CN1203353C - 制造电泳显示器的方法 - Google Patents

制造电泳显示器的方法 Download PDF

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CN1203353C
CN1203353C CNB018014496A CN01801449A CN1203353C CN 1203353 C CN1203353 C CN 1203353C CN B018014496 A CNB018014496 A CN B018014496A CN 01801449 A CN01801449 A CN 01801449A CN 1203353 C CN1203353 C CN 1203353C
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梁荣昌
陈美英
吴让二
陈仙海
臧宏玫
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E Ink California LLC
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
    • G02F1/166—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field characterised by the electro-optical or magneto-optical effect
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/165—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on translational movement of particles in a fluid under the influence of an applied field
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    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
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    • G02F1/133305—Flexible substrates, e.g. plastics, organic film
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/13—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • G02F1/1339—Gaskets; Spacers; Sealing of cells

Abstract

本发明涉及一种制造微型杯阵列的方法。此种阵列可以有多种用途，例如视频显示。这种微型杯特别适用于电泳或液晶显示器。

Description

制造电泳显示器的方法
本发明所属技术领域
本发明涉及电泳显示器，尤其涉及一种制造这种显示器的新颖方法。
与本发明相关的背景技术
电泳显示器是基于悬浮在溶剂中的带电荷颜料微粒的电泳现象制成的一种非发射性的装置。其在1969年首次提出。这类显示器通常包括具有电极的两块板，这两块板彼此相对放置并由间隔物分隔开。通常，其中的一块电极板是透明的。包含有一种被染色的溶剂和带电荷颜料微粒的悬浮物被密封在二个电极板之间。当在二电极之间施加一个电压差时，颜料微粒将迁移到一侧，该颜料的颜色或该溶剂的颜色依电压差的极性显现。
为避免不希望的微粒迁移(诸如沉淀)，在先技术在二个电极之间划分区间。然而，在分区式电泳显示器的情况下，形成分区与悬浮物密封处理会遇到某些困难。此外，难于在分区式电泳显示器中保持不同颜色的悬浮物分离。
因此现有技术试图把悬浮物密封在微胶囊中。美国专利第5,961,804号以及第5,930,026号说明了微胶囊化的电泳显示器。该文献披露的显示器具有基本上二维的微胶囊排列，其中各微胶囊含有由一介电质流体与一带电荷颜料微粒悬浮物(在视觉上与介电质溶剂对比)所组成的电泳组分。该微胶囊的形成可借助于界面聚合、原位聚合，或者诸如物理处理、液体内固化或简单/复杂凝聚等其他已知的工艺。在微胶囊形成后，可将其注入装有二个隔离电极的室中，或“印刷”或涂布在透明导电膜上。所述微胶囊也可被固定到一透明基材或粘合剂中，亦即其本身被夹在所述二个电极之间。
