CN1145682C - 微电子装置用的小片粘附粘合剂 - Google Patents

微电子装置用的小片粘附粘合剂 Download PDF

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Publication number
CN1145682C
CN1145682C CNB991113950A CN99111395A CN1145682C CN 1145682 C CN1145682 C CN 1145682C CN B991113950 A CNB991113950 A CN B991113950A CN 99111395 A CN99111395 A CN 99111395A CN 1145682 C CN1145682 C CN 1145682C
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chain
alkyl
aryl
independently
carbon atom
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CN1248603A (zh
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D���ն���
D·赫尔
R·A·舒尔茨
徐平永
S·R·麦克劳林
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Henkel And Ip Holding LLC
United States Henkel Ip LLC
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National Starch and Chemical Investment Holding Corp
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Abstract

一种用于将电子元件粘合到基体上的热塑性或热固性粘合剂,其中该粘合剂由固化组合物就地固化,所述固化组合物含有一种或多种单一或多官能马来酰亚胺化合物,或一种或多种除马来酰亚胺化合物之外的单一或多官能乙烯基化合物,或马来酰亚胺和乙烯基化合物的混合物,一种固化引发剂和任选地一种或多种填料。

Description

微电子装置用的小片粘附粘合剂
本发明涉及用作微电子装置或半导体封装材料粘合剂的组合物。
粘合剂组合物,尤其是导电粘合剂以各种目的用于半导体和微电子装置的制造和装配。最主要的用途是将集成电路芯片粘合到机身或其它基体上,和将电路封装材料粘合或装配到印刷线路板上。
对电子封装材料中导电粘合剂的要求是应具有良好的机械强度,对元件或载体无影响的固化特性以及可与工业中目前使用的设备相适应的触变特性。
粘合剂粘合或互联工艺的另一重要方面是对粘合进行再加工的能力。对于大体积商品的单个芯片封装材料来说,失效芯片可以丢弃,不会造成大量的损失。但是,当丢弃只有一个失效芯片的多芯片封装件时,则变得昂贵;因此,再处理失效元件的能力成为制备工艺的一个优点。今天,半导体工业中的一个主要研究方面是开发一种粘合剂,它们不仅在粘合强度和柔软性方面要满足所有要求,而且还应能进行再处理,即可以除去失效元件而不破坏基体。
本发明提供一种电子装置用的粘合剂组合物,它们含有一种或多种单一或多官能的马来酰亚胺化合物,或者除马来酰亚胺外的一种或多种单一或多官能的乙烯基化合物,或者含马来酰亚胺或乙烯基化合物的混合物,一种固化引发剂,和任选地一种或多种填料。该组合物可进行再处理。
在另一实施方式中,本发明涉及由上述的可固化粘合剂组合物得到的固化粘合剂。
在另一实施方式中,本发明涉及微电子装配件,包括用固化的粘合剂组合物粘合到基体上的电子元件,所述组合物由含一种或多种单-或多官能马来酰亚胺化合物,或一种或多种单-或多官能乙烯基化合物,或马来酰亚胺和乙烯基化合物的混合物,一种固化引发剂和任选地一种或多种填料的组合物制得。
本发明粘合剂组合物中使用的马来酰亚胺和乙烯基化合物是可固化的化合物,是指能聚合的、交联或未交联的化合物。正如该说明书中使用的,“固化”是指交联或未交联的聚合反应。现有技术中所指的“交联”是两种聚合物链通过桥元素、分子基团、或化合物的连接,通常在加热时发生。当交联密度增加时,材料的性能可从热塑性改变成热固性。
可以通过单一或多官能化合物的定向选择和用量选择制备交联密度范围宽的聚合物。反应用的多官能化合物的比例越大,交联密度就越大。如果要求有热塑性特性,那么粘合剂组合物可用单官能化合物制备以限制交联密度。可加入少量的多官能化合物,以使组合物具有一定的交联性和强度,条件是将多官能化合物的用量限制到不会削弱所要求的热塑性的量。在这些参数中,单个粘合剂的强度和弹性可满足特定的最终使用要求。
在需要再处理装配件和使用热塑性材料的那些情况下,电子元件可与基体分离,并且可以加热任何残余的粘合剂,直到它们变软,易于除去。
也可控制交联密度,使得固化粘合剂具有宽范围的玻璃转变温度,以经受随后的加工处理和操作温度。
在本发明粘合剂组合物中,马来酰亚胺化合物和乙烯基化合物可单独使用或者混合使用。马来酰亚胺或乙烯基化合物,或两者在固化封装粘合剂组合物中的占有量按有机组分存在量计(任何填料除外)为2-98%(重量)。
粘合剂组合物还含有至少一种游离基引发剂,对游离基引发剂的化学种类予以限制,它们应分解具有一个或多个不成对电子的分子碎片,具有高的反应性并且使用寿命较短,能够借助链机理引发化学反应。游离基引发剂的用量是有机化合物(任何填料除外)重量的0.1-10%(重量),优选0.1-3.0%(重量)。游离基固化机理使得快速固化并使得组合物在固化前具有长的存储期限。优选的游离基引发剂包括过氧化物,例如过辛酸丁酯和过氧化二枯基,和偶氮化合物,例如2,2′-偶氮双(2-甲基-丙腈)和2,2’-偶氮双(2-甲基-丁腈)。
另外,粘合剂组合物可含一种光引发剂,来代替游离基引发剂,固化过程可通过UV辐射引发。光引发剂的用量是有机化合物(任何填料除外)重量的0.1-10%(重量),优选1-5.0%(重量)。在某些情况下,要求有光引发剂和游离基引发剂同时存在。例如,固化过程可通过UV辐射引发,在后来的加工步骤中,可通过加热完成固化,实现游离基固化。
这些组合物的固化温度一般为80-200℃,固化的有效时间在1分钟至60分钟的范围内。应该清楚:每种粘合剂组合物的时间和温度固化曲线将可改变,可使用不同的组合物来绘制固化曲线,使得它们适于特定的工业制造工艺。
合适的用于该粘合剂的导电填料是银、铜、金、钼、铂。在某些情况下,需要非导电填料以调整流变性,例如三氧化二铝、二氧化硅和聚四氟乙烯。
本说明书全文中使用的符号C(O)是指羰基。
                马来酰亚胺化合物
适用于本发明粘合剂组合物的马来酰亚胺化合物具有由式[M-Xm]n-Q表示或由式[M-Zm]n-K表示的结构。对于这些具体的结构式,当下标“n”为1的整数时,化合物是单官能的化合物;当下标“n”为2-6的整数时,化合物是多官能化合物。
[M-Xm]n-Q,或式:[M-Zm]n-K
式[M-Xm]n-Q表示如下的一些化合物,其中:
M是具有下列结构式的马来酰亚胺部分
Figure C9911139500111
其中R1是H或C1-C5烷基;
每个X独立地代表选自结构式(1)-(IV)的芳基:
Figure C9911139500112
Q是直链或支链烷基、烷氧基、亚烷基、烯化氧、芳基、芳氧基烷基胺、烷基硫化物、亚烷基胺、亚烷基硫化物或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与X连接;
或Q是具有下列结构式的尿烷:
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50;
或Q是具有下列结构式的酯:
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;
或Q是具有下列结构式的硅氧烷:
-(CR1 2)e[SiR4-O]f-SiR4 2-(CR1 2)g-
