JP6370527B2 - Liquid crystal medium - Google Patents

Description

  The present invention uses liquid crystal media, its use in liquid crystal displays, and these liquid crystal displays, in particular the ECB (electrically controlled birefringence) effect with dielectrically negative liquid crystals in the homeotropic starting orientation. It relates to a liquid crystal display. The liquid crystal medium according to the invention stands out in the display according to the invention by a particularly high response time with a short response time.

  The display using the ECB effect is a so-called VAN (vertically aligned nematic) display, an IPS (in-plane switching) display (for example: Yeo, SD, paper 15.3: “ A LC Display for the TV Application ", SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pages 758 and 759 (Nt. In addition, it is currently the most important liquid crystal display for TV applications. It has been established as one of three more recent types of play.

  The most important designs that should be mentioned are: MVA (multi-domain vertical alignment: multi-domain vertical alignment, eg: Yoshihide, H. et al., Paper 3.1: “MVA LCD for Notebook or Mobile PCs” SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book I, pp. 6-9 (Non-patent Document 2) and Liu, CT et al., Paper 15.1: “A 46-inch TFT-LCD HDTV Technol ( SID 2004 International Symposium, Digest of Technical Papers, XXX , Book II, 750-753 (Non-patent Document 3)), PVA (patterned vertical alignment: patterned vertical alignment, for example: 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, XXXV, Book II, pages 760 to 763 (non-patent document 4) and ASV (advanced super view, for example, advanced super view) Fukuoka, Hirofumi, Paper 15.2: “Development of High Q ality LCDTV ", SID 2004 International Symposium, Digest of Technical Papers, XXXV, is Book II, pp. 754-757 (Non-Patent Document 5)).

  In a general form, for example, at a SID seminar in Souk in June 2004, seminar M-6: “Recent Advances in LCD Technology”, seminar lecture notes, M-6 / 1 to M-6 / 26 (non-patented) Reference 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). ing. For example: Kim, Hyeon Kyong et al., Paper 9.1: “A57-in. Wide UXGA TFT-LCD for HDTV Application”, SID 2004 International Symposium, Digest of Technical Papers, Non-Patents XX10, XX Although the response time of recent ECB displays has already been significantly improved by the overdrive addressing method as in Reference 8), achieving a response time compatible with video can be achieved especially in switching of halftones. It is still a problem that has not been solved to a satisfactory extent.

  ECB displays such as ASV displays use negative dielectric anisotropy (Δε) liquid crystal media, while TN and all conventional IPS displays to date use positive dielectric anisotropy liquid crystal media.

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

  In displays, in general, that is, even in displays with these effects, the operating voltage must be as low as possible, so 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 value of dielectric anisotropy is used. In general, at most a relatively low proportion of neutral compounds is used, and if possible, compounds having a dielectric anisotropy of the opposite sign to the medium are not used. Therefore, in the case of a liquid crystal medium having a negative dielectric anisotropy for an ECB display, a compound having a negative dielectric anisotropy is mainly used. The liquid crystal medium used is generally composed mainly of a liquid crystal compound having a negative dielectric anisotropy, and usually consists essentially of it.

  In general, liquid crystal displays are intended to have the lowest possible address voltage, so in the media used by this application, typically at most significant amounts of dielectrically neutral liquid crystal compounds and Generally, only very small amounts of dielectrically positive compounds are used, or no further use.

  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 insufficient transmission in the display.

  In addition, the address voltage of prior art displays is often too high, especially for displays that are not directly or continuously connected to a power supply network such as, for example, a display intended for portable use.

  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 for displays for television or 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 inadequate for many applications, so it seems desirable to find further optimization approaches.

  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 to a significant extent.

  Surprisingly, it has been found that it is possible to achieve a liquid crystal display having a short response time in an ECB display and at the same time having a sufficiently wide nematic phase, a preferred birefringence (Δn) and a high voltage holding ratio. It was issued.

  This type of medium is used in particular for electro-optic displays that are addressed in an active matrix based on the ECB effect and for in-plane switching (IPS) displays. The medium according to the invention preferably has a negative dielectric anisotropy.

  The principle of electrically controlled birefringence, the ECB (electrically controlled birefringence) effect or the DAP (deformation of aligned phases) effect was first described in 1971 (MF Schiekel) And K. Fahrenschon, “Deformation of nematic liquids with vertical orientation”, Appl. Phys. Lett. 19 (1971), 3912. 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), p. 30 (Non-patent Document 12)), J. Am. Duchene (Displays 7 (1986), 3 (Non-Patent Document 13)) and H.C. In order to be suitable for use for advanced information display elements based on the ECB effect in a report by Schad (SID 82 Digest Techn. Papers (1982), p. 244 (Non-Patent Document 14)) It was shown that the liquid crystal phase must have a high value for the ratio K ₃ / K ₁ between, a high value for the optical anisotropy Δn, and a value of −0.5 or less for the dielectric anisotropy Δε. Electro-optic display elements based on the ECB effect have a homeotropic edge orientation (VA technology, ie 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, an LC phase that must satisfy a number of requirements is required. Of particular importance here are chemical resistance to moisture, air and physical effects such as heat, radiation in the infrared, visible and ultraviolet regions and direct and alternating electric fields.

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

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

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

  Two technologies are distinguished: for example TFTs comprising compound semiconductors such as CdSe or TFTs based on polycrystalline and in particular amorphous silicon. At present, the latter technology is the most commercially important worldwide.

  The TFT matrix is applied to 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. The technology can also be extended to full color displays, in which a mosaic of red, green and blue filters is placed so that the filter elements face each switchable pixel.

  Most TFT displays that have been used so far usually operate with a polarizer orthogonal to the transmission and are backlit. For television applications, IPS cells or ECB (or VAN) cells are used, while monitors typically use IPS cells or TN cells, and notebook computers, laptops and portable applications typically use TN cells. Is used.

  As used herein, the term MLC display refers to any matrix display with integrated nonlinear elements, ie, active matrix plus varistor or diode (MIM, ie metal-insulator-metal). ) And other passive devices.

