CN107082836B - 碳纳米管导电微球的制备方法及导电胶 - Google Patents

碳纳米管导电微球的制备方法及导电胶 Download PDF

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CN107082836B
CN107082836B CN201710322106.7A CN201710322106A CN107082836B CN 107082836 B CN107082836 B CN 107082836B CN 201710322106 A CN201710322106 A CN 201710322106A CN 107082836 B CN107082836 B CN 107082836B
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TCL Huaxing Photoelectric Technology Co Ltd
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Abstract

本发明提供一种碳纳米管导电微球的制备方法及导电胶。该碳纳米管导电微球的制备方法与现有的先制备塑料或树脂微球再镀导电金属的两步法相比较，不需要分别制备塑料或树脂微球与导电层，而是以喷雾造粒的方式使得苯乙烯单体、交联剂、及引发剂发生交联反应形成聚合物微球的同时将碳纳米管掺杂在聚合物微球内，仅需一步便制备出以碳纳米管作为导电介质的碳纳米管导电微球，能够简化工艺，减少工序，节约成本；碳纳米管掺杂于聚合物微球内，能够减轻碳纳米管与树脂热失配的影响，保证导电微球的导电性能；且整个制备过程无重金属盐，能够降低生物毒性，不污染环境。

Description

碳纳米管导电微球的制备方法及导电胶
技术领域
本发明涉及显示器件技术领域，尤其涉及一种碳纳米管导电微球的制备方法及导电胶。
背景技术
目前，薄膜晶体管液晶显示器(Thin Film Transistor Liquid CrystalDisplay，TFT-LCD)多采用掺杂有导电金球的框胶来导通上、下基板，形成单向导电通路。当上、下基板贴合后，包裹在导电金球外层的金属，能够传输电子起到导通作用，导电金球的内核为具有弹性的树脂或塑料，能够发生形变，缓和上、下基板贴合后的压力。
在现有技术中，应用于TFT-LCD框胶或异方性导电胶(Anisotropic ConductiveFilm，ACF)内的导电金球的制备方法一般先通过聚合反应、热固化等方法制备出塑料或树脂微球作为母球，再在塑料或树脂微球表面镀导电金属形成导电层。此类制备方法存在几点不足：
(1)、需要先制备塑料或树脂微球再镀导电金属，业内通常称为“两步法”，涉及到微球的制备与粒径控制、以及导电金属的电镀沉积工艺等，工艺比较繁琐、复杂；
(2)、塑料或树脂微球的材料为高分子聚合物，与导电金属层的热收缩率相差较大，容易在制备过程中产生热应力，导致导电金属层和微球表面热失配，造成导电金属层脱离剥落而影响导电金球的导电性能；
(3)、导电金属一般为金(Au)、银(Ag)、铝(Al)、铜(Cu)、镍(Ni)等，Cu、Al、Ni价格便宜，导电性好但容易氧化，影响导电性；Ag具有良好导电性以及化学稳定性，但容易在潮湿环境下出现电子迁出的现象；Au在镀膜工艺时所使用的金盐大多为氰化物，毒性非常大，镀金过程中容易产生重金属污染，并且Au为稀有贵金属，成本很高。
随着显示技术的发展，出现了以碳纳米管(Carbon nanotube，CNT)作为导电介质的导电球。专利CN201510662918.7介绍了一种利用CNT包覆树脂微球的导电微球的制备方法，该方法本质上仍为两步法，工艺较复杂。
发明内容
本发明的目的在于提供一种碳纳米管导电微球的制备方法，能够简化工艺，减少工序，节约成本，减轻热失配的影响，保证导电微球的导电性能，且不污染环境。
本发明的另一目的在于提供一种导电胶，其内的碳纳米管导电微球易于制作，成本较低，受热失配的影响较小，导电性能优良，且不污染环境。
为实现上述目的，本发明首先提供一种碳纳米管导电微球的制备方法，包括如下步骤：
步骤S1、提供苯乙烯单体、交联剂、及引发剂，将所述苯乙烯单体、交联剂、及引发剂按比例混合，得到第一种液体；
