CN100399444C - 在光学介质制品上涂覆标记物的方法 - Google Patents
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- CN100399444C CN100399444C CNB2003801094256A CN200380109425A CN100399444C CN 100399444 C CN100399444 C CN 100399444C CN B2003801094256 A CNB2003801094256 A CN B2003801094256A CN 200380109425 A CN200380109425 A CN 200380109425A CN 100399444 C CN100399444 C CN 100399444C
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Abstract
一种赋予光学制品(46)以标记物(54)的方法,其包括:修饰光学制品(46)表面(44)上的预定位置以改变预定位置的表面能;以均匀薄膜的形式将标记物(54)涂覆在光学制品(46)的整个表面(44)上;以及将标记物(54)保留在经修饰的预定位置,同时将标记物(54)从未修饰区域除去。该方法还包括:使光学制品(46)进行产生离心力的旋转运动;以及将标记物(54)保留在经修饰的预定位置,同时借助于离心力将标记物(54)从未修饰区域除去。一种光学制品(46),其包括由包括以下步骤的方法制成的识别标记:将染料溶解在合适的溶剂中以形成溶液,修饰光学制品(46)表面(44)上的预定位置以改变预定位置的表面能,将该溶液涂覆在光学制品(46)的整个表面(44)上,使光学制品(46)进行产生离心力的旋转运动,以及将染料保留在经修饰的预定位置,同时借助于离心力将染料从光学制品(46)表面(44)的未修饰位置除去。
Description
技术领域
本发明一般性地涉及用于识别目的的标记领域。更具体地,本发明涉及使用在精确控制的预定位置上局部分布的标记物来标记旋转的光学介质制品的体系和方法。
背景技术
标记塑料制品对于包括光学存储介质的防盗版的多种应用都是非常需要的。目前光学存储介质得到广泛应用。光学存储介质可用于保存音乐、数据和软件,而且已经成为用于在可靠的封装(reliable package)内分配大量信息的标准介质。作为计算机时代的结果,整个世界范围内的非法CD和DVD拷贝的数量增加。这种趋势的一个原因是家用PC、空白CD-R、空白DVD-R以及快速CD和DVD刻录机(burner)变得更加便宜且可更广泛获得,因此实际上任何人都能够建立一个小型光盘生产厂。音乐和软件的盗版问题影响这些工业的每一个部门。当消费者购买了一张盗版拷贝而不是一张合法唱片时,零售商、批发商、艺术家、作曲家、出版者和音像公司都受到影响。认为每年要制造几亿张伪造CD和DVD,且每年要销售几亿张CD-R和DVD-R。
在塑料材料中使用标记物进行识别是本领域已知的技术。已经将紫外和近红外荧光染料加入聚合物中用于识别目的。在常规方法中,将近红外荧光团引入聚碳酸酯基体中。这些常规方法的缺点是,在正常使用条件下,所述条件包括暴露在紫外线中、高的环境温度等,如果任何染料老化或者沥出,则会产生错误信号。而且,聚合物中的添加剂会改变荧光强度的比率。
为了标记光学介质,将标记物涂覆在制品上的一个或多个确定位置上而不是涂覆在整个表面上是有利的。而且,将所述标记物涂覆在正在进行旋涂工艺的制品上是有利的,由于所得到的涂层的质量、旋涂工艺的高速和低生产成本,因此旋涂工艺是用于向光学介质涂覆涂层的常用方法。
发明内容
在本发明的各个实施方案中,描述了用于在光学介质制品的精确控制的预定位置涂覆标记物的方法。光学介质制品的实例包括但不限于CD、CD-R、CD-RW、DVD、DVD-R、DVD-RW、蓝光光盘(Blu-ray)以及本领域已知的其它任何光学存储介质。在光学制品上涂覆标记物达到不同的目的。这些目的包括但不限于防剽窃保护、识别、标记、装饰性涂覆和通常用于光学介质制品的其它任何应用。
在一个实施方案中,在光学介质制品的生产过程中,在该制品上加入光谱标记物。光谱标记物是具有有利于识别聚合物和聚合物制品的若干性质的材料。这些标记物是表现出以下性质的化合物:比色、光折变、光致变色、热致变色、荧光、弹性散射、非弹性散射和对于引入光学介质制品中有用的其它任何光学性质。为了涂覆光谱标记物,修饰制品的表面以改变其表面能。当精确控制的预定位置的表面能变化时,溶解在合适溶剂中的被涂覆的标记物被吸引到预处理区域。可以选择和/或修饰光学制品的材料以提供保持标记物位于制品表面所需的性质。这些修饰包括但不限于不同的共聚物材料、添加剂、封端和本领域已知的其它任何修饰。
