CN112063082A - 氟系基板、铜箔基板及印刷电路板 - Google Patents
氟系基板、铜箔基板及印刷电路板 Download PDFInfo
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- CN112063082A CN112063082A CN201910614981.1A CN201910614981A CN112063082A CN 112063082 A CN112063082 A CN 112063082A CN 201910614981 A CN201910614981 A CN 201910614981A CN 112063082 A CN112063082 A CN 112063082A
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- Prior art keywords
- fluorine
- inorganic filler
- reinforcing material
- material layer
- substrate
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Abstract
本发明公开一种氟系基板、铜箔基板及印刷电路板。氟系基板包括一增强材料层和一氟系树脂层，增强材料层包括一基材和一第一无机填料，第一无机填料附着于基材上，并分散于增强材料层中，第一无机填料的粒径为0.02微米至1微米。氟系树脂层包覆增强材料层，氟系树脂层包括一第二无机填料，第二无机填料的粒径为大于1微米至100微米。
Description
技术领域
本发明涉及一种氟系基板、铜箔基板及印刷电路板，特别是涉及一种适用于高频传输的氟系基板、铜箔基板及印刷电路板。
背景技术
随着科技的进步，高频传输已是无法避免的趋势。为因应高频传输的需求，业界对于电路基板的特性要求也因此日益提升。一般而言，高频基板需具有较高的介电常数(dielectric constant，Dk)、较低的介电损耗(dielectric dissipation factor，Df)以及较高的导热特性，借此兼具良好的介电性能以及热传导特性。使电路基板可应用于基站天线、卫星雷达、汽车用雷达、无线通信天线或是功率放大器的高频电路基板。
氟系基板因具有较低的介电损耗以及可通过树脂含量调控介电常数的优势，而被广泛应用于高频电路基板。现有技术中，通常会于氟系基板中添加高含量的无机填料，以提升其介电性能以及热传导特性。然而，当无机填料的含量过高时，会导致铜箔与氟系基板间的接着性不佳，于加工钻孔或镀孔操作时，铜箔容易自氟系基板上脱落。且无机填料的含量过高时，无机填料容易分散不均，进而影响氟系基板特性的均匀性和稳定性。
为了解决上述无机填料的信赖性问题，现有技术中提供了在铜箔与氟系基板间设置接着膜材，或涂布接着树脂的技术手段，以提升铜箔与氟系基板的接着强度。但设置接着膜材或涂布接着树脂的方式，成本较高且制造过程较为繁琐。另外，接着膜材或接着树脂的存在，会影响整体氟系基板的特性，而无法兼具高介电和高热传导的特性。
发明内容
本发明所要解决的技术问题在于，针对现有技术的不足提供一种氟系基板、铜箔基板及印刷电路板。
为了解决上述的技术问题，本发明所采用的其中一技术方案是，提供一种氟系基板。氟系基板包括一增强材料层和一氟系树脂层，增强材料层包括一基材和一第一无机填料，第一无机填料附着于基材上并分散于增强材料层中，第一无机填料的粒径为0.02微米至1微米。氟系树脂层包覆增强材料层，氟系树脂层包括一第二无机填料，第二无机填料的粒径为大于1微米至100微米。
