CN1446371A - 抗染污性硬涂层 - Google Patents

抗染污性硬涂层 Download PDF

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Publication number
CN1446371A
CN1446371A CN01813797A CN01813797A CN1446371A CN 1446371 A CN1446371 A CN 1446371A CN 01813797 A CN01813797 A CN 01813797A CN 01813797 A CN01813797 A CN 01813797A CN 1446371 A CN1446371 A CN 1446371A
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China
Prior art keywords
hard conating
layer
nhco
substrate
perfluorinated polyether
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Pending
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CN01813797A
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English (en)
Inventor
裘章华
刘军钪
布鲁斯·D·克卢格
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3M Innovative Properties Co
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3M Innovative Properties Co
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Publication of CN1446371A publication Critical patent/CN1446371A/zh
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Abstract

本发明提供了抗染污性硬涂覆薄膜，其包括一基本上透明的基板，一包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和一包含全氟化聚醚的抗染污层。所述抗染污层可以非常薄，从而降低全氟化聚醚的成本。所述薄膜具有非常好的耐磨、耐脏和抗眩光性，以及非常好的层间粘合性和耐久性。所述薄膜可以是单一挠性基板或层叠挠性基板的形式。可调整所述薄膜或层叠的尺寸，使之适合电子显示设备如个人数字助理或蜂窝电话的显示屏。

Description

抗染污性硬涂层
发明领域
本发明涉及保护性薄膜和涂层。
发明背景
光学显示设备，尤其触摸板显示设备，通常有一个暴露的由热塑性膜或板制成的观看面。通常使用的热塑性聚合物具有非常好的光透性、尺寸稳定性和抗冲击性，但不幸的是却具有很弱的耐磨性。光学显示设备，例如个人数字助理(“PDA”)、蜂窝电话、触摸显示屏和可移动计算机滤器会经常与使用者的脸部或手指、触针、珠宝和其他物体接触。例如，面部的油脂会不利地影响蜂窝电话显示屏的对比度、色彩饱和度或亮度。投影电视和膝上型计算机的屏幕较少受到触摸，但是有时仍会受到触碰、刮擦或染污。结果，在日常的使用中显示设备的表面易于划伤、磨损和变脏。这会导致显示设备失去清晰度和透明度，有时甚至不能辨认或失去作用。可以使用保护膜或涂层来保护这些显示设备。
用于PDA、蜂窝电话和其他显示设备的保护膜可以从很多商业途径获得，包括A.R.M(SECURERTM屏幕保护器)，CompanionLinkSoftware，Inc.(COMPANIONLINKTM PDA屏幕保护器)，EC Film(PDA屏幕保护器)，Fellowes Corporation(WrightRIGHTTM PDA屏幕保护器)，PerfectData Coporation(SILKYBOARDTM PDA键盘和屏幕保护器)，ROTA Technology Inc.(RT-PDS屏幕保护器和RT-MPS移动电话屏幕保护器)，Swann Communications(PDA PLUSTM屏幕保护器)，Sanwa Supply Inc.(LCD-PDA屏幕保护器)和VSPS(V.S.保护屏)。通常这些产品以按规格裁切好的平纹塑料膜单板形式出售，但是有些产品至少在膜的部分表面有织纹或带色彩。据说以上提到的部分保护膜能使PDA屏幕不被染污。观看屏保护装置也出现在例如美国专利No.4,907,090(Ananian)；6,059,628(Yoo等)；6,250,765(Murakami)和Re.35，318(Warman)中。日本已公开的专利申请2000-020240(Kokai)中提到了最外层为粗糙面的触摸板装置。
硬涂层也被用于保护信息显示设备的表面。这些硬涂层通常包含无机氧化物微粒，例如，以纳米尺寸分散在粘结剂前体树脂基质中的氧化硅，这些硬涂层有时被称为“陶瓷体”(ceramers)。例如，美国专利No.5,104,929(Bilkadi`929)中描述了UV固化性的陶瓷体涂层，其包含分散在质子基团取代的丙烯酸酯或酰胺中的胶态氧化硅颗粒。Bilkadi`929中描述并已命名为3M 906抗磨损涂层的陶瓷体已经在信号装置(signage)上作为硬涂层使用。
美国专利No.6,132,861(Kang等，`861)，6,238,798B1(Kang等，`798)和6,245,833B1(Kang等，`833)及已公开的PCT申请WO99/57185(Huang等)中描述了含有无机氧化物胶体微粒、可固化粘结剂前体和某种氟化物的混合物的陶瓷体组合物。这些组合物以单层涂层的形式形成抗污、抗磨损的硬涂层。
PCT公开申请No.WO 00/24576(Janssen等)中提到了防涂写的透明板片层叠。整个板片层叠应用于玻璃或塑料窗户、信号装置或显示设备上，一旦最上层的板片破损可以将其移走。板片层叠中板片可以包含可任选的防粘层。该防粘层据说优选包含选自丙烯酸酯、甲基丙烯酸酯、聚氨酯、聚烯烃、硅树脂、氟化物例如碳氟化合物，及以上物质混合物的材料。在实施例7中，3M 906抗磨损涂层作为板片层叠中聚碳酸酯板片上的抗磨损防粘层使用。在美国专利No.5,002,326(Westfield等)和Offenlegungsschrift DE 36 37 188 A1(Altmann等)中提到了用于汽车窗上的可移除的塑料板片层叠。
美国专利No.5,851,674(Pellerite等)中描述了自组装的氟化硅烷膜，其可以应用于多层抗反射膜的顶层从而形成具有抗染污性的涂层。
美国专利No.6,204,350(Liu等)中描述了包括含有氟化聚合物的烷氧基硅烷的可固化涂层组合物。
发明概述
由3M 906抗磨损涂层制成的涂层容易形成污迹、着色和钢笔或铅笔痕迹。要将Kang等的`798和Kang等的`833组合物组分混合而不产生絮凝是很困难的。由于氟化物及其在硬涂层的应用的高昂的成本，这些组合物也相对昂贵。Pellerite等的薄膜对从3M 906抗磨损涂层等陶瓷体制备而来的薄膜的粘附力不够。
本发明一方面提供一种显示元件，其包含一基本上透明的基板，一包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和一在硬涂层之上包含全氟化聚醚的抗染污层。
本发明还为具有信息显示区的显示设备提供了信息显示器保护器，所述的保护器包括一基本上透明的一般为平面的挠性基板，在所述基板的一面具有粘合剂层，另一面上具有包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和在硬涂层之上包含全氟化聚醚的抗染污层。
本发明还提供了用于具有显示屏的便携式电子设备的信息显示器保护器，所述的保护器包括基本上透明的层叠挠性板片，所述板片在一面上具有粘合剂层，在另一面上具有包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和在硬涂层之上包含全氟化聚醚的抗染污层。对板片层叠进行切割从而使得板片能够适合所述显示屏。通过将所述层叠附着于显示器的一部分或附着于显示器盖，可以方便地存储所述层叠。
本发明还提供一抗染污性硬涂布薄膜，其包括一般为平面的挠性基板，所述基板在至少一面上具有包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和在硬涂层之上包含全氟化聚醚的抗染污层。
本发明还提供制备抗染污性硬涂层的方法，包括在基板上涂步包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的陶瓷体涂料并使之固化，和在陶瓷体涂层上涂步包含可经自由基聚合的氟化物的抗染污层并使之固化。
本发明还提供制备显示元件的方法，包括向基本上透明的基板上施加一包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的可固化硬涂层，使硬涂层固化，向硬涂层上施加包含全氟化聚醚的可固化抗染污层，并使抗染污层固化。
此外，本发明还提供用于具有信息显示区的设备的信息显示器保护器的方法，所述的方法包括：
a)向基本上透明、一般为平面的基板的一面上施加包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的可固化硬涂层，使该硬涂层固化，向硬涂层上施加包含全氟化聚醚的可固化抗染污层，并使该抗染污层固化；和
b)向所述基板的另一面上施加粘合剂层。
本发明还提供制备用于具有信息显示区的便携式电子设备的信息显示器保护器的方法，包括进行如上步骤a)和b)；使已涂覆的基板形成层叠板片；和改造所述层叠以使所述板片适合所述信息显示区。
本发明还提供连续的辊对辊(roll to roll)制造方法，用于制备信息显示器的糙化屏幕保护器板片，所述方法包括：
