CN1460060A - 含有具有不锈钢外观的聚合物基础涂层的涂敷制品 - Google Patents
含有具有不锈钢外观的聚合物基础涂层的涂敷制品 Download PDFInfo
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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聚合物层和在聚合物层上的气相沉积的堆叠层,堆叠层包括与包含耐火金属或耐火金属合金、氮气和氧气的反应产物的层交替的包含耐火金属或耐火金属合金的层,其中这些反应产物的总氮和氧含量为约4-约32原子百分比,氮含量至少为约3原子百分比。
Description
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护性有机涂层(如由丙烯酸类、聚氨酯类、环氧类等组成的涂层)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,且易于受酸的侵蚀。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多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的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。涂层是装饰性的和也提供耐腐蚀性、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。
制品首先在它的表面上沉积聚合物基础涂层。然后在聚合物基础涂层的顶部,通过气相沉积如物理气相沉积,沉积夹层或堆叠层。更特别地,直接沉积在基材表面上的第一层由聚合物组成。位于聚合物层上的是由如下物质组成的气相沉积保护性夹层或堆叠层:与包含耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物的层交替的包含耐火金属或耐火金属合金的层。在夹层或堆叠层上是由耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物组成的颜色层。耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物是耐火金属或耐火金属合金、氮气和氧气的反应产物,其中氮和氧含量较低,即,低于化学计量。这些耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物的总氮和氧含量为约4-约32原子百分比,优选约5-约28原子百分比,氮含量至少为约3原子百分比,优选至少约4原子百分比。
附图简述
图1是含有多层涂层基材一部分的不按比例的横截面图,该多层涂层包括聚合物基础涂层,在聚合物基础涂层上的保护性夹层或堆叠层和在堆叠层上的颜色层;
图2是相似于图1的视图,区别在于在聚合物层和夹层或堆叠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,区别在于在聚合物层和堆叠层中间存在铬层;和
图4是相似于图1的视图,区别在于在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,将聚合物或树脂层涂敷到制品表面上。通过气相沉积在聚合物表面上涂敷第二层或系列层。聚合物层尤其用作使制品表面变平的基础涂层。
聚合物基础涂层13可以由热塑性和热固性聚合物或树脂材料两者组成。这些聚合物或树脂材料包括公知的、常规和可购得的聚碳酸酯、环氧聚氨酯、聚丙烯酸酯、聚甲基丙烯酸酯、尼龙、聚酯、聚丙烯、聚环氧化物、醇酸树脂和含苯乙烯聚合物如聚苯乙烯、苯乙烯-丙烯腈(SAN)、苯乙烯-丁二烯、丙烯腈-丁二烯-苯乙烯(ABS)、及其共混物和共聚物。
聚碳酸酯描述在U.S.专利Nos.4,579,910和4,513,037中,这两个文献在此引入作为参考。
尼龙和聚酰胺可以通过二胺和二羧酸的反应制备。一般用于制备尼龙的二胺和二羧酸通常包含2-约12个碳原子。尼龙也可通过另外的聚合制备。它们描述在聚酰胺树脂”中,D.E.Floyd,ReinholdPublishing Corp.,纽约,1958,该文献在此引入作为参考。
聚环氧化物描述在H.Lee和K.Nevill的“环氧树脂”中,McGraw-Hill,纽约,1957,和描述在U.S.专利Nos.2,633,458、4,988,572、4,680,076、4,933,429和4,999,388中,所有这些文献在此引入作为参考。
聚酯是芳族二羧酸和二元醇的缩聚产物。芳族二羧酸包括对苯二甲酸、间苯二甲酸、4,4’-二苯基二羧酸、2,6-萘二羧酸等。二元醇包括含有2-约10个碳原子的低级链烷二醇,例如,乙二醇、丙二醇、环己烷二甲醇等。聚酯的一些说明性非限制性例子包括聚对苯二甲酸乙二醇酯、聚对苯二甲酸丁二醇酯、聚间苯二甲酸乙二醇酯、和聚(对苯二甲酸1,4-环己烷二亚甲基酯)。它们公开于U.S.专利Nos.2,465,319、2,901,466和3,047,539中,所有文献在此引入作为参考。
聚丙烯酸酯和聚甲基丙烯酸酯是来自如下物质聚合的聚合物或树脂:一种或多种丙烯酸酯,例如丙烯酸甲酯、丙烯酸乙酯、丙烯酸丁酯、丙烯酸2-乙基己酯等,以及甲基丙烯酸酯,例如甲基丙烯酸甲酯、甲基丙烯酸乙酯、甲基丙烯酸丁酯、甲基丙烯酸己酯等。以上丙烯酸酯和甲基丙烯酸酯单体的共聚物也包括在当它于其中出现时的术语“聚丙烯酸酯”和“聚甲基丙烯酸酯”中。以提供用于本发明实施的聚丙烯酸酯树脂的单体丙烯酸酯和甲基丙烯酸酯的聚合可以通过任何公知的聚合技术完成。
