CN107234851A - 高频高速覆铜板制作方法及其覆铜板 - Google Patents

高频高速覆铜板制作方法及其覆铜板 Download PDF

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CN107234851A
CN107234851A CN201710485086.5A CN201710485086A CN107234851A CN 107234851 A CN107234851 A CN 107234851A CN 201710485086 A CN201710485086 A CN 201710485086A CN 107234851 A CN107234851 A CN 107234851A
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李洪彬
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Chongqing Dekai Industry Ltd By Share Ltd
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Abstract

本发明提供了一种高频高速覆铜板制作方法，将低分子量聚苯醚与双酚A型氰酸酯树脂进行共混性改，制备得到改良后的PPO/CE树脂；将改良后的PPO/CE树脂与填料、阻燃剂等按照一定比例加工混合而成，配制成生产频率高频高速覆铜板专用的胶水；再对增强材料进行预处理；然后将预处理后的NE玻璃纤维布与PPO/CE树脂在含浸机中经过预浸、含浸、排气、烘干等单元操作后制备成半固化片；制备好的半固化片交错堆叠，将叠制好的半固化片与一种高频超低轮廓度电解铜箔（VLP）组装成本后，在热机中经过高温、高压压制成型。这种方法生产出来的高频高速覆铜板在降低介电常数和介质损耗因子的条件下，也能满足覆铜板的其他性能要求，以能够适用于高频高速印制线路板的制作。

