CN102918455B - 电泳媒质 - Google Patents
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Abstract
一种电泳媒质,包括连续相和非连续相。非连续相包括多个微滴,每个微滴包括流体和置于流体内且能够在施加到该电泳媒质上的电场的作用下移动通过该流体的至少一个带电颗粒。连续相围绕并封装非连续相,并包括聚合物粘合剂和盐,该盐具有含至少一个氟原子的阴离子并且在25°C下具有按重量计的至少约0.25%的水溶性。
Description
相关申请
本申请涉及专利号为7,012,735的美国专利和公开号为2009/0122389的美国专利申请。
技术领域
本发明涉及用于生产电泳显示器的电泳媒质,用于这种媒质中的粘合剂以及利用这种粘合剂形成的电泳显示器。
背景技术
此处使用的术语“双稳的”和“双稳定性”取其在本领域中的常规含义,指的是包括具有第一和第二显示状态的显示元件的显示器,所述第一和第二显示状态至少有一种光学性质不同,从而通过有限持续时间的寻址脉冲驱动任一给定元件以呈现其第一或第二显示状态之后,在该寻址脉冲终止后,该状态将持续至少几倍于(例如至少4倍于)改变该显示元件的状态所需的寻址脉冲的最小持续时间的时间。美国专利第7,170,670号示出,某些基于颗粒的电泳显示器不仅在处于它们的极端黑色和白色状态时具有稳定的灰度,在处于它们的中间灰度状态时也具有稳定的灰度,且一些其他类型的电光显示器也同样如此。尽管为了方便起见,此处的术语“双稳的”被用于涵盖双稳的和多稳的显示器,但上述类型的显示器更适合被称作“多稳的”,而非双稳的。
许多年来,电泳显示器一直是一个广泛研究和开发的课题。在基于微粒的电泳显示器中,多个带电粒子在电场作用下移动通过流体。电泳显示器相比液晶显示器具有良好的亮度和对比度、宽视角、状态的双稳定性和低功耗的性质。然而长期存在的电泳显示器的图像质量问题阻碍了其广泛使用。例如,构成电泳显示器的颗粒易于沉降,这就导致这种显示器的使用寿命不足。
如以上所说,电泳媒质需要有流体存在。在大部分现有的电泳媒质中,该流体为液体,但电泳媒质也可以用气态流体制成;参见例如Kitamura,T.等人的“Electrical toner movement for electronic paper-like display”IDWJapan,2001,Paper HCSl-1,以及Yamaguchi,Y.等人的“Toner display usinginsulative particles charged triboelectrically”,IDW Japan,2001,PaperAMD4-4)。还可以参见美国专利第7,321,459和7,236,291号。当媒质在允许沉降的取向上使用时,例如在媒质于垂直面内放置的招牌中使用时,由于与基于液体电泳媒质相同的颗粒沉降现象,这种基于气体的电泳媒质容易遭受同样的问题。实际上,在基于气体的电泳媒质中的颗粒沉降问题比基于液体的电泳媒质更严重,因为与液体相比,气态悬浮流体的粘度更低,从而使电泳颗粒的沉降更快。
转让给或权属于麻省理工学院(MIT)和伊英克(E Ink)公司的大量专利和申请描述了在封装的电泳和其他电光媒质中使用的各种技术。这种封装的媒质包含大量的小囊,每一个小囊本身包含内部相以及环绕内部相的囊壁,该内部相包含流体媒质中的电泳移动粒子。典型地,这些囊本身被保持在聚合物粘合剂内以形成位于两个电极之间的连贯层。在这些专利和申请中描述的技术包括:
(a)电泳颗粒、流体和流体添加物;参见例如美国专利第7,002,728和7,679,814号;
