CN109575516A - 高分子基质复合物及应用其的预浸物、印刷电路板 - Google Patents

高分子基质复合物及应用其的预浸物、印刷电路板 Download PDF

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Publication number
CN109575516A
CN109575516A CN201810533035.XA CN201810533035A CN109575516A CN 109575516 A CN109575516 A CN 109575516A CN 201810533035 A CN201810533035 A CN 201810533035A CN 109575516 A CN109575516 A CN 109575516A
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Prior art keywords
polymer matrix
matrix compound
woven
strengthening material
prepreg
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塔朗·阿姆拉
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ITEQ ELECTRONIC CO Ltd
ITEQ Corp
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ITEQ ELECTRONIC CO Ltd
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Abstract

本发明公开一种高分子基质复合物以及使用该高分子基质复合物的预浸物及印刷电路板。高分子基质复合物包括聚合物树脂以及具有自1.5至4.8的介电常数以及10GHz下低于0.003的损耗因子的非织造强化材料。印刷电路板使用包括高分子基质复合物的层合物作为核心层，核心层是包夹于至少两个外层之间。本发明所公开的高分子基质复合物以及使用高分子基质复合物的层合物、预浸物及印刷电路板通过使用特定的非织造强化材料，可以有效降低传输延迟以及编织效应。

Description

高分子基质复合物及应用其的预浸物、印刷电路板
技术领域
本发明涉及一种高分子基质复合物及应用其的预浸物、印刷电路板，特别是涉及一种用于消除传输延迟以及编织效应的高分子基质复合物。
背景技术
印刷电路板(PCB)通常是以介电材料，诸如含浸于一高分子基质中的织造玻璃材料，而制造。由含浸于高分子基质中的织造玻璃材料所形成的复合物的一侧或两侧被以铜层合(clad)以形成用于PCB应用中的层合物。
在多数的应用中，高分子基质是环氧树脂或是经改质的环氧树脂，而聚酰亚胺、双马来酰亚胺三嗪、氰酸酯以及聚苯醚类的聚合物也可以被使用。在一些射频(RF，radiofrequency)应用中，聚丁二烯、聚异戊二烯以及其等的衍生物被与硬化剂、加速剂以及诸如填料以及耐燃剂的添加剂一同使用。由于织造玻璃材料大多为E型玻璃(E-glass)，L型玻璃(L-glass)以及其他低介电常数(Dk)及特殊类型的玻璃的使用增加，举例而言，S型玻璃(S-glass)以及T型玻璃(T-glass)是用于一些特殊的应用中。
玻璃以及高分子基质的介电常数(permittivity或dielectric constant)的差异是非常显著的。在使用较常被使用的E型玻璃的情况下，E型玻璃的Dk是高于6.0(依据量测的频率而定)，而用作基质的高分子的Dk通常是在约3.0，借此产生用于信号传播的非均一(non-homogeneous)介质。
