CN1239559C - 层压材料用清漆、由该清漆制得的层压材料、印刷布线板 - Google Patents
层压材料用清漆、由该清漆制得的层压材料、印刷布线板 Download PDFInfo
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Abstract
本发明涉及一种层压板或层压材料用清漆,其特征在于,包含:混合(a)环氧树脂、(b)双氰胺及(c)含咪唑环的化合物,使(c)成分含量为(a)成分的0.001~0.03重量%,在有机溶剂中,于70℃以上低于140℃的温度下反应进行热处理,以便使两成分在无溶剂下可相溶化的热处理物;以及(d)无机填料。另外本发明还涉及由该清漆制得的层压板或层压材料、以及使用如此的层压板或层压材料构成的印刷布线板。
Description
技术领域
本发明是有关于电绝缘用阻燃性层压板或层压材料用的清漆,由该清漆制得的电绝缘用阻燃性层压板或层压材料,及使用该电绝缘用阻燃性层压板或层压材料的印刷布线板。
技术背景
近年来,电绝缘用层压板(本发明中层压板包含单面、或双面贴合有金属箔的层压板,即金属面层压板)及层压材料由于高刚性化、高电容率化或低电容率化、无卤化等要求,而趋于大量含有各种无机填料。尤以对无卤化,为避免燃烧时产生所谓戴奥辛的问题,为不使用卤素类阻燃剂而维持阻燃性,大多添加大量无机类氧化物或氢氧化物。
然而,在以往一般所用的环氧树脂以双氰胺固化的树脂中,若添加大量无机填料,则层压时常因树脂与填料起分离,而成为不均匀的层压板。此是几乎不见于以其它固化剂(酚醛清漆树脂等)固化的树脂中,而为双氰胺固化中的特殊现象,其于使用仅含苯酚酚醛清漆骨架或甲酚酚醛清漆骨架的环氧树脂时尤为显著。如此的不均匀的层压板,有各种层压板特性差,尤其是焊锡耐热性差的问题。不起如此的树脂与填料的分离的环氧树脂固亦存在,但为使不含卤元素而能满足电绝缘用层压板·印刷布线板所要求的耐热性及可靠性,必须使用具有诸如酚醛清漆骨架的刚直结构的环氧树脂。为解决这些问题,日本专利特开平11-60951公开,以聚硅氧烷低聚物处理无机填料表面,提高树脂/填料间的粘着性并改善分散性的方法。但是,如此的填料的表面处理制造成本高,难于适用平时所用的层压板或层压材料。
发明内容
本发明人等对树脂与填料的分离是何种作用所引起进行了详细的探讨,结果发现该问题起因于树脂与双氰胺的相溶性差。即,双氰胺对大部份的环氧树脂,尤其是苯酚酚醛清漆骨架或甲酚酚醛清漆骨架的环氧树脂缺乏相溶性,溶剂挥发后于环氧树脂中析出。因而在层压材料中固化反应极不均匀,考虑该不均匀是无机填料的分离的主因。
特开平8-3283,美国专利第5143756号,EP0472830及特开平5-140352均例示有以预反应使环氧树脂与双氰胺相溶化的方法。这些均仅为层压板特性的均匀化,对大量使用无机填料时的效果全无提及,无法对应目前的以填料提高机能的普及趋势。另外,通常的双氰胺固化的环氧树脂组合物仅施以预反应时,会有保存稳定性的问题。例如,特开平9-263647中即指出,为求保存稳定性,期望双氰胺能以非相溶分散状态存在于环氧树脂中。即,使用环氧树脂与双氰胺的层压板或层压材料用清漆,必须同时并存避免无机填料的分离的相溶性以及保存稳定性。
本发明的目的在于提供,清漆保存稳定性优良,不起树脂与无机填料的分离的层压板或层压材料用清漆;及使用该清漆的均匀且能抑制膨胀的发生并具有优良耐热性及高度可靠性的电绝缘用层压板或层压材料;以及使用该层压板或层压材料的印刷布线板。
本发明是为解决这些课题,而于双氰胺固化环氧树脂层压板导入大量无机填料,使均匀分散。
即,含有下述热处理物以及无机填填料(d),
所述热处理物是通过以下所述方式获得,即,具有下述式(1)所示的结构并且选自苯酚酚醛清漆型环氧树脂、邻甲苯酚酚醛清漆型环氧树脂中的一种或两种的环氧树脂(a)与双氰胺(b)以及下述式(2)所示的含咪唑环的化合物(c),在使(c)成分含量为(a)成分的0.001~0.03重量%的条件下进行混合,然后在选自甲基乙基酮、甲基异丁基酮、乙二醇、二乙二醇、2-甲氧基乙醇、2-(2-甲氧基乙基)乙醇、2-乙氧基乙醇、2-(2-乙氧基乙基)乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、环己酮的有机溶剂中一种或两种以上的有机溶剂中,于70℃以上低于140℃的温度下反应,进行处理,以便使(a)和(b)成分在无溶剂下可相溶化,由此得到热处理物,
