CN107304282B - 热固性树脂组合物及搭载有电子部件的基板 - Google Patents
热固性树脂组合物及搭载有电子部件的基板 Download PDFInfo
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- CN107304282B CN107304282B CN201710259355.6A CN201710259355A CN107304282B CN 107304282 B CN107304282 B CN 107304282B CN 201710259355 A CN201710259355 A CN 201710259355A CN 107304282 B CN107304282 B CN 107304282B
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- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
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Abstract
本发明涉及热固性树脂组合物及搭载有电子部件的基板。本发明的课题在于提供能够通过回流焊接后的加热及真空操作除去空隙的热固性树脂组合物及搭载有电子部件的基板。本发明的解决手段为:本实施方式涉及的热固性树脂组合物包含液态的环氧树脂、配合单羧酸及多乙烯基醚而形成的半缩醛酯、固化剂、和填料。
Description
技术领域
本发明涉及在电路基板上搭载电子部件(表面安装部件)时使用的热固性树脂组合物及使用了所述热固性树脂组合物的搭载有电子部件的基板。
背景技术
一直以来,作为将电子部件搭载于电路基板的表面安装技术,以下的方法A、B是已知的。作为方法A,在电路基板上涂布焊剂(flux),使用回流焊装置安装电子部件后,清洗焊剂,然后,填充底部填充材料(underfill material)并进行热固化。作为方法B,先在电路基板上涂布具有焊剂作用的底部填充材料,搭载电子部件后,利用回流焊装置同时进行焊接和底部填充材料的热固化。
由于伴随电子设备的小型化而要求电子部件的多针(pin)化和连接间距的缩小化,导致接合部的焊料体积减少,电路基板与电子部件之间的间隙不断变窄,因此,以往的方法中存在电子设备的可靠性降低的问题。
上述的方法A中,存在焊剂的清洗变得不充分、容易残留离子性成分的问题,以及难以利用毛细管现象来填充底部填充材料的问题。另外,上述的方法B中,由于回流(reflow)温度高于底部填充材料的固化温度,因此,底部填充材料在回流后完全固化,存在产生大量的空隙(void)(其是由于在除去焊料、铜的氧化膜时生成的水的原因而形成的)的问题。另外,在涂布了底部填充材料的电路基板上临时放置电子部件时,存在底部填充材料在卷入了空气的状态下固化、产生大量的空隙的问题。
为了解决这样的问题,提出了下述方法:在电路基板表面的至少一部分上涂布热固性树脂组合物,将电子部件搭载于电路基板上,进行回流焊接,实施真空操作及/或低于涂布树脂的固化温度的加热,然后将涂布树脂加热固化(参见专利文献1)。
现有技术文献
专利文献
专利文献1:日本特开2013-59807号公报
发明内容
发明要解决的课题
然而,已发现在上述方法中存在下述问题:即使在回流焊接之后实施低于固化温度的加热,也不易发生热固性树脂组合物的软化,难以利用真空操作除去空隙。因此,期望开发出能够利用回流焊接之后的加热及真空操作除去空隙的热固性树脂组合物。
本发明是为了解决上述的课题而作出的,其目的在于,提供能够通过回流焊接之后的加热及真空操作除去空隙的热固性树脂组合物及搭载有电子部件的基板。
用于解决课题的手段
