TWI518175B - Liquid crystal composition and liquid crystal display device employing the same - Google Patents

Liquid crystal composition and liquid crystal display device employing the same Download PDF

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TWI518175B
TWI518175B TW104114861A TW104114861A TWI518175B TW I518175 B TWI518175 B TW I518175B TW 104114861 A TW104114861 A TW 104114861A TW 104114861 A TW104114861 A TW 104114861A TW I518175 B TWI518175 B TW I518175B
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liquid crystal
independently
ocf
compound
hydrogen
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TW104114861A
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TW201639949A (en
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黃婉毓
李清田
王俊智
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達興材料股份有限公司
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Priority to TW104114861A priority Critical patent/TWI518175B/en
Priority to US14/806,153 priority patent/US9598639B2/en
Priority to KR1020150104607A priority patent/KR101798287B1/en
Priority to JP2015145898A priority patent/JP6166313B2/en
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Publication of TWI518175B publication Critical patent/TWI518175B/en
Priority to CN201610303795.2A priority patent/CN106147790A/en
Publication of TW201639949A publication Critical patent/TW201639949A/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/42—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40
    • C09K19/44—Mixtures of liquid crystal compounds covered by two or more of the preceding groups C09K19/06 - C09K19/40 containing compounds with benzene rings directly linked
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL 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
    • G02F1/00—Devices 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
    • G02F1/01—Devices 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 
    • G02F1/13—Devices 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 liquid crystals, e.g. single liquid crystal display cells
    • G02F1/133—Constructional arrangements; Operation of liquid crystal cells; Circuit arrangements
    • G02F1/1333—Constructional arrangements; Manufacturing methods
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/06—Non-steroidal liquid crystal compounds
    • C09K19/34—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring
    • C09K19/3402—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom
    • C09K2019/3422—Non-steroidal liquid crystal compounds containing at least one heterocyclic ring having oxygen as hetero atom the heterocyclic ring being a six-membered ring
    • C09K2019/3425—Six-membered ring with oxygen(s) in fused, bridged or spiro ring systems

Description

液晶組成物及包含其之液晶顯示元件 Liquid crystal composition and liquid crystal display element including the same

本發明是有關於一種液晶組成物，且特別是有關於一種具有高介電常數異向性及低轉動黏度的液晶組成物，及包含其之液晶顯示元件。 The present invention relates to a liquid crystal composition, and more particularly to a liquid crystal composition having high dielectric anisotropy and low rotational viscosity, and a liquid crystal display element comprising the same.

液晶顯示器具有重量輕、省電、無輻射與全彩顯示等優點，因此已成為最普遍的顯示器產品。近年來，隨著技術不斷提升，以及對高解析度、高反應速率與高畫質的要求，液晶顯示器已由扭轉向列(twisted nematic,TN)、超扭轉向列(super twisted nematic,STN)與雙穩態扭轉向列(bistable twisted nematic,BTN)等被動式驅動顯示方式，發展成具有薄膜電晶體(thin film transistor,TFT)的主動矩陣式液晶顯示器。隨著廣視角技術的需求，橫向電場(in-plane switching,IPS)、邊界電場切換(fringe field switching,FFS)、垂直配向(vertical alignment,VA)與聚合物穩定配向(polymer sustained alignment,PSA)等液晶顯示方式的開發與突破，對於未來面板的應用與發展是相當重要的。 Liquid crystal displays have the advantages of light weight, power saving, no radiation and full color display, so they have become the most common display products. In recent years, with the continuous improvement of technology and the requirements for high resolution, high reaction rate and high image quality, liquid crystal displays have been twisted nematic (TN), super twisted nematic (STN). With the passive drive display mode such as bistable twisted nematic (BTN), it has developed into an active matrix liquid crystal display with a thin film transistor (TFT). With the demand of wide viewing angle technology, in-plane switching (IPS), fringe field switching (FFS), vertical alignment (VA) and polymer sustained alignment (PSA) The development and breakthrough of liquid crystal display methods are very important for the application and development of future panels.

對於液晶顯示器來說，目前需要的是具有高介電常數異向性(dielectric constant anisotropy,△ε)、低轉動黏度(rotational viscosity,γ1)、適當的折射率(birefringence)以及 範圍廣的操作溫度的液晶介質。特別是，當液晶介質具有較高的介電常數異向性時，可以降低液晶顯示裝置的閾值電壓(threshold voltage,Vth)；當液晶介質具有較低的轉動黏度時，可以加快應答(response)速度；當液晶介質具有較高的澄清點時，可擴大液晶介質的應用操作溫度範圍。 For liquid crystal displays, what is required is a dielectric constant anisotropy (Δε), a low rotational viscosity (γ1), a suitable refractive index (birefringence), and A wide range of operating temperature liquid crystal media. In particular, when the liquid crystal medium has a high dielectric anisotropy, the threshold voltage (Vth) of the liquid crystal display device can be lowered; when the liquid crystal medium has a low rotational viscosity, the response can be accelerated. Speed; when the liquid crystal medium has a high clearing point, the application operating temperature range of the liquid crystal medium can be expanded.

本發明提供一種液晶組成物，具有高介電常數異向性、低轉動黏度、以及寬液晶相範圍，且採用該液晶組成物製作液晶顯示元件，可使液晶顯示元件具有更好顯示效能及品質。 The invention provides a liquid crystal composition having high dielectric anisotropy, low rotational viscosity, and wide liquid crystal phase range, and the liquid crystal display element is prepared by using the liquid crystal composition, so that the liquid crystal display element can have better display performance and quality. .

根據本發明之實施例，本發明提供一種液晶組成物，包含至少一種具有式(I)所示結構之化合物，以及至少一種具有式(II)所示結構之化合物： According to an embodiment of the present invention, there is provided a liquid crystal composition comprising at least one compound having the structure of the formula (I), and at least one compound having the structure of the formula (II):

其中，R1係為氫、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1及Z2係獨立為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2；i為0或1；A1、A2、 A3、及A4係獨立地為 或，且A1、A2、A3、及A4至少一者為 、或；其中R2係獨立地為氫、或鹵素； R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；m、n、或o 係獨立地為1或0；以及，當m+n+o<3時，A1非為 Wherein R 1 is hydrogen, C 1-15 alkyl, C 2-15 alkenyl or, in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 and Z 2 are independently a single bond, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 ( CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH=CH-, -CH =CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 ; i is 0 Or 1; A 1 , A 2 , A 3 , and A 4 are independently or And at least one of A 1 , A 2 , A 3 , and A 4 is ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or / and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 3 , Z 4 , and Z 5 are independently a single bond, - CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -( CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C ≡C-, -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; m, n, or o are independently 1 or 0; , when m + n + o <3, A 1 is a non-

根據本發明另一實施例，本發明亦提供一種液晶顯示元件，其中該液晶顯示元件，包括如前所述的液晶化合物。 According to another embodiment of the present invention, the present invention also provides a liquid crystal display element, wherein the liquid crystal display element comprises a liquid crystal compound as described above.

為讓本發明的上述特徵和優點能更明顯易懂，下文特舉實施方式作詳細說明如下。 The above described features and advantages of the present invention will be more apparent from the following description.

在本文中，由「一數值至另一數值」表示的範圍，是一種避免在說明書中一一列舉該範圍中的所有數值的概要性表示方式。因此，記載了某一特定數值範圍，等同於揭露了該數值範圍內的任意數值以及由該數值範圍內的任意數值界定出的較小數值範圍，如同在說明書中明文寫出該任意數值和該較小數值範圍一樣。例如，記載「含量為10~80%」的範圍，就等同於揭露了「含量為20%~40%」的範圍，無論說明書中是否列舉其他數值。 In the present specification, the range represented by "a value to another value" is a schematic representation that avoids enumerating all the values in the range in the specification. Therefore, a particular numerical range is recited and is equivalent to the disclosure of any numerical value in the range of the value and the numerical range defined by any value in the numerical range, as the The smaller value range is the same. For example, the description of the "content of 10 to 80%" is equivalent to the disclosure of the "content of 20% to 40%", regardless of whether other values are listed in the specification.

