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CN102264853A - 膜状粘合剂和各向异性导电粘合剂 - Google Patents

膜状粘合剂和各向异性导电粘合剂 Download PDF

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Publication number
CN102264853A
CN102264853A CN2009801522260A CN200980152226A CN102264853A CN 102264853 A CN102264853 A CN 102264853A CN 2009801522260 A CN2009801522260 A CN 2009801522260A CN 200980152226 A CN200980152226 A CN 200980152226A CN 102264853 A CN102264853 A CN 102264853A
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China
Prior art keywords
epoxy
film adhesive
resins
conductive particle
resin
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CN2009801522260A
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年冈英昭
奥田泰弘
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Sumitomo Electric Industries Ltd
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Sumitomo Electric Industries Ltd
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Publication of CN102264853A publication Critical patent/CN102264853A/zh
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Abstract

本发明提供一种膜状粘合剂，该膜状粘合剂通过包含以下物质作为必须成分而易于混合、具有高挠性，并且具有高粘合强度，作为必须成分的所述物质包括：分子量大于或等于30,000的双酚A苯氧树脂、分子量小于或等于500的环氧树脂、甲基丙烯酸缩水甘油酯共聚物、橡胶改性环氧树脂以及潜在性固化剂，其中所述甲基丙烯酸缩水甘油酯共聚物的环氧当量优选小于或等于1000。

Description

膜状粘合剂和各向异性导电粘合剂
技术领域
本发明涉及膜状粘合剂，该膜状粘合剂用于对电子部件和基板(包括电极、电路等)进行粘合和电连接。
背景技术
随着电子装置尺寸的减小和功能的进步，用于结构元件的接线端子也越来越狭小。因此，在电子封装领域中，人们使用了多种能够容易地在这些端子之间进行连接的膜状粘合剂。例如，人们使用膜状粘合剂以将集成电路(IC)芯片粘合至柔性印刷线路板(柔性印刷电路或FPC)上，以及将IC芯片粘合至具有铟锡氧化物(ITO)电极电路的玻璃板上等。
