CN101470229A - 图案反射光学结构 - Google Patents
图案反射光学结构 Download PDFInfo
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- CN101470229A CN101470229A CNA2008101720729A CN200810172072A CN101470229A CN 101470229 A CN101470229 A CN 101470229A CN A2008101720729 A CNA2008101720729 A CN A2008101720729A CN 200810172072 A CN200810172072 A CN 200810172072A CN 101470229 A CN101470229 A CN 101470229A
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Abstract
一种包含光透射基片的光学结构，其中，将表面浮雕图案施加到所述光透射基片上，如全息图。反射材料图案层被应用在表面浮雕图案部分上，以形成文字数字符号、条形码或图解或绘画图案。为使表面浮雕图案的暴露部分产生期望的光学效果，在反射材料图案层和表面浮雕图案暴露部分上使用了光学活性涂层。在一些具体结构中，光学活性涂层为变色薄膜或包含变色片。任选地，光学活性涂层材料的折射率可与光透射基片的折射率显著匹配，以使未被反射材料覆盖的表面浮雕图案区部分不显示表面浮雕图案的光学效果。
Description
本申请是申请日为2004年9月16日、申请号为2004800258037，以及发明名称为“图案反射光学结构”的中国申请的分案申请。
发明背景
1.技术领域
[001]本发明通常涉及一种表面浮雕装置。特别的，本发明涉及与图案反射结构相关的装置，如全息图或衍射光栅。
2.背景技术
[002]衍射图、浮雕和相关领域的全息图因其美观实用而得到了广泛应用。一般来说，衍射光栅本质上是由材料中的许多线或槽构成的重复结构，以形成凹凸结构。如果衍射光栅在反射面每毫米的成百上千的线的范围内有隔开的槽，则可在可见光谱区内得到期望的光学效果。装饰效果就是由衍射光栅得到的一种彩虹视觉效果。
[003]在二维全息图的构建中采用衍射光栅技术，观察者视觉上将产生三维图形的幻觉。通过使用交叉激光束，基于聚合物折射率的不同也可生成三维全息图，所述交叉激光束包括一束参考光束和一束物光束。这样的全息图被称为体积全息图或3D全息图。而且，在各种目标物上使用全息图形以防止伪造也得到了广泛应用。
[004]目前，表面浮雕全息图也有多种应用，应用范围包括应用于礼物的装饰性包装、银行票据和信用卡等防伪文档。二维全息图通常是利用在塑料表面形成的衍射图形。在某些情况下，浮雕于这种表面的全息图形无需进一步处理即肉眼可见；然而，为得到最好的光学效果，通常需要加一层反射膜，典型的是在浮雕表面加一层薄金属(如铝)。反射层可以明显提高衍射图案浮雕的可视性。
[005]即使被封装在硬质塑料中，各种第一级衍射结构都存在一个明显缺陷，所述第一级衍射结构包括全息图和光栅图。当使用漫射光源(如普通的室内灯光或阴天的日光)来照射全息图时，所有的衍射级都将会扩展、重叠，从而使得衍射色彩丢失，全息图中包含的很多视觉信息也不会被显示。在这样的观测条件下，浮雕表面通常只能看见银色反射，并且所有这些图案看起来像银色或至多是淡而柔和的色彩。因此，为了看见图案，一般要求使用直接高光照射全息图。这意味着为了得到最好的观测效果，照射光必须按与观测角度相同的角度入射。
[006]由于防伪全息图已得到广泛的应用，因此造假者也非常渴望复制信用卡、银行票据及类似物上经常使用的全息图。因此，防伪全息图要真正安全，必须克服的困难是防止这样的全息图很容易被伪造。一步和两步光学复制、直接机械复制和甚至重组已在互联网上得到广泛的讨论。人们已经采用各种方法来阻止这些措施，但在反措施中，没有发现任何一种对策单独采用时具有有效的威慑。
[007]防伪全息图的另一个问题是对于大多数人来说，辨认和记住用于验证目的的全息图所生成的各种图像是困难的。由于其特征的复杂性和装饰性衍射包装的混乱，一般人最终辨认防伪全息图的能力大打折扣。因此，大多数人习惯于确认这种安全图案的存在与否而不是验证其图像的真实性。这为低级的伪造品和真正的防伪全息图的商业全息图替代品的使用提供了可趁之机。
