CN1041578C - 用于板面安装的环氧模塑组合物 - Google Patents
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Abstract
本发明涉及是用于板面安装的环氧模塑组合物。该组合物含有多官能环氧树脂和多官能固化剂同时还含有硅氧烷橡胶颗立有机官能硅氧烷流体和高填充量的二氧化硅。
Description
本发明涉及一种对于板面安装集成电路(IC)封装可提供高信赖度和高耐封装开裂的环氧模塑化合物配方。按惯例，集成电路(IC)封装一直是采用标准环氧模塑化合物配方进行灌封的，与电路板的连接包括通过电路板内的孔洞插入封装的插头和在很高的温度下(215-260℃)焊接该伸出的插头。该电路板限制热量流到灌封装置中；因此，封装经受很小的热焊接应力，从而对于封装开裂具有很高的可信赖度。
当前，在IC封装方面的发展趋势是趋向于板面安装型。这些封装不通过板上的孔洞插入而是直接安装到板上。通常这些封装比常规的封装薄，而且，这种板面安装技术可使封装焊接到电路板的两侧，因此使有效空间加倍，在这种焊接方法中，整个封装和电路都要被暴露到高温下。这种暴露增加了封装经受的热焊接应力；这些封装很薄加之它们又经受高温提高了封装开裂的可能性。塑料灌封吸收的任何湿气使封装开裂的问题更为严重。因此很有必要开发一种可防止这种焊接引起封装开裂的环氧模塑化合物配方并提供可从塑料灌封得到的其它性能(低应力，优良的可模塑性，低离子，等)。
日本专利申请No．01-276653披露一种板面安装环氧灌封剂，该灌封剂含有多官能环氧树脂，多官能固化剂和液态硅氧烷橡胶。
日本专利申请No．02-69514披露一种与其粒度要求低于3μm的二氧化硅颗粒结合使用的多官能环氧树脂。
日本专利申请No．63-226951披露的是线型酚醛清漆-有机聚硅氧烷嵌段共聚物、多官能环氧树脂，多官能固化剂和二氧化硅。
本发明的目在于提供一种在215℃下具有高挠曲强度从而可消除板面安装应用中遇到的因焊接而引起封装开裂问题的环氧模塑化合物配方并且也提供优良的低应力特性。
本发明还有一个目的则是提供一种环氧模塑组合物，该组合物含有高填充量的二氧化硅颗粒以便提供低吸湿性并减少该模塑组合物的热膨胀系数，另外该组合物在模塑条件下还将有足够的流动性。
本发明的一个具体实施方案将提供一种用于板面安装的低应力环氧灌封组合物。该板面安装环氧灌封剂含有(A)5-15％的多官能环氧树脂、(B)2．5-8％的多官能苯酚固化剂、(C)70-85％的熔融二氧化硅填料、(D)0．25-3％的硅氧烷橡胶粉末、和(E)0．25-3％的硅氧烷流体。这种组合物提供低应力性能和耐焊接引起的封装开裂和低吸湿性。
在另一个具体实施方案中，本发明将提供一种环氧模塑组合物，该组合物由于其中含有高填充量的二氧化硅，因此将提供优良的模塑性。
本发明的最佳实施方案说明于下：
(A)用于本发明的环氧树脂的是多官能型的，最好是三苯酚甲烷衍生的树脂。该多官能树脂可以单独使用，或与常规的EOCN树脂、疏水烃环氧树脂、双酚衍生的环氧树脂、双酚A树脂等结合使用。该多官能树脂将赋予该组合物高温下的挠曲强度并减少焊接引起的开裂现象。
(B)用于本发明的固化剂是多官能型的，最好，是三苯酚甲烷衍生物。该树脂可以单独使用或者与常规的苯酚酚醛清漆固化剂、疏水烃苯酚酚醛清漆、对苯二甲撑二甲醚酚醛清漆(xylok novolaks)等结合使用。该多官能固化剂将赋予高温挠曲强度并减少焊接引起的开裂现象。
(C)用于本发明的熔融二氧化硅是以高重量百分含量填充到组合物中的，以便减少模塑化合物配方的吸湿性也为了减少热膨胀系数。通常熔融二氧化硅的用量是从大约70％到大约85％(按配方重量计)，最好是从配方的75％到85％。对于降低吸湿性和降低热膨胀系数而言其填充量最好大于大约79％(按重量计)。所用的熔融二氧化硅可以是压碎的颗粒状，或者是球状，或者是两者的混合物。恰当地选择粒度、形状和填充量将可在赋予低吸湿性和低膨胀系数的同时也赋予良好的模塑性。最好该熔融二氧化硅是65-85％的球状二氧化硅和大约35-15％的压碎二氧化硅的掺混物。
(D)用于本发明的硅氧烷橡胶粉末最好是球形的并且其粒度小于50μm。使用该橡胶颗粒的作用在于减少热膨胀系数和减少模量。也可以使用粒度为＞50μm的压碎颗粒状的硅氧烷橡胶，但是它们不能有效地减少热膨胀系数的模量。
(E)用于本发明的硅氧烷流体是液态的，最好含有有机官能基团。最好的硅氧烷流体是那些既含有环氧官能基又含有多亚烷氧官能基的硅氧烷流体。这些流体在减少模量和降低模塑化合物配方粘度方面是很有效的。使用只含一种官能基或含其它官能基的流体将限制本发明中改进的可能性。组合物的制备方法；