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表H、具有1-5个碳原子的烷基、或芳基,e和g独立地是1-10,f是1-50;和
m是0或1,以及n是1-6。
优选的组合物是脂族双马来酰亚胺,其中马来酰亚胺官能度通过尿烷或尿素链连接到主链上,例如是下列优选的化合物:
Figure C9911139500131
and
Figure C9911139500132
式[M-Zm]n-K表示如下的一些化合物,其中:
M是具有下列结构式的马来酰亚胺部分
其中R1是H或C1-C5烷基;
Z是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与K连接;
或Z是具有下列结构式的尿烷:
Figure C9911139500134
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;和v是0-50;
或Z是具有下列结构式的硅氧烷:
-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表H、具有1-5个碳原子的烷基、或芳基,e和g独立地是1-10,f是1-50;
K是选自具有结构式(VI)-(XIII)的芳基(尽管示出只有一个键代表与芳基K连接,应认为代表所述的并由n定义的任何数量的附加键):
其中P是1-100
Figure C9911139500142
其中p是1-100:
其中R5、R6和R7是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接;或R5、R6和R7是具有结构式
-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CH3)g-的硅氧烷,
其中R1取代基是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e是1-10和f是0-50;
Figure C9911139500152
和(XII)
和m是0或1,和n是1-6。
更优选的马来酰亚胺化合物,尤其是用作再处理的组合物是N-丁基苯基马来酰亚胺和N-乙基苯基马来酰亚胺。
                乙烯基化合物
适用于本发明粘合剂组合物的乙烯基化合物(马来酰亚胺除外)具有下列结构式:
      or
                           或
Figure C9911139500163
对于这些具体的结构式,当下标“n”为1的整数时,化合物是单官能的化合物;当下标“n”为2-6的整数时,化合物是多官能化合物。
在这些结构式中,R1和R2是H或具有1-5个碳原子的烷基,或与形成乙烯基的碳一起形成5-9元的环;B是C、S、N、O、C(O)、O-C(O)、C(O)-O、C(O)NH或C(O)N(R8),其中R8是C1-C5烷基;m是0或1;n是1-6;和X、Q、Z和K具有上述含义。
优选地,B是O、C(O)、C(O)-O、C(O)NH或C(O)N(R8);更优选地,B是O、C(O)、O-C(O)、C(O)-O、或C(O)N(R8)。
优选的用作粘合剂的乙烯基化合物是乙烯基醚或链烯基硫化物。合适的乙烯基化合物的实例是下列化合物:
and
              其它组合物组分
根据需粘附的基体的性质,粘合剂还可含有偶合剂。本文所使用的偶合剂是含有可聚合官能团(与马来酰亚胺和其它乙烯基化合物反应)和能与基体表面上存在的金属氢氧化物缩合的官能团的化学物质。对于特定的基体来说,这类偶合剂和它们在组合物中的优选用量在本领域中是已知的。合适的偶合剂是硅烷、硅酸酯、金属丙烯酸盐或甲基丙烯酸盐、钛酸盐和含螯合剂的化合物,例如膦、硫醇和乙酰乙酸酯。当有偶合剂存在时,它们的用量通常是马来酰亚胺和其它单官能乙烯基化合物重量的至多10%(重量),优选0.1-3.0%(重量)。
另外,粘合剂组合物可含有使所得到的固化粘合剂具有额外柔韧性和韧度的化合物。这类化合物可以是任何热固性或热塑性材料,具有的Tg为50℃或50℃以下,通常是聚合物材料,其特征是,在醚基存在下和无环状结构时,化学键可自由转动。合适的这类改性剂包括聚丙烯酸酯、聚(丁二烯)、聚THF(聚合四氢呋喃)、CTBN(羧基封端的丁二烯-丙烯腈)橡胶和聚丙二醇。当有增韧化合物存在时,其用量是马来酰亚胺和其它单官能乙烯基化合物重量的至多约15%(重量)。
如果硅氧烷部分不是马来酰亚胺或乙烯基化合物结构,那么可向封装材料配方中加入硅氧烷,使其具有弹性。合适的硅氧烷是甲基丙烯酰氧基丙基端聚二甲基硅氧烷和氨基丙基端聚二甲基硅氧烷,由United Chemical Technologies等销售。
也可加入其它添加剂,例如粘合促进剂,可使用的种类和用量在本领域中是众所周知的。
                    特性
这些组合物将在工业化可接受的小片粘附粘合剂的范围内适用。对于在80×80密耳2硅小片上的粘合剂来说,工业上适用的小片剪切值的范围是在室温下大于或等于1Kg,在240℃下大于或等于0.5kg,对于500×500密耳2小片的翘曲来说,在室温下的范围是低于或等于70微米。×80密耳2硅小片上的粘合剂来说,工业上适用的小片剪切值的范围是在室温下大于或等于1Kg,在240℃下大于或等于0.5kg,对于500×500密耳2小片的翘曲来说,在室温下的范围是低于或等于70微米。
热膨胀系数(CTE)是指定材料在温度变化时单位尺寸的改变。不同的材料将具有不同的膨胀率。如果需粘附在一起的部件的CTE差值很大,那么热循环会引起粘附部件的弯曲、断裂或分层。在典型的半导体装配件中,芯片的CTE是2或3ppm/℃;对于有机电路板基体来说,CTE大于30ppm/℃;因此,粘合剂的CTE介于基体和小片之间是最好的。
当聚合物在应用中被加热时,它们将移向介于硬、玻璃态至软、橡胶态之间的过渡区域内。已知该区域是玻璃转变区域或Tg。如果绘制聚合物膨胀与温度的曲线图,那么玻璃转变区域是在较低温度/玻璃区域的热膨胀系数和较高温度/橡胶区域热膨胀系数之间的交叉处。在该区域上方,膨胀率明显地提高。因此,优选地是聚合物的玻璃转变要比应用期间经受的标准操作温度高,并且如果需要进行再处理的话,玻璃转变温度比任何再处理温度低。
本发明的其它实施方式包括具有式[M-Xm]n-Q和[M-Zm]n-K的马来酰亚胺,正如本文所描述的,其中Q和Z可以是具有下列结构式的酯
Figure C9911139500181
或结构式
Figure C9911139500182
其中p为1-100,
每个R3独立地代表烷基或烷氧基链,链上至多有100个原子,其中链上可含有芳基取代基,或
具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
本发明另一实施方式包括具有下列结构式的乙烯基化合物
Figure C9911139500191
正如本文所描述的,B是C、S、N、O、C(O)、C(O)NH或C(O)N(R),其中R8是C1-C5烷基。
本发明另一实施方式包括具有下列结构式的乙烯基化合物
正如本文所描述的,其中Q和Z可以是具有下列结构式的酯
或结构式
Figure C9911139500196
其中p为1-100,
每个R3独立地代表烷基或烷氧基链,链上至多有100个原子,其中链上可含有芳基取代基,或
具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基或芳基,e和g分别是1-
                   实施例
制备各种马来酰亚胺和乙烯基化合物并配制成粘合剂组合物。测定未固化组合物的粘度和触变指数,固化外形、玻璃转变温度、热膨胀系数、热机械分析和某些情况下固化组合物的再处理性。
                 实施例1
      制备丁二烯-丙烯腈双马来酰亚胺
