CN110192149A - 有色有机颜料和含有该颜料的电泳显示介质 - Google Patents
有色有机颜料和含有该颜料的电泳显示介质 Download PDFInfo
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- CN110192149A CN110192149A CN201880007312.1A CN201880007312A CN110192149A CN 110192149 A CN110192149 A CN 110192149A CN 201880007312 A CN201880007312 A CN 201880007312A CN 110192149 A CN110192149 A CN 110192149A
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- electrophoretic display
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- SXYOAESUCSYJNZ-UHFFFAOYSA-L zinc;bis(6-methylheptoxy)-sulfanylidene-sulfido-$l^{5}-phosphane Chemical compound [Zn+2].CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C.CC(C)CCCCCOP([S-])(=S)OCCCCCC(C)C SXYOAESUCSYJNZ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- G—PHYSICS
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Abstract
一种电泳显示介质,其包括前电极和后电极,所述前电极和后电极中的至少一个是透明的,以及包含位于所述前电极和后电极之间的多种颜料的封装的分散液。所述多种颜料包括第一类有机颜料颗粒和第二类有机颜料颗粒。所述第一类有机颜料颗粒具有第一颜色和第一电荷极性。所述第二类有机颜料颗粒具有与所述第一颜色不同的第二颜色和与所述第一电荷极性相同的第二电荷极性。所述第一类有机颜料颗粒和第二类有机颜料颗粒中的至少一类包含二氧化硅涂层和共价键合至所述二氧化硅涂层的聚合物稳定剂。
Description
相关申请的交叉引用
本申请要求2017年1月20日提交的序列号为62/448,683的美国临时申请的优先权和权益,其内容通过引用整体并入本文。
发明领域
本发明涉及电泳显示介质中使用的有机颜料。更具体地,在一个方面,本发明涉及包含具有相似电荷极性的多种不同颜色的有机颜料的电泳体系。
发明背景
当应用于材料或显示器时,术语“电光”在本文中以其在成像领域中的常规含义使用,是指具有在至少一种光学性质上不同的第一显示状态和第二显示状态的材料,通过向材料施加电场,该材料从其第一显示状态改变至其第二显示状态。虽然光学特性通常是人眼可感知的颜色,但它可能是另一种光学特性,例如光学透射、反射、发光,或者在用于机器读取的显示器的情况下,是在可见光范围之外的电磁波长反射率变化的意义上的伪彩色。
一些电光材料在材料具有固体外表面的意义上是固体,尽管这些材料可能并且通常具有内部液体填充或气体填充空间。这种使用固体电光材料的显示器在下文中为方便起见可称为“固体电光显示器”。因此,术语“固体电光显示器”包括旋转双色元件显示器、封装电泳显示器、微区电泳显示器和封装液晶显示器。
术语“双稳态的”和“双稳态”在本文中以其在本领域中的常规含义使用,以指代包括显示元件的显示器,所述显示元件具有在至少一种光学性质方面不同的第一显示状态和第二显示状态,例如黑色和白色,并且使得在通过有限持续时间的寻址脉冲驱动任何给定元件之后,以在寻址脉冲终止之后呈现其第一显示状态或第二显示状态,该状态将持续改变显示元件状态所需的寻址脉冲的最小持续时间至少几次,例如至少四次。一些基于颗粒的电泳显示器不仅在其极端黑色和白色状态下稳定,而且在三种或更多种状态下也是稳定的,例如具有三种或更多种颜色的多色显示器。为方便起见,这里可以使用术语“双稳态的”来覆盖具有两种或更多种显示状态的显示元件。
一种类型的电光显示器是基于颗粒的电泳显示器,其中多个带电颗粒在电场的影响下移动通过流体,这种显示器多年来一直是密集研究和开发的主题。与液晶显示器相比,电泳显示器可以具有良好的亮度和对比度、宽视角、状态双稳态和低功耗的属性。然而,这些显示器的长期图像质量的问题阻碍了它们的广泛使用。例如,构成电泳显示器的颗粒倾向于沉降,导致这些显示器的使用寿命不足。
授让给或署名为麻省理工学院(MIT)、E Ink公司、E Ink Californi a、LLC和相关公司的许多专利和申请描述了封装和微区电泳及其它电光介质中使用的各种技术。封装的电泳介质包括许多小囊,每个小囊本身包括在流体介质中含有电泳移动颗粒的内相和围绕内相的囊壁。通常,囊本身保持在聚合物粘合剂内以形成位于两个电极之间的粘附层。在微区电泳显示器中,带电颗粒和流体没有封装在微囊内,而是保留在载体介质(通常是聚合物膜)内形成的多个腔内。这些专利和申请中描述的技术包括:
(a)电泳颗粒、流体和流体添加剂;参见例如第7,002,728和7,679,814号的美国专利;
(b)囊、粘合剂和封装方法;参见例如第6,922,276和7,411,719号的美国专利;
(c)微区结构、壁材料和形成微区的方法;参见例如第7,072,095和9,279,906号的美国专利;
(d)填充和密封微区的方法;参见例如第7,144,942和7,715,088号的美国专利;
(e)含有电光材料的膜和子组件;参见例如第6,982,178和7,839,564号的美国专利;
(f)显示器中使用的背板、粘合剂层和其它辅助层和方法;参见例如第7,116,318和7,535,624号的美国专利;