例如，在球磨机中混合和掺混各种材料，并可以将该掺混物进行压紧以便容易处理，如果需要，还可以在挤压机中进行预软化或熔融混合，通常该掺混物可用任何合适的设备，例如传送机，送到差动辊式研磨机中，该研磨机包括一个热辊和一个冷辊，两辊沿着它们的纵向保持在1至6毫米之间的间距放置着，该距离称做辊隙。该辊隙可以调节，以获得所需尺寸的片材。
该差动辊式研磨机基本上可以是本技术领域已知的任何一种该类型研磨机。通常，该研磨机的各个辊子是在相反方向上以不同的表面速度围绕它们各自的纵轴进行转动，而该轴是近似水平的配置着。通常，各辊的相对转动速度比为1．1∶1和1．3∶1之间，并且其热辊的转速通常从大约10至30转／分。各个辊子通过任何适当的轴承装置转动式地安装在适当的支撑物上。
这样的合适的轴承装置的例子有滚柱轴承、滚珠轴承和套筒轴承。该支撑装置可以是框架或任何固着在基础或地基上的结构组件。各辊是采用任何一种合适的转动装置，例如电机或蒸汽机而被转动的，而这些转动装置是通过任何一种适合的装置如链条、皮带或齿轮连接到辊子的中心传动轴上的。通常，强制传动机械例如链条或齿轮是最好的。
通常热辊的表面温度是在掺混物中树脂的熔融温度附近，即是该树脂熔融温度的上下波动20℃的温度。但是在该温度下应不足以使掺混物在研磨机热辊上停留时间内使树脂固化。通常，热辊的表面温度为65℃和120℃之间，并且是由任何合适的加热装置或机械例如通过热辊的热水循环或电加热元件等维持该温度，而对于一些特殊的树脂而言该热辊温度可高达130℃。
下面提供的实施例是为了说明本发明的一些具体实施方案。但是它们将不限制在说明书和权利要求中充分描述的本发明的范围。实验方法：环氧模塑化合物的螺线流动度(EMMI)
该方法是使用一台装配有直径为1．75″的压铸料巢和EMMI螺线流动度模具的压铸模塑机测定热固性树脂的流动特性。
该压机压板温度控制器被设定成能产生175±3℃的模塑温度，并且压铸机压铸活塞压力被设定为1000磅／英寸2(Psia)。压铸机压铸活塞速度被设定在1-4英寸／秒的范围内。粒状料样被加到后铸料巢中产生0．12-0．14英寸的余胶厚度，并起动压铸循环。使该试样至少固化90秒。打开模具并测定最大程度地继续流动部分。该螺线流动度数据列入表中标为“螺线流动度”的栏目中；所列之值表示测得的流动度，单位为英寸。热力学分析-CTE测定：
将四个圆柱形模塑的后固化颗粒(5mm×5mm)放到烘箱中退火，并以10℃／分的升温速度将烘箱从25℃加热到240℃。冷却之后，在10℃／分的升温条件下测量25℃到250℃的膨胀曲线。对于Tg之前的膨胀曲线划一切线并从该切线的斜率测定Tg以下的热膨胀系数(CTE)。该数据记录在表上标为“CTE”的栏目中，该值的单位记成ppm／k。吸湿性；
模塑一个2″×1／8″的圆盘并进行后固化。将其从后固化箱中取出并使其在干燥器中进行固化。然后将该试样于85℃／85％相对湿度的箱内放置168小时。从箱内取出盘子并使其冷却，以重量分析法测定摄入的湿气，吸湿性记录在标为“吸湿”的栏目中，以增加的重量百分数表示，按照公式(W168-W0)／W0×100来计算该值，式中W0是时间为零时的重量，W168是在箱内放置168小时结束时的重量。挠曲性；
将材料的试样模制成5″×1／2″×1／4″并进行后固化，然后按ASTM D790方法并在可产生记录于下表各数据的相关温度下对该试样进行试验。使用预先放在干燥箱内的待测试样来测定215℃下的挠曲强度(表1中记录在“215℃挠曲强度”的条目中)和室温下的挠曲模量(记录在表1的室温挠曲模量条目中)。使用预先放在85℃／85％的相对湿度箱内饱和168小时的待测试样于215℃测定湿挠曲强度数据(在表1的“215°湿挠曲强度”条目中)。模量值的单位记为MPsi，强度值单位记为psi。缩略语：
下面指出用于本申请中的各缩略语的定义。FS762压碎的熔融二氧化硅FS762，平均粒度为13．4μm(由Denki Kagaku Kogyo Kabushiki Kaisha提供的)FB74球状熔融二氧化硅FB74平均粒度为31．5μm，(由Denki Kagabu Kogyo Kabushiki Kaisha提供的)FS20压碎的熔融二氧化硅FS20，平均粒度为5．6μm，(由DenkiKagaku Kogyo Kabushiki Kaisha提供的)橡胶球状硅氧烷橡胶AY49-281，粒度分布为3-30μm(由Toray／Dow Corning Silicone提供的)流体反应性硅氧烷流体Q2-8347(由Dow Corning Corporation提供的)EOCN环氧树脂ECN 195XL-25(由Sumitomo Chemical CoLtd．提供的)PN苯酚酚醛清漆树脂，Tamanol 758(由Arakawa ChemicalIndustries提供的)EPPN环氧树脂EPPN 502H(由Nippon Kayaku CoLtd．提供的)MEH苯酚树脂MEH7500(Meiwa Kasei，KK)BDMA苄基二甲胺(由AldrichChemcalComarg提供的)
