CN104684727B - 阻隔膜构造及其制造方法 - Google Patents

阻隔膜构造及其制造方法 Download PDF

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CN104684727B
CN104684727B CN201380042256.2A CN201380042256A CN104684727B CN 104684727 B CN104684727 B CN 104684727B CN 201380042256 A CN201380042256 A CN 201380042256A CN 104684727 B CN104684727 B CN 104684727B
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layer
substrate
coating
polymeric
topcoating
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CN104684727A (zh
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约瑟夫·C·斯帕尼奥拉
马克·A·勒里希
托马斯·P·克伦
艾伦·K·纳赫蒂加尔
克里斯托弗·S·莱昂斯
盖伊·D·乔利
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3M Innovative Properties Co
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Abstract

一种阻隔膜,该阻隔膜包括:基底;与基底相邻的基础聚合物层;与基础聚合物层相邻的氧化物层;与氧化物层相邻的粘附调整层;以及与粘附调整层相邻的顶部涂层聚合物层。任选的无机层可施加在顶部涂层聚合物层上方。包含粘附调整层提供了增强的抗湿性,以及顶部涂层聚合物层对下面的阻隔堆叠层的改善的剥离强度粘附性。

Description

阻隔膜构造及其制造方法
本发明是在政府支持下根据能源部授予的批号3053、合同号DE-EE0004739完成的。政府在本发明中享有一定的权利。
相关专利申请
本申请要求2012年8月8日提交的美国临时申请61/680,963和2013年3月13日提交的美国临时申请61/779455在35U.S.C.§119(e)下的权益。
技术领域
本公开整体涉及阻隔膜和制造阻隔膜的方法。
背景技术
聚合物和氧化物诸如氧化铝或氧化硅的多层堆叠在一次涂覆工艺中沉积在柔性聚合物膜上,以使得阻隔膜能够抵抗水分渗透。这些阻隔膜可通过多种生产方法来制备,包括液体涂覆技术,诸如溶液涂覆、辊涂、浸涂、喷涂、旋涂;以及干法涂覆技术,诸如用于固体材料热蒸发的化学气相沉积(CVD)、等离子体增强化学气相沉积(PECVD)、溅射和真空工艺。此类阻隔膜和方法的实例可在以下文献中找到:例如,美国专利5,440,446(Shaw等人);5,877,895(Shaw等人);6,010,751(Shaw等人);7,018,713(Padiyath等人);以及6,413,645(Graff等人),这些专利均以引用方式并入本文,如同全文示出一样。这些阻隔膜作为玻璃封装材料的柔性替代物在显示器、照明和太阳能市场中具有多种应用。
发明内容
本申请的发明者试图开发出具有改善的耐候性和抗层间分层能力的阻隔膜。
一种阻隔膜的一些实施例包括基底、与基底相邻的基础聚合物层、与基础聚合物层相邻的氧化物层、与氧化物层相邻的粘附调整层;以及与粘附调整层相邻的顶部涂层聚合物层。在一些实施例中,顶部涂层聚合物包括丙烯酸酯。任选地,无机层可位于顶部涂层聚合物层上。在一些实施例中,粘附调整层为粘附促进层。在其它实施例中,粘附调整层为剥离层。
