CN108456387B - 一种无玻纤型聚四氟乙烯胶片、制作方法及其应用 - Google Patents
一种无玻纤型聚四氟乙烯胶片、制作方法及其应用 Download PDFInfo
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Abstract
本发明公开了一种无玻纤型聚四氟乙烯胶片、制作方法及其应用。本发明无玻纤型聚四氟乙烯胶片的制作方法包括:(1)将填料与有机助剂相混合,通过搅拌充分混合均匀,烘干后得到表面改性的填料;(2)将改性后的填料和聚四氟乙烯粉料进行混合,使改性后的填料均匀分散在聚四氟乙烯中,得到混合物料;(3)将混合物料加热熔融挤出,均匀涂覆于柔性金属箔上,经过高温烘烤烧结成膜后分离,得到无玻纤型聚四氟乙烯胶片。本发明无玻纤型聚四氟乙烯胶片的制备方法简单、易行,易于大规模生产,且用于生产覆铜板,制备得到的覆铜箔基板具有均一的介电性能和优异的尺寸稳定性等优点。
Description
技术领域
本发明属于覆铜板技术领域,特别是涉及一种无玻纤型聚四氟乙烯胶片、制作方法及其应用。
背景技术
印刷电路用覆铜板是一种极其重要的电子工业基础材料。传统的覆铜板都是用来制造印刷电路板,对电子元器件起到制成和互相连接、互相绝缘的作用。近年来,有些特种覆铜板也用来直接制造印刷电子元器件。由于电子产品的小型、轻量、薄型化,迫使印刷电路板必须具备种种高质量和高技术特性,使印刷电路板制造技术直接涉及到当代多种高新技术,其最主要、最重要的材料覆铜板,也就必须随之具备种种高质量和高技术特性,因此,覆铜板在电子信息产业中的地位变的越来越重要,一个国家的覆铜板技术水平,也是制约该国家电子信息产业发展的因素之一。
传统的电子电路用覆铜板基板的生产工艺为玻璃纤维布浸渍胶液,经烘箱烘烤制备得到胶片,再裁切、叠配、压合,最终成型得到覆铜板。为了提高覆铜板的性能,以及改善覆铜板制备工艺流程,现有技术中对传统覆铜板工艺作出了进一步改进。
中国专利公开CN107509312A采用经过不同工艺烧结煅烧、不同粒径混合等特殊工艺处理的硅酸镁、氧化钛、钛酸锶、钛酸钙、钛酸镁、钛酸钡等粉料混合作为填料制作覆铜板,得到的覆铜板介电常数高且损耗低。
中国专利公开CN104943267A采用介电常数更低的二氧化硅气凝胶为填料,大大降低了基板的介电常数,同时通过对聚四氟乙烯进行改性处理,降低了聚四氟乙烯的热膨胀系数,提高了铜箔和玻璃纤维布的粘结性。上述技术都是基于填料、树脂进行的改进。
覆铜板通常采用玻纤布作为增强材料,所以覆铜板的介电常数、介质损耗因子不但与玻纤布的种类有关,还与玻纤布本身的的厚度及厚度均匀性等性质有很大关联。由于玻纤布在水平经纬方向给板子提供了一定的力学强度,但是在竖直方向提供的力学支撑就没有水平方向上那么明显,这就造成板子的尺寸稳定性在水平和竖直方向存在较大的差异,最直观的差异体现就是板材Z-CTE值较X/Y-CTE值要大很多。
作为高频覆铜板,最为核心的性能指标就是介电性能,而使用玻纤布增强制备出来的高频板往往存在着介电性能均一性较差的问题。众所周知,玻纤布的编织都存在空洞和经纬交叉点,而常规PTFE高频板的介电性能跟PTFE与玻纤布的比例有紧密关系,因此这就造成玻纤布空洞位置和经纬交叉点位置的介电性能不一致,这会对高频板后续的加工和线路设计造成困扰,对终端的应用会造成更严重的影响。
因此急需寻求新思路和新工艺来开发高频胶片,本发明借鉴复合材料的成型工艺,使用无机填料代替玻纤布来增强制备出高频胶片。
发明内容