苯乙烯-丙烯腈和丙烯腈-丁二烯-苯乙烯树脂和它们的制备,尤其公开于U.S.专利Nos.2,769,804、2,989,517、2,739,142、3,991,136和4,387,179中,所有这些文献在此引入作为参考。
醇酸树脂公开于“醇酸树脂技术”中,Patton,IntersciencePublishers,NY,NY,1962,和公开于U.S.专利Nos.3,102,866、3,228,787和4,511,692中,所有这些文献在此引入作为参考。
环氧聚氨酯和它们的制备,尤其公开于U.S.专利Nos.3,963,663、4,705,841、4,035,274、4,052,280、4,066,523、4,159,233、4,163,809、4,229,335和3,970,535中,所有这些文献在此引入作为参考。特别有用的环氧聚氨酯是电涂在制品上的那些。这样的可电沉积环氧聚氨酯描述在上述U.S.专利Nos.3,963,663、4,066,523、4,159,233、4,035,274和4,070,258中。
这些聚合物材料可非必要地包含常规和公知的填料如云母、滑石和玻璃纤维。
可以通过任何公知和常规的方法如浸渍、喷涂、刷涂和电沉积将聚合物基础涂层13涂敷到基材表面上。
聚合物层13,尤其用于使基材表面变平、覆盖制品表面中的任何划痕或缺陷和提供平滑和均匀的表面用于继续层如气相沉积层的沉积。
聚合物基础涂层13的厚度至少有效使制品或基材的表面变平。一般情况下,此厚度至少为约0.12μm,优选至少约2.5μm,和更优选至少约5μm。厚度上限范围应当不超过约250μm。
在一些情况下,依赖于基材材料和聚合物基础涂层的类型,聚合物基础涂层并不能充分地粘合到基材上。在这样的状况下,在基材上沉积底漆层以改进聚合物基础涂层对基材的粘合。底漆层可以尤其由卤化聚烯烃组成。卤化聚烯烃是一般可市售的常规和公知的聚合物。优选的卤化聚烯烃是氯化和溴化聚烯烃,更优选是氯化聚烯烃。卤化聚烯烃,特别是氯化聚烯烃和它们的制备方法一起,尤其公开于U.S.专利Nos.5,319,032、5,840,783、5,385,979、5,198,485、5,863,646、5,489,650和4,273,894中,所有这些文献在此引入作为参考。
底漆层的厚度是有效改进聚合物基础涂层对基材粘合的厚度。一般情况下此厚度至少为约0.25μm。厚度上限不是关键的且一般由次要的如成本和外观的考虑来控制。一般情况下应当不超过约125μm的上限厚度。
在一个实施方案中,如图3所示,位于聚合物层13和气相沉积层之间的是一个或多个电镀层21。这些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。厚度上限一般不是关键的且由次要的如成本的考虑来决定。然而,一般情况下,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。厚度上限范围一般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。
在聚合物层,或如存在的电镀层上,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,至少沉积由如下组成的夹层或堆叠层32:与由耐火金属含氮和氧化合物或耐火金属合金含氮和氧化合物组成的层36交替的包括耐火金属或耐火金属合金的层34。
包括耐火金属或耐火金属合金的层34包括铪、钽、钛、锆、锆-钛合金、锆-铪合金等,优选铪、钛、锆或锆-钛合金。
包括耐火金属含氮和氧化合物和耐火金属合金含氮和氧化合物的层36是耐火金属或耐火金属合金、氧气和氮气的反应产物。在这些耐火金属含氮和氧化合物和耐火金属合金含氮和氧化合物中,总氮和氧含量为约4-约32原子百分比,优选约5-约28原子百分比,最小氮含量至少为约3原子百分比,优选至少约4原子百分比。因此,例如,氮含量是6原子百分比和氧含量是20原子百分比,氮含量是8原子百分比和氧含量是8原子百分比,氮含量是15原子百分比和氧含量是2原子百分比。氧的存在量一般至少为约1原子百分比。
这些反应产物的氮含量一般尤其对具有不锈钢颜色的涂层有影响。氮含量为至少约3原子百分比到约22原子百分比,优选至少约4原子百分比到约16原子百分比。氮含量不应当超过约22原子百分比,优选约16原子百分比,或涂层损失了它的不锈钢外观和开始具有镍颜色。因此,氮含量对于具有不锈钢颜色的涂层是关键的。
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氧化物或耐火金属合金氧化物,耐火金属氮化物或耐火金属合金氮化物,和耐火金属氧-氮化物或耐火金属合金氧-氮化物组成。因此,例如,锆、氧气和氮气的反应产物包括氧化锆,氮化锆和氧-氮化锆。包括氧化锆和氮化锆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,且尤其公开于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。
夹层或堆叠层32的平均厚度一般为约500埃-1μm,优选约0.1μm-0.9μm,和更优选约0.15μm-0.75μm。夹层或堆叠层一般包含约4-约100个交替层34和36,优选约8-约50个交替层34和36。
每个层34和36的厚度一般至少为约15埃,优选至少约30埃,和更优选至少约75埃。一般情况下,层34和36应当不厚于约0.38μm,优选约0.25μm,和更优选约0.1μm。
形成堆叠层32的方法是通过采用溅射或阴极弧蒸发以沉积耐火金属如锆或钛的层34,随后通过反应性溅射或反应性阴极弧蒸发以沉积耐火金属含氮和氧化合物或金属合金含氮和氧化合物的层36。