利用这些现有工艺方法，特别是美国专利第5,930,026号、第5,961,804号以及第6,017,584号所披露的微胶囊方法制备的电泳显示器有许多缺点。例如，用微胶囊方法制造的电泳显示器，由于微胶囊壁的化学性质受到对环境变化的敏感度(特别是对于湿度与温度的敏感度)的不利影响。第二，由于胶囊的薄壁面与较大微粒尺寸，用微胶囊制造的电泳显示器具有较差的抗刮性。为改进该显示器的操作性，微胶囊被嵌埋于大量的聚合物基材中。但是，由于二电极间距增大，使响应时间变长；而且，由于颜料微粒的低有效负载，使对比度降低。因为电荷控制剂在该微胶囊制备期间趋于扩散至水/油界面，致使难以增加颜料微粒上的表面电荷密度。微胶囊中颜料微粒的低电荷密度或ζ电位也使其灵敏度变低。此外，因为微胶囊的大微粒尺寸和与大范围分布，对于色彩应用而言，此类型的现有技术的电泳显示器具有的分辨率与寻址能力较低。
为了避免不希望的微粒移动，诸如侧向迁移或沉淀，现有技术采用光刻法将电泳显示器分割成比较小的单元。现有技术中的处理，是分批次进行的，并且需要溶剂显影。现有技术还披露了一种辊对辊微模压工艺。因此需要一种不需要溶剂的高产出的制造方法，用于电泳或液晶显示器中的微型杯(micro-cups)的生产。
发明综述
本发明提出了一种微型杯阵列的制造方法及用途。
根据本发明的一个方面，提供了一种是利用涂布有热塑性或热固性前体物组分(例如紫外光固化树脂)的预成型凸模制作微型杯阵列的方法。然后，使此树脂与具有图案化的导电层的转移片(或塑料基板)接触，并且可以选择性地将它加热。模子对准于导体图案。可向转移片施加均匀的压力，以帮助改善转移片和树脂之间的粘合，以及控制微型杯底部的厚度。通过暴露于辐射(例如紫外光(UV))而固化树脂。一旦树脂固化之后，从凸模脱出以产生微型杯阵列。凸模也可以选择性地预先涂脱模剂，例如蜡、聚硅氧烷或氟化聚合物。如果需要的话，也可以后固化微型杯阵列。
根据本发明的第二方面，提供了一种使用微型杯阵列的电泳显示器的制造方法。用于全彩电泳显示器的制造方法包括：层叠预先制成的微型杯和一层正性光致抗蚀剂，将正性光致抗蚀剂进行图形曝光，选择性地打开一定数量的微型杯，接着把抗蚀剂显影、把打开的微型杯填充着色的电泳流体，并用密封工艺将填充的微型杯密封起来。可以重复这些步骤，以生成填充了不同颜色的电泳流体的密封微型杯。
根据本发明的第三方面，提供了一种使用微型杯阵列的电泳显示器。对微型杯阵列填充介电流体，而该流体包含至少一种带电荷的颜料悬浮体，其是在一种有色的介电溶剂或溶剂混合物中。然后密封微型杯。层叠该密封的阵列和涂有胶层的导电膜。
附图简要描述
图1是根据本发明的电泳显示器的示意图。
图2是转移模(也就是凸模)的示意图。
图3是生产工艺的示意图，其通过将紫外光固化组合物转移涂布至凸模上。
图4是制造黑白电泳显示器或其它单色电泳显示器的流程图。
图5是制造多色电泳显示器的流程图。
图6是以本发明的方法所制备的典型微型杯阵列。
发明详述
以下述定义和实施例作为参考的方式详细描述本发明。本文所引述的所有专利和出版物，结合于此作为参考文献。
定义
除非在本专利说明书中另有定义，否则在此所用的技术术语皆根据本领域技术人员通常使用并了解的惯用定义而被使用。在此，下述的词汇或缩写(不论是以单数形式或复数形式使用)，具有所述的意义：
“微型杯(micro-cup)”一词，是指由转移模压所生成的杯状凹处。
在本专利说明书中，术语“盒”是指由一密封微型杯所形成的独立的单位。该盒以分散于溶剂或溶剂混合物中的带电荷颜料微粒填充。
当说明该微型杯或盒时，术语“有明确定义的”是指该微型杯或盒具有根据本工艺的特定参数预定的明确的形状、尺寸、纵横比。
“纵横比”一词为电泳显示器中一般所知的词汇。于本申请中，它是指微型杯的深度对宽度或深度对长度的比例。
优选实施例的详细描述
如图1所示，根据本发明的电泳显示器包括有二个电极板(10，11)(至少其中一个为透明的(10))，以及位于该二个电极之间密封的一层明确定义的盒层(12)。该盒有明确定义的形状与尺寸，并以分散在经染色的介电溶剂中的带电荷颜料微粒填充。当施加电压差于二电极之间时，该带电荷微粒将迁移至一侧，这样可透过透明导电膜看见颜料的颜色或溶剂的颜色。至少该二导体之一是被图案化的。用于制备该电泳显示器的工艺涉及几个方面。
I.微型杯的制备
凸模的制备
