CN101855083A - 用于光电组件的粘结剂和粘合剂 - Google Patents

用于光电组件的粘结剂和粘合剂 Download PDF

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CN101855083A
CN101855083A CN200880116008A CN200880116008A CN101855083A CN 101855083 A CN101855083 A CN 101855083A CN 200880116008 A CN200880116008 A CN 200880116008A CN 200880116008 A CN200880116008 A CN 200880116008A CN 101855083 A CN101855083 A CN 101855083A
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T·H·怀特赛兹
曹岚
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Abstract

一种光电组件包括粘结剂层和光电材料层。所述粘结剂层包含聚合物粘结剂材料和离子材料,所述离子材料的阳离子或阴离子中的一种固定于所述聚合物粘结剂材料。所述离子材料降低所述聚合物粘结剂材料的体电阻率且当加热至50℃时所述离子材料不被去除。在一种相似的包括粘结剂层和光电材料层的光电组件中,所述粘结剂层包含聚合物粘结剂材料,该聚合物粘结剂材料已经经受渗析或渗滤来去除具有小于3,500的分子量的有机物,使得所述粘结剂材料具有含量为基于所述粘结剂层和光电材料层总重量计的不超过500ppm的N-甲基吡咯烷酮。

Description

用于光电组件的粘结剂和粘合剂
本发明涉及第WO2003/104884号、第WO2004/023195号、第WO2005/041160号、第WO2005/073777号和WO2007/104003号国际申请公开,以及第PCT/US2006/60049号和第PCT/US2006/62399号国际申请。对于有关本发明的背景技术信息,读者参考这些国际申请。
本发明涉及可用于生产光电显示器的光电组件,并涉及用于这样的组件的粘结剂(adhesive)和粘合剂(binder)。更具体地,本发明提供了具有受控体电阻率的粘结剂和粘合剂组合物,以及掺入这样的粘结剂的光电组件和显示器。本发明特别地但非排他性旨在用于包含封装电泳介质的显示器。然而,本发明还可利用多种其他类型的固体光电介质,在该意义上它们具有固体的外表面,尽管所述介质可以并且常常具有含有流体(液体或气体)的内腔。因此,术语“固体光电显示器”包括封装电泳显示器、封装液晶显示器以及以下所讨论的其他类型的显示器。本文公开的粘结剂可被用于除了光电显示器以外的用途。
关于光电显示器的背景术语和现有技术在第7,012,600号美国专利中被详细讨论,读者为进一步的信息而参考该专利。因此,所述术语和现有技术将在下文中简要概述。
用于材料或显示器的术语“光电”在本发明中以其在成像领域中的传统含义来使用,是指具有在至少一种光学性质上不同的第一和第二显示状态的材料,通过向该材料施加电场是其从其第一显示状态改变为其第二显示状态。一些光电材料为固体,在该意义上它们具有固体的外表面,尽管所述材料可以并且确实常常具有内部充满液体或气体的空间。为方便起见,这样的利用固体光电材料的显示器在下文中可被称为“固体光电显示器”。因此,术语“固体光电显示器”包括旋转式双色拧转球元件显示器(rotatingbichromal member display)、封装电泳显示器、微电池电泳显示器以及封装液晶显示器。
本文的术语“双稳态的”和“双稳态”以它们在本领域中的传统含义来使用,是指显示器包括具有在至少一种光学性质上不同的第一和第二显示状态的显示器元件,并且使得在任何给定的元件借助于有限时间的寻址脉冲而被驱动以呈现其第一或第二显示状态之后,在寻址脉冲终止后,该状态将持续至少几次,例如至少四次(改变显示器元件的状态所需的寻址脉冲的最少时间)。
已知几种类型的光电显示器,例如:
(a)旋转式双色拧转球元件显示器,(参见,例如,第5,808,783号;第5,777,782号;第5,760,761号;第6,054,071号;第6,055,091号;第6,097,531号;第6,128,124号;第6,137,467号以及第6,147,791号美国专利);
(b)电色显示器,(参见,例如,O′Regan,B.等人,Nature 1991,353,737;Wood,D.,Information Display,18(3),24(2002年3月);Bach,U.等人,Adv.Mater.,2002,14(11),845;和第6,301,038号;第6,870.657号;以及第6,950,220号美国专利);
(c)电湿润显示器(参见,Hayes,R.A.等人,″Video-Speed Electronic PaperBased on Electro wetting″,Nature,425,383-385(2003年9月25日)和第2005/0151709号美国专利申请);
(d)基于粒子的电泳显示器,在该显示器中大量带电粒子在电场的影响下贯穿流体移动(参见,第5,930,026号;第5,961,804号;第6,017,584号;第6,067,185号;第6,118,426号;第6,120,588号;第6,120,839号;第6,124,851号;第6,130,773号;和第6,130,774号美国专利;第2002/0060321号;第2002/0090980号;第2003/0011560号;第2003/0102858号;第2003/0151702号;第2003/0222315号;第2004/0014265号;第2004/0075634号;第2004/0094422号;第2004/0105036号;第2005/0062714号;和第2005/0270261号美国专利申请公开;第WO 00/38000号;第WO 00/36560号;第WO00/67110号;和第WO 01/07961号国际申请公开;第1,099,207 B1号和第1,145,072 B1号欧洲专利;以及在前述第7,012,600号美国专利中讨论的其他MIT和E Ink的专利和专利申请)。