本申请的发明人发现,通过使结束回流焊接的时刻的环氧基的反应率为40%以下,能够利用回流焊接之后的加热及真空操作除去空隙。
作为能够使结束回流焊接的时刻的环氧基的反应率为40%以下的热固化组合物,本发明包含以下的方案。
[1]
热固性树脂组合物,其包含:
液态的环氧树脂;
由单羧酸及多乙烯基醚(polyvinyl ether)合成的半缩醛酯(hemiacetalester);
固化剂;和
填料。
[2]
如[1]所述的热固性树脂组合物,其中,所述半缩醛酯是由相对于所述环氧树脂的环氧基而言为0.2~0.4当量的单羧酸、和相对于所述单羧酸的羧基而言为1.0~1.5当量的多乙烯基醚进行合成而形成的。
[3]
如[1]或[2]所述的热固性树脂组合物,其中,所述固化剂含有氰基胍和三聚氰胺。
[4]
如[1]~[3]中任一项所述的热固性树脂组合物,其中,所述固化剂含有相对于所述环氧树脂的环氧基而言为0.4~0.5当量的氰基胍、和相对于所述环氧基而言为0.08~0.18当量的三聚氰胺。
[5]
如[1]~[4]中任一项所述的热固性树脂组合物,其中,所述填料含有10~40质量%的平均粒径为0.5~5μm的球状填料。
[6]
如[1]~[5]中任一项所述的热固性树脂组合物,其中,所述填料中含有的0.3μm以下的微粒的累积含有率为所述填料的总量的10质量%以下。
[7]
如[1]~[6]中任一项所述的热固性树脂组合物,其中,于220~260℃进行10~20秒回流后的所述环氧树脂中的环氧基的反应率为40%以下。
[8]
搭载有电子部件的基板,其具有:
电路基板;
安装于所述电路基板上的电子部件;和
将[1]~[7]中任一项所述的热固性树脂组合物进行热固化而得到的固化物,所述固化物被设置于所述电路基板与所述电子部件之间。
发明的效果
根据本发明,能够使结束回流焊接的时刻的环氧基的反应率为40%以下,从而能够通过回流焊接之后的加热及真空操作除去空隙。
附图说明
图1是用于说明应用了本实施方式的热固性树脂组合物的表面安装技术的一个方式的工序剖面图。
附图标记说明
1...电路基板、2...焊盘、3...未固化的热固性树脂组合物、4...电子部件、9...焊料凸点、10...热固性树脂组合物的固化物。
具体实施方式
以下,根据需要,一边参照附图,一边对本发明的实施方式(以下称为“本实施方式”)进行详细说明,但本发明并不限于此,可在不脱离其主旨的范围内进行各种变形。
在应用本实施方式涉及的热固性树脂组合物的表面安装技术中,通常用于电连接的焊料为主要含有锡、银和铜的合金,其熔点为约220℃,在回流焊接工序中,实施通过120~160℃的预加热进行的1分钟左右的加热、和用于连接焊料的10秒左右的220~260℃的加热。
因此,热固性树脂组合物在回流焊接工序中开始进行各种反应。
1)由半缩醛酯的解离反应生成羧酸
2)焊料、铜的氧化膜(金属氧化物)与羧酸的反应
3)羧酸与环氧树脂的反应
4)羧酸与热固化剂的成盐反应
5)羧酸金属盐与环氧树脂的反应
6)环氧树脂与热固化剂的反应
结果,即使在回流焊接后再次进行加热,仍然不易发生热固性树脂组合物的软化,从而难以利用真空操作除去空隙,除去因卷入的空气、氧化膜除去时生成的水而产生的空隙是困难的。
经过深入研究,结果发现,通过使回流后的环氧树脂的反应率为40%以下,能够利用回流后的加热及真空操作除去电路基板与电子部件之间的空隙。
(热固性树脂组合物)
为了使回流后的环氧树脂的反应率为40%以下,本实施方式涉及的热固性树脂组合物包含液态的环氧树脂、配合单羧酸及多乙烯基醚而形成的半缩醛酯、固化剂、和填料。以下,对于本实施方式涉及的热固性树脂组合物包含的各成分进行详细说明。
本申请的用于表面安装技术的热固性树脂组合物中含有液态的环氧树脂。环氧树脂具有作为基体树脂的功能。另外,环氧树脂在固化反应时还与后述的活化剂(羧酸)反应,具有使活化剂失活的功能。由此,固化后的涂布树脂变得极具热稳定性,在加热时(例如,底部填充树脂的加热固化时)不会发生腐蚀反应或产生分解气体。
