WO2019154740A1

WO2019154740A1 - Liquid-crystal medium

Info

Publication number: WO2019154740A1
Application number: PCT/EP2019/052567
Authority: WO
Inventors: Nils Greinert; Matthias Bremer; Patrick SUESS; Anna Lisa HAWLITSCHEK; Renate SEEGER
Original assignee: Merck Patent Gmbh
Priority date: 2018-02-06
Filing date: 2019-02-04
Publication date: 2019-08-15
Also published as: CN111712556A; CN111712556B; TW201936907A; EP3749733A1

Abstract

The present invention relates to a liquid crystal (LC) medium comprising polymerizable compounds, to a process for itspreparation, to itsuse for optical, electro-optical and electronic purposes, in particular in LC displays, and to LC displays comprising it.

Description

Liquid-crystal medium

The present invention relates to a liquid crystal (LC) medium comprising polymerizable compounds, to a process for its preparation, to its use for optical, electro-optical and electronic purposes, in particular in flexible LC displays, and to LC displays comprising it.

Background of the Invention Free form LC displays and flexible LC displays have recently found widespread interest which combine the advantages of variable shape and robustness.

Free form LC displays can have a permanent shape other than the flat shape of rigid flat panel displays, for example a curved shape, or can even have a variable shape. The simplest form of the first type are curved TVs that have been developed in the recent past and offer the viewer an enhanced viewing experience. Thereby it is possible to provide displays which are not only shaped in one but in two dimensions, and which can be used for example as car dashboards or advertising screens.

Flexible displays, another type of free form displays, have also been developed, and have been proposed for example for use in mobile phones or smart watches utilizing the advantages of flexibility. Further potential applications are foldable or Tollable mobile phones, as well as extra-large screens for presentations or home entertainment, which, due to their size, require to be Tollable or foldable for being transported or stowed.

Advantageously such devices are based on plastic substrates instead of rigid glass substrates as used in conventional, unflexible LC displays.

Another display concept,’unbreakable’ displays, are also based on plastic substrates and refers to a display design featuring particular robustness, durability, and resistance against mechanical impact. The use of flexible plastic substrates instead of glass substrates reduces the risk of damage, especially for handheld, high value devices like mobile phones, e.g. when dropped accidentally or becoming otherwise damaged during normal use. One of the main technical challenges of LC displays with curved or flexible substrates is that a constant LC layer thickness (also referred to as "LC cell gap" or simply "cell gap") is critical for proper device operation. In LC displays usually a proper combination of defined LC layer thickness and LC material properties ensures that the pixels can be switched between a black state and light transmitting state. In case of a varying layer thickness, undesired interference with the gap distance between the substrates can result in visible optical defects. It should therefore be ensured that the LC layer thickness is not altered by the bending or the lack of rigidity of flexible plastic substrates.

Another advantage of flexible plastic substrates is that they can be provided with a lower thickness than glass substrates, thereby enabling the

manufacturing of thinner LC displays. However, due to their higher flexibility it is necessary to ensure a constant cell gap for the reasons described above.

In conventional LC displays with rigid glass substrates, usually spacer particles are added to the LC layer in order to define and maintain a constant LC layer thickness. A possible solution for free form displays is to adapt this concept by incorporating supporting structures, like for example polymer walls, that can both resist compression and bind the two substrates together. A suitable manufacturing process could be to prefabricate the polymer wall structures, spread the LC mixture on the substrate, and subsequently close the panel with the top substrate. However, potential problems with this approach are for example that spreading of the LC mixture is obstructed by the support structures, and that bonding to the top substrate might not be sufficient. There is thus a great demand for free form or unbreakable LC displays which are based on flexible substrates like e.g. plastic substrates, and which have a constant cell gap even when deviating from a flat shape.

An alternative solution for manufacturing free form displays with constant LC layer thickness is to create the polymer wall structures by means of a patterened photopolymerization process after the display has been assembled.

This is schematically illustrated in Fig. 1a-c showing a polymer wall formation process. Fig. 1a shows an LC mixture consisting of LC host molecules

(rods), polymerizable monomer (dots), and photo-initiator (not shown). As shown in Fig. 1b the LC mixture is filled into the display, or the LC mixture is spread on a first substrate and a second substrate is applied on top thereof, and UV radiation (indicated by the arrows) is applied through a photomask. The growing polymer will phase separate from the LC medium, and as a result polymer walls are formed in the irradiated regions in the shape of the mask pattern as shown in Fig. 1c, while the LC phase of the LC host molecules (rods) in the pixel area is restored. The polymer walls technique as described above thus enables the

manufacturing of free form and robust displays by using specific

polymerisable LC compositions. In addition, it enables the manufacturing of flexible LC displays that combine the advantages of low thickness and robustness.

The formation of polymer walls by this method for LC display applications has been described in prior art and has been suggested for use in a variety of display modes. Also, in prior art LC mixtures have been developed for the realization of LC displays with flexible substrates. These LC mixtures contain reactive polymer precursors that allow the formation of polymer walls in the display by the patterned photopolymerization method as described above,

For example, US6130738 and EP2818534 A1 disclose an LC display that comprises polymer walls formed from one or two polymerizable monomers that are contained in the LC host mixture.

However, the currently used LC mixtures and monomers for use in flexible LC displays with polymer wall formation do still have several drawbacks and leave room for further improvement. For example, it was observed that the polymerizable compounds and LC media used in prior art do often show insufficient phase separation between the polymer walls and the LC molecules of the LC host mixture. This leads on the one hand to the undesired inclusion of LC molecules in the polymer walls, and on the other hand to increased amounts of polymer molecules dissolved or dispersed in the LC host mixture, both of which can negatively influence the display performance.

Thus, LC molecules trapped in the polymer wall can lead to reduced transparency and contrast of the display, a deterioration of the electrooptical response due to formation of domains with different switching speed, and decreased adhesion of the polymer walls to the substrates. On the other hand, undesired amounts of polymer molecules in the LC host mixture can negatively affect the LC mixture properties.

Moreover, it was observed that the thickness of the polymer walls is often not constant but varying, which can lead to non-uniform pixel size. Besides the polymer walls do often still not show sufficient stability against mechanical pressure on the one hand and sufficient elasticity on the other hand. Also, the polymer walls are often too thick, which reduces transparency and contrast of the display.

