KR101803118B1

KR101803118B1 - Polymerizable compounds and use thereof in liquid crystal displays

Info

Publication number: KR101803118B1
Application number: KR1020137001870A
Authority: KR
Inventors: 안드레아스 타우거벡; 알렉산더 한; 아힘 괴츠
Original assignee: 메르크 파텐트 게엠베하
Priority date: 2010-06-25
Filing date: 2011-06-01
Publication date: 2017-11-29
Also published as: JP2013535033A; KR20170117225A; TW201204701A; KR101902726B1; CN103922932A; WO2011160764A1; KR20130132736A; CN102959048B; JP2015025130A; TWI532714B; DE102011103182A1; CN102959048A; JP5694525B2; JP6125470B2

Abstract

The present invention relates to polymerizable compounds, processes and intermediates for making them, and their optical, electro-optical and electronic applications, in particular liquid crystal (LC) media and LC displays, sustained alignment ") type of LC display.

Description

[0001] POLYMERIZABLE COMPOUNDS AND USE THEREOF IN LIQUID CRYSTAL DISPLAYS [0002]

The present invention relates to polymerizable compounds, methods and intermediates for making them, and to optical, electro-optical and electronic purposes, in particular liquid crystal (LC) media and LC displays, in particular PS ("polymer- Polymer-sustained alignment ") type of LC display.

Currently used liquid crystal displays (LC displays) are usually TN ("twisted nematic") type displays. However, such a display is disadvantageous in that the viewing-angle dependency of the contrast is strong. Also known are so-called VA ("vertically aligned") displays with a wide viewing angle. The LC cell of the VA display contains a layer of a LC medium with generally negative dielectric (DC) anisotropy between the two transparent electrodes. In the switch-off state, the molecules of the LC layer have an aligned or sloping homeotropic alignment perpendicular (homotrophically) to the electrode surface. When voltage is applied to both electrodes, the LC molecules are rearranged in parallel to the electrode surface.

Also known are OCB ("optically compensated bends") displays based on birefringence effects and having an LC layer with so-called "bend" alignment and generally positive (DC) anisotropy. When a voltage is applied, the LC molecules are rearranged in a direction perpendicular to the electrode surface. In addition, OCB displays typically contain one or more birefringent optical retardation films to prevent undesirable translucency of the bend cell in the dark. OCB displays have wider viewing angles and shorter response times than TN displays.

In addition, there is also a so-called < RTI ID = 0.0 > IPS (< / RTI > "In-plane switching") display is also known. When a voltage is applied to the electrodes, an electric field having a significant component parallel to the LC layer is generated between these electrodes. This causes re-alignment of the LC molecules in the layer plane.

Similarly, unlike the IPS display, only one of the substrates is structured in a comb-like manner, while the other electrode contains two electrodes on the same substrate, while the other electrode is a non-structured so-called FFS (See, for example, SHJung et al., Jpn. J. Appl. Phys., Volume 43 , No. 3, 2004, 1028). This results in a strong electric field having both a strong, so-called "fringe field," a strong electric field adjacent to the edge of the electrode, and a strong vertical component and strong horizontal component throughout the cell. IPS displays as well as FFS displays have low viewing angle dependence of contrast ratio.

In a more recent type of VA display, the uniform alignment of the LC molecules is limited to a number of relatively small domains within the LC cell. There may also be a disclination between these domains, also known as the tilt domain. A VA display with a tilted domain has a larger viewing angle dependence of contrast ratio and gray tint than a conventional VA display. This type of display can also be manufactured more simply because further processing of the electrode surface, e.g. rubbing, for uniform alignment of molecules in the switch-on state is no longer necessary. Instead, the preferential orientation of the tilt or pretilt angle is controlled by the special design of the electrodes.

In the case of the so-called MVA ("multi-domain vertically aligned") display, this is typically achieved by an electrode with a protrusion that causes local line inclination. As a result, the LC molecules are aligned in parallel to the electrode surface in different directions within a defined different region of the cell upon application of a voltage. Thereby achieving "controlled" switching, and inhibiting the formation of an interfering disclination line. This arrangement improves the viewing angle of the display, but decreases its transmissivity.

Further development of the MVA uses protrusions only on one electrode face and the opposite electrode has a slit, thereby improving translucency. The slotted electrode generates a non-uniform electric field in the LC cell upon application of the voltage, which means that controlled switching is still being achieved. In order to further improve the light transmittance, the gap between the slits and the protrusions can be increased, but this actually increases the response time.

In the case of so-called PVA (patterned VA), the protrusions are completely unnecessary in that both electrodes are structured as slits on both sides, thereby increasing the contrast ratio and improving the light transmittance, but this is technically difficult, Making it more sensitive to effects (such as "tapping"). However, for many applications such as monitors, especially TV screens, it is required to shorten the response time of the display and to improve the contrast ratio and luminance (transmittance).

Also called PS (polymer-persisted) or PSA (polymer-persisted alignment) displays, which are also used with the term " PS (polymer-stabilized) In the case of such a display, a small amount (e.g., less than 0.3 wt.%, Typically less than 1 wt.%) Of one or more polymerizable compounds is added to the LC medium and after introduction into the LC cell, Is generally polymerized or cross-linked in situ by UV light polymerization. It has also proved particularly suitable to add polymerizable mesogenic or liquid crystal compounds, also known as "reactive mesogens" or "RM", to the LC mixture.

Unless otherwise stated, the term "PSA" is then used to denote a PS display or a PSA display.

On the other hand, the PS (A) principle is also used in various conventional LC displays. Thus, for example, PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS and PSA-TN displays are known. In general, the polymerization of polymerizable compounds is preferably carried out by applying a voltage in the case of PSA-VA and PSA-OCB displays, and in the case of PSA-IPS displays with or without voltage. As can be demonstrated in the test cell, the PS (A) method produces a line gradient in the cell. Thus, in the case of a PSA-OCB display, the bend structure can be stabilized so that an offset voltage can be eliminated or reduced. For a PSA-VA display, this has a positive impact on response time. For PSA-VA displays, standard MVA or PVA pixel and electrode designs can be used. However, it is also possible to obtain a very good light transmittance with a very good contrast ratio while at the same time, for example, by having only one structured electrode surface and having no projections at all, thereby greatly simplifying the manufacture.

In addition, so-called positive-VA displays have proven to be particularly preferred embodiments. As in conventional VA displays, the initial alignment of the liquid crystals in an initial state in which no voltage is applied is homeotropic, i.e., substantially perpendicular to the substrate. However, unlike a conventional VA display, a positive-VA display uses a LC medium having a positive dielectric anisotropy. When a voltage is applied to an interdigital electrode that creates an electric field substantially parallel to the LC medium layer, the LC molecules turn into an alignment substantially parallel to the substrate. Also, this type of interdigital electrode is often used in IPS displays. The corresponding polymer-stabilized (PSA) can significantly reduce the response time, which has proven advantageous in the case of positive-VA displays.

PSA-VA displays are described, for example, in JP 10-036847 A, EP 1 170 626 A2, US 6,861,107, US 7,169,449, US 2004/0191428 A1, US 2006/0066793 A1 and US 2006/0103804 A1. PSA-OCB displays are described, for example, in T. -J-. Chen et al., Jpn. J. Appl. Phys. 45, 2006, 2702-2704; H. Kim, L. -C-. Chien, Jpn. J. Appl. Phys. 43, 2004, 7643-7647. PSA-IPS displays are described, for example, in US 6,177,972 and Appl. Phys. Lett. 1999, 75 (21), 3264). PSA-TN displays are described, for example, in Optics Express 2004, 12 (7), 1221.

Like the conventional LC display described above, the PSA display can be driven as an active-matrix or passive-matrix display. In the case of an active-matrix display, the individual pixels are usually addressed by integrated non-linear active elements such as transistors (e.g., thin film transistors ("TFTs")) as is known from the prior art, , The individual pixels are usually addressed by a multiplex method known from the prior art.

In particular, for monitors and especially TV applications, there is a continuing need to optimize contrast time and brightness (and thus transmittance) as well as response times of LC displays. The PSA method can provide significant advantages here. In the case of the PSA-VA, PSA-IPS, PSA-FFS and PSA-positive-VA displays in particular, the reduction of the response time (which is related to the pre-calibratable measurable in the test cell) can be achieved without serious adverse effects on other variables have.

In the prior art, polymerizable compounds of the following general formula were used:

In this formula,

P represents a polymerizable group, generally an acrylate or methacrylate group as described, for example, in US 7,169,449.

However, the problem arises that not all combinations of an LC mixture (also referred to herein as an "LC host mixture") plus a polymerizable component (typically RM) are suitable for PSA displays, For example, the so-called "voltage holding ratio" (VHR or HR) is inadequate in TFT display products. Furthermore, it has been found that, in use in PSA displays, the LC mixtures and RMs known from the prior art still have some disadvantages. Thus, not all known RMs that are soluble in the LC mixture are suitable for use in a PSA display. In addition, it is often difficult to find a suitable selection criterion for RM in addition to direct measurements of PRECAST on PSA displays. If the polymerization with UV light (which may be beneficial for certain applications) without the addition of photoinitiator is desired, the choice of suitable RM is further reduced.

In addition, the combination of the selected LC host mixture / RM should have the lowest possible rotational viscosity and the highest possible electrical properties. In particular, you should have the highest possible VHR. In the PSA display, a high VHR is particularly needed after UV light irradiation, because UV exposure is a necessary part of the display manufacturing process, but also occurs as a normal exposure during the driving of the final display.

In particular, new materials available for PSA displays, which produce small pre-squared angles, would be desirable. It is desirable to have a material that produces a smaller pre-squared angle than previously known materials during polymerisation at the same exposure time and / or, in use, a (larger) pre-exposure square, which can be achieved using known materials, Substances that are already attainable will be desirable. Thus, the manufacturing time ("tact time ") of the display can be shortened and the cost of the manufacturing process can be reduced.

Another problem in the manufacture of PSA displays is the presence or removal of un-polymerized RM residuals after the polymerization step, particularly to produce a pre-scan square on the display. For example, unreacted RMs of this type may be polymerized in an uncontrolled manner, for example during drive after the display finish, thereby negatively affecting the properties of the display.

Thus, PSA displays known in the art often exhibit undesirable effects of so-called "afterimage" or "image burn ". That is, the image generated in the LC display is still visible by temporary addressing of these pixels after the electric field is switched off in individual pixels or after other pixels are addressed.

Such "afterimage" can occur on the one hand if an LC host mixture with low VHR is used. The UV element of sunlight or backlighting can cause undesirable decomposition reactions of the internal LC molecules and thus begin to generate ionic or free-radical impurities. They can be deposited in particular on the electrode or in the alignment layer, where they can reduce the effective applied voltage. This effect can also be observed in conventional LC displays that do not include polymer components.

In addition, additional "afterimage" effects caused by the presence of un-polymerized RM are often observed in PSA displays. The uncontrolled polymerization of the residual RM starts here by UV light from the environment or by backlighting. In the switched display area, this changes the tilt angle after a number of addressing cycles. Thus, a change in transmittance may occur in the switched region, but remains unchanged in the non-switched region.

It is therefore desirable that the polymerization of the RM proceeds as completely as possible during the manufacture of the PSA display and that the presence of the un-polymerized RM in the display is excluded or at least reduced as far as possible. To this end, there is a need for materials that enable highly efficient and complete polymerization. In addition, a control reaction of these residual amounts may be preferable. This will be simpler if the RM polymerizes more rapidly and effectively than the known materials to date.

Thus, there is still a great demand for PSA displays of the VA and OCB type, and LC media and polymerizable compounds for use in these displays, which do not have the above-mentioned disadvantages or only have only minor improvements and have improved properties. In particular, it is possible to achieve a high resistivity, as well as a wide operating temperature range, even a short response time at low temperatures, a low threshold voltage, a small squareness, a large number of gray shades, a high contrast ratio and a wide viewing angle, There is a great demand for materials for use in PSA displays and PSA displays having advantageous low temperature stability known as " VHR " and "LTS ", i.e. stability of the LC mixture for spontaneous crystallization from individual components do.

SUMMARY OF THE INVENTION The present invention has the object of providing a method and a device which have, without having or with reduced disadvantages as described above, to be polymerized as quickly and completely as possible, to form a low pretilt angle as early as possible, Particularly RM, and an LC medium comprising the same, suitable for use in a PSA display, preferably at the same time, enabling a very high resistivity value, a low threshold voltage and a short response time. In addition, the LC medium should have desirable LC phase characteristics and high VHR and LTS values.

It is a further object of the present invention to provide a novel RM, especially for optical, electro-optic and electronic products, and to a process and an intermediate suitable for the preparation thereof.

In particular, it is an object of the present invention to provide a polymerizable compound that produces a greater maximum line tilt after photopolymerization, which achieves the desired line warp more rapidly and significantly shortens the manufacturing time of the LC display.

This object is achieved according to the present invention by providing the materials, processes and LC displays described herein. In particular, it has been surprisingly found that some or all of the foregoing objectives may be met by providing a PSA display that contains at least one polymerized compound according to the present invention or by including at least one polymerizable compound according to the present invention Lt; RTI ID = 0.0 > LC < / RTI >

The use of this type of polymerizable compound in LC media and PSA displays in accordance with the present invention allows the desired pre-crystallization to be accomplished more quickly and significantly shortens the display manufacturing time. This is demonstrated in conjunction with the LC medium by exposure time-dependent pre-gradient measurement in a VA gradient cell. In particular, it is possible to achieve line warpage without the addition of a photoinitiator.

Since the polymerizable compound in the display according to the present invention exhibits a significantly faster polymerization rate in the PSA display, less unreacted residual amount also remains in the LC cell to improve its electro-optical properties, This becomes simpler.

JP 2000-281629 A discloses a cholesteric polymer film prepared therefrom for use as a rod-like polymerizable compound of the following structural formula and as a reflective polarizer:

WO 2008/121585 A1 describes a 1-vinylpyrene of the following structure as a monomer for use in compensation films:

However, the use of these compounds for the production of pre-cast squares in PSA displays is neither described nor apparent from JP 2000-281629 A or WO 2008/121585.

In addition, the use of polymerizable compounds according to the present invention in PSA displays due to polymerization in situ polymerization in situ for the rapid formation of tilt angles is not described or apparent from the prior art.

It has also been found, surprisingly, that the polymerizable compounds according to the invention for use in PSA displays exhibit considerably faster tilt angles and faster and more complete polymerization than the polymerizable compounds known in the prior art. This was confirmed by a direct comparison experiment. This result is not described or apparent from the prior art.

