CN1289621C - 可阳离子聚合的粘合剂组合物和各向异性导电粘合剂组合物 - Google Patents

可阳离子聚合的粘合剂组合物和各向异性导电粘合剂组合物 Download PDF

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CN1289621C
CN1289621C CN 02817905 CN02817905A CN1289621C CN 1289621 C CN1289621 C CN 1289621C CN 02817905 CN02817905 CN 02817905 CN 02817905 A CN02817905 A CN 02817905A CN 1289621 C CN1289621 C CN 1289621C
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composition
cationically polymerizable
vinyl ether
epoxy
monomer
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CN1555405A (zh
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山口裕显
弘重裕司
秋山良太
北村哲
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3M Innovative Properties Co
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
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Abstract

一种可阳离子聚合粘合剂，其包括可阳离子聚合单体，可阳离子聚合催化剂和稳定剂，该单体选自环氧单体、乙烯基醚单体及其混合物，其中，稳定剂至少是一种下列分子式(I)表示的酰胺，式中，R1是具有1-30个碳原子的烷基，或者含1个或两个不饱和键和2-30个碳原子的链烯基，每个R2分别是氢或具有1-10个碳原子的烷基。

Description

可阳离子聚合的粘合剂组合物和各向异性导电粘合剂组合物
                          发明的详细说明
本发明涉及可显示极佳粘合强度的可阳离子聚合粘合剂组合物，以及可显示良好导电性或导热性的、并同时显示极佳粘合强度的各向异性导电或导热粘合剂组合物。
利用阳离子聚合的可阳离子聚合组合物具有广泛的用途，例如，在涂料油墨和粘合剂领域中。尤其，在粘合剂的使用中，由于它的高固化速率和免受氧阻滞，可阳离子聚合组合物是有利的。然而，可阳离子聚合组合物的快速固化性，在一些情况下会发生粘合强度降低。尤其是，如果粘合剂组合物是完全涂覆和铺展在粘附体上，并由于反应的快速进行，则在与粘附体表面接触前固化，就不能得到足够高的粘合强度。为了解决这个问题，选择可阳离子聚合化合物和聚合催化剂，它们分别具有低的反应性，其程度不影响在要求温度下的固化性能，或者，加入能抑制粘合剂组合物聚合的稳定剂，均是有效的。通过这些方法，可阳离子聚合组合物的存储稳定性也同时得到改进。
例如，日本未审查专利公报(公开)4-227625，描述了将特殊的胺作为稳定剂加入到环氧树脂组合物中，该组合物包括环氧树脂和特殊的铁-芳烃配合物引发剂，并陈述了通过这种胺的加入，即使环氧树脂组合物通过光辐射活化后，在室温的存储稳定性保证30天以上，并且组合物可在高温快速固化。
日本未审查专利公报(公开)8-511572描述了包含阳离子可固化单体、有机金属配阳离子盐和特殊稳定添加剂的可能量聚合组合物，并阐述：通过具有这种构成，提高该组合物存储稳定性和适用期。
日本未审查专利公报(公开)5-262815，描述了含有可阳离子聚合化合物和热潜催化剂的反应性组合物，该热潜催化剂包括路易斯酸及给电子化合物的配合物，并阐述：通过具有这种构成，提高了组合物的存储稳定性，并赋予聚合物极佳的物理性能。
