CN1193081C - 具有烯丙基或乙烯基的环氧树脂芯片固定粘合剂 - Google Patents

具有烯丙基或乙烯基的环氧树脂芯片固定粘合剂 Download PDF

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CN1193081C
CN1193081C CNB011225637A CN01122563A CN1193081C CN 1193081 C CN1193081 C CN 1193081C CN B011225637 A CNB011225637 A CN B011225637A CN 01122563 A CN01122563 A CN 01122563A CN 1193081 C CN1193081 C CN 1193081C
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M·R·博诺
Y·K·辛
G·霍尔恩
M·索布查克
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Abstract

具有增强粘接强度的粘合剂组合物，它包含基础树脂和带烯丙基或乙烯基官能度的环氧树脂。该组合物可用于微电子行业。

Description

具有烯丙基或乙烯基的环氧树脂芯片固定粘合剂
技术领域
本发明涉及由于带烯丙基或乙烯基不饱和度的环氧树脂的存在而具有改进粘合力的芯片固定(die attach)粘合剂。
背景技术
在半导体封装的加工和组装方面，粘合剂组合物具有非常广泛的用途，例如将集成电路芯片粘接到引线框架或其它基板上，将电路组件粘接或组装到印刷线路板上。对于这些应用的主要的要求是快速固化和高粘结强度，习惯上都是采用环氧树脂来实现的。但是环氧树脂具有脆性，于是我们评估和采用了别的树脂材料使芯片固定粘合剂具有柔性、疏水性以及其它性质。然而替代树脂材料反过来又不总是具备环氧树脂提供的强大粘合力。因此，就需要研制出一种芯片固定粘合剂，它具有综合平衡的性能以满足对在半导体封装生产中所用粘合剂的各种要求。
发明内容
本发明是一种粘合剂组合物，它包括(a)可经自由基聚合而固化，即具有碳-碳不饱和度的树脂，或者可经硅氢化作用(hydrosilation)而固化，即含有硅-氢基团的树脂；(b)含有烯丙基或乙烯基不饱和度的环氧化合物；(c)树脂固化剂和环氧固化剂；(d)任选的一种或多种填料。组合物还可包括粘接促进剂或偶联剂。发明者们发现加入含烯丙基或乙烯基不饱和度的环氧化合物，可使含碳-碳不饱和度的基础树脂的粘合力获得意想不到的提高。在另一种实施方案中，本发明是用发明的粘合剂将半导体芯片粘接到基板上的半导体封装。
可作为微电子应用中的粘合剂的自由基可固化树脂包括，例如Ciba Specialty Chemicals生产的马来酰亚胺、Gelest生产的硅氧烷和聚硅氧烷、BASF生产的聚醚、Uniqema或Bayer生产的聚酯、Elf-Atochem生产的聚丁二烯、Bayer或BASF生产的聚氨基甲酸酯、Sartomer或UCB Radcure生产的丙烯酸酯树脂。经硅氢化作用固化的硅氧烷和聚硅氧烷可以是线性或环状聚合物，且每个分子至少含有两个硅-氢官能度。聚醚、聚酯和聚氨基甲酸酯最好包含末端不饱和度，但也可以在聚合物链中包含不饱和度。从业者将会选择特定的树脂以在最终制剂中提供特殊材料性质，如流变性、亲水性或疏水性、韧性、强度、或者柔性。该树脂将占粘合剂组合物的10-80％(重量)。
环氧化合物可以是任何具有烯丙基或乙烯基官能度的环氧化合物。实例包括2，6-二缩水甘油苯基烯丙醚、二氧化苧烯、缩水甘油乙烯基苯甲醚或缩水甘油乙烯醚。环氧化合物将占粘合剂组合物的0.1-30％(重量)。
用于基础树脂的典型固化剂是自由基引发剂，它可以是热引发剂或光引发剂。引发剂占粘合剂组合物的量为0.1％-10％，最好为0.1％-3.0％(重量)。优选的热引发剂包括过氧化物，例如过氧辛酸丁酯、过氧化二枯基以及偶氮化合物，如2，2’-偶氮双(2-甲基-丙腈)和2，2’-偶氮双(2-甲基-丁腈)。优选光引发剂系列是Ciba Specialty Chemicals的商标为Irgacure的引发剂。在一些制剂中，光固化和热固化都是需要的，举例来说，固化过程由辐照开始，在随后的步骤中则用热来结束固化。
用于环氧树脂上的环氧官能度的典型固化剂是路易斯碱，例如胺，如从Air Products购买的Ancamine 2337xs和4，4’-双(对氨基环己基)甲烷；咪唑，如Shikoku Chemicals的产品curezol 2E4MZ-CN；酰胺，如Air Products的产品二氰胺(Dicyanamide)；聚酰胺，如Henkel的产品Versamide 140；叔胺，如Air Products的产品Amicure DBU。也可选用路易斯酸代替路易斯碱来引发阳离子固化，如Rhodia的产品Rhodorasil 2074[(甲苯基枯基)碘四(五氟苯基)硼酸盐]或GeneralElectric的产品GE UV9380C。组合物中用于环氧官能度的固化剂将占总配方的0.1-3％(重量)。
一般，这些组合物将在70℃-250℃的温度范围内固化，并在10秒到3小时内完成固化。各配方的时间温度固化曲线图将随各配方组分的变化而变化，但对于熟悉本领域的技术人员而言，不需要做不恰当的试验就可调节固化曲线的参数。
