need for improved printable compositions (also known as inks) comprising a seed metal catalyst for electroless plating. It is desirable to apply (e.g., print) such improved compositions to a conductive pattern having the desired color for optical effects, stability for successful manufacturing, and electroless printing properties.

然而，所產生的具有導電線圖案之物件必須高度透明而當在反射線可見之照明條件下觀察其時卻不可見。針對此目的，已決定用黑化劑處理導電線(例如，由銅組成)之外表面以減小金屬絲線之反射率。 However, the resulting article having a conductive line pattern must be highly transparent and invisible when viewed under illumination conditions in which the reflected line is visible. For this purpose, it has been decided to treat the outer surface of the conductive wire (for example, composed of copper) with a blackening agent to reduce the reflectance of the metal wire.

然而，在一些裝納透明基材之兩側上提供有導電圖案之電容式觸控螢幕的顯示器裝置中，「經黑化之」導電絲線之頂表面可以模糊，但底表面可見且透過透明基材反射。 However, in some display devices in which a capacitive touch screen having a conductive pattern is provided on both sides of a transparent substrate, the top surface of the "blackened" conductive wire may be blurred, but the bottom surface is visible and transparent. Material reflection.

為維持導電圖案中之細線，需要施覆薄的晶種金屬觸媒油墨層，即，施覆僅夠引起無電電鍍。若油墨鋪設過大，則油墨將蔓延且提供更寬的線及由此降小物件之透明度。除此之外，此等更粗的線在最終物件中更可見但持續時間更短。因此，圖案中需要更細的線但此使得經無電電鍍之金屬在線中透過透明基材更可見。 In order to maintain the fine lines in the conductive pattern, it is necessary to apply a thin seed metal catalyst ink layer, that is, the coating is only sufficient to cause electroless plating. If the ink is laid too large, the ink will spread and provide a wider line and thus less transparency of the object. In addition to this, these thicker lines are more visible in the final object but have a shorter duration. Therefore, a thinner line is required in the pattern but this makes the electrolessly plated metal more visible through the transparent substrate in the line.

用於此等材料中之有用的晶種金屬觸媒包含金屬，諸如銀或銅之顆粒。為所需性質，足量的此等金屬顆粒可佔油墨或可印刷組合物之總重量10%至50%。此等量之金屬顆粒一般具反射性且可透過透明基材輕易看見，由此增大所得導電圖案之能見度。減小晶種金屬觸媒及經無電電鍍之金屬之反射性之一種嘗試係添加足量的著色劑(諸如碳黑)至可印刷組合物(油墨)使得晶種金屬觸媒不可見。然而，添加足量的此等著色劑至油墨而不非所欲地增加油墨中金屬顆粒之黏度及凝 結(聚集或聚結)係困難的。 Useful seed metal catalysts for use in such materials include metals such as silver or copper particles. To the desired nature, a sufficient amount of such metal particles can comprise from 10% to 50% by weight of the total weight of the ink or printable composition. Such equal amounts of metal particles are generally reflective and readily visible through the transparent substrate, thereby increasing the visibility of the resulting conductive pattern. One attempt to reduce the reflectivity of the seed metal catalyst and the electrolessly plated metal is to add a sufficient amount of color former (such as carbon black) to the printable composition (ink) such that the seed metal catalyst is not visible. However, adding a sufficient amount of such colorants to the ink undesirably increases the viscosity and condensation of the metal particles in the ink. Junctions (aggregation or coalescence) are difficult.

通常使用分散劑(或分散助劑)以維持顆粒材料在懸浮液中儘量長的時間以用於各種用途。然而，尚不可輕易地使用已知的具有特定顆粒之分散劑以最小化沉降及可能非所欲地增加所給組合物之黏度之顆粒間相互作用。一般而言，各種工業中需要大量研究及工程化以尋求所選顆粒材料之最佳分散劑，無論該等所選顆粒材料係金屬性、有機性或無機性。此對於設計用於無電電鍍操作之晶種金屬觸媒而言尤其真實。 Dispersing agents (or dispersing aids) are typically employed to maintain the particulate material in the suspension for as long as possible for a variety of uses. However, it has not been readily possible to use known dispersants having specific particles to minimize settling and possibly undesirably increase the interparticle interaction of the viscosity of the given composition. In general, a great deal of research and engineering is required in various industries to find the best dispersant for the selected particulate material, whether the selected particulate material is metallic, organic or inorganic. This is especially true for seed metal catalysts designed for electroless plating operations.

因此，需要提供一種具有經減小之反射性、顆粒凝結受到限制之小的均勻粒度分佈及使用(例如)柔版印刷施覆細線圖案之適宜黏度之晶種金屬觸媒可印刷組合物(油墨)。 Accordingly, it is desirable to provide a seed metal catalyst printable composition having a reduced uniformity, a small uniform particle size distribution that is limited by particle condensation, and a suitable viscosity, such as flexographic printing of a fine line pattern. ).

為解決上述問題，本發明提供一種非水性組合物，其含有基於非水性組合物總重量計至少10重量%的量之在有機稀釋劑中之經分散之經碳塗覆的金屬顆粒，該等經分散之經碳塗覆的金屬顆粒具有等於或小於0.6μm之中值直徑，及係用具有至少2,000且至多(含)100,000之重量平均分子量(M_w)並含有含氮單元之顆粒分散劑分散，該中值直徑係使用動態光散射法測得， 其中，當在該非水性組合物含有至多(含)25重量%之經分散之經碳塗覆的金屬顆粒時，其在20℃進行至少24小時的沉降測試時未呈現視覺上的沉降。 In order to solve the above problems, the present invention provides a non-aqueous composition comprising dispersed carbon-coated metal particles in an organic diluent in an amount of at least 10% by weight based on the total weight of the non-aqueous composition, the dispersed metal particles coated with carbon having a value equal to or less than 0.6μm in diameter, and having lines of at least 2,000 and up to (inclusive) of 100,000 weight average molecular weight (M _w) and containing particles of a nitrogen-containing dispersant unit Dispersion, the median diameter is measured by dynamic light scattering, wherein when the non-aqueous composition contains at most 25% by weight of dispersed carbon coated metal particles, it is at least 20 ° C No visual subsidence was observed during the 24 hour sedimentation test.

在一些實施例中，此等非水性組合物為非水性可光固化組合物，其等各包含：以基於非水性可光固化組合物總重量計至少10重量%的量存在之經分散之經碳塗覆的金屬顆粒，及該等經分散之經碳塗覆的金屬顆粒具有等於或小於0.6μm之中值直徑，且係用具有至少2,000且至多 (含)100,000之重量平均分子量(M_w)並含有含氮單元之顆粒分散劑分散，該中值直徑係使用動態光散射法測得，有機稀釋劑，可UV固化組分，及視需要之UV光引發劑，其中，當在該非水性可光固化組合物含有至多(含)25重量%之經分散之經碳塗覆的金屬顆粒時，其在20℃進行至少24小時的沉降測試時未呈現視覺上的沉降。 In some embodiments, the non-aqueous compositions are non-aqueous photocurable compositions, each of which comprises: a dispersed dispersion present in an amount of at least 10% by weight based on the total weight of the non-aqueous photocurable composition The carbon-coated metal particles, and the dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 μm, and have a weight average molecular weight of at least 2,000 and at most 100,000 (M _{w )} And dispersing a particulate dispersant containing a nitrogen-containing unit, the median diameter being measured by dynamic light scattering, an organic diluent, a UV-curable component, and optionally a UV photoinitiator, wherein, when in the non-aqueous state The photocurable composition contained at most (inclusive) 25% by weight of dispersed carbon coated metal particles which did not exhibit visual settling upon at least 24 hours of sedimentation testing at 20 °C.

本發明提供本文中所述之經獨特分散之經碳塗覆的金屬顆粒之許多優點。特定言之，此等經碳塗覆的金屬顆粒可使用獨特選擇的顆粒分散劑輕易地以更高濃度(例如，至少10重量%)分散於非水性組合物中。 The present invention provides many of the advantages of the uniquely dispersed carbon coated metal particles described herein. In particular, such carbon coated metal particles can be readily dispersed in a non-aqueous composition at a higher concentration (e.g., at least 10% by weight) using a uniquely selected particulate dispersant.

亦可在經碳塗覆的金屬顆粒併入由無電電鍍方法形成之導電線圖案中時減小該等經碳塗覆的金屬顆粒之反射性。 The reflectivity of the carbon-coated metal particles can also be reduced when the carbon-coated metal particles are incorporated into the conductive pattern formed by the electroless plating method.

使用根據本發明之顆粒分散劑可最小化將增大非水性組合物之黏度之顆粒間相互作用。透過尤其更充分地分散經碳塗覆的金屬顆粒，更高量的此等顆粒可「加載」至非水性組合物中而黏度無非所欲地增加。 The use of a particulate dispersant according to the present invention minimizes the interparticle interaction that will increase the viscosity of the non-aqueous composition. By dispersing the carbon coated metal particles more particularly, a higher amount of such particles can be "loaded" into the non-aqueous composition and the viscosity is undesirably increased.

根據本發明使用之特定分散劑亦促進分解及不易沉降之小經碳塗覆的金屬顆粒之穩定。此對於金屬顆粒諸如銀奈米顆粒而言係嚴重問題，因為根據如下所顯示之導自Stokes定律之沉降速度，沉降速率取決於金屬粒度及顆粒密度(銀金屬為10.5g/cm³)： The particular dispersant used in accordance with the present invention also promotes the stabilization of small carbon coated metal particles which decompose and which are less likely to settle. This is a serious problem for metal particles such as silver nanoparticles because the sedimentation rate depends on the metal particle size and particle density (silver metal is 10.5 g/cm ³ ) according to the settling velocity derived from Stokes' law as shown below:

其中Vs為顆粒沉降速度(m/sec)(垂直向下，若ρ_顆粒>ρ_流體；垂直向上，若ρ_顆粒<ρ_流體)，g為重力加速度(m/sec²)，ρ_顆粒為顆粒質量密度(kg/m³)，ρ_流體為流體質量密度(kg/m³)，μ為動態黏度(kg/m*s)及R為顆粒半徑(m)。因此，可看出金屬顆粒之沉降速率隨著R²而增大且因此隨粒度大大地改變。 Where Vs is the particle settling velocity (m/sec) (vertical downward, if ρ _particles > ρ _fluid ; vertical upward, if ρ _particles < ρ _fluid ), g is gravity acceleration (m/sec ² ), ρ _particles are particle mass Density (kg/m ³ ), ρ _fluid is fluid mass density (kg/m ³ ), μ is dynamic viscosity (kg/m*s) and R is particle radius (m). Therefore, it can be seen that the sedimentation rate of the metal particles increases with R ² and thus greatly changes with the particle size.

亦已觀察到本發明之非水性組合物(包括非水性可光固化組合物)展現經改良之存放期而在印刷工作之間或在印刷系統之接收小攪動之區域中無沉降。 It has also been observed that the non-aqueous compositions of the present invention (including non-aqueous photocurable compositions) exhibit improved shelf life without settling between printing operations or in areas of the printing system that receive small agitation.

當使用如下所述之適宜印刷裝置(例如，柔版印刷部件)「印刷」本發明之非水性組合物時，所得圖像展現印刷線中之經改良之顆粒分佈均勻性。此優點達成使用更少量的昂貴經碳塗覆的金屬顆粒更佳地覆蓋給定印刷區及經改良之均勻度提供期望之更不透光之暗線。對於更小的經碳塗覆的金屬顆粒之覆蓋均勻度更大，與使用更大經聚結之金屬顆粒時之情況相比，無電電鍍活性改良。 When the non-aqueous composition of the present invention is "printed" using a suitable printing device (e.g., a flexographic printing member) as described below, the resulting image exhibits improved particle distribution uniformity in the printed line. This advantage achieves the use of a smaller amount of expensive carbon coated metal particles to better cover a given printing zone and improved uniformity to provide a desired darker line that is less opaque. The coverage uniformity for the smaller carbon-coated metal particles is greater, and the electroless plating activity is improved as compared with the case where larger coalesced metal particles are used.

以下論述係關於本發明之各種實施例及當可能更期望一些實施例用於特定用途時，所揭示的實施例不應被解釋為或另視為限制本發明之如下所主張之範疇。此外，熟悉此項技術者應明瞭以下揭示內容具有相比所明確描述及任一實施例之論述中更寬廣之應用。 The following discussion of the various embodiments of the present invention and the embodiments of the present invention are not to be construed as limiting the scope of the invention as claimed. Moreover, it will be apparent to those skilled in the art that the following disclosure has a broader application than the explicit description and the discussion of any embodiment.

定義definition

如本文中定義非水性組合物及非水性可光固化組合物之各種組分時所使用，除非另作指明，否則單數形式「一」及「該」意欲包括一或多種該等組分(即，包括複數個指示物)。 As used herein, the singular forms "a" and "the" are intended to include one or more of the , including a plurality of indicators).

未明確定義於本申請案中之各術語應理解為具有為熟悉此項技 術者所習慣或通常接受之含義。若術語之解釋使得術語在其上下文中無含義或基本上無含義，則可從標準印刷字典查取術語定義。 Terms not expressly defined in this application should be understood as having familiarity with the art. The meaning that the surgeon is accustomed to or generally accepted. If the term is interpreted such that the term has no meaning or substantially no meaning in its context, the term definition can be found from the standard printed dictionary.

在本文中指定的各種範圍中使用數值範圍，除非另外明確指明，否則應理解為近似值，如同在所述範圍中之最小值及最大值二者前面加字眼「約」。如此，所述範圍上下略微的變動可用於達成與該等範圍中之值實質上相同的結果。此外，此等範圍之揭示內容意欲為包含介於最小值與最大值之間之每一個值之連續範圍。 Ranges of values used in the various ranges specified herein are to be understood as approximations, unless the context clearly indicates otherwise. As such, slight variations in the range above and below can be used to achieve substantially the same results as the values in the ranges. Moreover, the disclosure of such ranges is intended to encompass a continuation of each of the values between the minimum and the maximum.

中值粒徑[Dv(50%)]係使用動態光散射法測得。例如，可使用可從Malvern Instruments,Ltd.購買獲得之Malvern Zetasizer Nano ZS進行此方法。此設備之使用說明可與該設備一起獲得。 The median diameter [Dv (50%)] was measured using a dynamic light scattering method. For example, this method can be carried out using a Malvern Zetasizer Nano ZS available from Malvern Instruments, Ltd. Instructions for use of this device can be obtained with this device.

除非另作指明，否則術語「顆粒分散劑」、「分散劑」及「分散助劑」意指等效物。 Unless otherwise specified, the terms "particulate dispersant", "dispersant" and "dispersing aid" mean equivalents.

術語「環氧單體」、「不飽和單體」、「官能寡聚物」、「金屬顆粒」及「交聯劑」以其常見含義用於本文中且為一般技術者所熟知。 The terms "epoxy monomer", "unsaturated monomer", "functional oligomer", "metal particle" and "crosslinker" are used herein in their ordinary meaning and are well known to those of ordinary skill in the art.

如本文中所使用，所有分子量為可使用已知程序及設備測得之重量平均分子量(M_w)，假若該等值尚未為文獻中已知。例如，可使用尺寸排除層析法(SEC)測得M_w及值在本文中表示為聚(甲基丙烯酸甲酯)當量重量。 As used herein, all molecular weights are weight average molecular weights ( _Mw ) that can be measured using known procedures and equipment, provided that such values are not known in the literature. For example, _Mw and values can be determined using size exclusion chromatography (SEC) as expressed herein as poly(methyl methacrylate) equivalent weight.

如本文中所使用，術語「光固化」意指官能寡聚物及單體或甚至聚合物回應於此等材料之照射(例如，使用適宜波長之紫外(UV)、可見或紅外輻射照射)聚合形成交聯聚合物網路。可在交聯劑之存在下進行光固化。 As used herein, the term "photocuring" means the polymerization of a functional oligomer and a monomer or even a polymer in response to irradiation of such materials (eg, irradiation with ultraviolet (UV), visible or infrared radiation of a suitable wavelength). A crosslinked polymer network is formed. Photocuring can be carried out in the presence of a crosslinking agent.

使用術語「可光固化」來定義將在用適宜輻射照射(例如，在適宜環境中用輻射諸如紫外(UV)、可見或紅外輻射照射)時聚合或交聯之材料(或組分)。 The term "photocurable" is used to define a material (or component) that will be polymerized or crosslinked when irradiated with a suitable radiation (eg, when irradiated with radiation, such as ultraviolet (UV), visible or infrared radiation, in a suitable environment).

術語「可光固化組分」係指可參與可光固化反應之有機化學化 合物(聚合或非聚合)。此等化合物可為在照射時提供光固化之單一反應物，或其等可與其他共反應物(諸如光引發劑或酸觸媒)組合以在照射時提供光固化。 The term "photocurable component" refers to organic chemical reaction that can participate in photocurable reactions. Compound (polymerized or non-polymerized). Such compounds may be a single reactant that provides photocuring upon irradiation, or the like, in combination with other co-reactants, such as photoinitiators or acid catalysts, to provide photocuring upon irradiation.

除非另外指明，否則術語「非水性可光固化組合物」係指本發明之包括一或多種引發或促進光固化之組分之實施例，該等非水性可光固化組合物可用於實施下文中所述之各種方法及可用於提供下文中所述之物件。此等非水性可光固化組合物主要具有有機溶劑或液態有機組分且具有基於總非水性可光固化組合物重量計少於5重量%或甚至少於1重量%之水。 Unless otherwise indicated, the term "non-aqueous photocurable composition" refers to embodiments of the present invention that include one or more components that initiate or promote photocuring, which may be used in the practice of The various methods described can be used to provide the items described below. These non-aqueous photocurable compositions primarily have an organic solvent or liquid organic component and have less than 5% by weight or even at least 1% by weight water based on the weight of the total non-aqueous photocurable composition.

本文中使用術語「聚合」以意指例如藉由共價鍵結使許多更小分子諸如單體組合形成為大分子或聚合物之極大的分子。該等單體可經組合以僅形成線性大分子或其等可經組合以形成通常稱為交聯聚合物之三維大分子。可在實施本發明中進行之一種類型之聚合為酸催化(陽離子)聚合。另一類型之聚合為存在可自由基聚合材料及適宜的自由基生成光引發劑情況下之自由基聚合。在本發明之一些有用的實施例中，可同時採用酸催化聚合及自由基聚合兩種聚合。 The term "polymerization" is used herein to mean, for example, by covalent bonding, many smaller molecules, such as monomer combinations, are formed into macromolecules or macromolecules of polymers. The monomers can be combined to form only linear macromolecules or the like, which can be combined to form a three-dimensional macromolecule, commonly referred to as a crosslinked polymer. One type of polymerization that can be carried out in the practice of the invention is acid catalyzed (cationic) polymerization. Another type of polymerization is free radical polymerization in the presence of a free radically polymerizable material and a suitable free radical generating photoinitiator. In some useful embodiments of the invention, both acid catalyzed and free radical polymerizations can be employed simultaneously.

可藉由至少2個例如使用電子顯微法針對乾層獲得的個別測量值之平均確定本文中所述之層之平均乾厚。 The average dry thickness of the layers described herein can be determined by averaging at least 2 individual measurements obtained for the dry layer, for example using electron microscopy.

類似地，本文中所述之線、網格線或其他圖案特徵之平均乾厚或乾寬可為至少2個例如使用電子顯微法獲得的個別測量值之平均。 Similarly, the average dry or dry width of the lines, gridlines, or other pattern features described herein can be an average of at least 2 individual measurements, such as obtained using electron microscopy.

使用「光化輻射」以指能夠產生根據本發明之光固化或光聚合作用及具有至少200nm且至多(含)1400nm，且通常至少200nm且至多(含)750nm，或甚至至少300nm且至多(含)700nm之波長之任何電磁輻射。術語「曝光輻射」亦指此類光化輻射。 By using "actinic radiation" to mean photocurable or photopolymerizable according to the invention and having at least 200 nm and at most 1400 nm, and usually at least 200 nm and at most 750 nm, or even at least 300 nm and at most (including Any electromagnetic radiation of a wavelength of 700 nm. The term "exposure radiation" also refers to such actinic radiation.

本文中使用術語「UV輻射」以指具有至少200nm且至多(含)400nm之波長(λ_max)之電磁輻射。 The term "UV radiation" is used herein to mean electromagnetic radiation having a wavelength (λ _max ) of at least 200 nm and at most 400 nm.

用途use

即使當在非水性可光固化組合物含有大量的本文中所述之經碳塗覆的金屬顆粒時，在實施本發明中亦可能發生光固化，且該等非水性可光固化組合物可用於多種技術，諸如圖形藝術成像(例如，在彩色打樣系統中，作為可光固化油墨用於油墨噴塗、或其他成像製程)、電子保形塗層、經塗覆之磨料、磁性介質及可光固化組合物以及本文中所述之無電電鍍製程中。 Even when the non-aqueous photocurable composition contains a large amount of the carbon-coated metal particles described herein, photocuring may occur in the practice of the present invention, and the non-aqueous photocurable compositions may be used for A variety of technologies, such as graphic art imaging (for example, in color proofing systems, as photocurable inks for ink spraying, or other imaging processes), electronic conformal coatings, coated abrasives, magnetic media, and photocurable The composition and the electroless plating process described herein.

另外，本發明之含有經碳塗覆的金屬顆粒之分散液之非水性組合物可有利地用於生產電子材料、磁性材料、磁性記錄材料、光學材料、氣體感測材料、催化材料、燒結材料、光反射膜、光吸收膜或塗層、功能性組件中之中間層及其他的熟悉技術者參考此教示當可輕易明瞭之材料。 Further, the non-aqueous composition of the present invention containing a dispersion of carbon-coated metal particles can be advantageously used for producing electronic materials, magnetic materials, magnetic recording materials, optical materials, gas sensing materials, catalytic materials, sintered materials. Light reflective films, light absorbing films or coatings, intermediate layers in functional components, and others familiar with this teaching are referred to as readily identifiable materials.

因此，在經碳塗覆的金屬顆粒之分散液需要用於任何特定目的之任何情況中，本發明之非水性組合物具有各種用途。 Therefore, the non-aqueous composition of the present invention has various uses in any case where the dispersion of the carbon-coated metal particles is required for any particular purpose.

本發明之非水性組合物尤其適用為各含有至少一種可光固化組分之非水性可光固化組合物。此等非水性可光固化組合物可光固化呈任何有用的形式，例如，呈在各種基材上之塗層、纖維、在各種基材上之圖案、可光固化形式及模製物件、及磨料。 The non-aqueous compositions of the present invention are especially useful as non-aqueous photocurable compositions each containing at least one photocurable component. These non-aqueous photocurable compositions are photocurable in any useful form, for example, as coatings on various substrates, fibers, patterns on various substrates, photocurable forms, and molded articles, and Abrasive.

更特定言之，該等非水性可光固化組合物可用於各種物件或裝置中需要有效光固化之多種目的。例如，此等非水性可光固化組合物可設計以對所選輻射波長敏感且可使用(例如)以提供晶種金屬觸媒之接著可進一步例如使用無電電鍍程序處理以形成導電金屬圖案之圖案。此等導電金屬圖案可設計並併入各種裝置中，包括(但不限於)觸控螢幕或其他的可用於許多消費、工業及商業產品中之顯示器裝置。 More specifically, such non-aqueous photocurable compositions are useful for a variety of purposes in applications or devices that require effective photocuring. For example, such non-aqueous photocurable compositions can be designed to be sensitive to selected radiation wavelengths and can be used, for example, to provide a seed metal catalyst, which can then be further processed, for example, using an electroless plating process to form a pattern of conductive metal patterns. . Such conductive metal patterns can be designed and incorporated into a variety of devices including, but not limited to, touch screens or other display devices that can be used in many consumer, industrial, and commercial products.

觸控螢幕技術可包括不同觸控感測組態，包含電容型及電阻型觸控感測器。電阻型觸控感測器包括數個彼此相對之層，相鄰層間有 一可藉由加工期間形成的隔板保持之間隙。電阻型觸控螢幕面板可包含數個層，包括兩個由可藉由隔板建立之間隙隔開的薄、金屬、導電層。當物體諸如觸控筆、手掌或指尖下壓面板外表面上的某一點時，此兩金屬層接觸及形成連接而引起電流變化。此觸控事件被發送至控制器以用於進一步處理。 Touch screen technology can include different touch sensing configurations, including capacitive and resistive touch sensors. The resistive touch sensor includes a plurality of layers facing each other with adjacent layers A gap that can be maintained by a spacer formed during processing. The resistive touch screen panel can comprise several layers, including two thin, metallic, conductive layers separated by gaps that can be created by the spacers. When an object such as a stylus, palm or fingertip presses a point on the outer surface of the panel, the two metal layers contact and form a connection causing a change in current. This touch event is sent to the controller for further processing.

電容型觸控感測器可用於具有對觸控敏感之特徵之電子裝置中。此等電子裝置可包括(但不限於)電視機、監視器、自動傳送機器及可調適以呈現影像包括文字、圖形、視訊影像、電影、靜止影像及演示之投影機。可用於此等顯示器裝置之影像裝置可包含陰極射線管(CRS)、投影機、平板液晶顯示器(LCD)、LED系統、OLED系統、電漿系統、電致發光顯示器(ECD)及場發射顯示器(FED)。例如，本發明可用於製造可併入具有對觸控敏感之特徵之電子裝置中之電容型觸控感測器以提供計算裝置、電腦顯示器、可攜式媒體播放器(包含電子閱讀器)、行動電話及其他可攜式通訊裝置。 Capacitive touch sensors can be used in electronic devices that are sensitive to touch. Such electronic devices may include, but are not limited to, televisions, monitors, automatic transfer machines, and projectors that are adapted to present images including text, graphics, video images, movies, still images, and presentations. Imaging devices that can be used with such display devices can include cathode ray tubes (CRS), projectors, flat panel liquid crystal displays (LCDs), LED systems, OLED systems, plasma systems, electroluminescent displays (ECD), and field emission displays ( FED). For example, the present invention can be used to manufacture a capacitive touch sensor that can be incorporated into an electronic device having touch-sensitive features to provide a computing device, a computer display, a portable media player (including an e-reader), Mobile phones and other portable communication devices.

在可單程建立微導電特徵之高體積捲繞式製造製程中製造可撓且視需要柔性之觸控感測器之系統及方法可使用本發明。該等非水性可光固化組合物可與多個印刷部件(諸如多個柔版印刷板)一起用於此等系統及方法中以自提供於其等多個印刷部件中之圖案之預定設計形成多個高解析度導電影像。多個圖案可印刷在如下文更詳細描述之透明基材之一或兩側上。例如，一個預定圖案可形成於透明基材之一側上及一不同預定圖案可形成於透明基材之相對側上。所印刷的非水性可光固化組合物之圖案可接著「印刷」呈透明基材一或兩側上之圖案，該等所印刷的圖案可例如使用無電金屬電鍍進一步處理以提供導電金屬圖案。 Systems and methods for making flexible and optionally flexible touch sensors in a high volume roll-to-roll manufacturing process that can establish micro-conducting features in a single pass can be used with the present invention. The non-aqueous photocurable compositions can be used in conjunction with a plurality of printing components, such as a plurality of flexographic printing plates, in such systems and methods to form a predetermined design from a pattern provided in a plurality of printing components thereof. Multiple high-resolution conductive images. The plurality of patterns can be printed on one or both sides of the transparent substrate as described in more detail below. For example, a predetermined pattern may be formed on one side of the transparent substrate and a different predetermined pattern may be formed on the opposite side of the transparent substrate. The pattern of the printed non-aqueous photocurable composition can then be "printed" into a pattern on one or both sides of the transparent substrate, which can be further processed, for example, using electroless metal plating to provide a conductive metal pattern.

