CN1250457A - 聚合物涂覆的介电粒子及配制物和制备它的方法 - Google Patents

聚合物涂覆的介电粒子及配制物和制备它的方法 Download PDF

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CN1250457A
CN1250457A CN98803274A CN98803274A CN1250457A CN 1250457 A CN1250457 A CN 1250457A CN 98803274 A CN98803274 A CN 98803274A CN 98803274 A CN98803274 A CN 98803274A CN 1250457 A CN1250457 A CN 1250457A
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pigment particles
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J·H·陈
F·E·舒伯特
W-H·侯
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Abstract

用于电泳显示的适当涂覆的颜料粒子,包括具有预定密度的颜料粒子和在颜料粒子上涂覆聚合物涂层,其中涂层含有一种近氟化聚合物,并且其中氟化聚合物的密度与颜料粒子的密度基本相同。当涂覆的聚合物涂层的密度与颜料粒子的密度基本相同时,即使粒子包含粒径分布,颜料粒子的密度也不会明显地改变。在一个优选的实施方案中,颜料粒子含有一种密度为1.43g/ml的二芳基化物黄颜料,以从密度为1.41g/ml的2,3,4,5,6-五氟苯乙烯单体制备的聚合物涂覆。

Description

聚合物涂覆的介电粒子及配制物和制备它的方法
本发明涉及应用于电泳图像显示、静电印刷或其类似中的、涂覆以氟聚合物的介电颜料粒子,及其相应的配制物和制备它的方法。
电泳效应是人所共知的,现有的技术中充斥着大量的描述此效应的专利和文献。如本领域熟练技术人员所知,电泳效应发生的原理是,某些粒子,当悬浮在一种介质中时,能够带上电荷并进而被诱导穿过介质迁移到带有相反电荷的电极。静电印刷和电泳图像显示器(EPID)利用电泳效应来产生所要的图像。利用电泳效应的设备,优选例如见美国专利4,732,830,于1988年3月22日授权给Frank J.DiSanto等,标题ELECTROPHORETIC DISPLAY PANELS AND ASSOCIATEDMETHODS,转让给Copytele公司,即本文中的受让人。
在现有的EPID技术中,介电粒子悬浮于透明的或同介电粒子相比呈光学对照色的流体介质中。为在粒子和悬浮介质之间产生最强烈的光学对比,希望是浅色的粒子悬浮在深色的介质中或者黑色的粒子悬浮在逆光透明的介质中。有大量的颜料粒子和分散介质组合物在技术中是已知的。比如参见美国专利4,298,444,于1981年11月3日授权给K.Muller等,标题ELECTROPHORETIC DISPLAY。
在现有的技术中,已证明很难制备介电的、均一粒径的、并具有匹配常用悬浮介质的密度的黑色电泳粒子。结果是,EPID通常采取将容易制备的浅色电泳颜料粒子悬浮在含有深色染料的介质中。此类EPID例见美国专利4,655,897,授权给DiSanto等;美国专利4,093,534,授权给Carter等;美国专利4,298,448,授权给Muller等;和美国专利4,285,801,授权给Chiang。如下专利给出了黄颜料粒子的用途,都授权给Frederic E.Schubert并转让给Copytele公司,见本文中的受让人;美国专利5,380,362,授权于1995年1月10日,标题SUSPENSION FOR USE IN ELECTROPHORETIC IMAGE DISPLAYSYSTEMS;美国专利5,403,518,授权于1995年4月4日,标题FORMULATIONS FOR IMPROVED ELECTROPHORETIC DISPLAY SUSPENSIONSAND RELATED METHODS;及美国专利5,411,656,授权于1995年5月2日,标题GAS ABSORPTION ADDITIVES FOR ELECTROPHORETICSUSPENSION。此三篇专利在此参考引用。
