CN116852815A - 一种三维成型ptfe基覆铜板及其制备方法 - Google Patents
一种三维成型ptfe基覆铜板及其制备方法 Download PDFInfo
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Abstract
本发明属于覆铜板制备领域，具体涉及一种三维成型PTFE基覆铜板及其制备方法。本发明以石墨烯、正硅酸乙酯、PTFE纤维为原料，通过3D打印技术构造形成PTFE三维结构介质层，并以铜粉、钛粉、PTFE乳液为原料在铜箔与介质层间压制形成过渡层，通过过渡层的辅助能有效增强铜箔与介质层之间的结合力。最终制备得到的PTFE基覆铜板，表现出低于2的介电常数，且介电损耗低于0.0016，表明更有利于信号的高速、低延迟、无损耗传输。同时，该覆铜板力学性能优异，剥离强度能达到2.32N/mm。
Description
技术领域
本发明属于覆铜板制备领域，具体涉及一种三维成型PTFE基覆铜板及其制备方法。
背景技术
随着电子工业的迅猛发展，印刷线路板在电子元器件中起到了关键的连接和支撑作用，而覆铜板又是线路板的基础材料，因此在众多的电子产品中有着广泛的应用。
PTFE分子链中含有C-F键，且具有对称结构，同时由于F原子较大，使PTFE的分子链呈现出螺旋结构，这些结构特征赋予了PTFE优异的特性，如优异的介电特性、绝缘性、高耐热性、耐化学稳定性及耐候性等，其是最适合用于覆铜板生产的树脂材料。现有技术中，通常将PTFE与陶瓷填料混合，并通过构建形成三维多孔结构来容纳更多的空气，进而降低覆铜板的介电常数。然而，由于PTFE为热塑性高分子材料，虽然能够经过重复加热成型，但其熔点较高（熔点为327℃左右），且熔融粘度极大，因此常规的熔融挤出、注塑成型等工艺均不适用于PTFE基覆铜板的三维成型加工，制约了低介电常数PTFE基覆铜板的研究和发展。
发明内容
针对现有技术中PTFE基覆铜板的三维成型加工困难，制约了低介电常数PTFE基覆铜板的研究和发展问题，本发明提供一种三维成型PTFE基覆铜板及其制备方法，以石墨烯、正硅酸乙酯、PTFE纤维为原料，通过3D打印技术构造形成PTFE三维结构介质层，并以铜粉、钛粉、PTFE乳液为原料在铜箔与介质层间压制形成过渡层，通过过渡层的辅助能有效增强铜箔与介质层之间的结合力，最终制备得到的PTFE基覆铜板具有较低的介电常数，且力学性能优异。
本发明第一方面提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液置于球磨机中，抽真空后进行球磨，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液中，滴入氨水充分反应后，进行热处理，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合，在热水浴中搅拌，待冷却后加入N,N-二甲基甲酰胺溶液，继续搅拌，制得溶胶B；
S3：以铜箔为基底，将粉末A在其表面压制成膜，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
S5：将S4中3D打印后获得的材料进行冷冻干燥，得到三维成型PTFE基覆铜板。
进一步的，步骤S1中，铜粉、钛粉、PTFE乳液的质量比为1:1:3；球磨时间为40~60min，球磨转速为1000~1200rpm，真空度为0.1×10-2Pa~1.0×10-2Pa。
进一步的，步骤S2中，石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol。
进一步的，步骤S2中，无水乙醇溶液的浓度为99.5%，石墨烯与无水乙醇溶液的质量比为1:100。
进一步的，步骤S2中，正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L，在80~85℃热水浴中搅拌5~6h。
进一步的，步骤S2中，热处理过程为：置于80~90℃下热处理5~6h。
进一步的，步骤S2中，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1。
进一步的，步骤S3中，压制过程为：将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，在铜箔上形成过渡层。
进一步的，所述真空热压的压强为10~20MPa，时间为2~3h，温度为400~450℃。
进一步的，步骤S4中，所述三维网状模型的网眼面积为0.0001~0.04mm2，并将模型分层处理，打印时分层打印，层数为2~6层，层高10~200μm。
进一步的，步骤S3、S4中，所述3D打印过程中的成型参数为：成形室温度：-20~-15℃；针头针管温度：20~25℃；点胶针头内径10~100μm；挤出速度：200~400μm/s；剪切速度：10~15mm/s。
进一步的，冷冻干燥为：先在≤-80℃条件下低温保存，再于0.02~0.05mbar、-55~-50℃的环境下进行40~48h的冻干处理。