非水性組合物Non-aqueous composition

在本發明非水性組合物之最簡形式中，該等非水性組合物基本 上由以下組成：(a)如下文所述之相同或不同組成之經分散之經碳塗覆的金屬顆粒；(b)一或多種如下文所述之顆粒分散劑；及(c)如下文所述之有機稀釋劑(液態有機材料)，諸如有機溶劑介質，其中分散該等經碳塗覆的金屬顆粒(及可能選用之其他組分)。 In the simplest form of the non-aqueous composition of the present invention, the non-aqueous compositions are basically Composition consisting of: (a) dispersed carbon coated metal particles of the same or different composition as described below; (b) one or more particulate dispersing agents as described below; and (c) The organic diluent (liquid organic material), such as an organic solvent medium, in which the carbon coated metal particles (and possibly other components) are dispersed.

(a)經碳塗覆的金屬顆粒(a) Carbon coated metal particles

通常，各非水性組合物中僅使用一種類型(組成)之經碳塗覆的金屬顆粒，但其亦可包含不彼此干擾之來自相同或不同類別之金屬之不同類型經碳塗覆的金屬顆粒之混合物。一般而言，各經碳塗覆的金屬顆粒具有淨中性電荷。一般而言，該等經碳塗覆的顆粒為非磁性，意指其不顯示明顯磁性，及因此，本發明之非水性組合物亦一般為非磁性。 Typically, only one type (composition) of carbon coated metal particles is used in each non-aqueous composition, but it may also comprise different types of carbon coated metal particles from the same or different classes of metals that do not interfere with each other. a mixture. In general, each carbon coated metal particle has a net neutral charge. In general, the carbon coated particles are non-magnetic, meaning that they do not exhibit significant magnetic properties, and therefore, the non-aqueous compositions of the present invention are also generally non-magnetic.

可用的經碳塗覆的金屬顆粒可包括至少部分地塗覆碳之金屬顆粒。該等金屬顆粒係由一或多種選自貴金屬、半貴金屬、第IV族金屬中之一或多種類別或其組合之金屬(即，純金屬或金屬合金)組成。可用的貴金屬包括(但不限於)金、銀、鈀、鉑、銠、銥、錸、汞、釕及鋨。可用的半貴金屬包括(但不限於)鐵、鈷、鎳、銅、碳、鋁、鋅及鎢。可用的第IV族金屬包括(但不限於)錫、鈦及鍺。貴金屬諸如銀、鈀及鉑尤其有用，及鎳及銅之半貴金屬亦尤其有用。錫尤其可用於第IV族金屬類別中。在許多實施例中，於非水性可光固化組合物中使用純銀或銅。因此，在實施本發明中，術語「金屬」意指與「金屬性」相同，但除術語「金屬」及「金屬性」不欲包括金屬鹽、金屬氧化物及金屬氫化物以外。 Useful carbon coated metal particles can include metal particles that are at least partially coated with carbon. The metal particles are comprised of one or more metals (ie, pure metals or metal alloys) selected from one or more of the noble metal, semi-precious metal, and Group IV metals, or a combination thereof. Useful precious metals include, but are not limited to, gold, silver, palladium, platinum, rhodium, ruthenium, osmium, mercury, ruthenium and osmium. Useful semi-precious metals include, but are not limited to, iron, cobalt, nickel, copper, carbon, aluminum, zinc, and tungsten. Useful Group IV metals include, but are not limited to, tin, titanium, and antimony. Precious metals such as silver, palladium and platinum are especially useful, and semi-precious metals of nickel and copper are also particularly useful. Tin is especially useful in the Group IV metal category. In many embodiments, pure silver or copper is used in the non-aqueous photocurable composition. Therefore, in the practice of the invention, the term "metal" means the same as "metallic", except that the terms "metal" and "metal" are not intended to include metal salts, metal oxides and metal hydrides.

由所述金屬組成之金屬顆粒一般至少部分地表面塗覆碳。該碳可為非晶形、sp2混成或類石墨烯性質。 The metal particles composed of the metal are generally at least partially surface coated with carbon. The carbon can be amorphous, sp2 mixed or graphene-like in nature.

因此，用於非水性組合物中之尤其有用的材料為經碳塗覆的銀顆粒、經碳塗覆的銅顆粒或(在一些實施例中)經碳塗覆的銀顆粒及經 碳塗覆的銅顆粒之混合物，其等均使用一或多種如下文所述之顆粒分散劑被分散在有機溶劑介質中。 Thus, particularly useful materials for use in non-aqueous compositions are carbon coated silver particles, carbon coated copper particles or, in some embodiments, carbon coated silver particles and A mixture of carbon coated copper particles, which are all dispersed in an organic solvent medium using one or more particulate dispersing agents as described below.

該等經碳塗覆的金屬顆粒係設計成當在懸浮液中藉由動態光散射技術測得情況下具有等於或小於0.6μm、或小於0.2μm、或更有可能小於0.1μm之中值粒徑。此等經碳塗覆的金屬顆粒一般具有0.005μm之最小中值直徑。 The carbon-coated metal particles are designed to have a median particle size equal to or less than 0.6 μm, or less than 0.2 μm, or more likely less than 0.1 μm, as measured by dynamic light scattering techniques in suspension. path. These carbon coated metal particles typically have a minimum median diameter of 0.005 μm.

此等經碳塗覆的金屬顆粒可呈任何幾何形狀存在，包括(但不限於)球體、桿、柱體、立方體、圓錐體、稜錐體、絲線、薄片、小板及其組合，且其形狀及大小可為均勻或非均勻。可使用呈個別顆粒或少許顆粒之聚結物之經碳塗覆的金屬顆粒來達成本發明之最佳優點。 The carbon coated metal particles may be present in any geometric shape including, but not limited to, spheres, rods, cylinders, cubes, cones, pyramids, wires, sheets, platelets, and combinations thereof, and The shape and size can be uniform or non-uniform. The carbon coated metal particles in the form of individual particles or agglomerates of a few particles can be used to achieve the best advantages of the present invention.

非水性組合物中該一或多種顆粒分散劑各用於分散經碳塗覆的金屬顆粒以防止其在亦含有機稀釋劑之非水性組合物(如下文中所述)中凝聚或聚結。謹慎地選擇此等顆粒分散劑以便本發明可提供所需優點。首先，各顆粒分散劑具有至少2,000且至多(含)100,000或更特定言之至多(含)50,000之重量平均分子量(M_w)。最可用的顆粒分散劑各具有至少3,000且至多(含)30,000之M_w。 The one or more particulate dispersants in the non-aqueous composition are each used to disperse the carbon coated metal particles to prevent them from agglomerating or coalescing in a non-aqueous composition (as described below) that also contains an organic diluent. These particulate dispersants are carefully selected so that the present invention provides the desired advantages. First, each particle dispersant has a weight average molecular weight ( _Mw ) of at least 2,000 and up to (inclusive) 100,000 or, in particular, up to 50,000. The most useful particulate dispersants each have an _{Mw of} at least 3,000 and up to 30,000.

除此之外，各可用的顆粒分散劑包含兩個或更多個含氮單元，例如醯胺(羧酸、磺酸、亞磺酸、磷酸、膦酸及許多可形成醯胺之其他酸)、胺(一級、二級、三級)、氧化胺、脒(醯胺亞胺)、偶氮、胺基甲酸酯(carbamate)(脲烷(urethanes))、碳二亞胺、重氮(diazo)、重氮(diazonium)、烯胺、胍(脲之亞胺)、芳族雜環(吡啶、嘧啶、噠嗪、吡嗪、吡咯、咪唑、吡唑、噁唑(ozazole)、異噁唑、噻唑、吲哚、吲嗪、喹啉、異喹啉)、肼、腙、異羥肟酸、醯亞胺、亞胺(Schiff鹼)、硝酸酯(硝酸之酯)、腈(氰化物)、亞硝酸酯(亞硝酸之酯)、硝基/亞硝基(亞硝基苯、硝基苯、硝基甲烷、N-亞硝基脲)、硝酮(亞胺N-氧化物)、肟(羥胺之亞胺)或脲(甲酸之雙醯胺，諸如N-甲基脲、N-甲基硫 脲縮二脲脲基甲酸、脲唑)單元或片段。一些尤其可用的含氮單元為醯胺、胺及亞胺單元。一般而言，各顆粒分散劑具有多個含氮單元(因為其為至少寡聚)及具有至少2,000之M_w。此等含氮單元使得顆粒分散劑強力固著至經碳塗覆的金屬顆粒。 In addition, each of the available particulate dispersants comprises two or more nitrogen-containing units, such as decylamine (carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid, and many other acids which form guanamine). , amines (primary, secondary, tertiary), amine oxides, hydrazine (amidimide), azo, carbamate (urethanes), carbodiimides, diazo ( Diazo), diazonium, enamine, hydrazine (imide), aromatic heterocycle (pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, ozazole, dysentery) Azole, thiazole, anthracene, pyridazine, quinoline, isoquinoline), hydrazine, hydrazine, hydroxamic acid, quinone imine, imine (Schiff base), nitrate (ester of nitric acid), nitrile (cyanide) ), nitrite (ester of nitrous acid), nitro/nitroso (nitrosobenzene, nitrobenzene, nitromethane, N-nitrosourea), nitrone (imine N-oxide) Or a unit or fragment of hydrazine (imine of hydroxylamine) or urea (diguanamine of formic acid, such as N-methylurea, N-methylthiourea biureturonic acid, urea). Some particularly useful nitrogen-containing units are the guanamine, amine and imine units. In general, each particle dispersant has a plurality of nitrogen containing units (because it is at least oligomeric) and has a _{Mw of} at least 2,000. These nitrogen-containing units cause the particulate dispersant to be strongly fixed to the carbon-coated metal particles.

各顆粒分散劑亦含有與有機聚合物相容且與用於非水性組合物之有機溶劑介質中之有機溶劑相容之官能基。就極性、非水性組合物而言，可用的含氮單元包括酯、丙烯酸酯或醚基或其組合。 Each particulate dispersant also contains a functional group that is compatible with the organic polymer and that is compatible with the organic solvent used in the organic solvent medium of the non-aqueous composition. For polar, non-aqueous compositions, useful nitrogen-containing units include esters, acrylates or ether groups or combinations thereof.

一些尤其有用的顆粒分散劑為包含酯單元(諸如彼等於聚酯或(甲基)丙烯酸聚合物(均聚物及共聚物)中發現者)之有機聚合物。 Some particularly useful particulate dispersants are organic polymers comprising ester units such as those found in polyester or (meth)acrylic polymers (homopolymers and copolymers).

在其他實施例中，顆粒分散劑為含有選自至少一種(一或多種)以下類別(i)至(iv)之單元之有機聚合物：(i)諸如於乙烯基吡啶中之吡啶單元；(ii)如可於聚乙烯亞胺中發現之亞胺單元(諸如-伸烷基-NH-單元)，包括乙烯亞胺及丙烯亞胺單元；(iii)醯亞胺單元[-C(=O)-NH-C(=O)-單元]；及(iv)胺單元(一級、二級及三級胺基)。 In other embodiments, the particulate dispersant is an organic polymer comprising units selected from the group consisting of at least one of (a) to (iv): (i) a pyridine unit such as in vinyl pyridine; Ii) an imine unit (such as an -alkyl-NH- unit) which is found in polyethyleneimine, including ethyleneimine and propylene imine units; (iii) quinone imine units [-C(=O) -NH-C(=O)-unit]; and (iv) amine units (primary, secondary and tertiary amine groups).

若需要則可使用來自相同或不同類別材料之此等顆粒分散劑之混合物。 Mixtures of such particulate dispersants from the same or different classes of materials may be used if desired.

可用的具有此等特徵之顆粒分散劑之一些實例為以下材料，包括一些市售產品：含有聚乙烯亞胺片段之共聚物，例如Solsperse^® 35000及Solsperse^® 39000(Lubrizol)；呈嵌段、支化、超支化及梳狀結構形式之含有酯及胺單元之共聚物，諸如Disperbyk^®-2155、Disperbyk^®-2152、Disperbyk^®-2013、BYK^®-9077(BYK/Altana)及Efka^® PX 4731及Efka^® PX 4732(BASF)；含有脂族或芳族胺單元之丙烯酸系嵌段共聚物，諸如Efka^® PX 4701(BASF)；及含有脂族或芳族胺單元之共聚物，諸如Disperbyk^®-2118(BYK/Altana)及Tetronic^® 150R(BASF)。 Some examples of these particle dispersants having the features of the following materials available, including some of commercially available products: polyethyleneimine copolymer containing fragments, e.g. Solsperse ^® 35000 and Solsperse ^® 39000 (Lubrizol); as a block, branched, , hyperbranched and forms of comb copolymer containing structural units of the esters, and amines, such as ^{Disperbyk ® -2155, Disperbyk ® -2152,} Disperbyk ® -2013, BYK ® -9077 (BYK / Altana) and Efka ^® PX 4731 and Efka ^® PX 4732 (BASF); acrylic block copolymers containing aliphatic or aromatic amine units, such as Efka ^® PX 4701 (BASF); and copolymers containing aliphatic or aromatic amine units, such as Disperbyk ^® - 2118 (BYK/Altana) and Tetronic ^® 150R (BASF).

以下必需組分包含於非水性組合物中，以使得顆粒分散劑與經分散之經碳塗覆的金屬顆粒之重量比為至少1：100或甚至至少3：100且至多(含)10：100或至多(含)30：100之量。此等重量係指各非水性組合物中所有顆粒分散劑之總重量及所有經碳塗覆的金屬顆粒之總重量。 The following essential components are included in the non-aqueous composition such that the weight ratio of the particulate dispersant to the dispersed carbon coated metal particles is at least 1:100 or even at least 3:100 and at most 10:100 Or at most (inclusive) 30:100. These weights refer to the total weight of all particulate dispersants in each non-aqueous composition and the total weight of all carbon coated metal particles.

除此之外，各非水性組合物中經碳塗覆的金屬顆粒之量為基於非水性組合物(包含有機稀釋劑)總重量計至少10重量%或至少15重量%且至多(含)60重量%或甚至至多(含)70重量%。利用此資訊，熟悉技術者可接著確定所選顆粒分散劑針對所選經碳塗覆的金屬顆粒之可用且最佳的量。 In addition, the amount of carbon-coated metal particles in each non-aqueous composition is at least 10% by weight or at least 15% by weight and at most 60% based on the total weight of the non-aqueous composition (including the organic diluent). % by weight or even up to 70% by weight. Using this information, the skilled artisan can then determine the available and optimal amount of selected particulate dispersant for the selected carbon coated metal particles.

在一些尤其有用的實施例中，非水性組合物包含以為基於非水性組合物總重量計至少15重量%且至多(含)60重量%之濃度存在之經分散之經碳塗覆的銀顆粒，且該等經分散之經碳塗覆的銀顆粒具有如上所述測得之小於0.5μm之中值直徑。 In some particularly useful embodiments, the non-aqueous composition comprises dispersed carbon coated silver particles in a concentration of at least 15% by weight and up to 60% by weight, based on the total weight of the non-aqueous composition, And the dispersed carbon coated silver particles have a median diameter of less than 0.5 [mu]m as measured as described above.

非水性組合物(包括下文所述之非水性可光固化組合物)亦一般包含非水性組合物之組分溶解或分散其中之充作非水性(有機)溶劑或溶劑組合之有機稀釋劑。 Non-aqueous compositions, including the non-aqueous photocurable compositions described hereinafter, also generally comprise an organic diluent which is a component of the non-aqueous composition dissolved or dispersed therein as a non-aqueous (organic) solvent or combination of solvents.

在本發明之一些實施例中，有機稀釋劑為含有一或多種諸如以下之惰性有機溶劑之有機溶劑介質：2-乙氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、1-甲氧基-2-丙醇(Dowanol PM)、4-庚酮、3-庚酮、2-庚酮、環戊酮、環己酮、碳酸二乙酯、乙酸2-乙氧基乙酯、丁酸N-丁酯、丙酮、二氯甲烷、異丙醇、乙二醇及乳酸甲酯。此等所列惰性有機溶劑之混合物可以任何適宜體積或重量比用於有機溶劑介質中。可由熟悉此項技術者利用本文中所提供之教示輕易 地判定其他可用的有機溶劑。所謂「惰性」意指有機溶劑不會明顯參與任何化學反應。 In some embodiments of the invention, the organic diluent is an organic solvent medium containing one or more inert organic solvents such as 2-ethoxyethanol, 2-(2-methoxyethoxy)ethanol, 2 -(2-ethoxyethoxy)ethanol, 1-methoxy-2-propanol (Dowanol PM), 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone , diethyl carbonate, 2-ethoxyethyl acetate, N-butyl butyrate, acetone, dichloromethane, isopropanol, ethylene glycol and methyl lactate. Mixtures of such listed inert organic solvents can be employed in the organic solvent medium in any suitable volume or weight ratio. It is easy for those skilled in the art to utilize the teachings provided in this article. Other available organic solvents are determined. By "inert" is meant that the organic solvent does not significantly participate in any chemical reaction.

當一或多種可光固化組分(如下文所述)呈液態有機化合物存在時，此等一或多種可光固化組分可充作有機稀釋劑及個別惰性有機溶劑可能係非必需的。在此等情況中，有機稀釋劑可視為「反應性」稀釋劑。或者，一或多種反應性稀釋劑可與一或多種惰性有機溶劑(如上文所述)組合使用以形成適宜之有機稀釋劑。 When one or more photocurable components (as described below) are present as a liquid organic compound, such one or more photocurable components may be employed as organic diluents and individual inert organic solvents may not be necessary. In such cases, the organic diluent can be considered a "reactive" diluent. Alternatively, one or more reactive diluents can be used in combination with one or more inert organic solvents (as described above) to form a suitable organic diluent.

可審慎地根據所使用的特定材料、用於施覆所得非水性組合物之裝置及所需性質(包括組合物均勻度)來選擇有機稀釋劑的量。 The amount of organic diluent can be selected with care according to the particular materials employed, the means for applying the resulting non-aqueous composition, and the desired properties, including composition uniformity.

例如，有機稀釋劑可提供基於非水性組合物總重量計至少10重量%且至多(含)90重量%或至少20重量%且至多(含)80重量%。有機稀釋劑通常包含很少水或沒有水，意指水以基於非水性組合物總重量計小於5重量%或甚至小於1重量%之量存在。 For example, the organic diluent can provide at least 10% by weight and up to 90% by weight or at least 20% by weight and up to 80% by weight, based on the total weight of the non-aqueous composition. The organic diluent typically contains little or no water, meaning that water is present in an amount of less than 5% by weight or even less than 1% by weight, based on the total weight of the non-aqueous composition.

雖然不是非水性組合物之必要條件，但視需要且期望之組分為基於非水性組合物總重量計至少0.5重量%且至多(含)20重量%或通常至少1重量%且至多(含)10重量%含量之碳黑。 Although not a necessary condition for the non-aqueous composition, the components as needed and desired are at least 0.5% by weight and at most 20% by weight or usually at least 1% by weight and at most (including) based on the total weight of the non-aqueous composition. 10% by weight of carbon black.

如上所述，本發明之非水性組合物可為進一步含有一或多種如-下文所述之可光固化組分之非水性可光固化組合物。亦可利用下文中提供之教示判定此等組分之量，但一般而言，僅儘量多的一或多種可光固化組分可在特定用途中提供足夠的光固化。 As stated above, the non-aqueous composition of the present invention may be a non-aqueous photocurable composition further comprising one or more photocurable components as described below. The amounts of such components can also be determined using the teachings provided below, but in general, only as many of the one or more photocurable components as possible provide sufficient photocuring in a particular application.

本發明之一些尤其可用的非水性可光固化組合物包含：至少10重量%或甚至至少15重量%且至多(含)60重量%或至多(含)70重量%含量之經分散之經碳塗覆的金屬顆粒，所有含量均係基於非水性可光固化組合物總重量計，及該等經分散之經碳塗覆的金屬顆粒具有等於或小於0.6μm之中值直徑，且藉由至少2,000且至多(含)100,000之M_w並含有含氮單元之顆粒分散劑分散，該中值直徑係 使用動態光散射法判定，均如上文所述，有機稀釋劑(如上文所述)，可UV固化組分(如下文所述)，及視需要之UV光引發劑(如下文所述)，其中，當在非水性可光固化組合物含有至多(含)25重量%之經分散之經碳塗覆的金屬顆粒時，其在20℃進行至少24小時的沉降測試時未呈現視覺上的沉降(該測試進一步於上文定義)。 Some particularly useful non-aqueous photocurable compositions of the present invention comprise: at least 10% by weight or even at least 15% by weight and up to 60% by weight or up to 70% by weight of dispersed carbon coating The coated metal particles are all based on the total weight of the non-aqueous photocurable composition, and the dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 μm, and are at least 2,000 And at most (including) 100,000 M _w and containing a particulate dispersant dispersion of nitrogen-containing units, the median diameter is determined using dynamic light scattering, both as described above, organic diluent (as described above), UV a curing component (as described below), and optionally a UV photoinitiator (as described below), wherein when the non-aqueous photocurable composition contains up to 25% by weight of dispersed carbon When the coated metal particles were subjected to a sedimentation test for at least 24 hours at 20 ° C, no visual sedimentation was exhibited (this test is further defined above).

在此等非水性可光固化組合物中，經分散之經碳塗覆的金屬顆粒可包括經分散之經碳塗覆的銀顆粒或經分散之經碳塗覆的銅顆粒或經分散之經碳塗覆的銀顆粒及經分散之經碳塗覆的銅顆粒二者之混合物，其等均述於下文中。 In such non-aqueous photocurable compositions, the dispersed carbon coated metal particles may comprise dispersed carbon coated silver particles or dispersed carbon coated copper particles or dispersed Mixtures of both carbon coated silver particles and dispersed carbon coated copper particles are described below.

除此之外，此等非水性可光固化組合物中顆粒分散劑與經分散之經碳塗覆的金屬顆粒之重量比可為至少1：100且至多(含)30：100。 Additionally, the weight ratio of particulate dispersant to dispersed carbon coated metal particles in such non-aqueous, photocurable compositions can be at least 1:100 and up to 30:100.

在一些尤其可用的非水性可光固化組合物中，經分散之經碳塗覆的金屬顆粒可以基於非水性可光固化組合物總重量計至少15重量%且至多(含)60重量%之量存在，及該等經分散之經碳塗覆的金屬顆粒(諸如經碳塗覆的銀顆粒或經碳塗覆的銅顆粒)具有如使用如上文所述之動態光散射法測得之小於0.5μm之中值直徑。 In some particularly useful non-aqueous photocurable compositions, the dispersed carbon coated metal particles may be at least 15% by weight and up to 60% by weight based on the total weight of the non-aqueous photocurable composition. The presence, and the dispersed carbon coated metal particles, such as carbon coated silver particles or carbon coated copper particles, have a value of less than 0.5 as measured using dynamic light scattering as described above. Mm median diameter.

可藉由以一或多種該等顆粒分散劑使用適宜之分散裝置適宜地分散經碳塗覆的金屬顆粒來製備本發明之非水性組合物。此等兩種必需組分可混合或分散於可有效分散經碳塗覆的金屬顆粒之有機稀釋劑(例如有機溶劑介質)(如上文所述)中。 The non-aqueous composition of the present invention can be prepared by suitably dispersing carbon-coated metal particles with one or more of such particulate dispersing agents using a suitable dispersing device. These two essential components may be mixed or dispersed in an organic diluent (e.g., an organic solvent medium) (as described above) that is effective to disperse the carbon coated metal particles.

用於分散經碳塗覆的金屬顆粒之方法包括(但不限於)球磨研磨、介質研磨、磁性攪拌、高速均質化、高壓均質化、震動器振蕩及超音波處理。超音波處理尤其可用於用含在有機稀釋劑中之顆粒分散劑來分散經碳塗覆的金屬顆粒。 Methods for dispersing carbon coated metal particles include, but are not limited to, ball milling, media milling, magnetic agitation, high speed homogenization, high pressure homogenization, vibrator oscillation, and ultrasonic treatment. Ultrasonic treatment is especially useful for dispersing carbon coated metal particles with a particulate dispersant contained in an organic diluent.

介質研磨技術亦可用於碎磨用於本發明中之固體顆粒，諸如經碳塗覆的金屬顆粒。可用磨碎機、球磨機、介質研磨機或振動研磨機使用適宜之由二氧化矽、氮化矽、砂、氧化鋯、氧化鋁、氧化鈦、氧化釔、經氧化釔穩定之氧化鋯、矽酸鋯、玻璃、鋼鐵或任何其他的已知用於此等用途之材料組成之介質來達成介質研磨。 Media milling techniques can also be used to pulverize solid particles used in the present invention, such as carbon coated metal particles. A suitable miller, tantalum nitride, sand, zirconia, alumina, titania, yttria, yttria-stabilized zirconia, tannic acid may be used by a grinder, a ball mill, a media mill or a vibrating mill. Zirconium, glass, steel or any other medium known to be used for such purposes to achieve media milling.

本發明之非水性可光固化組合物可進一步包含基於非水性可光固化組合物總量計至少0.5重量%且至多(含)20重量%或至少1重量%且至多(含)10重量%含量之經分散之碳黑。 The non-aqueous photocurable composition of the present invention may further comprise at least 0.5% by weight and at most 20% by weight or at least 1% by weight and at most 10% by weight based on the total of the non-aqueous photocurable composition. Dispersed carbon black.

經酸催化之可光固化化學：Acid catalyzed photocurable chemistry:

在本發明之一些實施例中，非水性可光固化組合物包含一或多種可UV固化組分，其中至少一種為經酸催化之可光固化組分。此等非水性可光固化組合物可進一步包含光酸產生劑。 In some embodiments of the invention, the non-aqueous photocurable composition comprises one or more UV curable components, at least one of which is an acid catalyzed photocurable component. These non-aqueous photocurable compositions may further comprise a photoacid generator.

一些可用的經酸催化之可光固化組分可為可光固化環氧材料。可用於本發明中之可陽離子光固化環氧材料(「環氧化物」)為具有至少一個環氧乙烷環之有機化合物，該環氧乙烷環顯示於下式中： Some of the useful acid catalyzed photocurable components can be photocurable epoxy materials. The cationic photocurable epoxy material ("epoxide") useful in the present invention is an organic compound having at least one oxirane ring, which is shown in the following formula:

其可藉由開環機制聚合。此等環氧材料包括單體環氧化合物及聚合類型之環氧化物且可為脂族、環脂族、芳族或雜環。此等材料一般每分子平均具有至少一個可聚合環氧基，或通常每分子具有至少約1.5個或甚至至少約2個可聚合環氧基。聚合環氧材料包括具有末端環氧基之線性聚合物(例如，聚氧伸烷基二醇之二縮水甘油醚)、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)及具有側環氧基之聚合物(例如，甲基丙烯酸縮水甘油酯聚合物或共聚物)。 It can be polymerized by an open loop mechanism. Such epoxy materials include monomeric epoxy compounds and polymeric types of epoxides and may be aliphatic, cycloaliphatic, aromatic or heterocyclic. Such materials generally have an average of at least one polymerizable epoxy group per molecule, or typically at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule. Polymeric epoxy materials include linear polymers having terminal epoxy groups (eg, diglycidyl ethers of polyoxyalkylene glycols), polymers having backbone (backbone) ethylene oxide units (eg, polybutylene) a diene polyepoxide) and a polymer having a pendant epoxy group (for example, a glycidyl methacrylate polymer or copolymer).

