CN111748078A - 填孔用固化性树脂组合物 - Google Patents
填孔用固化性树脂组合物 Download PDFInfo
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- CN111748078A CN111748078A CN202010212164.6A CN202010212164A CN111748078A CN 111748078 A CN111748078 A CN 111748078A CN 202010212164 A CN202010212164 A CN 202010212164A CN 111748078 A CN111748078 A CN 111748078A
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- resin composition
- curable resin
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- curing agent
- epoxy resin
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Abstract
本发明为填孔用固化性树脂组合物。[课题]提供:适合作为印刷电路基板的通孔或导通孔的填孔用的固化性树脂组合物。[方案]一种填孔用固化性树脂组合物,其至少含有下述成分(A)~(C):(A)双酚E型环氧树脂、(B)3官能以上的环氧树脂、和(C)多胺型固化剂,且所述填孔用固化性树脂组合物的依据JIS‑C2161:2010测得的、100℃下的胶凝时间为30分钟以下。
Description
技术领域
本发明涉及固化性树脂组合物、特别是作为印刷电路基板的通孔或导通孔的填孔用途的固化性树脂组合物。
背景技术
对于多层印刷电路基板,为了应对部件的安装密度的上升和电路布线的复杂化,将由具有绝缘性的树脂构成的绝缘层、与印刷有导体图案的导电层交替层叠而成。而且,以贯通多个导电层和绝缘层的方式,形成经镀覆的通孔。
而且,必然期望开发出用于填充该通孔的孔部的填孔用树脂组合物,还提出了应对其的技术。
例如,专利文献1中,作为填充性等优异的填孔用树脂组合物,公开了如下技术:包含液态环氧树脂、液态酚醛树脂、固化催化剂和2种填料。
现有技术文献
专利文献
专利文献1:日本特开2001-19834号
发明内容
发明要解决的问题
在印刷电路基板的通孔中填充填孔用树脂组合物并使其固化的情况下,通常其表面成凸状。然而,未固化的其它树脂层、例如涂布、干燥、显影后、热固化前的未固化的阻焊层预先层叠于基板上的情况下,在通孔中填充填孔用树脂组合物,并干燥(预固化)、正式固化后,或在无干燥工序下进行正式固化后,该组合物与上述未固化的阻焊层接触,从而该组合物的一部分构成成分有时会扩散并渗透至该阻焊层。其结果,应填充至通孔内的填孔用树脂组合物的容量整体减少而填充量变得不充分,其固化后,以从通孔表面向通孔内部侧埋没的方式,有时在其表面形成凹陷。
对于该凹陷,在之后进行镀覆工序时引起镀覆的附着不良,或在进一步形成阻焊层时引起其密合不良,甚至还有妨碍精密图案的形成的担心,因此,是必须避免的课题之一。
关于这一点,仅凭借采用上述专利文献1中记载的、包含液态环氧树脂、液态酚醛树脂、固化催化剂和2种填料作为填孔用树脂组合物的技术,上述那样的、未固化的其它树脂层、例如涂布、干燥、显影后、热固化前的未固化的阻焊层预先层叠于基板上的情况下,在通孔中填充填孔用树脂组合物并进行干燥(预固化),无法充分防止正式固化后有时产生的通孔表面的凹陷。
因此,基于本发明人的研究的结果,获得了如下见解:用多胺型固化剂来调节固化速度对上述的填孔用树脂组合物的固化后的凹陷的发生有较大影响。
