TWI600748B - A nematic liquid crystal composition, and a liquid crystal display device using the nematic liquid crystal composition - Google Patents

A nematic liquid crystal composition, and a liquid crystal display device using the nematic liquid crystal composition Download PDF

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TWI600748B
TWI600748B TW102123101A TW102123101A TWI600748B TW I600748 B TWI600748 B TW I600748B TW 102123101 A TW102123101 A TW 102123101A TW 102123101 A TW102123101 A TW 102123101A TW I600748 B TWI600748 B TW I600748B
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liquid crystal
carbon atoms
crystal composition
general formula
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Go Sudo
Shotaro Kawakami
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Dainippon Ink & Chemicals
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Description

向列型液晶組成物及使用其之液晶顯示元件
本發明係關於一種可用作液晶顯示材料,介電各向異性(dielectric anisotropy)(△ε)顯示負值之向列型液晶組成物及使用其之液晶顯示元件。
液晶顯示元件被使用於鐘錶、計算器以及家用之各種電氣設備、測量機器、汽車用面板、文字處理機、電子記事簿、列印機、電腦、電視等。作為液晶顯示方式,其具有代表性者可列舉:TN(扭轉向列,twist nematic)型、STN(超扭轉向列,supertwist nematic)型、DS(動態光散射,dynamic light scattering)型、GH(賓-主,guest-host)型、IPS(橫向電場切換,in plane switching)型、OCB(光學補償雙折射,optical compensated birefringence)型、ECB(電控雙折射,electrically controlled birefringence)型、VA(垂直配向,vertical alignment)型、CSH(彩色超垂面型,colour super homeotropic)型、或者FLC(鐵電液晶,ferroelectric liquid crystal)等。又,作為驅動方式,亦可列舉:靜態驅動、多工驅動、單純矩陣方式、藉由TFT(薄膜電晶體,thin-film transistor)或TFD(薄膜二極體,thin-film diode)等驅動之主動矩陣(AM,active-matrix)方式。
該等顯示方式中,IPS型、ECB型、VA型、或CSH型等具有使用△ε顯示負值之液晶組成物的特徵。該等中,尤其是進行AM驅動 之VA型顯示方式被使用於要求高速應答、廣視角之顯示元件、例如電視等用途中。