可光固化環氧材料可為單一化合物或其可為不同的每分子含有 一個、兩個或更多個環氧基之環氧材料之混合物。由環氧材料中之總環氧基數除以存在的含環氧分子總數來判定每分子之「平均」環氧基數。 The photocurable epoxy material can be a single compound or it can be different for each molecule A mixture of one, two or more epoxy-based epoxy materials. The "average" number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy by the total number of epoxy-containing molecules present.

環氧材料可自低分子量單體材料至高分子量聚合物變化且其可在主鏈及取代基(或側基)性質上大大地不同。例如，主鏈可為任何類型及其上的取代基可為室溫下不會實質上干擾所需陽離子光固化製程之任何基團。允許的取代基之示例包括(但不限於)鹵素、酯基、醚、磺酸酯基、矽氧烷基、硝基及磷酸酯基。環氧材料之分子量可為至少58且至多(含)100,000或甚至更高。 Epoxy materials can vary from low molecular weight monomer materials to high molecular weight polymers and can vary greatly in backbone and substituent (or pendant) properties. 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. Examples of permissible substituents include, but are not limited to, halogen, ester, ether, sulfonate, decyloxy, nitro, and phosphate groups. The molecular weight of the epoxy material can be at least 58 and up to, including 100,000 or even higher.

可用的環氧材料包括含有環己烯氧化物基團之其等環氧材料，諸如環氧環己烷羧酸酯，諸如3,4-環氧環己基甲基-3,4-環氧環己烷羧酸酯、3,4-環氧-2-甲基環己基甲基-3,4-環氧-2-甲基環己烷羧酸酯及雙(3,4-環氧-6-甲基環己基甲基)己二酸酯。可用的具此種性質之環氧材料之更詳細的清單提供於美國專利3,117,099(Proops等人)中。 Useful epoxy materials include epoxy materials such as cyclohexene oxide groups, such as epoxycyclohexane carboxylates, such as 3,4-epoxycyclohexylmethyl-3,4-epoxy rings. Hexane carboxylate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylate and bis(3,4-epoxy-6 -Methylcyclohexylmethyl) adipate. A more detailed list of useful epoxy materials of this nature is provided in U.S. Patent 3,117,099 (Proops et al.).

其他可用的環氧材料包括為藉由使多元酚與過量的氯醇諸如表氯醇[例如，2,2-雙-(2,3-環氧丙氧基苯酚)-丙烷之二縮水甘油醚]反應獲得之多元酚縮水甘油醚之縮水甘油醚單體。此類型之環氧材料之其他實例述於美國專利3,018,262(Schroeder)及「Handbook of Epoxy Resins」,Lee及Neville,McGraw-Hill Book Co.,New York(1967)中。 Other useful epoxy materials include diglycidyl ethers by reacting a polyhydric phenol with an excess of a chlorohydrin such as epichlorohydrin [eg, 2,2-bis-(2,3-epoxypropoxyphenol)-propane] The glycidyl ether monomer of the polyphenol glycidyl ether obtained by the reaction. Other examples of epoxy materials of this type are described in U.S. Patent 3,018,262 (Schroeder) and "Handbook of Epoxy Resins", Lee and Neville, McGraw-Hill Book Co., New York (1967).

其他可用的環氧材料為樹脂，諸如衍生自與縮水甘油反應之丙烯酸酯(諸如丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油酯)、與一或多種烯系不飽和可聚合單體共聚合之共聚物。 Other useful epoxy materials are resins such as those derived from the copolymerization of acrylates such as glycidyl acrylate and glycidyl methacrylate reacted with glycidol, copolymerized with one or more ethylenically unsaturated polymerizable monomers. Things.

其他可用的環氧材料為表氯醇類(諸如表氯醇)、環氧烷(諸如環氧丙烷及氧化苯乙烯)、烯基氧化物(諸如丁二烯氧化物)及縮水甘油酯(諸如甘油酸乙酯)。 Other useful epoxy materials are epichlorohydrins (such as epichlorohydrin), alkylene oxides (such as propylene oxide and styrene oxide), alkenyl oxides (such as butadiene oxide), and glycidyl esters (such as Ethyl glycerate).

其他可用的環氧材料為具有環氧官能性或環氧基(諸如環己基環 氧基)之聚矽氧，尤其係其等具有聚矽氧主鏈之環氧材料。此等環氧材料之商業實例包括購自Momentive之UV 9300、UV 9315、UV 9400、UV 9425聚矽氧材料。 Other useful epoxy materials are epoxy functional or epoxy (such as cyclohexyl rings) The polyoxyl of oxy) is especially an epoxy material having a polyfluorene backbone. Commercial examples of such epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 polyoxyl materials available from Momentive.

聚合環氧材料可視需要包含其他的室溫下不會實質上干擾非水性可光固化組合物之陽離子光固化之官能性。例如，可光聚合環氧材料亦可包含可自由基聚合官能性。 The polymeric epoxy material may optionally contain other cationic photocuring functionalities that do not substantially interfere with the non-aqueous photocurable composition at room temperature. For example, the photopolymerizable epoxy material can also comprise free radically polymerizable functionality.

可光聚合環氧材料可包括兩種或更多種不同環氧材料之摻合物或混合物。此等摻合物之實例包括可光聚合環氧材料之兩種或更多種分子量分佈，諸如一或多種低分子量(低於200)環氧材料與一或多種中間分子量(自200至10,000)可光聚合環氧材料之摻合物或一或多種該可光聚合環氧材料與具有一或多種更高分子量(高於約10,000)環氧材料之摻合物。或者或另外，可光聚合環氧材料可包括具有不同化學性質(諸如脂族及芳族性質)或不同官能性(諸如極性及非極性性質)之環氧材料之摻合物。其他的可陽離子聚合單體或聚合物可另外併入至可光聚合環氧材料中。 The photopolymerizable epoxy material can comprise a blend or mixture of two or more different epoxy materials. Examples of such blends include two or more molecular weight distributions of photopolymerizable epoxy materials, such as one or more low molecular weight (less than 200) epoxy materials and one or more intermediate molecular weights (from 200 to 10,000) A blend of photopolymerizable epoxy materials or a blend of one or more of the photopolymerizable epoxy materials with one or more higher molecular weight (greater than about 10,000) epoxy materials. Alternatively or additionally, the photopolymerizable epoxy material can include blends of epoxy materials having different chemical properties, such as aliphatic and aromatic properties, or different functionalities, such as polar and non-polar properties. Other cationically polymerizable monomers or polymers may additionally be incorporated into the photopolymerizable epoxy material.

一或多種可光固化環氧材料以適宜量包含於非水性可光固化組合物中以提供所需要的有效光固化(或光聚合)。例如，該一或多種可光聚合環氧材料可以基於非水性可光固化組合物總重量計至少5重量%且至多(含)50重量%或通常至少10重量%且至多(含)40重量%之量存在。 One or more photocurable epoxy materials are included in the non-aqueous photocurable composition in an appropriate amount to provide the desired effective photocuring (or photopolymerization). For example, the one or more photopolymerizable epoxy materials can be at least 5% by weight and up to (including) 50% by weight or typically at least 10% by weight and up to (including) 40% by weight, based on the total weight of the non-aqueous photocurable composition. The amount exists.

各種化合物可用作光酸產生劑用於產生適宜之酸以參與環氧材料之光固化。有些該等「光酸產生劑」為酸性及其他為非離子性。熟悉此項技術者參考本文中所提供之教示將輕易明瞭除了彼等下文所述者外之其他的可用光酸產生劑。適用作光酸產生劑之各種化合物可從各種商業來源購買或使用已知的合成方法及起始材料製得。 Various compounds can be used as photoacid generators to produce suitable acids to participate in photocuring of epoxy materials. Some of these "photoacid generators" are acidic and others are nonionic. Those skilled in the art will readily appreciate other available photoacid generators in addition to those described below with reference to the teachings provided herein. Various compounds suitable for use as photoacid generators can be purchased from various commercial sources or prepared using known synthetic methods and starting materials.

可用於實施本發明之鎓鹽酸產生劑包括(但不限於)重氮之鹽、 鏻、錪或鋶鹽，包括聚芳基重氮、鏻、錪或鋶鹽。錪或鋶鹽包括(但不限於)二芳基錪及三芳基鋶鹽。可用的相對陰離子包括(但不限於)錯合金屬鹵離子，諸如四氟硼酸根、六氟銻酸根、三氟甲磺酸根、六氟砷酸根、六氟磷酸根及芳烴磺酸根。鎓鹽亦可為具有多個鎓鹽部分之寡聚或聚合化合物以及具有單一鎓鹽部分之分子。 The hydrazine hydrochloride generator useful in the practice of the invention includes, but is not limited to, a salt of diazonium, Barium, strontium or barium salts, including polyaryldiazo, hydrazine, hydrazine or sulfonium salts. The phosphonium or phosphonium salts include, but are not limited to, diarylsulfonium and triarylsulfonium salts. Useful relative anions include, but are not limited to, mismatched metal halides such as tetrafluoroborate, hexafluoroantimonate, triflate, hexafluoroarsenate, hexafluorophosphate, and arene sulfonate. The onium salt may also be an oligomeric or polymeric compound having a plurality of onium salt moieties and a molecule having a single onium salt moiety.

可用的芳族錪鹽之實例包括(但不限於)四氟硼酸二苯基錪；四氟硼酸二(4-甲基苯基)錪；四氟硼酸苯基-4-甲基苯基錪；四氟硼酸二(4-庚基苯基)錪；六氟磷酸二(3-硝基苯基)錪；六氟磷酸二(4-氯苯基)錪；四氟硼酸二(萘基)錪；四氟硼酸二(4-三氟甲基苯基)錪；六氟磷酸二苯基錪；六氟磷酸二(4-甲基苯基)錪；六氟砷酸二苯基錪；四氟硼酸二(4-苯氧基苯基)錪；六氟磷酸苯基-2-噻吩基錪；六氟磷酸3,5-二甲基吡唑基-4-苯基錪；六氟銻酸二苯基錪；四氟硼酸2,2'-二苯基錪；六氟磷酸二(2,4-二氯苯基)錪；六氟磷酸二(4-溴苯基)錪；六氟磷酸二(4-甲氧基苯基)錪；六氟磷酸二(3-羧基苯基)錪；六氟磷酸二(3-甲氧基羰基苯基)錪；六氟磷酸二(3-甲氧基磺醯基苯基)錪；六氟磷酸二(4-乙醯胺基苯基)錪；六氟磷酸二(2-苯并噻吩基)錪；及六氟銻酸二苯基錪；及其混合物。可依Beringer等人，J.Am.Chem.Soc.81,342(1959)之教示複分解對應之芳族錪單鹽(諸如，例如，硫酸氫二苯基錪)製得此等化合物。 Examples of useful aromatic sulfonium salts include, but are not limited to, diphenylphosphonium tetrafluoroborate; bis(4-methylphenyl)phosphonium tetrafluoroborate; phenyl-4-methylphenylphosphonium tetrafluoroborate; Di(4-heptylphenyl)phosphonium tetrafluoroborate; bis(3-nitrophenyl)phosphonium hexafluorophosphate; bis(4-chlorophenyl)phosphonium hexafluorophosphate; di(naphthyl)phosphonium tetrafluoroborate Di(4-trifluoromethylphenyl)phosphonium tetrafluoroborate; diphenylphosphonium hexafluorophosphate; bis(4-methylphenyl)phosphonium hexafluorophosphate; diphenylphosphonium hexafluoroarsenate; tetrafluoro Di(4-phenoxyphenyl)phosphonium borate; phenyl-2-thienyl hexafluorophosphate; 3,5-dimethylpyrazolyl-4-phenylphosphonium hexafluorophosphate; hexafluoroantimonate Phenylhydrazine; 2,2'-diphenylphosphonium tetrafluoroborate; bis(2,4-dichlorophenyl)phosphonium hexafluorophosphate; bis(4-bromophenyl)phosphonium hexafluorophosphate; (4-methoxyphenyl)fluorene; bis(3-carboxyphenyl)phosphonium hexafluorophosphate; bis(3-methoxycarbonylphenyl)phosphonium hexafluorophosphate; bis(3-methoxy) hexafluorophosphate Sulfhydrylphenyl)anthracene; bis(4-acetamidophenyl)phosphonium hexafluorophosphate; bis(2-benzothienyl)phosphonium hexafluorophosphate; and diphenylphosphonium hexafluoroantimonate; mixture. Such compounds can be prepared according to the teachings of Beringer et al., J. Am. Chem. Soc. 81, 342 (1959), which are metathesis corresponding to aromatic sulfonium mono-salts such as, for example, diphenyl sulfonium hydrogen sulfate.

其他的適宜錪鹽包括述於美國專利5,545,676(Palazzotto等人)第2欄(第28行至第46行)以及美國專利3,729,313(Smith)、3,741,769(Smith)、3,808,006(Smith)、4,250,053(Smith)及4,394,403(Smith)中之化合物。 Other suitable sulfonium salts include those described in U.S. Patent 5,545,676 (Palazzotto et al.) at column 2 (lines 28 to 46) and U.S. Patents 3,729,313 (Smith), 3,741,769 (Smith), 3,808,006 (Smith), 4,250,053 (Smith). And compounds in 4,394,403 (Smith).

有用的錪鹽可為單鹽(例如，含有陰離子，諸如氯離子、溴離子、碘離子或C₄H₅SO₃ ^-)或金屬錯合鹽(例如，含有SbF₆ ^-、PF₆ ^-、BF₄ ^-、肆(全氟苯基)硼酸根或SbF₅OH₃₁AsF₆ ^-)。若需要，則可使用任何此 等相同或不同類別之錪鹽之混合物。 Useful phosphonium salts can be mono-salts (eg, containing an anion such as chloride, bromide, iodide or C ₄ H ₅ SO ₃ ^- ) or a metal-missing salt (eg, containing SbF ₆ ^- , PF ₆ ^- , BF) ₄ ^- , fluorene (perfluorophenyl) borate or SbF ₅ OH ₃₁ AsF ₆ ^- ). Mixtures of any of these same or different classes of cerium salts can be used if desired.

例示性鋶鹽包括(但不限於)四氟硼酸三苯基鋶、四氟硼酸甲基二苯基鋶、六氟磷酸二甲基苯基鋶、六氟磷酸三苯基鋶、六氟銻酸三苯基鋶、六氟砷酸二苯基萘基鋶、六氟磷酸三甲苯基鋶、六氟銻酸甲氧苯基二苯基鋶、四氟硼酸4-丁氧基苯基二苯基鋶、六氟磷酸4-氯苯基二苯基-鋶、六氟磷酸三(4-苯氧基苯基)鋶、六氟砷酸二(4-乙氧基苯基)甲基鋶、四氟硼酸4-丙酮基苯基二苯基鋶、六氟磷酸4-硫基甲氧基苯基二苯基鋶、六氟銻酸二(甲氧基磺醯基苯基)甲基鋶、六氟銻酸二(硝基苯基)苯基鋶、六氟磷酸二(甲氧甲醯基苯基)甲基鋶、四氟硼酸4-乙醯胺基苯基二苯基鋶、六氟磷酸二甲基萘基鋶、四氟硼酸三氟甲基二苯基鋶、六氟銻酸對-(苯基噻吩基)二苯基鋶、六氟磷酸對-(苯基噻吩基)二苯基鋶、六氟銻酸二-[對-(苯基噻吩基)]苯基鋶、六氟磷酸二-[對-(苯基噻吩基)]苯基鋶、4,4'-雙(二苯基鋶)二苯硫醚雙(六氟銻酸根)、4,4'-雙(二苯基鋶)二苯基硫醚雙(六氟磷酸根)、六氟磷酸10-甲基吩噁鋶、六氟磷酸5-甲基噻蒽、六氟磷酸10-苯基-9,9-二甲基9-氧硫 、四氟硼酸10-苯基-9-側氧基9-氧硫、四氟硼酸5-甲基-10-側氧基噻蒽、六氟磷酸5-甲基-10,10-二側氧基噻蒽及其混合物。 Exemplary onium salts include, but are not limited to, triphenylsulfonium tetrafluoroborate, methyldiphenylphosphonium tetrafluoroborate, dimethylphenylphosphonium hexafluorophosphate, triphenylsulfonium hexafluorophosphate, hexafluoroantimonic acid Triphenylsulfonium, diphenylnaphthylphosphonium hexafluoroarsenate, trimethylphenylphosphonium hexafluorophosphate, methoxyphenyldiphenylphosphonium hexafluoroantimonate, 4-butoxyphenyldiphenyltetrafluoroborate Bismuth, 4-chlorophenyldiphenyl-fluorene hexafluorophosphate, tris(4-phenoxyphenyl)phosphonium hexafluorophosphate, bis(4-ethoxyphenyl)methylhydrazine hexafluoroarsenate, four 4-acetonylphenyldiphenylphosphonium fluoroborate, 4-thiomethoxyphenyldiphenylphosphonium hexafluorophosphate, bis(methoxysulfonylphenyl)methylhydrazine hexafluoroantimonate, six Di(nitrophenyl)phenylphosphonium fluoroantimonate, bis(methoxymethylphenylphenyl)methylphosphonium hexafluorophosphate, 4-ethylguanidinophenyldiphenylphosphonium tetrafluoroborate, hexafluorophosphoric acid Dimethylnaphthyl fluorene, trifluoromethyldiphenyl sulfonium tetrafluoroborate, p-(phenylthienyl)diphenyl sulfonium hexafluoroantimonate, p-(phenylthienyl)diphenyl hexafluorophosphate Bismuth, hexafluoroantimonate di-[p-(phenylthienyl)]phenylhydrazine, hexafluorophosphate di-[p-(phenylthienyl)]benzene Bismuth, 4,4'-bis(diphenylfluorene)diphenyl sulfide bis(hexafluoroantimonate), 4,4'-bis(diphenylfluorene)diphenyl sulfide bis(hexafluorophosphate) , 10-methylphenoxyphosphonium hexafluorophosphate, 5-methylthiazolidine hexafluorophosphate, 10-phenyl-9,9-dimethyl 9-oxosulfide hexafluorophosphate , tetrafluoroboric acid 10-phenyl-9-sideoxy 9-oxosulfuric acid , 5-fluoro-10-oxoxythiazide tetrafluoroborate, 5-methyl-10,10-di-oxythiophene hexafluorophosphate, and mixtures thereof.

鋶鹽對於使用而言係期望的及應可溶於任何惰性有機溶劑(述於下文)中且其亦應係貯存穩定，意指其當在與其他組分(特別是電子受體光敏劑及電子供體共起始劑)混合時在暴露於適宜輻射之前不會自發地促進聚合。因此，特定鎓鹽之選擇可出於就其他組分及量而言最佳性質進行。 The phosphonium salt is desirable for use and should be soluble in any inert organic solvent (described below) and it should also be storage stable, meaning that it is when combined with other components (especially electron acceptor photosensitizers and The electron donor co-initiator) does not spontaneously promote polymerization prior to exposure to suitable radiation. Thus, the choice of a particular onium salt can be made for optimum properties with respect to other components and amounts.

尤其可用的鋶鹽包括(但不限於)三芳基取代之鹽，諸如經混合之六氟銻酸三芳基鋶(例如，以UVI-6974從Dow Chemical Company購得)、經混合之六氟磷酸三芳基鋶(例如，以UVI-6990從Dow Chemical Company購得)及六氟磷酸芳基鋶(例如，以SarCa^TM KI85從Sartomer Company購得)。 Particularly useful onium salts include, but are not limited to, triaryl substituted salts, such as mixed triarylsulfonium hexafluoroantimonate (e.g., commercially available from Dow Chemical Company as UVI-6974), mixed hexafluorophosphate triaryl sulfonium group (e.g., in UVI-6990 commercially available from Dow Chemical Company) and aryl sulfonium hexafluorophosphate (e.g., in SarCa ^TM KI85 available from Sartomer Company).

一或多種鎓鹽(諸如錪鹽或鋶鹽)可一般以基於非水性可光固化組合物總重量計至少0.05重量%且至多(含)10重量%或通常至少0.1重量%且至多(含)10重量%或甚至至少0.5重量%且至多(含)5重量%之量存於非水性可光固化組合物中。 The one or more onium salts (such as a phosphonium or phosphonium salt) may generally be at least 0.05% by weight and at most 10% by weight or usually at least 0.1% by weight and at most (inclusive) based on the total weight of the non-aqueous photocurable composition. 10% by weight or even at least 0.5% by weight and up to 5% by weight of the non-aqueous photocurable composition.

非離子光酸產生劑亦可用於本發明中，該等化合物包括(但不限於)重氮甲烷衍生物，諸如(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。 Nonionic photoacid generators may also be used in the present invention, including but not limited to, diazomethane derivatives such as, for example, bis(phenylsulfonyl)diazomethane, bis(p-toluenesulfonate) Diazomethane, bis(xylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)-diazomethane, bis(cyclopentylsulfonyl)diazomethane, bis(n-butylsulfonate) Dimethylmethane, bis(isobutylsulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane, bis(n-propylsulfonyl)diazomethane, double (iso) Propylsulfonyl)diazomethane, bis(t-butylsulfonyl)diazomethane, bis(n-pentylsulfonyl)diazomethane, bis(isopentylsulfonyl)diazomethane, Bis(2nd pentylsulfonyl)diazomethane, bis(third amylsulfonyl)diazomethane, 1-cyclohexylsulfonyl-1-(tert-butylsulfonyl)diazomethane , 1-cyclohexylsulfonyl-1-(third amylsulfonyl)diazomethane and 1-tripentylsulfonyl-1-(tert-butylsulfonyl)diazomethane.

非離子光酸產生劑亦可包括乙二肟衍生物，諸如(例如)雙-o-(對-甲苯磺醯基)-α-二甲基乙二肟、雙-o-(對-甲苯磺醯基)-α-二苯基乙二肟、雙-o-(對-甲苯磺醯基)-α-二環己基乙二肟、雙-o-(對-甲苯磺醯基)-2,3-戊二酮乙二肟、雙-o-(對-甲苯磺醯基)-2-甲基-3,4-戊二酮乙二肟、雙-o-(正丁烷磺醯基)-α-二甲基乙二肟、雙-o-(正丁烷磺醯基)-α-二苯基乙二肟、雙-o-(正丁烷磺醯基)-α-二環己基乙二肟、雙-o-(正丁烷磺醯基)-2,3-戊二酮乙二肟、雙-o-(正丁烷磺醯基)-2-甲基-3,4-戊二酮乙二肟、雙-o-(甲烷磺醯基)-α-二甲基乙二肟、雙-o-(三氟甲烷磺醯基)-α-二甲基乙二肟、雙-o-(1,1,1-三氟乙烷磺醯基)-α-二甲基乙二肟、雙-o-(第三丁烷磺醯基)-α-二甲基乙二肟、雙-o-(全氟辛烷磺醯 基)-α-二甲基乙二肟、雙-o-(環己烷磺醯基)-α-二甲基乙二肟、雙-o-(苯磺醯基)-α-二甲基乙二肟、雙-o-(對-氟苯磺醯基)-α-二甲基乙二肟、雙-o-(對-第三丁基苯磺醯基)-α-二甲基乙二肟、雙-o-(二甲苯磺醯基)-α-二甲基乙二肟或雙-o-(樟腦磺醯基)-α-二甲基乙二肟。 The nonionic photoacid generator may also include a quinone derivative such as, for example, bis-o-(p-toluenesulfonyl)-α-dimethylglyoxime, bis-o-(p-toluene) Mercapto)-α-diphenylethylenediazine, bis-o-(p-toluenesulfonyl)-α-dicyclohexylethylenedifluoride, bis-o-(p-toluenesulfonyl)-2, 3-pentanedione, bis-o-(p-toluenesulfonyl)-2-methyl-3,4-pentanedione, bis-o-(n-butanesulfonyl) -α-dimethylglyoxime, bis-o-(n-butanesulfonyl)-α-diphenylglyoxime, bis-o-(n-butanesulfonyl)-α-dicyclohexyl Ethylene dioxime, bis-o-(n-butanesulfonyl)-2,3-pentanedione ethanedioxime, bis-o-(n-butanesulfonyl)-2-methyl-3,4- Ethylene diketone, bis-o-(methanesulfonyl)-α-dimethylglyoxime, bis-o-(trifluoromethanesulfonyl)-α-dimethylglyoxime, double -o-(1,1,1-trifluoroethanesulfonyl)-α-dimethylglyoxime, bis-o-(t-butanesulfonyl)-α-dimethylglyoxime , double-o-(perfluorooctanesulfonate) -α-dimethylglyoxime, bis-o-(cyclohexanesulfonyl)-α-dimethylglyoxime, bis-o-(phenylsulfonyl)-α-dimethyl Ethylene dioxime, bis-o-(p-fluorophenylsulfonyl)-α-dimethylglyoxime, bis-o-(p-t-butylphenylsulfonyl)-α-dimethyl b Diterpene, bis-o-(xylsulfonyl)-α-dimethylglyoxime or bis-o-(camphorsulfonyl)-α-dimethylglyoxime.

此等光酸產生劑亦可包括雙碸衍生物，諸如(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)。 These photoacid generators may also include biguanide derivatives such as, for example, bisnaphthylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonyl Methane, bispropylsulfonyl methane, diisopropylsulfonyl methane, bis-p-toluenesulfonyl methane, bisphenylsulfonyl methane, 2-cyclohexyl-carbonyl-2-(p-toluenesulfonate) Propane (β-keto oxime derivative) and 2-isopropyl-carbonyl-2-(p-toluenesulfonyl)propane (β-keto oxime derivative).

