CN1120850A - 用于电子器件的可再加工的聚(乙烯-乙烯醇)粘合剂 - Google Patents

用于电子器件的可再加工的聚(乙烯-乙烯醇)粘合剂 Download PDF

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CN1120850A
CN1120850A CN94191697A CN94191697A CN1120850A CN 1120850 A CN1120850 A CN 1120850A CN 94191697 A CN94191697 A CN 94191697A CN 94191697 A CN94191697 A CN 94191697A CN 1120850 A CN1120850 A CN 1120850A
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binder
electroconductibility
reprocessing
temperature
composition
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J·-M·P·普佐尔
P·B·霍格顿
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3M Co
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Minnesota Mining and Manufacturing Co
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Abstract

本发明提供适合用来粘接电子器件的可二次加工、半晶质、热塑性粘合剂组合物。这种较好以粘合剂膜形式提供的粘合剂组合物包括一种或多种聚(乙烯-乙烯醇)共聚物。

Description

用于电子器件的可再加工的聚(乙烯-乙烯醇)粘合剂
                   发明的领域
本发明涉及粘合剂组合物，特别涉及具有尤其适用于电子行业的性能的聚(乙烯-乙烯醇)粘合剂组合物。具体地说，这种粘合剂组合物当被用于集成电路、硬性电路或软性电路时，具有二次加工或可修整性。更具体地，这种粘合剂组合物适合用作将半导体装到导电基底上的倒装片直接粘合膜。
                   发明的背景
电子装置，象袖珍式计算器、电子表和便携式计算机，要用到各种各样以集成电路元件为基础的半导体(器件)。一般来讲，半导体是先装配在晶片板上然后再切成单个的片子(Chip)的。这些片子典型地被做成单片封装，然后再借助某种低温焊接装到电路板上。但是在某些场合，为了缩小产品尺寸和提高产品性能，直接把未封装的片子装到电路板上。预计，这种“倒装片”封装法的效益随着输入-输出次数、时钟码速率频率以及功率密度的不断加大将会提高。
用于倒装片连结的最普遍的结合手段是焊球互接(solder bumpinterconnection)。采用这种方法，金属焊接接头既提供片子和基底间机械的也提供电气的互接。这种方法存在着对间距方面的内在限制，同时对片子与基底之间热膨胀系数(CTE)和弹性模量上的失配也极其敏感。这种失配造成焊接接头内的高剪应力，这会有损于整个组件的可靠性。参见R.R.Tummalla和E.J.Rymaszewski，<微电子技术封装手册>，(Van Nostrand Reinhold，1989)PP280-309；366-391；和K.Nakamura，＜Nikkei Microdevices＞，1987年6月。重大事故的直接原因就是因这种应力导致在焊接头或片子内部出现任何裂纹。
U.S.专利号4,749,120(Hatada)和U.S.专利号4,942,140(Dotsvki)披露一种焊球倒装连接的可替代方法。上述参考文献披露了保持片子与基底间压力接合的电气连接的液态、可固化粘合剂体系。界面处粘合剂的存在倾向于缓解剪应变，从而提供了更大的容许热膨胀系数(CTE)和弹性模量失配的容量。可是，要具有实用性，该粘合剂既使在这种应力和100℃以上的温度条件下仍必须能承受稳定接触力。这些参考文献认为必须使用高度可交联性粘合剂才能提供这样程度的稳定性。
对于液态粘合剂的一个担心之处在于，为保证放置模具的期间整个模接合表面是湿润的，必须施用过量的粘合剂，而结果过量粘合剂会流到不希望有粘合剂的部位。而且，预料象这种可固化材料要再加工不是不可能就是很困难。
