CN107735436B - 用于涂布制品的方法 - Google Patents

用于涂布制品的方法 Download PDF

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Publication number
CN107735436B
CN107735436B CN201680035104.3A CN201680035104A CN107735436B CN 107735436 B CN107735436 B CN 107735436B CN 201680035104 A CN201680035104 A CN 201680035104A CN 107735436 B CN107735436 B CN 107735436B
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article
antimicrobial
precursor
layer
coating
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CN107735436A (zh
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王英男
缪卓南
江争
刘焕明
郝少康
黄家伟
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Master Dynamic Ltd
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Master Dynamic Ltd
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    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
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  • Physical Vapour Deposition (AREA)
  • Materials For Medical Uses (AREA)
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Abstract

一种向制品的表面提供抗菌涂层的方法，所述方法包括如下步骤：将抗菌前体层施加到待施加抗菌涂层的制品的表面，其中所述抗菌前体层是待形成涂层的前体；和将来自中性分子氢通量发射源的中性分子氢通量引向制品的表面。在中性氢分子撞击制品表面处或表面上的分子后，抗菌前体层的键选择性断裂，并且其中选择性断裂的键与其自身或与所述表面处的其他化学基团或其组合交联，从而在制品的表面上形成抗菌涂层。

Description

用于涂布制品的方法
技术领域
本发明涉及一种用于将涂层施加到制品的方法和由此获得的涂布制品。更特别地，本发明提供一种用于将涂层施加到制品的方法，如功能性涂层。
背景技术
在涂布需要将涂层施加到表面的构件或制品中，本领域的技术包括使用离子加速等的放电和加速相关技术。
例如，在本领域中，通常由金属基、硅基和镍磷(Ni-P)基材料形成的机械表构件或微型零件可能需要涂布。
由于高精度和衬底材料特征，在金属零件上进行的常规机械加工和电镀通常不能满足制造期间对于高精度和不导电类微型零件的关键要求。