其他類別之可用的非離子光酸產生劑包括二磺基衍生物，諸如(例如)二苯基二碸及二環己基二碸；磺酸硝基苄酯衍生物，諸如(例如)對甲苯磺酸2,6-二硝基苄酯及對甲苯磺酸2,4-二硝基苄酯；磺酸酯衍生物，諸如(例如)1,2,3-三(甲磺醯基氧基)苯、1,2,3-三(三氟甲磺醯基氧基)苯及1,2,3-三(對甲苯磺醯基氧基)苯；及N-羥基醯亞胺之磺酸酯，諸如(例如)N-羥基琥珀醯亞胺甲磺酸酯、N-羥基琥珀醯亞胺三氟甲磺酸酯、N-羥基琥珀醯亞胺乙磺酸酯、N-羥基琥珀醯亞胺1-丙磺酸酯、N-羥基琥珀醯亞胺2-丙磺酸酯、N-羥基琥珀醯亞胺1-戊磺酸酯、N-羥基琥珀醯亞胺1-辛磺酸酯、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-苯基琥珀醯亞胺甲磺酸酯、N-羥基馬來醯亞胺甲磺酸酯、N-羥基馬來醯亞胺乙磺酸酯、N-羥基-2-苯基馬來醯亞胺甲磺酸酯、N-羥基戊二醯亞 胺甲磺酸酯、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磺酸酯、N-羥基萘二甲醯亞胺苯磺酸酯、N-羥基-5-降冰片烯-2,3-二甲醯亞胺甲磺酸酯、N-羥基-5-降冰片烯-2,3-二甲醯亞胺三氟甲磺酸酯、N-羥基-5-降冰片烯-2,3-二甲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-降冰片烯-2,3-二甲醯亞胺全氟-1-丁磺酸酯。 Other classes of useful nonionic photoacid generators include disulfo derivatives such as, for example, diphenyl difluorene and dicyclohexyl difluorene; nitrobenzyl sulfonate derivatives such as, for example, p-toluene Acid 2,6-dinitrobenzyl ester and 2,4-dinitrobenzyl p-toluenesulfonate; sulfonate derivatives such as, for example, 1,2,3-tris(methylsulfonyloxy) Benzene, 1,2,3-tris(trifluoromethanesulfonyloxy)benzene and 1,2,3-tris(p-toluenesulfonyloxy)benzene; and sulfonate of N-hydroxyquinone Such as, for example, N-hydroxysuccinimide mesate, N-hydroxy amber imine triflate, N-hydroxy amber imine ethanesulfonate, N-hydroxy amber imine 1-propane sulfonate, N-hydroxysuccinimide 2-propane sulfonate, N-hydroxysuccinimide 1-pentane sulfonate, N-hydroxysuccinimide 1-octane sulfonate, N -hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide Benzene sulfonate, N-hydroxysuccinimide 2,4,6-trifluorobenzenesulfonate, N-hydroxysuccinimide 2,4,6-trimethylbenzenesulfonic acid , N-hydroxysuccinimide 2,4,6-trichlorobenzenesulfonate, N-hydroxysuccinimide 4-cyano-benzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonic acid Ester, N-hydroxysuccinimide 2-naphthalene sulfonate, N-hydroxy-2-phenyl succinimide mesate, N-hydroxymaleimine mesylate, N-hydroxyl醯iminoethanesulfonate, N-hydroxy-2-phenylmaleimide mesylate, N-hydroxypentadienyl Amine mesylate, N-hydroxypentamethylene benzene sulfonate, N-hydroxyphthalimidomethanesulfonate, N-hydroxyphthalimidobenzenesulfonate, N -hydroxyphthalic acid imine trifluoromethanesulfonate, N-hydroxyphthalic acid imine p-toluenesulfonate, N-hydroxynaphthyldimethylenimine mesylate, N-hydroxynaphthalene Dimethyl imidate benzene sulfonate, N-hydroxy-5-norbornene-2,3-dimethyl sulfoximine mesylate, N-hydroxy-5-norbornene-2,3-dimethyl醯iminotrifluoromethanesulfonate, N-hydroxy-5-norbornene-2,3-dimethylimine imine p-toluenesulfonate, N-hydroxynaphthylimine imine triflate And N-hydroxy-5-norbornene-2,3-dimethylimine imine perfluoro-1-butanesulfonate.

一或多種非離子光酸產生劑可以基於非水性可光固化組合物總重量計至少0.05重量%且至多(含)10重量%或通常至少0.1重量%且至多(含)10重量%或甚至至少0.5重量%且至多(含)5重量%之量存於非水性可光固化組合物中。 The one or more nonionic photoacid generators may be at least 0.05% by weight and at most 10% by weight or usually at least 0.1% by weight and at most 10% by weight or even at least based on the total weight of the non-aqueous photocurable composition An amount of 0.5% by weight and up to 5% by weight is present in the non-aqueous photocurable composition.

本文中所述之一些非水性可光固化組合物(特別是彼等含有可光聚合環氧材料及光酸產生劑者)可含有一或多種電子供體光敏劑。可用的電子供體光敏劑應可溶於非水性可光固化組合物中，不含將實質上干擾陽離子光固化製程之官能性，且具有在至少150nm且至多(含)1000nm之波長範圍內之光吸收(敏感性)之能力。 Some of the non-aqueous photocurable compositions described herein (especially those containing photopolymerizable epoxy materials and photoacid generators) may contain one or more electron donor photosensitizers. Useful electron donor photosensitizers should be soluble in the non-aqueous photocurable composition, free of functionalities that would substantially interfere with the cationic photocuring process, and have a wavelength range of at least 150 nm and at most 1000 nm. The ability to absorb light (sensitivity).

適宜之電子供體光敏劑回應於自輻射所吸收的光子引發鎓鹽(或其他光酸產生劑)之化學轉變。電子供體光敏劑應亦具有在電子供體光敏劑已吸收光(即，光致電子轉移)後還原光酸產生劑之能力。因此，電子供體光敏劑在自輻射吸收光子後立刻大體上具有將電子供給光酸產生劑之能力。 Suitable electron donor photosensitizers are responsive to the chemical conversion of the photon induced by the self-irradiation to the onium salt (or other photoacid generator). The electron donor photosensitizer should also have the ability to reduce the photoacid generator after the electron donor photosensitizer has absorbed light (i.e., photoelectron transfer). Thus, the electron donor photosensitizer generally has the ability to supply electrons to the photoacid generator immediately after self-radiation absorbs photons.

當需要極快速的固化(諸如，薄的經施覆之非水性可光固化組合物之膜之固化)時，使用光固化製程，在所需輻射波長下，電子供體光敏劑可具有至少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。 When very fast curing is required, such as curing of a thin film of a coated non-aqueous photocurable composition, a photocuring process can be used, the electron donor photosensitizer can have at least 1000 at the desired wavelength of radiation. The extinction coefficient of liters-mole ^-1 cm ^-1 and usually at least 50,000 liters-mole ^-1 cm ^-1 .

例如，各電子供體光敏劑一般具有至少0.4V且至多(含)3V(相對於SCE)或更通常至少0.8V且至多(含)2V(相對於SCE)之氧化電位。 For example, each electron donor photosensitizer typically has an oxidation potential of at least 0.4 V and at most 3 V (relative to SCE) or more typically at least 0.8 V and at most 2 V (relative to SCE).

一般而言，許多不同類別之化合物可用作電子供體光敏劑用於各種反應物。可用的電子供體光敏劑包括(但不限於)芳族化合物，諸如萘、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(fluoranthene)。 In general, many different classes of compounds are useful as electron donor photosensitizers for various reactants. Useful electron donor photosensitizers include, but are not limited to, aromatic compounds such as naphthalene, 1-methylnaphthalene, anthracene, 9,10-dimethoxyanthracene, benzo[a]anthracene, anthracene, phenanthrene, benzene And [c] phenanthrene and fluoranthene.

其他可用的關於三重激發態之電子供體光敏劑為羰基化合物，諸如9-氧硫酮及酮。酮(包括芳族酮，諸如芴酮)及香豆素染料(諸如酮基香豆素，諸如彼等具有強供電子部分(諸如二烷胺基)者)亦可用作電子供體光敏劑。咸信其他的適宜電子供體光敏劑包括染料、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、對位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 for triplet excited states are carbonyl compounds such as 9-oxosulfur Ketone and ketone. Ketones (including aromatic ketones such as anthrone) and coumarin dyes (such as ketocoumarins, such as those having a strong electron donating moiety such as a dialkylamine group) can also be used as electron donor photosensitizers. . Other suitable electronic donor photosensitizers include Dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, para-substituted aminostyryl ketone compounds, amine-based triaryl Methane, merocyanine, squarylium dye and pyridinium dye.

亦可使用選自相同或不同類別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 classes of materials may also be used.

各種可用的電子供體光敏劑可從各種商業來源購得且可輕易地發現以用於本發明中。 A wide variety of available electron donor photosensitizers are commercially available from various commercial sources and are readily found for use in the present invention.

當使用時，一或多種電子供體光敏劑可以基於非水性可光固化組合物總重量計至少0.000001重量%且至多(含)5重量%且通常至少0.0001重量%且至多(含)2重量%之量存於非水性可光固化組合物中。所需電子供體光敏劑之精確量根據總體非水性可光固化組合物、其所欲用途及消光係數改變。 When used, the one or more electron donor photosensitizers can be at least 0.000001% by weight and up to (including) 5% by weight and typically at least 0.0001% by weight and up to 2% by weight, based on the total weight of the non-aqueous photocurable composition. The amount is present in the non-aqueous photocurable composition. The exact amount of electron donor photosensitizer required will vary depending upon the overall non-aqueous photocurable composition, its intended use, and extinction coefficient.

在一些實施例中，電子供體光敏劑為芘、苯并芘、苝或苯并苝，其係以基於非水性可光固化組合物總重量計至少0.0001重量%且至多(含)2重量%之量存在。 In some embodiments, the electron donor photosensitizer is ruthenium, benzoxanthene, anthracene or benzofluorene, which is at least 0.0001% by weight and up to 2% by weight based on the total weight of the non-aqueous photocurable composition. The amount exists.

在本發明之一些非水性可光固化組合物中，電子供體光敏劑可 改由一或多種電子受體光敏劑及一或多種電子供體共引發劑之組合替代。 In some non-aqueous photocurable compositions of the invention, the electron donor photosensitizer can Instead, it is replaced by a combination of one or more electron acceptor photosensitizers and one or more electron donor co-initiators.

可用的電子受體光敏劑應可溶於非水性可光固化組合物中，不含將實質上干擾陽離子光固化製程之官能性，且具有在至少150nm且至多(含)1000nm之波長範圍內之光吸收(敏感性)之能力。 Useful electron acceptor photosensitizers should be soluble in the non-aqueous photocurable composition, free of functionalities that would substantially interfere with the cationic photocuring process, and have a wavelength range of at least 150 nm and at most 1000 nm. The ability to absorb light (sensitivity).

適宜之電子受體光敏劑回應於自輻射所吸收的光子引發鎓鹽之化學轉變。電子受體光敏劑應亦具有在電子受體光敏劑已吸收光(即，光致電子轉移)後將電子供體共引發劑(述於下文)氧化成陽離子自由基之能力。因此，電子受體光敏劑在自輻射吸收光子後立刻大體上具有自電子供體共引發劑接受電子之能力。 Suitable electron acceptor photosensitizers initiate chemical transformation of the phosphonium salt in response to photons absorbed by the self-irradiation. The electron acceptor photosensitizer should also have the ability to oxidize the electron donor co-initiator (described below) to cationic free radicals after the electron acceptor photosensitizer has absorbed light (i.e., photoelectron transfer). Thus, the electron acceptor photosensitizer generally has the ability to accept electrons from the electron donor co-initiator immediately after self-radiation absorbs photons.

當需要極快速的固化(諸如，薄的經施覆之組合物之膜之固化)時，使用光固化製程，在所需輻射波長下，電子受體光敏劑可具有至少1000公升-莫耳^-1cm^-1且通常至少10,000公升-莫耳^-1cm^-1之消光係數。 When required extremely rapid curing (such as, a thin film of the coating composition was applied to the cured composition), using the photocurable process, at a desired wavelength of radiation, electron acceptor photosensitizers have at least 1000 liters - mole ^- An extinction coefficient of ¹ cm ^-1 and usually at least 10,000 liters - mol ^{- 1} cm ^-1 .

一般而言，許多不同類別之化合物可用作電子受體光敏劑用於各種反應物，其限制條件為滿足上述能量要求。可用的電子受體光敏劑包括(但不限於)氰基芳族化合物，諸如1-氰基萘、1,4-二氰基萘、9,10-二氰基蒽、2,9,10-三氰基蒽、2,6,9,10-四氰基蒽；芳族酸酐及醯亞胺，諸如1,8-萘二羧酸、1,4,6,8-萘四羧酸、3,4-苝二羧酸及3,4,9,10-苝四羧酸酐或醯亞胺；縮合吡啶鎓鹽，諸如喹啉鎓、異喹啉鎓、菲啶鎓、吖啶鎓及吡喃鎓鹽。 In general, many different classes of compounds are useful as electron acceptor photosensitizers for various reactants, with the proviso that the above energy requirements are met. Useful electron acceptor photosensitizers include, but are not limited to, cyanoaromatic compounds such as 1-cyanonaphthalene, 1,4-dicyanophthalene, 9,10-dicyanoguanidine, 2,9,10- Tricyanoguanidine, 2,6,9,10-tetracyanoindole; aromatic anhydrides and quinone imines such as 1,8-naphthalenedicarboxylic acid, 1,4,6,8-naphthalenetetracarboxylic acid, 3 , 4-indanedicarboxylic acid and 3,4,9,10-decanetetracarboxylic anhydride or quinone imine; condensed pyridinium salts such as quinolinium, isoquinolinium, phenanthridine, acridinium and pyran鎓 salt.

其他可用的關於三重激發態之電子受體光敏劑為羰基化合物，諸如醌，諸如，具有吸電子取代基(諸如氯及氰基)之苯-、萘-、蒽-醌。酮(包括芳族酮，諸如芴酮)及香豆素染料(諸如酮基香豆素，諸如彼等具有強吸電子部分者(諸如吡啶鎓))亦可用作電子受體光敏劑。咸信其他適宜之電子受體光敏劑包括染料、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、對位取代之胺基苯乙烯酮化合物、胺基三芳基甲烷、部花青素、方酸菁染料及吡啶鎓染料。二芳基酮及其他芳族酮(諸如芴酮)為可用的電子受體光敏劑。 Other useful electron acceptor photosensitizers for the triplet excited state are carbonyl compounds such as hydrazine, such as benzene-, naphthalene-, fluorene-fluorene having electron-withdrawing substituents such as chlorine and cyano. Ketones (including aromatic ketones such as anthrone) and coumarin dyes (such as ketocoumarins, such as those having a strong electron withdrawing moiety such as pyridinium) can also be used as electron acceptor photosensitizers. Other suitable electronic receptor photosensitizers include Dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, porphyrin, aromatic polycyclic hydrocarbon, para-substituted aminostyrene ketone compound, aminotriaryl Methane, merocyanine, squaraine dye and pyridinium dye. Diaryl ketones and other aromatic ketones such as anthrone are useful electron acceptor photosensitizers.

只要滿足上述電化學要求，亦可使用選自相同或不同類別材料之電子受體光敏劑之混合物。 Mixtures of electron acceptor photosensitizers selected from the same or different classes of materials may also be used provided that the above electrochemical requirements are met.

各種可用的電子受體光敏劑可從各種商業來源購得。 A wide variety of available electron acceptor photosensitizers are commercially available from a variety of commercial sources.

該一或多種電子受體光敏劑可以基於非水性可光固化組合物總重量計至少0.000001重量%且至多(含)5重量%及通常至少0.0001重量%且至多(含)2重量%之量存於非水性可光固化組合物中。 The one or more electron acceptor photosensitizers may be present in an amount of at least 0.000001% by weight and at most (inclusive) 5% by weight and typically at least 0.0001% by weight and up to 2% by weight, based on the total weight of the non-aqueous photocurable composition. In a non-aqueous photocurable composition.

藉由將一或多種電子供體共引發劑併入非水性可光固化組合物中，電子受體光敏劑之使用高度有效，各電子供體共引發劑具有至少0.1V且至多(含)3V(相對於SCE)之氧化電位。因此，此等電子供體共引發劑應可溶於非水性可光固化組合物中。亦可藉由考慮其他因素(諸如貯存穩定性及所選可光聚合環氧材料、光酸產生劑及電子受體光敏劑之性質)來選擇電子供體共引發劑。 The use of an electron acceptor photosensitizer is highly effective by incorporating one or more electron donor co-initiators into the non-aqueous photocurable composition, each electron donor co-initiator having at least 0.1 V and at most 3 V. Oxidation potential (relative to SCE). Therefore, such electron donor co-initiators should be soluble in the non-aqueous photocurable composition. The electron donor co-initiator can also be selected by considering other factors such as storage stability and the nature of the selected photopolymerizable epoxy material, photoacid generator, and electron acceptor photosensitizer.

可用的電子供體共引發劑為烷基芳族聚醚、芳基烷基胺基化合物，其中該芳基係經一或多個包括(但不限於)羧酸、羧酸酯、酮、醛、磺酸、磺酸酯及腈基之吸電子基取代。例如，芳基二烷基二胺基化合物適用，其中該芳基為經取代或未經取代之苯基或萘基(諸如，具有一或多個如上所述之吸電子基之苯基或萘基)，及此兩烷基獨立地包含1至6個碳原子。 Useful electron donor co-initiators are alkyl aromatic polyethers, arylalkylamine based compounds wherein the aryl group is one, but not limited to, carboxylic acids, carboxylic acid esters, ketones, aldehydes. Substituting electron withdrawing groups of sulfonic acids, sulfonic acid esters and nitrile groups. For example, an aryldialkyldiamine compound is suitable wherein the aryl group is a substituted or unsubstituted phenyl or naphthyl group (such as a phenyl or naphthalene having one or more electron withdrawing groups as described above) And the two alkyl groups independently comprise from 1 to 6 carbon atoms.

可用的電子供體共引發劑可輕易地從多種商業來源獲得。 Useful electron donor co-initiators are readily available from a variety of commercial sources.

一般而言，該一或多種電子供體共引發劑可以基於非水性可光固化組合物總重量計至少0.001重量%且至多(含)10重量%或更通常至少0.005重量%且至多(含)5重量%或甚至至少0.01重量%且至多(含)2重 量%之量存在。 In general, the one or more electron donor co-initiators can be at least 0.001% by weight and up to (including) 10% by weight or more typically at least 0.005% by weight and up to (including) based on the total weight of the non-aqueous photocurable composition. 5 wt% or even at least 0.01 wt% and at most 2 The amount of % is present.

如上所述，所有該等含有各種必需且視需要之組分之非水性可光固化組合物可包含基於非水性可光固化組合物總重量計至少0.5重量%且至多(含)20重量%或至少1重量%且至多(含)10重量%含量之經分散之碳黑。 As noted above, all such non-aqueous photocurable compositions containing various necessary and optional components may comprise at least 0.5% by weight and up to 20% by weight, based on the total weight of the non-aqueous photocurable composition, or At least 1% by weight and up to (including) 10% by weight of the dispersed carbon black.

本發明之非水性可光固化組合物之一些實施例可包含以下各組分：(a)如上所述之可光聚合環氧材料、(b)如上所述之光酸產生劑、(c)如上所述之電子供體光敏劑、(d)如上所述之經分散之經碳塗覆的金屬顆粒與如上所述之任何顆粒分散劑、(e)有機稀釋劑，諸如，如上所述之有機溶劑介質、(f)可自由基聚合材料及(g)自由基光引發劑，其中：該可光聚合環氧材料每分子具有至少兩個可聚合環氧基，該光酸產生劑為錪或鋶，及該等經分散之經碳塗覆的金屬顆粒為如使用如上所述之動態光散射法測得之具有等於或小於0.5μm之中值直徑之經分散之經碳塗覆的銀顆粒。 Some embodiments of the non-aqueous photocurable composition of the present invention may comprise the following components: (a) a photopolymerizable epoxy material as described above, (b) a photoacid generator as described above, (c) An electron donor photosensitizer as described above, (d) a dispersed carbon coated metal particle as described above, and any particulate dispersant as described above, (e) an organic diluent, such as described above An organic solvent medium, (f) a radically polymerizable material, and (g) a radical photoinitiator, wherein: the photopolymerizable epoxy material has at least two polymerizable epoxy groups per molecule, and the photoacid generator is ruthenium Or 鋶, and the dispersed carbon-coated metal particles are dispersed carbon-coated silver having a median diameter equal to or less than 0.5 μm as measured by dynamic light scattering as described above. Particles.

自由基可光固化化學：Free radical photocurable chemistry:

在其他實施例中，非水性可光固化組合物包含一或多種可UV固化組分，其中至少一者為可自由基光固化組分且該非水性可光固化組合物可進一步包含自由基光引發劑以在光固化期間提供自由基。 In other embodiments, the non-aqueous photocurable composition comprises one or more UV curable components, at least one of which is a free radical photocurable component and the non-aqueous photocurable composition can further comprise free radical photoinitiation The agent provides free radicals during photocuring.

該一或多種可自由基聚合化合物可存在以提供可自由基聚合官能性，包括烯系不飽和可聚合單體、寡聚物或聚合物(諸如單官能或多官能丙烯酸酯(亦包括甲基丙烯酸酯))。此等可自由基聚合化合物包含至少一個烯系不飽和可聚合鍵(部分)且其等在許多實施例中可包含兩個或更多個此等不飽和部分。此類型之適宜材料含有至少一個烯系不飽和可聚合鍵且具有進行加成(或自由基)聚合之能力。此等可自由 基聚合材料包括單-、二-或聚-丙烯酸酯及甲基丙烯酸酯，包括(但不限於)丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸乙酯、甲基丙烯酸異丙酯、丙烯酸正己酯、丙烯酸十八酯、丙烯酸烯丙酯、二丙烯酸甘油酯、三丙烯酸甘油酯、二丙烯酸乙二醇酯、二丙烯酸二乙二醇酯、二甲基丙烯酸三乙二醇酯、二丙烯酸1,3-丙二醇酯、二甲基丙烯酸1,3-丙二醇酯、二丙烯酸1,4-丁二醇酯、二丙烯酸1,6-己二醇酯、二丙烯酸新戊二醇酯、二甲基丙烯酸新戊二醇酯、三羥甲基丙烷三丙烯酸酯、三甲基丙烯酸1,2,4-丁三醇酯、二丙烯酸1,4-環己二醇酯、季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、季戊四醇四甲基丙烯酸酯、二季戊四醇六丙烯酸酯、山梨糖醇六丙烯酸酯、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三-羥乙基-異氰尿酸酯三甲基丙烯酸酯；該等聚乙二醇之雙丙烯酸酯及雙甲基丙烯酸酯具有200至(含)500之分子量，丙烯酸酯單體(諸如彼等述於美國專利4,652,274(Boettcher等人)中者)及丙烯酸酯寡聚物(諸如彼等述於美國專利4,642,126(Zader等人)中者)之可共聚合混合物；及乙烯基化合物(諸如苯乙烯及苯乙烯衍生物)、鄰苯二甲酸二烯丙酯、琥珀酸二乙烯酯、己二酸二乙烯酯及鄰苯二甲酸二乙烯酯。若需要則可使用兩種或更多種此等可自由基聚合材料之混合物。 The one or more free-radically polymerizable compounds may be present to provide free-radical polymerizable functionality, including ethylenically unsaturated polymerizable monomers, oligomers or polymers (such as monofunctional or polyfunctional acrylates (including methyl groups) Acrylate)). These free radically polymerizable compounds comprise at least one ethylenically unsaturated polymerizable bond (portion) and the like may, in many embodiments, comprise two or more such unsaturated moieties. Suitable materials of this type contain at least one ethylenically unsaturated polymerizable bond and have the ability to undergo addition (or free radical) polymerization. These are free The base polymeric materials include mono-, di- or poly-acrylates and methacrylates including, but not limited to, methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate , octadecyl acrylate, allyl acrylate, glyceryl diacrylate, glyceryl triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, diacrylic acid 1, 3-propylene glycol ester, 1,3-propanediol dimethacrylate, 1,4-butylene glycol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, dimethacrylic acid Neopentyl glycol ester, trimethylolpropane triacrylate, 1,2,4-butane triol methacrylate, 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate Ester, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, bis[1-(2-propenyloxy)]-p-ethoxyphenyldimethylmethane, double [ 1-(3-propenyloxy-2-hydroxy)]-p-propoxyphenyldimethylmethane and tris-hydroxyethyl -isocyanurate trimethacrylate; the diacrylates and dimethacrylates of the polyethylene glycols have a molecular weight of from 200 to 500, acrylate monomers (such as those described in US patents) 4,652,274 (Boettcher et al.) and copolymerizable mixtures of acrylate oligomers such as those described in U.S. Patent 4,642,126 (Zader et al.); and vinyl compounds (such as styrene and styrene derived). And diallyl phthalate, divinyl succinate, divinyl adipate and divinyl phthalate. Mixtures of two or more such free radically polymerizable materials can be used if desired.

此等材料可從許多商業來源購買或使用已知的合成方法及起始材料製得。 Such materials can be purchased from a number of commercial sources or prepared using known synthetic methods and starting materials.

雖然該一或多種可自由基聚合材料的量無特別限制，但其可以基於非水性可光固化組合物總重量計至少10重量%且至多(含)90重量%或通常至少20重量%且至多(含)85重量%之量存於非水性可光固化組合物中，且可基於期望之所得的經光固化之組合物之組合物溶解度及機械強度性質最佳化。 Although the amount of the one or more radically polymerizable materials is not particularly limited, it may be at least 10% by weight and at most 90% by weight or usually at least 20% by weight and at most based on the total weight of the non-aqueous photocurable composition The amount of (inclusive) 85% by weight is present in the non-aqueous photocurable composition and can be optimized based on the desired solubility and mechanical strength properties of the resulting photocurable composition.

一或多種自由基光引發劑亦可存於非水性可光固化組合物中以產生自由基。此等自由基光引發劑包括任何的具有在暴露於實施本發明中使用的光固化輻射(諸如紫外線或可見光輻射)後立刻產生自由基之能力之化合物。例如，自由基光引發劑可選自三嗪化合物、9-氧硫化合物、安息香化合物、咔唑化合物、二酮化合物、硼酸鋶化合物、重氮化合物及聯咪唑化合物及將為熟悉此項技術者所可輕易明瞭之其他化合物。此等化合物之混合物可選自相同或不同類別。 One or more free radical photoinitiators may also be present in the non-aqueous photocurable composition to generate free radicals. Such free radical photoinitiators include any compound having the ability to generate free radicals upon exposure to photocuring radiation (such as ultraviolet or visible radiation) used in the practice of the present invention. For example, the free radical photoinitiator can be selected from the group consisting of triazine compounds, 9-oxosulfur The compound, the benzoin compound, the carbazole compound, the diketone compound, the bismuth borate compound, the diazo compound, and the biimidazole compound, and other compounds which will be readily apparent to those skilled in the art. Mixtures of such compounds may be selected from the same or different classes.

亦可用的是二苯甲酮化合物(諸如二苯甲酮、苯甲醯基苯甲酸酯、苯甲醯基苯甲酸甲酯、4-苯基二苯甲酮、羥基二苯甲酮、丙烯酸酯化之二苯甲酮、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(諸如2,2'-二乙氧基苯乙酮、2,2'-二丁氧基苯乙酮、2-羥基-2-甲基苯丙酮、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-1-酮)。此類型之其他可用化合物述於例如美國專利7,875,416(Park等人)中。 Also useful are benzophenone compounds (such as benzophenone, benzhydryl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxybenzophenone, acrylic acid). Esterified benzophenone, 4,4'-bis(dimethylamino)benzophenone and 4,4'-bis(diethylamino)benzophenone), anthraquinone compounds and benzene Ethyl ketone compounds (such as 2,2'-diethoxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloro Acetophenone, p-t-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichloro Benzophenone, 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)-but-1- ketone). Other useful compounds of this type are described, for example, in U.S. Patent 7,875,416 (Park et al.).

許多此等自由基光引發劑可從各種商業來源獲得。 Many of these free radical photoinitiators are available from a variety of commercial sources.

一或多種自由基光引發劑可以基於非水性可光固化組合物總重量計至少0.3重量%且至多(含)10重量%或通常至少0.4重量%且至多(含)10重量%或甚至至少0.5重量%且至多(含)5重量%之量存於非水性可光固化組合物中。 The one or more free radical photoinitiators may be at least 0.3% by weight and at most 10% by weight or usually at least 0.4% by weight and at most 10% by weight or even at least 0.5 based on the total weight of the non-aqueous photocurable composition. The amount by weight and up to 5% by weight is present in the non-aqueous photocurable composition.

在一些此等實施例中，非水性可光固化組合物包含一或多種如上所述之可自由基聚合材料、一或多種如上所述之自由基光引發劑、如上所述之經分散基之經碳塗覆的銀顆粒、有機溶劑介質，其中丙烯酸酯係呈一種該可自由基聚合組分存在。 In some such embodiments, the non-aqueous photocurable composition comprises one or more free-radically polymerizable materials as described above, one or more free-radical photoinitiators as described above, a dispersed group as described above Carbon coated silver particles, an organic solvent medium in which the acrylate is present as one of the radical polymerizable components.

