CN113199834A - 一种热塑性覆铜板及制备方法 - Google Patents
一种热塑性覆铜板及制备方法 Download PDFInfo
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Abstract
本申请提供一种热塑性覆铜板及制备方法,该方法中,以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料;将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒;所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板;将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板。与现有技术相比,改性聚苯硫醚塑料薄板采用短玻璃纤维和无机填料增强,无机填料具有很好的均质特性,使得覆铜板的三个方向均具有较低的热膨胀系数。
Description
技术领域
本申请涉及高频电路板基材,具体涉及一种热塑性覆铜板及制备方法。
背景技术
随着第五代(5G)无线移动通信技术的发展和成熟,5G技术将与工业智能化、远程医疗、L4/L5自动驾驶以及车联网等深度融合,实现真正的“万物互联”。5G技术中,要求更小型化的基站设备和天线,更低的插入损耗(例如介质损耗和导体损耗),高可靠性。通常情况下,使用高频高速电路板制备基站设备、天线等5G连网设备,因此要求作为高频高速电路板的基材的覆铜板具备以下条件:(1)具有稳定的介电常数,使得电路板阻抗连续稳定;(2)介质损耗必须小,使得信号损耗较小;(3)与铜箔的热膨胀系数尽量一致,避免电路板在高温下因材料与铜箔的热膨胀系数不同而发生不同的膨胀,从而导致PTH(Plated ThroughHole,镀通孔工艺)过孔的可靠性失效。
覆铜板的结构参考图1所示的结构示意图,包括位于中间层的介质材料浸渍连续玻璃纤维布01,以及分布于介质材料浸渍连续玻璃纤维布01两侧的铜箔02。其中,介质材料可选用PTFE(Poly tetra fluoroethylene,聚四氟乙烯)、LCP(liquid crystal polymer,液晶聚合物)、碳氢树脂、改性环氧树脂以及GE树脂中的一种。在一种浸渍工艺中,选用不同热固性介质材料加入浸渍液,采用预固化方法制备成半固化片,然后按照厚度要求将半固化片和铜箔叠在一起,高温压合获得覆铜板。其中,半固化片由于浸渍有介质材料而具有介质材料的特性,从而满足5G要求。
PTFE由于具有极低的介电常数,较小的损耗介质损耗,成为目前主流的介质材料。PTFE的Z轴CTE(coefficient of thermal expansion,热膨胀系数)比铜高出一个数量级,由于现有玻璃纤维布浸渍工艺中,玻璃纤维布增强只在水平X轴和Y轴方向规则排列,在Z轴方向无任何补强作用,而且成型工艺单一,很难改善覆铜板的Z轴膨胀系数,导致难以满足5G技术对于覆铜板的要求。
发明内容
本申请提供一种热塑性覆铜板及制备方法,以解决现有介质材料浸渍连续玻璃纤维布获得的覆铜板难以满足Z轴膨胀系数要求的问题。
本申请的第一方面,提供一种热塑性覆铜板的制备方法,包括:
以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料;
将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒;
所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板;
将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板,其中,带胶铜箔所用胶为高频胶。
可选的,所述无机填料选自SiO2空心微球或中空石英粉。
可选的,所述无机填料还包括Al2O3或MgSiO3。
可选的,所述硅烷偶联剂在所述分散媒介的总量中所占质量比为2~10%。
可选的,纯水、乙醇以及硅烷偶联剂按重量比为纯水:乙醇:硅烷偶联剂=50:45:5混合。
