CN1109702C - 印刷线路板用环氧树脂组合物及其层压板 - Google Patents
印刷线路板用环氧树脂组合物及其层压板 Download PDFInfo
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- CN1109702C CN1109702C CN96195163A CN96195163A CN1109702C CN 1109702 C CN1109702 C CN 1109702C CN 96195163 A CN96195163 A CN 96195163A CN 96195163 A CN96195163 A CN 96195163A CN 1109702 C CN1109702 C CN 1109702C
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- epoxy resin
- wiring board
- printed
- pwb
- composition epoxy
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Abstract
本发明涉及一种印刷线路板用环氧树脂组合物,所述的环氧树脂组合物系将(a)将苯酚类和羟基苯甲醛的缩合物环氧化而得到的环氧树脂及(b)双酚A与甲醛的缩合物、(c)阻燃剂、(d)固化促进剂作为必要成分掺合而成。本发明又提供了一种吸湿性低、具有优异的耐热性和耐高温特性、耐电腐蚀性及耐加热变色性和高Tg的印刷线路板用层压板。
Description
技术领域
本发明涉及一种用于制造印刷线路板等的印刷线路板用环氧树脂组合物及使用该环氧树脂组合物的印刷线路板用层压板。
背景技术
随着电子仪器的小型化、高性能化的发展,对其中所装置的印刷线路板也提出了其线路板多层、薄板、通孔孔径细化及其间距减小等的高密度化要求。再有,近年来,在将半导体芯片直接载于印刷线路板上后用树脂封装的、如针孔栅网阵列及球形栅网阵列等的半导体封装电路(软件包)上使用了印刷线路板。在用于半导体封装电路上时,印刷线路板在其制造过程中经过175℃以上的高温下的引线焊接及树脂封装工序。其时,发生印刷线路板的强度和弹性率不足,导致焊接引线的接合不良和树脂封装后发生翘曲和扭曲等的问题。为了提高在175℃以上高温下的强度和弹性率等高温特性,有必要使印刷线路板具有高于以往的Tg(玻璃化)温度。半导体封装电路用的印刷线路板被要求具有高于迄今为止的印刷线路板所具有的高密度布线。半导体封装用的印刷线路板要求高于以往的高密度布线,其绝缘的可靠性是重要的。
对应于上述这些要求,作为印刷线路板的绝缘材料,人们发展了提高环氧树脂Tg温度的方法。作为提高Tg的方法,如在特开昭60-155453号公报上所见,将多功能环氧树脂用二氰二酰胺硬化的环氧树脂系列被广泛研究。然而,二氰二酰胺硬化的环氧树脂系的缺点是:其吸湿性变高,很难满足伴随今后印刷线路板更高的高密度化要求而需要的高绝缘可靠性。特别是,在其绝缘特性中,构成绝缘材料上或绝缘材料内布线及电路图案或电极等的金属在高湿度的环境下,由于电位差的作用产生绝缘材料上或移行于绝缘材料内的金属电化学腐蚀(电蚀),发生所述的电蚀成为很大的问题。
对此,用多功能性的苯酚类作固化剂的印刷线路板,可使吸水率变低,耐电蚀性变得良好。但是,使用这种多功能性苯酚类的印刷线路板有时会发生这样的问题:因多功能性苯酚类的种类不同,加热处理时,有时会发生变色。在特开昭62-28168号公报上提出了为提高所述的耐加热变色性,将苯酚或双酚A作为主原料的高比例邻位苯酚·甲醛树脂掺用于固化剂的方案,但是,根据该方案,所得到的印刷线路板不具有耐175℃以上高温使用的Tg。
本发明系鉴于上述情况而作,本发明的目的在于:提供一种环氧树脂组合物,该组合物在用于制造印刷线路板时吸湿性低,可制造具有优异的耐热性和高温特性、耐电蚀性、耐加热变色性,且具有高Tg的印刷线路板。
本发明的目的又在于:使用上述环氧树脂组合物,提供一种具有优异的耐热性和高温特性、耐电蚀性、耐加热变色性,且具有高Tg的印刷线路板用层压板。