通过用多胺型固化剂来提高固化速度,从而能更有效地抑制填孔用树脂组合物的溶液渗透至阻焊层,由此明确,能防止固化后的填孔用树脂组合物形成凹陷。
从以上的观点出发,本发明的课题在于,提供如下新型的填孔用树脂组合物:通过组合使用2种环氧树脂、与规定的固化起始温度的多胺型固化剂作为通孔或导通孔的填孔用树脂组合物,从而具有更快的固化速度,由此,即使与未固化的其它树脂层、例如未固化的阻焊层接触的状态下进行固化,也可以防止引起其表面凹陷那样的填充不良的担心。
用于解决问题的方案
即,发现:上述课题可以通过如下填孔用固化性树脂组合物而解决:
所述填孔用固化性树脂组合物至少含有下述成分(A)~(C):
(A)双酚E型环氧树脂、
(B)3官能以上的环氧树脂、和
(C)多胺型固化剂,
且所述填孔用固化性树脂组合物的依据JIS-C2161:2010测得的、100℃下的胶凝时间为30分钟以下。
其中优选的一个方案为(C)多胺型固化剂具有95℃以下的固化起始温度。
另外,其它优选的方案中,上述填孔用固化性树脂组合物还含有咪唑型固化剂。
另外,更优选的方案中,上述填孔用固化性树脂组合物还含有无机填料。
进而,其它优选的方案中,本发明还涉及:由上述填孔用固化性树脂组合物形成的固化物、和具有该固化物的电子部件。
本发明中,作为填孔用固化性树脂组合物(以下,也简称为固化性树脂组合物)的主要成分,使用(A)双酚E型环氧树脂和(B)3官能以上的环氧树脂,并且采用(C)多胺型的固化剂作为固化剂。进一步,还具有如下构成:本发明的固化性树脂组合物的依据JIS-C2161:2010测得的、100℃下的胶凝时间为30分钟以下。
将上述构成的本发明的固化性树脂组合物填充于通孔、导通孔时,即使与未固化的阻焊层等未固化的其它树脂层接触,也能抑制在该组合物固化后引起在其表面产生凹陷的填充不良的担心。
关于这一点,也与本发明的固化性树脂组合物用多胺型固化剂来调节固化速度有关。详细情况在实施例中后述,但确认了,具有本发明的构成的固化性树脂组合物与具有除此以外的构成的固化性树脂组合物相比,胶凝时间更短,即,固化速度更快。该组合物在填充后迅速形成固化物,因此认为,能够有效地抑制成分在填充时渗透或扩散至未固化的其它树脂层、例如未固化的阻焊层等。
以下,对这样的本发明的固化性树脂组合物的各成分进行说明。
[(A)双酚E型环氧树脂]
印刷电路基板的通孔等填孔用途中使用的树脂组合物通常作为液态树脂组合物(填孔墨)使用,因此,为了在无溶剂下成为糊剂状,液态的环氧树脂、特别是固化后的填孔材料的机械性质、电性质、化学性质优异、粘接性也良好,因此,广泛使用有热固化型的环氧树脂组合物。
其中,本发明中,由于粘度低且耐热性高,而采用更适合作为填孔用途的树脂的双酚E型环氧树脂。
作为双酚E型环氧树脂,例如可以使用EPOXMKR710或R1710(AIR WATER INC制)等。它们均不易结晶化、保存稳定性良好,因此,是适宜的材料。
对于该(A)双酚E型环氧树脂的含量,基于固化性树脂组合物的总质量,为1%~40%、优选为5%~30%。
[(B)3官能以上的环氧树脂]
本发明中使用的(B)3官能以上的环氧树脂也可以理解为在1分子中具有3个以上环氧基的树脂。
本发明中,通过也组合使用该(B)3官能以上的环氧树脂,从而能进行更迅速的固化。
作为这样的(B)3官能以上的环氧树脂,例如可以举出苯酚酚醛清漆型环氧树脂、烷基苯酚酚醛清漆型环氧树脂、液态氨基苯酚型环氧树脂(特别是三缩水甘油基氨基苯酚型环氧树脂)、萘型环氧树脂、二环戊二烯型环氧树脂、缩水甘油基胺型环氧树脂、三羟基苯基甲烷型环氧树脂、四羟苯基乙烷型环氧树脂、苯二甲酸二缩水甘油酯树脂、脂环式环氧树脂、醇醚型环氧树脂。作为(B)3官能以上的环氧树脂的具体的制品,例如可以举出ADEKARESINEP-3980S(ADEKA株式会社制)、ADEKA RESINEP-3950S(ADEKA株式会社制)、jER-630(三菱化学株式会社制)。
