CN116333361A - 一种高频柔性电子基膜的制备方法 - Google Patents

一种高频柔性电子基膜的制备方法 Download PDF

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CN116333361A
CN116333361A CN202310455505.6A CN202310455505A CN116333361A CN 116333361 A CN116333361 A CN 116333361A CN 202310455505 A CN202310455505 A CN 202310455505A CN 116333361 A CN116333361 A CN 116333361A
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张献
肖超
余媛媛
丁欣
王艳艳
宫艺
田兴友
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Anhui Zhongke Yushun Technology Co ltd
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Abstract

本发明公开了一种高频柔性电子基膜的制备方法，采用涂布的方式在聚酰亚胺膜表面快速构建一层致密的氟碳树脂层。特殊设计的配方使得氟树脂可以充分浸润聚酰亚胺膜和高频铜箔表面的微观间隙，涂层孔隙率、热膨胀系数大幅下降。氟树脂涂层起到三个效果：1.提高聚酰亚胺膜与高频铜箔剥离强度；2.降低PI/氟树脂复合膜整体介电常数和介电损耗；3.降低聚酰亚胺膜吸水率。

Description

一种高频柔性电子基膜的制备方法
技术领域
本发明涉及电子基膜技术领域，更具体地说，涉及一种高频柔性电子基膜的制备方法。
背景技术
聚酰亚胺(PI)膜具有优良的力学性能、电性能、化学稳定性以及很宽的耐温范围，是目前柔性覆铜板(FCCL)常用的基材。传统的技术路线是在PI表面涂覆铜箔胶黏剂，将铜箔与PI粘接一起，然后刻蚀线路制成。其中铜箔表面需要粗化，PI基膜表面需要进行改性处理以提高二者的剥离强度。
随着5G通讯的发展，传统PI制成的FCCL介电常数和介电损耗水平开始无法满足高频信号的传输需求。一方面，基材介电常数过高造成信号传输延迟，另一方面，基材介电损耗过高导致信号损耗严重。此外，高频通讯所采用的铜箔粗糙度大幅降低，传统PI基材与高频铜箔剥离力无法达到使用要求。
目前市场上高频柔性覆铜板材料主要有液晶聚合物(LCP)、聚四氟乙烯(PTFE)以及改性热塑性聚酰亚胺(MPI)。其中，LCP薄膜加工难度较大，无法大量生产，且关键原料依赖日本进口。PTFE基材覆铜板依然面临诸多技术难题，比如PTFE本身力学强度差、与铜箔热膨胀系数差异大、与高频铜箔粘接力不足等。改性MPI可以通过加热与铜箔贴合，但是其高频介电性能不如LCP和氟树脂。因此，高频通讯行业迫切需要一种新型的柔性基材，来同时满足低介电常数、低介电损耗、低吸水率、高剥离强度、匹配的热膨胀系数等诸多指标。
发明内容
本发明的目的在于提供一种高频柔性电子基膜的制备方法，用以解决上述背景技术中存在的技术问题。
本发明技术方案提供一种高频柔性电子基膜的制备方法，包括如下制备步骤：
S1：将如下质量份数的各组分：水性氟乳液60～73份、去离子水25～35份、分散剂0.3～0.5份、润湿剂0.3～0.5份、流平剂0.3～0.5份、消泡剂0.3～0.5份、增稠剂0.3～0.5份、无机填料0.5～2.5份混合分散30-40min得到涂料；
S2：将涂料均匀涂布在处理后的聚酰亚胺膜上；
S3：将涂布后的聚酰亚胺膜在80℃～120℃条件下干燥10～20min干燥，然后在300～380℃条件下烧结5min～10min得到高频电子基膜；
其中，所述水性氟乳液为PTFE乳液、PFA乳液、PVDF乳液、FEP乳液、ETFE乳液中的一种。
在一个优选地实施例中，聚酰亚胺膜为热塑性聚酰亚胺膜、热固性聚酰亚胺膜、改性聚酰亚胺膜中的一种。
在一个优选地实施例中，处理聚酰亚胺膜的方式为等离子表面处理、电晕处理、或处理液处理中的一种。
在一个优选地实施例中，分散剂为阴离子分散剂，为十二烷基硫酸钠、十二烷基苯磺酸钠和脂肪醇聚氧乙烯醚硫酸钠的一种。
在一个优选地实施例中，润湿剂为FC-4430、TEGO Twin4100、TEGO Wet260、DC209、KYC-515的一种。
在一个优选地实施例中，流平剂为BYK333、BYK348、KYC-616、TEGO Glide410、TEGOGlide100的一种。
在一个优选地实施例中，消泡剂为BYK-012、BYK-015、BYK-024、TEGO Foamex 810、TEGO 825、中的一种。
在一个优选地实施例中，增稠剂为C0-602、C-5、TEGO 3010、BYK440、BYK420中的一种。