步骤S2、提供分散剂、表面活性剂、及碳纳米管，将所述分散剂、表面活性剂、及碳纳米管溶解、分散在乙醇中，得到第二种液体；
步骤S3、将第一种液体与第二种液体按比例混合，得到混合液体；
步骤S4、将所述混合液体溶于极性溶剂中，得到待喷雾干燥的浆料；
步骤S5、将所述待喷雾干燥的浆料放入喷雾造粒干燥机中，控制喷雾造粒干燥机的入口温度、出口温度、压力、及转盘转速，使所述极性溶剂快速蒸发，所述分散剂将苯乙烯单体、交联剂、引发剂、及碳纳米管粘结成型为碳纳米管导电微球雏形；
步骤S6、升温并保温，使所述碳纳米管导电微球雏形内的苯乙烯单体、交联剂、及引发剂充分反应交联，得到碳纳米管导电微球。
所述步骤S1中，苯乙烯单体、交联剂、及引发剂三者的重量百分比为：60％≤苯乙烯单体≤90％，10％≤交联剂≤40％，引发剂≤5％；
所述交联剂为二乙烯基苯、过氧化物交联剂、硅烷类交联剂中的一种或多种；
所述引发剂为亚硫酸氢钠、过硫酸铵、过硫酸钾、过氧化二苯甲酰、过氧化苯甲酸叔丁酯、偶氮二异丁氰中的一种或多种。
所述过氧化物交联剂为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化氢二异丙苯中的一种或多种；
所述硅烷类交联剂为乙烯基三乙氧基硅烧、乙烯基三乙氧基硅烷中的一种或二者的混合。
所述步骤S2中，分散剂、表面活性剂、及碳纳米管三者的重量百分比为：分散剂≤10％、表面活性剂≤10％、80％≤碳纳米管＜100％。
所述分散剂为聚乙烯醇；
所述表面活性剂为十六烷基三甲基溴化铵、十二烷基硫酸钠、月桂基硫酸钠、十二烷基苯磺酸钠中的一种或多种。
所述步骤S3中，第一种液体与第二种液体的体积比为：10:1～1:10。
所述步骤S4中，所述极性溶剂为乙醇；
所述混合液体与极性溶剂的体积比为：1:10～10:1；
待喷雾干燥的浆料的粘度为：0.1cp～50cp。
所述待喷雾干燥的浆料的粘度≤10cp。
所述步骤S5中，喷雾造粒干燥机的入口温度为150℃～500℃，出口温度为0℃～200℃，转盘转速为50rpm～150rpm；
所述步骤S6中，升温后的温度为75℃～85℃，保温的时间为4h～5h。
本发明还提供一种导电胶，包括经上述碳纳米管导电微球的制备方法所制备出的碳纳米管导电微球。
本发明的有益效果：本发明提供的一种碳纳米管导电微球的制备方法，与现有的先制备塑料或树脂微球再镀导电金属的两步法相比较，不需要分别制备塑料或树脂微球与导电层，而是以喷雾造粒的方式使得苯乙烯单体、交联剂、及引发剂发生交联反应形成聚合物微球的同时将碳纳米管掺杂在聚合物微球内，仅需一步便制备出以碳纳米管作为导电介质的碳纳米管导电微球，能够简化工艺，减少工序，节约成本；碳纳米管掺杂于聚合物微球内，能够减轻碳纳米管与树脂热失配的影响，保证导电微球的导电性能；且整个制备过程无重金属盐，能够降低生物毒性，不污染环境。本发明提供的一种导电胶，包括经上述碳纳米管导电微球的制备方法所制备出的碳纳米管导电微球，该碳纳米管导电微球易于制作，成本较低，受热失配的影响较小，导电性能优良，且不污染环境。
附图说明
为了能更进一步了解本发明的特征以及技术内容，请参阅以下有关本发明的详细说明与附图，然而附图仅提供参考与说明用，并非用来对本发明加以限制。
附图中，
图1为本发明的碳纳米管导电微球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1，本发明首先提供一种碳纳米管导电微球的制备方法，包括如下步骤：
步骤S1、提供苯乙烯单体、交联剂、及引发剂，将所述苯乙烯单体、交联剂、及引发剂按比例混合，得到第一种液体。
具体地，所述苯乙烯单体、交联剂、及引发剂三者的重量百分比为：60％≤苯乙烯单体≤90％，10％≤交联剂≤40％，引发剂≤5％。
所述交联剂为二乙烯基苯(DVB)、过氧化物交联剂、硅烷类交联剂中的一种或多种。进一步地，所述过氧化物交联剂为过氧化二异丙苯(DCP)、过氧化苯甲酰(BPO)、二叔丁基过氧化物(DTBP)、过氧化氢二异丙苯(DBHP)中的一种或多种；所述硅烷类交联剂为乙烯基三乙氧基硅烧(例如美国联合碳化物公司的A1522)、乙烯基三乙氧基硅烷(例如美国联合碳化物公司的A151)中的一种或二者的混合。