热固性树脂组合物包含常温下为液态的环氧树脂,优选实质上不包含溶剂。通过使热固性树脂组合物不包含溶剂,能够防止由溶剂挥发时产生的气体导致的空隙的产生。
所谓液态的环氧树脂,是指常温下为液态的环氧树脂,例如,可举出在常温下具有流动性的环氧树脂。作为这样的液态环氧树脂,例如粘度(室温,mPa·s)为20000以下,特别优选为1000~10000。液态环氧树脂的环氧当量(EEW)为100~400,优选为100~200。另外,液态环氧树脂的重均分子量(Mw)为200~1000,优选为300~600。
优选地,作为液态环氧树脂,包括双酚A型环氧树脂、双酚F型环氧树脂、缩水甘油胺型环氧树脂、脂环式环氧树脂等,可使用这些树脂中的一种以上。
双酚A型环氧树脂由下式表示,可使用这些树脂中的一种以上。
[化学式1]
[上式中,n表示0或1。G表示缩水甘油基。]
液态双酚F型环氧树脂由下式表示,可使用这些树脂中的一种以上。
[化学式2]
[上式中,n表示0或1。G表示缩水甘油基。]
半缩醛酯通过使单羧酸与多乙烯基醚反应而合成。半缩醛酯中的羧酸作为用于提高焊接性的活化剂而发挥功能。对于羧酸而言,其会于室温直接与环氧树脂中的环氧基反应,因此,通过使羧酸与乙烯基醚进行反应而形成半缩醛酯,能够抑制羧酸与环氧树脂的反应。进而,为了使半缩醛酯不在预加热时发生解离并进行反应,半缩醛酯的解离温度为170℃以上是合适的。通过将羧酸进行半缩醛酯化,能够抑制热固性树脂的低温副反应,从而能够提高热固性树脂组合物的保存稳定性。
作为进行半缩醛酯化的羧酸,使用在1分子中具有1个羧基的单羧酸,以使得即使在解离后与环氧树脂反应、也不会发生由交联反应导致的凝胶化。单羧酸可以是脂肪族系、芳香族系、多环芳香族系、杂环系中的任意单羧酸,芳香族单羧酸、多环芳香族单羧酸会与环氧基反应而成为非反应性的侧链,因此从耐热性的方面考虑是优选的。
单羧酸的配合量优选相对于环氧树脂的环氧基而言为0.2~0.4当量。相对于1当量的环氧基而言,单羧酸小于0.2当量的情况下,焊料的氧化膜除去性变差,发生连接不良,大于0.4当量的情况下,由于单羧酸与环氧基的反应导致环氧基被消耗而减少,固化性降低。
作为进行半缩醛酯化的乙烯基醚,可使用在1分子中具有2个以上的乙烯基的多乙烯基化合物,但为了降低半缩醛酯自身的粘度,优选脂肪族多乙烯基醚、脂环式多乙烯基醚。
多乙烯基醚的配合量优选相对于单羧酸的羧基而言为1至1.5当量。相对于1当量的单羧酸而言,多乙烯基醚小于1.0当量的情况下,未半缩醛化的羧酸于室温也与环氧树脂进行反应而被消耗,导致连接性降低,大于1.5当量的情况下,过量的乙烯基醚残留而成为产生空隙的原因,并且,固化物的耐热性降低。
使用单乙烯基醚作为乙烯基醚的情况下,用于进行半缩醛化的乙烯基醚配合量增多,有时会导致空隙的产生、固化物的耐热性降低等问题。另外,对于使用了多元羧酸和多乙烯基醚的半缩醛酯而言,由于会发生高分子量化而生成凝胶,因此,其与环氧树脂的相容性降低,配合物无法变得均匀。
对于单羧酸和多乙烯基醚而言,为了使它们自身不会气化而产生空隙,使用沸点为200℃以上的单羧酸和多乙烯基醚。
固化剂是用于与环氧树脂反应而形成三维交联结构的成分。作为固化剂,为了使回流焊接后的环氧基的反应率为40%以下、且能够于通常的固化温度(150~180℃)完全固化,优选使用氰基胍及三聚氰胺。通过使用氰基胍及三聚氰胺,在短时间的加热中不会发生固化反应,因此,即使在回流时也能够防止热固性树脂组合物固化。
氰基胍的配合量优选相对于环氧树脂的环氧基而言为0.4~0.5当量。氰基胍小于0.4当量的情况下,环氧基的反应没有完成,发生固化不良,大于0.5当量的情况下,由于回流工序导致固化反应过度进行,后脱泡性降低,残留空隙。
