CN114536923B - 一种高介电常数的含氟树脂基高导热高频覆铜板 - Google Patents
一种高介电常数的含氟树脂基高导热高频覆铜板 Download PDFInfo
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- CN114536923B CN114536923B CN202210323995.XA CN202210323995A CN114536923B CN 114536923 B CN114536923 B CN 114536923B CN 202210323995 A CN202210323995 A CN 202210323995A CN 114536923 B CN114536923 B CN 114536923B
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- fluorine
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 229910052731 fluorine Inorganic materials 0.000 title claims abstract description 107
- 239000011737 fluorine Substances 0.000 title claims abstract description 107
- 239000011347 resin Substances 0.000 title claims abstract description 94
- 229920005989 resin Polymers 0.000 title claims abstract description 94
- 239000000203 mixture Substances 0.000 claims abstract description 35
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- 239000006185 dispersion Substances 0.000 claims abstract description 20
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011889 copper foil Substances 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 239000000839 emulsion Substances 0.000 claims description 41
- 239000007822 coupling agent Substances 0.000 claims description 29
- 238000005245 sintering Methods 0.000 claims description 28
- 239000007787 solid Substances 0.000 claims description 28
- -1 polytetrafluoroethylene Polymers 0.000 claims description 25
- 239000002033 PVDF binder Substances 0.000 claims description 23
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 23
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 22
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 22
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 17
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 229910052582 BN Inorganic materials 0.000 claims description 14
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- 238000002360 preparation method Methods 0.000 claims description 4
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 3
- 239000004952 Polyamide Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
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- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000010981 drying operation Methods 0.000 claims description 2
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229920002493 poly(chlorotrifluoroethylene) Polymers 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 239000005023 polychlorotrifluoroethylene (PCTFE) polymer Substances 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