式中:R1是氢原子、直链或支链状的碳原子数1~12的烷基或碳原子数为2~5的烯基,R2是取代或非取代的直链或支链状的碳原子数1至12的亚烷基、取代或非取代的碳原子数2至5的亚烯基、取代或非取代的碳原子数6至12的亚芳基,n是2以上的整数,
式中,R3、R4及R5分别为氢原子、甲基、乙基或苯基,R6为取代或非取代的直链或支链状的碳原子数1至12的亚烷基,取代或非取代的碳原子数6至20的亚芳基。
另外本发明还涉及由该清漆制得的层压板或层压材料、以及使用如此的层压板或层压材料构成的印刷布线板。
具体实施方式
作为本发明所使用的含于层压板或层压材料用清漆中的成分(a),优选具有下式(1)的结构的环氧树脂:
式中:R1是氢原子或任意的1价有机基,R2是任意的2价有机基,
以及而n是2以上的整数,此类环氧树脂亦可2种以上适当组合使用。
在式(1)中,作为R1中1价有机基的例如有,直链或支链的碳原子数1至12的烷基、碳原子数2至5的烯基等。作为优选的R1为氢原子,或选自甲基、辛基、壬基、癸基、十二基、叔丁基及乙烯基的有机基,更优选为氢原子或甲基。另外,作为R2中2价有机基例如有,取代或非取代的直链或支链的碳原子数1至12的亚烷基,取代或非取代的碳原子数2至5的亚烯基,取代或非取代的碳原子数6至12的亚芳基等,更优选为选自亚甲基、乙撑、二甲基二环戊亚二烯基、4,5-二甲基-1,2-苯二甲基的二价有机基,更优选为亚甲基。特别是作为(a)成分使用将酚醛树脂的羟基环氧化所制备的苯酚酚醛清漆类环氧树酯时,本发明的效果可得以很大发挥。具体而言,优选的有苯酚酚醛清漆环氧树脂、邻甲苯酚酚醛清漆环氧树脂、二环戊二烯改质苯酚酚醛清漆环氧树脂、酚化聚丁二烯环氧树脂、对乙烯苯酚酚醛清漆环氧树脂、二甲苯改质苯酚酚醛清漆环氧树脂等。其中从价格、供给量等观点来看,最优选苯酚酚醛清漆环氧树脂及邻甲苯酚酚醛清漆环氧树脂。另外,n是2以上的整数,优选为2至6的整数。
作为(b)成分的双氰胺,为化学式为H2NC(=NH)NHC≡N的化合物,可以使用市售品。
另外,作为(c)成分,可用咪唑、2-和/或4-及/或5-取代咪唑类、N-取代咪唑类,具体而言,可以使用咪唑、2-甲基咪唑、2-乙基咪唑、2-丙基咪唑、2-丁基咪唑、2-苯基咪唑、4-甲基咪唑、2,4-二甲基咪唑、2-乙基-4-甲基咪唑、2-丁基-4-甲基咪唑、2-苯基-4-甲基咪唑、苯并咪唑、1,2-二甲基咪唑、1-甲基-2-乙基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、咪唑·环氧丙基化合物反应产物、咪唑·二环氧丙基化合物反应产物、2-乙基-4-甲基咪唑·二环氧丙基化合物反应产物等。特别优选常温保存稳定性优良且加热时显示快速促进反应作用的掩蔽咪唑类,特别优选式(2)所示的化合物为佳:
式中,R3、R4及R5分别为氢原子、甲基、乙基或苯基,R6为任意的2价有机基,
在式(2)中,作为R6中2价有机基例如有,取代或非取代的直链或支链的碳原子数1至12的亚烷基,取代或非取代的碳原子数6至20的亚芳基等,作为取代基例如有,烷基、芳基等。优选的例如有(1,4-亚苯基、4,4’-亚联苯基、3,3’,5,5’-四甲基-4,4’-亚联苯基、4,4’-二亚苯基甲烷基、2,4’-二亚苯基甲烷基、2,2’-二亚苯基甲烷基、2,2-双(4-亚苯基)丙烷基等,更优选的为2,2-双(4-亚苯基)丙烷基。
(c)成分,依据添加量促进环氧树脂的固化性,但是通常是用环氧树脂的0.1至1.0重量%左右。但是,本发明中,其含量须为(a)成分的0.001至0.03重量%。这是由于通过环氧树脂与双氰胺的相溶化反应而促进固化的缘故,所需的添加量远低于通常的环氧树脂与双氰胺组成的树脂组合物。另外,(c)成分的添加量,与层压板或层压材料用清漆,或层压材料的保存稳定性密切相关,如本发明的以少量添加即可维持充分的固化性,对于保存稳定性是极其有利的。即,(c)成分的添加量,若高于上述范围,则相溶化反应后,清漆的凝胶时间过短,清漆或层压材料的保存稳定性差,若添加量低于上述范围,则层压材料的固化性差,层压板的特性恶化。