  This type of MLC display is particularly suitable for television applications, monitors and laptops, or high information density displays in, for example, automobile products or aircraft. In addition to problems with contrast angle dependence and response time, MLC displays also have problems due to the specific resistance of the liquid crystal mixture not being sufficiently high [TOGASHHI, S .; SEKIGUCHI, K .; TANABE, H .; , YAMAMOTO, E .; SORIMACHI, K .; TAJIMA, E .; WATANABE, H .; And SHIMIZU, H .; Proc. Eurodisplay 84, September 1984: A210-288, Matrix LCD Controlled by Double Stage Diode Rings, page 141ff, Paris (Non-patent Document 15); Proc. Eurodisplay 84, September 1984, Design of Thin Film Transistors for Matrix Addressing of Television Liquid Display, 145ff, Paris (Non-Patent Document 16). As the resistance decreases, the contrast of the MLC display deteriorates. The specific resistance of the liquid crystal mixture generally decreases over the life of the MLC display due to interaction with the internal surface of the display, so for displays that must have an acceptable resistance value over a long operating period. High (initial) resistance is very important.

  The compounds of formula I are described, for example, in JP 2005-047 980 (Patent Document 1) as components of liquid crystal mixtures in combination with substantially dielectrically neutral indanes. The publication also mentions the preparation of compounds of formula I. German Patent Application No. 10 2008 01 46 49.8, which has not yet been published, describes compounds of formula I in combination with negative dielectric anisotropy indanes.

  The compounds of the formula II are, for example, EP 0 364 538 (Patent Document 3), EP 0 363 548 (Patent Document 4) and German Patent 39 06 058 (Patent Document 3). Document 5), which also describes the synthesis of several compounds of this type. Other compounds of formula II are prepared analogously.

  The disadvantages of the MLC displays disclosed so far are that these displays have a relatively low contrast, a relatively high viewing angle dependency, and difficulty in producing halftones, and Based on their insufficient voltage holding ratio and their inadequate lifetime.

  Therefore, it has a wide operating temperature range, a short response time and a low threshold voltage at the same time as a very high specific resistance. Thanks to these, various halftones can be generated, in particular, a good and stable voltage holding ratio. There continues to be a great demand for MLC displays.

Japanese Patent Laying-Open No. 2005-047 980 German Patent Application No. 10 2008 01 46 49.8 European Patent No. 0 364 538 European Patent No. 0 363 548 German Patent No. 39 06 058

Yeo, S .; D. 15.3: “A LC Display for the TV Application”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pages 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, 6-9. Liu, C.I. T.A. 15.1 “A 46-inch TFT-LCD HDTV Technology (hereinafter omitted)”, SID 2004 International Symposium, Digest of Technical Papers, XXXV, Book II, pages 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 P, 76, X Shigeta, Mitzhiro and Fukuoka, Hirofumi, Paper 15.2: “Development of High Quality LCDTV”, SID 2004 International Symposium, Digest of Tech 7, 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 XXV, XXV M.M. F. Schieckel and K.C. Fahrenshon, “Deformation of nematic liquids with vertical orientation in electrical fields”, Appl. Phys. Lett. 19 (1971), 3912 J. et al. F. Kahn, Appl. Phys. Lett. 20 (1972), 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), p. 30 J. et al. Duchene, Displays Volume 7 (1986), 3 pages H. Schad, SID 82 Digest Techn. Papers (1982), p. 244 TOGASHHI, S.M. SEKIGUCHI, K .; TANABE, H .; , YAMAMOTO, E .; SORIMACHI, K .; TAJIMA, E .; WATANABE, H .; And SHIMIZU, H .; Proc. Eurodisplay 84, September 1984: A210-288, Matrix LCD Controlled by Double Stage Diode Rings, 141ff, Paris STROMER, M.M. Proc. Eurodisplay 84, September 1984, Design of Thin Film Transistors for Matrix Addressing of Television Liquid Displays, page 145ff, Paris

  The present invention is not only for monitors and television applications, but also for mobile phones and navigation systems, based on the ECB or IPS effect, and does not have the disadvantages indicated above or only to a lesser extent, At the same time, it aims to provide an MLC display having a very high specific resistance value. In particular, for mobile phones and navigation systems, it must be ensured that they operate even at very high and very low temperatures.

  Surprisingly, it has now 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 therefore relates to a liquid-crystalline medium based on a mixture of polar compounds and comprising at least one compound of formula I and at least one compound of formula II.

  The mixture according to the invention is very good at −30 ° C. and −40 ° C. with a very wide nematic phase range with a clearing point above 85 ° C., a very favorable value for the capacity threshold, a relatively high value for retention. Show low temperature 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 by a high negative dielectric anisotropy.

The present invention
a) preferably a first dielectrically negative component (component A) comprising one or more compounds of formula I;
b) a second dielectrically negative component (component B) comprising one or more compounds of formula II;
c) Dielectrically neutral components (component C) consisting of one or more compounds of formula III as optional components;
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;
e) A dielectric negative nematic medium comprising, as an optional component, a chiral component (component E) composed of one or more kinds of chiral compounds.

