JP5546771B2 - Liquid crystal medium and liquid crystal display - Google Patents

Description

  The present invention relates to a liquid crystal medium, preferably a dielectrically positive nematic medium comprising one or more dielectrically neutral compounds and one or more dielectrically positive compounds, and a liquid crystal display comprising these media, In particular, it relates to displays addressed by an active matrix, in particular TN-, IPS-, FFS- or OCB-type displays.

  A liquid crystal display (LCD) is widely used for displaying information. LCDs are used for direct view displays as well as projection displays. The electro-optic modes used are, for example, twisted nematic (TN)-, super twisted nematic (STN)-, optically compensated bend (OCB)-and electrically controlled birefringence EC (B). Electrically Controlled Birefringence (Mode) and various variations thereof, for example, Vertically Aligned Nematic (VAN), Patterned ITO Vertically Nematic (PVA), Patterned ITO Nematically Stabilized Polymer Vertical alignment nematic (PSVA: Polymer Stab) There are other modes, such as an optimized Vertically Aligned Nematic (-) and Multi-domain Vertically Aligned Nematic (MVA) mode. All of these modes use an electric field that is substantially perpendicular to the substrate and the liquid crystal layer, respectively. In addition to these modes, an electro-optic mode using an electric field substantially parallel to the substrate and the liquid crystal layer, for example, an in-plane switching (IPS: In Plane Switching) mode (for example, German Patent No. 4000451). (Disclosed in Patent Document 1) and European Patent No. 0588568 (Patent Document 2) and a fringe field switching (FFS) mode. In particular, these electro-optic modes are used for LCDs for modern desktop monitors and even for displays for television and multimedia applications. The liquid crystals according to the invention are preferably used in these types of displays.

  For these displays, there is a need for new liquid crystal media with improved properties. In particular, the contrast ratio needs to be improved for many types of applications. Thus, there is a need for liquid crystal media with improved behavior. Their rotational viscosities should be 100 mPa · s or less, preferably 90 mPa · s or less, in particular 80 mPa · s or less. In addition to this parameter, the medium should suitably exhibit a wide range of nematic phases, appropriate birefringence (Δn), and the dielectric anisotropy (Δε) is high enough to allow a reasonably low operating voltage. Should be. Preferably, Δε should be higher than 4, very preferably higher than 5, but it is disadvantageous for at least a reasonably high specific resistance, which is another requirement, and is preferably 15 or less, in particular 10 or less. Yes, most preferably within the range of 5-9, especially for active matrix addresses.

  The display according to the invention is preferably addressed by an active matrix LCD (AMD for short), preferably a thin film transistor (TFT) matrix. However, the liquid crystals of the present invention can also be beneficially used in displays with other known addressing means.

  Liquid crystal compositions suitable for LCDs and particularly IPS displays are disclosed in, for example, JP-A-07-181439 (Patent Document 3), European Patent 0667555 (Patent Document 4), European Patent 0673986 (Patent Document 5). German Patent No. 19509410 (Patent Literature 6), German Patent No. 19528106 (Patent Literature 7), German Patent No. 19528107 (Patent Literature 8), International Patent Application Publication No. 96/23851 (Patent Literature) 9) and International Patent Application Publication No. 96/28521 (Patent Document 10). However, these compositions have significant drawbacks with respect to physical properties. For example, when comparing a display to a display operating in one of the VA modes that has recently been intensely competitive, for example for television displays, most of those drawbacks are among the other disadvantages due to undesirably low contrast ratios. Connected.

German Patent No. 4000451 European Patent No. 0588568 Japanese Patent Application Laid-Open No. 07-181439 European Patent No. 0667555 European Patent No. 0673986 German Patent No. 19509410 German Patent No. 19528106 German Patent No. 19528107 International Patent Application Publication No. 96/23851 International Patent Application Publication No. 96/28521

Thus, for practical applications such as a wide nematic phase range, suitable optical anisotropy Δn depending on the display mode used, high Δε, low viscosity, especially low rotational viscosity (γ ₁ ) and a particularly high contrast ratio in the display There is a great demand for liquid crystal media with suitable properties.

  Surprisingly, it has now been found that suitable phase ranges, suitably high values of Δε and Δn and suitably low viscosity liquid crystal media can be realized, which do not exhibit the disadvantages of prior art materials or at least It is shown only to a small extent by special case.

  These improved liquid crystal media of the present application have at least the following (selected from one or more dielectrically neutral compounds of formula I, one or more groups of compounds of formulas II and III, greater than 3 A dielectrically positive compound having anisotropy, and one or more dielectrically neutral compounds of formula IV).

  One or more dielectrically neutral compounds of formula I.

式中、
Ｒ^１１およびＲ^１２は、それぞれ互いに独立に、好ましくは炭素数１〜７の、アルキル、アルコキシ、フッ素化されたアルキルまはたフッ素化されたアルコキシ、好ましくは炭素数２〜７の、アルケニル、アルケニルオキシ、アルコキシアルキルまたはフッ素化されたアルケニルであり、Ｒ^１１は好ましくはアルケニル、より好ましくは１−Ｅ−アルケニル、最も好ましくはビニルであり、Ｒ^１２は好ましくはアルキル、より好ましくはｎ−アルキル、最も好ましくはメチルまたはエチルである。

Where
R ¹¹ and R ¹² are each independently of each other preferably alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms, preferably alkenyl having 2 to 7 carbon atoms, Alkenyloxy, alkoxyalkyl or fluorinated alkenyl, R ¹¹ is preferably alkenyl, more preferably 1-E-alkenyl, most preferably vinyl, and R ¹² is preferably alkyl, more preferably n-alkyl. Most preferably, it is methyl or ethyl.

