CN1656034A - 具有美观涂层的制品 - Google Patents
具有美观涂层的制品 Download PDFInfo
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- CN1656034A CN1656034A CNA03812369XA CN03812369A CN1656034A CN 1656034 A CN1656034 A CN 1656034A CN A03812369X A CNA03812369X A CN A03812369XA CN 03812369 A CN03812369 A CN 03812369A CN 1656034 A CN1656034 A CN 1656034A
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Images
Classifications
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Abstract
本发明涉及一种制品，例如汽车透明体，包括第一基材和至少一种沉积在所述基材至少一部分之上的美观涂层。所述至少一种美观涂层为所述制品提供由－10≤a*≤0和－15≤b*≤5所限定的颜色和在8－50％范围的反射率。
Description
相关申请的交叉引用
本申请要求2002年5月31日申请的美国临时申请序列号60/384857的权益，其全部内容都引入本文，供作参考。
发明背景
1.发明领域
本发明总体上涉及制造涂敷制品的方法，例如(但不限于)桌面、浴室门、隔板、和汽车透明体，还涉及由此制成的制品。
2.技术现状
在今天的汽车市场上，主要重点放在车辆式样中。对于车辆销售来说，车辆外观与车辆的机械可靠性或安全特性同样重要。因此，汽车制造商尽一切所能来提高车辆式样。这些式样改进包括向顾客提供更多的颜色选择和提供具有金属薄片的颜色以使车辆具有“多色效果”。
尽管这些式样改进通常都已经被消费者充分接受，但是，到目前为止，仍然存在着这样一个问题，即使有新的车辆油漆罩面层，汽车透明体(例如(但不限于)挡风玻璃、侧窗、后窗、月光篷顶和遮阳篷顶)依旧通常是灰色或中性颜色的。除了提供防阳光性能，这些常规透明体对于车辆式样没有改进。
在非汽车领域，业已知道提供其中颜色由基材和涂层之间的干涉效应产生的涂敷制品。如本领域技术人员所知道的，术语“干涉效应”是指电磁波振幅随着距离或时间的变化，它是由电磁辐射(例如可见光)波的叠加而引起的。这些电磁波可以是在光学薄膜涂层中的一个或多个层的界面处的反射或透射的结果。例如，US6164777公开了具有由交替的不同折射率材料制成的干涉涂层的塑料接触镜。US5923471公开了用于加热灯的具有交替的氧化锆和氧化硅层的“热镜”。美国专利公开文本US2003/0031842A1公开了一种具有图案外观(由一个或多个普通透明薄膜涂层之间的肉眼可观察到的反差提供)的制品。干涉涂层和涂敷制品的其它实例公开在美国专利US5619059、US4902581、US5112693、和瑞士专利339575之中。
尽管这些公开的涂层适合于它们的预期目的，但是在试图将干涉涂层结合到汽车透明体之中时仍需要考虑许多其它问题。例如，在美国，政府法规要求所有挡风玻璃都必须具有至少70％的光线的(可见的)透光率(Lta)。在欧洲，要求的最小Lta是75％。由于干涉涂层的存在，将会对透明体的透光率产生不利的影响。
提供一种制造美学上是令人愉快的且能用来改进汽车式样的汽车透明体的方法将是受人欢迎的。提供一种能够使透明体的颜色与汽车油漆颜色相符或相匹配成为可能的汽车透明体也将是受人欢迎的。如果这类透明体还能符合对于汽车透明体政府要求的规格，则将是更加受人欢迎的。
发明概述
本发明的制品如汽车透明体，包括第一基材和至少一种沉积在所述基材至少一部分之上的美观涂层。所述至少一种美观涂层可为所述制品提供由-10≤a*≤0和/或-15≤b*≤5所限定的颜色和/或在8-50％范围的可见光反射率。例如，制品可具有的a*值在-5至0范围之内，如-4至-1，如-4至-1.5。制品可具有的b*值在-10至+4范围之内，如-8至+3。制品可具有的反射率在8-25％范围之内，如8-20％，如16-20％，如9-18％。本发明制品可为层压制品或整体制品。在一种特定实施方式中，对于汽车透明体来说，所述可见光反射率可在8-30％范围之内。
在一种非限制性实施方式中，所述制品具有银色外观，且所述美观涂层提供的a*值是在-4至0范围之内，其b*值是在-10至-6范围之内。在另一种非限制性实施方式中，所述制品具有白镴(pewter)外观，且所述美观涂层提供的a*值是在-5至-1范围之内，其b*值是在-3至+3范围之内。
一种制造制品如具有至少一种美观涂层的汽车透明体的方法，包括沉积至少一种美观涂层在第一基材的至少一部分上的步骤。所述至少一种美观涂层沉积的厚度足以为第一基材提供由-5≤a*≤0和/或-15≤b*≤5所限定的颜色和/或在8-50％例如8-30％范围的可见光反射率。
附图简要说明
图1所示为结合本特征的涂敷制品的侧视截面示意图(不按比例)；
图2所示为结合本发明特征的层压汽车物体的侧视截面示意图(不按比例)；
图3所示为表1中选择样品的a*和b*值的曲线图；
图4所示为表1中选择样品的反射率(R1)相对光学厚度(nd)的曲线图；
图5所示为表1中选择样品的R1相对厚度的曲线图；和
图6所示为图5所示样品的L*相对厚度的曲线图。
优选实施方式说明
本文所用的空间或方向术语如“内”、“外”、“左”、“右”“之上”、“之下”等，与附图所示的本发明有关。但是，应该理解，本发明可假定多种可选择取向，因此，这些术语不能认为是限制性的。而且，本文所用的在说明书和权利要求书中使用的表示尺寸、物理特征等的所有数值，可理解为在所有情形可由术语“约”来修饰。因此，除非有相反的指示，下述说明书和权利要求书中所列举的数值，都可根据本发明寻求得到的所需性能进行变化。无论如何，不希望限制等同原则适用本发明权利要求书的范围，每个数值应当至少按照所报告的有效数字的数值和根据使用常规的四舍五入法进行解释。而且，本文所述所有范围应当理解为包含在其中的任意和全部子范围。例如，所称“1-10”应该认为是包括在最小值1和最大值10之间(端值在内)的任意和所有子范围；也就是说，以最小值1或更大为起点和以最大值10或更小为终点的所有子范围，例如5.5-10。而且，本文所用的术语“沉积在……之上”、“涂敷在……之上”或“提供在……之上”表示沉积、涂敷或提供在……之上，但不是必需与该表面进行接触。例如，一种物质“沉积在”基材“之上”，不排除存在着一个或多个其它的相同或不同组成的材料位于所沉积材料与所述基材之间。另外，所有本文引用的参考文献都应该理解为可以它们的全部内容结合到本文中。术语“美观涂层”是指一种提供用来提高所述基材的美观性能的涂层，如颜色、色调、色相、或可见光反射率，但不必是所述基材的防阳光性能。但是，所述美观涂层也能提供美观以外的性能，例如，紫外线(VU)辐射吸收或反射和/或红外线(IR)吸收或反射。所述美观涂层也可仅仅通过降低通过所述制品的可见光透光率而提供某些防阳光效果。在下述讨论中，折射率数值是相对于550nm参比波长的数值。术语“可见区”或“可见光”是指电磁辐射具有380-780nm范围的波长。术语“红外区”或“红外线辐射”是指电磁辐射具有大于780-100000nm范围的波长。术语“紫外区”或“紫外线辐射”表示电磁能具有300nm至小于380nm范围的波长。术语“光学厚度”表示材料相对于550nm的折射率(无量纲的)乘以其物理厚度(以埃()计)的乘积。本文所述可见的(光线的)透光率(Lta)数值(Y，x，y)是那些可通过使用C.I.E.(1976)标准光源“A”，采用2°观察器(与美国联邦标准一致)，在380-770nm波长范围内，使用Lambda 9分光光度计(可自Perkin-Elmer获得)或BYK-Gardner TCS分光光度计(可自BYK-Gardner获得)检测得到的数值。反射颜色数值L*、a*、b*(无论R1或R2)是通过使用光源“D65”，采用10°观察器，测量得到的(这在汽车领域是常规的)。术语“膜”是指具有所需的或选择的组成的涂层区域。“层(layer)”包括一个或多个“膜”。“涂层”或“涂层叠层”由一个或多个“层”组成。