为解决与液态体系有关的问题，粘合剂可以以自持膜的形式供应。这种膜能按照模板的尺寸准确地裁切，这就为在准确的模板部位进行模接合提供精确数量的粘合剂。U.S.专利号4,820,446(Prud′homme)提出一种能修整的电子行业用热塑性粘合剂。但是，该粘合剂及其他相关的粘合剂的一个缺点是，他们往往表现出在较高的应力和温度下的高变形性，这就造成其接触稳定性差。故而，这种粘合剂只能应用在应力不大的场合。从而使这种粘合剂几乎专门用来把重量轻的软性电路粘到其他器件上，因为在这些场合下热应力极小。
虽然某些高可交联性、热固性粘合剂膜在高应力场合有足够的性能，但这些粘合剂的缺点是不能再加工。U.S.专利号4,769,399(Scheng)披露象这样一种在高温下具有出色剪切强度的不可再加工粘合剂的一例。
Pujol等，U.S.专利号5,143,785和共同未决的专利申请序列号07 816 854(Hall等)披露了用于电子行业的可再加工、可交联体系。这种体系提供了非常理想的可再加工性能，可惜，若是一种非反应性的可再加工粘合剂就将提供进一步的优越性，例如更长的存放期。
U.S.专利号5,061,549(Shores)描述适合电子行业用的热活性粘合剂膜。该粘合剂的主要成分是一种Vicat软化点为70-280℃的热塑性聚合物。Shores列举了数种热塑性聚合物(等3列，第14-48行)然而却未能认识到半晶质聚合物的有利效果。虽然非晶态热塑性聚合物确实提供了用于粘合电路器件时粘合时间短和可修整/可再加工性，但是他们不具有为提供高尺寸稳定性所需要的玻璃转化温度(Tg)以上的强度，也不具有能在粘合过程中产生充分润湿的陡峭的熔点(Tm)附近粘度-温度梯度。
欧洲专利申请号302,620Az(Exxon Chemical公司)披露以聚(乙烯-乙烯醇)为主要成分辅以异氰酸酯和增粘剂的可交联热熔粘合剂。象热固性粘合剂体系一样，这些粘合剂一旦被交联便不能再加工。而且，这种粘合剂的固化时间超过15分钟，这对电子消费产品的高效大量生产是不理想的。H.Kempe和M.Kempe在＜PlasteKautsch＞，34，210-211，1987中简述了以聚(乙烯-乙烯醇)为钢的粘合剂涂层的应用。
除热望和热固性粘合剂体系之外，用于电气互接可能有兴趣的是热望一热固性共混物。这种混合物旨在改善热固性材料的高温性能和/或改善热固性材料的断裂韧性。参见U.S.专利号3,530,087(Hayes等)；以及R.S.Bauer，“韧化高性能环氧树脂：用热塑性塑料的改性”，第34届美国材料及加工工艺进展协会国际会议论文集，1989，5月8-11日。
然而，尽管迄今一直沿用热塑性粘合剂、热固性粘合剂以及其混合物，但是大多数目前已知的互连手段当应用在要求苛刻的场合，例如FDCA(联邦国防通讯管理局)用途时，均未能充分地解决上面提到的问题。因此，依然需要一种非反应性、可再加工的粘合剂，它既允许在不太高的温度下快速粘合而且还具有足以耐受很大应力和/或高温，至少在使用温度范围内，的模量。这种粘合剂还应当在加工温度下是可再加工的，这种加工温度足以低到当取下片子时不致损坏基底。对这种粘合剂还要求：具有在室温下较长的存放时限(即存放稳定)；在很宽的粘接温度范围内有很低的粘度以便提供良好流动性；能耐受最高85℃和85％相对湿度的条件；而且能做成在重新配置时的设计操作温度下基本无粘性的薄膜供应。
                          发明的概要
本发明提供一种可再加工热塑性粘合剂组合物，包括一种或多种适合于电子器件粘接的半晶质聚合物。这种粘合剂组合物，较好提供不粘或稍带粘性的粘合剂薄膜，它包括聚(乙烯-乙烯醇)共聚物，共聚物的玻璃转变温度Tg为30°-70℃，较好40°-60℃；结晶温度Tc为115°-155℃，较好125°-145℃；熔点Tm典型地在130°-170℃之间，较好在140°-160℃之间。图2表示的是Tg、Tc和Tm分别做为半晶质、热塑性共聚物中乙烯和乙烯醇的相对数量的函数的曲线。
本发明粘合剂组合物较好包括硅烷偶联剂，还可以包含导电性颗粒以及其他添加剂，尤其是被选用来控制粘合剂膜室温“发粘”的添加剂。
本发明粘合剂组合物在固化粘合剂组合物的Tc以下20℃的温度下的模量大于50MPa，较好大于100MPa。