其中,优选液态的氨基苯酚型环氧树脂、尤其优选三缩水甘油基氨基苯酚型环氧树脂。
对于该(B)3官能以上的环氧树脂的含量,基于固化性树脂组合物的总质量,为3%~30%、优选为5%~20%。
[(C)多胺型固化剂]
本发明中,作为固化剂,使用多胺型固化剂,例如可以举出改性脂肪族多胺、改性芳香族多胺等。
作为改性脂肪族多胺类,可以举出乙二胺、丙二胺、丁二胺、六亚甲基二胺、二亚乙基三胺、三亚乙基四胺或五亚乙基六胺的改性多胺等。
另外,作为改性芳香族多胺类,可以举出苯二胺或苯二甲胺的改性多胺等。
其中,从更快的固化速度的观点出发,优选具有95℃以下的固化起始温度,更优选具有80℃以下的固化起始温度。
作为(C)多胺型固化剂的具体的制品,例如可以举出FUJICURE FXR-1020(株式会社T&K TOKA制)、FUJICURE FXR-1081(株式会社T&K TOKA制)。
本发明中的(C)多胺型固化剂它们可以单独使用,或根据情况使用2种以上。
另外,作为(C)多胺型固化剂的含量,优选跟(A)双酚E型环氧树脂和(B)3官能以上的环氧树脂反应、且以能达成充分的固化的方式进行调节。
对于其含量,基于本发明的固化性树脂组合物中的(A)双酚E型环氧树脂、(B)3官能以上的环氧树脂、和包含的情况下其它环氧树脂的总质量,为0.5%~30质量%、优选为1%~20质量%。如果为0.5%~30质量%的范围内,则不仅固化性树脂组合物在低温下的固化性优异,而且保存稳定性也良好。
[咪唑型固化剂]
本发明中,在(C)多胺型固化剂的基础上,也可以组合使用以往使用的咪唑型固化剂。上述情况下,由固化性树脂组合物形成的固化物的耐热性进一步改善,故优选。
需要说明的是,用固化起始温度低的咪唑型固化剂将胶凝时间调节为较快,也无法得到使用多胺型固化剂时的防凹陷发生效果。
作为咪唑型固化剂,例如可以举出2-甲基咪唑、2-乙基-4-甲基咪唑、1,2-二甲基咪唑、1-苄基-2-甲基咪唑、1-苄基-2-苯基咪唑、1-氰基乙基-2-甲基咪唑、1-氰基乙基-2-乙基-4-甲基咪唑、1-氰基乙基-2-十一烷基咪唑、1-氰基乙基-2-苯基咪唑、2,4-二氨基-6-[2’-甲基咪唑基-(1’)]-乙基-均三嗪的异氰脲酸加成体(在咪唑的1位的N上加成有异氰脲酸)等。
另外,作为其市售品的例子,可以举出2MZ、2MZ-P、2PZ、2PZ-PW、2P4MZ、C11Z-CNS、2PZ-CNS、2PZCNS-PW、2MZ-A、2MZA-PW、C11Z-A、2E4MZ-A、2MA-OK、2MAOK-PW、2PZ-OK、2MZ-OK、2PHZ、2PHZ-PW、2P4MHZ、2P4MHZ-PW、2E4MZ·BIS、VT、VT-OK、MAVT、MAVT-OK(四国化成工业株式会社制)。
这些咪唑型固化剂当然可以组合使用2种以上。
另外,对于咪唑型固化剂的含量,基于本发明的固化性树脂组合物中的(A)双酚E型环氧树脂、(B)3官能以上的环氧树脂和包含的情况下其它环氧树脂的总质量,为0.5%~12质量%、优选为1%~10质量%。
[无机填料]
本发明的固化性树脂组合物中,可以还含有通常的树脂组合物中使用的无机填料。
具体而言,例如可以举出二氧化硅、硫酸钡、碳酸钙、氮化硅、氮化铝、氮化硼、氧化铝、氧化镁、氢氧化铝、氢氧化镁、氧化钛、云母、滑石、诺易堡硅土(Neuburg silica)、有机膨润土等非金属填料、铜、金、银、钯、硅等金属填料。
本发明的固化性树脂组合物中,这些无机填料可以单独使用,或也可以组合使用2种以上。
其中,体积膨胀性低和印刷性优异的二氧化硅、体积膨胀性低和研磨性优异的碳酸钙是适合的。