优选地，第一无机填料和第二无机填料为二氧化硅、二氧化钛、氢氧化铝、氧化铝、氢氧化镁、氧化镁、碳酸钙、氧化硼、氧化钙、钛酸锶、钛酸钡、钛酸钙、钛酸镁、氮化硼、氮化铝、碳化硅、二氧化铈或其任意组合。
优选地，增强材料层的厚度为40微米至100微米。
优选地，氟系树脂层的厚度为70微米至180微米。
优选地，基材为一纤维布，第一无机填料填补于纤维布的孔隙以及纤维布的纱束的间隙。
优选地，增强材料层中第一无机填料的含量为50wt％至80wt％。
优选地，氟系树脂层中第二无机填料的含量为20wt％至70wt％。
优选地，氟系树脂层完整包覆增强材料层。
为了解决上述的技术问题，本发明所采用的另外一技术方案是，提供一种铜箔基板。铜箔基板包括一氟系基板和一铜箔，铜箔设置于氟系基板上，氟系基板包括一增强材料层和一氟系树脂层。增强材料层包括一基材和一第一无机填料。其中，第一无机填料附着于基材上并分散于增强材料层中，第一无机填料的粒径为0.02微米至1微米。氟系树脂层包覆增强材料层，氟系树脂层包括一第二无机填料，第二无机填料的粒径为大于1微米至100微米。
为了解决上述的技术问题，本发明所采用的另外一技术方案是，提供一种印刷电路板。印刷电路板包括一氟系基板和一电路层，电路层设置于氟系基板上。氟系基板包括一增强材料层和一氟系树脂层。增强材料层包括一基材和一第一无机填料。其中，第一无机填料附着于基材上并分散于增强材料层中，第一无机填料的粒径为0.02微米至1微米。氟系树脂层包覆增强材料层，氟系树脂层包括一第二无机填料，第二无机填料的粒径为大于1微米至100微米。
本发明的其中一有益效果在于，本发明所提供的氟系基板、铜箔基板及印刷电路板，其能通过“氟系树脂层包覆于所述增强材料层外”、“调控第一无机填料的粒径为0.02微米至1微米”以及“调控第二无机填料的粒径为大于1微米至100微米”的技术特征，使氟系基板、铜箔基板及印刷电路板兼具良好的介电性能和热传导特性，且仍具有良好的接着信赖性。
为使能更进一步了解本发明的特征及技术内容，请参阅以下有关本发明的详细说明与附图，然而所提供的附图仅用于提供参考与说明，并非用来对本发明加以限制。
附图说明
图1为本发明第一实施例的铜箔基板的侧视剖面示意图。
图2为图1中增强材料层的立体示意图。
图3为图2的III部分的放大示意图。
图4为图2的IV部分的放大示意图。
图5为本发明铜箔基板的制作方法的流程图。
图6为本发明第二实施例的铜箔基板的侧视剖面示意图。
图7为本发明第三实施例的铜箔基板的侧视剖面示意图。
具体实施方式
以下是通过特定的具体实施例来说明本发明所公开有关“氟系基板、铜箔基板及印刷电路板”的实施方式，本领域技术人员可由本说明书所公开的内容了解本发明的优点与效果。本发明可通过其他不同的具体实施例加以施行或应用，本说明书中的各项细节也可基于不同观点与应用，在不悖离本发明的构思下进行各种修改与变更。另外，本发明的附图仅为简单示意说明，并非依实际尺寸的描绘，事先声明。以下的实施方式将进一步详细说明本发明的相关技术内容，但所公开的内容并非用以限制本发明的保护范围。
应当可以理解的是，虽然本文中可能会使用到“第一”、“第二”、“第三”等术语来描述各种组件，但这些组件不应受这些术语的限制。这些术语主要是用以区分一组件与另一组件。另外，本文中所使用的术语“或”，应视实际情况可能包括相关联的列出项目中的任一个或者多个的组合。