在另一个实施方案中,将溶解在合适溶剂中的光谱标记物涂覆在光学介质制品的整个表面。在某些应用中,不必将标记物溶解在溶剂中。当光学制品受到离心力时,标记物被保留在以前修饰过的区域中并且在离心力的作用下除去未修饰区域的标记物。在一个实施方案中,可以借助于常规的光学介质制品读出器中使用的激光器来读出标记物。在另一个实施方案中,可以在光盘驱动器的外部读出标记物。
在又一个实施方案中,本发明提供了一种包含识别标记的光学制品,该识别标记是通过包括以下步骤的方法制造的:将染料溶解在合适的溶剂中以形成溶液,修饰光学制品表面的预定位置以改变该预定位置的表面能,在光学制品的整个表面上涂覆该溶液,使光学制品进行产生离心力的旋转运动,以及保留位于经修饰的预定位置的染料,同时在离心力的作用下除去光学制品表面的未修饰位置的染料。
在再一个实施方案中,光谱标记物的材料包括有机和无机染料和颜料、纳米晶体、纳米粒子、量子点、有机荧光团、无机荧光团和本领域已知的其它任何染料。在其它实施方案中,所述材料的尺寸为约1纳米-约10微米,且可以溶解或分散的形式将所述材料加入溶液中。这些染料和颜料的激发波长可以在或者可以不在光学介质播放器和记录器中使用的激光二极管的工作范围内,而且其中读出标记物是使用光学介质制品的播放器或者记录器的激光或者使用光盘驱动器外部的光源进行的。
本申请包括:
1、一种赋予光学存储介质(46)以光谱标记物(54)的方法,其包括:
修饰光学存储介质(46)涂层表面(44)上的预定位置以改变预定位置的表面能;
以均匀薄膜的形式将光谱标记物(54)涂覆在光学存储介质(46)涂层的整个表面(44)上;以及
将光谱标记物(54)保留在经修饰的预定位置,同时从未修饰区域除去光谱标记物(54)。
2、项1的方法,其还包括:
使光学存储介质(46)进行产生离心力的旋转运动;以及
将光谱标记物(54)保留在经修饰的预定位置,同时借助于离心力从未修饰区域除去光谱标记物(54)。
3、项1的方法,其中光谱标记物(54)是选自有机染料和颜料、无机染料和颜料、纳米晶体、纳米粒子、量子点、有机荧光团和无机荧光团的染料。
4、项1的方法,其中光学存储介质(46)包括光学透明的基片(26),所述基片(26)的激光入射面或者与反射层相邻的数据层上涂布有光谱标记物(54),且其中所述反射层被溅射在光学透明的基片(26)上。
5、项1的方法,其中光谱标记物(54)的激发波长位于光学介质制品播放器或记录器中使用的激光二极管(42)的工作范围内,且其中光谱标记物(54)的读出是由光学介质制品播放器或记录器的激光器进行的。
6、项2的方法,其中光谱标记物(54)的激发波长位于光学介质制品播放器或记录器中使用的激光二极管(42)的工作范围之外,且其中光谱标记物(54)的读出是在光学介质制品播放器的外部进行的。
7、项1的方法,其中选择和/或修饰光学存储介质(46)的材料以提供保持溶解光谱标记物(54)位于光学存储介质涂层表面(44)所需的性质。
8、项7的方法,其中所述修饰包括不同的共聚物材料、表面偏析(surface-segregating)添加剂和封端。
9.项1的方法,其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
10.项1的方法,其中使用光诱导表面修饰法来修饰光学存储介质表面(44)上的预定位置。
11.项1的方法,其还包括通过在光学存储介质(46)的涂层的整个或者部分表面(44)上涂覆纯溶剂来洗去多余的光谱标记物(54)。
12.项1的方法,其中光谱标记物(54)不干扰光学存储介质(46)的光学性质。
13.一种标记光学存储介质(46)的方法,其包括:
使用辐射源修饰光学存储介质(46)涂层表面(44)上的预定位置;
将染料溶解在合适的溶剂中以形成溶液;
将该溶液以均匀薄膜的形式涂覆在光学存储介质(46)的涂层表面(44);
将染料保留在光学存储介质(46)涂层表面(44)上的经修饰的预定位置上以形成光谱标记物(54);和
将染料从光学存储介质(46)涂层表面(44)上的未修饰位置除去。
14.项13的方法,其还包括:
当光学存储介质进行旋转运动时,将溶液以均匀薄膜的形式涂覆在光学存储介质(46)的涂层表面(44);以及
利用旋转运动产生的离心力将染料从光学存储介质(46)涂层表面(44)的未修饰位置除去。
15.项13的方法,其中所述染料是荧光团。
16.项13的方法,其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
17.一种光学存储介质(46),其包括通过包括以下步骤的方法制成的光谱标记物(54):将染料溶解在合适的溶剂中以形成溶液,修饰光学存储介质(46)表面(44)上的预定位置以改变预定位置的表面能,将溶液涂覆在光学存储介质(46)的整个表面(44)上,使光学存储介质(46)进行产生离心力的旋转运动,以及将染料保留在预定位置,同时借助于离心力将染料从光学存储介质(46)表面(44)的未修饰位置除去。
18.项17的光学存储介质(46),其中光谱标记物(54)不干扰光学存储介质(46)的光学性质。