作为二氧化硅,可以为非晶、晶体,均可,也可以为它们的混合物。特别优选非晶(熔融)二氧化硅。另外,作为碳酸钙,可以为天然的重质碳酸钙、合成的沉降碳酸钙,均可。特别适合的是,研磨性优异的碳酸钙。
这样的无机填料的形状可以举出球状、针状、板状、鳞片状、中空状、不定形状、六角状、立方状、薄片状等,但从无机填料的高填充的观点出发,优选球状。
另外,这些无机填料的平均粒径优选0.1~25μm。平均粒径如果为0.1μm以上,则比表面积小且由于填料彼此的聚集作用的效果而良好地分散,而且容易增加填料的填充量。另一方面,如果为25μm以下,则对通孔的填充性变良好,进而具有在填孔的部分形成导电层时平滑性变得良好的效果。更优选为1~10μm。
需要说明的是,平均粒径是指平均一次粒径。平均粒径(D50)可以通过激光衍射/散射法而测定。
对于这些无机填料的含量,基于本发明的固化性树脂组合物中的(A)双酚E型环氧树脂、(B)3官能以上的环氧树脂、和包含的情况下其它环氧树脂的总质量,为300%以下、优选为250%以下。如果为300%以下,则可以容易对固化性树脂组合物进行液态糊剂化,可以得到良好的印刷性和填孔性,此外固化物体现充分低的体积膨胀性,且还体现良好的研磨性。
[其它成分]
本发明的固化性树脂组合物中,当然也可以进一步根据所需的特性含有除上述成分以外的其它成分。
作为这样的成分,例如可以举出硼酸酯化合物、对苯二酚、对苯二酚单甲醚、叔丁基邻苯二酚、连苯三酚、吩噻嗪等公知常用的热阻聚剂、粘土、高岭土、有机膨润土、蒙脱土等公知常用的增稠剂或触变剂、有机硅系、氟系、高分子系等的消泡剂和/或流平剂、咪唑系、噻唑系、三唑系、硅烷偶联剂等密合性赋予剂那样的公知常用的添加剂类。
[固化物]
本发明的固化性树脂组合物可以利用一直以来采用的方法、例如丝网印刷法、辊涂法、模涂法等容易地填充至印刷电路基板的导通孔、通孔等孔部。此时,如从孔部少许溢出那样以凸状完全填充。接着,使孔部由本发明的固化性树脂组合物所填充的印刷电路板在例如70℃~110℃下进行10分钟~120分钟左右干燥(预固化),在约120~180℃下进行约10~180分钟左右的加热(正式固化),使固化性树脂组合物固化,从而可以形成固化物。
如上述使本发明的固化性树脂组合物固化后,通过公知的物理研磨方法去除从印刷电路板表面溢出的固化物的不需要部分,可以平坦化。之后,将表面的布线层图案化为规定图案,而可以形成规定的电路图案。需要说明的是,根据需要利用高锰酸钾水溶液等进行固化物的表面粗糙化后,通过化学镀等可以在固化物上形成布线层。
[电子部件]
另外,本发明还提供一种电子部件,其具有上述固化物。
通过使用本发明的固化性树脂组合物,从而提供高品质、耐久性和可靠性得以维持的电子部件。
需要说明的是,本发明中电子部件是指电子电路中使用的部件,还包括:印刷电路板、晶体管、发光二极管、激光二极管等有源部件、以及电阻、电容器、电感器、连接器等无源部件。
发明的效果
根据本发明,作为印刷电路基板的通孔的填孔用固化性树脂组合物,可以提供:即使存在其它树脂层、例如阻焊层,也不会引起填充不良情况,固化后不产生表面凹陷的组合物。因此,对起因于这样的通孔的填孔的不良情况的精密图案的形成造成不良影响的担心低。
附图说明
图1为示意性示出对印刷电路基板的通孔填充了填孔用固化性树脂组合物时的状态的截面图。
图2为示意性示出对印刷电路基板的通孔填充了本发明的填孔用固化性树脂组合物并固化时的状态的截面图。
图3为示意性示出对印刷电路基板的通孔填充了现有的填孔用固化性树脂组合物并固化时的状态的截面图。
附图标记说明
1印刷电路基板 2通孔 3阻焊剂组合物 4铜镀层 5实施例1~4的固化性树脂组合物 5’比较例1和2的固化性树脂组合物 6通孔表面 7凹陷
具体实施方式
