相關申請案之交互參照Cross-reference to related applications
本申請案主張2023年9月18日所提交之美國臨時專利申請案第63/538,901號之優先權，該案之揭露以引用方式整體併入本文中。This application claims priority to U.S. Provisional Patent Application No. 63/538,901 filed on September 18, 2023, the disclosure of which is incorporated herein by reference in its entirety.
隨著電腦及資訊通訊設備之高性能、高功能化、網路化之發展，為了高速傳輸並處理大容量的資訊，操作信號趨於高頻化，因此對用於電路基材之材料存在需求，特別係那些使用寬頻電子設備（諸如行動通訊設備）者。With the development of high performance, high functionality and networking of computers and information and communication equipment, in order to transmit and process large amounts of information at high speed, operating signals tend to be high-frequency. Therefore, there is a demand for materials used in circuit substrates, especially those using broadband electronic equipment (such as mobile communication equipment).
預浸材料連同經金屬包覆之層壓體及預浸材一起用於構建各種電子應用中之多層印刷線路板。Prepreg materials are used along with metal-clad laminates and prepregs to construct multi-layer printed circuit boards for a variety of electronic applications.
根據本發明之某些態樣，一種預浸材物品包括一介電基材（層），該介電基材（層）包含：全氟共聚物基質，其包括氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。該物品可進一步包含導電包覆，其設置於該介電基材之一表面上。實施例可包括下列特徵中之一者或二或更多者之任何組合。According to certain aspects of the present invention, a prepreg article includes a dielectric substrate (layer), the dielectric substrate (layer) comprising: a perfluoro copolymer matrix, which includes a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The article may further include a conductive coating, which is disposed on a surface of the dielectric substrate. Embodiments may include any combination of one or two or more of the following features.
在一些態樣，該L-玻璃織物包括L-玻璃、NL-玻璃、L2-玻璃、或其組合之紗線。In some aspects, the L-glass fabric includes yarns of L-glass, NL-glass, L2-glass, or combinations thereof.
一種預浸材物品可具有在20 µm與200 µm之間、30 µm與90 µm之間、或30 µm與60 µm之間之厚度。A prepreg article may have a thickness between 20 µm and 200 µm, between 30 µm and 90 µm, or between 30 µm and 60 µm.
在一些態樣，一種預浸材物品在10 GHz下具有在2.10與2.70之間、或在2.10與2.40之間之介電常數。一介電基材在0至100℃之溫度範圍內可具有其值在-250 ppm/℃至+50 ppm/℃之間之熱係數。在某些態樣，介電基材在10 GHz下具有小於0.0015、在0.0006與0.001之間、或在0.0006與0.0008之間之散逸因數。In some aspects, a prepreg article has a dielectric constant between 2.10 and 2.70, or between 2.10 and 2.40 at 10 GHz. A dielectric substrate can have a thermal coefficient between -250 ppm/°C and +50 ppm/°C over a temperature range of 0 to 100°C. In certain aspects, the dielectric substrate has a dissipation factor of less than 0.0015, between 0.0006 and 0.001, or between 0.0006 and 0.0008 at 10 GHz.
一種預浸材物品可具有界定X-Y平面之平面形狀，且其中該預浸材物品在X-Y平面中之熱膨脹係數係在5 ppm/℃與25 ppm/℃之間、在14 ppm/℃與20 ppm/℃之間、或在16 ppm/℃與22 ppm/℃之間。A prepreg article may have a planar shape defining an X-Y plane, and wherein the coefficient of thermal expansion of the prepreg article in the X-Y plane is between 5 ppm/°C and 25 ppm/°C, between 14 ppm/°C and 20 ppm/°C, or between 16 ppm/°C and 22 ppm/°C.
在一些態樣，該氟化全氟共聚物包括具有第一熔體流動速率之第一氟化四氟乙烯/六氟丙烯及具有第二熔體流動速率之第二四氟乙烯/六氟丙烯。In some aspects, the fluorinated perfluoro copolymer includes a first fluorinated tetrafluoroethylene/hexafluoropropylene having a first melt flow rate and a second tetrafluoroethylene/hexafluoropropylene having a second melt flow rate.
在一些態樣，該全氟共聚物基質中每百萬個碳原子之羧基端基之數目足以使該預浸材物品不形成導電陽極絲。在一些態樣，該全氟共聚物基質包括每百萬個碳原子一數目之羧基端基，其足以為該預浸材物品在該介電基材與導電包覆之間提供大於2 lb/吋之剝離強度。全氟共聚物基質可包括例如每百萬個碳原子在5與200個之間之羧基端基，或每百萬個碳原子在30與70個之間之羧基端基。In some aspects, the number of carboxyl end groups per million carbon atoms in the perfluoro copolymer matrix is sufficient to prevent the prepreg article from forming conductive anode filaments. In some aspects, the perfluoro copolymer matrix includes a number of carboxyl end groups per million carbon atoms sufficient to provide the prepreg article with a peel strength greater than 2 lb/inch between the dielectric substrate and the conductive coating. The perfluoro copolymer matrix can include, for example, between 5 and 200 carboxyl end groups per million carbon atoms, or between 30 and 70 carboxyl end groups per million carbon atoms.
全氟共聚物基質可具有在10 g/10分鐘與30 g/10分鐘之間、或在10 g/10分鐘與20 g/10分鐘之間之熔體流動速率。全氟共聚物基質在288℃下可具有至少10秒之耐浮焊性(solder float resistance)。The perfluorocopolymer matrix may have a melt flow rate between 10 g/10 minutes and 30 g/10 minutes, or between 10 g/10 minutes and 20 g/10 minutes. The perfluorocopolymer matrix may have a solder float resistance of at least 10 seconds at 288°C.
L-玻璃織物可具有小於100 g/m2、或小於50 g/m2之基礎重量。在一些態樣，L-玻璃織物具有在10 µm與100 µm之間、或在10 µm與30 µm之間之厚度。L-玻璃織物可包括胺基矽烷或甲基丙烯酸酯矽烷表面化學處理；可經電漿處理或經電暈處理；可用氟聚合物浸漬；可包括氟聚合物塗層；可具有在0°與60°之間之水接觸角；及/或可在併入該預浸材物品中之前用氟聚合物處理來預處理。The L-glass fabric may have a basis weight of less than 100 g/m2 , or less than 50 g/m2. In some aspects, the L-glass fabric has a thickness between 10 μm and 100 μm, or between 10 μm and 30 μm. The L-glass fabric may include an aminosilane or methacrylate silane surface chemical treatment; may be plasma treated or corona treated; may be impregnated with a fluoropolymer; may include a fluoropolymer coating; may have a water contact angle between 0° and 60°; and/or may be pre-treated with a fluoropolymer treatment prior to incorporation into the prepreg article.
在一些態樣，一介電基材包括在5與20體積百分比之間的該L-玻璃織物及在80與95體積百分比之間的該全氟共聚物基質。In some aspects, a dielectric substrate includes between 5 and 20 volume percent of the L-glass fabric and between 80 and 95 volume percent of the perfluorocopolymer matrix.
在某些態樣，該添加劑材料包括無機粒子，諸如但不限於氧化鈰、二氧化鈦、二氧化矽、鈦酸鋇、鈦酸鈣、氧化鋅、或其組合之粒子。該添加劑材料可包括熱固性聚合物。添加劑材料可以小於2%之該全氟共聚物基質之體積百分比存在於該全氟共聚物基質中，及/或可均質地分散於整個該全氟共聚物基質中。In some aspects, the additive material includes inorganic particles, such as but not limited to particles of bismuth oxide, titanium dioxide, silicon dioxide, barium titanate, calcium titanate, zinc oxide, or a combination thereof. The additive material may include a thermosetting polymer. The additive material may be present in the perfluorocopolymer matrix at a volume percentage of less than 2% of the perfluorocopolymer matrix and/or may be homogeneously dispersed throughout the perfluorocopolymer matrix.
在一些態樣，導電包覆係設置於該介電基材之兩個相對表面上。合適之導電包覆可包括例如銅箔。導電包覆可藉由層壓程序設置於該介電基材之該表面上。在一些態樣，該導電包覆具有小於72 µm、或在5 µm與18 µm之間之厚度；小於1 µm之均方根(root mean square, RMS)粗糙度，及/或小於0.5 µm之RMS粗糙度。In some embodiments, the conductive coating is disposed on two opposing surfaces of the dielectric substrate. Suitable conductive coatings may include, for example, copper foil. The conductive coating may be disposed on the surface of the dielectric substrate by a lamination process. In some embodiments, the conductive coating has a thickness of less than 72 μm, or between 5 μm and 18 μm; a root mean square (RMS) roughness of less than 1 μm, and/or an RMS roughness of less than 0.5 μm.
一種印刷線路板可包括如本文所述之一預浸材物品，其具有相鄰導電包覆，諸如具有導體圖案之覆銅層壓體。在某些態樣，一通孔係穿過該板之厚度而界定，且可選地一銅膜電鍍該通孔。A printed circuit board may include a prepreg article as described herein, having an adjacent conductive coating, such as a copper-clad laminate having a conductive pattern. In some aspects, a through hole is defined through the thickness of the board, and a copper film is optionally electroplated into the through hole.
一種多層印刷線路板可包括具有多個如本文所述之印刷線路板之一多層層壓結構。在一些態樣，熱塑性黏著劑係設置於該層壓結構中之相鄰印刷線路板之間。該熱塑性黏著劑可在較該全氟共聚物基質之熔點低0與200℃之間之溫度下黏合；或在較該全氟共聚物基質之熔點低0與50℃之間之溫度下黏合。在一些態樣，熱固性黏著劑係設置於該層壓結構中之相鄰印刷線路板之間。該熱固性黏著劑可在150℃與250℃之間之溫度下固化。A multilayer printed circuit board may include a multilayer laminated structure having a plurality of printed circuit boards as described herein. In some embodiments, a thermoplastic adhesive is disposed between adjacent printed circuit boards in the laminated structure. The thermoplastic adhesive may be bonded at a temperature between 0 and 200°C lower than the melting point of the perfluorocopolymer matrix; or bonded at a temperature between 0 and 50°C lower than the melting point of the perfluorocopolymer matrix. In some embodiments, a thermosetting adhesive is disposed between adjacent printed circuit boards in the laminated structure. The thermosetting adhesive may be cured at a temperature between 150°C and 250°C.