作為△ε為負的液晶組成物,揭示有使用如下之具有2,3-二氟伸苯基骨架之液晶化合物(A)及(B)(參照專利文獻1)的液晶組成物。
該液晶組成物中使用作為△ε約為0之液晶化合物的液晶化合物(C)及(D),但未能使液晶電視等要求高速應答之液晶組成物實現足夠低之黏性。
另一方面,亦已揭示有使用液晶化合物(E)之液晶組成物,且介紹了組合有上述液晶化合物(D)之折射率各向異性△n較小之液晶組成物(參照專利文獻2)或為改善應答速度而添加有液晶化合物(F)之液晶組成物(參照專利文獻3)。
另外,亦已揭示有使用液晶化合物(G)及液晶化合物(F) 之液晶組成物(參照專利文獻4),但業界要求更加高速應答化。
揭示有於液晶化合物(A)及液晶化合物(G)組合△ε約為0之式(I)表示之液晶化合物而成之液晶組成物(參照專利文獻5)。然而,認為由於在液晶顯示元件之製造步驟中將液晶組成物注入至液晶單元中時係設定為極低壓,故而蒸氣壓較低之化合物會揮發,因而無法增加其含量。因此,該液晶組成物中對以式(I)表示之液晶化合物之含量加以限定,雖顯示較大之△n,但存在黏度非常高之問題。
進而,於專利文獻6或專利文獻7中,亦已揭示有使用具有經氟取代之聯三苯基構造之化合物的液晶組成物。
另一方面,於專利文獻8中,揭示有藉由使用(式1)表示之指數較大之液晶材料而提高垂面(homeotropic)液晶單元之應答速度的技術,但尚不充分。
FoM=K33.△n2/γ1 (式1)
K33:彈性常數
△n:折射率各向異性
γ1:旋轉黏性
根據以上所述,液晶電視等要求高速應答之液晶組成物中,不使折射率各向異性(△n)及向列相-等向性液體相轉移溫度(Tni)降低,並且要求使黏度(η)足夠小、旋轉黏性(γ1)足夠小,使彈性常數(K33) 增大。
[專利文獻1] 日本特開平8-104869號
[專利文獻2] 歐洲專利申請案公開第0474062號
[專利文獻3] 日本特開2006-37054號
[專利文獻4] 日本特開2001-354967號
[專利文獻5] WO2007/077872
[專利文獻6] 日本特開2003-327965號
[專利文獻7] WO2007/077872號
[專利文獻8] 日本特開2006-301643號
本發明所欲解決之問題在於提供一種液晶組成物,其不使折射率各向異性(△n)及向列相-等向性液體相轉移溫度(Tni)降低,具有黏度(η)足夠小、旋轉黏性(γ1)足夠小、彈性常數(K33)較大,並且絕對值較大之負的介電各向異性(△ε),進而提供一種使用其之VA型等之顯示品質優異、應答速度迅速之液晶顯示元件。
本發明者對各種聯三苯衍生物及氟苯衍生物進行研究,發現藉由將特定之化合物加以組合,可解決上述問題,從而完成本發明。
本發明係提供一種液晶組成物,其含有1種或2種以上以通式(I)所表示之化合物作為第一成分且其含量為3質量%~45質量%,含 有1種或2種以上具有絕對值為3以上之負的△ε之液晶化合物作為第二成分,
(式中,R11表示碳數2~8之烯基或碳數2~8之烯氧基,R12表示碳數1~8之烷基、碳數1~8之烷氧基、碳數2~8之烯基或碳數2~8之烯氧基);另外,本發明係提供一種使用該液晶組成物之液晶顯示元件。
本發明之液晶組成物係不使△n及Tni降低,而使η足夠小、γ1足夠小,且K33較大者,藉由使用該液晶組成物,可提供一種VA型等之顯示品質優異、應答速度迅速之液晶顯示元件。
本發明之液晶組成物含有1種或2種以上以通式(I)所表示之化合物作為第一成分,且其含量為3質量%~45%質量,更佳為5質量%~30%質量,特佳為7質量%~25質量%。
通式(I)之R11更佳為表示碳數4~8之烯基或碳數4~8之烯氧基,特佳為碳數4~5之烯基,R12更佳為表示碳數1~5之烷基、碳數1~5之烷氧基、碳數4~8之烯基或碳數4~8之烯氧基,特佳為碳數1~3之烷基或碳數4~5之烯基。
通式(I)較佳為通式(I-A)。
式中,R13表示碳數4~8之烯基或碳數4~8之烯氧基。更具體而言,較佳為式(I-A1)或(I-A2)所表示之化合物。