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原子を有し無置換のアルキルまたはアルケニル基（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原子が互いに直接連結しないようにして、−Ｏ−、−Ｓ−、

Where
R ¹¹ and R ¹² are each independently of each other 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 atoms Are not directly connected to each other, -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い。）、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、特には、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、特には、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 may be replaced by -O-CO-. ), Preferably an unsubstituted alkyl, alkenyl, alkoxy or alkenyloxy group, particularly preferably one of R ¹¹ and R ¹² represents an alkyl or alkenyl group and the other is an alkyl, alkenyl, alkoxy or alkenyloxy group R ¹¹ is particularly preferably linear 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 —, wherein R ¹² is alkoxy , In particular, C ₂ H ₅ —O— or n—C ₄ H ₉ —O—,

好ましくは、

Preferably,

および、存在するのであれば、その他は、それぞれ互いに独立に、

And, if present, the others 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、
および、特に好ましくは、

Represents
And particularly preferably

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個、または存在するのであれば、それより多いＺ^１１〜Ｚ^１３は単結合を表し、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、特に好ましくは、０を表す。

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. 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, particularly 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原子を有し無置換のアルキルまたはアルケニル基（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原子が互いに直接連結しないようにして、−Ｏ−、−Ｓ−、

Where
R ²¹ and R ²² are each independently 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 atoms Are not directly connected to each other, -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い。）、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、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、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、全ての基における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、特には、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、特には、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 may be replaced by -O-CO-. ), Preferably an unsubstituted alkyl, alkenyl, alkoxy or 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 And preferably, independently of one another, alkyl having 1 to 7 C atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5 C atoms, 1 to 7 Alkoxy having C atoms, preferably n-alkoxy, particularly preferably n-alkoxy having 1 to 5 C atoms, or 2 to 7 C atoms, preferably 2 to 4 C atoms. Represents alkoxyalkyl, alkenyl or alkenyloxy, preferably alkenyl, provided that 1 in all groups Or more H atoms, a halogen atom, 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, 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 _{E-n-C 3 H 7} -CH = CH-

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

および、存在するのであれば、その他は、それぞれ互いに独立に、

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

（ただし、
Ｌ^２１およびＬ^２２は、互いに独立に、＝Ｃ（Ｘ^２）−を表し、また、あるいは、Ｌ^２１およびＬ^２２の一方は＝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^２１およびＬ^２２の両方が＝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を表す。）
特に好ましくは、

(However,
L ²¹ and L ²² represent, independently of each other, ═C (X ² ) —, or alternatively one of L ²¹ and L ²² also represents ═N—, but preferably of L ²¹ and L ²² At least one represents = C (-F)-and the other represents = C (-F)-or = C (-Cl)-, and particularly preferably both 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. )
Particularly preferably,

特に好ましくは、

Particularly preferably,

および、非常に特に好ましくは、

And very particularly preferably

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個、または存在するのであれば、それより多い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。

Represents
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
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、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 2 to 4 C atoms, preferably alkenyloxy,

好ましくは、

Preferably,

を表し、
好ましくは、

Represents
Preferably,

好ましくは、

Preferably,

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。

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およびＲ^４２、Ｒ^５１およびＲ^５２は、それぞれ互いに独立に、Ｈ、１５個までのＣ原子を有し無置換のアルキルまたはアルケニル基（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原子が互いに直接連結しないようにして、−Ｏ−、−Ｓ−、

Where
R ⁴¹ and R ⁴² , R ⁵¹ and R ⁵² are each independently of one another H, an unsubstituted alkyl or alkenyl group having up to 15 C atoms (but in addition to one or more CH in these groups). _{The two} groups are such that O atoms are not directly linked 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い。）、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、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、全ての基における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^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、特には、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、特には、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、
特に好ましくは、Ｒ^５１およびＲ^５２の一方、好ましくは、Ｒ^５１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^４１は直鎖状のアルキル、特には、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、特には、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 may be replaced by -O-CO-. ), Preferably an unsubstituted alkyl, alkenyl, alkoxy or 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, independently of one another, alkyl having 1 to 7 C atoms, preferably n-alkyl, particularly preferably n-alkyl having 1 to 5 C atoms, 1 to 7 C atoms Alkoxy, preferably n-alkoxy, particularly preferably n-alkoxy having 1 to 5 C atoms, or alkoxy having 2 to 7 C atoms, preferably 2 to 4 C atoms Represents alkyl, alkenyl or alkenyloxy, preferably alkenyl, provided that one or more in all groups H atoms, a halogen atom, preferably, may be replaced by F atoms,
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 _{E-n-C 3 H 7} -CH = CH-
Particularly preferably, one of R ⁵¹ and R ⁵² , preferably R ⁵¹ represents an alkyl or alkenyl group, the other represents an alkyl, alkenyl, alkoxy or alkenyloxy group, particularly preferably R ⁴¹ 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 _{E-n-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、また、あるいは、Ｌ^４１およびＬ^４２の一方は＝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の両方が＝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、存在するのであれば、その他の環は、それぞれ互いに独立に、

L ⁴¹ and L ⁴² , independently of each other, represent ═C (X ⁴ ) —, or alternatively one of L ⁴¹ and L ⁴² also represents ═N—, but preferably of L ⁴¹ and L ⁴² At least one represents = C (-F)-and the other represents = C (-F)-or = C (-Cl)-, and particularly preferably both 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, if present, the other rings are independently of each other,

好ましくは、

Preferably,

特に好ましくは、

Particularly preferably,

を表し、

Represents

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、
好ましくは、

Represents
Preferably,

を表し、
特に好ましくは、

Represents
Particularly preferably,

および、存在するのであれば、その他は、それぞれ互いに独立に、

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

好ましくは、

Preferably,

好ましくは、

Preferably,

を表し、
また、

Represents
Also,

は、共に単結合を表してもよく、
ただし、

May both represent a single bond,
However,

を表す場合、好ましくは、
Ｒ^５２はＨを表し、
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個、または存在するのであれば、それより多いＺ^４１〜Ｚ^４３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、
Ｚ^５１〜Ｚ^５３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個、または存在するのであれば、それより多いＺ^５１〜Ｚ^５３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、
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を表し、
ただし、式ＩＩの化合物は式ＩＶの化合物より除外される。

Preferably represents
R ⁵² represents H;
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,
Z ⁵¹ to Z ⁵³ 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 ^{51 to} Z ⁵³ 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,
However, compounds of formula II are excluded from compounds of formula IV.

  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 than one compounds of the formula I.

As a compound of formula I,
a) compounds in which R ¹¹ and / or R ¹² represent H, preferably alkyl, alkenyl or alkoxy having up to 6 C atoms, and R ¹² very particularly preferably represents alkoxy or alkenyloxy,
b) R ¹¹ and R ¹² both represent alkyl, provided that the alkyl groups may be the same or different;
c) Compounds in which R ¹¹ represents straight-chain alkyl, vinyl, 1E-alkenyl or 3-alkenyl are particularly preferred.