[008]为了打击伪造者，全息图公司已借助于更复杂的图像，如当防伪图案旋转时，可以生成多种图案。这些增强图案可为观众提供高水平的“flash”或美的吸引力。不幸的是，这种增加的复杂性并不能相应地增加安全性，因为这种复杂的图案很难被理解，即使可能的话，回忆起这些图案也是一件很困难的事。
[009]因此，开发在各种光线条件下可增强观测性能的改进的防伪产品具有明显的优势，并且所述防伪产品能够应用到各种防伪应用中以使伪造更加困难。
发明摘要
[010]本发明涉及一种可显示表面浮雕图案的效果的光学结构，所述表面浮雕图案如全息图或衍射光栅，所述表面浮雕图案带有文字数字符号、条形码或图解或绘画图案和在所述图案周围的辅助光学效果。
[011]特别的是本发明中的光学结构包含了带表面浮雕图案的光透射基片，所述表面浮雕图案位于所述光透射基片上，以提供全息图或其它表面浮雕结构。反射材料图案层被应用在所述表面浮雕图案的部分区域，以形成图案或结构，如文字数字符号、条形码或图解或绘画图案。所述反射材料图案层的应用可使所述表面浮雕图案的其他部分不被反射体遮盖，或者称之为“暴露”。光学活性涂层被应用于所述反射材料图案层和表面浮雕图案的暴露部分，以使暴露于所述光学活性涂层的表面浮雕图案部分显示期望的光学效果。
[012]在一些具体结构中，所述光学活性涂层可以是变色薄膜或包含变色薄片。可选的，所述光学活性涂层的材料的折射率应与所述光透射基片的折射率匹配，这样就具有光学消除所述暴露部分的表面浮雕图案的效果。
[013]本发明的这些及其其它特征将在下面的描述和权利要求书中详细阐述，也可以通过实施上述描述而得到进一步了解。
附图说明
[014]为进一步澄清本发明上述的和其它的优点与特征，下面将根据附图中的具体实施例对本发明进行更详细描述。必须指出的是，所述附图只描述了本发明的特殊具体结构，但并不限于此。本发明的附加特征和细节通过附图所描述和解释，其中：
[015]图1是根据本发明一个具体实施例的光学结构的示意图；
[016]图2是根据本发明另一个具体实施例的光学结构的示意图；
[017]图3是根据本发明又一个具体实施例的光学结构的示意图；
[018]图4是根据本发明再一个具体实施例的光学结构的示意图；
[019]图5也是根据本发明另一个具体实施例的光学结构示的意图；
[020]图6是根据本发明又一个具体实施例的光学结构的示意图；和
[021]图7A和7B是根据本发明另一个具体实施例的防伪物品的示意图。
发明内容
[022]本发明直接涉一种光学结构，所述光学结构包括表面浮雕图案的，所述表面浮雕图案能够提供光学效果，如全息图；还包括位于所述表面浮雕图案下面的图案反射结构，以及位于所述图案层和未被所述图案层覆盖的表面浮雕图案部分下的光学活性涂层。最终的光学结构可显示唯一的光学效果。
[023]以示意图的形式阐述了本发明的各个要素，其中相同的结构使用相同的参考标志。
[024]图1描述了光学结构20，包括光透射层22，所述光透射层22在其内表面或下表面含有表面浮雕图案24。
[025]使用图案反射层26是为了支承表面浮雕图案。如图所示，图案反射层可以直接应用于表面浮雕图案上，或在表面浮雕图案和图案反射层之间可以有一个或多个透射层。
[026]使用“图案”反射层概念意味着，在表面浮雕图案24上应用反射层可得到期望的“图案”或设计。不局限于实施例，图案反射层可以以文字、数字、条形码和/或图解或绘画图案的形式出现。
[027]光透射层22更适宜使用可直接在其表面形成浮雕结构的材料制成。适用于层22的材料包括塑料，如聚氯乙稀、聚碳酸酯、聚丙烯酸酯和PET型G。
[028]表面浮雕图案24可以采用各种形式，包括衍射光栅、全息图(如二维和三维全息图)、角反射器、零级衍射图案、叠栅图(moiré pattern)或其它光干涉图案，和上述各种方式如全息图/光栅图或其它干涉图案的组合，所述衍射光栅、全息图或其它光干涉图包括基于尺寸约为0.1μm至约10μm微结构图，优选尺寸约为0.1μm至约1μm。比如，