作为(d)成分可用大部份的工业用市售无机填料。通常,层压板因是将树脂溶解于有机溶剂成清漆,浸润于纸、玻纤基材制作涂布纸或布,将之种层压合而成,必须能于清漆中均匀分散,而不易于清漆中沉降、分离,并对清漆粘度无显著影响等。具体而言,可用1种或2种以上选自氢氧化铝、氢氧化镁、氧化硅、云母、滑石、氧化铝、碳酸镁、碳酸钡、碳酸钙、氧化钛等的无机填料。尤其是作为阻燃剂,在使用多以大量使用的氢氧化铝及氢氧化镁时,本发明可发挥很大的效果。
(a)成分环氧树脂与(b)成分的双氰胺的反应,主要是环氧基与双氰胺的氨基及亚氨基的开环加成反应,已知双氰胺除此以外还经过复杂反应机制,详细的反应产物的结构仍不明白。推测该反应产物兼具环氧环的开环结构、双氰胺的氰基及亚氨基,使环氧树脂与双氰胺二者相溶,作为两者的相溶化剂起作用。且环氧树脂与双氰胺的相溶化对非反应性添加物无机填料的分散性及分离是否有何作用虽不清楚,但却可见相溶化反应与无机填料的分散性及分离之间具有明确相关、即,以(a)成分环氧树脂与(b)成分双氰胺,在(c)成分的共存下于适当有机溶剂中反应,可明显改善所制作的层压板中所见的因无机填料的分离而起的不平坦,伴随的各种层压板特性也有很大变化。该相溶化反应,优选在70℃以上低于140℃进行,在80℃以上低于120℃进行反应时效率最佳。作为使用的有机溶剂是使用可溶解(a)、(b)及(c)三成分的有机溶剂。作为该类有机溶剂具体可以举出甲基乙基酮、甲基异丁基酮、乙二醇、二乙二醇、2-甲氧基乙醇、2-(2-甲氧基乙基)乙醇、2-乙氧基乙醇、2-(2-乙氧基乙基)乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-吡咯烷酮、环己酮等,也可由其中选取2种以上混合使用。环氧树脂与双氰胺的相溶化反应行为随二者的配比而异,从相溶化速度及固化物特性的平衡的观点来看,在(b)成分双氰胺的重量与(a)成分环氧当量比中,优选(b)重量(g)/((a)重量(g)/环氧当量)=7.35至11.55。若该数值大于11.55时,相溶化反应所需时间非常长,若小于7.35则固化物的交联密度低,所得层压板的刚性、耐热性差。
在本发明的清漆、层压板、层压材料及使用这些制成的印刷布线板中,除(a)、(b)、(c)及(d)的四成分以外,可添加阻燃剂、颜料、粘着助剂及抗氧化剂等。另外,本发明尤其适用于无卤清漆、层压板、层压用材料及使用这些制成的印刷布线板。这是由于,为使无卤而维持阻燃性,必须大量添加无机阻燃剂,但根据本发明却可轻易达成。这里所谓无卤,是指氯或溴的量各占清漆、层压板、层压材料或印刷布线板总重不及0.1重量%的清漆、层压板、层压材料及印刷布线板。
本发明的层压板或层压材料用清漆,通过与通常的电绝缘用层压板的制造方法相同的制造方法,可制造层压材料或层压板、及用这些层压板或层压材料制成的印刷布线板。即,将本发明的清漆浸润于玻纤布、玻纤不织布、或有机纤维布等并加热干燥使溶剂挥发,同时通过使环氧树脂稍作固化反应,可制成具有所需固化性及流动性的层压材料。另外,将该层压材料以数片重叠,上下敷以金属箔,进而夹于平滑传热板间,以可维持环氧树脂能充分进行固化反应的150℃以上,优选170℃以上的装置加热加压,即可制作金属面层压板。再以将该金属面层压板的金属箔蚀刻等方法进行电路加工,并进行开孔、镀层、抗油墨印刷等,即可制作印刷布线板。
实施例
以下通过实施例及比较例更具体说明本发明,但本发明并非仅限于这些实施例。
在实施例及比较例的环氧树脂、固化促进剂、及有机阻燃剂中使用下述的物质。其它的层压板、层压材料的添加剂、无机填料、玻纤布、铜箔等,除特加说明外,可使用一般用于化工业及电子业的原料。
环氧树脂A:大日本油墨化学工业(株)制甲酚酚醛清漆型环氧树脂,商品名:N-673(环氧当量210)
环氧树脂B:Dow Plastics公司制苯酚酚醛清漆型环氧树脂,商品名:DEN 438(环氧当量178)
固化促进剂A:双酚A型环氧树脂(Japan Epoxy Resin(株)制,商品名:Epicote 828)与2-乙基咪唑(四国化成工业(株)制)商品名:2EZ)的反应产物
固化促进剂B:四国化成工业(株)制2-乙基-4-甲基咪唑,商品名:2E4MZ
有机阻燃剂A:大八化学工业(株)制磷酸三苯酯,商品名:TPP
有机阻燃剂B:大八化学工业(株)制磷酸三甲苯酯,商品名:TCP
层压板的特性评价,对于阻燃性是依UL-94垂直法以燃烧时间评价,平均燃烧时间5秒以下且最长燃烧时间10秒以下分类为V-0,平均燃烧时间25秒以下且最长燃烧时间30秒以下为V-1,其以上的燃烧时为HB。焊锡耐热性是将试验片(25毫米×25毫米双面有铜)浮于加热至260℃及288℃的焊锡槽中,以肉眼观察300秒内有无膨胀发生。表中的各符号指,○:无变化,×:发生膨胀。