在一些组合物中需要加入有机或无机填料。合适的传导性填料是炭黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、氮化硼、金刚石以及矾土。合适的非传导性填料是蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙、玻璃、熔凝硅石、热解法二氧化硅、硫酸钡的颗粒；和卤化乙烯聚合物，如四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。虽然是任意的，但当填料存在时，其含量将占组分的20％-90％(重量)。
合适的粘接促进剂或偶联剂是硅烷、硅酸酯、金属丙烯酸盐或甲基丙烯酸盐、钛酸盐以及含螯合配体的化合物，如膦、硫醇、乙酰乙酸酯(acetoacetate)。当存在时，偶联剂的含量最多为10％(重量)，最好为0.1％-3.0％(重量)。
下面的实施例是对本发明的进一步说明，而非对本发明的限制。
具体实施方式
采用称为JESD22-A112的JEDEC Solid State TechnologyAssociation的试验方案对半导体封装进行可靠性试验，所用半导体包括用粘合剂粘接于引线框架(leadframe)的连接焊片(bond pad)上的硅片，被封在模塑复合体(molding compound)内的芯片(die)和引线框架。在该方法中，半导体封装在85℃和85％相对湿度条件下被放置168小时，随后暴露于240℃的采用锯齿形分布的标准回流焊的红外线烘箱中达5分钟。部件的可靠性破坏表现为部件接口的脱层或模塑复合体有裂缝。
上述试验中，发明者将芯片粘接于引线框架以检测粘合剂的性能，它是用芯片固定粘合剂将芯片粘接于引线框架的非密封组件。在这些试验中，非密封组件在175℃的烘箱中固化30分钟。固化之后，这些组件被分为两组。在暴露于热的干燥环境中后，包括先在240℃下1分钟，随后在175℃下4小时，测试第一组的芯片的剪切强度。
在暴露湿热环境中，包括在85％相对湿度和85℃下168小时后，测试第二组的芯片剪切强度。
经过上述处理后，将各组件加热至250℃，之后将芯片从基板上剪切下来。一些组件表现为将芯片粘接到引线框架的粘结剂内聚模式破坏(cohesive mode failure)，另一些组件表现为将芯片粘接到引线框架的粘结剂粘合模式失效(adhesive mode failure)。
在采用经相同粘结剂粘接的密封包装进行的JEDEC测试方法中，那些发生内聚模式破坏的粘结剂具有较高的可靠性；而在采用经相同粘结剂粘接的密封包装进行的JEDEC测试方法中，那些发生粘合模式失效的粘结剂给出了洁净的金属表面，具有较低可靠性。
在以下实施例中，对含有或不含有带烯丙基或乙烯基官能度的环氧树脂的制剂，采用上述方案测试其在热的干燥环境下的芯片剪切强度和其在湿热环境下的芯片剪切强度(以千克力计)。所用芯片是粘接于裸铜或镀银引线框架的12.5mm×12.5mm×0.38mm的硅片。
粘结剂组合物和测试结果列于下表中，从该表可知，含有带烯丙基或乙烯基官能度的环氧树脂的粘结剂制剂在湿热环境下的芯片剪切力测试中内聚模式破坏，而不含带烯丙基或乙烯基官能度的环氧树脂的制剂则粘合模式破坏。因此，数据显示含有带乙烯基或烯丙基不饱和度的环氧化合物的制剂可提高粘结剂性能以及半导体包装可靠性。组合物用重量百分比表示。
                                     实施例1
组合物实施例1   含有烯丙基官能度的环氧树脂     不含烯丙基官能度的环氧树脂
  专用双马来酰亚胺           19.04％           19.04％
  4，4’-双马来酰亚胺基-二苯甲烷 0.52％ 0.52％
  (2，6-二缩水甘油苯基烯丙)环氧树脂           1.2％           ----
  双-酚-F环氧树脂           ----           1.57％
  聚(丁二烯)(Ricon 130)           2.61％           2.61％
  聚酯乙烯醚树脂(Alllied signalVE1312)           1.57％           1.57％
  肉桂醇与二异氰酸酯二聚体的加成化合物 3.39％ 3.39％
  甲基丙烯酰氧基硅烷(Witco-A-174)           0.4％           0.4％
  1，1-二(叔戊基过氧)环己烷(Witco USP90MD)           0.65％           0.65％
  2-乙基4-甲基咪唑-CN           0.25％           0.25％
  薄银片           70％           70％
  总量           100％           100％
实施例1的性能   镀银引线框架   裸铜引线框架   镀银引线框架   裸铜引线框架
  30分钟/175℃固化芯片翘曲，于RT 15.5μ 8.3 μ 18.6μ 7.1μ
  于250℃下的热干燥芯片剪切力   14.1kg内聚破坏   12.3kg内聚破坏   1.3kg粘合失效   1.8kg粘合失效
于250℃下的热湿芯片剪切力   7.3kg内聚破坏   6.24kg内聚破坏   1.3kg粘合失效   1.6kg粘合失效
                                    实施例2