另一方面，在液晶显示器中，玻璃制显示板的电极部件和上面安装激活显示板所需的驱动IC、称作TCP(载带封装)柔性电路的连接，是通过插入各向异性导电粘合薄膜热压粘合。连接间距通常为100-200微米。然而，由于显示部件变成十分有限，连接间距变成更细，最近几年，要求连接间距50微米或以下。这更细的连接间距由于热压粘合时的热量，通过TCP的膨胀和收缩，造成间距滑动的问题。为了解决这个问题，需要在较低温能热压粘合的各向异性的导电粘合薄膜。而且，为了提高生产能力，还需要在较短时间内能热压粘合的各向异性导电粘合薄膜。为了满足这些要求，提出了使用阳离子聚合机理和具有高反应性的各向异性导电粘合薄膜。
例如，日本未审查专利公报(公开)8-511570，描述了各向异性导电粘合剂组合物，它包括可固化的环氧树脂，热塑性树脂，有机金属配阳离子，稳定添加剂，固化速率增强剂和导电颗粒，并阐述在温度120-125℃，可达到热固化。
                       发明解决的问题
通过这些稳定剂的使用，改进得到的粘合剂组合物的存储寿命，并使热压粘合可在低温进行，但是，粘合强度不够高。
本发明的目的是提供具有长存储寿命的可阳离子聚合粘合剂组合物，它能在低温热压粘合，并保证极佳的粘合强度。
                      解决问题的方法
为了解决上述问题，本发明提供可阳离子聚合粘合剂组合物，它包括(A)选自环氧单体、乙烯基醚单体及其混合物的可阳离子聚合单体，(B)阳离子聚合催化剂和(C)稳定剂，其中至少一种由下列分子式(I)表示的酰胺用作(C)稳定剂：
(其中R1是具有1-30个碳原子的烷基，或者，含一个或两个不饱和键和具有2-30个碳原子的链烯基，R2分别是氢或具有1-10个碳原子的烷基)。
较好地，所述稳定剂(C)至少是一种下列分子式(I’)表示的酰胺：
Figure C0281790500062
其中，R1是具有1-30个碳原子的烷基，或者，含一个或两个不饱和键和具有2-30个碳原子的链烯基。
根据本发明，提供上述可阳离子聚合粘合剂组合物，以及包括导电或导热颗粒的各向异性导电或导热的粘合剂组合物。
                      实施发明的方式
如上所述，本发明的可阳离子聚合粘合剂组合物由(A)可阳离子聚合单体，(B)阳离子聚合催化剂和(C)分子式(I)表示的酰胺作为稳定剂组成。各构成组分，在下面描述。
可阳离子聚合单体
可阳离子聚合单体选自环氧单体、乙烯基醚单体及其混合物。环氧单体的例子包括分别具有可阳离子聚合官能团的1，2-环醚，1，3-环醚和1，4-环醚，但是环氧单体限于没有抑制阳离子聚合基团，例如含胺、硫或磷的官能团的单体。这环氧单体优选脂环族环氧树脂或含缩水甘油基的环氧树脂。
脂环族环氧树脂是分子中具有平均2个或更多个脂环环氧基团的化合物，其例子包括分子中具有两个环氧基团的化合物，如乙烯基环己烯二氧化物(例如，ERL-4206，Union Carbide Japan生产)，3，4-环氧环己基甲基-3，4-环氧环己烷羧酸酯(例如，UVR-6105和UVR-6110，Union Carbide Japan生产)，己二酸二(3，4-环氧环己)酯(例如UVR-6128，Union Carbide Japan生产)和2-(3，4-环氧环己基-5，5-螺-3，4-环氧)环己烷-间-二氧杂环己烷(例如，ERL-4234，Union Carbide Japan生产)，和分子内具有3，4或更多个环氧基团的多官能脂环族环氧树脂(例如，Epolide GT，Daicel ChemicalIndustries Ltd.生产)。
脂环族环氧树脂的环氧当量通常为90-500，优选100-400，更优选120-300，最优选210-235。如果环氧当量小于90，热固化后的韧性及粘合强度会降低，导致连接可靠性降低，但如果环氧当量超过500，整个体系的粘度过分地增大，其结果，在热压粘合呈现不良的流动性，或者降低反应性，从而降低连接的可靠性。
