CN114919253B - 一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法 - Google Patents

一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法 Download PDF

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CN114919253B
CN114919253B CN202210606414.3A CN202210606414A CN114919253B CN 114919253 B CN114919253 B CN 114919253B CN 202210606414 A CN202210606414 A CN 202210606414A CN 114919253 B CN114919253 B CN 114919253B
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polytetrafluoroethylene
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CN114919253A (zh
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王洋
徐莎
张黄平
钱云贵
胡新利
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Zhongshan Allstar Electronic Materials Co ltd
Huawei Device Co Ltd
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Abstract

本发明公开了一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法。所述含增粘层的聚四氟乙烯柔性覆铜板的结构，从上到下依次包括上铜箔层、上可溶性聚四氟乙烯层、上增粘层、基层、下增粘层、下可溶性聚四氟乙烯层和下铜箔层；所述增粘层包括增粘层胶水；所述增粘层胶水包括1,3‑双(4‑氨基苯氧基)苯、2,2‑双(3‑氨基‑4‑羟基苯基)六氟丙烷和4,4'‑氧双邻苯二甲酸酐反应合成的聚合物。本发明制备的含增粘层的聚四氟乙烯柔性覆铜板的力学性能得到有效提高，稳定性较好，同时还保证了较高的电学性能，具有良好的应用前景。

Description

一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法
技术领域
本发明涉及柔性覆铜板制造技术领域，特别是涉及一种含增粘层的聚四氟乙烯柔性覆铜板及其制备方法。
背景技术
随着全球5G技术不断进步，越来越多的电子产品朝着高频高速方向发展，而为了满足电子产品中线路板高传播速度，低信号损失的功能要求，传统的FR-4等材料已不能适用。
聚四氟乙烯具有极小的介电常数(10GHz-Dk值2.1)与介电损耗(10GHz-Df值0.002)，极低的吸水率(＜0.1％)，是制备高频高速基板材料的最佳选择，备受相关科研工作者的青睐。但由于聚四氟乙烯本身惰性的分子结构，F-C链分子间作用力小，造成它一方面力学性能较弱，加工困难，另一方面也很难与其他高分子材料(如聚酰亚胺膜)粘附，基板材料剥离强度低，下游PCB(印制电路板)厂在线路板制备过程中极易出现爆板等问题。使得聚四氟乙烯在线路板领域中的使用困难重重，难以发挥优良的介电性能。
综上所述，亟需研发一种机械性能好、剥离强度高，同时能够保证介电性能的新型柔性覆铜板，以解决现有技术中存在的问题，满足实际生产的需求。
发明内容
基于此，有必要提供一种新型含增粘层的聚四氟乙烯柔性覆铜板，以克服现有技术的不足。
