CN1370810A - 粘合剂组合物和用于半导体器件的粘合片材 - Google Patents

粘合剂组合物和用于半导体器件的粘合片材 Download PDF

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CN1370810A
CN1370810A CN02105054A CN02105054A CN1370810A CN 1370810 A CN1370810 A CN 1370810A CN 02105054 A CN02105054 A CN 02105054A CN 02105054 A CN02105054 A CN 02105054A CN 1370810 A CN1370810 A CN 1370810A
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binder composition
epoxy
butadiene
block copolymer
semiconducter device
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CN02105054A
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CN1254507C (zh
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小林正治
冈修
吉井康弘
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Tomoegawa Co Ltd
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Tomoegawa Paper Co Ltd
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C09J163/08—Epoxidised polymerised polyenes
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract

一种用于半导体器件的粘合剂组合物,含有作为主要组分的(A)环氧树脂,(B)酚醛树脂,(C)环氧化的苯乙烯－丁二烯－苯乙烯嵌段共聚物,和(D)二氨基硅氧烷化合物。该粘合剂组合物的耐热性、热循环试验和耐湿性优良。本发明还提供了一种使用上述粘合剂组合物的粘合片材。

Description

粘合剂组合物和用于半导体器件的粘合片材
发明的背景技术
1.发明领域
本发明涉及使用各种半导体的半导体器件中适用的粘合剂组合物和粘合片材，尤其是具有其中在由集成电路绝缘层和导电电路组成的集成电路板上层叠集成电路芯片这一结构的半导体器件，即一种表面安装型的半导体器件和一种多层集成电路芯片型的半导体器件，本发明尤其还涉及一种粘合剂组合物和一种粘合片材用于粘接集成电路芯片或辐射器板，或在集成电路板上进行高密度的层压，亦即将集成电路芯片与集成电路板、绝缘层粘接在一起，使得在集成电路板、集成电路芯片和辐射器片，辐射器片和集成电路板、和/或集成电路芯片上具有较高密度的叠层。
2.相关现有技术的说明
随着便携式个人计算机和移动电话的最近发展，对尺寸小、较薄以及多功能的电子部件的需求增加。
为了满足这些需求，电子零部件的尺寸必须随整体化比例的增加而降低，而且需要高密度安装电子零部件的技术。
近年来至于构成电子零部件核心的集成电路封装件，典型地使用外围安装(periphery-mounting)型封装件如QFP(四线扁平封装)和SOP(小外型封装)。然而，近来被称为BGA(球栅阵列)、CSP(电路尺寸片封装件)和BOC(Board on chip)的表面安装型的集成电路封装件和被称为MCP(多芯片封装件)的多层集成电路芯片型的集成电路封装件被公认为可进行高密度安装的集成电路封装件。
在BGA、CSP和BOC中，焊球作为与外部的连接端子，以平面格状的形式存在于其背面上。集成电路电极(半导体集成电路)通过集成电路板或布线图式电路配电板与印刷电路板的电极相连接。根据集成电路板类型，现已开发出塑料BGA(下文称为“P-BGA”)、陶瓷BGA(下文称为“C-BGA”)、带状(tape)BGA(下文称为“T-BGA”)、增强型BGA(下文称为“E-BGA”)等。
直到最近才广泛使用P-BGA，一种可在QFP中使用的丝焊技术。然而，利用TAB(带自动焊接)技术的T-BGA变得更普遍，因为它具有致密作用(针脚倍增)且在热辐射方面性能优良。
CSP是通过进一步减少尺寸和致密化BGA而制造的封装件，它被称为“微型BGA”或“小节距BGA(fine pitch BGA)”。由于其结构，CSP具有优良的电学可靠性如低阻抗和快速频率响应。
小节距BGA的一个实例如图1的横截面所示。
在该实例中集成电路板1由绝缘层2和在绝缘层2的一个表面上由导电电极3等形成的导电电路组成，且在其中具有中心空洞。集成电路板1在集成电路芯片5上通过粘合层4层叠。集成电路芯片5通过在其上形成的凸起用金属线6与导电电极3相连接。布线和连接均用树脂7包覆。在导电电极3未被树脂7包覆的那部分上形成布线8，并在该布线上形成焊球9，从而达到BGA与外部的电连接。
小节距BGA的另一实例如图2的横截面所示。在该实例中集成电路板1由绝缘层2和在绝缘层2表面上形成的导电电极3组成，绝缘层2上提供有多个用于焊接导电电极的通孔，其中在所述用于焊接的该侧上没有形成导电电极3。第一块集成电路芯片5a和加强板10通过粘合层4层叠到绝缘层2上所形成的导电电极3上，和第二块集成电路芯片5b通过粘合层4层叠到第一块集成电路芯片5a上。集成电路芯片5a和5b通过在其上形成的凸起用金属线6与导电电极3相连接。布线和连接均用树脂7包覆。在绝缘层2所提供的通孔中形成焊球9，从而与导电电极3连接和使BGA与外部电连接。
小节距BGA的另一实例如图3的横截面所示。在该实例的小节距BGA中，导电电极3和集成电路芯片5通过粘合层4层叠到辐射器板11的一个表面上。在导电电极3中没有粘合层4的那一个表面上，有绝缘层2，所述绝缘层具有用于焊接导电电极3的通孔，从而构成集成电路板1。集成电路芯片与通过在其上形成的凸起用金属线6与导电电极3相连接。布线与连接均用树脂7包覆，在绝缘层2所提供的通孔中形成焊球9，从而与导电电极3连接和使BGA与外部电连接。
