CN104130735B - 石墨烯球导电胶的制备方法及该石墨烯球导电胶 - Google Patents
石墨烯球导电胶的制备方法及该石墨烯球导电胶 Download PDFInfo
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- CN104130735B CN104130735B CN201410352367.XA CN201410352367A CN104130735B CN 104130735 B CN104130735 B CN 104130735B CN 201410352367 A CN201410352367 A CN 201410352367A CN 104130735 B CN104130735 B CN 104130735B
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- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
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Abstract
本发明提供一种石墨烯球导电胶的制备方法及该石墨烯球导电胶，所述石墨烯球导电胶的制备方法包括以下步骤：步骤1、提供单体、引发剂、分散剂和溶剂制备一单体混合物，并采用该单体混合物制得高分子微球；步骤2、对所述高分子微球进行加热或等离子刻蚀预处理；步骤3、采用化学气相沉积方法在经步骤2预处理过的高分子微球表面或内部包覆或生长石墨烯，制得石墨烯球；步骤4、称取一定比例的环氧树脂、固化剂、促进剂，混合搅拌至分散均匀，制得环氧树脂胶体系；步骤5、将步骤3制得的石墨烯球分散于所述环氧树脂胶体系中，获得石墨烯球导电胶预备材料；步骤6、将所述石墨烯球导电胶预备材料进行脱泡处理，得到石墨烯球导电胶。
Description
技术领域
本发明涉及液晶显示器技术领域，尤其涉及一种石墨烯球导电胶的制备方法及该石墨烯球导电胶。
背景技术
现有大多数薄膜晶体管液晶显示器(TFT-LCD)都是采用单边引出电极的方式，通过导电点将Array(阵列)侧和CF(彩色滤光片)侧的共通电极连接到同一玻璃基板上，通过压贴在该单一基板上的驱动芯片实现驱动。这种导电点一般由热固型环氧树脂、玻璃纤维及1wt％～2wt％的导电金球构成。导电金球(Auball)是以粒径均匀的球状、有弹性的高分子材料(例如丙烯酸树脂)为基体，通过化学法先在其表面镀一层镍，而后置换镀上一层金，形成一种弹性形变性能良好的导电塑料微粒子，它的直径一般为5～8μm，电导率要求达到2.4×105Scm-1。传统的化学镀法制备导电金球的过程，即先通过对基体进行清洗、微蚀、敏化、活化使基体表面修饰上可以引发化学反应的活性中心钯，再化学镀镍和金，这也是目前工业上常用的制备导电金球的工艺。但这种方法存在一些缺陷：其一，高分子基体材料表面因敏化过程而会吸附一些锡离子，可能会影响镍镀层的附着力和均一性；其二，由于化学镀金过程的自催化氧化还原反应为：Au(CN)2 -+Ni→Au+Ni2++2CN-，随着反应的进行，镀液中会产生镍离子，而为了控制镀层的结晶结构，镀液中会加入ppm级钴离子，这些游离的金属离子可能会引起高分子微球基体的团聚，对镀金过程产生不利影响；其三，镀金过程中使用的金盐大多是氰化物，毒性非常大；另外，经过两次化学镀工艺后，金属镍(Ni)的回收再利用比较困难，而直接废弃则不利于环境保护。
为解决化学镀法制备导电金球的上述缺陷，专利CN102352495B采用逐层自组装法，舍弃了氯化亚锡和剧毒的氰化物，在微蚀后的高分子基体表面吸附带正电的聚合物，将其置于带负电的贵金属溶胶中(金或铂溶胶)，最后通过化学镀法在微球表面镀一层金，该法简化了预处理工艺，得到的微球表面的金层光滑致密，但该法要得到壳厚为几百埃的核壳粒子需要反复进行繁琐的沉积、提纯等操作，比较费时，而且贵金属溶胶使用量大、价格昂贵，因而该法成本较高。
