CN114889268B - 一种量子点光扩散板材及其制备方法和应用 - Google Patents

一种量子点光扩散板材及其制备方法和应用 Download PDF

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CN114889268B
CN114889268B CN202210260127.1A CN202210260127A CN114889268B CN 114889268 B CN114889268 B CN 114889268B CN 202210260127 A CN202210260127 A CN 202210260127A CN 114889268 B CN114889268 B CN 114889268B
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light diffusion
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杨金山
陈平绪
叶南飚
付锦锋
王林
刘学亮
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Chengdu Kingfa Sci & Tech Advanced Materials Co ltd
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Abstract

本发明提供一种量子点光扩散板材及其制备方法和应用。本发明的量子点光扩散板材,以添加了光扩散剂母粒和量子点母粒的聚苯乙烯(GPPS)为光扩散层,在光扩散层的上下表面各复合一层保护层,该保护层为经SMA树脂和EAA树脂共混改性的PMMA树脂层,能够有效改善PMMA树脂层与GPPS层这两种不同材质层的层间结合力,进而显著提高材料的使用寿命。其中,本发明的量子点光扩散板材的总透光率在40%以上,可高达60%;雾度>85%,可高达97%;表面硬度等级可达到2H等级;在辐照600h后,光老化色差值达到△E≤1.5水平,可低至0.5。

Description

一种量子点光扩散板材及其制备方法和应用
技术领域
本发明属于光扩散材料技术领域,具体设计一种量子点光扩散板材及其制备方法和应用。
背景技术
光扩散材料是能够使光通过而又能有效扩散光的材料,它能将点、线光源转化成线、面光源,散射角大,导光性好,透光均匀。因而广泛应用在液晶显示与LED照明及成像显示系统中。它的主要功能是使入射光充分散射,实现更柔和、均匀的照射效果。
光扩散材料一般以透明树脂为基体,通过添加一定比例的光扩散剂和其他助剂而制成。常用的透明基材有聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)、聚苯乙烯(GPPS)和聚丙烯(PP)等。聚苯乙烯由于具有良好的刚性、尺寸稳定性、高透光率、低雾度及成本较低等优点,越来越多背光显示装置及LED灯管罩采用聚苯乙烯基光扩散材料制备。
目前制备聚苯乙烯基光扩散材料常采用聚苯乙烯树脂添加合适比例的光扩散剂共混挤出造粒。光扩散剂多采用具有球形结构的有机硅、交联的PMMA微球、聚苯乙烯微球等有机聚合物粒子。虽然添加这些光扩散剂能较好的实现较高的透光率同时能有效扩散光,但是整体成本较高、制备工艺复杂,尤其是微球结构的光扩散剂。且聚苯乙烯(GPPS)光扩散板的缺点也是显而易见的,比如透明度较差,表面耐划伤性能较差,耐候性较差,易黄变,耐溶剂能也较差。
随着产品的升级,对光扩散板材的性能也有了更高的要求,例如随着量子点显示技术的发展与进步,量子点光扩散材料近年来有了进步,并开始有产品问世,如电视背板量子点薄膜。有别于传统液晶显示的是,量子点显示以蓝光LED为光源,量子点薄膜在蓝光激发下会激发出纯正的绿光和红光,进而混合蓝光形成高质量的白光,这种特殊的纳米技术实现了显示器的高色域覆盖,还原了色彩。
通过将量子点添加到GPPS树脂中可以制备得到量子点光扩散板材,在聚苯乙烯光扩散板上下表面各复合一层保护涂层,虽然能够提高光扩散板的性能,但是保护层与光扩散板材的层间结合力较差,是影响其广泛使用的重要影响因素。
