TW202200717A - Support ink compositions and methods of use thereof in additive manufactured electronics - Google Patents
Support ink compositions and methods of use thereof in additive manufactured electronics Download PDFInfo
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本揭示案係關於使用增材製造來製造包括空隙之電子組件的系統、方法及組合物。特定言之，本揭示案係關於藉由使用水溶性支撐油墨，使用例如噴墨列印製造包括空隙之複合組件。The present disclosure relates to systems, methods, and compositions for manufacturing electronic components including voids using additive manufacturing. In particular, the present disclosure relates to the fabrication of composite components including voids using, for example, ink jet printing by using water-soluble support inks.
在過去幾年內，增材製造及自由形式製造過程在自電腦***體直接製造物件方面取得了一些顯著進步。舉例而言，快速原型設計技術允許比需要根據工程圖對材料塊進行專門機器加工且通常被外包之習知機械加工過程更快速、更有成本效益地製造出諸多物件（例如原型零件及模具），同時將對物件的專有知識保留在內部。Over the past few years, additive manufacturing and free-form manufacturing processes have made some notable advances in manufacturing objects directly from computer-controlled media. For example, rapid prototyping techniques allow many objects (such as prototype parts and molds) to be manufactured faster and more cost-effectively than conventional machining processes that require specialized machining of blocks of material from engineering drawings and are often outsourced , while keeping proprietary knowledge of the object in-house.
類似於其他快速原型設計技術，增材製造（AM）習知地涉及使用待製造之組件/部件的三維（3D）電腦輔助設計（CAD），在CAD包內自該設計產生立體微影（STL）或其他適合格式之檔案。隨後可對檔案（例如，STL）進行處理且實際上幾乎沿Z軸將其切成一定厚度，以匹配系統之分配能力的厚度。此產生物件之一系列平面橫截面層（庫）。Similar to other rapid prototyping techniques, additive manufacturing (AM) conventionally involves the use of three-dimensional (3D) computer-aided design (CAD) of components/parts to be manufactured, from which stereolithography (STL) is generated within a CAD package ) or other files in a suitable format. The file (eg, STL) can then be processed and actually cut to a thickness almost along the Z-axis to match the thickness of the system's dispensing capabilities. This produces a series of planar cross-section layers (libraries) of objects.
增材製造過程允許直接（不使用工具）自3D CAD資料產生高度複雜的幾何結構，藉此准許產生呈現高解析度表面之物件。儘管此等過程適用於詳述所產生物件之各種表面特性，但此類方法產生其中具有空隙之複雜物件很費勁，例如用於就導電組件及介電/樹脂組件（當將該等組件全部併入至設法製造之物件中時）而言產生凹坑、空層、埋孔（或通孔）。The additive manufacturing process allows the generation of highly complex geometries directly (without the use of tools) from 3D CAD data, thereby allowing the creation of objects that exhibit high-resolution surfaces. While these processes are suitable for detailing the various surface properties of the objects produced, such methods are laborious to produce complex objects with voids in them, such as are used for conductive components and dielectric/resin components (when all of these components are combined together) pits, voids, buried vias (or vias) when incorporated into the object being manufactured).
因此，需要能夠高效且精確地製造包括空隙之組件之複雜物件的組合物、系統及方法。Accordingly, there is a need for compositions, systems and methods that can efficiently and accurately fabricate complex objects including components of voids.
在各種例示性實施中，揭示使用增材製造（例如噴墨列印）形成或製造包括導電及樹脂/介電成分之組件的方法，以及促進包括空隙之組件或物件之製造的支撐油墨組合物之例示性實施。In various exemplary implementations, disclosed are methods of forming or fabricating components including conductive and resin/dielectric components using additive manufacturing (eg, inkjet printing), and supporting ink compositions that facilitate the manufacture of components or objects including voids An exemplary implementation of .
在例示性實施中，本發明提供一種包括丙烯酸酯聚合物及其衍生物中之至少一者的預固化支撐油墨組合物，其中其丙烯酸酯衍生物中之至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化水溶性共聚物；預固化丙烯酸酯寡聚物及/或其衍生物及水溶性共聚物之界面活性劑；光引發劑（PI），其中該水溶性共聚物與該PI之間的比率（w/w）在1:1與4:1之間。In an exemplary implementation, the present invention provides a pre-cured supported ink composition comprising at least one of an acrylate polymer and derivatives thereof, wherein at least one of the acrylate derivatives thereof is each pre-cured; including having Precured water-soluble copolymers of main chains of aromatic and aliphatic monomers; surfactants of precured acrylate oligomers and/or derivatives thereof and water-soluble copolymers; photoinitiators (PI), wherein the The ratio (w/w) between the water-soluble copolymer and the PI is between 1:1 and 4:1.
在另一例示性實施中，本發明提供一種使用噴墨印表機製造包括空隙之三維組件的方法，該方法包括：提供噴墨列印系統，其包括：第一列印頭，其經大小設定且經組態以分配介電樹脂組合物；第二列印頭，其經大小設定且經組態以分配導電油墨組合物；第三列印頭，其經大小設定且經組態以分配支撐油墨組合物，其中該支撐油墨組合物包括丙烯酸酯聚合物及其衍生物中之至少一者，其中其丙烯酸酯衍生物中之至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化共聚物；界面活性劑；光引發劑（PI），其中該共聚物與該PI之間的比率（w/w）在1:1與4:1之間；輸送機，其可操作地耦接至該第一列印頭、該第二列印頭及該第三列印頭，該輸送機經組態以將基板輸送至該第一列印頭、第二列印頭及第三列印頭中之每一者；及電腦輔助製造（「CAM」）模組，其包括：與非暫時性儲存通信的至少一個處理器，該儲存上儲存有一組可執行指令，該第可執行指令在執行時經組態使得所CPM：接收表示具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的3D可視化檔案；及產生表示用於列印包括該等空隙之該組件的第一實質上2D層之檔案，其中該CAM模組經組態以控制該第一列印頭、該第二列印頭及該第三列印頭中之每一者；提供該介電樹脂組合物、該導電油墨組合物及該支撐油墨組合物；使用該CAM模組，獲得用於列印之包括該等空隙之該組件的該第一實質上2D層，該2D層包括：表示介電樹脂油墨之圖案；表示導電油墨之圖案；及表示支撐油墨組合物之圖案；使用該第一列印頭，形成對應於該介電樹脂之該圖案；固化對應於具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的該2D層中該樹脂表示的該圖案；使用該第二列印頭，形成對應於導電油墨表示之該圖案；燒結對應於該導電油墨之該圖案；移除該基板，藉此製造包括該等空隙之該組件的第一層，其中在形成及固化對應於包括空隙之該組件之該第一實質上2D層中該介電樹脂表示的該圖案的步驟，及形成及燒結對應於包括空隙之該組件之該第一實質上2D層中該導電油墨表示之圖案的步驟中之至少一者之前或之後，使用該第三列印頭，形成對應於該支撐油墨表示之該圖案；及固化對應於包括該等空隙之該組件之該第一2D層中該支撐油墨組合物的該圖案。In another exemplary implementation, the present invention provides a method of fabricating a three-dimensional component including voids using an ink jet printer, the method comprising: providing an ink jet printing system comprising: a first print head that is sized set and configured to dispense dielectric resin composition; second printhead sized and configured to dispense conductive ink composition; third printhead sized and configured to dispense A support ink composition, wherein the support ink composition includes at least one of an acrylate polymer and derivatives thereof, wherein at least one of its acrylate derivatives is each precured; including having aromatic and aliphatic monomers Precured copolymer of the backbone of the body; Surfactant; Photoinitiator (PI), wherein the ratio (w/w) between the copolymer and the PI is between 1:1 and 4:1; Conveyor , which is operably coupled to the first print head, the second print head and the third print head, the conveyor is configured to convey the substrate to the first print head, the second row each of a printhead and a third printhead; and a computer-aided manufacturing ("CAM") module including: at least one processor in communication with non-transitory storage on which a set of executable instructions is stored , which, when executed, is configured such that the CPM: receives a 3D visualization file representing components having resin/dielectric and metal/conductive components (with voids therein); and generates representations for printing including the a file of a first substantially 2D layer of the component of the void, wherein the CAM module is configured to control each of the first printhead, the second printhead, and the third printhead; providing the dielectric resin composition, the conductive ink composition and the supporting ink composition; using the CAM module, obtaining the first substantially 2D layer of the component including the voids for printing, the 2D The layers include: a pattern representing a dielectric resin ink; a pattern representing a conductive ink; and a pattern representing a supporting ink composition; using the first print head, forming the pattern corresponding to the dielectric resin; curing corresponding to having a resin The pattern represented by the resin in the 2D layer of components of dielectric and metal/conductive components (with voids therein); using the second print head, forming the pattern corresponding to the conductive ink representation; sintering corresponding to the conductive ink the pattern of ink; removing the substrate thereby fabricating the first layer of the component including the voids, wherein the dielectric resin in forming and curing the first substantially 2D layer corresponding to the component including the voids The step of representing the pattern, and before or after at least one of the steps corresponding to the steps of forming and sintering the pattern represented by the conductive ink in the first substantially 2D layer of the component including voids, uses the third printing head, forming the pattern corresponding to the support ink representation; and curing the pattern corresponding to the support ink composition in the first 2D layer of the component including the voids.
用於製造具有樹脂/介電及/或導電成分之組件及/或物件（其中具有空隙）的方法及組合物之此等及其他特點將自以下實施方式在結合圖式及實例閱讀時顯而易見，該等圖式及實例為例示性的，而非限制性的。These and other features of methods and compositions for making components and/or articles having resin/dielectric and/or conductive components with voids therein will be apparent from the following embodiments when read in conjunction with the drawings and examples, The drawings and examples are illustrative and not restrictive.
本發明提供用於製造具有樹脂/介電及/或導電成分之組件及/或物件（具有空隙）的系統、方法及組合物之例示性實施。The present disclosure provides exemplary implementations of systems, methods, and compositions for making components and/or objects (with voids) having resin/dielectric and/or conductive components.
本文所述之方法可用於在使用例如噴墨列印裝置之連續增材製造過程中，以一遍次形式或使用若干遍次形成具有樹脂/介電及/或導電成分之組件及/或物件（具有空隙（係指移除或移動材料產生的空間））。由於一些增材製造方法能夠列印具有樹脂/介電以及導電/金屬成分兩者之組件及/或物件，因此需要可耐受此過程之獨特需求的支撐油墨。舉例而言，支撐油墨經調適以在相對較低溫度下為液體，使得發生噴射過程（換言之，具有0.1與1.0之間的韋伯數。The methods described herein can be used to form components and/or objects with resin/dielectric and/or conductive components in one pass or using several passes in a continuous additive manufacturing process using, for example, an inkjet printing device ( Has voids (meaning spaces created by removing or moving material). Since some additive manufacturing methods are capable of printing components and/or objects with both resin/dielectric and conductive/metallic components, there is a need for support inks that can withstand the unique demands of this process. For example, the support ink is adapted to be liquid at relatively low temperatures such that the jetting process occurs (in other words, with a Weber number between 0.1 and 1.0.
