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TWI441857B - 電泳介質 - Google Patents

電泳介質 Download PDF

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TWI441857B
TWI441857B TW100111770A TW100111770A TWI441857B TW I441857 B TWI441857 B TW I441857B TW 100111770 A TW100111770 A TW 100111770A TW 100111770 A TW100111770 A TW 100111770A TW I441857 B TWI441857 B TW I441857B
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electrophoretic medium
electrophoretic
salt
layer
medium
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TW201144366A (en
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Eva Chen
Richard M Webber
David D Miller
Jonathan Kim Nguyen
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E Ink Corp
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    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/165Devices 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
    • G02F1/166Devices 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
    • G02F1/167Devices 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 by electrophoresis
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/165Devices 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
    • G02F1/1675Constructional details
    • G02F1/16757Microcapsules
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F1/00Devices 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
    • G02F1/01Devices 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 
    • G02F1/165Devices 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
    • G02F1/1675Constructional details
    • G02F2001/1678Constructional details characterised by the composition or particle type
    • GPHYSICS
    • G02OPTICS
    • G02FOPTICAL 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
    • G02F2202/00Materials and properties
    • G02F2202/06Materials and properties dopant

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  • Physics & Mathematics (AREA)
  • Nonlinear Science (AREA)
  • Health & Medical Sciences (AREA)
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  • Electrochemistry (AREA)
  • Molecular Biology (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Electrochromic Elements, Electrophoresis, Or Variable Reflection Or Absorption Elements (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Description

電泳介質
本申請案係關於美國專利第7,012,735號及美國專利申請案公告第2009/0122389號。
本發明係關於可用於製造電泳顯示器之電泳介質、用於此介質之黏合劑、及使用此黏合劑所形成之電泳顯示器。
名詞「雙穩態(bistable)」及「雙穩性(bistability)」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,假定為其第一或第二顯示狀態在已終止定址脈衝後此狀態仍持續至少數次(例如至少4次)之改變顯示元件狀態所需定址脈衝的最小時間。美國專利第7,170,670號證明一些可為灰階之粒子為主電泳顯示器不僅在其極端黑白狀態,亦在其中間灰階狀態穩定,且亦適用於一些其他型式之電光顯示器。此型顯示器被適當地稱為「多穩態」而非雙穩態,雖然為了方便而可在此使用名詞「雙穩態」涵蓋雙穩態與多穩態顯示器。
多年來電泳顯示器已成為深入研發之標的。在粒子為主電泳顯示器中,複數帶電粒子在電場影響下移動通過流體。在相較於液晶顯示器時,電泳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。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而造成這些顯示器之不當使用壽命。
如上所示,電泳介質需要流體存在。在大部分先行技藝電泳介質中,此流體為液體,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 display”,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。在將介質用於允許此沉降之定向時,例如將介質分配於垂直面之信號,此氣體為主電泳介質顯然易有如液體為主電泳介質由於粒子沉降造成之相同型式問題。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,粒子沉降顯然在氣體為主電泳介質中為較在液體為主中嚴重之問題。
讓渡予或麻省理工學院(MIT)及E Ink Corporation擁有之許多專利及申請案揭述各種用於封包電泳及其他電光介質之技術。此經封包介質係包含許多小囊,其本身各包含在流體介質中含有電泳地移動粒子之內相、及包圍該內相之囊壁。一般而言,該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揭述之技術係包括:
(a) 電泳粒子、流體與流體添加劑;參見例如美國專利第7,002,728與7,679,814;
