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TWI395017B - 可重複加工之液晶膜及其製造方法 - Google Patents

可重複加工之液晶膜及其製造方法 Download PDF

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Publication number
TWI395017B
TWI395017B TW97148718A TW97148718A TWI395017B TW I395017 B TWI395017 B TW I395017B TW 97148718 A TW97148718 A TW 97148718A TW 97148718 A TW97148718 A TW 97148718A TW I395017 B TWI395017 B TW I395017B
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Taiwan
Prior art keywords
liquid crystal
crystal film
reprocessable
film according
thermoplastic polymer
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TW97148718A
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English (en)
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TW201022783A (en
Inventor
Chih Lung Chin
Chang Hung Wu
Shih Hsien Liu
Kung Lung Cheng
Yih Her Chang
Jer Young Chern
Ching Yu Chen
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Ind Tech Res Inst
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Priority to TW97148718A priority Critical patent/TWI395017B/zh
Priority to US12/418,545 priority patent/US20100151228A1/en
Publication of TW201022783A publication Critical patent/TW201022783A/zh
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Publication of TWI395017B publication Critical patent/TWI395017B/zh

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  • Physics & Mathematics (AREA)
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  • Nonlinear Science (AREA)
  • Dispersion Chemistry (AREA)
  • Mathematical Physics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Liquid Crystal (AREA)

Description

可重複加工之液晶膜及其製造方法
本發明係有關於一種液晶膜，且特別是有關於一種可重複加工之電可調光液晶膜。
電可調光玻璃(electrically switchable glass)又稱智慧型玻璃(smart glass)，屬建築裝飾特種玻璃之一，其中間夾有液晶膜，利用液晶的特性，通過電控改變電流的大小調節透光率，可實現玻璃從透明到不透明的轉換。電控調光玻璃現已廣泛應用於高檔辦公室、商業、醫院、住宅、機房、汽車以及航太等領域，亦可作為投影機之螢幕。