19.项17的光学存储介质(46),其还包括通过在光学存储介质(46)的整个表面(44)涂覆纯溶剂,将多余的染料从光学存储介质(46)表面(44)的未修饰区域除去。
20.项17的光学存储介质(46),其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
21.一种赋予光学存储介质(46)以光谱标记物(54)的方法,其包括:
修饰光学存储介质(46)表面(44)上的预定位置以改变预定位置的表面能;
以均匀薄膜的形式将光谱标记物(54)涂覆在光学存储介质(46)的整个表面(44);以及
将光谱标记物(54)保留在未修饰位置,同时将光谱标记物(54)从经修饰的预定位置除去。
22.项21的方法,其还包括:
使光学存储介质(46)进行产生离心力的旋转运动;以及
将光谱标记物(54)保留在未修饰位置,同时借助于离心力将光谱标记物(54)从经修饰的预定位置除去。
23.项21的方法,其中光学存储介质(46)包括光学透明的基片(26),所述基片(26)的激光入射面或者与反射层相邻的数据层上涂布有光谱标记物(54),且其中所述反射层被溅射在光学透明的基片(26)上。
24.项21的方法,其中使用化学修饰法来修饰光学存储介质(46)表面(44)上的预定位置。
附图说明
下面参考附图说明本发明的多个具体实施方案。在这些图中,使用相同附图标记表示相同元件。
图1是根据本发明的一个示例性实施方案,说明在旋转的光学介质制品上涂覆标记物的主要步骤的功能性方框图;
图2是根据本发明的一个示例性实施方案,说明旋涂装置影响沉积材料的示意图;
图3是根据本发明的一个示例性实施方案,说明光学介质和光学介质读出器的实例的示意图;
图4是光学介质制品(DVD)的透视图,其根据本发明的一个示例性实施方案,说明溶剂在经修饰的宏观区域上的保持力;
图5是图3的光学介质制品的透视图,其根据本发明的一个示例性实施方案,说明制品旋转时刚刚完成染料沉积之后的制品表面;
图6是图4的光学介质制品的透视图,其根据本发明的一个示例性实施方案,说明在除去多余染料的洗涤步骤之后保留染料的制品的经修饰和染料处理的区域;以及
图7是跨过沉积在旋转光学介质制品上的6个点测得的在650nm处的空间分辨反射率变化的图形示意图。
具体实施方式
根据需要,这里公开了本发明的具体实施方案,但是,应当理解,所公开的实施方案仅仅是本发明的示例,其可以多种形式和替代形式体现。这里公开的具体结构性和功能性细节不应理解为限制性的,而是仅仅以用于教导本领域的技术人员以不同的方式使用本发明的代表性基础的形式作为权利要求书的基础。在所有附图中,相同元件具有相同的附图标记。下面将要描述的方法适用于标记光学介质制品,但是,在原则上也适用于标记用于多种应用的塑料制品。
下面参考小型光盘(CD)描述本发明方法,但是,该方法可以用于任何光学制品,例如CD、CD-R、CD-RW、DVD-R、DVD-RW、蓝光光盘等。为了实施本发明方法,首先提供基体。所述基体可以为任何类型,且应当事先以凹洞(pit)和/或连续沟道的形式在至少一面上进行信息编码。通常,CD是透明聚碳酸酯塑料的注塑制品。在生产过程中,塑料被压有微小突起(bump),所述微细突起排列成单个的、连续的、极长的数据螺旋轨道。数据螺旋轨道从光盘内部盘旋到外部。当形成透明聚碳酸酯时,将反射薄层(通常是铝、银或金)溅射在光盘上,覆盖微小突起。然后将丙烯酸(酯)薄层喷涂在反射层上以保护反射层并提供用于标记的表面。当讨论CD时,经常提到的是凹洞而不是突起。凹洞出现在反射面,而突起出现在激光器读出的一面。光学介质播放器执行寻找和读出作为光学介质制品上的突起而被存储的数据的任务。
光学制品基体的材料在类型上不重要,应当优选具有高的透光性。所述材料的实例包括但不限于热塑性树脂例如聚碳酸酯、聚甲基丙烯酸甲酯等,以及热固性树脂例如环氧树脂等。当然,透光的热塑性树脂例如聚碳酸酯是优选的。可以选择和/或修饰光学制品的材料以提供在表面上保留溶解染料所需的性质。这些修饰可以包括但不限于不同的共聚物材料、添加剂、封端和本领域已知的其它任何修饰。
在形成聚合物的聚合反应中,生长的聚合物链的端部具有反应性基团,可用于聚合物链的继续生长。当发生导致引入不含该反应性基团的结构部分的替代反应时,所述链继续链增长的能力终止。具有这种端基的链称作被封端。例如,光学制品通常由聚碳酸酯制成,当碳酸二苯酯和双酚A反应时,生成具有反应性羟基的生长聚合物,所述羟基可用于聚合物链的继续生长。当发生导致引入不含该反应性羟基的结构部分的替代反应时,所述链的继续链延长的能力终止。现有技术中已经公开了多种封端剂,包括在美国专利4,774,315、5,028,690、5,043,203、5,644,017和5,668,202中公开的封端剂。
任选地,可以通过缩聚法制造聚碳酸酯光学制品,所述缩聚法涉及双酚单体和光气或碳酸二苯酯以及被选择用于改变任选被处理和未处理光学制品的表面能的任选单体。能够修饰表面能的共聚单体或添加剂的实例包括封端单体例如单官能酚、导致增加的端基形成的支化剂、含硅氧烷的单体和添加剂、抗静电剂、防雾剂、表面偏析(surface-segregating)添加剂以及其它添加剂。
