CN114592168A - 生物活性涂覆基板 - Google Patents

生物活性涂覆基板 Download PDF

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Publication number
CN114592168A
CN114592168A CN202111483507.3A CN202111483507A CN114592168A CN 114592168 A CN114592168 A CN 114592168A CN 202111483507 A CN202111483507 A CN 202111483507A CN 114592168 A CN114592168 A CN 114592168A
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China
Prior art keywords
bioactive
layer
coated substrate
copper
zirconium
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Pending
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CN202111483507.3A
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English (en)
Inventor
B·R·安顿
尼古拉斯·皮特森
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Vapor Technologies Inc
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Vapor Technologies Inc
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Publication of CN114592168A publication Critical patent/CN114592168A/zh
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
    • A01N25/34—Shaped forms, e.g. sheets, not provided for in any other sub-group of this main group
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0015—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterized by the colour of the layer
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • A—HUMAN NECESSITIES
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    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/0676—Oxynitrides
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/083—Oxides of refractory metals or yttrium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/087—Oxides of copper or solid solutions thereof
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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Abstract

一种生物活性涂覆基板，包括底基板、布置在该底基板上的指示层、以及布置在该指示层上的生物活性层。特征在于，该指示层具有与该生物活性层足够不同的颜色以当该生物活性层磨损掉时被用户在视觉上感知到。

