CN1788062A - 用于电子设备的具有电稳定性和良好抗冲击性的导电性粘合剂组合物 - Google Patents
用于电子设备的具有电稳定性和良好抗冲击性的导电性粘合剂组合物 Download PDFInfo
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- CN1788062A CN1788062A CNA2004800052335A CN200480005233A CN1788062A CN 1788062 A CN1788062 A CN 1788062A CN A2004800052335 A CNA2004800052335 A CN A2004800052335A CN 200480005233 A CN200480005233 A CN 200480005233A CN 1788062 A CN1788062 A CN 1788062A
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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
- C08G59/182—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 using pre-adducts of epoxy compounds with curing agents
- C08G59/184—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 using pre-adducts of epoxy compounds with curing agents with amines
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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
- C08G59/68—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 catalysts used
- C08G59/686—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 catalysts used containing nitrogen
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Abstract
一种组合物,其含有a)至少一种环氧树脂和脂肪胺的混合物,其中环氧官能团/胺的比率大于1;b)导电性填料;c)一种或一种以上的腐蚀抑制剂、氧清除剂或两者都包括;d)作为固化剂/催化剂的咪唑;和e)任选其它添加剂如有机溶剂、流动添加剂、粘合促进剂和流变改良剂。环氧官能度过量的环氧树脂和脂肪胺的反应生成具有残余活性环氧基团的柔性树脂。该组合物显示出优于不含有该混合物的其它传导性粘合剂组合物的改进的电稳定性和抗冲击性。
Description
发明领域
本发明涉及适宜在微电子设备或半导体组件中用作导电性材料以提供电稳定的相互联结的组合物。
发明背景
在半导体组件和微电子设备的制造和组装中,为了各种目的使用导电性组合物。例如,用导电性粘合剂将集成电路芯片粘接在基片上(模连接粘合剂)或将电路组件粘接在印刷电路板上(表面组装导电性粘合剂)。
在整个电子工业中,将零件焊接在基片上的主要技术使用也被称为共熔焊膏的金属焊膏合金,其含有重量含量为63%的锡和37%的铅。将它作为焊膏施用在电路板上,将焊膏加热到高于它的熔化温度(183℃)时会使焊膏熔化并形成接头。作为另一个选择,可将电路板通过焊膏的熔融波从而形成接头将电子元件连接在电路板上。在任一情况中,用助熔剂除去金属表面的表面氧化物从而使熔化的焊膏牢固地连接在表面上并且形成具有优良的抗冲击性的可靠的焊接接头。尽管焊膏技术已经存在了几十年,它还是有一些缺点。合金中的铅对环境不友好。已经提出了许多环境法规来征税、限制或禁止在电子焊膏中使用铅。其次,高加工温度需要使用更昂贵的热稳定基片并且不适合在电子工业中变的越来越来普遍的软性基片。另一个缺点是在回流过程之后需要额外步骤来清除来自助熔剂的残留物,这是昂贵和低效率的过程。
