CN115302870B - 一种覆铜箔层压板及其应用 - Google Patents
一种覆铜箔层压板及其应用 Download PDFInfo
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- CN115302870B CN115302870B CN202210790282.4A CN202210790282A CN115302870B CN 115302870 B CN115302870 B CN 115302870B CN 202210790282 A CN202210790282 A CN 202210790282A CN 115302870 B CN115302870 B CN 115302870B
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- clad laminate
- prepreg
- copper clad
- emulsion
- copper
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- 239000000835 fiber Substances 0.000 claims abstract description 84
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- 229920005989 resin Polymers 0.000 claims abstract description 68
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 63
- 239000004744 fabric Substances 0.000 claims abstract description 63
- 239000000839 emulsion Substances 0.000 claims abstract description 55
- 239000011230 binding agent Substances 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims abstract description 22
- 239000012784 inorganic fiber Substances 0.000 claims abstract description 21
- 239000011889 copper foil Substances 0.000 claims abstract description 19
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 15
- 239000011737 fluorine Substances 0.000 claims abstract description 15
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 12
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- 239000010949 copper Substances 0.000 claims description 44
- 239000011342 resin composition Substances 0.000 claims description 32
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- 239000003063 flame retardant Substances 0.000 claims description 20
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 13
- 229920001955 polyphenylene ether Polymers 0.000 claims description 12
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
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- 239000007822 coupling agent Substances 0.000 claims description 7
- 239000003999 initiator Substances 0.000 claims description 7
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- 239000004977 Liquid-crystal polymers (LCPs) Substances 0.000 claims description 6
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 claims description 6
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- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052580 B4C Inorganic materials 0.000 claims description 4
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims description 4
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 claims description 4
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- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 4
