CN1774427A - 用于复制保护压缩盘的瞬时光学状态改变材料 - Google Patents
用于复制保护压缩盘的瞬时光学状态改变材料 Download PDFInfo
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Abstract
至少在3位和7位被供电子和吸电子基团取代的吩噻嗪化合物。包括图1所示的那些化合物。这些化合物用于对光学数据存储介质提供复制保护。
Description
发明背景
发明领域
本发明一般涉及的是对用于光盘阅读器的波长，尤其是CD光学阅读器产生的波长有反应的瞬时光学状态改变保密材料。这种材料可直接应用于光学介质以实现复制保护。更具体地说，该瞬时光学状态改变保密材料可用于制造光学可读数字存储介质，能保护存储到其上的信息不被常规光学介质阅读器复制，但允许通过同样的光学阅读器从数字存储介质中读取信息。
相关技术领域的说明
数据以光学形变或位于介质的一层或多层中的不连续位置的标记的形式被储存在光学介质上。这种形变或标记使光反射性发生改变。要阅读光学介质上的数据，需使用光学介质播放器或阅读器。当介质或激光头旋转时，光学介质播放器或阅读器通常发出一个激光小点，即“读出”点，穿过盘基片照射到含有这种光学形变或标记的数据层。两种通用型的光学介质是CD盘，单面(single-side，SS)单层(single-layer，SL)盘提供约650兆字节的最大存储空间；和单面(SS)单层(SL)盘提供约4.37GB(1GB＝231字节)的DVD盘。
在常规的“只读”型光学介质(例如，“CD-ROM”)，通常用一系列金属化的凹槽和槽脊来编码数据。从非金属化面导出的“读出”点以读出点的光被反射回到阅读器的光电传感器内的方式被反射。当从激光阅读面访问(reference)时，凹槽在技术上被称为凸起(bump)。凹槽和槽脊之间的跃迁，以及这种跃迁之间的时间选择，代表通道位。因此凹槽和槽脊自身并不是零或一序列的代表。通常在CD中，14个通道位构成在称为8到14调制的过程中翻译成8比特数据值的数据码位(EFM)。
在塑料介质表面上形成的显微凹槽以轨道排列，通常以始于介质中心终于介质外缘的螺旋形轨道放射状地间隔。介质的凹槽面通常被一反射层例如薄层铝或金涂覆。当从激光阅读面访问观察时，金属化面所见到的“凹槽”也被称为“凸起”。通常把一层漆涂覆在凹槽面上作为保护层。
由光学介质播放器或阅读器测定的从只读介质表面反射的光强度依据沿信息道存在或缺少凹槽而变化。当读出点在槽脊上时，从盘直接反射的光比读出点在凹槽上时更多。由于疵点引起的误差可能干扰读取，所有的光盘都采取误差管理策略以消除这些误差的影响。
光学阅读器，例如CD或DVD阅读器，具有发现和阅读以凸起的形式储存在CD上的数据的功用。在常规的播放器中，驱动马达旋转光盘。CD驱动马达被设计来根据正在阅读的轨道精确控制盘的转速在200到500rpm。激光和透镜系统将光聚集在凸起上，光拾取器接收反射光。一个跟踪机械装置移动激光组件，使激光束能跟随螺旋轨道，通常当播放CD时从中心向外移动激光。当激光从盘中心向外移动时，由于凸起的速度等于盘旋转速度(rpm)的半径倍，凸起更快地移经激光。当激光从盘中心逐渐向外阅读时，常规采用一个主轴电机来降低CD的速度，使得激光以一个恒定的速度来阅读，这样就能以恒定的速度从盘读取数据。
所使用的半导体激光、其波长范围及其其操作温度都会影响阅读器光拾取器(PUH)读取的波长。目前DVD阅读器使用产生约630到约660nm波长的激光，标准DVD阅读器测定650±5nm的波长，而标准的DVD-R阅读器测定650+10/-5nm的波长。目前CD阅读器使用产生约770nm到约830nm波长的激光，而具有PUH的标准的CD阅读器阅读约780nm的波长。如本领域技术人员所知，PUH只能检测出离入射激光束有一定偏差的反射束。例如，典型的DVD-R需要径向偏差不大于±0.80°和切向偏差不大于±0.30°。
目前可用的大多数市售软件、视频、音频和娱乐部件以只读光学格式记录。原因之一是数据复制成只读格式比数据复制成可写和可重写光学格式便宜得多。另一原因是从阅读可靠性的立场来看，只读格式较少有问题。例如，某些CD阅读器/播放器在阅读CD-R介质方面有问题，该介质有较低的反射率，从而需要较高功率的阅读激光，或者较好“调谐”到特定波长的激光。
由于尺寸较小和其生产中涉及的资源较便宜，所有种类的光学介质都显著降低了包含在销售内容中例如软件、视频和音频产品、以及游戏中的制造成本。很不幸地，这也提高了盗版者的盈利，并且某些介质例如视频和音频比起其他数据存储介质有更好的盗版复制品销售到大众。据介质经销商报告，由于高质量的复制件有数十亿美元潜在的销售损失。
盗版者通常通过从光学介质提取逻辑数据，把它复制到磁带上，并把磁带放在母版装置中来制造光学母版。盗版者有时也使用CD或DVD可记录介质复制装置来制造分布式介质的复制品，这些复制品可被直接出售或作为预制母版用于产生一个新的用于复制的玻璃母版。从一单张母版可压制成几十万的盗版光学介质，并且储存在光学介质上的信息质量没有下降。因为消费者要求光学介质保持高的质量，而且由于这一介质易于以较低的成本复制，假冒就非常盛行。
与本申请具有共同的发明人的WO 02/03386 A2公开了通过检测盘上的光学不均匀性或改变，和/或在重读光学存储介质的特定区域时读出信号的改变，尤其是由光敏感材料，例如染料引起的改变来防止从光学存储介质复制数据的方法，这些染料，可通过吸收、反射、折射或影响入射束来影响读出波长。假如在盘上预期有不均匀或改变的位置上未检测到不均匀性或读出信号的改变，可以使用软件控制来拒绝访问内容。WO 02/03386 A2的公开在此整体引用作为参考。