由下述讨论将会理解，本发明所述美观涂层可用于制造层压或非层压的制品中，例如单层制品。将首先对本发明示例性整体制品进行说明，接着，将对本发明的示例性层压制品进行说明。至于“整体”是表示具有单一结构基材或主要层(ply)，例如玻璃层。所述示例性制品(无论层压制品或整体制品)是以汽车侧窗进行说明的。但是，本发明不局限于汽车侧窗，它可用于任意制品，例如(但不限于)绝缘玻璃元件、住宅或商用层压窗(如天窗)、浴室门、隔板、桌面、或用于陆地、空中、空间、水上和水下运载工具的透明体如汽车挡风玻璃、后窗、遮阳篷顶、月光篷顶等。
图1图示说明了结合本发明特征的示例性涂敷制品10。所述制品10包括一个基材12，它具有第一主表面14和第二主表面16。本发明至少一种美观涂层20提供在至少一个所述主表面14、16的至少一部分之上。在图1所示的示例性实施方式中，所述至少一种美观涂层20，提供在全部或基本全部的第一表面14之上。至于“沉积在基本全部的第一表面之上”表示所述至少一种美观涂层20覆盖了所述表面的大部分，而不是在离散的区域中形成。在一种实施方式中，所述至少一种美观涂层20可被提供在除了邻近或沿着第一表面14的周边边缘的非涂敷区域之外的全部第一表面14之上。在另一种实施方式中，当美观涂层妨碍所需的电磁辐射透过率时，一个或多个更小区域的所述涂层可被消去或被除去(或在涂敷之前被掩蔽)，如对于天线和“Easy-Pass”涂敷。如下将作更详细的描述，任选的功能性涂层22，可沉积在一个或多个所述主表面14、16的至少一部分之上，例如，在所述至少一种美观涂层20和所述基材12之间，或者沉积在所述美观涂层20之上，或者，所述美观涂层20可结合到所述功能性涂层的涂层叠层之中。如下所述，任选的保护涂层24可提供在所述至少一种美观涂层20的至少一部分之上。任选的涂层30如陶瓷涂层或遮光条带，也可沉积在第二主表面16的至少一部分之上。
在本发明的广泛应用中，所述基材12不限于本发明，可为任意具有任何所需特征的材料，如对于可见光不透明、半透明或透明的材料。至于“透明”是表示具有大于0-100％的通过所述基材的透光率。或者，所述基材可以是半透明或不透明的。至于“半透明”是表示能够允许电磁能(如可见光)透过所述基材，但散射这种能量，使得在基材与观察者相对一侧的物体不能清楚地可见。至于“不透明”是表示具有0％的可见光透光率。合适的基材实例包括(但不限于)塑料基材(如丙烯酸类聚合物，如聚丙烯酸酯；聚烷基甲基丙烯酸酯，如聚甲基丙烯酸甲酯、聚甲基丙烯酸乙酯、聚甲基丙烯酸丙酯等；聚氨酯；聚碳酸酯；聚烷基对苯二甲酸酯，如聚对苯二甲酸乙二醇酯(PET)、聚对苯二甲酸丙二醇酯、聚对苯二甲酸丁二醇酯等；含聚硅氧烷聚合物；或任意用于制备这些聚合物的单体或其任意混合物的共聚物)；金属基材，例如(但不限于)镀锌钢、不锈钢、和铝；陶瓷基材；砖基材；玻璃基材；或任意上述物质的混合物或组合。例如，所述基材可为常规的无色钠钙玻璃，即“透明玻璃”，或者可为带色彩的或着色玻璃、硼硅酸盐玻璃、含铅玻璃、回火的、非回火的、退火的、或热强化玻璃。所述玻璃可为任意类型，如常规的浮法玻璃或平板玻璃，且可为任意具有任意光学性能的组成，例如，任意数值的可见光辐射透射、紫外线辐射透射、红外线辐射透射、和/或总的阳光能量透射。典型汽车类玻璃可具有如蓝色、绿色、青铜色、灰色，这些玻璃的非排他性实例包括可自PPG Industries，Inc.of Pittsburgh，Pennsylvania购买得到的玻璃，商品名称为Solex玻璃、Solargreen玻璃、Solextra玻璃、和VistaGrayTM玻璃。这些玻璃可为未回火的、热处理的、或热强化玻璃。本文所述术语“热处理的”表示加热到足以弯曲或退火或回火所述玻璃的温度。所述术语“热强化的”表示退火的、回火的、或至少部分回火的。虽然不限制于本发明，适合于所述基材12的实例，公开在US4746347、US4792536、US5240886、US5385872、和US5393593之中。所述基材12可为任意所需的尺寸，例如长度、宽度、形状、或厚度。对于常规汽车透明体来说，所述基材12典型地可达10mm厚，如1-10mm厚，如低于10mm厚，如1-5mm厚，如1.5-2.5mm，如1.6-2.3mm。所述基材12可为平板基材，或者可为成形的、弯曲的、或曲面的。至于术语“平板基材”是表示基本以单一几何平面放置的基材，例如，由常规浮法玻璃方法制得的玻璃。而“成形的”或“弯曲的”是表示不是平板的基材。
所述至少一种美观涂层20，可为干涉涂层，用来为所述涂敷制品10提供美观特征，但它不会或仅会轻微地影响所述涂敷制品10的防阳光性能。本文所用术语“干涉涂层”是指由于干涉效应(如前所述)能够产生颜色(例如在透射或反射中)的涂层。在一种实施方式中，所述美观涂层20包括一层或多层的涂层材料，具有足以能够为所述涂敷制品10提供可见光反射率在8-50％范围的厚度，例如反射率为8-30％，例如8-25％，例如8-20％，例如16-20％，例如9-18％。所述美观涂层20可提供在由-10≤a*≤0限定的色空间之内的反射颜色，例如在-8至0范围之内，例如在-6至0，例如-5至0，例如-4至-1，例如-4至-1.5。所述美观涂层20可提供范围在-15≤b*≤5的b*值，例如-10至+4，例如-8至+3。
如本领域技术人员所知，物体(特别是玻璃)的颜色，是高度主观性的。观察到的颜色将依赖于照明条件和观察者的喜好。为了在定量的基准上评价，业已经开发了多种色级体系。一种被国际照明协会(CIE)采用的确定颜色的方法，是使用主波长(DW)和色纯度(Pe)。对于一种给定颜色的这两种技术标准的数值，可通过计算来自所谓颜色的三色值X、Y、Z的颜色坐标x和y而确定。所述颜色坐标标绘在1931 CIE色度图上，并与CIE标准光源C的坐标进行数量对比，后者标记在CIE出版号No.15.2中。这种比较可在所述色度图上提供色空间，以确定所述玻璃颜色的色纯度和主波长。
在另一种色级体系中，颜色是以色调和明度来进行规定的。这种体系通常称作CIELAB颜色体系。色调区分颜色如红色、黄色、绿和蓝色等颜色。明度或数值区分明或暗的程度。这些特征的数值(它们标记为L*、a*和b*)，是由三色值(X、Y、Z)计算得到的。L*指示颜色的明度或暗度，并表示该颜色处于的明度平面。a*指示在红(+a*)绿(-a*)坐标轴上该颜色的位置。b*指示在黄(+b*)蓝(-b*)坐标轴上该颜色的位置。当所述CIELAB体系的直角坐标转换为柱面极坐标时，所得到的颜色体系被称作CIELCH颜色体系，它以明度(L*)、和色调角(H°)和色度(C*)来确定颜色。L*指示在所述CIELAB体系中颜色的明度或暗度。色度(或饱和度或强度)区分颜色的强度或清晰度(即明亮相对于晦暗)，它是从该色空间中心到所测量的矢量距离。颜色的色度越低，即其强度越小，则该颜色越接近于所谓的中性颜色。对于所述CIELAB体系来说，C*＝(a*2+b*2)1/2。色调角区分颜色如红色、黄色、绿和蓝色，它是从所述红(+a*)轴逆时针方向测得的经过所述CIELCH色空间中心的自所述a*、b*坐标延伸矢量的角度数值。
能够理解，颜色可以以任意的这些颜色体系进行表征，本领域技术人员可以从观察玻璃或复合透明体的透光率曲线计算出等价的DW和Pe数值；L*、a*、b*数值；和L*、C*、H°数值。颜色计算的详细讨论公开在US5792559中。在该文献中，颜色是通过使用所述CIELAB体系(L*a*b*)计算得到。但是，也应该明白，这仅是为了讨论的方便，所公开的颜色可由任意常规体系来确定，如上述的那些体系。
在一种实施方式中，所述美观涂层20包括一层或多层金属氧化物涂层材料，所具有的厚度足以产生由-10≤a*≤0和-15≤b*≤5限定的干涉效应颜色且反射率在8-50％范围内如8-30％。可用于本发明的示例性材料包括(但不限于)氧化硅、氧化铝、氧化锌、氧化锡、氧化铌、氧化钽、氧化锆、氧化钛、碳(本领域人员常称作“类金刚石碳”或DLC)、氧化铝、锌和锡材料(例如(但不限于)锡酸锌)和金属的氧化物、氮化物、或氮氧化物如氮氧化硅、或含有任意一种或多种上述材料的任意混合物。
