CN113844129A - 一种无卤、低介电损耗、高耐热覆铜板的制备方法 - Google Patents

一种无卤、低介电损耗、高耐热覆铜板的制备方法 Download PDF

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CN113844129A
CN113844129A CN202111066750.5A CN202111066750A CN113844129A CN 113844129 A CN113844129 A CN 113844129A CN 202111066750 A CN202111066750 A CN 202111066750A CN 113844129 A CN113844129 A CN 113844129A
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resin
parts
copper
clad plate
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李凌云
刘政
杨永亮
郑宝林
栾好帅
姜晓亮
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明属于覆铜板生产技术领域，涉及一种无卤、低介电损耗、高耐热覆铜板的制备方法。本发明的树脂胶液中，在环氧树脂骨架中引入联苯基团，可以提高其耐热性，以及减少自由体积从而提高韧性和降低吸水性，制造出的PCB在高温无铅焊过程中产生的应力有所减少。BT改性PPO树脂既保留了BT树脂原本具有的优良的耐热性，很低的耐金属离子迁移性，并具有良好的尺寸稳定性，还大幅改善了其介电性能和机械加工性能。本发明制得的覆铜板板材的T288可达到120min不分层，Tg高达230℃，Df小于0.006，适应高频高速电路板的高度层设计，而且大大提高了封装效率和PCB板可靠性。