因此,需要开发一种力学性能和光扩散性能均较好的量子点光扩散板材。
发明内容
本发明的目的在于,为了克服现有的量子点光扩散板材在使用过程中容易分层的缺陷,同时为了进一步提高量子点光扩散板材的光扩散性能和力学强度,提供一种力学性能和光扩散性能均较好的量子点光扩散板材。
本发明的另一目的在于,提供所述量子点光扩散板材的制备方法。
本发明的另一目的在于,提供所述量子点光扩散板材在成像显示领域中的应用。
为实现上述目的,本发明采用如下技术方案:
一种量子点光扩散板材,包括GPPS量子点光扩散芯层和位于GPPS量子点光扩散芯层上下表面的PMMA保护层;
其中,所述PMMA保护层包括按照如下重量分计算的组分:
本发明的量子点光扩散板材,以添加了光扩散剂母粒和光量子点母粒的聚苯乙烯(GPPS)为光扩散层,在光扩散层的上下表面各复合一层保护层,该保护层为经SMA(苯乙烯马来酸酐共聚物)树脂和EAA(乙烯丙烯酸共聚物)树脂共混改性的PMMA树脂层。
PMMA树脂本身具有较好的透光性能和较高的表面硬度,在保护聚苯乙烯光扩散板材的同时,不影响光扩散板材的光扩散性(透光率和雾度),还可以通过添加耐候剂等助剂,提高材料的耐候性能。但是研究发现,由于PMMA树脂具有较高的表面硬度,其与GPPS光扩散层的粘合性能较差,尤其是添加量子点以后,表面极性进一步下降,如选用常规的粘合剂,则会影响板材的光扩散性能,尤其是透光率。本发明的发明人通过大量试验研究发现,如在PMMA保护层中添加的SMA树脂和EAA树脂进行共混改性,可以在不影响PMMA树脂的硬度和透光率的基础上,能够有效改善PMMA树脂层与GPPS层这两种不同材质层的层间结合力,进而显著提高材料的使用寿命。
常规的GPPS量子点光扩散芯层均可用于本发明中,所述GPPS量子点光扩散芯层包括按照如下重量分计算的组份:
需要说明的是,常规市售的中高粘度GPPS树脂均可用于本发明中,可选地,所述GPPS树脂在200℃、5kg条件下的熔体流动速率≤5g/10min。较高的熔体粘度有利于光扩散剂母粒及量子点母粒更好地分散在GPPS树脂基体中。所述GPPS树脂在200℃、5kg条件下的熔体流动速率在2.0~3.0g/10min范围内,得到的板材的性能较好。
优选地,所述PMMA树脂在230℃、3.16kg载荷下的熔体流动速率为2~10g/10min。
本发明中,GPPS树脂和PMMA树脂的熔体流动速率按照ISO 1133-1:2011标准方法检测得到。
可选地,所述光扩散剂为有机硅光扩散剂或无机光扩散剂中的一种或几种的组合。
常规的量子点均可用于本发明中,可选地,所述量子点为Cd系量子点或ZnSe/ZnS量子点中的一种或几种的组合。
现有市售的常规MA(马来酸酐)含量的SMA树脂均可用于本发明中,现有市售的SMA树脂中MA的重量含量为15~30%。
现有市售的常规AA(丙烯酸)含量的EAA树脂均可用于本发明中,优选地,EAA树脂中AA的重量含量一般为8~25%,进一步优选为18~20%。
可选地,所述耐候剂为紫外线吸收剂和/或光稳定剂。
优选地,所述耐候剂为紫外线吸收剂和光稳定剂按照1:1~1.5组成的混合物。
优选地,所述紫外线吸收剂为苯并三唑类紫外线吸收剂,包括但不限于2-(2'-羟基-5'-甲基苯基)苯并三唑(UV-P)或2-(2′-羟基-3′,5′-二叔丁基苯基)-5-氯苯并三唑(UV-327)中的一种或几种的组合。
优选地,所述光稳定剂为受阻胺类光稳定剂(HALS),包括但不限于HALS 944、HALS770DF中的一种或几种的组合。
优选地,所述量子点光扩散板材中,GPPS量子点光扩散芯层和PMMA保护层(指的是单面表层的保护层,即上表层或下表层)的厚度比为1:0.05~0.15。
本发明的光扩散板材的厚度可以为1.0~2.0mm。
优选地,GPPS量子点光扩散芯层和PMMA保护层中所述的其它添加剂独立地选自润滑剂、抗氧剂或着色剂中的一种或几种的组合。
优选地,所述PMMA保护层包括按照如下重量份计算的组分:
所述量子点光扩散板材的制备方法,包括如下步骤:
将所述GPPS量子点光扩散芯层的各组分原料和所述PMMA保护层的各组分原料分别混合均匀后,从不同的加料口加入到共挤挤出机中,经熔融挤出后,得到所述量子点光扩散板材。
需要说明的是,为了进一步提高材料的性能,我们在制备过程中,一般会将光扩散剂和量子点分别与基体树脂(例如GPPS)制备成母粒,以提高光扩散剂和量子点在基体树脂中的分散性能。
优选地,光扩散母粒中光扩散剂的重量含量为2~10%;量子点母粒中量子点的重量含量为2~10%。
优选地,所述混合在高速混合机中进行,所述高速混合机的转速为500~800rpm。
优选地,所述挤出机为三层共挤挤出机。需要说明的是,所述量子点光扩散板材中,各层的厚度比可以通过控制挤出机的螺杆转速比,板材的厚度可通过牵引辊的牵引速度进行调控。
优选地,挤出的温度(螺杆温度)为80~220℃,具体从加料口到机头依次设为:一区温度80~100℃、二区温度180~200℃、三区温度200~220℃、四区温度200~220℃、换网器温度200~220℃、过渡区温度200~220℃、模头温度200~220℃。
上述量子点光扩散板材在成像显示领域中的应用也在本发明的保护范围之内,具体可用于制备液晶显示屏背板或LED照明灯的灯罩及面板。
与现有技术相比,本发明的有益效果是:
本发明的量子点光扩散板材,以添加了光扩散剂母粒和量子点母粒的聚苯乙烯(GPPS)为光扩散层,在光扩散层的上下表面各复合一层保护层,该保护层为经SMA树脂和EAA树脂共混改性的PMMA树脂层,能够有效改善PMMA树脂层与GPPS层这两种不同材质层的层间结合力,进而显著提高材料的使用寿命。其中,本发明的量子点光扩散板材的总透光率在40%以上,可高达60%;雾度>85%,可高达97%;表面硬度等级可达到2H等级;在辐照600h后,光老化色差值达到△E≤1.5水平,可低至0.5。
附图说明
图1为本发明的量子点光扩散板材的结构示意图。
具体实施方式
以下结合具体实施例和附图来进一步说明本发明,但实施例并不对本发明做任何形式的限定。除非特别说明,本发明采用的试剂、方法和设备为本技术领域常规试剂、方法和设备。除非特别说明,本发明所用试剂和材料均为市购。
本发明的实施例采用以下原料:
聚苯乙烯(GPPS):
1#:GPPS-1050,200℃、5kg载荷下的熔体流动速率为2.0g/10min,购自佛山道达尔;
2#:GPPS-500N,200℃、5kg载荷下的熔体流动速率为3.0g/10min,购自独山子石化;
3#:GPPS WD-500E,200℃、5kg载荷下的熔体流动速率为5.0g/10min,购自上海赛科;
光扩散剂:
1#:有机硅光扩散剂,KMP-590,购自日本信越;
2#:二氧化硅,HDK H2000,购自德国瓦克;
量子点:
1#:CdSe/ZnS量子点,OA-21158-25,购自星紫(上海)新材料;
2#:InP/ZnS量子点,OA-26158-25,购自星紫(上海)新材料;
PMMA树脂:
1#:PMMA 205,230℃、3.16kg载荷下的熔体流动速率为2.5g/10min,购自镇江奇美;
2#:PMMA 207,230℃、3.16kg载荷下的熔体流动速率为8.0g/10min,购自镇江奇美;
SMA树脂:
SMA-1:SZ10010,MA重量含量为25%,购自荷兰POLYSCOPE;
SMA-2:SMA-700,MA重量含量为18%,购自上海华雯;
EAA树脂:
EAA-1:5990I,AA重量含量为20%,购自美国陶氏化学;
EAA-2:3004,AA重量含量为9.7%,购自美国陶氏化学;
EAA-3:U00563,AA重量含量为18wt%,购自美国PLASTICS;
EMA树脂:AC1330,购自美国杜邦;
耐候剂:
1#-紫外线吸收剂UV-P:市售;
2#-光稳定剂HALS 770DF:市售;
其它添加剂:
润滑剂:硬脂酸钙,市售;
需要说明的是,本发明中,各实施例和对比例中使用的耐候剂和其它添加剂相同。
实施例1~14
本实施例提供一系列量子点光扩散板材,按照表1~2中的配方,按照包括如下步骤的制备方法制备得到:
S1.光扩散母粒的制备
