CN113844130A - 一种高Tg高频覆铜板的制备方法 - Google Patents

一种高Tg高频覆铜板的制备方法 Download PDF

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CN113844130A
CN113844130A CN202111066807.1A CN202111066807A CN113844130A CN 113844130 A CN113844130 A CN 113844130A CN 202111066807 A CN202111066807 A CN 202111066807A CN 113844130 A CN113844130 A CN 113844130A
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resin
parts
preparation
copper
clad plate
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刘政
李凌云
姜晓亮
杨永亮
郑宝林
栾好帅
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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，尤其涉及一种高Tg高频覆铜板的制备方法。本发明中双酚A型环氧树脂中的环氧基和羟基赋予树脂反应性，使树脂固化物具有很强的内聚力和粘接力；醚键和羟基是极性基团，有助于提高树脂浸润性和粘附力；苯环赋予聚合物耐热性和刚性；异丙撑基减小分子间作用力，赋予树脂一定韧性从而提高玻璃化转变温度。本发明工艺压制所得的覆铜板具有较高玻璃化转变温度(Tg)>215℃、DK≤3.8、Df≤0.007、热分层时间(T288)>120min，基本可以满足5G通信所用电子产品以及智能设备的使用要求。

Description

一种高Tg高频覆铜板的制备方法
技术领域
本发明属于覆铜板生产技术领域，尤其涉及一种高Tg高频覆铜板的制备方法。
背景技术
为了适应电子工业的快速发展以及人工智能产业的不断成熟，家电、通讯工具以及智能穿戴设备也正不断的在向小、轻、薄的方向发展，印制电路板(PCB)基板的性能也不断地进步。而其中，5G技术的发展拉动了高速高频覆铜板的快速发展。目前在玻璃布基覆铜板总量中FR-4覆铜板的生产量占总产的90％以上。5G建设中需要的毫米波(30-300GHZ)决定覆铜板基材必须是高频覆铜板才能满足频段要求，所以说毫米波这项技术需要更多的宏基站，进而加大了对高频覆铜板的需求。5G建设过程中所需的另一项技术MassiveMIMO也将刺激了高频覆铜板的不断研发，该项技术的发展意味着天线振子、馈电网络系统将使用更多的高频覆铜板。另外为解决5G信号覆盖不足的问题，将大量建设微小基站，更是全方位的刺激高速高频覆铜板的全面发展。
高Tg印制板当温度升高到某一区域时，基板将由“玻璃态”转变为“橡胶态”，此时的温度称为该板的玻璃化温度(Tg)。也就是说，Tg是基材保持刚性的最高温度(℃)。普通PCB基板材料在高温下，不但产生软化、变形、熔融等现象，同时还表现在机械、电气特性的急剧下降，一般板材的Tg为130度以上，高Tg一般大于170度，中等Tg约大于150度。通常Tg≥170℃的PCB印制板，称作高Tg印制板。基板的Tg提高了，印制板的耐热性、耐潮湿性、耐化学性、耐稳定性等特征都会提高和改善。Tg值越高，板材的耐温度性能越好，尤其在无铅制程中，高Tg应用比较多。高Tg意味的是高耐热性。随着电子工业的飞跃发展，特别是以计算机为代表的电子产品，向着高功能化、高多层化发展，需要PCB基板材料的更高的耐热性作为重要的保证。以SMT、CMT为代表的高密度安装技术的出现和发展，使PCB在小孔径、精细线路化、薄型化方面，越来越离不开基板高耐热性的支持。所以一般的FR-4与高Tg的FR-4的区别是在热态下，特别是在吸湿后受热下，其材料的机械强度、尺寸稳定性、粘接性、吸水性、热分解性、热膨胀性等各种性能存在差异，高Tg产品的这些性能明显要优于普通的PCB基板材料。
发明内容
本发明针对上述现有技术存在的不足，目的在于提供一种高Tg高频覆铜板的制备方法，本发明制备的覆铜板玻璃化转变温度达到215℃以上，热分层时间大于1200s，介电常数在3.6-3.9之间，介质损耗低于0.007，热分层时间(T288)>120min。
为实现以上目的，采用的具体技术方案如下：
一种高Tg高频覆铜板的制备方法，包括如下步骤：
(1)制备树脂胶液：按重量份计，将10～50份DCPD型环氧树脂、9～25份双酚A型环氧树脂、3～20份DDS固化剂、0.1～0.8份咪唑类催化剂、10～30份无机填料、10～60份无卤阻燃填料加入溶剂中，在充分搅拌下，乳化分散均匀2小时后制备得到树脂胶液；
(2)将玻璃纤维布浸渍在步骤(1)制得的树脂后，经过150-170℃烘烤4～7min，制得粘结片；
(3)取若干张步骤(2)制得的粘结片叠合在一起，一面或双面覆以18～35μm铜箔，得板材；将板材放置在不锈钢板之间，然后置于真空压机中，在10～40kgf/cm2、170～220℃条件下热压120～180分钟制成。
其中，所述咪唑类催化剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、DMAP中的至少一种；所述无机填料为滑石粉、硅微粉、云母粉、钛白粉中的至少一种；所述无卤阻燃填料为氢氧化铝、氮系阻燃剂、磷系阻燃剂、三氧化二锑、氢氧化镁中的至少一种；所述溶剂为丙酮、丁酮、甲苯、二甲苯、丙二醇单甲醚、环已酮中的至少一种。
优选的，所用玻璃纤维布型号为1035或2116。
优选的，步骤(1)中胶液的凝胶时间为260秒～390秒，胶液固体含量为50～70％(171℃)。