所述引发剂为亚硫酸氢钠(NaHSO3)、过硫酸铵((NH4)2S2O8)、过硫酸钾(K2S2O8)、过氧化二苯甲酰(BPO)、过氧化苯甲酸叔丁酯(BPB)、偶氮二异丁氰(AIBN)中的一种或多种。
步骤S2、提供分散剂、表面活性剂、及碳纳米管，将所述分散剂、表面活性剂、及碳纳米管溶解、分散在乙醇中，得到第二种液体。
步骤S3、将第一种液体与第二种液体按比例混合，得到混合液体。
具体地，第一种液体与第二种液体的体积比为：10:1～1:10，通过这个比例来调节后续步骤中所形成的聚苯乙烯树脂微球与碳纳米管的比例以调节最终制得的碳纳米管导电微球的力学性能和电学性能。
所述分散剂、表面活性剂、及碳纳米管三者的重量百分比为：分散剂≤10％、表面活性剂≤10％、80％≤碳纳米管＜100％。
进一步地，所述分散剂为聚乙烯醇(PVA)；所述表面活性剂为十六烷基三甲基溴化铵(CTAB)、十二烷基硫酸钠(SDS)、月桂基硫酸钠(SLS)、十二烷基苯磺酸钠(SDBS)中的一种或多种。
步骤S4、将所述混合液体溶于乙醇等极性溶剂中，得到待喷雾干燥的浆料。
具体地，所述混合液体与极性溶剂的体积比为：1:10～10:1，通过这个比例来调节所述待喷雾干燥的浆料的粘度，使得待喷雾干燥的浆料的粘度为：0.1cp～50cp，优选待喷雾干燥的浆料的粘度≤10cp。
步骤S5、将所述待喷雾干燥的浆料放入喷雾造粒干燥机中，控制喷雾造粒干燥机的入口温度在150℃～500℃、出口温度在0℃～200℃、转盘转速在50rpm～150rpm、及压力，使90％以上的极性溶剂在20秒内快速蒸发，所述浆料初步干燥，所述分散剂起到粘结剂的作用而将苯乙烯单体、交联剂、引发剂、及碳纳米管粘结成型为碳纳米管导电微球雏形。
该步骤S5通过喷雾造粒干燥机来进行喷雾造粒，将所述待喷雾干燥的浆料喷入喷雾造粒干燥机的造粒塔，在喷雾热风的作用下，所述待喷雾干燥的浆料干燥、团聚，从而得到球状团粒，即碳纳米管导电微球雏形，且在碳纳米管导电微球雏形中，苯乙烯单体、交联剂、引发剂、及碳纳米管是相互混合掺杂的。
使用喷雾造粒干燥机的优势在于干燥速度快，可通过调节所述待喷雾干燥的浆料的粘度、喷雾造粒干燥机的入口温度、出口温度、转盘转速、压力、风机速度等参数来调节碳纳米管导电微球雏形的粒径大小、粒径分布等，工艺可调节性能较好。
步骤S6、升温至75℃～85℃并保温4h～5h，使所述碳纳米管导电微球雏形内的苯乙烯单体、交联剂、及引发剂充分反应交联，得到碳纳米管导电微球，并提高碳纳米管导电微球的内聚力及机械强度。
上述方法使得苯乙烯单体、交联剂、及引发剂发生交联反应形成聚合物微球的同时将碳纳米管掺杂在聚合物微球内，而不是像现有技术那样应用两步法先制备塑料或树脂微球再镀导电金属，因此可以称为“一步法”，能够简化工艺，减少工序，节约成本；所述碳纳米管作为导电介质起到导电作用，所述聚合物微球起到支撑作用并在受热压时产生变形，由于碳纳米管是掺杂在聚合物微球内，能够减轻碳纳米管与树脂热失配的影响，保证导电微球的导电性能；另外，整个制备过程无重金属盐，能够降低生物毒性，不污染环境。
基于同一发明构思，本发明还提供一种导电胶，包括胶材、及分散在所述胶材内的碳纳米管导电微球。所述胶材可选择ACF导电胶胶材；所述碳纳米管导电微球经上述方法制备，即碳纳米管掺杂在聚合物微球内，该碳纳米管导电微球易于制作，成本较低，受热失配的影响较小，导电性能优良，且不污染环境。
综上所述，本发明的碳纳米管导电微球的制备方法，与现有的先制备塑料或树脂微球再镀导电金属的两步法相比较，不需要分别制备塑料或树脂微球与导电层，而是以喷雾造粒的方式使得苯乙烯单体、交联剂、及引发剂发生交联反应形成聚合物微球的同时将碳纳米管掺杂在聚合物微球内，仅需一步便制备出以碳纳米管作为导电介质的碳纳米管导电微球，能够简化工艺，减少工序，节约成本；碳纳米管掺杂于聚合物微球内，能够减轻碳纳米管与树脂热失配的影响，保证导电微球的导电性能；且整个制备过程无重金属盐，能够降低生物毒性，不污染环境。本发明的导电胶，包括经上述碳纳米管导电微球的制备方法所制备出的碳纳米管导电微球，该碳纳米管导电微球易于制作，成本较低，受热失配的影响较小，导电性能优良，且不污染环境。
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 (10)

