CN116178890A - 热固性树脂组合物、pcb用半固化片及pcb用覆铜板 - Google Patents
热固性树脂组合物、pcb用半固化片及pcb用覆铜板 Download PDFInfo
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Abstract
本发明公开一种热固性树脂组合物,包括有脂环族环氧树脂80‑120份;促进剂0.01‑0.2份;填料55‑250份;脂环酸二酐45‑150份。本发明通过采用CPODA与脂环族环氧树脂复配使用,显著提高环氧树脂‑酸酐体系中的抗高温黄变性能,从而获得了一种耐高温黄变的环氧树脂组合物,适用于对耐温色变要求高的覆铜板、半固化片等产品中。
Description
技术领域
本发明涉及覆铜板领域技术,尤其是指一种热固性树脂组合物、PCB用半固化片及PCB用覆铜板。
背景技术
现在市面上常用环氧树脂主要为双酚A型环氧树脂和多官能基酚醛环氧树脂,它们都具有良好的热稳定性、化学稳定性、尺寸稳定性、力学性能、绝缘性、粘结性和成型加工性等,广泛应用于电子元器件、粘结材料、涂料和复合材料等领域。
但这些环氧树脂材料在高温或紫外强光条件下易发生光化学反应,导致环氧树脂降解,树脂材料变黄,机械性能降低;同时在制备过程中,往往会在反应体系中加入固化剂如双氰胺,而双氰胺含有胺类基团,导致环氧树脂-胺类固化体系在高温下很容易发生热氧化,严重的色变,不利于应用,特别是白光显示之LED、IC封装载板等领域中,对产品颜色限制严格,尤其是对树脂组合物抗黄变性提出了更高要求。为了实现耐高温黄变与紫外强光的特性,树脂和固化剂是该类固化体系迫切需要解决的问题。
发明内容
有鉴于此,本发明针对现有技术存在之缺失,其主要目的是提供一种热固性树脂组合物、PCB用半固化片及PCB用覆铜板,该热固性树脂组合物具备非常优异的高温耐黄变性能,适用于对耐温色变要求高的覆铜板、半固化片等产品中。
为实现上述目的,本发明采用如下之技术方案:
一种热固性树脂组合物,包括有脂环族环氧树脂80-120份;促进剂0.01-0.2份;填料55-250份;脂环酸二酐45-150份。
作为一种优选方案,进一步包括有其他酸酐类固化剂50-75份。
作为一种优选方案,所述其他酸酐类固化剂为六氢苯酐、偏苯三酸酐、苯酐、顺酐、四氢苯酐、甲基四氢苯酐和甲基六氢苯酐中的一种或一种以上。
作为一种优选方案,所述甲基六氢苯酐结构式如下:
R1、R2、R3、R4、R5和R6均为-H或-CH3,且R1、R2、R3、R4、R5和R6中至少有一个是-CH3。
作为一种优选方案,所述脂环族环氧树脂为3,4-环氧环己基甲酸-3,4-环氧环己基甲酯和聚[(2-环氧乙烷基)-1,2-环己二醇]2-乙基-2-(羟甲基)-1,3-丙二醇醚中的一种或一种以上。
作为一种优选方案,所述脂环族环氧树脂的环氧当量:酸酐当量比为在(0.5-1.5):1。
作为一种优选方案,所述促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-乙基-4-苯基咪唑、苄基二甲胺、溴化丁基三苯基磷盐、4,4’-二氨基二苯砜过氧化苯甲酸叔丁酯、3,3’-二氨基二苯砜过氧化苯甲酸叔丁酯、偶氮二异丁氰和有机金属盐或有机金属盐的络合物中的一种或一种以上。
作为一种优选方案,所述填料为二氧化钛,以增加树脂组合物制作的印制电路板的白度。