装置有二维、微机生成的图像(可从瑞士的OVD Kinegram公司购买)，其中的各个图案元素就是用光衍射微结构填充而成的。这些微结构为典型尺寸小于1μm的非常细小的表面调制结构。除了传统的全息图外，本发明适用于任何可以在树脂层内浮雕出图案的浮雕结构。这包括衍射表面、“蛾眼(moth-eye)”型结构、有多角度视觉的全息结构，其中每个所述视觉都有一个不同的全息特征或图像，或者包括来自镍主导装置的高分辨率浮雕，其中原始薄片是使用高分辨激光刻蚀而成的。
[029]用于制造表面浮雕图案24的方法是该领域的技术人员所熟知的。例如，层22表面可以用人们熟知的方法浮雕制成，如在高压下将它与热的镍浮雕薄片紧紧压在一起即可。其它方法包括光刻法和塑料基片紧靠图案表面的压模法。
[030]在某一方法中，光学结构20可利用浮雕热塑性薄膜而制成，即先加热软化薄膜的表面，然后将薄膜通过浮雕滚筒，使得软化表面呈现衍射光栅或全息图。通过该方法，可有效地制造出无限长的带衍射光栅或全息图的薄片。另外一种制造光学结构20的方法是将一卷覆盖有可用紫外线(UV)固化的聚合物(如PMMA)的塑料膜通过一套可透射紫外线的滚筒，其中滚筒可将图案引入UV固化的聚合物。当聚合物通过可透射UV滚筒时，将被UV光固化。
[031]一旦光透射层和附属的表面浮雕结构制备好后，应将反射材料沉积在期望的图案上，以得到图案反射层26。虽然可以使用别的反射或甚至是部分反射/部分透射材料，但是目前优先用作图案反射层的材料是金属，如铝、银、镍、银-钯、银-铜合金、铜、金和类似物。虽然我们知道为得到期望的效果，该层可以是部分透射的，但是为改善附属表面浮雕图案的光学特性，该层首选的应该是实质上不透明的。当反射层实质上不透明时，金属层的典型厚度约为50～100nm。
[032]目前，首选将图案反射层应用于期望的图案/结构中有两种方法。一种方法是使用标准的光刻技术，其中图案是通过掩模法利用紫外线固化在金属层上形成一层光刻胶，然后用碱溶液(如氢氧化钠)去除光刻胶。另一种方法是在真空卷绕镀膜机中，通过在浮雕表面使用非浸湿型油的照相凹版印刷图案顺序制得金属层图像，其中图案金属层是在沉积过程中制备完成的。当金属沉积在浮雕表面上时，通过油蒸发而生成图案。在没有油的地方，金属将沉积并粘附在树脂层或基片表面上。在有油的地方，由于存在沉积金属冷凝热，油将蒸发，浮雕结构(如全息图)将保留在没有金属层的区域，即可得到非金属浮雕结构。
[033]虽然这两种制备图案反射层的方法是目前首选的，但是将会意识到，了解此处所讲的期望的结构的该领域的普通技术人员可以识别制备图案反射层的替代方法。
[034]图2描述了与图1相似的结构，但是为制备光学结构30，在光透射层22上增加光透射基片32。当用于制备光透射层22的材料为软性材料时，这个具体结构是非常有用的，因为基片32可为光学结构提供物理保护和/或刚性。另外，光透射层22的内表面有制备好的表面浮雕图案，并与图案反射层相连。
[035]目前，首选使用适用于模压的可热塑的材料来制备光透射基片32，其中包括塑料，如聚酯；聚对苯二甲酸乙二醇酯(PET)，如PET型G；聚碳酸酯，丙烯酸树酯，如聚丙烯酸树酯(包括聚甲基丙烯酸甲酯(PMMA))；聚氯乙烯；聚偏二氯乙烯；聚苯乙烯；纤维素双乙酸酯和纤维素三醋酸酯及其混合物或共聚物和类似物。在一个优选实施例中，光透射基片32实质上由透明材料如聚碳酸酯制成。基片32适宜厚度约为3μm～100μm，优选厚度约为12μm～25μm。虽然基片32是作为一个单层来描述的，但它可以由多层基片材料制成。
[036]图3描述了与图1相似的光学结构，但是图案反射层26和表面浮雕图案24的暴露部分下有附加层42。层42可以用来保护图案反射层26和表面浮雕图案24，也可为光学结构40增加光学特性。例如，层42可以是有颜色的、光透射和/或不透明的。层42可以是单层，也可以是多层结构。当层42为图1中的结构增加光学特性时，在这里它指的是“光学活性”涂层。
[037]图4为使用光活性涂层的例子，其中描述了包含一个含表面浮雕图案24和图案反射层26的光透射层22的光学结构50。光学活性多层光学涂层58可用一层薄膜光学堆制作，其用于图案反射层和表面浮雕图案的暴露区。
[038]在图4中，多层光学涂层58包括部分吸收/部分透射层52，下文将称之为“吸收”层，光学介电层54和反射层56。根据美国专利5,135,812，在这里通过参考将其全部内容结合入本发明中，这些层将为光学结构50增加变色特性，这意味着色彩将由于视角不同而改变。