  A dielectrically positive compound selected from the group of one or more compounds of the formulas II and III and having a dielectric anisotropy greater than 3.

式中、
Ｒ^２およびＲ^３は、それぞれ互いに独立に、炭素数１〜７のアルキル、アルコキシ、フッ素化されたアルキルまはたフッ素化されたアルコキシ、炭素数２〜７のアルケニル、アルケニルオキシ、アルコキシアルキルまたはフッ素化されたアルケニルであり、Ｒ^２およびＲ^３は、好ましくは、アルキルまたはアルケニルであり、

Where
R ² and R ³ are each independently of each other alkyl of 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl of 2 to 7 carbons, alkenyloxy, alkoxyalkyl or Fluorinated alkenyl, R ² and R ³ are preferably alkyl or alkenyl,

Ｌ^２１、Ｌ^２２、Ｌ^３１およびＬ^３２は、それぞれ互いに独立に、ＨまたはＦであり、好ましくは、Ｌ^２１および／またはＬ^３１はＦであり、
Ｘ^２およびＸ^３は、それぞれ互いに独立に、ハロゲン、炭素数１〜３のハロゲン化されたアルキルまたはアルコキシ、または炭素数２または３のハロゲン化されたアルケニルまたはアルケニルオキシであり、好ましくは、Ｆ、Ｃｌ、−ＯＣＦ_３または−ＣＦ_３、最も好ましくは、Ｆ、Ｃｌまたは−ＯＣＦ_３であり、
Ｚ^３は、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−または単結合であり、好ましくは、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−または単結合であり、最も好ましくは、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−または単結合であり、および
ｌ、ｍ、ｎおよびｏは、それぞれ互いに独立に、０または１である。

L ²¹ , L ²² , L ³¹ and L ³² are each independently H or F, preferably L ²¹ and / or L ³¹ is F;
X ² and X ³ are each independently of each other halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms, or halogenated alkenyl or alkenyloxy having 2 or 3 carbon atoms, preferably F , Cl, —OCF ₃ or —CF ₃ , most preferably F, Cl or —OCF ₃ ,
Z ³ is —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —COO—, trans—CH═CH—, trans—CF═CF—, —CH ₂ O— or a single bond, _{-CH 2 CH 2 -, - COO-} , a trans -CH = CH- or a single bond, and most preferably, -COO-, is trans -CH = CH- or a single bond, and l, m, n and o is 0 or 1 independently of each other.

  • One or more dielectrically neutral compounds of formula IV.

式中、
Ｒ^４１およびＲ^４２は、それぞれ互いに独立に、上で式ＩＩにおいてＲ^２に与えられる意味を有し、好ましくは、Ｒ^４１はアルキルでＲ^４２はアルキルまたはアルコキシであるか、または、Ｒ^４１はアルケニルでＲ^４２はアルキルであり、

Where
R ⁴¹ and R ⁴² each independently of one another have the meaning given for R ² in formula II above, preferably R ⁴¹ is alkyl and R ⁴² is alkyl or alkoxy, or R ⁴¹ is Alkenyl and R ⁴² is alkyl;

Ｚ^４１およびＺ^４２は、それぞれ互いに独立に、および、Ｚ^４１が２回存在する場合は、これらもそれぞれ互いに独立に、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−、−Ｃ≡Ｃ−または単結合であり、好ましくは、それらの少なくとも一つは単結合であり、および
ｐは、０、１または２、好ましくは０または１であり、
但し、式Ｉの化合物は除外される。

Z ⁴¹ and Z ⁴² are each independently of each other, and when Z ⁴¹ is present twice, they are also each independently of each other, —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, trans —CF═CF—, —CH ₂ O—, —CF ₂ O—, —C≡C— or a single bond, preferably at least one of them is a single bond, and p is 0, 1 Or 2, preferably 0 or 1,
However, compounds of formula I are excluded.

  In a preferred embodiment of the present invention, the liquid crystal medium according to the present application comprises one or more compounds of formula I-1, preferably selected from the group of compounds of formulas I-1 to I-4.

式中、
Ｒ^１２は上で式Ｉにおいて与えられる意味を有し、好ましくは、アルキル、１−Ｅ−アルケニルまたは３−アルケニルであり、より好ましくは、アルキル、最も好ましくは、メチルまたはエチルである。

Where
R ¹² has the meaning given above in formula I and is preferably alkyl, 1-E-alkenyl or 3-alkenyl, more preferably alkyl, most preferably methyl or ethyl.

  In a preferred embodiment of the invention, the liquid crystal medium according to the present application comprises one or more compounds selected from the group of compounds of formulas II-1 to II-3.

式中、
パラメーターは上で式ＩＩにおいて与えられるそれぞれの意味を有し、および式ＩＩ−３中でパラメーターＬ^２３およびＬ^２４は、それぞれ互いに、および他のパラメーターと独立に、ＨまたはＦである。

Where
The parameters have their respective meanings given in formula II above, and in formula II-3, parameters L ²³ and L ²⁴ are H or F, respectively, independently of each other and other parameters.