(b)囊、粘合剂和封装方法;参见例如美国专利第5,930,026;6,067,185;6,130,774;6,172,798;6,249,271;6,327,072;6,392,785;6,392,786;6,459,418;6,839,158;6,866,760;6,922,276;6,958,848;6,987,603;7,061,663;7,071,913;7,079,305;7,109,968;7,110,164;7,202,991;7,242,513;7,304,634;7,339,715;7,391,555;7,411,719;7,477,444;和7,561,324号;和美国专利申请公开号第2004/0112750;2005/0156340;2007/0057908;2007/0091417;2007/0223079;2008/0023332;2008/0130092;2008/0264791;2009/0122389;和2010/0044894号;
(c)包含电光材料的膜和子组件;参见例如美国专利第6,982,178和7,839,564号;
(d)用在显示器中的背板、粘合层和其他辅助层以及方法;参见例如美国专利第7,116,318号;和7,535,624;
(e)色彩的形成和色彩的调节;参见例如美国专利第7,075,502号;和美国专利申请公开号2007/0109219;
(f)用于驱动显示器的方法;参见例如美国专利第7,012,600和7,453,445号;
(g)显示器的申请;参见例如美国专利第7,312,784号;和美国专利申请公开号2006/0279527;以及
(h)非电泳显示器,如美国专利第6,241,921;6,950,220;和7,420,549;和美国专利申请公开号2009/0046082。
前述的很多专利和申请认识到,在封装的电泳媒质中围绕离散的微囊的壁可以由连续相代替,因而产生所谓的聚合物分散的电泳显示器,其中电泳媒质包含多个离散的电泳流体微滴以及连续相聚合物材料,并且尽管没有与每个单独的微滴关联的离散的囊膜,但可以把这种聚合物分散的电泳显示器中的电泳流体的离散颗粒看作囊或微囊;参见例如前述的美国专利第6,866,760号。因此,为了本申请的目的,将这样的聚合物分散的电泳媒质看作是封装的电泳媒质的子类。
与此相关的电泳显示器类型称为“微单元电泳显示器”。在微单元电泳显示器中,带电颗粒和流体不封装在微囊中,而是保持在形成于载体媒质中的多个腔内,该载体媒质一般为聚合物薄膜。参见例如转让给SipixImaging公司的美国专利第6,672,921和6,788,449号。
尽管电泳媒质通常是不透明的(例如,由于在许多电泳媒质中,粒子基本上阻挡可见光通过显示器的透射)并且工作在反射模式下,但是可以使许多电泳显示器工作在所谓的“快门模式”下,在该模式下一种显示状态是基本上不透明的而一种显示状态是光透射的。参见例如前述的美国专利第6,130,774和6,172,798号,和美国专利第5,872,552;6,144,361;6,271,823;6,225,971;和6,184,856号。与电泳显示器类似但是依赖于电场强度变化的介电泳显示器可以工作在类似的模式下;参见美国专利第4,418,346号。其他类型的电光显示器也能够工作在快门模式下。
封装的电泳显示器一般不受传统电泳设备的聚集和沉降失效模式的影响并且具有另外的优点,例如可以在各种不同柔性和刚性衬底上印刷或者涂覆该显示器。(使用“印刷”一词旨在包括所有形式的印刷和涂覆,包括但并不局限于:预计量式涂覆,例如小块模具型涂覆(patch die coating),狭缝式或挤压式涂覆,坡流式或阶式涂覆,淋幕式涂覆;压辊涂覆,例如辊式刮刀涂覆、前向和反向辊涂覆;凹版印刷涂覆;浸渍涂覆;喷涂;弯液面涂覆;旋涂;刷涂;气刀涂覆;丝网印刷工艺;静电印刷工艺;热印刷工艺;喷墨印刷工艺;电泳沉积(参见美国专利第7,339,715号);以及其它类似的技术)。因此,得到的显示器可以为柔性。另外,由于显示器媒质可以是(使用各种方法)印刷的,可以廉价地制作显示器本身。
