CN113637449A - 一种高频胶黏剂及用其制备的高频覆铜板用保护膜 - Google Patents
一种高频胶黏剂及用其制备的高频覆铜板用保护膜 Download PDFInfo
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Abstract
本发明公开一种高频胶黏剂及用其制备的高频覆铜板用保护膜。该高频胶黏剂，按重量份计，包括改性聚酰亚胺树脂55～78份、环氧改性氟树脂2～5份、聚四氟乙烯粉料10～20份、阻燃剂10～20份。本发明通过改性聚酰亚胺树脂、环氧改性氟树脂、聚四氟乙烯粉料、阻燃剂制备的高频胶黏剂满足低Dk和Df值，且具优异的耐老化、优异的耐化性等特性，能满足天线信号传输的高可靠性、低延时性；本发明通过在PI膜上涂布高频胶黏剂、覆合离型层制备高频覆铜板用保护膜，设备通用性强、工艺简单、良率高、成本低，能够实现量产化的MPI，比LCP材料在市场上更高的性价比。
Description
技术领域
本发明涉及覆铜板的制备技术领域，尤其涉及一种高频胶黏剂及用其制备的高频覆铜板用保护膜。
背景技术
FPC是以聚酰亚胺或聚酯薄膜为基材制成的一种具有高度可靠性，绝佳的可挠性印刷电路板，在智能手机、平板中均有广泛应用。随着5G信息时代的兴起，材料的革新推陈出新，5G的天线是本次变革的核心，天线材料尤为重要，为达到信号高速传输的高可靠性，天线材料需具备低Dk和Df值(Dk≤3.0，Df≤0.0005)。
现有FPC天线保护材料，是在PI上涂覆环氧胶黏剂，覆合离型纸熟化制成，能满足4G厘米波的需求，但无法满足5G传输10毫米波的要求。LCP(液晶聚合物)和MPI(改性聚酰亚胺)材料具有介电常数小、介电损耗低的优势，可用于5G天线材料。LCP材料技术门槛高、设备昂贵，工艺复杂，良率低，成本高；MPI材料具有制备简单、成本低的优势，但其具有较高的Dk值和吸水率以及较低的剥离强度，无法满足天线材料的需求。
发明内容
有鉴于此，有必要提供一种高频胶黏剂及用其制备的高频覆铜板用保护膜，用以解决现有技术中MPI材料Dk值和吸水率高、剥离强度低的技术问题。
本发明的第一方面提供一种高频胶黏剂，按重量份计，包括改性聚酰亚胺树脂55～78份、环氧改性氟树脂2～5份、聚四氟乙烯粉料10～20份、阻燃剂10～20份。
本发明的第二方面提供一种高频胶黏剂的制备方法，包括以下步骤：
将改性聚酰亚胺树脂、环氧改性氟树脂、聚四氟乙烯粉料和阻燃剂混合均匀得到高频胶黏剂。
本发明的第三方面提供一种高频覆铜板用保护膜，包括依次叠层设置的PI膜、高频胶黏剂层和离型层；高频胶黏剂层由本发明第一方面提供的高频胶黏剂形成。
本发明的第四方面提供一种高频覆铜板用保护膜的制备方法，包括以下步骤：
将本发明第一方面提供的高频胶黏剂涂覆在PI膜一侧，并在110～130℃烘烤2～5分钟去除溶剂，然后在70～80℃条件下覆合离型层，得到高频覆铜板用保护膜。
与现有技术相比，本发明的有益效果为：
本发明通过改性聚酰亚胺树脂、环氧改性氟树脂、聚四氟乙烯粉料、阻燃剂制备的高频胶黏剂满足低Dk和Df值，且具优异的耐老化、优异的耐化性等特性，能满足天线信号传输的高可靠性、低延时性；
本发明通过在PI膜上涂布高频胶黏剂、覆合离型层制备高频覆铜板用保护膜，设备通用性强、工艺简单、良率高、成本低，能够实现量产化的MPI，比LCP材料在市场上更高的性价比。
具体实施方式