一些用于制备阻隔膜的方法的实施例包括以下步骤:提供基底、将基础聚合物层施加到基底、将氧化物层施加到基础聚合物层、将粘附调整层施加到氧化物层;以及将顶部涂层聚合物层施加于粘附调整层上。
单独的粘附促进层提供了增强的抗湿性、以及顶部涂层对下面的阻隔堆叠层的改善的剥离强度粘附性。
单独的剥离层将临时性保护层施加到氧化物层和聚合物层中的一者并且随后去除,从而形成了改善的阻隔组件。在一些实施例中,将保护层施加到氧化物层以在处理期间保护氧化物层。在处理期间包含保护层减少了氧化物层中的缺陷形成。在一些实施例中,随后在下游处理期间将保护层从氧化物层去除。在一些实施例中,立即通过施加粘合剂层和/或顶部片材或保护衬片来保护所暴露的氧化物层。
本申请的其它特征和优点在以下连同两幅附图一起考虑的详细说明书中进行描述或提及。
附图说明
附图包含在本说明书中并构成本说明书的一部分,并且它们结合具体实施方式阐明本发明的优点和原理。在这些附图中,
图1为示出具有粘附调整层的阻隔膜的示意性横截面;以及
图2为示出用于制备阻隔膜的方法的示意图。
附图未必按比例绘制。应当理解,在给定附图中用于指示部件的数字的使用并不旨在限制另一附图中标记有相同数字的部件。
具体实施方式
在以下详细说明中,可参考形成本说明一部分的一组附图,并且在附图中通过例证的方式示出若干具体实施例。应当理解,在不脱离本发明的范围或实质的情况下,设想并可做出其它实施例。
若干方法可用于制备多层阻隔膜中的氧化物层,如上所述。这些方法中的每一种均提供了独特的挑战。在一些情况下,多层阻隔膜中的各层之间的粘附性对于所期望的应用是不足的。例如,聚合物层(例如,聚酯层、丙烯酸酯或甲基丙烯酸酯层)可能不具有对相邻的聚合物层的良好的粘附性。另选地,聚合物层可能不具有对相邻的氧化物层的良好的粘附性。例如,当使用溅射工艺来形成氧化物层时,可能会发生粘附性问题。在溅射工艺中,可用于形成阻隔氧化物层的沉积能量一般是较高的。相比之下,沉积聚合物层中所涉及的能量一般较低,并且这种沉积能量差异可导致粘附性问题。为增加各层之间的粘附性,具体地讲是初始粘附性,硅低价氧化物的薄型溅射层(例如,无机“接合”层)已被证明为可用的。这个无机接合层元件随后可与基底层(一种氧化物)和聚合物封堵层两者形成化学键。用于制备无机接合层的溅射工艺必须在具有精确的功率和气体流设置的情况下来进行,以改善粘附性能。这种沉积工艺历史上易受噪声影响,这导致聚合物层的粘附性多变且较低。甚至当阻隔堆叠的初始粘附性合格时,低价氧化物和聚合物层之间或相邻的聚合物层之间的粘附性在暴露于85℃和85%相对湿度的加速老化条件时已显示出缺点。此外,氧化物层的缺陷可能会在处理期间发生。氧化物层的缺陷可能会降低聚合物层和氧化物层之间的粘附性,从而导致对水进入、降解和/或阻隔膜从其意图保护的设备分层的增大的易感性。一种用于制备阻隔膜的更稳健的解决方案是所需的。
本申请的发明者试图开发出具有改善的耐候性和抗层间分层能力的阻隔膜。在一个方面,发明者认识到需要增加阻隔膜的各层之间的粘附性。在另一方面,发明者认识到需要在处理期间临时性地保护氧化物层以减少缺陷形成。
图1为阻隔膜10的示意性横截面。膜10包括按以下顺序布置的层:基底12;基础聚合物层14;无机层(例如,氧化物层)16;单独的粘附调整层18;顶部涂层聚合物层20;以及任选的无机层21。尽管仅示出两个聚合物层(14、20)和两个无机层(16、21),但膜10可包括位于基底10和顶部涂层聚合物层20或无机层21之间的聚合物和氧化物的另外的交替的层。尽管图1中粘附调整层18定位在无机层16和顶部涂层聚合物层20之间,但应当理解粘附调整层可存在于任何聚合物-聚合物或聚合物-氧化物交界处。具体地,粘附调整层可设置在基底和基础聚合物层之间、基础聚合物层和氧化物层之间、氧化物层和顶部涂层聚合物层之间、和/或顶部涂层聚合物层上。
