CN1078972A - 一种扭转向列薄膜及其制备方法和含该薄膜的显示装置 - Google Patents

一种扭转向列薄膜及其制备方法和含该薄膜的显示装置 Download PDF

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CN1078972A
CN1078972A CN 93105738 CN93105738A CN1078972A CN 1078972 A CN1078972 A CN 1078972A CN 93105738 CN93105738 CN 93105738 CN 93105738 A CN93105738 A CN 93105738A CN 1078972 A CN1078972 A CN 1078972A
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S·J·皮肯
G·R·莫尔曼
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Abstract

本发明涉及一种扭转向列薄膜，它包括一种非交联的液晶聚合物，该聚合物具有75℃以上的Tg，而且在Tg和Tni之间，其转动粘度低于5000帕斯卡秒(Pa·s)。这种扭转向列薄膜应用在显示器中。本发明还涉及制备这些扭转向列薄膜的方法，将所述扭转向列薄膜用于光学数据存储和可写入的高密度盘中，以及包括这种扭转薄膜的显示器件。

Description

一种扭转向列薄膜及其制备方法和含该薄膜的显示装置
本发明涉及一种含液晶聚合物的扭转向列薄膜。该薄膜用于显示装量中。图1为显示装置的结构示意图。
图1为显示装置的剖面图，其组成为一个有源的扭转层(4)，它可通过透明电极(6)进行通、断转接；还有一个无源的扭转层(3)；基片(2)设置在二个扭转层(3)和(4)的两边；在两个最外边的基片的外边，有起偏器(1)；在有源扭转层的下方的起偏器下面，装有一个反光镜(5)。
具体地说本发明涉及显示装置的无源扭转层(3)。对于无源层，利用由低分子量液晶材料组成的扭转向列层，例如Kirk Othmer的Encyclopedia of Technology，3rd ed.(New York：Wiley &Sons)vol.7p.728所述。或者可利用双折射薄膜，例如一种拉伸聚合物薄膜。然而，后者不能取得最佳的对比度。虽然使用低分子量液晶材料的确会取得好的对比度，但是还伴有其它的缺点。其中之一就是和低分子量液晶材料是低粘度的情况有关。对无源扭转层的性能来说很重要的是，扭转结构在该层整个宽度中都要保持完整。因此，为了获得一种扭转的、形状固定的结构，在刚性基片之间用隔离物将低分子量材料密封。换句话说，要制造出一个封闭的、刚性的元件。本技术领域目前的趋势是，寻找一种类似于低分子量液晶层的具有扭转向列结构的无源层，该层不必借助于隔离物在基层之间进行密封，但却可以形成一种独立式的柔性薄膜。这种薄膜已经制出，例如在EP-A1-0423881中，通过定向液晶单体形成一种扭转结构，然后例如通过紫外照射固化单体形成聚合物网，从而固定此结构。这种方法的缺点是，这种固定方式对薄膜的柔性有不利的影响，而这种固定方式又是保持扭转结构所必需的。该方法的第二个缺点是，仅可使用交联的液晶单体。再有，该薄膜固化时可能会产生皱缩，难以预先确定薄膜的厚度。这种皱缩的又一个缺点是，在薄膜里可能会形成极细的裂缝。本发明的目的是，生产出一种类似于低分子量液晶层结构的扭转向列结构薄膜，它有柔性，还具有能保持形状不变的扭转结构。
为此，根据本发明的扭转向列薄膜含有一种非交联的液晶聚合物，该聚合物的Tg＞75℃，它在Tg和Tni转动粘度(Y)低于5000帕斯卡·秒(Pa·S)。
使用玻璃化温度Tg大于75℃的聚合物可以获得在室温下稳定的薄膜，同时不用隔离物就能保持它的扭转结构。较高的Tg不必通过交联来固定其扭转结构，同时使薄膜能保持柔性。由于聚合物不被固化，所以也不会发生皱缩现象。因此，可以预先确定薄膜的厚度。在聚合物定向的温度范围内，所用聚合物的粘度必须是足够低的(聚合物在Tg和Tni之间定向，Tni是聚合物从向列状态至均质状态的转变温度)。如果粘度太高，聚合物层完全形成扭转结构要花费太长的时间，或者甚至薄膜不可能全部定向。
