CN104704027A - 挠性金属层压板及其制备方法 - Google Patents
挠性金属层压板及其制备方法 Download PDFInfo
- Publication number
- CN104704027A CN104704027A CN201480002537.XA CN201480002537A CN104704027A CN 104704027 A CN104704027 A CN 104704027A CN 201480002537 A CN201480002537 A CN 201480002537A CN 104704027 A CN104704027 A CN 104704027A
- Authority
- CN
- China
- Prior art keywords
- polyimide resin
- resin layer
- flexible metal
- veneer sheet
- porous polyimide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 78
- 239000002184 metal Substances 0.000 title claims abstract description 78
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000004519 manufacturing process Methods 0.000 title description 4
- 229920001721 polyimide Polymers 0.000 claims abstract description 146
- 239000009719 polyimide resin Substances 0.000 claims abstract description 133
- 239000011347 resin Substances 0.000 claims abstract description 76
- 229920005989 resin Polymers 0.000 claims abstract description 76
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000011737 fluorine Substances 0.000 claims abstract description 41
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 41
- 239000002245 particle Substances 0.000 claims abstract description 34
- 238000002360 preparation method Methods 0.000 claims description 30
- 229920005575 poly(amic acid) Polymers 0.000 claims description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 5
- 238000009998 heat setting Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 239000004411 aluminium Substances 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229920000840 ethylene tetrafluoroethylene copolymer Polymers 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 2
- 239000005977 Ethylene Substances 0.000 claims description 2
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical compound FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 229920006259 thermoplastic polyimide Polymers 0.000 claims 1
- 239000000126 substance Substances 0.000 description 40