本发明还提供在导电表面之间生成一种可再加工粘合剂结合从而构成导电粘合复合物的方法。该方法包括的步骤是：提供本发明可再加工粘合剂膜；提供有一个或多个导电粘合点的导电基底；提供一个或多个导电器件，每器件具有一个导电粘合表面；将可再加工粘合剂置于每个导电粘合点和每个导电器件之间；施加充分的热量和/或压力并保持充足的时间，最后在每个导电粘合点和每个导电器件之间生成一种可再加工粘合剂结合。该可再加工粘合剂在粘合剂膜Tc以下20℃的温度下的模量大于50MPa。导电基底典型地为印刷电路板，具有适合于同集成电路、软性电路、硬性电路等粘接的导电粘合点。
本发明粘合剂要求的粘合时间在200℃或更低的温度，较好在185℃或更低的温度典型地短于30秒，较好短于20秒。
本文所用“半晶质聚合物”的定义是表现出晶质行为的聚合物。半晶质聚合物既表现出晶体熔化也表现出玻璃态转变温度。例如见0dian著<聚合原理(第二版)>，John Wiley&Sons，New York，(1981)，25及30页。
“熔融温度”在此指在半晶质聚合物中发生固态到液态的相转变时的温度。
本文所指的“结晶温度”或者“再结晶温度”是当半晶质聚合物内发生从液态到固态的相转变时的温度，因为在半晶质聚合物内存在着固液间相转变滞后，这依据达到这种转变所经由的温度而定，即是加热的固态向液态转变还是冷却的液态向固态转变。
本发明可再加工粘合剂可以典型地在200℃以下，较好170℃以下被整体去除。整体去除本发明可再加工粘合剂典型地在Tm之下进行，因为使用过分高的温度可能有损于基底或它上面的导电器件。为去除残留的残余物可能还需要使用适当的溶剂。较好的是，该可再加工粘合剂膜被从选自由下面构成的组的基底上去除：导电材料，例如铜、金、银、铝、镍和焊锡；电介质，例如陶瓷、玻璃、硅以及环氧树脂/玻璃层合物；以及聚合物膜，例如聚酰亚胺和PET。
                     附图说明
图1是上面可以施用本发明粘合剂组合物的集成电路、印刷电路板等的示意性平面视图；
图2画出了作为乙烯含量函数的温度(Tc、Tm、Tg)的曲线；以及
图3画出了作为本发明粘合剂温度函数的弹性模量。
                    详细说明
本发明可再加工粘合剂组合物可以用一种或多种的半晶质热塑性聚(乙烯-乙烯醇)聚合物制造，聚合物的Tg为30°-70℃，Tc为115°-155℃，以及Tm为130°-170℃。该粘合剂膜在整个要求的使用温度范围具有足够高的剪切强度，而其剪切强度在其Tc以上却下降得足够迅速以致到达熔融温度Tm时该粘合剂具有可再加工性。这里所说“剪切强度”系指为将片子从玻璃基底上剪切地拆离所需要的力。
一般地本行业的专业人员不会选乙烯和乙烯醇的共聚物作为粘合剂组合物聚合物成分，因为这些共聚物本质上是“非粘性”的。这类共聚物以其低大气氧透过率著称，因而被用作食品的包装材料，例如用来做塑料猫食瓶用树脂中的成分。用于电子模板组装的粘合剂一般承受异常高剪力，原因是微电子电路片子、粘合剂以及与片子粘结的基底的热膨胀系数(CTE)之间存在“失配”。当在这种高剪力粘合剂应用场合中使用非晶态热塑性聚合物时，通常要求聚合物Tg超过使用环境中会碰到的最高温度(Tmax)，以便保证有充分的抗蠕变性，保持片子与基底之间的电接触。正是出于这个原因，许多电子模板组装粘合剂都要经“固化”(化学交联)以便把Tg提高到Tmax以上。
在用于本发明粘合剂的半晶质聚合物中，与应力松弛相关的有害蠕变发生在再结晶温度(Tc)以上，且Tc又高于Tg。因此，半晶质聚合物一般地提供具有比非晶质热塑性聚合物获得的为高的Tmax值的粘合剂。较好的用于可再加工粘合剂的半晶质聚合物是那些其模量在再结晶温度(Tc)和熔融温度(Tm)之间锐减的半晶质聚合物，正如图3所表明的那样。
本发明粘合剂为膜型材料，典型地敷在防粘衬里(release liner)上。由于按这种配方的聚合物的热塑性特性，这种组合物为快速粘合的粘合剂而且是可修整的。尽管Tg比较低，但由于聚(乙烯-乙烯醇)是半晶质的，所以在高温下仍能保持高度尺寸稳定。这种聚合物的结晶温度在115℃到155℃之间，这就保证了再结晶以后有强的键合内聚力。这种半晶质特性还提供了Tm附近陡峭的粘度-温度梯度，从而在粘合操作过程中提供极好的润湿，见图3。
同样较好地，本发明可再加工粘合剂膜在室温下能存放至少一个月保持稳定，在粘合温度下具有足够低的粘度从而提供了良好的流动性能，在不太高的温度下，例如145℃-225℃，更好在150-215℃，且最好在160℃-200℃范围内能迅速粘合，此外在最高85℃和85％相对湿度的条件下能基本上保持稳定。