现今，印刷电路板被用于多种高速数字通信应用中，且是用以路由(routing)、切换(switching)以及储存数据的主要工具。随着网络的爆炸性以及指数增长，对于更快速的数据传输速率的需求持续增加。实质上地，此代表每个通道必须传输更多的数据，且每个信道是电路板上的一条传输线。该数据是被编码为高频波形，每个波形通常编码2或4位。在每波形编码2位的情况下，现有使用中的技术称为NRZ或PAM2(即等级2的脉波振幅调变)技术，而在每波形编码4位的情况下，使用PAM4(即等级4的脉波振幅调变)技术。当一条传输线作为对比标准时，差分信号被使用。使用差分信号的一个益处是会产生较低的奈奎斯特频率(Nyquist frequency)：奈奎斯特或载子频率是在使用NRZ传输方式时一半的数据速率，在使用PAM4传输方式时1/4的数据速率。对于单端线(其中数据是通过单一线路发送)而言，需要较高频的谐波；例如，对于发送28Gbps(每秒千兆位-每秒109位)，需要高达70GHz的频率分量(基频的第5谐波)。这样高频的问题在于在介电质中信号幅度损失是该导体的频率的正函数(成正比)，或是铜损为频率的平方根的函数。
电磁波在介质中的传播速度是与介电常数的平方根成反比。换句话说，介电常数越高，信号传播越慢。在典型的背板应用中，通道的长度非常长且可以高达一公尺或是更长。由于现有技术是依赖织造玻璃强化层合物，包括强化材以及树脂的材料会是异质的(heterogeneous)。因此，彼此间隔并形成差分对的的两条传输线通常横跨具有不同介电常数的路径，导致在具有较高介电常数的路径上的信号发生延迟。此现象在数字工程领域已知为“传输延迟(skew)”。随着产业趋向PAM4(并且潜在地，PAM8或更高)的信号传输，传输延迟成为信号传递中更为重要的因子。
已知许多方式来减轻信号延迟，其中最主要的是使用呈一角度而布线的线路。此是有效的方式，但导致对于电路板上的空间无效率的利用，并再次导致浪费面积并增加废料，同时仍导致显著的传输延迟。使用多层预浸物以数据上地平均介电常数的差异同样不是非常有效，由于此途径增加电路板的厚度且仍无法完全解决问题。
使用平板玻璃、偏光玻璃(spread glass)或具有相较于>6.0的Dk的E型玻璃的玻璃，例如具有约4.8的Dk的玻璃同样无法完全解决传输延迟的问题。使用未强化热塑性片材的效果同样受限，此是由于这些电路板通常需要进行超过这些材料的容忍度的高温处理，致使这些材料的机械及热特性变差而导致产品不适合用于制造大多数的电路板。
发明内容
本发明是有关一种高分子基质复合物，其用以减轻与传输延迟以及编织效应(fiber weave effect)相关的损失。本发明使用具有特定范围的Dk以及损耗因子的非织造强化材料来达到上述效果。
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，提供一种高分子基质复合物，其包括聚合物树脂以及具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子的非织造强化材料(non-woven fabric)。
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，提供一种层合物，其包括由上述高分子基质复合物所制成的至少一强化层。
更进一步地，所述的高分子基质复合物进一步包含至少一织造强化材料、一微米尺寸填料、一纳米尺寸填料、一有机短纤纤维、一无机短纤纤维以及一耐燃剂。
更进一步地，所述耐燃剂是一含卤素的耐燃剂。
更进一步地，所述非织造强化材料是经过一表面增强处理的非织造强化材料。
更进一步地，所述非织造强化材料是聚四氟乙烯。
更进一步地，所述非织造强化材料包含一液晶聚合物。
更进一步地，所述非织造强化材料为石英。
更进一步地，所述非织造强化材料是玻璃。
为了解决上述的技术问题，本发明所采用的另外再一技术方案是，提供一种预浸物，其包括部分固化且以具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子的非织造强化材料含浸的树脂部分。
