CN100508690C - 印刷电路板用层压板及其制造方法 - Google Patents

印刷电路板用层压板及其制造方法 Download PDF

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CN100508690C
CN100508690C CNB2006100576153A CN200610057615A CN100508690C CN 100508690 C CN100508690 C CN 100508690C CN B2006100576153 A CNB2006100576153 A CN B2006100576153A CN 200610057615 A CN200610057615 A CN 200610057615A CN 100508690 C CN100508690 C CN 100508690C
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CN1863433A (zh
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申畯植
崔哲豪
孙暻镇
尹今姬
李尚烨
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Samsung Electro Mechanics Co Ltd
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Abstract

本发明涉及印刷电路板用层压板,该层压板通过将由液晶聚酯纤维形成的织物或无纺布引入液晶聚酯树脂中而制造,因而具有低介电常数和低损耗因子,适合用于高频范围(GHz或更高),并表现出优异的热性能和高可靠性,得到高的可加工性。

Description

印刷电路板用层压板及其制造方法
技术领域
一般而言,本发明涉及印刷电路板(PCB)用层压板及其制造方法,更具体而言,涉及PCB用层压板,该层压板通过将由液晶聚酯纤维形成的织物或无纺布引入到液晶聚酯树脂中而制造,因而该层压板具有低介电常数和低介电损耗因子,甚至在高频范围内也是如此,并表现出优异的热性能,本发明还涉及该PCB用层压板的制造方法。
背景技术
通常,用于封装基板的半固化片和覆铜层压板(CCL)主要是利用BT(双马来酰亚胺三嗪)树脂和环氧树脂(例如:高Tg FR-4)制造。
此外,将BT或环氧树脂(例如,清漆)与玻璃布混合制备B阶半固化片。所制备的半固化片与铜箔一起层压成多层,加热并压制,从而制造CCL。
就这一点来说,相对于使用环氧树脂,优选使用BT树脂。这是因为BT树脂的热性能(高Tg)、电性能和铜箔剥离强度均优于环氧树脂,并且在结构上是稳定的。
在这些性能中,特别是热性能(Tg)被认为是最重要的。原因在于封装基板应该是十分可靠的。也就是说,由于热膨胀系数(CTE)在Tg温度以下和以上是不同的,因而可由于制造过程中的非均匀体积收缩而导致封装基板产生脆性和翘曲。制造过程中,在Tg温度以下和以上反复进行非均匀的热膨胀和热收缩,因而产生残余应力,导致成品的脱层和翘曲。
具有上述性能的传统封装材料是通过将具有低热膨胀系数但是介电常数高为约6.2的玻璃布(例如,E玻璃型玻璃布)引入到BT或环氧树脂中而制造的。因此,其介电常数达3.5~4,并且损耗因子也很大。结果,该传统封装材料难以用于高频范围(GHz)。
