CN1033065A - 热固性树脂组合物及由其制得的预浸料和层压板材 - Google Patents
热固性树脂组合物及由其制得的预浸料和层压板材 Download PDFInfo
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- CN1033065A CN1033065A CN88107546A CN88107546A CN1033065A CN 1033065 A CN1033065 A CN 1033065A CN 88107546 A CN88107546 A CN 88107546A CN 88107546 A CN88107546 A CN 88107546A CN 1033065 A CN1033065 A CN 1033065A
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Abstract
本发明提供一种热固性树脂组合物,该组合物包
含(a)一种用通式(I)代表的聚(对-羟基苯乙烯)衍
生物的预聚物。式(I)中,A为卤素,R1为含2~4个
碳原子的链烯基或链烯酰基,m表示1~4的数,n表
示1~100的数。(b)一种环氧改性的聚丁二烯,和(c)
一种芳族马来酰亚胺化合物。并提供使用该树脂组
合物的预浸料和层压板材。
Description
本发明涉及一种热固性树脂组合物和由其制得的预浸料和层压板材。特别是涉及一种适用于制造多层印刷电路板的层压材料、该层压材料的特点是具有极好的耐火性、耐热性和电性能,而且固化时的收缩率低。
迄今主要用于制造多层印刷电路板的层压材料都采用酚树脂、环氧树脂、聚酰亚胺等树脂,并在树脂中加入了溴化改性树脂或添加剂型阻燃剂以使其具有很好的耐火性。特别是对于一些大型计算机来说,由于它们所要求的密度越来越高,已采用耐热性和尺寸稳定性都很好的聚酰亚胺型树脂。但是,近年来,随着大型计算机运算速度的提高,开始需要采用介电常数低的印刷电路板以提高信号发送率。为了提供这种介电常数低的层压材料,人们已研制了含有聚四氟乙烯(PTFE)树脂或聚丁二烯树脂的层压板材。例如,Proc.NEPCON(1981),第160~169页及日本专利申请公开第126,451/80号就介绍了这种层压板材。
此外,日本专利申请公开第33,050/86号公开了一种介电常数很低的耐火树脂组合物,它含有一种聚(对-羟基苯乙烯)衍生物和一种环氧化聚丁二烯。
但PTFE层压板材的热膨胀系数大,由于PTFE树脂是热塑性的,玻璃化温度低,因而高温时尺寸稳定性不足。特别是在多层粘合中其通孔可靠性是不能令人满意的。此外,PTFE由于缺乏合适的溶剂,一般是用热熔压粘合法粘合的,这样它那非常高的熔化温度是不利的。另一方面,聚丁二烯树脂的分子结构使它具有易于燃烧的缺点,因此必须在其中加入添加剂型阻燃剂(如十溴二苯醚和磷酸三苯酯)或活性阻燃剂(如异丁烯酸三溴苯酯和丙烯酸三溴苯酯)以使其具有耐火性。但加入这些阻燃剂会使聚丁二烯树脂原有的优良的电性能、耐热性和尺寸稳定性变坏。
本发明的一个目的是提供具有很好的耐火性和很低的介电常数并能象聚酰亚胺层压材料那样高密度布线的层压材料,作为可取代迄今用于大型计算机的聚酰亚胺型多层印刷线路板的材料。
本发明的第一项内容涉及一种耐火热固性树脂组合物,该组合物是下面的通式(Ⅰ)所代表的聚(对一羟基苯乙烯)衍生物的预聚物、通式(Ⅱ)所代表的环氧改性的聚丁二烯和通式(Ⅳ)所代表的芳族马来酰亚胺化合物的混合物:
式中A为卤素,R1为含2~4个碳原子的链烯基或链烯酰基,m表示1~4的数,n表示1~100的数;
式中B为缩水甘油醚型环氧共聚物,n表示4~100的数;
式中R2为至少含一个苯环的芳基,n表示1~4的数。
本发明的第二项内容涉及用上述树脂组合物制得的预浸料,该预浸料是用通式(Ⅰ)所代表的聚(对一羟基苯乙烯)衍生物的预聚物、通式(Ⅱ)所代表的环氧改性的聚丁二烯和通式(Ⅲ)所代表的芳族马来酰亚胺化合物溶于溶剂中所获得的清漆那样的溶液浸渍纤维状基层材料而得:
式中A为卤素,R1为含2~4个碳原子的链烯基或链烯酰基(如烯丙基,丁烯基,乙烯基,丙烯酰基,异丁烯酰基和环氧异丁烯酰基),m表示1~4的数,n表示1~100的数;
式中,B为缩水甘油醚型环氧共聚物,n表示4~100的数;