Accordingly, the present invention relates to compounds of the following general formula I (hereinafter also referred to as "polymerizable compounds according to the present invention") in liquid crystal (LC) media and LC displays of the PS or PSA (polymer- Lt; RTI ID = 0.0 > of:

I

In this formula,

W ¹ and W ² are each independently selected from the group consisting of -CY ₂ CY ₂ -, -CY═CY-, -CY ₂ -O-, -O-CY ₂ -, -C (O) -O-, -OC O) -, -C (R ^c R ^d ) -, -O-, -S- or -NR ^e -

Y represents, in each case, the same or different, H or F,

R ^a and R ^b are each independently of each other, P-Sp-, H, F , Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, SF 5, 1 to Linear or branched alkyl having 25 carbon atoms wherein one or more non-adjacent CH ₂ groups are each, independently of one another, arylene, -C (R ^0, ^{) = C (R 00) -} , -C≡C-, -N (R 0) -, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O- C-O- and at least one H atom may be replaced by F, Cl, Br, I, CN or P-Sp-), or aryl or heteroaryl (preferably 2-25 carbons Atoms and may also contain two or more fused rings and are optionally mono- or polysubstituted by L, with the proviso that at least one of the radicals R ^a and R ^b represents the group P-Sp- &Lt; / RTI &

R ^c , R ^d and R ^e are each independently of the other H, or straight-chain or branched alkyl having 1 to 12 carbon atoms,

P represents, in each case, the same or different, a polymerizable group,

Sp represents in each case, the same or different, a spacer group or a single bond,

A ¹ and A ² are each, independently of one another, an aromatic, heteroaromatic, alicyclic or heterocyclic group (preferably having 4 to 25 carbon atoms, which may contain fused rings, - or multiple substitution), < RTI ID = 0.0 >

L is in each case the same or different and is selected from the group consisting of P-Sp-, OH, CH ₂ OH, halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, (R ^x ) ₂ , -C (═O) Y ¹ , -C (═O) R ^x , -N (R ^x ) ₂ , optionally substituted silyl or an optionally substituted carbon or hydrocarbon group,

R ^x is selected from the group consisting of P-Sp-, H, halogen, linear, branched or cyclic alkyl having from 1 to 25, preferably 1 to 12 carbon atoms wherein one or more non-adjacent CH ₂ groups are O and / -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O- in such a way that the S atoms are not directly connected to each other, The H atom may be further substituted by F, Cl or P-Sp-)

Y ¹ represents halogen,

Z ¹ and Z ² are each independently selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O -, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, - (CH ₂ ) _n -, -CF ₂ CH ₂ - _{-CH 2 CF 2 -, - (} CF 2) n -, -CH = CH-, -CF = CF-, -CH = CF-, -CF = CH-, -C≡C-, -CH = CH- COO-, -OCO-CH = CH-, -CH 2 -CH 2 -COO-, -OCO-CH 2 -CH 2 -, -C (R 0 R 00) -, -C (R y R z) - Or a single bond,

R ⁰ and R ⁰⁰ are each independently of one another, in each case identically or differently, H or alkyl having 1 to 12 carbon atoms,

R ^y and R ^z each independently represent H, F, CH ₃ or CF ₃ ,

n represents, in each case, the same or different, 1, 2, 3 or 4,

p and q each independently represent 0, 1 or 2,

r represents, in each case, the same or different, 0, 1 or 2;

The present invention also relates to a LC medium comprising at least one compound of the general formula I and at least one further compound which may be mesogenic, liquid crystalline and / or polymerizable.

The present invention also relates to a LC medium comprising at least one compound of the general formula I and a polymer obtainable by polymerizing at least one further compound which may be mesogenic, liquid crystalline and / or polymerizable.

In addition,

A polymerizable component A) comprising at least one compound of the general formula I, and

- liquid crystal component B) (hereinafter also referred to as "LC host mixture") comprising one or more, preferably two or more, of the above-mentioned low molecular weight compounds (monomeric and non-

&Lt; / RTI >

The present invention also relates to a process for the preparation of a compound of formula I as described hereinbefore and hereinafter, wherein one or more low molecular weight liquid crystalline compounds or LC host mixtures as described hereinbefore and hereinafter are mixed with one or more compounds of general formula I and optionally further liquid crystal compounds and / And a method for producing the LC medium.

The present invention also relates to PS and PSA displays, in particular LC media, for producing inclination angles of LC media by in-situ polymerization of compounds of general formula I in a PSA display, preferably by application of an electric field or a magnetic field And to the use of the compounds of the general formula I according to the invention and the LC medium in PS and PSA displays.

The present invention also relates to LC displays, in particular PS or PSA displays, particularly preferably PSA-VA, PSA-OCB, PSA-IPS, PSA- FFS, PSA-VA or PSA-positive-Tn display.

The present invention also relates to a method of manufacturing a semiconductor device comprising two substrates and two electrodes, wherein at least one substrate is transparent to light and at least one substrate has one or two electrodes, Component and a low molecular weight component wherein the polymerized component is preferably obtained by polymerizing at least one polymerizable compound in the LC medium between the substrates of the LC cell, And wherein at least one of the polymerizable compounds is a compound of the general formula (I).

The present invention also relates to a process for the preparation of a LC medium comprising one or more low molecular weight liquid crystal compounds as described hereinbefore and hereinafter or an LC host mixture and one or more compounds of the general formula I in the presence of two substrates as described above and LC And introducing the polymerizable compound into the cell, preferably by applying a voltage to the electrode, to polymerize the polymerizable compound.

PS and PSA displays according to the present invention have two electrodes, preferably in the form of a transparent layer, applied to one or both of the substrates forming the LC cell. For example, one electrode may be applied to two substrates, respectively, as in a PSA-VA, PSA-OCB or PSA-TN display according to the present invention, or a PSA-Positive- Two electrodes are applied to only one of the two substrates and the remaining substrates do not have electrodes as in the IPS or PSA-FFS display.

The present invention also relates to novel compounds of the general formula I, processes for their preparation and novel intermediates used or obtained therefrom.

The following meanings apply to the foregoing and the following.

The terms "tilt" and "tilt angle" relate to the tilted alignment of LC molecules of the LC medium relative to the surface of the cell in an LC display (preferably a PS or PSA display herein). The angle of tilt herein represents the average angle (less than 90 DEG) between the longitudinal molecular axis of the LC molecules (LC director) and the plane-parallel outer plate surface forming the LC cell. A small value of the tilt angle (i. E., A large deviation from the 90 angle) corresponds to a large tilt. A suitable method for measuring the tilt angle is shown in the embodiment. Unless otherwise stated, the inclination angle values described above and below relate to such a measurement method.

The term "mesogenic group" is well known to those skilled in the art and is described in the literature and refers to a group that contributes to induce an LC phase in an essentially low molecular weight or polymeric material due to its anisotropic attraction and repulsion. The mesogenic group-containing compound (mesogenic compound) itself need not have the LC phase. In addition, the mesogenic compound may exhibit LC phase behavior only after mixing with other compounds and / or after polymerization. Typical mesogenic groups are, for example, rigid rod-shaped or disc-shaped units. An overview of terms and definitions used in connection with mesogenic or LC compounds is provided in Pure Appl. Chem. 73 (5), 888 (2001)) and C.I. Tschierske, G. Pelzl and S. Diele, Angew. Chem. 2004, 116, 6340-6368.

The term "spacer group" (also referred to hereinabove and hereinafter as "Sp") is also known to those skilled in the art and is described in the literature (for example, Pure Appl. Chem. 73 (5), 888 (2001) C. Tschierske, G. Pelzl and S. Diele, Angew. Chem., 2004, 116, 6340-6368). Unless otherwise stated, the term "spacer group" or "spacer " hereinbefore and hereinafter refers to a flexible group linking a mesogenic group and a polymerizable group to each other in a polymerizable mesogenic compound.

The term "reactive mesogen" or "RM" refers to a compound containing one mesogenic group and at least one functional group suitable for polymerization, also referred to as a polymerizable or P group.

The term "low molecular weight compounds" and "non-polymerizable compounds " refer to generally monomeric compounds which do not contain any functional groups suitable for polymerization under conventional conditions known to those skilled in the art, .

The term "organic group" refers to a carbon or hydrocarbon group.

The term "carbon group" refers to a monovalent or polyvalent organic group containing one or more carbon atoms, preferably 1 to 40 carbon atoms, which does not contain additional atoms (e.g., -C? C-) Such as N, O, S, P, Si, Se, As, Te, or Ge (e.g., carbonyl, etc.). The term "hydrocarbon group" refers to a carbon group that additionally contains one or more H atoms and optionally contains one or more heteroatoms such as N, O, S, P, Si, Se, As, Te or Ge.

The term "halogen" denotes F, Cl, Br or I.

The carbon or hydrocarbon group may be a saturated or unsaturated group. The unsaturated group is, for example, an aryl, alkenyl or alkynyl group. Carbon or hydrocarbon radicals having more than three carbon atoms may be linear, branched and / or cyclic, and may also have spiro linkages or condensation rings.

The terms "alkyl", "aryl", "heteroaryl" and the like also include multivalent groups such as alkylene, arylene, heteroarylene, and the like.

The term "aryl" denotes an aromatic carbon group or a group derived therefrom. The term "heteroaryl " refers to" aryl "as defined above containing one or more heteroatoms.

Preferred carbon and hydrocarbon groups are optionally substituted alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl having 1 to 40, preferably 1 to 25, particularly preferably 1 to 18 carbon atoms Alkylcarbonyloxy and alkoxycarbonyloxy, aryl or aryloxy optionally having 6 to 40, preferably 6 to 25 carbon atoms and optionally substituted 6 to 40, preferably 6, Alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having from 1 to 25 carbon atoms.

Further preferred carbon and hydrocarbon groups are a C ₁ -C ₄₀ alkyl, C ₂ -C ₄₀ alkenyl, C ₂ -C ₄₀ alkynyl, C ₃ -C ₄₀ allyl, C ₄ -C ₄₀ alkyl diene yl, C ₄ - C ₄₀ polyenes yl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ alkylaryl, C ₆ -C ₄₀ aryl, C ₆ -C ₄₀ alkyl, aryloxy, C ₆ -C ₄₀ arylalkyloxy, C ₂ -C ₄₀ heteroaryl, C ₄ -C ₄₀ cycloalkyl, C ₄ -C ₄₀ cycloalkenyl, and the like. C ₁ -C ₂₂ alkyl, C ₂ -C ₂₂ alkenyl, C ₂ -C ₂₂ alkynyl, C ₃ -C ₂₂ allyl, C ₄ -C ₂₂ alkyl diene yl, C ₆ -C ₁₂ aryl, C ₆ - C ₂₀ arylalkyl, and C ₂ -C ₂₀ heteroaryl group is particularly preferred.

Further preferred carbon and hydrocarbon groups are straight, branched or cyclic alkyl radicals having 1 to 40, preferably 1 to 25 carbon atoms, which are unsubstituted or mono-, di- or trisubstituted by F, Cl, Br, or is a multi-substituted, one or more non-adjacent CH ₂ groups are each independently of one another, O and / or = C (R ^x) in such a way S atoms are not directly connected to each other, -C (R ^x) -, -C≡C -, -N (R ^x ) -, -O-, -S-, -CO-, -CO-O-, -O-CO- or -O-CO-O-.

R ^x is preferably H, halogen, a straight, branched or cyclic alkyl chain having from 1 to 25 carbon atoms, wherein at least one non-adjacent carbon atom is further replaced by -O-, -S-, - CO-, -CO-O-, -O-CO-, -O-CO-O-, and at least one H atom may be further substituted with fluorine, an optionally substituted 6-40 An aryl or aryloxy group having one to twenty carbon atoms, or a heteroaryl or heteroaryloxy group having from 2 to 40 carbon atoms, which is optionally substituted.

Preferred alkoxy groups include, but are not limited to, methoxy, ethoxy, 2-methoxy-ethoxy, n-propoxy, i-propoxy, n-butoxy, N-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, n-undecoxy, n-dodecoxy and the like.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s- butyl, t- butyl, 2- methylbutyl, N-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, purple, heptyl, heptyl, cycloheptyl, n-octyl, cyclooctyl, N-butyl, 2,2,2-trifluoroethyl, perfluorooctyl, perfluorohexyl, and the like.

Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, and the like.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, and the like.

Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, and the like.

The aryl and heteroaryl groups may be single or multiple rings, i.e. they may contain one ring (e.g., phenyl) or two or more rings, which may also be fused (e.g., naphthyl) ), Or may contain a combination of fused and linked rings. The heteroaryl group preferably contains one or more heteroatoms selected from O, N, S and Se.

Mono-, bi- or tricyclic heteroaryl groups having from 6 to 25 carbon atoms and mono-, bi- or tricyclic heteroaryl groups having from 2 to 25 carbon atoms are particularly preferred and they are optionally fused Contains a ring and is optionally substituted. 5, 6 or 7-membered aryl and heteroaryl groups are furthermore preferred, wherein one or more CH groups may also be replaced by N, S or O in such a way that the O and / or S atoms are not directly connected to one another.

Preferred aryl groups include, for example, phenyl, biphenyl, terphenyl, [1,1 ': 3', 1 "] terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene, pyrene, dihydropyrenes , Chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, and the like.

Preferred heteroaryl groups are, for example, 5-membered rings such as pyrrole, pyrazole, imidazole, 1,2,3-triazole, 1,2,4-triazole, tetrazole, furan, thiophene, selenophen, oxa Sol, isoxazole, 1,2-thiazole, 1,3-thiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,2,5-oxadiazole, , 3,4-oxadiazole, 1,2,3-thiadiazole, 1,2,4-thiadiazole, 1,2,5-thiadiazole, 1,3,4-thiadiazole, 6 - a cyclic ring such as pyridine, pyridazine, pyrimidine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, 1,2,4,5- Tetrazine, 1,2,3,4-tetrazine, 1,2,3,5-tetrazine, or condensing groups such as indole, isoindole, indolizine, indazole, benzimidazole, benzotriazole, , Naphthoimidazole, phenanthymidazole, pyridimidazole, pyrazinimidazole, quinoxaline imidazole, benzoxazole, naphthoxazole, anthoxazole, phenanthoxazole, isoxazole, benzo Benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5,6-quinoline, benzo-6,7-quinoline, benzo-7,8-quinoline, benzoisoquinoline, Acenidine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimidine, quinoxaline, phenazine, naphthyridine, azacavazole, benzocarboline, phenanthridine, phenanthroline, thieno [2,3b ] Thiophene, thieno [3,2b] thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazothiophene, or combinations thereof. In addition, the heteroaryl group may be substituted with alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

The (non-aromatic) alicyclic and heterocyclic group includes both a saturated ring (i.e., a ring containing only a single bond) and a partially unsaturated ring (i.e., a ring which may contain multiple bonds). The heterocyclic group preferably contains one or more heteroatoms selected from Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups may contain a single ring, i.e. only one ring (e.g. cyclohexane), or a polycyclic ring, i.e. a plurality of rings (e.g., decahydronaphthalene or bicyclooctane) have. A saturated group is particularly preferred. Further preferred are mono-, bi- or tricyclic groups having 3 to 25 carbon atoms, which optionally contain fused rings and are optionally substituted. Further preferred are 5, 6, 7 or 8-membered carbocyclic groups, wherein further one or more carbon atoms may be replaced by Si and / or one or more CH groups may be replaced by N and / The adjacent CH ₂ group may be substituted with -O- and / or -S-.

Preferred alicyclic and heterocyclic groups include, for example, 5-membered groups such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrrolidine, 6-membered groups such as cyclohexane, , Tetrahydropyran, tetrahydrothiopyran, 1,3-dioxane, 1,3-dithiane, piperidine, 7-membered groups such as cycloheptane, and fused groups such as tetrahydronaphthalene, 1,3-diyl, bicyclo [2.2.2] octane-1,4-diyl, spiro [3.3] heptane-2,6-diyl, dicyclohexylcarbodiimide, , Octahydro-4,7-methanoindan-2,5-diyl.

Preferred substituents are, for example, substituents for increasing the glass transition temperature (T _g ) in a solubilization-promoting group such as alkyl or alkoxy, an electron-withdrawing group such as fluorine, nitro or nitrile, t-butyl or an optionally substituted aryl group.

