CN108864384B - 量子点分散树脂成型体、量子点分散胶体以及发光器件 - Google Patents
量子点分散树脂成型体、量子点分散胶体以及发光器件 Download PDFInfo
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Abstract
本发明公开了量子点分散树脂成型体、量子点分散胶体以及发光器件。其中量子点分散树脂成型体,包括分散于丙烯酸酯聚合物中的量子点,丙烯酸酯聚合物的至少一部分重复单元中包括C=C双键,所述重复单元的聚合度n≥2。该量子点分散树脂成型体由量子点分散胶体交联固化形成。该量子点分散树脂成型体可用于制备发光器件。本发明提供的量子点分散树脂成型体具有优异的氧气阻隔性能,有利于提高量子点的稳定性。
Description
技术领域
本发明涉及量子点分散树脂成型体、量子点分散胶体以及发光器件。
背景技术
量子点由于粒径在1~10nm,比表面积大,且表面含有大量不饱和悬键,导致了量子点的高度不稳定性,尤其是对水和氧气高度敏感。一般来讲,量子点的失效主要来源于表面配体的水解或氧化。在制作量子点膜的过程中,分散介质多用丙烯酸酯类树脂,然而丙烯酸酯类树脂的阻隔性能有限,还需要通过阻隔膜来提高阻隔性能,但是使用阻隔膜提高阻隔性能的成本很高,不利于推广。此外,还可以通过环氧树脂复配丙烯酸酯树脂来提高阻隔性能,但是环氧树脂的加入一方面会导致量子点效率降低,另一方面环氧树脂易黄化,从而导致量子点膜亮度降低。
发明内容
为了克服现有技术的不足,本发明的目的之一在于提供一种量子点分散树脂成型体,具有优异的氧气阻隔性能,其量子点的稳定性好。
本发明的目的之二在于提供一种量子点分散胶体,适于制备得到阻隔性能优异的量子点分散树脂成型体。
本发明的目的之三在于提供一种发光器件,其包括具有优异阻隔性能的量子点分散树脂成型体。
本发明的目的之一采用如下技术方案实现:
一种量子点分散树脂成型体,包括分散于丙烯酸酯聚合物中的量子点,所述丙烯酸酯聚合物的至少一部分重复单元中包括C=C双键,所述重复单元的聚合度n≥2。
所述丙烯酸酯聚合物中的不饱和的C=C双键具有结合氧气的功能,可以有效避免氧气将量子点氧化,也即提高了所述量子点分散树脂成型体对氧气的阻隔性能,使得量子点的稳定性得到提升。此外,C=C双键的增加,并不会影响量子点的发光效率,因此本发明的量子点分散树脂成型体在不影响量子点的发光效率的同时,提高了量子点的稳定性。
值得一提的是,所述丙烯酸酯聚合物即由丙烯酸酯类单体和/或丙烯酸酯预聚合物聚合形成的高分子材料,同时至少一部分制备所述丙烯酸酯聚合物的单体和/或预聚合除了含有烯丙基活性官能团外,还含有至少一个C=C双键,从而由丙烯酸酯类单体和/或丙烯酸酯预聚合物聚合形成的所述丙烯酸酯聚合物的重复单元中包括至少一个C=C双键。
本发明的目的之二采用如下技术方案实现:
一种量子点分散胶体,包括分散介质以及分散在所述分散介质中的量子点,所述分散介质包括:功能性丙烯酸酯树脂、非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体;所述功能性丙烯酸酯树脂选自功能性丙烯酸酯预聚物和/或功能性丙烯酸酯单体;所述功能性丙烯酸酯预聚物的分子链上除了包括烯丙基活性官能团外,还包括至少一个C=C双键;所述功能性丙烯酸酯单体的分子结构中除了包括烯丙基活性官能团外,还包括至少一个C=C双键。
值得一提的是,本发明所述的非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体仅相对于本发明所述的功能性丙烯酸酯预聚物以及功能性丙烯酸酯单体而言,也即非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体包含烯丙基活性官能团,但是除了烯丙基活性官能团外,不再含有不饱和的C=C双键,因此非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体聚合后形成的重复单元中,不包含C=C双键。