组合物样实施例2   含有烯丙基官能度的环氧树脂   不含烯丙基官能度的环氧树脂
  带丙烯酸酯官能度的聚丁二烯(Ricon，1756)            10.5％         10.5％
  带马来酸酐官能度的聚丁二烯(Ricon，130MA10)            2.0％         2.0％
  1，6-二醇二丙烯酸酯(SartomerSR238)            2.0％         2.0％
  异冰片基丙烯酸酯(SartomerSR506)            5.0％         5.0％
  1，1-二(叔戊基过氧)环己烷(Witco USP，90MD)            0.5％         0.5％
  丙烯酸十二烷基酯(SartomerSR335)            2.5％         2.5％
  2，6-二缩水甘油苯基烯丙醚            2.0％         0％
  2-乙基4-甲基咪唑-CN            0.2％         0％
  薄银片            75％         75％
  总量            100％         100％
实施例2的性能   镀银引线框架   裸铜引线框架   镀银引线框架   裸铜引线框架
  室温下的芯片翘曲固化30分钟/175℃加1分钟/220℃或加4小时/174℃*脱层 22.5μ26.6μ19.7μ 17.0μ17.5μ12.1μ
  于250C热干燥芯片剪切力破坏类型   6.6kg内聚破坏   1.3kg粘合失效
  于250C热湿芯片剪切力破坏类型   2.8kg内聚破坏   1kg粘合失效
注意：
两种制剂对于镀银引线框架的粘合力都令人满意。
                                    实施例3
组合物实施例3   含有烯丙基官能度的环氧树脂   不含烯丙基官能度的环氧树脂
    Sycar树脂*         13.96         11.56
    聚丁二烯(Ricon树脂，Ricon 130) 2.33 1.93
    带马来酸酐官能度的聚(丁二烯)(Ricon树脂，Ricon 130/MAg)
    带马来酸酐官能度的聚(丁二烯)(Ricon树脂，Ricon 130/MA20)         0.23         0.20
    二烯丙基双酚-A(Bi-Max)         1.63         1.35
    二乙烯醚(ISP Tech，DVE-3)         1.16         0.96
    (2，6-二缩水甘油苯基烯丙醚)环氧树脂         ----         2.90
    1，3-双(环氧丙氧丙基)四甲基二硅氧烷(Gelest，SIB 1115.0)         ----         0.58
    Rhodorsil 2074(Rhone Poulenc)         ----         0.6
    热解法二氧化硅(Degussa，812S)         0.5         0.5
    银粉(Chemet，K-0082P)         78         78
    铂络合物*(Sivento Inc.，CPC 085)         0.4         0.4
    铂络合物*(Sivento Inc.，CPS 925-P)         0.4         0.4
    总量         100％         100％
    实施例3的性能**
    粘接于PBGA上的360×360密耳Si芯片在85/85下经48小时后的芯片剪切强度，于200℃ 17.0±1.5 15.3±3.2
破坏类型 芯片背面粘合失效         焊锡表层80％脱落
*将浓缩溶液用环状甲基乙烯基硅氧烷稀释至约5000ppm Pt浓度。
**粘合剂组合物被调制在金属引线框架上，然后将其放在对流烘箱内用30分钟将温度从室温升至175℃，然后在175℃保持15分钟进行固化。

Claims (5)

1.一种芯片固定粘合剂组合物，它包括：
(a)可经自由基聚合或者硅氢化作用而固化的树脂，其所占的量为10％-80％重量；
(b)含有乙烯基或烯丙基官能度的环氧化合物，其所占的量为0.1％-30％重量；
(c)用于环氧化合物的固化剂，其所占的量为0.1％-3％重量；和
(d)用于树脂的固化剂，其所占的量为0.1％-10％重量。
2.依照权利要求1的芯片固定粘合剂组合物，其中树脂选自马来酰亚胺、聚醚、聚酯、聚丁二烯、聚氨基甲酸酯、丙烯酸酯、硅氧烷和聚硅氧烷。
3.依照权利要求1的芯片固定粘合剂组合物，其中环氧化合物选自2，6-二缩水甘油苯基烯丙醚、二氧化槚烯、缩水甘油乙烯基苯甲醚和缩水甘油乙烯醚。
4.依照权利要求1的芯片固定粘合剂组合物，该组合物还包括填料，该填料选自炭黑、石墨、金、银、铜、铂、钯、镍、铝、碳化硅、氮化硼、金刚石、矾土、蛭石、云母、硅灰石、碳酸钙、二氧化钛、沙、玻璃、熔凝硅石、热解法二氧化硅、硫酸钡、四氟乙烯、三氟乙烯、1，1-二氟乙烯、氟乙烯、1，1-二氯乙烯和氯乙烯。
5.依照权利要求1的芯片固定粘合剂组合物，该组合物还包括填料，该填料所占的量为20％-90％重量。
