CN111205439A - 白光嵌段聚合物、墨水组合物及其制备方法 - Google Patents

白光嵌段聚合物、墨水组合物及其制备方法 Download PDF

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CN111205439A
CN111205439A CN202010142372.3A CN202010142372A CN111205439A CN 111205439 A CN111205439 A CN 111205439A CN 202010142372 A CN202010142372 A CN 202010142372A CN 111205439 A CN111205439 A CN 111205439A
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light block
block polymer
ink composition
white light
white
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张仕杰
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Shenzhen China Star Optoelectronics Semiconductor Display Technology Co Ltd
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Priority to CN202010142372.3A priority Critical patent/CN111205439A/zh
Priority to PCT/CN2020/080557 priority patent/WO2021174603A1/zh
Priority to US16/759,747 priority patent/US20220041799A1/en
Publication of CN111205439A publication Critical patent/CN111205439A/zh
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Abstract

本申请提供一种白光嵌段聚合物、墨水组合物及其制备方法，白光嵌段聚合物使得喷墨打印时只需要打印一种墨水，简化喷墨打印制程，同时避免出现不同色光的像素点串色的问题。墨水组合物通过使白光嵌段聚合物、有机溶剂、表面张力调节剂以及粘度调节剂进行合适的配比，以使得墨水组合物适用于喷墨打印。