三聚氰胺的配合量优选相对于环氧树脂的环氧基而言为0.08~0.18当量。三聚氰胺小于0.08当量的情况下,也同样地,环氧基的反应没有完成,发生固化不良,大于0.12当量的情况下,由于回流工序导致固化反应过度进行,后脱泡性降低,残留空隙。
填料是基于减小固化后的环氧树脂组合物的热膨胀系数、提高热导率的目的而添加的,优选使用二氧化硅、氧化铝等的微球状填料。
对于球状填料而言,为了抑制环氧树脂组合物的粘度上升,平均粒径优选为0.5μm以上,另外,为了不阻碍焊料凸点的润湿延展,平均粒径优选为5μm以下。使用了平均粒径小于0.5μm的球状填料的情况下,填料的表面积变得过大,组合物的粘度升高,后脱泡性降低,平均粒径大于5μm的情况下,在焊料连接时发生填料的啮入,连接性降低。
另外,进一步优选球状填料中含有的0.3μm以下的微粒合计为球状填料的10质量%以下。这是因为,球状填料中含有的0.3μm以下的微粒的累积含有率大于10质量%的情况下,填料的表面积增大,因此组合物的粘度升高,后脱泡性降低。
球状填料的含量优选为10质量%以上且40质量%以下。球状填料的含量小于10质量%的情况下,固化收缩变大,在芯片、电路基板与环氧树脂组合物之间容易产生间隙,为大于40质量%的情况下,后脱泡性和连接性降低。
热固性树脂组合物中,作为其他的添加剂,可含有硅油等消泡剂、硅烷偶联剂、AEROSIL等。
对于本实施方式涉及的热固性树脂组合物而言,于220~260℃进行10~20秒热处理后的上述环氧树脂中的环氧基的反应率为40%以下。由此,即使在这样的热处理条件下实施回流焊接,也能够抑制热固性树脂发生固化。
根据本实施方式涉及的热固性树脂组合物,在回流焊接后,能够通过比该回流焊接的热处理温度更低的温度(80℃~160℃)下的再加热而使其软化,从而能够通过实施真空操作而除去树脂中包含的空隙。
(表面安装方法)
接着,对于应用本实施方式涉及的热固性树脂组合物的表面安装方法进行说明。
如图1A所示的那样准备印刷布线基板等电路基板1。接着,如图1B所示的那样,在电路基板1表面上的至少一部分(包括整个表面)上涂布本申请的热固性树脂组合物3。例如,可在电路基板1上的至少金属表面的一部分上进行涂布。作为金属,可举出例如纯金属(铜等)及合金(焊料等),可以是这些金属中的一种以上。热固性树脂组合物3的层厚通常为10~50μm。
接着,如图1C所示的那样,在电路基板1上临时放置电子部件4。该进行临时放置的工序中,存在由于空气的卷入而产生气泡10的情况。本实施方式涉及的热固性树脂组合物也可应用于大型的电子部件、例如50mm见方以上的表面安装技术。作为电子部件4,具体而言可举出封装部件(BGA部件、CSP部件、MCM部件、IPM部件、IGBT部件等)、半导体芯片等。
接着,如图1D所示的那样,进行回流焊接。回流焊接包括预加热工序(120~140℃,40~80秒)、升温工序(140~220℃,5~15秒)、回流工序(220~260℃,10秒~30秒)。若加热时间过长,则有时会发生涂布树脂的固化反应,因此不优选。该回流焊接时,存在下述情况:位于熔融焊料表面的氧化物等由于热固性树脂组合物中的半缩醛酯而发生还原等,结果生成水等。该生成的水等蒸发并膨胀,导致进一步产生气泡10。
接着,如图1E所示的那样,基于脱泡的目的,进行真空操作及/或低于热固性树脂组合物的固化温度的加热。由此,因临时放置电子部件时的空气卷入(图1C)、回流工序中焊料氧化膜的除去(图1D)而产生的水和气泡10被除去。真空操作条件优选为例如真空度1~500(特别优选为50~300)kPa、1~60(特别优选为5~30)分钟。