请参阅图1所示，图1为本发明第一实施例的铜箔基板的侧视剖面示意图。本发明提供一种铜箔基板1，其包括一增强材料层10、一氟系树脂层20和一铜箔30。本发明的铜箔基板1兼具有优异的介电特性和良好的热传导特性，而可应用于高频电路板。并且，本发明可在不设置接着膜层或不涂布接着树脂的情况下，使铜箔基板1具有较高的剥离强度。即使后续在钻孔或镀孔的制程时，铜箔30仍具有良好的接着信赖性，不会轻易与氟系树脂层20分离。
本实施例中，增强材料层10包括一基材11和一第一无机填料12。增强材料层10的厚度为40微米至100微米。基材11可以是一纤维布或绝缘纸，但不以此为限。基材11的材料可以是玻璃纤维、碳纤维、石墨纤维、氧化铝纤维、碳化硅纤维、氮化硅纤维、硼纤维或其组合物。较佳的，基材11的材料可以是玻璃纤维，但不以此为限。
第一无机填料12附着于基材11上，并平均分散于增强材料层10中除了基材11的部分。第一无机填料12的粒径为0.02微米至1微米(例如20至1000纳米之间的正整数)。第一无机填料12可以是二氧化硅、二氧化钛、氢氧化铝、氧化铝、氢氧化镁、氧化镁、碳酸钙、氧化硼、氧化钙、钛酸锶、钛酸钡、钛酸钙、钛酸镁、氮化硼、氮化铝、碳化硅、二氧化铈或其任意组合。
其中，二氧化硅可以为熔融型或是结晶型的二氧化硅，若考虑整体铜箔基板1的介电特性，较优选为熔融型二氧化硅。二氧化钛可以是金红石(rutile)、锐钛矿(anatase)或板钛矿(brookite)构型的二氧化钛，若考虑整体铜箔基板1的介电特性，较优选为金红石构型的二氧化钛。
请合并参阅图2至4所示，图2为本发明中增强材料层10的示意图。图3和图4分别为图2中III部分和IV部分的局部放大图。在本实施例中，基材11为一纤维布，若进一步观察增强材料层10的结构，可发现一部分的第一无机填料12，填补于纤维布的孔隙(如图2所示)。而另一部份的第一无机填料12，填补于纤维布的纱束111于末端或中段的间隙中(如图3、4所示)。本发明通过第一无机填料12的使用，可提升基材11本身的结构强度，更可提升增强材料层10于X-Z平面上的介电常数稳定性以及尺寸安定性。
再请参阅图1所示，氟系树脂层20包覆增强材料层10。具体来说，氟系树脂层20可以是形成于增强材料层10的相对两侧，夹设于增强材料层10外(如图1所示)，也可以完整包覆于增强材料层10外。氟系树脂层20的厚度为70微米至180微米。
氟系树脂层20中包括一第二无机填料21，第二无机填料21的粒径为大于1微米至100微米(例如1至100微米之间的正整数)，第二无机填料21设置于增强材料层10上，并分散于氟系树脂层20。第二无机填料21可以是二氧化硅、二氧化钛、氢氧化铝、氧化铝、氢氧化镁、氧化镁、碳酸钙、氧化硼、氧化钙、钛酸锶、钛酸钡、钛酸钙、钛酸镁、氮化硼、氮化铝、碳化硅、二氧化铈或其任意组合。
前述增强材料层10和氟系树脂层20所构成的结构合称作氟系基板。而氟系基板中的第一无机填料12和第二无机填料21可以是相同或不同的材料。于其中一实施例，当第一无机填料12和第二无机填料21为相同材料时，可提升增强材料层10和氟系树脂层20之间的兼容性，以增加铜箔基板1的剥离强度。于另一实施例中，第一无机填料12和第二无机填料21可以是不同的材料，并可通过选用不同材料的无机填料，以调整铜箔基板1的介电常数或其他特性。
铜箔30设置于氟系树脂层20上，并可依铜箔基板1的种类不同，选择设置不同数量的铜箔30。例如：选择于氟系基板上设置一铜箔30，可制得单面铜箔基板(如图1所示)；若选择于氟系基板上设置二铜箔30，可制得双面铜箔基板(如图7所示)。关于双面铜箔基板的具体结构，将于后详述。
请合并参阅图1、5所示，图5为本发明铜箔基板1的制备方法的流程图。铜箔基板1的制备方法包括以下步骤：首先，提供一基材11(步骤S100)。于基材11上施以一第一溶液(步骤S102)。干燥施有第一溶液的基材11，以形成一增强材料层10(步骤S104)。
