CN1240470A - 管芯连接粘合剂组合物 - Google Patents
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Abstract
提供了将半导体器件连接到衬底上的新颖的热可再加工管芯连接粘合剂组合物。所述组合物包括:(a)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和(b)以低于管芯连接组合物90%(重量)的有效量存在的至少一种导热和/或导电材料,以提供导电介质。
Description
发明领域
本发明涉及一种粘合剂组合物。一方面,本发明涉及适合于将半导体器件连接到承载衬底上的管芯连接粘合剂组合物。
发明背景
管芯连接粘合剂用于将诸如硅管芯或芯片的半导体器件粘结到诸如引线框或印刷电路板的衬底上。在半导体组件的组装过程中,管芯连接粘合剂在器件连线和灌封过程中将器件牢固地保持在原地。通过在粘合剂配方中加入导电和/或导热填料,可在器件和衬底间得到电的和/或热的接触。
通常使用的管芯连接粘合剂的实例是低熔点焊锡、导电环氧和导电聚酰亚胺。低熔点焊锡通常是金的合金。将“预制品”,一种切成半导体芯片的形状和尺寸的金属薄片,覆盖在组件要求的衬底上,并加热到接近预制品熔点的温度。然后可将芯片以摩擦运动放在预制品上。低熔点焊锡很昂贵而且很难加工。导电环氧通常是含有导电填料的低粘度膏体。用通常的手段将环氧施加到衬底上,然后将器件与涂覆的衬底接触。然后环氧可一步固化。导电聚酰亚胺与导电环氧相似。
用热固性管芯连接粘合剂,主要是基于环氧的制剂将半导体器件粘结到衬底上。置换失效芯片的再加工过程通常涉及对下面的衬底和上面的器件加热,并用剪切力从衬底上移开模片。在历史上,由于器件小且彼此间分隔很开,使得再加工相对简单。然而,出现的安装技术如多芯片模件同时使用较大的器件和器件间较小的间隙,从而提高了再加工过程中破坏衬底的可能性。这样,理想的是提供使再加工更容易进行的管芯连接粘合剂组合物。
发明概述
根据本发明,提供了一种热可再加工管芯连接组合物,包括:
(a)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(b)以低于管芯连接组合物90%(重量)的有效量的至少一种导热和/或导电材料,以提供导电介质。
这种管芯连接组合物提供容易再加工的半导体板和/或半导体组件。
本发明的详细描述
可有多种方法产生热可再加工交联树脂的聚合物链。热可再加工交联树脂可通过具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物通过Diels-Alder加成反应相互连接制得。在一个实施方案中,2,5-二烷基取代的呋喃基团可连接在聚合物链上或形成聚合物链的一部分。
形成Diels-Alder加成物的呋喃与亲二烯体可逆反应可表示为:2,5-二烷基 亲二烯体 DIELS-ALDER取代的呋喃 加成物其中Y是C<或N-。对于热可再加工交联树脂,所有或部分Diels-Alder加成物通过加热可转化为呋喃和亲二烯体,使树脂成为液态(可流动材料)。
在其分子结构中含有两个或更多亲二烯体的交联剂也可用于该实施方案。这些亲二烯体通过化学键或桥基互相连接。因此,本发明也考虑这样的管芯连接粘合剂组合物,它们包括带2,5-二烷基取代的呋喃片断的聚合物,和分子结构中含有两个或更多亲二烯体的交联剂。亲二烯体也可连接在聚合物链上或形成聚合物链的一部分。也可使用在其分子结构中含有两个或更多个2,5-二烷基取代的呋喃基团的交联剂。
在另一个实施方案中,亲二烯体可连接在聚合物链上,所述聚合物也与2,5-二烷基取代的呋喃基团连接,或作为聚合物链的一部分包含2,5-二烷基取代的呋喃基团。因此,含有2,5-二烷基取代的呋喃的聚合物也可包含2,5-二烷基取代的呋喃片断和亲二烯体片断。
2,5-二烷基取代的呋喃可以或不可以在其3-和4-位置被取代。优选的取代基是诸如例如烷基或烷氧基团的惰性取代基,通常具有10个以下的碳原子,如甲基、乙基、1-丙基、甲氧基和1-己氧基基团。含有2和5位置未被取代的呋喃的树脂易产生可导致不可逆胶凝的副反应,并影响其可逆性。
2,5-二烷基取代的呋喃基团可与交联树脂聚合物的聚合物链连接。所述基团可直接通过化学键或通过二价有机桥基连接,呋喃或呋喃的3-或4-位置的任何取代基可起到连接点作用。在呋喃的2-和5-位置的烷基取代基可以相同或不同,并将通常具有10个以下碳原子。合适的烷基基团的实例是甲基、乙基、2-丙基和1-己基。合适的可与聚合物链连接的呋喃基团的实例是2,5-二甲基呋喃-3-基、2,5-二乙基-3-甲基呋喃-4-基、5-乙基糠基或5-(1-丁基)糠基。
可与2,5-二烷基取代的呋喃基团连接的聚合物链的类型并不重要。合适的聚合物链是聚烯烃,如聚乙烯、聚丙烯、聚苯乙烯、聚丙烯酸或乙烯和丙烯酸或丙烯酸酯的共聚物,一氧化碳与烯属不饱和化合物的无规或交替共聚物(关于这些共聚物的进一步描述参照下文),或含有杂原子的链,如聚酰胺或聚酯。优选2,5-二烷基取代的呋喃形成聚合物骨架本身的结构单元。在这种情况下,尤其优选呋喃的每个2,5-二烷基取代基是亚烷基,该亚烷基同样形成聚合物链部分并可以或不可以被取代。
这种结构可通过呋喃化一氧化碳与烯属不饱和化合物的共聚物制得,所述共聚物在其聚合物链中含有1,4-二羰基结构,即通过将这些1,4-二羰基结构转化为呋喃片断。另外,含有2,5-二烷基取代的呋喃的聚合物可通过将一氧化碳与烯属不饱和化合物在强酸存在下反应直接制得。
在其聚合物链中含有1,4-二羰基结构的一氧化碳与烯属不饱和化合物的优选交替共聚物已经公知。它们可用由例如EP-A-121965、EP-A-181014和EP-A-516238的方法通过钯催化聚合反应制备。这样制备的聚合物是一氧化碳与烯属不饱和化合物的交替共聚物,该共聚物的聚合物链以交替排列方式含有源于一氧化碳的单体单元(即羰基)和源于烯属不饱和化合物的单体单元,使得聚合物链的每第四个碳原子属于羰基。含有1,4-二羰基结构的一氧化碳与烯属不饱和化合物的交替共聚物可以是无规共聚物,即该共聚物的聚合物链含有无规顺序的单体单元。后者的共聚物可使用例如US-A-2495286和US-A-4024326公开的方法通过自由基引发的聚合反应制备。
一氧化碳与烯属不饱和化合物的共聚物的呋喃化可通过本领域公知的方法进行,例如由A.Sen等(聚合物科学杂志,A部分,聚合物化学,32(1994),p841)公开的使用五氧化二磷作为脱水剂,或者如US-A-3979373中公开的在例如对甲苯磺酸的强酸存在下加热。这些方法使聚合物链中1,4-二羰基片断根据所选择的反应条件以不同的转化率转化为呋喃片断。
优选地采用一氧化碳与烯属不饱和化合物的交替共聚物进行呋喃化,因为这些共聚物在聚合物骨架中1,4-二羰基的含量较高,从而可结合较多量的呋喃基团而有效地完成呋喃化。然而,如果要求的呋喃化程度低,可使羰基转化为呋喃基团的转化率低。
