CN103122221B - 具有改善的预粘合加工性的各向异性导电膜和半导体装置 - Google Patents

具有改善的预粘合加工性的各向异性导电膜和半导体装置 Download PDF

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Publication number
CN103122221B
CN103122221B CN201210447575.9A CN201210447575A CN103122221B CN 103122221 B CN103122221 B CN 103122221B CN 201210447575 A CN201210447575 A CN 201210447575A CN 103122221 B CN103122221 B CN 103122221B
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adhesive layer
conductive film
anisotropic conductive
reaction monomers
methyl
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CN103122221A (zh
Inventor
高连助
金镇圭
鱼东善
李吉镛
曹长铉
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Guo Dujianduansucai
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Daiichi Woolen Co ltd
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    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/52—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/10—Adhesives in the form of films or foils without carriers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
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    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
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    • C09J9/00—Adhesives characterised by their physical nature or the effects produced, e.g. glue sticks
    • C09J9/02—Electrically-conducting adhesives
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Abstract

本发明公开了一种各向异性导电膜和包括该膜的半导体装置，所述各向异性导电膜包括导电粘合剂层和堆叠其上的绝缘粘合剂层。在各向异性导电膜中，导电粘合剂层的反应单体的量高于绝缘粘合剂层的反应单体的量，以改善所述各向异性导电层对玻璃的附着性，从而解决在预粘合中的缺陷。

Description

具有改善的预粘合加工性的各向异性导电膜和半导体装置
技术领域
本发明涉及一种各向异性导电膜，所述各向异性导电膜包括导电粘合剂层和其上堆叠的绝缘粘合剂层，更具体地，涉及一种各向异性导电膜，其中，导电粘合剂层比绝缘粘合剂层具有更高量的反应单体，以改善所述各向异性导电膜对玻璃的附着性，从而防止在预粘合过程中的加工失败。
背景技术
通常，各向异性导电膜（ACF）是指膜状粘合剂，其中导电颗粒，例如包含镍颗粒或金颗粒的金属颗粒，或涂金属的聚合物树脂颗粒分散在树脂如环氧树脂中。各向异性导电膜表示具有在其厚度方向呈现导电性质且在其表面方向呈现绝缘性质的电各向异性和粘合性的聚合物层。当各向异性导电膜置于将被连接的电路板之间并且在特定条件下经受加热和加压时，电路板的电路端子通过导电颗粒电连接，并且绝缘粘合剂树脂填充相邻电路端子间的间隙以使导电颗粒彼此绝缘，从而提供电路端子间的高绝缘性能。