另外，構成支撐油墨組合物，使得其將在噴射過程之後進行快速固化過程。此外，在固化過程之後，支撐油墨組合物之熔點經調適得足夠高，使得燒結懸浮於導電油墨中之金屬/導電奈米粒子。由於支撐油墨之熔融溫度相對較高（例如，在約180℃與約240℃之間），合適的移除支撐油墨組合物以形成所需空隙之方法應藉由溶解。此約束條件意謂支撐油墨之化學組成應不同於介電/樹脂成分，其方式為允許選擇性溶解支撐油墨而不影響樹脂/介電油墨。本文所揭示及主張之支撐油墨組合物允許在將具有樹脂/介電及/或導電成分之完全組件及/或物件（具有空隙）浸沒於缺乏氘之水（「淡水」或DDW）後相對快速移除。移除支撐油墨進一步經調適，以不影響介電組件之介電特性及導電組件之電特性。In addition, the support ink composition is constructed such that it will undergo a rapid curing process after the jetting process. Furthermore, after the curing process, the melting point of the support ink composition is adjusted high enough to sinter the metal/conductive nanoparticles suspended in the conductive ink. Since the melting temperature of the support ink is relatively high (eg, between about 180°C and about 240°C), a suitable method of removing the support ink composition to form the desired voids would be by dissolution. This constraint means that the chemical composition of the support ink should be different from the dielectric/resin composition in a way that allows selective dissolution of the support ink without affecting the resin/dielectric ink. The supporting ink compositions disclosed and claimed herein allow for relatively rapid immersion of complete components and/or objects (with voids) having resin/dielectric and/or conductive components in deuterium-deficient water ("fresh water" or DDW) remove. The removal of the support ink is further adapted so as not to affect the dielectric properties of the dielectric components and the electrical properties of the conductive components.
因此且在例示性實施中，本發明提供一種包括丙烯酸酯聚合物及其衍生物中之至少一者的預固化支撐油墨組合物，其中其丙烯酸酯衍生物中之至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化水溶性共聚物；適於抑制該等預固化丙烯酸酯寡聚物及/或其衍生物與該水溶性共聚物之交聯的界面活性劑；光引發劑（PI），其中該水溶性共聚物與該PI之間的比率（w/w）在1:1與4:1之間。Accordingly, and in exemplary implementations, the present invention provides a pre-cured supported ink composition comprising at least one of an acrylate polymer and its derivatives, wherein at least one of its acrylate derivatives is each pre-cured; Precured water-soluble copolymers comprising backbones having aromatic and aliphatic monomers; interfacial activity suitable for inhibiting crosslinking of such precured acrylate oligomers and/or derivatives thereof with the water-soluble copolymers agent; a photoinitiator (PI), wherein the ratio (w/w) between the water-soluble copolymer and the PI is between 1:1 and 4:1.
如本文所用，術語「支撐」係指支撐材料之一或多個層，該支撐材料用於在製造本文所述之物件及組件期間為具有樹脂/介電及/或導電成分之建構組件及/或物件（具有空隙）的複數個層提供結構支撐。此外，在預固化丙烯酸酯聚合物及/或水溶性共聚物之情形下，術語「預固化」表示使至少一種基質材料（例如，支撐油墨之聚合物基質）至少部分地固化。舉例而言，在預固化丙烯酸酯聚合物及/或水溶性共聚物中，至少部分地固化。另外，「至少部分地固化」可包含實質上充分固化。此外，在本揭示案之情形下，術語「部分固化」意謂預固化丙烯酸酯聚合物及/或水溶性共聚物暴露至約60℃與約180℃之溫度下持續約30分鐘與約180分鐘之間的固化程度。在例示性實施中，藉由使未固化丙烯酸酯聚合物及/或未固化水溶性共聚物之混合物經受固化條件同時混合混合物以達到所需部分固化度，得到預固化丙烯酸酯聚合物及/或水溶性共聚物。As used herein, the term "support" refers to one or more layers of support material used to build components having resin/dielectric and/or conductive components and/or during manufacture of the articles and components described herein or multiple layers of objects (with voids) to provide structural support. Furthermore, in the context of pre-curing acrylate polymers and/or water-soluble copolymers, the term "pre-curing" means at least partially curing at least one matrix material (eg, a polymer matrix that supports the ink). For example, in pre-cured acrylate polymers and/or water-soluble copolymers, at least partially cured. Additionally, "at least partially cured" can include substantially fully cured. Furthermore, in the context of this disclosure, the term "partially cured" means that the pre-cured acrylate polymer and/or water soluble copolymer is exposed to a temperature of about 60°C and about 180°C for about 30 minutes and about 180 minutes degree of solidification. In an exemplary implementation, the precured acrylate polymer and/or the mixture of the uncured acrylate polymer and/or the uncured water-soluble copolymer is obtained by subjecting the mixture of uncured acrylate polymer and/or uncured water-soluble copolymer to curing conditions while mixing the mixture to achieve the desired degree of partial cure Water-soluble copolymer.
就對預固化組件之處理而言，取決於支撐油墨之應用，在處理期間變化的變量可為以下中之至少一者：
● 丙烯酸酯聚合物/寡聚物類型；
● 丙烯酸酯聚合物/寡聚物數量平均分子量（
在某一實施中，監測在上文所揭示之參數中的至少一者變化之後的固化可藉由例如以下進行： ● 監測混合物相比於完全固化介電材料之玻璃轉移溫度（Tg ）（例如使用DSC）； ● 監測無間隙體積之變化（例如使用DMA、膨脹計、DSC） ● 監測溶解時間及條件（例如，時間-溫度溶解表）；及 ● 監測預固化聚合物/寡聚物之交聯密度（v e ）（例如使用TGA）；In a certain implementation, monitoring curing after a change in at least one of the parameters disclosed above can be performed, for example, by: Monitoring the glass transition temperature (T g ) of the mixture compared to the fully cured dielectric material ( e.g. using DSC); ● monitoring changes in void-free volume (eg using DMA, dilatometer, DSC) ● monitoring dissolution times and conditions (eg, time-temperature dissolution tables); and ● monitoring precured polymer/oligomer changes crosslink density ( ve ) (eg using TGA );
在某些例示性實施中，混合物中二丙烯酸酯聚合物/寡聚物（雙官能）之濃度在50%與75%之間，Tg 在約45℃與約70℃之間，且交聯密度（v e ）在約5.5×103 莫耳/m-3 與約17×103 莫耳/m-3 之間。In certain exemplary implementations, the concentration of diacrylate polymer/oligomer (difunctional) in the mixture is between 50% and 75%, the Tg is between about 45°C and about 70°C, and the crosslinking is The density ( ve ) is between about 5.5×10 3 mol/m −3 and about 17×10 3 mol/m −3 .
在例示性實施中，用於製造本文所述之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法及系統中所用的支撐油墨組合物可為對光化輻射透明，以適應經由支撐之「回閃」暴露。在例示性實施中，「光化輻射」係指能夠固化用於立體微影之樹脂油墨組合物的能量光束，該立體微影諸如紫外射線、電子束、X射線或徑向射線。因此，用於產生本文所述之具有樹脂/介電及/或導電成分之組件及/或物件（具有空隙）中所用的「光化輻射可固化樹脂/介電或支撐組合物」可為樹脂組合物，其在用一或多種上文所述之光化輻射（能量光束）照射後固化。In an exemplary implementation, the support ink composition used in the methods and systems for making components described herein having resin/dielectric and metal/conductive components having voids therein can be transparent to actinic radiation to Adapt to "flashback" exposure via support. In an exemplary implementation, "actinic radiation" refers to a beam of energy capable of curing resin ink compositions for stereolithography, such as ultraviolet rays, electron beams, X-rays, or radial rays. Thus, the "actinic radiation curable resin/dielectric or support composition" used in producing components and/or articles (with voids) having resin/dielectric and/or conductive components described herein may be a resin A composition that cures upon irradiation with one or more of the actinic radiations (energy beams) described above.
此類反向暴露使得對最靠近支撐之層中光可聚合樹脂油墨組合物之至少一部分進行固化。適合的支撐油墨組合物之實例可包括例如約50%（w/w）與90%（w/w）之間的該預固化丙烯酸酯寡聚物及其衍生物中之至少一者；約10%（w/w）與20%（w/w）之間的該水溶性共聚物；約5%（w/w）與10%（w/w）之間的該PI；及不超過1%（w/w）之該界面活性劑，其中該界面活性劑不活化交聯。Such reverse exposure allows curing of at least a portion of the photopolymerizable resin ink composition in the layer closest to the support. An example of a suitable supporting ink composition can include, for example, between about 50% (w/w) and 90% (w/w) of at least one of the pre-cured acrylate oligomers and derivatives thereof; about 10 Between % (w/w) and 20% (w/w) of the water-soluble copolymer; between about 5% (w/w) and 10% (w/w) of the PI; and not more than 1% (w/w) of the surfactant, wherein the surfactant does not activate crosslinking.
舉例而言，本文所揭示之支撐油墨組合物中所用的水溶性共聚物包括具有芳族及脂族單體之主鏈，該水溶性共聚物的重量平均分子量（
同樣，在例示性實施中，本文所揭示之支撐油墨組合物中所用的預固化丙烯酸酯聚合物主鏈的重量平均分子量（
水溶性共聚物及/或丙烯酸酯聚合物及其衍生物之選擇隨例如以下中之至少一者而變化： ● 介電（DI）/樹脂油墨組合物； ● DI/樹脂油墨及物件之機械需求； ● 金屬/導電成分之燒結溫度； ● 固化類型及條件 ● 物件內之空隙大小及位置； ● 相對於噴嘴陣列*中之噴嘴大小的聚合物單元延展長度 換言之，聚合物長度藉由用聚合物之重量平均分子量除以主鏈單體之分子量且將單元數目乘以由平均黏結長度計算出的特徵單元長度來計算，得出以展開形式的聚合物之理論長度。因為聚合物具有凝固之傾向，所以其特徵延展長度不大於噴嘴孔口直徑為有益的。The choice of water-soluble copolymers and/or acrylate polymers and derivatives thereof varies, for example, as at least one of the following: ● Dielectric (DI)/resin ink compositions; ● Mechanical requirements for DI/resin inks and objects; ● Sintering temperature of metal/conductive components; ● Curing type and conditions ● The size and position of the gap in the object; ● Length of polymer unit extension relative to the size of the nozzles in the nozzle array* In other words, the polymer length is calculated by dividing the weight average molecular weight of the polymer by the molecular weight of the backbone monomers and multiplying the number of units by the characteristic unit length calculated from the average bond length to give the polymer in expanded form. theoretical length. Because the polymer has a tendency to solidify, it is beneficial that its characteristic extension is no greater than the diameter of the nozzle orifice.
同樣，為了使基於上文所鑑別之需求的效能最佳化，組合物可藉由例如以下中之至少一者調節： ● 改變水溶性共聚物或丙烯酸酯聚合物及/或其衍生物之重量平均分子量，其中分子量愈高則機械強度愈大，組合物黏度愈高且溶解愈慢； ● 改變該單體單元，形成該水溶性共聚物或該丙烯酸酯聚合物及/或其衍生物； ● 改變水溶性共聚物或丙烯酸酯聚合物及其衍生物之預固化程度，其中較高的預固化程度增大了機械強度且增加了溶解時間； ● 改變相對組件之濃度； ● 增加/降低該支撐油墨組合物中PI之濃度，其中較高的PI濃度增大了機械強度且增加了溶解時間。Likewise, to optimize performance based on the needs identified above, the composition can be adjusted by, for example, at least one of the following: ● Change the weight average molecular weight of the water-soluble copolymer or acrylate polymer and/or its derivatives, wherein the higher the molecular weight, the higher the mechanical strength, the higher the viscosity of the composition and the slower the dissolution; ● changing the monomer unit to form the water-soluble copolymer or the acrylate polymer and/or its derivatives; ● Change the pre-curing degree of water-soluble copolymer or acrylate polymer and its derivatives, wherein higher pre-curing degree increases mechanical strength and increases dissolution time; ● Change the concentration of relative components; • Increase/decrease the PI concentration in the support ink composition, where higher PI concentrations increase mechanical strength and increase dissolution time.