[039]已发现这种结构具有有用的光学性质。在图案反射层遮盖表面浮雕图案的部分，可产生如图1的结构中所观察到的光学效果。然而，在没有反射层的表面浮雕图案部分多层光学涂层将产生唯一的光学效果。例如，在图案铝反射层位于显示全息图的表面浮雕图案下的情况，将可以看到一系列标准的全息色彩，所述全息色彩为典型的彩虹色，其中色彩随倾角的增大由蓝向红变化。在多层光学涂层58直接应用于表面浮雕图案的区域，全息图可显示不同的视觉色彩，这是由于涂层58将生成可以修正全息图的衍射/干涉效果的特殊色彩。
[040]吸收层52的适宜厚度约为30-300埃，优选厚度约为50-100埃。吸收层可由半透明的材料制成，如灰色金属，包括铬、镍、钛、钒、钴和钯，也可以是其它金属，如铁、钨、钼、铌、铝及类似物。也可以使用上述金属的各种组合物和合金，如镍铬铁合金(Ni-Cr-Fe)或镍铬合金。吸收层52也可以使用其它吸收材料，包括金属化合物，如金属低氧化合物、金属硫化物、金属氮化物、金属碳化物、金属磷化物、金属硒化物、金属硅化物及其组合物，也可以是碳、锗、氧化铁、混合于介电层的金属和类似物。
[041]光学介电层54是在吸收层18上通过传统沉积工艺形成，如使用电子束或耐热的PVD、化学气相沉积(CVD)、等离子体增强化学气相沉积(PECVD)、直流(DC)反应溅射、射频(RF)溅射或类似工艺。形成有效光学厚度的介电层可使光学结构50获得变色特性。典型地，该层的光学厚度以四分之一波长光学厚度(QWOT)为单位来表示，即是满足QWOT条件时的期望波长。介电层54的光学厚度范围约为在大约400nm设计波长时的2个QWOT，到在大约700nm设计波长时的9个QWOT，最优范围为在大约400-700nm设计波长时的2-6个QWOT，所述光学厚度取决于所期望的色移。适合制备介电层54的材料包括具有高折射率系数的材料(定义为折射率大于1.65的材料)，也包括折射率系数低的材料(定义为折射率等于少于1.65的材料)。
[042]适用于介电层54的高折射率材料包括硫化锌(ZnS)、氧化锌(ZnO)、二氧化锆(ZrO2)、二氧化钛(TiO2)、碳(C)、氧化铟(In2O3)、氧化铟锡(ITO)、五氧化二钽(Ta2O5)、氧化铈(CeO2)、氧化钇(Y2O3)、氧化铕(Eu2O3)、氧化铁，如四氧化三铁(Fe3O4)和氧化铁(Fe2O3)，氮化铪(HfN)、碳化铪(HfC)、氧化铪(HfO2)、氧化镧(La2O3)、氧化镁(MgO)、氧化钕(Nd2O3)、氧化镨(Pr6O11)、氧化钐(Sm2O3)、氧化锑(Sb2O3)、碳化硅(SiC)、氮化硅(Si3N4)、氧化硅(SiO)、三氧化硒(Se2O3)、氧化锡(SnO2)、三氧化钨(WO3)及其组合物和类似物。适用于介电层54的低折射率材料包括氧化硅(SiO2)、氧化铝(Al2O3)、氟化物如氟化镁(MgF2)、氟化铝(AlF3)、氟化铈(CeF3)、氟化镧(LaF3)、氟化铝钠(如Na3AlF6或Na5Al3F14)、氟化钕(NdF3)、氟化钐(SmF3)、氟化钡(BaF2)、氟化钙(CaF2)、氟化锂(LiF)及其组合物，或其它任何折射率大约等于或低于1.65的低折射率材料。例如，可用作低折射率材料的有机单体或聚合体，包括二烯或烯烃，如丙烯酸酯(例如，甲基丙烯酸酯)；全氟烯烃；聚四氟乙烯(Teflon)；氟化乙烯丙稀(FEP)及其组合物与类似物。
[043]反射层56可在介电层54上通过传统沉积工艺形成，如PVD、溅射或类似工艺。反射层56的适宜厚度约为300-1000埃，优选厚度约为500-1000埃。根据期望的色彩效果，反射层56最适宜用不透明的高折射率金属制备而成，例如铝、银、铜、金、铂、铌、锡及其组合物和合金，以及类似物。也可以使用其它金属，例如铬、镍、钛、钒、钴和钯、或钴-镍合金，其它金属也可象其他反射材料一样用于制备合适厚度的反射层56。
[044]图5示意性描述了光学结构中的另一个实施例。图5显示了光学结构60，所述光学结构60具有在透射层22上形成的表面浮雕图案24和位于表面浮雕图案下的图案反射层26。一种包含悬浮薄片64的透射物质被应用在图案反射层和光学浮雕图案暴露部分下，当透射物质硬化或固化后，形成包含悬浮薄片64的透射层62。为得到期望的光学效果，使用的特殊薄片不必像图示那样平整，可以是任何期望的颜料或颗粒物，或是以不同间隔定位。然而，当所述薄片纵横比高而且平整，以至于它们与层22平行时，将产生最强烈的变色效果。用于连接图5的具体结构的合适变色薄片与美国专利编号5,135,812描述的形式相同，此处通过参考将其结合入本发明中。