Preferably, the medium comprises a compound selected from the group of compounds of formulas II-1 to II-3 where L ²¹ and L ²² or both L ²³ and L ²⁴ are F.

  Preferably the medium comprises one or more compounds of formula II-1, preferably selected from the group of compounds of formulas II-1a to II-1d.

式中、
パラメーターは上で与えられるそれぞれの意味を有し、好ましくは、
Ｌ^２１およびＬ^２２の両方がＦで、Ｌ^２３およびＬ^２４の両方がＨであるか、または
Ｌ^２１、Ｌ^２２、Ｌ^２３およびＬ^２４の全てがＦである。

Where
The parameters have their respective meanings given above, preferably
Both L ²¹ and L ²² are F and both L ²³ and L ²⁴ are H, or L ²¹ , L ²² , L ²³ and L ²⁴ are all F.

  Particularly preferred compounds of formula II-1 are:

式中、Ｒ^２は、上で与えられる意味を有する。

In which R ² has the meaning given above.

In a preferred embodiment, the medium comprises one or more compounds selected from the group of compounds of formulas II-2 and II-3, wherein L ²¹ , L ²² , L ²³ and L ²⁴ are all F.

  Preferably the medium comprises one or more of the formula II-2, preferably a compound selected from the group of compounds of the formulas II-2a to II-2c.

式中、
パラメーターは上で与えられるそれぞれの意味を有し、好ましくは、
Ｌ^２１およびＬ^２２の両方がＦである。

Where
The parameters have their respective meanings given above, preferably
Both L ²¹ and L ²² are F.

  Preferably the medium comprises one or more compounds selected from the group of compounds of formulas II-3a to II-3e.

式中、
パラメーターは上で与えられるそれぞれの意味を有する。

Where
The parameters have their respective meanings given above.

Preferably the medium comprises one or more compounds selected from the group of compounds of formulas II-3a to II-3e, wherein L ²¹ and L ²² , or both L ²³ and L ²⁴ are F.

In a preferred embodiment, the medium comprises one or more compounds selected from the group of compounds of formulas II-3a to II-3e, wherein L ²¹ , L ²² , L ²³ and L ²⁴ are all F.

  Particularly preferred compounds of formula II-3 are:

式中、Ｒ^２は、上で与えられる意味を有する。

In which R ² has the meaning given above.

  In a further preferred embodiment of the invention, the medium comprises one or more compounds selected from the group of compounds of formula III-1 and III-2.

式中、
パラメーターは上で式ＩＩＩにおいて与えられるそれぞれの意味を有する。

Where
The parameters have their respective meanings given above in formula III.

  Preferably the medium comprises one or more compounds of formula III-1, preferably selected from the group of compounds of formulas III-1a to III-1j.

式中、
パラメーターは上で与えられるそれぞれの意味を有し、Ｌ^３３〜Ｌ^３６は、それぞれ互いに独立にＨまたはＦである。

Where
The parameters have their respective meanings given above, and L ^{33 to} L ³⁶ are each independently H or F.

  Preferred compounds of formula III-1a are selected from the group of compounds of formulas III-1a-1 to III-1a-4.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1b are selected from the group of compounds of formula III-1b-1 and III-1b-2, preferably III-1b-2.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1c are selected from the group of compounds of formula III-1c-1 to III-1c-5.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1d and III-1e are selected from the group of compounds of formula III-1d-1 and III-1e-1.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1f are selected from the group of compounds of formula III-1f-1 to III-1f-5.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1g are selected from the group of compounds of formula III-1g-1 to III-1g-5.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-1h are selected from the group of compounds of formulas III-1h-1 to III-1h-3.

式中、
Ｒ^３は上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferred compounds of formula III-2 are selected from the group of compounds of formula III-2a and III-2b.

式中、
パラメーターは上で与えられるそれぞれの意味を有し、パラメーターＬ^３３およびＬ^３４は、それぞれ互いに、および他のパラメーターと独立に、ＨまたはＦである。

Where
The parameters have their respective meanings given above, and parameters L ³³ and L ³⁴ are H or F, respectively, independently of each other and other parameters.

  Preferred compounds of formula III-2a are selected from the group of compounds of formula III-2a-1 to III-2a-6.

式中、
Ｒ^３は、上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  The medium according to the invention can comprise one or more compounds of the formula III-3 instead of or in addition to the compounds of the formula III-1 and / or III-2.

式中、
パラメーターは上で式ＩＩＩにおいて与えられるそれぞれの意味を有する。好ましくは、これらの化合物は式ＩＩＩ−３ａの化合物である。

Where
The parameters have their respective meanings given above in formula III. Preferably these compounds are compounds of formula III-3a.

式中、
Ｒ^３は、上で与えられる意味を有する。

Where
R ³ has the meaning given above.

  Preferably, the compound of formula IV is selected from the group of compounds of formula IV-1 to IV-5.

