TW201107430A - Electrophoretic particles - Google Patents

Abstract

In electrophoretic media, it is advantageous to use pigment particles having polymer shells comprising from 0.1 to 5 mole per cent of repeating units derived from a fluorinated acrylate or fluorinated methacrylate monomer. The polymer desirably has a branched chain structure with side chains extending from a main chain.

Description

201107430 六、發明說明： 【發明所屬之技術領域】 本發明關於電泳粒子（即用於電泳介質之粒子）及此 電泳粒子之製造方法。本發明亦關於電泳介質及加入此粒 子之顯示器。更特定言之，本發明關於其表面經聚合物修 改之電泳粒子。 本申請案關於本申請人之國際申請案第 WO 02/093 246號，讀者可參考作爲背景資訊》 【先前技術】 電泳顯示器近年來已成爲深入硏發之標的。相較於液 晶顯示器時，此顯示器可具有良好之亮度與對比、寬視角 、狀態雙穩性、及低電力消耗的屬性。（名詞「雙穩」及 「雙穩性」在此係以其在此技藝之習知意義使用而指稱包 含具有第一與第二顯示狀態（至少一種光學性質不同）之 顯示元件的顯示器，及使得在已藉有限期間之定址脈衝驅 動任何指定元件後，假設爲其第一或第二顯示狀態在終止 定址脈衝後此狀態持續至少數次（例如至少4次），改變 顯示元件之狀態所需定址脈衝之最小期間。）儘管如此， 這些顯示器之長期影像品質問題使其無法普及地使用。例 如組成電泳顯示器之粒子趨於沉降，造成這些顯示器之不 當使用壽命。 讓渡予或麻省理工學院與E Ink Corporation擁有之許 多專利及申請案近來已公開而敘述各種用於封包電泳與介 質之技術。此封包介質包含許多小囊，其本身各包含一種 .201107430 在流體介質中含電泳地移動粒子之內相、及包圍此內相之 囊壁。一般而言，此囊本身係保持在聚合黏合劑內而形成 位於兩個電極間之內聚層。這些專利及申請案所述之技術 包括： (a) 電泳粒子、流體與流體添加劑；參見例如美國專 利第 5,961，804;6,017,584;6，120,588;6，120,839: 6,262,706； 6,2 62,8 3 3； 6,3 00,93 2； 6,3 23,989； 6,3 77,3 87 ;6,515,649 ； 6,538,801 ； 6,580,545 ； 6,652,075 ； 6,693,620 ； 6,72 1,083 ； 6,727,88 1 ； 6,822,782 ； 6,870,66 1 ；7,002,728 ； 7,038,655 ； 7，170,670 ; 7,180,649 ； 7,230,750； 7,230,751； 7,236,290； 7,247,379： 7,312,916 ;7,375,875; 7,411，720; 7,532,388;與 7,679,814號；及 美國專利申請案公告第 2005/00 1 2980 ; 2006/0202949 ; 2008/0013155 ； 2008/0013156 ； 2008/0266245 ； 2008/0266246 ； 2009/0009852 ； 2009/0027762 ； 2009/0206499; 2009/0225398;與 2010/0045592 號； (b) 囊、黏合劑與封包方法；參見例如美國專利第 6,922,276 與 7,411，719 號； (c) 含電光材料之膜與次組件；參見例如美國專利第 6,982，178號；及美國專利申請案公告第2007/0 1 092 1 9號 ， (d) 背板、黏著層與其他輔助層、及用於顯示器之方 法：參見例如美國專利第7,116,318與7,535,624號； (e) 顏色形成與顏色調整；參見例如美國專利第 -4- 201107430 7,075,5 02號；及美國專利申請案公告第2007/0 1 092 1 9號 » (f) 驅動顯示器之方法；參見例如美國專利第 7,012,600 與 7,453,445 號；及 (g) 顯示器之應用；參見例如美國專利第7,312,784 號；及美國專利申請案公告第2006/0279527號》 如例如美國專利第6,870,66 1號所討論，已知之電泳 介質（封包與未封包）可分成兩種主要型式，爲了方便而 在以下各稱爲「單粒子」與「雙粒子」。單粒子介質僅具 有單型電泳粒子懸浮在其至少一種光學特徵與粒子不同之 經著色懸浮介質中。雙粒子介質具有兩種不同型式（至少 一種光學特徵不同）之粒子、及懸浮流體（其可未著色或 經著色，但是一般未著色）。兩型粒子之電泳移動力不同 :此移動力差異可爲極性（此型在以下可稱爲「電荷相反 雙粒子」介質）及/或大小。單及雙粒子電泳顯示器均可爲 光學特徵位於兩種已述極端光學狀態中間之中間灰態。 —些上述專利及公開申請案揭示在各囊內具有三或更 多不同型式之粒子的封包電泳介質。爲了本發明之目的， 此多粒子介質係視爲雙粒子介質之次物種。 許多上述專利及申請案認爲在封包電泳介質中包圍不 連續微囊之壁可被連續相取代，如此製造所謂之聚合物分 散電泳顯示器，其中電泳介質包含多個不連續電泳流體微 滴、及聚合物材料之連續相，而且此聚合物分散電泳顯示 器內之不連續電泳流體微滴可視爲囊或微囊，即使各個別201107430 VI. Description of the Invention: [Technical Field] The present invention relates to an electrophoretic particle (i.e., a particle used for an electrophoretic medium) and a method of producing the electrophoretic particle. The invention also relates to electrophoretic media and displays incorporating such particles. More specifically, the present invention relates to electrophoretic particles whose surface has been modified by a polymer. In the present application, the applicant's international application No. WO 02/093 246, the reader may refer to as background information. [Prior Art] Electrophoretic displays have become the subject of intensive development in recent years. Compared to liquid crystal displays, this display has good brightness and contrast, wide viewing angle, state bistability, and low power consumption. (The terms "bistable" and "bistable" are used herein to refer to a display having display elements having first and second display states (at least one optical property is different), as used in the conventional sense of the art, and Equivalently, after the specified pulse is driven by the address pulse for a limited period of time, it is assumed that the first or second display state is required to change the state of the display element at least several times (eg, at least four times) after terminating the address pulse. The minimum period of address pulse.) Nevertheless, the long-term image quality problems of these displays make them unusable for use. For example, particles that make up an electrophoretic display tend to settle, causing improper display of these displays. A number of patents and applications owned by MIT or MIT and E Ink Corporation have recently been published to describe various techniques for encapsulating electrophoresis and media. The encapsulating medium comprises a plurality of sachets, each of which comprises a type. 201107430 In the fluid medium, the inner phase of the particles is moved electrophoretically, and the wall surrounding the inner phase. Generally, the bladder itself is held within the polymeric binder to form an inner cohesive layer between the two electrodes. The techniques described in these patents and applications include: (a) Electrophoretic particles, fluids and fluid additives; see, for example, U.S. Patent Nos. 5,961,804; 6,017,584; 6,120,588; 6,120,839: 6,262,706; 6,2 62,8 3 3; 6,3 00,93 2; 6,3 23,989; 6,3 77,3 87 ;6,515,649 ; 6,538,801 ; 6,580,545 ; 6,652,075 ; 6,693,620 ; 6,72 1,083 ; 6,727,88 1 ; 6,822,782 ; 6,870,66 1 ; 7,002,728; 7,038,655; 7,170,670; 7,180,649; 7,230,750; 7,230,751; 7,236,290; 7,247,379: 7,312,916; 7,375,875; 7,411,720; 7,532,388; and 7,679,814; and U.S. Patent Application Publication No. 2005/00 1 2980; 2006/0202949; /0013155 ; 2008/0013156 ; 2008/0266245 ; 2008/0266246 ; 2009/0009852 ; 2009/0027762 ; 2009/0206499 ; 2009/0225398 ; and 2010/0045592 ; (b) capsules, adhesives and packaging methods; see for example U.S. Patent Nos. 6,922,276 and 7,411,719; (c) Films and sub-assemblies containing electro-optic materials; see, for example, U.S. Patent No. 6,982,178; and U.S. Patent Application Publication No. 2007/0 1 092 1 9 (d) Backsheets, adhesive layers and other auxiliary layers, and methods for use in displays; see, for example, U.S. Patent Nos. 7,116,318 and 7,535,624; (e) Color formation and color adjustment; see, e.g., U.S. Patent No. 4-201107430 7,075, 5 02; and U.S. Patent Application Publication No. 2007/0 1 092 1 9» (f) methods of driving a display; see, for example, U.S. Patent Nos. 7,012,600 and 7,453,445; and (g) display applications; see, for example, U.S. Patent No. 7, 312, 784; and U.S. Patent Application Publication No. 2006/0279527. As known, for example, in U.S. Patent No. 6,870,661, known electrophoretic media (packaged and unencapsulated) can be divided into two main types, for convenience. The following are called "single particle" and "double particle". Single-particle media have only single-type electrophoretic particles suspended in a colored suspending medium whose at least one optical characteristic is different from the particles. Two-part media have two different types (at least one optical feature is different) of particles, and a suspending fluid (which may be uncolored or colored, but generally uncolored). The electrophoretic mobility of the two types of particles is different: the difference in mobility can be polar (this type can be referred to below as the "charge opposite two-particle" medium) and/or size. Both single and dual particle electrophoretic displays can be optically characterized by an intermediate gray state intermediate the two extreme optical states already described. - The above patents and published applications disclose encapsulated electrophoretic media having three or more different types of particles within each capsule. For the purposes of the present invention, this multiparticulate medium is considered to be a sub-species of a two-particle medium. Many of the above patents and applications recognize that the walls surrounding the discontinuous microcapsules in the encapsulated electrophoretic medium can be replaced by a continuous phase, thus producing a so-called polymer dispersed electrophoretic display, wherein the electrophoretic medium comprises a plurality of discrete electrophoretic fluid droplets, and a continuous phase of polymeric material, and the discrete electrophoretic fluid droplets in the polymer dispersed electrophoretic display can be considered as capsules or microcapsules, even if individual