发明揭示
即,本发明提供了一种印刷线路板用环氧树脂组合物,所述环氧树脂组合物系将(a)将苯酚类和羟基苯甲醛的缩合物环氧化而得到的环氧树脂及(b)双酚A和甲醛的缩合物、(c)选自如,双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂、双酚F酚醛清漆型环氧树脂、脂环族环氧树脂、脂肪族链状环氧树脂、缩水甘油酸酯型环氧树脂、缩水甘油胺型环氧树脂、海因型环氧树脂、异氰脲酸型环氧树脂。其它,可使用的有如二功能苯酚类的缩水甘油醚、二功能醇的缩水甘油醚等的卤化物、如双酚A、双酚F、聚乙烯基苯酚、或者苯酚、甲酚、烷基苯酚、儿茶酚、双酚F等的酚醛树脂的卤化物、三氧化锑、亚磷酸三苯酯等至少一种阻燃剂、及(d)至少由一种醚化合物组成的固化促进剂作为必要成分掺合而成。
又,本发明提供了一种印刷线路板用层压板,上述层压板系将由上述的印刷线路板用环氧树脂组合物组成的树脂清漆浸渍基体材料,干燥后得到预浸渍片,将所制得的预浸渍片叠合,在其一面或二面贴合金属箔,加热,加压成型而得。
实施本发明的最佳方式。
以下详细说明本发明。
(a)的环氧树脂系将苯酚类和羟基苯甲醛的缩合物环氧化而制得。作为苯酚类较好的可以使用苯酚、甲酚、具有丙基、叔丁基等烷基的一元苯酚类等,特别好的是使用苯酚。作为羟基苯甲醛,较好的是,可以使用邻羟基苯甲醛、间羟基苯甲醛、对羟基苯甲醛、香草醛、丁香醛、2,4-二羟基苯甲醛、原儿茶醛等,特别好的是使用邻羟基苯醛。
苯酚类与羟基苯甲醛的缩合反应并无特别的限制,但较好的是,在酸催化剂存在下,使0.1~3摩尔,较好的是使0.3~1.5摩尔的羟基苯甲醛与1摩尔的苯酚类反应。
用例如环氧氯丙烷等的环氧化剂使所得到的缩合物环氧化,得到(a)的环氧树脂。
作为(a)的环氧树脂原料的苯酚类和羟基苯甲醛、环氧化剂的种类并无特别的限制,关于其缩合反应及环氧化反应的方法也并无特别的限制。但是,作为较好的(a)的环氧树脂可举出以下述方法所得的环氧树脂:在有盐酸等的酸催化剂存在下,在80~250℃的温度下使0.1~3摩尔的邻羟基苯甲醛与1摩尔的苯酚反应1~6小时,至少使3当量的环氧氯丙烷与所得的缩合物的羟基反应,得到环氧树脂。较好的是,所述环氧树脂的重均分子量为700~5,000,其软化温度为40~140℃,其环氧当量为130~280。
又,在本发明中,也可并合使用除了(a)环氧树脂以外的环氧树脂。例如,可以使用双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、联酚型环氧树脂、酚醛型环氧树脂、甲酚酚醛型环氧树脂、双酚F酚醛型环氧树脂、双酚A型环氧树脂、脂环族环氧树脂、脂肪族链状环氧树脂、缩水甘油酸酯型环氧树脂、缩水甘油胺型环氧树脂、海因型环氧树脂、异氰脲酸型环氧树脂,及其它,如二功能苯酚类的缩水甘油醚、二功能醇的缩水甘油醚及其加氢化合物等。可任意并合使用这些环氧树脂中的几种。
除了(a)环氧树脂以外的环氧树脂的配合比例,较好的是对于(a)的环氧树脂100重量份为0~200重量份。更好的是在10~100重量份。
关于(b)的双酚A和甲醛的缩合物的分子量并无限制,但以重均分子量250~20,000为宜。缩合物中也可含有双酚A的单体。缩合反应较好的是,在酸催化剂存在下,使0.1~6.0摩尔的甲醛与1摩尔的双酚A在80~250℃下反应。
作为双酚A与甲醛的缩合物的优选举例,可举出羟基当量为100~130的双酚A酚醛树脂。
该双酚A和甲醛的缩合物是作为固化剂添加的,其配合量最好是,(b)的缩合物的苯酚性羟基的当量配合至相对于(a)的环氧树脂的环氧基为0.5~1.5当量的范围。更好的是,配合至相对于(a)的环氧树脂的环氧基为0.9~1.1当量的范围。
另外,也可并合使用除了双酚A和甲醛的缩合物以外的固化剂。也可以使用双酚F型环氧树脂、聚乙烯基苯酚、或者,使用苯酚、甲酚、烷基苯酚、儿茶酚、从双酚F等制得的酚醛清漆树脂等。这些化合物的使用量并无特别的限制,可以并合使用这些化合物的几种。这些化合物的配合比例较好的是,以对于(b)的双酚A和甲醛的缩合物的100重量份的0~100重量份为宜。
