CN1180411C - 光记录介质和光记录方法 - Google Patents

光记录介质和光记录方法 Download PDF

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CN1180411C
CN1180411C CNB008173486A CN00817348A CN1180411C CN 1180411 C CN1180411 C CN 1180411C CN B008173486 A CNB008173486 A CN B008173486A CN 00817348 A CN00817348 A CN 00817348A CN 1180411 C CN1180411 C CN 1180411C
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liquid crystal
film
orientation
light
crystal film
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CN1411599A (zh
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佐飞裕一
夫
安田章夫
伸
山本真伸
D·奈尔
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Sony Deutschland GmbH
Sony Corp
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Sony Corp
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Abstract

由光取向性膜和液晶薄膜相邻接触形成光记录介质。对该光取向性膜和液晶薄膜进行光照，在使光取向性膜取向的同时，由该光照导致温度上升，使液晶薄膜的粘度降低，在光取向性膜和液晶薄膜的界面通过分子间力使液晶薄膜中的液晶分子按照光取向性膜的取向而取向，通过液晶分子的取向保持记录信息。由此，使用光取向性膜可以实现充分的信号量，确保热稳定性和对光照的稳定性。

Description

光记录介质和光记录方法
技术领域
本发明涉及光取向性膜和液晶薄膜组合的新颖光记录介质，还涉及光记录方法。
背景技术
近年来，对于使用偶氮苯的光取向有机膜的应用在深入的探讨中，例如研究了其作为光盘记录材料的应用。
使用光取向有机膜的光盘，由于均为有机膜，如果适当地焚烧处理，不会残留有害物质。以此作为可复写光记录介质，与现在主流的光磁介质和相变记录介质相比非常有利。因为环境问题是产业上非常大的一个课题。
上述的光取向有机膜用于光盘的时候，信号检出是采用读取偶氮苯取向时所产生的双折射的方法。
但是，光取向有机膜的双折射一般都非常小，因此，为了取得高的变调度，必须使膜厚变厚。
另一方面，在光盘上以高密度进行记录的时候，为了提高透镜的数值孔径NA，光源波长变短，这种情况下焦点深度变浅，记录膜的膜厚必须变薄，结果双折射的信号量不得不减小。
为此，也尝试开发了双折射大的材料，但是不是材料的制造工艺复杂，难以大量生产，就是有消除特性差的问题。
另外，一般来说，如此的光取向有机膜热稳定性、对光照的稳定性等方面存在许多问题，还没有达到实用的地步。
此外，作为上述光取向有机膜的记录方式，分子取向通过直线偏振光的照射相应于偏振光的方向发生变化(光取向)，利用这个事实，采用把分子取向的方向作为信息而进行记录的方式，但是当光盘再现的时候，也有光的照射，由于再现光的照射，分子取向发生变化，记录的信息丧失，造成问题。
