CN1936068B - 具有图案化的装饰性涂层的制品 - Google Patents
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Abstract
一种具有装饰性的、可见图案的多色表面外观的制品,该制品包括衬底和通过气相淀积在至少一部分衬底上提供的第一涂层,该涂层包括具有第一颜色的第一材料。该涂层包括随机排列的穿透,通过该穿透可以看见一部分下层表面,该下层表面包括具有第二颜色的第二材料,该第二颜色不同于第一颜色。所述穿透形成包括用人的肉眼可区分的特征的装饰性图案。
Description
发明领域
本发明总体涉及其上提供有装饰性涂层或终饰的制品以及制造该制品的方法。更具体地,本发明涉及其上提供有多颜色(multi-tone)涂层的制品以及制造该制品的方法。
背景技术
使用物理气相淀积(PVD)或化学气相淀积(CVD)法在制品上提供着色涂层。目前,在诸如管道设备、家用五金件(例如门把手和铰链)、汽车产品、娱乐产品和各种其他产品之类的商品上,可以获得各种颜色的PVD涂层。
与常规聚合物和电镀涂层相比,PVD和CVD装饰性涂层一般具有许多性能优点,如高硬度、耐磨性、耐腐蚀性、耐化学试剂性等。虽然可以获得各种颜色的PVD和CVD涂层,但目前可获得的PVD和CVD涂层一般在整个衬底表面都是均一颜色。然而,对于某些特定的应用,可能需要使用具有可见图案的、多色外观的PVD或CVD涂层(如用于形成具有例如条纹、斑纹、镶大理石的、“古式的”、“古色的”或“仿古磨损的”的终饰或者具有与表面终饰相结合的装饰性或信息性的数字图像的产品)。
用于在如上所述产品上形成图案化的装饰性终饰的常规方法通常使用聚合物涂层进行着色或保护。使用涂料、漆等以在衬底表面直接形成图案化的终饰的方法是公知的。通过对衬底进行热处理、化学处理和/或机械处理以制造图案化的终饰的方法也是公知的,但是这种处理过的表面通常不耐用,而且需要聚合物外涂层以防刮擦和腐蚀。聚合物涂层易受刮擦、溶剂和家用化学品影响而可能出现小孔,通过该小孔可以引起衬底的腐蚀。
相反地,PVD涂层一般非常硬并且耐磨和耐化学品,在许多应用上都优于基于聚合物的涂层。虽然图案化的PVD和CVD涂层已经用于电子工业上以制备印刷集成电路,但是这种涂层通常不用于提供装饰性涂层(如可见图案的多色装饰性涂层)。这种图案化的PVD和CVD涂层一般由针对电学性能(与装饰相反)选择的材料制成,并用于制造非装饰性图案,这种图案太小,以至于不对其进行放大,人的肉眼就根本看不见。此外,这种图案化工艺(process)通常仅仅处理平面衬底,并且一次只处理一个单衬底,因而不适合于消费品的批量生产。
使用PVD和/或CVD方法为制品提供具有图案化的外观的装饰性涂层将是有利的,这种装饰性涂层在正常使用时将不会被磨掉或擦掉、耐刮擦和耐腐蚀、能够抵制常规的家用化学品和溶剂,并且在日光或暴露在室外条件下不会老化或褪色。提供这样的具有装饰性涂层的制品也是有利的:该涂层提供令人愉悦的审美外观,该外观肉眼可见,并且由适合批量生产的常规方法制得。还希望能够提供展示本领域普通技术人员通过阅读本申请文件即可理解的一种或多种上述的或其它优点的涂层、制品和方法。
发明内容
一个示例性实施例涉及一种具有装饰性的、可见图案的多色表面外观的制品,所述制品包括:衬底;第一涂层,通过气相淀积提供在所述衬底上,所述第一涂层包括具有第一颜色的第一材料;第二涂层,通过气相淀积提供在所述第一涂层的至少一部分上,所述第二涂层包括具有第二颜色的第二材料,所述第二颜色不同于所述第一颜色;其中,所述第二涂层包括随机排列的穿透,通过所述穿透可以看见下层表面的一部分,所述第一涂层包括所述下层表面;其中所述穿透形成包括人的肉眼可区别出的特征的装饰性图案。
另一个示例性实施例涉及一种用于制造具有装饰性涂层的制品的方法,所述方法包括:在低于一个大气压下,使用物理或化学气相淀积法在真空室中将至少第一涂层淀积到衬底表面的至少一部分上,其中所述至少第一涂层包括第一涂层和第二涂层,所述第一涂层包括具有第一颜色的第一材料,所述第二涂层包括具有第二颜色的第二材料;和使用非均匀图案化工艺对所述第二涂层进行图案化,以形成具有穿透的图案化的涂层,通过所述穿透可以看见所述下层表面的一部分,所述下层表面包括所述第一材料,所述第一颜色视觉上与所述第二颜色可对比;其中所述非均匀图案化工艺包括在利用非均匀修整工艺对掩膜层进行图案化之前或同时在所述第二涂层上应用所述掩膜层,包括在所述掩膜层中形成穿透,通过所述穿透使得所述第二涂层的一部分暴露出来;其中,所述图案化的第二涂层包括装饰性图案,所述图案包括通过人的肉眼可区别的特征。
另一个示例性实施例涉及一种用于制备具有装饰性表面的制品的方法,所述方法包括:使用气相淀积法将第一材料层淀积到衬底上,所述第一材料层包括具有第一颜色的第一材料;使用气相淀积法将第二材料层淀积到所述第一材料层上面,所述第二材料层包括具有第二颜色的第二材料,所述第二颜色不同于所述第一颜色;以及移除部分所述第二材料层以形成延伸穿过所述第二层的孔,所述孔以随机配置排列;其中,通过所述孔可看见部分所述第一层,从而在所述制品上形成装饰性图案。
附图简述
图1为根据示例性实施例,其上提供有装饰性涂层的制品的照片;
图2为根据示例性实施例,其上提供有装饰性涂层的制品的照片;
图3为根据示例性实施例,阐述制造具有装饰性涂层制品的方法中的步骤的流程图;
图4-9为其上提供有装饰性涂层的制品的部分截面示意图,用于阐述图3的流程图所表示的示例性方法中的步骤;
图10为根据一种示例性实施例,阐述制造具有装饰性涂层的制品的方法中的步骤的流程图;