多層印刷線路板可包括一通孔，其係穿過該多層印刷線路板之厚度之至少一部分而界定；及可選地，電鍍該通孔之一銅膜。The multi-layer printed wiring board may include a through hole defined through at least a portion of the thickness of the multi-layer printed wiring board; and optionally, a copper film is electroplated in the through hole.
一種可與5G通訊網路一起使用之天線可包括本文所述之一印刷線路板。An antenna that can be used with a 5G communication network may include a printed circuit board as described herein.
根據本發明之某些態樣，一種製造一多層印刷線路板之方法包括提供如本文所述之多個印刷線路板；及層壓該多個印刷線路板，以形成一多層層壓結構。層壓多個印刷線路板可包括使用一熱塑性預浸材黏附相鄰印刷線路板。該熱塑性預浸材可在較該相鄰全氟共聚物基質之熔點低0與100℃之間之溫度下，或在較該相鄰全氟共聚物基質之熔點低0與50℃之間之溫度下黏合。該方法可包括透過例如紫外線雷射鑽孔程序來穿過該多層層壓結構之厚度之至少一部分而界定一通孔。According to certain aspects of the present invention, a method of manufacturing a multi-layer printed circuit board includes providing a plurality of printed circuit boards as described herein; and laminating the plurality of printed circuit boards to form a multi-layer laminated structure. Laminating the plurality of printed circuit boards may include adhering adjacent printed circuit boards using a thermoplastic prepreg. The thermoplastic prepreg may be bonded at a temperature between 0 and 100°C lower than the melting point of the adjacent perfluorocopolymer matrix, or at a temperature between 0 and 50°C lower than the melting point of the adjacent perfluorocopolymer matrix. The method may include defining a through hole through at least a portion of the thickness of the multi-layer laminated structure by, for example, an ultraviolet laser drilling process.
根據本發明之某些態樣，一種製造一層壓物品之方法包括：形成具有第一及第二聚合物膜之一層狀物品，各膜具有包括氟化四氟乙烯/六氟丙烯共聚物之全氟共聚物基質，及能夠吸收紫外光之添加劑材料；L-玻璃織物，其係設置於該第一與該第二聚合物膜之間；及導電包覆，其經設置以與該第一膜接觸；及將熱及壓力施加至該層狀物品，以形成該層壓物品。將熱及壓力施加至該層狀物品可包括在經加熱壓板中壓製該層狀物品及/或在卷對卷層壓程序中加工該層狀物品。將熱及壓力施加至該層狀物品可包括對該層狀物品施加較該全氟共聚物基質之熔點大10℃與80℃之間之溫度。將熱及壓力施加至該層狀物品可包括對該層狀物品施加在250℃與350℃之間之溫度。將熱及壓力施加至該層狀物品可包括對該層狀物品施加在50 psi與1000 psi之間之壓力。According to certain aspects of the present invention, a method of making a laminated article includes: forming a laminated article having first and second polymer films, each film having a perfluoro copolymer matrix including fluorinated tetrafluoroethylene/hexafluoropropylene copolymer, and an additive material capable of absorbing ultraviolet light; an L-glass fabric disposed between the first and second polymer films; and a conductive coating disposed in contact with the first film; and applying heat and pressure to the laminated article to form the laminated article. Applying heat and pressure to the laminated article may include pressing the laminated article in a heated press plate and/or processing the laminated article in a roll-to-roll lamination process. Applying heat and pressure to the laminated article may include applying a temperature between 10° C. and 80° C. greater than the melting point of the perfluorocopolymer matrix to the laminated article. Applying heat and pressure to the laminated article may include applying a temperature between 250° C. and 350° C. to the laminated article. Applying heat and pressure to the laminated article may include applying a pressure between 50 psi and 1000 psi to the laminated article.
在某些態樣，在熔融加工及擠出程序中形成該第一膜及該第二膜。該方法可包括用氟聚合物處理來處理該L-玻璃織物。此類處理可包括用氟聚合物塗層塗佈該L-玻璃織物；此可包括以溶液塗佈程序塗佈該L-玻璃織物及/或將氟聚合物粒子沉積在該L-玻璃織物之一表面上。In certain aspects, the first film and the second film are formed in a melt processing and extrusion process. The method may include treating the L-glass fabric with a fluoropolymer treatment. Such treatment may include coating the L-glass fabric with a fluoropolymer coating; this may include coating the L-glass fabric with a solution coating process and/or depositing fluoropolymer particles on a surface of the L-glass fabric.
根據一些態樣，一種多層層壓體包括一第一層，該第一層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。該多層層壓體可具有一第二層，該第二層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化全氟共聚物及非氟化全氟共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光；及導電包覆，其係設置於該介電基材之表面上。在某些態樣，導電包覆係設置於該第二層之該介電基材之多個表面上。According to some aspects, a multi-layer laminate includes a first layer, the first layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The multi-layer laminate may have a second layer, the second layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated perfluoro copolymer and a non-fluorinated perfluoro copolymer; an L-glass fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light; and a conductive coating, which is disposed on a surface of the dielectric substrate. In some aspects, a conductive coating is disposed on multiple surfaces of the dielectric substrate of the second layer.
根據一些態樣，一種多層層壓體包括一第一層，該第一層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。該多層層壓體可具有一第二層，該第二層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化全氟共聚物及非氟化全氟共聚物；石英織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光；及導電包覆，其係設置於該介電基材之表面上。在某些態樣，導電包覆係設置於該第二層之該介電基材之多個表面上。According to some aspects, a multi-layer laminate includes a first layer, the first layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The multi-layer laminate may have a second layer, the second layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated perfluoro copolymer and a non-fluorinated perfluoro copolymer; a quartz fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light; and a conductive coating, which is disposed on a surface of the dielectric substrate. In some aspects, a conductive coating is disposed on multiple surfaces of the dielectric substrate of the second layer.
在隨附圖式及以下實施方式中闡述一或多個實施方案之細節。其他特徵及優點將從實施方式及圖式、及從申請專利範圍中顯而易見。The details of one or more embodiments are described in the accompanying drawings and the following detailed description. Other features and advantages will be apparent from the detailed description and drawings, and from the scope of the claims.
本發明之物品及方法係關於具有一介電基材之預浸材物品，該介電基材包括：全氟共聚物基質，其包含氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。本發明之預浸材物品可係可撓性的。本文所述之預浸材物品可在高頻（例如10 GHz）下具有低介電常數及低散逸。本文所述之預浸材物品可具有有益於用作高頻應用中印刷線路板之基材之性質，諸如用於5G蜂巢式通訊網路中之天線、或與企業伺服器通訊硬體一起使用、及其他應用。The articles and methods of the present invention relate to prepreg articles having a dielectric substrate, the dielectric substrate comprising: a perfluoro copolymer matrix comprising a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric embedded in the perfluoro copolymer matrix; and an additive material dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The prepreg articles of the present invention may be flexible. The prepreg articles described herein may have low dielectric constants and low dissipation at high frequencies (e.g., 10 GHz). The prepreg articles described herein may have properties that are beneficial for use as a substrate for printed circuit boards in high-frequency applications, such as antennas used in 5G cellular communication networks, or used with enterprise server communication hardware, and other applications.
參照圖1，預浸材物品100包括由全氟共聚物基質110與L-玻璃織物形成之介電基材102。1 , a prepreg article 100 includes a dielectric substrate 102 formed of a perfluoro copolymer matrix 110 and an L-glass fabric.
如下文所進一步論述，全氟共聚物基質110可為介電基材102提供低介電常數及低散逸因數。全氟共聚物基質110包括完全氟化全氟共聚物（本文中稱為「氟化全氟共聚物(fluorinated perfluorocopolymer)」），諸如完全氟化四氟乙烯/六氟丙烯共聚物。As discussed further below, the perfluorocopolymer matrix 110 can provide a low dielectric constant and a low dissipation factor for the dielectric substrate 102. The perfluorocopolymer matrix 110 includes a fully fluorinated perfluorocopolymer (referred to herein as a "fluorinated perfluorocopolymer"), such as a fully fluorinated tetrafluoroethylene/hexafluoropropylene copolymer.
在一些實例中，全氟共聚物之組成係由全氟共聚物中存在之羧基端基之數目（例如數目濃度）指示。此類羧基端基之非限制性實例包括-COF、-CONH2、-CO2CH3、及-CO2H且係藉由聚合態樣判定，諸如聚合介質、起始劑、鏈轉移劑（若存在）、及緩衝劑（若存在）之選擇。全氟共聚物中存在之每百萬個碳原子之羧基端基之數目可在5與200之間，替代地在30與70之間，或替代地在35與55之間。此羧基端基之數目可經選擇以在全氟共聚物基質110與L-玻璃織物108及相鄰可選導電包覆（當存在時）之間達到足夠的黏著性，同時亦達到足夠低的介電常數及散逸因數。例如，可選擇羧基端基之數目使得預浸材物品100中無CAF形成。In some examples, the composition of the perfluorocopolymer is indicated by the number (e.g., numerical concentration) of carboxyl end groups present in the perfluorocopolymer. Non-limiting examples of such carboxyl end groups include -COF, -CONH2 , -CO2 CH3 , and -CO2 H and are determined by the polymerization behavior, such as the selection of the polymerization medium, initiator, chain transfer agent (if present), and buffer (if present). The number of carboxyl end groups per million carbon atoms present in the perfluorocopolymer may be between 5 and 200, alternatively between 30 and 70, or alternatively between 35 and 55. The number of carboxyl end groups can be selected to achieve sufficient adhesion between the perfluorocopolymer matrix 110 and the L-glass fabric 108 and the adjacent optional conductive coating (when present), while also achieving a sufficiently low dielectric constant and dissipation factor. For example, the number of carboxyl end groups can be selected so that no CAF is formed in the prepreg article 100.