在膜状粘合剂中，有树脂组合物中包含导电颗粒的各向异性导电粘合剂(ACF：各向异性导电膜)和不包含导电颗粒的非导电膜(NCF)。这两种膜状粘合剂均通过以下方式加以使用：将膜状粘合剂放在待连接对象之间，并进行加热加压以使得所述对象粘合在一起。当使用各向异性导电粘合剂时，通过加热加压使得粘合剂中的树脂流动，从而将待连接对象上的相对电极之间的间隙密封，同时部分导电颗粒被困在相对电极之间，从而建立了电连接。当使用非导电膜时，通过加热加压使得树脂组合物流动，从而将电极(即待连接对象)彼此直接接触，由此建立了电连接。这些膜状粘合剂需要显示出如下性能：导电性能，即，使在厚度方向上彼此相对的电极之间的电阻(连接电阻)降低的性能；以及绝缘性能，即，使在表面方向上彼此相邻的电极之间的电阻(绝缘电阻)增加的性能。
由于膜状粘合剂用于连接精密仪器设备(例如，液晶显示器(LCD))的周边部分，因此其需要具有较高的连接可靠性。因此，除了导电/绝缘性能以外，膜状粘合剂还需要耐环境性。例如，其性能通过高温高湿测试、热循环测试等加以评估。
环氧型热固性树脂组合物主要用作构成膜状粘合剂的绝缘树脂组合物。例如，广泛应用的有将固化剂与热固性树脂(例如，环氧树脂、苯氧树脂或相似成分等)组合在一起的树脂组合物。
环氧树脂具有高耐热性和耐湿性，但其固化材料极脆且缺乏韧性(挠性)。因此，可能会因裂纹的产生而发生剥离，并且粘合强度低。当在连接中受热而发生固化收缩时，环氧树脂即显示出粘合强度；然而，固化收缩会在粘合界面和粘合剂内部产生应力。由固化收缩引起的应力与粘合剂的储存弹性模量成比例增加。由于环氧树脂在固化后显示出高储存弹性模量，因此在固化收缩时所产生的应力较高，残余应力会残留在粘合界面和粘合剂内部，因此一旦粘合剂在高温高湿情况下被释放，即会发生界面剥离。
为了弥补环氧树脂的这些缺点，将诸如丙烯酸酯橡胶或丁腈橡胶(NBR)之类的橡胶材料或诸如丙烯酸树脂之类的热塑性树脂与环氧树脂的组合使用，从而付与膜状粘合剂挠性。例如，专利文献1公开了用于电路连接的各向异性导电构件，其中将用于付与挠性的环氧化丁二烯成分与萘系环氧树脂和苯氧树脂组合使用。
发明内容
技术问题
付与挠性的上述材料与环氧树脂的相容性非常低。含有这种材料的膜状粘合剂处于所谓的海岛结构状态，在这种状态中，环氧树脂处于分散在橡胶材料中的状态或类似状态，而非完全溶解在橡胶材料中。为了形成这种分散状态，膜状粘合剂的构成成分必须彻底混合，即，必须使用特殊搅拌器进行混合，或必须严格控制制备条件。根据专利文献1，通过使用引入了官能团(环氧基团)的环氧化聚丁二烯作为付与挠性的成分，从而提高了与环氧树脂的相容性。然而，相对于其分子量，官能团的比率较低，因此效果不好。
本发明解决了上述问题，并且提供了一种具有高挠性、能够增强粘合强度、并且由易于混合的成分构成的膜状粘合剂。
解决问题的方法
本发明提供了一种膜状粘合剂，其包含以下物质作为必须成分：分子量大于或等于30,000的双酚A苯氧树脂、分子量小于或等于500的环氧树脂、甲基丙烯酸缩水甘油酯共聚物、橡胶改性环氧树脂以及潜在性固化剂(本申请的发明的第一方面)。
甲基丙烯酸缩水甘油酯共聚物是通过将甲基丙烯酸缩水甘油酯与其他共聚性单体共聚而制备的聚合物，并且其具有从聚合物主链分支出来的环氧基团。由于与环氧树脂的相容性得以提高，因此抑制了相分离，从而易于将该共聚物与环氧树脂混合。由于该共聚物为挠性成分，因此其能够付与膜状粘合剂以挠性并且可提高粘合强度。
甲基丙烯酸缩水甘油酯共聚物的环氧当量优选小于或等于1000(本申请的发明的第二方面)。当环氧当量大(即，分子链中的环氧基团的数目少)时，则与环氧树脂的相容性降低。在固化过程中，分子链中的环氧基团通过与环氧树脂发生反应，能够形成网络结构。这样便能够抑制高温、高湿度条件下的热膨胀，并且能够改善长期连接可靠性。当环氧当量大于1000时，与环氧树脂反应的反应位点数目少，因而不能形成有效的网络结构。因此，耐热性和耐湿性降低。