本发明的目的在于提供一种无玻纤型聚四氟乙烯胶片、制作方法及其应用。本发明无玻纤型聚四氟乙烯胶片的制备方法简单、易行,易于大规模生产,且用于生产覆铜板,制备得到的覆铜箔基板具有均一的介电性能和优异的尺寸稳定性等优点。
为了达到上述的目的,本发明采取以下技术方案:
一种无玻纤型聚四氟乙烯胶片的制作方法,包括以下步骤:
(1)将填料与有机助剂相混合,通过搅拌充分混合均匀,烘干后得到表面改性的填料;
(2)将步骤(1)改性后的填料和聚四氟乙烯粉料进行混合,使改性后的填料均匀分散在聚四氟乙烯中,得到混合物料;
(3)将步骤(2)的混合物料加热熔融挤出,均匀涂覆于柔性金属箔上,经过高温烘烤烧结成膜后分离,得到无玻纤型聚四氟乙烯胶片。
在上述方法中,通过填料替代传统的玻璃纤维板,以克服“玻纤布效应”,进一步地,所述填料包括二氧化硅、二氧化钛、二氧化铝、钛酸钡、氮化硼、硫酸钡、碳酸钙中的一种或多种,优选二氧化硅、二氧化钛、二氧化铝。
在上述方法中,进一步地,所述有机助剂包括分散剂、偶联剂、表面活性剂、稳定剂、增韧剂、滑爽剂中的一种或多种,优选分散剂、偶联剂、表面活性剂、稳定剂,有机助剂能够完全包覆于无机填料表面,以提高无机填料与聚四氟乙烯的相容性。
在上述方法中,进一步地,各个组份在无玻纤型聚四氟乙烯胶片中所占的质量比如下:聚四氟乙烯25~75%,填料25~80%,助剂0.5%~5%。
在上述方法中,进一步地,所述步骤(2)通过高速混料机进行混合。
在上述方法中,进一步地,所述步骤(3)为:将步骤(2)的混合物料加热熔融,通过高压挤出,均匀涂覆于柔性金属箔上,经过卧式高温烤箱高温烘烤烧结成膜后,再逐级降温,完成最终烧成膜与金属箔分离。
进一步地,所述卧式高温烤箱的温度控制程序如下:第一高温段:控制温度为350-390℃,使聚四氟乙烯充分烧结,并使之与改性的无机填料充分混合均匀,排除内部细微气泡,保持时间为40~150min;第二中温段:控制温度为200-350℃,主要使聚四氟乙烯分子链重新排列,同时释放内应力,保持时间为60~200min;第三降温段:控制温度为80-200℃,保持时间为50~120min,让成型的胶片冷却,使其与金属箔分离。得到的无玻纤型聚四氟乙烯胶片具有很好的尺寸稳定性,无机填料分布均匀,且胶片电气性能优越。
本发明另提供一种通过上述制备方法制备得到的无玻纤型聚四氟乙烯胶片。
本发明还提供一种上述制备方法制备得到的无玻纤型聚四氟乙烯胶片在覆铜板中的应用。
本发明具有以下技术特点:
1)本发明创造性的使用无机填料代替传统增强材料玻纤布,打破了传统覆铜板行业通过浸渍工艺制备胶片的固有思路,制作方法简单、易行,易于大规模生产。
2)本发明生产的无玻纤型聚四氟乙烯胶片生产出的高频覆铜箔基板具有均一的介电性能和优异的尺寸稳定性。
具体实施方式
以下具体实施例是对本发明提供的方法与技术方案的进一步说明,但不应理解成对本发明的限制。
实施例1:一种无玻纤型聚四氟乙烯胶片的制作方法:
(1)称取150g填料二氧化硅与4.5g有机助剂硅烷偶联剂相混合,通过搅拌充分混合均匀,烘干后得到表面改性的填料;
(2)将步骤(1)改性后的填料和500g聚四氟乙烯粉料通过高速混料机进行混合,使改性后的填料均匀分散在聚四氟乙烯中,得到混合物料;
(3)将步骤(2)的混合物料加热熔融,通过高压挤出,均匀涂覆于柔性金属箔上,经过卧式高温烤箱高温烘烤烧结成膜后,再逐级降温,完成最终烧成膜与金属箔分离。