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- 239000011787 zinc oxide Substances 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 229920006231 aramid fiber Polymers 0.000 claims description 3
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- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
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- OUPYOLABCAXGHH-UHFFFAOYSA-N [Ba].[Rb] Chemical compound [Ba].[Rb] OUPYOLABCAXGHH-UHFFFAOYSA-N 0.000 claims description 2
- VNSWULZVUKFJHK-UHFFFAOYSA-N [Sr].[Bi] Chemical compound [Sr].[Bi] VNSWULZVUKFJHK-UHFFFAOYSA-N 0.000 claims description 2
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- IQONKZQQCCPWMS-UHFFFAOYSA-N barium lanthanum Chemical compound [Ba].[La] IQONKZQQCCPWMS-UHFFFAOYSA-N 0.000 claims description 2
- DUPIXUINLCPYLU-UHFFFAOYSA-N barium lead Chemical compound [Ba].[Pb] DUPIXUINLCPYLU-UHFFFAOYSA-N 0.000 claims description 2
- IJBYNGRZBZDSDK-UHFFFAOYSA-N barium magnesium Chemical compound [Mg].[Ba] IJBYNGRZBZDSDK-UHFFFAOYSA-N 0.000 claims description 2
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
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- YIMPFANPVKETMG-UHFFFAOYSA-N barium zirconium Chemical compound [Zr].[Ba] YIMPFANPVKETMG-UHFFFAOYSA-N 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- 229910002115 bismuth titanate Inorganic materials 0.000 claims description 2
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical class C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 claims description 2
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- DKDQMLPMKQLBHQ-UHFFFAOYSA-N strontium;barium(2+);oxido(dioxo)niobium Chemical compound [Sr+2].[Ba+2].[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O.[O-][Nb](=O)=O DKDQMLPMKQLBHQ-UHFFFAOYSA-N 0.000 claims description 2
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- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 1
- QMQVIEKDJWQHKY-UHFFFAOYSA-N C1(=CC=CC=C1)O.CN(C)CN Chemical compound C1(=CC=CC=C1)O.CN(C)CN QMQVIEKDJWQHKY-UHFFFAOYSA-N 0.000 description 1
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- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000000100 Hibiscus rosa sinensis Nutrition 0.000 description 1
- 229920002121 Hydroxyl-terminated polybutadiene Polymers 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 240000008254 Rosa chinensis Species 0.000 description 1
- 235000000664 Rosa chinensis Nutrition 0.000 description 1
- 235000016785 Rosa della China Nutrition 0.000 description 1
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- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