本發明之液晶組成物同時含有式(I-A1)及(I-A2)所表示之化合物亦較佳。
本發明之液晶組成物含有1種或2種以上具有絕對值為3以上之負的介電各向異性(△ε)之液晶化合物作為第二成分,更佳為含有具有絕對值為4以上之負的介電各向異性(△ε)之液晶化合物,特佳為含有具有絕對值為5以上之負的介電各向異性(△ε)之液晶化合物。再者,液晶化合物之介電各向異性(△ε)係製備對25℃下介電各向異性約為0之液晶組成物中添加10質量%之液晶化合物所成之組成物,自該組成物之介電各向異性(△ε)之測定值進行外插而求出者。
本發明之液晶組成物係含有1種或2種以上第二成分,較佳為含有1種~15種,更佳為含有2種~10種。
第二成分之含量較佳為10質量%~90質量%,更佳為20質量%~80質量%,特佳為30質量%~70質量%。
第二成分較佳為通式(II-A)及(II-B)所表示之化合物。
式中,R1及R2分別獨立地表示碳數1~8之烷基、碳數1~8之烷氧基、碳數2~8之烯基或碳數2~8之烯氧基,R1及R2中所存在之1個-CH2-或不鄰接之2個以上之-CH2-可分別獨立地取代為-O-及/或-S-,另外,R1及R2中所存在之1個或2個以上之氫原子可分別獨立地取代為氟原子或氯原子。環A及環B分別獨立地表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、1,4-伸環己烯基(1,4-cyclohexenylene)、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基。p及q分別獨立地表示0、1或2。
式中之R1及R2更佳為分別獨立地表示直鏈狀之碳數1~5之烷基、碳數1~5之烷氧基、碳數2~5之烯基或碳數2~5之烯氧基。更詳細而言,為使彈性常數K33較大,R1更佳為碳數2~5之烯基。
式中之環A及環B更佳為分別獨立地表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基或2,3-二氟-1,4-伸苯基,特佳為反-1,4-伸環己基或1,4-伸苯基。
式中之p及q更佳為分別獨立地表示0或1。
通式(II-A)所表示之化合物更佳為通式(II-A1)及(II-A2) 所表示之化合物,通式(II-B)所表示之化合物更佳為通式(II-B1)。
式中,R3及R4分別獨立地表示碳數1~8之烷基或碳數2~8之烯基,R3及R4中所存在之1個或2個以上之氫原子可分別獨立地取代為氟原子。
式中之R3及R4更佳為分別獨立地表示直鏈狀之碳數1~5之烷基或碳數2~5之烯基。更詳細而言,為使彈性常數K33較大,特佳為R3及R4中之某一者為碳數2~5之烯基。
本發明之液晶組成物亦可進而含有1種或2種以上選自以通式(III-A)~通式(III-J)所表示之化合物群中之化合物作為第三成分,更佳為含有1種~10種選自通式(III-A)、(III-D)、(III-F)、(III-G)及(III-H)中之化合物。
式中,R5表示碳數1~5之烷基或碳數2~5之烯基,R6表示碳數1~5之烷基、碳數1~5之烷氧基、碳數2~5之烯基或碳數2~5之烯氧基。再者,於通式(III-A)中,更佳為R5為碳原子數2~5之烯基,R6為碳原子數1~5之烷基。
本發明之液晶組成物亦可含有1種或2種以上通式(V)所表示之化合物作為其他成分。
式中,R21及R22分別獨立地表示碳數1~8之烷基、碳數1~8之烷氧基,較佳為碳數1~5之烷基。
本發明之液晶組成物較佳為同時含有通式(I)、通式(II-A1)及通式(II-A2)所表示之化合物,更佳為同時含有通式(I)、通式(II-A1)、通式(II-A2)及通式(III-A)所表示之化合物。同時含有通式(I)、通式(II-A1)、通式(II-A2)及通式(II-B1)所表示之化合物亦較佳,同時含有通式(I)、通式(II-A1)、通式(II-A2)、通式(II-B1)及通式(III-A)所表示之化合物亦更佳。另外,特佳為同時含有通式(I)、通式(II-A1)、通式(II-A2)、通式(III-A)及通式(V)所表示之化合物。