式中、
Ｒ^４１およびＲ^４２は、上で一般的に式ＩＶにおいて与えられるそれぞれの意味を有し、
通常、特に式ＩＶ−１およびＩＶ−５において、Ｒ^４１は、好ましくは、アルキルまたはアルケニル、好ましくは、アルケニルであり、Ｒ^４２は、好ましくは、アルキルまたはアルケニル、好ましくは、アルキルであり、
あるいは、式ＩＶ−２において、Ｒ^４１およびＲ^４２の両方は、好ましくは、アルキルであり、
式ＩＶ−４において、Ｒ^４１は、好ましくは、アルキルまたはアルケニル、好ましくは、アルキルであり、Ｒ^４２は、好ましくは、アルキルまたはアルコキシ、好ましくは、アルコキシである。

Where
R ⁴¹ and R ⁴² have the respective meanings generally given above in formula IV;
Usually, particularly in formulas IV-1 and IV-5, R ⁴¹ is preferably alkyl or alkenyl, preferably alkenyl, R ⁴² is preferably alkyl or alkenyl, preferably alkyl,
Alternatively, in formula IV-2, both R ⁴¹ and R ⁴² are preferably alkyl,
In formula IV-4, R ⁴¹ is preferably alkyl or alkenyl, preferably alkyl, and R ⁴² is preferably alkyl or alkoxy, preferably alkoxy.

  Preferably the medium is one or more compounds selected from the group of compounds of formulas IV-1, IV-4 and IV-5, preferably one or more compounds of formula IV-1 and formulas IV-4 and IV One or more compounds selected from the group of −5, most preferably one or more compounds of each of formulas IV-1 and IV-5.

  In a preferred embodiment of the invention, the medium is from formula IV-5, more preferably from its respective sub-formula, formula CCP-Vn and / or CCP-nV-m and / or CCP-Vn-m. One or more selected, more preferably selected from the formula CCP-Vn and / or CCP-V2-n, most preferably selected from the group of the formulas CCP-V-1 and CCP-V2-1 Of the compound. Definitions of these abbreviations (acronyms) are given in Table B below.

  In a further preferred embodiment of the invention, which may be the same as or different from the foregoing, the liquid crystal medium according to the invention is of the formula selected from the group of compounds of the formulas IV-1 to IV-5 as shown above One or more compounds of IV and one or more compounds selected from the group of compounds of formula IV-6 to IV-11, most preferably formula IV-10.

式中、
Ｒ^４１およびＲ^４２は、それぞれ互いに独立に、炭素数１〜７のアルキル、アルコキシ、フッ素化されたアルキルまたはフッ素化されたアルコキシ、炭素数２〜７のアルケニル、アルケニルオキシ、アルコキシアルキルまたはフッ素化されたアルケニルであり、
Ｌ^４は、ＨまたはＦである。

Where
R ⁴¹ and R ⁴² each independently represent alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated. Alkenyl
L ⁴ is H or F.

  The medium according to the invention can comprise one or more dielectrically positive compounds of the formula V instead of or in addition to the compounds of the formulas II and / or III.

式中、
Ｒ^５は、炭素数１〜７のアルキル、アルコキシ、フッ素化されたアルキルまたはフッ素化されたアルコキシ、炭素数２〜７のアルケニル、アルケニルオキシ、アルコキシアルキルまたはフッ素化されたアルケニルであり、好ましくは、アルキルまたはアルケニルであり、

Where
R ⁵ is alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl, preferably , Alkyl or alkenyl,

Ｌ^５１およびＬ^５２は、それぞれ互いに独立にＨまたはＦであり、好ましくは、Ｌ^５１はＦであり、
Ｘ^５は、ハロゲン、炭素数１〜３のハロゲン化されたアルキルまたはアルコキシ、炭素数２または３のハロゲン化されたアルケニルまたはアルケニルオキシであり、好ましくは、Ｆ、Ｃｌ、−ＯＣＦ_３または−ＣＦ_３、最も好ましくはＦ、Ｃｌまたは−ＯＣＦ_３であり、
Ｚ^５は、−ＣＨ_２ＣＨ_２−、−ＣＦ_２ＣＦ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−または−ＣＨ_２Ｏ−、好ましくは、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−またはトランス−ＣＨ＝ＣＨ−、最も好ましくは、−ＣＯＯ−または−ＣＨ_２ＣＨ_２−であり、
ｑは、０または１である。

L ⁵¹ and L ⁵² are each independently H or F, preferably L ⁵¹ is F;
X ⁵ is halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms, halogenated alkenyl or alkenyloxy having 2 or 3 carbon atoms, preferably F, Cl, —OCF ₃ or —CF ₃ , most preferably F, Cl or —OCF ₃ ,
Z ⁵ is —CH ₂ CH ₂ —, —CF ₂ CF ₂ —, —COO—, trans—CH═CH—, trans—CF═CF— or —CH ₂ O—, preferably —CH ₂ CH _2. -, - COO- or trans -CH = CH-, most preferably, -COO- or _-CH 2 CH ₂ -,
q is 0 or 1.

  The compound of formula V is preferably selected from the group of compounds of formula V-1 and V-2.

式中、
パラメーターは、上で与えられるそれぞれの意味を有し、
パラメーターＬ^５３およびＬ^５４は、それぞれ互いに、および他のパラメーターと独立に、ＨまたはＦであり、
好ましくは、Ｚ^５は−ＣＨ_２−ＣＨ_２−である。

Where
The parameters have their respective meanings given above,
Parameters L ⁵³ and L ⁵⁴ are each H and F, independently of each other and other parameters,
Preferably Z ⁵ is —CH ₂ —CH ₂ —.

