CN1460065A - 具有不锈钢外观的涂敷制品 - Google Patents

具有不锈钢外观的涂敷制品 Download PDF

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CN1460065A
CN1460065A CN02801087A CN02801087A CN1460065A CN 1460065 A CN1460065 A CN 1460065A CN 02801087 A CN02801087 A CN 02801087A CN 02801087 A CN02801087 A CN 02801087A CN 1460065 A CN1460065 A CN 1460065A
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refractory metal
layer
goods
nickel
metal alloy
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陈国存
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Vapor Technologies Inc
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    • Y10T428/12542—More than one such component
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Abstract

采用具有不锈钢外观的多层装饰和保护性涂层涂敷的制品(图4)。该涂层包括在所述制品表面上的一个或多个电镀层和在电镀层上的气相沉积的耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的反应产物，其中耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的所述反应产物的氮含量为约3－约22原子百分比。

Description

具有不锈钢外观的涂敷制品
                        发明领域
本发明涉及采用具有不锈钢外观或颜色的多层装饰和保护性涂层涂敷的制品，特别是黄铜制品。
                        发明背景
目前对于各种黄铜制品如龙头、龙头罩、门旋钮、门把手、门锁眼盖等的实际情况是首先擦亮和抛光制品的表面到高光泽和然后涂敷保持性有机涂层(如由丙烯酸类、聚氨酯类、环氧类物等组成的涂层)到此抛光的表面上。此体系的缺点是擦亮和抛光操作的劳动强度较大，特别是如果制品具有复杂的形状。同样，已知有机涂层并不总是如所需耐用的，和易于受酸的侵蚀。因此，如下情况是相当有利的：如果黄铜制品，或事实上其它制品，塑料、陶瓷、或金属，可以含有提供制品装饰性外观以及提供耐磨性、抗磨性和耐腐蚀性的涂层。在本领域已知的是可以将层涂层涂敷到制品上，它提供装饰性外观以及提供耐磨性、抗磨性和耐腐蚀性。此多层涂层包括由耐火金属氮化物如氮化锆或氮化钛组成的装饰和保护性颜色层。此颜色层，当它是氮化锆时，提供黄铜色，和当它是氮化钛是提供金色。
U.S.专利Nos.5,922,478，6,033,790和5,654,108尤其描述了这样的涂层，它提供具有装饰性颜色的制品，如抛光的黄铜，且也提供耐磨性、抗磨性和耐腐蚀性。如果可以提供这样的涂层是非常有利的，该涂层提供与包含氮化锆或氮化钛的涂层基本相同的性能但不是黄铜色的或金色的，是不锈钢色的。本发明提供这样的涂层。
                          发明概述
本发明涉及含有沉积在制品至少一部分表面上的装饰和保护性多层涂层的制品如塑料、陶瓷或金属制品。更特别地，本发明涉及含有沉积在其表面上的某些特定类型材料的多个重叠层的制品或基材，特别是金属制品如铝、黄铜或锌。涂层是装饰性的且也提供耐腐蚀性、耐磨性和抗磨性。涂层提供不锈钢外观，即具有不锈钢颜色色调。因此，在其上含有涂层的制品表面模拟了不锈钢表面。
制品首先含有沉积在它的表面上的一个或多个电镀层。然后在电镀层的顶部，通过气相沉积如物理气相沉积，沉积一个或多个气相沉积层。直接沉积在基材表面上的第一层由镍组成。第一层可以是单一的或它可以由两个不同的镍层，例如直接沉积在基材表面上的半光亮镍层和重叠在半光亮镍层上的光亮镍层组成。在电镀层上是由耐火金属或耐火金属合金如锆、钛、铪、钽或锆-钛合金，优选锆、钛或锆-钛合金组成的触击层。在触击层上布置的是由如下物质组成的保护和装饰性颜色层：(i)耐火金属氮化物或耐火金属合金氮化物或(ii)耐火金属或耐火金属合金、氮气和氧气的反应产物，其中氮含量较低，即，低于化学计量。耐火金属氮化物，耐火金属合金氮化物，耐火金属、氮气和氧气的反应产物或耐火金属合金、氮气和氧气的反应产物的低于化学计量的氮含量为约3-约22原子百分比，优选约4-约16原子百分比。
                        附图简述