在多个实施方案中,提供了用于在光学制品例如CD表面上的预定位置涂覆光谱标记物的方法。光谱标记物是具有有利于识别聚合物和聚合物制品性质的材料。初始地,将标记物材料溶解或分散在合适的液体溶剂(方框10)中,从而以溶液或分散液的形式提供标记薄层,后来使用旋涂技术涂覆该溶液或分散液。在一个替代实施方案中,不必将标记物溶解在合适的溶剂中。用于溶解标记物材料的液体溶剂可以是能够溶解或分散染料并对光学制品表面没有腐蚀性的任何液体。优选地,溶剂包括水、甲醇、乙醇、异丙醇和甲氧基丙醇。这些溶剂可以单独或者组合使用。
在一个替代实施方案中,当染料不是能够溶解于液体介质中的化合物时,所述染料可以与黏合剂用树脂连用。所用黏合剂用树脂应当具有低浓度,以便不会不利地影响制品的厚度和制品的光学性质。可以将黏合剂用树脂溶解在溶剂中,不溶性染料可以与黏合剂用树脂结合并变得可分散在液体介质中。所用黏合剂用树脂的类型不重要。优选地,可以使用热塑性聚合物,例如包括树脂,例如聚苯乙烯、聚(α-甲基苯乙烯)、聚茚、聚(4-甲基-1-丙烯)、聚乙烯基吡啶、聚乙烯醇缩甲醛、聚乙烯醇缩乙醛、聚乙烯醇缩丁醛、聚乙酸乙烯酯、聚乙烯醇、聚氯乙烯、聚1,2-二氯乙烯、聚乙烯基甲醚、聚乙烯基乙醚、聚乙烯基苄基醚、聚乙烯基甲基酮(polyvinyl methyl ketone)、聚(N-乙烯基咔唑)、聚(N-乙烯基吡咯烷酮)、聚丙烯酸甲酯、聚丙烯酸乙酯、聚丙烯酸、聚丙烯腈、聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丁酯、聚甲基丙烯酸苄酯、聚甲基丙烯酸环己酯、聚甲基丙烯酸、聚酰胺甲基丙烯酸酯(polyamide methacrylate)、聚甲基丙烯腈、聚乙醛、吡啶和三氯乙醛的产物(polychloral)、聚氧化乙烯、聚氧化丙烯、聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、双酚和碳酸的聚碳酸酯、聚(二乙二醇/碳酸二烯丙基酯)、尼龙-6、尼龙-6,6、尼龙-12、尼龙-6,12、聚天门冬氨酸乙酯、聚谷氨酸乙酯、聚赖氨酸、聚脯氨酸、聚(.γ.-L-谷氨酸苄酯)(poly(.gamma.-benzyl-L-glutamate))、甲基纤维素、羟丙基纤维素、乙酰基纤维素、三乙酸纤维素、三丁酸纤维素、聚氨酯树脂等;有机聚硅氧烷例如聚(苯基甲基硅烷);有机聚锗化合物、以及上述聚合物或树脂中的单体成分的共聚物或共缩聚物。
仍然参见图1,在向光学制品上涂布含染料的溶液之前,在光学制品表面制造精确控制的预定位置用于接收和保留染料。光学介质上的精确控制的一个预定位置(位置专一性的(site-specific))或多个预定位置被定义为用于沉积可用于识别目的的标记物的局部区域。在一个替代实施方案中,例如为了防止预定位置保留染料,可对预定位置进行化学修饰,例如通过喷涂硅树脂。预定位置可以具有任何方便的形状,例如线形、环形、矩形、椭圆形等。预定区域的表面积、标记物数目和位置可视具体的涂覆方法而定。
使用例如来自汞灯的紫外(UV)线(方框11)或者通过化学修饰来改变预定位置的表面能。可以穿过掩膜曝光预定位置,下面将对其进行详细描述。当改变确定位置的表面能时,溶解在溶剂中的被涂覆的标记物优选被吸引到预处理区域或者被排斥离开预处理区域。通过使用紫外光源所产生的高能光子氧化表面从而对表面进行修饰。也可以使用本领域已知的其它类型的表面修饰方法。其它光源也可以用于此目的。表1中给出了部分光源的列表。
光源 | 发射光谱范围(nm) |
连续波光源:氙弧灯汞弧灯氘灯钨灯发光二极管二极管激光器氩离子激光器脉冲光源:氮激光器Nd:YAG激光器染料激光器 | 200-1000250-600180-420320-2500不同的二极管覆盖370-1500nm的范围不同的二极管激光器覆盖约400-1500nm的范围350-514nm的几条线337nm三倍频-355;四倍频-266倍频200-450 |
表1.用于在光学介质制品上沉积标记物的光源
通常,为了修饰光学制品表面的未遮蔽区域,可以将物理遮蔽系统与多种染料沉积技术连用。掩膜包括一个或多个贯穿布置的洞或者在其内布置的孔。一个或多个洞或孔中的每一个例如都可以基本上为圆形、长方形、正方形、矩形、三角形或者更为复杂的形状。将掩膜布置在与光学制品表面相邻的位置,从而选择性地阻挡或者防止通过多个孔中的每一个孔的光接触光学制品表面的预定位置。可以将光闸(shutter)布置在掩膜上方。光闸是通过开启/关闭来选择性地允许/阻止光线接触光学制品表面的机械装置。在一个实施例中,可以将具有约1mm-约10mm的孔的掩膜放置在光学制品表面上。然后穿过掩膜施加紫外光以改变表面能并修饰制品的未遮蔽区域。在制品表面上,被修饰区域的厚度和形状会不同。通常,掩膜包括板、片、膜、涂层等。根据具体的涂覆方法,掩膜可以不是该系统中的必要组件。