有几种不同的电泳介质的变体。电泳介质可使用液态流体或固态流体;对于气态流体而言,参见,例如,Kitamura,T.,等人,″Electrical toner movementfor electronic paper-like display″,IDW日本,2001,Paper HCSl-1;和Yamaguchi,Y.,等人,″Toner display using insulative particles charged triboelectrically″,IDW日本,2001,Paper AMD4-4);第2005/0001810号美国专利公开;第1,462,847号;第1,482,354号;第1,484,635号;第1,500,971号;第1,501,194号;第1,536,271号;第1,542,067号;第1,577,702号;第1,577,703号;和第1,598,694号欧洲专利申请;以及第WO 2004/090626号;第WO2004/079442号;和第WO 2004/001498号国际申请。所述介质可以被封装,其包括许多小包囊,各个小包囊自身包括含有悬浮于液态悬浮介质中的电泳流动粒子的内相和包围所述内相的包囊壁。通常,所述胶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粘结层(coherent layer),见前述的MIT和E Ink的专利和专利申请。供选择地,封装电泳介质中包围离散的微胶囊的壁可以被连续相取代,由此产生所谓的聚合物分散电泳显示器,其中所述电泳介质包括大量离散的电泳流体的液滴和聚合物材料的连续相,参见,例如,第6,866,760号美国专利。出于本申请的目的,这样的聚合物分散电泳介质被认为是封装电泳介质的亚类。另一种变体是所谓的“微电池电泳显示器”,其中带电粒子和流体保留在载体介质(通常聚合物膜)中形成的多个空腔内,参见,例如,第6,672,921和6,788,449号美国专利。
尽管电泳介质通常是不透明的(由于,例如在多种电泳介质中,粒子基本上阻断可见光通过显示器的透射)并且以反射模式来运行,许多电泳显示器可以被制造成以所谓的“快门模式”来运行,在该模式中一种显示状态是基本不透明的,而一种显示状态是透光的。参见,例如,前述的第6,130,774号和第6,172,798号美国专利;和第5,872,552号;第6,144,361号;第6,271,823号;第6,225,971号;和第6,184,856号美国专利。与电泳显示器相似但依赖于电场强度变化的介电电泳显示器可以以相似模式运行,参见,第4,418,346号美国专利。其他类型的光电显示器也能够以快门模式运行。
封装电泳显示器通常不遭受传统电泳组件的群集故障模式和沉降故障模式,并且提供了进一步的优点,例如能够在许多种柔性和刚性基底上印刷或涂覆显示器。(单词“印刷”的使用旨在包括所有形式的印刷和涂覆,包括,但不限于:预计量式涂覆,例如贴片模具式涂覆,狭缝式涂覆或挤压式涂覆,斜板式涂覆或层叠式涂覆,帘式涂覆;辊式涂覆,例如辊式刮刀涂覆,顺辊式涂覆和逆辊式涂覆;凹版式涂覆;浸渍式涂覆;喷雾式涂覆;液面弯曲式涂覆(meniscus coating);旋转式涂覆;刷式涂覆;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号美国专利;和其他相似的技术)。因此,所得的显示器可以为柔性的。另外,因为显示器介质可以被印刷(利用多种方法),显示器本身可以被便宜地制造。
其他类型的光电介质,例如,聚合物分散液晶,也可以用于本发明的显示器。
光电显示器通常包括光电材料层和置于光电材料的相对侧的至少另外两层,这两层中的一层为电极层。在大多数这样的显示器中,这两层均为电极层,并且构造所述电极层中的一层或两层以限定显示器的像素。例如,一个电极层可被构造成延长行电极(elongate row electrodes),另一电极层可以被构造成与延长行电极成直角的列电极,像素由行电极和列电极的交叉点来限定。供选择地,且更常见的是,一个电极层具有单个连续的电极形式,而另一个电极层被构造成像素电极的矩阵,这两个电极层各自限定显示器的一个像素。在旨在与触针、印刷头或与显示器分离的相似可移动电极一起使用的另一种类型的光电显示器中,临近光电层的层中仅一层包含电极,位于光电层相对面的层通常为旨在防止可移动电极损害光电层的保护层。
三层式光电显示器的制造通常包括至少一种层压操作。例如,在几个前述的MIT和E Ink专利和专利申请中,描述了一种用于制造封装电泳显示器的工艺,其中,将包含位于粘合剂中的胶囊的封装电泳介质涂覆到位于塑料膜上的包含氧化铟锡(ITO)柔性基底上或相似的电导涂层(用作最终显示器的一个电极)上,将胶囊/粘合剂涂层干燥以形成与基底牢固粘着的电泳介质粘结层。单独制备后面板,该后面板包含像素电极阵列和连接像素电极以驱动电路的合适的导体布置。为了形成最终的显示器,使用层压粘结剂将其上具有胶囊/粘合剂层的基底层压至后面板。(可以利用非常相似的工艺来制备可与触针或相似的可移动电极一起使用的电泳显示器,该工艺通过用触针或其他可移动的电极可以在其上滑动的简单保护层(诸如塑料膜)来代替后面板)。在上述工艺的一个优选形式中,后面板本身是柔性的,并且通过将像素电极和导体印刷在塑料膜上或其他柔性基底上来制备。通过该工艺大量生产显示器的显而易见的层压技术是利用层压粘结剂的滚动层压。相似的制造技术可用于其他类型的光电显示器。
如在前述第6,982,178号美国专利(参见,第3栏第63行至第5栏第46行)中所讨论的,许多用于固体光电显示器的部件和用于制造这样的显示器的方法是从用于液晶显示器(LCD′s)的技术中衍化而来的。然而,用于组装LCD′s的方法不能用于固体光电显示器。LCD′s的组装通常是通过在分开的玻璃基底上形成后面板和前电极,然后将这些部件粘结固定在一起,使得它们之间留有小孔隙,在真空下放置所得的组件,并将该组件浸没于液晶浴中,使得液晶穿过后面板和前电极之间的孔隙来流动。最后,随着液晶处于适当位置,孔隙被封闭以提供最终的显示器。