Description

白光嵌段聚合物、墨水组合物及其制备方法
技术领域
本申请涉及有机发光二极管技术领域，尤其涉及一种白光嵌段聚合物、墨水组合物及其制备方法。
背景技术
溶液制程制备有机发光二极管(Organic Light Emitting Diode，OLED)器件，特别是喷墨打印制备有机发光二极管器件，由于其在大面积面板制备过程中具有低成本、无需金属掩模版和高的材料利用率等优势，溶液制程制备有机发光二极管器件收到越来越多的关注。
一般而言，有机发光二极管器件中包含有多层结构，例如空穴传输层(HoleTransport Layer，HTL)、发光层(Emitting Layer，EML)以及电子传输层(ElectronTransport Layer，ETL)等。其中，发光层一般包括红光有机发光层、蓝光有机发光层以及绿光有机发光层，红光有机发光层、蓝光有机发光层以及绿光有机发光层由于分别使用了三种不同的墨水，喷墨打印三者时需要分开打印，增加制程的复杂性，即便使用高精密的打印仪器，发出不同光的有机发光层还是会存在串行的问题而导致像素点发光异常。
发明内容
本申请的目的在于提供一种白光嵌段聚合物、墨水组合物及其制备方法，以解决采用喷墨打印打印三种不同颜色墨水存在的串扰问题。
为实现上述目的，本申请提供一种白光嵌段聚合物，所述白光嵌段聚合物具有黄光嵌段，或/和，所述白光嵌段聚合物具有红光嵌段和绿光嵌段；所述白光嵌段聚合物具有蓝光嵌段；
其中，所述蓝光嵌段选自聚芴、聚芴衍生物、聚苯、聚苯衍生物、聚咔唑以及聚咔唑衍生物中的至少一种，所述黄光嵌段选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种，所述红光嵌段选自聚二噻吩苯并噻二唑，所述绿光嵌段选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种。
在上述白光嵌段聚合物中，所述蓝光嵌段选自聚芴，所述黄光嵌段选自聚苯并噻二唑，所述红光嵌段选自聚二噻吩苯并噻二唑，所述绿光嵌段选自聚苯并噻二唑。
在上述白光嵌段聚合物中，所述白光嵌段聚合物具有如下式(1)所示结构，
Figure BDA0002399535660000021
其中，所述x、所述y以及所述z为对应聚合物主链占所述白光嵌段聚合物的摩尔百分比，所述x、所述y以及所述z均大于0且小于1，且所述x、所述y以及所述z满足公式x+y+z＝1以及y＝x+z。
在上述白光嵌段聚合物中，所述x:y:z＝(0.35-0.45):0.5:(0.05-0.15)。
在上述白光嵌段聚合物中，所述x:y:z＝0.4:0.5:0.1。
在上述白光嵌段聚合物中，所述白光嵌段聚合物的数均分子量为1000-10000。
一种墨水组合物，按重量百分比计，所述墨水组合物包括：
Figure BDA0002399535660000022
在上述墨水组合物中，按重量百分比计，所述墨水组合物包括：
Figure BDA0002399535660000031
在上述墨水组合物中，所述有机溶剂选自乙二醇丁醚醋酸酯、丙二醇乙醚以及均四甲苯中的至少一种。
在上述墨水组合物中，所述表面张力调节剂选自咪唑、咪唑衍生物、苯酚以及对苯二酚中的至少一种，所述粘度调节剂选自所述醇、醚、酯以及有机胺中的至少一种。
一种上述墨水组合物的制备方法，所述制备方法包括如下步骤：
将0.001wt％-10wt％上述白光嵌段聚合物加入到60wt％-90wt％有机溶剂中溶解，得第一溶液；
向所述第一溶液中加入0.01wt％-15wt％表面张力调节剂以及0.01wt％-15wt％粘度调节剂，混合均匀，得所述墨水组合物。
有益效果：本申请提供一种白光嵌段聚合物、墨水组合物及其制备方法，白光嵌段聚合物以使得喷墨打印时只需要打印一种墨水，简化喷墨打印制程，同时避免出现不同色光的像素点串色的问题。墨水组合物通过使白光嵌段聚合物、有机溶剂、表面张力调节剂以及粘度调节剂进行合适的配比，以使得墨水组合物适用于喷墨打印。
进一步地，通过选择高沸点的有机溶剂，以使得油墨组合物更适用于喷墨打印制程。
附图说明
图1为本申请实施例一白光嵌段聚合物的合成路线。
具体实施方式
下面将结合本申请实施例中的附图，对本申请实施例中的技术方案进行清楚、完整地描述。显然，所描述的实施例仅仅是本申请一部分实施例，而不是全部的实施例。基于本申请中的实施例，本领域技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本申请保护的范围。
本申请提供一种白光嵌段聚合物，白光嵌段聚合物具有黄光嵌段，或/和，白光嵌段聚合物具有红光嵌段和绿光嵌段；白光嵌段聚合物具有蓝光嵌段，
其中，蓝光嵌段选自聚芴、聚芴衍生物、聚苯、聚苯衍生物、聚咔唑以及聚咔唑衍生物中的至少一种，黄光嵌段聚合物选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种，红光嵌段选自聚二噻吩苯并噻二唑，绿光嵌段选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种。
本申请白光嵌段聚合物至少包括特定的蓝光嵌段、特定的红光嵌段以及特定的绿光嵌段，或白光嵌段聚合物至少包括特定的蓝光嵌段以及特定的黄光嵌段，以使得白光嵌段聚合物发出白光，该白光嵌段聚合物应用于有机发光二极管显示器时，采用喷墨打印只需要打印一种墨水，简化喷墨打印制程，避免不同的像素点串色的风险，降低有机发光二极管显示器的材料和工艺成本。
可以理解的是，可以根据实际需要调整组成白光嵌段聚合物的各嵌段的比例。也可以从增强白光嵌段聚合物的柔性的角度，在白光嵌段聚合物的侧链上引入柔性侧链，例如长的烷基链。也可以从增强白光嵌段聚合物的溶解性的角度，在白光嵌段聚合物的侧链上引入带有氨正离子的侧链，以改善分子的溶解性和成膜性。
白光嵌段聚合物具有如下式(1)所示结构，
Figure BDA0002399535660000041
其中，x、y以及z为对应聚合物主链占白光嵌段聚合物的摩尔百分比，x、y以及z均大于0且小于1，且x、y以及z满足公式x+y+z＝1以及y＝x+z。
其中，x:y:z＝(0.35-0.45)：0.5：(0.05-0.15).
进一步地，x:y:z＝0.4:0.5:0.1。
其中，白光嵌段聚合物的数均分子量为1000-10000。进一步地，白光嵌段聚合物的数均分子量为2000-8000。例如白光嵌段聚合物的数均分子量为3000、4000、5000以及6000。
具体地，以下结合具体实施例对上述方案进行描述。
实施例一
本实施例提供一种白光嵌段聚合物，白光嵌段聚合物的合成过程如图1所示，白光嵌段聚合物的制备方法包括如下步骤：
将0.4mmol的有机化合物1、0.5mmol的有机化合物2以及0.1mmol有机化合物3和2mmol的碳酸钾加入到70mL的溶剂中，氮气保护条件下加入0.1mmol催化剂(三苯基膦)钯，加热至85℃反应72h后，冷却至室温，用三氯甲烷溶解后，在丙酮中沉降三次，得白光嵌段聚合物。
实施例二
本实施例提供一种墨水组合物，墨水组合物包括0.001g实施例一制得的白光嵌段聚合物、90g均四甲苯、0.5g咪唑以及9.499g乙二胺。
本实施例墨水组合物的制备方法包括如下步骤：
将0.001g实施例一制得的白光嵌段聚合物加入至90g甲苯中，搅拌，得第一溶液；
向第一溶液中加入0.5g咪唑以及9.499g乙二胺，混合均匀，得墨水组合物。
实施例三
本实施例提供一种墨水组合物，墨水组合物包括9g实施一制得的白光嵌段聚合物、61g丙二醇乙醚、15g苯酚以及15g乙醇。
本实施例墨水组合物的制备方法包括如下步骤：
将9g实施例一制得的白光嵌段聚合物加入至61g丙二醇乙醚中，搅拌，得第一溶液；
向第一溶液中加入15g苯酚以及15g乙醇，混合均匀，得墨水组合物。
实施例四
本实施例提供一种墨水组合物，墨水组合物包括5g实施例一制得的白光嵌段聚合物、75g乙二醇丁醚醋酸酯、10g对苯二酚以及10g丙醇。
本实施例墨水组合物的制备方法包括如下步骤：
将5g实施一制得的白光嵌段聚合物加入至75g乙二醇丁醚醋酸酯中，搅拌，得第一溶液；
向第一溶液中加入10g对苯二酚以及10g丙醇，混合均匀，得墨水组合物。
实施例五
本实施例提供一种墨水组合物，墨水组合物包括0.01g实施例一制得的白光嵌段聚合物、85g乙二醇丁醚醋酸酯、5g对苯二酚以及9.99g三乙胺。
本实施例墨水组合物的制备方法包括如下步骤：
将0.01g实施一制得的白光嵌段聚合物加入至85g乙二醇丁醚醋酸酯中，搅拌，得第一溶液；
向第一溶液中加入5g对苯二酚以及9.99g三乙胺，混合均匀，得墨水组合物。
实施例六
本实施例提供一种墨水组合物，墨水组合物包括3g实施例一制得的白光嵌段聚合物、85g均四甲苯、6g咪唑以及6g乙二胺。
本实施例墨水组合物的制备方法包括如下步骤：
将3g实施例一制得的白光嵌段聚合物加入至85g均四甲苯中，搅拌，得第一溶液；
向第一溶液中加入6g咪唑以及6g乙二胺，混合均匀，得墨水组合物。
上述实施例二至实施例六的墨水组合物通过喷墨打印以形成墨滴，经真空干燥成膜后，再在空气中热处理以进一步去除溶剂，以形成白光有机发光层。白光有机发光层搭配红色滤光片、蓝色滤光片以及绿色滤光片以分别发出红光、蓝光以及绿光，不用分别通过喷墨打印制得不同色光对应的有机膜层，简化了打印制程，避免不同色光的的像素点出现串色。
以上实施例的说明只是用于帮助理解本申请的技术方案及其核心思想；本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本申请各实施例的技术方案的范围。

