CN109575482B - 一种用于高频覆铜板的基板材料及其制备方法 - Google Patents

一种用于高频覆铜板的基板材料及其制备方法 Download PDF

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CN109575482B
CN109575482B CN201811429961.9A CN201811429961A CN109575482B CN 109575482 B CN109575482 B CN 109575482B CN 201811429961 A CN201811429961 A CN 201811429961A CN 109575482 B CN109575482 B CN 109575482B
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张启龙
王浩
杨辉
朱志才
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Abstract

本发明涉及基板材料制备,旨在提供一种用于高频覆铜板的基板材料及其制备方法。该基板材料由(100‑x)wt%的聚四氟乙烯和x wt%的改性Li2TiO3组成,其中30≤x≤70;所述改性Li2TiO3的化学式为(0.92‑a)Li2TiO3‑aMgO‑0.08LiF,其中0≤a≤0.175。本发明的基板材料具有优异的介电性能和低的热膨胀系数(12ppm/℃~77ppm/℃),可用于高频覆铜板的制作。本发明操作简单,无需特殊设备和繁琐的实验流程,生产成本低,普适性强,具有很好的工业化基础和应用前景。

Description

一种用于高频覆铜板的基板材料及其制备方法
技术领域
本发明涉及一种适用于高频覆铜板的基板材料及其制备方法,属于材料科学与工程领域。
背景技术
随着电子科技及信息行业的高速发展,电子产品朝着高密度化、多功能化及信号传输高频化、高速化方向发展。印制电路板(PCB)是电子设备的血脉,电子信号通过PCB电路中的电流传输。为了适应高频和高速数据传输的需要,除了在电路设计和PCB制造方面的要求外,高性能的电路基材至关重要。针对电信号的损失,为PCB增加速度和信号的完整性,PCB基材需要选用低介电常数和介质损耗的材料。而普通的PI和FR-4基材在高频信号的传输中会较大程度的影响信号的完整性。高频覆铜板综合了有机基板和陶瓷基板的优势,具有介电性能优异、成本低、易加工等特点,在卫星通信、5G通信、电子导航、雷达系统等电子行业具有极大的应用前景。
为满足电子设备的高频高速要求,高频覆铜板的基板材料应具有较低的介电常数、低的介电损耗,同时还要兼具与铜箔相匹配的热膨胀系数和高热稳定性。聚四氟乙烯(PTFE)具有低介电常数、低介电损耗、高化学和热学稳定性等特点,是高频基板最为理想的有机基体材料。然而,PTFE存在热膨胀系数大(~109ppm/℃)、导热率低、附着能力差等问题,限制了其应用拓展,需要进行改性以满足实际使用要求。
目前,采用陶瓷、玻纤等无机填料填充PTFE制备复合材料已成为最常用的改性方法,并取得的了一定成效,已开发出介电常数2~4和介电常数10左右的基板材料,但介电常数在4~8之间的基板材料研究较少。Rogers公司虽开发了RT/duroid6006,RO3006和RO3206三种介电常数为6.15±0.15的高频基板,但它们具有非常大的介电常数温度系数,分别为-410ppm/℃,-262ppm/℃和-212ppm/℃。电路系统为了补偿介电常数的较大温度系数所造成的变化,需要额外的电路或机械结构,但这会增加设备的尺寸和成本。因此,开发低介质损耗、介电常数4-8、低介电常数温度系数的高频基板材料具有重要的意义。
发明内容
本发明要解决的问题是,克服现有技术的不足,提供一种用于高频覆铜板的基板材料及其制备方法。
为解决技术问题,本发明解决方案是:
提供一种用于高频覆铜板的基板材料,该基板材料由(100-x)wt%(质量百分比)的聚四氟乙烯和x wt%的改性Li2TiO3组成,其中30≤x≤70;所述改性Li2TiO3的化学式为(0.92-a)Li2TiO3-aMgO-0.08LiF,其中0≤a≤0.175。
本发明进一步提供了前述基板材料的制备方法,包括以下步骤:
(1)按照摩尔比例(0.92-a)∶(0.92-a)∶a∶0.08,取粉末状原料Li2CO3、TiO2、MgO和LiF,其中0≤a≤0.175;混合均匀后在950℃烧结4h;进一步研磨后,得到陶瓷填料;
(2)按照质量比例40~50∶1,取陶瓷填料和含氟偶联剂;将陶瓷填料分散在乙醇中后,加入含氟偶联剂;在30℃下搅拌4h,经烘干处理,得到含氟偶联剂修饰的陶瓷填料,即改性Li2TiO3