基于脱泡目的的加热以低于热固性树脂组合物的固化温度的条件进行。通过该加热,热固性树脂组合物软化,脱水·脱泡得以进行,不仅如此,该软化后的热固性树脂组合物还使得电路基板表面上的凹凸被吸收(平坦化)·均匀化。具体而言,作为基于脱泡目的的加热条件,优选为例如60~150(特别优选为80~130)℃、1~60(特别优选为10~20)分钟。
之后,如图1F所示的那样将热固性树脂组合物加热固化,制成固化物10。作为加热固化条件,可以为固化剂的固化反应开始温度以上(具体而言为150~200℃)、1~4小时。由此,环氧树脂与固化剂进行反应,形成三维交联结构。另外,此时,由半缩醛酯的解离反应生成羧酸,羧酸与环氧树脂发生反应,从而丧失了作为活化剂的活化能力。因此,由于羧酸不会残留,故而消除了由腐蚀等导致可靠性降低的原因。
通过上述操作,制造了本申请涉及的搭载有电子部件的基板。如上所述,在上述的搭载有电子部件的基板的制造方法中,不需要设置个别的焊剂。
通过上述操作制造的本实施方式涉及的搭载有电子部件的基板具有:电路基板1;安装于电路基板1上的电子部件4;和设置于电路基板1与电子部件4之间的、将本实施方式涉及的热固性树脂组合物3进行热固化而得到的固化物10。
利用本实施方式涉及的搭载有电子部件的基板,能够抑制在电路基板1与电子部件4之间的接合材料10中产生空隙,因此,能够提高电路基板1与电子部件4的电连接及机械性接合的可靠性,进而能够提高搭载有电子部件的基板的可靠性。
(实施例)
以下,利用实施例及比较例对本发明更具体地进行说明。本发明不受以下实施例的任何限定。
如下表1、2所示的那样,分别计量环氧树脂、半缩醛酯、氰基胍、三聚氰胺、球状填料,使用搅拌机混合30分钟,用三辊式研磨机使混合物分散。将得到的环氧树脂组合物在真空下(100kPa)进行10分钟搅拌·脱泡,得到实施例及比较例的热固性树脂组合物。表1、2所示的数值表示将环氧树脂作为100质量份时的质量份。另外,表1、2中,所谓“0.3μm以下”,表示0.3μm以下的微粒的累积含有率。表1、2中记载了使用的填料的平均粒径,平均粒径利用激光衍射·散射法测定。
[半缩醛酯的合成]
表1、2所示的半缩醛酯是如下述这样合成的。
合成例1(参见实施例1)
将25.34质量份(相对于环氧树脂的环氧基而言相当于0.29当量)的乙氧基苯甲酸(当量166,沸点315℃)和18.13重量份(相对于乙氧基苯甲酸的羧基而言相当于1.35当量)的环己烷二甲醇二乙烯基醚(当量88,沸点310℃)混合,于80℃搅拌10小时使其反应。反应结束后,实施反应物的FT-IR测定,确认了羧基的吸收消失。
合成例2(实施例16)
使用了24.00质量份(相对于环氧树脂的环氧基而言相当于0.30当量)的甲氧基苯甲酸(当量152,沸点200℃)和21.53质量份(相对于甲氧基苯甲酸的羧基而言相当于1.35当量)的三乙二醇二乙烯基醚(当量101,沸点220℃),除此以外,与合成例1同样地进行反应,实施反应物的FT-IR测定,确认了羧基的吸收消失。
合成例3(比较例1)
使用了15.95质量份(相对于环氧树脂的环氧基而言相当于0.30当量)的作为2官能羧酸的癸二酸(当量101,沸点386℃)和18.33质量份(相对于癸二酸的羧基而言相当于1.35当量)的作为单乙烯基醚的异丙基单乙烯基醚(当量86,沸点55℃),除此以外,与合成例1同样地进行反应,实施反应物的FT-IR测定,确认了羧基的吸收消失。
需要说明的是,表1、2所示的合成例1、2及3中的羧酸的栏的数值表示用于合成的羧酸相对于环氧基而言的当量。另外,乙烯基醚的栏的数值表示用于合成的乙烯基醚相对于羧基而言的当量。
另外,对于利用2官能以上的羧酸和2官能以上的乙烯基醚进行的半缩醛化而言,由于在反应中发生高分子化而生成凝胶化物,因此不理想。
[电路基板和芯片]