为了使本发明的目的、技术方案及优点更加清楚明白，以下结合实施例，对本发明进行进一步详细说明。应当理解，此处所描述的具体实施例仅仅用以解释本发明，并不用于限定本发明。
本发明的第一方面提供一种高频胶黏剂，按重量份计，包括改性聚酰亚胺树脂55～78份、环氧改性氟树脂2～5份、聚四氟乙烯粉料10～20份、阻燃剂10～20份。
本发明的高频胶黏剂以改性聚酰亚胺树脂作为主体，加入环氧改性氟树脂能够提高附着力，加入聚四氟乙烯和阻燃剂，不仅进一步减小的Dk和Df值，还提高了阻燃性能。
本发明中，改性聚酰亚胺树脂通过将酸酐单体、二胺单体反应得到，且改性聚酰亚胺树脂的分子量为80～100万。在该分子量范围内，能使所得保护膜材料兼具良好的柔韧性和剥离力。
进一步地，酸酐单体为均苯四甲酸二酐(PMDA)、3,3',4,4'-二苯酮四酸二酐(4，4'-BTDA)、4,4'-氧双邻苯二甲酸酐(4，4'-ODPA)中的一种或几种。
进一步地，二胺单体包括普通二胺单体和含氟二胺单体；普通二胺单体为对苯二胺(PPDA)、P,P'-二氨基二苯醚(P，P'-ODA)中的一种或几种；含氟二胺单体为P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷(P，P'-BDAF)、2,2-双(4-氨基苯基)六氟丙烷(6FpDA)中的一种或几种。
进一步地，酸酐单体占单体总量的45％～55％，二胺单体占单体总量的45％～55％，含氟二胺单体占二胺单体总量的5％～10％。在该比例范围内，能使所得保护膜材料兼具良好的柔韧性和较低Dk和Df值。
更进一步地，酸酐单体占单体总量的50％，普通二胺单体占单体总量的46％，含氟二胺单体占单体总量的4％。
在本发明的一些具体实施方式中，改性聚酰亚胺树脂的合成步骤为：在15～20℃条件下，将酸酐单体溶解至有机溶剂中，分批次加入二胺单体，在15～20℃反应4～5h，得到改性聚酰亚胺树脂。具体地，二胺单体每次加入减一半，控制添加次数在4-5次。
进一步地，有机溶剂为二甲基乙酰胺、二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种。
进一步地，单体总量与有机溶剂的质量比为1：3～6。在本发明的一些具体实施方式中，单体总量与有机溶剂的质量比为1：4。
本发明中，环氧改性氟树脂为4-氟-4′,4″-二缩水甘油醚三苯基甲烷。
进一步地，环氧改性氟树脂与聚四氟乙烯的质量比为1：(2～4)。进一步为1:3。
本发明中，阻燃剂为次磷酸盐阻燃剂。在本发明的一些具体实施方式中，阻燃剂为次磷酸铝、次磷酸钙、次磷酸镁、次磷酸镧、次磷酸铈中的一种或几种。
本发明的第二方面提供一种高频胶黏剂的制备方法，包括以下步骤：
将改性聚酰亚胺树脂、环氧改性氟树脂、聚四氟乙烯粉料和阻燃剂混合均匀得到高频胶黏剂。
本发明的第三方面提供一种高频覆铜板用保护膜，包括依次叠层设置的PI膜、高频胶黏剂层和离型层；高频胶黏剂层由本发明第一方面提供的高频胶黏剂形成。
本发明中，PI膜为高频PI膜，厚度为5～50μm。在本发明的一些具体实施方式中，PI膜为杜邦高频EN系列PI膜，其Dk值为3.0，Df值为0.0003。
本发明中，高频胶黏剂层的厚度为10～35μm。
本发明中，离型层的厚度为20～200μm。
本发明的第四方面提供一种高频覆铜板用保护膜的制备方法，包括以下步骤：