随着重量轻、紧凑和小尺寸IT装置及平板显示器分辨率增加的最新趋势，装置的电路宽度逐渐变窄。在这种情况下，包含于粘合剂层中的用于连接电路的导电颗粒聚集，不可避免地引起短路。因而，通常广泛使用具有多层结构的各向异性导电膜以克服这样的问题。
现在的多层各向异性导电膜具有绝缘粘合剂层堆叠在离型膜如聚对苯二甲酸乙二醇酯（PET）膜上，并且导电粘合剂层堆叠其上的结构。其中，导电粘合剂层包含导电颗粒，并且比绝缘粘合剂层具有更低量的反应单体，从而呈现高熔融粘度。
当使用这样的各向异性导电膜时，在粘合中，具有相对高熔融粘度的导电粘合剂层最大程度地抑制导电颗粒的流动性，并且具有相对低熔融粘度的绝缘粘合剂层填充电极间的间隙以防止短路。
但是，常规的各向异性导电膜具有较差的预粘合加工性。特别是在使用各向异性导电膜的模制过程中，各向异性导电膜经历预粘合过程，其中各向异性导电膜布置在玻璃上并通过热压制固定，然后移除离型膜。这里，由于常规的各向异性导电膜包含粘合于玻璃的比邻接离型膜的绝缘粘合剂层具有更高量的熔融粘度的导电粘合剂层，所以导电粘合剂层对玻璃具有低附着性。从而，在预粘合过程中，当移除离型膜时，各向异性导电膜也由玻璃分离，引起加工失败。
进一步，当这样的加工失败发生在最终压制时，玻璃经历再加工过程以移除胶带和各向异性导电膜的手动预粘合过程，而不是被丢弃，因此这是个问题。
因而，存在对导电粘合剂层具有增强的附着性的各向异性导电膜以改善预粘合加工性的需要。
下面文献中公开了多层各向异性导电膜的实例。
日本专利公开2010-37539（2010年2月18日公开）公开了一种多层各向异性导电膜，所述多层各向异性导电膜包含两种类型的具有不同的一分钟半衰期的有机过氧化物作为聚合引发剂以在低温下达到快速固化。
日本专利公开2007-257947（2007年10月4日公开）公开了一种多层各向异性导电膜，其中，纳米二氧化硅添加到绝缘粘合剂层以增强绝缘粘合剂层的粘结强度。
韩国专利公开10-2010-0010694（2010年2月2日公开）公开了一种多层各向异性导电膜，所述各向异性导电膜包含比绝缘粘合剂层具有更高熔融粘度并包括多个孔的导电粘合剂层，并可用于精细间距。
考虑到导电粘合剂层的附着性，这些公开仅仅旨在使导电粘合剂层比绝缘粘合剂的熔融粘度更高，以便防止导电颗粒的流动，但是从未提及改善导电粘合剂层的附着性的方面，即，解决预粘合中的缺陷。
发明内容
如上述，本发明的发明人认识到在使用各向异性导电膜中的预粘合中出现的缺陷，其中，因为导电粘合剂层的附着性低，导电粘合剂层比绝缘粘合剂具有更低的熔融粘度。为了解决这个问题，发明人通过使导电粘合剂层中的反应单体的量高于绝缘粘合剂层中的反应单体的量，开发出了一种具有极好的附着性的各向异性导电膜。
具体地，本发明旨在提供一种各向异性导电膜，所述各向异性导电膜具有增强的导电粘合剂层附着性以在仍具有作为常规多层各向异性导电膜主要作用的防止短路的性质的同时，获得极好的预粘合加工性。
根据本发明的一个方面，提供了一种各向异性导电膜，所述各向异性导电膜包括导电粘合剂层和堆叠在导电粘合剂层上的绝缘粘合剂层，其中，导电粘合剂层中的反应单体的量高于绝缘粘合剂层中的反应单体的量。
根据本发明的另一个方面，导电粘合剂层的反应单体的量可为绝缘粘合剂层的反应单体量的1至2倍。
根据本发明的再一个方面，提供了一种各向异性导电膜，基于各向异性导电膜的总重量，所述各向异性导电膜包含20至45wt%的反应单体和55至80wt%的粘合剂树脂，其中所述各向异性导电膜包含具有不同剥离强度值的至少两层。
根据本发明的另一个方面，提供了一种各向异性导电膜，基于各向异性导电膜的总重量，所述各向异性导电膜包括45至75wt%的热塑性树脂、1至10wt%的导电颗粒和20至45wt%的反应单体，并且所述各向异性导电膜在25℃、1MPa和1秒条件下具有3至10gf／mm的剥离强度值。
根据本发明的另一个方面，所述反应单体可包括选自由2-甲基丙烯酰氧基乙基磷酸酯、三(甲基)丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种。
根据本发明的另一个方面，提供了一种通过所述各向异性导电膜连接的半导体装置。
所述半导体装置可包括布线基板、附着于所述布线基板的芯片固定侧的各向异性导电膜和固定在所述膜上的半导体芯片；