Description

生物活性涂覆基板
相关申请的交叉引用
本申请要求于2020年12月7日提交的美国临时申请序列号63/122,240的权益，该临时申请的公开内容在此通过援引以其全部内容并入本文。
技术领域
在至少一个方面，本发明涉及一种通过物理气相沉积和/或相关方法形成的具有生物活性的特性的涂层体系，尤其是具有磨损指示物的基于铜的抗微生物PVD涂层。
背景技术
物理气相沉积(PVD)是用于薄膜形成或涂覆基板的技术。PVD涉及材料的蒸发，然后该材料凝结在表面上，形成涂层。PVD可能导致大颗粒的沉积，这经常被认为是缺陷。这些大颗粒可松散地结合到涂覆的层。可以使用机械方法去除这些大颗粒，但去除留下小孔，这也经常被认为是缺陷。例如，阴极电弧蒸发(CAE)(PVD的形式，涉及在阴极靶的表面上的高电流，低电压电弧)产生大颗粒。由于大颗粒和小孔被认为是缺陷，因此付出巨大努力来消除或减少大颗粒的尺寸和数量。
具有生物活性的特性的涂层可用于各种用途。生物活性材料是指对生物具有生物效应或生理效应的材料。例如，生物活性的材料包括导致生物的正常生物功能或生理机制改变的材料。如本文使用的，生物活性包括对微生物有益和有害的影响或对微生物的正常功能的改变。一种常见的生物活性的材料是抗微生物物质。抗微生物涂层具有许多用途。通常抗微生物涂层抑制微生物(像病毒、细菌或真菌生物体)生长或将其杀死。一个特别相关的实例包括通过使用抗微生物材料防止可传染疾病的传播。抗微生物材料还可以用于卫生用途。防止疾病传播和加强卫生的期望导致在开发抗微生物材料方面作出了重大努力。在医疗保健设施和健康治疗中使用抗微生物材料可以提供重大益处。保健设施(如医院)呈现出独特的环境，该环境组合了高浓度病菌和具有脆弱的免疫力的个体。因此，设施(如医院)从抗微生物表面极大地受益。用于医疗设备的抗微生物材料可以减少消毒的负担并防止疾病传播。此外，负担得起的抗微生物表面可以在与生物接触的任何表面上呈现出益处。例如，烹饪中涉及的表面或通常触摸的表面(像门把手)可以从抗微生物特性极大地受益。甚至主要是装饰性的表面，如果负担得起，也可以从抗微生物特性获益并且帮助抑制有害或不希望的抗微生物生物的传播和生长。
但是生产抗微生物材料可能是困难且昂贵的。此外，抗微生物材料可能具有其他不希望的特性。例如，一些抗微生物材料可能过于软。其他抗微生物材料可能具有差的耐磨性。
Figure BDA0003396432810000021
是包括分散在有机基质中的银颗粒的抗微生物涂层。涉及有机基质的抗微生物涂层可能具有涂漆的美学外观。在一些应用中，涂漆的外观可能是不希望的。一些抗微生物涂层可以使用纳米颗粒气相沉积以在涂层的表面上沉积具有抗微生物特性的纳米颗粒。例如，来自布鲁泰克公司(Protec)的
Figure BDA0003396432810000022
是使用纳米颗粒的抗微生物涂层。然而，使用纳米颗粒可能是复杂且昂贵的。此外，此类涂层可能具有易碎的表面或差的耐磨性。抗微生物材料的另一个实例包括各种金属。例如，已知银具有抗微生物特性。然而，如上所述，银可能是昂贵的，并且它的特性可能不适合用于许多应用。例如，银的外观或耐磨性可能不适合用于某些应用。
因此，需要一种抗微生物涂层，该涂层解决了这些问题中的一个或多个或为现有的抗微生物材料提供了替代方案。
发明内容
在至少一个方面，提供了一种生物活性涂覆基板。该生物活性涂覆基板包括底基板、布置在该底基板上的指示层、以及布置在该指示层上的生物活性层。特征在于，该指示层具有与该生物活性层足够不同的颜色以当该生物活性层磨损掉时被用户在视觉上感知到。
在另一方面，提供了一种生物活性涂覆基板。该生物活性涂覆基板包括底基板、布置在底基板上的底层；以及布置在底层上的多个交替的生物活性层和中间层。特征在于，底层和/或中间层中的至少一个是指示层，该指示层具有与生物活性层足够不同的颜色以当生物活性层中的一个或多个磨损掉时被用户在视觉上感知到。
在还另一方面，提供了一种生物活性涂覆基板。该生物活性涂覆基板包括底基板、布置在底基板上的最外面的生物活性层、以及布置在最外面的生物活性层下的指示层。
附图说明
图1A是具有生物活性层和指示层的生物活性涂覆基板的示意性截面。
图1B是具有多个交替的生物活性层、中间层的生物活性涂覆基板的示意性截面，且至少一个层是指示层。
具体实施方式