当光学制品表面已被预处理且标记物已经溶解在合适的溶剂中时,将该溶液或分散液涂覆在制品的整个表面。在本发明的实践中,当制品进行旋转、另一种类型的运动或者不运动时,将该溶液涂覆在制品上(方框12)。由于所得到的涂层的质量、旋涂法的高速和低制造成本,因此旋涂法是用于向光学制品上涂布涂层的常用方法。参见图2,旋涂法涉及利用旋转元件22加速旋转基片26上的溶液材料24(沉积材料)。手动或者使用计算机控制的装置和输送装置28将溶液材料24沉积在基片的中心。再次参见图1,该溶液可以作为流动涂层被涂覆在光学制品的整个表面。在替代实施方案中,气相沉积或者溶剂流延(casting)可能是合适的方法。旋涂法后面的物理原理涉及转速控制的离心力与溶剂粘度所决定的粘滞力之间的平衡。可以通过改变溶液粘度、固体含量、角速度和旋转时间来控制旋涂技术。
仍然参见图1,由旋涂过程产生的离心力将溶液从制品中心拉向制品的外边缘。染料被吸引到预处理位置且被保留在这些位置,但是染料不被吸引到未处理区域并从这些区域被除去(方框18)。在任选步骤(方框20)中,通过在制品的整个表面上涂覆纯溶剂从而将多余的染料从制品表面洗去。
整个标记过程可以手动或者自动控制。例如,可以使用注射器型仪器手动将一种或多种溶有染料的溶液从样品库中取出并手动转移到光学制品表面。在自动体系中,该体系的一些功能被自动执行,例如样品选择或转移。溶剂浓度可以通过程序控制从而增加、保持不变、下降或者任何其它功能。优选地,为了快速和正确地选择样品和合适的测量法,以完全自动的方式例如使用自动取样器将样品从各自的容器中取出并转移。可以对自动取样器的微处理器设定程序以指挥自动取样器从样品瓶中取出样品放入转移装置28中,然后指挥该装置。在一个实施方案中,对自动取样器设定程序从而根据所需标记物自动地对一种溶液,然后对另一种溶液进行取样。优选地,自动取样器的微处理器包括可被编程以用于各种取样方案的用户界面。自动取样器也可以手动控制。
优选地,通过转移装置28的运动或者通过光学制品的运动,例如使用可编程的x、y、z阶段等,转移装置28可相对于光学制品表面运动。通过对两种或多种含染料的溶液使用不同的加料速率并且同时在x、y或z方向上移动标记物来形成连续流动涂层。在一个实施方案中,可以将染料涂覆在预处理区域,旋涂,然后干燥。接着,可使用第二种不同的染料溶液处理表面的另一个区域并重复旋涂过程。根据所需的应用,可以重复该过程任意次数。
光谱标记物的材料可以包括本领域已知的任何染料。所述染料包括有机和无机染料和颜料、纳米晶体和纳米粒子、量子点,以及可以溶解或分散的形式加入溶液中的、尺寸为约1纳米(nm)-约10微米的其它任何类型的材料。光谱标记物的实例包括有机和无机化合物。
有机化合物的实例包括有机染料、有机荧光团、荧光染料、红外吸收染料、紫外吸收染料、光致变色染料、热致变色染料以及可用于此目的的其它已知染料。染料的具体实例包括呫吨染料例如罗丹明B(rhodamine B)、罗丹明6G、曙红(eosine)、焰红染料B等;吖啶染料例如吖啶橙、吖啶红等;偶氮染料例如乙基红、甲基红等;卟啉染料;酞菁染料;菁染料例如3,3’-二乙基硫碳菁碘化物(3,3’-diethylthiacarbocyanine iodide)、3,3’-二乙氧基二碳菁碘化物(3,3’-diethyloxadicarbocyanine iodide)等;部花菁(merocyanine)染料;苯乙烯基型染料;氧杂菁(oxonol)染料;三芳基甲烷染料;亚甲基蓝;酚蓝等。根据所需的应用,这些染料可以单独或者组合使用。有机化合物的宽的含量范围取决于有机化合物的类型和用途。例如,荧光染料可以ppm的剂量加入树脂黏合剂中,这是本领域已知的。
标记物结合到具体的预定位置并且当受到特定波长的光激发时发荧光。合适的波长范围是约640nm-约1100nm。表2中给出了这些材料的非限制性实例。
标记材料 | 激发波长(nm) | 发射波长(nm) |
三(二(4-溴)-苯甲酰甲烷)-单(菲咯啉)铕(III)(Tris(di(4-bromo)-benzoylmethane)-mono(phenanthroline)europium(III)) | ~400 | ~615 |
三(二联苯酰甲烷)-单(菲咯啉)铕(III)(Tris(dibiphenoylmethane)-mono(phenanthroline)europium(III)) | ~410 | ~615 |
三(2-苯基吡啶)铱(III) | ~400 | ~515 |
甲酚紫(Cresyl violet) | ~600 | ~630 |
耐尔蓝(Nile blue) | ~633 | ~675 |
噁嗪1 | ~645 | ~670 |
噁嗪4 | ~615 | ~660 |
罗丹明700 | ~645 | ~700 |
DDI | ~710 | ~745 |
IR125 | ~795 | ~840 |
DTTCI | ~760 | ~815 |