图11-15为其上提供有装饰性涂层的制品的部分截面示意图,用于阐述图10的流程图所表示的示例性方法中的步骤;
图16为根据示例性实施例,其上提供有装饰性涂层的制品的照片;
图17为根据示例性实施例,其上提供有装饰性涂层的制品的照片;
图18为根据示例性实施例,阐述制造具有装饰性涂层的制品的方法中的步骤的流程图;
图19-22为其上提供有装饰性涂层的制品的部分截面示意图,用于阐述图18的流程图所表示的示例性方法中的步骤。
具体实施方式
根据一个示例性实施例,提供了一种制品或产品,该制品或产品包括其上提供有可见图案的、多色外观的装饰性涂层。各种制品或产品中的任意一种可以使用下述各个示例性实施例中所述的方法制得,所述制品或产品包括但不限于管道设备组件(如龙头、把手、喷嘴、水槽、排水法兰、停止阀、管道、浴缸排水管等)、家用五金件(如门把手、铰链、抽屉/橱柜拉手等)、浴室五金件(毛巾杆、安全抓杆等)、窗户和门(如淋浴门等)、汽车产品(如汽车装饰部件、标志、轮盖等)、刀、医疗器具、餐具、娱乐产品、运动物品(如高尔夫球棍、滑冰用具等)、室内或室外照明产品(如灯、支架(fixture)等)、耐气候的信息指示牌(weather proof informational signs)以及其他各种产品或制品中的任意一种。应当注意的是,本发明并不适合于微处理器或电子芯片等的制备。
根据一个示例性实施例,在衬底上提供(如使用PVD和/或CVD工艺进行淀积)至少一个涂层或材料层,之后将掩膜材料施加在该涂层上。然后通过随机或非均匀修整工艺对该掩膜材料进行图案化,从而形成穿透(penetration)(如小孔或洞),该穿透使得部分下层涂层暴露出来。随后通过化学蚀刻移除涂层的暴露部分,留下随机或非均匀排列的穿透,通过该穿透能够使得具有对比性颜色(contrasting color)的下层涂层或衬底表面可见。
按照这种方式,可以提供具有可见图案、多色外观的装饰性涂层的制品,该制品包括通过真空淀积工艺淀积在衬底上的至少一种涂层材料。根据各种示例性实施例,可以通过诸如阴极电弧蒸发或溅射之类的PVD技术,或者通过诸如热丝或离子束PECVD之类的CVD法来提供(例如,淀积)所述至少一个涂层。
可以使用耐蚀刻工艺的图案化的掩膜层,通过蚀刻对涂层进行图案化,以移除未受掩膜保护的区域中的涂层。随后使用溶剂移除掩膜层,从而暴露出涂层表面的未蚀刻区域。所述涂层材料被选择来具有与通过蚀刻工艺而暴露出的下层表面形成对比的颜色。作为选择,可以采用某种方式通过阳极电镀或者其他方式的化学或物理地修整涂层的非掩蔽区域的方法来制造具有对比性颜色的区域,所采用方式可以获得具有与掩蔽区域颜色相对比的颜色的区域。下层表面可以是衬底表面或者可以是选择为具有所需装饰性外观和/或提供其他所需性能的下层涂层。
根据其他示例性实施例,可以通过在具有穿透的图案化的掩膜层之上提供涂层来对涂层进行图案化,所述穿透暴露出部分衬底表面(或另一下层表面)。在提供所述涂层之后,将掩膜层溶于溶剂中,由此使淀积在掩膜材料上的涂层材料松散且被移除,同时在通过掩膜层中的穿透而暴露的所述部分衬底表面上,将已经淀积的涂层留在适当的位置。后一种类型的工艺被称为“剥离”(lift-off)工艺。
可以用于蚀刻或剥离工艺的图案化的掩膜层可以通过将掩膜材料层非均匀地淀积在衬底上而形成,例如可以通过镂花涂装或通过将掩膜材料均匀地淀积在衬底表面上,随后通过非均匀地移除工艺(例如滚动抛光(barrel tumbling))在终饰介质中对掩膜层进行图案化,从而移除部分掩膜层、形成穿透(例如小孔或洞),通过该穿透使得部分下层表面暴露出来。下面将详细描述根据各个示例性实施例用于形成装饰性的图案化的掩膜层的各种方法。
如同这里使用的,所用术语“衬底”指装饰性涂层下面的制品的全部或部分,并且可以包括任何表面保护层或制备层,例如电镀或聚合物最下面的一层。根据各种示例性实施例,衬底可以包括各种材料,诸如金属(例如黄铜、锌、不锈钢、锡、铜、铁基合金等)、塑料(诸如热固性或诸如聚乙烯或丙烯腈-丁二烯-苯乙烯(ABS)材料之类的热塑性材料等)、陶瓷、玻璃(如建筑型玻璃(如浴室门等))和/或复合材料(如金属基质材料、聚合物基质材料、陶瓷和玻璃基质材料、碳石墨基质材料、纤维增强复合材料等)。
衬底可以被电镀上防腐蚀和/或表面平整层,所述防腐蚀和/或表面平整层包括例如镍、铬、铜、钴、锌、镉、锡、铅、金、黄铜、青铜、铑、铂、镍-锡合金以及其他已知的电镀材料。衬底还可以包括保护性和/或表面平整聚合物层、衬底材料或所采用涂层的阳极电镀层或其他任何已知的与真空淀积和图案化工艺兼容的表面制备(surface preparation)材料。
在此所用的术语“装饰性涂层”指对制品提供所需表面外观的涂层(如具有图案化的、多色外观的可见涂层)。在某些实施例中,除了提供所需表面外观,装饰性涂层还可以对下层衬底提供各种实用特征,如一定程度耐磨、耐刮划、耐失去光泽和/或耐腐蚀性。这种涂层也可以用于其他功能性目的,如增加切割边缘的强度,或提高表面的耐磨性(例如在涂层的外观对消费者购买欲望存在贡献的情况下)。
术语“图案”或“图案化”指包括具有穿透(小孔或洞)的涂层或掩膜层,通过该穿透使得不同颜色(例如对比色)的下层涂层或衬底可见。术语“可见图案”指图案化的涂层或者层,在所述涂层或者层中,至少某些图案特征(区域)具有足够的尺寸和/与周围特征相比有着足够的颜色对比,从而使得这些特征无需放大就可以通过肉眼轻易区分出来,例如,包括但不限于最小线尺寸大于约1毫米的特征。这种可见特征也可以由更小的点或成形像素(shaped pixel)组成,所述点或成形像素单独来说是人眼看不见的,但组合在一起是可见的。术语“装饰性图案”指至少部分地具有所需美学吸引力外观的图案。术语“信息图案”指为提供清晰可见文本显示或数字图像显示而选择的图案,所述显示也起装饰性作用。
