CN1395604A - 半导体用粘接膜、带有半导体用粘接膜的导线框及使用了该导线框的半导体装置 - Google Patents

半导体用粘接膜、带有半导体用粘接膜的导线框及使用了该导线框的半导体装置 Download PDF

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Publication number
CN1395604A
CN1395604A CN01803793A CN01803793A CN1395604A CN 1395604 A CN1395604 A CN 1395604A CN 01803793 A CN01803793 A CN 01803793A CN 01803793 A CN01803793 A CN 01803793A CN 1395604 A CN1395604 A CN 1395604A
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Prior art keywords
semiconductor
adhesive film
film
lead frame
resin
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Granted
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CN01803793A
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CN1238458C (zh
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田边义行
松浦秀一
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Showa Denko Materials Co ltd
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Hitachi Chemical Co Ltd
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    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J179/00—Adhesives based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09J161/00 - C09J177/00
    • C09J179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09J179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49503—Lead-frames or other flat leads characterised by the die pad
    • H01L23/49513—Lead-frames or other flat leads characterised by the die pad having bonding material between chip and die pad
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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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    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/02—Non-macromolecular additives
    • C09J11/06—Non-macromolecular additives organic
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    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
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    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/35—Heat-activated
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    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49503—Lead-frames or other flat leads characterised by the die pad
    • H01L23/4951—Chip-on-leads or leads-on-chip techniques, i.e. inner lead fingers being used as die pad
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    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
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    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
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Abstract

本发明涉及半导体用粘接膜、带有半导体用粘接膜的导线框及由该带有半导体用粘接膜的导线框和半导体元件粘接而成的半导体装置。所述粘接膜具备在支撑膜的两面设有粘接剂层的三层结构，其中的粘接剂层含有(A)玻璃化温度为130～300℃、吸水率在3重量％以下、挤出长度在2mm以下的耐热的热塑性树脂，(B)环氧树脂和(C)作为环氧树脂硬化剂的三苯酚类化合物。

Description

半导体用粘接膜、带有半导体用粘接膜的 导线框及使用了该导线框的半导体装置
技术领域
本发明涉及半导体用粘接膜、带有半导体用粘接膜的导线框以及使用了该导线框的半导体装置。
背景技术
近年来，随着高性能大容量化，半导体芯片逐渐大型化，但因为印刷电路设计上的制约以及电器小型化的要求，安装半导体芯片的部件要求具有较小的外形。针对此倾向，对半导体芯片的高密度化和高密度组装已经提出了若干新型实际安装方案。其中，利用对记忆元件所提议的芯片上与导线粘接的LOC结构，可使芯片内配线和有线搭接合理化，由缩短配线带来信号高速化及包装体积的小型化。
在这种新型的实用包装中，由于粘接界面与半导体芯片和导线框的材质不同，其粘接的可靠性对半导体部件的可靠性产生非常大的影响。芯片部件组装作业时耐受工艺温度的可靠性、粘接作业性是很重要的方面，此外，避免由于吸湿和湿热时的粘接可靠性所引起的基板组装时焊料回流引发芯片部件出现裂缝，也是非常重要的。
以往，上述粘接使用的是糊状的粘接剂或是在耐热性材质上涂布粘接剂。作为方法之一提出了使用聚酰亚胺树脂制成的热溶性粘接膜的方案(参照日本专利公开公报平5-105850号、日本专利公开公报平5-112760号、日本专利公开公报平5-112761号)。但是，热溶性粘接剂中的粘接剂树脂的Tg较高，粘接时需要的温度就变得很高，这可能给半导体芯片、特别是铜制的导线框等被覆材料带来热损伤。并且，若为了赋予低温粘接性而降低Tg，则耐热可靠性变差，粘接剂树脂固有的弹性率变高，不能缓解基板组装时焊料回流的受热过程中在芯片和导线框之间产生的热应力，导致芯片部件出现裂缝。
发明的揭示
本发明提供了半导体装置中可低温粘接的半导体用粘接膜。
另外，本发明还提供了将此半导体用粘接膜打穿后贴在导线框的规定位置而形成的带有半导体用粘接膜的导线框。
本发明进一步提供了借助此半导体用粘接膜将导线框和半导体元件粘接起来的具有优良可靠性的半导体装置。
本发明促进了兼具低温粘接性和半导体装置的耐回流开裂性的半导体用粘接膜的开发，结果发现在粘接剂层中使用含有具备特定特性的耐热的热塑性树脂、环氧树脂及作为环氧树脂硬化剂的三苯酚类化合物的粘接剂可解决前述问题，从而完成了本发明。
即，本发明涉及在支撑膜的两面设有粘接剂层的三层结构的半导体用粘接膜(本发明1的粘接膜)，其中的粘接剂层含有(A)玻璃化温度为130～300℃、吸水率在3重量％以下、挤出长度在2mm以下的耐热的热塑性树脂，(B)环氧树脂和(C)作为环氧树脂硬化剂的三苯酚类化合物。