在3升配有加料漏斗、机械搅拌器、内部温度探测器和氮气输入/输出口的四颈烧瓶中,将氨基封端的丁二烯丙烯腈(由BF Goodrich销售,商标为Hycar树脂1300×42 ATBN,其中结构中的m和n是整数,使得数均分子量为3600)(450克,500毫摩尔,按胺当量重量AEW=450克计)溶解在CHCl3(1000毫升)中。将搅拌溶液置于氮气下,在冰浴上冷却。在加料漏斗中加入CHCl3(50毫升)的马来酐(98.1克,1摩尔)并在30分钟内将该溶液加入到反应物中,保持内部反应温度在10℃以下。在冰浴上搅拌该混合物30分钟,然后使其温热至室温,再搅拌4小时。向所得到的浆料中加入乙酐(Ac2O)(653.4克,6摩尔)、三乙胺(Et3N)(64.8克,0.64摩尔)和乙酸钠(NaOAc)(62.3克,0.76摩尔)。加热反应物至轻度回流5小时,使其冷却至室温,随后用H2O(1升)、饱和NaHCO3(1升)和H2O(2×1升)进行萃取。真空除去溶剂,得到马来酰亚胺封端的丁二烯丙烯腈。
             实施例2制备由三(环氧基丙基)异氰脲酸酯
衍生的三(马来酰亚胺)
在2升配有机械搅拌器、内部温度探测器和氮气输入/输出口的三颈烧瓶中,将三(环氧基丙基)异氰脲酸酯(99.0克,0.33摩尔)溶解在THF(500毫升)中。向该溶解中加入羟苯基马来酰亚胺(189.2克,1摩尔)和苄基二甲胺(1.4克,0.05%(重量))。加热该溶液至80℃达7小时。使反应物冷却至室温,过滤,用5%HCl水溶液(500毫升)和蒸馏水(1升)洗涤滤液。将得到的固体三连氮三(马来酰亚胺)在室温下进行真空干燥。
                  实施例3
       制备马来酰亚氨基乙基棕榈酸酯
在2升配有机械搅拌器、内部温度探测器、加料漏斗和氮气输入/输出口的三颈烧瓶中,将棕榈酰氯(274.9克,1摩尔)溶解在Et2O(500毫升)中。在剧烈搅拌下,加入蒸馏水(500毫升)的NaHCO3(84.0克,1摩尔)溶液,在氮气下,在冰浴上冷却该溶液。在加料漏斗中加入Et2O(100毫升)的羟乙基马来酰亚胺(141克,1摩尔)的溶液,使该溶液在30分钟的期间内加入到反应物中,在加入期间,保持内部T<10℃。在冰浴上再搅拌反应物30分钟,然后使其温热至室温,搅拌4小时。将反应物转移到分液漏斗中,用蒸馏水(500毫升)、5%HCl水溶液(500毫升)和蒸馏水(2×500毫升)洗涤离析的有机层。离析有机相,用无水MgSO4进行干燥,过滤并真空除去溶剂,得到脂族马来酰亚胺。
             实施例4
    制备由5-异氰酰-1-(异氰酰甲基)
-1,3,3-三甲基环己烷衍生的双马来酰亚胺
在1升配有机械搅拌器、加料漏斗和氮气输入/输出口的三颈烧瓶中,将5-异氰酰-1-(异氰酰甲基)-1,3,3-三甲基环己烷(111.15克,0.5摩尔)溶解在THF(500毫升)中。将反应物置于氮气下,搅拌下加入二月桂酸二丁基锡(催化剂Sn″)(6.31克,10毫摩尔)和羟乙基马来酰亚胺(141克,1摩尔),在70℃下加热所得到的混合物4小时。在加料漏斗中加入溶解在THF(100毫升)中的羟乙基马来酰亚胺(141克,1摩尔)。在30分钟内,向异氰酸酯溶液中加入该溶液,在70℃下,再加热所得到的混合物4小时。使反应物冷却至室温,真空除去溶剂。将所得到的油溶解在CH2Cl2(1升)中,用10%HCl水溶液(1升)和蒸馏水(2×1升)洗涤。用MgSO4干燥离析的有机相,过滤并真空除去溶剂,得到马来酰亚胺。
                实施例5
   制备由Pripol 2033衍生的二聚二乙烯基醚
    “二聚二乙烯基醚”(和环状异构体)
在2升配有机械搅拌器的三颈烧瓶中,在氮气下,将双(1,10-菲咯啉)Pd(OAc)2(0.21克,0.54毫摩尔)溶解在丁基乙烯基醚(8.18克,81.7毫摩尔)、庚烷(100毫升)和“二聚二醇”(由Unichema销售,商标为Pripol 2033,15.4克,27.2毫摩尔)的混合物中。加热溶液至轻度回流6小时。使溶液冷却至室温,随后倒入活性碳中(20克)并搅拌1小时。过滤所得到的浆料,真空除去过量的丁基乙烯基醚和庚烷,得到二乙烯基醚,一种黄色油。产物具有合格的1HNMR,FT-IR和13C NMR光谱特征。粘度通常约为100cps。
              实施例6
      制备由二聚二醇(Pripol 2033)
        衍生的二聚二丙烯酸酯
在1升配有机械搅拌器、加料漏斗和内部温度探测器的三颈烧瓶中,在氮气下,将二聚二醇(由Unichema销售,商标为Pripol 2033,284.4克,500毫摩尔)溶解在无水丙酮(500毫升)中。向该溶液中加入三乙胺(101.2克,1摩尔),在冰浴上冷却溶液至4℃。将溶解在无水丙酮(100毫升)中的丙烯酰氯(90.5克,1摩尔)加入到加料漏斗中,在60分钟的期间内加入到搅拌的反应溶液中,保持内部温度<10℃。在冰浴上再搅拌溶液2小时,然后使其温热至室温,搅拌4小时。通过旋转蒸发器除去所有溶剂,并使剩余的残留物溶解在CH2Cl2(1升)中。用5%HCl水溶液(800毫升)和H2O(2×800毫升)洗涤该溶液。用无水MgSO4干燥离析的有机相,过滤,并真空除去溶剂,得到一种油状的二丙烯酸酯。
                实施例7
        制备N-乙基苯基马来酰亚胺
将4-乙基苯胺(12.12克)溶解在50毫升无水乙醚中,并缓慢加入在冰浴上冷冻的100毫升无水乙醚的9.81克马来酐搅拌溶液。在加入完成后,将反应混合物搅拌30分钟。过滤并干燥淡黄色的晶体。用乙酐(200毫升)溶解马来酸和20克乙酸钠。在160℃油浴中加热反应混合物。回流3小时后,使溶液冷却至室温,置于1升在冰水中的烧杯中,剧烈搅拌1小时。吸滤产物,用己烷再结晶。将收集的结晶物质在50℃的真空炉中干燥过夜。FTIR和NMR分析表明了乙基马来酰亚胺的特征。
              实施例8
        制备双(链烯基硫化物)
在3升配有机械搅拌器和迪安-斯达克蒸馏装置的三颈烧瓶中,将二聚酸(由Unichema销售,商标为Empol 1024)(574.6克,1摩尔)和炔丙醇(112.1克,2摩尔)溶解在甲苯(1升)中。加入浓H2SO4(6毫升),回流溶液6小时,直到36毫升的水被共沸蒸馏掉。使溶液冷却至室温,用水(2×1升)洗涤,用无水MgSO4干燥,真空除去溶剂,得到一种油状炔丙酯中间体。
在1升配有回流冷凝器、机械搅拌器和内部温度探测器的三颈烧瓶中,在氮气下,将该酯中间体(650.7克,1摩尔)溶解在THF(200毫升)中。加入月桂基硫醇(404.8克,2摩尔)和2,2′-偶氮双(2,4-二甲基戊腈)(由DuPont销售,商标为Vazo 52)(11克),在冰浴上,搅拌下加热所得到的混合物至70℃达7小时。使反应物冷却至室温,真空除去溶剂,得到一种油状链烯基硫化物。
               实施例A
         制备6-马来酰亚氨基己酸
Figure C9911139500252
              6-马来酰亚氨基己酸
采用已知工艺合成酸官能化马来酰亚胺,6-马来亚氨基己酸。在500毫升配有机械搅拌器、内部温度探测器和加料漏斗的四颈烧瓶中,将氨基己酸(100克,7.6×10-1摩尔)溶解在冰醋酸(50毫升)中。在加料漏斗中加入已经溶解在乙腈(75毫升)中的马来酐(74.8克,7.6×10-1摩尔)溶液。将该溶液在室温下在1小时内滴加到氨基己酸中,保持内部反应温度低于35℃。在加入完成后,搅拌反应物3小时。过滤反应浆料,在真空炉(P约25T)中,在70℃下干燥经离析的滤液过夜,得到166克白色固体(95%)。产物酰胺酸具有FT-IR和1H NMR光谱特征,与文献数据一致。
在1升配有机械搅拌器和迪安-斯达克分水器的三颈烧瓶中,在氮气下将上述酰胺酸(166克,7.2×10-1摩尔)溶解在甲苯(200毫升)、苯(200毫升)和三乙胺(211毫升,1.51摩尔)的溶液中。加热溶液回流4小时,在迪安-斯达克分水器中收集产生的水。向反应烧瓶中加入蒸馏水(400毫升),溶解在反应期间从总溶液中分离出来的大部分产物的三乙基铵盐。离析水层,用50%HCl酸化至pH约1,用乙酸乙酯(600毫升)萃取。用蒸馏水(400毫升)洗涤有机层。用MgSO4干燥离析的有机层,接着真空除去溶剂,得到一种白色固体(76.2克,50%)。光谱分析产物的6-马来酰亚氨基己酸的FT-IR和1H NMR与文献中的产品一致。
                  实施例B
          制备“二聚二酯双马来酰亚胺”
Figure C9911139500261
     “二聚二酯双马来酰亚胺”(和环状异构体)
