TWI700325B - 使用在有色電泳顯示介質中的聚合物添加劑 - Google Patents
使用在有色電泳顯示介質中的聚合物添加劑 Download PDFInfo
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- TWI700325B TWI700325B TW107105160A TW107105160A TWI700325B TW I700325 B TWI700325 B TW I700325B TW 107105160 A TW107105160 A TW 107105160A TW 107105160 A TW107105160 A TW 107105160A TW I700325 B TWI700325 B TW I700325B
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Abstract
本發明揭示出一種可併入電泳顯示器中而包括一分散液的電泳介質,該分散液包括一非極性流體、複數個第一帶電荷有色粒子、聚異丁烯及一選自於乙烯基芳香烴與至少一種具有2至5個碳及至少一個雙鍵的烴之共聚物的添加劑。該共聚物及該共聚物對聚異丁烯之比率係經選擇,以便維持雙穩定性性能同時改良該顯示器的顏色狀態性能。
Description
相關申請案之相互參照
本申請案主張2017年2月15日提出的美國臨時專利申請案案號62/459,174之優先權及利益,其內容全文以參考方式併入本文。
本發明係關於一種有色電泳顯示器及能促進在該有色顯示器中的電泳介質之雙穩定性且沒有降低顏色性能的聚合物添加劑。
粒子基底的電泳顯示器為密集研究及發展之標的已有數年之久。在此類顯示器中,複數個帶電荷粒子(有時指為顏料粒子)會於電場影響下移動通過流體。該電場典型由導電膜或電晶體諸如場效應電晶體提供。當與液晶顯示器比較時,電泳顯示器具有好的明亮度及對比、寬視角、狀態雙穩定性及低電力消耗。但是,此電泳顯示器具有比LCD顯示器慢的切換速度,及電泳顯示器典型太慢而無法顯示即時影像。額外地,電泳顯示器在低溫下可因為流體黏度限制電泳粒子之移動而遲 緩。雖然有這些缺點,但可在日常產品中找到電泳顯示器,諸如電子書(電子閱讀器)、手機及手機外殼、智慧卡、招牌、手錶、貨架標籤及隨身碟。
電泳影像顯示器(EPID)典型包含一對間隔開的板狀電極。其至少一片電極板係透明,典型在觀看側上。在該二片電極板間封裝一由介電溶劑構成且具有帶電荷顏料粒子分散在其中之電泳流體。該電泳流體可具有一種型式的帶電荷顏料粒子,其係分散在一具有對比顏色之溶劑或溶劑混合物中。於此情況中,當在二片電極板間施加電壓差時,該顏料粒子會受極性與該顏料粒子相反的板之吸引而漂移。因此,在透明板處顯示出的顏色可係溶劑之顏色或顏料粒子之顏色。逆轉板極性將造成粒子漂移至相對的板,因此顏色將逆轉。任擇地,該電泳流體可具有二種型式具有對比顏色且攜帶相反電荷之顏料粒子,及該二種型式的顏料粒子係分散在清澈的溶劑或溶劑混合物中。於此情況中,當在二片電極板間施加電壓差時,該二種型式的顏料粒子將移動至在顯示胞元中之相反端(頂端或底部)。因此,將在顯示胞元之觀看側處看見該二種型式的顏料粒子之一種顏色。
許多屬於Massachusetts Institute of Technology(MIT),E Ink Corporation,E Ink California,LLC及相關公司或以其名義申請的專利及申請案描述出多種使用於囊封型及微胞型電泳及其它光電介質之技術。在微胞型電泳顯示器中,該帶電荷顏料粒子被保留在於典型為聚合物膜之載體介質內所形成的複 數個空腔中。在這些專利及申請案中所描述的技術包括:(a)電泳粒子、流體及流體添加劑;參見例如美國專利案號5,961,804;6,017,584;6,120,588;6,120,839;6,262,706;6,262,833;6,300,932;6,323,989;6,377,387;6,515,649;6,538,801;6,580,545;6,652,075;6,693,620;6,721,083;6,727,881;6,822,782;6,831,771;6,870,661;6,927,892;6,956,690;6,958,849;7,002,728;7,038,655;7,052,766;7,110,162;7,113,323;7,141,688;7,142,351;7,170,670;7,180,649;7,226,550;7,230,750;7,230,751;7,236,290;7,247,379;7,277,218;7,286,279;7,312,916;7,375,875;7,382,514;7,390,901;7,411,720;7,473,782;7,532,388;7,532,389;7,572,394;7,576,904;7,580,180;7,679,814;7,746,544;7,767,112;7,848,006;7,903,319;7,951,938;8,018,640;8,115,729;8,119,802;8,199,395;8,257,614;8,270,064;8,305,341;8,361,620;8,363,306;8,390,918;8,582,196;8,593,718;8,654,436;8,902,491;8,961,831;9,052,564;9,114,663;9,158,174;9,341,915;9,348,193;9,361,836;9,366,935;9,372,380;9,382,427;及9,423,666;及美國專利申請案公開案號2003/0048522;2003/0151029;2003/0164480;2003/0169227;2003/0197916;2004/0030125;2005/0012980;2005/0136347;2006/0132896;2006/0281924;2007/0268567;2009/0009852;2009/0206499;2009/0225398;2010/0148385;2011/0217639;2012/0049125;2012/0112131; 