在本文中，有時以鍵線式(skeletal formula)表示化合物結構。這種表示法可以省略碳原子、氫原子以及碳氫鍵。當然，結構式中有明確繪出原子或原子基團的，則以繪示者為準。 In this context, the structure of a compound is sometimes represented by a skeletal formula. This representation can omit carbon atoms, hydrogen atoms, and carbon-hydrogen bonds. Of course, if the atom or atomic group is clearly drawn in the structural formula, the person who prescribes it shall prevail.

根據本發明實施例，本發明提供一種液晶組成物，其具有高介電常數異向性、低轉動黏度、以及寬液晶相範圍。此外，根據本發明其他實施例，本發明提供一種液晶顯示元件，包含上述液晶組成物，可使液晶顯示元件具有更好顯示效能及品質。 According to an embodiment of the present invention, there is provided a liquid crystal composition having high dielectric anisotropy, low rotational viscosity, and a wide liquid crystal phase range. Further, according to other embodiments of the present invention, the present invention provides a liquid crystal display element comprising the above liquid crystal composition, which enables the liquid crystal display element to have better display performance and quality.

根據本發明實施例，本發明所述之液晶組成物，包含至少一種具有式(I)所示結構之化合物，以及至少一種具有式(II)所示結構之化合物： According to an embodiment of the present invention, the liquid crystal composition of the present invention comprises at least one compound having the structure represented by the formula (I), and at least one compound having the structure represented by the formula (II):

其中，R1可為氫、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1及Z2可獨立為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2；i可為0或1；A1、A2、 A3、及A4可獨立地為 或，且A1、A2、A3、及A4至少一者為 、或；其中R2可獨立地為氫、或鹵素； R4及R5可獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5可獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、 -CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；m、n、或o 可獨立地為1或0；以及，當m+n+o<3時，A1非為 Wherein R 1 may be hydrogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 and Z 2 may independently be a single bond, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 ( CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH=CH-, -CH =CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 ; 0 or 1; A 1 , A 2 , A 3 , and A 4 may be independently or And at least one of A 1 , A 2 , A 3 , and A 4 is ,or Wherein R 2 may independently be hydrogen or halogen; R 4 and R 5 may independently be hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 3 , Z 4 , and Z 5 may independently be a single bond, - CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -( CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C ≡C-, -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; m, n, or o may independently be 1 or 0; , + n-when O + m <. 3, is the non-A. 1

根據本發明實施例，R1可例如為氫、甲基、乙基、丙基、正丁基、戊基、己基、庚基、辛基、氟甲基、氟乙基、氟丙基、氟丁基、氟戊基、氟己基、氟庚基、氟辛基、氟壬基、氟癸基、甲氧基、乙氧基、丙氧基、正丁氧基、戊氧基、己氧基、庚氧基、辛氧基、氟甲氧基、氟乙氧基、甲氧基甲基、甲氧基乙基、乙烯基、或丙烯基。此外，在上述官能基中，任意碳上之氫原子可被鹵素原子取代、或/及任意之-CH2-可被-O-、-CO-或-COO-取代。若-CH2-被-O-、-CO-或-COO-取代時，-O-、-CO-及-COO-任兩者不直接相連。在本文中，氟烷基、或氟烷氧基係指至少一氫被氟所取代之烷基或烷氧基、或是多個氫被鹵素所取代之烷基或烷氧基，舉例來說，本文中所述之氟甲基包含單氟甲基、二氟甲基、或是三氟甲基。 According to an embodiment of the present invention, R 1 may be, for example, hydrogen, methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl, fluoroethyl, fluoropropyl, fluoro. Butyl, fluoropentyl, fluorohexyl, fluoroheptyl, fluorooctyl, fluoroindolyl, fluoroindolyl, methoxy, ethoxy, propoxy, n-butoxy, pentyloxy, hexyloxy , heptyloxy, octyloxy, fluoromethoxy, fluoroethoxy, methoxymethyl, methoxyethyl, vinyl, or propenyl. Further, in the above functional group, a hydrogen atom on any carbon may be substituted by a halogen atom, or/and any -CH 2 - may be substituted by -O-, -CO- or -COO-. When -CH 2 - is substituted by -O-, -CO- or -COO-, neither -O-, -CO- and -COO- are directly linked. As used herein, fluoroalkyl or fluoroalkoxy refers to an alkyl or alkoxy group in which at least one hydrogen is replaced by fluorine, or an alkyl or alkoxy group in which a plurality of hydrogens are replaced by a halogen, for example, The fluoromethyl group described herein includes a monofluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

根據本發明實施例，Z1、Z2、Z3、Z4、及Z5可獨立地為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2。 According to an embodiment of the present invention, Z 1 , Z 2 , Z 3 , Z 4 , and Z 5 may independently be a single bond, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡ C-, or -CH=CH-; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 .

在本發明實施例中，m、n、或o可獨立地為1或0。換言之，m+n+o可為3、2、1、或0。在本發明實施方式中，當 m+n+o為2、1、或0時，A1可為 、或。此外，當m+n+o為3時，A1 可為、或 In an embodiment of the invention, m, n, or o may independently be 1 or 0. In other words, m+n+o can be 3, 2, 1, or 0. In the embodiment of the present invention, when m+n+o is 2, 1, or 0, A 1 may be ,or . In addition, when m+n+o is 3, A 1 can be ,or

根據本發明實施例，A1、A2、A3、及A4可獨立 地為 According to an embodiment of the invention, A 1 , A 2 , A 3 , and A 4 may be independently

R4可為氫、氟、甲基、乙基、丙基、正丁基、戊基、己基、庚基、辛基、氟甲基、氟乙基、氟丙基、氟丁基、氟戊基、氟己基、氟庚基、氟辛基、甲氧基、乙氧基、丙氧基、正丁氧基、戊氧基、己氧基、庚氧基、辛氧基、氟甲氧基、氟乙氧基、甲氧基甲基、甲氧基乙基、乙烯基、或丙烯基。此外，在上述官能基中，任意碳上之氫原子可被鹵素原子取代、或/及任意之-CH2-可被-O-、-CO-或-COO-取代。若-CH2-被-O-、-CO-或-COO-取代時，-O-、-CO-及-COO-任兩者不直接相連。此外，R5可為H、F、-CF3、-OCF3、-OCHCF2、-OCF2CFCF2、或-OCH2CF3。在本文中，氟烷基、或氟烷氧基係指至少一氫被氟所取代之烷基或烷氧基、或是多個氫被鹵素所取代之烷基或烷氧基，舉例來說，本文中所述之氟甲基包含單氟甲基、二氟甲基、或是三氟甲基。 R 4 may be hydrogen, fluorine, methyl, ethyl, propyl, n-butyl, pentyl, hexyl, heptyl, octyl, fluoromethyl, fluoroethyl, fluoropropyl, fluorobutyl, fluoropentane , fluorohexyl, fluoroheptyl, fluorooctyl, methoxy, ethoxy, propoxy, n-butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, fluoromethoxy , fluoroethoxy, methoxymethyl, methoxyethyl, vinyl, or propenyl. Further, in the above functional group, a hydrogen atom on any carbon may be substituted by a halogen atom, or/and any -CH 2 - may be substituted by -O-, -CO- or -COO-. When -CH 2 - is substituted by -O-, -CO- or -COO-, neither -O-, -CO- and -COO- are directly linked. Further, R 5 may be H, F, -CF 3 , -OCF 3 , -OCHCF 2 , -OCF 2 CFCF 2 , or -OCH 2 CF 3 . As used herein, fluoroalkyl or fluoroalkoxy refers to an alkyl or alkoxy group in which at least one hydrogen is replaced by fluorine, or an alkyl or alkoxy group in which a plurality of hydrogens are replaced by a halogen, for example, The fluoromethyl group described herein includes a monofluoromethyl group, a difluoromethyl group, or a trifluoromethyl group.