全氟共聚物中羧基端基之分析及定量可透過全氟聚合物之所屬技術領域中具有通常知識者已知之紅外光譜方法進行。熱穩定的端基-CF3（氟化之產物）之存在可由在氟處理之後不存在不穩定的端基推論。相較於其他端基，-CF3端基之存在可導致全氟共聚物之散逸因數降低。The analysis and quantification of carboxyl end groups in the perfluorocopolymers can be performed by infrared spectroscopy methods known to those skilled in the art of perfluoropolymers. The presence of the thermally stable end group -CF3 (product of fluorination) can be inferred from the absence of unstable end groups after fluorine treatment. The presence of -CF3 end groups can result in a lower dissipation factor of the perfluorocopolymers compared to other end groups.
在一些態樣，全氟共聚物係由水性分散液聚合製成，且聚合態(as-polymerized)可含有每106個碳原子至少約400個反應性端基。大部分此等端基係熱不穩定的，因為當暴露於熱（諸如在擠出及膜形成期間、或膜層壓條件下遇到的熱）時，其等可經歷化學反應，諸如分解及去羧，而使擠出之聚合物變色、或填充不均勻氣泡、或兩者。為了製造本文所述之氟化全氟共聚物，將聚合之全氟共聚物穩定，以藉由熱穩定的-CF3端基置換實質上所有的反應性端基。穩定化之實例方法係將氟聚合物暴露於氟化劑（諸如元素氟），此係全氟聚合物之所屬技術領域中具有通常知識者已知之穩定化程序。In some aspects, the perfluorocopolymer is made by aqueous dispersion polymerization and may contain at least about 400 reactive end groups per 106 carbon atoms as-polymerized. Most of these end groups are thermally unstable because when exposed to heat (such as encountered during extrusion and film formation, or under film lamination conditions), they may undergo chemical reactions such as decomposition and decarboxylation, causing discoloration of the extruded polymer, filling of uneven bubbles, or both. To make the fluorinated perfluorocopolymers described herein, the polymerized perfluorocopolymer is stabilized to replace substantially all of the reactive end groups with thermally stable -CF3 end groups. An example method of stabilization is to expose the fluoropolymer to a fluorinating agent (such as elemental fluorine), which is a stabilization procedure known to those skilled in the art for perfluoropolymers.
全氟共聚物基質110可包括嵌入其中之L-玻璃織物108，諸如編織L-玻璃織物（例如，編織成織物之L-玻璃、NL-玻璃、或L2-玻璃紗線）。在一些態樣，嵌入全氟共聚物基質110中之L-玻璃織物108可由偏光玻璃(spread glass)（例如L-玻璃）束形成。L-玻璃織物108可使得介電基材102之x-y平面中之熱膨脹係數(coefficient of thermal expansion, CTE)能夠匹配相鄰可選導電包覆（當存在時）之CTE。因此，L-玻璃織物108之存在可導致預浸材物品100具有高度的平坦度，例如足以使預浸材物品的多個層之間在鑽孔程序期間能夠對準之平坦度。例如，在包含多個預浸材物品100之多層層壓體中，高度的平坦度使在穿過多層層壓體結構之厚度之導孔之鑽孔期間能夠對準。不受理論束縛，咸信L-玻璃織物108之熱膨脹係數(CTE)與全氟共聚物基質110之CTE之間之差異、連同L-玻璃織物108之相對低模數（例如，相較於石英織物）使得L-玻璃織物108在多層層壓體冷卻期間之收縮足夠小以避免在多層層壓體中產生波紋。The perfluorocopolymer matrix 110 may include an L-glass fabric 108 embedded therein, such as a woven L-glass fabric (e.g., L-glass, NL-glass, or L2-glass yarns woven into a fabric). In some aspects, the L-glass fabric 108 embedded in the perfluorocopolymer matrix 110 may be formed from a bundle of spread glass (e.g., L-glass). The L-glass fabric 108 may enable the coefficient of thermal expansion (CTE) of the dielectric substrate 102 in the x-y plane to match the CTE of an adjacent optional conductive coating (when present). Therefore, the presence of the L-glass fabric 108 may result in the prepreg article 100 having a high degree of flatness, such as a flatness sufficient to enable alignment between multiple layers of the prepreg article during a drilling process. For example, in a multi-ply press comprising a plurality of prepreg articles 100, a high degree of flatness enables alignment during drilling of vias through the thickness of the multi-ply press structure. Without being bound by theory, it is believed that the difference between the coefficient of thermal expansion (CTE) of the L-glass fabric 108 and the CTE of the perfluorocopolymer matrix 110, together with the relatively low modulus of the L-glass fabric 108 (e.g., compared to a quartz fabric), causes the contraction of the L-glass fabric 108 during cooling of the multi-ply press to be sufficiently small to avoid generating ripples in the multi-ply press.
L-玻璃之組成係顯示於表1中。亦顯示E-玻璃之組成以供比較。L-玻璃具有較全氟共聚物基質110低的CTE，諸如在2.5 ppm/℃與4 ppm/℃之間、在2.5 ppm/℃與3 ppm/℃之間、或在3 ppm/℃與4 ppm/℃之間之CTE。藉由調整全氟共聚物基質110對編織玻璃織物108之體積比率，介電基材102在x-y平面中之CTE可與可選金屬箔之面內CTE匹配，從而提供具有尺寸穩定性之預浸材物品100。例如，介電基材102可包括在5與20體積百分比之間的編織L-玻璃織物108及在80與95體積百分比之間的全氟共聚物基質110。介電基材102之x-y平面中之CTE可在5與25 ppm/℃之間、在16與22 ppm/℃之間、或在14與20 ppm/℃之間，從而提供小於約0.1%之尺寸穩定性。相比之下，單獨全氟共聚物基質110之CTE可在100與300 ppm/℃之間。
L-玻璃具有低介電常數，諸如在10 GHz下在4.0與5.0之間、在4.5與5.0 GHz之間、或在4.5與4.8 GHz之間之介電常數。因此，即使存在嵌入全氟共聚物基質110中之L-玻璃織物108，介電基材102仍可具有低介電常數及低損耗。L-玻璃亦具有低散逸因數，諸如在10 GHz下在0.002與0.003之間、在10 GHz下0.002、在10 GHz下0.0023、在10 GHz下0.0025、在10 GHz下0.0028、或在10 GHz下0.003之散逸因數。L-glass has a low dielectric constant, such as between 4.0 and 5.0 at 10 GHz, between 4.5 and 5.0 GHz, or between 4.5 and 4.8 GHz. Thus, the dielectric substrate 102 can have a low dielectric constant and low loss even with the presence of the L-glass fabric 108 embedded in the perfluorocopolymer matrix 110. The L-glass also has a low dissipation factor, such as between 0.002 and 0.003 at 10 GHz, 0.002 at 10 GHz, 0.0023 at 10 GHz, 0.0025 at 10 GHz, 0.0028 at 10 GHz, or 0.003 at 10 GHz.
編織L-玻璃織物108具有小於約100 µm、在約30 µm與100 µm之間、或在10 µm與30 µm之間之厚度，有助於實現薄介電基材102。L-玻璃織物108之基礎重量係小於約1000 g/m2、小於約50 g/m2、或在10 g/m2與50 g/m2之間。在一具體實例中，L-玻璃織物108係NL1035 NL-玻璃織物(Asahi Kasei Corporation, Tokyo, Japan)。The woven L-glass fabric 108 has a thickness of less than about 100 μm, between about 30 μm and 100 μm, or between 10 μm and 30 μm, which facilitates a thin dielectric substrate 102. The basis weight of the L-glass fabric 108 is less than about 1000 g/m2 , less than about 50 g/m2 , or between 10 g/m2 and 50 g/m2. In one specific example, the L-glass fabric 108 is NL1035 NL-glass fabric (Asahi Kasei Corporation, Tokyo, Japan).
在一些實例中，使編織L-玻璃織物108經受一或多種表面處理，以改善全氟共聚物基質110對編織L-玻璃織物108之纖維之潤濕性以移除殘餘有機物質，或以機械地改變纖維之表面以增強L-玻璃織物108之纖維與全氟共聚物基質110之間的黏著性。表面處理之目的可係促進L-玻璃纖維被全氟共聚物實質上完全潤濕，使得全氟共聚物完全包封L-玻璃纖維（例如L-玻璃紗線）束。全氟共聚物對L-玻璃纖維束之充分包封及黏著使介電基材102能夠實質上不含空隙（例如無孔），繼而有助於防止導電陽極絲之形成及在後加工期間（例如，在穿過預浸材物品100之厚度形成導孔之期間）電遷移之發生。In some examples, the braided L-glass fabric 108 is subjected to one or more surface treatments to improve the wettability of the fibers of the braided L-glass fabric 108 by the perfluoro copolymer matrix 110 to remove residual organic matter, or to mechanically change the surface of the fibers to enhance adhesion between the fibers of the L-glass fabric 108 and the perfluoro copolymer matrix 110. The purpose of the surface treatment may be to promote substantially complete wetting of the L-glass fibers by the perfluoro copolymer so that the perfluoro copolymer completely encapsulates the L-glass fiber (e.g., L-glass yarn) bundle. The full encapsulation and adhesion of the perfluoro copolymer to the L-glass fiber bundles enables the dielectric substrate 102 to be substantially free of voids (e.g., pores), which in turn helps prevent the formation of conductive anode filaments and the occurrence of electrical migration during post-processing (e.g., during the formation of vias through the thickness of the prepreg article 100).