2013/0161565;2013/0193385;2013/0244149;2014/0011913;2014/0078024;2014/0078573;2014/0078576;2014/0078857;2014/0104674;2014/0231728;2014/0339481;2014/0347718;2015/0015932;2015/0177589;2015/0177590;2015/0185509;2015/0218384;2015/0241754;2015/0248045;2015/0301425;2015/0378236;2016/0139483;及2016/0170106;(b)微胞結構、壁材料及形成微胞的方法;參見例如美國專利案號7,072,095及9,279,906;(d)用以裝填及密封微胞的方法;參見例如美國專利案號7,144,942及7,715,088;(e)包括光電材料的膜及次組合;參見例如美國專利案號6,982,178及7,839,564;(f)使用於顯示器的背板、黏著層及其它輔助層及方法;參見例如美國專利案號7,116,318及7,535,624;(g)顏色形成及顏色調整;參見例如美國專利案號7,075,502及7,839,564;(h)用以驅動顯示器的方法;參見例如美國專利案號7,012,600及7,453,445;(i)顯示器之應用;參見例如美國專利案號7,312,784及8,009,348;及(j)非電泳顯示器,如在美國專利案號6,241,921及美國專利申請案公開案號2015/0277160中所描述;及囊封及微胞技術除了顯示器外的應用,參見例如美國專利 申請案公開案號2015/0005720及2016/0012710。
許多商業電泳介質基本上僅顯示出二種顏色及在黑色與白色極端間之梯度,已知為「灰階」。此電泳介質係在具有第二不同顏色的有色流體中使用單一型式具有第一顏色之電泳粒子(在此情況中,當該粒子係位於與該顯示器的觀看表面毗連時將顯示出第一顏色,及當該粒子與觀看表面間隔開時將顯示出第二顏色);或在無色流體中具有不同的第一及第二顏色之第一及第二型式電泳粒子。在後者情況中,當該第一型式粒子係位於與該顯示器的觀看表面毗連時,其顯示出第一顏色;及當該第二型式粒子係位於與觀看表面毗連時,其顯示出第二顏色。典型來說,該二種顏色係黑色及白色。
若想要全彩顯示器時,可在單色(黑色及白色)顯示器之觀看表面上沈積一濾色片陣列。具有濾色片陣列的顯示器依賴區域共用及顏色摻合來產生顏色刺激。可獲得的顯示區域係在諸如紅色/綠色/藍色(RGB)或紅色/綠色/藍色/白色(RGBW)之三或四種原色間共用,及該濾波器可呈一維(條紋)或二維(2x2)重覆圖案安排。在技藝中亦知曉其它原色之選擇或多於三原色。所選擇的三種(在RGB顯示器的情況中)或四種(在RGBW顯示器的情況中)子畫素足夠小,以便在意欲的視距處,它們一起視學摻合成具有均勻顏色刺激的單一畫素(「顏色摻合」)。
雖然表面上簡單,電泳介質及電泳裝置顯示出複雜行為。例如,已經發現簡單的「開/關」電壓脈衝 不足以在電子閱讀器中達成高品質的文字。反而,在狀態間需要複雜的「波形」來驅動粒子及保證顯示出新的文字而不保留先前文字之記憶,即,「鬼影」。參見例如,美國專利申請案案號20150213765。與電場的複雜性併合,該內相,即,該粒子(顏料)與流體之混合物可由於在施加電場後,於帶電荷物種與週圍環境(諸如囊封介質)間的交互作用而具有出乎意料的行為。額外地,此出乎意料的行為可產生自在該流體、顏料或囊封介質中之雜質。此外,難以預測電泳顯示器將如何因應在該內相組成物中的變化。
例如,已在美國專利案號7,170,670中發現,將某些聚合物諸如聚異丁烯加入在電泳顯示器中所使用的懸浮流體,其於影像穩定性,即,雙穩定性上所提供的增加可大於由於加入聚合物而造成的流體黏度增加。此外,在懸浮流體中使用這些聚合物允許實質上增加影像穩定性而沒有過量增加顯示器的切換時間。但是,已發現當使用在有色電泳介質中時,引進這些聚合物會造成顏色狀態衰退。
因此,對改良的電泳介質及具有改良的雙穩定性而沒有犧牲顏色狀態性能之顯示器有需求。
本發明之態樣提供一種電泳介質,其包括一非極性流體、複數個至少第一組帶電荷有色粒子、聚異丁烯、及一選自於乙烯基芳香烴與至少一種經取代或未經取代而具有2至5個碳及至少一個雙鍵的烴之共聚物 的添加劑。對該共聚物及該共聚物對聚異丁烯之比率進行選擇,以便維持雙穩定性性能同時改良顯示器的顏色狀態性能。
所提到之此作例證的具體實例並不限制或界定本揭示,而是提供實施例來輔助了解本揭示。在【實施方式】中討論額外的具體實例,及於此提供進一步描述。可藉由檢驗此專利說明書或藉由實行所顯現的一或多個具體實例進一步了解由該一或多個不同具體實例所提供之優點。
本發明之電泳介質可例如被囊封在微胞或蛋白質凝聚物中,如於【先前技術】章節中有討論。此外,本發明之電泳介質可被分散在一聚合物基質中。如在【先前技術】中討論般,可將該經囊封或經聚合物分散的電泳介質併入前面板(FPL)及/或光電顯示器中。此材料可使用來產生電泳影像顯示器(EPID)、招牌或將在接收信號後改變外觀之架構材料。
圖1係使用在表1中所提供的資料,以紅色狀態(紅色a*)值對聚異丁烯濃度所繪製之曲線圖。
可藉由包括於本文中所描述的添加劑組合來改良多種型式之電泳介質性能。例如,當與缺乏共聚物之電泳介質的顏色性能比較時,聚異丁烯與根據本發明之共聚物之組合可改良電泳介質的雙穩定性,和維持或改良顏色狀態性能。
用語「雙穩定及雙穩定性」於本文中係以其在技藝中習知的意義使用,其指為包含具有至少一種光學性質不同的第一及第二顯示狀態之顯示元件的顯示器,其在任何所提供的元件已經藉由有限時期的定址脈衝驅動至假設其第一或第二顯示狀態後,於該定址脈衝已終止後,該狀態將存留一段時期,其中該時期係改變該顯示元件的狀態所需要之最小定址脈衝時期至少數倍,例如,至少四倍。已在美國專利案號7,170,670中顯示出,能有灰階之某些粒子基底的電泳顯示器不僅其極端的黑色及白色狀態穩定,而且其中間灰色狀態亦穩定,及此對某些其它型式的光電顯示器亦真實。此型式的顯示器合適地稱為多穩定而非雙穩定,然而為了方便,於本文中所使用的用語「雙穩定」可涵蓋雙穩定及多穩定型顯示器二者。
在本發明的一個具體實例中,該電泳介質包含一分散液。該分散液可包含一非極性流體、複數個第一帶電荷粒子、聚異丁烯、及一選自於乙烯基芳香烴與至少一種經取代或未經取代而具有2至5個碳與至少一個雙鍵的烴之共聚物的添加劑。
為了保證聚異丁烯及該共聚物實質上不吸附在該電泳粒子上,想要該添加劑與非極性懸浮流體組合應該於室溫下係該流體對該聚異丁烯及共聚物係至少一θ溶劑。為了擴大提高影像穩定性之溫度範圍,若該流體對該影像穩定性添加劑係至少中等好的溶劑至好的溶劑時,其係最理想。一種選擇適當添加劑/流體組合之方 法為繪製出該組合的本質黏度對該添加劑分子量之圖;想要的組合有該本質黏度之對數對該分子量之對數的最好線性擬合之斜率係至少0.5的那些,及想要的範圍係約0.55至約0.8。
典型來說,在電泳顯示器中所使用的懸浮流體係非極性脂肪烴(單獨或與鹵化烴組合),及使用此流體時,最好該添加劑基本上係無會造成該添加劑與在電泳粒子上的化學位置交互作用或會物理性吸附至電泳粒子表面之官能基(諸如可離子化或離子取代基)的烴聚合物。