Description

一种无卤、低介电损耗、高耐热覆铜板的制备方法
技术领域
本发明属于覆铜板生产技术领域，尤其涉及一种无卤、低介电损耗、高耐热覆铜板的制备方法。
背景技术
虽然欧盟(WEEE)及RoHS指令对含溴类阻燃剂没有明确禁用，但这类含溴型覆铜板，燃烧或电器火灾时，会释放出大量有毒气体(溴化型)，发烟量大；在PCB作热风整平和元件焊接时，板材受高温(>200℃)影响，也会释放出微量的溴化氢；是否也会产生有毒气体，还在评估中。日本及欧洲的一些电子电器整机厂已将禁用范围扩展至全部含卤阻燃剂。无论是预测数据还是实际销售数据，都显示出无卤型覆铜板正处于快速增长期。
随着5G通讯技术的广泛普及，电子产品日新月异，需要更快的数据传输速度，也需要***操作频率更高，同时无铅焊接要求材料耐受更高的温度，这就对印制电路板提出了更高要求，原来在覆铜板上普遍应用的环氧酚醛树脂体系由于本身有很大的介电损耗，限制了它在高频高速领域的应用。国外很多先进国家纷纷开发出了各种高性能的树脂材料，如BT树脂，PPE，SMA，PI，PTFE等，以满足电子通讯技术的发展要求，这些树脂的合理应用，在覆铜板研发上具有重要意义。
发明内容
本发明针对上述现有技术存在的不足，提供一种无卤、低介电损耗、高耐热覆铜板的制备方法。
具体技术方案如下：
一种无卤、低介电损耗、高耐热覆铜板的制备方法，包括如下步骤：
(1)按重量份数计，将20-40份联苯型环氧树脂、60-90份BT改性PPO树脂，10-40份含磷阻燃剂，1-20份交联固化剂及固化促进剂、0.1-1份分散剂、40-100份溶剂，10-50份填充材料混合，乳化搅拌均匀；
(2)将低介电电子级玻璃纤维布浸渍在步骤(1)制得的树脂后，经过100-200℃的上胶机，制得半固化片；
(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，在100-250℃、70-150kgf/cm条件下热压150-300min，制得无卤、低介电损耗、高耐热覆铜板。
在上述技术方案的基础上，本发明还可以做如下改进：
步骤(1)中，所述联苯型树脂为以含联苯(biphenyl)结构酚醛树脂为主链的环氧树脂，此树脂中的芳香环占比高，在甲苯和丁酮中同样具有高流动性、优异的溶解性及低粘度，可以提前溶解于溶剂中配制成溶液。所述联苯型树脂结构为：
Figure BDA0003258730590000021
其中，BT改性PPO树脂为PPO树脂与BT树脂按照9：1的质量比共混得到，所述BT树脂为Arocy B—10与4,4′–二胺基二苯甲烷双马来酰亚胺共聚得到的的B-阶段预聚体,也提前溶解于溶剂中；
其中，所述含磷阻燃剂为磷腈化合物或间苯二酚双[二(2,6-二甲基苯基)磷酸酯中的至少一种，其中，磷腈化合物含磷量为13％wt，是以P、N交替双键排列为主链结构的一类无机化合物，以环状或线性结构存在，并在磷原子上接入苯氧基，苯氧基的引入使磷腈化合物成为无机化合物和有机化合物相结合的产物，是一种良好的无卤的环保型绿色阻燃剂。其结构式如下：
Figure BDA0003258730590000031
其中，所述间苯二酚双[二(2,6-二甲基苯基)磷酸酯为一种缩聚型磷酸酯阻燃剂，其中磷含量为10.5％wt。
其中，所述交联固化及固化促进剂为2-乙基辛酸锌、2-甲基4-乙基咪唑或硅烷偶联剂KH-560中的至少一种，为保证投料准确，微量添加的固化剂或固化促进剂可配成10％溶液添加。
其中，所述分散剂为BYK W-903型湿润分散剂，所述溶剂为甲苯、丙酮或丁酮、二甲苯中的一种或两种以上。
其中，所述填充材料为高纯超细球形纳米非晶态硅微粉和氢氧化铝中的一种或两种以上，硅微粉中SiO2含量达99.9％，粒径平均为3-5μm，最大粒径不超过20μm,最后添加。
优选的，步骤(2)中，半固化片胶化时间控制在80-100秒；
优选的，步骤(3)中，可根据不同厚度要求调整半固化片的数量，将板材与不锈钢板上下对应叠合后铺高耐热毛毡，送入真空压机，在100-250℃、70-150kgf/cm条件下热压180-240min，制得无卤、低介电损耗、高耐热的覆铜板。
与现有技术相比，本发明的有益效果是：
(1)本发明将低介电型的E-GLASS玻纤布浸渍特制树脂胶液，其树脂胶液中联苯型(biphenyl)环氧树脂在环氧树脂骨架中引入联苯基团，一方面可以提高其耐热性，一方面可以减少自由体积以提高韧性和降低吸水性。另外，在环氧树脂中联苯结构的存在，使交联官能团(环氧基)之间的分子量增大，它在热态时弹性模量有所降低，且具有高韧性的特点，使它制造出的PCB在高温无铅焊过程中产生的应力有所减少。
(2)BT改性PPO树脂既保留了BT树脂原本具有的优良的耐热性，很低的耐金属离子迁移性，并具有良好的尺寸稳定性，还大幅改善了其介电性能，降低了其介电损耗和介电常数，而且机械加工性能得到很大改善。
(3)本发明使用的含磷阻燃剂由于独特的自熄功能，具有较高的热分解温度和阻燃效果，可以达到UL-94VO级阻燃性能，阻燃性能大大优于传统阻燃体系。且发烟及有毒气体少，是一种环境友好型阻燃材料，能满足欧盟RollS指令及WEEE指令的要求。
(4)胶液中加入的球形硅，粒径小，分散性好，使PCB板具有较低的成型收缩率和很好的尺寸稳定性。而浸渍使用的玻纤布也是低介电型的E-glass玻纤布。本发明制得的覆铜板板材的T288可达到120min不分层，Tg高达225℃，Df小于0.006，适应高频高速电路板的高度层设计，而且大大提高了封装效率和PCB板可靠性。
具体实施方式
以下结合实例对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。
实施例1
(1)制备树脂胶液：按重量份数计，将22份联苯型环氧树脂、85份BT改性PPO树脂(Arocy B—10和4,4′–二胺基二苯甲烷双马来酰亚胺的B-阶段预聚体与PPO树脂以1：9的质量比共混)，20份含磷阻燃剂磷腈化合物(含磷量13％wt)，0.5份固化促进剂2-乙基辛酸锌，0.01份2-甲基4-乙基咪唑、0.4份分散剂BYK W-903、100份溶剂丁酮，80份填充材料高纯超细球形纳米非晶态硅微粉，20份氢氧化铝混合，乳化搅拌均匀；
(2)将低介电型的电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过170℃的上胶机，制得半固化片。
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在170-250℃、120kgf/cm2条件下热压180min，制得无卤低介电损耗、高Tg的覆铜板。
对比例1
(1)制备树脂胶液：按重量份数计，将40份PPE树脂(双羟基封端聚苯醚低聚物)、140份双环戊二烯环氧树脂、10份DDS树脂、0.3份交联固化剂2-甲基4-乙基咪唑,、0.5份分散剂BYK W-903、100份溶剂丙酮和20份阻燃剂四溴双酚A，40份填充材料高纯超细球形纳米非晶态硅微粉混合，乳化搅拌均匀；
(2)将低介电型的电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过170℃的上胶机，制得半固化片。
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在170-250℃、120kgf/cm2条件下热压180min，制得无卤低介电损耗、高Tg的覆铜板。
实施例2
(1)制备树脂胶液：按重量份数计，将35份联苯型环氧树脂、75份BT改性PPO树脂(Arocy B—10和4,4′–二胺基二苯甲烷双马来酰亚胺的B-阶段预聚体与PPO树脂以1：9的质量比共混)，10份含磷阻燃剂间苯二酚双[二(2,6-二甲基苯基)磷酸酯(含磷量10.5％wt)，10份磷腈化合物(含磷量13％wt)，0.5份固化促进剂2-乙基辛酸锌，0.01份2-甲基4-乙基咪唑、0.5份分散剂BYK W-903、100份溶剂丁酮，100份填充材料高纯超细球形纳米非晶态硅微粉混合，乳化搅拌均匀；
(2)将低介电型的电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过170℃的上胶机，制得半固化片。
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在170-250℃、120kgf/cm2条件下热压180min，制得低介电损耗、高Tg的覆铜板。
(2)将低介电型的电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过180℃的上胶机，制得半固化片。
(3)取6张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在165-235℃、70-150kgf/cm2条件下热压200min，制得无卤低介电损耗、高Tg的覆铜板。
实施例3
(1)制备树脂胶液：按重量份数计，将60份联苯型环氧树脂丁酮溶液(50％wt)、140份BT改性PPO树脂溶液(Arocy B—10和4,4′–二胺基二苯甲烷双马来酰亚胺的B-阶段预聚体与PPO树脂以1：9的质量比共混，并溶于丁酮中，50％wt)，18份磷腈化合物(含磷量13％wt)，0.5份固化促进剂2-乙基辛酸锌，0.01份2-甲基4-乙基咪唑、0.5份分散剂BYK W-903、10份溶剂甲苯，100份填充材料高纯超细球形纳米非晶态硅微粉混合，乳化搅拌均匀；
(2)将低介电型的电子级玻璃纤维布浸渍在步骤(1)制得的树脂胶液中，经过180℃的上胶机，制得半固化片。
(3)取4张步骤(2)制得的半固化片叠加在一起，双面各覆有一张18μm铜箔，得板材；将板材与不锈钢板上下对应叠合，铺高耐热毛毡，送入真空压机，在170-235℃、130kgf/cm2条件下热压200min，制得低介电损耗、高Tg的覆铜板。
实施例1-3与对比例1所得样品的性能对比结果如表1所示。
表1.实施例1-3与对比例1所得样品的性能对比
Figure BDA0003258730590000071
由表1可以看出，相比于对比例1，采用本发明方案的实施例1-3制备的覆铜板，其阻燃、介电损耗、Tg、T288的测试效果均优异很多，证明本发明制备的无卤覆铜板具有较低的介电损耗、较高耐热性与更佳的阻燃性。本发明制得的覆铜板板材的T288可达到120min不分层，Tg高达230℃，Df小于0.006，适应高频高速电路板的高度层设计，而且大大提高了封装效率和PCB板可靠性。
以上所述仅为本发明的较佳实施例，并不用以限制本发明，凡在本发明的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本发明的保护范围之内。

