CN113930212A - 一种低介电损耗挠性热固型粘结剂及其制备方法 - Google Patents
一种低介电损耗挠性热固型粘结剂及其制备方法 Download PDFInfo
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Abstract
本发明公开一种低介电损耗挠性热固型粘结剂及其制备方法。以无溶剂计,由以下各组分组成:双酚A型氰酸酯10~30质量份、烯丙基改性的双马来酰亚胺10~40质量份、环氧改性橡胶5~50质量份、固化促进剂0.005~1.0质量份和填料0~40质量份;其中环氧改性橡胶为SBS嵌段共聚物、或SIS嵌段共聚物、或SIBS嵌段共聚物分子链中的双键被部分环氧化的产物,其环氧当量为1000~2500g/eq。该热固型性粘结剂用于挠性覆铜板时具有较好的柔韧性,极低的介电常数、介电损耗和吸水率,较高的剥离强度和优异的耐浸焊性能,对铜箔的粘接力较大,同时原料来源不受限且制备方法简单易行。
Description
技术领域
本发明属于挠性覆铜板用的特种树脂材料领域,具体涉及一种低介电损耗挠性热固型粘结剂及其制备方法。
背景技术
随着5G通讯和移动互联网的高速发展,移动终端,包括手机、平板、笔记本电脑等的天线、数据传输和处理系统对具有低介电常数,特别是低介电损耗的挠性印制电路板基材(即挠性覆铜板)的需求大幅增加。
目前,市面上常见的挠性覆铜板均是以聚酰亚胺或对苯二甲酸乙二醇酯等柔性薄膜为绝缘基膜直接粘接、或通过胶粘剂粘接在铜箔上制备而成。但现用的绝缘基膜和胶粘剂类别(丙烯酸酯类和环氧树脂类)均不能满足上述5G通讯终端对其挠性覆铜板的低介电常数(≤3.5)和低介电损耗(≤0.01)的要求。例如,丙烯酸酯类挠性覆铜板用胶粘剂在1GHz时的介电常数和介电损耗分别≥3.2和≥0.03,环氧树脂类挠性覆铜板用胶粘剂在1GHz时的介电常数和介电损耗分别≥3.5和≥0.02。
近年,市面上虽然出现了以液晶聚合物和改性聚酰亚胺为代表的挠性覆铜板基材用的低介电常数和低介电损耗的树脂,但前者原料薄膜的来源极为有限,加工性能相对较差,且分子结构的可设计性较为单一,改性的空间较小;后者虽然在集成电路产业有良好的应用基础,但具有低介电常数和低介电损耗的改性聚酰亚胺(微孔型、含氟型或非氟型)目前普遍存在单体合成和聚合工艺复杂且要求高、或力学强度低、或吸水率偏大、或与铜结合力偏低、或含卤危害、或来源有限、或成本高等问题。
而目前已经产业化和商品化,且具有低介电常数(≤3.5)和低介电损耗(≤0.01)特性的树脂材料,例如聚四氟乙烯、碳氢树脂、改性聚苯醚、改性双马来酰亚胺、氰酸酯或三嗪树脂等,均仅限于用来制备常规的硬质覆铜板。特别是,其中的聚四氟乙烯、碳氢树脂和特殊的聚苯醚原材料已被国外,特别是欧美等国家所垄断导致其来源也受到极大的限制。
发明内容
为了克服现有技术的不足,本发明的主要目的是提供一种低介电损耗挠性热固型粘结剂及其制备方法。该热固型性粘结剂用于挠性覆铜板时具有较好的柔韧性,极低的介电常数、介电损耗和吸水率,较高的剥离强度和优异的耐浸焊性能,对铜箔的粘接力较大,同时原料来源不受限且制备方法简单易行。
为了实现上述目的,本发明采取的技术方案如下:
提供一种低介电损耗挠性热固型粘结剂,以无溶剂计,由以下各组分组成:双酚A型氰酸酯10~30质量份、烯丙基改性的双马来酰亚胺10~40质量份、环氧改性橡胶5~50质量份、固化促进剂0.005~1.0质量份和填料0~40质量份;其中所述环氧改性橡胶为(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(SBS)、或(苯乙烯-异戊二烯-苯乙烯)嵌段共聚物(SIS)、或(苯乙烯-异戊二烯/丁二烯-苯乙烯)嵌段共聚物(SIBS)分子链中的双键被部分环氧化的产物,其环氧当量为1000~2500g/eq。