优选在气相沉积如反应性溅射期间,在零(不引入气体)到在所需值下引入气体之间改变(脉冲)氮气和氧气的流量,以在夹层32中形成耐火金属或耐火金属合金的层36与耐火金属或耐火金属合金、氮气和氧气的反应产物的层34的多个交替层。
在夹层或堆叠层32上是颜色层38。颜色层38由耐火金属或耐火金属合金、氮气和氧气的反应产物组成。颜色层38由如与层36相同的含氮和氧化合物组成,例如,颜色层38具有与层36包含的化合物相同的氮和氧含量。颜色层38的厚度至少有效提供颜色,更具体地为提供不锈钢颜色。一般情况下,此厚度至少为约25埃,和更优选至少约500埃。厚度上限范围不是关键的且依赖于次要的如成本的考虑。一般情况下不超过约0.75μm,优选约0.65μm,和更优选约0.5μm的厚度。
改变颜色层38中的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。
除夹层或堆叠层32和颜色层38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在堆叠层32和聚合物或电镀层之间沉积的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堆叠层32对聚合物或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31一般位于堆叠层32和聚合物或电镀层中间。层31的厚度一般至少有效使层31用作触击层,即用以改进堆叠层32对其下的层的粘合。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)或溅射,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”,AcademicPress,1991;R.Boxman等人,“真空弧科学和技术手册”,NoyesPub.,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在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、铪或锆组成,和耐火金属合金由锆-钛合金组成。
另外的气相沉积层可包括不是上述耐火金属或耐火金属合金、氮气和氧气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,耐火金属氮化物和耐火金属合金氮化物,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38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39。该层39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。这些氧化物和它们的制备是常规和公知的。
层39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39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39应当足够薄使得它并不使其下的颜色层38的颜色变暗。即层39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39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38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,将龙头清洗和干燥。
通过标准和常规的高体积低压枪将基础涂层聚合物组合物涂敷到清洁和干燥的龙头上。该聚合物由35wt%苯乙烯化丙烯酸类树脂,30wt%蜜胺甲醛树脂,和35wt%双酚A环氧树脂组成。将聚合物溶于足够的溶剂以提供包含约43wt%固体的聚合物组合物。在龙头上涂敷基础涂层之后,使龙头静置20分钟用于环境溶剂闪蒸。然后将龙头在375°F下焙烧两小时。获得的固化聚合物基础涂层的厚度为约20μm。
将聚合物涂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,该真空腔适于通过泵抽空。通过用于改变进入腔室的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的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且连接到可变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。
将涂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和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100℃。
然后将聚合物涂敷的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2×10-1毫巴压力的速率下引入氩气。在聚合物层上涂敷堆叠层。在足以提供约6-16原子百分比氮和氧含量的流量下,周期性地向真空腔室中引入氮气和氧气流。此氮气流是氩气、氮气和氧气总物流的约4-20%,和氧气流是氩气、氮气和氧气总物流的约4-20%。在流动期间弧放电在大约500安培下持续。将氮气和氧气流量脉冲,即将它周期性地从总流量约10%-20%和约零的流量改变。氮气和氧气脉冲的周期是1到2分钟(30秒到1分钟开启,然后关闭)。脉冲沉积的总时间是约15分钟,导致10-15个层的堆叠,每个层的厚度为约2.5埃-约75埃。