为了形成构成集成电路板的绝缘层2，通常使用的板材有聚酰亚胺树脂、环氧树脂、酚醛树脂等。而且，为了形成粘合层4，常规使用环氧树脂/NBR(丙烯腈-丁二烯共聚物)基粘合剂、环氧树脂/酚醛树脂基粘合剂和橡胶改性的环氧树脂/酚醛树脂基粘合剂。
集成电路封装件被驱动时，由于集成电路所产生的热量，达到100℃或更高的温度，和集成电路封装件经历从室温到高温(100℃或更高)的温度变化。因此，要求集成电路封装件具有耐热性，能经受该情况下的应力变化，在高温条件下的耐湿性以及应力松弛性能。
特别是近年来，安装密度增加，结果导电金属线的比例变大，从而必需将不同热膨胀系数的材料粘接在一起。还要求集成电路封装件能经受该情况下所产生的应力。然而，由上述组分组成的粘合剂不足以经受长期的温度变化，也不足以耐受高温和高湿度的条件。
更具体地说，由于在室温和高温(100℃或更高)之间的温度变化反复循环而导致的应力作用，所以在上述构成集成电路板的绝缘层2和集成电路芯片5之间，或在层叠板内部常会发生层离现象。而且，作为增加安装密度的方法，可层叠绝缘层以形成三维布线图。该方法也有同样的缺陷。在这种层叠型高密度安装方法中，作为层叠基质，在许多情况下，除了玻璃环氧树脂板外，还可使用TAB板、性板等，以便使封装件变薄，其中的大多数材料是聚酰亚胺树脂等。
一般来说，聚酰亚胺树脂等很难粘接，且易受吸水、界面等条件的影响。因此，要求吸水低和粘合力优良的粘合剂组合物。
而且，在层叠型高密度安装方法中，必须在层叠过程中嵌入布线图。因此，要求粘合剂组合物在嵌入期间树脂不发生流动和在粘接期间不发泡。
而且，由于近年来的无铅趋势所伴随的IR回流温度的升高，在回流期间粘合剂中所含有的水可能蒸发并将粘合剂推开，从而使引起气泡的水蒸气爆破，即所谓的爆玉米花现象。因此，为了除去引起爆玉米花现象的水含量，可在除湿条件下处理回流前的半成品。然而，在除湿条件下的处理要求大量人力和财力，因此需要一种粘合剂组合物，即使不在除湿条件下处理也不会产生爆玉米花现象。
而且，从半导体部分的应用角度考虑，要求粘合剂组合物具有电学可靠性。
发明概述
本发明已克服上述缺陷，和其中之一的目的是提供一种粘合剂组合物和一种用于半导体器件的粘合片材，它们克服了半导体器件如BGA和CSP中所使用的传统的粘合剂组合物的缺陷或克服了由温度的循环变化所产生的层离缺陷；换句话说，它们在应力松弛和耐受热/热循环试验方面是优良的。
本发明另一目的是提供一种粘合剂组合物和一种用于半导体器件的粘合片材，其中粘合剂树脂在粘接和固化期间不流动和不发泡，而这种现象在传统的粘合剂组合物中会发生。
本发明另一目的是提供一种粘合剂组合物和一种用于半导体器件的粘合片材，所述半导体器件的电学可靠性以及与铜、聚酰亚胺等的粘接强度优良。
本发明再一目的是提供一种粘合剂组合物和一种用于半导体器件的粘合片材，它克服了传统的粘合剂组合物的缺陷或粘合剂组合物所含有的水在回流期间蒸发而产生的爆玉米花现象；换句话说，它具有优良的耐湿性。
为了达到这些目的，本发明一方面提供了一种用于半导体器件的粘合剂组合物，其中包括(A)环氧树脂，(B)酚醛树脂，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物。
优选地，以官能团的当量比来表示，(A)环氧树脂与(B)酚醛树脂之比为1∶0.6-1∶1.4。
优选地，(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的比例占粘合剂组合物总固含量的30-80重量％。
优选地，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物中丁二烯与苯乙烯之重量比为1/99-70/30。
优选地，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物的环氧当量为140-6000。
优选地，(D)二氨基硅氧烷化合物是以下通式(1)表示的，在两端均具有氨基的二氨基硅氧烷化合物：
Figure A0210505400071
其中R1是具有1-10个碳原子的亚烷基和n是0-10的整数。
优选地，(D)二氨基硅氧烷化合物占粘合剂组合物总固含量的0.3-10重量％。
本发明的另一方面提供了一种用于半导体器件的粘合片材，其中包括一种载体和如上所述的一种粘合剂组合物，所述粘合剂组合物至少在载体的一个表面上层叠。
优选地，载体包括绝缘膜或防粘膜。
附图的简要说明
图1是涂覆本发明粘合剂组合物的集成电路封装件(小节距BGA)实例的横截面视图。
图2是涂覆本发明粘合剂组合物的集成电路封装件(小节距BGA)另一实例的横截面视图。
图3是涂覆本发明粘合剂组合物的集成电路封装件(小节距BGA)再一实例的横截面视图。
优选实施方案的详细说明
现详细描述本发明的实施方案。
本发明用于半导体器件的粘合剂组合物由(A)环氧树脂，(B)酚醛树脂，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物组成。
现详细描述本发明用于半导体器件的粘合剂组合物的每一组分。
(A)环氧树脂
作为环氧树脂，可单独或结合使用任何在一个分子中具有两个或多个环氧乙烷环结构的树脂如缩水甘油基醚、缩水甘油基酯、缩水甘油基胺、线性脂族环氧化物和脂环族环氧化物。
实例包括双官能团的环氧树脂如双酚A型环氧树脂、双酚F型环氧树脂、双酚S型环氧树脂和萘型环氧树脂，多官能团缩水甘油基胺型环氧树脂如三缩水甘油基异氰脲酸酯型环氧树脂、三缩水甘油基-对氨基苯酚型环氧树脂、四缩水甘油基二氨基二苯甲烷型环氧树脂、四缩水甘油基间亚二甲苯基二胺型环氧树脂和四缩水甘油基-1，3-双氨甲基环己烷型环氧树脂，多官能团缩水甘油基醚型环氧树脂如四苯基缩水甘油基醚乙烷型环氧树脂和三苯基缩水甘油基醚甲烷型环氧树脂，多官能团可熔酚醛树脂型环氧树脂如苯酚型环氧树脂和烷基苯酚型环氧树脂，和多官能团线型酚醛树脂型环氧树脂如苯酚型环氧树脂和甲酚型环氧树脂。
其中双酚型环氧树脂因其低价格，和多官能团环氧树脂因其绝缘性和耐热性被特别优选使用。
