JP2011517464A - Liquid crystal media - Google Patents

Abstract

（式中、パラメータは請求項１において示される意味を有する。）
【選択図】なしA liquid crystal medium is provided.
The present invention relates to a) a first dielectrically negative component (component A) comprising one or more dielectrically negative compounds (one or more) of formula (I), b ) A dielectric negative liquid crystal medium having a second dielectric negative component (component B) comprising one or more dielectric negative compounds (one or more) of formula (II). The invention further relates to the use of liquid crystal media in electro-optic displays, in particular in active matrix displays based on VA, ECB, PALC, FFS or IPS effects, and such displays.

(Wherein the parameters have the meaning indicated in claim 1).
[Selection figure] None

Description

  The present invention provides a liquid crystal medium and its use in liquid crystal displays, and in particular these liquid crystal displays, in particular the ECB (Electrically Controlled Birefringence) effect with dielectrically negative liquid crystals whose initial orientation is homeotropic. The present invention relates to a liquid crystal display to be used. The liquid crystal medium according to the invention stands out because of the particularly short response time and at the same time a high voltage holding ratio in the display according to the invention.

  A display using the ECB effect is a so-called VAN (Vertical Aligned Nematic) display, an IPS (In-Plane Switching) display (for example: Yeo, SD, paper 15.3: “ An LC Display for the TV Application ", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pages 758 and 759 (Nt. In addition to displays, more recent of the most important liquid crystal displays at present It has been established as one of three types, particularly for television applications.

  The most important designs that must be mentioned are: MVA {multidomain vertical alignment; Multi-Domain Vertical Alignment, eg: Yoshihide, H. et al. Et al., 3.1: “MVA LCD for Notebook or Mobile PCs (hereinafter abbreviated)” SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pages 6 to 9 (Non-Patent Documents 2 to 9) . T.A. 15.1 “A46-inch TFT-LCD HDTV Technology (hereinafter omitted)”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pages 750 to 753} (Non-patent Document 3) PVA {Patterned Vertical Alignment; Patterned Vertical Alignment, eg: Kim, Sang Soo, Paper 15.4: "Super PVA Sets New State-of-the-Art for LCD DTV", SID 2004 InternationalTyp , XXXV, Book II, pages 760 to 763 (non- Patent Document 4)} and ASV {Advanced Super Field of View; Advanced Super View, eg: Shigeta, Mitzuhiro and Fukuoka, Hirofumi, Paper 15.2: "Development of High quat iD, D empir of High 200 ft. , Book II, pp. 754-757 (Non-patent Document 5)}.

  In general terms, these techniques are, for example, SID seminars at Souk in June 2004, Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6 / 1 to M-6 / 26 (Non-Patent Document 6) and Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7 / 1 to M-7 / 32 (Non-Patent Document 7) Has been. For example: Kim, Hyeon Kyeong et al., Paper 9.1: “A57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XX106, XX Although the response time of recent ECB displays has already been significantly improved by the addressing method by overdrive as in Patent Document 8), achieving a response time corresponding to video can be achieved particularly in switching of halftones. It is still a problem that has not been solved to a satisfactory extent.

  TN and all conventional IPS displays until now use liquid crystal media with positive dielectric anisotropy, whereas ECB displays such as ASV displays use liquid crystal media with negative dielectric anisotropy (Δε) To do.

  In this type of liquid crystal display, liquid crystal is used as a dielectric, and its optical characteristics change reversibly when a voltage is applied.

  In general, in the display, that is, also in the display according to the effects described above, since the operating voltage must be as low as possible, in general, all have the same sign of dielectric anisotropy and are as high as possible. A liquid crystal medium mainly composed of a liquid crystal compound having a dielectric anisotropy is used. In general, a relatively small proportion of neutral compound is used, and if possible, a compound having a dielectric anisotropy of the opposite sign to the medium is not used. Therefore, in the case of a liquid crystal medium having a negative dielectric anisotropy for an ECB display, most use a compound having a negative dielectric anisotropy. The liquid crystal media utilized generally consist mostly of liquid crystal compounds with negative dielectric anisotropy, usually more essentially.

  In the medium used by this application, a liquid crystal display having the lowest possible address voltage is generally intended, so at most a considerable amount of dielectrically neutral liquid crystal compound is used, Only very small amounts of dielectrically positive compounds are used, and more typically none.

  Prior art liquid crystal media with correspondingly low address voltages have relatively low electrical resistance values or low voltage holding ratios, often resulting in undesirable flicker and / or inadequate transmission in the display. .

  In addition, in many cases, the address voltage of prior art displays is particularly large for displays that are not directly or permanently connected to a power supply system such as, for example, a display for portable applications.

  In addition, the phase range must be wide enough for the intended application.

In particular, the response time of the liquid crystal medium in the display must be improved, i.e. shortened. This is particularly important in displays for television and multimedia applications. In order to improve the response time, it has been repeatedly proposed in the past to optimize the rotational viscosity (γ ₁ ) of the liquid crystal medium, ie to achieve a medium with the lowest possible rotational viscosity. However, the results achieved here are in many cases inappropriate for the application and therefore it seems desirable to find further optimization techniques.

  Accordingly, there is a great demand for liquid crystal media that do not have the disadvantages of the media from the prior art, or at least have been significantly reduced.

  Surprisingly, it has been found that liquid crystal displays can be achieved which have a short response time in an ECB display and at the same time have a sufficiently wide nematic phase, a preferred birefringence (Δn) and a high voltage holding ratio.

  This type of medium is used in particular for electro-optic displays with active-matrix addresses based on the ECB effect and for IPS (In-Plane Switching) displays. The medium according to the invention preferably has a negative dielectric anisotropy.

  The principle of electrically controlled birefringence, ie ECB (Electrically Controlled Birefringence) effect or DAP (deformation of aligned phases) effect was first described in 1971 (MF Schiekel and K. Fahrenschon, “Deformation of nematic liquids with vertical orientations”, Appl. Phys. Lett., 1991 (1971). After that, J.H. F. Kahn (Appl. Phys. Lett. 20 (1972), 1193 (Non-Patent Document 10)) and G. Labrunie and J.M. The report by Robert (J. Appl. Phys. 44 (1973), 4869 (Non-patent Document 11)) continued.

J. et al. Robert and F.M. Clerc (SID 80 Digest Techn. Papers (1980), 30 (Non-patent Document 12)), J. Am. Duchene (Displays 7 (1986), 3 (Non-Patent Document 13)) and H.C. According to a report by Schad (SID 82 Digest Techn. Papers (1982), 244 (Non-Patent Document 14)), in order to be suitable for use for a high information content display element based on the ECB effect, Was shown to have a high value of the elastic constant ratio K ₃ / K ₁ , a high value of optical anisotropy Δn, and a dielectric anisotropy value Δε of −0.5 or less. . Electro-optical display elements based on the ECB effect have a homeotropic edge orientation (VA technology: Vertically Aligned). Dielectrically negative liquid crystal media can also be used in displays that use the so-called IPS effect.

  In order to apply this effect industrially in an electro-optic display element, a liquid crystal medium is required which must satisfy a number of requirements. Here, chemical stability against physical effects such as moisture, air and heat, radiation in the infrared, visible and ultraviolet regions, direct current and alternating electric fields is of particular importance.

  Furthermore, an LC phase that can be used industrially needs to have a liquid crystal mesophase and a low viscosity in a suitable temperature range.

  The series of compounds having a liquid crystal mesophase disclosed to date does not include a single compound that satisfies all these requirements. Therefore, in order to obtain a substance that can be used as the LC phase, a mixture of 2 to 25 compounds, preferably 3 to 18 compounds, is generally prepared.

  Matrix liquid crystal displays (MLC displays) are known. Non-linear elements that can be used to switch each individual pixel are, for example, active elements (ie, transistors). The term “active matrix” is used, but a thin film transistor (TFT) generally disposed on a glass plate as a substrate is generally used.

  A distinction is made between two technologies: TFTs comprising compound semiconductors such as CdSe, or TFTs based on polycrystalline, especially amorphous silicon. Currently, the latter technique is the most commercially important in the world.

  The TFT matrix is formed on the inner surface of one glass plate of the display, while the other glass plate has a transparent counter electrode on its inner surface. Compared to the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technique can also be applied to a full-color display, in which a mosaic of red, green and blue filters is arranged so that the filter element faces each switchable pixel.

  The TFT displays that have been most used to date usually operate transmissively with orthogonal polarizers and are backlit. IPS cells or ECB (or VAN) cells are used for television applications, while monitors typically use IPS cells or TN cells, while laptops, laptops and portable applications are usually TN cells. Is used.

  As used herein, the term MLC display comprises any matrix display with integrated nonlinear elements, ie, passive elements such as varistors or diodes (MIM, ie metal-insulator-metal) in addition to the active matrix. The display is also covered.

  This type of MLC display is particularly suitable for television applications, monitors and notebook computers, or high density information displays, for example, in automobile manufactures or aircraft. In addition to problems with contrast angular dependence and response time, problems arise in MLC displays because the specific resistance of the liquid crystal mixture is not high enough [TOGASHHI, S .; SEKIGUCHI, K.K. TANABE, H .; , YAMAMOTO, E.I. , SORIMACHI, K.K. TAJIMA, E.I. WATANABE, H .; SHIMIZU, H .; Proc. Eurodisplay, Vol. 84, September 1984, A210-288, “Matrix LCD Controlled by Double Stage Diode Rings”, page 141ff, Paris, (Non-patent Document 15); Proc. Eurodisplay, Vol. 84, September 1984, “Design of Thin Film Transistors for Matrix Addressing of Television Liquid Displays”, pp. 145ff, Paris, 145ff. As the resistance decreases, the contrast of the MLC display deteriorates. The specific resistance of the liquid crystal mixture generally decreases over the lifetime of the MLC display due to interaction with the internal surface of the display, so for displays that must have an acceptable resistance over a long period of operation. High (initial) resistance is very important.

  The compounds of formula I in combination with practically dielectrically neutral indanes are described, for example, in JP 2005-047980 A (Patent Document 1) as components of liquid crystal mixtures. Examples of indane having negative dielectric anisotropy include, for example, German Patent Application Publication No. 101 35 499 (Patent Document 2), German Patent Application Publication No. 103 54 404 (Patent Document 3), and German Patents. This is disclosed in Japanese Patent Application No. 10 2004 046 103 (Patent Document 4).

  The disadvantages of the MLC displays disclosed so far are their relatively low contrast, relatively high viewing angle dependence, and the difficulty in producing halftones in these displays, as well as their inadequate Based on voltage holding ratios and their poor lifetime.

  Thus, it has a very high specific resistance and at the same time has a wide operating temperature range, a short response time and a low threshold voltage, which can give rise to various gray levels, in particular good and There is a continuing strong demand for MLC displays with stable voltage holding ratios.