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- 150000002460 imidazoles Chemical class 0.000 description 1
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- 239000011810 insulating material Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000007561 laser diffraction method Methods 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000007257 malfunction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- OOHAUGDGCWURIT-UHFFFAOYSA-N n,n-dipentylpentan-1-amine Chemical compound CCCCCN(CCCCC)CCCCC OOHAUGDGCWURIT-UHFFFAOYSA-N 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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- RERMPCBBVZEPBS-UHFFFAOYSA-N tris(2,6-dimethylphenyl)phosphane Chemical compound CC1=CC=CC(C)=C1P(C=1C(=CC=CC=1C)C)C1=C(C)C=CC=C1C RERMPCBBVZEPBS-UHFFFAOYSA-N 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
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Abstract
本发明提供一种覆铜箔层压板及其应用,所述覆铜箔层压板包括预浸料层和设置于所述预浸料层两侧的铜箔;所述预浸料层包括芯层预浸料和设置于所述芯层预浸料两侧的无纺布预浸料;所述芯层预浸料中包括至少一张有机纤维布预浸料;所述无纺布预浸料中的无纺布由无机纤维和粘结剂组成,所述粘结剂选自含氟树脂乳液、聚烯烃乳液、聚苯醚树脂或氰酸酯树脂中的任意一种或至少两种的组合。本发明将包含特定的无纺布预浸料与有机纤维布预浸料复配,形成特定的层叠结构,使所述覆铜箔层压板具有低介电损耗,介电一致性和均匀性好,耐热性优异,力学强度和柔韧性高,具有高频高速的传输特性,充分满足了板材在高性能、小型化的电子产品中的应用需求。
Description
技术领域
本发明属于覆铜板技术领域,具体涉及一种覆铜箔层压板及其应用。
背景技术
近年来,信息技术飞速发展,各类具有高速信息处理功能的电子设备已成为日常生活中不可或缺的部分,计算机、手机、智能穿戴设备等电子产品面向高性能化、高功能化和网络化发展,为了高速传输和处理大容量信息,高频化和高速化是电子信息技术的主要发展方向。印制电路板是电子产品的重要组成部分,其各项性能都要求与电子信息技术的高频高速化发展相匹配。覆铜板作为制备印制电路板的基材,其制程和性能直接影响了印制电路板的水平。
在高频电路中,电信号传输损失用介电损耗、导体损失与辐射损失之和表示,电信号频率越高,则介电损耗、导体损失和辐射损失越大。由于传输损失使电信号衰减,破坏电信号的可靠性,同时该损耗从高频电路辐射,可能造成电子设备故障,因此,减小介电损耗、导体损耗和辐射损耗是十分必要的。研究表明,电信号的介电损耗与形成电路的绝缘体的介质损耗角正切及所使用的电信号频率的乘积成正比,因此,作为绝缘体,可以通过选择介质损耗角正切小的绝缘材料,以抑制介电损耗的增大。
覆铜板通常由铜箔与多张预浸料压合而成,预浸料包括增强材料与树脂组合物,高频信号传输的特性对预浸料的介电性能也提出了更高的要求,尤其要求预浸料具有低的介电损耗。为了获得性能更好的预浸料,研究人员一方面致力于树脂材料的开发,另一方面也将增强材料的性能优化作为研究重点。
无机纤维布是目前最常用的增强材料之一,例如玻璃纤维布、石英纤维布等,其在绝缘性、强度、耐热性等方面都具有良好的表现。但是,玻璃纤维布采用经纬编织而成,极易形成布纹,制备的覆铜板均匀性欠佳,导致覆铜板不同位置的介电常数、介电损耗、热膨胀性能有所不同,进而影响信号传输。与玻璃纤维布相比,有机纤维布的刚性较低,在柔韧性、耐磨性和加工性方面具有一定的优势,然而,有机纤维布也具有经纬编织结构,属于各向异性的增强材料,使包含其的覆铜板产生布纹,在不同位置/方向上的性能有所不同,对信号传输带来不利影响。
无纺布具有增强和各向同性的特点,近年来被广泛用于覆铜板中。例如CN102029746A公开了一种覆铜板,所述覆铜板包括:至少一层玻纤布增强半固化片、覆合于玻纤布增强半固化片两侧的玻纤纸增强半固化片以及覆合于玻纤纸增强半固化片上的铜箔;其中,玻纤纸即由玻璃纤维和粘结剂制成的无纺布,玻纤纸增强半固化片的引入降低了布纹的出现几率,提高了覆铜板的电气可靠性。CN108130784A公开了一种用于CEM-3覆铜箔板的E玻璃纤维纸及其制作方法,所述E玻璃纤维纸是由电子级的E型玻璃纤维和环氧树脂粘结剂制成的,是良好的CEM-3覆铜箔板基材。但是,现有的无纺布中的粘结剂主要包括环氧树脂粘结剂、丙烯酸酯类粘结剂、三聚氰胺类粘结剂或聚乙烯醇类粘结剂等,导致无纺布的介电损耗高,无法用于高频产品中,而且无纺布的增强效果、力学性能和耐热性都具有很大的改进空间。
总体而言,目前常用的纤维布增强的覆铜板的均匀性欠佳,影响电子产品的信号传输,而无纺布增强的覆铜板的介电损耗高,无法满足高频传输的性能要求。因此,本领域亟需开发一种兼具优异的介电性能、均匀性、力学性能和耐热性的覆铜板,以与高频传输的发展方向相适应。
发明内容
针对现有技术的不足,本发明的目的在于提供一种覆铜箔层压板及其应用,所述覆铜箔层压板中,通过无纺布的设计,以及无纺布预浸料与有机纤维布预浸料的复配,使其具有介电损耗低、力学强度高、介电一致性好、耐热性佳的特性,能够满足高频传输的高性能电子产品中的应用需求。