電可調光玻璃的調光原理是：在自然狀態下(斷電不加電場)，它內部液晶的排列是無規則的，使得入射光經過液晶層會發生散射，呈乳白色，即不透明。當加上電場(通電)以後，液晶分子從無序排列變為定向有序排列，入射光可以通過液晶層，形成透明狀態。
習知電可調光玻璃所用之液晶膜為一種聚合物分散型液晶膜(Polymer dispersed liquid crystal film；PDLC film)，其扭曲或受壓時會有漏光現象，因此不適合應用於曲面(例如車窗玻璃)，其原因可能是因為單體聚合時將液晶排出而產生大小不一的液晶微粒所造成。此外，習知之調光液晶膜無法重覆貼合/加工，且無法以成捲式連續製程 (Roll－to－Roll process)生產。
為解決上述問題，有必要提出一種可重複加工之電可調光液晶膜，其可以成捲式連續製程生產，且不會因扭曲或受壓而有漏光現象。
本發明提供一種可重複加工之液晶膜，包括：一第一基板；一第一導電層，設置於第一基板上；以及，一液晶層，設置於第一導電層上，液晶層包含微膠囊化液晶微粒分散於一熱塑性高分子中。
本發明另提供一種可重複加工之液晶膜的製造方法，包括下列步驟：混合微膠囊化液晶微粒與接著劑以形成一液晶塗料，其中接著劑為一熱塑性高分子水溶液；將液晶塗料塗佈於一覆有導電層之基板；以及，將塗佈於該基板上之液晶塗料乾燥成膜。
為讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉出較佳實施例，並配合所附圖式，作詳細說明如下：
本發明使用微膠囊化液晶與熱塑型高分子接著劑均勻混合製作成液晶塗料，可進行大面積生成捲式連續塗佈製程，且本發明所製作之可調光液晶薄膜具可重複貼合性/ 加工性，且不會因扭曲或輕壓而有漏光現象，具有高度隱蔽性。
以下將配合第1圖說明本發明電可調光液晶膜之製作流程。首先，微膠囊化液晶與熱塑型高分子接著劑均勻混合以形成液晶塗料(步驟S100)。習知聚合物分散型液晶(Polymer dispersed liquid crystal；PDLC)係將液晶直接分散於高分子基質中，而本發明所用之微膠囊化液晶(PDMLC；polymer dispersed microencapsulated liquid crystal)則是更包括一微膠囊外壁(capsule wall)包覆液晶材料，使液晶以微膠囊化的方式分散於高分子基質中。上述液晶材料例如是向列相(Nematic)、膽固醇相(Cholesteric)、層列相(Smectic)、或強誘電性(ferroelectric)液晶，而微膠囊外壁為一高分子材料，例如聚氨酯(polyurethane)、聚脲(polyurea)、聚丙烯酸、環氧樹脂、聚酯等。有關微膠囊化液晶的組成與製備方式可參考美國專利US 6120701。微膠囊化液晶的粒徑約1~6μm。應注意的是，藉由將含有微膠囊化液晶的分散液進行離心處理可以篩選出大小相近之粒徑，此為使用微膠囊化液晶的優點之一。
本發明所使用之熱塑型高分子接著劑為一熱塑性高分子水溶液，其濃度例如約5~35%，較佳約10~30%(重量百分比)。熱塑性高分子接著劑包括(但不限於)：聚乙烯醇(PVA)、聚氨酯(PU)、聚氨酯(polyurethane)、聚丙烯酸、聚乙烯吡咯烷酮(PVP)、聚醋酸乙烯酯(PVAc)、或前述之組合，其中又聚乙烯醇較佳。在一實施例中，熱塑性高分子 的重量平均分子量約27000~32000，平均聚合度約550~650。本發明特徵之一係使用低離子含量之熱塑性高分子作為接著劑，其離子含量較佳小於100ppm，更佳小於1000ppm。使用之低離子含量熱塑性高分子接著劑可以避免造成漏電流，因而改善電可調光液晶膜的性能。
在一實施例中，將微膠囊化液晶與熱塑性高分子水溶液以1：1－3重量比於室溫下均勻混合，即可製備出液晶塗料，其固含量約20－60%，較佳約30－50%，在25℃下之黏度約800－2000 cps，較佳約1000－1200 cps。
接著，將含有微膠囊化液晶與接著劑之液晶塗料塗佈在一覆有導電層之基板上，例如氧化銦錫－聚對苯二甲酸乙二酯(ITO－PET)基板(步驟S110)，並將液晶塗料乾燥成膜(步驟S120)，形成一液晶層。最後，再與另一片覆有導電層之基板進行貼合(步驟130)，即可形成本發明之電可調光玻璃。