a)将基本上不含溶剂的可固化陶瓷体组合物沉积到基本上透明的基板与辊间的辊隙区中，所述陶瓷体组合物包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒，所述辊的平均表面粗糙度为至少0.1微米；
b)以足够的速度移动辊，同时向辊隙施加足够的压力，以在辊隙中形成陶瓷体组合物珠；
c)在陶瓷体组合物抵附在辊上的同时，(使用例如紫外照射)通过基板固化该陶瓷体组合物；
d)从辊上取下固化的陶瓷体涂层；
e)向固化的陶瓷体涂层上施加包含全氟化聚醚的可固化的抗染污层；和
f)使所述抗染污层固化。
所述抗染污层可以非常薄，从而降低全氟化聚醚的用量和成本。本发明的制品具有非常好的耐磨和耐脏性，以及非常好的耐久性。
附图简要描述
图1是含本发明显示元件的电容式触摸屏的简要侧视图。
图2是含本发明显示元件的电阻式触摸屏的简要侧视图。
图3是本发明的信息显示器保护器的简要侧视图。
图4是PDA的平面图，其屏幕已经被图3的信息显示器保护器所覆盖。
图5是本发明的屏幕保护器层叠的简要侧视图。
图6是PDA的透视图，其屏幕已经被图3的信息显示器保护器所覆盖，内前盖上附着有图5的保护器层叠。
图7是含本发明显示元件的可去除式计算机私密滤波器的简要侧视图。
图8是含本发明显示元件的扩展分辨率视屏的简要侧视图。
图9是用来评价抗墨性的等级图。
详细描述
本发明的显示元件和其组件在此有时使用表示取向的词例如“上部”，“顶上”，“上方”或“前面”等来表示或描述。使用这些以及类似的术语只是为了便于指代朝向显示设备的正常观察者的一般方位(相对于通过信息显示设备的光路而言)。同样地，在此使用表示取向的词例如“下方”，“在....之下”，“在.....下面”，或“在......后面”等来表示或描述本发明的的显示元件和其组件。使用这些以及类似的术语只是为了便于指代朝向显示设备的一般方位(相对于光路而言)。本领域技术人员应当理解，本发明的的显示元件可以多种取向和位置使用。
本发明的信息显示器保护器可用于多种具有不同信息显示区构造的信息显示器。这些显示器包括多字符显示器，尤其是多字符多行显示器，例如液晶显示器(“LCD”)，等离子体显示器，前投影和背投显示器，阴极射线管(“CRT”)和信号装置。本发明的信息显示器保护器也可用于单字符显示器或二进制显示器例如发光二极管(“LED”)，信号灯和开关。本发明的信息显示器保护器可用于发光或非发光显示器。本发明的信息显示器保护器尤其适用于信息显示区是观看屏形式的显示器，其观看屏上有一个在正常使用状态下易于损坏的观看表面。
本发明的显示器元件可以在很多便携式和非便携式信息显示器设备中使用，包括PDA、蜂窝电话(包括PDA/蜂窝电话的组合)、触摸屏、腕表、汽车导航系统、全球定位系统、深度计、计算器、电子图书、CD或DVD播放机、投影电视屏幕、计算机监视器、笔记本计算机显示器、计量器、仪表面板盖、信号装置例如图形显示器(包括室内和室外图形、缓冲器粘贴板等)，反射板等等。这些设备具有平面的观看面，或非平面的观看面，例如通常CRT的稍微弯曲表面。通常显示元件安装在信息显示设备的观看面之上或贴近于观看面，而不是放置在距之一定距离之外。
下面参照图1，其中以示意形式画出了一个电容式(capacitive)触摸面板显示器，一般标记为10。观看表面11使得观看者(图1中没有画出)可以从成象装置12看见图象。成象装置12可以是能够显示信息的多种装置类型的任何一种，包括透射式、反射式或透反式液晶显示器，阴极射线管，微反射镜阵列，和印刷面板或其他背景。一般为平面的基板13用于保护成象装置12并提供对观看表面11的支承。基板13通常由玻璃或塑料比如聚碳酸酯或聚对苯二甲酸乙二醇酯制成。基板13的上表面覆盖以透明的薄导电涂层14。涂层14通常由金属或合金比如铟锡氧化物制成，或者由导电聚合物制成。硬涂层16位于涂层14之上，用于提供对划痕和磨擦的防护以助于保护涂层14和其下的基板13免受损伤。硬涂层16具有糙化的上表面17。是否包含这种粗糙表面是可选择的。它对显示器10提供了眩光保护，并使得更容易用触针在显示器10上书写。抗染污层18足够薄，使得硬涂层16的糙化上表面17能复制在观看表面11上。抗染污层18具有抗油性和抗墨性，有助于使硬涂层16避免由于暴露于污染物比如皮肤油脂、化妆品、铅笔芯、墨水和偶然的污垢中而变脏或染污。若受到染污后，抗染污层18也可以使硬涂层的清洗变得容易。因此，如果有必要的话，使用者可以在偶然或有意的情况下用钢笔或铅笔在显示器上进行书写，然后轻而易举地除去铅笔或墨水造成的斑迹。本领域技术人员应当理解，一般位于显示器10角部的电极(图1中未画出)用于对用作电容器的导电涂层14施加电压和充电。电荷被泄漏并补充，同时控制器(图1中同样没有画出)对从各电极流出的电流量进行测量。导电触针或手指与观看表面11的接触提高了导电涂层14的电容，从而当发生触摸时有更多的电流流过。通过比较从各电极流过的电流来确定触摸位置。
尽管在图1中没有画出，可以在硬涂层之上或者抗染污层之上施加一个任选的抗静电涂层，以防止灰尘和其他污染物附着在显示器上。而且，可以任选地在基板13的下表面上形成另外一层硬涂层16。这有助于保护基板13免受损伤并且有助于降低显示器10的眩光和重影。
图2表示一个电阻式(resistive)触摸面板显示器，一般标记为20。观看表面21使得观看者(图2中没有画出)可以从成象装置12看见图象。显示器10的基板22位于成象装置12之上，通常由玻璃或塑料比如聚碳酸酯或聚对苯二甲酸乙二醇酯制成。基板22的上表面覆盖有一薄层任选的硬涂层24a，该硬涂层24a用作透明的薄导电性涂层25a的底涂层和粘合助剂。类似的薄导电性涂层25b经任选的硬涂层24b附着于挠性薄膜23。挠性薄膜23的上表面涂布了硬涂层26。硬涂层26提供对划痕和磨擦的防护以助于保护挠性薄膜23免受损伤。硬涂层26具有任选的糙化上表面，如图1显示器中的。抗染污层28足够薄，使得硬涂层26的糙化上表面27能复制在观看表面21上。抗染污层28具有抗油性和抗墨性，有助于使硬涂层26避免变脏或染污。如果需要，也可提供任选的抗静电层，如图1显示器中的。隔片29位于涂层25a之上，正常地使涂层25a上表面和涂层25b下表面间隔限定的距离。本领域技术人员将会理解，手指或触针与观看表面21的接触导致薄膜23弯曲并使涂层25b与涂层25a接触，从而使得电流在这些层间流过。控制器(没有在图2中示出)可通过比较来自印制在导电层25a和25b上的不同电极或母线(没有在图2中示出)的电流，识别接触位点。
本领域技术人员将会理解，可在本发明中使用其他类型的触敏装置。例如，触敏装置可经由循导声波、表面声波或近场成象来工作。触敏装置还可经由非接触机制来工作，如经由扫描红外传感器，例如经由合适的光束阵的构造，以及位于显示器上表面的光传感器。
图3显示了本发明的信息显示器保护器，通常标志为30。挠性薄膜33的下表面涂有一层粘合剂34，其上施加有保护性衬片32。粘合剂34的下表面具有微观纹理。具有微观纹理的粘合剂层的使用是可选择的。当使用于显示屏时，微观纹理可以使气泡从保护器30的下方逸出，从而在保护器30和屏幕间产生很好的光耦合。薄膜33的上表面涂布了硬涂层36。硬涂层36具有任选的粗糙上表面37，从而对显示屏提供了眩光保护。抗染污层38足够薄以致硬涂层36的粗糙上表面37能复制在保护器30的观看面31上。如果需要，也可以提供抗静电层。
图4显示了一个PDA，通常标明为40，在其上使用了图3所示的信息显示器保护器30。使用者简单地将粘合剂34上的衬片32撕掉，将保护器30置于屏幕42的中央，然后通过按压使保护器30贴紧。保护器30用做PDA屏幕的屏幕保护器，优选将其预切至稍小的尺寸使得保护器30的边缘几乎延伸至屏幕42的周界，但仍然能够在需要时容易地将保护器30去除。糙化的观看面31降低了眩光，并使在屏幕42上的书写变得更加容易，尤其当使用书写笔的时候。抗染污层38(未在图4中显示)具有抗油污和抗油墨特性，有助于使保护器30中硬涂层36(也未在图4中显示)避免变脏或受染污。这一点在当使用者无意中使用钢笔或铅笔而不是书写笔在屏幕42上进行书写的时候尤其有用。
图5显示了一叠50四个如图3所示类型的PDA信息显示器保护器。该层叠50具有一个衬片32，起着保护最下层信息显示器保护器的粘合剂层34a的作用。其余的信息显示器保护器可以分别通过将粘合剂层34b、34c和34d压在抗染污层38a、38b和38c上而互相粘附。使用者可以将最上层的保护器从层叠中撕下并将其粘附在PDA屏幕上，如图4所示。如果如此施加的保护器以后变旧或破损，则可以从PDA屏幕上撕下并用层叠50中另一保护器替代。
使用者可以将层叠粘附到显示设备或其盒子或盖子上对其进行储存。图6显示了一个PDA，通常标为60。将保护器30(在基板33上)从层叠50的顶层撕下并施加在PDA 60的屏幕42上。衬片32已经从层叠50撕下，从而层叠50能够粘附在PDA前盖62的内表面64上。尽管没有在图6中显示，但是层叠可以粘附在PDA 60的后部或单独的PDA盒子的任何可用表面上。如果层叠50含有较低数目的保护器(例如，10个以下，更优选5个以下)，它将不会使前盖上印刷的图形(例如一些PDA上提供的印刷GRAFFITITM字母符号指引)变得过分模糊，并且粘附在内表面时不会影响PDA盖子或盒子的关闭。由于层叠50可以储存在PDA上，因此当需要的时候备用的保护器30随手可得。这是比当今以单片形式出售的PDA屏幕保护器产品的通常储存方式更方便的储存方式。当屏幕42上的保护器30变旧或破损时，可以从层叠50上撕下新的保护器。例如，如图6所示，可以通过将粘合剂层34c从抗染污层38b剥除而撕下层叠50中的下一个保护器。
图7显示可去除式计算机私密滤波器，通常标明为70。百叶窗式光控制薄膜72使得观看者能经观看表面71看到来自下方成象装置12的图象，同时防止远离主观看轴的观察者看到这些图象。基板层74经粘合剂层73附着于光控制薄膜72的上下表面。硬涂层75和77有助于保护基板层74和薄膜72，避免其受到损伤，抗染污层76和78提供抗油性和抗墨性，有助于避免硬涂层75和77受染污。硬涂层77和其抗染污层78优选进行糙化，以减少眩光。由于滤波器70经常从显示器移除和重置到显示器上，在滤波器的两个主表面上均使用硬涂层和抗染污层有助于搬运和清洁，即便使用者偶然地握持滤波器的前后面而不是抓住其边缘进行搬运。如果需要，可在滤波器的两主表面或其中一面之上或紧挨下方采用任选的抗静电涂层(没有在图7中示出)。