此处所用的术语“随机”和“非均匀”指在材料层中所形成的孔或洞的排列意欲表示在形成图案之前,其中孔或洞的具体位置没有预定的排列。用于获得这种随机或非均匀排列的各种技术将在下面进行更详细的描述。这种排列不像例如在微处理器等的制造中所用的掩膜中所采用的排列,后者具有在晶片等等上所形成的一组或者预定的图案(例如,诸如导电线、通路之类的特征会正确地排列起来以提供所需功能)。
通过阅读本公开应该理解的是,使用随机图案化技术可以形成更大的可区分图案(如动物图像)。例如,可以采用具有在其中形成的剪切块(cutout)的掩膜来覆盖衬底。剪切块可以具有所需形状(如动物图像)。未被掩膜所覆盖的衬底部分(相应于剪切块)可以使用随机或非均匀方式来图案化,以形成延伸穿过衬底的孔。当移除掩膜时,由掩膜所覆盖的部分将不会被图案化(如将不会具有延伸穿过的孔),未被掩膜所覆盖的衬底的部分中将具有随机或非均匀图案结构。观察衬底即可发现由随机或非均匀图案定义的图像(如动物)。
术语“对比性颜色”指在通常的室外或室内光照条件下通过肉眼能够与第一颜色可视区分的第二颜色。
图1和图2为根据示例性实施例,使用用于提供装饰性涂层或终饰的方法100而制造的制品10和20的照片。图3用于阐述方法100的示例性步骤的流程图,图4-9用于阐述方法100中的步骤的制品200的横截面示意图。
在图4所示的步骤110中,在包括材料212的衬底210上,提供包括材料222的第一层或涂层220。根据一个示例性实施例,材料222为相对暗色的材料。例如,材料222可以是在低于一个大气压下采用阴极电弧蒸发工艺在真空室中施加到衬底210上的锆的碳氧化物或氧-碳-氮化合物(oxy-carbo-nitride)。根据另一个示例性实施例,材料222为在较低压力的真空淀积工艺中,采用热丝PEVCD法形成的类金刚石(diamond-like carbon,DLC)涂层。如下所述,各种其他材料也可以用于层220。
在图5所示的步骤120中,在层220上提供材料232的第二层或涂层230。根据一个示例性实施例,材料232具有与材料222不同的颜色(如更亮的颜色)。例如,材料232可以是诸如通过阴极电弧蒸发施加到层220上的锆的氮化物之类的材料。
根据一个示例性实施例,层220和230的厚度在约0.3-0.5微米之间。根据另一个示例性实施例,也可以使用厚度大于0.5微米或小于0.3微米的层。例如,在除了提供装饰性外观之外,还需要涂层起到诸如防止刮伤或防止腐蚀蚀作用之类的某些功能的情况下,可以使用更厚的涂层(如在约0.5-5微米范围内)。还应当注意,根据不同的示例性实施例,层220的厚度与层230的厚度可以相同或不同。
在提供层230之后,将制品200从真空室中移除,并在图6中所示的步骤130中涂覆相对薄的掩膜或掩膜层240(如包括诸如防水永久油墨之类的材料242)。根据一个示例性实施例,层240的厚度在约0.1微米-0.5微米之间。根据各种其他示例性实施例,掩膜层的厚度可以在约0.01微米-50微米之间。
在图7所示的步骤140中,将层240的一部分移除(如层240被随机或非均匀地图案化)。根据一个示例性实施例,制品200放置在带有塑料滚动介质的滚筒中,并且滚动直至层240部分地而非全部地移除并使得层230的一部分暴露为止。例如,根据一个示例性实施例,在大约3到15分钟之间的滚动操作中使用平均直径为大约10mm和20mm的塑料滚动介质,以移除层240的一部分。
如图7所示,在该工艺中,在层240上形成多个孔或洞244(例如穿透)(留下掩蔽或覆盖部分层230的层240的区域或面积(area)246)。应当注意的是,根据处理条件和其他因素,孔244可以是各种形状和大小。通过对滚动介质材料、载体液体、填充级别和其他已知参数进行选择,可以通过对层240的非均匀的移除而产生可视特征。根据其他示例性实施例,可以对掩膜层进行图案化,以产生所需的重复图案(例如,可以将其淀积,使其具有干涉图案(例如,可以通过控制诸如氧化层之类的层的厚度来控制颜色,从而即使由于光干涉导致材料透明,也可以形成明显的颜色),可以通过丝网(silk screen)法、光刻工艺、喷溅工艺(例如,喷涂)、烫印(stamp)或模板(stencile)、激光图案化或其他任何合适的方法来施加图案)。根据另一个示例性实施例,可以将蚀刻剂喷射到掩膜材料上以在掩膜中形成图案,而不是在掩膜材料上喷射。
在图8所示的步骤150中,在蚀刻过程中将层230的暴露部分(即,位于层240中所形成的孔244的下面的层230的那些部分)移除。根据一个示例性实施例,制品200放置在蚀刻溶液中,该蚀刻溶液溶解暴露区域中的层230,在层230中形成孔234(例如,穿透、洞等),通过孔234使得较暗层220可见。在蚀刻工艺中由层240的区域246覆盖的层230的区域或面积236保留在层230上。
在图9所示的步骤160中,将层240移除(即,在步骤140后保留在层230之上的部分层240)。通过使用配制成能够选择性移除该层而不破坏其他层的有机溶剂(如丙酮、TCE等)或蚀刻剂(酸或碱)来移除层240。
根据另一个示例性实施例,仅使用单一的真空淀积层。图10用于显示方法300中的步骤的流程图,图11-15为使用方法300制备制品400的步骤的横截面示意图。
在图11所示的步骤310中,包括材料422的层或涂层420被提供在包括材料412的衬底410上。根据一个示例性实施例,层420为采用阴极电弧蒸发直接淀积在衬底表面上的锆的碳氧化物层。
