CN115505259A - 一种树脂组合物、树脂胶液、半固化片及其覆铜板 - Google Patents

一种树脂组合物、树脂胶液、半固化片及其覆铜板 Download PDF

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CN115505259A
CN115505259A CN202210986262.4A CN202210986262A CN115505259A CN 115505259 A CN115505259 A CN 115505259A CN 202210986262 A CN202210986262 A CN 202210986262A CN 115505259 A CN115505259 A CN 115505259A
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resin composition
copper
resin
glue solution
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刘俊秀
秦伟峰
王丽亚
付军亮
陈长浩
姜大鹏
刘政
李凌云
栾好帅
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SHANDONG JINBAO ELECTRONICS CO Ltd
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Abstract

本发明属于复合材料技术领域，尤其涉及一种树脂组合物、树脂胶液、半固化片及其覆铜板，树脂组合物，包括以下重量份的组分：改性聚偏氟乙烯混合物：60‑120份；氰酸酯：60‑120份：聚丁二烯：1‑8份；有机金属盐催化剂：0.05‑0.3份；促进剂：0.05‑0.2份；阻燃剂：35‑50份；无机填料：80‑100份。本发明在改性聚偏氟乙烯混合物的制备中添加钛酸钡陶瓷粉，可以增强粘合力、增强韧性；同时降低树脂组合物的固化温度，提高存储稳定性；其在树脂胶液中应用，提高了胶液的存储稳定性；在半固化片、覆铜板中应用，不仅有效的改善了耐热性，同时也提高了电性能，具备较低的介电常数和介电损耗，较好的力学强度，高耐热，高玻璃化温度，而且大大降低了成本。