为了解决上述的技术问题，本发明所采用的另外再一技术方案是，提供一种印刷电路板，其包括至少两外层以及包夹于两外层之间的核心层。核心层包含至少一强化层，强化层由上述高分子基质复合物所形成。
更进一步地，所述印刷电路板进一步包含设置在至少两层所述外层与所述核心层之间的一接着片，其中，所述接着片是由一预浸物所形成，所述预浸物包括部分固化并含浸有一非织造强化材料的一树脂部分，所述非织造强化材料具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子。
更进一步地，所述层合物进一步包含设置在所述强化层上的至少一金属层。
本发明的其中一有益效果在于，本发明所提供的高分子基质复合物以及使用高分子基质复合物的产品，其能通过“具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子的非织造强化材料”的技术方案，以消除传输延迟的现象。
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为本发明实施例所提供的层合物的剖面示意图；以及
图2为本发明实施例所提供的印刷电路板的剖面示意图。
具体实施方式
以下是通过特定的具体实例来说明本发明所公开有关“用于消除传输延迟以及编织效应的高分子基质复合物”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。
本发明的实施例提供可以用于电子产业中的高分子基质复合物。高分子基质复合物可以包括聚合物树脂以及非织造强化材料(non-woven fabric)。聚合物树脂是作为基质，而非织造强化材料可以被含浸于聚合物树脂中或是涂布于聚合物树脂上。非织造强化材料是随机并连续存在于聚合物树脂中，因此，相较于非随机及均一的织造物，不会产生不均一(heterogeneity)的区域。
本发明中的聚合物树脂可以包括一或多种已知对于制造预浸物以及层合物材料有用的基础树脂。基础树脂通常为热固性或是热塑性树脂，诸如，但不限于：环氧树脂、以聚亚苯基醚为主的树脂，氰尿酸酯树脂，双马来酰亚胺树脂，聚酰亚胺树脂，酚醛树脂，呋喃树脂，二甲苯甲醛树脂，酮甲醛树脂，尿素树脂，三聚氰胺树脂，苯胺树脂，醇酸树脂，不饱和聚酯树脂，邻苯二甲酸二烯丙酯树脂，氰尿酸三烯丙酯树脂，三嗪树脂，聚氨酯树脂，硅氧树脂以及其等的任意组合或是混合物。在本发明的其中一个实施例中，聚合物树脂具有约3.0的介电常数。然而，本发明并不限制于此。
具体而言，在本发明的实施例中，聚合物树脂为环氧树脂，或是包括环氧树脂。环氧树脂的一些实例包括酚型环氧树脂，诸如那些以双酚A的二缩水甘油醚为主、以苯酚-甲醛酚醛清漆或甲酚-甲醛酚醛清漆的聚缩水甘油醚为主、以三(对羟基苯酚)甲烷的三缩水甘油醚为主，或以四苯乙烷的四缩水甘油醚为主的环氧树脂；胺类为主的环氧树脂，诸如以四缩水甘油基-亚甲基二苯胺为主或以对氨基甘醇的三缩水甘油醚为主的胺类环氧树脂；以及环脂族类的环氧树脂，诸如以3,4-环氧环己基甲基-3,4-环氧环己烷羧酸酯为主的环氧树脂。该用语“环氧树脂”同时代表包含过量的环氧基(例如，前述种类的环氧化基)的化合物与及芳香族二羟基化合物的反应产物。这些化合物可以是经卤素取代的。在本发明的一个较佳实施例中，聚合物树脂包括环氧树脂，此环氧树脂是双酚A衍生物，特别是FR-4。FR-4是由过量的双酚A二甘醇醚与四溴双酚A通过推进反应(advancing reaction)所制造的。环氧树脂与双马来酰亚胺树脂，氰酸酯树脂和/或双马来酰亚胺三嗪树脂的混合物也可以被用于被发明的实施例中。