表面處理可包括熱處理以自L-玻璃纖維之表面移除殘餘有機物質（例如殘餘澱粉），使得乾淨的L-玻璃表面暴露於全氟共聚物。表面處理可包括在L-玻璃纖維之表面上添加助黏劑，諸如甲基丙烯酸酯矽烷、乙烯基矽烷、胺基矽烷、或氟矽烷。表面處理可包括電漿處理或電暈處理。表面處理可包括用聚合物塗層處理，諸如氟聚合物，例如全氟烷(PFA)、氟化乙烯丙烯(FEP)、或Teflon™非晶氟聚合物，以在L-玻璃纖維之表面上形成聚合物（例如氟聚合物）膜。例如，可將L-玻璃織物浸入含有氟聚合物之分散液之溶液中，以在L-玻璃纖維之表面上形成氟聚合物之單層。表面處理可包括用氟化矽烷處理，以在L-玻璃纖維之表面上形成氟化分子之層，例如單層。可施加表面處理之組合，諸如熱處理、接著電漿處理或電暈處理。施加至L-玻璃織物108之（多個）表面處理可改善全氟共聚物基質110對纖維之潤濕性，使全氟共聚物基質110能夠更好地包封L-玻璃織物108之纖維及全氟共聚物基質110與L-玻璃織物108之纖維之間的黏著性更強，從而有助於形成可抵抗CAF形成之無空隙介電基材102。Surface treatment may include heat treatment to remove residual organic matter (e.g., residual starch) from the surface of the L-glass fiber, so that the clean L-glass surface is exposed to the perfluoro copolymer. Surface treatment may include adding an adhesion promoter such as methacrylate silane, vinyl silane, amino silane, or fluorosilane to the surface of the L-glass fiber. Surface treatment may include plasma treatment or corona treatment. Surface treatment may include treatment with a polymer coating such as a fluoropolymer, such as perfluoroalkane (PFA), fluorinated ethylene propylene (FEP), or Teflon™ amorphous fluoropolymer to form a polymer (e.g., fluoropolymer) film on the surface of the L-glass fiber. For example, the L-glass fabric may be immersed in a solution containing a dispersion of a fluoropolymer to form a monolayer of the fluoropolymer on the surface of the L-glass fiber. The surface treatment may include treatment with a fluorinated silane to form a layer, such as a monolayer, of fluorinated molecules on the surface of the L-glass fibers. A combination of surface treatments may be applied, such as a heat treatment followed by a plasma treatment or a corona treatment. The surface treatment(s) applied to the L-glass fabric 108 may improve the wettability of the fibers by the perfluoro copolymer matrix 110, allowing the perfluoro copolymer matrix 110 to better encapsulate the fibers of the L-glass fabric 108 and provide stronger adhesion between the perfluoro copolymer matrix 110 and the fibers of the L-glass fabric 108, thereby facilitating the formation of a void-free dielectric substrate 102 that is resistant to CAF formation.
L-玻璃織物108之潤濕性可藉由水接觸角(water contact angle, WCA)表徵。表面處理後之L-玻璃織物108可具有在0°與60°之間之WCA。添加劑材料112能夠吸收紫外(UV)光，例如具有在180 nm與400 nm之間之波長的光，且可分散於全氟共聚物基質110中。UV反應性添加劑材料112之存在可使預浸材物品100能夠藉由UV雷射鑽孔，例如用於形成電路結構，諸如穿過預浸材物品100之厚度之導孔。The wettability of the L-glass fabric 108 can be characterized by a water contact angle (WCA). The surface treated L-glass fabric 108 can have a WCA between 0° and 60°. The additive material 112 is capable of absorbing ultraviolet (UV) light, such as light having a wavelength between 180 nm and 400 nm, and can be dispersed in the perfluorocopolymer matrix 110. The presence of the UV reactive additive material 112 can enable the prepreg article 100 to be drilled by UV laser, such as for forming circuit structures, such as vias through the thickness of the prepreg article 100.
再次參照圖1，添加劑材料112可分散（例如均質地分散）於全氟共聚物基質110中。添加劑材料112係能夠吸收UV光之材料，使得預浸材物品100可藉由UV鑽孔程序加工，例如以在預浸材物品100之頂部表面與底部表面106之間形成導孔。添加劑材料112可以小於3%之體積百分比、在介電基材102之1與3體積百分比之間，在介電基材102之1 vol.%、1.25 vol.%、1.5 vol.%、2 vol.%、或2.5 vol%存在於介電基材102中。添加劑材料112可係具有相對低介電常數之材料，諸如在10與1000之間之介電常數，使得在全氟共聚物基質110中包括添加劑材料112不會顯著增加介電基材102之介電常數或散逸因數。例如，以小於介電基材102之3體積%包括添加劑材料112可造成介電基材102之介電常數增加小於10%、小於5%、或小於2%。1 , the additive material 112 may be dispersed (e.g., homogeneously dispersed) in the perfluorocopolymer matrix 110. The additive material 112 is a material capable of absorbing UV light, so that the prepreg article 100 may be processed by a UV drilling process, for example, to form a via between the top surface and the bottom surface 106 of the prepreg article 100. The additive material 112 may be present in the dielectric substrate 102 at a volume percentage of less than 3%, between 1 and 3 volume percentages of the dielectric substrate 102, at 1 vol.%, 1.25 vol.%, 1.5 vol.%, 2 vol.%, or 2.5 vol.% of the dielectric substrate 102. The additive material 112 may be a material having a relatively low dielectric constant, such as a dielectric constant between 10 and 1000, such that including the additive material 112 in the perfluorocopolymer matrix 110 does not significantly increase the dielectric constant or dissipation factor of the dielectric substrate 102. For example, including the additive material 112 at less than 3 volume % of the dielectric substrate 102 may result in an increase in the dielectric constant of the dielectric substrate 102 of less than 10%, less than 5%, or less than 2%.
在一些態樣，添加劑材料112包含無機粒子，諸如氧化鈰(CeO2)、二氧化鈦(TiO2)、二氧化矽(SiO2)、鈦酸鋇(BaTiO3)、鈦酸鈣(CaTiO3)、氧化鋅(ZnO)、或其他合適材料、及其組合之粒子。粒子可具有小於約5 µm、小於約2 µm、小於約1 µm、或小於約0.5 µm之直徑，例如在0.1 µm與0.5 µm之間。例如，較小的粒子通常較類似組成之較大的粒子更有效吸收UV光。在一些實例中，添加劑材料112係有機（例如聚合物）添加劑，諸如低損耗熱固性材料，諸如聚醯亞胺，其係摻入全氟共聚物基質110中。在一些實例中，無機粒子及有機添加劑兩者皆用作添加劑材料。In some aspects, the additive material 112 includes inorganic particles, such as particles of caesium oxide (CeO2 ), titanium dioxide (TiO2 ), silicon dioxide (SiO2 ), barium titanate (BaTiO3 ), calcium titanate (CaTiO3 ), zinc oxide (ZnO), or other suitable materials, and combinations thereof. The particles can have a diameter of less than about 5 μm, less than about 2 μm, less than about 1 μm, or less than about 0.5 μm, such as between 0.1 μm and 0.5 μm. For example, smaller particles are generally more effective at absorbing UV light than larger particles of similar composition. In some examples, the additive material 112 is an organic (eg, polymer) additive, such as a low-loss thermosetting material, such as polyimide, which is incorporated into the perfluorocopolymer matrix 110. In some examples, both inorganic particles and organic additives are used as additive materials.
在可選實施例中，諸如銅箔之導電包覆可設置於介電基材102之一或兩個表面上。預浸材物品之相鄰可選導電包覆（諸如銅箔層）提供可在其上界定導電圖案之平台，例如使得可撓性層壓體可用作印刷線路板。導電包覆可透過印刷及蝕刻進行各種圖案化，且亦可包括附加金屬化。In an alternative embodiment, a conductive overlay, such as copper foil, may be disposed on one or both surfaces of the dielectric substrate 102. The optional conductive overlay, such as a copper foil layer, adjacent to the prepreg article provides a platform on which a conductive pattern may be defined, for example, so that the flexible laminate may be used as a printed circuit board. The conductive overlay may be patterned in various ways by printing and etching, and may also include additional metallization.
在一些實例中，相鄰可選導電包覆係藉由機械程序（例如卷對卷層壓程序）設置於介電基材102之（多個）表面106上。例如，導電包覆可係電沉積銅箔或輥軋銅箔。在一些實例中，導電包覆諸如銅箔係沉積（例如電解電鍍）至介電基材102上。In some examples, an adjacent optional conductive coating is disposed on the surface(s) 106 of the dielectric substrate 102 by a mechanical process (e.g., a roll-to-roll lamination process). For example, the conductive coating can be an electrodeposited copper foil or a roll-rolled copper foil. In some examples, the conductive coating, such as a copper foil, is deposited (e.g., electrolytically plated) onto the dielectric substrate 102.
可選導電包覆可具有小於約72 µm、小於約18 µm、或在10 µm與18 µm之間之厚度。可選導電包覆可具有低均方根(RMS)粗糙度，諸如小於1 µm、或小於0.5 µm之RMS粗糙度，如藉由非接觸干涉測量法所測量。可選導電包覆之低RMS粗糙度有助於維持由預浸材物品100製成之電路系統之低插入損耗。在一些實例中，可選導電包覆之RMS粗糙度經選擇以平衡低插入損耗（例如，可藉由低RMS粗糙度達到）與可選導電包覆與介電基材102之間的良好黏著性（例如，可藉由較高RMS粗糙度達到）。例如，如上文所論述，介電基材102與可選導電包覆之間足夠高的剝離強度係大於2 lb./吋、大於4 lb./吋、在2與20 lb./吋之間、或在4與20 lb./吋之間之剝離強度。The optional conductive coating may have a thickness of less than about 72 μm, less than about 18 μm, or between 10 μm and 18 μm. The optional conductive coating may have a low root mean square (RMS) roughness, such as an RMS roughness of less than 1 μm, or less than 0.5 μm, as measured by non-contact interferometry. The low RMS roughness of the optional conductive coating helps maintain low insertion loss of a circuit system made from the prepreg article 100. In some examples, the RMS roughness of the optional conductive coating is selected to balance low insertion loss (e.g., achievable by a low RMS roughness) with good adhesion between the optional conductive coating and the dielectric substrate 102 (e.g., achievable by a higher RMS roughness). For example, as discussed above, a sufficiently high peel strength between the dielectric substrate 102 and the optional conductive encapsulation is a peel strength greater than 2 lb./inch, greater than 4 lb./inch, between 2 and 20 lb./inch, or between 4 and 20 lb./inch.