  Preferably, the compound of formula V-1 is selected from the group of compounds of formulas V-1a and V-1b.

式中、Ｒ^５は、上で与えられる意味を有する。

In which R ⁵ has the meaning given above.

  Preferably, the compound of formula V-2 is selected from the group of compounds of formulas V-2a to V-2d.

式中、Ｒ^５は、上で与えられる意味を有する。

In which R ⁵ has the meaning given above.

  In a preferred embodiment, the liquid crystal medium according to the invention comprises one or more compounds of the formula VI.

式中、
Ｒ^６１およびＲ^６２は、それぞれ互いに独立に、上で式ＩＩにおいてＲ^２に与えられる意味を有し、好ましくは、Ｒ^６１はアルキルで、Ｒ^６２はアルキルまたはアルケニルであり、

Where
R ⁶¹ and R ⁶² each independently of one another have the meaning given for R ² in formula II above, preferably R ⁶¹ is alkyl and R ⁶² is alkyl or alkenyl,

Ｚ^６１およびＺ^６２は、それぞれ互いに独立に、および、Ｚ^６１が２回ある場合は、これらもそれぞれ互いに独立に、−ＣＨ_２ＣＨ_２−、−ＣＯＯ−、トランス−ＣＨ＝ＣＨ−、トランス−ＣＦ＝ＣＦ−、−ＣＨ_２Ｏ−、−ＣＦ_２Ｏ−または単結合であり、好ましくは、それらの少なくとも１つは単結合であり、および
ｒは、０、１または２であり、好ましくは、０または１である。

Z ⁶¹ and Z ⁶² are each independently of each other, and when Z ⁶¹ is twice, they are also independently of each other, —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, trans— CF═CF—, —CH ₂ O—, —CF ₂ O— or a single bond, preferably at least one of them is a single bond, and r is 0, 1 or 2, preferably , 0 or 1.

  Preferably, the compound of formula VI is selected from the group of compounds of formula VI-1 and VI-2.

式中、
Ｒ^６１およびＲ^６２は、上で式ＶＩにおいて与えられるそれぞれの意味を有し、Ｒ^６１は、好ましくは、アルキル、より好ましくはｎ−アルキルであり、
式ＶＩ−１において、Ｒ^６２は、好ましくは、アルケニル、好ましくは、−（ＣＨ_２）_２−ＣＨ＝ＣＨ−ＣＨ_３であり、
式ＶＩ−２において、Ｒ^６２は、好ましくは、アルキルである。

Where
R ⁶¹ and R ⁶² have the respective meanings given above in formula VI, R ⁶¹ is preferably alkyl, more preferably n-alkyl,
In formula VI-1, R ⁶² is preferably alkenyl, preferably — (CH ₂ ) ₂ —CH═CH—CH ₃ ,
In formula VI-2, R ⁶² is preferably alkyl.

  Preferred compounds of formula VI-1 are compounds of formula PP-n-2Vm, more preferably of formula PP-1-2V1. Definitions of these abbreviations (acronyms) are given in Table B below.

  Preferred compounds of formula VI-2 are of formula PGP-nm, more preferably formula PGP-3-m, more preferably formula PGP-3-2, PGP-3-3, PGP-3-4 and PGP. It is a compound selected from -3-5. Definitions of these abbreviations (acronyms) are given in Table B below.

  Preferably, the liquid-crystalline medium according to the invention comprises compounds selected from the group of compounds of formulas I to VI, preferably I to IV and VI, most preferably I to IV, more preferably consisting mostly of these, More preferably consisting essentially of these, most preferably all consisting of them.

  In this application, the term “comprising”, in the context of a composition, includes the single or multiple types of components or single or multiple types of compounds in which the referenced item, such as a medium or component, is in question. Unless otherwise clearly defined, the total concentration is preferably 10% or more, most preferably 20% or more.

  Unless explicitly defined otherwise in this context, the term “consists largely of” refers to the single or multiple components or single or multiple compounds in which the item being referred to is in question. It means 55% or more, preferably 60% or more, and most preferably 70% or more.

  Unless otherwise explicitly defined in this context, the term “consisting essentially of” refers to the component or compounds or compounds or compounds that the referenced item is in question. It means 80% or more, preferably 90% or more, most preferably 95% or more.

  Unless explicitly defined otherwise in this context, the term “consisting of all” refers to the single or multiple components or single or multiple compounds in which the item being referred to is in question. % Or more, preferably 99% or more, and most preferably 100.0%.

  In the medium of the present invention, other mesogenic compounds, which are not clearly described above, can be advantageously used as optional components. Such compounds are known to those skilled in the art.

  The liquid crystal medium according to the invention is characterized by a clearing point of 70 ° C. or higher, preferably 75 ° C. or higher.

The Δn at 589 nm (Na ^D ) and 20 ° C. of the liquid crystal medium according to the present invention is preferably in the range of 0.070 to 0.160, more preferably in the range of 0.080 to 0.145. Most preferably, it is in the range of 0.090 to 0.130.

  In a first particularly preferred embodiment of the present invention, the Δn of the liquid crystal medium is in the range of 0.090 to 0.130, more preferably in the range of 0.095 to 0.125, more preferably. It is in the range of 0.100 to 0.120, most preferably in the range of 0.105 to 0.115.