本发明可再加工粘合剂尤其适用于电子行业。许多种电子器件包含一个或多个的硅片。这些片子一般为矩形或正方形且尺寸很小，倒如单边只几毫米(mm)。每只片子有至少一个，且经常是许多导电端子，都必须同基底上的导电通路电气连接，以便构成一个所需要的完整电路。这些通路可能包括粘在基底上的金属薄膜成条，例如银、金、铜等，也可以由粘合剂或油墨条构成，这些条本身可以是导电的也可以凭着其中含有的导电颗粒而被赋予了导电性。
本发明可再加工粘合剂作为一种FDCA粘合方法中的组装手段尤其有用。FDCA粘合方法直接把裸片粘到导电基底上。某些片子带有焊球(焊球片子)，它们是用来桥接粘合剂层并直接与基底相连。不带焊球的片子是典型地采用内部充满导电颗粒的粘合剂来粘结的，导电颗粒便构成了基底和片子之间导电通路。FDCA粘合方法可见诸于“关于用于第一级微电子互连的粘合剂的应用调查(Investigations Into The Use of Adhensives For Level-1Microelectronic Interconnections)”P.B.Hogerton等人，<电子封装材料科学>专题论文集，4月24-29日，1989年。
工业上粘合温度通常介于145℃到225℃，更通常地介于160℃到200℃。当使用先有技术粘合剂时，粘合时间可从数分钟到几小时，然而，作为工业上可行的大批量电子器件组装生产线而言，本发明粘合剂只需要30秒或更短时间，较好不到20秒的粘合时间。
本发明的可再加工粘合剂组合物较好以薄膜形式提供，在设计的操作温度下这种薄膜不发粘或稍带粘性。这种粘合剂膜比液态或糊状粘合剂优越之处包括容易操作、片子套准精确、以及能在待粘片子上配置数量恰到好处的粘合剂，以避免浪费。
加工温度是用粘合剂把片子粘到基底上去时的温度。该温度必须足够低以便在加工期间片子或基底不受到损伤，又必须足够高以便粘合剂能充分地把片子粘到基底上。
图1是本发明粘合剂组合物尤其适用的集成电路、印刷电路板等的示意性平面视图。画出的印刷电路板10具有软性电路端子20、印刷电路板端子30和印刷电路板端子40。本发明粘合剂，例如可用于将软性电路50与软性电路端子20粘接；将印刷电路板60与印刷电路板端子30粘接；以及将TAB，即带状自动粘接，引线框70与印刷电路板端子40粘接。
TAB引线框72如图示地被粘接到印刷电路板10上。印刷电路板60具有倒装片61-66。倒装片66在图上表示的是被装到印刷电路板60之前的位置。本发明粘合剂可以被用来将倒装片61-66粘到印刷电路板60上。图1上还表示出一块液晶显示片80。该液晶显示片80上粘有软性电路50。如图示，倒装片90和TAB引线框100也同液晶显示片80粘接。
图2画出了作为本发明粘合剂中乙烯含量的函数的熔点(Tm)曲线A、结晶温度(Tc)曲线B以及玻璃转化温度(Tg)曲线C。这张图只不过是典型的本发明粘合剂的一个一般化例子，且绝无给可以使用的共聚物或粘合剂做一界定的意图。图2中所示粘合剂在56％乙烯处的Tg是55℃、Tc是142℃，而在180-230℃区间具有10-30秒的粘合时间。使用的共聚物分子量与熔融粘度是相关的，正如图2中的例子所表明的。
图3画出的是作为温度(℃)函数的本发明粘合剂的弹性模量(E′)的曲线。上面的模量数值M对应于100MPa，下面的模量线对应于50MPa。本发明粘合剂在Tc以下20℃处的模量大于50MPa。图3中温度线B对应于粘合剂Tc以下20℃。图3中线A代表粘合剂的Tc。图3中模量对温度做出的曲线200表明，该粘合剂在Tc以下20℃处的模量大于100MPa。
                     偶联剂
本发明粘合剂组合物还可以包含偶联剂以促进粘合剂同给定基底的粘合。硅烷偶联剂较好，且其数量较好为组合物的0.1-5％(重量)，更好1％(重量)。
较好的硅烷偶联剂具有分子式：
                 P(4-n)Si2n其中：
P代表至多含12个碳原子的有机取代基，例如丙基，它应具有官能性取代基象巯基、环氧基、环氧丙氧基(glycidoxy)、烯丙酰、异丁烯酰和氨基；
Z代表可水解基团，例如烷氧基，较好是甲氧或乙氧基；以及
n是1、2或3，较好是3。
除硅烷偶联剂之外，钛酸酯和锆酸酯偶联剂亦可使用。参见，例如J.Cromyn的<结构粘合剂>，有关偶联剂一章，由A.J.Kinloch编，Elsevier应用科学出版社出版，1986，269-312页。第270页提供了环氧和胺硅烷偶联剂的例子。第306-308页讨论了使用钛酸酯和锆酸酯偶联剂。