JP 2005-047980 A German Patent Application Publication No. 101 35 499 German Patent Application Publication No. 103 54 404 German Patent Application Publication No. 10 2004 046 103

Yeo, S .; D. , Paper 15.3: “A LC Display for the TV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, 758 and 759. Yoshihide, H.C. Et al., 3.1: “MVA LCD for Notebook or Mobile PCs (hereinafter abbreviated)” SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6-9. Liu, C.I. T.A. 15.1 “A46-inch TFT-LCD HDTV Technology (hereinafter omitted)”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, 750-753. Kim, Sang Soo, Paper 15.4: “Super PVA Sets New State-of-the-Art for LCD-TV”, SID 2004 International Symposium, Digest of Technical Papers B, X 76, X. Shigeta, Mitzhiro and Fukuoka, Hirofumi, Paper 15.2: “Development of High Quality LCDTV”, SID 2004 International Symposium, DiXestVX 75, Digest of Tech 7 Seminar M-6: “Recent Advances in LCD Technology”, Seminar Lecture Notes, M-6 / 1 to M-6 / 26 Miller, Ian, SID Seminar 2004, Seminar M-7: “LCD-Television”, Seminar Lecture Notes, M-7 / 1 to M-7 / 32 Kim, Hyeon Kyeong et al., Paper 9.1: “A57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXV 109, XXV M.M. F. Schieckel and K.C. Fahrenshon, “Deformation of nematic liquids with vertical orientation in electrical fields”, Appl. Phys. Lett. Volume 19 (1971), page 3912 J. et al. F. Kahn, Appl. Phys. Lett. Volume 20 (1972), page 1193 G. Labrunie and J.M. Robert, J.M. Appl. Phys. 44 (1973), 4869 J. et al. Robert and F.M. Clerc, SID 80 Digest Techn. Papers (1980), 30 J. et al. Duchene, Displays 7 (1986), 3 H. Schad, SID 82 Digest Techn. Papers (1982), 244 TOGASHHI, S.A. SEKIGUCHI, K.K. TANABE, H .; , YAMAMOTO, E.I. , SORIMACHI, K.K. TAJIMA, E.I. WATANABE, H .; SHIMIZU, H .; Proc. Eurodisplay, 84, September 1984, A210-288, “Matrix LCD Controlled by Double Stage Diode Rings”, page 141ff, Paris STROMER, M.M. Proc. Eurodisplay, Volume 84, September 1984, “Design of Thin Film Transistors for Matrix Addressing of Television Liquid Displays”, page 145ff.

  The present invention is not only for monitor and television applications, but also for mobile phones and navigation systems, and is based on the ECB or IPS effect and does not have the above-mentioned defects or only to a reduced extent. At the same time, it aims to provide an MLC display having a very high specific resistance value. In particular, the display must be guaranteed to function at very high and very low temperatures for mobile phones and navigation systems.

  It has now surprisingly been found that in these display elements this object can be achieved if a nematic liquid crystal mixture comprising at least one compound of formula I and at least one compound of formula II is used.

  The invention thus relates to a liquid-crystalline medium based on a mixture of polar compounds comprising at least one compound of formula I and at least one compound of formula II.

  The mixtures according to the invention have a very wide nematic phase range with a clearing point above 85 ° C., a very favorable value of the capacity threshold, a relatively high value retention and at the same time very good low temperatures at −30 ° C. and −40 ° C. It exhibits stability as well as very low rotational viscosity. Furthermore, the mixtures according to the invention are distinguished by a good ratio of clearing point and rotational viscosity and a large negative dielectric anisotropy.

The present invention
a) a first dielectrically negative component (component A), preferably consisting of one or more compounds of formula I;
b) a second dielectrically negative component (component B) consisting of one or more compounds of formula II, and c) optionally a dielectrically neutral compound consisting of one or more compounds of formula III Component (component C), and d) as an optional component, a further dielectrically negative component (component D) consisting of one or more compounds selected from the group of compounds of the formulas IV and V, and e) optional The present invention relates to a dielectrically negative nematic containing a chiral component (component E) comprising at least one chiral compound as a component.

式中、
Ｒ^１１およびＲ^１２は、それぞれ互いに独立に、Ｈ、１５個までのＣ原子を有する無置換のアルキルまたはアルケニル基を表し、ただし加えて、これらの基における１個以上のＣＨ_２基は、Ｏ原子が互いに直接結合しないようにして、−Ｏ−、−Ｓ−、

Where
R ¹¹ and R ¹² each independently represent H, an unsubstituted alkyl or alkenyl group having up to 15 C atoms, but in addition, one or more CH ₂ groups in these groups are O The atoms are not directly bonded to each other so that -O-, -S-,

−Ｃ≡Ｃ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−、−ＣＯ−Ｏ−または−Ｏ−ＣＯ−で置き換えられていてもよく、好ましくは、無置換のアルキル、アルケニル、アルコキシまたはアルケニルオキシ基を表し、特に好ましくは、Ｒ^１１およびＲ^１２の一方はアルキルまたはアルケニル基を表し、他方は、アルキル、アルケニル、アルコキシまたはアルケニルオキシ基を表し、特に好ましくは、Ｒ^１１は直鎖状のアルキルまたはアルケニル、特に、ＣＨ_２＝ＣＨ−、Ｅ−ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_２＝ＣＨ−ＣＨ_２−ＣＨ_２−、ＣＨ_３−ＣＨ＝ＣＨＣ_２Ｈ_４−、ＣＨ_３−、Ｃ_２Ｈ_５−、ｎ−Ｃ_３Ｈ_７−、ｎ−Ｃ_４Ｈ_９−またはｎ−Ｃ_５Ｈ_１１−を表し、Ｒ^１２はアルコキシ、特に、Ｃ_２Ｈ_５−Ｏ−またはｎ−Ｃ_４Ｈ_９−Ｏ−を表し、

—C≡C—, —CF ₂ —O—, —O—CF ₂ —, —CO—O— or —O—CO— may be substituted, preferably unsubstituted alkyl, alkenyl, alkoxy Or an alkenyloxy group, particularly preferably one of R ¹¹ and R ¹² represents an alkyl or alkenyl group, the other represents an alkyl, alkenyl, alkoxy or alkenyloxy group, particularly preferably R ¹¹ represents a straight chain Alkyl or alkenyl in particular, CH ₂ ═CH—, E—CH ₃ —CH═CH—, CH ₂ ═CH—CH ₂ —CH ₂ —, CH ₃ —CH═CHC ₂ H ₄ —, CH ₃ — _{, C 2 H 5 -, n} -C 3 H 7 -, n-C 4 H 9 - or _{n-C 5 H 11} - ^{represents, R 12} is alkoxy, _{particularly,} C ₂ H 5 -O-, or n- C ₄ H ₉ —O—

および、他は、存在するのであれば、それぞれ互いに独立に、

And others, if present, are independent of each other,

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

非常に特に好ましくは、

Very particularly preferably,

を表し、
Ｚ^１１〜Ｚ^１３は、それぞれ互いに独立に、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＨ_２−Ｏ−、−Ｏ−ＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−、−ＣＦ_２−ＣＦ_２−または単結合、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−または単結合を表し、特に好ましくは、１つ、または存在するのであれば、それより多くのＺ^１１〜Ｚ^１３が単結合を表し、非常に特に好ましくは、Ｚ^１１〜Ｚ^１３の全てが単結合を表し、
ｍおよびｎは、それぞれ互いに独立に、０または１を表し、および
（ｍ＋ｎ）は、好ましくは、０または１、非常に好ましくは、０を表す。

Represents
Z ^{11 to} Z ¹³ are each independently of each other —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —CO—O. _{-, - O-CO -,} - CF 2 -O -, - O-CF 2 -, - CF 2 -CF 2 - or a single bond, _{preferably, -CH 2 -CH 2 -, -} CH = CH-, —C≡C—, —CF ₂ —O—, —O—CF ₂ — or a single bond, particularly preferably one or more Z ^{11 to} Z ¹³ if present, is a single bond. Represents a bond, very particularly preferably all of Z ^{11 to} Z ¹³ represent a single bond,
m and n each independently represent 0 or 1, and (m + n) preferably represents 0 or 1, very preferably 0.

式中、
Ｒ^２１およびＲ^２２は、それぞれ互いに独立に、Ｈ、１５個までのＣ原子を有する無置換のアルキルまたはアルケニル基を表し、ただし加えて、これらの基における１個以上のＣＨ_２基は、Ｏ原子が互いに直接結合しないようにして、−Ｏ−、−Ｓ−、

Where
R ²¹ and R ²² , independently of one another, represent H, an unsubstituted alkyl or alkenyl group having up to 15 C atoms, but in addition, one or more CH ₂ groups in these groups are O The atoms are not directly bonded to each other so that -O-, -S-,

−Ｃ≡Ｃ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−、−ＣＯ−Ｏ−または−Ｏ−ＣＯ−で置き換えられていてもよく、好ましくは、無置換のアルキル、アルケニル、アルコキシまたはアルケニルオキシ基を表し、特に好ましくは、Ｒ^２１およびＲ^２２の一方はアルキルまたはアルケニル基を表し、他方は、アルキル、アルケニル、アルコキシまたはアルケニルオキシ基、好ましくは、互いに独立に、１〜７個のＣ原子を有するアルキル、好ましくは、ｎ−アルキル、特に好ましくは、１〜５個のＣ原子を有するｎ−アルキル、１〜７個のＣ原子を有するアルコキシ、好ましくは、ｎ−アルコキシ、特に好ましくは、１〜５個のＣ原子を有するｎ−アルコキシ、または、２〜７個のＣ原子を有する、好ましくは、２〜４個のＣ原子を有するアルコキシアルキル、アルケニルまたはアルケニルオキシ、好ましくは、アルケニルを表し、ただし、全ての基において１個以上のＨ原子はハロゲン原子、好ましくは、Ｆ原子で置き換えられていてもよく、
特に好ましくは、Ｒ^２１およびＲ^２２の一方、好ましくは、Ｒ^２１がアルキルまたはアルケニル基を表し、他方が、アルキル、アルケニル、アルコキシまたはアルケニルオキシ基を表し、特に好ましくは、Ｒ^２１は直鎖状のアルキル、特に、ＣＨ_３−、Ｃ_２Ｈ_５−、ｎ−Ｃ_３Ｈ_７−、ｎ−Ｃ_４Ｈ_９−またはｎ−Ｃ_５Ｈ_１１−、またはアルケニル、特に、ＣＨ_２＝ＣＨ−、Ｅ−ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_２＝ＣＨ−ＣＨ_２−ＣＨ_２−、Ｅ−ＣＨ_３−ＣＨ＝ＣＨ−ＣＨ_２−ＣＨ_２−またはＥ−ｎ−Ｃ_３Ｈ_７−ＣＨ＝ＣＨ−を表し、

—C≡C—, —CF ₂ —O—, —O—CF ₂ —, —CO—O— or —O—CO— may be substituted, preferably unsubstituted alkyl, alkenyl, alkoxy Or an alkenyloxy group, particularly preferably one of R ²¹ and R ²² represents an alkyl or alkenyl group and the other is an alkyl, alkenyl, alkoxy or alkenyloxy group, preferably 1-7 independently of each other Alkyl, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5 C atoms, alkoxy having 1 to 7 C atoms, preferably n-alkoxy, especially Preferably n-alkoxy having 1 to 5 C atoms or 2 to 7 C atoms, preferably 2 to 4 C atoms Kishiarukiru, alkenyl or alkenyloxy, preferably alkenyl, provided that one or more H atoms of the halogen atom in all groups, preferably, may be replaced by F atoms,
Particularly preferably, one of R ²¹ and R ²² , preferably R ²¹ represents an alkyl or alkenyl group and the other represents an alkyl, alkenyl, alkoxy or alkenyloxy group, particularly preferably R ²¹ is linear alkyl, in _{particular, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, n-C 4 H 9 - or _{n-C 5 H 11} -, or alkenyl, _especially, CH 2 = CH-, E—CH ₃ —CH═CH—, CH ₂ ═CH—CH ₂ —CH ₂ —, E—CH ₃ —CH═CH—CH ₂ —CH ₂ —, or En—C ₃ H ₇ —CH═CH -

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

および、他方は、存在するのであれば、それぞれ互いに独立に、

And the other, if present, are independent of each other,

を表し、
Ｌ^２１およびＬ^２２は、互いに独立に、＝Ｃ（Ｘ^２）−を表し、Ｌ^２１およびＬ^２２の一方は、二者択一的に、＝Ｎ−も表し、ただし、好ましくは、Ｌ^２１およびＬ^２２の少なくとも一方が＝Ｃ（−Ｆ）−を表し、他方が＝Ｃ（−Ｆ）−または＝Ｃ（−Ｃｌ）−を表し、特に好ましくは、、Ｌ^２１およびＬ^２２の両者が＝Ｃ（−Ｆ）−を表し、
Ｘ^２は、Ｆ、Ｃｌ、ＯＣＦ_３、ＣＦ_３、ＣＨ_３、ＣＨ_２Ｆ、ＣＨＦ_２、好ましくは、ＦまたはＣｌ、特に好ましくは、Ｆを表し、