这些微型零件可以通过微机电系统(MEMS)技术(诸如深度反应离子蚀刻(DRIE)和紫外线光刻(光刻))以及电铸成形(Galvanoformung)、模铸(Abformung)(UV-LIGA)制造。由于这些技术的生产能力和表面精饰要求的限制，诸如溅射、电子束等的方法可以用于微型零件沉积。在本领域中，将基于溅射的沉积技术用于MEMS制造。其可以通过调节功率、DC/RF转换、持续时间和压力来控制，例如对于膜厚度、宽度和均匀性控制。
对于常规溅射型沉积，其通常在高真空值下进行，并且在施加溅射和引入真空室等之前，借助于诸如压力式固定装置的机构将待涂布的样品或制品固定到固持器件。
在这些本领域的方法中，存在如下缺陷，包括在溅射沉积方法期间压力固定装置可覆盖的样品或制品上存在一些未涂布的盲区，并且这可能导致溅射源背面的涂层表面不均匀。此外，任何膜或涂层可能通过接触膜与压制性固定装置之间的硬接触而相对容易地被刮掉。
对于构件、样品和制品，包括硅基构件、样品和制品，使用现有技术的沉积方法来精确控制厚度(包括在纳米级)可能会遇到困难，因为在一些应用中，可能要求微型零件的所有表面用薄膜同时沉积。
在其它应用中，需要将非常薄的涂层施加到制品，诸如由金属或金属合金形成的制品，由此这些涂层必须能经受至少标称量的摩擦冲击，而所述制品不会磨损或耗损。
同样，在本领域已知的这些方法中，提供的可能是美观的或功能性的和厚度均匀的这些涂层通常会被耗损、剥离或具有不均匀的厚度。
本发明的目的
本发明的一个目的在于提供一种涂布制品的方法，其克服了或至少部分改善了与现有技术有关的至少一些缺陷。
发明内容
在第一方面中，本发明提供向制品的表面提供抗菌涂层的方法，所述方法包括如下步骤：
(i)将抗菌前体层施加到待施加抗菌涂层的制品的表面，其中所述抗菌前体层是待形成涂层的前体；和
(ii)将来自中性分子氢通量(hydrogen flux)发射源的中性分子氢通量引向制品的表面；
其中在中性氢分子撞击制品表面处或表面上的分子后，抗菌前体层的键选择性断裂，并且其中选择性断裂的键与其自身或与所述表面处的其他化学基团(chemicalmoieties)交联，从而在制品的表面上形成抗菌涂层。
在本发明的一个实施方式中，选择性断裂的键是C-H键和Si-H键中的任一者或者是C-H键与Si-H键的组合。
所述方法还可以包括在施加前将至少第一层前体施加到制品的表面的步骤，其中在将抗菌层前体施加到制品之前将所述第一层前体施加到制品的表面，并且安置在制品的表面与抗菌层前体之间。
将来自中性分子氢通量发射源的中性分子氢通量引向制品的表面后，所述第一层前体的材料的键选择性地断裂并且与制品表面处的其它化学基团交联。
将来自中性分子氢通量发射源的中性分子氢通量引向制品的表面后，抗菌前体层的断裂的键与所述第一层交联。
所述第一层前体在制品表面上形成分子单层或分子级厚度的层。所述第一层前体可以形成光学透明层。
在一个实施方式中，所述第一层前体由11-巯基十一烷酸形成。
在另一个实施方式中，通过如下步骤将所述第一层前体施加到制品的表面：在溶液中提供11-巯基十一烷酸的第一层前体溶液，由此将制品浸泡在11-巯基十一烷酸溶液中预定量的时间并移出，其中干燥后在制品上形成所述第一层前体，并且优选所述第一层前体溶液是50Mm 11-巯基十一烷酸的乙醇溶液。
在另一个实施方式中，所述抗菌前体层由包含抗菌化合物的抗菌前体溶液提供，并且所述抗菌化合物可以是壳聚糖。
所述抗菌前体溶液可以是包含壳聚糖、聚合物、酸和表面活性剂的溶液。优选地，所述抗菌前体溶液由壳聚糖、聚季铵盐-6、乙酸和吐温20(Tween 20)在去离子水中形成，并且更优选地，所述抗菌前体溶液由约1:1比率的壳聚糖和聚季铵盐-6，乙酸和约0.005重量％吐温20在去离子水中形成。
所施加的抗菌涂层优选是分子单层或分子级厚度的层，并且所述抗菌涂层优选是光学透明的。