在一个优选地实施例中，无机填料为钛白粉、氮化硼、金刚石中的一种。
在一个优选地实施例中，涂布方式为喷涂、刮涂、辊涂、逗号涂布或狭缝涂布
本发明技术方案的有益效果是：
采用涂布的方式在聚酰亚胺膜表面快速构建一层致密的氟碳树脂层。特殊设计的配方使得氟树脂可以充分浸润聚酰亚胺膜和高频铜箔表面的微观间隙，涂层孔隙率、热膨胀系数大幅下降。氟树脂涂层起到三个效果：1.提高聚酰亚胺膜与高频铜箔剥离强度；2.降低PI/氟树脂复合膜整体介电常数和介电损耗；3.降低聚酰亚胺膜吸水率。
引入的无机填料使得涂层与铜箔的热膨胀系数接近，提高了贴合铜箔后的尺寸稳定性。分散剂的加入一方面是使无机填料分散均匀，一方面是提高了无机填料的储存稳定性。加入的润湿剂主要是降低氟树脂的表面张力，使氟树脂可以充分浸润聚酰亚胺膜。增稠剂的加入一方面是调节氟树脂的粘度使氟树脂可以适合多种涂布方式，一方面是可以提高氟树脂的耐水性、降低吸水率。
附图说明
图1为本发明实施例五在10000x下的扫描电镜图，
图2为本发明实施例五在1000x下的扫描电镜图，
图3为本发明对比例一在10000x下的扫描电镜图，
图4为本发明实施例与对比例180°剥离力图。
具体实施方式
下面结合附图和具体实施方式对本发明作进一步详细的说明。本发明的实施例是为了示例和描述方便起见而给出的，而并不是无遗漏的或者将本发明限于所公开的形式。很多修改和变化对于本领域的普通技术人员而言是显而易见的。选择和描述实施例是为了更好说明本发明的原理和实际应用，并且使本领域的普通技术人员能够理解本发明从而设计适于特定用途的带有各种修改的各种实施例。
实施例一
将60份的水性氟乳液PTFE，35份的去离子水，分散剂十二烷基硫酸钠、润湿剂TEGOTwin4100、流平剂BYK333、消泡剂BYK-024、增稠剂C-5各0.5份和无机填料钛白粉2.5份混合分散30min，将所得的水性氟涂料涂布在等离子表面处理后的聚酰亚胺膜上，80℃干燥10min，300℃烧结5min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃，压力为0.1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为喷涂。
实施例二
将73份的水性氟乳液PFA，25份的去离子水，分散剂十二烷基苯磺酸钠、润湿剂FC-443、流平剂BYK348、消泡剂BYK-012、增稠剂BYK-012各0.3份和0.5份的无机填料氮化硼混合分散40min，将所得的水性氟涂料涂布在电晕处理过的聚酰亚胺膜上，120℃干燥20min，380℃烧结10min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度400℃，压力为1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热固性聚酰亚胺膜；涂布方式为刮涂。
实施例三
将62份的水性氟乳液PVDF，35份的去离子水，分散剂脂肪醇聚氧乙烯醚硫酸钠、润湿剂TEGO Wet260、流平剂KYC-616、消泡剂BYK-015、增稠剂BYK440各0.5份和0.5份的无机填料金刚石混合分散40min，将所得的水性氟涂料涂布在处理液处理过的聚酰亚胺膜上，80℃干燥10min，300℃℃烧结5min，即得到高频电子膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度400℃，压力为1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为改性聚酰亚胺膜；涂布方式为辊涂。
实施例四
将66份的水性氟乳液FEP，30份的去离子水，分散剂十二烷基硫酸钠、润湿剂DC209、流平剂TEGO Glide410、消泡剂TEGO 825、增稠剂BYK420各0.3份和2.5份的无机填料钛白粉混合分散35min，将所得的水性氟涂料涂布在等离子表面处理后聚酰亚胺膜上，100℃干燥15min，350℃烧结8min，即得到高频电子膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度380℃，压力为0.5Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为逗号涂布。
实施例五
将60份的水性氟乳液ETFE，35份的去离子水，分散剂十二烷基硫酸钠、润湿剂KYC-515、流平剂TEGO Glide100、消泡剂TEGO Foamex 810、增稠剂BYK420各0.5份和2.5份的增白剂混合分散30min，将所得的水性涂料涂料在等离子表面处理后聚酰亚胺膜上，80℃～120℃干燥10～20min，300℃～380℃烧结5～10min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃～400℃，压力为0.1～1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为改性聚酰亚胺膜，涂布方式为狭缝涂布。