在公开文本WO 02/03386 A2中描述的一个优选实施方案含有光敏感材料，该材料位于光盘上的光学状态改变保密材料，其在一种光学状态下不会对读出信号的数据读取有不良作用，但曝光到光学阅读器入射束的波长下会转化成另一种光学状态，优选以延时形式，确实影响读出信号的数据读出。在WO 02/03386 A2描述的一个优选实施方案中，光学状态改变保密材料仅仅瞬时改变光学状态，其光学状态过一段时间就会恢复。
需要确定可以WO 02/03386 A2所述方式用于实现光盘的复制保护的最佳瞬时光学状态改变保密材料，特别是当用其各自的ISO/IEC标准阅读器阅读时符合ISO/IEC标准的CD和DVD。特别是需要确定能用于这种复制保护方法，而不需改动光学介质阅读器的材料。
定义
“数据形变(data deformation)”：在代表存储数据并能被光学阅读器读出的数据项上或数据项中的结构变动。
“光学介质”：能存储能被光学阅读器读出的数字数据的任一几何形状(不必是圆形的)的介质。
“光学阅读器”：用来读取光学介质的阅读器(如下定义)。
“光学状态改变数据形变”：指与光学状态改变保密材料关联的代表数据的项目上的光学形变，用光学阅读器读出的数据形变随光学状态改变保密材料的光学状态而变。
“光学状态改变保密材料”：指通过从最初的光学状态到另一种光学状态的光学状态改变用于验证、鉴别或保护光学介质的无机或有机材料。
“持久的瞬时光学状态改变保密材料”：指在光学阅读器阅读光学介质时，光学状态能进行超过30次改变的瞬时光学状态改变保密材料。
“阅读器”：能够检测记录在光学介质上的数据的任一设备。术语“阅读器”的意思包括，但不限于播放器。例如CD和DVD阅读器。
“只读光学介质”：具有以一系列凹槽和槽脊代表的数字数据的光学介质。
“记录层”：用于阅读、播放或加载到计算机的在其上记录有数据的光学介质的一部分。所述数据可包括软件程序、软件数据、音频文件和视频文件。
“重读”：对记录在介质上的起初已被阅读后的一部分数据进行阅读。
“瞬时光学状态改变保密材料”：指通过在第一种光学状态到第二种光学状态之间瞬时改变光学状态，并在一段时间后自发回复到上述第一种光学状态，用于验证、鉴别或保护数据项的无机或有机材料，该材料在光学阅读器阅读下能以该光学阅读器检测的方式进行这种光学状态改变多于一次。
“瞬时光学状态改变数据形变”：指与瞬时光学状态改变保密材料相关联的代表数据的项目上的光学形变，用光学阅读器读出的数据形变随瞬时光学状态改变保密材料的光学状态而变。
“临时的瞬时光学状态改变保密材料”：指在光学阅读器阅读光学介质时，光学状态能进行少于30次改变的瞬时光学状态改变保密材料。
为本公开的其余部分起见，无论这些所述术语是否是其最初的定义，这些术语都被理解为上述定义。
发明概述
本发明提供一种可被光学阅读器阅读的复制保护光学介质，该介质采用在约770nm到约830nm的波长范围易于产生可测(由光学阅读器判断)的光学相变的瞬时光学状态改变保密材料，该材料含有某些下式的噻嗪衍生物：
其中，R1-R6是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基或卤素，X和Y均可是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基和卤素中任一，假如X或Y中任何一个是相对于噻嗪骨架的强供电子基团，则X或Y中的另一个是相对于噻嗪骨架的强吸电子基团。
附图简述
插入并构成说明书部分的附图用来说明本发明目前优选的实施方案，并与上文给出的概括说明和下文给出的优选实施方案的详细说明一起用来解释本发明的原理。
图1示出本发明的噻嗪化合物当被约770nm到约830nm的波长照射时表现出光学状态改变。
发明详述
本发明提供一种含有瞬时光学状态改变保密材料的复制保护的光学介质，当曝露于典型的CD光学阅读器的波长下，即，约770nm到约830nm时，该材料可显示出光学状态改变。
已经发现了如下结构通式的某些“推—拉”型的噻嗪染料用光学阅读器在约770nm到约830nm的波长进行操作时可显示出可检测的光学状态改变：
其中，R1-R6是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基或卤素，X和Y是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基和卤素中任一，假如X或Y中任何一个是相对于噻嗪骨架的强供电子基团，则X或Y中的另一个是相对于噻嗪骨架的强吸电子基团。
在3位和7位连接强供电子和吸电子基团，就可以得到推—拉结构。与亚甲蓝比较，这种结构有显著的红移。
范例“推—拉”噻嗪化合物的制备
实施例1：吩噻嗪5-鎓四碘化物水合物
在5℃搅拌吩噻嗪(2.13g，11毫摩尔)的氯仿(75毫升)溶液，并在1小时内滴加碘(8.38g，66毫摩尔)的氯仿(175毫升)溶液进行处理。在5℃再搅拌混合物30分钟，过滤所得沉淀物，用氯仿清洗，然后保持在室温真空下直到重量恒定。产生黑色粉末，7.10g(90％)。
实施例2：3-(二甲基氨基)吩噻嗪5-鎓三碘化物
在室温下搅拌吩噻嗪5-鎓四碘化物水合物(0.417g，0.57毫摩尔)的甲醇(10毫升)溶液，并滴加二甲基胺(1.14毫摩尔)的甲醇(2毫升)溶液进行处理。在室温下搅拌混合物3小时直到根据TCL(二氧化硅，CH3OH/TEA)监测到起始材料消耗掉。过滤沉淀物，用少量的甲醇清洗，产生黑色固体，0.30g(84％)。
实施例3：[7-(二甲基氨基)吩噻嗪-3-亚基]甲烷-1，1-二腈