图8显示扩展分辨率视屏，通常标明为80。在丙烯酸类屏幕82的后表面上覆盖有聚乙烯醇缩丁醛的热塑层83，该热塑层已被热层压到小玻璃珠单层85上，该小玻璃珠单层85被粘结到增强对比度的含碳黑的氨基甲酸酯珠粘合层84中。基板87经粘合剂层86附着于屏幕82的上表面。基板87也可热层压到屏幕82的上表面。硬涂层88有助于保护基板87和屏幕82，避免其受到损伤，抗染污层89提供抗油性和抗墨性，有助于避免硬涂层88受染污。硬涂层88和抗染污层89优选进行糙化，以减少屏幕80的观看表面81上的眩光。如果需要，也可在观看表面81上或紧挨下方采用任选的抗静电涂层(没有在图8中示出)。
很多种基板材料可以在本发明中使用。基板应该是基本上透明的，也就是，基板在预期的波长和在预期的观看条件下应该具有足够的透明度或半透明度，因此显示元件不会阻止应用或观看下边的信息显示。合适的基板材料包括玻璃，透明或半透明陶瓷，以及热固性和热塑性聚合物，例如聚碳酸酯、聚(甲基)丙烯酸酯(例如，聚甲基丙烯酸甲酯或“PMMA”)、聚烯烃(例如，聚丙烯或“PP”)、聚氨酯、聚酯(例如，聚对苯二甲酸乙二醇酯或“PET”)、聚酰胺、聚酰亚胺、酚醛树脂、纤维素二乙酸酯、纤维素三乙酸酯、聚苯乙烯、苯乙烯-丙烯腈共聚物、环氧树脂等。通常部分按照预期使用中要达到的光学和机械性能选择基板。这些机械性能通常包括刚性、尺寸稳定性和耐冲击性。基板的厚度通常也取决于预期的用途。在大多数的应用中，优选基板的厚度小于约1mm，更优选小于约0.1mm，最优选在约0.02mm至约0.2mm之间。基板可以是挠性或刚性的。优选自承性聚合物膜形式的挠性基板。特别优选从聚酯例如PET，或聚烯烃例如PP(聚丙烯)、PE(聚乙烯)和PVC(聚氯乙烯)等制备而来的挠性膜。采用常规制膜技术例如将基板树脂挤压成膜，和可任选的对挤出膜单轴或双轴取向，而将基板制成膜。对基板进行处理以改善基板和硬涂层之间的粘合力，可以采用例如，化学处理方法、电晕处理方法例如空气或氮气电晕、等离子体、火焰或光化学辐射法。若需要的话，可在基板和硬涂层之间使用可任选的粘结层以增加层间粘附力。基板的另一面可使用上述处理方法进行处理，以改善基板和粘合剂之间的粘附力。
硬涂层是坚韧的抗磨损层，其可以保护基板和下方的信息显示器，使之避免由于刻划、磨损和溶剂的原因而造成的损害。优选硬涂层含有分散在粘结剂基质中的纳米尺寸的无机氧化物微粒。通常通过将可固化液体陶瓷体组合物涂布在基板上形成硬涂层，在原位固化组合物形成硬化膜。合适的涂布方法包括，例如，旋转涂布、刮刀涂布、口模式涂布、线材涂布、溢流涂布、填料、喷雾、辊涂、浸涂、刷涂、泡沫应用等。
很多的无机氧化物微粒可用于硬涂层中。优选微粒的形状基本为球形，尺寸相对统一。微粒可以是具有基本上为单分散尺寸的分布或通过将两种或多种基本上单分散分布混合而获得的多样式分布。由于聚集会导致无机氧化物微粒的沉淀或硬涂层的凝胶化，因此优选无机氧化物微粒是并且保持基本非聚集状态(基本上是离散的)。优选无机氧化物微粒的大小是胶体尺寸，即，优选具有平均微粒直径从约0.001至约0.2微米之间，更优选小于约0.05微米，最优选小于约0.03微米。这些尺寸范围促进了无机氧化物微粒在粘结剂树脂中的分散，并且使陶瓷体具有理想的表面性能和光清晰度。可以通过使用电子透射显微镜法计数给定直径的无机氧化物微粒来测量无机氧化物微粒的平均微粒大小。优选的无机氧化物微粒包括胶态氧化硅、胶态氧化钛、胶态氧化铝、胶态氧化锆、胶态氧化钒(vanadia)、胶态氧化铬(chromia)、胶态氧化铁、胶态氧化锑、胶态氧化锡及其混合物。无机氧化物微粒可以由或基本上由单一氧化物例如氧化硅组成，或可以包含几种氧化物的组合，例如氧化硅和氧化铝，或核心是一种类型的氧化物(或核心为除了金属氧化物以外的材料)且在其上沉积了另一类型的氧化物。氧化硅是特别优选的无机微粒。无机氧化物微粒的理想形式是在液体媒介中含有无机氧化物微粒胶体分散体的溶胶。该溶胶可以通过多种技术制备，并以多种形式存在，包括水溶胶(其中水作为液体媒介)，有机溶胶(其中有机液体起同样作用)，和混合溶胶(其中的液体媒介同时包括水和有机液体)，例如，如美国专利No.5,648,407(Goetz等)和5,677,050(Bilkadi等)所述，其内容引入本文作为参考。特别优选无定型氧化硅水溶胶。优选的溶胶通常包含基于整个溶胶重量的从约2至约50重量％，优选从约25至约45重量％的胶态无机氧化物微粒。优选的溶胶可以从供应商得到，例如ONDEO Nalco Co.(例如，NALCOTM 1040，1042，1050，1060，2327和2329胶态氧化硅)，Nyacol Nano Technologies，Inc.(例如，NYACOLTM AL20胶态氧化铝和NYACOLTM A1530，A1540N和A1550胶态五氧化二锑)，和W.R.Grace and Co.(例如，LUDOXTM胶态氧化硅)。正如Bilkadi等描述那样，可以对无机微粒表面进行“丙烯酸酯官能化”。溶胶的pH值可以与粘结剂的pH相匹配，并可以含有抗衡离子或水溶性化合物(例如，铝酸钠)，正如Kang等、798所描述的那样。
硬涂层可以通过将无机氧化物微粒的水溶胶与可经自由基固化的粘结剂前体(例如，在暴露于合适的固化能量源时发生的交联反应中会沉淀的一个或多个可经自由基固化的单体、寡聚物或聚合物)混合而方便地制备。为了基本上地除去所有的水，在使用前，得到的组合物通常要进行干燥。此干燥步骤有时称为“反萃取”。为了增强粘性并有助于陶瓷体组合物对基板的涂布，在使用前通常向得到的陶瓷体组合物中加入有机溶剂。涂布后，干燥陶瓷体组合物以除去任何加入的溶剂，然后为了使可经自由基固化的粘结剂前体至少部分固化，通过将干燥的组合物暴露在合适的能量源下使陶瓷体组合物至少部分硬化。
优选硬涂层中每一百份按重量计的粘结剂含有约10至约50，更优选约25至约40份按重量计的无机氧化物微粒。更优选硬涂层从含有约15至约40％丙烯酸酯官能化的胶态氧化硅而来，最优选约15至约35％丙烯酸酯官能化胶态氧化硅。
硬涂层中可以使用多种粘结剂。优选粘结剂从可经自由基聚合的前体衍生而来，所述的可聚合前体在硬涂层组合物涂布在基板上后可光致固化。尤其优选Bilkadi描述的质子基团取代的丙烯酸酯或酰胺或Bilkadi等描述的烯键式不饱和单体等粘结剂前体。合适的粘结剂前体包括多元醇的多丙烯酸或多甲基丙烯酸酯，例如二醇的二丙烯酸或二(甲基丙烯酸)酯，二醇包括1，2-亚乙基二醇、二缩三(乙二醇)、2，2-二甲基-1，3-丙二醇、1，3-环戊二醇、1-乙氧基-2，3-丙二醇、2-甲基-2，4-戊二醇、1，4-环己二醇、1，6-己二醇、1，2-环己二醇、1，6-环己二甲醇、间苯二酚、邻苯二酚、双酚A和邻苯二甲酸双(2-羟乙基)酯；三元醇的三丙烯酸酯或三(甲基丙烯酸)酯，三元醇包括丙三醇、1，2，3-丙烷三甲醇、1，2，4-丁三醇、1，2，5-戊三醇、1，3，6-己三醇、1，5，10-癸三醇、焦棓酚、间苯三酚和2-苯基-2，2-羟甲基乙醇；四元醇的四丙烯酸酯或四(甲基丙烯酸)酯，四元醇包括1，2，3，4-丁四醇、1，1，2，2-四羟甲基乙烷、1，1，3，3-四羟甲基丙烷，以及季戊四醇四丙烯酸酯；五元醇的五丙烯酸酯或五(甲基丙烯酸)酯，五元醇包括核糖醇；六元醇的六丙烯酸或六(甲基丙烯酸)酯，六元醇包括山梨醇、一缩二(季戊四醇)、二羟基乙基乙内酰脲；以及它们的混合物。粘结剂还可以从Kang等`798所述的一个或多个单官能单体而来。优选粘结剂包含Bilkadi等所述的一种或多种N，N-二取代丙烯酰胺和或N-取代-N-乙烯基-酰胺单体。更优选硬涂层从含有按陶瓷体组合物中固体总重量计的约20至约80％的烯键式不饱和单体和约5至约40％N，N-二取代丙烯酰胺单体或N-取代-N-乙烯基-酰胺单体的陶瓷体组合物制备而来。
优选所选择的硬涂层中的无机微粒、粘结剂和其他组分能够使固化的硬涂层具有接近基板的折射率。这有助于减少可能的Moiré模式或其他的可见干涉带。
正如以上提到的，硬涂层可以从含水涂层组合物制备得到，所述组合物在进行涂布前通过反萃取除水并任选以溶剂稀释帮助涂布。本领域技术人员将会认识到所需溶剂和溶剂量的选择将取决于硬涂层(或粘结层)中各个组分的性质及所希望的基板和涂布条件。Kang等`798描述了几种有用的溶剂、溶剂量和涂料粘性。
硬涂层可以与不同的试剂交联以增强内聚强度或硬涂层的耐久性。优选的交联试剂具有相对多的可用官能团，并包括三和四丙烯酸酯，例如季戊四醇三丙烯酸酯和季戊四醇四丙烯酸酯。当使用的时候，优选交联试剂的用量按每100份粘结剂重量计为小于约60重量份，更优选为按重量计约30至约50份。
本领域技术人员还将会认识到硬涂层可以包含其他可任选的辅助试剂，例如表面处理试剂、表面活性剂、抗静电试剂(例如导电聚合物)、均化剂、引发剂(例如光引发剂)、光敏剂、UV吸收剂、稳定剂、抗氧化剂、填充料、润滑剂、颜料、染料、增塑剂、悬浮剂等。Kang等`798中对这些辅助试剂进行了详尽的讨论，并推荐了使用量。
如果通过将胶态无机氧化物微粒水溶液与粘结剂前体混合制备硬涂层，那么优选溶胶的pH使微粒具有带负电的表面电荷。例如，如果无机微粒主要是氧化硅微粒的话，优选溶胶的pH为大于7的碱性，更优选大于8，最优选大于9。优选溶胶含有氢氧化铵或类似物，从而NH4 +可以作为含负表面电荷微粒的抗衡阳离子。如果想对胶态无机氧化物微粒进行表面处理的话，那么可以将适当的表面处理试剂混入溶胶中，例如，正如Kang等`833所描述的，在此通过引用并入该文献的公开内容。然后将可经自由基固化的粘结剂前体加入陶瓷体组合物。将陶瓷体组合物进行反萃取除去基本上所有的水分。例如，除去约98％的水分，在陶瓷体组合剩余约2％的水分，这是合适的。当所有水分基本上都被除去后，优选加入如Kang等`798所述类型的有机溶剂，加入量为使陶瓷体组合物含有按重量计从约5％至约99％的固体(优选从约10至约70％)。在加入溶剂后，可以加入其他想加的辅助试剂。