(g)颜色形成和颜色调整;参见例如第6,017,584;6,545,797;6,664,944;6,788,452;6,864,875;6,914,714;6,972,893;7,038,656;7,038,670;7,046,228;7,052,571;7,075,502;7,167,155;7,385,751;7,492,505;7,667,684;7,684,108;7,791,789;7,800,813;7,821,702;7,839,564;7,910,175;7,952,790;7,956,841;7,982,941;8,040,594;8,054,526;8,098,418;8,159,636;8,213,076;8,363,299;8,422,116;8,441,714;8,441,716;8,466,852;8,503,063;8,576,470;8,576,475;8,593,721;8,605,354;8,649,084;8,670,174;8,704,756;8,717,664;8,786,935;8,797,634;8,810,899;8,830,559;8,873,129;8,902,153;8,902,491;8,917,439;8,964,282;9,013,783;9,116,412;9,146,439;9,164,207;9,170,467;9,170,468;9,182,646;9,195,111;9,199,441;9,268,191;9,285,649;9,293,511;9,341,916;9,360,733;9,361,836;9,383,623;和9,423,666号的美国专利;和公开号为2008/0043318;2008/0048970;2009/0225398;2010/0156780:2011/0043543;2012/0326957;2013/0242378;2013/0278995;2014/0055840;2014/0078576;2014/0340430;2014/0340736;2014/0362213;2015/0103394;2015/0118390;2015/0124345;2015/0198858;2015/0234250;2015/0268531;2015/0301246;2016/0011484;2016/0026062;2016/0048054;2016/0116816;2016/0116818;和2016/0140909的美国专利申请;
(h)用于驱动显示器的方法;参见例如第7,012,600和7,453,445号的美国专利;
(i)显示器的应用;参见例如第7,312,784和8,009,348号的美国专利;和
(j)非电泳显示器,如第6,241,921号的美国专利和公开号为2015/0277160的美国专利申请中所述;和显示器以外的封装和微区技术的应用;参见例如公开号为2015/0005720和2016/0012710的美国专利申请。
许多上述专利和申请认识到,封装的电泳介质中的离散微囊周围的壁可以被连续相代替,从而产生所谓的聚合物分散的电泳显示器,其中电泳介质包括多个电泳流体的离散液滴和聚合物材料的连续相,并且即使没有离散囊膜与每个单独液滴相关联,这种聚合物分散的电泳显示器内的电泳流体的离散液滴也可以被认为是囊或微囊;例如,参见上述第6,866,760号的美国专利。因此,出于本申请的目的,这种聚合物分散的电泳介质被认为是封装的电泳介质的子种类。
电泳显示器通常包括一层电泳材料和设置在电泳材料的相对侧上的至少两个其它层,这两个层中的一个层是电极层。在大多数这样的显示器中,两个层都是电极层,并且电极层中的一个或两个被图案化以限定显示器的像素。例如,一个电极层可以被图案化成细长的行电极而另一个电极层被图案化成与行电极成直角延伸的细长的列电极,像素由行电极和列电极的交叉点限定。供选择地,并且更常见地,一个电极层具有单个连续电极的形式,而另一个电极层被图案化为像素电极矩阵,每个像素电极限定显示器的一个像素。在另一种类型的电泳显示器中,该显示器旨在与触针、打印头或与显示器分开的类似可移动电极一起使用,与电泳层相邻的层中仅一个层包括电极,该电泳层的相对侧上的层通常是用于防止可移动电极损坏电泳层的保护层。
封装的电泳显示器通常不会遭受传统电泳装置的聚集和沉降失效模式,并且提供了进一步的优点,例如在各种柔性和刚性基板上印刷或涂覆显示器的能力。(“印刷”一词的使用旨在包括所有形式的印刷和涂覆,包括但不限于:预计量涂覆,例如小块模具涂覆(patch die coating)、狭缝或挤出涂覆、坡流或阶流涂覆、幕式涂覆;辊涂,例如辊衬刮刀涂覆、正向和反向辊涂;凹版涂覆;浸涂;喷涂;弯月面涂覆;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(参见第7,339,715号的美国专利);以及其它类似技术。)因此,所得到的显示器可以是柔性的。此外,因为可以(使用各种方法)印刷显示介质,所以可以廉价地制造显示器本身。
然而,封装的电泳显示器的使用寿命仍然低于完全期望的。看起来这种使用寿命受到诸如颗粒聚集成簇的趋势等因素的限制,这些因素阻止颗粒完成显示器在其光学状态之间切换所需的运动。电泳颗粒的物理性质和表面特性可以通过将各种材料吸附到颗粒表面上,或者将各种材料化学键合到这些表面上来改变。例如,在含有有机颜料的电泳显示器中,具有不同化学基团的单体可通过分散聚合在颜料上形成聚合物涂层,并且这些涂层可与电荷控制剂反应以提供具有不同电荷强度的有色颗粒。然而,已经观察到,随着颜色数量的增加,由于涂覆的聚合物结构的相似性,一些不同颜色的聚合物涂覆的颜料可能难以彼此分离。一种供选择的方法是使用无机有色颜料,但有机颜料的颜色强度和亮度优于无机颜料。因为有机颜料是优选的,所以需要改善的彩色电光显示器,其包含含有多个有色有机颗粒的电泳介质。
发明概述
根据本发明的一个方面,电泳显示介质包括前电极和后电极以及包含位于前电极和后电极之间的多种颜料的封装的分散液。前电极和后电极中的至少一个可以是透明的。多种颜料包括第一类有机颜料颗粒和第二类有机颜料颗粒。第一类有机颜料颗粒可具有第一颜色和第一电荷极性。第二类有机颜料颗粒可以具有与第一颜色不同的第二颜色和与第一电荷极性相同的第二电荷极性。第一类有机颜料颗粒和第二类有机颜料颗粒中的至少一种包括二氧化硅涂层和结合至二氧化硅涂层的聚合物稳定剂。