图1是含有多层涂层基材一部分的横截面图，该多层涂层包括双镍基础涂层和直接在顶部镍层上的颜色和保护性层，该颜色和保护性层由耐火金属氮化物，耐火金属合金氮化物，或耐火金属或耐火金属合金、氮气和氧气的反应产物组成；
图2是相似于图1的视图，区别在于在顶部镍层和耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的反应产物颜色层中间存在耐火金属或耐火金属合金的触击层(strike layer)；
图3是相似于图2的视图，区别在于在顶部镍层和耐火金属触击层中间存在铬层；和
图4是相似于图3的视图，区别在于在耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的反应产物颜色层上存在耐火金属氧化物或耐火金属合金氧化物层。
                      优选实施方案的描述
制品或基材12可以由如下物质组成：可以在其上涂敷镀敷层的任何材料，如塑料，如ABS、聚烯烃、聚氯乙烯、和酚醛树脂，陶瓷，金属或金属合金。在一个实施方案中，它由金属或金属合金如铜、钢、黄铜、锌、铝、镍合金等组成。
在本发明中，如图1-4所示，通过镀敷如电镀将第一层或系列层涂敷到制品表面上。通过气相沉积将第二系列层涂敷到电镀层的表面上。电镀层尤其用作使制品表面变平的基础涂层。在本发明的一个实施方案中，可以在制品表面上沉积镍层13。镍层可以是由镀敷沉积的任何常规镍，如光亮镍、半光亮镍、缎光镍等。可以通过常规和公知的电镀工艺将镍层13沉积在基材12的至少一部分表面上。这些工艺包括使用常规的电镀浴，例如Watts浴作为镀敷溶液。典型地这样的浴包含硫酸镍、氯化镍、和溶于水的硼酸。也可以使用所有的氯化物、氨基磺酸盐和氟硼酸盐镀敷溶液。这些浴可非必要地包括许多公知和通常使用的化合物如流平剂，增白剂等。为生产镜面光亮镍层，将至少一种类别I增白剂和至少一种类别II增白剂加入到镀敷溶液中。类别I增白剂是包含硫的有机化合物。类别II增白剂是不包含硫的有机化合物。类别II增白剂也可引起变平，且当加入到没有含硫的类别I增白剂的镀敷浴中时，导致半光亮镍沉积物。这些类别I增白剂包括烷基萘和苯磺酸、苯和萘二和三磺酸、苯和萘磺酰胺、和磺酰胺如糖精、乙烯基和烯丙基磺酰胺和磺酸。类别II增白剂一般是不饱和有机材料，例如，炔属或烯属醇、乙氧基化和丙氧基化炔属醇、香豆素、和醛。这些类别I和类别II增白剂对于本领域技术人员是公知和容易购得的。它们尤其描述在U.S.专利No.4,421,611中，该文献在此引入作为参考。
镍层可以由单一层如半光亮镍、缎光镍或光亮镍组成，或它可以是包含两个不同镍层，例如由半光亮镍组成的层和由光亮镍组成的层的双层。镍层的厚度一般有效使制品的表面变平且提供改进的耐腐蚀性。此厚度一般为从约2.5μm，优选约4μm到约90μm。
如在本领域已知的那样，在基材上沉积镍层之前，通过放入常规和公知的酸浴，将基材进入酸活化。
在如图1-4所示的一个实施方案中，镍层13实际上由两个不同镍层14和16组成。层14由半光亮镍组成而层16由光亮镍组成。此双镍沉积物对其下的基材提供改进的耐腐蚀性。通过常规电镀工艺直接在基材12表面上沉积半光亮、无硫板14。然后将包含半光亮镍层14的基材12放入光亮镍镀敷浴中且在半光亮镍层14上沉积光亮镍层16。
半光亮镍层和光亮镍层的厚度是至少有效提供改进耐腐蚀性和/或使制品表面变平的厚度。一般情况下，半光亮镍层的厚度至少为约1.25μm，优选至少约2.5μm，和更优选至少约3.5μm。厚度上限一般不是关键的且由次要的如成本的考虑来支配。然而，一般情况下，不应当超过约40μm，优选约25μm，和更优选约20μm的厚度。光亮镍层16的厚度至少为约1.2μm，优选至少约3μm，和更优选至少约6μm。光亮镍层的厚度上限范围不是关键的且一般由如成本的考虑来控制。然而，一般情况下，不应当超过约60μm，优选约50μm，和更优选约40μm的厚度。光亮镍层16也用作流平层，它倾向于覆盖或填充基材中的缺陷。
在一个实施方案中，如图3和4所示，位于镍层13和气相沉积层31之间的是一个和多个另外的电镀层21。这些另外的电镀层包括但不限于铬、锡-镍合金等。当层21由铬组成时，它可以通过常规和公知的铬电镀技术沉积在镍层13上。这些技术与各种铬镀敷浴一起公开于Brassard，“装饰性电镀-转变中的工艺”，Metal Finishing，105-108页，1988年6月；Zaki，“铬镀敷”，PF Directory，146-160页；和U.S.专利Nos.4,460,438、4,234,396和4,093,522中，所有这些文献在此引入作为参考。
铬镀敷浴是公知和可购得的。典型的铬镀敷浴包含铬酸或其盐，和催化剂离子如硫酸根或氟离子。催化剂离子可以由硫酸或其盐和氟硅酸提供。该浴可以在约112-116°F的温度下操作。典型地在铬镀敷中，在约5-9伏下采用约150安培每平方英尺的电流密度。
铬层的厚度一般至少为约0.05μm，优选至少约0.12μm，和更优选至少约0.2μm。一般情况下，厚度上限不是关键的且由次要的如成本的考虑来决定。然而，铬层的厚度不应当超过约1.5μm，优选约1.2μm，和更优选约1μm。