可選導電包覆（諸如銅箔）可具有至少約99.9%之純度。可選導電包覆（諸如銅箔）之表面化學可能受表面處理（諸如用鋅、熱穩定性添加劑處理、及用以抵抗氧化之處理）影響。此等表面處理可施加至可選導電包覆（諸如銅箔）之一或兩個表面。已發現諸如鐵及鋅之元素有效增強剝離強度而不明顯降低介電基材102之電氣性能。The optional conductive overlay (such as copper foil) may have a purity of at least about 99.9%. The surface chemistry of the optional conductive overlay (such as copper foil) may be affected by surface treatments (such as treatment with zinc, thermal stabilizing additives, and treatments to resist oxidation). Such surface treatments may be applied to one or both surfaces of the optional conductive overlay (such as copper foil). Elements such as iron and zinc have been found to effectively enhance the peel strength without significantly degrading the electrical properties of the dielectric substrate 102.
預浸材物品100係平面結構，其可具有小於約200 µm、小於約100 µm、在20 µm與200 µm之間、在30 µm與90 µm之間、或在30 µm與60 µm之間之沿著z軸之厚度。介電基材102之厚度可構成預浸材物品100之大部分厚度。例如，介電基材102可具有小於約200 µm、小於約100 µm、在20 µm與200 µm之間、在30 µm與90 µm之間、或在30 µm與60 µm之間之沿著z軸之厚度。The prepreg article 100 is a planar structure that may have a thickness along the z-axis of less than about 200 μm, less than about 100 μm, between 20 μm and 200 μm, between 30 μm and 90 μm, or between 30 μm and 60 μm. The thickness of the dielectric substrate 102 may constitute a majority of the thickness of the prepreg article 100. For example, the dielectric substrate 102 may have a thickness along the z-axis of less than about 200 μm, less than about 100 μm, between 20 μm and 200 μm, between 30 μm and 90 μm, or between 30 μm and 60 μm.
預浸材物品100之介電基材102可具有低介電常數，例如在10 GHz下小於約2.7、在2.1與2.7之間、或在2.1與2.4之間之介電常數。介電基材102可具有熱係數，其值在0至100℃之溫度範圍內係在-250與50 ppm/℃之間，例如在-100與50 ppm/℃之間或在-50與25 ppm/℃之間。介電基材102亦可具有低散逸因數，例如在10 GHz下小於0.0015之散逸因數，諸如小於0.001或小於0.0008，例如在0.0002與0.001之間、例如在0.0006與0.001之間、例如在0.0006與0.0008之間。The dielectric substrate 102 of the prepreg article 100 may have a low dielectric constant, such as a dielectric constant of less than about 2.7, between 2.1 and 2.7, or between 2.1 and 2.4 at 10 GHz. The dielectric substrate 102 may have a thermal coefficient, whose value is between -250 and 50 ppm/°C in the temperature range of 0 to 100°C, such as between -100 and 50 ppm/°C or between -50 and 25 ppm/°C. The dielectric substrate 102 may also have a low dissipation factor, such as a dissipation factor less than 0.0015 at 10 GHz, such as less than 0.001 or less than 0.0008, such as between 0.0002 and 0.001, such as between 0.0006 and 0.001, such as between 0.0006 and 0.0008.
預浸材物品100之改善電氣性質（例如低介電常數及低散逸因數）使設計者能夠實現插入損耗之改善，例如相對於現有可撓性材料，給定特性阻抗改善高達25%或更多。The improved electrical properties of the prepreg article 100 (e.g., low dielectric constant and low dissipation factor) enable designers to achieve improvements in insertion loss, such as up to 25% or more for a given characteristic impedance relative to existing flexible materials.
介電基材102之熱膨脹係數(CTE)與相鄰可選導電包覆層之CTE在預浸材物品100之x-y平面中係類似的。例如，當相鄰可選導電包覆層係銅箔時，介電基材102在x-y平面中之CTE可在5與25 ppm/℃之間，例如在16與22 ppm/℃之間、例如或在14與20 ppm/℃之間。介電基材102與相鄰可選導電包覆層之間之CTE值之匹配為預浸材物品100提供尺寸穩定性，例如小於約0.1%之尺寸穩定性，例如使得當使預浸材物品100經受溫度變化時，將其原始尺寸保持在約0.1%內。The coefficient of thermal expansion (CTE) of the dielectric substrate 102 and the CTE of the adjacent optional conductive encapsulant are similar in the x-y plane of the prepreg article 100. For example, when the adjacent optional conductive encapsulant is copper foil, the CTE of the dielectric substrate 102 in the x-y plane may be between 5 and 25 ppm/°C, such as between 16 and 22 ppm/°C, such as or between 14 and 20 ppm/°C. The matching of the CTE values between the dielectric substrate 102 and the adjacent optional conductive encapsulant provides dimensional stability to the prepreg article 100, such as dimensional stability of less than about 0.1%, such as to maintain the original dimensions of the prepreg article 100 within about 0.1% when the prepreg article 100 is subjected to temperature changes.
預浸材物品100之相鄰可選導電包覆層可強力黏附至介電基材。例如，在介電基材102與相鄰可選導電包覆之間之剝離強度可大於2 lb./吋，例如大於4 lb./吋、例如在2與20 lb./吋之間、或在4與20 lb./吋之間。預浸材物品100針對彎曲可係機械性堅固的，且可在電子裝置中常見的彎曲半徑上彎曲，而不會使預浸材物品100之組件中之任一者失效。此可撓性促進預浸材物品100安裝至裝置中。The adjacent optional conductive coating of the prepreg article 100 can be strongly adhered to the dielectric substrate. For example, the peel strength between the dielectric substrate 102 and the adjacent optional conductive coating can be greater than 2 lb./inch, such as greater than 4 lb./inch, such as between 2 and 20 lb./inch, or between 4 and 20 lb./inch. The prepreg article 100 can be mechanically strong against bending and can bend over a bend radius common in electronic devices without failing any of the components of the prepreg article 100. This flexibility facilitates installation of the prepreg article 100 into a device.
預浸材物品100可藉由UV雷射鑽孔且可與金屬化技術相容，例如電漿金屬化，使得通孔可穿過預浸材物品100之厚度（例如，沿著預浸材物品100之z軸）形成。預浸材物品100之介電基材102在288℃下具有至少5秒、至少10秒、至少30秒、或至少60秒之耐浮焊性，例如在5與20秒之間、在10與15秒之間、在10與30秒之間、在10與60秒之間、或在30與60秒之間。The prepreg article 100 may be UV laser drilled and may be compatible with metallization techniques, such as plasma metallization, such that through-holes may be formed through the thickness of the prepreg article 100 (e.g., along the z-axis of the prepreg article 100). The dielectric substrate 102 of the prepreg article 100 has a solder float resistance at 288° C. of at least 5 seconds, at least 10 seconds, at least 30 seconds, or at least 60 seconds, such as between 5 and 20 seconds, between 10 and 15 seconds, between 10 and 30 seconds, between 10 and 60 seconds, or between 30 and 60 seconds.
預浸材物品100可用於印刷線路板，例如用於可撓性印刷電路板天線。例如，預浸材物品100之尺寸及電氣性質可使預浸材物品100適用於高頻應用中，諸如用於可在5G通訊網路上使用之行動裝置之天線（如下文所進一步論述）、或與汽車雷達一起使用、或其他高頻應用。在一些實例中，多個預浸材物品100本身可層壓至多層電路板結構中。預浸材物品100實質上不含空隙且可抵抗導電陽極絲之形成，其有助於預浸材物品100作為印刷線路板基材之電氣可靠性。Prepreg article 100 may be used in printed circuit boards, such as for flexible printed circuit board antennas. For example, the dimensions and electrical properties of prepreg article 100 may make prepreg article 100 suitable for use in high frequency applications, such as for use in antennas for mobile devices that may be used on 5G communication networks (as further discussed below), or for use with automotive radar, or other high frequency applications. In some examples, multiple prepreg articles 100 may themselves be laminated into a multi-layer circuit board structure. Prepreg article 100 is substantially free of voids and resists the formation of conductive anode filaments, which contributes to the electrical reliability of prepreg article 100 as a printed circuit board substrate.
預浸材物品100之介電基材102之低介電常數及低散逸因數至少部分地歸因於全氟共聚物基質110之組成。全氟共聚物基質110包括完全氟化全氟共聚物，諸如氟化四氟乙烯/六氟丙烯共聚物。The low dielectric constant and low dissipation factor of the dielectric substrate 102 of the prepreg article 100 are at least partially due to the composition of the perfluoro copolymer matrix 110. The perfluoro copolymer matrix 110 includes a fully fluorinated perfluoro copolymer, such as a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer.
介電基材102之足夠低的介電常數係在10 GHz下小於約2.7之介電常數，例如在2.1與2.7之間、例如在2.1與2.4之間。介電基材102之足夠低的散逸因數係在10 GHz下小於0.0015之散逸因數，諸如在0.0002與0.001之間、例如在0.0006至0.001之間、例如在0.0006與0.0008之間。A sufficiently low dielectric constant for the dielectric substrate 102 is a dielectric constant of less than about 2.7 at 10 GHz, such as between 2.1 and 2.7, such as between 2.1 and 2.4. A sufficiently low dissipation factor for the dielectric substrate 102 is a dissipation factor of less than 0.0015 at 10 GHz, such as between 0.0002 and 0.001, such as between 0.0006 and 0.001, such as between 0.0006 and 0.0008.