Description

高频高速覆铜板制作方法及其覆铜板
技术领域
本发明涉及覆铜板制备技术领域，具体涉及高频高速覆铜板制作方法及其覆铜板。
背景技术
在2017年3月发布的我国“十三五”信息产业发展指南中个，提出“加快推进5G研发，突破5G核心关键技术，支持标准研发和技术验证，积极推动5G国际标准研制，启动5G商用服务。使我国成为5G技术、标准、产业及应用的领先国家之一”。随着电子信息产业的高速化、高频化以及人们环保意识的调高，现有的覆铜板由于介电常数高、介电损耗大、耐高温性能差、尺寸稳定性不足等缺点已经无法满足在高频条件下使用。
发明内容
针对现有技术中的缺陷，本发明提供一种高频高速覆铜板制作方法及其覆铜板，介电常数小、介电损耗小，能够适用于高频高速印制线路板的制作。
本发明提供的一种高频高速覆铜板制作方法，包括以下步骤：
S1、改良树脂的制备：将低分子量聚苯醚PPO630与双酚A型氰酸酯树脂CEO1PO进行共混性改，制备得到PPO/CE树脂；
S2、专用胶水的配制：改良后的PPO/CE树脂与2-乙基-3-甲基咪唑、过氧化二异丙苯、4,4-二氨基二苯砜、二甲苯和阻燃剂按照比例加工混合而成，配制成生产高频高速覆铜板的专用胶水；
S3、增强材料预处理：选取NE玻璃纤维布作为增强材料，并在40℃下烧30min，然后自然冷却至室温；再将加热处理过的NE玻璃纤维布浸在处理液中10-15min，自然风干30-45min，然后将其放置在100℃的电热鼓风箱中烘干2H；
S4、半固化片的制备：将处理后的NE玻璃纤维布与PPO/CE树脂在含浸机中经过预浸、含浸、排气、烘干等单元操作后制备成半固化片；
S5、热压成型：制备好的半固化片经叠制、组合后送入热压机，在高温高压的条件下压制成型。
进一步的，S1中共混改性的具体方法为：
S11、将低分子量聚苯醚、双酚A型氰酸酯树脂和二甲苯放入容器中，在100℃下搅拌至溶液呈透明状；
S12、停止加热，将溶液降温至60℃，制备得到PPO/CE树脂。
进一步的，S2中专用胶水的配制具体方法为：
分别加入过氧化二异丙苯、2-乙基-3-甲基咪唑、4,4-二氨基二苯砜和阻燃剂到改良后的PPO/CE树脂中，在130℃下回流加热搅拌反应2H，然后冷却至室温。
进一步的，在S3中，玻璃布处理液为将硅烷偶联剂配成1%的水溶液，然后用冰醋酸调至PH=3~4，常温搅拌反应30min。
进一步的，其由树脂体系、NE玻璃纤维布和铜箔制备而成，树脂体系由以下重量百分含量的组分组成：
低分子量聚苯醚（PPO630） 12%-34%
双酚A型氰酸酯树脂（CEO1PO） 5%-16%
2-乙基-3-甲基咪唑 0.5%-2%
过氧化二异丙苯 2%-5%
4,4-二氨基二苯砜（DDS） 7%-24%
二甲苯 30%-53%
阻燃剂 4%-20%。
进一步的，阻燃剂由以下重量百分含量的组分组成：
溴化环氧树脂 10%-30%
硼酸铝晶须 5%-10%
氢氧化铝粉末 10%-30%
丙酮 25%-50%。
由上述技术方案可知，本发明的有益效果：
本发明提供了一种高频高速覆铜板制作方法，将低分子量聚苯醚与双酚A型氰酸酯树脂进行共混性改，制备得到改良后的PPO/CE树脂；然后将改良后的PPO/CE树脂与2-乙基-3-甲基咪唑、过氧化二异丙苯、4,4-二氨基二苯砜、二甲苯和阻燃剂按照一定比例加工混合而成，配制成生产高频高速覆铜板的专用胶水；再对增强材料NE型低介电常数玻璃纤维布进行预处理；然后将预处理后的NE玻璃纤维布与PPO/CE树脂在含浸机中经过预浸、含浸、排气、烘干等单元操作后制备成半固化片；制备好的半固化片以特定张数交错堆叠，然后将叠制好的半固化片与一种高频超低轮廓度电解铜箔（VLP）组装成本后，在热机中经过高温、高压压制成型。这种方法生产出来的高频高速覆铜板在降低介电常数和介质损耗因子的条件下，也能满足覆铜板的其他性能要求，以能够适用于高频高速印制线路板的制作。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍。在所有附图中，类似的元件或部分一般由类似的附图标记标识。附图中，各元件或部分并不一定按照实际的比例绘制。
图1为本发明高频高速覆铜板制作方法的流程示意图。
具体实施方式
下面将结合附图对本发明技术方案的实施例进行详细的描述。以下实施例仅用于更加清楚地说明本发明的技术方案，因此只作为示例，而不能以此来限制本发明的保护范围。
需要注意的是，除非另有说明，本申请使用的技术术语或者科学术语应当为本发明所属领域技术人员所理解的通常意义。
请参阅图1，本实施例提供的一种高频高速覆铜板制作方法，包括以下步骤：
将低分子量聚苯醚PPO630与双酚A型氰酸酯树脂CEO1PO进行共混性改得到PPO/CE树脂，并制备专用胶水：
（1）将低分子量聚苯醚、双酚A型氰酸酯树脂和二甲苯放入容器中，在100℃下搅拌至溶液呈透明状；
（2）停止加热，将溶液降温至60℃；
（3）分别加入过氧化二异丙苯、2-乙基-3-甲基咪唑、4,4-二氨基二苯砜和阻燃剂，在130℃下回流加热搅拌反应2H，然后冷却至室温。