在一些实施例中,粘附调整层18为粘附促进层,该粘附促进层改善了膜10的抗湿性和阻隔膜10的剥离强度粘附性。在其它实施例中,粘附调整层为剥离层,该剥离层可为氧化物层提供临时性保护。用于阻隔膜10的各层的示例性材料在下文和实例部分中确定。
图2为系统22的图解,该图示出了用于制备阻隔膜10的示例性方法。系统22处于真空下,并且包括用于接收和移动基底12的冷冻转筒24(如由膜26表示),从而提供移动的幅材。蒸发器28施加基础聚合物,该基础聚合物由固化单元30进行固化,以在转筒24沿着箭头25所示的方向推进膜时形成基础聚合物层14。氧化物溅射单元32施加氧化物,以在转筒24推进膜26时形成无机层16。对于基础聚合物和氧化物的另外的交替的层,转筒24可沿着与箭头25相反的方向反向旋转,并且随后再次推进膜26,以施加另外的交替的基础聚合物层和氧化物层,并且可根据要求或需要对交替的层重复该子过程多次。一旦基础聚合物和氧化物的交替的层完成,则转筒24进一步推进膜,并且蒸发器34沉积粘附调整层。转筒24进一步推进膜,并且蒸发器36沉积顶部涂层聚合物层20。粘附调整层18和顶部涂层聚合物层20可单独固化。另选地,粘附调整层18和顶部涂层聚合物层20可由固化单元38一起固化。顶部涂层聚合物层20可包括例如辐射固化的单体(例如(甲基)丙烯酸酯)。实例部分更详细地描述了使用系统22来制备阻隔膜10的示例性工艺。
尽管系统22在图2中示出,但应当理解粘附调整层可存在于如上所述的任何交界处。在一些实施例中,一个或多个层可包括粘附促进层。在其它实施例中,一个或多个层可包括剥离层。在另外其它实施例中,第一层可包括粘附促进层,而第二层可包括剥离层。因此,系统22可包括另外的蒸发器和/或固化单元,或现有的蒸发器/固化单元的位置可改变。另选地,对于另外的交替的氧化物层、粘附调整层和顶部聚合物层,转筒24可沿着与箭头25相反的方向反向旋转,并且随后再次推进膜26,以便施加另外的交替的氧化物层、粘附调整层和顶部聚合物层。可根据要求或需要对交替的层重复这个子过程多次。
粘附促进材料常常具有与至少一个相邻层反应性或能够与至少一个相邻层进行非反应性交互的至少一个部分。在一些实施例中,所述部分与两个相邻层反应和/或能够与两个相邻层进行非反应性交互。用于在粘附促进层中使用的示例性材料包括例如硅烷(例如,硅烷偶联剂、烷氧基硅烷、卤代硅烷、乙酰氧基硅烷、环状氮杂硅烷、和氨基官能硅烷)、异羟肟酸、磷酸酯、膦酸酯、膦酸、锆酸盐、钛酸盐等等,所有这些示例性材料都具有另外的反应性基团,诸如,例如(甲基)丙烯酸酯和环氧树脂。其它合适的粘附促进材料包括在以下与本申请同一日提交的共同待审的专利申请中描述的那些材料:“阻隔膜、制备阻隔膜的方法以及包括阻隔膜的制品(Barrier Film,Method of Making the Barrier Film,andArticles Including the Barrier Film)”(代理人案卷号70169US002)、“包括脲-丙烯酸酯硅烷的复合材料层(Composite Layers Including Urea Acrylate Silanes)”(代理人案卷号69821US002)、“包括二氨基甲酸酯硅烷的复合材料层(Composite LayersIncluding Diurethane Silanes)”(代理人案卷号69822US002)、以及“包括脲-氨基甲酸酯-丙烯酸酯硅烷的复合材料层(Composite Layers Including Urea Urethane AcrylateSilanes)”(代理人案卷号69823US002),所有这些专利申请均以引用方式并入本文。