凸模(24)可用任何适当的方法制备，例如光致抗蚀处理后，接着蚀刻或电镀。制作凸模的示意性实施例见图2。用于凸模的主模板则可以用任何适当的方法制造，例如电镀。采用电镀法时，在一玻璃基板上喷镀一层通常为3000的籽金属薄层，例如铬镍铁合金(chrome inconel)。接着涂布光致抗蚀剂层，并以紫外光曝光。一掩模被置于紫外光与光致抗蚀剂层之间。该光致蚀刻剂的曝光区域变硬。然后用适当的溶剂清洗，去除未曝光区域。干燥所保留的固化光致抗蚀剂，并再次喷镀一层籽金属薄层。之后主模准备就绪，可以进行电铸成形。用于电铸成形的典型材料是镍钴合金。此外，该主模可由镍制作，如摄影光学仪器工程师学会会刊卷1663，pp.324(1992)中《薄镀层光学介质的连续制作》(“Continuousmanufacturing of thin cover sheet optical media”，SPIE Proc.)中所说明的，采用氨基磺酸镍(nickel sulfamate)电铸或无电镍沉积。该模具的底座(22)通常约50至400微米。该主模也可用其他微工程技术制作，包括电子束写入、干式蚀刻、化学蚀刻、激光写入或激光干涉，如《精密光学复制技术》见摄影光学仪器工程师学会会刊(“Replication techniques for micro-optics”，SPIE Proc.)卷3099，pp.76-82(1997)中说明。此外，该模具可使用塑料、陶瓷、金属，利用光加工制作。
如此制备的凸模(24)通常具有大约1至500微米之间的凸起(20)，优选的是在大约2至100微米之间，更优选的是大约4至50微米。凸模可以是带、辊、片的形式。对于连续制造而言，优选的是带型的模子。
微型杯的制作
微型杯可以用批次工艺或是连续的辊对辊工艺制作。后者提供连续、低成本、高产出的制造技术，以制造电泳或液晶显示器中用的隔间。该工艺如图3所示。在涂布紫外光固化树脂以前，如果需要，可采用脱模剂，以帮助脱模过程。紫外光固化树脂(30)在配送前可以先除气，并且可以非必选地加入一种溶剂。这种溶剂(如果有的话)可以容易地蒸发。该紫外光固化树脂(30)可以任何适当的方式配送于凸模(24)上，例如涂布、滴落、倾倒等。配送器(32)可以是移动式的或固定式的。将一种具有粘合促进特性的塑料基板或转移片(34)层叠在紫外光固化树脂上。
用于制备微型杯的热塑性或热固性前体物，可以是多官能团的丙烯酸酯或甲基丙烯酸酯、乙烯醚、环氧化物，以及它们的低聚物、聚合物和同类物。最优选的是多官能团的丙烯酸酯及其低聚物。多官能团的环氧化物与多官能的丙烯酸酯的组合也非常有用，可获得所要的物理机械性能。通常，也添加赋予挠性的可交联的低聚物，例如氨基甲酸乙酯丙烯酸酯或聚酯丙烯酸酯，以改善模压微型杯的弯曲强度。该组合物可以包含聚合物、低聚物、单体和添加剂，或者只有低聚物、单体和添加剂。适合的树脂实施例包括但不限于丙烯酸系树脂、聚酯(例如聚对苯二甲酸乙二酯和聚萘酸乙二酯)、芳族聚酰胺、聚酰胺、聚酰亚胺、聚环烯烃、聚砜(polysulfone)、环氧化物，及它们的组合物。其他树脂为多价的丙烯酸酯或甲基丙烯酸酯、多价的乙烯基化合物(包括乙烯基苯、乙烯基硅烷、乙烯基醚)、多价的环氧化物、多价的丙烯化物，以及包含那些可交联的官能团的低聚物、聚合物等等。
这类材料的玻璃化温度(或Tg)范围通常从约-70℃到约150℃，优选是从约-20℃到约50℃。微模压过程通常是在高于Tg的温度下进行。可以采用加热凸模，或加热模子基座，以控制模压的温度和压力。
适合的塑料为聚对苯二甲酸乙二酯(polyethylene terephthalate)、聚萘酸乙二酯(polyethylene naphthate)、聚碳酸酯、聚氟乙烯、芳族聚酰胺(polyaramid)、聚酰亚胺、聚环烯烃、聚砜(polysulfone)、环氧化物和其复合物。如果需要的话，可以施加压力，以确保树脂和塑料之间有适当的接合，并控制微型杯底板的厚度。可以采用层压辊、真空模压成型、加压装置或任何其它类似的装置来施加压力。如果凸模是金属的并且不透明，则典型的塑料基板对于用来固化树脂的光化性辐射而言是透明的。反之，凸模可以是透明的，而塑料基板对于光化性辐射而言是不透明的。为了将模压特征良好地转移到转移片上，塑料基板必须对于紫外光固化树脂具有良好的粘合性。模子或前体物组分(例如可固化树脂)也可以非必选地加热到40℃至约200℃之间。
II.悬浮体/分散体的制备