聚合物的可定向性可以由转动粘度(Y)来确定。它的大小表示外力场的数值，该外力场是为了扭转排列好的液晶聚合物的导向子必须施加的(即，液晶聚合物的中介组分基团(mesogenic group)所指方向)。W.H.de Jeu Physical Properties of LiguidCrystalline Matarials(New York：Gordon and Breach SciencePublishers Ltd，1980)，第7章108-110页，G.Vertogen和W.H.de Jeu Thermotropic Liquid Crystals，Fundamentals(Barlin Heidelberg：Sptinger-Vetlag，1988)P147-153中都对测定这种转动粘度的技术进行了描述。这些出版物以及R.P.Raynes博士的论文“向列液晶的宏观特性”(该论文在1989年7月17-21日英国南安普顿大学化学系主办的“液晶科技的仪器方法大会”上发表)也都表明，如果不能测量到转动粘度，那么可以取有效粘度做为一个准则。实际上已发现，有效粘度与转动粘度有相同的数量级。有效粘度可以借助于任一个合适的粘度计或流变计来测定(例如，一种锥形板粘度计或couette粘度计)。
不用说，聚合物薄膜的可定向性也取决于薄膜的厚度。薄膜的厚度越大，转动粘度就需越低。一般使用的薄膜厚度为2～10μm。
2μm厚的、Tg和Tni之间转动粘度为10,000Pa·S的聚合物薄膜的定向时间长达13分钟左右。3μm厚的薄膜的定向时间长达30分钟。如此长的定向期对于商业应用是不能接受的，因为所希望的定向期最多为10分钟。
当使用在Tg和Tni之间的转动粘度为3700Pa·s、层厚为2μm的聚合物时，定向期约为5分钟，这是可以被接受的。
当薄膜厚度大于5μm时，转动粘度(Y)将会低于600Pa·S。表明转动粘度(Y)与层厚度关系的一个完善的准则是：Y·(厚度)2≤3*10-a。
原则上说，所有满足上述Tg和转动粘度(Y)要求的液晶聚合物都可以使用。本领域的技术人员可以很容易地检查出一种特定的液晶聚合物是否适用于扭转向列液晶聚合物薄膜。
满足上述要求的聚合物可以选自液晶聚氨基甲酸酯、聚酯、聚酰亚胺、聚(甲基)丙烯酸酯、聚硅氧硅、聚酰胺、聚碳酸酯等等。
最好使用液晶侧链聚酯和聚氨基甲酸酯，因为它们除了具有一个易于预先确定的Tg以及一个最佳的转动粘度外，它们还易于制备，合理的热和化学稳定性，以及合理的紫外线射稳定性。
我们发现，特别适合的是具有按下述结构式1的中介组分基团的液晶聚氨基甲酸酯和聚酯。
结构式1
Figure A93105738.800111
其中：
R1＝-卤素，-R2，-OR2，
Figure A93105738.800122
-CN或-CF3
R2＝-H或有1～3个碳原子的烷基；
R3可能代表与R1相同的基，但它从R1中任意选出；
Q是连接中介组分基团和聚合物主链的单体部分；
n是0或1；
m是0或1；
y是从0到3的一个整数；
p是从2到4的一个整数；
R4＝有1～12个碳原子的烷基；
x是从1到6的一个整数；
Z＝-C＝N-，-N＝C-，
Figure A93105738.800123
-C＝C-
这些液晶聚合物的制备方法类似于公知的液晶聚合物的制备方法。
对于液晶侧链聚氨基甲酸酯的特殊制备方法，可参见荷兰专利申请9102191(尚未向公众公开)，在这里参考引用了该申请。在该申请中，通过(例如)二异氰酸酯与包含符合结构式1的中介组分基团的二醇发生反应，来获取液晶侧链聚氨基甲酸酯。
对于液晶侧链聚酯的特殊制备方法，参照EP-A-0478052(公开日：1992年4月l日)
本发明还涉及扭转向列薄膜的制备方法。在定向过程中，将Tg
一个扭转向列薄膜，和
一对分别布置在无源的扭转向列薄膜和液晶单元外侧的起偏器，
其特征在于该扭转向列薄膜为前述权利要求1-3和7中的任一项所述的薄膜。
基于同一发明构思的另一方法如以下所述。将液晶双官能单体放置在两个定向基片之间，以便进行定向，从而形成一扭转结构，然后进行聚合。在这种情况下，该单体混合物的转动粘度(Y)应低于5000帕斯卡·秒(Pa·S)。当然，如果为了获得稳定的独立式的薄膜，最后的聚合物的Tg必须大于75℃。另外如需要在定向后可以将定向基片去掉。
当然可使用具有中介组分基团的适用单体，并且该单体例如是二醇、二异氰酸酯、羟基异氰酸酯、二羧酸和羟基羧酸。在这些双官能单体中，该双官能部分(如结构式1中的单体部分Q)将成为聚台物主链的一部分，而且中介组分基团通常被当作侧基进行连接。
现在所述的向列薄膜除在显示器中使用外，还可以用于光学数据存储和可写入的高密度盘中。
在这种情况下，将向列薄膜放置在交叉的起偏器之间。通过激光器的照射就可以写入信息，而在照射点处扭转向列结构被破坏。当用激光器扫描(读出)已写入的薄膜时，在照射点处将不发生传输。该扭转向列薄膜最好包含一种染料，以便在近红外区域进行吸收，这样就可以使用固态激光器进行写入。这种固态激光器比较便宜且尺寸小。
本发明还涉及含有本发明的薄膜的一种显示装置。