在本发明的实施方式中，所述制品的表面可以由金属或金属合金形成；由包含选自如下组的成分的贵金属形成，所述组含有金、金基合金、银、铂等；由聚合材料形成；或由硅或硅基材料形成。
所述制品可以是珠宝、钟表构件、医疗装置、医疗仪器、植入物、卫生仪器、容器、器皿、包装材料等的物品。
在第二方面中，本发明提供一种施加有抗菌涂层的制品，其中所述抗菌涂层是根据第一方面的方法施加至制品的。
在第三方面中，本发明提供一种在制品的表面上提供涂层的方法，所述方法包括如下步骤：
(i)将第一层前体施加到制品的表面；
(ii)在所述第一层前体上将外层前体施加到制品；和
(iii)将来自中性分子氢通量发射源的中性分子氢通量引向制品的表面；
其中在中性氢分子撞击制品表面处或表面上的分子后，所述第一前体层的键选择性断裂，并且其中选择性断裂的键至少与所述表面处的其他化学基团交联，从而在制品的表面上形成第一层；并且
其中在中性氢分子撞击制品表面处或表面上的分子后，外层前体层的键选择性断裂，并且其中选择性断裂的键至少与所述第一层的其他化学基团交联，从而在制品上形成涂层。
在一个实施方式中，选择性断裂的键是C-H键和Si-H键中的任一者或者是C-H键与Si-H键的组合。
在另一个实施方式中，所述外层前体包含抗菌化合物，使得涂层是抗菌涂层。
在另一个实施方式中，所述外层前体包含防湿化合物，使得涂层是防湿涂层。
所述第一层优选是分子单层或分子级厚度的层，使得在交联后，所述第一层是光学透明的。
优选地，所述涂层是分子单层或分子级厚度的层，使得在交联后，涂层是光学透明的。
在第四方面中，本发明提供一种施加有涂层的制品，其中所述涂层是根据第三方面的方法施加至制品的。
附图说明
现在参考附图描述本发明的实例，其中：
图1显示根据本发明的用于将涂层施加到制品的系统的一个实施方式的示意图；
图2显示根据ASTM E2149标准在接种细菌后一小时对具有施加到金表面的抗菌涂层的制品进行抗菌评价的结果；
图3显示图2的结果的概述；
图4显示根据国际标准ISO22196在接种细菌后24小时对具有施加到金表面的抗菌涂层的制品进行抗菌评价的结果；
图5显示图4的结果的概述；
图6显示珠宝毒性结果，根据ASTM F 2923-14-儿童珠宝的特定衬底材料中的总镉含量；以及根据ASTM F 2923-14-儿童珠宝的油漆和表面涂层中的可溶性重金属；
图7显示珠宝毒性结果，根据ASTM F 2923-14-儿童珠宝中的总铅含量；以及根据ASTM F 2923-14-镍释放；
图8显示珠宝毒性结果，根据ASTM F 2000-14-成人珠宝中的总铅含量；以及根据ASTM F 2999-14-成人珠宝中特定衬底材料的总镉含量；并且
图9显示珠宝毒性结果，根据ASTM F 2999-14-成人珠宝的油漆和表面涂层中的可溶性重金属；和根据ASTM F 2999-14-镍释放。
具体实施方式
本发明提供一种将涂层施加到制品表面的方法，由此可以在制品的表面上形成分子级的非常薄的涂层。
在本发明的实施方式中，本发明提供适用于施加到珠宝制品的抗菌涂层，从而向佩戴这些珠宝制品的人提供健康益处。在这些应用中，不改变制品的光学外观是非常重要的，本发明特别适用。本发明提供一种光学透明涂层，其不可通过观察来检测，并且有迹象表明存在这种涂层。
此外，在诸如珠宝的应用中，要求涂层在正常使用中不易磨损或耗损，因此，如本发明所提供的适用于珠宝的涂层必须能耐受这种耗损。
本发明提供的其它涂层(诸如防湿涂层)也可以被施加在分子级的层中，使得光可以透过而没有任何涂层存在的迹象。由于这种涂层非常薄并且在分子范围内，所以重要的是涂层被良好地粘附或附着到制品上，并且该涂层能耐受通常适用的耗损，例如当施加到。