一氧化碳与烯属不饱和化合物的共聚物可基于烃作为烯属不饱和化合物。优选的共聚物基于烯属不饱和烃,合适的是α-烯烃,尤其是具有10个以下碳原子的α-烯烃。非常合适的是脂族α-烯烃,尤其是具有3到6个碳原子的脂族α-烯烃,更尤其是直链的脂族α-烯烃,如丙烯、1-丁烯、1-戊烯和1-己烯。最优选丙烯。共聚物可以是部分有规的或无规的、有规立构的或无规立构的。
含有2,5-二烷基取代的呋喃的聚合物(其中基于丙烯和一氧化碳的聚合物被呋喃化)可由以下通式表示:
得到Diels-Alder加成物的亲二烯体的精确性能并不重要,只要Diels-Alder加成物具有使交联树脂具有可再加工性这样的热稳定性。通常可再加工交联树脂可以再加工的最低温度取决于所用半导体器件要求的最高温度。再加工适合于在100℃,优选130℃,到250℃,优选到200℃的温度下进行。
合适的亲二烯体官能团可用Y=Y表示,其中Y是C<或N-,或-C≡C-。优选的亲二烯体是例如具有连接在乙炔片断两侧的吸电子基团,如酯基和酮基。实例是丁炔二醇酸(即乙炔二羧酸)的单酯和二酯,以及取代的丁-2-炔-1,4-二酮。其它合适的亲二烯体是含有包括在5-或6-元环中的丁-2-烯-1,4-二酮的化合物,尤其是具有以下通式的化合物:其中X指O,S,N-、P-或-R-,其中R是亚烷基,其中至少一个自由价由桥基占据,所述桥基将亲二烯体与其中一个聚合物链或与另一个亲二烯体连接,其中剩余的价(如果有的话)由低级烷基或酰基取代基,或优选的由氢占据。合适的低级烷基取代基适合含有4个以下碳原子,并且是例如甲基或乙基。该通式的亲二烯体优选的是马来酸酐尤其是马来酰亚胺的环状衍生物(即X表示O或尤其是N-)。
其它合适的亲二烯体的实例包括双(三唑啉二酮)、双(2,3-二氮杂萘二酮)、醌、双(三聚氰基乙烯)、双(偶氮二羧酸酯);二丙烯酸酯、马来酸或富马酸聚酯、乙炔二羧酸酯聚酯。
如上文指出的,在一个实施方案中使用了在其分子结构中包含两个或更多个亲二烯体的交联剂,从所述亲二烯体中可得到Diels-Alder加成物。亲二烯体可通过一个或多个桥基互相连接。例如,三个亲二烯体可通过三价桥基互相连接。然而,使用通过二价桥基使两个亲二烯体互相连接的交联剂就足够了。亲二烯体也可通过化学键互相连接。
交联剂桥基的分子量和化学性能都可以在较大范围内不同。已经发现交联剂的这些差别导致覆盖了大范围的机械特性的可再塑性交联树脂。桥基可以在桥键上仅仅含有碳原子,但也可能在桥键上含有杂原子,如氧、硅或氮原子。桥基可以是柔性或刚性的。
例如,具有柔性聚合物链的聚合物桥基,如聚(烯化氧)或聚硅氧烷,具有大于300的数均分子量,得到似橡胶的可再加工交联树脂。当聚合物柔性链具有1500-5000或更大量级的数均分子量时,可得到代替热塑性橡胶的可再加工交联树脂。
同样,这种合适的交联剂是二马来酰亚氨基封端的聚烯化氧,如聚环氧乙烷或聚环氧丙烷,和二马来酰亚氨基封端的聚硅氧烷,如通式为H2N-CH2-[O-SiR2]n-O-CH2-NH2的聚硅氧烷二马来酰亚胺,其中n是平均大于10、尤其在20-70范围内的整数,每个R独立地是烷基,尤其是低于5个碳原子的烷基,优选是甲基。使用二氨基封端的聚环氧丙烷的二马来酰亚胺,尤其是数均分子量至少为300、更尤其在1500-5000范围内时可得到非常好的结果。
还使用低分子量桥基,即通常低于20个碳原子的桥基。环脂族和芳族桥基使桥基具有刚性。低分子量环脂族和芳族桥基往往得到可再塑性交联树脂,该树脂硬且脆,并具有较高的玻璃化转变温度。环脂族和芳族低分子量桥基的实例是桥中含有降冰片烷骨架的基团、1,3-亚苯基和下列通式的基团:-f-CH2-f、-f-O-f-O-f-、-f-O-f-SO2-f-O-f-和-f-C(CH3)2-f-,其中-f-指1,4-亚苯基。其它合适的桥基是亚烷基和氧化羰基(酯)和它们的结合。合适的低分子量交联剂是例如肼的二马来酰亚胺、2,4-二氨基甲苯、六亚甲基二胺、十二亚甲基二胺、具有如下通式的二胺:和低分子量的二氨基封端的(聚)硅氧烷,如通式为:H2N-CH2-[O-SiR2]n-O-CH2-NH2的聚硅氧烷,其中n的范围平均为1-10,优选1-5,基团R优选为甲基。上述通式的二元胺的异构体混合物可从HOECHST商购。使用二(4-马来酰亚氨基苯基)甲烷和二甲基二[(N-马来酰亚氨基甲基)氧基]硅烷可得到很好的结果。
其它基于马来酸酐的合适的交联剂是具有如下通式的化合物:其中A指前面描述的桥基,尤其是桥上具有低于20个碳原子的桥基。更尤其桥基A是亚烷基,如六亚甲基,或-D-O-CO-或-CO-O-D-O-CO-,其中D指二价烃基,例如诸如六亚甲基的亚烷基。
其它合适的交联剂是基于丁炔二酸和二元醇的聚酯,如乙二醇、聚乙二醇、丙二醇或聚丙二醇。这些聚酯可以是低分子量的交联剂,如如上所述的,或它们的数均分子量为例如大于400,如在2000-6000的范围内。
本发明还涉及交联剂,如二马来酰亚氨基封端的聚烯化氧,尤其是二马来酰亚氨基封端的聚环氧丙烷。这些交联剂的数均分子量至少为300,优选在1500-5000范围内。聚硅氧烷二马来酰亚胺的通式为H2N-CH2-[O-SiR2]n-O-CH2-NH2,其中n是至少为1的整数,每个R独立地为烷基,尤其是低于5个碳原子的烷基,优选为甲基。二马来酰亚氨基封端的聚硅氧烷可通过使用公知的方法将马来酰亚胺与甲醛N-羟甲基化,随后在碱和水的存在下与合适的二氯代二烷基硅烷反应来制备。
正如前面所提及的,某些实施方案涉及的交联剂在其分子结构中含有2,5-二烷基呋喃片断。在这些交联剂中,2,5-二烷基取代的呋喃基可通过化学键或桥基相互连接。这些桥基的性质通常与含有两个或更多个亲二烯体的交联剂的桥基(如前所述)的性质相同。合适的交联剂的实例是前面描述的二(5-乙基糠基)己二酸酯和(5-乙基糠基)乙酸与二元胺的二酰胺。
2,5-二烷基取代的呋喃片断和/或亲二烯体片断通过化学键合的方式或桥基方式连接到聚合物上。这些桥基可以与交联剂的桥基类型相同。随后将给出实施例。当聚合物是聚苯乙烯时,马来酰亚胺作为亲二烯体可通过聚苯乙烯与N-氯代甲基马来酰亚胺的氯化锡(IV)催化烷基化反应使其附着在聚苯乙烯上;当聚合物是(苯乙烯/马来酸酐)共聚物时,5-乙基糠基可通过在吡啶中用5-乙基糠基醇酯化(苯乙烯/马来酸酐)共聚物使其附着在(苯乙烯/马来酸酐)共聚物上。当聚合物是一氧化碳与烯属不饱和化合物的共聚物(聚合物链含有1,4-二羰基结构)时,可通过将共聚物与合适的取代伯烃基胺反应,例如使用US-A-3979374中已知的方法使2,5-二烷基呋喃和亲二烯体附着在其上。在该反应中,1,4-二羰基结构转化为吡咯结构,形成聚合物链的一部分,并由取代烃基N-取代。例如,一氧化碳与含有1,4-二羰基结构的烯属不饱和化合物的共聚物可与马来酸单酰胺和六亚甲基二胺反应,或与马来酸单酰胺和二(4-氨基苯基)甲烷反应,形成从酰胺基片断到马来酰亚胺片断的闭环。这样将产生在聚合物链中具有N-(6-马来酰亚胺己基)吡咯或N-{4-[(4’-马来酰亚胺苯基)甲基]苯基}吡咯片断的聚合物。当需要使用含有2,5-二烷基取代的呋喃片断和亲二烯体片断的聚合物时,一氧化碳与烯属不饱和化合物的共聚物的1,4-二羰基结构的一部分可转化为呋喃片断,1,4-二羰基结构的另一部分可转化为N-取代的吡咯结构,其中N-取代基包括亲二烯体。