在一些實例中，全氟共聚物基質110及L-玻璃織物108與可選導電包覆之間的黏著性之充分性係藉由介電基材102與可選相鄰導電包覆層之間之剝離強度判定。例如，若剝離強度大於2 lb./吋，例如大於4 lb./吋，例如在2與20 lb./吋之間或在4與20 lb./吋之間，則黏著性係足夠的。在一些實例中，全氟共聚物基質110及L-玻璃織物108與相鄰可選導電包覆之間的黏著性之充分性係藉由預浸材物品100抵抗導電陽極絲(conductive anodic filament, CAF)之形成的傾向判定，其在下文進一步論述。In some examples, the adequacy of adhesion between the perfluorocopolymer matrix 110 and the L-glass fabric 108 and the optional conductive coating is determined by the peel strength between the dielectric substrate 102 and the optional adjacent conductive coating layer. For example, if the peel strength is greater than 2 lb./inch, such as greater than 4 lb./inch, such as between 2 and 20 lb./inch or between 4 and 20 lb./inch, then the adhesion is sufficient. In some examples, the adequacy of adhesion between the perfluorocopolymer matrix 110 and the L-glass fabric 108 and the adjacent optional conductive coating is determined by the tendency of the prepreg article 100 to resist the formation of conductive anodic filaments (CAF), which is further discussed below.
氟化全氟共聚物之熔體流動速率(melt flow rate, MFR)可影響全氟共聚物基質110及L-玻璃織物108與相鄰可選導電包覆層之間的黏著性。具有高MFR之聚合物在預浸材物品100之層壓期間較具有較低MFR之聚合物更容易流動。全氟共聚物基質110在層壓程序（在下文更詳細地論述）期間之流動可使全氟共聚物基質110能夠完全包封L-玻璃織物108之纖維，產生實質上不含空隙（例如無孔）之介電基材102。無空隙介電基材102可抵抗CAF形成。The melt flow rate (MFR) of the fluorinated perfluorocopolymer can affect the adhesion between the perfluorocopolymer matrix 110 and the L-glass fabric 108 and the adjacent optional conductive coating layer. Polymers with high MFR flow more easily during lamination of the prepreg article 100 than polymers with lower MFR. The flow of the perfluorocopolymer matrix 110 during the lamination process (discussed in more detail below) can enable the perfluorocopolymer matrix 110 to completely encapsulate the fibers of the L-glass fabric 108, resulting in a dielectric substrate 102 that is substantially free of voids (e.g., pores). The void-free dielectric substrate 102 can resist CAF formation.
氟化全氟共聚物具有高熔點，諸如在200℃與300℃之間，例如在220℃與300℃之間、在240℃與280℃之間、例如約265℃。氟化全氟共聚物之高熔點導致全氟共聚物基質100耐高溫並為介電基材102提供足夠的耐浮焊性，諸如在288℃下至少5秒、至少10秒、至少30秒、或至少60秒之耐浮焊性，例如在5與20秒之間、在10與15秒之間、在10與30秒之間、在10與60秒之間、或在30與60秒之間，如根據IPC-TM-650測試方法所測量。The fluorinated perfluoro copolymer has a high melting point, such as between 200° C. and 300° C., such as between 220° C. and 300° C., between 240° C. and 280° C., such as about 265° C. The high melting point of the fluorinated perfluoro copolymer causes the perfluoro copolymer matrix 100 to withstand high temperatures and provides the dielectric substrate 102 with sufficient solder float resistance, such as at least 5 seconds, at least 10 seconds, at least 30 seconds, or at least 60 seconds of solder float resistance at 288° C., such as between 5 and 20 seconds, between 10 and 15 seconds, between 10 and 30 seconds, between 10 and 60 seconds, or between 30 and 60 seconds, as measured according to the IPC-TM-650 test method.
可選擇全氟共聚物基質110之組成以使介電基材102能夠與電漿處理相容，例如用於穿過預浸材物品100之厚度形成之通孔的金屬化。The composition of the perfluorocopolymer matrix 110 may be selected to render the dielectric substrate 102 compatible with plasma processing, such as for metallization of vias formed through the thickness of the prepreg article 100 .
如上文所論述，預浸材物品100之介電基材102實質上不含空隙，且在全氟共聚物基質110與L-玻璃織物108之間具有足夠的黏著性，其使預浸材物品100能夠抵抗導電陽極絲(CAF)之形成。CAF係由於例如由施加電場誘導之金屬電遷移而例如在介電基材之空隙或弱區域中形成之金屬絲。CAF形成可導致電氣失效，例如當CAF在穿過印刷線路板之導孔之間建立短路路徑時。當在整個測試持續期間電阻下降小於十倍（在初始96小時平衡期之後電阻大於10 M歐姆）時，預浸材物品可被視為沒有CAF形成。在施加在100 VDC與1000 VDC之間之電壓下，CAF測試可持續多達1000小時或更長，例如取決於應用標準。As discussed above, the dielectric substrate 102 of the prepreg article 100 is substantially free of voids and has sufficient adhesion between the perfluoro copolymer matrix 110 and the L-glass fabric 108 that enables the prepreg article 100 to resist the formation of conductive anode filaments (CAFs). CAFs are metal filaments that form, for example, in voids or weak areas of a dielectric substrate due to metal electromigration induced, for example, by an applied electric field. CAF formation can lead to electrical failure, for example when the CAF establishes a short circuit path between vias through a printed circuit board. The prepreg article can be considered free of CAF formation when the resistance drops less than ten times over the entire test duration (resistance greater than 10 MOhms after an initial 96-hour equilibration period). At applied voltages between 100 VDC and 1000 VDC, CAF testing can last up to 1000 hours or longer, e.g. depending on the application standard.
再次參照圖1，預浸材物品100之介電基材102可實質上不含空隙且在全氟共聚物基質110與L-玻璃織物108之間具有強黏著性。此係例如藉由全氟共聚物之本質（例如反應性端基之數目濃度）、L-玻璃織物108之表面化學、及製造參數（諸如壓力及溫度）（在下文論述）達到。此外，在一些態樣，在全氟共聚物基質110中之L-玻璃織物108之配置使得L-玻璃織物108之纖維與最近的可選導電包覆之間實質上無接觸。因此，介電基材102中之CAF形成最少，且預浸材物品100可用作可靠且堅固的印刷線路板基材。Referring again to FIG. 1 , the dielectric substrate 102 of the prepreg article 100 can be substantially free of voids and have strong adhesion between the perfluoro copolymer matrix 110 and the L-glass fabric 108. This is achieved, for example, by the nature of the perfluoro copolymer (e.g., the number concentration of reactive end groups), the surface chemistry of the L-glass fabric 108, and the manufacturing parameters (e.g., pressure and temperature) (discussed below). In addition, in some embodiments, the configuration of the L-glass fabric 108 in the perfluoro copolymer matrix 110 is such that there is substantially no contact between the fibers of the L-glass fabric 108 and the nearest optional conductive coating. Therefore, CAF formation in the dielectric substrate 102 is minimized, and the prepreg article 100 can be used as a reliable and robust printed circuit board substrate.
多個預浸材物品100可層壓在一起以形成多層層壓體或多層印刷線路板。中心預浸材物品100可包括頂部導電包覆及底部導電包覆。預浸材物品100可各自包括單一可選導電包覆。預浸材物品100可透過黏著劑層黏合至中心預浸材物品100。黏著劑層可係例如可在較預浸材物品100之全氟共聚物基質110之熔點低之溫度下黏合之黏著劑。在一些實例中，黏著劑層係熱塑性黏著劑，其能夠在較相鄰層壓體全氟共聚物基質110之熔點低0℃與50℃之間之溫度下黏合。由本文所述之預浸材物品100製成之印刷線路板可用於各種應用中，例如高頻應用，諸如高頻通訊應用。例如，包括一或多個可撓性層壓體預浸材物品100之本印刷線路板可用於可在5G通訊網路上操作之通訊裝置（例如行動通訊裝置）之天線或天線饋線。例如，預浸材物品100可用作用於通訊裝置天線或天線饋線之印刷線路板之基材，以連接位於不同平面上之裝置之電子組件。包括一或多個預浸材物品100之本印刷線路板可用於通訊網路設備中，諸如用於蜂巢式通訊網路之塔中之傳輸天線中。包括預浸材物品100之印刷線路板亦可用於其他應用中，諸如用於行動計算裝置中之相機饋線。Multiple prepreg articles 100 may be laminated together to form a multi-layer laminate or a multi-layer printed circuit board. The central prepreg article 100 may include a top conductive coating and a bottom conductive coating. The prepreg articles 100 may each include a single optional conductive coating. The prepreg articles 100 may be bonded to the central prepreg article 100 via an adhesive layer. The adhesive layer may be, for example, an adhesive that can bond at a temperature lower than the melting point of the perfluorocopolymer matrix 110 of the prepreg article 100. In some examples, the adhesive layer is a thermoplastic adhesive that is capable of bonding at a temperature between 0°C and 50°C lower than the melting point of the perfluorocopolymer matrix 110 of the adjacent laminate. Printed circuit boards made from the prepreg articles 100 described herein can be used in various applications, such as high-frequency applications, such as high-frequency communication applications. For example, the printed circuit board including one or more flexible laminate prepreg articles 100 can be used in antennas or antenna feeds for communication devices (such as mobile communication devices) that can operate on 5G communication networks. For example, the prepreg article 100 can be used as a substrate for a printed circuit board used for an antenna or antenna feed of a communication device to connect electronic components of the device located on different planes. The printed circuit board including one or more prepreg articles 100 can be used in communication network equipment, such as in transmission antennas used in towers of cellular communication networks. A printed circuit board including the prepreg article 100 may also be used in other applications, such as camera feeds in mobile computing devices.