为了提供这种涂布方法，本发明人使用中性分子氢通量发射源，将该中性分子氢通量发射源引向已经通过向制品施加前体涂层来预处理的制品，在向所述制品施加中性分子氢通量后形成涂层。
为了在本发明中使用，这种中性分子氢通量可以用来自Lau，W.M.Leo等人的申请第13/255,038号的US9,113,544所述的方式提供，并且所述案以交叉引用的方式并入本文中。
可以提供中性分子氢通量来在制品表面上提供涂层的方式包括如下步骤：
(a)形成等离子体并从所述等离子体中提取能量在约50eV至约1keV范围内的质子流；之后
(b)将质子流引入腔室中并将氢分子引入腔室中；
(c)通过使来自所述质子流的质子与氢分子碰撞而将动能赋予所述氢分子来产生高能氢分子；
(d)通过所述高能氢分子与其他氢分子之间的级联碰撞，产生动能在约1eV至约100eV范围内的中性分子氢通量，从而引起高能氢分子的所有方向散射；和
(e)将中性分子氢通量引向衬底表面，使得在中性氢分子撞击表面处或表面上含有C-H键和Si-H键的任一者或组合的分子后，C-H键和Si-H键选择性断裂。
中性分子氢与前体层碰撞后，选择性破裂的键与其自身或与表面处的其他化学基团交联，从而使得表面特性改变，或者是所述交联的组合。
参考图1，显示了可以将根据本发明的涂层施加到制品的方式的系统100的示意图。在本发明的实施方式中，发射源120是中性分子氢通量发射源，并且发射元素是中性分子氢155。
中性分子氢通量发射源120将中性分子氢155的通量引向支撑构件110，使得中性氢分子155撞击制品130的表面140处或表面140上的分子后，制品130的表面140处或表面140上的分子的元素之间的键选择性断裂。
中性分子氢通量发射源120包含氢等离子体源170，其中将氢气130传递到氢通量发射源120，使氢等离子体145被加速至腔室125，并且将中性分子氢通量发射155引向制品130。
氢等离子体源170可以是选自以下组的等离子体源，所述组包括DC等离子体、RF等离子体、普通微波等离子体或电子回旋共振(ECR)微波等离子体。
在适用于本发明的一个实施方式中，中性分子氢通量发射源120将动能在约1eV至约100eV范围内的中性分子氢155通量引向支撑构件110，使得中性氢分子撞击制品表面处或表面上含有C-H键和Si-H键的任一者或组合的分子后，C-H键和Si-H键选择性断裂。
通过如下步骤提供本发明所用的用于断开键的中性分子氢通量发射流，来断开制品表面处或表面上的分子中的C-H和Si-H分子键的任一者或组合。
本发明方法使用上述方法来提供必需的涂层。
如本领域技术人员所了解，本发明所用的上述断键和交联工序中的化学反应是复杂的，并且需要考虑许多参数，包括控制中性分子氢通量发射流的量，能级，功率，制品表面处的材料，形成前体材料以形成涂层的材料特性，形成涂层的前体材料的化学和物理特性，用于形成抗菌涂层的前体材料的功能属性和生物属性，佩戴相关特性，前体层的施加和厚度等。
下文描述根据本发明的抗菌涂布方法和其应用的实施例。
1.实施例-抗菌涂布系统和材料
根据本发明，提供了一种抗菌涂布系统来用于将抗菌涂层施加到由金形成的制品的表面，其中上面施加涂层的外表面由金形成。
为了向本实施例中的这种制品提供抗菌涂层，该方法包括以下主要步骤：
(i)将第一层前体施加到制品的表面；
(ii)在所述第一层前体上将抗菌前体层施加到制品；和
(iii)将来自中性分子氢通量发射源的中性分子氢通量引向制品的表面。
1.1第一层前体
借助于包含50Mm 11-巯基十一烷酸的乙醇溶液的第一溶液将本实施例中的第一层前体施加到制品。