Claims (10)

1.一种无卤、低介电损耗、高耐热覆铜板的制备方法，其特征在于，包括如下步骤：
(1)制备胶液：按重量份数计，将20-40份联苯型环氧树脂、60-90份BT改性PPO树脂，10-40份含磷阻燃剂，1-20份交联固化剂及固化促进剂、0.1-1份分散剂、40-100份溶剂，10-50份填充材料混合，乳化搅拌均匀；
(2)将低介电电子级玻璃纤维布浸渍在步骤(1)制得的树脂后，经过100-200℃的上胶机，制得半固化片；
(3)取若干张步骤(2)制得的半固化片叠加在一起，双面各覆有一张铜箔，得板材；将板材与不锈钢板上下对应叠合，送入真空压机，在100-250℃、70-150kgf/cm2条件下热压150-300min，制得无卤、低介电损耗、高耐热覆铜板。
2.根据权利要求1所述的制备方法，其特征在于，所述联苯型树脂为以含联苯(biphenyl)结构酚醛树脂为主链的环氧树脂，在甲苯和丁酮中同样具有高流动性、优异的溶解性及低粘度，所述联苯型环氧树脂的结构为：
Figure FDA0003258730580000011
3.根据权利要求1所述的制备方法，其特征在于，BT改性PPO树脂为PPO树脂与BT树脂按照9：1的质量比共混得到，所述BT树脂为Arocy B—10与4,4′–二胺基二苯甲烷双马来酰亚胺共聚得到的的B-阶段预聚体。
4.根据权利要求1所述的制备方法，其特征在于，所述含磷阻燃剂为磷腈化合物、间苯二酚双[二(2,6-二甲基苯基)磷酸酯中的至少一种。
5.根据权利要求4所述的制备方法，其特征在于，所述磷腈化合物含磷量为13％wt，结构式如下：
Figure FDA0003258730580000021
6.根据权利要求4所述的制备方法，其特征在于，所述间苯二酚双[二(2,6-二甲基苯基)磷酸酯为一种缩聚型磷酸酯阻燃剂，其中磷含量为10.5％wt。
7.根据权利要求1所述的制备方法，其特征在于，所述交联固化及固化促进剂为2-乙基辛酸锌、2-甲基4-乙基咪唑或硅烷偶联剂KH-560中的至少一种。
8.根据权利要求1所述的制备方法，其特征在于，所述分散剂为BYK W-903型湿润分散剂。
9.根据权利要求1所述的制备方法，其特征在于，所述溶剂为甲苯、丙酮或丁酮、二甲苯中的至少一种。
10.根据权利要求1所述的制备方法，其特征在于，所述填充材料为高纯超细球形纳米非晶态硅微粉和氢氧化铝中的至少一种，所述硅微粉中SiO2含量达99.9％，粒径平均为3-5μm，最大粒径不超过20μm。
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