非织造强化材料可以具有介于约1.5至约4.8的介电常数以及在10GHz之下低于0.003的损耗因子。在本发明的一个较佳实施例中，织造强化材料的介电常数是自约1.8至4.8。上述介电常数的范围是在非织造强化材料被与聚合物树脂组合以形成经树脂含浸的强化材料之前所测量，以及/或是在非织造强化材料与聚合物树脂被并入强化预浸物及/或层合物之前所测量。此处所述及的“介电常数”以及介电常数的范围或是数值是由Bereskin测试方法所测得，或是由切口后置法(slit post method)所测得。具体而言，由于PCB产业通常需要在3.0至3.5左右的Dk，将强化材料的Dk控制在低于4.8可以达到整体层合物具有低介电常数的效果。
非织造强化材料可以是片状或是基础材料(ground material)，这些材料可以被用于制造用于形成预浸物或是层合物的基材片材，而预浸物或是层合物适用于印刷电路板的制造过程中。在一个较佳的实施例中，非织造强化材料是片状材料。
举例而言，非织造强化材料可以包括选自于聚四氟乙烯(PTFE)、石英、玻璃材料、液晶聚合物以及任何其等的组合。具体而言，非织造强化材料可以是非织造PTFE垫/纸，且是选择性地与其他成分及结合剂掺杂，或是可以是石英垫/纸或是液晶聚合物。例如，上述成分可以包括短纤(chopped)PTFE纤维、短纤(chopped)玻璃纤维、填料诸如氮化硼以及熔融二氧化硅。
非织造强化材料的量可以依据使用高分子基质复合物所制造的产品的需求而变化。举例而言，基于高分子基质复合物的总重量，非织造强化材料的含量可以是介于约5％以及约70％之间，且较佳是约5％至约60％。另外，基于高分子基质复合物的总重量，包括填料以及耐燃剂以及其他添加剂的聚合物树脂的含量是介于约95％及约30％之间，且较佳约95％至约40％。
在本发明的一个实施例中，非织造强化材料是受到表面增强处理，用以改良其对聚合物树脂的黏着力。该表面增强处理可以包括电晕处理，或是使用耦合剂。
在本发明的实施例中，该高分子基质复合物可以进一步包括织造强化材料、微米尺寸填料、纳米尺寸填料、有机短纤纤维、无机短纤纤维、阻燃剂、溶剂，以及其他添加物的至少一种。
举例而言，织造强化材料可以包括：无机纤维布，包括各种玻璃布(glass cloth，例如，纱束布、短纤垫、表面毡等)、金属纤维布及类似物；由液晶纤维制造的织造布(例如，全芳族聚酰胺纤维、全芳族聚酯纤维，以及聚吲哚纤维)、由合成纤维素制造的织造布(例如，聚乙烯醇纤维、聚酯纤维以及丙烯酸纤维)、天然纤维布(例如，棉布、麻布以及毛毡)、碳纤维布，以及天然纤维素(cellulosic)布(例如，筏纸、棉纸及纸-玻璃组合纤维纸)。
在本发明的实施例中，织造强化材料是具有自约3.5至7.0，或是更高的介电常数的织造玻璃布料，例如，是低Dk玻璃且具有自3.5至约4.5的介电常数，E型玻璃、R型玻璃、ECR玻璃、5-玻璃、C型玻璃、Q型玻璃以及其他任何已知可以用于制备玻璃布强化预浸物及层合物的织造玻璃布。
复合物中的其他添加剂可以包括起始剂或是催化剂。起始剂或是催化剂的实例包括但不限于，过氧化物或偶氮型聚合反应起始剂。一般而言，被选用的起始剂或是催化剂可以是任何已知可用于树脂合成或是固化的化合物，无论其是否发挥上述(树脂合成或是固化)的功能。
耐燃剂可以是任何已知可用于用以制造预浸物以及层合物的高分子基质复合物的耐燃材料。耐燃剂可以包含卤素，或是不含卤素。或者是，或是额外地，高分子基质复合物可以包括卤素，诸如溴以赋予经固化的树脂耐燃特性。
可被包括于高分子基质复合物的溶剂通常被用于溶解高分子基质复合物中的组分，以及控制高分子基质复合物的黏度，以及/或是将一组分，诸如非织造强化材料维持在悬浮分散液中。在此情况下，对于所属技术领域具有通常知识者为已知与热固性树脂系统并用的溶剂可被使用。例如，溶剂可以包括甲乙酮、甲苯、二甲基甲酰胺(DMF)以及其等的任意混合物。
高分子基质复合物可以进一步包括各种其他选择性地组分，包括填料、增韧剂、黏着促进剂、消泡剂、整平剂、染料以及颜料。例如，荧光染料可以微量被添加至高分子基质复合物，以使得由其制成的层合物在销售时于光学检测设备下暴露至紫外光(UV light)时放出荧光。