本发明所使用的环氧树脂环氧当量优选为100-4000，更优选为100-2000和特别优选为100-1000。若环氧当量小于100，树脂可能保持部分不固化，从而引起发泡。若环氧当量超过4000，树脂在溶剂中几乎不溶，导致与其它树脂不相容。
更具体地说，作为本发明优选使用的环氧树脂，可提及的是，Yuka ShellEpoxy K.K.所供应的那些，双酚型环氧树脂如商品名为Epikote 806，828，834和1001的那些，双官能团环氧树脂如YX-4000和YX-4000H(二苯基型)，Epikote152，154，180S65，1032H60和157S70(多官能团线型酚醛树脂)和604(四缩水甘油基二苯甲烷型)；Dainippon Ink & Chemicals，Inc.所供应的那些，多官能团环氧树脂如商品名为HP-7200和HP-7200H(二环型)的那些；Nippon Kayaku Co.，Ltd.所供应的那些，多官能团环氧树脂如商品名为EOCNI02S，103S，104S，1020(间-甲酚线型酚醛树脂)，EPPN501H和502H(三苯甲烷型)。
可有利地使用环氧卤化物，特别是环氧溴化物以赋予阻燃性。环氧溴化物的实例包括Yuka Shell Epoxy K.K.所供应的商品名为Epikote 5045，5046和5050以及Nippon Kayaku Co.，Ltd.所供应的商品名为Bren-S，Bren-105和Bren-301的那些。
(B)酚醛树脂
酚醛树脂与环氧树脂反应形成三维网状结构。
本发明所使用的酚醛树脂的实例包括酚醛树脂如可熔酚醛树脂、线型酚醛树脂、甲酚线型酚醛树脂、间苯二酚树脂和二甲苯树脂，其中优选线型酚醛树脂，因其优良的反应性以及优良的耐湿性和耐热性。
以官能团的当量比来表示，环氧树脂与酚醛树脂之比为1∶0.6-1∶1.4，优选1∶0.7-1∶1.1。
在环氧树脂与酚醛树脂的上述比例中，若环氧树脂与酚醛树脂的比例小于1∶0.6，则固化的树脂发脆，另一方面，若环氧树脂与酚醛树脂的比例大于1∶1.4，则粘合力不利地降低。
(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物
环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物是在苯乙烯-丁二烯-苯乙烯嵌段共聚物中衍生于共轭二烯烃化合物并被环氧化的双键化合物。上述的苯乙烯-丁二烯-苯乙烯嵌段共聚物是苯乙烯化合物和丁二烯化合物的嵌段共聚物，在及苯乙烯-丁二烯-苯乙烯嵌段共聚物中衍生于共轭二烯烃化合物的双键可被部分氢化。
上述的苯乙烯-丁二烯-苯乙烯嵌段共聚物是指由苯乙烯化合物聚合物嵌段A和丁二烯化合物聚合物嵌段B所组成的嵌段共聚物，其中苯乙烯化合物聚合物嵌段A是苯乙烯化合物基的聚合物嵌段而丁二烯化合物聚合物嵌段B是丁二烯化合物基的聚合物嵌段。苯乙烯化合物与丁二烯化合物的共聚重量比为1/99-70/30，特别优选10/90-60/40。
苯乙烯-丁二烯-苯乙烯嵌段共聚物的数均分子量在5000-600000范围内，优选10000-500000，和分子量分布(重均分子量(Mw)与数均分子量(Mn)之比)为10或更低。
苯乙烯-丁二烯-苯乙烯嵌段共聚物的分子结构可以是直链、支链、星形或其任选的结合形式。例如，可使用至少一种选自A-B，A-B-A，B-A-B-A，A-B-A-B-A等的苯乙烯化合物-丁二烯化合物嵌段共聚物结构。
作为构成苯乙烯-丁二烯-苯乙烯嵌段共聚物的苯乙烯化合物，至少一种可选自，例如苯乙烯、α-甲基苯乙烯、对叔丁基苯乙烯、对甲基苯乙烯、1，1-二苯基苯乙烯等，其中优选苯乙烯。
作为构成苯乙烯-丁二烯-苯乙烯嵌段共聚物的丁二烯化合物，至少一种可选自，例如丁二烯、2，3-二甲基-1，3-丁二烯、苯基-1，3-丁二烯等，其中优选丁二烯。
可使用任何方法作为制备用作本发明材料的苯乙烯-丁二烯-苯乙烯嵌段共聚物，只要所制备的嵌段共聚物具有上述结构。
通过上述的苯乙烯-丁二烯-苯乙烯嵌段共聚物或其部分氢化产物与环氧化试剂如氢过氧化物、过酸等在惰性溶剂中反应可得到本发明所使用的环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物。用于环氧化的氢过氧化物包括过氧化氢、氢过氧化叔丁基、氢过氧化枯烯等，过酸包括过甲酸、过乙酸、过苯甲酸、三氟代过苯甲酸等。其中过乙酸因价格低和稳定性高是优选的环氧化试剂。环氧化过程中，根据需要可加入催化剂。例如，在过酸情况下，可使用碱如碳酸钠或酸如硫酸。在氢过氧化物的情况下，通过使用钨酸和苛性钠的混合物与过氧化氢结合有机酸与过氧化氢结合或六羰基钼与过氧化叔丁基结合可获得催化效果。例如，为了降低材料的粘度和通过稀释环氧化试剂而获得的稳定作用，可使用惰性溶剂，和在过乙酸的情况下，可使用芳族化合物、醚、酯等。特别优选的溶剂是己烷、环己烷、甲苯、苯、乙酸乙酯、四氯化碳或氯仿。
对环氧化试剂的用量没有特别限制，根据不同的因素如所使用的具体的环氧化试剂、所需的环氧化程度、所使用的嵌段共聚物等来决定各种情况下最适宜的用量。环氧化反应条件没有特别限制，可使用的反应温度范围可根据所使用的环氧化试剂的活性来决定。例如，在过乙酸的情况下，优选0-70℃，因为如果低于0℃，导致反应缓慢，和如果超过70℃，则过乙酸分解。不需额外加工反应混合物，和例如搅拌混合物2-10小时就足够了。通过合适的方法如在不良溶剂中沉淀，将反应混合物投入热水同时搅拌并蒸馏除去溶剂或直接脱溶剂可分离所得到的环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物。
由此得到的(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的环氧当量优选为140-6000，更优选200-2000。若环氧当量小于140，所得到的聚合物弹性如伸长性和弹性增加改进较小；若环氧当量超过6000，环氧化所得到的具体性能如增加的相容性改进较小。
粘合剂组合物中环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的优选比例占总固含量的30-80重量％。若小于30重量％，树脂可能太硬且粘合力降低；若超过80重量％，则在应用和固化期间会不利地发生树脂流动和发泡。而且，若超过80重量％，树脂中可能产生气孔，导致高温下发泡。