(c)的阻燃剂只要是通常被称为阻燃剂的化合物即可,可以是任何阻燃剂化合物。例如,双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂、酚醛清漆型环氧树脂、甲酚酚醛清漆型环氧树脂、双酚A酚醛清漆型环氧树脂、双酚F酚醛清漆型环氧树脂、脂环族环氧树脂、脂肪族链状环氧树脂、缩水甘油酸酯型环氧树脂、缩水甘油胺型环氧树脂、海因型环氧树脂、异氰脲酸型环氧树脂。其它,可使用的有如二功能苯酚类的缩水甘油醚、二功能醇的缩水甘油醚等的卤化物、如双酚A、双酚F、聚乙烯基苯酚、或者苯酚、甲酚、烷基苯酚、儿茶酚、双酚F等的酚醛树脂的卤化物、三氧化锑、亚磷酸三苯酯等。其中,特别优选的是四溴双酚A、四溴双酚A的缩水甘油醚、苯酚与甲醛的缩合物的缩水甘油醚的溴化物。
(c)的阻燃剂的配合比例是,对于(a)的环氧树脂100重量份为20~500重量份,更好的是在30~200重量份。
作为(d)的固化促进剂,可使用至少一种咪唑化合物,特别是,使用其亚氨基被丙烯腈、异氰酸酯、三聚氰氨丙烯酸酯等保护的咪唑化合物,则可以得到其储存稳定性为以往的二倍以上的预浸渍片。
作为这里所使用的咪唑化合物,当然可包括含有咪唑环的化合物,也可为包括含有咪唑啉基的化合物。例如,咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-十一烷基咪唑、1-苄基-2-甲基咪唑、2-十七烷基咪唑、4,5-二苯基咪唑、2-甲基咪唑啉、2-苯基咪唑啉、2-十一烷基咪唑啉、2-十七烷基咪唑啉、2-异丙基咪唑、2,4-二甲基咪唑、2-苯基-4-甲基咪唑、2-乙基咪唑啉、2-异丙基咪唑啉、2,4-二甲基咪唑啉、2-苯基-4-甲基咪唑啉等。作为亚氨基的保护剂,有丙烯腈、苯二异氰酸酯、甲苯胺二异氰酸酯、萘二异氰酸酯、亚甲基双苯基异氰酸酯、三聚氰氨丙烯酸酯等。
在上述各种咪唑化合物中,作为其亚氨基被保护的咪唑化合物特别优选的是1-氰乙基-2-乙基-4-甲基咪唑。
可以并合使用这些固化促进剂中的几种,其配合比例较好的是:对于环氧树脂100重量份为0.01~5重量份,更好的是在0.05~2重量份。如其使用量少于0.01重量份,则促进效果不大;而大于5重量份,则其储存稳定性差。
本发明中的环氧树脂组合物可用于各种形式,但在涂布或浸渍于基体材料上时则往往使用溶剂。这些溶剂包括丙酮、甲乙酮、甲苯、二甲苯、甲基异丁基酮、乙酸乙酯、乙二醇一甲醚、 N,N-二甲基乙酰胺、甲醇、乙醇等,也可混合使用其中几种。
本发明有关的环氧树脂组合物中,也可以掺合结晶二氧化硅、熔融二氧化硅、氧化铝、锆石、硅酸钙、碳酸钙、碳化硅、氮化硅、氮化硼、氧化铍耐火材料、氧化镁、氧化锆、镁橄榄石、滑石、尖晶石、莫来石、二氧化钛等的粉体及钛酸钾、碳化硅、氮化硅、氧化铝等单晶纤维、玻璃纤维等一种以上。
无机填充剂的配合比例较好的是对于(a)、(b)、(c)的总重量的100重量份在650重量份以下,更好的是在200重量份以下。配合使用时,为2~650重量份。
将配合上述各种成分制得的清漆浸渍于玻璃织物、玻璃无纺布或以纸、玻璃以外的成分作为成分的织物等基体材料上,在干燥炉内、80-200℃的范围内进行干燥。由此,制得印刷线路板用的预浸渍板。叠合数块所述的预浸渍板,视需要,在其一侧面或二侧面覆上铜箔之类的金属箔。在150-190℃、20-80kgf/cm2范围内加热、加压,制得印刷线路板用的层压板。
又,使用该预浸渍板粘合印刷线路板,由此,制得多层的印刷线路板。
再有,在预浸渍板制造过程中的干燥是指:在使用溶剂的场合去除溶剂,在不使用溶剂的场合,使其在室温下失去流动性。
本发明由使用将苯酚类和羟基苯甲醛的缩合物环氧化而得到的环氧树脂、双酚A和甲醛的缩合物、上述特定的阻燃剂及上述特定的固化促进剂,得到一种环氧树脂组合物,该环氧树脂组合物由于比起以往的环氧树脂组合物来,缩水甘油醚基和酚式羟基的反应率高,其固化物的交联密度增高。所以,用于印刷线路板时吸湿性低,可得到具有优异的耐热性和高温特性、耐电蚀性、耐加热变色性,且具有高Tg的环氧树脂组合物。