(3)向聚四氟乙烯乳液中加入改性Li2TiO3,搅拌分散均匀,得到混合分散液;
(4)向混合分散液中加入乙醇,继续搅拌4h,经静置、过滤后,在120℃下烘干4h,得到聚四氟乙烯与改性Li2TiO3的混合物;
(5)将聚四氟乙烯和改性Li2TiO3的混合物用球磨机破碎成粉末,再经模压、烧结制备得到用于高频覆铜板的基板材料。
本发明中,所述步骤(1)中,进一步研磨时,研磨至粒度为1~3μm。
本发明中,所述步骤(2)中,将陶瓷填料分散在乙醇中时,控制乙醇与陶瓷填料质量比为5∶1;烘干温度为120℃。
本发明中,所述步骤(2)中,含氟偶联剂是下述的任意一种:全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷、全氟辛基三乙氧基硅烷;含氟偶联剂的质量浓度为1.33g/cm3,质量分数为97%。
本发明中,所述步骤(3)中,控制聚四氟乙烯乳液和改性Li2TiO3的用量,使步骤(5)最终获得的基板材料中,聚四氟乙烯与改性Li2TiO3的质量比为(100-x)∶x,30≤x≤70。
本发明中,所述步骤(3)中,所述聚四氟乙烯乳液的质量浓度为1.51g/cm3,质量分数为60%。
本发明中,所述步骤(4)中,向混合分散液中加入乙醇时,乙醇的添加量是混合分散液质量的15%。
本发明中,所述步骤(5)中,用球磨机破碎成粉末时,控制球磨机转速为300r/min,球磨后的粉末粒径为200~400μm。
本发明中,所述步骤(5)中,控制模压压力为100kg/cm2,模压时间为5min;烧结的温度为380℃。
与现有技术相比,本发明的有益效果是:
1、本发明所提供的基板材料,具有优异的介电性能:介电常数4~8、低的介电损耗(tanδ≤0.002),低的介电常数温度系数(-165ppm/℃~+9ppm/℃);同时具有低的热膨胀系数(12ppm/℃~77ppm/℃),可用于高频覆铜板的制作。
2、本发明操作简单,无需特殊设备和繁琐的实验流程,生产成本低,普适性强,具有很好的工业化基础和应用前景。
具体实施方式
本发明将参照下述的实施例进一步详细说明,但这些实施例并不是为了限制本发明的范围。
本发明中,用于高频覆铜板的基板材料是由(100-x)wt%(质量百分比)的聚四氟乙烯和x wt%的改性Li2TiO3组成,其中30≤x≤70;所述改性Li2TiO3的化学式为(0.92-a)Li2TiO3-aMgO-0.08LiF,其中0≤a≤0.175。
制备该基板材料的制备方法,包括以下步骤:
(1)按照摩尔比例(0.92-a)∶(0.92-a)∶a∶0.08,取粉末状原料Li2CO3、TiO2、MgO和LiF,其中0≤a≤0.175;混合均匀后在950℃烧结4h;进一步研磨至粒度为1~3μm,得到陶瓷填料,即改性Li2TiO3
(2)按照质量比例40~50∶1,取陶瓷填料和含氟偶联剂;将陶瓷填料分散在乙醇中,控制乙醇与陶瓷填料质量比为5∶1;加入含氟偶联剂,在30℃下搅拌4h,经120℃烘干处理,得到含氟偶联剂修饰的陶瓷填料,即改性Li2TiO3;含氟偶联剂是下述的任意一种:全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷、全氟辛基三乙氧基硅烷;含氟偶联剂的质量浓度为1.33g/cm3,质量分数为97%。
(3)向PTFE乳液中加入含氟偶联剂修饰的陶瓷填料,搅拌分散均匀,得到混合分散液;PTFE乳液的质量浓度为1.51g/cm3,质量分数为60%。控制聚四氟乙烯乳液和改性Li2TiO3的用量,使步骤(5)最终获得的基板材料中,聚四氟乙烯与改性Li2TiO3的质量比为(100-x)∶x,30≤x≤70。
(4)向混合分散液中加入乙醇,乙醇的添加量是混合分散液质量的15%;继续搅拌4h,经静置、过滤后,在120℃下烘干4h,得到PTFE和改性Li2TiO3的混合物;
(5)将PTFE和改性填料的混合物用球磨机破碎成粉末,再经模压、烧结制备得到用于高频覆铜板的基板材料。该步骤中,控制球磨机转速为300r/min,球磨后的粉末粒径为200~400μm。模压压力为100kg/cm2,模压时间为5min;烧结的温度为380℃。表1为各实施例中不同配方组成及制备过程的控制参数:
表2为各实施例中不同配方的组成与性能表
从表2中可以看出,本发明所提供的基板材料具有低的介电损耗(tanδ≤0.002),较稳定的介电常数温度系数(-165ppm/℃~+9ppm/℃)和低的热膨胀系数(12ppm/℃~77ppm/℃),而且操作简单、无繁琐实验流程;因此符合高频覆铜板的制作要求。