S 201107430 微滴崎不附帶不連續囊膜；參見例如上述美國專利第 6,866,760號。因而爲了本發明之目的，此聚合物分散電泳 介質係視爲封包電泳介質之次物種。 如上所示，電泳介質需要流體之存在。在大部分先行 技藝電泳介質中，此流體爲一種液體，但是電泳介質可使 用氣態流體製造；參見例如Kitamura，T.等人之”Electrical toner movement for electronic paper-like display55, IDW Japan， 2001，Paper HCS1-1，及 Yamaguchi, Y.等人之”Toner display using insulative particles charged triboelectrically’’， IDW Japan，2001，Paper AMD4-4)。亦參見美國專利第 7,321，459 與7，236,291號。在將介質以可如此沉降之定向使用時，此 氣體爲主電泳介質似易有如液體爲主電泳介質由於粒子沉 降造成之相同型式問題，例如將介質配置於垂直面之跡象 。事實上，由於氣態懸浮流體相較於液體之較低黏度使電 泳粒子更快速地沉降，粒子沉降似在氣體爲主電泳介質中 爲較液體爲主嚴重之問題。 一種相關型式之電泳顯示器爲所謂之「微胞電泳顯示 器」。在微胞電泳顯示器中，帶電粒子與流體均不封包於 微囊內，而是保留在多個於載體介質（一般爲聚合物膜） 內形成之穴內。參見例如美國專利第 6,672,92 1與 6,788,449 號，其均讓渡予 Sipix Imaging, Inc.。 長久已知電泳粒子之物理性質與表面特徵可藉由在粒 子表面上吸附各種材料，或者將材料化學地鍵結至這些表 面而修改。後來發現由於操作條件之變化可能造成部分或 201107430 全部修改材料離開粒子表面，因而造成粒子之電泳性質的 不欲變化；修改材料可能沉積在電泳顯示器內之其他表面 上，其可能引起進一步之問題，以修改材料簡單地塗覆電 泳粒子不完全令人滿意。因而已發展將修改材料固定於粒 子表面之技術。 上述WO 02/093246號專利敘述多種塗覆聚合物電泳 粒子β教示可用於此塗覆聚合物粒子之多種單體爲特定之 氟化單體，而且此專利申請案含作業例20,其中將大約10 莫耳％之氟化單體組合約90莫耳％之非氟化單體而形成聚 合物塗層。 【發明內容】 現已發現，在電泳粒子之聚合物殼中使用相當小莫耳 比例（不超過約5莫耳％ )之氟化丙烯酸酯或氟化甲基丙 烯酸酯單體（特別是甲基丙烯酸2,2,2-三氟乙酯，以下簡 稱爲”TFEM”）產生上述WO 02/093 246號專利未提及之顯 著優點。特定言之，使用此氟化單體可調整顏料粒子上之 電荷。 在一個態樣中，本發明提供一種在流體中包含多個顏 料粒子之電泳介質，顔料粒子具有化學地鍵結至顏料粒子 之聚合物，其中聚合物包含約〇_1至約5莫耳％之衍生自氟 化丙烯酸酯或氟化甲基丙烯酸酯單體的重複單元。 本發明之電泳介質可加入上述WO 02/093246號專利 所述聚合物殼之任何選用特點。聚合物在經塗覆粒子中之 較佳比例一般爲實質上如上述WO 02/093246號專利所述 201107430 ，即粒子有約4至約15,希望爲約8至約12重量％之聚合 物粒子鍵結粒子。粒子可包含金屬氧化物或氫氧化物，例 如鈦白。聚合物可包含帶電或可帶電基，例如胺基或羧酸 基。聚合物可包含主鏈及多個自主鏈延伸之側鏈，各側鏈 包含至少約4個碳原子。一般而言，聚合物係由二或更多 種丙烯酸酯及/或甲基丙烯酸酯單體形成。 —般而言，氟化單體係組合非氟化丙烯酸酯或甲基丙 烯酸酯單體使用（即聚合物可包含衍生自氟化與非氟化丙 烯酸酯或甲基丙烯酸酯單體之殘基），此目的之較佳單體 爲甲基丙烯酸月桂酯。氟化單體對非氟化單體之莫耳比例 可改變，但是氟化單體一般包含聚合物中全部單體之約1 至約5莫耳％。其較佳爲含至少三個氟原子之高氟化單體 。指定較佳氟化單體爲甲基丙烯酸2,2,2-三氟乙酯，但是 亦可使用其他氟化單體，例如丙烯酸2，2,3，4,4,4 -六氟丁酯 與丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯。 本發明擴展至一種包含本發明電子介質、及至少一個 排列以對電泳介質施加電場之電極的電泳顯示器，及一種 包含此顯示器之電子書閱讀器、可攜式電腦、桌上型電腦 、行動電話、智慧卡、標誌、錶、架標籤（shelf label)、或 快閃驅動裝置（flash drive)。 【實施方式】 在詳細討論本發明之電泳介質及方法之前，相信希望 簡短地敘述其中意圖使用這些介質之—些型式之電泳顯示 器。S 201107430 Microdrops does not carry a discontinuous capsule; see, for example, the aforementioned U.S. Patent No. 6,866,760. Thus, for the purposes of the present invention, the polymer dispersed electrophoretic medium is considered to be a sub-species of the encapsulated electrophoretic medium. As indicated above, the electrophoretic medium requires the presence of a fluid. In most prior art electrophoretic media, the fluid is a liquid, but the electrophoretic medium can be made using a gaseous fluid; see, for example, Kitamura, T. et al. "Electrical toner movement for electronic paper-like display 55, IDW Japan, 2001, Paper. HCS1-1, and Yamaguchi, Y. et al. "Toner display using insulative particles charged triboelectrically'', IDW Japan, 2001, Paper AMD 4-4). See also U.S. Patents 7,321,459 and 7,236,291. When the medium is used in such an orientation that it can be so settled, the gas as the main electrophoretic medium tends to have the same type of problem as the liquid-based electrophoretic medium is caused by particle sedimentation, such as the indication that the medium is disposed in a vertical plane. In fact, due to the lower viscosity of the gaseous suspension fluid compared to the liquid, the electrophoretic particles settle more quickly, and the sedimentation of the particles appears to be a more serious problem in liquid-based electrophoretic media. A related type of electrophoretic display is a so-called "micro-cell electrophoretic display". In a microelectrophoresis display, both charged particles and fluid are not encapsulated within the microcapsules, but remain in a plurality of pockets formed within the carrier medium (typically a polymeric film). See, for example, U.S. Patent Nos. 6,672,92 1 and 6,788,449, each assigned to Sipix Imaging, Inc. It has long been known that the physical and surface characteristics of electrophoretic particles can be modified by adsorbing various materials on the surface of the particles or by chemically bonding the materials to these surfaces. It was later discovered that due to changes in operating conditions, some or all of the 201107430 modified materials may leave the surface of the particles, causing undesirable changes in the electrophoretic properties of the particles; modifying the material may deposit on other surfaces within the electrophoretic display, which may cause further problems. Simply coating the electrophoretic particles with modified materials is not entirely satisfactory. Thus, techniques have been developed to fix modified materials to the surface of the particles. The above-mentioned WO 02/093246 patent describes a plurality of coated polymer electrophoretic particles β teaching that a plurality of monomers which can be used for coating the polymer particles are specific fluorinated monomers, and this patent application contains Working Example 20, which will be approximately 10 mole % of fluorinated monomer combines about 90 mole % of non-fluorinated monomer to form a polymer coating. SUMMARY OF THE INVENTION It has now been found that a relatively small molar ratio (not more than about 5 mole %) of fluorinated acrylate or fluorinated methacrylate monomer (especially methyl) is used in the polymer shell of the electrophoretic particles. 2,2,2-trifluoroethyl acrylate, hereinafter abbreviated as "TFEM", yields significant advantages not mentioned in the above-mentioned WO 02/093246. In particular, the use of this fluorinated monomer adjusts the charge on the pigment particles. In one aspect, the invention provides an electrophoretic medium comprising a plurality of pigment particles in a fluid, the pigment particles having a polymer chemically bonded to the pigment particles, wherein the polymer comprises from about 〇_1 to about 5 mol% Repetitive units derived from fluorinated acrylate or fluorinated methacrylate monomers. The electrophoretic medium of the present invention can be incorporated into any of the optional features of the polymer shell described in the above-mentioned WO 02/093246. The preferred proportion of polymer in the coated particles is generally substantially as described in the above-mentioned WO 02/093246 patent 201107430, i.e., particles having from about 4 to about 15, desirably from about 8 to about 12 weight percent polymer particles. Bond particles. The particles may comprise a metal oxide or hydroxide, such as titanium white. The polymer may comprise a charged or chargeable group, such as an amine or carboxylic acid group. The polymer may comprise a backbone and a plurality of side chains of autonomous chain extension, each side chain comprising at least about 4 carbon atoms. In general, the polymer is formed from two or more acrylate and/or methacrylate monomers. In general, a fluorinated single system is used in combination with a non-fluorinated acrylate or methacrylate monomer (ie, the polymer may comprise residues derived from fluorinated and non-fluorinated acrylate or methacrylate monomers). The preferred monomer for this purpose is lauryl methacrylate. The molar ratio of fluorinated monomers to non-fluorinated monomers can vary, but fluorinated monomers generally comprise from about 1 to about 5 mole percent of all monomers in the polymer. It is preferably a highly fluorinated monomer having at least three fluorine atoms. The preferred fluorinated monomer is 2,2,2-trifluoroethyl methacrylate, but other fluorinated monomers such as 2,2,3,4,4,4-hexafluorobutyl acrylate may also be used. 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl acrylate. The invention extends to an electrophoretic display comprising the electronic medium of the invention and at least one electrode arranged to apply an electric field to the electrophoretic medium, and an e-book reader, portable computer, desktop computer, mobile phone including the display , smart card, logo, watch, shelf label, or flash drive. [Embodiment] Before discussing the electrophoretic medium and method of the present invention in detail, it is believed that it is desirable to briefly describe some types of electrophoretic displays in which these media are intended to be used.