Represents
L ²¹ and L ²² independently of each other represent ═C (X ² ) —, and one of L ²¹ and L ²² alternatively represents ═N—, but preferably L ²¹ And at least one of L ²² represents = C (-F)-and the other represents = C (-F)-or = C (-Cl)-, and particularly preferably, both of L ²¹ and L ²² are = C (-F)-
X ² represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ , preferably F or Cl, particularly preferably F,

好ましくは、

Preferably,

を表してもよく、
特に好ましくは、

May represent
Particularly preferably,

ただし、

However,

を表す場合、好ましくは、Ｒ^２２はＨを表し、
Ｚ^２１〜Ｚ^２３は、それぞれ互いに独立に、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＦ_２−、−ＣＦ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ_２−Ｏ−、−Ｏ−ＣＨ_２−、−Ｏ−、−ＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−または単結合、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−または単結合を表し、特に好ましくは、１つ、または存在するのであれば、それより多くのＺ^２１〜Ｚ^２３は単結合を表し、非常に特に好ましくは、全てが単結合を表し、
ｌおよびｏは、それぞれ互いに独立に、０または１を表し、および
（ｌ＋ｏ）は、好ましくは、０または１を表す。

Preferably, R ²² represents H;
Z ²¹ to Z ²³ each, independently of one _{another, -CH 2 -CH 2 -, -} CH 2 -CF 2 -, - CF 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH-, —CF═CH—, —CH═CF—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —O—, —CH ₂ —, —CO—O—, —O—. CO—, —CF ₂ —O—, —O—CF ₂ — or a single bond, preferably —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —CF ₂ —O—, Represents —O—CF ₂ — or a single bond, particularly preferably one or, if present, more Z ^{21 to} Z ²³ represents a single bond, very particularly preferably all are single bonds. Represents a bond,
l and o each independently represent 0 or 1, and (l + o) preferably represents 0 or 1.

式中、
Ｒ^３１およびＲ^３２は、それぞれ互いに独立に、Ｒ^１１およびＲ^１２に与えられる意味の１つを有し、好ましくは、１〜７個のＣ原子を有するアルキル、好ましくは、ｎ−アルキル、特に好ましくは、１〜５個のＣ原子を有するｎ−アルキル、１〜７個のＣ原子を有するアルコキシ、好ましくは、ｎ−アルコキシ、特に好ましくは、２〜５個のＣ原子を有するｎ−アルコキシ、２〜７個のＣ原子を有する、好ましくは、２〜４個のＣ原子を有するアルコキシアルキル、アルケニルまたはアルケニルオキシ、好ましくは、アルケニルオキシを表し、

Where
R ³¹ and R ³² each independently of one another have one of the meanings given for R ¹¹ and R ¹² , preferably alkyl having 1 to 7 C atoms, preferably n-alkyl, in particular Preferably n-alkyl having 1 to 5 C atoms, alkoxy having 1 to 7 C atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 2 to 5 C atoms Represents alkoxyalkyl, alkenyl or alkenyloxy having 2 to 7 C atoms, preferably having 2 to 4 C atoms, preferably alkenyloxy,

好ましくは、

Preferably,

を表し、
好ましくは、

Represents
Preferably,

を表し、
好ましくは、

Represents
Preferably,

を表し、
および、存在しているのであれば、好ましくは、

Represents
And, if present, preferably

を表し、
Ｚ^３１〜Ｚ^３３は、それぞれ互いに独立に、Ｚ^１１〜Ｚ^１３に与えられる意味の１つを有し、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−または単結合、好ましくは、−ＣＨ_２−ＣＨ_２−または単結合、特に好ましくは、単結合を表し、
ｐおよびｑは、それぞれ互いに独立に、０または１を表し、
（ｐ＋ｑ）は、好ましくは、０または１、好ましくは０を表す。

Represents
Z ^{31 to} Z ³³ each independently have one of the meanings given to Z ^{11 to} Z ¹³ , preferably —CH ₂ —CH ₂ —, —CH═CH—, —C≡C— , -COO- or a single bond, _preferably, -CH 2 -CH ₂ - or a single bond, particularly preferably represents a single bond,
p and q each independently represent 0 or 1,
(P + q) preferably represents 0 or 1, preferably 0.

式中、
Ｒ^４１、Ｒ^４２、Ｒ^５１およびＲ^５２は、それぞれ互いに独立に、Ｒ^２１およびＲ^２２に与えられる意味の１つを有し、好ましくは、１〜７個のＣ原子を有するアルキル、好ましくは、ｎ−アルキル、特に好ましくは、１〜５個のＣ原子を有するｎ−アルキル、１〜７個のＣ原子を有するアルコキシ、好ましくは、ｎ−アルコキシ、特に好ましくは、２〜５個のＣ原子を有するｎ−アルコキシ、２〜７個のＣ原子を有する、好ましくは、２〜４個のＣ原子を有するアルコキシアルキル、アルケニルまたはアルケニルオキシ、好ましくは、アルケニルオキシを表し、
特に好ましくは、Ｒ^４１およびＲ^４２の一方、好ましくは、Ｒ^４１はアルキルまたはアルケニル基を表し、他方は、アルキル、アルケニル、アルコキシまたはアルケニルオキシ基を表し、特に好ましくは、Ｒ^２１は直鎖状のアルキル、特に、ＣＨ_３−、Ｃ_２Ｈ_５−、ｎ−Ｃ_３Ｈ_７−、ｎ−Ｃ_４Ｈ_９−またはｎ−Ｃ_５Ｈ_１１−、またはアルケニル、特に、ＣＨ_２＝ＣＨ−、Ｅ−ＣＨ_３−ＣＨ＝ＣＨ−、ＣＨ_２＝ＣＨ−ＣＨ_２−ＣＨ_２−、Ｅ−ＣＨ_３−ＣＨ＝ＣＨ−ＣＨ_２−ＣＨ_２−またはＥ−ｎ−Ｃ_３Ｈ_７−ＣＨ＝ＣＨ−を表し、

Where
R ⁴¹ , R ⁴² , R ⁵¹ and R ⁵² each independently of one another have one of the meanings given for R ²¹ and R ²² , preferably alkyl having 1 to 7 C atoms, preferably N-alkyl, particularly preferably n-alkyl having 1 to 5 C atoms, alkoxy having 1 to 7 C atoms, preferably n-alkoxy, particularly preferably 2 to 5 C N-alkoxy having atoms, alkoxyalkyl having 2 to 7 C atoms, preferably having 2 to 4 C atoms, alkenyl or alkenyloxy, preferably alkenyloxy,
Particularly preferably, one of R ⁴¹ and R ⁴² , preferably R ⁴¹ represents an alkyl or alkenyl group, the other represents an alkyl, alkenyl, alkoxy or alkenyloxy group, particularly preferably R ²¹ is linear alkyl, in _{particular, CH 3 -, C 2 H} 5 -, n-C 3 H 7 -, n-C 4 H 9 - or _{n-C 5 H 11} -, or alkenyl, _especially, CH 2 = CH-, E—CH ₃ —CH═CH—, CH ₂ ═CH—CH ₂ —CH ₂ —, E—CH ₃ —CH═CH—CH ₂ —CH ₂ —, or En—C ₃ H ₇ —CH═CH -

Ｌ^４１およびＬ^４２は、互いに独立に、＝Ｃ（Ｘ^４）−を表し、Ｌ^４１およびＬ^４２の一方は、二者択一的に、＝Ｎ−も表し、ただし、好ましくは、Ｌ^４１およびＬ^４２の少なくとも一方は＝Ｃ（−Ｆ）−を表し、他方は＝Ｃ（−Ｆ）−または＝Ｃ（−Ｃｌ）−を表し、特に好ましくは、、Ｌ^４１およびＬ^４２の両者が＝Ｃ（−Ｆ）−を表し、
Ｘ^４は、Ｆ、Ｃｌ、ＯＣＦ_３、ＣＦ_３、ＣＨ_３、ＣＨ_２Ｆ、ＣＨＦ_２、好ましくは、ＦまたはＣｌ、特に好ましくは、Ｆを表し、
および、他の環は、存在するのであれば、それぞれ互いに独立に、

L ⁴¹ and L ⁴² independently of each other represent ═C (X ⁴ ) —, and one of L ⁴¹ and L ⁴² alternatively represents ═N—, but preferably L ⁴¹ And at least one of L ⁴² represents ═C (—F) —, and the other represents ═C (—F) — or ═C (—Cl) —, and particularly preferably, both of L ⁴¹ and L ⁴² are = C (-F)-
X ⁴ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ , preferably F or Cl, particularly preferably F,
And the other rings, if present, are independently of each other,

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

を表し、
好ましくは、

Represents
Preferably,

、特に好ましくは、

, Particularly preferably

を表し、

Represents

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

を表し、
他は、存在するのであれば、それぞれ互いに独立に、

Represents
Others, if present, are independent of each other,

好ましくは、

Preferably,

を表し、

Represents

Ｚ^４１〜Ｚ^４３およびＺ^５１〜Ｚ^５３は、それぞれ互いに独立に、Ｚ^１１〜Ｚ^１３に与えられる意味の１つを有し、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−Ｏ−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＯＯ−または単結合、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−Ｏ−または単結合、特に好ましくは、−ＣＨ_２−Ｏ−または単結合を表し、
Ｚ^４１〜Ｚ^４３は、好ましくは、それぞれ互いに独立に、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−ＣＦ_２−、−ＣＦ_２−ＣＨ_２−、−ＣＦ_２−ＣＦ_２−、−ＣＨ＝ＣＨ−、−ＣＦ＝ＣＨ−、−ＣＨ＝ＣＦ−、−Ｃ≡Ｃ−、−ＣＨ_２−Ｏ−、−Ｏ−ＣＨ_２−、−Ｏ−、−ＣＨ_２−、−ＣＯ−Ｏ−、−Ｏ−ＣＯ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−または単結合、好ましくは、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−、−ＣＦ_２−Ｏ−、−Ｏ−ＣＦ_２−または単結合を表し、特に好ましくは、１つ、または存在するのであれば、それより多いＺ^４１〜Ｚ^４３が単結合を表し、非常に特に好ましくは全てが単結合を表し、
ｒおよびｓは、それぞれ互いに独立に、０または１を表し、
（ｒ＋ｓ）は、好ましくは、０または１を表し、
ｔおよびｕは、それぞれ互いに独立に、０または１を表し、
（ｔ＋ｕ）は、好ましくは、０または１、好ましくは、０を表す。

Z ^{41 to} Z ⁴³ and Z ^{51 to} Z ⁵³ each independently have one of the meanings given to Z ^{11 to} Z ¹³ , preferably —CH ₂ —CH ₂ —, —CH ₂ —O. —, —CH═CH—, —C≡C—, —COO— or a single bond, preferably —CH ₂ —CH ₂ —, —CH ₂ —O— or a single bond, particularly preferably —CH ₂ —. Represents O- or a single bond,
Z ⁴¹ to Z ⁴³ is a preferably mutually _{independently, -CH 2 -CH 2 -, -} CH 2 -CF 2 -, - CF 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH—, —CF═CH—, —CH═CF—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —O—, —CH ₂ —, —CO—O—, _{-O-CO -, - CF 2} -O -, - O-CF 2 - or a single bond, _{preferably, -CH 2 -CH 2 -, -} CH = CH -, - C≡C -, - CF 2 - Represents O—, —O—CF ₂ — or a single bond, particularly preferably one or, if present, more Z ^{41 to} Z ⁴³ represent a single bond, very particularly preferably all Represents a single bond,
r and s each independently represent 0 or 1,
(R + s) preferably represents 0 or 1,
t and u each independently represent 0 or 1,
(T + u) preferably represents 0 or 1, preferably 0.