石墨烯由于具有高的电导率(106Scm-1)、大的载流子迁移率(105cm2V–1s–1)、好的机械性能(1060GPa)和优异的柔韧性而成为研究的热点，被广泛应用于锂离子电池、超级电容器、太阳能电池、半导体、液晶显示器、传感器等领域。专利EP2537801A1在密闭容器中对有机化合物预烤，有机物裂解产生含碳和氢的气体,经过随后的热等静压处理(HIP)，得到生长在有机物空隙和表面的厚度约为1nm的石墨烯花。将带有机物内核的石墨烯花加入溶剂中，经过超声，即可得到石墨烯分散液。该法是快速大量生成高质量石墨烯的一种有效方法，所生成的石墨烯花保持有石墨烯特有的高电导率特性。
发明内容
本发明的目的在于提供一种石墨烯球导电胶的制备方法，该方法工艺简单，使用的原料来源丰富、价格低廉，且都无毒无害，利于环保。
本发明的目的还在于提供一种石墨烯球导电胶，具有结构独特、导电性能优异、环境友好等优点，可用于TFT-LCD中取代导电金球，也可用于其它导电点材料。为实现上述目的，本发明提供一种石墨烯球导电胶的制备方法，包括如下步骤:
步骤1、提供单体、引发剂、分散剂和溶剂制备一单体混合物，并采用该单体混合物制得高分子微球；
步骤2、对所述高分子微球进行加热或等离子刻蚀预处理；
步骤3、采用化学气相沉积方法在经步骤2预处理过的高分子微球表面或内部包覆或生长石墨烯，制得石墨烯球；
步骤4、称取一定比例的环氧树脂、固化剂、促进剂，混合搅拌至分散均匀，制得环氧树脂胶体系；
步骤5、将步骤3制得的石墨烯球分散于所述环氧树脂胶体系中，获得石墨烯球导电胶预备材料；
步骤6、将所述石墨烯球导电胶预备材料进行脱泡处理，得到石墨烯球导电胶。
所述步骤1中，所述单体是丙烯酸、苯乙烯、甲基丙烯酸甲酯或二乙烯基苯；所述引发剂是偶氮二异丁腈或过氧化苯甲酰中的一种或二者的混合物；所述分散剂是聚乙烯吡咯烷酮、聚乙二醇、聚乙醇或聚丙烯酸；所述溶剂是乙醇、甲醇或异丙醇中的一种或几种与水的混合物。
所述单体的用量占所述单体混合物的8wt％～42wt％；所述引发剂的用量占所述单体混合物的0.11wt％～5.2wt％；所述分散剂的用量占所述单体混合物的4.9wt％～21wt％；所述溶剂的用量占所述单体混合物的3wt％～56wt％。
所述步骤2中，所述加热预处理的方法为：将所述高分子微球在惰性气氛，100-500℃下预处理0.5-5h，得到多孔的高分子微球。
所述步骤2中，所述等离子刻蚀预处理的方法为：用反应耦合等离子体对所述高分子微球进行刻蚀，所述反应耦合等离子体为六氟化硫和氧气，在80-150℃下预处理2min～1h，得到活化后的高分子微球。
所述步骤3中，所述化学气相沉积方法的具体步骤为：将经步骤2预处理过的高分子微球置于化学气相沉积反应腔体内，对腔体抽真空后，向腔体内通入由甲烷、氢气及其它辅助气体组成的混合气体，采用红外线、热辐射、激光、微波、等离子体、紫外线或热感应方法中的一种或几种对经步骤2预处理过的高分子微球进行加热，在高分子微球表面或内部生成石墨烯。
所述甲烷占所述混合气体的体积比为1％～10％；所述氢气占所述混合气体的体积比为50％～99％；所述其它辅助气体为水蒸汽、氮气或氩气中的一种或几种。
所述步骤4中，所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述促进剂是二-乙基-四甲基咪唑、咪唑、二甲基咪唑或三乙胺；
所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5wt％。
所述步骤5中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30。