为了克服该问题,继续针对以下两方面进行了大量努力,即开发具有优异的热膨胀系数但是具有高的介电常数和损耗因子的基板材料以替代玻璃布,和开发具有低的介电常数和损耗因子的基板材料以替代BT或环氧树脂。
首先,为了替代玻璃布,已经提出了制造基板材料的方法,包括将具有低的介电常数和损耗因子的液晶聚合物无纺布引入到传统BT或环氧树脂中。该方法优点在于可极大地降低玻璃布的高介电常数和损耗因子,但是缺点在于BT或环氧树脂具有过高的介电常数,不适合用于高频范围,并且其损耗因子增加,因而在高于Tg(约180℃)的温度下发生快速热膨胀。
其次,已经提出利用具有优异热膨胀系数的玻璃布和作为绝缘材料的具有远低于BT或环氧树脂的介电常数和损耗因子的聚四氟乙烯(Teflon)来制造基板材料的方法。在这种情况下,所制造的基板材料具有低的介电常数和损耗因子,以及优异的热膨胀系数,但是价格昂贵且可加工性差。
同时,热塑性液晶聚合物作为用于FCCL(柔性覆铜层压板)的聚酰亚胺的替代材料正受到关注,所述FCCL是柔性和刚性&柔性PCB材料。原因在于液晶聚合物可克服聚酰亚胺的缺点(高吸水率、尺寸不稳定性以及高介电常数(Dk)和损耗因子(Df))。此外,液晶聚合物甚至在高频(GHz)范围内也具有低的介电常数和损耗因子,由此表现出优异的电性能。
因此,已经全面尝试将液晶聚合物用作基板材料和层间绝缘材料以替代传统上用于柔性和刚性柔性PCB中的聚酰亚胺,这依靠的是液晶聚合物优异的电性能,如低介电常数、低损耗因子和低热膨胀系数。
具体而言,日本和美国的化学公司迄今已经生产出FCCL和绝缘膜,并且与PCB制造商共同研究该层压板和膜至高频范围(GHz)的应用和发展以及下一代柔性和刚性&柔性PCB。此外,对具有上述优异性能的液晶聚合物在封装基板上的应用研究正在进行中。
然而,当单独使用具有上述优异性能的液晶聚合物时,刚度显得不足。因此,该聚合物只能有限地用于柔性和刚性&柔性PCB中,并且难以应用于半导体封装基板。因此,迫切需要开发一种新型封装基板材料,其具有适合用于高频范围的低介电常数和损耗因子、低热膨胀系数、高可靠性、低成本和出色的可加工性。
发明内容
因此,鉴于现有技术中所存在的上述问题,进行了本发明,本发明的目的在于提供一种PCB用层压板,其中将液晶聚合物织物或液晶聚合物无纺布用作液晶聚合物树脂中的增强材料,以克服被认为是液晶聚合物的缺点的低刚度,同时使其优点最大化,以用于封装基板。
本发明的另一目的在于提供制造该PCB用层压板的方法。
根据实现上述目的的本发明的一个方面,提供一种PCB用层压板,其通过将由介电常数为2.5-3.0、液晶熔点为260-350℃的液晶聚酯纤维形成的织物或无纺布引入到液晶熔点为280-360℃的液晶聚酯树脂中而制造。
在本发明的层压板中,液晶聚酯树脂的液晶熔点优选低于液晶聚酯纤维的液晶熔点。
此外,液晶聚酯树脂优选包括由下列化学式1、2、3和4所代表的重复单元,其中基于液晶聚酯树脂的量,化学式1的重复单元的用量为20-70mol%,化学式2的重复单元的用量为7-30mol%,化学式3的重复单元的用量为7-30mol%,化学式4的重复单元的用量为7-30mol%:
化学式1
—O—Ar1—CO—
化学式2
—CO—Ar2—CO—
化学式3
—O—Ar3—O—
化学式4
—X—Ar4—Y—
在化学式1-4中,Ar1-Ar4相同或不同,各自为C6-C12芳基,X为—NH—,Y为—O—或—NH—。
此外,液晶聚酯纤维优选具有1-15μm的平均厚度。
此外,层压板优选包含5-60重量%的由液晶聚酯纤维形成的一体化织物或无纺布。