一般来说，再现光和记录光的光量差为1∶10左右，差别要在此之上，由于激光性能等的限制，难以设计。为此，例如再现10次就相当于记录1次的受光量，结果记录信息因再现而丧失。
作为避免出现此种情况的手法，使记录光源和再现光源处于不同波长，使得在分光特性上对再现光的吸收少，这样的方法是有效的。
但是，以此方法，必须在同一装置内装入2种波长的光源，导致装置变大，成本增加。而且，由于再现时使用红光等长波长的激光，聚光斑会变大，难以提高记录密度，不合适。
发明的公开
本发明的目的在于获得以下性质的新型光记录介质和光记录方法，可以使用光取向性膜同时获得充分的信号量，而且热稳定性和对光照稳定性佳，不会因再现光照射丧失记录信息。
本发明的光记录介质，其特征在于将光取向性膜与液晶薄膜相邻层合，通过液晶薄膜中的液晶分子的取向保持记录信息。
另外，本发明的光记录方法，其特征在于是对由光取向性膜和液晶薄膜相邻层合形成的光记录介质照射光，使上述光取向性膜取向的同时，因光照产生的温度上升降低上述液晶薄膜的粘度，通过上述光取向性膜和液晶薄膜界面上的分子间力，使上述液晶薄膜中的液晶分子依上述光取向性膜的取向而取向，通过该液晶分子的取向保持记录信息。
本发明通过使液晶薄膜和光取向性膜相邻设置，将记录信息保持在液晶薄膜中，实现了稳定地记录再现。就是说，在照射记录光的时候光取向性膜取向，在冷却过程中液晶薄膜依光取向膜固定，保持记录信息。根据此方法可以以同一波长再现记录，可以实现高密度地记录。
由此，本发明的光记录介质和光记录方法利用了光取向性膜的性能和液晶薄膜的性能，可以进行稳定地高密度记录再现。
其优点在于，先取向性膜不直接用于信号的检出，仅仅用于记录时的取向，故光取向性膜的膜厚可以变薄。由此，取向的分子数少，反应速度快；薄的情况下可望把取向的分子抑制在面内；另外，透光度高，有利于多层化，由于这些优点，在高密度化上是有利的。
而且，光取向型膜的双折射越小越好，这样层材料的选择范围就广了。
再者，采用荧光发光层作为液晶薄膜的时候，由于可以任意选择荧光波长，在成为多层介质的情况下，信号检出也可以容易地进行。就是说，由于别的层的信号和波长可以不同，层间信号的干扰可以有可能降低到理想的程度。
液晶薄膜也可以采用双折射大的材料，这样的情况下，即使单层也可以检出大的信号。
而且，即使光取向性膜的取向性低，由于液晶薄膜取向度高，可以获得取向度增强的效果。
进一步，本发明的最有效的效果是实现以光取向性膜单层不可能实现的以同一波长记录·再现。特别是可以采用蓝色光源记录·再现，可以高密度地记录。蓝色光源作为荧光的激发光也是合适的。
此外，由于本发明所用的材料均为有机物，具有只要适当地焚烧处理，就不会残留有害物质的优点。以此作为可复写光记录介质，与现在主流的光磁记录介质和相变记录介质相比非常有利。因为环境问题是产业上非常大的一个课题。
附图简要说明
图1是表示适用于本发明的光记录介质的一个构成例的示意断面图。
图2是表示适用于本发明的光记录介质的另一个构成例的示意断面图。
图3是表示直线偏振光入射到聚芴聚合物的时候荧光的偏振特性的示意图。
图4是表示圆偏振光入射到聚芴聚合物的时候荧光的偏振特性的示意图。
图5是表示采用双折射性液晶薄膜的时候光记录介质的构成例的示意断面图。
图6是表示适用于采用多层结构的光记录介质的一个构成例的示意断面图。
图7是表示采用多层结构的时候各液晶薄膜的发光光谱的设定例的特性图。
实施发明的最佳方案
以下参照附图对适用于本发明的光记录介质和光记录方法进行说明。