以下,示出实施例和比较例,对本发明具体地进行说明,但本发明当然不限定于以下的实施例。
需要说明的是,只要没有其它特别说明,表示的“份”和“%”就基于质量。
实施例
如下述,制作实施例1~4、以及比较例1和2的固化剂组合物。
<实施例1>
将双酚E型环氧树脂(EPOXMKR710;AIR WATER INC制)50份、双酚A型环氧树脂(jER-828;三菱化学株式会社制)10份、3官能以上的环氧树脂(三缩水甘油基氨基苯酚)(jER-630;三菱化学株式会社制)40份、具有95℃以下的固化起始温度的多胺型固化剂2(FUJICURE FXR-1081;株式会社T&K TOKA制)6份、咪唑型固化剂(2MZA-PW;四国化成工业株式会社制)6份、作为无机填料的超微粒重质碳酸钙(Softon1800;备北粉化工业株式会社制)150份和非晶二氧化硅(SO-C2;Admatechs Co.,Ltd.制)50份进行预混合,之后,用三辊磨使其分散混合,得到实施例1的固化性树脂组合物。
<实施例2>
使用具有95℃以下的固化起始温度的多胺型固化剂1(FUJICUREFXR-1020;株式会社T&K TOKA制)代替具有95℃以下的固化起始温度的多胺型固化剂2,除此之外与实施例1同样地得到实施例2的固化性树脂组合物。
<实施例3>
用具有95℃以下的固化起始温度的多胺型固化剂1(FUJICURE FXR-1020;株式会社T&K TOKA制)20份代替具有95℃以下的固化起始温度的多胺型固化剂2,且未使用咪唑型固化剂,除此之外与实施例1同样地得到实施例3的固化性树脂组合物。
<实施例4>
未使用双酚A型环氧树脂,除此之外与实施例3同样地得到实施例4的固化性树脂组合物。
<比较例1>
将双酚A型环氧树脂(jER-828;三菱化学株式会社制)100份、咪唑型固化剂(2MZA-PW;四国化成工业株式会社制)6份、作为无机填料的超微粒重质碳酸钙(Softon1800;备北粉化工业株式会社制)150份和非晶二氧化硅(SO-C2;Admatechs Co.,Ltd.制)50份进行预混合,之后,用三辊磨使其分散混合,得到比较例1的固化性树脂组合物。
<比较例2>
将双酚E型环氧树脂(EPOXMKR710;AIR WATER INC制)50份、双酚A型环氧树脂(jER-828;三菱化学株式会社制)10份、3官能以上的环氧树脂(三缩水甘油基氨基苯酚)(jER-630;三菱化学株式会社制)40份、具有超过95℃的固化起始温度的多胺型固化剂(FUJICURE FXR-1030;株式会社T&K TOKA制)6份、咪唑型固化剂(2MZA-PW;四国化成工业株式会社制)6部、作为填充材料的超微粒重质碳酸钙(Softon1800;备北粉化工业株式会社制)150份和非晶二氧化硅(SO-C2;Admatechs Co.,Ltd.制)50份进行预混合,之后,用三辊磨使其分散混合,得到比较例2的固化性树脂组合物。
将这些实施例1~4、以及比较例1和2的组成示于下述的表1。
[表1]
表1.固化性树脂组合物的组成
*1:EPOXMKR710(AIR WATER INC制)
*2:jER-828(三菱化学株式会社制)
*3:jER-630(三菱化学株式会社制)三缩水甘油基氨基苯酚(3官能环氧树脂)
*4:FUJICURE FXR-1020(株式会社T&K TOKA制)
*5:FUJICURE FXR-1081(株式会社T&K TOKA制)
*6:FUJICURE FXR-1030(株式会社T&K TOKA制)
*7:2MZA-PW(四国化成工业株式会社制※固化起始温度100℃以上)
*8:Softon1800(备北粉化工业株式会社制)
*9:SO-C2(Admatechs Co.,Ltd.制)
<试验例1>