  The medium according to the invention is preferably dielectrically negative.

  The medium according to the invention preferably comprises one, two, three or more than four, preferably one, two or more compounds of the formula I.

A compound of formula I,
a) R ¹¹ and / or R ¹² represents H, preferably alkyl, alkenyl or alkoxy having up to 6 C atoms, R ¹² very particularly preferably represents alkoxy or alkenyloxy,
b) both R ¹¹ and R ¹² represent alkyl (the alkyl groups may be the same or different),
c) Particularly preferred are those in which R ¹¹ represents linear alkyl, vinyl, 1E-alkenyl or 3-alkenyl.

When R ¹¹ and / or R ¹² represent alkenyl, this is preferably CH ₂ ═CH—, CH ₃ —CH═CH—, CH ₂ ═CH—C ₂ H ₄ — or CH ₃ —CH═CH. -C ₂ H ₄ -.

  The compounds of formula I are preferably selected from the group of compounds of formulas I-1 to I-4, preferably from the group of formulas I-1 and I-3, particularly preferably of formula I-1.

式中、パラメータは、式Ｉにおいて上で与えられるそれぞれの意味を有し、好ましくは、
式Ｉ−１およびＩ−２において、
Ｚ^１１は、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−Ｏ−または単結合、好ましくは、−ＣＨ_２−Ｏ−または単結合、特に好ましくは、−ＣＨ_２−Ｏ−を表し、
式Ｉ−３およびＩ−４において、
Ｚ^１１は、−ＣＨ_２−ＣＨ_２−または単結合、好ましくは、単結合を表し、
Ｚ^１２は、−ＣＨ_２−ＣＨ_２−、−ＣＨ_２−Ｏ−または単結合、好ましくは、−ＣＨ_２−Ｏ−または単結合、特に好ましくは、−ＣＨ_２−Ｏ−を表す。

In which the parameters have the respective meaning given above in formula I, preferably
In formulas I-1 and I-2,
Z ¹¹ _{is, -CH 2 -CH 2 -, -} CH 2 -O- or a single bond, preferably, _-CH 2 -O- or a single bond, particularly preferably represents _-CH 2 -O-,
In formulas I-3 and I-4,
Z ¹¹ represents —CH ₂ —CH ₂ — or a single bond, preferably a single bond,
Z ¹² _{is, -CH 2 -CH 2 -, -} CH 2 -O- or a single bond, preferably, _-CH 2 -O- or a single bond, particularly preferably represents _-CH 2 -O-.

  Very particular preference is given to compounds of the formulas I-1a, I-1b, I-3a and I-3b which are the following compounds:

式中、パラメータは上で与えられる意味を有し、Ｒ^１１は、好ましくは、１〜７個、好ましくは、１〜５個のＣ原子を有するアルキル、好ましくは、ｎ−アルキルを表し、Ｒ^１２は、好ましくは、１〜５個、好ましくは、２〜４個のＣ原子を有するアルコキシを表す。

In which the parameters have the meaning given above, R ¹¹ preferably represents alkyl having 1 to 7, preferably 1 to 5 C atoms, preferably n-alkyl, R ¹² preferably represents alkoxy having 1 to 5, preferably 2 to 4 C atoms.

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

式中、パラメータは式ＩＩに上で示されるそれぞれの意味を有し、好ましくは、
Ｒ^２１は、アルキルまたはアルケニルを表し、および
Ｒ^２２は、アルキル、アルケニル、アルコキシまたはアルケニルオキシを表し、
Ｚ^２１は、単結合を表し、および
ｒは、０を表す。

In which the parameters have the respective meanings indicated above in formula II, preferably
R ²¹ represents alkyl or alkenyl, and R ²² represents alkyl, alkenyl, alkoxy or alkenyloxy,
Z ²¹ represents a single bond, and r represents 0.

  Very particular preference is given to compounds of the formula II-2a.

式中、Ｒ^２１は上で与えられる意味を有し、好ましくは、１〜７個、好ましくは１〜５個のＣ原子を有するアルキル、好ましくは、ｎ−アルキルを表す。

In which R ²¹ has the meaning given above and preferably represents alkyl having 1 to 7, preferably 1 to 5, C atoms, preferably n-alkyl.

In a further preferred embodiment, the medium comprises one or more compounds of formula III
Where

を表し、
ここで、２個の隣接している環は、非常に特に好ましくは、直接結合しており、より正確には、好ましくは、

Represents
Here, two adjacent rings are very particularly preferably directly bonded, more precisely, preferably

を表し、
ただし、フェニレン環中の１個以上のＨ原子は、互いに独立に、ＦまたはＣＮ、好ましくはＦにより置き換えられていてもよく、シクロヘキシレン環または２個のシクロヘキシレン環の１個の隣接しない１個または２個のＣＨ_２基は、Ｏ原子により置き換えられていてもよい。

Represents
However, one or more H atoms in the phenylene ring may be replaced independently of each other by F or CN, preferably F, and one non-adjacent 1 of a cyclohexylene ring or two cyclohexylene rings. One or two CH ₂ groups may be replaced by an O atom.

  In a further preferred embodiment, the medium is from the group of compounds of formula III-1 to III-11, preferably from the group of compounds of formula III-1 to III-9, preferably from group III-1 to III-6. Particular preference is given to one or more compounds of the formula III selected from the groups III-1 and III-4.

式中、パラメータは式ＩＩＩに上で示されるそれぞれの意味を有し、
Ｙ^３はＨまたはＦを表し、および好ましくは、
Ｒ^３１は、アルキルまたはアルケニルを表し、および
Ｒ^３２は、アルキル、アルケニルまたはアルコキシ、好ましくは、アルキルまたはアルケニル、特に好ましくは、アルケニルを表す。

In which the parameters have the respective meanings indicated above in formula III;
Y ³ represents H or F, and preferably
R ³¹ represents alkyl or alkenyl, and R ³² represents alkyl, alkenyl or alkoxy, preferably alkyl or alkenyl, particularly preferably alkenyl.

The medium is particularly preferably
-Formula III-1c, particularly preferably
-R ³¹ represents a vinyl or ^{1-propenyl, R 32} is alkyl, preferably, it represents a n- alkyl, particularly ^{preferably, R 31} represents a ^vinyl, Formula III-1 ^{R 32} represents propyl, and - Formula III-1d, particularly preferably
Formula III-1 in which -R ³¹ and R ³² independently of one another represent vinyl or 1-propenyl, preferably R ³¹ represents vinyl, particularly preferably R ³¹ and R ³² represent vinyl.
One or more compounds of formula III-1 selected from the group of (one or multiple).

  In a further preferred embodiment, the medium is of formula III-1a to III-1e, preferably of formula III-1a and / or formula III-1c and / or III-1d, particularly preferably of formula III-1c and / or Or III-1d, very particularly preferably comprising one or more compounds of the formula III-1 selected from the group of compounds of the formulas III-1c and III-1d.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌおよびａｌｋｅｎｙｌ’は、互いに独立に、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl and alkenyl ′ represent, independently of one another, alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  The medium according to the invention particularly preferably has a compound of formula III-1, in particular a compound of formula III-1c, in an amount of 20% by weight or more, in particular 25% by weight or more, very particularly preferably of 30% by weight or more. Including.

式中、
ｎは、３、４または５であり、Ｒ^ｅはＨまたはＣＨ_３を表す。

Where
n is 3, 4 or 5, and R ^e represents H or CH ₃ .

  In a further preferred embodiment, the medium is a compound of formula III selected from the group of compounds of formula III-1a and III-1b, preferably formula III-1a and / or III-1b, particularly preferably formula III-1a. -1 or more compounds. In this embodiment, preferably the medium does not comprise a compound of formula III, preferably a compound of formula III-1, containing one alkenyl end group or a plurality of alkenyl end groups, ie preferably formula III The compounds of -1c to III-1e are not included. In this embodiment, the medium particularly preferably contains one or more compounds selected from the group of compounds of the formulas CC-2-3, CC-2-5, CC-3-4 and CC-3-5. However, the acronyms (abbreviations) are described in Tables A to C, and are shown by way of example in Table D.

  In a further preferred embodiment, the medium is of formula III-2a to III-2d, preferably of formula III selected from the group of compounds of formula III-2a and / or III-2b, particularly preferably of formula III-2b -1 or more types of compounds are included.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、および
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms, and alkenyl has 2 to 7 C atoms, preferably 2 to 5 Represents an alkenyl having a C atom.

  In a further preferred embodiment, the medium comprises one or more compounds of formula III-3 selected from the group of compounds of formulas III-3a to III-3c.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  The proportion of these biphenyls in the whole mixture is preferably 3% by weight or more, particularly 5% by weight or more.

  Preferred compounds of formula III-3a and III-3b are those of the following formulae:

式中、パラメータは、上で示される意味を有する。

In which the parameters have the meanings indicated above.

  Particularly preferred compounds of formula III-3b are those of the following formulae:

および、これらの中でも、特に、最後の式のものである。

And among these, in particular, the last one.

In a preferred embodiment, the medium is one or more compounds of formula III-4, particularly preferably R ³¹ represents vinyl or 1-propenyl, R ³² represents alkyl, preferably n-alkyl, particularly preferably , R ³¹ represents vinyl and R ³² represents methyl, which includes one or more compounds (one type or many types).

  In a further preferred embodiment, the medium is of formula III-4a to III-4d, preferably of formula III selected from the group of compounds of formula III-4a and / or III-4b, particularly preferably of formula III-4b -4 of one or more compounds.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

In a preferred embodiment, the medium is one or more compounds of formula III-5, particularly preferably one which R ³¹ represents alkyl, vinyl or 1-propenyl and R ³² represents alkyl, preferably n-alkyl. Including the above compounds (one kind or many kinds).

  In a further preferred embodiment, the medium is of formula III-5a to III-5d, preferably of formula III-5a and / or III-5b, particularly preferably of formula III-5a and / or of formula III-5e III-5h, preferably comprising one or more compounds of the formula III-5, selected from the group of compounds of the formula III-5e, preferably of formula III-5e and / or III-5f, particularly preferably of formula III-5e.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  In a further preferred embodiment, the medium is a compound of formula III-6a to III-6c, preferably of formula III-6a and / or III-6b, particularly preferably selected from the group of compounds of formula III-6a Including one or more compounds of -6.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  Particularly preferably, the medium according to the invention is preferably of formula III-6a selected from the group of compounds of PGP-2-3, PGP-3-3 and PGP-3-4, and preferably of formula PGP-1. Including one or more compounds selected from compounds of formula III-6b selected from the group of -2V, PGP-2-2V and PGP-3-2V, with the acronyms (abbreviations) in Table A- This is illustrated in C and illustrated by way of example in Table D.

  In a further preferred embodiment, the medium comprises one or more compounds of formula III-10 selected from the group of compounds of formulas III-10a and III-10b.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表す。

Where
alkyl and alkyl ′ represent, independently of one another, alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms.

  In a further preferred embodiment, the medium comprises one or more compounds of formula III-11 of formula III-11a.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表す。

Where
alkyl and alkyl ′ represent, independently of one another, alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms.

  In a preferred embodiment, the medium comprises one or more compounds of formula IV selected from the group of compounds of formulas IVA-IVD, preferably IVA-IVC, very particularly preferably IVA and IVB.

