DE102011119144A1 - Liquid-crystalline medium and liquid-crystal display - Google Patents

Abstract

The present invention relates to dielectrically positive liquid-crystalline media containing one or more compounds of the formula in which the parameters have the respective meanings given in the specification, and optionally one or more further dielectrically positive compounds and optionally one or more further dielectrically neutral compounds, and liquid-crystal displays containing these media , especially active matrix displays and especially TN, IPS and FFS displays.

Description

Field of the invention

The present invention relates to liquid crystalline media and liquid crystal displays containing these media, especially to displays addressed by an active matrix, and more particularly to Twisted Nematic (TN), In Plane Switching (IPS) or Fringe Field Switching (FFS) displays.

State of the art and problem to be solved

Liquid crystal displays (LCDs) are used in many areas to display information. LCDs are used for both direct-view and projection-type displays. As electro-optical modes, for example, Twisted Nematic (TN), Super Twisted Nematic (STN), Optically Compensated Bend (OCB) and Electrically Controlled Birefringence (ECB) are used along with their various modifications and others. All of these modes use an electric field that is substantially perpendicular to the substrates or to the liquid crystal layer. In addition to these modes, there are also electro-optic modes that use an electric field that is substantially parallel to the substrates or the liquid crystal layer, such as the in-plane switching (IPS) mode (such as in DE 40 00 451 and EP 0 588 568 disclosed) and in Fringe Field Switching (FFS) mode, where there is a strong so-called "fringe field", a strong electric field near the edge of the electrodes and throughout the cell an electric field which has both a strong vertical component has a strong horizontal component. Especially these two latter electro-optical modes are used for LCDs in modern desktop monitors and are intended for use in displays for television and multimedia applications. The liquid crystals according to the present invention are preferably used in displays of this kind. Generally, FFS displays use dielectrically positive, liquid-crystalline media with rather smaller values of dielectric anisotropy, but in IPS displays as well, partially liquid-crystalline media with a dielectric anisotropy of only about 3 or even below are used.

These displays require new liquid-crystalline media with improved properties. In particular, the response times for many types of applications need to be improved. Therefore, liquid-crystalline media with lower viscosities (η), especially with lower rotational viscosity rates (γ ₁ ), are required. The rotational viscosity should be 80 mPa · s or less, preferably 60 mPa · s or less, and especially 55 mPa · s or less, especially for monitor applications. In addition to this parameter, the media must have a range of nematic phase of suitable width and position, as well as a suitable birefringence (Δn). In addition, the dielectric anisotropy (Δε) should be high enough to allow a reasonably low operating voltage. Preferably, Δε should be higher than 2 and very preferably higher than 3, but preferably not higher than 15 and in particular not higher than 12, since this would be contrary to an at least reasonably high specific resistance.

For applications as displays for notebooks or other mobile applications, the rotational viscosity should preferably be 120 mPa · s or less, and more preferably 100 mPa · s or less. Here, the dielectric anisotropy (Δε) should preferably be higher than 8 and more preferably higher than 12.

Preferably, the displays according to the present invention by an active matrix (active matrix LCDs, short AMDs), preferably by a matrix of thin-film transistors (TFTs), addressed. However, the liquid crystals according to the invention can also be advantageously used in displays with other known addressing agents.

There are many different display modes using composite systems of low molecular weight liquid crystal materials together with polymeric materials. These are z. B. polymer dispersed liquid crystal (PDLC), nematic curvilinearily aligned phase (NCAP) and polymer network (PN) systems such as in WO 91/05 029 disclosed, or axially symmetric microdomain (ASM) systems and others. In contrast, the modes particularly preferred according to the present invention employ the liquid crystal medium as such, oriented on surfaces. These surfaces are typically pretreated to achieve uniform orientation of the liquid crystal material. The display modes according to the present invention preferably use an electric field that is substantially parallel to the compound layer.

Liquid crystal compositions that are suitable for LCDs and especially for IPS displays are, for. B. off JP 07-181 439 (A) . EP 0 667 555 . EP 0 673 986 . DE 195 09 410 . DE 195 28 106 . DE 195 28 107 . WO 96/23 851 and WO 96/28 521 known. However, these compositions have serious disadvantages. Most of them, among other shortcomings, lead to unfavorably long response times, have too low resistivity values, and / or require operating voltages that are too high. There is also a need to improve the low temperature performance of the LCDs. Here, both an improvement of the operating characteristics, as well as the shelf life and, in particular, the stability to visible light and UV radiation, but also against heat and especially against a combination of heat and light and / or UV radiation necessary.

ist bekannt, sie wird z. B. in Miéville, P. et al, Angew. Chem. 2010, 122, Seiten 6318–6321 erwähnt. Sie ist von verschiednen Herstellern kommerziell erhältlich und wird z. B. in Formulierungen für Vorläufer für Polyolefine, Polystyrole, Polyamide, Beschichtungen und PVC als Polymerisationsinhibitor und, insbesondere in Kombination mit UV-Absorbern, als Licht- bzw. UV-Schutz eingesetzt.The compound TEMPOL, the following formula

is known, it is z. In Miéville, P. et al, Angew. Chem. 2010, 122, pages 6318-6321 mentioned. It is commercially available from various manufacturers and z. B. in formulations for precursors for polyolefins, polystyrenes, polyamides, coatings and PVC as a polymerization inhibitor and, in particular in combination with UV absorbers, used as light or UV protection.

sind Bestandteile des unter der Bezeichnung „Cyasorb UV-3852S” von der Firma Cytec, West Paterson, USA kommerziell erhältlichen Produkts, das als Licht-Stabilisator z. B. in Formulierungen für Kunststoffteile aus Polypropylen für die Automobilindustrie und für Gartenmöbel eingesetzt wird.Compounds of the following formula

are components of the product commercially available under the name "Cyasorb UV-3852S" from Cytec, West Paterson, USA, which is used as a light stabilizer z. B. is used in formulations for plastic parts made of polypropylene for the automotive industry and garden furniture.

"Cyasorb UV-3853S" according to the manufacturer contains 50% HALS in a LDPE resin and a mixture of different HALS, wherein the alkyl radical "R" in Cyasorb UV-3853S substantially "C ₁₁ to C ₂₀ " alkyl and predominantly "C ₁₆ bis C ₁₈ "is alkyl. According to NA / 867, 09.01.2001, NICAS, Government of Australia, "Cyasorb UV-3852S" contains 50% polyethylene and the HALS component of "Cyasorb UV-3852S" esters of the following acids: Ester of the acid R Proportion of compound to HALS / wt% stearic acid - (CH _{2) 16} -CH ₃ ≈ 40-65 palmitic - (CH ₂ ) ₁₄ -CH ₃ ≈31-49 Heptadecanoic Acid - (CH _{2) 18} -CH ₃ ≈ 0.3-4.8 myristic - (CH ₂ ) ₁₂ -CH ₃ ≈ 0.1-3.0 oleic acid - (CH ₂ ) ₇ -CH = CH- (CH ₂ ) ₇ -CH 3 ≈ 0.2-4.0 other C ₁₁ to C ₂₀ ≈ 0.2-6.2

However, such compounds have not found use in liquid crystalline media.

Many liquid crystal media, especially those with large polarities, or high dielectric anisotropy, do not meet the high stability requirements required for practical applications.

There is therefore a considerable need for liquid-crystalline media with suitable properties for practical applications, such as a broad nematic phase range, suitable optical anisotropy Δn corresponding to the type of display used, a high Δε and especially low viscosities for particularly short switching times.

Present invention

Surprisingly, it has now been found that liquid-crystalline media having a suitably high Δε, a suitable phase range and suitable Δn can be realized which do not have the disadvantages of the prior art materials or at least only to a considerably lesser extent.

enthalten, und/oder Verbindungen, die eine Strukturelement der Formel

enthalten, wobei diese Strukturelemente optional weitere Substituenten tragen können, bevorzugt Alkyl oder Halogen.It has surprisingly been found here that the compounds of the formula I lead to a considerable, in many cases sufficient, stabilization of liquid-crystal mixtures and in particular in combination with other stabilizers, in particular with ortho- (tert-butyl) -phenol derivatives or di-ortho- (tert Butyl) phenol derivatives, ie compounds which are a structural element of the formula

contain, and / or compounds that are a structural element of the formula

contain, wherein these structural elements can optionally carry further substituents, preferably alkyl or halogen.

• – eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Verbindungen der Formel I
  
  worin R¹¹ bis R¹⁴ jeweils unabhängig voneinander Alkyl mit 1 bis 4 C-Atomen, bevorzugt alle vier CH₃, X¹ H oder O* (also ein einfach gebundenes O-Atom mit einem radikalischen Elektron), bevorzugt O*, Z¹ -O-, -(CO)-O-, -O-(CO)-, -O-(CO)-O-, -NH-, -NY⁰¹- oder -NH-(CO)-, Y¹ und Y⁰¹ jeweils unabhängig voneinander geradkettiges oder verzweigtes Alkyl mit 1 bis 20 C-Atomen, bevorzugt mit 1 bis 10 C-Atomen und besonders bevorzugt mit 15 C-Atomen, auch Cycloalkyl, Cycloalkylalkyl, oder Alkylcyloalkyl, wobei in allen diesen Gruppen eine oder mehrere -CH₂- Gruppen durch -O- so ersetzt sein können, dass im Molekül keine zwei O-Atome direkt miteinander verbunden sind, bedeutet, und, im Fall, dass Z¹ -O-(CO)-O- bedeutet,
  
  bedeuten kann,
• – gegebenenfalls eine oder mehrere Verbindungen ausgewählt aus der Gruppe der Verbindungen der Formeln II und III
  
  worin R² und R³ unabhängig voneinander Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy mit 1 bis 7 C-Atomen, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen und vorzugsweise R² und R³ Alkyl oder Alkenyl,
  
  bei jedem Erscheinen unabhängig voneinander
  
  bevorzugt
  
  L²¹, L²², L³¹ und L³² unabhängig voneinander H oder F, vorzugsweise L²¹ und/oder L³¹ F, X² und X³ unabhängig voneinander Halogen, halogeniertes Alkyl oder Alkoxy mit 1 bis 3 C-Atomen oder halogeniertes Alkenyl oder Alkenyloxy mit 2 oder 3 C-Atomen, vorzugsweise F, Cl, -OCF₃ oder -CF₃, ganz bevorzugt F, Cl oder -OCF₃, Z³ -CH₂CH₂-, -CF₂CF₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O- oder eine Einfachbindung, vorzugsweise -CH₂CH₂-, -COO-, trans- -CH=CH- oder eine Einfachbindung und ganz bevorzugt -COO-, trans- -CH=CH- oder eine Einfachbindung und m und n unabhängig voneinander 0, 1, 2 oder 3, m bevorzugt 1, 2 oder 3 und n bevorzugt 0, 1 oder 2 und besonders bevorzugt 1 oder 2, bedeuten, und
• – gegebenenfalls eine oder mehrere Verbindungen der Formel IV
  
  worin R⁴¹ und R⁴² unabhängig voneinander die oben unter Formel II für R² angegebene Bedeutung besitzen, vorzugsweise R⁴¹ Alkyl und R⁴² Alkyl oder Alkoxy oder R⁴¹ Alkenyl und R⁴² Alkyl,
  
  unabhängig voneinander und bei zweifachem Auftreten von
  
  auch diese unabhängig voneinander
  
  vorzugsweise eines oder mehrere von
  
  Z⁴¹ und Z⁴² unabhängig voneinander und bei zweifachem Auftreten von Z⁴¹ auch diese unabhängig voneinander -CH₂CH₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O-, -CF₂O-, -C≡C- oder eine Einfachbindung, vorzugsweise eines oder mehrere von ihnen eine Einfachbindung und p 0, 1 oder 2, vorzugsweise 0 oder 1 bedeutet.

These improved liquid crystalline media according to the present invention included

• - One or more compounds selected from the group of compounds of formula I.
  
  wherein R ¹¹ to R ^{14 are} each independently alkyl having 1 to 4 carbon atoms, preferably all four CH ₃ , X ¹ H or O * (ie a single bonded O atom with a free-radical electron), preferably O *, Z ¹ -O-, - (CO) -O-, -O- (CO) -, -O- (CO) -O-, -NH-, -NY ⁰¹ - or -NH- (CO) -, Y ¹ and Y ^{01 are} each, independently of one another, straight-chain or branched alkyl having 1 to 20 C atoms, preferably having 1 to 10 C atoms and particularly preferably 15 C atoms, also cycloalkyl, cycloalkylalkyl, or alkylcycloalkyl, where one or more of these groups is -CH ₂ - groups can be replaced by -O- so that in the molecule no two O atoms are directly connected to each other, means, and, in the case that Z ^{1 is} -O- (CO) -O-,
  
  can mean
• - optionally one or more compounds selected from the group of compounds of formulas II and III
  
  wherein R ² and R ³ are each independently alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 carbon atoms and preferably R ² and R ^{3 is} alkyl or alkenyl .
  
  at each appearance independently
  
  prefers
  
  L ²¹ , L ²² , L ³¹ and L ³² are each independently H or F, preferably L ²¹ and / or L ³¹ F, X ² and X ^{3 are} independently halogen, halogenated alkyl or alkoxy having 1 to 3 carbon atoms or halogenated alkenyl or alkenyloxy having 2 or 3 C atoms, preferably F, Cl, -OCF ₃ or -CF ₃ , more preferably F, Cl or -OCF ₃ , Z ³ -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, - COO, trans- CH = CH-, trans- -CF = CF-, -CH ₂ O- or a single bond, preferably -CH ₂ CH ₂ -, -COO-, trans- CH = CH- or a single bond and most preferably -COO-, trans- -CH = CH- or a single bond and m and n are independently 0, 1, 2 or 3, m is preferably 1, 2 or 3 and n is preferably 0, 1 or 2 and particularly preferably 1 or 2, and
• Optionally one or more compounds of formula IV
  
  in which R ⁴¹ and R ⁴² independently of one another have the meaning given above for R ² under formula II, preferably R ^{41 is} alkyl and R ^{42 is} alkyl or alkoxy or R ^{41 is} alkenyl and R ^{42 is} alkyl,
  
  independently of each other and in case of double occurrences of
  
  also these independently
  
  preferably one or more of
  
  Z ⁴¹ and Z ^42, independently of one another and also in the case of Z ^41, also represent these independently of one another -CH ₂ CH ₂ -, -COO-, trans -CH = CH-, trans-CF = CF-, -CH ₂ O- , -CF ₂ O-, -C≡C- or a single bond, preferably one or more of them is a single bond and p is 0, 1 or 2, preferably 0 or 1.

The compounds of the formulas II and III are preferably dielectrically positive compounds, preferably with a dielectric anisotropy of more than 3.

The compounds of the formula IV are preferably dielectrically neutral compounds, preferably having a dielectric anisotropy in the range from -1.5 to 3.

The liquid-crystalline media according to the present application preferably contain a total of 10 ppm to 10,000 ppm, preferably 50 ppm to 2,000 ppm, and very particularly preferably 100 ppm to 1,000 ppm of compounds of the formula I.

These compounds are outstandingly suitable as stabilizers in liquid-crystal mixtures. In particular, they stabilize the "Voltage Holding Ratio" (short VHR or only HR) of the mixtures after UV exposure.

The individual compounds of the formula II and / or III are used in a concentration of 1 to 20%, preferably from 1 to 15%. These limits apply in particular if in each case two or more homologous compounds, ie compounds of the same formula, are used. If only one single substance, ie only one homologue, of the compounds of one formula is used, its concentration can be in the range from 2 to 20%, preferably from 3 to 14%.

worin die Parameter die oben unter Formel I angegebenen Bedeutungen haben.In a preferred embodiment of the present invention, the media according to the invention each contain one or more compounds of the formula IA selected from the group of the compounds of the formulas I-1 to I-7, preferably of the formulas I-1 and / or I-2:

wherein the parameters have the meanings given above under formula I.

worin die entsprechenden Parameter die oben unter Formel I angegebenen Bedeutungen haben und
R und R' jeweils unabhängig voneinander die oben bei Y¹ gegeben Bedeutung haben und bevorzugt Alkyl, besonders bevorzugt n-Alkyl,
bedeuten.In a more preferred embodiment of the present invention, the media according to the invention each contain one or more compounds of the formula I selected from the group of the following compounds

wherein the corresponding parameters have the meanings given above under formula I and
R and R 'each independently of one another have the meaning given above for Y ¹ and preferably alkyl, particularly preferably n-alkyl,
mean.