如本领域熟练技术人员所知,用于EPID的电泳粒子的选择是非常重要的,它决定EPID的效果和生成图像的质量。理想的情况是,电泳粒子应该具有理想的电荷质量比,有赖于其粒径和表面电荷;理想的电荷质量比是希望的,以实现良好高速静电沉积以及粒子运动在电压改变时的快速反转。还有,希望采用与其中悬浮有的粒子流体介质的密度基本相同的电泳粒子。通过选用与悬浮介质密度基本相同的电泳粒子,保证电泳粒子穿过介质的迁移与EPID定向及重力无关。粒子因此会在流体介质中保持无规分散。
对用于EPID或其它电泳设备的电泳粒子施以聚合物涂覆是有优点的。粒子所带的适当涂层可具有增强粒子散光能力的作用。当聚合物涂覆的粒子撞击透明的屏幕电极(从而从屏幕上取代流体介质)时,会得到更亮的色彩和更强烈的图像(同采用非涂覆粒子的情况相比)。除此之外,为提高EPID的效率和半衰期,很自然地希望采用稳定的并且不易与悬浮介质发生相互作用的电泳粒子;悬浮介质可以包括比如芳香或脂肪族溶剂,包括苯、甲苯、烃油、壬烷(novane)、癸烷或其类似物等,它们可能会跟用于EPID的一些典型颜料粒子发生反应。同未涂覆粒子相比,聚合物涂覆的颜料粒子给出更硬和更抗溶剂的复合体。
而且,适当涂覆的电泳粒子更不易粘附到电泳室内表面上。近几年来,注意力已经被引向通过在粒子表面吸附聚合物以实现分散体的稳定上。比如参见P.Murau和B.Singer的文章,刊登于Vol.49,No.9,Journal of Applied Physics(1978),标题为“The Understandingand Elimination of Some Suspension Instabilities in anElectrophoretic Display”。也参见美国专利5,403,518,授权给Schubert,参见前文,以及美国专利4,285,801,于1981年8月25日授权给Anne A.Chiang,标题为ELECTROPHORETIC DISPLAYCOMPOSITION。
如果两个覆有聚合物吸附层的胶体粒子彼此接近,一旦聚合物层开始渗透就会产生空间位阻。按照Murau和Singer的提法,吸附在胶体粒子上的聚合物分子并不是平铺在表面上的。而是,一部分的烃长链(自由端基、侧链及环体)游离于表面并被流体所包围。
已发现高氟聚合物用作颜料粒子涂层是有利的,因为它们具有低的临界表面张力而倾向产生防粘特性。比如见M.Hudlicry和A.E.Pavlath的文章,刊登于Vol.187,pp.983,ACS Monograph(1995),标题为“Properties of Fluorinated Compounds II”。当用作颜料粒子涂层时,全氟聚合物较低的表面张力会减少颜料粒子表面与含有其中分散有粒子的悬浮介质的溶剂之间的相互作用。
可是,涂覆电泳粒子有缺点。如所述,希望采用与流体介质,其中有粒子悬浮,的密度基本相同的电泳粒子。可是,因为未涂覆的颜料粒子含有相当宽的粒径分布,均一厚度的涂层会产生不同密度的粒子分布。
因此,本发明的一个目的是给出聚合物涂覆的颜料粒子,其中涂覆粒子的密度保持与其中悬浮有粒子的流体介质的密度基本相同。本发明的优势包括给出适当涂覆的颜料粒子,其具有增强的散射光能力以产生更明亮的色彩;更硬、更耐溶剂的复合体;以及对电泳室内表面的防粘性。
涂覆颜料粒子的现有方法所存在的问题和缺点在本发明中得到克服,本发明包括具有预定密度颜料粒子的选择以及颜料粒子上聚合物涂层的涂敷,其中涂层包括高氟聚合物,并且其中聚合物密度与颜料粒子密度基本相同。当采用密度与颜料粒子密度基本相同的聚合物涂层时,即使粒子含有粒径分布,颜料粒子的密度也不会有明显改变。
在一个优选的实施方案中,颜料粒子包括密度为1.43g/ml的二芳基化物黄颜料,涂覆以制备自密度为1.41g/ml的2,3,4,5,6-五氟苯乙烯单体的聚合物。这些涂覆的颜料粒子优选悬浮在包括四氯乙烯和仲丁基苯混合物的介质中,介质平衡至比重为1.43g/ml。本发明涂覆颜料粒子的方法包括聚合反应技术,其中五氟苯乙烯单体,在分散于有机溶剂中的颜料粒子的存在下借助自由基聚合反应引发剂聚合。
图1,唯一的图例,是简图,是一种EPID截视图,它含有本发明的粒子。