可與本文所述之預固化丙烯酸酯一起使用的光引發劑可為例如自由基光引發劑。此等自由基光引發劑可為例如以下中之一者：來自CIBA SPECIALTY CHEMICAL之Irgacure®500及Darocur®1173、Irgacure®819、Irgacure®184、TPO-L（(2,4,6,三甲基苯甲醯)）苯基亞膦酸乙酯）二苯甲酮及苯乙酮化合物及類似者。舉例而言，自由基光引發劑可為陽離子光引發劑，諸如六氟銻酸三芳基鋶混合鹽。所用自由基光引發劑之另一實例為以下中之至少一者：2-異丙基噻噸酮（ITX）、2,4-二乙基噻噸酮（DETX）、二苯甲酮、4-甲基二苯甲酮、4-二甲基胺基苯甲酸乙酯（EDAB）及2,2-二甲氧基-2-苯基苯乙酮。在例示性實施中，使用兩個或更多個PI，例如ITX及EDAB，或在另一實例中，EDAB、ITX及DETX。Photoinitiators that can be used with the precured acrylates described herein can be, for example, free radical photoinitiators. Such free radical photoinitiators may be, for example, one of the following: Irgacure® 500 and Darocur® 1173, Irgacure® 819, Irgacure® 184, TPO-L ((2,4,6, trimethyl) from CIBA SPECIALTY CHEMICAL phenylbenzyl)) ethyl phenylphosphinate) benzophenone and acetophenone compounds and the like. For example, the free radical photoinitiator may be a cationic photoinitiator, such as a mixed salt of triaryl perionium hexafluoroantimonate. Another example of a free radical photoinitiator used is at least one of the following: 2-isopropylthioxanthone (ITX), 2,4-diethylthioxanthone (DETX), benzophenone, 4 - Methyl benzophenone, ethyl 4-dimethylaminobenzoate (EDAB) and 2,2-dimethoxy-2-phenylacetophenone. In an exemplary implementation, two or more PIs are used, such as ITX and EDAB, or in another example, EDAB, ITX, and DETX.
此外，形成本文所述之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法可進一步包括在使用第一列印頭及/或第二列印頭之步驟之前提供可剝離或可移除基板的步驟。在例示性實施中，術語「可剝離」係指可以可移除方式施加至表面（諸如由用於形成本文所述之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法、組合物及套組產生之表面）且附著至表面，且隨後可藉由力自彼表面移除。根據本發明之組合物及方法的可剝離膜可以黏著方式及以可移除方式施加至安置於印表機之傳送帶上的夾盤，且借助於以強制性方式移除，暴露具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）之層。In addition, the methods of forming the components described herein with resin/dielectric and metal/conductive compositions having voids therein may further include providing a peelable prior to the step of using the first printhead and/or the second printhead or steps to remove the substrate. In an exemplary implementation, the term "peelable" refers to a process that can be applied to a surface in a removable manner, such as by a method used to form the components described herein having resin/dielectric and metal/conductive compositions with voids therein , compositions and kits) and adhere to a surface, and can then be removed from that surface by force. The peelable films according to the compositions and methods of the present invention can be adhesively and removably applied to a chuck placed on a conveyor belt of a printer, and by means of forced removal, exposing resin/intermediate Layers of components of electrical and metallic/conductive components having voids therein.
可移除基板亦可為粉末（例如陶瓷粉末），其可施加至該夾盤，壓緊且隨後移除。基板之選擇可取決於（例如）具有樹脂/介電及金屬/導電成分之最終組件（其中具有空隙）的使用及結構。此外，基板之移除可在整個組件之製造、第一2D層之製造結束時或在其間之任何階段進行。The removable substrate can also be a powder (eg ceramic powder) that can be applied to the chuck, compacted and then removed. The choice of substrate can depend, for example, on the use and structure of the final assembly with resin/dielectric and metal/conductive components with voids therein. Furthermore, the removal of the substrate can be done at the end of fabrication of the entire assembly, at the end of fabrication of the first 2D layer, or at any stage in between.
形成本文所述之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法可包括提供基板（例如可剝離膜）之步驟。列印頭（及其衍生物；應理解為係指將材料以控制方式沈積、傳送或產生於表面上的任何裝置或技術）沈積樹脂及/或導電油墨可經組態以按需求，換言之，隨各種預選過程參數（諸如輸送機速度、所需導電層厚度、層類型、層顏色及其類似物）變化提供油墨小液滴。可移除或可剝離基板亦可為相對剛性材料，例如玻璃或晶體（例如藍寶石）。另外或替代地，可剝離基板可為可撓性（例如可捲起）基板（或膜），使得基板易於自具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）剝離，例如聚(伸萘二甲酸伸乙酯）（PEN）、聚醯亞胺（例如，DuPont的Kaptone® ）、矽聚合物、聚(對苯二甲酸伸乙酯）（PET）、聚(四氟乙烯）（PTFE）膜等。此外，基板可為例如陶瓷粉末。The methods of forming the components described herein with resin/dielectric and metal/conductive components having voids therein may include the step of providing a substrate (eg, a peelable film). A printhead (and its derivatives; should be understood to mean any device or technique that deposits, transports or produces material in a controlled manner on a surface) depositing resin and/or conductive ink can be configured to on demand, in other words, The ink droplets are provided as a function of various preselected process parameters such as conveyor speed, desired conductive layer thickness, layer type, layer color, and the like. The removable or peelable substrate can also be a relatively rigid material, such as glass or a crystal (eg, sapphire). Additionally or alternatively, the peelable substrate may be a flexible (eg, rollable) substrate (or film) such that the substrate is easily peeled from components having resin/dielectric and metal/conductive components (with voids therein), such as poly (ethylene terephthalate) (PEN), polyimides (eg, Kaptone ® from DuPont), silicone polymers, poly(ethylene terephthalate) (PET), poly(tetrafluoroethylene) (PTFE) film, etc. Furthermore, the substrate may be, for example, a ceramic powder.
在藉由沈積組件樹脂之實質上2D層及/或金屬材料來製造或形成本文所述之複合物件及組件中，支撐層或結構可沈積為本文所述之複合物件及組件之實質上2D表示的一部分。此支撐可為可移除的且位於隨後列印的懸垂部分下方或未由部件或組件材料自身支撐之預期空腔中。支撐結構可利用與沈積部件材料相同的沈積技術建構。在例示性實施中，CAM模組可產生額外幾何形狀，其充當用於所形成之3D可視化檔案之懸垂或自由空間片段的支撐結構，該檔案表示具有樹脂/介電及金屬/導電成分之組件（其中具有空隙），且在其他情況下，所形成之複合物件及組件的側壁。支撐材料可經組態以（例如）在製造期間附著至部件材料，且當完成列印過程時可自本文所述之完全複合物件及組件移除。In fabricating or forming the composite objects and components described herein by depositing substantially 2D layers of component resin and/or metallic materials, support layers or structures may be deposited as substantially 2D representations of the composite objects and components described herein a part of. This support may be removable and located under a subsequently printed overhang or in an intended cavity that is not supported by the part or component material itself. The support structure can be constructed using the same deposition techniques as the deposition component materials. In an exemplary implementation, the CAM module may generate additional geometries that act as support structures for overhangs or free space segments of the resulting 3D visualization file representing components with resin/dielectric and metal/conductive components (with voids therein), and in other cases, the sidewalls of composite articles and assemblies formed. The support material can be configured to adhere to the part material, eg, during manufacture, and can be removed from the fully composite articles and assemblies described herein when the printing process is complete.
待用於本文所揭示之支撐油墨組合物中之適合的界面活性劑為例如陰離子界面活性劑，諸如C8 至C12 烷基苯磺酸酯、C12 至C16 烷磺酸酯、C12 至C16 烷基硫酸酯、C12 至C16 烷基磺基丁二酸酯及C12 至C16 硫酸化乙氧基化烷醇及非離子型界面活性劑，諸如C6 至C12 烷基酚乙氧基化物、C12 至C20 烷醇烷氧基化物，及環氧乙烷與環氧丙烷之嵌段共聚物。同樣，聚矽氧聚合物可藉由接枝聚醚基團進行改質，得到聚矽氧-聚醚共聚物。此等共聚物在水性介質中表現為界面活性劑，因為其具有疏水性及親水性組件。因此且在例示性實施中，界面活性劑可為例如經聚醚改質之聚(二甲基矽氧烷）（PDMS）。Suitable surfactants to be used in the propped ink compositions disclosed herein are, for example, anionic surfactants such as C8 to C12 alkylbenzene sulfonates, C12 to C16 alkanesulfonates , C12 to C16 alkyl sulfates, C12 to C16 alkyl sulfosuccinates and C12 to C16 sulfated ethoxylated alkanols and nonionic surfactants such as C6 to C12 alkanes Base phenol ethoxylates, C12 to C20 alkanol alkoxylates, and block copolymers of ethylene oxide and propylene oxide. Similarly, polysiloxane polymers can be modified by grafting polyether groups to obtain polysiloxane-polyether copolymers. These copolymers behave as surfactants in aqueous media because of their hydrophobic and hydrophilic components. Thus, and in an exemplary implementation, the surfactant may be, for example, polyether-modified poly(dimethylsiloxane) (PDMS).
