CN104046368B - 一种液晶薄膜及其制备方法和温度响应器件、圆偏振片 - Google Patents
一种液晶薄膜及其制备方法和温度响应器件、圆偏振片 Download PDFInfo
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Abstract
本发明涉及一种液晶薄膜,由胆甾相液晶与氢键自组装类手性材料混合形成复合体系,再经紫外光辐照聚合而得到的。本发明还涉及所述液晶薄膜的制备方法及具体应用。本发明所述液晶薄膜,其原料来源广泛并且成本低廉,制备工艺简便,降低了对紫外光强度控制的要求,可以大面积生产。所得液晶薄膜具有高的反射率与透过率,宽的反射区域。
Description
技术领域
本发明涉及一种液晶薄膜及其制备方法和温度响应器件、圆偏振片,属于液晶显示技术领域。
背景技术
通过在向列相液晶中掺入手性添加剂可以得到胆甾相液晶。在胆甾相液晶中,液晶分子的长轴围绕以螺旋轴做周期性旋转,形成螺旋结构。液晶分子长轴旋转360度所经过的距离被称为螺距P,P的大小与液晶中手性添加剂的含量成反比。胆甾相液晶由于这种特殊的螺旋结构而具有选择性布拉格反射的光学特性。单一螺距的胆甾相液晶可反射入射光的反射波宽Δλ=ΔnP,其中Δn为液晶材料的双折射率。在反射波宽范围内,与胆甾相液晶螺旋结构相同的光被反射,与胆甾相液晶螺距结构相反的光被透射;而在反射波宽范围外,两种旋相的光均被透过。因此,胆甾相液晶可广泛应用于无光损失的反射式偏振片、液晶显示器光增强膜、红外光屏蔽薄膜材料等领域。
在可见光范围内,单一螺距的胆甾相液晶的反射波宽通常在150nm以下。研究证明,形成螺距的梯度分布或非均匀分布可以非常有效地拓宽胆甾相液晶的反射波宽。陈钰雯等人(CN1549036A)利用在电极上产生非均匀电场的方法,使接近电极的液晶螺距增大,而远离电极的液晶螺距基本不变,从而使反射带宽增大。此种方法的不足之处在于需要在反射膜中引入特殊形状的电极对其光学性能产生影响,而且此种电极也难于加工。
另外,高分子稳定液晶即通过分散在液晶中的交联高分子网络来稳定和固定液晶分子指向矢的排列,从而得到理想的液晶分子宏观取向分布,是一种获得胆甾相液晶螺距特殊分布的常用手段。D.J.Broer等人(CN1198819A)使用可光聚合的复合材料体系(包括可光聚合胆甾醇丙烯酸酯,可光聚合向列相丙烯酸酯,染料等),利用非常弱的紫外线(辐射强度小于0.05mW/cm2)进行照射,使单体有充分的时间进行扩散,形成螺距梯度,从而得到对于整个可见光波段的选择性反射的偏振片。由于单体在液晶中的扩散程度与紫外强度有关,因此这种方法所形成的带宽对于紫外照射强度十分敏感,在制造过程中要使用单色光传感器对偏振片进行检测,一旦达到所需带宽,就要立刻提高紫外照射强度,可见该方法所需设备较为复杂,工艺较难控制。
发明内容
为了克服上述技术缺陷,本发明提供一种液晶薄膜及其制备方法和温度响应器件、圆偏振片。所述液晶薄膜具有高的反射率和透过率,制备工艺简便,成本低廉,适合推广利用。
为了实现上述目的,本发明采用如下技术方案:
一种液晶薄膜,由胆甾相液晶与氢键自组装类手性材料混合形成复合体系,经紫外光辐照聚合而得到的。
其中,所述胆甾相液晶由如下重量份的组分制得:手性液晶性可聚合单体5-20份,小分子向列相液晶65-90份,手性添加剂5-15份,光引发剂0.5-5份。
所述手性液晶性可聚合单体优选如下化合物中的一种或两种以上:
所述小分子向列相液晶为向列相温度在低温-50-0℃,高温65-150℃区间内的向列相液晶混合物。本发明所述小分子向列相液晶均为市售产品,优选SLC1717。
所述手性添加剂优选如下化合物中的一种或两种以上:
所述光引发剂优选为Irgacure651,其结构式为:
本发明所述的胆甾相液晶可采用本领域常规方法按上述比例均匀混合制备而得,优选溶剂挥发法或者加热熔融法。
所述氢键自组装类手性材料包括氢键的受体和给体,氢键的给体和受体可以是具有相同旋向的手性材料,也可以是具有不同旋向的手性材料,还可以是给体(受体)为手性材料,受体(给体)为无手性材料。
在本发明中,所述氢键的给体优选如下化合物中的一种或两种以上:
所述氢键的受体优选如下化合物中的一种或两种以上:
所述氢键的给体与受体的摩尔比1:(1.2-2.2)。
在本发明中,所述胆甾相液晶与氢键自组装类手性材料的质量比为(4-20):1。