HDITCI | ~780 | ~825 |
CdSe纳米粒子,晶体直径=2.8nm | ~520 | ~535 |
CdSe纳米粒子,晶体直径=3.4nm | ~545 | ~560 |
CdSe纳米粒子,晶体直径=4.0nm | ~575 | ~585 |
CdSe纳米粒子,晶体直径=4.7nm | ~595 | ~610 |
CdSe纳米粒子,晶体直径=5.6nm | ~625 | ~640 |
表2.用于荧光标记旋转光学介质制品的材料
其它结合到具体预定位置的非荧光标记物也是可用的。表3中给出了这些材料的非限制性实例和合适的检测波长。
标记材料 | 吸收波长(nm) |
光致变色醌 | 400-800 |
光致变色紫罗碱(viologens) | 400-800 |
螺噁嗪(spirooxazines) | 400-750 |
螺吡喃(spiropyrans) | 400-750 |
表3.用于非荧光标记旋转光学介质制品的材料
下面的实例给出了其它类型的标记物,这些实例并非要限制本发明的范围。这些标记物包括热致变色化合物。热致变色化合物的实例包括可从Matsui-color获得的几种染料。它们还包括红外吸收化合物例如酞菁染料、钴或铂复合物/螯合物;一些瓮染料(VAT dyes)例如蒽醌和亚甲基蓝;尼格罗黑(nigrosine)化合物例如Keystone Black R or Anirox,以及尤其具有掺杂形式的共轭聚合物/低聚物(聚苯胺、聚亚苯基、聚噻吩、聚吡咯及其衍生物)。其它吸热化合物的实例包括微胶囊化的(microencapsulated)可喷涂型液晶。它们例如可从Liquid Crystal Resources,Inc.获得,具有宽的转变温度范围。室温液晶的一个实例是得自Liquid Crystal Resources,Inc.的SPC/R25C5W。热敏散射化合物(temperature sensitive scattering compounds)的实例包括室温下在基体中恰好高于临界浓度的盐,以及室温下低于下部临界会溶温度(LCST)的聚合物共混物。具有折射率变化的材料的实例包括液晶高分子,开发用于全息存储的聚合物,在全息存储中,当温度升高时这些聚合物的折射率或者双折射发生变化。具有尺寸稳定性变化的材料的实例包括例如具有高的热膨胀系数的材料。
荧光团的激发波长位于常规的光学介质读出器/记录器中使用的多种可得光源和激光二极管的工作范围内。在一个实施方案中,可使用激光二极管读出光谱标记物。在一个替代实施方案中,在光盘驱动器的外部读出标记物。虽然下面讨论光学介质读出器的一个实施方案,但是应当理解,可以使用本领域已知的任何光学介质读出器来实施本发明的方法。常规的光学读出器包括与跟踪装置连接的光学读/写读取装置。通常,在工作过程中,将光学读/写头和跟踪装置置于与旋转的光学存储介质表面相邻的位置。图3示出了该构造。
参见图3,光学读/写头40包括光源42例如激光二极管等,其可工作用于发射编码/未编码的光例如激光等至光学存储介质46的表面44。光学读/写头40还包括光接收装置48例如光电二极管等,其可工作用于接收来自光学存储介质46表面44的编码/未编码的光例如激光或类似光线。反射元件50例如半反射镜、分光器等,以及聚焦透镜52或其它聚焦光学元件也可以用于向光学存储介质46表面44发射光线和/或接收来自光学存储介质46表面44的光线。
使用光学读/写头40,通过选择性地定位跟踪装置56和光学读/写头40,从光学存储介质46表面44的预定位置读出光谱标记物54和数据。通常,跟踪装置56包括活动式地连接至一个或多个导轨60的读取载体装置58,一部分导轨可以成线状。一个或多个导轨60可以与伺服电动机62等一起工作,以相对于光学存储介质46表面44线性地移动跟踪装置56和光学读/写头40。
其它标记光学制品的方法可以包括将染料溶解在合适的溶剂中以及通过合适的涂布方法例如旋涂、浸涂(浸渍)、转印法、丝网印刷法等用含染料的试剂溶液涂布光学制品。染料被吸收到预处理区域内或上,并且被保留在制品表面。任选地,可以通过使用纯溶剂洗涤制品表面从而将多余染料从未处理区域除去。
其它标记光学制品的方法可以包括将染料溶解在合适的溶剂中以及通过合适的涂布方法用含染料的试剂溶液涂布光学制品的整个或部分表面。任选地,可以通过使用纯溶剂洗涤制品表面从而将一些染料涂层从表面区域除去。
将标记物涂覆在光学介质制品表面达到多个目的,例如识别、防盗版、标记、装饰性涂覆,以及通常用于光学介质制品的其它任何应用。
实施例1
将具有约5mm孔的掩膜置于数字化视频光盘(DVD)的表面上。为了修饰制品的未遮掩区域,穿过掩膜施加光线。使用低强度手持汞灯作为光源来修饰光学制品的表面。当曝光完成时,移去掩膜并将水倒在具有修饰区域的制品表面。图4示出证明溶剂在光学介质制品(DVD)的预定修饰的宏观区域上保持力的试验结果。然后将有机染料(亚甲基蓝)溶解在水中,并将该溶液倒在上述修饰的、旋转的光学介质制品上。紧接着染料沉积之后的制品表面示于图5中。然后使用纯溶剂洗涤表面以除去多余的染料。如图6所示,离心力对溶液的作用结果是,制品的修饰区域保留染料,但是未修饰区域不保留染料。图7示出了穿过沉积在旋转的光学介质制品上的其中一个点所测得的、在650nm处的空间分辨反射率变化。