Another problem observed with hitherto used materials is that they do not always fulfil the requirement of good phase separation, thus leading to increased polymerization time, and high degree of crosslinking, thus leading to poor wall stability especially under mechanical stress.

It is therefore desirable to have available improved LC mixtures and

monomers for use in flexible LC displays which can overcome the drawbacks of materials used in prior art as described above.

The present invention is based on the object of providing novel suitable materials, in particular LC host mixtures comprising polymerizable monomers, for use in flexible LC displays with polymer walls, which do not have the disadvantages indicated above or do so only to a reduced extent. In particular, the invention is based on the object of providing LC media comprising polymerizable monomers, which enable the formation of polymer walls in a time- and cost-effective manner, and which are suitable for mass production. The formed polymer walls should show clear phase separation from the LC host mixture, without or with a reduced amount of defects or LC molecules trapped in the polymer wall, and without or with a reduced amount of polymer molecules dissolved in the LC host mixture. Also, the polymer walls should show constant thickness, high elasticity, high stability against mechanical or thermal stress, and good adhesion to the substrates.

Another object of the invention is to provide improved LC host mixtures for flexible displays which should show high specific resistance values, high VHR values, high reliability, low threshold voltages, short response times, high birefringence, show good UV absorption especially at longer wavelengths, allow quick and complete polymerization of the monomers contained therein, and reduce or prevent the occurrence of image sticking in the display.

Another object of the invention is to provide LC displays with polymer walls that show high transparency in the addressed state, good contrast, high switching speed and a large operating temperature range.

Another object of the present invention is to provide an improved technical solution for enabling LCD technology for free form, thin and unbreakable LC displays based on flexible substrates, preferably flexible plastic substrates, with constant cell gap, low thickness and high stability.

Another object of the invention is to provide polymerizable LC media for the manufacturing of LC displays with polymer walls, which enable at the same a good phase separation and a high degree of crosslinking.

The above objects have been achieved in accordance with the present invention by materials and processes as described and claimed hereinafter.

Thus, it has surprisingly been found that at least some of the above-mentioned objects can be achieved by using an LC medium which comprises one or more monomers that are capable of being polymerized by radical polymerization, and further comprises a RAFT (reversible addition- fragmentation chain transfer) agent.

The inventors of the present invention have now surprisingly found that by polymerizing the monomers in the LC medium by RAFT polymerization in the presence of the RAFT agent it is possible to form polymer walls which enable good phase separation and a high degree of crosslinking, and show constant thickness, high elasticity, high stability against mechanical pressure, and good adhesion to the substrates.

It has also been surprisingly found that the polymerizable sytems according to the present invention can also be used to form spacers to maintain a constant cell gap between the substrates of the LC display. This can support or even replace the spacer materials that are normally used in prior art.

RAFT polymerization and RAFT agents are known in prior art for the synthesis of polymers with a controlled molecular weight and chain length and a low polydispersity. However, their use in the formation of polymer walls for flexible LC displays has hitherto not been disclosed or suggested.

Summary of the Invention

The invention relates to a liquid crystal (LC) medium comprising a

polymerizable component A and a liquid-crystalline component B, hereinafter also referred to as "LC host mixture", wherein component B comprises, and preferably consists of, one or more mesogenic or liquid-crystalline

compounds, and component A comprises one or more polymerizable compounds comprising a straight-chain or branched hydrocarbon group having from 1 to 30 C atoms, or a monocyclic hydrocarbon group having from 3 to 24 ring atoms, or a bi- or polycyclic hydrocarbon group having from 4 to 30 ring atoms, and attached thereto one or more polymerizable groups that are capable of radical polymerization, a RAFT (reversible addition-fragmentation chain transfer) agent, optionally a polymerization initiator.

The liquid-crystalline component B of an LC medium according to the present invention is hereinafter also referred to as "LC host mixture", and preferably contains LC compounds that are selected only from low-molecular-weight compounds which are unpolymerizable, and optionally contains further additives like stabilizers or chiral dopants.

The invention furthermore relates to an LC medium or LC display as described above and below, wherein the polymerizable compounds, or the compounds of component A, are polymerized by RAFT polymerization.

The invention furthermore relates to a process of forming polymer walls in an LC medium as described above and below, comprising the step of subjecting one or more polymerizable compounds or a component A as described above and below to RAFT polymerization in the LC medium.

The invention furthermore relates to a process for preparing an LC display, comprising the process of forming polymer walls as described above and below.

The invention furthermore relates to a process for preparing an LC medium as described above and below, comprising the steps of mixing an LC host mixture or LC component B as described above and below, with one or more polymerizable compounds or component A as described above and below, and optionally with further LC compounds and/or additives.

The invention further relates to the use of LC medium in LC displays, preferably in flexible LC displays.

The invention furthermore relates to an LC display comprising an LC medium as described above and below.

The invention furthermore relates to an LC display comprising polymer walls obtainable by RAFT polymerization of one or more polymerizable compounds or a polymerizable component A as described above and below, or comprising an LC medium as described above and below.

The invention furthermore relates to an LC display comprising spacers obtainable by RAFT polymerization of one or more polymerizable compounds or a polymerizable component A as described above and below, or comprising an LC medium as described above and below.

The LC display according to the present invention is preferably a flexible LC display, and preferably a TN, OCB, IPS, FFS, posi-VA, VA or UB-FFS display.

In another preferred embodiment the LC display according to the present invention is a display of the polymer stabilized alignment (PSA) mode, preferably a flexible LC display, and preferably a PS-TN, PS-OCB, PS-IPS, PS-FFS, PS-posi-VA, PS-VA or PS-UB-FFS display.

In another preferred embodiment the LC display according to the present invention is a display of the self-aligned (SA) mode, preferably a flexible LC display, and preferably a SA-VA or SA-FFS display.

The invention furthermore relates to an LC display comprising two

substrates, at least one which is transparent to light, an electrode provided on each substrate or two electrodes provided on only one of the substrates, and located between the substrates a layer of an LC medium as described above and below, wherein the polymerizable compounds are polymerized by radical polymerization between the substrates of the display.