现在将详细参考本发明目前优选的组合物、实施例和方法，它们构成了本发明人目前已知的实施本发明的最佳模式。附图不一定按比例绘制。然而，应理解，所披露的实施例仅仅是本发明的示例，本发明可以以不同的替代性形式实施。因此，本文披露的具体细节不应解释为限制性的，而仅仅解释为本发明任何方面的代表性基础和/或用于传授本领域技术人员以各种方式采用本发明的代表性基础。
除了在实例中或另外明确指出之外，本说明书中表示材料的量或反应和/或使用条件的所有数值数量应理解为在描述本发明的最宽范围时由词语“约”修饰。通常优选在规定的数值限度内的实践。此外，除非有相反的明确规定，否则百分比、“份数”和比值是按重量计的；与本发明相结合，将一组或一类材料描述为对于给定的目的是适合的或优选的意味着该组或该类中的任何两个或更多个成员的混合物同样是适合的或优选的；以化学术语对成分进行描述是指在添加到该描述中指定的任何组合中时的成分，并且一旦混合后，不一定排除混合物的成分之间的化学相互作用；首字母缩写或其他缩写的第一个定义适用于本文相同缩写的所有后续用法，并且经必要的变更适用于最初定义的缩写的正常语法变体；并且，除非有相反的明确规定，否则特性的测量是通过与之前或之后针对同一特性引用的相同技术确定的。
还必须注意，如本说明书和所附权利要求中所使用的，除非上下文另外清楚地指出，否则单数形式“一个/种(a/an)”和“该”包括复数指代物。例如，以单数形式对组分的引用旨在包括多个组分。
短语“由……构成”意指“包括”或“包含”。典型地，该短语用于指示物体由材料形成。
术语“包含”与“包括”、“具有”、“含有”、或“特征为”同义。这些术语是包含性和开放性的，并且不排除另外的、未列举的要素或方法步骤。
短语“由……组成”排除权利要求中未指定的任何要素、步骤或成分。当此短语出现在权利要求的主体的条款中，而不是紧跟在前序之后时，它只限制该条款中列出的要素；其他要素作为整体未被排除在该权利要求之外。
短语“基本上由……组成”将权利要求的范围限制于指定的材料或步骤，以及不实质地影响所要求保护主题的一个或多个基础且新颖特征的那些。
关于术语“包含”、“由……组成”和“基本上由……组成”，在本文使用这三个术语之一的情况下，本发明披露和要求保护的主题可包括使用其他两个术语中的任一个。
术语“基本上”、“通常”或“约”可以在本文中用于描述所披露的或所要求保护的实施例。术语“基本上”可以修饰本披露中披露或要求保护的值或相对特征。在此类情况下，“基本上”可以意味着它修饰的值或相对特征是在该值或相对特征的±0％、0.1％、0.5％、1％、2％、3％、4％、5％或10％内。
还应该理解，整数范围明确地包括所有中间整数。例如，整数范围1至10明确包括1、2、3、4、5、6、7、8、9和10。类似地，范围1至100包括1、2、3、4....97、98、99、100。类似地，当需要任何范围时，介于中间的数字(其是上限与下限之间的差除以10的增量)可以被认为是可替代的上限或下限。例如，如果范围是1.1至2.1，则可以选择以下数字1.2、1.3、1.4、1.5、1.6、1.7、1.8、1.9和2.0作为下限或上限。在本文所述的具体实例中，浓度、温度和反应条件(例如，压力、流速等)可以用四舍五入为三位有效数字的所示值的加或减50％来实施。在改进方案中，浓度、温度和反应条件(例如，压力、流速等)可以用实例中提供的值的四舍五入为三位有效数字的所示值的加或减30％来实施。在另一个改进方案中，浓度、温度和反应条件(例如流速等)可以用实例中提供的值的四舍五入为三位有效数字的所示值的加或减10％来实施。
在本文所述的实例中，浓度、温度和反应条件(例如，压力、流速等)可以用实例中提供的值的四舍五入为或截断(舍位)为两位有效数字的所示值的加或减50％来实施。在改进方案中，浓度、温度和反应条件(例如，压力、流速等)可以用实例中提供的值的四舍五入为或截断(舍位)为两位有效数字的所示值的加或减30％来实施。在另一个改进方案中，浓度、温度和反应条件(例如，压力、流速等)可以用实例中提供的值的四舍五入为或截断(舍位)为两位有效数字的所示值的加或减10％来实施。
对于表示为具有多个字母和数字下标的经验化学式(例如，CH2O)的所有化合物，下标的值可以是四舍五入或截断(舍位)为两位有效数字的所示值的加或减50％。例如，如果指示CH2O，式C(0.8-1.2)H(1.6-2.4)O(0.8-1.2)的化合物。在改进方案中，下标的值可以是四舍五入或截断(舍位)为两位有效数字的所示值的加或减30％。在还另一个改进方案中，下标的值可以是四舍五入或截断(舍位)为两位有效数字的所示值的加或减20％。