所述至少一种美观涂层20还包括一种或多种添加剂或掺杂剂，以影响所述至少一种美观涂层20的性能，如折射率、光催化活性、和本领域技术人员已知的其它性质。掺杂剂的实例包括(但不限于)钠、镍、过渡金属、和含有任意一种或多种前述物质的混合物。
所述至少一种美观涂层20可为任意厚度，以获得如上所述所需的颜色和反射率。本领域技术人员将会理解，所述至少一种美观涂层20的具体厚度可根据选用的材料而变化，以获得所述所需的颜色和反射率。所述至少一种美观涂层20具有的最小厚度大于0。在一种非限制性实施方式中，所述至少一种美观涂层20的最大厚度为20000，例如15000，例如10000。对于大于约1.5微米的光学厚度来说，所述至少一种美观涂层20可表现出厚膜性态(例如，其定义见“Optics ofThin Films”，A.Vasicek，North Holland Publishing Company，Amsterdam，Interscience Publishers Inc.New York，NY，1960，pg.139)。例如，折射率约1.5的氧化硅，可在物理厚度约9167(或约1微米)时表现出厚膜性态，折射率约2.5的氧化钛在约5500(约0.5微米)时表现出厚膜性态。在一种非限制性实施方式中，所述美观涂层20可具有的厚度在大于0-20000 范围内，例如大于0-10000，大于0-5000，例如大于0-1000，例如100-500。另外，所述至少一种美观涂层20，当它进行沉积时，在整个表面上没有必要是均匀厚度。例如，所述至少一种美观涂层20可以是非均匀的或变动的厚度(例如，具有较高或较低的厚度区域)，以便在所述涂敷表面上提供能够感觉到的色差，例如彩虹效果。
除了上述的a*、b*尺寸之外，所述涂敷制品10还具有足以能够为所述涂敷制品10提供所需水平的明度以获得美学上令人愉快外观的L*值。在一种非限制性实施方式中，所述涂敷制品10具有的L*值在45-55范围之内。
对用于向前的汽车透明体(例如挡风玻璃和前侧窗)来说，所述涂敷制品10可具有的Lta值大于或等于70％，例如大于或等于75％。对于非向前的视觉面板(例如“隐避玻璃”)来说，所述Lta值可小于75％，例如小于70％。
为了为所述涂敷制品10(特别是层压汽车透明体)提供美学上受人欢迎的光泽或光彩，所述涂敷(层压)制品10可具有范围在8-50％的可见光反射率，例如8-30％，例如8-25％，例如8-20％，例如15-25％，例如16-20％，例如9-19％。本领域技术人员将会理解，对于层压制品来说，所述反射率通常采用所述层压制品的外部反射率来限定。所述“外部反射率”表示具有美观涂层提供在一个内部表面如2号表面或3号表面上的该外部表面(1号表面)的反射率。
所述至少一种美观涂层20可为具有两层或多层的具有不同折射率的涂层材料的多层涂层叠层。例如，所述至少一种美观涂层20可包括至少一种具有第一(低的)折射率的第一层和至少一种提供在第一层之上的具有第二(高的)折射率的其它层。一种替代方案是，所述至少一种美观涂层可具有第一(低的)折射率层、第二(高的)折射率层、和第三(中等)折射率层，第一、第二和第三层可以任意所需的顺序进行沉积。例如，第二(高的)折射率层可提供在第一(低的)折射率层之上，而第三(中等)折射率层沉积在第二(高的)折射率层之上。一种替代方案是，所述美观涂层可包括第一(中等)折射率层、提供在第一层之上的第二(低的)折射率层、和提供在第二层之上的第三(高的)折射率层。
术语“低的”、“中等”、和“高的”可以是针对所述涂层叠层材料的相对术语。例如，在涂层叠层中，“中等”折射率材料可为任意的具有折射率大于所述“低的”折射率材料(即所述叠层材料中具有最低相对折射率数值的材料)折射率的材料，“高的”折射率材料可为任意的具有折射率大于所述中等折射率材料折射率的材料。在一种实施方式中，所述材料可以是在最接近所述基材(例如玻璃)上沉积“中等”折射率材料，所述“低的”折射率材料沉积在所述中等折射率材料之上，所述“高的”折射率材料沉积在所述低的折射率材料之上。一种用来说明这种结构的示例性涂层叠层是：氧化铝层沉积在基材上，氧化硅层沉积在所述氧化铝层上，氧化钛层沉积在所述氧化硅层上。在一种特定实施方式中，所述“低的折射率”材料可具有低于1.7的折射率。所述“高的折射率”材料可具有大于2.1的折射率。所述“中等折射率”材料可具有范围在1.7-2.1之间的折射率。在这种实施方式中，氧化硅和氧化铝是低的折射率材料的实例。氧化钛将是高的折射率材料的实例。锡酸锌和氧化锆是中等折射率材料的实例。在一种示例性的两层体系中，第一涂层层可含有锡酸锌，第二涂层层可含有氧化钛。在一种实施方式中，所述锡酸锌层可具有的厚度在100-300范围之内，例如200，所述氧化钛层具有的厚度在100-300范围之内，例如200。
所述至少一种美观涂层20可包括单一层，例如(但不限于)氧化锆。在一种实施方式中，所述单一氧化锆层可具有的厚度是在70-700范围之内。在另一种实施方式中，所述美观涂层20可包括一种或多种分级(graded)的层。“分级的”是表示这样一种涂层，在从所述层的一个表面或界面向相对表面或界面移动时，其一种或多种成分的分数提高，而一种或多种其它成分的分数降低。例如，在一种实施方式中，所述美观涂层20可包括分级的氧化硅-氧化锆层(即这样的层，其组成从一个表面上的0wt％氧化锆和100wt％氧化硅变化到相对表面上的100wt％氧化锆和0wt％氧化硅)，任选的氧化锆层沉积在所述分级层之上。在另一种实施方式中，所述分级的层可具有的厚度为2000，所述任选氧化锆层可具有的厚度为10000。在另一方面所述分级的层可从一种类型材料如氧化物变化为另一种类型材料如氮化物。例如，所述分级层可从氧化硅变化为氮化硅。
所述至少一种美观涂层20可以任意常规方法进行沉积，例如(但不限于)磁控管溅射汽相沉积(MSVD)、热解沉积如化学汽相沉积(CVD)、喷雾热解、大气压力CVD(APCVD)、低压CVD(LPCVD)、等离子体增强CVD(PEVCD)、等离子体辅助CVD(PACVD)、或电阻或电子束加热的热蒸发、阴极电弧沉积、等离子体喷雾沉积、湿法化学沉积(例如溶胶-凝胶、镜面镀银等)、或任意其它理想的方法。在一种实施方式中，所述至少一种美观涂层20可通过MSVD法进行沉积。MSVD涂敷装置和方法的实例，对于本领域技术人员来说是已知的，例如，公开在US4379040、US4861669、US4898789、US4898790、US4900633、US4920006、US4938857、US5328768、和US5492750之中。在所述MSVD法中，金属或金属合金的氧化物可通过在含氧气氛中溅射含金属或金属合金的阴极以沉积金属氧化物或金属合金氧化物膜到所述基材表面上而实现沉积。在一种实施方式中，所述美观涂层20沉积在全部或基本全部所述表面14上，即不沉积形成离散的涂敷区域。所述至少一种美观涂层20可沉积在平板基材之上，接着所述基材以任意常规方法进行弯曲或成形。一种替代方案是，所述至少一种美观涂层20可沉积在弯曲表面上，例如，业已被弯曲或成形的基材上。
在如图1所示的整体实施方式中，任选功能性涂层22可沉积在一个或多个所述表面14、16之上，如位于所述基材12和所述至少一种美观涂层20之间，沉积在所述美观涂层20之上，或者所述美观涂层20可结合到所述性涂层22的涂层叠层之中。所述功能性涂层22可为任意所需的类型。本文所用的术语“功能性涂层”是指这样一种涂层，它能够改进其沉积于其上的所述基材的一种或多种物理性质，例如，光学、热学、化学、机械性能，而且在随后加工过程中它不易于完全地从所述基材上除去。所述功能性涂层22可以具有一种或多种由相同或不同组成或功能的功能性涂层薄膜或层。
所述功能性涂层22可为导电涂层，如用来制造可加热窗的导电涂层，如US5653903和US5028759所述，或者可为用作天线的单一薄膜或多层薄膜涂层。同样地，所述功能性涂层22可为防阳光涂层。本文所用术语“防阳光涂层”是指由一个或多个层或薄膜组成的涂层，该薄膜能够影响所述涂敷制品的阳光性能，例如(但不限于)阳光辐射数量，例如自所述涂敷制品反射和/或透过所述涂敷制品的可见光、红外线、或紫外线辐射，遮蔽系数等。所述防阳光涂层可以阻挡、吸收或过滤选择部分的太阳光谱，例如(但不限于)IR、UV、和/或可见光光谱。可用于实施本发明的防阳光涂层实例可在下述文献中找到，例如(但不限于)US4898789、US5821001、US4716086、US4610771、US4902580、US4716086、US4806220、US4898790、US4834857、US4948677、US5059295、和US5028759、以及美国专利申请序列号09/058440。一种替代方案是，所述功能性涂层22可为能影响所述涂敷制品发射率的涂层。