根據一些態樣，一種多層層壓體包括一第一層，該第一層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。該多層層壓體可具有一第二層，該第二層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化全氟共聚物及非氟化全氟共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光；及導電包覆，其設置於該介電基材之一表面上。在某些態樣，導電包覆係設置於第二層之介電基材之一個表面上。在某些態樣，導電包覆係設置於第二層之介電基材之多個表面上。在某些態樣，導電包覆係設置於第二層之介電基材之相對表面上。According to some aspects, a multi-layer laminate includes a first layer, the first layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric embedded in the perfluoro copolymer matrix; and an additive material dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The multi-layer laminate may have a second layer, the second layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated perfluoro copolymer and a non-fluorinated perfluoro copolymer; an L-glass fabric embedded in the perfluoro copolymer matrix; and an additive material dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light; and a conductive coating disposed on one surface of the dielectric substrate. In some embodiments, the conductive coating is disposed on one surface of the second dielectric substrate. In some embodiments, the conductive coating is disposed on multiple surfaces of the second dielectric substrate. In some embodiments, the conductive coating is disposed on opposite surfaces of the second dielectric substrate.
根據一些態樣，一種多層層壓體包括一第一層，該第一層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化四氟乙烯/六氟丙烯共聚物；L-玻璃織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光。該多層層壓體可具有一第二層，該第二層包含一介電基材，該介電基材具有：全氟共聚物基質，其包含氟化全氟共聚物及非氟化全氟共聚物；石英織物，其嵌入該全氟共聚物基質中；及添加劑材料，其分散於該全氟共聚物基質中，其中該添加劑材料能夠吸收紫外光；及導電包覆，其設置於該介電基材之一表面上。在某些態樣，導電包覆係設置於第二層之介電基材之一個表面上。在某些態樣，導電包覆係設置於第二層之介電基材之多個表面上。在某些態樣，導電包覆係設置於第二層之介電基材之相對表面上。According to some aspects, a multi-layer laminate includes a first layer, the first layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated tetrafluoroethylene/hexafluoropropylene copolymer; an L-glass fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light. The multi-layer laminate may have a second layer, the second layer comprising a dielectric substrate, the dielectric substrate having: a perfluoro copolymer matrix, which includes a fluorinated perfluoro copolymer and a non-fluorinated perfluoro copolymer; a quartz fabric, which is embedded in the perfluoro copolymer matrix; and an additive material, which is dispersed in the perfluoro copolymer matrix, wherein the additive material is capable of absorbing ultraviolet light; and a conductive coating, which is disposed on one surface of the dielectric substrate. In some embodiments, the conductive coating is disposed on one surface of the second dielectric substrate. In some embodiments, the conductive coating is disposed on multiple surfaces of the second dielectric substrate. In some embodiments, the conductive coating is disposed on opposite surfaces of the second dielectric substrate.
本文所述之多層層壓體可提供意想不到之益處。例如，電氣性能益處包括比習知市售熱固性樹脂基預浸材/系統更低之介電常數及損耗正切。此等特性可顯著改善設計靈活性及性能（特別係插入損耗）。The multi-layer laminates described herein can provide unexpected benefits. For example, electrical performance benefits include lower dielectric constant and loss tangent than conventional commercially available thermoset resin-based prepregs/systems. These properties can significantly improve design flexibility and performance (particularly insertion loss).
另外，此類多層層壓體提供與黏著性相關之益處。本文所述之預浸材物品100之黏著性對用於箔層壓結構（諸如對於印刷線路板上之外層）之更佳（即更平滑）的銅箔提供更佳（即更強）的黏著性。本文所述之多層層壓體之層之組合在此類外層上提供較低的插入損耗跡線，因為該等多層層壓體藉由較低的Dk而獲得有利的幾何結構，並藉由改善的黏著性而獲得更平滑的銅。Additionally, such multi-layer laminates provide benefits related to adhesion. The adhesion of the prepreg article 100 described herein provides better (i.e., smoother) adhesion to better (i.e., smoother) copper foils used in foil laminate structures (such as for outer layers on printed circuit boards). The combination of layers of the multi-layer laminates described herein provide lower insertion loss traces on such outer layers because the multi-layer laminates achieve favorable geometry through lower Dk and smoother copper through improved adhesion.
本文所述之預浸材物品100可藉由眾所周知之層壓程序製造。例如，L-玻璃織物108可設置於兩個全氟共聚物膜之間。各全氟共聚物膜可具有在10 µm與100 µm之間之厚度，例如在10 µm與80 µm之間、或在10 µm與60 µm之間。可選導電包覆可設置於各別全氟共聚物膜上。例如，可選導電包覆係電沉積銅箔或輥軋退火銅箔。各導電包覆具有小於約72 µm之厚度，例如小於約18 µm，或例如在10 µm與18 µm之間。The prepreg article 100 described herein can be manufactured by a well-known lamination process. For example, the L-glass fabric 108 can be disposed between two perfluoro copolymer films. Each perfluoro copolymer film can have a thickness between 10 μm and 100 μm, such as between 10 μm and 80 μm, or between 10 μm and 60 μm. An optional conductive coating can be disposed on each perfluoro copolymer film. For example, the optional conductive coating is an electrodeposited copper foil or a roll-annealed copper foil. Each conductive coating has a thickness of less than about 72 μm, such as less than about 18 μm, or such as between 10 μm and 18 μm.
可將上述材料之層加熱並壓製，以壓實材料之層，從而形成預浸材物品100。選擇層壓程序之參數（例如溫度、時間、及壓力）以達到全氟共聚物之目標黏度，其使全氟共聚物能夠流動，從而潤濕及包封L-玻璃織物108之玻璃束，並使全氟共聚物與可選導電包覆之間具有良好黏著性。溫度可大於全氟共聚物之熔點，例如較全氟共聚物之熔點高10℃與100℃之間。例如，溫度可在275℃與375℃之間，例如在290℃與350℃之間、例如290℃、310℃、330℃、或350℃。溫度上升速率可在1與5℃/分鐘之間，例如1℃/分鐘、2℃/分鐘、3℃/分鐘、或4℃/分鐘。施加至材料之層之壓力可在100 psi與1000 psi之間，例如在50 psi與1000 psi之間、或在100 psi與6000 psi之間。停留時間（例如，用於靜態層壓程序）可在30分鐘與120分鐘之間，例如30分鐘、60分鐘、90分鐘、或120分鐘。 實例The layers of the above materials may be heated and pressed to compact the layers of materials to form the prepreg article 100. The parameters of the layer pressing process (e.g., temperature, time, and pressure) are selected to achieve a target viscosity of the perfluoro copolymer that enables the perfluoro copolymer to flow, thereby wetting and encapsulating the glass strands of the L-glass fabric 108, and to provide good adhesion between the perfluoro copolymer and the optional conductive coating. The temperature may be greater than the melting point of the perfluoro copolymer, such as between 10° C. and 100° C. above the melting point of the perfluoro copolymer. For example, the temperature may be between 275° C. and 375° C., such as between 290° C. and 350° C., such as 290° C., 310° C., 330° C., or 350° C. The temperature ramp rate may be between 1 and 5°C/min, such as 1°C/min, 2°C/min, 3°C/min, or 4°C/min. The pressure applied to the layer of material may be between 100 psi and 1000 psi, such as between 50 psi and 1000 psi, or between 100 psi and 6000 psi. The dwell time (e.g., for a static lamination process) may be between 30 minutes and 120 minutes, such as 30 minutes, 60 minutes, 90 minutes, or 120 minutes.Example
下列聚合物乃用於此等實例中。The following polymers were used in these examples.
FEP1：一種高度氟化可熔融加工樹脂，其具有約7 g/10 min之MFR，由約11.75%之HFP（六氟丙烯）及約88.25%之TFE（四氟乙烯）所組成，其中樹脂中每百萬個碳原子之羧基端基數目係在20與40之間。FEP1: A highly fluorinated melt-processable resin having an MFR of about 7 g/10 min, composed of about 11.75% HFP (hexafluoropropylene) and about 88.25% TFE (tetrafluoroethylene), wherein the number of carboxyl end groups per million carbon atoms in the resin is between 20 and 40.
FEP2：一種高度氟化可熔融加工樹脂，其具有約20 g/10 min之MFR，由約10.4%之HFP及約1.2%之PEVE及88.4%之TFE所組成，其中樹脂中每百萬個碳原子之羧基端基數目係在20與40之間。FEP2: A highly fluorinated melt-processable resin having an MFR of about 20 g/10 min, composed of about 10.4% HFP, about 1.2% PEVE and 88.4% TFE, wherein the number of carboxyl end groups per million carbon atoms in the resin is between 20 and 40.