本发明所述液晶薄膜的反射波宽可根据氢键自主装类手性材料种类和含量进行任意调节,优选反射波宽为300nm-2200nm,更优选350-750nm。
本发明中,复合体系在室温下具有均一螺距P1,在高温下具有均一螺距P2。利用氢键自组装类手性材料在氢键断裂前后螺旋扭曲力不同,从而导致体系中螺距不同,并由紫外光辐照固定氢键断裂时的螺距(P1或P2)。由于距离聚合物网络的位置远近不同,聚合物网络对氢键分子的锚定作用也不同,在靠近聚合物网络较近处,锚定作用强,氢键分子难以进行自组装,这一区域的螺距变化小;在距离聚合物网络较远处,锚定作用弱,氢键分子易于进行自组装,这一区域的螺距变化大,从而使体系内呈现非均匀分布的螺距。
本发明所述液晶薄膜为在高温条件下具有宽波反射特性的液晶薄膜或在室温条件下具有宽波反射特性的液晶薄膜。
本发明还提供上述液晶薄膜的制备方法,将胆甾相液晶与氢键自组装类手性材料混合形成复合体系,经波长为365nm,光强为0.001-100mW/cm2的紫外光辐照5-240min而得;优选紫外辐照条件为光强1.2-3.3mW/cm2,时间18-30min,更优选光强1.2mW/cm2,时间30min。
在上述制备方法中,所述紫外光辐照可以在室温或氢键断裂温度条件下进行。
其中,所述复合体系在室温条件下经紫外光辐照时,螺距P1固定,再将复合体系加热至氢键断裂温度,氢键断裂,由于氢键分子与聚合物网络远近不同,从而得到在高温条件下具有宽波反射特性的液晶薄膜。
本发明还提供一种温度响应智能器件,其含有上述在高温条件下具有宽波反射特性的液晶薄膜。当所述智能器件只反射单一螺距的光时,代表环境温度未超过氢键断裂温度;当所述智能器件能够实现宽波反射时,代表环境温度已超过氢键断裂温度。
或者,所述复合体系先加热至氢键断裂温度条件下经紫外光辐照,固定螺距P2,再将复合体系降温至室温,氢键自组装,由于氢键分子与聚合物网络远近不同。从而形成在室温条件下具有宽波反射特性的液晶薄膜。
本发明还提供一种圆偏振片,其是由上述在室温条件下具有宽波反射特性的液晶薄膜制得。所述圆偏振片可作为无光损失的反射式圆偏振片、液晶显示器中光增亮膜等液晶元件。
本发明所述液晶薄膜,其原料来源广泛并且成本低廉,制备工艺简便,降低了对紫外光强度控制的要求,可以大面积生产。所得液晶薄膜具有高的反射率与透过率,宽的反射区域。
附图说明
图1为本发明液晶薄膜制备的流程示意图。
图2为实施例1中所用复合体系的变温红外测试。
图3为实施例1中所制备的液晶薄膜的反射波谱图。
图4为实施例4中所制备的液晶薄膜的反射波谱图。
具体实施方式
以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例1室温下具有宽波反射特性的液晶薄膜的制备
1)胆甾相液晶的制备:将手性液晶性可聚合单体Ch1(0.0632g)、小分子向列相液晶SLC1717(0.1174g)、手性添加剂5CBB(0.0296g)、手性添加剂ZLI-4572(0.012g)和光引发剂Irg651(Irgacure651)(0.001g)充分混合均匀,采用溶剂挥发法制备而得;
2)将氢键的受体CBS(0.01442g)和氢键的给体CHG(0.02558g)加入步骤1)所得胆甾相液晶中形成复合体系,其在室温下具有P1螺距;
步骤1)、步骤2)所述组分如下:
3)对复合体系进行变温红外测试如图2所示,确定复合体系中氢键断裂温度220℃(T1);对复合体系进行变温的紫外/可见/近红外分光光度计测试,确定复合体系在氢键断裂前后的螺距(P1,P2);如图1中(1)、(2)所示。
4)氢键断裂温度下聚合
将复合体系灌入液晶盒中,置于热台上,控制热台温度为上述氢键断裂温度T1,并使用UV光辐照,所述辐照强度为365nm,1.2mW/cm2;辐照时间30min;使复合体系中液晶性可聚合单体聚合形成聚合物网络,从而固定复合体系的螺距P2;如图1中(3)所示。
5)将液晶盒降温到室温,如图1中(4)所示。在靠近聚合物网络近的一侧,锚定作用强,氢键分子难以进行自组装,这一区域的螺距变化小,倾向为P2;在靠近聚合物网络近的一侧,锚定作用弱,氢键分子易于进行自组装,降低到室温后,这一区域的螺距变化大,倾向为P1,从而形成了螺距在P1和P2之间的非均匀分布,得到室温条件下具有反射波宽为400nm-800nm的液晶薄膜。所得液晶薄膜的反射波谱如图3所示。