本发明的一个目的在于，提供一种含增粘层的聚四氟乙烯柔性覆铜板，所述含增粘层的聚四氟乙烯柔性覆铜板的结构，从上到下依次包括上铜箔层、上可溶性聚四氟乙烯层、上增粘层、基层、下增粘层、下可溶性聚四氟乙烯层和下铜箔层；
其中，
所述基层与上可溶性聚四氟乙烯层之间通过上增粘层相粘结；
所述基层与下可溶性聚四氟乙烯层之间通过下增粘层相粘结；
所述增粘层包括增粘层胶水；
所述增粘层胶水包括1,3-双(4-氨基苯氧基)苯、2,2-双(3-氨基-4-羟基苯基)六氟丙烷和4,4'-氧双邻苯二甲酸酐反应合成的聚合物。
进一步地，所述基层为改性聚酰亚胺膜(MPI)。
进一步地，所述基层的表面张力不低于58dyn。
进一步地，所述基层的10GHz介电常数≤3.5。
进一步地，所述基层的10GHz介电损耗≤0.004。
进一步地，所述基层的吸水率≤1.0。
进一步地，所述聚合物的粘度为30000-40000cp。
进一步地，所述上增粘层和下增粘层的厚度为5-15μm，所述上可溶性聚四氟乙烯层和下可溶性聚四氟乙烯层的厚度为15-30μm，所述基层的厚度为25-40μm，所述上铜箔层和下铜箔层的厚度为12-18μm。
本发明的另一个目的在于，提供上述含增粘层的聚四氟乙烯柔性覆铜板的制备方法，包括如下步骤：
(1)制备增粘层胶水
S1.将1,3-双(4-氨基苯氧基)苯溶解于有机溶剂中，得到预聚物；
S2.将4,4'-氧双邻苯二甲酸酐和2,2-双(3-氨基-4-羟基苯基)六氟丙烷加入所述预聚物中，反应后，加入有机溶剂调节粘度到便于涂布的30000-40000cp，得到增粘层胶水；
(2)涂布增粘层
将所述增粘层胶水涂布于基层两面，烘干得到复合膜A；
(3)制备可溶性聚四氟乙烯悬浮液
将可溶性聚四氟乙烯粉料、分散剂、无机填料、所述增粘层胶水和有机溶剂加入容器中，搅拌均匀得到可溶性聚四氟乙烯悬浮液；
(4)涂布可溶性聚四氟乙烯层
将所述可溶性聚四氟乙烯悬浮液涂布于所述复合膜A两面，烘干得到复合膜B；
(5)复合膜烧结
将所述复合膜B高温烧结，得到介质层；
(6)压合铜箔
将铜箔置于所述介质层两面，压合后，得到所述含增粘层的聚四氟乙烯柔性覆铜板。
进一步地，步骤(3)中，所述分散剂选自三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、聚丙烯酰胺、脂肪酸聚乙二醇酯中的一种或多种。
进一步地，步骤(3)中，所述无机填料选自陶瓷粉、硅微粉、二硫化钼中的一种或多种。
进一步地，步骤(3)中，所述有机溶剂选自环己酮、N-甲基吡咯烷、二甲基乙酰胺中的一种或多种。
进一步地，步骤(5)中，所述高温烧结的温度为320-380℃，时间为15-30min。
进一步地，步骤(6)中，所述铜箔的粗糙度为0.6-1.5μm。
进一步地，步骤(6)中，所述铜箔选自电解铜箔和压延铜箔中的一种，优选为压延铜箔。
进一步地，步骤(6)中，所述压合的温度为320-380℃，压合压力为30-60bar。
本发明具有以下有益效果：
1.增粘层聚合物一方面具有与基层MPI相似的醚基与亚胺环结构，另一方面又具有羟基与含氟侧链官能团，可以有效起到粘结可熔性聚四氟乙烯层与MPI基材的作用，同时，增粘层自身分子间内聚力较大，而且耐高温性能良好，使得介质层满足柔性覆铜板应用的力学性能和剥离强度。
2.在介质层高温烧结阶段，增粘层界面与可熔性聚四氟乙烯层界面互相穿插熔融，同时增粘层小分子物质脱水缩聚形成大分子聚合物，增加了界面上可熔性聚四氟乙烯层在增粘层上的物理铆合点，进一步提高了界面剥离强度和机械强度。
3.本发明采用含氟二酐合成增粘层聚合物，降低了增粘层的吸水率和介电损耗，制备出的柔性覆铜板具有极好的耐离子迁移率和介电性能。
附图说明
图1为本发明实施例1制备的含增粘层的聚四氟乙烯柔性覆铜板的结构示意图；
其中，1-上铜箔层；2-上可溶性聚四氟乙烯层；3-上增粘层；4-基层；5-下增粘层；6-下可溶性聚四氟乙烯层；7-下铜箔层。