在一些实施例中,粘附促进层为硅烷偶联剂。这种类型的材料的特性是其与刚溅射沉积的金属氧化物层(诸如,例如刚溅射的具有表面羟基-硅烷醇(Si-OH)基团的SiO2层)上的金属-羟基(金属-OH)基团反应的能力。可充分控制存在于多过程真空室中的水蒸气的量,以便促进以足够高的表面浓度形成Si-OH基团,从而提供增加的键合位点。在监测残余气体并使用水蒸气源的情况下,可控制真空室中的水蒸气的量,以确保适当生成Si-OH基团。
通常,剥离层和至少一个相邻层之间的粘附性足够低以使得能够在适当条件下去除所述相邻层,但并非低至使得各层由于通常在正常加工和处理操作中遇到力而过早地分开。用于剥离层的示例性材料包括硅氧烷、氟化材料(例如,包含氟代烷基或氟代亚烷基或全氟聚醚部分的单体、低聚物或聚合物)、可溶材料、烷基链(例如,包含12-36个碳原子的直链的、支链的和/或环状的烃部分)等等。
本文所述的膜和方法通过添加单独的粘附调整层,改善了蒸汽沉积的多层阻隔涂层的总体粘附性和在暴露于湿气之后的粘附性保持。在一些实施例中,在蒸汽涂覆工艺期间施加粘附调整层,在蒸汽涂覆工艺中粘附调整层吸附或冷凝到刚用硅和铝的氧化物溅射涂覆的移动的幅材基底上。吸附或冷凝的层随后可暴露于后续的处理步骤,例如暴露于固化(例如,电子束辐射)、另外的无机层溅射和/或另外的聚合物层沉积。通过添加粘附促进层,剥离强度粘附性得到很大改善,特别是在暴露于高热和湿度条件之后。另外,添加粘附调整层消除了对接合层的需要,这大大简化了涂覆工艺和阻隔涂层堆叠构造。所得的阻隔涂层保持了高阻隔性和光传输性能。
用于在基底、基础聚合物层和/或顶部涂层聚合物层中使用的示例性聚合物包括在美国专利申请公布2012/0003448(Weigel等人)中列出的那些聚合物,该专利申请全文以引用方式并入本文。
本申请的阻隔膜还可包括顶部片材。在一些实施例中,顶部片材使用压敏粘合剂附着到阻隔膜。可形成顶部片材的可用材料包括聚酯、聚碳酸酯、聚醚、聚酰亚胺、聚烯烃、含氟聚合物以及它们的组合。用于在顶部片材中使用的示例性材料包括在美国专利申请公布2012/0003448(Weigel等人)中列出的那些材料,该专利申请全文以引用方式并入本文。
在实施例中,本申请的阻隔膜用于封装太阳能设备。在此类实施例中,通常需要顶部片材能够抗寒耐热并抵抗由紫外(UV)光引起的降解。由UV光(例如,从280到400nm的范围内)引起的光氧化降解可导致聚合物膜的颜色变化以及光学和机械性能的劣化。本文所述的顶部片材可为光伏器件提供例如耐用的、抗寒耐热的面涂层。基底是大体耐磨且耐冲击的,并且当例如光伏器件暴露于户外元素时可防止光伏器件的降解。
在一些示例性实施例中,可直接用本文所述的方法来封装柔性电子设备。例如,可将这些设备附接到柔性承载基底,并且可沉积掩模以保护电连接件在无机层、(共)聚合物层或其它层沉积期间免受这些层的影响。可使组成多层阻隔组件的无机层、(共)聚合物层和其它层如本公开中其它地方所描述的那样沉积,并且随后可将掩膜去除,从而使电连接件暴露。
在一个示例性的直接沉积或直接封装实施例中,湿气敏感的设备为湿气敏感的电子设备。湿气敏感的电子设备可以是例如有机、无机或有机/无机混合半导体器件,包括:例如,光伏器件,诸如铜铟镓(二)硒化物(CIGS)太阳能电池;显示设备,诸如有机发光显示器(OLED)、电致变色显示器、电泳显示器、或液晶显示器(LCD)诸如量子点LCD显示器;OLED或其它电致发光的固态照明设备,或它们的组合等。