The invention furthermore relates to a process for manufacturing an LC display as described above and below, comprising the steps of filling or otherwise providing an LC medium as described above and below between the substrates of the display, and polymerizing the polymerizable compounds by radical polymerization. The displays according to the invention have two electrodes, preferably in the form of transparent layers, which are applied to one or both of the substrates. In some displays, for example in TN, OCB or VA displays, one electrode is applied to each of the two substrates. In other displays, for example in IPS, FFS or UB-FFS displays, both electrodes are applied to only one of the two substrates.

The polymerizable compounds of the polymerizable component are preferably polymerized by radical photopolymerization, very preferably by radical UV photopolymerization, further preferably by thermal cationic polymerization.

Brief Description of the Drawings

Fig. 1 schematically illustrates the polymer wall formation process in displays according to prior art and according to the present invention.

Fig. 2-7 show polarization microscope images of test cells containing polymerizable mixtures P1 -P6 according to the invention after polymerization.

Terms and Definitions

RAFT (reversible addition-fragmentation chain transfer) polymerization is a type of living polymerization or controlled radical polymerization, more precisely a reversible deactivation radical polymerization (RDRP), which is mediated by a RAFT agent.

RAFT polymerization allows the controlled synthesis of polymers with a well defined molecular weight and degree of polymerization which have a low polydispersity or are even monodisperse. The control of the polymerization reaction is achieved by reversible chain transfer reactions. Therein a propagating radical chain reacts with the RAFT agent and forms an

intermediate RAFT adduct radical which, due to the structure of the RAFT agent, may undergo a fragmentation reaction in either direction, to give either the starting species or a radical and a polymeric RAFT agent. The leaving group radical then reacts with another monomer to start another growing polymer chain. Thereby the chance of propagation is equally distributed among the growing chains. As a result the formed polymer chains have a narrow polydispersity (PD). The average chain length of the polymer is proportional to the concentration of the RAFT agent and to the conversion of monomer into polymer. A detailed description of the RAFT polymerization process can be found in the literature, for example in the following brochure of Sigma-Aldrich and the articles cited therein https://www.sigmaaldrich.com/content/dam/sigma- aldrich/docs/SAJ/Brochure/1/controlled-radical-polymerization-guide.pdf

As described on page 19 of the above-cited brochure, "in an ideal living polymerization, all chains are initiated at the beginning of the reaction, grow at a similar rate, and survive the polymerization: there is no irreversible chain transfer or termination. If initiation is rapid with respect to propagation, the molecular weight distribution is very narrow and chains can be extended by further adding monomers into the reaction. In a radical polymerization all chains cannot be simultaneously active. In RDRP, such as RAFT

polymerization, these attributes are displayed in the presence of reagents that are capable of reversibly deactivating propagating radicals such that the majority of living chains are maintained in a dormant form, and reaction conditions that support a rapid equilibrium between the active and dormant chains. Under these conditions, molecular weights can increase linearly with conversion, molecular weight distributions can be very narrow and the majority of the polymerization product should be comprised of dormant chains."

RAFT polymerization can be carried out by adding a RAFT agent to a system that is conventionally used in free radical polymerization, including the typically employed monomers, further components like initiators and solvents, and reaction conditions, Thus, for example, monomers with polymerizable groups like (meth)acrylate, (meth)acrylamide, acrylonitrile, styrene or a derivative thereof, butadiene, vinyl acetate and N-vinylpyrrolidone can be used. Typical classes of RAFT agents include thiocarbonylthio compounds such as dithioesters, di- or trithiocarbonates, di- or trithiocarbamates and xanthates. Above and below, the term "free form display" will be understood to mean a display that has either a permanent shape other than a plane-parallel shape, like for example a curved shape, or a flexible display. The term "flexible display" will be understood to mean a display which is bendable without breaking, like for example a display having flexible plastic substrates instead of rigid glass substrates and not comprising any other rigid layers. The term "curved display" will be understood to mean a display which has top and bottom subtrates that are not plane-parallel but curved.

Above and below, the term "flat display with reduced touch Mura sensitivity" will be understood to mean a display wherein irregular luminosity variation defects, which are caused by touching the front screen of a display, are reduced.

Above and below, the term“bi- or polycyclic group” will be understood to mean a group that consists of two or more fused rings, i.e. rings that share at least one common atom (in contrast to rings that are connected via covalent bonds between atoms belonging to different rings), wherein fusion of the rings occurs a) across a sequence of atoms (bridgehead), like for example in

bicyclo[2.2.1]heptane (norbornane) or tricyclo[3.3.3.1]decane (adamantane), hereinafter also referred to as“bridged bi- or polycyclic groups”,

b) across a bond between two atoms, like for example in bicyclo[4.4.0]decane (decalin), hereinafter also referred to as“fused bi- or polycyclic groups” c) at a single atom (spiro atom), like for example in spiro[4.5]decane, hereinafter also referred to as“spirocyclic groups”.

Unless indicated otherwise, the abbreviation "RM" is used above and below when referring to a reactive mesogen.

Above and below, polymerizable compounds or RMs with one polymerizable reactive group are also referred to as "monoreactive", polymerizable compounds or RMs with two polymerizable reactive groups are also referred to as "direactive", and polymerizable compounds or RMs with three

polymerizable reactive groups are also referred to as "trireactive". Unless indicated otherwise, the expression "LC mixture" is used when referring to the LC host mixture (i.e. without the RMs or polymerizable compounds), while the expression "LC medium" is used when referring to the LC host mixture plus the RM(s) or polymerizable compounds.

Unless stated otherwise, the polymerizable compounds and RMs are preferably selected from achiral compounds. As used herein, the terms "active layer" and "switchable layer" mean a layer in an electrooptical display, for example an LC display, that comprises one or more molecules having structural and optical anisotropy, like for example LC molecules, which change their orientation upon an external stimulus like an electric or magnetic field, resulting in a change of the transmission of the layer for polarized or unpolarized light.

As used herein, the terms "reactive mesogen" and "RM" will be understood to mean a compound containing a mesogenic or liquid crystalline skeleton, and one or more functional groups attached thereto which are suitable for polymerization and are also referred to as "polymerizable group" or "P".