将光扩散剂和部分GPPS树脂按照重量比为1:9的比例,在高速混合机中混合均匀后,加入双螺杆挤出机中,在180~210℃下经熔融挤出制备得到;
S2.量子点母粒的制备
将量子点和部分GPPS树脂按照重量比为1:9的比例,在高速混合机中混合均匀后,加入双螺杆挤出机中,在180~210℃下经熔融挤出制备得到;
S3.量子点光扩散板材的制备
按照表1~2中所示的配方,将GPPS量子点光扩散芯层的各组分原料(GPPS树脂、S1.得到的光扩散剂母粒、S2.得到的量子点母粒)在高速混合机中混合均匀后,加入到三层共挤挤出机的主机加料口;PMMA保护层的各组分原料在高速混合机中混合均匀后,加入到三层共挤挤出机的辅机加料口;上述原料分别经过各单螺杆挤出机熔融塑化(其中,挤出的温度(螺杆温度)为80~220℃,具体从加料口到机头依次设为:一区温度80~100℃、二区温度180~200℃、三区温度200~220℃、四区温度200~220℃、换网器温度200~220℃、过渡区温度200~220℃、模头温度200~220℃),然后从T型口模中挤出成片状物,该挤出的片状物用多个冷却辊冷却,经牵引辊牵引、切割后得到所述量子点光扩散板材(示意图如图1所示)。
表1实施例1~7的量子点光扩散板材中各组分含量(重量份)
注:本发明的各实施例中,默认上/下保护层的厚度相同。
表2实施例8~14的量子点光扩散板材中各组分含量(重量份)
注:本发明的各实施例中,默认上/下保护层的厚度相同。
对比例1
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,未添加SMA树脂和EAA树脂。
对比例2
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,SMA树脂的添加量替换为13份。
对比例3
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,将SMA树脂和EAA树脂替换为EMA。
对比例4
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,将PMMA保护层中的SMA树脂和EAA树脂替换添加到GPPS量子点光扩散芯层材料中。
对比例5
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,将PMMA保护层中的EAA树脂替换为SMA树脂(即,未添加EAA树脂)。
对比例6
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,将PMMA保护层中的SMA树脂替换为EAA树脂(即,未添加SMA树脂)。
对比例7
本对比例提供一种量子点光扩散板材,配方与实施例2的不同之处在于,EAA树脂的添加量替换为1.5份。
性能测试
对上述实施例和对比例制备得到的量子点光扩散板材裁切成100mm×100mm的方形板材样品,对其性能进行测试,具体测试项目及测试方法如下:
1.光扩散性能测试:
按照GB/T2410-2008标准对样品的透光率进行测试;使用雾度计按照ASTM D1003-2013标准测试样品的雾度。
2.表面硬度:使用铅笔硬度计并根据国家标准GB/T 6739-1996进行测试得到。
3.耐光老化性能:采用ISO 4892.2-2013的标准进行试验,测试条件:0.51W/m2,其中102min干燥,18min喷淋,连续辐照30个周期,共计600小时;
另外,本发明还对在上述模拟环境下模拟600h后的光扩散板材的透光率进行了测试。
测试结果详见表5:
表5性能测试结果
由上述结果可以看出:
本发明的各实施例制备得到的多层(三层)共挤量子点光扩散板材,具有良好的光学性能、较高的表面硬度和耐光老化性能,具体地:光扩散板材的透光率在40%以上,可高达60%;雾度>85%,可高达97%;表面硬度等级可达到2H等级;在辐照600h后,光老化色差值达到△E≤1.5水平,可低至0.5。同时还具有较长的使用时间,能够在600h氙灯老化模拟测试后,透光率的保持率均在90%以上,可高达98.3%。