可选的,无机填料、短玻璃纤维以及滑石粉按以下质量配比添加:
无机填料:3~10重量份;
短玻璃纤维:20~30重量份;
滑石粉:5~10重量份;
其中,基于1kg计为1重量份。
可选的,所述改性无机填料和聚苯硫醚塑料颗粒按质量比为改性无机填料:聚苯硫醚塑料颗粒=1:(1.5-2)混合。
可选的,所述短玻璃纤维的直径为5μm~15μm,长径比为(3~8):1。
可选的,所述热塑性覆铜板的单向尺寸最大为600mm,厚度为0.5mm~3mm。
本申请的第二方面,提供一种由第一方面任意一种可能实现方式提供的制备方法制备而成的热塑性覆铜板,包括:作为中间介质层的改性聚苯硫醚塑料薄板;覆盖于所述中间介质层两面的铜箔;以及设置于所述中间介质层和所述铜箔之间的高频胶;所述高频胶用于粘合所述中间介质层和所述铜箔。
由以上技术方案可知,本申请提供一种热塑性覆铜板及制备方法,该方法中,以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料;将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒;所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板;将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板。采用该方法制备而成的覆铜板具有优异的机械性能和热稳定性以及介电稳定性。与现有技术相比,本申请提供的改性PPS薄板作为中间介质层,且改性PPS薄板采用短玻璃纤维和无机填料增强,解决了四氟乙烯浸渍连续玻璃纤维布覆铜板只在水平方向提供较低的膨胀系数的问题。本申请中间介质层是由大量的是短玻璃纤维和无机填料增强,无机填料具有很好的均质特性,使得覆铜板的三个方向均具有较低的热膨胀系数,均介于20ppm~30ppm。
附图说明
为了更清楚地说明本申请的技术方案,下面将对实施例中所需要使用的附图作简单地介绍,显而易见地,对于本领域普通技术人员而言,在不付出创造性劳动的前提下,还可以根据这些附图获得其他的附图。
图1为现有技术提供的覆铜板的结构示意图;
图2为本申请实施例提供的一种热塑性覆铜板的制备方法的工艺流程图;
图3为本申请实施例提供的压合过程中的层叠结构的结构示意图;
图4为本申请实施例提供的一种热塑性覆铜板的结构示意图。
具体实施方式
下面将结合本申请实施例中的附图,对本申请实施例中的技术方案进行清楚、完整的描述,显然,所描述的实施例仅仅是本申请一部分实施例,而不是全部的实施例。基于本申请中的实施例,本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例,都属于本申请保护的范围。
现有浸渍工艺中,如果选用碳氢树脂作为介质材料,获得的覆铜板高频基材可以很好地改善Z轴膨胀系数,且提供极低的DK(介电常数)和DF(介质损耗),但是目前具备以上技术能力且可以量产商业化的的厂商主要是美国罗杰斯,Isola,且碳氢树脂核心专利和技术把控在日本和美国企业中。国内生益科技、华正新材等覆铜板企业可以提供覆铜技术,但核心材料供应链不可控,因此亟需国产替代,但短期内国内很难提供优异的热固性树脂方案替代美国碳氢树脂方案。
基于此,本申请实施例提供一种热塑性覆铜板的制备方法,该制备方法的工艺流程图如图2所示,包括以下步骤:
步骤101,以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料。
所述无机填料选自SiO2空心微球或中空石英粉。其中,SiO2空心球能够降低聚苯硫醚的Dk和Df,且能够改善聚苯硫醚挤出制备而成的薄板的尺寸稳定性,空心球典型的可选3M公司的iM30k。
所述短玻璃纤维的直径为5μm~15μm,长径比为(3~8):1。短玻璃纤维填充的主要目的是改性聚苯硫醚的机械强度,耐热性以及热膨胀系数。
步骤101中添加的无机填料除了包括用于改善聚苯硫醚的Dk和Df的SiO2空心微球或中空石英粉以外,还可以包括Al2O3或MgSiO3。添加Al2O3或MgSiO3可以改善材料的热导率以及挤出加工性能。