式中、パラメータは上で示される意味を有するが、式ＩＶＡにおいて、

In which the parameters have the meanings indicated above, but in formula IVA:

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

Ｒ^４１は、アルキルを表し、
Ｒ^４２は、アルキルまたはアルコキシ、特に好ましくは、（Ｏ）Ｃ_ｖＨ_２ｖ＋１を表し、
Ｘ^４１およびＸ^４２は、両者ともＦを表し、
Ｚ^２１およびＺ^２２は、互いに独立に、単結合、−ＣＨ_２−ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＨ_２Ｏ−、−ＯＣＨ_２−、−Ｏ−、−ＣＨ_２−、−ＣＦ_２Ｏ−または−ＯＣＦ_２−、好ましくは、単結合または−ＣＨ_２ＣＨ_２−、特に好ましくは、単結合を表し、
ｐは、１または２を表し、および
ｖは、１〜６を表す。

R ⁴¹ represents alkyl,
R ⁴² represents alkyl or alkoxy, particularly preferably (O) C _v H _{2v + 1} ,
X ⁴¹ and X ⁴² both represent F;
Z ²¹ and Z ²² are each independently a single bond, —CH ₂ —CH ₂ —, —CH═CH—, —CH ₂ O—, —OCH ₂ —, —O—, —CH ₂ —, —CF. ₂ O— or —OCF ₂ —, preferably a single bond or —CH ₂ CH ₂ —, particularly preferably a single bond,
p represents 1 or 2, and v represents 1-6.

  In a preferred embodiment, the medium comprises one or more compounds of formula IV selected from the group of compounds of formulas IV-1 to IV-14.

式中、
Ｙ^４１〜Ｙ^４６は、互いに独立に、ＨまたはＦを表し、および
Ｘ^４１およびＸ^４２は両者ともＨを表すか、またはＸ^４１およびＸ^４２の一方がＨを表し、他方がＦを表し、
しかしながら、好ましくは最多で４つ、特に好ましくは最多で３つ、非常に特に好ましくは１つまたは２つのＹ^４１〜Ｙ^４６、Ｘ^４１およびＸ^４２がＦを表し、
および
他のパラメータは、式ＩＶにおいて上で示されるそれぞれの意味を有し、好ましくは、
Ｒ^４１は、アルキルまたはアルケニルを表し、および
Ｒ^４２は、アルキル、アルケニル、アルコキシまたはアルケニルオキシ、好ましくは、（Ｏ）Ｃ_ｖＨ_２ｖ＋１を表し、および
ｖは、１〜６の整数を表す。

Where
Y ^{41 to} Y ⁴⁶ independently of each other represent H or F, and X ⁴¹ and X ⁴² both represent H, or one of X ⁴¹ and X ⁴² represents H and the other represents F;
However, preferably at most 4, particularly preferably at most 3, very particularly preferably 1 or 2 of Y ⁴¹ to Y ⁴⁶ , X ⁴¹ and X ⁴² represent F,
And the other parameters have the respective meanings indicated above in formula IV, preferably
R ⁴¹ represents alkyl or alkenyl, and R ⁴² represents alkyl, alkenyl, alkoxy or alkenyloxy, preferably (O) C _v H _{2v + 1} , and v represents an integer of 1-6.

  In a further preferred embodiment, the medium is of the formula IV-1a selected from the group of compounds of the formulas IV-1a to IV-1d, preferably of formulas IV-1b and / or IV-1d, particularly preferably of IV-1b One or more compounds.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  Preferred compounds of formula IV-1c and IV-1d are compounds of the following formulas:

式中、ｖは上で示される意味を有する。

In which v has the meaning indicated above.

  More preferred compounds of formula IV-1 are compounds of the following formula:

式中、Ｒ^４１は式ＩＶに上で示されるそれぞれの意味を有する。

In which R ⁴¹ has the respective meaning indicated above in formula IV.

  In a preferred embodiment, the medium is a compound of formula IV-3 selected from the group of compounds of formula IV-3a to IV-3d, preferably formula IV-3b and / or IV-3d, particularly preferably IV-3b. Contains more than one type of compound.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  The concentration of these biphenyl compounds in the overall mixture is preferably 3% by weight or more, in particular 5% by weight or more, very particularly preferably 5 to 25% by weight.

  In a further preferred embodiment, the medium is of formula IV-4a selected from the group of compounds of formula IV-4a to IV-4d, preferably of formula IV-4a and / or IV-4b, particularly preferably of IV-4b. One or more compounds.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  Preferred compounds of formula IV-4c and IV-4d are compounds of the following formulas:

式中、ｖは上で示される意味を有する。

In which v has the meaning indicated above.

  In a further preferred embodiment, the medium comprises one or more compounds of formula IV-4 of the following sub-formula IV-4e.

式中、
Ｒ^４１は、上で示される意味を有し、および
ｍおよびｚは、それぞれ独立に、１〜６の整数を表し、および
ｍ＋ｚは、好ましくは、１〜６の整数を表す。

Where
R ⁴¹ has the meaning indicated above, and m and z each independently represents an integer from 1 to 6, and m + z preferably represents an integer from 1 to 6.

  In a further preferred embodiment, the medium comprises one or more compounds of formula IV-5 selected from the group of compounds of formula IV-5a to IV-5d, preferably formula IV-5b and / or IV-5d. Including.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  Preferred compounds of formula IV-5c and IV-5d are compounds of the following formulas:

式中、ｖは上で示される意味を有する。

In which v has the meaning indicated above.

  In a further preferred embodiment, the medium comprises a group of compounds of formula IV-6a to IV-6d, preferably formula IV-6a and / or IV-6c, particularly preferably formula IV-6a and / or formula IV Comprising one or more compounds of formula IV-6, selected from the group of compounds from -6e to IV-6m.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

式中、
Ｒは、Ｒ^４１に上で与えられる意味を有し、および
ｍは、１〜６の整数を表す。

Where
R has the meaning given above for R ⁴¹ , and m represents an integer of 1-6.

  R is preferably straight-chain alkyl or alkoxy each having 1 to 6 C atoms, or alkoxyalkyl, alkenyl or alkenyloxy having 2 to 6 C atoms, particularly preferably 1 to 5 Represents an alkyl having the following C atoms, preferably methyl, ethyl, propyl, butyl, or additionally alkoxy having 1 to 5 C atoms, preferably hexyl, methoxy, ethoxy, propoxy or butoxy.

  In a further preferred embodiment, the medium comprises a group of compounds of formula IV-7a to IV-7d, preferably formula IV-7a and / or IV-7c, particularly preferably formula IV-7a, and / or formula IV Comprising one or more compounds of formula IV-7, selected from the group of compounds of −7e to IV-7i.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜５個のＣ原子を有し、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 5 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

式中、
Ｒは、Ｒ^４１に上で与えられる意味を有し、
ｍは、１〜６の整数を表す。

Where
R has the meaning given above for R ⁴¹ ;
m represents an integer of 1 to 6.

  R is preferably straight-chain alkyl or alkoxy each having 1 to 6 C atoms, or alkoxyalkyl, alkenyl or alkenyloxy having 2 to 6 C atoms, particularly preferably 1 to 5 Represents an alkyl having the following C atoms, preferably methyl, ethyl, propyl, butyl, or additionally alkoxy having 1 to 5 C atoms, preferably hexyl, methoxy, ethoxy, propoxy or butoxy.

  In a further preferred embodiment, the medium comprises one or more compounds of the formula IV-8, selected from the group of compounds of the formulas IV-8a and IV-8b, particularly preferably IV-8b.

式中、パラメータは上で示される意味を有する。

In which the parameters have the meanings indicated above.

  In a further preferred embodiment, the medium comprises one or more compounds of formula IV-9 selected from the group of compounds of formulas IV-9a to IV-9d.

式中、パラメータは上で示される意味を有し、好ましくは、
Ｒ^４２は、Ｃ_ｖＨ_２ｖ＋１を表し、および
ｖは、１〜６の整数を表す。

In which the parameters have the meanings indicated above, preferably
R ⁴² represents C _v H _{2v + 1} , and v represents an integer of 1 to 6.

  In a further preferred embodiment, the medium comprises one or more compounds of formula IV-10 selected from the group of compounds of formulas IV-10a to IV-10e.

式中、パラメータは上で示される意味を有し、好ましくは、
Ｒ^４２は、Ｃ_ｖＨ_２ｖ＋１を表し、および
ｖは、１〜６の整数を表す。

In which the parameters have the meanings indicated above, preferably
R ⁴² represents C _v H _{2v + 1} , and v represents an integer of 1 to 6.

  In a further preferred embodiment, the medium comprises one or more compounds of the formula IV-11, selected from the group of compounds of the formulas IV-11a and IV-11b, particularly preferably IV-11b.

式中、パラメータは上で示される意味を有する。

In which the parameters have the meanings indicated above.

  In a further preferred embodiment, the medium is of formula IV-14a to IV-14d, preferably selected from the group of compounds of formula IV-14a and / or IV-14b, particularly preferably of formula IV-14b 14 of one or more compounds.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子を有し、好ましくは２〜５個のＣ原子を有するアルキルを表し、
ａｌｋｏｘｙは、１〜７個のＣ原子を有する、好ましくは２〜４個のＣ原子を有するアルコキシを表し、
ａｌｋｅｎｙｌは、２〜７個のＣ原子を有する、好ましくは２〜５個のＣ原子を有するアルケニルを表す。

Where
alkyl and alkyl ′ independently of one another represent alkyl having 1 to 7 C atoms, preferably 2 to 5 C atoms,
alkoxy represents alkoxy having 1 to 7 C atoms, preferably 2 to 4 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms.

  In a further preferred embodiment, the medium preferably contains one or more compounds of formula V selected from the group of compounds of formulas V-1 to V-8, preferably of formulas V-7 and / or V-8 ( Additionally) including.

式中、パラメータは式Ｖに上で示されるそれぞれの意味を有し、好ましくは、
Ｒ^５１は、アルキルまたはアルケニルを表し、および
Ｒ^５２は、アルキル、アルケニル、アルコキシまたはアルケニルオキシを表す。

In which the parameters have the respective meanings indicated above in formula V, preferably
R ⁵¹ represents alkyl or alkenyl, and R ⁵² represents alkyl, alkenyl, alkoxy or alkenyloxy.

  In this embodiment, preferably when the medium comprises one or more compounds of formula V-7 and / or V-8, the medium consists essentially of compounds of formula I, II, III and V Can do.

  In a further preferred embodiment, the medium contains one or more compounds containing fluorinated phenanthrene units, preferably a compound of formula V, preferably selected from the group of compounds of formulas V-9 and V-10. Including (additionally).

式中、パラメータは式Ｖに上で示されるそれぞれの意味を有し、好ましくは、
Ｒ^５１は、アルキルまたはアルケニルを表し、および
Ｒ^５２は、アルキル、アルケニル、アルコキシまたはアルケニルオキシを表す。

In which the parameters have the respective meanings indicated above in formula V, preferably
R ⁵¹ represents alkyl or alkenyl, and R ⁵² represents alkyl, alkenyl, alkoxy or alkenyloxy.

  In a further preferred embodiment, the medium comprises (additionally) one or more compounds containing fluorinated dibenzofuran units, preferably a compound of formula V, preferably of formula V-11.

式中、パラメータは式Ｖに上で示されるそれぞれの意味を有し、好ましくは、
Ｒ^５１は、アルキルまたはアルケニルを表し、および
Ｒ^５２は、アルキル、アルケニル、アルコキシまたはアルケニルオキシを表す。

In which the parameters have the respective meanings indicated above in formula V, preferably
R ⁵¹ represents alkyl or alkenyl, and R ⁵² represents alkyl, alkenyl, alkoxy or alkenyloxy.

  One chiral compound or a plurality of chiral compounds that can be used in component E of the liquid crystal medium according to the invention is selected from known chiral dopants. Component E preferably consists essentially of one or more compounds selected from the group of compounds of the following formulas VI to VIII, particularly preferably essentially, very particularly preferably substantially completely.