实施例1
基于以下配方制作无卤层压板和层压材料用清漆。首先,仅配合环氧树脂A、双氰胺、固化促进剂A、2-甲氧基乙醇,于室温将双氰胺大部份溶解,其次升温至100℃,反应2小时,得黄色粘稠均匀溶液。之后,冷却至30℃,添加其它成分成为清漆。将之浸润于玻纤布(重量:105g/平方米),于160℃干燥4分钟得层压材料。以8片该层压材料重叠,于其双面敷以18微米的单面粗化电解铜箔,于185℃压力4MPa下加热加压60分钟成形制作厚0.8毫米的双面铜面层压板。对清漆调制后以及于25℃保存2周后的凝胶时间的变化率及层压板的特性进行评价,结果示于表1中。
原料 重量份
环氧树脂A 100
双氰胺 4.5
固化促进剂A 0.006
有机阻燃剂A 15
氢氧化铝 65
2-甲氧基乙醇 55
甲基乙基酮 45
实施例2~5
如同实施例1,调制层压板、层压材料用清漆,制作层压材料及层压板。配方、凝胶时间变化率及层压板的特性示于表1中。
比较例1
如同实施例1,调制层压板、层压材料用清漆,制作层压材料及层压板。但是所有配合均于室温进行。以该清漆浸润于玻纤布(重量:105g/平方米),于160℃干燥4分钟得层压材料。但是,于层压材料中全面地析出白色双氰胺结晶。如同实施例1,以该层压材料8片重叠,于其双面敷以18微米的单面粗化电解铜箔,于185℃压力4MPa下加热加压60分钟成形制作层压板,但加热加压中大部份树脂未固化而原状流出,无法制作正常板厚的层压板。
比较例2
比较例1中调制的清漆,于170℃干燥20分钟得层压材料,如同实施例1制作层压板。虽于层压材料中全面地析出白色的双氰胺结晶,仍可制作正常板厚的层压板。而以化学蚀刻去除层压板的铜箔,于层压板全面可见有鳞状的氢氧化铝及树脂的分离。该层压板的配方、凝胶时间变化率及层压板的特性示于表1中。
比较例3
如同实施例1,调制层压板、层压材料用清漆。首先,仅配合环氧树脂A、双氰胺、固化促进剂A、2-甲氧基乙醇,于65℃反应20小时,之后于室温添加其它成分。将之浸润于玻纤布(重量:105g/平方米),于140℃干燥10分钟得层压材料。但是,于层压材料中全面地析出白色的双氰胺结晶。如同比较例1制作层压板,所得层压板以化学蚀刻去除层压板的铜箔,结果在层压板全面可见有鳞状的氢氧化铝及树脂的分离。该种层板的配方、凝胶时间保特率及层压板的特性示于表1中。
比较例4
仅变更固化促进剂A的量,如同实施例1调制层压板、层压材料用清漆。将之浸润于玻纤布(重量:105g/平方米),于160℃干燥3分钟得层压材料,如同实施例1加热加压制作层压板。但是在层压材料中未见双氰胺的析出,层压材料的流动性明显降低,成形时树脂熔融流动不足,端部成形不良。该层压板的配方、清漆凝胶时间保持率及层压板的特性示于表1中。另外,为使溶剂不充分挥发,不作3分钟以下的加热条件的层压材料的干燥。
表1
实施例1 | 实施例2 | 实施例3 | 实施例4 | 实施例5 | 比较例1 | 比较例2 | 比较例3 | 比较例4 | ||
配方 | 环氧树脂A | 100 | 100 | 100 | 100 | 100 | 100 | 100 | 100 | |
环氧树脂B | 100 | |||||||||
双氰胺 | 4.5 | 4.5 | 5.3 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | 4.5 | |
固化促进剂A | 0.006 | 0.006 | 0.006 | 0.006 | 0.006 | 0.006 | 0.006 | 0.300 | ||
固化促进剂B | 0.006 | |||||||||
有机阻燃剂A | 15 | 15 | 15 | 15 | 15 | 15 | 15 | 15 | ||
有机阻燃剂B | 17 | |||||||||
氢氧化铝 | 65 | 65 | 65 | 65 | 65 | 65 | 65 | 65 | ||
氢氧化镁 | 55 | |||||||||
2-甲氧基乙醇 | 55 | 55 | 55 | 55 | 55 | 55 | 55 | 55 | 55 | |
甲基乙基酮 | 45 | 45 | 45 | 45 | 40 | 45 | 45 | 45 | 45 | |