对比例一
将水性氟乳液PTFE直接涂布在等离子表面处理后的聚酰亚胺膜上，80℃干燥10min，300℃烧结5min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃，压力为0.1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为喷涂
对比例二
将73份的水性氟乳液PFA，25份的去离子水、润湿剂FC-443、流平剂BYK348、消泡剂BYK-012、增稠剂BYK-012各0.3份和0.5份的无机填料氮化硼混合分散40min，将所得的水性氟涂料涂布在电晕处理过的聚酰亚胺膜上，120℃干燥20min，380℃烧结10min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度400℃，压力为1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热固性聚酰亚胺膜；涂布方式为刮涂。
对比例三
将63.3份的水性氟乳液PVDF，35份的去离子水，分散剂十二烷基硫酸钠、润湿剂TEGO Twin4100、流平剂BYK333、消泡剂BYK-024、增稠剂C-5各0.25份和无机填料钛白粉0.45份充分搅拌分散后，将所得的水性氟涂料涂布在等离子表面处理后的聚酰亚胺膜上，80℃干燥10min，300℃烧结5min，即得到电子基膜，将此电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃，压力为0.1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为喷涂。
对比例四
将60.7份的水性氟乳液PTFE，35份的去离子水，分散剂十二烷基硫酸钠、润湿剂TEGO Twin4100、流平剂BYK333、消泡剂BYK-024、增稠剂C-5各0.35份和无机填料钛白粉2.55份充分搅拌分散后，将所得的水性氟涂料涂布在等离子表面处理后的聚酰亚胺膜上，80℃干燥10min，300℃烧结5min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃，压力为0.1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为喷涂。
对比例五
将73份的水性氟乳液，25.5份的去离子水，分散剂十二烷基硫酸钠、润湿剂OT-75、流平剂BYK348、消泡剂BYK-024、增稠剂TEGO 3010各0.3份充分搅拌分散后，将所得的水性氟涂料涂布在等离子表面处理后的聚酰亚胺膜上，80℃干燥10min，300℃烧结5min，即得到高频电子基膜，将此高频电子基膜(有涂层面)与高频铜箔(铜箔面)热压，热压温度350℃，压力为0.1Mpa，热压后的复合膜裁成长为15cm，宽10mm的长条，测试其180°剥离力；其中聚酰亚胺膜为热塑性聚酰亚胺膜；涂布方式为喷涂。
由图1-所示的实施例五的两张SEM可以发现，合适的助剂配方可以显著改善氟乳液成膜性(包括流平性、润湿性和相容性)。涂层平整度高，可以实现与高频铜箔的紧密贴合。涂层微观上分布纳米级别的小孔，这种小孔可以提供与高频铜箔匹配的粗糙度，产生物理咬合锚固作用，可以进一步提高涂层与铜箔的剥离力。
由图3所示的对比例一的扫描电镜图可以发现，单纯将水性氟乳液直接涂布于聚酰亚胺膜表面，涂层平整度很差，在10000x下发现明显的非均匀相分离结构。这是由于水性氟乳液的表面张力很大，湿膜在聚酰亚胺膜表面干燥脱水的过程中，不同部位的表面张力不同。液体会从表面张力低的地方迁移到表面张力高的地方，导致干膜的平整度下降。此外，单纯将多种氟树脂混合时，由于极性差异，不同树脂之间很难达到纳米级别的混合程度，导致固化后的涂层呈现不均匀的相分离结构。
由图4可知：
(1)通过对比实施例和对比例一发现，纯的水性氟乳液的剥离力(3.2N/10mm)明显要低于改性的水性氟涂料，其中，实施例五的剥离力最高，能达到10N/10mm，是纯的水性氟乳液的3.1倍。
(2)通过对比实施例和对比例二、五发现，分散剂和无机填料能明显提高电子基膜与高频铜箔间的粘接力
(3)通过对比实施例和对比例三、四发现，助剂的比例控制在0.3～0.5份较为合适，无机填料的比例控制在0.5～2.5份较为合适。
显然，所描述的实施例仅仅是本发明的一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域及相关领域的普通技术人员在没有作出创造性劳动的前提下所获得的所有其他实施例，都应属于本发明保护的范围。本发明中未具体描述和解释说明的结构、装置以及操作方法，如无特别说明和限定，均按照本领域的常规手段进行实施。