可再加工交联树脂所基于的聚合物的分子量可有较大不同。合适的聚合物可具有从至少500,优选700,到30000,优选到20000范围的数均分子量。
存在于热可再加工交联树脂中的Diels-Alder加成物的量取决于存在于形成Diels-Alder加成物的组分中2,5-二烷基呋喃基的量和亲二烯体的量。本领域普通技术人员将了解到,需要存在某一最小量的Diels-Alder加成物使得交联树脂在低于Diels-Alder加成物转化为2,5-二烷基取代的呋喃和亲二烯体的温度下为固体材料。还将了解到,该最小量取决于树脂所基于的聚合物的分子量和类型,如果使用任何交联剂,还取决于每分子交联剂中亲二烯体或2,5-二烷基呋喃基团的数量(即官能度)。较小的聚合物分子量要求较多的Diels-Alder加成物的量。当使用具有较高官能度的交联剂时Diels-Alder加成物的量可较少。
通常,通过使用呋喃基与酮基比为1∶16到4∶1的含有2,5-二烷基呋喃的聚合物,可得到好的结果。2,5-二烷基取代的呋喃基团与亲二烯体的摩尔比通常为10∶1到1∶5,优选5∶1到1∶3。
传导材料
为了使粘合剂具有导热或导电性,在管芯连接组合物中掺入有效量的导热或导电材料。优选的导热材料是例如氧化铍、氮化硼、氧化铝(单晶)、涂覆有铜的氮化铝(参见US5288769)等。通过在管芯连接粘合剂配方中掺入导电材料(填料)获得电接触,导电材料如银、镍、铜和铝颗粒以及这些金属的合金。在管芯连接膏状组合物中使用粉末状或薄片状的导电材料。优选的导热和/或导电材料的用量范围是管芯连接粘合剂组合物总量的60%(重量)、优选70%(重量)至90%(重量)、优选80%(重量),尽管所使用的量可以更少或更多。
管芯连接粘合剂
热可再加工管芯连接指可通过加热液化管芯连接组合物(粘合剂)从衬底除去器件。当管芯连接组合物是可流动状态时,组合物是液化的。器件可去除而无需使用剪切力或过量的力。
本发明热可再加工管芯连接组合物包括(a)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(b)以低于管芯连接组合物90%(重量)的有效量的至少一种导热和/或导电材料,以提供导电介质。
热可再加工管芯连接组合物可以在热可再加工管芯连接组合物的熔融温度下加工和/或再加工。通常,热可再加工管芯连接组合物可以在从100℃,优选130℃,到250℃,优选200℃的温度范围内进行加工和/或再加工。如果树脂在高温下延时加热,例如在200℃下延时加热12小时,组合物就进行了不可逆交联,不再热可逆。
热可再加工管芯连接组合物或粘合剂也可含有其它添加剂,如离子净化剂(如磷酸三钙)、自由基抑制剂(如氢醌、吩噻嗪)、弹性改性剂(如硅氧烷)和其它在管芯连接粘合剂中使用的常规添加剂。为得到较长的再加工时间,优选使用离子净化剂和/或自由基抑制剂。
将半导体器件连接到衬底上的方法包括:
(a)提供衬底;
(b)在衬底上于足可以使管芯连接粘合剂组合物转化为液态的温度下分散热可再加工管芯连接粘合剂组合物由此制得粘合剂连接的衬底,该组合物含有:
(i)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(ii)以低于管芯连接组合物90%(重量)的有效量的至少一种导热和/或导电材料,以提供导电介质;
(c)当粘合剂为液态时,将半导体器件连接到粘合剂连接的衬底的热可再加工管芯连接粘合剂的表面,由此将半导体器件粘结到衬底上;以及
(d)冷却热可再加工管芯连接粘合剂,得到组件。可在粘合剂随时间完全冷却前,或通过加热以保持或将粘合剂再液化成可流动材料,将半导体器件放置在粘合剂上。可通过使用标准设备,如将管芯连接连接组合物各成分混合,并将组合物精确分散在衬底上的注射器或静态混合器,将管芯连接连接组合物分散在衬底上。
半导体器件可粘结到各种衬底,如各种金属、陶瓷或包括印刷电路板(PCB)如带芯片的板的层状衬底上;可粘结到焊接框架上,然后通过树脂转换模压成诸如双列直插式组件(DIP)和塑料四重平板组件(PQFP)的组件;以及诸如球珊格阵列(BGA)的其它组件结构。失效器件的维修和再加工对于管芯连接粘合剂变得日益重要。多芯片模板(MCM)使用现有的封装技术,唯一不同的是许多裸露芯片通过粘合剂连接在衬底上并封装在一起。例如,BGA结构可有许多通过粘合剂连接在衬底上的管芯连接、从管芯连接连接到衬底的自粘胶带、作为一个组件涂覆所有管芯连接的灌封剂、和形成从BGA衬底到印刷电路衬底的连接的焊接球。由于半导体器件和邻近的元件如其它半导体器件之间的间隙越来越近,维修和再加工而不损坏邻近器件变得相当困难。本发明的热可再加工管芯连接粘合剂使得用户在间隙很近的器件和高密度的衬底上可容易地进行维修和再加工。
粘结在半导体器件一侧和衬底另一侧的热可再加工管芯连接粘合剂组合物可通过以下步骤再加工,包括
(a)将管芯连接粘合剂组合物加热到高到足以使管芯连接粘合剂组合物转化为液态的温度,所述组合物包括
(i)由具有大于一个官能度的亲二烯体与含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(ii)以低于管芯连接组合物90%(重量)的有效量存在的至少一种导热或导电材料,以提供导电介质,由此得到液态管芯连接粘合剂组合物;
(b)从液态管芯连接粘合剂组合物移开半导体器件;
(c)可选地,分散新的热可再加工管芯连接粘合剂组合物,所述组合物含有
(i)由具有大于一个官能度的亲二烯体与含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(ii)以低于管芯连接组合物90%(重量)的有效量存在的至少一种导热或导电材料,以提供导电介质;
(d)可选地,在液态管芯连接粘合剂表面提供另一个半导体器件,由此将另一个半导体器件连接到管芯连接粘合剂上;和
(e)将液态管芯连接粘合剂冷却到足以低到固化树脂的温度。
可以后烘烤管芯连接粘合剂组合物,以加强管芯连接的热性能和机械性能(如玻璃化转变温度和机械强度)。为了保持交联树脂的热可再加工性,可将管芯连接粘合剂加热到从70℃,优选90℃,到200℃,优选160℃的温度范围内的某一温度达4小时。如果不要求热可再加工性,可将管芯连接粘合剂组合物在从150℃,优选180℃,到300℃,优选250℃的温度范围内的某一温度后烘烤达4小时,以改善热性能。
例举的实施方案
以下例举的实施方案描述了本发明的新型环氧树脂组合物,它们用于例举目的而不对本发明形成限制。
实施例1