此外,层压板还可包含选自二氧化硅、氧化铝、氧化钛、碳酸钙、碳、石墨及其混合物的填料。
根据本发明的另一方面,提供制造PCB用层压板的方法,所述方法包括以下步骤:(a)提供由液晶聚酯纤维形成的织物或无纺布,所述液晶聚酯纤维具有2.5-3.0的介电常数和260-350℃的液晶熔点;(b)将由液晶聚酯纤维形成的织物或无纺布引入到液晶聚酯溶液中以得到一体化的液晶聚酯织物或无纺布,所述液晶聚酯溶液包含溶剂和液晶熔点为280-360℃的液晶聚酯树脂;(c)干燥所述一体化的液晶聚酯织物或无纺布;和(d)层压所述干燥的液晶聚酯织物或无纺布以形成多层,随后加热和压制该层压的液晶聚酯织物或无纺布。
在本发明的方法中,优选步骤(c)在50-200℃下进行0.5-2小时,并且步骤(d)在200-400℃下进行0.5-4小时。
此外,优选在惰性气氛中进行步骤(c)和(d)。
根据本发明的又一步骤,提供通过在本发明的层压板的至少一个表面上层压铜箔而制造的CCL。
根据本发明的再一方面,提供一种PCB,其包含外电路层、至少一个内电路层和在其中具有电连接电路层的通孔的绝缘层,其中所述绝缘层是本发明的层压板。
附图说明
图1是根据本发明顺序示出制造PCB用层压板的方法的图;
图2是根据本发明顺序示出利用所述PCB用层压板制造CCL的方法的图。
具体实施方式
下文将参照附图详细说明本发明。
根据本发明,提供一种新型基板材料,其优点在于具有低的介电常数和损耗因子,适合用于高频范围,这归功于使用液晶聚合物树脂和液晶聚合物织物或液晶聚合物无纺布。此外,该基板材料具有低吸水率、出色的尺寸稳定性和优异的热性能。因此,期望本发明的基板材料在未来极大地影响PCB的高功能化和微型化。
作为参考,用作基板材料的液晶聚酯、聚酰亚胺、BT和环氧树脂的主要性能总结于下表1中。
表1
Figure C200610057615D00081
注:CTE:热膨胀系数,
    CHE:吸湿膨胀系数,
    Dk:介电常数,
    Df:损耗因子。
参考示出根据本发明的PCB用层压板制造方法的图1,本发明的PCB用层压板的制造方法如下所述。
首先,将由液晶聚酯纤维形成的织物或无纺布制成液晶聚酯织物或无纺布进给部件10。
液晶聚酯纤维具有1-15μm的平均厚度、2.5-3.0的介电常数和260-350℃、优选320-350℃的液晶熔点,所述液晶聚酯纤维作为增强材料而引入到下述液晶聚酯树脂中,以表现出合适的模量性能、出色的钻孔加工性、低介电常数、低损耗因子和优异的热性能。该液晶聚酯纤维具有适用于封装材料的刚度,以及高耐热性、低介电常数、低吸水率等。因而,可以克服现有玻璃布的问题(高介电常数和损耗因子)。
液晶聚酯纤维不受具体限制,现有技术中已知的任何材料只要其充分满足上述所需性能就可使用。
接着,将由聚酯纤维形成的织物或无纺布引入到液晶聚酯溶液中成为液晶聚酯溶液一体化部件20,所述液晶聚酯溶液包含溶剂和液晶熔点为280-360℃的液晶聚酯树脂。
虽然所述溶剂不受具体限制,但是可优选使用非质子溶剂或含有卤素原子的溶剂。所用溶剂的量不受具体限制,只要其溶解该液晶聚酯树脂即可,并且可根据其用途适当确定。液晶聚酯用量为1-100重量份,优选5-15重量份,适合于表现出可加工性和经济的优点,所述用量基于100重量份的溶剂。
液晶聚酯树脂的熔点为280-360℃,优选300-320℃,使得不仅介电常数和损耗因子而且在Tg以上和以下温度的热膨胀系数均保持很低。具体而言,液晶聚酯树脂应该具有低于所引入的液晶聚合物纤维的熔点,以使当通过预干燥、层压和高温热处理的后续步骤制造层压板时,由液晶聚合物纤维形成的织物或无纺布能够在不低于液晶聚合物树脂热变形温度的温度下进行热处理而不改变其物理性能。