  Δε at 1 kHz and 20 ° C. of the liquid crystal medium according to the present invention is preferably 3 or more, more preferably 4 or more, most preferably 5 or more, while Δε is preferably 12 or less, more preferably 10 or less, most preferably. Is 7 or less.

  Preferably, the nematic phase of the medium of the present invention is at least 0 ° C. or lower to 80 ° C. or higher, more preferably at least −20 ° C. or lower to 80 ° C. or higher, most preferably at least −30 ° C. or lower to 80 ° C. or higher, particularly Is at least −40 ° C. to 90 ° C.

  Preferably the liquid crystal medium comprises one or more compounds of formula I, II, III, IV, V and VI, preferably of formula I, II, III and IV, 50% to 100% of the total amount, more preferably 70% to 100%, more preferably 80% to 100%, particularly 90% to 100%.

  More preferably, the liquid crystal medium comprises one or more compounds of formulas I, II, III, IV, V and VI, preferably of formulas I, II, III and IV, more preferably consisting mostly of these. More preferably consisting essentially of these, most preferably all consisting of them.

  The compound of formula I is preferably in the medium at a total concentration of 1% to 30%, more preferably 2% to 20%, more preferably 2% to 15%, most preferably 3% to 12% of the total mixture. Used in.

  According to a preferred embodiment of the present invention, the compound of formula I is preferably used at a total concentration of 1% to 20% of the total mixture, more preferably 2% to 15%, most preferably 3% to 12%. Is done.

  Compounds of formula II and III are preferably at a total concentration of 15% to 55% of the total mixture, more preferably 20% to 50%, more preferably 25% to 45%, most preferably 30% to 40%. Used in the medium.

  The compound of formula II is preferably in the medium at a total concentration of 1% to 40%, more preferably 2% to 30%, more preferably 3% to 20%, most preferably 5% to 15% of the total mixture. Used in.

  The compound of formula III is preferably in the medium at a total concentration of 5% to 45%, more preferably 10% to 40%, more preferably 15% to 35%, most preferably 20% to 30% of the total mixture. Used in.

  The compound of formula IV is preferably in the medium at a total concentration of 20% to 75%, more preferably 30% to 70%, more preferably 40% to 65%, most preferably 50% to 70% of the total mixture. Used in.

  The compound of formula V is preferably in the medium at a total concentration of 0% to 30%, preferably 1% to 30%, more preferably 5% to 20%, most preferably 10% to 20% of the total mixture. used.

  The compound of formula VI is preferably used in the medium at a total concentration of 0% to 30%, preferably 0% to 15%, most preferably 1% to 10% of the total mixture.

  Optionally, the medium according to the invention can further comprise a liquid crystal compound in order to adjust the physical properties. Such compounds are known to the expert. Their concentration in the medium according to the invention is preferably 0% to 30%, more preferably 0.1% to 20%, most preferably 1% to 15%.

Preferably, the medium according to the invention is
Formula II-1-c-1, preferably Formula PUQU-nF; and / or Formula III-1a, preferably Formula III-1a-1 and / or III-1a-4; and / or Formula III-1g, preferably of formula III-1g-3 and / or III-1g-4 and / or III-1g-5, more preferably of formula PGU-n-F and / or GGP-n-F and / or GGP -N-CL; and / or Formula III-1h, preferably Formula III-1h-3; and / or Formula IV-1, preferably CCP-Vn and / or CCP-V2-n and / or Or CCP-nV2-m, more preferably the formula CCP-V-1 and / or CCP-V2 and / or CCP-V2-1 and / or CCP-V2-2 and / or And CCP-1V2-1; and / or Formula IV-5, preferably Formula CC-n-V and / or CC-n-Vm, more preferably Formula CC-3-V and / or CC-4-V. And / or CC-5-V and / or CC-3-V1; and / or Formula IV-11, preferably formula CPPC-nn and / or CGPC-nm, more preferably formula CPPC-3. -3 and / or CPPC-5-3 and / or CPPC-5-5 and / or CGPC-3-3 and / or CGPC-5-3 and / or CPGC-5-5;
One or more compounds.

  In this application, the term “dielectrically positive” means that the compound or component is Δε> 3.0, and the term “dielectrically neutral” is −1.5 ≦ Δε ≦ 3.0. That is, the term “dielectrically negative” means that Δε <−1.5, where Δε is determined at a frequency of 1 kHz and 20 ° C. The dielectric anisotropy of each compound is determined from the results of a 10% solution of each individual compound in the nematic host mixture. When the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The volume of the test mixture is determined in both cells having a homeotropic orientation and cells having a homogeneous orientation. The cell spacing of both types of cells is approximately 20 μm. The applied voltage is a square wave with a root mean square value typically between 0.5 V and 1.0 V at room temperature at a frequency of 1 kHz, however, always selected below the capacity threshold of the respective test mixture. Is done.

Δε is defined as (epsilon _{||-epsilon ⊥),} whereas, epsilon _av is defined as (epsilon _|| + 2ε _⊥) / 3.

  For dielectrically positive compounds, mixture ZLI-4792 is used as the host mixture for dielectrically neutral and dielectrically negative compounds, respectively, both as host mixtures, both from Merck, Germany It is. The dielectric constant of the compound is determined from the change in the respective value of the host mixture upon addition of the compound of interest. Extrapolate that value to 100% concentration of the compound of interest.