(D)二氨基硅氧烷化合物
本发明所使用的二氨基硅氧烷化合物是以下通式(1)表示的，在两端均具有氨基的二氨基硅氧烷化合物：
Figure A0210505400121
其中R1是具有1-10个碳原子的亚烷基和n是0-10的整数。
粘合剂组合物中二氨基硅氧烷化合物的比例优选占总固含量的0.3-10重量％，更优选0.3-5重量％。若小于0.3重量％，与其它树脂的相容性和吸水能力降低；若超过10重量％，在通常条件下粘合力显著降低。
作为以上通式(I)表示的、两端具有氨基的二氨基硅氧烷化合物，可提及的是，例如Toshiba Silicone Co.，Ltd.所供应的商品名为TSL9306和TSL9886的那些。
在本发明的粘合剂组合物中优选加入偶联剂以改进与粘合体的粘合力。
作为偶联剂，特别优选具有端氨基或端环氧基的那些作为其有机端基。基于100重量份(A)环氧树脂，(B)酚醛树脂，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物的总量，偶联剂优选加入0.1-15重量份。
而且，为了促进环氧树脂的固化，可视需要使用固化促进剂如咪唑及其衍生物、咪唑啉及其衍生物或叔胺，基于100重量份上述组分(A)-(D)的总量，用量为0.01-5重量份。
而且，为了调整热膨胀系数和导热性以及控制可加工性，本发明用于半导体器件的粘合剂组合物优选含有有机或无机填料。
作为本发明所使用的无机填料，可提及的是，例如无水二氧化硅、熔融态二氧化硅、氧化铝、氧化钛、氧化铍、氧化镁、碳酸钙、氮化钛、氮化硅、氮化硼、硼化钛、硼化钨、碳化硅、碳化钛、碳化锆、碳化钼、云母、氧化锌、碳黑、氢氧化铝、氢氧化钙、氢氧化镁和用三甲基甲硅烷氧基进行表面处理的那些等。
作为有机填料，可提及的是，例如聚酰亚胺、聚酰胺-酰亚胺、聚醚酮、聚醚-酰亚胺、聚酯-酰亚胺、尼龙和硅氧烷。
基于100重量份(A)环氧树脂，(B)酚醛树脂，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物的总量，填料优选含有2-95重量份，更优选2-50重量份。
在有机溶剂中溶解上述主要组分(A)-(D)和各种添加剂以制备粘合剂溶液。本发明所使用的有机溶剂没有特别限制。可适量地任选单独或结合使用例如甲苯、二甲苯、甲乙酮、四氢呋喃等。粘合剂溶液优选制备成含有至少20重量％固含量。若固含量小于20重量％，可能难以制备均匀的粘合片材。
本发明用于半导体器件的粘合片材由载体和该载体的至少一个表面上粘附的上述粘合剂组合物组成。
载体的实例包括防粘膜、绝缘膜以及剥离纸，其中优选使用防粘膜和绝缘膜。
作为用作防粘膜和绝缘膜的膜材料，优选使用聚酯如聚对苯二甲酸乙二酯、聚烯烃如聚乙烯、聚酰亚胺、聚酰胺、聚醚砜、聚亚苯硫醚、聚醚酮和三乙酰纤维素，其中更优选使用聚酯、聚烯烃和聚酰亚胺。优选使用由这些材料形成的以及用脱模剂如硅氧烷进行防粘处理的防粘膜。
通过将上述粘合剂组合物溶解在有机溶剂中而制备的粘合剂溶液涂覆到膜的一个或两个表面上并干燥以形成粘合层，优选对粘合层进行半固化处理。
在具体的加工和使用条件下，例如缩短固化时间和嵌入导电图案，适当控制半固化状态以防止树脂流动和发泡。优选通过陈化等手段控制半固化状态，尽管不限于具体的方法。
粘合层的干燥厚度为3-200微米，优选5-100微米。
视需要为了便于保存，用保护膜覆盖其上形成的粘合层的膜，待使用时除去所述保护膜。
本发明用于半导体器件的粘合剂组合物和粘合片材适用于各种电子零部件，特别适用于半导体，在所述半导体中含绝缘层和导电电路的集成电路板具有在电路表面或背面上粘附的集成电路芯片。实例包括利用TAB技术的T-BGA和表面安装型CSP。更具体地说，本发明的粘合剂组合物和粘合片材可有利地用在图1、2和3所示的半导体器件中，作为粘合剂用于粘接集成电路芯片和绝缘层和/或集成电路板的导电电路。
实施例
以下实施例进一步详细说明本发明，但不能理解为对本发明的限制。
如下所述首先合成环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物。
合成实施例1
向配有搅拌器和冷凝管的烧瓶中加入300g苯乙烯-丁二烯-苯乙烯嵌段共聚物(商品名：TR2000，由Japan Synthetic Rubber Co.，Ltd.供应，数均分子量：100000；苯乙烯/丁二烯的共聚比(重量)为40/60)，以及1500g溶解所述共聚物的乙酸乙酯。然后在40℃下，在搅拌下连续滴加169g 30重量％过乙酸的乙酸乙酯溶液3小时以进行环氧化反应。反应液体回落到室温后，将其从烧瓶中取出，加入大量的甲醇中进行分离、过滤、水洗和干燥，得到环氧当量为520的环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物。
合成实施例2
向配有搅拌器和冷凝器的烧瓶中加入300g苯乙烯-丁二烯-苯乙烯嵌段共聚物(商品名：TR2000，由Japan Synthetic Rubber Co.，Ltd.供应，数均分子量：100000；苯乙烯/丁二烯的共聚比(重量)为40/60)，以及1500g溶解所述共聚物的乙酸乙酯。然后在40℃下，在搅拌下连续滴加169g 15重量％过乙酸的乙酸乙酯溶液3小时以进行环氧化反应。反应液体回落到室温后，将其从烧瓶中取出，加入大量的甲醇中进行分离、过滤、水洗和干燥，得到环氧当量为1000的环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物。
合成实施例3
向配有搅拌器和冷凝器的烧瓶中加入300g苯乙烯-丁二烯-苯乙烯嵌段共聚物(商品名：TR2000，由Japan Synthetic Rubber Co.，Ltd.供应，数均分子量：100000；苯乙烯/丁二烯的共聚比(重量)为40/60)，以及1500g溶解所述共聚物的乙酸乙酯。然后在40℃下，在搅拌下连续滴加169g 5重量％过乙酸的乙酸乙酯溶液3小时以进行环氧化反应。反应液体回落到室温后，将其从烧瓶中取出，加入大量的甲醇中进行分离、过滤、水洗和干燥，得到环氧当量为2000的环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物。