液晶聚酯树脂不受具体限制,只要其充分满足上述所需性能即可。优选的是,液晶聚酯树脂具有由以下化学式1、2、3和4所代表的重复单元:
化学式1
—O—Ar1—CO—
化学式2
—CO—Ar2—CO—
化学式3
—O—Ar3—O—
化学式4
—X—Ar4—Y—
在化学式1-4中,Ar1-Ar4相同或不同,各自为C6-C12芳基,X为—NH—,Y为—O—或—NH—。
优选的是,液晶聚酯树脂包含20-70mol%的化学式1的重复单元、7-30mol%的化学式2的重复单元、7-30mol%的化学式3的重复单元、7-30mol%的化学式4的重复单元,适合于表现出所需性能。
此外,一体化时间不受具体限制,但是适当控制结合时间以制造包含5-60重量%的由液晶聚酯纤维形成的一体化织物或无纺布的层压板。
出于减小热膨胀系数和吸水率以及增加模量的目的,液晶聚酯溶液还可根据需要包含填料。此外,还可以包含添加剂,包括相容剂、染料、颜料、抗静电剂等。
所述填料选自无机材料如二氧化硅、氧化铝、氧化钛、碳酸钙等和有机材料如碳、石墨等以及其混合物。填料优选具有0.1-10μm的平均粒径。如果填料具有超出上限的平均粒径,则会容易发生集聚且表面平坦度会下降。基于液晶聚酯溶液的用量,填料用量为5-60体积%,优选10-40体积%,以实现经济的优点并表现出所需的性能。
随后,将一体化的液晶聚酯织物或无纺布在50-200℃下预干燥0.5-2小时,优选在100-150℃下预干燥1-2小时,层压为多层且达到期望厚度,并在200-400℃下加热和压制0.5-4小时,优选在200-280℃下进行1-2小时,完全干燥并热处理以除去干燥部件30中的溶剂,从而得到最终层压板40。
当制造层压板40时,利用本领域技术人员所公知的方法在层压板的一个表面或两个表面上层压铜箔,以制造覆铜层压板。
就这一点而论,应该考虑到液晶聚酯织物或无纺布和液晶聚酯树脂的所有熔点,来进行加热、压制和热处理过程。
也就是说,为了改变基板厚度、改善基板粘合强度以及防止基板脱层和开裂,在不低于液晶聚酯树脂的热变形温度即熔点的温度下进行热处理过程,而层压过程可以根据需要在不高于液晶聚酯树脂的热变形温度即熔点的温度下进行。因而,应该考虑液晶聚酯织物或无纺布和液晶聚酯树脂的所有熔点,根据所需用途来适当设定热处理过程的温度。
在空气气氛或惰性气氛如氮气中进行干燥过程,优选在惰性气氛中进行。
如果在过高温度下进行预干燥过程,则会由于快速溶剂蒸发而发生收缩和翘曲。此外,在层压和热处理过程中,应该注意在过高温度下加热和压制会导致液晶聚酯织物或无纺布的物理性能改变。
因为传统半固化片处于未固化的B阶,必须通过在高温下长时间加热和压制来进行固化和层压过程。然而,当根据本发明的方法使用液晶聚合物树脂时,液晶聚合物树脂具有热塑性能,因而可以通过短时间加热和压制来进行层压。因此,可以减少制造成本和时间。
此外,虽然传统上使用的未固化B阶半固化片的缺点在于由于产品变形而仅可贮存约3个月,但是本发明的层压板可以容易地进行处理,而没有变形问题。
而且,本发明的液晶聚合物可在高于Tg的温度下热膨胀。然而,该膨胀程度远小于普通的热固性树脂。此外,选择性使用填料,导致热膨胀系数下降。并且,吸水率减小而模量增加。
将本发明的CCL或层压板应用于普通的PCB制造过程,因而可用作外层或内层基板或作为电路层间的绝缘层。