在1升配有机械搅拌器、迪安-斯达克分水器和内部温度探测器的四颈烧瓶中,在氮气下将Pripol 2033(“二聚二醇”,Uniqema,92.4克,1.69×10-1摩尔)、6-马来酰亚氨基己酸(75.0克,3.55×10-1摩尔)和H2SO4(0.50毫升,约8.5×10-3摩尔)在甲苯中制浆。加热反应物至轻度回流2小时,在迪安-斯达克分水器中收集离析的水。取出分水器,蒸馏掉反应物中的约50毫升甲苯溶剂,除去痕量的水分,酯化平衡至完全。使反应物冷却至室温,加入其它的甲苯(100毫升)(实验室规模,优选在此时加入二乙醚而不是甲苯),用饱和NaHCO3水溶液(300毫升)和蒸馏水(300毫升)洗涤该溶液。离析有机层,用无水MgSO4进行干燥,真空除去溶剂,得到一种橙色油(107.2克,68%)。经二氧化硅或氧化铝的短塞通过洗脱树脂的甲苯溶液进一步提纯该物质。液相双马来酰亚胺树脂具有合格的FT-IR,1H NMR,和13C NNR数据,η通常约为2500cps。
               实施例C
    制备“癸基二醇二酯双马来酰亚胺”
         “癸基二醇二酯双马来酰亚胺”
按实施例B所述的一般步骤制备,只是用癸基二醇(29.5克,1.69×10-1摩尔)代替Pripol 2033。该方法制得一种固体,中等溶解度的双马来酰亚胺(54.9克,58%)。该产物具有合格的FT-IR和1H NMR数据。
                实施例D
        制备“甘油三酯三(马来酰亚胺)”
按实施例B的要点制备,只是用甘油(10.4克,1.13×10-1摩尔)代替Pripol2033。产物是一种粘性的液体,具有合格的FT-IR和1H NMR数据。
                实施例E
      制备“IPDI的双(氨基甲酸间-硝基苄酯)”
Figure C9911139500282
      “IPDI的双(氨基甲酸间-硝基苄酯)”
在2升配有机械搅拌器、回流冷凝器和内部温度探测器的三颈烧瓶中,在氮气下,将异佛尔酮二异氰酸酯(“IPDI”,100.0克,4.5×10-1摩尔),间-硝基苄基醇(137.8克,9.0×10-1摩尔)和二月桂酸二丁基锡(2.8克,4.5×10-3摩尔)溶解在无水甲苯(1500毫升)中。加热所得到的溶液至90℃达4小时。在试样的固体部分的IR中未观察到异氰酸酯带。使溶液冷却至室温,用蒸馏水(100毫升)洗涤。离析有机层,真空除去溶剂,得到一种黄色液体,具有合格的FT-IR和1H NMR特征。
                  实施例F
        制备“IPDI的双(氨基甲酸间-氨基苄酯)”
       “IPDI的双(氨基甲酸间-氨基苄酯)”
在500毫升配有磁性搅拌器的三颈园底烧瓶中,在氮气下,将实施例E的二硝基化合物(8.28克,1.57×10-2摩尔)溶解在乙醇(100毫升)中。加入环己烷(28.6毫升,2.82×10-1摩尔),接着加入5%Pd/C(4.14克)。使得到的浆料轻度回流6.5小时。该溶液过滤的等分试样的FT-IR在1529厘米-1和1352厘米-1处没有硝基拉伸带。使所有溶液冷却至室温并过滤。真空除去溶剂,得到一种黄色半固体(6.6克,90%),具有合格的FT-IR和1H NMR光谱特征。
                实施例G
  制备“IPDI的双(氨基甲酸间-马来酰亚氨基苄酯)”
Figure C9911139500292
   “IPDI的双(氨基甲酸间-马来酰亚氨基苄酯)”
在250毫升配有磁性搅拌器和加料漏斗的四颈烧瓶中,在氮气下,将实施例F的二胺(6.6克,1.41×10-2摩尔)溶解在丙酮(60毫升)中,并冷却至4℃。在30分钟的期间内,加入已溶解在丙酮(20毫升)中的马来酐(2.76克,2.82×10-2摩尔)。在4℃下搅拌所得到的溶液1小时,接着使其温热至室温并搅拌过夜。根据在约1810厘米-1处没有酐拉伸带的判断,FT-IR分析表明没有残留的马来酐。
向上述酰胺酸溶液中加入乙酐(8.5毫升,9.0×10-2摩尔)、三乙胺(1.26毫升,9.0×10-3摩尔)和乙酸钠(0.88克,1.1×10-2摩尔)。使所得到的溶液在氮气下轻度回流4小时。使反应物冷却至室温,真空除去所有溶剂。将得到的粘性溶液再溶解在二氯甲烷(200毫升)中,用蒸馏水(3×200毫升)萃取。然后用无水MgSO4干燥有机相,过滤并真空除去溶剂,得到一种淡棕色固体(6.75克,76%)。该物质具有合格的FT-IR和1H NMR光谱特征。
                 实施例H
    制备“DDI 1410的双(氨基甲酸间-硝基苄酯)”
  “DDI的双(氨基甲酸间-硝基苄酯)”(和环状异构体)
在1升配有机械搅拌器、回流冷凝器和内部温度探测器的四颈烧瓶中,在氮气下,将DDI 1410(Henkel,“二聚二异氰酸酯”,99.77克,1.65×10-1摩尔,按13.96%NCO计)、间-硝基苄醇(50.8克,3.32×10-1摩尔)和二月桂酸二丁基锡(0.5毫升,8.3×10-4摩尔)溶解在甲苯(150毫升)中。加热反应物至85℃达2.5小时。根据缺乏2272厘米-1带的判断,反应物等分试样的FT-IR分析表明异氰酸酯官能度完全消耗完。在真空中,从反应物中除去溶剂,得到一种黄色油,该油在室温下放置时固化(152.4克,102%(痕量甲苯))。该固体具有合格的FT-IR和1H NMR光谱特征。
               实施例I
   制备“DDI 1410的双(氨基甲酸间-氨基苄酯)”
Figure C9911139500311
“DDI 1410的双(氨基甲酸间-氨基苄酯)”(和环状异构体)
在1升配有机械搅拌器和回流冷凝器的三颈烧瓶中,在氮气下,将实施例H的二胺产物(39.6克,4.32×10-2摩尔)和氯化亚锡二水合物(97.55克,4.32×10-1摩尔)制浆在乙酸乙酯(300毫升)中。加热反应物至轻度回流并剧烈搅拌3小时。使溶液冷却至室温,用饱和NaHCO3溶液调节pH7-8。使混合物通过25微米的过滤器,得到一种分离成浑浊水层和中度透明的有机层的混合物。离析水层,用乙酸乙酯(100毫升)进行洗涤。合并有机层,用蒸馏水(300毫升)洗涤并用无水MgSO4进行干燥。过滤浆料,真空除去滤液中的溶剂,得到一种黄色、粘稠的固体(33.8克,92%)。
               实施例J
  制备“DDI 1410的双(氨基甲酸间-马来酰亚氨基苄酯)”
Figure C9911139500312
   “DDI 1410的双(氨基甲酸间-马来酰亚氨基酯)”(和环状异构体)
在2升配有机械搅拌器、内部温度探测器和加料漏斗的四颈烧瓶中,在氮气下,将马来酐(15.4克,1.57×10-2摩尔)溶解在丙酮(300毫升)中。在冰浴上冷却溶液至约4℃。向加料漏斗中加入己溶解在丙酮(70毫升)中实施例I制备的二胺溶液(63.4克,7.48×10-2摩尔)并在30分钟内加入到马来酐溶液中,保持内部温度<10℃。搅拌所得到的溶液1小时,接着使其温热至室温,并搅拌2小时。
向该酰胺酸溶液中加入乙酐(24.7毫升,2.62×10-1摩尔)、三乙胺(6.25毫升,4.48×10-2摩尔)和乙酸锰四水合物(0.37克,1.50×10-3摩尔)。加热该溶液至轻度回流6.5小时,然后使其冷却至室温。真空除去所有溶剂,将制得的深色溶液溶解在二乙醚(500毫升)中。用蒸馏水(500毫升)洗涤该溶液。然后用饱和NaHCO3水溶液(500毫升)洗涤离析的有机层,并再次用蒸馏水(500毫升)洗涤。离析有机相,用无水MgSO4干燥,真空除去溶剂,得到一种粘性橙色油。该物质具有FT-IR、1H NMR和13C NMR光谱特征,与所期望的双马来酰亚胺产物的一致。
                  实施例AA
低应力小片粘附粘合剂制剂和对各种引线框的小片剪切强度
粘度为9011cps(5rpm,锥体和板)和触变指数为5.36的银填充小片粘附粘合剂制剂的制备是在室温下采用机械混合器将下列各组分混合:
实施例B的液态双马来酰亚胺:               2.644克
实施例5的二聚二乙烯基醚:                 2.644克
Ricon 131MA20(Ricon Resins,Inc.):       0.661克