特性 | 清漆凝胶时间(秒) | 480 | 475 | 423 | 482 | 491 | 682 | 682 | 624 | 199 |
清漆凝胶时间保持率(%.25℃,2周) | 85 | 84 | 87 | 85 | 80 | 85 | 85 | 82 | 32 | |
层压板外观(铜箔蚀刻后) | 良好 | 良好 | 良好 | 良好 | 良好 | 全面碎白点纹 | 鳞状斑纹 | 鳞状斑纹 | 良好 | |
阻燃性(平均燃烧时间(秒)/判定) | 1.7V-O | 2.1V-O | 1.5V-O | 2.3V-O | 2.2V-O | 2.3V-O | 3.5V-O | 4.2V-O | 3.2V-O | |
焊锡耐热性(260℃) | ○ | ○ | ○ | ○ | ○ | ○ | × | ○ | ○ | |
焊锡耐热性(288℃) | ○ | ○ | ○ | ○ | ○ | × | × | × | ○ |
由表1的结果可知,所有实施例中,各原料单以于室温混合制作清漆时所产生的鳞状树脂及填料的分离可予抑制,可得均匀的层压板。另外,即使对于焊锡耐热性,也可以确认抑制膨胀的发生,作为层压板的可靠性提高。另一方面,未实施相溶化反应的比较例1及2,或以本发明外的条件作相溶化反应的比较例3,均于成形时有树脂及填料的分离发生,无法制造均匀的层压板。而添加本发明范围外的固化促进剂量的比较例4,除无法确保适当固化性以外,清漆保存稳定性亦不足。由这些结果可知本发明的有效及其优点。
实施例6至10
在以实施例1~5所得的双面铜面层压板的表面上,通过减除法形成电路(测试图样)。进而,为提升粘着性,对所制作的2片有电路的双面铜面层压板表面作粗化处理,其间夹持以各实施例所得的2片层压材料并叠合,再于外侧重叠层压材料2片及18微米单面粗化的电解铜箔,如同实施例1层压压合制作6层印刷布线板。在该印刷布线板中以通常方法作外层电路加工,形成通孔,以抗油墨印刷或作部件构装,确认在通常的印刷布线板制程中可顺利制造,并确认符合JIS C 6484及6486所规定的玻纤环氧树脂层压板的品质与可靠性要求。
根据本发明可以提供:通过使环氧树脂与双氦胺具有良好保存稳定性并相溶化而抑制树脂和无机填料的分离的层压板或层压材料用清漆;及使用该清漆制得的均匀并抑制膨胀发生的具优良耐热性及高度可靠性的电绝缘用阻燃性层压板或层压材料;进而使用该层压板或层压材料的印刷布线板。
Claims (8)
1.一种层压材料用清漆,其特征在于,含有下述热处理物以及无机填料(d),
所述热处理物是通过以下所述方式获得,即,具有下述式(1)所示的结构并且选自苯酚酚醛清漆型环氧树脂、邻甲苯酚酚醛清漆型环氧树脂中的一种或两种的环氧树脂(a)与双氰胺(b)以及下述式(2)所示的含咪唑环的化合物(c),在使(c)成分含量为(a)成分的0.001~0.03重量%的条件下进行混合,然后在选自甲基乙基酮、甲基异丁基酮、乙二醇、二乙二醇、2-甲氧基乙醇、2-(2-甲氧基乙基)乙醇、2-乙氧基乙醇、2-(2-乙氧基乙基)乙醇、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基-2-比咯烷酮、环己酮的有机溶剂中一种或两种以上的有机溶剂中,于70℃以上低于140℃的温度下反应,进行处理,以便使(a)成分和(b)成分在无溶剂下可相溶化,由此得到热处理物,
式中:R1是氢原子、直链或支链状的碳原子数1~12的烷基或碳原子数为2~5的烯基,R2是取代或非取代的直链或支链状的碳原子数1至12的亚烷基、取代或非取代的碳原子数2至5的亚烯基、取代或非取代的碳原子数6至12的亚芳基,n是2以上的整数,
式中,R3、R4及R5分别为氢原子、甲基、乙基或苯基,R6为取代或非取代的直链或支链状的碳原子数1至12的亚烷基,取代或非取代的碳原子数6至20的亚芳基。
2.如权利要求1所述的层压材料用清漆,其特征在于,(d)成分是1种或2种以上选自氢氧化铝、氢氧化镁、氧化硅、云母、滑石、氧化铝、碳酸镁、碳酸钡、碳酸钙、氧化钛中的无机填料。
3.如权利要求1或2所述的层压材料用清漆,其特征在于,(a)成分环氧当量与(b)成分双氰胺的重量的比为,(b)重量(g)/((a)重量(g)/环氧当量)=7.35~11.55。
4.如权利要求1或2所述的层压材料用清漆,其特征在于,在整个成分中所含的氯或溴的量,占清漆总重量低于0.1重量%。