优选陶瓷体组合物在涂料重量足以使固化硬涂层的厚度为从约1至约100微米的条件下进行涂布，更优选从约2至约50微米，最优选从约3至约30微米。涂布后，若有溶剂的话，使用热和/或真空等方式将其除去。然后使用适当的能量形式，例如热能、可见光、紫外光或电子束照射等通过照射的方式固化所涂布的陶瓷体组合物。由于相对低的成本和固化技术的速度原因，当前优选采用在环境条件下的紫外光照射的方式。另外，可以任选性地对硬涂层表面进行粗糙或纹理化处理以形成无光泽表面。可以采用多种本领域技术人员所熟悉的方式完成，包括使用合适的已充珠或粗糙化的工具对硬涂层进行压纹，所述充珠或粗糙化通过如下方式进行：向硬涂层加入石英砂或玻璃珠等适当的小微粒填充料，或针对合适的糙化母件进行固化，如美国专利No.5,175,030(Lu等)和5,183,597(Lu)所述。
抗染污层包含全氟化聚醚。优选的全氟化聚醚中含有随机分布的全氟化烯化氧-(CnF2nO)-重复单元例如为-CF2O-或-[(CF2)n-CF2-m(CF3)mO]-(其中m是0或1，n优选为1至7)，侧基(例如，端基)可聚合(例如，丙烯酸酯或甲基丙烯酸酯)基团。合适的全氟化聚醚包括那些在美国专利No.3,810,874(Mitsch等)，4,321,404(Williams等)，4,472,480(Olson)，4,567,073(Larson等‘073)，4,830,910(Larson等‘910)和5,306,758(Pellerite)所述的，在此通过引用这些文献并入其公开内容。一小类优选的抗染污层从下式的全氟化聚醚衍生而来：
       Y-(CaF2aO)bCaF2a-Y       (I)
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量从约500至约20,000。
另一小类优选的抗染污层从下式代表的全氟化聚醚衍生来：
Zc-A-(CF2O)e(CF2CF2-m(CF3)mO)fCF2-A-Zd(II)
式中每个Z是丙烯酸酯或甲基丙烯酸酯基团；m是0或1；c和d为0至3，条件是c+d至少为2；当M是0的时候，e和f比5大；当m是1时，e可以是0，f比5大；每个A是c+1或d+1价连接基，例如，优选的连接基A包括：
          -OCH2-
        -OCH2CH2NHCO-
       -OCH2CH2CH2NHCO-
Figure A0181379700251
等。
另一小类优选的抗染污层从下式代表的全氟化聚醚衍生而来：
   Y-(CF2O)g(CF2CF2O)hCF2-Y  (III)
式中每个Y与上述的定义一样，g和h大于5。此类Y为丙烯酸酯基团的全氟化聚醚可从下式代表的全氟化聚醚二酯转化而来：CH3OOC(CF2O)g(CF2CF2O)hCF2COOCH3  (IV)所述二酯可以从Ausimont USA以FOMBLINTM二酯形式购买到。
更优选一小类的抗染污层从下式代表的全氟化聚醚衍生来：
         Y-(CF2CFCF3O)gCFCF3-Y       (VI)
式中每个Y和g与上述的定义一样。此类Y为丙烯酸酯基团的全氟化聚醚可从下式代表的全氟化聚醚二酯转化而来：
      CH3OOC(CF2CFCF3O)gCFCF3COOCH3  (VI)所述二酯可以从E.I.du Pont de Nemours Co.以KRYTOXTM二酯形式购买到。
尤其优选的全氟化聚醚包括：(C2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2，(C2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3，F(CF(CF3)CF2O)25CF2CF3，C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9，CH2＝CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH＝CH2，CH2＝CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH＝CH2，(HOCH2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2，(C2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3，(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)2，(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)2，(C2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)3，(C2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2，和
Figure A0181379700261
如果需要，抗染污层可含其他可相容的氟化物，例如与全氟化聚醚掺合的全氟化表面活性剂、丙烯酸全氟化烷基酯和甲基丙烯酸全氟化烷基酯。如果需要，也可在抗染污层中加入其他辅助试剂，例如可溶的或可互混的光引发剂。
优选利用有助于全氟化聚醚涂布到硬涂层上的溶剂施加全氟化聚醚。本领域技术人员将会理解所需溶剂和溶剂量的选择依赖于硬涂层中组分和抗染污层的性质以及所希望的涂布条件。在推荐的溶解水平为或高于20％固体的条件下，优选的溶剂包括氟化溶剂，例如氢氟代醚(hydrofluoroether)和全氟化辛烷(尤其当全氟化聚醚在其骨架上不包含极性连接基的时候)，和烃类溶剂，例如甲基·乙基酮和乙酸乙酯。在加入溶剂后，可以加入任何其他所需的辅助试剂。
可以采用多种常规的涂布方法，包括以上提到的方法，将全氟化聚醚施加于硬涂层。优选凹槽辊涂布、凹口试杆涂布、逆转辊涂布和幕涂。由于凹口试杆涂布和凹槽辊涂布能够在非常薄层厚度，在约1至约5微米湿厚度下应用，因此是特别优选的方法。优选抗染污层以涂料重量足以使固化抗染污层的厚度在约0.005至约2微米进行涂覆，所述厚度更优选约0.01至约0.1微米，最优选约0.02至0.08微米。对湿涂料进行干燥，通常采用强迫通风热空气箱。干燥的涂料可以使用能量源进一步固化(至部分或完全固化的状态)。优选的能量源包括能够提供约5至60毫焦耳/平方厘米(mJ/cm2)UV“C”剂量的紫外灯固化设备。优选在包含少量氧气，例如，小于约100份/百万份的环境中进行固化。氮气是优选的环境。
显示元件可任选在基板的背面包括粘合剂。优选粘合剂是透明的或足够透明，从而不会影响观看下方的显示设备。粘合剂可以是从自然产品(例如，橡胶基粘合剂)而来，或者是合成材料，例如均聚物、无规共聚物、接枝共聚物、或嵌段共聚物。粘合剂可以是交联或未交联的，若需要的话，可以具有压敏性。Dahlquist标准给出了可接受的压敏粘合剂(PSA)的定量描述，该标准表明储能模量(G’)小于约3×105帕斯卡(在室温，约22℃至22℃，10弧度/秒下测量)的材料具有压敏性，然而G’超过此数值的材料则没有压敏性。优选非压敏性的粘合剂，尤其那些具有选择性粘附力的粘合剂，例如，对于皮肤低附着力或无粘性，但是对于目标表面例如显示器的表面具有高粘性的粘合剂。显示设备元件上涂布上这样的非压敏性的粘合剂后很容易处理并应用到显示器表面，而且需要的时候可以清除干净。美国专利No.5,389,438(Miller等)，5,851,664(Bennett等)，6,004,670(Kobe等)和6,099,682(Krampe等)中描述了适用的低附着力或无粘性的粘合剂。尤其优选热塑性嵌段共聚物弹性体(嵌段A和B嵌段或片段的共聚物，其同时表现出热塑性和弹性)。可用的热塑性嵌段共聚物弹性体包括多嵌段共聚物，其具有放射状、线形A-B二嵌段、和线形A-B-A三嵌段结构，也包括这些共聚物的混合物。可购买到的适用的热塑性嵌段共聚物弹性体包括SOLPRENETM类材料(Philips PetroleumCo.)，FINAPRENETM类材料(FINA)，TUFPRENETM和ASAPRENETM类材料(Asahi)，STEREONTM类材料(Firestone Synthetic Rubber & LatexCo)，EUROPRENE SOL TTM类材料(Enichem)，VECTORTM类材料(Dexco Polymers)和CARIFLEX TRTM类材料(Shell Chemical Co)。其他适用的粘合剂材料包括高度交联的丙烯酸类粘合剂、如美国专利No.5,670,598(Leir等)所述的硅氧烷聚脲弹性体、SEPTONTM类材料(Kuraray Co.Ltd.)和KRATONTM类材料(Shell Chemical Co.)所描述的如KRATON D-1101，D-1102，D-1107，D-1111，D-1112，D-1113，D-1114PX，D-1116，D-1117，D-1118，D-1119，D-1122X，D-1124，D-1125PX，D-1160，D-1165，D-1161，D-1184，D-1193，D-1300，D-1320X，D-4141，D-4158，D-4433，RP-6485，RP-6409，RP-6614，RP-6906，RP-6912，G-1650，G-1651，G-1652，G-1654，G-1657，G-1701，G-1702，G-1726，G-1730，G-1750，G-1765，G-1780，FG-1901，FG-1921，FG-1924，和TKG-101.。也可以使用粘合剂材料的混合物。
可任选性地对粘合剂(或保护粘合剂使其免受污染并挤压粘合剂的衬片)进行微观纹理处理以使其提供排气和易于处理的特性(正如美国专利No.6,197,397描述的)。通常单板片的粘合剂层或板片层叠的最下层会附有衬片。如果粘合剂是粘性粘合剂，那么优选衬片面向粘合剂的一面有防粘涂料，例如硅树脂防粘涂料。如果粘合剂为低附着力或无粘性，那么由平纹纸或其他低表面能材料制成的衬片就足够了，不需要防粘涂料。
可以调整板片的大小(使用本领域技术人员熟悉的技术)以便使之能适合目标信息显示器设备的显示区。可用的技术包括冲切、纵切和激光切割。
以下将利用实施例对本发明进一步进行描述。除非另外注明，所有的份数和百分比都是按重量计的。采用了下列测评方法：抗墨性