甲基丙烯酸缩水甘油酯共聚物的玻璃化转变温度(Tg)优选为低于双酚A苯氧树脂的玻璃化转变温度(本申请的发明的第三方面)。一般地，为了提高耐热性和耐湿性，膜状粘合剂所包含的树脂成分的玻璃化转变温度在固化后必须较高。这是因为，较高的玻璃化转变温度会降低高温度范围内的热膨胀系数，并且会减轻高温、高湿度环境下的特性改变。
膜状粘合剂还优选包含导电颗粒(本申请的发明的第四方面)。包含导电颗粒的膜状粘合剂可以用作各向异性导电粘合剂。
长径比大于或等于5的导电颗粒优选沿膜的厚度方向进行取向，以进一步提高各向异性导电率(本申请的发明的第五方面)。“沿膜的厚度方向进行取向”是指导电颗粒的纵向方向与膜表面垂直。
发明效果
根据本发明，可以获得具有高挠性、能够提高粘合强度、并且由易于混合的成分构成的膜状粘合剂。
附图简要说明
[图1]图1的(a)部分和(b)部分为示出了本发明所使用的导电颗粒长径比的测量方法的示意图。
[图2]图2为示出了导电颗粒沿膜厚度方向进行取向的情况的示意性横截面视图。
具体实施方式
现对本发明的实施方案进行描述。以下实施例并不限制本发明的范围。在附图说明中，相同的标号表示相同的元件，并且省略了重复的描述。附图中的尺寸比率并不一定与说明中的尺寸比率相同。
本发明提供了一种膜状粘合剂，其包含以下物质作为必须成分：分子量大于或等于30,000的双酚A苯氧树脂、分子量小于或等于500的环氧树脂、甲基丙烯酸缩水甘油酯共聚物、橡胶改性环氧树脂以及潜在性固化剂。
甲基丙烯酸缩水甘油酯共聚物是通过将甲基丙烯酸缩水甘油酯与其他共聚性单体共聚而得到的聚合物，并且其具有从聚合物主链分支出来的环氧基团。由于与环氧树脂的相容性得以提高，因此抑制了相分离，从而易于将该共聚物与环氧树脂混合。由于该共聚物为挠性成分，因此能够付与膜状粘合剂以弹性并且可提高粘合强度。
除上述成分以外，膜状粘合剂还包含橡胶改性环氧树脂。与甲基丙烯酸缩水甘油酯共聚物相同，橡胶改性环氧树脂也为挠性成分，并且当将其与甲基丙烯酸缩水甘油酯共聚物组合使用时，能够进一步增强膜状粘合剂的挠性。相对于环氧树脂和苯氧树脂的总量，橡胶改性环氧树脂的混合比率优选为1重量％至30重量％。
橡胶改性环氧树脂可以是在结构中含有橡胶和/或聚醚的任何环氧树脂。其具体例子包括：通过分子内化学键合的方式与羧基修饰的丁腈弹性体结合的环氧树脂(CTBN修饰的环氧树脂)；以及橡胶改性环氧树脂，例如丁腈橡胶改性环氧树脂(NBR-改性环氧树脂)、氨基甲酸乙酯改性环氧树脂和有机硅改性环氧树脂。它们可以单独使用或组合使用。
在这些橡胶改性环氧树脂中，优选使用NBR改性环氧树脂，这是因为其与环氧树脂及苯氧树脂的相容性较高。
甲基丙烯酸缩水甘油酯共聚物的环氧当量优选为小于或等于1000。当环氧当量大(即，分子链中环氧基团的数目少)时，则与环氧树脂的相容性降低。在固化过程中，分子链中的环氧基团通过与环氧树脂反应，能够形成网络结构。这样便能够抑制高温、高湿度条件下的热膨胀并且改善长期连接可靠性。当环氧当量大于1000时，与环氧树脂反应的位点数目较少。因此不能形成有效的网络结构，并且耐热性和耐湿性降低。
甲基丙烯酸缩水甘油酯共聚物的玻璃化转变温度(Tg)优选为低于双酚A苯氧树脂的玻璃化转变温度。一般地，为了提高耐热性和耐湿性，膜状粘合剂中的树脂成分的玻璃化转变温度在固化后必须升高。这是因为，高玻璃化转变温度会降低高温度范围内的热膨胀系数，并且会减轻高温、高湿度环境下的特性改变。