适合用于本发明的功能性涂层实例是自PPG Industries，Inc.ofPittsburgh，Pennsylvania商购获得的SUNGATE和SOLARBAN系列涂层。这类功能性涂层通常含有一种或多种含介电或抗反射材料的抗反射膜，如金属氧化物或金属合金的氧化物，它们对于可见光是透明的。所述功能性涂层也可含有一种或多种含反射金属的红外线反射膜，如贵金属如金、铜或银、或其结合或合金，它还可含有底漆薄膜或位于所述金属反射层之上和/或之下的阻挡薄膜如钛、镍、铬、或其它本领域已知的底漆。所述功能性涂层可具有任意所需数目的红外线反射膜，如1个或多个银层，例如2个或多个银层，例如3个或多个银层。
如图1所示，任选的保护涂层24可沉积在所述至少一种美观涂层20之上。所述保护涂层24可为任意所需的厚度。在一种示例性实施方式中，所述保护涂层24具有的厚度范围为100-50000，如500-50000，例如500-10000，如100-2000。在另外非限制性实施方式，所述保护涂层24可具有的厚度范围为100-10微米，如101-1000，或1000-1微米，或1-10微米，或200-1000。而且，所述保护涂层24可具有非均匀的厚度。至于“非均匀厚度”是表示所述保护涂层24厚度可在某一给定单位区域内变动，例如，所述保护涂层24可具有高和低的点和面。
所述保护涂层24可任意所需的材料或材料混合物。在一种示例性实施方式中，所述保护涂层24可包括一种或多种金属氧化物材料，例如(但不限于)氧化铝、氧化硅、或其混合物。例如，所述保护涂层可为单一涂层，它含有范围为0-100wt％氧化铝和/或0-100wt％氧化硅，如5-100wt％氧化铝和95-0wt％氧化硅，如10-90wt％氧化铝和90-10wt％氧化硅，如15-90wt％氧化铝和85-10wt％氧化硅，50-75wt％氧化铝和50-25wt％氧化硅，如50-70wt％氧化铝和50-30wt％氧化硅，35-100wt％氧化铝和65-0wt％氧化硅，例如70-90wt％氧化铝和10-30wt％氧化硅，如75-85wt％氧化铝和15-25wt％氧化硅，如88wt％氧化铝和12wt％氧化硅，例如65-75wt％氧化铝和25-35wt％氧化硅，例如70wt％氧化铝和30wt％氧化硅，如60wt％-小于75wt％氧化铝和大于25wt％-40wt％氧化硅。也可存在其它材料，如铝、铬、铪、钇、镍、硼、磷、钛、锆、和/或其氧化物，例如用来调节所述涂层24的折射率。在一种实施方式中，所述保护涂层的折射率可在1-3范围之内，例如1-2，例如1.4-2，例如1.4-1.8。
一种替代方案是，所述保护涂层24可为多层涂层，它由单独形成的金属氧化物材料层形成，例如(但不限于)由形成于另一种含金属氧化物层(例如含氧化硅和/或氧化铝的第二层)之上的含金属氧化物层(例如含氧化硅和/或氧化铝的第一层)形成的双层。所述多层保护涂层24的各个单层可为任意所需的厚度。
在一种实施方式中，所述保护涂层24可包括形成在所述功能性涂层之上的第一层和形成在第一层之上的第二层。在一种非限制性实施方式中，第一层可包括氧化铝或含氧化铝和氧化硅的混合物或合金。例如，第一层可含有氧化硅/氧化铝混合物，具有大于5wt％氧化铝，如大于10wt％氧化铝，如大于15wt％氧化铝，如大于30wt％氧化铝，如大于40wt％氧化铝，如50-70wt％氧化铝，如范围在70-100wt％氧化铝和30-0wt％氧化硅。在一种非限制性实施方式中，第一层具有的厚度范围为大于0-1微米，如50-100，如100-250，如101-250，如100-150，例如大于100-125。第二层可含有氧化硅或氧化硅和氧化铝的混合物或合金。例如，第二层可含有氧化硅/氧化铝混合物，具有大于40wt％氧化硅，如大于50wt％氧化硅，如大于60wt％氧化硅，如大于70wt％氧化硅，如大于80wt％氧化硅，例如范围在80-90wt％氧化硅和10-20wt％氧化铝。在一种非限制性实施方式中，第二层具有的厚度范围为大于0-2微米，如50-5000，如50-2000，如100-1000，如300-500，如350-400。
例如，涂层30可为常规的装饰遮阳条带，如彩色陶瓷条带。所述涂层30可以常规方法提供在表面16之上，例如沿着所述表面16的周边。
图2图示说明结合本发明特征的层压制品40。所述层压制品40包括第一坯料或层42，它具有外部主表面44和内部主表面46。第二坯料或层48与第一层42间隔放置，并具有外部主表面50和内部主表面52。所述层42和48可与聚合物材料56层压到一起，例如(但不限于)塑料材料如聚乙烯醇缩丁醛或相似材料。所述聚合物材料56可包括任意聚合物材料。所述“聚合物材料”可包括一种聚合物成分，或者可包括由不同聚合物成分组成的混合物，例如(但不限于)一种或多种塑料材料，例如(但不限于)一种或多种热固性或热塑性材料。所述聚合物层56可粘合所述层(ply)在一起。有用的热固性成分包括聚酯、环氧树脂、酚醛塑料、和聚氨酯如反应喷射成形聚氨酯(RIM)热固性材料和其混合物。有用的热塑性材料包括：热塑性聚烯烃如聚乙烯和聚丙烯，聚酰胺如尼龙，热塑性聚氨酯、热塑性聚酯、丙烯酸类聚合物、乙烯基聚合物、聚碳酸酯、丙烯腈-丁二烯-苯乙烯(ABS)共聚物、EPDM橡胶、其共聚物和混合物。
合适的丙烯酸类聚合物包括一种或多种丙烯酸、甲基丙烯酸和其烷基酯的共聚物，例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸羟乙酯、甲基丙烯酸丁酯、丙烯酸乙酯、丙烯酸羟乙酯、丙烯酸丁酯和丙烯酸2-乙基己酯。其它合适的丙烯酸类聚合物和其制备方法公开在US5196485之中。
有用的聚酯和醇酸树脂可采用已知方法通过多元醇如乙二醇、丙二醇、丁二醇、1，6-已二醇、新戊二醇、三羟甲基丙烷和季戊四醇与多羧酸如己二酸、马来酸、富马酸、苯二酸、苯偏三酸或干燥油脂肪酸进行缩合而制得。合适聚酯材料实例公开在US5739213和US5811198之中。
有用的聚氨酯包括聚合多元醇如聚酯多元醇或丙烯酸多元醇与多异氰酸酯的反应产物，多异氰酸酯包括芳族二异氰酸酯如4，4’-二苯基甲烷二异氰酸酯、脂族二异氰酸酯如1，6-六亚甲基二异氰酸酯、和脂环族二异氰酸酯如异佛尔酮二异氰酸酯和4，4’-亚甲基-二(环己基异氰酸酯)。本文所用术语“聚氨酯”是所需包括聚氨酯以及聚脲、和聚(氨酯-脲)。
合适环氧功能性材料公开在US5820987之中。
合适乙烯基树脂包括聚乙烯醇缩乙醛、聚乙烯醇缩甲醛、和聚乙烯醇缩丁醛。
所述聚合物层56可具有任意所需的厚度，例如，在一种非限制性实施方式中，对聚乙烯丁醛来说，其厚度范围可为0.50-0.80mm，例如0.76mm。所述聚合物材料可具有任意所需的折射率。在一种实施方式中，所述聚合物材料具有的折射率范围为1.4-1.7，例如1.5-1.6。在图2所示的实施方式中，所述美观涂层20沉积在第一层42的内部主表面46的至少一部分之上。如图2所示，如上所述的任选功能性涂层22可沉积在一个或多个所述层42、48的主表面之上。在图2所示的示例性实施方式中，所述功能性涂层22沉积在第一层42的内部表面46之上。任选的保护涂层24也可涂敷在所述至少一种美观涂层20之上。另外，任选涂层30例如不透明或彩色遮阳条带也可提供在所述表面44、46、50或52中的一个之上，例如沿着所述表面46的周边。所述层压制品40，由于所述至少一种美观涂层20的存在，可具有由-10≤a*≤0、-15≤b*≤5(在所述涂层30的外部区域)、和反射率在8-50％例如8-30％、例如10-25％、例如15-25范围所限定的颜色。例如，所述美观涂层20可层压在两块玻璃板之间、两块聚合物板之间(例如PVB)、或玻璃板和聚合物板之间，等等。在用于向前的汽车视觉区域，所述制品40可具有的Lta值大于等于70％，例如大于等于75％。在一种实施方式中，所述制品40的L*值是在45-55范围之内。