由于没有铅、低的加工温度并且不需要焊接助熔剂和接下来的清理助熔剂的步骤而使组装方法简化,导电性粘合剂提供了优于传统焊接组装的一些优点。有以下导电性粘合剂所需要的特性:在室温下使用寿命长、固化温度相对低和固化时间相对短、对于丝网印刷的良好流变能力、固化后足以运送电流的导电性、固化后具有合乎需要的与基片的粘合力、长时间在高温和潮湿中稳定的电阻和良好的冲击强度。
对商业可获得的粘合剂的提前检测得出结论:由于受电阻和冲击需求的限制,导电性粘合剂只适用于特定的应用。一些销售商声称在发展抗冲击的粘合剂上获得了成功,而一些销售商声称在稳定的接触电阻上获得了成功。但他们中没有一个成功地同时获得抗冲击性和稳定的接触电阻,尤其是对于锡/铅表面。事实上,许多粘合剂销售商已经承认冲击强度和电阻稳定性是相互排斥的参数。
水存在时具有不同电化学势的两种导体会形成电化学电池。导体起到负极和正极的作用,并且环境潮气提供接通正极和负极的必要的水介质。具有较低电化学势的金属作为正极,结果其失去电子{ }并腐蚀金属。具有较高电化学势的金属作为负极{ }。氧气与这种过程有关但并不直接和正极金属反应。金属离子Mn+将和OH-结合并形成金属氢氧化物,其通过演变成金属氧化物而稳定,该金属氧化物经过一段时间在正极表面上形成。金属氧化物一般是不导电的,结果减少了金属电路的导电性。
当组合物中的填料与相接触电路或基片是相同的金属时,问题就不那么严重了。这样例如,当在银基片上使用银填充的组合物时,使用含有环氧树脂和银填料的导电性组合物的半导体组件就不容易出现电化学失效。然而,如果在镀镍的基片上使用上述组合物,在高湿度的情况中就会产生电化学腐蚀。
然而,这些组合物容易受到环境条件的影响,并且高温和高湿度会造成用这些组合物制备的组件随时间电阻相当大地增加。这种失效可能的模式是在组合物中的导电性填料与其它接触金属的表面,如金属铅框架或其它电路的交界面处的电路的电化学腐蚀。
这些组合物的另一个弱点是当含有该组合物的组件掉落或被撞击时,它们对冲击的抵抗力。大部分导电性粘合剂经常被认为是高Tg的刚性材料。这种刚性将有效地阻止在撞击试验温度即环境温度下机械能的分散。这样当整个组件从高处落下时,导电性粘合剂会破裂或零件脱离基片。当含有高填充量的导电性填料时,导电性粘合剂的抗冲击性变得更差。
因此提供用于半导体封装操作的形成电稳定组件的导电性材料是有益的。提供导电性粘合剂也是有益的,当暴露在恶劣的环境条件中并受到冲击时,该导电性粘合剂可以提供改进的接触电阻。同时,粘合剂具有相对长的保存期限也很重要。
附图简介
图1图示了三种导电性粘合剂制剂的接触电阻随着时间的变化。
图2图示了粘合剂在85℃/85%相对湿度中的接触电阻随着时间的变化。
发明简述
本发明是一种组合物,其含有a)至少一种环氧树脂和脂肪胺的混合物,其中环氧官能团/胺的比率大于1;b)导电性填料;c)一种或一种以上的腐蚀抑制剂、氧清除剂或这两者;d)作为固化剂/催化剂的咪唑;和e)任选其它的添加剂如有机溶剂、流动添加剂、粘合促进剂和流变改良剂。环氧官能团过量的环氧树脂和脂肪胺的预反应生成具有柔性结构和残余活性环氧基团的预聚物。该组合物显示出优于其它不含有该混合物的粘合剂的改进的电稳定性和抗冲击性和更稳定的保存期限。对于100重量%的总量,混合物的含量为10到90重量%;填料的含量为约30到90重量%;腐蚀抑制剂和/或氧清除剂的含量不超过10重量%(但不是0%);固化剂的含量不超过10重量%(但不是0%);有机溶剂的含量至多为50重量%;和任选组分的含量不超过10重量%。
发明详述