鉴于以下描述,本发明的这些和其它方面将是显而易见的。
附图简述
附图仅以实施例而非限制的方式描绘了根据本发明构思的一种实施方式。
该附图描绘了根据本发明一个实施方案的电泳显示装置。
详述
在以下详细描述中,通过实施例阐述了许多具体细节,以便提供对相关教导的透彻理解。然而,对于本领域技术人员来说显而易见的是,可以在没有这些细节的情况下实践本教导。
根据本发明的一个实施方案,提供了一种电泳显示介质,其可以结合到电光显示器中。电光显示器可包括前电极和后电极,前电极和后电极中的至少一个是透明的,以及包含位于前电极和后电极之间的多种颜料的封装的分散液。多种颜料可包含第一类有机颜料颗粒和第二类有机颜料颗粒。第一类有机颜料颗粒可以具有第一颜色和第一电荷极性,而第二类有机颜料颗粒可以具有第二颜色和第二电荷极性。第一颜色和第二颜色也可以不同,而第一电荷极性和第二电荷极性相同。
电泳显示介质可任选地还包括具有第三颜色和第三电荷极性的第三类有机颜料,第三颜色和第三电荷极性两者均不同于第一颜色和第二颜色以及第一电荷极性和第二电荷极性。第一、第二和第三类有机颜料颗粒中的每一种可包括但不限于CI颜料PR254、PR122、PR149、PG36、PG58、PG7、PB28、PB15:1、PB15:2、PB15:3、PB15:4、PY83、PY138、PY150、PY151、PY154、PY155或PY20,以及颜色索引手册中描述的其它常用有机颜料,“New PigmentApplication Technology”(CMC Publishing Co,Ltd,1986)和“Printing InkTechnology”(CMC Publishing Co,Ltd,1984)。具体实施例包括Clariant Hostaperm RedD3G 70-EDS、Hostaperm Pink E-EDS、PV fast red D3G、Hostaperm red D3G 70、Hostaperm Blue B2G-EDS、Hostaperm Yellow H4G-EDS、Novoperm Yellow HR-70-EDS、Hostaperm Green GNX、BASF Irgazine Red L 3630、Cinquasia Red L 4100HD和IrgazinRed L 3660HD;太阳化学酞菁蓝、酞菁绿、二芳基黄或二芳基AAOT黄。此外,第一、第二和第三类有机颜料颗粒的颜色可以独立地着色为例如红色、绿色、蓝色、青色、品红色或黄色。
除了颜色之外,颗粒还可以具有其它不同的光学特性,例如光学透射率、反射率、发光,或者在用于机器读取的显示器的情况下,在可见光范围之外电磁波长反射率变化的意义上的伪彩色。
根据本发明的各种实施方案,第一类有机颜料颗粒和第二类有机颜料颗粒中的至少一种包含二氧化硅涂层,聚合物稳定剂可以结合至该涂层。在一个实施方案中,聚合物稳定剂可包含含有硅烷偶联基团的聚合物,并且硅烷基团共价键合至二氧化硅涂层。在另一个实施方案中,聚合物稳定剂可以离子键合至具有硅烷基团的硅烷偶联剂,并且硅烷基团可以共价键合至二氧化硅涂层。
现在具体参考附图,电泳流体可包括分散在封装的分散液,例如介电溶剂或溶剂混合物中的四类颗粒。为了便于说明,如图所示,四类颜料颗粒可以被称为第一类颗粒(11)、第二类颗粒(12)、第三类颗粒(13)和第四类颗粒(14)。然而,使用仅四类颜料颗粒,利用电泳流体的显示装置可以显示至少五种不同的颜色状态,这导致全色显示。分散液可以根据本领域技术人员已知的任何方法,例如微囊、微区或聚合物基体封装并封装至任何尺寸或形状,例如球形,并且可以具有毫米范围或微米范围的直径,但优选为约十至约几百微米。
可以采用各种涂覆方法为有机颜料颗粒提供二氧化硅涂层。例如,美国专利3,639,133中描述的涂覆方法,提供了涂覆方法的实施例,其内容通过引用整体并入本文。在涂覆有机颜料颗粒之前,可以通过使用各种已知方法,例如超声、球磨、喷射研磨等,首先使有机颜料颗粒的含水浆料解聚和均化来制备颗粒。可以将分散剂添加到含水浆料中以保持颜料颗粒的解聚集。在一种方法中,将有机颜料颗粒分散在乙醇和原硅酸四乙酯的溶液中,并在室温下在碱性条件下反应20小时,以在颗粒上形成通常均匀的二氧化硅涂层。涂层的厚度优选为0.5至10nm,更优选为1至5nm。
在二氧化硅涂层沉积完成后,在将二氧化硅涂覆的颗粒与反应混合物分离之前,反应混合物的pH可降低至约4以下,优选降低至约3。使用硫酸可方便地实现pH的降低,但也可使用其它酸,例如硝酸、盐酸和高氯酸。通过离心方便地将颗粒与反应混合物分离。分离后,不必干燥颗粒。相反,二氧化硅涂覆的颗粒可以容易地再分散在介质中,通常是含水的醇介质,以用于在颗粒上形成聚合物稳定剂的方法的下一步骤。这使得二氧化硅涂覆的颜料颗粒在其经受可聚合或聚合引发基团的附着过程时,能够保持在非聚集和非熔融的形式,从而允许用这些基团完全覆盖颜料颗粒,并防止在微囊中形成颜料颗粒的大聚集体,该大聚集体通常将最终由二氧化硅涂覆的颜料形成。当二氧化硅涂覆的颜料用于小的微囊(直径小于约100μm)时,防止形成这种聚集体尤其重要,并且这种小的微囊是理想的,因为它们降低了电泳介质的工作电压和/或切换时间。
根据本发明的第一实施方案,聚合物稳定剂可以使用本领域技术人员已知的各种聚合技术衍生自一种或多种单体或大分子单体。例如,二氧化硅涂覆的有机颜料颗粒上的聚合物稳定剂可通过无规接枝聚合(RGP)、离子无规接枝聚合(IRGP)和原子转移自由基聚合(ATRP)获得,如第6,822,782号的美国专利中所述,其内容通过引用整体并入本文。如本说明书和权利要求书中通篇所用,“大分子单体”是指具有一个使其能够作为单体的端基的大分子。