Vorzugsweise enthalten die Medien gemäß der vorliegenden Erfindung zusätzlich zu den Verbindungen der Formel 1, bzw. deren bevorzugter Unterformeln, eine oder mehrere dielektrisch positive Verbindungen mit einer dielektrischen Anisotropie von mehr als 3, ausgewählt aus der Gruppe der Formeln II und III.In an even more preferred embodiment of the present invention, the media according to the invention in each case contain one or more compounds of the formula I selected from the group of the following compounds of the formulas I-1a-1, I-1a-2, I-1b-1 to I- 1b-4, I-5a-1, I-5a-2, I-6a-1 and I-6a-2, most preferably selected from the group of compounds I-1a-1, I-1a-2, I -1b-1 and I-1b-2 and most preferably selected from the group of compounds of formulas I-1a-1 and I-1a-2:

Preferably, the media according to the present invention contain in addition to the compounds of formula 1, or their preferred sub-formulas, one or more dielectrically positive compounds having a dielectric anisotropy of more than 3, selected from the group of formulas II and III.

worin die Parameter die jeweiligen oben unter Formel II angegebenen Bedeutungen besitzen und L²³ und L²⁴ unabhängig voneinander H oder F, bevorzugt L²³ F bedeutet und

gegebenen Bedeutungenhat und bei Formeln II-1 und II-4 X² bevorzugt F oder OCF₃, besonders bevorzugt F und bei Formel II-3 vorzugsweise

unabhängig voneinander

bedeuten,
und/oder ausgewählt sind aus der Gruppe der Verbindungen der Formeln III-1 und III-2:

worin die Parameter die unter Formel III gegeben Bedeutung haben.In a preferred embodiment of the present invention, the media according to the invention comprise one or more compounds selected from the group of the compounds of the formulas II-1 to II-4, preferably of the formulas II-1 and / or II-2

wherein the parameters have the respective meanings given above under formula II and L ²³ and L ²⁴ independently of one another are H or F, preferably L ²³ F and

has given meanings and in formulas II-1 and II-4 X ² preferably F or OCF ₃ , more preferably F and in formula II-3 preferably

independently of each other

mean,
and / or are selected from the group of the compounds of the formulas III-1 and III-2:

wherein the parameters have the meaning given under formula III.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und die Parameter L³¹ und L³² unabhängig voneinander und von den anderen Parametern H oder F bedeuten.In a preferred embodiment, the media according to the present invention comprise, alternatively or in addition to the compounds of the formulas III-1 and / or III-2, one or more compounds of the formula III-3

wherein the parameters have the respective meanings given above and the parameters L ³¹ and L ³² independently of one another and of the other parameters mean H or F.

The media according to the invention preferably contain one or more compounds selected from the group of the compounds of the formulas II-1 to II-4, in which L ²¹ and L ²² and / or L ²³ and L ^{24 are} both F.

In a preferred embodiment, the media contain one or more compounds selected from the group of compounds of formulas II-2 and II-4, wherein L ²¹ , L ²² , L ²³ and L ^{24 are} all F.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und L²³ bis L²⁵ unabhängig voneinander und von den anderen Parametern H oder F bedeuten und
bei den Verbindungen der Formel II-1d und II-1e die Verbindungen der Formel I ausgeschlossen sind und
vorzugsweise
in den Formeln II-1a und II-1b
L²¹ und L²² beide F bedeuten,
in den Formeln II-1c und II-1d
L²¹ und L²² beide F und/oder L²³ und L²⁴ beide F bedeuten und
in Formel II-1e
L²¹, L²² und L²⁵ F bedeuten und jeweils die anderen Parameter die jeweiligen oben gegebenen Bedeutungen haben.Preferably, the media contain one or more compounds of formula II-1. The compounds of the formula II-1 are preferably selected from the group of the compounds of the formulas II-1a to II-1f

wherein the parameters have the respective meanings given above and L ²³ to L ²⁵ independently of one another and of the other parameters H or F mean and
in the compounds of the formula II-1d and II-1e the compounds of the formula I are excluded and
preferably
in formulas II-1a and II-1b
L ²¹ and L ²² both mean F,
in the formulas II-1c and II-1d
L ²¹ and L ²² both F and / or L ²³ and L ^{24 are} both F and
in formula II-1e
L ²¹ , L ²² and L ^{25 are} F and in each case the other parameters have the respective meanings given above.

worin R² die oben angegebene Bedeutung besitzt.Especially preferred compounds of formula II-1 are

wherein R ^{2 has} the meaning given above.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und L²⁵ bis L²⁸ unabhängig voneinander H oder F, bevorzugt L²⁷ und L²⁸ beide H, besonders bevorzugt L²⁶ H bedeuten und die anderen Parameter die jeweiligen oben gegebenen Bedeutungen.The media preferably comprise one or more compounds of the formula II-2 which are preferably selected from the group of the compounds of the formulas II-2a to II-2j

wherein the parameters have the respective meanings given above and L ²⁵ to L ²⁸ independently of one another are H or F, preferably L ²⁷ and L ^{28 are} both H, particularly preferably L ²⁶ H and the other parameters are the respective meanings given above.

The media according to the invention preferably contain one or more compounds selected from the group of the compounds of the formulas II-2a to II-2j, in which L ²¹ and L ²² both denote F and / or L ²³ and L ²⁴ both denote F and the other parameters denote the respective ones have the meanings given above.

In a preferred embodiment, the media according to the invention contain one or more compounds selected from the group of the compounds of the formulas II-2a to II-2j, wherein L ²¹ , L ²² , L ²³ and L ²⁴ all denote F and the other parameters are the respective ones above given meanings.

worin R² und X² die oben angegebenen Bedeutungen besitzen und X² bevorzugt F.Especially preferred compounds of formula II-2 are the compounds of the following formulas

wherein R ² and X ^{2 have} the meanings given above and X ^{2 is} preferably F.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und L²¹ und L²² vorzugsweise beide F bedeuten. The media according to the invention preferably comprise one or more compounds of the formula II-3, preferably selected from the group of the compounds of the formulas II-3a to II-3c

wherein the parameters have the respective meanings given above and L ²¹ and L ^{22 are} preferably both F.

worin die Parameter die oben gegebene Bedeutung haben und X² bevorzugt F oder OCF₃, besonders bevorzugt F, bedeutet.In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula II-4, preferably of the formula II-4a

wherein the parameters have the meaning given above and X ^{2 is} preferably F or OCF ₃ , more preferably F means.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und die Parameter L³³ und L³⁴ unabhängig voneinander und von den anderen Parametern H oder F bedeuten.The media according to the invention preferably comprise one or more compounds of the formula III-1, preferably selected from the group of the compounds of the formulas III-1a and III-1b

wherein the parameters have the respective meanings given above and the parameters L ³³ and L ³⁴ independently and from the other parameters H or F.

worin R³ die oben angegebene Bedeutung besitzt.The media according to the invention preferably comprise one or more compounds of the formula III-1a, preferably selected from the group of the compounds of the formulas III-1a-1 to III-1a-6

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt.The media according to the invention preferably comprise one or more compounds of the formula III-1b, preferably selected from the group of the compounds of the formulas III-1b-1 to III-1b-4, preferably of the formula III-1b-4

wherein R ^{3 has} the meaning given above.

worin die Parameter die oben gegebene Bedeutung haben und bevorzugt worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und die Parameter L³³, L³⁴, L³⁵ und L³⁶ unabhängig voneinander und von den anderen Parametern H oder F bedeuten.The media according to the invention preferably contain one or more compounds of the formula III-2, preferably selected from the group of the compounds of the formulas III-2a to III-2j

wherein the parameters have the meaning given above and preferably wherein the parameters have the respective meanings given above and the parameters L ³³ , L ³⁴ , L ³⁵ and L ³⁶ independently of one another and from the other parameters H or F.

worin R³ die oben angegebene Bedeutung besitzt.The media according to the invention preferably comprise one or more compounds of the formula III-2a, preferably selected from the group of the compounds of the formulas III-2a-1 to III-2a-5

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt. The media according to the invention preferably contain one or more compounds of the formula III-2b, preferably selected from the group of the compounds of the formulas III-2b-1 and III-2b-2, preferably of the formula III-2b-2

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt.The media according to the invention preferably comprise one or more compounds of the formula III-2c, preferably selected from the group of the compounds of the formulas III-2c-1 to III-2c-6

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt.The media according to the invention preferably comprise one or more compounds selected from the group of the compounds of the formulas III-2d and III-2e, preferably selected from the group of the compounds of the formulas III-2d-1 and III-2e-1

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt. The media according to the invention preferably comprise one or more compounds of the formula III-2f, preferably selected from the group of the compounds of the formulas III-2f-1 to III-2f-5

wherein R ^{3 has} the meaning given above.

worin R³ die oben angegebene Bedeutung besitzt.Preferably, the media according to the invention comprise one or more compounds of the formula III-2g, preferably selected from the group of the compounds of the formulas III-2g-1 to III-2g-5

wherein R ^{3 has} the meaning given above.

worin die Parameter die oben gegebene Bedeutung haben und bevorzugt X³ F bedeutet.The media according to the invention preferably comprise one or more compounds of the formula III-2h, preferably selected from the group of the compounds of the formulas III-2h-1 to III-2h-3, preferably of the formula III-2h-3

wherein the parameters have the meaning given above and preferably X ³ F means.

worin die Parameter die oben gegebene Bedeutung haben und bevorzugt X³ F bedeutet.The media according to the invention preferably comprise one or more compounds of the formula III-2i, preferably selected from the group of the compounds of the formulas III-2i-1 and III-2i-2, particularly preferably of the formula III-2i-2

wherein the parameters have the meaning given above and preferably X ³ F means.

worin die Parameter die oben gegebene Bedeutung haben.The media according to the invention preferably comprise one or more compounds of the formula III-2j, preferably selected from the group of the compounds of the formulas III-2j-1 and III-2j-2, particularly preferably of the formula III-2j-1

wherein the parameters have the meaning given above.