电泳显示器通常包括一层电泳材料和位于电泳材料相对两侧的至少另外两层,其中一层作为电极层。大多这样的显示器中,这两层都是电极层,一层或两层电极层被图案化以限定显示器的像素。例如,一个电极层可被图案化成细长形行电极,另一个可被图案化成与行电极成直角的细长形列电极,像素被限定在行电极和列电极的相交处。可替代地,或更常见地,一个电极层的形式为单个连续电极,另一个电极层被图案化成像素电极的矩阵,每个像素电极限定显示器的一个像素。另一种类型的旨在与触笔、印刷头或者类似的与显示器分开的可移动电极一起使用的电泳显示器中,与电泳层相邻的层中仅有一层包含电极,电泳层相对侧的一层通常为保护层,其旨在防止可移动电极损坏电泳层。
三层电泳显示器的制造通常包括至少一次层压操作。例如,上面所述的麻省理工学院(MIT)和伊英克(E Ink)公司的几个专利和申请中,描述了封装电泳显示器的制造工艺,在该工艺中,在粘合剂中包含囊的封装电泳媒质被涂在包含铟锡氧化物(ITO)的柔性基板上或位于塑料薄膜上类似的导电涂层(作为最终显示器的一个电极)上,囊/粘合剂涂层干燥后形成牢牢粘结在基板上的电泳介质连贯层。单独地,准备背板,该背板包含像素电极阵列和具有适当布局的导线,以将像素电极连接到驱动电路。为了形成最终的显示器,使用层压粘合剂将其上具有囊/粘合剂层的基板层压在背板上。(通过将背板替换为简单的保护层(例如,塑料薄膜),可以使用非常类似的工艺来制备能够与触笔或者其它类似的移动电极一起使用的电泳显示器,其中触笔或者其它的移动电极可以在保护层上面滑动)。在这种工艺的一种优选形式中,背板本身是柔性的并且通过将像素电极和导线印刷在塑料薄膜或其它柔性基底上制备而成。用于通过这种工艺而大规模生产显示器的一个公知层压技术是使用层压粘合剂的辊压层压技术。类似的制造技术可以用来生产其它类型的显示器。例如,微单元电泳媒质也可以用与封装电泳介质大体相同的方式被层压在背板上。
如前述美国专利第6,982,178号中所讨论的(见第3栏,第63行到第5栏第46行),许多用于电泳显示器的组件和用来制造这种显示器的方法都源自液晶显示器(LCD)中使用的技术,液晶显示器当然也是电光显示器,尽管它使用一种液体而不是固体媒质。例如,电泳显示器可以使用有源矩阵背板,其包括晶体管或二极管阵列和相应的像素电极阵列,以及透明基底上“连续”的前电极(从电极延伸过多个像素,通常是整个显示器这个意义上来说),这些组件基本上和LCD中的相同。然而,组装LCD的方法不能用于电泳显示器。LCD的组装方法通常是将背板和前电极形成在分离的玻璃基底上,然后将这些组件牢固地粘在一起,并在它们之间留有小的间隙,将得到的组装件在真空条件下放置,并将组装件浸没在液晶中,因此,液晶通过背板和前电极间的间隙流动。最终,使液晶就位,密封缝隙以提供最终的显示器。
这种LCD的组装过程不能轻易地转移到电泳显示器上。因为电泳材料是固态的,它必须在背板和前电极彼此固定之前存在于背板和前电极间。此外,液晶材料仅需要简单放置于背板和前电极之间,不需要依附于其中任何一个,与液晶材料不同的是,电泳媒质一般需要与两者固定在一起;大多数情况下,电泳层形成于前电极上,因为这比在包含电路的背板上形成电泳层更容易,然后,通常用粘合剂覆盖电泳层的整个表面,并在热、压力和可能的真空条件下实施层压,以将前电极/电泳层的组合作为整体层压至背板。因此,大多数现有的用于电泳显示器的最终层压方法基本上都是批处理方法,在这种方法中,(通常)电泳媒质、层压粘合剂和背板在最终组装之间被放置到一起,需要提供一种能够更好地适应大规模生产的方法。