Silquest A-174(Witco Corp.):             0.040克
USP-90MD(Witco Corp.):                   0.099
XD0026(NSCC商业机密):                    0.119
SF-96银粉                                 23.794
按如下描述,将制成的浆料分散到各种金属引线框中,并将120×120密耳2硅小片置于粘合剂珠中,制成约1密耳的粘合层。将试样在200℃下“快速固化”60秒,测定在室温和240℃下小片的剪切强度。然后将这些试样在升高的温度和湿度(85℃/85%RH)下处理48小时。再次测定室温和240℃下的小片剪切强度。结果示于表1中。
                              表1
马来酰亚胺/乙烯基醚小片粘附粘合剂的小片剪切强度(DSS)
       未暴露在湿度下              暴露在湿度下(48小时/85℃/85RH)
固化外形 60s/200℃ 60s/200℃
试验温度 25℃ 240℃ 25℃ 240℃
Cu引线框DSS(kg) 4.88+/-0.25 1.46+/-0.35 6.54+/-0.82 1.84+/-0.76
Ag-Cu引线框DSS(kg) 5.29+/-0.34 2.17+/-0.43 9.50+/-1.88 1.56+/-0.72
Pd-CuDSS(kg) 5.52+/-0.39 1.99+/-0.44 11.9+/-1.3 3.53+/-0.66
在85℃/85%RH下饱和后,这些装置典型的湿度提高值是0.18%(重量)。固化期间的重量损失是0.16+/-0.05%(重量)。
                    实施例BB
    马来酰亚胺/乙烯基醚小片粘附粘合剂的HAST试验
与实施例AA类似,将120×120密耳的小片粘附到各种组合物的引线框上,所使用的组合物是实施例AA中所给出的。然后将粘附的小片进行“快速固化”(60s/200℃)和“快速烘箱固化”(15分钟/175℃)。将所制成的固化装置置于模拟的HAST试验条件(130℃,85%RH)下130小时。根据在室温和升高温度下测定小片的剪切强度(DSS),表明该装置具有极好的粘附性,如表2所述。
           表2
在模拟HAST试验后的剪切强度
固化外形 60s/200℃ 15分钟/175℃
试验温度 25℃ 240℃ 25℃ 240℃
Cu引线框DSS(kg) 15.3+/-1.8 1.12+/-0.35 17.2+/-0.8 1.25+/-0.39
Ag-Cu引线框DSS(kg) 16.3+/-1.9 2.81+/-0.55 14.8+/-1.8 2.6+/-1.6
Pd-CuDSS(kg) 15.7+/-1.7 3.04+/-0.46 14.4+/-0.7 2.96+/-0.90
             实施例CC
用马来酰亚胺/乙烯基醚小片粘附粘合剂粘合的大片的翘曲
用实施例AA所述的小片粘附组合物将500×500密耳2小片粘合到Pd-Cu引线框上。“快速固化”装配件,并测定几种温度和时间下的翘曲。结果示于表3中。当这种粘合剂作为“低应力材料”时,具有极好的性能。
                     表3
500×500密耳2小片上马来酰亚胺/乙烯基醚小片粘附粘合剂的翘曲
温度随时间的变化 1分钟/200℃ +1分钟/240℃ +4小时/175℃
翘曲(微米) 10.4+/-1.3 11.9+/-1.4 14.1+/-1.6
                实施例DD
马来酰亚胺/乙烯基醚小片粘附粘合剂的热分析
采用降压压力计,用实施例AA的组合物制备约1密耳的膜。在热板上“快速固化”(60秒,200℃)或烘箱固化(4小时/175℃)该膜,由动力学分析(DMA)来确定特性。结果示于表4中。
              表4
马来酰亚胺/乙烯基醚小片粘附膜的热分析
固化外形 60s/200℃ 4小时/175℃
Tg(℃) -1 35
-65℃模量(E′)(psi) 421300 513900
100℃模量(E′)(psi) 5864 23980
在低应力粘合剂的Tg下,该材料具有较低的模量。在温度高于Tg时,材料的模量足以耐线连接条件,而没有损坏。
在下面的数个段落中包括本发明的其它实施方式:
1.一种用于将电子元件粘合到基体上的粘合剂组合物,含有一种马来酰亚胺化合物和选自游离基引发剂、光引发剂和它们混合物的固化引发剂,马来酰亚胺化合物具有式[M-Xm]n-Q,其中m是0或1,n是1-6,和
(a)M是具有下列结构式的马来酰亚胺部分
其中R1是H或具有1-5个碳原子的烷基;
(b)X是选自具有下述结构式的芳基:
(c)Q是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与X连接。
2.根据段落1的固化粘合剂组合物,其中Q是直链或支链烷基、烷氧基、亚烷基或烯化氧,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
3.根据段落2的固化粘合剂组合物,其中Q是直链或支链烷基,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
4.根据段落1的固化粘合剂组合物,其中Q是具有下列结构式的尿烷:
Figure C9911139500353
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50。
5.根据段落1的固化粘合剂组合物,其中Q是具有下列结构式的酯:
Figure C9911139500361
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链上可含有芳基取代基。
6.根据段落1的固化粘合剂组合物,其中Q是具有下列结构式的酯:
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链;其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR12)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
7.根据段落1的固化粘合剂组合物,其中Q是具有下列结构式的酯:
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
8.一种固化粘合剂组合物,含有一种马来酰亚胺化合物和选自游离基引发剂、光引发剂和它们混合物的固化引发剂,马来酰亚胺化合物具有式[M-Zm]n-K,其中m是0或1,n是1-6,和
(a)M是具有下列结构式的马来酰亚胺部分
Figure C9911139500371
其中R1是H或具有1-5个碳原子的烷基;
(b)K是选自具有下述结构式的芳基:
Figure C9911139500372
其中P是1-100
其中p是1-100;
其中R5、R6和R7是直链或支链烷基、烷氧基、、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接;
或R5、R6和R7是具有结构式
-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CH3)g-的硅氧烷,
其中R1取代基是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e是1-10和f是1-50;
Figure C9911139500391
(c)Z是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与K连接。
9.根据段落8的固化粘合剂组合物,其中Z是直链或支链烷基、烷氧基、亚烷基或烯化氧,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
10.根据段落8的固化粘合剂组合物,其中Z是直链或支链烷基,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
11.根据段落8的固化粘合剂组合物,其中Z是具有下列结构式的尿烷:
Figure C9911139500401