(b) 囊、黏合劑與封包方法;參見例如美國專利第5,930,026、6,067,185、6,130,774、6,172,798、6,249,271、6,327,072、6,392,785、6,392,786、6,459,418、6,839,158、6,866,760、6,922,276、6,958,848、6,987,603、7,061,663、7,071,913、7,079,305、7,109,968、7,110,164、7,202,991、7,242,513、7,304,634、7,339,715、7,391,555、7,411,719、7,477,444、與7,561,324號,及美國專利申請案公告第2004/0112750、2005/0156340、2007/0057908、2007/0091417、2007/0223079、2008/0023332、2008/0130092、2008/0264791、2009/0122389、與2010/0044894號;
(c) 含有電光材料之膜與次組件;參見例如美國專利第6,982,178與7,839,564號;
(d) 用於顯示器之底板、黏著層與其他輔助層、及方法;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7,075,502號及美國專利申請案公告第2007/0109219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;
(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;以及。
(h) 非電泳顯示器,如美國專利第6,241,921、6,950,220與7,420,549號,及美國專利申請案公告第2009/0046082號所揭述。
許多上述專利及申請案認為在經封包電泳介質中包圍離散微囊之壁可被連續相取代,如此製造所謂之聚合物分散性電泳顯示器,其中電泳介質係包含複數離散電泳流體滴、及聚合物材料之連續相,且此聚合物分散性電泳顯示器內之離散電泳流體滴可被視為囊或微囊,即使個別滴均不帶有離散囊膜;參見例如上述美國專利第6,866,760號。因而為了本申請案之目的,此聚合物分散性電泳介質係視為經封包電泳介質之次物種。
一種相關型式之電泳顯示器為所謂之「微胞(microcell)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,而是保留在於載體介質(一般為聚合膜)內所形成之複數穴內。參見例如美國專利第6,672,921與6,788,449號,其均讓渡予Sipix Imaging,Inc.。
雖然電泳介質經常為不透明(由於例如在許多電泳介質中,粒子實質上阻擋可見光穿透顯示器)且係以反射模式操作,其可使許多電泳顯示器以所謂之「快門模式」操作,其中一種顯示狀態為實質上不透明且另一種為透光性。參見例如上述美國專利第6,130,774與6,172,798號、及美國專利第5,872,552、6,144,361、6,271,823、6,225,971、與6,184,856號。類似電泳顯示器但依賴電場強度變化之二電泳顯示器可以類似模式操作;參見美國專利第4,418,346號。其他型式之電光顯示器亦可以快門模式操作。
經封包電泳顯示器一般未遭受傳統電泳顯示器之簇聚與沉降失敗模式且提供進一步之優點,如在廣泛種類之撓性與剛性基板上印刷或塗覆顯示器之能力。(使用文字「印刷(“printing”)」係意圖包括所有之印刷與塗覆形式,其包括但不限於:前計量塗覆,如補片模塗覆、縫式或擠壓塗覆、滑動或串接塗覆、簾式塗覆;輥式塗覆,如刮刀輥式塗覆、正反輥式塗覆;凹版塗覆;浸式塗覆;噴灑塗覆;彎式塗覆;旋轉塗覆;刷式塗覆;空氣刀塗覆;絲網印刷法;靜電印刷法;熱印刷法;噴墨印刷法;電泳沉積(參見美國專利第7,339,715號);及其他類似技術。)如此生成之顯示器可為撓性。此外,因為可印刷(使用各種方法)顯示介質,所以可使顯示器本身不昂貴。