式中,R2为至少含一个苯环的芳基,n表示1~4的数。
本发明的第三项内容涉及用上述树脂组合物制得的层压板材,该层压板材是通过预浸料的层迭与粘合而得,而该预浸料则是用通式(Ⅰ)所代表的聚(对一羟基苯乙烯)衍生物的预聚物、通式(Ⅱ)所代表的环氧改性的聚丁二烯和通式(Ⅲ)所代表的芳族马来酰亚胺所组成的组合物浸渍纤维状基层材料而得。
式中,A为卤素,R1为含2~4个碳原子的链烯基或链烯酰基(如烯丙基,丁烯基,乙烯基,丙烯酰基,异丁烯酰基和环氧异丁烯酰基),m表示1~4的数,n表示1~100的数;
式中,B为缩水甘油醚型环氧共聚物,n表示4~100的数;
式中,R2为至少含一个苯环的芳基,n表示1~4的数。
图1为代表本发明的一个具体方案的多层印刷线路板的剖面透视图。
本发明的热固性树脂组合物包含用上述通式(Ⅰ)、(Ⅱ)和(Ⅲ)所代表的三种组分。通式(Ⅰ)所代表的化合物的典型例子有聚(对一羟基苯乙烯)的乙烯基醚、异丁烯基醚或烯丙基醚的溴化产物或其丙烯酸酯、异丁烯酸酯或环氧异丁烯酸酯的溴化产物。可根据需要,只使用其中的一种或将其中的两种或两种以上一起使用。
通式(Ⅱ)所代表的环氧改性的聚丁二烯是本发明所使用的热固性树脂之一,用于使聚丁二烯改性的缩水甘油醚型环氧树脂的具体例子有二环氧甘油醚双酚A,二环氧甘油醚2,2′一二溴双酚A、二环氧甘油醚2,2′,4,4′-四溴双酚A、二环氧甘油醚2,2′-二甲基双酚A、二环氧甘油醚2,2′,4一三甲基双酚A、苯酚线型环氧树脂和邻甲酚线型环氧树脂。可根据需要只使其中的一种或将其中的两种或两种以上一起使用。
通式(Ⅲ)所代表的芳族马来酰亚胺化合物是本发明使用的热固性树脂之一,其具体例子有双马来酰亚胺,如N,N′一间一亚苯基双马来酰亚胺,N,N′一对一亚苯基双马来酰亚胺,N,N′-4,4′一二苯甲烷双马来酰亚胺,N,N-4,4′-(二苯醚)双马来酰亚胺,N,N′-亚甲基二(3一氯-对-亚苯基)-双马来酰亚胺,N,N′-4,4′-(二苯砜)双马来酰亚胺,N,N′-间二甲苯双马来酰亚胺,N,N′-4,4′一二苯基环己烷双马来酰亚胺,N,N′-4,4′一二苯基丙烷双马来酰亚胺,2,2′一二〔4-(4-马来酰亚胺苯氧基)苯基〕丙烷,2,2一二〔3-甲基-4-(4-马来酰亚胺苯氧基)苯基〕丙烷,2,2一二〔4-(4-马来酰亚胺苯氧基)苯基六氟丙烷,2,2′一二(4-马来酰亚胺苯基)六氟丙烷,1,3一二(3-马来酰亚胺苯氧基)苯和3,3′一双马来酰亚胺二苯酮;以及单马来酰亚胺,如N-苯基马来酰亚胺,N-3-氯苯基马来酰亚胺,N-邻-甲苯基马来酰亚胺,N-间-甲苯基马来酰亚胺,N-对-甲苯基马来酰亚胺,N-邻-甲氧苯基马来酰亚胺,N-间-甲氧苯基马来酰亚胺,N-对-甲氧苯基马来酰亚胺,N-苄基马来酰亚胺,N-吡啶基马来酰亚胺,N-羟苯基马来酰亚胺,N-乙酸基苯基马来酰亚胺胺,N-二氯苯基马来酰亚胺,N-二苯酮马来酰亚胺,N-(二苯醚)马来酰亚胺和N-乙酰苯基马来酰亚胺。可根据需要只使用其中的一种将其中的两种或两种以上一起使用。
用于本发明的芳族马来酰亚胺化合物在提高耐热性方面的效果胜于脂族马来酰亚胺化合物。
在含上述通式(Ⅰ)、(Ⅱ)和(Ⅲ)所代表的三种组分的混合物的热固性树脂组合物中加入游离基聚合引发剂和环氧固化剂能使该组合物的固化加速。
游离基聚合引发剂的典型例子有过氧化苯甲酰,过氧化二枯基,过氧化甲乙酮,过氧月桂酸叔丁酯,过氧邻苯二甲酸二叔丁酯,过氧化二苄基,2,5一二甲基一2,5一二(过氧化叔丁基)己烷,过氧化叔丁基枯基,氢过氧化叔丁基,过氧化二叔丁基,2,5一二甲基-2,5一二(过氧化叔丁基)己炔(3),氢过氧化二异丙苯,氢过氧化对 烷,氢过氧化蒎烷,2,5一二甲基己烷一2,2一二氢过氧化物和氢过氧化枯烯。它们的加入量宜为树脂组合物重量的0.1~10%。