對含有脂肪烴/鹵化烴懸浮流體之電泳介質來說,該添加劑較佳為如在下列進一步描述的共聚物與聚異丁烯(聚-2-甲基丙烯)之組合。亦可選擇性使用多種其它型式的聚合物,例如聚矽氧烷,特別是聚二甲基矽氧烷。具有合適於使用在本發明中的分子量範圍之不貴、於高溫下穩定、具抗氧化性及不包括容易反應或可離子化組分之聚異丁烯可商業購得。如已經提到,在該聚合物中不想要有離子或可離子化組分,因為此等組分被釋放進懸浮流體中可造成電泳粒子的電荷及因此其電泳移動率上不想要的改變。該聚異丁烯想要具有數量平均分子量超過100,000,及較佳範圍係約150,000至約3,000,000,及重量平均分子量係超過100,000及較佳範圍係約300,000至約3,000,000;可使用類似的分子量範圍的其它聚合物。落在這些分子量範圍內的聚異丁烯類可容易地從例如Sigma-Aldrich,Inc.,P.O.Box 2060, Milwaukee Wis.53201,於目錄編號18145-5及18146-3下商業購得。該聚異丁烯亦想要具有黏度平均分子量範圍在約200,000至1,200,000克/莫耳內。如上述提到,對根據本發明的多個具體實例所製造之電泳介質來說,在該添加劑組合中所包括的共聚物可係乙烯基芳香烴與經取代或未經取代且具有2至5個碳及至少一個雙鍵的烴之共聚物。可包括在該共聚物中的乙烯基芳香烴包括但不限於:苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、44-丁基苯乙烯、4-環己基苯乙烯、4-十二烷基苯乙烯、2,4-二異丙基苯乙烯、2,4,6-三甲基苯乙烯、2-乙基-4-苄基苯乙烯、4-(苯基丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基蒽、4-甲氧基苯乙烯、單氯苯乙烯、二氯苯乙烯、二乙烯基苯、茚、甲基茚及其組合。苯乙烯係較佳。該經取代或未經取代且具有2至5個碳及至少一個雙鍵的烴之實施例包括但不限於乙烯、丙烯、異戊二烯、丁烯及丁二烯。在一個具體實例中,最好該共聚物係苯乙烯、乙烯與丙烯的聚合產物。
該共聚物較佳為不吸附在粒子上及可包含具有可溶於該流體的第一嵌段及不可由該流體膨潤的第二嵌段之二嵌段共聚物。該二嵌段共聚物可包含一第一聚苯乙烯嵌段及一第二聚烯烴例如聚異戊二烯嵌段。此嵌段共聚物可商業購得及包括例如從苯乙烯及聚(乙烯丙烯)製得的團聚二嵌段共聚物,諸如Kraton(註冊商標)G1701、G1702或G1730,其全部可從Kraton Polymers,Inc,Belpre,Ohio獲得。
當該懸浮流體係相等重量份的脂肪烴與鹵化烴之混合物時,存在有實質比例的芳香族基團可造成該添加劑有差的溶解度或吸附到電泳粒子上。因此,應該對該共聚物添加劑的乙烯基芳香烴單體單元對烯烴單體單元之比率進行選擇,以便避免在懸浮流體上有不想要的效應。該共聚物較佳為包括約10至約50百分比的苯乙烯,更佳為20至約40百分比,以重量計。
用以改良在任何特定系統中之雙穩定性及顏色性能的添加劑量會隨著所需要的影像穩定程度、添加劑之分子量及該介質可容忍的最大切換時間而變化。但是,作為一般指導,想要以該懸浮流體之約0.1至約2.5重量百分比的量加入該結合的添加劑(即,聚異丁烯與共聚物之結合重量),及較佳量為約0.5至約1重量百分比。依該聚合物的分子量而定,低於約0.1百分比時,該聚合物除了對懸浮流體黏度增加有貢獻外,其在影像穩定性上產生些微或無增加;同時該聚合物濃度大於約2.5百分比時,所造成的黏度增加可造成無法接受之切換時間。在該分散液中,該聚異丁烯對共聚物的重量比率可係1:5至5:1,更佳為1:3至3:1。
本發明之電泳介質可包括一或多種型式的帶電荷粒子。為了本發明之目的,該粒子係帶電荷或能獲得電荷(即,具有或能獲得電泳移動率)的任何組分,及在某些情況中,此移動率可係零或接近零(即,粒子將不移動)。例如,該電泳介質可包括第一、第二、第三、第 四、第五或第六型式的帶電荷粒子。該粒子可在電荷、密度、疏水性及/或ζ-電位上變化。多種粒子群組的組合可相對於彼此具有相反電荷極性。同樣地,該粒子可具有不同顏色,諸如品紅、紅色、橙色、黃色、綠色、青綠色、藍色、紫色、黑色及白色。例如,在本發明的一個具體實例中,該電泳介質可包含複數個第一、第二及第三帶電荷粒子分散於非極性流體中,其中該第一帶電荷粒子係品紅、紅色、黃色、綠色、青綠色或藍色,該第二帶電荷粒子係白色及具有與該第一帶電荷粒子之電荷相反的電荷,及該第三帶電荷粒子係黑色及具有與該第一帶電荷粒子的電荷類似之電荷。
在本發明的多個具體實例中,所使用之粒子亦可選擇性包括無色或透明粒子。該電泳介質可額外包括界面活性劑,諸如離子界面活性劑,即,具有四級胺頭端基團之界面活性劑。
已由熟習電泳顯示器該項技術者知曉,在該粒子之選擇上有更多彈性。對該電泳粒子的典型考慮為其光學性質、電性質及表面化學。該顏料亦應該不溶於該懸浮流體。該粒子可經表面處理,以便改良帶電荷性或與帶電荷試劑之交互作用,或改良分散性。該等粒子可例如係無機粒子、純淨的顏料、染料式(色澱)顏料或顏料/聚合物複合物、或帶電荷或能獲得電荷的任何其它組分。
無機顏料之實施例包括但不限於:TiO2、ZrO2、ZnO、Al2O3、CI顏料黑色26或28、或其類似物(例 如,錳鐵黑(manganese ferrite black spinel)或銅鉻黑(copper chromite black spinel))。例如,可以諸如氧化鋁或氧化矽之金屬氧化物來塗佈諸如二氧化鈦粒子的粒子。
有用的純淨顏料包括但不限於:PbCrO4、Cyan blue GT 55-3295(American Cyanamid Company,Wayne,N.J.)、Cibacron Black BG(Ciba Company,Inc.,Newport,Del.)、Cibacron Turquoise Blue G(Ciba)、Cibalon Black BGL(Ciba)、Orasol Black BRG(Ciba)、Orasol Black RBL(Ciba)、Acetamine Black、CBS(E.I.du Pont de Nemours and Company,Inc.,Wilmington,Del.,於此之後縮寫為「du Pont」)、Crocein Scarlet N Ex(du Pont)(27290)、Fiber Black VF(du Pont)(3023S)、Luxol Fast Black L(du Pont)(Solv.Black 17)、Nirosine Base No.424(du Pont)(50415 B)、Oil Black BG(du Pont)(Solv.Black 16)、Rotalin Black RM(du Pont)、Sevron Brilliant Red 3 B(du Pont)、Basic Black DSC(Dye Specialties,Inc.)