增强材料预处理：选取NE玻璃纤维布作为增强材料，并在40℃下烧30min，然后自然冷却至室温；再将加热处理过的NE玻璃纤维布浸在处理液中10-15min，自然风干30-45min，然后将其放置在100℃的电热鼓风箱中烘干2H。玻璃布处理液为将硅烷偶联剂配成1%的水溶液，然后用冰醋酸调至PH=3~4，常温搅拌反应30min。
半固化片的制备：将处理后的NE玻璃纤维布与PPO/CE树脂在含浸机中经过预浸、含浸、排气、烘干等单元操作后制备成半固化片。
热压成型：制备好的半固化片经叠制、组合后送入热压机，在高温高压的条件下压制成型。
介电常数DK是电极间充以某种物质时的电容与同样构造的真空电容器的电容之比，通常表示某种材料储存电能能力的大小。通过印制板上电信号的电流方向通常是正负交替变化的，相当于对基板进行不断充电、放电的过程。在互换中，电容量会影响信号传输速度。而这种影响，在高速传送的装置中显得更为明显。当DK大时，表示储存电能能力大，电路中电信号传输速度就会变慢。当DK小时，表示储存电能能力小，充、放电过程就快，从而使传输速度加快。所以，在高频传输中，要求介电常数DK低。NE玻纤布的介电常数DK=4.4，低于常用的E型玻纤布DK=6.6，因此使用NE玻纤布可以降低材料的介电常数。
介质损耗因子Df，也叫介质损耗角正切，绝缘材料或电介质在交变电场中，由于介质电导和介质极化的滞后效应，使电介质内流过的电流向量和电压向量之间产生一定的相位差，即形成一定的相角，此相角的正切值即介质损耗因子Df,由介质电导和介质极化的滞后效应引起的能量损耗叫做介质损耗。Df越高，介质电导和介质极化滞后效应越明显，电能损耗或信号损失越多，是电介质损耗电能的能力，也是绝缘材料损失信号能力的表征物理量。
聚苯醚（PPO）树脂由于其本身优异的电气性能、机械性能、耐湿性能以及尺寸稳定性，在覆铜板制造领域有着极为广泛的应用。但聚苯醚树脂存在耐锡焊性差、耐卤代烃和芳香烃等溶剂性差等不足。因而需要对聚苯醚树脂进行改性使其能形成交联固化的热固性树脂，提高其综合性能。改性的途径可以分为以下几种。第一种是在聚苯醚分子结构中引入可交联的活性基团使之成为热固性聚合物；第二种是通过共混性或穿网络技术引入其他高性能热固性树脂，形成相容共混的热固性树脂体系。与传统的环氧覆铜板相比，环氧/氰酸酯体系具有较低的介电常数，且随着氰酸酯树脂含量的增加而减小，因为氰酸酯树脂本身具有极好的介电性能。此外，环氧/氰酸酯体系的吸水很小，氰酸酯取代了传统环氧活性氢固化剂，这也是其介电性能优良的一个重要原因。
覆铜板其由树脂体系、NE玻璃纤维布和铜箔制备而成，树脂体系由以下重量百分含量的组分组成：
低分子量聚苯醚（PPO630） 12%-34%
双酚A型氰酸酯树脂（CEO1PO） 5%-16%
2-乙基-3-甲基咪唑 0.5%-2%
过氧化二异丙苯 2%-5%
4,4-二氨基二苯砜 7%-24%
二甲苯 30%-53%
阻燃剂 4%-20%。
作为上述方案的进一步改进，阻燃剂由以下重量百分含量的组分组成：
溴化环氧树脂 10%-30%
硼酸铝晶须 5%-10%
氢氧化铝粉末 10%-30%
丙酮 25%-50%。
覆铜板的介电性能主要取决于树脂和增强材料，进行改性双马体系介电性 能测试，结果如下表：
由此可知，在阻燃剂的配比中，溴化环氧树脂含量为10％-30％，硼酸铝晶 须为5％-10％，氢氧化铝粉末为10％-30％时即能改善介电性能，又能满足阻燃要 求。
实施例1
将12%低分子量聚苯醚、10%双酚A型氰酸酯树脂和53%二甲苯放入容器中，在100℃下搅拌至溶液呈透明状；停止加热，将溶液降温至60℃；再分别加入5%过氧化二异丙苯、1%2-乙基-3-甲基咪唑、15%4,4-二氨基二苯砜、0.4%溴化环氧树脂、0.4%硼酸铝晶须、1.0%氢氧化铝粉末、2.2%丙酮，在130℃下回流加热搅拌反应2H，然后冷却至室温。测量其介电常数为3.2，满足要求。
实施例2
将20%低分子量聚苯醚、15%双酚A型氰酸酯树脂和二甲苯42%放入容器中，在100℃下搅拌至溶液呈透明状；停止加热，将溶液降温至60℃；再分别加入2%过氧化二异丙苯、0.5%2-乙基-3-甲基咪唑、12%4,4-二氨基二苯砜、1.2%溴化环氧树脂、1%硼酸铝晶须、2%氢氧化铝粉末、4.3%丙酮，在130℃下回流加热搅拌反应2H，然后冷却至室温。测量其介电常数为3.0，满足要求。
实施例3
将34%低分子量聚苯醚、10%双酚A型氰酸酯树脂和30%二甲苯放入容器中，在100℃下搅拌至溶液呈透明状；停止加热，将溶液降温至60℃；再分别加入4%过氧化二异丙苯、1.2%2-乙基-3-甲基咪唑、7%4,4-二氨基二苯砜、2%溴化环氧树脂、1%硼酸铝晶须、4.8%氢氧化铝粉末、6%丙酮，在130℃下回流加热搅拌反应2H，然后冷却至室温。测量其介电常数为3.3，满足要求。
最后应说明的是：以上各实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述各实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的范围，其均应涵盖在本发明的权利要求和说明书的范围当中。