1.一种碳纳米管导电微球的制备方法，其特征在于，包括如下步骤：
步骤S1、提供苯乙烯单体、交联剂、及引发剂，将所述苯乙烯单体、交联剂、及引发剂按比例混合，得到第一种液体；
步骤S2、提供分散剂、表面活性剂、及碳纳米管，将所述分散剂、表面活性剂、及碳纳米管溶解、分散在乙醇中，得到第二种液体；
步骤S3、将第一种液体与第二种液体按比例混合，得到混合液体；
步骤S4、将所述混合液体溶于极性溶剂中，得到待喷雾干燥的浆料；
步骤S5、将所述待喷雾干燥的浆料放入喷雾造粒干燥机中，控制喷雾造粒干燥机的入口温度、出口温度、压力、及转盘转速，使所述极性溶剂快速蒸发，所述分散剂将苯乙烯单体、交联剂、引发剂、及碳纳米管粘结成型为碳纳米管导电微球雏形；
步骤S6、升温并保温，使所述碳纳米管导电微球雏形内的苯乙烯单体、交联剂、及引发剂充分反应交联，得到碳纳米管导电微球；
所述步骤S1中，苯乙烯单体、交联剂、及引发剂三者的重量百分比为：60％≤苯乙烯单体≤90％，10％≤交联剂≤40％，引发剂≤5％。
2.如权利要求1所述的碳纳米管导电微球的制备方法，其特征在于，
所述交联剂为二乙烯基苯、过氧化物交联剂、硅烷类交联剂中的一种或多种；
所述引发剂为亚硫酸氢钠、过硫酸铵、过硫酸钾、过氧化二苯甲酰、过氧化苯甲酸叔丁酯、偶氮二异丁氰中的一种或多种。
3.如权利要求2所述的碳纳米管导电微球的制备方法，其特征在于，所述过氧化物交联剂为过氧化二异丙苯、过氧化苯甲酰、二叔丁基过氧化物、过氧化氢二异丙苯中的一种或多种；
所述硅烷类交联剂为乙烯基三乙氧基硅烷。
4.如权利要求1所述的碳纳米管导电微球的制备方法，其特征在于，所述步骤S2中，分散剂、表面活性剂、及碳纳米管三者的重量百分比为：分散剂≤10％、表面活性剂≤10％、80％≤碳纳米管＜100％。
5.如权利要求4所述的碳纳米管导电微球的制备方法，其特征在于，所述分散剂为聚乙烯醇；
所述表面活性剂为十六烷基三甲基溴化铵、十二烷基硫酸钠、十二烷基苯磺酸钠中的一种或多种。
6.如权利要求1所述的碳纳米管导电微球的制备方法，其特征在于，所述步骤S3中，第一种液体与第二种液体的体积比为：10:1～1:10。
7.如权利要求1所述的碳纳米管导电微球的制备方法，其特征在于，所述步骤S4中，所述极性溶剂为乙醇；
所述混合液体与极性溶剂的体积比为：1:10～10:1；
待喷雾干燥的浆料的粘度为：0.1cp～50cp。
8.如权利要求7所述的碳纳米管导电微球的制备方法，其特征在于，所述待喷雾干燥的浆料的粘度≤10cp。
9.如权利要求1所述的碳纳米管导电微球的制备方法，其特征在于，所述步骤S5中，喷雾造粒干燥机的入口温度为150℃～500℃，出口温度为0℃～200℃，转盘转速为50rpm～150rpm；
所述步骤S6中，升温后的温度为75℃～85℃，保温的时间为4h～5h。
10.一种导电胶，其特征在于，包括经权利要求1至9任一项所述的碳纳米管导电微球的制备方法所制备出的碳纳米管导电微球。
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US20180327267A1 (en) 2018-11-15
US10435302B2 (en) 2019-10-08
US20200002173A1 (en) 2020-01-02

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