电光显示器往往较为昂贵;例如,在便携式计算机中的彩色LCD的成本通常占整个计算机全部成本的较大部分。随着电光显示器的应用扩展到如移动电话和个人数码助理(PDA)等比便携式电脑的成本低得多的设备,面临着极大减少这种显示器成本的压力。如前所述的这种可以通过印刷技术在柔性基底上形成一些固态光电媒质层的能力,开辟了通过大规模生产技术,例如使用生产铜版纸、聚合物薄膜和类似的媒质的商业设备的压辊涂覆法,来降低显示器电光组件成本的可能性。
前述美国专利第6,982,178号中描述了一种组装固态电光显示器(包括电泳显示器)的方法,这种方法适合大规模生产。基本上,该专利描述了所谓的"前面板层压组件"("FPL"),它依次包括:透明导电层;与透光导电层电接触的固态电光媒质层;粘合剂层;及释放板。通常情况下,透明导电层被承载在透光基底上,优选为柔性的,在这种意义上,所用基底可以手动卷绕成直径为10英寸(254毫米)的圆桶(比如说)而不发生永久性变形。术语“透光”用在此专利和此处是意味着所指的层可以透过足够的光,使观察者可以通过该层看到电光媒质的显示状态的变化,通常可穿过导电层和相邻基底(如果存在的话)而看到;在电光媒质显示非可见光波长反射率的变化的情况下,术语“透光”应当被解释为是指对相关非可见光波长的透光。基板通常为聚合物薄膜,厚度范围通常在1至25密耳(25至634微米),优选为大约2至10密耳(51至254微米)。导电层通常是金属或金属氧化物薄层,例如铝或ITO,也可能是导电聚合物。包覆铝或ITO的聚(乙烯对苯二甲酸酯)薄膜(PET)可从商业上获得,例如,特拉华州威尔明顿的杜邦公司的“包覆铝的迈拉”(“迈拉”是注册商标),这类商业化的材料可以很好地用于前面板层压组件上。
前述美国专利第6,982,178号中还描述了一种在前面板层压组件合并到显示器前测试前面板层压组件中的电光媒质的方法。在该测试方法中,在释放板上提供导电层,并在该导电层和电光媒质对侧的导电层之间施加足以改变电光媒质光学状态的电压。观察电光媒质,发现媒质中的任何缺陷,从而避免将有缺陷的电光媒质层压到显示器而引起整个显示器的报废,而不仅仅是有缺陷的前面板层压组件的报废。
前述美国专利第6,982,178号中还描述了第二种测试前面板层压组件中的电光媒质的方法,该方法通过在释放板上放置静电荷,从而在电光媒质上形成图像。通过与上述相同的方法观察此图像以检测光电媒质中的任何缺陷。
通过从前面板层压组件移除释放板并在能够有效引起粘合层粘附到背板的条件下使背板接触粘合层,使用这种前面板层压组件来组装电光显示器,从而将粘合层、电光媒质层和导电层固定在背板上。此过程很好适应大批量生产,这是因为通常使用卷对卷涂覆技术,然后切成用于特定背板所需要的任何尺寸的片,可大规模生产前面板层压组件,。
前述美国专利第7,561,324号中描述了所谓“双释放片”技术,基本上是前述美国专利第6,982,178号中前面板层压组件技术的简化。一种形式的双释放片包括夹在两粘合层间的固态电光媒质层,一层或两层粘合层被释放片覆盖。另一种形式的双释放片包括夹在两释放片间的固态电光媒质层。两种形式的双释放膜都旨在用于前面已讨论过的从前面板层压组件组装电光显示器大致相似的工艺中,但包括两次单独的层压;通常,在第一次层压中,双释放片被层压到前电极以形成前部子组件,然后,在第二次层压中,该前部子组件被层压至背板以形成最终显示器,但是,如果需要,这两步层压可以颠倒顺序。
美国专利第7,839,564号描述了一种所谓“反向前面板层压组件”技术,是前述美国专利第6,982,178号中的前面板层压组件技术的变型。这种反向前面板层压组件依次包括:透光保护层和透光导电层中的至少一个;粘合层;固态电光媒质层;以及释放片。这种反向前面板层压组件被用于形成包含位于电光层和前电极或前基板间的层压粘合剂层的电光显示器;通常为薄层的第二粘合剂层存在或可以不存在于电光层和背板间。这种光电显示器可以兼具良好分辨率和良好的低温性能。