用于制备多层阻隔组件的合适方法以及合适的透明多层阻隔涂层的实例可在以下文献中找到:美国专利5,440,446(Shaw等人);5,877,895(Shaw等人);6,010,751(Shaw等人);以及7,018,713(Padiyath等人)。在一个目前优选的实施例中,制品或膜中的阻隔组件可通过在类似于美国专利5,440,446(Shaw等人)和7,018,713(Padiyath等人)中所述的系统的辊到辊式真空室中将各个层沉积到基底上而制成。
实例
除非另外指明,否则实例中的所有份数、百分比和比率均按重量计。除非不同地指出,否则所使用的溶剂和其他试剂可购自威斯康星州密尔沃基的西格玛奥尔德里奇化学公司(Sigma-Aldrich Chemical Company;Milwaukee,WI)。
比较层合构造A和层合构造1-2的制备
通过使用0.05mm厚的压敏粘合剂(PSA)(可以商品名“3M OPTICALLY CLEARADHESIVE 8172P”购自明尼苏达州圣保罗的3M公司(3M Company,St.Paul,MN)),将22.9cm×15.2cm的阻隔膜层合到乙烯四氟乙烯聚合物片材(ETFE)(0.05mm厚,可以商品名“NORTONETFE”购自新泽西州韦恩的圣戈本功能塑料公司(St.Gobain Performance Plastics,Wayne,NJ)),来制备比较层合构造A和层合构造1-2,其中阻隔膜的顶部涂层聚合物层与ETFE片材相邻。分别使用比较例A和实例1-2的阻隔膜来制备比较层合构造A和层合构造1-2。随后将阻隔膜的聚对苯二甲酸乙二酯(PET)侧布置在0.14mm(0.0056in)厚、21.6cm×14cm的PTFE涂覆的铝箔(可以商品名“8656K61”购自加利福尼亚州圣塔菲泉的麦克马斯特凯尔公司(McMaster-Carr,Santa Fe Springs,CA))上。PTFE涂覆的铝箔在每个维度上都比阻隔膜小1.27cm,从而使PET的一部分暴露。将13mm(0.5in)宽的干燥的封边胶带(可以商品名“SOLARGAIN EDGE TAPE SET LP01”购自俄亥俄州梭伦的实唯高技术公司(TrusealTechnologies Inc.,Solon,OH))围绕PTFE涂覆的铝箔的周边布置,以便将层合的阻隔片材固定到PTFE层。将0.38cm(0.015in)厚的封装剂膜(可以商品名“JURASOL”购自伊利诺伊州唐纳格罗夫的侏罗膜片公司(JuraFilms,Downer Grove,IL))布置在PTFE涂覆的铝箔的铝侧上。将与第一层合的阻隔片材在构成上相同的第二层合的阻隔片材的PET层设置在封装剂膜上方,以形成层合构造。使该构造在150℃下真空层合持续12min。
测试方法
光谱透射
使用光谱仪(型号“LAMBDA 900”,可从马萨诸塞州华尔顿的珀金埃尔默公司(PerkinElmer,Waltham,MA)商购获得)来测量光谱透射。光谱透射被报告为在0°入射角下介于400nm和700nm之间的平均透射百分比(Tvis)。
水蒸气传输速率
根据ASTM F-1249-06,“使用调制红外传感器对穿过塑料膜和片材的水蒸气传输速率的标准测试方法(Standard Test Method for Water Vapor Transmission RateThrough Plastic Film and Sheeting Using a Modulated Infrared Sensor)”中概述的过程、使用MOCONModel 700WVTR测试系统(可购自明尼苏达州明尼阿波利斯的膜康公司(MOCON,Inc,Minneapolis,MN))来测量比较例A和实例1-2的阻隔膜的水蒸气传输速率(WVTR)。使用约50℃的温度和约100%的相对湿度(RH),并且以克/平方米/天(g/m2/天)来表示WVTR。测试系统最低检测限为0.005g/m2/天。在一些情况下,所测量的WVTR低于最低检测限,并且被报告为<0.005g/m2/天。