须注意的是，树脂组成物被用于制造预浸物以及层合物。在制造方法期间，非织造强化材料是以上述聚合物树脂、选择性的添加剂以及溶剂含浸，或以其他方式和这些组分相互关联，且大部份的溶剂是自高分子基质复合物移除以形成预浸物以及层合物。
上述高分子基质复合物是特别适用于用以制造印刷电路板的预浸物及/或层合物的制备。层合物可以被部分固化或是b阶段处理(b-staged)以形成现有技术的“预浸物”-在此状态下，这些预浸物可以被与额外材料片迭放以形成c阶段(c-staged)或完全固化的层合片。或是，树脂可以被制造成c阶段或完全固化的材料片。
在本发明的实施例中，高分子基质复合物可以通过批次或连续制造方法来制造预浸物。预浸物通常是使用一核心材料，诸如一卷织造玻璃网(布料)而制造，核心材料被退绕于一系列的驱动辊上。该织造玻璃网接着通过涂布区，在该处，该织造玻璃网通过含有热固性树脂系统(包括聚合物树脂)、溶剂以及其他组分的槽体，而织造玻璃网变得含有饱和的聚合物树脂。饱和的织造玻璃网接着通过一对计量辊，该对计量辊将过量的聚合物树脂由饱和的织造玻璃网移除。在其后，经聚合物树脂涂布的织造玻璃网沿干燥塔的长度方向移动一预定期间，直到溶剂被自该织造玻璃网蒸发。第二树脂层以及后续的树脂层可以通过重复这些步骤被施加至织造玻璃网，直到预浸物被完成。此时，预浸物被卷绕至辊。织造玻璃网可以以织造布料材料、纸、塑料片、毛毡，及/或特定材料诸如玻璃纤维颗粒或颗粒材料所取代。
在另一个用以制造预浸物或层合物材料的方法中，高分子基质复合物的组分在常温常压下被预先在混合容器中混合。预混物的黏度是约600-1000cps，且可以通过自预混物添加或移除溶剂而调整。布料基材诸如E型玻璃通过包括经预混的高分子基质复合物的浸渍槽(dip tank)被拉起，通过烘箱塔，在该处过量溶剂被排除，且预浸物在各种制造过程中，基于玻璃织造的形式、树脂含量以及厚度需求，被卷取或以片材覆盖以利成型，在铜(Cu)箔之间层叠。
高分子基质复合物还可作为薄层，通过狭缝模具或其他相关涂布技术而施用至Cu箔基材(RCC-resin coated Cu)。
上述高分子基质复合物、预浸物以及经过树脂涂布的铜箔(RCC)可被用于制造层合物，例如用于通过批次或连续方法制造印刷电路板的层合物。
请参阅图1。图1为本发明实施例所提供的层合物的剖面示意图。如图1所示，本发明实施例所提供的层合物L包括由前述高分子基质复合物所制造的强化层1，以及两层金属层2，例如铜箔。在本发明中，层合物L可以包括强化层1以及设置在强化层1上的至少一金属层2。需要注意的是，在本发明中，金属层2可以由非金属层取代。另外，层合物L可以进一步包括织物层(未显示)以允许高分子基质复合物中的聚合物树脂含浸入其中。
在本发明的另一个实施例中，层合物L可以由单一或多层的强化层1来形成，以形成非包覆(unclad)层合物。
在用以制造本发明实施例所提供的层合物的一个例示连续方法中，以铜(外层2)、预浸物(用以型成强化层1)以及薄织物片的形式的连续片材被连续地退绕至一系列的驱动辊上以形成织物的层叠网(layered web)，其邻近于预浸物片以及邻近于铜箔片，使得预浸物片位于铜箔片以及织物片之间。该层叠网接着受到热及压力的处理一段时间，该段时间足以导致预浸物中的树脂迁移至织物材料中，并完全固化树脂。在所得的层合物中，树脂迁移至织物中导致树脂层的厚度(铜箔材料与织物片材料之间的距离)降低并接近零，由于如上所述的层体的组合由三层的网状转变成单一层合片。在本方法的另一个实施方式中，单一预浸物树脂片可以被施用至织物材料层的一侧，而此组合再被包夹于两层铜层之间。在此之后，热及/或压力被施加至该迭层，以使得树脂材料流动并完全含浸织物层，并且导致两层铜箔都黏附至该中央的层合物上。
在本发明的另一个实施方式中，经高分子基质复合物涂布的铜片可以在层合物制造的同时被制造。具体而言，通过将高分子基质复合物的薄涂层施用至两片不同的连续移动铜片、自铜片移除任何过量的高分子基质复合物以控制厚度，并接着在热及/或压力条件下部分地固化树脂，可以形成经b阶段树脂涂覆铜的片材。经b阶段树脂涂覆铜的片材可以接着直接用于层合物的制造方法中。