Unless stated otherwise, the term "polymerizable compound" as used herein will be understood to mean a polymerizable monomeric compound. As used herein, the term "low-molecular-weight compound" will be

understood to mean to a compound that is monomeric and/or is not prepared by a polymerization reaction, as opposed to a "polymeric compound" or a "polymer". As used herein, the term "unpolymerizable compound" will be understood to mean a compound that does not contain a functional group that is suitable for polymerization under the conditions usually applied for the polymerization of the RMs or polymerizable compounds. The term "mesogenic group" as used herein is known to the person skilled in the art and described in the literature, and means a group which, due to the anisotropy of its attracting and repelling interactions, essentially contributes to causing a liquid-crystal (LC) phase in low-molecular-weight or polymeric substances. Compounds containing mesogenic groups (mesogenic corn- pounds) do not necessarily have to have an LC phase themselves. It is also possible for mesogenic compounds to exhibit LC phase behaviour only after mixing with other compounds and/or after polymerization. Typical mesogenic groups are, for example, rigid rod- or disc-shaped units. An overview of the terms and definitions used in connection with mesogenic or LC compounds is given in Pure Appi. Chem. 2001 , 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368.

The term "spacer group", hereinafter also referred to as "Sp", as used herein is known to the person skilled in the art and is described in the literature, see, for example, Pure Appi Chem. 2001 , 73(5), 888 and C. Tschierske, G. Pelzl, S. Diele, Angew. Chem. 2004, 116, 6340-6368. As used herein, the terms "spacer group" or "spacer" mean a flexible group, for example an alkylene group, which connects the mesogenic group and the polymerizable group(s) in a polymerizable mesogenic compound. Above and below,

denote a trans-1 ,4-cyclohexylene ring, and

denote a 1 ,4-phenylene ring. Above and below "organic group" denotes a carbon or hydrocarbon group.

"Carbon group" denotes a mono- or polyvalent organic group containing at least one carbon atom, where this either contains no further atoms (such as, for example, -CºC-) or optionally contains one or more further atoms, such as, for example, N, O, S, B, P, Si, Se, As, Te or Ge (for example carbonyl, etc.). The term "hydrocarbon group" denotes a carbon group which additionally contains one or more H atoms and optionally one or more heteroatoms, such as, for example, N, O, S, B, P, Si, Se, As, Te or Ge.

Halogen" denotes F, Cl, Br or I.

-CO-, -C(=0)- and -C(O)- denote a carbonyl group, i.e.

-CS-, -C(=S)- and -C(S)- denote a thiocarbonyl group, i.e.

A carbon or hydrocarbon group can be a saturated or unsaturated group.

Unsaturated groups are, for example, aryl, alkenyl or alkynyl groups. A carbon or hydrocarbon radical having more than 3 C atoms can be straight- chain, branched and/or cyclic and may also contain spiro links or condensed rings.

The terms "alkyl", "aryl", "heteroaryl", etc., also encompass polyvalent groups, for example alkylene, arylene, heteroarylene, etc.

The term "aryl" denotes an aromatic carbon group or a group derived therefrom. The term "heteroaryl" denotes "aryl" as defined above, containing one or more heteroatoms, preferably selected from N, O, S, Se, Te, Si and

Ge.

Preferred carbon and hydrocarbon groups are optionally substituted, straight- chain, branched or cyclic, alkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy having 1 to 40, preferably 1 to 20, very preferably 1 to 12, C atoms, optionally substituted aryl or aryloxy having 5 to 30, preferably 6 to 25, C atoms, or optionally substituted alkylaryl, arylalkyl, alkylaryloxy, arylalkyloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy having 5 to 30, preferably 6 to 25, C atoms, wherein one or more C atoms may also be replaced by hetero atoms, preferably selected from N, O, S, Se, Te, Si and Ge.

Further preferred carbon and hydrocarbon groups are C1-C20 alkyl, C2-C20 alkenyl, C2-C20 alkynyl, C3-C20 allyl, C₄-C2o alkyldienyl, C₄-C2o polyenyl, Ce- C20 cycloalkyl, C₄-Cis cycloalkenyl, C6-C30 aryl, C6-C3o alkylaryl, C6-C30 arylalkyl, C6-C30 alkylaryloxy, C6-C3o arylalkyloxy, C2-C30 heteroaryl, C2-C30 heteroaryloxy.

Particular preference is given to C1 -C12 alkyl, C2-C12 alkenyl, C2-C12 alkynyl, C6-C25 aryl and C2-C25 heteroaryl.

Further preferred carbon and hydrocarbon groups are straight-chain, branched or cyclic alkyl having 1 to 20, preferably 1 to 12, C atoms, which are unsubstituted or mono- or polysubstituted by F, Cl, Br, I or CN and in which one or more non-adjacent CFI2 groups may each be replaced, independently of one another, by -C(R^S1)=C(R^S1)-, -CºC-, -N(R^S1)-, -0-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O - in such a way that O and/or S atoms are not linked directly to one another, and

R^S1 denotes H, F, Cl, CN, a straight-chain, branched or cyclic alkyl chain having 1 to 25 C atoms, in which, in addition, one or more non-adjacent C atoms may be replaced by -O-, -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- and in which one or more FI atoms may be replaced by F or Cl, or denotes an optionally substituted aryl or aryloxy group with 6 to 30 C atoms, or an optionally substituted heteroaryl or heteroaryloxy group with 2 to 30 C atoms.

Preferred alkyl groups are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, s-butyl, t-butyl, 2-methylbutyl, n-pentyl, s-pentyl, cyclopentyl, n-hexyl, cyclohexyl, 2-ethyl hexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, dodecanyl, trifluoromethyl, perfluoro- n-butyl, 2,2,2-trifluoroethyl, peril uorooctyl, perfluorohexyl, etc. Preferred alkenyl groups are, for example, ethenyl, propenyl, butenyl, pentenyl, cyclopentenyl, hexenyl, cyclohexenyl, heptenyl, cycloheptenyl, octenyl, cyclooctenyl, etc.