[045]除了因表面浮雕图案24和图案反射层26组合而观察到的变色效果，层62中的悬浮变色薄片将导致另外的变色效果。因使用悬浮薄片而非图4中的连续结构增加了额外的光学效果，这将取决于如薄片64加到透射层62的分量、薄片64的尺寸和纵横比、薄片64的光学特征和薄片的其它特征这样一些因素。
[046]图6描述了与图5中光学结构60相似的光学结构70，区别在于图6的具体结构中使用了一种其折射率与透射层22折射率相匹配的材料来制备透射层72。这种匹配可以有效地“去掉”层22和72之间的光学边界，如图6中点线所示。换句话说，表面浮雕图案24与图案反射体26的组合可得到前面讨论的光学效果，但在图案24上使用折射率匹配材料72将不会显示与表面浮雕图案相关的光学效果。因此，在图6的具体结构中，在表面浮雕图案中没有被图案反射层26覆盖的部分可观察到的唯一光学效果是由悬浮在材料72上的薄片64所引起的。
[047]可以理解，折射率匹配层也可用于与图3具体结构的相关结构，其结果是将在应用图案反射体26的表面浮雕图案24的区域中观察到光学效果，但在没有反射体遮盖的表面浮雕图案区域将不会观察到这种表面浮雕效果。
[048]也可以理解，通过选择上面描述的各种特征的组合，可以得到多种效果。例如，可以只在层22的部分区域加上表面浮雕图案24，也可以在整个表面上加上表面浮雕图案。不同类型的表面浮雕图案可用于透射层22的不同位置。为获得不同的光学效果，可以使用不同的材料以使图案反射体26各个部分各不相同。可以使用多种类型的薄片64，而不是单一组分和结构的薄片；或者可以在光学结构某一区域使用一种类型的薄片，而在另一区域使用不同类型的薄片。为提供期望的光学效果，可将各种类型的多层膜大量使用于表面浮雕图案24和图案反射体26的组合中。例如，薄膜光学膜堆可以包括其它光学涂层，如所有的电介质系统，其中，不仅可以观察到光学偏移效果，而且可观察到红外信号，且可用作一种隐形防伪特性。
[049]图7A和7B描述了利用本发明特征的热印金属薄片的结构。热印图案在保护安全文档中特别有用，如货币、支票、签证、护照、证书、身份证和类似物。热印图案在需要商标保护领域也非常有用，如医药品、化妆品、电子产品、软件、服装或其它具备被伪造特性的产品。在后一种情况中，热印图案可以粘贴在包装盒、容器或产品本身上。
[050]图7A描述了一种本发明所述的热印图案80的结构。举一个例子来说明，如图3所示的光学结构40可以夹在载片82与热释放层84和热活性胶86之间，其中光学结构40一侧是热释放层84，另一侧是热活性胶86。图7A描述了应用于安全文档88的热印装置80。图7B描述了使用该结构的结果，由于高分辨的浮雕技术和光学活性涂层技术同时具备以使图案具有与真实图案相同的光学特征，所述结构不仅提供视觉感染力，而且不易被仿造，所述高分辨的浮雕技术如全息技术、图案结构。
[051]本发明也可以在不偏离其本质或内在特性的情况下采用其它特殊的方式进行具体阐述。可仅像图示的一样从各个方面来考察描述的具体结构，但不限于此。因此，本发明的范围不是前面描述的范围而是下面的权利要求的范围。所有与权利要求的等价内涵和范围内的改变都属于本发明的范围。
Claims (8)
1.一种光学结构，包括：
光透射基片，所述光透射基片包含第一表面和相对的第二表面，其中所述第二表面包括形成于其上的表面浮雕图案；
反射材料图案层，所述反射材料图案层被运用于所述光透射基片的所述表面浮雕图案的部分区域，以使所述表面浮雕图案的部分区域被所述反射材料覆盖，所述表面浮雕图案的其他部分被暴露；和
光学活性涂层，所述光学活性涂层位于所述表面浮雕图案的所述图案层和所述暴露部分下而且与它们接触，其中，所述光学活性涂层的折射率实质上与所述光透射基片的折射率匹配，以使在所述表面浮雕图案暴露部分将不显示所述表面浮雕图案的光学效果，其中，所述光学活性涂层包含可给所述表面浮雕图案的所述暴露部分增加期望的光学效果的薄片。
2.根据权利要求1所限定的光学结构，其特征在于，所述薄片具有随入射观察角度或入射到其上的光的角度的变化而颜色发生变化的变色特性。