- 239000004642 Polyimide Substances 0.000 description 14
- 239000011889 copper foil Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 9
- 229920002313 fluoropolymer Polymers 0.000 description 9
- 239000004811 fluoropolymer Substances 0.000 description 9
- 229920000106 Liquid crystal polymer Polymers 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 238000009826 distribution Methods 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000002250 absorbent Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000003595 mist Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920000573 polyethylene Polymers 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229920003002 synthetic resin Polymers 0.000 description 4
- 239000011324 bead Substances 0.000 description 3
- ANSXAPJVJOKRDJ-UHFFFAOYSA-N furo[3,4-f][2]benzofuran-1,3,5,7-tetrone Chemical compound C1=C2C(=O)OC(=O)C2=CC2=C1C(=O)OC2=O ANSXAPJVJOKRDJ-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- -1 polydimethylsiloxane Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000011664 signaling Effects 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 description 1
- 229920001774 Perfluoroether Polymers 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000004205 dimethyl polysiloxane Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 238000000875 high-speed ball milling Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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Abstract
本发明涉及一种挠性金属层压板及其制备方法,其中所述挠性金属层压板包括多孔聚酰亚胺树脂层,所述多孔聚酰亚胺树脂层包含30重量%至95重量%的聚酰亚胺树脂和5重量%至70重量%的含氟树脂颗粒,其中所述多孔聚酰亚胺树脂层中分布着直径为0.05μm至20μm的微孔。
Description
技术领域
本发明涉及一种挠性金属层压板以及所述挠性金属层压板的制备方法,更具体而言涉及一种具有低介电常数、低吸水性和高弹性的挠性金属层压板以及一种用于制备所述挠性金属层压板的方法。
背景技术
近来,随着电子设备微型化、高速和各种功能结合的趋势,电子设备内部的信号传输速度或电子设备外部的信号传输速度也在变快。因此,需要一种使用具有比现有绝缘体更低的介电常数和介电损耗系数的绝缘体的印刷电路板。
鉴于上述趋势,近来尝试将比现有聚酰亚胺具有更低介电常数且更加不易受吸水性影响的液晶聚合物(LCP)应用于挠性印刷电路板中。但是,尽管应用了LCP,由于LCP的介电常数(Dk=2.9)与聚酰亚胺(Dk=3.2)没有明显差异,因此基于LCP的改善程度甚微,另外,由于LCP的耐热性低以至于在锡焊过程中可能会产生问题,并且由于LCP具有热塑性,因此在使用激光的穿孔过程中,存在与使用现有聚酰亚胺的PCB制造方法的相容性问题。