電泳顯示器通常包含一層電泳材料、及配置於電泳材料相反側之至少二其他層,此二層之一為電極層。在大部分此種顯示器中,該二層均為電極層,且將電極層之一或兩者圖案化以界定顯示器之像素。例如可將一電極層圖案化成為長形列電極,及將另一層圖案化成為對該列電極以直角行進之長形行電極,該像素係由列與行電極之交叉點所界定。或者且更常為一電極層具有單一連續電極之形式,及將另一電極層圖案化成為像素電極之矩陣,其各界定顯示器之一個像素。在另一型欲用於鐵筆、印刷頭、或與顯示器分開之類似可移動電極的電泳顯示器中,相鄰電泳層之層僅一層包含電極,而電泳層相反側之層一般為欲防止可移動電極損壞電泳層之保護層。
製造三層電泳顯示器通常涉及至少一種積層操作。例如許多上述MIT及E Ink專利及申請案揭述一種製造經封包電泳顯示器之方法,其中將在黏合劑中包含囊之經封包電泳介質塗覆在於塑膠薄膜上包含氧化銦錫(ITO)或類似導電性塗層(其作為最終顯示器之一個電極)的撓性基板上,該囊/黏合劑塗層係乾燥以形成堅固地黏附至該基板之電泳介質的內聚層。分別地,其製備含有像素電極陣列、及將像素電極連接驅動電路之合適導體排列的底板。為了形成最終顯示器,其使用積層黏著劑將其上具有囊/黏結劑層之基板積層於底板。(其可使用非常類似之方法,藉由以尖筆或其他可移動電極可在其上滑動之簡單保護層(如塑膠薄膜)代替底板,而製備可用於尖筆或類似之可移動電極的電泳顯示器。)在此方法之一個較佳形式中,底板本身為撓性,且係藉由將像素電極與導體印刷在塑膠薄膜或其他撓性基板上而製備。藉此方法量產顯示器之顯而易知積層技術為使用積層黏合劑之捆式積層。類似之製造技術可用於其他型式之顯示器。例如可將微胞電泳介質以如經封包電泳介質之實質上相同方式積層於底板。
如上述美國專利第6,982,178號所討論(參見第3欄第63行至第5欄第46行),許多用於電泳顯示器之組件、及用於製造此顯示器之方法係源自用於液晶顯示器(LCD)(雖然使用液態而非固態介質,但是當然亦為電光顯示器)之技術。例如電泳顯示器可利用包含電晶體或二極體陣列與對應之像素電極陣列的主動矩陣底板、及透明基板上之「連續」前電極(就延伸通過多個像素且一般為整個顯示器之電極而言),這些組件係本質上與LCD中相同。然而用於組合LCD之方法無法用於電泳顯示器。LCD通常藉由在分別之玻璃基板上形成底板與前電極,然後將這些組件黏著固定在一起但其間留下小孔,將所生成之組件置於真空下,及將該組件浸泡於液晶浴中,使得液晶流經底板與前電極間之孔而組合。最後液晶在定位而將孔密封而提供最終之顯示器。
此LCD組合方法無法容易地轉移至電泳顯示器。因為電泳材料為固態,所以其必須在將此二個體彼此固定之前存在於底板與前電極之間。此外,與僅置於前電極與底板之間(但未附著)的液晶材料相反,電泳介質通常必須固定於兩者;在大部分之情形,電泳層係在前電極上形成,因為如此通常較將在含有電路之底板上形成此層容易,然後一般藉由以黏著劑覆蓋電泳層之全部表面且在熱、壓力、可能及真空下積層,而將前電極/電泳層組合積層於底板。因而大部分先行技藝之最終電泳顯示器積層用方法本質上為其中(一般)恰在最終組合前使電泳介質、積層黏著劑與底板在一起的分批方法,且希望提供較佳地適用於量產之方法。
電光顯示器通常為昂貴的;例如可攜式電腦之彩色LCD一般佔全部電腦成本之高比例。隨著電光顯示器已在遠比可攜式電腦便宜之裝置(如行動電話及個人數位助理(PDA))普及,降低此顯示器之成本有極大之壓力。以如以上所討論之對撓性基板的印刷技術形成一些固態電光介質之層的能力,則開啟使用量產技術(如用於製造塗料紙、聚合膜及類似媒體之市售設備的輥對輥塗覆)降低顯示器之電光組件的成本之可能性。