在提供层420之后,将制品400从真空室中移除,并在图12中所示的步骤320中涂覆相对薄的掩膜或掩膜层440(例如,由诸如防水永久油墨之类的材料442制成)。根据一个示例性实施例,层440的厚度在约0.5微米-5.0微米之间。根据各种其他示例性实施例,掩膜层的厚度可以在约0.01微米-50微米之间。
在图13所示的步骤330中,按照与图7相关的上述描述,将层440的一部分移除。在该工艺中,在层440上形成多个孔或洞444(留下掩蔽或覆盖部分层420的层440的区域或面积446)。应当注意的是,根据处理条件和其他因素,孔244可以是各种形状和大小。通过对滚动介质材料、载体液体、填充级别和其他已知参数进行选择,可以通过层440的非均匀移除产生可视特征。根据其他示例性实施例,可以对掩膜层进行图案化,以产生所需的重复图案(例如,可以将其淀积,使其具有干涉图案(如可以通过控制诸如氧化层之类层的厚度来控制颜色,从而即使由于光干涉导致材料透明也可以形成明显的颜色),可以通过丝网法、光刻工艺、喷溅工艺(例如,喷涂)、烫印或模板法、激光图案化或其他任何合适的方法来施加图案)。根据另一个示例性实施例,也可以将蚀刻剂喷射到掩膜材料上以在掩膜中形成图案,而不是在掩膜材料上喷射。
在图14所示的步骤340中,在蚀刻工艺中将层420的暴露部分(即,在层420中形成的孔444的下面的层440的那些部分)移除。根据一个示例性实施例,制品400放置在蚀刻溶液中,该蚀刻溶液溶解暴露区域中的层420,在层420中形成孔424(例如,穿透、洞等),通过孔424使得衬底410可见。在蚀刻工艺中由层440的区域446覆盖的层420的区域或面积426保留在衬底410上。
在图15所示的步骤350中,将层440移除(即,在步骤340后保留在层420上的部分层440)。通过使用配制成能够选择性移除该层而不破坏其他层的有机溶剂(如丙酮、TCE等)或蚀刻剂(酸或碱)来移除层440。
如以上根据图3-15所述的方法100和300,可以用于形成包括穿透(如孔234和424)的可见图案化的层,通过该穿透可以看见下层材料(如图9中的层220和图15中的衬底410)。根据一个示例性实施例,这种下层材料具有与覆盖层材料不同的颜色。通过这种方式,可以生产具有呈现条纹、斑纹、镶大理石的、古式的、古色的、仿古磨损的等终饰的制品。根据图3-9所示和所述的实施例使用多层淀积工艺,而关于图10-15所示和所述的实施例使用单层淀积工艺。根据其他各种示例性实施例,可以提供(如淀积)不同的层数(如三层和三层以上),并且对所述层进行图案化,以便可以合适地提供所需表面特征和外观。
根据另一种示例性实施例,可以通过机械和化学处理对涂层直接图案化,以将具有不同颜色的下层表面的部分暴露出来。按照这种方式,可以制得如图9-15所示的制品,而无需使用掩膜层。例如,可以将颜色较暗的锆的碳氧化物层与塑料介质在研磨浆料中滚动一段受控的时间,以形成穿透的装饰性图案,所述穿透将具有不同颜色的下层表面部分(如锆的氮化物的下层)暴露出来。纹理表面可以用抛光化合物进行抛光,以移除突起处的涂层和具有不同颜色的下层表面的暴露部分。采用刷子、烫印等非均匀地使用化学蚀刻剂,也可以用于直接对着色层进行图案化。
图16和17为阐述使用根据示例性实施例的用于提供装饰性涂层和终饰的方法500所制得的制品30和40的照片。根据示例性实施例,方法500可以称为“剥离工艺”,将在下面进行更详细的描述。图18为阐述方法500的示例性步骤的流程图,图19-22为显示方法500中的步骤的制品600的横截面示意图。
在图19所示的步骤510中,在制品600的衬底610上直接提供层640(例如,包括类似于上述材料242的材料642的蚀刻掩膜层)。
在图20所示的步骤520中,类似于以上根据图7所述的层240,对层640进行图案化(例如,采用滚动工艺)。该工艺的结果是在层640中形成孔644,留下掩蔽和覆盖部分衬底610的区域和面积646。
在图21所示的步骤530中,可以在层640和衬底610上提供包括材料622的层620,从而材料622既在层640的剩余部分646上,还在层640中所形成的孔644中(例如,制品600可以放置在真空室中并涂覆有层620)。根据一个示例性实施例,层620具有不同于衬底610的颜色。
在图22所述的步骤540中,采用同时也将淀积在层640上的层620部分移除的方式,将层640的剩余部分646移除(例如,采用溶剂溶解或以其他方式移除),由此在层620中形成可见图案的穿透,通过该穿透可以看见具有不同颜色的下面的衬底。如图22所示,由于层640的剩余部分和层620的上面部分的移除,在层620中形成孔624。在将部分646移除之后,在步骤530中在孔644中形成的层620的区域或面积626留下,并且掩蔽或覆盖衬底610的下面区域。
虽然根据图18-22所示和所述的实施例阐述了在下面的衬底610上直接提供层640,根据另一个示例性实施例,衬底可以包括在提供掩膜层(例如,层640)之前在其上提供的材料层。按照这种方式,可以提供图案层620,从而形成于其中的孔或穿透使得下面材料层可见(例如,如图9所示,显示了在下面的基色层220上提供的图案层230)。因而,在基色层的真空淀积之后,进行这种类型的剥离工艺,从而使得通过采用剥离工艺在顶层中形成的穿透,可以看见基色层。例如,剥离工艺可以用于避免必须蚀刻很难蚀刻的材料,诸如DLC。
例如,为示例而非限制性目的,适合于实现在各种示例性实施例中所描述的方法的已知PVD(物理气相淀积)真空工艺包括阴极电弧蒸发法、溅射法、热和电子束蒸发法和离子束溅射法,其中阴极电弧蒸发法和溅射法是优选PVD工艺。优选化学气相淀积(CVD)法包括热丝等离子增强化学气相淀积(PECVD)法和离子束PECVD法,并包括使用电子回旋共振(ECR)、微波或射频激发的等离子和离子源法。在各种示例性实施例中,PVD和CVD法也可以结合使用,例如,通过采用热丝PECVD法淀积暗灰或黑色的类金刚石,然后采用阴极电弧蒸发淀积ZrN涂层。根据一个示例性实施例,可以与本发明所公开的方法结合使用的物理气相淀积装置可以包括,可以从科罗拉多州玻尔得的气相科技购买到的VT 3000或VT 1500型批处理涂覆器。