根据本发明的各向异性导电膜对导电粘合剂层具有增强的附着性，从而提供极好的预粘合加工性。
更具体地，根据本发明，导电粘合剂层中的反应单体的量高于绝缘粘合剂层中的反应单体的量，以增强预粘合中对导电粘合剂层的附着性，从而有助于移除离型膜。进而，在最终压制中，由于导电粘合剂层的快速反应性，所以与绝缘粘合剂层的流动性相比，导电粘合剂层的流动性显著降低，从而防止短路。
具体实施方式
现在将详细地描述本发明的示例性实施方式。在此将省略本领域技术人员公知的细节。并且在此，不定冠词“一个（a）”、“一种（an）”和它们的派生词不排除复数。
根据本发明的一个方面，提供了一种各向异性导电膜，所述各向异性导电膜包括导电粘合剂层和堆叠其上的绝缘粘合剂层，其中，导电粘合剂层中的反应单体的量高于绝缘粘合剂层中的反应单体的量。
所述各向异性导电膜在导电粘合剂层和玻璃间具有极好的附着性，并且在预粘合中在绝缘粘合剂层和离型膜间具有极好的释放力，从而防止加工缺陷。
基于导电粘合剂层的总重量，所述导电粘合剂层中的反应单体的量可为25至50wt%，优选30至45wt%。
基于绝缘粘合剂层的总重量，所述绝缘粘合剂层中的反应单体的量可为20至40wt%，优选25至35wt%。
根据本发明的另一个方面，导电粘合剂层的反应单体的量可为绝缘粘合剂层的反应单体的量的1至2倍，优选1至1.8倍，更优选1.1至1.5倍。
根据本发明的再一个方面，提供了一种各向异性导电膜，基于各向异性导电膜的总重量，所述各向异性导电膜包括20至45wt%的反应单体和55至80wt%的粘合剂树脂，优选25至40wt%的反应单体和60至75wt%的粘合剂树脂，其中所述各向异性导电膜包含具有不同剥离强度值的至少两层，为上层（导电粘合剂层）和下层（绝缘粘合剂层）
上层在25℃和1MPa1秒下可具有3至10gf／mm的剥离强度值，并且下层在同样条件下可具有2至7gf／mm的剥离强度值。
根据本发明的另一个方面，提供了一种各向异性导电膜，基于各向异性导电膜的总重量，所述各向异性导电膜包括45至75wt%的热塑性树脂、1至10wt%的导电颗粒和20至45wt%的反应单体，优选60至70wt%的热塑性树脂、1至10wt%的导电颗粒和25至40wt%的反应单体，并且所述各向异性导电膜具有400至800%的伸长率。
导电粘合剂层和/或绝缘粘合剂层的反应单体可为(甲基)丙烯酸酯单体、优选选自由具有磷酸酯基的丙烯酸酯、具有羟基的丙烯酸酯、具有环氧基的丙烯酸酯、三(甲基)丙烯酸酯和异氰脲酸酯组成的组中的至少一种，更优选选自由2-甲基丙烯酰氧基乙基磷酸酯、三（甲基）丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种，进一步优选(甲基)丙烯酸-2-羟乙酯。
根据本发明的另一个方面，提供了一种通过所述各向异性导电膜连接的半导体装置。
所述半导体装置可包括布线基板、附着于布线基板的芯片固定侧的各向异性导电膜和固定在所述膜上的半导体芯片。
本发明中使用的布线基板和半导体芯片没有具体限制，且可包含本领域中通常使用的任何布线基板和半导体芯片。
本发明的制造半导体装置的方法没有具体限制，且可包含本领域中通常使用的任何方法。
本发明的各向异性导电膜中，导电粘合剂层可包括粘合剂树脂、反应单体、自由基引发剂和导电颗粒，并且绝缘粘合剂层可包括粘合剂树脂、反应单体和自由基引发剂。下文中，将详细描述各个组分。
（a）粘合剂
本发明中使用的粘合剂树脂可包括例如热塑性树脂、丙烯酸树脂、聚氨酯树脂、聚氨酯丙烯酸酯树脂、聚酯型聚氨酯树脂、或丁腈橡胶（NBR）树脂。
热塑性树脂
本发明中使用的热塑性树脂可包括选自由丙烯腈树脂、苯氧基树脂、丁二烯树脂、丙烯酸树脂、聚氨酯树脂、聚氨酯丙烯酸酯树脂、聚酰胺树脂、烯烃树脂、硅树脂和NBR树脂组成的组中的至少一种，但不限于此。
热塑性树脂可具有1000至1000000g/mol的重均分子量。在该范围内，可获得合适的膜强度，不发生相分离，并且由于对被粘物降低的粘附性而不劣化粘结强度。
导电粘合剂层中，基于导电粘合剂层的总重量，热塑性树脂的量可为50至80wt%，优选60至75wt%。绝缘粘合剂层中，基于绝缘粘合剂层的总重量，热塑性树脂的量可为50至90wt%，优选65至85wt%。
丙烯酸树脂
本发明中使用的丙烯酸树脂可通过丙烯酸单体和/或与丙烯酸单体可聚合的单体的聚合而获得。例如，丙烯酸树脂可通过聚合选自由具有C2至C10烷基的(甲基)丙烯酸酯、(甲基)丙烯酸、乙酸乙烯酯及其改性丙烯酸单体组成的组的至少一种单体来制备。聚合方法无具体限制。