按上述方案,优选的,所述低介电损耗挠性热固型粘结剂,以无溶剂计,由以下各组分组成:双酚A型氰酸酯15~30质量份、烯丙基改性的双马来酰亚胺15~35质量份、环氧改性橡胶10~45质量份、固化促进剂0.05~0.5质量份和填料0~30质量份。
按上述方案,所述低介电损耗挠性热固型粘结剂还包括有机溶剂,固含量为10~80wt%。优选地,固含量为20~50wt%。优选地,所述有机溶剂选自丁酮、甲苯、二甲苯、环己烷、环己酮等中的一种或多种。
按上述方案,所述烯丙基改性的双马来酰亚胺为二烯丙基双酚A、烯丙基甲酚、烯丙基酚环氧树脂中的一种或几种与二苯甲烷双马来酰亚胺(BDM)反应的产物。
按上述方案,所述的(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(SBS)、或(苯乙烯-异戊二烯-苯乙烯)嵌段共聚物(SIS)、或(苯乙烯-异戊二烯/丁二烯-苯乙烯)嵌段共聚物(SIBS)的分子链中苯乙烯链段的含量10~40%,200℃/5kg条件下的熔融指数为1~35g/10min。
按上述方案,所述固化促进剂为咪唑、2-甲基咪唑(2MI)、2-苯基咪唑、2-乙基-4-甲基咪唑(2E4MI)、DMP-10、DMP-30、二甲基苄胺、二环脒、4-二甲氨基吡啶(DMAP)中的一种或多种组合物。
按上述方案,所述填料为外形不限的二氧化硅(硅微粉)、二氧化钛(钛白粉)、二氧化锆、三氧化二铝、氧化镁、硅酸钙、钛酸钡、氮化硼、氮化铝、碳化硼、聚四氟乙烯粉体中的一种或多种。
提供上述低介电损耗挠性热固型粘结剂的制备方法,包括以下步骤:
将双酚A型氰酸酯、烯丙基改性的双马来酰亚胺、环氧改性橡胶和有机溶剂加入到容器中,在室温至120℃之间搅拌使其充分溶解并混合均匀;然后再加入填料,研磨分散均匀;最后加入固化促进剂,使其充分搅拌均匀,即得到低介电损耗挠性热固型粘结剂。
提供一种上述低介电损耗挠性热固型粘结剂在挠性覆铜板上的应用。
本发明提供的低介电损耗挠性热固型粘结剂中,以低介电特性的氰酸酯树脂和烯丙基改性的双马来亚酰胺树脂为主体树脂,并通过低介特性且具有良好耐热性和柔韧性的环氧改性橡胶协调其刚性,赋予组合物良好的柔韧性,一方面环氧改性橡胶中的环氧基可与氰酸酯树脂的氰酸酯基发生化学反应,提升树脂和橡胶之间的相容性,同时反应过程中也不会产生二次极性基团,不影响整体介电性能;同时配合调控环氧改性橡胶中环氧基团的含量(环氧当量1000~2500g/eq),所得粘结剂组合物固化后具有良好的柔韧性,用于覆铜板时覆铜板具有良好的耐折性。
本发明的有益效果为:
1.本发明提供一种低介电损耗挠性热固型粘结剂,所述热固型粘结剂选用具有低介电特性的氰酸酯树脂和烯丙基改性的双马来亚酰胺树脂为主体树脂,配合具有低介电特性且具有良好耐热性和柔韧性的环氧改性橡胶,再进一步配合固化促进剂和填料,组分之间兼容性好,所得热固型粘结剂在具有低介电常数(3.1~3.5)和低介电损耗(0.007~0.01)的特性的同时,还具有良好的柔韧性,获得了满足要求的低介电损耗挠性热固型粘结剂。
2.该热固型粘结剂的耐热性、吸水率、力学性能,对铜箔或聚酰亚胺薄膜的粘接性能、加工性能等均可与目前挠性覆铜板领域现用的普通环氧树脂类胶粘剂相媲美,且原料来源不受限,制备方法简单易行。
具体实施方式
为了使本领域的技术人员能够更好的理解本发明的技术方案,下面将进行详细说明,但本发明的保护范围不仅限于此。