虽然本发明可以应用于许多不同领域,其中希望采用含带相反电荷粒子的分散体,比如涂料、油墨和电泳墨粉,但它特别适合应用在同电泳图像显示器(EPID)相关的领域。因此,本发明结合一种典型的EPID进行描述。
参考图1,它表示的是一个简单电泳图像显示器10片段的截视图,被放大以显示每一个像素。如本领域熟练技术人员所知,EPID含有一定体积的置于阳极14和阴极16之间的电泳分散体12。阳极14和阴极16以铟-锡-氧化物(ITO)或类似化合物薄层的形式沉积在玻璃底盘18、20上。ITO层的沉积方式是当透过玻璃底盘18和20看时是几乎透明的。
电泳分散体12含有大量的介电电泳粒子22悬浮在流体介质24中。电泳粒子22具有基本等于流体介质24的密度,以便保持无规分散,不受EPID定位或重力效应的影响。按照本发明,粒子涂覆以聚合物涂层26。当在阳极14和阴极16之间施加以足够的电子偏转时,有赖于极性,粒子22迁移至阴极16或阳极14,并且取代靠近ITO层的暗色介质,从而产生明亮的像素。反转电压产生暗的像素。
为制备应用有本发明聚合物涂层的电泳悬浮体的颜料粒子,任何已知的方法都可采用。优选二芳基化物黄颜料,名为AAOT黄#374-73,由Sun Chemical Company制造。这种黄色颜料具有密度1.43/ml。按照本发明的一个优选的实施方案,用作悬浮体介质24的溶剂是四氯乙烯和仲丁基苯。四氯乙烯的高比重1.62g/ml,允许借助密度较低的仲丁基苯将比重平衡至1.43g/ml。因此,溶剂可以平衡至达到与颜料粒子密度基本相同的比重。
当根据本发明涂敷聚合物涂层时,即使选用宽的粒径分布,颜料粒子的密度也不会明显改变。选用2,3,4,5,6-五氟苯乙烯作为待聚合单体并涂成涂层。当此单体聚合时,产生起颜料粒子有效涂层作用的氟聚合物,其具有低的临界表面张力。五氟苯乙烯具有密度1.41g/ml,当用于制备AAOT黄颜料#374-73的聚合物涂层时,涂层密度与颜料粒子的密度大约相同以便保持粒子密度的均一性。
考虑到本发明的聚合物涂覆颜料粒子的工艺,可替换的聚合配方列于表I和表II:表I物质                          质量(g)颜料                          1.184,4″-偶氮双(4-氰基戊酸)     0.05五氟苯乙烯                    0.75癸烷                          30.0乙醇                          5.0表II物质                         质量(g)颜料                         1.184,4″-偶氮双(4-氰基戊酸)    0.05五氟苯乙烯                   0.50仲丁基苯                     30.0乙醇                         3.0
材料在温度控制的转鼓反应器中混合。反应混合物在32rpm和60摄氏度下鼓转大约24小时,然后在70摄氏度下鼓转12小时。所得涂覆粒子以己烷和醇的洗液清洗。然后在真空烘箱中干燥。对给定的应用来讲,通过改变表I或表II的配方,或改变制备工艺的其它反应参数,涂覆的电泳颜料粒子的物理特性会任选改变。
如所述,颜料优选二芳基化物黄颜料,名为AAOT黄#374-73,因为此颜料的密度为1.43g/ml,以及优选单体2,3,4,5,6-五氟苯乙烯,其密度为1.41g/ml。但是,本领域熟练技术人员所知的其它颜料粒子和单体也可采用,关键是颜料粒子密度与单体密度基本相同,以及优选具有高氟原子含量的聚合物涂层。其它的颜料粒子可以包括比如汉撒黄、芳基化物黄、Hostaperm黄、Novoperm黄和其它任何适宜的有机颜料。
还有,本领域熟练技术人员可知其它自由基聚合反应引发剂或溶剂也可采用。4,4″-偶氮双(4-氰基戊酸)优选作为聚合反应引发剂;可是,其它的自由基聚合反应引发剂可以包括2,2″-偶氮双(2-甲基-丁腈)、过氧化苯甲酰、过氧化月桂酰、过氧化辛酰及其类似物。优选的癸烷或仲丁基苯溶剂可以以烃溶剂替换,比如苯基二甲苯基乙烷、甲苯、苯、二甲苯、环己烷、苯基辛烷、辛烷和十六烷十氢化萘。
本领域熟练技术人员所做的符合本发明描述的任何等同、变化以及改进都倾向于包括在附录权利要求所定义的本发明范围内。