对该微型杯填充以分散在介电溶剂中的带电荷颜料微粒。该分散体可根据本领域已知方法制备，如记载于美国专利第6,017,584号，第5,914,806号，第5,573,711号，第5,403,518号，第5,380,362号，第4,680,103号，第4,285,801号，第4,093,534号，第4,071,430号，第3,668,106号，电气和电子工程师协会会报-《电子装置》(IEEETrans.Electron Device)，ED-24，827(1977)，以及J.Appl.Phys.49(9)，4820(1978)中的方法。该带电荷的颜料微粒在视觉上与悬浮于其中的介质存在反差。该介质为介电溶剂，最好具有低粘滞性且介电常数为约2至约30之间，为达到高微粒移动速率，优选为约2至约15之间。适当的介电溶剂的实例包括如十氢化萘(DECALIN)、5-亚乙基-2-降冰片烯(5-ethylidene-2-norbornene)、脂肪油、蜡下油(paraffin oil)等碳氢化合物；如甲苯、二甲苯、苯基二甲苯乙烷、十二烷基苯和烷基奈等芳香族碳氢化合物；如全氟代十氢化萘(perfluorodecalin)、全氟甲苯(perfouorotoluene)、全氟二甲苯、二氯三氟甲苯(dichlorobenzotrifluoride)、3，4，5-三氯三氟甲苯(3，4，5-trichlorobenzotrifluoride)、氯五氟基苯(chloropentafluoro-benzene)、二氯壬烷(dichlorononane)、五氯苯等的卤化溶剂；诸如来自明尼苏达州St.Paul的3M公司的FC-43、FC-70和FC-5060的全氟溶剂；低分子量的含卤素的聚合物，如自奥勒岗州Portland的TCI America的聚全氟丙烯醚(poly(perfluoropropylene oxide))；聚氯三氟乙烯，如来自新泽西州RiverEdge的Halocarbon Product公司的卤烃油(Halocarbon oil)；全氟聚烷基醚(perfluoropolyalkylether)，如来自Ausimont的Galden，或是来自特拉华州DuPont的Krytox油和脂K-Fluid系列。在一个优选具体实施例中，使用聚氯三氟乙烯作为介电溶剂。在另一优选的实施例中，使用聚全氟丙烯醚(poly(perfluoropropylene oxide))作为介电溶剂。
该悬浮介质可为染料或颜料所着色。非离子偶氮与蒽醌染料特别地有用。有用的染料的例子非限定性地包括：亚利桑那州PylamProducts公司生产的油溶红EGN(Oil Red EGN)，苏丹红(SudanRed)，苏丹蓝(Sudan Blue)，油溶蓝(Oil Blue)，Macrolex蓝，溶剂蓝35(Solvent Blue 35)，亚利桑那州Pylam Products公司的PylamSpirit黑和Fast Spirit黑，Aldrich公司的苏丹黑B(Sudan Black B)，BASF公司的Thermoplastic Black X-70，以及Aldrich公司的蒽醌蓝，蒽醌黄114，蒽醌红111，135，蒽醌绿28。对于不溶性颜料的情形，用于使介质产生颜色的颜料颗粒亦可分散于该介电介质中。这些有色颗粒优选为不带电荷的。如果用于在介质中产生颜色的颜料颗粒是带电荷的，则其最好带有与该带电荷颜料微粒相反的电荷。若二种颜料微粒带有相同的电荷，则其应具有不同的电荷密度或不同的电泳移动速率。在任何情况下，用于产生介质颜色的染料或颜料必需具有化学稳定性，并与悬浮体中的其它组分相容。此外，也可以使用聚合型染料(例如染料接枝聚合物)或是接枝染料(例如接有低聚物/单体的染料)。
该带电荷颜料微粒可为有机或无机颜料，如自Sun化学制品公司的TiO2、酞菁蓝(phthalocyanine blue)、酞菁绿(phthalocyaninegreen)、二芳基黄(diarylide yellow)、二芳基AAOT黄(diarylideAAOT Yellow)、喹吖啶酮(quinacridone)、偶氮(azo)、若丹明(rhodamine)、苝系颜料(perylene pigment series)；自Kanto化学制品公司的汉撒黄G(Hansa yellow G)颗粒，以及Fisher公司的碳灯黑(Carbon Lampblack)。优选的是亚微粒子尺寸。该微粒应具有可接受的光学特性，不应被介电溶剂膨胀或软化，并且应该是化学稳定的。在正常的工作条件下，所产生的悬浮物亦必须稳定且能抗沉淀、乳化或凝结。
该颜料微粒可具有自然电荷，或可使用电荷控制剂直接使之带电，或可在悬浮于介电溶剂时获得电荷。