根據本發明實施例，該具有式(I)所示結構之化 合物可包含、及/或 ，其中R1可為 氫、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2可獨立地為氫、或鹵素；Z1及Z2可獨立為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；以及，i可為0或1。 According to an embodiment of the present invention, the compound having the structure represented by the formula (I) may comprise And/or Wherein R 1 may be hydrogen, C 1 - 15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 may independently be hydrogen or halogen; Z 1 and Z 2 may independently be a single bond, -COO-, -OCO-, -CF 2 O- , -OCF 2 -, -C≡C-, or -CH=CH-; and, i can be 0 or 1.

根據本發明實施例，該具有式(II)所示結構之化 合物可包含、及/或 ，其中A2、A3、及A4 係獨立地為、或，其中R2可獨立地為 氫、或鹵素；R4及R5可獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5可獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、 -OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、n、或o可獨立地為1或0。 According to an embodiment of the present invention, the compound having the structure represented by the formula (II) may comprise And/or Where A 2 , A 3 , and A 4 are independently ,or Wherein R 2 may independently be hydrogen or halogen; R 4 and R 5 may independently be hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 4 and Z 5 may independently be a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- , -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, m, n, or o may independently be 1 or 0.

根據本發明實施例，該具有式(II)所示結構之化 合物可包含、及/或 ，其中A2、及A3可獨立 地為、或，其中R2可獨立地為氫、或 鹵素；R4及R5可獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子可被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5可獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、或n可獨立地為1或0。 According to an embodiment of the present invention, the compound having the structure represented by the formula (II) may comprise And/or Where A 2 and A 3 are independently ,or Wherein R 2 may independently be hydrogen or halogen; R 4 and R 5 may independently be hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom may be substituted by a halogen atom, or/and any -CH 2 - may be substituted by -O-, -CO- or -COO-; Z 4 and Z 5 may independently be a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- , -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, m, or n may independently be 1 or 0.

根據本發明實施例，該具有式(II)所示結構之化 合物可包含，其中A1、 A2、A3、及A4係獨立地為、或；R2係 獨立地為氫、或鹵素；R4可為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5可獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，R5可為H、F、-CF3、-OCF3、-OCHCF2、-OCF2CFCF2、或-OCH2CF3。 According to an embodiment of the present invention, the compound having the structure represented by the formula (II) may comprise Wherein A 1 , A 2 , A 3 , and A 4 are independently ,or R 2 is independently hydrogen or halogen; R 4 may be hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is halogen Atom substituted, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 3 , Z 4 , and Z 5 may independently be a single bond, -CH 2 -, -( CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH =CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, R 5 may be H, F, -CF 3 , -OCF 3 , -OCHCF 2 , -OCF 2 CFCF 2 , or -OCH 2 CF 3 .

根據本發明實施例，該具有式(II)所示結構之化 合物可包含，其中R2可 獨立地為氫、或鹵素；R4可為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；以及，R5可為H、F、-CF3、-OCF3、-OCHCF2、-OCF2CFCF2、或-OCH2CF3。 According to an embodiment of the present invention, the compound having the structure represented by the formula (II) may comprise Wherein R 2 may independently be hydrogen or halogen; R 4 may be hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is The halogen atom is substituted, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; and R 5 may be H, F, -CF 3 , -OCF 3 , -OCHCF 2 , -OCF 2 CFCF 2 or -OCH 2 CF 3 .

在本發明實施例中，所述之液晶組成物，包含至少一種具有式(I)所示結構之化合物，以及至少一種具有式(II)所示結構之化合物。其中，該具有式(I)所示結構之化合物 可包含，其中R1係為氫、C1-5 烷基、C2-5烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2；此外，該具有式(II)所示結構之化合物 的A1、A2、A3、及A4係獨立地為 、或，且A1、A2、A3、及A4至少一者 為(當A2、A3、及/或A4為時， 其對應的m、n、及/或o係為1)；R2係獨立地為氫、或鹵素；R4及R5係獨立地為氫、鹵素、C1-5烷基、C2-5烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5係獨立地為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；以及，m、n、或o係獨立地為1或0。 In an embodiment of the invention, the liquid crystal composition comprises at least one compound having the structure represented by the formula (I), and at least one compound having the structure represented by the formula (II). Wherein the compound having the structure represented by the formula (I) may comprise Wherein R 1 is hydrogen, C 1-5 alkyl, C 2-5 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 is a single bond, -COO-, -OCO-, -CF 2 O-, -OCF 2 - , -C≡C-, or -CH=CH-; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 ; in addition, the structure represented by formula (II) The compounds A 1 , A 2 , A 3 , and A 4 are independently ,or And at least one of A 1 , A 2 , A 3 , and A 4 is (When A 2 , A 3 , and / or A 4 are Wherein, the corresponding m, n, and/or o is 1); R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-5 alkyl, C 2-5 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or / and any -CH 2 - is substituted by -O-, -CO- or -COO-; 3 , Z 4 , and Z 5 are independently a single bond, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, or -CH=CH-; and, m , n, or o are independently 1 or 0.

在本發明實施例中，本發明所述之液晶組成物，包含至少一種具有式(I)所示結構之化合物，以及至少一種具有式(II)所示結構之化合物。其中，該具有式(I)所示結構之化合物可包含具有式(I-1)所示結構之化合物 ，其中R1係為氫、或C1-5 烷基；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2；其中，具有式(II)所示結構之化合物包含具有式(II-1)所示結構之化合物 、具有式(II-2)所示結 構之化合物、具有式 (II-3)所示結構之化合物 、或具有式 (II-4)所示結構之化合物 (II-4))；其中，R4係為氫、或C1-5烷基；R5係為H、F、CF3、-OCF3、-OCH=CF2、-OCH2-CF3、或-OCF2CFCF2。 In the embodiment of the present invention, the liquid crystal composition of the present invention comprises at least one compound having the structure represented by the formula (I), and at least one compound having the structure represented by the formula (II). Wherein the compound having the structure represented by the formula (I) may comprise a compound having the structure represented by the formula (I-1) Wherein R 1 is hydrogen or C 1-5 alkyl; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 ; wherein, the structure represented by formula (II) The compound contains a compound having the structure represented by the formula (II-1) a compound having the structure represented by formula (II-2) a compound having the structure represented by formula (II-3) Or a compound having the structure represented by formula (II-4) (II-4)); wherein R 4 is hydrogen or C 1-5 alkyl; R 5 is H, F, CF 3 , -OCF 3 , -OCH=CF 2 , -OCH 2 -CF 3 , or -OCF 2 CFCF 2 .

根據本發明實施例，該具有式(I)所示結構之化合物可例如包含 、或上述化合物之 任意組合。 According to an embodiment of the present invention, the compound having the structure represented by the formula (I) may, for example, comprise Or any combination of the above compounds.

根據本發明實施例，該具有式(II)所示結構之化 合物可例如包含 、或上述化合物 之任意組合。 According to an embodiment of the present invention, the compound having the structure represented by the formula (II) may, for example, comprise Or any combination of the above compounds.

具有式(I)所示結構之化合物搭配具有式(II)所示結構之化合物，可使所得之液晶組成物具有高介電常數異向性、低轉動黏度以及寬液晶向列相範圍。因此，使用本發明所述之液晶組成物的液晶顯示元件可以具有較佳的顯示效能、及較低的驅動電壓。 The compound having the structure represented by the formula (I), in combination with the compound having the structure represented by the formula (II), can give the obtained liquid crystal composition a high dielectric anisotropy, a low rotational viscosity, and a wide liquid crystal nematic phase range. Therefore, the liquid crystal display element using the liquid crystal composition of the present invention can have better display performance and a lower driving voltage.