环氧固化剂的典型例子有4,4′一二氨基二环己基甲烷,1,4一二氨基环己烷,2,6一二氨基吡啶,间一苯二胺,对苯二胺,4,4′一二氨基二苯基甲烷,2,2′一二(4一氨基苯)丙烷,4,4′一二氨基苯氧化物,4,4′一二氨基苯砜,二(4一氨基苯)甲膦氧化物,二(4-氨基苯)苯膦氧化物,二(4-氨基苯)甲胺,1,5一二氨基萘,间一苯二甲基二胺,1,1′一二(对一氨基苯)一呋咱,对一苯二甲基二胺,六亚甲基二胺,6,6′一二氨基-2,2′一二吡啶基,4,4′一二氨基二苯酮,4,4′一二氨基偶氮苯,二(4一氨基苯)苯甲烷,1,1′一二(4一氨基苯)环己烷,1,1′一二(4一氨基-3-甲基苯基)环己烷,2,5一二(间一氨基苯)-1,3,4,一噁二唑,2,5一二(对一氨基苯)-1,3,4-噁二唑,2,5一二(间-氨基苯)噻唑并(4,5-d)噻唑,5,5′一二(间-氨基苯)2,2′一二(1,3,4-噁二唑基),4,4′一二氨基二苯基醚,4,4′一二(6-氨基苯)-2,2′一二噻唑,间一二(4-对-氨基苯-2-噻唑基)苯,4,4′一二氨基-N-苯甲酰苯胺,4,4′一二氨基苯苯甲酸酯,N,N′一二(4一氨基苄基)-对-苯二胺,4,4′一亚甲基二(2一二氯苯胺),苯胍胺,甲基胍胺,四甲基丁二胺,邻苯二甲酸酐,1,2,4一苯三酸酐,1,2,4,5一苯四酸酐,二苯酮四甲酸酐,乙二醇二(脱水1,2,4-苯三酸酯),甘油三-(脱水1,2,4-苯三酸酯),马来酐,2-甲基咪唑,2-苯基咪唑,2-乙基-4-甲基咪唑,1-氰乙基-2-乙基-4-甲基咪唑,2-十-烷基咪唑和2-十七烷基咪唑。至少使用一种这样的固化剂。固化剂的合适用量宜为环氧改性的聚丁二烯的重量的0.1~30%,最好为0.3~10%。
游离基聚合引发剂和环氧固化剂根据需要也可一起使用。
上述热固性树脂组合物的混合比例可根据需要而异。一般,当通式(Ⅰ)所代表的聚(对一羟基苯乙烯)衍生物所占的比例增加时,耐火性和机械强度会改善,而柔韧性则降低,固化时的收缩增大。当通式(Ⅱ)所代表的环氧改性的聚丁二烯所占的比例增加时,柔韧性和与铜箔的粘合力会改善,而耐热性则会降低。当通式(Ⅲ)所代表的芳族马来酰亚胺所占的比例增加时,耐火性和耐热性会改善,固化时的收缩会减少,且尺寸稳定性也会改善。
制备本发明的热固性树脂组合物时,宜使通式(Ⅰ)的组分占10~60%(重量),最好为20~40%(重量);宜使通式(Ⅱ)的组分占10~60%(重量),最好为10~30%(重量);宜使通式(Ⅲ)的组分占20~70%(重量),最好为30~60%(重量)。
在本发明的组合物中还可根据需要加入第四种组分-芳香胺。
芳香胺的例子有4,4′一二氨基二苯基甲烷,4,4′一二氨基二苯基砜,4,4′一二氨基二苯基醚,2,2一二〔4-(4-氨基苯氧基)-苯基〕丙烷,2,2一二〔4-(4-氨基苯氧基)苯基〕-六氟丙烷,4,4′一二(3一氨基苯氧基)二苯基,和1,3一二(3-氨基苯氧基)苯。
下面将介绍制造本发明的层压板材的一般方法。
首先,将聚(对一羟基苯乙烯)衍生物、环氧改性的聚丁二烯和芳族马来酰亚胺溶于一种有机溶剂,制得清漆。可以采用的有机溶剂的例子有甲苯,二甲苯,丙酮,甲乙酮,甲基异丁基酮,N,N一二甲基甲酰胺,N-甲基吡咯烷酮,二甲亚砜,三氯乙烯,三氯乙烷,二氯甲烷,二噁烷和乙酸乙酯。
可根据需要将清漆加热,使其进行初步反应,以调节树脂在制备层压板材时的流动性和胶凝时间。此外,还可在清漆中加入偶合剂以提高清漆与基层材料的粘合力。然后再在这样制得的清漆中加入游离基聚合引发剂和环氧固化剂以制成浸渍用清漆。
然后用这样制得的浸渍用清漆浸渍片状基层材料,浸渍后在室温至170℃的温度下干燥,使预浸料不粘手。干燥温度的选择取决于所采用的溶剂和引发剂的种类。最后,将这样制得的预浸料按所需层数迭合,在100~250℃温度和1~100公斤力/厘米2的压力下进行热固化以获得层压板材。
几乎所有常用于层压材料的片状材料均可用于本发明。无机纤维的例子有各种玻璃(如含SiO2、Al2O3和其它成分的E玻璃、C玻璃、A玻璃、S玻璃、D玻璃和YM-31-A玻璃,以及由石英制得的Q玻璃)的纤维和陶瓷纤维。有机纤维的例子有由具有芳香族聚酰胺-酰亚胺骨架的高分子化合物制成的芳基酰胺纤维。
虽然本发明的树脂组合物固化时收缩率很低的原因还不清楚,但可以认为这是由于加入了马来酰亚胺化合物。
由于固化时的收缩率很低,在固化产物即层压板材等之中积聚的应力也小,因而很少发现有裂纹产生。
实施例
实施例1
将50重量份溴化聚(对一羟基苯乙烯)的异丁烯酸酯(酯的分子量为7,000~12,000,含溴量为42%)、30重量份用二环氧甘油醚双酚A改性的聚丁二烯和20重量份2,2′一二〔4-4(马来酰亚胺苯氧基)苯基)丙烷溶于由100重量份甲基异丁基酮和150重量份丙酮组成的混合溶剂中,并在搅拌下将该溶液在50~70℃下加热,再将0.5重量份用作游离基聚合引发剂的2,5一二甲基-2,5一二(过氧化叔丁基)己炔(3)和2重量份用作环氧固化剂的苯胍胺加入该溶液中,并搅拌所得的混合物,直至其完全溶解为止。从而获得清漆。