含缩水甘油基团的环氧树脂是分子中具有平均两个或更多个缩水甘油基团的化合物，其例子包括双酚A型缩水甘油醚(例如，Epikote 828，Yuka Shell Epoxy生产)和酚醛清漆型环氧(例如，Epikote 154，Yuka Shell Epoxy K.K.生产)。
含缩水甘油基团的环氧树脂的环氧当量通常为170-5500，优选170-1000，更优选170-500，最优选175-210。如果环氧当量小于170，热固化后的韧性及粘合强度会降低，但如果环氧当量超过5500，整个体系的粘度过分地增大，其结果，在热压粘合呈现不良的流动性，或者降低反应性，从而降低连接的可靠性。
乙烯基醚单体具有双键的高电子密度，形成非常稳定的碳氧离子，所以，这单体在阳离子聚合中具有高的反应性。为了不抑制阳离子聚合，乙烯基醚单体限于不含氮的，其例子包括甲基乙烯基醚，乙基乙烯基醚，叔丁基乙烯基醚，异丁基乙烯基醚，三甘醇二乙烯基醚和1，4-环己烷二甲醇二乙烯基醚。优选的乙烯基醚单体的例子包括三甘醇二乙烯基醚(例如，Rapi-Cure DVE-3，ISP Japan K.K.生产)和环己烷二甲醇二乙烯基醚(例如，Rapi-Cure CHVE，ISP Japan K.K.生产)。
这些环氧单体和乙烯基醚单体可分别使用和作为其混合物使用。可使用大量的环氧单体和乙烯基醚单体。尤其，优选使用脂环族环氧树脂和含缩水甘油基团环氧树脂的混合物。脂环族环氧树脂具有改进粘合剂组合物的快速固化性和低温固化性的作用，并且由于它的低粘度，还具有提高粘合剂组合物对粘合体粘着的作用。另一方面，含缩水甘油基团的环氧树脂具有在活化后延长粘合剂组合物可使用时间的作用。因此，通过结合使用脂环族环氧树脂和含缩水甘油基团环氧树脂，得到的粘合剂组合物可显示良好的脂环族环氧树脂的低温快速固化性，和含缩水甘油基团环氧树脂的室温长期存储稳定性的综合性能。脂环族环氧树脂/含缩水甘油基团环氧树脂掺合之比通常为5∶95-98∶2，优选40∶60-94∶6，更优选50∶50-80∶20。如果脂环族环氧树脂的量低于5重量％(以脂环族环氧树脂和含缩水甘油基团环氧树脂的总量计)，低温的固化性能会降低，从而不能提供足够高的粘合强度和连接可靠性，但如果脂环族环氧树脂的量超过98重量％，即使在室温附近，固化反应也容易进行，因此，活化后的可使用时间会缩短。可阳离子聚合单体的掺合量优选从10到90重量份/100重量份的整个组合物。
阳离子聚合催化剂
阳离子聚合催化剂是在紫外线辐射下或者在加热和催化下产生阳离子活性中心并催化环氧环开环反应的化合物如路易斯酸。这种阳离子聚合催化剂的例子包括芳基重氮鎓盐，二芳基碘盐、三芳基锍盐，三芳基硒盐和铁-芳烃配合物。它们当中，铁-芳烃配合物因为它们的热稳定性是特别优选的，其具体例子包括二甲苯-环戊二烯合铁(II)(三(三氟甲基磺酰基)甲基化物，六氟磷酸异丙基苯-环戊二烯合铁(II)和二(η-1，3，5-三甲基苯)铁(II)三(三氟甲基磺酰基)甲基化物。阳离子聚合催化剂的其它例子在日本未审查专利公报8-511572中揭示。
阳离子聚合催化剂用量，通常为每100重量份的可阳离子聚合单体，从0.05到10.0重量份，优选从0.075到7.0重量份，更优选从0.1-4.0重量份，最优选从1.0到2.5重量份。如果用量小于0.05重量份，在低温的固化性能会降低到不能提供足够高的粘合强度和连接可靠性，但如果它超过10.0重量份，即使在接近室温，固化反应也容易进行，所以，在室温的存储稳定性会降低。
稳定剂
稳定剂具有有效控制本发明粘合剂组合物固化速率的作用。在本发明中，稳定剂是具有这样结构的酰胺：氨或胺的氢被酰基取代，如上面分子式(I)所示。
酰胺的具体例子包括乙酰胺，丙酰胺，正丁酰胺，月桂酰胺，N，N-二甲基乙酰胺，油(酸)酰胺和芥酸酰胺。
稳定剂的掺合量优选0.000005-0.02重量份/100重量份的整个粘合剂组合物。稳定剂对阳离子聚合催化剂的当量优选0.03-1.0。如果掺合量小于0.03，预计不能起稳定剂作用，但如果它超过1.0，对粘合体的粘合性能是不好的。当量优选0.05-0.8，优选0.1-0.5。