导电性粘合剂通常是由酚醛树脂、环氧树脂或树脂的混合物组成的。通过将本发明的树脂与其它组分,如伯胺、作为催化剂的咪唑和作为腐蚀抑制剂的8-羟基喹啉的混合物引入,产生的导电性粘合剂提供了有益的电稳定性和抗冲击性。另外,本发明的导电性粘合剂具有良好的丝网印刷性、良好的保存期限、低的固化温度、低的接触电阻和与铜基片良好的粘合力。
本发明的导电性粘合剂含有a)至少一种环氧树脂和脂肪胺的混合物,其中环氧官能团/胺的比率大于1;b)导电性填料;c)一种或一种以上的腐蚀抑制剂、氧清除剂或这两者;d)作为固化剂/催化剂的咪唑;和e)任选的其它添加剂如有机溶剂、流动添加剂、粘合促进剂和流变改良剂。环氧官能团过量的环氧树脂和脂肪胺的预反应生成具有柔性结构和残余活性环氧基团的预聚物。特别选择组分来获得所用特定树脂的理想的性能平衡。
本发明所用优选的环氧树脂包括双酚-A和双酚-F的单官能和多官能的缩水甘油醚、脂肪族和芳香族环氧树脂、饱和的和不饱和环氧树脂,或脂环族环氧树脂或它们的混合物。脂肪族环氧树脂包括FlexEpoxy1。
Flex Epoxy1
芳香族环氧树脂包括RAS-1、RAS-5和Flex Epoxy-3。
不饱和环氧树脂的例子包括Cardolite NC513。
本发明中优选单独的或与非缩水甘油醚环氧化物混合的缩水甘油醚环氧化物。这种类型的优选的环氧树脂是双酚A树脂。另一种优选的环氧树脂是包括Flex Epoxy-1环氧树脂的脂肪族环氧树脂。最优选的环氧树脂是双酚F类型的树脂。通常通过一摩尔双酚F树脂和两摩尔表氯醇反应来制备这些树脂。还有一种优选的环氧树脂类型是环氧线型酚醛树脂。环氧线型酚醛树脂通常是通过酚醛树脂和表氯醇反应制备的。可以使用的其它环氧树脂的类型是二环戊二烯-苯酚环氧树脂、萘树脂、环氧官能的丁二烯丙烯腈共聚物、环氧官能的聚二甲基硅氧烷及其混合物。商业上可获得的双酚-F类型树脂可以从CVCSepcialty Chemicals,Maple Shade,New Jersey以名称8230E获得,还可以从Resolution Performance Products Ltd.以名称RSL1739获得。在商业上双酚-A类型树脂可以从ResolutionPerformance Products Ltd.以名称EPON 828获得,并且双酚-A和双酚-F的混合物可以从Nippon Chemical Company以名称ZX-1059获得。
合乎需要的伯胺化合物,如聚氧化丙烯二胺,与环氧官能过量的环氧树脂化合生成以环氧官能团封端的预聚物。尤其优选的伯胺是脂肪胺、二胺或三胺。商业上可获得的脂肪胺的例子是Jeffamine(Huntsman)。
除了树脂,在导电性粘合剂组合物中还包括作为催化剂的咪唑。咪唑给导电性粘合剂提供了不同于其它催化剂如二氰胺和叔胺所提供的性能的性能。可以包括在组合物中的优选的咪唑包括非N取代的咪唑如2-苯基-4-甲基咪唑、2-苯基咪唑和咪唑。其它可用的咪唑组分包括烷基取代的咪唑、N-取代的咪唑和它们的混合物。
导电性材料可以含有导电性填料。典型的导电性填料是银、铜、金、钯、铂、碳黑、碳纤维、石墨、铝、铟锡氧化物、镀银的铜、镀银的铝、铋、锡、铋-锡合金、镀金属的玻璃球、镀银的纤维、镀银的球和掺锑的锡氧化物。
为了抑制形成金属氧化物,通常使用腐蚀抑制剂。腐蚀抑制剂在这里被定义为具有孤对电子的任何化合物,如含氮、硫和氧的化合物,其可以和金属结合并且阻止电化学正极上金属的反应。典型的腐蚀抑制剂是1,10-phenathiodine、吩噻嗪、苯并三唑、苯并咪唑、巯基苯并噻唑、二氰胺、3-异丙氨基-1-丁炔、炔丙基喹啉鎓溴化物、3-苄氨基-1-丁炔、二炔丙基醚、二炔丙基硫醚、己酸炔丙酯、二氨基庚烷、菲咯啉、胺、二胺、三胺、六亚甲基酰亚胺、十亚甲基酰亚胺、六亚甲基亚胺苯甲酸酯、六亚甲基亚胺-3,5-二硝基苯甲酸酯、六亚甲基四胺、d-肟基-b-乙烯基奎宁环、苯胺、6-N-乙基嘌呤、1-乙氨基-2-十八烷基咪唑啉、吗啉、乙醇胺、氨基苯酚、2-羟基喹啉、6-羟基喹啉、8-羟基喹啉、吡啶及其衍生物、喹啉及其衍生物、吖啶、咪唑及其衍生物、甲苯胺、硫醇、苯硫酚及其衍生物、硫化物、亚砜、硫代磷酸酯、硫脲和哌啶。