在例示性實施中，本文所述之支撐油墨組合物用於所提供之系統及方法。因此且在例示性實施中，本發明提供一種使用噴墨印表機製造包括空隙之三維組件的方法，該方法包括：提供噴墨列印系統，其包括：第一列印頭，其可操作以分配介電樹脂組合物；第二列印頭，其可操作以分配導電油墨組合物；第三列印頭，其可操作以分配支撐油墨組合物，其中該支撐油墨組合物包括丙烯酸酯聚合物及其衍生物（係指例如在未受保護末端、分支長度及頻率等之間變化）中之至少一者，其中其丙烯酸酯衍生物中之至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化水溶性共聚物；適於抑制該等預固化丙烯酸酯寡聚物及/或其衍生物與該水溶性共聚物之交聯的界面活性劑；光引發劑（PI），其中該水溶性共聚物與該PI之間的比率（w/w）在1:1與4:1之間；輸送機，其可操作地耦接至該第一列印頭、該第二列印頭及該第三列印頭，該輸送機經組態以將基板輸送至該第一列印頭、第二列印頭及第三列印頭中之每一者；及電腦輔助製造（「CAM」）模組，其與該第一列印頭、第二列印頭及第三列印頭中之每一者通信，該CAM模組包含中央處理模組（CPM），其中所CPM進一步包括：與非暫時性儲存裝置通信的至少一個處理器，該儲存裝置經組態以儲存指令，該等指令在由該至少一個處理器執行時使得該CAM藉由執行包括以下之步驟來控制該噴墨列印系統：接收表示包括複合組件之該AME電路的3D可視化檔案；及產生具有複數個檔案之檔案庫，每一檔案表示用於列印AME電路之實質上2D層，該AME電路包括在相同檔案上含有的複合組件、支撐油墨圖案、導電油墨圖案及介電油墨圖案，其中該CAM模組經組態以控制該第一列印頭、該第二列印頭及該第三列印頭中之每一者；提供該介電樹脂組合物、該導電油墨組合物及該支撐油墨組合物；使用該CAM模組，自該庫獲得用於列印之包括該等空隙的該組件之第一層檔案，該第一層包括：表示介電樹脂油墨之圖案；表示導電油墨之圖案；及表示支撐油墨組合物之圖案；使用該第一列印頭，在該基板上形成對應於該介電樹脂之該圖案；使用光化輻射，固化對應於該介電樹脂之該圖案；使用該第二列印頭，在該基板或該介電樹脂圖案上形成對應於該導電油墨之該圖案；獨立地在固化及使用熱之步驟之前或之後，燒結對應於該導電油墨之該圖案；移除該基板，藉此製造包括該等空隙之該組件的第一層，其中在形成及固化對應於包括空隙之該組件之第一層中之該介電樹脂表示之該圖案的步驟，及形成及燒結對應於包括空隙之該組件之第一層中該導電油墨表示之圖案的步驟中之至少一者之前或之後，使用該第三列印頭，形成對應於該支撐油墨之該圖案；在固化該介電樹脂之步驟及/或燒結該導電油墨圖案之步驟同時、之前或之後，使用光化輻射，固化該支撐油墨圖案。In an exemplary implementation, the support ink compositions described herein are used in the provided systems and methods. Accordingly, and in an exemplary implementation, the present invention provides a method of fabricating a three-dimensional component including voids using an ink jet printer, the method comprising: providing an ink jet printing system comprising: a first print head operable to dispense a dielectric resin composition; a second printhead operable to dispense a conductive ink composition; a third printhead operable to dispense a support ink composition, wherein the support ink composition comprises an acrylate polymer at least one of its derivatives and derivatives thereof (meaning, for example, varying between unprotected ends, branch lengths and frequencies, etc.), wherein at least one of its acrylate derivatives is each precured; including those with aromatic and pre-cured water-soluble copolymers of the main chain of aliphatic monomers; surfactants suitable for inhibiting the cross-linking of these pre-cured acrylate oligomers and/or derivatives thereof with the water-soluble copolymers; photoinitiated agent (PI), wherein the ratio (w/w) between the water-soluble copolymer and the PI is between 1:1 and 4:1; a conveyor operably coupled to the first print head , the second print head and the third print head, the conveyor configured to convey the substrate to each of the first print head, the second print head and the third print head; and a computer-aided manufacturing ("CAM") module in communication with each of the first, second, and third print heads, the CAM module including a central processing module (CPM) ), wherein the CPM further includes: at least one processor in communication with a non-transitory storage device configured to store instructions that, when executed by the at least one processor, cause the CAM to include The inkjet printing system is controlled by the following steps: receiving a 3D visualization file representing the AME circuit including composite components; and generating a file library having a plurality of files, each file representing a substantial 2D representation of the AME circuit for printing layer, the AME circuit includes composite components, supporting ink patterns, conductive ink patterns, and dielectric ink patterns contained on the same file, wherein the CAM module is configured to control the first printhead, the second printhead head and each of the third print head; providing the dielectric resin composition, the conductive ink composition, and the supporting ink composition; using the CAM module, obtaining from the library for printing includes A first layer file of the component of the voids, the first layer comprising: a pattern representing a dielectric resin ink; a pattern representing a conductive ink; and a pattern representing a supporting ink composition; using the first print head, in The pattern corresponding to the dielectric resin is formed on the substrate; actinic radiation is used to cure the pattern corresponding to the dielectric resin; the second print head is used to form the pattern corresponding to the substrate or the dielectric resin in the pattern of the conductive ink; independently before or after the steps of curing and applying heat, sintering the pattern corresponding to the conductive ink; removing the substrate, thereby producing the first layer of the component comprising the voids , wherein in the steps of forming and curing the pattern represented by the dielectric resin in the first layer corresponding to the component including voids, and forming and sintering a first corresponding to the component including voids Before or after at least one of the steps of the pattern represented by the conductive ink in the layer, using the third print head, the pattern corresponding to the support ink is formed; the step of curing the dielectric resin and/or sintering the Simultaneously with, before or after the step of the conductive ink pattern, actinic radiation is used to cure the support ink pattern.
此外，該組的可執行指令在執行時經進一步組態使得所CPM產生用於後續列印包括空隙之組件的實質上2D層之庫，每一層包括表示以下中之至少一者的圖案：在包括空隙之組件的後續實質上2D層中之介電樹脂、導電油墨及支撐油墨組合物以及其列印次序，且另外，使用該CAM模組，獲得表示用於列印包括空隙之組件的後續層的所產生檔案；及重複用於後續層的之驟，以完成包括該等空隙之該組件的列印。Furthermore, the set of executable instructions, when executed, is further configured such that the CPM generates a library of substantially 2D layers for subsequent printing of components including voids, each layer including a pattern representing at least one of: Subsequent substantially 2D layers of the dielectric resin, conductive ink and support ink composition of the component including voids and their printing order, and additionally, using the CAM module, obtain a subsequent representation for printing the component including voids the resulting file for the layer; and repeat the steps for subsequent layers to complete the printing of the component including the voids.
此外，在本揭示案之情形下，術語「可操作」意謂系統及/或裝置及/或程式或某一元件或步驟在功能上經完全功能設定大小、調適且校準，包括用於在啟動時（無關於是否供電或耦接、實施、實現、達成）或當可執行程式由與該系統及/或該裝置相關聯的至少一個處理器執行時執行所敍述功能且符合可適用的可操作性需求。關於系統及AME電路，術語「可操作」意謂系統及/或電路具有完全功能且經校準，包括用於在由至少一個處理器執行時進行所敍述功能之邏輯且符合可適用的可操作性要求。Furthermore, in the context of this disclosure, the term "operable" means that the system and/or device and/or program or some element or step is functionally fully functionally sized, adapted and calibrated, including for use at startup when (regardless of whether or not powered or coupled, implemented, realized, achieved) or when the executable program is executed by at least one processor associated with the system and/or the device to perform the recited function and consistent with applicable operable sexual needs. With respect to systems and AME circuits, the term "operable" means that the systems and/or circuits are fully functional and calibrated, including logic for carrying out the recited functions when executed by at least one processor and consistent with applicable operability Require.
因此，在完成整個物件之列印（換言之，根據其次序列印庫中之檔案，該檔案衍生自表示增材製造電子產品（AME）組件之3D檔案）後，該方法進一步包括將包括該等空隙之該組件浸沒於水中，例如水（換言之，再蒸餾水（DDW）或缺乏氘之水）；及溶解該支撐油墨，其中溶解該支撐之步驟的水溫度在約24℃與約70℃之間持續約15分鐘與120分鐘之間，藉此形成沈積有該支撐油墨圖案之空隙。Thus, after completing the printing of the entire object (in other words, according to the file in the subsequent serial print library, the file being derived from the 3D file representing the Additively Manufactured Electronics (AME) component), the method further includes including the voids submerging the component in water, such as water (in other words, redistilled water (DDW) or deuterium-deficient water); and dissolving the support ink, wherein the water temperature of the step of dissolving the support lasts between about 24°C and about 70°C Between about 15 minutes and 120 minutes, thereby forming voids in which the supporting ink pattern is deposited.
在例示性實施中，用於製造本文所述之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法及系統中所用的列印系統可進一步包括又一功能列印頭，該等列印頭經組態以分配不同於所用之初始支撐油墨組合物的第二支撐油墨組合物。使用額外支撐油墨頭，該方法可進一步包括提供額外支撐油墨組合物；在使用該第一列印頭、該第二列印頭或任何其他功能列印頭（及其任何變換）之步驟之後、依序或同時，使用額外支撐油墨列印頭，形成預定圖案，該預定圖案對應於額外支撐表示，其由來自3D可視化檔案之CAM模組產生且表示為用於列印之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的實質上2D層中的圖案。In an exemplary implementation, the printing system used in the methods and systems for fabricating the components described herein with resin/dielectric and metal/conductive compositions having voids therein may further include a further functional print head, The printheads are configured to dispense a second support ink composition different from the initial support ink composition used. Using an additional support ink head, the method may further include providing an additional support ink composition; after the step of using the first print head, the second print head, or any other functional print head (and any permutations thereof), Sequentially or simultaneously, using additional support ink printheads, a predetermined pattern is formed, the predetermined pattern corresponding to the additional support representation generated by the CAM module from the 3D visualization file and represented as a resin/dielectric for printing and a pattern in a substantially 2D layer of components of metal/conductive components with voids therein.
可隨後進一步處理（例如固化、冷卻、交聯及類似者）對應於第一或額外支撐油墨組合物之圖案表示的預定圖案，以使圖案功能化為如上所述之支撐。其後可視需要對每個順序層重複沈積支撐油墨組合物之過程。The predetermined pattern corresponding to the pattern representation of the first or additional support ink composition may then be further processed (eg, curing, cooling, cross-linking, and the like) to functionalize the pattern into a support as described above. The process of depositing the supporting ink composition may thereafter be repeated as desired for each sequential layer.
術語「形成」（及其變體「形成」等）在例示性實施中係指使用此項技術中已知之任何合適的方式泵送、噴射、傾倒、釋放、置換、點塗、循環或以其他方式置放流體或材料（例如，導電油墨）與另一材料（例如，基板、樹脂或另一層）接觸。The term "form" (and its variants "form", etc.) in exemplary implementations refers to pumping, spraying, pouring, releasing, displacing, dispensing, circulating or otherwise using any suitable means known in the art The manner in which a fluid or material (eg, conductive ink) is placed in contact with another material (eg, a substrate, resin, or another layer).
同樣地，其他功能「頭」可位於介電/樹脂列印頭及/或導電（含金屬）列印頭之前、之間或之後。此等可包含經組態以在預定波長（□）例如在190 nm與約400 nm之間（例如365 nm）下發射電磁輻射的電磁（例如，光化）輻射源，其在例示性實施中可用於加快及/或調節及/或促進可結合用於導電油墨中之金屬奈米粒子分散液使用的光可聚合樹脂固化。其他功能頭可為包含紅外燈之加熱元件，具有各種油墨之額外列印頭（例如，預焊接連接性油墨、各種組件（例如電容器、電晶體及類似物）之標記列印）及前述之組合。Likewise, other functional "heads" may be located before, between, or after the dielectric/resin printheads and/or the conductive (metal-containing) printheads. These may include electromagnetic (eg, actinic) radiation sources configured to emit electromagnetic radiation at predetermined wavelengths (□), such as between 190 nm and about 400 nm (eg, 365 nm), in an exemplary implementation Can be used to accelerate and/or regulate and/or facilitate curing of photopolymerizable resins that can be used in conjunction with metal nanoparticle dispersions used in conductive inks. Other functional heads may be heating elements including infrared lamps, additional print heads with various inks (eg, pre-solder connectivity inks, indicia printing of various components such as capacitors, transistors, and the like), and combinations of the foregoing .
在本揭示案之情形下，術語「燒結」表示藉由加熱及/或壓力來壓實且形成固體物質之材料而不使其熔融至液化的過程。用於緻密化之驅動力為自由能的變化，其由懸浮於導電油墨中之奈米粒子之表面積降低及表面自由能降低引起。燒結可形成經改質但較低能量之固態與固態黏性界面，其固態/液態及/或固態/固態及/或固態/空氣自由能總體降低。此外，在某些實施中進行的燒結及固化使用獨立階段且不在列印系統之相同空間內進行。應進一步注意，經燒結導電油墨內之金屬奈米粒子的濃度經組態以超過三維位點滲濾臨限值。In the context of the present disclosure, the term "sintering" refers to the process of compacting and forming a solid mass of material by heat and/or pressure without melting it to liquefaction. The driving force for densification is the change in free energy caused by the reduction in the surface area and surface free energy of the nanoparticles suspended in the conductive ink. Sintering can form a modified but lower energy solid and solid viscous interface with an overall reduction in solid/liquid and/or solid/solid and/or solid/air free energy. Furthermore, the sintering and curing performed in some implementations use separate stages and are not performed in the same space of the printing system. It should be further noted that the concentration of metal nanoparticles within the sintered conductive ink is configured to exceed the three-dimensional site percolation threshold.