在约35摄氏度的升高的温度下将制品浸泡在第一溶液中约10分钟的时间段。
接着从第一溶液移出制品并且用乙醇冲洗。
应了解，视待涂布制品而定，上述参数可能需要一些变化。
接着例如借助于吹风机干燥制品直到干燥，之后将抗菌前体层施加到制品。
1.2抗菌层前体
为了将抗菌前体层施加到制品，其中欲将所述抗菌前体层施加在第一层前体上，借助于包含抗菌化合物的第二溶液施加抗菌前体层。
在本实施例中，抗菌化合物是壳聚糖，并且所述第二溶液在去离子水中包含约1:1比例的壳聚糖和聚季铵盐-6、乙酸和约0.005重量％吐温20。
将制品浸泡在第二溶液中约60秒，之后以约2000微米/秒的相对中等线速度移出样品。将这种浸泡和移出工序重复多次，例如五次。
应了解，视待涂布制品而定，上述参数可能需要一些变化。
在完成浸泡和移出工序之后，将制品在约45摄氏度的升高的温度下干燥约15分钟，从而形成抗菌涂层前体。
1.3中性分子氢通量暴露
在抗菌涂层前体的形成完成后，接着将制品暴露于中性分子氢通量，例如参考图1所述，由此中性氢分子撞击，第一前体层的键选择性地断裂，并且其中选择性断裂的键至少与表面处的其他化学基团交联，从而在制品的表面上形成第一层。
中性氢分子撞击分子使得抗菌前体层的键选择性断裂，其中选择性断裂的键至少与第一层的其他化学基团交联，从而在金制品上形成抗菌涂层。
根据本发明，例如以参考图1所述的方式使制品暴露于中性分子氢通量。
使用如下所述的标准试验和分析方案评价上述实施例的有效性。
2.抗菌评价
为了评价本发明提供的抗菌涂层在施加到金衬底时的抗菌有效性，使用如下国际标准进行独立的试验实验室分析。
2.1 1小时后的细菌活性
根据ASTM E2149标准“在动态接触条件下测定固定的抗微生物剂的抗微生物活性(Determining the Antimicrobial Activity of Immobilized Antimicrobial AgentsUnder Dynamic Contact Condition)”进行试验，以确定暴露于细菌一小时后抗菌涂层的有效性。
用于分析的硅晶片样品上面具有金层，其中使用参考以上实施例1描述的抗菌系统用抗菌涂层涂布金层，并通过使用参考图1描述的方法并且为本发明申请人所有的装置暴露于中性分子氢通量，该装置使用微波功率。
向试验实验室提供五个样品，三个施加有抗菌涂层，并且两个用于对照试验。
用具有如下的菌落形成单位/毫升(CFU/mL)的含有大肠杆菌(AATCC 25922)的悬浮液接种样品：
(i)未处理样品的初始CFU/mL270,000vs.处理样品，和
(ii)未处理样品的初始CFU/mL170,000,000vs.2000x摩擦的涂布样品和10000x摩擦的涂布样品。
图2中再现分析实验室提供的结果，并且图3中再现1小时后的结果的概述。
如图3所示，一小时后，对于抗菌涂层未暴露于摩擦的样品，细菌减少大于99.9％。
对于具有抗菌涂层并且摩擦2000x和10000x的样品，细菌分别减少41.5％和30.5％。
2.2 24小时后的细菌活性
根据国际标准ISO22196“塑料和其他无孔表面上的抗菌活性测量(Measurementof antibacterial activity on plastics and other non-porous surfaces)”进行试验，以确定暴露于细菌24小时后抗菌涂层的有效性。
使用参考以上实施例1描述的抗菌系统用抗菌涂层涂布用于分析的上面具有金层的硅晶片样品，并通过使用再次参考图1描述的方法并且为本发明申请人所有的装置暴露于中性分子氢通量。
向试验实验室提供五个样品，三个施加有抗菌涂层，并且两个用于对照试验。