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50。
12.根据段落8的固化粘合剂组合物,其中Z是具有下列结构式的酯:
Figure C9911139500402
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基。
13.根据段落8的固化粘合剂组合物,其中Z是具有下列结构式的酯:
Figure C9911139500403
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链;其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基或芳基,e和g分别是1-10和f是1-50。
14.根据段落8的固化粘合剂组合物,其中Z是具有下列结构式的酯:
Figure C9911139500404
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CH1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
15.根据段落8-14任一项的固化粘合剂组合物,其中K是
其中p是1-100。
16.根据段落8-14任一项的固化粘合剂组合物,其中K是
其中R5、R6和R7是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接。
17.根据段落8-14任一项的固化粘合剂组合物,其中K是
Figure C9911139500421
18.一种固化粘合剂组合物,含有乙烯基化合物和选自游离基引发剂、光引发剂和它们的混合物的固化引发剂,乙烯基化合物具有下列式
Figure C9911139500422
其中m是0或1,n是1-6;和
(a)R1和R2是H或具有1-5个碳原子的烷基,或与形成乙烯基的碳一起形成5-9元的环;
(b)B是C、S、N、O、C(O)、C(O)NH或C(O)N(R8),其中R8是具有1-5个碳原子的烷基;
(c)X是选自具有下列结构式的芳基
(d)Q是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与X连接。
19.根据段落18的固化粘合剂组合物,其中Q是直链或支链烷基、烷氧基、亚烷基或烯化氧,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
20.根据段落19的固化粘合剂组合物,其中Q是直链或支链烷基,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
21.根据段落18的固化粘合剂组合物,其中Q是具有下列结构式的尿烷:
Figure C9911139500431
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50。
22.根据段落18的固化粘合剂组合物,其中Q是具有下列结构式的酯:
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基。
23.根据段落18的固化粘合剂组合物,其中Q是具有下列结构式的酯:
Figure C9911139500433
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链;其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
24.根据段落18的固化粘合剂组合物,其中Q是具有下列结构式的酯:
Figure C9911139500441
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
25.一种固化粘合剂组合物,含有乙烯基化合物和选自游离基引发剂、光引发剂和它们的混合物的固化引发剂,乙烯基化合物具有下列式
其中m是0或1,n是1-6;和
(a)R1和R2是H或具有1-5个碳原子的烷基,或与形成乙烯基的碳一起形成5-9元的环;
(b)B是C、S、N、O、C(O)、C(O)NH或C(O)N(R8),其中R8是具有1-5个碳原子的烷基;
(c)K是选自具有下列结构式的芳基
Figure C9911139500451
其中p是1-100;
Figure C9911139500452
其中p是1-100;
其中R6、R6和R7是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接;
或R5、R6和R7是具有结构式
-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CH3)g-的硅氧烷,
其中R1取代基是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e是1-10和f是1-50;
Figure C9911139500461
(d)Z是直链支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与X连接。
26.根据段落25的固化粘合剂组合物,其中Z是直链或支链烷基、烷氧基、亚烷基或烯化氧,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
27.根据段落25的固化粘合剂组合物,其中Z是直链或支链烷基,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基。
28.根据段落25的固化粘合剂组合物,其中Z是具有下列结构式的尿烷:
其中:每个R3独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50。
29.根据段落25的固化粘合剂组合物,其中Z是具有下列结构式的酯:
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基。
30.根据段落25的固化粘合剂组合物,其中Z是具有下列结构式的酯:
Figure C9911139500473
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链;其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
31.根据段落25的固化粘合剂组合物,其中Z是具有下列结构式的酯;
Figure C9911139500481
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
32.根据段落25-31任一项的固化粘合剂组合物,其中K是
其中p是1-100。
33.根据段落25-31任一项的固化粘合剂组合物,其中K是
其中R5、R6和R7是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接。
34.根据段落25-31任一项的固化粘合剂组合物,其中K是
Figure C9911139500491
35.一种固化粘合剂组合物,含有段落1-17任一项所述的马来酰亚胺化合物和段落18-34任一项所述的乙烯基化合物和固化引发剂。
36.一种固化粘合剂组合物,含有段落1-17任一项所述的马来酰亚胺,或段落18-34任一项所述的乙烯基化合物,或段落1-17任一项所述的马来酰亚胺和段落18-34任一项所述的乙烯基化合物的混合物,和一种阴离子或阳离子固化引发剂。
37.一种电子装配件,含有用上述段落任一项的组合物制备的固化粘合剂组合物粘合到基体上的电子元件。

Claims (5)

1.一种用于将电子元件粘合到基体上的可固化粘合剂组合物,含有一种马来酰亚胺化合物和选自游离基引发剂、光引发剂和它们混合物的固化引发剂,马来酰亚胺化合物具有式[M-Xm]n-Q,其中m是0或1,n是1-6,和
(a)M是具有下列结构式的马来酰亚胺部分
其中R1是H或具有1-5个碳原子的烷基;
(b)X是选自具有下述结构式的芳基:
(c)Q是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与X连接;或