实施例2A
以1.5wt%的浓度将酞菁金属复合物(Sands SDS8303)溶解在DowanolPM溶剂中。将大约3ml的溶液分散在距中心孔约20mm的未镀金属膜的聚碳酸酯CD基片的表面。然后以约1000rpm旋转该基片,将溶液分散在CD的表面。然后干燥该涂层过夜。使用Steag Unijet CD电镀机以约40-60nm的厚度在基片的涂布面溅射铝。得到的CD在650nm处的吸光度为0.37,在聚碳酸酯基片和铝反射层之间夹有酞菁染料涂层。
实施例2B
按照实施例2A制造其它涂布的CD,不同的是将涂层溶液分散在距中心孔约40mm处。然后,在旋涂染料溶液之后,再次旋转光盘,同时使用Dowanol PM溶剂在从距中心孔约45mm处至光盘边缘洗涤基片。洗涤步骤的结果是,只有~5mm的染料涂层带保留在光盘表面。
实施例2C
按照实施例2B制造其它涂布的CD,但是将铝溅射在染料涂布的光盘上,导致在聚碳酸酯基片和反射层之间夹有染料涂层。
实施例2D
按照实施例2A制造其它涂布的CD,但是涂层溶液含有存在于DowanolPM中的1.3wt%Lambdachrome IR125染料和15wt%聚(甲基丙烯酸甲酯)。得到的CD在780nm处的吸光度为0.54,在聚碳酸酯基片和铝反射层之间夹有含IR125染料的PMMA涂层。
实施例2E
按照实施例2D制造其它涂布的CD,但是涂层溶液含有存在于DowanolPM中的1.3wt%罗丹明800染料和15wt%聚(甲基丙烯酸甲酯)。得到的CD在650nm处的吸光度为0.1,在聚碳酸酯基片和铝反射层之间夹有含有罗丹明800染料的PMMA涂层。
很明显,根据本发明方法,已经提供了用于在精确控制的预定位置标记旋转光学介质制品的方法。虽然已经参考优选实施方案和实施例描述了本发明的方法,但是其它实施方案和实施例也可以执行相似的功能和/或实现相似的结果。权利要求书意指涵盖属于本发明的实质和范围内的所有等同实施方案和实施例。
Claims (24)
1.一种赋予光学存储介质(46)以光谱标记物(54)的方法,其包括:
修饰光学存储介质(46)涂层表面(44)上的预定位置以改变预定位置的表面能;
以均匀薄膜的形式将光谱标记物(54)涂覆在光学存储介质(46)涂层的整个表面(44)上;以及
将光谱标记物(54)保留在经修饰的预定位置,同时从未修饰区域除去光谱标记物(54)。
2.权利要求1的方法,其还包括:
使光学存储介质(46)进行产生离心力的旋转运动;以及
将光谱标记物(54)保留在经修饰的预定位置,同时借助于离心力从未修饰区域除去光谱标记物(54)。
3.权利要求1的方法,其中光谱标记物(54)是选自有机染料和颜料、无机染料和颜料、纳米晶体、纳米粒子、量子点、有机荧光团和无机荧光团的染料。
4.权利要求1的方法,其中光学存储介质(46)包括光学透明的基片(26),所述基片(26)的激光入射面或者与反射层相邻的数据层上涂布有光谱标记物(54),且其中所述反射层被溅射在光学透明的基片(26)上。
5.权利要求1的方法,其中光谱标记物(54)的激发波长位于光学介质制品播放器或记录器中使用的激光二极管(42)的工作范围内,且其中光谱标记物(54)的读出是由光学介质制品播放器或记录器的激光器进行的。
6.权利要求2的方法,其中光谱标记物(54)的激发波长位于光学介质制品播放器或记录器中使用的激光二极管(42)的工作范围之外,且其中光谱标记物(54)的读出是在光学介质制品播放器的外部进行的。
7.权利要求1的方法,其中选择和/或修饰光学存储介质(46)的材料以提供保持溶解光谱标记物(54)位于光学存储介质涂层表面(44)所需的性质。
8.权利要求7的方法,其中所述修饰包括不同的共聚物材料、表面偏析添加剂和封端。
9.权利要求1的方法,其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
10.权利要求1的方法,其中使用光诱导表面修饰法来修饰光学存储介质表面(44)上的预定位置。
11.权利要求1的方法,其还包括通过在光学存储介质(46)的涂层的整个或者部分表面(44)上涂覆纯溶剂来洗去多余的光谱标记物(54)。
12.权利要求1的方法,其中光谱标记物(54)不干扰光学存储介质(46)的光学性质。
13.一种标记光学存储介质(46)的方法,其包括:
使用辐射源修饰光学存储介质(46)涂层表面(44)上的预定位置;
将染料溶解在合适的溶剂中以形成溶液;
将该溶液以均匀薄膜的形式涂覆在光学存储介质(46)的涂层表面(44);
将染料保留在光学存储介质(46)涂层表面(44)上的经修饰的预定位置上以形成光谱标记物(54);和
将染料从光学存储介质(46)涂层表面(44)上的未修饰位置除去。