用具有如下的菌落形成单位/毫升(CFU/mL)的含有大肠杆菌(AATCC 25922)的悬浮液接种样品，其中对于每个样品使用0.4ml的接种物：
(i)未处理样品的初始CFU/mL270,000vs.处理样品，和
(ii)未处理样品的初始CFU/mL570,000,000vs.2000x摩擦的涂布样品和10000x摩擦的涂布样品。
图4中再现分析实验室提供的结果，并且图5中再现24小时后的结果的概述。
如图5所示，24小时后，对于抗菌涂层未暴露于摩擦的样品，细菌减少大于99.9％。
对于具有抗菌涂层并且摩擦2000x和10000x的样品，细菌分别减少61.2％和41.2％。
2.3抗菌评价的结论
用细菌接种后1小时和24小时的两个试验的结果展示，本发明提供的抗菌涂层在施加到具有金表面的制品且没有任何摩擦时基本上杀死所有细菌。
对于施加摩擦的样品，抗菌涂层在1小时和24小时后都显著减少了细菌的量。
结果展示，尽管抗菌涂层仅具有分子级厚度，但是当施加到金制品(诸如被穿戴的珠宝物品)时，抗菌涂层仍然显著减少了制品表面上的细菌量。
由此，本发明提供了一种适用于施加到珠宝制品(诸如由金形成的珠宝制品)的抗菌涂层。
尽管在本实施例中，壳聚糖被用作抗菌剂，但是在其它实施例中并且在本发明的范围内可以使用其它抗菌剂。
3.珠宝制品适用性评价
为了展示本发明的抗菌涂层对于珠宝制品的适用性和标准相符性，针对儿童珠宝和成人珠宝两者评价涂有金的制品并且就相关标准进行了分析。
3.1儿童珠宝适用性评价
施加到硅晶片上的金的抗菌涂层(其中将抗菌涂层施加到金表面)由外部试验机构就以下标准进行评价：
(i)ASTM F 2923-14-儿童珠宝的特定衬底材料中的总镉含量
(ii)ASTM F 2923-14-儿童珠宝的油漆和表面涂层中的可溶性重金属
(iii)ASTM F 2923-14-儿童珠宝中的总铅量含量
(iv)ASTM F 2923-14-镍释放
参考图6和图7，重现了所提供的试验的结果。如所展示，在任何涂布样品中都没有发现元素，由此每个试验报告“ND”，这意指“未检测到”元素，表示此时元素的量小于方法检测限。
3.2成人珠宝适用性评价
施加到硅晶片上的金的抗菌涂层(其中将抗菌涂层施加到金表面)由外部试验机构就以下标准评价：
(i)ASTM F 2000-14-成人珠宝中的总铅量含量
(ii)ASTM F 2999-14-成人珠宝的特定衬底材料中的总镉含量
(iii)ASTM F 2999-14-成人珠宝的油漆和表面涂层中的可溶性重金属
(iv)ASTM F 2999-14-镍释放
参考图8和图9，重现了所提供的试验的结果。如所展示，在任何涂布样品中都没有发现元素，由此每个试验报告“ND”，这意指“未检测到”元素，表示此时元素的量小于方法检测限。
3.3珠宝制品适用性评价
分析结果展示，具有根据本发明的抗菌涂层的金制品没有可检测元素(这些元素根据标准珠宝试验标准可能是有毒的)，因此符合珠宝的标准要求。
因此，本发明提供一种适用于儿童和成人两者的珠宝制品的抗菌涂层。
4.抗菌涂层的珠宝适用性
珠宝制品经常与人的皮肤接触，因此，其上细菌的存在造成了健康风险和担忧。特别地，儿童可能无意中将珠宝制品表面上存在的细菌转移到其口中，这进一步造成了健康风险。此外，由于一些珠宝制品延伸穿过人的真皮，例如用于穿耳的耳环，所以来自珠宝上存在的细菌的细菌感染的风险增加。
此外，由于一些珠宝制品(诸如戒指)在人的手上或靠近人的手，在日常使用和与物体和其他人接触中，细菌可能会转移到珠宝制品上，从而使佩戴者面临风险。珠宝制品(诸如戒指)经常具有华丽的结构和几何形状，其包含凹陷和槽口(rebate)以及难以接近的区域(诸如宝石镶嵌架周围的区域)，从而提供细菌寄存和生长的位置。由于珠宝的性质，使用者通常不愿意非常规律地清洁珠宝制品，并且在手洗珠宝制品(诸如戒指)的情况下可能不能充分清洁并保留有细菌。