根據本發明實施例，所述之液晶組成物，除了包含具有式(I)及式(II)所示結構之化合物外，可更包含至少一種具有式(III)所表示之化合物。 According to an embodiment of the present invention, the liquid crystal composition may further comprise at least one compound represented by the formula (III) in addition to the compound having the structure represented by the formula (I) and the formula (II).

其中，R6係為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R7係為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代，例如：氫、氟、-CH3、-C2H5、-C3H8、-C2H3、-OCF3、-OCH=CF2、-OCH2-CF3、或-OCF2CFCF2；A5、A6、以及 A7可獨立地為、或，其中R2可獨立地 為氫、或鹵素；Z6、以及Z7係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，p係為1或0。 Wherein R 6 is hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; R 7 is hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-, for example: hydrogen, fluorine, -CH 3 , -C 2 H 5 , -C 3 H 8 , -C 2 H 3 , -OCF 3 , -OCH=CF 2 , -OCH 2 -CF 3 , or -OCF 2 CFCF 2 ; A 5 , A 6 , and A 7 may independently ,or Wherein R 2 may independently be hydrogen or halogen; Z 6 and Z 7 are independently a single bond, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O ( CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, p is 1 or 0.

由於以下說明使用多種液晶化合物，為求表示的簡潔，下文將以代號組合來表示，其中以正常字型顯示的數字代表碳數等於該數字的烷基，以及每一代號分別表示的結構單元整理於下表。此外，該代號組合係以表內所示結構位置直接組合，舉例來說，3CPGF表示結構為下式的化合物： (非為 )。 Since the following description uses a plurality of liquid crystal compounds, for the sake of simplicity of the description, the following will be represented by a combination of numbers, in which the numbers shown in the normal font represent the alkyl groups whose carbon number is equal to the number, and the structural unit representation of each code number In the table below. In addition, the code combination is directly combined with the structural positions shown in the table. For example, 3CPGF represents a compound having the following structure: (not for ).

根據本發明實施例，該具有式(III)所表示之化合物可包含3CCV、3CCV1、3CC4、3CC5、3CPN、3CPTP2、3CPTP4、3CPTPO2、VCCGF、3CCPF、2CPPF、3CPPF、3CPP2、2CPGF、3CPGF、3CPUF、3CCPOCF3、3CCGOCF3、 5PP1、3PPV、3PGUF、V2PTP2V、1PTPO2、3PTPO1、3PTPO2 3PUQUF、或上述化合物之任意組合。 According to an embodiment of the present invention, the compound represented by the formula (III) may include 3CCV, 3CCV1, 3CC4, 3CC5, 3CPN, 3CPTP2, 3CPTP4, 3CPTPO2, VCCGF, 3CCPF, 2CPPF, 3CPPF, 3CPP2, 2CPGF, 3CPGF, 3CPUF, 3CCPOCF3, 3CCGOCF3, 5PP1, 3PPV, 3PGUF, V2PTP2V, 1PTPO2, 3PTPO1, 3PTPO2 3PUQUF, or any combination of the above compounds.

本發明所述液晶組成物中，可更包含熟悉此項技術者已知及文獻中所述具有式(I)、式(II)、以及式(III)所示結構之外的液晶化合物，或其他添加劑例如對掌性摻雜劑、UV穩定劑、抗氧化劑、自由基淨化劑、奈米粒子等等。 The liquid crystal composition of the present invention may further comprise a liquid crystal compound which is known to the person skilled in the art and which has a structure other than the structure represented by the formula (I), the formula (II), and the formula (III), or Other additives such as palmitic dopants, UV stabilizers, antioxidants, free radical scavengers, nanoparticles, and the like.

根據本發明實施例，以該液晶組成物總重為100wt%計算，其中包括該式(I)所示液晶化合物的用量範圍可約為0.1wt%至90wt%、較佳為2wt%至50wt%、最佳為2.5wt%至25wt%；以及，該式(II)所示化合物的用量範圍可約為0.1wt%至90wt%、較佳為2wt%至50wt%、最佳為2.5wt%至35wt%。根據本發明另一實施例，以該液晶組成物總重為100wt%計算，其中更包含該式(III)所示化合物的用量範圍可約為0.1wt%至90wt%、較佳為50wt%至85wt%、最佳為60wt%至85wt%。 According to an embodiment of the present invention, the total weight of the liquid crystal composition is 100 wt%, and the liquid crystal compound represented by the formula (I) may be used in an amount ranging from about 0.1 wt% to 90 wt%, preferably from 2 wt% to 50 wt%. , preferably from 2.5 wt% to 25 wt%; and the compound of the formula (II) may be used in an amount ranging from about 0.1 wt% to 90 wt%, preferably from 2 wt% to 50 wt%, most preferably from 2.5 wt% to 35wt%. According to another embodiment of the present invention, the total weight of the liquid crystal composition is 100% by weight, and the compound further comprising the compound of the formula (III) may be used in an amount ranging from about 0.1% by weight to 90% by weight, preferably 50% by weight to 85 wt%, most preferably from 60 wt% to 85 wt%.

本發明的又一實施方式提出一種液晶顯示元件。該液晶顯示元件的特徵在於，包括任一種前述實施方式中的液晶組成物。當然，該液晶顯示元件也可以具有其他已知的液晶顯示元件的構件，例如基板、偏光片、彩色濾光片或配向膜等等。除了內含的液晶組成物以外，此液晶顯示元件的製造方法和構成元件可以從習知技術中任意選擇，因此不在此贅述。 Yet another embodiment of the present invention provides a liquid crystal display element. The liquid crystal display element is characterized by comprising the liquid crystal composition of any of the foregoing embodiments. Of course, the liquid crystal display element may also have other known members of the liquid crystal display element, such as a substrate, a polarizer, a color filter or an alignment film, and the like. The manufacturing method and constituent elements of the liquid crystal display element can be arbitrarily selected from the prior art except for the liquid crystal composition contained therein, and thus will not be described herein.

由於本實施方式的液晶顯示元件採用了含有前述由式1表示的液晶化合物的液晶組成物，因此不但具有閾值電壓低以 及應答速度快的優點，還適於在較寬的溫度範圍下使用且具良好的顯示品質。 Since the liquid crystal display element of the present embodiment employs a liquid crystal composition containing the liquid crystal compound represented by Formula 1 described above, it has a low threshold voltage. And the advantage of fast response speed, it is also suitable for use in a wide temperature range and has good display quality.

為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例，來說明本發明所述之液晶化合物、及包含其之液晶組成物。 The liquid crystal compounds of the present invention, and liquid crystal compositions comprising the same, will be described in more detail below in order to explain the above and other objects, features and advantages of the present invention.

液晶化合物 Liquid crystal compound

製備例1：化合物2doPUF的合成 Preparation Example 1: Synthesis of Compound 2doPUF

在氮氣下將依序加入45mL的THF(四氫呋喃)及6.4mL的二異丙胺於一反應瓶中。將反應瓶溫度降至0℃後，慢慢滴入16mL的正丁基鋰(2.5M)。接著，於0℃下攪拌30分鐘後，再加入9g(0.032mol)之化合物1，並攪拌1小時。接著，將8.5g(0.03mol)之化合物2溶於10mL的THF中，加入先前製備的烯胺試劑。將該混合物回溫至室溫後，加熱至迴流。18小時後，加入50mL的水中止反應。以乙酸乙酯反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯與正己烷的體積比例為1：10)純化獲得5.1g的化合物3(棕色液體)。上述反應之反應式如下所示： 45 mL of THF (tetrahydrofuran) and 6.4 mL of diisopropylamine were sequentially added to a reaction flask under nitrogen. After the reaction flask temperature was lowered to 0 ° C, 16 mL of n-butyllithium (2.5 M) was slowly added dropwise. Then, after stirring at 0 ° C for 30 minutes, 9 g (0.032 mol) of Compound 1 was further added and stirred for 1 hour. Next, 8.5 g (0.03 mol) of Compound 2 was dissolved in 10 mL of THF, and the previously prepared enamine reagent was added. After the mixture was warmed to room temperature, it was heated to reflux. After 18 hours, the reaction was stopped by adding 50 mL of water. The mixture was extracted three times with ethyl acetate and the organic layer was collected, then the water was removed with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally by column chromatography (the volume ratio of ethyl acetate to n-hexane was 1:10) Purification afforded 5.1 g of compound 3 (brown liquid). The reaction formula of the above reaction is as follows:

接著，依序加入30mL的THF、2.9g(8mmol)化合物3及30mL鹽酸水溶液(2N)於一反應瓶中。在室溫下攪拌2小時後，加入50mL的水中止反應。以乙酸乙酯反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯與正己烷的體積比例為1：10)純化獲得1.9g的化合物4(淡黃色固體)。上述反應之反應式如下所示： Next, 30 mL of THF, 2.9 g (8 mmol) of Compound 3 and 30 mL of an aqueous hydrochloric acid solution (2N) were sequentially added to a reaction flask. After stirring at room temperature for 2 hours, the reaction was stopped by adding 50 mL of water. The mixture was extracted three times with ethyl acetate and the organic layer was collected, then the water was removed with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally by column chromatography (the volume ratio of ethyl acetate to n-hexane was 1:10) Purification afforded 1.9 g of compound 4 (light yellow solid). The reaction formula of the above reaction is as follows:

接著，將15mL的THF、0.3g(0.1mmol)化合物4、0.26g(0.14mmol)的3,4,5-三氟苯硼酸、3mL的碳酸鉀水溶液(1N)、以及0.05g的三苯基磷鈀鹽(Pd(PPh3)4)加入一反應瓶中。在加熱至迴流並反應18小時後，加入50mL的水中止反應。以乙酸乙酯反覆進行三次萃取並收集有機層，再以無水硫酸鎂去除水份、過濾及減壓濃縮，最後利用管柱層析法(沖提液為乙酸乙酯與正己烷的體積比例為1：10)純化獲得0.3g的化合物2doPUF(白色固體)。上述反應之反應式如下所示： Next, 15 mL of THF, 0.3 g (0.1 mmol) of Compound 4, 0.26 g (0.14 mmol) of 3,4,5-trifluorobenzeneboronic acid, 3 mL of an aqueous potassium carbonate solution (1 N), and 0.05 g of triphenyl group Phosphorus palladium salt (Pd(PPh 3 ) 4 ) was added to a reaction flask. After heating to reflux and reacting for 18 hours, 50 mL of water was added to stop the reaction. The mixture was extracted three times with ethyl acetate and the organic layer was collected, then the water was removed with anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure, and finally by column chromatography (the volume ratio of ethyl acetate to n-hexane was 1:10) Purification afforded 0.3 g of compound 2doPUF (white solid). The reaction formula of the above reaction is as follows:

製備例2：化合物3RIGUQUF的合成 Preparation 2: Synthesis of Compound 3 RIGUQUF

將229g的化合物5、357g的氯化鋁加入2L的反應瓶中，並加熱迴流3小時。然後，移除多餘的氯化鋁，並加入1.2L的二氯甲烷。接著，將溫度降至5℃，加入3200g的氯化鋁。接著，在加熱至迴流並反應5小時後，將反應液倒入鹽酸和冰的混合物中進行水解，萃取，並以矽膠分離。接著，移除溶劑，以得到168.8g的化合物6(淡黃色固體、產率為80%)。上述反應之反應式如下所示： 229 g of Compound 5 and 357 g of aluminum chloride were placed in a 2 L reaction flask and heated to reflux for 3 hours. Then, excess aluminum chloride was removed and 1.2 L of dichloromethane was added. Next, the temperature was lowered to 5 ° C, and 3200 g of aluminum chloride was added. Next, after heating to reflux and reacting for 5 hours, the reaction liquid was poured into a mixture of hydrochloric acid and ice to carry out hydrolysis, extraction, and separation with tannin. Next, the solvent was removed to give 168.8 g of Compound 6 (yellow solid, yield 80%). The reaction formula of the above reaction is as follows:

接著，將168.8g的化合物6、650ml的乙醇加入一反應瓶中。將溫度控制在10℃以下，分批加入45g的硼氫化鈉(NaBH4)。將溫度升至室溫，並持續攪拌3小時。在反應完成之後，移除乙醇，再加入450ml的10%的鹽酸水溶液，進行水解，以二氯甲烷萃取，以水清洗，乾燥，移除溶劑，得到170g的化合物7(淡黃色固體)。上述反應之反應式如下所示： Next, 168.8 g of Compound 6, 650 ml of ethanol was added to a reaction flask. The temperature was controlled below 10 ° C, and 45 g of sodium borohydride (NaBH 4 ) was added in portions. The temperature was raised to room temperature and stirring was continued for 3 hours. After completion of the reaction, ethanol was removed, and 450 ml of a 10% aqueous hydrochloric acid solution was added thereto, followed by hydrolysis, extraction with dichloromethane, washing with water, drying, and removal of solvent to obtain 170 g of Compound 7 (light yellow solid). The reaction formula of the above reaction is as follows:

接著，將170g的化合物7、1.2L的苯、以及8g的對甲苯磺酸加入一反應瓶中，並加熱迴流3小時。在反應完成之後，以水洗至中性，並移除苯。以750ml的石油醚以及矽膠進行過濾。移除石油醚，得到148g的化合物8(淡黃色油狀物)。上述反應之反應式如下所示： Next, 170 g of Compound 7, 1.2 L of benzene, and 8 g of p-toluenesulfonic acid were placed in a reaction flask, and heated under reflux for 3 hours. After the reaction was completed, it was washed with water until neutral, and benzene was removed. It was filtered with 750 ml of petroleum ether and silicone. Petroleum ether was removed to give 148 g of compound 8 (yellow oil). The reaction formula of the above reaction is as follows:

將1.5L的甲酸、300ml的30%的雙氧水(H2O2)加入一反應瓶中，並以水浴將温度控制於35℃至40℃之間。然後，加入148g的化合物8。在室温下攪拌12小時。將反應液倒入大量水中，以析出白色固體，並進行過濾。將3L的7%的硫酸水溶液加入5L的三頸瓶中，並加熱至沸騰。然後，於反應瓶中加入上述的白色固體。之後，以水蒸汽蒸餾，以得到64g的化合物9(白色固體。上述反應之反應式如下所示： 1.5 L of formic acid, 300 ml of 30% hydrogen peroxide (H 2 O 2 ) were added to a reaction flask, and the temperature was controlled between 35 ° C and 40 ° C in a water bath. Then, 148 g of Compound 8 was added. Stir at room temperature for 12 hours. The reaction solution was poured into a large amount of water to precipitate a white solid, which was filtered. 3 L of a 7% aqueous solution of sulfuric acid was added to a 5 L three-necked flask and heated to boiling. Then, the above white solid was added to the reaction flask. Thereafter, it was distilled by steam to obtain 64 g of Compound 9 (white solid. The reaction formula of the above reaction is as follows:

將64g的化合物9、90ml的乙二醇、600ml的甲苯以及3g的對甲苯磺酸加入1L的三頸瓶中，並加熱迴熱廻流3.5小時。停止加熱，並以水洗至中性。接著，移除 甲苯，並以500ml的石油醚以及矽膠分離。之後，移除石油醚，並用150ml的異丙醇進行再结晶，以得到61g的化合物10(淡黃色固體)。上述反應之反應式如下所示： 64 g of compound 9, 90 ml of ethylene glycol, 600 ml of toluene and 3 g of p-toluenesulfonic acid were placed in a 1 L three-necked flask and heated to reflux for 3.5 hours. Stop heating and wash with water until neutral. Next, toluene was removed and separated with 500 ml of petroleum ether and silicone. Thereafter, petroleum ether was removed and recrystallized from 150 ml of isopropyl alcohol to give 61 g of compound 10 (yellowish solid). The reaction formula of the above reaction is as follows:

