CN101031413A - 用于生产低卷曲平薄芯层压板的层压板组成 - Google Patents

用于生产低卷曲平薄芯层压板的层压板组成 Download PDF

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CN101031413A
CN101031413A CNA2005800178291A CN200580017829A CN101031413A CN 101031413 A CN101031413 A CN 101031413A CN A2005800178291 A CNA2005800178291 A CN A2005800178291A CN 200580017829 A CN200580017829 A CN 200580017829A CN 101031413 A CN101031413 A CN 101031413A
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laminate
resin
copper foil
hot strength
prepreg
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凯茜·亨德里克斯
凯茜·凯利
马丁·乔特
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Isola USA Corp
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    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
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    • B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract

层压板卷曲减少的覆铜箔层压板，其含有拉伸强度小于47千磅/平方英寸的铜箔。

Description

用于生产低卷曲平薄芯层压板的层压板组成
技术领域
本发明涉及在印刷电路板产业中使用的层压板，尤其涉及具有低卷曲(reduced curl)的层压板。
背景技术
电子产业界为满足消费者对更高功能性和更低成本的电脑和电子设备的需求不断试图提高产品的性能。由于电路板厂商为满足更高密度互连的需求不断降低层压板的构造厚度，诸如层压板卷曲等层压板的物理外形成为更加突出的问题。因此，需要一种层压板系统，可以始终如一地加工以提供诸如低卷曲(low curl)等良好特性。
发明内容
本发明提供层压板以及制备层压板的方法，在平板上测量时，始终如一地呈现低卷曲。
因此，一方面，本发明提供一种覆铜箔层压板，其包括半固化片(prepreg)以及与该半固化片至少一个表面相连接的铜箔，其中，该铜箔的拉伸强度小于47千磅/平方英寸。
附图说明
图1表示包括铜拉伸强度在内的多个参数与层压板的平均卷曲的函数。
图2表示包括铜拉伸强度在内的多个参数与层压板的卷曲范围的函数。
图3表示包括铜拉伸强度在内的多个参数与层压板的平均卷曲的函数。
图4表示包括铜拉伸强度在内的多个参数与层压板的卷曲范围的函数。
具体实施方式
如上所述，本发明提供覆铜层压板，其包括半固化片以及与该半固化片至少一个表面相连接的铜箔。所述铜的拉伸强度低于在现有技术中通常用于制备层压板的铜的拉伸强度。令人惊奇地，在平板上测量时，本发明的层压板的卷曲降低了。
优选地，本发明使用的铜箔的拉伸强度小于47千磅/平方英寸(ksi)，更优选小于46千磅/平方英寸，进一步优选小于45千磅/平方英寸。特别是在优选的实施例中，拉伸强度为44千磅/平方英寸，或小于44千磅/平方英寸。拉伸强度的下限优选约为42千磅/平方英寸。该铜箔可以为在层压板和半固化片产业中通常所用的任何厚度。优选地，所述铜箔为1盎司(oz)或0.5盎司，并具有如上所述的拉伸强度。
在薄芯层压板中，通过降低铜拉伸强度来降低层压板卷曲特别有效。例如，已经发现由拉伸强度为44千磅/平方英寸的铜箔制成的千分之4英寸的薄芯层压板在平板上测量时具有小于0.25英寸的平均卷曲值。通常薄芯层压板的总层压厚度为千分之8英寸或小于千分之8英寸。优选地，薄芯层压板为单层板(singleply)，即包括一层半固化片，其每个面上层压有铜箔。
所述连接有低拉伸强度铜箔的半固化片通常包括用热固性树脂浸渍的芯材。
在本产业中公知的任何芯材都可用于本发明的层压板中。有用的芯材实例包括但不限于：玻璃纤维、无纺玻璃布、纺织玻璃布和纸。优选的芯材为纺织玻璃布。
热固性树脂通常作为树脂组合物被转移到芯材上，因此其包括溶剂和任选的添加剂。所述组合物中的热固性树脂可以为用于层压板/半固化片产业中的任何类型。有用的树脂包括但不限于聚酰亚胺树脂、含聚酰亚胺的树脂体系、以及包括酚醛清漆树脂(novolac resin)在内的环氧树脂。优选的树脂包括FR4型树脂，其为环氧树脂，所述环氧树脂为双酚A的衍生物，并且还包括由过量双酚A缩水甘油醚与四溴双酚A发生高级反应制得的树脂。一个特别优选的树脂为FR406，其可以从Isola Laminate Systems，Chandler，Arizona，U.S.A.获得。对薄芯层压板而言，优选的树脂具有高模量，例如FR406。以树脂组合物的固体重量作为100％基准，树脂在树脂组合物中所占的量为约30％～约90％，优选为约50％～约80％，更优选为约60％～70％。