worin die Parameter die jeweiligen oben unter Formel III angegebenen Bedeutungen besitzen. Alternatively or in addition to the compounds of the formulas III-1 and / or III-2, the media according to the present invention may contain one or more compounds of the formula III-3

wherein the parameters have the respective meanings given above under formula III.

worin R³ die oben angegebene Bedeutung besitzt.These compounds are preferably selected from the group of formulas III-3a and III-3b

wherein R ^{3 has} the meaning given above.

worin R⁴¹ und R⁴² die jeweiligen oben unter Formel IV angegebenen Bedeutungen besitzen und in den Formeln IV-1, IV-6 und IV-7 R⁴¹ vorzugsweise Alkyl oder Alkenyl, vorzugsweise Alkenyl, und R⁴² vorzugsweise Alkyl oder Alkenyl, vorzugsweise Alkyl bedeutet. In Formel IV-2 R⁴¹ und R⁴² vorzugsweise Alkyl bedeuten. In Formel IV-5 R⁴¹ vorzugsweise Alkyl oder Alkenyl, stärker bevorzugt Alkyl, und R⁴² vorzugsweise Alkyl, Alkenyl oder Alkoxy, stärker bevorzugt Alkenyl oder Alkoxy und in Formeln IV-4 und IV-8 R⁴¹ vorzugsweise Alkyl und R⁴² vorzugsweise Alkyl oder Alkoxy, stärker bevorzugt Alkoxy, bedeutet.Preferably, the liquid-crystalline media according to the present invention contain a dielectrically neutral component, component C. This component has a dielectric anisotropy in the range of -1.5 to 3. Preferably, it contains dielectrically neutral compounds having a dielectric anisotropy in the range of -1.5 to 3, more preferably it is predominantly, even more preferably essentially consists of, and especially preferably consists entirely of. Preferably, this component contains one or more dielectrically neutral compounds, more preferably it consists predominantly, even more preferably substantially, and most preferably it consists entirely of dielectrically neutral compounds having a dielectric anisotropy in the range of -1.5 to 3 of the formula IV. Preferably, the dielectrically neutral component, component C, contains one or more compounds selected from the group of compounds of formulas IV-1 to IV-8

wherein R ⁴¹ and R ^{42 have} the respective meanings given above under formula IV and in the formulas IV-1, IV-6 and IV-7 R ^{41 is} preferably alkyl or alkenyl, preferably alkenyl, and R ^{42 is} preferably alkyl or alkenyl, preferably alkyl means. In formula IV-2, R ⁴¹ and R ^{42 are} preferably alkyl. In formula IV-5 R ^{41 is} preferably alkyl or alkenyl, more preferably alkyl, and R ^{42 is} preferably alkyl, alkenyl or alkoxy, more preferably alkenyl or alkoxy and in formulas IV-4 and IV-8 R ^{41 is} preferably alkyl and R ^{42 is} preferably alkyl or alkoxy, more preferably alkoxy.

Preferably, the dielectrically neutral component, component C, contains one or more compounds selected from the group of compounds of formulas IV-1, IV-5, IV-6 and IV-7, preferably one or more compounds of formula IV-1 and one or more compounds selected from the group of the formulas IV-5 and IV-6, more preferably in each case one or more compounds of the formulas IV-1, IV-5 and IV-6 and very preferably in each case one or more compounds of formulas IV-1, IV-5, IV-6 and IV-7.

In a preferred embodiment, the media according to the invention comprise one or more compounds of the formula IV-4, more preferably selected from their respective sub-formulas of the formula CP-Vn and / or CP-nV-m and / or CP-Vn-m, more preferably the Formula CP-Vn and / or CP-V2-n and most preferably selected from the group of the formulas CP-V-1 and CP-V2-1. The definitions of these abbreviations (acronyms) are given below in Table D, or from Tables A to C.

In a preferred embodiment, the media of the invention contain one or more compounds of formula IV-5, more preferably selected from their respective sub-formulas of formula CCP-Vn and / or CCP-nV-m and / or CCP-Vn-m, more preferably Formula CCP-Vn and / or CCP-V2-n and most preferably selected from the group of the formulas CCP-V-1 and CCP-V2-1. The definitions of these abbreviations (acronyms) are given below in Table D, or from Tables A to C.

In a likewise preferred embodiment, the media according to the invention contain one or more compounds of the formula IV-1, more preferably selected from their respective sub-formulas, the formula CC-nm, CC-nV, CC-n-Vm, CC-VV, CC-V -Vn and / or CC-nV-Vm, more preferably of the formulas CC-nV and / or CC-n-Vm and most preferably selected from the group of the formulas CC-3-V, CC-4-V, CC-5 -V CC-3-V1, CC-4V1, CC-5-V1, CC-3-V2 and CC-V-V1. The definitions of these abbreviations (acronyms) are also given below in Table D, or from Tables A to C.

worin
R⁴¹ und R⁴² unabhängig voneinander Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy mit 1 bis 7 C-Atomen, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen bedeuten und
L⁴ H oder F bedeutet.In a further preferred embodiment of the present invention, which may be the same as or different from the preceding one, the liquid crystal mixtures according to FIG the present invention, the component C, the compounds of formula IV selected from the group of compounds of formulas IV-1 to IV-8 as shown above and optionally of the formulas IV-9 to IV-15 contains, preferably predominantly thereof, and quite preferably completely consists of:

wherein
R ⁴¹ and R ⁴² independently of one another are alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms and
L ⁴ H or F means.

In a preferred embodiment, the media of the invention contain one or more compounds of formula IV-10, more preferably selected from their respective sub-formulas of formula CPP-3-2, CPP-5-2 and CGP-3-2, more preferably of formula CPP -3-2 and / or CGP-3-2 and most preferably the formula CPP-3-2. The definitions of these abbreviations (acronyms) are given below in Table D, or from Tables A to C.

worin
R⁵¹ und R⁵² unabhängig voneinander die oben unter Formel II für R² angegebene Bedeutung besitzen, vorzugsweise R⁵¹ Alkyl und R⁵² Alkyl oder Alkenyl bedeutet,

bei zweifachem Auftreten, bei jedem Auftreten jeweilsunabhängig voneinander

vorzugsweise einer oder mehrere von

bedeuten,
Z⁵¹ und Z⁵² unabhängig voneinander und bei zweifachem Auftreten von Z⁵¹ auch diese unabhängig voneinander -CH₂CH₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O-, -CF₂O- oder eine Einfachbindung bedeuten, vorzugsweise eines oder mehrere von ihnen eine Einfachbindung bedeutet/bedeuten, und
r 0, 1 oder 2, vorzugsweise 0 oder 1, besonders bevorzugt 1, bedeutet. The liquid-crystalline media according to the present invention preferably comprise one or more compounds of the formula V

wherein
R ⁵¹ and R ⁵² independently of one another have the meanings given above under formula II for R ² , preferably R ⁵¹ denotes alkyl and R ⁵² denotes alkyl or alkenyl,

when occurring twice, each time independently of each other

preferably one or more of

mean,
Z ⁵¹ and Z ⁵² independently of one another and at present twice, Z ^51, also these independently of one another, -CH ₂ CH ₂ -, -COO-, trans- -CH = CH-, -CF = CF- trans-, -CH ₂ O- , -CF ₂ O- or a single bond, preferably one or more of them is a single bond means /, and
r is 0, 1 or 2, preferably 0 or 1, particularly preferably 1.

The compounds of formula V are preferably dielectrically neutral compounds having a dielectric anisotropy in the range of -1.5 to 3.

worin R⁵¹ und R⁵² die jeweiligen oben unter Formel V angegebenen Bedeutungen besitzen und R⁵¹ vorzugsweise Alkyl bedeutet und in Formel V-1 R⁵² vorzugsweise Alkenyl, vorzugsweise -(CH₂)₂-CH=CH-CH₃, und in Formel V-2 R⁵² vorzugsweise Alkyl oder Alkenyl, vorzugsweise -CH=CH₂, -(CH₂)₂-CH=CH₂ oder -(CH₂)₂-CH=CH-CH₃, bedeutet.The media according to the invention preferably contain one or more compounds selected from the group of the compounds of the formulas V-1 and V-2

wherein R ⁵¹ and R ^{52 have} the respective meanings given above under formula V and R ^{51 is} preferably alkyl and in formula V-1 R ^{52 is} preferably alkenyl, preferably - (CH ₂ ) ₂ -CH = CH-CH ₃ , and in formula V-2 R ^{52 is} preferably alkyl or alkenyl, preferably -CH = CH ₂ , - (CH ₂ ) ₂ -CH = CH ₂ or - (CH ₂ ) ₂ -CH = CH-CH ₃ .

Preferably, the media according to the invention contain one or more compounds selected from the group of compounds of formulas V-1 and V-2, wherein R ^{51 is} preferably n-alkyl and in formula V-1 R ^{52 is} preferably alkenyl and in formula V-2 R ^{52 is} preferably n-alkyl.