The preferred substituents represented as "L" in the above and below, for example, F, Cl, Br, I, OH, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, C (= O ) and ^{_{N (R x) 2, -C}} (= O) Y 1, -C (= O) R x, -C (= O) OR x, -N (R x) 2, wherein R ^x is in the Y ¹ is selected from the group consisting of halogen and optionally substituted silyl having 4 to 40, preferably 4 to 20, ring atoms, optionally substituted aryl or heteroaryl, and 1 to 25 carbon atoms Alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein at least one H atom is optionally substituted with F or Cl < RTI ID = 0.0 > .

"Substituted silyl group or an aryl group" is preferably ^{halogen, -CN, R 0, -OR 0} , -CO-R 0, -CO-OR 0, -O-CO-R 0 or -O-CO-OR ⁰ , Wherein R < ⁰ > has the meaning given above.

Particularly preferred substituents L are, for example, _{F, Cl, CN, NO 2} , CH 3, C 2 H 5, OCH 3, OC 2 H 5, COCH 3, COC 2 H 5, COOCH 3, COOC 2 H 5, CF 3 , OCF ₃ , OCHF ₂ , OC ₂ F ₅ , and further phenyl.

Is preferably

, Wherein L has one of the meanings given above.

The polymerizable group P is a group suitable for polymerization reactions such as free-radical or ion chain polymerization, multiple addition or polycondensation, or suitable for polymer-like reactions such as addition or condensation reactions on the main polymer chain. Particularly preferred are groups for chain polymerization, in particular groups containing -C = C-double bonds or -C? C-triple bonds, and groups suitable for ring-opening polymerization, such as oxetane or epoxide groups.

Preferred groups P are CH ₂ = CW ¹ -CO-O-, CH ₂ = CW ¹ -CO-,

_{^{, CH 2 = CW 2 - (}} O) k3 -, CW 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH-, CH 3 - CH = CH-O-, (CH 2 = CH) 2 CH-OCO-, (CH 2 = CH-CH 2) 2 CH-OCO-, (CH 2 = CH) 2 CH-O-, (CH 2 = _{CH-CH 2) 2 N-,} (CH 2 = CH-CH 2) 2 N-CO-, HO-CW 2 W 3 -, HS-CW 2 W 3 -, HW 2 N-, HO-CW 2 W ^{_{^{3 -NH-, CH 2 = CW 1}}} -CO-NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, CH 2 = CH- (CO) k1 -Phe- (O) k2 -, Phe-CH = CH-, HOOC-, OCN- and W ⁴ W ⁵ W ⁶ Si-, wherein W ¹ is selected from the group consisting of H, F, Cl, CN, CF ₃ , one represents alkyl having carbon atoms, in particular H, F, Cl or CH _3, W ² and W ³ are each independently of one another, H or 1-alkyl, especially H, methyl, ethyl having one to five carbon atoms or n -Propyl, W ⁴ , W ⁵ and W ⁶ are each independently of one another, Cl, one to represent the 5-oxa-alkyl or oxa-carbonyl alkyl having carbon atoms, W ⁷ and W ⁸ are each independently of one another, H, Cl, or 1 to 5 carbon atoms represents alkyl having, Phe denotes 1,4-phenylene, which optionally is substituted by P-Sp- as defined in the radical L one or more non-, k _1, k ₂ and k ₃ are each independently of one another , 0 or 1, k ₃ preferably represents 1, and k ₄ represents an integer of 1 to 10.

Particularly preferred groups P are CH ₂ = CW ¹ -CO-O-, CH ₂ = CW ¹ -CO-,

_{^{, CH 2 = CW 2 -O-,}} CW 1 = CH-CO- (O) k3 -, CW 1 = CH-CO-NH-, CH 2 = CW 1 -CO-NH-, (CH 2 = CH) _{2 CH-OCO-, (CH 2} = CH-CH 2) 2 CH-OCO-, (CH 2 = CH) 2 CH-O-, (CH 2 = CH-CH 2) 2 N-, (CH 2 = _{CH-CH 2) 2 N-} CO-, CH 2 = CW 1 -CO-NH-, CH 2 = CH- (COO) k1 -Phe- (O) k2 -, CH 2 = CH- (CO) k1 - _{Phe- (O) k2 -, Phe} -CH = CH- and W ⁴ W ⁵ W ⁶ is selected from the group consisting of Si-, wherein W ¹ is H, F, Cl, CN, CF 3, phenyl, or 1-5 one represents an alkyl, in particular H, F, Cl or CH ₃ with the carbon atoms, W ² and W ³ are each independently of the other, H, or 1, 2, 3, 4, or alkyl, especially having 5 carbon atoms, H, methyl, ethyl or n-propyl, W ⁴ , W ⁵ and W ⁶ are each, independently of one another, Cl, oxalalkyl or oxacarbonylalkyl having 1 to 5 carbon atoms, W ⁷ and W ⁸ represent, independently of one another, H, Cl or alkyl having 1 to 5 carbon atoms, Phe represents 1,4-phenylene, k ₁ , k ₂ and k ₃ each independently represent 0 or 1, k ₃ preferably represents 1, and k ₄ represents an integer of 1 to 10.

A very particularly preferred group P is CH ₂ ═CW ¹ -CO-O-, especially CH ₂ ═CH-CO-O-, CH ₂ ═C (CH ₃ ) -CO-O- and CH ₂ ═CF-CO-O -, added to _{CH 2 = CH-O-, (} CH 2 = CH) 2 CH-O-CO-, (CH 2 = CH) 2 CH-O-,

&Lt; / RTI >

In addition, a very particularly preferred group P ^a And P ^b are selected from the group consisting of vinyloxy, acrylate, methacrylate, fluoroacrylate, chloroacrylate, oxetane, 3-ethyloxetane and epoxide groups, particularly preferably acrylate or methacryl Lt; / RTI >

A preferred spacer group Sp is selected from the general formula Sp "-X" wherein the radical "P-Sp-" follows the general formula "P-Sp" -X "-"

Sp "represents alkylene of 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms, which is optionally mono- or polysubstituted by F, Cl, Br, I or CN, wherein one or more non-adjacent CH ₂ The groups may additionally, independently of one another, be replaced by -O-, -S-, -NH-, -N (R ⁰ ) -, -Si (R ⁰⁰ R ⁰⁰⁰ ) -, -CO-, -CO-O- , -O-CO-, -O-CO-O-, -S-CO-, -CO-S-, -N (R 00) -CO-O- , -O-CO-N (R 00) -, -N (R 00) -CO-N (R 00) -, may be replaced by -CH = CH- or -C≡C-,

X "is -O-, -S-, -CO-, -CO- O-, -O-CO-, -O-CO-O-, -CO-N (R 00) -, -N (R 00 ^{) -CO-, -N (R 00)} -CO-N (R 00) -, -OCH 2 -, -CH 2 O-, -SCH 2 -, -CH 2 S-, -CF 2 O-, - OCF ₂ -, -CF ₂ S-, -SCF ₂ -, -CF ₂ CH ₂ -, -CH ₂ CF ₂ -, -CF ₂ CF ₂ -, -CH═N-, -N═CH-, -N ^{= N-, -CH = CR 0 -} , -CY 2 = CY 3 -, -C≡C-, -CH = CH-CO-O-, -O-CO-CH = CH- or a single bond, and means ,

R ⁰⁰ and R ⁰⁰⁰ each independently of one another denote H or alkyl having 1 to 12 carbon atoms,

Y ² and Y ³ are each, independently of one another, H, F, Cl or CN.

X 'is preferably -O-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR ⁰ -, -NR ⁰ -CO-, -NR ⁰ - CO-NR < ⁰ > - or a single bond.

Typical spacer groups Sp "is, for example, _{- (CH 2) p1 -,} - (CH 2 CH 2 O) q1 -CH 2 CH 2 -, -CH 2 CH 2 -S-CH 2 CH 2 -, -CH 2 CH ₂ -NH-CH ₂ CH ₂ - or ^{- (SiR 00 R 000 -O)} p1 - and, where p1 is an integer from 1 to 12, q1 is an integer of 1 to 3, R ⁰⁰ and R ⁰⁰⁰ is in the Have the stated meaning.

A particularly preferred group -Sp "-X" - is _{- (CH 2) p1 -,} - (CH 2) p1 -O-, - (CH 2) p1 -O-CO-, - (CH 2) p1 -O- CO-O-, wherein p1 and q1 have the meanings indicated above.

Especially preferred groups Sp "are, for example, straight chain ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, Ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methyliminoethylene, 1-methylalkylene, ethenylene, prophenylene and butenylene.

In a further preferred embodiment of the present invention, P in formula I represents a radical containing two or more polymerizable groups (a multifunctional polymerizable radical). Suitable radicals of this type, and polymerizable compounds containing them, and methods for their preparation are described, for example, in US 7,060,200 B1 or US 2006/0172090 A1. Particularly preferred multifunctional polymerizable radicals are selected from the following formulas:

In this formula,

Alkyl represents a single bond or a linear or branched alkylene having 1 to 12 carbon atoms, wherein one or more non-adjacent CH ₂ groups are each, independently of one another, O and / or S atoms are not directly connected to one another manner as ^{-C (R 00) = C (} R 000) -, -C≡C-, -N (R 00) -, -O-, -S-, -CO-, -CO-O-, -O -CO- or -O-CO-O-, one or more H atoms may also be replaced by F, Cl or CN, R ⁰⁰ and R ⁰⁰⁰ have the meanings indicated above,

aa and bb each independently represent 0, 1, 2, 3, 4, 5 or 6,

X has one of the meanings given for X '

P ¹ to P ⁵ each independently of one another have one of the meanings mentioned for P ^a .

Particularly preferred compounds of general formula I are those of general formula IA:

IA

In this formula,

R ¹ , R ^b , W ¹ , W ² , A ¹ , A ² , Z ¹ , Z ² , L, p, q and r have the meanings given in formula I or any of the meanings given above and below.

Compounds of general formula I and IA are particularly preferred,

A ¹ and A ² are each, independently of one another, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl wherein at least one CH group in these groups is further substituted by N Cyclohexane-1,4-diyl, wherein one or more non-adjacent CH ₂ groups may be further substituted with O and / or S, 1,4-cyclohexylene, bicyclo [ 1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane- 1,4-diyl, spiro [3.3] heptane-2,6-diyl, piperidine- Diesters, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan-2,5-diyl, octahydro- 7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 6H-benzo [c ] Chromene-3,8-diyl, 9H-fluorene-2,7-diyl, 9,9-dimethyl-9H-fluorene- Dioyl, 2-oxo-2H-chromen-7-yl , 4-phenyl-2-oxo-2H-chromen-7-yl, 4-oxo-4H-chromen- All of these groups may be unsubstituted or mono- or polysubstituted by L, with very particular preference being given to cyclohexane and aromatic groups in all of these groups,

L is _{P-Sp-, OH, CH 2} OH, F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, -C (= O) N (R x _{) 2, -C (= O)} Y 1, -C (= O) R x, -N (R x) 2, silyl, which are optionally substituted, aryl of 6 to 20 carbon atoms which are optionally substituted, 1 Straight or branched alkyl or alkoxy having from 1 to 25, preferably from 1 to 12, carbon atoms, or straight or branched alkenyl having from 2 to 25, preferably from 2 to 12 carbon atoms, Alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, in which at least one H atom may be replaced by F, Cl, P or P-Sp-,

Y ¹ represents halogen,

R ^x is selected from the group consisting of P-Sp-, H, halogen, linear, branched or cyclic alkyl having from 1 to 25, preferably 1 to 12 carbon atoms wherein one or more non-adjacent CH ₂ groups are additionally O -O-, -O-CO- or -O-CO-O- in such a manner that the S atoms and / or S atoms are not directly connected to each other, One or more H atoms may be further substituted by F, Cl or P-Sp-).

Further preferred compounds of the formulas I, IA and the subformulae described above and below are selected from one or more of the following preferred embodiments which can be combined with one another if desired:

- W ¹ and W ² are each independently of one another -CH ₂ CH ₂ -, -CH═CH-, -CH ₂ -O-, -O-CH ₂ -, -C (R ^c R ^d ) O-,

Both W ¹ and W ² do not simultaneously represent -CH = CH-, preferably when Y is H or F both do not simultaneously represent -CY = CY-,

- R ^c and R ^d are each, independently of one another, H or alkyl having 1 to 6 carbon atoms, preferably H, methyl or ethyl,

- only one or both of the radicals W ¹ and W ² represent -N (R ^e ) and R ^e represents H or alkyl having 1 to 6 carbon atoms, preferably H, methyl or ethyl,

- one of the radicals W ¹ and W ² represents -CH ₂ CH ₂ - or -CH═CH- and the other represents -CH ₂ CH ₂ -, -CH ₂ O-, -OCH ₂ - or -C (CR ^c R ^d ) ₂ -, wherein R ^c and R ^d are preferably methyl,

- one of the radicals W ¹ and W ² represents -CH ₂ CH ₂ - and the other represents -CH ₂ O- or -OCH ₂ -

- one of the radicals W ¹ and W ² represents -CH = CH- and the other represents -CH ₂ O- or -OCH ₂ -

- one of the radicals W ¹ and W ² represents -CH ₂ CH ₂ - and the other represents -C (CH ₃ ) ₂ -

- one of the radicals W ¹ and W ² represents -CH = CH- and the other represents -C (CH ₃ ) ₂ -

- W ¹ represents -CH ₂ CH ₂ -, W ² represents -CH ₂ O-,

- W ¹ represents -CH = CH-, W ² represents -CH ₂ O-,

- W ¹ and W ² represent -CH ₂ CH ₂ -

- W ¹ and W ² represent -CH = CH-,

- Y represents H,

One of the radicals R & lt ^; ^a & gt ^; and R < ^b & gt ^; represents P-Sp- and the other is different from P-

- R ^a and R ^b represent the same or different radicals P-Sp-,

- R ^a and R ^b may represent a P-Sp-, one of the radicals R ^a and R ^b in the Sp is a single bond, the other of the radicals R ^a and R ^b Sp is different from a single bond, and preferably Quot; represents a group of the general formula Sp "-X" -, wherein such a radical P-Sp- follows the general formula P-Sp &

R ^a and R ^b represent the same or different radicals P-Sp-, wherein both radicals Sp represent a single bond,

- one of the radicals R ^a and R ^b represents or contains the group P-Sp- and the other represents a non-polymerizable group, preferably selected from linear or branched alkyl having 1 to 25 carbon atoms and, wherein one or more non-adjacent CH ₂ groups are each independently of one another additionally, O and / or -C (R ⁰⁰⁾ in such a way S atoms are not directly connected to each other, ^{= C (R 000) -,} -C≡C ^{-, -N (R 00) -} , -O-, -S-, -CO-, -CO-O-, -O-CO- , or may be replaced by -O-CO-O-, one or more H The atom may be further substituted by F, Cl, Br, I or CN,

- R ^a and R ^b are different from H,

One of the radicals R & lt ^; ^a & gt ^; and R < ^b & gt ^; represents P-Sp- and the other is different from H,

- radicals R ^a or R ^b different from P-Sp- are alkyl having 1 to 12, preferably 5 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms or alkoxy having 2 to 11 carbon atoms Alkenyl, wherein at least one H atom in every radical may be further substituted by F,

R ^a and / or R ^b represents straight-chain or branched alkyl having 1 to 25, preferably 1 to 12, carbon atoms, wherein one or more non-adjacent CH ₂ groups are each, independently of one another, O and / or S atoms in a way that is not directly connected to each other ^{-C (R 00) = C (} R 000) -, -C≡C-, -N (R 00) -, -O-, -S-, -CO -, -CO-O-, -O-CO- or -O-CO-O- and at least one H atom may be further substituted by F, Cl, Br, I or CN,