上述步驟S110~S130較佳係整合於一成捲式連續製程進行，以製作出大面積成捲式之液晶薄膜。如第2圖所示，以驅動滾輪30將整捲之ITO－PET薄膜展開，例如可用線速約2－4公尺/分鐘的速度展開。當ITO－PET薄膜15通過滾輪10時，將步驟S110所得之液晶塗料20經由一狹縫塗佈頭(slot die)40塗佈至ITO－PET薄膜上，之後經過一乾燥箱60進行乾燥成膜。乾燥箱60例如是具有多段溫度區之烘箱，溫度範圍較佳可從40℃至90℃。成膜後再經由熱貼合輪80以例如約90－110℃與另一片ITO－PET薄膜25貼 合，即可連續生成電可調光液晶薄膜35，最後並藉由捲取滾輪50捲取之。應注意的是，第2圖所示之裝置僅為成捲式連續製程的一種實施方式，但本發明並非以此為限。
請參見第3圖，其顯示本發明實施例之電可調光液晶薄膜的剖面示意圖。如圖中所示，本發明之電可調光液晶薄膜包括一第一基板100、一第一導電層150設置於第一基板100上、以及一液晶層300設置於第一導電層150上。液晶層300包含複數個微膠囊化液晶微粒320分散於一熱塑性高分子310中，其中微膠囊化液晶微粒320是由微膠囊外壁320b與內部之液晶分子320a所構成。液晶層300中微膠囊化液晶微粒320與熱塑性高分子310的重量比較佳為1：2，更佳約1：1.5。在液晶層300之上更包括一第二導電層250與第二基板200。第一導電層150與第二導電層250係作為電極以控制液晶320a的排列方向。在不加電場的情況下，微膠囊化液晶微粒320內部的液晶分子320a排列是無規則的，入射光在液晶層300內發生散射，而呈不透明。當加上電場以後，液晶分子320a從無序排列變為定向有序排列，入射光完全可以通過，形成透明狀態。
在第3圖中，第一導電層150與第二導電層250例如是氧化銦錫(ITO)、氧化銦鋅(IZO)、氧化鋁鋅(AZO)等透明導電層。第一基板100與第二基板200除了PET外，亦可以是其他透明高分子材料，例如聚碳酸酯(PC)、聚萘二甲酸乙二酯(PEN)、聚亞醯胺(PI)、聚醚碸(PES)等。此外，如果是應用在非連續製程，也可使用硬質透明基材，例如玻 璃。液晶層300的厚度約從10－20μm，可視所需要之性質是高透光(薄膜)或高遮蔽(厚膜)而定。藉由調控液晶塗料之黏度、狹縫塗佈頭之寬度、基材移動之線速，即可隨意控制液晶層的厚度。
本發明之電可調光液晶膜的優點之一是不會因扭曲或受壓而有漏光現象，其原因可能是所使用之微膠囊化液晶可篩選微粒大小的分佈，並使液晶微滴可固定於液晶薄膜中不易受外界壓力而有流動或變形現象。此特性使得本發明之電可調光液晶膜可特別應用於具有曲面的物件上(例如車窗玻璃、或具有曲面之造型玻璃)，而傳統電可調光液晶膜則會因扭曲漏光無法作此類應用。
本發明之電可調光液晶膜的另一優點是具有可重複貼合性/加工性。由於本發明所用之接著劑為熱塑性高分子，因此液晶層300上的第二基材200(含第二導電層250)可重複多次撕開、再貼合而不影響其光電性質，具有可重工性，而傳統使用熱固性接著劑(如環氧樹脂)的電可調光液晶膜一旦與另一基材貼合後即無法撕開，對於後續的加工較為不利。
第4圖顯示本發明另一實施例之電可調光液晶薄膜的剖面示意圖。在此實施例中，係於液晶層300乾燥後改用一離型膜400貼合於液晶層300表面，以取代第3圖中的第二基材200與第二導電層250。離型膜400的材質例如是PET、聚丙烯(PP)、聚乙烯(PE)、聚氯乙烯(PVC)、矽氧樹脂(silicone)等，厚度可從10~100μm。藉由將第2圖之 ITO－PET薄膜25取代成離型膜，本發明可製作出成捲且具有離型膜之液晶薄膜。此具有離型膜之產品可視實際電可調光玻璃的尺寸之決定後再裁切成適當尺寸，取下離型膜後即可與另一片具有預定尺寸之ITO－PET薄膜或其他類型之導電基板(例如ITO－玻璃基板)貼合，具有製程上可調性。
【合成例：微膠囊化液晶微粒】
將2.5克聚氨酯(Desmodur N－3200,Bayer Corp.)與40克液晶(DH－032,工研院自製；△n＝0.19、Tc＝89℃)於60℃下均勻混合。將上述混合溶液加入200克之10%聚乙烯醇水溶液進行攪拌，然後於50－55℃下以3000rpm，3分鐘進行乳化得到粒徑1－10μm之顆粒。之後加入25克之10%三乙烯二胺(Triethylene Diamine)與25克之10%三乙醇胺(Triethanolamine)於55℃下反應10小時。反應完畢後，加入20克之10%氫氧化銨，靜置過夜。最後將所得漿料以5000 rpm轉速進行離心，得到粒徑分佈1－5μm之微膠囊化液晶微粒。