老化测试
将利用比较例A和实例1-2的阻隔膜制备的层合构造布置在被设定为约85℃的温度和约85%的相对湿度的环境舱(型号“SE-1000-3”,可购自密歇根州霍兰德的热测实业公司(Thermotron Industries,Holland,MI))中持续0小时(初始)、250小时和500小时。
T-剥离测试方法
通过剥离PTFE层而将比较例A以及实例1和实例2的老化和未老化的阻隔膜从层合构造去除。随后将阻隔膜分割成1.0in宽(2.54cm)的区段。根据ASTM D 1876-08“用于粘合剂的抗剥离性的标准测试方法(Standard Test Method for Peel Resistance ofAdhesives)(T剥离测试)”中概述的过程,将这些区段布置在拉伸强度测试机(可以商品名“INISIGHT 2SL”(带有Testworks 4软件)购自明尼苏达州伊登普雷里的MTS公司(MTS,EdenPrairie,MN))中。使用254mm/min(10英寸/分钟)的剥离速度。粘附性以牛顿/厘米(N/cm)报告为介于0.05cm和5.95cm之间的4个剥离测量的平均值。
比较例A
美国专利5,440,446(Shaw等人)和7,018,713(Padiyath等人)均以引用方式并入本文,通过在这两个专利中所描述的类似涂布机的真空涂布机上,用基础聚合物层、无机硅铝氧化物(SiAlOx)阻隔层和顶部涂层聚合物层的叠堆覆盖聚对苯二甲酸乙二酯(PET)基底膜(可以商品名“XST 6642”购自特拉华州威尔明顿的杜邦公司(E.I.DuPont de Nemours,Wilmington,DE))来制备阻隔膜。按以下方式形成各个层:
层1(基础聚合物层):将一卷350米长的0.127mm厚×366mm宽的PET膜加载到辊到辊真空处理室中。对该室进行抽气,直至压力降到1×10-5托。保持4.8米/分钟的幅材速度,同时保持PET膜的后侧与冷却到-10℃的涂覆转筒接触。在后侧与转筒接触的情况下,以0.02kW的等离子体功率用氮等离子体来处理膜前侧表面。随后,用三环癸烷二甲醇二丙烯酸酯单体(可以商品名“SR-833S”购自宾夕法尼亚州埃克斯顿的美国沙多玛公司(SartomerUSA,Exton,PA))来涂覆膜前侧表面。在进行涂覆之前,将该单体在真空下脱气至20毫托的压力,加载到注射器泵中,并且以1.33mL/min的流速泵送穿过以60kHz的频率工作的超声喷雾器、到达维持在260℃下的加热的蒸发室中。将所得的单体蒸汽流冷凝到膜表面上,并且使用在7.0kV和4mA下工作的多细丝电子束固化枪进行电子束交联,以形成720nm厚的基础聚合物层。
层2(无机层):紧接于基础聚合物层沉积之后并且在PET膜的后侧仍与转筒接触的情况下,将SiAlOx层溅射沉积在23m长的基础聚合物层顶上。使用两个交流电(AC)电源来控制两对阴极;其中每个阴极容纳两个90%Si/10%Al溅射靶(可购自俄亥俄州梅菲尔德山庄的美题隆公司(Materion Corporation,Mayfield Heights,OH))。在溅射沉积期间,来自每个电源的电压信号被用作比例-积分-微分控制环路的输入,以便维持到每个阴极的预先确定的氧气流速。AC电源使用5000瓦特的功率,在3.5毫托的溅射压力下以包含450标准立方厘米/分(sccm)氩气和63sccm氧气的气体混合物来溅射90%的Si/10%的Al靶。以上操作提供了沉积在层1的基础聚合物层顶上的30nm厚的SiAlOx层。