首先，适用于本发明的光记录介质的基本结构如图1所示。
图1所示的光记录介质，是在基板1上依次层合形成光取向性膜2、液晶薄膜3，在其上覆盖保护膜4而得，记录光和再现光从基板1一侧照射。
或者如图2所示，在基板1上依次层合液晶取向膜3、光取向性膜2，仍然从基板1一侧照射记录光、再现光。
这里，作为上述光取向性膜2，例如可以利用偶氮苯的光异构化反应。
                        反-偶氮苯                                     顺-偶氮苯          …(1)
偶氮苯有反式和顺式的异构体，反式对热稳定。沿反式体的长轴照射平行的偏振光，反式体吸收光变为顺式，但很快恢复反式。这种情况下，恢复方向与激发前不一定相同。因此，持续照射直线偏振光，由于与偏振光平行的偶氮苯始终处于激发的不稳定位置，最后偶氮苯取向在与直线偏振光垂直的方向上。
而且，本发明的光记录介质中，该光取向型膜2在阻断光以后的取向稳定性与记录无关，比较容易实现结构的最佳化。当然，由于有必要改变液晶薄膜3的取向，优选偶氮苯与高分子主链键连。
就是说，由于偶氮苯的作用，高分子主链移动，由于高分子主链与相邻的液晶薄膜3结合，液晶薄膜取向，信息记录在液晶薄膜中。为此，作为上述偶氮苯的取代基的具体例子，例如有下面结构式(2)所示的取状基。
应予说明，即使不与高分子主链结合液晶的取向也可能发生变化，此方面也有研究报告(第18次国际液晶会议摘要集27B-5-1)。
上述光取向性膜2的膜厚度，只要是光取向性膜2可以发挥功能的厚度即可。具体来说，10nm左右以上即可，双折射小的情况下，膜厚也可以厚一些。双折射大的情况下，到达液晶薄膜3的偏振光有时会紊乱，液晶薄膜产生的信号的偏振光也会紊乱，膜厚应尽量薄。而且，膜厚薄，取向的分子数少，反应速度快，可望获得把取向方向抑制在同平面内的效果，基于以上理由，光取向性膜2的膜厚应当尽可能的薄，例如优选在30nm以下。
在上述光取向性膜2的上面(下面)，相邻层合形成上述液晶薄膜3。
该液晶薄膜3可以使用任意的液晶材料，不过在此使用的是产生与取向方向平行的直线偏振的荧光的材料作为液晶膜。作为这样的材料，具体来说有聚芴聚合物。
在此，显示荧光发光型液晶聚芴聚合物的具体结构。
此材料可以有各种形态，在此显示一例。相应于光记录材料的形态，例如，通过改变这些聚芴的结构，改变发光光谱也是可以的。
在具有基本结构的式(3)～式(6)中，或者在该聚合物的两端加上端帽(end cap)的时候的分子结构如式(7)～式(9)所示。加上端帽具有提高荧光效率和提高发光的偏振特性的优点。另外，式(10)～式(27)显示其它例子。
Figure C0081734800091
Figure C0081734800121
Figure C0081734800141
Figure C0081734800151
将上述液晶薄膜3设定为室温下粘度高，取向方向不容易发生变化的状态。记录的时候，因光照发生升温，这时候粘度降低，取向方向容易发生变化，由于与光取向性膜2的分子间键的作用达到同一方向的取向。即使遮断光该方向也保持，粘度上升，信息得以保持。
上述光取向性膜2和液晶薄膜3均以旋涂法成膜。不过，也可以用蒸镀法成膜。在进行旋涂法的时候，因为光取向性膜2通常是相对于溶剂溶解性低的材料，例如使用THF(四氢呋喃)等作为溶剂。相反的，此种状况对于液晶薄膜3的旋涂却是合适的。其原因是因为液晶薄膜3旋涂之时光取向性膜2不会溶解。液晶薄膜3的溶剂可以使用溶解度较高者。具体来说，例如可以举出甲苯等。应予说明，如果光取向性膜2溶解性也高，那么使用蒸镀法就不会有问题。