Preferred alkynyl groups are, for example, ethynyl, propynyl, butynyl, pentynyl, hexynyl, octynyl, etc. Preferred alkoxy groups are, for example, methoxy, ethoxy, 2-methoxy- ethoxy, n-propoxy, i-propoxy, n-butoxy, i-butoxy, s-butoxy, t-butoxy, 2- methylbutoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n- decoxy, n-undecoxy, n-dodecoxy, etc.

Preferred amino groups are, for example, dimethylamino, methylamino, methylphenylamino, phenylamino, etc.

Aryl and heteroaryl groups can be monocyclic or polycyclic, i.e. they can contain one ring (such as, for example, phenyl) or two or more rings, which may also be fused (such as, for example, naphthyl) or covalently bonded (such as, for example, biphenyl), or contain a combination of fused and linked rings. Heteroaryl groups contain one or more heteroatoms, preferably selected from O, N, S and Se.

Particular preference is given to mono-, bi- or tricyclic aryl groups having 6 to 25 C atoms and mono-, bi- or tricyclic heteroaryl groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6- or 7-membered aryl and heteroaryl groups, in which, in addition, one or more CH groups may be replaced by N,

S or O in such a way that O atoms and/or S atoms are not linked directly to one another.

Preferred aryl groups are, for example, phenyl, biphenyl, terphenyl,

[1 ,1 ':3',1 "]terphenyl-2'-yl, naphthyl, anthracene, binaphthyl, phenanthrene,

9,10-dihydro-phenanthrene, pyrene, dihydropyrene, chrysene, perylene, tetracene, pentacene, benzopyrene, fluorene, indene, indenofluorene, spirobifluorene, etc. 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, selenophene, oxazole, isoxazole, 1 ,2-thiazole, 1 ,3-thiazole, 1 ,2,3- oxadiazole, 1 ,2,4-oxadiazole, 1 ,2,5-oxadiazole, 1 ,3,4-oxadiazole, 1 ,2,3- thiadiazole, 1 ,2,4-thiadiazole, 1 ,2,5-thiadiazole, 1 ,3,4-thiadiazole, 6-membered rings, 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 condensed groups, such as indole, isoindole, indolizine, indazole,

benzimidazole, benzotriazole, purine, naphthimidazole, phenanthrimidazole, pyridimidazole, pyrazinimidazole, quinoxalinimidazole, benzoxazole, naphthoxazole, anthroxazole, phenanthroxazole, isoxazole, benzothiazole, benzofuran, isobenzofuran, dibenzofuran, quinoline, isoquinoline, pteridine, benzo-5, 6-quinoline, benzo-6, 7-quinoline, benzo-7, 8-quinoline, benzoisoquin- oline, acridine, phenothiazine, phenoxazine, benzopyridazine, benzopyrimi- dine, quinoxaline, phenazine, naphthyridine, azacarbazole, benzocarboline, phenanthridine, phenanthroline, thieno[2,3b]thiophene, thieno[3,2b]thiophene, dithienothiophene, isobenzothiophene, dibenzothiophene, benzothiadiazo- thiophene, or combinations of these groups.

The aryl and heteroaryl groups mentioned above and below may also be substituted by alkyl, alkoxy, thioalkyl, fluorine, fluoroalkyl or further aryl or heteroaryl groups.

The (non-aromatic) alicyclic and heterocyclic groups encompass both saturated rings, i.e. those containing exclusively single bonds, and also partially unsaturated rings, i.e. those which may also contain multiple bonds. Heterocyclic rings contain one or more heteroatoms, preferably selected from Si, O, N, S and Se.

The (non-aromatic) alicyclic and heterocyclic groups can be monocyclic, i.e. contain only one ring (such as, for example, cyclohexane), or polycyclic, i.e. contain a plurality of rings (such as, for example, decahydronaphthalene or bicyclooctane). Particular preference is given to saturated groups. Preference is furthermore given to mono-, bi- or tricyclic groups having 5 to 25 ring atoms, which optionally contain fused rings and are optionally substituted. Preference is furthermore given to 5-, 6-, 7- or 8-membered carbocyclic groups, in which, in addition, one or more C atoms may be replaced by Si and/or one or more CH groups may be replaced by N and/or one or more non-adjacent CH2 groups may be replaced by -O- and/or -S-.

Preferred alicyclic and heterocyclic groups are, for example, 5-membered groups, such as cyclopentane, tetrahydrofuran, tetrahydrothiofuran, pyrroli dine, 6-membered groups, such as cyclohexane, silinane, cyclohexene, tetrahydropyran, tetrahydrothiopyran, 1 ,3-dioxane, 1 ,3-dithiane, piperidine, 7-membered groups, such as cycloheptane, and fused groups, such as tetrahydronaphthalene, decahydronaphthalene, indane, bicyclo[1.1.1 ]- pentane-1 ,3-diyl, bicyclo[2.2.2]octane-1 ,4-diyl, spiro[3.3]heptane-2,6-diyl, octahydro-4,7-methanoindane-2,5-diyl.

Preferred substituents are, for example, solubility-promoting groups, such as alkyl or alkoxy, electron-withdrawing groups, such as fluorine, nitro or nitrile, or substituents for increasing the glass transition temperature (Tg) in the polymer, in particular bulky groups, such as, for example, t-butyl or optionally substituted aryl groups.

Preferred substituents, hereinafter also referred to as L^s, are, for example, F, Cl, Br, I, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^s)₂, -C(=0)Y^s, - C(=0)R^s, -N(R^s)₂, straight-chain or branched alkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy or alkoxycarbonyloxy each having 1 to 25 C atoms, in which one or more H atoms may optionally be replaced by F or Cl, optionally substituted silyl having 1 to 20 Si atoms, or optionally substituted aryl having 6 to 25, preferably 6 to 15, C atoms, wherein R^s denotes FI, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CFI₂-groups are optionally replaced by -0-, -S-, -CO-, -CO-0-, -O-CO-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more FI atoms are each optionally replaced by F or Cl,

Y^s denotes halogen, preferably F.

"Substituted silyl or aryl" preferably means substituted by halogen, -CN, R°, -OR⁰, -CO-R⁰, -CO-O-R⁰, -O-CO-R⁰ or -O-CO-O-R⁰, wherein R° denotes

FI or alkyl with 1 to 20 C atoms.