如所指示，用以實施用於製造具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的方法可具有導電油墨列印頭，該油墨可含有不同金屬。舉例而言，用於所揭示之系統及方法中的導電油墨組合物可包括（例如）：銀（Ag）奈米粒子，同時一或多種導電油墨可包括不同金屬，例如銅或金。同樣，亦可使用其他金屬（例如，Al）或金屬前驅體，且所提供之實例不應視為限制性的。As indicated, the method used to implement the method for fabricating components having resin/dielectric and metal/conductive components with voids therein may have conductive ink printheads, the inks may contain different metals. For example, conductive ink compositions used in the disclosed systems and methods can include, for example, silver (Ag) nanoparticles, while one or more conductive inks can include different metals, such as copper or gold. Likewise, other metals (eg, Al) or metal precursors may also be used, and the examples provided should not be considered limiting.
可在DI/樹脂油墨組合物沈積及固化及/或第二導電油墨沈積及燒結及/或支撐油墨組合物沈積及固化中之每一者之前或之後採取其他類似功能步驟（且因此用於影響此等步驟之構件）。此等步驟可包含（但不限於）：加熱步驟（受加熱元件或熱空氣影響）；光固化或暴露於任何其他適當的光化輻射源（使用例如UV光源）；乾燥（例如使用真空區及加熱元件）；（反應性）電漿沈積（例如使用加壓電漿槍及電漿束控制器）；在塗佈之前使諸如{4-[(2-羥基十四基)-烴氧基]-苯基}-苯基六氟銻酸錪交聯至DI/樹脂聚合物溶液或用作與金屬前驅體或奈米粒子之分散劑；退火或促進氧化還原反應。Other similar functional steps may be taken before or after each of the DI/resin ink composition deposition and curing and/or the second conductive ink deposition and sintering and/or the supporting ink composition deposition and curing (and thus serve to affect the components of these steps). Such steps may include (but are not limited to): heating steps (influenced by heating elements or hot air); photocuring or exposure to any other suitable source of actinic radiation (using eg a UV light source); drying (eg using a vacuum zone and heating element); (reactive) plasma deposition (eg using a pressurized plasma gun and plasma beam controller); -Phenyl}-phenyl iodonium hexafluoroantimonate is crosslinked to DI/resin polymer solutions or used as a dispersant with metal precursors or nanoparticles; annealing or promoting redox reactions.
在某些例示性實施中，可在樹脂或導電部分上使用雷射（例如選擇性雷射燒結/熔融、直接雷射燒結/熔融）或電子束熔融。應注意，導電成分之燒結可甚至在環境下進行，藉此將該導電部分列印於物件之DI/樹脂/支撐部分的頂部上。應注意，導電層可沈積於樹脂層之間，與樹脂層上方之塗層圖案分開且不同。舉例而言，導電層可沈積於支撐層上方，其在移除之後將獨立於任何樹脂材料。In certain exemplary implementations, a laser (eg, selective laser sintering/melting, direct laser sintering/melting) or electron beam melting may be used on the resin or conductive portion. It should be noted that sintering of the conductive component can even be done at ambient, whereby the conductive portion is printed on top of the DI/resin/support portion of the object. It should be noted that the conductive layer may be deposited between the resin layers, separate and distinct from the coating pattern over the resin layers. For example, a conductive layer can be deposited over a support layer, which after removal will be independent of any resinous material.
因此，在例示性實施中，將導電噴墨油墨沈積至基板上，藉此形成第一列印導電圖案層之步驟及/或將DI/樹脂油墨沈積至可移除基板上及/或可移除支撐之步驟在加熱、光固化乾燥、沈積電漿、交聯、退火、促進氧化還原反應、燒結、熔融步驟或包括前述中之一或多者的步驟組合之前、之後或與其同時進行。Thus, in exemplary implementations, the steps of depositing a conductive inkjet ink onto a substrate, thereby forming a first printed conductive pattern layer, and/or depositing a DI/resin ink onto a removable substrate and/or removable The step of removing the support is performed before, after, or concurrently with the heating, photocuring drying, plasma deposition, crosslinking, annealing, redox promotion, sintering, melting step, or a combination of steps including one or more of the foregoing.
在例示性實施中，調配導電油墨及/或DI/樹脂油墨組合物及/或支撐油墨組合物考慮到沈積工具所施加之需求（若存在）（例如列印頭，就組合物之黏度及表面張力而言）及沈積表面特徵（例如親水性或疏水性，及所用可剝離或可移除基板或支撐材料之界面能）。使用例如具有壓電頭之噴墨列印，導電油墨及/或DI/樹脂油墨及支撐油墨組合物的黏度（在40℃與55℃之間量測）可例如不低於約5 cP，例如不低於約8 cP或不低於約10 cP且不高於約30 cP，例如不高於約20 cP或不高於約15 cP。同樣，導電油墨及/或DI/樹脂油墨組合物及/或支撐油墨組合物可經調適以具有在約25 mN/m與約35 mN/m之間，例如在約29 mN/m與約31 mN/m之間的動態表面張力（係指當油墨小液滴在列印頭噴嘴陣列的孔口處形成時的表面張力），藉由在50 ms之表面老化及25℃下最大鼓泡壓力張力所量測。動態表面張力可經調配以提供與可剝離基板、支撐材料、樹脂層或其組合之小於85°的接觸角。In an exemplary implementation, the conductive ink and/or the DI/resin ink composition and/or the support ink composition are formulated taking into account the demands imposed by the deposition tool, if any, (eg, print heads, in terms of viscosity and surface of the composition) tension) and deposition surface characteristics (such as hydrophilicity or hydrophobicity, and the interfacial energy of the peelable or removable substrate or support material used). Using, for example, ink jet printing with piezoelectric heads, the viscosity of the conductive ink and/or DI/resin ink and support ink composition (measured between 40°C and 55°C) may be, for example, not less than about 5 cP, eg No less than about 8 cP or no less than about 10 cP and no more than about 30 cP, eg, no more than about 20 cP or no more than about 15 cP. Likewise, the conductive ink and/or DI/resin ink composition and/or support ink composition can be adapted to have between about 25 mN/m and about 35 mN/m, such as between about 29 mN/m and about 31 mN/m Dynamic surface tension between mN/m (referring to the surface tension when ink droplets are formed at the orifice of the printhead nozzle array) by surface aging at 50 ms and maximum bubbling pressure at 25°C Tension is measured. The dynamic surface tension can be formulated to provide a contact angle with the peelable substrate, support material, resin layer, or a combination thereof of less than 85°.
在例示性實施中，使用銀形成之導電部分圖案使用奈米銀懸浮液之油墨列印。具有樹脂/介電及金屬/導電成分之3D組件（其中具有空隙）之2D表示的導電部分，以及本文支撐油墨可在燒結期間藉由例如具有較高縱橫比之具有較薄或較小特點的銀奈米粒子顯著提高品質。換言之，藉由具有縱橫比R遠高於1 （R＞＞1）之導電奈米粒子。具有高縱橫比可歸因於（例如）油墨在夾盤上之基板之運動方向上的流動定向而產生奈米粒子之對準，或在另一例示性實施中，藉由自列印頭的孔***出過程及基板之進展。In an exemplary implementation, patterns of conductive portions formed using silver are printed using inks of nanosilver suspensions. Conductive portions of 2D representations of 3D components with resin/dielectric and metal/conductive components (with voids therein), and support inks herein can be produced during sintering by, for example, having thinner or smaller features with higher aspect ratios. Silver nanoparticles significantly improve quality. In other words, by having conductive nanoparticles with an aspect ratio R much higher than 1 (R>>1). Having a high aspect ratio can be attributed to, for example, the orientation of the ink flow in the direction of motion of the substrate on the chuck, resulting in nanoparticle alignment, or in another exemplary implementation, by self-printing The orifice injection process and the progress of the substrate.
在例示性實施中，術語「夾盤」意欲意謂用於支撐、固持或保持基板或工件之機構。夾盤可包含一或多個零件。在一個例示性實施中，夾盤可包含載物台及***物（平台）之組合，經加套或以其他方式經組態以加熱及/或冷卻且具有另一類似組件，或其任何組合。In an exemplary implementation, the term "chuck" is intended to mean a mechanism for supporting, holding, or retaining a substrate or workpiece. A chuck can contain one or more parts. In one exemplary implementation, the chuck may comprise a combination of a stage and an insert (platform), jacketed or otherwise configured to heat and/or cool and have another similar component, or any combination thereof .
在例示性實施中，允許具有樹脂/介電及金屬/導電成分之3D組件（其中具有空隙）之連續或半連續噴墨列印的噴墨油墨組合物及方法可藉由在可移除基板或任何後續層上方在預定距離處例如以二（X-Y）（應理解，列印頭亦可在Z軸上移動）維形式當操縱列印頭（或基板）時一次從一個孔口排出本文所提供之液體油墨之小液滴而圖案化。列印頭之高度可隨層之數目而變化，保持例如固定距離。在例示性實施中，每一小液滴可經組態以根據命令藉由例如壓力脈衝經由可變形壓電晶體自可操作地耦接至孔口之阱沿預定軌跡到達基板。第一噴墨導電油墨之列印可為累加性的且可容納更大數目個層。用於本文所述之方法的所提供之噴墨列印頭可提供等於或低於約3 µm-10,000 µm之最小層膜厚度。In an exemplary implementation, inkjet ink compositions and methods that allow continuous or semi-continuous inkjet printing of 3D components with resin/dielectric and metal/conductive components having voids therein can be achieved by printing on removable substrates or any subsequent layer at a predetermined distance such as in a two (XY) (it should be understood that the print head can also move in the Z axis) dimension when manipulating the print head (or substrate) from one orifice at a time. Patterned with small droplets of supplied liquid ink. The height of the print head can vary with the number of layers, maintaining eg a fixed distance. In an exemplary implementation, each droplet can be configured to follow a predetermined trajectory to the substrate by, for example, a pressure pulse via a deformable piezoelectric crystal from a well operably coupled to an orifice on command. Printing of the first inkjet conductive ink can be additive and can accommodate a greater number of layers. The provided inkjet printheads for use in the methods described herein can provide minimum layer thicknesses equal to or less than about 3 μm to 10,000 μm.
用於所述方法及可實施於系統中的各種列印頭當中操縱的輸送機可經組態以約5 mm/秒與約1000 mm/秒之間的速度移動。例如夾盤之速度可取決於例如：所需產出量、過程中所用之列印頭的數目、具有樹脂/介電及金屬/導電成分之所列印組件（其中具有空隙）之層的數目及厚度、DI/樹脂油墨及/或支撐油墨組合物之固化時間、油墨溶劑之蒸發速率、分配在導電油墨及/或DI/樹脂油墨組合物及/或支撐油墨組合物之間的列印頭的距離，及類似者或包括前述中之一或多者的因子之組合。The conveyors used in the methods and maneuvered among the various print heads that can be implemented in the system can be configured to move at speeds between about 5 mm/sec and about 1000 mm/sec. For example, the speed of the chuck may depend on, for example, the desired throughput, the number of print heads used in the process, the number of layers of printed components with resin/dielectric and metal/conductive compositions (with voids in them) and thickness, curing time of DI/resin ink and/or support ink composition, evaporation rate of ink solvent, print head distributed between conductive ink and/or DI/resin ink composition and/or support ink composition distance, and the like or a combination of factors including one or more of the foregoing.
在例示性實施中，具有不同熱機械特徵參數之導電油墨及/或DI/樹脂油墨組合物及/或支撐油墨組合物之每一小液滴的體積各自的範圍可在0.5到300皮升（pL）之間，例如1至4 pL且視驅動脈衝之強度及油墨之特性而定。用於排出單個小液滴之波形可為10 V至約70 V脈衝，或約16 V至約20 V，且可以約0.1 kHz與約18 kHz之間的頻率排出。In an exemplary implementation, the volume of each droplet of the conductive ink and/or DI/resin ink composition and/or supporting ink composition with different thermomechanical characteristics may each range from 0.5 to 300 picoliters ( pL), for example 1 to 4 pL and depends on the intensity of the drive pulse and the properties of the ink. The waveform used to expel a single droplet can be a 10 V to about 70 V pulse, or about 16 V to about 20 V, and can be expelled at a frequency between about 0.1 kHz and about 18 kHz.