、Hectolene Black(Dye Specialties,Inc.)、Azosol Brilliant Blue B(GAF,Dyestuff and Chemical Division,Wayne,N.J.)(Solv.Blue 9)、Azosol Brilliant Green BA(GAF)(Solv.Green 2)、Azosol Fast Brilliant Red B(GAF)、Azosol Fast Orange RA Conc.(GAF)(Solv.Orange 20)、Azosol Fast Yellow GRA Conc.(GAF)(13900 A)、Basic Black KMPA(GAF)、Benzofix Black CW-CF(GAF)(35435)、Cellitazol BNFV Ex Soluble CF(GAF) (Disp.Black 9)、Celliton Fast Blue AF Ex Conc(GAF)(Disp.Blue 9)、Cyper Black IA(GAF)(Basic Black 3)、Diamine Black CAP Ex Conc(GAF)(30235)、Diamond Black EAN Hi Con.CF(GAF)(15710)、Diamond Black PBBA Ex(GAF)(16505);Direct Deep Black EA Ex CF(GAF)(30235)、Hansa Yellow G(GAF)(11680);Indanthrene Black BBK Powd.(GAF)(59850)、Indocarbon CLGS Conc.CF(GAF)(53295)、Katigen Deep Black NND Hi Conc.CF(GAF)(15711)、Rapidogen Black 3 G(GAF)(Azoic Black 4)、Sulphone Cyanine Black BA-CF(GAF)(26370)、Zambezi Black VD Ex Conc.(GAF)(30015)、Rubanox Red CP-1495(The Sherwin-Williams Company,Cleveland,Ohio)(15630)、Raven 11(Columbian Carbon Company,Atlanta,Ga.)(具有粒子尺寸約25微米的碳黑團聚物)、Statex B-12(Columbian Carbon Co.)(平均粒子尺寸33微米的爐黑)及鉻綠。
色澱顏料係具有染料沈澱在其上或經染色的粒子。沈澱色料係容易可溶的陰離子染料之金屬鹽。這些有下列染料:偶氮、三苯基甲烷或包括一或多個磺酸或羧酸基團之蒽醌結構。它們通常藉由鈣、鋇或鋁鹽沈澱到基質上。典型的實施例有孔雀藍沈澱色料(Cl顏料藍色24)及Persian橙色(Cl酸橙色7之沈澱色料)、Black M Toner(GAF)(碳黑與沈澱在沈澱色料上之黑色染料的混合物)。
染色型式的暗色粒子可從任何吸光材料建 構,諸如碳黑或無機黑色材料。該暗色材料亦可進行選擇性吸收。例如,可使用暗綠色顏料。亦可藉由以金屬氧化物來染色乳膠而形成黑色粒子,此乳膠共聚物係由下列之任何組成:丁二烯、苯乙烯、異戊二烯、甲基丙烯酸、甲基丙烯酸甲酯、丙烯腈、氯乙烯、丙烯酸、苯乙烯磺酸鈉、醋酸乙烯酯、氯苯乙烯、二甲基胺基丙基甲基丙烯醯胺、甲基丙烯酸異氰基乙酯及N-(異丁氧基甲基丙烯醯胺)及選擇性包括共軛的二烯化合物,諸如二丙烯酸酯、三丙烯酸酯、二甲基丙烯酸酯及三甲基丙烯酸酯。該黑色粒子亦可藉由分散聚合技術形成。
可將根據本發明的多個具體實例之電泳介質併入顯示器中,或併入前面板或逆轉式前面板中以與背板耦合而製得顯示器。許多前述提及的專利及申請案了解到可例如將包括上述顏料與添加劑之分散液囊封在微膠囊中。再者,可由一連續相置換在囊封的電泳介質中環繞該分立的微膠囊之壁,因此製造出所謂的聚合物分散型電泳顯示器,其中該電泳介質包含複數個分立的電泳流體滴及聚合材料連續相,及在此聚合物分散型電泳顯示器內之分立的電泳流體滴可視為膠囊或微膠囊,即使無與每個各別滴相關的分立膠囊膜;參見例如美國專利案號6,866,760。此外,為了本申請案的目的,此聚合物分散型電泳介質視為經囊封的電泳介質之次物種。相關型式的電泳顯示器係所謂的微胞電泳顯示器。在微胞電泳顯示器中,該帶電荷粒子及流體未被囊封在微膠囊內,反而是保留在於典型為聚合物膜的載體介質內形成 之複數個空腔中。參見例如美國專利案號6,672,921及6,788,449,二者屬於Sipix Imaging,Inc.。
囊封型電泳顯示器典型不會遭遇到傳統電泳裝置的聚集化及沉降失敗模式,並提供進一步優點,諸如將該顯示器印刷或塗佈在廣泛多種可撓及堅硬的基材上之能力。(用字「印刷」之使用意欲包括全部形式的印刷及塗佈,包括但不限於:預計量供給式塗佈法,諸如方塊式模具塗佈法(patch die coating)、狹縫或擠壓塗佈法、滑動或階式塗佈法、簾幕塗佈法;輥塗法,諸如輥襯刀塗法(knife over roll coating)、前向及逆向輥塗法;凹版塗佈法;浸沾塗佈法;噴灑塗佈法;彎月液面塗佈法;旋轉塗佈法;刷塗法;氣刀塗佈法;絲網印刷方法;靜電印刷方法;熱印刷方法;噴墨印刷方法;電泳沈積法(參見美國專利案號7,339,715);及其它類似技術。)因此,所產生的顯示器係可撓。再者,因為該顯示介質可進行印刷(使用多種方法),該顯示器其自身可不貴地製得。
前述提及的美國專利案號6,672,921、6,788,449及6,866,760描述出電泳顯示器之組合方法。基本上,此專利描述出一種積層板,其包含一光透射導電層及一與該導電層電接觸的固體光電介質層。典型來說,將該光透射導電層載攜於較佳為可撓的光透射基材上,在觀念上,該基材可繞著直徑(大約)10英吋(254毫米)的滾筒手動地纏繞而沒有永久變形。在此專利及本文中所使用的用語「光透射」意謂著因此設計之層能透射 足夠的光,以便觀察者能夠看穿該層而觀察到該光電介質的顯示狀態變化,其中正常將看穿該導電層及毗連基材(若存在時);在該光電介質於不可見波長處顯示出反射性改變的情況中,當然該用語「光透射」應該解釋為指為該相關的不可見波長之穿透。該基材典型將係一聚合物膜,及正常將具有厚度在範圍約1至約25密耳(25至634微米)內,較佳為約2至約10密耳(51至254微米)。該導電層合宜地係一薄金屬或金屬氧化物層,例如,鋁或氧化銦錫(ITO);或可係一導電聚合物。塗佈鋁或ITO的聚(對酞酸乙二酯)(PET)膜可商業購得,例如,如為來自E.I.du Pont de Nemours & Company,Wilmington DE之鋁化的Mylar(Mylar係註冊商標),及可在該前面板中使用此商業材料而具有好的結果。