本发明还涉及在支撑膜的两面设有粘接剂层的三层结构的半导体用粘接膜上(本发明2的粘接膜)，其中的粘接剂层含有(A)玻璃化温度为130～300℃的耐热的热塑性树脂，(B)环氧树脂和(C)作为环氧树脂硬化剂的三苯酚类化合物；前述三层结构的粘接膜的吸水率在3重量％以下、挤出长度在2mm以下。
本发明还涉及导线框上贴有上述半导体用粘接膜的带有半导体用粘接膜的导线框。
本发明进一步涉及用上述半导体用粘接膜将带有半导体用粘接膜的导线框与半导体元件粘接起来的半导体装置。
附图的简单说明
图1为本发明的半导体用粘接膜的截面图。
图2为使用本发明的半导体用粘接膜制得的半导体装置的截面图。
实施发明的最佳方式
本发明1的粘接膜中使用的耐热的热塑性树脂(A)为玻璃化温度在130～300℃的范围内、吸水率在3重量％以下、挤出长度在2mm以下的耐热性树脂，因而最好使用聚酰亚胺树脂和聚酰胺树脂。聚酰亚胺树脂指的是聚酰亚胺树脂、聚酰胺酰亚胺树脂、聚酯酰亚胺树脂、聚醚酰亚胺树脂等含有亚氨基的树脂。
如果玻璃化温度超过此范围，则吸水率超过3重量％，挤出长度超过2mm，这样使用本发明的半导体用粘接膜制得的半导体装置的耐回流开裂性会下降。
本发明使用的耐热的热塑性树脂的玻璃化温度最好在180～250℃的范围内。吸水率较好是在2.5重量％以下，更好的是在2.0重量％以下。挤出长度较好的是在1mm以下，更好的是在0.55mm以下。
这里，将耐热的热塑性树脂膜在130℃干燥1小时，测定重量后，在25℃的蒸馏水中浸泡24小时，再次测定重量，通过公式{(浸泡后的重量-浸泡前的重量)/浸泡前的重量}×100％可求出耐热的热塑性树脂的吸水率。将耐热的热塑性树脂制成的19mm×50mm、厚25μm的膜在温度为350℃、压力为3MPa的条件下加热施压1分钟，在长边方向的中央部分测定此时从膜原来的长边沿直角方向挤出的树脂长度，即耐热的热塑性树脂的挤出长度。
本发明2的粘接膜所使用的耐热的热塑性树脂(A)基于与上述本发明1相同的理由，其玻璃化温度也应该为130～300℃。可使用的耐热的热塑性树脂(A)的具体实施例及较好的实施例也与本发明1所述相同。本发明2的粘接膜规定并不是耐热的热塑性树脂本身的吸水率和挤出长度，而是在支撑膜的两面设有粘接层的三层结构的半导体用粘接膜的吸水率在3重量％以下、挤出长度在2mm以下。吸水率和挤出长度的更佳范围也与本发明1相同。
本发明2的粘接膜的吸水率的测定除了用三层结构的粘接膜代替耐热的热塑性树脂(A)膜之外，其他都与本发明1所述方法相同。另外，本发明2的粘接膜的挤出长度的测定也是如此，除了用三层结构的粘接膜替代耐热的热塑性树脂(A)膜(即，对粘接膜的厚度无限制)，切取与上述相同大小(19mm×50mm)的膜片之外，其他都与本发明1所述方法相同。
本发明的半导体用粘接膜兼备了上述发明1和发明2的特征。
以下，对本发明1的粘接膜、本发明2的粘接膜及使用了这两种粘接膜的的带有半导体用粘接膜的导线框与半导体装置进行说明。
本发明的粘接膜中所含的环氧树脂只要是分子中至少含有2个环氧基的环氧树脂即可，对其无特别限定。如下面(1)～(3)表示的化合物等。
Figure A0180379300071
式中，Z1表示2价有机基团，Z2表示4价有机基团，Z3表示3价有机基团。
这些环氧树脂的具体例子包括双酚A二缩水甘油醚、双酚F二缩水甘油醚、双酚AD二缩水甘油醚、双酚S二缩水甘油醚、2，6-二甲苯酚二缩水甘油醚、水合双酚A二缩水甘油醚、1，4-环己烷二甲醇二缩水甘油醚、羟基二苯酚二缩水甘油醚、环氧乙烷加成双酚二缩水甘油醚、环氧丙烷加成双酚A二缩水甘油醚、聚乙二醇二缩水甘油醚、聚丙二醇二缩水甘油醚、新戊二醇二缩水甘油醚、1，6-己二醇二缩水甘油醚、酚醛清漆树脂的缩水甘油醚、甲酚清漆树脂的缩水甘油醚、萘树脂的缩水甘油醚、三官能的缩水甘油醚、四官能的缩水甘油醚、二聚环戊二烯酚醛树脂的缩水甘油醚、二聚酸的缩水甘油酯、三官能的缩水甘油胺、四官能的缩水甘油胺、萘树脂的缩水甘油胺、多硫化合物改性环氧树脂、聚丁二烯改性环氧树脂等。其中可含有一官能的环氧体。
环氧树脂的环氧当量较好为50～600，更好为150～500。