在整个本申请中，在引用公开案的情况下，这些公开案的披露内容特此通过援引以其全部内容并入本申请，以更全面地描述本发明所属领域的状态。
缩写：
“DLC”意指类金刚石。
“CAE”意指阴极电弧蒸发。
“PVD”意指物理气相沉积。
图1A和图1B提供了涂覆有生物活性层且具有指示层的基板的截面。参照图1A，生物活性涂覆基板10包括底基板12和布置在底基板上且任选地与其接触的指示层14。术语“底基板”是指被涂覆以形成下面所述的生物活性的基板之前的基板。生物活性层16布置在指示层14上且任选地与其接触。特征在于，指示层14可以充当最外面的生物活性层16被损坏的视觉指示。特别是，指示层具有与生物活性层足够不同的颜色以当生物活性层磨损掉时被用户在视觉上感知到，从而为用户提供生物活性层16被损坏的视觉警示。关于设置各层的颜色以便可以确定颜色差异，应该理解的是，以上所述的层中的每一个的颜色都可以通过调整层的厚度和/或化学计量来独立地改变。在改进方案中，指示层14典型地具有从约20至300nm的厚度。在另一个改进方案中，生物活性层16具有从约50至1500nm的厚度。生物活性涂覆基板10的层中的每一个都可以通过CVD、PVD(可以为溅射)或CAE制造。
图1B提供了具有多个交替的生物活性层和中间层22的生物活性涂覆基板的示意性截面。在该变体中，生物活性涂覆基板10’包括底基板12和任选的布置在底基板上且任选地与其接触的底层18。多个交替的生物活性层16’和中间层22布置在基板12和底层18(如果存在)上。典型地，可以存在1至10个生物活性层16’和1至10个中间层22。特征在于，底层18和/或中间层22中的至少一个是指示层。典型地，涂覆的基板10’的最外层是生物活性层。在改进方案中，底层18和/或中间层22可以由锆碳氮化物、锆氮化物、锆碳氧化物、锆氮氧化物或锆碳氮氧化物构成。在另一个改进方案中，中间层22也可以是生物活性层，但是具有与它在相反面接触的生物活性层不同的厚度和/或化学计量。就这方面而言，中间层22可以由如以下所述的各种铜合金构成。在另一个改进方案中，中间层22可以由金属氮化物构成。例如，中间层22可以由锆氮化物(ZrN)、钛氮化物(TiN)、锆碳氧化物(ZrOC)、锆氧化物(ZrO2)、类金刚石(DLC)或其组合构成。在另一个变体中，中间层22中的一个或多个可以是指示层。生物活性涂覆基板10的层中的每一个都可以通过CVD、PVD(可以为溅射)或CAE制造。
在改进方案中，底层18和/或中间层22各自独立地具有从约20至300nm的厚度。在另一个改进方案中，生物活性层16具有从约50至1500nm的厚度。
在图1A和图1B中描绘的涂覆的基板的一些变体中，指示层可以由锆碳氮化物、锆氮化物、锆碳氧化物、锆氮氧化物或锆碳氮氧化物、钛氮化物、锆氧化物、钛氧化物、或类金刚石构成。指示层14典型地具有从约20至300nm的厚度。应理解的是，本发明的实施例不受用于沉积指示层14和生物活性层16的具体沉积方法的限制。例如，这些层可以通过CVD、PVD(可以为溅射)或CAE制造。
图1A和图1B的生物活性层16和16’可以是具有生物活性特性的任何材料。特别地，生物活性层16和16’是抗微生物层。因此，生物活性层16和16’可以包括具有抗微生物特性的材料。在改进方案中，生物活性层16和16’可以由选自由以下组成的组的组分(具有抗微生物特性)构成：生物活性的金属、生物活性的金属合金、生物活性的含金属的化合物(例如金属氧化物)、及其组合。例如，生物活性层16和16’可以由以下构成：铜金属、银金属、含铜金属的化合物、含银金属的化合物、及其组合。
在另一个改进方案中，生物活性层16和16’可以由选自由以下组成的组的组分构成：铜合金、含铜的化合物、及其组合。此类含铜的化合物包括呈+1或+2氧化态的铜原子或其铜原子的组合。含铜的化合物的实例包括但不限于铜、铜氧化物、铜氮化物、含碳原子的铜氧化物、及其组合。在一个变体中，铜合金包括铜和镍。典型地，每种铜合金包括生物活性层的总重量的从约8至28重量％的量的镍，其中铜是以生物活性层的总重量的从约72至92重量％的量存在。在改进方案中，铜合金包括生物活性层的总重量的从约10至25重量％的量的镍和生物活性层的总重量的从约75至90重量％的量的铜。在一些变体中，铜合金可以独立地包括额外的元素，如铁、锆、钨、铬、及其组合。在改进方案中，这些额外的元素中的每一种独立地以生物活性层的总重量的从约0.01至约5重量％的量存在。在改进方案中，这些额外的元素中的每一种独立地以生物活性层的总重量的从约0.01至约5重量％的量存在。铜合金的实例是从位于肯塔基州路易斯维尔的奥林黄铜公司(Olin Brass)可商购的