In a preferred embodiment, the media of the invention contain one or more compounds of formula V-1, more preferably their sub-formula PP-n-2Vm, even more preferably of formula PP-1-2V1. The definitions of these abbreviations (acronyms) are given below in Table D, or from Tables A to C.

In a preferred embodiment, the media of the present invention more preferably contain one or more compounds of Formula V-2, more preferably their sub-formulas PGP-nm, PGP-nV, PGP-n-2Vm, PGP-n-2V and PGP-n-2Vm preferably their sub-formulas PGP-3-m, PGP-n-2V and PGP-n-V1, most preferably selected from the formulas PGP-3-2, PGP-3-3, PGP-3-4, PGP-3-5 , PGP-1-2V, PGP-2-2V and PGP-3-2V. The definitions of these abbreviations (acronyms) are also given below in Table D, or from Tables A to C.

worin
R⁶ Alkyl, Alkoxy, fluoriertes Alkyl oder fluoriertes Alkoxy mit 1 bis 7 C-Atomen, Alkenyl, Alkenyloxy, Alkoxyalkyl oder fluoriertes Alkenyl mit 2 bis 7 C-Atomen und vorzugsweise Alkyl oder Alkenyl bedeutet,

unabhängig voneinander

L⁶¹ und L⁶² unabhängig voneinander H oder F bedeuten, vorzugsweise L⁶¹ F bedeutet,
X⁶ Halogen, halogeniertes Alkyl oder Alkoxy mit 1 bis 3 C-Atomen oder halogeniertes Alkenyl oder Alkenyloxy mit 2 oder 3 C-Atomen, vorzugsweise F, Cl, -OCF₃ oder -CF₃, ganz bevorzugt F, Cl oder -OCF₃ bedeutet,
Z⁶ -CH₂CH₂-, -CF₂CF₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O- oder -CF₂O-, vorzugsweise -CH₂CH₂-, -COO- oder trans- -CH=CH- und ganz bevorzugt -COO- oder trans- -CH=CH- bedeutet und
q 0 oder 1 bedeutet.Alternatively or in addition to the compounds of the formulas II and / or III, the media according to the present invention may contain one or more dielectrically positive compounds of the formula VI

wherein
R ⁶ denotes alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms and preferably alkyl or alkenyl,

independently of each other

L ⁶¹ and L ⁶² independently of one another denote H or F, preferably L ⁶¹ denotes F,
X ^{6 is} halogen, halogenated alkyl or alkoxy having 1 to 3 C atoms or halogenated alkenyl or alkenyloxy having 2 or 3 C atoms, preferably F, Cl, -OCF ₃ or -CF ₃ , more preferably F, Cl or -OCF ₃ means
Z ^{6 is} -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -COO-, trans -CH = CH-, trans- -CF = CF-, -CH ₂ O- or -CF ₂ O-, preferably - CH ₂ CH ₂ -, -COO- or trans -CH = CH- and most preferably -COO- or trans- CH = CH- and
q is 0 or 1.

worin die Parameter die jeweiligen oben angegebenen Bedeutungen besitzen und die Parameter L⁶³ und L⁶⁴ unabhängig voneinander und von den anderen Parametern H oder F bedeuten und Z⁶ vorzugsweise -CH₂-CH₂- bedeutet.Preferably, the media according to the present invention comprise one or more compounds of the formula VI, preferably selected from the group of the compounds of the formulas VI-1 and VI-2

wherein the parameters have the respective meanings given above and the parameters L ⁶³ and L ⁶⁴ independently of one another and of the other parameters are H or F and Z ^{6 is} preferably -CH ₂ -CH ₂ -.

worin R⁶ die oben angegebene Bedeutung besitzt.Preferably, the compounds of formula VI-1 are selected from the group of compounds of formulas VI-1a and VI-1b

wherein R ^{6 has} the meaning given above.

worin R⁶ die oben angegebene Bedeutung besitzt.The compounds of the formula VI-2 are preferably selected from the group of the compounds of the formulas VI-2a to VI-2d

wherein R ^{6 has} the meaning given above.

worin
R⁷ die oben unter Formel II für R² angegebene Bedeutung besitzt,
einer der Ringe von

vorzugsweise

und die anderen dieselbe Bedeutung besitzen oder unabhängig voneinander

Z⁷¹ und L⁷² unabhängig voneinander -CH₂CH₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O-, -CF₂O- oder eine Einfachbindung bedeuten, vorzugsweise eines oder mehrere von ihnen eine Einfachbindung bedeutet/bedeuten und ganz bevorzugt beide eine Einfachbindung,
t 0, 1 oder 2, vorzugsweise 0 oder 1, stärker bevorzugt 1 bedeutet und
X⁷ die oben unter Formel II für X² angegebene Bedeutung besitzt oder alternativ unabhängig von R⁷ eine der für R⁷ angegebenen Bedeutungen besitzen kann,
enthalten.In addition, the liquid-crystal media according to the present invention may contain one or more compounds of formula VII

wherein
R ^{7 has} the meaning given above under formula II for R ² ,
one of the rings of

preferably

and the others have the same meaning or independent of each other

Z ⁷¹ and L ⁷² independently of one another denote -CH ₂ CH ₂ -, -COO-, trans -CH = CH-, trans- -CF = CF-, -CH ₂ O-, -CF ₂ O- or a single bond, preferably one or more of them is a single bond, and most preferably both are a single bond,
t is 0, 1 or 2, preferably 0 or 1, more preferably 1 and
X ^{7 has} the meaning given above for X ² under formula II or, alternatively, independently of R ^{7 may have} one of the meanings given for R ⁷ ,
contain.

The compounds of the formula VII are preferably dielectrically positive compounds.

worin
R⁸¹ und R⁸² unabhängig voneinander die oben unter Formel II für R² angegebene Bedeutung besitzen und

Z⁸¹ und Z⁸² unabhängig voneinander -CH₂CH₂-, -COO-, trans- -CH=CH-, trans- -CF=CF-, -CH₂O-, -CF₂O- oder eine Einfachbindung, vorzugsweise eines oder mehrere von ihnen eine Einfachbindung und ganz bevorzugt beide eine Einfachbindung,
L⁸¹ und L⁸² unabhängig voneinander C-F oder N, vorzugsweise einer von L⁸¹ und L⁸² oder beide C-F und ganz bevorzugt beide C-F und
s 0 oder 1 bedeutet, enthalten.In addition, the liquid-crystal media according to the present invention may contain one or more compounds of the formula VIII

wherein
R ⁸¹ and R ⁸² independently of one another have the meaning given above for R ² under formula II, and

Z ⁸¹ and Z ^{82 are} independently -CH ₂ CH ₂ -, -COO-, trans- -CH = CH-, trans- -CF = CF-, -CH ₂ O-, -CF ₂ O- or a single bond, preferably one or more of them is a single bond and most preferably both a single bond,
L ⁸¹ and L ^{82 are} independently CF or N, preferably one of L ⁸¹ and L ⁸² or both CF and most preferably both CF and
s is 0 or 1, included.

The compounds of the formula VIII are preferably dielectrically negative compounds.

worin
R⁸¹ und R⁸² die jeweiligen oben unter Formel VIII angegebenen Bedeutungen besitzen.The media according to the invention preferably comprise one or more compounds of the formula VIII, preferably selected from the group of the compounds of the formulas VIII-1 to VIII-3

wherein
R ⁸¹ and R ^{82 have} the respective meanings given above under formula VIII.

In formulas VIII-1 to VIII-3, R ^{81 is} preferably n-alkyl or 1-E-alkenyl and R ^{82 is} preferably n-alkyl or alkoxy.

The liquid-crystalline media according to the present invention preferably contain one or more compounds selected from the group of the compounds of the formulas I to VIII, preferably of the formulas I to VII and more preferably of the formulas I and II and / or III and / or IV and / or VI. Most preferably, they are predominantly, even more preferably essentially, and most preferably, completely composed.

In this application, "contained" in the context of compositions means that the entity in question, i. H. the medium or component, the specified component or components or compound or compounds, preferably in a total concentration of 10% or more, and more preferably 20% or more.

"Predominantly consist of" in this context means that the entity in question contains 55% or more, preferably 60% or more, and more preferably 70% or more of the indicated component or components or compound or compounds.

"Substantially consisting of" in this context means that the entity in question contains 80% or more, preferably 90% or more and most preferably 95% or more of the indicated component or components or compound or compounds.

"Virtually consist of" or "consist entirely of" in this context means that the entity in question contains 98% or more, preferably 99% or more and most preferably 100% of the stated component or components or compound or compounds.

Other mesogenic compounds, which are not explicitly mentioned above, can be used optionally and advantageously in the media according to the present invention. Such compounds are known to the person skilled in the art.

The liquid crystal media according to the present invention preferably have a clearing point of 70 ° C or more, more preferably 75 ° C or more, more preferably 80 ° C or more, and most preferably 85 ° C or more.