实施例2、实施例4~5的结果表明,本发明选择的熔体流动速率范围内的GPPS树脂基体均可用于本发明中,且制备得到的光扩散板材的光扩散性能(透光率和雾度)较好,但低熔体流动速率(高粘度)基材的表现要更优。
实施例2、实施例6的结果表明,普通光扩散母粒均可用于本发明,但无机光扩散母粒的透光性能较差,但是在少量添加量的情况下,透光率可达到40%。
实施例2、实施例7的结果表明,普通量子点均可用于本发明,且制备得到的量子点光扩散板材的性能较好,能够满足基本使用要求。
实施例2、实施例8~9的结果表明,常规的PMMA树脂、SMA树脂均可用于本发明中,且制备得到的光扩散板材具有良好的光扩散性能(透光率和雾度)。
实施例2、实施例10的结果表明,其它添加剂的添加与否对制备得到的光扩散板材的性能的影响较小。
实施例2、实施例11~12的结果表明,保护层表层与芯层的厚度比在本发明的范围内,对制备得到的光扩散板材的性能的影响较小。
实施例2、实施例13~14的结果表明,EAA树脂中,随着EAA树脂中AA含量的增加,得到的板材的初始透光率和雾度呈现上升趋势,且逐渐趋于平缓。表明合适AA含量的EAA树脂能够使得板材的性能得到提升。
实施例2、对比例1~2、对比例5~7的结果表明,在保护层中添加合适量的SMA树脂和EAA树脂,可以在不影响材料光扩散性能的前提下,起到增强层间粘合力的作用;对比例1未添加SMA树脂和EAA树脂、对比例5和6分别单独添加了SMA树脂和EAA树脂,得到的量子点光扩散板材的层间增粘效果并不好,造成老化后透光率显著下降;对比例2添加了较大量的SMA树脂、对比例7添加了大量的EAA树脂,制备得到的量子点光扩散板材的整体光扩散性能以及硬度显著下降。
对比例3添加了常规的层间粘合剂,但是会显著影响光扩散板的透光率保持率和雾度以及耐候性能;对比例4将SMA树脂和EAA树脂添加到GPPS量子点光扩散芯层中,SMA树脂也有起到增强层间粘合力的作用,但是会显著影响光扩散板的透光保持率。
上述结果表明,只有将合适添加量的SMA树脂和EAA树脂添加到PMMA保护层中时,才会起到增强层间粘合力的作用。
以上所述的具体实施方式,对本发明的目的、技术方案和有益效果进行了进一步详细说明,所应理解的是,以上所述仅为本发明的具体实施方式而已,并不用于限定本发明的保护范围,凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。

Claims (10)

1.一种量子点光扩散板材,其特征在于,包括GPPS量子点光扩散芯层和位于GPPS量子点光扩散芯层上下表面的PMMA保护层;
其中,所述PMMA保护层包括按照如下重量份计算的组分:
2.根据权利要求1所述量子点光扩散板材,其特征在于,所述GPPS量子点光扩散芯层包括按照如下重量份计算的组分:
3.根据权利要求2所述量子点光扩散板材,其特征在于,所述GPPS树脂在200℃、5kg条件下的熔体质量流动速率≤5g/10min。
4.根据权利要求3所述量子点光扩散板材,其特征在于,所述GPPS树脂在200℃、5kg条件下的熔体质量流动速率为2.0~3.0g/10min。
5.根据权利要求2所述量子点光扩散板材,其特征在于,所述光扩散剂为有机硅光扩散剂或无机光扩散剂中的一种或几种的组合。
6.根据权利要求1所述量子点光扩散板材,其特征在于,PMMA保护层中所述耐候剂为紫外线吸收剂和/或光稳定剂。
7.根据权利要求1所述量子点光扩散板材,其特征在于,GPPS量子点光扩散芯层和PMMA保护层单面的厚度比为1:0.05~0.15。
8.根据权利要求1所述量子点光扩散板材,其特征在于,所述EAA树脂中,AA的重量含量为8~25%。
9.权利要求1~8任一项所述量子点光扩散板材的制备方法,其特征在于,包括如下步骤:
将所述GPPS量子点光扩散芯层的各组分原料和所述PMMA保护层的各组分原料分别混合均匀后,从不同的加料口加入到共挤挤出机中,经熔融挤出后,得到所述量子点光扩散板材。
10.权利要求1~8任一项所述量子点光扩散板材在成像显示领域中的应用。
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