使用黑色的SHARPIETM细尖永久记号笔(Sanford Corp.)，从未涂覆抗染污层的区域向涂覆了抗染污层的区域画一条接近3cm长的细线。使用如图9所示的等级表，按照所得线的外观相应地标记从0(完全可润湿的)至6(完全不可润湿的)的数值。越高的数值代表越优越的抗染污性。铅笔硬度
将一系列硬度值从6B-1B、HB、F到1H-9H逐渐增加的铅笔以1kg的负载附着在一手持辊压测试台上，并且，对于每一个测试的铅笔硬度使之滚动穿过已涂布基板3或5次基板。根据对涂层不产生划痕或凹陷的最高铅笔硬度对涂层进行评级。当采用3次穿行时，根据3次中最高的2次进行指定分级；当采用5次穿行时，根据5次中最高的3次进行指定分级。因而，铅笔硬度值越高表示膜硬度越好。理想的涂层等级应该优于3H级。耐久性
将包裹有干粗平布的2Kg砝码或包裹有0000级钢丝绒的200g砝码在涂布后的基板上来回摩擦几次。定时性地停止摩擦并用上述的SHARPIN记号笔在摩擦过的表面上书写。以墨水起珠并能用干软棉纸擦掉而不留下墨迹的最大擦写循环数来确定耐久性等级。对于一些能经历非常高数值摩擦循环的涂层来说，在多次摩擦之后(例如200次)停止摩擦，耐久性等级注明为比测试停止时的摩擦数值大。理想的等级应该是粗平布耐久性级别优于40次摩擦循环，钢丝绒耐久性级别优于60次摩擦循环。带粘附性
根据ASTM D3359-97测试法，通过用尖刀对涂层刻划交叉排线，以及应用并取出经交叉刻划排线的带状剥离条，评估涂料层对基板的粘附力。使用所述测试法中给出的5分制级别评价所取出的涂料量。根据ASTM D-3330测试法，使用IMASSTM SP-2000型剥离测试仪，在2.3m/分剥离速率下工作(方法A，180°剥离)，评估剥离粘附性。光学性质
使用MPC 3100分光光度计(Shimadzu Scientific Instruments)测评反射性。膜样品粘附到背部用黑带敷盖的载玻片上。测量总的反射和第一表面反射并记录为入射照明百分比。使用HAZE-GARD PLUSTM测试仪(Byk Gardner，Inc.)测评平均可见光透射率、浊度和透明度。使用MICRO-TRI-GLOSSTM仪表(Byk Gardner，Inc.)在20、60或85度下测评光泽度。
实施例1-24
如下制备陶瓷体组合物，首先在反应器里将51.5份可固化的粘结剂前体PETA(季戊四醇三丙烯酸酯)加热至接近49℃。向PETA中加入88份NALCOTM 2327胶态氧化硅溶胶(40％固体，平均微粒尺寸为20纳米的氧化硅溶胶，Nalco Corp.)。得到的混合物中含有32.4份胶态氧化硅微粒。15.6份DMA(N，N-二甲基丙烯酰胺)随后加入混合物中。0.15份BHT(丁基化的羟基甲苯)与0.02份吩噻嗪混合后加入前述混合物中。将混合物置于温和的真空蒸馏(在100±20mm汞柱和52±2℃下)进行“反萃取”直到除去大部分液体。少量水分残留在经干燥的产品中。得到的干燥陶瓷体前体用14/1异丙醇/蒸馏水混合物稀释至固体量为50％，然后使用相同的醇/水混合液稀释至固体量为25％。向稀释后的产品中加入0.7份IRGACURETM184光引发剂(Ciba Specialty Chemicals)得到可光致固化的陶瓷体组合物。
使用迈耶棒(Meyer Rod)或者凹槽辊将陶瓷体组合物涂布到0.04mm PET膜上，组合物的涂布量足以使干燥后的涂层厚度达到约3至约5微米。湿涂层在70℃下进行干燥，并使用UV H灯在能量密度为10-60mJ/cm2 UVC和氮气吹扫下进行固化。
将一系列全氟化聚醚溶解在不同量的HFE-7100TM C4F9OCH3氢氟代醚溶剂(3M)中，然后利用迈耶棒将得到的溶液涂布到固化后的硬涂层样品上，涂布量足以使干燥后的涂层厚度达到约0.03至约0.2微米，这样就把抗染污层敷在了固化的硬涂层上。湿涂层在70℃下进行干燥，并使用UV H灯在能量密度为5mJ/cm2 UVC和氮气吹扫下进行固化。
制备了三个对照组合物和24个制剂进行测评。下表1列出了每个对照样或实施例的硬涂层涂布方法；全氟化聚醚、光引发剂(若有)和辅助试剂(若有)的名称；及使用的HFE溶剂的量。下表2列出了观察到的抗墨性、铅笔硬度、耐久性结果及涂布的对照样和实施例的外观评价。词条“ND”表示没有测量的数值。
                  表1对照或实施例    陶瓷体    全氟化聚醚        PFPE中光        PFPE中辅助   溶剂份数
            涂布方法  (PFPE)份数        引发剂份数      试剂份数对照1           无        无(普通PET)       凹槽辊    无对照2(仅陶瓷体)对照3           无        0.1 PFPE-A1      0.0015 R20748               20 HFE14(无陶瓷体)
l           迈耶棒    0.1 PFPE-A        0.0015 R2074                 20 HFE
2           迈耶棒    0.1 PFPE-A        0.0015 R2074                 40 HFE
3           迈耶棒    0.1 PFPE-B2      0.0015 R2074                 40 HFE
4           迈耶棒    0.1 PFPE-A        0.0015 R2074    0.01 A17412 40 HFE
5           迈耶棒    0.1 PFPE-AJ       0.0015 R2074                 40 HFE
                      0.01 PFPE-C3
6           迈耶棒    0.1 PFPE-A/       0.0015 R2074                 40 HFE
                      0.01 PFPE-D4
7           凹槽辊    0.1 PFPE-A/       0.0015 R2074/                40 HFE
                      0.1 PFPE-E5      0.004 DEAP9
8           凹槽辊    0.1 PFPE-F6                                   20 HFE
9           凹槽辊    0.1 PFPE-F                                     40 HFElO           凹槽辊    0.1 PFPE-F        0.004 D-117310              40 HFE11           凹槽辊    0.1 PFPE-E        0.004 I-18411               40 HFE12           凹槽辊    0.1 PFPE-E        0.004 I-184                  20 HFE13           凹槽辊    0.1 PFPE-E        0.004 I-184                  80 HFE14           凹槽辊    0.1 PFPE-E        0.004 D-1173                 40 HFE15           凹槽辊    0.1 PFPE-E        0.004 D-1173                 20 HFE对照或实施例    陶瓷体    全氟化聚醚    PFPE中光         PFPE中辅助       溶剂份数
            涂布方法  (PFPE)份数    引发剂份数       试剂份数
16          凹槽辊    0.1 PFPE-E    0.004 D-1173                       80 HFE
17          凹槽辊    0.1 PFPE-E    0.004 D-1173                       160 HFE
18          凹槽辊    0.1 PFPE-E    0.004 D-1173                       1600 HFE
19          凹槽辊    0.1 PFPE-E    0.004 D-1173     0.04 A174         40 HFE
20          凹槽辊    0.1 PFPE-E    0.004 D-1173     0.05 K1514        40 HFE
21          凹槽辊    0.1 PFPE-E/   0.004 D-1173                       40 HFE
                      0.05 PFPE-D
22          凹槽辊    0.1 PFPE-E/   0.004 D-1173                       40 HFE
                      0.05 PFPE-A
23          凹槽辊    0.1 PFPE-E/   0.004 D-1173                       40 HFE
                      0.05 PEPE-G6
24          凹槽辊    0.1 PFPE-H7    0.004 D-1173                     40 HFE注释：1.PFPE-A是(C2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2.2.PFPE-B是(C2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3.3.PFPE-C是KRYTOXTM 1514全氟代醚流体F(CF(CF3)CF2O)25CF2CF3(E.I.DuPont de Nemours & Co.).4.PFPE-D是C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9.5.PFPE-E是CH2=CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH＝CH2.6.PFPE-F是CH2＝CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH＝CH2.7.PFPE-G是(HOCH2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2.8.PFPE-H是：