通过混合这些可阳离子聚合单体，阳离子聚合催化剂和稳定剂，可得到本发明的可阳离子聚合粘合剂组合物。通过将导电颗粒加入到这粘合剂组合物，可得到各向异性导电粘合剂组合物，通过加入导热颗粒，可得到导热粘合剂组合物。
可使用的导电颗粒的例子包括导电颗粒，如碳颗粒和铜、镍、金、锡、锌、铂、钯、铁、钨、钼，焊锡等金属颗粒。也可在进一步用金属等的导电涂层覆盖颗粒表面后，使用这些颗粒。而且，也可使用玻璃珠、硅石、石墨、陶瓷或聚合物如聚乙烯、聚苯乙烯、酚树脂、环氧树脂、丙烯酸树脂和苯胍胺树脂的非导电颗粒，它们的表面用金属等的导电涂层覆盖。导电颗粒的形状没有特别的限制，但通常优选接近球状。这颗粒可具有稍微粗糙或有尖峰的表面。形状也可是椭圆状或长圆柱状。
使用的导电颗粒的平均粒度，可根据用于连接的电极宽度和相邻电极之间的间隔而改变。例如，在电极宽度50微米，相邻电极间的间隔50微米(即电极间距100微米)的情况下，平均粒度适合为在3-20微米。通过使用各向异性导电粘合薄膜，平均粒度在这范围内的导电颗粒分散在该薄膜中，可得到足够好的导电特性，同时，可良好地防止相邻电极之间的短路。由于用于电路基片相互连接的电极间距通常为50-1000微米，导电颗粒的平均粒度优选2-40微米。如果平均粒度小于2微米，颗粒埋在电极表面上的凹坑里，并不能起导电颗粒的功能，但如果它超过40微米，相邻电极之间很容易发生短路。
导电颗粒的加入量可根据所用电极的面积和导电颗粒的平均粒度而变化。当每个电极上有一些导电颗粒(例如从2-10)个时，通常可得到良好的连接。在再降低电阻的情况下，导电颗粒可掺合在粘合剂中，这样，存在10-300个导电颗粒。而且，在热压粘合时使用高压的情况下，电极上导电颗粒的数目可增加到300-1000个，以分散压力，从而达到良好的连接。以不包括导电颗粒的粘合剂总体积计，导电颗粒的量通常为0.1-30体积％，优选0.5-10体积％，更优选1-5体积％。如果此量小于0.1体积％，在粘合时在电极上很可能没有导电颗粒，连接的稳定性会降低，但如果此量超过30体积％，相邻电极之间很容易发生短路。
通过将导热颗粒加入到本发明可阳离子聚合粘合剂组合物中得到的导热粘合剂组合物，用于热源，例如，电子部件和散热片之间，或电子部件和电路基片之间，用作热源热分布上的传热界面。可使用的导热颗粒的例子包括氧化铝、硅石、氮化硼、氧化镁和碳纤维的颗粒。导热颗粒的形状不限于颗粒形式，但可使用各种形状，如板和针状物。考虑到它们的用途，导热颗粒大小优选为0.1-500微米。也可结合使用具有不同粒度的导热颗粒。导热颗粒对100重量份粘合剂组合物之比，优选100-1000份。
各向异性导电或导热粘合剂组合物优选以薄膜的形式使用。薄膜可通过在适当的有机溶剂中制备含粘合剂组合物的涂料溶液得到，有机溶剂如甲基乙基酮(MEK)，将涂料溶液以适合的涂布方式(如刮涂器)施涂到分隔片上，并干燥涂层薄膜。这时，可在分隔片的一个表面或两个表面上形成硅基或氟基剥离剂的剥离层。在使用紫外激活型聚合催化剂作为阳离子聚合催化剂的情况下，除了上面所述的用有机溶剂形成膜外，可通过粘合剂组合物的热熔和挤出成型得到薄膜。除非紫外线辐射和甚至在温度100℃或以上用几分钟至几小时时间也几乎不进行反应，紫外激活型阳离子聚合催化剂是非常热稳定的。这样形成的薄膜厚度优选5-100微米，以达到必需的良好的填充，从而使电路基片通过热压粘合相互连接时在连接部件中，不存在间隙。
根据最终用途，除上述组分外，本发明的可阳离子聚合粘合剂组合物还可含有其它添加剂。可加到粘合剂组合物中的添加剂例子包括阳离子聚合促进剂(例如，草酸二叔丁酯)，抗氧化剂(例如，受阻酚基抗氧化剂)，二醇(例如二(苯氧基乙醇)芴)，偶合剂(例如，硅烷偶合剂，如γ-环氧丙氧基丙基三甲氧基硅烷和β-(3，4-环氧环己基)乙基三甲氧基硅烷)，链转移试剂，敏化剂(例如，蒽)，增粘剂，热塑性弹性体或树脂，填料(例如，硅石)，流动调节剂，增塑剂，消泡剂和色料。而且，也可加入不包括酰胺的稳定剂。它们的例子包括通过捕获在阳离子聚合中用作阳离子活性种的路易斯酸等，抑制或禁止阳离子聚合反应的稳定剂，它们的具体例子包括冠醚，如15-冠-5，1，10-菲咯啉及其衍生物，甲苯胺，如N，N-二乙基-间甲苯胺，膦，如三苯基膦，以及三嗪。