TPP三苯基膦(由Aldrich Chemicm Company提供的)Dicyand二氰基二酰胺-G(由SKW Trostberg提供的)Sb205五氧化二锑，Na free Nyacol 1590(由PQ Corp．提供的)BisA四溴双酚-A BA59P(由Great Laks Chemical提供的)C Black Printex炭黑(由Degussa Corporation提供的)UL Wax UL蜡(由Hoechst-Celanese Corporation提供的)OP Wax OP蜡(由Hoechst-Celanese Corporation提供的)Psi磅／英寸2ppm百万分之几份试验方法：
按下述方法制备600克各批的试验试样，每种成分的用量按表中所列总批量的百分数计。每种材料的重量克数可以通过将表中所列的百分数乘以600倍的办法计算出来。将二氧化硅、硅烷和BD-MA放入到一台含氧化铝研磨介质的陶瓷制的球磨机中并研磨15分钟。取出这样处理过的二氧化硅并将其与液体硅氧烷(Q2-8347)进行掺混。然后将该材料再与配方中的其它成分一起放入球磨机中并且再研磨2小时。最好将所得的细粉末从研磨机中卸出来。
将该细粉末在前辊为热辊后辊为冷辊的二辊式差动研磨机中进行加工，如例1，前辊上的平均温度为95℃，并且前辊各部分上的温度不低于90℃或不高于100℃。又如其它各实施例，前辊上的平均温度为105℃，并且前辊上的温度不低于100℃或不高于110℃。各辊之间的间隙是1．02毫米。完成用树脂浸润填料之后将材料在研磨机上加工处理2-3分钟。在这拟定的2-3分钟内，模塑化合物的片材被切割10次并且再到研磨机上处理以便改进其混合程度。
完成研磨之后，该材料从辊上被剥下来，然后使其冷却并被造粒。该材料作为备用材料。该材料或是直接使用或是如试验方法中所述那样预成形成颗粒后使用。
表1序号 1 2 3 4 5 6 7 8 9成份FS762 75 75 79 - - - - - -FB74/FS20 - - - 75 75 75 79 79 79橡胶 1.5 1.5 1.5 0 1.5 1.5 0 1.5 1.5流体 1.5 1.5 1.5 1.5 0 1.5 1.5 0 1.5E0CN 12.507 - - - - - - - -PN 6.122 - - - - - - - -EPPN - 12.248 9.617 13.399 13.399 12.413 10.768 10.768 9.781MEH - 6.243 4.901 6.83 6.83 6.326 5.488 5.488 4.985B0MA 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003 0.003TPP 0.171 0.127 0.099 0.139 0.139 0.128 0.111 0.111 0.101Dicyand - 0.18 0.18 0.18 0.18 0.18 0.18 0.18 0.18Sb205 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2 1.2Bis A 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9 0.9C Black 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2UL Wax 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.20P Wax 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2
性能螺线流动度 31 19 11.5 39.3 36.6 29 25 16.3 23.3室温挠曲模量 2.26 2.19 2.49 2.08 2.24 1.98 2.49 2.7 2.37215℃挠曲强度 1795 6320 7380 4580 5240 4900 4990 6160 3840CTE 13.3 15.7 12.9 19.9 18.6 17 13.3 13.9 14.2吸湿 0.41 0.67 0.59 0.55 0.56 0.52 0.47 0.49 0.42215℃湿挠曲 1590 3050 3620 2760 2810 2880 3120 3290 2380