本发明的粘接剂层中包含的环氧树脂硬化剂为分子中含有3个羟苯基的三苯酚类化合物。该三苯酚类化合物的较好例子如以下通式(a)所示。式(a)中，R1～R10分别独立地表示氢原子、碳原子数1～10的烷基、碳原子数5～10的环烷基、苯基、羟基。R5表示氢原子、碳原子数1～10的烷基、碳原子数5～10的环烷基或苯基，更好的是表示氢原子或碳原子数1～10的烷基。D表示4价有机基团。4价有机基团D的具体例子如下所示。
Figure A0180379300081
通式(a)中的≡D-R5的具体例子如下所示。
三苯酚类化合物具体包括4，4’，4”-次甲基三苯酚、4，4’-[1-[4-1-(4-羟基苯基)-1-甲基乙基]苯基]次乙基]双酚、4，4’，4”-次乙基三[2-甲基苯酚]、4，4’，4”-次乙基三苯酚、4，4’-[(2-羟基苯基)亚甲基]双[2-甲基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2-甲基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2，3-二甲基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2，6-二甲基苯酚]、4，4’-[(3-羟基苯基)亚甲基]双[2，3-二甲基苯酚]、2，2’-[(2-羟基苯基)亚甲基]双[3，5-二甲基苯酚]、2，2’-[(4-羟基苯基)亚甲基]双[3，5-二甲基苯酚]、4，4’-[(2-羟基苯基)亚甲基]双[2，3，5-三甲基苯酚]、4，4’-[(2-羟基苯基)亚甲基]双[2，3，6-三甲基苯酚]、4，4’-[(3-羟基苯基)亚甲基]双[2，3，6-三甲基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2，3，6-三甲基苯酚]、4，4’-[(2-羟基苯基)亚甲基]双[2-环己基-5-甲基苯酚]、4，4’-[(3-羟基苯基)亚甲基]双[2-环己基-5-甲基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2-环己基-5-甲基苯酚]、4，4’-[(3，4-二羟基苯基)亚甲基]双[2-甲基苯酚]、4，4’-[(3，4-二羟基苯基)亚甲基]双[2，6-二甲基苯酚]、4，4’-[(3，4-二羟基苯基)亚甲基]双[2，3，6-三甲基苯酚]、4-[双(3-环己基-4-羟基-6-甲基苯基)甲基]-1，2-苯二醇、4，4’-[(2-羟基苯基)亚甲基]双[3-甲基苯酚]、1，3，3-三(4-羟基苯基)丁烷、4，4’-[(2-羟基苯基)亚甲基]双[2-异丙基苯酚]、4，4’-[(3-羟基苯基)亚甲基]双[2-异丙基苯酚]、4，4’-[(4-羟基苯基)亚甲基]双[2-异丙基苯酚]、2，2’-[(3-羟基苯基)亚甲基]双[3，5，6-三甲基苯酚]、2，2’-[(4-羟基苯基)亚甲基]双[3，5，6-三甲基苯酚]、4，4’-[(2-羟基苯基)亚甲基]双[2-环己基苯酚]、4，4’-[(3-羟基苯基)亚甲基]双[2-环己基苯酚]、4，4’-[1-[4-[1-(4-羟基-3，5-二甲基苯基)-1-甲基乙基]苯基]次乙基]双[2，6-二甲基苯酚]、4，4’，4”-次甲基三[2-环己基-5-甲基苯酚]、4，4’-[1-4-[1-(3-环己基-4-羟基苯基)-1-甲基乙基]苯基]次乙基]双[2-环己基苯酚]、2，2’-[(3，4-二羟基苯基)亚甲基]双[3，5-二甲基苯酚]、4，4’-[(3，4-二羟基苯基)亚甲基]双[2-异丙基苯酚]、2，2’-[(3，4-二羟基苯基)亚甲基]双[3，5，6-三甲基苯酚]、4，4’-[(3，4-二羟基苯基)亚甲基]双[2-环己基苯酚]、α，α’，α”-三(4-羟基苯基)-1，3，5-三异丙基苯等。
本发明的粘接膜中使用的粘接剂中，对应于100重量份的耐热的热塑性树脂，环氧树脂的用量较好为1～100重量份，更好为2～50重量份；前述环氧树脂硬化剂的用量较好为0.02～120重量份，更好为0.1～80重量份，最好为1～20重量份。
如果环氧树脂的用量超过100重量份、环氧树脂硬化剂的用量超过120重量份，则膜的成形性变差。如果环氧树脂的用量不足1重量份且环氧树脂硬化剂的用量不足0.02重量份，则低温下的粘接性变差，导致粘接不佳。