本发明中使用的粘合剂树脂中的丙烯酸树脂的量没有具体限制，基于膜的总重量，可为0~40wt%。
聚氨酯树脂
本发明使用的聚氨酯树脂可为具有氨基甲酸乙酯键的聚合物树脂，可通过异佛尔酮二异氰酸酯、聚四乙二醇等聚合制备，但不限于此。聚氨酯树脂可具有50000~100000g/mol的重均分子量。
基于膜的总重量，本发明中使用的粘合剂树脂中的聚氨酯树脂的量可为0~40wt%。
聚氨酯丙烯酸酯树脂
本发明中可用的聚氨酯丙烯酸酯树脂可通过异氰酸酯、多元醇、二醇和羟基丙烯酸酯的共聚获得。
异氰酸酯可包括选自由芳族二异氰酸酯、脂族二异氰酸酯、脂环族二异氰酸酯组成的组中的至少一种。例如，异氰酸酯可包括选自由四亚甲基-1,4-二异氰酸酯、六亚甲基-1,6-二异氰酸酯、环己基-1,4-二异氰酸酯、亚甲基双（4-环己基异氰酸酯）、异佛尔酮二异氰酸酯和4,4-亚甲基双（环己基二异氰酸酯）组成的组中的至少一种。
所述多元醇可包括选自由聚酯多元醇、聚醚多元醇和聚碳酸酯多元醇组成的组中的至少一种。多元醇可通过二羧酸化合物和二醇化合物的缩聚获得。二羧酸化合物的实例可包括琥珀酸、戊二酸、间苯二甲酸、己二酸、辛二酸、壬二酸、葵二酸、十二烷二酸、六氢邻苯二甲酸、对苯二甲酸、邻苯二甲酸、四氯邻苯二甲酸、1,5-萘二羧酸、富马酸、马来酸、衣康酸、柠康酸、中康酸和四氢邻苯二甲酸，但不限于此。二醇化合物的实例可包括乙二醇、丙二醇、1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇和1,4-环己烷二甲醇，但不限于此。此外，合适的聚醚多元醇的实例可包括聚乙二醇、聚丙二醇和聚四乙二醇，但不限于此。
二醇的实例可包括选自由1,3-丙二醇、1,3-丁二醇、1,4-丁二醇、1,5-戊二醇、1,6-己二醇、新戊二醇、二乙二醇、二丙二醇、三乙二醇、四乙二醇、二丁二醇、2-甲基-1,3-戊二醇、2,2,4-三甲基-1,3-戊二醇和1,4-环己烷二甲醇组成的组中的至少一种，但不限于此。
制造聚氨酯丙烯酸酯树脂的聚合方法没有具体限制。
本发明中使用的粘结剂树脂中的聚氨酯丙烯酸酯树脂的量没有具体限制，基于膜的总重量，可为0~30wt%。
聚酯型聚氨酯树脂
本发明中可使用的聚酯型聚氨酯树脂可通过聚酯多元醇和二异氰酸酯的反应获得。
所述聚酯多元醇是指具有多个酯基和多个羟基的聚合物。所述聚酯多元醇可通过二羧酸和二醇的反应获得。
二羧酸的实例可包括对苯二甲酸、邻苯二甲酸、己二酸和辛二酸。优选使用这些芳族或脂族二羧酸。
二醇的实例可包括乙二醇、丙二醇、1,4-丁二醇、己二醇、新戊二醇、二乙二醇和三乙二醇。优选使用这些二醇。
二异氰酸酯的实例可包括2,4-甲苯二异氰酸酯（2,4-TDI）、4,4'-二苯基甲烷二异氰酸酯（MDI）、1,6-六亚甲基二异氰酸酯（HDI）和异佛尔酮二异氰酸酯（IPDI）。优选使用这些芳族、脂环族或脂族二异氰酸酯。
NBR树脂
本发明中可使用的NBR树脂是通过丙烯腈和丁二烯乳液聚合获得的共聚物。关于共聚物中丙烯腈和丁二烯的量没有具体限制，并且关于聚合方法也没有具体限制。NBR可具有50000~2000000g/mol的重均分子量。
本发明中使用的粘合剂树脂中NBR树脂的量没有具体限制，基于膜的总重量，可为0~15wt%。
（b）反应单体
反应单体是指通常具有小于1000的重均分子量并实际上引发固化反应的化合物。本发明中的反应单体可包括(甲基)丙烯酸酯单体。
基于导电粘合剂层的总重量，导电粘合剂层的反应单体的量可为25~50wt%。在该范围内，导电粘合剂层可在附着性上提高，从而防止预粘合中的加工缺陷。同样，粘合剂层的流动性被适当控制，以避免由导电颗粒的流动引起的短路。优选地，反应单体的量可为30~45wt%。
基于绝缘粘合剂层的总重量，绝缘粘合剂层的反应单体的量可为20~40wt%，优选25~35wt%。
导电粘合剂层的反应单体的量可大于绝缘粘合剂层的反应单体的量。
导电粘合剂层的反应单体的量可为绝缘粘合剂层的反应单体的量的1至2倍。在该范围内，在预粘合中，导电粘合剂层比绝缘粘合剂层具有更高的附着性。进一步，导电粘合剂层的导电颗粒的流动性被控制以防止短路。
优选导电粘合剂层的反应单体的量可为绝缘粘合剂层的反应单体的量1至1.8倍，更优选1.1至1.5倍。
(甲基)丙烯酸酯单体