Figure A0181379700341
9.R2074是RHODORSILTM2074二芳基碘鎓四(五氟代苯基硼酸盐)，获自Rodia.10.DEAP是2，2-二乙氧基乙酰苯11.D-1173是DAROCURETM 1173 2-羟基-2-甲基-1-苯基-丙-1-酮，获自Ciba Specialty Chemicals.12.I-184是IRGACURETM184 1-羟基环己基·苯基酮(Ciba Specialty Chemicals).13.A-174是A-174γ-甲基丙烯酰氧基丙基三甲氧基硅烷(Union Carbide Corp.).14.HFE是HFE-7100TM C4F9OCH3氢氟代醚溶剂(3M).
                         表2实施例      抗墨性   硬度    透明度     耐久性，    耐久性，
                                    粗平布      钢丝绒对照A       无       HB      透明       无          无对照B       无       N       透明       无          无对照C       4        ND      透明       无          无1         5        ND      透明       2           72         5        ND      透明       5           123         5        ND      透明       6           144         4        ND      透明       60          1005         5        ND      透明       15          406         4        ND      透明       10          307         4        ND      稍混浊     15          608         5      ＞3H      透明       250         14009         5      ＞3H      透明       200         60010        2        ND      混浊       ND          ND11        5        ND      透明       300         45012        5        ND      透明       200         30013        5        ND      透明       300         45014        5      ＞3H      透明       250         50015        5        ND      透明     ＞100       ＞50016        5        ND      透明       250         50017        4        ND      透明       100         35018        1        ND      透明       ND          ND19        4        ND      透明       250         80020        4        ND      稍混浊   ＞100       ＞30021        5        ND      透明     ＞100       ＞60022        4        ND      稍混浊     100         20023        4        ND      透明       300       ＞60024        4        ND      透明       100         200
使用烯键式不饱和全氟化聚醚得到了特别好的结果。尽管抗染污层非常薄，但是它们形成的涂层具有非常好、非常耐久的抗墨性。
实施例14的薄膜用来测量通过膜的平均可见光透射率。测出的透射率为93.8％，这接近于未经涂覆的0.13mm厚的PET膜样品的透射率(94.5％)。
实施例25-32
采用实施例1-24的方法制备显示元件：在HFE-7100溶剂中溶解不同量的PFPE-F，并将得到的抗染污涂料溶液涂布到固化后的硬涂层样品上，涂布量足以使干燥后的涂层厚度达到约0.03至约0.2微米。一半的实施例包含IRGACURE 184光引发剂，另一半则没有使用光引发剂。湿涂层在70℃下进行干燥，并使用UV H灯在能量密度为35mJ/cm2 UVC和氮气吹扫下进行固化。表3中列出了每个实施例中全氟化聚醚和光引发剂的用量，并列出了观察到的耐久性结果。
表3实施例     PFPE-F，％   光引发剂％     耐久性，粗平布  耐久性，钢丝绒25       0.25         无             200             60026       0.50         无             250             140027       1            无             400             100028       2            无             300             200029       0.25         4              20              6030       0.50         4              300             100031       1            4              300             180032       2            4              400             2500
表3中的结果表示出很好的耐久性。
实施例33-37
采用实施例1-24的方法，制备显示元件：在HFE-7100溶剂中溶解不同量的全氟化聚醚和0.01％RHODORSIL 2074光引发剂，并将得到的抗染污涂料溶液涂布到固化后的硬涂层样品上，涂布量足以使干燥后的涂层厚度达到约0.08微米。湿涂层在70℃下进行干燥，并使用UV H灯在能量密度为12mJ/cm2 UVC和氮气吹扫下进行固化。表4列出了每个实施例中全氟化聚醚的名称和观察到的耐久性结果。
                  表4实施例    全氟聚醚       耐久性，   耐久性，
                     粗平布     钢丝绒33      PFPE-I1       15         5034      PFPE-J2       6          835      PFPE-K3       30         1536      PFPE-L4       2          1237      PFPE-M5       8          191.PFPE-I是(C2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3.2.PFPE-J是(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)23.PFPE-K是(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)24.PFPE-L是(C2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)35.PFPE-M是(C2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2
表4中结果证明了多种全氟化聚醚在很低的涂层厚度下的应用。
实施例38
在放在冰浴里的第一容器中加入1份BAYTRONTMP聚(3，4-亚乙基二氧噻吩)聚(苯乙烯磺酸酯)导电性聚合物溶液(Bayer Corp.)，然后在搅拌下慢慢加入6.5份N，N-二甲基乙酰胺。在第二容器中，将实施例1-24中反萃取后的干燥陶瓷体前体用14∶1的异丙醇/蒸馏水混合液稀释至固体含量为65％，3.1份得到的稀释组合物与0.05份2，4，6-三甲基苯甲酰基二苯基膦氧化物光引发剂混合。搅拌下第二容器里混合物缓慢加入第一容器中已冷却的混合物中。得到的陶瓷体组合物中含有17％的固体。进一步用72/9/19的异丙醇/乙醇/正丁醇溶剂混合液稀释至三个不同的固体含量水平，如下表5所示：
表5陶瓷体溶液     陶瓷体    溶剂混合物   ％固体
1          50份      50份         8.5
2          85份      15份         14.45
3          80份      20份         13.6