Description

一种树脂组合物、树脂胶液、半固化片及其覆铜板
技术领域
本发明属于复合材料技术领域，尤其涉及一种树脂组合物、树脂胶液、半固化片及其覆铜板。
背景技术
随着电子行业的发展迅速，对覆铜板性能的要求越来越高，三大便携型电子产品，卫星传输及通讯电子产品向小型化、高频高速化方向发展。特别是应用在高频高速的移动通讯领域，随着5G信号传输的发展，必须要求信号传输的速度越来越快，信号的频率也越来越高，因此要求作为信号传输载体的印制线路板材料必须降低其介电常数，同时材料的介电损耗因子也足够小。传统的FR-4覆铜板采用环氧树脂作为基体树脂，其介电性能已不能满足此要求。
聚合物基介电复合材料具有比重小、耐腐蚀、易加工成型等优点，因而成为目前热控制领域的理想材料，特别是在电气电子领域。为了顺应微电子集成、组装技术的发展，电子元器件的标准要求越来越小型化、精细化、多功能化，从而对功率输出的要求也急剧增加，这无疑会导致电子设备长时间大量地产热，热量在器件中迅速积累，工作温度快速提高，带来了器件无法及时散热、电子设备寿命短、可靠性降低的问题。然而，大多数聚合物都是热绝缘体，其热导率一般在0.1～0.5W/(m·k)之间，聚合物电介质受限于相对低的工作温度，不能满足如今的电力需求应用，现有导热聚合物基材料已无法满足高性能和极端条件下的高导热和高介电性能等方面的要求。因此，开发具有低介电损耗、高导热系数、低成本等综合性能优良的聚合物基复合材料势在必行。
发明内容
本发明针对上述的现有技术存在的不足，提供一种树脂组合物、树脂胶液、半固化片及其覆铜板。
本发明的具体的技术方案如下：
本发明的第一目的在于提供一种树脂组合物，包括以下重量份的组分：
改性聚偏氟乙烯混合物：60-120份；氰酸酯：60-120份：聚丁二烯：1-8份；有机金属盐催化剂：0.05-0.3份；促进剂：0.05-0.2份；阻燃剂：35-50份；无机填料：80-100份。
本发明采用上述技术方案具有如下技术效果：
采用以上树脂组合物具备较低的介电常数和介电损耗，较好的力学强度，高耐热，高Tg、高导热系数、低成本等综合性能，能及时散热，防止器件内部工作温度过高，并在短时高温下维持正常的工作效率。
进一步地，所述改性聚偏氟乙烯混合物制备步骤如下：
(1)取20-40份硅微粉和20-40份钛酸钡陶瓷粉放入玛瑙研钵中研磨20-40min；
(2)在(1)中研磨完的混合物中加入30-60份聚偏氟乙烯继续研磨20-40min；
(3)把(2)制得的混料置入专用模具中，温度为190℃-220℃，压力为15MPa-20MPa，保压30min-50min，热压成型后得到改性聚偏氟乙烯混合物。
本发明采用上述进一步技术方案具有如下技术效果：
在改性聚偏氟乙烯混合物的制备中，钛酸钡陶瓷粉的添加可以增强粘合力、增强韧性；同时降低树脂组合物的固化温度，提高存储稳定性。
进一步地，所述氰酸酯为双酚A型氰酸酯、双酚E型氰酸酯、双酚F型氰酸酯、双酚M型氰酸酯或双环戊二烯双酚A型氰酸酯中的一种或几种的组合。
进一步地，所述有机金属盐催化剂为乙酰丙酮钴、乙酰丙酮锌、乙酰丙酮铁、乙酰丙酮锰、乙酰丙酮铝、乙酰丙酮铜、环烷酸锌、环烷酸钛或环烷酸钴中的一种或几种的组合。
进一步地，所述促进剂为甲酸、乙酸、草酸、柠檬酸、苯磺酸、水杨酸或对甲苯磺酸中的一种或几种的组合。
进一步地，所述无机填料为氢氧化铝、氢氧化镁、空心玻璃微珠、二氧化硅、云母、高岭土、滑石粉、硫酸钡、氮化硼、氮化硅、硅酸铝或硅酸镁中的一种或几种的组合。
进一步地，所述阻燃剂为含溴阻燃剂或含磷阻燃剂，所述含溴阻燃剂为十溴二苯乙烷、溴化聚苯乙烯、溴代三嗪、五溴苄酯或溴化环氧中的一种或几种的组合；所述含磷阻燃剂选自以下物质中的一种或几种的组合：为磷酸三苯酯、磷酸三甲苯酯、间苯二酚双[二(2，6-二甲基苯基)磷酸酯]、二乙基次磷酸铝或9，10-二氢-9氧杂-10-磷杂菲10-氧化物中的一种或几种的组合。
本发明的第二目的在于提供一种树脂胶液，将上述树脂组合物溶解或分散在溶剂中得到，所述溶剂为60-120重量份。
进一步地，所述树脂胶液的制备方法：将所述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在溶剂中即可得到。
本发明的第三目的在于提供一种半固化片，采用上述树脂组合物制备所得。
进一步地，所述半固化片的制备方法：将增强材料浸渍上述树脂胶液后，在80-160℃下烘烤1-10min后得到。
本发明的第四目的在于提供一种覆铜板，采用上述半固化片制备所得。
进一步地，所述覆铜板的制备方法：取多张表面平整且涂覆均匀的上述半固化片，上下附上铜箔，置于预热到140℃-180℃的真空热压机中，在5min内升至200℃-220℃保持90min-120min；同时，压力1min升至1.0MPa，保压90min-120min，制得覆铜板。
本发明的有益效果为：
本发明的改性聚偏氟乙烯混合物以硅微粉为填料，聚偏氟乙烯作为聚合物基体，再填充高介电性的钛酸钡陶瓷制作而成，添加钛酸钡陶瓷粉，可以增强粘合力、增强韧性；同时降低树脂组合物的固化温度，提高存储稳定性。本发明的改性聚偏氟乙烯树脂组合物在树脂胶液中应用，提高了胶液的存储稳定性；在半固化片、覆铜板中应用，不仅有效的改善了耐热性，同时也提高了电性能，具备较低的介电常数和介电损耗，较好的力学强度，高耐热，高玻璃化温度，而且大大降低了成本。本发明的树脂组合物很适合应用于5G高频印制线路板材料。
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、改性聚偏氟乙烯混合物的制备：
(1)按重量组份，取20份硅微粉和20份钛酸钡陶瓷粉放入玛瑙研钵中研磨20min；
(2)在(1)中研磨完的混合物中加入30份聚偏氟乙烯继续研磨20min；
(3)把(2)制备的混料置入专用模具中，温度为190℃，压力为15MPa，保压30min，热压成型后得到改性聚偏氟乙烯混合物。