将所得的清漆置于蒸发器中,在减压和40~50℃下加热,除去空气和溶剂,以获得固体树脂组合物。将该树脂组合物置于一用脱模剂处理过的模具中,在130°~150℃下加热使其变为液体,并在减压下除去空气和泡沫,然后在170℃下热固化120分钟,在200℃下热固化120分钟,在230℃下热固化120分钟,以获得树脂片材。
实施例2~13和比较实例1~6
用基本上与实施例1相同的方法制备树脂片材,所不同的是按表1和2所示的比例进行混合。
在实施例11和比较实例4中所用的溴化聚(对一羟基苯乙烯)的丙烯酸酯的分子量为7,000~12,000,含溴量为45%;在实施例12和比较实例5中使用的溴化聚(对一羟基苯乙烯)的烯丙醚的分子量为7,000~12,000,含溴量为43%;在实施例13和比较实例6中所用的溴化聚(对一羟基苯乙烯)的环氧异丁烯酸酯的分子量为7,000~12,000,含溴量为35%。
表3所示为上述实施例和比较实施例中制得的树脂片材的重要特性。
实施例14
将50重量份溴化聚(对一羟基苯乙烯)的异丁烯酸酯(该酯的分子量为7,000~12,000,含溴量为42%)、30重量份用二环氧甘油醚双酚A改性的聚丁二烯和20重量份2,2′一二〔4-(4-马来酰亚胺苯氧基)苯基〕丙烷溶于由100重量份甲基异丁基酮和150重量份二甲基甲酰胺组成的混合溶剂中,并在搅拌下将该溶液在100°~120℃下加热30分钟。再将0.5重量份用作游离基聚合引发剂的2,5一二甲基-2,5一二(过氧化叔丁基)己炔(3)和2重量份用作环氧固化剂的苯胍胺加入该溶液中,并搅拌所得的混合物,直至其完全溶解为止,从而获得清漆。
用所得的清漆浸渍玻璃布(E玻璃,0.1毫米厚),在室温下晾干,然后在150℃下干燥10~20分钟以获得不粘手的预浸料。然后将10层预浸料迭合,在40公斤力/厘米2的压力和130℃的温度下加热30分钟,再在170℃下压制1小时和在220℃下压制2小时以获得层压板材。
实施例15~21和比较实例7~10
层压板材的制备方法基本上与实施例14相同,但按照表4所示的比例进行混合。
在实施例19中,所用的溴化聚(对一羟基苯乙烯)的丙烯酸酯的分子量为7,000~12,000,含溴量为45%;在实施例20中,所用的溴化聚(对一羟基苯乙烯)的烯丙醚的分子量为7,000~12,000,含溴量为43%;在实施例21中,所用的溴化聚(对一羟基苯乙烯)的环氧异丁酸酯的分子量为7,000~12,000,含溴量为35%。
比较实施例11和12分别代表环氧树脂层压板材和聚酰亚胺树脂层压板材。
比较例13
将50重量份1,2一聚丁二烯预聚物和50重量份甲酚线型环氧改性的聚丁二烯溶于二甲苯中以获得固体含量为20~30%(重量)的清漆。再将2重量份用作游离基聚合引发剂的过氧化二枯基和1重量份用作环氧固化剂的2-乙基-4-甲基咪唑加入该清漆中。然后,重复实施例14的操作以获得层压板材。
表5所示为在上述实施例和比较实施例中所获得的层压板材的重要特性。
实施例22
用表6所示的树脂组合物在按照实施例14所述的方法制得的预浸料的两面分别粘合一层厚度为35微米的铜箔,铜箔的与预浸料接触的一面事先使之粗糙。将该组件在30公斤力/厘米2的压力和130℃的温度下加热30分钟,在170℃下加热1小时,在200℃下加热2小时,以获得敷铜的层压板材。绝缘层的厚度为100微米。用光蚀刻方法处理该敷铜层压板材,以形成内层电路图形,包括信号层、电源层、匹配层等。然后用下面的方法处理电路图形的铜表面以形成双面布置组合电路板材。
用三氯乙烯洗涤→浸在氯化铜/盐酸溶液(1)中(40°~50℃,2分钟)→水洗→浸在10%硫酸中(室温,2分钟)→水洗→吹空气→浸在形成氧化膜的溶液(2)中(70°~80℃,2分钟)→水洗→干燥(100℃,30分钟)。
溶液组成
(1)浓盐酸300克,氯化铜50克,蒸馏水650克(用于使铜表面粗糙)。
(2)氢氧化钠5克,三代磷酸钩10克,亚氯酸钠30克,蒸馏水955克(用于使铜表面稳定)完成上述处理后,将所生成的线路板和上述预浸料树脂片材结合成图1所示的结构,以形成30层线路导电层2。然后进行粘合,粘合的条件为在40公斤/厘米2压力下在170℃保持90分钟和在220℃下保持90分钟以制备多层印刷电路板。