製備非水性可光固化組合物Preparation of non-aqueous photocurable compositions

為製備本發明之非水性可光固化組合物，以任何適宜方式將各種組分(包括必需組分及視需要之組分)在例如適宜之有機稀釋劑(諸如有機溶劑介質)中組合，可光固化組分充作有機稀釋劑(如上所述)除外。因此，此等組合製程可將適宜之如上所述之經分散之經碳塗覆的金屬顆粒(包括如上所述之顆粒分散劑)及一或多種可光固化組分(如上所述)在有機稀釋劑中混合。此等可光固化組分可包括可UV固化組分及UV光引發劑。或者，該等可光固化組分可包括可聚合環氧材料及光酸產生劑。 To prepare the non-aqueous photocurable compositions of the present invention, the various components, including the essential components and optional components, are combined, for example, in a suitable organic diluent (such as an organic solvent medium) in any suitable manner. The photocurable component is used as an organic diluent (as described above). Thus, such combined processes may employ suitably dispersed carbon coated metal particles (including particulate dispersants as described above) and one or more photocurable components (as described above) in organic Mix in the diluent. These photocurable components can include a UV curable component and a UV photoinitiator. Alternatively, the photocurable components may include a polymerizable epoxy material and a photoacid generator.

所得非水性可光固化組合物可呈25℃下具有至少1厘泊且至多(含)100,000厘泊黏度之流體、凝膠或糊劑提供。非水性可光固化組合物可由習知方法施覆至多種基材(述於下文)且使用各種固化裝置及輻射源在1秒或至多10分鐘或更長時間內光固化至無黏性狀態。在光固化的同時或之前，可使用適宜之乾燥方法移除任何惰性有機溶劑。 The resulting non-aqueous photocurable composition can be provided as a fluid, gel or paste having a viscosity of at least 1 centipoise and at most 100,000 centipoise at 25 °C. The non-aqueous photocurable composition can be applied to a variety of substrates (described below) by conventional methods and photocured to a tack-free state for 1 second or up to 10 minutes or longer using various curing devices and radiation sources. At the same time as or before photocuring, any inert organic solvent can be removed using a suitable drying method.

可用於此混合之尤其可用的惰性有機溶劑(除了上文所述之其等之外)包括(但不限於)丙酮、甲醇、乙醇、異丙醇、1-甲氧基-2-丙醇(Dowanol PM)、二氯甲烷及其不會明顯與非水性可光固化組合物之任何反應性組分反應之混合物。 Particularly useful inert organic solvents (other than those described above) which may be employed in the mixing include, but are not limited to, acetone, methanol, ethanol, isopropanol, 1-methoxy-2-propanol ( Dowanol PM), methylene chloride and mixtures thereof which do not significantly react with any of the reactive components of the non-aqueous photocurable composition.

物件object

本發明之非水性可光固化組合物可如上所述調配且使用任何適宜方法施覆至任何適宜基材(述於下文)之一或兩個支撐側(平面側)。例如，非水性可光固化組合物可使用(例如)浸塗、輥塗、漏斗式塗佈、噴塗、旋塗、油墨噴塗、光微影壓印、使用柔版印刷部件(諸如柔版印刷板及柔版印刷套筒)之柔版印刷、使用微影印刷板之微影印刷及使用適宜印刷部件之凹版或凹雕印刷以均勻或逐個圖案方法施覆至支撐側任一側或兩側。使用柔版印刷部件之柔版印刷尤其可用於提 供預定之非水性可光固化組合物之圖案，及此方法可用於在基材之一或兩個支撐側上提供多個相同或不同非水性可光固化組合物圖案。此等製程之更多細節提供於下文中。 The non-aqueous photocurable compositions of the present invention can be formulated as described above and applied to one or both of the support sides (planar sides) of any suitable substrate (described below) using any suitable method. For example, non-aqueous photocurable compositions can be used, for example, by dip coating, roll coating, funnel coating, spray coating, spin coating, ink coating, photolithography, using flexographic printing components such as flexographic printing plates. Flexographic printing of flexographic printing sleeves, lithographic printing using lithographic printing plates, and gravure or intaglio printing using suitable printing components are applied to either side or both sides of the support side in a uniform or pattern-by-pattern manner. Flexographic printing using flexographic printing parts is especially useful for lifting A pattern of predetermined non-aqueous photocurable compositions, and the method can be used to provide a plurality of identical or different non-aqueous photocurable composition patterns on one or both of the support sides. Further details of these processes are provided below.

所施覆之非水性可光固化組合物可經形成且乾燥呈均勻層或乾燥呈預定圖案。所得物件在如下文所述進行光固化之前可視為「前驅」物件。 The applied non-aqueous photocurable composition can be formed and dried to a uniform layer or dried in a predetermined pattern. The resulting article can be considered a "precursor" item prior to photocuring as described below.

如下文更詳細地描述，用於此等物件之基材可由任何有用的材料構成且可為例如由金屬材料、玻璃、紙料(paperstock)(任何類型之纖維素材料)或陶瓷構成之任何適宜尺寸及形狀之個別膜或薄片，或其可為材料之連續網，諸如連續聚合物網。 As described in more detail below, the substrate for such articles can be constructed of any useful material and can be any suitable, for example, made of metallic materials, glass, paperstock (any type of cellulosic material), or ceramic. Individual films or sheets of size and shape, or they may be a continuous web of material, such as a continuous polymeric web.

上文描述非水性組合物(包括非水性可光固化組合物)之必需且視需要之組分之各種量，但應明瞭該等量係指含有此等組分之溶液或分散液。然而，應明瞭，在施覆至適宜之基材，及視需要乾燥，且接著光固化之後，於所施覆之非水性組合物中各種組分之量不同。可從施覆至基材前的非水性組合物中組分的量相關資訊輕易地計算得其餘組分(若(例如)已移除惰性有機溶劑)之個別量及相對量。 The various amounts of the essential and optional components of the non-aqueous compositions (including the non-aqueous photocurable compositions) are described above, but it should be understood that such amounts refer to solutions or dispersions containing such components. However, it should be understood that the amounts of the various components in the non-aqueous composition applied are different after application to a suitable substrate, and drying as needed, and then photocuring. The individual amounts and relative amounts of the remaining components (if, for example, the inert organic solvent has been removed) can be readily calculated from information relating to the amount of components in the non-aqueous composition applied to the substrate.

例如，在經乾燥之非水性組合物(包括經乾燥之非水性可光固化組合物)中，經碳塗覆的金屬顆粒可以至少10重量%且至多(含)90重量%之量存在，顆粒分散劑可以至少1重量%且至多(含)30重量%之量存在，碳顆粒可以至多(含)20重量%之量存在，及可光固化組分(述於上文中，固化前)可以至多(含)90重量%之量存在。 For example, in a dried non-aqueous composition (including a dried non-aqueous photocurable composition), the carbon coated metal particles may be present in an amount of at least 10% by weight and at most 90% by weight, granules The dispersant may be present in an amount of at least 1% by weight and up to 30% by weight, the carbon particles may be present in an amount of up to 20% by weight, and the photocurable component (described above, before curing) may be at most It is present in an amount of 90% by weight.

非水性可光固化組合物之用途Use of non-aqueous photocurable composition

本文中所述之非水性可光固化組合物可使用適宜之輻射(包括紫外光或可見光化光或二者)光固化(或光聚合)。一或多種適宜光源可用於曝光製程。各前驅物件可個別地呈單一元件曝光，或在下文所述之替代實施例中，連續聚合物網之一或兩個支撐側上多個部分中之構成 多個前驅物件(包含多個可光固化圖案)之網(例如，捲繞式連續聚合物網)可個別地在連續聚合物網通過曝光站時或在曝光裝置以所需路徑通過連續聚合物網時曝光。相同或不同非水性可光固化組合物可施覆(例如，使用柔版印刷)於基材之兩個支撐側上，無論基材呈單一元件形式或呈連續聚合物網形式。在許多實施例中，可使用本文中所述之非水性可光固化組合物在基材(或連續聚合物網)之相對支撐側上形成不同導電金屬圖案。 The non-aqueous photocurable compositions described herein can be photocured (or photopolymerized) using suitable radiation, including ultraviolet or visible light or both. One or more suitable light sources can be used in the exposure process. Each of the precursor articles may be individually exposed as a single component, or in an alternative embodiment described below, in one or both of the continuous polymer webs A web of multiple precursor articles (including a plurality of photocurable patterns) (eg, a wound continuous polymer web) can be individually passed through the continuous polymer as the continuous polymer web passes through the exposure station or through the exposure device in a desired path. Net time exposure. The same or different non-aqueous photocurable compositions can be applied (e.g., using flexographic printing) on both support sides of the substrate, whether in the form of a single component or in the form of a continuous polymer network. In many embodiments, the non-aqueous photocurable compositions described herein can be used to form different conductive metal patterns on opposite support sides of a substrate (or continuous polymeric web).

可使用具有至少184.5nm至(含)700nm之波長及至少1mJ/cm²且至多(含)1000mJ/cm²或更通常至少1mJ/cm²且至多(含)800mJ/cm²之強度之UV或可見光輻射達成期望之光固化。 May be used to at least 184.5nm (inclusive) and wavelength of 700nm of at least 1mJ / cm ² and up (with) 1000mJ / cm ² or more typically at least 1mJ / cm ² and up (with) the UV intensity 800mJ / cm ² in or Visible light radiation achieves the desired photocuring.

當在將非水性可光固化組合物均勻地施覆至適宜基材時，所得的均勻乾燥層可藉由通過適宜之具有所需圖案之光罩(遮蔽元件)曝光輻射「圖像化」或選擇性地曝光(或圖案化)，且接著使用適宜之溶解或分散未光固化之材料之「顯影」溶液適當地移除未交聯(未固化)之可光固化組合物。可在基材之兩個(相對)支撐側上進行此等特徵或步驟。除此之外，可視需要使用相同或不同光罩在經乾燥之層中形成多個圖案。 When the non-aqueous photocurable composition is uniformly applied to a suitable substrate, the resulting uniform dried layer can be "imaged" by exposure radiation through a suitable mask (shielding element) having a desired pattern or The film is selectively exposed (or patterned) and then the uncrosslinked (uncured) photocurable composition is suitably removed using a "developing" solution suitable to dissolve or disperse the non-curable material. These features or steps can be performed on the two (opposite) support sides of the substrate. In addition to this, it is possible to form a plurality of patterns in the dried layer using the same or different masks as needed.

更特定言之，可使用如下文所述之方法在適宜基材上形成一或多種非水性可光固化組合物之預定圖案。 More specifically, a predetermined pattern of one or more non-aqueous photocurable compositions can be formed on a suitable substrate using methods as described below.

可用於提供前驅物件之適宜基材(在相關技術中亦稱為「接收元件」)可由任何適宜材料構成，只要該材料不抑制非水性可光固化組合物之目的。例如，可用的基材可由包括(但不限於)以下之材料形成：聚合膜、金屬、紙料、剛性或可撓玻璃(未經處理或經由例如四氟化碳電漿、疏水性氟或矽氧烷防水材料處理)、矽或陶瓷晶圓、織物及其組合(諸如各種膜之層壓物或紙及膜之層壓物)，其限制條件係可以適宜方法在其上形成非水性可光固化組合物之均勻層或圖案且接 著輻射以在其至少一個接收(支撐)表面上形成均勻經固化層或一或多個經光固化圖案。基材可為透明、半透明或不透光及剛性或可撓。許多可用的基材為透明且具有至少90%之積合透射率，及此等透明基材亦可為可撓，諸如連續聚合物網。 A suitable substrate (also referred to in the related art as a "receiving member") that can be used to provide a precursor article can be constructed of any suitable material as long as the material does not inhibit the non-aqueous photocurable composition. For example, useful substrates can be formed from materials including, but not limited to, polymeric films, metals, paper stock, rigid or flexible glass (untreated or via, for example, carbon tetrafluoride plasma, hydrophobic fluorine or ruthenium). Oxymethane waterproofing material treatment), tantalum or ceramic wafers, fabrics and combinations thereof (such as laminates of various films or laminates of paper and film), the limitation of which is a suitable method for forming non-aqueous light thereon a uniform layer or pattern of the cured composition The radiation is directed to form a uniform cured layer or one or more photocured patterns on at least one of its receiving (supporting) surfaces. The substrate can be transparent, translucent or opaque and rigid or flexible. Many useful substrates are transparent and have an integrated transmission of at least 90%, and such transparent substrates can also be flexible, such as a continuous polymeric web.

基材可包含一或多個輔助聚合或非聚合層或一或多個在施覆非水性可光固化組合物前施覆的其他材料之圖案。例如，基材之任一個或兩個支撐(平面)表面可藉由例如底漆層處理或電或機械處理(諸如粒化)以賦予該表面「接收表面」來改良非水性可光固化組合物與所得的經光固化層或經光固化圖案之黏著。可在基材上配置黏著層以提供各種性質來回應於刺激(例如，該刺激可為熱活化、溶劑活化或化學活化)且該黏著層可充作接收層。 The substrate may comprise one or more auxiliary polymeric or non-polymeric layers or one or more patterns of other materials applied prior to application of the non-aqueous photocurable composition. For example, any one or both of the support (planar) surfaces of the substrate may be modified by, for example, a primer layer treatment or electrical or mechanical treatment (such as granulation) to impart a "receiving surface" to the surface to improve the non-aqueous photocurable composition. Adhesion to the resulting photocured layer or photocured pattern. An adhesive layer can be disposed on the substrate to provide various properties in response to the stimulus (eg, the stimulus can be heat activated, solvent activated, or chemically activated) and the adhesive layer can act as a receiving layer.

在一些實施例中，基材可包含配置於基材上之作為接收表面之個別接收層，該接收層及基材可由高度接收非水性可光固化組合物之材料(諸如適宜聚合材料)構成。當在25℃下測量時，此等接收層可具有至少0.05μm且至多(含)10μm或通常至少0.05μm且至多(含)3μm之乾厚。 In some embodiments, the substrate can comprise an individual receiving layer disposed on the substrate as a receiving surface, the receiving layer and substrate being comprised of a material that highly receives the non-aqueous photocurable composition, such as a suitable polymeric material. These receiving layers may have a dry thickness of at least 0.05 [mu]m and at most (inclusive) 10 [mu]m or typically at least 0.05 [mu]m and at most (inclusive) 3 [mu]m when measured at 25[deg.]C.

可藉由暴露於如例如美國專利5,492,730(Balaba等人)及5,527,562(Balaba等人)及美國專利申請公開案2009/0076217(Gommans等人)中所述之電暈放電、機械磨損、火焰處理或氧電漿或藉由塗覆各種聚合膜(諸如聚(偏二氯乙烯))或芳族聚矽氧烷處理基材(特別是聚合基材)之支撐側。 Corona discharge, mechanical abrasion, flame treatment or as described in, for example, U.S. Patent Nos. 5,492,730 (Balaba et al.) and 5,527,562 (Balaba et al.) and U.S. Patent Application Publication No. 2009/0076217 (Gommans et al.). Oxygen plasma or a support side of a substrate (particularly a polymeric substrate) is treated by coating various polymeric films such as poly(vinylidene chloride) or aromatic polyoxyalkylene.

用於形成呈連續網之前驅物件之適宜基材材料包括(但不限於)金屬膜或箔、於聚合物上之金屬膜(諸如，於導電聚合膜上之金屬膜)、撓性玻璃、半導電有機或無機膜、有機或無機介電膜或此等材料之兩個或更多個層之層壓物。例如，可用的連續網基材可包括聚合膜(諸如聚(對苯二甲酸乙二酯)膜、聚(萘二甲酸乙二酯)膜、聚醯亞胺膜、 聚碳酸酯膜、聚丙烯酸酯膜、聚苯乙烯膜、聚烯烴膜及聚醯胺膜)、金屬箔(諸如鋁箔、纖維素紙或經樹脂塗覆或經玻璃塗覆之紙)、紙板網及金屬化聚合膜。 Suitable substrate materials for forming a continuous mesh precursor include, but are not limited to, a metal film or foil, a metal film on the polymer (such as a metal film on a conductive polymeric film), flexible glass, and a half A conductive organic or inorganic film, an organic or inorganic dielectric film or a laminate of two or more layers of such materials. For example, useful continuous web substrates can include polymeric films such as poly(ethylene terephthalate) films, poly(ethylene naphthalate) films, polyimine films, Polycarbonate film, polyacrylate film, polystyrene film, polyolefin film and polyamide film), metal foil (such as aluminum foil, cellulose paper or resin coated or glass coated paper), cardboard mesh And metallized polymeric film.

尤其可用的基材為經如上所述表面處理或未經如上所述表面處理之由聚(對苯二甲酸乙二酯)、聚(萘二甲酸乙二酯)、聚碳酸酯或聚(偏二氯乙烯)構成之透明聚酯膜。 Particularly useful substrates are those which have been surface treated as described above or which have not been surface treated as described above, from poly(ethylene terephthalate), poly(ethylene naphthalate), polycarbonate or poly(poly) A transparent polyester film composed of dichloroethylene).

在一些實施例中，可將第一聚合物乳膠及第二聚合物乳膠混合，在基材上形成經乾燥之底塗層以黏著具有使用非水性可光固化組合物形成之細線之圖案化材料。該第一聚合物乳膠可包含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。該第二聚合物乳膠可包含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。除此之外，該混合物之乾燥塗層可具有至少15%且至多(含)50%之表面極性。 In some embodiments, the first polymer latex and the second polymer latex may be mixed to form a dried undercoat layer on the substrate to adhere the patterned material having the fine lines formed using the non-aqueous photocurable composition. . The first polymer latex can comprise a first polymer and a first surfactant such that the dried coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex can comprise a second polymer and a second surfactant such that the dried coating of the second polymer latex has a surface polarity of less than or equal to 27%. In addition to this, the dried coating of the mixture may have a surface polarity of at least 15% and up to 50%.

本文中所述之該第一及第二聚合物中之至少一者包含含有至少部分地衍生自(甲基)丙烯酸縮水甘油酯(意指丙烯酸縮水甘油酯、甲基丙烯酸縮水甘油酯或二者)之重複單元之乙烯基聚合物，及在大多數實施例中，該第一及第二聚合物各至少部分地衍生自(甲基)丙烯酸縮水甘油酯。此外，該第一聚合物及第二聚合物中之至少一者係可交聯的，且可諸如在基材之乾燥或各種熱處理期間例如於塗覆至適宜支撐件後交聯。 At least one of the first and second polymers described herein comprises at least partially derived from glycidyl (meth)acrylate (meaning glycidyl acrylate, glycidyl methacrylate or both) The vinyl polymer of the repeating unit, and in most embodiments, the first and second polymers are each at least partially derived from glycidyl (meth)acrylate. Additionally, at least one of the first polymer and the second polymer is crosslinkable and can be crosslinked, such as during drying of the substrate or various heat treatments, such as after application to a suitable support.

尤其可用的第一聚合物為至少部分地衍生自一或多種具有縮水甘油基官能基之烯系不飽和可聚合單體之乙烯基聚合物，諸如丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油酯。因此，該第一聚合物可為衍生自(甲基)丙烯酸縮水甘油酯之均聚物，但其更可能為衍生自(甲基)丙烯酸縮水甘油酯及一或多種其他烯系不飽和可聚合單體之共聚物。術 語「縮水甘油基」係指含有連接至具有1至4個碳原子之烷基(亦可進一步取代之直鏈或分支鏈烷基)(諸如甲基、乙基、異丙基及第三丁基)之環氧乙烷環之基團。 Particularly useful first polymers are vinyl polymers derived at least in part from one or more ethylenically unsaturated polymerizable monomers having a glycidyl functional group, such as glycidyl acrylate and glycidyl methacrylate. Thus, the first polymer may be a homopolymer derived from glycidyl (meth)acrylate, but it is more likely to be derived from glycidyl (meth)acrylate and one or more other ethylenically unsaturated polymerizable a copolymer of monomers. Operation The term "glycidyl" refers to an alkyl group (which may be further substituted with a straight or branched alkyl group) having one to four carbon atoms (such as methyl, ethyl, isopropyl and tributyl). a group of the oxirane ring of the group).

該第一聚合物尤其以使一或多種(甲基)丙烯酸縮水甘油酯與一或多種(甲基)丙烯酸烷酯共聚合方式設計得到，其中該酯烷基具有至少2個碳原子，包括(但不限於)丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸環己酯、甲基丙烯酸環己酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸烯丙酯、甲基丙烯酸羥乙酯、丙烯酸羥乙酯及熟悉此項技術者將輕易明瞭之其他者。尤其可用的共單體為(甲基)丙烯酸烷酯，其中該酯烷基具有至少4個碳原子，包括(但不限於)丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯及甲基丙烯酸環己酯。 The first polymer is especially designed by copolymerizing one or more glycidyl (meth)acrylates with one or more alkyl (meth)acrylates, wherein the ester alkyl group has at least 2 carbon atoms, including But not limited to) ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, methyl Allyl acrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate and others familiar with the art will readily recognize others. Particularly useful comonomers are alkyl (meth)acrylates wherein the ester alkyl group has at least 4 carbon atoms including, but not limited to, n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, N-hexyl acrylate and cyclohexyl methacrylate.

該第二聚合物乳膠可包含一或多種第二聚合物及一或多種第二表面活性劑(述於下文)，使得該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。 The second polymer latex may comprise one or more second polymers and one or more second surfactants (described below) such that the dried coating of the second polymer latex has less than or equal to 28% or less or Equal to 27% of the surface polarity.

尤其可用的第二聚合物為至少部分地衍生自一或多種具有縮水甘油基官能基之烯系不飽和可聚合單體之乙烯基聚合物，諸如(甲基)丙烯酸縮水甘油酯，例如丙烯酸縮水甘油酯及甲基丙烯酸縮水甘油酯，如上文針對第一聚合物所述。因此，該第二聚合物可為衍生自(甲基)丙烯酸縮水甘油酯之均聚物或衍生自(甲基)丙烯酸縮水甘油酯及一或多種其他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。 Particularly useful second polymers are vinyl polymers derived at least in part from one or more ethylenically unsaturated polymerizable monomers having a glycidyl functional group, such as glycidyl (meth)acrylate, such as acrylic acid shrinkage Glycerides and glycidyl methacrylate as described above for the first polymer. Thus, the second polymer may be a homopolymer derived from glycidyl (meth)acrylate or a copolymer derived from glycidyl (meth)acrylate and one or more other ethylenically unsaturated polymerizable monomers. . The term "glycidyl" is defined above.

該第二聚合物尤其藉由使一或多種(甲基)丙烯酸縮水甘油酯與一或多種共單體(諸如一或多種(甲基)丙烯酸烷酯)共聚合設計得到，其中該酯烷基具有至少2個碳原子，包括(但不限於)丙烯酸乙酯、甲基丙烯酸乙酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸環己酯、甲 基丙烯酸環己酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、甲基丙烯酸烯丙酯、甲基丙烯酸羥乙酯、丙烯酸羥乙酯及熟悉此項技術者將輕易明瞭之其他者。尤其可用的共單體為(甲基)丙烯酸烷酯，其中該酯烷基具有至少4個碳原子，諸如丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸正己酯、甲基丙烯酸正己酯及甲基丙烯酸環己酯。 The second polymer is designed, in particular, by copolymerizing one or more glycidyl (meth)acrylates with one or more comonomers, such as one or more alkyl (meth)acrylates, wherein the ester alkyl group Has at least 2 carbon atoms, including but not limited to ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, A Cyclohexyl acrylate, lauryl acrylate, lauryl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and others familiar with the art will readily recognize others. Particularly useful comonomers are alkyl (meth)acrylates wherein the ester alkyl group has at least 4 carbon atoms, such as n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, and Cyclohexyl methacrylate.

該第一聚合物乳膠包含一或多種第一表面活性劑，其各為烷基磺酸鈉鹽，其中該烷基具有至少10個碳原子。例如，該第一表面活性劑可為α-烯烴(C₁₄-C₁₆)磺酸鈉，或該第一表面活性劑可為由R-CH₂-CH=CH-CH₂-S(=O)₂O^-Na⁺表示之化合物(其中R為C₁₀、C₁₁或C₁₂烴基)或此等具有為C₁₀至C₁₂烴基中任一者之不同R基之化合物之混合物。一種考用的含有第一表面活性劑之市售產品為Rhodacal^® A246L(可例如從Rhodia獲得)。若需要則可使用此等第一表面活性劑之混合物。 The first polymer latex comprises one or more first surfactants, each of which is an alkyl sulfonate sodium 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₎ sulfonate, or the first surfactant may be a _{R-CH 2 -CH = CH-} CH 2 -S (= O a compound represented by ₂ O ^- Na ⁺ (wherein R is a C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon group) or a mixture of such compounds having a different R group which is any one of C ₁₀ to C ₁₂ hydrocarbon groups. One kind of test with a commercial product containing a first surface active agents as Rhodacal ^® A246L (available, for example from Rhodia). Mixtures of such first surfactants can be used if desired.

該第二聚合物乳膠包含一或多種第二表面活性劑，其各為具有至少3個環氧乙烷單元之烷基酚硫酸銨鹽。例如，該第二表面活性劑可為硫酸聚乙氧基壬基酚之銨鹽，或該第二表面活性劑可由R'-苯基-(O-CH₂CH₂)_n-S(=O)O₂ ^-NH₄ ⁺表示，其中R'為C₈至C₁₂烴基及n為至少3且至多(含)10，或n更可能為至少3且至多(含)6。一種可用的含有第二表面活性劑之市售產品為Rhodapex^® CO-436(可例如從Rhodia獲得)。若需要則可使用此等第二表面活性劑之混合物。 The second polymer latex comprises 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 salt of polyethoxylated nonylphenol sulfate, or the second surfactant may be R'-phenyl-(O-CH ₂ CH ₂ ) _n -S (=O ) O ₂ ^- NH ₄ ^+, where R 'a C ₈ to C ₁₂ hydrocarbon group, and n is at least 3 and up to (including) 10, or at least more likely to be n 3 and up (with) 6. One useful commercial product containing the second surfactant is Rhodapex ^® CO-436 (available, for example from Rhodia). A mixture of such second surfactants can be used if desired.

該第一聚合物乳膠及第二聚合物乳膠各可使用乳液聚合製備或呈顆粒乳液聚合產物之水性分散液獲得。 The first polymer latex and the second polymer latex can each be obtained by emulsion polymerization or as an aqueous dispersion of a particulate emulsion polymerization product.

可用的基材可具有所需的根據由其形成之物件之最終用途而定之乾厚。例如，基材乾厚(包含所有處理及輔助層)可為至少0.001mm且至多(含)10mm，及尤其就透明聚合膜而言，基材乾厚可為至少0.008mm且至多(含)0.2mm。 Useful substrates can have the desired dry thickness depending on the end use of the article from which they are formed. For example, the dry thickness of the substrate (including all of the treatment and auxiliary layers) can be at least 0.001 mm and up to 10 mm, and especially for transparent polymeric films, the dry thickness of the substrate can be at least 0.008 mm and at most 0.2. Mm.

用於製備本文中所述之物件之基材可呈各種形式，諸如(例如)任 何尺寸或形狀之個別薄片及連續網(諸如，適用於捲繞式操作之透明聚合基材之連續網，包括透明聚酯網)提供。此等連續聚合物網可分成或形成可用於形成相同或不同經光固化圖案之個別第一、第二及額外部分。 The substrate used to prepare the articles described herein can be in various forms such as, for example, any Individual sheets and continuous webs of any size or shape, such as a continuous web suitable for use in a roll-to-roll transparent polymeric substrate, including a clear polyester web, are provided. These continuous polymeric webs can be divided or formed into individual first, second and additional portions that can be used to form the same or different photocurable patterns.