本發明之液晶組成物之25℃下介電各向異性(△ε)為-2.0~-8.0,較佳為-2.0~-6.0,更佳為-2.0~-5.0,特佳為-2.5~-4.0。
本發明之液晶組成物之20℃下折射率各向異性(△n)為0.08~0.14,更佳為0.09~0.13,特佳為0.09~0.12。更詳細而言,於對應較薄之單元間隙時,較佳為0.10~0.13,於對應較厚之單元間隙時,較佳為0.08~ 0.10。
本發明之液晶組成物之20℃下黏度(η)為10~30mPa.s,更佳為10~25mPa.s,特佳為10~22mPa.s。
本發明之液晶組成物之20℃下之旋轉黏性(γ1)為60~130mPa.s,更佳為60~110mPa.s,特佳為60~100mPa.s。
本發明之液晶組成物之向列相-等向性液體相轉移溫度(Tni)為60℃~120℃,更佳為70℃~100℃,特佳為70℃~85℃。
本發明之液晶組成物中,除上述化合物以外,亦可含有通常之向列型液晶、層列型液晶、膽固醇型液晶、抗氧化劑、紫外線吸收劑、聚合性單體等。
例如,較佳為含有聯苯衍生物、聯三苯衍生物等聚合性化合物作為聚合性單體,且其含量為0.01%~2%。更詳細而言,本發明之液晶組成物較佳為含有一種或兩種以上以通式(IV)所表示之聚合性單體。
式中,R7及R8分別獨立地表示以下之式(R-1)~式(R-15)之任一者,X1~X8分別獨立地表示三氟甲基、三氟甲氧基、氟原子或氫原子。
通式(IV)中之聯苯骨架之構造更佳為式(IV-11)~式(IV-14),特佳為式(IV-11)。
含有式(IV-11)~式(IV-14)所表示之骨架之聚合性化合物,其聚合後之配向約束力最合適,可獲得良好之配向狀態。
例如,同時含有通式(I)、通式(II-A1)、(II-A2)、通式(III-A)及通式(IV)的含聚合性化合物之液晶組成物可達成低黏度(η)、低旋轉黏性(γ1)及大的彈性常數(K33),故而使用其之PSA(polymer stabilized alignment,聚合物穩定配向)模式或PSVA(polymer stabilized vertical-alignment,聚合物穩定垂直配向)模式之液晶顯示元件可實現高速應答。
使用本發明之液晶組成物之液晶顯示元件有效地利用高速應答之顯著特徵,尤其可用作主動矩陣驅動用液晶顯示元件,可應用於VA模式、PSVA模式、PSA模式、IPS模式或ECB模式。
[實施例]
以下列舉實施例進一步詳細地說明本發明,但本發明並不限定於該等實施例。另外,以下之實施例及比較例之組成物中的「%」表示『質量%』。
實施例中關於化合物之記載係使用以下簡記符號。
(側鏈)
-n -CnH2n+1 碳數n之直鏈狀烷基
n- CnH2n+1- 碳數n之直鏈狀烷基
-On -OCnH2n+1 碳數n之直鏈狀烷氧基
nO- CnH2n+1O- 碳數n之直鏈狀烷氧基
-V -CH=CH2
V- CH2=CH-
-V1 -CH=CH-CH3
1V- CH3-CH=CH-
-2V -CH2-CH2-CH=CH3
V2- CH3=CH-CH2-CH2-
-2V1 -CH2-CH2-CH=CH-CH3
1V2- CH3-CH=CH-CH2-CH2
-T- -C≡C-
(環構造)
實施例中所測定之特性係如下所述。
Tni:向列相-等向性液體相轉移溫度(℃)
△n:20℃下之折射率各向異性
△ε:25℃下之介電各向異性
η:20℃下之黏度(mPa.s)
γ1:20℃下之旋轉黏性(mPa.s)
K33:20℃下之彈性常數K33(pN)
(比較例1、2及實施例1、2、3)
製備由表1所記載之組成構成之LC-A(比較例1)、LC-B(比較例2)、LC-1(實施例1)、LC-2(實施例2)及LC-3(實施例3),且測定其物性值。結果係如下所示。