Figure BDA0003396432810000081
White Bronze和
Figure BDA0003396432810000082
Rose。
在其他变体中，生物活性层16和16’包括银、银合金、含银的化合物(例如银氧化物)、或其任何组合。可以展现出抗微生物特性的其他金属包括但不限于镓(Ga)、金(Au)、镁(Mg)、钛(Ti)和锌(Zn)。生物活性层16和16’可以包括金属、金属氧化物或金属合金的组合。这包括例如包括铜(Cu)和银(Ag)的生物活性层16。
在一个改进方案中，一个或多个生物活性层16和16’中的每一个独立地由CuOx构成，其中x是从0.6至1.2。在另一个改进方案中，一个或多个生物活性层16和16’中的每一个独立地由CuOaNb构成，其中a是从0.0至1.2且b是从0.01至0.4。在还另一个改进方案中，一个或多个生物活性层16和16’中的每一个独立地由CuOcCd构成，其中c是从0.0至1.2且d是从0.01至0.4。在变体中，一个或多个生物活性层14和14’中的每一个独立地由铜金属、CuOx、CuOaNb和CuOcCd的任何组合构成；因此，一个或多个生物活性层16和16’中的每一个独立地由以下构成：铜金属、CuOx、CuOaNb和CuOcCd的组合，或铜金属和CuOx的组合，或铜金属和CuOaNb的组合；铜金属和CuOcCd的混合物，或铜金属、CuOx和CuOaNb的组合，或铜金属、CuOx和CuOcCd的组合，或铜金属、CuOaNb和CuOcCd的组合，或CuOx、CuOaNb和CuOcCd的组合，或CuOx和CuOaNb的组合，或CuOaNb和CuOcCd的组合，或CuOx、CuOaNb和CuOcCd的组合。一些合适的生物活性层可以由CuxOy、CuxNy、CuxOyNz和CuxOyCz构成，其中x可以是1、2或3；y可以是1、2或3；并且z可以是1、2或3。
在另一个变体中，一个或多个生物活性层由铜金属合金和选自由以下组成的组的组分的混合物构成：锆氮化物、钛氮化物、锆碳氧化物、锆氧化物、类金刚石、及其组合。
在另一个变体中，层16和16’由铜合金和以下中的至少一种的混合物构成：锆氮化物、钛氮化物、锆碳氧化物、锆氧化物、或类金刚石。
指示层14、底层18、中间层22以及生物活性层16和16’可以施加于任何合适的基板12。合适的基板12可以由任何材料构成，该材料展现出在这些层中的每一个的操作(即，使用生物活性涂覆基板的温度)或沉积温度下的热稳定性。特别地，基板12在至少80℃的温度下应该是热稳定的。在改进方案中，基板12在至少250℃的温度下应该是热稳定的。在一些改进方案中，合适的基板12可以由导电的任何材料构成。例如，可以构成底基板的合适的材料包括但不限于金属、金属合金和/或碳材料。可以构成底基板的合适的材料的额外的实例包括但不限于不锈钢、镀铬镍黄铜、镀铬镍铜锌、镀铬镍铜ABS塑料、以及镀铬镍铜铝。
在另一个变体中，底层18和中间层22独立地由锆或钛、碳和氮构成，其中锆以至少50摩尔％的量存在，且碳和氮中的每一种分别以至少0.02摩尔％和0.1摩尔％的量存在。在改进方案中，底层18和中间层22独立地由具有下式的化合物构成：
M1-x-yCxNy
其中M是锆或钛并且x是0.0至0.3并且Y是0.1至0.5。在改进方案中，x是0.0至0.2并且y是0.2至0.3。在另一个改进方案中，x是至少(以递增优选顺序)0.0、0.02、0.03、0.04、0.05、0.07或0.09且至多(以递增优选顺序)0.5、0.4、0.3、0.25、0.2、0.15或0.11。类似地，在此改进方案中，y是至少(以递增优选顺序)0.1、0.15、0.2、0.25、0.27或0.29且至多(以递增优选顺序)0.6、0.5、0.40、0.35、0.33或0.31。在另外的改进方案中，底层由Zr0.60C0.10N0.30所述的锆碳氮化物构成。