【實施例1】
將合成例之微膠囊化液晶微粒與20%聚乙烯醇水溶液依照1：1.5(重量比)在室溫下比例均勻混合，即可配製出液晶塗料，塗料之黏度為1000~1100cps(25℃)、固含量約 為42%。上述所用之聚乙烯醇的重量分子量為27000－32000，聚合度為550－650，鈉離子含量低於60ppm。
以第2圖所示之裝置，將PET－ITO薄膜經狹縫塗佈頭塗上液晶塗料後(塗幅寬為1.1公尺)，進入五段式烘箱(溫度40~90℃)乾燥，以線速約為4公尺/分鐘移動速度移動，最後經過約100℃熱貼合輪與另一片PET－ITO薄膜貼合，連續生成電可調光液晶薄膜，厚度控制為15μm。
【實施例2】
同實施例1，但其中液晶塗料改由微膠囊化液晶微粒與20%聚乙烯醇水溶液、20%聚氨酯(PU)水溶液依照1：1.29：0.21(重量比)在室溫下均勻混合，塗料之黏度為800~900cps(25℃)、固含量約為42%。
【電可調光液晶膜之光電性分析】
將實施例1、2成捲之電可調光液晶膜裁切後經玻璃膠合加工製程製作出之電可調光玻璃，尺寸為寬1.1公尺、長3公尺。以明晰度儀(EDTM公司之儀器)量測其光電性質，其結果如第5圖所示，其中實施例1之電可調光液晶膜具有高透光度(T%＝65% @ 45V)已優於Polytronix公司之市售商品PolyvisionTM (T%＝54% @ 45V)。
【不同膜厚之電可調光液晶膜之光電性分析】
依照實施例1之製程，但控制不同狹縫頭至基材的間距，可塗佈出不同的濕膜厚度，再進行乾燥、貼合等製程後可分別製作乾膜厚度為10μm與17μm(此厚度未包含PET－ITO基材的厚度)的電可調光液晶膜，量測其透光度。結果如下表與第6圖所示：膜厚大(17μm)的透光度差(7%~66%)，即遮蔽力好；膜厚小(10μm)的透光度好(10%~70%)，即遮蔽力差。
【可重複加工/貼合測試】
量測實施例1之電可調光薄膜樣品未撕開及撕開－貼合3次之透光度對電壓關係圖，撕開－貼合實驗為將撕開之樣品經過護貝機(貼合溫度為100℃)後量測其光電性，其結果如第7圖所示，未撕開前與撕開－貼合3次後樣品之光電性質差異不大。
【扭曲不透光測試】
將長21cm、寬8cm之Polytronix公司之市售商品 PolyvisionTM 摺出直徑為6cm之中空圓柱狀，量測此薄膜之在不同電壓下之穿透度，其結果如第8圖所示，Polytronix商品經量測後當V＝0時，未扭曲時穿透度為3%；扭曲後穿透度提升至為15%，相差12%。
同樣地，將長21cm、寬8cm之實施例1電可調光薄膜樣品摺出直徑為6cm之中空圓柱狀，量測此薄膜之在不同電壓下之穿透度，其結果如第9圖所示，當V＝0時，未扭曲時穿透度為6%；扭曲後穿透度提升至為7%，僅相差1%，證實本發明電之可調光薄膜在扭曲時具有不會漏光，可貼合至曲面玻璃上仍具備高隱蔽性。
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何所屬技術領域中具有通常知識者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
S100－S130‧‧‧流程步驟
10、30、50‧‧‧滾輪
15、25‧‧‧ITO－PET薄膜
20‧‧‧液晶塗料
35‧‧‧電可調光液晶薄膜
40‧‧‧狹縫塗佈頭
60‧‧‧乾燥箱
80‧‧‧熱貼合輪
100、200‧‧‧基板
150、250‧‧‧導電層
300‧‧‧液晶層
310‧‧‧熱塑性高分子
320‧‧‧微膠囊化液晶微粒
320a‧‧‧液晶分子
320b‧‧‧微膠囊外壁
400‧‧‧離型膜
第1圖顯示本發明實施例之液晶膜的製作流程。
第2圖顯示一種用以製作本發明之液晶膜的成捲式連續製程設備。
第3圖為本發明一實施例之液晶膜的剖面示意圖。
第4圖為本發明另一實施例之液晶膜的剖面示意圖。
第5~9圖為本發明實施例之光電性質測試結果。

Claims (23)

  1. 一種可重複加工之液晶膜，包括：一第一基板；一第一導電層，設置於該第一基板上；以及一液晶層，設置於該第一導電層上，該液晶層包含微膠囊化液晶微粒分散於一熱塑性高分子中，其中該微膠囊化液晶微粒包括一微膠囊外壁包覆一液晶材料。