在多层粘合过程中,将导销插入板材四个角上的孔中,以防止错位。在多层粘合后,用微型钻钻出一直径为0.3或0.6毫米的小孔,并在该孔的全部表面上化学镀铜以形成通孔导体4。接着,用浸蚀的方法形成最外层的电路,这样就完成了多层印刷电路板的制作。
在本实施例中,能制得尺寸为570毫米×400毫米×约3.5毫米(厚)的多层印刷电路板,在该电路板中线的宽度为70微米或100微米,Channel/grid比为2~3/1.3毫米,层与层的切变比(Shear)约为100微米或小于100微米。玻璃布约占绝缘层的30%(体积)。
在图1中,1和3表示绝缘层,2表示电路导体层,4为一通孔;1为上述镀铜的层压板基层,3为预浸料树脂片材。
实施例23~29和比较实例14~17
多层印刷电路板的制作方法与实施例22相同,但分别使用表6所示的树脂组合物。
表7所示为利用从多层印刷电路板上切下的试片测定的焊接耐热性和热冲击特性的试验结果。
热分解温度是在升温速率为5℃/分的空气中用10毫克研成粉末的树脂样品测定的,并以重量损失达到5%的温度作为热分解温度。
线膨胀系数的测定方法是在升温速率为2℃/分的情况下测量在厚度方向的热膨胀并根据50℃~200℃之间的尺寸变化计算出线膨胀系数。
固化时的体积收缩率是根据固体在固化前后的比重的差别计算而得。
弯曲强度是用切成25×50毫米大小的层压板材测定的,测定时两个支点之间的距离为30毫米,在室温和180℃下的弯曲速率为1毫米/分。
介电常数是按照JISC6481的方法测定的,系测定1MHz频率时的静电容量。
焊接耐热性和挠曲特性是按照JISC 6481的方法评定的,测定焊接耐热性时是在试样在260℃下经受300秒后检查其外观。
本发明的树脂组合物与以前的低介电常数的树脂组合物相比,固化时的体积收缩率较小,因此模压性能好。
用本发明的树脂组合物制得的层压材料,具有与公认的低介电常数材料-聚丁二烯型材料差不多的低介电常数。由于本发明的材料的介电常数低达3.5左右,而目前用作大型计算机的多层印刷电路板的环氧型材料和聚酰亚胺型材料的介电常数为4.7,因此采用本发明的材料能使信号发送延迟时间缩短15%。
而且,用本发明的树脂组合物制作多层印刷电路板能获得具有极好的热冲击特性的基层。
按照本发明能获得收缩率低的树脂组合物,并能提供具有极好的抗龟裂性、耐热性和耐火性的低介电常数层压板材。
Claims (14)
2、按照权利要求1所述的热固性树脂组合物,该组合物包含:
(a)10~60%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~60%(重量)上述环氧改性的聚丁二烯,和
(c)20~70%(重量)上述芳族马来酰亚胺化合物。
3、按照权利要求1所述的热固性树脂组合物,该组合物包含:
(a)20~40%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~30%(重量)上述环氧改性的聚丁二烯,和
(c)30~60%(重量)上述芳族马来酰亚胺化合物。
4、热固性树脂组合物,该组合物包含:
(a)一种用通式(Ⅰ)代表的聚(对一羟基苯乙烯)衍生物的预聚物
式中,A为卤素,R1为含2~4个碳原子的链烯基或链烯酰基,m表示1~4的数,n表示1~100的数。
(b)一种用通式(Ⅱ)代表的环氧改性的聚丁二烯
式中,B为缩水甘油醚型环氧共聚物,n表示4~100的数,
(c)一种用通式(Ⅲ)代表的芳族马来酰亚胺化合物
式中,R2为至少含一个苯环的芳基,n表示1~4的数。
5、按照权利要求4所述的热固性树脂组合物,该组合物包含
(a)10~60%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~60%(重量)上述环氧改性的聚丁二烯,和
(c)20~70%(重量)上述芳族马来酰亚胺化合物。
6、按照权利要求4所述的热固性树脂组合物,该组合物包含
(a)20~40%(重量)上述聚(对一羟基苯乙烯)衍生物预聚物,
(b)10~30%(重量)上述环氧改性的聚丁二烯,和
(c)30~60%(重量)上述芳族马来酰亚胺化合物。
8、按照权利要求7所述的预浸料,其中所述的热固性树脂组合物包含:
(a)10~60%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~60%(重量)上述环氧改性的聚丁二烯,和
(c)20~70%(重量)上述芳族马来酰亚胺化合物。
9、按照权利要求7所述的预浸料,其中所述的热固性树脂组合物包含
(a)20~40%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~30%(重量)上述环氧改性的聚丁二烯,和
(c)30~60%(重量)上述芳族马来酰亚胺化合物。
10、一种包含纤维状基层材料和热固性树脂组合物的预浸料,所述的热固性树脂组合物包含
11、按照权专要求10所述的预浸料,其中所述的热固性树脂组合物包含:
(a)10~60%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~60%(重量)上述环氧改性的聚丁二烯,和
(c)20~70%(重量)上述芳族马来酰亚胺化合物。
12、按照权利要求10所述的预浸料,其中所述的热固性树脂组合物包含
(a)20~40%(重量)上述聚(对一羟基苯乙烯)衍生物的预聚物,
(b)10~30%(重量)上述环氧改性的聚丁二烯,和
(c)30~60%(重量)上述芳族马来酰亚胺化合物。
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JP62277446A JPH072829B2 (ja) | 1987-11-04 | 1987-11-04 | 積層板 |
JP277446/87 | 1987-11-04 |
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CN1033065A true CN1033065A (zh) | 1989-05-24 |
CN1009006B CN1009006B (zh) | 1990-08-01 |
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US (2) | US4931507A (zh) |
EP (1) | EP0315211B1 (zh) |
JP (1) | JPH072829B2 (zh) |
KR (1) | KR960007765B1 (zh) |
CN (1) | CN1009006B (zh) |
DE (1) | DE3853868T2 (zh) |
Cited By (6)
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CN101443368B (zh) * | 2006-05-18 | 2012-08-29 | 弗来克塞斯股份有限公司 | 含有双柠康酰亚胺、双衣康酰亚胺和/或柠康酰亚氨基衣康酰亚胺的组合物 |
CN104093779A (zh) * | 2012-01-19 | 2014-10-08 | 伊索拉美国有限公司 | 合成树脂以及由其制造的清漆、预浸料和层压板 |
CN104349599A (zh) * | 2013-08-06 | 2015-02-11 | 味之素株式会社 | 部件安装基板的制造方法 |
WO2018227756A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 聚合物树脂组合物及其在高频电路板中的应用 |
WO2018227746A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 一种聚合物树脂及其在高频电路板中的应用 |
WO2018227789A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 一种聚合物树脂组合物及其在高频电路板中的应用 |
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EP0234450B1 (en) * | 1986-02-19 | 1994-10-12 | Hitachi, Ltd. | Thermosetting resin and prepreg and laminate using the same |