为达此目的,本发明采用以下技术方案:
第一方面,本发明提供一种覆铜箔层压板,所述覆铜箔层压板包括预浸料层和设置于所述预浸料层两侧的铜箔;所述预浸料层包括芯层预浸料和设置于所述芯层预浸料两侧的无纺布预浸料;所述芯层预浸料中包括至少一张有机纤维布预浸料;所述无纺布预浸料中的无纺布由无机纤维和粘结剂组成,所述粘结剂选自含氟树脂乳液、聚烯烃乳液、聚苯醚树脂或氰酸酯树脂中的任意一种或至少两种的组合。
本发明提供的覆铜箔层压板中,与铜箔接触的预浸料为无纺布预浸料,所述无纺布预浸料中的无纺布由无机纤维和特定的粘结剂组成,赋予所述无纺布低的介电损耗和优异的耐热性,且无纺布中纤维各向分布一致,厚度一致,均匀性好,拉伸强度高,可在浸渍介电性能优异的热固性树脂组合物时添加较多的填料,制备低介电损耗的高频覆铜箔层压板。
本发明将包含特定无纺布的无纺布预浸料与有机纤维布预浸料复配,形成特定的层叠结构,克服了纤维布预浸料与铜箔接触的位置出现布纹、白点等缺陷,使所述覆铜箔层压板的介电损耗低,介电性能优异,介电一致性和均匀性好,力学强度和柔韧性高,耐热性好,可靠性佳,充分满足了板材在制备高性能、小型化的电子产品中的应用需求。
需要说明的是,所述芯层预浸料两侧的两张无纺布预浸料相同或不同,即两张无纺布预浸料中的无纺布和/或热固性树脂组合物相同或不同。两张无纺布预浸料中的无纺布均由无机纤维和粘结剂组成,所述粘结剂相同或不同,各自独立地选自含氟树脂乳液、聚烯烃乳液、聚苯醚树脂或氰酸酯树脂中的任意一种或至少两种的组合。
所述芯层预浸料中包括至少一张有机纤维布预浸料,例如有机纤维布预浸料的张数可以为1、2、3、4、5、6、7、8、9或10等。此外,所述芯层预浸料中还包括可选地无纺布预浸料,所述芯层预浸料中的有机纤维布预浸料与可选地无纺布预浸料以任意可行的方式/顺序叠合。
所述芯层预浸料中有机纤维布预浸料的张数≥2时,多张有机纤维布预浸料(包括有机纤维布和/或热固性树脂组合物)相同或不同。
优选地,所述有机纤维布预浸料中的有机纤维布由有机纤维纱编织而成。
优选地,所述有机纤维纱包括液晶高分子纤维纱、氟树脂纤维纱或芳纶纤维纱中的任意一种或至少两种的组合。
优选地,所述有机纤维布的单重(又称单位面积质量)为20-200g/m2,例如可以为30g/m2、40g/m2、50g/m2、70g/m2、90g/m2、100g/m2、110g/m2、130g/m2、150g/m2、170g/m2或190g/m2等,进一步优选20-100g/m2。
优选地,所述无机纤维选自E玻璃纤维、NE玻璃纤维、L玻璃纤维、石英纤维、氧化铝纤维、氮化硼纤维、碳化硅纤维、氧化锌纤维、氧化镁纤维、氮化硅纤维、碳化硼纤维、氮化铝纤维、氧化铝晶须、氮化硼晶须、碳化硅晶须、氧化锌晶须、氧化镁晶须、氮化硅晶须、碳化硼晶须或氮化铝晶须的任意一种或至少两种的组合。
优选地,所述无机纤维的平均直径<10μm,例如可以为9μm、8μm、7μm、6μm、5μm、4μm、3μm、2μm或1μm等,进一步优选1-5μm。
优选地,所述无机纤维的平均长度为1-100mm,例如可以为2mm、5mm、8mm、10mm、20mm、30mm、40mm、50mm、60mm、70mm、80mm或90mm等,进一步优选1-10mm。
示例性地,所述无机纤维的平均直径和平均长度可采用扫描电子显微镜观察测试得到。
为了使所述无纺布及包含其的所述覆铜箔层压板具有更低的介电损耗,优选地,所述粘结剂为含氟树脂乳液。
优选地,所述含氟树脂乳液选自聚全氟乙丙烯(FEP)乳液、聚偏氟乙烯(PVDF)乳液、聚四氟乙烯(PTFE)乳液、四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)乳液、乙烯-四氟乙烯共聚物乳液、聚三氟氯乙烯(PCTFE)乳液或乙烯-三氟氯乙烯共聚物乳液中的任意一种或至少两种的组合。
优选地,所述含氟树脂乳液的固含量为30-70%,例如可以为32%、35%、38%、40%、42%、45%、48%、50%、52%、55%、58%、60%、62%、65%或68%等。
优选地,所述含氟树脂乳液中乳胶颗粒的粒径为0.10-0.40μm,例如可以为0.12μm、0.15μm、0.18μm、0.20μm、0.22μm、0.25μm、0.28μm、0.30μm、0.32μm、0.35μm或0.38μm等。
示例性地,所述含氟树脂乳液中乳胶颗粒的粒径采用激光衍射法测试,测试仪器马尔文激光粒度仪,型号MS3000。
优选地,所述聚烯烃乳液选自不饱和聚丁二烯树脂乳液、苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SBS)乳液、氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物(SEBS)乳液或丁苯树脂乳液中的任意一种或至少两种组合。
优选地,所述聚烯烃乳液的固含量为30-70%,例如32%、35%、38%、40%、42%、45%、48%、50%、52%、55%、58%、60%、62%、65%或68%等。
优选地,所述无纺布的单重(又称单位面积质量)为20-200g/m2,例如可以为30g/m2、40g/m2、50g/m2、70g/m2、90g/m2、100g/m2、110g/m2、130g/m2、150g/m2、170g/m2或190g/m2等,进一步优选20-100g/m2。
优选地,所述无纺布中无机纤维的质量百分含量为60-95%,例如可以为62%、65%、68%、70%、72%、75%、78%、80%、82%、85%、88%、90%、92%或94%等。
优选地,所述无纺布中粘结剂的质量百分含量为5-40%,例如8%、10%、12%、15%、18%、20%、22%、25%、28%、30%、32%、35%或38%等。
优选地,所述粘结剂可以根据需要添加溶剂去溶解稀释到合适的粘度,来使得制备的无纺布中的纤维、粘结剂分散均匀,溶剂示例性地包括但不限于包括去离子水等。溶剂会随着无纺布制备过程的烘干、烧结而挥发。
优选地,所述粘结剂还可以包括消泡剂、分散剂、增稠剂、填料等。