- Sp represents a single bond,

- Sp is - (CH ₂ ) _{p 1} -, - (CH ₂ ) _{p 1} -O-, - (CH ₂ ) _{p 1} -O-CO- or - (CH ₂ ) _{p 1} -O-COO-, CH ₂ ) _{p 1} - or - (CH ₂ ) _{p 1} -O-, wherein p 1 represents an integer of 1 to 12, preferably 1 to 5, particularly preferably 1 to 3,

- Sp and / or Sp "denotes an alkylene radical having 1 to 5, preferably 1 to 3 carbon atoms,

A ¹ and A ² are each, independently of one another, in each case identical or different, phenylene-1,4-diyl, naphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene Diyl, decahydronaphthalene-2,6-diyl, trans-cyclohexylene-1,4-diyl and dibenzofuran-3,7-diyl, In which one or two CH groups in such a ring in the abovementioned radicals containing an unsaturated or aromatic ring may also be replaced by N and the individual rings in all the aforementioned radicals may also be mono- or polysubstituted with L and as set forth above and below Yes,

- A ¹ and A ² represent phenylene-1,4-diyl which may be mono- or polysubstituted by L as defined above and below,

L does not represent or can not contain a polymerizable group,

L represents a non-polymerizable group and is preferably selected from F, Cl, -CN and straight-chain or branched alkyl having 1 to 25, particularly preferably 1 to 10 carbon atoms, And the non-adjacent CH ₂ groups are further each independently of one another, in which the O and / or S atoms are not directly linked to each other, -C (R ⁰⁰ ) ═C (R ⁰⁰⁰ ) -, -C≡C-, -N ^{R 00) -, -O-, -S-} , -CO-, -CO-O-, -O-CO-, may be substituted by -O-CO-O-, one or more H atoms are added to the F , Cl, Br, I or CN,

- L represents a F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN or -SCN, preferably F,

- in one or both radicals (L) _r , r represents 1,

- in one or both radicals (L) _r , r represents 1 and L represents F,

L is a straight or branched alkyl or alkoxy having 1 to 12 carbon atoms, or a straight or branched alkenyl having 2 to 12 carbon atoms, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyl Alkoxy or alkoxycarbonyloxy, wherein at least one H atom in all such groups may be further substituted with F, Cl or P-Sp-,

- L represents P-Sp-,

Z ¹ and Z ² are each, independently of one another, in each case identical or different, -O-, -CO-O-, -OCO-, -OCH ₂ -, -CH ₂ O-, -CF ₂ O- , -OCF ₂ -, -CH ₂ CH ₂ -, -CH═CH-, -CF═CF-, -CH═CF-, -CF═CH-, -C≡C-, and a single bond ,

Z ¹ and Z ² represent a single bond,

Z ¹ and Z ² are different from -C? C-,

- p is 0 and q is 0,

- p is 1 and q is 1,

p is 0, q is 1, p is 1 and q is 0,

- when W ¹ and W ² represent -CH = CH-, Z ¹ is not -C≡C- and A ¹ is not 1,4-phenylene, particularly preferably is not an aromatic radical,

When W ¹ and W ² represent -CH = CH-, Z ² is not -C≡C- and A ² is not 1,4-phenylene, particularly preferably is not an aromatic radical,

- R ^a - (A ¹ -Z ¹ ) _p - and - (Z ² -A ² ) _q -R ^b is not halogen.

Particularly preferred compounds of formula I and IA are selected from the group consisting of the following sub-formulas:

In this formula,

Sp, L, and r have one of the meanings given above and below,
P ^a and P ^b each independently of one another have one of the meanings given for P,
R 'and R "are each independently of the other H, or an alkyl having 1 to 12 carbon atoms, preferably methyl or ethyl,
s1 represents 0 or 1;

In the compounds of the general formulas I, IA and sub general formulas I1 to I28, P, P ^a and P ^b preferably represent acrylate or methacrylate, further fluoroacrylate.

In the general formula (I) and (IA) and compounds of sub-formulas I1 to I28, Sp is preferably a _{- (CH 2) p1 -,} - (CH 2) p1 -O-, - (CH 2) p1 -O-CO- Or - (CH ₂ ) _p1 -O-CO-O-, or an enantiomer thereof, wherein p1 is an integer of 1 to 12, preferably 1 to 6, particularly preferably 1, 2, 3 or 4 , And their connection to the adjacent benzene ring is achieved through the O atom.

In addition, the present invention relates to novel compounds of the general formulas I and IA and their sub-formulas described above and below, wherein when W ¹ and W ² represent -CH = CH-, then Z ¹ is - not a C≡C- / No, or a ¹ is 1,4-phenylene, and particularly preferably not an aromatic radical, Z ² is not a -C≡C- / or a ² is not 1,4-phenylene , Particularly preferably is not an aromatic radical and is not 1-vinylpyrrole.

In addition, the present invention relates to novel intermediates for the preparation of compounds of general formula I, selected from the following general formula II, preferably the following general formula IIA:

II

IIA

In this formula,

Q, and r have the meaning of formula I, or a group as defined above or below, wherein W ¹ , W ² , Sp, L, A ¹ , A ² , Z ¹ , Z ² ,
G and G 'each independently represent a H atom or a protecting group.

Suitable protecting groups G are known to those skilled in the art. Preferred protecting groups are alkyl, acyl and alkylsilyl or arylsilyl groups, 2-tetrahydropyranyl or methoxymethyl.

Particularly preferred intermediates of the general formulas II and IIA are selected from the group consisting of the sub-general formulas I1 to I28 mentioned above, wherein P ^a in each case means GO- and P ^b in each case is -O-G ', Where G and G' preferably mean H.

Particularly suitable and preferred compounds of the general formulas I and II and their lower general formulas and processes for the preparation of intermediates are illustrated by way of example in the following scheme and preferably include one or more of the steps described below.

Compounds and intermediates of the general formulas I and II and sub-general formulas thereof are known to those skilled in the art and are described in standard work of organic chemistry such as in Houben-Weyl, Methoden der organischen Chemie, Thieme-Verlag, Stuttgart Can be prepared similarly to the described method.

For example, the compounds of general formula I are synthesized by esterifying or etherifying intermediates of general formula II using corresponding acids, acid derivatives, or halogenated compounds containing P groups. As shown in Scheme 1, compounds of the general formula I wherein P ^a and P ^b represent P-Sp- and P represents, for example, an acrylate or methacrylate group are prepared by reacting ^a base and optionally 4- ( (Meth) acryloyl chloride or (meth) acrylic anhydride in the presence of an acid derivative such as (meth) acryloyl chloride or (meth) acrylic anhydride in the presence of a base Can be obtained by esterification. The alcohols may also be esterified using (meth) acrylic acid in the presence of a dehydrating agent, for example, by the Steglich method using dicyclohexylcarbodiimide (DCC).

Accordingly, the present invention further relates to a process for the preparation of a compound of general formula I which esterifies or etherifies a compound of formula II with a corresponding acid, acid derivative, or halogenated compound containing a group P in the presence of a dehydrating agent .

Scheme 1

(R = H or _{^{CH 3; W 1, W 2}} , Sp, L, A 1, A 2, Z 1, Z 2, p, q and r are as defined in Formula II)

(P. Soustek et al., Dyes and Pigments 78 (2008)) to give the parent moiety 4,5,9,10-tetrahydropyrene ( 1 , W = W '= CH ₂ CH ₂ ) 139-147), which can be selectively functionalized by halogenation (Scheme 2). AD Abell et al., J. Chem. Soc., Perkin Trans. 1, 1997, 1663-1668]), 2,7-dibromo -4,5,9,10- from 4,5,9,10- tetrahydro-pyrene 4 according to tetrahydro-pyrene (5, Hal = Br). H. Suzuki, Organic Syntheses, Coll. Vol. 6, p. 700 (1988)] to give the corresponding 2,7-diiodo-4,5,9,10-tetrahydropyrene ( 5 , Hal = I).

Scheme 2

For example, a boronic acid can be prepared from a dihalogen compound ( 5 ) by a metal bond using butyllithium and a reaction with a boric acid ester, and oxidized to obtain phenol ( 6 ). Other alternatives are described in SL Buchwald et al., J. Am. Chem. Soc. 2006, 128, 10694-10695] with KOH in the presence of a palladium catalyst. (Meth) acrylate ( 7 ) is obtained by esterification using acrylic acid.

Scheme 3

(R = H or CH ₃₎

Diisopropylboronate is obtained by a single metal bond in the presence of triisopropylborate, which is hydrolyzed and oxidized to give the monohydroxyl compound ( 8 , Scheme 4) which is further converted in the second step . Thus, the Sonogashira coupling to the terminal alkyne gives the alkyne 9 , from which the compound 10 containing the spacer group can be obtained by hydrogenation and esterification.

Scheme 4

(R = H or CH _3, for example, p1 = 1 to 12)

Correspondingly, [S. Derivative 12 can be obtained from commercially available 4H-cyclopenta [def] phenanthrene 11 (Scheme 5), as described in Song et al., Tetrahedron Letters 2008, 49, 3582-3587 Compounds 13 and 14 can be obtained according to scheme 3 and 4, respectively.

Scheme 5

(R = H or CH _3, for example, p1 = 1 to 12)

To obtain the suitable intermediates such as compound 5, 8, or 12 corresponding unsaturated aromatic compound of 15 to 18 to the furnace. Suitable reaction conditions for the aromatization are, for example, treatment with dichlorodicyanobenzoquinone (DDQ) in an inert solvent (VV Filichev et al., Chemistry - A European Journal 2008, 14 (32), 9968-9980) ) Or halogenation without hydrogen halide (P. Soustek et al., Dyes and Pigments 78 (2008) 139-147; S. Song et al., Tetrahedron Letters 49 (2008) 3582-3587).

(R = H or CH _3, for example, p1 = 1 to 12)

Flavidin 19 is a natural product and is isolated from orchids (see, e.g., GK Jayaprakasha et al., Bioorganic & Medicinal Chemistry 2004, 12, 5141-5146).

(R = H or CH ₃₎

The derivative 20 according to the present invention Obtained from the above-mentioned 19 ; Aromatics 21 as described above are obtained.

The intermediates shown in the schemes can be further converted to the compounds according to the invention by various standard reactions (Scheme 6). For example, an aryl derivative 23 can be obtained from an aryl metal compound by a transition metal-catalyzed coupling reaction such as Suzuki coupling ( 22 , M = -B (OH) ₂ ) 0.0 > 25 < / RTI >

Scheme 6

(R = H or CH ₃ ; M = B (OH) ₂ , ZnHal, MgHal, Hal = halogen; G, W ¹ , W ² , A ¹ , Z ¹ , p, Sp are as described in formula II)

The present invention further relates to processes for the preparation of compounds of the general formulas I and II, in particular to the preparation of compounds of the general formula I from compounds of the general formula II.

When producing a PSA display, the polymerizable compound is polymerized or polymerized by in situ polymerization in an LC medium between the substrates of the LC display with voltage application (where one compound contains two or more polymerizable groups) . The polymerization can be carried out in a single step. In addition, first, a voltage is applied to generate a pretilt angle to perform polymerization in the first step, and subsequently to the second polymerization step, the unreacted compound in the first step is polymerized or crosslinked It is also possible to combine them ("final cure").

Suitable and preferred polymerization methods are, for example, thermal polymerization or photopolymerization, preferably photopolymerization, in particular UV photopolymerization. In addition, one or more initiators may optionally be added thereto. Suitable conditions for such polymerization and suitable types and amounts of initiator are known to those skilled in the art and are described in the literature. Suitable for free-radical polymerization are, for example, commercially available photoinitiators Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), Irgacure 907 (registered trademark), Irgacure 369 Darocure 1173 (registered trademark) (Ciba AG)). When an initiator is used, the ratio is preferably 0.001 to 5% by weight, particularly preferably 0.001 to 1% by weight.

The polymerisable compounds according to the invention are also suitable for the polymerization without the use of initiators, for example in the case of considerable material costs such as less material costs and less contamination of the LC medium by possible residual amounts of initiators or their decomposition products Accompanied by an advantage. Thus, the polymerization can also be carried out without the addition of an initiator. Thus, in a preferred embodiment, the LC medium does not contain any polymerization initiator at all.

The polymerizable component A) or the LC medium may also comprise one or more stabilizers, for example to prevent undesirable spontaneous polymerization of the RM during storage or transport. Suitable types and amounts of stabilizers are known to those skilled in the art and are described in the literature. For example, the commercially available stabilizer Irganox (R) series (Shibaegae) such as Irganox (R) 1076 is particularly suitable. When a stabilizer is used, the proportion of the stabilizer based on the total amount of RM or polymerizable component A) is preferably from 10 to 10,000 ppm, particularly preferably from 50 to 500 ppm.

The LC medium according to the invention for use in PSA displays preferably comprises less than 5% by weight, particularly preferably less than 1% by weight, very particularly preferably less than 0.5% by weight of polymerisable compounds, And polymerizable compounds of the following general formula.

Particularly preferred are LC media comprising one, two or three polymerizable compounds according to the invention.

Also preferred is a LC medium wherein the polymerizable component (component A)) comprises solely the polymerizable compound according to the invention.

Also preferred is a LC medium in which component B) is a LC compound or LC mixture (which has a nematic liquid crystal phase).

Also preferred are the achiral polymerizable compounds according to the invention and the LC medium, wherein the compounds of component A) and / or B) are solely selected from the group consisting of achiral compounds.

Also, the polymerizable component or component A) comprises one or more polymerizable compounds according to the invention containing one polymerizable group (one reactive); And one or more polymerizable compounds according to the invention (this reactive or multi-reactive) containing two or more, preferably two polymerizable groups, are preferred.

Also preferred are LC media and PSA displays comprising only the polymerizable component or the polymerizable compound according to the invention (this reactive), wherein component A) contains two polymerizable groups.

The proportion of said polymerizable component or component A) in the LC medium according to the invention is preferably less than 5%, particularly preferably less than 1%, very particularly preferably less than 0.5%.

The proportion of said liquid crystal component or component B) in the LC medium according to the invention is preferably greater than 95%, particularly preferably greater than 99%.

The polymerizable compounds according to the present invention can be polymerized individually but also include mixtures comprising two or more polymerizable compounds according to the invention or mixtures comprising at least one polymerizable compound according to the invention and further polymerizable compounds ) (Which is preferably mesogenic or liquid crystalline) may be polymerized. In the case of polymerization of such a mixture, a copolymer is formed. The present invention also relates to polymerizable mixtures as described above and below. The polymerizable compounds and comonomers are mesogenic or non-mesogenic, preferably mesogenic or liquid crystalline.