层3(顶部涂层聚合物层):紧接于SiAlOx层沉积之后并且在PET膜的后侧仍与转筒接触的情况下,将丙烯酸酯单体(与层1的单体相同)冷凝到层2上,并且如层1中所描述的那样进行交联,不同的是使用在7kV和5mA下工作的多细丝电子束固化枪。以上操作提供了在层2顶上的720nm厚的顶部涂层聚合物层。
使用以上所述的测试方法来测量比较例A的阻隔膜的初始T剥离粘附性、光谱透射(Tvis)和水蒸气传输速率(WVTR)。随后按照以上概述的过程,使阻隔膜老化持续250小时和500小时。针对老化的样本,测量T剥离粘附性。结果报告在下表1中。
实例1
如比较例A中所描述的那样制备阻隔膜,除了在层2上方并且在即将沉积和冷凝顶部涂层聚合物层(层3)之前沉积粘附促进材料(即,汽化和冷凝)。随后,使阻隔膜进行电子束交联,如比较例A中所述。
使用环状氮杂硅烷(可以商品名“1932.4”购自宾夕法尼亚州莫里斯维尔的盖里斯特公司(Gelest,Morrisville,PA))作为粘附促进材料。
使用以上所述的测试方法来测量实例1的阻隔膜的初始T剥离粘附性、光谱透射(Tvis)和水蒸气传输速率(WVTR)。随后按照以上概述的过程,使阻隔膜老化持续250小时和500小时。针对老化的样本,测量T剥离粘附性。结果报告在下表1中。
实例2
如实例1中所描述的那样制备阻隔膜,除了粘附促进材料为(3-丙烯酰氧基丙基)三甲氧基硅烷(可以商品名“SIA0A200.0”购自盖里斯特公司(Gelest))。
使用以上所述的测试方法来测量实例2的阻隔膜的初始T剥离粘附性、光谱透射(Tvis)和水蒸气传输速率(WVTR)。随后按照以上概述的过程,使阻隔膜老化持续250小时和500小时。针对老化的样本,测量T剥离粘附性。结果报告在下表1中。
表1
本文所提及的所有参考文献均以引用方式并入。
如本文所使用,词语“在……上”和“与……相邻”涵盖以下两者:层直接和间接位于某物上,其它层有可能位于两者之间。
如本文所用,术语“(一个或多个)主表面”是指在具有三组相对表面的三维形状上的具有最大表面积的(一个或多个)表面。
除非另外指明,否则本发明和权利要求书中用来表述特征尺寸、数量和物理特性的所有数字在所有情况下均应理解为被术语“约”修改。因此,除有相反的说明,否则在上述说明书和所附权利要求书中列出的数值参数均为可根据本领域技术人员利用本文所公开的教导内容而寻求获得期望的特性而改变的近似值。
除非本文内容以其他方式明确说明,否则本说明书和所附权利要求书中使用的单数形式“一个”、“一种”和“所述”涵盖具有多个指代物的实施例。除非本文内容以其他方式明确说明,否则本公开和所附权利要求书中使用的术语“或”的含义一般来讲包括“和/或”。
公开了本发明的各种实施例和具体实施。所公开的实施例仅为举例说明而非限制之目的而给出。上述具体实施以及其它具体实施均在以下权利要求书的范围内。本领域的技术人员将会知道,本公开可以通过除所公开的那些以外的实施例和具体实施实行。本领域的技术人员将会知道,可以在不脱离本发明基本原理的条件下对上述实施例和具体实施的细节做出多个更改。应当理解,本发明不旨在用本文所述的示例性实施例和实例进行不当地限制,并且上述实施例和实例仅以举例的方式提出,本发明的范畴旨在仅由本文如下所述的权利要求限定。另外,在不脱离本发明的实质和范围的前提下,对本发明的各种修改和更改对本领域技术人员将是显而易见的。因此,本专利申请的范围应当仅由以下权利要求书确定。

Claims (25)

1.一种阻隔膜,其包括:
基底;
与所述基底相邻的基础聚合物层;
与所述基础聚合物层相邻的氧化物层;
与所述氧化物层相邻的蒸气沉积的粘附调整剥离层;以及
与所述粘附调整剥离层相邻的顶部涂层聚合物层。
2.根据权利要求1所述的阻隔膜,其还包括位于所述基底和所述顶部涂层聚合物层之间的所述基础聚合物层和所述氧化物层的多个交替的层。
3.根据权利要求1所述的阻隔膜,其中所述基底包括柔性透明膜。