CNB011225637A 2000-07-07 2001-07-05 具有烯丙基或乙烯基的环氧树脂芯片固定粘合剂 Expired - Lifetime CN1193081C (zh)

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Families Citing this family (42)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6822047B2 (en) * 2003-01-02 2004-11-23 National Starch And Chemical Investment Holding Corporation Adhesive with carboxyl benzotriazole for improved adhesion to metal substrates
US7884174B2 (en) * 2003-05-05 2011-02-08 Designer Molecules, Inc. Imide-linked maleimide and polymaleimide compounds
DE10351429B4 (de) * 2003-11-04 2013-10-31 Epcos Ag SAW Bauelement mit Klebestelle und Verwendung dafür
US7875688B2 (en) * 2004-06-04 2011-01-25 Designer Molecules, Inc. Free-radical curable polyesters and methods for use thereof
US7795362B2 (en) * 2004-07-16 2010-09-14 Designer Molecules, Inc. Olefin oligomers containing pendant maleimide groups
US20060235137A1 (en) * 2005-04-18 2006-10-19 Eunsook Chae Die attach adhesives with improved stress performance
US8043534B2 (en) * 2005-10-21 2011-10-25 Designer Molecules, Inc. Maleimide compositions and methods for use thereof
US8378017B2 (en) * 2005-12-29 2013-02-19 Designer Molecules, Inc. Thermosetting adhesive compositions
ATE397647T1 (de) * 2006-03-06 2008-06-15 Umicore Ag & Co Kg Zusammensetzung zur befestigung von hochleistungshalbleiter
CN102336890B (zh) * 2006-03-29 2015-09-16 汉高股份两合公司 辐射或热可固化的防渗密封胶
US20070236542A1 (en) * 2006-03-29 2007-10-11 Graham David C Adhesive Compositions, Micro-Fluid Ejection Devices, and Methods for Attaching Micro-Fluid Ejection Heads
US8530573B2 (en) 2006-05-10 2013-09-10 Designer Molecules, Inc. Modified calcium carbonate-filled adhesive compositions and methods for use thereof
US8287686B2 (en) * 2006-07-24 2012-10-16 Designer Molecules, Inc. Derivatives of poly(styrene-co-allyl alcohol) and methods for use thereof
US7825188B2 (en) * 2006-12-19 2010-11-02 Designer Molecules, Inc. Thermoplastic elastomer with acyloxyphenyl hard block segment
WO2008077140A2 (en) * 2006-12-19 2008-06-26 Designer Molecules, Inc. Hydrolytically resistant thermoset monomers
CN101210162B (zh) * 2006-12-28 2011-11-30 西安西电变压器有限责任公司 一种半导体胶及其制备方法
WO2008092168A2 (en) * 2007-01-26 2008-07-31 Designer Molecules, Inc. Methods for the preparation of imides, maleimides and maleimide-terminated polyimide compounds