另一些添加剂
按据需要，可在该粘合剂组合物中加入一些导电颗粒，包括例如U.S.专利号4,606,962(Reylek等)和4,740,657(Tsukagoski等).Reylek描述了导电、热导电颗粒，其在粘合剂粘合温度下变形性至少不亚于基本上纯净的球形银粒子。颗粒的厚度超过颗粒之间粘合剂的厚度。Reylek描述的颗粒较好基本上呈球形且由象银或金，或者一种以上的金属，例如“一种焊料表层与一种或者熔点更高的金属核(如铜)或者一种非金属核”(第4列，第20-21行)，制成。上述以及其他导电颗粒(例如非球形和/或厚度(直径)小于粘合剂前述厚度的)均适用于本发明粘合剂组合物。
含于本发明粘合剂组合物中的传导性颗粒可以无规地分散于其中，也可以按要求的构形排列成均一的阵列。为节省导电颗粒的用量，可以让颗粒仅分布在准备与各个导体接触的粘合剂膜区域。
可以在粘合剂组合物中加入其他填料。使用填料可以提供的好处是提高粘合力、提高模量和降低热膨胀系数。有用的填料包括但不限于：硅石颗粒、硅酸盐颗粒、石英颗粒、陶瓷颗粒、玻璃珠、惰性纤维以及云母颗粒。较好地，该填料是微晶硅石颗粒。
重要的是，粘合剂组合物的离子性杂质含量要低。电子工业规定粘合剂萃取性离子含量要低。规定包括Cl-、Na+、K+和NH4 +不得超过10ppm。这样极低的离子含量对防止金属被腐蚀和将粘合剂的传导性，除通过存在的传导性金属颗粒之外，维持在尽量低的水平是重要的。
下面给出的例子不过为说明起见，并非界定，全部百分数指重量而言。
实施例1-6
按下述方法制备了本发明粘合剂组合物，各种成分及数量载于表1。首先把聚合物溶解于甲醇和水，温度60℃。趁热在溶液中加入硅石和传导性颗粒。用刮刀涂布机把粘合剂组合物涂到TeflonTM膜上。粘合剂涂层厚度借助刮刀和衬底之间的距离调节设定在20-40μm之间。将粘合剂膜在50℃下干燥1小时然后存放在干燥器中。
                         表1
                    实施例1-6的配方成分
              实施例1   实施例2   实施例3   实施例4   实施例5   实施例6聚(乙烯-乙烯醇)    14.92               15.25     15.17               12.42SCE1051聚(乙烯-乙烯醇)                                            11.09EPG1151聚(乙烯-乙烯醇)             19.284408M32硅石L207A3         23.30             23.79     23.67      19.28      37.27环氧丙氧基丙基三    0.45    0.60                 0.46       0.39      0.62甲氧基硅烷(3-GPMS)甲醇                54.31   72.17     55.47     55.24      69.24      45.22水                  5.37    7.95      5.49      5.46                  4.47金/镍/聚苯乙烯传导性颗粒4          1.651.由Eval公司，美国，Lisle，Illinois提供2.由杜邦公司提供的Selar OH3.Novacite.由Malvern Minerals公司提供4.Fine Pearl，由Sumitomo Chemical<住友化学>提供。
实施例7
通过模板剪切强度的测定评估了实施例1、2、4、5和6中每一个的粘合力。该试验的目的是测定将片子剪切剥离基底所需的外力。该粘合强度是在一台剪力试验机上对粘在25mm×25mm×1mm的玻璃滑动片上的2mm×2mm×1mm玻璃片子测定的。
采用了下列的方法把片子粘到滑片上去。粘合剂是这样被转移到片子上去的，将片子放到膜上然后借热活化和压力使粘合剂变粘。当片子被从防粘衬底上取下时，上面已覆盖了一层均匀的粘合剂。随后把片子放到滑片上。粘合是在一台模板粘合机上，在180℃以及2.5MPa压力下维持数秒钟完成的。