(甲基)丙烯酸酯单体可包括但不具体限于选自由单(甲基)丙烯酸-6-己二醇酯、(甲基)丙烯酸-2-羟乙酯、(甲基)丙烯酸-2-羟丙酯、(甲基)丙烯酸-2-羟丁酯、(甲基)丙烯酸-2-羟基-3-苯氧基丙酯、(甲基)丙烯酸-1,4-丁二醇酯、2-羟基烷基(甲基)丙烯酰基磷酸酯、(甲基)丙烯酸-4-羟基环己酯、单(甲基)丙烯酸新戊二醇酯、三羟甲基乙烷二(甲基)丙烯酸酯、三羟甲基丙烷二(甲基)丙烯酸酯、三(甲基)丙烯酸季戊四醇酯、五(甲基)丙烯酸二季戊四醇酯、六(甲基)丙烯酸季戊四醇酯、六(甲基)丙烯酸二季戊四醇酯、二(甲基)丙烯酸甘油酯、叔氢糠基(甲基)丙烯酸酯（t-hydrofurfuryl(meth)acrylate）、(甲基)丙烯酸异癸酯、(甲基)丙烯酸-2-(2-乙氧基乙氧基)乙酯、(甲基)丙烯酸十八酯、(甲基)丙烯酸月桂酯、(甲基)丙烯酸-2-苯氧基乙酯、(甲基)丙烯酸异冰片酯、(甲基)丙烯酸三癸酯、乙氧基化的壬基苯酚(甲基)丙烯酸酯、二(甲基)丙烯酸乙二醇酯、二(甲基)丙烯酸二乙二醇酯、二(甲基)丙烯酸三乙二醇酯、二(甲基)丙烯酸叔乙二醇酯、聚乙二醇二(甲基)丙烯酸酯、二(甲基)丙烯酸-1,3-丁二醇酯、二(甲基)丙烯酸三丙二醇酯、乙氧基化的双酚A二(甲基)丙烯酸酯、环己烷二甲醇二(甲基)丙烯酸酯、苯氧基叔乙二醇二(甲基)丙烯酸酯（phenoxy-t-glycoldi(meth)acrylate）、2-甲基丙烯酰氧基乙基磷酸酯、二羟甲基三环癸烷二(甲基)丙烯酸酯、三羟甲基丙烷苯甲酸酯丙烯酸酯、(甲基)丙烯酸磷酸乙氧酯（acidphosphoxyethyl(meth)acrylate）、2-丙烯酰氧基邻苯二甲酸酯、三羟甲基丙烷丙烯酸酯、四羟甲基甲烷四丙烯酸酯、2-羟基-1,3-二丙烯酰氧基丙烷、2,2-双[4-(丙烯酰氧基聚甲氧基)苯基]丙烷、2,2-双[4-(丙烯酰氧基聚乙氧基)苯基]丙烷、丙烯酸二环戊烯酯、丙烯酸三环辛酯、三(丙烯酰氧基乙基)异氰酸酯、异氰脲酸环氧乙烷改性的二丙烯酸酯、聚氨酯丙烯酸酯和它们的组合组成的组中的至少一种。
本发明中使用的反应单体可为(甲基)丙烯酸酯单体，优选选自由具有磷酸酯基的丙烯酸酯、具有羟基的丙烯酸酯、具有环氧基的丙烯酸酯、三(甲基)丙烯酸酯和异腈脲酸酯组成的组中的至少一种，更优选选自由2-甲基丙烯酰氧基乙基磷酸酯、三(甲基)丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种，更优选(甲基)丙烯酸-2-羟乙酯。
在用于导电粘合剂层的反应单体中，2-甲基丙烯酰氧基乙基磷酸酯的量没有具体地限制，基于导电粘合剂层的的总重量，可优选为0~5wt%。
在用于导电粘合剂层的反应单体中，三(甲基)丙烯酸季戊四醇酯的量没有具体地限制，基于导电粘合剂层的总重量，可优选为0~20wt%。
在用于导电粘合剂层的反应单体中，(甲基)丙烯酸-2-羟乙酯的量没有具体地限制，基于导电粘合剂层的的总重量，可优选为0~20wt%。
在用于绝缘粘合剂层的反应单体中，2-甲基丙烯酰氧基乙基磷酸酯的量没有具体地限制，基于导电粘合剂层的的总重量，可优选为0~5wt%。
在用于绝缘粘合剂层的反应单体中，三(甲基)丙烯酸季戊四醇酯的量没有具体地限制，基于绝缘粘合剂层的的总重量，可优选为0~15wt%。
在用于绝缘粘合剂层的反应单体中，(甲基)丙烯酸-2-羟乙酯的量没有具体地限制，而是基于绝缘粘合剂层的的总重量，可优选为0~15wt%。
（c）自由基引发剂
本发明中使用的自由基引发剂可包含光固化引发剂、热固化引发剂中的至少一种。优选使用热固化引发剂。
自由基引发剂的量没有具体地限制，基于膜的总重量，可优选为0.5~10wt%。
光固化引发剂
该光固化引发剂的实例可包括二苯甲酮、邻苯甲酰苯甲酸甲酯、4-苯甲酰基-4-甲基二苯硫醚、异丙基噻吨酮、二乙基噻吨酮、4-二乙基苯甲酸乙酯、安息香醚、苯甲酰丙醚、2-羟基-2-甲基-1-苯基-1-丙酮和二乙氧基苯乙酮，但不限于此。
热固化引发剂
所述热固化引发剂可包括但不限于过氧化物引发剂和偶氮引发剂。
过氧化物引发剂实例可包括：过氧化苯甲酰、月桂基过氧化物、过氧月桂酸叔丁酯、1,1,3,3-四甲基丁基过氧化-2-乙基己酸酯和氢过氧化枯烯，但不限于此。
偶氮引发剂的实例可包括：2,2'-偶氮双(4-甲氧基-2,4-二甲基戊腈)、2,2'-偶氮双(2-二甲基丙酸)二甲酯和2,2'-偶氮双(N-环己基-2-甲基丙酰胺)，但不限于此。
（d）导电颗粒