适当的电荷控制剂是本领域熟知的；其可为聚合或非聚合性质，并且可为离子的或非离子的，包括自Chevron化学制品公司的离子表面活性剂，如气溶胶邻联甲苯胺(Aerosol OT)、十二烷基苯磺酸钠(dodecylbenzenesulfonate)、OLOA 1200；金属皂，如碱式石油磺酸钙(basic calcium petroleumsulphonate)、碱式水杨酸烷基钙(basic calcium alkyl salicylate)、水杨酸烷基锌(zinc alkyl salicylate)、烷基二苯醚二磺酸盐(alkyldiphenyloxide sulphonate)(是Dow化学制品公司的Dowfax表面活性剂)，聚丁烯丁二酰亚胺(polybutene succinimide)、顺丁烯二酸酐共聚物(maleic anhydride copolymers)、乙烯基吡咯烷酮共聚物(vinylpyrrolidone copolymer)(如来自International SpecialtyProducts的Ganex)、(甲基)丙烯酸共聚物((meth)acrylic acidcopolymers)、N，N-二甲基胺基乙基(甲基)丙烯酸乙酯共聚物[N，N-dimethylaminoethyl](meth)acrylate copolymers]。氟化表面活性剂在全氟化碳溶剂中作为溶剂电荷控制剂特别有用。这些包括FC氟化表面活性剂，如3M公司的FC-170C、FC-171、FC-176、FC430、FC431和FC-740；以及Zonyl氟化表面活性剂，如Dupont公司的FSA、FSE、FSN、FSN-100、FSO、FSO-100、FSD和UR。
可通过任何熟知的方法制备适当的带电颜料分散体，包括研磨、碾磨、球磨、气流磨(microfluidizing)以及超声波技术。例如，将细粉末形式的颜料微粒加入悬浮溶剂，所获混合物被球磨数小时，将高度团聚的干颜料粉分散成最初的微粒。虽然不是最理想的，但是在该球磨过程，可对该悬浮物添加用于产生悬浮介质颜色的染料或颜料。
可通过使用适当的聚合物将该微粒微囊化，以消除颜料微粒的沉淀或乳化，使其比重与介电溶剂的比重一致。可用化学或物理方法完成颜料微粒的微囊化。典型的微囊化工艺包括界面聚合、原位聚合、相分离、凝聚、静电涂布、喷雾干燥、流化床涂布以及溶剂蒸发。
就黑/白的电泳显示器而言，该悬浮物包含分散于黑色溶剂中的带电荷的白色二氧化钛(TiO2)微粒，或分散于一种介电溶剂中的带电荷黑色微粒。黑色染料或染料混合物可被用于产生溶剂的黑色，如Pylam Products公司(亚利桑那州)的Pylam Spirit黑和FastSpirit黑，Aldrich公司的苏丹黑B，BASF公司的Thermoplastic BlackX-70，或一种不可溶的黑色颜料如碳黑。对于其它有色悬浮物来说，有多种可能性。对于减色系统而言，带电荷的二氧化钛(TiO2)微粒可悬浮于蓝绿色、黄色或品红色的介电溶剂中。该蓝绿色、黄色或品红色可使用染料或颜料产生。对于加色系统而言，带电荷的二氧化钛微粒可悬浮于红色、绿色或蓝色的介电溶剂中，其中该红色、绿色或蓝色亦可使用染料或颜料产生。大多数的应用最好采用这种红色、绿色或蓝色系统。
III.微型杯的密封
微型杯的密封可用多种方法完成。一种优选的方法是将包含有多官能团的丙烯酸酯、丙烯酸化低聚物及光敏引发剂的紫外光固化组分，分散于一种含有散布在染色介电溶剂中的带电荷颜料微粒的电泳流体中。该紫外光固化组分与该介电溶剂不互溶，且具有比该介电溶剂及颜料微粒小的比重。此二种成分(紫外光固化组分与电泳流体)在径向混合器中被完全地混合，并采用如Myrad棒、凹印板、刮刀片、开槽涂布或开缝涂布等精确的涂布机械装置，立即涂布于该微型杯上。用扫杆刮刀或类似的装置将过量的流体刮除。可用少量的弱溶剂或者溶剂混合物，如异丙醇、甲醇或其水性溶液等，清洗微型杯的分隔壁顶端表面上残留电泳流体。挥发性的有机溶剂可用于控制该电泳流体的粘滞性与覆盖性。接着烘干填充的微型杯，该紫外光固化组分浮在电泳流体的顶部。在紫外光固化层浮到表面期间或之后，将其进行固化，密封微型杯。紫外光或其他辐射形式，如可见光、红外线及电子束等，皆可用于将该微型杯固化和密封。可选地，也可使用热或湿气将该微型杯固化并密封，如果适当的话，可采用热或湿气可固化组分。
具有所需密度并对丙烯酸酯单体和低聚物有溶解度差别的优选介电溶剂组为卤化烃及其衍生物。可用表面活性剂改善电泳流体与密封材料之间界面的粘合性与润湿性。有用的表面活性剂包括3M公司的FC表面活性剂、DuPont的Zonyl氟化表面活性剂、氟化丙烯酸酯、氟化甲基丙烯酸酯、氟取代长链醇类、全氟取代的长链羧酸及其衍生物。
可选地，如果这种密封前体物至少部分地与介电溶剂相容，则可将电泳流体及密封前体物依次涂布于微型杯。这样，可通过涂布一层热固性前体物薄层(该前体物是辐射、热、湿气或界面反应可固化的)，并将其固化于经填充的微型杯表面上，以完成此密封过程。界面聚合后进行紫外光固化，对于密封过程极为有利。通过界面聚合形成一个薄的分隔层，使电泳层与外敷层之间的互相混合明显得到抑制。该密封接着通过后固化步骤完成，优选为紫外光辐射或其他光辐射。为进一步降低互混程度，最好外敷层的比重明显低于电泳流体的比重。可用挥发性有机溶剂调整涂层的粘度和厚度。当挥发性溶剂用于外敷层时，优选为与该介电溶剂不相混溶。这种二步涂布方法，对所用染料至少部分地溶解于热固性前体物情形特别适用。