用于基色层(如层220)和图案化的涂层(如层230、420和620)的优选材料包括各种已知材料,例如诸如锆、钛、铪、镉、钪之类的金属的氮化物、氧化物、碳化物、氮氧化物、碳氧化物、碳氮化物和碳氧氮化物,以及包含此种金属的合金。更优选的材料包括含有锆的那些材料、尤其是锆的氮化物、碳氧化物和碳氧氮化物以及锆合金,如Zr-Ti和Zr-Sc。术语金属的氮化物、氧化物、碳化物、氮氧化物、碳氧化物、碳氮化物和碳氧氮化物是指金属与活性成分氧、氮和碳的相应组合的化合物和混合物。这些术语指化学计量和非化学计量的化合物,所述化学计量和非化学计量的化合物是指相对于按照公式所比例进行组合所需的量,一种或几种成分不足或过量的化合物。它们尤其还表示一种或几种活性成分不足的亚化学计量化合物。
用于基色层和图案化的涂层的材料还可以包括碳,尤其是作为类金刚石或DLC的无定型、通常为氢化玻璃状的硬型碳。DLC可以通过包括热丝或离子束PECVD法在内的各种已知方法进行真空淀积,其中来自热丝或离子束源的电流用于离子化含碳气体(carbon-bearing gas),如甲烷或乙炔。DLC是一种当厚度增加时外观逐渐变灰直到接近黑色的半透明材料。由于DLC不为用于金属基层的蚀刻剂所侵蚀,因此DLC作为基色层是有利的,在这种基色层上可以淀积锆基或其它金属基的图案化层。用于基色层和图案化的涂层的优选材料还包括诸如铝、铌、钛、锆和铪之类的金属的阳极电镀层。阳极化是指湿化学(wet-chemical)电解法,通过该方法使得金属层被氧化。控制厚度的透明阳极化层呈现在整个干扰光谱范围内的干扰色。多孔阳极化层可以使用已知的有机染料进行染色,以产生包括黑色和灰色在内的各种颜色的耐用的着色终饰。
已知的蚀刻方法包括采用已知酸、碱和商业蚀刻溶液的湿化学蚀刻。使用二氟化铵的稀溶液对诸如ZrN、ZrOC等材料进行蚀刻也是已知的。蚀刻还可以通过使用等离子蚀刻方法在真空系统中完成。在有些情况下,为了防止下层表面过度蚀刻,希望在下层表面与图案化层之间使用蚀刻停止层。当两种色层为类似材料且使用相同方法蚀刻时,尤其希望使用这种蚀刻停止层。蚀刻停止层可以是透明材料,这样无需移除蚀刻停止层即可看见下层表面;或者可以是随后可以通过不破坏颜色层的方法移除的非透明材料。由于镉不被二氟化铵主动地蚀刻并且与锆化合物和下层的电镀叠层(plating stack)电镀性相容,因此镉可以作为蚀刻停止材料的可能侯选材料。
掩膜材料(例如,用于形成掩膜层240、440和640)可以包括任何可以抵抗用于对要被图案化的涂层的非掩蔽区域进行修整的修整工艺,并且可通过为了在掩膜层中产生所需图案而选择的修整工艺而自身被图案化的材料。合适的材料可以包括油墨、光阻材料、涂料、漆、蜡和金属薄膜。
用于随机地或非均匀地对掩膜层进行图案化的方法包括诸如刮擦、磨砂、用金属、布或磨砂轮进行抛光、在陶瓷、坚果壳、研磨介质中进行滚动抛光、喷砂等已知工艺。也可以使用诸如光刻(通过焦点成像或激光扫描技术)和离子束平版印刷法的工艺。
可以通过喷射、浓缩、或在涂层表面上的掩膜材料的小滴或条纹的结合,通过丝网或模板、使用含有掩膜材料的笔或标记器进行书写、使用具有掩膜材料的橡胶印记进行印花、以及其它已知的非均匀地将这些材料施加到表面上的方法,可以将随机或非均匀的图案化的掩膜层直接淀积在涂层表面上。用于非均匀地施加掩膜层的优选方法为使用由光刻工艺产生的丝网。这种丝网可以产生包括几何图像或随机装饰性图案、企业标志、数字图像和文本在内的图像的掩膜层。这种丝网上去的图案可以包括较小的点或各种尺寸的成形像素,这种小点或象素用人眼不能单独分辨出来,但可以共同结合成视觉可分辨的特征图案。
根据另一个示例性实施例,用于对掩膜层图案化的非均匀修整工艺包括在诸如塑料或陶瓷粒子、坚果壳、耐磨介质等之类的介质中滚动抛光或振动抛光。用于产生具有图案的掩膜层的一种示例性方法包括下述步骤:a)将防水掩膜层均匀或半均匀地施加于部件的表面上,b)在部分装填有塑料滚动介质,优选但不是必须具有载体液体的桶中,将多个部件滚动一段充分的时间,以移除部分而不是全部的掩膜层。由滚动而产生的图案中的所需的重要部分(accent)可以通过以非均匀的方式使用掩膜剂产生,这种方式使得掩膜层在有些区域较厚,在其它区域较薄或根本不存在。
应当注意的是,在此所述的各种方法可以使用多次以获得所需的效果。例如,可以将具有不同颜色的多种涂层施用于制品上,以获得具有多色(例如,在制品表面上可以看见三种或更多种不同的颜色)表面外观的制品。本领域的普通技术人员通过阅读本发明即可理解,根据特定应用的制品所需的外观,可以使用任意数量的层或层的组合。
根据另一个示例性实施例,可以使用类似于上述的图案化方法以制备其上具有一个或多个像、图画、标志、标记或其它信息的制品。例如,可以提供掩膜材料,并对其进行图案化,以包括标识语,之后可以蚀刻下层,以使得标识语图案中的下层暴露。应该理解的是许多变化都是可能的。
提供下述实施例是为阐述目的而不是限制目的。本领域技术人员阅读本发明后可以理解,根据各种其它示例性实施例,方法和层材料的各种其它组合均可在衬底表面制备具有图案的装饰性涂层。还应该理解的是,具有两种以上颜色的图案化的涂层可以通过重复使用在此公开的技术和材料而制得。
示例1