热塑性弹性体或树脂，优选在本发明的可阳离子聚合粘合剂组合物形成粘合薄膜时加入。热塑性弹性体或树脂增加粘合薄膜的成膜性，同时，提高粘合薄膜的耐冲击性，减小固化反应产生的残留内应力，提高粘合可靠性。热塑性弹性体是一种在某一温度以下通常称为热塑性弹性体的聚合化合物，它们由作为受限相硬段和表现橡胶弹性的软段组成。该弹性体的例子包括苯乙烯基热塑性弹性体。苯乙烯基弹性体是嵌段共聚物，例如：在硬段中包括苯乙烯单元，在软段中包括聚丁二烯或聚异戊二烯单元。它们的典型例子包括苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)和苯乙烯-异戊二烯-苯乙烯嵌段共聚物(SIS)，另外包括苯乙烯-(乙烯-丁烯)-苯乙烯嵌段共聚物(SEBS)和苯乙烯-(乙烯-丙烯)苯乙烯嵌段共聚物(SEPS)，这里在软段中的二烯组分是氢化的。而且，可使用具有反应基团的苯乙烯基热塑性弹性体，比如：用甲基丙烯酸缩水甘油酯环氧改性的弹性体，以及环氧化共轭二烯的不饱和键的弹性体。由于反应基团的高极性，具有反应基团的弹性体提高与环氧树脂的相容性，所以，使与环氧树脂掺混合的范围加宽，同时，由于反应基团通过与环氧树脂的交联反应。而加入到交联结构中，保证了固化后的耐热性和耐湿性，由此提高粘合的可靠性。环氧化苯乙烯基弹性体的例子包括Epofriend A1020(Daicel Chemical Industries，Ltd.生产)。在本发明中，也可用热塑性树脂代替性弹性体。粘合剂必须通过流化。在粘合薄膜的热压粘合时除去，这样，在粘合基片上的电路之间可得到良好的电连接。所以，热塑性树脂的Tg宜为热压粘合温度(例如，从100-130℃)或以下。这热塑性树脂的例子包括聚苯乙烯树脂，丙烯酸树脂，苯氧基树脂及其组合。
热塑性弹性体或树脂的量通常为10-900重量份，优选20-500重量份，更优选30-200重量份，最优选40-100重量份/100重量份可阳离子聚合单体。如果此量小于10重量份，粘合剂组合物的成膜性会降低，但如果此量超过900重量份，作为整体的粘合剂组合物降低在低温的流动性，粘合时在导电颗粒和电路基片之间形成不良的接触，导致增大电阻或降低连接可靠性，有时候还降低粘合强度。
在可阳离子聚合粘合剂组合物的情况下，含上述组分的本发明各向异性导电粘合剂组合物或导热粘合剂组合物，例如以粘合薄膜的形式，在将薄膜放置在基片上(预粘合)后，要粘合的其他基片，通过压粘头(最后粘合)热压粘合到粘合剂组合物上，由此粘合两个基片。在阳离子聚合催化剂是紫外可活化的阳离子聚合催化剂的情况下，至少在最后粘合前，必须通过辐射紫外线，激活粘合剂组合物。
基片的修理，尤其用常规粘合剂组合物粘合的电路基片，更具体地，在连接部件分开电路基片，以及在一个或两个电路基片上除去粘合剂残留物的操作，优选使用下列有机溶剂来进行。电路基片连接部件使用层合机，即所谓加热器，如烙铁，压缩器和干燥器在100-180℃加热5-10秒钟。在电路基片热的时候，剥离一块电路基片。随后，分开的电路基片表面，用有机溶剂(如丙酮、甲苯或甲乙酮(MEK))湿润的棉拭强烈擦拭30-60秒钟，除去粘合剂残留物。电路基片的表面再用有机溶剂湿润的棉拭洗涤。这时必须注意：不要使有机溶剂与相邻电路连接部件接触。
然而，在使用本发明的可阳离子聚合粘合剂组合物的情况下，电路基片可不使用有机溶剂来修理。例如，将用本发明的各向异性导电粘合剂组合物热压粘合的两个电路基片，在100-250℃范围内加热到适当温度，对它们施加使电路基片相互分开的力，由此，分开两个电路基片而不使电路基片严重损坏。在各向异性导电粘合剂组合物保留在电路基片上的情况下，仍处在加热状态的残留物可再用工具用机械方法擦净，工具由(至少末端部分)木头、纸、或聚合物构成，或者由在所用温度不熔融的金属构成。对于修理液态面板的柔性电路和玻璃电路之间的连接部件，可使用从柔性电路侧将仪器连接到热源(如热压器头)的方法，或者，使用将玻璃电路放置在热板上并加热电路的方法。