DI/樹脂油墨可經調適以在列印頭儲集器內具有穩定性。舉例而言，固體內含物（亦即若膠態懸浮液，則懸浮固體，或若溶液，則為溶質）可在約5與約100重量%之間。同樣，懸浮油墨固體，換言之，乳膠油墨可藉由額外適合之界面活性劑均勻分散於溶劑中。相反，適合之界面活性劑可能並非必需的，且油墨可藉由併入光敏性單體/寡聚物及其多官能丙烯酸酯之組合而具有100%活性，其中可能不會發生明顯沈降。DI/resin inks can be adapted to have stability within the printhead reservoir. For example, the solid content (ie, the suspended solids if a colloidal suspension, or the solute if a solution) can be between about 5 and about 100% by weight. Likewise, suspended ink solids, in other words latex inks, can be homogeneously dispersed in a solvent by means of additional suitable surfactants. Conversely, a suitable surfactant may not be necessary, and the ink may be 100% active by incorporating a combination of photosensitive monomers/oligomers and their multifunctional acrylates, where significant sedimentation may not occur.
在例示性實施中，用於可實施於本文所述之系統中之方法的DI/樹脂形成油墨可為包括以下之懸浮液、乳液或溶液組合物：單體、寡聚物或包括前述之組合。In exemplary implementations, the DI/resin-forming inks used in the methods that can be implemented in the systems described herein can be suspension, emulsion, or solution compositions comprising: monomers, oligomers, or combinations comprising the foregoing .
起始樹脂主鏈可使用引發劑，例如過氧化苯甲醯（BP）及其他含過氧化物之化合物進行。如本文所用，術語「引發劑」一般係指引發化學反應之物質，特定言之引發聚合之任何化合物，或產生引發聚合之反應性物質，包含例如且不限於共引發劑及/或光引發劑。The starting resin backbone can be carried out using initiators such as benzyl peroxide (BP) and other peroxide-containing compounds. As used herein, the term "initiator" generally refers to a substance that initiates a chemical reaction, in particular any compound that initiates polymerization, or produces a reactive substance that initiates polymerization, including, for example and without limitation, co-initiators and/or photoinitiators .
術語「活單體」、「活寡聚物」、「活聚合物」或其對應物（例如共聚單體）組合在例示性實施中係指具有能夠形成自由基反應之至少一個官能基的單體、短單體基團或聚合物（換言之，反應可持續且以其他方式藉由端基終止）。浸漬有多孔顆粒之活單體、活寡聚物或其組合的量將隨設法形成之板、膜或薄片的所需物理化學特徵變化。活單體、活寡聚物或其組合的數量平均分子量（
在例示性實施中，交聯劑、共聚單體、共寡聚物、共聚合物或包括前述中之一或多者的組合物用於所提供之樹脂油墨中，可為一部分或經組態以在樹脂油墨組合物內形成溶液、乳液或懸浮液。In exemplary implementations, crosslinkers, comonomers, co-oligomers, co-polymers, or compositions comprising one or more of the foregoing are used in the provided resin inks, which may be a portion or configured To form a solution, emulsion or suspension within the resin ink composition.
在另一例示性實施中，DI/樹脂油墨組合物包括能夠使用本文所提供之光引發劑進行光引發的聚合物之活性組件。此類活單體、活寡聚物、活聚合物或其組合可為例如多官能丙烯酸酯，可為以下中之至少一者：1,2-乙二醇二丙烯酸酯、1,3-丙二醇二丙烯酸酯、1,4-丁二醇二丙烯酸酯、1,6-己二醇二丙烯酸酯、二丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、乙氧基化新戊二醇二丙烯酸酯、丙氧基化新戊二醇二丙烯酸酯、三丙二醇二丙烯酸酯、雙酚-A-二縮水甘油醚二丙烯酸酯、羥基特戊酸新戊二醇二丙烯酸酯、乙氧基化雙酚-A-二縮水甘油醚二丙烯酸酯、聚乙二醇二丙烯酸酯、三羥甲基丙烷三丙烯酸酯、乙氧基化三羥甲基丙烷三丙烯酸酯、丙氧基化三羥甲基丙烷三丙烯酸酯、丙氧基化甘油三丙烯酸酯、參(2-丙烯醯基氧基乙基)異氰尿酸酯、季戊四醇三丙烯酸酯、乙氧基化季戊四醇三丙烯酸酯、季戊四醇四丙烯酸酯、乙氧基化季戊四醇四丙烯酸酯、二(三羥甲基丙烷)四丙烯酸酯、二季戊四醇五丙烯酸酯及二季戊四醇六丙烯酸酯。In another exemplary implementation, a DI/resin ink composition includes a reactive component of a polymer capable of being photoinitiated using the photoinitiators provided herein. Such living monomers, living oligomers, living polymers, or combinations thereof may be, for example, multifunctional acrylates, which may be at least one of the following: 1,2-ethylene glycol diacrylate, 1,3-propanediol Diacrylate, 1,4-Butanediol Diacrylate, 1,6-Hexanediol Diacrylate, Dipropylene Glycol Diacrylate, Neopentyl Glycol Diacrylate, Ethoxylated Neopentyl Glycol Diacrylate Esters, Propoxylated Neopentyl Glycol Diacrylate, Tripropylene Glycol Diacrylate, Bisphenol-A-Diglycidyl Ether Diacrylate, Hydroxypivalate Neopentyl Glycol Diacrylate, Ethoxylated Bis Phenol-A-Diglycidyl Ether Diacrylate, Polyethylene Glycol Diacrylate, Trimethylolpropane Triacrylate, Ethoxylated Trimethylolpropane Triacrylate, Propoxylated Trimethylol Propane triacrylate, propoxylated glycerol triacrylate, sam(2-acryloyloxyethyl) isocyanurate, pentaerythritol triacrylate, ethoxylated pentaerythritol triacrylate, pentaerythritol tetraacrylate , Ethoxylated pentaerythritol tetraacrylate, bis(trimethylolpropane) tetraacrylate, dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate.
DI/樹脂油墨部分之列印圖案可由富含樹脂油墨組合物（例如懸浮液、乳液、溶液及其類似物）製成。術語「富含樹脂」係指其中包含與將DI/樹脂油墨層結合至底層基板、導電層或結合至具有樹脂/介電及金屬/導電成分之另一組件（其中具有空隙）之層所需的聚合物樹脂組件之比例相比更大比例之聚合物樹脂組件的組合物或支撐部分及其組合。舉例而言，富含樹脂組件層可包含數量為總DI/樹脂油墨重量之至少95重量%的聚合物DI/樹脂。The printed pattern of the DI/resin ink portion can be made from resin rich ink compositions such as suspensions, emulsions, solutions, and the like. The term "resin-rich" refers to the inclusion of a layer required to bond a DI/resin ink layer to an underlying substrate, a conductive layer, or to another component with resin/dielectric and metal/conductive components (with voids therein) The proportion of the polymer resin component is compared to a larger proportion of the polymer resin component of the composition or support portion and combinations thereof. For example, the resin-rich component layer can include polymeric DI/resin in an amount of at least 95 wt% of the total DI/resin ink weight.
在例示性實施中，在與由CAM模組執行的用於製造之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）相關的參數選擇中使用的參數可為例如：所需列印產出量、層中之樹脂圖案、層中之導電圖案、所需樹脂層色彩、樹脂圖案之著色次序、層中之DI/樹脂之固化需求及/或導電/金屬油墨組合物圖案的燒結需求、（可移除式）支撐層之需要及位置，或包括前述中之一或多者的參數之組合。In an exemplary implementation, the parameters used in the parameter selection performed by the CAM module for the manufacture of components having resin/dielectric and metal/conductive components with voids therein may be, for example: Print yield, resin pattern in layer, conductive pattern in layer, desired resin layer color, color sequence of resin pattern, curing requirement of DI/resin in layer and/or sintering of conductive/metallic ink composition pattern Requirement, need and location of the (removable) support layer, or a combination of parameters including one or more of the foregoing.
術語「模組」之使用並不暗示描述或主張作為模組之部分的組件或功能性全部組態在共同封裝中。實際上，模組之各種組件中之任一者或全部（無論控制邏輯或其他組件）可組合在單一封裝中或分開維持，且可進一步分佈於多個群組或封裝中或跨多個部位分佈。另外，術語「模組」在本文中用以指軟體電腦程式碼及/或用以提供歸因於模組之功能性的任何硬體或電路系統。另外，術語「模組」或「組件」亦可指執行於計算系統上的軟體目標或常式。本文所述之不同組件、模組、引擎及服務可實施為執行於計算系統上之目標或過程（例如，作為單獨線程）。The use of the term "module" does not imply description or claim that the components or functionality that are part of the module are all configured in a common package. Indeed, any or all of the various components of a module (whether control logic or other components) may be combined in a single package or maintained separately, and may be further distributed in multiple groups or packages or across multiple locations distributed. Additionally, the term "module" is used herein to refer to software computer code and/or any hardware or circuitry used to provide functionality attributable to the module. Additionally, the terms "module" or "component" may also refer to software objects or routines that execute on a computing system. The different components, modules, engines, and services described herein can be implemented as objects or processes executing on a computing system (eg, as separate threads).
CAM模組可包括：2D庫，其儲存由具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）之3D可視化檔案轉換的檔案；至少一個處理器，其與各種列印頭、輸送機、夾盤、任何額外功能「頭」及庫通信；非暫時性儲存媒體，其儲存一組可操作指令以供至少一個處理器執行；微機械噴墨列印頭，其與至少一個處理器通信且與庫通信；及列印頭（或列印頭的）介面電路，其與2D檔案庫、記憶體及微機械噴墨列印頭通信，該2D檔案庫經組態以提供對功能層具有特異性之列印操作參數；預處理電腦輔助設計/電腦輔助製造（CAD/CAM）產生的與待製造之具有樹脂/介電及金屬/導電成分之3D組件（其中具有空隙）相關聯的資訊，藉此獲得複數個2D檔案；將在預處理步驟中處理的複數個2D檔案自具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）、3D可視化檔案載入至2D檔案庫中；及使用2D檔案庫，指示至少一個處理器按預定次序列印具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）之預定層。The CAM module may include: a 2D library that stores files converted from 3D visualization files of components having resin/dielectric and metal/conductive components (with voids in them); at least one processor that communicates with various print heads, transport machine, chuck, any additional functional "heads" and library communications; a non-transitory storage medium that stores a set of operational instructions for execution by at least one processor; a micromachined inkjet printhead that communicates with at least one processor communicate and communicate with the library; and a printhead (or printhead's) interface circuit that communicates with a 2D file library, memory, and a micromachined inkjet printhead, the 2D file library being configured to provide access to functional layers Specific print operation parameters; preprocessing CAD/CAM generated 3D components associated with resin/dielectric and metal/conductive components (with voids) to be fabricated information, thereby obtaining a plurality of 2D files; the plurality of 2D files processed in the preprocessing step are loaded into the 2D file library from components with resin/dielectric and metal/conductive components (with voids therein), 3D visualization files and using the 2D archive, instructing at least one processor to print predetermined layers of components having resin/dielectric and metal/conductive components in a predetermined order, with voids therein.