(d)Q是具有下列结构式的酯
Figure C9911139500031
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;或
(e)Q是具有下列结构式的尿烷:
Figure C9911139500032
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50;
(f)Q是具有下列结构式的酯:
Figure C9911139500033
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50;或
(g)Q是具有下列结构式的酯:
Figure C9911139500041
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立代表具有具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
2.一种固化粘合剂组合物,含有一种马来酰亚胺化合物和选自游离基引发剂、光引发剂和它们混合物的固化引发剂,马来酰亚胺化合物具有式[M-Zm]n-K,其中m是0或1,n是1-6,和
(a)M是具有下列结构式的马来酰亚胺部分
Figure C9911139500042
其中R1是H或具有1-5个碳原子的烷基;
(b)K是选自具有下述结构式的芳基:
其中p是1-100;
Figure C9911139500052
其中p是1-100;
其中R5、R6和R7是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基和芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与芳香环连接;
或R5、R6和R7是具有结构式
-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CH3)g-的硅氧烷,
其中R1取代基是H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基或芳基,e是1-10和f是1-50;
(c)Z是直链或支链烷基、烷氧基、烷基胺、烷基硫化物、亚烷基、烯化氧、亚烷基胺、亚烷基硫化物、芳基、芳氧基或芳基硫化物,它们可含悬挂于链上或作为链上的部分主链的饱和或不饱和的环状或杂环取代基,其中任何存在的杂原子可以或可以不直接与K连接;或
(d)Z是具有下列结构式的酯
Figure C9911139500071
其中:R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;或
(e)Z是具有下列结构式的尿烷:
其中:每个R2独立地代表具有1-18个碳原子的烷基、芳基、或芳烷基;R3代表烷基或烷氧基链,在链上至多有100个原子,其中链可含有芳基取代基;X代表O、S、N或P;和v是0-50;或
(f)Z是具有下列结构式的酯:
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,该链可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-O]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基或芳基,e和g分别是1-10和f是1-50;或
(g)Q是具有下列结构式的酯:
Figure C9911139500074
其中p是1-100,和
每个R3可独立地代表链上至多有100个原子的烷基或烷氧基链,其中链上可含有芳基取代基;或
每个R3独立地代表具有结构式-(CR1 2)e-[SiR4 2-0]f-SiR4 2-(CR1 2)g-的硅氧烷,
其中每个部分的R1取代基独立地代表H或具有1-5个碳原子的烷基,每个部分的R4取代基独立地代表具有1-5个碳原子的烷基、或芳基,e和g分别是1-10和f是1-50。
3.一种固化粘合剂组合物,含有权利要求1或2的马来酰亚胺化合物和固化引发剂。
4.一种固化粘合剂组合物,含有权利要求1或2的马来酰亚胺化合物,和一种阴离子或阳离子固化引发剂。
5.一种电子装配件,含有用上述任一项权利要求的组合物制备的固化粘合剂组合物粘合到基体上的电子元件。
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US6852814B2 (en) * 1994-09-02 2005-02-08 Henkel Corporation Thermosetting resin compositions containing maleimide and/or vinyl compounds
US6355750B1 (en) * 1998-07-02 2002-03-12 National Starch And Chemical Investment Holding Corporation Dye attach adhesives for use in microelectronic devices
KR100789332B1 (ko) * 2000-05-18 2007-12-28 내쇼날 스타치 앤드 케미칼 인베스트멘트 홀딩 코포레이션 비닐 에테르 및 카바메이트 또는 유레아 작용기를 가진 다이 부착용 접착제
US6441213B1 (en) * 2000-05-18 2002-08-27 National Starch And Chemical Investment Holding Corporation Adhesion promoters containing silane, carbamate or urea, and donor or acceptor functionality
CN1109086C (zh) * 2000-07-19 2003-05-21 湖北省化学研究所 一种柔性印刷电路用的反应型阻燃胶粘剂及制备
US6887916B2 (en) * 2000-12-28 2005-05-03 Kimberly-Clark Worldwide, Inc. Materials having controlled shrinkage and patterns and methods of making same
US6798074B2 (en) * 2002-03-04 2004-09-28 Motorola, Inc. Method of attaching a die to a substrate
US6831132B2 (en) * 2002-03-28 2004-12-14 Henkel Corporation Film adhesives containing maleimide compounds and methods for use thereof
US6803406B2 (en) 2002-03-29 2004-10-12 National Starch And Chemical Investmnet Holding Corporation Electron donors, electron acceptors and adhesion promoters containing disulfide
CN101488480A (zh) * 2002-06-17 2009-07-22 亨凯尔公司 间层电介质和预施涂的模片连接粘合剂材料
US7176044B2 (en) * 2002-11-25 2007-02-13 Henkel Corporation B-stageable die attach adhesives
US8513375B2 (en) * 2003-05-05 2013-08-20 Designer Molecules, Inc. Imide-linked maleimide and polymaleimide compounds
MXPA05012039A (es) * 2003-05-05 2006-05-31 Advanced Applied Adhesives Compuestos maleimida imida-enlazados y polimaleimida.