优选地,所述无纺布为低介电损耗无纺布,10GHz的介电损耗<0.0015,例如10GHz的介电损耗可以为0.0014、0.0013、0.0012、0.0011、0.0010、0.0009、0.0008或0.0007等。
本文中介电常数和介电损耗采用SPDR(split post dielectric resonator)法进行测试,频率为10GHz。
优选地,所述无纺布采用如下方法进行制备,所述方法包括:将无机纤维与粘结剂混合,浸渍,经过抄纸成型后干燥,得到所述无纺布。通过调整无机纤维、粘结剂、溶剂的比例及添加量、车速来获得不同单重的无纺布。
优选地,所述浸渍的时间为40-50min,例如41min、43min、45min、47min或49min等。
优选地,所述干燥的温度为120-150℃,例如122℃、125℃、128℃、130℃、132℃、135℃、138℃、140℃、142℃、145℃或148℃等。
优选地,所述干燥的时间为1-30min,例如1min、3min、5min、8min、10min、13min、15min、18min或20min等。
优选地,所述粘结剂为含氟树脂乳液,所述干燥后包括烧结的步骤,使含氟树脂熔融成膜。
优选地,所述烧结的温度为250℃-350℃,例如250℃、270℃、290℃、300℃、320℃、340℃或350℃等。
优选地,所述烧结的时间为1-30min,例如1min、3min、5min、8min、10min、13min、15min、18min、20min、23min、26min或30min等。
优选地,所述有机纤维布预浸料包括有机纤维布和附着于所述有机纤维布上的第一热固性树脂组合物。
优选地,所述有机纤维布预浸料中第一热固性树脂组合物的质量百分含量为60-95%,例如可以为62%、65%、68%、70%、72%、75%、78%、80%、82%、85%、88%、90%、92%或94%等。
优选地,所述无纺布预浸料包括无纺布和附着于所述无纺布上的第二热固性树脂组合物。
优选地,所述无纺布预浸料中第二热固性树脂组合物的质量百分含量为60-95%,例如可以为62%、65%、68%、70%、72%、75%、78%、80%、82%、85%、88%、90%、92%或94%等。
优选地,所述第一热固性树脂组合物、第二热固性树脂组合物各自独立地包括树脂,以及可选地交联剂、可选地引发剂、可选地阻燃剂、可选地填料、可选地偶联剂中的任意一种或至少两种的组合。
优选地,所述树脂选自聚苯醚树脂、聚烯烃树脂、多官能乙烯基芳香族聚合物、马来酰亚胺化合物或氰酸酯树脂中的任意一种或至少两种的组合。
优选地,所述聚苯醚树脂为含不饱和基团的聚苯醚,进一步优选为不饱和基团封端的聚苯醚。
优选地,所述不饱和基团包括乙烯基、乙烯基苯基、乙烯基苄基、丙烯酸酯基或甲基丙烯酸酯基中的任意一种或至少两种组合。
优选地,所述聚烯烃树脂包括聚丁二烯树脂、丁二烯-苯乙烯共聚物或苯乙烯-丁二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种的组合。
可选地,所述聚丁二烯树脂为极性基团改性聚丁二烯树脂,所述极性基团改性聚丁二烯树脂选自环氧改性聚丁二烯树脂、马来酸酐改性聚丁二烯树脂、丙烯酸改性聚丁二烯树脂、羟基封端的聚丁二烯树脂、羧基封端的聚丁二烯树脂、胺改性的聚丁二烯树脂中的任意一种或至少两种的组合。
本发明中,所述聚苯醚树脂、聚烯烃树脂为热固性树脂,其中包含可交联的活性基团,所述活性基团优选为不饱和C=C,例如含不饱和基团的聚苯醚中的不饱和键,聚烯烃树脂中丁二烯聚合形成的1,2-乙烯基等。
优选地,所述树脂包括含不饱和基团的聚苯醚、聚丁二烯树脂、丁二烯-苯乙烯共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物或马来酰亚胺化合物中的任意一种或至少两种的组合。
在一个优选实施方式中,所述树脂以重量份计包括:聚丁二烯树脂20-60份(例如25份、30份、35份、40份、45份、50份或55份等),马来酰亚胺化合物10-50份(例如15份、20份、25份、30份、35份、40份或45份等)。
在另一优选实施方式中,所述树脂以重量份计包括:含不饱和基团的聚苯醚50-90份(例如55份、60份、65份、70份、75份、80份或85份等),苯乙烯-丁二烯共聚物10-50份(例如15份、20份、25份、30份、35份、40份或45份等)。
优选地,所述交联剂包括异氰脲酸三烯丙酯、聚异氰脲酸三烯丙酯、三烯丙酯三聚氰酸酯、邻苯二甲酸二烯丙酯、三甲基丙烯酸、二乙烯基苯或多官能丙烯酸酯中的任意一种或至少两种的组合。
优选地,以所述树脂的质量为100份计,所述交联剂的质量为1-40份,例如可以为3份、5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份或38份等。
优选地,所述引发剂包括有机过氧化物、有机胺、有机膦、磷酸酯、亚磷酸酯、磷酸、酚类化合物、咪唑类化合物、三氟化硼及其络合物中的任意一种或至少两种的组合,进一步优选有机过氧化物。
优选地,所述引发剂包括α,α'-二(叔丁基过氧化间异丙)苯、过氧化二异丙苯、过氧化苯甲酰、叔丁基过氧化异丙苯、1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔、过氧化辛酸叔丁酯、过氧化苯甲酸叔丁酯、三级胺、三级胺盐、四级胺盐化合物、2,4,6-三(二甲胺基甲胺)苯酚、苄基二甲胺、咪唑类化合物、三戊基酚酸胺、单酚化合物、多酚化合物、三氟化硼及其有机物的络合物、磷酸或亚磷酸三苯酯中的任意一种或至少两种的组合。
优选地,所述引发剂包括α,α'-二(叔丁基过氧化间异丙)苯、过氧化二异丙苯、过氧化苯甲酰、叔丁基过氧化异丙苯、1,1-双(叔己基过氧化)-3,3,5-三甲基环己烷、2,5-二甲基-2,5-二(叔丁基过氧基)-3-己炔、过氧化辛酸叔丁酯或过氧化苯甲酸叔丁酯中的任意一种或至少两种的组合。
优选地,以所述树脂的质量为100份计,所述引发剂的质量为0.1-7份,例如可以为0.5份、1份、1.5份、2份、2.5份、3份、3.5份、4份、4.5份、5份、5.5份、6份或6.5份等。