式中、
Ｒ^６１およびＲ^６２、Ｒ^７１〜Ｒ^７３およびＲ^８は、それぞれ互いに独立に、式ＩＩにおいてＲ^２１に上で与えられる意味を有し、あるいは、Ｈ、ＣＮ、Ｆ、Ｃｌ、ＣＦ_３、ＯＣＦ_３、ＣＦ_２ＨまたはＯＣＦ_２Ｈを表し、Ｒ^６１およびＲ^６２の少なくとも一方はキラル基を表し、
Ｚ^６１およびＺ^６２、Ｚ^７１〜Ｚ^７３およびＺ^８は、それぞれ互いに独立に、−ＣＨ_２ＣＨ_２−、−ＣＨ＝ＣＨ−、−ＣＯＯ−、−Ｏ−ＣＯ−または単結合を表し、好ましくは、Ｚ^６１、Ｚ^６２、Ｚ^７１、Ｚ^７４およびＺ^７５は単結合を表し、Ｚ^６３、Ｚ^７２およびＺ^７３は−ＣＯＯ−または単結合を表し、Ｚ^７２は、好ましくは、−ＣＯＯ−を表し、Ｚ^７３およびＺ^８は−Ｏ−ＣＯ−を表し、

Where
R ⁶¹ and R ⁶² , R ^{71 to} R ⁷³ and R ⁸ each independently of one another have the meaning given above for R ²¹ in formula II, or alternatively H, CN, F, Cl, CF ₃ , OCF ₃ , CF ₂ H or OCF ₂ H, at least one of R ⁶¹ and R ⁶² represents a chiral group,
Z ⁶¹ and Z ⁶² , Z ^{71 to} Z ⁷³ and Z ⁸ each independently represent —CH ₂ CH ₂ —, —CH═CH—, —COO—, —O—CO— or a single bond, Z ⁶¹ , Z ⁶² , Z ⁷¹ , Z ⁷⁴ and Z ⁷⁵ represent a single bond, Z ⁶³ , Z ⁷² and Z ⁷³ represent —COO— or a single bond, and Z ⁷² preferably represents —COO— Z ⁷³ and Z ⁸ represent —O—CO—,

ｕおよびｖ、およびｘ、ｙおよびｚは、それぞれ互いに独立に、０または１を表し、好ましくは、
ｕおよびｖの両方が０を表し、および
ｘおよびｖの両方が１を表す。

u and v, and x, y and z each independently of one another represent 0 or 1,
Both u and v represent 0, and both x and v represent 1.

  Particularly particularly preferred embodiments of the present invention satisfy one or more of the following conditions.

  i. The liquid crystal medium has a birefringence of 0.095 or higher.

  ii. The liquid crystal medium comprises one or more compounds selected from the group of sub-formulas I-1 to I-4.

  iii. The concentration of the individual congener compounds of the formula I is in the range of 1-20%, preferably 2-15%, particularly preferably 3-10%.

  iv. The total proportion of compounds of formula II in the mixture is 10% by weight or more.

  v. The concentration of the individual congener compounds of the formula II is in the range 2-15%, preferably 3-12%, particularly preferably 4-10%.

  vi. The proportion of compounds of the formula III in the mixture as a whole is not less than 10%, preferably not more than 70%, particularly preferably not less than 20% by weight.

  vii. The liquid crystal medium comprises one or more particularly preferred compounds of the formulas III-1c and III-1d selected from the following subformulae:

式中、ａｌｋｙｌは上で与えられる意味を有し、好ましくは、それぞれの場合で互いに独立に、１〜６個、好ましくは２〜５個のＣ原子を有するアルキル、特に好ましくは、ｎ−アルキルを表す。

In which alkyl has the meaning given above, preferably in each case, independently of one another, alkyl having 1 to 6, preferably 2 to 5, C atoms, particularly preferably n-alkyl. Represents.

  viii. The liquid crystal medium comprises one or more compounds of formula III selected from the group of formulas below.

式中、Ｒ^３１およびＲ^３２は上で示される意味を有し、Ｒ^３１およびＲ^３２は、好ましくは、それぞれ互いに独立に、１個または２〜７個のＣ原子をそれぞれ有する直鎖状のアルキル、アルコキシまたはアルケニル基、特に好ましくは、直鎖状のアルキル、更には、アルケニルを表す。

In which R ³¹ and R ³² have the meanings indicated above, and R ³¹ and R ³² are preferably each independently of one another linear, each having 1 or 2 to 7 C atoms. Alkyl, alkoxy or alkenyl groups, particularly preferably straight-chain alkyl and furthermore alkenyl.

  The proportion of these compounds in the mixture is preferably 5 to 40% by weight.

  ix. The liquid crystal medium has the following formula: CC-n-V and / or CC-n-Vm (for example: preferably CC-5-V, preferably at a concentration up to 25%, preferably CC-3-V CC-n at concentrations up to 60% and / or CC-3-V1 preferably at concentrations up to 25% and / or CC-4-V preferably at concentrations up to 40%) -M and / or CC-n-Om (eg: preferably CC-3-2 and / or CC-3-3 and / or CC-3-4 and / or CC-3-O2 and / or CCP-5 -O2), CP-n-m and / or CP-n-Om (eg: preferably CP-3-2 and / or CP-5-2 and / or CP-3-O1 and / or CP-3- O2), PP-n-Vm ( For example: preferably PP-n-2V), PP-n-lVm (eg: preferably PP-n-2V1), CCP-n-m (eg: preferably CCP-n-1), CPP-n-m One or more compounds of formula III selected from the group of compounds CGP-nm and CCOC-nm, preferably in a total concentration of 10% to 70%, provided that the initials The meaning of (abbreviation) is explained in Tables A to C and illustrated by way of example in Table D.

x. Liquid crystal media
-2% to 80% by weight of one or more compounds of formula I;
-2% to 80% by weight of one or more compounds of formula II;
-2% to 80% by weight of one or more compounds of the formula III and / or -2% to 80% by weight of one or more compounds selected from the group of compounds of the formulas IV and / or V Consists essentially of.

  xi. 1 to 15% by weight, in particular 2 to 12% by weight, of one or more compounds of the formula I, wherein the liquid-crystalline medium has four 6- or 10-membered rings or ring structures, per individual compound, Very particularly preferably, it is contained in an amount of 3 to 8% by weight.

  xii. The liquid crystal medium preferably contains one or more compounds of the formula IV in an amount of 2% by weight or more, in particular 5% by weight or more, very particularly preferably 5% by weight or more and 25% by weight or less, per individual compound belonging to the same group. In particular, it is contained in the range of 2 wt% to 12 wt%.

  xiii. The liquid crystal medium is of formula IV-1 to IV-3, preferably of formula IV-1 and / or IV-3, preferably of formula IV-1b and / or IV-1d and / or IV-3b and / or Or IV-3d, particularly preferably one or more compounds of IV-1b and / or IV-3b, preferably in a total concentration of 60% or less, in particular of 2% by weight or more per individual compound belonging thereto, in particular It is contained in a concentration of 5% by weight or more, very particularly preferably 5% by weight or more and 20% by weight or less.

  xiv. The liquid crystal medium is preferably of formula IV-4 and / or IV-5, preferably of formula IV-4b and / or IV-4d and / or IV-5b and / or IV-5d, particularly preferably IV-4b. And / or one or more compounds of IV-5b, preferably in a total concentration of 60% or less, more than 2% by weight, in particular 5% by weight, very particularly preferably 5% by weight, per individual compound of the same genus It is contained at a concentration of -20% by weight or less.

  xv. The liquid crystal medium is preferably one or more compounds of formula IV-6 and / or IV-7, preferably of formula IV-6a and / or IV-7a, preferably in a total concentration of 50% or less, preferably of formula In a concentration of 2% to 10% by weight per individual compound of the same genus IV-6 and in a concentration of 2% to 20% by weight per individual compound of the same genus of formula IV-6.

  xvi. The liquid-crystalline medium preferably contains one or more compounds of the formula IV in an amount of preferably 2% by weight or more, in particular 5% by weight or more, very particularly preferably from 5% to 25% by weight, especially for each individual compound. 2 to 12% by weight.

  xvii. The liquid-crystalline medium preferably contains one or more compounds of the formula V in an amount of preferably 3% by weight or more, in particular 5% by weight or more, very particularly preferably 5% to 25% by weight, in particular, per individual compound. 2 to 20% by weight.

  The invention further relates to an electro-optical display comprising an active matrix addressing on the basis of the ECB effect, characterized in that it contains the liquid-crystal medium according to the invention as a dielectric.

The liquid crystal mixture preferably has a nematic phase range of at least 60 degrees and a flow viscosity ν ₂₀ of up to 30 mm ² · s ⁻¹ at 20 ° C.

The liquid crystal mixture according to the invention has a Δε of about −0.5 to −8.0, in particular about −2.5 to −6.0, where Δε represents the dielectric anisotropy. The rotational viscosity γ ₁ is preferably 200 mPa · s or less, particularly 170 mPa · s or less.

  The birefringence Δn in the liquid crystal mixture is generally between 0.06 and 0.16, preferably between 0.08 and 0.12.

  The mixtures according to the invention are suitable for all VA-TFT applications such as, for example, VAN, MVA, (S) -PVA and ASV. They are further suitable for negative Δε IPS (In-Plane Switching), FFS (Fringe Field Switching) and PALC applications.

  The nematic liquid crystal mixture in the display according to the invention generally comprises two components A and B which themselves consist of one or more individual compounds.

  For component A, one (or many) individual compounds (one or many) having a Δε value of −0.8 or less are preferably selected. The lower the proportion of A in the overall mixture, the more negative this value must be.

  For component B, one (or many) individual compounds (one or many) having a Δε value of −0.8 or less are preferably selected. The lower the proportion of B in the overall mixture, the more negative this value must be.

Component C has a clear nematogenicity and a flow viscosity at 20 ° C. of 30 mm ² · s ⁻¹ or less, preferably 25 mm ² · s ⁻¹ or less.

Particularly preferred individual compounds in component C are very low viscosity nematic liquid crystals having a flow viscosity at 20 ° C. of 18 mm ² · s ⁻¹ or less, preferably 12 mm ² · s ⁻¹ or less.

  Component C is monotropic or enantiotropic nematic and can prevent the generation of a smectic phase in the liquid crystal mixture to very low temperatures. For example, when various high nematogenic materials are added to the smectic liquid crystal mixture in each case, the nematogenic properties of these materials can be compared by the degree to which the achieved smectic phase can be suppressed.

  Many suitable materials are known to the person skilled in the art from the literature. Particular preference is given to compounds of the formula III.

  In addition, these liquid crystal phases may also contain more than 18 components, preferably 18-25 components.

  The phase preferably comprises 4-15, in particular 5-12, particularly preferably not more than 10, compounds of the formulas I and II and / or III and / or IV and / or V.

  In addition to compounds selected from the group of formulas I to V, other constituents may also be present, for example in amounts up to 45% of the total mixture, but preferably up to 35%, in particular up to 10%. .

  The other constituents are preferably, in particular, azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexylbenzoic acid esters, phenyl or cyclohexylcyclohexanecarboxylic acid esters, phenylcyclohexanes, cyclohexyl Biphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl or cyclohexyldioxanes, optionally halogenated stilbenes, benzylphenyl ethers, tolans and substituted Selected from nematic or nematogenic substances, which are known substances classified as cinnamic acid esters.

  The most important compounds suitable as constituents of this type of liquid crystal phase can be characterized by the formula IX.