将甲醇和丙烯(重量比约为2∶1)充入高压釜中,加热到90℃,然后充入一氧化碳达到72bar压力。注射重量比为0.6∶0.62∶1的乙酸钯、1,3-二(二乙基膦基)-丙烷、三氟甲烷磺酸和0.3的吡啶,在四氢呋喃和甲醇溶液(15∶1体积比)中得到的催化剂溶液,在反应过程中,通过连续供给一氧化碳,保持反应釜压力恒定在72bar。除去溶剂得到数均分子量为733的丙烯/CO交替共聚物。
实施例2
将实施例1的数均分子量为733的丙烯-CO交替共聚物溶解在甲苯中,在催化量的对甲苯磺酸存在下,通过加热回流进行环化。得到的聚合物用C-13NMR分析,通过在107、114、147和153ppm中心周围出现的C-13NMR信号(呋喃共振),表明在初始聚酮中有82%的酮环化成呋喃(呋喃∶酮为2.28∶1)。
实施例3
于171℃(340°F)混合实施例2制备的呋喃化聚酮和化学计量的甲苯二胺二马来酰亚胺(Compimide Resin TDAB,Technochemie Gmbh)制得一体系。混合物从凝胶板上移开并在室温储存。将掩盖有焊锡的8层(环氧玻璃纤维)印刷电路板置于171℃(340°F)的凝胶板上,使之加热达到该温度。将混合体系分散到电路板上,并将硅芯片置于体系的上部,使之粘结到板上。将电路板从凝胶板上移开,冷却到室温。随着体系在室温形成交联固体,留下的模片粘结在电路板上。电路板再次放回到热的凝胶板上,加热一分钟。随着粘结体系回复到未交联的液体状态,芯片可容易地从电路板上除去。通过仍然存在的粘合剂膜又可使芯片重新连接到电路板原来的位置上。
实施例4
用与实施例1相似的方式,从丙烯和乙烯制备数均分子量为1472的烯烃/CO交替共聚物(27%乙烯,73%丙烯)。将共聚物溶解在甲苯中,在催化量的对甲苯磺酸存在下,通过加热回流进行环化。得到的聚合物用C-13NMR分析,表明在初始聚酮中有56%的酮环化成呋喃(呋喃∶酮为0.64∶1)。
实施例5
凝胶板设置为171℃(340°F),将实施例4制备的呋喃化聚酮分散在板上。将化学计量的TDAB混合到呋喃化的聚酮中,直到得到均匀的混合物。将混合物从凝胶板上移开,在室温下储存。
实施例6
将ICI园锥和平板粘度计设置在175℃温度,并在设定点保持平衡。将少量实施例5的混合物放置在平板上,使之达到该温度。落下圆锥并旋转,在圆锥和平板间获得好的薄膜。通过提起圆锥检查,确认形成好的薄膜。随后将混合物恒温90秒钟,当圆锥以固定速度旋转时得到两个粘度读数。提起圆锥,将混合物从圆锥和平板上取下。在室温下冷却混合物,直到形成交联固体。以上步骤,即装载在ICI圆锥和平板上、在175℃测量粘度、取下混合物、冷却到室温,对同一混合物重复三次。三次粘度的读数依次为3-5厘泊、3-5厘泊和3-5厘泊。该试验表面混合物在室温下的交联状态和175℃下的低粘度非交联液态能可逆地交替转变。
实施例7
用与实施例1相似的方式制备数均分子量为1616的丙烯/CO交替共聚物,所不同的是在催化剂溶液中用1,3-二(二-邻甲氧苯基膦基)丙烷代替1,3-二(二乙基膦基)丙烷。将共聚物溶解在甲苯中,在催化量的对甲苯磺酸存在下,通过加热回流进行环化。得到的聚合物用C-13NMR分析,表明在初始聚酮中有57%的酮环化成呋喃(呋喃∶酮为0.66∶1)。
实施例8
凝胶板设置为171℃(340°F),将实施例7制备的呋喃化聚酮分散在板上。将化学计量的甲苯二苯胺二马来酰亚胺(Compimide ResinMDAB,Technochemie Gmbh)和0.2摩尔吩噻嗪(Phenothiazine,Aldrich Chemical)/每mol MDAB混合到呋喃化的聚酮中,直到得到均匀的混合物。然后将混合物从凝胶板上移开,在室温下储存。将少部分的混合物置于171℃(340°F)的凝胶板上,并与60%(重量)的银粉(银粉,-325目,Johnson Matthey)混合。混合各成分,然后将混合物移开,在室温下储存。
实施例9
将ICI园锥和平板粘度计设置在175℃温度,并在设定点保持平衡。将少量实施例8的混合物放置在平板上,并使之达到该温度。落下圆锥并旋转,在圆锥和平板间获得好的薄膜。通过提起圆锥检查,确认形成好的薄膜。随后将混合物恒温90秒钟,当圆锥以固定速度旋转时得到两个粘度读数。提起圆锥,将混合物从圆锥和平板上取下。在室温下冷却混合物,直到形成交联固体。以上步骤,即装载在ICI圆锥和平板上、在175℃测量粘度、取下混合物、冷却到室温,对同一混合物重复三次。三次粘度的读数依次为70-75厘泊、75-80厘泊和75-80厘泊。该试验表面混合物在室温下的交联状态和175℃下的低粘度非交联液态能交替转变。
实施例10
掩盖有焊锡的8层(环氧玻璃纤维)印刷电路板置于171℃(340°F)的凝胶板上,使之加热达到该温度。将实施例8制备的银粉填充的体系分散在电路板上,并将硅芯片置于体系的上部,使之粘结到板上。将电路板从凝胶板上移开,冷却到室温。随着体系在室温形成交联固体,留下的模片粘结在电路板上。电路板再次放回到热的凝胶板上,加热一分钟。随着粘结体系回复到未交联的液体状态,芯片可容易地从电路板上除去。通过仍然存在的粘合剂膜又可使芯片重新连接到电路板原来的位置上,并将电路板从凝胶板上移开,冷却到室温。以上步骤,即将电路板放回热的表面、移开芯片、重新将芯片粘结到电路板上、冷却到室温,另外重复两次。
实施例11
将实施例7制备的呋喃化聚酮和化学计量的TDAB以及6.5%(重量)的吩噻嗪加热到180℃,混合后倒入3.2mm(1/8英寸)厚的金属模板中。将模板急冷,测试所得铸件的性能。发现试样的弯曲模量为43bar(628磅/英寸2),该值与由双酚A环氧制造、用酸酐固化剂固化的交联环氧的值相近。介电常数和分散因子分别为3.17和0.013。
实施例12
实施例7制备的呋喃化聚酮与化学计量比为2∶1的MDAB、0.1mol吩噻嗪/每mol MDAB,和0.015gm 2-乙基己酸/每gm呋喃化聚酮反应。用差示扫描热量计以20℃/分钟的斜率对试样进行扫描。玻璃化转化的开始温度发生在105℃。
实施例13
实施例4制备的呋喃化聚酮与化学计量的TDAB和0.1mol吩噻嗪/每mol TDAB,于171℃(340°F)下在凝胶板上反应。将试样研磨并与水以10∶1的比例(水∶试样)置于Parr弹中。Parr弹在60℃保持20小时,通过离子色谱法分析水抽提物中的离子。抽提物中含有14ppm乙酸、<3ppm甘醇酸酯、甲酸酯、丙酸酯、<0.25ppm氯、<1ppm硝酸盐、1.7ppm硫酸盐、4.8ppm钠、0.8ppm镁、2.5ppm钙和0.2ppm铵离子。
Claims (10)
1、一种热可再加工的管芯连接粘合剂组合物,包括:
(a)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(b)以低于管芯连接组合物90%(重量)的有效量的至少一种导热和/或导电材料,以提供导电介质。
2、权利要求1的热可再加工的管芯连接粘合剂组合物,其中交联树脂在100-250℃的温度范围内可再加工。
3、权利要求1或2的热可再加工的管芯连接粘合剂组合物,其中亲二烯体是具有连接在乙炔片断两侧的吸电子基团的炔或马来酸酐的环化衍生物。