  The component having the nematic phase at the measurement temperature of 20 ° C. is measured as it is, and all the others are treated in the same manner as the compound measurement.

In this application, the term “threshold voltage” means optical threshold, unless otherwise stated, and is given for 10% relative contrast (V ₁₀ ), and the term “saturation voltage” means optical saturation. Is given for 90% relative contrast (V ₉₀ ). The capacitive threshold voltage (V ₀ ), also called the Fredericks threshold (V _Fr ), is used only when explicitly stated.

  The ranges of parameters given in this application all include limit values unless explicitly stated otherwise.

Throughout this application, unless stated otherwise, all concentrations are given in weight percent and relate to each complete mixture, all temperatures are given in degrees Celsius, and all temperature differences are also Given in degrees Celsius. All physical properties are determined or determined by “Merck Liquid Crystals, Physical Properties of Liquid Crystals” November 1997, Merck, Germany, and are given for a temperature of 20 ° C. unless otherwise stated . The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltage, as well as all other electro-optical properties, were determined by a test cell prepared by Merck, Germany. The test cell for the determination of Δε had a cell spacing of about 20 μm. The electrode was a circular ITO electrode with an area of 1.13 cm ² and a guard ring. The alignment layer was lecithin for homeotropic alignment (ε _‖ ) and polyimide AL-1054 made by Nippon Synthetic Rubber Co. for homogeneous alignment (ε _⊥ ). The capacity was determined by a frequency response analyzer Solatron 1260 using a sine wave having a voltage of 0.3 V _rms . The light used in the electro-optic measurement was white light. The equipment configuration used was a commercially available equipment from the company Atlantic Melchers, Germany. The characteristic voltage was determined under vertical observation. The threshold (V ₁₀ ) -medium gray (V ₅₀ )-and saturation (V ₉₀ ) voltages were determined at 10%, 50% and 90% relative contrast, respectively.

  The liquid crystal medium according to the present invention can further contain additives and chiral dopants in conventional concentrations. The total concentration of these further components ranges from 0% to 10%, preferably from 0.1% to 6%, based on the total mixture. The concentration of each individual compound used is preferably in the range of 0.1% to 3%. The concentrations of these and similar additives are not considered in the concentration values and ranges of the liquid crystal components and compounds of the liquid crystal media of the present application. This is also true for the concentration of the dichroic dye used in the mixture and is not taken into account when the concentration of the compounds and components of the host mixture is specified respectively. The concentration of each additive is always given for the final doped mixture.

  The liquid crystal medium of the present invention according to the present invention consists of several compounds, preferably 3-30, more preferably 4-20, and most preferably 4-16. These compounds are mixed in a conventional manner. As a rule, the required amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. It is particularly easy to observe the completion of the dissolution process when the temperature is above the clearing point of the compound used at higher concentrations. However, the medium is prepared by other conventional methods, such as the use of so-called pre-mixtures which can be homologous compound mixtures or eutectic mixtures, or so-called multi-bottle systems where the components themselves are ready to use. You can also

  By using appropriate additives, displays that use liquid crystal media as they are, such as TN, TN-AMD, ECB-AMD, VAN-AMD, IPS-AMD, FFS-AMD LCD, or PDLC, NCAP, PN LCD In particular, the liquid crystal medium according to the invention can be modified so that it can be used in all known liquid crystal displays, such as displays that use liquid crystal media in composite systems, such as ASM-PA LCD.

  The melting point T (C, N) of the liquid crystal, the transition T (S, N) from the smectic phase (S) to the nematic (N) phase, and the clearing point T (N, I) are given in degrees Celsius.

  In the present application and particularly in the following examples, the structure of the liquid crystal compound is represented by an abbreviation also referred to as “acronym”. The conversion from the abbreviation to the corresponding structure is performed uniquely according to the following three tables A to C.

All the groups C _n H _{2n + 1} , C _m H _{2m + 1} and C ₁ H _{2l + 1} are each preferably a straight-chain alkyl group with n, m and l carbon atoms, —CH═CH— is preferably trans, Each is E vinylene.

  Table A lists symbols used for ring structure elements, Table B lists symbols used for linking groups, and Table C lists symbols used for the left and right terminal groups of the molecule.

  Table D lists examples of molecular structures along with their respective codes.

式中、ｎおよびｍはそれぞれ整数であり、３つの点「．．．」は、この表の他の記号のためのスペースを表す。

Where n and m are each integers, and the three points "..." represent space for other symbols in this table.

  Preferably, the liquid-crystalline medium according to the invention comprises, in addition to the compound of formula I, one or more compounds selected from the group of compounds of the formulas in the table below.

表Ｅに、本発明による液晶媒体中で好ましくは使用されるキラルドーパントを列記する。

Table E lists the chiral dopants that are preferably used in the liquid crystal media according to the invention.

本発明の好ましい実施形態において、本発明による媒体は、表Ｅの化合物群より選択される１種類以上の化合物を含む。

In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds selected from the group of compounds of Table E.

  Table F lists the stabilizers preferably used in the liquid crystal medium according to the invention.