实施例
以下,根据实施例详细说明本发明,但是,本发明并不限于这些实施例。
实施例1
用甲乙酮溶解苯酚邻羟基苯甲醛酚醛清漆型环氧树脂(环氧当量170)100重量份和双酚A酚醛清漆型环氧树脂(羟基当量114)46重量份及四溴双酚A(溴含量58重量%,羟基当量272)51重量份。配合1-氰乙基-2-乙基-4-甲基咪唑0.3重量份作为固化促进剂,制得不挥发物65%(重量)的清漆。
实施例2
用甲乙酮溶解苯酚邻羟基苯甲醛酚醛清漆型环氧树脂54重量份和溴化双酚A型环氧树脂(溴含量49重量%,环氧当量400)46重量份及双酚A酚醛清漆树脂50重量份。配合1-氰乙基-2-乙基-4-甲基咪唑0.3重量份作为固化促进剂,制得不挥发物65%(重量)的清漆。
实施例3
用甲乙酮溶解苯酚邻羟基苯甲醛酚醛清漆型环氧树脂36重量份和溴化苯酚酚醛清漆型环氧树脂(溴含量35.3重量%,环氧当量284)64重量份及双酚A酚醛清漆树脂50重量份。配合1-氰乙基-2-乙基-4-甲基咪唑0.3重量份作为固化促进剂,制得不挥发物65%(重量)的清漆。
实施例4
在实施例1中,除了掺合以六亚甲基二异氰酸酯保护的2-乙基-4-甲基咪唑0.5重量份以取代1-氰乙基-2-乙基-4-甲基咪唑之外,其它以如同实施例1的配方,制得清漆。
比较例1
在实施例1中,除了使用邻甲酚酚醛清漆型树脂(环氧当量195)100重量份和双酚A酚醛清漆树脂38重量份及四溴双酚A48重量份以取代苯酚邻羟基苯甲醛酚醛清漆型环氧树脂之外,其它以如同实施例1的配方,制得清漆。
比较例2
在实施例1中,除了用酚醛清漆树脂(羟基当量106)43重量份及四溴双酚A50重量份取代双酚A酚醛清漆树脂之外,其它以如同实施例1的配方,制得清漆。
比较例3
将预先溶解于乙二醇单甲醚中的双氰胺1重量份掺合于低溴化环氧树脂(溴含量21重量%,环氧当量485)80重量份和苯酚水相醛酚醛清漆型环氧树脂20重量份中。作为固化催化剂配合1-氰乙基-2-乙基-4-甲基咪唑0.2重量份,制得不挥发物65%(重量)的清漆。
比较例4
在比较例3中,除了使用邻甲酚酚醛清漆型环氧树脂取代苯酚邻羟基苯甲醛酚醛清漆型环氧树脂之外,其它以如同比较例3的配方,制得清漆。
各个实施例及比较例1-4的主要配方示于表1。表1中的配合量单位为重量份。又,将在各个实施例及比较例1-4中所制得的清漆浸渍于0.2mm的玻璃织物上,160℃下加热2-5分钟,得到预浸渍板。关于所制得的预浸渍板测试其在刚制造后及在25℃温度、相对湿度为50%RH的条件下保存60日后的胶凝时间,由此评价其保存稳定性。又,叠合4块所制得的预浸渍板,在其二面覆以18μm的铜箔,在175℃、90分钟、2.5MPa的加压条件下制得二面覆铜的层压板。测定所得二面覆铜层压板的Tg、焊锡耐热性、吸水率、耐电蚀性、加热变色性及其在常温下及200℃时的挠曲强度、弯曲弹性率。这些测试结果示于表2及表3。又,可以确认,这些二面覆铜层压板具有完全相当于UL-94VO的阻燃性能。
表1
项目 | 实施例 | 比较例 | ||||||
1 | 2 | 3 | 4 | 1 | 2 | 3 | 4 | |
苯酚邻羟基苯甲醛酚醛清漆型环氧树脂(环氧当量170) | 100 | 54 | 36 | 100 | - | 100 | 20 | - |
溴化双酚A酚醛清漆型环氧树脂(含溴率49重量%,环氧当量400) | - | 46 | - | - | - | - | - | - |
低溴环氧树脂(含溴率21重量%环氧当量485) | - | - | - | - | - | - | 80 | 80 |
溴化苯酚酚醛清漆型环氧树脂(含溴率35.3重量%,环氧当量284) | - | - | 64 | - | - | - | - | - |
邻甲酚A酚醛清漆型树脂(环氧当量195) | - | - | - | - | 100 | - | - | 20 |
双酚A酚醛清漆型树脂(羟基当量114) | 46 | 50 | 50 | 46 | 38 | - | - | - |
四溴双酚A(含溴率5 8重量%,羟基当量272) | 51 | - | - | 51 | 48 | 50 | - | - |