5.一种层压材料,其特征在于,使用了权利要求1或2所述的层压材料用清漆。
6.如权利要求5所述的层压材料,其特征在于,在整个成分中所含的氯或溴的量,占层压材料总重量低于0.1重量%。
7.一种印刷布线板,其特征在于,是用权利要求5所述的层压材料制成。
8.如权利要求7所述的印刷布线板,其特征在于,在整个成分中所含的氯或溴的量,占电路板总重量低于0.1重量%。
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JP2000380174 | 2000-12-14 | ||
JP380175/00 | 2000-12-14 | ||
JP380174/2000 | 2000-12-14 | ||
JP2000380175 | 2000-12-14 | ||
JP380174/00 | 2000-12-14 | ||
JP380175/2000 | 2000-12-14 |
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CN1471552A CN1471552A (zh) | 2004-01-28 |
CN1239559C true CN1239559C (zh) | 2006-02-01 |
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CNB018180868A Expired - Fee Related CN1239559C (zh) | 2000-12-14 | 2001-12-12 | 层压材料用清漆、由该清漆制得的层压材料、印刷布线板 |
Country Status (12)
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US (2) | US7041399B2 (zh) |
EP (1) | EP1359175B1 (zh) |
JP (2) | JP4100172B2 (zh) |
KR (1) | KR100777500B1 (zh) |
CN (1) | CN1239559C (zh) |
AT (1) | ATE380213T1 (zh) |
AU (1) | AU2002222609A1 (zh) |
DE (1) | DE60131778T2 (zh) |
ES (1) | ES2295107T3 (zh) |
MY (1) | MY137550A (zh) |
TW (1) | TWI290934B (zh) |
WO (1) | WO2002048236A1 (zh) |
Families Citing this family (9)
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WO2002048236A1 (fr) * | 2000-12-14 | 2002-06-20 | Hitachi Chemical Co., Ltd. | Vernis pour stratifie ou preimpregne, stratifie ou preimpregne produit avec ce vernis et carte a circuit imprime formee avec ce stratifie ou ce preimpregne |
JP5260639B2 (ja) * | 2007-06-14 | 2013-08-14 | ビーエーエスエフ ソシエタス・ヨーロピア | エポキシドの硬化のための触媒 |
JP5136573B2 (ja) * | 2009-02-24 | 2013-02-06 | 日立化成工業株式会社 | ワニス、プリプレグ、樹脂付きフィルム、金属箔張積層板、プリント配線板 |
TWI494363B (zh) * | 2009-09-04 | 2015-08-01 | Iteq Corp | An epoxy resin composition and a film and a substrate made of the epoxy resin composition |
CN101733585B (zh) * | 2010-02-10 | 2012-09-19 | 北京海斯迪克新材料有限公司 | 一种晶圆级芯片封装凸点保护层及其形成工艺 |