用于形成聚合物稳定剂的合适单体可包括但不限于苯乙烯、α-甲基苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、乙烯基吡啶、n-乙烯基吡咯烷酮、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸二甲氨基乙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正十八烷基酯、甲基丙烯酸正十八烷基酯、丙烯酸2-全氟丁基乙酯、甲基丙烯酸2,2,2三氟乙酯、甲基丙烯酸2,2,3,3四氟丙酯、丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、丙烯酸2,2,3,3,3-五氟丙酯、丙烯酸2,2,3,3-四氟丙酯、甲基丙烯酸2,2,3,4,4,4-六氟丁酯和甲基丙烯酸2,2,3,3,4,4,4-七氟丁酯等。大分子单体可以含有选自丙烯酸酯基团、乙烯基基团或其组合的末端官能团。
在本发明的方法中,可聚合单体或大分子单体可以使用任何双官能化合物附着到二氧化硅涂覆的颜料颗粒的表面上,所述双官能化合物具有一个能够共价键合至二氧化硅涂层的基团和另一个能够共价键合或离子键合至单体或大分子单体的基团。在一个实施例中,化合物可以是具有至少一个可聚合基团的硅烷,例如上面列出的可聚合单体(例如甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯)。
聚合物稳定剂可以由反应性和可聚合的单体或大分子单体形成,该单体或大分子单体吸附、结合至或化学键合至用于桥接二氧化硅涂层和聚合物稳定剂的双官能化合物。聚合物稳定剂决定了体系的粒径和胶体稳定性,并且优选具有长的聚合链,其可以使复合颜料颗粒稳定在烃溶剂中。
在描述用于提供期望的可聚合或引发官能度的试剂时,我们不排除聚合物稳定剂可能是“双官能的”的可能性。例如,已知聚合引发剂(例如具有多于一个离子位点的4,4'-偶氮双(4-氰基戊酸)),并且这种引发剂可用于本发明方法中。此外,如前所述,双官能化合物可以具有大分子单体的形式,该大分子单体含有具有与颗粒表面键合能力的重复单元和具有期望的可聚合或引发官能团的其它重复单元,并且这种大分子单体双官能化合物可以形成将通常包含这两种类型的多个重复单元的聚合物稳定剂。
用于与二氧化硅涂覆的颜料键合的优选官能团类别是硅烷偶联基团,尤其是三烷氧基硅烷偶联基团。用于将可聚合基团连接到二氧化钛和类似颜料上的一种特别优选的试剂是上述甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯,其可以商品名Z6030购自Dow ChemicalCompany,Wilmington,Del。也可以使用相应的丙烯酸酯。
用作聚合物稳定剂的一类大分子单体可以是丙烯酸酯封端的聚硅氧烷,例如Gelest、MCR-M11、MCR-M17或MCR-M22。适用于该方法的另一类大分子单体是PE-PEO大分子单体,如下所示:
RmO--[--CH2CH2O--]n--CH2-苯基-CH=CH2;或者
RmO--[--CH2CH2--]n-C(=O)--C(CH3)=CH2。
取代基R可以是聚乙烯链,n为1-60,并且m为1-500。这些化合物的合成可见于Dongri Chao等人,Polymer Journal,第23卷,第9期,1045(1991)和Koichi Ito等人,Macromolecules,1991,24,2348。另一类合适的大分子单体是PE大分子单体,如下所示:
CH3--[--CH2--]n--CH2O--C(=O)--C(CH3)=CH2。
在这种情况下,n为30-100。这类的大分子单体的合成可见于Seigou Kawaguchi等人,Designed Monomers and Polymers,2000,3,263。
当选择双官能化合物以在颗粒上提供可聚合或引发官能度时,应注意试剂中两个基团的相对位置。对于聚合物制造领域的技术人员来说应该是显而易见的,键合至颗粒的可聚合或引发基团的反应速率可以变化很大,这取决于该基团是否牢固地保持靠近颗粒表面,或者该基团是否与该表面间(在原子尺度上)隔开,并且从而可以延伸到颗粒周围的反应介质中,这对于该基团的化学反应来说是有利得多的环境。通常,优选的是,在两个官能团之间的直链中存在至少三个原子;例如,上述甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯在甲硅烷基和烯属不饱和基团之间提供四个碳原子和一个氧原子链,而前述4-乙烯基苯胺将氨基(或实际活性形式的重氮基)与乙烯基团分开苯环的整个宽度,相当于大约三个碳链的长度。
在上述任何方法中,可以调节和控制所用试剂的量(例如,有机核颜料颗粒、二氧化硅壳材料和用于形成聚合物稳定剂的材料)以在所得复合颜料颗粒中获得期望的有机含量。此外,本发明的方法可包括多于一个阶段和/或多于一种类型的聚合。
如上所述,根据本发明的各种实施方案制备的颗粒分散在封装流体中。期望聚合物稳定剂与封装的流体高度相容。在实践中,电泳介质中的悬浮液通常是基于烃的,尽管流体可以包含一定比例的卤化碳,卤化碳用于增加流体的密度,且因此减小流体密度和颗粒密度之间的差异。因此,重要的是在本发明方法中形成的聚合物稳定剂与封装的流体高度相容,且因此聚合物稳定剂本身包含主要比例的烃链;除了为带电目的提供的基团外,如下所述,大量的强离子基团是不期望的,因为它们使聚合物稳定剂在烃悬浮液中的溶解性降低,且因而不利地影响颗粒分散体的稳定性。而且,如已经讨论的,至少当其中使用颗粒的介质包含脂族烃悬浮液(如通常情况下)时,聚合物稳定剂具有主链和远离主链延伸的多个侧链的支化的或“梳状”结构是有利的。这些侧链中的每一个应具有至少约四个,优选至少约六个碳原子。明显更长的侧链可能是有利的;例如,一些优选的聚合物稳定剂可具有月桂基(C12)侧链。侧链本身可以是支化的;例如,每个侧链可以是支化的烷基基团,例如2-乙基己基基团。据信(尽管本发明决不受这种观点的限制),由于烃链对烃基悬浮液的高亲和力,聚合物稳定剂的支链在刷状或树状结构中通过大量液体彼此分散开,因此增加了颗粒对悬浮液的亲和力和颗粒分散的稳定性。