本发明的粘接膜中使用的粘接剂，可根据需要使用硬化促进剂，对为使环氧树脂硬化而使用的硬化促进剂没有特别的限制。可使用咪唑类、二氰基二酰胺衍生物、二羧酸二酰肼、三苯基膦、四苯基鏻硼酸四苯酯、2-乙基4-甲基咪唑硼酸四苯酯、1，8-二氮杂环(5，4，0)十一碳烯-7-硼酸四苯酯等。这些硬化促进剂可单独使用，也可2种以上并用。从保存稳定性出发，所用硬化催化剂的添加量对应于100重量份环氧树脂，通常在50重量份以下，例如，0.01～50重量份，更好的是在20重量份以下。
为了提高与支撑膜的粘接性，还可在本发明的粘接膜所用的粘接剂中添加偶合剂。例如，γ-(2-氨基乙基)氨基丙基三甲氧基硅烷、γ-(2-氨基乙基)氨基丙基甲基二甲氧基硅烷、氨基硅烷、γ-甲基丙烯酰氧基丙基三甲氧基硅烷、γ-环氧丙氧基丙基三甲氧基硅烷、甲基三甲氧基硅烷、甲基三乙氧基硅烷、乙烯基三乙酰氧基硅烷、六甲基二硅氮烷、γ-苯胺基丙基三甲氧基硅烷、乙烯基三甲氧基硅烷等硅烷偶合剂，三异硬脂酰基钛酸异丙酯、三辛酰基钛酸异丙酯、三月桂基苯磺酰基钛酸异丙酯、三(焦磷酸二辛酯)钛酸异丙酯等碳酸酯类偶合剂，乙酰烷氧基铝二异丙酯等铝系偶合剂等。
从耐热性、与导线框的粘接性考虑，偶合剂的添加量对应于100重量份耐热的热塑性树脂一般为0.5～20重量份，更好为2～10重量份。
本发明所用的支撑膜最好是聚酰亚胺、聚酰胺、聚砜、聚苯硫、聚醚醚酮、聚丙烯酸酯、聚碳酸酯等绝缘性耐热性树脂膜。对支撑膜的厚度无特别限定，通常为5～20μm，更好为20～75μm。
支撑膜的玻璃化温度最好比本发明所用粘接剂的玻璃化温度高，一般在200℃以上，更好的是在250℃以上。支撑膜的吸水率一般在3重量％以下，更好的是在2重量％以下。
本发明所用的支撑膜最好是具备玻璃化温度在250℃以上、吸水率在2重量％以下、热膨胀系数在3×10-5/℃以下的绝缘性耐热性树脂膜，考虑以上各点，聚酰亚胺膜最令人满意。
支撑膜最好经表面处理后再使用。这是为了提高支撑膜和粘接剂层的粘接力，防止支撑膜与粘接剂层剥离。
支撑膜的表面处理方法包括碱处理法、硅烷偶合剂处理法等化学处理的方法，砂磨处理等物理处理方法，以及等离子处理和日冕处理等。最好根据粘接剂的种类采用最适的处理方法。对于本发明中支撑膜的表面处理，化学处理或等离子处理特别适用。
对在支撑膜上形成粘接剂层的方法没有特别的限定，通常是将用于形成粘接剂层的耐热的热塑性树脂、环氧树脂及环氧树脂硬化剂溶于有机溶媒中，制成粘接剂漆。这里使用的有机溶媒只要能够将上述材料溶解并混合均匀即可，对其无特别限定，可使用二甲基甲酰胺、二甲基乙酰胺、N-甲基-2-吡咯烷酮、二甲亚砜、二乙二醇二甲醚、甲苯、苯、二甲苯、甲基乙基甲酮、四氢呋喃、二噁烷等。
将以上得到的粘接剂漆涂在支撑膜上后，加热处理除去溶剂或酰亚胺化。将上述方法重复2次，制得三层结构的粘接膜。
为除去溶剂而对涂布了粘接剂漆的支撑膜进行加热处理时的处理温度只要能够除去溶剂即可。
对涂布方法没有特别的限定，可采用滚筒涂布法、翻转滚筒涂布法、凹版印刷涂布法，反涂法、点涂法等。此外，也可将支撑膜浸入粘接剂漆中进行涂布，但厚度控制较难。
支撑膜上形成的各粘接剂层的厚度一般为1～75μm，较好为10～30μm。粘接剂层的厚度如果不足1μm，则粘接性和生产性变差，如果超过75μm，则成本提高。
以上制得的粘接膜的结构如图1所示。这种膜可作为半导体用粘接剂使用。图1中，1为支撑膜，2为粘接剂层。
使用本发明的粘接膜，可以良好的操作性和原料利用率简便地制得可靠性优良的带有粘接膜的导线框。例如，将本发明的粘接膜剪切成指定大小的膜片，然后使膜片与导线框粘接的方法。只要能够准确地剪切成指定形状，可采用任何方法来对粘接膜进行剪切，但考虑到操作性，最好采用冲孔金属模具来剪切膜片，将切成的冲孔膜片粘接在导线框上即可。此时的粘接温度通常为150～300℃，最好为200～250℃。粘接温度如果低于150℃，则不能获得足够的粘接力，如果超过300℃，则可能会导致粘接剂层的热劣化以及导线框的氧化。粘接压力通常为0.1～20MPa，最好为0.3～10MPa。粘接压力如果低于0.1MPa，则粘接力可能不足，如果超过20MPa，则粘接剂会挤出规定位置，尺寸精度可能会变差。加压时间只要以在上述粘接温度、粘接压力下能够完成粘接所需时间即可，但考虑到操作性，一般为0.3～60秒，更好为0.5～10秒。
此外，使用本发明的粘接膜，可以良好的操作性和原料利用率制得可靠性优良的半导体装置。
本发明的粘接膜可以替代以往使用了银糊的部件中的银糊或是用于使用多个芯片的多元芯片部件、COL(Chip On Lead)构造的部件，特别适用于LOC(Lead On Chip)构造的半导体装置。由于能够低温粘接，所以不适用于LOC构造中的以往常用的TSOP(Thin Small Outline Package)，还适用于QFP(QuadFlatpack Package)构造、层叠构造的半导体装置。