S 201107430 本發明之電泳介質可爲任何上述E Ink與MIT專利及 申請案所述之型式’而且現在參考附圖之第1至4圖敘述 此介質之較佳具體實施例》 第1A與1B圖所不之第一電泳顯示器（通常稱爲1〇〇 )包含一種封包電泳介質（通常稱爲102)，其包含多個囊 104(第1A與1B圖僅顯示其一），各含懸浮液ι〇6及分散 於其中之多個單型粒子108 (爲了描述之目的而假設爲黑 色）。粒子108係電泳地移動且可由碳黑形成。在以下說明 中假設粒子108帶正電，雖然當然如果需要亦可使用帶負 電粒子。（粒子1〇8之三角形、及以下所討論其它粒子之正 方形與圓形係純粹爲了可在附圖中容易地區別各種型式之 粒子而以描述之方式使用，而且絕非對應實際粒子之物理 形式，其一般爲實質上球形。然而本顯示器不排除使用非 球形粒子。）顯示器1〇〇進一步包含一種形成觀看者經其 觀看顯示器100之觀看表面的常用透明前電極110、及多 個各界定顯示器100之一個像素的不連續後電極112 (第 1A與1B圖僅顯示一個後電極112)。爲了容易描述及理解 ，第1A與1B圖僅顯示形成後電極112界定之像素的單一 微囊，雖然實際上各像素通常使用大量（20個或更多）之 微囊。後電極112係安裝在基板114上。 懸浮液106係著色使得觀看者經前電極110觀看顯示 器1〇〇無法見到位於第1A圖所示相鄰後電極112之位置的 粒子108。懸浮液106之必要顔色可藉由將染料溶於液體 而提供。由於經著色懸浮液106與粒子108使電泳介質102 201107430 呈現不透明，後電極Π2與基板114可爲透明或不透明， 因爲通過不透明電泳介質102無法見到。 囊104與粒子108可製成大範圍之大小。然而通常較 佳爲囊之厚度垂直於電極測量爲約15至5 00微米之範圍， 而粒子108 —般具有約0.25至約2微米之直徑。 第1Α圖顯示後電極112帶負電且前電極110帶正電 之顯示器100。在此條件下，帶正電粒子108被負後電極 1 1 2吸引，如此位於相鄰後電極.1 1 2，在此其對經前電極1 1 0 觀看顯示器1〇〇之觀看者被經著色液體106隱藏。因而第 1Α圖所示像素對觀看者顯示液體106之顏色，其爲了描述 之目的假設爲白色。（雖然顯示器100在第1Α與1Β圖中 描述成後電極112在底部，實際上爲了顯示器100之最大 可視性，前後電極一般均垂直地配置。通常在此所述本發 明之介質與顯示器絕不依賴重力控制粒子之移動；此重力 下移動實際上太慢而無法用於控制粒子移動。） 第1Β圖顯示前電極11〇相對後電極112爲負之顯示器 1〇〇。由於粒子108帶正電，其被帶負電前電極110吸引， 如此粒子108移至相鄰前電極110,而且像素顯示粒子108 之黑色。 在第1Α與1Β圖中，囊104係描述成實質上菱鏡 (prismatic)形式，具有顯著地大於其高度（垂直這些面） 之寬度（平行電極面）。此菱鏡形狀之囊104爲蓄意的。如 果囊104爲本質上球形，則在第18圖所示之黑態中，粒子 趨於聚集在囊之最高部分，囊中央正上方置中之有限 -10- 201107430 區域。觀看者看見之顔色則爲此中央黑色區域與包圍此中 央區域之白色環帶的本質上平均顏色，在此白色液體106 爲可見到。如此即使是在此假定黑態，觀看者見到灰色而 非純黑色，及兩個極端光學狀態間之對比因而有限。相反 地，以第1A與1B圖所示菱鏡形式之微囊，粒子108覆蓋 囊之本質上全部截面使得可見到無或至少非常少之白色液 體，而且增強囊之極端光學狀態間之對比。進一步討論此 點，及在電泳層中完成囊之緊密塡充的需要性，讀者可參 考上述美國專利第6,067,185號，及對應之公告國際申請案 WO 99/1 0767號。亦如上述E Ink與MIT專利及申請案所 述，爲了對電泳介質提供機械整體性，微囊通常嵌於固態 黏合劑內，但是在第1至3圖爲了易於描述而省略此黏合 劑。 第2A與2B圖所示之第二電泳顯示器（通常稱爲200 )包含封包電泳介質（通常稱爲202)，其包含多個囊204 ，各含懸浮液206且多個帶正電黑色粒子108分散於其中 ，與以上討論之第一顯示器100所討論相同。顯示器200 進一步包含前電極110、後電極112、與基板114，其均與 第一顯示器100之對應號碼相同。然而除了黑色粒子108 ，多個帶負電粒子218懸浮於液體206，其爲了本發明之 目的假設爲白色。 —般而言，液體206未著色（即本質上透明），雖然其 中可能存在一些顏色以調整顯示器之各種狀態的光學性質 。第2A圖顯示具相對所描述像素之後電極112爲帶正電之S 201107430 The electrophoretic medium of the present invention may be of the type described in the above-mentioned E Ink and MIT patents and applications, and a preferred embodiment of the medium will now be described with reference to Figures 1 to 4 of the accompanying drawings. Figs. 1A and 1B The first electrophoretic display (commonly referred to as 1 〇〇) comprises a packet of electrophoretic medium (commonly referred to as 102) comprising a plurality of capsules 104 (only panels 1A and 1B are shown), each containing a suspension ι 〇6 and a plurality of single-type particles 108 dispersed therein (assumed to be black for purposes of description). The particles 108 are electrophoretically moved and may be formed of carbon black. In the following description it is assumed that the particles 108 are positively charged, although of course negatively charged particles can be used if desired. (The triangles of particles 1〇8, and the squares and circles of the other particles discussed below are used purely for the purpose of easily distinguishing the various types of particles in the drawings, and are in no way corresponding to the physical form of the actual particles. It is generally substantially spherical. However, the present display does not preclude the use of non-spherical particles.) The display 1 further includes a conventional transparent front electrode 110 that forms a viewing surface through which the viewer views the display 100, and a plurality of defined displays A discontinuous rear electrode 112 of one pixel of 100 (only the one rear electrode 112 is shown in FIGS. 1A and 1B). For ease of description and understanding, Figures 1A and 1B show only a single microcapsule that forms the pixels defined by the back electrode 112, although in practice each pixel typically uses a large number (20 or more) of microcapsules. The rear electrode 112 is mounted on the substrate 114. The suspension 106 is colored such that the viewer sees through the front electrode 110 that the display 108 does not see the particles 108 located adjacent the adjacent back electrode 112 shown in Figure 1A. The necessary color of the suspension 106 can be provided by dissolving the dye in a liquid. Since the electrophoretic medium 102 201107430 is rendered opaque by the colored suspension 106 and particles 108, the back electrode Π 2 and the substrate 114 may be transparent or opaque because it is not visible through the opaque electrophoretic medium 102. The bladder 104 and the particles 108 can be made to a wide range of sizes. Preferably, however, the thickness of the bladder is measured in the range of from about 15 to 500 microns perpendicular to the electrode, while the particles 108 generally have a diameter of from about 0.25 to about 2 microns. Figure 1 shows a display 100 with the back electrode 112 negatively charged and the front electrode 110 positively charged. Under this condition, the positively charged particles 108 are attracted by the negative back electrode 1 1 2, so that they are located adjacent to the rear electrode .1 1 2, where they are viewed by the viewer through the front electrode 1 1 0 The coloring liquid 106 is hidden. Thus the pixel shown in Figure 1 shows the color of the liquid 106 to the viewer, which is assumed to be white for purposes of description. (Although display 100 is depicted in Figures 1 and 1 as rear electrode 112 at the bottom, in practice for the maximum visibility of display 100, the front and rear electrodes are generally vertically disposed. Generally, the media and display of the present invention are not described herein. Depending on gravity, the movement of the particles is controlled; this movement under gravity is actually too slow to control the movement of the particles.) Figure 1 shows a display 1 前 with the front electrode 11 〇 opposite the back electrode 112. Since the particles 108 are positively charged, they are attracted by the negatively charged front electrode 110, such that the particles 108 move to the adjacent front electrode 110, and the pixels display the black color of the particles 108. In Figures 1 and 1 , the capsule 104 is depicted as a substantially prismatic form having a width (parallel electrode faces) that is significantly greater than its height (vertical to these faces). This prismatic shaped capsule 104 is deliberate. If the capsule 104 is substantially spherical, then in the black state shown in Figure 18, the particles tend to accumulate in the highest part of the capsule, centered in the center of the capsule, in the limited -10- 201107430 region. The color seen by the viewer is the essentially average color of the central black zone and the white annulus surrounding the central zone, where the white liquid 106 is visible. Thus, even if the black state is assumed here, the viewer sees gray instead of pure black, and the contrast between the two extreme optical states is limited. Conversely, with the microcapsules in the form of mirrors shown in Figures 1A and 1B, the particles 108 cover the entire cross-section of the capsule such that no or at least very few white liquids are visible, and the contrast between the extreme optical states of the capsule is enhanced. Further discussion of this and the need to complete the tight filling of the capsules in the electrophoretic layer is described in the above-referenced U.S. Patent No. 6,067,185, the disclosure of which is incorporated herein by reference. As also described in the above-mentioned E Ink and MIT patents and applications, in order to provide mechanical integrity to the electrophoretic medium, the microcapsules are usually embedded in a solid binder, but the binders are omitted in Figures 1 to 3 for ease of description. The second electrophoretic display (generally referred to as 200) shown in Figures 2A and 2B comprises a packet electrophoretic medium (commonly referred to as 202) comprising a plurality of capsules 204 each containing a suspension 206 and a plurality of positively charged black particles 108 Dispersed therein is the same as discussed above for the first display 100 discussed above. The display 200 further includes a front electrode 110, a rear electrode 112, and a substrate 114, both of which are identical to the corresponding numbers of the first display 100. However, in addition to the black particles 108, a plurality of negatively charged particles 218 are suspended in the liquid 206, which is assumed to be white for the purposes of the present invention. In general, liquid 206 is uncolored (i.e., substantially transparent), although some color may be present to adjust the optical properties of the various states of the display. Figure 2A shows that electrode 112 is positively charged after having a relatively described pixel