可藉由下列方式執行該光電顯示器之組合:在有效造成黏著層黏附至背板之條件下,以黏著劑將上述積層板接附至背板,因此將該黏著層、光電介質層及導電層穩固至該背板。此方法良好適應於大量製造,因為該前面板典型可使用捲繞式塗佈技術大量製造,然後切割成使用特定背板所需要的任何尺寸片。
除了本發明之添加劑外,該電泳介質亦可包括電荷控制劑(CCAs)。例如,該顏料粒子可以帶電荷或可帶電荷基團官能化或塗佈表面。該CCAs可被吸附至粒子,它們可共價鍵結至粒子的表面,及它們可存在於電荷複合物中,或經由凡得瓦爾力鬆散連結。電荷控制劑經常藉由未充分了解及未經控制的方法讓粒子帶電 荷,及可導致該電泳介質不合意地具有高導電度。同樣地,因為該電荷控制劑僅物理吸附到粒子上而未向那裏鍵結,條件改變可造成該電荷控制劑與該粒子部分或完全脫附,因此在粒子的電泳特徵上有不想要的改變。該脫附的電荷控制劑可再吸附至在該電泳介質內之其它表面上,及此再吸附具有造成額外問題的潛力。
包含四級胺且包含長度至少10個碳原子的單體之不飽和聚合物尾部的電荷控制劑係較佳。該四級胺包含鍵結至有機分子例如烷基或芳基之四級銨陽離子[NR1R2R3R4] +。該四級胺電荷控制劑典型包括接附至該帶電荷銨陽離子的長非極性尾部,諸如由Akzo Nobel以ARQUAD之商品名提供的脂肪酸四級胺家族。可購買純化形式的四級胺電荷控制劑,或可購買已形成四級胺電荷控制劑的反應產物作為該電荷控制劑。例如,可購買SOLSPERSE 17000(Lubrizol Corporation),其如為12-羥基-十八烷酸同元聚合物與N,N-二甲基-1,3-丙二胺及硫酸氫甲酯之反應產物。其它有用的離子電荷控制劑包括但不限於十二烷基苯磺酸鈉、金屬肥皂、聚丁烯琥珀醯亞胺、馬來酸酐共聚物、乙烯基吡啶共聚物、乙烯吡咯啶酮共聚物、(甲基)丙烯酸共聚物或(甲基)丙烯酸N,N-二甲基胺基乙基酯共聚物、Alcolec LV30(大豆卵磷脂)、Petrostep B100(石油磺酸鹽)或B70(磺酸鋇)、OLOA 11000(琥珀醯亞胺無灰分分散劑)、OLOA 1200(聚異丁烯琥珀醯亞胺類)、Unithox 750(乙氧基化物)、Petronate L(磺酸鈉)、Disper BYK 101、2095、185、116、9077 & 220及ANTITERRA系列。
可以每100克帶電荷粒子多於1克電荷控制劑之濃度將該電荷控制劑加入至該電泳介質。例如,該電荷控制劑對帶電荷粒子比率可係1:30(重量/重量),例如,1:25(重量/重量),例如,1:20(重量/重量)。該電荷控制劑可具有平均分子量大於12,000克/莫耳,例如,大於13,000克/莫耳,例如,大於14,000克/莫耳,例如,大於15,000克/莫耳,例如,大於16,000克/莫耳,例如,大於17,000克/莫耳,例如,大於18,000克/莫耳,例如,大於19,000克/莫耳,例如,大於20,000克/莫耳,例如,大於21,000克/莫耳。例如,該電荷控制劑之平均分子量可在14,000克/莫耳至22,000克/莫耳間,例如,在15,000克/莫耳至20,000克/莫耳間。在某些具體實例中,該電荷控制劑具有平均分子量約19,000克/莫耳。
可在該聚合物塗層中額外使用含或不含帶電荷基團的電荷控制劑,以便對該電泳粒子提供好的電泳移動率。可使用安定劑來防止該電泳粒子團聚,和防止電泳粒子不可逆地沈積到膠囊壁上。任一種組分皆可從寬分子量範圍的材料(低分子量、寡聚或聚合物)建構,及可係單一純化合物或混合物。可選擇性使用電荷控制劑或電荷導向體。這些構成物典型由低分子量界面活性劑、聚合物試劑或一或多種組分之摻合物所組成,及提供其以便安定或其它方面修改在電泳粒子上的電荷符號及/或電荷大小。額外有關聯的顏料性質有粒子尺寸分佈、化學組成物及耐光性。
除了溶解度外,如已經指示出,應該根據諸如密度及折射率之性質來選擇包括該粒子的非極性懸浮流體。較佳的懸浮流體具有低介電常數(約2)、高體積電阻係數(約1015歐姆-公分)、低黏度(少於5厘斯(「cst」))、低毒性及環境衝擊、低水溶解度(少於每百萬份10份(「ppm」))及低折射率(小於1.2)。
可以基於化學惰性、與電泳粒子相配的密度、或與電泳粒子及定界膠囊二者的化學相容性之考量,來選擇該非極性流體(在經囊封的電泳顯示器之情況中)。當想要移動粒子時,該流體的黏度應該低。
非極性有機溶劑,諸如經鹵化的有機溶劑、飽和的線性或分枝烴(例如,C6-C18分枝的烷烴或C7-C10分枝的烷烴)、聚矽氧油及低分子量的含鹵素聚合物係某些有用的非極性流體。該非極性流體可包含單一流體。但是,該非極性流體經常將係多於一種流體的摻合物以調整其化學及物理性質。再者,該非極性流體可包括額外的表面改質劑以修改該電泳粒子或定界膠囊之表面能量或電荷。亦可在該懸浮流體中包括用於微囊封方法的反應物或溶劑(例如,油可溶性單體)。亦可將額外的電荷控制劑加入至該懸浮流體。
有用的有機溶劑包括但不限於環氧化合物,諸如環氧癸烷及環氧十二烷;乙烯醚類,諸如環己基乙烯基醚及Decave(International Flavors & Fragrances,Inc.,New York,N.Y.的註冊商標);及芳香烴,諸如甲苯及萘。有用的鹵化有機溶劑包括但不限於:四氟二溴 乙烯、四氯乙烯、三氟氯乙烯、1,2,4-三氯苯及四氯化碳。這些材料具有高密度。有用的烴包括但不限於:十二烷、十四烷、Isopar(註冊商標)系列中的脂肪烴(Exxon,Houston,Tex.)、Norpar(註冊商標)(正石蠟液體系列)、Shell-Sol(註冊商標)(Shell,Houston,Tex.)及Sol-Trol(註冊商標)(Shell)、石油腦及其它石油溶劑。這些材料通常具有低密度。有用的聚矽氧油實施例包括但不限於:八甲基環矽氧烷及較高分子量的環狀矽氧烷、聚(甲基苯基矽氧烷)、六甲基二矽氧烷及聚二甲基矽氧烷。這些材料通常具有低密度。有用的低分子量含鹵素聚合物包括但不限於:聚(氯三氟乙烯)聚合物(Halogenated Hydrocarbon Inc.,River Edge,N.J.)、Galden(註冊商標)(來自Ausimont,Morristown,N.J.的全氟化醚)或來自du Pont(Wilmington,Del.)的Krytox(註冊商標)。在較佳具體實例中,該懸浮流體係聚(氯三氟乙烯)聚合物。在特別佳的具體實例中,此聚合物具有聚合程度約2至約10。可獲得許多在黏度、密度及沸點範圍內的上述材料。