例如，使用以上制得的带有粘接膜的导线框，在未粘接导线框但已经使半导体芯片与粘接剂层的一面粘接后，进行粘接膜的硬化处理，然后用金属丝等使导线框和半导体芯片等粘接，再用环氧树脂等成形材料进行转移密封，就制得了LOC结构的半导体装置。
半导体芯片的粘接温度通常为150～300℃，更好为200～250℃。粘接温度如果不足150℃，则不能获得足够的粘接力，如果超过300℃，则会出现粘接剂层热劣化和导线框氧化等问题。粘接压力一般为0.1～20MPa，更好为0.3～10MPa。粘接压力如果不足0.1MPa，则不能获得足够的粘接力，如果超过20MPa，则粘接剂可能会被挤压出规定位置而导致尺寸精度变差，从而破坏半导体芯片。
加压时间只要是在上述粘接温度、粘接压力下可完成粘接的时间即可，考虑到操作性，一般为0.3～60秒，更好为0.5～10秒。
硬化处理的温度通常为150～200℃，最好为170～180℃。硬化处理温度如果不足150℃，则硬化不够充分，如果超过200℃，则可能出现导线框氧化。硬化时间通常为15～75分钟，最好为30～60分钟。硬化时间如果不足15分钟，则硬化不够充分，如果超过75分钟，则操作性差。粘接膜的硬化处理还可包括用环氧树脂等成形材料进行转移成形密封后的密封材料硬化步骤。
以下，通过实施例对本发明进行说明，但本发明并不仅限于以下实施例。
实施例1～4、比较例1
使用以下聚酰胺酰亚胺A～C作为耐热的热塑性树脂，按照表2～3的配比，调制得No.1～5的漆(No.1～4：分别为本发明的实施例1～4、No.5为比较例1)。
聚酰胺酰亚胺A、B及C分别由以下方法合成。
聚酰胺酰亚胺A的合成
在氮氛围气中，在容量为5升的装配有温度计、搅拌机、氮气导入管及分馏塔的四口烧瓶中加入2，2-双[4-(4-氨基苯氧基)苯基]丙烷210g(0.5摩尔)，使其溶于N-甲基-2-吡咯烷酮1200g中。将此溶液冷却至-10℃，在此温度下加入偏苯三酰氯105.3g(0.5摩尔)使温度不超过-5℃。待偏苯三酰氯溶解后，加入三乙胺76g使温度不超过5℃。室温下连续搅拌1小时后，于180℃反应9小时，完成酰亚胺化。将所得反应液投入甲醇中，使聚合物分离。干燥后，使其溶于二甲基甲酰胺，投入甲醇中使聚合物再次分离。接着，减压干燥并精制，得到聚酰胺酰亚胺A的粉末。将得到的聚酰胺酰亚胺A粉末60g溶于200g的N-甲基-2-吡咯烷酮中，制得粘接剂漆。将此漆铺在玻璃板上，厚度为90μm，100℃干燥10分钟后，从玻璃板上剥离，再用铁框固定，分别在200℃和300℃干燥10分钟，得到厚度为25μm的粘接剂膜。制得的膜的玻璃化温度为230℃、吸水率为1.8重量％、挤出长度为0.2mm。
聚酰胺酰亚胺B的合成
在氮氛围气中，在容量为5升的装配有温度计、搅拌机、氮气导入管及分馏塔的四口烧瓶中加入2，2-双[4-(4-氨基苯氧基)苯基]丙烷143.5g(0.35摩尔)和1，3-双(氨基丙基)四甲基二硅氧烷37.2g(0.15摩尔)，使它们溶于N-甲基-2-吡咯烷酮1200g中。将此溶液冷却至-10℃，在此温度下加入偏苯三酰氯105.3g(0.5摩尔)使温度不超过-5℃。待偏苯三酰氯溶解后，加入三乙胺76g使温度不超过5℃。室温下连续搅拌1小时后，于180℃反应9小时，完成酰亚胺化。将所得反应液投入甲醇中，使聚合物分离。干燥后，使其溶于二甲基甲酰胺，投入甲醇中使聚合物再次分离。接着，减压干燥并精制，得到聚酰胺酰亚胺B的粉末。将得到的聚酰胺酰亚胺B粉末60g溶于200g的N-甲基-2-吡咯烷酮中，制得粘接剂漆。将此漆铺在玻璃板上，厚度为90μm，100℃干燥10分钟后，从玻璃板上剥离，再用铁框固定，分别在200℃和300℃干燥10分钟，得到厚度为25μm的粘接剂膜。制得的膜的玻璃化温度为190℃、吸水率为1.5重量％、挤出长度为0.4mm。
聚酰胺酰亚胺C的合成