上述美國專利第6,982,178號揭述一種極適合量產之組合固態電光顯示器(包括電泳顯示器)的方法。本質上,此專利揭述所謂之「前板積層物」(“FPL”),其依序包含透光性導電層、電接觸導電層之一層固態電光介質、黏合層及脫模片。一般而言,透光性導電層係以基板可人工地捲繞於(如)直徑10吋(254毫米)之圓筒而不會永久性變形的方式承載於透光性基板(較佳為撓性)上。在此專利中及在此所使用之名詞「透光性」係表示如此設計之層傳送足以使透過此層觀看者觀察到電光介質之顯示狀態變化之光,其通常係透過導電層與相鄰基板(若有)而觀看;在電光介質顯示非可見光波長之反射度變化的情形,名詞「透光性」當然應解讀成係指稱相關非可見光波長之穿透。基板一般為聚合膜,且通常具有約1至約25密耳(25至634微米),較佳為約2至約10密耳(51至254微米)之範圍的厚度。導電層方便地為例如鋁或ITO之薄金屬或金屬氧化物層,或者可為導電性聚合物。塗有鋁或ITO之之聚(對酞酸伸乙酯)(PET)膜為市售,例如得自德拉瓦州Wilmington之E.I. du Pont de Nemours & Company的「鋁化Mylar」(”Mylar”為註冊商標),且可將此市售材料用於前板積層物而獲得良好之結果。
上述美國專利第6,982,178號亦揭述一種用於在將前板積層物倂入顯示器中之前,測試前板積層物中電光介質之方法。在此測試方法中,脫模片具有導電層,且將足以改變電光介質之光學狀態的電壓施加於此導電層與電光介質相反側導電層之間。然後觀察電光介質以顯現介質中之任何缺陷,如此避免將缺陷電光介質積層於顯示器中,造成破壞全部顯示器(不僅缺陷前板積層物)之代價。
上述美國專利第6,982,178號亦揭述一種用於測試前板積層物中電光介質之第二方法,其係藉由將靜電荷置於脫模片上,如此在電光介質上形成影像。然後以如前之相同方式觀察此影像以偵測電光介質中之任何缺陷。
使用此前板積層物之電光顯示器的組合可藉由從前板積層物移除脫模片,及在有效地造成黏著層黏附底板之條件下將黏著層與底板接觸,因而將黏著層、電光介質層與導電層固定於底板而進行。此方法極適合量產,因為可將前板積層物量產(一般使用輥對輥塗覆技術),然後切成用於指定底板所需之任何大小之片。
上述美國專利第7,561,324號揭述所謂之「雙重脫模片」,其本質上為上述美國專利第6,982,178號的前板積層物之簡化版本。一種形式之雙重脫模片係包含包夾於二黏著層之間的一層固態電光介質,黏著層之一或兩者均被脫模片覆蓋。另一種形式之雙重脫模片係包含包夾於二脫模片之間的一層固態電光介質。兩種形式之雙重脫模片均欲用於通常類似由已揭述之前板積層物組合電光顯示器,但是涉及兩次分別之積層的方法之方法;一般而言,其在第一次積層中將雙重脫模片積層於前電極而形成前次組件,然後在第二次積層中將前次組件積層於底板而形成最終顯示器,雖然如果需要則可將此二積層之次序反轉。
上述美國專利第7,839,564號揭述所謂之「反式前板積層物」,其為上述美國專利第6,982,178號所揭述之前板積層物的變體。此反式前板積層物依序包含透光性保護層與透光性導電層至少之一、黏著層、一層固態電光介質及脫模片。此反式前板積層物係用於形成在電光層與前電極或前基板之間具有一層積層黏著劑的電光顯示器,其在電光層與底板之間可存在或無第二黏合(一般為薄)層。此電光顯示器可組合良好之解析度與良好之低溫性能。
由以上之討論明顯可知,電泳顯示器為複雜之系統,其可包含(1)電泳粒子本身,其可為具有核/殼構造及/或聚合物塗層之錯合粒子;(2)包圍電泳粒子之流體;(3)此流體中之添加劑,如電荷控制劑、界面活性劑、分散聚合物等;(4)包圍電泳粒子與流體之囊壁;包圍囊、滴或微胞之黏合劑或其他連續相;(5)一層或以上之黏著層;及(6)一層或以上之電極層。未令人意外,現僅部分地了解關於此系統之複雜性,此顯示器之電光性質與用於形成該顯示器之各種材料的機械、物化及電性質之間的確實關係。例如已知如果用於前板積層物之黏著劑的導電度不足,則可能負面地影響顯示器之電光性能。上述美國專利第7,012,735號揭述將此黏著劑以鹽或其他材料摻雜以改良其導電度而獲得之優點,用於此目的之較佳摻雜劑為六氟磷酸四丁銨(以下稱為”TBAHFP”)。該專利亦揭述類似地以鹽(包括TBAHFP)摻雜黏合劑之優點。
摻雜黏合劑的問題之一係設計以降低或克服所謂之「白色狀態降解」或”WSD”。WSD本身係在顯示器操作期間因顯示器之白色極端光學狀態的反射度(一般在常用之CIE L*a*b*顏色空間中測得之L*值)降低而顯現。實驗上已發現,實得之WSD量係依操作能率循環、電泳介質之內相(電泳粒子加流體)的溫度及組成物而定。現已發現,美國專利申請案公告第2010/0289736號所揭述型式且黏合劑中無離子性摻雜劑之特定電泳介質在25℃以20%之能率循環操作的前48小時實得2-9 L*單位之WSD。此WSD程度對許多應用為無法接受,其在這些條件下操作240小時後須為不大於約3 L*單位(且希望為相當小)之WSD。