本发明的可阳离子聚合粘合剂组合物的另一个特性在于：例如，在形成粘合薄膜的情况下，在制得的溶液状态下，组合物是高度稳定的。一般，当制备的可阳离子聚合组合物具有高的反应性时，它的溶液必需非常小心地操作，例如，通过调节温度，由此不造成爆炸反应并不使溶液固化。然而，本发明的组合物含有少量酰胺，并且酰胺作为溶液的阻聚合剂，因此，可防止溶液固化。
实施例
各向异性导电粘合薄膜的制备
1.0克脂环族环氧树脂(商品名Cyracure UVR6128，Union Carbide Japan Ltd.生产，环氧当量：200)，5.0克含缩水甘油基团的线型酚醛清漆环氧树脂(Epikote 154，YukaShell Epoxy Ltd.生产，环氧当量：178)，4.0克苯氧基树脂(PKHC，Phenoxy AssociatesLtd.生产，OH当量：284)和表1所示的、对催化剂预定当量重量的酰胺(实施例1：油酰胺(分子量：281)；实施例2：芥酸酰胺(分子量338)；实施例3：月桂酰胺(分子量73)；实施例4：正丁酰胺(分子量87))，与10克甲乙酮混合，搅拌混合物直至形成均匀的溶液。溶液中加入导电颗粒(通过在二乙烯基苯共聚物表面上形成镍层、并在其上面重叠金得到的颗粒，平均粒度：5微米)，在最后固体中占3体积％，继续搅拌直至导电颗粒彻底分散。另外，0.060克阳离子聚合催化剂(二(η-1，3，5-三甲基苯)铁(II)-三(三氟甲基磺酰基)甲基化物)，0.009克稳定剂(N，N-二乙基-间甲苯胺)，0.2克硅烷偶合剂(Silane Coupling Agent A187，Nippon Unicar Co.，Ltd.生产，γ-环氧丙氧基丙基三甲氧基硅烷和0.6克甲乙酮混合，并搅拌直至形成均匀的溶液。将该溶液加入到上面制备的分散溶液中，接着进一步搅拌。这样得到的各向异性导电粘合剂组合物的分散溶液，用刮涂器。施涂到作为隔片的硅氧烷处理的聚酯薄膜上，然后在60℃干燥10分钟，得到各向异性导电粘合薄膜，厚度20微米(E1-4)。
4.0克含缩水甘油基的双酚A型环氧树脂(Epikote YL980，Yuka Shell Epoxy Ltd.的商品名，环氧当量：189)，2.0克含缩水甘油基线型酚醛清漆环氧树脂(Epikote 154，Yuka Shell Epoxy Ltd.的商品名，环氧当量：178)4.0克苯氧基树脂(PKHC，PhenoxyAssociates Ltd.生产，OH当量：284)和表2所示的、对催化剂预定当量重量的酰胺(油酰胺(分子量：281))，与10克甲乙酮混合，搅拌混合物直至形成均匀溶液。此后，以上面相同的方式处理溶液，得到各向异性导电粘合薄膜，厚度20微米(E5和E6)。
为了比较，除了省去酰胺(C1)，以实施例1中相同方式制备各向异性导电粘合薄膜，或者除了将酰胺的量改变为对催化剂为1当量(C2和C3)或省略酰胺(C4)以实施例5中相同方式制备各向异性导电粘合薄膜。
这样制备的各向异性导电粘合薄膜(宽度2毫米，长度4厘米)用ITO(铟锡氧化物)薄膜粘到0.7毫米厚的玻璃板上，在60℃，压力1.0MPa热压粘合4秒钟，然后剥离分隔片聚酯薄膜(预粘合)。此后，将包含25微米厚的聚酰亚胺薄膜和分布在该薄膜上的镀金铜线路的柔性电路(导线间距70微米，导线宽度35微米和厚度12微米)定位，并固定在上面预粘合的各向异性导电粘合薄膜上。用普通加热型压机，在这样的条件下(即各向异性导电粘合薄膜部分在180℃和在2.0MPa加热8-10秒钟)热压它们，由此完成电路连接(主粘合)。
粘合强度的评估
将这样用ITO薄膜通过热压粘合到玻璃板上形成的柔性电路切成5毫米的宽度，以50毫米/分钟的速率，以与带有ITO薄膜的玻璃板成90°的方向拉，记录它们的最大值。