4.根据权利要求1所述的阻隔膜,其中所述基础聚合物层包括丙烯酸酯。
5.根据权利要求1所述的阻隔膜,其中所述氧化物层包括无机硅铝氧化物层。
6.根据权利要求1所述的阻隔膜,其还包括施加到所述顶部涂层聚合物层的无机层。
7.根据权利要求6所述的阻隔膜,其中所述无机层包括无机硅铝氧化物层。
8.根据权利要求1所述的阻隔膜,其中所述顶部涂层聚合物层包括丙烯酸酯。
9.根据前述权利要求中任一项所述的阻隔膜,其中粘附调整剥离层还存在于所述基底和所述基础聚合物层之间、以及所述基础聚合物层和所述氧化物层之间中的一者。
10.一种用于制备阻隔膜的方法,该方法包括:
提供基底;
将基础聚合物材料施加到所述基底,以形成基础聚合物层;
将氧化物材料施加到所述基础聚合物材料,以形成氧化物层;
将粘附调整剥离材料蒸气沉积在所述氧化物材料上,以形成粘附调整剥离层;以及
在所述粘附调整剥离材料上形成顶部涂层聚合物层。
11.根据权利要求10所述的方法,其中将所述基础聚合物材料施加到所述基底包括使基础聚合物材料蒸发到所述基底上,以及使所述蒸发的基础聚合物材料固化以形成基础聚合物层。
12.根据权利要求10或11所述的方法,其中施加所述氧化物材料包括将氧化物材料溅射沉积到所述基础聚合物材料上。
13.根据权利要求10所述的方法,该方法还包括:
重复地将基础聚合物材料施加到所述基底以及将氧化物材料施加到所述基础聚合物材料,以在所述基底和所述顶部涂层聚合物层之间形成所述基础聚合物材料和所述氧化物材料的交替的层。
14.根据权利要求10所述的方法,其中所述顶部涂层聚合物层包括丙烯酸酯,并且形成所述顶部涂层聚合物层包括使所述粘附调整剥离材料和所述丙烯酸酯共同蒸发,以及使所述共同蒸发的粘附调整剥离材料和丙烯酸酯固化。
15.根据权利要求10所述的方法,该方法还包括:
使所述粘附调整剥离材料和所述顶部涂层聚合物层中的至少一者固化。
16.根据权利要求10所述的方法,其中所述基础聚合物材料包括丙烯酸酯。
17.根据权利要求10所述的方法,其中施加所述氧化物材料包括将无机硅铝氧化物层施加到所述基础聚合物层。
18.根据权利要求10所述的方法,该方法还包括:
将无机材料施加到所述顶部涂层聚合物层。
19.根据权利要求18所述的方法,其中施加所述无机材料包括施加无机硅铝氧化物层。
20.根据权利要求10所述的方法,其中粘附调整剥离层还设置在所述基底和所述基础聚合物层之间、以及所述基础聚合物层和所述氧化物材料之间中的一者。
21.一种阻隔膜,其包括:
基底;
基础聚合物层;
氧化物层;
蒸气沉积的粘附调整剥离层;以及
顶部涂层聚合物层。
22.根据权利要求21所述的阻隔膜,其中所述粘附调整剥离层设置在所述基底和所述基础聚合物层之间、所述基础聚合物层和所述氧化物层之间、以及所述氧化物层和所述顶部涂层聚合物层之间中的一者。
23.根据权利要求21所述的阻隔膜,其中所述粘附调整剥离层设置在所述顶部涂层聚合物层上。
24.根据权利要求1所述的阻隔膜,其中所述基底选自聚合物膜或电子设备,所述电子设备包括有机发光设备(OLED)、电泳发光设备、液晶显示器、薄膜晶体管、光伏器件、或它们的组合。
25.根据权利要求10所述的方法,其中所述基底选自聚合物膜或电子设备,所述电子设备包括有机发光设备(OLED)、电泳发光设备、液晶显示器、薄膜晶体管、光伏器件、或它们的组合。
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US20150213990A1 (en) 2015-07-30
US10947618B2 (en) 2021-03-16
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