向3-(二甲基氨基)吩噻嗪5-鎓三碘化物(0.15g，0.24毫摩尔)的甲醇(10毫升)溶液加入丙二腈(0.095克，1.44毫摩尔)和碳酸钠(0.28克，2.88毫摩尔)，在室温下搅拌混合物2小时，用UV-Vis监测反应。然后向反应混合物中加入盐水和二氯甲烷，分离二氯甲烷层，用水、盐水洗涤并干燥(硫酸钠)。用柱色谱(二氧化硅，二氯甲烷)纯化，产生深蓝带，去除溶剂，产生紫色固体。
在图1中列出本发明的其他范例噻嗪化合物。
关于优选实施方案的声明
尽管本发明是就优选的实施方案来描述的，本领域技术人员会容易察觉到可以对本发明进行各种改变和/或修改，而不偏离如所附权利要求书所阐述的本发明的精神或范围。本文引用的所有文件在此全文引用。
Claims (2)
1.具有如下结构的化合物：
其中，R1-R6是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基或卤素，X和Y均可是氢、烷基、芳基、烷氧基、硫代烷氧基、烷氨基、硝基、氨基和卤素中任一，假如X或Y中任何一个是相对于噻嗪骨架的强供电子基团，则X或Y中的另一个是相对于噻嗪骨架的强吸电子基团，
其中，所述化合物被应用于光学介质，并在所述光学介质上可被能够产生从约770nm到约830nm波长的光学阅读器检测到光学状态从一种起始光学状态到第二种光学状态的瞬时改变。
2.如权利要求1所述的化合物，其中该化合物在某种意义上与光学数据形变关联，这样，当该化合物在其起始光学状态和第二种光学状态时光学数据形变的读数是不同的。
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| US20080193873A1 (en) * | 2002-06-17 | 2008-08-14 | Verification Technologies, Inc. | Changing light absorption by disruption of conjugation |
| US7176308B2 (en) * | 2002-06-17 | 2007-02-13 | Verification Technologies, Inc. | Processes for preparing novel methylene blue derivative |
| US6952392B2 (en) * | 2002-06-17 | 2005-10-04 | Verification Technologies, Inc. | Laser reactive dyes for DVD copy protection system |
| US20040152017A1 (en) * | 2002-06-17 | 2004-08-05 | Rakesh Vig | Bis-propyl amine analog and composition |
| US7368221B2 (en) * | 2002-06-17 | 2008-05-06 | Verification Technologies, Inc. | Changing light absorption by disruption of conjugation |
| BR0311927A (pt) * | 2002-06-17 | 2005-04-05 | Verification Technologies Inc | Materiais para proteção de cópias de meio óptico, que reagem transientemente a um feixe de leitora |
| US7344823B2 (en) * | 2002-09-26 | 2008-03-18 | Verification Technologies, Inc. | Transient optical state change materials useful in copy-protected compact discs |
| US7391691B2 (en) * | 2003-08-29 | 2008-06-24 | General Electric Company | Method for facilitating copyright protection in digital media and digital media made thereby |
| US20060072444A1 (en) * | 2004-09-29 | 2006-04-06 | Engel David B | Marked article and method of making the same |
| US7459259B2 (en) | 2004-09-29 | 2008-12-02 | Sabic Innovative Plastics Ip B.V. | Marked article and method of making the same |
| US7101997B2 (en) * | 2004-10-07 | 2006-09-05 | Honeywell International Inc. | Method for producing phenothiazinium compounds |
| US20060165391A1 (en) * | 2005-01-13 | 2006-07-27 | Verification Technologies, Inc. | Copy protection for video content contained in the VOB file structure |