式中、ＬおよびＥは、それぞれ、１，４−二置換ベンゼンおよびシクロヘキサン環、４，４’−二置換ビフェニル、フェニルシクロヘキサンおよびシクロへキシルシクロヘキサン構造、２，５−二置換ピリミジンおよび１，３−ジオキサン環、２，６−二置換ナフタレン、ジ−およびテトラヒドロナフタレン、キナゾリンおよびテトラヒドロキナゾリンより成る群からの炭素またはヘテロ環式環構造を表す。

Wherein L and E are 1,4-disubstituted benzene and cyclohexane rings, 4,4′-disubstituted biphenyl, phenylcyclohexane and cyclohexylcyclohexane structures, 2,5-disubstituted pyrimidine and 1,3, respectively. Represents a carbon or heterocyclic ring structure from the group consisting of a dioxane ring, 2,6-disubstituted naphthalene, di- and tetrahydronaphthalene, quinazoline and tetrahydroquinazoline.

G is, -CH = CH -, - N (O) = N -, - CH = CQ -, - CH = N (O) -, - C≡C -, - CH 2 -CH 2 -, - CO- O—, —CH ₂ —O—, —CO—S—, —CH ₂ —S—, —CH═N—, —COO—Phe—COO—, —CF ₂ O—, —CF═CF—, — OCF ₂ —, —OCH ₂ —, — (CH ₂ ) ₄ —, — (CH ₂ ) ₃ O— or a C—C single bond, Q represents halogen, preferably chlorine or —CN, R ⁹¹ and R ⁹² each represent an alkyl, alkenyl, alkoxy, alkanoyloxy or alkoxycarbonyloxy having up to 18, preferably up to 8 carbon atoms, or one of these groups is CN, NC _{, NO 2, NCS, CF 3} , OCF 3, F, Cl or B A representative.

In most of these compounds, R ⁹¹ and R ⁹² are different from each other, and one of these groups is usually an alkyl or alkoxy group. Other variants of the proposed substituents are also common. Many of such materials or mixtures thereof are also commercially available. All these substances can be prepared by methods known from the literature.

  The concentration of the compound of formula IX in the whole mixture is preferably 1% to 25%, particularly preferably 1% to 15%, very particularly preferably 2% to 9%.

  The medium according to the invention may also contain a dielectrically positive compound, the total concentration of which is preferably not more than 10% by weight, based on the whole medium.

In a preferred embodiment, the liquid crystal medium according to the invention as a whole is based on the whole mixture, 5% to 60%, preferably 10% to 50%, preferably 15% to 40%, in particular Preferably 20% to 35%, very particularly preferably 25% to 30% or less of component A, and 1% to 45%, preferably 2% to 40%, preferably 3% More than 35%, particularly preferably 5% -30%, very particularly preferably 10% -20% component B, and 5% -80%, preferably 25% -75. %, Particularly preferably 35% to 70%, very particularly preferably 40% to 65% of component C.

  Different preferred rings of different component concentrations can be combined with one another as desired, but the total concentration of all compounds and all components does not exceed 100% in each case.

  In a preferred embodiment, the liquid crystal medium according to the invention comprises components A and C and preferably one or more components selected from the group of components B, D and E, wherein the liquid crystal medium is Preferably the majority is particularly preferably essentially complete, very particularly preferably substantially complete.

  The liquid-crystalline media according to the invention are preferably at least −20 ° C. or lower and 70 ° C. or higher, in particular in each case, particularly preferably −30 ° C. or lower to 80 ° C. or higher, very particularly preferably −40 ° C. or lower to 85 ° C. As described above, most preferably, it has a nematic phase from −40 ° C. to 90 ° C.

  In the present specification, the expression “having a nematic phase” means that the smectic phase and crystallization are not confirmed at low temperatures at the corresponding temperature on the one hand, and on the other hand, no transparency occurs even when heated from the nematic phase. Means. The low temperature study is conducted in a flow viscometer at the corresponding temperature and is confirmed by storage for at least 100 hours in a test cell having a cell thickness corresponding to the electro-optic application. A medium is said to be stable at this temperature if the storage stability at a temperature of −20 ° C. in the corresponding test cell is 1000 hours or more. At temperatures of −30 ° C. and −40 ° C., the corresponding times are 500 hours and 250 hours, respectively. At high temperatures, the clearing point is measured in a capillary tube by conventional methods.

  In a preferred embodiment, the liquid crystal medium according to the invention is characterized by a medium to low region of optical anisotropy value. The birefringence value is preferably in the range from 0.065 to 0.130, particularly preferably in the range from 0.080 to 0.120, very particularly preferably from 0.085 to 0.1. Within the range of 110 or less.

  In this embodiment, the liquid crystal medium according to the present invention has a negative dielectric anisotropy, preferably 2.7 to 5.3, preferably 4.5 or less, preferably 2.9 to 4. An absolute value (| Δε |) of relatively high dielectric anisotropy within a range of 5 or less, particularly preferably from 3.0 to 4.0, very particularly preferably from 3.5 to 3.9. Have.

The liquid crystal medium according to the invention is 1.7 V to 2.5 V, preferably 1.8 V to 2.4 V, particularly preferably 1.9 V to 2.3 V, very particularly preferably 1.95 V. It has a relatively low threshold voltage (V ₀ ) in the range of ˜2.1V or less.

In a further preferred embodiment, the liquid crystal medium according to the present invention is preferably from 5.0 to 7.0, preferably from 5.5 to 6.5, and even more preferably from 5.7 to 6.4. In the following, it is particularly preferable that the average dielectric anisotropy (ε _av ≡ (ε _‖ ) having a relatively low value in the range of 5.8 to 6.2, very particularly preferably 5.9 to 6.1. the + 2ε _⊥) / 3), preferably has.

  In a preferred embodiment particularly suitable for use in LCD television displays, the liquid-crystalline media according to the invention are preferably 1.7 to 4.9, preferably up to 4.3, preferably 2.3 to 4. It has an absolute value (| Δε |) of dielectric anisotropy within a range of 0 or less, particularly preferably 2.8 or more and 3.8 or less.

In this embodiment, the liquid crystal medium according to the present invention has a threshold voltage (V ₀ ) in the range of 1.9 V to 2.5 V, preferably 2.1 V to 2.3 V.

  In addition, the liquid crystal medium according to the present invention has a high voltage holding ratio in the liquid crystal cell. In a newly filled cell, in a cell at 20 ° C., the voltage holding ratio is 95% or higher, preferably 97% or higher, particularly preferably 98% or higher, very particularly preferably 99% or higher. In the cell after 5 minutes in the oven, the voltage holding ratio is 90% or more, preferably 93% or more, particularly preferably 96% or more, very particularly preferably 98% or more.

  In general, herein, liquid crystal media having a low address voltage or threshold voltage have a lower voltage holding ratio than those having a higher address voltage or threshold voltage, and vice versa.

  Also preferably, these preferred values for the individual physical properties are also maintained by the medium according to the invention in each case in combination with each other.

  In this application, unless stated otherwise, the term “compound (multiple)”, also referred to as “compound (one or multiple)”, means both one and multiple compounds.

  Unless indicated otherwise, generally the individual compounds in the mixture in each case at a concentration of from 1% to 30%, preferably from 2% to 30%, particularly preferably from 3% to 16% Is used.

In the present invention, the following definitions apply in connection with the identification of the components of the composition, unless otherwise indicated in individual cases:
-"Contains": the concentration of the constituent components in question in the composition is preferably 5% or more, particularly preferably 10% or more, very particularly preferably 20% or more,
“Mostly”: the concentration of the constituents in question in the composition is preferably 50% or more, particularly preferably 55% or more, very particularly preferably 60% or more,
“Consisting essentially of”: the concentration of the constituent in question in the composition is preferably at least 80%, particularly preferably at least 90%, very particularly preferably at least 95%, and “substantially Completely complete ": The concentration of the constituents in question in the composition is preferably 98% or more, particularly preferably 99% or more, very particularly preferably 100.0%.

  This applies to the medium as a composition together with the constituents of the medium which may be components or compounds, and also to the constituents together with the constituents of the medium which is a compound. The term includes only with respect to the concentration of the individual compounds relative to the whole medium, preferably the concentration of the compound in question is 1% or more, particularly preferably 2% or more, very particularly preferably 4% or more. It means that.

  In the present invention, “≦” means below, preferably below, and “≧” means above, preferably above.

  In the present invention,

は、トランス−１，４−シクロヘキシレンを表し、および

Represents trans-1,4-cyclohexylene, and

は、１，４−フェニレンを表す。

Represents 1,4-phenylene.

  In the present invention, the expression “dielectrically positive compound” means a compound having Δε> 1.5, and the expression “dielectrically neutral compound” is one having −1.5 ≦ Δε ≦ 1.5. The expression “dielectrically negative compound” means that Δε <−1.5. As used herein, the dielectric anisotropy of a compound is 1 kHz in at least one test cell of homeotropic and uniform surface orientation with 10% compound dissolved in a liquid crystal host and in each case a cell thickness of 20 μm. In determining the volume of the resulting mixture. The measurement voltage is typically between 0.5V and 1.0V, but is always lower than the capacity threshold of the respective liquid crystal mixture under consideration.

  The host mixture used for dielectrically positive and dielectrically neutral compounds is ZLI-4792, and that used for dielectrically negative compounds is ZLI-2857, both of which are manufactured by Merck, Germany. is there. The value of the individual compound considered is obtained from the change in the dielectric constant of the host mixture after the addition of the compound considered and is extrapolated to 100% of the compound used. The compounds considered are dissolved in an amount of 10% in the host mixture. If the solubility of the material is too low for this purpose, the concentration is halved stepwise until it can be studied at the desired temperature.

  If necessary, the liquid-crystalline media according to the invention may also contain further additives, such as, for example, stabilizers and / or pleochroic dyes and / or chiral dopants in conventional amounts. The total amount of these additives used is preferably 0% to 10%, particularly preferably 0.1% to 6%, based on the total amount of the mixture. The concentration of the individual compounds used is preferably from 0.1% to 3%. The concentrations of these and similar additives are generally not considered when specifying the concentration and concentration range of the liquid crystal compound in the liquid crystal medium.

  In a preferred embodiment, the liquid-crystalline medium according to the invention comprises a polymer precursor comprising one or more reactive compounds, preferably reactive mesogens, and optionally, for example, polymerization initiators and / or polymerization regulators. Additional additives are included in conventional amounts. The total amount of these additives used is 0% to 10%, preferably 0.1% to 2%, based on the total amount of the mixture. The concentrations of these and similar additives are not taken into account when specifying the concentration and concentration range of the liquid crystal compound in the liquid crystal medium.

  The composition comprises a plurality of types of compounds, preferably from 3 to 30 types, particularly preferably from 6 to 20 types, very particularly preferably from 10 to 16 types, which are conventional Mixed in the way. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the major component of the mixture. This can be done effectively by raising the temperature. Completion of the melting operation is particularly easily seen when the selected temperature is above the clearing point of the main constituent. However, it is also possible to prepare liquid crystal mixtures, for example using premixes or in other conventional methods from so-called “multi-bottle systems”.

The mixtures according to the invention are very clear with a very good low temperature stability at −30 ° C. and −40 ° C., simultaneously with a clearing point above 65 ° C., a very desirable value of the capacity threshold, a relatively high value of voltage holding ratio. Shows a wide nematic phase range. Furthermore, the mixtures according to the invention are distinguished by a low rotational viscosity γ ₁ .

  It will also be appreciated by those skilled in the art that the media according to the present invention for use in VA, IPS, FFS or PALC displays are compounds in which, for example, H, N, O, Cl, F are replaced by the corresponding isotopes. Can be included.

  The structure of the liquid crystal display according to the present invention corresponds to a conventional configuration as described in, for example, European Patent Application No. 0 240 379.

  By utilizing suitable additives, the liquid crystal phase according to the invention can be modified to be used in any of the previously disclosed types, for example ECB, VAN, IPS, GH or ASM-VA-LCD displays. it can.

  Table E below shows possible dopants that can be added to the mixtures according to the invention. If the mixture contains one or more dopants, it is used in an amount of 0.01 to 4% by weight, preferably 0.1 to 1.0% by weight.