在沉积堆叠层之后,将氮气和氧气流量保留在足以提供约5-28原子百分比的总氮和氧含量的流量下,此氮气和氧气流量是氩气、氮气和氧气总流量的约4-约30%,持续约5-10分钟的时间,以在堆叠层顶部形成颜色层。在沉积此颜色层之后,终止氮气流和将大约0.1标准升每分钟的氧气流引入30秒到1分钟的时间。形成厚度为约50埃-125埃的氧化锆薄层。在该最后沉积阶段结束时将弧熄灭,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 (11)
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:
由聚合物组成的层;
由如下组成的堆叠层:与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层交替的由耐火金属或耐火金属合金组成的层;
由耐火金属或耐火金属合金、氮气和氧气的反应产物组成的颜色层,
其中耐火金属或耐火金属合金、氮气和氧气的所述反应产物的总氮和氧含量为约4-约32原子百分比和氮含量至少为约3原子百分比。
2.权利要求1的制品,其中所述总氮和氧含量为约5-约28原子百分比和氮含量至少为约4原子百分比。
3.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。
4.权利要求1的制品,其中耐火金属或耐火金属合金触击层在所述聚合物层上。
5.权利要求1的制品,其中铬层在所述聚合物层上。
6.权利要求5的制品,其中耐火金属或耐火金属合金触击层在所述铬层上。
7.权利要求1的制品,其中所述耐火金属选自铪、锆和钛。
8.权利要求1的制品,其中所述耐火金属合金是锆-钛合金。
9.权利要求3的制品,其中所述耐火金属选自锆、钛和铪。
10.权利要求6的制品,其中所述耐火金属选自锆、钛和铪。
11.权利要求6的制品,其中耐火金属合金是锆-钛合金。
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US09/827,005 US6558816B2 (en) | 2001-04-05 | 2001-04-05 | Coated article with polymeric basecoat having the appearance of stainless steel |
US09/827,005 | 2001-04-05 |
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CN1460060A true CN1460060A (zh) | 2003-12-03 |
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US (2) | US6558816B2 (zh) |
EP (1) | EP1296819B1 (zh) |
JP (1) | JP2004537436A (zh) |
CN (1) | CN1460060A (zh) |
AT (1) | ATE365104T1 (zh) |
BR (1) | BR0204757A (zh) |
CA (1) | CA2408960C (zh) |
DE (1) | DE60220754T2 (zh) |
DK (1) | DK1296819T3 (zh) |
TW (1) | TW592978B (zh) |
WO (1) | WO2002081198A1 (zh) |
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CN101119860B (zh) * | 2005-02-17 | 2012-08-22 | 桑德维克知识产权股份公司 | 涂敷的金属产品、其制备方法及该方法的用途 |
CN102877065A (zh) * | 2012-09-26 | 2013-01-16 | 广州海鸥卫浴用品股份有限公司 | 一种涂层沉积方法 |
CN106457753A (zh) * | 2014-03-07 | 2017-02-22 | 南澳大利亚大学 | 用于塑料基材的装饰涂层 |
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US6558816B2 (en) * | 2001-04-05 | 2003-05-06 | Vapor Technologies, Inc. | Coated article with polymeric basecoat having the appearance of stainless steel |
US6551722B2 (en) * | 2001-04-11 | 2003-04-22 | Masco Corporation Of Indiana | Coated article having a stainless steel color |
US20040038068A1 (en) * | 2002-08-26 | 2004-02-26 | Finch John G. | Coated article with polymeric basecoat cured at low temperatures |
US20040099369A1 (en) * | 2002-11-22 | 2004-05-27 | Sparks Darrell L. | Composite sheet with mirror finish |
US9074357B2 (en) | 2011-04-25 | 2015-07-07 | Delta Faucet Company | Mounting bracket for electronic kitchen faucet |