为改善固化树脂的化学性能和电学性能，所述树脂合成物可以任选地包括一种或多种填料。可以通过填料改变特性的实例包括但不限于热膨胀系数、降低热膨胀系数(lowing CTE)、增加模量、和降低半固化片粘性。可用的填料的非限制性实例包括颗粒状的Teflon、滑石、石英、陶瓷，金属氧化物颗粒诸如二氧化硅、二氧化钛、氧化铝、二氧化铈、黏土、氮化硼、硅灰石、及其混合物。优选的填料包括煅烧粘土或熔融二氧化硅。另一优选的填料是硅烷处理的二氧化硅。使用时，以树脂组合物的固体重量作为100％基准，填料在热固性树脂组合物中所占的量为约0％～约20％，优选约0％～约10％。
热固性树脂组合物可以包括一种或多种增韧剂。所述增韧剂加入树脂组合物中以改善最终复合材料和层压板的可钻性。可用的增韧剂包括甲基丙烯酸甲酯/丁二烯/苯乙烯共聚物、甲基丙烯酸酯丁二烯苯乙烯核壳微粒、及其混合物。优选的增韧剂为甲基丙烯酸酯丁二烯苯乙烯核壳微粒，其可从Rohm& Haas(100Independence Mall West，Philadelphia，PA)获得，售出的商品名为Paraloid。使用时，以树脂组合物的固体重量作为100％基准，增韧剂在热固性树脂组合物中所占的量为约1％～约5％，优选约2％～约4％。
为在半固化片加工过程中提高树脂固化速率，任选将一种或多种固化剂加入到热固性树脂组合物中。所选的固化剂可以是任何已知的可加速热固性树脂固化速率的试剂。优选的固化剂包括可产生自由基的过氧化剂诸如二异丙苯过氧化物或过氧苯甲酸叔丁酯(可商业获得，例如从Akzo-Nobel PolymerChemicals LLC，Chicago，商品名为Triganox-C)。另一优选固化剂包括乙酰丙酮金属络合物(金属乙酰丙酮)。更优选的固化剂为二异丙苯过氧化物。使用时，以树脂组合物的固体重量作为100％基准，固化剂在热固性树脂组合物中所占的量优选为约0％～约30％，更优选约12％～约25％。
该热固性树脂组合物可以包括一种或多种阻燃剂。可用于制造复合材料和层压板的树脂组合物中的任何已知阻燃剂均可使用。可用的阻燃剂的实例包括但不限于缩水甘油醚化的双官能醇的卤化物，诸如双酚A、双酚F、聚乙烯基苯酚或苯酚、甲氧甲酚、烷基酚、邻苯二酚等酚醛清漆树脂的卤化物，诸如双酚F的酚醛清漆树脂，无机阻燃剂诸如三氧化二锑、红磷、氢氧化锆、偏硼酸钡、氢氧化铝和氢氧化镁，以及含磷阻燃剂诸如四苯基膦、磷酸三甲酚二苯酯(tricresyl-diphenyl phosphate)、磷酸三乙酯、磷酸甲酚二苯酯、磷酸二甲基苯酚二苯酯、酸式磷酸酯、含氮的磷酸酯化合物以及含卤素的磷酸酯化合物。
通常将一种或多种溶剂加入到树脂组合物中以提供树脂的溶解性、控制树脂粘度并保持树脂成分处于悬浮分散状态，以及促进树脂向芯材的转移。本领域技术人员所知晓的任何可与热固性树脂体系共用的溶剂都可使用。特别有用的溶剂包括甲基戊基酮(MAK)、甲基乙基酮(MEK)、甲苯、γ-丁内酯(BLO)、丙二醇甲乙醚醋酸酯(PMA)或其混合物。溶剂的选择通常由树脂的固化方法而决定。当树脂用热空气固化时，酮类是典型的优选溶剂。当树脂用红外线固化时，酮类和甲苯的混合物就是典型的优选溶剂。使用时，以组合物总重量的重量百分比计，溶剂在热固性树脂组合物中所占的量为约20％～约50％。
该热固性树脂组合物可以进一步包括其它添加剂，诸如消泡剂、均化剂(leveling agent)、染料及颜料。例如，荧光染料可以以痕量加入到树脂组合物中，使得层压板被暴露在电路板厂商光学检测设备的紫外光线下时能发出荧光。有用的荧光染料是高度共轭的共轭二烯染料。这种染料的一个实例是UVITEXOB(2，5-噻吩二基双(5-叔丁基-1，3-苯并噁唑)，其可以从Ciba Specialty Chemicals，Tarrytown，New York获得。
半固化片通常由芯材，诸如未卷绕进驱动辊的卷状纺织玻璃网而制备。该纺织玻璃网进入了涂覆区域，在那里，纺织玻璃网通过盛有热固性树脂组合物的池，所述热固性树脂组合物包括溶剂和上述讨论过的其它组分。在涂覆区域中，纺织玻璃网被树脂所饱和。被树脂饱和的纺织玻璃网然后通过一对计量卷轴，除去被树脂饱和的纺织玻璃网中过量的树脂，其后，树脂涂覆的纺织玻璃网向前行进干燥塔的长度，经过一段选定的时间，直到纺织玻璃网上的溶剂挥发尽。在纺织玻璃网上进行的第二次和接下来的涂覆树脂过程可通过重复上述步骤实现，直到完成半固化片的制备，于是半固化片被卷至滚轴之上。
层压过程通常需要将一层或多层半固化片层堆叠在一片或两片导电的箔片(诸如铜箔)之间。层压方法和参数可以广泛地变化，并且通常为本领域普通技术人员所知晓。在一个典型的固化周期内，堆叠层保持约40磅/平方英寸至约900磅/平方英寸的压力，并且处于约30英寸汞柱的真空度下。堆叠层的温度在约20分钟的时段里从约180上升至约375。堆叠层保持约375的温度75分钟，其后堆叠层经过20分钟的时段从375的温度冷却至75的温度。
在生产层压板的另一个过程中，热固性树脂组合物于环境温度和压力下在一个混合容器中被预混合。预混合物的粘度为大约600-1000厘泊，并且可以通过添加或移除树脂中的溶剂来调整。使纤维基质(通常是但不限于无碱玻璃纤维(E-glass))经过含有预混合树脂的浸渍池，经过烘烤塔，在烘烤塔中过量的溶剂被驱除，然后半固化片被卷起或铺展成一定大小，再在铜箔间层合成各种各样的构造，这些构造取决于玻璃纤维纺织的样式、树脂的含量以及所需要的厚度。