采用实施例1-24的方法和第18号迈耶棒，将每一陶瓷体溶液都涂布到0.13mm厚的PET膜上。涂布后的PET基板在93℃干燥3分钟，然后使涂层两次通过以能量密度为400-600mJ/cm2 UVA工作的UVD灯进行固化。干燥的陶瓷体涂层厚度为1至2微米。用序号为2或3的陶瓷体溶液涂布的一些样品进行了再次涂布并再次固化，因此所得的干燥陶瓷体涂层厚度为2至4微米。随后用1份PFPE-F(CH2＝CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH＝CH2)，0.04份IRGACURE 184光引发剂，93份HFE-7100溶剂和23份甲基·乙基酮溶剂制备好的全氟化聚醚抗染污涂层溶液涂布已用陶瓷体涂布的样品。所述全氟化聚醚溶液以足以使干燥后抗染污涂层厚度达到约0.05-0.1微米的涂布量来施用。采用实施例1-24的方法，干燥抗染污涂层，在以能量密度10-60mJ/cm2 UVC工作的UV H灯下进行固化。表6列出了陶瓷体溶液编号，陶瓷体溶液涂层的数目，陶瓷体涂层的厚度，所涂布的基板的电导率、抗墨性和带粘附性数值：
表6陶瓷体溶液  陶瓷体涂层    陶瓷体厚 电导率       抗墨性    带粘附性
编号        数        度，微米
1           1         1-2      1×1012     5         5
2           1         1-2      1.5×1010   5         5
2           2         2-4      7×109      5         4
3           1         1-2      4×1010     5         5
3           2         2-4      1.5×1010   5         4
实施例39
3颈反应器上安装真空蒸馏头和冷凝器、机械搅拌、加热套和用于控制加热的热电偶。反应器中加入6,718份NALCOTM 1042酸性水溶胶(购自ONDEO Nalco Co.，pH3.5的溶胶，含有34％平均直径为20纳米的氧化硅微粒)，1,122份丙烯酸羟乙酯，562份甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯，2份丁基化的羟基甲苯和0.2份吩噻嗪。混合物在室温下搅拌1小时，然后在加热至55℃，保持约45分钟。通过真空泵缓缓使容器中压力降低，以除去挥发物而不产生过度的泡沫。当泡沫减退的时候，使用高真空以除去挥发物。这需要约6-7个小时的蒸馏。解除真空，然后向反应器中加入792份SR 444季戊四醇三丙烯酸酯(Sartomer，Inc.)。再次使用高真空，除掉残余的挥发物。当蒸馏完成后，将容器中的物质经细筛目粗平布过滤，得到不含溶剂的100％固体陶瓷体硬涂层。
利用充珠法使三个镀铬金属辊粗糙化，其平均表面粗糙度(Ra)值分别达到0.36、0.44和0.57微米。在一系列采用一个糙化金属辊和一0.05mm厚的聚对苯二酸乙二醇酯(PET)膜或0.13mm厚的聚甲基丙烯酸甲酯(PMMA)膜的批次中，将糙化涂层施加到所述薄膜上，使用上述不含溶剂的陶瓷体硬涂层组合物。将可固化陶瓷体组合物沉积到薄膜与金属辊间的辊隙区中，向辊隙施加压力，以足以在辊隙中形成陶瓷体组合物珠的速率移动辊，并使用以能量密度约400mJ/cm2UVA工作的UV D灯(Fusion Systems，Inc.)固化薄膜上的陶瓷体组合物，从而形成糙化涂层。从辊上取下固化陶瓷体涂层和薄膜。固化陶瓷体涂层表面是糙化辊表面的复写。使用实施例27的方法，将HFE-7100溶剂中含1％PFPE-F全氟化聚醚的可固化抗染污层施加并固化到已固化的陶瓷体涂层上，其中使用以能量密度15mJ/cm2 UVC工作的UV H灯。采用装备了5微米滤器的携液模具，将已涂布的薄膜的背面涂布上35％KRATONTM D-1107弹性体在甲苯中的溶液，以获得厚0.03mm的非粘性、无孔隙粘合剂涂层。
对已涂覆的薄膜评价反射性、透射性、浊度、透明度、光泽度、抗墨性和耐久性。作为比较，对普通可商购PDA屏幕保护器(WrightRIGHTTM PDA屏幕保护器，Fellowes Corporation)进行类似的评价。结果如下表7所示。
表7
  批号   基板/粗糙度    ％总反射率     ％第一表面反射率     ％透射率     浊度     透明度     20°光泽度   60°光泽度   85°光泽度   抗墨性   耐久性，钢丝绒   铅笔硬度
  对照1   PVC/ND2    7.186     3.999     80.2     28.2     53.6     7.9   38.3   47.8   0   4   2B
   39-1   PET/0.36    4.853     2.187     93.9     32.8     58.2     8.9   27.4   57   5   1000   ＞3H
   39-2   PET/0.44    4.068     1.358     93.7     44.8     34.3     3.7   16.9   34   5   500   ＞3H
   39-3   PET/0.57    3.899     1.205     93.6     49.5     29.8     4   15.7   32.7   5   1000   ＞3H
   39-4   PMMA/0.36    4.383     1.46     95.4     32.2     57.6     9.9   28.7   61.4   ND   ND   ND
   39-5   PMMA/0.44    3.833     1.392     95.3     43.9     34.1     4.8   18.7   43.9   ND   ND   ND
   39-6   PMMA/0.57    3.566     1.14     95.2     48.6     29.6     4.6   16.9   38.4   ND   ND   ND
1 WrightRIGHTTM PDA屏幕保护器，Fellowes Corporation
2 ND＝未测出
将已涂布的PET薄膜的粘合剂涂布面压到普通纸衬片上，然后将所述薄膜冲切成矩形，形成定制的屏幕保护器，其尺寸已被调整为恰好处于类似于图6所示PDA的PALMTM Vx PDA(Palm ComputingCorp.)屏幕的周界之内。所述屏幕保护器几乎覆盖了整个屏幕，而在屏幕的曲线型下边缘与在下边缘的端点间延伸的弦之间留下小块未覆盖的区域。所述屏幕保护器还可手动修整，以恰好处于类似于图4所示PDA的IPAQTM彩色PDA(Compaq Corp.)屏幕的周界之内。从衬片上取下屏幕保护器，压置到PDA屏幕上，使用信用卡边帮助去除薄膜下的气泡。所述薄膜使户内和户外眩光大大降低，同时并没有不适当地降低PDA屏幕的可见度。当本发明的屏幕保护器不存在时，光反射造成难于在某些角度读取屏幕。屏幕保护器上进行的无光修整使得较易于使用触针在屏幕上书写，因为触针头在屏幕上打滑的可能性被降低。也可将钢笔或铅笔用于在PDA屏幕保护器上进行书写。少量墨水或石墨移转到屏幕保护器上，但使用织物很容易去除，而不会在屏幕保护器表面留下任何可观测到的损坏。相反，若将钢笔或铅笔用于在未经保护的PDA屏幕上直接进行书写，则屏幕通常会被永久性地损坏。
实施例40
采用标准制垫设备，将5层如实施例39所述的经粘合剂涂覆的板片彼此直接层压。最下方的板片层压到普通纸衬片上，所得的层叠冲切成型，以形成垫。调整所述垫的尺寸，使之恰好处于如实施例39所述的PALMTM Vx PDA(Palm Computing Corp.)屏幕的周界之内。从垫上取下衬片，将所述垫附着到PDA的内前盖上。从垫片上取下最上方的屏幕保护器，并使用实施例39所述的信用卡边将其压置到PDA屏幕上。该屏幕保护器的优点如实施例39所述，可令PDA携带附加的屏幕保护器，以提供备用。
实施例41
在一系列批次中，在实施例27的已涂覆薄膜的背面使用刮刀涂布机涂布上两种不同的粘合剂并在70℃干燥15分钟。得到的涂布了粘合剂的样品施加到玻璃上，停留时间有所变化，然后评价180°剥离粘附性。表8中列出了批号、粘合剂名称、干燥粘合剂厚度和测得的剥离粘附性数值。
表8
  批号   粘合剂     粘合剂厚度，mm         180°剥离强度，g/mm宽度
  初始     12小时，  72小时，   170小时，25℃      70℃       70℃
    1    RD-9751   0.03                                  58       80        110        1032    RD-975     0.05                                  74       104       132        1272    RD-975     0.08                                  86       117       126        1293    11072     0.05                                  6        18        19         143    1107       0.08                                  28       41        39         31
1  RD-975丙烯酸类粘合剂(3M)
2  在甲苯中的28％KRATONTM 1107弹性体(Shell Chemical Co.)溶液
对于本领域技术人员而言，在不背离本发明范围和精神情况下对本发明作出的多种改进和改变是显而易见的。本发明不应限于此处所列举的内容，这些内容应理解为只是用于解释说明。

Claims (33)

1.一种显示元件，其包括基本上透明的基板，包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和在硬涂层之上包含全氟化聚醚的抗染污层。
2.权利要求1的元件，其中所述硬涂层包含分散在经自由基固化的粘结剂中的胶态无机氧化物微粒。
3.权利要求2的元件，其中所述胶态无机氧化物微粒包含胶态氧化硅微粒。
4.权利要求1的元件，其中所述粘结剂由一种或多种可共聚的可经自由基固化的单体、低聚物、聚合物或其组合衍生而来。
5.权利要求1的元件，其中所述粘结剂包括导电性聚合物。
6.权利要求1的元件，其中所述抗染污层从下式的全氟化聚醚衍生而来：