任选使用的有机溶剂是用来基本上溶解树脂系统和调节导电性粘合剂的粘度使粘合剂最适于丝网印刷和润湿部件终端。可以使用的溶剂包括γ-丁内酯、缩水甘油基醚,如1,4-丁二醇二缩水甘油醚;乙烯基醚,如亚乙基乙烯基醚,和乙烯基酯,如亚乙基乙烯基酯,和丙烯酸酯,如甲基丙烯酸甲酯、二乙基二醇、一乙基醚、一缩二乙二醇二亚甲基醚、二价酸酯溶剂、卡必醇、乙酸卡必酯、丁基卡必醇、乙酸丁基卡必酯、丙酮、甲乙酮、环己酮、乙酸一缩二乙二醇一乙基醚酯、乙酸一缩二乙二醇一丁基醚酯和一缩二丙二醇一甲基醚。最优选的溶剂是γ-丁内酯。
任选如果需要可以加入合适的流动添加剂、粘合促进剂、导电性添加剂和流变改良剂。任选的流动添加剂包括硅聚合物、丙烯酸乙酯/丙烯酸2-乙基己酯共聚物、酸的烷醇铵盐、酮肟的磷酸酯或它们的混合物。合适的粘合促进剂包括各种形式的硅烷。合适的流变改良剂包括热塑性树脂并优选聚乙烯醇缩醛。合适的导电性添加剂包括酸酐、戊二酸、柠檬酸、磷酸和其它酸催化剂。
在另一个实施方案中,本发明是一种提高导电性组合物的冲击强度的方法,其包括在组合物中使用混合物。
申请人已经发现粘合剂可以提高粘合剂的冲击强度,该粘合剂含有至少一种环氧树脂和脂肪胺的混合物和作为固化剂或催化剂的咪唑,其中环氧官能团/胺的比率大于1∶1。含有该混合物的导电性粘合剂比含有相同或相似组分的物理混合物的导电性粘合剂具有更好的电稳定性、更大的强度和更长的保存限期。
本发明该实施方案的粘合剂组合物含有至多约10到90重量%的树脂混合物;约30到90重量%的导电性填料;约0.1到10重量%的腐蚀抑制剂和/或氧清除剂;约0.1到10重量%的作为催化剂的咪唑;约0到50重量%的有机溶剂;和约0到5重量%的粘合促进剂、流动添加剂、流变改良剂或其它添加剂,对于100重量%的总量来说。优选地,树脂混合物的含量是约10到60重量%,导电性填料的含量是约40到90重量%,腐蚀抑制剂和/或氧清除剂的含量是约0.1到5重量%,作为催化剂的咪唑含量为约1到5重量%,有机溶剂的含量为约0到20重量%和其它的添加剂的含量为约0到约5重量%。
本发明还可以通过以下实施例被进一步描述。
实施例
实施例1.制备预聚物的试样和环氧树脂-胺系统物理混合物的试样。制备环氧树脂和胺的物理混合物(组分A)是通过将重量%为55.56的一种双酚-A的二缩水甘油基醚和双酚-F的二缩水甘油基醚(从Tohto Kasei Co.以ZS1059商业获得的)的混合物和44.44重量%的聚(氧基(甲基-1,2-乙烷二基)、α-(2-氨基甲基乙基)ω-2(2-氨甲基乙氧基)(从Huntsman Petrochemical Co.以Jeffamine®D-2000商业获得的)混合得到的。通过在常规烘箱中在120℃下加热物理混合物6个小时得到预聚物(组分B)。用IR光谱检测组分A和B并且组分B在波长为3439em-1处显示吸收峰,这表示在试样中存在羟基官能团。组分A没有在波长为3439cm-1处显示吸收峰,这表示没有羟基官能团。胺和环氧系统的典型的聚合反应生成具有羟基官能团的直链。预聚物的光谱显示了这个事实。
在预聚物的光谱中在波长3439cm-1处的吸收峰指示试样中存在羟基官能团,但物理混合物却没有(在波长3439cm-1处没有吸收峰)。通过布氏(Brookfield)粘度计测量组分A和B的粘度。粘度表示在表1中。
表1.预聚物和物理混合物的粘度
组分A | 组分A | 组分B | 组分B | |
时间(小时) | 粘度(cPa) | 粘度的变化(%) | 粘度(cPa) | 粘度的变化(%) |
0 | 28.4 | 0 | 1495 | 0 |
7 | - | - | 1556 | 4 |
24 | - | - | 1720 | 15 |
48 | 70.7 | 149 | - | - |
72 | - | - | 2027 | 36 |
96 | 127.5 | 349 | - | - |
如表1所示,物理混合物的粘度变化得快而预聚物的粘度却不是这样。这样预聚物比物理混合物更加耐贮存并且工作寿命更长。