该LCD组装工艺不能被容易地转化为固体光电显示器。因为光电材料是固体,它必须在后面板和前电极相互固定之前存在于这两个整体之间。另外,与简单位于前电极和后面板之间而不附着于其中任一个的液晶材料相比,固体光电介质通常需要与两者均固定,在大多数情况中,在前电极上形成固体光电介质,因为这通常比在含有电路的后面板上形成介质容易,并且然后,通常通过用粘结剂覆盖整个光电介质表面并在热、压力和可能真空下层压来将前电极/光电介质的组合层压至后面板。因此,大多数用于固体电泳显示器的最终层压的现有技术方法基本是批处理方法,其中(通常)在最终的组装之前立即将光电介质、层压粘结剂和后面板组合在一起,希望提供更好地适于大量生产的方法。
第6,982,178号美国专利描述了一种组装良好地适于大量生产的固体光电显示器(包括封装电泳显示器)的方法。基本上,该专利描述了所谓的“前面板层压板(“FPL”)”,其按顺序包括透光的电导层、与所述电导层电接触的固体光电介质层、粘结剂层以及释放片。通常,在透光基底(优选为柔性的)上将带有透光的电导层,这是在该基底可人工地被包绕在直径10英寸(254mm)的圆筒(比如说)而无永久变形的意义上而言的。本专利和本文中使用的术语“透光的”的意思是由此定义透过足够光的层以使得观察者能够通过该层观察光电介质的显示状态的变化,该变化通常将通过电导层和邻近的基底(如果存在的话)而观察到,在光电介质呈现出在非可见波长反射率变化的情况中,术语“透光”应该当然被解释为是指透过相关的非可见波长。
第6,982,178号美国专利还描述了一种在将前面板层压板并入显示器之前检测前面板层压板中的光电介质的方法。在该检测方法中,释放片配备有电导层,并且在该电导层和位于光电介质相对面的电导层之间施加足以改变该光电介质的光状态的电压。然后,对于光电介质的观察将揭示了介质中的任意缺陷,由此避免将缺陷的光电介质层压至显示器中(具有所产生的刮伤整个显示器的代价,不仅仅是缺陷的前面板层压板)。
第6,982,178号美国专利还描述了第二种检测前面板层压板中的光电介质的方法,该方法通过将静电电荷置于释放片上,由此形成关于光电介质的图像。然后,在检测到光电介质中的任何缺陷之前以前述相同方式观察该图像。
利用这样的前面板层压板来组装光电显示器可以通过如下步骤进行:从前面板层压板去除释放片,并在有效导致粘结剂层与后面板粘结的条件下使粘结剂层与后面板接触,由此将粘结剂层、光电介质层以及电导层固定于后面板。由于通常可以利用滚动式涂覆技术来大量生产前面板层压板且然后将其切割成用于特定后面板所需要的任何尺寸的碎片,因此该工艺良好地适于大量生产。
第2004/0155857号美国专利申请公开描述了所谓的“双释放片”,其基本为前述第6,982,178号美国专利的前面板层压板的简化形式。双释放片的一种形式包括夹在两个粘结剂层之间的固体光电介质,所述粘结剂层的一层或两层被释放片覆盖。所述双释放片的另一种形式包括夹在两个释放片之间的固体光电介质层。两种形式的双释放膜均旨在用于通常与已经描述的由前面板层压板组装光电显示器的工艺相似但包括两个分开的层压的工艺;通常,在第一层压中,将双释放片层压至前电极以形成前次组件,然后在第二层压中,将所述前次组件层压至后面板以形成最终的显示器,但如果希望可以将这两个层压的顺序颠倒。
前述的2007/0109219描述了一种所谓的“反转式前面板层压板”,其为前述第6,982,178号美国专利中描述的前面板层压板的变体。该反转式前面板层压板按顺序包括:透光保护层和透光电导层中的至少一个;粘结剂层;固体光电介质层;以及释放片。该反转式前面板层压板用于形成具有在光电层和前电极或前基底之间的层压粘结剂层的光电显示器;在光电层和后面板之间可以存在或不存在另一通常薄的粘结剂层。这样的光电显示器可以将良好的分辨率和良好的低温性能组合起来。
如前述第7,012,735号和第7,173,752号美国专利中所讨论的,用于光电显示器(或在用于生产这样的光电显示器的前面板层压板、反转式前面板层压板、双释放膜或其他次组件中)的层压粘结剂的选择提出了某些特别的问题。由于层压粘结剂通常位于电极之间(其施加改变光电介质的电状态所需的电场),因此所述粘结剂的电性质通常至关重要。所述层压粘结剂还需要满足几个力学和流变学标准,包括粘结剂的强度、柔性、在层压温度下耐压和流动的能力等。可以满足所有相关电学和力学标准的可商购获得的粘结剂的数量少,且实际上,大多数合适的层压粘结剂为某些聚氨酯,例如第2005/0107564号美国申请公开中描述的那些。这些聚氨酯基于四甲基二甲苯二异氰酸盐(TMXDI-系统名1,3-双(1-异氰酸基-1-甲基乙基)-苯)与聚丙二醇和2,2-双(羟甲基)丙酸的聚合,利用六亚甲基二胺进行链增长。在制备聚氨酯之后,通过利用三乙胺中和并利用水稀释而将其分散为含水乳液状的悬浮液。然而,实际上,不可能通过控制用于聚氨酯的制造的材料的比例而使其电导率不同。
因此,对于许多光电显示器和光电组件中的使用而言,聚氨酯粘结剂不具有足够的电导性,并且已知通过使用盐或其他材料掺杂来提高其电导率,如前述第7,012,735号和第7,173,752号美国专利中所描述的。用于该目的的优选掺杂剂是四丁基六氟磷酸铵(下文称为“TBAHFP”)。不幸的是,已经发现以该方式配制的粘结剂可以损害包含由某些有机半导体制造的晶体管的有源矩阵后面板(active matrix backplanes)。本发明提供了供选择形式的层压粘结剂,当其用于含有有机半导体的显示器时可以减轻或消除现有技术粘结剂所造成的问题。本发明还延伸至用于光电显示器的粘合剂的改性以减轻或消除包含有机半导体的显示器中由现有技术粘合剂所造成的问题。
本发明具有两个主要方面。第一方面涉及以不允许材料从粘结剂层扩散出来的方式将离子材料加入到粘结剂层中。第二方面涉及对粘结剂材料或粘合剂进行预处理以去除可能损害有机半导体的某些可扩散物质。
因此,一方面,本发明提供了一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包括聚合物粘结剂材料和离子材料,所述离子材料的阳离子或阴离子中的一种固定于所述聚合物粘结剂材料,并且其阳离子和其阴离子中的另一种自由地贯穿所述聚合物粘结剂材料来迁移,所述离子材料降低所述聚合物粘结剂材料的体电阻率,并且将所述聚合物粘结剂材料加热至50℃所述离子材料不被去除。