Claims (10)

1.一种高频柔性电子基膜的制备方法，其特征在于，包括如下制备步骤：
S1：将如下质量份数的各组分：水性氟乳液60～73份、去离子水25～35份、分散剂0.3～0.5份、润湿剂0.3～0.5份、流平剂0.3～0.5份、消泡剂0.3～0.5份、增稠剂0.3～0.5份、无机填料0.5～2.5份混合分散30-40min得到涂料；
S2：将涂料均匀涂布在处理后的聚酰亚胺膜上；
S3：将涂布后的聚酰亚胺膜在80℃～120℃条件下干燥10～20min干燥，然后在300～380℃条件下烧结5min～10min得到高频电子基膜；
其中，所述水性氟乳液为PTFE乳液、PFA乳液、PVDF乳液、FEP乳液、ETFE乳液中的一种。
2.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述聚酰亚胺膜为热塑性聚酰亚胺膜、热固性聚酰亚胺膜、改性聚酰亚胺膜中的一种。
3.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，处理所述聚酰亚胺膜的方式为等离子表面处理、电晕处理、或处理液处理中的一种。
4.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述分散剂为阴离子分散剂，为十二烷基硫酸钠、十二烷基苯磺酸钠和脂肪醇聚氧乙烯醚硫酸钠的一种。
5.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述润湿剂为FC-4430、TEGOTwin4100、TEGOWet260、DC209、KYC-515的一种。
6.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述流平剂为BYK333、BYK348、KYC-616、TEGOGlide410、TEGOGlide100的一种。
7.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述消泡剂为BYK-012、BYK-015、BYK-024、TEGOFoamex810、TEGO825、中的一种。
8.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述增稠剂为C0-602、C-5、TEGO3010、BYK440、BYK420中的一种。
9.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述无机填料为钛白粉、氮化硼、金刚石中的一种。
10.根据权利要求1所述的一种高频柔性电子基膜的制备方法，其特征在于，所述涂布方式为喷涂、刮涂、辊涂、逗号涂布或狭缝涂布。
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