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- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- XIUFWXXRTPHHDQ-UHFFFAOYSA-N prop-1-ene;1,1,2,2-tetrafluoroethene Chemical group CC=C.FC(F)=C(F)F XIUFWXXRTPHHDQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 3
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- 239000000243 solution Substances 0.000 description 17
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 7
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- VBGGLSWSRVDWHB-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(trifluoromethoxy)silane Chemical compound FC(F)(F)O[Si](OC(F)(F)F)(OC(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBGGLSWSRVDWHB-UHFFFAOYSA-N 0.000 description 4
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
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- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
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- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
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- BDAWXSQJJCIFIK-UHFFFAOYSA-N potassium methoxide Chemical compound [K+].[O-]C BDAWXSQJJCIFIK-UHFFFAOYSA-N 0.000 description 1
- LPNYRYFBWFDTMA-UHFFFAOYSA-N potassium tert-butoxide Chemical compound [K+].CC(C)(C)[O-] LPNYRYFBWFDTMA-UHFFFAOYSA-N 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
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Classifications
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Abstract
本发明属于通信材料技术领域,尤其涉及一种高介电常数的含氟树脂基高导热高频覆铜板。本发明通过先配制含氟树脂混合物均匀分散液,再制得含氟树脂基复合糊状物,然后刮涂、烘干、烧结制得含氟树脂基介质片,最后与铜箔叠合的方式,制得最终的含氟树脂基高导热高频覆铜板。
Description
技术领域
本发明属于通信材料技术领域,尤其涉及一种高介电常数的含氟树脂基高导热高频覆铜板。
背景技术
作为电子元器件主要载体的覆铜板,其集成度越来越高、线路越来越精细,为保证电子元器件工作的稳定性,覆铜板除了要拥有稳定的绝缘性、热-机械性能之外,还需要拥有良好的散热功能。
金属基覆铜板拥有最好的散热能力,但其制造成本居高不下、生产难度大,仅多用于高电流模块。氧化铝基、氮化铝基和氮化硅基等陶瓷基板也拥有良好的热导率,但是陶瓷基板机械性能较差。
以FR-4为代表的传统环氧树脂基覆铜板,虽拥有优异的热-机械稳定性,但其热导率只有0.25W/mK。所以出现了向树脂基体中填充大量无机导热材料的覆铜板类型,其虽可以提升复合材料的热导率,但其加工性能明显下降,且制品脆性增大、树脂基体与铜箔的粘结性变差。此外,其横向和纵向散热效果一致,不能满足大功率器件对横向快速散热的要求,进而难以满足当下高速、高频、无损和大容量信息传送的需求。
更进一步的,以聚四氟乙烯(PTFE)为代表的含氟树脂,因其特有的化学结构而拥有其他聚合物树脂无法比拟的低介电常数、低介电损耗、高热稳定性和化学稳定性等多种优异性能。自美国专利US3136680优先报道以来,PTFE已被普遍用作覆铜板的基体材料。但是,含氟树脂本身的热导率极低(0.15W/mK),限制了它更为广泛的应用,所以,开发高导热的含氟树脂基高频覆铜板迫在眉睫。
发明内容
本发明提供一种高介电常数的含氟树脂基高导热高频覆铜板,其能通过先配制含氟树脂混合物均匀分散液,再制得含氟树脂基复合糊状物,然后刮涂、烘干、烧结制得含氟树脂基介质片,最后与铜箔叠合的方式,制得最终的含氟树脂基高导热高频覆铜板。
本发明解决上述问题采用的技术方案是:一种高介电常数的含氟树脂基高导热高频覆铜板,所述覆铜板的制备方法依次包括以下步骤:
a、配制固含量为20-75wt/v%的含氟树脂混合物均匀分散液;
b、在所述含氟树脂混合物均匀分散液中,先添加絮凝剂溶液,再搅拌混合,最后倒去溶剂,得到含氟树脂基复合糊状物;
c、在平板上将所述含氟树脂基复合糊状物刮涂成膜,再依次经过烘干、烧结以及剥离步骤,制得含氟树脂基介质片;
d、将所述含氟树脂基介质片与铜箔叠合,经层压工艺,制得最终的含氟树脂基高导热高频覆铜板。
进一步优选的技术方案在于:所述频覆铜板的介电常数≥5.0。