热固性树脂组合物也可使用槽口模头技术或其它涂覆技术直接涂覆在铜基片上(RCC-覆树脂铜)。
下面的实施例是对本发明各种方面起说明作用的，但不用来限制本发明的范围。
实施例
进行了一系列的实验以在数量上测定各种材料和过程因素对层压板卷曲的影响。于是，制备出单层薄芯层压板并测量其卷曲量。发现尽管存在许多对卷曲现象作贡献的因素，铜箔的拉伸强度对其具有最大的影响。在薄芯构造为千分之4英寸或更小时，较低的铜箔拉伸强度可减少大约50％的卷曲。这种改变显然可以被引入当前的制造系统中与其它不那么重要的过程因素相协调。
实施例1
具有一个嵌套因素(层压机)的24次实验以随机重复的方式运行，其中两个因素有三个等级，还有两个因素有两个等级。每本书18个层压板在每一台层压机中使用。使用MinitabTM 13.32软件的一般线性模型(GLM)在0.05级上进行分析。实验因素的分析研究如下所述：
实验因素
因素                     等级
·层压机(升温)           1(升温4.42/分钟)，2(升温3.5/分钟)
·纸的层数               6，12
·B阶构造                1×70％，2×66％，1×63％以及70％使用106
                         纤维和FR406树脂
·铜拉伸强度，千磅/平方44(21.4％)，47(20.4％)，52(17.2％)*英寸，1.0盎司，20℃
*相应的20℃下延伸率示于()中
测量的响应
·四个角中每一个角的卷曲测量值的平均值
·四个卷曲测量值的范围
·测量Tg’s以确保所有样本均已固化
·纱线丝间空隙(IXV’s)
·面板厚度
原料和工艺过程
芯的构造。研究了三种不同的芯的构造，都使用Hexcel 106 CS4552纤维和FR406树脂：
1x树脂占70％(.002``芯)，[纤维的厚度，固化的树脂]
2x树脂占66％(.0035``芯)以及
1每种树脂各占63％和70％(.0035``芯)。
铜。研究了拉伸强度(以20℃时每千磅/平方英寸计)分别为44、47和51的1.0盎司铜箔。该箔，是由供应厂商指定的THE-NT-TWB铜箔，从Circuit Foil，Fremont，California处获得。
层压。[标的数字表示工厂内的标记]
        样本                      层压机
        A                         1
        B                         2
结果
因为层压机是嵌套因素，唯一可直接在两台层压机之间进行的分析是方差分析(ANOVA)，它显示出相关的卷曲贡献值作为工艺过程的结果。在该情况下，升温是参数。
以英寸计的所有测量P11(升温4.42/分钟)P22(3.5/分钟)值
  平均值   标准差   总数   平均值   标准差   总数
  卷曲平均值卷曲范围   0.2620.298   0.1090.152   288288   0.1970.242   0.0790.178   216216
P1是层压机1；P2是层压机2。
层压机2应用了较慢的加热速率，在各种条件下总的卷曲都较少。数据的扩展范围大，归因于其它三个因素使用了极端的等级。然后分析了每一台层压机的主要效应和相互作用，结果如下述附图中所示。
实验因素层压机1和层压机2在层压板卷曲(平均值和范围)上的效应如附图1-4中所示。特别的，附图1和2分别表示层压机1的层压板卷曲的平均值和范围。附图3和4分别表示层压机2的层压板卷曲的平均值和范围。在附图中，纸指的是纸的层数；B-阶指的是芯的构造；铜指的是铜拉伸强度；分层(lam)指的是层压板在书或堆叠的层压板内的位置；面板指的是层压板上单独面板的位置。
平均卷曲
对于两台层压机生产的层压板，层压板和单独面板的卷曲的可变性呈现出了总的生产过程中的差异，该差异对卷曲有重要的贡献。上述结论被主要因素图中卷曲的大的差异所证明。该模型占层压机1(较快升温)中总差异的67％以及层压机2(较慢升温)中总差异的69％。
各因素中可以控制的是每本书中使用的纸的层数、铜拉伸强度以及B阶构造。上述三项都对层压机1的卷曲有重要贡献，但此时只有B阶构造和铜拉伸强度对层压机2的卷曲是重要的。数据显示了较低的铜拉伸强度有助于较少的卷曲。
卷曲范围
对于两台层压机生产的层压板，层压板和单独面板的卷曲的可变性呈现出了总的生产过程中的差异，该差异对卷曲的起重要贡献。上述结论被主要因素图(附图1-4)中卷曲的大的差异所证明。该模型占层压机1(较快升温)中总差异的81％以及层压机2(较慢升温)中总差异的77％。
各因素中可以控制的是每本书中使用的纸的层数、铜拉伸强度以及B阶构造。在这三项中，对于层压机1，纸的层数是唯一可以控制的重要的主要效应。对于层压机2，铜拉伸强度和B阶构造之间的相互作用是重要的。因为所做的分析是分等级的，这意味着如果相互作用是重要的，它的分量的主要效应也是重要的。数据显示了较低的铜拉伸强度有助于较少的卷曲。
总之，上述结果显示了尽管存在许多对卷曲现象作贡献的因素，铜箔的拉伸强度对其具有最大的影响。较低的铜箔拉伸强度被发现对于减少薄芯层压板构造的卷曲具有重要作用。
尽管本发明通过具体实施方式进行了描述，可以理解为在不脱离本发明精神的情况下，可对本发明进行改进。本发明的范围不能被考虑为由本发明前述的说明书的详细说明和实施例所限定，而是由后附的权利要求书所限定。