表示用於製造之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的3D可視化檔案可為：asm、STL、IGES、STEP、Catia、SolidWorks、ProE、3D工作室、Gerber、Rhino或包括前述中之一或多者之檔案；且其中表示至少一個實質上2D層（且上傳至庫）之檔案可為例如JPEG、GIF、TIFF、BMP、PDF檔案或包括前述中之一或多者之組合。3D visualization files representing components with resin/dielectric and metal/conductive components (with voids in them) for fabrication can be: asm, STL, IGES, STEP, Catia, SolidWorks, ProE, 3D Studio, Gerber, Rhino or a file including one or more of the foregoing; and wherein the file representing at least one substantially 2D layer (and uploaded to the library) may be, for example, a JPEG, GIF, TIFF, BMP, PDF file or include one or more of the foregoing combination of.
在某些例示性實施中，CAM模組進一步包括用於製造一或多個具有樹脂/介電及金屬/導電成分之組件（其中具有空隙），例如電子組件、機器部件、USB連接器、列印電路板（參見例如圖1A、1B）及類似者的電腦程式產品。列印組件可為例如醫療裝置、電子裝置，其包括離散導電組件及各自的介電/樹脂組件兩者，且兩者視情況同時或依序且連續地列印。術語「連續」及其變體意欲意謂以實質上不間斷的過程列印。在另一例示性實施中，連續係指沿層、部件或結構之長度不存在顯著斷裂之層、部件或結構。In certain exemplary implementations, the CAM module further includes components for fabricating one or more components having resin/dielectric and metal/conductive compositions (with voids therein), such as electronic components, machine parts, USB connectors, columns Computer program products of printed circuit boards (see eg Figures 1A, 1B) and the like. Printing components may be, for example, medical devices, electronic devices that include both discrete conductive components and respective dielectric/resin components, and both are printed simultaneously or sequentially and continuously, as appropriate. The term "continuous" and variations thereof are intended to mean printing in a substantially uninterrupted process. In another exemplary implementation, continuous refers to a layer, component, or structure without significant breaks along the length of the layer, component, or structure.
舉例而言，且如圖1所繪示，使用所述方法列印PCB。使用所述系統連續地列印包括所示空隙之整個PCB，藉此使用預固化支撐油墨組合物且用導電油墨及DI/樹脂油墨組合物列印該支撐油墨組合物，且隨後移除該支撐油墨組合物以形成所示空隙。For example, and as depicted in FIG. 1, a PCB is printed using the method. The entire PCB including the voids shown is continuously printed using the system, whereby a pre-cured support ink composition is used and the support ink composition is printed with a conductive ink and a DI/resin ink composition, and the support is subsequently removed ink composition to form the voids shown.
控制本文所述之列印過程的電腦可包括：電腦可讀非暫時性儲存媒體，其具有包括在其中之電腦可讀程式碼，該電腦可讀程式碼在由數位計算裝置中之處理器執行時在例示性實施中使三維噴墨列印單元執行以下步驟：預處理電腦輔助設計/電腦輔助製造（CAD/CAM）產生與待製造之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）相關聯的資訊（換言之，表示該組件之3D可視化檔案），藉此獲得複數個2D檔案（換言之，該檔案表示用於列印該組件之層的至少一個實質上2D層），每一2D檔案對以特定次序之預定層具有特異性；將預處理步驟中處理的複數個2D檔案載入至2D檔案庫上；將導電材料之小液滴流自該三維噴墨列印單元之噴墨列印頭導引於基板之表面處；將DI/樹脂油墨材料之小液滴流自該三維噴墨列印單元之另一噴墨列印頭導引於基板之表面處；或者或另外地將支撐油墨組合物之小液滴流自該三維噴墨列印單元之又一噴墨列印頭導引於基板之表面處；在夾盤上的基板之x-y平面中相對於基板移動第一、第二及第三噴墨頭，其中在基板之x-y平面中相對於基板移動第一、第二及第三噴墨頭，在基板上以具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）的逐層製造進行複數個層中之每一層的製備。A computer controlling the printing process described herein may include a computer-readable non-transitory storage medium having computer-readable code embodied therein for execution by a processor in a digital computing device In an exemplary implementation, the three-dimensional inkjet printing unit is caused to perform the following steps: Preprocessing Computer Aided Design/Computer Aided Manufacturing (CAD/CAM) to produce and to be fabricated components having resin/dielectric and metal/conductive components (wherein information (in other words, a 3D visualization file representing the component), thereby obtaining a plurality of 2D files (in other words, the file representing at least one substantially 2D layer of the layers used to print the component), each A 2D file is specific to a predetermined layer in a specific order; the plurality of 2D files processed in the preprocessing step are loaded onto the 2D file library; small droplets of conductive material are streamed from the 3D inkjet printing unit An ink jet print head is directed at the surface of the substrate; droplets of DI/resin ink material are directed at the surface of the substrate from another ink jet print head of the 3D ink jet print unit; or or A stream of droplets of supporting ink composition is additionally directed from a further inkjet print head of the three-dimensional inkjet printing unit at the surface of the substrate; moving relative to the substrate in the xy plane of the substrate on the chuck First, second and third inkjet heads, wherein the first, second and third inkjet heads are moved relative to the substrate in the xy plane of the substrate, on the substrate with resin/dielectric and metal/conductive components. Layer-by-layer fabrication of components (with voids therein) involves the preparation of each of a plurality of layers.
如所指示，使用使用儲存於非暫時性儲存媒體上之可執行指令所提供之系統及裝置所揭示之可實施方法為利用處理器可讀媒體（諸如各種電腦程式）之電腦化方法。電腦程式（軟體及/或固體）可包括用於進行本文所述之方法之步驟的程式碼構件，以及包括儲存於可由電腦讀取之媒體上之程式碼構件的電腦程式產品，諸如硬碟、CD-ROM、DVD、USB記憶棒或儲存媒體，當電腦程式產品載入於電腦之主記憶體中且藉由電腦進行時，儲存媒體可經由諸如網際網路或內部網路之資料網路存取。As indicated, implementable methods disclosed using systems and devices provided using executable instructions stored on non-transitory storage media are computerized methods using processor-readable media, such as various computer programs. A computer program (software and/or solid state) may include code means for carrying out the steps of the methods described herein, as well as computer program products including code means stored on a computer-readable medium, such as a hard disk, CD-ROMs, DVDs, USB sticks or storage media, when the computer program product is loaded into the main memory of the computer and executed by the computer, the storage media can be stored via a data network such as the Internet or an intranet Pick.
因此，術語「非暫時性儲存媒體」及「非暫時性電腦可讀儲存媒體」定義為包含但未必限於可含有、儲存或保留程式、資訊及資料之任何媒體。非暫時性儲存媒體及非暫時性電腦可讀儲存媒體可包含許多實體媒體中之任一者，諸如電子、磁性、光學、電磁或半導體媒體。適合的非暫時性儲存媒體及非暫時性電腦可讀儲存媒體之更特定實例包含但不限於諸如硬碟機、磁帶、隨機存取記憶體（RAM）、唯讀記憶體（ROM）、固態磁碟機（SSD）、串列AT附接（SATA）、可抹除可程式化唯讀記憶體（EPROM）、快閃驅動機、光碟（CD）或數位視訊磁碟（DVD）之磁性電腦磁片。Accordingly, the terms "non-transitory storage medium" and "non-transitory computer-readable storage medium" are defined to include, but not necessarily be limited to, any medium that may contain, store or retain programs, information and data. Non-transitory storage media and non-transitory computer-readable storage media can include any of a number of physical media, such as electronic, magnetic, optical, electromagnetic, or semiconductor media. More specific examples of suitable non-transitory storage media and non-transitory computer-readable storage media include, but are not limited to, such as hard disk drives, magnetic tapes, random access memory (RAM), read only memory (ROM), solid state magnetic Magnetic Computer Magnetic Disk Drive (SSD), Serial AT Attachment (SATA), Erasable Programmable Read-Only Memory (EPROM), Flash Drive, Compact Disc (CD) or Digital Video Disk (DVD) piece.
另外，非暫時性儲存媒體可位於執行程式之第一電腦（例如，所提供之3D噴墨印表機）中，及/或可位於經由網路（諸如網際網路）與第一電腦通信之第二不同電腦中。在後種情況下，第二電腦可將程式指令進一步提供至第一電腦以供執行。術語「記憶體裝置」亦可包含兩個或更多個記憶體裝置，其可駐留於不同部位中，例如，經由網路連接的不同電腦中。因此，舉例而言，位圖庫可駐留於遠離與所提供之3D噴墨印表機耦接之CAM模組之記憶體裝置上，且可由所提供之3D噴墨印表機存取（例如，藉由廣域網路）。Additionally, the non-transitory storage medium may be located in the first computer executing the program (eg, the provided 3D inkjet printer), and/or may be located in communication with the first computer via a network, such as the Internet in a second different computer. In the latter case, the second computer may further provide program instructions to the first computer for execution. The term "memory device" may also include two or more memory devices, which may reside in different locations, eg, in different computers connected via a network. Thus, for example, the bitmap library can reside on a memory device remote from the CAM module coupled to the provided 3D inkjet printer, and can be accessed by the provided 3D inkjet printer (eg, over a wide area network).
除非另外特定陳述，否則如自以下論述顯而易見，應瞭解，貫穿本說明書，利用諸如「處理」、「獲得」、「使用」、「列印」、「形成」、「載入」、「通信」、「偵測」、「計算」、「判定」、「分析」或其類似者之術語的論述係指電腦或計算系統或類似電子計算裝置之動作及/或程序，該等動作及程序將諸如電晶體架構之表示為實體的資料操縱及/或變換成類似地表示為實體結構（換言之，樹脂或金屬/導電）層之其他資料。Unless specifically stated otherwise, as will be apparent from the following discussion, it should be understood that throughout this specification, use of terms such as "processing," "obtaining," "using," "printing," "forming," "loading," "communicating" , "detection," "compute," "determine," "analyze," or the like, refer to the actions and/or procedures of a computer or computing system or similar electronic computing device, such actions and procedures as Data representations of transistor architectures are manipulated and/or transformed into other data similarly represented as layers of solid structures (in other words, resin or metal/conducting).
此外，如本文所用，術語「2D檔案庫」係指一起定義具有樹脂/介電及金屬/導電成分之單AME組件（其中具有空隙）或具有樹脂/介電及金屬/導電成分之複數個組件（其中具有空隙）的一組給定檔案，每一組件用於給定目的。術語亦可用以指一組2D檔案或任何其他柵格圖形檔案格式（影像表示為像素之集合，通常呈矩形網格形式，例如BMP、PNG、TIFF、GIF），其能夠被編索引、搜尋及重新組裝，以提供給定組件之結構層，無論搜尋係針對整個組件或給定特定層。Furthermore, as used herein, the term "2D archive" refers to a single AME component (with voids therein) that together defines a single AME component with resin/dielectric and metal/conductive components or a plurality of components with resin/dielectric and metal/conductive components A given set of profiles (with gaps in them), each component for a given purpose. The term can also be used to refer to a set of 2D files or any other raster graphics file format (an image is represented as a collection of pixels, usually in the form of a rectangular grid, such as BMP, PNG, TIFF, GIF) that can be indexed, searched, and Reassemble to provide structural layers for a given component, whether the search is for the entire component or for a given specific layer.