本发明所述至少一种美观涂层20提供具有受人欢迎的美学特征的制品，例如整体或层压制品。结合有本发明所述至少一种美观涂层的制品特别适用于汽车透明体，为所述透明体提供美学特征，例如颜色和/或反射性，它们能够突出所述汽车的外部和/或内部颜色，并能改善所述汽车的整体式样。
在本发明的更广泛方面，按照本发明制成的汽车透明体可制成所需的颜色，以便匹配或衬托所述汽车体的颜色。例如，如上所述，在一种实施方式中，所述制品具有银色外观，且所述美观涂层能提供a*值在-4至0范围之内，b*值在-10至-6范围之内。在另一种实施方式中，所述制品具有白镴(pewter)外观，且所述美观涂层能提供a*值在-5至-1范围之内，其b*值是在-3至+3范围之内。另外，本发明所述至少一种美观涂层可降低所述装饰遮阳条带30与其余透明体之间的不连贯视觉界面。
下述实施例是用来例证性说明本发明，它们不应被认为限制本发明到它们的具体细节。
实施例I
通过常规MSVD沉积，制备多个结合有至少一种本发明涂层的涂敷制品的样品，并测试其反射颜色(L*、a*、b*)和透光率(Lta)。
样品A(层压的)
2.0mm厚的透明玻璃(可购自PPG Industries，Inc.of Pittsburgh，Pennsylvania)/200锡酸锌/200氧化钛/0.76mm聚乙烯醇缩丁醛/2.3mm Solex玻璃(可购自PPG Industries，Inc.of Pittsburgh，Pennsylvania)。这种层压结构具有72.70％的Lta值和分别为52.27、-2.35和-8.97的反射L*a*b*颜色。
样品B(层压的)
2.0mm厚的透明玻璃/240锡酸锌/160氧化钛/0.76mm聚乙烯醇缩丁醛/2.3mm VistaGray玻璃(可购自PPG Industries，Inc.ofPittsburgh，Pennsylvania)。这种层压结构具有70.55％的Lta值和分别为47.74、-2.03和-5.68的反射L*a*b*颜色。
样品C(整体的)
2.3mm厚的透明玻璃/350氧化锆。
这种结构具80.32％的Lta值和分别为50.29、-1.76和-8.09的反射L*a*b*颜色。
样品D(整体的)
2.3mm厚的透明玻璃/475氧化锆。
这种结构具75.57％的Lta值和分别为54.98、-2.28和-7.54的反射L*a*b*颜色。
样品E(具有保护涂层的整体制品)
4.0mm厚的透明玻璃/200锡酸锌/200氧化钛/20000铝硅氧化物。
这种结构具有74％的Lta值和分别为53、-2.4和-9.0的反射L*a*b*颜色。
实施例II
按照本发明方法制备另外的样品1-50，组成和各种不同测得的光学特征如下述表1所示。
在表1中，术语“mono”表示整体，即非层压的。所有非标记“mono”的样品都是采用两块标记类型的玻璃层压的。所有样品都采用2.3mm玻璃作为表1中标注类型的基材进行涂敷的。术语“VG”(表1或图3-6中)表示所述玻璃是VistaGray玻璃(可购自PPG Industries，Inc.of Pittsburgh，Pennsylvania)。术语“SL”(表1或图3-6中)表示所述玻璃是Solex玻璃(也可购自PPG Industries，Inc.ofPittsburgh，Pennsylvania)。术语“Clr”表示透明浮法玻璃(可购自PPG Industries，Inc)。术语“ox metal”表示所述涂层是以金属进行溅射并通过在1300°F(703℃)的加热炉中加热2.5min转化为氧化物的，之后进行层压。所述词语“反应喷射”是表示所述涂层是以氧化物进行溅射，然后在320°F(160℃)加热炉中10min，之后进行层压。除非另有相反规定，所有厚度数值均是以埃为单位。所报告的光学数值是使用Lambda 9分光光度计(可自Perkin-Elmer获得)或BYK-Gardner TCS分光光度计(可自BYK-Gardner获得)检测得到的。所述光学厚度是使用折射率数值为氧化钛2.58和氧化锆2.12计算得到的。每平方厘米的微克数是由x-射线荧光确定的。厚度数值是由每平方厘米的微克数计算得出的。对于整体制品来说，R1表示所述制品涂敷侧的反射率，R2表示所述制品非涂敷侧的反射率。对于层压制品来说，R1表示最接近所述涂层的外部表面的反射率，R2表示离所述涂层最远的外部表面的反射率。所述“clr/clr”标记是两块浮法玻璃的层压制品，以作为参照。
| 表1 | |||||||||||||||||||
| TCS光度计 | Lambda 9 | ||||||||||||||||||
| A 2° | D65 10° | D65 10° | 自L*算得 | ||||||||||||||||
| 样品号 | 未涂敷窗 | 涂层材料 | ug/cm^2 | 光学厚度 | 厚度* | 透射率 | R1 | R2 | 阳光性能 | ||||||||||
| nd | 埃 | Y | x | y | L* | a* | b* | L* | a* | b* | A，2° | TSET | R1 | R2 | |||||
| 1 | VG | TiO2 | ox metal | 2.6 | 107 | 77.05 | 0.4458 | 0.4132 | 36.96 | -0.85 | -4.87 | 36.02 | -1.12 | -3.20 | 76.48 | 56.00 | 9.52 | 9.02 | |
| 2 | VG | TiO2 | ox metal | 5.1 | 211 | 71.94 | 0.4508 | 0.4154 | 47.34 | -1.15 | -11.90 | 44.47 | -1.96 | -8.37 | 71.21 | 52.74 | 16.28 | 14.17 | |
| 3 | VG | TiO2 | ox metal | 7.7 | 318 | 66.51 | 0.4539 | 0.4161 | 55.24 | -2.19 | -12.14 | 51.14 | -2.92 | -8.35 | 23.16 | 19.39 | |||
| 4 | VG | TiO2 | ox metal | 10.3 | 425 | 62.19 | 0.4539 | 0.4151 | 60.30 | -3.06 | -8.67 | 55.53 | -3.85 | -5.25 | 28.46 | 23.45 | |||
| 5 | VG | TiO2 | ox metal | 12.9 | 533 | 59.80 | 0.4499 | 0.4125 | 62.31 | -3.79 | -2.69 | 57.30 | -4.37 | -0.02 | 30.77 | 25.23 | |||
| 6 | VG | TiO2 | ox metal | 15.6 | 644 | 59.50 | 0.4417 | 0.4084 | 61.59 | -4.36 | 8.02 | 56.70 | -4.71 | 8.95 | 29.93 | 24.62 | |||
| 7 | VG | TiO2 | ox metal | 18.3 | 756 | 61.55 | 0.4341 | 0.4059 | 58.56 | -3.55 | 20.12 | 54.07 | -3.71 | 18.69 | 26.55 | 22.04 | |||
| 8 | SL | TiO2 | ox metal | 2.6 | 107 | 82.62 | 38.01 | -1.44 | -5.18 | 10.09 | |||||||||
| 9 | SL | TiO2 | ox metal | 5.1 | 211 | 77.35 | 47.63 | -1.51 | -11.84 | 76.30 | 59.32 | 16.50 | |||||||
| 10 | SL | TiO2 | ox metal | 7.7 | 318 | 71.46 | 55.64 | -2.41 | -12.04 | 70.19 | 55.49 | 23.56 | |||||||
| 11 | SL | TiO2 | ox metal | 10.3 | 425 | 66.63 | 60.62 | -3.2 | -8.62 | 28.82 | |||||||||