在氮氛围气中，在容量为5升的装配有温度计、搅拌机、氮气导入管及分馏塔的四口烧瓶中加入2，2-双[4-(4-氨基苯氧基)苯基]丙烷61.5g(0.15摩尔)和1，3-双(氨基丙基)四甲基二硅氧烷86.8g(0.35摩尔)，使它们溶于N-甲基-2-吡咯烷酮1200g中。将此溶液冷却至-10℃，在此温度下加入偏苯三酰氯105.3g(0.5摩尔)使温度不超过-5℃。待偏苯三酰氯溶解后，加入三乙胺76g使温度不超过5℃。室温下连续搅拌1小时后，于180℃反应9小时，完成酰亚胺化。将所得反应液投入甲醇中，使聚合物分离。干燥后，使其溶于二甲基甲酰胺，投入甲醇中使聚合物再次分离。接着，减压干燥并精制，得到聚酰胺酰亚胺C的粉末。将得到的聚酰胺酰亚胺C粉末60g溶于200g的N-甲基-2-吡咯烷酮中，制得粘接剂漆。将此漆铺在玻璃板上，厚度为90μm，100℃干燥10分钟后，从玻璃板上剥离，再用铁框固定，分别在200℃和300℃干燥10分钟，得到厚度为25μm的粘接剂膜。制得的膜的玻璃化温度为100℃、吸水率为1.0重量％、挤出长度为3.5mm。
                         表1
耐热的热塑性树脂 玻璃化温度(℃)     吸水率(重量％)   挤出长度(mm)
  聚酰胺酰亚胺A     230      1.8      0.2
  聚酰胺酰亚胺B     190      1.5      0.4
  聚酰胺酰亚胺C     100      1.0      3.5
表2～3中的各种符号的含义如下所述。
YDCN-702：东部化成(株)制，甲酚清漆型环氧树脂(环氧当量220)，
ESCN-195：住友化学工业(株)，甲酚清漆型环氧树脂(环氧当量200)，
N865-E：大日本油墨(株)制，双酚清漆型环氧树脂(环氧当量208)，
BEO-60E：新日本理化学(株)制，环氧乙烷加成双酚型环氧树脂(环氧当量373)，
DEM-100：新日本理化学(株)制，环己烷二甲醇型环氧树脂(环氧当量155)，
TrisP-TC：本州化学(株)制，三苯酚清漆(OH当量160)，化学名：α，α′，α″-三(4-羟基苯基)-1，3，5-三异丙基苯，式(a1)，
TrisP-PA：本州化学(株)制，三苯酚清漆(OH当量141)，化学名：4，4’-[1-[4-[1-(4-羟基苯基)-1-甲基乙基]苯基]次乙基]双酚，式(a2)，
TrisP-PHBA：本州化学(株)制，三苯酚清漆(OH当量97)，化学名4，4′，4”-次甲基三苯酚，式(a3)，
TrisP-HAP：本州化学(株)制，三苯酚清漆(OH当量102)，化学名4，4′，4”-次乙基三苯酚，式(a4)。DMAc：二甲基乙酰胺DMF：二甲基甲酰胺NMP：N-甲基-2-吡咯烷酮
                        表2配比表
    成分                         清漆编号
    No.1      No.2     No.3     No.4
耐热的热塑性树脂重量份     A100      B100     A100     B100
    环氧树脂重量份   YDCN-70210    ESCN19520    N-86525   BEO-60E20
  环氧树脂硬化剂重量份   TrisP-TC7.3   TrisP-PA14.1  TrisP-TC7.3   TrisP-HAP5.5
    溶剂重量份     DMAc500     NMP350     DMF450     DMAc500
     表3配比表
    成分     清漆编号
     No.5
耐热的热塑性树脂重量份     C100
    环氧树脂重量份    YDCN-70210
  环氧树脂硬化剂重量份     TrisP-TC7.3
    溶剂重量份     DMAc500
将这些漆涂布在厚度为50μm的经过表面化学处理的聚酰亚胺膜(宇部兴产(株)制，商品名：ュ一ピレッスS)的各面，厚度为100μm。各面分别在100℃和200℃干燥10分钟后，得到两面具有25μm厚的粘接剂层的图1所示半导体用粘接膜(实施例1～4分别使用清漆编号No.1～4的漆，比较例1使用清漆编号No.5的漆)。
对实施例1～4及比较例1的粘接膜的膜成形性、粘接性、耐回流开裂性进行评估，评估结果见表4。
<膜成形性评估法>
确认在上述条件下制得的粘接膜的粘接剂层是否发粘，没有发粘的判定为良好，出现发粘现象的则为不良。
<低温粘接性评估法>
用冲孔金属模具将粘接膜打成薄长方形，以0.2mm的间隔贴在厚度为0.15mm的铜合金制导线框上，形成宽幅0.2mm的内导线。然后，在温度250℃、压力3MPa的条件下加压3秒，制得带有粘接膜的导线框。使此带有粘接膜的导线框从2m的高度落下，观察落到地面时有无粘接膜片脱落。无粘接膜片脱落的判定为良好，有粘接膜片脱落的为不良。