本发明的可用于导电粘合剂层的导电颗粒可包括金属颗粒，例如金、银、镍、铜、锡或焊料颗粒；碳颗粒；涂金属的树脂颗粒，例如苯并鸟嘌呤颗粒、聚甲基丙烯酸甲酯（PMMA）颗粒、丙烯酸共聚物颗粒、聚苯乙烯颗粒或它们涂有金、银、镍、铜，锡或焊料的改性树脂颗粒；和其上进一步涂有绝缘颗粒或绝缘膜的绝缘处理的导电颗粒，但不限于此。
导电颗粒的合适量可根据各向异性导电膜的用途而改变，但是基于导电粘合剂层的总重量，可优选0.5~20wt%。在该范围内，可合适地获得传导性，并且可防止短路。更优选地，导电颗粒的量为1~10wt%。
导电颗粒的尺寸（平均直径）没有具体限制，但是可为0.1到10μm的范围。在该范围内，可达到满意的粘结强度和连接可靠性。优选第，导电颗粒的尺寸在1~5μm的范围。
(e)粘合剂层的厚度
导电粘合剂层的厚度
导电粘合剂层的厚度根据导电颗粒的尺寸确定在适当的范围内。例如，如果导电颗粒具有3μm的尺寸，导电粘合剂层的厚度可在4~6μm的范围。
绝缘粘合剂层的厚度
绝缘粘合剂层的厚度根据电极间的空间或空间之间的距离大小确定。优选，例如6~20μm的范围
绝缘粘合剂层的厚度可厚于导电粘合剂层的厚度。
在本发明中，剥离强度通过如下过程测量。
为了测量导电粘合剂层的剥离强度，将多层各向异性导电膜在室温（25℃）下放置1小时，然后将1.5mm宽的各向异性导电膜片在无图案玻璃上在实测温度25℃和1MPa下预粘合1秒，然后移除PET离型膜。然后，准备比预粘合在玻璃上具有1.5mm宽的各向异性导电膜长5cm的粘合剂带（NittoCo.）。将粘合剂带置于预粘合在玻璃上的各向异性导电膜上，并通过辊压橡胶压辊两次附着于其上。
以同样的方法，制备三个的相同样品。布置每个样品，使得暴露在玻璃外的粘合剂带的一部分放置在UTM上，然后测量每个样品的剥离强度值，并计算平均剥离强度。
绝缘粘合剂层的剥离强度值以与导电粘合剂层相同的方法测量，但粘合剂带附着于多层各向异性导电膜，并且移除离型膜，然后在与测量导电粘合剂层的剥离强度相同的条件下在无图案玻璃上预压制各向异性导电膜，然后测量绝缘粘合剂层的剥离强度值。
以下，通过下面的实施例、对比例和实验例对本发明进行详细地说明。但这些实施例仅用于说明的目的，而不应解释为限制各实施方式的范围。
实施例1和2以及对比例1和2：多层各向异性导电膜的制备
实施例1：导电粘合剂层的反应单体的量高于绝缘粘合剂层的反应单体的量的各向异性导电膜的制备
(1)导电粘合剂层
将包括5wt%的NBR树脂（N-34，NipponZeonCo.）、24wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、28wt%丙烯酸粘合剂（AOF-7003，AekyungChemical）和12wt%聚氨酯丙烯酸酯（NPC7007，NanuxInc.）的粘合剂树脂；包括1wt%of2-甲基丙烯酰氧基乙基磷酸酯、12wt%的三(甲基)丙烯酸季戊四醇酯和12wt%的(甲基)丙烯酸-2-羟乙酯的反应单体；3wt%的作为热固化引发剂的月桂基过氧化物；和作为导电颗粒的3μm导电颗粒（SekisuiChemical）混合以制造具有4μm厚度的导电粘合剂层。
（2）绝缘粘合剂层
将包括5wt%NBR树脂（N-34，NipponZeonCo.）、29wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、30wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）和12wt%的聚氨酯丙烯酸酯（NPC7007，NanuxInc.）的粘合剂树脂；包括1wt%的2-甲基丙烯酰氧基乙基磷酸酯、10wt%的三(甲基)丙烯酸季戊四醇酯和10wt%的(甲基)丙烯酸-2-羟乙酯的反应单体；和3wt%的作为热固化引发剂的月桂基过氧化物混合以制造具有10μm厚度的绝缘粘合剂层。
将绝缘粘合剂层堆叠在导电粘合剂层上，从而制备多层各向异性导电膜。
实施例2：导电粘合剂层的反应单体的量高于绝缘粘合剂层的反应单体的量的各向异性导电膜的制备
（1）导电粘合剂层
以与实施例1的（1）相同方式制备导电粘合剂层，区别在于使用20wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、22wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）、17wt%三(甲基)丙烯酸季戊四醇酯和17wt%的(甲基)丙烯酸-2-羟乙酯。