CN102770474B (zh) * | 2010-02-24 | 2016-06-22 | 日立化成工业株式会社 | 清漆、预浸料片、含有树脂的膜、被覆金属箔的层叠板、印制电路布线板 |
JP5569270B2 (ja) * | 2010-09-06 | 2014-08-13 | 住友ベークライト株式会社 | プリプレグ、金属張積層板、プリント配線板及び半導体装置 |
JP6579892B2 (ja) * | 2014-10-03 | 2019-09-25 | 東京応化工業株式会社 | 硬化性組成物 |
CN118620184A (zh) * | 2023-03-07 | 2024-09-10 | 华为技术有限公司 | 胶囊型咪唑类固化剂及其制造方法、包含该胶囊型咪唑类固化剂的固化性组合物 |
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JPS5938235A (ja) * | 1982-08-30 | 1984-03-02 | Hitachi Chem Co Ltd | エポキシ樹脂プリプレグの製造法 |
CA1326096C (en) | 1988-08-19 | 1994-01-11 | Katugi Kitagawa | Epoxy resin powder coating composition with excellent adhesibility |
US5143756A (en) * | 1990-08-27 | 1992-09-01 | International Business Machines Corporation | Fiber reinforced epoxy prepreg and fabrication thereof |
JP2956378B2 (ja) * | 1992-09-21 | 1999-10-04 | 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及びエポキシ樹脂積層板 |
JP2956379B2 (ja) * | 1992-09-21 | 1999-10-04 | 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及びエポキシ樹脂積層板 |
JPH083283A (ja) * | 1994-06-27 | 1996-01-09 | Matsushita Electric Works Ltd | エポキシ樹脂組成物、プリプレグ及び積層板 |
US5994429A (en) * | 1995-03-10 | 1999-11-30 | Toshiba Chemical Corporation | Halogen-free flame-retardant epoxy resin composition |
JP3322134B2 (ja) * | 1996-01-26 | 2002-09-09 | 松下電工株式会社 | プリプレグの製造方法 |
US5837355A (en) * | 1996-11-07 | 1998-11-17 | Sumitomo Bakelite Company Limited | Multilayer printed circuit board and process for producing and using the same |
JP2000136292A (ja) | 1998-11-04 | 2000-05-16 | Shin Kobe Electric Mach Co Ltd | コンポジット金属箔張り積層板 |
JP2000239419A (ja) * | 1999-02-19 | 2000-09-05 | Hitachi Chem Co Ltd | 印刷配線板用プリプレグ及びこれを用いた印刷配線板 |
WO2002048236A1 (fr) * | 2000-12-14 | 2002-06-20 | Hitachi Chemical Co., Ltd. | Vernis pour stratifie ou preimpregne, stratifie ou preimpregne produit avec ce vernis et carte a circuit imprime formee avec ce stratifie ou ce preimpregne |