在本发明的另一个实施例中，织物材料，无论是具有或不具有前处理的织物材料，可以被连续地进给至含有本发明所提供的高分子基质复合物的浴中，使得织物材料是以高分子基质复合物含浸。高分子基质复合物可以在方法中此阶段被选择性地部分固化。接着，一或二层铜箔层可以被与经高分子基质复合物含浸的织物片的第一及/或第二平面表面相互关联以形成网，在此之后，热及/或压力被施加于网上以完全固化高分子基质复合物。
本发明进一步提供借由使用上述层合物以及预浸物所形成的印刷电路板。参考图2，其显示本发明实施例所提供的印刷电路板的剖面示意图。图2所示的印刷电路板B包括层合物L作为核心层、两层包夹层合物L的外层4，以及设置在层合物L以及两层外层4之间的两层接着片3。
作为核心层的层合物L可以是上述包括强化层1以及至少一金属层2(或是非金属层)的层合物L。接着层3可以通过上述预浸物而形成。换句话说，预浸物可以由包含具有自1.5至4.8的介电常数以及在10GHz下0.003的损耗因子的非织造强化材料的高分子基质复合物所制造。
实施例的有益效果
本发明的其中一有益效果在于，本发明所提供的高分子基质复合物以及使用高分子基质复合物的产品，其能通过“具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子的非织造强化材料”的技术方案，以消除传输延迟的现象。
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 (12)

1.一种高分子基质复合物，其特征在于，所述高分子基质复合物包括：
一聚合物树脂；以及
一非织造强化材料，其具有自1.5至4.8的介电常数以及在10GHz下低于0.003的耗损因子。
2.根据权利要求1所述的高分子基质复合物，其特征在于，所述高分子基质复合物进一步包含至少一织造强化材料、一微米尺寸填料、一纳米尺寸填料、一有机短纤纤维、一无机短纤纤维以及一耐燃剂。
3.根据权利要求2所述的高分子基质复合物，其特征在于，所述耐燃剂是一含卤素的耐燃剂。
4.根据权利要求1所述的高分子基质复合物，其特征在于，所述非织造强化材料是经过一表面增强处理的非织造强化材料。
5.根据权利要求1所述的高分子基质复合物，其特征在于，所述非织造强化材料是聚四氟乙烯。
6.根据权利要求1所述的高分子基质复合物，其特征在于，所述非织造强化材料包含一液晶聚合物。
7.根据权利要求1所述的高分子基质复合物，其特征在于，所述非织造强化材料为石英。
8.根据权利要求1所述的高分子基质复合物，其特征在于，所述非织造强化材料是玻璃。
9.一种预浸物，其特征在于，所述预浸物包括：一树脂部分，所述树脂部分经部分固化且含浸有一非织造强化材料，所述非织造强化材料具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子。
10.一种印刷电路板，其特征在于，所述印刷电路板包括：
至少两层外层；以及
一核心层，其包夹于至少两层所述外层之间；
其中所述核心层包括一层合物，所述层合物包含至少一强化层，至少一所述强化层是由如权利要求1所述的高分子基质复合物所形成。
11.根据权利要求10所述的印刷电路板，其特征在于，所述印刷电路板进一步包含设置在至少两层所述外层与所述核心层之间的一接着片，其中，所述接着片是由一预浸物所形成，所述预浸物包括部分固化并含浸有一非织造强化材料的一树脂部分，所述非织造强化材料具有自1.5至4.8的介电常数以及在10GHz下低于0.003的损耗因子。
12.根据权利要求10所述的印刷电路板，其特征在于，所述层合物进一步包含设置在所述强化层上的至少一金属层。
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