將42g的化合物10、23.1g的間氟苯硼酸、70g的碳酸鈉、300ml的水、300ml的乙醇、600ml的甲苯以及2g的Pd(PPh3)4加入2L的三頸瓶中。然後，在氮氣保護下，加熱迴流6小時。將所得到的灰黑色固體，進行石油醚管柱層析。再結晶，以得到38g的化合物11(淡黃色固體)。上述反應之反應式如下所示： 42 g of Compound 10, 23.1 g of m-fluorophenylboronic acid, 70 g of sodium carbonate, 300 ml of water, 300 ml of ethanol, 600 ml of toluene and 2 g of Pd(PPh3)4 were placed in a 2 L three-necked flask. Then, under a nitrogen atmosphere, the mixture was heated under reflux for 6 hours. The obtained gray-black solid was subjected to petroleum ether column chromatography. Recrystallization gave 38 g of compound 11 (yellow solid). The reaction formula of the above reaction is as follows:

將38g的化合物11、200ml的84%的甲酸水溶液以及150ml的甲苯加入500ml的三頸瓶中。然後，將溫度控制在20℃，攪拌20小時。在反應完成後，以水萃取分離，再以異丙醇結晶處理，以得到28g的化合物12(淡黃色固體)。上述反應之反應式如下所示： 38 g of compound 11, 200 ml of an 84% aqueous formic acid solution and 150 ml of toluene were placed in a 500 ml three-necked flask. Then, the temperature was controlled at 20 ° C and stirred for 20 hours. After completion of the reaction, it was separated by water extraction, and then crystallized from isopropyl alcohol to give 28 g of Compound 12 (light yellow solid). The reaction formula of the above reaction is as follows:

將3.3g的鎂屑、50ml的無水THF、一粒碘以及幾滴溴丙烷加入500ml的三頸瓶中。然後，在氮氣保護下稍微加熱。待反應引發後，滴加18g的溴丙烷和150ml的無水THF的混合物進行迴流1小時。將反應溫度降至-10℃，再滴加28g的化合物12和150ml的無水THF的混合物。將溫度控制在-10℃，攪拌12小時。接著，將反應液倒入鹽酸和冰的混合物中水解，並用甲苯萃取分離兩次。將提取液蒸餾至250ml左右，再加入1g的對甲苯磺酸迴流2小時，以得到棕紅色油狀物。之後，進行管柱層析，並再結晶純化，以得到10g的化合物13(淡黃色固體)。上述反應之反應式如下所示： 3.3 g of magnesium turnings, 50 ml of anhydrous THF, one iodine and a few drops of bromopropane were placed in a 500 ml three-necked flask. Then, it was heated slightly under the protection of nitrogen. After the reaction was initiated, a mixture of 18 g of bromopropane and 150 ml of anhydrous THF was added dropwise to reflux for 1 hour. The reaction temperature was lowered to -10 ° C, and a mixture of 28 g of Compound 12 and 150 ml of anhydrous THF was further added dropwise. The temperature was controlled at -10 ° C and stirred for 12 hours. Next, the reaction liquid was poured into a mixture of hydrochloric acid and ice to be hydrolyzed, and extracted twice with toluene. The extract was distilled to about 250 ml, and further added with 1 g of p-toluenesulfonic acid for 2 hours to obtain a brownish red oil. Thereafter, column chromatography was carried out, and recrystallization purification was carried out to obtain 10 g of Compound 13 (yellow solid). The reaction formula of the above reaction is as follows:

接著，將10g的化合物13、1g的5%的Pd/C、100ml的乙醇以及100ml的甲苯加入1L的氫氣釜中，，在25℃下加氫氣6小時，以得到9.5g的化合物14(白色固體)。上述反應之反應式如下所示： Next, 10 g of the compound 13, 1 g of 5% Pd/C, 100 ml of ethanol, and 100 ml of toluene were placed in a 1 L hydrogen kettle, and hydrogen gas was added at 25 ° C for 6 hours to obtain 9.5 g of the compound 14 (white solid). The reaction formula of the above reaction is as follows:

將9.5g的化合物14、4.2g的t-BuOK以及100ml的無水THF加入250ml的三頸瓶中。然後，在氮氣保護下，將溫度降至-100℃，並滴加17ml的n-BuLi(2.4M)。滴加完 畢後，將溫度控制在-100℃，攪拌1小時。加入9.5g的硼酸三異丁酯和50ml的無水THF的混合物。滴加完畢後，將溫度控制在-100℃，攪拌1小時後，將溫度升至室溫進行水解，以得到7.2g的化合物15(黃色固體)。上述反應之反應式如下所示： 9.5 g of compound 14, 4.2 g of t-BuOK and 100 ml of anhydrous THF were placed in a 250 ml three-necked flask. Then, under a nitrogen atmosphere, the temperature was lowered to -100 ° C, and 17 ml of n-BuLi (2.4 M) was added dropwise. After the dropwise addition was completed, the temperature was controlled at -100 ° C and stirred for 1 hour. A mixture of 9.5 g of triisobutyl borate and 50 ml of anhydrous THF was added. After completion of the dropwise addition, the temperature was controlled at -100 ° C, and after stirring for 1 hour, the temperature was raised to room temperature to carry out hydrolysis to obtain 7.2 g of Compound 15 (yellow solid). The reaction formula of the above reaction is as follows:

將7.2g的化合物15、9.4g的雙苯氟醚環溴化合物、10.2g的碳酸鈉、50ml的水、50ml的乙醇、100ml的甲苯以及0.25g的Pd(PPh3)4加入500ml的三頸瓶中。然後，在氮氣保護下，進行加熱迴流6小時。在常規處理之後，得到淡黃色油狀物。進行石油醚管柱層析，並在乙醇下再結晶多次。，以得到5g的化合物3RIGUQUF(白色固體)。上述反應之反應式如下所示： 7.2 g of compound 15, 9.4 g of diphenylfluoroether cyclobromide compound, 10.2 g of sodium carbonate, 50 ml of water, 50 ml of ethanol, 100 ml of toluene and 0.25 g of Pd(PPh3)4 were added to a 500 ml three-necked flask. in. Then, heating under reflux for 6 hours under nitrogen atmosphere. After the usual workup, a pale yellow oil was obtained. The petroleum ether column was subjected to column chromatography and recrystallized several times under ethanol. To give 5 g of compound 3 RIGUQUF (white solid). The reaction formula of the above reaction is as follows:

液晶組成物的製備及性質測試 Preparation and properties testing of liquid crystal compositions

實施例1-11 Example 1-11

將液晶化合物以表1所示的比例(重量百分比)混合，藉此製備實施例1至實施例11的液晶組成物。 The liquid crystal compositions were mixed at a ratio (% by weight) shown in Table 1, whereby the liquid crystal compositions of Examples 1 to 11 were prepared.

接著，對實施例1至實施例11的液晶組成物分別進行澄清點(Tni)、介電常數異向性(△ε)、轉動黏度(γ1)、光學異向性(△n)的測量，其中實施例1至實施例11的測量結果如表2所示。液晶化合物及液晶組成物的前述性質分別是透過以下方法進行測定。 Next, the liquid crystal compositions of Examples 1 to 11 were subjected to measurement of a clearing point (Tni), a dielectric anisotropy (Δε), a rotational viscosity (γ1), and an optical anisotropy (Δn), respectively. The measurement results of Examples 1 to 11 are shown in Table 2. The above properties of the liquid crystal compound and the liquid crystal composition were measured by the following methods, respectively.