强度FB74／FS20是80份FB74与20份FS20的二氧化硅混合物。
Claims (10)
1．用于集成电路板面安装的低应力环氧模塑组合物，它包括：
a)从5％-15％的多官能环氧树脂；
b)从2．5％-8％的多官能固化剂；
c)从70％-85％的熔融二氧化硅，它是以包括球状和压碎颗粒两种形态的混合物形式存在的；
d)从0．25-3％的球状硅氧烷橡胶颗粒和
e)从0．25-3％的有机官能型的硅氧烷流体。
2．按照权利要求1的组合物，其中的多官能环氧树脂是三苯酚甲烷衍生物。
3．按照权利要求1的组合物，其中的多官能固化剂是三苯酚甲烷衍生物。
4．按照权利要求1的组合物，其中熔融二氧化硅用量至少为配方重量的75％，并且该二氧化硅是由65-85％的球形二氧化硅和由35-15％压碎的二氧化硅组成的一种混合物。
5．按照权利要求1的组合物，其中硅氧烷流体具有环氧基和多亚烷氧基两种官能基。
6．用权利要求1的组合物灌封的集成电路。
7．用权利要求2的组合物灌封的集成电路。
8．用权利要求3的组合物灌封的集成电路。
9．用权利要求4的组合物灌封的集成电路。
10．用权利要求5的组合物灌封的集成电路。
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| US69388291A | 1991-05-01 | 1991-05-01 | |
| US693,882 | 1991-05-01 |
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| CN (1) | CN1041578C (zh) |
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Also Published As
| Publication number | Publication date |
|---|---|
| AU1519592A (en) | 1992-11-05 |
| KR100234942B1 (ko) | 1999-12-15 |
| MY110809A (en) | 1999-05-31 |
| ATE142370T1 (de) | 1996-09-15 |
| EP0511833A3 (en) | 1992-12-30 |
| AU660666B2 (en) | 1995-07-06 |
| KR920021646A (ko) | 1992-12-18 |
| IE921403A1 (en) | 1992-11-04 |
| MX9202065A (es) | 1992-12-01 |
| DE69213308D1 (de) | 1996-10-10 |
| SG38926A1 (en) | 1999-09-21 |
| NO921632D0 (no) | 1992-04-28 |
| EP0511833A2 (en) | 1992-11-04 |
| PH30678A (en) | 1997-09-16 |
| NO921632L (no) | 1992-11-02 |
| DE69213308T2 (de) | 1997-01-30 |
| ZA923022B (en) | 1992-12-30 |
| IL101664A (en) | 1996-01-31 |
| EP0511833B1 (en) | 1996-09-04 |
| FI921981A0 (fi) | 1992-04-30 |
| FI921981A (fi) | 1992-11-02 |
| JP3340462B2 (ja) | 2002-11-05 |
| BR9201580A (pt) | 1992-12-15 |
| TW252138B (zh) | 1995-07-21 |
| US5434199A (en) | 1995-07-18 |
| CN1069147A (zh) | 1993-02-17 |
| CA2066497A1 (en) | 1992-11-02 |
| NZ242461A (en) | 1994-04-27 |
| IL101664A0 (en) | 1992-12-30 |
| JPH05152467A (ja) | 1993-06-18 |
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