（2）绝缘粘合剂层
以与实施例1的（2）相同方式制备绝缘粘合剂层，区别在于使用27wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、28wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）、12wt%的三(甲基)丙烯酸季戊四醇酯和12wt%的(甲基)丙烯酸-2-羟乙酯。
将绝缘粘合剂层堆叠于导电粘合剂层上，从而制备多层各向异性导电膜。
对比例1：绝缘粘合剂层的反应单体的量高于导电粘合剂层的反应单体的量的各向异性导电膜的制备
（1）导电粘合剂层
以与实施例1的（1）相同方式制备导电粘合剂层，区别在于使用40wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）、6wt%的三(甲基)丙烯酸季戊四醇酯和6wt%的(甲基)丙烯酸-2-羟乙酯。
（2）绝缘粘合剂层
以与实施例1的（2）相同方式制备绝缘粘合剂层。
将绝缘粘合剂层堆叠于导电粘合剂层上，从而制备多层各向异性导电膜。
对比例2：绝缘粘合剂层的反应单体的量高于导电粘合剂层的反应单体的量的各向异性导电膜的制备
（1）导电粘合剂层
以与实施例1的（1）相同方式制备导电粘合剂层，区别在于使用31wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、38wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）、3wt%的三(甲基)丙烯酸季戊四醇酯和4wt%的(甲基)丙烯酸-2-羟乙酯。
（2）绝缘粘合剂层
以与实施例1的（2）相同方式制备绝缘粘合剂层，区别在于使用17wt%的聚氨酯粘合剂（NPC7007T，NanuxInc.）、18wt%的丙烯酸粘合剂（AOF-7003，AekyungChemical）、22wt%的三(甲基)丙烯酸季戊四醇酯和22wt%的(甲基)丙烯酸-2-羟乙酯。
将绝缘粘合剂层堆叠于导电粘合剂层上，从而制备多层各向异性导电膜。
实施例1和2以及对比例1和2中的反应单体的量示于表1中。
表1
实验例1：预粘合加工性和剥离强度的测量
评价根据实施例1和2以及对比例1和2的多层各向异性导电膜的导电粘合剂层和绝缘粘合剂层的剥离强度值。
为了测量各导电粘合剂层的剥离强度值，将各多层各向异性导电膜置于室温（25℃）下1小时，然后将1.5mm宽的各向异性导电膜片在25℃的实测温度和1MPa在无图案玻璃上预压制1秒，然后移除PET离型膜。然后，准备比预粘合在玻璃上的具有1.5mm宽的各向异性导电膜长5cm的粘合剂带（NittoCo.）。将粘合剂带置于预粘合在玻璃上的各向异性导电膜上，并通过辊压橡胶压辊两次附着于其上。
以同样的方法，制备三个相同样品。布置每个样品，使得粘合剂带暴露于玻璃外的一部分置于UTM上，然后测量每个样品的剥离强度，并计算平均剥离强度。
各绝缘粘合剂层的剥离强度值以如上同样的方式测量，但是粘合剂带附着于多层各向异性导电膜，并且移除离型膜，然后在与测量导电粘合剂层的剥离强度值相同的条件在无图案玻璃上预压制各向异性导电膜，然后，测量绝缘粘合剂层的剥离强度值。
根据实施例1和2以及对比例1和2中的导电粘合剂层和绝缘粘合剂层的剥离强度值示于表2中。
表2
实验例2:粘结强度可靠性的测量
将根据实施例1和2以及对比例1和2的每种各向异性导电膜通过在70℃的实测温度下预粘合1秒并在180℃和4.5MPa下最终压制5秒连接于金属电极玻璃（Mo/Al/Mo结构，SamsungElectronics）和膜上芯片（COF，SamsungElectronics），从而制备每种膜的10个样品。评价每种膜的样品的初始粘结强度，并计算平均值。
每种膜的10个样品在高温高湿下、在85℃和85%RH储存500小时进行可靠性测试，然后在可靠性测试后评价粘结强度，并计算平均值。
实验例3：连接电阻可靠性的测量
将根据实施例1和2以及对比例1和2的每个多层各向异性导电膜置于室温（25℃）下1小时，然后通过在70℃的实测温度预粘合1秒并在180℃和4.5MPa下压制5秒而连接到通过在用厚度的氧化铟锡（ITO）涂布的无图案玻璃上形成四探针可测图案而获得的COF（SamsungElectronics）上，从而制备每种膜的10个样品。用四探针法评价样品的初始连接电阻（根据ASTMF43-64T），并计算平均值。