通过以上讨论明显看出电泳显示器是一个复杂的***,其中可能包括(1)电泳颗粒本身,器可以是具有核/壳结构和/或聚合物涂层的复合粒子;(2)电泳颗粒周围的流体;(3)流体的添加物,如电荷控制剂、表面活性剂和分散的聚合物等;(4)电泳颗粒和流体周围的囊壁;囊、微滴或微单元周围的粘合剂或其他连续相;(5)一个或多个粘合层;以及(6)一个或多个电极层。不足为奇的是,鉴于这一***的复杂性,这种显示器的电光性能和用于组成显示器的各种材料的机械、物理-化学和电性能之间的确切关系只是部分地被理解。例如,已知如果前面板层压组件中使用的粘合剂的电导率不足,则显示器的电光性能可能会受到不良影响。前述美国专利第7,012,735号描述了通过向粘合剂掺杂盐或其它材料以提高其电导率而获得的益处,用于此目的优选掺杂剂是四丁基六氟磷酸铵(以下简称“TBAHFP”)。同一个专利还描述了类似的用盐掺杂显示器粘合剂的优点,包括例如TBAHFP。
粘合剂掺杂所要减少或克服的其中一个问题是所谓“白色状态退化”或“WSD”。WSD本身表现为显示器工作期间的极端白色光学状态的反射率(通常以CIE L*a*b*色彩空间的L*值来度量)的降低。根据经验发现,出现WSD的量取决于操作占空比、温度和电泳媒质的内部相成分(电泳颗粒和流体)。美国专利申请公开号2010/0289736中描述的电泳媒质类型,粘合剂内缺乏离子掺杂剂,已被发现在25°C、20%操作占空比的条件下在第一个48工作小时内,出现2-9L*个单位的WSD。对于大多数需要在这些条件下、经历240小时的操作后WSD不能大于(最好大大少于)约3L*个单位的应用来说,这种程度的WSD是不可接受的。
虽然离子掺杂剂(通常是一种盐)掺入粘合剂可减少WSD,但选择合适的盐具有相当大的困难。在实践中,电泳显示器内部相中使用的流体是有机材料,通常是低分子量碳氢化合物,粘合剂是由水溶液或分散剂形成的聚合物,最常见的粘合剂的类型是作为水的乳胶形式添加的聚亚氨酯。乳胶与囊混合(存在这种囊时),或内部相乳化在乳胶中(在聚合物-分散的电泳媒质的情况下)。然后乳胶和囊或微滴形成的浆被涂敷在基底上,该浆层被干燥后形成连贯的电泳层。乍看起来,离子掺杂剂应该是一种可溶于水的盐,可以容易地以水溶液的形式添加到水的聚合物胶乳中。然而,发现普通的水溶性盐如氯化钠却不能有效地减轻WSD;例如向上述2010/0289736中所述类型的电泳媒质的粘合剂中添加相当于250-350ppm的TBAHPF的摩尔量的氯化钠,在25°C温度、20%操作占空比的条件下,经历240小时后WSD约为7.5L*单位。一些疏水性(不溶于水)的盐可以取得更好的结果;例如,在相同条件下,添加250-350ppm的美国专利第7,012,735号中曾提到的TBAHPF,WSD约为1L*。这些盐对WSD的影响依赖于浓度,而且它们对较宽范围EO性能(包括例如薄膜晶体管(TFT)性能、图像稳定性和停留态依赖性)的影响对浆中其它组分的浓度敏感。显然与浆掺杂剂相互作用而影响EO性能的其它组分包括TritonX100(聚乙二醇辛基苯基醚)和用于将盐分散成溶液的溶剂。
令人遗憾的是,不溶于水的盐带来了其他问题。至关重要的是盐应该均匀分散在整个粘合剂内,只简单地将盐分散在水中并不足以产生这种均匀分散。实际上,有必要将这类盐溶解于合适的水溶性有机溶剂内,并将溶解在这种溶剂中的盐溶液添加到形成粘合剂的乳胶中。当然,选择的溶剂必须不能对囊或微滴、粘合剂本身或最终干燥的电泳层的性能有任何不利影响。在实践中,合适的溶剂仅限于N-甲基吡咯烷酮(NMP)、四氢呋喃和丙酮。在电泳层干燥期间很难去除有机溶剂的所有痕迹(trace),因为干燥条件仅限于包含有挥发性的有机液体的囊或微滴能够容忍的条件。已知残留在已干燥电泳层或粘合层中的有机溶剂的痕迹会导致严重的问题;例如,见前述2009/0122389,它描述了残留在已干燥的粘合层内的NMP痕迹会导致对含有有机半导体的背板的损坏。还发现残留在干燥粘合剂内的有机溶剂痕迹对显示器的电光性能有负面影响;例如,这种有机溶剂影响了白色状态边缘和显示器黑色状态的黑度。