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 of formulas I-1 and I-3, particularly preferably of the group of formula I-1.

式中、パラメータは、式Ｉにおいて上に与えられるそれぞれの意味を有し、および好ましくは、

In which the parameters have the respective meaning given above in formula I, and preferably

特に好ましくは、互いに独立に

Particularly preferably, independently of each other

を表す。

Represents.

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

式中、パラメータは上で与えられる意味を有し、および好ましくは、
式Ｉ−１ａおよびＩ−２ａ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−３ａおよびＩ−４ａ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、および
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 meaning given above, and preferably
In Formulas I-1a and I-2a,
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-3a and I-4a,
Z ¹¹ represents —CH ₂ —CH ₂ — or a single bond, preferably a single bond, and Z ¹² represents —CH ₂ —CH ₂ —, —CH ₂ —O— or a single bond, preferably — CH ₂ —O— or a single bond, particularly preferably —CH ₂ —O— is represented.

  The following compounds are very particularly preferred: compounds of the formulas I-1a-1, I-1a-2, I-3a-1 and I-3a-2.

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 and 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 to II-5, preferably formula II-2.

式中、
Ｒ^２１およびＲ^２２は、上で与えられる意味を有し、および
Ｒ^２１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^２２は、好ましくは、１〜５個、特に好ましくは２〜４個のＣ原子を有するアルキルを表し、
Ｘ^２２〜Ｘ^２６は、互いに独立に、ＨまたはＦを表し、および
Ｘ^２７およびＸ^２８の一方はＨを表し、他方はＨまたはＦを表し、
好ましくは、存在する全てのＸ^２２〜Ｘ^２８がＨを表すか、または、Ｘ^２２〜Ｘ^２８の１個または２個がＦを表し、その他はＨを表す。

Where
R ²¹ and R ²² have the meanings given above, and R ²¹ preferably represents alkyl having 1 to 7, preferably 1 to 5 C atoms, preferably n-alkyl. ,
R ²² preferably represents alkyl having 1 to 5, particularly preferably 2 to 4 C atoms,
X ^{22 to} X ²⁶ each independently represent H or F, and one of X ²⁷ and X ²⁸ represents H, the other represents H or F,
Preferably, all X ^{22 to} X ²⁸ present represent H, or one or two of X ^{22 to} X ²⁸ represents F and the others represent H.

  In a particularly preferred embodiment, the medium is of formula II-1 selected from the group of compounds of formula II-1a to II-1d, preferably of formula II-1b and / or II-1d, particularly preferably of formula II-1b Contains 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.

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

  In a further preferred embodiment, the medium is a compound of formula II-2a to II-2d, preferably of formula II-2a and / or II-2c, particularly preferably of formula II-2a, and / or of formula II-2e. -One or more compounds of formula II-2 selected from the group of compounds of II-2i.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子、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、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、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 an 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 is alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms Represents.

式中、
Ｒは、Ｒ^４１について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 preferably has 1 to 6 C atoms each and is linear alkyl or alkoxy, or alkoxyalkyl, alkenyl or alkenyloxy having 2 to 6 C atoms, particularly preferably 1 Alkyl having ˜5 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 is a compound of formula II-3a to II-3d, preferably formula II-3a and / or II-3c, particularly preferably a group of compounds of formula II-3a, and / or formula II-3e. Includes one or more compounds of Formula II-3 selected from the group of compounds of ~ II-3m.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子、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、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、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 an 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, and alkenyl is alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms Represents.

式中、
Ｒは、Ｒ^４１について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 preferably has 1 to 6 C atoms each and is linear alkyl or alkoxy, or alkylalkoxy, alkenyl or alkenyloxy having 2 to 6 C atoms, particularly preferably 1 Alkyl having ˜5 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 formula III, wherein

ただし、２個の隣接する環は、非常に特に好ましくは、直接連結しており、
より正確に好ましくは、

However, two adjacent rings are very particularly preferably linked directly,
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で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一方の１個または２個の隣接していないＣＨ_２基は、Ｏ原子で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 either one or two of the cyclohexylene ring or two cyclohexylene rings. Non-adjacent CH ₂ groups may be replaced by O atoms.

  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. Particularly preferably 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、および
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, and 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
Formula III-1, wherein -R ³¹ represents vinyl or 1-propenyl, R ³² represents alkyl, preferably n-alkyl, particularly preferably R ³¹ represents vinyl and R ³² represents propyl,
-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 more).

  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、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、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及びａｌｋｅｎｙｌ’は、互いに独立に、２〜７個のＣ原子、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 an 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 comprises a compound of the formula III-1, in particular a compound of the formula III-1c ′, in an amount of preferably 20% or more, in particular 25% or more, very particularly preferably 30% or more.

式中、
ｎは、３、４、５であり、および、Ｒ^ｅはＨまたはＣＨ_３を表す。

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

  In a further preferred embodiment, the medium is of formula III-1a selected from the group of compounds of formula III-1a and III-1b, preferably of formula III-1a and / or III-1b, particularly preferably of formula III-1a. One or more compounds. In this embodiment, the medium preferably does not comprise a compound of formula III, preferably formula III-1, containing one alkenyl end group or a plurality of alkenyl end groups, ie preferably formula III-1c Does not include the compound of ~ III-1e. In this embodiment, the medium particularly preferably comprises 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, acronyms (abbreviations) are described in Tables AC and illustrated 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、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、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、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 an 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 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、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、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 an 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 ratio of these biphenyls in the whole mixture is preferably 3% or more, particularly 5% 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:

これらの中でも、特に、最後の式のものが好ましい。

Among these, the last formula is particularly preferable.

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

  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、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、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、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 an 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 or more).

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 one or more of the formula III-5 selected from the group of compounds of the formula III-5e to III-5h, preferably the formula III-5e and / or III-5f, particularly preferably the formula III-5e Contains compounds.