对于实施例1~4、以及比较例1和2的各固化性树脂组合物,通过测定其胶凝时间,进行了涉及固化速度的快慢的试验。
依据JIS-C2161:2010中规定的热板法,用热板型凝胶化试验机(GT-D;株式会社Eucaly技研制)进行了胶凝时间的测定。
将用注射器量取了实施例1~4、以及比较例1和2的各固化性树脂组合物0.5mL的试样载置于设定为100℃的凝胶化试验机的热板上,边使搅拌针相对于热板面维持为90度的角度,边用针尖以90±10次/分钟的速度使试样搅拌成圆状。此时,将搅拌针变得无法旋转或者试样变得不粘合在针尖上等试样成为凝胶状时作为终点,测定从载置试样直至终点为止的时间。重复该操作3次,将它们的平均时间作为胶凝时间。各固化性树脂组合物的胶凝时间如表2所示。
<试验例2>
对于实施例1~4、以及比较例1和2的各固化性树脂组合物,填充至通孔后,进行关于使其固化时的表面有无凹陷的试验。
试验方法
如图1所示那样,用丝网印刷,在经图案形成的多层印刷电路基板1的通孔2部分以外,整面涂布阻焊剂组合物3(制品名:PSR-4000G23K;太阳油墨制造株式会社制),使得干燥膜厚成为20μm,然后在80℃下干燥30分钟,自然冷却至室温。然后,利用30℃的1wt%碳酸钠水溶液,将该基板在喷射压力0.2MPa的条件下进行90秒显影,得到图案。需要说明的是,图1~3中的符号4表示铜镀层。
接着,通过丝网印刷法,在得到的评价用多层印刷电路基板1的通孔2中,填充实施例1~4的固化性树脂组合物5、以及比较例1和2的各固化性树脂组合物5’,立于支架,在以基板相对于载置面成为90度±10度的角度的方式载置的状态下,在热风循环式干燥炉(制品名:DF610;Yamato Science Co.,Ltd.制)中,在80℃下进行60分钟干燥(预固化),之后,在150℃下进行30分钟加热(正式固化),从而使各固化性树脂组合物固化。
进行固化后的基板截面的光学显微镜观察(倍率:200倍),根据下述评价基准进行填充有固化性树脂组合物的通孔2的孔部的填充性评价。
无凹陷:通孔2的表面6平滑、且从其表面上向下方未发生凹陷(参照图2)。需要说明的是,即使从表面6的表面上向下方发生凹陷,该凹陷也达不到通孔内部,看作无凹陷。
有凹陷:在通孔2的表面6,从其表面上向通孔内部侧发生较大的凹陷7(参照图3)。
将结果示于下述表2。
[表2]
表2.试验结果
<结果>
对于实施例1~4的固化性树脂组合物,胶凝时间更短、且也观察不到固化后的表面的凹陷。
与此相对,对于比较例1和2的固化性树脂组合物,胶凝时间更长,且如图3所示那样,在表面观察到明显的凹陷7。认为这是由于,源自长的胶凝时间、即慢的固化速度而组合物中的一部分成分会渗透或扩散至与其接触的阻焊层3,使其容量损失。
而且,对于实施例1~4的固化性树脂组合物,在270℃下的5次循环的回流焊后无裂纹,确认了作为填孔用固化性树脂组合物没有问题。
Claims (6)
1.一种填孔用固化性树脂组合物,其至少含有下述成分(A)~(C):
(A)双酚E型环氧树脂、
(B)3官能以上的环氧树脂、和
(C)多胺型固化剂,
且所述填孔用固化性树脂组合物的依据JIS-C2161:2010测得的、100℃下的胶凝时间为30分钟以下。
2.根据权利要求1所述的填孔用固化性树脂组合物,其中,所述(C)多胺型固化剂具有95℃以下的固化起始温度。
3.根据权利要求1或2所述的填孔用固化性树脂组合物,其还含有咪唑型固化剂。
4.根据权利要求1~3中任一项所述的填孔用固化性树脂组合物,其还含有无机填料。
5.一种固化物,其是由权利要求1~4中任一项所述的填孔用固化性树脂组合物形成的。
6.一种电子部件,其具有权利要求5所述的固化物。
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