3.根据权利要求1所限定的光学结构，其特征在于，所述薄片中的每一个包含一薄膜光学膜堆，所述薄膜光学膜堆包括：
部分吸收、部分透射层；介电层；和反射层。
4.根据权利要求1所限定的光学结构，其特征在于所述反射材料图案层是不透明的。
5.根据权利要求1所述的光学结构，其特征在于，所述反射材料图案层被使用以形成绘画图案。
6.根据权利要求1所述的光学结构，其特征在于，所述反射材料图案被使用以形成文字数字符号。
7.根据权利要求1所述的光学结构，其特征在于，所述反射材料图案层被使用以形成图解图案。
8.根据权利要求1所述的光学结构，其特征在于，所述表面浮雕图案从包括衍射光栅图案、全息图图案、角反射器、零级衍射图案、叠栅图及其组合的组中选择。
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2004
- 2004-09-16 KR KR1020067004030A patent/KR101040095B1/ko active IP Right Grant
- 2004-09-16 UA UAA200602802A patent/UA87281C2/ru unknown
- 2004-09-16 CN CNB2004800258037A patent/CN100504661C/zh active Active
- 2004-09-16 EP EP04769474.0A patent/EP1664939B1/en active Active
- 2004-09-16 CA CA002529344A patent/CA2529344A1/en not_active Abandoned
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- 2004-09-16 EP EP07003019A patent/EP1777595A3/en not_active Withdrawn
- 2004-09-16 WO PCT/IB2004/003119 patent/WO2005026848A2/en active Application Filing
- 2004-09-16 EP EP18176927.4A patent/EP3441825A1/en active Pending
- 2004-09-17 TW TW093128288A patent/TWI383275B/zh active
Also Published As
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|---|---|
| TWI383275B (zh) | 2013-01-21 |
| WO2005026848A2 (en) | 2005-03-24 |
| EP1664939B1 (en) | 2018-12-12 |
| TW200513813A (en) | 2005-04-16 |
| US6987590B2 (en) | 2006-01-17 |
| CA2529344A1 (en) | 2005-03-24 |
| EP1664939A2 (en) | 2006-06-07 |
| EP3441825A1 (en) | 2019-02-13 |
| KR20060067966A (ko) | 2006-06-20 |
| DK1664939T3 (en) | 2019-03-25 |
| CN100504661C (zh) | 2009-06-24 |
| CN1849566A (zh) | 2006-10-18 |
| WO2005026848A3 (en) | 2005-05-19 |
| US20050063067A1 (en) | 2005-03-24 |
| EP1777595A3 (en) | 2010-08-25 |
| KR101040095B1 (ko) | 2011-06-09 |
| EP1777595A2 (en) | 2007-04-25 |
| UA87281C2 (ru) | 2009-07-10 |
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