在某些具體實例中,該非極性流體將包括一光學吸收染料。此染料必需可溶於流體中,但是通常將不溶於該膠囊的其它組分中。在染料材料之選擇上有更大彈性。該染料可係純化合物或染料的摻合物以達成特別的顏色,包括黑色。該染料可具螢光性,此將製造出一螢光性質與粒子的位置相依之顯示器。該染料可具光活化性,能在以可見或紫外光照射後改變成另一種顏色 或變成無色,此提供另一種獲得光學回應的方法。該染料亦可藉由例如熱、光化學或化學擴散方法聚合而在該定界外殼內形成一固體吸收聚合物。
將證實一些已由熟習電泳顯示器該項技術者知曉的染料係有用。有用的偶氮染料包括但不限於油紅染料、及蘇丹紅及蘇丹黑系列染料。有用的蒽醌染料包括但不限於油藍染料及Macrolex藍系列染料。有用的三苯基甲烷染料包括但不限於Michler’s hydrol、孔雀石綠、結晶紫及Auramine O。
亦可加入粒子分散安定劑來防止粒子絮凝或附著至膠囊壁。對使用在電泳顯示器中作為懸浮流體之典型高電阻率液體來說,可使用非水性界面活性劑。這些包括但不限於:二醇醚、炔屬二醇、烷醇醯胺、山梨糖醇衍生物、烷基胺、四級胺、咪唑啉類、二烷基氧化物及磺化琥珀酸酯。
可以數種不同方法達成該內相之囊封。許多用於微囊封的合適程序詳述在Microencapsulation,Processes and Applications,(I.E.Vandegaer,編輯),Plenum Press,New York,N.Y.(1974);及Gutcho,Microcapsules and Microencapsulation Techniques,Noyes Data Corp.,Park Ridge,N.J.(1976)二者中。該等方法分成數種一般類別,其全部可應用至本發明:界面聚合、就地聚合、物理方法諸如共擠壓及其它相分離方法、液體內硬化及簡單/複雜的共凝聚。
應該證實許多材料及方法在調配本發明之顯 示器時有用。對形成膠囊之簡單共凝聚方法有用的材料包括但不限於:明膠、聚(乙烯醇)、聚(醋酸乙烯酯)及纖維素衍生物,諸如例如,羧甲基纖維素。對複雜共凝聚方法有用的材料包括但不限於:明膠、阿拉伯膠、卡拉膠(carageenan)、羧甲基纖維素、水解的苯乙烯酐共聚物、瓊脂、藻酸酯、酪蛋白、白蛋白、甲基乙烯基醚共馬來酸酐及纖維素酞酸酯。對相分離方法有用的材料包括但不限於:聚苯乙烯、聚(甲基丙烯酸甲酯)(PMMA)、聚(甲基丙烯酸乙酯)、聚(甲基丙烯酸丁酯)、乙基纖維素、聚(乙烯基吡啶)及聚丙烯腈。對就地聚合方法有用的材料包括但不限於:含有醛、三聚氰胺或尿素與甲醛的聚羥基醯胺;三聚氰胺或尿素與甲醛的縮合物之可溶於水的寡聚物;及乙烯基單體,諸如例如,苯乙烯、甲基丙烯酸甲酯(MMA)及丙烯腈。最後,對界面聚合方法有用的材料包括但不限於:二醯基氯,諸如例如,癸二醯基、己二醯基;及二或聚胺或醇;及異氰酸鹽。有用的乳化聚合材料可包括但不限於:苯乙烯、醋酸乙烯酯、丙烯酸、丙烯酸丁酯、丙烯酸三級丁酯、甲基丙烯酸甲酯及甲基丙烯酸丁酯。
可將所製造的膠囊分散進可硬化型載體中,產生一可使用習知的印刷及塗佈技術來印刷或塗佈在大及任意塑形或彎曲表面上之墨液。
在本發明的上下文中,熟習該項技術者將根據想要的膠囊性質來選擇囊封程序及壁材料。這些性質包括膠囊半徑之分佈;膠囊壁的電、機械、擴散及光學 性質;及與膠囊內相之化學相容性。
該膠囊壁通常具有高電阻率。雖然可使用具有相對低電阻率的壁,此會在需要相對較高定址電壓時限制性能。該膠囊壁亦應該機械性強大(然而若所完成的膠囊粉末係被分散在可硬化的聚合物黏著劑中用於塗佈時,機械強度非為關鍵)。該膠囊壁通常應該不具多孔性。但是,若想要使用產生多孔膠囊的囊封程序時,這些可在後加工步驟(即,第二囊封)中進行外層塗佈。再者,若該膠囊係被分散在可硬化的黏著劑中時,該黏著劑將提供封閉該孔洞。該膠囊壁應該光學透明。但是,可對該壁材料進行選擇以與該膠囊的內相(即,懸浮流體)或欲分散該膠囊的黏著劑之折射率相配。對某些應用(例如,間插在二片固定電極間)來說,想要單分散型膠囊半徑。
適合於本發明的囊封技術包括於負電荷、經羧基取代的線性烴聚電解質材料存在下,在油/水乳液的水相中,於尿素及甲醛間聚合。所產生的膠囊壁係一尿素/甲醛共聚物,其分立地包圍住該內相。該膠囊係清澈、機械性強大且具有好的電阻率性質。
就地聚合的相關技術使用油/水乳液,其係藉由在水性環境中分散該電泳流體(即,該介電質液體包括該顏料粒子之懸浮液)而形成。該等單體進行聚合以形成一對內相的親和力比對水相高之聚合物,因此繞著該經乳化的油狀小滴縮合。在一種就地聚合方法中,於聚(丙烯酸)存在下縮合尿素與甲醛(參見例如,美國專利案號 4,001,140)。在美國專利案號4,273,672所描述的其它方法中,於水溶液中攜帶之任何多種交聯劑將繞著微觀的油小滴沈積。此交聯劑包括醛類,特別是甲醛、乙二醛或戊二醛;礬;鋯鹽;及多異氰酸酯。
該共凝聚方法亦使用油/水乳液。透過溫度、pH及/或相對濃度之控制,讓一或多種膠體凝聚(即,團聚)出水相及繞著該油狀小滴沈積作為外殼,因此產生微膠囊。合適於共凝聚的材料包括明膠及阿拉伯膠。參見例如,美國專利案號2,800,457。
界面聚合方法依賴油可溶單體存在於電泳組成物中,其再一次係呈現如為在水相中的乳液。在微疏水小滴中的單體與引進該水相中之單體反應,於小滴與環繞的水性介質間之界面處聚合及繞著該小滴形成外殼。雖然所產生的壁相當薄及可滲透,此方法不需要某些其它方法的高溫特徵,因此就介電質液體之選擇來說獲得較大彈性。
可將額外的材料加入至該囊封介質以改良該電泳顯示器之架構。例如,可使用塗佈輔助劑來改良該經塗佈或印刷的電泳墨液材料之均勻性及品質。可加入潤溼劑以調整在該塗層/基材界面處之界面張力及調整該液體/空氣表面張力。該潤溼劑包括但不限於:陰離子及陽離子界面活性劑;及非離子物種,諸如聚矽氧或含氟聚合物基底的材料。可使用分散劑來修改在膠囊與黏著劑間之界面張力,於絮凝及粒子沈澱上提供控制。
在其它具體實例中,可於微製造的胞元,即, 諸如由E Ink製造呈MICROCUP之商品名的微胞中包括該電泳介質。一旦以電泳介質填充該微胞時,密封該微胞,將電極(或電極陣列)接附至該微胞及以電場驅動該經填充的微胞而產生一顯示器。
如例如在美國專利案號6,930,818中所描述,可使用陽模來壓印一導電基材,於其上形成一透明導體膜。然後,在該導體膜上塗佈一熱塑性或熱固性前驅物層。該熱塑性或熱固性前驅物層係在溫度高於該熱塑性或熱固性前驅物層之玻璃轉換溫度下,藉由呈滾筒、板或帶形式的陽模進行壓印。一旦形成,在硬化該前驅物層以顯露出微胞陣列期間或後,對該模具脫模。可藉由冷卻、藉由輻射、熱或水分交聯達成該前驅物層之硬化。若藉由UV輻射達成該熱固性前驅物之硬化時,UV可從該膜片之底部或頂端輻射到該透明導體膜上,如顯示在美國專利6,930,818之圖2a及2b中。任擇地,可將UV燈放置在模具內。於此情況中,該模具必需透明以允許UV光通過預圖案化的陽模輻照在該熱固性前驅物層上。