本發明之液晶組成物LC-1、LC-2及LC-3之黏度(η)較小、旋轉黏性(γ1)較小、彈性常數(K33)較大,故而γ1/K33為5.9、5.6、5.8,係與比較例之LC-A及LC-B之該值相比非常小之值。對使用該等之液晶顯示元件之應答速度進行測定,結果LC-1、LC-2及LC-3為3.2~3.5msec係充分之高速應答,相對於此,LC-A為4.2msec,LC-B為4.1msec。進而,測定電壓保持率(VHR),確認具有較高之VHR。再者,單元厚度為3.5μm,配向膜為JALS2096,應答速度之測定條件如下:Von為5.5V,Voff為1.0V,測定溫度為20℃,使用AUTRONIC-MELCHERS公司之DMS301。VHR之測定條件如下:電壓5V、頻率60Hz、溫度60℃,使用Toyo Corporation之VHR-1。
另外,即便改變液晶單元注入條件(壓力及ODF法(one drop filling method,滴下式注入法)’物性值亦未見變化。
(比較例3及實施例4)
製備由表2所記載之組成構成之LC-C(比較例3)及LC-4(實施例4),且測定其物性值,結果如下所示。
本發明之液晶組成物之LC-4之黏度(η)較小、旋轉黏性(γ1)較小、彈性常數(K33)較大,故而γ1/K33為5.9,係與比較例之LC-C之該值相比非常小之值。對使用該等之液晶顯示元件之應答速度進行測定,結果LC-4為3.6msec係充分之高速應答,相對於此,LC-C為4.3msec。進而,測定電壓保持率(VHR),確認具有較高之VHR。再者,單元厚度為3.5μm,配向膜為JALS2096,應答速度之測定條件如下:Von為5.5V,Voff為1.0V,測定溫度為20℃,使用AUTRONIC-MELCHERS公司之DMS301。VHR之測定條件如下:電壓5V、頻率60Hz、溫度60℃,使用Toyo Corporation之VHR-1。
另外,即便改變液晶單元注入條件(壓力及ODF法),物性值亦未見變化。
(比較例4、實施例5、實施例6及實施例7)
製備由表3所記載之組成構成之LC-D(比較例4)、LC-5(實施例5)、LC-6(實施例6)及LC-7(實施例7),且測定其物性值,結果如下所示。
本發明之液晶組成物之LC-5、LC-6及LC-7之黏度(η)較小、旋轉黏性(γ1)較小、彈性常數(K33)較大,故而γ1/K33為與比較例之LC-D之該值相比非常小之值。
(比較例5及實施例8)
製備由表4所記載之組成構成之LC-E(比較例5)及LC-8(實施例8),且測定其物性值,結果如下所示。
本發明之液晶組成物之LC-8之黏度(η)較小、旋轉黏性(γ1)較小、彈性常數(K33)較大,故而γ1/K33為5.7,係與比較例之LC-E之該值相比非常小之值。
根據以上所述,確認本發明之液晶組成物係不使△n及Tni降低,具有η足夠小、旋轉黏性γ1足夠小、彈性常數K33較大且絕對值較大之負的介電各向異性(△ε)者,並且使用其之VA型液晶顯示元件之顯示品質優異、應答速度迅速。

Claims (16)

  1. 一種液晶組成物,含有1種或2種以上以通式(I)所表示之化合物作為第一成分且其含量為3質量%~45質量%,含有1種或2種以上具有絕對值為3以上之負的△ε之液晶化合物即選自以通式(II-A)所表示之化合物中的化合物作為第二成分; (式中,R11表示碳數2~8之烯基或碳數2~8之烯氧基,R12表示碳數1~8之烷基、碳數1~8之烷氧基、碳數2~8之烯基或碳數2~8之烯氧基), (式中,R1及R2分別獨立地表示碳數1~8之烷基、碳數1~8之烷氧基、碳數2~8之烯基或碳數2~8之烯氧基,R1及R2中所存在之1個-CH2-或不鄰接之2個以上之-CH2-可分別獨立地取代為-O-及/或-S-,另外,R1及R2中所存在之1個或2個以上之氫原子可分別獨立地取代為氟原子或氯原子;p表示0、1或2)。