酚醛清漆型树脂(羟基当量106) | - | - | - | - | - | 43 | - | - |
双氰胺 | - | - | - | - | - | - | 1.0 | 1.0 |
1-氰乙基-2-乙基-4-甲基咪唑 | 0.3 | 0.3 | 0.3 | - | 0.3 | 0.3 | 0.3 | 0.3 |
异氰酸酯保护的咪唑 | - | - | - | 0.5 | - | - | - |
表2
实施例 | 1 | 2 | 3 | 4 | |
预浸渍板胶凝时间(秒) | 刚制造后 | 122 | 121 | 120 | 125 |
60天后 | 100 | 103 | 101 | 121 |
Tg | 205 | 200 | 195 | 210 | |
焊锡耐热性 | OK | OK | OK | OK | |
吸水率(重量%) | 0.56 | 0.45 | 0.48 | 0.59 | |
直至破坏天数 | >250 | >250 | >250 | >250 | |
加热变色性 | ○ | ○ | ○ | ○ | |
挠曲强度 | 常温 | 620 | 638 | 660 | 600 |
200℃ | 82 | 84 | 78 | 86 | |
弯曲 | 常温 | 22.6 | 23.1 | 23.3 | 22.5 |
200℃ | 13.3 | 13.1 | 13.1 | 13.4 |
表3
比较例 | 1 | 2 | 3 | 4 | |
预浸渍板胶凝时间(秒) | 刚制造后 | 122 | 121 | 117 | 120 |
60天后 | 101 | 100 | 95 | 98 | |
Tg | 137 | 175 | 162 | 132 | |
焊锡耐热性 | NG | OK | NG | OK | |
吸水率(重量%) | 0.55 | 0.58 | 1.12 | 1.05 | |
直至破坏天数 | 205 | 200 | 50 | 1.05 | |
加热变色性 | ○ | × | △ | △ | |
挠曲强度 | 常温 | 618 | 633 | 621 | 642 |
200℃ | 32 | 57 | 35 | 25 | |
弯曲 | 常温 | 22.8 | 23.1 | 22.7 | 23.5 |
200℃ | 10.4 | 12.4 | 10.2 | 9.5 |
试验方法如下:
Tg:蚀刻铜箔,用TMA(热机分析)测定。单位:℃。
焊锡耐热性:蚀刻铜箔,在加压蒸煮试验器中保持2小时后,浸渍于260℃的焊锡中20秒,肉眼观测其外观。表中NG表示出现白斑和发生膨胀,OK表示没有出现白斑和没有发生膨胀。
吸水率:蚀刻铜箔,从加压蒸煮试验器中保持4小时前后的重量之差算出吸收率。单位:重量%。
加热变色性:蚀刻铜箔,在空气中160℃下处理5小时之后,目测评价。无变色者作为○,有若干变色者作为△,变色者作为×。
耐电腐蚀性试验:使用通孔壁间隔为350μm的试验布线图案,就各试样测得其400孔的绝缘电阻的经时变化。试验条件为在85℃、90%RH的气氛中外加100V电压,测得直至发生破坏的时间。
弯曲试验:按JIS C6481的试验方法,在常温下及200℃下测定。单位:挠曲强度(GPa),弯曲弹性率(MPa)。
从上述结果可以明白:
就环氧树脂而言,使用苯酚邻羟基苯甲醛酚醛清漆型环氧树脂的实施例1-4的Tg高至195℃以上,焊锡耐热性、耐电腐蚀性优良。又,其200℃下的挠曲强度、弯曲弹性率较其常温下的挠曲强度和弯曲弹性率的降低甚少。另外,在使用异氰脲酸保护的咪唑作为固化催化剂的实施例4的预浸渍板的保存稳定性能良好。
再者,使用了双酚A酚醛清漆树脂的实施例1~4及比较例1具有良好的耐加热变色性。
相比之下,在环氧树脂中使用邻甲酚酚醛清漆型环氧树脂的比较例1及使用酚醛清漆树脂取代双酚A酚醛清漆树脂的比较例2的环氧树脂组合物其Tg低,200℃下的挠曲强度、弯曲弹性率也皆低。在使用酚醛清漆树脂作为固化剂的比较例2的耐加热变色性差,另外,使用双氰胺的比较例3及4的吸水率大,耐电腐蚀性差。