实施例2.通过五种被咪唑催化并含有环氧树脂-脂肪胺预聚物的不同的粘合剂制剂来检测导电性粘合剂的初始接触电阻。配方通过首先将线型酚醛树脂(Novolac)1166在120℃下溶解在γ-丁内酯中来制备该制剂。将溶液冷却到室温,并加入剩余的组分并且用机械搅拌器彻底混合。制剂的组成显示在表2中。
表2.含有环氧树脂-脂肪胺预聚物的导电性粘合剂
组分 | 配方A | 配方B | 配方C | 配方D | 配方E |
线型酚醛树脂1166 | 0.72 | 0.72 | 0.61 | 0.61 | 0.72 |
γ-丁内酯 | 5.62 | 5.62 | 4.75 | 4.75 | 5.62 |
组分B | 14.06 | 14.06 | 11.78 | 11.88 | 14.06 |
4-甲基-2-苯基咪唑 | 0.72 | 0.72 | 0.60 | 0.60 | 0.72 |
8-羟基喹啉 | 1.30 | 1.30 | 1.10 | 1.10 | 1.30 |
BYK-W9010 | 0.07 | 0.07 | 0.06 | 0.06 | 0.07 |
己二酸 | - | - | - | - | 0.03 |
银SF-98 | 77.51 | - | - | - | - |
银SF-W | - | 77.52 | - | - | - |
银SF-80 | - | - | 81.0 | - | - |
银SF-84 | - | - | - | 81.0 | - |
银SF-85HV | - | - | - | - | 77.48 |
将配制好的粘合剂模印在陶瓷板或FR-4板上并且将电阻(0805零欧姆)放在粘合剂的上面。将整个FR-4板在150℃下固化并将整个陶瓷板在175℃下固化1个小时。当板冷却到室温时,用Keithley 2010万用表的四点探针测量初始接触电阻。初始电阻的结果显示在表3中。
表3.导电性粘合剂的初始电阻
配方A | 配方B | 配方C | 配方D | 配方E | |
电阻(mΩ) | 24 | 26 | 22 | 24 | 22 |
如表3所示,含有预聚物的导电性粘合剂全部具有满足需求的初始电阻。
同样地,用双酚-A/双酚-F环氧树脂和柔性环氧树脂形成一种导电性粘合剂,并且不使用柔性环氧树脂形成另一种导电性粘合剂。为了配制上述粘合剂,将组分一起混合,然后加入银并且用机械搅拌器混合。制剂和它们的电阻显示在表4中。
表4.具有初始电阻的双酚-A/双酚-F环氧树脂
组分 | 配方O | 配方F |
ZX1059 | 19.32 | 4.95 |
Flex Epoxy 1 | 0 | 14.37 |
BYK A187 | 0.2 | 0.2 |
Curpen | 2.48 | 2.48 |
2-乙基4-甲基咪唑CN | 0.99 | 0.99 |
8-羟基喹啉 | 1.8 | 2.68 |
银SF-98 | 74.33 | 74.33 |
电阻(mΩ) | 22 | 56 |
实施例3.按照与实施例2的试样相同的方法制备另外的两种试样,并且它们的配方如表5所示。
表5.含有不同催化剂和腐蚀抑制剂的导电性粘合剂
组分 | 配方G | 配方H |
线型酚醛树脂HT 9490 | 0.72 | 0.72 |
BCaA | 6.0 | 6.0 |
组分B | 14.39 | 14.39 |
Dyhard 100S | 1.21 | 1.21 |
HEKARM/敌草隆 | 0.61 | 0.61 |
8-羟基喹啉 | - | 2.72 |
BYK-A1120 | 0.08 | 0.08 |
银SF-96 | 76.99 | 76.99 |
在试样被配制并放置在板上之后,测量初始接触电阻。然后将板放置在潮湿的箱中,该箱保持在85℃并且相对湿度为85%,定时用Keithley 2010万用表测量接触电阻。如图1所示,不含有任何腐蚀抑制剂的试样电阻值变化更加明显。而且,当使用咪唑作为催化剂并将腐蚀抑制剂加入到配方中时,在高温和高湿度的条件中电阻更稳定得多。