本发明第二方面提供一种上述的制备方法制备得到的三维成型PTFE基覆铜板。
上述本发明的一种或多种技术方案取得的有益效果如下：
1.本发明通过将正硅酸乙酯、PTFE纤维混合，利用碱性环境使得正硅酸乙酯在PTFE纤维表面水解生成SiO2，纤维状的PTFE能够更好的与SiO2接触，更加有效地利用SiO2陶瓷材料来弥补PTFE本身固有的质地软、热膨胀系数较大等缺点。石墨烯的引入则能基于其多层结构来提高SiO2的负载量，同时石墨烯对于机械性能的提升也有重要影响。
本发明采用3D打印技术将介质层材料构造成三维网络结构，能够在容纳充足的空气的同时，缓冲冷热环境下引起的体积变化，进而实现降低介电常数的同时，有效维持使用过程中介质层结构的稳定性，增长使用寿命。然而，直接将介质层通过3D打印的形式结合在铜箔上，铜箔与介质层之间的结合力较差，使用过程中容易脱落，因此本发明在铜箔与介质层之间设置过渡层，进而有效改善介质层与铜箔的结合力。
2.本发明所提供的三维成型PTFE基覆铜板，表现出低于2的介电常数，且介电损耗低于0.0016，表明更有利于信号的高速、低延迟、无损耗传输。同时，该覆铜板力学性能优异，剥离强度能达到2.32N/mm。
具体实施方式
为了使得本领域技术人员能够更加清楚地了解本发明的技术方案，以下将结合具体的实施例与对比例详细说明本发明的技术方案。
实施例1
本实施例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液（铜粉、钛粉、PTFE乳液的质量比为1:1:3）置于球磨机中，抽真空后进行球磨，球磨时间为50min，球磨转速为1000rpm，真空度为0 .5×10-2Pa，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol，石墨烯与无水乙醇溶液的质量比为1:100），置于80℃下热处理6h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在80℃热水浴中搅拌6h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S3：以铜箔为基底，将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，真空热压的压强为20MPa，时间为2h，温度为400℃，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.0001mm2，并将模型分层处理，打印时分层打印，层数为6层，层高10μm；
3D打印过程中的成型参数为：成形室温度：-20℃；针头针管温度：20℃；点胶针头内径10μm；挤出速度：200μm/s；剪切速度：15mm/s；
S5：将S4中3D打印后获得的材料先在-80℃条件下低温保存，再于0.02mbar、-55℃的环境下进行40h的冻干处理，得到三维成型PTFE基覆铜板。
实施例2
本实施例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液（铜粉、钛粉、PTFE乳液的质量比为1:1:3）置于球磨机中，抽真空后进行球磨，球磨时间为40min，球磨转速为1200rpm，真空度为0 .1×10-2Pa，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol，石墨烯与无水乙醇溶液的质量比为1:100），置于80℃下热处理5h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在85℃热水浴中搅拌5h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S3：以铜箔为基底，将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，真空热压的压强为10MPa，时间为3h，温度为450℃，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.04mm2，并将模型分层处理，打印时分层打印，层数为2层，层高200μm；
3D打印过程中的成型参数为：成形室温度：-20℃；针头针管温度：20℃；点胶针头内径100μm；挤出速度：400μm/s；剪切速度：15mm/s；
S5：将S4中3D打印后获得的材料先在-80℃条件下低温保存，再于0.05mbar、-50℃的环境下进行48h的冻干处理，得到三维成型PTFE基覆铜板。
实施例3