因此,有必要提供一种无需将有机溶剂引入粘合剂而将离子掺杂剂添加到用于电泳媒质的粘合剂的方法,并且本发明提供了这种方法。
发明内容
现在发现阴离子中含氟且具有至少有限水溶性的某些盐可用作电泳媒质的粘合剂的离子掺杂剂。这些液体盐可被添加到水的聚合物分散系用于形成像水溶液状的粘合剂;某些在室温或近室温条件下是液态的盐也可以作为纯液态盐而添加。
因此,本发明一方面提供一种电泳媒质,包括连续相和非连续相,非连续相包括多个微滴,每个微滴包括流体和置于流体内且能够在施加到该电泳媒质上的电场作用下移动通过该流体的至少一个带电颗粒。连续相围绕并封装非连续相,并包括聚合物粘合剂和盐,该盐具有含至少一个氟原子的阴离子并且在25°C下具有按重量计至少约0.25%的水溶性。电泳媒质可以是封装的或分散聚合物型,即在每个微滴和粘合剂之间可以有或可以没有囊壁。电泳媒质也可以是微单元类型。基于粘结剂固形物含量,含氟的盐的量在约50至约10,000ppm的范围,一般约100至1000ppm。
本发明电泳媒质优选的盐类具有包含至少三个氟原子的阴离子。例如该盐具有六氟磷酸阴离子。该盐也可具有咪唑阳离子,特别优选的盐是3-丁基-1-甲基咪唑六氟磷酸盐。(应该指出在美国专利第7,012,735号中提到的四丁基六氟磷酸铵不具备可用于本发明的充分的水溶性)。可替代地,该盐可具有四氟硼酸或三氟甲磺酸(triflate)阴离子。
如已经提到的,本发明的电泳媒质所用的盐在温度为25°C下应具有至少约0.25%(按重量计算)的水溶性,以便将该盐以水溶液形式添加到粘合剂中。比较令人满意的是在25°C下具有至少约1.0%以及优选更大(按重量计算)的水溶性的盐,从而能够将盐以1%的水溶液的形式添加到粘合剂。在粘合剂内加过量的水和盐是不理想的,因为盐/粘合剂混合物通常与电泳媒质内部相的囊或微滴混合在一起,涂覆在基底上然后干燥或暴露于能够有效促使电泳媒质在基底上形成连贯层的条件。若将过量的水和盐加入到粘合剂内可能延迟基底上电泳媒质的干燥,因此是不希望的。
本发明所用的一些盐的熔点不大于约25°C,因此在室温下是液态;例如前述的3-丁基-1-甲基咪唑六氟磷酸盐(以下简称“BMIHFP”)在室温下是液态。尽管这些液态盐可以直接分散在水的聚合物分散系或乳胶而不用任何溶剂,但优选的仍是以稀释的水溶液的形式加入这些盐,因为使用这样的水溶液可以使盐在整个粘合剂内分散的更均匀。
本发明延伸到电泳组件,所述电泳组件包括本发明的电泳媒质和粘附于电泳媒质的粘合层。电泳媒质的一个或两个暴露表面和粘合层可以被释放片所覆盖。
本发明的电泳组件的形式为前面板层压件,依次包括,基底(可以包含透光导电层)、电泳媒质、粘合层和释放片。可替代地,本发明的电泳组件的形式为反向前面板层压件,依次包括,基底(可以包含透光导电层)、粘合层、电泳媒质和释放片。第二粘合层可以插在电泳媒质和释放片之间。本发明的电泳组件的形式也可以为上述的双释放片。
本发明还提供了用于形成本发明电泳媒质的工艺。该工艺包括形成聚合物的水分散系;向该聚合物的水分散系中添加水的盐溶液,该盐的阴离子含有至少一个氟原子,并且在25°C下具有按重量计至少约0.25%的水溶性;向所述聚合物的含盐水分散系添加包含电泳内部相的囊或这种内部相的微滴;将所得混和物涂覆到基底;将基底上的涂层暴露于能够有效促使涂覆的分散物形成基底上电泳媒质连贯层的条件下。