下文中,为了方便起见,固定于所述聚合物粘结剂材料的离子材料的阳离子或阴离子将被称为“固定离子”,而贯穿所述聚合物粘结剂材料自由迁移的阳离子或阴离子将被称为“流动离子”。通常,所述固定离子将与聚合物粘结剂化学键合,并且下文讨论用于提供与聚氨酯粘结剂键合的这样的离子的多种技术。然而,这样的化学键合并非绝对必要,条件是所述固定离子不能贯穿所述聚合物粘结剂来迁移,例如,所述固定离子可以形成与所述聚合物粘结剂不同但与其链缠结的聚合物的部分。
在光电组件的一种形式中,离子材料包括固定于聚合物粘结剂材料的季铵或鏻阳离子和羧酸盐阴离子。所述聚合物粘结剂材料可以包括聚氨酯。供选择地,所述离子材料可以包含固定于聚合物粘结剂材料的季铵或鏻阳离子,和六氟磷酸盐、四丁基硼酸盐或四苯基硼酸盐阴离子。在光电组件的另一种形式中,所述离子材料包括从碱性单体和选自磺酸盐、硫酸盐、六氟磷酸盐、四氟硼酸盐、双(甲烷磺酰)亚胺盐、磷酸盐以及膦酸盐流动阴离子衍生的重复单元。所述碱性单体可以包括,例如,乙烯基吡啶、β-二甲基氨基乙基丙烯酸盐、N-甲基(乙烯基吡啶)或N-苄基(乙烯基吡啶)、N-烷基-N′-乙烯基咪唑或N-烷芳基-N′-乙烯基咪唑以及β-(三甲基氨基乙基)丙烯酸盐或β-(三甲基氨基乙基)甲基丙烯酸盐。
在这样的光电组件中,所述光电材料可包括旋转式双色拧转球元件或电色材料。供选择地,所述光电材料可以包括一种电泳材料,所述电泳材料包含置于流体中的并且能够在电场的影响下贯穿流体移动的大量带电粒子。所述带电粒子和流体可以被限制在许多胶囊或微电池内。供选择地,所述带电粒子和流体可以作为由包含聚合材料的连续相包围的许多离散的液滴而存在。
本发明延伸至包含本发明的光电组件的光电显示器、前面板层压板、反转式前面板层压板或双释放膜。
本发明还提供了一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包含一种已经经受渗析或渗滤以去除具有小于约3,500的分子量的有机物的聚合物粘结剂材料。
本发明还提供了一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包括聚合物粘结剂材料,该聚合物粘结剂材料具有含量为不超过基于粘结剂层和光电材料层总重量计的约500ppm的N-甲基吡咯烷酮。
在这样的光电组件中,所述聚合物粘结剂材料可以包括聚氨酯。,N-甲基吡咯烷酮的含量优选不超过基于粘结剂层和光电材料层总重量计的约200ppm,并且希望地为100ppm。
在这样的光电组件中,所述光电材料可以包括旋转式双色元件或电泳材料。供选择地,所述光电材料可以包括电泳材料,所述电泳材料包含置于流体中的并且能够在电场的影响下贯穿流体移动的大量带电粒子。所述带电粒子和流体可被限制在许多胶囊或微电池内。供选择地,所述带电粒子和流体可以作为由包含聚合材料的连续相包围的许多离散的液滴而存在。所述流体可以为液态的或气态的。
本发明延伸至包含本发明的光电组件的光电显示器、前面板层压板、反转式前面板层压板或双释放膜。
本发明还提供了一种电泳介质,所述电泳介质包括连续相和非连续相,所述非连续相包含许多液滴,各液滴包含悬浮流体和置于该悬浮流体中且当向电泳介质施加电场时能够贯穿流体流动的至少一种粒子,所述连续相包围并封装所述非连续相并且包含已经经受渗析或渗滤而去除具有小于约3,500的分子量的有机物的聚合物粘合剂。所述电泳介质可以为封装类型或聚合物分散类型,即,在各液滴和粘合剂之间可以是胶囊壁或不是胶囊壁。
本发明还提供了一种电泳介质,所述电泳介质包括连续相和非连续相,所述非连续相包含许多液滴,各液滴包含悬浮流体和置于该悬浮流体中且当向电泳介质施加电场时能够贯穿流体流动的至少一种粒子,所述连续相包围并封装所述非连续相并且包含聚合物粘结剂,所述聚合物粘结剂具有含量为不超过基于电泳介质的重量计的约1000ppm的N甲基聚吡咯烷酮。
本发明延伸至包含本发明的光电组件或电泳介质的光电显示器、前面板层压板、反转式前面板层压板或双释放膜。
本发明的显示器可用于其中已经使用现有技术光电显示器的任何应用。因此,例如,本发明的显示器可以用于电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签(shelf label)以及闪存驱动器。
附图中的唯一图是显示在以下实施例5中获得的光学状态读数的图表。
如上所述,本发明具有两个主要方面,第一方面涉及将非扩散的离子材料加入到粘结剂层中,而第二方面涉及经渗析或渗滤的粘结剂材料和/或粘合剂在电泳介质和显示器中的用途。以下将本发明的这两个主要方面主要分开讨论,但将易于显而易见的是本发明的两个方面可以被并入单个的物理显示器中。
A部分:非可扩散的离子材料
如上所述,一方面,本发明提供了一种光电组件,该组件包括光电层和粘结剂层。所述粘结剂层含有离子材料,所述离子材料中的一种离子不能贯穿粘结剂层迁移而其他离子可以贯穿粘结剂层迁移。这种类型的离子材料防止离子扩散出粘结剂层和潜在地损害了离子扩散至其中的其他层(例如,有机半导体层)。
聚合物粘结剂层中的离子电导已经显示通过“跳跃(hopping)”机制来产生,其中解离的游离离子在离子聚集体(离子对和较高的聚集体)之间穿移,大多数这些聚集体基本上是中性的。根据本发明,离子材料的阴离子和阳离子中的仅一中能够移动。所述固定离子被限制在单个位置,而所述流动离子仍旧自由迁移。合适的离子材料的一个实例是聚合物盐,例如,聚合物羧酸盐的离子盐。在该情况中,羧酸盐离子有效地不可移动,因为它有效地结合到聚合物链且仅能与聚合物一起作为整体来移动。另一方面,所述阳离子抗衡离子可以自由参与跳跃运动,而它可移动的速率取决于与阴离子羧酸盐的静电相互作用的强度、粘结剂介质中羧酸盐抗衡离子聚集体的浓度、介质的粘度以及该抗衡离子被介质溶解的自由能。
如在前述第7,012,735号美国专利中描述的离子掺杂的粘结剂中,在本发明中大量阳离子是有利的,因为它们具有与离子聚集体状态吸引的低静电能量,且因此容易从它们中解离。作为一个实例,季铵碱可以用于中和聚氨酯上的羧酸官能团,导致如上所述能够支持离子导电的季铵羧酸盐聚合物。
离子材料的选择使得在干燥之后最终粘结剂层的电导率可以通过改变聚氨酯的羧酸含量以及还通过所使用的阳离子来变化和调整是希望的。例如,在其中聚氨酯上的羧酸基团被以给定羧酸含量的季铵碱中和的前述系统中,预期电导率按照如下顺序增长:
四甲基铵<四乙基铵<四丁基铵等。
也可以使用磷盐,由于中心原子的尺寸较大,因而磷盐应该比含氮的类似物具有稍高的电导性。其他阳离子种类(例如,金属络合离子)也可以用于该目的。由于离子是介质的固有部分且不能因此作为分离的晶体相来进行相分离,所以粘结剂中离子材料的溶解性在该方法中不是问题。
聚合物粘结剂的酸性组分还可以通过使用具有较高解离常数的基团来取代羧酸组分而制备更强的酸性,所述具有较高解离常数的基团,例如硫酸单酯、磺酸、亚磺酸、膦酸、次膦酸基团或磷酸酯,只要具有至少一种可解离的质子存在。预期季铵盐和其他大的阳离子将最希望被用于抗衡离子,因为其尺寸大并且在干燥的低极性粘结剂介质中的相对高程度离子解离。基于氮的酸如果被结合到足以吸电子的官能团(例如RSO2-NH-SO2R),也可以使用。在该情况中,可以使用几乎任何流动离子,包括叔铵,因为甚至在干燥的粘结剂中流动离子以质子化的形式存在。然而,基于较大的胺(即,具有较长烷基尾的胺)的流动离子仍可能是优选的,因为它们在尺寸上显著较大,并因此包含它们的离子对会更可解离。
供选择地,所述粘结剂上的羧酸盐基团可以与非强布郎斯台德酸(Bronsted acid)的流动离子(即,不具有酸性质子)一起使用,诸如上述季阳离子。
其中阳离子是固定离子的粘结剂组合物可以通过使用聚合物主链中的季铵基团或将其用作侧链并优选使用大的阴离子(例如,六氟磷酸盐、四丁基硼酸盐、四苯基硼酸盐等)作为流动离子而构建。季铵基团可以被磷、锍或其他无可解离的氢的阳离子基团取代,包括通过与金属阳离子络合形成的那些。后者的实例包括聚醚/锂离子包合络合物,尤其是环聚醚(例如,18-冠-6)或具有过渡金属离子的聚胺络合物。在该情况中,阴离子流动离子可包括上述列出的那些类型的离子,加上碱性更强的材料,例如羧酸盐或甚至酚盐。
供选择的固定阳离子粘结剂材料包括含有重复单元的聚合物,该重复单元衍生自碱性单体连同非良好布郎斯台德受体的流动阴离子;所述碱性单体例如,聚(乙烯基吡啶)、聚(β-二甲基氨基乙基丙烯酸盐)等、和含有这样的基团的共聚物,所述非良好布郎斯台德受体的流动阴离子(例如,磺酸盐、硫酸盐、六氟磷酸盐、四氟硼酸盐、双(甲磺酰基)亚胺盐、磷酸盐、膦酸盐等)。衍生自这样的氨基单体的季盐也可以使用,例如聚(N-甲基(乙烯基吡啶)或N-苄基(乙烯基吡啶))、聚(N-烷基-N′-乙烯基咪唑)或聚(N-烷芳基-N′-乙烯基咪唑)和聚(β-三甲铵乙基)丙烯酸盐或聚(β-三甲铵乙基)甲基丙烯酸盐的盐,以及包含这些离子基团的乙烯基共聚合物。如先前所述,较大的流动离子为优选。
这些化学改性的技术不限于聚氨酯,但可应用于具有合适结构的任何聚合物。例如,基于乙烯基的聚合物可含有阴离子或阳离子固定离子。
B部分:经渗析或渗滤的粘结剂材料和/或粘合剂
如已经指明的,本发明的一方面减轻或消除由来自粘结剂层的离子掺杂剂迁移至光电显示器的其他层引起的问题,尤其是对包含由某些有机半导体制成的有源矩阵后面板的损害。然而,已经发现,这些问题的原因不限于离子掺杂剂,而包括存在于现有技术粘结剂和粘合剂组合物中的其他逸散物,其可以以与离子掺杂剂相似的方式从粘结剂层或粘合剂层迁移至光电显示器的其他层。一种这样的特别受关注的逸散物是N-甲基吡咯烷酮(NMP),其被用作聚氨酯制备中的溶剂。在一些情况中可以受关注的其他逸散物包括在聚氨酯的制备中使用的其他溶剂,和来自聚合反应的可渗析的不易表征的低分子量分子。已经发现通过仔细干燥粘结剂层去除NMP改进了该层的储存稳定性。层压粘结剂的渗析去除NMP还有其他低分子量材料,且甚至更有效。本发明的非可扩散的离子材料粘结剂组合物可经受渗析,这是由于电中性防止固定离子和流动离子显著分离,且在渗析之后,所述粘结剂材料含很少或不含可扩散的材料。因此,已经发现本发明的粘结剂可以特别有效减轻层压粘结剂对含有有机半导体的后面板的性能的有害作用。渗滤也可以代替渗析来使用。
如先前指明的,本发明的非可扩散的离子粘结剂材料可以通过渗析或渗滤纯化。然而,通过渗析合成这些粘结剂材料也可以是有用的。例如,可以通过在合适的水溶性金属盐溶液中渗析聚合物溶液将聚胺或聚醚的水溶液部分转化为阳离子络合物。
在将传统聚氨酯粘结剂与传统的离子掺杂剂一起混合之前,渗析或渗滤也可以用于从该粘结剂去除NMP和其他逸散物。因此,如已经指明的,在其第二个主要方面,本发明提供了一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包含聚合物粘结剂材料,所述聚合物粘结剂材料已经经受渗析或渗滤而去除具有小于约3,500的分子量的有机物。这样的渗析或渗滤可用于去除除了其他物质以外的NMP、四氢呋喃(THF)以及丙酮。相似地,本发明的第二个方面还提供了一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包含聚合物粘结剂材料,在所有情况中,所述聚合物粘结剂材料具有不超过基于粘结剂层和光电材料层的总重量计的约500ppm的N-甲基吡咯烷酮、优选地不超过约200ppm,并且希望地不超过约100ppm。
本发明的第二方面还提供了一种电泳介质,该介质包括连续相和非连续相,所述非连续相包含许多液滴,各液滴包含悬浮流体和置于该悬浮流体中且当向电泳介质施加电场时能够贯穿流体移动的至少一种粒子,所述连续相包围和封装所述非连续相并包含聚合物粘合剂,所述聚合物粘合剂已经经受渗析或渗滤而以去除具有小于约3,500分子量的有机物。所述电泳介质可以是封装或聚合物分散的类型,即,在各液滴和粘合剂之间可以是胶囊壁或不是胶囊壁。本发明的第二个方面还提供了一种电泳介质,该电泳介质包括连续相和非连续相,所述非连续相包含许多液滴,各液滴包含悬浮流体和置于该悬浮流体中且当将向电泳介质施加电场时能够贯穿流体移动的至少一种粒子,所述连续相包围和封装所述非连续相,并包含聚合物粘合剂,在所有情况中所述聚合物粘合剂具有不超过基于电泳介质(即,所述连续相和非连续相的组合)的重量计的约1000ppmN-甲基吡咯烷酮、四氢呋喃和丙酮、优选地不超过约400ppm,并且希望地不超过约200ppm。