Preferably, the nematic phase of the media of the invention extends at least from 0 ° C or less to 70 ° C or more, more preferably at least from -20 ° C or less to 75 ° C or more, even more preferably at least -30 ° C or less to 75 ° C or more and especially at least from -40 ° C or less to 80 ° C or more.

The Δε of the liquid crystal medium according to the invention at 1 kHz and 20 ° C is preferably 2 or more, more preferably 3 or more, even more preferably 4 or more, and most preferably 6 or more. Preferably, Δε is 30 or less, more preferably Δε is 20 or less.

The .DELTA.n of the liquid crystal media according to the present invention, at 589 nm (Na ^D) and 20 ° C preferably in the range of 0.070 or more to 0.150 or less, more preferably in the range of 0.080 or more to 0.140 or less, still more preferably in the range from 0.090 or more to 0.135 or less and most preferably in the range of 0.100 or more to 0.130 or less.

In a first preferred embodiment of the present application, the Δn of the liquid crystal media according to the present invention is preferably 0.080 or more to 0.120 or less, more preferably in the range of 0.090 or more to 0.110 or less, and most preferably in the range of 0.095 or more to 0.105 or less, while Δε is preferably in the range of 6 or more to 11 or less, preferably in the range of 7 or more to 10 or less, and more preferably in the range of 8 or more to 9 or less.

In this embodiment, the nematic phase of the media of the invention preferably extends at least from -20 ° C or less to 70 ° C or more, more preferably at least from -20 ° C or less to 70 ° C or more, most preferably at least -30 ° C or less to 70 ° C or more and especially at least from -40 ° C or less to 70 ° C or more.

In a second preferred embodiment of the present application, the Δn of the liquid crystal media according to the present invention is preferably 0.100 or more to 0.140 or less, more preferably in the range of 0.110 or more to 0.130 or less, and most preferably in the range of 0.115 or more to 0.125 or less, while Δε is preferably in the range of 7 or more to 13 or less, preferably in the range of 9 or more to 12 or less, and more preferably in the range of 10 or more to 11 or less.

In this embodiment, the nematic phase of the media of the invention preferably extends at least from -20 ° C or less to 80 ° C or more, more preferably at least from -20 ° C or less to 85 ° C or more, even more preferably at least -30 ° C or less to 80 ° C or more and especially at least from -40 ° C or less to 85 ° C or more.

According to the present invention, the compounds of formula I are preferably together in the media in a total concentration of from 1% to 50%, more preferably from 1% to 30%, more preferably from 2% to 30%, more preferably from 3% to 30% %, and more preferably from 5% to 25% of the total mixture.

The compounds selected from the group of formulas II and III are preferably used in a total concentration of from 2% to 60%, more preferably from 3% to 35%, even more preferably from 4% to 20% and most preferably from 5% to 15%. the total mixture used.

The compounds of formula IV are preferably used at a total concentration of from 5% to 70%, more preferably from 20% to 65%, even more preferably from 30% to 60% and most preferably from 40% to 55% of the total mixture.

The compounds of formula V are preferably used in a total concentration of from 0% to 30%, more preferably from 0% to 15% and most preferably from 1% to 10% of the total mixture.

The compounds of formula VI are preferably used in a total concentration of from 0% to 50%, more preferably from 1% to 40%, even more preferably from 5% to 30% and most preferably from 10% to 20% of the total mixture.

Optionally, the media of the invention may contain other liquid crystal compounds to adjust the physical properties. Such compounds are known to the person skilled in the art. Their concentration in the media according to the present invention is preferably 0% to 30%, more preferably 0.1% to 20%, and most preferably 1% to 15%.

The concentration of the compound of the formula CC-3-V in the media according to the invention in a preferred embodiment may be 50% to 65%, more preferably 55% to 60%.

The liquid-crystal media preferably contain a total of 50% to 100%, more preferably 70 to 100% and most preferably 80% to 100% and especially 90% to 100% of the compounds of the formulas I to VII, preferably selected from the group of the compounds of the formulas Formulas IA, IB and II to VI, particularly preferably of the formulas I to V, in particular of the formulas IA, IB, II, III, IV, V, and VII and very particularly preferably the formulas IA, IB, II, III, IV and V. Preferably, they are predominantly of it, and most preferably they consist almost entirely thereof. In a preferred embodiment, the liquid-crystal media each contain one or more compounds of each of these formulas.

In the present application, the term dielectrically positive describes compounds or components with Δε> 3.0, dielectrically neutral with -1.5 ≤ Δε ≤ 3.0 and dielectrically negative with Δε <-1.5. Δε is determined at a frequency of 1 kHz and 20 ° C. The dielectric anisotropy of each compound is determined from the results of a solution of 10% of each individual compound in a nematic host mixture. If the solubility of each compound in the host mixture is less than 10%, the concentration is reduced to 5%. The capacities of the test mixtures are determined in a cell with homeotropic as well as homogeneous orientation. The layer thickness is about 20 μm for both cell types. The applied voltage is a square wave with a frequency of 1 kHz and an effective value of typically 0.5V to 1.0V, but is always chosen to be below the capacitive threshold for the particular test mixture.

Δε is delineated as (ε _|| - ε _⊥ ), while _εchchschn. (ε _|| + 2ε _⊥ ) / 3.

As a host mixture, the mixture ZLI-4792 is used for dielectrically positive compounds and the mixture ZLI-3086 for dielectrically neutral as well as for dielectrically negative compounds, both from Merck KGaA, Germany. The absolute values of the dielectric constants of the compounds are determined from the change in the respective values of the host mixture upon addition of the compounds of interest. The values are extrapolated to a concentration of the compounds of interest of 100%.

Components which have a nematic phase at the measuring temperature of 20 ° C are measured as such, all others are treated as compounds.

The term threshold voltage in the present application refers to the optical threshold and is given for 10% relative contrast (V ₁₀ ), the term saturation voltage refers to optical saturation and is given for 90% relative contrast (V ₉₀ ), in both cases, if not expressly stated otherwise. The capacitive threshold voltage (V ₀ ), also called the Freedericks threshold V _Fr , is only used if expressly stated.

The parameter ranges given in this application all include the limits unless expressly stated otherwise.

The different upper and lower limits given for different ranges of properties provide additional preferred ranges in combination.

Throughout this application, the following terms and definitions apply unless expressly stated otherwise. All concentrations are given in percentage by weight and refer in each case to the total mixture, all temperatures and all temperature differences are given in degrees Celsius or degree of difference. All physical properties will be after "Merck Liquid Crystals, Physical Properties of Liquid Crystals", as of Nov. 1997, Merck KGaA, Germany , and are listed for a temperature of 20 ° C, unless otherwise stated. The optical anisotropy (Δn) is determined at a wavelength of 589.3 nm. The dielectric anisotropy (Δε) is determined at a frequency of 1 kHz. The threshold voltages as well as all other electro-optical properties are determined with test cells manufactured at Merck KGaA, Germany. The test cells for the determination of Δε have a layer thickness of approximately 20 μm. The electrode is a circular ITO electrode with a surface area of 1.13 cm ² and a guard ring. The alignment layers are SE-1211 from Nissan Chemicals, Japan, for homeotropic alignment (ε _|| ) and polyimide AL-1054 from Japan Synthetic Rubber, Japan, for homogeneous alignment (ε _⊥ ). Capacitance is determined using a Solatron 1260 frequency response analyzer using a sine wave with a voltage of 0.3 V _rms . The light used in the electro-optical measurements is white light. In this case, a structure with a commercially available device DMS Fa. Autronic Melchers, Germany is used. The characteristic stresses were determined under vertical observation. The threshold voltage (V ₁₀ ), mid-gray voltage (V ₅₀ ) and saturation voltage (V ₉₀ ) were determined for 10%, 50% and 90% relative contrast, respectively.

The liquid crystal media according to the present invention may include further additives and chiral dopants in the usual concentrations. The total concentration of these other ingredients is in the range of 0% to 10%, preferably 0.1% to 6%, based on the total mixture. The concentrations of the individual compounds used are preferably each in the range of 0.1% to 3%. The concentration of these and similar additives is not taken into account in the specification of the values and concentration ranges of the liquid crystal components and compounds of the liquid crystal media in this application.

The liquid-crystal media according to the invention consist of several compounds, preferably from 3 to 30, more preferably from 4 to 20 and most preferably from 4 to 16 compounds. These compounds are mixed in a conventional manner. In general, the desired amount of the compound used in the smaller amount is dissolved in the compound used in the larger amount. If the temperature is above the clearing point of the compound used in the higher concentration, the completion of the dissolution process is particularly easy to observe. However, it is also possible, the media in other conventional ways, for example using so-called premixes, which may be z. B. may be homologous or eutectic mixtures of compounds, or using so-called "multi-bottle" systems whose ingredients are themselves ready mixtures.

By adding suitable additives, the liquid crystal media according to the present invention can be modified to be useful in all known types of liquid crystal displays, either by using the liquid crystal media per se, such as TN, TN-AMD, ECB-AMD, VAN-AMD, IPS-AMD, FFS-AMD LCDs or in composite systems, such as PDLC, NCAP, PN LCDs and especially in ASM-PA LCDs.