14.权利要求13的方法,其还包括:
当光学存储介质进行旋转运动时,将溶液以均匀薄膜的形式涂覆在光学存储介质(46)的涂层表面(44);以及
利用旋转运动产生的离心力将染料从光学存储介质(46)涂层表面(44)的未修饰位置除去。
15.权利要求13的方法,其中所述染料是荧光团。
16.权利要求13的方法,其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
17.一种光学存储介质(46),其包括通过包括以下步骤的方法制成的光谱标记物(54):将染料溶解在合适的溶剂中以形成溶液,修饰光学存储介质(46)表面(44)上的预定位置以改变预定位置的表面能,将溶液涂覆在光学存储介质(46)的整个表面(44)上,使光学存储介质(46)进行产生离心力的旋转运动,以及将染料保留在预定位置,同时借助于离心力将染料从光学存储介质(46)表面(44)的未修饰位置除去。
18.权利要求17的光学存储介质(46),其中光谱标记物(54)不干扰光学存储介质(46)的光学性质。
19.权利要求17的光学存储介质(46),其还包括通过在光学存储介质(46)的整个表面(44)涂覆纯溶剂,将多余的染料从光学存储介质(46)表面(44)的未修饰区域除去。
20.权利要求17的光学存储介质(46),其中光谱标记物(54)用于识别、防盗版、标记和装饰性涂覆。
21.一种赋予光学存储介质(46)以光谱标记物(54)的方法,其包括:
修饰光学存储介质(46)表面(44)上的预定位置以改变预定位置的表面能;
以均匀薄膜的形式将光谱标记物(54)涂覆在光学存储介质(46)的整个表面(44);以及
将光谱标记物(54)保留在未修饰位置,同时将光谱标记物(54)从经修饰的预定位置除去。
22.权利要求21的方法,其还包括:
使光学存储介质(46)进行产生离心力的旋转运动;以及
将光谱标记物(54)保留在未修饰位置,同时借助于离心力将光谱标记物(54)从经修饰的预定位置除去。
23.权利要求21的方法,其中光学存储介质(46)包括光学透明的基片(26),所述基片(26)的激光入射面或者与反射层相邻的数据层上涂布有光谱标记物(54),且其中所述反射层被溅射在光学透明的基片(26)上。
24.权利要求21的方法,其中使用化学修饰法来修饰光学存储介质(46)表面(44)上的预定位置。
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US10/317,772 | 2002-12-12 | ||
US10/317,772 US20040115421A1 (en) | 2002-12-12 | 2002-12-12 | Methods for application of tags onto optical media articles |
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CN100399444C true CN100399444C (zh) | 2008-07-02 |
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JP (1) | JP2006510154A (zh) |
KR (1) | KR20050091719A (zh) |
CN (1) | CN100399444C (zh) |
AT (1) | ATE358873T1 (zh) |
AU (1) | AU2003298755A1 (zh) |
DE (1) | DE60313034T2 (zh) |
WO (1) | WO2004055802A1 (zh) |
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CN1745423A (zh) | 2006-03-08 |
EP1573728A1 (en) | 2005-09-14 |
AU2003298755A1 (en) | 2004-07-09 |
WO2004055802A1 (en) | 2004-07-01 |
US20040115421A1 (en) | 2004-06-17 |
DE60313034T2 (de) | 2007-12-13 |
DE60313034D1 (de) | 2007-05-16 |
ATE358873T1 (de) | 2007-04-15 |
JP2006510154A (ja) | 2006-03-23 |
EP1573728B1 (en) | 2007-04-04 |
KR20050091719A (ko) | 2005-09-15 |
US20050167510A1 (en) | 2005-08-04 |
US7508499B2 (en) | 2009-03-24 |
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