再参考图2,其示出利用本发明的层压板制造CCL的方法。
将多个层压板40与约18微米或更薄的铜箔(例如,电沉积铜箔或轧制铜箔)一起层压成层叠部件60,所述铜箔具有表面粗糙度,插入到铜箔进给部件50中,利用加热和压制装置如V压机或加热辊加热和压制成加热和压制部件70,并且为了最终检验而修整成修整部件80,以制造具有不同厚度的CCL90。
这样,具有优异性能的本发明基板材料可以采用与制造基板材料(半固化片和CCL)的传统方法相同的方式制造,同时采用无变化的传统过程而不加入额外的过程。
此外,通过采用液晶聚合物树脂和液晶聚酯织物或无纺布制造的本发明的层压板或CCL的优点在于其具有远低于传统热固性树脂的介电常数和损耗因子,因而可以用于高频范围。此外,该层压板或CCL具有极低的热膨胀系数,因此满足封装基板材料所需的高可靠性。
而且,为了确保阻燃性,本发明的基板材料不含传统上用于环氧树脂的溴(Br)或氯(Cl),因而是无卤素的。此外,本发明材料具有优异的耐热性且可以是无Pb的,这取决于焊接上对于Pb的使用限制。因此,本发明的基板材料被认为是环境友好的。
此外,克服了包含环氧树脂和玻璃布的传统层压板的缺点,如钻孔加工性差(钻孔磨损)、在利用钻孔机或铣削机加工时产生粉末(这导致杂质和透孔/废料(opens/shorts))。
根据以下实施例可以更好地理解本发明,所述实施例是为举例说明而提出,并非是用来限制本发明。
实施例1
将10重量份具有约300℃液晶熔点的液晶聚酯树脂溶解于100重量份作为溶剂的N-甲基吡咯烷酮中,以制备液晶聚酯溶液。将由液晶聚酯纤维形成的无纺布(VECRUS,得自Kuraray)在室温下引入到所制备的溶液中持续约8分钟,所述液晶聚酯纤维具有约10μm的平均厚度、2.8的介电常数和约330℃的液晶熔点。将一体化的无纺布在氮气气氛下于约100℃预干燥约1小时,与铜箔一起在约250℃下加热和压制约2小时,热处理并彻底干燥,从而制造本发明的CCL。测量所制造的CCL的介电常数、损耗因子、热膨胀系数和吸水率。结果示于下表2中。
对比实施例1
采用与实施例1相同的方法制造CCL,但是采用BT清漆替代液晶聚酯溶液。测量所制造的CCL的介电常数、损耗因子、热膨胀系数和吸水率。结果示于下表2中。
对比实施例2
采用与实施例1相同的方法制造CCL,但是采用环氧清漆替代液晶聚酯溶液。测量所制造的CCL的介电常数、损耗因子、热膨胀系数和吸水率。结果示于下表2中。
对比实施例3
采用与实施例1相同的方法制造CCL,但是分别采用PTFE清漆和玻璃布替代液晶聚酯溶液和由液晶聚酯纤维形成的无纺布。测量所制造的CCL的介电常数、损耗因子、热膨胀系数和吸水率。结果示于下表2中。
表2
 
实施例1 对比实施例1 对比实施例2 对比实施例3
Dk(1GHz) <2.8 3.1~3.3 2.9~3.1 2.6
Df(1GHz) <0.0015 0.0035 0.0027 0.002
CTE 18 20~30 20~30 9.5
吸水率 <0.02 0.18 1.2 <0.02
由表2明显可见,采用BT树脂和液晶聚酯无纺布得到的CCL(对比实施例1)和采用环氧树脂和液晶聚酯无纺布得到的CCL(对比实施例2)具有高热膨胀系数、高介电常数和高损耗因子,因而不适用于高频范围。此外,采用PTFE树脂和玻璃布得到的CCL(对比实施例3)具有低介电常数、低损耗因子和低吸水率,但具有高制造成本、差的加工性和低粘合强度。如果将该CCL应用于制造多层PCB,则会引起问题。然而,采用液晶聚酯树脂和液晶聚酯无纺布得到的CCL(实施例1)具有低介电常数、低损耗因子以及优异的热性能和可加工性。