经常将具有高玻璃化转变温度的苯氧树脂用作树脂成分，以提高固化后的玻璃化转变温度。膜状粘合剂被置于待连接对象之间，并通过加热加压以将待连接对象粘合在一起。由于具有高玻璃化转变温度的苯氧树脂在加热加压过程中不会显示出充分的流动性，因此树脂成分会过多地留在电极(待连接对象)之间，而留下的树脂成分会固化成为绝缘膜，这样便会导致连接失效。当使用玻璃化转变温度低于苯氧树脂的玻璃化转变温度的甲基丙烯酸缩水甘油酯共聚物时，则可以提高膜状粘合剂整体的流动性。需要指出，玻璃化转变温度是使用动态粘弹性测量(动态力学分析或DMA)装置测定的。
甲基丙烯酸缩水甘油酯共聚物是通过将甲基丙烯酸缩水甘油酯与其他共聚性单体共聚而得到的聚合物。共聚性单体的例子包括：丙烯酸及丙烯酸衍生物，例如丙烯酸甲酯和丙烯酸酯；富马酸衍生物，例如富马酸二甲酯和富马酸二乙酯；以及苯乙烯和苯乙烯衍生物，例如α-甲基苯乙烯。由于丙烯酸衍生物可以提高甲基丙烯酸缩水甘油酯共聚物与环氧树脂和苯氧树脂之间的相容性，因此优选将丙烯酸衍生物用作共聚性单体。
对甲基丙烯酸缩水甘油酯共聚物的分子量没有特别限定，但从与环氧树脂相容性的角度来看，其重均分子量优选为小于或等于100,000。
相对于环氧树脂和苯氧树脂的总量，甲基丙烯酸缩水甘油酯共聚物的含量优选为1重量％至30重量％。这是因为，当甲基丙烯酸缩水甘油酯共聚物树脂的含量超过30％时，固化后的耐热性不够高。当甲基丙烯酸缩水甘油酯共聚物树脂含量小于1重量％时，则不能达到充分提高挠性的效果，并且粘合强度会降低。“树脂成分”是指热固性树脂和热挠性树脂，例如环氧树脂、苯氧树脂、甲基丙烯酸缩水甘油酯共聚物、橡胶改性环氧树脂等。
本发明所使用的环氧树脂在加热时与固化剂迅速反应，且显示出粘合性。对环氧树脂的类型没有特别限定。环氧树脂的例子包括双酚型环氧树脂，例如那些在结构中具有双酚A、双酚F、双酚S以及双酚AD的双酚型环氧树脂；酚醛型环氧树脂；联苯型环氧树脂；以及双环戊二烯型环氧树脂。
环氧树脂的分子量小于或等于500。当使用低分子量的环氧树脂时，交联密度增加，从而能够增强粘合性能。由于环氧树脂在加热时与固化剂迅速反应，因此粘合强度提高。
在上述环氧树脂中，本发明所使用的苯氧树脂具有较高的分子量。在本发明中，使用了分子量大于或等于30,000的双酚A苯氧树脂。使用具有高分子量的苯氧树脂会提高成膜性。此外，可提高树脂在连接温度下的熔融粘度，并且在不会扰乱下述导电颗粒的取向的情况下即可建立连接。
当将具有低分子量的环氧树脂与具有高分子量的苯氧树脂组合使用时，可以平衡膜状粘合剂的性质。环氧树脂与苯氧树脂的混合比优选为环氧树脂/苯氧树脂＝10/90至70/30。就以四氢呋喃(THF)作为展开剂的凝胶渗透色谱(GPC)测定出的聚苯乙烯而言，分子量为重均分子量。
本发明所使用的潜在性固化剂可以适当地选自已知的用于环氧树脂的固化剂。潜在性固化剂在低温下具有较高的储藏稳定性，且很少在室温下引起固化反应。然而，在特定条件下(例如，在加热条件下)，其会迅速引起固化反应。潜在性固化剂的例子包括咪唑型固化剂、酰肼型固化剂、胺型固化剂(例如，三氟化硼胺复合物、胺酰亚胺、聚胺型固化剂、叔胺以及烷基脲型固化剂)、双氰胺型固化剂及它们的改性材料。它们可以单独使用或使用两种或多种的混合物。
上述潜在性固化剂中，优选使用咪唑型潜在性固化剂。可使用已知的咪唑型潜在性固化剂作为咪唑型潜在性固化剂。例如，可以使用咪唑类化合物与环氧树脂的加合物。咪唑类化合物的例子包括咪唑、2-甲基咪唑、2-乙基咪唑、2-丙基咪唑、2-十二烷基咪唑、2-苯基咪唑、2-苯基-4-甲基咪唑以及4-甲基咪唑。
为了能够同时充分获得相矛盾的长期储藏性和快速固化性，优选的是，这些潜在性固化剂被高分子材料(例如，聚氨酯类材料或聚酯类材料)或无机物(例如镍、铜等的金属薄膜、或硅酸钙薄膜)包覆而被微囊化。因此特别优选微囊化的咪唑类潜在性固化剂。