微电子行业有关选择和使用粘合剂的规定要求至少具有6MPa的粘合强度(MIL(军用规范)标准883C，方法5011)。示于表2的结果表明，用聚(乙烯-乙烯醇)粘合剂组合物获得了高粘合力。
                   表2
聚(乙烯-乙烯醇)粘合剂组合物的粘合力
粘合剂实施列号    剪切强度(MPa)
      1               16.5
      2               11.7
      4               16.3
      5               12.8
      6               18.0
实施例8
按倒装片直接安装法采用实施例1-6的粘合剂组合物把硅片粘到载于玻璃基底上的电路上去。试验片子(0.5mm×7mm×7mm)上载有120个金焊接点(焊点节距：0.2mm)用于电气连接。电路是采用铟锡氧化物配置的以允许做4探头电阻测量。铟锡氧化物为0.1μm厚，表面电阻为20Ω/每块。
粘合剂膜转移到片子的有效面上的方法是，将膜放在一热板表面加热到150-180℃然后稍施压力将之压合在片子上。经数秒钟后，将层合构造从热板上取下。
在片子与衬底上的导电电极套准之后，就进行最后的倒装片在玻璃衬底上的安装。粘合是通过在200℃。加压(约10MPa)下保持30秒钟完成的。
用4探头法测量了互接电阻。测定了平均、最小和最大电阻。表3的数据是测得的电阻值。因为在测量时涉及到2个接点，故这些数据代表了2倍的实际互接电阻；它们还包括玻璃基底上的铟锡氧化物电路的电阻以及硅片上连接金接点的铝条的电阻。考虑到上述诸因素，当一个值小于2Ω时就表明互接良好。
            表3
   玻璃上倒装片的互接电阻
粘合剂     R平均.   R最小.   R最大.
实施例号    (Ω)    (Ω)     (Ω)
   3         1.0     0.6      2.1
   4         1.4     0.8      2.5
   5         1.8     0.6      3.4
表3的数据表明，当采用聚(乙烯-乙烯醇)组合物把倒装片粘在玻璃上时获得了良好的电气连接。
实施例9
在热老化和湿老化条件下对得自实施例8的试样(实施例3和4)做了环境试验。
在1000小时的100℃热老化条件下，实施例3的粘合剂组合物保持了电气连结未发现断路。
在1000小时的60℃、95％相对湿度(HR)湿老化条件下，实施例4的粘合剂组合物保持了电气连接未发现断路。
实施例10
采用了实施例1的粘合剂组合物把软性电路粘到印刷电路板上。软性电路是由宽10mm×厚50μm的聚酰亚胺带制成，上面用铜做了金属喷镀并用一层12μm厚的铅-锡焊料保护起来。带上有17条间隔为0.4mm(节距)的导电线。印刷电路板是FR-4环氧玻璃层合物，做了铜以及12μm厚铅-锡焊料金属喷镀，节距与上面近似。
借助热活化和稍施压把一片3mm×8mm的粘合剂膜转移到软性电路上。最后把带子放到电路板上，套准条纹，在带子上加2MPa的压力同时把粘合剂加热到200℃保持30秒钟便完成了在电路板上的粘合，整个过程是采用热棒式粘合机进行的。
用4探头法测量了互接电阻。测定了平均电阻、最小电阻和最大电阻。表4和表5所示数据是测得的电阻。因为在每个试样上做了2个粘合点，故这些数据代表2倍的实际互接电阻；数据还包括电路板电阻和软性电路电阻。考虑到上述诸因素，数值小于0.5Ω时便表明互接良好。
               表4
     软性电路与电路板的互接电阻
 粘合剂    R平均.   R最小.  R最大.
实施例号    (Ω)    (Ω)    (Ω)
   1        0.21     0.19   0.24
表4数据表明，当采用聚(乙烯-乙烯醇)组合物把软性电路粘到电路板上时，获得了良好的电气连接。
实施例11
采用了下列方法试验粘合剂的可修整性。按照实施例10所述制备了试样。把选自上述试样的环氧玻璃层合物基底加热至150℃，在此温度下很容易地把软性电路剥离。然后把电路板上的残留粘合剂揩净。按照实施例10所述的粘合步骤把一新的软性电路用一片新的粘合剂在200℃下经30秒钟粘到这块电路板上。再加工前、后所测得的连接数据列于表5。
                  表5
         再加工前后的互接电阻粘合剂实施例号     再加工前R        再加工后R
           R平均.R最小.R最大.R平均.R最小.R最大.