本实施例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液（铜粉、钛粉、PTFE乳液的质量比为1:1:3）置于球磨机中，抽真空后进行球磨，球磨时间为60min，球磨转速为1000rpm，真空度为0 .1×10-2Pa，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol，石墨烯与无水乙醇溶液的质量比为1:100），置于90℃下热处理5h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在80℃热水浴中搅拌5h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S3：以铜箔为基底，将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，真空热压的压强为15MPa，时间为2h，温度为450℃，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.0025mm2，并将模型分层处理，打印时分层打印，层数为5层，层高50μm；
3D打印过程中的成型参数为：成形室温度：-15℃；针头针管温度：25℃；点胶针头内径20μm；挤出速度：300μm/s；剪切速度：10mm/s；
S5：将S4中3D打印后获得的材料先在-90℃条件下低温保存，再于0.03mbar、-50℃的环境下进行45h的冻干处理，得到三维成型PTFE基覆铜板。
实施例4
本实施例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液（铜粉、钛粉、PTFE乳液的质量比为1:1:3）置于球磨机中，抽真空后进行球磨，球磨时间为40min，球磨转速为1100rpm，真空度为0.8×10-2Pa，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol，石墨烯与无水乙醇溶液的质量比为1:100），置于85℃下热处理6h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在85℃热水浴中搅拌5h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S3：以铜箔为基底，将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，真空热压的压强为20MPa，时间为2h，温度为430℃，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.01mm2，并将模型分层处理，打印时分层打印，层数为3层，层高100μm；
3D打印过程中的成型参数为：成形室温度：-15℃；针头针管温度：25℃；点胶针头内径50μm；挤出速度：200μm/s；剪切速度：10~15mm/s；
S5：将S4中3D打印后获得的材料先在-90℃条件下低温保存，再于0.02mbar、-55℃的环境下进行43h的冻干处理，得到三维成型PTFE基覆铜板。
对比例1
本对比例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol，石墨烯与无水乙醇溶液的质量比为1:100），置于80℃下热处理6h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在80℃热水浴中搅拌6h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S2：将溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在铜箔的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.0001mm2，并将模型分层处理，打印时分层打印，层数为6层，层高10μm；
3D打印过程中的成型参数为：成形室温度：-20℃；针头针管温度：20℃；点胶针头内径10μm；挤出速度：200μm/s；剪切速度：15mm/s；
S3：将S2中3D打印后获得的材料先在-80℃条件下低温保存，再于0.02mbar、-55℃的环境下进行40h的冻干处理，得到三维成型PTFE基覆铜板。
对比例2
本对比例提供一种三维成型PTFE基覆铜板的制备方法，具体步骤如下：
S1：将铜粉、钛粉、PTFE乳液（铜粉、钛粉、PTFE乳液的质量比为1:1:3）置于球磨机中，抽真空后进行球磨，球磨时间为50min，球磨转速为1000rpm，真空度为0 .5×10-2Pa，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将正硅酸乙酯、PTFE纤维溶于无水乙醇溶液（无水乙醇溶液的浓度为99.5%）中，滴入氨水充分反应后（正硅酸乙酯、PTFE纤维、氨水的摩尔比为2mol:50g:8mol，PTFE纤维与无水乙醇溶液的质量比为1:10），置于80℃下热处理6h，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合（正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L），在80℃热水浴中搅拌6h，待冷却后加入N,N-二甲基甲酰胺溶液，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1，继续搅拌后制得溶胶B；