潜在性固化剂与树脂成分(例如，环氧树脂、苯氧树脂以及甲基丙烯酸缩水甘油酯共聚物)的混合比率优选为树脂成分总重量的5重量％至90重量％。当潜在性固化剂的比率小于5重量％时，固化速率降低且可能导致固化不充分。当其比率大于90重量％时，固化剂倾向于不发生反应，而这可能降低耐热性和耐湿性。
膜状粘合剂还优选包含导电颗粒。包含导电颗粒的膜状粘合剂可以用作各向异性导电粘合剂。导电颗粒的例子包括金、银、铜、镍、及它们的合金的金属颗粒以及碳。也可使用按以下方法制备的颗粒：以金属、ITO等物质包覆由非导电玻璃、陶瓷、塑料或金属氧化物构成的芯的表面，从而在芯表面上形成导电层。对导电颗粒的形状没有特别限定。可以使用球形颗粒或长针形颗粒。
当将长度与直径比(长径比)大于或等于5的导电颗粒用作所述导电颗粒时，可在不增加导电颗粒含量的同时降低连接电阻。因此可以实现良好的电连接，并且可以将表面方向上的绝缘电阻维持为较高水平。导电颗粒的长径比通过电荷耦合器件(CCD)显微镜直接测量。如图1的(a)部分所示，长径比为导电颗粒1的长度L与直径R的比值。导电颗粒并非一定呈平直的形状，即使当其具有一些弯曲和/或分支部分时仍可使用。在这种情况下，如图1的(b)部分所示，通过将导电颗粒的最大长度(图中箭头的长度)假设为长度L来测定长径比。导电颗粒的“直径”为与长度方向垂直的横截面的直径。当横截面不为圆形时，将横截面的最大长度假定为导电颗粒的直径。
可将市售可得的针状导电颗粒用作长径比大于或等于5的导电颗粒。通过连接许多微细的金属颗粒而形成的针状颗粒也是优选的。更优选的是，长径比为10至100。导电颗粒的直径优选为1μm以下，这是因为这样的导电颗粒可在细间距电极之间进行连接。
构成微细金属颗粒的金属的例子包括：具有铁磁性的单一金属，例如Fe、Ni和Co；或具有铁磁性的金属的复合物。当使用具有铁磁性的金属时，颗粒通过其自身的磁性进行取向，或者如下文所述，可通过利用磁场使导电颗粒进行取向。
长径比大于或等于5的导电颗粒优选沿膜的厚度方向进行取向，以进一步提高各向异性导电性。“沿膜的厚度方向进行取向”是指导电颗粒的纵向方向与膜的表面垂直。图2为示出了导电颗粒沿膜厚度方向进行取向的情况的示意性横截面视图。膜状粘合剂的树脂成分2中的针状导电颗粒1沿膜的厚度方向进行取向(图中箭头方向)。对使导电颗粒沿膜的厚度方向进行取向的方法没有特别限定。如上文所述，当使用具有铁磁性的导电颗粒时，使导电颗粒进行取向的优选方法的例子为这样一种方法，该方法包括：使导电颗粒分散在树脂溶液中，将所得分散液涂布在基板上，沿与基板表面相交的方向对该基板施加磁场，从而使导电颗粒进行取向，并且(例如)将基板上的溶剂去除以使分散液凝固并固化，从而将取向固定。
根据用途的不同，在0.01体积％至30体积％(相对于膜状粘合剂的总体积)的范围内来选取导电颗粒的含量。为了防止由过量导电颗粒而引起的表面方向上的绝缘性能的退化，导电颗粒的含量更优选为0.01体积％至10体积％。
只要不损害本发明的实质，除上述基本成分以外，本发明的膜状粘合剂还可以包含其他热固性树脂、热挠性树脂等。可以包含诸如固化促进剂、聚合抑制剂、敏化剂、硅烷偶联剂、阻燃剂以及触变剂之类的添加剂。
本发明的膜状粘合剂可通过混合上述成分而获得。由于本发明所使用的甲基丙烯酸缩水甘油酯共聚物具有与环氧树脂和苯氧树脂的良好相容性，因此容易混合且不需要特殊的搅拌器。例如，可以通过以下方法容易地制备树脂成分的溶液：将环氧树脂、苯氧树脂、甲基丙烯酸缩水甘油酯共聚物、潜在性固化剂等以及溶剂放入容器中，并以离心型搅拌混合器将其简单混合几分钟。用辊涂机等来施加该溶液以形成薄膜，并且通过干燥等方式去除溶剂以得到膜状粘合剂。