IV.单色电泳显示器的制备
通过图4所示的流程图说明此工艺。所有的微型杯都用同色组分的悬浮物填充。该工艺可为连续的辊对辊工艺，包括如下步骤：
1.如上文所述制备微型杯。简言之，将紫外光固化组合物转移至凸模，固化该组合物，并且使用转移片将形成的部分脱模，从而制成微型杯。此工艺可以是分批的或辊对辊连续制作。
2.从固化的树脂层脱模，最好在树脂以适当方式硬化期间或之后进行。
3.用一种带电荷颜料分散体(64)填充上述方法制成的微型杯阵列(63)，分散体在着色介电溶剂中，该介电溶剂包含至少一种与该溶剂不相容的热固性前体物，并且该前体物较溶剂与颜料微粒比重低。
4.在该热固性前体物分离并于该液相上面形成一表面浮层期间或之后，通过将该热固性前体物固化密封微型杯，优选采用如紫外光辐射(65)或加热或湿气，因而形成包含有在染色介电溶剂中的颜料分散体的密封电泳盒。
5.将预涂布有胶层(67)的第二导电膜(66)覆盖于经密封的电泳盒阵列，其中该胶层(67)可为压敏粘合剂、热熔粘合剂或一种热、湿气或辐射固化粘合剂。
可采用如紫外光(68)等的辐射，透过该上层导电膜对胶层进行后固化(如果该上层导电膜对这类辐射是透明的)。在该层叠步骤完成后，成品可被切割(69)和组装。
上述微型杯的制备可以方便地以另一种分批制造的工序取代。可通过在电泳流体表面直接涂布并固化热固性前体物的组合物层，完成对微型杯的密封。
V.多色电泳显示器的制备
对于多色电泳显示器的制备而言，需要额外的步骤以产生包含不同颜色悬浮物的微型杯。这些额外的步骤包括：(1)将一种正性作用干膜光致抗蚀剂覆盖于制成的微型杯，该光致抗蚀剂由以下成分组成：至少一种如马萨诸塞州Worcester，Saint-Gobain公司的可去除载体PET-4851，如Shipley公司的酚醛树脂正性光致抗蚀剂Microposit S1818，以及一种碱性显影胶层，如National Starch公司的Nacor72-8685与BF Goodrich公司的Carboset 515的混合物；(2)将光致抗蚀剂进行图形曝光，除去可移除的载体膜，以及用一种显影剂，如Shipley公司的经稀释的Microposit 351显影剂，将该正性光致抗蚀剂显影，从而选择性地开启特定数目的微型杯；(3)用包含带电荷白色颜料(二氧化钛)微粒和第一原色染料或颜料的电泳流体填充开启的微型杯；以及(4)按照单色显示器制备中说明的方法，将经填充的微型杯密封。这些附加的步骤可重复，以形成用第二和第三原色的电泳流体填充的微型杯。
更特别地，可根据图5所示步骤制备一种多色电泳显示器。
1.如上文所述，在导电膜(71)上使用紫外光固化树脂(70)制造微型杯(72)。
2.最好在树脂固化期间或之后，从该固化的树脂层脱模。
3.将一正性干膜光致抗蚀剂覆盖于所制成的微型杯阵列(72)，其中至少包含有一胶层(73)、一正性光致抗蚀剂(74)，以及一可去除的塑料保护片(图中未示出)。
4.用紫外光、可见光或其他辐射将该正性光致抗蚀剂进行图形曝光(图5c)，除去保护片，在曝光区域显影、开杯。步骤3和4的目的，是在预定区域选择性地开启微型杯(图5d)。
5.用带电荷白色颜料分散体(75)填充开启的微型杯，分散体所在介电溶剂包含至少一种第一原色的染料或颜料，以及与该溶剂不相容的热固性前体物(76)，并且该前体物较溶剂与颜料微粒比重低。
6.在热固性前体物(76)分离并在液相上面形成一表面浮层的期间或之后，采用热、湿气或例如紫外光的辐射，来固化热固性前体物(76)，密封微型杯，以形成包含第一原色的电泳流体的封闭电泳盒(图5e)。密封步骤优选采用紫外光固化。
7.可以重复上述步骤5～6，以在不同区域产生包含不同颜色电泳流体的有明确定义的盒(图5c～5g)。
8.将预涂布有胶层(78)的一个预制图形的第二透明导电膜(77)，套准层叠于密封的电泳盒阵列，其中所述胶层(78)可为压敏粘合剂、热熔粘合剂或一种热、湿气或辐射固化粘合剂。
9.粘合剂硬化。
上述微型杯的制备方法，可以方便地以另一种分批制造的工序取代。可通过在电泳流体表面直接涂布并固化热固性前体物的组合物层，完成对微型杯的密封。
用本方法制造的显示器可以达到仅一张纸的厚度。该显示器的宽度可为涂布片的宽度(通常为3至90英寸)。该显示器的长度可为数英寸至数千英尺，取决于卷的大小。
实施例
以下所描述的制备和实施例，是为便于本领域技术人员能够更清楚地了解并实施本发明，不应理解为是对本发明范围的限制，而仅仅对是本发明的说明和示范。
实施例1