将每种膜的10个样品在高温高湿下、在85℃和85%RH储存500小时进行可靠性测试，然后评价可靠性测试后的连接电阻（根据ASTMD117），并计算平均值。
实验例4：短路发生的测量
基于测试100次后短路引起的问题比率，评价根据实施例1和2以及对比例1和2的每个多层各向异性导电膜的短路发生。
将根据实施例1和2以及对比例1和2的每个多层各向异性导电膜置于室温（25℃）下1小时，然后通过在70℃的实测温度预粘合1秒并在180℃和4.5MPa压制5秒，连接到通过在用厚度的氧化铟锡（ITO）涂布的无图案玻璃上形成二探针可测图案而获得的COF（STEMCO）上，从而制备每种膜的100个样品。对每种膜的样品施加50V电压，然后计算允许导电的样品数量。
实验例5：伸长率的测量
将根据实施例1和2以及对比例1和2的每个多层各向异性导电膜切成1.5mm宽和3cm长的片。由该片移除离型膜2cm，将该片的离型膜移除的部分固定在UTM上，并将其它部分（离型膜仍保留的部分）固定于UTM膜的相反侧，然后用5-N荷载单元以50mm/min拉该片，当该片断裂时测量伸长率。
实验例2至5的结果示于表3中。
表3
在表2和表3中，根据实施例1和2的各向异性导电膜具有极好的剥离强度，呈现极好的预粘合加工性以及粘结强度和连接电阻上的高可靠性，而没有短路。
但是，根据对比例1的各向异性导电膜具有粘结强度和连接电阻上的高可靠性，没有短路，但是由于低的预粘合加工性而导致加工失败。根据对比例2的各向异性导电膜由于低的剥离强度而呈现出较差的预粘合加工性，并引起短路。
因而，认为导电粘合剂层和绝缘粘合剂层中的反应单体的量是决定多层各向异性导电膜物理性质的重要因素。同样，认为当导电粘合剂层中的反应单体的量高于绝缘粘合剂层中反应单体的量时，各向异性导电膜呈现出极好的物理性质。
尽管本发明的说明书中提供了一些实施方式，但对本领域技术人员显然的是，各实施方式仅以说明的方式提出，并能进行各种修改、变更、替换和等效实施方式而不背离本发明的精神和范围。本发明的范围应仅由所附权利要求书限定。

Claims (8)

1.一种各向异性导电膜，所述各向异性导电膜包括导电粘合剂层和堆叠在所述导电粘合剂层上的绝缘粘合剂层，其中，所述导电粘合剂层的反应单体的量高于所述绝缘粘合剂层中的反应单体的量，其中所述反应单体的量是指在各自层中的相对重量百分含量，其中，所述导电粘合剂层的反应单体的量是所述绝缘粘合剂层的反应单体的量的大于1倍至2倍。
2.如权利要求1所述的各向异性导电膜，其中，基于所述导电粘合剂层的总重量，所述导电粘合剂层的反应单体的量是25至50wt％，并且基于所述绝缘粘合剂层的总重量，所述绝缘粘合剂层的反应单体的量是20至40wt％。
3.如权利要求1至2中任意一项所述的各向异性导电膜，其中，所述导电粘合剂层和/或所述绝缘粘合剂层的反应单体包括选自由2-甲基丙烯酰氧基乙基磷酸酯、三(甲基)丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种。
4.一种各向异性导电膜，基于所述各向异性导电膜的总重量，所述各向异性导电膜包括20至45wt％的反应单体和55至80wt％的粘合剂树脂，其中所述各向异性导电膜包括导电粘合剂层和堆叠在所述导电粘合剂层上的绝缘粘合剂层，并且所述导电粘合剂层的剥离强度高于所述绝缘粘合剂层的剥离强度，其中，所述导电粘合剂层的反应单体的量是所述绝缘粘合剂层的反应单体的量的大于1倍至2倍，其中所述剥离强度是在25℃、1MPa下预粘合1秒后测量。
5.如权利要求4所述的各向异性导电膜，其中，所述反应单体包括选自由2-甲基丙烯酰氧基乙基磷酸酯、三(甲基)丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种。
6.如权利要求4所述的各向异性导电膜，其中所述各向异性导电膜具有400至800％的伸长率。
7.如权利要求6所述的各向异性导电膜，其中，所述反应单体包括选自由2-甲基丙烯酰氧基乙基磷酸酯、三(甲基)丙烯酸季戊四醇酯和(甲基)丙烯酸-2-羟乙酯组成的组中的至少一种。
8.一种半导体装置，所述半导体装置包括：
布线基板；
附着于所述布线基板的芯片固定侧的各向异性导电膜；和
固定在所述各向异性导电膜上的半导体芯片；
其中，所述各向异性导电膜为权利要求1至7中任意一项所述的各向异性导电膜。
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