具体实施方式
为了更清楚地说明本发明的技术方案，列举如下实施例。实施例中所出现的原料、反应和后处理手段，除非特别声明，均为市面上常见原料，以及本领域技术人员所熟知的技术手段。
本发明中的词语“优选的”、“优选地”、“更优选的”等是指，在某些情况下可提供某些有益效果的本发明实施方案。然而，在相同的情况下或其他情况下，其他实施方案也可能是优选的。此外，对一个或多个优选实施方案的表述并不暗示其他实施方案不可用，也并非旨在将其他实施方案排除在本发明的范围之外。
应当理解，除了在任何操作实例中，或者以其他方式指出的情况下，表示例如说明书和权利要求中使用的成分的量的所有数字应被理解为在所有情况下被术语“约”修饰。因此，除非相反指出，否则在以下说明书和所附权利要求中阐述的数值参数是根据本发明所要获得的期望性能而变化的近似值。
本发明中所述的“上、下”的含义指的是阅读者正对附图时，阅读者的上方即为上，阅读者的下方即为下，而非对本发明的装置机构的特定限定。
当部件、元件或层被称为“位于”、“结合至”、“连接至”或“联接至”另一元件或层时，其可直接位于、结合至、连接至或联接至该另一部件、元件或层，或可存在中间元件或中间层。相反，当元件被称为“直接位于”、“直接结合至”、“直接连接至”或“直接联接至”另一元件或层时，可能不存在中间元件或中间层。其他用于描述元件之间的关系的词语应当以类似的方式来进行解释(例如，“在......之间”与“直接在......之间”、“邻近”与“直接邻近”等)。本文所用术语“和/或”包括相关联的列出项中的一个或多个的任何和所有组合。
本发明所指的份数，均为质量份数。
本发明对比例中的MPI膜牌号为株洲时代华鑫LK型MPI，表面张力为62dyn。
本发明实施例中的可溶性聚四氟乙烯膜牌号为华夏神州DS705，介电常数2.1，介电损耗0.0005，抗张强度35Mpa，吸水率0.01％，熔点310℃。
本发明实施例中的分散剂为三乙基己基磷酸。
本发明实施例中的无机填料为二硫化钼。
本发明实施例中的双钢带压合设备型号为E166-42“Alice”。
本发明实施例中的铜箔为高频电解铜，粗糙度(Rz值)为1.2μm。
实施例1
一种含增粘层的聚四氟乙烯柔性覆铜板，所述含增粘层的聚四氟乙烯柔性覆铜板的结构，从上到下依次包括上铜箔层(12μm)、上可溶性聚四氟乙烯层(20μm)、上增粘层(10μm)、基层(40μm)、下增粘层(10μm)、下可溶性聚四氟乙烯层(20μm)和下铜箔层(12μm)；所述含增粘层的聚四氟乙烯柔性覆铜板的整体厚度为124μm。
其中，
所述基层与上可溶性聚四氟乙烯层之间通过上增粘层相粘结；
所述基层与下可溶性聚四氟乙烯层之间通过下增粘层相粘结；
所述增粘层包括增粘层胶水；
所述基层为MPI膜；
上述含增粘层的聚四氟乙烯柔性覆铜板的制备方法包括如下步骤：
(1)制备增粘层胶水
S1.将50份1,3-双(4-氨基苯氧基)苯溶解于N-甲基吡咯烷酮中，得到预聚物；
S2.将48份4,4'-氧双邻苯二甲酸酐和2份2,2-双(3-氨基-4-羟基苯基)六氟丙烷加入所述预聚物中，30℃下反应8h，然后加入N-甲基吡咯烷酮调节聚合物粘度为30000cp，得到增粘层胶水；
(2)涂布增粘层
将所述增粘层胶水涂布于MPI膜两面，150℃烘干，得到复合膜A，厚度为60μm；
(3)制备可溶性聚四氟乙烯悬浮液
将45份可溶性聚四氟乙烯粉料、4.5份分散剂、4.5份无机填料、6份所述增粘层胶水和46份N-甲基吡咯烷酮加入容器中，搅拌均匀得到可溶性聚四氟乙烯悬浮液；
(4)涂布可溶性聚四氟乙烯层
将所述可溶性聚四氟乙烯悬浮液涂布于所述复合膜A两面，150℃烘干，得到复合膜B，厚度为100μm；
(5)复合膜烧结
将所述复合膜B于加热炉中320℃高温烧结30min，得到介质层；
(6)压合铜箔