電腦輔助設計/電腦輔助製造（CAD/CAM）產生與用於使用基於經轉換CAD/CAM資料封裝之噴墨列印的方法、程式及庫中待製造之具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）相關聯的資訊可例如為IGES、DXF、DMIS、NC檔案、GERBER®檔案、EXCELLON®、STL、EPRT檔案、asm、STEP、Catia、SolidWorks、ProE、3D工作室、Rhino檔案及包括前述中之一或多者的3D檔案封裝。另外，附接至圖形物件之屬性傳送製造所需的元資訊，且可精確界定列印次序、影像（換言之，圖案）及影像之結構（例如，樹脂、支撐或金屬），從而將製造資料自設計（例如，3D可視化CAD）高效且有效地傳送至製造（例如用於CAM之2D層檔案庫）。因此且在例示性實施中，使用預處理演算法，將本文所述之GERBER®、EXCELLON®、DWG、DXF、STL、EPRT ASM及其類似物轉化成2D檔案。Methods, programs and libraries for computer-aided design/computer-aided manufacturing (CAD/CAM) generation and use for inkjet printing using packages based on converted CAD/CAM data to be manufactured with resin/dielectric and metal/conductive components The information associated with the components (with voids in them) can be, for example, IGES, DXF, DMIS, NC files, GERBER® files, EXCELLON®, STL, EPRT files, asm, STEP, Catia, SolidWorks, ProE, 3D Studio, Rhino Files and 3D file packages including one or more of the foregoing. In addition, attributes attached to graphical objects convey the meta-information required for manufacturing and can precisely define the printing order, images (in other words, patterns), and the structure of the images (eg, resin, support, or metal), thereby transferring manufacturing data from Design (eg, 3D visualization CAD) is efficiently and effectively transferred to manufacturing (eg 2D layer archive for CAM). Thus, and in an exemplary implementation, GERBER®, EXCELLON®, DWG, DXF, STL, EPRT ASM, and the like described herein are converted into 2D files using preprocessing algorithms.
如本文所用，術語「包括」及其派生詞意欲為指定所陳述特點、元件、組件、群組、整體及/或步驟之存在但不排除其他未陳述特點、元件、組件、群組、整體及/或步驟之存在的開放術語。前述內容亦適用於具有類似含義之字詞，諸如術語「包含」、「具有」及其衍生詞。As used herein, the term "comprising" and its derivatives are intended to specify the presence of stated features, elements, components, groups, integers and/or steps but not to exclude other unrecited features, elements, components, groups, integers and and/or an open term for the existence of a step. The foregoing also applies to words of similar meaning, such as the terms "comprising", "having" and their derivatives.
本文所揭示之所有範圍皆包括端點，且各端點可獨立地彼此組合。「組合」包括摻合物、混合物、合金、反應產物及其類似物。除非本文中另有指示或與上下文明顯矛盾，否則本文之術語「一」及「該/該等」不表示數量之限制，且應解釋為涵蓋單個及多個。如本文所用，後綴「（s）」意欲包含其修飾之術語的單數及複數兩者，由此包含彼術語之一或多者（例如，成分包含一或多個成分）。在本說明書通篇中提及「一個例示性實施」、「另一例示性實施」、「例示性實施」等（當存在時）意謂結合例示性實施所述之特定元件（例如，特點、結構及/或特徵）包含於本文所述之至少一個例示性實施中，且可能或可能不存在於其他例示性實施中。此外，應理解，所述元件可在各種例示性實施中以任何合適的方式組合。All ranges disclosed herein are inclusive of the endpoints, and each endpoint is independently combinable with each other. "Combination" includes blends, mixtures, alloys, reaction products, and the like. Unless otherwise indicated herein or clearly contradicted by context, the terms "a" and "the/the" herein do not denote quantitative limitations and should be construed to encompass both single and plural. As used herein, the suffix "(s)" is intended to include both the singular and the plural of the term it modifies, thereby including one or more of that term (eg, an element includes one or more elements). References throughout this specification to "one exemplary implementation," "another exemplary implementation," "exemplary implementation," etc., when present, mean that particular elements (eg, features, structures and/or features) are included in at least one exemplary implementation described herein, and may or may not be present in other exemplary implementations. Furthermore, it should be understood that the described elements may be combined in any suitable manner in the various exemplary implementations.
本文所揭示之所有範圍皆包括端點，且各端點可獨立地彼此組合。此外，在本文中，術語「第一」、「第二」、「第三」及其類似術語不表示任何順序、數量或重要性，而是用於表示一個元件與另一個元件。All ranges disclosed herein are inclusive of the endpoints, and each endpoint is independently combinable with each other. Furthermore, herein, the terms "first," "second," "third," and similar terms do not denote any order, quantity, or importance, but rather are used to denote one element over another.
同樣地，術語「約」意謂量、大小、參數及其他數量及特徵並非且無需為準確的，而可視需要為近似的及/或更大或更小，從而反映容限、轉換因子、捨入、量測誤差及其類似者，以及本領域中熟習此項技術者已知的其他因素。通常，無論是否明確地陳述，量、尺寸、調配物、參數或其他數量或特徵皆為「約」或「近似」的。Likewise, the term "about" means that quantities, magnitudes, parameters, and other quantities and characteristics are not and need not be exact, but can be approximated and/or larger or smaller as desired, reflecting tolerances, conversion factors, rounding input, measurement error and the like, as well as other factors known to those skilled in the art. Often, amounts, dimensions, formulations, parameters or other quantities or characteristics are "about" or "approximately" whether or not expressly stated.
此外，本發明提供一種包括丙烯酸酯聚合物、寡聚物及其衍生物中之至少一者的預固化支撐油墨組合物，其中其丙烯酸酯衍生物中之至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化水溶性共聚物；界面活性劑；光引發劑（PI），其中該水溶性共聚物與該PI之間的比率（w/w）在1:1與4:1之間，其中（i）該支撐油墨為懸浮液、乳液及溶液中之至少一者，（ii）包括約50%（w/w）與90%（w/w）之間的該預固化丙烯酸酯單體及其衍生物中之至少一者；約10%（w/w）與20%（w/w）之間的該共聚物；約5%（w/w）與10%（w/w）之間的該PI；及不超過1%（w/w）之該界面活性劑，其中該界面活性劑不活化交聯，其中（iii）該共聚物主鏈之重量平均分子量（
在另一例示性實施中，本發明提供一種使用噴墨印表機製造包括空隙之三維增材製造電子產品（AME）的方法，該方法包括：提供噴墨列印系統，其包括：第一列印頭，其可操作以分配介電樹脂組合物；第二列印頭，其可操作以分配導電油墨組合物；第三列印頭，其可操作以分配支撐油墨組合物，其中該支撐油墨組合物包括丙烯酸酯聚合物、寡聚物及其衍生物中之至少一者，其中該丙烯酸酯聚合物、寡聚物、其衍生物中之該至少一者各自經預固化；包括具有芳族及脂族單體之主鏈的預固化水溶性共聚物；適於抑制該等預固化丙烯酸酯寡聚物及/或其衍生物與該水溶性共聚物之交聯的界面活性劑；光引發劑（PI），其中該水溶性共聚物與該PI之間的比率（w/w）在1:1與4:1之間；輸送機，其可操作地耦接至該第一列印頭、該第二列印頭及該第三列印頭，該輸送機經組態以將基板輸送至該第一列印頭、第二列印頭及第三列印頭中之每一者；及電腦輔助製造（「CAM」）模組，其與該第一列印頭及該第二列印頭中之每一者通信，該CAM進一步包含中央處理模組（CPM），該中央處理模組包括至少一個處理器，該至少一個處理器與非暫時性電腦可讀儲存裝置通信，該可讀儲存裝置經組態以儲存指令，該等指令在由該至少一個處理器執行時使得該CAM藉由執行包括以下之步驟來控制該噴墨列印系統： 接收表示包括該等空隙之AME電路的3D可視化檔案；及產生具有複數個檔案之檔案庫，各檔案表示用於列印包括該等空隙之該AME電路的實質上2D層及該實質上2D層之列印次序，其中各層包括在相同層檔案上的介電油墨圖案、導電油墨圖案及支撐油墨圖案，且其中該CAM模組經組態以控制該第一列印頭、該第二列印頭及該第三列印頭中之每一者；提供該介電樹脂組合物、該導電油墨組合物及該支撐油墨組合物；使用該CAM模組，自該庫獲得第一層檔案；使用該第一列印頭，在該基板上形成對應於該介電樹脂之該圖案；使用光化輻射，固化對應於介電樹脂表示之該圖案；使用該第二列印頭，形成對應於導電油墨表示之該圖案；使用熱及壓力中之至少一者，燒結對應於該導電油墨之該圖案；在形成及固化對應於該介電樹脂表示之該圖案的步驟，及形成及燒結對應於該導電油墨表示之圖案的步驟中之至少一者之前或之後，使用該第三列印頭，形成對應於該支撐油墨表示之該圖案；使用光化輻射，固化對應於包括該等空隙之該組件之該第一2D層中該支撐油墨組合物的該圖案；使用該CAM模組，自該庫獲得後續層檔案；使用該第一列印頭，形成對應於該後續層檔案中之該介電樹脂的該圖案；重複固化對應於該介電樹脂表示之該圖案的步驟至自該庫獲得後續層檔案之步驟，至完成該庫中之該實質上2D層檔案的列印；及 移除該基板，藉此製造包括該等空隙之該AME（在溶解該支撐油墨之後），該方法進一步包括（x）將包括該等空隙之該AME浸沒於再蒸餾水（DDW）或缺乏氘之水中；及將支撐油墨溶解於DDW中，藉此形成空隙（換言之，在列印庫中之所有檔案之後，對應於支撐油墨位置之區域），其中（xi）固化該第一層中之該介電樹脂及該支撐油墨中之至少一者（無論在該基板上、CI圖案或DI圖案上）的步驟包括加熱、光聚合、乾燥、沈積電漿、交聯、退火、促進氧化還原反應、纏結或包括前述中之一或多者的組合，其中（xii）該支撐油墨組合物經組態以具有在約180℃與約220℃之間的熔融溫度，同時（xiii）溶解該支撐之步驟的水溫度在約23℃與約70℃之間，其中（xiv）該支撐油墨組合物包括： 約50%（w/w）與90%（w/w）之間的該預固化丙烯酸酯聚合物、寡聚物及其衍生物中之至少一者；約10%（w/w）與20%（w/w）之間的該水溶性共聚物；約5%（w/w）與10%（w/w）之間的該PI；及不超過1%（w/w）之該界面活性劑，其中該界面活性劑不活化交聯，其中（xv）該預固化水溶性共聚物主鏈之重量平均分子量（
儘管已根據一些例示性實施描述了使用基於經轉換3D可視化CAD/CAM資料封裝用於具有樹脂/介電及金屬/導電成分之組件（其中具有空隙）之3D列印的前述揭示內容，但其他例示性實施對於一般熟習此項技術者將顯而易見。此外，所述例示性實施僅作為實例呈現且並不意欲限制本發明之範疇。實情為，本文所述之新穎方法、程式、檔案庫及系統可在不脫離其精神之情況下以多種其他形式體現。因此，熟習此項技術者將由本文中之揭示內容顯而易見其他組合、省略、取代及修改。While the foregoing disclosure has been described according to some exemplary implementations using translated 3D visualization-based CAD/CAM data packaging for 3D printing of components having resin/dielectric and metal/conductive components with voids therein, other Exemplary implementations will be apparent to those of ordinary skill in the art. Furthermore, the exemplary implementations are presented by way of example only and are not intended to limit the scope of the invention. Indeed, the novel methods, programs, archives and systems described herein may be embodied in a variety of other forms without departing from the spirit thereof. Accordingly, other combinations, omissions, substitutions and modifications will be apparent to those skilled in the art from the disclosure herein.
無none
為了更好地理解具有樹脂/介電及/或導電成分之組件及/或物件（具有空隙）的系統、製造方法及組合物，關於其例示性實施，參考隨附實例及圖式，其中：For a better understanding of systems, methods of manufacture, and compositions of components and/or articles (with voids) having resin/dielectric and/or conductive components, with respect to exemplary implementations thereof, reference is made to the accompanying examples and drawings, wherein:
圖1A、1B繪示了在溶解本文所揭示之支撐油墨組合物之前及之後具有介電成分的具有空隙之物件。1A, 1B depict a voided article with a dielectric component before and after dissolving the support ink compositions disclosed herein.
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