本发明还提供一种石墨烯球导电胶，包括石墨烯球和环氧树脂胶体系，其中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30；所述环氧树脂胶体系包括环氧树脂、固化剂和促进剂；所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；所述促进剂是二-乙基-四甲基咪唑、咪唑、二甲基咪唑或三乙胺；所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5％wt％。
本发明的有益效果：本发明的石墨烯球导电胶的制备方法采用CVD法在高分子微球表面或内部生长石墨烯，制得石墨烯球，将石墨烯球与环氧树脂胶体系按一定比例混合后，制成石墨烯球导电胶。该方法工艺简单，使用的原料来源丰富、价格低廉，且都无毒无害，利于环保。本发明的石墨烯球导电胶具有结构独特、导电性能优异、环境友好等优点，可用于TFT-LCD中取代导电金球，也可用于其它导电点材料，如各向异性导电胶(ACP)和各向异性导电膜(ACF)等，具有巨大的商业开发价值和市场应用前景。
附图说明
下面结合附图，通过对本发明的具体实施方式详细描述，将使本发明的技术方案及其它有益效果显而易见。
附图中，
图1为本发明石墨烯球导电胶的制备方法的流程图。
具体实施方式
为更进一步阐述本发明所采取的技术手段及其效果，以下结合本发明的优选实施例及其附图进行详细描述。
请参阅图1，本发明提供一种石墨烯球导电胶的制备方法，包括以下步骤：
步骤1、提供单体、引发剂、分散剂和溶剂制备一单体混合物，并采用该单体混合物制得高分子微球；
其中，所述单体是丙烯酸、苯乙烯、甲基丙烯酸甲酯或二乙烯基苯，所述单体的用量占所述单体混合物的8wt％～42wt％；
所述引发剂是偶氮二异丁腈或过氧化苯甲酰中的一种或二者的混合物，所述引发剂的用量占所述单体混合物的0.11wt％～5.2wt％；
所述分散剂是聚乙烯吡咯烷酮、聚乙二醇、聚乙醇或聚丙烯酸，所述分散剂的用量占所述单体混合物的4.9wt％～21wt％；
所述溶剂是乙醇、甲醇或异丙醇中的一种或几种与水的混合物，所述溶剂的用量占所述单体混合物的3wt％～56wt％。
步骤2、对所述高分子微球进行加热或等离子刻蚀预处理；
所述加热预处理的方法为：将所述高分子微球在惰性气氛(氮气或氩气)，100-500℃下预处理0.5-5h，得到多孔的高分子微球。
所述等离子刻蚀预处理的方法为：用反应耦合等离子体对所述高分子微球进行刻蚀，所述反应耦合等离子体为六氟化硫和氧气，在80-150℃下预处理2min～1h，得到活化后的高分子微球。
步骤3、采用化学气相沉积方法在经步骤2预处理过的高分子微球表面或内部包覆或生长石墨烯，制得石墨烯球；
所述化学气相沉积方法的具体步骤为：将经步骤2预处理过的高分子微球置于化学气相沉积(CVD)反应腔体内，对腔体抽真空后，向腔体内通入由甲烷、氢气及其它辅助气体组成的混合气体，采用红外线、热辐射、激光、微波、等离子体、紫外线或热感应方法中的一种或几种对经步骤2预处理过的高分子微球进行加热，在高分子微球表面或内部生成石墨烯；
所述甲烷占所述混合气体的体积比为1％～10％；所述氢气占所述混合气体的体积比为50％～99％；所述其它辅助气体为水蒸汽(H2O)、氮气(N2)或氩气(Ar)中的一种或几种。
所述步骤3中，通过调节CVD腔体中的混合气体的流量可以控制石墨烯生长层数，通过工艺优化得到具有最佳电导率的石墨烯球。
步骤4、提供环氧树脂、固化剂、促进剂，混合搅拌至分散均匀，制得环氧树脂胶体系；
所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；
所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；
所述促进剂是二-乙基-四甲基咪唑、咪唑、二甲基咪唑或三乙胺。所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5wt％。