用于制造微型杯的液体配方组分的制备
所用的液体配方示于表1。液体配方组分在使用前事先使用超声波除气10分钟。配方X-021比配方X-023或X-024所制成的微型杯底部厚。
                表1-用于转移成型的配方
编号     成分(供货商) 描述 X-021 X-023 X-024
1   Ebecryl 3605(UCB Chemicals) 环氧丙烯酸酯 56.07 53.67 48.60
2   Ebecryl 4827(UCB Chemicals) 胺基甲酸乙酯丙烯酸酯 11.21 10.73 9.72
3   HDODA(UCB Chemicals) 单体 28.04 26.84 33.43
4   Ebecryl 1360(UCB Chemicals) 润滑剂 0.00 4.29 4.20
5   Irgacure 500(Ciba SpecialtyChemicals公司) 光引发剂 4.67 4.47 4.05
  总计 100.00  100.00  100.00
使用移动的或固定式的配送器可方便地配送液体配方。如果使用固定式的配送器，则应接着精确地进行保留凸模特征的刮涂。
实施例2
微型杯的制造
采用光刻技术做出有四个分区的凸模，以制出图6所示尺寸的微型杯。凸模主要由镍制成，并且突起大约10微米高。对模子施以脱模剂(选用Frekote700-NC)。使用微吸移管把几滴所要的液体配方(例如实施例1所述)涂于凸模上。然后将聚对苯二甲酸乙酯膜(来自DuPont的Mylar或Melinex膜)层叠于已涂布的凸模上。用具有一组配套橡胶辊的GBC层合器来进行层合。辊的温度设定在60℃，速度为每分钟1～30英尺。涂布物透过PET膜用紫外光进行曝光5分钟。
以本发明的技术所做的微型杯尺寸列于表2。用配方X-021所制造的微型杯底部比较厚(大约10微米)；用配方X-023和X-024制造的微型杯底部比较薄(小于约5微米)。
              表2-用各种配方和膜在膜上转移成型
  编号 样本 配方     膜3   四区分 h1(微米) d2(微米)
    1 F021A X-021 Melinex 725/500克     3   8～10     10
    2 F023B X-023 Melinex 453/92克     2   12     ～0
    3 F023B X-023 Melinex 453/92克     1   12     2
    4 F024A X-024 Melinex 725/500克     4   11～12     4.5
    5 F024B X-024 Melinex 453/92克     2   12～13     1～3
1.h：微型杯的高度
2.d：微型杯底部厚度
3.膜种类/膜厚度(标准计量)
虽然本发明已经参考其特定的具体实施例而加以描述，但是对于本领域技术人员来说，可以容易地对上述实施方案进行多种修改和改进，或应用于其它领域。可以做多种的改变，以及有多种的等效物可以取代。此外，可以做许多修改来适合特殊的情况、材料、组分、工艺、一个工艺步骤或多个步骤，而不偏离本发明的目的、精神和范围。所有这些改动均在本发明专利申请权利要求范围内。
组件符号说明
10电极板
11电极板
12盒
20凸起
22模具的底座
24凸模
30紫外光固化树脂
32配送器
34塑料基板或转移片
63微型杯阵列
64带电颜料分散体
65辐射
66第二导电膜
67胶层
68辐射
69切割
70紫外光固化树脂
71导电膜
72微型杯
73胶层
74正性光致抗蚀剂
75带电的白色颜料分散体
76热固性前体物
77第二导电膜
78胶层

Claims (30)

1.一种制造微型杯阵列的方法，包括：
a.将热固性或热塑性前体物组分涂布于凸模上，以便在所述凸模上形成一层连续的前体物层，所述凸模具有多个凸起，用于形成所要制造的微型杯阵列；
b.将所述前体物层与转移片接触；
c.将所述前体物固化，以形成微型杯阵列；以及
d.将所述微型杯阵列从凸模中脱模。
2.根据权利要求1所述的方法，其中所述固化是通过暴露于热、湿气或辐射实现的。
3.根据权利要求1所述的方法，其中所述前体物组分包括可交联树脂、单体、低聚物，或聚合物。
4.根据权利要求1所述的方法，其中所述可交联树脂、单体、低聚物、聚合物选自：多价的丙烯酸酯、多价的甲基丙烯酸酯、多价的乙烯基化合物、多价的环氧化物、多价的丙烯化物，以及包含那些可交联官能团的低聚物、聚合物。
5.根据权利要求1所述的方法，其中所述前体物组分是在接近或高于其玻璃化温度下进行涂布的。