形成这种梳状聚合物有两种基本方法。第一种方法使用固有地提供必要侧链的单体。通常,这种单体在长链的一端具有单个可聚合基团(至少四个,优选至少六个碳原子)。已发现在本发明方法中给出良好结果的这类单体包括丙烯酸己酯、丙烯酸2-乙基己酯和甲基丙烯酸月桂酯。甲基丙烯酸异丁酯和丙烯酸2,2,3,4,4,4-六氟丁酯也已成功使用。在一些情况下,可能期望限制在这种方法中形成的侧链的数量,并且这可以通过使用单体的混合物(例如,甲基丙烯酸月桂酯和甲基丙烯酸甲酯的混合物)形成无规共聚物来实现,在无规共聚物中只有一些重复单元带有长侧链。在以RGP-ATRP方法为代表的第二种方法中,使用单体混合物进行第一聚合反应,这些单体中的至少一种带有引发基团,从而产生含有这种引发基团的第一聚合物。然后通常在与第一聚合反应不同的条件下使该第一聚合反应的产物经受第二聚合,以使聚合物中的引发基团在原始聚合物上引发另外的单体的聚合,从而形成所需的侧链。如同上面讨论的双官能试剂,我们不排除在两种聚合反应之间可以实现引发基团的一些化学改性的可能性。在这种方法中,侧链本身不需要严重支化并且可以由小单体,例如甲基丙烯酸甲酯形成。
连接到颗粒上的烯属或类似的可自由基聚合基团的自由基聚合可以使用常规的自由基引发剂,例如偶氮二(异丁腈)(AIBN)在升高的反应温度,优选60-70℃下进行,而ATRP聚合可以使用常规的金属配合物进行,如Wang,J.S.等人,Macromolecules 1995,23,7901,和J.Am.Chem.Soc.1995,117,5614,以及Beers,K.等人,Macromolecules 1999,32,5772-5776中所述。还参见第5,763,548;5,789,487;5,807,937;5,945,491;4,986,015;6,069,205;6,071,980;6,111,022;6,121,371;6,124,411;6,137,012;6,153,705;6,162,882;6,191,225;以及6,197,883号的美国专利。这些文献和专利的全部公开内容在此引入作为参考。目前优选的用于进行ATRP的催化剂是在联吡啶(Bpy)存在下的氯化亚铜。
其中带有可聚合基团的颗粒在引发剂存在下与单体反应本发明的RGP方法,当反应混合物中的单体聚合时,将不可避免地导致一些未附着到颗粒上的“游离”聚合物的形成。可以通过用未附着的聚合物可溶于其中的溶剂(通常是烃)反复洗涤颗粒来除去未附着的聚合物,或者(至少在金属氧化物或其它致密颗粒的情况下)通过从反应混合物中离心分离出处理过的颗粒(有或没有预先加入溶剂或稀释剂),将颗粒重新分散在新鲜溶剂中,并重复这些步骤,直到未附着聚合物的比例降低到可接受的水平来除去未附着的聚合物。(未附着的聚合物比例下降后,可对聚合物样品进行热重分析。)从经验上看,1重量%级的少量未附着的聚合物的存在对处理过的颗粒的电泳性能没有任何严重的有害影响;实际上,在一些情况下,根据未附着的聚合物和悬浮液的化学性质,在电泳显示器中使用颗粒之前,可能没有必要将具有附着的聚合物稳定剂的颗粒与未附着的聚合物分离。
如已经指出的,已经发现,存在应该在电泳颗粒上形成聚合物稳定剂的量的最佳范围,并且在颗粒上形成过量的聚合物可能降低它们的电泳特性。最佳范围将随许多因素而变化,这些因素包括被涂覆颗粒的密度和尺寸、颗粒旨在用于其中的悬浮介质的性质、以及颗粒上形成的聚合物的性质,并且对于任何特定的颗粒、聚合物和悬浮介质,最佳范围最好根据经验确定。然而,通过一般指导,应该注意的是,颗粒越致密,聚合物的最佳重量比例越低,并且颗粒被分的越细,聚合物的最佳比例越高。通常,颗粒应涂覆有至少颗粒的约2重量%,理想的至少颗粒的约4重量%。在大多数情况下,聚合物的最佳比例范围将为颗粒的约4重量%至约15重量%,通常为约6重量%至约15重量%,最理想的是约8重量%至约12重量%。
为了引入用于产生颜料颗粒的电荷的官能团,可以将共聚单体加入到聚合反应介质中。共聚单体可以直接使复合颜料颗粒带电,或者与显示液中的电荷控制剂相互作用,从而为复合颜料颗粒带来期望的电荷极性和电荷密度。合适的共聚单体可包括乙烯基苄基氨基乙基氨基-丙基-三甲氧基硅烷、甲基丙烯酰氧基丙基三甲氧基硅烷、丙烯酸、甲基丙烯酸、乙烯基磷酸、2-丙烯酰氨基-2-甲基丙烷磺酸、甲基丙烯酸2-(二甲基氨基)乙酯、N-[3-(二甲基氨基)丙基]甲基丙烯酰胺等。合适的共聚单体还可包括氟化丙烯酸酯或甲基丙烯酸酯,如丙烯酸2-全氟丁基乙酯、甲基丙烯酸2,2,2-三氟乙酯、甲基丙烯酸2,2,3,3-四氟丙酯、丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、丙烯酸2,2,3,3,3-五氟丙酯、丙烯酸2,2,3,3-四氟丙酯、甲基丙烯酸2,2,3,4,4,4-六氟丁酯或甲基丙烯酸2,2,3,3,4,4,4-七氟丁酯。供选择地,可以通过用于为颜料提供可聚合或引发官能度的双官能稳定剂将带电荷或可带电荷的基团引入聚合物中。
官能团,例如酸性或碱性基团,可以在聚合过程中以“封端”形式提供,然后可以在形成聚合物后解封。例如,由于ATRP不能在酸存在下引发,如果期望在聚合物内提供酸性基团,可以使用酯如丙烯酸叔丁酯或甲基丙烯酸异冰片酯,并且这些单体在最终聚合物中的残基水解以提供丙烯酸残基或甲基丙烯酸残基。
当期望在颜料颗粒上产生带电荷或可带电荷的基团以及单独附着在颗粒上的聚合物稳定剂时,用两种试剂的混合物处理颗粒(在二氧化硅涂覆后)可能非常方便,其中一种带有带电荷或可带电荷的基团(或最终将被处理以产生期望的带电荷或可带电荷的基团的基团),并且其中另一种带有可聚合或引发聚合的基团。理想地,两种试剂具有相同或基本相同的与颗粒表面反应的官能团,因此,如果发生反应条件的微小变化,试剂与颗粒反应的相对速率将以类似的方式改变,并且,带电荷或可带电荷基团的数量与可聚合或引发聚合的基团的数量之间的比率将保持基本恒定。应当理解,可以通过改变混合物中使用的两种(或更多种)试剂的相对摩尔量来改变和控制该比例。提供可带电位点但不提供可聚合或引发聚合的基团的试剂的实例包括3-(三甲氧基甲硅烷基)丙胺、N-[3-(三甲氧基甲硅烷基)丙基]二亚乙基三胺、N-[3-(三甲氧基甲硅烷基)丙基]乙烯和1-[3-(三甲氧基甲硅烷基)丙基]脲;所有这些硅烷试剂可购自United Chemical Technologies,Inc.,Bristol,Pa.,19007。如已经提到的,提供可聚合基团但不提供带电荷或可带电荷基团的试剂的实例是甲基丙烯酸3-(三甲氧基甲硅烷基)丙酯。