作为保护膜4，使用一般用于光记录介质的紫外线固化树脂，但是因为其旋涂之际会溶解液晶薄膜3，故与液晶薄膜3之间用SiN或者SiO等介电体成膜为50～100nm厚，加以保护。
作为基板1，与以光磁记录膜或者相变化膜作为记录层的光记录介质同样，采用导引沟形成为螺旋状的基板。为与光学系统相适应，获得聚焦和寻迹等各特性，使用结构和尺寸等最佳化者。
作为上述基板1的材质，也可以使用聚碳酸酯，但是旋涂光取向性膜2的时候，因为溶剂溶解性高，也会溶解基板1，故与光取向性膜2之间用SiN或者SiO等介电体成膜为50～100nm厚，进行保护。此时，由于有光的多重干涉，设定介电体层的厚度以获得最大的信号检出。
在具有上述构成的光记录介质中，信息的记录是如上所述利用温度的上升使液晶薄膜3的取向方向调整到与入射的直线偏振光相垂直的方向上而实现的。就是说，与光磁记录膜或者相变化膜同样，记录时以较高强度的光仅对记录标记的部分入射，再现时以温度不会上升的强度的光入射，检出信号。光取向性膜2是因光量而取向度发生变化的所谓“光子模式”，因为实际的记录是通过液晶薄膜3进行的，是以包括存在临界温度的所谓热模式的机制进行记录的。
光取向性膜2是光子模式的，因此，只要没有充分的光照，取向度就低，液晶薄膜3分子彼此的结合力强，取向度高。因此，即使例如光取向性膜2的取向度低，方向规一的液晶薄膜3的取向度变高，可以获得所谓取向度增强的效果。就是说，即使光取向性膜2没有充分取向也可以，可以以低能量高对比度地记录。
在此，对上述发射荧光的液晶薄膜3的特性进行说明。
衬底使用聚酰亚胺膜代替光取向性膜2，在该聚酰亚胺膜上，测定聚芴聚合物的取向不同时的荧光发光。结果如图3和图4所示。此图是在聚酰亚胺上测得的，不过对于取向后的光取向性膜2也是相同的。聚酰亚胺膜中所用的聚酰亚胺的结构如式(28)所示。
图3是激发激光为407nm，以直线偏振光入射时的荧光，聚芴的取向方向与激光的方向平行的情况、垂直的情况下的光谱。如图所示，与激发光的方向平行时，荧光强度大，例如使消除时的取向方向与记录标记的取向方向相垂直，以直线偏振光作为再现光入射时，可以观测到荧光强度的改变。
图4是以激光作为圆偏振光向聚芴聚合物入射时的荧光特性。即，是将检测元件设置在检测器的前面，其角度与激发光平行或者垂直时候的观测光量的光谱。由图可见，荧光本身也是直线偏振光。就是说，聚芴的取向方向以消除、记录标记之间相互垂直记录时，观测圆偏振光的再现光，通过在检测器之前设置检测元件，观测到荧光强度的改变。
以上，对于构成液晶薄膜3的材料以聚芴聚合物为例进行了说明，液晶薄膜3中不使用聚芴聚合物的例子也是可能的。
就是说，可以选择液晶薄膜3中所用的液晶材料本身无发光特性，只是与光取向性膜2的结合特性良好的材料。
为此，在该液晶薄膜中掺杂2色性荧光色素，与液晶材料相结合而取向。作为2色性荧光色素，例如可举出式(29)所示的色素。应予说明，式中的R表示烷基链。
Figure C0081734800181
此时，与聚芴聚合物那样含有发光分子的液晶材料以单体应用的情况不同，是分别选定液晶分子和发光分子后混合使用的，这样材料的选择范围广，容易最佳化。
以下，就使用具有双折射性的材料作为上述液晶薄膜的情况加以说明。
双折射大的液晶材料可以选择的范围比较广，其基本分子结构是必须要为棒状。基本的膜结构如图5所示。
基本上与图1所示相同，为检出因双折射而将偏振光旋转后的反射光，在液晶薄膜3上设计了反射膜5。