6.根据权利要求5所述的方法，其中所述玻璃化温度是从约-70℃到约150℃。
7.根据权利要求6所述的方法，其中所述玻璃化温度是从约-20℃到约50℃。
8.根据权利要求1所述的方法，其中所述前体物组分还包括增塑剂、有机溶剂或溶剂混合物。
9.根据权利要求1所述的方法，其中所述凸模选自带、辊、和片。
10.根据权利要求9所述的方法，其中所述凸模是带。
11.根据权利要求1所述的方法，其中所述凸模或所述前体物被加热到约40℃至约200℃之间。
12.根据权利要求1所述的方法，其中所述微型杯阵列在从所述凸模脱模后进行后固化。
13.根据权利要求1所述的方法，其中所述转移片选自聚对苯二甲酸乙二酯、聚萘酸乙二酯、聚碳酸酯、聚氟乙烯、芳族聚酰胺、聚酰亚胺、聚环烯烃、聚砜、环氧化物，以及其组合物。
14.一种制造用于电泳或液晶显示器的微型杯的方法，包括以下步骤：
a.将热固性或热塑性前体物组分涂布于凸模上，以便在所述凸模上形成一层连续的前体物层，所述凸模具有多个凸起，用于形成所要制造的微型杯阵列；
b.使所述前体物层与一具有面对所述前体物层的图形化的透明导体层的透明基板接触；
c.对所述基板均匀地施加压力；
d.使所述前体物层硬化，以形成附着于所述透明基板的微型杯阵列；以及
e.将所述微型杯阵列从所述凸模加以脱模。
15.根据权利要求14所述的方法，其中所述固化是通过将前体物暴露于热、湿气或辐射实现的。
16.根据权利要求14所述的方法，其中所述前体物组分包括可交联的树脂、单体、低聚物，或聚合物。
17.根据权利要求14所述的方法，其中所述可交联的树脂、单体、低聚物或聚合物从多价的丙烯酸酯或多价的甲基丙烯酸酯，多价的乙烯化物，多价的环氧化物、多价的丙烯化物，以及包含那些可交联的官能基团的低聚物、聚合物中选择。
18.根据权利要求14所述的方法，其中所述前体物组分是在接近或高于其玻璃化温度下进行涂布的。
19.根据权利要求18所述的方法，其中所述玻璃化温度是从约-70℃到约150℃。
20.根据权利要求19所述的方法，其中所述玻璃化温度是从约-20℃到约50℃。
21.根据权利要求14所述的方法，其中所述前体物组分还包括增塑剂、有机溶剂、或溶剂混合物。
22.根据权利要求14所述的方法，其中所述凸模选自带、辊、和片。
23.根据权利要求22所述的方法，其中所述凸模是带。
24.根据权利要求14所述的方法，其中所述凸模或所述前体物被加热到约40℃至约200℃之间。
25.根据权利要求14所述的方法，其中所述微型杯阵列在从所述凸模脱模后进行后固化。
26.根据权利要求14所述的方法，其中所述透明基板选自：聚对苯二甲酸乙二酯、聚萘酸乙二酯、聚碳酸酯、聚氟乙烯、芳族聚酰胺、聚酰亚胺、聚环烯烃、聚砜、环氧化物，以及其组合物。
27.根据权利要求14所述的方法，其中所述图形化的透明导体层包括铟锡氧化线，其宽度与所述凸模的所述突起图案的宽度一致。
28.根据权利要求14所述的方法，其中所述图案化的透明导体层与所述凸模的所述突起图案套合。
29.根据权利要求1或14所述的方法，还包括以下步骤：
将所述微型杯用介电流体填充，所述介电流体包含至少一种分散于介电溶剂或溶剂混合物中的带电荷颜料悬浮体；
密封经过填充的所述微型杯，以形成电泳盒阵列；以及层叠所述电泳盒阵列和预先涂布有胶层的导电膜。
30.根据权利要求1或14所述的方法，还包括如下步骤：
将所述微型杯阵列层叠一层正性光致抗蚀剂，以密封所述微型杯；
将所述正性光致抗蚀剂进行图形曝光，以便有选择性地打开预定区域的微型杯；
将打开的微型杯用介电流体填充，所述介电流体包含至少一种分散于介电溶剂或溶剂混合物中的白色颜料分散体，
所述溶剂或溶剂混合物中包含具有第一色的染料或颜料分散体；
将所述微型杯密封，以便形成电泳盒；
使用不同颜色的介电流体在不同的区域重复前述图形曝光、填充和密封的步骤；
去除残留的正性光致抗蚀剂；以及
用具有预涂胶层的导电膜层叠所述电泳盒阵列。
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CA2412380A1 (en) 2002-01-03
JP2006259771A (ja) 2006-09-28
TW567349B (en) 2003-12-21
WO2002001281A2 (en) 2002-01-03
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CN1439112A (zh) 2003-08-27
WO2002001281A8 (en) 2002-03-28

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