根据一个工作示例,用镍铬双层电镀叠层对黄铜龙头把柄进行电镀,以对把柄提供铬色表面。在低于一个大气压下,使用阴极电弧蒸发在真空室中将包括锆的碳氧化物的涂层淀积在部件上。随后也使用阴极电弧蒸发施加锆的亚化学计量氮化物的第二涂层。将耐水永久油墨的蚀刻掩膜层施加在部件上。使用塑料介质对部件进行滚动抛光或振动批量(mass)抛光操作,以部分地移除油墨。然后用氟化氢铵稀溶液对部件进行蚀刻,以移除暴露在已移除掩膜层的区域中的部分顶层涂层。最后,将部件浸渍在溶剂(如丙酮、TCE等)中以移除油墨。由油墨保护的区域中的顶层涂层仍然保持原封不动,从而提供可见图案化的“古色锡铅合金(aged pewter)”表面外观。
示例2
根据一个理论示例,用具有铬色表面的铜、镍和铬电镀叠层对注塑塑料淋浴喷雾房进行电镀。将部件安装在真空室中并涂覆上一层厚度约为0.4微米的锆的碳氧化物的暗灰色层。将部件从真空室中移除,并使用自动刷拭系统以形成条纹的方式非均匀地施加漆掩膜材料,并使碳氧化物层表面的至少一部分暴露于掩膜层的穿透(非覆盖区域)中。然后使用氟化氢铵稀溶液对部件进行蚀刻,以移除所暴露出的部分的涂料层。最后,使用溶剂漂洗部件,以移除漆掩膜材料,从而使剩余的未被蚀刻的碳氧化物层表面暴露出来,最后形成具有黑色背景和铬色光泽的或者相反颜色的“仿古的”终饰,其中黑色背景和铬色光泽或者相反颜色取决于涂层表面的被掩蔽区域和未掩蔽区域的表面积的比例。
示例3
根据另一个理论示例,使用具有铬色表面的铜、镍和铬电镀叠层对锌印模压铸的浴盆喷管进行电镀。在部件上形成了防水油墨或丙烯酸漆的薄蚀刻掩膜层。然后使用马达线或纤维轮将部件以随机或以形成条纹的方式进行自动或手动“线刷(wire-brushed)”,由此在蚀刻掩膜层中产生刮擦图案,从而使得铬色衬底表面的一部分暴露出来。将部件安装在真空室中,并涂覆有暗灰色或黑色的类金刚石层。可以通过离子束或热丝PECVD对类金刚石进行淀积,其厚度至少为约0.2微米,优选至少为约0.3微米-0.5微米或更大,其中较厚的涂层形成较深的颜色。在淀积类金刚石之前,可以选择性地淀积例如包括锆的薄金属粘合层。然后将部件从真空系统中移除,并放置在带有超声搅拌的溶剂浴中。用溶剂将掩膜层溶解,并且还将在掩膜层的未刮擦部分顶部所淀积的部分DLC层移除。在通过掩膜层中的刮擦而形成的衬底表面的暴露部分上面所淀积的DLC保留在衬底表面上,提供装饰性灰色或黑色古式图案,所述图案再现了在掩膜层中的刮擦图案。本领域技术人员可以理解,使用其他暗颜色材料如锆的碳氧化物和碳氧氮化物可以获得类似的图案。
示例4
根据另一种理论示例,为了提供水平平滑的衬底表面,首先用已知工艺对注塑型塑料汽车装饰部件涂覆聚合物底层。将部件安装在真空室中,通过热丝或离子束PECVD法涂覆暗灰色或黑色类金刚石层。然后使用阴极电弧蒸发将部件涂覆上锆-钛氮化物的层。将部件从真空室中移除,通过图案化的丝网将永久油墨掩膜材料施加在部件上,由此形成具有诸如公司标识、数字图像或其他装饰性或信息图案之类的选定图案的非连续掩膜层。然后将部件浸渍在氟化氢铵稀溶液中,直至没有被掩膜层所保护的区域的锆-钛氮化物都被移除,在暗灰色或黑色背景上留下具有可见图案的耐用的亮黄色图像。
示例5
根据另一个理论示例,用已知方法对不锈钢调羹进行抛光和清洁,并将其安装在真空室中,并且通过PECVD涂覆厚度优选为至少约0.3微米-1微米的灰色或黑色DLC底色层。可选择性地,在淀积类金刚石之前,可以先淀积包括例如锆的薄金属粘合层。然后采用阴极电弧蒸发将锆的氮化物层淀积在类金刚石层上面。将部件从真空室中移除,并在部件上形成防水油墨掩膜层。在具有塑料滚动介质的桶中对部件进行滚动抛光,直至部分而不是全部的掩膜层被移除。然后将部件浸渍在氟化氢铵稀溶液中,直至没有被掩膜层所覆盖的区域中的锆的氮化物都被移除。如果掩蔽区域比未掩蔽区域大,由此制得例如具有图案化的装饰性“铜黑色(brass on black)”外观的调羹。如果掩蔽区域与未掩蔽区域相对较小,由此制得例如黄铜上具有图案化的装饰性“黑色仿古”终饰的调羹。
示例6
根据另一理论示例,使用包括例如镍-锡合金的已知材料对黄铜门把手进行电镀。将部件安装在真空室中,采用阴极电弧蒸发涂覆上锆的氮化物层。然后通过溅射法在部件上涂覆铝层。将部件从真空室中移除,并形成永久油墨掩膜层,随后使用如上所述的滚动抛光法进行图案化。然后通过已知的电化学方法将通过掩膜层中的穿透所暴露的部分铝涂层进行氧化黑色(black-anodized)处理。用溶剂将掩膜层移除,用不损坏下层锆底层的碱性蚀刻剂(如NaOH)将铝层的未氧化部分移除。由此形成例如耐用的装饰性“黑色仿古”终饰。
示例7
根据一个工作示例,用具有铬色表面的具有绸缎纹理的镍铬电镀叠层对黄铜毛巾环进行电镀。在低于一个大气压下,使用阴极电弧蒸发法在真空室中将包括黑色的锆的碳氧化物的涂层淀积在部件上,涂层厚度为0.4微米。然后使用磁电管溅射法形成0.25微米厚的铜层。使用塑料介质对部件进行振动批量抛光操作,以部分地移除铜,将下层锆的碳氧化物层的一部分暴露出来。随后仍然使用阴极电弧蒸发法形成0.15微米厚的最后的黄铜色的锆的碳氮化物的涂层。然后用过氧化氢和硫酸稀溶液对铜剥离层进行蚀刻。最后,将部件放入超声波水浴中以移除直接位于铜上的上层的松散附着的锆的碳氮材料。在通过振动抛光将铜移除的区域中,锆的碳氮化物保持原封不动,从而提供可见图案化的“耐气候黄铜”表面外观。
示例8