为了对热固性树脂组合物进行评价,作为电路基板1,使用了设有连接盘(connection land)的电路基板(30mm见方,厚度0.4mm,连接盘数196,连接盘间距300μm,连接盘表面处理为镀镍-金),作为电子部件,使用了试验用TEG芯片(4.2mm见方,厚度0.4mm,凸点数196,凸点间距300μm,焊料种类为含有96.5质量%的锡、3.0质量%的银和0.5质量%的铜的合金)。另外,为了进行导通试验,将电路基板和评价用TEG芯片构成菊花链(daisychain)电路。
[试验方法]
使用分配器(dispenser)在电路基板的焊盘部上涂布3mg的实施例及比较例的热固性树脂组合物。在其上方载置评价用TEG芯片,使用回流焊装置(预加热:120~140℃、60秒;升温:140~220℃、8秒;回流:220~260℃、12秒)进行焊接。焊接结束后,使用附带热板的真空室,加热至120℃,实施真空操作(达到的真空度为100kPa,15分钟)。真空操作后,从真空室中取出,使用干燥机,于160℃加热2小时进行固化,得到安装有TEG的基板。
[评价方法和判定基准]
对于通过上述操作得到的安装有TEG的基板,如表1、2所示的那样,从空隙(后脱泡性)、固化性、焊料连接性、低固化收缩性的观点进行评价。各评价的评价方法和判定基准如下所示。
(空隙:后脱泡性)
关于对空隙的确认,用磨光机对安装基板的TEG芯片进行研磨,直到热固性树脂的固化物露出为止,使用20倍的显微镜以目视观察。将完全没有空隙的情况评价为◎,将大小为75μm(即凸点间距离的一半)以下的空隙为3个以下的情况评价为○,将空隙的大小超过75μm的情况、及具有4个以上的空隙的情况评价为×。
(固化性)
关于固化性,使用具有2mm见方的开口的150目(Mesh)的丝网板,以约50μm的厚度在与上述相同的电路基板上印刷热固性树脂组合物,对于在与上述相同的条件下进行固化后的热固性树脂组合物,按照JIS K 5600-5-4刮擦硬度(铅笔法)进行测定,将铅笔硬度为2H以上、且进一步将该测定涂膜再次于160℃加热1小时后铅笔的划痕没有变化(变形、消失)的情况评价为○,将铅笔硬度为H以下、或由于再加热而导致铅笔的划痕发生变化的情况评价为×。
(焊料连接性)
关于焊料连接性,使用设置于安装基板上的菊花链电路实施导通试验,将导通的情况评价为○,将未导通的情况评价为×。
(低固化收缩性)
关于低固化收缩性,对于安装了评价用TEG芯片的电路基板,削出截面,使用50倍的显微镜观察截面,将截面完全被填充的情况评价为○,将在电路基板侧或TEG芯片侧存在间隙的情况评价为×。
[回流后的环氧基的反应率]
根据试验前的热固性树脂组合物的FT-IR图中的位于910cm-1处的环氧基的吸收峰相对于位于1508cm-1处的苯环的吸收峰的强度之比、和回流后的热固性树脂组合物的FT-IR图中的苯环与环氧基的吸收峰的强度之比,算出环氧基的反应率。
[关于实施例及比较例的结果]
对于实施例而言,确认到总体而言空隙少、后脱泡性优异。尤其是满足下述条件的实施例1~16在表1中列举的全部评价试验中均得到了高的评价:1)包含液态的环氧树脂;2)包含由相对于环氧树脂的环氧基而言为0.2~0.4当量的单羧酸(苯甲酸)、和相对于所述单羧酸的羧基而言为1.0~1.5当量的多乙烯基醚进行合成而形成的半缩醛酯;3)包含含有相对于环氧树脂的环氧基而言为0.4~0.5当量的氰基胍、和相对于环氧基而言为0.08~0.18当量的三聚氰胺的固化剂;以及4)含有10~40质量%的平均粒径为0.5~5μm的球状填料;5)填料中含有的0.3μm以下的微粒的累积含有率为所述填料的总量的10质量%以下;6)于220~260℃进行10~20秒回流后的环氧树脂中的环氧基的反应率为40%以下。
实施例17~31的结果比实施例1~16差。具体如下所示。
实施例17中,羧酸被环氧基消耗,导致氧化膜除去性不充分。