如上文所述,本发明提供了一种电泳媒质,其具有的粘合剂包含一种含氟阴离子的盐。已发现将这种盐添加至电泳媒质的粘合剂可以有效降低媒质的WSD;例如,添加一摩尔量的BMIHFP(相当于250-350ppm)到上述2010/0289736所述类型的电泳媒质,在25°C、以20%占空比工作240小时后电泳媒质WSD值由5.4L*单位降低到1.1至1.5L*单位。添加同样量的BMIHFP也可以有效地将黑态退化(“DSD”(dark state degradation)-以与WSD极其类似的方式测量,当然除了DSD本身表示为媒质的黑态的L*数值的增加)从2.0L*单位降低到0.5-0.9L*单位。WSD和黑态退化的改善的实现伴随着媒质其它重要电光性能的降低,例如,绝对白态和黑态的L*值。
如上文所述,已发现向电泳媒质的粘合剂中添加盐(如BMIHPF和TBAHPF)可以有效控制WSD。使用可溶于水的盐(如BMIHPF)优于不溶于水的盐(如四丁基六氟磷酸铵,TBAHFP),这是因为可溶于水的盐可以被运载到水溶性的囊浆液(即:囊和聚合物分散系或乳胶的混合物)而不需要向浆添加有机溶剂(如NMP);这些溶剂很难从电泳层去除并且对其它电光性能参数(例如,白态边缘、黑态等)有负面的影响。
尽管仅为举例说明,现在给出下面的例子,以详细说明用于本发明的优选试剂、条件和技术。
实施例1
为了示出使用BMIHPF和TBAHPF取得的结果,制备了一系列上述专利申请2010/0289736中所述类型的电泳媒质类型。每一个内部相包含0.03%(按重量计算)的Triton表面活性剂(除了含350ppm TBAHPF的媒质,其所需的表面活性剂的重量百分比是0.05%)。粘合剂掺入(a)没有盐添加剂(对照例);(b)相当于350ppm TBAHPF的摩尔量的BMIHPF;(c)250ppm和(d)350ppm的TBAHPF。TBAHPF作为NMP溶液添加,同时利用该媒质制备单像素实验性显示器,使用标准测试协议来测试WSD、白和黑边缘以及开花模糊度(blooming)。结果如下面表1所示:
表1
从表1的数据,可以看出用BMIHPF代替TBAHPF可减少白态边缘(白态图像幻影的度量标准)近乎一半,并且尽管DS边缘上升,对于大多数使用的电泳媒质,有较低的白态边缘值对TFT的性能更加重要。注意,使用BMIHPF时,尽管敷霜度性能恶化了,实验室和工业化规模的实验证明通过调整粘合剂的配方可以明显降低敷霜度数值;如下表2所示,其给出使用和表1相似的电泳媒质制备的单像素实验性显示器的白态和黑态边缘以及敷霜度数据,不同之处在于表2中的媒质含90或180ppm(真实数据,而不是相当于TBAHPF的数据)的BMIHPF:
表2
如下表3所示,通过实验也发现,在0°C进行动态范围(显示器极限黑和白光学态之间L*单位的差别)测试中,包含BMIHPF的电泳媒质比包含等摩尔TBAHPF的媒质可以有更好的低温表现,其中除了350ppmTBA媒质的表面活性剂成分是0.05%,其余的表面活性剂成分是0.03%。
表3
BMIPF6进一步特别的优势是具有轻微水溶性,可以作为稀释(~1%w/w)的水溶液加至墨水层。
实施例2
本实施例示出本发明中使用六氟磷酸盐、四氟硼酸盐和三氟甲磺酸盐具有的优点。
利用多种水可溶性盐重复上面实施例1的实验,在每种情况下,所用粘合剂是美国专利第7,012,735号中描述的常用的聚亚安酯粘合剂,掺杂500ppm的TBAHPF。结果如下面表4所示。
表4
标记为*的两种盐本质上不溶于水,需要作为NMP溶液添加。因此,WSD图像与其它盐不可比,此处没有给出。
Claims (20)
1.一种电泳媒质,其包括连续相和非连续相,所述非连续相包括多个微滴,每个微滴包括流体和置于所述流体内且能够在施加到该电泳媒质上的电场的作用下移动通过该流体的至少一个带电颗粒,所述连续相围绕并封装所述非连续相,并包括聚合物粘合剂和盐,所述盐具有含至少一个氟原子的阴离子,其特征在于,所述盐在25℃下具有按重量计至少0.25%的水溶性。