根据另一工作示例,用具有铬色表面的铜、镍和铬电镀叠层对锌龙头把手进行电镀。在低于一个大气压下,使用阴极电弧蒸发法在真空室中淀积0.5微米厚的包括金色锆的氮化物层的涂层。不对真空室进行通风,随后使用电磁管溅射法形成0.2微米厚的铬的第二涂料层。最后,仍然不通风,使用阴极电弧蒸发法形成0.5微米厚的锆的碳氮化物的暗色层。将耐水永久油墨的蚀刻掩膜层施加在部件上。使用塑料介质对部件进行转动抛光或振动批量抛光操作以移除部分油墨。然后将部件用氟化氢铵稀溶液进行蚀刻,以移除掩膜层已经被移除的区域中所暴露出来的顶层暗色涂料层部分。第一蚀刻在铬“蚀刻停止”层停止。接着,将部件浸渍在5%氢氧化钠溶液中,在该溶液中通过保持部件在相对于同一浴室中的扁平不锈钢电压为+8.0伏的条件下,对所暴露的铬进行阴极蚀刻。该最后的蚀刻步骤选择性地对铬进行蚀刻;将下层的金色的铬的氮化物区域暴露出来。最后,用丙酮洗涤部件以移除油墨。由油墨所保护的区域的上层暗色涂料层保持原封不动,从而提供可见图案化的“古色锡铅合金”表面外观。
注意到根据各种示例性实施例所示和所述的制品和方法仅为示意性目的是很重要的。虽然在该公开中仅详细描述了几个实施例,但本领域技术人员在阅读本公开后很容易想到,在本质上不背离权利要求中所述的主题的新型启示和优点的情况下,可以对本发明进行各种修改(如尺寸、大小、结构、形状和各种元素的比例、参数值、设置安排、所用材料、颜色、定位等的变化)。因此,所有这些变化都包括在本发明权利要求限定的范围内。任何工艺或方法步骤的顺序都可以根据其他示例性实施例进行变化或重新排序。在不背离所附权利要求限定的本发明范围的情况下,在设计、操作条件和优选或其他示例性实施例的设置上可以作出各种其他替换、修改、改变和省略。
Claims (58)
1.一种具有装饰性的、可见图案的多色表面外观的制品,所述制品包括:
衬底;
第一涂层,通过气相淀积提供在所述衬底上,所述第一涂层包括具有第一颜色的第一材料;
第二涂层,通过气相淀积提供在所述第一涂层的至少一部分上,所述第二涂层包括具有第二颜色的第二材料,所述第二颜色不同于所述第一颜色;
其中,所述第二涂层包括随机排列的穿透,通过所述穿透可以看见下层表面的一部分,所述第一涂层包括所述下层表面;
其中所述穿透形成包括人的肉眼可区别出的特征的装饰性图案。
2.如权利要求1所述的制品,其中,在低于一个大气压下,采用物理气相淀积工艺或化学气相淀积工艺在真空室中对所述第二涂层进行淀积。
3.如权利要求2所述的制品,其中,所述物理气相淀积工艺包括阴极电弧蒸发。
4.如权利要求2所述的制品,其中,所述化学气相淀积工艺包括热丝PECVD工艺。
5.如前述权利要求中的任意一项所述的制品,其中,所述第二材料包括金属。
6.如权利要求5所述的制品,其中,所述第二材料还包括选自由氮、氧和碳组成的组中的至少一种材料。
7.如权利要求6所述的制品,其中,所述第二材料包括选自由锆、钪、钛、铬、铪、碳组成的组中的至少一种材料和含有金属的阳极化层。
8.如权利要求1-4和6-7中任意一个所述的制品,其中,所述第一材料包括金属。
9.如权利要求8所述的制品,其中,所述第一材料还包括选自由氮、氧和碳组成的组中的至少一种材料。
10.如权利要求9所述的制品,其中,所述第一材料包括选自由锆、钛、铬、铪和钪组成的组中的至少一种材料。
11.如权利要求10所述的制品,其中,所述第二材料包括锆和钪中的至少一种。
12.如权利要求1-4和6-7中任意一个所述的制品,其中,所述第一材料包括锆、氧和碳,所述第二材料包括锆和氮。
13.如权利要求1-4和6-7中任意一个所述的制品,其中,所述第一材料包括类金刚石。
14.一种用于制造具有装饰性涂层的制品的方法,所述方法包括:
在低于一个大气压下,使用物理或化学气相淀积法在真空室中将至少第一涂层淀积到衬底表面的至少一部分上,其中所述至少第一涂层包括第一涂层和第二涂层,所述第一涂层包括具有第一颜色的第一材料,所述第二涂层包括具有第二颜色的第二材料;和
使用非均匀图案化工艺对所述第二涂层进行图案化,以形成具有穿透的图案化的涂层,通过所述穿透可以看见所述下层表面的一部分,所述下层表面包括所述第一材料,所述第一颜色视觉上与所述第二颜色可对比;
其中所述非均匀图案化工艺包括在利用非均匀修整工艺对掩膜层进行图案化之前或同时在所述第二涂层上应用所述掩膜层,包括在所述掩膜层中形成穿透,通过所述穿透使得所述第二涂层的一部分暴露出来;
其中,所述图案化的第二涂层包括装饰性图案,所述图案包括通过人的肉眼可区别的特征。
15.如权利要求14所述的方法,其中,所述第一材料和所述第二材料中的至少一种包括类金刚石。
16.如权利要求14所述的方法,其中,所述第二材料包括金属。
17.如权利要求16所述的方法,其中,所述第二材料还包括选自由氮、氧和碳组成的组中的至少一种材料。
18.如权利要求17所述的方法,其中,采用阴极电弧蒸发工艺和热丝PECVD法中的一种,对所述第二涂层进行淀积。
19.如权利要求17所述的方法,其中,所述第二材料包括选自由锆、钪、钛、铬、铪和碳组成的组中的至少一种元素。
20.如权利要求14-19中任意一项所述的方法,其中,所述第二材料包括含有金属的阳极化层。
21.如权利要求14-19中任意一项所述的方法,其中,所述非均匀图案化工艺包括蚀刻工艺。
22.如权利要求14-19中任意一项所述的方法,其中,所述非均匀图案化工艺包括剥离工艺。
23.如权利要求14-19中任意一项所述的方法,其中,所述非均匀图案化工艺包括滚动抛光工艺或振动抛光工艺。
24.如权利要求14-19中任意一项所述的方法,其中,所述非均匀图案化工艺包括形成非连续的所述掩膜层。
25.如权利要求24所述的方法,其中,所述非均匀图案化工艺包括移除位于所述掩膜层中的穿透下方的部分所述第二涂层。
26.如权利要求24所述的方法,其中,所述掩膜层中的穿透是采用线刷或纤维刷形成的。
27.如权利要求24所述的方法,其中,所述掩膜层中的穿透是通过光刻工艺形成的。
28.如权利要求24所述的方法,其中,所述掩膜层中的穿透是通过非均匀地施加掩膜材料形成的。