Particularly suitable mesogenic comonomers suitable for use in PSA displays are selected, for example, from the following general formulas:

In this formula,

P ¹ and P ² are each, independently of one another, a polymerizable group, preferably P, having one of the meanings mentioned hereinbefore and hereinafter, particularly preferably acrylate, methacrylate, fluoroacrylate , Oxetane, vinyloxy or an epoxide group,

Sp ¹ and Sp ² each represent, independently of each other, a single bond or a spacer group, preferably having one of the meanings mentioned hereinbefore and hereinafter for Sp, and particularly preferably - (CH ₂ ) _p1 -, - (CH ₂ ) _{p 1} -O-, - (CH ₂ ) _{p 1} -CO-O- or - (CH ₂ ) _p1 -O-CO-O- wherein p1 is an integer from 1 to 12, The linkage to the adjacent ring of the group mentioned above occurs through the O atom,

Also, at least one of the radicals P ¹ -Sp ¹ - and P ² -Sp ² - may represent R ^aa , provided that at least one of the radicals P ¹ -Sp ¹ - and P ² -Sp ² - ^aa ,

R ^aa represents H, F, Cl, CN, or straight chain or branched alkyl having 1 to 25 carbon atoms, wherein one or more non-adjacent CH ₂ groups may also be, independently of one another, O and / or S atoms manner that is not directly connected to each other in the ^{C (R 0) = C (} R 00) -, -C≡C-, -N (R 0) -, -O-, -S-, -CO-, -CO-O -, -O-CO- or -O-CO-O- and at least one H atom may also be replaced by F, Cl, CN or P ¹ -Sp ¹ - Alkoxy, alkenyl, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, wherein the alkyl, alkenyl, alkynyl, alkynyl, alkynyl, Said alkenyl and alkynyl radical having two or more carbon atoms and the branched radical having three or more carbon atoms,

R ⁰ and R ⁰⁰ are each independently of one another, in each case identically or differently, H, or alkyl having 1 to 12 carbon atoms,

R ^y and R ^z each independently represent H, F, CH ₃ or CF ₃ ,

Z ¹ represents -O-, -CO-, -C (R ^y R ^z ) - or -CF ₂ CF ₂ -

Z ² and Z ³ are each independently of one another, -CO-O-, -O-CO- , -CH 2 O-, -OCH 2 -, -CF 2 O-, -OCF 2 - or - (CH ₂₎ _n -, _wherein n is 2, 3 or 4,

L is in each case the same or different and is selected from the group consisting of F, Cl, CN or optionally mono- or polyfluorinated straight or branched alkyl having 1 to 12 carbon atoms, alkoxy, alkenyl, alkynyl, alkyl Carbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy, preferably F,

L ' and L "each independently represent H, F or Cl,

r represents 0, 1, 2, 3 or 4,

s represents 0, 1, 2 or 3,

t represents 0, 1 or 2,

x is 0 or 1;

In addition to the polymerizable compounds described above, the LC medium for use in an LC display according to the present invention may comprise an LC mixture comprising at least one, preferably at least two, low molecular weight (i.e., monomeric or unpolymerized) "Host mixture"). The LC mixture comprising two or more low molecular weight compounds is stable or non-reactive to the polymerization reaction under the conditions used for polymerizing the polymerizable compound. In general, suitable host mixtures are any LC mixtures suitable for use in conventional VA and OCB displays. Suitable LC mixtures are known to the person skilled in the art and described in the literature, for example mixtures for VA displays are described in EP 1 378 557 A1 and mixtures for OCB displays are described in EP 1 306 418 A1 and DE 102 24 046 A1 &Lt; / RTI >

In a first preferred embodiment of the present invention, the LC medium comprises an LC host mixture based on a compound having negative dielectric anisotropy. These LC media are particularly suitable for use in PSA-VA displays. Particularly preferred embodiments of this type of LC medium are mentioned in the following sections a) to x):

a) a LC medium comprising at least one compound selected from the group consisting of the following general formulas CY and / or PY:

In this formula,

a represents 1 or 2,

b represents 0 or 1,

The

Lt; / RTI >

R ¹ and R ² are each, independently of one another, alkyl having from 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are replaced by -O- , -CH = CH-, -CO-, -OCO- or -COO-), preferably alkyl or alkoxy having 1 to 6 carbon atoms,

Z ^x and Z ^y are each independently of one another -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CO-O -, -O-CO-, -C ₂ F ₄ -, -CF═CF-, -CH═CH-CH ₂ O- or a single bond, preferably a single bond,

L ¹ to L ⁴ each independently represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ .

Preferably, the radicals L ¹ and L ² both represent F, or one of the radicals L ¹ and L ² represents F and the other represents Cl, or the radicals L ³ and L ⁴ both represent F , One of the radicals L ³ and L ⁴ represents F and the other represents Cl.

The compound of formula CY is preferably selected from the group consisting of the following sub-formulas:

In this formula,

a represents 1 or 2,

Alkyl and alkyl ^* each independently of one another represent a straight-chain alkyl radical having from 1 to 6 carbon atoms,

Alkenyl represents a straight-chain alkenyl radical having 2 to 6 carbon atoms,

(O) represents an oxygen atom or a single bond.
Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH (CH 2} ) 2 - represents a.

The compound of formula PY is preferably selected from the group consisting of the following sub-formulas:

In this formula,

Alkenyl represents a straight-chain alkenyl radical having 2 to 6 carbon atoms,

(O) represents an oxygen atom or a single bond.

Alkenyl preferably _{CH 2 = CH-, CH 2 =} CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH (CH 2} ) 2 - represents a.

b) a LC medium further comprising one or more compounds of the general formula ZK:

ZK

In this formula,

The

Lt; / RTI >

The

Lt; / RTI >

R ³ and R ⁴ each independently of one another represent alkyl having 1 to 12 carbon atoms, wherein one or two non-adjacent CH ₂ groups are also optionally replaced by -O-, -CH-CH-, -CO-, -O-CO- or -CO-O-,

Z ^y represents -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -CO-O-, -C ₂ F ₄ -, and -CF = CF-, -CH = CH- CH 2 O- or a single bond, preferably a single bond.

Compounds of formula ZK are preferably selected from the following sub-formulas:

In this formula,

Alkyl and alkyl ^* each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms,

Alkenyl represents a straight-chain alkenyl radical having 2 to 6 carbon atoms.

c) a LC medium further comprising one or more compounds of the general formula DK:

DK

In the above formula, the individual radicals in each case have the same or different meanings as follows:

R ⁵ and R ⁶ has one of the meanings set forth for each independently of the other, the R ^1,

The

Lt; / RTI >

The

Lt; / RTI >

e represents 1 or 2;

The compound of formula DK is preferably selected from the group consisting of the following sub-formulas:

In this formula,

Alkyl and alkyl ^* are each independently of the other, one to six represents a straight-chain alkyl radicals having carbon atoms, alkenyl and alkenyl ^* is alkenyl radical straight, each independently, having 2 to 6 carbon atoms from each other . Alkenyl and alkenyl ^* are preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH- (CH ₂ ) ₂ -.

d) a LC medium further comprising one or more compounds of the general formula LY:

LY

In this formula,

The

Lt; / RTI >

f represents 0 or 1,

R ¹ and R ² each independently of one another represent alkyl having 1 to 12 carbon atoms, wherein one or two non-adjacent CH ₂ groups are also optionally replaced by -O- , -CH = CH-, -CO-, -OCO- or -COO-,

L ¹ and L ² each independently of one another represent F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ .

Preferably, the radicals L ¹ and L ² both represent F, or one of the radicals L ¹ and L ² represents F and the other represents Cl.

The compounds of the general formula LY are preferably selected from the group consisting of the following sub-formulas:

In this formula,

R ¹ is a straight-chain alkyl radical having from having alkyl is 1 to 6 carbon atoms as described above meaning, (O) represents an oxygen atom or a single bond, v is an integer of 1-6. R ¹ is preferably straight-chain alkyl having 1 to 6 carbon atoms or straight-chain alkenyl having 2 to 6 carbon atoms, especially CH ₃ , C ₂ H ₅ , nC ₃ H ₇ , nC ₄ H ₉ , _{nC 5 H 11, CH 2 =} CH-, CH 2 = CHCH 2 CH 2 -, CH 3 -CH = CH-, CH 3 -CH 2 -CH = CH-, CH 3 - (CH 2) 2 -CH = _{CH-, CH 3 - (CH 2} ) 3 -CH = CH- or _{CH 3 -CH = CH- (CH 2} ) 2 - represents a.

e) a LC medium further comprising one or more compounds selected from the group consisting of the following general formulas G1 to G4:

In this formula,

Alkyl represents C ₁ _-6 -alkyl, L ^x represents H or F, and X represents F, Cl, OCF ₃ , OCHF ₂ or OCH = CF ₂ . Compounds of formula G1 in which X represents F are particularly preferred.

f) a LC medium further comprising one or more compounds selected from the group consisting of the following general formulas:

In this formula,

R ⁵ has ^one of the meanings given for R ¹ , alkyl represents C ₁ _-6 -alkyl, d represents 0 or 1, z and m are each, independently of one another, an integer from 1 to 6 . In this compound, R ⁵ is particularly preferably C ₁ _-6 -alkyl, C ₁ _-6 -alkoxy or C _2-6 -alkenyl, and d is preferably 1. The LC medium according to the invention preferably comprises at least 5% by weight of one or more compounds of the abovementioned general formula.

g) a LC medium further comprising at least one biphenyl compound selected from the group consisting of the following general formulas:

In this formula,

Alkyl and alkyl ^* are each independently of the other, one to six represents a straight-chain alkyl radicals having carbon atoms, alkenyl and alkenyl ^* is alkenyl radical straight, each independently, having 2 to 6 carbon atoms from each other . Alkenyl and alkenyl ^* are preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH (CH ₂ ) ₂ -.

The proportion of biphenyls of the general formulas B1 to B3 in the LC mixture is preferably at least 3% by weight, in particular at least 5% by weight.

Compounds of formula B2 are particularly preferred.

The compounds of the general formulas B1 to B3 are preferably selected from the group consisting of the following sub-formulas:

In this formula,

Alkyl ^* represents an alkyl radical having 1 to 6 carbon atoms. The medium according to the invention particularly preferably comprises one or more compounds of the general formula B1a and / or B2c.

h) a LC medium further comprising at least one terphenyl compound of the following general formula T:

T

In this formula,

Are each, independently of one another,

Lt; / RTI >

L ⁵ represents F or Cl, preferably F,

L ⁶ represents F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ , preferably F.

The compounds of formula (T) are preferably selected from the group consisting of the following sub-formulas:

In this formula,

R represents a straight chain alkyl or alkoxy radical having 1 to 7 carbon atoms, R ^* represents a straight-chain alkenyl radical having 2 to 7 carbon atoms, (O) represents an oxygen atom or a single bond, m represents an integer of 1 to 6; R ^* is preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH (CH ₂ ) ₂ -.

R preferably represents methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy, ethoxy, propoxy, butoxy or pentoxy.

The LC medium according to the invention preferably comprises terphenyl of the general formula T and its sub-formulas in an amount of from 0.5 to 30% by weight, in particular from 1 to 20% by weight.

Especially preferred are the compounds of the above formulas T1, T2, T3 and T21. In these compounds, R is preferably alkyl or alkoxy each having 1 to 5 carbon atoms.

If the? N of the mixture according to the invention is intended to be 0.1 or more, preferably terphenyl is used in the mixture. Preferred mixtures comprise from 2 to 20% by weight of at least one terphenyl compound selected from the group of compounds of the general formula T, preferably of the general formula T1 to T22.

i) a LC medium further comprising at least one compound selected from the group consisting of the following general formulas:

In this formula,

R ¹ and R ² have the meanings as described above, and preferably each independently of one another represents straight-chain alkyl having 1 to 6 carbon atoms or straight-chain alkenyl having 2 to 6 carbon atoms.

A preferred medium contains at least one compound selected from the general formulas O1, O3 and O4.

k) a LC medium further comprising at least 3% by weight, especially at least 5% by weight, very particularly preferably 5 to 30% by weight, of at least one compound of the following formula FI:

FI

In this formula,

The

Lt; / RTI >

R ⁹ is H, CH _3, C ₂ H _5, or represents nC ₃ H _7, (F) denotes an optional fluorine substituents, q denotes 1, 2 or 3, R ⁷ means described for R ¹ Lt; / RTI >

Particularly preferred compounds of the above formula FI are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁷ preferably represents straight-chain alkyl, and R ⁹ represents CH ₃ , C ₂ H ₅ or nC ₃ H ₇ . Compounds of the general formulas FIl, FI2 and FI3 are particularly preferred.

m) a LC medium further comprising at least one compound selected from the group consisting of the following general formulas:

In this formula,

R ⁸ has the meanings given for R ¹ and alkyl is a straight chain alkyl radical having 1 to 6 carbon atoms.

n) compounds containing tetrahydronaphthyl or naphthyl units, for example a LC medium further comprising at least one compound selected from the group consisting of the following general formulas:

In this formula,

R ¹⁰ and R ¹¹ are each, independently of one another, a straight-chain alkyl or alkoxy having one of the meanings given for R ¹ , preferably having from 1 to 6 carbon atoms or a straight-chain Z ¹ and Z ² are each independently of one another -C ₂ H ₄ -, -CH═CH-, - (CH ₂ ) ₄ -, - (CH ₂ ) ₃ O-, -O _{2) 3 -, -CH = CH} -CH 2 CH 2 -, -CH 2 CH 2 CH = CH-, -CH 2 O-, -OCH 2 -, -CO-O-, -O-CO-, - _{C 2 F 4 -, -CF =} CF-, -CF = CH-, -CH = CF-, -CH 2 - , or represents a single bond.

o) a LC medium further comprising at least one difluoro-dibenzochroman and / or chroman of the following formulas, preferably in an amount of from 3 to 20% by weight, in particular from 3 to 15% by weight:

In this formula,

R ¹¹ and R ¹² each independently of one another have the significance given above, ring M is trans-1,4-cyclohexylene or 1,4-phenylene, Z ^m is -C ₂ H ₄ -, -CH _2- O-, -OCH ₂ -, -CO-O- or -O-CO-, and c is 0 or 1.

Particularly preferred compounds of the above formulas BC and CR are selected from the group consisting of the following sub-formulas:

In this formula,

Alkyl and alkyl ^* each independently represent a straight-chain alkyl radical having 1 to 6 carbon atoms, (O) represents an oxygen atom or a single bond, alkenyl and alkenyl ^* each, independently of one another, Lt; / RTI > to 6 carbon atoms. Alkenyl and alkenyl ^* are preferably CH ₂ ═CH-, CH ₂ ═CHCH ₂ CH ₂ -, CH ₃ -CH═CH-, CH ₃ -CH ₂ -CH═CH-, CH ₃ - (CH ₂ ) ₂ -CH = CH-, CH ₃ - (CH ₂ ) ₃ -CH = CH- or CH ₃ -CH = CH (CH ₂ ) ₂ -.

Very particular preference is given to mixtures comprising one, two or three compounds of the general formula BC2.

p) a LC medium further comprising at least one fluorinated phenanthrene and / or dibenzofurane of the general formula PH and BF:

In this formula,

R ¹¹ and R ¹² each independently of one another have the above described meanings, b represents 0 or 1, L represents F and r represents 1, 2 or 3.