产业上的可利用性
使用本发明的供印刷线路板用的环氧树脂组合物制造印刷线路板,可以制得吸湿性低、具有优异的耐热性和耐高温特性、耐电腐蚀性及耐加热变色性的印刷线路板。
Claims (12)
1.一种印刷线路板用环氧树脂组合物,所述的环氧树脂组合物系将(a)将苯酚类和羟基苯甲醛的缩合物环氧化而得到的环氧树脂及(b)双酚A与甲醛的缩合物、(c)至少一种阻燃剂、及(d)至少由一种咪唑化合物组成的固化促进剂作为必要成分掺合而成,所述咪唑化合物的亚氨基被丙烯腈、异氰酸酯或三聚氰胺丙烯酸酯保护,对于100重量份(a)的环氧树脂配合0.01-5重量份的(d)的固化促进剂。
2.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(a)的环氧树脂系将苯酚与邻羟基苯甲醛的缩合物环氧化而制得。
3.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(b)的双酚A与甲醛的缩合物为双酚A酚醛清漆树脂。
4.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(b)的缩合物的酚式羟基对于(a)的环氧树脂的环氧基而言为0.5~1.5当量的范围。
5.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(c)的阻燃剂为四溴双酚A。
6.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(c)的阻燃剂为四溴双酚A的缩水甘油醚。
7.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(c)的阻燃剂为苯酚与甲醛的缩合物的缩水甘油醚。
8.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(d)的固化促进剂为异氰酸酯保护的咪唑。
9.一种印刷线路板用的层压板,其特征在于,将由权利要求1所述的印刷线路板用环氧树脂组合物组成的树脂清漆浸渍于基体材料上,得到预浸渍板,叠合该预浸渍板,将其一个侧面或二个侧面覆以金属箔,加热,加压而制得。
10.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,对于100重量份(a)的环氧树脂配合30-200重量份的(c)的阻燃剂。
11.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(c)的阻燃剂为溴化双酚A型环氧树脂。
12.如权利要求1所述的印刷线路板用环氧树脂组合物,其特征在于,所述(d)的固化促进剂为1-氰乙基-2-乙基-4-甲基咪唑。
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US7078816B2 (en) * | 2004-03-31 | 2006-07-18 | Endicott Interconnect Technologies, Inc. | Circuitized substrate |
JP4634856B2 (ja) * | 2005-05-12 | 2011-02-16 | 利昌工業株式会社 | 白色プリプレグ、白色積層板、及び金属箔張り白色積層板 |
JP4961903B2 (ja) * | 2006-04-27 | 2012-06-27 | 日立化成工業株式会社 | エポキシ樹脂組成物、エポキシ樹脂プリプレグ、金属張積層板および印刷配線板 |
FR2929622B1 (fr) * | 2008-04-04 | 2011-03-04 | Eads Europ Aeronautic Defence | Revetements mesostructures comprenant un agent texturant particulier, pour application en aeronautique et aerospatiale |