JP4783984B2 (ja) * | 2001-02-15 | 2011-09-28 | 日立化成工業株式会社 | 樹脂組成物およびその用途ならびにそれらの製造方法 |
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2001
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- 2001-12-12 US US10/450,176 patent/US7041399B2/en not_active Expired - Lifetime
- 2001-12-12 ES ES01270570T patent/ES2295107T3/es not_active Expired - Lifetime
- 2001-12-12 MY MYPI20015665A patent/MY137550A/en unknown
- 2001-12-12 JP JP2002549762A patent/JP4100172B2/ja not_active Expired - Fee Related
- 2001-12-12 EP EP01270570A patent/EP1359175B1/en not_active Expired - Lifetime
- 2001-12-12 KR KR1020037007965A patent/KR100777500B1/ko active IP Right Grant
- 2001-12-12 AT AT01270570T patent/ATE380213T1/de active
- 2001-12-12 DE DE2001631778 patent/DE60131778T2/de not_active Expired - Lifetime
- 2001-12-12 AU AU2002222609A patent/AU2002222609A1/en not_active Abandoned
- 2001-12-12 CN CNB018180868A patent/CN1239559C/zh not_active Expired - Fee Related
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Also Published As
Publication number | Publication date |
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ATE380213T1 (de) | 2007-12-15 |
TWI290934B (en) | 2007-12-11 |
DE60131778D1 (de) | 2008-01-17 |
US7041399B2 (en) | 2006-05-09 |
US20060141262A1 (en) | 2006-06-29 |
EP1359175A4 (en) | 2005-10-19 |
MY137550A (en) | 2009-02-27 |
JP2008163329A (ja) | 2008-07-17 |
KR20030061445A (ko) | 2003-07-18 |
US20040034129A1 (en) | 2004-02-19 |
EP1359175A1 (en) | 2003-11-05 |
US7390571B2 (en) | 2008-06-24 |
JP4100172B2 (ja) | 2008-06-11 |
WO2002048236A1 (fr) | 2002-06-20 |
CN1471552A (zh) | 2004-01-28 |
DE60131778T2 (de) | 2008-10-30 |
ES2295107T3 (es) | 2008-04-16 |
EP1359175B1 (en) | 2007-12-05 |
JPWO2002048236A1 (ja) | 2004-04-15 |
KR100777500B1 (ko) | 2007-11-16 |
AU2002222609A1 (en) | 2002-06-24 |
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