All temperatures, such. B. the melting point T (K, N) or T (K, S), the transition from the smectic (S) to the nematic (N) phase T (S, N) and the clearing point T (N, I) of the liquid crystals are given in degrees Celsius. All temperature differences are indicated in degrees of difference.

Tabelle B: Verknüpfungsgruppen E -CH₂CH₂- Z -CO-O- V -CH=CH- Zl -O-CO- X -CF=CH- O -CH₂-O- Xl -CH=CF- Ol -O-CH₂- B -CF=CF- Q -CF₂-O- T -C≡C- Ql -O-CF₂- W -CF₂CF₂- T -C≡C- Tabelle C: Endgruppen Linke Seite Rechte Seite, Verwendung allein -n- C_nH_2n+1- -n -C_nH_2n+1 -nO- C_nH_2n+1-O- -nO -O-C_nH_2n+1 -u- CH₂=CH- -V -CH=CH₂ -nV- C_nH_2n+1-CH=CH- -nV -C_nH_2n-CH=CH₂ -Vn- CH₂=CH-C_nH_2n+1- -Vn -CH=CH-C_nH_2n+1 -nVm- C_nH_2n+1-CH=CH-C_mH_2m- -nVm -C_nH_2n-CH=CH-C_mH_2m+1 -N- N=C- -N -C≡N -S- S=C=N- -S -N=C=S -F- F- -F -F -CL- Cl- -CL -Cl -M- CFH₂- -M -CFH₂ -D- CF₂H- -D -CF₂H -T- CF₃- -T -CF₃ -MO- CFH₂O- -OM -OCFH₂ -DO- CF₂HO- -OD -OCF₂H -TO- CF₃O- -OT -OCF₃ -OXF- CF₂=CH-O- -OXF -O-CH=CF₂ -A- H-C≡C- -A -C≡C-H -nA- C_nH_2n+1-C=C- -An -C=GC_nH_2n+1 -NA- N≡C-C≡C- -AN -C≡C-C≡N Verwendung zusammen miteinender und mit anderen -...A...- -C≡C- -...A... -C≡C- -...V...- CH=CH- -...V... -CH=CH- -...Z...- -CO-O- -...Z... -CO-O- -...Zl...- -O-CO- -...Zl... -O-CO- -...K...- -CO- -...K... -CO- -...W...- -CF=CF- -...W... -CF=CF- worin n und m jeweils ganze Zahlen bedeuten und die drei Punkte „...” Platzhalter für andere Abkürzungen aus dieser Tabelle sind. In der folgenden Tabelle werden Beispielstrukturen zusammen mit ihren jeweiligen Abkürzungen angegeben. Diese werden gezeigt, um die Bedeutung der Regeln für die Abkürzungen zu demonstrieren. Weiterhin stellen sie Verbindungen dar, die vorzugsweise verwendet werden. Tabelle D: Beispielstrukturen

worin n, m und l bevorzugt unabhängig voneinander 1 bis 7 bedeuten.In the present invention, and more particularly in the following examples, the structures of the mesogenic compounds are indicated by abbreviations, also referred to as acronyms. In these acronyms, the chemical formulas are abbreviated as follows using 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-1 , C _m H _2m-1 and C _l H _{2l-1 are} straight-chain alkyl or alkenyl , preferably 1-E-alkenyl, each with n, m or 1 C atoms. In Table A, the codes used for the ring elements of the core structures of the compounds are listed, while in Table B, the linking groups are shown. Table C gives the meanings of the codes for the left and right end groups. The acronyms are composed of the codes for the ring elements with optional join groups, followed by a first hyphen and the codes for the left end group, as well as a second hyphen and the codes for the right end group. Table D summarizes example structures of compounds with their respective abbreviations. Table A: Ring elements.

Table B: Link Groups e -CH ₂ CH ₂ - Z -CO-O- V -CH = CH- zl -O-CO- X CF = CH- O -CH ₂ -O- xl -CH = CF- Oil -O-CH ₂ - B CF = CF Q -CF ₂ -O- T -C≡C- ql -O-CF ₂ - W -CF ₂ CF ₂ - T -C≡C- Table C: end groups Left side Right side, Use alone -n- C _n H _{2n + 1} - -n -C _n H _{2n + 1} -no- C _n H _{2n + 1} -O- -NO -OC _n H _{2n + 1} -u CH ₂ = CH- -V -CH = CH ₂ -nV- C _n H _{2n + 1} -CH = CH- -nv -C _n H _2n -CH = CH ₂ -Vn- CH ₂ = CH-C _n H _{2n + 1} - Vn -CH = CH-C _n H _{2n + 1} -nVm- C _n H _{2n + 1} -CH = CH-C _m H _2m - -nVm -C _n H _2n -CH = CH-C _m H _{2m + 1} -N- N = C- -N -C≡N -S S = C = N- -S -N = C = S -F- F- -F -F -CL- Cl CL -Cl -M- CFH ₂ - -M -CFH ₂ D- CF ₂ H -D -CF ₂ H -T- CF ₃ - -T -CF ₃ -NOT A WORD- CFH ₂ O- -OM -OCFH ₂ -DO- CF ₂ HO- --OD -OCF ₂ H -to- CF ₃ O- --OT -OCF ₃ -OXF- CF ₂ = CH-O- -OXF -O-CH = CF ₂ -A- HC≡C- -A -C≡CH -n / A- C _n H _{2n + 1} -C = C- -At -C = GC _n H _{2n + 1} -N / A- N≡CC≡C- -AT -C≡CC≡N Use together with one another and with others -... A ...- -C≡C- -... A ... -C≡C- -... ...- V CH = CH- -... V ... -CH = CH- -... Z ...- -CO-O- -... Z ... -CO-O- -... Zl ...- -O-CO- -... Zl ... -O-CO- -... K ...- CO- -... K ... CO- -... W ...- CF = CF -... W ... CF = CF where n and m are integers and the three dots "..." are placeholders for other abbreviations in this table. The following table shows sample structures along with their respective abbreviations. These are shown to demonstrate the importance of the rules for the abbreviations. Furthermore, they are compounds which are preferably used. Table D: Example Structures

wherein n, m and 1 are preferably independently from 1 to 7.

In the following table, Table E, example compounds are compiled which can be used in the mesogenic media according to the present invention as additional stabilizers.

Table E

In a preferred embodiment of the present invention, the mesogenic media contain one or more compounds selected from the group of compounds of Table E.

In the following Table F, example compounds are summarized, which can be used in the mesogenic media according to the present invention preferably as chiral dopants.

Table F

In a preferred embodiment of the present invention, the mesogenic media contain one or more compounds selected from the group of compounds of Table F.

Preferably, the mesogenic media according to the present application contain two or more, preferably four or more, compounds selected from the group consisting of the compounds of the above tables.

• – sieben oder mehr, vorzugsweise acht oder mehr Einzelverbindungen, vorzugsweise von drei oder mehr, besonders bevorzugt von vier oder mehr, unterschiedlichen Formeln, ausgewählt aus der Gruppe der Verbindungen der Tabelle D.

The liquid crystal media according to the present invention preferably contain

• - seven or more, preferably eight or more individual compounds, preferably of three or more, more preferably of four or more, different formulas selected from the group of compounds of Table D.

Examples

The following examples illustrate the present invention without limiting it in any way.

From the physical properties, however, it will be apparent to those skilled in the art which properties can be achieved and in which areas they are modifiable. In particular, therefore, the combination of the various properties that can preferably be achieved, well defined for the expert.

There are prepared liquid crystal mixtures having the composition and the properties as indicated in the following tables.

Examples substance

The following substances are preferred substances of the formula I according to the present application.

applications

Application Example 1

Comparative Example 1 and Application Examples 1.1 to 1.3

Mixture M1: composition Physical Properties connection T (N,) = 95.5 ° C No. abbreviation c /% n _e (20 ° C, 589.3 nm) = 1.5762 1 MUQU-3-F 8.0 Δn (20 ° C, 589.3 nm) = 0.0922 2 CCGU3-F 7.0 ε _|| (20 ° C, 1 kHz) = 7.0 3 PGUQU-3-F 2.0 Δε (20 ° C, 1 kHz) = 4.3 4 CC-3-V 41.0 k ₁ (20 ° C) = 15.8 pN 5 CC-3-V1 14.0 k ₃ (20 ° C) = 18.4 pN 6 CCP-V-1 8.0 γ ₁ (20 ° C) = 73 mPa · s 7 CCP-V-21 14.0 V ₀ (20 ° C) = 2.03V 8th PGP-2-4 2.0 9 CPGP-4-3 4.0 F 100.0 Comment: nzb: to be determined.