实施例2室温下具有宽波反射特性的液晶薄膜的制备
按照实施例1的方法制备室温下具有宽波反射特性的液晶薄膜。区别在于:步骤1)中,胆甾相液晶由如下组分制得:手性液晶性可聚合单体Ch1(0.0562g),小分子向列相液晶SLC1717(0.1286g)、手性添加剂CB15(0.005g)、手性添加剂ZLI-4571(0.007g)和光引发剂Irg651(0.0015g)。
步骤2)中,氢键的受体CBS(0.01084g)和氢键的给体YXG(0.00916g)。
步骤3)中,氢键断裂温度200℃;
步骤4)中,所述辐照强度为365nm,2mW/cm2;辐照时间25min;将液晶盒降温到室温,得到室温条件下具有反射波宽为400nm-550nm的液晶薄膜。
实施例3室温下具有宽波反射特性的液晶薄膜的制备
按照实施例1的方法制备室温下具有宽波反射特性的液晶薄膜。区别在于:步骤1)中,胆甾相液晶由如下组分制得:手性液晶性可聚合单体Ch1(0.0362g),小分子向列相液晶SLC1717(0.0592g)、手性添加剂5CBB(0.0148g)、手性添加剂ZLI-4572(0.006g)和光引发剂Irg651(0.0015g)。
步骤2)中,氢键的受体BTS(0.007874g)和氢键的给体YXG(0.012126g)。
步骤3)中,氢键断裂温度240℃;
步骤4)中,所述辐照强度为365nm,3.3mW/cm2;辐照时间18min;将液晶盒降温到室温,得到室温条件下具有反射波宽为900nm-1200nm的液晶薄膜。
实施例4室温下具有宽波反射特性的液晶薄膜的制备
按照实施例1的方法制备室温下具有宽波反射特性的液晶薄膜。区别在于:步骤1)中,胆甾相液晶由如下组分制得:手性液晶性可聚合单体Ch1(0.0362g),小分子向列相液晶SLC1717(0.0592g)、手性添加剂5CBB(0.0148g)、手性添加剂ZLI-4572(0.006g)和光引发剂Irg651(0.0015g)。
步骤2)中,氢键的受体WJHS(0.005174g)和氢键的给体YXG(0.012126g)。
步骤3)中,氢键断裂温度190℃;
步骤4)中,所述辐照强度为365nm,3.3mW/cm2;辐照时间18min;
将液晶盒降温到室温,得到室温条件下具有反射波宽为800nm-1000nm的液晶薄膜。
将实施例1-4得到的液晶薄膜按照本领域常规方法制成圆偏振片,可作为无光损失的反射式圆偏振片。
实施例5高温下具有宽波反射特性的液晶薄膜的制备
1)胆甾相液晶的制备:将手性液晶性可聚合单体Ch2(0.0425g)、小分子向列相液晶SLC1717(0.1254g)、手性添加剂5CBB(0.0316g)、手性添加剂ZLI-4572(0.012g)和光引发剂Irg651(0.001g)充分混合均匀,采用加热熔融法制备而得;
2)将氢键的受体BTS(0.0071g)和氢键的给体CHG(0.0229g)加入胆甾相液晶中,形成复合体系;
步骤1)、步骤2)所述组分如下:
3)对复合体系进行变温红外测试,确定复合体系中氢键断裂温度250℃(T1);对复合体系进行变温的紫外/可见/近红外分光光度计测试,确定复合体系在氢键断裂前后的螺距(P1,P2);
4)复合体系在室温条件下经紫外光辐照,所述辐照强度为365nm,1.2mW/cm2;辐照时间30min,固定螺距P1;
5)再将复合体系加热至氢键断裂温度,氢键断裂,由于氢键分子与聚合物网络远近不同,从而得到在高温条件下反射波宽300nm-1000nm的液晶薄膜,所得液晶薄膜的反射波谱如图4所示。
实施例6高温下具有宽波反射特性的液晶薄膜的制备
按照实施例5的方法制备高温下具有宽波反射特性的液晶薄膜。区别在于:手性液晶性可聚合单体Ch2(0.0635g)、小分子向列相液晶SLC1717(0.2411g)、手性添加剂S811(0.0305g)和光引发剂Irg651(0.002g)充分混合均匀,采用加热熔融法制备而得;
步骤2)中,氢键的受体BTS(0.0071g)和氢键的给体CHG(0.0229g);
步骤3)中,氢键断裂温度250℃;
步骤4)中,所述辐照强度为365nm,2.2mW/cm2;辐照时间20min;
将液晶盒降温到室温,得到室温条件下具有反射波宽为800nm-1000nm的液晶薄膜。
实施例7高温下具有宽波反射特性的液晶薄膜的制备