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子、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、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、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 an 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、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、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、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 an 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、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、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、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 an 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 the formula III-6a selected from the group of compounds PGP-2-3, PGP-3-3 and PGP-3-4, and preferably of the formula PGP- 1 or more compounds selected from compounds of formula III-6b selected from the group of 1-2V, PGP-2-2V and PGP-3-2V, provided that the acronym (abbreviation) This is described 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、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 selected from the group of compounds 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、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 to IVD, preferably IVA to 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中において、

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、両者が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-9.

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の両方が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を表すが、
好ましくは最大で４つ、特に好ましくは最大で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に上で示されるそれぞれの意味を有し、および好ましくは、
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_ｖＨ２_ｖ＋１を表し、および
ｖは、１〜６の整数を表す。

Where
Y ^{41 to} Y ⁴⁶ each independently represent H or F, and both X ⁴¹ and X ⁴² represent H, or one of X ⁴¹ and X ⁴² represents H and the other represents F But,
Preferably at most 4, particularly preferably at most 3, very particularly preferably one or two 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, and preferably
R ⁴¹ represents alkyl or alkenyl, and R ⁴² represents alkyl, alkenyl, alkoxy or alkenyloxy, preferably (O) C _v H2 _{v + 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、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、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、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 an 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-3a and / or IV-3b, 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、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、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、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 an 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, and alkenyl is alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms Represents.

  Preferred compounds of formula IV-3c and IV-3d are those of the following formulae:

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-3 of the following sub-formula IV-3e.

式中、
Ｒ^４１は、上で示される意味を有し、
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;
m and z each independently represents an integer of 1 to 6, and m + z preferably represents an integer of 1 to 6.

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

式中、
ａｌｋｙｌおよびａｌｋｙｌ’は、互いに独立に、１〜７個のＣ原子、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、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、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 an 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, and alkenyl is alkenyl having 2 to 7 C atoms, preferably 2 to 5 C atoms Represents.

  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-8 selected from the group of compounds of formula IV-8a and IV-8b, particularly preferably formula 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、
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} ,
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、
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} ,
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-9 selected from the group of compounds of formula IV-9a to IV-9d, preferably formula IV-9a and / or IV-9b, particularly preferably IV-9b. Contains 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、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、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、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 an 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 is preferably 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).

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 where the medium comprises one or more compounds of formula V-7 and / or V-8, the medium may consist essentially of compounds of formula I, II, III and V .

  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.

  In a further preferred embodiment, the medium preferably comprises (additionally) one or more compounds containing fluorinated indane units selected from the group of compounds of the formulas V-12a and V-12b.

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、および好ましくは、
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し、
Ｚ^５１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 V, and preferably
R ⁵¹ represents alkyl or alkenyl, and R ⁵² represents alkyl, alkenyl, alkoxy or alkenyloxy,
Z ⁵¹ represents a single bond, and r represents 0.

  Very particular preference is given to compounds of the formula V-12b '.

式中、Ｒ^５１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 ⁵¹ has the meaning given above and preferably represents alkyl having 1 to 7, preferably 1 to 5, C atoms, preferably n-alkyl.

  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 is preferably largely, particularly preferably essentially, very particularly preferably substantially complete, from one or more compounds selected from the group of compounds of the formulas VI to VIII below.

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でＲ^２１に上で与えられる意味を有するか、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 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—,

を表し、
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は、両者が０を表し、および
ｘおよびｖは、両者が１を表す。

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

  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 includes one or more compounds selected from the group of sub-formulas I-1 to I-4.

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

  iv. The proportion of the compound of formula II in the overall mixture is 10% or more, preferably 50% or less, particularly preferably 15% or more.

  v. The liquid-crystalline medium comprises one or more compounds of the formula II-1, preferably II-1b and / or II-1d, particularly preferably II-1b, preferably at a total concentration of 60% or less and In a concentration of 2% or more, in particular 5% or more, very particularly preferably from 5% to 15%.

  vi. The liquid crystal medium comprises one or more compounds of formula II-2 and / or II-3, preferably of formula II-2a and / or II-3a, preferably in a total concentration of 50% or less, and preferably In concentrations of 2% to 10% per individual homologous compound of formula II-3 and in concentrations of 2% to 15% per homologous individual compound of formula II-3.

  vii. The proportion of the compound of formula III in the overall mixture is 10% or more, preferably 70% or less, particularly preferably 15% or more.

  viii. The liquid crystal medium comprises one or more particularly preferred compounds of the formulas III-1c and III-1d selected from the subformulas described below.

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.

  ix. 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、それぞれ１個または２個〜７個のＣ原子を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、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. Represents an alkyl, alkoxy or alkenyl group, particularly preferably a linear alkyl, and further an alkenyl.

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

  x. The liquid crystal medium comprises one or more compounds of the formula III selected from the group of compounds of the following formula, preferably in a total concentration of 10% to 70%: CC-n-V and / or CC -N-Vm (e.g .: preferably CC-5-V, preferably at concentrations up to 25%, CC-3-V, preferably at concentrations up to 60% and / or CC-3-V1 CC-n-m and / or CC-n-Om (e.g. preferably: at a concentration of up to 25% and / or at a concentration of CC-4-V, preferably up to 40%) 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, P-3-2 and / or CP-5-2 and / or CP-3-O1 and / or CP-3-O2), PP-n-Vm (eg: preferably PP-n-2V), PP -N-lVm (eg: preferably PP-n-2V1), CCP-n-m (eg: preferably CCP-n-1), CPP-n-m, CGP-n-m and CCOC-n -M, where the meaning of the acronym (abbreviation) is explained in Tables AC and illustrated by example in Table D.

xi. Liquid crystal media
2% to 80% of one or more compounds of formula I;
2% to 80% of one or more compounds of formula II;
Essentially from 2% to 80% of one or more compounds of the formula III and / or 2% to 80% of one or more compounds selected from the group of compounds of the formulas IV and / or V Become.

  xii. The liquid-crystalline medium contains 4 to 6 or 10-membered rings or one or more compounds of the formula I having 1 to 15%, in particular 2 to 12%, very particularly preferred for each compound Is included in an amount of 3% to 8%.