US20080202694A1 (en) * 2007-02-26 2008-08-28 Serbicki Jeffrey P Fluid flow path in microfluidic device
US20100113643A1 (en) * 2007-04-09 2010-05-06 Designer Molecules, Inc. Curatives for epoxy adhesive compositions
US8431655B2 (en) * 2007-04-09 2013-04-30 Designer Molecules, Inc. Curatives for epoxy compositions
US7868113B2 (en) 2007-04-11 2011-01-11 Designer Molecules, Inc. Low shrinkage polyester thermosetting resins
US20100056671A1 (en) * 2007-04-12 2010-03-04 Designer Molecules, Inc. Polyfunctional epoxy oligomers
WO2008130894A1 (en) * 2007-04-16 2008-10-30 Designer Molecules, Inc. Low temperature curing acrylate and maleimide based formulations and methods for use thereof
US20080292801A1 (en) * 2007-05-23 2008-11-27 National Starch And Chemical Investment Holding Corporation Corrosion-Preventive Adhesive Compositions
US7928153B2 (en) 2007-08-14 2011-04-19 Designer Molecules, Inc. Thermosetting polyether oligomers, compositions and methods for use thereof
US8398898B2 (en) * 2008-02-23 2013-03-19 Designer Molecules, Inc. Soluble metal salts for use as conductivity promoters
EP2250227A4 (en) * 2008-02-25 2013-08-21 Henkel Ag & Co Kgaa OUT OF THEIR PUNCHING CHIP FIXING PASTE
WO2009117729A2 (en) 2008-03-21 2009-09-24 Designer Molecules, Inc. Anti-bleed compounds, compositions and methods for use thereof
US8308892B2 (en) 2008-04-09 2012-11-13 Designer Molecules, Inc. Di-cinnamyl compounds and methods for use thereof
US8158748B2 (en) 2008-08-13 2012-04-17 Designer Molecules, Inc. Hetero-functional compounds and methods for use thereof
US8217120B2 (en) * 2008-08-13 2012-07-10 Designer Molecules, Inc. Functionalized styrene oligomers and polymers
US8013104B2 (en) * 2008-08-13 2011-09-06 Designer Molecules, Inc. Thermosetting hyperbranched compositions and methods for use thereof
US8008419B2 (en) * 2008-08-13 2011-08-30 Designer Molecules, Inc. Siloxane monomers and methods for use thereof
US8288591B2 (en) * 2008-11-20 2012-10-16 Designer Molecules, Inc. Curing agents for epoxy resins
US20110014354A1 (en) * 2009-07-20 2011-01-20 David Christopher Graham Adhesive compositions and methods for use in failure analysis
US8415812B2 (en) * 2009-09-03 2013-04-09 Designer Molecules, Inc. Materials and methods for stress reduction in semiconductor wafer passivation layers
US8710682B2 (en) * 2009-09-03 2014-04-29 Designer Molecules Inc, Inc. Materials and methods for stress reduction in semiconductor wafer passivation layers