S -11- .201107430 前電極110的顯示器200。帶正電粒子108係靜電地保持 相鄰後電極112，而帶負電粒子218係靜電地保持靠近前 電極110。因而由於可見到白色粒子218且隱藏黑色粒子 108,通過前電極110觀看顯示器200之觀看者見到白色像 素。 第2B圖顯示具相對所描述像素之後電極112爲帶負 電之前電極110的顯示器2 00 »如第1B圖所示之對應光學 狀態，帶正電粒子108現在靜電地被負前電極110吸引， 而帶負電粒子218係靜電地被正後電極112吸引。因而粒 子108移至相鄰前電極110，及像素顯示粒子108之黑色 ，其隱藏白色粒子218。 第3A與3B所示之本發明第三電泳顯示器（通常稱爲 300)包含封包電泳介質（通常稱爲302)，其包含多個囊 304。顯示器300進一步包含前電極110、後電極112、與 基板114，其均與前述顯示器100及200之對應號碼相同 。顯示器300類似上述顯示器200，液體306未著色且白 色帶負電粒子218懸浮於其中。然而顯示器300異於顯示 器200在於紅色帶負電粒子320之存在，其具有實質上較 白色粒子218低之電泳移動性。 第3A圖顯示具相對所描述像素之後電極112爲帶正 電之前電極110的顯示器300。帶負電白色粒子218與帶 負電紅色粒子320均被前電極110吸引，但是由於白色粒 子218具有實質上較高之電泳移動力，其先到達前電極110 (應注意，第3A圖所示光學狀態通常藉由將第3B圖所示S -11- .201107430 Display 200 of front electrode 110. The positively charged particles 108 electrostatically hold adjacent rear electrodes 112, while the negatively charged particles 218 are electrostatically held close to the front electrode 110. Thus, as the white particles 218 are visible and the black particles 108 are hidden, the viewer viewing the display 200 through the front electrode 110 sees the white pixels. Figure 2B shows display 200 with electrode 112 as negatively charged electrode 110 with respect to the described pixel. » A corresponding optical state as shown in Figure 1B, positively charged particles 108 are now electrostatically attracted by negative front electrode 110, and The negatively charged particles 218 are electrostatically attracted by the positive rear electrode 112. Thus, the particles 108 move to the adjacent front electrode 110, and the pixels display the black color of the particles 108, which hide the white particles 218. The third electrophoretic display (commonly referred to as 300) of the present invention shown in Figures 3A and 3B comprises a packet electrophoretic medium (commonly referred to as 302) comprising a plurality of pockets 304. The display 300 further includes a front electrode 110, a rear electrode 112, and a substrate 114, both of which are identical to the corresponding numbers of the aforementioned displays 100 and 200. Display 300 is similar to display 200 described above, with liquid 306 uncolored and white negatively charged particles 218 suspended therein. However, display 300 differs from display 200 in the presence of red negatively charged particles 320, which have substantially lower electrophoretic mobility than white particles 218. Figure 3A shows display 300 with electrode 112 being positively charged front electrode 110 with respect to the described pixel. Both the negatively charged white particles 218 and the negatively charged red particles 320 are attracted by the front electrode 110, but since the white particles 218 have a substantially higher electrophoretic moving force, they first reach the front electrode 110 (note that the optical state shown in Fig. 3A) Usually by showing Figure 3B