本发明中用于制备低介电损耗挠性热固型粘结剂的主要原料来源如下:
(1)烯丙基改性的双马来酰亚胺:将1-20质量份的烯丙基改性物(二烯丙基双酚A、烯丙基甲酚、烯丙基酚环氧树脂中的一种或几种)投入共沸点为140℃的甲苯与二甲苯混合溶剂中,137℃加热搅拌至全溶后形成20-40wt%的溶液。往该溶液投入5-30质量份的二苯甲烷双马来酰亚胺(BDM)粉末,137℃搅拌0.5h后冷却至室温即成烯丙基改性的双马来酰亚胺。
(2)环氧改性橡胶:可直接使用日本大赛璐公司的牌号为EPOFRIEND AT501和CT310环氧化热塑性弹性体(环氧当量分别为1055g/eq和2125g/eq,苯乙烯含量均为40%),也可使用市面上常见的(苯乙烯-丁二烯-苯乙烯)嵌段共聚物(SBS)、或(苯乙烯-异戊二烯-苯乙烯)嵌段共聚物(SIS)、或(苯乙烯-异戊二烯/丁二烯-苯乙烯)嵌段共聚物(SIBS),例如美国Kraton公司的DSBS、SIS或SIBS系列产品,再经过环氧改性的产物。该环氧改性的步骤如下:
将100质量份的待改性橡胶(例如实施例3~5中的美国科腾公司SBS-D1118、SIS-D1119和SIBS-D1170等,但不限于此)用丁酮溶解成固含量10~30wt%的溶液;然后加入25~40质量份的甲酸,在30~50℃搅拌均匀后在1h内缓慢匀速地加2~10质量份双氧水,滴完后继续反应1~5h;最后用适量的碳酸钠中和反应液至中性,再依次经分液、水洗、分离和干燥等步骤得到相应的环氧改性橡胶。
(3)其他原料双酚A型氰酸酯树脂、固化促进剂和填料均为市售品,在此就不一一列举。
实施例1~6按照表1的组分和质量份配比进行制备,具体制备方法如下:
将双酚A型氰酸酯、烯丙基改性的双马来酰亚胺、环氧改性橡胶和有机溶剂加入到容器中,在室温至120℃之间搅拌使其充分溶解并混合均匀;然后再加入填料,研磨分散均匀;最后加入固化促进剂,使其充分搅拌均匀,即得到低介电损耗挠性热固型粘结剂。
表1实施例1~6配方(单位:质量份)
将实施例1~6所得低介电损耗挠性热固型粘结剂按照如下步骤制样和测试:
制样:将上述热固型粘结剂的胶液均匀的涂布在适当的离型膜上,经过烘烤除去有机溶剂,控制胶层厚度25μm;然后将其通过封塑机转移到25μm的PI膜,另一面也辅以相应的铜箔毛面,再经快压或层压固化。
参照IPC-TM-650检测方法,分别测试由上述热固型粘结剂制备的挠性覆铜板的剥离强度、耐焊性(288℃)、吸水率、10GHz下的介电常数和介电损耗、耐折性等,具体结果见表2。
表2实施例1-6的性能指标测试结果
由于目前国内、外还没有正式的关于低介电常数和低介电损耗的挠性印制电路板基材(包括挠性覆铜板、纯胶片等)的国家标准、国际标准,以及行业标准,而目前已经商品化的液晶聚合物(LCP)或改性聚酰亚胺(MPI)类的挠性印制电路板基材(包括挠性覆铜板、纯胶片等)产品的主要技术或质量指标均是以各自厂家的内控标准为主。因此,对于由本发明所述的粘结剂组合物所对应挠性覆铜板的相关技术指标参照挠性印制电路板基材国际标准(IPC4203/19普通“环氧类纯胶片”)和高频、高速硬质覆铜板行业的普遍接受的经验值来对上述表2的测试结果进行说明。具体如下:
实施例1~6中测试剥离强度、耐焊性(288℃)和吸水率的结果均满足国际标准(IPC4203/19挠性印制电路板用的普通“环氧类纯胶片”)标准对应的要求(分别为剥离强度≥0.7N/mm、288℃±5℃/10s耐焊通过、吸水率≤4.0%)。同时,实施例1~6样品在10GHz下的介电常数(Dk为3.1~3.5)和介电损耗(Df为0.0066~0.0091),符合高频、高速硬质覆铜板行业中低介电常数和介电损耗的要求。此外,实施例1~6样品的耐折性(R=2mm)也可以达到普通的挠性印制电路板用的环氧类胶粘剂同等水平(≥300次)。