本发明对于阻燃剂没有特别限定,具有阻燃效果的阻燃剂均可应用于所述所述第一热固性树脂组合物、第二热固性树脂组合物中。
优选地,所述阻燃剂包括氮系阻燃剂、卤系阻燃剂(例如含溴阻燃剂和/或含氯阻燃剂)、磷系阻燃剂或金属氢氧化物阻燃剂中的任意一种或至少两种的组合。
优选地,所述阻燃剂包括十溴二苯醚、乙基-双(四溴苯邻二甲酰亚胺)、十溴二苯基乙烷、三(2,6-二甲基苯基)膦、10-(2,5-二羟基苯基)-9,10-二氢-9-氧化-10膦菲-10-氧化物、2,6-二(2,6-二甲基苯基)膦基苯或10-苯基-9,10-二氢-9-氧化-10-膦菲-10-氧化物中的任意一种或至少两种的组合。
优选地,以所述树脂的质量为100份计,所述阻燃剂的质量为1-40份,例如可以为3份、5份、8份、10份、12份、15份、18份、20份、22份、25份、28份、30份、32份、35份或38份等。
优选地,所述填料包括二氧化硅、二氧化钛、氮化硼、氮化铝、碳化硅、氧化铝、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、铌酸钾、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜或钛酸铅-铌镁酸铅中的任意一种或至少两种的组合。
优选地,所述二氧化硅包括结晶型二氧化硅、无定型二氧化硅、球型二氧化硅中的任意一种或至少两种的组合。
优选地,所述填料的中值粒径(D50)为0.5-20μm,例如可以为1μm、2μm、3μm、4μm、5μm、6μm、7μm、8μm、9μm、10μm、11μm、13μm、15μm、17μm或19μm等,进一步优选1-15μm,更进一步优选4-10μm。
示例性地,所述填料的粒径采用MS3000马尔文激光粒度仪测试得到。
优选地,以所述树脂的质量为100份计,所述填料的质量为1-300份,例如可以为5份、10份、20份、30份、50份、70份、90份、100份、120份、150份、180份、200份、220份、250份或280份等。
优选地,所述偶联剂包括硅烷偶联剂、钛酸酯偶联剂、硼酸酯偶联剂、锆酸酯偶联剂或磷酸酯偶联剂中的任意一种或至少两种的组合,进一步优选硅烷偶联剂。
上述的热固性树脂组合物中还可以包含可选地其他助剂,以提高预浸料的使用性能和加工性等。
上述的热固性树脂组合物中还可以加入溶剂,溶剂的添加量由本领域技术人员根据工艺需求来选择,使树脂组合物达到适合使用的粘度,以便于热固性树脂组合物的浸渍、涂覆等即可。后续在烘干、半固化或完全固化环节,热固性树脂组合物中的溶剂会部分或完全挥发。
作为本发明的溶剂,没有特别限定,一般可选用丙酮、丁酮、环己酮等酮类,甲苯、二甲苯等芳香烃类,醋酸乙酯、醋酸丁酯等酯类,甲醇、乙醇或丁醇等醇类,乙基溶纤剂、丁基溶纤剂、乙二醇单甲醚、卡必醇或丁基卡必醇等醇类,N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或N-甲基-2-吡咯烷酮等含氮类;溶剂可以单独使用,也可两种或两种以上混合使用。优选丙酮、丁酮、环己酮等酮类,以及甲苯、二甲苯等芳香烃类。
示例性地,本发明中的预浸料(无纺布预浸料、有机纤维布预浸料)的制备方法为:采用热固性树脂组合物的树脂胶液浸润增强材料后,干燥,得到所述预浸料;所述增强材料为无纺布或有机纤维布。
优选地,所述干燥的温度为100-180℃,例如105℃、110℃、115℃、120℃、125℃、130℃、135℃、140℃、145℃、150℃、155℃、160℃、165℃、170℃或175℃等。
优选地,所述铜箔与预浸料层之间还包括粘结层。
优选地,所述粘结层涂覆于铜箔上(即采用涂树脂铜箔与预浸料层叠合)或以树脂膜的形式存在。
优选地,所述粘结层的材料包括含氟树脂、聚苯醚树脂、聚丁二烯树脂、苯乙烯-丁二烯共聚物、苯乙烯-丁二烯-苯乙烯三嵌段共聚物、多官能乙烯基芳香族共聚物、有机硅树脂、氰酸酯树脂或马来酰亚胺化合物中的任意一种或至少两种的组合。
优选地,所述覆铜箔层压板的制备方法包括:将第一无纺布预浸料、芯层预浸料和第二无纺布预浸料叠合成预浸料层,在所述预浸料层的两侧压合铜箔后,固化,得到所述覆铜箔层压板。
优选地,所述固化在压机中进行。
优选地,所述固化的温度为170-280℃,例如180℃、190℃、200℃、210℃、220℃、230℃、240℃、250℃、260℃或270℃等。
优选地,所述固化的压力为1-10MPa,例如1.5MPa、2MPa、3MPa、4MPa、5MPa、6MPa、7MPa、8MPa或9MPa等。
优选地,所述固化的时间为30-150min,例如40min、50min、60min、70min、80min、90min、100min、110min、120min、130min、140min或145min等。
第二方面,本发明提供一种印制电路板,所述印制电路板包括如第一方面所述的覆铜箔层压板。
相对于现有技术,本发明具有以下有益效果:
本发明提供的覆铜箔层压板中,将包含特定无纺布的无纺布预浸料与有机纤维布预浸料复配,形成特定的层叠结构,使预浸料与铜箔接触的位置不会出现布纹、白点等缺陷,使所述覆铜箔层压板具有低介电损耗,10GHz的介电损耗<0.0020,力学强度和柔韧性高,弯曲强度≥150MPa,介电一致性和均匀性好,耐热性优异,288℃热应力>5min,兼具优异的介电性能、均匀性、耐热性、力学性能和柔韧性,具有高频高速的传输特性,充分满足了板材在制备高性能、小型化的电子产品中的应用需求。
具体实施方式
下面通过具体实施方式来进一步说明本发明的技术方案。本领域技术人员应该明了,所述实施例仅仅是帮助理解本发明,不应视为对本发明的具体限制。
本发明以下具体实施方式中,用于无纺布的原料如下:
(1)无机纤维
平均直径为5μm的E玻璃纤维,中国巨石股份有限公司;
平均直径为5μm的NE玻璃纤维,中国巨石股份有限公司;
平均直径分别为1μm和5μm的石英纤维,中国神玖。
(2)粘结剂
聚全氟乙丙烯(FEP)乳液,粒径为0.20μm,固含量为50%,日本大金公司的ND-110;
四氟乙烯-全氟烷基乙烯基醚共聚物(PFA)乳液,粒径为0.20μm,固含量为55%,日本大金公司的AD-2CR;