            (Ω) (Ω)  (Ω)  (Ω)  (Ω)  (Ω)
   1       0.23  0.19  0.26  0.23  0.21  0.25
经再加工后，未发现显著的差异。又获得了良好的电气连接。该聚(乙烯-乙烯醇)组合物是可修整的粘合剂。
实施例12
对取自实施例10的试样在湿老化、热老化和热循环条件下进行了环境试验。经1000小时的测试后，测量了互接电阻。
                 表6
软性电路与电路板在环境试验后的互接电阻粘合剂                       R平均.    R最小.    R最大.实施例号    试验              (Ω)     (Ω)      (Ω)1      热循环-40，+105℃*    0.24     0.21      0.261      热循环-55，+125℃*    0.26     0.23      0.291      热老化100℃           0.22     0.20      0.251      热老化125℃           0.28     0.24      0.311      湿老化60℃，95％RH    0.23     0.21      0.261      湿老化85℃，85％RH    0.26     0.21      0.351      湿老化60℃，95％RH    0.26     0.24      0.29
    15V偏压*6小时循环
表6结果表明，未发生接触电阻方面的显著恶化。聚(乙烯-乙烯醇)组合物在环境试验条件下表现出高稳定性。
下面的对照例说明，只采用非晶质、热塑性聚合物作为高分子量树脂成分的膜型粘合剂，在典型应用中遇到的极端温、湿度条件下不能保持适当的低接触电阻。
对照的非晶质聚合物A
用牌号为B76的热塑性聚(乙烯醇缩丁醛)树脂制备了30微米厚膜形粘合剂。B76的重均分子量约为50,000，Tg为50℃，由Monsanto(孟山都)Chemical Corp.，Saint Louis，Mo，提供。此薄膜粘合剂是由70％(固体)的溶液浇注成的，溶液的制法是，先将B76聚合物溶解于二甲苯，随后顺序加入异丙醇和水，生成的溶液其中溶剂相占95％(重量)(二甲苯∶异丙醇为60∶40)而水占5％(重量)。粘合剂膜是通过把聚合物溶液刮刀涂布在TeflonTM膜的衬底上制备的。调节刮刀与衬底的间距使粘合剂的厚度调整在20-40μm之间。粘合剂在80℃干燥1小时，并储存在干燥器内以备粘合及测试。
按照实施例8的步骤将此薄膜粘合剂用来把硅试验片子粘到铟锡氧化物镀层的玻璃衬底上，然后进行试验。所用的粘合条件如下：温度＝185℃，压力＝140KPa，粘合时间＝30秒。试验结果示于表7。
                表7
      倒装片与玻璃的互接电阻
室温老化     R平均.    R最小.    R最大.
(小时)        (Ω)     (Ω)       (Ω)
试样1∶0      5.1      2.0       15.4
试样1∶15     6.9      2.4       33.9
试样2∶0      8.0      2.3       53.8
试样2∶15    10.0      3.0      2.0E＋16
(3断路)
鉴于室温接触电阻不稳定，B76被判定为不适合用作电子模板安装粘合剂，于是便没有再进行类似实施例9的更为苛刻的环境试验。
对比的非晶质聚合物B
用代号为B98的热塑性聚(乙烯醇缩丁醛)树脂制备了28μm厚的薄膜粘合剂。B98的重均分子量为37,000，Tg65℃，由Monsanto Chemical Corp.，Saint Louis，MO，提供。该薄膜粘合剂是由85％(固体)溶液浇注成的，溶液的制备是，首先把B98聚合物溶解于二甲苯，继而顺序加入异丙醇和水，生成的溶液中溶剂相占95％(重量)(二甲苯：异丙醇为60∶40)而水占5％(重量)。薄膜粘合剂是用刮涂布将聚合物溶液涂布到TeflonTM膜衬底上制备的。粘合剂的厚度借助调节刮刀与衬底的间距被调整在20-40μm之间。将粘合剂在80℃下干燥1小时然后储存在干燥器中以备粘合及试验。
用粘合剂膜按实施例8的步骤把试样硅片粘到铟锡氧化物涂层的玻璃衬底上。采用的粘合条件如下：温度＝275℃，压力＝70KPa，粘合时间＝10秒。试验粘合物自然冷却到35℃然后解除粘合压力。试验结果载于表8。
               表8
      倒装片对玻璃的互接电阻
室温老化   R平均.  R最小.  R最大.