FEP3：一種部分氟化可熔融加工樹脂，其具有約30 g/10 min之MFR，由約10.4%之HFP及約1.2%之PEVE及88.4%之TFE所組成，其中樹脂中每百萬個碳原子之羧基端基數目係在100與200之間。 實例1：帶有L-玻璃織物之預浸材物品之機械表徵FEP3: A partially fluorinated melt-processible resin having an MFR of about 30 g/10 min, composed of about 10.4% HFP and about 1.2% PEVE and 88.4% TFE, wherein the number of carboxyl end groups per million carbon atoms in the resin is between 100 and 200.Example 1: Mechanical characterization of prepreg articles with L-glass fabric
進行實驗以研究預浸材物品之特性。將由約31%之FEP1、約60%之FEP2、約8%之FEP3連同1 wt%之Chemours TiPure™R101二氧化鈦所組成之混合物在熔體中混合，以形成MFR係約15 g/10 min且每百萬個碳原子之總羧基端基在30與60之間之摻合物。隨後將此混合物澆注成約56 µm之膜，該膜之一側又進行電暈處理，以增強黏著性，其中經電暈處理之該側與強化材料直接接觸。將一層FEP膜放置在Asahi Kasei (Japan)之NL1035 L-玻璃織物之兩側以形成預浸材物品。用於形成層壓體之全氟共聚物膜之厚度係56 µm。離形材料之厚度係50 µm。將材料在300℃之停留溫度及200 psi之壓力下於熱油真空壓機中層壓，停留時間為60分鐘，真空度為1 atm，且上升速率為2℃/分鐘。在測試前，使樣本在23℃及50%相對濕度下平衡24小時。Experiments were conducted to investigate the properties of prepreg articles. A mixture of about 31% FEP1, about 60% FEP2, about 8% FEP3, and 1 wt% Chemours TiPure™ R101 titanium dioxide was mixed in a melt to form a blend having an MFR of about 15 g/10 min and a total carboxyl end groups per million carbon atoms between 30 and 60. This mixture was then cast into a film of about 56 µm, which was corona treated on one side to enhance adhesion, wherein the corona treated side was in direct contact with the reinforcement material. A layer of FEP film was placed on both sides of an Asahi Kasei (Japan) NL1035 L-glass fabric to form a prepreg article. The thickness of the perfluorocopolymer film used to form the laminar body was 56 µm. The thickness of the release material was 50 µm. The materials were laminated in a hot oil vacuum press at a dwell temperature of 300°C and a pressure of 200 psi, a dwell time of 60 minutes, a vacuum of 1 atm, and a ramp rate of 2°C/min. The samples were equilibrated at 23°C and 50% relative humidity for 24 hours prior to testing.
測試預浸材物品之各種特性，包括擠出、離形品質、厚度、芯吸、288℃/60sec浮焊、截面、樹脂含量、密度、介電常數、散逸因數、及尺寸穩定性。用於執行此等測試之測試方法如下： - 擠出：測量局部之樹脂流量，報告四個側之平均值。 - 離形品質：內部定性評估，其中得分1 =差，及5 =佳。 - 厚度：根據IPC TM-650 2.2.18使用Thwing-Albert ProGage測量預浸材z軸厚度。 - 芯吸：內部測試方法，其中在1/8''沖孔內進行墨水流量測量，目的係評估樹脂對玻璃之黏著性品質。 - 浮焊：使用IPC TM-650 2.4.13在288℃下測試60秒。 - 截面：根據IPC TM-650 2.1.1之光學微截面檢測技術。 - 樹脂含量：根據IPC TM-650 2.3.16.1c進行測試。 - 密度：根據IPC TM-650 2.3.5b測量比重。 - 介電常數：根據IPC TM-650 2.5.5.15進行10GHz面內測量。 - 散逸因數：根據IPC TM-650 2.5.5.15進行10GHz面內測量。 - 尺寸穩定性：根據IPC TM-650 2.2.4c之方法A測量。Prepreg articles are tested for various properties including extrusion, release quality, thickness, wicking, 288°C/60sec solder float, cross section, resin content, density, dielectric constant, dissipation factor, and dimensional stability. The test methods used to perform these tests are as follows:- Extrusion: localized resin flow is measured and the average of four sides is reported.- Release Quality: internal qualitative evaluation where a score of 1 = poor and 5 = good.- Thickness: prepreg z-axis thickness is measured using a Thwing-Albert ProGage per IPC TM-650 2.2.18.- Wicking: internal test method where ink flow is measured in a 1/8'' punched hole to evaluate the quality of the resin adhesion to glass.- Solder Float: Tested at 288°C for 60 seconds using IPC TM-650 2.4.13.- Cross-Section: Tested using the optical micro-sectioning technique of IPC TM-650 2.1.1.- Resin Content: Tested in accordance with IPC TM-650 2.3.16.1c.- Density: Specific gravity measured in accordance with IPC TM-650 2.3.5b.- Dielectric Constant: Measured in-plane at 10 GHz in accordance with IPC TM-650 2.5.5.15.- Dissipation Factor: Measured in-plane at 10 GHz in accordance with IPC TM-650 2.5.5.15.- Dimensional Stability: Measured in accordance with IPC TM-650 2.2.4c, Method A.
測試結果如下表2所示。
對各種多層層壓體組成物在一定頻率範圍內之插入損耗值進行建模。插入損耗(dB)經計算為10 Log 10 (P2 / P1)，其中P1係初始功率（傳輸），P2係插入後之功率（接收）。通常，插入損耗係使用負數為報告之慣例（以dB表示），其指示頻率點處或沿傳輸線之點上或傳輸線之接收端處之信號功率（或透過如空氣、空間之任何路徑無線發送之信號）。在此範例中，對電路設計特徵（接地平面間距及特性阻抗）建立了相同的限制。Insertion loss values for various multi-layer piezo compositions over a range of frequencies are modeled. Insertion loss (dB) is calculated as 10 Log 10 (P2 / P1), where P1 is the initial power (transmitted) and P2 is the power after insertion (received). Insertion loss is usually reported using the convention of a negative number (expressed in dB) indicating the power of a signal at a frequency point or point along a transmission line or at the receiving end of a transmission line (or a signal sent wirelessly through any path such as air or space). In this example, the same limits are established for the circuit design features (ground plane spacing and characteristic impedance).
此等值如圖2所示並如下所述。These values are shown in Figure 2 and described below.
白點/線：最佳曲線-顯示最高性能 - 層壓體係複合物上之銅箔包覆，其使用PFA基樹脂配方（增強UV雷射機械加工之添加劑）及編織L-玻璃（低Dk）強化材料 - 預浸材係FEP基樹脂配方（增強UV雷射機械加工之添加劑）及編織L-玻璃（低Dk）強化材料White dots/lines: Best curve - shows highest performance- Laminate is copper foil over composite using PFA based resin formulation (additive for UV laser machining enhancement) and woven L-glass (low Dk) reinforcement- Prepreg is FEP based resin formulation (additive for UV laser machining enhancement) and woven L-glass (low Dk) reinforcement
白色填滿點、黑色線條及輪廓：第二條曲線-中等性能 - 層壓體係複合物上之銅箔包覆，其使用PFA基樹脂配方（增強UV雷射機械加工之添加劑）及編織L-玻璃（低Dk）強化材料 - 預浸材係市售PPS增強熱固性樹脂系統，其具有編織L-玻璃（低Dk）強化材料White fill points, black lines and outlines: Second curve - medium performance- Laminate is copper foil wrap on composite using PFA based resin formulation (additive to enhance UV laser machining) with woven L-glass (low Dk) reinforcement- Prepreg is a commercial PPS reinforced thermoset resin system with woven L-glass (low Dk) reinforcement
黑點/線：第三條曲線-單獨比較系統之最高性能 - 層壓體係覆銅市售PPS增強熱固性樹脂系統，其具有編織L-玻璃（低Dk）強化材料 - 預浸材係市售PPS增強熱固性樹脂系統，其具有編織L-玻璃（低Dk）強化材料Black dots/lines: Third curve - highest performance of systems compared individually- Laminate is a copper-clad commercial PPS-reinforced thermoset resin system with braided L-glass (low Dk) reinforcement- Prepreg is a commercial PPS-reinforced thermoset resin system with braided L-glass (low Dk) reinforcement
藍色調之點/線顯示為第4條及第5條曲線 - 層壓體係覆銅市售PPS增強熱固性樹脂系統，其具有編織L-玻璃（低Dk）強化材料 - 預浸材係市售PPS增強熱固性樹脂系統，其具有編織L-玻璃（低Dk）強化材料The blue dots/lines are shown as curves 4 and 5- Laminate is a copper-clad commercial PPS-reinforced thermoset resin system with braided L-glass (low Dk) reinforcement- Prepreg is a commercial PPS-reinforced thermoset resin system with braided L-glass (low Dk) reinforcement
表2中之數值證明本發明內之多層層壓體提供最高性能，並且在寬廣的頻率範圍內之插入損耗具有顯著改善。此項改善代表更高之信號保真度，信號更清晰、且損壞更少。The values in Table 2 demonstrate that the multi-layer laminate of the present invention provides the highest performance with significant improvement in insertion loss over a wide frequency range. This improvement translates into higher signal fidelity, cleaner signals, and less corruption.
100:預浸材物品 102:介電基材 106:表面 108:L-玻璃織物 110:全氟共聚物基質 112:添加劑材料100: Prepreg article102: Dielectric substrate106: Surface108: L-glass fabric110: Perfluoro copolymer matrix112: Additive material
圖1係可撓性預浸材物品之示意圖。 圖2示出各種多層層壓體之插入損耗值。Figure 1 is a schematic diagram of a flexible prepreg article.Figure 2 shows the insertion loss values of various multi-layer laminates.
100:預浸材物品100: Prepreg items
102:介電基材102: Dielectric substrate
106:表面106: Surface
108:L-玻璃織物108:L-Glass fabric
110:全氟共聚物基質110: Perfluoro copolymer matrix
112:添加劑材料112: Additive materials
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US202363538901P | 2023-09-18 | 2023-09-18 | |
| US63/538,901 | 2023-09-18 |
| Publication Number | Publication Date |
|---|---|
| TW202513685Atrue TW202513685A (en) | 2025-04-01 |
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW113134176ATW202513685A (en) | 2023-09-18 | 2024-09-10 | Prepreg article |
| Country | Link |
|---|---|
| TW (1) | TW202513685A (en) |
| WO (1) | WO2025064368A1 (en) |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TWI686293B (en)* | 2019-06-21 | 2020-03-01 | 台燿科技股份有限公司 | Metal-clad laminate and manufacturing method of the same |
| TWI725538B (en)* | 2019-09-04 | 2021-04-21 | 台燿科技股份有限公司 | Metal-clad laminate, printed circuit board, and method for manufacturing the same |
| JP7502218B2 (en)* | 2021-02-26 | 2024-06-18 | 信越化学工業株式会社 | Resin substrate with dielectric properties that are less dependent on frequency |
| Publication number | Publication date |
|---|---|
| WO2025064368A1 (en) | 2025-03-27 |
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