| 12 | SL | TiO2 | ox metal | 12.9 | 533 | 64.25 | 62.59 | -3.93 | -2.58 | 31.10 | |||||||||
| 13 | SL | TiO2 | ox metal | 15.6 | 644 | 64 | 61.94 | -4.48 | 7.5 | 30.33 | |||||||||
| 14 | SL | TiO2 | ox metal | 18.3 | 756 | 67.42 | 57.33 | -2.57 | 22.93 | 25.26 | |||||||||
| 15 | Mono | TiO2 | ox metal | 2.6 | 277 | 107 | 87.25 | 0.4493 | 0.4098 | 41.92 | -0.29 | -8.42 | 41.76 | -0.56 | -8.17 | 12.45 | 12.35 | ||
| 16 | Mono | TiO2 | ox metal | 5.1 | 543 | 211 | 77.16 | 0.4571 | 0.4128 | 56.25 | -1.04 | -14.02 | 55.80 | -1.69 | -13.72 | 24.16 | 23.71 | ||
| 17 | Mono | TiO2 | ox metal | 7.7 | 820 | 318 | 67.45 | 0.4611 | 0.4132 | 65.39 | -1.99 | -12.00 | 64.81 | -2.85 | -11.86 | 34.54 | 33.81 | ||
| 18 | Mono | TiO2 | ox metal | 10.3 | 1098 | 425 | 60.82 | 0.4597 | 0.4113 | 70.29 | -2.49 | -7.52 | 69.65 | -3.38 | -7.61 | 41.16 | 40.25 | ||
| 19 | Mono | TiO2 | ox metal | 12.9 | 1375 | 533 | 57.48 | 0.4518 | 0.4067 | 72.10 | -2.96 | -0.40 | 71.43 | -3.89 | -0.60 | 43.81 | 42.82 | ||
| 20 | Mono | TiO2 | ox metal | 15.6 | 1662 | 644 | 57.93 | 0.4395 | 0.4006 | 70.93 | -3.63 | 11.15 | 70.30 | -4.57 | 10.59 | 42.09 | 41.18 | ||
| 21 | Mono | TiO2 | ox metal | 18.3 | 1950 | 756 | 61.99 | 0.4265 | 0.3963 | 66.85 | -2.56 | 27.70 | 66.21 | -3.57 | 26.99 | 36.43 | 35.60 | ||
| 22 | Mono | ZrO2 | ox metal | 3.8 | 189 | 89 | 89.46 | 0.4469 | 0.4086 | 37.26 | -0.58 | -3.25 | 37.22 | -0.66 | -3.19 | 9.68 | 9.66 | ||
| 23 | Mono | ZrO2 | ox metal | 7.9 | 394 | 186 | 86.02 | 0.4489 | 0.4094 | 43.70 | -0.84 | -6.72 | 43.48 | -1.14 | -6.62 | 13.63 | 13.48 | ||
| 24 | Mono | ZrO2 | ox metal | 12.0 | 598 | 282 | 81.45 | 0.4511 | 0.4099 | 50.38 | -41.35 | -8.03 | 50.07 | -1.80 | -7.98 | 18.74 | 18.48 | ||
| 25 | Mono | ZrO2 | ox metal | 15.9 | 792 | 374 | 76.97 | 0.4522 | 0.4100 | 55.56 | -1.71 | -7.35 | 55.21 | -2.31 | -7.43 | 23.48 | 23.13 | ||
| 26 | Mono | ZrO2 | ox metal | 20.1 | 1001 | 472 | 73.77 | 0.4520 | 0.4095 | 58.74 | -1.88 | -5.59 | 58.41 | -2.58 | -5.74 | 26.75 | 26.39 | ||
| 表1 | |||||||||||||||||||
| TCS光度计 | Lambda9 | ||||||||||||||||||
| A2° | D6510° | D65 10° | 自L*算得 | ||||||||||||||||
| 样品号 | 未涂敷窗 | 涂层材料 | ug/cm^2 | 光学厚度 | 厚度* | 透射率 | R1 | R2 | 阳光性能 | ||||||||||
| nd | 埃 | Y | x | y | L* | a* | b* | L* | a* | b* | A，2° | TSET | R1 | R2 | |||||
| 27 | Mono | ZrO2 | ox metal | 24.2 | 1206 | 569 | 71.06 | 0.4496 | 0.4081 | 61.06 | -1.95 | -1.90 | 60.69 | -2.74 | -2.08 | 29.32 | 28.90 | ||
| 28 | Mono | ZrO2 | ox metal | 28.3 | 1410 | 665 | 70.24 | 0.4466 | 0.4068 | 61.42 | -1.91 | 1.80 | 61.12 | -2.74 | 1.63 | 29.73 | 29.39 | ||
| 29 | SL | ZrO2 | ox metal | 3.8 | 89 | 83.73 | 0.4415 | 0.4119 | 35.55 | -1.56 | -2.06 | 35.44 | -1.72 | -1.86 | 8.78 | 8.72 | |||
| 30 | SL | ZrO2 | ox metal | 7.9 | 186 | 82.14 | 0.4426 | 0.4124 | 39.12 | -1.76 | -4.36 | 38.68 | -2.35 | -3.64 | 10.73 | 10.47 | |||
| 31 | SL | ZrO2 | ox metal | 12.0 | 282 | 79.94 | 0.4438 | 0.4127 | 43.16 | -1.98 | -5.84 | 42.41 | -2.96 | -4.78 | 13.27 | 12.77 | |||
| 32 | SL | ZrO2 | ox metal | 15.9 | 374 | 77.69 | 0.4443 | 0.4128 | 46.81 | -2.26 | -5.87 | 45.78 | -3.54 | -4.70 | 15.87 | 15.11 | |||
| 33 | SL | ZrO2 | ox metal | 20.1 | 472 | 76.08 | 0.4442 | 0.4126 | 49.02 | -2.57 | -4.85 | 47.75 | -3.86 | -3.72 | 17.61 | 16.60 | |||
| 34 | SL | ZrO2 | ox metal | 24.2 | 569 | 74.28 | 0.4429 | 0.4119 | 50.97 | -2.70 | -1.79 | 49.49 | -4.16 | -0.89 | 19.24 | 17.99 | |||
| 35 | SL | ZrO2 | ox metal | 28.3 | 665 | 74.12 | 0.4416 | 0.4412 | 51.27 | -2.71 | 0.52 | 49.85 | -4.12 | 1.18 | 19.50 | 18.29 | |||