步骤5、将步骤3制得的石墨烯球分散于所述环氧树脂胶体系中，获得石墨烯球导电胶预备材料；
其中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30。
步骤6、将所述石墨烯球导电胶预备材料进行脱泡处理，得到石墨烯球导电胶。
本发明还提供一种石墨烯球导电胶，包括石墨烯球和环氧树脂胶体系，其中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30；所述环氧树脂胶体系包括环氧树脂、固化剂和促进剂；所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；所述促进剂是二-乙基-四甲基咪唑、咪唑、二甲基咪唑或三乙胺；所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5％wt％。
综上所述，本发明的石墨烯球导电胶的制备方法采用CVD法在高分子微球表面或内部生长石墨烯，制得石墨烯球，将石墨烯球与环氧树脂胶体系按一定比例混合后，制成石墨烯球导电胶。该方法工艺简单，使用的原料来源丰富、价格低廉，且都无毒无害，利于环保。与传统的化学镀法制备导电金球的过程相比，可避免化学镀法中使用的氯化亚锡和有毒金盐；由于CVD法制备石墨烯使用的原料为来源广、易制备的碳氢化合物，可解决贵金属溶胶、金盐等价格昂贵的问题；同时该方法不需要使用氯化亚锡对基体进行敏化，避免了锡离子对包覆层的干扰。本发明的石墨烯球导电胶具有结构独特、导电性能优异、环境友好等优点，可用于TFT-LCD中取代导电金球，也可用于其它导电点材料，如各向异性导电胶(ACP)和各向异性导电膜(ACF)等，具有巨大的商业开发价值和市场应用前景。
以上所述，对于本领域的普通技术人员来说，可以根据本发明的技术方案和技术构思作出其他各种相应的改变和变形，而所有这些改变和变形都应属于本发明后附的权利要求的保护范围。
Claims (8)
1.一种石墨烯球导电胶的制备方法，其特征在于，包括以下步骤：
步骤1、提供单体、引发剂、分散剂和溶剂制备一单体混合物，并采用该单体混合物制得高分子微球；
步骤2、对所述高分子微球进行等离子刻蚀预处理；
步骤3、采用化学气相沉积方法在经步骤2预处理过的高分子微球表面或内部包覆或生长石墨烯，制得石墨烯球；
步骤4、称取一定比例的环氧树脂、固化剂、促进剂，混合搅拌至分散均匀，制得环氧树脂胶体系；
步骤5、将步骤3制得的石墨烯球分散于所述环氧树脂胶体系中，获得石墨烯球导电胶预备材料；
步骤6、将所述石墨烯球导电胶预备材料进行脱泡处理，得到石墨烯球导电胶；
所述步骤2中，所述等离子刻蚀预处理的方法为：用反应耦合等离子体对所述高分子微球进行刻蚀，所述反应耦合等离子体为六氟化硫和氧气，在80-150℃下预处理2min～1h，得到活化后的高分子微球。
2.如权利要求1所述的石墨烯球导电胶的制备方法，其特征在于，所述步骤1中，所述单体是丙烯酸、苯乙烯、甲基丙烯酸甲酯或二乙烯基苯；所述引发剂是偶氮二异丁腈或过氧化苯甲酰中的一种或二者的混合物；所述分散剂是聚乙烯吡咯烷酮、聚乙二醇或聚丙烯酸；所述溶剂是乙醇、甲醇或异丙醇中的一种或几种与水的混合物。
3.如权利要求2所述的石墨烯球导电胶的制备方法，其特征在于，所述单体的用量占所述单体混合物的8wt％～42wt％；所述引发剂的用量占所述单体混合物的0.11wt％～5.2wt％；所述分散剂的用量占所述单体混合物的4.9wt％～21wt％；所述溶剂的用量占所述单体混合物的3wt％～56wt％。
4.如权利要求1所述的石墨烯球导电胶的制备方法，其特征在于，所述步骤3中，所述化学气相沉积方法的具体步骤为：将经步骤2预处理过的高分子微球置于化学气相沉积反应腔体内，对腔体抽真空后，向腔体内通入由甲烷、氢气及其它辅助气体组成的混合气体，采用红外线、热辐射、激光、微波、等离子体、紫外线或热感应方法中的一种或几种对经步骤2预处理过的高分子微球进行加热，在高分子微球表面或内部生成石墨烯。