除了有色有机颜料颗粒之外,根据本发明的电泳显示介质的各种实施方案还可包含至少一类无机颜料颗粒。无机颜料颗粒也可以用二氧化硅和聚合物稳定剂涂覆,如例如第6,822,782号的美国专利中所述。白色颗粒可以由无机颜料形成,例如TiO2、ZrO2、ZnO、Al2O3、Sb2O3、BaSO4、PbSO4等。黑色颗粒可以由CI颜料黑26或28等(例如,锰铁黑尖晶石或亚铬酸铜黑尖晶石)、炭黑、硫化锌及其组合形成。
通常,四类颗粒分为两组-高电荷组和低电荷组。在两组带相反电荷的颗粒中,一组携带比另一组更强的电荷。因此,四类颜料颗粒也可称为高正颗粒、高负颗粒、低正颗粒和低负颗粒。
例如,红色颗粒(R)和白色颗粒(W)可以是第一组带相反电荷的颗粒,并且在该组中,红色颗粒是高正颗粒,而白色颗粒是高负颗粒。蓝色颗粒(B)和绿色颗粒(G)可以是第二组带相反电荷的颗粒,并且在该组中,蓝色颗粒是低正颗粒,而绿色颗粒是低负颗粒。
在另一个实施例中,红色颗粒可以是高正颗粒;白色颗粒可以是高负颗粒;蓝色颗粒可以是低正颗粒,而黄色颗粒可以是低负颗粒。应当理解,本发明的范围广泛地包括任何颜色的颗粒,只要这四类颗粒具有视觉上可区分的颜色即可。
也如图所示,利用本发明的显示液的显示层具有两个表面,即观看侧的第一表面(17)和第一表面的相对侧的第二表面(18)。显示液夹在两个表面之间。在第一表面(17)的一侧,存在公共电极(15),其是透明电极层(例如,ITO),遍布显示层的整个顶部。在第二表面(18)侧,存在包括多个像素电极(16a)的电极层(16)。
像素电极在第7,046,228号的美国专利中有所描述,其内容通过引用整体并入本文。注意,虽然对于像素电极层提到了利用薄膜晶体管(TFT)背板的有源矩阵驱动,但是本发明的范围包括其它类型的电极寻址,只要电极提供期望的功能即可。
图中两条竖直虚线线之间的每个空间表示像素。如图所示,每个像素具有对应的像素电极。通过施加到公共电极的电压和施加到相应像素电极的电压之间的电位差为像素产生电场。
流体中四类颗粒的百分比可以变化。例如,一种类型的颗粒可占电泳液体积的0.1%至50%,优选0.5%至15%。
还应注意,四类颗粒可具有不同的粒径。有用的尺寸范围可以为1nm至高达约100μm。例如,较小的颗粒可具有范围为约50nm至约800nm的尺寸。较大颗粒的尺寸可以是较小颗粒尺寸的约2至约50倍,更优选约2至约10倍。
电泳颗粒的密度可以基本上与悬浮(即电泳)液的密度相匹配。如本文所定义的,如果悬浮液的各自密度差为约0至约2克/毫升(“g/ml”),则悬浮液的密度与颗粒的密度“基本上匹配”。该差异优选为约0至约0.5g/ml。
其中分散有四类颗粒的溶剂是透明和无色的。对于高颗粒迁移率,它优选具有低粘度和范围为约2至约30,优选约2至约15的介电常数。合适的介电溶剂的实施例包括烃类如异链烷烃(isopar)、十氢化萘(DECALIN)、5-亚乙基-2-降冰片烯、脂肪油、石蜡油、硅液,芳香烃如甲苯、二甲苯、苯基二甲苯基乙烷、十二烷基苯或烷基萘,卤化溶剂如全氟萘烷、全氟甲苯、全氟二甲苯、二氯三氟甲苯、3,4,5-三氯三氟苯、氯五氟苯、二氯壬烷或五氯苯,以及全氟化溶剂如来自3M Company,St.Paul MN的FC-43、FC-70或FC-5060,低分子量含卤素聚合物如来自TCI America、Portland、Oregon的聚(全氟环氧丙烷),聚(三氟氯乙烯)如来自Halocarbon Product,River Edge,NJ的Halocarbon Oils,全氟聚烷基醚如来自Ausimont的Galden、或者来自DuPont、Delaware的Krytox油和润滑脂K-Fluid系列,来自Dow-corning的聚二甲基硅氧烷基硅油(DC-200)。
在一个实施方案中,“低电荷”颗粒携带的电荷可以小于“高电荷”颗粒携带的电荷的约50%,或约5%至约30%。在另一个实施方案中,“低电荷”颗粒可以小于“高电荷”颗粒携带的电荷的约75%,或约15%至约55%。在另一个实施方案中,所示电荷水平的比较适用于具有相同电荷极性的两类颗粒。
可以根据ζ电位测量电荷强度。在一个实施方案中,ζ电位由具有CSPU-100信号处理单元的Colloidal Dynamics AcoustoSizerΠM,ESA EN#Attn流通池(flow throughcell)(K:127)确定。仪器常数,如样品中所用溶剂的密度、溶剂的介电常数、溶剂中的声速、溶剂的粘度,所有这些都在测试温度(25℃)下在测试前输入。将颜料样品分散在溶剂(通常是具有少于12个碳原子的烃流体)中,并稀释至5-10重量%。样品还含有电荷控制剂(Solsperse购自Lubrizol Corporation,Berkshire Hathaway公司;“Solsperse”是注册商标),电荷控制剂与颗粒的重量比为1:10。测定稀释样品的质量,然后将样品加载到流通池中以测定ζ电位。
“高正”颗粒和“高负”颗粒的大小可以相同或不同。同样,“低正”颗粒和“低负”颗粒的大小可以相同或不同。
还应注意,在相同的流体中,两组高-低电荷颗粒可具有不同水平的电荷差。例如,在一组中,低正电荷颗粒的电荷强度可以是高正电荷颗粒的电荷强度的30%,而在另一组中,低负电荷颗粒的电荷强度可以是高负电荷颗粒的电荷强度50%。
可以使用在聚合物涂层中有或没有带电基团的电荷控制剂,以为电泳颗粒提供良好的电泳迁移率。稳定剂可用于防止电泳颗粒的聚集,以及防止电泳颗粒不可逆地沉积在囊壁上。任一组分都可以由多种分子量(低分子量、低聚物或聚合物)的材料构成,并且可以是单一的纯化合物或混合物。用于改性和/或稳定颗粒表面电荷的电荷控制剂如液体调色剂、电泳显示器、非水性涂料分散体和发动机油添加剂领域中通常已知的那样应用。在所有这些领域中,可以将带电物质添加到非水介质中以增加电泳迁移率或增加静电稳定性。这些材料也可以改善空间稳定性。假设不同的带电理论,包括选择性离子吸附、质子转移和接触带电。
可以使用任选的电荷控制剂或电荷导向剂。这些组分通常由低分子量表面活性剂、聚合物试剂或一种或多种组分的共混物组成,并用于稳定或以其它方式改变电泳颗粒上电荷的符号和/或大小。可能相关的其它颜料性质是粒径分布、化学组成和耐光性。