进一步优选的技术方案在于:步骤a中,所述含氟树脂混合物包括聚四氟乙烯乳液、四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液、其他含氟树脂乳液、聚偏二氟乙烯、表面由偶联剂和部分含氟聚合物共同修饰的氮化硼、辅助填料以及氨水。
在本发明的步骤a中,所述含氟树脂混合物均匀分散液通过搅拌方式混合制得,搅拌混合操作的温度为15-50℃、时间为24-96h。
在本发明的步骤a中,所述聚偏二氟乙烯的添加量占所述含氟树脂混合物的0.5-10wt%,所述氨水的浓度为1-28wt%,所述氨水的体积为所述聚偏二氟乙烯质量的0.1-300倍,所述氨水的体积单位为L,所述聚偏二氟乙烯的质量单位为kg。
进一步优选的技术方案在于:步骤a中,所述其他含氟树脂乳液为聚全氟乙丙烯、乙烯-四氟乙烯共聚物、聚三氟氯乙烯以及乙烯-三氟氯乙烯共聚物中的任意一种或几种混合物的乳液。
在本发明的步骤a中,所述其他含氟树脂乳液的固含量为20-70wt/v%,粘度9-45mPa•s (25℃),所述其他含氟树脂乳液的用量占含氟树脂混合物的百分比≤20wt%。
进一步优选的技术方案在于:步骤a中,所述表面由偶联剂和部分含氟聚合物共同修饰的氮化硼中的所述偶联剂为硅烷偶联剂,所述部分含氟聚合物为乙烯-四氟乙烯共聚物、乙烯-三氟氯乙烯共聚物以及聚偏二氟乙烯中的任意一种或几种混合物的乳液。
在本发明的步骤a中,所述表面由偶联剂和部分含氟聚合物共同修饰的氮化硼的制备方法具体如下。
第一、配置偶联剂的水/醇混合溶液,并将其pH值调节到2-5之间,在20-60℃下搅拌活化5-30min后,得到活化的偶联剂溶液。
第二、同时,将氮化硼混入溶剂A中,经球磨得到均匀分散液,然后向该均匀分散液中加入碱溶液,并于30-110℃下超声反应4-96h,接着,向该均匀分散液中倒入酸溶液,将其pH值调节到4-7之间,然后倒入所述活化的偶联剂溶液,并于30-80℃下继续搅拌反应4-24h之后,经过滤-水洗多次,最后再用有机溶剂淋洗1-3遍,得到偶联剂改性的氮化硼。
第三、配置固含量为1-40wt/v%偶联剂改性的氮化硼的均匀分散液,再加入部分含氟聚合物乳液,于20-60℃下继续搅拌0.5-72h,过滤除去溶剂后,再经烘干制备得到表面由偶联剂和部分含氟聚合物共同修饰的氮化硼。
其中,偶联剂的水/醇混合溶液中所述的醇为甲醇、乙醇以及异丙醇中的任意一种或几种混合物。
其中,溶剂A、碱溶液溶剂、酸溶液溶剂这三者均为水、丙酮、甲醇、乙醇以及异丙醇中的任意一种或几种混合物。
其中,碱溶液中的碱为氢氧化锂、氢氧化钠、氢氧化钾、甲醇锂、甲醇钠、甲醇钾、乙醇锂、乙醇钠、乙醇钾或叔丁醇钾中的任意一种或几种混合物。
其中,所述偶联剂为硅烷偶联剂,其用量占氮化硼的0.1-10wt%。
其中,所述部分含氟聚合物乳液的固含量为10-70wt/v%,粘度为7-45mPa•s (25℃),其用量占氮化硼的1-10v/wt%。
最后,所述表面由偶联剂和部分含氟聚合物共同修饰的氮化硼,其粒径D50控制在0.3-40um之间,其用量占含氟树脂混合物的5-55wt%。
进一步优选的技术方案在于:步骤b中,所述絮凝剂为聚酰胺、聚酰亚胺、聚醚酰亚胺以及聚乙烯醇中的任意一种或几种混合物。
在本发明的步骤b中,所述絮凝剂加入后再在25-100℃的条件下搅拌0.5-24h。
进一步优选的技术方案在于:步骤c中,所述平板的材质为陶瓷或者金属,所述烘干操作的温度为50-200℃、时间为10min-24h,所述烧结操作的温度为150-370℃、时间为0.5-72h,烧结气氛为氮气或氩气。
进一步优选的技术方案在于:步骤c中,所述含氟树脂基介质片的厚度为0.1-10mm。
进一步优选的技术方案在于:步骤d中,所述层压工艺的温度为150-370℃,层压压力为70-250kg/cm2,层压时间为2-72h,在惰性气体气氛下进行。
进一步优选的技术方案在于:步骤d中,所述含氟树脂基介质片的数量≥1张,所述铜箔的数量为1或2张。
本发明具有以下优点。
第一,聚四氟乙烯(PTFE)、四氟乙烯-全氟烷氧基乙烯基醚共聚物(PFA)和部分含氟聚合物的工业化产品,常常残留诸如-CH2-和-CHF-等“缺陷”官能团,这些官能团在氨水存在的情况下,彼此间、或与聚偏二氟乙烯(PVDF)间能发生脱-HF交联反应,由此可以在含氟树脂基体中引入交联网络结构,因为交联网络结构的建立,可显著降低板材的热膨胀系数,提高板材的弯曲强度、机械刚度和尺寸稳定性。
第二,PVDF是一种廉价的部分含氟聚合物,它的引入降低了含氟树脂基高导热高频覆铜板的生产成本。
第三,引入连续法改性得到的表面由偶联剂和部分含氟聚合物共同修饰的氮化硼,使其与含氟树脂之间的相互作用力提升、相容性提高,最终提高含氟树脂基介质片的机械性能和介电性能,降低热膨胀系数(CTE)。
第四,氮化硼作为高导热填料,在经过上述修饰改性之后,在含氟树脂基介质片内建立良好的导热愈渗网络,从而显著提高高导热高频覆铜板在其厚度方向上的热导率。
第五,四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(PFA)的加入,降低了PTFE的加工温度。
第六,用该含氟树脂混合物的分散液,经浸渍玻纤布、烘干制得的半固化片,具有含胶量均匀、浸胶质量佳、树脂附着力强、表面平整、韧性和粘性适宜的优点。
第七,本发明通过使用低熔点的含氟树脂大幅提高了传统氟树脂的加工性能,偶联剂的使用同时增强了无机填料和玻纤布与树脂基体之间的相互作用力,提升了无机填料、加工助剂等在氟树脂内的分散性,确保了高频覆铜板各项性能的稳定性。
第八,本发明操作过程简单、制备条件温和、生产成本低、易于批量化和规模化生产、普适性强,具有良好的工业化生产基础和广阔的应用前景。
附图说明
图1为本发明6个实施例、1个对比例中的高导热高频覆铜板用含氟树脂基介质片的主要性能测试结果。
具体实施方式
以下所述仅为本发明的较佳实施例,并非对本发明的范围进行限定。
合成例1
取120份BN (D50=10um)混合于3500份纯水中,经球磨分散30min后,向其中加入70份NaOH,在80℃下经超声辅助反应8h之后,再加入乙酸调节pH值在6-7之间,得到活化BN的反应液。