S -12- 201107430 光學狀態之電極的極性急劇地反轉而產生，如此強迫白色 粒子218與紅色粒子320橫越過囊3 04之厚度，及如此可 使白色粒子218因其移動力較大而造成其在紅色粒子320 之前到達其相鄰前電極1 1 0之位置）。如此白色粒子2 1 8形 成緊鄰前電極110之連續層，因而隱藏紅色粒子320。因 而由於可見到白色粒子218且隱藏紅色粒子320，通過前 電極ΠΟ觀看顯示器300之觀看者看見白色像素。 第3B圖顯示具相對所描述像素之後電極112爲帶負 電之前電極110的顯示器300。帶負電白色粒子218與帶 負電紅色粒子3 20均被後電極112吸引，但是由於白色粒 子218具有較高之電泳移動力，在第3B圖所示光學狀態係 藉由將第3A圖所示光學狀態之電極的極性急劇地反轉而 產生時，白色粒子218較紅色粒子3 20先到達後電極112 ，使得白色粒子218形成緊鄰後電極112之連續層，而留 下紅色粒子320之連續層面對前電極110。因而由於可見 到紅色粒子320且隱藏白色粒子218，通過前電極110觀 看顯示器300之観看者看見紅色像素。 第4A與4B圖描述本發明之聚合物分散電泳介質及用 以製造此介質之方法。此聚合物分散介質含非球形微滴， 而且係使用製造一種在其形成後實質上可收縮之膜的膜形 成材料製備。用於此目的之較佳不連續相爲明膠，雖然或 可使用其他蛋白質材料，可能與可交聯聚合物。將液態材 料（其最終形成連續相）與微滴之混合物形成及塗覆在基 板上形成如第4A圖描述之結構。第4A圖顯示在形成膜之 3 -13- 201107430 方法中包含微滴412分散於液態介質414之層410，此層 410已被塗覆在事先具有透明導電材料（如氧化銦錫）之 層418的基板416(較佳爲撓性聚合膜，如聚酯膜）上。 液態材料形成含本質上球形微滴4 1 2之相對厚層4 1 0 ;如 第4A圖所示。在層410已形成固態連續層後，使層較佳爲 在大約室溫（雖然如果希望則可將層加熱）乾燥足以將明 膠脫水之時間，如此造成層厚度之實質上減小及製造第4B 圖描述之型式，此經乾燥及收縮層在第4B圖中稱爲410’ 。層之垂直收縮（即垂直於基板416表面之收縮）事實上 將原始球形微滴壓縮成扁橢圓體，其垂直於表面之厚度實 質上較其平行於表面之橫向尺寸小。實際上通常將微滴充 分地緊密塡充使相鄰微滴之橫向邊緣彼此接觸，使得微滴 之最終形式更接近地類似不規則稜鏡而非扁橢圓體。亦如 第4B圖所示，超過一層微滴可存在於最終介質。在介質爲 第4B圖所示其中微滴爲多分散（即存在大尺寸範圍之微滴 )之型式時，此多層之存在因其降低基板之小面積不被任 何微滴覆蓋的機會而有利；因此多層有助於確保電泳介質 爲完全不透明，及在由此介質形成之顯示器中，基板之任 何部分均不被看見。然而在使用本質上單分散微滴（即實 質上均爲同尺寸之微滴）之介質時，其通常能建議將介質 塗覆在收縮後產生緊密塡充單層微滴之層，參考美國專利 第6,839,158號。因爲其在微封包電泳介質中無相對硬之微 囊壁，本發明之聚合物分散介質中之微滴可趨於較微囊更 密集地塡充成緊密塡充單層。S -12- 201107430 The polarity of the electrode of the optical state is sharply reversed, thus forcing the white particles 218 and the red particles 320 to traverse the thickness of the capsule 404, and thus the white particles 218 may be caused by the large moving force thereof. It reaches the position of its adjacent front electrode 1 1 0 before the red particles 320). The white particles 2 1 8 thus form a continuous layer in close proximity to the front electrode 110, thus hiding the red particles 320. Thus, as the white particles 218 are visible and the red particles 320 are hidden, the viewer viewing the display 300 through the front electrode 看见 sees the white pixels. Figure 3B shows display 300 with electrode 112 being negatively charged front electrode 110 with respect to the described pixel. Both the negatively charged white particles 218 and the negatively charged red particles 3 20 are attracted by the rear electrode 112, but since the white particles 218 have a higher electrophoretic moving force, the optical state shown in Fig. 3B is by the optical shown in Fig. 3A. When the polarity of the electrode of the state is sharply reversed, the white particles 218 reach the rear electrode 112 earlier than the red particles 3 20 such that the white particles 218 form a continuous layer adjacent to the back electrode 112, leaving a continuous layer of red particles 320. Pair the front electrode 110. Thus, since the red particles 320 are visible and the white particles 218 are hidden, the viewer viewing the display 300 through the front electrode 110 sees the red pixels. Figures 4A and 4B depict a polymer dispersed electrophoretic medium of the present invention and a method for making the medium. The polymer dispersion medium contains non-spherical droplets and is prepared using a film forming material which produces a film which is substantially shrinkable after it is formed. The preferred discontinuous phase for this purpose is gelatin, although other proteinaceous materials may be used, possibly with crosslinkable polymers. A mixture of liquid material (which ultimately forms a continuous phase) and droplets is formed and coated on a substrate to form a structure as depicted in Figure 4A. Figure 4A shows a layer 410 comprising droplets 412 dispersed in a liquid medium 414 in a method of forming a film, which layer 410 has been coated with a layer 418 previously having a transparent conductive material (e.g., indium tin oxide). The substrate 416 (preferably a flexible polymeric film such as a polyester film). The liquid material forms a relatively thick layer 4 1 0 containing essentially spherical droplets 4 1 2; as shown in Figure 4A. After the layer 410 has formed a solid continuous layer, the layer is preferably dried at about room temperature (although the layer can be heated if desired) to be sufficient to dehydrate the gelatin, thereby causing substantial reduction in layer thickness and fabrication of the fourth layer. The figure depicts a pattern in which the dried and contracted layer is referred to as 410' in Figure 4B. The vertical shrinkage of the layer (i.e., the contraction perpendicular to the surface of the substrate 416) actually compresses the original spherical droplet into a flat ellipsoid having a thickness perpendicular to the surface that is substantially smaller than its transverse dimension parallel to the surface. In practice, the droplets are typically sufficiently tightly packed so that the lateral edges of adjacent droplets contact each other such that the final form of the droplets more closely resembles an irregular ridge rather than a oblate ellipsoid. As also shown in Figure 4B, more than one layer of droplets may be present in the final medium. In the case where the medium is shown in Fig. 4B in which the droplets are polydisperse (i.e., droplets having a large size range), the presence of the plurality of layers is advantageous because it reduces the chance that the small area of the substrate is not covered by any droplets; The multilayer thus helps to ensure that the electrophoretic medium is completely opaque, and that no part of the substrate is visible in the display formed by the medium. However, when using a medium that is essentially monodisperse droplets (ie, droplets that are substantially the same size), it is generally recommended to apply the medium to a layer that is tightly packed to form a single layer of droplets after shrinking, with reference to US patents. No. 6,839,158. Because of the absence of relatively hard microcapsule walls in the microencapsulated electrophoretic medium, the droplets in the polymeric dispersion medium of the present invention tend to be more densely packed into a tighter monolayer than the microcapsules.