Claims (6)

1.一种高频高速覆铜板制作方法，其特征在于：包括以下步骤：
S1、改良树脂的制备：将低分子量聚苯醚PPO630与双酚A型氰酸酯树脂CEO1PO进行共混性改，制备得到PPO/CE树脂；
S2、专用胶水的配制：改良后的PPO/CE树脂与2-乙基-3-甲基咪唑、过氧化二异丙苯、4,4-二氨基二苯砜、二甲苯和阻燃剂按照比例加工混合而成，配制成生产高频高速覆铜板的专用胶水；
S3、增强材料预处理：选取NE玻璃纤维布作为增强材料，并在40℃下烧30min，然后自然冷却至室温；再将加热处理过的NE玻璃纤维布浸在处理液中10-15min，自然风干30-45min，然后将其放置在100℃的电热鼓风箱中烘干2H；
S4、半固化片的制备：将处理后的NE玻璃纤维布与PPO/CE树脂在含浸机中经过预浸、含浸、排气、烘干等单元操作后制备成半固化片；
S5、热压成型：制备好的半固化片经叠制、组合后送入热压机，在高温高压的条件下压制成型。
2.根据权利要求1所述的高频高速覆铜板制作方法，其特征在于：所述S1中共混改性的具体方法为：
S11、将低分子量聚苯醚、双酚A型氰酸酯树脂和二甲苯放入容器中，在100℃下搅拌至溶液呈透明状；
S12、停止加热，将溶液降温至60℃，制备得到PPO/CE树脂。
3.根据权利要求2所述的高频高速覆铜板制作方法，其特征在于：所述S2中专用胶水的配制具体方法为：
分别加入过氧化二异丙苯、2-乙基-3-甲基咪唑、4,4-二氨基二苯砜和阻燃剂到改良后的PPO/CE树脂中，在130℃下回流加热搅拌反应2H，然后冷却至室温。
4.根据权利要求3所述的高频高速覆铜板制作方法，其特征在于：在S3中，玻璃布处理液为将硅烷偶联剂配成1%的水溶液，然后用冰醋酸调至PH=3~4，常温搅拌反应30min。
5.一种覆铜板，其特征在于：其由树脂体系、NE玻璃纤维布和铜箔制备而成，所述树脂体系由以下重量百分含量的组分组成：
低分子量聚苯醚（PPO630） 12%-34%
双酚A型氰酸酯树脂（CEO1PO） 5%-16%
2-乙基-3-甲基咪唑 0.5%-2%
过氧化二异丙苯 2%-5%
4,4-二氨基二苯砜（DDS） 7%-24%
二甲苯 30%-53%
阻燃剂 4%-20%。
6.根据权利要求5所述的覆铜板，其特征在于：所述阻燃剂由以下重量百分含量的组分组成：
溴化环氧树脂 10%-30%
硼酸铝晶须 5%-10%
氢氧化铝粉末 10%-30%
丙酮 25%-50%。
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