澄清點(Tni，單位：℃)：使用差示掃描量熱儀(DSC；廠商：TA；型號：Q200)，將液晶化合物或液晶組成物置於鋁盤中精秤0.5mg至10mg，並在鋁盤壓錠後以DSC進行相變溫度測試，即藉由液晶化合物或液晶組成物因相變化而出現的吸熱峰及放熱峰的起始點來得到相變化溫度。由於液晶化合物或液晶組成物為向列相(nematic phase)，因此由室溫升溫的圖譜上會出現向列相轉變為液相的吸熱峰，可讀出澄清點的溫度。 Clarification point (Tni, unit: °C): using a differential scanning calorimeter (DSC; manufacturer: TA; model: Q200), the liquid crystal compound or liquid crystal composition is placed in an aluminum pan fine scale 0.5mg to 10mg, and in aluminum After the disk was pressed, the phase change temperature was measured by DSC, that is, the phase change temperature was obtained by the endothermic peak of the liquid crystal compound or the liquid crystal composition due to the phase change and the starting point of the exothermic peak. Since the liquid crystal compound or the liquid crystal composition is a nematic phase, an endothermic peak which changes from a nematic phase to a liquid phase appears on the spectrum which is raised from room temperature, and the temperature of the clearing point can be read.

介電常數異向性(△ε)：將待測液晶組成物裝入液晶盒中，於溫度25℃下，對該液晶盒施加0V至20V的電壓，並量測得電容對電壓的曲線(C-V curve)。在C-V curve中，高電壓區及低電壓區皆會呈現水平，在低電壓區讀取電容C ⊥、在高電壓區讀取電容C ∥，並可藉公式由C ⊥、C ∥換算為ε ⊥、ε ∥，介電常數異向性(△ε)=ε ∥-ε ⊥。 Dielectric anisotropy (Δε): The liquid crystal composition to be tested is placed in a liquid crystal cell, and a voltage of 0 V to 20 V is applied to the liquid crystal cell at a temperature of 25 ° C, and a capacitance versus voltage curve is measured ( CV curve). In the CV curve, both the high voltage region and the low voltage region will be horizontal, the capacitor C ⊥ is read in the low voltage region, and the capacitor C 读取 is read in the high voltage region, and can be converted into ε by C ⊥ and C 借 by the formula. ⊥, ε ∥, dielectric anisotropy (Δε) = ε ∥ - ε ⊥.

另外，在獲得各個液晶組成物的△ε後，藉由母液的已知△ε，並透過外插方式得出對應的待測液晶化合物的△ε。 Further, after obtaining Δε of each liquid crystal composition, the corresponding Δε of the liquid crystal compound to be tested is obtained by the known Δε of the mother liquid and by extrapolation.

光學異向性(△n)：利用一目鏡上安裝有偏光板的阿貝(Abbe)折射儀(廠商：ATAGO；型號：DR-M2)對各個液晶組成物進行量測。首先，在阿貝折射儀的主稜鏡表面以單方向刷上配向液，並以無塵布沿同一方向擦拭配向，接著在主稜鏡上滴加少量待測的液晶組成物，在測試溫度25℃，使用波長為589nm的濾光片進行光學異向性的測量。當偏光方向與擦拭方向平行時，測得的折射率為n ∥；當偏光方向與擦拭方向垂直時，測得的折射率為n ⊥；光學異向性(△n)=n ∥-n ⊥。 Optical anisotropy (Δn): Each liquid crystal composition was measured by an Abbe refractometer (manufacturer: ATAGO; model: DR-M2) on which a polarizing plate was attached. First, the alignment liquid is brushed in a single direction on the main surface of the Abbe refractometer, and the alignment is wiped in the same direction with a dust-free cloth, and then a small amount of the liquid crystal composition to be tested is dropped on the main crucible at the test temperature. Optical anisotropy was measured at 25 ° C using a filter with a wavelength of 589 nm. When the polarizing direction is parallel to the wiping direction, the measured refractive index is n ∥; when the polarizing direction is perpendicular to the wiping direction, the measured refractive index is n ⊥; optical anisotropy (Δn)=n ∥-n ⊥ .

另外，在獲得各個液晶組成物所測得的△n後，藉由母液的已知△n，並透過外插方式得出對應的待測液晶化合物的△n。 Further, after obtaining Δn measured by each liquid crystal composition, the corresponding Δn of the liquid crystal compound to be tested is obtained by the known Δn of the mother liquid and by extrapolation.

轉動黏度(γ1，單位：mPa．s)： 如前述測得介電常數異向性(△ε)之後，軟體即可由△ε值進行轉動黏度(γ1)的換算。 Rotational viscosity (γ1, unit: mPa.s): After the dielectric anisotropy (Δε) is measured as described above, the soft body can be converted from the rotational viscosity (γ1) by the Δε value.

實施例12-20及比較例1-2 Examples 12-20 and Comparative Examples 1-2

將液晶化合物以表3所示的比例(重量百分比)混合，藉此製備實施例12-20及比較例1-2的液晶組成物。 The liquid crystal compounds were mixed at a ratio (% by weight) shown in Table 3, whereby liquid crystal compositions of Examples 12 to 20 and Comparative Example 1-2 were prepared.

接著，對實施例12-20及比較例1-2的液晶組成物分別進行澄清點(Tni)、介電常數異向性(△ε)、轉動黏度(γ1)、光學異向性(△n)的測量，其中實施例12-20及比較例1-2的測量結果如表4所示。 Next, the liquid crystal compositions of Examples 12 to 20 and Comparative Example 1-2 were subjected to a clearing point (Tni), a dielectric anisotropy (Δε), a rotational viscosity (γ1), and an optical anisotropy (Δn). The measurement results of Examples 12-20 and Comparative Example 1-2 are shown in Table 4.

由表2、以及4可得知，實施例1-20所述的液晶組成物因為同時包含式(I)與式(II)的化合物，所以具有較低的轉動黏度或/且較高的介電異方性，因此本發明所述液晶組成物可滿足液晶顯示器在高應答速度與低啟動電壓二方 面的需求。另一方面，同時包含式(I)與式(II)的液晶組成物具有較寬的液晶範圍，可提供液晶顯示器所需的廣的操作溫寬。比較例1的液晶組成物不包含具有式(I)結構的化合物，其轉動黏度較高且介電異方性較低，由於比較例2的液晶組成物不包含具有式(II)結構的化合物，觀察到在室溫析出，室溫下不是液晶態，無法量測其性質。實施例1-20所述的液晶組成物符合業界需求的介電常數異向性、轉動黏度、及光學異向性，因此可預期地，同時採用符合本發明式(I)及(II)化合物之液晶組成物，應用於液晶顯示元件時，可擁有省電的特性。 As can be seen from Tables 2 and 4, the liquid crystal compositions described in Examples 1-20 have a lower rotational viscosity or/and a higher dielectric because they contain both the compound of the formula (I) and the formula (II). Electrical anisotropy, so the liquid crystal composition of the present invention can satisfy the high response speed and low starting voltage of the liquid crystal display Face demand. On the other hand, the liquid crystal composition containing both the formula (I) and the formula (II) has a wide liquid crystal range, and can provide a wide operating temperature required for a liquid crystal display. The liquid crystal composition of Comparative Example 1 does not contain a compound having the structure of the formula (I), and has a high rotational viscosity and a low dielectric anisotropy, since the liquid crystal composition of Comparative Example 2 does not contain a compound having the structure of the formula (II). It was observed that it precipitated at room temperature, and it was not in a liquid crystal state at room temperature, and its properties could not be measured. The liquid crystal compositions described in Examples 1-20 meet the dielectric anisotropy, rotational viscosity, and optical anisotropy of the industry, and thus it is expected to simultaneously employ compounds of the formula (I) and (II) according to the present invention. The liquid crystal composition can have power saving characteristics when applied to a liquid crystal display element.