因此，从卫生和安全观点来看，固有地需要降低暴露于珠宝制品上的细菌的风险。
与可能需要抗菌涂层的多种其他制品不同，珠宝制品对这种抗菌涂层具有具体的要求：
(i)其必须在暴露于细菌时具有杀灭和减少细菌的适合效力，
(ii)其必须是光学上不可见的，并且不会损害珠宝制品所具有的任何美学效果，诸如改变由金形成的珠宝制品的金的光学特性，
(iii)其在施加到珠宝时，不得对触感产生任何变化，因为使用者必须经历与未处理材料相同的触感，以免损害价值和人的身体期望，
(iv)其必须能经受日常的正常耗损和撕扯，因为在使用期间珠宝制品的表面固有地会被磨损和耗损，
(v)其必须符合标准，并且将涂层施加到珠宝制品时所使用的加工和方法不得使涂层或待施加制品的衬底的化学结构产生任何改变(这将导致可能有毒的元素或化合物释放)，并符合相关珠宝标准；并且其不得具有任何可能有毒的元素或化合物，并符合相关珠宝标准，
(vi)用于施加涂层的方法不得使珠宝制品的表面造成任何破坏，并且
(vii)其在最终从制品表面耗损或在破坏时应能够再施加。
如上文所展示，本发明提供一种适用于珠宝制品的表面的抗菌涂层并且如下满足上述要求：
(1)已经展示并独立评价了对细菌的作用的有效性，
(2)通过将涂层施加成单层或分子级，涂层不能被肉眼辨别，并且其存在需要科学分析技术，
(3)由于涂层被施加成这种薄层以及其材料，所以其存在不可能借助于感觉检测，因此触觉完全不变，
(4)标准试验展示，尽管涂层的施加量极少，但在大量耗损的情况下，涂层仍对细菌有效，
(5)已经展示并且独立评价了与珠宝毒性评价标准的相符性，
(6)本发明方法不需要改变表面来施加抗菌涂层，并且
(7)本发明方法能再应用至抗菌涂层已被从其去除或磨损的制品。
在优选实施方式中，本发明提供了一种在制品表面上形成抗菌涂层的方法，其克服了现有技术中的缺陷和缺点。
现有技术的解决方案不提供均匀涂层，特别是对于需要非常薄的膜涂层的制品，其缺陷包括由于不均匀性造成的制品光学方面的变化，不足的“环绕”，由此涂层不能适当地围绕制品的边缘延伸，从而使得涂层从制品剥落和剥离。
此外，当需要这种涂层是光学透明的时，现有技术的解决方案不能将非常薄的涂层容易地施加到制品。
本发明提供如下的技术方案，其通过提供使得能够将更均匀且结合良好的涂层施加到制品的方法来解决现有技术的缺陷。
现有技术的其它缺陷为在制品的边缘上存在最小的沉积或涂层形成，这提供美学上较差的产品，从而产生较低的产量并增加了检查时间和对设计要求满足情况的确定。
此外，现有技术的这些技术由于薄涂层和缺乏与制品的施加有涂层的表面相邻的边缘的“环绕”而得到如下制品，其涂层易于从制品剥落或剥离，从而产生较低的产量并增加了检查时间和对设计要求满足情况的确定。这也可能导致在一段时间后损坏(failure)，从而具有不利的商业影响。
更进一步地，这些现有技术需要将制品从其所放置的衬底上移出，这可能损害涂层的完整性并产生一些剥落，再次产生较低的产量并增加了检查时间和对设计要求满足情况的确定。
尽管在实施例中，壳聚糖被用作抗菌剂，但是在其它实施例中并且在本发明的范围内可以使用其它抗菌剂。
尽管所提供的实施例涉及将抗菌涂层施加到金表面，特别是关于珠宝制品的适用性。然而，本领域技术人员应了解，本发明还适用于形成薄涂层，例如防湿涂层。
在其他或替代性实施方式、本发明和其方法中，制品可以由金属或金属合金形成，由包含金基合金、银、铂等的贵金属形成，或由聚合物材料形成；或由硅或硅基材料形成。