配置2wt% H2O/乙醇混合溶液100份,加入0.7份偶联剂KH550和2.3份偶联剂KH570,于55℃下搅拌5min后,将体系的pH值调节到3-5之间,并继续搅拌15min,得到活化复合偶联剂溶液。
将活化复合偶联剂溶液倒入活化BN的反应液中,在60℃下继续搅拌4h后,经过滤、多次水洗涤产物直至滤液pH值在7-8之间;最后,将滤饼依次经乙醇、甲苯淋洗后,得到KH570/KH550共同修饰的改性BN。
配置固含量为30%的KH570/KH550共同修饰的改性BN均匀分散液,加入5份ETFE乳液(杜邦Teflon® 532-6210),于45℃下继续搅拌2h,过滤除去溶剂,烘干得到表面由KH570/KH550和ETFE共同修饰的改性BN。
合成例2
取120份BN (D50=20um)混合于3500份纯水中,经球磨分散30min后,向其中加入80份NaOH,在80℃下经超声辅助反应12h之后,再加入乙酸调节pH值在6-7之间,得到活化BN的反应液。
配置2wt% H2O/乙醇混合溶液100份,加入0.8份偶联剂全氟癸基三甲氧基硅烷和3.5份偶联剂KH570,于50℃下搅拌10min后,将体系的pH值调节到3-5之间,并继续搅拌20min,得到活化复合偶联剂溶液。
将活化复合偶联剂溶液倒入活化BN的反应液中,在60℃下继续搅拌5h后,经过滤、多次水洗涤产物直至滤液pH值在7-8之间;最后,将滤饼依次经乙醇、甲苯淋洗后,得到全氟癸基三甲氧基硅烷/KH570共同修饰的改性BN。
配置固含量为30%的全氟癸基三甲氧基硅烷/KH570共同修饰的改性BN的均匀分散液,加入6份ETFE乳液(杜邦Teflon® 532-6210),于30℃下搅拌2h。过滤除去溶剂,烘干得到表面由全氟癸基三甲氧基硅烷/KH570和ETFE共同修饰的改性BN。
实施例 1
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、10份氧化硅、10份氧化铝、150份氧化钛、120份合成例1中的改性BN、5份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入丙酮,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.8mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为360℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
实施例 2
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、10份氧化硅、10份氧化铝、150份氧化钛、120份合成例2中的改性BN、5份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入丙酮,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.8mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为365℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
实施例 3
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、10份氧化硅、10份氧化铝、150份氧化钛、120份合成例1中的改性BN、3份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入乙酸乙酯,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.8mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为350℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为360℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
实施例 4
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、10份氧化硅、10份氧化铝、150份氧化钛、120份合成例2中的改性BN、3份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入乙酸乙酯,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.8mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为360℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
实施例 5
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、200份氧化钛、190份钛酸钡、120份合成例1中的改性BN、5份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入丙酮,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.6mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为360℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
实施例 6