上述反射膜5的厚度，在反射率高的金属膜的情况下，优选为40nm以上。作为反射率高的金属，例如可举出Al或Ag等。作为反射膜5，不使用金属膜，例如层合折射率不同的介电体，也可以获得高的反射率。此种反射膜可以在金属膜热传导性过好，热特性不佳的情况下使用。
液晶薄膜3的膜厚，当其双折射的大小为Δn，膜厚为d时，设定为大致d＝λ/8Δn。
再现时的直线偏振光以与取向方向成45°倾角入射，这样，反射的偏振光成为圆偏振光，其方向因偏振方向而成为左圆偏振光或右圆偏振光。
这样，之所以把上述膜厚设定为大致d＝λ/8Δn而不是正好d＝λ/8Δn的理由是，在光取向性膜的界面和光取向性膜和基板的界面上有反射存在，存在光的多重干涉效果，因此，多少与正好是入射光成为圆偏振光的d＝λ/8Δn有些偏差的缘故。准确的膜厚是通过对多重干涉进行计算而适当设定的。
最后，显示使用具有荧光发光的材料作为液晶薄膜，使用多层光取向性膜和液晶薄膜组(对)时候的例子。
此例的光记录介质，可以多层记录，实现高密度化。其结构如图6所示。
本例中，由光取向性膜2和液晶薄膜3层合的对，通过缓冲层6多层重叠。
光取向性膜2和液晶薄膜3的成膜方法与如图1所示的例子相同，不同的是，“对”之间的缓冲层6。其起的作用是将各记录层之间隔离开焦点深度以上，可以得到无论焦点汇聚在哪一层，来自其它层的符号间干涉抑制在最低限度的效果。
为此，将缓冲层6的膜厚设为数μm以上，这种膜厚程度对隔离各“对”是必要的。例如，此例中是10μm。
缓冲层6的材料必须透明，此例中使用了紫外线固化树脂，不过也可以使用聚碳酸酯和粘接材料来加以实现。为抑制光吸收，光取向性膜2和液晶薄膜3的膜厚以薄为好。
在多层的时候，液晶薄膜3的发光光谱，各组分别采用不同的波长。例如图7所示那样。
例如，从接近基板1处的液晶薄膜3起依次命名为LC1、LC2等，令LC1具有最短的荧光发光波长，LC2通过分子结构的改变光谱略微向长波方向迁移。LC3以后依次进行。
再现时，通过使用滤色片，或者棱镜，可以实现不泄漏其它层的光，提高S/N，提高记录密度。
另外，如果是只读光盘，也可以通过使缓冲层6薄些，把所有层抑制在焦点深度内，再现时同时检出所有层的荧光，按照光波长分离信号，可以实现高密度且高传输率的光盘。

Claims (6)

1.光记录介质，包含基板、光取向性膜和液晶薄膜，所述光取向性膜和液晶薄膜相邻接触层合，通过液晶薄膜内的液晶分子的取向保持记录信息，上述液晶薄膜发与取向方向相平行的直线偏振光的荧光。
2.权利要求1记载的光记录介质，其特征在于在对上述液晶薄膜照射直线偏振光作为激发光时，当该激发光的偏振方向与分子取向平行时，荧光的发光最大，垂直时，荧光的发光最小。
3.权利要求1记载的光记录介质，其特征在于上述液晶薄膜中含有聚芴聚合物作为液晶分子。
4.权利要求1记载的光记录介质，其特征在于上述光取向性膜和液晶薄膜2层为1组，层合至少2组以上，而且，在上述各组之间设置缓冲层，该缓冲层具有光透过性。
5.权利要求1记载的光记录介质，其特征在于上述光取向性膜和液晶薄膜2层为1组，层合至少2组以上，而且，各组液晶薄膜发出波长彼此不同的荧光。
6.光记录方法，其特征在于对由光取向性膜和液晶薄膜相邻接触形成的光记录介质，通过相对运动的光源，根据记录信息照射光，在使上述光取向性膜取向的同时，由该光照导致温度上升，使液晶薄膜的粘度降低，在上述光取向性膜和液晶薄膜的界面通过分子间力使上述液晶薄膜中的液晶分子依上述光取向性膜的取向而取向，在没有光照、温度下降的过程中，上述液晶薄膜的液晶分子固定在上述光取向性膜的取向方向上，从而保持上述记录信息。
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