用DSC(差示扫描量热计)放热性质的评价
如果酰胺过分抑制环氧化合物的聚合反应，聚合反应进行得不好，在DSC的测量中，这表现为放热峰温度升高，或热值减小。所以，在50-200℃的范围测量放热能量，得到的值与无酰胺的情况相比较。在测量时，温度升高的速率设定于10℃/分钟。
连接状态的评价
用数字万用表测量有ITO薄膜的玻璃板和柔性电路之间的连接电阻。
评价结果示于表1和表2。
                                         表1
  实施例   比较例
  组合物   E1   E2   E3   E4   C1   C2   C3
  UVR6128   1   1   1   1   1   1   1
  Epikote154   5   5   5   5   5   5   5
  PKHC   4   4   4   4   4   4   4
  稳定剂   0.009   0.009   0.009   0.009   0.009   0.009   0.009
  硅烷偶合剂A187   0.2   0.2   0.2   0.2   0.2   0.2   0.2
  阳离子聚合催化剂   0.06   0.06   0.06   0.06   0.06   0.06   0.06
  酰胺(对催化剂的当量)   油酰胺0.0015(0.1)   芥酸酰胺0.0018(0.1)   月桂酰胺0.0011(0.1)   正丁酰胺0.0005(0.1)   无   油酰胺0.015(1)   芥酸酰胺0.018(1)
  开始温度(℃)   97   100   99   100   102   95   99
  DSC放热峰温度(℃)   108   108   108   108   105   105   108
  DSC放热能量(卡/克)   287   298   298   298   299   68   83
  连接电阻(欧姆)   1.8   2.0   1.6   1.7   2.2   1.8   2.2
  平均粘合强度(N/m)   663   698   707   679   503   586   705
  破坏方式   内聚   内聚   内聚   内聚   ITO界面   ITO界面   ITO界面
                             表2
  实施例   比较例
  组合物   E5   E6   C4
  UVR6128   4   4   4
  Epikote154   2   2   2
  PKHC   4   4   4
  稳定剂   0.009   0.009   0.009
  硅烷偶合剂A187   0.2   0.2   0.2
  阳离子聚合催化剂   0.06   0.06   0.06
  酰胺(对催化剂当量)   油酰胺0.0015(0.1)   油酰胺0.0045(0.3)   无
  开始温度(℃)   94   101   96
  DSC放热峰温(℃)   122   128   121
  DSC放热能量(卡/克)   297   292   307
  连接电阻(欧姆)   1.5   1.6   1.6
  平均粘合强度(N/m)   690   590   632
  破坏方式   内聚   内聚   ITO界面
从上面的表可明显看出：在本发明的实施例中，与不加酰胺情况(C1)相比，差动扫描量热计的测量揭示：既不降低放热能量，在放热峰温度也无差异。由此证实：加入适量的酰胺不影响粘合剂组合物的固化反应。在实施例和比较例中，连接电阻和剥离粘合强度是令人满意的，但在破坏方式上有差异。更具体地说，在任一比较例中，破坏方式是ITO表面与粘合剂之间的界面破坏，而在加入适量酰胺的任实施例中，破坏方式是粘合剂的内聚破坏，揭示在界面粘合良好。
                         发明的效果