接着如下所述制备粘合剂组合物。
实施例1-18和对比实施例1-5
在室温到60℃范围内，将(A)环氧树脂，(B)酚醛树脂，(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物，硅烷偶联剂，固化促进剂和填料，每一种物质的用量见表1，溶解在甲乙酮中制备溶液。调整溶液的固含量为35重量％，从而得到本发明的粘合剂组合物和对比实施例的粘合剂组合物。表1所示的组分的名称见表2。
对于填料，相对于100重量份总量的(A)环氧树脂，(B)酚醛树脂，(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物和硅烷偶联剂，列出了其配混比例。
而且，在对比实施例3中，用苯乙烯-丁二烯-苯乙烯嵌段共聚物替代(C)环氧苯乙烯-丁二烯-苯乙烯嵌段共聚物。
表1
                                                组分                备注
                                               ％重量 重量份 (A)/(B)官能团的当量比 (C)的比例(重量％) (C)中丁二烯/苯乙烯的重量比
(A)环氧树脂 (B)酚醛树脂 (C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物 苯乙烯-丁二烯-嵌段共聚物 (D)二氨基硅氧烷化合物 硅烷偶联剂 固化促进剂 填料
A-1  A-2   A-3  A-4     B-1 B-2     C-1  C-2  C-3   D-1   D-2   E-1   E-2   E-3
  实施例1   24.2     14.5     56.5   1.7   2.9   0.2     1/0.8   56.5   60/40
  实施例2 20.1     18.7     56.6   1.7   2.9     1/0.8   56.6   60/40
  实施例3  26.5     12.4     56.5   1.7   2.9     1/0.8   56.5   60/40
  实施例4  33.1     15.4     47.1   1.4   3     1/0.8   47.1   60/40
  实施例5 29.2     13.7     52.2   1.6   3.3     1/0.9   52.2   60/40
  实施例6 20.2     18.8  56.6   1.4   3     1/0.8   56.6   60/40
  实施例7 20.8     19.3  58.4   1.5     1/0.8   58.4   60/40
  实施例8  32     14.9  45.6     4.6     2.9     1/0.9   45.6   60/40
  实施例9   23.6     14  54.8     4.5   2.9   0.2     1/0.8   54.8   60/40
  实施例10  27.3     12.8     58.3   1.6     1/0.9   58.3   60/40
  实施例11   24     14.3  55.8     5.7   0.2     1/0.8   55.8   60/40
  实施例12 29.3     13.7     52.1   1.6   3.3     1/0.9   52.1   60/40
  实施例13 28.7     26.7     40     4.6     1/0.8   40   60/40
  实施例14 19.5     9.1     70   1.4     1/0.9   70   60/40
  实施例15 17.2  5.1     70     4.7     3     1/0.8   70   60/40
  实施例16 15.7  9.9     70   1.4     3     1/0.8   70   60/40
  实施例17  26.5     12.4     56.6   1.6   2.9     3     1/0.9   56.6   60/40
  实施例18 15.7  9.9     70   1.4     3     5     1/0.8   70   60/40
对比实施例1  65.8     30   0.9     3   0.3       -   30   60/40
对比实施例2   65.8     30   0.9     3   0.3       -   30   60/40
对比实施例3   28.1     16.8     54.8   0.3     1/0.3    -     -
对比实施例4 20.1     20.4     56.5     3     1/0.9   56.5   60/40
对比实施例5 1.1     0.9     95     3     1/15.8   95   60/40
表2
   组分   符号                             内容
(A)环氧树脂   A-1 四缩水甘油基二苯甲烷型环氧树脂(商品名：Epikote604，Yuka Shell Epoxy K.K.供应)
  A-2 双环型环氧树脂  (商品名：HP-7200，Dainippon Ink& Chemicals，Ins.供应)
  A-3 二苯基型环氧树脂(商品名：Epikote YX4000H，Yuka ShellEpoxy K.K.供应)
  A-4 双环环氧树脂  (商品名：HP-7200，Dainippon Ink &Chemicals，Ins.供应)
(B)酚醛树脂   B-1 线型酚醛树脂(商品名：Shonol CKM2400，ShowaHighpolymer Co.，Ltd.供应)