一种PCB用半固化片,其由前述的热固性树脂组合物制备而成。
一种PCB用覆铜板,其由前述的PCB用半固化片制备而成。
本发明与现有技术相比具有明显的优点和有益效果,具体而言,由上述技术方案可知:
本发明通过采用CPODA与脂环族环氧树脂复配使用,显著提高环氧树脂-酸酐体系中的抗高温黄变性能,从而获得了一种耐高温黄变的环氧树脂组合物,适用于对耐温色变要求高的覆铜板、半固化片等产品中。
本发明通过将脂环酸二酐与其他酸酐类固化剂复配加入反应体系中,可以显著提高反应体系中的抗高温黄变性能,从而获得了一种耐高温黄变的环氧树脂组合物,适用于对耐温色变要求高的覆铜板、半固化片等产品中。
为更清楚地阐述本发明的特征和功效,下面结合具体实施例来对本发明进行详细说明。
具体实施方式
本发明揭示一种热固性树脂组合物,包括有脂环族环氧树脂80-120份;促进剂0.01-0.2份;填料55-250份;脂环酸二酐45-150份。
该脂环族环氧树脂为3,4-环氧环己基甲酸-3,4-环氧环己基甲酯和聚[(2-环氧乙烷基)-1,2-环己二醇]2-乙基-2-(羟甲基)-1,3-丙二醇醚中的一种或一种以上;并且,脂环族环氧树脂的环氧当量:酸酐当量比为在(0.5-1.5):1。
该促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-乙基-4-苯基咪唑、苄基二甲胺、溴化丁基三苯基磷盐、4,4’-二氨基二苯砜过氧化苯甲酸叔丁酯、3,3’-二氨基二苯砜过氧化苯甲酸叔丁酯、偶氮二异丁氰和有机金属盐或有机金属盐的络合物中的一种或一种以上。
该填料为二氧化钛,以增加树脂组合物制作的印制电路板的白度。
以及,进一步包括有其他酸酐类固化剂50-75份;该其他酸酐类固化剂为六氢苯酐、偏苯三酸酐、苯酐、顺酐、四氢苯酐、甲基四氢苯酐和甲基六氢苯酐中的一种或一种以上;其中,该甲基六氢苯酐结构式如下:
R1、R2、R3、R4、R5和R6均为-H或-CH3,且R1、R2、R3、R4、R5和R6中至少有一个是-CH3。
本发明还揭示一种PCB用半固化片,由前述热固性树脂组合物制备而成,其制备过程如下:将上述各树脂按组份加入至溶剂中,该溶剂为酮类溶剂、芳香族类溶剂、醇醚溶剂中的一种或几种的混合,如:丙酮、丁铜、环己酮、甲苯、丙二醇甲醚;搅拌混合成均匀的树脂胶水,使用玻璃布浸入混合均匀的胶水中,并于170℃烘烤5分钟把溶剂烘干形成PCB用半固化片。
以及,本发明还揭示一种PCB用覆铜板,由前述PCB用半固化片制备而成,其制备过程如下:在前述PCB用半固化片的上下表面各覆盖一张1oz HTE铜箔,在真空热压机中高温固化,固化温度大于190℃,固化时间大于100分钟,固化压力为350PSI,即可制得PCB用覆铜板。
然后依据IPC-TM-650标准之测试方法测试覆铜板的物理性能,取实施例和对比例中制备的大小为10cm×20cm蚀刻后的基板,在260℃回流焊中分别进行空气热老化(分别进行3次、6次)后,取出观察基板的颜色(以白色打印纸为参照背景),颜色按顺序依次加深,分别描述为水白色,微黄色,浅黄色,深黄色,黄褐色。并对基板测试白度及反射率,以表征环氧树脂组合物的耐高温黄变性能。在下文的实施例中均采用此实施方法。
采用以下的实施例与对比例是对本发明的一个详细说明,但并非对本发明的范围作出界定,各实施例与对比例所使用的原料如表1所示,各实施例与对比例的性能测试结果如表2所示。
材料 | 生产厂家 | 型号 |