聚四氟乙烯(PTFE)乳液,粒径为0.25μm,固含量为55%,日本大金公司的D210C;
聚烯烃乳液,粒径为0.1μm,固含量为45%,北京燕山石化。
制备例1
无纺布A,由E玻璃纤维和粘结剂组成,所述粘结剂为FEP乳液,具体制备方法如下:
以重量份计,将95份E玻璃纤维(平均直径为5μm)与5份FEP乳液和适量的去离子水混合后浸渍45min,经抄纸成型后,于150℃烘箱中干燥,再置于高温烘箱中300℃烧结30min,取出冷却,得到单重为20g/m2的无纺布A。
制备例2
无纺布B,由NE玻璃纤维和粘结剂组成,所述粘结剂为FEP乳液,具体制备方法如下:
以重量份计,将85份NE玻璃纤维(平均直径为5μm)与15份PFA乳液和适量的去离子水混合后浸渍45min,经抄纸成型后,于150℃烘箱中干燥,再置于高温烘箱中300℃烧结30min,取出冷却,得到单重为75g/m2的无纺布B。
制备例3
无纺布C,由NE玻璃纤维和粘结剂组成,所述粘结剂为PTFE乳液,具体制备方法如下:
以重量份计,将60份NE玻璃纤维(平均直径为5μm)与40份PTFE乳液和适量的去离子水混合后浸渍45min,经抄纸成型后,于150℃烘箱中干燥,再置于高温烘箱中330℃烧结30min,取出冷却,得到单重为75g/m2的无纺布C。
制备例4
无纺布D,由石英纤维和粘结剂组成,所述粘结剂为聚烯烃乳液,具体制备方法如下:
以重量份计,将85份石英纤维(平均直径为1μm和5μm,重量比为1:4)、与15份聚烯烃乳液混合后浸渍45min,经抄纸成型后,于120℃烘箱中充分干燥,取出冷却,得到单重为120g/m2的无纺布E。
本发明以下具体实施方式中,用于覆铜箔层压板的原料如下:
(1)无纺布
采用制备例1-4提供的无纺布,具体材料及参数如表1所示:
表1
无纺布D1,由环氧粘结剂和平均直径为13μm的E玻璃纤维组成,单重为75g/m2,购自陕西华特;
无纺布D2,由丙烯酸酯粘结剂和平均直径为13μm的E玻璃纤维组成,单重为75g/m2,购自陕西华特;
无纺布D3,由三聚氰胺粘结剂和平均直径为13μm的E玻璃纤维组成,单重为75g/m2,购自陕西华特。
(2)有机纤维布
液晶高分子纤维(LCP)有机纤维布,单重为48g/m2,金发科技;
芳纶有机纤维布,单重为50g/m2,山东京博控股集团有限公司;
聚四氟乙烯(PTFE)有机纤维布,单重为24g/m2,大金科技。
(3)热固性树脂组合物
热固性树脂组合物A,以重量份计包括如下组分:30份双马来酰亚胺(BMI-5100,大和化成株式会社),40份聚丁二烯(B2000,日本曹达株式会社),70份硅微粉(SJF0100E,壹石通股份有限公司),2份过氧化苯甲酰。按照前述配方量将热固性树脂组合物A溶于50份二甲苯中,混合均匀,得到均一的树脂胶液A。
热固性树脂组合物B,以重量份计包括如下组分:70份聚苯醚树脂MMA-PPE(SA9000,SABIC公司),30份苯乙烯-丁二烯共聚物(R100,Sartomer公司),3份过氧化异丙苯,15份含溴阻燃剂乙基-双(四溴苯邻二甲酰亚胺)(BT-93W,雅宝公司,溴含量67.2%)。按照前述配方量将热固性树脂组合物B与70份甲苯溶剂混合,充分搅拌分散均匀,得到均一的树脂胶液B。
实施例1
一种覆铜箔层压板,包括预浸料层以及设置于所述预浸料层两侧的铜箔;所述预浸料层包括有机纤维布预浸料(芯层预浸料)和设置于所述有机纤维布预浸料两侧的无纺布预浸料;所述有机纤维布预浸料为LCP有机纤维布预浸料,所述无纺布预浸料中的无纺布为无纺布A(制备例1)。
所述覆铜箔层压板的制备方法如下:
(1)用无纺布A浸渍树脂胶液A,155℃烘烤干燥5min,得到热固性树脂组合物的质量百分含量为60%的无纺布预浸料;用LCP有机纤维布浸渍树脂胶液B,155℃烘烤干燥5min,得到热固性树脂组合物的质量百分含量为95%的有机纤维布预浸料;
(2)将步骤(1)得到的无纺布预浸料和有机纤维布预浸料按照“1张无纺布预浸料-1张有机纤维布预浸料-1张无纺布预浸料”的顺序叠合,在其上下两侧覆盖铜箔,于压机中210℃、5MPa固化2h,得到所述覆铜箔层压板。
对所述覆铜箔层压板进行如下性能测试:
(1)介电损耗因子Df:使用谐振腔法(SPDR)法进行测定,频率为10GHz;
(2)热应力:按照IPC-650方法测试板材288℃的热应力;
(3)弯曲强度:按照IPC-650方法测试板材的弯曲强度;
(4)布纹:采用扫描电子显微镜(SEM,SU3500,日本日立株式会社)观察板材横截面,判断是否有布纹;
具体测试结果如表2所示。
实施例2-6,比较例1-5
一种覆铜箔层压板,其与实施例1的区别在于,预浸料的种类或层叠结构不同,具体如表2和表3所示;其中,“热固性树脂组合物比例(%)”意指有机纤维布预浸料/无纺布预浸料中的热固性树脂组合物的质量百分含量,“结构”意指两张铜箔之间的预浸料层的层叠结构。按照实施例1中相同的方法制备覆铜箔层压板并对其进行性能测试,测试结果如表2和表3所示。
表2
表3
根据表2-3的性能测试结果可知,本发明将包含特定无纺布的无纺布预浸料与有机纤维布预浸料复配,形成特定的层叠结构,使所述覆铜箔层压板在10GHz的介电损耗<0.0020,可低至0.0013-0.0019,力学强度高,柔韧性好,弯曲强度为150-172MPa,介电一致性和均匀性好,预浸料与铜箔接触的位置不会出现布纹、白点等缺陷,耐热性优异,288℃热应力>5min,兼具介电损耗低、介电一致性和均匀性好、耐热性好、力学强度高、柔韧性好的特性,能够实现高频高速的信号传输,充分满足了板材在制备高频高性能和小型化的电子产品中的应用需求。
对比实施例2与比较例1-2可知,如果覆铜箔层压板中不包含有机纤维布预浸料(比较例1),则板材的弯曲强度只有95MPa,难以满足覆铜箔层压板支撑的要求;如果覆铜箔层压板中不包含无纺布预浸料(比较例2),则会存在明显的布纹缺陷,使板材的均匀性不佳。
本发明通过无纺布中粘结剂的设计,使所述无纺布具有低的介电损耗,纤维各向分布一致,均匀性好,强度高,耐热性佳,进而使包含其的覆铜箔层压板具有低介电损耗、优异的耐热性和可靠性。对比实施例1与比较例3-5的性能数据可知,现有的无纺布作为增强材料,板材的介电损耗Df高,且热应力仅有3s,无法满足高频传输和耐热性的要求。