4、权利要求3的热可再加工的管芯连接粘合剂组合物,其中亲二烯体选自在5元环中含有丁-2-烯-1,4-二酮片断的化合物,和在6元环中含有丁-2-烯-1,4-二烯片断的化合物。
5、权利要求3的热可再加工的管芯连接粘合剂组合物,其中热可再加工树脂另外含有选自二马来酰亚氨基封端的聚烯化氧、二马来酰亚氨基封端的聚硅氧烷、肼的二马来酰亚胺、2,4-二氨基甲苯、六亚甲基二胺、十二亚甲基二胺,和以下通式的取代的和不取代的二胺的交联剂残基:
6、权利要求1或2的热可再加工的管芯连接粘合剂组合物,其中含有2,5-二烷基取代呋喃的聚合物通过将一氧化碳与至少一种烯族不饱和化合物反应制得。
7、权利要求1或2的热可再加工的管芯连接粘合剂组合物,其中在含有2,5-二烷基取代呋喃的聚合物中的2,5-二烷基取代呋喃基团与亲二烯体以10∶1到1∶5的摩尔比结合。
8、权利要求1或2的热可再加工的管芯连接粘合剂组合物,另外包含(c)自由基抑制剂和/或离子净化剂。
9、一种将半导体器件连接到衬底上的方法,包括:
(a)提供衬底;
(b)至少在部分所述衬底上,于足可以使管芯连接粘合剂组合物转化为液态的温度下分散热可再加工管芯连接粘合剂组合物由此制得粘合剂连接的衬底,该组合物含有:
(i)由具有大于一个官能度的至少一种亲二烯体与至少一种含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(ii)以低于管芯连接组合物90%(重量)的有效量存在的至少一种导热和/或导电材料,以提供导电介质;
(c)当粘合剂为液态时,将半导体器件连接到粘合剂连接的衬底的热可再加工管芯连接粘合剂的表面,由此将半导体器件粘结到衬底上;以及
(d)将管芯连接粘合剂冷却到足以固化树脂的低的温度,从而得到组件。
10、权利要求9的方法,另外包括以下步骤:
(e)将组件的热可再加工管芯连接粘合剂组合物加热到高到足够使管芯连接粘合剂组合物转化为液态的温度,从而得到液态管芯连接粘合剂组合物;
(f)从液态管芯连接粘合剂组合物上移开半导体器件;
(g)可选地,分散新的热可再加工管芯连接粘合剂组合物,所述组合物含有
(i)由具有大于一个官能度的亲二烯体与含有2,5-二烷基取代的呋喃的聚合物反应制得的热可再加工交联树脂,和
(ii)以低于管芯连接组合物90%(重量)的有效量存在的至少一种导热或导电材料,以提供导电介质;
(h)可选地,在液态管芯连接粘合剂表面提供另一个半导体器件,由此将另一个半导体器件连接到管芯连接粘合剂上;和
(i)将液态管芯连接粘合剂冷却到足以低到固化树脂的温度,从而提供再加工的组件。
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Cited By (4)
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CN103314435A (zh) * | 2011-01-14 | 2013-09-18 | 国际商业机器公司 | 可逆粘合性热界面材料 |
CN103374318A (zh) * | 2012-04-20 | 2013-10-30 | 合肥杰事杰新材料股份有限公司 | 一种热可逆胶粘剂、制备方法及其应用 |
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Families Citing this family (35)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5912282A (en) * | 1996-12-16 | 1999-06-15 | Shell Oil Company | Die attach adhesive compositions |
US6274389B1 (en) | 1997-01-17 | 2001-08-14 | Loctite (R&D) Ltd. | Mounting structure and mounting process from semiconductor devices |
US6316528B1 (en) | 1997-01-17 | 2001-11-13 | Loctite (R&D) Limited | Thermosetting resin compositions |
JP4190611B2 (ja) * | 1998-03-13 | 2008-12-03 | パナソニック株式会社 | 部品装着方法、及び部品装着装置 |
US6971163B1 (en) * | 1998-04-22 | 2005-12-06 | Dow Corning Corporation | Adhesive and encapsulating material with fluxing properties |
SG78377A1 (en) * | 1998-07-02 | 2001-02-20 | Nat Starch Chem Invest | Method of making electronic component using reworkable adhesives |
SG85658A1 (en) * | 1998-07-02 | 2002-01-15 | Nat Starch Chem Invest | Package encapsulants prepared from allylated amide compounds |
US6350840B1 (en) * | 1998-07-02 | 2002-02-26 | National Starch And Chemical Investment Holding Corporation | Underfill encapsulants prepared from allylated amide compounds |
US7019410B1 (en) * | 1999-12-21 | 2006-03-28 | Micron Technology, Inc. | Die attach material for TBGA or flexible circuitry |
US6271335B1 (en) * | 2000-01-18 | 2001-08-07 | Sandia Corporation | Method of making thermally removable polymeric encapsulants |
US6570245B1 (en) | 2000-03-09 | 2003-05-27 | Intel Corporation | Stress shield for microelectronic dice |