代替由铬组成的层21，它可以由锡-镍合金，即锡和镍的合金组成。锡-镍合金层可以通过常规和公知的锡-镍电镀工艺沉积在基材表面上。这些工艺和镀敷浴是常规和公知的，且尤其公开于U.S.专利Nos.4,033,835、4,049,508、3,887,444、3,772,168和3,940,319中，所有这些文献在此引入作为参考。
锡-镍合金层优选由代表原子组成SnNi的约60-70wt％锡和约30-40wt％镍，更优选约65％锡和35％镍组成。镀敷浴包含足够量的镍和锡以提供上述组成的锡-镍合金。
市售的锡-镍镀敷工艺是购自ATOTECH的NiColloyTM工艺，且描述在它们的技术信息表No：NiColloy，1994年10月30日中，该文献在此引入作为参考。
锡-镍合金层21的厚度一般至少为约0.25μm，优选至少约0.5μm，和更优选至少约1.2μm。厚度上限范围不是关键的且一般依赖于经济考虑。一般情况下，不应当超过约50μm，优选约25μm，和更优选约15μm的厚度。
在电镀层上，通过气相沉积如物理气相沉积和化学气相沉积，优选物理气相沉积，至少沉积如下物质组成的保护和装饰性颜色层32：(i)耐火金属氮化物，(ii)耐火金属合金氮化物，(iii)耐火金属、氮气和氧气的反应产物，(iV)耐火金属合金、氮气和氧气的反应产物，(v)耐火金属碳氮化物，或(vi)耐火金属合金碳氮化物。
此颜色层32具有不锈钢颜色或色调，它尤其是由于(i)耐火金属氮化物，(ii)耐火金属合金氮化物，(iii)耐火金属、氮气和氧气的反应产物，(iV)耐火金属合金、氮气和氧气的反应产物，(v)耐火金属碳氮化物，或(Vi)耐火金属合金碳氮化物的较低的、低于化学计量的氮和氧含量而致。该较低的低于化学计量氮含量为约3-约22原子百分比，优选约4-约16原子百分比。
耐火金属或耐火金属合金、氮气和氧气的反应产物一般由耐火金属或耐火金属合金氧-氮化物，耐火金属或耐火金属合金氧化物，和耐火金属或耐火金属合金氮化物组成。耐火金属氧化物和耐火金属合金氧化物包括，但不限于氧化铪、氧化锆、氧化钛和锆-钛合金氧化物。耐火金属氮化物和耐火金属合金氮化物包括，但不限于氮化铪、氮化锆、氮化钛和锆-钛合金氮化物。包括氧化锆和氮化锆合金的这些金属氧化物和金属氮化物和它们的制备和沉积是常规和公知的，和尤其公开于U.S.专利No.5,367,285中，该文献的公开内容在此引入作为参考。
在由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的保护和装饰性颜色层32中，改变氧含量会使不锈钢颜色层更带蓝色或带黄色。增加氧含量会使颜色层具有带蓝色的色调。降低氧含量会使颜色层具有带黄色的色调。
此颜色和保护层32的厚度是至少有效提供不锈钢颜色和提供抗磨性、耐擦划性和耐磨性的厚度。一般情况下，此厚度至少为约1,000埃，优选至少约1,500埃，和更优选至少约2,500埃。厚度上限范围一般不是关键的且依赖于次要的如成本的考虑。一般情况下不应当超过约0.75μm，优选约0.5μm的厚度。
沉积层32的一种方法是通过采用反应性溅射或反应性阴极弧蒸发的物理气相沉积。反应性阴极弧蒸发和反应性溅射一般相似于普通的溅射和阴极弧蒸发，区别在于将反应气体引入腔室，它与移除的目标材料反应。因此，在其中氮化锆是层32的情况下，阴极由锆组成，而氮气是引入腔室的反应气体。
除保护性颜色层32以外，可以非必要地存在另外的气相沉积层。这些另外的气相沉积层可包括由耐火金属或耐火金属合金组成的层。耐火金属包括铪、钽、锆和钛。耐火金属合金包括锆-钛合金、锆-铪合金和钛-铪合金。耐火金属层或耐火金属合金层31一般尤其用作改进颜色层32对顶部电镀层粘合的触击层。如图2-4所示，耐火金属或耐火金属合金触击层31一般位于颜色层32和顶部电镀层中间。层31的厚度一般至少有效使层31用作触击层。一般情况下，此厚度至少为约60埃，优选至少约120埃，和更优选至少约250埃。厚度上限范围不是关键的且一般依赖于如成本的考虑。然而，一般情况下，层31应当不厚于约1.2μm，优选约0.5μm，和更优选约0.25μm。
通过常规和公知的气相沉积技术包括物理气相沉积技术如阴极弧蒸发(CAE)和溅射，沉积耐火金属或耐火金属合金层31。溅射技术和设备尤其描述于J.Vossen和W.Kern的“薄膜工艺II”，Academic Press，1991；R.Boxman等人，“真空弧科学和技术手册”，Noyes Pub.，1995；和U.S.专利Nos.4,162,954和4,591,418中，所有这些文献在此引入作为参考。
简单地，在溅射沉积工艺中，将耐火金属(如钛或锆)目标(它是阴极)和基材放入真空腔室中。将腔室中的空气抽空以在腔室中产生真空条件。将惰性气体，如氩气引入腔室。将气体粒子电离和向目标加速以移除钛或锆原子。然后将移除的目标材料典型地作为涂膜沉积在基材上。
在阴极弧蒸发中，将典型地几百安培的电弧撞击金属阴极如锆或钛的表面。弧蒸发阴极材料，它然后冷凝在基材上，形成涂层。