Claims (11)

1.一种覆铜层压板，其包括半固化片以及与该半固化片至少一个表面相连接的铜箔，其中铜箔的拉伸强度小于47千磅/平方英寸。
2.权利要求1所述的覆铜层压板，其中所述铜箔的拉伸强度小于45千磅/平方英寸。
3.权利要求2所述的覆铜层压板，其中所述铜箔的拉伸强度为42千磅/平方英寸或更高。
4.权利要求1所述的覆铜层压板，其中所述铜箔是0.5盎司或1盎司铜箔。
5.权利要求1所述的层压板，其中所述的半固化片包括热固性树脂和芯材。
6.权利要求5所述的层压板，其中所述的热固性树脂是高模量树脂。
7.权利要求5所述的层压板，其中所述的热固性树脂是FR4树脂。
8.权利要求5所述的覆铜层压板，其中所述的芯材选自如下组成的组：玻璃纤维、无纺玻璃布和纸。
9.权利要求1所述的覆铜层压板，其中所述的层压板是单层层压板。
10.权利要求9所述的覆铜层压板，其中所述的层压板是薄芯层压板。
11.一种薄芯层压板，其包括：
包括FR106树脂和芯材的半固化片；以及
与该半固化片至少一个表面相连接的铜箔，其中所述铜箔的拉伸强度小于45千磅/平方英寸，并且所述层压板的总厚度为千分之4英寸或更少。
CNA2005800178291A 2004-06-01 2005-05-24 用于生产低卷曲平薄芯层压板的层压板组成 Pending CN101031413A (zh)

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KR100867906B1 (ko) 2008-11-10
JP2013136253A (ja) 2013-07-11
KR20070085107A (ko) 2007-08-27
WO2005118279A3 (en) 2006-07-27
WO2005118279A2 (en) 2005-12-15
US20050266756A1 (en) 2005-12-01
JP2008500918A (ja) 2008-01-17
EP1758735B1 (en) 2012-06-27
CA2578584C (en) 2011-12-20
US8263225B2 (en) 2012-09-11
EP1758735A4 (en) 2010-06-16
JP2015131489A (ja) 2015-07-23
EP1758735A2 (en) 2007-03-07
JP6282239B2 (ja) 2018-02-21
CA2578584A1 (en) 2005-12-15

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