  B-2 线型酚醛树脂(商品名：Shonol BGR555，ShowaHighpolymer Co.，Ltd.供应)
(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物   C-1                   合成实施例1
  C-2                   合成实施例2
  C-3                   合成实施例3
苯乙烯-丁二烯-苯乙烯嵌段共聚物            苯乙烯-丁二烯-苯乙烯嵌段共聚物(商品名：TR2000，Japan Synthetic Rubber Co.，Ltd.供应)
(D)二氨基硅氧烷化合物   D-1 二氨基硅氧烷(商品名：TSL9306，Toshiba Silicone Co.，Ltd.供应)
  D-2 二氨基硅氧烷(商品名：TSL9886，Toshiba  Silicone Co.，Ltd.供应)
硅烷偶联剂   E-1 环氧基硅烷偶联剂(商品备：SilaAce S510，ChissoCorporation供应)
E-2     环氧基硅烷偶联剂(商品备：SilaAce S530，ChissoCorporation供应)
E-3     氨基硅烷偶联剂(商品备：SilaAce S310，ChissoCorporation供应)
  固化促进剂   咪唑基环氧树脂固化剂(商品名：Curezole 2E4MZ，Shikoku Chemicals Corp.供应)
    填料   无水二氧化硅(商品名：Aerosil R972，Nippon AerosilCo.，Ltd.供应)
然后根据下列参数评估本发明的粘合剂组合物和对比实施例的粘合剂组合物：
1.相容性
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为30微米，在热空气对流干燥器中在130℃下干燥5分钟，在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠，接着在70℃/10小时下进行陈化制备粘合片材。
然后，用显微镜观察每一粘合片材表面上的粘合剂组合物，评估其相容性，结果见表3，其中○表示相容性好和×表示相容性差，例如大理石状的外观表示相容性差。
从表3的评估结果可明显证明使用本发明粘合剂组合物的粘合片材同其所含的组分相容性好。另一方面，对比实施例3-5的粘合片材同粘合剂组合物中的组分相容性差，导致实际应用中产生问题。
2.粘合力
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为30微米，在热空气对流干燥器中在130℃下干燥5分钟，在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠，接着在70℃/10小时下进行陈化以制备用于测试粘合力的粘合片材。
然后剥离掉聚乙烯保护膜的同时，将每一粘合片材热压粘接到厚度为50微米的聚酰亚胺膜(商品名：Upilex 50S，Ube Industries，Ltd.供应)上。然后将每一粘合片材上的聚对苯二甲酸乙二酯膜剥离掉，使粘合层热压粘接到厚度为50微米的聚酰亚胺膜(商品名：Upilex 50S，Ube Industries，Ltd.供应)上，接着在150℃下加热1小时固化粘合层，制备用于测试粘合力的样品。用Shimadzu Corp.供应的Tensilon测试90度剥离的粘合力。
在恒温和恒湿试验后还测试进行相同评估的样品的粘合力，所述试验在恒温和恒湿烘箱中进行，试验条件如下：温度121℃，湿度100％RH，和时间300小时。
与铜箔的粘接
除了以上的聚酰亚胺膜(商品名：Upilex 50S，Ube Industries，Ltd.供应)被厚度为18微米的铜箔(商品名：JTC-A，Japan Energy Corp.供应)替代外，用与上述相同的方式制备并测试评估样品与铜箔的粘接。
而且，在与评估聚酰亚胺膜的粘接相同的条件下，也对样品进行恒温和恒湿试验，其后测试其粘合力。
粘合层与聚酰亚胺膜和铜箔的粘接的评估结果见表3。
从表3的评估结果可明显证明本发明的粘合剂组合物在恒温和恒湿试验后的粘合力为0.7kg/cm或更高，而对比实施例的粘合剂组合物容易从聚酰亚胺膜和铜箔二者上剥离，导致实际应用中产生问题。
3.对回流的耐受性
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为30微米，在热空气对流干燥器中在130℃下干燥5分钟制备粘合片材，在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠。
然后剥离掉聚乙烯保护膜的同时，将每一粘合片材热压粘接到厚度为200微米和2.5cm×2.5cm大小的、具有蚀刻铜部分的玻璃纤维增强环氧树脂板(商品名：CCL-EL170，Mitubishi Gas Chemical Co.，Inc.供应)上。
然后从每一粘合片材中剥离聚对苯二甲酸乙二酯膜，得到0.9cm×0.7cm的玻璃片，在0.1Mpa压力下和140℃下热压粘接3分钟，接着在90℃下加热1小时和还在150℃下加热2小时固化粘合层，从而制备对回流耐受性的评估样品。
在85℃和85％RH条件下将这些评估样品放置在恒温和恒湿的烘箱中48小时，流经温度设定为260℃的IR回流炉，然后观察是否存在剥离和发泡。结果见表3。
每一实施例和对比实施例中制备五个评估样品，表3列出了没有发生剥离和发泡的评估样品数量。从表3的评估结果可明显看出本发明的粘合剂组合物不产生剥离和发泡，而对比实施例中的那些则产生剥离和发泡。
4.热循环试验
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为50微米，在热空气对流干燥器中在130℃下干燥5分钟制备粘合片材，接着在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠。
然后在剥离聚对苯二甲酸乙二酯膜的同时，将每一粘合片材热压粘接到厚度为200微米和2.5cm×2.5cm大小的、具有蚀刻铜部分的玻璃纤维增强的环氧树脂板(商品名：CCL-EL170，Mitubishi Gas Chemical Co.，Inc.供应)上。