| 36 | VG | ZrO2 | ox metal | 3.8 | 89 | 77.93 | 0.4447 | 0.4126 | 34.59 | -1.17 | -1.64 | 34.18 | -1.24 | -1.05 | 8.30 | 8.10 | |||
| 37 | VG | ZrO2 | ox metal | 7.9 | 186 | 76.54 | 0.4456 | 0.4129 | 38.15 | -1.36 | -4.12 | 36.94 | -1.47 | -2.69 | 10.17 | 9.51 | |||
| 38 | VG | ZrO2 | ox metal | 12.0 | 282 | 74.52 | 0.4467 | 0.4132 | 42.48 | -1.70 | -5.73 | 40.40 | -1.86 | -3.76 | 12.81 | 11.49 | |||
| 39 | VG | ZrO2 | ox metal | 15.9 | 374 | 72.22 | 0.4474 | 0.4134 | 46.32 | -2.08 | -5.74 | 43.53 | 2.39 | -3.51 | 15.51 | 13.52 | |||
| 40 | VG | ZrO2 | ox meatl | 20.1 | 472 | 70.89 | 0.4475 | 0.4132 | 48.42 | -2.31 | -4.80 | 45.32 | -2.67 | -2.66 | 17.13 | 14.77 | |||
| 41 | VG | ZrO2 | ox metal | 24.2 | 569 | 69.57 | 0.4462 | 0.4124 | 50.45 | -2.48 | -1.77 | 47.00 | -2.91 | -0.02 | 18.80 | 16.02 | |||
| 42 | VG | ZrO2 | ox metal | 28.3 | 665 | 68.73 | 0.4447 | 0.4117 | 50.78 | -2.48 | 1.13 | 47.19 | -2.80 | 2.38 | 19.08 | 16.16 | |||
| 43 | VG | ZrO2 | react sput | 7.4 | 208 | 77.38 | 36.04 | -1.1 | -2.43 | 9.03 | |||||||||
| 44 | VG | ZrO2 | react sput | 10.5 | 296 | 76.51 | 38.05 | -1.04 | -3.2 | 10.12 | |||||||||
| 45 | VG | ZrO2 | react sput | 13.3 | 375 | 74.86 | 41.39 | -1.74 | -4.05 | 12.11 | |||||||||
| 46 | VG | ZrO2 | react sput | 14.5 | 409 | 75.28 | 40.45 | -1.63 | -2.4 | 11.52 | |||||||||
| 47 | VG | ZrO2 | react sput | 17.7 | 499 | 74.04 | 43.14 | -1.93 | -1.89 | 13.25 | |||||||||
| 48 | VG | ZrO2 | react sput | 19.3 | 544 | 73.54 | 43.62 | -2.04 | -0.38 | 72.80 | 53.83 | 13.58 | |||||||
| 49 | VG | ZrO2 | react sput | 22.0 | 620 | 72.43 | 45.58 | -2.17 | 0.92 | 71.52 | 53.09 | 14.96 | |||||||
| 50 | VG | ZrO2 | react sput | 24.7 | 696 | 71.19 | 44.49 | -2.52 | 2.32 | 70.31 | 52.30 | 14.18 | |||||||
| Clr/Clr | 88.79 | 34.73 | -0.79 | -0.43 | 8.36 | ||||||||||||||
图3-6是表示选自表1样品的各种不同光学特征。图3所示为选自表1样品的a*和b*值的曲线图。图4所示为选自表1样品的反射率(R1)相对光学厚度(nd)的曲线图。图5所示为选自表1样品的R1相对厚度的曲线图。图6所示为图5所示样品的L*相对厚度的曲线图。
本领域技术人员将能够理解，在图3-6报告的数值之间的数值(即标绘曲线之间的数值)，可通过使用不同类型玻璃(例如不同颜色玻璃)和/或通过使用改变所述美观涂层中金属氧化物结合物或混合物而获得。另外，这类数值可通过包含金属氮化物和/或氮氧化物和/或用金属氮化物和/或氮氧化物取代在制造样品中所用的氧化物材料而获得。
本领域技术人员将能够容易地理解，在不背离前述说明所公开的概念时，可以对本发明作改进。因此，本文所述的特定实施方式，仅是例证说明性的，而不是用来限制本发明的范围，本发明范围将由随后权利要求书的全部范围和其任意和全部等价物给出。
Claims (50)
1.一种涂敷制品，包括：
第一基材；
和至少一种沉积在所述基材至少一部分之上的美观涂层，所述美观涂层为所述制品提供由-10≤a*≤0和-15≤b*≤5所限定的颜色和在8-50％范围的可见光反射率。
2.权利要求1所述制品，包括第二基材，美观涂层沉积在第一和第二基材之间。
3.权利要求1所述制品，其中，所述制品是成形制品。
4.权利要求1所述制品，其中，第一基材选自玻璃或聚合物材料。
5.权利要求4所述制品，其中，第一基材是回火或退火玻璃。
6.权利要求1所述制品，其中，所述美观涂层包括至少一种金属氧化物。
7.权利要求1所述制品，其中，所述美观涂层包括氧化铝、氧化锡、氧化铌、氧化钽、类金刚石碳、氧化锆、氧化钛、含锌和锡的氧化物、和硅的氧化物、氮化物或氮氧化物的至少一种、和含上述一种或多种的任意混合物。
8.权利要求7所述制品，其中，所述美观涂层的厚度在大于0到20000范围之内。
9.权利要求7所述制品，其中，所述美观涂层包括至少一锡酸锌层和至少一氧化钛层。
10.权利要求9所述制品，其中，所述锡酸锌层的厚度在100-300范围之内，所述氧化钛层的厚度在100-300范围之内。
11.权利要求1所述制品，其中，所述美观涂层包括氧化锆，其厚度在70-700范围之内。
12.权利要求1所述制品，其中，所述美观涂层包括一种或多种中等折射率材料、低的折射率材料、和高的折射率材料。
13.权利要求1所述制品，其中，所述美观涂层包括至少一分级的层。
14.权利要求1所述制品，其中，所述美观涂层具有非均匀的厚度。
15.权利要求1所述制品，其中，所述美观涂层沉积在所述基材的基本全部主表面上。
16.权利要求2所述制品，其中，第一基材是透明玻璃，第二基材是彩色玻璃。
17.权利要求2所述制品，其中，所述制品还包括位于第一基材和第二基材之间的聚合物材料。
18.权利要求1所述制品，其中，所述制品的L*值在45-55范围之内。
19.权利要求1所述制品，其中，所述制品的Lta大于或等于70％。
20.权利要求1所述制品，其中，所述制品的可见光反射率在10-25％范围之内。
21.权利要求1所述制品，其中，所述制品的可见光反射率在16-20％范围之内。
22.权利要求1所述制品，其中，所述制品的可见光反射率在8-30％范围之内。
23.权利要求1所述制品，包括保护涂层，它沉积在所述美观涂层的至少一部分之上，所述保护涂层含有氧化硅、氧化铝、氧化锆和其混合物的至少一种。
24.权利要求23所述制品，其中，所述保护涂层的厚度在5000-50000范围之内。
25.权利要求24所述制品，其中，所述保护涂层的厚度在10000-20000范围之内。
26.权利要求1所述制品，其中，所述美观涂层是多层涂层叠层的一部分。
27.权利要求26所述制品，其中，所述涂层叠层包括至少一种金属层。
28.权利要求27所述制品，其中，所述金属层是红外线反射层。
29.权利要求27所述制品，其中，所述金属层包括银或金中的至少一种。
30.一种制造具有至少一种美观涂层制品的方法，包括以下步骤：
将至少一美观涂层沉积在第一基材的至少一部分上；