  2. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該熱塑性高分子包括：聚乙烯醇(PVA)、聚氨酯(PU)、聚氨酯(polyurethane)、聚丙烯酸、聚乙烯吡咯烷酮(PVP)、聚醋酸乙烯酯(PVAc)、或前述之組合。
  3. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該熱塑性高分子之離子含量小於100ppm。
  4. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該熱塑性高分子之離子含量小於1000ppm。
  5. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該熱塑性高分子之重量平均分子量約27000~32000。
  6. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該熱塑性高分子之平均聚合度約550~650。
  7. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該液晶層之厚度約10-20μm。
  8. 如申請專利範圍第1項所述之可重複加工之液晶膜，更包括：一第二導電層設置於該液晶層上，以及一第 二基板，設置於該第二導電層上。
  9. 如申請專利範圍第1項所述之可重複加工之液晶膜，更包括一離型膜設置於該液晶層上。
  10. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該微膠囊化液晶微粒之粒徑約1~6μm。
  11. 如申請專利範圍第1項所述之可重複加工之液晶膜，其中該第一基板係設置於一曲面上。
  12. 一種可重複加工之液晶膜的製造方法，包括下列步驟：混合微膠囊化液晶微粒與接著劑以形成一液晶塗料，其中該接著劑為一熱塑性高分子水溶液，且該微膠囊化液晶微粒包括一微膠囊外壁包覆一液晶材料；將該液晶塗料塗佈於一覆有導電層之基板；以及將塗佈於該基板上之液晶塗料乾燥成膜。
  13. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該熱塑性高分子水溶液之濃度約5~35%。
  14. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該熱塑性高分子水溶液之濃度約10~30%。
  15. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該液晶塗料之固含量約20-60%。
  16. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該可塑性高分子包括：聚乙烯醇、聚 氨酯、聚氨酯、聚丙烯酸、聚乙烯吡咯烷酮、聚醋酸乙烯酯、或前述之組合。
  17. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該熱塑性高分子之離子含量小於1000ppm。
  18. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該熱塑性高分子之離子含量小於100ppm。
  19. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中該液晶塗料約於40~90℃的溫度下乾燥成膜。
  20. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中於乾燥成膜後更包括：與另一覆有導電層之基板進行貼合。
  21. 如申請專利範圍第12項所述之可重複加工之液晶膜的製造方法，其中於乾燥成膜後更包括：與一離型膜進行貼合。
  22. 如申請專利範圍第12~21項任一項所述之可重複加工之液晶膜的製造方法，其係以一成捲式連續製程進行。
  23. 如申請專利範圍第21項所述之可重複加工之液晶膜的製造方法，更包括：將該液晶膜貼合至一曲面上。
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