也可加入电荷辅助剂。这些材料提高了电荷控制剂或电荷导向剂的有效性。电荷辅助剂可以是多羟基化合物或氨基醇化合物,并且优选以至少2重量%的量溶于悬浮液中。含有至少两个羟基基团的多羟基化合物的实例包括但不限于乙二醇、2,4,7,9-四甲基癸炔-4,7-二醇、聚(丙二醇)、五乙二醇、三丙二醇、三乙二醇、甘油、季戊四醇、甘油三(12-羟基硬脂酸酯)、丙烯甘油单羟基硬脂酸酯和乙二醇单羟基硬脂酸酯。在同一分子中含有至少一个醇官能团和一个胺官能团的氨基醇化合物的实例包括但不限于三异丙醇胺、三乙醇胺、乙醇胺、3-氨基-1-丙醇、邻氨基苯酚、5-氨基-1-戊醇和四(2-羟乙基)乙二胺。电荷辅助剂优选以约1至约100毫克/克(“mg/g”),更优选约50至约200mg/g颗粒质量的量存在于悬浮液中。
通常,认为带电是由于连续相中存在的一些部分与颗粒表面之间的酸碱反应。因此,有用的材料是那些能够参与这种反应或本领域已知的任何其它带电反应的材料。
有用的不同非限制性类别的电荷控制剂包括有机硫酸盐或磺酸盐、金属皂、嵌段或梳状共聚物、有机酰胺、有机两性离子和有机磷酸盐和膦酸盐。有用的有机硫酸盐和磺酸盐包括但不限于双(2-乙基己基)磺基琥珀酸钠、十二烷基苯磺酸钙、石油磺酸钙、中性或碱性二壬基萘磺酸钡、中性或碱性二壬基萘磺酸钙、十二烷基苯磺酸钠盐和十二烷基硫酸铵。有用的金属皂包括但不限于碱性或中性的石油酸钡,石油酸钙,环烷酸的Co-盐、Ca-盐、Cu-盐、Mn-盐、Ni-盐、Zn-盐和Fe-盐,硬脂酸的Ba-盐、A1-盐、Zn-盐、Cu-盐、Pb-盐和Fe-盐,二价和三价金属羧酸盐,例如三硬脂酸铝、辛酸铝、庚酸锂、硬脂酸铁、二硬脂酸铁、硬脂酸钡、硬脂酸铬、辛酸镁、硬脂酸钙、环烷酸铁、环烷酸锌、Mn-和Zn-的庚酸盐、以及Ba-、Al-、Co-、Mn-和Zn-的辛酸盐。有用的嵌段或梳状共聚物包括但不限于(A)用对甲苯磺酸甲酯季铵化的甲基丙烯酸2-(N,N-二甲基氨基)乙酯的聚合物和(B)聚(甲基丙烯酸2-乙基己酯)的AB二嵌段共聚物,以及具有聚(12-羟基硬脂酸)的油溶性尾部并具有约1800的分子量、悬垂在聚(甲基丙烯酸甲酯-甲基丙烯酸)的油溶性锚基上的梳状接枝共聚物。有用的有机酰胺包括但不限于聚异丁烯琥珀酰亚胺,例如OLOA 371或1200(可以从Chevron Oronite Company LLC,Houston,Tex.获得),或Solsperse 19000和Solsperse 17000(可以从Avecia Ltd.,Blackley,Manchester,英国获得;“Solsperse”是注册商标)和N-乙烯基吡咯烷酮聚合物。有用的有机两性离子包括但不限于卵磷脂。有用的有机磷酸盐和膦酸盐包括但不限于具有饱和和不饱和酸取代基的磷酸化的甘油单酯和甘油二酯的钠盐。
可以添加颗粒分散稳定剂以防止颗粒絮凝或附着到囊壁。对于在电泳显示器中用作悬浮液的典型高电阻率液体,可以使用非水表面活性剂。这些包括但不限于乙二醇醚、炔属乙二醇、烷醇酰胺、山梨糖醇衍生物、烷基胺、季胺、咪唑啉、二烷基氧化物和磺基琥珀酸盐。
如果期望双稳态电泳介质,可能期望在悬浮液中包括数均分子量超过约20,000的聚合物,该聚合物在电泳颗粒上基本上不吸收;为此目的,聚(异丁烯)是优选的聚合物。参见第7,170,670号的美国专利,其全部公开内容通过引用并入本文。
实施例
以下实施例作为本发明的说明性实施方案给出,并不旨在限制本发明的范围。
样品1
将30g有机铜酞菁蓝颜料分散在100ml乙醇和5ml水溶剂混合物中。然后加入1.5g氨以升高pH。加入3g三乙氧基硅烷(TEOS),并将混合物在室温下搅拌20小时。涂覆后,通过在乙醇中洗涤-离心-再分散过程三次纯化颗粒。
然后通过将二氧化硅涂覆的有机颜料颗粒与30g甲基丙烯酰氧基丙基三甲氧基硅烷在150g甲基乙基酮(MEK)溶剂中混合并在60-65℃下回流,使二氧化硅涂覆的有机颜料颗粒官能化。然后通过在异丙醇(IPA)中洗涤-离心-再分散过程两次纯化经官能化的颗粒。
在官能化二氧化硅涂覆的颜料上的聚合物生长是通过在甲苯中的自由基聚合完成的。将15g硅烷化颜料加入到50g甲苯中并在三颈烧瓶中超声处理1小时。将30g丙烯酸2-乙基己酯单体加入烧瓶中,并将N2吹扫到烧瓶中20分钟以除去氧气,然后将烧瓶加热至65℃。将0.2g AIBN的甲苯溶液加入烧瓶中。反应20小时后,通过在甲苯中洗涤-离心-再分散过程三次纯化颗粒。
制备电泳墨水介质用于光电性能测试,所述电泳墨水介质包含24%聚合物涂覆的氧化钛颗粒、16wt%的来自样品1的实例的蓝色颗粒、5wt%的聚合物涂覆的红色颗粒、5wt%的聚合物涂覆的黄色颗粒和0.4%的17000以及异链烷烃溶剂中的其它电荷助剂。
对比样品1
重复用于制备样品1的程序,除了在于用无机铝酸钴蓝色尖晶石颗粒代替铜酞菁蓝颜料。此外,封装的流体含有超过15重量%的无机蓝色颜料颗粒。
对比样品2
重复用于制备样品1的程序,除了在形成聚合物稳定剂之前未用二氧化硅涂覆有机铜酞菁蓝颜料。
测试方法
通过第6,859,302号的美国专利中描述的微区填充密封技术将电泳介质密封在两个透明ITO-PET电极之间。使用相同的驱动顺序由波形发生器驱动测试样品。使用X-riteiOne分光光度计在D65照度设定下进行L*a*b*光学性能的测量。
测试根据样品1、对比样品1和对比样品2的包含颜料颗粒的电泳介质的结果在下面的表1、2和3中提供。
表1.含有样品1的电泳介质的电光性能
蓝色状态 | 红色状态 | 黄色状态 | |
L* | 23.62 | 25.53 | 64.94 |
a* | -4.06 | 33.23 | 1.88 |
b* | -22.01 | 17.52 | 44.76 |
表2.含有对比样品1的电泳介质的电光性能
蓝色状态 | 红色状态 | 黄色状态 | |
L* | 28 | 26.5 | 65.7 |
a* | -0.3 | 41.8 | 13.1 |
b* | -14.2 | 28.5 | 60.8 |
表3.含有对比样品2的电泳介质的电光性能
蓝色状态 | 红色状态 | 黄色状态 | |
L* | 25 | 25.7 | 60.2 |
a* | -11.7 | -7.4 | -0.1 |