  2. 如申請專利範圍第1項之液晶組成物,其25℃下之介電各向異性(△ε)為-2.0~-8.0之範圍,20℃下之折射率各向異性(△n)為0.08~0.14之範圍,20℃下之黏度(η)為10~30mPa.s之範圍,20℃下之旋轉黏性γ 1為60~130mPa.s之範圍,向列相-等向性液體相轉移溫度(Tni)為60℃~120℃之範圍。
  3. 如申請專利範圍第1或2項之液晶組成物,其進而含有選自以通式 (II-B)所表示之化合物中的1種或2種以上化合物作為第二成分; (式中,R1及R2分別獨立地表示碳數1~8之烷基、碳數1~8之烷氧基、碳數2~8之烯基或碳數2~8之烯氧基,R1及R2中所存在之1個-CH2-或不鄰接之2個以上之-CH2-可分別獨立地取代為-O-及/或-S-,另外,R1及R2中所存在之1個或2個以上之氫原子可分別獨立地取代為氟原子或氯原子;環A及環B分別獨立地表示反-1,4-伸環己基、1,4-伸苯基、2-氟-1,4-伸苯基、3-氟-1,4-伸苯基、3,5-二氟-1,4-伸苯基、2,3-二氟-1,4-伸苯基、1,4-伸環己烯基、1,4-雙環[2.2.2]伸辛基、哌啶-1,4-二基、萘-2,6-二基、十氫萘-2,6-二基或1,2,3,4-四氫萘-2,6-二基;q表示0、1或2)。
  4. 如申請專利範圍第1或2項之液晶組成物,其中,第二成分之含量為10~90質量%。
  5. 如申請專利範圍第3項之液晶組成物,其中,通式(II-A)及(II-B)為通式(II-A1)、(II-A2)及(II-B1); (式中,R3及R4分別獨立地表示碳數1~8之烷基或碳數2~8之烯基,R3及R4中所存在之1個或2個以上之氫原子可分別獨立地取代為氟原子)。
  6. 如申請專利範圍第5項之液晶組成物,其含有1種或2種以上選自以通式(III-A)~(III-J)所表示之化合物群中之化合物作為第三成分; (式中,R5表示碳數1~5之烷基或碳數2~5之烯基,R6表示碳數1~5之烷基、碳數1~5之烷氧基、碳數2~5之烯基或碳數2~5之烯氧基)。
  7. 如申請專利範圍第5項之液晶組成物,其同時含有通式(I)、通式(II-A1)及通式(II-A2)所表示之化合物。
  8. 如申請專利範圍第6項之液晶組成物,其同時含有通式(I)、通式(II-A1)、通式(II-A2)及通式(III-A)所表示之化合物。
  9. 如申請專利範圍第6項之液晶組成物,其同時含有通式(I)、通式(II-A1)、通式(II-A2)、通式(II-B1)及通式(III-A)所表示之化合物。
  10. 如申請專利範圍第6項之液晶組成物,其含有1種或2種以上以通式(V)所表示之化合物; (式中,R21及R22分別獨立地表示碳數1~8之烷基、碳數1~8之烷氧基)。
  11. 如申請專利範圍第10項之液晶組成物,其同時含有通式(I)、通式(II-A1)、通式(II-A2)、通式(V)及通式(III-A)所表示之化合物。
  12. 如申請專利範圍第1或2項之液晶組成物,其含有聚合性化合物。
  13. 如申請專利範圍第12項之液晶組成物,其含有1種或2種以上以通式(IV)所表示之聚合性單體作為聚合性化合物; (式中,R7及R8分別獨立地表示以下之式(R-1)~式(R-15)之任一者,X1~X8分別獨立地表示三氟甲基、三氟甲氧基、氟原子或氫原子);
  14. 一種液晶顯示元件,其係使用申請專利範圍第1至13項中任一項之液晶組成物者。
  15. 一種主動矩陣驅動用液晶顯示元件,其係使用申請專利範圍第1至13項中任一項之液晶組成物者。
  16. 一種VA模式、PSA模式、PSVA模式、IPS模式或ECB模式用液晶顯示元件,其係使用申請專利範圍第1至13項中任一項之液晶組成物者。
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