上述测试数据仅为本发明的典型配方或测试数据,并不用于限制本发明,本发明的保护范围由权利要求书限定。任何熟悉本技术领域的研究人员在本发明公示的技术范围内,根据本发明的的配方及思路进行替换或改变,均属于本发明的保护范围之内。
Claims (10)
1.一种低介电损耗挠性热固型粘结剂,其特征在于,以无溶剂计,由以下各组分组成:双酚A型氰酸酯10~30质量份、烯丙基改性的双马来酰亚胺10~40质量份、环氧改性橡胶5~50质量份、固化促进剂0.005~1.0质量份和填料0~40质量份;其中所述环氧改性橡胶为(苯乙烯-丁二烯-苯乙烯)嵌段共聚物、或(苯乙烯-异戊二烯-苯乙烯)嵌段共聚物、或(苯乙烯-异戊二烯/丁二烯-苯乙烯)嵌段共聚物分子链中的双键被部分环氧化的产物,其环氧当量为1000~2500g/eq。
2.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,以无溶剂计,由以下各组分组成:双酚A型氰酸酯15~30质量份、烯丙基改性的双马来酰亚胺15~35质量份、环氧改性橡胶10~45质量份、固化促进剂0.05~0.5质量份和填料0~30质量份。
3.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,所述烯丙基改性的双马来酰亚胺为二烯丙基双酚A、烯丙基甲酚、烯丙基酚环氧树脂中的一种或几种与二苯甲烷双马来酰亚胺反应的产物。
4.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,所述环氧改性橡胶中,(苯乙烯-丁二烯-苯乙烯)嵌段共聚物、或(苯乙烯-异戊二烯-苯乙烯)嵌段共聚物、或(苯乙烯-异戊二烯/丁二烯-苯乙烯)嵌段共聚物的分子链中苯乙烯链段的含量10~40%,200℃/5kg条件下的熔融指数为1~35g/10min。
5.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,所述固化促进剂为咪唑、2-甲基咪唑、2-苯基咪唑、2-乙基-4-甲基咪唑、DMP-10、DMP-30、二甲基苄胺、二环脒、4-二甲氨基吡啶中的一种或多种组合物。
6.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,所述填料为外形不限的二氧化硅、二氧化钛、二氧化锆、三氧化二铝、氧化镁、硅酸钙、钛酸钡、氮化硼、氮化铝、碳化硼、聚四氟乙烯粉体中的一种或多种。
7.根据权利要求1所述的低介电损耗挠性热固型粘结剂,其特征在于,所述低介电损耗挠性热固型粘结剂还包括有机溶剂,固含量为10~80wt%。
8.根据权利要求7所述的低介电损耗挠性热固型粘结剂,其特征在于,所述有机溶剂选自丁酮、甲苯、二甲苯、环己烷、环己酮中的一种或多种。
9.一种权利要求1-8任一项所述的低介电损耗挠性热固型粘结剂的制备方法,其特征在于,包括以下步骤:
将双酚A型氰酸酯、烯丙基改性的双马来酰亚胺、环氧改性橡胶和有机溶剂加入到容器中,在室温至120℃之间搅拌使其充分溶解并混合均匀;然后再加入填料,研磨分散均匀;最后加入固化促进剂,使其充分搅拌均匀,即得到低介电损耗挠性热固型粘结剂。
10.一种权利要求1-8任一项所述的低介电损耗挠性热固型粘结剂在挠性覆铜板上的应用。
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