| US7892618B2 (en) | 2005-03-21 | 2011-02-22 | Sony Corporation | Deterring theft of optical media |
| EP1872482A4 (en) * | 2005-04-18 | 2009-12-23 | Veriloc Llc | ULTRAVIOLET ACTIVATION SYSTEM FOR PREVENTING DIGITAL PIRACY FROM RECORDING MEDIA |
| EP1872481A4 (en) * | 2005-04-18 | 2009-12-23 | Veriloc Llc | RECORDING MEDIA WITH PIRATE PROTECTION |
| US8258481B2 (en) * | 2005-04-25 | 2012-09-04 | Sony Dadc Us Inc. | System and method for selectively enabling or disabling an optical device |
| US20070050585A1 (en) * | 2005-08-24 | 2007-03-01 | Sony Dadc Us Inc. | Selectively enabling playback of content on an optical medium |
| WO2007053643A2 (en) * | 2005-11-01 | 2007-05-10 | Verification Technologies, Inc. | Hard-coat for anti-shrink-anti-copy optical medium |
| WO2008002928A2 (en) * | 2006-06-27 | 2008-01-03 | Veriloc Llc | Optical disc carrying case with activation window |
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| JPH08122836A (ja) * | 1994-10-19 | 1996-05-17 | Mitsubishi Chem Corp | 非線形光学材料用色素及びそれを含有する非線形光学材料 |
| US5815484A (en) | 1995-12-28 | 1998-09-29 | Hide And Seek Technologies L.L.C. | Copy protectable optical media device and methodology therefor |
| US6011772A (en) * | 1996-09-16 | 2000-01-04 | Spectradisc Corporation | Machine-readable optical disc with reading-inhibit agent |
| US6228440B1 (en) | 1998-07-28 | 2001-05-08 | Motorola, Inc. | Perishable media information storage mechanism and method of fabrication |
| US6641886B1 (en) | 1999-03-23 | 2003-11-04 | Flexplay Technologies, Inc. | Directory read inhibitor for optical storage media |
| WO2002002301A1 (en) | 2000-06-30 | 2002-01-10 | Verification Technologies Inc. | Copy-protected optical media and method of manufacture thereof |
| BR0311927A (pt) * | 2002-06-17 | 2005-04-05 | Verification Technologies Inc | Materiais para proteção de cópias de meio óptico, que reagem transientemente a um feixe de leitora |
| US7344823B2 (en) * | 2002-09-26 | 2008-03-18 | Verification Technologies, Inc. | Transient optical state change materials useful in copy-protected compact discs |
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| WO2004029672A2 (en) | 2004-04-08 |
| WO2004029672A3 (en) | 2005-01-27 |
| US20040121262A1 (en) | 2004-06-24 |
| US7344823B2 (en) | 2008-03-18 |
| MXPA05004250A (es) | 2006-04-27 |
| EP1551817A2 (en) | 2005-07-13 |
| CA2503684A1 (en) | 2004-04-08 |
| EP1551817A4 (en) | 2009-09-23 |
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