硅烷偶联剂一端的硅氧键和无机填料表面通过分子间作用力结合,使得硅烷偶联剂附着在无机填料表面,硅烷偶联剂另一端的极性分子改善无机填料在PPS(Phenylenesulfide,聚醚类塑料)的分布,减小无机物和有机高分子之间的界面作用,从而减低改性材料的Dk和Df。硅烷偶联剂可选KH560,KH570,或者其他酞酸酯系列偶联剂,比如:美国肯瑞奇公司的KR238S,一种双(二辛氧基焦磷酸酯)乙撑酞酸酯。
本申请实施例中,所述硅烷偶联剂在所述分散媒介的总量中所占质量比为2~10%。
可选的,纯水、乙醇以及硅烷偶联剂按重量比为纯水:乙醇:硅烷偶联剂=50:45:5混合。
可选的,无机填料、短玻璃纤维以及滑石粉按以下质量配比添加:无机填料:3~10重量份;短玻璃纤维:20~30重量份;滑石粉:5~10重量份;其中,基于1kg计为1重量份。
可选的,所述改性无机填料和聚苯硫醚塑料颗粒按质量比为改性无机填料:聚苯硫醚塑料颗粒=1:(1.5-2)混合。
步骤102,将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒。
该步骤中,挤出改性选用常规的PPS挤出机,挤出后切割得到改性PPS粒料,即改性聚苯硫醚塑料颗粒。
步骤103,所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板。
该步骤中,PPS注塑后用真空高温压机热压合覆铜。改性后的PPS粒料可选用传统的注塑工艺制备改性PPS薄板作为高频覆铜板的中间介质层,注塑机可选日本日钢J650AD大型卧室注塑机。
本申请实施例推荐的注塑工艺参数如下:PPS粒料的干燥温度120℃~150℃,干燥时间2h;模具温度:120℃~140℃;溶胶温度:320℃~330℃;注射压力:100-150MPa;螺杆类别:标准螺杆;注射速度:中高速;回料速度:50-80rpm。
本申请实施例推荐的挤出工艺参数如下:分三区对料筒加温,使熔体保持一定黏度成型,即:一区:295-310℃;二区:310-320℃;三区:300-310℃;接头:290-300℃;挤出螺杆速度:8-10r/min。
步骤104,将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板,其中,带胶铜箔所用胶为高频胶。
该步骤中,热辊压工艺所用压机可选德国LAUFFER制造的一种油压式高温压机,型号为RMV2100。利用高温导热油,使真空高温压机的油压温度最高可达400℃且稳定。压合温度和压力参考高频胶固化参数。高频胶固化推荐参数:温度最高不超过220℃;升温速率推荐4℃~10℃/min;180~220℃保温1~2小时;然后降温到室温,降温速率不要超过升温速率。
铜箔可选电解铜箔、压延铜箔、反转铜箔以及低轮廓电解铜箔,厚度可选18um,35um或70um。
压合过程中的层叠结构参考图3所示的结构示意图。在该层叠结构中,核心层是位于中间的改性PPS薄板1,改性PPS薄板1上下叠铜箔2,然后叠缓冲层3和钢板4作为辅助压合材料。其中,缓冲层是为了防止压合过程中改性PPS薄板变形或者受损而设置。
通过上述工艺制备而成的热塑性覆铜板的单向尺寸最大为600mm,厚度为0.5mm~3mm。
本申请实施例中,使用PPS挤出-热辊压连续覆铜工艺替代传统覆铜行业中高温油压机传压工艺,可卷对卷连续生产,极大提高了覆铜效率。也就是说,在挤出机挤出改性PPS薄板后立即将板材和已经配套准备好的带胶铜箔共同对接入高温压机压延,得到覆铜板。高温压机可选金属辊或者硅橡胶辊,温度推荐使用180℃~220℃,辊间隙根据覆铜板厚度要求设置。