  xiii. The liquid-crystalline medium preferably contains one or more compounds of the formula IV in an amount of preferably 2% or more, in particular 5% or more, very particularly preferably 5% or more and 25% or less, per individual homologous compound. Is included in the range of 2% to 12%.

  xiv. The liquid crystal medium is a compound of formula IV-1 to IV-2, preferably IV-1 and / or IV-2, preferably formula IV-1b and / or IV-1d, particularly preferably IV-1b. The above compounds are preferably at a total concentration of 60% or less and at a concentration of 2% or more, in particular 5% or more, very particularly preferably 5% or more to 20% or less per individual homologous compound. Including.

  xv. The liquid crystal medium is preferably of formula IV-3 and / or IV-4, preferably of formula IV-3b and / or IV-3d and / or IV-4b and / or IV-4d, particularly preferably IV-4b and / or Or one or more compounds of IV-4b, preferably at a total concentration of 60% or less and per individual homologous compound of 2% or more, in particular 5% or more, very particularly preferably 5% or more Included at concentrations up to -20%.

  xvi. The liquid-crystalline medium comprises one or more compounds of the formula IV, preferably in an amount of 2% or more, in particular 5% or more, very particularly preferably 5% to 25%, in particular 2% to Within the range of 12%.

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

  xviii. The liquid crystal medium preferably contains one or more compounds selected from compounds of formulas V-12a and V-12b, preferably at a total concentration of 10% or more. The concentration of the individual homologous compounds of the formulas V-12a and / or V-12b is preferably 2% to 15%, preferably 3% to 12%, particularly preferably 4% to 10%.

  The invention further relates to an electro-optic 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 wide and a flow viscosity ν ₂₀ of at most 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 types of components A and B, which components themselves consist of one or more individual compounds.

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

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

Component C has a pronounced 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, at 20 ℃ 18mm ² · ^{s -1} or less, preferably has a flow viscosity of 12 mm ² · ^{s -1} or less, which is significantly low viscosity nematic liquid crystal.

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

  Many suitable materials are known to those 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 the compound selected from the group of formulas I to V, other components 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%. I do not care.

  The other constituents are preferably nematic or nematogenic substances, in particular azoxybenzenes, benzylideneanilines, biphenyls, terphenyls, phenyl or cyclohexylbenzoates, phenyl or cyclohexylcyclohexanecarboxylates , Phenylcyclohexanes, cyclohexylbiphenyls, cyclohexylcyclohexanes, cyclohexylnaphthalenes, 1,4-biscyclohexylbiphenyls or cyclohexylpyrimidines, phenyl or cyclohexyldioxanes, optionally halogenated stilbenes, benzylphenyl ethers Selected from the known substances classified into classes, tolans and substituted cinnamic 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によって形成される群からの炭素環構造またはヘテロ環構造を表し、
Ｇは、−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_２Ｏ−、−ＣＦ＝ＣＦ−、−ＯＣＦ_２−、−ＯＣＨ_２−、−（ＣＨ_２）_４−、−（ＣＨ_２）_３Ｏ−またはＣ−Ｃ単結合を表し、Ｑはハロゲン、好ましくは塩素、または−ＣＮを表し、Ｒ^９１およびＲ^９２は、それぞれ、１８個まで、好ましくは８個までの炭素原子を有するアルキル、アルケニル、アルコキシ、アルカノイルオキシまたはアルコキシカルボニルオキシを表し、あるいは、これらの基の１つは、ＣＮ、ＮＣ、ＮＯ_２、ＮＣＳ、ＣＦ_３、ＯＣＦ_３、Ｆ、ＣｌまたはＢｒ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 carbocyclic or heterocyclic structure from the group formed by 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 represents 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 Br Represent.

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. In addition to the proposed substituents, different ones are also common. Many 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 component, the total concentration of which is preferably not more than 10% 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, from 5% to 60%, preferably from 10% to 50%, preferably from 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.

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

  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, which are preferably For the most part are particularly preferably essentially, very particularly preferably substantially complete.

  The liquid-crystalline medium according to the invention is preferably in each case at least −20 ° C. or lower and 70 ° C. or higher, particularly preferably −30 ° C. or lower to 80 ° C. or higher, very particularly preferably −40 ° C. or lower to 85 ° C. It has a nematic phase of -40 ° C or higher, most preferably -40 ° C or lower to 90 ° C or higher.

  The expression “having a nematic phase” means here that, on the one hand, the smectic phase and crystallization are not observed at low temperatures at the corresponding temperature, and on the other hand, no heating occurs from the nematic phase. Means. The inspection at low temperature is performed 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-optical application. A medium is considered stable at this temperature if the storage stability at −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 the capillaries by conventional methods.

  In a preferred embodiment, the liquid crystal medium according to the invention is characterized by a value of optical anisotropy in the medium to low range. 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 0.5 or less, particularly preferably from 3.0 to 4.0, very particularly preferably from 3.5 to 3.9, a relatively high absolute value of dielectric anisotropy (| Δε |) 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 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 or less, particularly preferably 5.8 or more and 6.2 or less, very particularly preferably 5.9 or more and 6.1 or less, preferably a relatively low value of the average dielectric anisotropy (ε _av ≡ having a (ε _|| + 2ε _⊥) / 3).

  In a preferred embodiment particularly suitable for use in LCD television displays, the liquid-crystalline medium according to the invention is preferably from 1.7 to 4.9, preferably up to 4.3, preferably from 2.3 to 4.0. In particular, the absolute value of dielectric anisotropy (| Δε |) is particularly preferably in the range of 2.8 to 3.8.

In this embodiment, the liquid crystal medium according to the present invention has a threshold voltage (V ₀ ) value 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 the cell at 20 ° C. in a freshly filled cell, these are 95% or more, preferably 97% or more, particularly preferably 98% or more, very particularly preferably 99% or more, at 100 ° C. in the oven for 5 minutes. In later cells, these are 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, in each case in combination with one another, are maintained by the medium according to the invention.