在步骤S102中，于基材11上施以第一溶液的方式，可以是将基材11含浸于第一溶液中，或是将第一溶液涂布于基材11上。第一溶液中包括：浓度为50wt％至80wt％的第一无机填料12、浓度为10wt％至40wt％的氟系树脂、浓度为1wt％至10wt％的含氟聚合物、浓度为0.1wt％至50wt％的低分子量聚四氟乙烯以及浓度为0.1wt％至10wt％的含浸助剂。
在本实施例中，氟系树脂可以是聚四氟乙烯树脂，但不以此为限。含氟聚合物可以是四氟乙烯/全氟烷氧基乙烯基醚共聚物(PFA)或全氟乙烯丙烯共聚物(FEP)。低分子量聚四氟乙烯可通过热裂解降解法或辐照降解法制得，低分子量聚四氟乙烯的分子量为2000至200000。较佳的，低分子量聚四氟乙烯的分子量为10000至100000。含浸助剂可以是但不限于：羟乙基纤维素、硝化纤维素、聚甲基苯乙烯、聚甲基丙烯酸甲酯、聚乙二醇或其任意组合。含浸助剂的添加可调整树脂组成物的黏度，而可避免因黏度过高导致表面粗糙，而影响增强材料层10的成膜平整性。或是避免因黏度过低，导致增强材料层10表面形成有孔洞。
于基材11上施以第一溶液后，第一无机填料12会填补于基材11的缝隙，并平均分散设置于基材11上。第一无机填料12的使用，可提升基材11本身的结构强度，以及提升增强材料层10于X-Z平面上介电常数的均匀性。由于第一无机填料12是填补于基材11的缝隙，故较不会有因第一无机填料12含量过高，而影响接着信赖性的问题。
在步骤S104中，干燥施有第一溶液的基材11，以形成增强材料层10的方式，可以包括三阶段的升温步骤：使基材11依序于80℃至120℃的温度下干燥、于200℃至240℃的温度下烘烤，以及于340℃至360℃的温度下烧结。且在干燥、烘烤和烧结的各个步骤中，至少维持20分钟。然而，本发明不以此为限。
铜箔基板1的制备方法包括：于增强材料层10上施以一第二溶液(步骤S106)。干燥施有第二溶液的增强材料层10，以于增强材料层10上形成一氟系树脂层20，而制得氟系基板(步骤S108)。
在步骤S106中，于增强材料层10上施以第二溶液的步骤，可以是将增强材料层10含浸于第二溶液中，或是将第二溶液涂布于增强材料层10外。第二溶液中包括浓度为20wt％至70wt％的第二无机填料21、浓度为10wt％至70wt％的氟系树脂、浓度为1wt％至10wt％的含氟聚合物、浓度为0.1wt％至50wt％的低分子量聚四氟乙烯以及浓度为0.1wt％至10wt％的含浸助剂。其中，第二溶液中的氟系树脂、含氟聚合物、低分子量聚四氟乙烯和含浸助剂，与第一溶液中相似，故于此不再赘述。
通过调控含氟聚合物的含量，可使氟系树脂层20具有良好的加工性。举例来说，若氟系树脂层20中含氟聚合物的用量大于10wt％时，在热压铜箔的过程中容易出现流胶，而影响铜箔基板1的加工性和厚度均匀性。若氟系树脂层20中含氟聚合物的用量小于1wt％时，则铜箔30容易剥落。
低分子量聚四氟乙烯(分子量为2000至200000，较佳分子量为10000至100000)因分子链较短，而具有较佳的排列能力。因此，在适当温度下进行烧结或压合制程时，低分子量聚四氟乙烯的添加，可增加氟系树脂层20的结晶度，进而提升氟系树脂层20的热传导系数。
于增强材料层10上施以第二溶液后，第二无机填料21会设置于增强材料层10上。
在步骤S108中，干燥施有第二溶液的增强材料层10制得氟系基板的方式，可以包括三阶段的升温步骤：使增强材料层10依序于80℃至120℃的温度下干燥、200℃至240℃的温度下烘烤，以及在340℃至360℃的温度下烧结。且在干燥、烘烤和烧结的各个步骤中，至少维持20分钟。然而，本发明不以此为限。