2.根据权利要求1所述的电泳媒质,其中每个微滴和所述周围连续相之间具有囊壁。
3.根据权利要求1所述的电泳媒质,其中每个微滴与所述连续相直接接触。
4.根据权利要求1所述的电泳媒质,其为微单元媒质,其中所述连续相的形式为承载媒质,具有形成于其内部的多个腔,所述非连续相被保持在所述腔内。
5.根据权利要求1所述的电泳媒质,其中所述盐具有至少含三个氟原子的阴离子。
6.根据权利要求5所述的电泳媒质,其中所述盐含有六氟磷酸阴离子。
7.根据权利要求6所述的电泳媒质,其中所述盐含有咪唑阳离子。
8.根据权利要求7所述的电泳媒质,其中所述盐包含3-丁基-1-甲基咪唑六氟磷酸盐。
9.根据权利要求5所述的电泳媒质,其中所述盐含有四氟硼酸或三氟甲烷磺酸阴离子。
10.根据权利要求1所述的电泳媒质,其中存在于所述粘合剂中的所述盐的量为粘合剂的固态成分的百万分之50-百万分之10000。
11.根据权利要求10所述的电泳媒质,其中存在于所述粘合剂中的所述盐的量为粘合剂的固态成分的百万分之100-百万分之1000。
12.根据权利要求1所述的电泳媒质,其中在25℃下,所述盐在水里的溶解度按重量至少为1%。
13.一种电泳组件,包括根据权利要求1所述的电泳媒质层和粘附于电泳媒质的粘合层。
14.一种前面板层压组件,依次包括:基底、电泳媒质层、粘合层和释放片,其中所述电泳媒质是根据权利要求1所述的电泳媒质。
15.根据权利要求14所述的前面板层压组件,其中所述基底包括透光导电层。
16.一种反向前面板层压组件,依次包括:基底、粘合层、电泳媒质层和释放片,其中电泳媒质是根据权利要求1所述的电泳媒质。
17.根据权利要求16所述的反转前面板层压组件,还包括插在所述电泳媒质层和所述释放片之间的第二粘合层。
18.一种双释放片,包括夹在两粘合层之间的电泳媒质层,其至少一个粘合层暴露的面被释放片覆盖,其中所述电泳媒质是根据权利要求1所述的电泳媒质。
19.一种双释放片,包括夹在两释放片之间的电泳媒质层,其中电泳媒质是根据权利要求1所述的电泳媒质。
20.一种形成电泳媒质的方法,该方法包括形成聚合物的水分散系;向该聚合物的水分散系中添加水的盐溶液,该盐的阴离子含有至少一个氟原子;向所述聚合物的含盐水分散系添加包含电泳内部相的囊或这种内部相的微滴;将所得混和物涂覆到基底;将涂覆到基底的混合物暴露于能够有效促使涂覆的分散物在所述基底上形成电泳媒质连贯层的条件下,其特征在于,所述盐在25℃下具有按重量计至少0.25%的水溶性。
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US20110286080A1 (en) | 2011-11-24 |
CN102918455A (zh) | 2013-02-06 |
EP2553522B1 (en) | 2016-03-23 |
HK1177786A1 (zh) | 2013-08-30 |
WO2011123847A3 (en) | 2011-12-29 |
WO2011123847A2 (en) | 2011-10-06 |
EP2553522A4 (en) | 2013-10-16 |
US8446664B2 (en) | 2013-05-21 |
TWI441857B (zh) | 2014-06-21 |
TW201144366A (en) | 2011-12-16 |
KR101485234B1 (ko) | 2015-01-22 |
JP2013524280A (ja) | 2013-06-17 |
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