  For example, stabilizers that can be added to the mixtures according to the invention in amounts of preferably 0.01 to 6% by weight, in particular 0.1 to 3% by weight, are set forth in Table F below.

  For purposes of the present invention, all concentrations are given in weight percent unless otherwise specified, and relate to the corresponding mixture or mixture component unless otherwise specified.

  Unless indicated otherwise, it is shown in this application such as melting point T (C, N), smectic (S) to nematic (N) phase transition T (S, N) and clearing point T (N, I). All temperature values are given in degrees Celsius (° C.) and all temperature differences are shown correspondingly in degrees of difference (° or degrees).

In the present invention, the term “threshold voltage” relates to a capacity threshold (V ₀ ), also known as the Fredericks threshold, unless otherwise specified.

  All physical properties are determined or determined in accordance with Merck liquid crystal, liquid crystal physical properties, November 1997, according to Merck, Germany, and in each case a temperature of 20 ° C. is used unless otherwise stated. As applied, Δn is determined at 589 nm and Δε is determined at 1 kHz.

The electro-optical properties, for example the threshold voltage (V ₀ ) (capacitive measurement), are determined in the same manner as the switching properties in a test cell manufactured at Merck Japan. The measurement cell has a soda-lime glass substrate, which is rubbed orthogonally to each other, and has a polyimide alignment layer (SE-1211 (dilution ratio 1: 1) with diluent ^** 26), which has the effect of homeotropic alignment of the liquid crystal. (Manufactured by Nissan Chemical Co., Ltd., Japan) and is configured in an ECB or VA structure. The surface area of the transparent and substantially square ITO electrode is 1 cm ² .

  Unless indicated otherwise, no chiral dopant is added to the liquid crystal mixture used, but the liquid crystal mixture is also particularly suitable for applications that require this type of doping.

The voltage holding ratio is determined in a test cell manufactured by Merck Japan. The measurement cell has a substrate made of soda-lime glass, and is composed of a polyimide alignment layer (AL-3046, manufactured by Japan Synthetic Rubber Co., Ltd.) rubbed orthogonally with a layer thickness of 50 nm. The layer thickness is uniformly 6.0 μm. The surface area of the transparent ITO electrode is 1 cm ² .

The voltage holding ratio is determined after 5 minutes (HR ₁₀₀ ) in ovens at 20 ° C. (HR ₂₀ ) and 100 ° C. The voltage used has a frequency of 60 Hz.

The rotational viscosity is determined using the rotating permanent magnet method, and the flow viscosity is determined with a modified Uverod viscometer. For the liquid crystal mixtures ZLI-2293, ZLI-4792 and MLC-6608, all products of Merck in Darmstadt, Germany, the rotational viscosity values determined at 20 ° C. are 161 mPa · s, 133 mPa · s and 186 mPas, respectively. S and the fluid viscosity values (ν) are 21 mm ² s ⁻¹ , 14 mm ² s ⁻¹ and 27 mm ² s ⁻¹ , respectively.

Use the following symbols:
V ₀ is the capacity threshold voltage (V) at 20 ° C.,
n _e is the extraordinary refractive index measured at 20 ° C. and 589 nm,
n ₀ is the normal refractive index measured at 20 ° C. and 589 nm,
Δn is the optical anisotropy measured at 20 ° C. and 589 nm,
ε _⊥ is the dielectric sensitivity perpendicular to the director at 20 ° C. and 1 kHz,
ε _‖ is the dielectric sensitivity parallel to the director at 20 ° C. and 1 kHz,
Δε is dielectric anisotropy at 20 ° C. and 1 kHz,
cl. p. Or T (N, I) is the clearing point (° C),
γ ₁ is the rotational viscosity (mPa · s) measured at 20 ° C.,
K ₁ is the elastic constant (pN) for “spray” deformation at 20 ° C.,
K ₂ is the elastic constant (pN) for “twist” deformation at 20 ° C.,
K ₃ is the elastic constant (pN) for “bend” deformation at 20 ° C., and LTS is the low temperature stability (phase stability) determined in the test cell.

  The following examples illustrate the invention without limitation. However, they show the person skilled in the art the concept of preferred mixtures of the compounds preferably used and their respective concentrations and their combinations with one another. In addition, the examples illustrate possible properties and combinations of properties.

In the present invention and in the following examples, the structure of the liquid crystal compound is indicated using an acronym and the conversion to the chemical formula is performed according to Tables A to C below. All groups _{C n H 2n + 1, C} m H 2m + 1 and _C l _{H 2l + 1} or _{C n H 2n, C m H} 2m and _C l _{H 2l,} it if it, each n, m and l C atoms A linear alkyl group or an alkylene group having Table A shows the codes for the core ring elements of the compound, Table B lists the bridging units, and Table C lists the meanings of the symbols for the left and right end groups of the molecule. The acronym is composed of a code for the ring element with an optional bridging group, followed by a code for the first hyphen and left end group, and a code for the second hyphen and right end group. Table D shows exemplary structures of the compounds with their respective abbreviations.
<Table A: Ring element>

＜表Ｂ：架橋単位＞

<Table B: Crosslinking unit>

＜表Ｃ：末端基＞

<Table C: End groups>

表中、ｎおよびｍは、それぞれ整数であり、３つの点「．．．」は、この表からの他の略号のための場所を表す。

In the table, n and m are each integers, and the three points "..." represent places for other abbreviations from this table.

  In addition to the compounds of formula I, the mixtures according to the invention preferably comprise one or more compounds of the following compounds:

Use the following abbreviations:
(N, m and z each independently represent an integer, preferably 1-6)
<Table D>

表Ｅに、本発明による混合物において好ましく使用されるキラルドーパントを示す。
＜表Ｅ＞

Table E shows the chiral dopants preferably used in the mixtures according to the invention.
<Table E>

表Ｅからの化合物群より選択される化合物。
＜表Ｆ＞
（ここで、ｎは１〜１２の整数を表す。）

A compound selected from the group of compounds from Table E.
<Table F>
(Here, n represents an integer of 1 to 12.)

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から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 from Table F.

<Example of mixture>
<Examples 1.1 and 1.2>
<Example 1.1>

  <Example 1.2>

<Examples 2.1 and 2.2>
<Example 2.1>

  <Example 2.2>

<Examples 3.1 and 3.2>
<Example 3.1>

  <Example 3.2>

  <Example 4>

  <Example 5>

  <Example 6>

  Different ones of the exemplary mixtures already mentioned may be appropriately mixed with each other, thereby achieving a mixture of properties with similar advantages. In particular, the number of components of the mixture increases as a result, in most cases leading to an increase in the storage stability of the mixture, especially at low temperatures.

Claims (15)

a) a first dielectrically negative component (component A) comprising one or more compounds of formula I;
b) a liquid crystal medium with negative dielectric anisotropy comprising a second dielectrically negative component (component B) comprising one or more compounds of formula II.

(Where
R ¹¹ and R ¹² each independently represent H, an unsubstituted alkyl or alkenyl group having up to 15 C atoms, but in addition, one or more CH ₂ groups in these groups are O The atoms are not directly bonded to each other so that -O-, -S-,

_{-C≡C -, - CF 2 -O -} , - O-CF 2 -, - CO-O- or may be replaced by -O-CO-,

Represents
And others, if present, are independent of each other,

Represents
Z ^{11 to} Z ¹³ are each independently of each other —CH ₂ —CH ₂ —, —CH═CH—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —CO—O. _{-, - O-CO -,} - CF 2 -O -, - O-CF 2 -, - CF 2 -CF 2 - or a single bond,
m and n each independently represents 0 or 1. )

(Where
R ²¹ and R ²² , independently of one another, represent H, an unsubstituted alkyl or alkenyl group having up to 15 C atoms, but in addition, one or more CH ₂ groups in these groups are O The atoms are not directly bonded to each other so that -O-, -S-,

—C≡C—, —CF ₂ —O—, —O—CF ₂ —, —CO—O— or —O—CO— may be substituted, provided that all groups have one or more H The atom may be replaced by a halogen atom,

Represents
And the other, if present, are independent of each other,

Represents

Together, it may represent a single bond,
L ²¹ and L ²² each independently represent = C (X ⁴ )-, and one of L ²¹ and L ²² alternatively represents = N-
X ⁴ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ ,
Z ²¹ to Z ²³ each, independently of one _{another, -CH 2 -CH 2 -, -} CH 2 -CF 2 -, - CF 2 -CH 2 -, - CF 2 -CF 2 -, - CH = CH-, —CF═CH—, —CH═CF—, —C≡C—, —CH ₂ —O—, —O—CH ₂ —, —O—, —CH ₂ —, —CO—O—, —O—. CO—, —CF ₂ —O—, —O—CF ₂ — or a single bond is represented, and l and o each independently represents 0 or 1. ) 2. The medium according to claim 1, further comprising c) a dielectrically neutral component (component C) comprising one or more compounds of the formula III.

(Where
R ³¹ and R ³² each independently of one another have one of the meanings given to R ¹¹ and R ¹² ;

Represents
Z ^{31 to} Z ³³ each independently have one of the meanings given to Z ^{11 to} Z ¹³ ,
p and q each independently represent 0 or 1. ) d) additionally comprising a further dielectrically negative component (component D) consisting of one or more compounds selected from the group of compounds of the formulas IV and V Medium.

(Where
R ⁴¹ , R ⁴² , R ⁵¹ and R ⁵² each independently of one another have one of the meanings given to R ²¹ and R ²² ;

Represents
And the other rings, if present, are independently of each other,

Represents
L ⁴¹ and L ⁴² each independently represent ═C (X ⁴ ) —, and one of L ⁴¹ and L ⁴² alternatively represents ═N—
X ⁴ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F, CHF ₂ ,

Represents
Others, if present, are independent of each other,

Represents

It also represents a single bond,
Z ^{41 to} Z ⁴³ and Z ^{51 to} Z ⁵³ each independently have one of the meanings given to Z ^{11 to} Z ¹³ ,
r and s each independently represent 0 or 1,
t and u each independently represents 0 or 1; )   The medium according to any one of claims 1 to 3, further comprising e) a chiral component (component E) consisting of one or more chiral compounds.   5. The medium according to claim 1, comprising a first dielectrically negative component (component A) comprising a plurality of compounds of formula I according to claim 1.   6. A medium according to any one of the preceding claims, characterized in that the proportion of compounds of formula I in the mixture is not less than 15% by weight as a whole. The medium according to claim 1, comprising one or more compounds selected from the group of compounds of the formulas I-1 to I-4.

(Wherein the parameters have the meaning given in claim 1)   8. The proportion in the mixture of compounds of the formulas I-1 to I-4 as defined in claim 7 is 20% by weight or more in total. Medium. 2 to 80% by weight of one or more compounds of formula I;
2 to 80% by weight of one or more compounds of formula II,
2 to 80% by weight of one or more compounds of formula III, and / or 2 to 80% by weight of one or more compounds of formula IV and / or V,
9. A medium according to any one of the preceding claims, characterized in that the total content of all compounds of the formulas I to V in the medium is not more than 100% by weight.   An electro-optical display comprising the liquid crystal medium according to claim 1 as a dielectric.   11. A display according to claim 10, comprising an active-matrix addressing device.   12. Display according to claim 10 or 11, characterized in that it is based on VA, ECB, PALC, FFS or IPS effect.   Use of a liquid crystal medium according to any one of claims 1 to 9 in an electro-optic display.   Use of a liquid crystal medium according to claim 13 in an electro-optic display having an active-matrix addressing device. A method for preparing a medium according to any one of claims 1 to 10, comprising
One or more compounds of formula I as given in claim 1 with one or more compounds of formula II as given in claim 1 and / or any one of claims 2-3 and 7. A method comprising mixing with one or more compounds and / or one or more further liquid crystal compounds and / or one or more additives as described in the paragraph.