Claims (20)

1.电泳悬浮体,包括大量的颜料粒子悬浮在流体介质中,其中颜料粒子具有预定的密度并涂覆以氟化聚合物,其具有与颜料粒子密度基本相同的密度。
2.权利要求1的电泳悬浮体,其中颜料粒子选自二芳基化物黄、汉撒黄、芳基化物黄、Hostaperm黄和Novoperm黄。
3.权利要求1的电泳悬浮体,其中颜料粒子包括密度约1.43g/ml的黄色二芳基化物颜料。
4.权利要求1的电泳悬浮体,其中聚合物材料包括聚合的五氟苯乙烯单体。
5.权利要求4的电泳悬浮体,其中单体是密度约1.41g/m1的2,3,4,5,6-五氟苯乙烯。
6.权利要求3的电泳悬浮体,其中流体介质包括四氯乙烯和仲丁基苯的混合物,平衡至比重大约为1.43g/ml。
7.权利要求1的电泳悬浮体,其中颜料粒子包括密度约1.43g/ml的黄色二芳基化物颜料粒子;并且其中氟化聚合物材料包括一种聚合物,其制备自密度约1.41g/ml的2,3,4,5,6-五氟苯乙烯单体的聚合反应。
8.用于涂覆应用在电泳设备上的颜料粒子的配制物,其包括混合物:
(a)具有一定预定密度的大量颜料粒子;
(b)自由基聚合反应引发剂;
(c)五氟苯乙烯单体,其密度基本等于颜料粒子密度;和
(d)一种有机溶剂。
9.权利要求8的配制物,其中大量颜料粒子选自二芳基化物黄、汉撒黄、芳基化物黄、Hostaperm黄和Novoperm黄;其中自由基聚合反应引发剂选自4,4′-偶氮双(4-氰基戊酸)、2,2′-偶氮双(2-甲基-丁腈)、过氧化苯甲酰、过氧化月桂酰、过氧化辛酰;以及其中有机溶剂包括脂肪和芳香族烃溶剂的混合物,选自癸烷、仲丁基苯、苯基二甲苯基乙烷、甲苯、苯、二甲苯、环己烷、苯基辛烷、辛烷和十六烷十氢化萘。
10.权利要求8的配制物,其中大量颜料粒子(a)进一步包括大约1.18g密度约1.43g/ml的二芳基化物黄颜料。
11.权利要求10的配制物,其中自由基聚合反应引发剂(b)进一步包括大约0.02-0.06g的4,4'-偶氮双(4-氰基戊酸)。
12.权利要求11的配制物,其中五氟苯乙烯单体(c)进一步包括大约0.50-2.00g密度大约1.41g/ml的2,3,4,5,6-五氟苯乙烯。
13.权利要求12的配制物,其中有机溶剂(d)进一步包括大约30-35g癸烷和3-7g醇的混合物。
14.权利要求11的配制物,其中五氟苯乙烯单体(c)进一步包括大约0.50g密度约1.41g/ml的2,3,4,5,6-五氟苯乙烯。
15.权利要求14的配制物,其中有机溶剂(d)进一步包括大约30g仲丁基苯和3.0g醇的混合物。
16.涂覆应用在电泳设备上的颜料粒子的方法,包括以下步骤:
(a)混合具有预定密度的大量颜料粒子;自由基聚合反应引发剂;密度基本等于颜料粒子密度的五氟苯乙烯单体;和有机溶剂的混合物,接着
(b)加热和鼓转步骤(a)的混合物使五氟苯乙烯单体聚合并涂覆颜料粒子。
17.权利要求16的方法,进一步包括以有机溶剂洗液清洗所得粒子的步骤。
18.权利要求16的方法,其中步骤(a)进一步包括将约1.18g密度约1.43g/ml的黄色二芳基化物颜料粒子、0.05g的4,4'-偶氮双(4-氰基戊酸)、0.75g密度约1.41g/ml的2,3,4,5,6-五氟苯乙烯的混合物;和大约30g癸烷和5.0g醇的混合物混合。
19.权利要求16的方法,其中步骤(a)进一步包括将约1.18g密度约1.43g/ml的黄色二芳基化物颜料粒子、0.05g的4,4'-偶氮双(4-氰基戊酸)、0.50g密度约1.41g/ml的2,3,4,5,6-五氟苯乙烯的混合物;和大约30g仲丁基苯和3.0g醇的混合物混合。
20.权利要求16的方法,其中加热和鼓转混合物的步骤进一步包括在约32rpm和约60摄氏度的条件下鼓转混合物24小时,然后在70摄氏度下鼓转12小时。
CN98803274A 1997-02-21 1998-02-11 聚合物涂覆的介电粒子及配制物和制备它的方法 Pending CN1250457A (zh)

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CN113423751A (zh) * 2019-04-24 2021-09-21 伊英克公司 电泳粒子、介质和显示器及其制造方法
CN113423751B (zh) * 2019-04-24 2024-03-12 伊英克公司 电泳粒子、介质和显示器及其制造方法
CN112117467A (zh) * 2019-06-19 2020-12-22 原子能与替代能源委员会 用于形成用作气体扩散层的疏水性导电微孔层的方法
CN112117467B (zh) * 2019-06-19 2023-10-31 原子能与替代能源委员会 用于形成用作气体扩散层的疏水性导电微孔层的方法

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WO1998037136A1 (en) 1998-08-27

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