当要使用导电颗粒时，可通过以下方法制备膜状粘合剂：将导电颗粒加入树脂成分的溶液中以制备分散液，用相同的方式来施加分散液以形成膜，并且通过干燥等方式去除溶剂。为了使导电颗粒进行取向，可以在膜的形成阶段，使导电颗粒通过沿膜状粘合剂的厚度方向上施加的磁场。当导电颗粒通过该磁场时，这些颗粒发生取向，并且在之后的去除溶剂步骤中，已取向的导电颗粒的状态被固定。虽然对膜状粘合剂的厚度没有特别限定，但其厚度通常为10μm至50μm。
实施例
实施例1
(涂布液的制备)
以50/20/15/15/30的重量比使用以下物质：作为苯氧树脂的双酚A环氧树脂(Epikote 1256(分子量：约50,000，Tg：约98℃)，由Japan Epoxy Resins株式会社生产)；作为环氧树脂的双酚F液体环氧树脂(Epikote 806(分子量：约350)，由Japan Epoxy Resins株式会社生产)；作为甲基丙烯酸缩水甘油酯共聚物的甲基丙烯酸缩水甘油酯-苯乙烯共聚物(Marproof G-0250S(环氧当量：310，分子量：约20,000，Tg：约74℃)，由NOF公司生产)；作为橡胶改性环氧树脂的NBR改性环氧树脂(TSR960，由DIC公司生产)；以及作为潜在性固化剂的微囊化咪唑型固化剂(NOVACURE HX3932，由Asahi Kasei Epoxy株式会社生产)。将卡必醇醋酸酯和乙酸丁酯的混合溶剂(以重量计，其混合比例为1∶1)加入到这些物质中。用离心式搅拌混合器进行简单混合3分钟。由此制备了固含量为60％的树脂溶液。将长度分布为1μm至12μm的针状镍微粒(长径比：5至60)作为导电颗粒加入到树脂溶液中，使得导电颗粒的含量相对于总固含量(树脂组合物+镍粉末)为0.2体积％。用离心式搅拌混合器将该混合物搅拌3分钟，以形成均匀分散液，从而制备用于粘合剂的涂布液。
(膜状粘合剂的制备)
用刮板将以上制备的涂布液施加在经脱模处理的聚对苯二甲酸乙二醇酯(PET)膜上，之后在磁通密度为100mT的磁场中，于60℃下干燥并固化30分钟。最终得到厚度为20μm的膜状粘合剂。
(连接电阻的评价)
制备以下两种电路板：具有124条镀金铜质电路的挠性印刷电路板(FPC)，所述镀金铜质电路宽50μm，高16μm，并以50μm的间距排列；以及具有ITO电路的玻璃板，所述ITO电路宽150μm，并以50μm的间距排列。将FPC和玻璃板彼此相对排列以形成菊花链，通过该菊花链，可以在124个连续位点处测定连接电阻，并将上述所得膜状粘合剂放在FPC和玻璃板之间。当加热至190℃时，施加5MPa的压力12秒，以粘合FPC和玻璃板。最终得到了由FPC和玻璃板构成的组件。以四端子法对124个连续位点处的对组件电阻进行测定，其中这124个连续位点是通过ITO电极、膜状粘合剂以及镀金铜质电路进行连接的。将电阻除以124以确定一个位点的连接电阻。
(热和湿度测试)
将由FPC和玻璃板构成的组件放入恒热-恒湿器中，设定温度为85℃且湿度为85％，100小时后取出。之后按照上文所述方式测定连接电阻。
(粘合强度的评价)
将FPC从由FPC和玻璃板构成的组件中剥离，并使用AutographAG-500G(由Shimadzu株式会社生产)测定90°剥离强度。对初始状态下的组件以及经过热和湿度测试的组件进行该粘合强度的测量。
比较例1
按照实施例1的方式制备厚度为20μm的膜状粘合剂，不同之处在于：未添加橡胶改性环氧树脂，并且将各成分的混合比改为苯氧树脂/环氧树脂/甲基丙烯酸缩水甘油酯共聚物/潜在性固化剂＝50/20/30/30。同样进行一系列评估。
比较例2
按照实施例1制备厚度为20μm的膜状粘合剂，不同之处在于：未添加甲基丙烯酸缩水甘油酯共聚物，并且将各成分的混合比改为苯氧树脂/环氧树脂/橡胶修饰环氧树脂/潜在性固化剂＝50/20/30/30。同样进行一系列评估。