本发明的量子点分散胶体在固化后,形成量子点分散树脂成型体,也即量子点分散在高分子量的聚合物中,由于部分形成聚合物的单体或预聚物除了包含烯丙基活性官能团外,还包含C=C双键,单体或预聚合通过烯丙基活性官能团聚合,而其中的C=C双键不参与反应,因此最后得到的聚合物的一部分重复单元中,包含有C=C双键,这部分C=C双键能够与氧气结合,从而提高了聚合物的阻氧性能。
进一步地,所述非功能性丙烯酸酯类单体包括单官能度丙烯酸酯和/或多官能度丙烯酸酯;
所述单官能度丙烯酸酯选自以下一种或多种:(甲基)丙烯酸异冰片酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、3,3,5-三甲基环己基丙烯酸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、2-苯氧基乙基(甲基)丙烯酸酯、(甲基)四氢呋喃丙烯酸酯、(甲基)丙烯酸酯缩水甘油酯、丙烯酰吗啉、(甲基)丙烯酸-2-乙基己酯;
所述多官能度丙烯酸酯选自以下一种或多种:三羟甲基丙烷三(甲基)丙烯酸酯、乙氧化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯。
进一步地,所述非功能性丙烯酸酯预聚物选自聚氨酯丙烯酸酯、饱和聚酯丙烯酸酯、环氧丙烯酸酯树脂、有机硅改性丙烯酸酯中的一种或多种。
进一步地,所述功能性丙烯酸酯预聚物选自以下一种或几种:不饱和聚酯改性丙烯酸、聚丁二烯改性丙烯酸酯、聚异戊二烯改性丙烯酸酯。
进一步地,所述功能性丙烯酸酯单体选自以下一种或几种:双环戊二烯丙烯酸酯、双环戊二烯乙氧基丙烯酸酯、双环戊二烯甲基丙烯酸酯、双环戊二烯乙氧基甲基丙烯酸酯。
进一步地,所述量子点分散胶体还包括分散于所述分散介质中的以下一种或多种物质:光扩散粒子、光引发剂以及抗氧剂。
进一步地,所述功能性丙烯酸酯树脂的添加量为所述分散介质总质量的5%~50%。
本发明的目的之三采用如下技术方案实现:
一种发光器件,包括初始光源以及所述量子点分散胶体制备的量子点分散树脂成型体,所述初始光源与所述量子点分散树脂成型体接触或不接触设置。
进一步地,所述量子点分散树脂成型体为膜层状或管状或纤维状或透镜状或圆顶状。
具体实施方式
下面,结合具体实施方式,对本发明做进一步描述,需要说明的是,在不相冲突的前提下,以下描述的各实施例之间或各技术特征之间可以任意组合形成新的实施例。
本发明提供一种量子点分散树脂成型体,包括分散于丙烯酸酯聚合物中的量子点,所述丙烯酸酯聚合物的至少一部分重复单元中包括C=C双键,所述重复单元的聚合度n≥2。
所述量子点分散树脂成型体由量子点分散胶体交联固化形成,所述量子点分散胶体包括分散介质以及分散在所述分散介质中的量子点,所述分散介质包括:功能性丙烯酸酯树脂、非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体;所述功能性丙烯酸酯树脂选自功能性丙烯酸酯预聚物和/或功能性丙烯酸酯单体;所述功能性丙烯酸酯预聚物的分子链上除了包括烯丙基活性官能团外,还包括至少一个C=C双键;所述功能性丙烯酸酯单体的分子结构中除了包括烯丙基活性官能团外,还包括至少一个C=C双键。
在所述量子点分散胶体中添加光引发剂,然后将量子点分散胶体置于基材上,进行光固化,从而得到成型的所述量子点分散树脂成型体。
优选地,所述非功能性丙烯酸酯类单体包括单官能度丙烯酸酯和/或多官能度丙烯酸酯;所述单官能度丙烯酸酯选自以下一种或多种:(甲基)丙烯酸异冰片酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、3,3,5-三甲基环己基丙烯酸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、2-苯氧基乙基(甲基)丙烯酸酯、(甲基)四氢呋喃丙烯酸酯、(甲基)丙烯酸酯缩水甘油酯、丙烯酰吗啉、(甲基)丙烯酸-2-乙基己酯;所述多官能度丙烯酸酯选自以下一种或多种:三羟甲基丙烷三(甲基)丙烯酸酯、乙氧化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯。
所述非功能性丙烯酸酯预聚物选自聚氨酯丙烯酸酯、饱和聚酯丙烯酸酯、环氧丙烯酸酯树脂、有机硅改性丙烯酸酯中的一种或多种。