按照实施例5的方法制备高温下具有宽波反射特性的液晶薄膜。区别在于:手性液晶性可聚合单体Ch2(0.0635g)、小分子向列相液晶SLC1717(0.2411g)、手性添加剂S811(0.0305g)和光引发剂Irg651(0.002g)充分混合均匀,采用加热熔融法制备而得;
步骤2)中,氢键的受体BTS(0.0071g)和氢键的给体YSLG(0.0198g);
步骤3)中,氢键断裂温度170℃;
步骤4)中,所述辐照强度为365nm,2.2mW/cm2;辐照时间20min;
将液晶盒降温到室温,得到室温条件下具有反射波宽为800nm-1000nm的液晶薄膜。
实施例8高温下具有宽波反射特性的液晶薄膜的制备
按照实施例5的方法制备高温下具有宽波反射特性的液晶薄膜。区别在于:手性液晶性可聚合单体Ch2(0.0635g)、小分子向列相液晶SLC1717(0.2411g)、手性添加剂S811(0.0305g)和光引发剂Irg651(0.002g)充分混合均匀,采用加热熔融法制备而得;
步骤2)中,氢键的受体BTS(0.0279g)和氢键的给体LBDG(0.0129g);
步骤3)中,氢键断裂温度260℃;
步骤4)中,所述辐照强度为365nm,1.2mW/cm2;辐照时间30min;
将液晶盒降温到室温,得到室温条件下具有反射波宽为800nm-1000nm的液晶薄膜。
将实施例5-8所得液晶薄膜按照本领域常规方法制成温度响应智能器件,即当智能器件只反射单一螺距的光时表明环境温度没有超过氢键断裂温度,当智能器件能够实现宽波反射时,意味着环境温度超过氢键断裂温度。
虽然,上文中已经用一般性说明及具体实施方案对本发明作了详尽的描述,但在本发明基础上,可以对之作一些修改或改进,这对本领域技术人员而言是显而易见的。因此,在不偏离本发明精神的基础上所做的这些修改或改进,均属于本发明要求保护的范围。
Claims (10)
1.一种液晶薄膜,其特征在于,由胆甾相液晶与氢键自组装类手性材料混合形成复合体系,经紫外光辐照聚合而得到的;
所述胆甾相液晶由如下重量份的组分制得:手性液晶性可聚合单体5-20份,小分子向列相液晶65-90份,手性添加剂5-15份,光引发剂0.5-5份;
所述氢键自组装类手性材料包括氢键的受体和给体,所述氢键的给体选自如下化合物中的一种或两种以上:
所述氢键的受体选自如下化合物中的一种或两种以上:
所述氢键的给体与氢键的受体的摩尔比为1:(1.2-2.2);
所述胆甾相液晶与氢键自组装类手性材料的质量比为(4-20):1。
2.根据权利要求1所述的液晶薄膜,其特征在于,所述手性液晶性可聚合单体选自以下化合物中的一种:
3.根据权利要求1所述的液晶薄膜,其特征在于,所述小分子向列相液晶为SLC1717。
4.根据权利要求1所述的液晶薄膜,其特征在于,所述手性添加剂选自以下化合物中的一种或两种以上:
5.根据权利要求1所述的液晶薄膜,其特征在于,所述光引发剂为Irgacure651。
6.根据权利要求1-5任一项所述的液晶薄膜,其特征在于,所述的液晶薄膜为在高温条件下具有宽波反射特性的液晶薄膜或在室温条件下具有宽波反射特性的液晶薄膜。
7.一种权利要求1-6任一所述的液晶薄膜的制备方法,其特征在于,将胆甾相液晶与氢键自组装类手性材料混合形成复合体系,经波长为365nm,光强为0.001-100mW/cm2的紫外光辐照5-240min而得。
8.根据权利要求7所述的制备方法,其特征在于,所述复合体系在室温条件下经紫外光辐照后,再加热至氢键断裂温度,得到在高温条件下具有宽波反射特性的液晶薄膜;所述复合体系先加热至氢键断裂温度经紫外光辐照后,再降温至室温,氢键自组装,得到在室温条件下具有宽波反射特性的液晶薄膜。
9.一种温度响应智能器件,其特征在于,含有权利要求6所述的在高温条件下具有宽波反射特性的液晶薄膜。
10.一种圆偏振片,其特征在于,由权利要求6所述的在室温条件下具有宽波反射特性的液晶薄膜制得。
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US20150353828A1 (en) | 2015-12-10 |
CN104046368A (zh) | 2014-09-17 |
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