Particularly preferred substituents L are, for example, F, Cl, CN, N0₂, CFb, C₂H₅, OCHS, OC₂H₅, COCHS, COC₂H₅, COOCHS, COOC₂H₅, CF₃, OCF₃, OCFIF₂, OC₂F5, furthermore phenyl.

in which L has one of the meanings indicated above and r is 0, 1 , 2, 3 or 4.

The polymerizable group P, P^x or P¹·² is a group which is suitable for a free- radical polymerization. Particular preference is given to groups for chain polymerization, in particular those containing a C=C double bond or -CºC- triple bond, and groups which are suitable for polymerization with ring opening, such as, for example, oxetane or epoxide groups.

Preferred groups P, P^x and P^{1 2} are selected from the group consisting of

CH₂)₂N-CO-, CH₂=CW¹-CO-NH-, CH₂=CH-(C00)ki-Phe-(0)k2-, CH₂=CH- (CO)_ki-Phe-(0)_k2-, Phe-CH=CH-, which W¹ denotes H, F, Cl, CN, CF₃, phenyl or alkyl having 1 to 5 C atoms, in particular FI, F, Cl , CFI₃ or C₂Fl5, W² denotes FI or alkyl having 1 to 5 C atoms, in particular FI, methyl, ethyl or n-propyl, W³ and W⁴ each, independently of one another, denote FI, Cl or alkyl having 1 to 5 C atoms, Phe denotes 1 ,4-phenylene, which is optionally substituted by one or more radicals L as defined above which are other than R-Sp-, ki, k₂ and k₃ each, independently of one another, denote 0 or 1 , k₃ preferably denotes 1 , and k₄ denotes an integer from 1 to 10.

Very preferred groups P, P^x and P^{1 2} are selected from the group consisting of CH₂=CW¹-CO-0-, in particular CH₂=CH-CO-0-, CH₂=C(CH₃)-C0-0- and CH₂=CF-CO-0-, furthermore CH₂=CH-0-, (CH₂=CH)₂CH-0-C0-, and

(CH₂=CH)₂CH-0-. Further preferred polymerizable groups P, P^x and P¹·² are selected from the group consisting of vinyloxy, acrylate, methacrylate, ethacrylate (which is CH₂=CW¹-C0-0- wherein W¹ is ethyl), fluoroacrylate and chloroacrylate, most preferably from acrylate and methacrylate.

If Sp, Sp^x or Sp¹·² is different from a single bond, it is preferably selected of the formula Sp"-X", so that the respective radical P-Sp- conforms to the formula P-Sp"-X"-, wherein

Sp" denotes straight-chain ir branched alkylene having 1 to 40, preferably 1 to 20, C atoms, which is optionally mono- or polysubstituted by F, Cl,

CN or P, and in which, in addition, one or more non-adjacent CFh groups may each be replaced, independently of one another, by -0-, - S-, -NH-, -N(R⁰)-, -Si(R°R⁰⁰)-, -CO-, -CO-0-, -O-CO-, -0-C0-0-, -S-CO-

, -CO-S-, -N(R⁰⁰)-CO-O-, -0-CO-N(R°)-, -N(R°)-CO-N(R⁰⁰)-, -CH=CH- or -CºC- in such a way that O and/or S atoms are not linked directly to one another, X" denotes -O-, -S-, -CO-, -C0-0-, -O-CO-, -0-C0-0-, -CO-N(R⁰)-, -N(R°)- CO-, -N(R°)-CO-N(R⁰⁰)-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, - OCF2-, -CF2S-, -SCF2-, -CF2CH2-, -CH2CF2-, -CF2CF2-, -CH=N-, - N=CH-, -N=N-, -CH=CR⁰-, -CY²=CY³-, -CºC-, -CH=CH-C0-0-, -O-CO- CFI=CFI- or a single bond,

R° and R°° each, independently of one another, denote FI or alkyl having 1 to 20 C atoms, and

Y² and Y³ each, independently of one another, denote FI, F, Cl or CN.

X" is preferably -0-, -S-, -CO-, -COO-, -OCO-, -O-COO-, -CO-NR⁰-, -NR°- CO-, -NR°-CO-NR°°- or a single bond.

Typical spacer groups Sp, Sp^x, Sp¹·² and -Sp"-X"- are, for example, -(CFh)pi-, -(CH₂CH₂0)qi-CH₂CH₂-, -CH₂CH₂-S-CH₂CH₂-, -CH₂CH₂-NH-CH₂CH₂- or -(SiR°R⁰⁰-O)_pi-, in which p1 is an integer from 1 to 20, q1 is an integer from 1 to 6, and R° and R⁰⁰ have the meanings indicated above. Particularly preferred groups Sp, Sp^x, Sp¹·² and -Sp”-X”- are -(CH₂)_PI-, -(CH₂)_PI- 0-, -(CH₂)_PI-0-C0-, -(CH₂)_PI-C0-0-, -(CH₂)_PI-0-C0-0-, in which p1 and q1 have the meanings indicated above.

Particularly preferred groups Sp" are, in each case straight-chain, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, dodecylene, octadecylene, ethyleneoxyethylene, methyleneoxybutylene, ethylenethioethylene, ethylene-N-methylimino- ethylene, 1-methylalkylene, ethenylene, propenylene and butenylene. Detailed Description of the Invention

The LC medium and the process of preparing polymer walls according to the present invention provide significant advantages over the materials and processes of prior art, like better phase separation between the polymer walls and the LC molecules, and the formation of stronger and harder polymer walls with higher stability against mechanical and/or thermal stress.

In the method of preparing polymer walls in an LC display two processes occur simultaneously: a) polymerization of the polymerizable monomers by chain propagation in the LC medium and b) phase separation between the LC molecules and the propagating polymer chains. However, the

polymerization reaction is usually much faster, typically in the range of a few milliseconds, while the phase separation is much slower, typically in the range of several minutes.