Particular preference is given to compounds of the general formulas PH and BF selected from the group consisting of the following sub-formulas:

In this formula,

R and R 'each independently of one another represent a straight chain alkyl or alkoxy radical having 1 to 7 carbon atoms.

q) a LC medium which does not contain a compound containing a terminal vinyloxy group (-O-CH = CH ₂ ), in addition to the polymerizable compounds according to the invention, in particular compounds of the general formula I or of the sub-

r) A LC medium comprising preferably 1 to 5, preferably 1, 2 or 3 polymerizable compounds selected from the polymerizable compounds according to the invention, in particular compounds of the general formula I or lower order formulas thereof.

s) LC medium in which the proportion of polymerisable compounds, in particular compounds of general formula I or of the sub-formulas thereof, in the whole mixture is from 0.05 to 5%, preferably from 0.1 to 1%.

t) LC medium comprising 1 to 8, preferably 1 to 5, compounds of the abovementioned general formulas CY1, CY2, PY1 and / or PY2. The proportion of these compounds in the whole mixture is preferably 5 to 60%, particularly preferably 10 to 35%. The content of each of these compounds is preferably 2 to 20% in each case.

u) a LC medium comprising 1 to 8, preferably 1 to 5, compounds of the abovementioned general formulas CY9, CY10, PY9 and / or PY10. The proportion of these compounds in the whole mixture is preferably 5 to 60%, particularly preferably 10 to 35%. The content of each of these compounds is preferably 2 to 20% in each case.

v) a LC medium comprising 1 to 10, preferably 1 to 8, compounds of the general formula ZK, in particular the compounds of the general formulas ZK1, ZK2 and / or ZK6. The proportion of these compounds in the total mixture is preferably 3 to 25%, particularly preferably 5 to 45%. The content of each of these compounds is preferably 2 to 20% in each case.

w) LC medium in which the proportion of compounds of the general formula CY, PY and ZK in the whole mixture is more than 70%, preferably more than 80%.

x) PSA-VA display wherein the pre-scan angle is preferably 85 DEG or less, particularly preferably 80 DEG or less.

In a second preferred embodiment of the present invention, the LC medium comprises an LC host mixture based on a compound having a positive dielectric anisotropy. This type of LC medium is particularly suitable for use in PSA-OCB, PSA-TN, PSA-positive-VA, PSA-IPS or PSA-FFS displays. A particularly preferred embodiment of such a display is as follows:

A LC medium comprising at least one compound selected from the group consisting of compounds of the following formulas AA and BB:

In addition to the compounds of the general formula AA and / or BB, a LC medium comprising at least one compound of the following general formula CC:

CC

In the general formulas AA, BB and CC,

Are each, independently of one another, in each case identical or different,

Lt; / RTI >

Are each, independently of one another, in each case identical or different,

Lt; / RTI >

R ²¹ , R ³¹ , R ⁴¹ and R ⁴² each independently of one another represent alkyl, alkoxy, oxaalkyl or fluoroalkyl having 1 to 9 carbon atoms or alkenyl having 2 to 9 carbon atoms,

X ⁰ represents F, Cl, halogenated alkyl or alkoxy having 1 to 6 carbon atoms, or halogenated alkenyl or alkenyloxy having 2 to 6 carbon atoms,

Z ³¹ is -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, particularly preferably -COO-, trans-CH = CH- or a single bond,

Z ⁴¹ and Z ⁴² are independently selected from the group consisting of -CH ₂ CH ₂ -, -COO-, trans-CH═CH-, trans-CF═CF-, -CH ₂ O-, -CF ₂ O-, Bond, preferably a single bond,

L ²¹ , L ²² , L ³¹ and L ³² are H or F,

g is 1, 2 or 3,

h is 0, 1, 2 or 3;

X ⁰ is preferably selected from the group consisting of F, Cl, CF ₃ , CHF ₂ , OCF ₃ , OCHF ₂ , OCFHCF ₃ , OCFHCHF ₂ , OCFHCHF ₂ , OCF ₂ CH ₃ , OCF ₂ CHF ₂ , OCF ₂ CHF ₂ , OCF ₂ CF ₂ OCF ₂ CF ₂ , OCF ₂ CF ₃ , CHF ₂ , OCF ₂ CF ₂ CHF ₂ , OCFHCF ₂ CF ₃ , OCFHCF ₂ CHF ₂ , OCF ₂ CF ₂ CF ₃ , OCF ₂ CF ₂ CClF ₂ , OCClFCF ₂ CF ₃ or CH = CF ₂ , Or OCF ₃ .

The compound of formula AA is preferably selected from the group consisting of the following general formulas:

In this formula,

A ²¹ , R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings described in the general formula AA, L ²³ and L ²⁴ each independently of one another are H or F, and X ⁰ preferably represents F. Particularly preferred are compounds of the general formulas AA1 and AA2.

Particularly preferred compounds of formula AA1 are selected from the group consisting of compounds of the following sub-formulas:

In this formula,

R ⁰ has one of the meanings given for the general formulas AA1 to R ²¹ ,
X ⁰ , L ²¹ and L ²² have the meanings indicated in the general formula AA1,
L ²³ , L ²⁴ , L ²⁵ and L ²⁶ are each independently H or F,
X ⁰ is preferably F.

Very particularly preferred compounds of the formula AA1 are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁰ has the meanings set forth for R ²¹ in formula AA1.

Particularly preferred compounds of formula AA2 are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁰ has the meanings set forth for R ²¹ in formula AA1, X ^0, L ²¹ and L ²² has the meaning given in the general formula ^{AA, L 23, L 24,} L 25 and L ²⁶ are each independently of one another , H or F, and X ⁰ preferably represents F.

Very particularly preferred compounds of the formula AA2 are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁰ has the meanings set forth for R ²¹ in formula AA1.

Particularly preferred compounds of formula AA3 are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁰ has the meanings given for the general formulas AA 1 to R ²¹ , X ⁰ , L ²¹ and L ²² have the meanings indicated in the general formula AA 3, and X ⁰ preferably represents F.

Particularly preferred compounds of formula AA4 are selected from the group consisting of the following sub-formulas:

AA4a

In this formula,

R ⁰ has the meanings set forth for R ²¹ in formula AA1.

The compound of formula BB is preferably selected from the group consisting of the following sub-formulas:

In this formula,

A ³¹ , A ³² , R ³¹ , X ⁰ , L ³¹ and L ³² have the meanings indicated in the general formula BB, and X ⁰ preferably represents F. Particularly preferred are compounds of the general formulas BB1 and BB2.

Particularly preferred compounds of formula BB1 are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formulas BB 1,
X ⁰ , L ³¹ and L ³² have the meanings indicated in the general formula BB1,
X ⁰ preferably represents F.

Very particularly preferred compounds of formula BB1a are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formulas BB 1.

Very particularly preferred compounds of formula BB1b are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formulas BB 1.

Particularly preferred compounds of formula BB2 are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁰ has one of the meanings given for R ²¹ in the general formula BB 2, X ⁰ , L ³¹ and L ³² have the meanings given in the general formula BB 2, and L ³³ , L ³⁴ , L ³⁵ and L ³⁶ are each Independently represents H or F, and X < ⁰ > preferably represents F;

Very particularly preferred compounds of formula BB2a are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2b are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2c are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of the formulas BB2d and BB2e are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2f are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of the formula BB2g are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2h are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2i are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Very particularly preferred compounds of formula BB2k are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB 2.

Alternatively or additionally to the compounds of the general formulas BB1 and / or BB2, the LC medium may comprise one or more compounds of the general formula BB3 defined above.

Particularly preferred compounds of formula BB3 are selected from the group consisting of the following sub-formulas:

In this formula,

R ³ has the meanings given for R ³¹ in the general formula BB ³ .

In addition to the compounds of the general formulas AA and / or BB, the LC medium according to the second preferred embodiment preferably has a dielectric anisotropy of -1.5 to +3 selected from the group consisting of compounds of the general formula CC as defined above Lt; RTI ID = 0.0 > pharmaceutically < / RTI >

Particularly preferred compounds of formula CC are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁴¹ and R ⁴² have the meanings indicated in the general formula CC and are preferably each independently of one another selected from the group consisting of alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy having 1 to 7 carbon atoms or 2 to 7 carbon atoms Alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl, and L < ⁴ > represents H or F;

In addition to or alternatively to compounds of the general formula CC, the LC medium according to the second preferred embodiment preferably comprises one or more oils having a dielectric anisotropy of -1.5 to +3 selected from the group consisting of compounds of the general formula DD Includes totally neutral compounds:

DD

In this formula,

A ⁴¹ , A ⁴² , Z ⁴¹ , Z ⁴² , R ⁴¹ , R ⁴² and h have the meanings indicated in the general formula CC.

Particularly preferred compounds of formula DD are selected from the group consisting of the following sub-formulas:

In this formula,

R ⁴¹ and R ⁴² have the meanings indicated in the general formula DD, R ⁴¹ preferably represents alkyl, and in general formula DD 1, R ⁴² is preferably alkenyl, particularly preferably - (CH ₂ ) ₂ - It represents CH = CH-CH _3, in the general formula DD2, R ⁴² is preferably _{alkyl, - (CH 2) 2 -CH} = CH 2 or - (CH ₂₎ shows the ₂ -CH = CH-CH _3.

The concentration of the compounds of the general formulas AA and BB in the LC medium according to the invention is preferably 2% to 60%, particularly preferably 3% to 35%, very particularly preferably 4% to 30% to be.

The concentration of the compounds of the general formulas CC and DD in the LC medium according to the invention is preferably from 2% to 70%, in particular from 5% to 65%, particularly preferably from 10% to 60%, very particularly preferably from 2% Is preferably 10% (preferably 15%) to 50%.

The combination of the low molecular weight compounds and the polymerized compounds described above as constituents of the LC host mixture according to the above described preferred embodiments is characterized by a high threshold voltage, low rotational viscosity and very good low temperature stability in the LC medium according to the invention, Achieves lumen points and high HR values, and allows fast generation of particularly small pretilt angles on PSA displays. In particular, compared to media from the prior art, the LC media in PSA displays exhibit a significantly shortened response time, especially also gray-tone response time.

The liquid crystal mixture has a rotational viscosity at 20 DEG C of preferably not less than 80 K, particularly preferably not less than 100 K in a nematic phase range and not more than 250 mPa-s, preferably not more than 200 mPa-s.

In a VA-type display according to the present invention, the molecules in the layer of the LC medium have a homeotropic alignment (homeotropic alignment) or a sloping homeotropic alignment with respect to the electrode surface in the switch-off state. When a voltage is applied to the electrode, the LC molecules are rearranged such that the longitudinal molecular axis is parallel to the electrode surface.

The LC medium according to the first preferred embodiment of the present invention, particularly used in displays of the PSA-VA type, exhibits a temperature in the range of preferably about -0.5 to -10, especially about -2.5 to -7.5 at 20 DEG C and 1 kHz And has a negative dielectric anisotropy ??.

The birefringence? N of the LC medium according to the first preferred embodiment of the present invention used in particular for displays of the PSA-VA type is preferably less than 0.16, particularly preferably 0.06 to 0.14, very particularly preferably 0.07 to 0.12.

In an OCB-type display according to the present invention, the molecules in the layer of the LC medium are in the "bend" alignment state. When a voltage is applied, the LC molecules are rearranged such that the longitudinal molecular axis is perpendicular to the electrode surface.

The LC medium according to the present invention used in the PSA-OCB type of display preferably has a positive dielectric anisotropy ?? according to the second preferred embodiment of the present invention, preferably at about +4 To < RTI ID = 0.0 > + 17. &Lt; / RTI >

The birefringence? N of the LC medium according to the second preferred embodiment of the present invention used in the OCB type display is preferably 0.14 to 0.22, particularly 0.16 to 0.22.

The LC medium according to the second preferred embodiment of the present invention used in particular for displays of the PSA-TN, PSA-positive-VA, PSA-IPS or PSA-FFS type, +30, particularly preferably in the range of +2 to +17, very particularly preferably in the range of +3 to +15.

The birefringence Δn of the LC medium according to the second preferred embodiment of the present invention used in displays of the PSA-TN, PSA-IPS or PSA-FFS type is preferably 0.07 to 0.15, particularly preferably 0.08 to 0.13 to be.

The LC medium according to the invention may also comprise further additives known to the person skilled in the art and described in the literature, for example polymerization initiators, inhibitors, stabilizers, surface-active substances or chiral dopants. These may be polymerizable or non-polymerizable. Thus, the polymerizable additive is classified as a polymerizable component or component A). Thus, the non-polymerizable additive is classified as non-polymerizable component or component B).

The LC medium may comprise, for example, at least one compound selected from the group consisting of chiral dopants, preferably compounds from Table B below.

It is also possible to add to the LC medium, for example, 0 to 15% by weight of a purple dye, further nanoparticles, a conductive salt, preferably ethyldimethyldodecylammonium 4-hexylbenzoate, tetrabutylammonium tetra (See for example Haller et al., Mol. Cryst. Liq. Cryst. 24 , 249-258 (1973)), or the complex anions of the nematic phase with respect to the dielectric anisotropy, viscosity and / Or materials for modifying the alignment can be added. Materials of this type are described, for example, in DE-A 22 09 127, 22 40 864, 23 21 632, 23 38 281, 24 50 088, 26 37 430 and 28 53 728.

The individual components of the preferred embodiments a) to z) of the LC medium according to the invention are known or can be easily derived by those skilled in the art from the prior art, since their preparation is based on the standard methods described in the literature. The corresponding compounds of the above formula CY are described, for example, in EP-A-0 364 538. Corresponding compounds of the general formula ZK are described, for example, in DE-A-26 36 684 and DE-A-33 21 373.

The LC medium which can be used in accordance with the invention can be prepared in a customary manner, for example by mixing one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above and optionally further liquid crystal compounds and / or additives . In general, the desired amount of component used in lesser amounts, advantageously at high temperature, is dissolved in the constituent component of the main component. It is also possible to mix a solution of the components in an organic solvent, for example acetone, chloroform or methanol, and after thorough mixing, the solvent may be removed again, for example by distillation. The present invention also relates to a process for the preparation of the LC medium according to the invention.

Needless to say, the LC medium according to the present invention may contain, for example, compounds in which H, N, O, Cl, F are substituted with the corresponding isotopes.

The structure of an LC display according to the present invention corresponds to the conventional geometry of a PSA display as described in the above cited prior art. In particular, the electrode on the color filter surface is also preferably a projection-free geometry in which only the electrodes on the TFT surface are not structured and only have the slots. A particularly suitable and preferred electrode structure for PSA-VA displays is described, for example, in US 2006/0066793 A1.

The following examples illustrate the present invention without limiting it. However, the following examples show those skilled in the art the preferred mixture of compounds, and their respective concentrations and combinations thereof with each other. In addition, the following examples illustrate achievable characteristics and combinations of characteristics.

The following abbreviations are used:

(n, m, z: independently of each other, 1, 2, 3, 4, 5 or 6 in each case)

Table A

In a preferred embodiment of the invention, the LC medium according to the invention comprises at least one compound selected from the group consisting of the compounds in Table A above.

Table B below shows possible chiral dopants that can be added to the LC medium according to the invention.

Table B

The LC medium preferably comprises 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, of a dopant. The LC medium preferably comprises at least one dopant selected from the group consisting of compounds of Table B above.

Table C below shows possible stabilizers which may be added to the LC medium according to the invention, where n is an integer from 1 to 12, preferably 1, 2, 3, 4, 5, 6, 7 or 8 And the terminal methyl group is not shown).

Table C

The LC medium preferably comprises 0 to 10% by weight, especially 1 to 5% by weight, particularly preferably 1 to 1% by weight of stabilizer. The LC medium preferably comprises one or more stabilizers selected from the group consisting of the compounds of Table C above.

Table D below illustrates exemplary compounds that can be used as reactive mesogen compounds, preferably in a LC medium according to the present invention.

Table D

In a preferred embodiment of the present invention, the mesogenic medium comprises one or more compounds selected from the group consisting of compounds of Table D.

In addition, the following abbreviations and symbols are used:

V ₀ represents the capacitive threshold voltage [V] at 20 ° C.

n _e represents an extraordinary refractive index at 20 ° C and 589 nm.

n ₀ represents the ordinary refractive index at 20 ° C and 589 nm.

[Delta] n indicates optical anisotropy at 20 [deg.] C and 589 nm.