因此,作为上述问题的解决方法,已尝试降低用作现有挠性电路板的绝缘体的聚酰亚胺的介电常数。例如,美国专利第4816516号公开了通过混合聚酰亚胺和含氟聚合物来制备模塑制品的方法。但是,上述专利不涉及需要低介电常数的电子设备产品,而是涉及模塑制品,并且实际上使用了具有高热膨胀系数和低玻璃化转变温度的聚酰亚胺。另外,需将聚酰亚胺树脂加工成薄膜状以便在印刷电路板中使用,但上述美国专利并未公开制备成薄膜状的铜箔层压板。
另外,美国专利第7026032号公开了一种通过将含氟聚合物细粉分散于聚酰亚胺中来降低制品的介电常数的方法。上述美国专利公开了相比于绝缘体的内芯,含氟聚合物细粉更多地分布于绝缘体的外表面的内容。但是,如上述美国专利所述,由于含氟聚合物在绝缘体最外层中的含量最多,在外表面的含氟聚合物会使水分的渗透及吸收降低,因此降低总的吸水性,但可能会发生在由聚酰亚胺构成的现有挠性铜箔层压板中所不存在的问题。例如,在上述美国专利中公开的聚酰亚胺树脂与覆盖层、预浸材料和ACF的粘合力可能较低,在上述美国专利中公开的聚酰亚胺树脂的热膨胀系数(CTE)过高而无法应用于挠性铜箔层压板,并且在所述聚酰亚胺树脂的表面存在过量的氟树脂,因此在PCB制备过程中,氟树脂可能会在收板工艺(receivingprocess)所施加的约380℃的温度下熔融,也存在铜箔线路从绝缘体剥离的风险。
因此,为制备具有低介电常数的印刷电路板,需要开发一种具有低介电常数、低热膨胀系数、高弹性和低吸水性的材料。
现有技术文献:
专利文献
(专利文献1)美国专利第4816516号
(专利文献2)美国专利第7026032号
发明内容
发明目的
本发明的目的是提供一种具有低介电常数、低吸水性和高弹性的挠性金属层压板。
本发明的另一目的是提供一种用于制备具有低介电常数、低吸水性和高弹性的挠性金属层压板的方法。
技术方案
本发明提供一种挠性金属层压板,其包括多孔聚酰亚胺树脂层,所述多孔聚酰亚胺树脂层包含30重量%至95重量%的聚酰亚胺树脂和5重量%至70重量%的含氟树脂颗粒,其中在所述多孔聚酰亚胺树脂层中分布着直径为0.05μm至20μm的微孔。
本发明还提供一种用于制备挠性金属层压板的方法,其包括以下步骤:在约280至320℃的温度范围内改变升温速度,使包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物热固化,从而形成多孔聚酰亚胺树脂层;以及在所述多孔聚酰亚胺树脂层的至少一面上沉积所述金属薄膜层。
下面,详细说明本发明的具体实施例的挠性金属层压板以及所述挠性金属层压板的制备方法。
根据本发明的一个实施方案,提供一种挠性金属层压板,其包括多孔聚酰亚胺树脂层,所述多孔聚酰亚胺树脂层包含30重量%至95重量%的聚酰亚胺树脂和5重量%至70重量%的含氟树脂颗粒,其中在所述多孔聚酰亚胺树脂层中分布着直径为0.05μm至20μm的微孔。
现有技术中已知,通过添加含氟聚合物树脂来降低应用于挠性金属层压板的聚合物树脂例如聚酰亚胺等的介电常数的方法。然而,代表性的含氟树脂,例如聚四氟乙烯(PTFE)、四氟乙烯-六氟丙烯共聚物(FEP)和全氟烷氧基树脂(PFA)的热膨胀系数分别为135ppm、150ppm和230ppm,其远高于常规聚酰亚胺所具有的热膨胀系数(10ppm至30ppm),为了显著降低聚酰亚胺的介电常数,需引入约10重量%至60重量%的氟树脂,因此整体热膨胀系数势必会增大。
相反地,一个实施方案的挠性金属层压板包含其中分布着许多具有预定尺寸的气孔的多孔聚酰亚胺树脂层,因此能够在显著降低介电常数的同时确保高弹性,并且容易将热膨胀系数调整到作为挠性金属层压板使用时的最佳范围内。
在多孔聚酰亚胺树脂层的制备过程中,混合聚酰亚胺树脂或其前体(例如,聚酰胺酸等)与含氟树脂,并在高温中进行热处理的过程,由于所述聚酰亚胺树脂或其前体与含氟树脂之间的热膨胀系数的差异,最终可制备出其中分布着具有预定尺寸的许多气孔的多孔聚酰亚胺树脂层或多孔聚合物树脂膜。
具体而言,在多孔聚酰亚胺树脂层的制备过程中,将包含聚酰亚胺树脂或其前体(例如,聚酰胺酸等)以及含氟树脂颗粒的树脂组合物涂布到规定的基板上,并在约280至320℃的温度范围内在改变升温速度的同时升高组合物的温度,从而在多孔聚酰亚胺树脂层内形成直径为0.05μm至20μm或0.1μm至5μm的微孔。