适用于这些涂层的其它制品包括钟表构件、医疗装置、医疗仪器、植入物、卫生仪器、容器、器皿、包装材料等。

Claims (21)

1.一种向制品的表面提供抗菌涂层的方法，所述方法包括如下步骤：
(i)将抗菌前体层施加到待施加抗菌涂层的制品的表面上，其中所述抗菌前体层是待形成涂层的前体；和
(ii)将来自中性分子氢通量发射源的中性分子氢通量引向所述制品的所述表面；
其中在中性氢分子撞击制品的所述表面处或所述表面上的分子后，所述抗菌前体层的键选择性断裂，并且其中所述选择性断裂的键与其自身或与所述表面处的其他化学基团或其组合交联，从而在所述制品的所述表面上形成抗菌涂层，
其中所述制品的所述表面由金属或金属合金形成，且
其中所述方法还包括在施加前将至少第一层前体施加到所述制品的所述表面的步骤，其中在将所述抗菌层前体施加到所述制品之前将所述第一层前体施加到所述制品的所述表面，并且安置在所述制品的所述表面与所述抗菌层前体之间，其中所述第一层前体由11-巯基十一烷酸形成。
2.根据权利要求1所述的方法，其中所述选择性断裂的键是C-H键和Si-H键中的任一者或者是C-H键与Si-H键的组合。
3.根据权利要求1所述的方法，其中将来自所述中性分子氢通量发射源的中性分子氢通量引向所述制品的所述表面后，所述第一层前体的材料的键选择性地断裂并且与所述制品的所述表面处的其它化学基团交联。
4.根据权利要求1所述的方法，其中将来自所述中性分子氢通量发射源的中性分子氢通量引向所述制品的所述表面后，所述抗菌前体层的断裂的键与所述第一层交联。
5.根据权利要求1所述的方法，其中所述第一层前体在所述制品的所述表面上形成单层。
6.根据权利要求1所述的方法，其中所述第一层前体形成光学透明层。
7.根据权利要求1所述的方法，其中通过如下步骤将所述第一层前体施加到所述制品的表面：在溶液中提供11-巯基十一烷酸的第一层前体溶液，由此将所述制品浸泡在所述11-巯基十一烷酸溶液中预定量的时间并移出，其中干燥后在所述制品上形成所述第一层前体。
8.根据权利要求1所述的方法，其中所述第一层前体溶液是50Mm 11-巯基十一烷酸的乙醇溶液。
9.根据权利要求1或2所述的方法，其中所述抗菌前体层通过包含抗菌化合物的抗菌前体溶液提供。
10.根据权利要求1或2所述的方法，其中所述抗菌化合物是壳聚糖。
11.根据权利要求9所述的方法，其中所述抗菌前体溶液是包含壳聚糖、聚合物、酸和表面活性剂的溶液。
12.根据权利要求9所述的方法，其中所述抗菌前体溶液由壳聚糖、聚季铵盐-6、乙酸和吐温20在去离子水中形成。
13.根据权利要求9所述的方法，其中所述抗菌前体溶液由1:1比率的壳聚糖和聚季铵盐-6、乙酸和0.005重量％吐温20在去离子水中形成。
14.根据权利要求1或2所述的方法，其中所施加的所述抗菌涂层是分子单层或分子级厚度的层。
15.根据权利要求1或2所述的方法，其中所述抗菌涂层是光学透明的。
16.根据权利要求1或2所述的方法，其中所述制品的所述表面由包含选自如下组的成分的贵金属形成，所述组包含金、金基合金、银和铂。
17.根据权利要求1或2所述的方法，其中所述制品是珠宝物品。
18.根据权利要求1或2所述的方法，其中所述制品是钟表构件。
19.根据权利要求1或2所述的方法，其中所述制品是医疗装置、医疗仪器、植入物或卫生仪器。
20.根据权利要求1或2所述的方法，其中所述制品是容器、器皿或包装材料。
21.一种施加有抗菌涂层的制品，其中所述抗菌涂层是根据前述权利要求中任一项所述的方法施加至所述制品的。
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