ε _⊥ shows the dielectric permittivity perpendicular to the director at 20 ° C and 1 kHz.

ε _∥ indicates the permittivity parallel to the director at 20 ° C and 1 kHz.

?? indicates dielectric anisotropy at 20 占 폚 and 1 kHz.

cl.p., and T (N, I) represents the longevity point [° C].

? ₁ represents the rotational viscosity [mPa.s] at 20 占 폚.

K ₁ represents the elastic constant at 20 ° C, the "splay" strain [pN].

K ₂ represents the elastic constant at 20 ° C, "twist" strain [pN].

K ₃ represents the elastic constant at 20 ° C, "bend" strain [pN].

Unless otherwise expressly stated, all concentrations herein are expressed in weight percent and refer to the entire mixture, that is, the LC medium comprising all solids or liquid crystal components without solvent.

(S, N) on the nematic (N) phase on Smectic (S) and the temperature T (S, N) on the nematic Point T (N, I) is expressed in degrees Celsius (° C). m.p. represents a melting point, and cl.p. represents a luminescent point. C is a crystalline state, N is a nematic phase, S is a smectic phase, and I is an isotropic phase. The data between the symbols represents the transition temperature.

Unless otherwise explicitly stated in each case, all properties are described in Merck Liquid Crystals, Physical Properties of Liquid Crystals, Status Nov. 1997, Merck KGaA, Germany] and a temperature of 20 ° C is applied, Δn is measured at 589 nm and Δε is measured at 1 kHz.

In the present invention, the term "threshold voltage" relates to a capacitive threshold value (V ₀ ), also known as the Freedericks threshold, unless explicitly stated otherwise. In an embodiment, the optical threshold value may be quoted for a 10% relative contrast ratio (Cl ₀ ), as is commonly used.

The display used to measure the capacitive threshold voltage consists of two planar-parallel glass outer plates separated by 20 [mu] m, each having an inner electrode layer and an upper un rubbed polyimide alignment layer Resulting in homeotropic edge alignment of the molecules.

The display or test cell used to measure the tilt angle consists of two planar-parallel glass outer plates separated by 4 占 퐉, each having an inner electrode layer and an upper polyimide alignment layer, where two The polyimide layers are rubbed non-parallel to each other to cause homeotropic edge alignment of the liquid crystal molecules.

The polymerizable compound can be applied to a display or test cell by irradiating a defined intensity of UVA light (typically 365 nm) for a predetermined time while simultaneously applying voltage (typically 10 V to 30 V alternating current, 1 kHz) Lt; / RTI > In the examples, a 28 mW / cm ² mercury vapor lamp was used and the intensity was measured using a standard UV meter (Ushio UNI meter) equipped with a 365 nm band-pass filter Respectively.

The inclination angle was measured by a rotation determination experiment (Autronic-Melchers TBA-105). Small values (i.e., large deviations from 90 [deg.]) Represent large slopes.

The VHR values are measured as follows: 0.3% of the polymerizable monomeric compound is added to the LC host mixture and the resulting mixture is analyzed in a TN-VHR test cell (rinsed at 90 °, TN-polyimide alignment layer, layer thickness d Is about 6 [micro] m). The HR value is determined after 5 minutes at 100 ° C before and after UV exposure (solar test) for 2 hours at 1 V, 60 Hz, 64 μs pulses (measuring device: Autronic-Melchizer VHRM-105).

A bottle containing 1 g of the LC / RM mixture was stored at -10 DEG C to investigate the low temperature stability (also referred to as " LTS ") (i.e. stability of the LC mixture against spontaneous individual crystallization of the components at low temperatures) , And regularly confirms whether the mixture is crystallized or not.

Example One

7- (2- Methyl acryloyloxy ) -4,5,9,10- Tetrahydropyrenes -2-yl 2- Methyl acrylate

1.1 2,7- Diiodo -4,5,9,10- Tetrahydropyrenes

7.30 g (36.2 mmol) of 4,5,9,10-tetrahydropyrene, 3.30 g (14.5 mmol) of periodic acid and 9.00 g (35.5 mmol) of iodine were dissolved in 2.2 ml of concentrated sulfuric acid solution in 70 ml of glacial acetic acid And 15 ml of water at 70 < 0 > C for 1 hour. Subsequently, the solution was added to ice water and extracted three times with ethyl acetate. The combined organic phases were washed with dilute sodium hydrosulfite solution and saturated sodium hydrogen carbonate solution and dried over sodium sulfate. The solvent was removed in vacuo and the residue was chromatographed on silica gel with toluene / heptane (2: 1). The crude product was crystallized from heptane / toluene (1: 1) to give 2,7-diiodo-4,5,9,10-tetrahydropyrene as a colorless solid.

¹ H-NMR (CDCl ₃ )? = 2.80 ppm (s, 8 H, CH ₂ ), 7.43 (s, 4 H, Ar-H).

1.2 4,5,9,10- Tetrahydropyrenes -2,7- Diol

Initially, 3.20 g (6.80 mmol) of 2,7-diiodo-4,5,9,10-tetrahydropyrene was introduced into 40 ml of dioxane and a solution of 1.50 g (26.7 mmol) Potassium hydroxide, 300 mg (0.522 mmol) of bis (dibenzylideneacetone) palladium and 450 mg of 2-di-tert-butylphosphino-2 ', 4', 6'-triisopropylbiphenyl Was added and the batch was heated at 80 < 0 > C for 3 hours. The solution was subsequently diluted with 100 ml of toluene and extracted with water. The combined aqueous phases were acidified with dilute hydrochloric acid and extracted three times with ethyl acetate. The combined organic phases were washed with water and dried over sodium sulfate. The solvent was removed in vacuo and the residue was chromatographed on silica gel with toluene / ethyl acetate (7: 3) and the crude product was recrystallized from toluene / heptane (1: 1) , 10-tetrahydropyran-2,7-diol as colorless crystals.

¹ H-NMR (CDCl ₃ )? = 2.80 ppm (s, 8 H, CH ₂ ), 4.73 (s, 2H, OH), 6.54 (s, 4 H, Ar-H).

1.3 7- (2- Methyl acryloyloxy ) -4,5,9,10- Tetrahydropyrenes -2-yl 2- methyl - acrylate

900 mg (3.55 mmol) of 4,5,9,10-tetrahydropyrene-2,7-diol are suspended in 15 ml of dichloromethane, 1.3 ml of pyridine and 50 mg of DMAP are added, Was ice-cooled while dropwise adding a solution of 1.5 g (9 mmol) of acrylic acid anhydride in 25 ml of dichloromethane. After 30 minutes, the cooling water was removed and the batch was left stirring at room temperature overnight. Subsequently, the solution was filtered through silica gel, the eluent was evaporated and the crude product was recrystallized from heptane / toluene to give 7- (2-methylacryloyloxy) -4,5,9,10-tetrahydro Pyrene-2-yl 2-methylacrylate 146 C < / RTI > as colorless crystals.

Example 2

7- [4- (2- Methyl acryloyloxy ) Boot Ynyl] -4,5,9,10- Tetrahydropyrenes -2-yl 2- Methyl acrylate

2.1 2,7- Dive Lomo -4,5,9,10- Tetrahydropyrenes

Initially, 20.6 g (94.6 mmol) of 4,5,9,10-tetrahydropyrenes were introduced into 160 ml of trimethyl phosphate and 17 ml (332 mmol) of bromine solution in 40 ml of trimethylphosphate was added Lt; RTI ID = 0.0 > 25 C < / RTI > The batch was stirred for an additional 3 hours, added to 800 ml of ice water, and excess bromine was decomposed by the addition of sodium hydrosulfite solution. After 15 min, the precipitated product was filtered off by suction, warmed to dissolve in toluene, filtered through silica gel, and recrystallized from toluene / heptane (1: 1) to give 2,7-dibromo-4,5 , 9,10-tetrahydropyrene as colorless crystals.

2.2 7- Bromo -4,5,9,10- Tetrahydropyrenes -2-ol

Initially, 6.40 g (16.9 mmol) of 2,7-dibromo-4,5,9,10-tetrahydropyrene and 7 ml (30 mmol) of triisopropylborate were introduced into 200 ml of THF, Was added a solution of 15 ml (24 mmol) of 15% n-butyllithium in tetrahydrofuran at -70 < 0 > C. Upon completion of the addition, the mixture was stirred for an additional hour, hydrolyzed using 2 M hydrochloric acid, dissolved, and extracted twice with MTB ether. The combined organic phases were evaporated and vigorously stirred while suspending the residue in a mixture of 100 ml of toluene, 20 ml of 2 M sodium hydroxide solution and 20 ml of water and 10 ml of 30% hydrogen peroxide was added at 40 < 0 & Slowly added. Upon completion of the addition, the batch was stirred for an additional hour, added to 100 ml of water, and acidified using 2 M hydrochloric acid. The aqueous phase was separated and extracted three times with ethyl acetate. The combined organic phases were washed with a solution of ammonium iron (II) sulfate and a saturated sodium chloride solution and dried over sodium sulfate. The solvent was removed in vacuo, the residue was chromatographed on silica gel with dichloromethane and the crude product was recrystallized from toluene to give 7-bromo-4,5,9,10-tetrahydropyran-2-ol As colorless crystals.

2.3 7- (4- Hydroxy Boot Ynyl) -4,5,9,10- Tetrahydropyrenes -2-ol

Initially, 8.80 g (28.3 mmol) of 7-bromo-4,5,9,10-tetrahydropyran-2-ol was introduced into 100 ml of THF and 1.7 g (2.42 mmol) of bis 0.4 g (2.10 mmol) of copper (I) iodide and 11 ml of diisopropylamine were added and a solution of 5.0 g (78.3 mmol) 1-butyne in 20 ml THF Was added dropwise at 65 < 0 > C over 1 hour. Upon completion of the addition, the batch was stirred for an additional 2 hours, added to water, and acidified with 2 N hydrochloric acid. The aqueous phase was separated and extracted three times with ethyl acetate. The combined organic phases were washed with water, dried over sodium sulfate and the solvent was removed in vacuo. The crude product was filtered through silica gel with dichloromethane / ethyl acetate (4: 1) and recrystallized with toluene to give 7-iodo-9,10-dihydrophenanthrene-2-ol as a colorless solid .

2.4 7- [4- (2- Methyl acryloyloxy ) Boot Ynyl] -4,5,9,10- Tetrahydropyrenes -2-yl 2- Methyl acrylate

In analogy to example 1, 7- (4-hydroxybut-1-ynyl) -4,5,9,10-tetrahydropyran-2- But-1-ynyl] -4,5,9,10-tetrahydropyran-2-yl 2-methylacrylate Gt; 121 C < / RTI > as colorless crystals.

Example 3

4- [7- (2- Methyl acryloyloxy ) -4,5,9,10- Tetrahydropyrenes Yl] butyl 2- methyl - Acrylate

3.1 7- (4- Hydroxybutyl ) -4,5,9,10- Tetrahydropyrenes -2-ol

7- (4-Hydroxybut-1-ynyl) -4,5,9,10-tetrahydropyran-2-ol was fully hydrogenated on palladium / activated carbon catalyst in THF. The catalyst was filtered off, the solvent was removed in vacuo and the residue was recrystallized from toluene to give 7- (4-hydroxybutyl) -4,5,9,10-tetrahydropyran-2-ol as a colorless solid .

3.2 4- [7- (2- Methyl acryloyloxy ) -4,5,9,10- Tetrahydropyrenes Yl] butyl 2- Acrylic Ray The

Similarly to Example 1, the title compound was obtained from 7- (4-hydroxybutyl) -4,5,9,10-tetrahydropyran-2-ol 4- [7- (2-methylacryloyloxy) , 9,10-tetrahydropyran-2-yl] butyl 2-methylacrylate Gt; 110 C < / RTI > as colorless crystals.

Example 4

4,4- Dimethyl -6- (2- Methyl acryloyloxy ) -8,9- Dihydro -4H- Cyclopenta [ def] phenanthren-2-yl 2- Methyl acrylate

4.1 2,6- Dive Lomo -4,4- Dimethyl -8,9- Dihydro -4H- Cyclopenta [def] phenanthrene

Initially, 3.50 g (19.9 mmol) of 4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene (CAS No. 1035304-31-4) was introduced into the trimethyl phosphate , And gently cooled at 25 [deg.] C with dropwise addition of 3.5 ml (68 mmol) of bromine solution in 10 ml of trimethylphosphate. The batch was stirred at room temperature for 4 hours, added to 150 ml of ice water and 100 ml of toluene, and excess bromine was decomposed using sodium hydrosulfite solution. The aqueous phase was separated and extracted once with toluene. The combined organic phases were washed with water, dried over sodium sulfate and the solvent was removed in vacuo. The crude product was filtered through silica gel with toluene / heptane (1: 1) and recrystallized with toluene / heptane (1: 1) to give 2,6-dibromo-4,4- -Dihydro-4H-cyclopenta [def] phenanthrene as colorless crystals.

^{1 H-NMR (500 MHz,} CDCl 3) δ = 1.48 ppm (s, 6 H, CH 3), 3.08 (s, 4 H, CH 2), 7.24 (s, 2 H, Ar-H), 7.33 ( s, 2 H, Ar-H).

4.2 4,4- Dimethyl -8,9- Dihydro -4H- Cyclopenta [def] phenanthrene -2,6- Diol

Dibromo-4,9-dihydro-4H-cyclopenta [def] phenanthrene with 4,6-dibromo-4,4- , 9-dihydro-4H-cyclopenta [def] phenanthrene-2,6-diol as colorless crystals.

^{1 H-NMR (400 MHz,} CDCl 3) δ = 1.46 ppm (s, 6 H, CH 3), 3.04 (s, 4 H, CH 2), 4.59 (s, br. 2 H, OH), 6.55 ( d, J = 1.7 Hz, 2H, Ar-H), 6.67 (d, J = 1.7 Hz, 2H, Ar-H).

4.3 4,4- Dimethyl -6- (2- Methyl acryloyloxy ) -8,9- Dihydro -4H-cyclopenta [ def ] Phenanthren-2-yl2- Methyl acrylate

In analogy to example 1, from 4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene-2,6- Methyl acryloyloxy) -8,9-dihydro-4H-cyclopenta [def] phenanthrene-2-yl 2-methylacrylate 77 " C < / RTI > as colorless crystals.

Example 5

4,4- Dimethyl -6- (2- Methyl acryloyloxy ) -4H- Cyclopenta [def] phenanthrene 2-yl 2-methyl- Acrylic Ray The

5.1 2,6- Dive Lomo -4,4- Dimethyl -4H- Cyclopenta [def] phenanthrene

Initially, 2.20 g (5.82 mmol) of 2,6-dibromo-4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] phenanthrene, 1.10 g (6.18 mmol) N- Bromosuccinimide and 50 mg of azobis (isobutyronitrile) were introduced into 30 ml of carbon tetrachloride and boiled by heating slowly. After 3 hours, the batch was cooled to 60 DEG C and a solution of 1.5 g of sodium acetate in 20 ml of glacial acetic acid was added and the mixture was subsequently stirred at 70 DEG C for 4 hours. Subsequently, the solution was added to dichloromethane, washed twice with water, dried over sodium sulfate and evaporated in vacuo. The residue was filtered through silica gel with toluene and recrystallized with heptane to give 2,6-dibromo-4,4-dimethyl-4H-cyclopenta [def] phenanthrene as colorless crystals.