如已经指出的,本发明的第二个方面可用于从光电显示器中使用的层压粘结剂和/或粘合剂去除NMP和可能其他逸散物。在许多情况中,从粘合剂去除逸散物比从层压粘结剂去除逸散物更重要。层压粘结剂层的制备通常包括将可流动形式的粘结剂涂覆到释放片上,然后将粘结剂层干燥,使得在所述释放片上形成粘结剂的粘结层。在干燥步骤过程中的高温和低涂覆速度足以驱除大部分的挥发性有机物,例如,已经发现以50,000ppm的NMP涂覆的层压粘结剂在干燥之后仅具有200ppm的NMP。另外,由于仅在干燥过程中存在的层为层压粘结剂和释放片(将粘结剂层压至光电介质仅在干燥步骤之后发生),干燥条件的选择可以仅基于层压粘结剂本身的性质,且不需要考虑光电介质的性质。相比之下,用于光电介质的粘合剂通常与介质的非连续相混合在一起,以形成淤浆,所述淤浆然后被涂覆并干燥形成电泳介质。因此,在该情况中,干燥条件必须考虑非连续相的性质,特别是关注挥发性非连续相溶剂的同步去除。最后,从质量控制的观点出发,去除具有损害任何后面板(预期光电介质可以与之接触)的可能性的所有材料表现为良好的保险措施,使得未知组分(其浓度可随未知或对照改变)的数量被保持至最小,显而易见地,作为良好制造工艺的物质,已知组合物的纯材料的使用是非常合乎需要的。
渗析和渗滤均为熟知的纯化胶体和聚合物悬浮液的方法。在这两种技术中,通过位于洗液(通常水或缓冲溶液)相对侧的半透膜限定悬浮液。可以穿过膜的且可溶于洗液的分子在设备的两个区域之间平衡,并通过交换洗液来从悬浮液中去除。通常,所述膜由允许低分子量物质选择性通过的材料制成,且水通常用作溶剂;在本发明中,已发现具有约3.5kD截留分子量(MWCO)的膜是有用的。由于NMP是水溶性溶剂,这些技术良好地适于去除该污染物。同时,其他可溶性物质(有些具有潜在的有害性质)也可以被去除。不需要通过略微蒸发去除物质,如通过干燥去除的情况中。通过调整膜的性质,可以改变被去除的分子的种类。例如,如果在特定的层压粘结剂或粘合剂存在的水溶性寡聚物中,片段是个问题,具有较高MWCO的膜可以被用于去除这样的片段,多种具有不同MWCO’s的半透膜可商购获得。
渗析或渗滤可以用于本发明的工艺,但对于商业生产而言,渗滤通常是优选的。渗析是一种简单的平衡工艺,而渗滤应用高流动条件和高跨膜压力以加速通过膜的大量运输。渗滤基本上比渗析快速,并且可以在防止材料的稀释液被纯化的条件下应用,如在渗析中的通常情况。渗滤是可容易调整的工艺,并且实验室规模和生产规模的设备可以以合理的价格获得。渗滤是良好建立的工业程序,广泛用于生物化学和其他工业。
本发明人已经揭示渗析和渗滤均有效地从商业聚氨酯胶乳的悬浮液去除NMP。已经发现使用具有低MWCO(3.5kD)的膜对聚氨酯胶乳进行渗析和渗滤可以在几小时内将NMP含量减少超过一个数量级。例如,通过渗滤将一种聚氨酯粘合剂的NMP含量从约14%(140,000ppm)减少至约500ppm。当使用渗析时,NMP去除的效率可受到胶乳的稀释度的限制,这使得乳液难以涂覆,尤其在层压粘结剂的情况中。可通过在减压下蒸发多余的水分来浓缩胶乳,但这是笨拙的方法。纯化的聚氨酯胶乳的分子量分布的测量显示其基本上与原材料一致,即在渗析过程中无聚合物损失。当经渗析的材料取代未经渗析的粘合剂和层压粘结剂使用时,观察到许多优点。
首先,有机半导体后面板性能降低被大量消除。如果仅对粘合剂且非层压粘结剂进行渗析可获得相同的结果。然而,如果省略粘合剂渗析,则有机半导体装置的性能经历严重降低。
第二个优点是使用经渗析的材料,电池带宽电阻(前面板层压板的电导率的测量)较高,通常达约50%。较高的电池带宽电阻对运行晶体管的导通状态电导率提出了较少的要求(也就是说,较低的截留率是可允许的)。这对于有机半导体晶体管来说是特别重要的特性,有机晶体管的截留率通常不如无机晶体管的截留率高。
第三个优点是由经渗析的胶乳制备的电泳介质的光电特性具有些许改进。如下文实施例5中所述,相对于使用未经渗析的材料,使用经渗析的聚氨酯胶乳导致约2L*的动态范围(介质的极白和极黑光电状态之间的差异)的改进(使用L*的常用CIE定义)。
现在给出(但仅通过例示的方式)下列实施例以显示用于本发明的优选试剂、条件以及技术的详细情况。
实施例1:利用四丁基氢氧化铵中和来合成TMXDI-PPO聚氨酯
在该实施例中制备的聚氨酯与下文实施例2中制备的现有技术聚氨酯相似,除了具有较高的酸含量。
在配备磁力搅拌器、冷凝器以及进氮口的三颈圆底烧瓶中制备预聚物。在氮下进行反应。将四甲基二甲苯二异氰酸酯(TMXDI,由Aldrich Chemical公司供应,16.34g,0.067mol)、聚(丙二醇)二醇(由Aldrich Chemical公司供应,平均Mn ca.2000,33.5g,0.0168mol)以及二月桂酸二丁基锡(由AldrichChemical公司供应,0.04g)装入烧瓶,并在90℃下于油浴中将混合物加热2小时。之后,将1-甲基-2-吡咯烷酮(购自Aldrich,8.5g)的2,2-双(羟甲基)丙酸(购自Aldrich,3.35g,0.025mol)溶液加入至烧瓶,并且使得在90℃下再继续反应2小时,以获得末端为NCO的预聚物。然后,将反应混合物的温度降低至70℃。将四丁基氢氧化铵(NBu4OH)(购自Aldrich,6.15g,0.0237mol)和去离子水(100g)分开装入配备有机械搅拌器、温度计和进氮口的500mL夹套玻璃反应器中,并且将所得的混合物在氮下加热至35℃。然后,将预聚物混合物缓慢地加入到NBu4OH水溶液中,以在机械搅拌和氮气氛下将该预聚物转化为水性分散体。在分散步骤之后,在35℃下使用溶于小量水的六亚甲基二胺(购自Aldrich)进行链增长反应。从pH测量值来确定链增长反应的终点。最后,将所得的分散体加热至50℃1小时,以确保任何残留的异氰酸酯基团被水消耗。
实施例2:使用三乙胺中和来合成TMXDI-PPO聚氨酯(对照)
重复实施例1达到获得末端为NCO的预聚物的点,并且反应混合物的温度降低至70℃的点。之后,经30分钟的时间缓慢加入三乙胺(购自Aldrich,2.4g,0.0237mol),以中和羧酸。然后,在机械搅拌和氮气氛下将该反应混合物缓慢地加入到500mL夹套玻璃反应器中的35℃去离子水中,以将预聚物转化为水性分散体。以实施例1中的相同方式进行链增长反应并将分散体最终加热至50℃。
实施例3:由实施例1和2中制备的材料来制备实验性单像素显示器