在施覆非水性可光固化組合物後，可藉由不會不利影響其餘組分或過早地引起光固化之乾燥或預烘焙程序移除有機稀釋劑之任何惰性有機溶劑。可用的乾燥條件可係低為室溫持續短到5秒且至多(含)數小時，取決於製造製程。在大多數製程(諸如下文所述之捲繞式製程)中，乾燥條件可係，於足夠高的溫度下在至少5秒以內移除惰性有機溶劑之至少90%。 After application of the non-aqueous photocurable composition, any inert organic solvent that removes the organic diluent can be removed by a drying or pre-baking procedure that does not adversely affect the remaining components or prematurely cause photocuring. Useful drying conditions can be as low as room temperature for as little as 5 seconds and up to (inclusive) hours, depending on the manufacturing process. In most processes, such as the roll-to-roll process described below, the drying conditions may be such that at least 90% of the inert organic solvent is removed in at least 5 seconds at a sufficiently high temperature.

任一所施覆的均勻非水性可光固化組合物層可具有至少0.1μm且至多(含)10μm或通常至少0.2μm且至多(含)1μm之乾厚，及最佳乾厚可根據所得均勻經光固化層之所欲用途定製，該層一般具有約與未光固化非水性可光固化組合物之均勻層相同之乾厚。此一均勻層可施覆至基材之兩個(相對)支撐側，該等均勻層可具有相同或不同化學組成或乾厚。 Any of the uniformly applied non-aqueous photocurable composition layers may have a dry thickness of at least 0.1 μm and at most 10 μm or usually at least 0.2 μm and at most 1 μm, and the optimum dry thickness may be uniform according to the obtained Customized for the intended use of the photocurable layer, the layer typically has a dry thickness that is about the same as the uniform layer of the non-curable non-aqueous photocurable composition. This uniform layer can be applied to the two (opposite) support sides of the substrate, which may have the same or different chemical composition or dry thickness.

非水性可光固化組合物之任一所施覆的圖案可包含具有至少0.2μm且至多(含)100μm或通常至少5μm且至多(含)10μm之平均乾寬之線之網格(或其他形狀，包括圓形或不規則網狀結構)，及最佳乾寬可根據所得均勻經光固化層之所欲用途定製，該圖案一般具有尺寸基本上與未光固化網格線相同之經光固化且導電之網格線。 The pattern applied by any of the non-aqueous photocurable compositions may comprise a grid (or other shape) having a line having an average dry width of at least 0.2 μm and at most 100 μm or usually at least 5 μm and at most 10 μm. , including circular or irregular mesh structures, and the optimum dry width can be tailored to the desired use of the resulting uniform photocurable layer, which typically has the same amount of light as the uncured grid lines. Cured and conductive grid lines.

因此，本發明可用於提供包含基材及均勻層或由本發明之非水性可光固化組合物構成之圖案之物件，其中此等物件可視為「前驅」物件，意指其等一般為先於光固化前所形成的物件。於光固化非水性可光固化組合物後，前驅物件現視為中間(經光固化)物件。 Accordingly, the present invention can be used to provide articles comprising a substrate and a uniform layer or a pattern of the non-aqueous photocurable composition of the present invention, wherein such articles can be considered as "precursor" articles, meaning that they are generally preceded by light. The object formed before curing. After photocuring the non-aqueous, photocurable composition, the precursor article is now considered an intermediate (photocured) article.

在一些實施例中，該相同或不同非水性可光固化組合物可以適 宜方法施覆於基材之兩個支撐側(平面表面)上以形成「雙覆層(duplex)」或雙側前驅物件，及各施覆的非水性可光固化組合物可呈相同或不同均勻層或預定圖案形式。 In some embodiments, the same or different non-aqueous photocurable compositions may be suitable Preferably, the method is applied to two support sides (planar surfaces) of the substrate to form a "duplex" or a double-sided precursor, and each of the applied non-aqueous photocurable compositions may be the same or different. A uniform layer or a predetermined pattern.

在許多實施例中，使用衍生自柔版印刷板前驅物之浮凸元件(諸如彈性浮凸元件(柔版印刷部件))於基材(例如，呈捲繞式連續網)之一或兩個(相對)支撐側上施覆非水性可光固化組合物之圖案，其中許多元件係此項技術中已知的及某些可例如以Cyrel^® Flexographic Photopolymer Plates從DuPont及Flexcel SR及NX Flexographic plates及Flexcel Direct Flexographic plates從Eastman Kodak Company購得。 In many embodiments, one or both of the substrate (eg, in a wound continuous web) is used with a relief element (such as an elastic relief element (flexographic printing member)) derived from a flexographic printing plate precursor. (relative) non-aqueous coating applied to a support photocurable composition of the pattern on the upper side, wherein a number of system elements known in the art and may be, for example, in certain Cyrel ^® Flexographic Photopolymer Plates from DuPont and Flexcel SR and NX Flexographic plates and Flexcel Direct Flexographic plates are commercially available from Eastman Kodak Company.

尤其可用的彈性浮凸元件係衍生自柔版印刷板前驅物及柔版印刷套筒前驅物，其各可經適當圖像化(且視需要進行處理)以提供用於「印刷」或施覆適宜圖案之浮凸元件。 Particularly useful elastic relief elements are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be suitably imaged (and processed as needed) to provide for "printing" or application. A embossed component of a suitable pattern.

例如，可用的彈性浮凸元件可由一或多個具有或不具有基材之彈性層構成，其中可使用適宜之成像裝置產生浮凸圖像。 For example, useful elastic relief elements can be constructed from one or more elastic layers with or without a substrate, wherein a suitable image forming device can be used to create the relief image.

例如，具有構成最上層浮凸表面之浮凸層及具有相對從最上層浮凸表面算起至少50μm之平均浮凸圖像深度(圖案高度)或通常具有至少100μm之平均浮凸圖像深度之彈性浮凸元件(例如，柔版印刷部件)可例如如美國專利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)中所述由成像曝光彈性浮凸元件前驅物(諸如柔版印刷部件前驅物)中之彈性可光聚合層製得。此等彈性可光聚合層可通過適宜罩幕影像(mask image)圖像化以提供彈性浮凸元件(例如，柔版印刷板或柔版印刷套筒)。在一些實施例中，包含浮凸圖案之浮凸層可配置於如所述Ali等人專利中所描述之適宜基材上。其他可用的材料及用於提供彈性浮凸圖像之圖像形成方法(包括顯影)亦述於所述Ali等人專利中。浮凸層(及柔版印刷部件)可不同以提供非水性可光固化組合物之不同圖案至基材之相同或相對支 撐側。 For example, having an embossed layer constituting the uppermost embossed surface and having an average embossed image depth (pattern height) of at least 50 μm from the uppermost embossed surface or generally having an average embossed image depth of at least 100 μm Elastic relief elements (e.g., flexographic printing elements) may be elastically floated by imagewise exposure as described in U.S. Patent Nos. 7,799,504 (Zwadlo et al.) and 8,142,987 (Ali et al.), and U.S. Patent Application Publication No. 2012/0237871 (Zwadlo). An elastic photopolymerizable layer in a convex element precursor such as a flexographic printing member precursor. These elastic photopolymerizable layers can be imaged by a suitable mask image to provide an elastic relief element (eg, a flexographic printing plate or a flexographic printing sleeve). In some embodiments, the relief layer comprising the relief pattern can be disposed on a suitable substrate as described in the Ali et al. patent. Other useful materials and image forming methods (including development) for providing elastic relief images are also described in the Ali et al. patent. The relief layer (and the flexographic printing member) can be varied to provide the same pattern or relative support of the different patterns of the non-aqueous photocurable composition to the substrate. Support side.

在其他實施例中，如例如美國專利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)中所述，使用或不使用一體式遮罩，自可直接(或切除)雷射雕刻之彈性體浮凸元件前驅物提供彈性浮凸元件。可在無可光聚合彈性材料所需要之溶劑處理或顯影的情況下製得經直接雕刻之浮凸元件。 In other embodiments, for example, U.S. Patent Nos. 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 No. 2002/0136969 (Hiller et al.), 2003/0129530 (Leinenback) Etc., 2003/0136285 (Telser et al.), 2003/0180636 (Kanga et al.) and 2012/0240802 (Landry-Coltrain et al.), with or without an integrated mask, can be directly (or The laser engraved elastomeric relief element precursor is provided with a resilient relief element. The directly engraved embossed elements can be produced without the solvent treatment or development required for the photopolymerizable elastomeric material.

當使用彈性浮凸元件時，可以適宜方法將非水性可光固化組合物施覆至彈性浮凸元件中之最上層浮凸表面(凸起的表面)。此施覆可使用適宜裝置達成且希望儘量少地塗覆至浮凸凹入部之側(傾斜部分)或凹入上。可使用網紋輥系統或其他輥施覆系統(特別是低體積網紋輥，低於25億立方微米/平方英寸(63.5億立方微米/平方公分))及相關削刀(skive knives)。可藉由控制黏度或厚度或選擇適宜之施覆裝置達成最佳計量非水性可光固化組合物至最上層浮凸表面上。 When a resilient relief element is used, the non-aqueous photocurable composition can be applied to the uppermost raised surface (raised surface) of the elastic relief element in a suitable manner. This application can be achieved using suitable means and it is desirable to apply as little as possible to the side (inclined portion) or recess of the relief recess. An anilox roll system or other roll application system (especially a low volume anilox roll, less than 2.5 billion cubic micrometers per square inch (6.35 billion cubic micrometers per square centimeter)) and associated knives can be used. The optimal metering of the non-aqueous photocurable composition can be achieved by controlling the viscosity or thickness or selecting a suitable application device to the uppermost relief surface.

例如，非水性可光固化組合物可經調配以具有針對此塗覆之至少1cps(厘泊)且至多(含)5000cps或至少1cps至至多(含)1500cps之黏度。浮凸圖像上非水性可光固化組合物之厚度一般受限於足量，如此可輕易地轉移至基材，但施覆期間不會太多流過凹入中之彈性浮凸元件之邊緣。 For example, the non-aqueous photocurable composition can be formulated to have a viscosity of at least 1 cps (centipoise) and at most (inclusive) 5000 cps or at least 1 cps up to (inclusive) 1500 cps for the coating. The thickness of the non-aqueous photocurable composition on the embossed image is generally limited by a sufficient amount so that it can be easily transferred to the substrate, but does not flow too much through the edge of the concave embossed element during application. .

因此，可自網紋或其他輥給墨系統以一定量進料非水性可光固化組合物以獲得各印刷前驅物件(呈均勻層或圖案)。在一個實施例 中，可使用第一輥以將非水性可光固化組合物自「油墨」盤或計量系統轉移至計量輥或網紋輥。該非水性可光固化組合物一般經計量以當在將其自網紋輥轉移至印刷板滾筒時達成均勻厚度。當呈連續網之基材通過捲繞式處理系統自印刷板滾筒移至壓印滾筒時，壓印滾筒施加壓力至將非水性可光固化組合物之圖像自彈性浮凸元件轉移至基材之印刷板滾筒。 Thus, the non-aqueous photocurable composition can be fed to the ink system from a web or other roll feed system to obtain each printed precursor (in a uniform layer or pattern). In one embodiment In this case, a first roll can be used to transfer the non-aqueous photocurable composition from the "ink" tray or metering system to the metering roll or anilox roll. The non-aqueous, photocurable composition is typically metered to achieve a uniform thickness as it is transferred from the anilox roll to the printing plate cylinder. When the substrate in the continuous web is moved from the printing plate cylinder to the impression cylinder by the wound processing system, the impression cylinder applies pressure to transfer the image of the non-aqueous photocurable composition from the elastic relief element to the substrate. Printing plate cylinder.

在已施覆非水性可光固化組合物至彈性浮凸元件之最上層浮凸表面(或凸起的表面)後，移除任何惰性有機溶劑之至少25重量%以在浮凸圖像之最上層浮凸表面上形成更黏沉積物可係有用的。惰性有機溶劑之此移除可以任何方法，例如，使用熱空氣噴射機，在室溫下蒸發，或在烘箱中於高溫下加熱，或此項技術中已知的用於移除溶劑之其他方法達成。 After the non-aqueous photocurable composition has been applied to the uppermost raised surface (or raised surface) of the elastic relief element, at least 25% by weight of any inert organic solvent is removed to maximize the relief image It may be useful to form a more viscous deposit on the upper embossed surface. This removal of the inert organic solvent can be by any method, for example, using a hot air jet, evaporating at room temperature, or heating at elevated temperatures in an oven, or other methods known in the art for removing solvent. Achieved.

當前驅物件中之非水性可光聚合組合物呈網格線或其他形狀之均勻層或預定圖案於基材上(於基材之一或兩個支撐側上)時，即可用如上所述來自適宜光源諸如螢光燈或LED之適宜輻射輻射以在基材上提供經光固化層或一或多個經光固化圖案。例如，光固化可藉由使用具有至少190nm且至多(含)700nm之波長(λ_max)及至少1,000微瓦/cm²且至多(含)80,000微瓦/cm²之強度之UV-可見光輻射達成。用於產生此輻射之輻射系統可由例如呈1至50個放電燈形式之一或多個紫外線燈，例如，氙、金屬鹵化物、金屬弧(諸如，具有自數毫米至約10個大氣壓之所需操作壓力之低、中或高壓汞蒸氣放電燈)組成。該等燈可包含能夠透射至少190nm且至多(含)700nm或通常至少240nm且至多(含)450nm之波長之光之外殼。該燈外殼可由石英(諸如spectrocil或Pyrex)組成。可用於提供紫外線輻射之典型燈為(例如)中壓汞弧，諸如GE H3T7弧及Hanovia 450W弧燈。可使用各種燈之組合進行光固化，該等燈中一部分或全部可在惰性氛圍中操作。當使用UV燈時， 照射於基材(或所施覆的層或圖案)上之輻射通量衝擊可設計為足以實現在1至20秒以內以連續方法(例如以捲繞式操作)足夠快速地光固化所施覆的非水性可光固化組合物。 When the non-aqueous photopolymerizable composition in the current article is in a uniform layer or a predetermined pattern of grid lines or other shapes on the substrate (on one or both of the support sides), it can be obtained as described above. Suitable radiation radiation, such as a fluorescent lamp or LED, is suitable for providing a photocured layer or one or more photocured patterns on the substrate. For example, by using the photocurable may have at least 190nm and up (with) the wavelength of 700 nm (λ _max), and at least 000 microwatts / cm ² and up to (including) a UV-visible light intensity of 80,000 microwatts / cm ² of radiation reached . The radiation system for generating such radiation may be, for example, in the form of one to 50 discharge lamps or a plurality of ultraviolet lamps, for example, helium, metal halides, metal arcs (such as having from a few millimeters to about 10 atmospheres) It consists of low, medium or high pressure mercury vapor discharge lamps that require operating pressure. The lamps may comprise an outer casing capable of transmitting light having a wavelength of at least 190 nm and at most 700 nm or typically at least 240 nm and at most 450 nm. The lamp housing can be composed of quartz such as spectrocil or Pyrex. Typical lamps that can be used to provide ultraviolet radiation are, for example, medium pressure mercury arcs, such as GE H3T7 arcs and Hanovia 450W arc lamps. Photocuring can be carried out using a combination of various lamps, some or all of which can be operated in an inert atmosphere. When a UV lamp is used, the radiant flux impingement on the substrate (or applied layer or pattern) can be designed to be sufficiently fast to achieve a continuous process (eg, in a roll-up operation) within 1 to 20 seconds. A non-aqueous photocurable composition applied by photohardening.

用於光固化中之LED輻射裝置可具有350nm或更大之峰值發射波長。LED裝置可包含兩種或更多種類型之具有不同的大於或等於350nm之峰值發射波長之元件。具有350nm或更大之峰值發射波長且具有紫外線-發光二極體(UV-LED)之LED裝置之商業實例為可從Nichia Corporation獲得之NCCU-033。 The LED radiation device used in photocuring may have a peak emission wavelength of 350 nm or more. The LED device can comprise two or more types of elements having different peak emission wavelengths greater than or equal to 350 nm. A commercial example of an LED device having a peak emission wavelength of 350 nm or greater and having an ultraviolet-emitting diode (UV-LED) is NCCU-033 available from Nichia Corporation.

此針對前驅物件之輻射獲得包含基材(例如，個別薄片或連續網)且其上具有衍生自基材之一或兩個支撐側上非水性可光固化組合物之經光固化層或一或多個經光固化圖案中任一者之中間物件。 This radiation for the precursor article results in a substrate comprising a substrate (eg, individual sheets or continuous webs) having a photocured layer derived from one or both of the support side of the non-aqueous photocurable composition or An intermediate object of any of the plurality of photocured patterns.

所得的中間物件可以此形式用於一些應用中，但在大多數實施例中，該等中間物件係經進一步處理以在均勻經光固化層或經光固化圖案上併入導電金屬，其各包含用為用於例如使用無電金屬電鍍程序進一步施覆導電金屬之「晶種」材料之經碳塗覆的金屬顆粒。例如，如上所述之無電「晶種」經碳塗覆的金屬顆粒可包括可無電電鍍銅、鉑、鈀或其他的如下文所述之金屬之銀、鈀或鉑顆粒。 The resulting intermediate articles may be used in some applications in some applications, but in most embodiments, the intermediate articles are further processed to incorporate conductive metals on a uniform photocured layer or a photocured pattern, each comprising The carbon coated metal particles are used to further coat the "seed" material of the conductive metal, for example, using an electroless metal plating process. For example, the electroless "seed" carbon coated metal particles as described above may comprise silver, palladium or platinum particles which may be electrolessly plated with copper, platinum, palladium or other metals as described below.

一種有用的方法係在印刷站中使用呈堆疊之多個柔版印刷板(例如，依上文所述製得)，其中各堆疊具有其自身印刷板滾筒而使用各柔版印刷版以印刷個別基材，或可使用印刷板之堆疊以印刷連續聚合物網中(一或兩個支撐側上)之多個部分。該相同或不同非水性可光固化組合物可使用多個柔版印刷板「印刷」或施覆至此基材(相同或相對支撐側上)。 One useful method is to use a plurality of flexographic printing plates in a stack (for example, as described above) in a printing station, wherein each stack has its own printing plate cylinder and each flexographic printing plate is used to print individual The substrate, or a stack of printing plates, can be used to print portions of the continuous polymer web (on one or both support sides). The same or different non-aqueous photocurable compositions can be "printed" or applied to the substrate (on the same or opposite support side) using a plurality of flexographic printing plates.

在其他實施例中，中央加壓滾筒可併與安裝在印刷壓力機框架上之單一加壓滾筒一起使用。隨著基材(或接收元件)進入印刷壓力機框架，其與加壓滾筒接觸及用非水性可光固化組合物印刷適宜之圖 案。或者，可使用印刷站配置在水平線上且藉由共同線軸件驅動之線上柔版印刷製程。該等印刷站可偶聯至曝光站、切割站、摺疊機及其他後處理設備。熟悉此項技術者可利用可在此項技術中取得的資訊輕易地判定其他適用之設備及站之配置。例如，WO 2013/063084(Jin等人)中描述圓形(in-the-round)成像製程。 In other embodiments, the central pressure roller can be used with a single pressure roller mounted on the frame of the printing press. As the substrate (or receiving element) enters the printing press frame, it is in contact with the pressurized roller and printed with a non-aqueous photocurable composition. case. Alternatively, an online flexographic process in which the printing station is disposed on a horizontal line and driven by a common spool member can be used. These printing stations can be coupled to exposure stations, cutting stations, folding machines and other aftertreatment equipment. Those skilled in the art can easily determine the configuration of other applicable devices and stations using information available in this technology. For example, an in-the-round imaging process is described in WO 2013/063084 (Jin et al.).

可立刻將本文中所述之具有所述經光固化之含有經分散之經碳塗覆的金屬顆粒之圖案之中間物件浸泡於水基無電金屬電鍍浴液或溶液中，或可僅將中間物件(例如，呈捲起的連續網)連同經光固化之圖案儲存以用於在稍後時間使用。 The intermediate member having the photocured pattern containing the dispersed carbon-coated metal particles described herein may be immediately immersed in a water-based electroless metal plating bath or solution, or only the intermediate member may be (eg, a continuous web that is rolled up) is stored along with the photocured pattern for use at a later time.

例如，可使各中間物件與併入經光固化圖案中之經碳塗覆的金屬顆粒中的金屬相同或不同的無電電鍍金屬接觸。在大多數實施例中，然而，無電電鍍金屬為與用於分散在經光固化之圖案中之經碳塗覆的金屬顆粒中之金屬不同的金屬。 For example, each intermediate article can be contacted with an electroless plating metal that is the same or different from the metal incorporated into the carbon coated metal particles in the photocurable pattern. In most embodiments, however, the electroless plating metal is a different metal than the metal used to disperse the carbon coated metal particles in the photocured pattern.

此時可使用將可能無電「電鍍」於經碳塗覆的金屬顆粒上之任何金屬，但在大多數實施例中，無電電鍍金屬可為例如銅(II)、銀(I)、金(IV)、鈀(II)、鉑(II)、鎳(II)、鉻(II)及其組合。銅(II)、銀(I)及鎳(II)為特別適於經碳塗覆的銀、銅或鈀顆粒之無電電鍍金屬。 Any metal that may be "electroplated" onto the carbon coated metal particles may be used at this point, but in most embodiments, the electroless plating metal may be, for example, copper (II), silver (I), gold (IV). ), palladium (II), platinum (II), nickel (II), chromium (II), and combinations thereof. Copper (II), silver (I) and nickel (II) are electroless plated metals that are particularly suitable for carbon coated silver, copper or palladium particles.

該一或多種無電電鍍金屬可以基於總溶液重量計至少0.01重量%且至多(含)20重量%的量存於水基無電電鍍浴液或溶液中。 The one or more electroless plating 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 20% by weight, based on the total solution weight.

可使用已知的溫度及時間條件進行無電電鍍，因為此等條件係各種教科書及科學文獻中所熟知的。亦已知於水基無電電鍍溶液中包含各種添加劑(諸如金屬錯合劑或穩定劑)。可利用時間及溫度差以改變金屬無電電鍍厚度或金屬無電電鍍沉積速率。 Electroless plating can be carried out using known temperature and time conditions, as such 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 water-based electroless plating solutions. Time and temperature differences can be utilized to vary the metal electroless plating thickness or metal electroless plating deposition rate.

一種可用的水基無電電鍍溶液或浴液為可包含甲醛作為還原劑之無電銅(II)電鍍浴液。乙二胺四乙酸(EDTA)或其鹽可呈銅錯合劑存在。例如，銅無電電鍍可在室溫下根據所需沉積速率及電鍍速率及電 鍍金屬厚度進行數秒至至多數小時。 One useful water-based electroless plating solution or bath is an electroless copper (II) plating bath which may 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 be used at room temperature depending on the desired deposition rate and plating rate and electricity. The metal plating thickness is a few seconds up to most hours.

其他可用的水基無電電鍍溶液或浴液包括銀(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水基無電浴液或溶液(諸如，Mallory等人在Electroless Plating：Fundamentals and Applications 1990中所述之其等)。 Other useful water-based electroless plating solutions or baths include silver (I) with EDTA and sodium tartrate, silver (I) with ammonia and glucose, copper (II) with EDTA and dimethylamine borane, copper (II) and Citrate and hypophosphite, nickel (II) and lactic acid, acetic acid and hypophosphite and other industry standard water-based electroless baths or solutions (such as those described by Mallory et al. in Electroless Plating: Fundamentals and Applications 1990) Wait).

於無電電鍍程序以在基材一或相對支撐側之一或多個部分上提供導電金屬圖案之後，可自水基無電電鍍浴液或溶液移去所得產品物件且可使用蒸餾水或去離子水或另一水基溶液洗滌以移除任何殘留的無電電鍍化學品。此時，經無電電鍍之金屬一般係穩定的且可用於其所欲目的以形成各種具有所需導電金屬網格線或導電金屬金屬連接器(或BUS連接器或電極)之導電物件。 After the electroless plating process is performed to provide a conductive metal pattern on one or more portions of the substrate or the opposite support side, the resulting product article may be removed from the water-based electroless plating bath or solution and distilled or deionized water or Another water based solution is washed to remove any residual electroless plating chemicals. At this point, the electrolessly plated metal is generally stable and can be used for its intended purpose to form a variety of electrically conductive articles having desired conductive metal grid lines or conductive metal metal connectors (or BUS connectors or electrodes).

在一些實施例中，所得產品物件可如例如US 2014/0071356(Petcavich)之[0048]中所述用水在室溫下或如WO 2013/169345(Ramakrishnan等人)之[0027]中所述用去離子水在低於70℃之溫度下沖洗或洗滌。 In some embodiments, the resulting product item can be used with water at room temperature or as described in WO 2013/169345 (Ramakrishnan et al.) [0027] as described in, for example, US 2014/0071356 (Petcavich) [0048] The deionized water is rinsed or washed at a temperature below 70 °C.

為出於視覺或耐久性原因而改變經無電電鍍之金屬之表面，可使用多種後處理，包括表面電鍍再至少另一(第三或更多)金屬(諸如鎳或銀)於經無電電鍍之金屬上(此程序有時稱為「包覆」)，或建立足以改變表面顏色及散射性質而不降低經無電電鍍之(第二)金屬之導電性之金屬氧化物、金屬硫化物或金屬硒化物層係可行的。根據用於該方法之各種包覆程序中之金屬，可能需要用呈水基晶種金屬觸媒溶液之另一晶種金屬觸媒處理經無電電鍍之金屬以促進另一金屬沉積。 In order to change the surface of the electrolessly plated metal for visual or durability reasons, various post treatments may be used, including surface plating followed by at least one other (third or more) metal (such as nickel or silver) for electroless plating. On metal (this process is sometimes referred to as "coating"), or to establish a metal oxide, metal sulfide or metal selenium sufficient to alter the surface color and scattering properties without reducing the conductivity of the (second) metal that is electrolessly plated. The layer is feasible. Depending on the metal used in the various coating procedures used in the process, it may be desirable to treat the electrolessly plated metal with another seed metal catalyst in a water-based seed metal catalyst solution to promote deposition of another metal.

此外，可使用相同或不同條件依序進行多次水基無電金屬電鍍溶液處理。亦可在適宜情況下於室溫或低於70℃之溫度下進行連續洗滌或沖洗步驟。 In addition, multiple water-based electroless metal plating solution treatments may be performed sequentially using the same or different conditions. A continuous washing or rinsing step can also be carried out at room temperature or below 70 ° C where appropriate.

另外，可使用相同或不同無電電鍍金屬及相同或不同無電電鍍條件依序多次進行無電電鍍程序。 Alternatively, the electroless plating process can be performed multiple times using the same or different electroless plating metals and the same or different electroless plating conditions.

適用於進行本發明之一些實施例之方法及設備的一些細節述於例如US 2014/0071356(如上文所述)及WO 2013/169345(如上文所述)中。適用於尤其以捲繞方法製造導電物件之製造系統的其他細節提供於WO2014/070131(在2012年10月29日由Petcavich及Jin申請)中。 Some details of methods and apparatus suitable for carrying out some embodiments of the invention are described, for example, in US 2014/0071356 (as described above) and WO 2013/169345 (as described above). Further details of a manufacturing system suitable for the manufacture of electrically conductive articles, in particular by a winding method, are provided in WO 2014/070131 (filed on October 29, 2012 by Petsavich and Jin).

可用於進行本發明之設備及步驟特徵之另一系統述於美國序號14/146,867(在2014年1月3日由Shifley申請)中。 Another system that can be used to carry out the apparatus and step features of the present invention is described in U.S. Serial No. 14/146,867, filed on Jan. 3, 2014 by Shifley.