(小时)     (Ω)    (Ω)    (Ω)试样1∶0        1.6     0.6     7.2试样1∶22       1.8     0.6     8.2
经判定，B98薄膜粘合剂已通过室温老化试验，故继而对其进行了类似于实施例9的环境试验。环境测试的条件如下：温度＝60℃，相对湿度＝95％，时间＝73小时。环境老化试验结束后，在原来的60对接点中只有3对的接触电阻小于100,000Ω，故而判定B98热塑性聚合物不适合用作电子模固定的粘合剂。
本专业的行家将很清楚，可以对本发明做出多种多样的修改和变换仍不偏离本发明的范围和精神。

Claims (10)

1.一种可再加工的热塑性粘合剂组合物，包括一种或多种Tg在30°-70℃之间，Tc在115°-155℃之间的半晶质聚(乙烯-乙烯醇)共聚物，和至少一种选自传导性颗粒、偶联剂和填料的添加剂，这样，所说粘合剂组合物便具有在粘合剂组合物Tc以下20℃大于50MPa的模量，且提供MILSTD883C，方法5011测定大于10MPa的粘合强度。
2.权利要求1的可再加工热塑性粘合剂组合物，其中所说组合物的Tg为40℃-60℃，Tc为125°-145℃。
3.权利要求1的可再加工热塑性粘合剂组合物，其中所说粘合剂膜在固化粘合剂组合物的Tc以下20℃温度时的模量大于100MPa 。
4.权利要求1的可再加工热塑性粘合剂组合物，包含0.1-5％(重量)的硅烷偶联剂。
5.权利要求4的粘合剂组合物，其中所说硅烷偶联剂具有下列(通)式：
       P(4-n)SiZn其中：
P代表至多含12个碳原子的有机取代基，例如丙基，它应该具有选自由巯基、环氧基、环氧甲氧基、烯丙酰、异丁烯酰和氨基构成宫能取代基部分；
Z代表一个可水解基团，以及
n是1、2或3。
6.一种用于在两个导电表面间形成可再加工粘合剂结合从而构成一种导电性粘合复合物的方法，包括下列步骤：
(a)提供一种符合权利要求1的可再加工粘合剂膜；
(b)提供有一个或多个导电性粘合点的异电性基底；
(c)提供一个或多个每个均具有导电性粘合表面的导电性器件；
(d)把所说可再加工粘合剂置于每个所说一个或多个导电性粘合点和所说一个或多个导电性器件的每个所说导电性粘合表面之间；以及
(e)施加足够的热量和/或压力，保持足够的时间以便在每个导电性粘合点和每个导电性粘合表间之间形成一种可再加工粘合剂结合；其中每个所说一个或多个可再加工粘合剂结合在该粘合剂膜Tc以下20℃温度具有大于50MPa的模量。
7.权利要求6的方法，其中所说导电性基底是印刷电路板。
8.权利要求7的方法，其中所说一个或多个导电性器件选自集成电路或软性电路。
9.权利要求6的方法，其中所说导电性粘合表面包括选自由金、银、铜、铝、镍以及焊料构成的组的材料。
10.权利要求6的方法，其中所说可再加工粘合剂膜被加热到介乎于145℃和225℃之间的温度以形成所说可再加工粘合剂结合，所说热量的施加时间少于30秒钟。
CN94191697A 1993-04-05 1994-02-22 用于电子器件的可再加工的聚(乙烯-乙烯醇)粘合剂 Pending CN1120850A (zh)

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CN1303660C (zh) * 2001-10-23 2007-03-07 国家淀粉及化学投资控股公司 用粘合剂薄膜将半导体管芯粘结到衬底的半导体封装方法

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US7776940B2 (en) 2005-12-20 2010-08-17 3M Innovative Properties Company Methods for reducing bond strengths, dental compositions, and the use thereof
US7896650B2 (en) 2005-12-20 2011-03-01 3M Innovative Properties Company Dental compositions including radiation-to-heat converters, and the use thereof
US8026296B2 (en) 2005-12-20 2011-09-27 3M Innovative Properties Company Dental compositions including a thermally labile component, and the use thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1303660C (zh) * 2001-10-23 2007-03-07 国家淀粉及化学投资控股公司 用粘合剂薄膜将半导体管芯粘结到衬底的半导体封装方法

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