JP4080546B2 (ja) † | 1997-01-21 | 2008-04-23 | ダウ グローバル テクノロジーズ インコーポレイティド | エポキシ硬化系のための潜触媒 |
JP3184485B2 (ja) * | 1997-11-06 | 2001-07-09 | 三井金属鉱業株式会社 | 銅張積層板用樹脂組成物、樹脂付き銅箔、多層銅張り積層板および多層プリント配線板 |
JP2006225484A (ja) * | 2005-02-16 | 2006-08-31 | Murata Mfg Co Ltd | 複合誘電体材料及び電子部品 |
JP5266685B2 (ja) * | 2006-09-29 | 2013-08-21 | 日立化成株式会社 | 熱硬化性樹脂組成物並びにこれを用いたプリプレグ及び積層板 |
US8568961B2 (en) * | 2008-11-25 | 2013-10-29 | Lord Corporation | Methods for protecting a die surface with photocurable materials |
US9093448B2 (en) | 2008-11-25 | 2015-07-28 | Lord Corporation | Methods for protecting a die surface with photocurable materials |
CN101643565B (zh) * | 2009-08-24 | 2010-07-21 | 广东生益科技股份有限公司 | 复合材料、用其制作的高频电路基板及其制作方法 |
JP6885000B2 (ja) * | 2016-07-19 | 2021-06-09 | 昭和電工マテリアルズ株式会社 | 半導体再配線層形成用樹脂フィルム、半導体再配線層形成用複合フィルム、それらを用いた半導体装置及び半導体装置の製造方法 |
WO2018150771A1 (ja) * | 2017-02-20 | 2018-08-23 | Jsr株式会社 | 感光性樹脂組成物、硬化膜およびその製造方法ならびに電子部品 |
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JPS5573726A (en) * | 1978-11-28 | 1980-06-03 | Fujitsu Ltd | Heat-resistant resin composition |
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JPS6011634B2 (ja) * | 1979-03-24 | 1985-03-27 | 富士通株式会社 | 耐熱性積層板 |
JPS55127425A (en) * | 1979-03-24 | 1980-10-02 | Fujitsu Ltd | Heat-resistant resin composition and heat-resistant laminated sheet |
JPS6133050A (ja) * | 1984-07-26 | 1986-02-15 | Ricoh Co Ltd | ル−プ通信方式 |
JPS61243844A (ja) * | 1985-04-23 | 1986-10-30 | Hitachi Ltd | 熱硬化性樹脂組成物 |
US4743647A (en) * | 1985-08-02 | 1988-05-10 | Amoco Corporation | Prepreg resin from aromatic bismaleimide and ethylenically unsaturated coreactant |
JPH0680094B2 (ja) * | 1986-02-19 | 1994-10-12 | 株式会社日立製作所 | 難燃性樹脂組成物 |
EP0234450B1 (en) * | 1986-02-19 | 1994-10-12 | Hitachi, Ltd. | Thermosetting resin and prepreg and laminate using the same |