可在某一方法中使用本發明之非水性可光固化組合物以提供一或多種導電物件。此方法包括提供透明基材之連續網[其實例述於上文，且可尤其為聚(對苯二甲酸乙二酯)之連續網]。 The non-aqueous photocurable compositions of the present invention can be used in a method to provide one or more electrically conductive articles. This method includes providing a continuous web of transparent substrates [examples of which are described above, and may in particular be continuous webs of poly(ethylene terephthalate)].

該方法亦包括在透明基材之連續網之至少第一部分上形成包含可光固化組分及如上所述之經分散之經碳塗覆的金屬顆粒之非水性可光固化組合物(如本文中所述)之可光固化圖案。接著光固化可光固化圖案以在連續網之第一部分上形成經光固化之圖案，該經光固化之圖案包含經分散之經碳塗覆的金屬顆粒(如上文所述)作為晶種金屬觸媒位點。此經光固化之圖案可接著在連續網之第一部分上無電電鍍導電金屬(如上文所述)。 The method also includes forming a non-aqueous photocurable composition comprising a photocurable component and dispersed carbon coated metal particles as described above on at least a first portion of a continuous web of transparent substrate (as herein The photocurable pattern of the). The photocurable pattern is then photocured to form a photocured pattern on the first portion of the continuous web, the photocured pattern comprising dispersed carbon coated metal particles (as described above) as a seed metal contact Media spot. This photocured pattern can then be electrolessly plated with a conductive metal (as described above) on the first portion of the continuous web.

此方法可進一步包括：使用相同或不同非水性可光固化組合物在連續網之與第一部分不同的一或多個其他部分上進行如上所述之形成、光固化及無電電鍍特徵再一或多次。依此方式，可在基材之相同或不同支撐側上形成多個經光固化且無電電鍍之圖案。所得導電圖案之組成、圖案或導電率可相同，或其等之任何或所有此等特徵可全部不同(如根據客戶需要預定)。 The method may further comprise: using the same or different non-aqueous photocurable composition to form one or more of the above-described formation, photocuring, and electroless plating features on one or more other portions of the continuous web that are different from the first portion Times. In this manner, a plurality of photocurable and electroless plating patterns can be formed on the same or different support sides of the substrate. The composition, pattern or conductivity of the resulting conductive pattern may be the same, or any or all of these features may be all different (e.g., as desired by the customer).

因此，該方法可用於提供複數個前驅物件，包括： 藉由使用柔版印刷部件施覆非水性可光固化組合物至連續網之第一部分在第一部分上形成第一可光固化圖案，使該包括第一可光固化圖案之連續網前進接近曝光輻射，及由此在第一部分上形成第一經光固化圖案，藉由使用柔版印刷部件施覆相同或不同非水性可光固化組合物至連續網之第二部分在該第二部分上形成第二可光固化圖案，使該包括第二可光固化圖案之連續網前進接近曝光輻射，及由此在第二部分上形成第二經光固化圖案，視情況，使用相同或不同非水性可光固化組合物及相同或不同柔版印刷部件以類似方法在連續網之一或多個其他各別部分上形成一或多個其他經光固化圖案，及捲起該包括多個經光固化圖案之連續網，或立刻使用連續網以用於進一步處理，諸如無電電鍍。 Therefore, the method can be used to provide a plurality of precursor objects, including: Forming the first photocurable pattern on the first portion by applying the non-aqueous photocurable composition to the first portion of the continuous web using the flexographic printing member to advance the continuous web comprising the first photocurable pattern to the exposure radiation And thereby forming a first photocured pattern on the first portion, by applying the same or different non-aqueous photocurable composition to the second portion of the continuous web using the flexographic printing member to form a second portion a second photocurable pattern, the continuous web comprising the second photocurable pattern being advanced to the exposure radiation, and thereby forming a second photocured pattern on the second portion, optionally using the same or different non-aqueous light Forming the cured composition and the same or different flexographic printing members in a similar manner to form one or more other photocurable patterns on one or more other portions of the continuous web, and rolling up the plurality of photocurable patterns Continuous web, or use a continuous web immediately for further processing, such as electroless plating.

因此，該方法可進一步包括：自包括多個經光固化圖案之連續網形成多個導電物件，及將個別導電物件組裝成相同或不同個別裝置(諸如，相同或不同觸控螢幕顯示器或裝置)。 Accordingly, the method can further include forming a plurality of electrically conductive articles from a continuous web comprising a plurality of photocured patterns, and assembling the individual electrically conductive articles into the same or different individual devices (such as the same or different touch screen displays or devices) .

此方法亦可包括：無電電鍍連續網中之多個經光固化圖案各者以形成多個導電物件，該多個導電物件可由相同或不同使用者組裝成相同或不同個別裝置。該等裝置可為觸控螢幕或其他的亦包括適宜控制器、外殼及用於任何類型之所需經網路通訊之軟體之顯示器裝置。或者，該等裝置可為此觸控螢幕或其他顯示器裝置之子組件。 The method can also include electroless plating a plurality of photocurable patterns in the continuous web to form a plurality of electrically conductive articles that can be assembled into the same or different individual devices by the same or different users. Such devices may be touch screens or other display devices that also include suitable controllers, housings, and software for any type of network communication required. Alternatively, the devices can be sub-components of the touch screen or other display device.

在一些實施例中，該方法可用於製造包括觸控螢幕之裝置，該方法包括：將一或多個個別導電物件組裝成裝置外殼以形成觸控螢幕區 域，該一或多個個別導電物件各包含包含已無電電鍍至衍生自本發明之非水性可光固化組合物之經光固化圖案之導電金屬之導電圖案。 In some embodiments, the method can be used to fabricate a device including a touch screen, the method comprising: assembling one or more individual conductive articles into a device housing to form a touch screen region The one or more individual electrically conductive articles each comprise a conductive pattern comprising a conductive metal that has been electrolessly plated to a photocurable pattern derived from the non-aqueous photocurable composition of the present invention.

依照使用本發明製得之可用的產品物件可調配成包含導電金屬網格線、導電金屬連接器(電引線或BUS連接器)之適宜圖案之電容型觸控螢幕感測器。例如，可藉由印刷本發明之非水性可光固化組合物為預定圖案，接著所印刷的圖案無電電鍍如上所述之適宜金屬，形成導電金屬網格線及導電金屬連接器之圖案。 The available product items made in accordance with the present invention can be incorporated into a capacitive touch screen sensor comprising a suitable pattern of conductive metal grid lines, conductive metal connectors (electric leads or BUS connectors). For example, a pattern of conductive metal grid lines and conductive metal connectors can be formed by printing a non-aqueous photocurable composition of the present invention into a predetermined pattern, followed by electroless plating of a suitable metal as described above.

本發明提供至少以下實施例及其組合，但如熟悉此項技術者將從本發明之教示明瞭，特徵之其他組合視為屬於本發明： The present invention provides at least the following embodiments and combinations thereof, but those skilled in the art will recognize from the teachings of the present invention that other combinations of features are considered to belong to the present invention:

1. 一種含有基於非水性組合物總重量計至少10重量%的量之在有機稀釋劑中之經分散之經碳塗覆的金屬顆粒之非水性組合物，該等經分散之經碳塗覆的金屬顆粒具有等於或小於0.6μm之中值直徑，及係用具有至少2,000且至多(含)100,000之重量平均分子量(M_w)並含有含氮單元之顆粒分散劑分散，該中值直徑係使用動態光散射法測得，其中，當在該非水性組合物含有至多(含)25重量%之經分散之經碳塗覆的金屬顆粒時，其在20℃進行至少24小時的沉降測試時未呈現視覺上的沉降。 A non-aqueous composition comprising dispersed carbon coated metal particles in an organic diluent in an amount of at least 10% by weight based on the total weight of the non-aqueous composition, the dispersed carbon coated The metal particles have a median diameter equal to or less than 0.6 μm, and are dispersed by a particle dispersant having a weight average molecular weight (M _w ) of at least 2,000 and at most 100,000 and containing a nitrogen-containing unit, the median diameter system Using a dynamic light scattering method, wherein when the non-aqueous composition contains at most 25% by weight of the dispersed carbon-coated metal particles, it is not subjected to a sedimentation test at 20 ° C for at least 24 hours. Presents a visual subsidence.

2. 如實施例1之非水性組合物，其含有經分散之經碳塗覆的銀顆粒或經分散之經碳塗覆的銅顆粒、或經分散之經碳塗覆的銀顆粒及經分散之經碳塗覆的銅顆粒二者之混合物。 2. A non-aqueous composition according to embodiment 1 comprising dispersed carbon coated silver particles or dispersed carbon coated copper particles, or dispersed carbon coated silver particles and dispersed a mixture of both carbon coated copper particles.

3. 如實施例1或2之非水性組合物，其中該顆粒分散劑與該等經分散之經碳塗覆的金屬顆粒之重量比為至少1：100且至多(含)30：100。 3. The non-aqueous composition of embodiment 1 or 2, wherein the weight ratio of the particulate dispersant to the dispersed carbon coated metal particles is at least 1:100 and at most 30:100.

4. 如實施例1至3中任一項之非水性組合物，其中該等經分散之經碳塗覆的金屬顆粒係以基於非水性組合物總重量計至少15重量%且至多(含)70重量%的量存在。 4. The non-aqueous composition of any one of embodiments 1 to 3, wherein the dispersed carbon coated metal particles are at least 15% by weight and at most (inclusive) based on the total weight of the non-aqueous composition. An amount of 70% by weight is present.

5. 如實施例1至4中任一項之非水性組合物，其中該顆粒分散劑具有至少2,000且至多(含)50,000之M_w。 Examples 1 to 5. The non-aqueous composition according to any one of embodiments 4, wherein the particle dispersant is at least 2,000 and up to (including) M _w 50,000 of.

6. 如實施例1至5中任一項之非水性組合物，其進一步含有基於非水性組合物總重量計至多(含)20重量%的量之經分散之碳黑。 6. The non-aqueous composition according to any one of embodiments 1 to 5, which further comprises, in an amount of up to 20% by weight, based on the total weight of the non-aqueous composition, of the dispersed carbon black.

7. 如實施例1至6中任一項之非水性組合物，其中該顆粒分散劑為含有酯單元之有機聚合物。 7. The non-aqueous composition according to any one of embodiments 1 to 6, wherein the particulate dispersant is an organic polymer containing an ester unit.

8. 如實施例1至7中任一項之非水性組合物，其中該顆粒分散劑為含有選自至少一種以下類別(i)至(iv)之單元之有機聚合物：(i)吡啶單元；(ii)亞胺單元；(iii)醯亞胺單元；及(iv)胺單元。 8. The non-aqueous composition according to any one of embodiments 1 to 7, wherein the particulate dispersant is an organic polymer comprising a unit selected from the group consisting of at least one of the following classes (i) to (iv): (i) a pyridine unit (ii) an imine unit; (iii) a quinone imine unit; and (iv) an amine unit.

9. 如實施例1至8中任一項之非水性組合物，其中該等經分散之經碳塗覆的金屬顆粒為以基於非水性組合物總重量計至少15重量%且至多(含)60重量%之濃度存在之經分散之經碳塗覆的銀顆粒，及該等經分散之經碳塗覆的銀顆粒具有如使用動態光散射法測得之小於0.5μm之中值直徑。 The non-aqueous composition according to any one of embodiments 1 to 8, wherein the dispersed carbon-coated metal particles are at least 15% by weight and at most (including) based on the total weight of the non-aqueous composition. The dispersed carbon coated silver particles present at a concentration of 60% by weight, and the dispersed carbon coated silver particles have a median diameter of less than 0.5 μm as measured using dynamic light scattering.

10. 如實施例1至9中任一項之非水性組合物，其中該有機稀釋劑為含有2-乙氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、1-甲氧基-2-丙醇、4-庚酮、3-庚酮、2-庚酮、環戊酮、環己酮、碳酸二乙酯、乙酸2-乙氧基乙酯、丁酸N-丁酯及乳酸甲酯中至少一者之有機溶劑介質。 10. The non-aqueous composition according to any one of embodiments 1 to 9, wherein the organic diluent is 2-ethoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2) -ethoxyethoxy)ethanol, 1-methoxy-2-propanol, 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, acetic acid An organic solvent medium for at least one of 2-ethoxyethyl ester, N-butyl butyrate, and methyl lactate.

11. 如實施例1至10中任一項之非水性組合物，其係非水性可光固化組合物，其進一步含有可光固化組分及視需要之UV光引發劑。 11. The non-aqueous composition of any of embodiments 1 to 10 which is a non-aqueous photocurable composition further comprising a photocurable component and optionally a UV photoinitiator.

12. 如實施例11之非水性組合物，其中該可光固化組分為可UV固化組分。 12. The non-aqueous composition of embodiment 11, wherein the photocurable component is a UV curable component.

13. 如實施例11或12之非水性組合物，其中該可光固化組分為經酸催化之可光固化組分及該非水性組合物進一步含有光酸產生劑。 13. The non-aqueous composition of embodiment 11 or 12, wherein the photocurable component is an acid catalyzed photocurable component and the non-aqueous composition further comprises a photoacid generator.

14. 如實施例11至13中任一項之非水性組合物，其中該可光固化組分為可光聚合環氧材料。 The non-aqueous composition of any one of embodiments 11 to 13, wherein the photocurable component is a photopolymerizable epoxy material.

15. 如實施例11至14中任一項之非水性組合物，其中該可光固化組分為每分子具有至少兩個可聚合環氧基之可光聚合環氧材料，及該光酸產生劑為錪或鋶化合物。 The non-aqueous composition according to any one of embodiments 11 to 14, wherein the photocurable component is a photopolymerizable epoxy material having at least two polymerizable epoxy groups per molecule, and the photoacid generation The agent is a ruthenium or osmium compound.

16. 如實施例11或12之非水性組合物，其中該可光固化組分為可自由基光固化組分，及該非水性組合物進一步含有自由基光引發劑。 16. The non-aqueous composition of embodiment 11 or 12, wherein the photocurable component is a free-radically photocurable component, and the non-aqueous composition further comprises a free radical photoinitiator.

17. 如實施例16之非水性組合物，其中該可光固化組分包括丙烯酸酯。 17. The non-aqueous composition of embodiment 16, wherein the photocurable component comprises an acrylate.

18. 一種包括基材且在基材之一或兩個支撐側上具有如實施例1至18中任一項之非水性組合物之乾燥層或乾燥圖案中任一者之物件。 18. An article comprising a substrate and having any one of a dry layer or a dried pattern of the non-aqueous composition of any of embodiments 1 to 18 on one or both of the support sides of the substrate.

19. 如實施例18之物件，其中該基材為連續聚合物網。 19. The article of embodiment 18 wherein the substrate is a continuous polymer network.

20. 如實施例18之物件，其中該基材包括金屬、玻璃、紙料或陶瓷。 20. The article of embodiment 18, wherein the substrate comprises metal, glass, paper stock or ceramic.

21. 如實施例18或19之物件，其中該基材為包括聚酯之連續網。 21. The article of embodiment 18 or 19 wherein the substrate is a continuous web comprising polyester.

22. 如實施例18、19或21中任一項之物件，其中該基材為連續聚合物網及該非水性組合物係呈多個圖案配置於該基材之兩支撐側上。 The article of any one of embodiments 18, 19 or 21, wherein the substrate is a continuous polymer web and the non-aqueous composition is disposed in a plurality of patterns on the two support sides of the substrate.

23. 一種包括基材且在基材之一或兩個支撐側上具有衍生自如實施例11至17中任一項之非水性組合物之經光固化組合物之乾燥層或乾燥圖案中任一者之物件。 23. A dry or dried pattern comprising a substrate and having a photocurable composition derived from the non-aqueous composition of any of embodiments 11 to 17 on one or both of the support sides of the substrate Objects.

24. 如實施例23之物件，其中該基材為連續聚合物網。 24. The article of embodiment 23 wherein the substrate is a continuous polymer network.

25. 如實施例23或24之物件，其中該經光固化之組合物係呈一或多個圖案配置於基材之一或兩個支撐側上。 25. The article of embodiment 23 or 24, wherein the photocurable composition is disposed on one or both of the support sides in one or more patterns.

26. 如實施例23至25中一個或多個實施例之物件，其中該基材為連續聚合物網及該經光固化之組合物係呈多個圖案配置於該基材之兩個支撐側上。 26. The article of one or more of embodiments 23 to 25, wherein the substrate is a continuous polymer web and the photocurable composition is disposed in a plurality of patterns on two support sides of the substrate on.

27. 如實施例23至26中任一項之物件，其中該基材為聚酯之連續網。 The article of any of embodiments 23 to 26, wherein the substrate is a continuous web of polyester.

28. 一種提供前驅物件之方法，該方法包括：提供透明基材之連續網，在該連續網之至少一個支撐側上的一或多個部分上形成一或多個衍生自如實施例11至17中任一項之非水性可光固化組合物之可光固化圖案。 28. A method of providing a precursor article, the method comprising: providing a continuous web of transparent substrates, forming one or more of the one or more portions on at least one of the support sides of the continuous web derived from Examples 11 through 17 A photocurable pattern of a non-aqueous photocurable composition according to any one of the preceding claims.

29. 如實施例28之方法，其進一步包括：光固化一或多個可光固化圖案以在連續網之一或多個部分上形成一或多個經光固化之圖案，該一或多個經光固化之圖案各包括作為晶種金屬觸媒位點之經分散之經碳塗覆的金屬顆粒，及用導電金屬無電電鍍連續網之一或多部分上的該一或多個經光固化之圖案各者。 29. The method of embodiment 28, further comprising: photocuring the one or more photocurable patterns to form one or more photocured patterns on one or more portions of the continuous web, the one or more The photocured patterns each comprise dispersed carbon coated metal particles as a seed metal catalyst site, and the one or more photocured materials on one or more portions of the electroless electroless plating continuous web Each of the patterns.

30 如實施例29之方法，其進一步包括：使用相同或不同非水性可光固化組合物在連續網之多個部分上進行形成、光固化及無電電鍍特徵多次，該多個部分相同或不同。 30. The method of embodiment 29, further comprising: forming, photocuring, and electroless plating features on the plurality of portions of the continuous web using the same or different non-aqueous photocurable compositions, the plurality of portions being the same or different .

31. 如實施例28至30中任一項之方法，其係用於提供複數個前驅物件，該方法包括：藉由使用一或多個柔版印刷部件將非水性可光固化組合物施覆至連續網一或兩個支撐側上的多個部分以在該多個部分上形成多個可光固化圖案， 使該包括多個可光固化圖案之連續網前進接近曝光輻射，及由此形成多個經光固化之圖案，及捲起該包括多個經光固化之圖案之連續網。 31. The method of any of embodiments 28 to 30 for providing a plurality of precursor articles, the method comprising: applying a non-aqueous photocurable composition by using one or more flexographic printing members And a plurality of portions on one or both of the support sides of the continuous web to form a plurality of photocurable patterns on the plurality of portions, The continuous web comprising a plurality of photocurable patterns is advanced adjacent to the exposure radiation, and thereby a plurality of photocured patterns are formed, and the continuous web comprising the plurality of photocured patterns is rolled up.

32. 如實施例28至31中任一項之方法，其中該基材為連續聚酯網。 The method of any one of embodiments 28 to 31, wherein the substrate is a continuous polyester mesh.

33. 如實施例32之方法，其中該基材為包括聚(對苯二甲酸乙二酯)之連續聚酯網。 33. The method of embodiment 32, wherein the substrate is a continuous polyester web comprising poly(ethylene terephthalate).

34. 一種用於在基材上形成多個導電圖案之方法，該方法包括：提供包括基材且在基材之一或兩個支撐側上配置多個包括作為晶種金屬觸媒之經分散之經碳塗覆的金屬顆粒之經光固化之圖案之前驅物件，該多個經光固化之圖案係藉由一或多種如實施例11至17中任一項所定義之非水性可光固化組合物提供，及無電電鍍該多個經光固化之圖案各者以形成多個導電圖案。 34. A method for forming a plurality of conductive patterns on a substrate, the method comprising: providing a substrate comprising and disposing a plurality of substrates on one or both of the support sides including dispersion as a seed metal catalyst a photocured pattern precursor of the carbon coated metal particles, the plurality of photocurable patterns being non-aqueous photocurable as defined by any one of embodiments 11 to 17 The composition provides, and electrolessly electroplating the plurality of photocured patterns to form a plurality of conductive patterns.

35. 一種形成多個電子裝置之方法，該方法包括：提供包括基材且在基材之一或兩個支撐側上配置多個包括經分散之經碳塗覆的金屬顆粒之經無電電鍍且經光固化之圖案之物件，該多個經無電電鍍且經光固化之圖案係藉由一或多種如實施例1至17中任一項所定義之非水性可光固化組合物提供，且藉由該多個經無電電鍍且經光固化之圖案形成多個導電物件，及製造該多個導電物件以形成多個電子裝置。 35. A method of forming a plurality of electronic devices, the method comprising: providing an electroless plating comprising a substrate and disposing a plurality of dispersed carbon coated metal particles on one or both of the support sides The photocured pattern of the article, the plurality of electrolessly plated and photocured patterns are provided by one or more non-aqueous photocurable compositions as defined in any one of embodiments 1 to 17, and Forming a plurality of electrically conductive articles from the plurality of electrolessly plated and photocured patterns, and fabricating the plurality of electrically conductive articles to form a plurality of electronic devices.

以下實例經提供以繪示本發明之實施，但不旨在以任何方式限制。 The following examples are provided to illustrate the practice of the invention, but are not intended to be limiting in any way.

採用以下分散劑篩選測試以判定本發明之實施中適於分散經碳 塗覆的銀顆粒之顆粒分散劑。此測試可類似地用於判定適宜地分散其他經碳塗覆的金屬顆粒(諸如經碳塗覆的銅顆粒及經碳塗覆的鉑顆粒)之可用的顆粒分散劑。 The following dispersant screening tests were used to determine the suitability for dispersion of carbon in the practice of the present invention. A particle dispersant of coated silver particles. This test can be similarly used to determine useful particle dispersants for suitably dispersing other carbon coated metal particles, such as carbon coated copper particles and carbon coated platinum particles.

初始分散劑篩選測試(0.5重量%經碳塗覆的銀顆粒)：Initial dispersant screening test (0.5 wt% carbon coated silver particles):

使用經碳塗覆的銀顆粒，使用少量之經碳塗覆的銀顆粒及過量之所測試顆粒分散劑(「分散劑」)(顆粒分散劑的重量與經碳塗覆的銀顆粒的重量之比為10：1)，來進行此測試。藉由伴隨攪拌添加2.5g所需分散劑至47.5g 1-甲氧基-2-丙醇(Sigma-Aldrich)直到分散劑完全溶解形成分散劑溶液，製得5重量%所測試分散劑之溶液。接著，伴隨攪拌將0.02g經碳塗覆的銀顆粒(NovaCentrix,Ag-25-ST3,25nm具體平均粒徑，Austin TX)添加至20ml玻璃小瓶內的4g 5重量%之分散劑溶液。所得非水性組合物各在環境溫度下用超音波探針系統(Vibra-Cell VC600,Sonics & Materials,Inc.)處理2分鐘且接著目測評估沉降。此係在讓懸浮液在室溫(20℃)下靜置24小時後藉由目測觀測進行。以下評級標度用於評估經分散之經碳塗覆的銀顆粒之沉降：5=透明溶液，完全沉降；4=淺灰色溶液，幾近完全沉降；3=寬灰色帶位於黑色懸浮液上方，部分沉降；2=窄灰色帶位於黑色懸浮液上方，一些局部沉降但少於評級「3」；及1=黑色懸浮液無表觀沉降。 Using carbon coated silver particles, using a small amount of carbon coated silver particles and an excess of the tested particle dispersant ("dispersant") (the weight of the particle dispersant and the weight of the carbon coated silver particles) The ratio is 10:1) to perform this test. A solution of 5% by weight of the tested dispersant was prepared by adding 2.5 g of the desired dispersant to 47.5 g of 1-methoxy-2-propanol (Sigma-Aldrich) with stirring until the dispersant was completely dissolved to form a dispersant solution. . Next, 0.02 g of carbon-coated silver particles (NovaCentrix, Ag-25-ST3, 25 nm specific average particle size, Austin TX) were added to 4 g of a 5% by weight dispersant solution in a 20 ml glass vial with stirring. The resulting non-aqueous compositions were each treated with an ultrasonic probe system (Vibra-Cell VC600, Sonics & Materials, Inc.) for 2 minutes at ambient temperature and then visually assessed for sedimentation. This was carried out by visual observation after allowing the suspension to stand at room temperature (20 ° C) for 24 hours. The following rating scales were used to evaluate the sedimentation of the dispersed carbon coated silver particles: 5 = clear solution, complete settling; 4 = light gray solution, nearly complete settling; 3 = wide gray band above the black suspension, Partial settling; 2 = narrow gray band above the black suspension, some local settlement but less than rating "3"; and 1 = black suspension without apparent settling.

分散劑篩選測試之結果概述於下表I中。 The results of the dispersant screening test are summarized in Table I below.

接著選擇表I中提供沉降評級為3或更小之分散劑以用於另一輪測試，但經碳塗覆的銀顆粒之濃度更高，經濃縮之分散劑測試如下。 A dispersant having a settling rating of 3 or less is then provided in Table I for another round of testing, but the concentration of carbon coated silver particles is higher, and the concentrated dispersant is tested as follows.

經濃縮之分散劑測試(50重量%經碳塗覆的銀顆粒)：Concentrated dispersant test (50% by weight carbon coated silver particles):

此評估係設計以評估具有遠遠較少分散劑與經碳塗覆的銀顆粒重量比(4或5重量%分散劑與經碳塗覆的銀顆粒重量%)之濃縮調配物中之分散劑。僅表徵其中值粒度，因為其過於濃縮而無法目測評估沉降行為。衍生自光散射測量之粒度分佈藉由顯示非水性組合物中含在懸浮液中之大聚結物程度以提供顆粒分散劑(分散劑)效果之良好指示。 This evaluation was designed to evaluate the dispersant in a concentrated formulation with a much lower weight ratio of dispersant to carbon coated silver particles (4 or 5 wt% dispersant to carbon coated silver particles wt%) . Only the median particle size was characterized because it was too concentrated to visually assess the sedimentation behavior. The particle size distribution derived from light scattering measurements is a good indication of the effectiveness of the particulate dispersant (dispersant) by showing the extent of macroaggregates contained in the suspension in the non-aqueous composition.

藉由伴隨攪拌添加2.5g所需分散劑至47.5g 1-甲氧基-2-丙醇直到分散劑完全溶解以提供分散劑溶液來製得5重量%所測試分散劑之溶液。接著，伴隨攪拌將8g經碳塗覆的銀顆粒(NovaCentrix Ag-25-ST3,25nm確定平均粒徑，Austin TX)添加至60ml瓶(LDPE，從Nalgene獲得)內的8g 5重量%分散劑溶液。在環境溫度(20℃)下用超音波探針系統(Vibra-Cell VC600,Sonics& Materials,Inc.)處理所得非水性組合物2至4分鐘。移去約0.2g懸浮液及藉由動態光散射使用Malvern Zetasizer Nano-ZS(「ZEN」)設備測量中值粒徑並表示為Dv(50%)。所有尺寸數據係基於體積加權分佈及等效球形直徑模型。結果顯示於下表II中。 A solution of 5% by weight of the tested dispersant was prepared by adding 2.5 g of the desired dispersant to 47.5 g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved to provide a dispersant solution. Next, 8 g of carbon-coated silver particles (NovaCentrix Ag-25-ST3, 25 nm average particle size, Austin TX) were added to 8 g of a 5 wt% dispersant solution in a 60 ml bottle (LDPE, obtained from Nalgene) with stirring. . The resulting non-aqueous composition was treated with an ultrasonic probe system (Vibra-Cell VC600, Sonics & Materials, Inc.) at ambient temperature (20 ° C) for 2 to 4 minutes. Approximately 0.2 g of the suspension was removed and the median particle size was measured by dynamic light scattering using a Malvern Zetasizer Nano-ZS ("ZEN") apparatus and expressed as Dv (50%). All dimensional data is based on a volume weighted distribution and an equivalent spherical diameter model. The results are shown in Table II below.