在本发明的优选实施方案中，耐火金属由钛或锆，优选锆组成，和耐火金属合金由锆-钛合金组成。
另外的气相沉积层也可包括不是上述氮化物的耐火金属化合物和耐火金属合金化合物。这些耐火金属化合物和耐火金属合金化合物包括耐火金属氧化物和耐火金属合金氧化物；耐火金属碳化物和耐火金属合金碳化物；和耐火金属碳氮化物和耐火金属合金碳氮化物。
在本发明的一个实施方案中，如图4所示，在颜色层32上沉积由耐火金属氧化物或耐火金属合金氧化物组成的层34。该层34的耐火金属氧化物和耐火金属合金氧化物包括，但不限于氧化铪、氧化钽、氧化锆、氧化钛、和锆-钛合金氧化物，优选氧化钛、氧化锆、和锆-钛合金氧化物，和更优选氧化锆。这些氧化物和它们的制备是常规和公知的。
层34有效向涂层提供改进的耐化学品，如酸或碱性能。包含耐火金属氧化物或耐火金属合金氧化物的层34的厚度一般至少有效提供改进的耐化学品性能。一般情况下此厚度至少为约10埃，优选至少约25埃，和更优选至少约40埃。层34应当足够薄使得它并不使其下的颜色层32的颜色变暗。即层34应当足够薄使得它是非不透明的或基本透明的。一般情况下层34应当不厚于约0.10μm，优选约250埃，和更优选约100埃。
可以通过指定的不锈钢颜色标准控制或预定涂层的不锈钢颜色。在其中颜色层32由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的情况下，可以通过总气体流中氮气对氧气比例的增加或减少，将不锈钢颜色调节到轻微更带黄色或带蓝色。可以完全地匹配于不锈钢的抛光或刷光表面润饰。
为更容易理解本发明，提供以下实施例。实施例是说明性和并不将本发明限定于此。
                          实施例1
将黄铜龙头放入包含标准和公知的肥皂、洗涤剂、抗絮凝剂等的常规浸泡清洁剂浴中，将该浴保持在8.9-9.2的pH和180-200°F的温度下约10分钟。然后将黄铜龙头放入常规超声波碱性清洁剂浴中。超声波清洁剂浴的pH为8.9-9.2，其被保持在约160-180°F的温度下，且包含常规和公知的肥皂、洗涤剂、抗絮凝剂等。在超声波清洁之后，将龙头清洗和放入常规碱性电清洁剂浴中。该电清洁剂浴被保持在约140-180°F的温度，约10.5-11.5的pH下，且包含标准和常规的洗涤剂。然后将龙头清洗两次和放入常规酸活化剂浴中。酸活化剂浴的pH为约2.0-3.0，其处于环境温度下，且包含氟化钠基酸盐。然后将龙头清洗两次和放入光亮镍镀敷浴中约12分钟。光亮镍浴一般是保持在约130-150°F的温度，约4.0的pH下，包含NiSO4，NiCl2，硼酸，和增白剂的常规浴。在龙头表面上沉积平均厚度为约10μm的光亮镍层。将光亮镍镀敷的龙头清洗三次和然后放入常规、可市购的六价铬镀敷浴中，使用常规铬镀设备约7分钟。该六价铬浴是常规和公知的浴，它包含约32盎司/加仑铬酸。该浴也包含常规和公知的铬镀敷添加剂。该浴保持在约112-116°F的温度下，和采用混合硫酸盐/氟化物催化剂。铬酸对硫酸盐比例是约200∶1。在光亮镍层表面上沉积约0.25μm的铬层。将龙头在去离子水中充分清洗和然后干燥。将铬镀敷的龙头放入阴极弧蒸发镀敷容器中。容器一般是包含真空腔室的圆筒形外壳，该真空腔室适于通过泵抽空。通过用于改变进入腔室氩气流量的可调节阀门，将氩气源连接到腔室。此外，通过用于改变进入腔室氮气和氧气流量的可调节阀门，将氮气和氧气源连接到腔室。
将圆筒形阴极安装在腔室中心和连接到可变D.C.电源的负输出上。将电源的正侧连接到腔室壁上。阴极材料包括锆。
将镀敷的龙头安装在转轴上，将16个这样的转轴安装在围绕阴极外部的环上。整个环围绕阴极旋转而每个转轴也围绕它自身的轴旋转，导致所谓的行星运动，它对于围绕每个转轴安装的多个龙头提供对阴极的均匀曝露。该环典型地在几个rpm下旋转，而每个转轴相对于每个环回转进行几个回转。转轴与腔室被电隔离且设置有可旋转接触使得可以在涂敷期间将偏压施加到基材上。
将真空腔室抽空到约10-5-10-7托的压力且加热到约150℃。
然后将电镀龙头进行高偏压弧等离子体清洁，其中将约500伏的(负)偏压施加到电镀龙头上同时将大约500安培的弧撞击和保持在阴极上。清洁的持续时间大约是5分钟。
在足以保持约1-5毫托压力的速率下引入氩气。在3分钟时间期间内，在铬镀敷龙头上沉积平均厚度为约0.1μm的锆层。阴极弧沉积工艺包括施加D.C.电源到阴极上以达到约500安培的电流，向容器中引入氩气以保持容器中压力在1-5毫托下和以上述行星方式旋转龙头。
在沉积锆层之后，在锆层上沉积氮化锆的保护和颜色层。将氮气流引入真空腔室中，同时弧放电持续在大约500安培。氮气流是会产生具有氮含量为约4-16原子百分比的氮化锆层的物流。此物流是总氩气、氮气和氧气流的约4-20％，且被持续约20-35分钟以形成厚度为约1,500埃-2,500埃的氮化锆层。在沉积此氮化锆层之后，终止该氮气流和将大约20-80标准升每分钟的氧气流持续约10-60秒。形成厚度为约20埃-100埃的氧化锆薄层。将弧熄灭，将真空腔室排气和取出涂敷制品。
尽管已经为了说明的目的描述了本发明的某些实施方案，应理解在本发明总的范围中可以有各种实施方案和改进。