将上述实施例1和2中制备的聚氨酯分开涂覆到厚度(干燥的)约20μm的金属化释放膜上。在带传输干燥炉中于60℃并且以1ft/min(约5.1mm/sec)的传输速率对经涂覆的聚合物膜进行干燥,已知这些条件将NMP的含量减小至非常低的水平。基本如第7,002,728号美国专利的实施例4中所描述的分开制备电泳介质,并将其涂覆至氧化铟锡(ITO)涂覆的5mil(127μm)聚对(苯二甲酸乙二酯)(PET)膜的表面上(一个表面涂覆ITO)。将两个次组件相互层压,使电泳层与层压粘结剂相接触以形成前述第6,982,178号美国专利中所述的前面板层压板。从前面板层压板剥脱释放片,并将余下的层(包括PET膜上的碳黑层)层压至实验性单像素2英寸(51mm)见方的后面板,以形成实验性单像素显示器。无添加的掺杂剂加入到任何粘结剂涂层中。在50%相对湿度下调节实验性显示器(如在几个前述的E Ink专利和专利申请中所讨论的,电泳显示器的光电性质随电泳层的湿度而变化,且因此在检测前在标准条件下调节试验样品是希望的)。
然后,检测实验性显示器的光电性质,该检测是通过在不同电压下使用250毫秒脉冲将实验性显示器驱动至其黑光状态和白光状态,测定黑光状态和白光状态的反射率,以及将这些反射率转化至为传统的L*值,其中,L*具有通常的CIE定义:
L*=116(R/E0)1/3-16,
其中,R是反射率,R0是标准的反射率值。下表1显示了以不同电压实现的动态范围(黑光状态和白光状态的L*值之间的差异):
表1
  层压粘结剂中和剂   电伏(V)  动态范围(L)
  三乙胺(对照)   7.5  7.1
  10  14.1
  12.5  20.0
  15  24.4
  层压粘结剂中和剂   电伏(V)  动态范围(L)
  四丁基氢氧化铵(本发明)   7.5  21.5
  10  30.7
  12.5  35.4
  15  37.7
从表1将看出,本发明的层压粘结剂显示在所有驱动电压下显著大于对照粘结剂的动态范围。该改进与从电导率差异所预期的一致,且与使用具有较低酸含量的现有技术掺杂粘结剂发现的相似。使用三乙胺中和的对照粘结剂显示了对于很强电阻性的层压粘结剂期望的光电反应。在操作过程中显示器的目测观察显示了具有对照粘结剂的显示器仅显示在显示器边缘的小量发光,而使用本发明的粘结剂的显示器表现了大量的发光。高度的发光也与具有高电导率的粘结剂一致。
实验性显示器还经受低温检测。如在几个前述E Ink专利和专利申请中所讨论的,电泳显示器的光电性质在低温下趋于快速降低,这至少部分因为层压粘结剂的电导率随温度的降低而降低。为了确定本发明的实验性显示器的低温行为,使用250或500毫秒的15V脉冲在+25至-25℃的温度下驱动显示器,并使用驱动脉冲结束之后2分钟所取的反射率值测定动态范围。(在取反射率值之前的这两分钟停顿允许某些影响反射率值消散的短期效应)。以前述的相同方式将获得的反射率值转变为动态范围值,结果示于下列表2中。
表2
  温度℃   驱动脉冲(ms)   动态范围(L)
  25   250   35.1
  15   250   35.8
  5   250   33.4
  -5   250   25.5
  -5   500   31.2
  -15   500   20.2
  -25   500   4.4
从表2中的数据将看出,本发明的粘结剂提供了低至约-10℃的合适性能,条件是使用脉冲长度补偿,即,条件是在低温下延长驱动脉冲。该低温性能与高度掺杂的现有技术层压粘结剂的低温性能具有可比性。
实施例4:通过渗析纯化本发明的层压粘结剂
将以上实施例1中制备的层压粘结剂样品(49.3g,35%wt.固体)置于渗析膜管(Fisher(注册商标)再生的纤维素膜,MWCO 3500)中。在使用夹具封闭该管两端之后,将该管浸没于连续补充、搅拌的水槽中约4小时。然后,在该时间结束时,回收61.6g材料,其中固体含量29.5%(95%回收率)。一开始,NMP含量为4.4%,在渗析之后,其含量为1.4%。NMP含量可用作去除其他水溶性低分子量材料的替代指标。
使用以上实施例4中所制备的经渗析的层压粘结剂与现有技术层压粘结剂(经渗析和未经渗析的)和专有的有机半导体后面板对显示器的预备性长期储存试验表明,本发明的经渗析的层压粘结剂比现有技术粘结剂具有显著较好的长期储存特性。
实施例5:经渗析的粘合剂和层压粘合剂在电泳显示器中的应用
基本如第2008/0074730号美国专利申请公开的实施例2中所述合成一种聚氨酯胶乳,并且将其用作下文描述的实验中的粘合剂。基本如第2005/0107564号美国专利申请公开的实施例2中所述合成另一种聚氨酯胶乳,并且将其用作这些实验中的层压粘结剂。
基本如第7,002,728号美国专利的实施例7中所述来制备实验性单像素显示器,但使用前述粘合剂和层压粘结剂,所述层压粘结剂掺杂有180ppm的四丁基六氟磷酸铵。如下生产了四组实验性显示器:
(A)对粘合剂或层压粘结剂均不进行渗析;
(B)基本如上文实施例4中所述对粘合剂进行渗析,但未对层压粘结剂进行渗析;
(C)基本如上文实施例4中所述未对粘合剂进行渗析,但对层压粘合剂进行渗析;以及
(D)基本如上文实施例4中所述对粘合剂和层压粘结剂均进行渗析。
然后,基本如第7,002,728号美国专利的实施例7中所述对四组实验性显示器的光电性质进行检测,但使用300毫秒的±15V脉冲,并且测量极白和极黑状态反射率,并将其转化为CIE L*单位。结果示于附图的唯一图表中。在各组读数中,左侧条代表显示器的极白状态,中心条代表极黑状态,而右侧条代表动态范围(即,以L*单位测量的极白和极黑状态之间的差异)。
从图表中将见的是,粘合剂和层压粘结剂的渗析对显示器的光电性质均无不良作用。确实,其中粘合剂经渗析的两种显示器(B和D)显示了改进的白色状态,显示器C和D显示了改进的黑色状态(黑色状态的改进当然由较低的L*值表示)。其中粘合剂和层压粘结剂均经渗析的显示器D显示了四组显示器的最大动态范围。
使用100和500毫秒持续时间的±15V脉冲和100、300以及500毫秒的±10V脉冲重复光电检测。在所有情况中,所获得的结果与图中显示的那些一致。
当使用有机晶体管将在上文(A)-(D)中提到的含有粘合剂和层压粘结剂组合的前面板层压板层压至后面板时,观察到含有未经渗析的粘合剂的前面板层压板造成有机晶体管快速降解,而含有经渗析的粘合剂的前面板层压板未造成有机晶体管快速降解。使用经渗析的层压粘结剂观察到相似但较小的作用。