将所述涂层沉积到足以为第一基材提供由-10≤a*≤0和-15≤b*≤5所限定的颜色和在8-30％范围的可见光反射率。
31.权利要求30所述方法，包括沉积所述涂层以提供可见光反射率在10-25％范围之内。
32.权利要求30所述方法，包括沉积所述美观涂层以提供可见光反射率在16-20％范围之内。
33.权利要求30所述方法，包括沉积所述美观涂层以提供L*在45-55范围之内。
34.权利要求30所述方法，其中，所述美观涂层包括至少一种金属氧化物。
35.权利要求30所述方法，其中，所述美观涂层包括氧化铝、氧化锡、氧化铌、氧化钽、类金刚石碳、氧化锆、氧化钛、含锌和锡的氧化物、和硅的氧化物、氮化物或氮氧化物的至少一种、和含上述一种或多种的任意混合物。
36.权利要求30所述方法，其中，所述涂层是多层涂层，且所述方法包括将具有第一折射率的第一涂层材料沉积在所述基材的至少一部分之上，和将至少一种具有第二折射率的第二涂层材料沉积在第一涂层材料的至少一部分之上，其中，第一折射率不同于第二折射率。
37.权利要求36所述方法，其中，第一材料是锡酸锌，第二材料是氧化钛。
38.权利要求37所述方法，包括将所述锡酸锌沉积到100-300范围的厚度，和将所述氧化钛沉积到100-300范围的厚度。
39.权利要求30所述方法，包括：
提供第二基材；
布置第一基材和第二基材，使所述美观涂层位于第一和第二基材之间；和
用至少一种聚合物材料将第一和第二基材层压到一起，以形成层压制品。
40.权利要求39所述方法，其中，第一基材是透明玻璃，第二基材是彩色玻璃。
41.权利要求30所述方法，包括沉积所述美观涂层使其厚度在50-600范围之内。
42.权利要求30所述方法，还包括将功能性涂层沉积在所述基材的至少一部分之上。
43.权利要求30所述方法，包括将保护涂层沉积在所述美观涂层的至少一部分之上。
44.权利要求39所述方法，包括将至少一种功能性涂层沉积在至少一所述基材的至少一部分之上；和
层压所述基材，使得所述美观涂层和所述功能性涂层位于所述两个基材之间。
45.权利要求44所述方法，其中，所述功能性涂层包括至少一银层。
46.权利要求30所述方法，包括加热处理所述制品以回火或弯曲所述制品。
47.权利要求42所述方法，其中，所述功能性涂层包括至少一金属层，且所述方法包括加热处理所述制品以回火或弯曲所述制品。
48.权利要求47所述方法，其中，所述金属层含有银。
49.权利要求1所述制品，其中，所述制品是选自汽车挡风玻璃、侧窗、后窗、月光篷顶或遮阳篷顶的汽车透明体。
50.一种车辆，包括：
具有外部和/或内部颜色的车辆；和
至少一种具有颜色的透明体，其中，所述透明体的颜色能够匹配或衬托所述车辆外部和/或内部颜色。
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| PCT/US2003/017031 WO2003101903A2 (en) | 2002-05-31 | 2003-05-30 | Article having an aesthetic coating |
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-
2003
- 2003-05-28 US US10/446,973 patent/US7588829B2/en not_active Expired - Lifetime
- 2003-05-30 AU AU2003240953A patent/AU2003240953A1/en not_active Abandoned
- 2003-05-30 WO PCT/US2003/017031 patent/WO2003101903A2/en active Application Filing
- 2003-05-30 CN CN03812369XA patent/CN1656034B/zh not_active Expired - Lifetime
- 2003-05-30 EP EP03731456A patent/EP1615856A1/en not_active Ceased
- 2003-05-30 JP JP2004509600A patent/JP5430814B2/ja not_active Expired - Lifetime
- 2003-05-30 KR KR1020047019518A patent/KR100626487B1/ko active IP Right Grant
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2006
- 2006-02-16 HK HK06102002A patent/HK1081519A1/xx not_active IP Right Cessation
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101808821B (zh) * | 2007-08-24 | 2013-11-06 | Ppg工业俄亥俄公司 | 交通工具透明体 |
| CN102791645A (zh) * | 2010-03-10 | 2012-11-21 | 旭硝子欧洲玻璃公司 | 高反射率的玻璃板 |
| CN102791645B (zh) * | 2010-03-10 | 2016-11-16 | 旭硝子欧洲玻璃公司 | 高反射率的玻璃板 |
| CN103339079A (zh) * | 2010-10-08 | 2013-10-02 | 葛迪恩实业公司 | 可回火三层防反射涂层、包括可回火三层防反射涂层的涂层制品和/或制作其的方法 |
| CN111201205A (zh) * | 2018-09-20 | 2020-05-26 | 法国圣戈班玻璃厂 | 具有光学和美学特性的物品 |
| CN112739534A (zh) * | 2018-10-15 | 2021-04-30 | 克勒克纳彭塔普拉斯特有限公司 | 具有金属性外观的热成型复合膜 |
| CN112955578A (zh) * | 2019-02-04 | 2021-06-11 | 宝马股份公司 | 高频可穿透的构件和用于制造构件的方法 |
| US11821074B2 (en) | 2019-02-04 | 2023-11-21 | Bayerische Motoren Werke Aktiengesellschaft | High-frequency-transparent component and method for producing the same |
| CN114845867A (zh) * | 2020-12-02 | 2022-08-02 | 法国圣戈班玻璃厂 | 在载具外表面上具有半透明反射印刷铭文的用于载具的具有可电控光学特性的层压装配玻璃 |
| CN114133226A (zh) * | 2021-12-30 | 2022-03-04 | 苏州晶生新材料有限公司 | 一种光学镀层基材及使用方法 |
Also Published As
| Publication number | Publication date |
|---|---|
| US20030224181A1 (en) | 2003-12-04 |
| JP5430814B2 (ja) | 2014-03-05 |
| CN1656034B (zh) | 2012-12-26 |
| KR100626487B1 (ko) | 2006-09-20 |
| WO2003101903A2 (en) | 2003-12-11 |
| HK1081519A1 (en) | 2006-05-19 |
| AU2003240953A1 (en) | 2003-12-19 |
| JP2005527461A (ja) | 2005-09-15 |
| EP1615856A1 (en) | 2006-01-18 |
| KR20050010019A (ko) | 2005-01-26 |
| US7588829B2 (en) | 2009-09-15 |
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