TWI651387B (zh) * 2013-09-30 2019-02-21 漢高智慧財產控股公司 用於大型晶粒半導體封裝之導電黏晶薄膜及供其製備之組合物
CN105602460B (zh) * 2016-01-18 2018-05-25 厦门百安兴新材料有限公司 一种可快速固化双组份弹性填缝剂及其制备方法
CN105647400B (zh) * 2016-01-18 2018-08-31 佛山市佳密特防水材料有限公司 一种双组份弹性填缝剂及其制备方法
JP6424868B2 (ja) * 2016-09-07 2018-11-21 信越化学工業株式会社 シラン変性共重合体、その製造方法および密着向上剤
DE102021129372A1 (de) 2021-11-11 2023-05-11 Thyssenkrupp Steel Europe Ag Verfahren zum Verkleben von Blechbauteilen

Family Cites Families (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4115361A (en) * 1976-11-22 1978-09-19 Texaco Development Corp. Polyether urea epoxy additives
GB1552046A (en) * 1977-02-02 1979-09-05 Ciba Geigy Ag Film adhesives
JPS57143320A (en) * 1981-02-28 1982-09-04 Mitsubishi Gas Chem Co Inc Novel curable resin composition
JPS59196378A (ja) * 1983-04-22 1984-11-07 Hitachi Ltd 半導体素子接合用接着剤と半導体装置およびその製造法
US4564563A (en) * 1983-09-30 1986-01-14 Electro Materials Corp. Of America Solderable conductor
US4612209A (en) * 1983-12-27 1986-09-16 Ciba-Geigy Corporation Process for the preparation of heat-curable adhesive films
US4654382A (en) * 1984-06-08 1987-03-31 The Yokohama Rubber Co., Ltd. Adhesive compositions
US4595604A (en) * 1984-07-18 1986-06-17 Rohm And Haas Company Conductive compositions that are directly solderable and flexible and that can be bonded directly to substrates
US4595606A (en) * 1984-07-18 1986-06-17 Rohm And Haas Company Solderable conductive compositions having high adhesive strength
US4902732A (en) * 1985-09-30 1990-02-20 Shin-Etsu Chemical Co., Ltd. Epoxy resin-based curable compositions
JPS62207354A (ja) * 1986-03-07 1987-09-11 Sumitomo Chem Co Ltd 熱硬化性樹脂組成物
CA1326673C (en) * 1986-12-26 1994-02-01 Yasuhisa Saito Imide compound and composition containing the same
JPH01261429A (ja) 1988-04-11 1989-10-18 Dainippon Ink & Chem Inc 多層プリント回路基板の製造方法
JP2573661B2 (ja) 1988-07-09 1997-01-22 キヤノン株式会社 感光感熱型接着剤
JP2833111B2 (ja) * 1989-03-09 1998-12-09 日立化成工業株式会社 回路の接続方法及びそれに用いる接着剤フィルム
US5034473A (en) * 1989-08-17 1991-07-23 National Starch And Chemical Investment Holding Company Composition of polyepoxide derived from alkoxy-substituted allylphenol and carboxy-terminated polyester or polyamide
US5043102A (en) * 1989-11-29 1991-08-27 Advanced Products, Inc. Conductive adhesive useful for bonding a semiconductor die to a conductive support base