S3：以铜箔为基底，将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，真空热压的压强为20MPa，时间为2h，温度为400℃，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
其中，三维网状模型的网眼面积为0.0001mm2，并将模型分层处理，打印时分层打印，层数为6层，层高10μm；
3D打印过程中的成型参数为：成形室温度：-20℃；针头针管温度：20℃；点胶针头内径10μm；挤出速度：200μm/s；剪切速度：15mm/s；
S5：将S4中3D打印后获得的材料先在-80℃条件下低温保存，再于0.02mbar、-55℃的环境下进行40h的冻干处理，得到三维成型PTFE基覆铜板。
表1为本发明中实施例1~4及对比例1、对比例2所制备的三维成型PTFE基覆铜板测得的性能数据：
表1
通过表1中的测试数据可知，实施例1~4所提供的三维成型PTFE基覆铜板表现出低于2的介电常数，且介电损耗低于0.0016，表明更有利于信号的高速、低延迟、无损耗传输。同时，实施例1~4所提供的三维成型PTFE基覆铜板剥离强度优异，表明本发明提供的制备方法有助于提升PTFE基覆铜板的力学性能。而对比例1、对比例2中的覆铜板，介电常数、介质损耗均偏高，且剥离强度偏低，表明过渡层的设置、石墨烯的引入对于三维成型PTFE基覆铜板的性能提升来说具有显著影响。
Claims (10)
1.一种三维成型PTFE基覆铜板的制备方法，其特征在于：包括以下具体步骤：
S1：将铜粉、钛粉、PTFE乳液置于球磨机中，抽真空后进行球磨，将球磨产物过滤、干燥、研磨，得到粉末A；
S2：将石墨烯、正硅酸乙酯、PTFE纤维溶于无水乙醇溶液中，滴入氨水充分反应后，进行热处理，然后过滤、洗涤得到前驱体；将前驱体、蒸馏水、乙醇、盐酸混合，在热水浴中搅拌，待冷却后加入N,N-二甲基甲酰胺溶液，继续搅拌，制得溶胶B；
S3：以铜箔为基底，将粉末A在其表面压制成膜，在铜箔上形成过渡层；
S4：将S2得到的溶胶B转移到注射器中，安装到3D打印设备上，使用三维软件对所需打印的复合材料建模，形成三维网状模型，将模型导入打印设备，在过渡层的基础上进行3D打印，形成介质层；
S5：将S4中3D打印后获得的材料进行冷冻干燥，得到三维成型PTFE基覆铜板。
2.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S1中，铜粉、钛粉、PTFE乳液的质量比为1:1:3；球磨时间为40~60min，球磨转速为1000~1200rpm，真空度为0.1×10-2Pa~1.0×10-2Pa。
3.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S2中，石墨烯、正硅酸乙酯、PTFE纤维、氨水的质量摩尔比为5g:2mol:50g:8mol；
无水乙醇溶液的浓度为99.5%，石墨烯与无水乙醇溶液的质量比为1:100。
4.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S2中，正硅酸乙酯、蒸馏水、乙醇、盐酸的摩尔比为1:4:6:0.05，盐酸的浓度为0.1mol/L，在80~85℃热水浴中搅拌5~6h；
热处理过程为：置于80~90℃下热处理5~6h。
5.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S2中，N,N-二甲基甲酰胺与正硅酸乙酯的摩尔比为1:1。
6.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S3中，压制过程为：将粉末A在铜箔上模压得到预压片，再将预压片继续真空热压，在铜箔上形成过渡层；
所述真空热压的压强为10~20MPa，时间为2~3h，温度为400~450℃。
7.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S4中，所述三维网状模型的网眼面积为0.0001~0.04mm2，并将模型分层处理，打印时分层打印，层数为2~6层，层高10~200μm。
8.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：步骤S4中，所述3D打印过程中的成型参数为：成形室温度：-20~-15℃；针头针管温度：20~25℃；点胶针头内径10~100μm；挤出速度：200~400μm/s；剪切速度：10~15mm/s。
9.如权利要求1所述的三维成型PTFE基覆铜板的制备方法，其特征在于：冷冻干燥为：先在≤-80℃条件下低温保存，再于0.02~0.05mbar、-55~-50℃的环境下进行40~48h的冻干处理。
10.权利要求1~9任一项所述的制备方法制备得到的三维成型PTFE基覆铜板。
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