Claims (15)

1.一种在其至少一部分表面上含有具有不锈钢外观的保护和装饰性涂层的制品，包括：
至少一个由镍组成的层；
由耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的反应产物组成的颜色层，其中所述耐火金属氮化物，耐火金属合金氮化物或耐火金属或耐火金属合金、氮气和氧气的所述反应产物的氮含量为约3-约22原子百分比。
2.权利要求1的制品，其中所述氮含量至少为约4-约16原子百分比。
3.权利要求1的制品，其中由耐火金属或耐火金属合金组成的层在所述至少一个由镍组成的层上。
4.权利要求1的制品，其中由耐火金属氧化物或耐火金属合金氧化物组成的层在所述颜色层上。
5.权利要求3的制品，其中由耐火金属氧化物或耐火金属合金氧化物组成的层在在所述颜色层上。
6.权利要求1的制品，其中所述颜色层由耐火金属或耐火金属合金、氮气和氧气的反应产物组成。
7.权利要求1的制品，其中所述颜色层由耐火金属氮化物或耐火金属合金氮化物组成。
8.权利要求1的制品，其中由铬组成的层在所述至少一个由镍组成的层上。
9.权利要求8的制品，其中由耐火金属或耐火金属合金组成的层在由铬组成的所述层上。
10.权利要求1的制品，其中由锡和镍合金组成的层在所述至少一个由镍组成的层上。
11.权利要求10的制品，其中由耐火金属或耐火金属合金组成的层在所述由锡和镍合金组成的层上。
12.权利要求1的制品，其中所述至少一个由镍组成的层由一个镍层组成。
13.权利要求1的制品，其中所述至少一个由镍组成的层由两个镍层组成。
14.权利要求1的制品，其中所述涂层具有刷光不锈钢润饰的外观。
15.权利要求1的制品，其中所述耐火金属选自锆、钛和铪。
CN02801087A 2001-04-05 2002-04-04 具有不锈钢外观的涂敷制品 Pending CN1460065A (zh)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US09/827,187 2001-04-05
US09/827,187 US20020150785A1 (en) 2001-04-05 2001-04-05 Coated article having the appearance of stainless steel