US6426552B1 (en) | 2000-05-19 | 2002-07-30 | Micron Technology, Inc. | Methods employing hybrid adhesive materials to secure components of semiconductor device assemblies and packages to one another and assemblies and packages including components secured to one another with such hybrid adhesive materials |
US6421253B1 (en) | 2000-09-08 | 2002-07-16 | Powerwave Technologies, Inc. | Durable laminated electronics assembly using epoxy preform |
SG97938A1 (en) * | 2000-09-21 | 2003-08-20 | Micron Technology Inc | Method to prevent die attach adhesive contamination in stacked chips |
US7176044B2 (en) * | 2002-11-25 | 2007-02-13 | Henkel Corporation | B-stageable die attach adhesives |
JP2004307859A (ja) * | 2003-04-05 | 2004-11-04 | Rohm & Haas Electronic Materials Llc | 電子デバイス製造 |
US7896650B2 (en) | 2005-12-20 | 2011-03-01 | 3M Innovative Properties Company | Dental compositions including radiation-to-heat converters, and the use thereof |
US7776940B2 (en) | 2005-12-20 | 2010-08-17 | 3M Innovative Properties Company | Methods for reducing bond strengths, dental compositions, 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 |
US20080085572A1 (en) * | 2006-10-05 | 2008-04-10 | Advanced Chip Engineering Technology Inc. | Semiconductor packaging method by using large panel size |
US20110018127A1 (en) * | 2008-03-31 | 2011-01-27 | Byoungchul Lee | Multilayer UV-Curable Adhesive Film |
CN102099431A (zh) * | 2008-03-31 | 2011-06-15 | 汉高有限公司 | 多层紫外线可固化粘合膜 |
WO2010123765A2 (en) * | 2009-04-20 | 2010-10-28 | Henkel Corporation | Thin bond line semiconductor packages |
EP2440627B1 (en) | 2009-06-11 | 2015-03-04 | Henkel US IP LLC | Thermally reversible hot melt adhesive composition containing multifunctional diene and dienophile compounds |
US9096784B2 (en) | 2010-07-23 | 2015-08-04 | International Business Machines Corporation | Method and system for allignment of graphite nanofibers for enhanced thermal interface material performance |
US9257359B2 (en) | 2011-07-22 | 2016-02-09 | International Business Machines Corporation | System and method to process horizontally aligned graphite nanofibers in a thermal interface material used in 3D chip stacks |
US20130127069A1 (en) * | 2011-11-17 | 2013-05-23 | International Business Machines Corporation | Matrices for rapid alignment of graphitic structures for stacked chip cooling applications |
US9245813B2 (en) | 2013-01-30 | 2016-01-26 | International Business Machines Corporation | Horizontally aligned graphite nanofibers in etched silicon wafer troughs for enhanced thermal performance |
US9090004B2 (en) | 2013-02-06 | 2015-07-28 | International Business Machines Corporation | Composites comprised of aligned carbon fibers in chain-aligned polymer binder |
US9085719B2 (en) | 2013-03-18 | 2015-07-21 | International Business Machines Corporation | Thermally reversible thermal interface materials with improved moisture resistance |
US9082744B2 (en) | 2013-07-08 | 2015-07-14 | International Business Machines Corporation | Method for aligning carbon nanotubes containing magnetic nanoparticles in a thermosetting polymer using a magnetic field |