US9057184B2 (en) | 2011-10-19 | 2015-06-16 | Delta Faucet Company | Insulator base for electronic faucet |
US9333698B2 (en) | 2013-03-15 | 2016-05-10 | Delta Faucet Company | Faucet base ring |
US10393363B2 (en) | 2017-04-25 | 2019-08-27 | Delta Faucet Company | Illumination device for a fluid delivery apparatus |
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-
2001
- 2001-04-05 US US09/827,005 patent/US6558816B2/en not_active Expired - Fee Related
- 2001-12-19 US US10/026,036 patent/US6764775B2/en not_active Expired - Fee Related
-
2002
- 2002-04-04 BR BR0204757A patent/BR0204757A/pt not_active Application Discontinuation
- 2002-04-04 EP EP02715265A patent/EP1296819B1/en not_active Expired - Lifetime
- 2002-04-04 JP JP2002579215A patent/JP2004537436A/ja active Pending
- 2002-04-04 WO PCT/US2002/010336 patent/WO2002081198A1/en active IP Right Grant
- 2002-04-04 CA CA 2408960 patent/CA2408960C/en not_active Expired - Fee Related
- 2002-04-04 CN CN02801082A patent/CN1460060A/zh active Pending
- 2002-04-04 DK DK02715265T patent/DK1296819T3/da active
- 2002-04-04 AT AT02715265T patent/ATE365104T1/de not_active IP Right Cessation
- 2002-04-04 DE DE2002620754 patent/DE60220754T2/de not_active Expired - Lifetime
- 2002-04-30 TW TW91109003A patent/TW592978B/zh not_active IP Right Cessation
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101119860B (zh) * | 2005-02-17 | 2012-08-22 | 桑德维克知识产权股份公司 | 涂敷的金属产品、其制备方法及该方法的用途 |
CN102877065A (zh) * | 2012-09-26 | 2013-01-16 | 广州海鸥卫浴用品股份有限公司 | 一种涂层沉积方法 |
CN102877065B (zh) * | 2012-09-26 | 2014-12-10 | 广州海鸥卫浴用品股份有限公司 | 一种涂层沉积方法 |
CN106457753A (zh) * | 2014-03-07 | 2017-02-22 | 南澳大利亚大学 | 用于塑料基材的装饰涂层 |
CN106457753B (zh) * | 2014-03-07 | 2019-05-10 | 南澳大利亚大学 | 用于塑料基材的装饰涂层 |
Also Published As
Publication number | Publication date |
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DE60220754T2 (de) | 2008-03-06 |
TW592978B (en) | 2004-06-21 |
ATE365104T1 (de) | 2007-07-15 |
US20020146595A1 (en) | 2002-10-10 |
DE60220754D1 (de) | 2007-08-02 |
EP1296819A1 (en) | 2003-04-02 |
WO2002081198A1 (en) | 2002-10-17 |
US20020146596A1 (en) | 2002-10-10 |
EP1296819B1 (en) | 2007-06-20 |
US6558816B2 (en) | 2003-05-06 |
DK1296819T3 (da) | 2007-10-29 |
US6764775B2 (en) | 2004-07-20 |
CA2408960A1 (en) | 2002-10-17 |
JP2004537436A (ja) | 2004-12-16 |
BR0204757A (pt) | 2003-04-29 |
CA2408960C (en) | 2005-11-08 |
EP1296819A4 (en) | 2006-10-18 |
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