雖然對黏合劑添加離子性摻雜劑(一般為鹽)則降低WSD,但是合適鹽之選擇為相當困難。實際上,用於電泳顯示器之內相的流體為有機材料,一般為低分子量烴,且黏合劑為由水溶液或分散液所形成之聚合物,黏合劑之最常見型式為以水性乳膠形式添加之聚胺基甲酸酯。將乳膠與囊混合(在此囊存在時),或者將內相在乳膠中乳化(在聚合物分散性電泳介質之情形)。然後將由乳膠與囊或滴所形成之漿液塗覆在基板上,及將漿液層乾燥而形成內聚電泳層。乍看下離子性摻雜劑似乎為水溶性鹽,其可易於以水溶液之形式加入水性聚合物乳膠。然而發現如氯化鈉之簡單水溶性鹽無法有效地移動WSD;例如對上述美國專利申請案公告第2010/0289736號所揭述型式之電泳介質的黏合劑添加莫耳量等於250-350 ppm之TBAHPF的氯化鈉,則在25℃以20%之能率循環操作240小時後產生約7.5 L*單位之WSD。某些疏水性(水不溶性)鹽獲得較佳之結果;例如美國專利第7,012,735號所述,添加250-350 ppm之TBAHPF則在相同條件下產生約1 L*單位之WSD。這些鹽對WSD之影響為濃度依附性,且其對更大範圍之EO性能(包括例如此薄膜電晶體(TFT)性能、影像安定性及靜態依附性)的影響係對漿液中其他成分之濃度敏感。顯然與漿液摻雜劑交互作用而影響EO性能之其他成分,係包括Triton X100及用於將溶劑輸送至溶液中的溶劑。
不幸地,此水不溶性鹽有其他之問題。將鹽均勻地分散於全部黏合劑中為重要的,且將鹽僅分散於水中不足以產生此均勻分散液。實際上必須將鹽溶於合適之與水互溶有機溶劑中,且將該鹽於溶劑中之溶液加入由其形成黏合劑之乳膠。當然所選擇之溶劑必須不對囊或滴、黏合劑本身、或最終乾燥電泳層之性質具有任何負面影響。合適之溶劑實際上限於N-甲基吡咯啶酮(NMP)、四氫呋喃與丙酮。在乾燥期間難以從電泳層移除全部微量之有機溶劑,因為乾燥條件限於含有揮發性有機流體之囊或滴可容忍的條件。已知殘留在乾燥電泳層或黏著層中之微量有機溶劑造成嚴重之問題;參見例如上述之2009/0122389號專利,其揭述因殘留在乾燥黏著層中之殘量NMP而對含有有機半導體之底板造成損壞。亦已發現殘留在乾燥黏合劑中之殘量有機溶劑會對顯示器之電光性能具有負面影響;例如此有機溶劑已負面地影響顯示器之白色狀態邊緣及暗態暗度。
因而需要一種將離子性摻雜劑加入用於電泳介質的黏合劑,但不將有機溶劑引入黏合劑之方法,且本發明提供此方法。
現已發現,其可在電泳介質之黏合劑中使用陰離子中含有氟且具有至少有限之水溶解度的特定鹽作為離子性摻雜劑。其可將這些液態鹽加入用以形成如水溶液之黏合劑的水性聚合物分散液;在或接近室溫為液態之特定鹽亦可如純液態鹽而添加。
因而本發明之一個態樣提供一種電泳介質,其係包含連續相及不連續相;該不連續相係包含複數滴,其各包含流體、及至少一個配置於該流體內且在對電泳介質施加電場時可移動通過流體之帶電粒子;該連續相係包圍且封包該不連續相,及包含聚合黏合劑與鹽;該鹽係具有含有至少一個氟原子之陰離子,且在25℃之水溶解度為至少約0.25重量%。電泳介質可為經封包或聚合物分散性型,即其可或不為各滴與黏合劑之間的囊壁。電泳介質亦可為微胞型。含氟鹽可以按黏合劑之固體含量計為約50至約10,000 ppm,且通常為約100至約1000 ppm之量存在。
用於本發明電泳介質之較佳鹽為具有含有至少三個氟原子之陰離子者。該鹽例如可具有六氟磷酸鹽陰離子。該鹽亦可具有咪唑陽離子,具體較佳鹽為六氟磷酸3-丁基-1-甲基咪唑鹽。(應注意,美國專利第7,012,735號所述之六氟磷酸四丁銨的水溶性不足以用於本發明)。或者,該鹽可具有四氟硼酸鹽或三氟甲磺酸鹽(triflate)陰離子。