E -14- 201107430 與預期相反，實驗上已發現在介質乾燥期間微滴不凝 集。然而其不排除在本發明之特定具體實施例中可能發生 相鄰囊間之一些壁破裂，如此提供微滴間部分連接的可能 性》 在乾燥步驟期間發生之微滴變形程度，及因此之微滴 之最終形式，可因控制水於明膠中之比例、及此溶液對微 滴之比例而改變。例如使用2至1 5重量％之明膠溶液、及 使用200克之各明膠溶液與50克之非水性內相（其形成微 滴）進行實驗。爲了製造厚30微米之電泳介質最終層，其 必須塗覆厚139微米之2%明膠溶液/內相混合物層；在乾 燥時此層製造厚30微米之電泳介質，其含92.6體積％之微 滴。另一方面，爲了製造相同厚度之電泳介質，其塗覆厚 93微米之15 %明膠溶液/內相混合物，及在乾燥時製造含 6 2.5體積％之微滴的電泳介質。由2%明膠溶液製造之介質 承受粗魯處理時較所期望爲脆弱；由含5至15重量％之明 膠的明膠溶液製造之介質具有令人滿意之機械性質。 微滴在最終電泳介質中之變形程度亦受微滴之起初大 小、及此起初大小與電泳介質之最終層厚度間關係影響。 實驗顯示微滴之平均起初大小越大及/或此平均起初大小 對最終層厚度之比例越大，則在最終層中微滴由球形變形 越多。通常較佳爲微滴之平均起初大小爲最終層厚度之約 2 5 %至約4 00%。例如在其中最終層厚度爲30微米之前述實 驗中，以1 0至1 0 0微米之起初平均微滴大小得到良好之結 果。 3 -15- 201107430 明膠藉溶膠/凝膠轉變形成膜，但是本 溶膠/凝膠轉變形成其膜之膜形成材料。例 體或寡聚物之聚合、藉單體或寡聚物之交 輻射硬化'或藉任何其他已知之膜形成方 ’在其中首先形成膜然後造成厚度收縮之 中，此收縮不必藉明膠膜收縮之相同類型 ，而是可自膜去除水性或非水性溶劑、交 何其他之習知步驟完成。 在本發明之聚合物分散電泳介質中， 電泳介質之至少40%，而且較佳爲約50至 見美國專利第6,866,760號。應強調，用於 散介質之微滴可具有第1至3圖所描述粒 任何組合。 本發明可應用於第1至4圖所示之任 泳介質。然而本發明不限於封包及聚合物 而且亦可應用於微胞及未封包介質。 由以下實例明顯可知，在用於電泳顯 合物殻中使用控制量之氟化單體，增加帶 位，及在此如此情形所常見，負粒子爲白 )，所得之增加負Γ電位本身顯露改良（較 :電位隨氟化單體在聚合物殼中之比例 。然而高於約5莫耳％之氟化單體則特定 態影像損失（測爲不驅動顯示器經一段時 後顯示器之暗態變化）開始增加，及暗態 發明不限於藉此 如膜形成可藉單 聯、藉聚合物之 法完成。類似地 本發明較佳變體 的脫水機構完成 聯聚合膜、或任 其希望微滴包含 約8 0體積％ ;參 本發明聚合物分 子與懸浮流體之 何形式的封包電 分散電泳介質， 示器之粒子的聚 負電粒子之Γ電 色粒子（如鈦白 :反射性）之白態 增加而越來越負 缺點變明顯。暗 間（如2分鐘） 本身變成較不暗 -16- .201107430 ，因而負面地影響顯示器之動態範圍（按L*單位測量之顯 示器的暗與白態間之差異，（其中L*具有一般CIE定義： L* = 116(R/R〇)1/3-16， 其中R爲反射度及R〇爲標準反射値））。因而通常較佳爲將 氟化單體在聚合物殼中之莫耳比例保持在約0.1至約5,希 望爲約1至5莫耳％之範圍。期了解，氟化單體之最適比 例可隨使用之指定氟化單體（特別是其氟化程度）、使用之 其他單體、及其他因素（包括存在於電泳介質之其他粒子 )而稍微改變。通常氟化單體之最適比例似爲約1莫耳％ ，因爲此氟化單體含量產生Γ電位程度實質上大量增加， 同時避免上述較高氟化單體附帶之缺點。 用於本發明電泳介質之塗覆聚合物粒子可藉任何上述 WO 02/09 3 246號專利所述方法製造。在一種此方法中，將 欲形成之其上塗覆聚合物之粒子、與具有可反應及鍵結至 粒子之官能基與可聚合之官能基（例如側接乙烯基或其他 乙烯不飽和基）之二官能基試劑反應。 現在僅藉描述之方式以下實例顯示用於本發明之特佳 試劑、條件及技術的範圍。 實例1:在聚合物殼中含甲基丙烯酸2,2,2-三氟乙酯與甲 基丙烯酸月桂酯之白色鈦白顔料之製備 實質上如上述PCEP申請案所述而製備表面經甲基丙 烯酸3-(三甲氧基矽烷基）丙酯官能化之DuPont R-794鈦 白》在1公升塑膠瓶中，藉超音波將500克之此顏料分散 於426克（500毫升）之甲苯。將1公升之套玻璃反應器E -14- 201107430 Contrary to expectations, it has been experimentally found that the droplets do not aggregate during drying of the medium. However, it does not exclude that some wall ruptures between adjacent capsules may occur in a particular embodiment of the invention, thus providing the possibility of partial connection between droplets" the extent of droplet deformation that occurs during the drying step, and thus The final form of the drop can be varied by controlling the proportion of water in the gelatin and the ratio of the solution to the droplets. For example, an experiment is carried out using 2 to 15% by weight of a gelatin solution, and using 200 g of each gelatin solution and 50 g of a non-aqueous internal phase (which forms droplets). In order to produce a final layer of electrophoretic medium having a thickness of 30 microns, it must be coated with a 2% thick gelatin solution/internal phase mixture layer of 139 microns; this layer is made to produce a 30 micron thick electrophoretic medium containing 92.6% by volume of droplets upon drying. . On the other hand, in order to manufacture an electrophoretic medium of the same thickness, it was coated with a 15 μm gelatin solution/internal phase mixture having a thickness of 93 μm, and an electrophoretic medium containing 62.5 vol% of droplets was produced upon drying. Media made from 2% gelatin solution are less fragile when subjected to rude treatment; media made from gelatin solution containing 5 to 15% by weight of gelatin have satisfactory mechanical properties. The degree of deformation of the droplets in the final electrophoretic medium is also affected by the initial size of the droplets and the relationship between the initial size and the final layer thickness of the electrophoretic medium. Experiments have shown that the larger the average size of the droplets at the beginning and/or the greater the ratio of the average size to the thickness of the final layer, the more the droplets are deformed by the spheres in the final layer. It is generally preferred that the average initial size of the droplets is from about 25 % to about 400% of the thickness of the final layer. For example, in the foregoing experiment in which the final layer thickness was 30 μm, a good result was obtained with an initial average droplet size of 10 to 100 μm. 3 -15- 201107430 Gelatin forms a film by sol/gel conversion, but the sol/gel transition forms a film forming material of its film. Polymerization of the precursor or oligomer, by radiation hardening of the monomer or oligomer 'or by any other known film forming means in which the film is first formed and then caused to shrink in thickness, the shrinkage does not have to shrink by gelatin film The same type, but can be accomplished by removing the aqueous or non-aqueous solvent from the membrane, and by other conventional steps. In the polymer dispersed electrophoretic medium of the present invention, the electrophoretic medium is at least 40%, and preferably about 50 to see U.S. Patent No. 6,866,760. It should be emphasized that the droplets used in the bulk medium may have any combination of the particles described in Figures 1 to 3. The present invention can be applied to any of the swimming media shown in Figures 1 to 4. However, the invention is not limited to packets and polymers and can also be applied to micelles and unencapsulated media. It is apparent from the following examples that the use of a controlled amount of fluorinated monomer in the electrophoretic ampoule shell, increasing the band position, and as is often the case here, the negative particles are white), the resulting increase in the negative zeta potential itself is revealed Improved (compared to: potential with the proportion of fluorinated monomer in the polymer shell. However, higher than about 5 mol% of fluorinated monomer is a specific state of image loss (measured not to drive the display after a period of time after the dark state of the display The change) begins to increase, and the dark state invention is not limited thereto, as the film formation can be accomplished by means of a single polymer, by means of a polymer. Similarly, the dehydration mechanism of the preferred variant of the invention completes the polymerization film, or any desired droplet Containing about 80% by volume; in the form of a polymer-dispersed electrophoretic medium of the polymer molecule and the suspension fluid of the present invention, the white state of the electro-negative particles of the particles of the indicator (such as titanium white: reflective) The increase and the more negative defects become obvious. The dark space (such as 2 minutes) itself becomes less dark-16-.201107430, thus negatively affecting the dynamic range of the display (the dark and white state of the display measured in L* units) The difference, (where L* has the general CIE definition: L* = 116(R/R〇) 1/3-16, where R is the reflectance and R〇 is the standard reflection 値)). Therefore, it is generally preferred to use fluorine. The molar ratio of the monomer in the polymer shell is maintained in the range of from about 0.1 to about 5, desirably in the range of from about 1 to 5 mole %. It is understood that the optimum ratio of fluorinated monomer can be specified with the use of the specified fluorinated single The body (especially its degree of fluorination), other monomers used, and other factors, including other particles present in the electrophoretic medium, vary slightly. Typically, the optimum ratio of fluorinated monomers appears to be about 1 mol% because This fluorinated monomer content produces a substantially substantial increase in the zeta potential while avoiding the disadvantages associated with the higher fluorinated monomers described above. The coated polymer particles useful in the electrophoretic media of the present invention can be borrowed from any of the above WO 02/09 3 246 Made by the method described in the patent. In one such method, the particles on which the polymer is to be formed are formed, and the functional groups which are reactive and bonded to the particles are polymerizable with the functional group (for example, vinyl or The other difunctional reagent of the ethylenically unsaturated group is reacted. The following examples by way of illustration only show the range of particularly preferred reagents, conditions and techniques for use in the present invention. Example 1: 2,2,2-trifluoroethyl methacrylate and methacrylic acid in a polymer shell Preparation of a white titanium white pigment of lauryl ester A DuPont R-794 titanium white functionalized on the surface of 3-(trimethoxydecyl) propyl methacrylate was prepared essentially as described in the above PCEP application. In the bottle, 500 grams of this pigment was dispersed in 426 grams (500 ml) of toluene by ultrasonic. A 1 liter glass reactor was placed.

S -17- 201107430 裝以1.7158莫耳之單體，分有甲基丙烯酸月桂酯與TFEM 以產生各單體之所需莫耳濃度。TFEM之莫耳比例爲0.1、 1、5、10、25與50莫耳％，其餘爲甲基丙烯酸月桂酯《將 顏料分散液加入反應器，及將反應器以氮沖洗且加熱至 65 °C。將事先溶於110毫升之甲苯的自由基引發劑（5.0克 之2,2’-偶氮貳（2-甲基丙腈），AIBN)經60分鐘逐滴加入 。將容器在氮下以連續攪動在65 °C加熱過夜，然後暴露於 大氣。然後將混合物分配至4個1公升塑膠瓶中，及將大 約5 00毫升之其他甲苯加入各瓶。將瓶劇烈地攪拌。將顏 料以3 5 00 rpm離心20分鐘而隔離。將上清液丟棄，及對 各瓶加入大約70 0毫升之甲苯而將顏料清洗2次，劇烈地 攪拌以分散顏料，而且以3 500 rpm離心20分鐘。將顏料 風乾，然後在65 °C真空乾燥過夜。實行熱重分析（TGA)， 及產生6.7%至9.7重量％間之聚合物濃度。使用Colloidal Dynamics ZetaProbe 對分散於具界面活性劑（Solsperse 17K) 之Isopar E的樣品實行Γ電位測量。Γ電位數示於第5圖 〇 由第5圖之資料得知，Γ電位之程度隨聚合物殼中 TFEM增加而增加。 實例2:使用本發明電泳粒子之顯示器之製備 按以下方式將以上實例1製備之塗覆聚合物鈦白粒子 轉換成電泳顯示器。 部分A:囊之製備 使用實例1製備之顏料及以下步驟製備明膠-***S -17- 201107430 Packed with 1.7158 moles of monomer, lauryl methacrylate and TFEM are added to produce the desired molar concentration of each monomer. The molar ratio of TFEM is 0.1, 1, 5, 10, 25 and 50 mol%, and the rest is lauryl methacrylate. The pigment dispersion is added to the reactor, and the reactor is flushed with nitrogen and heated to 65 °C. . A free radical initiator (5.0 g of 2,2'-arsenazo (2-methylpropionitrile), AIBN) previously dissolved in 110 ml of toluene was added dropwise over 60 minutes. The vessel was heated under continuous agitation at 65 ° C under nitrogen and then exposed to the atmosphere. The mixture was then dispensed into four 1 liter plastic bottles and approximately 500 milliliters of other toluene was added to each bottle. The bottle was stirred vigorously. The pigment was isolated by centrifugation at 3 5 00 rpm for 20 minutes. The supernatant was discarded, and about 70 ml of toluene was added to each vial to wash the pigment twice, vigorously stirred to disperse the pigment, and centrifuged at 3 500 rpm for 20 minutes. The pigment was air dried and then dried under vacuum at 65 °C overnight. Thermogravimetric analysis (TGA) was carried out and a polymer concentration of between 6.7% and 9.7% by weight was produced. Zeta potential measurements were performed on samples of Isopar E dispersed with a surfactant (Solsperse 17K) using Colloidal Dynamics ZetaProbe. The zeta potential number is shown in Fig. 5. From the data in Fig. 5, the degree of zeta potential increases as the TFEM in the polymer shell increases. Example 2: Preparation of display using electrophoretic particles of the present invention The coated polymer titanium white particles prepared in the above Example 1 were converted into an electrophoretic display in the following manner. Part A: Preparation of the capsules The pigments prepared in Example 1 and the following procedure were used to prepare gelatin-Arabic