b* | -22.8 | -2.2 | 40.9 |
比较三种不同电泳介质的结果,样品1的有色颗粒的电光性能提供了预料不到的改善结果。样品1的蓝色、红色和黄色光学状态中的每一个提供的值表明,与对比样品2的颗粒相比,颜色分离得到了很大改善,对比样品2的颗粒显示出红色状态的退化。如预期的,由样品1的有机颗粒提供的蓝色状态提供了优于对比样品1的无机颗粒的电光性能。因此,通过向有机颜料颗粒提供混合二氧化硅和聚合物稳定剂涂层,实现了改善的电光性能。
虽然本文已经示出和描述了本发明的优选实施方案,但是应该理解,这些实施方案仅作为实施例提供。在不脱离本发明的精神的情况下,本领域技术人员将想到许多变化、改变和替代。因此,所附权利要求旨在覆盖落入本发明的精神和范围内的所有这些变化。
Claims (20)
1.一种电泳显示器,其包括:
前电极和后电极,所述前电极和后电极中的至少一个是透明的;和
包含位于所述前电极和后电极之间的多种颜料的封装的分散液,所述多种颜料包括第一类有机颜料颗粒和第二类有机颜料颗粒,所述第一类有机颜料颗粒具有第一颜色和第一电荷极性,所述第二类有机颜料颗粒具有第二颜色和第二电荷极性,所述第一颜色和第二颜色不同,所述第一电荷极性和第二电荷极性相同,以及所述第一类有机颜料颗粒和第二类有机颜料颗粒中的至少一种包含二氧化硅涂层和结合至所述二氧化硅涂层的聚合物稳定剂。
2.权利要求1所述的电泳显示器,其中,所述第一类有机颜料和第二类有机颜料包括独立地选自PB15:1、PB15:2、PB15:3、PB15:4、PR 254、PR122、PR149、PG36、PG58、PG7、PY138、PY150、PY151、PY154和PY20的有机核。
3.权利要求2所述的电泳显示器,其中,所述第一类有机颜料和第二类有机颜料独立地着色为红色、绿色、蓝色、青色、品红色或黄色。
4.权利要求1所述的电泳显示器,其中,所述多种颜料还包括至少一类无机颜料颗粒。
5.权利要求4所述的电泳显示器,其中,所述无机颜料颗粒选自金属氧化物、锰铁黑、亚铬酸铜黑尖晶石、炭黑,硫化锌及其组合。
6.权利要求1所述的电泳显示器,其中,所述多种颜料还包括具有第三颜色和第三电荷极性的第三类有机颜料,所述第三颜色不同于所述第一颜色和第二颜色,并且所述第三电荷极性不同于所述第一电荷极性和第二电荷极性。
7.权利要求6所述的电泳显示介质,其中,所述第一类有机颜料、第二类有机颜料和第三类有机颜料独立地选自PB15:1、PB15:2、PB15:3、PB15:4、PR254、PR122、PR149、PG36、PG58、PG7、PY138、PY150、PY151、PY154和PY20。
8.权利要求7所述的电泳显示器,其中,所述第一类有机颜料和第二类有机颜料独立地着色为红色、绿色、蓝色、青色、品红色或黄色。
9.权利要求6所述的电泳显示器,其中,所述多种颜料还包括至少一类无机颜料颗粒。
10.权利要求1所述的电泳显示器,其中,所述聚合物稳定剂共价键合至硅烷偶联基团,所述硅烷偶联基团具有共价键合至所述二氧化硅涂层的硅烷基团。
11.权利要求10所述的电泳显示器,其中,所述聚合物稳定剂衍生自单体或大分子单体。
12.权利要求11所述的电泳显示器,其中,所述单体选自苯乙烯、α-甲基苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、乙烯基吡啶、n-乙烯基吡咯烷酮、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸二甲氨基乙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正十八烷基酯、甲基丙烯酸正十八烷基酯、丙烯酸2-全氟丁基乙酯、甲基丙烯酸2,2,2三氟乙酯、甲基丙烯酸2,2,3,3四氟丙酯、丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、丙烯酸2,2,3,3,3-五氟丙酯、丙烯酸2,2,3,3-四氟丙酯、甲基丙烯酸2,2,3,4,4,4-六氟丁酯和甲基丙烯酸2,2,3,3,4,4,4-七氟丁酯。
13.权利要求11所述的电泳显示器,其中,所述大分子单体含有选自丙烯酸酯基团、乙烯基基团或其组合的末端官能团。
14.权利要求1所述的电泳显示器,其中,所述聚合物稳定剂离子键合至具有硅烷基团的硅烷偶联剂,并且所述硅烷基团共价键合至所述二氧化硅涂层。
15.权利要求14所述的电泳显示器,其中,所述聚合物稳定剂衍生自含有可自由基聚合基团的单体或大分子单体。
16.权利要求15所述的电泳显示器,其中,所述单体选自苯乙烯、α-甲基苯乙烯、丙烯酸甲酯、甲基丙烯酸甲酯、丙烯酸正丁酯、甲基丙烯酸正丁酯、丙烯酸叔丁酯、甲基丙烯酸叔丁酯、乙烯基吡啶、n-乙烯基吡咯烷酮、丙烯酸2-羟基乙酯、甲基丙烯酸2-羟基乙酯、甲基丙烯酸二甲氨基乙酯、丙烯酸月桂酯、甲基丙烯酸月桂酯、丙烯酸2-乙基己酯、甲基丙烯酸2-乙基己酯、丙烯酸己酯、甲基丙烯酸己酯、丙烯酸正辛酯、甲基丙烯酸正辛酯、丙烯酸正十八烷基酯、甲基丙烯酸正十八烷基酯、丙烯酸2-全氟丁基乙酯、甲基丙烯酸2,2,2三氟乙酯、甲基丙烯酸2,2,3,3四氟丙酯、丙烯酸1,1,1,3,3,3-六氟异丙酯、甲基丙烯酸1,1,1,3,3,3-六氟异丙酯、丙烯酸2,2,3,3,3-五氟丙酯、丙烯酸2,2,3,3-四氟丙酯、甲基丙烯酸2,2,3,4,4,4-六氟丁酯和甲基丙烯酸2,2,3,3,4,4,4-七氟丁酯。
17.权利要求15所述的电泳显示器,其中,大分子单体含有选自丙烯酸酯基团、乙烯基基团或其组合的末端官能团。
18.权利要求1所述的电泳显示器,其中,所述分散液被封装在微囊内。
19.权利要求1所述的电泳显示器,其中,所述分散液被封装在微区内。
20.权利要求1所述的电泳显示器,其中,所述分散液被封装在聚合物基体内。
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WO2018136250A1 (en) | 2018-07-26 |
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