实施例4.将如实施例2的每个导电性粘合剂的试样模印在3″×1.5″空白的铜板上。模印的尺寸是25×25×0.33mm。然后将模拟铅芯片(PLCC)放置在被模印的粘合剂上,并且将整个板在175℃下加热一个小时。将板冷却到室温,通过将整个芯片-粘合剂-板组件在管内从36″或60″下落到坚硬的表面上来评价下落性能。管确保组件保持在垂直位置上并且在它和坚硬的表面接触时保持其位置。下落测试的结果列在表6中。
表6.下落性能
系统 | 0 | 0 | A(具有组分A) | A(具有组分B) | B | C | D | E | F |
#在36″处失败之前下落 | 0 | 2 | 3 | 6+ | 6+ | 6+ | 6+ | 6+ | 6+ |
#在60″处失败之前下落 | 0 | 0 | 1 | 4-5 | 5-6 | 4 | 4 | 4 | 4 |
粘合剂平均厚度(mil) | 6 | 13.3 | 12 | 7.13 | 7.09 | 7.36 | 7.72 | 9.25 | 11 |
如表6所示,含有柔性环氧树脂或脂肪胺的导电性粘合剂比不含有这些组分的粘合剂具有更好的下落测试性能。同样地,含有具有环氧树脂和胺的物理混合物的粘合剂的部件的下落测试没有得到令人满意的结果。含有使用预聚物的粘合剂的部件比不含有这些组分的粘合剂产生更好的效果。
实施例5.在变化的温度和湿度条件下测试不同温度下固化的粘合剂的性能。在两种组件中使用具有预聚物的配方A,其中一个组件在150℃下固化并且另一个组件在175℃下固化。上述试样下落测试的结果显示在表7中。
表7.具有不同固化温度的下落测试结果
配方A | 175℃固化 | 150℃固化 |
#在36″处失败之前下落 | 6+ | 6+ |
#在60″处失败之前下落 | 4-5 | 3 |
平均粘合剂厚度(mil) | 7.13 | 7.60 |
为了测试不同温度下固化的稳定性,将粘合剂放置在FR-4板上并在150℃下固化和放置在陶瓷板上并在175℃下固化。将两个组件都放在潮湿的箱中并在85℃/85%相对湿度中保存。当两种试样从容器中移出时,它们的电阻显示在图2中。如图2所示,在极端的条件中接触电阻并没有改变并且不取决于固化温度。
实施例6.将实施例2中所列出的具有电子部件的试样放置在FR-4板上并进行模具剪切试验。模具剪切试验显示了导电性粘合剂在铜基片上的粘附力。使用罗伊斯(Royce)552模具自动模具剪切测试机。全部的试验在室温进行。基片上的部件是具有锡/铅接线柱的0204零电阻器。模具剪切力测试机的自动移动端头将基片上的部件推出并且将最大的力纪录为模具剪切强度。结果显示在表8中。
表8.导电性粘合剂的粘合强度
试样 | A | B | C | D | E | F |
模具剪切强度(kgF) | 2.9 | 2.6 | 2.8 | 3.1 | 3.0 | 1.1 |
很明显,在不偏离本发明的精神和范围的前提下本领域技术人员可以对本发明进行很多更改和变化。只通过实施例的方法提供了这里描述的具体实施方案,并且本发明只被限于所附权利要求的条款和权利要求书赋予的等价物的全部范围。
Claims (14)
1.一种用于微电子设备的组合物,其包括
(a)可热固化的树脂体系,该体系含有至少一种环氧树脂和脂肪胺的混合物,
(b)导电性填料,
(c)腐蚀抑制剂,
(d)固化剂或催化剂,
(e)任选的有机溶剂,和
(f)任选的粘合促进剂、酚醛树脂、流动添加剂和流变改良剂中的一种或一种以上,其中环氧树脂中环氧官能团与脂肪胺中胺官能团的比率大于1。
2.根据权利要求1的组合物,其中对于100重量%的总量,
(a)所述混合物的含量是约10到约90重量%;
(b)所述导电性填料的含量是约30到约90重量%;
(c)所述腐蚀抑制剂的含量是至多约10重量%(但不是0%),
(d)所述固化剂或催化剂的含量是固化剂与树脂的比率不超过约10重量%(但不是0),
(e)所述有机溶剂的含量是约0到约10重量%,和
(f)粘合促进剂、流动添加剂和流变改良剂中的一种或一种以上,其含量是约0到约5重量%。
3.根据权利要求2的组合物,其中树脂的含量是约10到约60重量%。