优选的，步骤(2)中粘结片的树脂流动度为15～35％，含胶量为40～70％，凝胶时间为150～190秒(171℃)，所述的含胶量是指浸胶用树脂乳液纯固体占浸胶料片重量的百分比，所述的流动度是指浸胶用树脂乳液在1.4MPa、171±2℃流出的重量占浸胶用树脂乳液总重量的百分比。
与现有技术相比，本发明的有益效果是：
(1)本发明中双酚A型环氧树脂中的环氧基和羟基赋予树脂反应性，使树脂固化物具有很强的内聚力和粘接力；醚键和羟基是极性基团，有助于提高树脂浸润性和粘附力；苯环赋予聚合物耐热性和刚性；异丙撑基减小分子间作用力，赋予树脂一定韧性从而提高玻璃化转变温度。
(2)本发明中用DDS固化剂固化环氧树脂，可以提高产品的玻璃化转变温度、耐热性、尺寸稳定性，保证低吸水率和Low Dk/Df等。
(3)本发明工艺压制所得的覆铜板具有较高玻璃化转变温度(Tg)>215℃、DK≤3.8、Df≤0.007、热分层时间(T288)>120min，基本可以满足5G通信所用电子产品以及智能设备的使用要求。
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。
具体实施方式中，所述的“份”均为重量份。
实施例1
(1)制备树脂胶液：取DCPD型环氧树脂20份(环氧当量210～290g/eq)，双酚A型环氧树脂17份(环氧当量180～260g/eq)，DDS固化剂13份，DMAP0.21份，硅微粉15份，磷系阻燃剂10份，氮系阻燃剂10份，加入丁酮、二甲苯的溶剂中，在充分搅拌下配置成固体含量为66％的树脂溶液。
(2)用型号为1035和2116玻纤布浸渍上述树脂溶液，经170℃烘烤6分钟，制成粘结片。粘结片含胶量为55±5％，树脂的流动度为25±4％。
(3)取6片粘结片，叠合整齐，双面覆以18μm铜箔，放置在不锈钢板之间，然后置于真空压机中，在175±3℃、35kgf/cm2条件下热压180分钟，制成双面覆铜板。
实施例2
(1)制备树脂胶液：取DCPD型环氧树脂25份，双酚A型环氧树脂15份(环氧当量180～260g/eq)，DDS固化剂15份，2-甲基咪唑0.21份，DMAP0.11份，氢氧化铝15份，磷系阻燃剂10份，加入丙酮、丙二醇单甲醚的溶剂中，在充分搅拌下配置成固体含量为66％的树脂溶液。
(2)用型号为1035和2116玻纤布浸渍上述树脂溶液，经170℃烘烤6分钟，制成粘结片。粘结片含胶量为52±4％，树脂的流动度为24±3％。
(3)取6片粘结片，叠合整齐，双面覆以18μm铜箔，放置在不锈钢板之间，然后放于真空压机中，在190±6℃、40kgf/cm2条件下热压180分钟，制成双面覆铜板。
实施例3
(1)制备树脂胶液：取DCPD型环氧树脂25份，双酚A型环氧树脂18份(环氧当量180～260g/eq),DDS固化剂12份,2-乙基-4-甲基咪唑0.20份，DMAP 0.17份，氢氧化镁18份，磷系阻燃剂9份，钛白粉10份，加入适量丙酮、丁酮、二甲苯做溶剂，在充分搅拌下配置成固体含量为66％的树脂溶液。
(2)用型号为1035和2116玻纤布浸渍上述树脂溶液，经170℃烘烤9分钟，制成粘结片。粘结片含胶量为53±3％,树脂的流动度为25±3％。
(3)取6片粘结片，叠合整齐，双面覆以18μm铜箔,放置在不锈钢板之间，然后放于真空压机中，在185±3℃、40kgf/cm2条件下热压180分钟，制成双面覆铜板。
对比例1
(1)制备树脂胶液：取苯并噁嗪环氧树脂29份，苯酚-芳烷基环氧树脂13份，含磷酚醛树脂25份，2-乙基咪唑0.14份，三氧化二锑30份，硅微粉10份，加入适量丙酮、丁酮、二甲苯做溶剂,在充分搅拌下配置成固体含量为65％的树脂溶液。
(2)用型号为1035和2116玻纤布浸渍上述树脂溶液，经170℃烘烤7分钟，制成粘结片。粘结片含胶量为55±3％,树脂的流动度为21±3％。
(3)取6片粘结片，叠合整齐，双面覆以18μm铜箔,放置在不锈钢板之间，然后放于真空压机中，在220±3℃、40kgf/cm2条件下热压180分钟，制成双面覆铜板。
对比例2
(1)制备树脂胶液：取苯并噁嗪环氧树脂29份，DCPD型环氧树脂22份,邻甲酚型酚醛环氧树脂11份，咪唑0.11份，硅微粉14份，氢氧化铝10份,加入适量丙酮、丙二醇单甲醚做溶剂，在充分搅拌下配置成固体含量为65％的树脂溶液。
(2)用1035和2116玻纤布浸渍上述树脂溶液，经170℃烘烤7分钟，制成粘结片。粘结片含胶量为55±4％,树脂的流动度为25±4％。
(3)取6片粘结片，叠合整齐，双面覆以18μm铜箔,放置在不锈钢板之间，然后放于真空压机中，在220±3℃、40kgf/cm2条件下热压180分钟，制成双面覆铜板。
测试
对实施例1～3以及对比例1～2制备得到的覆铜板进行以下测试，测试结果如表1所示。
(1)玻璃化转变温度(Tg)，测试方法采用差示扫描量热仪分析(DSC)
(2)热膨胀系数(CTE)，测试方法采用热机械分析法(TMA)
(3)热分解温度(Td)，测试方法采用热重分析法(TGA)
(4)燃烧性，依据美国UL94垂直燃烧法测定
(5)热分层时间(T288)，测试方法采用热机械分析法(TMA)
(6)剥离强度，测试方法按照IPC-TM-650 2.4.9测量
(7)介电常数(Dk)和介质损耗(Df)，测试方法按照ASTM-D150和IPC-TM-6502.5.5.9测量
(8)加工性测试方法按照IPC-TM-650 2.4.7测量
(9)耐浸焊性测试方法IPC-TM-650 2.6.8测量
表1.实施例1～3与对比例1～2所得覆铜板的性能对比
Figure BDA0003258743110000061
Figure BDA0003258743110000071
由表1可以看出，与对比例1～2相比，实施例1～3树脂组合物制备的覆铜板具有高Tg、Tg能达到215℃以上，高耐热性、低吸水性、热分层时间(T288)>120min、良好的介电性能等优良的综合性能，且达到无卤阻燃要求，具有良好的加工性能。
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 (7)