Publications (1)

Publication Number Publication Date
CN1460065A true CN1460065A (zh) 2003-12-03

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EP (1) EP1296820A1 (zh)
CN (1) CN1460065A (zh)
BR (1) BR0204749A (zh)
CA (1) CA2408957A1 (zh)
WO (1) WO2002081195A1 (zh)

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Publication number Priority date Publication date Assignee Title
US20090047540A1 (en) * 2005-03-07 2009-02-19 Material Sciences Corporation Colored acrylic coated metal substrate
US7125613B1 (en) * 2005-03-07 2006-10-24 Material Sciences Corporation, Engineered Materials And Solutions Group, Inc. Coated metal article and method of making same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6196936B1 (en) * 1996-01-11 2001-03-06 Molecular Metallurgy, Inc. Coated golf club component
US6004684A (en) * 1997-04-30 1999-12-21 Masco Corporation Article having a protective and decorative multilayer coating
US6033790A (en) * 1997-04-30 2000-03-07 Masco Corporation Article having a coating
US5879532A (en) * 1997-07-09 1999-03-09 Masco Corporation Of Indiana Process for applying protective and decorative coating on an article
US6143424A (en) * 1998-11-30 2000-11-07 Masco Corporation Of Indiana Coated article
US6132889A (en) * 1999-07-30 2000-10-17 Vapor Technologies, Inc. Coated article

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WO2002081195A1 (en) 2002-10-17
EP1296820A1 (en) 2003-04-02
CA2408957A1 (en) 2002-10-17
US20020150785A1 (en) 2002-10-17
BR0204749A (pt) 2003-04-29

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