于其他实施例中，可多次重复步骤S106和步骤S108。也就是重复于增强材料层10上施以第二溶液并干燥的步骤，以便形成特定厚度的氟系树脂层20。由于氟系树脂层20的厚度可依需求进行调整，于本发明中，氟系树脂层20较佳的厚度为50微米至150微米(例如50至150微米之间的正整数)。
最后，铜箔基板1的制备方法包括：于氟系基板的氟系树脂层20上设置一铜箔30，制得一铜箔基板1(步骤S110)。设置铜箔30的方式是在温度为340℃至360℃、压力为45kg/cm2至55kg/cm2的条件下持续热压2小时，使铜箔30贴合于氟系树脂层20上。接着，以1℃/min至4℃/min的降温速率先降温至250℃，再调控以10℃/min的降温速率由250℃降至室温，从而提升氟系树脂层20的结晶度，并可改善铜箔基板1的导热特性。然而，本发明不以此为限。
根据上述内容，通过执行前述步骤S100至步骤S104，可形成增强材料层10。通过执行前述步骤S106和步骤S108，可于增强材料层10外形成氟系树脂层20。值得注意的是，氟系基板的制备方式并不限于上述，实际操作时可重复执行上述步骤S100至步骤S108，形成多个由氟系树脂层20/增强材料层10/氟系树脂层20所构成的结构。并且，可将多个氟系树脂层20/增强材料层10/氟系树脂层20所构成的结构堆叠设置，以达到目标的厚度，如图6所示。
图6为本发明第二实施例的铜箔基板1，其中，氟系基板是由依序堆叠设置的氟系树脂层20/增强材料层10/氟系树脂层20/氟系树脂层20/增强材料层10/氟系树脂层20所构成，而铜箔30形成于氟系树脂层20上，以形成一单面铜箔基板。
除此之外，亦可利用上述制备方法，制备得双面铜箔基板，也就是于氟系基板的相对两侧各设置一铜箔30。请参阅图7所示，图7为本发明第三实施例的铜箔基板的侧视剖面示意图。图7的铜箔基板1与图1的铜箔基板1的差异在于：氟系基板的相对两侧上都设置有一铜箔30。图7中的增强材料层10、氟系树脂层20以及铜箔30的结构与前述相似，于此不再赘述。
另外，于其他实施例中，铜箔基板1可再经由蚀刻显影，对铜箔30进行图案化，形成一电路层。进而制得兼具高介电和高热传导的特性的印刷电路板，且可适用于高频传输。
为了证实本发明的铜箔基板兼具高介电和高热传导的特性，本发明制备了不同的铜箔基板1，各铜箔基板1的制程参数如下表1所示。并对各铜箔基板1进行物性评估，评估方式包括：
(1)热传导分析测试：根据ASTM-D5470测试方法，使用界面材料热阻及热传导系数量测仪器(台湾瑞领科技股份有限公司；型号LW-9389)进行热传导分析测试。
(2)介电常数(10GHz)：使用介电分析仪(Dielectric Analyzer)(型号HP AgilentE4991A)，测试在频率10G Hz时的介电常数。
(3)介电损耗(10GHz)：使用介电分析仪(Dielectric Analyzer)(型号HP AgilentE4991A)，测试在频率10G Hz时的介电损耗。
(4)剥离强度测试：根据IPC-TM-650-2.4.8测试方法，测试铜箔基板的剥离强度。
表1：实施例1至4和比较例1至4的铜箔基板的制备条件和物性评估。
根据表1的结果所示，本发明通过调控增强材料层10中第一无机填料12的粒径大小，可制备获得兼具高介电特性、高热传导特性以及高剥离强度的氟系基板、铜箔基板1以及印刷电路板。具体来说，本发明的铜箔基板1的热传导系数为0.7W/mK至1.8W/mK、介电常数(10GHz)为3.5至11.4、介电损耗(10GHz)为0.0015至0.0020、剥离强度为10.3lb/in至13.3lb/in。