实施例18中,羧酸与环氧基进行反应,导致对于固化而言所必需的环氧基变得不足。
实施例19中,固化剂不足。
实施例20中,在回流时进行反应,发生凝胶化。
实施例21中,固化剂不足,导致固化不充分。
实施例22中,在回流时进行反应,发生凝胶化。另外,树脂在焊料熔融前发生固化,导致无法连接。
实施例23中,在固化后的截面观察中,在TEG侧产生了间隙。
实施例24中,组合物的粘度上升,无法进行后脱泡,粒子阻碍了焊料的润湿性,导致连接不良。
实施例25中,组合物的粘度上升,导致无法进行后脱泡。
实施例26中,大粒子阻碍了焊料的润湿性,导致连接不良。
实施例27中,组合物的粘度上升,导致无法进行后脱泡。
实施例28~31中,在回流时进行反应,发生凝胶化。树脂在焊料熔融前发生固化,导致无法连接。
对于比较例1而言,作为羧酸使用了2官能的癸二酸,由于回流的加热而导致环氧树脂发生三维固化,因此焊料连接性被阻碍,进而脱泡性降低,残留了大量的空隙。
对于比较例2而言,由于没有添加填料,因此,固化收缩变大,发生了底部填充材料与TEG芯片的剥离。
Claims (7)
1.热固性树脂组合物,其包含:
液态的环氧树脂;
由单羧酸及多乙烯基醚合成的半缩醛酯;
固化剂;和
填料;
所述固化剂含有氰基胍和三聚氰胺。
2.如权利要求1所述的热固性树脂组合物,其中,所述半缩醛酯是由相对于所述环氧树脂的环氧基而言为0.2~0.4当量的单羧酸、和相对于所述单羧酸的羧基而言为1.0~1.5当量的多乙烯基醚进行合成而形成的。
3.如权利要求1或2所述的热固性树脂组合物,其中,所述固化剂含有相对于所述环氧树脂的环氧基而言为0.4~0.5当量的氰基胍、和相对于所述环氧基而言为0.08~0.18当量的三聚氰胺。
4.如权利要求1或2所述的热固性树脂组合物,其中,所述填料含有10~40质量%的平均粒径为0.5~5μm的球状填料。
5.如权利要求1或2所述的热固性树脂组合物,其中,所述填料中含有的0.3μm以下的微粒的累积含有率为所述填料的总量的10质量%以下。
6.如权利要求1或2所述的热固性树脂组合物,其中,于220~260℃进行10~20秒回流后的所述环氧树脂中的环氧基的反应率为40%以下。
7.搭载有电子部件的基板,其具有:
电路基板;
安装于所述电路基板上的电子部件;和
将权利要求1~6中任一项所述的热固性树脂组合物进行热固化而得到的固化物,所述固化物被设置于所述电路基板与所述电子部件之间。
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CN1690119A (zh) * | 2004-04-26 | 2005-11-02 | 太阳油墨制造株式会社 | 热固性树脂组合物以及使用该组合物的多层印刷电路板 |
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US10870725B2 (en) | 2020-12-22 |
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DE102017108256A1 (de) | 2017-10-26 |
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JP6374434B2 (ja) | 2018-08-15 |
CN107304282A (zh) | 2017-10-31 |
TW201738312A (zh) | 2017-11-01 |
KR20170120513A (ko) | 2017-10-31 |
KR101900602B1 (ko) | 2018-09-19 |
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