JP6411537B2 (ja) * | 2014-03-06 | 2018-10-24 | ヘンケル・アクチェンゲゼルシャフト・ウント・コムパニー・コマンディットゲゼルシャフト・アウフ・アクチェンHenkel AG & Co. KGaA | 単結晶アルミナ充填ダイアタッチペースト |
JP6613649B2 (ja) * | 2014-06-23 | 2019-12-04 | 東洋インキScホールディングス株式会社 | 接着剤組成物、積層シート、太陽電池用裏面保護シート |
US9545011B2 (en) | 2015-05-13 | 2017-01-10 | International Business Machines Corporation | Dry film solder mask composite laminate materials |
US10359812B2 (en) | 2017-12-12 | 2019-07-23 | Motorola Mobility Llc | Device component exposure protection |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4113981A (en) * | 1974-08-14 | 1978-09-12 | Kabushiki Kaisha Seikosha | Electrically conductive adhesive connecting arrays of conductors |
US3979373A (en) * | 1975-06-13 | 1976-09-07 | Shell Oil Company | Polymeric furan derivative |
US4826932A (en) * | 1987-12-29 | 1989-05-02 | Shell Oil Company | Dioxolane containing polymer |
US5001542A (en) * | 1988-12-05 | 1991-03-19 | Hitachi Chemical Company | Composition for circuit connection, method for connection using the same, and connected structure of semiconductor chips |
US4975221A (en) * | 1989-05-12 | 1990-12-04 | National Starch And Chemical Investment Holding Corporation | High purity epoxy formulations for use as die attach adhesives |
US5002818A (en) * | 1989-09-05 | 1991-03-26 | Hughes Aircraft Company | Reworkable epoxy die-attach adhesive |
US5121190A (en) * | 1990-03-14 | 1992-06-09 | International Business Machines Corp. | Solder interconnection structure on organic substrates |
EP0454005B1 (en) * | 1990-04-26 | 1994-12-07 | E.I. Du Pont De Nemours And Company | Die attach adhesive composition |
US5120678A (en) * | 1990-11-05 | 1992-06-09 | Motorola Inc. | Electrical component package comprising polymer-reinforced solder bump interconnection |
US5288769A (en) * | 1991-03-27 | 1994-02-22 | Motorola, Inc. | Thermally conducting adhesive containing aluminum nitride |
US5274913A (en) * | 1991-10-25 | 1994-01-04 | International Business Machines Corporation | Method of fabricating a reworkable module |
US5233046A (en) * | 1991-11-04 | 1993-08-03 | Hay Allan S | Diarylacetylenes, enamines and acetylenic polymers and their production |
US5390082A (en) * | 1992-07-06 | 1995-02-14 | International Business Machines, Corp. | Chip carrier with protective coating for circuitized surface |
US5371328A (en) * | 1993-08-20 | 1994-12-06 | International Business Machines Corporation | Component rework |
US5360942A (en) * | 1993-11-16 | 1994-11-01 | Olin Corporation | Multi-chip electronic package module utilizing an adhesive sheet |
US5547149A (en) * | 1994-05-16 | 1996-08-20 | Flight Safety Systems Inc. | Aircraft airbag protection apparatus and method |
TW338044B (en) * | 1994-11-15 | 1998-08-11 | Shell Internattonale Res Mij B V | A cross linked resin |
ZA959606B (en) * | 1994-11-15 | 1996-05-29 | Shell Int Research | A cross-linked resin |