The use of a RAFT agent is expected to slow down the chain propagation reaction and thus level the time scales of the two processes. This is expected to enable a higher degree of phase separation, and to allow using a higher amount of di- or multireactive monomers which leads to the formation of polymer walls with higher stability and mechanical strength. The RAFT agent is preferably selected from thiocarbonyl compounds, very preferably from dithioesters, di- or trithiocarbonates, di- or trithiocarbamates, dithiobenzoates and xanthates. Suitable RAFT agents are commercially available for example from Sigma- Aldrich, and are also described in the literature, for example in the following brochure and the articles cited therein: https://www.sigmaaldrich.com/content/dam/sigma- aldrich/docs/SAJ/Brochure/1/controlled-radical-polymerization-guide.pdf

Preferably the RAFT agent is selected from formula I

wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings

X¹ -S-R^b, -0-R^b, -N(R^bR^c) or aryl or heteroaryl having 5 to 20 ring

atoms that is optionally substituted by L,

R^a straight-chain or branched or cyclic alkyl with 1 to 60 C atoms that is optionally fluorinated, and wherein one or more CFh-groups are optionally replaced by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -0-, -S-, -CO- or -CS- or by a polyglycol chain -(CFhCFhOV in such a way that O and/or S atoms are not linked directly to one another, and in which one or more FI atoms are optionally replaced by F, Cl, Br, I, CN or N3, or by a heterocyclic, aromatic or heteroaromatic group having 5 to 20 ring atoms that is optionally substituted by one or more groups L, or R^a is aryl or heteroaryl having 5 to 20 ring atoms, preferably phenyl, that is optionally substituted by one or more groups L,

R^b, R^c FI or one of the meanings given for R^a, or R^b and R^c together with the N-atom to which they are attached may also form a heterocyclic or heteroaromatic group with 5 to 8 ring atoms that is optionally substituted by L.

L F, Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^q)₂, - C(=0)Y^z, -C(=0)R^q, -N(R^q)₂, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight- chain or branched alkyl having 1 to 25 C atoms in which, in addition, one or more non-adjacent CFI₂ groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -O- , -S-, -CO-, -CS-, -CO-0-, -O-CO-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more FI atoms may be replaced by F, Cl, -CN,

R^q H, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to

25 C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -0-, -S-, -CO-, -C0-0-, -0-C0-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,

R°, R⁰⁰ FI or alkyl having 1 to 20 C atoms,

Y^z halogen, preferably F or Cl n an integer >1 , preferably from 1 to 300, or from 1 to 12.

Very preferably the RAFT agent is selected from the following subformulae

R^a, R^b, R^c one of the meanings given in formula I,

R^d straight-chain or branched alkylene with 2 to 30 C atoms, wherein one or more CFte groups are optionally replaced by -0-, -CO- or -( ChteChteOJn-, and wherein one or more H atoms are optionally replaced by CN,

R^e straight-chain or branched or cyclic alkyl with 1 to 20 C atoms that is optionally fluorinated, and wherein one or more CFte-groups are optionally replaced by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -0-, -S-, -CO-

,-CS- or -(ChteChteOJ_n- in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, Br, I, CN or N3, or by a heterocyclic, aromatic or heteroaromatic group having 5 to 20 ring atoms that is optionally substituted by one or more groups L, or R^c1 is aryl or heteroaryl having 5 to 20 ring atoms, preferably phenyl, that is optionally substituted by one or more groups L,

Ar aryl or heteroaryl with 5 to 8 ring atoms, very preferably phenyl, which is optionally substituted by one or more groups L as defined in formula I, n an integer >1 , preferably from 1 to 300 or from 1 to 12.

More preferably the RAFT agent is selected from the following subformulae

R^a1 H, R^b1 , -(CH₂CH₂0)_n-CH3, phenyl, pentafluorophenyl or R^a2 H, R^b1 , phenyl or CN,

R^b1 straight-chain or branched alkyl with 1 to 20 C atoms, wherein one or more H atoms are optionally replaced by OH, CN or N3,

R^d1 alkylene with 2 to 20 C atoms or -(CH₂CH₂0)_n-,

Y³, Y⁴ H, CHs, CN or phenyl

L one of the meanings given in formula I k O oM , n an integer >1 , preferably from 1 to 300 or from 1 to 12, r 0, 1 , 2, 3 or 4, s 0, 1 or 2. In the above formulae preferably Y³ and Y⁴ are not at the same time CN . Very preferably one of Y³ and Y⁴ is CH3 and the other is CN, or or both Y³ and Y⁴ are CH3, or one of Y³ and Y⁴ is H and the other is CH3 or CN, or both Y³ and Y⁴ are H, or one of Y³ and Y⁴ is H and the other is phenyl .

Further preferably, if in the above formulae one of Y³ and Y⁴ is CN then R^a2 is different from CN.

Most preferably the RAFT agent is selected from the following subformulae

-30-

I3b2

I3b3

I3b4

I4a1

I4b1

I4c1

I5a1N

wherein n is as defined above.

In a preferred embodiment the polymerizable component A comprises two or more RAFT agents, preferably selected from formula I and its preferred subformulae.

The concentration of the RAFT agents in the LC medium is preferably from 0.01 to 10%, very preferably from 0.1 to 8%, most preferably from 0.1 to 5%.

Preferably, the polymerizable compounds of component A are selected from compounds having one, two, three or four polymerizable groups, more preferably from compounds having one, two or three polymerizable groups, most preferably from compounds having one or two polymerizable groups.

Preferably, the polymerizable component A comprises one or more first polymerizable compounds comprising a straight-chain or branched hydrocarbon group having from 1 to 30 C atoms, or a monocyclic hydrocarbon group having from 3 to 24 ring atoms, or a bi- or polycyclic hydrocarbon group having from 4 to 30 ring atoms, and attached thereto (exactly) one polymerizable group, and one or more second polymerizable compounds comprising a straight-chain, branched or cyclic hydrocarbon group having from 1 to 30 C atoms, and attached thereto two or more polymerizable groups. Preferably component A of the LC medium comprises one or more first polymerizable compounds selected of formula II

P-Sp-G¹ II wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings

P a polymerizable group,

Sp a spacer group or a single bond,

G¹ a straight-chain or branched alkyl group with 1 to 20 C atoms, or a monocyclic alkyl group with 3 to 24 C atoms, that is optionally mono-, poly- or peril uorinated and is optionally substituted by one or more groups L, and wherein one or more CFI₂-groups are optionally replaced by -O-, -CO-, -O-CO- or -CO-O- such that O- atoms are not directly adjacent to one another, L F, Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^q)₂, -

C(=0)Y^z, -C(=0)R^q, -N(R^q)₂, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight- chain or branched alkyl having 1 to 25 C atoms in which, in addition, one or more non-adjacent CH₂ groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -O-

, -S-, -CO-, -C0-0-, -0-C0-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more H atoms may be replaced by F, Cl, -CN,

R^q FI, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to

25 C atoms, wherein one or more non-adjacent CFI₂-groups are optionally replaced by -O-, -S-, -CO-, -CO-0-, -O-CO-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more FI atoms are each optionally replaced by F or Cl, R°, R⁰⁰ H or alkyl having 1 to 20 C atoms,

Y^z halogen, preferably F or Cl. P is preferably acrylate or methacrylate.