将本发明第一方面提供的高频胶黏剂涂覆在PI膜一侧，并在110～130℃烘烤2～5分钟去除溶剂，然后在70～80℃条件下覆合离型层，得到高频覆铜板用保护膜。
实施例1
本实施例提供了一种高频胶黏剂，其通过以下步骤得到：
(1)在15～20℃条件下，将50kg均苯四甲酸二酐单体溶解至400kg二甲基乙酰胺中，分5次加入46kg对苯二胺单体和4kg P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷单体(二胺单体每次加入减一半)，在15～20℃反应4.5h，得到改性聚酰亚胺树脂；
(2)将70kg改性聚酰亚胺树脂、5kg环氧改性氟树脂、15kg聚四氟乙烯粉料和10kg次磷酸铝混合后经研磨、搅拌、分散得到高频胶黏剂。
本实施例还提供了一种高频覆铜板用保护膜，其通过以下步骤得到：
将上述高频胶黏剂涂覆在杜邦高频PI膜一侧，并在130℃烘烤5分钟去除溶剂，然后在80℃条件下覆合离型层，得到高频覆铜板用保护膜。其中，胶层厚度为25μm。
实施例2
(1)在15～20℃条件下，将45kg均苯四甲酸二酐单体溶解至400kg二甲基乙酰胺中，分5次加入50kg对苯二胺单体和5kg P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷单体(二胺单体每次加入减一半)，在15～20℃反应4h，得到改性聚酰亚胺树脂；
(2)将55kg改性聚酰亚胺树脂、5kg环氧改性氟树脂、20kg聚四氟乙烯粉料和20kg次磷酸铝混合后经研磨、搅拌、分散得到高频胶黏剂。
本实施例还提供了一种高频覆铜板用保护膜，其通过以下步骤得到：
将上述高频胶黏剂涂覆在杜邦高频PI膜一侧，并在110℃烘烤2分钟去除溶剂，然后在70℃条件下覆合离型层，得到高频覆铜板用保护膜。其中，胶层厚度为25μm。
实施例3
(1)在15～20℃条件下，将55kg均苯四甲酸二酐单体溶解至400kg二甲基乙酰胺中，分5次加入42kg对苯二胺单体和3kg P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷单体(二胺单体每次加入减一半)，在15～20℃反应5h，得到改性聚酰亚胺树脂；
(2)将78kg改性聚酰亚胺树脂、2kg环氧改性氟树脂、10kg聚四氟乙烯粉料和10kg次磷酸铝混合后经研磨、搅拌、分散得到高频胶黏剂。
本实施例还提供了一种高频覆铜板用保护膜，其通过以下步骤得到：
将上述高频胶黏剂涂覆在杜邦高频PI膜一侧，并在130℃烘烤5分钟去除溶剂，然后在80℃条件下覆合离型层，得到高频覆铜板用保护膜。其中，胶层厚度为25μm。
对比例1
与实施例1相比，区别仅在于，改性聚酰亚胺树脂的合成过程中，单体含量为：50kg均苯四甲酸二酐单体、48kg对苯二胺单体和2kg P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷单体。
对比例2
与实施例1相比，区别仅在于，改性聚酰亚胺树脂的合成过程中，单体含量为：50kg均苯四甲酸二酐单体、45kg对苯二胺单体和5kg P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷单体。
对比例3
与实施例1相比，区别仅在于，改性聚酰亚胺树脂的合成过程中，所得改性聚酰亚胺树脂的分子量为60万。
对比例4
与实施例1相比，区别仅在于，改性聚酰亚胺树脂的合成过程中，所得改性聚酰亚胺树脂的分子量为120万。