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、300份氧化钛、300份钛酸钡、120份合成例1中的改性BN、10份PVDF、50份市售氨水溶液(质量百分浓度为26%),在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入丙酮,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.6mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为360℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得具有高介电常数的含氟树脂基高导热高频覆铜板。
对比例 1
称取120份聚四氟乙烯乳液(杜邦Teflon® PTFE DISP30,固含量60%)、60份四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液(杜邦Teflon® PFAD 335D,固含量60%)、80份聚全氟乙丙烯乳液(杜邦Teflon® FEPD121,固含量54%)、10份氧化硅、10份氧化铝、150份氧化钛、120份合成例1中的改性BN,在25℃下搅拌混合24h后得到均匀分散液。
逐滴加入丙酮,在25℃下搅拌至不再出现白色粘稠沉淀物,倒去溶剂,得到含氟树脂基复合糊状物。
将该复合糊状物于干净的玻璃平板上刮成厚度约为0.8mm厚的膜,在70℃下烘干1h后,将玻璃平板和膜转移至氮气氛围中,并设定烧结温度为360℃、烧结时间为8h;烧结结束后待其自然降至室温,随后将膜从玻璃片上剥离,得到含氟树脂基介质片。
取1张该含氟树脂基介质片和2张loz铜箔,在压力为130-150kg/cm2、氮气气氛、温度为370℃情况下层压6h,制得高频覆铜板。
最后,对上述6个实施例、1个对比例中高频覆铜板用含氟树脂基介质片的主要性能进行测试,结果如附图1所示。
如对比例1所示,在未加入PVDF和氨水的情况下,高频覆铜板用含氟树脂基介质片导热系数只有0.9W/mK,在Z轴方向的热膨胀系数CTE高达80ppm/K。
而在引入PVDF和氨水的组合后,如实施例3,Z轴方向的热膨胀系数CTE显著降低至50ppm/K,导热系数提升至0.95W/mK;随着PVDF的用量增加,Z轴方向的热膨胀系数CTE可进一步降低,导热系数也有明显提升,如实施例1、6。
全氟偶联剂可进一步提高填料与含氟树脂的相容性,辅助提升高频覆铜板用粘结片的导热系数、降低热膨胀系数,如实施例2、4。在实际生产中,可综合考虑性能和成本的要求来选择偶联剂。
上面结合附图对本发明的实施方式作了详细说明,但是本发明不限于上述实施方式,在所述技术领域普通技术人员所具备的知识范围内,还可以在不脱离本发明宗旨的前提下做出各种修改。这些都是不具有创造性的修改,只要在本发明的权利要求范围内都受到专利法的保护。
Claims (9)
1.一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于所述覆铜板的制备方法依次包括以下步骤:
a、配制固含量为20-75wt/v%的含氟树脂混合物均匀分散液;
b、在所述含氟树脂混合物均匀分散液中,先添加絮凝剂溶液,再搅拌混合,最后倒去溶剂,得到含氟树脂基复合糊状物;
c、在平板上将所述含氟树脂基复合糊状物刮涂成膜,再依次经过烘干、烧结以及剥离步骤,制得含氟树脂基介质片;
d、将所述含氟树脂基介质片与铜箔叠合,经层压工艺,制得最终的含氟树脂基高导热高频覆铜板,
步骤a中,所述含氟树脂混合物包括聚四氟乙烯乳液、四氟乙烯-全氟烷氧基乙烯基醚共聚物乳液、其他含氟树脂乳液、聚偏二氟乙烯、表面由偶联剂和部分含氟聚合物共同修饰的氮化硼、辅助填料以及氨水,
步骤a中,所述聚偏二氟乙烯的添加量占所述含氟树脂混合物的0.5-10wt%,所述氨水的浓度为1-28wt%,所述氨水的体积为所述聚偏二氟乙烯质量的0.1-300倍,所述氨水的体积单位为L,所述聚偏二氟乙烯的质量单位为kg。
2.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:所述高频覆铜板的介电常数≥5.0。
3.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤a中,所述其他含氟树脂乳液为聚全氟乙丙烯、乙烯-四氟乙烯共聚物、聚三氟氯乙烯以及乙烯-三氟氯乙烯共聚物中的任意一种或几种混合物的乳液。
4.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤a中,所述表面由偶联剂和部分含氟聚合物共同修饰的氮化硼中的所述偶联剂为硅烷偶联剂,所述部分含氟聚合物为乙烯-四氟乙烯共聚物、乙烯-三氟氯乙烯共聚物以及聚偏二氟乙烯中的任意一种或几种混合物的乳液。
5.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤b中,所述絮凝剂为聚酰胺、聚酰亚胺、聚醚酰亚胺以及聚乙烯醇中的任意一种或几种混合物。
6.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤c中,所述平板的材质为陶瓷或者金属,所述烘干操作的温度为50-200℃、时间为10min-24h,所述烧结操作的温度为150-370℃、时间为0.5-72h,烧结气氛为氮气或氩气。
7.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤c中,所述含氟树脂基介质片的厚度为0.1-10mm。
8.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤d中,所述层压工艺的温度为150-370℃,层压压力为70-250kg/cm2,层压时间为2-72h,在惰性气体气氛下进行。
9.根据权利要求1所述的一种高介电常数的含氟树脂基高导热高频覆铜板,其特征在于:步骤d中,所述含氟树脂基介质片的数量≥1张,所述铜箔的数量为1或2张。
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