由以上技术方案可知,本申请实施例提供一种热塑性覆铜板的制备方法,该方法中,以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料;将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒;所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板;将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板。采用该方法制备而成的覆铜板具有优异的机械性能和热稳定性以及介电稳定性。与现有技术相比,本申请提供的改性PPS薄板作为中间介质层,且改性PPS薄板采用短玻璃纤维和无机填料增强,解决了四氟乙烯浸渍连续玻璃纤维布覆铜板只在水平方向提供较低的膨胀系数的问题。本申请中间介质层是由大量的是短玻璃纤维和无机填料增强,无机填料具有很好的均质特性,使得覆铜板的三个方向均具有较低的热膨胀系数,均介于20ppm~30ppm。
参考图4所示的结构示意图,本申请实施例提供一种热塑性覆铜板,包括:作为中间介质层的改性聚苯硫醚塑料薄板5;覆盖于所述中间介质层两面的铜箔7;以及设置于所述中间介质层5和所述铜箔7之间的高频胶6;所述高频胶6用于粘合所述中间介质层和所述铜箔。
在热塑性覆铜板中,改性聚苯硫醚塑料薄板采用短玻璃纤维和无机填料增强,解决了四氟乙烯浸渍连续玻璃纤维布覆铜板只在水平方向提供较低的膨胀系数的问题。本申请中间介质层是由大量的是短玻璃纤维和无机填料增强,无机填料具有很好的均质特性,使得覆铜板的三个方向均具有较低的热膨胀系数。
以上结合具体实施方式和范例性实例对本申请进行了详细说明,不过这些说明并不能理解为对本申请的限制。本领域技术人员理解,在不偏离本申请精神和范围的情况下,可以对本申请技术方案及其实施方式进行多种等价替换、修饰或改进,这些均落入本申请的范围内。本申请的保护范围以所附权利要求为准。
Claims (10)
1.一种热塑性覆铜板的制备方法,其特征在于,包括:
以纯水、乙醇以及硅烷偶联剂为分散媒介,加入无机填料、短玻璃纤维以及滑石粉,经高速搅拌后,过滤、烘干,制成改性无机填料;
将所述改性无机填料和聚苯硫醚塑料颗粒混合挤出造粒,制成改性聚苯硫醚塑料颗粒;
所述改性聚苯硫醚塑料颗粒经过注塑、挤出,得到改性聚苯硫醚塑料薄板;
将所述改性聚苯硫醚塑料薄板作为中间介质层,采用热辊压工艺在所述中间介质层的两面覆盖带胶铜箔,经压合后形成热塑性覆铜板,其中,带胶铜箔所用胶为高频胶。
2.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,所述无机填料选自SiO2空心微球或中空石英粉。
3.根据权利要求2所述的热塑性覆铜板的制备方法,其特征在于,所述无机填料还包括Al2O3或MgSiO3。
4.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,所述硅烷偶联剂在所述分散媒介的总量中所占质量比为2~10%。
5.根据权利要求4所述的热塑性覆铜板的制备方法,其特征在于,纯水、乙醇以及硅烷偶联剂按重量比为纯水:乙醇:硅烷偶联剂=50:45:5混合。
6.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,无机填料、短玻璃纤维以及滑石粉按以下质量配比添加:
无机填料: 3~10重量份;
短玻璃纤维: 20~30重量份;
滑石粉: 5~10重量份;
其中,基于1kg计为1重量份。
7.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,所述改性无机填料和聚苯硫醚塑料颗粒按质量比为改性无机填料:聚苯硫醚塑料颗粒=1:(1.5-2)混合。
8.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,所述短玻璃纤维的直径为5μm~15μm,长径比为(3~8):1。
9.根据权利要求1所述的热塑性覆铜板的制备方法,其特征在于,所述热塑性覆铜板的单向尺寸最大为600mm,厚度为0.5mm~3mm。
10.一种由权利要求1~9中任一项所述制备方法制备而成的热塑性覆铜板,其特征在于,包括:作为中间介质层的改性聚苯硫醚塑料薄板;覆盖于所述中间介质层两面的铜箔;以及设置于所述中间介质层和所述铜箔之间的高频胶;所述高频胶用于粘合所述中间介质层和所述铜箔。
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