雖然本發明已以實施方式揭露如上，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，在不脫離本發明的精神和範圍內，當可作些許的更動與潤飾，故本發明的保護範圍當視後附的申請專利範圍所界定者為準。 The present invention has been disclosed in the above embodiments, but it is not intended to limit the invention, and any one of ordinary skill in the art can make some changes and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (10)

一種液晶組成物，包含：至少一種具有式(I)所示結構之化合物 其中，R1係為氫、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1及Z2係獨立為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；R3係為-CH=CF2、-CH2-CF3、或-CF2CFCF2；i為0或1；以及至少一種具有式(II)所示結構之化合物 其中，A1、A2、A3、及A4係獨立地為 、或，且A1、A2、A3、及A4 至少一者為、或；其中R2 係獨立地為氫、或鹵素；R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；m、n、或o係獨立地為1 或0；以及，當m+n+o<3時，A1非為 A liquid crystal composition comprising: at least one compound having the structure represented by formula (I) Wherein R 1 is hydrogen, C 1-15 alkyl, C 2-15 alkenyl or, in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 and Z 2 are independently a single bond, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 ( CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH=CH-, -CH =CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; R 3 is -CH=CF 2 , -CH 2 -CF 3 , or -CF 2 CFCF 2 ; i is 0 Or 1; and at least one compound having the structure of formula (II) Wherein A 1 , A 2 , A 3 , and A 4 are independently ,or And at least one of A 1 , A 2 , A 3 , and A 4 is ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or / and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 3 , Z 4 , and Z 5 are independently a single bond, - CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -( CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C ≡C-, -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; m, n, or o are independently 1 or 0; , when m + n + o <3, A 1 is a non- 如申請專利範圍第1項所述之液晶組成物，其中該具有式(I)所示結構之化合物包含： 、及/或 ，其中R1係為氫、C1-15 烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1及Z2係獨立為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，i為0或1。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (I) comprises: And/or Wherein R 1 is hydrogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 and Z 2 are independently a single bond, -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 ( CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, -CH=CH-, -CH =CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, i is 0 or 1. 如申請專利範圍第1項所述之液晶組成物，其中該具有式(I)所示結構之化合物包含 、及/或 ，其中R1係為氫、C1-15 烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1及Z2係獨立為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；以及，i為0或1。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (I) comprises And/or Wherein R 1 is hydrogen, C 1-15 alkyl, C 2-15 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 and Z 2 are independently a single bond, -COO-, -OCO-, -CF 2 O- , -OCF 2 -, -C≡C-, or -CH=CH-; and, i is 0 or 1. 如申請專利範圍第1項所述之液晶組成物，其中具有式(II)所示結構之化合物包含 ，其中A2、A3、及A4 係獨立地為、或，其中R2係獨立地為 氫、或鹵素；R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、 -OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、n、或o係獨立地為1或0。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (II) comprises Where A 2 , A 3 , and A 4 are independently ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 4 and Z 5 are independently a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- , -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, m, n, or o are independently 1 or 0. 如申請專利範圍第1項所述之液晶組成物，其中具有式(II)所示結構之化合物包含 ，其中A2、及A3係獨立地 為、或，其中R2係獨立地為氫、或鹵素； R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、或n係獨立地為1或0。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (II) comprises Where A 2 and A 3 are independently ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 4 and Z 5 are independently a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- , -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, m, or n are independently 1 or 0. 如申請專利範圍第1項所述之液晶組成物，其中具有式(II)所示結構之化合物包含 ，其中A2、A3、及 A4係獨立地為、或，其中R2係獨立地為 氫、或鹵素；R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、-CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、n、或o係獨立地為1或0。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (II) comprises Where A 2 , A 3 , and A 4 are independently ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 4 and Z 5 are independently a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- , -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and, m, n, or o are independently 1 or 0. 如申請專利範圍第1項所述之液晶組成物，其中具有式(II)所示結構之化合物包含 ，其中A2、及A3係獨立地 為、或，其中R2係獨立地為氫、或鹵素； R4及R5係獨立地為氫、鹵素、C1-15烷基、C2-15烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z4、及Z5係獨立地為單鍵、-CH2-、-(CH2)2-、-(CH2)4-、-CH2O-、-OCH2-、-CF=CF-、-(CH2)2CF2O-、-(CH2)2OCF2-、-OCF2(CH2)2-、-CF2O(CH2)2-、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、 -CH=CH-、-CH=CH-(CH2)2-、或-(CH2)2-CH=CH-；以及，m、或n係獨立地為1或0。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (II) comprises Where A 2 and A 3 are independently ,or Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-15 alkyl, C 2-15 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 4 and Z 5 are independently a single bond, -CH 2 - , -(CH 2 ) 2 -, -(CH 2 ) 4 -, -CH 2 O-, -OCH 2 -, -CF=CF-, -(CH 2 ) 2 CF 2 O-, -(CH 2 ) 2 OCF 2 -, -OCF 2 (CH 2 ) 2 -, -CF 2 O(CH 2 ) 2 -, -COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C- -CH=CH-, -CH=CH-(CH 2 ) 2 -, or -(CH 2 ) 2 -CH=CH-; and m, or n is independently 1 or 0. 如申請專利範圍第1項所述之液晶組成物，其中具有 式(I)所示結構之化合物包含，其 中R1係為氫、C1-5烷基、C2-5烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；R2係獨立地為氫、或鹵素；Z1為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；R3係為-CH=CF2、或-CH2-CF3；其中，具有式(II)所示結構之 化合物的A1、A2、A3、及A4係獨立地為 、或，且A1、A2、A3、及 A4至少一者為；其中R2係獨立地為氫、或鹵 素；R4及R5係獨立地為氫、鹵素、C1-5烷基、C2-5烯基、或於上述官能基中，任意碳上之氫原子係被鹵素原子取代、或/及任意之-CH2-係被-O-、-CO-或-COO-取代；Z3、Z4、及Z5 係獨立地為單鍵、-COO-、-OCO-、-CF2O-、-OCF2-、-C≡C-、或-CH=CH-；以及，m、n、或o係獨立地為1或0。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (I) comprises Wherein R 1 is hydrogen, C 1-5 alkyl, C 2-5 alkenyl, or in the above functional group, the hydrogen atom on any carbon is substituted by a halogen atom, or/and any -CH 2 - Is substituted by -O-, -CO- or -COO-; R 2 is independently hydrogen or halogen; Z 1 is a single bond, -COO-, -OCO-, -CF 2 O-, -OCF 2 - , -C≡C-, or -CH=CH-; R 3 is -CH=CF 2 or -CH 2 -CF 3 ; wherein A 1 , A 2 of the compound having the structure of formula (II) , A 3 , and A 4 are independently ,or And at least one of A 1 , A 2 , A 3 , and A 4 is Wherein R 2 is independently hydrogen or halogen; R 4 and R 5 are independently hydrogen, halogen, C 1-5 alkyl, C 2-5 alkenyl, or any of the above functional groups, on any carbon The hydrogen atom is substituted by a halogen atom, or/and any -CH 2 - is substituted by -O-, -CO- or -COO-; Z 3 , Z 4 , and Z 5 are independently a single bond, - COO-, -OCO-, -CF 2 O-, -OCF 2 -, -C≡C-, or -CH=CH-; and, m, n, or o are independently 1 or 0. 如申請專利範圍第1項所述之液晶組成物，其中具有式(I)所示結構之化合物係包含 ，其中R1係為氫、或C1-5烷基； R3係為-CH=CF2、或-CH2-CF3；其中，具有式(II)所示結構之化合物包含 、或上述之組合，R4係為 氫、或C1-5烷基；R5係為H、F、OCF3、CF3、-OCH=CF2、或-OCH2-CF3。 The liquid crystal composition according to claim 1, wherein the compound having the structure represented by the formula (I) contains Wherein R 1 is hydrogen or C 1-5 alkyl; R 3 is -CH=CF 2 or -CH 2 -CF 3 ; wherein the compound having the structure represented by formula (II) comprises Or a combination of the above, R 4 is hydrogen or C 1-5 alkyl; and R 5 is H, F, OCF 3 , CF 3 , -OCH=CF 2 or -OCH 2 -CF 3 . 一種液晶顯示元件，包括如申請專利範圍第1項至第9項中任一項所述的液晶組成物。 A liquid crystal display element comprising the liquid crystal composition according to any one of claims 1 to 9.
TW104114861A 2014-07-23 2015-05-11 Liquid crystal composition and liquid crystal display device employing the same TWI518175B (en)

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