在还另一个变体中，底层18和中间层22独立地由锆或钛、碳和氧构成，其中锆以至少50摩尔％的量存在，且碳和氧中的每一种分别以至少0.02摩尔％和0.1摩尔％的量存在。在改进方案中，底层18和中间层22独立地由具有下式的化合物构成：
M1-x-yOxCy。
其中M是锆或钛并且x是0.1至0.4并且y是0.5至0.2。在另外的改进方案中，底层由Zr0.50O0.35C0.15所述的锆碳氧化物构成。
在获取指示层与生物活性层16和16’之间的颜色差异时，应理解的是，生物活性层16和16’以及指示层14(以及基板和其他层)可以特征在于相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*。在改进方案中，生物活性层(例如典型地是最外面的生物活性层)的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的至少一个与指示层的那个相差至少(以递增优选顺序)5％、10％、15％、20％、25％或50％。在另一个改进方案中，生物活性层(例如典型地是最外面的生物活性层)的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的每一个与指示层的那些相差至少(以递增优选顺序)5％、10％、15％、20％、25％或50％。在变体中，量化颜色空间中两点之间的距离的ΔE(2000)可以用来量化两种颜色之间的差异。两种颜色之间的视觉或明显的区别可能受到各种因素(包括观察者、质地和光泽度)的影响。在改进方案中，大于或等于1.0的ΔE对于指示物来说是足够的颜色差异。在另一个改进方案中，大于或等于2.0的ΔE是足够的颜色差异。在还另一个改进方案中，大于或等于5.0的ΔE是足够的颜色差异。在一些变体中，大于或等于以下的ΔE是足够的颜色差异：以递增优选顺序，2.0、5.0、8.0、10.0、15.0和20.0。
在另一个实施例中，图1A和图1B的生物活性涂覆基板包括在制品中。在改进方案中，有用的制品进一步包括指示层，如上所述。许多医疗保健或医院表面可以极大地得益于生物活性涂覆基板。例如，有用的制品可以包括但不限于床栏杆、竖板、床头柜、旋钮、把手、安全栏杆、手推车、推板、踢脚板、拖把板、担架板、龙头、排水管、水槽、水龙头、排水杆、饮水器部件、消毒器/肥皂分发器、干手器、常用按钮、头枕、淋浴头、台面、铰链、锁、闩锁、装饰、马桶或小便池硬件、灯开关、扶手、恒温控制器、电话、地砖、吊顶板、墙砖、仪器把手(例如药物递送系统、监测系统、病床、办公设备、手术室设备、支架和固定装置)、静脉输液架、托盘、平底锅、助行器、轮椅、键盘、计算机鼠标表面、运动设备、康复设备、理疗设备、灯、照明系统、盖子、衣架、遥控器、杯架、牙刷架、礼服按扣和窗台板。同样，大众或公共区域通常可以得益于具有生物活性涂覆基板的制品。例如，一些制品或表面可以包括但不限于购物车、购物车把手、儿童座椅、扶手、收银机键盘、收银机外壳、ATM、储物柜、电梯控制器、纸巾分配器、卫生纸分配器、自动售货机、和洗手间表面。类似的制品和表面可以对住宅区、公共交通、实验室、宗教聚会设施或任何经常访问的设施有益。其他用途可以包括但不限于书写用具、眼镜架、梳子、手机套、平板电脑套、耳机和开瓶器(举几个来说)。
虽然以上描述了示例性实施例，但并不意味着这些实施例描述了本发明的所有可能形式。相反，本说明书中使用的词语是描述性而不是限制性词语，并且应理解，在不脱离本发明的精神和范围的情况下，可以进行各种改变。另外，可以组合各种实现实施例的特征以形成本发明的进一步的实施例。

Claims (25)

1.一种生物活性涂覆基板，其包括：
底基板；
布置在所述底基板上的指示层；以及
布置在所述指示层上的生物活性层，其中所述指示层具有足以区分于所述生物活性层的颜色，从而当所述生物活性层磨损掉时能被用户在视觉上感知到。
2.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由选自由以下组成的组的组分构成：生物活性的金属、生物活性的金属合金、生物活性的含金属的化合物、及其组合。
3.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由选自由以下组成的组的组分构成：铜金属、铜氧化物、铜氮化物、含碳原子的铜氧化物、及其组合。