所述功能性丙烯酸酯预聚物选自以下一种或几种:不饱和聚酯改性丙烯酸、聚丁二烯改性丙烯酸酯、聚异戊二烯改性丙烯酸酯。
所述功能性丙烯酸酯单体选自以下一种或几种:双环戊二烯丙烯酸酯、双环戊二烯乙氧基丙烯酸酯、双环戊二烯甲基丙烯酸酯、双环戊二烯乙氧基甲基丙烯酸酯。
所述量子点分散树脂成型体可用于制备发光器件,将其应用于发光器件时,可以是膜层状或管状或纤维状或透镜状或圆顶状。
【实施例1】
量子点分散树脂成型体通过以下步骤制备得到:
将5质量份的量子点、30质量份的聚氨酯丙烯酸酯、50质量份的(甲基)丙烯酸异冰片酯、10质量份的三羟甲基丙烷三(甲基)丙烯酸酯、5质量份聚异戊二烯改性丙烯酸酯混合均匀;向上述混合物中加入光引发剂,然后将混合物置于基材上,进行光固化,最后得到实施例1的量子点分散树脂成型体。
【实施例2】
量子点分散树脂成型体通过以下步骤制备得到:
将5质量份的量子点、30质量份的聚酯丙烯酸酯、45质量份的(甲基)丙烯酸-2-乙基己酯、10质量份的乙氧化三羟甲基丙烷三(甲基)丙烯酸酯、10质量份聚丁二烯改性丙烯酸酯混合均匀;向上述混合物中加入光引发剂,然后将混合物置于基材上,进行光固化,最后得到实施例2的量子点分散树脂成型体。
【实施例3】
量子点分散树脂成型体通过以下步骤制备得到:
将5质量份的量子点、30质量份的环氧丙烯酸酯、30质量份的(甲基)丙烯酸缩水甘油脂、5质量份的季戊四醇三丙烯酸酯、30质量份的双环戊二烯甲基丙烯酸酯混合均匀;向上述混合物中加入光引发剂,然后将混合物置于基材上,进行光固化,最后得到实施例3的量子点分散树脂成型体。
【实施例4】
量子点分散树脂成型体通过以下步骤制备得到:
将5质量份的量子点、30质量份的有机硅丙烯酸酯、10质量份的(甲基)丙烯酸异癸酯、5质量份的三(2-羟乙基)异氰脲酸三丙烯酸酯、50质量份的双环戊二烯乙氧基甲基丙烯酸酯混合均匀;向上述混合物中加入光引发剂,然后将混合物置于基材上,进行光固化,最后得到实施例4的量子点分散树脂成型体。
【对比例1】
量子点分散树脂成型体通过以下步骤制备得到:
将5质量份的量子点、35质量份的聚氨酯丙烯酸酯、50质量份的(甲基)丙烯酸异冰片酯、10质量份的三羟甲基丙烷三(甲基)丙烯酸酯混合均匀;向上述混合物中加入光引发剂,然后将混合物置于基材上,进行光固化,最后得到对比例1的量子点分散树脂成型体。
对以上各实施例以及对比例制备得到的量子点分散树脂成型体进行发光效率的检测以及发光稳定性检测。发光效率的检测方法为:利用450nm蓝色LED灯作为背光光谱,利用积分球分别测试蓝色背光光谱和透过量子点复合材料的光谱,利用谱图的积分面积计算量子点发光效率。量子点发光效率=(红色量子点发射峰面积+绿色量子点发射峰面积)/(蓝色背光峰面积-透过量子点复合材料未被吸收的蓝色峰面积)*100%。发光稳定性通过以下方法进行评价:在高温蓝光光照(70℃,0.5W/cm2),高温高湿(65℃/95%RH)和高温储存(85℃)等老化条件下,检测量子点复合材料的效率变化和无效边大小。检测结果见表1、表2。
从表1和表2的检测结果可以看出,各实施例的量子点分散树脂成型体的量子点稳定性更好。
表1 各实施例以及对比例老化时发光效率的变化
表2 各实施例以及对比例老化时无效边的变化
上述实施方式仅为本发明的优选实施方式,不能以此来限定本发明保护的范围,本领域的技术人员在本发明的基础上所做的任何非实质性的变化及替换均属于本发明所要求保护的范围。
Claims (10)
1.一种量子点分散树脂成型体,包括分散于丙烯酸酯聚合物中的量子点,其特征在于,所述丙烯酸酯聚合物的至少一部分重复单元中包括C=C双键,所述重复单元的聚合度n≥2,所述量子点分散树脂成型体由量子点分散胶体交联固化形成,所述量子点分散胶体包括分散介质以及分散在所述分散介质中的量子点;
所述分散介质包括:功能性丙烯酸酯类物质、非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体;所述功能性丙烯酸酯类物质为功能性丙烯酸酯预聚物和功能性丙烯酸酯单体,或者所述功能性丙烯酸酯类物质为功能性丙烯酸酯单体;所述功能性丙烯酸酯预聚物的分子链上除了包括烯丙基活性官能团外,还包括至少一个C=C双键;所述功能性丙烯酸酯单体的分子结构中除了包括烯丙基活性官能团外,还包括至少一个C=C双键;