[实施例的有益效果]
本发明的其中一有益效果在于，本发明所提供的氟系基板、铜箔基板1及印刷电路板，其能通过“氟系树脂层20包覆所述增强材料层10”、“调控第一无机填料12的粒径为0.02微米至1微米”以及“调控第二无机填料21的粒径为大于1微米至100微米”的技术特征，使氟系基板、铜箔基板1以及印刷电路板兼具良好的介电性能和热传导特性，且仍具有良好的接着信赖性。
更进一步来说，本发明通过“调控增强材料层10中第一无机填料12的含量”以及“调控氟系树脂层20中第二无机填料21的含量”的技术特征，使基材11上附着有适量的第一无机填料12和第二无机填料21，在提升介电性能和热传导特性之余，仍可维持铜箔基板1以及印刷电路板的接着信赖性。
以上所公开的内容仅为本发明的优选可行实施例，并非因此局限本发明的权利要求书的保护范围，所以凡是运用本发明说明书及附图内容所做的等效技术变化，均包含于本发明的权利要求书的保护范围内。
Claims (10)
1.一种氟系基板，其特征在于，所述氟系基板包括：
一增强材料层，其包括一基材和一第一无机填料，所述第一无机填料附着于所述基材上并分散于所述增强材料层中；其中，所述第一无机填料的粒径为0.02微米至1微米；以及
一氟系树脂层，其包覆所述增强材料层，所述氟系树脂层包括一第二无机填料，所述第二无机填料的粒径为大于1微米至100微米。
2.根据权利要求1所述的氟系基板，其特征在于，所述第一无机填料和所述第二无机填料为二氧化硅、二氧化钛、氢氧化铝、氧化铝、氢氧化镁、氧化镁、碳酸钙、氧化硼、氧化钙、钛酸锶、钛酸钡、钛酸钙、钛酸镁、氮化硼、氮化铝、碳化硅、二氧化铈或其任意组合。
3.根据权利要求1所述的氟系基板，其特征在于，所述增强材料层的厚度为40微米至100微米。
4.根据权利要求1所述的氟系基板，其特征在于，所述氟系树脂层的厚度为70微米至180微米。
5.根据权利要求1所述的氟系基板，其特征在于，所述基材为一纤维布，所述第一无机填料填补于所述纤维布的孔隙以及所述纤维布的纱束的间隙。
6.根据权利要求1所述的氟系基板，其特征在于，所述增强材料层中所述第一无机填料的含量为50wt％至80wt％。
7.根据权利要求1所述的氟系基板，其特征在于，所述氟系树脂层中所述第二无机填料的含量为20wt％至70wt％。
8.根据权利要求1所述的氟系基板，其特征在于，所述氟系树脂层完整包覆所述增强材料层。
9.一种铜箔基板，其特征在于，所述铜箔基板包括：
一氟系基板，其包括：
一增强材料层，其包括一基材和一第一无机填料；其中，所述第一无机填料附着于所述基材上并分散于所述增强材料层中，所述第一无机填料的粒径为0.02微米至1微米；以及
一氟系树脂层，其包覆所述增强材料层，所述氟系树脂层包括一第二无机填料，所述第二无机填料的粒径为大于1微米至100微米；以及
一铜箔，其设置于所述氟系基板上。
10.一种印刷电路板，其特征在于，所述印刷电路板包括：
一氟系基板，其包括：
一增强材料层，其包括一基材和一第一无机填料；其中，所述第一无机填料附着于所述基材上并分散于所述增强材料层中，所述第一无机填料的粒径为0.02微米至1微米；以及
一氟系树脂层，其包覆所述增强材料层，所述氟系树脂层包括一第二无机填料，所述第二无机填料的粒径为大于1微米至100微米；以及
一电路层，其设置于所述氟系基板上。
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