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

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

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 ": 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 both the medium as a composition having those components, which can be components or compounds, and to the components having those components which are compounds. 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、

Represents trans-1,4-cyclohexylene,

は、１，４−フェニレンを表す。

Represents 1,4-phenylene.

  In the present invention, the term “dielectrically positive compound” means a compound having Δε> 1.5, and the term “dielectrically neutral compound” means that −1.5 ≦ Δε ≦ 1.5. The term “dielectrically negative compound” means Δε <−1.5. In the present description, the dielectric anisotropy of the compound refers to the homeotropic and homogeneous surface alignment with 10% compound dissolved in the liquid crystal host and the resulting mixture volume having a cell thickness of 20 μm in each case. By determining at 1 kHz in at least one test cell. 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. . The change in the dielectric constant of the host mixture after addition of the compound under consideration and extrapolation to 100% of the compound used gives the value of the individual compound under consideration. The compounds considered are dissolved in the host mixture in an amount of 10%. If the solubility of the substance is too low for this purpose, the concentration is halved in steps until the desired temperature can be studied.

  If desired, the liquid-crystalline media according to the invention also contain further additives, such as, for example, stabilizers and / or pleochroic dyes and / or chiral dopants in usual 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 also comprises one or more reactive compounds, preferably reactive mesogens and optionally further additives such as, for example, polymerization initiators and / or polymerization modulators. The containing polymer precursor is 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 style. 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 is advantageously done at high temperatures. When the selected temperature is higher than the clearing point of the main constituent, the completion of the melting operation can be seen particularly easily. However, it is also possible to prepare liquid crystal mixtures, for example in the use of premixes or other conventional methods from so-called “multi-bottle systems”.

The mixture according to the invention is very good at −30 ° C. and −40 ° C., with a very wide nematic phase range with a clearing point above 65 ° C., a very favorable value capacity threshold, a relatively high value retention. Excellent low temperature stability. 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. It can also be included.

  The structure of the liquid crystal display according to the present invention corresponds to the usual configuration as described, for example, in EP 0 240 379.

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

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

  For example, stabilizers which can be added to the mixture according to the invention in an amount of preferably 0.01 to 6%, in particular 0.1 to 3%, 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 the corresponding 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 according to “Melk liquid crystal, liquid crystal physical properties” November 1997, according to Merck, Germany, and in each case apply to a temperature of 20 ° C., unless otherwise stated, Δn is determined at 589 nm and Δε is determined at 1 kHz.

Electro-optical properties, for example threshold voltage (V ₀ ) (capacitive measurement), are determined as switching properties in a test cell manufactured at Merck Japan. The measuring cell has a soda-lime glass substrate, and is a polyimide alignment layer (SE-1211 (diluting ratio 1: 1) with diluent ^** 26), which is rubbed orthogonally to each other and has the effect of homeotropic alignment of liquid crystals. ECB or VA structure provided with Nissan Chemical Co., Ltd. in Japan. 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 soda-lime glass substrate, and is composed of a polyimide alignment layer (AL-3046, manufactured by Japan Synthetic Rubber Co., Japan) having a layer thickness of 50 nm and rubbed perpendicularly to each other. 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 in ovens at 20 ° C. (HR ₂₀ ) and 100 ° C. (HR ₁₀₀ ). 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, Darmstadt, Germany), the values of the rotational viscosities determined at 20 ° C. are 161 mPa · s, 133 mPa · s and The value (ν) of the flow viscosity is 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 _o 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 constant perpendicular to the director at 20 ° C. and 1 kHz,
ε _‖ is the dielectric constant 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.,
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 available properties and combinations of properties.

In the present invention and in the following examples, the structure of the liquid crystal compound is shown using acronyms 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 bonds, and Table C lists the meanings of the symbols for the left and right end groups of the molecule. The acronym consists of a code for a ring element that may have a linking group, followed by a code for the first hyphen and the left end group, and a code for the second hyphen and the right end group. Table D shows the schematic structures of the compounds along with their respective abbreviations.

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

Where 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 compounds mentioned below.

  The following abbreviations are used (n, m and z are each independently an integer, preferably 1 to 6).

表Ｅに、本発明による混合物において好ましく用いられるキラルドーパントを示す。

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

表Ｅからの化合物群より選択される化合物。

A compound selected from the group of compounds from Table E.

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 to 1.3>
<Example 1.1>

    <Example 1.2>

    <Example 1.3>

<Examples 2.1 and 2.2>
<Example 2.1>

    <Example 2.2>

また、既述の各種の実施例混合物をもう一つのものと混合してもよく、同様の有利な結果を与える。特に、これに一般に伴う、混合物の構成成分の数の増加により、通常、そのような混合物の保存安定性が改良される結果となる。

Also, the various example mixtures described above may be mixed with another, giving similar advantageous results. In particular, the generally associated increase in the number of components of the mixture usually results in improved storage stability of such mixtures.

Claims (30)

A negative dielectric anisotropy liquid crystal medium (however, clearing point except those less than 85 ° C..),
a) a first dielectric composed of one or more compounds selected from the group of compounds of the formulas Cn3f-n-m and Cn3f-n-Om (provided that the ratio to the total medium is 1 to 20% by weight) Negative component (component A),
b) one or more compounds selected from the group of compounds of the formulas PYP-n-m, PYP-nO-m and PYP-n-Om (provided that the ratio to the total medium is 5 to 50% by weight). A second dielectrically negative component (component B) comprising:
c) consisting of one or more compounds selected from the group of compounds of formulas III-1a to III-1e and III-4a to III-4d (provided that the proportion to the total medium is 35 to 70% by weight). A dielectrically neutral component (component C);
However, the liquid crystal medium comprises one or more dielectrically neutral alkenyl compounds selected from the group of compounds of formulas III-1c to III-1e and III-4b and III-4d (provided that the ratio to the total medium is 35% by weight) % Or more)
Wherein the liquid crystal medium comprises one or more dielectrically neutral alkenyl compounds selected from the group of compounds of formulas III-4b and III-4d;
d) one or more compounds selected from the group of compounds of the formulas IV-1a to IV-1d, IV-3a to IV-3d and IV-4a to IV-4d (provided that the ratio to the whole medium is from 5 to 80) A third dielectrically negative component (component D) consisting of:
However, the medium in which the total content of all the compounds in the medium is 100% by weight or less.