4.根据权利要求2的组合物,其中固化剂的含量是约1到约5重量%。
5.根据权利要求2的组合物,其中腐蚀抑制剂的含量是约0.1到约5重量%。
6.根据权利要求2的组合物,其中导电性填料的含量是约40到约90重量%。
7.根据权利要求1的组合物,其中导电性填料选自银、铜、金、钯、铂、碳黑、铋、锡、铋-锡合金、碳纤维、石墨、铝、铟锡氧化物、镀银的铜、镀银的铝、镀金属的玻璃球、镀银的纤维、镀银的球、掺锑的锡氧化物或它们的混合物。
8.根据权利要求8的组合物,其中导电性填料是银。
9.根据权利要求1的组合物,其中混合物含有约20到约100重量%的环氧树脂、约0到约99重量%的与环氧树脂中环氧化物的含量化学等价量的脂肪胺和约0.1到约10重量%的交联剂。
10.根据权利要求1的组合物,其中树脂选自双酚A和双酚F的单官能和多官能的缩水甘油醚、脂肪族和芳香族环氧树脂、饱和的和不饱和的环氧树脂或脂环族环氧树脂或它们的混合物。
11.根据权利要求1的组合物,其中腐蚀抑制剂选自1,10-phenathiodine、吩噻嗪、苯并三唑、苯并咪唑、巯基苯并噻唑、二氰胺、3-异丙氨基-1-丁炔、炔丙基喹啉鎓溴化物、3-苄氨基-1-丁炔、二炔丙基醚、二炔丙基硫醚、己酸炔丙酯、二氨基庚烷、菲咯啉、胺、二胺、三胺、六亚甲基酰亚胺、十亚甲基酰亚胺、六亚甲基亚胺苯甲酸酯、六亚甲基亚胺-3,5-二硝基苯甲酸酯、六亚甲基四胺、d-肟基-b-乙烯基奎宁环、苯胺、6-N-乙基嘌呤、1-乙氨基-2-十八碳烷基咪唑啉、吗啉、乙醇胺、氨基苯酚、2-羟基喹啉、6-羟基喹啉、8-羟基喹啉、吡啶及其衍生物、喹啉及其衍生物、吖啶、咪唑及其衍生物、甲苯胺、硫醇、苯硫酚及其衍生物、硫化物、亚砜、硫代磷酸酯、硫脲和哌啶。
12.根据权利要求11的组合物,其中腐蚀抑制剂是8-羟基喹啉。
13.根据权利要求1的组合物,其中有机溶剂是缩水甘油基醚、1,4-丁二醇二缩水甘油醚、乙烯基醚、亚乙基乙烯基醚、乙烯基酯,亚乙基乙烯基酯、丙烯酸脂、甲基丙烯酸甲酯和丁基卡必醇中的一种或一种以上。
14.根据权利要求1的组合物,其中催化剂或固化剂是咪唑。
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- 2004-02-18 KR KR1020057016031A patent/KR101170395B1/ko not_active IP Right Cessation
- 2004-02-18 EP EP04712396A patent/EP1597332B1/en not_active Expired - Lifetime
- 2004-02-18 AT AT04712396T patent/ATE394459T1/de not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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CN100393836C (zh) | 2008-06-11 |
DE602004013544D1 (de) | 2008-06-19 |
KR20050105502A (ko) | 2005-11-04 |
WO2004078870A1 (en) | 2004-09-16 |
US20040169162A1 (en) | 2004-09-02 |
EP1597332B1 (en) | 2008-05-07 |
US7108806B2 (en) | 2006-09-19 |
JP4602970B2 (ja) | 2010-12-22 |
JP2006524286A (ja) | 2006-10-26 |
EP1597332A1 (en) | 2005-11-23 |
KR101170395B1 (ko) | 2012-08-01 |
ATE394459T1 (de) | 2008-05-15 |
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