¹ H-NMR (400 MHz, CDCl ₃ )? = 1.66 ppm (s, 6 H, CH ₃ ), 7.67 (d, J = 1.2 Hz, 2H, Ar- -H), 7.97 (d, J = 1.2 Hz, 2H, Ar-H).

5.2 4,4- Dimethyl -4H- Cyclopenta [def] phenanthrene -2,6- Diol

In analogy to the synthetic procedure described in example 1.2, 2,6-dibromo-4,4-dimethyl-8,9-dihydro-4H-cyclopenta [def] -Cyclopenta [def] phenanthrene-2,6-diol as colorless crystals.

5.3 4,4- Dimethyl -6- (2- Methyl acryloyloxy ) -4H- Cyclopenta [def] phenanthrene -2-yl 2- Methyl acrylate

In analogy to example 1, from 4,4-dimethyl-4H-cyclopenta [def] phenanthrene-2,6-diol 4,4-dimethyl-6- (2-methylacryloyloxy) 4H-cyclopenta [def] phenanthren-2-yl 2-methylacrylate was dissolved in mp 170 < 0 > C as colorless crystals.

Examples One

The nematic LC mixture N1 is formulated as follows:

0.3% of the polymerizable monomer compound from the example shown below was added to the LC mixture N1 and the resulting mixture was applied to a VA e / o test cell (anti-parallel rubbed, VA-polyimide alignment layer, 4 [mu] m). The cell was irradiated with UV light having a strength of 50 mW / cm ² for a specified time by applying a voltage of 24 V (alternating current) to induce polymerization of the monomer compound. The inclination angle before and after the UV irradiation was measured by a rotation determination experiment (Otronic-Melchus TBA-105).

To determine the rate of polymerization, the residual content (wt%) of unpolymerized RM in the test cell after various exposure times was determined by the HPLC method. To this end, each mixture was polymerized under the conditions specified in the test cell. The mixture was then washed from the test cell using methyl ethyl ketone and measured.

For comparative purposes, the tests described above were carried out using the following polymerizable compounds C1 to C3 known in the prior art.

The tilt angle results are summarized in Table 1. The RM concentrations after various exposure times are summarized in Table 2.

Table 1 (t = exposure time)

Table 2 (t = exposure time)

As shown in Table 1, the small inclination angle after polymerization could be achieved earlier than in the monomers according to the invention (Examples 1 to 5) than monomers C1 to C3 from the prior art. Also, as shown in Table 2, a significantly faster polymerization rate is achieved in the monomers according to the invention (Examples 1 to 3) than monomers C1 to C3.

Claims

A liquid crystal medium comprising at least one compound of the general formula I:

I
In this formula,
W ¹ and W ² are each independently selected from the group consisting of -CY ₂ CY ₂ -, -CY═CY-, -CY ₂ -O-, -O-CY ₂ -, -C (O) -O-, -OC O) -, -C (R ^c R ^d ) -, -O-, -S- or -NR ^e -;
Y represents in each case, the same or different, H or F;
R ^a and R ^b are each independently of each other, P-Sp-, H, F , Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, SF 5, 1 to Lt; / RTI > represents linear or branched alkyl having 1 to 25 carbon atoms, or aryl or heteroaryl, wherein at least one of the radicals R ^a and R ^b represents or contains the group P-Sp-; The at least one non-adjacent CH ₂ group in the alkyl may additionally be, independently of one another, arylene, -C (R ⁰ ) ═C (R ⁰⁰ ) -, ^{-C≡C-, -N (R 0) -} , -O-, -S-, -CO-, -CO-O-, -O-CO- , or may be replaced by -O-CO-O- and , One or more H atoms may be further substituted with F, Cl, Br, I, CN or P-Sp-; Wherein said aryl or heteroaryl has from 2 to 25 carbon atoms and may also contain two or more fused rings and is optionally mono- or polysubstituted with L;
R ^c , R ^d and R ^e are each independently of the other H, or linear or branched alkyl having 1 to 12 carbon atoms;
P represents in each case, the same or different, a polymerizable group;
Sp in each case, identically or differently, represents a spacer group or a single bond;
A ¹ and A ² each independently of one another represent an aromatic, heteroaromatic, alicyclic or heterocyclic group; Having 4 to 25 carbon atoms, may contain fused rings and are optionally mono- or polysubstituted with L;
L is in each case the same or different and is selected from the group consisting of P-Sp-, OH, CH ₂ OH, halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, (R ^x ) ₂ , -C (= O) Y ¹ , -C (= O) R ^x , -N (R ^x ) ₂ , optionally substituted silyl, or an optionally substituted carbon or hydrocarbon group;
R ^x represents P-Sp-, H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 carbon atoms; In this alkyl, the one or more non-adjacent CH ₂ groups may additionally be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO - or -O-CO-O- and at least one H atom may be further substituted by F, Cl or P-Sp-;
Y ¹ represents halogen;
Z ¹ and Z ² are each independently selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O -, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, - (CH ₂ ) _n -, -CF ₂ CH ₂ - _{-CH 2 CF 2 -, - (} CF 2) n -, -CH = CH-, -CF = CF-, -CH = CF-, -CF = CH-, -C≡C-, -CH = CH- COO-, -OCO-CH = CH-, -CH 2 -CH 2 -COO-, -OCO-CH 2 -CH 2 -, -C (R 0 R 00) -, -C (R y R z) - Or a single bond;
R ⁰ and R ⁰⁰ are each independently of one another, in each case identically or differently, H or alkyl having 1 to 12 carbon atoms;
R ^y and R ^z each independently of one another denote H, F, CH ₃ or CF ₃ ;
n represents, in each case, the same or different, 1, 2, 3 or 4;
p and q each independently represent 0, 1 or 2;
r represents, in each case, the same or different, 0, 1 or 2;

The method according to claim 1,
Characterized in that the compound of general formula I is selected from compounds of the general formula IA:

IA
In this formula,
R ¹ , R ^b , W ¹ , W ² , A ¹ , A ² , Z ¹ , Z ² , L, p, q and r have the meanings given in claim 1.

The method according to claim 1,
In the compounds of the general formula I,
A ¹ and A ² are each, independently of one another, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, in which one or more CH groups can be further substituted by N; Cyclohexane-1,4-diyl in which one or more non-adjacent CH ₂ groups may be replaced by O and / or S; Cyclohexylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane- 1,4-diyl, spiro [3.3] heptane- Diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan- Diyl, octahydro-4,7-methanoindan-2,5-diyl, phenanthrene-2,7-diyl, anthracene-2,7-diyl, 9,10-dihydrophenanthren- , 7-diyl, 6H-benzo [c] chromen-3,8-diyl, 9H-fluorene- Dibenzofuran-3,7-diyl, 2-oxo-2H-chromen-7-yl, 4-phenyl- 6-yl or 4-phenyl-4-oxo-4H-chromen-6-yl, all of these groups being unsubstituted or mono- or polysubstituted by L;
L is _{P-Sp-, OH, CH 2} OH, F, Cl, Br, I, -CN, -NO 2, -NCO, -NCS, -OCN, -SCN, -C (= O) N (R x _{) 2, -C (= O)} Y 1, -C (= O) R x, -N (R x) 2, silyl, which are optionally substituted, aryl of 6 to 20 carbon atoms which are optionally substituted, 1 Straight or branched alkyl or alkoxy having from 1 to 25 carbon atoms, or straight or branched alkyl or alkoxy having from 2 to 25 carbon atoms, or straight or branched alkenyl having from 2 to 25 carbon atoms, alkynyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxy Carbonyloxy, in which at least one H atom in all these groups may be replaced by F, Cl, P or P-Sp-;
R ^x and Y ¹ have the meanings given in claim 1,
Liquid crystal medium.

A liquid crystal cell having two substrates and two electrodes, wherein at least one substrate is transparent to light and at least one substrate has one or two electrodes; And
A layer of a liquid crystal medium comprising a polymerized component and a low molecular weight component disposed between the substrates,
A liquid crystal display of the PS or PSA type,
Wherein the polymerized component is obtained by applying a voltage to the electrode and polymerizing at least one polymerizable compound in the liquid crystal medium between the substrates of the liquid crystal cell,
Wherein at least one of the polymerizable compounds is a polymerizable compound according to any one of claims 1 to 3,
Liquid crystal display.

The method according to claim 1,
A liquid crystal medium characterized by comprising at least one compound of the following formula CY and / or PY:

In this formula,
a represents 1 or 2;
b represents 0 or 1;

The

Lt; / RTI >
R ¹ and R ² are each, independently of one another, alkyl having from 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are optionally replaced by -O-, CH = CH-, -CO-, -O-CO- or -CO-O-;
Z ^x is _{-CH = CH-, -CH 2 O-,} -OCH 2 -, -CF 2 O-, -OCF 2 -, -O-, -CH 2 -, -CH 2 CH 2 - or a single bond, ;
L ¹ to L ⁴ are each, independently of one another, F, Cl, OCF ₃ , CF ₃ , CH ₃ , CH ₂ F or CHF ₂ .

The method according to claim 1,
A liquid crystal medium, characterized in that it comprises at least one compound of the general formula ZK:

ZK
In this formula,

The

Lt; / RTI >

The

Lt; / RTI >
R ³ and R ⁴ each independently of one another represent alkyl having 1 to 12 carbon atoms, wherein 1 or 2 non-adjacent CH ₂ groups may also be replaced by -O-, -CH = CH-, -CO-, -O-CO- or -CO-O-;
Z ^y represents -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF-, or represents a single bond.

delete

5. The method of claim 4,
PSA-FSA, PSA-Positive-VA or PSA-TN display, characterized in that the liquid crystal display is a PSA-VA, PSA-OCB, PSA-IPS, PSA-FFS.

delete

The method according to claim 1,
Polymerizable component A) comprising at least one polymerizable compound; And
A liquid crystal component B) comprising at least one low molecular weight compound,
Lt; / RTI >
Characterized in that said component A) comprises at least one polymerizable compound according to claim 1,
Liquid crystal medium.

11. The method of claim 10,
Wherein component B) comprises at least one compound selected from compounds of the following formulas CY, PY and ZK: liquid crystal medium:

[In the above formula,
a represents 1 or 2;
b represents 0 or 1;

The

Lt; / RTI >
R ¹ and R ² are each, independently of one another, alkyl having from 1 to 12 carbon atoms, in which one or two non-adjacent CH ₂ groups are optionally replaced by -O-, CH = CH-, -CO-, -O-CO- or -CO-O-;
Z ^x is _{-CH = CH-, -CH 2 O-,} -OCH 2 -, -CF 2 O-, -OCF 2 -, -O-, -CH 2 -, -CH 2 CH 2 - or a single bond ;
L ¹ to L ⁴ are each, independently of one another, F, _{Cl, OCF 3, CF 3,} CH 3, CH 2 F or CHF ₂ shows a];

ZK
[In the above formula,

The

Lt; / RTI >

The

Lt; / RTI >
R ³ and R ⁴ each independently of one another represent alkyl having 1 to 12 carbon atoms, wherein 1 or 2 non-adjacent CH ₂ groups may also be replaced by -O-, -CH = CH-, -CO-, -O-CO- or -CO-O-;
Z ^y represents -CH ₂ CH ₂ -, -CH═CH-, -CF ₂ O-, -OCF ₂ -, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -C ₂ F ₄ -, -CF = CF- or a single bond.

delete

The process according to any one of claims 1 to 3, comprising the step of esterifying or etherating the compound of formula II or IIA, in the presence of a dehydrating agent, with a corresponding acid, acid derivative, or halogenated compound containing P group A process for producing a compound according to any one of claims 1 to 3, wherein the P group is a polymerizable group,

In this formula,
W ¹ and W ² each independently of one another represent -CY = CY- or -C (R ^c R ^d ) -;
Y represents in each case, the same or different, H or F;
R < ^c > and R < ^d > each independently of the other represent H or straight chain or branched alkyl having 1 to 12 carbon atoms;
Sp in each case, identically or differently, represents a spacer group or a single bond;
A ¹ and A ² are each, independently of one another, 1,4-phenylene, naphthalene-1,4-diyl or naphthalene-2,6-diyl, in which one or more CH groups can be further substituted by N; Cyclohexane-1,4-diyl in which one or more non-adjacent CH ₂ groups may be replaced by O and / or S; Cyclohexylene, bicyclo [1.1.1] pentane-1,3-diyl, bicyclo [2.2.2] octane- 1,4-diyl, spiro [3.3] heptane- Diyl, piperidine-1,4-diyl, decahydronaphthalene-2,6-diyl, 1,2,3,4-tetrahydronaphthalene-2,6-diyl, indan- Diyl, octahydro-4,7-methanoindan-2,5-diyl, phenanthrene-2,7-diyl, anthracene-2,7-diyl, 9,10-dihydrophenanthren- , 7-diyl, 6H-benzo [c] chromen-3,8-diyl, 9H-fluorene- Dibenzofuran-3,7-diyl, 2-oxo-2H-chromen-7-yl, 4-phenyl- 6-yl or 4-phenyl-4-oxo-4H-chromen-6-yl, all of which may be unsubstituted or mono- or polysubstituted by L;
L is in each case the same or different and is selected from the group consisting of P-Sp-, OH, CH ₂ OH, halogen, -CN, -NO ₂ , -NCO, -NCS, -OCN, (R ^x ) ₂ , -C (= O) Y ¹ , -C (= O) R ^x , -N (R ^x ) ₂ , optionally substituted silyl, or an optionally substituted carbon or hydrocarbon group;
P represents in each case, the same or different, a polymerizable group;
R ^x represents P-Sp-, H, halogen, straight-chain, branched or cyclic alkyl having 1 to 25 carbon atoms; In this alkyl, the one or more non-adjacent CH ₂ groups may additionally be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO - or -O-CO-O- and at least one H atom may be further substituted by F, Cl or P-Sp-;
Y ¹ represents halogen;
Z ¹ and Z ² are each independently selected from the group consisting of -O-, -S-, -CO-, -CO-O-, -OCO-, -O-CO-O-, -OCH ₂ -, -CH ₂ O -, -SCH ₂ -, -CH ₂ S-, -CF ₂ O-, -OCF ₂ -, -CF ₂ S-, -SCF ₂ -, - (CH ₂ ) _n -, -CF ₂ CH ₂ - _{-CH 2 CF 2 -, - (} CF 2) n -, -CH = CH-, -CF = CF-, -CH = CF-, -CF = CH-, -C≡C-, -CH = CH- COO-, -OCO-CH = CH-, -CH 2 -CH 2 -COO-, -OCO-CH 2 -CH 2 -, -C (R 0 R 00) -, -C (R y R z) - Or a single bond;
R ⁰ and R ⁰⁰ are each independently of one another, in each case identically or differently, H or alkyl having 1 to 12 carbon atoms;
R ^y and R ^z each independently of one another denote H, F, CH ₃ or CF ₃ ;
n represents, in each case, the same or different, 1, 2, 3 or 4;
p and q each independently represent 0, 1 or 2;
r represents, in each case, the same or different, 0, 1 or 2;
G and G 'are each independently of the other a H atom or a protecting group selected from the group consisting of alkyl, acyl, alkylsilyl, arylsilyl, 2-tetrahydropyranyl and methoxymethyl, Said acyl having from 1 to 40 carbon atoms, said aryl having from 6 to 40 carbon atoms.

A liquid crystal cell having at least one substrate transparent to light and at least one substrate having two substrates and two electrodes having one or two electrodes, And introducing a liquid crystal medium according to any one of claims 1 to 11 and applying a voltage to the electrode to polymerize the polymerizable compound.