将铜箔置于所述介质层两面，使用双钢带压合设备压合后(压合压力40bar，温度350℃，线速1.5m/min)，得到所述含增粘层的聚四氟乙烯柔性覆铜板，厚度为124μm。
图1为本发明的含增粘层的聚四氟乙烯柔性覆铜板的结构示意图；
其中，1-上铜箔层；2-上可溶性聚四氟乙烯层；3-上增粘层；4-基层；5-下增粘层；6-下可溶性聚四氟乙烯层；7-下铜箔层。
实施例2
一种含增粘层的聚四氟乙烯柔性覆铜板，所述含增粘层的聚四氟乙烯柔性覆铜板的结构，从上到下依次包括上铜箔层(12μm)、上可溶性聚四氟乙烯层(15μm)、上增粘层(15μm)、基层(40μm)、下增粘层(15μm)、下可溶性聚四氟乙烯层(15μm)和下铜箔层(12μm)；所述含增粘层的聚四氟乙烯柔性覆铜板的整体厚度为124μm。
其中，
所述基层与上可溶性聚四氟乙烯层之间通过上增粘层相粘结；
所述基层与下可溶性聚四氟乙烯层之间通过下增粘层相粘结；
所述增粘层包括增粘层胶水；
所述基层为MPI膜；
上述含增粘层的聚四氟乙烯柔性覆铜板的制备方法包括如下步骤：
(1)制备增粘层胶水
S1.将50份1,3-双(4-氨基苯氧基)苯溶解于N-甲基吡咯烷酮中，得到预聚物；
S2.将48份4,4'-氧双邻苯二甲酸酐和2份2,2-双(3-氨基-4-羟基苯基)六氟丙烷加入所述预聚物中，35℃下反应8h，然后加入N-甲基吡咯烷酮调节聚合物粘度为40000cp，得到增粘层胶水；
(2)涂布增粘层
将所述增粘层胶水涂布于MPI膜两面，170℃烘干，得到复合膜A，厚度为70μm；
(3)制备可溶性聚四氟乙烯悬浮液
将45份可溶性聚四氟乙烯粉料、4.5份分散剂、4.5份无机填料、6份所述增粘层胶水和46份N-甲基吡咯烷酮加入容器中，搅拌均匀得到可溶性聚四氟乙烯悬浮液；
(4)涂布可溶性聚四氟乙烯层
将所述可溶性聚四氟乙烯悬浮液涂布于所述复合膜A两面，160℃烘干，得到复合膜B，厚度为100μm；
(5)复合膜烧结
将所述复合膜B于加热炉中380℃高温烧结15min，得到介质层；
(6)压合铜箔
将铜箔置于所述介质层两面，使用双钢带压合设备压合后(压合压力50bar，温度370℃，线速2.3m/min)，得到所述含增粘层的聚四氟乙烯柔性覆铜板，厚度为124μm。
对比例1
一种氟系柔性覆铜板，本对比例与实施例1的区别在于：本对比例不含上增粘层和下增粘层，其结构包括：上铜箔层(12μm)、上可溶性聚四氟乙烯层(30μm)、基层(40μm)、下可溶性聚四氟乙烯层(30μm)、下铜箔层(12μm)；
其中，所述上可溶性聚四氟乙烯层和下可溶性聚四氟乙烯层的成分为：45份可溶性聚四氟乙烯粉料、4.5份分散剂、4.5份无机填料和46份N-甲基吡咯烷酮；所述MPI膜的厚度为40μm；所述上可溶性聚四氟乙烯层和下可溶性聚四氟乙烯层的厚度为30μm；所述氟系柔性覆铜板的整体厚度为124μm；其他结构和制备方法与实施例1相同。
对比例2
一种氟系柔性覆铜板，本对比例与实施例1的区别在于：本对比例中的增粘层胶水为：将质量比5：10：15：15的4-氨基苯甲酸(4-氨基苯基)酯、1,3-双(3-氨基苯氧基)苯、对-亚苯基-双苯偏三酸酯二酐和双酚A型二醚二酐溶于N-甲基吡咯烷酮中，氮气氛围下40℃反应10h后得到所述增粘层胶水，其他结构和制备方法与实施例1相同。
测试例
对实施例1-2和对比例1-2制备的柔性覆铜板进行性能测试。
测试方法：
根据IPC-TM-650、JIS C6471、SPDR规定的测试方法进行吸水率、介电常数(Dk)、介电损耗(Df)，抗张强度、杨氏模量、剥离强度、尺寸稳定性、耐锡焊性能等性能测试。
测试结果如表1所示。
表1柔性覆铜板性能结果
根据表1可以看出，对比例1制备的氟系柔性覆铜板由于不含增粘层，其力学性能和剥离强度均未得到改善，吸水率和耐热性明显比本发明实施例差，存在较多缺陷；对比例2制备的氟系柔性覆铜板增加了增粘层，力学性能、剥离强度和耐热性得到改善，由于增粘层的吸水率和介电损耗比较大，氟系柔性覆铜板介质层整体的吸水率和介电损耗比本发明实施例差；本发明实施例制备的含增粘层的聚四氟乙烯柔性覆铜板在对比例2的基础上进一步有效改善了剥离强度和吸水率，稳定性更好，同时还保证了较低的介电损耗，具有良好的应用前景。