更具体而言,将包含聚酰亚胺树脂或其前体和含氟树脂颗粒的树脂组合物涂布到规定的基板上,在等于或小于300℃的温度范围内以3℃/min至10℃/min的速度、并在大于300℃的温度范围内以0.2℃/min至2℃/min的速度提高所涂布的组合物的温度,从而在多孔聚酰亚胺树脂层内形成直径为0.05μm至20μm或0.1μm至5μm的微孔。
当多孔聚酰亚胺树脂层中分布直径为0.05μm至20μm的微孔时,多孔聚酰亚胺树脂层可具有1.2g/cm2至1.9g/cm2或1.3g/cm2至1.5g/cm2的密度。
微孔可占多孔聚酰亚胺树脂层的0.1体积%至5体积%或0.2体积%至1体积%。
包含在多孔聚酰亚胺树脂层中的含氟树脂颗粒可具有0.05μm至9.5μm或1.0μm至5.0μm的平均粒径(D50)。当含氟树脂颗粒具有上述平均粒径时,合成的聚酰亚胺树脂与含氟树脂颗粒之间的热膨胀程度的差异,以及固化时收缩程度的差异可使所述聚酰亚胺树脂层形成为其中均匀分布着微小的气孔的多孔树脂层。
具体而言,含氟树脂颗粒的平均粒径(D50)可以是通过激光粒度分析仪测量的D50值。由于含氟树脂颗粒的粒度分布为正态分布,因此可以将D50设定为含氟树脂颗粒的平均粒径,其中D50为在粒度分布中基于最大值计的50%累积大小(正态分布图的下方面积的大小)的值。
多孔聚酰亚胺树脂层包含30重量%至95重量%的聚酰亚胺树脂和5重量%至70重量%的分布于包含聚酰亚胺树脂的基层中的含氟树脂颗粒,其中,包含聚酰亚胺树脂的基层可以是分布着直径为0.05μm至20μm的微孔的多孔聚酰亚胺树脂层。
含氟树脂颗粒可包括含氟聚合物,所述含氟聚合物包含至少一种选自聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物树脂(ETFE)、四氟乙烯-氯三氟乙烯共聚物(TFE/CTFE)和乙烯-氯三氟乙烯树脂(ECTFE)的聚合物。
另一方面,对包含在多孔聚酰亚胺树脂层中的聚酰亚胺树脂的具体特征并没有特别限制,可无特别限制地使用已知可用于挠性金属层压板中的聚酰亚胺树脂。
例如,聚酰亚胺树脂可具有1,000至500,000或10,000至300,000的重均分子量。如果所述聚酰亚胺树脂的重均分子量太小,则无法充分确保用作挠性金属层压板等时所需的机械性能。另外,如果聚酰亚胺树脂的重均分子量太大,则一个实施方案的聚酰亚胺树脂膜的弹性或机械性能可能会劣化。
具体而言,聚酰亚胺树脂可包括以下化学式1的重复单元。
[化学式1]
在化学式1中,Y1为4价的芳族有机官能团,X为2价的芳族有机官能团,并且n为1至300的整数。
Y1可包含选自以下化学式21至27的4价官能团。
[化学式21]
[化学式22]
在化学式22中,Y1为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数。
[化学式23]
在化学式23中,Y2和Y3可相同或不同,并分别为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数。
[化学式24]
在化学式24中,Y4、Y5和Y6可相同或不同,并分别为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数。
[化学式25]
[化学式26]
[化学式27]
在化学式21至27中,“*”表示键合点(bonding point)。
此外,化学式1中的Y1优选为选自化学式28至30的4价官能团,以使多孔聚酰亚胺树脂层在具有低介电常数、低吸水性和高弹性的同时,确保最佳的热膨胀系数。化学式1的重复单元中的Y1可相同或不同。
[化学式28]
[化学式29]
[化学式30]
在化学式28至30中,“*”表示键合点(bonding point)。
此外,在化学式1中,X可以是选自以下化学式31至34的2价官能团。
[化学式31]
在化学式31中,R1可以是氢、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3或-CF2CF2CF2CF3。
[化学式32]
在化学式32中,L1为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数,R1和R2可相同或不同,且分别为氢、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3或-CF2CF2CF2CF3。
[化学式33]
在化学式33中,L2和L3可相同或不同,且分别为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数,R1、R2和R3可相同或不同,且分别为氢、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3或-CF2CF2CF2CF3。