双酚A型环氧树脂 | 中国台湾南亚 | 128 |
酚醛环氧树脂 | 中国台湾南亚 | 704 |
脂环族环氧树脂 | 日本株式会社大赛璐 | 2021P |
脂环族环氧树脂 | 日本株式会社大赛璐 | 3150 |
双氰胺 | 河南欣之源 | DICY |
4,4'一二氨基二苯砜 | 河南欣之源 | DDS |
脂环族酸二酐 | 日本ENEOS株式会社 | CPODA |
甲基六氢苯酐 | 山东清洋 | MHHPA |
2-乙基-4甲基咪唑 | 日本四国化成 | 2E4MZ |
表1
表2
根据表2的数据进行分析,与对比例1-2相比,实施例1-6在添加脂环族环氧树脂和脂环族酸二酐能降低树脂组合物的膨胀系数和吸水率,具有低热膨胀率和优异耐湿热性;实施例1、3、5和实施例2、4、6中,同种树脂在完全添加脂环族酸二酐做固化剂能明显提高树脂组合物的Tg;同时,实施例1-6具有较高白度、反射率,在经过265℃回流焊6次后,能明显看出该树脂组合物所制作的基板不发黄,白度和反射率几乎不变;采用脂环族酸二酐做固化剂的树脂组合物不仅具有高白度、高反射率,也能耐高温黄变;在实施例7中减少一定比例的无机填料,其Z轴CTE高于实施例6,反射率和白度都低于实施例6;且采用脂环族酸二酐和甲基六氢苯酐复配使用,可以取得更为优异的效果;因此,本发明中采用脂环族环氧树脂和脂环族酸二酐所制作的覆铜板均具有高反射率、高白度、高玻璃化转变温度、低热膨胀率、优异的耐湿热性能,提高树脂组合物在PCB应用之可靠性。
以上所述,仅是本发明的较佳实施例而已,并非对本发明的技术范围作任何限制,故凡是依据本发明的技术实质对以上实施例所作的任何细微修改、等同变化与修饰,均仍属于本发明技术方案的范围内。
Claims (10)
1.一种热固性树脂组合物,其特征在于:包括有脂环族环氧树脂80-120份;促进剂0.01-0.2份;填料55-250份;脂环酸二酐45-150份。
2.根据权利要求1所述的热固性树脂组合物,其特征在于:进一步包括有其他酸酐类固化剂50-75份。
3.根据权利要求2所述的热固性树脂组合物,其特征在于:所述其他酸酐类固化剂为六氢苯酐、偏苯三酸酐、苯酐、顺酐、四氢苯酐、甲基四氢苯酐和甲基六氢苯酐中的一种或一种以上。
5.根据权利要求1所述的热固性树脂组合物,其特征在于:所述脂环族环氧树脂为3,4-环氧环己基甲酸-3,4-环氧环己基甲酯和聚[(2-环氧乙烷基)-1,2-环己二醇] 2-乙基-2-(羟甲基)-1,3-丙二醇醚中的一种或一种以上。
6.根据权利要求1所述的一种热固性树脂组合物,其特征在于:所述脂环族环氧树脂的环氧当量:酸酐当量比为在(0.5-1.5):1。
7.根据权利要求1所述的一种热固性树脂组合物,其特征在于:所述促进剂为2-甲基咪唑、2-乙基-4-甲基咪唑、2-苯基咪唑、2-乙基-4-苯基咪唑、苄基二甲胺、溴化丁基三苯基磷盐、4,4’-二氨基二苯砜过氧化苯甲酸叔丁酯、3,3’-二氨基二苯砜过氧化苯甲酸叔丁酯、偶氮二异丁氰和有机金属盐或有机金属盐的络合物中的一种或一种以上。
8.根据权利要求1所述的一种热固性树脂组合物,其特征在于:所述填料为二氧化钛。
9.一种PCB用半固化片,其特征在于:由权利要求1-7任一项的热固性树脂组合物制备而成。
10.一种PCB用覆铜板,其特征在于:由权利要求8的PCB用半固化片制备而成。
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