             Y-(CaF2aO)b-CaF2a-Y
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是这些重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量为约500至约20,000。
7.权利要求1的元件，其中所述全氟化聚醚包括至少一种如下化合物：
(C2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2，
(C2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3，
F(CF(CF3)CF2O)25CF2CF3，
C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9，
CH2＝CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH＝CH2，
CH2＝CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH＝CH2，
(HOCH2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2，
(C2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3，
(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)2，
(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)2，
(C2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)3，
(C2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2，
或
8.权利要求1的元件，其中所述硬涂层的厚度为约1微米至约100微米，所述抗染污层的厚度为约0.005微米-约2微米。
9.权利要求1的元件，其还包括基本上透明的粘合剂层。
10.权利要求9的元件，其中所述粘合剂与皮肤无粘性。
11.权利要求1的元件，其中所述基板具有两个主要面，在其中一面上是硬涂层和抗染污层，另一面上是粘合剂层。
12.权利要求1的元件，其还包括个人数字助理、蜂窝电话、触敏屏、腕表、汽车导向系统、全球定位系统、深度计、计算器、电子图书、CD播放机、DVD播放机、投影电视屏幕、计算机监视器、笔记本计算机显示器或仪器量表。
13.一种用于信息显示器的屏幕保护器，其包括基本上透明的一般为平面的挠性基板，所述基板的一面具有粘合剂层，另一面具有硬涂层和硬涂层之上的抗染污层，所述硬涂层包含分散在粘结剂基质中的无机氧化物微粒，所述抗染污层包含全氟化聚醚。
14.权利要求13的屏幕保护器，其中所述抗染污层从下式的全氟化聚醚衍生而来：
        Y-(CaF2aO)b-CaF2a-Y
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是这些重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量为约500至约20,000。
15.权利要求13的屏幕保护器，在屏幕保护器的硬涂层一面具有糙化表面。
16.一种用于具有显示屏的便携式电子设备的屏幕保护器，所述的保护器包括基本上透明的层叠挠性板片，所述板片在一面上具有粘合剂层，在另一面上具有包含分散在粘结剂基质中的无机氧化物微粒的硬涂层，和在硬涂层之上包含全氟化聚醚的抗染污层，所述板片层叠进行了切割从而使得板片能够适合所述显示屏。
17.权利要求16的屏幕保护器，其中所述层叠附着于个人数字助理上，或附着于个人数字助理的盖或盒体上。
18.权利要求16的屏幕保护器，其中所述粘合剂与皮肤无粘性，且所述屏幕保护器在其硬涂层一面具有糙化表面。
19.一种抗染污性硬涂层薄膜，其包括一般为平面的挠性基板，所述基板在其至少一面上具有硬涂层和硬涂层之上的抗染污层，所述硬涂层包含分散在粘结剂基质中的无机氧化物微粒，所述抗染污层包含全氟化聚醚。
20.权利要求19的薄膜，其中所述全氟化聚醚包括至少一种如下化合物：(C2H5O)2CH3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6SiCH3(OC2H5)2，(C2H5O)3SiC3H6NHCO(CF2O)15(C2F4O)13CF2CONHC3H6Si(OC2H5)3，F(CF(CF3)CF2O)25CF2CF3，C4H9NHCO(CF2O)15(C2F4O)13CF2CONHC4H9，CH2＝CHCOOC2H4NHCO(CF2O)15(C2F4O)13CF2CONHC2H4OOCCH＝CH2，CH2＝CHCOOCH2(CF2O)15(C2F4O)13CF2CH2OOCCH＝CH2，(HOCH2)2CH2NHCO(CF2O)15(C2F4O)13CF2CONHCH2(CH2OH)2，(C2H5O)3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3Si(OC2H5)3，(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)8CF2CONH(CH2)3SiCH3(OC2H5)2，(C2H5O)2CH3Si(CH2)3NHCO(CF2CF2O)14CF2CONH(CH2)3SiCH3(OC2H5)2，(C2H5O)3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3Si(OC2H5)3，(C2H5O)2CH3Si(CH2)3NHCO(CF2C(CF3)FO)12CF2CONH(CH2)3SiCH3(OC2H5)2，或
Figure A0181379700051
21.一种制备抗染污性硬涂层的方法，包括在基板上涂步包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的陶瓷体涂料并使之固化，和在陶瓷体涂层之上涂步包含可经自由基聚合的氟化物的抗染污层并使之固化。
22.制备显示元件的方法，包括向基本上透明的基板上施加一包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的可固化硬涂层，使硬涂层固化，向硬涂层上施加包含全氟化聚醚的可固化抗染污层，并使抗染污层固化。
23.权利要求22的方法，其中所述全氟化聚醚具有下式结构：
       Y-(CaF2aO)b-CaF2a-Y
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是这些重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量为约500至约20,000。
24.权利要求22的方法，其中所述基板具有第一和第二主表面，在所述第一主表面上施加了所述硬涂层，所述方法进一步包括将粘合剂施加到第二主表面上。
25.一种制备用于信息显示器的屏幕保护器的方法，包括：
a)向基本上透明、一般为平面的基板的一面上施加包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的可固化硬涂层，使该硬涂层固化，向硬涂层上施加包含全氟化聚醚的可固化抗染污层，并使该抗染污层固化；和
b)向所述基板的另一面上施加粘合剂层。
26.权利要求25的方法，其中所述全氟化聚醚具有下式结构：
       Y-(CaF2aO)b-CaF2a-Y
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是这些重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量为约500至约20,000。
27.一种制备用于具有显示屏的便携式电子设备的屏幕保护器的方法，包括：
a)向基本上透明、一般为平面的基板的一面上施加包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒的可固化硬涂层，使该硬涂层固化，向硬涂层上施加包含全氟化聚醚的可固化抗染污层，并使该抗染污层固化；
b)向所述基板的另一面上施加粘合剂层；
c)使已涂布的基板形成层叠板片；和
d)切割所述层叠以使所述板片适合所述显示屏。
28.权利要求27的方法，其中所述全氟化聚醚具有下式结构：
       Y-(CaF2aO)b-CaF2a-Y
式中每个Y包含与随机分布的-CaF2aO-重复单元链相连的可聚合基团，其中每个a都独立地为1至7，b是这些重复单元的数目，并且b的数值从1至300，因此全氟化聚醚的数均分子量为约500至约20,000。
29.一种连续的辊对辊制造方法，其用于制备信息显示器的糙化屏幕保护器板片，所述方法包括：
a)将基本上不含溶剂的可固化陶瓷体组合物沉积到基本上透明的基板与辊间的辊隙区中，所述陶瓷体组合物包含分散在可经自由基聚合的粘结剂基质中的无机氧化物微粒，所述辊的平均表面粗糙度为至少0.1微米；
b)以足够的速率移动辊，同时向辊隙施加足够的压力，以在辊隙中形成陶瓷体组合物珠；
c)在陶瓷体组合物抵附在辊上的同时，(使用例如紫外照射)通过基板固化该陶瓷体组合物；
d)从辊上取下固化的陶瓷体涂层；
e)向固化的陶瓷体涂层上施加包含全氟化聚醚的可固化的抗染污层；和
f)使所述抗染污层固化。
30.权利要求29的方法，其还包括将所述已涂覆的基板改造为尺寸适合所述电子显示设备屏幕的板片。
31.权利要求30的方法，其中所述设备包括便携式设备。
32.权利要求30的方法，其中所述设备包括个人数字助理。
33.权利要求29的方法，其中所述板片形成层叠。
CN01813797A 2000-08-07 2001-08-07 抗染污性硬涂层 Pending CN1446371A (zh)

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