29.如权利要求28所述的方法,其中,所述掩膜材料是采用烫印或者模板非均匀地施加的。
30.如权利要求28所述的方法,其中,所述掩膜材料是采用丝网工艺和喷射工艺中的至少一种工艺非均匀地施加的。
31.如权利要求24所述的方法,其中,所述掩膜层中的穿透是采用至少同时处理十个部件的批量抛光操作生成的。
32.如权利要求14所述的方法,其中,所述第一材料含有金属。
33.如权利要求32所述的方法,其中,所述第一材料还包括由氮、氧和碳组成的组中的至少一种成分。
34.如权利要求33所述的方法,其中,所述第一材料包括由锆、钛、铬、铪或钪组成的组中的至少一种成分。
35.如权利要求14所述的方法,其中,所述第一材料包括锆、氧和碳,所述第二材料包括锆和氮。
36.如权利要求14所述的方法,其中,所述第一材料包括碳。
37.如权利要求36所述的方法,其中,所述第二材料包括碳。
38.如权利要求14所述的方法,其中,所述第一材料包括含有金属的的阳极化层。
39.一种用于制备具有装饰性表面的制品的方法,所述方法包括:
使用气相淀积法将第一材料层淀积到衬底上,所述第一材料层包括具有第一颜色的第一材料;
使用气相淀积法将第二材料层淀积到所述第一材料层上面,所述第二材料层包括具有第二颜色的第二材料,所述第二颜色不同于所述第一颜色;以及
移除部分所述第二材料层以形成延伸穿过所述第二层的孔,所述孔以随机配置排列;
其中,通过所述孔可看见部分所述第一层,从而在所述制品上形成装饰性图案。
40.如权利要求39所述的方法,其中,移除部分所述第二材料层的步骤包括掩膜工艺。
41.如权利要求40所述的方法,其中,所述掩膜工艺包括在所述第二材料层上面提供掩膜,所述掩膜包括油墨、涂料、石蜡和金属中的至少一种。
42.如权利要求40所述的方法,其中,所述掩膜工艺包括在所述第二材料层上面提供掩膜,所述掩膜至少包括光致抗蚀剂。
43.如权利要求40所述的方法,其中,所述掩膜工艺包括在所述第二材料层上面提供掩膜,所述掩膜至少包括漆。
44.如权利要求41所述的方法,其中,移除部分所述第二材料层的步骤包括蚀刻工艺、剥离工艺和滚动抛光或振动抛光工艺中的至少一种。
45.如权利要求41所述的方法,其中,移除部分所述第二材料层的步骤包括形成具有穿透的非连续掩膜层,通过所述穿透使得所述第一涂层的一部分暴露出来。
46.如权利要求45所述的方法,其中,移除部分所述第二材料层的步骤包括移除在所述掩膜层中的穿透下方的部分所述第二材料层。
47.如权利要求45所述的方法,其中,所述掩膜层中的穿透是通过非均匀施加掩膜材料形成的。
48.如权利要求45所述的方法,其中,所述掩膜层中的穿透是采用至少同时处理十个部件的批量抛光操作生成的。
49.如权利要求41所述的方法,其中,所述第一材料包括金属和选自由氮、氧和碳组成的组中的至少一种材料。
50.如权利要求49所述的方法,其中,所述第一材料包括锆、钛、铬、铪和钪中的至少一种。
51.如权利要求41所述的方法,其中,采用热丝PECVD法和阴极电弧蒸发工艺中的至少一种,对所述第一涂层进行淀积。
52.如权利要求41所述的方法,其中,所述第一材料包括含有金属的阳极化层。
53.如权利要求41所述的方法,其中,所述第二材料包括金属和由氮、氧和碳组成的组中的至少一种成分。
54.如权利要求43所述的方法,其中,所述第二材料包括锆、钛、铬、铪或钪。
55.如权利要求41所述的方法,其中,所述第二材料包括锆、氧和碳,所述第一材料包括锆和氮。
56.如权利要求41所述的方法,其中,所述第一材料和所述第二材料中的至少一种包括类金刚石。
57.如权利要求41所述的方法,其中,所述第二材料包括碳。
58.如权利要求56所述的方法,其中,所述第一材料包括碳。
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- 2006-07-17 MX MXPA06008122A patent/MXPA06008122A/es active IP Right Grant
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- 2006-07-25 CN CN2006101074648A patent/CN1936068B/zh not_active Expired - Fee Related
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ES2395733T3 (es) | 2013-02-14 |
US8123967B2 (en) | 2012-02-28 |
US20080264903A1 (en) | 2008-10-30 |
PL1749898T3 (pl) | 2013-02-28 |
MXPA06008122A (es) | 2007-03-23 |
CN1936068A (zh) | 2007-03-28 |
CA2549981C (en) | 2012-07-24 |
EP1749898B1 (en) | 2012-09-26 |
CA2634297A1 (en) | 2007-02-01 |
EP1749898A2 (en) | 2007-02-07 |
CA2549981A1 (en) | 2007-02-01 |
US20070026205A1 (en) | 2007-02-01 |
EP1749898A3 (en) | 2008-06-25 |
CA2634297C (en) | 2013-11-19 |
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