該用以製備微胞的熱塑性或熱固性前驅物可係多官能基丙烯酸酯或甲基丙烯酸酯、乙烯基醚、環氧化合物及其寡聚物、聚合物及其類似物。通常亦加入授予彈性的可交聯寡聚物,諸如丙烯酸酯胺基甲酸酯或聚酯丙烯酸酯,以改良所壓印的微杯之抗彎曲性。該組成物可包括聚合物、寡聚物、單體及添加劑,或僅有寡聚物、單體及添加劑。
通常來說,該微胞可係任何形狀,及其尺寸及形狀可變化。在一個系統中,該微胞可係實質上均勻尺寸及形狀。但是,為了最大化光學效應,可製造出具有不同形狀及尺寸的混合物之微胞。例如,填充紅色分散液的微胞可具有與綠色微胞或藍色微胞不同形狀或尺寸。再者,畫素可由不同數目之不同顏色的微胞組成。例如,畫素可由一些小綠色微胞、一些大紅色微胞及一些小藍色微胞組成。三種顏色不需要具有相同形狀及數目。
該微胞的開口可係圓形、方形、矩形、六角形或任何其它形狀。在開口間之分割區域較佳為保持小以達成高顏色飽和及對比,同時維持想要的機械性質。因此,蜂窩形開口係超過例如圓形開口而較佳。
對反射性電泳顯示器來說,每個各別微胞的尺寸範圍可在約102至約5×105平方微米內,較佳為約103約5×104平方微米。該微胞的深度係在約3至約100微米之範圍內,較佳為約10至約50微米。該開口對壁比率係在約0.05至約100之範圍內,較佳為約0.4至約20。該開口從開口的邊緣至邊緣之距離通常在約15至約450微米的範圍內,較佳為約25至約300微米。
合在一起說,將由熟習該項技術者明瞭可在本發明上述特定具體實例中製得許多改變及改質而沒有離開本發明之範圍。此外,前述說明全部欲以闡明性及不以限制性觀念解釋。
現在提供實施例以顯示出本發明的較佳電泳介質之細節,然而其僅具闡明性。
為了闡明聚異丁烯(PIB)在顯示器的顏色性能上之效應,製備包括不同PIB濃度的四種分散液CS1、CS2、CS3及CS4(比較例)。
該四種電泳墨液介質樣品皆在異鏈烷烴溶劑中包括30%塗佈聚合物的氧化鈦粒子、7重量%紅色粒子及8%黑色粒子、PIB、0.2% Solsperse 19000及其它電荷佐藥。表1提供包含在每種樣品中的PIB濃度。
透過微胞裝填密封技術將該電泳介質密封在二片透明ITO-PET電極間以提供四個顯示器樣品。該測試樣品係使用相同驅動序列,由波形產生器驅動。在D65照明環境下,使用X-rite iOne分光光度計進行L*a*b*光學性能之測量。
圖1繪製出由顯示器顯示出及提供在表1中的紅色a*(Ra)值,其闡明隨著PIB濃度增加而減少。
使用與用以製備比較例相同的方法來製備三個電泳介質樣品,除了將苯乙烯-乙烯-丙烯共聚物加入至該分散液外。重覆及使用該光學測試方法以提供雙穩定性結果。
表2所提供的雙穩定性或影像穩定性結果係 藉由下列獲得:將每個樣品驅動至白色、黑色或紅色任一種狀態,讓該樣品與電源形成斷路,留下該樣品24小時,然後再次測量該光學狀態。表2中的△值係在儲存前後之光學值間的差異。
如由表2闡明,該有色電泳介質之影像穩定性可隨著聚異丁烯濃度增加而改良或維持,及當該共聚物係存在於該分散液中時,雖然聚異丁烯負載增加,其顏色性能(紅色a)顯示實質上改良。
藉由加入聚異丁烯與以苯乙烯及乙烯/丙烯為主的線性二嵌段共聚物之組合,不僅可維持及/或改良影像穩定性而且亦可達成較好的顏色狀態程度。因此,PIB與根據本發明的多個具體實例之共聚物的組合提供可被包括在電泳介質中來改良該介質性能之添加劑。
將由熟習該項技術者明瞭,可在本發明的上述特定具體實例中製得許多改變及改質而沒有離開本發明之範圍。此外,前述說明全部欲解釋為作例證用及非 為限制性觀念。
Claims (19)
- 一種電泳介質,其包含分散液,該分散液包含:(a)非極性流體;(b)複數個第一帶電荷粒子;(c)聚異丁烯;及(d)添加劑,其係包含乙烯、丙烯及乙烯基芳香烴的共聚物。
- 如請求項1之電泳介質,其中該乙烯基芳香烴係選自於由下列所組成之群:苯乙烯、α-甲基苯乙烯、2-甲基苯乙烯、3-甲基苯乙烯、4-甲基苯乙烯、44-丁基苯乙烯、4-環己基苯乙烯、4-十二烷基苯乙烯、2,4-二異丙基苯乙烯、2,4,6-三甲基苯乙烯、2-乙基-4-苄基苯乙烯、4-(苯基丁基)苯乙烯、1-乙烯基萘、2-乙烯基萘、乙烯基蒽、4-甲氧基苯乙烯、單氯苯乙烯、二氯苯乙烯、二乙烯基苯、茚、甲基茚及其組合。
- 如請求項1之電泳介質,其中該乙烯基芳香烴包含苯乙烯。
- 如請求項1之電泳介質,其中該添加劑係苯乙烯、乙烯及丙烯之共聚物。
- 如請求項1之電泳介質,其中在該共聚物中的苯乙烯重量百分比係20%至40%。
- 如請求項1之電泳介質,其中在該分散液中之聚異丁烯對添加劑的重量比率係1:5至5:1。
- 如請求項1之電泳介質,其中該第一帶電荷粒子係紅色、綠色、藍色、青綠色、黃色或品紅色。
- 如請求項7之電泳介質,更包含複數個第二帶電荷粒子分散在該非極性流體中。
- 如請求項8之電泳介質,其中該第二帶電荷粒子係白色或黑色。
- 如請求項9之電泳介質,其中該第二帶電荷粒子係白色,且該第一與第二帶電荷粒子具有相反的電荷極性。
- 如請求項10之電泳介質,其中該第二帶電荷粒子包含二氧化鈦。
- 如請求項10之電泳介質,其更包含複數個第三帶電荷粒子分散在該非極性流體中。
- 如請求項12之電泳介質,其中該第三帶電荷粒子係黑色,且該第一與第三帶電荷粒子具有相同電荷極性。
- 如請求項13之電泳介質,其中該第三帶電荷粒子包含碳黑或亞鉻酸銅。
- 如請求項1之電泳介質,其更包含離子界面活性劑。
- 如請求項1之電泳介質,其中該聚異丁烯與添加劑之結合的重量百分比係0.1至2.5%,以該分散液的總重量為基準。
- 如請求項1之電泳介質,其中該聚異丁烯與添加劑之結合的重量百分比係0.5至1%,以該分散液的總重量為基準。
- 如請求項1之電泳介質,其更包含複數個第二帶電荷粒子及複數個第三帶電荷粒子分散在該非極性流體中,其中該第一、第二或第三帶電荷粒子係紅色、綠色、藍色、青綠色、黃色、品紅色、白色或黑色。
- 如請求項1之電泳介質,其中該非極性流體包含C6-C18分枝烷烴。
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| TW107105160A TWI700325B (zh) | 2017-02-15 | 2018-02-13 | 使用在有色電泳顯示介質中的聚合物添加劑 |