所述功能性丙烯酸酯单体选自以下一种或几种:双环戊二烯丙烯酸酯、双环戊二烯乙氧基丙烯酸酯、双环戊二烯甲基丙烯酸酯、双环戊二烯乙氧基甲基丙烯酸酯。
2.一种量子点分散胶体,包括分散介质以及分散在所述分散介质中的量子点,其特征在于,所述分散介质包括:功能性丙烯酸酯类物质、非功能性丙烯酸酯预聚物以及非功能性丙烯酸酯单体;所述功能性丙烯酸酯类物质为功能性丙烯酸酯预聚物和功能性丙烯酸酯单体,或者所述功能性丙烯酸酯类物质为功能性丙烯酸酯单体;所述功能性丙烯酸酯预聚物的分子链上除了包括烯丙基活性官能团外,还包括至少一个C=C双键;所述功能性丙烯酸酯单体的分子结构中除了包括烯丙基活性官能团外,还包括至少一个C=C双键。
3.根据权利要求2所述的量子点分散胶体,其特征在于,所述非功能性丙烯酸酯类单体包括单官能度丙烯酸酯和/或多官能度丙烯酸酯;
所述单官能度丙烯酸酯选自以下一种或多种:(甲基)丙烯酸异冰片酯、(甲基)丙烯酸甲酯、(甲基)丙烯酸乙酯、(甲基)丙烯酸正丁酯、(甲基)丙烯酸环己酯、(甲基)丙烯酸异辛酯、(甲基)丙烯酸异癸酯、(甲基)丙烯酸月桂酯、3,3,5-三甲基环己基丙烯酸酯、(甲基)丙烯酸羟乙酯、(甲基)丙烯酸羟丙酯、2-苯氧基乙基(甲基)丙烯酸酯、(甲基)四氢呋喃丙烯酸酯、(甲基)丙烯酸酯缩水甘油酯、(甲基)丙烯酸-2-乙基己酯;
所述多官能度丙烯酸酯选自以下一种或多种:三羟甲基丙烷三(甲基)丙烯酸酯、乙氧化三羟甲基丙烷三(甲基)丙烯酸酯、丙氧化三羟甲基丙烷三丙烯酸酯、1,3-丁二醇二丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、二丙二醇二丙烯酸酯、三丙二醇二丙烯酸酯、新戊二醇二丙烯酸酯、聚乙二醇二丙烯酸酯、三环癸烷二甲醇二丙烯酸酯、季戊四醇三丙烯酸酯、三(2-羟乙基)异氰脲酸三丙烯酸酯、季戊四醇四丙烯酸酯、二季戊四醇六丙烯酸酯。
4.根据权利要求2所述的量子点分散胶体,其特征在于,所述非功能性丙烯酸酯预聚物选自聚氨酯丙烯酸酯、聚酯丙烯酸酯、环氧丙烯酸酯树脂、有机硅改性丙烯酸酯中的一种或多种。
5.根据权利要求2所述的量子点分散胶体,其特征在于,所述功能性丙烯酸酯预聚物选自以下一种或几种:不饱和聚酯改性丙烯酸、聚丁二烯改性丙烯酸酯、聚异戊二烯改性丙烯酸酯。
6.根据权利要求2所述的量子点分散胶体,其特征在于,所述功能性丙烯酸酯单体选自以下一种或几种:双环戊二烯丙烯酸酯、双环戊二烯乙氧基丙烯酸酯、双环戊二烯甲基丙烯酸酯、双环戊二烯乙氧基甲基丙烯酸酯。
7.根据权利要求2-6任一所述的量子点分散胶体,其特征在于,还包括分散于所述分散介质中的以下一种或多种物质:光扩散粒子、光引发剂以及抗氧剂。
8.根据权利要求2-6任一所述的量子点分散胶体,其特征在于,所述功能性丙烯酸酯类物质的添加量为所述分散介质总质量的5%~50%。
9.一种发光器件,包括初始光源,其特征在于,还包括由权利要求2-8任一所述的量子点分散胶体制备的量子点分散树脂成型体,所述初始光源与所述量子点分散树脂成型体接触或不接触设置。
10.根据权利要求9所述的发光器件,其特征在于,所述量子点分散树脂成型体为膜层状或管状或纤维状或透镜状或圆顶状。
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CN105425540B (zh) * | 2016-01-04 | 2019-11-05 | 京东方科技集团股份有限公司 | 量子点膜及其制备方法、量子点膜的图案化方法及显示器 |
CN108864384B (zh) * | 2018-05-08 | 2020-09-15 | 纳晶科技股份有限公司 | 量子点分散树脂成型体、量子点分散胶体以及发光器件 |
CN109251717A (zh) * | 2018-08-16 | 2019-01-22 | 纳晶科技股份有限公司 | 胶水组合物、量子点组合物、复合材料及其应用 |
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