4.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由选自由以下组成的组的组分构成：铜金属、铜合金、铜氧化物、铜氮化物、含碳原子的铜氧化物、及其组合。
5.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由选自由以下组成的组的组分构成：铜合金、含铜的化合物、及其组合。
6.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由铜金属合金和选自由以下组成的组的组分的混合物构成：锆氮化物、钛氮化物、锆碳氧化物、锆氧化物、类金刚石、及其组合。
7.如权利要求1所述的生物活性涂覆基板，其中，所述指示层由以下构成：锆碳氮化物、锆氮化物、锆碳氧化物、锆氮氧化物或锆碳氮氧化物、钛氮化物、锆氧化物、钛氧化物、或类金刚石。
8.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层具有从约50至1500nm的厚度并且所述指示层具有从20至300nm的厚度。
9.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由CuOx构成，其中x是从0.6至1.2。
10.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由CuOaNb构成，其中a是从0.0至1.2且b是从0.01至0.4。
11.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层由CuOcCd构成，其中c是从0.0至1.2且d是从0.01至0.4。
12.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的至少一个与所述指示层的那个相差至少5％。
13.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的每一个与所述指示层的那些相差至少5％。
14.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层和所述指示层的ΔE大于或等于2.0。
15.如权利要求1所述的生物活性涂覆基板，其中，所述生物活性层和所述指示层的ΔE大于或等于5.0。
16.一种生物活性涂覆基板，其包括：
底基板；
布置在所述底基板上的底层；以及
布置在所述底层上的多个交替的生物活性层和中间层，其中所述底层和/或所述中间层中的至少一个是指示层，所述指示层具有足以区分于所述生物活性层的颜色，从而当所述生物活性层中的一个或多个磨损掉时能被用户在视觉上感知到。
17.如权利要求16所述的生物活性涂覆基板，其包括1至10个生物活性层和1至10个中间层。
18.如权利要求16所述的生物活性涂覆基板，其中，每个生物活性层由选自由以下组成的组的组分构成：生物活性的金属、生物活性的金属合金、生物活性的含金属的化合物、及其组合。
19.如权利要求16所述的生物活性涂覆基板，其中，每个生物活性层由选自由以下组成的组的组分构成：铜金属、铜合金、铜氧化物、铜氮化物、含碳原子的铜氧化物、及其组合。
20.如权利要求16所述的生物活性涂覆基板，其中，所述底层和每个中间层由以下构成：锆碳氮化物、锆氮化物、锆碳氧化物、锆氮氧化物或锆碳氮氧化物、钛氮化物、锆氧化物、钛氧化物、或类金刚石。
21.如权利要求16所述的生物活性涂覆基板，其中，每个生物活性层具有从约50至1500nm的厚度，每个中间层具有从20至300nm的厚度，并且所述底层具有从20至300nm的厚度。
22.如权利要求16所述的生物活性涂覆基板，其中，最外面的生物活性层的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的至少一个与所述指示层的那个相差至少5％。
23.如权利要求16所述的生物活性涂覆基板，其中，最外面的生物活性层的相对于CIE标准光源D50的实验室色空间坐标L*、a*和b*的每一个与所述指示层的那些相差至少5％。
24.如权利要求16所述的生物活性涂覆基板，其中，最外面的生物活性层和所述指示层的ΔE大于或等于2.0。
25.如权利要求16所述的生物活性涂覆基板，其中，最外面的生物活性层和所述指示层的ΔE大于或等于5.0。
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