顯示於表II中之結果說明所評估的識別為測試2-2至2-17之分散劑可有效地分散具有理想地小的中值直徑(等於或小於0.6μm)之經碳塗覆的銀顆粒及因此為本發明之非水性組合物之實施例。 The results shown in Table II indicate that the evaluated dispersants identified as Tests 2-2 to 2-17 are effective for dispersing carbon coated silver having an ideally small median diameter (equal to or less than 0.6 μm). The granules and thus the examples of the non-aqueous compositions of the invention.

非水性可光固化組合物(21重量%經分散之經碳塗覆的銀顆粒)：Non-aqueous photocurable composition (21% by weight of dispersed carbon coated silver particles):

使用顯示於下表III中之各顆粒分散劑(分散劑)及經分散之經碳塗 覆的銀顆粒調配非水性可光固化組合物，及此等非水性可光固化組合物各用於製造導電物件。 Each of the particle dispersants (dispersants) and dispersed carbon coatings shown in Table III below were used. The coated silver particles are formulated with a non-aqueous photocurable composition, and such non-aqueous photocurable compositions are each used to make electrically conductive articles.

藉由伴隨攪拌添加2.5g分散劑至47.5g 1-甲氧基-2-丙醇直到分散劑完全溶解形成分散劑溶液來製得5重量%所需分散劑之溶液。接著，伴隨攪拌將8g經碳塗覆的銀顆粒(NovaCentrix Ag-25-ST3,25nm確定平均粒徑，Austin TX)添加至60ml瓶(LDPE，從Nalgene獲得)內的8g 5重量%分散劑溶液。在環境溫度(20℃)下用超音波探針系統(Vibra-Cell VC600,Sonics & Materials,Inc.)處理所得非水性組合物4分鐘。 A solution of 5% by weight of the desired dispersant was prepared by adding 2.5 g of a dispersant to 47.5 g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved to form a dispersant solution. Next, 8 g of carbon-coated silver particles (NovaCentrix Ag-25-ST3, 25 nm average particle size, Austin TX) were added to 8 g of a 5 wt% dispersant solution in a 60 ml bottle (LDPE, obtained from Nalgene) with stirring. . The resulting non-aqueous composition was treated with an ultrasonic probe system (Vibra-Cell VC600, Sonics & Materials, Inc.) for 4 minutes at ambient temperature (20 ° C).

藉由混合以下組分製備可光固化組分之溶液：27.33重量%環氧丙烯酸酯CN 153(6.02g,Sartomer)、18.82重量%聚(乙二醇)二丙烯酸酯(4.15g,M_n為250,Sigma-Aldrich)、4.04重量%聚(乙二醇)二丙烯酸酯(0.89g,M_n為575,Sigma-Aldrich)、20.62重量%季戊四醇四丙烯酸酯(4.55g,Sartomer)、混於50%碳酸丙二酯中之1.52重量%三芳基鋶鹽六氟磷酸鹽(0.34g,Sigma-Aldrich)、混於50%碳酸丙二酯中之1.52重量%三芳基鋶鹽六氟銻酸鹽(0.34g,Sigma-Aldrich)、4.55重量%自由基光引發劑羥基環己基苯基酮(1.0g,Sigma-Aldrich)、2.32重量%自由基光引發劑甲基-4'-(甲硫基)-2-嗎啉基苯丙酮(0.51g,Sigma-Aldrich)、0.002重量% 9-芴酮(0.0004g,Sigma-Aldrich)、3.81重量% 4-(二甲胺基)苯甲酸乙酯(0.84g,Sigma-Aldrich)及15.42重量% 1-甲氧基-2-丙醇(3.4g,Sigma-Aldrich)。 The following components may be prepared by mixing a solution of a photocurable component of: 27.33 wt% epoxy acrylate CN 153 (6.02g, Sartomer), 18.82 wt% poly (ethylene glycol) diacrylate (4.15g, M _n is 250, Sigma-Aldrich), 4.04% by weight of poly (ethylene glycol) diacrylate (0.89g, M _n of 575, Sigma-Aldrich), 20.62% by weight of pentaerythritol tetraacrylate (4.55g, Sartomer), mixed in 50 1.52% by weight of triarylsulfonium salt hexafluorophosphate (0.34 g, Sigma-Aldrich) in 1.5% propylene carbonate, 1.52% by weight of triarylsulfonium salt hexafluoroantimonate mixed in 50% propylene carbonate ( 0.34 g, Sigma-Aldrich), 4.55 wt% free radical photoinitiator hydroxycyclohexyl phenyl ketone (1.0 g, Sigma-Aldrich), 2.32 wt% free radical photoinitiator methyl-4'-(methylthio) -2-morpholinylpropiophenone (0.51 g, Sigma-Aldrich), 0.002% by weight of 9-fluorenone (0.0004 g, Sigma-Aldrich), 3.81% by weight of ethyl 4-(dimethylamino)benzoate (0.84 g, Sigma-Aldrich) and 15.42% by weight of 1-methoxy-2-propanol (3.4 g, Sigma-Aldrich).

伴隨攪拌將此可光固化組分溶液之樣品(22.04g)添加至含有經碳塗覆的銀顆粒(16g)之非水性組合物。接著使用具有轉子-定子探針(PRO Scientific,Inc.)之PRO 300D台式均質機以10,000rpm操作5分鐘使各非水性可光固化組合物混合，同時使得非水性可光固化組合物冷卻。 A sample (22.04 g) of this photocurable component solution was added to a non-aqueous composition containing carbon-coated silver particles (16 g) with stirring. Each non-aqueous photocurable composition was then mixed using a PRO 300D benchtop homogenizer with a rotor-stator probe (PRO Scientific, Inc.) at 10,000 rpm for 5 minutes while allowing the non-aqueous photocurable composition to cool.

移去約0.2g懸浮液及藉由動態光散射使用Malvern Zetasizer Nano-ZS(「ZEN」)設備測量中值粒徑並表示為Dv(50%)。所有尺寸數據係基於體積加權分佈及等效球形直徑模型。結果顯示於下表III中。 Approximately 0.2 g of the suspension was removed and the median particle size was measured by dynamic light scattering using a Malvern Zetasizer Nano-ZS ("ZEN") apparatus and expressed as Dv (50%). All dimensional data is based on a volume weighted distribution and an equivalent spherical diameter model. The results are shown in Table III below.

取出非水性可光固化組合物(亦視為「油墨」)之約2g樣品並置於窄玻璃小瓶中以評估24小時至約7天後之沉降及澄清。24小時後位於所得黑色非水性可光固化組合物頂部之無色流體之清晰帶指示無法維持經碳塗覆的銀顆粒懸浮。小瓶底部存在沉降物而不澄清指示經部分穩定之經碳塗覆的銀顆粒之懸浮液。此等評估之結果顯示於下表III中。 Approximately 2 g of the non-aqueous photocurable composition (also referred to as "ink") was taken and placed in a narrow glass vial to assess settling and clarification after 24 hours to about 7 days. The clear band of the colorless fluid on top of the resulting black non-aqueous photocurable composition after 24 hours indicates that the carbon coated silver particles could not be maintained in suspension. A sediment was present at the bottom of the vial without clarifying a suspension indicating partially stabilized carbon coated silver particles. The results of these assessments are shown in Table III below.

顯示於表III中之結果說明僅本發明界定之顆粒分散劑(分散劑)提供適當小的中值直徑之非水性可光固化組合物中之經分散之經碳塗覆的銀顆粒。除此之外，本發明非水性可光固化組合物顯示調配及使用期間無沉降或沉降物。 The results shown in Table III illustrate that only the particulate dispersant (dispersant) as defined herein provides dispersed carbon coated silver particles in a non-aqueous photocurable composition of a suitably small median diameter. In addition to this, the non-aqueous photocurable compositions of the present invention show no settling or sedimentation during formulation and use.

物件發明實例：非水性可光固化組合物於提供圖案化物件之用途Object invention example: use of a non-aqueous photocurable composition for providing a patterned article

本發明實例證實本發明之非水性可光固化組合物於製造適宜基材上具有可光固化圖案之前驅物件之用途。 The present invention demonstrates the use of the non-aqueous photocurable composition of the present invention to produce a photocurable pattern precursor prior to fabrication of a suitable substrate.

使用柔版印刷部件以印刷本發明非水性可光固化組合物(如下文所述)，該柔版印刷部件為已使用具有使用Kodak Square Spot雷射技術以12,800dpi之解析度寫入之預定圖案之遮罩成像之市售Kodak Flexcel NX柔版印刷板前驅物(Eastman Kodak Company)之樣品。使用製造商對此等柔版印刷部件所建議的已知條件UV曝光及處理(顯影)該柔版印刷板前驅物。所得柔版印刷板為1.14mm厚(包括PET膜)。用於固定柔版印刷板至印刷體滾筒之背襯膠帶為20密耳(0.051cm)厚、蕭氏(Shore)A硬度為55之1120 Beige膠帶(3M Company)。柔版印刷部件中之所得浮凸圖像設計包括具有在頂浮凸表面具有7μm寬度之細線之網格圖案。 A flexographic printing member is used to print a non-aqueous photocurable composition of the invention (as described below) that has been used with a predetermined pattern having a resolution of 12,800 dpi using Kodak Square Spot laser technology. A sample of the commercially available Kodak Flexcel NX Flexographic Plate Precursor (Eastman Kodak Company) was imaged by the mask. The flexographic printing plate precursor is UV exposed and processed (developed) using known conditions recommended by the manufacturer for such flexographic printing components. The resulting flexographic printing plate was 1.14 mm thick (including PET film). The backing tape used to hold the flexographic printing plate to the print cylinder was 20 mil (0.051 cm) thick and 1120 Beige tape (3M Company) having a Shore A hardness of 55. The resulting raised image design in the flexographic printing member includes a grid pattern having thin lines having a width of 7 μm on the top relief surface.

使用所述圖案化柔版印刷部件(如下文所述)，使用柔版模式之台式測試印刷機「IGT F1 Printability Tester」(IGT Testing Systems Inc.,Arlington Heights,IL)，將述於上表III中之本發明非水性可光固化組 合物3-1(Inv)印刷至PET[聚(對苯二甲酸乙二酯)膜[Melinex^® ST505,DuPont Teijin Films]基材上。用於施覆非水性可光固化組合物至柔版印刷部件之網紋輥系統具有如藉由IGT Testing Systems確定之1.3 BCMI及1803lpi之值。在環境溫度下使用20N之網紋力、10N之印刷力及0.20m/s之印刷速度來製作印刷圖案。自藉由所述的柔版印刷部件上之網格圖案印刷之圖案獲得基材上所印刷的平均線寬度。 Using the patterned flexographic printing component (as described below), the tabletop test press "IGT F1 Printability Tester" (IGT Testing Systems Inc., Arlington Heights, IL) using the flexo mode will be described in Table III above. in the present invention the non-aqueous photocurable compositions 3-1 (Inv) printed onto the PET [poly ^{[Melinex ® ST505, DuPont Teijin films} ] on a substrate (ethylene terephthalate) film. The anilox roll system for applying the non-aqueous photocurable composition to the flexographic printing member has a value of 1.3 BCMI and 1803 lpi as determined by IGT Testing Systems. A printed pattern was produced using a 20 N mesh force, a printing force of 10 N, and a printing speed of 0.20 m/s at ambient temperature. The average line width printed on the substrate is obtained from the pattern printed by the grid pattern on the flexographic printing member.

此等操作獲得包含非水性可光固化組合物印刷於PET基材上之圖案之物件。 These operations result in articles comprising a pattern of non-aqueous photocurable compositions printed on a PET substrate.

使用提供介於190至1500nm之間之輻射波長之Fusion 300 WPI中壓汞燈以UV輻射照射各非水性可光固化組合物印刷圖案，近似暴露量為298mJ/cm²，以光固化各印刷圖案。在透射及反射兩種模型中使用Olympus BH-2光學顯微鏡測量固化圖案之經印刷且光固化之平均線寬。 Each non-aqueous photocurable composition printed pattern was irradiated with UV radiation using a Fusion 300 WPI medium pressure mercury lamp providing a wavelength of radiation between 190 and 1500 nm with an approximate exposure of 298 mJ/cm ² to photocure each printed pattern. . The average line width of the printed and photocured cured pattern was measured using an Olympus BH-2 optical microscope in both transmission and reflection models.

此工作實例證實非水性可光固化組合物可成功地用於提供適宜基材上具有未光固化圖案之前驅物件，該等前驅物件進而可用於提供具有經光固化之圖案之中間物件。 This working example demonstrates that the non-aqueous photocurable composition can be successfully used to provide precursors having a non-curable pattern on a suitable substrate, which in turn can be used to provide an intermediate article having a photocured pattern.

發明實例：非水性可光固化組合物於提供導電物件的用途Inventive Example: Use of a Non-Aqueous Photocurable Composition for Providing a Conductive Article

上文所述之包含經光固化之圖案之物件可用作中間物件以用於進一步操作。特定言之，藉由在裝納Enplate^® Cu-406無電電鍍溶液(Enthone)之燒杯中於35℃浸泡中間物件10分鐘使該中間物件無電鍍銅，接著蒸餾水沖洗及用氮氣乾燥，以形成具有配置於PET基材上之導電圖案之產品物件。 The article comprising the photocured pattern described above can be used as an intermediate article for further manipulation. Specifically, the intermediate article is electroless copper-plated by soaking the intermediate article at 35 ° C for 10 minutes in a beaker containing Enplate ^® Cu-406 electroless plating solution (Enthone), followed by rinsing with distilled water and drying with nitrogen to form A product item of a conductive pattern disposed on a PET substrate.

已尤其參考本發明特定較佳實施例詳細地描述本發明，但應明瞭可在本發明之精神及範疇內進行變動及修改。 The present invention has been described in detail with reference to the preferred embodiments of the present invention, but it should be understood that modifications and modifications can be made within the spirit and scope of the invention.

Claims (35)

一種非水性組合物，其包含基於該非水性組合物總重量計至少10重量%的量之在有機稀釋劑中之經分散之經碳塗覆的金屬顆粒，該等經分散之經碳塗覆的金屬顆粒具有等於或小於0.6μm之中值直徑，及係用具有至少2,000且至多(含)100,000之重量平均分子量(M_w)並包含含氮單元之顆粒分散劑分散，該中值直徑係使用動態光散射法測得，其中，當該非水性組合物含有至多(含)25重量%之經分散之經碳塗覆的金屬顆粒時，其在20℃進行至少24小時的沉降測試時未呈現視覺上的沉降。 A non-aqueous composition comprising dispersed carbon coated metal particles in an organic diluent in an amount of at least 10% by weight based on the total weight of the non-aqueous composition, the dispersed carbon coated metal particles less than or equal to the value of 0.6μm in diameter, and having lines of at least 2,000 and up to (inclusive) of 100,000 weight average molecular weight (M _w) and a dispersant comprising a nitrogen-containing particles dispersed unit, using the median diameter based Dynamic light scattering method, wherein when the non-aqueous composition contains at most 25% by weight of dispersed carbon-coated metal particles, it does not exhibit visuality when subjected to a sedimentation test at 20 ° C for at least 24 hours. Settling on. 如請求項1之非水性組合物，其包含經分散之經碳塗覆的銀顆粒或經分散之經碳塗覆的銅顆粒、或經分散之經碳塗覆的銀顆粒及經分散之經碳塗覆的銅顆粒二者之混合物。 A non-aqueous composition according to claim 1 which comprises dispersed carbon coated silver particles or dispersed carbon coated copper particles, or dispersed carbon coated silver particles and dispersed A mixture of both carbon coated copper particles. 如請求項1之非水性組合物，其中該顆粒分散劑與該等經分散之經碳塗覆的金屬顆粒之重量比為至少1：100且至多(含)30：100。 The non-aqueous composition of claim 1, wherein the weight ratio of the particulate dispersant to the dispersed carbon-coated metal particles is at least 1:100 and at most 30:100. 如請求項1之非水性組合物，其中該等經分散之經碳塗覆的金屬顆粒係以基於該非水性組合物總重量計至少15重量%且至多(含)70重量%的量存在。 The non-aqueous composition of claim 1, wherein the dispersed carbon-coated metal particles are present in an amount of at least 15% by weight and up to 70% by weight, based on the total weight of the non-aqueous composition. 如請求項1之非水性組合物，其中該顆粒分散劑具有至少2,000且至多(含)50,000之M_w。 The non-aqueous composition of claim 1, wherein the particulate dispersant has a _{Mw of} at least 2,000 and up to 50,000. 如請求項1之非水性組合物，其進一步包含基於該非水性組合物總重量計至多(含)20重量%的量之經分散之碳黑。 The non-aqueous composition of claim 1, which further comprises dispersed carbon black in an amount of up to 20% by weight based on the total weight of the non-aqueous composition. 如請求項1之非水性組合物，其中該顆粒分散劑為包含酯單元之有機聚合物。 The non-aqueous composition of claim 1, wherein the particulate dispersant is an organic polymer comprising an ester unit. 如請求項1之非水性組合物，其中該顆粒分散劑為包含選自至少 一種以下類別(i)至(iv)之單元之有機聚合物：(i)吡啶單元；(ii)亞胺單元；(iii)醯亞胺單元；及(iv)胺單元。 The non-aqueous composition of claim 1, wherein the particulate dispersing agent comprises at least one selected from the group consisting of An organic polymer of the following classes (i) to (iv): (i) a pyridine unit; (ii) an imine unit; (iii) a quinone unit; and (iv) an amine unit. 如請求項1之非水性組合物，其中該等經分散之經碳塗覆的金屬顆粒為以基於該非水性組合物總重量計至少15重量%且至多(含)60重量%之濃度存在之經分散之經碳塗覆的銀顆粒，及該等經分散之經碳塗覆的銀顆粒具有如使用動態光散射法測得之小於0.5μm之中值直徑。 The non-aqueous composition of claim 1, wherein the dispersed carbon-coated metal particles are present in a concentration of at least 15% by weight and at most 60% by weight based on the total weight of the non-aqueous composition. The dispersed carbon coated silver particles, and the dispersed carbon coated silver particles have a median diameter of less than 0.5 [mu]m as measured using dynamic light scattering. 如請求項1之非水性組合物，其中該有機稀釋劑為包含2-乙氧基乙醇、2-(2-甲氧基乙氧基)乙醇、2-(2-乙氧基乙氧基)乙醇、1-甲氧基-2-丙醇、4-庚酮、3-庚酮、2-庚酮、環戊酮、環己酮、碳酸二乙酯、乙酸2-乙氧基乙酯、丁酸N-丁酯及乳酸甲酯中至少一者之有機溶劑介質。 The non-aqueous composition of claim 1, wherein the organic diluent comprises 2-ethoxyethanol, 2-(2-methoxyethoxy)ethanol, 2-(2-ethoxyethoxy) Ethanol, 1-methoxy-2-propanol, 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, An organic solvent medium for at least one of N-butyl butyrate and methyl lactate. 如請求項1之非水性組合物，其係非水性可光固化組合物，其進一步包含可光固化組分及視需要之UV光引發劑。 A non-aqueous composition according to claim 1 which is a non-aqueous photocurable composition further comprising a photocurable component and optionally a UV photoinitiator. 如請求項11之非水性組合物，其中該可光固化組分為可UV固化組分。 The non-aqueous composition of claim 11, wherein the photocurable component is a UV curable component. 如請求項11之非水性組合物，其中該可光固化組分為經酸催化之可光固化組分及該非水性組合物進一步包含光酸產生劑。 The non-aqueous composition of claim 11, wherein the photocurable component is an acid catalyzed photocurable component and the non-aqueous composition further comprises a photoacid generator. 如請求項13之非水性組合物，其中該可光固化組分為可光聚合環氧材料。 The non-aqueous composition of claim 13, wherein the photocurable component is a photopolymerizable epoxy material. 如請求項14之非水性組合物，其中該可光固化組分為每分子具有至少兩個可聚合環氧基之可光聚合環氧材料，及該光酸產生劑為錪或鋶化合物。 The non-aqueous composition of claim 14, wherein the photocurable component is a photopolymerizable epoxy material having at least two polymerizable epoxy groups per molecule, and the photoacid generator is a ruthenium or osmium compound. 如請求項11之非水性組合物，其中該可光固化組分為可自由基光固化組分，及該非水性組合物進一步包含自由基光引發劑。 The non-aqueous composition of claim 11, wherein the photocurable component is a radical photocurable component, and the non-aqueous composition further comprises a free radical photoinitiator. 如請求項16之非水性組合物，其中該可光固化組分包括丙烯酸酯。 The non-aqueous composition of claim 16, wherein the photocurable component comprises an acrylate. 一種物件，其包含基材且在該基材之一或兩個支撐側上具有如請求項1或11之非水性組合物之乾燥層或乾燥圖案中任一者。 An article comprising a substrate and having either a dry layer or a dried pattern of the non-aqueous composition of claim 1 or 11 on one or both of the support sides of the substrate. 如請求項18之物件，其中該基材為連續聚合物網。 The article of claim 18, wherein the substrate is a continuous polymer network. 如請求項18之物件，其中該基材包含金屬、玻璃、紙料(paperstock)或陶瓷。 The article of claim 18, wherein the substrate comprises metal, glass, paperstock or ceramic. 如請求項18之物件，其中該基材為包含聚酯之連續網。 The article of claim 18, wherein the substrate is a continuous web comprising polyester. 如請求項18之物件，其中該基材為連續聚合物網及該非水性組合物係呈多個圖案配置於該基材之兩個支撐側上。 The article of claim 18, wherein the substrate is a continuous polymer web and the non-aqueous composition is disposed in a plurality of patterns on the two support sides of the substrate. 一種物件，其包含基材且在該基材之一或兩個支撐側上具有衍生自如請求項11之非水性組合物之經光固化組合物之乾燥層或乾燥圖案中任一者。 An article comprising a substrate and having either a dried or dried pattern of a photocurable composition derived from the non-aqueous composition of claim 11 on one or both of the support sides of the substrate. 如請求項23之物件，其中該基材為連續聚合物網。 The article of claim 23, wherein the substrate is a continuous polymer network. 如請求項23之物件，其中該經光固化之組合物係呈一或多個圖案配置於基材之一或兩個支撐側上。 The article of claim 23, wherein the photocurable composition is disposed on one or both of the support sides in one or more patterns. 如請求項23之物件，其中該基材為連續聚合物網及該經光固化之組合物係呈多個圖案配置於該基材之兩個支撐側上。 The article of claim 23, wherein the substrate is a continuous polymer web and the photocurable composition is disposed in a plurality of patterns on the two support sides of the substrate. 如請求項23之物件，其中該基材為聚酯之連續網。 The article of claim 23, wherein the substrate is a continuous web of polyester. 一種提供前驅物件之方法，該方法包括：提供透明基材之連續網，在該連續網之至少一個支撐側上的一或多個部分上形成一或多個衍生自如請求項11之該非水性組合物之可光固化圖案。 A method of providing a precursor article, the method comprising: providing a continuous web of transparent substrates, forming one or more non-aqueous combinations derived from claim 11 on one or more portions on at least one support side of the continuous web The photocurable pattern of the object. 如請求項28之方法，其進一步包括： 光固化該一或多個可光固化圖案以在該連續網之該一或多個部分上形成一或多個經光固化之圖案，該一或多個經光固化之圖案各包含作為晶種金屬觸媒位點之經分散之經碳塗覆的金屬顆粒，及用導電金屬無電電鍍該連續網之該一或多部分上的該一或多個經光固化之圖案各者。 The method of claim 28, further comprising: Photocuring the one or more photocurable patterns to form one or more photocured patterns on the one or more portions of the continuous web, the one or more photocurable patterns each comprising as a seed crystal The carbon coated metal particles of the metal catalyst sites are dispersed, and the one or more photocured patterns on the one or more portions of the continuous web are electrolessly plated with a conductive metal. 如請求項29之方法，其進一步包括：使用相同或不同非水性組合物在該連續網之多個部分上進行形成、光固化及無電電鍍特徵多次，該多個部分相同或不同。 The method of claim 29, further comprising: forming, photocuring, and electroless plating features on the portions of the continuous web multiple times using the same or different non-aqueous compositions, the plurality of portions being the same or different. 如請求項28之方法，其係用於提供複數個前驅物件，該方法包括：藉由使用一或多個柔版印刷部件將該非水性組合物施覆至該連續網一或兩個支撐側上的多個部分以在該多個部分上形成多個可光固化圖案，使該包含該等多個可光固化圖案之連續網前進接近曝光輻射，及由此形成多個經光固化之圖案，及捲起該包含該等多個經光固化之圖案之連續網。 The method of claim 28, for providing a plurality of precursor articles, the method comprising: applying the non-aqueous composition to one or both of the support sides by using one or more flexographic printing members a plurality of portions to form a plurality of photocurable patterns on the plurality of portions, advancing the continuous web comprising the plurality of photocurable patterns toward exposure radiation, and thereby forming a plurality of photocured patterns, And rolling up the continuous web comprising the plurality of photocured patterns. 如請求項28之方法，其中該基材為連續聚酯網。 The method of claim 28, wherein the substrate is a continuous polyester mesh. 如請求項32之方法，其中該基材為包含聚(對苯二甲酸乙二酯)之連續聚酯網。 The method of claim 32, wherein the substrate is a continuous polyester web comprising poly(ethylene terephthalate). 一種用於在基材上形成多個導電圖案之方法，該方法包括：提供包含基材且在該基材之一或兩個支撐側上配置多個包括作為晶種金屬觸媒之經分散之經碳塗覆的金屬顆粒之經光固化之圖案之前驅物件，該多個經光固化之圖案係從一或多種如請求項11中所定義之非水性組合物提供，及 無電電鍍該多個經光固化之圖案各者以形成多個導電圖案。 A method for forming a plurality of conductive patterns on a substrate, the method comprising: providing a substrate comprising and disposing a plurality of on the one or both support sides of the substrate comprising dispersed as a seed metal catalyst a photocured pattern precursor of carbon coated metal particles, the plurality of photocurable patterns being provided from one or more non-aqueous compositions as defined in claim 11; Each of the plurality of photocured patterns is electrolessly plated to form a plurality of conductive patterns. 一種形成多個電子裝置之方法，該方法包括：提供包含基材且在該基材之一或兩個支撐側上配置多個包括經分散之經碳塗覆的金屬顆粒之經無電電鍍且經光固化之圖案之物件，該多個經無電電鍍且經光固化之圖案係從一或多種如請求項1中所定義之非水性組合物提供，且從該多個經無電電鍍且經光固化之圖案形成多個導電物件，及製造該多個導電物件以形成多個電子裝置。 A method of forming a plurality of electronic devices, the method comprising: providing an electroless plating comprising a substrate and disposing a plurality of dispersed carbon coated metal particles on one or both of the support sides of the substrate a photocured pattern of articles, the plurality of electrolessly plated and photocured patterns being provided from one or more non-aqueous compositions as defined in claim 1 and from the plurality of electrolessly plated and photocured The pattern forms a plurality of conductive articles, and the plurality of conductive articles are fabricated to form a plurality of electronic devices.