对于本领域技术人员而言，显然本发明不限于上述示范性实施例的细节，而且在不背离本发明的精神或基本特征的情况下，能够以其他的具体形式实现本发明。因此，无论从哪一点来看，均应将实施例看作是示范性的，而且是非限制性的，本发明的范围由所附权利要求而不是上述说明限定，因此旨在将落在权利要求的等同要件的含义和范围内的所有变化囊括在本发明内。
此外，应当理解，虽然本说明书按照实施方式加以描述，但并非每个实施方式仅包含一个独立的技术方案，说明书的这种叙述方式仅仅是为清楚起见，本领域技术人员应当将说明书作为一个整体，各实施例中的技术方案也可以经适当组合，形成本领域技术人员可以理解的其他实施方式。

Claims (7)

1.一种含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，所述含增粘层的聚四氟乙烯柔性覆铜板的结构，从上到下依次包括上铜箔层、上可溶性聚四氟乙烯层、上增粘层、基层、下增粘层、下可溶性聚四氟乙烯层和下铜箔层；
其中，
所述基层与上可溶性聚四氟乙烯层之间通过上增粘层相粘结；
所述基层与下可溶性聚四氟乙烯层之间通过下增粘层相粘结；
所述基层为改性聚酰亚胺膜；
所述增粘层包括增粘层胶水；
所述增粘层胶水包括1,3-双(4-氨基苯氧基)苯、2,2-双(3-氨基-4-羟基苯基)六氟丙烷和4,4'-氧双邻苯二甲酸酐反应合成的聚合物；
所述聚合物的粘度为30000-40000 cp；
包括如下步骤：
（1）制备增粘层胶水
S1. 将1,3-双(4-氨基苯氧基)苯溶解于有机溶剂中，得到预聚物；
S2. 将4,4'-氧双邻苯二甲酸酐和2,2-双(3-氨基-4-羟基苯基)六氟丙烷加入所述预聚物中，反应后，加入有机溶剂，得到增粘层胶水；
（2）涂布增粘层
将所述增粘层胶水涂布于基层两面，烘干得到复合膜A；
（3）制备可溶性聚四氟乙烯悬浮液
将可溶性聚四氟乙烯粉料、分散剂、无机填料、所述增粘层胶水和有机溶剂加入容器中，搅拌均匀得到可溶性聚四氟乙烯悬浮液；
（4）涂布可溶性聚四氟乙烯层
将所述可溶性聚四氟乙烯悬浮液涂布于所述复合膜A两面，烘干得到复合膜B；
（5）复合膜烧结
将所述复合膜B高温烧结，得到介质层；
（6）压合铜箔
将铜箔置于所述介质层两面，压合后，得到所述含增粘层的聚四氟乙烯柔性覆铜板。
2.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，所述基层的表面张力不低于58 dyn。
3.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，步骤（3）中，所述分散剂选自三乙基己基磷酸、十二烷基硫酸钠、甲基戊醇、聚丙烯酰胺、脂肪酸聚乙二醇酯中的一种或多种。
4.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，步骤（3）中，所述无机填料选自陶瓷粉、硅微粉、二硫化钼中的一种或多种。
5.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，步骤（5）中，所述高温烧结的温度为320-380℃，时间为15-30 min。
6.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，步骤（6）中，所述铜箔的粗糙度为0.6-1.5 μm。
7.根据权利要求1所述含增粘层的聚四氟乙烯柔性覆铜板，其特征在于，步骤（6）中，所述压合的温度为320-380℃，压合压力为30-60 bar。
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