(In the formula, n and m each independently represent an integer of 1 to 6.)

(In the formula, n and m each independently represent an integer of 1 to 6.)

(Where
alkyl and alkyl ′, independently of one another, represent an alkyl having 1 to 7 C atoms;
alkoxy represents alkoxy having 1 to 5 C atoms,
alkenyl and alkenyl ′ represent, independently of one another, alkenyl having 2 to 7 C atoms. )

(Where
alkyl and alkyl ′, independently of one another, represent an alkyl having 1 to 7 C atoms;
alkoxy represents alkoxy having 1 to 5 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms. )

(Where
alkyl and alkyl ′, independently of one another, represent an alkyl having 1 to 7 C atoms;
alkoxy represents alkoxy having 1 to 5 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms. )

(Where
alkyl and alkyl ′, independently of one another, represent an alkyl having 1 to 7 C atoms;
alkoxy represents alkoxy having 1 to 5 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms. )

(Where
alkyl and alkyl ′, independently of one another, represent an alkyl having 1 to 7 C atoms;
alkoxy represents alkoxy having 1 to 5 C atoms,
alkenyl represents alkenyl having 2 to 7 C atoms. )   The medium according to claim 1, wherein the clearing point is 90 ° C. or higher.   The medium according to claim 1, wherein the birefringence measured at 20 ° C. and 589 nm is 0.095 or more.   The medium according to claim 1, wherein the clearing point is 90 ° C. or higher, and the birefringence measured at 20 ° C. and 589 nm is 0.095 or higher. The ratio of one or more dielectrically neutral alkenyl compounds selected from the group of compounds of formulas III-4b and III-4d to the total medium is 3 to 16% by weight . 5. The medium according to any one of 4 . % of Total medium of a compound compound selected from the group of a) expression Cn3f-n-m and Cn3f-n-Om is any one of the claims 1-5, characterized in that 5 to 10 wt% The medium according to item. b) The proportion of the compound selected from the group of compounds of the formulas PYP-n-m, PYP-nO-m and PYP-n-Om with respect to the total medium is 5 to 19% by weight. The medium according to any one of to 6 . c) Formula III-1a~III-1e and a percentage of the total medium III-4a~III-4d of compound compound selected from the group claim, characterized in that a 35 to 47 wt% 1-7 The medium according to any one of the above. d) a percentage of the total medium formula IV-1a~IV-1d compound selected from the group of the compounds is according to any one of claims 1 to 8, characterized in that a 5 to 23 wt% Medium. d) The proportion of the compound selected from the group of compounds of the formulas IV-3a to IV-3d to the whole medium is 7 to 23% by weight, according to any one of claims 1 to 9 Medium. The ratio of the compound selected from the compound group of d) formula IV-4a-IV-4d with respect to the whole medium is 12-21 weight%, It is any one of Claims 1-10 characterized by the above-mentioned. Medium. Dielectrically neutral component (component C) is, according to any one of claims 1 to 11, characterized in that it comprises one or more compounds selected from the group of compounds consisting of formulas III-1c Medium. 13. The medium of claim 12 , wherein the compound of formula III-1c is selected from the group of compounds consisting of formula III-1c ′.

(Where
n is 3, 4, 5;
R ^e represents H or CH ₃ . ) 13. The medium of claim 12 , wherein the compound of formula III-1c is selected from the group of compounds consisting of formula CC-n-V.

(Where
alkyl represents an alkyl group having 1 to 7 C atoms. ) 15. The medium of claim 14 , wherein the compound of formula CC-n-V is a compound of formula CC-3-V.

13. The medium of claim 12 , wherein the compound of formula III-1c is selected from the group of compounds consisting of formula CC-n-V1.

(Where
alkyl represents an alkyl group having 1 to 7 C atoms. ) 17. The medium of claim 16 , wherein the compound of formula CC-n-V1 is a compound of formula CC-3-V1.

Dielectrically neutral component (component C) is, according to any one of claims 1 to 17, characterized in that comprises one or more compounds selected from the group of compounds consisting of formulas III-1d Medium. 19. The medium of claim 18 , wherein the compound of formula III-1d is a compound of formula CC-VV.

The medium according to any one of claims 1 to 19 , further comprising e) a chiral component (component E) comprising one or more chiral compounds. The medium according to any one of claims 1 to 20 , further comprising one or more kinds of compounds selected from the following compound group.

The medium according to claim 21 , comprising:

(In the formula, n represents an integer of 1 to 12.) Medium of claim 21 or 22, characterized in that it comprises the following compounds.

The medium according to any one of claims 21 to 23 , comprising the following compound.

As a dielectric, electro-optical displays, wherein it contains a liquid crystal medium as claimed in any one of claims 1-24. 26. A display as claimed in claim 25 , comprising an active matrix addressing device. 27. Display according to claim 25 or 26 , based on VA, ECB, PALC, FFS or IPS effect. During electro-optical displays, the use of the liquid crystal medium as claimed in any one of claims 1-24. During electro-optical display having active matrix addressing structure, the use of the liquid crystal medium as claimed in any one of claims 1-24. A method for preparing a medium according to claim 1, comprising one or more compounds selected from the group of compounds of the formulas Cn3f-n-m and Cn3f-n-Om, and the formulas PYP-n-m, PYP- one or more compounds selected from the group of nO-m and PYP-n-Om and one or more selected from the group of compounds of formulas III-1a to III-1e and III-4a to III-4d One compound selected from the group of compounds of the formulas IV-1a to IV-1d, IV-3a to IV-3d and IV-4a to IV-4d; A method comprising mixing the above compound and one or more additives as optional components.