申请人声明,本发明通过上述实施例来说明本发明的一种覆铜箔层压板及其应用,但本发明并不局限于上述实施例,即不意味着本发明必须依赖上述实施例才能实施。所属技术领域的技术人员应该明了,对本发明的任何改进,对本发明产品各原料的等效替换及辅助成分的添加、具体方式的选择等,均落在本发明的保护范围和公开范围之内。
Claims (27)
1.一种覆铜箔层压板,其特征在于,所述覆铜箔层压板包括预浸料层和设置于所述预浸料层两侧的铜箔;所述预浸料层包括芯层预浸料和设置于所述芯层预浸料两侧的无纺布预浸料;
所述芯层预浸料中包括至少一张有机纤维布预浸料;
所述无纺布预浸料中的无纺布由无机纤维和粘结剂组成,所述粘结剂选自含氟树脂乳液和/或聚烯烃乳液;
所述含氟树脂乳液选自聚全氟乙丙烯乳液、聚偏氟乙烯乳液、聚四氟乙烯乳液、四氟乙烯-全氟烷基乙烯基醚共聚物乳液、乙烯-四氟乙烯共聚物乳液、聚三氟氯乙烯乳液或乙烯-三氟氯乙烯共聚物乳液中的任意一种或至少两种的组合;
所述含氟树脂乳液的固含量为30-70%;
所述聚烯烃乳液选自不饱和聚丁二烯树脂乳液、苯乙烯-丁二烯-苯乙烯三嵌段共聚物乳液、氢化苯乙烯-丁二烯-苯乙烯三嵌段共聚物乳液或丁苯树脂乳液中的任意一种或至少两种组合;
所述聚烯烃乳液的固含量为30-70%;
所述无纺布中无机纤维的质量百分含量为60-95%,粘结剂的质量百分含量为5-40%;
所述无纺布预浸料包括无纺布和附着于所述无纺布上的第二热固性树脂组合物。
2.根据权利要求1所述的覆铜箔层压板,其特征在于,所述有机纤维布预浸料中的有机纤维布由有机纤维纱编织而成。
3.根据权利要求2所述的覆铜箔层压板,其特征在于,所述有机纤维纱包括液晶高分子纤维纱、氟树脂纤维纱或芳纶纤维纱中的任意一种或至少两种的组合。
4.根据权利要求1所述的覆铜箔层压板,其特征在于,所述有机纤维布的单重为20-200g/m2。
5.根据权利要求4所述的覆铜箔层压板,其特征在于,所述有机纤维布的单重为20-100g/m2。
6.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无机纤维选自E玻璃纤维、NE玻璃纤维、L玻璃纤维、石英纤维、氧化铝纤维、氮化硼纤维、碳化硅纤维、氧化锌纤维、氧化镁纤维、氮化硅纤维、碳化硼纤维或氮化铝纤维中的任意一种或至少两种的组合。
7.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无机纤维选自氧化铝晶须、氮化硼晶须、碳化硅晶须、氧化锌晶须、氧化镁晶须、氮化硅晶须、碳化硼晶须或氮化铝晶须中的任意一种或至少两种的组合。
8.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无机纤维的平均直径<10 μm。
9.根据权利要求8所述的覆铜箔层压板,其特征在于,所述无机纤维的平均直径为1-5μm。
10.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无机纤维的平均长度为1-100 mm。
11.根据权利要求10所述的覆铜箔层压板,其特征在于,所述无机纤维的平均长度为1-10 mm。
12.根据权利要求1所述的覆铜箔层压板,其特征在于,所述粘结剂为含氟树脂乳液。
13.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无纺布的单重为20-200 g/m2。
14.根据权利要求13所述的覆铜箔层压板,其特征在于,所述无纺布的单重为20-100g/m2。
15.根据权利要求1所述的覆铜箔层压板,其特征在于,所述有机纤维布预浸料包括有机纤维布和附着于所述有机纤维布上的第一热固性树脂组合物。
16.根据权利要求15所述的覆铜箔层压板,其特征在于,所述有机纤维布预浸料中第一热固性树脂组合物的质量百分含量为60-95%。
17.根据权利要求1所述的覆铜箔层压板,其特征在于,所述无纺布预浸料中第二热固性树脂组合物的质量百分含量为60-95%。
18.根据权利要求15所述的覆铜箔层压板,其特征在于,所述第一热固性树脂组合物、第二热固性树脂组合物各自独立地包括树脂,以及可选地交联剂、可选地引发剂、可选地阻燃剂、可选地填料、可选地偶联剂中的任意一种或至少两种的组合。
19.根据权利要求18所述的覆铜箔层压板,其特征在于,所述树脂选自聚苯醚树脂、聚烯烃树脂、多官能乙烯基芳香族聚合物、马来酰亚胺化合物或氰酸酯树脂中的任意一种或至少两种的组合。
20.根据权利要求19所述的覆铜箔层压板,其特征在于,所述聚烯烃树脂包括聚丁二烯树脂、丁二烯-苯乙烯共聚物或苯乙烯-丁二烯-苯乙烯三嵌段共聚物中的任意一种或至少两种的组合。
21.根据权利要求18所述的覆铜箔层压板,其特征在于,所述交联剂包括异氰脲酸三烯丙酯、聚异氰脲酸三烯丙酯、三烯丙酯三聚氰酸酯、邻苯二甲酸二烯丙酯、三甲基丙烯酸、二乙烯基苯或多官能丙烯酸酯中的任意一种或至少两种的组合。
22.根据权利要求18所述的覆铜箔层压板,其特征在于,所述引发剂包括有机过氧化物。
23.根据权利要求18所述的覆铜箔层压板,其特征在于,所述阻燃剂包括氮系阻燃剂、卤系阻燃剂、磷系阻燃剂或金属氢氧化物阻燃剂中的任意一种或至少两种的组合。
24.根据权利要求18所述的覆铜箔层压板,其特征在于,所述填料包括二氧化硅、二氧化钛、氮化硼、氮化铝、碳化硅、氧化铝、钛酸钡、钛酸锶、钛酸镁、钛酸钙、钛酸锶钡、钙钛酸钡、钛酸铅、锆钛酸铅、锆钛酸镧铅、钛酸镧钡、钛酸锆钡、二氧化铪、铌镁酸铅、铌镁酸钡、铌酸锂、铌酸钾、钽酸铝锶、铌酸钽钾、铌酸锶钡、铌酸钡铅、铌酸钛钡、钽酸铋锶、钛酸铋、钛酸钡铷、钛酸铜或钛酸铅-铌镁酸铅中的任意一种或至少两种的组合。
25.根据权利要求1所述的覆铜箔层压板,其特征在于,所述铜箔与预浸料层之间还包括粘结层。
26.根据权利要求25所述的覆铜箔层压板,其特征在于,所述粘结层涂覆于铜箔上或以树脂膜的形式存在。
27.一种印制电路板,其特征在于,所述印制电路板包括如权利要求1-26任一项所述的覆铜箔层压板。
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