JP5344394B2 (ja) * | 2008-07-10 | 2013-11-20 | 山栄化学株式会社 | 硬化性樹脂組成物、並びにハロゲンフリー樹脂基板及びハロゲンフリービルドアッププリント配線板 |
KR101084507B1 (ko) * | 2009-04-01 | 2011-11-18 | 아이디비켐(주) | 유기 인계 난연제 및 이의 제조방법 |
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1996
- 1996-06-20 KR KR1019970709418A patent/KR100271050B1/ko not_active IP Right Cessation
- 1996-06-20 EP EP96918862A patent/EP0835892B1/en not_active Expired - Lifetime
- 1996-06-20 WO PCT/JP1996/001707 patent/WO1997001591A1/ja active IP Right Grant
- 1996-06-20 CN CN96195163A patent/CN1109702C/zh not_active Expired - Fee Related
- 1996-06-20 DE DE69610771T patent/DE69610771T2/de not_active Expired - Fee Related
- 1996-06-22 TW TW085107522A patent/TW421664B/zh not_active IP Right Cessation
-
1998
- 1998-09-30 HK HK98111083A patent/HK1015388A1/xx not_active IP Right Cessation
-
2000
- 2000-04-03 US US09/541,515 patent/US6329474B1/en not_active Expired - Fee Related
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JPS57141419A (en) * | 1981-02-27 | 1982-09-01 | Mitsubishi Petrochem Co Ltd | Production of polyepoxide |
JPH0379621A (ja) * | 1989-05-12 | 1991-04-04 | Mitsubishi Electric Corp | 積層板用樹脂組成物 |
JPH03124735A (ja) * | 1989-10-06 | 1991-05-28 | Hitachi Chem Co Ltd | 印刷配線板用プリプレグの製造方法 |
Also Published As
Publication number | Publication date |
---|---|
US6329474B1 (en) | 2001-12-11 |
KR19990022948A (ko) | 1999-03-25 |
KR100271050B1 (ko) | 2001-03-02 |
EP0835892A1 (en) | 1998-04-15 |
DE69610771D1 (de) | 2000-11-30 |
DE69610771T2 (de) | 2001-02-22 |
TW421664B (en) | 2001-02-11 |
EP0835892B1 (en) | 2000-10-25 |
EP0835892A4 (en) | 1998-06-10 |
HK1015388A1 (en) | 1999-10-15 |
CN1189841A (zh) | 1998-08-05 |
WO1997001591A1 (en) | 1997-01-16 |
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