US5292812A (en) * 1990-01-24 1994-03-08 The Yokohama Rubber Co., Ltd. Adhesive of epoxy resin, CTBN and maleimide
JP2904536B2 (ja) * 1990-03-09 1999-06-14 株式会社日立製作所 半導体装置用接着剤組成物
JP2669247B2 (ja) * 1992-02-13 1997-10-27 信越化学工業株式会社 熱硬化性樹脂組成物
JPH0764913B2 (ja) * 1992-03-26 1995-07-12 旭化成工業株式会社 新しい硬化性ポリフェニレンエーテル・エポキシ樹脂組成物
US5496907A (en) * 1993-03-02 1996-03-05 H. B. Fuller Licensing & Financing, Inc. Wet adhesion monomers with ureido functionality and polymers prepared therefrom
US5459200A (en) * 1994-10-11 1995-10-17 Shell Oil Company Polyurethane coatings and adhesives containing monohydroxylated diene polymers and epoxidized derivatives thereof
US5717054A (en) * 1995-06-07 1998-02-10 National Starch & Chemical Investment Holding Corp. Epoxy resins consisting of flexible chains terminated with glycidyloxyphenyl groups for use in microelectronics adhesives
US5646315A (en) * 1995-06-07 1997-07-08 National Starch And Chemical Investment Holding Corporation Polyglydicylphenyl ethers of alkyloxy chains for use in microelectronics adhesives
US5863970A (en) * 1995-12-06 1999-01-26 Polyset Company, Inc. Epoxy resin composition with cycloaliphatic epoxy-functional siloxane
EP0780435A1 (en) * 1995-12-21 1997-06-25 National Starch and Chemical Investment Holding Corporation Flexible epoxy adhesives with low bleeding tendency
JPH1060138A (ja) 1996-08-27 1998-03-03 Matsushita Electric Works Ltd 配線基板材料
SG63803A1 (en) * 1997-01-23 1999-03-30 Toray Industries Epoxy-resin composition to seal semiconductors and resin-sealed semiconductor device
US5744533A (en) * 1997-06-04 1998-04-28 Johnson Matthey, Inc. Adhesive composition for bonding a semiconductor device
JPH11147929A (ja) 1997-11-18 1999-06-02 Nippon Kayaku Co Ltd エポキシ樹脂、エポキシ樹脂製造法、エポキシ樹脂組成物及びその硬化物
JP3247091B2 (ja) * 1997-11-28 2002-01-15 日立化成工業株式会社 光硬化性樹脂組成物及びこれを用いた感光性エレメント
US6583198B2 (en) 1997-11-28 2003-06-24 Hitachi Chemical Company, Ltd. Photo curable resin composition and photosensitive element
GB2332202A (en) * 1997-12-09 1999-06-16 Courtaulds Coatings Curable epoxy resin compositions
JP4275221B2 (ja) * 1998-07-06 2009-06-10 リンテック株式会社 粘接着剤組成物および粘接着シート
JP4573373B2 (ja) * 1999-05-20 2010-11-04 スリーエム イノベイティブ プロパティズ カンパニー 接着構造体

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