如已敘述,用於本發明電泳介質之鹽在25℃應具有至少約0.25重量%之水溶解度,使得可將該鹽以水溶液之形式加入黏合劑。其希望該鹽在25℃具有至少約1.0重量%之水溶解度,且越大越佳,使得可將該鹽以1重量%水溶液之形式加入黏合劑;其不希望隨鹽對黏合劑添加過量之水,因為鹽/黏合劑混合物通常與電泳介質之內相的囊或滴混合,塗覆在基板上,然後乾燥或暴露於在基板上有效地造成電泳介質之內聚層形成的條件。隨鹽對黏合劑添加過量之水可能延遲基板上電泳介質層之乾燥,如此為不欲的。
一些用於本發明之鹽係具有不大於約25℃之熔點,因此在室溫為液態;例如上述之六氟磷酸3-丁基-1-甲基咪唑鹽(以下稱為”BMIHFP”)在室溫為液態。雖然可將此液態鹽直接分散於水性聚合物分散液或乳膠中而不必使用溶劑,但仍較佳為將此鹽以稀釋水溶液之形式添加,因為顯然使用水溶液提供鹽在全部黏合劑中之較均勻分散。
本發明擴展至一種包含本發明電泳介質、及黏附該電泳介質之黏著層的電泳組合件。電泳介質與黏著層的暴露表面之一或兩者均可被脫模片覆蓋。
本發明之電泳組合件可為前板積層物之形式,其係依序包含基板(可包括透光性導電層)、電泳介質、黏著層及脫模片。或者本發明之電泳組合件可為反式前板積層物之形式,其係依序包含基板(可包括透光性導電層)、黏著層、電泳介質及脫模片。其可將第二黏著層配置於該電泳介質與脫模片之間。如上所述,本發明之電泳組合件可為雙重脫模片之形式。
本發明亦提供一種形成本發明電泳介質之方法。此方法係包含形成聚合物之水性分散液;將鹽之水溶液加入該聚合物之水性分散液,該鹽係具有含有至少一個氟原子之陰離子,且在25℃之水溶解度為至少約0.25重量%;將含有電泳內相之囊或此內相之滴加入該聚合物之含鹽水性分散液;將所獲得之混合物塗覆在基板上;及將基板上之塗層暴露於在基板上有效地造成經塗覆分散液形成電泳介質之內聚層的條件。
如以上所示,本發明提供一種電泳介質,其具有含有含氟陰離子之鹽的黏合劑。現已發現,將此鹽加入電泳介質之黏合劑則有效地降低該介質之WSD;例如添加莫耳量等於250-350 ppm之上述2010/0289736號專利所揭述型式之電泳介質的BMIHFP,則在25℃以20%之能率循環操作240小時後將該介質之WSD從5.4 L*單位降到1.1至1.5 L*單位。添加相同量之BMIHFP亦有效地將暗態降解(”DSD”-以類似WSD之方式測量,除了DSD本身當然因介質暗態之L*值增加而顯現)從2.0 L*單位降到0.5-0.9 L*單位。這些WSD及暗態降解之改良係降低介質之其他重要電光特徵(例如絕對白色及暗態L*值)而獲得。
如已指示,現已發現對電泳介質之黏合劑添加如BMIHPF與TBAHPF之鹽則有效地控制WSD。使用水溶性鹽(如BMIHPF)優於使用水不溶性鹽(如六氟磷酸四丁銨(TBAHPF)),因為不必添加有機溶劑(如NMP)之漿液即可將水溶性鹽輸送至水性囊漿液(即囊與聚合分散液或乳膠之混合物);這些溶劑難以從電泳層移除且已顯示對其他之電光性能參數(例如白色狀態邊緣、暗態等)具有負面影響。
以下之實施例係為了顯示用於本發明之特佳試劑、條件及技術的細節而產生,雖然僅為例證之方式。
<實施例1>
為了證明使用BMIHPF與TBAHPF所獲得之結果而製備上述2010/0289736號專利所揭述型式之一系列電泳介質。各內相係含有0.03重量%之Triton界面活性劑(除了含350 ppm之TBAHPF的介質,其需要0.05重量%之界面活性劑。)將黏合劑摻雜(a)無鹽添加劑(對照);(b)BMIHPF相等於350 ppm TBAHPF之莫耳量;(c) 250 ppm及(d) 350 ppm之TBAHPF。將TBAHPF如NMP溶液而加入,同時由介質製備單像素實驗顯示器,及使用標準測試協定測試WSD、白色與黑色邊緣及揮散。將結果示於以下表1:
由表1之資料可知,使用BMIHPF代替TBAHPF則將白色狀態邊緣(白色狀態中鬼影之測度)減少近半,且雖然DS邊緣增加,但在具有較低WS邊緣值之電泳介質的大部分用途中較TFT性能重要。應注意,雖然輝散性能因使用BMIHPF而惡化,但在實驗室及製造規模實驗中已證明改變黏著劑調配物則可顯著地降低輝散分數;參見以下表2,其報告使用類似用於以上表1之電泳介質而製備之像素實驗顯示器的白色狀態與暗態邊緣、及輝散資料,除了表2介質係含有90或180 ppm(實際值,非TBAHPF當量)之BMIHPF:
亦實驗地發現,根據在0℃所測量之動態範圍(顯示器之極端黑白光學狀態之間的L*單位差)所測量,含有BMIHPF之電泳介質產生較含有等量TBAHPF之介質為低的低溫性能,如以下表3所例證,其中界面活性劑含量為0.03重量%(除了350 ppm之TBA介質,其需要0.05%):
BMIPF6之進一步優點具體而言為微水溶性,且可如稀釋(~1%w/w)水溶液而加入印墨層。
<實施例2>
此實施例係例證六氟磷酸鹽、四氟硼酸鹽與triflate鹽均可用以獲得本發明之優點。
以多種水溶性鹽準備以上實施例1之實驗。在各情形,使用之黏著劑為美國專利第7,012,735號所揭述型式之客製聚胺基甲酸酯黏著劑,其摻雜500 ppm之TBAHPF。將結果示於以下表4。

Claims (20)

  1. 一種電泳介質,其係包含連續相及不連續相;該不連續相係包含複數滴,其各包含流體、及至少一個配置於該流體內且在對電泳介質施加電場時可移動通過流體之帶電粒子;該連續相係包圍且封包該不連續相,及包含聚合黏合劑與鹽;該鹽係具有含有至少一個氟原子之陰離子,且在25℃之水溶解度為至少約0.25重量%。
  2. 如申請專利範圍第1項之電泳介質,其中在各滴與包圍之連續相之間存在囊壁。
  3. 如申請專利範圍第1項之電泳介質,其中各滴係直接接觸該連續相。
  4. 如申請專利範圍第1項之電泳介質,其為微胞介質,其中連續相具有複數穴形成於其中之載體介質形式,不連續相則保留在穴內。
  5. 如申請專利範圍第1項之電泳介質,其中該鹽係具有含有至少三個氟原子之陰離子。
  6. 如申請專利範圍第5項之電泳介質,其中該鹽係具有六氟磷酸鹽陰離子。
  7. 如申請專利範圍第6項之電泳介質,其中該鹽係具有咪唑陽離子。
  8. 如申請專利範圍第7項之電泳介質,其中該鹽係包含六氟磷酸3-丁基-1-甲基咪唑鹽。
  9. 如申請專利範圍第5項之電泳介質,其中該鹽係具有四氟硼酸鹽或三氟甲磺酸鹽陰離子。
  10. 如申請專利範圍第1項之電泳介質,其中該鹽係以按黏合劑之固體含量計為約50至約10,000百萬分點之量存在於黏合劑。
  11. 如申請專利範圍第10項之電泳介質,其中該鹽係以按黏合劑之固體含量計為約100至約1000百萬分點之量存在於黏合劑。
  12. 如申請專利範圍第1項之電泳介質,其中該鹽在25℃之水溶解度為至少約1重量%。
  13. 一種電泳組合件,其係包含一層如申請專利範圍第1項之電泳介質及黏附該電泳介質之黏著層。
  14. 一種前板積層物,其係依序包含基板、一層電泳介質、黏著層及脫模片,其中該電泳介質為如申請專利範圍第1項之電泳介質。
  15. 如申請專利範圍第14項之前板積層物,其中該基板係包含透光性導電層。
  16. 一種反式前板積層物,其係依序包含基板、黏著層、一層電泳介質及脫模片,其中該電泳介質為如申請專利範圍第1項之電泳介質。
  17. 如申請專利範圍第16項之反式前板積層物,其進一步包含配置於該層電泳介質與脫模片之間的第二黏著層。
  18. 一種雙重脫模片,其係包含一層包夾於二黏著層之間的電泳介質,至少一黏著層之暴露表面係被脫模片覆蓋,其中該電泳介質為如申請專利範圍第1項之電泳介質。
  19. 一種雙重脫模片,其係包含一層包夾於二脫模片之間的電泳介質,其中該電泳介質為如申請專利範圍第1項之電泳介質。
  20. 一種形成電泳介質之方法,該方法係包含形成聚合物之水性分散液;將鹽之水溶液加入該聚合物之水性分散液,該鹽係具有含有至少一個氟原子之陰離子,且在25℃之水溶解度為至少約0.25重量%;將含有電泳內相之囊或此內相之滴加入該聚合物之含鹽水性分散液;將所獲得之混合物塗覆在基板上;及將基板上之塗層暴露於在基板上有效地造成經塗覆分散液形成電泳介質之內聚層的條件。
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