This mixture (mix M1) is prepared and divided into four parts. The first part is examined without adding another compound. To the other three parts of the mixture are added 100 ppm, 200 ppm and 500 ppm of the compound to be tested, here the compound of formula I-1a-2. In each case, four test cells are filled with the orientation layer AL-16301 (Japan Synthetic Rubber (JSR), Japan) and examined with regard to their voltage holding ratio. The initial value and the value after 2 hours of UV exposure are determined in a Suntest device from Heraeus, Germany. In each case the HR is measured at a temperature of 100 ° C, after 5 minutes in the oven. The results are summarized in the following table. example c (X) / ppm HR ₀ /% HR _UV (2 h) /% V1.0 0 99.6 45.7 1.1 100 99.6 46.7 1.2 200 99.5 51.0 1 _. 3 500 99.5 61.7 Note: X: compound of formula I-1a-2

The mixtures of application examples 1.1 to 1.3, which all contain a compound of the formula I, are distinguished, in particular, by excellent stability to UV irradiation. In the course of these three mixtures, the stability increases with increasing concentration of the compound of the formula I-1a-2.

The temperature stability is checked by a heat test. For this purpose, the HR is determined before and after heat exposure. The heat load is applied to the liquid crystal material in the bulk. For this purpose, 2 g of the material are stored in a sealed glass bottle for 4 h in an oven at a temperature of 150 ° C.

Application Example 2:

Comparative Example 2.0 and Application Example 2.1

As in Application Example 1, the mixture M1 is prepared and divided here into two parts. The first part is examined without adding another compound. To the second part of the mixture, 500 ppm of the compound to be tested, here the compound of formula I-1a-1, given. The two parts of the mixture are examined as described in Application Example 1. The results are summarized in the following table. example c (Y) / ppm HR ₀ /% HR _UV (2 h) /% V2.0 0 99.8 44.4 2.1 100 99.7 51.3 Comments: Y: compound of formula I-1a-1

The deviation of HR of the host in Comparative Example 2 from that in Comparative Example 1 is due to the reproducibility of the measurement method. Within a series of measurements in one example and the associated comparison measurements, the reproducibility is significantly better (about 1/2 to 1/3 times that) and thus the fluctuation range correspondingly much lower.

Comparative Examples V3.0 to V3.3

gegeben. Die Teile der Mischung werden wie unter Anwendungsbeispiel 1 beschrieben untersucht. Die Ergebnisse sind in der folgenden Tabelle zusammengestellt. Beispiel c(Z)/ppm HR₀/% HR_UV(2 h)/% V3.0 0 99,5 47,3 V3.1 100 99,6 46,3 V3.2 200 99,6 46,5 V3.3 500 99,6 50,1 Bemerkung: Z: Verbindung der oben angegeben Formel.As in Application Example 1, the mixture M1 is prepared and divided again into four parts. The first part is examined without adding another compound. The three further parts of the mixture, as in Application Example 1, 100 ppm, 200 ppm, and 500 ppm of the compound to be tested, here the compound of formula Z

given. The parts of the mixture are investigated as described in Application Example 1. The results are summarized in the following table. example c (Z) / ppm HR ₀ /% HR _UV (2 h) /% V3.0 0 99.5 47.3 V3.1 100 99.6 46.3 V3.2 200 99.6 46.5 V3.3 500 99.6 50.1 Note: Z: Compound of formula given above.

Here it can be clearly seen that this compound has no or almost no stabilizing effect on the HR of the mixture.

Application Example 4:

Comparative Example 4.0 and Application Example 4.1

As in Application Example 2, the mixture M1 is prepared and divided into two parts. The first part is examined without adding another compound. To the second part of the mixture are 500 ppm of the compound to be tested, here the compound "Cyasorb UV3852S" from the company Cytec, West Paterson, USA given the formula. The two parts of the mixture are investigated as described in Application Example 1. The results are summarized in the following table. example c (V) / ppm HR ₀ /% HR _UV (2 h) /% 4.0 0 99.8 44.4 4.1 500 99.8 47.0 Note: V: Compound Cyasorb UV3852-S

The stabilizing effect here is weaker than in Examples 1 and 2. However, it should be noted that the concentration of the compounds of the formula I in Cyasorb UV3852-S is only 50%, and that these compounds are predominantly long alkyl or alkenyl chains and thus have a high molecular weight. Thereby, the average concentration of the active N-containing molecular units, as compared to the compounds used in Examples 1 and 2, is also reduced.

QUOTES INCLUDE IN THE DESCRIPTION

This list of the documents listed by the applicant has been generated automatically and is included solely for the better information of the reader. The list is not part of the German patent or utility model application. The DPMA assumes no liability for any errors or omissions.

Cited patent literature

• DE 4000451 [0002]
• EP 0588568 [0002]
• WO 91/05029 [0006]
• JP 07-181439 (A) [0007]
• EP 0667555 [0007]
• EP 0673986 [0007]
• DE 19509410 [0007]
• DE 19528106 [0007]
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• WO 96/23851 [0007]
• WO 96/28521 [0007]

Cited non-patent literature

• Miéville, P. et al, Angew. Chem. 2010, 122, pages 6318-6321 [0008]
• "Merck Liquid Crystals, Physical Properties of Liquid Crystals", as of Nov. 1997, Merck KGaA, Germany [0104]

Claims (12)

Liquid crystal medium, characterized in that it contains one or more compounds of the formula I

wherein R ¹¹ to R ^{14 are} each independently of one another, alkyl having 1 to 4 C atoms, X ¹ H or O *, Z ^{1 is} -O-, - (CO) -O-, -O- (CO) -, -O - (CO) -O-, -NH-, -NY ⁰¹ - or -NH- (CO) -, Y ¹ and Y ⁰¹ , in each case independently of one another, straight-chain or branched alkyl having 1 to 20 C atoms, also cycloalkyl, Cycloalkylalkyl, or alkylcycloalkyl, where in all of these groups mentioned one or more -CH ₂ - groups may be replaced by -O- so that in Mplekül no two O atoms are directly connected to each other, and in the case that Z ¹ - O- (CO) -O- means Y ¹ alternatively also

can mean contains. Medium according to claim 1, characterized in that it comprises one or more compounds selected from the group of the compounds of the formulas II and III

in which R ² and R ^3, independently of one another, are alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 C atoms, alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl having 2 to 7 C atoms,

at each appearance independently

L ²¹ , L ²² , L ³¹ and L ^32, independently of one another, denote H or F, X ² and X ^3, independently of one another, halogen, halogenated alkyl or alkoxy having 1 to 3 C atoms or halogenated alkenyl or alkenyloxy having 2 or 3 C atoms, Z ^{3 is} -CH ₂ CH ₂ -, -CF ₂ CF ₂ -, -COO-, trans -CH = CH-, trans- -CF = CF-, -CH ₂ O- or a single bond and m and n are independent of each other 0, 1, 2 or 3, mean. Medium according to one of claims 3 or 2, characterized in that it contains one or more compounds of the formula IV

wherein R ⁴¹ and R ⁴² independently of one another have the meaning given in claim 2 above under formula II for R ² ,

independently of each other and in case of double occurrences of

also these independently

Z ⁴¹ and Z ⁴² independently of one another and also when L ^{41 is} present twice, they are also independently of one another -CH ₂ CH ₂ -, -COO-, trans- -CH = CH-, trans-CF = CF-, -CH ₂ O- , -CF ₂ O-, -C≡C- or a single bond and p is 0, 1 or 2, contains. Medium according to one or more of claims 1 to 3, characterized in that the total concentration of the compounds of formula I in the medium in the range of 10 ppm to 10,000 ppm. Medium according to one or more of claims 1 to 4, characterized in that the compounds of the formula I compounds selected from the group of compounds of the formulas total concentration of the compounds of formulas I-1 to I-7

wherein the parameters have the meanings given in claim 1, are. Medium according to one or more of claims 1 to 5, characterized in that it contains one or more compounds of the formula II as specified in claim 2 Medium according to one or more of claims 1 to 6, characterized in that it contains one or more compounds of the formula III as specified in claim 2. Medium according to one or more of claims 1 to 7, characterized in that it contains one or more dielectrically neutral compounds of the formula V

wherein R ⁵¹ and R ⁵² independently of one another have the meaning given for R ² under formula II in claim 2,

independent on each occurrence

Z ⁵¹ and Z ⁵² independently of one another and also in the case of a Z ⁵¹ occurrence, these are also independently of one another -CH ₂ CH ₂ -, -COO-, trans- -CH = CH-, trans-CF = CF-, -CH ₂ O- , -CF ₂ O- or a single bond and r 0, 1 or 2 means. Liquid crystal display, characterized in that it contains a medium according to one or more of claims 1 to 8. Display according to claim 9, characterized in that it is addressed by an active matrix. Use of a medium according to one or more of claims 1 to 8 in a liquid crystal display. Process for the preparation of a medium according to one or more of Claims 1 to 8, characterized in that one or more compounds of the formula I as given in Claim 1 have one or more of the compounds mentioned in one or more of Claims 2 and 3 / or one or more other mesogenic compounds and / or one or more additives.