[化学式34]
在化学式34中,L4、L5和L6可相同或不同,且分别为单键、-O-、-CO-、-S-、-SO2-、-C(CH3)2-、-C(CF3)2-、-CONH-、-COO-、-(CH2)n1-、-O(CH2)n2O-、-OCH2-C(CH3)2-CH2O-或-OCO(CH2)n3OCO-,并且n1、n2和n3分别为1至10的整数,R1、R2、R3和R4可相同或不同,且分别为氢、-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3或-CF2CF2CF2CF3.
特别地,如果化学式1中的X是以下化学式35的2价官能团,则多孔聚酰亚胺树脂层可具有低的介电常数、低的吸水性和高的弹性,并可确保最佳的热膨胀系数。X在化学式1的各个重复单元中可相同或不同。
[化学式35]
在化学式35中,R1和R2可相同或不同,且分别为-CH3、-CH2CH3、-CH2CH2CH2CH3、-CF3、-CF2CF3、-CF2CF2CF3或-CF2CF2CF2CF3。
另一方面,多孔聚酰亚胺树脂层可包括:30重量%至95重量%或40重量%至90重量%的聚酰亚胺树脂,其包含化学式1的重复单元和余量的含氟树脂颗粒。如果含氟树脂颗粒的含量太小,则最终制备的多孔聚酰亚胺树脂层可能无法具有充分低的介电常数或吸水性。另外,如果含氟树脂颗粒的含量太大,则挠性金属层压板的机械性能可能劣化,其因此容易破裂或损坏,并且包含在挠性金属层压板中的多孔聚酰亚胺树脂层的热膨胀系数可能会显著增大。
另一方面,多孔聚酰亚胺树脂层可具有0.1μm至100μm或1μm至50μm的厚度。
多孔聚酰亚胺树脂层在5GHz的干燥状态下,可具有2.7以下、或2.2至2.7、或2.3至2.6的介电常数(Dk)。常见的聚酰亚胺树脂在5GHz的干燥状态下,通常具有3.0以上的介电常数,相比之下,多孔聚酰亚胺树脂层可具有相对低的介电常数。
多孔聚酰亚胺树脂层在100℃至200℃的温度下可具有1ppm至28ppm的热膨胀系数。
由于铜箔(其为通常用于挠性金属层压板中的金属箔)的热膨胀系数为约18ppm,因此需使一个实施方案的聚酰亚胺树脂膜的热膨胀系数位于上述范围内,从而最小化由与金属箔的热膨胀系数的差异所导致的弯曲现象,以及最小化与构成印刷电路板的其他材料之间的收缩差异。
一个实施方案的挠性金属层压板可包括所述聚酰亚胺树脂膜和金属薄膜,并且金属薄膜可包含至少一种金属,其选自铜、铁、镍、钛、铝、银、金以及其合金。
金属薄膜可沉积于聚酰亚胺树脂膜的至少一面上。
具体而言,挠性金属层压板可包括一个金属薄膜或彼此相对的两个金属薄膜,在挠性金属层压板包括彼此相对的两个金属薄膜的情况下,聚酰亚胺树脂膜可位于彼此相对的两个金属薄膜之间。
金属薄膜表面的十点平均粗糙度(Rz)可为0.5μm至2.5μm。如果金属薄膜表面的十点平均粗糙度太小,则与聚合物树脂层的粘合力降低,并且如果金属薄膜表面的十点平均粗糙度太大,则表面粗糙度增大,从而导致在高频区域中传输损耗增大。
金属薄膜可具有0.1μm至50μm的厚度。
上述挠性金属层压板可进一步包括形成于所述聚酰亚胺树脂膜的至少一面上的聚酰亚胺树脂层。
具体而言,挠性金属层压板可进一步包括与聚酰亚胺树脂膜的两面相结合的第二和第三聚酰亚胺树脂膜或聚酰亚胺树脂层。第二和第三聚酰亚胺树脂膜可分别具有与上述聚酰亚胺树脂相同或不同的组成。
另外,第二及第三聚酰亚胺树脂膜可分别具有与上述聚酰亚胺树脂膜相同或不同的厚度,且厚度范围可为0.1μm至100μm、或1μm至50μm。
根据本发明的另一实施方案,提供一种用于制备挠性金属层压板的方法,其包括以下步骤:在约280至320℃的温度范围内改变升温速度,使包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物热固化,从而形成多孔聚酰亚胺树脂层;以及在所述多孔聚酰亚胺树脂层的至少一面上沉积金属薄膜。
在多孔聚酰亚胺树脂层的制备过程中,通过使包含聚酰亚胺树脂或其前体(例如,聚酰胺酸等)与含氟树脂颗粒的树脂组合物在280至320℃的温度范围内改变升温速度,可在多孔聚酰亚胺树脂层内形成直径为0.1μm至5μm的微孔。
具体而言,将包含聚酰亚胺树脂或其前体以及含氟树脂颗粒的树脂组合物涂布到规定的基板上,在等于或小于300℃的温度范围内以3℃/min至10℃/min的速度、以及在大于300℃的温度范围内以0.2℃/min至2℃/min的速度升高所涂布的组合物的温度,从而在多孔聚酰亚胺树脂层内形成直径为0.05μm至20μm、或0.1μm至5μm的微孔。即,形成多孔聚酰亚胺树脂层的步骤包括:在等于或小于300℃的温度范围内以3℃/min至10℃/min的速度升高树脂组合物的温度,以及在大于300℃的温度范围内以0.2℃/min至2℃/min的速度升高温度。