JPS6356548A (ja) * | 1986-08-27 | 1988-03-11 | Hitachi Ltd | 熱硬化性樹脂組成物、それを用いた積層板およびその製造方法 |
-
1987
- 1987-11-04 JP JP62277446A patent/JPH072829B2/ja not_active Expired - Lifetime
-
1988
- 1988-10-29 KR KR1019880014147A patent/KR960007765B1/ko not_active IP Right Cessation
- 1988-11-02 US US07/266,406 patent/US4931507A/en not_active Expired - Fee Related
- 1988-11-03 CN CN88107546A patent/CN1009006B/zh not_active Expired
- 1988-11-04 EP EP88118454A patent/EP0315211B1/en not_active Expired - Lifetime
- 1988-11-04 DE DE3853868T patent/DE3853868T2/de not_active Expired - Fee Related
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1990
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Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
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CN101443368B (zh) * | 2006-05-18 | 2012-08-29 | 弗来克塞斯股份有限公司 | 含有双柠康酰亚胺、双衣康酰亚胺和/或柠康酰亚氨基衣康酰亚胺的组合物 |
CN104093779A (zh) * | 2012-01-19 | 2014-10-08 | 伊索拉美国有限公司 | 合成树脂以及由其制造的清漆、预浸料和层压板 |
CN104349599A (zh) * | 2013-08-06 | 2015-02-11 | 味之素株式会社 | 部件安装基板的制造方法 |
CN104349599B (zh) * | 2013-08-06 | 2018-09-04 | 味之素株式会社 | 部件安装基板的制造方法 |
WO2018227756A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 聚合物树脂组合物及其在高频电路板中的应用 |
WO2018227746A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 一种聚合物树脂及其在高频电路板中的应用 |
WO2018227789A1 (zh) * | 2017-06-13 | 2018-12-20 | 广东生益科技股份有限公司 | 一种聚合物树脂组合物及其在高频电路板中的应用 |
Also Published As
Publication number | Publication date |
---|---|
DE3853868D1 (de) | 1995-06-29 |
DE3853868T2 (de) | 1995-09-21 |
US4931507A (en) | 1990-06-05 |
JPH01121356A (ja) | 1989-05-15 |
CN1009006B (zh) | 1990-08-01 |
JPH072829B2 (ja) | 1995-01-18 |
EP0315211A1 (en) | 1989-05-10 |
KR960007765B1 (ko) | 1996-06-12 |
KR890008186A (ko) | 1989-07-10 |
US5080965A (en) | 1992-01-14 |
EP0315211B1 (en) | 1995-05-24 |
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