Claims (10)

1.一种白光嵌段聚合物，其特征在于，所述白光嵌段聚合物具有黄光嵌段，或/和，所述白光嵌段聚合物具有红光嵌段和绿光嵌段；所述白光嵌段聚合物具有蓝光嵌段；
其中，所述蓝光嵌段选自聚芴、聚芴衍生物、聚苯、聚苯衍生物、聚咔唑以及聚咔唑衍生物中的至少一种，所述黄光嵌段选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种，所述红光嵌段选自聚二噻吩苯并噻二唑，所述绿光嵌段选自聚苯并噻二唑以及聚苯乙烯撑中的至少一种。
2.根据权利要求1所述的白光嵌段聚合物，其特征在于，所述白光嵌段聚合物具有如下式(1)所示结构，
Figure FDA0002399535650000011
其中，所述x、所述y以及所述z为对应聚合物主链占所述白光嵌段聚合物的摩尔百分比，所述x、所述y以及所述z均大于0且小于1，且所述x、所述y以及所述z满足公式x+y+z＝1以及y＝x+z。
3.根据权利要求2所述的白光嵌段聚合物，其特征在于，所述x:y:z＝(0.35-0.45):0.5:(0.05-0.15)。
4.根据权利要求3所述的白光嵌段聚合物，其特征在于，所述x:y:z＝0.4:0.5:0.1。
5.根据权利要求2所述的白光嵌段聚合物，其特征在于，所述白光嵌段聚合物的数均分子量为1000-10000。
6.一种墨水组合物，其特征在于，按重量百分比计，所述墨水组合物包括：
Figure FDA0002399535650000021
7.根据权利要求6所述的墨水组合物，其特征在于，按重量百分比计，所述墨水组合物包括：
Figure FDA0002399535650000022
8.根据权利要求6或7所述的墨水组合物，其特征在于，所述有机溶剂选自乙二醇丁醚醋酸酯、丙二醇乙醚以及均四甲苯。
9.根据权利要求6或7所述的墨水组合物，其特征在于，所述表面张力调节剂选自咪唑、咪唑衍生物、苯酚以及对苯二酚中的至少一种，所述粘度调节剂选自所述醇、醚、酯以及有机胺中的至少一种。
10.一种如权利要求6-9任一项所述墨水组合物的制备方法，其特征在于，所述制备方法包括如下步骤：
将0.001wt％-10wt％权利要求2所述的白光嵌段聚合物加入到60wt％-90wt％有机溶剂中溶解，得第一溶液；
向所述第一溶液中加入0.01wt％-15wt％表面张力调节剂以及0.01wt％-15wt％粘度调节剂，混合均匀，得所述墨水组合物。
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Application publication date: 20200529