树脂组合物的热处理或升温可在340℃至370℃或350℃至360℃的温度下完成。
在对包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物进行升温的过程中,如果在280℃以下至320℃或300℃以下的温度范围内升温速度太大,则包括在挠性金属层压板中的各个层可能会剥离,并且多孔聚酰亚胺树脂层的热膨胀系数可能会显著增大。
在对包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物进行升温的过程中,如果在280℃以上至320℃或300℃以上的温度范围内升温速度太小,则在聚酰亚胺树脂层中不易形成气孔,因此难以确保充足的多孔,且难以充分降低所形成的聚酰亚胺树脂层的密度或热膨胀系数。
另外,在对包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物进行升温的过程中,如果在280℃以上至320℃或300℃以上的温度范围内升温速度太大,则在多孔聚酰亚胺树脂层中可能会产生气泡,或多孔聚酰亚胺树脂层难以与挠性金属层压板的其他薄膜或层例如金属薄膜等牢固地结合或粘合。
由于直径为0.05μm至20μm的微孔分布在多孔聚酰亚胺树脂层中,因此多孔聚酰亚胺树脂层可具有1.2g/cm2至1.9g/cm2、或1.3g/cm2至1.5g/cm2的密度。
微孔可占多孔聚酰亚胺树脂层的0.1体积%至5体积%或0.2体积%至1体积%。
包含在多孔聚酰亚胺树脂层中的含氟树脂颗粒可具有0.05μm至9.5μm或1.0μm至5.0μm的平均粒径(D50)。
关于聚酰胺酸树脂及含氟树脂颗粒的详情包括关于一个实施方案的挠性金属层压板的上述内容。另外,关于由聚酰胺酸树脂制备聚酰亚胺树脂的详情也包括关于一个实施方案的挠性金属层压板的上述内容。
包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物可进一步包括分散剂,分散剂的具体实例可包括选自聚酯聚合物、聚醚改性的聚二甲基硅氧烷和聚酯/聚胺聚合物的至少一种。
先前,已知一种使用含氟分散剂或含氟表面活性剂使含氟树脂分散在聚酰胺酸或聚酰亚胺中的方法。然而,根据该方法,尽管可将所制备的聚合物树脂层的介电常数降低至某种程度,但是由于含氟分散剂或含氟表面活性剂的使用,所制备的聚合物树脂层的热膨胀系数会显著增大。相反地,如果用于制备多孔聚酰亚胺树脂层的树脂组合物包含分散剂,则多孔聚酰亚胺树脂层在具有低介电常数的同时不会具有过高的热膨胀系数,在挠性金属层压板或印刷电路板的制备过程中可以防止包含在聚酰亚胺树脂中的含氟树脂熔融。
树脂组合物可包含0.1重量份至25重量份或0.5重量份至10重量份的分散剂,基于100重量份的含氟树脂颗粒计。
另一方面,形成多孔聚酰亚胺树脂层的步骤可进一步包括:在进行热固化之前,在基板上涂布树脂组合物至0.1μm至200μm的厚度。
另外,在多孔聚酰亚胺树脂层的至少一面上沉积金属薄膜的步骤可进一步包括:在250℃至450℃的温度下,在施加500Kgf至3000Kgf的压力的同时,在多孔聚酰亚胺树脂层的至少一面上沉积金属薄膜,其中金属薄膜包含至少一种金属,其选自铜、铁、镍、钛、铝、银、金以及由这些金属中的2种或多种构成的合金。
有益效果
根据本发明,提供一种具有低介电常数、低吸水性、高弹性和最佳热膨胀系数的挠性金属层压板,以及制备所述挠性金属层压板的方法。
因此,本发明提供一种具有低的介电常数,并且具有现有聚酰亚胺绝缘体所具有的高耐热性、耐化学性、尺寸稳定性等特性的聚酰亚胺树脂膜,以作为由于最近笔记本电脑、电脑、手机等设备的数据传输速度增加而导致的数据丢失增加、或印刷电路板增厚和在印刷电路板中线路变窄的解决方案。
另外,提供一种使用低介电常数聚酰亚胺的低介电常数铜箔层压板。因此,在匹配阻抗的同时可制备更薄的印刷电路板,因此能够制备出更薄的便携式电子设备,并使印刷电路板的线宽变宽,因此可显著减少PCB制造公司的次品率,从而非常有助于降低制造成本。
附图说明
图1示出聚酰亚胺树脂的横截面SEM照片。
具体实施方式
下面,参考以下实施例更加详细地阐述本发明。但是,这些实施例仅用于说明本发明,并且本发明的范围并不限于这些实施例。
[制备例:制备聚酰胺酸溶液]
制备例1:制备包含含氟树脂的聚酰胺酸溶液(P1)