5.如权利要求4所述的石墨烯球导电胶的制备方法，其特征在于，所述甲烷占所述混合气体的体积比为1％～10％；所述氢气占所述混合气体的体积比为50％～99％；所述其它辅助气体为水蒸汽、氮气或氩气中的一种或几种。
6.如权利要求1所述的石墨烯球导电胶的制备方法，其特征在于，所述步骤4中，所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述促进剂是2-乙基-4-甲基咪唑、咪唑、二甲基咪唑或三乙胺；
所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5wt％。
7.如权利要求1所述的石墨烯球导电胶的制备方法，其特征在于，所述步骤5中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30。
8.一种石墨烯球导电胶，其特征在于，包括石墨烯球和环氧树脂胶体系，其中，所述环氧树脂胶体系与石墨烯球的质量比为100：2～30；所述环氧树脂胶体系包括环氧树脂、固化剂和促进剂；所述环氧树脂是双酚A型环氧树脂E44、双酚A型环氧树脂E51、双酚A型环氧树脂E54、双酚A型环氧树脂EPON826或双酚A型环氧树脂EPON828；所述环氧树脂的用量占所述环氧树脂胶体系的80wt％～95wt％；所述固化剂是六氢邻苯二甲酸酐、四氢邻苯二甲酸酐、丁二酸酰肼、己二酸酰肼、双氰胺或对苯二胺；所述固化剂的用量占所述环氧树脂胶体系的1wt％～12wt％；所述促进剂是2-乙基-4-甲基咪唑、咪唑、二甲基咪唑或三乙胺；所述促进剂的用量占所述环氧树脂胶体系的0.3wt％～5％wt％；
所述石墨烯球为由单体、引发剂、分散剂和溶剂组成的单体混合物所制得高分子微球经等离子刻蚀预处理后，通过化学气相沉积方法在其表面或内部包覆或生长而得到；
所述等离子刻蚀预处理的方法为：用反应耦合等离子体对所述高分子微球进行刻蚀，所述反应耦合等离子体为六氟化硫和氧气，在80-150℃下预处理2min～1h。
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| JP2017531278A (ja) | 2017-10-19 |
| KR102050198B1 (ko) | 2019-11-28 |
| GB2542318A (en) | 2017-03-15 |
| KR20190044131A (ko) | 2019-04-29 |
| KR102050199B1 (ko) | 2019-11-28 |
| KR20190044129A (ko) | 2019-04-29 |
| KR20170032402A (ko) | 2017-03-22 |
| US20170283665A1 (en) | 2017-10-05 |
| GB2542318B (en) | 2021-08-04 |
| GB201700828D0 (en) | 2017-03-01 |
| CN104130735A (zh) | 2014-11-05 |
| US20160280968A1 (en) | 2016-09-29 |
| WO2016011683A1 (zh) | 2016-01-28 |
| KR102050200B1 (ko) | 2019-11-28 |
| JP6369921B2 (ja) | 2018-08-08 |
| KR101980983B1 (ko) | 2019-05-21 |
| US9725625B2 (en) | 2017-08-08 |
| KR20190044130A (ko) | 2019-04-29 |
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