2、树脂胶液的制备：
一种树脂组合物，包括以下重量份的组分：改性聚偏氟乙烯混合物：60份；氰酸酯：60份：聚丁二烯：1份；有机金属盐催化剂：0.05份；促进剂：0.05份；阻燃剂：35份；无机填料：80份。
将上述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在60份的溶剂中即可得到树脂胶液。
3、半固化片的制备：
取23*35cm的玻璃布6张，将玻璃布浸渍到2中所述的树脂胶液后，在145℃下烘烤4min后得到半固化片。
4、覆铜板的制备：
取如上述3中新制备的表面平整且涂覆均匀的半固化片6片叠合整齐，上下附上铜箔，置于预热到140℃的真空热压机中，在5min内升至190℃保持90min；同时，压力1min升至1.0MPa，保压90min，制得覆铜板。
实施例2：
1、改性聚偏氟乙烯混合物的制备：
(1)按重量组份，取30份硅微粉和30份钛酸钡陶瓷粉放入玛瑙研钵中研磨30min；
(2)在(1)中研磨完的混合物中加入45份聚偏氟乙烯继续研磨30min；
(3)把(2)制备的混料置入专用模具中，温度为200℃，压力为18MPa，保压40min，热压成型后得到改性聚偏氟乙烯混合物。
2、树脂胶液的制备：
一种树脂组合物，包括以下重量份的组分：改性聚偏氟乙烯混合物：100份；氰酸酯：100份：聚丁二烯：4份；有机金属盐催化剂：0.15份；促进剂：0.1份；阻燃剂：48份；无机填料：90份。
将上述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在100份的溶剂中即可得到树脂胶液。
3、半固化片的制备：
取23*35cm的玻璃布4张，将玻璃布浸渍2中所述的树脂胶液后，在160℃下烘烤5min后得到半固化片。
4、覆铜板的制备：
取如上述3中新制备的表面平整且涂覆均匀的半固化片4片叠合整齐，上下附上铜箔，置于预热到160℃的真空热压机中，在5min内升至220℃保持90min；同时，压力1min升至1.0MPa，保压100min，制得覆铜板。
实施例3：
1、改性聚偏氟乙烯混合物的制备：
(1)按重量组份，取40份硅微粉和40份钛酸钡陶瓷粉放入玛瑙研钵中研磨40min；
(2)在(1)中研磨完的混合物中加入60份聚偏氟乙烯继续研磨40min；
(3)把(2)制备的混料置入专用模具中，温度为200℃，压力为15MPa，保压50min，热压成型后得到改性聚偏氟乙烯混合物。
2、树脂胶液的制备：
一种树脂组合物，包括以下重量份的组分：改性聚偏氟乙烯混合物：120份；氰酸酯：120份：聚丁二烯：8份；有机金属盐催化剂：0.3份；促进剂：0.2份；阻燃剂：50份；无机填料：100份。
将上述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在120份的溶剂中即可得到树脂胶液。
3、半固化片的制备：
取23*35cm的玻璃布8张，将玻璃布浸渍2中所述的树脂胶液后，在170℃下烘烤3min后得到半固化片。
4、覆铜板的制备：
取如上述3中新制备的表面平整且涂覆均匀的半固化片8片叠合整齐，上下附上铜箔，置于预热到180℃的真空热压机中，在5min内升至200℃保持120min；同时，压力1min升至1.0MPa，保压120min，制得覆铜板。
对比例1：
1、树脂胶液的制备：
一种树脂组合物，包括以下重量份的组分：聚偏氟乙烯：60份；氰酸酯：60份：聚丁二烯：1份；有机金属盐催化剂：0.05份；促进剂：0.05份；阻燃剂：35份；无机填料：80份。
将上述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在60份的溶剂中即可得到树脂胶液。
2、半固化片的制备：
取23*35cm的玻璃布4张，将玻璃布浸渍到1中所述的树脂胶液后，在160℃下烘烤5min后得到半固化片。
3、覆铜板的制备：
取如上述2中新制备的表面平整且涂覆均匀的半固化片4片叠合整齐，上下附上铜箔，置于预热到160℃的真空热压机中，在5min内升至220℃保持90min；同时，压力1min升至1.0MPa，保压100min，制得覆铜板。
对比例2：
1、树脂胶液的制备：
一种树脂组合物，包括以下重量份的组分：聚偏氟乙烯：120份；氰酸酯：120份：聚丁二烯：8份；有机金属盐催化剂：0.3份；促进剂：0.2份；阻燃剂：50份；无机填料：100份。
将上述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在120份的溶剂中即可得到树脂胶液。
2、半固化片的制备：
取23*35cm的玻璃布8张，将玻璃布浸渍1中所述的树脂胶液后，在170℃下烘烤3min后得到半固化片。
3、覆铜板的制备：
取如上述2中新制备的表面平整且涂覆均匀的半固化片8片叠合整齐，上下附上铜箔，置于预热到180℃的真空热压机中，在5min内升至200℃保持120min；同时，压力1min升至1.0MPa，保压120min，制得覆铜板。
实验测试结果：
表1实施例1-3与对比例1-2的实验测试结果统计表
Figure BDA0003801812580000081
通过上表结果显示，本发明所得树脂组合物在覆铜板的应用中，不仅有效的改善了覆铜板的耐热性，同时也提高了覆铜板的电性能，适用于高频高速覆铜板的制作。
可以理解，本发明是通过一些实施例进行描述的，本领域技术人员知悉的，在不脱离本发明的精神和范围的情况下，可以对这些特征和实施例进行各种改变或等效替换。另外，在本发明的教导下，可以对这些特征和实施例进行修改以适应具体的情况及材料而不会脱离本发明的精神和范围。因此，本发明不受此处所公开的具体实施例的限制，所有落入本申请的权利要求范围内的实施例都属于本发明所保护的范围内。