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| TWI550332B (zh) * | 2013-10-07 | 2016-09-21 | 電子墨水加利福尼亞有限責任公司 | 用於彩色顯示裝置的驅動方法 |
| US9361836B1 (en) | 2013-12-20 | 2016-06-07 | E Ink Corporation | Aggregate particles for use in electrophoretic color displays |
| TWI571688B (zh) | 2014-01-02 | 2017-02-21 | 電子墨水加利福尼亞有限責任公司 | 用於提升電泳顯示器影像穩定度之方法 |
| US9688859B2 (en) | 2014-02-06 | 2017-06-27 | E Ink Corporation | Electrophoretic particles and processes for the production thereof |
| EP3111277B1 (en) | 2014-02-24 | 2019-04-10 | E Ink California, LLC | Electrophoretic display |
| WO2015148398A1 (en) | 2014-03-25 | 2015-10-01 | E Ink California, Llc | Magnetophoretic display assembly and driving scheme |
| US20160012710A1 (en) | 2014-07-10 | 2016-01-14 | Sipix Technology Inc. | Smart medication device |
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2018
- 2018-02-12 CN CN201880010867.1A patent/CN110268317B/zh active Active
- 2018-02-12 PL PL18755063.7T patent/PL3583464T3/pl unknown
- 2018-02-12 US US15/893,747 patent/US10254622B2/en active Active
- 2018-02-12 JP JP2019538327A patent/JP6931704B2/ja active Active
- 2018-02-12 KR KR1020197022028A patent/KR102187730B1/ko active Active
- 2018-02-12 EP EP18755063.7A patent/EP3583464B1/en active Active
- 2018-02-12 ES ES18755063T patent/ES2947325T3/es active Active
- 2018-02-12 WO PCT/US2018/017742 patent/WO2018152041A1/en not_active Ceased
- 2018-02-13 TW TW109120570A patent/TWI780445B/zh active
- 2018-02-13 TW TW107105160A patent/TWI700325B/zh active
-
2019
- 2019-02-21 US US16/281,240 patent/US20190187534A1/en not_active Abandoned
-
2020
- 2020-08-18 JP JP2020138072A patent/JP2020187380A/ja not_active Withdrawn
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| US20030002132A1 (en) * | 2001-05-24 | 2003-01-02 | Xerox Corporation | Photochromic electrophoretic ink display |
| US20080013155A1 (en) * | 2006-07-11 | 2008-01-17 | E Ink Corporation | Electrophoretic medium and display with improved image stability |
| TW201402715A (zh) * | 2012-05-14 | 2014-01-16 | Merck Patent Gmbh | 用於電泳顯示器之粒子 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2020187380A (ja) | 2020-11-19 |
| CN110268317B (zh) | 2022-10-21 |
| ES2947325T3 (es) | 2023-08-04 |
| KR102187730B1 (ko) | 2020-12-07 |
| EP3583464A4 (en) | 2020-03-11 |
| JP6931704B2 (ja) | 2021-09-08 |
| WO2018152041A1 (en) | 2018-08-23 |
| CN110268317A (zh) | 2019-09-20 |
| EP3583464B1 (en) | 2023-06-07 |
| PL3583464T3 (pl) | 2023-10-02 |
| EP3583464C0 (en) | 2023-06-07 |
| US20190187534A1 (en) | 2019-06-20 |
| US10254622B2 (en) | 2019-04-09 |
| TWI780445B (zh) | 2022-10-11 |
| JP2020504336A (ja) | 2020-02-06 |
| US20180231864A1 (en) | 2018-08-16 |
| EP3583464A1 (en) | 2019-12-25 |
| KR20190091380A (ko) | 2019-08-05 |
| TW201835199A (zh) | 2018-10-01 |
| TW202035473A (zh) | 2020-10-01 |
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