比较例3
按照实施例1的方式尝试制备膜状粘合剂，不同之处在于：使用OH-封端的丙烯酸酯橡胶(AS-3000E，由Negami Chemical IndustrialCo.，Ltd.生产)替代甲基丙烯酸缩水甘油酯共聚物。但是，在进行了3分钟的离心搅拌后，未使环氧树脂和丙烯酸酯橡胶充分混合。树脂溶液仍然分离且不能形成为片状。结果在表中示出。
[表1]
Figure BPA00001390715200111
在使用了本发明膜状粘合剂的实施例1中，连接电阻较低，并且在高温、高湿度环境中放置100小时以后，连接电阻并未显著增大。在初始状态以及经过高温、高湿度测试以后，粘合强度均较高。
在比较例1中，反应速率降低，并且固化进展不充分，这可能是由于缺少橡胶改性环氧树脂而造成的。虽然连接电阻和粘合强度在初始状态时是令人满意的，但在高温和高湿度测试以后连接电阻和粘合强度则发生劣化。在比较例2中，由于缺少甲基丙烯酸缩水甘油酯共聚物，因此粘合剂没有显示出足够的挠性。与实施例1相比，粘合强度在初始状态以及经高温和高湿度测试后均较低。
本文所公开的实施方案和例子在各方面都是示例性的，而非限定性的。本发明的范围不是由上面的说明书部分限定而是由权利要求限定的，并且在与权利要求等同的范围和含义内的任何修改也包括在本发明的范围内。
工业实用性
本发明的膜状粘合剂适用于对基板、电子部件等进行粘合和电连接，从而在需要更小且更高功能的电子装置的领域，可以制作出更狭小的结构元件接线端子。
标号列表
1导电颗粒
2树脂成分
[专利文献1]
日本专利No.4110589

Claims (5)

1.一种膜状粘合剂，其包含以下物质作为必须成分：分子量大于或等于30,000的双酚A苯氧树脂、分子量小于或等于500的环氧树脂、甲基丙烯酸缩水甘油酯共聚物、橡胶改性环氧树脂以及潜在性固化剂。
2.根据权利要求1所述的膜状粘合剂，其中所述甲基丙烯酸缩水甘油酯共聚物的环氧当量小于或等于1000。
3.根据权利要求1或2所述的膜状粘合剂，其中所述甲基丙烯酸缩水甘油酯共聚物的玻璃化转变温度低于所述双酚A苯氧树脂的玻璃化转变温度。
4.根据权利要求1至3中任意一项所述的膜状粘合剂，还包含导电颗粒。
5.根据权利要求4所述的膜状粘合剂，其中所述导电颗粒的长度与直径比(长径比)大于或等于5，并且所述导电颗粒沿膜的厚度方向进行取向。
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CN105579544A (zh) * 2013-09-27 2016-05-11 琳得科株式会社 加热固化型磁化性粘接剂组合物及粘接片
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CN107431294A (zh) * 2015-03-20 2017-12-01 迪睿合株式会社 各向异性导电性膜及连接构造体
CN114582545A (zh) * 2015-03-20 2022-06-03 迪睿合株式会社 各向异性导电性膜及连接构造体
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CN108291130A (zh) * 2015-11-19 2018-07-17 3M创新有限公司 具有改善的失败模式的结构粘合剂
CN108291130B (zh) * 2015-11-19 2021-02-05 3M创新有限公司 具有改善的失败模式的结构粘合剂

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