Claims (10)

1.一种树脂组合物，其特征在于，包括以下重量份的组分：
改性聚偏氟乙烯混合物：60-120份；氰酸酯：60-120份：聚丁二烯：1-8份；有机金属盐催化剂：0.05-0.3份；促进剂：0.05-0.2份；阻燃剂：35-50份；无机填料：80-100份。
2.根据权利要求1所述的树脂组合物，其特征在于，所述改性聚偏氟乙烯混合物制备步骤如下：
(1)取20-40份硅微粉和20-40份钛酸钡陶瓷粉放入玛瑙研钵中研磨20-40min；
(2)在(1)中研磨完的混合物中加入30-60份聚偏氟乙烯继续研磨20-40min；
(3)把(2)制得的混料置入专用模具中，温度为190℃-220℃，压力为15MPa-20MPa，保压30min-50min，热压成型后得到改性聚偏氟乙烯混合物。
3.根据权利要求1所述的树脂组合物，其特征在于，所述氰酸酯为双酚A型氰酸酯、双酚E型氰酸酯、双酚F型氰酸酯、双酚M型氰酸酯或双环戊二烯双酚A型氰酸酯中的一种或几种的组合；
所述有机金属盐催化剂为乙酰丙酮钴、乙酰丙酮锌、乙酰丙酮铁、乙酰丙酮锰、乙酰丙酮铝、乙酰丙酮铜、环烷酸锌、环烷酸钛或环烷酸钴中的一种或几种的组合；
所述促进剂为甲酸、乙酸、草酸、柠檬酸、苯磺酸、水杨酸或对甲苯磺酸中的一种或几种的组合；
所述无机填料为氢氧化铝、氢氧化镁、空心玻璃微珠、二氧化硅、云母、高岭土、滑石粉、硫酸钡、氮化硼、氮化硅、硅酸铝或硅酸镁中的一种或几种的组合。
4.根据权利要求1所述的树脂组合物，其特征在于，所述阻燃剂为含溴阻燃剂或含磷阻燃剂，所述含溴阻燃剂为十溴二苯乙烷、溴化聚苯乙烯、溴代三嗪、五溴苄酯或溴化环氧中的一种或几种的组合；所述含磷阻燃剂选自以下物质中的一种或几种的组合：为磷酸三苯酯、磷酸三甲苯酯、间苯二酚双[二(2，6-二甲基苯基)磷酸酯]、二乙基次磷酸铝或9，10-二氢-9氧杂-10-磷杂菲10-氧化物中的一种或几种的组合。
5.一种树脂胶液，其特征在于，将权利要求1-4任一项所述树脂组合物溶解或分散在溶剂中得到，所述溶剂为60-120重量份。
6.根据权利要求5所述的树脂胶液，其特征在于，其制备方法为：将所述树脂组合物按照先溶解固体，再溶解液体，最后加入填料的顺序，溶解或分散在溶剂中即可得到。
7.一种半固化片，其特征在于，采用权利要求1-4任一项所述的树脂组合物制备所得。
8.根据权利要求7所述的半固化片，其特征在于，其制备方法为：将增强材料浸渍所述的树脂胶液后，在80-160℃下烘烤1-10min后得到。
9.一种覆铜板，其特征在于，采用权利要求7-8任一项所述的半固化片制备所得。
10.根据权利要求9所述的覆铜板，其特征在于，其制备方法为：取多张表面平整且涂覆均匀的所述半固化片，上下附上铜箔，置于预热到140℃-180℃的真空热压机中，在5min内升至200℃-220℃保持90min-120min；同时，压力1min升至1.0MPa，保压90min-120min，制得覆铜板。
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