S -18- 201107430 膠微囊。在25 0毫升之塑膠瓶中組合以下而製備內 成分 量 55% BK-444爲主黑色顏料(參見2009 年2月9日提出之正在審杳之申請案 序號第 61/150,827 號）/Isopar E 25.88 克 60軍暈°/〇白色顏料/Isopar E 106.77 克 13軍暈°/。聚異丁嫌/Isopar E 7.73 克 10 重量°/〇 Solsperse 17K/Isopar E 23.49 克 Isopar E 10.12 克 然後實質上如上述美國專利第6,822,782號 27-29所述，將所得混合物轉換成明膠·***膠微 部分B:顯示器之製備 將在以上部分A製備之微囊靜置及傾倒過量水 將囊混合重量比例爲8份囊對1份黏合劑之聚合黏 製造漿液。使用4 mil ( 101微米）間隙將漿液以之 米之目標塗層厚度棒塗在塗覆氧化銦錫（I TO)聚合膜 在60 °C輸送式烤箱中乾燥大約2分鐘，而且將所得 小片。 分別地將釋放片塗以如美國專利第7，0 1 2，7 3 5 之25微米層訂製聚胺甲酸酯層合黏著劑（摻有180 六氟磷酸四丁銨），及切成較微囊/聚合物膜片稍小 。將兩片膜使其通過上下輥設爲120°C之熱輥層合器 層層合，及將所得組合膜切成所需大小。去除釋放 ，實例 。然後 合劑以 18微 上，及 片切成 號所述 ppm之 之大小 而對塗 片，及 -19- .201107430 再一次通過使用93 °C之上下輥溫的層合器而將黏著劑層層 合帶有石墨層之2吋（51毫米）平方聚合物膜。自所得層 合物切下單像素顯示器，施加電連接，及將如此製造之實 驗用單像素顯示器在5 0%之相對濕度調節5曰。 實例3 :電光測試 使用 PR-650 SpectraScan Colorimeter 對在實例 2 製備 之單像素顯示器進行電光測量。在這些測試中使用2 5 0毫 秒15伏脈衝將顯示器重複地驅動至其黑白極端光學狀態 ，然後驅動至其黑或白極端光學狀態。在最終驅動脈衝後 約3秒（以消除特定暫態效應），然後在最終驅動脈衝後後 2分鐘，測量光學狀態之反射度，及比較兩次測量以偵測 任何影像不安定性（即影像缺乏雙穩性）。 結果示於第6圖（其中” DS”指暗態及”WS”指白態-由 於白態之影像不安定性造成反射度較低，白態影像不安定 値爲負），由其可知隨TFEM在聚合物殻中之含量超過1莫 耳％，影像不安定性有明顯之增加。在0. 1至1莫耳％之 TFEM，影像不安定性等於或較對照稍佳。第7圖（其中”DR” 指動態範圍）顯示在考量第6圖所示之影像不安定性之後 ，各顯示器之最大白態、最小暗態、及全部動態範圍。隨 TFEM含量增加見到光學狀態之控制之改良趨勢，但是不 包括10莫耳％。在較高TFEM含量之光學狀態改良減小可 歸因於第6圖所示之影像安定性降低。由第6及7圖可知 ，在聚合物殼中加入TFEM可改良光學狀態，特別是最終 動態範圍，及有提供改良光學狀態而無影像雙穩性損失之 TFEM窗，其爲電泳顯示器之主要優點。S -18- 201107430 Adhesive microcapsules. The following ingredients were combined in a 25 ml plastic bottle to prepare a 55% internal BK-444 main black pigment (see application number No. 61/150,827, filed on February 9, 2009) / Isopar E 25.88 grams of 60 military halo ° / 〇 white pigment / Isopar E 106.77 grams of 13 military halo ° /. Polyisobutylene/Isopar E 7.73 g 10 wt ° / 〇 Solsperse 17K / Isopar E 23.49 g Isopar E 10.12 g and then substantially converted into gelatin gum arabic as described in the above-mentioned U.S. Patent No. 6,822,782, 27-29 Micropart B: Preparation of the display The microcapsules prepared in the above section A were allowed to stand and the excess water was poured to mix the capsules in a weight ratio of 8 parts to 1 part of the adhesive to form a slurry. The target coating thickness of the slurry was applied to the coated indium tin oxide (I TO) polymeric film using a 4 mil (101 micron) gap and dried in a 60 ° C conveyor oven for approximately 2 minutes, and the resulting pellets were obtained. The release sheet is separately coated with a 25 micron layer custom polyurethane laminate adhesive (doped with 180 tetrabutylammonium hexafluorophosphate) as in U.S. Patent No. 7,0 1 2, 7 3 5 , and cut into The microcapsule/polymer membrane is slightly smaller. The two sheets were laminated by a hot roll laminator layer set to 120 ° C by means of upper and lower rolls, and the resulting combined film was cut into a desired size. Remove release, instance. Then, the mixture is applied to the smear at a size of 18 microliters, and the size of the tablet is cut into the number of ppm, and -19-.201107430 is again layered by using a laminator at a temperature of 93 ° C. A 2 吋 (51 mm) square polymer film with a graphite layer. A single-pixel display was cut from the resulting laminate, an electrical connection was applied, and the experimental single-pixel display thus fabricated was adjusted to 5 Torr at a relative humidity of 50%. Example 3: Electro-optic test Electro-optical measurements were made on a single-pixel display prepared in Example 2 using a PR-650 SpectraScan Colorimeter. In these tests, the display was repeatedly driven to its black and white extreme optical state using a 250 volt 15 volt pulse and then driven to its black or white extreme optical state. About 3 seconds after the final drive pulse (to eliminate specific transient effects), then 2 minutes after the final drive pulse, measure the reflectance of the optical state, and compare the two measurements to detect any image instability (ie lack of image) Bistability). The results are shown in Fig. 6 (where "DS" refers to the dark state and "WS" refers to the white state - due to the image instability of the white state, the reflectance is low, and the white image is unstable and negative), which is known to follow the TFEM. The content in the polymer shell exceeds 1 mol%, and the image instability is significantly increased. At TFEM of 0.1 to 1 mol%, the image instability is equal to or slightly better than the control. Figure 7 (where "DR" refers to the dynamic range) shows the maximum white state, the minimum dark state, and the full dynamic range of each display after considering the image instability shown in Figure 6. An improvement trend in the control of the optical state is seen as the TFEM content increases, but does not include 10 mol%. The reduction in optical state improvement at higher TFEM levels can be attributed to the reduced image stability shown in Figure 6. It can be seen from Figures 6 and 7 that the addition of TFEM to the polymer shell improves the optical state, especially the final dynamic range, and has a TFEM window that provides improved optical state without image bistability loss, which is a major advantage of electrophoretic displays. .