然后从每一粘合片材中剥离聚对苯二甲酸乙二酯膜，得到0.9cm×0.7cm的玻璃片，在0.1Mpa压力和140℃下与粘合层热压粘接3分钟，接着在90℃下加热1小时和还在150℃下加热2小时固化粘合层，从而制备对热循环试验的评估样品。
这些评估样品在-65℃到+150℃之间进行温度循环变化试验。然而，在此情况下，在500次循环的条件下进行试验，其中每一循环经历150℃的高温和-65℃的低温的温度历程30分钟。
温度循环试验结束后，观察剥离和发泡。结果见表3。
每一实施例和对比实施例中制备五个评估样品，表3列出了没有发生剥离和发泡的评估样品数量。从表3的评估结果可明显看出本发明的粘合剂组合物不产生剥离和发泡，而对比实施例中的那些则产生剥离和发泡。
5.吸水率
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为60微米，在热空气对流干燥器中在130℃下干燥5分钟制备粘合片材，接着在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠。
接着，按顺序从每一粘合片材中剥离聚乙烯保护膜和聚对苯二甲酸乙二酯膜，在150℃下加热1小时以固化粘合层，制备5cm×5cm用于吸水试验的评估样品。在下列条件下进行吸水试验：使用恒温和恒湿的烘箱：温度121℃，湿度100％RH，和时间24小时。
接着，使用下式计算吸水率，结果见表3。
吸水率＝(吸水后样品重量-吸水前样品重量)/吸水前样品重量×100(％)
从表3的评价结果可明显证明本发明的粘合剂组合物的吸水率低于0.7％，而对比实施例的粘合剂组合物的，吸水率超过1.0％，从而导致实际应用中产生问题。
6.伸长率
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，其干燥厚度为60微米，在热空气对流干燥器中在130℃下干燥5分钟制备粘合片材，接着在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠。
接着，按顺序从每一粘合片材中剥离聚乙烯保护膜和聚对苯二甲酸乙二酯膜，在150℃下加热1小时以固化粘合层，制备1cm×12cm用于伸长率评估的样品。使用Shimadzu Corp.供应的Tensilon进行测定，并根据下式计算伸长率。结果见表3。
伸长率＝(拉伸后样品的长度-拉伸前样品的长度)/拉伸前样品的长度×100(％)
从表3的结果可明显看出，本发明的粘合剂组合物的伸长率超过130％，而对比实施例1，2和4的粘合剂组合物的伸长率低，小于120％。
7.发泡和嵌入
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为30微米，在热空气对流干燥器中在130℃下干燥5分钟，在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠，接着在70℃/10小时下进行陈化以制备粘合片材。
另一方面，将光致抗蚀涂层热压粘接到撳闲园(商品名：Espanex，NipponSteel Chemical Co.，Ltd.供应)上，接着蚀刻并剥离抗蚀涂层以制备具有50微米/50微米导线/导线间距的梯形电路。在剥离聚乙烯保护膜的同时，将上述的每一粘合片材热压粘接到由此制备的电路之一上。接着剥离聚对苯二甲酸乙二酯膜，然后在150℃下加热1小时以固化粘合层。由此制备用于发泡和嵌入性能试验的评估样品。
接着，用显微镜评估发泡状态(判断梯形电路和粘合层之间是否存在发泡)和嵌入状态(判断梯形电路周围是否存在因不完全粘接而产生的孔隙)。结果见表3，其中○表示没有发泡或嵌入问题的那些和×表示同时存在发泡或嵌入问题的那些。
8.电学可靠性
将上述实施例1-18和对比实施例1-5的液体粘合剂组合物各自涂覆到厚度为38微米且进行过防粘处理的聚对苯二甲酸乙二酯膜上，以至其干燥厚度为30微米，在热空气对流干燥器中在130℃下干燥5分钟，在其上用厚度为50微米且进行过防粘处理的聚乙烯保护膜进行层叠，接着在70℃/10小时下进行陈化以制备粘合片材。
另一方面，将光致抗蚀涂层热压粘接到撳闲园(商品名：Espanex，NipponSteel Chemical Co.，Ltd.供应)上，接着蚀刻并剥离抗蚀涂层以制备具有50微米/50微米导线/导线间距的梳形电路。在剥离聚乙烯保护膜的同时，将上述的每一粘合片材热压粘接到由此制备的电路之一上。接着剥离聚对苯二甲酸乙二酯膜，然后在150℃下加热1小时以固化粘合层。由此制备用于电学可靠性评估的样品。
在调节到130℃和85％RH湿度的恒温和恒湿烘箱中，将每一评估样品放置300小时，同时对梳形电路施加5V的直流电。接着，评估梳形电路的状态。结果见表3，其中X表示梳形电路(铜箔部分)中遭受迁移的那些和○表示没有迁移的那些。从表3的结果可明显看出本发明的粘合剂组合物没有迁移。
表3
相容性   与聚酰亚胺膜的粘合力(kg/cm)      与铜箔膜的粘合力(kg/cm) 对回流的耐受性 热循环试验 吸水率(％) 伸长率(％) 发泡 嵌入 电学可靠性
在C.T.和H.试验之前 在C.T.和H.试验之后 在C.T.和H.试验之前 在C.T.和H.试验之后
  实施例1     ○     2.7     0.7     1.8     2.7     5/5     5/5     0.5     150     ○     ○     ○
  实施例2     ○     2.3     0.7     2.4     1.4     5/5     5/5     0.5     140     ○     ○     ○
  实施例3     ○     3.3     1.4     1.8     1.7     5/5     5/5     0.5     210     ○     ○     ○
  实施例4     ○     2.3     1.2     1.8     1     5/5     5/5     0.5     180     ○     ○     ○
  实施例5     ○     3     1.3     1.8     1.7     5/5     5/5     0.5     220     ○     ○     ○