在1L的聚乙烯(PE)瓶中充入氮气,加入765g二甲基乙酰胺(Dimethylacetamide,DMAc)、219g聚四氟乙烯(PTFE)微粉(粒径:约1.0μm至5.0μm)和765g直径为2mm的珠粒(bead),并在高速球磨(ball milling)机中搅拌。
在500mL的圆底烧瓶中加入其中分散有PTFE微粉的16g溶液、107g二甲基乙酰胺、13g均苯四甲酸二酐(Pyromellitic Dianhydride)、和20g 2,2’-双(三氟甲基)-4,4’-二氨基联苯,在50℃下,在通入氮气的同时使用搅拌机进行搅拌,使所得物反应10小时,从而获得粘度约为25,000cps的聚酰胺酸溶液(P1)。
制备例2:制备包含含氟树脂的聚酰胺酸溶液(P2)
在1L的聚乙烯(PE)瓶中充入氮气,加入765g二甲基乙酰胺(Dimethylacetamide,DMAc)、219g聚四氟乙烯(PTFE)微粉(粒径:约1.0至5.0μm)和765g直径为2mm的珠粒,并在高速球磨机中搅拌。
在500mL圆底烧瓶中加入其中分散有PTFE微粉的73g溶液、115g二甲基乙酰胺、11.609g均苯四甲酸二酐、17.391g 2,2’-双(三氟甲基)-4,4’-二氨基联苯,在50℃下,在通入氮气的同时使用搅拌机进行搅拌,使所得物反应10小时,从而获得粘度约为100,000cps的聚酰胺酸溶液(P2)。
制备例3:制备包含含氟树脂的聚酰胺酸溶液(P3)
在500mL圆底烧瓶中加入107g二甲基乙酰胺、13g均苯四甲酸二酐、20g 2,2’-双(三氟甲基)-4,4’-二氨基联苯,在50℃下,在通入氮气的同时使用搅拌机进行搅拌,使所得物反应10小时,从而获得粘度约为25,000cps的聚酰胺酸溶液(P3)。
[实施例1和2及比较例1和2:制备用于挠性金属层压板的聚酰亚胺树脂膜和挠性金属层压板]
实施例1和2
(1)制备聚酰亚胺树脂膜
将在制备例1至2中分别制备的聚酰胺酸溶液涂布于铜箔(厚度:12μm)的粗糙表面(matte surface)上,使最终厚度为25um,之后在80℃下干燥10分钟。在等于或小于300℃的温度范围内以5℃/min的速度从室温开始提升干燥产品的温度,并在大于300℃且小于350℃的温度范围内以1℃/min的速度进行固化。在完成固化后,刻蚀所述铜箔,从而制备厚度为25um的聚酰亚胺树脂膜。
(2)制备挠性金属层压板
在380℃下,通过向在实施例1和2中分别得到的聚酰亚胺树脂膜和厚度为12μm的铜箔施加1700Kgf的压力来将两者压合,从而制备出金属层压板。
比较例1
(1)制备聚酰亚胺树脂膜
以与实施例1相同的方法制备厚度为25μm的聚酰亚胺树脂膜,不同之处在于使用在制备例3中得到的聚酰胺酸溶液来代替在制备例1中制备的聚酰胺酸溶液。
(2)制备挠性金属层压板
在380℃下,通过向上述得到的聚酰亚胺树脂膜和厚度为12μm的铜箔施加1700Kgf的压力来将两者压合,从而制备出金属层压板。
比较例2
(1)制备聚酰亚胺树脂膜
将制备例2的聚酰胺酸溶液涂布在铜箔(厚度:12μm)的粗糙表面上,以使最终厚度为25um,之后在80℃下干燥10分钟。在氮化炉中,从室温开始提升所述干燥产品的温度,并在350℃下固化30分钟。
完成固化过程后,刻蚀所述铜箔,从而制备厚度为25μm的聚酰亚胺树脂膜。
(2)制备挠性金属层压板
在380℃下,通过向上述得到的聚酰亚胺树脂膜和厚度为12μm的铜箔施加1700Kgf的压力来将两者压合,从而制备出金属层压板。
[实验例]
1.实验例1:观察挠性金属层压板的横截面
通过SEM图确定在实施例1中得到的铜箔层压板的横截面。如随附的图1所示,可确定在实施例1中得到的聚酰亚胺树脂层中分布着直径为0.05μm至20μm的微孔。
2.实验例2:测量挠性金属层压板的物理性质
按照下述测量在上述实施例和比较例中得到的铜箔层压板的介电常数、CTE和吸收率,其结果在下表1中示出。
(1)介电常数的测量方法
将在实施例和比较例中得到的聚酰亚胺树脂膜在150℃下干燥30分钟,在25℃及50%RH的条件下,使用谐振器(Agiletn E5071BENA)通过分离介质谐振器(SPDR)方法测量各个聚酰亚胺树脂膜的介电常数。
(2)线性热膨胀系数(CTE)的测量方法
在实施例及比较例中得到的聚酰亚胺树脂膜的线性热膨胀系数根据IPC TM-6502.4.24.3的标准,在100℃至200℃的测量条件下,使用TMA/SDTA 840仪器(Mettler公司)进行测量。
(3)吸收率的测量方法
根据IPC TM-6502.6.2C的标准,将在实施例及比较例中得到的聚酰亚胺树脂膜在23℃的蒸馏水中浸渍24小时,并测量浸渍前后的待测物质量,从而算出吸收率。