Claims (12)

1.一种扭转向列薄膜，它包括一种液晶聚合物，其特征在于该液晶聚合物是一种非交联的液晶聚合物，它具有75℃以上的Tg并在Tg和Tni之间具有低于5000帕斯卡·秒(Pa·S)的转动粘度(Y)。
2.根据权利要求1所述的扭转向列薄膜，其特征在于该非交联液晶聚合物在Tg和Tni之间具有低于600Pa·S的转动粘度(Y)。
3.根据权利要求1所述的扭转向列薄膜，其特征在于该液晶聚合物为液晶侧链聚氨基甲酸酯或聚醋。
4.根据权利要求1或2所述的扭转向列薄膜，其特征在于该液晶聚合物包括一个中介组分基团，该基团符合基本结构式1：
Figure A93105738.800031
其中：
R1为-卤素，-R2，-OR2，
Figure A93105738.800032
Figure A93105738.800033
-CN或-CF3；
R2为-H或有1～3个碳原子的烷基；
R3可以表示和R1相同的基，但它独立地选自R1；
Q为单体部分，它将中介组分基团连接到聚合物主链上；
n为0或1；
m为0或1；
y为0至3的一个整数；
p为2到4的一整数；
R4为带有1-12个碳原子的烷基；
x为1到6中的一整数；
Z为-C＝N-，-N＝C-，
Figure A93105738.800041
Figure A93105738.800042
-C＝C-。
5.一种制备扭转向列薄膜的方法，在该方法中将液晶材料放置在两层不同定向方向的定向基片之间，其特征在于该液晶材料包括Tg为75℃以上、并在Tg和Tni之间具有低于5000帕斯卡·秒的转动粘度的液晶聚合物。
6.根据权利要求5所述的方法，其特征在于该液晶聚合物为液晶侧链聚氨基甲酸酯或聚酯。
7.根据权利要求5或6所述的方法，其特征在于该液晶侧链聚合物包括一个中介组分基团，该基团符合基本结构式1：
Figure A93105738.800051
其中：
R1为-卤素，-R2，-OR2，
Figure A93105738.800052
Figure A93105738.800053
-CN或-CF3；
R2为-H或有1-3个碳原子的烷基；
R3可以表示和R1相同的基，但它独立地选自R1；
Q为单体部分，它将中介组分基团连接到聚合物主链上；
n为0或1；
m为0或1；
y为0至3的一整数；
p为2到4的一个整数；
R4为带有1-12个碳原子的烷基；
x为1到6的一整数；
Z为-C＝N-，-N＝C-
Figure A93105738.800061
Figure A93105738.800062
-C＝C-
8.一种扭转向列薄膜，它包括一种液晶聚合物，其特征在于该液晶聚合物为非交联的，具有75℃以上的Tg，而且是从液晶单体混台物中获得的，该液晶单体混合物在Tg和Tni之间具有低于5000Pa·S的转动粘度。
9.一种制备扭转向列薄膜的方法，在该方法中，将液晶材料放置在两层不同取向方向的定向基片之间，其特征在于液晶材料包括液晶双官能单体混合物，并使该混合物定向以形成扭转结构，然后使其聚台，单体混合物的转动粘度(Y)在Tg和Tni之间低于5000Pa·S，最后的聚合物的Tg为75℃以上。
10.根据权利要求1-4中任一项的扭转向列薄膜用于光学数据存储的用途。
11.根据权利要求1-4中任一项的钮转向列薄膜用于可写入的高密度盘的用途。
12.一种显示装置，它包括：
一个液晶单元，它是由放置在两基片之间的扭转向列液晶材料形成的，
一个扭转向列薄膜，和
一对分别布置在无源的扭转向列薄膜和液晶单元外侧的起偏器，
其特征在于该扭转向列薄膜为前述权利要1-3和7中的任一个所述的薄膜。
CN93105738A 1992-04-09 1993-04-08 一种扭转向列薄膜及其制备方法和含该薄膜的显示装置 Pending CN1172824A (zh)

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