<耐回流开裂性评价法>
在温度250℃、压力3MPa的条件下，将半导体元件压在进行粘接性评估时制得的带有粘接膜的导线框的粘接剂层表面，历时3秒种。然后，用金属丝连接导线框与半导体元件，再用乙烯类环氧树脂成形材料(日立化成工业(株)制，商品名：CEL-9200)通过转移出现密封，在175℃下硬化6小时，制成图2所示半导体装置。图2中，3为粘接膜，4为半导体元件，5为导线框，6为密封材料，7为粘接导线，8为旁路。
所得半导体装置在温度85℃、湿度85％RH的高温高湿条件下放置168小时后，通入设定了温度的红外回流炉中，使该半导体装置的表面最高温度保持在240℃，历时20秒，然后，室温放置自然冷却，将上述操作重复2次，观察是否出现裂缝。没有裂缝的判定为良好，有裂缝的为不良。
             表4粘接膜的特性评估结果
    特性 实施例1 实施例2 实施例3 实施例4 实施例5
  膜成形性   良好   良好   良好   良好   良好
  低温粘接性   良好   良好   良好   良好   良好
耐回流开裂性   良好   良好   良好   良好   良好
表5三层结构的粘接膜的吸水率及挤出长度
(支撑膜：100μm、粘接剂层：各25μm)
粘接膜的吸水率(重量％)   粘接膜的挤出长度(mm)
实施例1      1.8      0.3
实施例2      1.7      0.4
实施例3      1.8      0.3
实施例4      1.7      0.5
比较例1      1.4      3.8
实施例1～4均满足本发明规定的项目，膜的形成性、低温粘接性、耐回流开裂性均良好。
比较例1中，耐热的热塑性树脂的Tg及挤出长度、粘接膜的挤出长度均超出了本发明规定的值，且耐回流开裂性较差。
产业上利用的可能性
本发明的半导体用粘接膜可在低温粘接，特别适用于使用了铜制导线框的带有粘接膜的导线框的制造。此外，由该带有粘接膜的导线框制得的半导体装置具有优良的耐回流开裂性和较高的可靠性。

Claims (13)

1.半导体用粘接膜，所述粘接膜具备在支撑膜的两面设有粘接剂层的三层结构，其中的粘接剂层含有(A)玻璃化温度为130～300℃、吸水率在3重量％以下、挤出长度在2mm以下的耐热的热塑性树脂，(B)环氧树脂和(C)作为环氧树脂硬化剂的三苯酚类化合物。
2.半导体用粘接膜，所述粘接膜具备在支撑膜的两面设有粘接剂层的三层结构，其中的粘接剂层含有(A)玻璃化温度为130～300℃的耐热的热塑性树脂，(B)环氧树脂和(C)作为环氧树脂硬化剂的三苯酚类化合物，前述三层结构的粘接膜的吸水率在3重量％以下、挤出长度在2mm以下。
3.如权利要求1所述的半导体用粘接膜，其中的粘接剂层含有100重量份耐热的热塑性树脂(A)、1～100重量份环氧树脂(B)及0.02～120重量份环氧脂硬化剂(C)。
4.如权利要求1所述的半导体用粘接膜，其中，耐热的热塑性树脂(A)为聚酰亚胺树脂、聚酰胺酰亚胺树脂、聚酯酰亚胺树脂、聚醚酰亚胺树脂或聚酰胺树脂。
5.如权利要求1所述的半导体用粘接膜，其中，环氧树脂硬化剂(C)为以下通式(a)表示的三苯酚化合物，式中，R1～R10分别独立地表示氢原子、碳原子数1～10的烷基、碳原子数5～10的环烷基、苯基或羟基，D表示4价有机基团。
6.如权利要求5所述的半导体用粘接膜，其中，通式(a)中的D为
7.如权利要求6所述的半导体用粘接膜，其中，通式(a)中的R5为氢原子或碳原子数1～10的烷基。
8.如权利要求7所述的半导体用粘接膜，其中，通式(a)中的≡D-R5为
Figure A0180379300032
9.如权利要求1所述的半导体用粘接膜，其中，支撑膜为选自聚酰亚胺、聚酰胺、聚砜、聚苯硫、聚醚醚酮、聚丙烯酸酯及聚碳酸酯的绝缘性耐热性树脂膜。
10.带有半导体用粘接膜的导线框，其中，导线框上贴有权利要求1所述的半导体用粘接膜。
11.带有半导体用粘接膜的导线框，其中，导线框上贴有权利要求2所述的半导体用粘接膜。
12.半导体装置，所述装置通过权利要求1所述的半导体用粘接膜粘接导线框和半导体元件而制得。
13.半导体装置，所述装置通过权利要求2所述的半导体用粘接膜粘接导线框和半导体元件而制得。
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