如前面几页所证明的，本发明的可阳离子聚合粘合剂组合物具有极佳的粘合性质，尤其在粘合剂和粘合体间界面处的粘合性质。而且，在用本发明可阳离子聚合粘合剂组合物粘合时，在修理时不需用有机溶剂，就可容易地从粘合体除去粘合剂。

Claims (14)

1.一种各向异性导电粘合剂组合物，其包括：
(A)可阳离子聚合单体，其选自环氧单体，乙烯基醚单体及其混合物，所述环氧单体选自环醚单体、脂环族环氧树脂和含缩水甘油基的树脂，并且所述环氧单体可以含有官能团，所述乙烯基醚单体选自甲基乙烯基醚、乙基乙烯基醚、叔丁基乙烯基醚、异丁基乙烯基醚、三甘醇二乙烯基醚和环己烷二甲醇二乙烯基醚；
(B)阳离子聚合催化剂；
(C)稳定剂；
其中，所述稳定剂(C)至少是一种下列分子式(I)表示的酰胺：
Figure C028179050002C1
式中，R1是具有1-30个碳原子的烷基，或含有一个或两个不饱和键和含有2-30个碳原子的链烯基，各R2分别是氢或具有1-10个碳原子的烷基；和
(D)导电颗粒。
2.一种导热粘合剂组合物，其包括：
(A)可阳离子聚合单体，其选自环氧单体，乙烯基醚单体及其混合物，所述环氧单体选自环醚单体、脂环族环氧树脂和含缩水甘油基的树脂，并且所述环氧单体可以含有官能团，所述乙烯基醚单体选自甲基乙烯基醚、乙基乙烯基醚、叔丁基乙烯基醚、异丁基乙烯基醚、三甘醇二乙烯基醚和环己烷二甲醇二乙烯基醚；
(B)阳离子聚合催化剂；
(C)稳定剂；
其中，所述稳定剂(C)至少是一种下列分子式(I)表示的酰胺：
式中，R1是具有1-30个碳原子的烷基，或含有一个或两个不饱和键和含有2-30个碳原子的链烯基，各R2分别是氢或具有1-10个碳原子的烷基；和
(D)导热颗粒。
3.如权利要求1所述的各向异性导电粘合剂组合物，其特征在于：所述的酰胺选自乙酰胺，丙酰胺，正丁酰胺，月桂酰胺，N，N-二甲基乙酰胺，油酸酰胺，芥酸酰胺及其混合物。
4.如权利要求1所述的各向异性导电粘合剂组合物，其特征在于：所述酰胺掺合量是0.000005-0.02重量份/100重量份的整个粘合剂组合物。
5.如权利要求1所述的各向异性导电粘合剂组合物，其特征在于：所述可阳离子聚合单体是脂环族环氧树脂，含缩水甘油基团的环氧树脂或它们的混合物。
6.如权利要求1所述的各向异性导电粘合剂组合物，其特征在于：所述阳离子聚合催化剂是热激活型阳离子聚合催化剂。
7.如权利要求1所述的各向异性导电粘合剂组合物，它是薄膜的形式。
8.如权利要求2所述的导热粘合剂组合物，其特征在于：所述的酰胺选自乙酰胺，丙酰胺，正丁酰胺，月桂酰胺，N，N-二甲基乙酰胺，油酸酰胺，芥酸酰胺及其混合物。
9.一种可阳离子聚合粘合剂组合物，其包括：
(A)可阳离子聚合单体，其选自环氧单体，乙烯基醚单体及其混合物，所述环氧单体选自环醚单体、脂环族环氧树脂和含缩水甘油基的树脂，并且所述环氧单体可以含有官能团，所述乙烯基醚单体选自甲基乙烯基醚、乙基乙烯基醚、叔丁基乙烯基醚、异丁基乙烯基醚、三甘醇二乙烯基醚和环己烷二甲醇二乙烯基醚；
(B)阳离子聚合催化剂；和
(C)稳定剂；
其中，所述稳定剂(C)至少是一种下列分子式(I’)表示的酰胺：
式中，R1是具有1-30个碳原子的烷基，或含有一个或两个不饱和键和含有2-30个碳原子的链烯基。
10.如权利要求9所述的可阳离子聚合粘合剂组合物，其特征在于：所述酰胺掺合量是0.000005-0.02重量份/100重量份的整个粘合剂组合物。
11.如权利要求9所述的可阳离子聚合粘合剂组合物，其特征在于：所述可阳离子聚合单体是脂环族环氧树脂，含缩水甘油基团的环氧树脂或它们的混合物。
12.如权利要求9所述的可阳离子聚合粘合剂组合物，其特征在于：所述阳离子聚合催化剂是热激活型阳离子聚合催化剂。
13.如权利要求9所述的可阳离子聚合粘合剂组合物，它是薄膜的形式。
14.如权利要求2所述的导热粘合剂组合物，它是薄膜的形式。
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