Claims (9)

1.一种用于高频覆铜板的基板材料,其特征在于,该基板材料由(100-x)wt%的聚四氟乙烯和x wt%的改性Li2TiO3组成,其中30≤x≤70;所述改性Li2TiO3的化学式为(0.92-a)Li2TiO3-aMgO-0.08LiF,其中0≤a≤0.175。
2.权利要求1所述基板材料的制备方法,其特征在于,包括以下步骤:
(1)按照摩尔比例(0.92-a)∶(0.92-a)∶a∶0.08,取粉末状原料Li2CO3、TiO2、MgO和LiF,其中0≤a≤0.175;混合均匀后在950℃烧结4h;进一步研磨后,得到陶瓷填料;
(2)按照质量比例40~50∶1,取陶瓷填料和含氟偶联剂;将陶瓷填料分散在乙醇中后,加入含氟偶联剂;在30℃下搅拌4h,经烘干处理,得到含氟偶联剂修饰的陶瓷填料,即改性Li2TiO3
(3)向聚四氟乙烯乳液中加入改性Li2TiO3,搅拌分散均匀,得到混合分散液;控制聚四氟乙烯乳液和改性Li2TiO3的用量,使步骤(5)最终获得的基板材料中,聚四氟乙烯与改性Li2TiO3的质量比为(100-x)∶x,30≤x≤70;
(4)向混合分散液中加入乙醇,继续搅拌4h,经静置、过滤后,在120℃下烘干4h,得到聚四氟乙烯与改性Li2TiO3的混合物;
(5)将聚四氟乙烯和改性Li2TiO3的混合物用球磨机破碎成粉末,再经模压、烧结制备得到用于高频覆铜板的基板材料。
3.根据权利要求2所述的方法,其特征在于,所述步骤(1)中,进一步研磨时,研磨至粒度为1~3μm。
4.根据权利要求2所述的方法,其特征在于,所述步骤(2)中,将陶瓷填料分散在乙醇中时,控制乙醇与陶瓷填料质量比为5∶1;烘干温度为120℃。
5.根据权利要求2所述的方法,其特征在于,所述步骤(2)中,含氟偶联剂是下述的任意一种:全氟癸基三甲氧基硅烷、全氟癸基三乙氧基硅烷、全氟辛基三乙氧基硅烷;含氟偶联剂的质量浓度为1.33g/cm3,质量分数为97%。
6.根据权利要求2所述的方法,其特征在于,所述步骤(3)中,所述聚四氟乙烯乳液的质量浓度为1.51g/cm3,质量分数为60%。
7.根据权利要求2所述的方法,其特征在于,所述步骤(4)中,向混合分散液中加入乙醇时,乙醇的添加量是混合分散液质量的15%。
8.根据权利要求2所述的方法,其特征在于,所述步骤(5)中,用球磨机破碎时,控制球磨机转速为300r/min,球磨后的粉末粒径为200~400μm。
9.根据权利要求2所述的方法,其特征在于,所述步骤(5)中,控制模压压力为100kg/cm2,模压时间为5min;烧结的温度为380℃。
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