1.一种高Tg高频覆铜板的制备方法，其特征在于，包括如下步骤：
(1)制备树脂胶液：按重量份计，将10～50份DCPD型环氧树脂、9～25份双酚A型环氧树脂、3～20份DDS固化剂、0.1～0.8份咪唑类催化剂、10～30份无机填料、10～60份无卤阻燃填料加入溶剂中，在充分搅拌下制备得到树脂胶液；
(2)将玻璃纤维布浸渍在步骤(1)制得的树脂后，经过150-170℃烘烤4～7min，制得粘结片；
(3)取若干张步骤(2)制得的粘结片叠合在一起，一面或双面覆以18～35μm铜箔，得板材；将板材放置在不锈钢板之间，然后置于真空压机中，在10～40kgf/cm2、170～220℃条件下热压120～180分钟制成。
2.根据权利要求1所述的制备方法，其特征在于，所述咪唑类催化剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、DMAP中的至少一种。
3.根据权利要求1或2所述的制备方法，其特征在于，所述无机填料为滑石粉、硅微粉、云母粉、钛白粉中的至少一种。
4.根据权利要求1所述的制备方法，其特征在于，所述无卤阻燃填料为氢氧化铝、氮系阻燃剂、磷系阻燃剂、三氧化二锑、氢氧化镁中的至少一种。
5.根据权利要求1所述的制备方法，其特征在于，所述溶剂为丙酮、丁酮、甲苯、二甲苯、丙二醇单甲醚、环已酮中的至少一种。
6.根据权利要求1所述的制备方法，其特征在于，步骤(1)中胶液的凝胶时间为260秒～390秒，胶液固体含量为50～70％(171℃)。
7.根据权利要求1所述的制备方法，其特征在于，步骤(2)中粘结片的树脂流动度为15～35％，含胶量为40～70％，凝胶时间为150～190秒(171℃)。
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