  实施例6     ○     2     0.7     1.6     1     5/5     5/5     0.5     160     ○     ○     ○
  实施例7     ○     1.8     0.7     1.3     1     5/5     5/5     0.7     140     ○     ○     ○
  实施例8     ○     2     1     1.8     1.4     5/5     5/5     0.7     180     ○     ○     ○
  实施例9     ○     2     0.8     1.4     0.8     5/5     5/5     0.5     140     ○     ○     ○
  实施例10     ○     3.3     1.3     1.6     1.2     5/5     5/5     0.5     210     ○     ○     ○
  实施例11     ○     1.8     0.8     1.4     1     5/5     5/5     0.5     180     ○     ○     ○
  实施例12     ○     3     1.3     1.8     1     5/5     5/5     0.5     160     ○     ○     ○
  实施例13     ○     1.4     0.8     1.4     0.8     5/5     5/5     0.5     140     ○     ○     ○
  实施例14     ○     2.7     1.3     1.8     1.3     5/5     5/5     0.7     260     ○     ○     ○
  实施例15     ○     1.8     1.1     1.2     1.1     5/5     5/5     0.5     180     ○     ○     ○
  实施例16     ○     1.6     1     1.2     0.8     5/5     5/5     0.5     140     ○     ○     ○
  实施例17     ○     2     1.1     1.6     1.4     5/5     5/5     0.6     200     ○     ○     ○
  实施例18     ○     1.3     1     1.1     0.8     5/5     5/5     0.6     130     ○     ○     ○
对比实施例1     ○     0.8     0     0.6     0     0/5     0/5     0.5     80     ○     ○     ×
对比实施例2     ○     0.8     0     0.8     0     0/5     0/5     1.0     100     ○     ○     ×
对比实施例3     ×     0.6     0     0.8     0     2/5     0/5     1.2     150     ×     ×     ×
对比实施例4     ×     0.9     0     0.8     0     0/5     2/5     1.0     120     ×     ○     ○
对比实施例5     ×     1.0     0     1.0     0     0/5     2/5     1.3     200     ×     ×     ×
(在上表中，C.T和H.试验是指恒温和恒湿试验)
如上所述，本发明用于半导体器件的粘合剂组合物具有优良的粘合力，在工业上可能提供用于半导体器件的粘合片材，其中所述粘合片材具有优良的耐回流、热循环试验、可加工性以及电学可靠性。而且，利用本发明用于半导体器件的粘合剂组合物，可改进表面安装型半导体器件的可靠性。

Claims (9)

1.一种用于半导体器件的粘合剂组合物，包括(A)环氧树脂，(B)酚醛树脂，(C)环氧化的苯乙烯-丁二烯-苯乙烯嵌段共聚物，和(D)二氨基硅氧烷化合物。
2.一种权利要求1的用于半导体器件的粘合剂组合物，其中以官能团的当量比来表示，所述(A)环氧树脂与所述(B)酚醛树脂之比是1∶0.6-1∶1.4。
3.一种权利要求1的用于半导体器件的粘合剂组合物，其中所术(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的比例占所述粘合剂组合物总固含量的30-80重量％。
4.一种权利要求1的用于半导体器件的粘合剂组合物，其中所述(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物中丁二烯与苯乙烯之重量比为1/99-70/30。
5.一种权利要求1的用于半导体器件的粘合剂组合物，其中所述(C)环氧化苯乙烯-丁二烯-苯乙烯嵌段共聚物的环氧当量为140-6000。
6.一种权利要求1的用于半导体器件的粘合剂组合物，其中所述(D)二氨基硅氧烷化合物是以下通式(1)表示的，在两端均具有氨基的二氨基硅氧烷化合物：
Figure A0210505400021
其中R1是具有1-10个碳原子的亚烷基和n是0-10的整数。
7.一种权利要求1的用于半导体器件的粘合剂组合物，其中所述(D)二氨基硅氧烷化合物占所述粘合剂组合物总固含量的0.3-10重量％。
8.一种用于半导体器件的粘合片材，包括一种载体和一种权利要求1-7任一项所述的粘合剂组合物，所述粘合剂组合物至少在所述载体的一个表面上层叠。
9.一种权利要求8的用于半导体器件的粘合片材，其中所述载体包括绝缘膜或防粘膜。
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