对比例5
与实施例1相比，区别仅在于，高频胶黏剂的制备过程中，原料含量为：70kg改性聚酰亚胺树脂、10kg环氧改性氟树脂、10kg聚四氟乙烯粉料和10kg次磷酸铝。
对比例6
与实施例1相比，区别仅在于，高频胶黏剂的制备过程中，原料含量为：70kg改性聚酰亚胺树脂、2kg环氧改性氟树脂、18kg聚四氟乙烯粉料和10kg次磷酸铝。
对上述实施例1和对比例1～6所得高频覆铜板用保护膜进行性能测试，结果见表1。
相关测试方法如下：
剥离强度：IPC-TM-650 2.4.9；
耐热性：IPC-TM-650 2.4.13；
吸水率：IPC-TM-650 2.6.2；
Dk和Df：IPC-TM-650 2.5.5.3。
表1
通过表1可以看出，本发明实施例1制备的高频覆铜板用保护膜具有良好的剥离强度、耐热性以及较低的吸水率、Dk、Df值。
以上所述，仅为本发明较佳的具体实施方式，但本发明的保护范围并不局限于此，任何熟悉本技术领域的技术人员在本发明揭露的技术范围内，可轻易想到的变化或替换，都应涵盖在本发明的保护范围之内。
Claims (10)
1.一种高频胶黏剂，其特征在于，按重量份计，包括改性聚酰亚胺树脂55～78份、环氧改性氟树脂2～5份、聚四氟乙烯粉料10～20份、阻燃剂10～20份。
2.根据权利要求1所述高频胶黏剂，其特征在于，所述改性聚酰亚胺树脂通过将酸酐单体、二胺单体反应得到，且所述改性聚酰亚胺树脂的分子量为80～100万。
3.根据权利要求2所述高频胶黏剂，其特征在于，所述酸酐单体为均苯四甲酸二酐、3,3',4,4'-二苯酮四酸二酐、4,4'-氧双邻苯二甲酸酐中的一种或几种；所述二胺单体包括普通二胺单体和含氟二胺单体；所述普通二胺单体为对苯二胺、P,P'-二氨基二苯醚中的一种或几种；所述含氟二胺单体为P,P-双[4-(4-氨基苯氧基苯基)]六氟丙烷、2,2-双(4-氨基苯基)六氟丙烷中的一种或几种。
4.根据权利要求3所述高频胶黏剂，其特征在于，所述酸酐单体占单体总量的45％～55％，所述二胺单体占单体总量的45％～55％，所述含氟二胺单体占所述二胺单体总量的5％～10％。
5.根据权利要求2所述高频胶黏剂，其特征在于，所述改性聚酰亚胺树脂的合成步骤为：在15～20℃条件下，将酸酐单体溶解至有机溶剂中，分批次加入二胺单体，在15～20℃反应4～5h，得到改性聚酰亚胺树脂。
6.根据权利要求5所述高频胶黏剂，其特征在于，有机溶剂为二甲基乙酰胺、二甲基甲酰胺、N-甲基吡咯烷酮中的一种或几种。
7.根据权利要求1所述高频胶黏剂，其特征在于，所述环氧改性氟树脂与聚四氟乙烯的质量比为1：(2～4)。
8.一种如权利要求1～7中任一项所述高频胶黏剂的制备方法，其特征在于，包括以下步骤：
将改性聚酰亚胺树脂、环氧改性氟树脂、聚四氟乙烯粉料和阻燃剂混合均匀得到高频胶黏剂。
9.一种高频覆铜板用保护膜，其特征在于，包括依次叠层设置的PI膜、高频胶黏剂层和离型层；所述高频胶黏剂层通过权利要求1～7中任一项所述高频胶黏剂形成。
10.一种高频覆铜板用保护膜的制备方法，其特征在于，包括以下步骤：
将权利要求1～7中任一项所述高频胶黏剂涂覆在PI膜一侧，并在110～130℃烘烤2～5分钟去除溶剂，然后在70～80℃条件下覆合离型层，得到高频覆铜板用保护膜。
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