本発明の好ましい実施形態において、本発明による媒体は、表Ｆの化合物群より選択される１種類以上の化合物を含む。

In a preferred embodiment of the invention, the medium according to the invention comprises one or more compounds selected from the group of compounds in Table F.

The liquid crystal medium according to the invention is preferably: 4 or more, preferably 6 or more, preferably 6 or more, preferably selected from the group of compounds in Table D,
7 or more, preferably 8 or more compounds selected from the group of formulas in Table D, preferably containing 3 or more different compounds of different formulas.

  The examples given below illustrate the invention without limiting it in any way.

  However, physical properties and composition explain to the expert what properties can be achieved and to what extent they can be varied. Thus, in particular, the combination of the various properties that can preferably be achieved is well defined for the expert.

<Example 1>
A liquid crystal mixture of the composition and properties given in the table below is realized.

この混合物は、ＩＰＳ−およびＦＦＳ−モード中で動作するディスプレイ、特に携帯用の用途に良く適している。

This mixture is well suited for displays operating in IPS- and FFS-modes, especially for portable applications.

<Example 2>
A liquid crystal mixture of the composition and properties given in the table below is realized.

この混合物は、ＩＰＳ−およびＦＦＳ−モード中で動作するディスプレイ、特に携帯用の用途に良く適している。

This mixture is well suited for displays operating in IPS- and FFS-modes, especially for portable applications.

Claims (9)

1% to 35% by weight of one or more compounds of the formula I,
• 15% to 55% by weight of one or more compounds selected from the group of compounds of the formulas II and III, provided that at least the compounds of the formulas III-1g-4, III-1g-5 and III-1h-3 One or more compounds selected from the group consisting of :
- 20 mass% to 75 weight% of one or more compounds of the formula IV (with the proviso that at least comprises one or more compounds selected from the group consisting of the compounds of formula IV-9.) And a (however, The total concentration of the compounds of formulas I, II, III and IV is not more than 100% by weight.) Liquid crystal medium.

(Where
R ¹¹ and R ¹² are each independently alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl. )

(Where
R ² and R ³ are each independently of each other alkyl of 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl of 2 to 7 carbons, alkenyloxy, alkoxyalkyl or Fluorinated alkenyl,

L ²¹ , L ²² , L ³¹ and L ³² are each independently H or F,
X ² and X ³ are each independently of each other halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms, or halogenated alkenyl or alkenyloxy having 2 or 3 carbon atoms,
Z ³ _{is, -CH 2 CH 2 -, -} CF 2 CF 2 -, - COO-, trans -CH = CH-, trans -CF = CF -, - a _CH 2 O- or a single bond, and l, m, n, and o are each independently 0 or 1, )

(Wherein R ³ has the meaning given above.)

(Wherein R ³ has the meaning given above.)

(Where
R ⁴¹ and R ⁴² each independently of one another have the meaning given for R ² in formula II above,

Z ⁴¹ and Z ⁴² are each independently of each other, and when Z ⁴¹ is present twice, they are also each independently of each other, —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, trans _{-CF = CF -, - CH 2} O -, - CF 2 O -, - C≡C- or a single bond, and p, Ri 0, 1 or 2 der,
However, compounds of formulas II and III are excluded from compounds of formula IV . )

(Where
R ⁴¹ and R ⁴² each independently represent alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated. Alkenyl
L ⁴ is H or F. ) The liquid crystal medium according to claim 1, wherein the compound of formula I is selected from the group of compounds of formulas I-1 to I-4.

(Where
R ¹² has the meaning given in claim 1 in formula I. ) 3. Liquid crystal medium according to claim 1 or 2 , comprising one or more compounds of the formula II as given in claim 1. Liquid crystal medium according to any one of claims 1 to 3 , comprising one or more compounds of the formula III as given in claim 1. The liquid crystal medium according to any one of claims 1 to 4, additionally comprising one or more compounds of the formula V.

(Where
R ⁵ is alkyl having 1 to 7 carbons, alkoxy, fluorinated alkyl or fluorinated alkoxy, alkenyl having 2 to 7 carbons, alkenyloxy, alkoxyalkyl or fluorinated alkenyl, Preferably, it is alkyl or alkenyl,

L ⁵¹ and L ⁵² are each independently H or F,
X ⁵ is halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms, or halogenated alkenyl or alkenyloxy having 2 or 3 carbon atoms,
Z ⁵ _{is, -CH 2 CH 2 -, -} CF 2 CF 2 -, - COO-, trans -CH = CH-, trans -CF = CF- or _-CH 2 is O-, and q is 0 or 1. ) The liquid crystal medium according to any one of claims 1 to 5 containing one or more compounds of formula VI additionally.

(Where
R ⁶¹ and R ⁶² each independently of one another have the meaning given to R ² in formula II in claim 1;

Z ⁶¹ and Z ⁶² are each independently of each other, and when Z ⁶¹ is present twice, they are each independently of each other, —CH ₂ CH ₂ —, —COO—, trans—CH═CH—, trans —CF═CF—, —CH ₂ O—, —CF ₂ O—, —C≡C— or a single bond, and r is 0, 1 or 2. ) The liquid crystal display containing the liquid-crystal medium as described in any one of Claims 1-6 . 8. A liquid crystal display according to claim 7 , which is addressed by an active matrix. Use of the liquid crystal medium according to any one of claims 1 to 6 in a liquid crystal display.