其中,卧式高温烤箱的温度控制程序如下:第一高温段:控制温度为365~380℃,使聚四氟乙烯充分烧结,并使之与改性的无机填料充分混合均匀,排除内部细微气泡,保持时间为80min;第二中温段:控制温度为200~250℃,主要使聚四氟乙烯分子链重新排列,同时释放内应力,保持时间为120min;第三降温段:控制温度为100~130℃,保持时间为60min,让成型的胶片冷却,使其与金属箔分离。
实施例2:将实施例1所得胶片通过如下方法制备覆铜板:
(1)根据客户不同介电性能和规格厚度的需求,利用特定的计算模型来算出叠配结构;
(2)根据叠配结构,进行板材叠制,上下表面覆上铜箔;
(3)将叠配好的材料送至高温真空热压机进行压合,压合温度380℃,压合压力60kg/cm2,保温保压时长为2h,即得到无玻纤型高频覆铜板。
对比例:玻璃纤维布型高频覆铜板的制备方法如下:
(1)将玻纤布通过装有PTFE乳液的胶槽,在玻纤布两侧浸渍上PTFE乳液,然后进入烤箱进行烘烤、冷却,最终得到含玻纤布的PTFE胶片(胶含量为60%);
(2)随后将制得的胶片根据先前设计的叠配结构进行叠配,然后送入高温真空热压机进行压合,压合温度380℃,压合压力30kg/cm2,保温保压时长为2h,即得到玻璃纤维布型高频覆铜板。
实施例2与对比例所制备得到的高频覆铜板的性能测定结果如下:
测试项目 | 无玻纤型高频覆铜板 | 玻璃纤维布型高频覆铜板 |
Dk@10GHz | 3.0 | 3.0 |
Df@10GHz | 0.0011 | 0.0019 |
Z-CTE(ppm/℃) | 24 | 62 |
从上述结果可以看出,本发明生产的无玻纤型聚四氟乙烯胶片生产出的高频覆铜箔基板具有优异的介电性能和尺寸稳定性。
以上实施例的说明只是用于帮助理解本发明方法及其核心思想。应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明原理的前提下,还可以对本发明进行若干改进和修饰,这些改进和修饰也落入本发明权利要求保护范围内。
Claims (6)
1.一种无玻纤型聚四氟乙烯胶片的制作方法,其特征如下,包括以下步骤:
(1)将填料与有机助剂相混合,通过搅拌充分混合均匀,烘干后得到表面改性的填料;
(2)将步骤(1)改性后的填料和聚四氟乙烯粉料进行混合,使改性后的填料均匀分散在聚四氟乙烯中,得到混合物料;各个组份在无玻纤型聚四氟乙烯胶片中所占的质量比如下:聚四氟乙烯25~75%,填料25~80%,助剂0.5%~5%,各原料用量之和为100%;
(3)将步骤(2)的混合物料加热熔融,通过高压挤出,均匀涂覆于柔性金属箔上,经过卧式高温烤箱高温烘烤烧结成膜后,再逐级降温,完成最终烧成膜与金属箔分离,得到无玻纤型聚四氟乙烯胶片;
所述卧式高温烤箱的温度控制程序如下:第一高温段:控制温度为350-390℃,保持时间为40~150min;第二中温段:控制温度为200-350℃,保持时间为60~200min;第三降温段:控制温度为80-200℃,保持时间为50~120min,让成型的胶片冷却,使其与金属箔分离。
2.如权利要求1所述的制作方法,其特征在于,所述填料包括二氧化硅、二氧化钛、钛酸钡、氮化硼、硫酸钡、碳酸钙中的一种或多种。
3.如权利要求1所述的制作方法,其特征在于,所述有机助剂包括分散剂、偶联剂、表面活性剂、稳定剂、增韧剂、滑爽剂中的一种或多种。
4.如权利要求1所述的制作方法,其特征在于,所述步骤(2)通过高速混料机进行混合。
5.如权利要求1-4任一项所述的制作方法制作得到的无玻纤型聚四氟乙烯胶片。
6.如权利要求5所述的无玻纤型聚四氟乙烯胶片在覆铜板中的应用。
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