US5912282A (en) * | 1996-12-16 | 1999-06-15 | Shell Oil Company | Die attach adhesive compositions |
US5760337A (en) * | 1996-12-16 | 1998-06-02 | Shell Oil Company | Thermally reworkable binders for flip-chip devices |
US5726391A (en) * | 1996-12-16 | 1998-03-10 | Shell Oil Company | Thermosetting Encapsulants for electronics packaging |
-
1996
- 1996-12-16 US US08/767,057 patent/US5912282A/en not_active Expired - Fee Related
-
1997
- 1997-12-12 ZA ZA9711198A patent/ZA9711198B/xx unknown
- 1997-12-12 MY MYPI97006002A patent/MY117024A/en unknown
- 1997-12-15 CA CA002275194A patent/CA2275194A1/en not_active Abandoned
- 1997-12-15 EP EP97954434A patent/EP0944685B1/en not_active Expired - Lifetime
- 1997-12-15 WO PCT/EP1997/007155 patent/WO1998027177A1/en not_active Application Discontinuation
- 1997-12-15 ID IDW990523A patent/ID21758A/id unknown
- 1997-12-15 CN CN97180678A patent/CN1101438C/zh not_active Expired - Fee Related
- 1997-12-15 BR BR9713936-0A patent/BR9713936A/pt unknown
- 1997-12-15 IL IL13014597A patent/IL130145A0/xx unknown
- 1997-12-15 HU HU0000802A patent/HUP0000802A3/hu unknown
- 1997-12-15 KR KR1019997005312A patent/KR20000069471A/ko not_active Application Discontinuation
- 1997-12-15 DE DE69733485T patent/DE69733485D1/de not_active Expired - Lifetime
- 1997-12-15 JP JP52734398A patent/JP2002503263A/ja not_active Withdrawn
- 1997-12-15 AU AU58587/98A patent/AU729363B2/en not_active Ceased
-
1998
- 1998-01-13 US US09/006,314 patent/US5973052A/en not_active Expired - Fee Related
-
1999
- 1999-03-08 US US09/264,434 patent/US6147141A/en not_active Expired - Fee Related
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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CN103298994A (zh) * | 2010-12-06 | 2013-09-11 | 尼亚加有限责任公司 | 生产绒毛类纺织品的方法和由该方法获得的纺织品 |
CN103298994B (zh) * | 2010-12-06 | 2016-03-23 | 阿盖恩Ip有限责任公司 | 生产绒毛类纺织品的方法和由该方法获得的纺织品 |
CN103314435A (zh) * | 2011-01-14 | 2013-09-18 | 国际商业机器公司 | 可逆粘合性热界面材料 |
CN103314435B (zh) * | 2011-01-14 | 2017-03-22 | 国际商业机器公司 | 可逆粘合性热界面材料 |
CN103374318A (zh) * | 2012-04-20 | 2013-10-30 | 合肥杰事杰新材料股份有限公司 | 一种热可逆胶粘剂、制备方法及其应用 |
CN111087741A (zh) * | 2019-12-26 | 2020-05-01 | 上海普利特复合材料股份有限公司 | 一种易于超声波焊接的聚丙烯改性材料及其制备方法 |
Also Published As
Publication number | Publication date |
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CA2275194A1 (en) | 1998-06-25 |
EP0944685B1 (en) | 2005-06-08 |
EP0944685A1 (en) | 1999-09-29 |
AU5858798A (en) | 1998-07-15 |
US6147141A (en) | 2000-11-14 |
US5973052A (en) | 1999-10-26 |
HUP0000802A3 (en) | 2001-05-28 |
IL130145A0 (en) | 2000-06-01 |
US5912282A (en) | 1999-06-15 |
JP2002503263A (ja) | 2002-01-29 |
WO1998027177A1 (en) | 1998-06-25 |
HUP0000802A2 (en) | 2000-07-28 |
ZA9711198B (en) | 1998-06-23 |
BR9713936A (pt) | 2000-03-28 |
KR20000069471A (ko) | 2000-11-25 |
AU729363B2 (en) | 2001-02-01 |
DE69733485D1 (de) | 2005-07-14 |
MY117024A (en) | 2004-04-30 |
CN1101438C (zh) | 2003-02-12 |
ID21758A (id) | 1999-07-22 |
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