S -20- 201107430 其他實驗已顯示其他氟化單體（即丙烯酸2,2,3,4,4,4-六氟丁酯與丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯） 以類似TFEM之方式調整白色顏料之Γ電位，而且可提供 相同之光學狀態改良。這些氟化單體產生Γ電位變化及光 學狀態變化之確實機構目前未知。 【圖式簡單說明】 第1A與1B圖爲通過本發明第一電泳顯示器之截面簡 圖，其中電泳介質在經著色懸浮流體中包含單型粒子。 第2A與2B圖爲大致各類似第1A與1B圖通過本發明 第二電泳顯示器之截面簡圖，其中電泳介質在未著色懸浮 流體中包含兩種不同型式（帶極性相反之電荷）之粒子。 第3A與3B圖爲大致各類似第2A與2B圖通過本發明 第三電泳顯示器之截面簡圖，其中電泳介質在未著色懸浮 流體中包含兩種不同型式（帶極性相同之電荷但電泳移動 性不同）之粒子。 第4A與4B圖描述本發明之聚合物分散電泳介質、及 用以製造此介質之方法。 第5圖爲顯示在以上實例1報告之實驗中，（（zeta) 電位隨聚合物殼中氟化單體比例之變動的條形圖。 第6圖爲顯示在以上實例3報告之實驗中，暗態與白 態不穩定性隨聚合物殼中氟化單體比例之變動的條形圖。 第7圖爲顯示在以上實例3報告之實驗中，最大白態 、最小暗態與總動態範圍隨聚合物殼中氟化單體比例之變 動的條形圖。S -20- 201107430 Other experiments have shown other fluorinated monomers (ie 2,2,3,4,4,4-hexafluorobutyl acrylate and acrylic acid 3,3,4,4,5,5,6,6 , 7,7,8,8,8-tridecafluorooctyl ester) Adjusts the zeta potential of the white pigment in a manner similar to TFEM, and provides the same optical state improvement. The exact mechanism by which these fluorinated monomers produce changes in zeta potential and optical state is currently unknown. BRIEF DESCRIPTION OF THE DRAWINGS Figs. 1A and 1B are schematic cross-sectional views of a first electrophoretic display according to the present invention, wherein an electrophoretic medium contains monotype particles in a colored suspension fluid. Figures 2A and 2B are schematic cross-sectional views of a second electrophoretic display according to the present invention, substantially similar to Figures 1A and 1B, wherein the electrophoretic medium comprises two different types of particles (with opposite polarity charges) in the uncolored suspension fluid. 3A and 3B are schematic cross-sectional views of the third electrophoretic display according to the present invention, wherein the electrophoretic medium contains two different types (charges of the same polarity but electrophoretic mobility) in the uncolored suspension fluid. Different) particles. Figures 4A and 4B depict a polymer dispersed electrophoretic medium of the present invention, and a method for making the medium. Figure 5 is a bar graph showing the variation of the (zeta) potential with the proportion of fluorinated monomer in the polymer shell in the experiment reported in Example 1 above. Figure 6 is a graph showing the experiment reported in Example 3 above. Bar graph of dark state and white state instability as a function of the proportion of fluorinated monomer in the polymer shell. Figure 7 is a graph showing the maximum white state, minimum dark state and total dynamic range in the experiment reported in Example 3 above. A bar graph showing the variation in the proportion of fluorinated monomers in the polymer shell.

S -21 - 201107430 【主要元件符號說明】 100 電泳顯示器 102 電泳介質 104 囊 106 懸浮液 1 08 粒子 110 前電極 112 後電極 114 基板 200 電泳顯示器 202 電泳介質 204 囊 206 懸浮液 2 18 粒子 3 00 電泳顯示器 302 電泳介質 304 囊 306 液體 320 粒子 4 10 層 4 1 0 5 層 4 12 微滴 4 14 液態介質 4 16 基板 4 18 層 -22-S -21 - 201107430 [Description of main components] 100 Electrophoretic display 102 Electrophoretic medium 104 Capsule 106 Suspension 1 08 Particle 110 Front electrode 112 Rear electrode 114 Substrate 200 Electrophoretic display 202 Electrophoretic medium 204 Capsule 206 Suspension 2 18 Particle 3 00 Electrophoresis Display 302 Electrophoretic Medium 304 Capsule 306 Liquid 320 Particle 4 10 Layer 4 1 0 5 Layer 4 12 Droplet 4 14 Liquid Medium 4 16 Substrate 4 18 Layer-22-

Claims (1)

.201107430 七、申請專利範圍·· ι_ —種電泳介質，其包含多個顏料粒子懸浮於流體，顏料 粒子具有化學地鍵結顏料粒子之聚合物，其中0.1至5 莫耳％之聚合物包含衍生自氟化丙烯酸酯或氟化甲基丙 烯酸酯單體之重複單元。 2.如申請專利範圍第2項之電泳介質，其中聚合物中1至 5莫耳％之單體包含氟化單體。 3_如申請專利範圍第1項之電泳介質，其中粒子具有顏料 之4至15重量％的化學地鍵結顏料粒子之聚合物。 4. 如申請專利範圍第3項之電泳介質，其中粒子具有顏料 之8至12重量％的化學地鍵結顏料粒子之聚合物。 5. 如申請專利範圍第1項之電泳介質，其中聚合物包含主 鏈、及多個自主鏈延伸之側鏈，各側鏈包含至少4個碳 原子。 6. 如申請專利範圍第1項之電泳介質，其中聚合物進一步 包含衍生自未氟化丙烯酸酯及/或甲基丙烯酸酯單體之 殘基。 7. 如申請專利範圍第1項之電泳介質，其中未氟化甲基丙 烯酸酯單體包含甲基丙烯酸月桂酯。 8. 如申請專利範圍第2項之電泳介質，其中氟化單體包含 丙烯酸2,2,2-三氟乙酯、丙烯酸2,2,3,4,4,4-六氟丁酯與 丙烯酸3,3,4,4,5,5,6,6,7,7,8,8,8-十三氟辛酯至少之一。 9. 如申請專利範圍第1項之電泳介質，其具有兩型至少一 種光學特徵不同且電泳移動性不同之粒子。 S -23- 201107430 i〇.如申請專利範圍第9項之電泳介質，其中兩型粒子帶有 極性相反之電荷。 n_如申請專利範圍第1項之電泳介質，其中顔料粒子及流 體係封包於多個囊或微胞中。 12. 如申請專利範圍第U項之電泳介質，其中囊係保持在 聚合黏合劑內。 13. 如申請專利範圍第1項之電泳介質，其中顏料粒子及流 體係如多個被包含聚合材料之連續相包圍之不連續微 滴而存在。 14. 如申請專利範圍第1項之電泳介質，其中流體爲氣態。 15. —種電泳顯示器’其包含如申請專利範圍第1項之電泳 介質、及至少一個排列以對電泳介質施加電場之電極。 16. —種電子書閱讀器、可攜式電腦、桌上型電腦、行動電 話、智慧卡、標誌、錶、架標縫（shelflabel)、或快閃驅 動裝置（flash drive)’其包含如申請專利範圍第15項之 顯示II。 -24-.201107430 VII. Patent application scope · · ι_ an electrophoretic medium containing a plurality of pigment particles suspended in a fluid, the pigment particles having a polymer chemically bonding pigment particles, wherein 0.1 to 5 mol% of the polymer comprises a derivative Repeating unit of self-fluorinated acrylate or fluorinated methacrylate monomer. 2. The electrophoretic medium of claim 2, wherein 1 to 5 mol% of the monomers in the polymer comprise fluorinated monomers. The electrophoretic medium according to claim 1, wherein the particles have a polymer of 4 to 15% by weight of the chemically bonded pigment particles. 4. The electrophoretic medium according to claim 3, wherein the particles have a polymer of 8 to 12% by weight of the chemically bonded pigment particles. 5. The electrophoretic medium according to claim 1, wherein the polymer comprises a main chain and a plurality of side chains extending from the autonomous chain, each side chain comprising at least 4 carbon atoms. 6. The electrophoretic medium of claim 1, wherein the polymer further comprises a residue derived from a non-fluorinated acrylate and/or methacrylate monomer. 7. The electrophoretic medium of claim 1, wherein the unfluorinated methacrylate monomer comprises lauryl methacrylate. 8. The electrophoretic medium according to claim 2, wherein the fluorinated monomer comprises 2,2,2-trifluoroethyl acrylate, 2,2,3,4,4,4-hexafluorobutyl acrylate and acrylic acid At least one of 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl ester. 9. The electrophoretic medium of claim 1, which has two types of at least one particle having different optical characteristics and different electrophoretic mobility. S -23-201107430 i. The electrophoretic medium of claim 9, wherein the two types of particles have opposite polarity charges. An electrophoretic medium according to claim 1, wherein the pigment particles and the flow system are encapsulated in a plurality of capsules or micelles. 12. The electrophoretic medium of claim U, wherein the capsule is held within the polymeric binder. 13. The electrophoretic medium of claim 1, wherein the pigment particles and the flow system are present as a plurality of discrete droplets surrounded by a continuous phase comprising a polymeric material. 14. The electrophoretic medium of claim 1, wherein the fluid is in a gaseous state. 15. An electrophoretic display' comprising an electrophoretic medium as in claim 1 of the patent application and at least one electrode arranged to apply an electric field to the electrophoretic medium. 16. An e-book reader, portable computer, desktop computer, mobile phone, smart card, logo, watch, shelf label, or flash drive' Display II of Article 15 of the patent scope. -twenty four-