出于说明的目的,但不应理解为限制本发明,已经公开了本发明的关于PCB用层压板及其制造方法的优选实施方案,本领域技术人员将理解可以在不背离本发明精神的情况下进行各种更改、添加和替换。
如上所述,本发明提供一种PCB用层压板及其制造方法。根据本发明,当制造层压板时,使用液晶聚酯树脂和液晶聚酯织物或无纺布来替代作为传统封装基板材料的热固性树脂(BT、环氧树脂)和玻璃纤维。因此,介电常数和损耗因子均减小,并且本发明的层压板因而适用于高频范围。此外,热膨胀系数在高于Tg的温度下很低并且可加工性优异,因此制造高可靠的层压板。
本发明的层压板可期望用于高频范围并且根据其改善的性能而适用于需要高可靠性的半导体封装基板。
根据上述教导可以对本发明进行许多更改和变化,而不背离所附权利要求中公开的本发明的范围和精神。

Claims (13)

1.印刷电路板用层压板,其通过将由液晶聚酯纤维形成的织物或无纺布引入到液晶熔点为280-360℃的液晶聚酯树脂中而制造,所述液晶聚酯纤维具有2.5-3.0的介电常数和260-350℃的液晶熔点。
2.权利要求1的层压板,其中液晶聚酯树脂的液晶熔点低于液晶聚酯纤维的液晶熔点。
3.权利要求1的层压板,其中液晶聚酯树脂包含由以下化学式1、2、3和4所代表的重复单元,其中基于液晶聚酯树脂的量,化学式1的重复单元的用量为20-70mol%,化学式2的重复单元的用量为7-30mol%,化学式3的重复单元的用量为7-30mol%,化学式4的重复单元的用量为7-30mol%:
化学式1
—O—Ar1—CO—
化学式2
—CO—Ar2—CO—
化学式3
—O—Ar3—O—
化学式4
—X—Ar4—Y—
在化学式1-4中,Ar1-Ar4相同或不同,各自为C6-C12芳基,X为—NH—,Y为—O—或—NH—。
4.权利要求1的层压板,其中液晶聚酯纤维具有1-15μm的平均厚度。
5.权利要求1的层压板,其中所述层压板包含5-60重量%的由液晶聚酯纤维形成的一体化的织物或无纺布。
6.权利要求1的层压板,还包含选自二氧化硅、氧化铝、氧化钛、碳酸钙、碳和石墨中的一种或两种以上填料。
7.制造印刷电路板用层压板的方法,包括以下步骤:
(a)提供由液晶聚酯纤维形成的织物或无纺布,所述液晶聚酯纤维具有2.5-3.0的介电常数和260-350℃的液晶熔点;
(b)将由上述液晶聚酯纤维形成的织物或无纺布引入到液晶聚酯溶液中以得到一体化的液晶聚酯织物或无纺布,所述液晶聚酯溶液包含溶剂和液晶熔点为280-360℃的液晶聚酯树脂;
(c)干燥所述一体化的液晶聚酯织物或无纺布;和
(d)层压所述干燥的液晶聚酯织物或无纺布以形成多层,并加热和压制所述层压液晶聚酯织物或无纺布。
8.权利要求7的方法,其中所述层压板包含5-60重量%的由液晶聚酯纤维形成的一体化的织物或无纺布。
9.权利要求7的方法,其中步骤(c)在50-200℃下进行0.5-2小时。
10.权利要求7的方法,其中步骤(d)在200-400℃下进行0.5-4小时。
11.权利要求7的方法,其中步骤(c)和(d)在惰性气氛中进行。
12.覆铜层压板,其通过在权利要求1-6中任一项的层压板的至少一个表面上层压铜箔而制造。
13.印刷电路板,包含外电路层、至少一个内电路层和在其中具有电连接电路层的通孔的绝缘层,其中所述绝缘层是权利要求1-6中任一项的层压板。
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