[表1]实验例2的测量结果
如表1所示,可确定在实施例1和2中得到的多孔聚酰亚胺树脂层中分布着直径为0.5μm至2μm的微孔,并且所述聚酰亚胺树脂层的密度为1.30至1.40g/cm2。另外,在实施例1和2中制备的多孔聚酰亚胺树脂层具有2.6以下的低介电常数、1.5%以下的低吸收率,以及12至22ppm的线性膨胀系数。
相反地,可确定在比较例1和2的聚酰亚胺树脂层中未形成微孔,其中比较例1呈现相对高的介电常数(2.9)、低的线性膨胀系数和高的吸收率;相比于具有相同PTFE含量的实施例2,比较例2具有相对高的密度和相对高的介电常数。
Claims (18)
1.一种挠性金属层压板,其包括多孔聚酰亚胺树脂层,所述多孔聚酰亚胺树脂层包含30重量%至95重量%的聚酰亚胺树脂和5重量%至70重量%的含氟树脂颗粒,
其中所述多孔聚酰亚胺树脂层中分布着直径为0.05μm至20μm的微孔。
2.根据权利要求1所述的挠性金属层压板,
其中所述多孔聚酰亚胺树脂层具有1.2g/cm2至1.9g/cm2的密度。
3.根据权利要求1所述的挠性金属层压板,
其中所述多孔聚酰亚胺树脂层包括0.1体积%至5体积%的所述微孔。
4.根据权利要求1所述的挠性金属层压板,
其中所述含氟树脂颗粒具有0.05μm至9.5μm的平均粒径(D50)。
5.根据权利要求1所述的挠性金属层压板,
其中所述聚酰亚胺树脂具有1,000至500,000的重均分子量。
6.根据权利要求1所述的挠性金属层压板,
其中所述多孔聚酰亚胺树脂层具有0.1μm至200μm的厚度。
7.根据权利要求1所述的挠性金属层压板,
其中所述含氟树脂颗粒包含至少一种选自聚四氟乙烯(PTFE)、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)、四氟乙烯-六氟丙烯共聚物(FEP)、乙烯-四氟乙烯共聚物树脂(ETFE)、四氟乙烯-氯三氟乙烯共聚物(TFE/CTFE)和乙烯-氯三氟乙烯树脂(ECTFE)的化合物。
8.根据权利要求1所述的挠性金属层压板,
其中所述多孔聚酰亚胺树脂层在5GHz的状态下具有2.7以下的介电常数。
9.根据权利要求1所述的挠性金属层压板,
其中所述挠性金属层压板包括一个或多个所述多孔聚酰亚胺树脂层。
10.根据权利要求1所述的挠性金属层压板,
所述挠性金属层压板进一步包括至少一个厚度为0.1μm至200μm的热塑性聚酰亚胺树脂层。
11.根据权利要求1所述的挠性金属层压板,
其中所述挠性金属层压板包括金属薄膜,所述金属薄膜包含至少一种选自铜、铁、镍、钛、铝、银、金和由这些金属中的两种或多种构成的合金的金属。
12.根据权利要求11所述的挠性金属层压板,
其中所述金属薄膜具有0.1μm至50μm的厚度。
13.根据权利要求11所述的挠性金属层压板,
其中所述金属薄膜沉积在所述多孔聚酰亚胺树脂层的至少一面上。
14.一种用于制备挠性金属层压板的方法,其包括以下步骤:在约280℃至320℃的温度范围内改变升温速度,使包含30重量%至95重量%的聚酰胺酸树脂和5重量%至70重量%的含氟树脂颗粒的树脂组合物热固化,从而形成多孔聚酰亚胺树脂层;以及
在所述多孔聚酰亚胺树脂层的至少一面上沉积所述金属薄膜。
15.根据权利要求14所述的方法,
其中形成所述多孔聚酰亚胺树脂层的步骤包括:在等于或小于300℃的温度范围内以3℃/min至10℃/min的速度、以及在大于300℃的温度范围内以0.2℃/min至2℃/min的速度升高所述树脂组合物的温度。
16.根据权利要求15所述的方法,
其中所述升温过程在340℃至370℃的温度下完成。
17.根据权利要求14所述的方法,
其中形成所述多孔聚酰亚胺树脂层的步骤进一步包括:在所述热固化之前,在基板上涂布所述树脂组合物至0.1μm至200μm的厚度。
18.根据权利要求14所述的方法,
其中在所述多孔聚酰亚胺树脂层的至少一面上沉积所述金属薄膜的步骤包括:在250℃至450℃的温度下,施加500Kgf至3000Kgf的压力,从而在所述多孔聚酰亚胺树脂层的至少一面上沉积金属薄膜,其中所述金属薄膜包含至少一种选自铜、铁、镍、钛、铝、银、金和由这些金属中的两种或多种构成的合金的金属。
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CN110066557A (zh) * | 2019-05-05 | 2019-07-30 | 广东生益科技股份有限公司 | 一种涂树脂铜箔及其制备方法、包含其的覆铜板和印制电路板 |
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