US7884174B2 (en) 2003-05-05 2011-02-08 Designer Molecules, Inc. Imide-linked maleimide and polymaleimide compounds
JP2007517875A (ja) * 2004-01-16 2007-07-05 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション シアヌレート核を有するマレイミド樹脂
CN1930263B (zh) * 2004-03-19 2012-02-29 住友电木株式会社 树脂组合物及采用该树脂组合物制作的半导体装置
US7160946B2 (en) * 2004-04-01 2007-01-09 National Starch And Chemical Investment Holding Corporation Method to improve high temperature cohesive strength with adhesive having multi-phase system
CN1774451A (zh) * 2004-05-13 2006-05-17 横滨橡胶株式会社 马来酰亚胺封端橡胶和用所述马来酰亚胺封端橡胶制备的可固化组合物
US20050267254A1 (en) * 2004-05-28 2005-12-01 Mizori Farhad G Functionalized urethanes and methods for use thereof
JP2008501826A (ja) * 2004-06-04 2008-01-24 デジグナー モレキュールズ インコーポレイテッド フリーラジカル硬化可能なポリエステル類およびその使用方法
US7875688B2 (en) * 2004-06-04 2011-01-25 Designer Molecules, Inc. Free-radical curable polyesters and methods for use thereof
US7875686B2 (en) * 2004-08-18 2011-01-25 Promerus Llc Polycycloolefin polymeric compositions for semiconductor applications
US20060284141A1 (en) * 2005-06-21 2006-12-21 Musa Osama M Metal salts of maleimide compounds as conductivity promoters
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
JP2009531516A (ja) * 2006-03-29 2009-09-03 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション 放射線−硬化性ゴム系接着剤/シーラント
US7691475B2 (en) * 2006-07-21 2010-04-06 3M Innovative Properties Company Anisotropic conductive adhesives
US7422707B2 (en) * 2007-01-10 2008-09-09 National Starch And Chemical Investment Holding Corporation Highly conductive composition for wafer coating
US20080262191A1 (en) * 2007-01-26 2008-10-23 Mizori Farhad G Methods for the preparation of imides, maleimides and maleimide-terminated polyimide compounds
US20080203566A1 (en) * 2007-02-27 2008-08-28 Chao-Yuan Su Stress buffer layer for packaging process
WO2008120772A1 (en) 2007-03-29 2008-10-09 Canon Kabushiki Kaisha Active energy ray curable liquid composition and liquid cartridge
US8158746B2 (en) 2007-03-29 2012-04-17 Canon Kabushiki Kaisha Active energy ray curable liquid composition and liquid cartridge
US7868113B2 (en) 2007-04-11 2011-01-11 Designer Molecules, Inc. Low shrinkage polyester thermosetting resins
US8063161B2 (en) * 2007-04-16 2011-11-22 Designer Molecules, Inc. Low temperature curing acrylate and maleimide based formulations and methods for use thereof
WO2009035958A2 (en) 2007-09-13 2009-03-19 3M Innovative Properties Company Low temperature bonding electronic adhesives
US8308892B2 (en) 2008-04-09 2012-11-13 Designer Molecules, Inc. Di-cinnamyl compounds and methods for use thereof
CN102149761B (zh) * 2008-08-08 2016-10-12 汉高知识产权控股有限责任公司 低温固化的组合物
US8008419B2 (en) 2008-08-13 2011-08-30 Designer Molecules, Inc. Siloxane monomers and methods for use thereof
US8637611B2 (en) 2008-08-13 2014-01-28 Designer Molecules, Inc. Amide-extended crosslinking compounds and methods for use thereof
US8415812B2 (en) * 2009-09-03 2013-04-09 Designer Molecules, Inc. Materials and methods for stress reduction in semiconductor wafer passivation layers
US8686162B2 (en) 2010-08-25 2014-04-01 Designer Molecules Inc, Inc. Maleimide-functional monomers in amorphous form
US8816021B2 (en) 2010-09-10 2014-08-26 Designer Molecules, Inc. Curable composition with rubber-like properties
JP6120072B2 (ja) * 2012-10-17 2017-04-26 Jsr株式会社 液晶配向剤
US20170360815A1 (en) * 2016-02-25 2017-12-21 Applied Biological Laboratories, Inc. Compositions and methods for protecting against airborne pathogens and irritants

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3403172A (en) 1964-01-03 1968-09-24 Agriculture Usa Hard, high-melting waxes from longchain n-allylamides
ZA702294B (en) * 1969-04-25 1971-02-24 Gen Electric Novel bis-imide compositions and polymers therefrom
JPS5610529A (en) * 1979-07-09 1981-02-03 Mitsubishi Gas Chem Co Inc Curable resin composition
FR2469421A1 (fr) 1979-11-09 1981-05-22 Rhone Poulenc Ind Procede d'encapsulation de composants electroniques a l'aide d'une matiere moulable a base d'un prepolymere thermodurcissable
DE3233912A1 (de) 1982-09-13 1984-03-15 Merck Patent Gmbh, 6100 Darmstadt Fotolacke zur ausbildung von reliefstrukturen aus hochwaermebestaendigen polymeren
US4581461A (en) * 1983-04-07 1986-04-08 National Starch And Chemical Corporation Maleated siloxane derivatives
US4806608A (en) * 1987-03-16 1989-02-21 Loctite Corporation Curable siloxane maleimide composition
US4886842A (en) * 1988-03-04 1989-12-12 Loctite Corporation Epoxy-amine compositions employing unsaturated imides
JP2718156B2 (ja) * 1989-03-20 1998-02-25 日立化成工業株式会社 耐熱性接着剤組成物
CA2013018A1 (en) * 1989-03-31 1990-09-30 Isao Kaneko Imide prepolymers, cured products, method for making, laminate preparation, and encapsulating compositions
JPH0855940A (ja) * 1994-08-12 1996-02-27 Sumitomo Chem Co Ltd 熱硬化性樹脂組成物
JPH10505599A (ja) * 1994-09-02 1998-06-02 クアンタム マテリアルズ,インコーポレイテッド マレイミド及び/又はビニル化合物を含有する熱硬化性樹脂組成物
JP2896755B2 (ja) * 1995-06-08 1999-05-31 株式会社巴川製紙所 電子部品用接着テープ
JPH1095958A (ja) * 1996-09-24 1998-04-14 Sumitomo Bakelite Co Ltd 半導体装置
JPH10101796A (ja) * 1996-09-30 1998-04-21 Matsushita Electric Works Ltd イミド樹脂組成物
US5840215A (en) * 1996-12-16 1998-11-24 Shell Oil Company Anisotropic conductive adhesive compositions
JPH10168413A (ja) 1996-12-16 1998-06-23 Sumitomo Bakelite Co Ltd 異方導電性接着剤
JP3601654B2 (ja) * 1997-05-16 2004-12-15 大日本インキ化学工業株式会社 マレイミド誘導体を含有する活性エネルギー線硬化性組成物及び該硬化性組成物の硬化方法
JP3599160B2 (ja) * 1997-05-16 2004-12-08 大日本インキ化学工業株式会社 マレイミド誘導体を含有する活性エネルギー線硬化性組成物及び該活性エネルギー線硬化性組成物の硬化方法

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