从前述内容将看出本发明可以提供层压粘结剂,所述层压粘结剂提供了与现有技术粘结剂有可比性的光电特性和低温性能,而避免使用可损害某些后面板以及可能导致其他问题的逸散离子。另外,本发明可以提供以下权利要求。

Claims (20)

1.一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包括聚合物粘结剂材料和离子材料,所述离子材料的阳离子和阴离子中的一种固定于所述聚合物粘结剂材料,并且其阳离子和其阴离子的另一种自由地贯穿聚合物粘结剂材料迁移,所述离子材料降低所述聚合物粘结剂材料的体电阻率,并且将所述聚合物粘结剂材料加热至50℃所述离子材料不被去除。
2.根据权利要求1所述的光电组件,其中,所述离子材料包括固定于所述聚合物粘结剂材料的季铵或鏻阳离子和羧酸盐阴离子。
3.根据权利要求1所述的光电组件,其中,所述聚合物粘结剂材料包括聚氨酯。
4.根据权利要求1所述的光电组件,其中,所述离子材料包括固定于所述聚合物粘结剂材料的季铵或鏻阳离子和六氟磷酸盐、四丁基硼酸盐或四苯基硼酸盐阴离子。
5.根据权利要求1所述的光电组件,其中,所述离子材料包含由碱性单体和选自磺酸盐、硫酸盐、六氟磷酸盐、四氟硼酸盐、双(甲烷磺酰)亚胺盐、磷酸盐以及膦酸盐的流动阴离子衍生的重复单元。
6.根据权利要求5所述的光电组件,其中,所述碱性单体包括乙烯基吡啶、β-二甲氨基乙基丙烯酸盐、N-甲基(乙烯基吡啶)或N-苄基(乙烯基吡啶)、N-烷基-N′-乙烯基咪唑或N-烷芳基-N′-乙烯基咪唑以及β-(三甲基氨基乙基)丙烯酸盐或β-(三甲基氨基乙基)甲基丙烯酸盐中的任何一种或多种。
7.根据权利要求1所述的光电组件,其中,所述光电材料包括电泳材料,所述电泳材料包含置于流体中的并且能够在电场影响下贯穿所述流体移动的大量带电粒子。
8.根据权利要求7所述的光电显示器,其中,所述流体是气态的。
9.一种包括根据权利要求1所述的光电组件的光电显示器、前面板层压板、反转式前面板层压板或双释放膜。
10.一种包括根据权利要求9所述的光电显示器的电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签或闪存驱动器。
11.一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包含聚合物粘结剂材料,所述聚合物粘结剂材料已经经渗析或渗滤来去除具有小于约3,500分子量的有机物。
12.一种光电组件,该组件包括粘结剂层和光电材料层,所述粘结剂层包含聚合物粘结剂材料,基于所述粘结剂层和所述光电材料层的总重量计,该聚合物粘结剂材料具有含量不超过500ppm的N-甲基吡咯烷酮。
13.根据权利要求12所述的光电组件,其中,所述聚合物粘结剂材料包括聚氨酯。
14.根据权利要求12所述的光电组件,该组件具有含量为不超过200ppm的N-甲基吡咯烷酮。
15.根据权利要求12所述的光电组件,其中,所述光电材料包括电泳材料,所述电泳材料包含置于流体中的并且能够在电场影响下贯穿流体移动的大量带电粒子。
16.根据权利要求15所述的光电显示器,其中,所述流体是气态的。
17.一种包含根据权利要求12所述的光电组件的光电显示器、前面板层压板、反转式前面板层压板或双释放膜。
18.一种包含根据权利要求17所述的光电显示器的电子书阅读器、便携式计算机、平板计算机、手机、智能卡、标示牌、手表、货架标签或闪存驱动器。
19.一种电泳介质,该介质包括连续相和非连续相,所述非连续相包括大量液滴,各液滴包括悬浮流体和被置于该悬浮流体中的且当向电泳介质施加电场时能够贯穿流体移动的至少一种粒子,所述连续相包围并封装所述非连续相并且包括聚合物粘合剂,所述聚合物粘合剂已经经渗析或渗滤来去除具有小于3,500的分子量的有机物。
20.一种电泳介质,该介质包括连续相和非连续相,所述非连续相包含大量液滴,各液滴包括悬浮流体和被置于该悬浮流体中的且当向电泳介质施加电场时能够贯穿流体移动的至少一种粒子,所述连续相包围并封装所述非连续相并且包括聚合物粘合剂,基于电泳介质重量计,所述聚合物粘合剂具有含量不超过1000ppm的N-甲基聚吡咯烷酮。
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US20160377952A1 (en) 2016-12-29
TWI451966B (zh) 2014-09-11
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US9964831B2 (en) 2018-05-08
KR20100074275A (ko) 2010-07-01
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EP2217440B1 (en) 2019-03-06
HK1145478A1 (zh) 2011-04-21
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US20090122389A1 (en) 2009-05-14
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US20160170282A1 (en) 2016-06-16
KR101379587B1 (ko) 2014-03-31
CN101855083B (zh) 2015-01-21
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EP2217440A1 (en) 2010-08-18
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KR102079851B1 (ko) 2020-02-20
EP3505585A1 (en) 2019-07-03
WO2009064642A1 (en) 2009-05-22
KR20120089372A (ko) 2012-08-09

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