Sp is preferably of the formula Sp"-X", so that the respective radical P-Sp- conforms to the formula P-Sp"-X"-, wherein Sp” and X” are as defined above. Sp is very preferably -(CFteJpi-, -(CH₂)_PI-0-, -(CH₂)_PI-0-C0-,

-(CH₂)_PI-C0-0-, -(CH₂)_PI-0-C0-0-, in which p1 is an integer from 1 to 12.

L is preferably selected from F, Cl, -CN and straight-chain or branched alkyl having 1 to 25, particularly preferably 1 to 10, C atoms, in which, in addition, one or more non-adjacent CFh groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -0-, -S-, -CO-, -CO-O- , -O-CO-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more FI atoms may be replaced by F, Cl, Br, I or CN.

L is very preferably selected from F, -CN, and alkyl or alkoxy with 1 to 6 C atoms that is optionally fluorinated, preferably F, Cl, CN, CFb, OCFI3, OCF3, OCF2FI or OCFFI2, very preferably F. Preferred compounds of formula II are selected from the following formulae

P-Sp-(CHW¹¹)n2-(CH₂)ni-(CHW¹²)n3-CH₃ 111

P-Sp-(CH₂)_n2-(CF₂)_ni-CFW¹³W¹⁴ M2

wherein the individual radicals, independently of each other and on each occurrence identically or differently, have the following meanings

P, Sp have the meanings given in formula II or one of the preferred meanings given above and below,

W¹¹, W¹² are H, F or straight-chain or branched Ci-Ci2-alkyl,

W¹³, W¹⁴ are H or F n1 is an integer from 2 to 15, n2, n3 are 0 or an integer from 1 to 3, Very preferred compounds of formula II are selected from the following formulae

wherein W is FI, CFb or C₂Fl₅, and W^{1 1} , W¹², W¹³, W¹⁴, n1 , n2 and n3 are as defined in formula 111 and M2, n4 is 0 or an integer from 1 to 15, s is 0 or 1 , and if s is 1 then n4 is not 0.

Further preferred compounds of formula II are selected from the following formulae



M4a4

M5a

M5b

M6a

M6b

M7a

In another preferred embodiment of the present invention component A of the LC medium comprises one or more first polymerizable compounds

comprising a polymerizable group and a bi- or polycylic hydrocarbon group having from 4 to 30 ring atoms, preferably from 6 to 25 ring atoms, which is preferably a non-aromatic hydrocarbon group.

Preferably component A of the LC medium according to this preferred embodiment comprises, in addition or alternatively to the compounds of formula II, one or more polymerizable compounds selected of formula IIA

P-Sp-G² IIA wherein P and Sp have the meanings given in formula II or one of the preferred meanings given above and below, and G² is a bi- or polycyclic hydrocarbon group, preferably a bridged or fused bi- or polycyclic alkyl group, having 4 to 30 ring atoms, preferably 6 to 25 ring atoms, which is optionally substituted by one or more groups L as defined in formula II.

Preferably the bi- or polycyclic hydrocarbon group or group G² is a bi-, tri- or tetracyclic group.

Preferably the bi- or polycyclic hydrocarbon group or group G² is a bridged bi- or polycyclic hydrocarbon group, i.e. which consists of fused hydrocarbon rings, preferably fused cycloalkyl rings, where fusion occurs across a sequence of atoms (bridgehead), preferably a bipodal bridge, like in bicyclo[2.2.1]heptane (norbornane), bicyclo[2.2.2]octane or

tricyclo[3.3.3.1]decane (adamantane).

In another preferred embodiment the present invention the bi- or polycyclic hydrocarbon group or group G^2A is a fused bi- or polycyclic hydrocarbon group, i.e. which consists of fused hydrocarbon rings, preferably fused cycloalkyl rings, where fusion occurs across a bond between two atoms, like in bicyclo[3.2.0]heptane or bicyclo[4.4.0]decane (decalin).

In yet another preferred embodiment the present invention the bi- or polycyclic hydrocarbon group or group G² is a spirocyclic group, i.e. which consists of fused hydrocarbon rings, preferably fused cycloalkyl rings, where fusion occurs at a single atom (spiro atom), like in spiro[3.3]heptane or spiro[4.5]decane.

The bi- or polycyclic group or group G² is optionally substituted by one or more substituents, preferably selected from the group L as defined above and below.

Preferably the bi- or polycyclic group or group G² is selected from the group consisting of bicyclo[1.1.1 ]pentyl, bicyclo[2.1 1]hexyl, bicyclo[2.2.1]heptyl (norbornyl), bicyclo[3.2.1]octyl, bicyclo[2.2.2]octyl, bicyclo[3.2.2]nonyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2]decyl, bicyclo[3.3.3]undecyl,

tricyclo[3.3.3.1]decyl (adamantyl), tricyclo[5.2.1.0]decyl (tetrahydrodicyclopentadiyl), bicyclo[2.1 .0]pentyl, bicyclo[2.2.0]hexyl, bicyclo[3.2.0]heptyl, bicyclo[4.2.0]octyl, bicyclo[3.3.0]octyl,

bicyclo[4.3.0]nonyl, bicyclo[4.4.0]decyl (decalin), spiro[2.2]pentyl,

spiro[3.2]hexyl, spiro[3.3]heptyl, spiro[4.3]octyl, spiro[4.4]nonyl,

spiro[4.5]decyl, all of which are optionally substituted by one or more groups L as defined in formula I.

Very preferably the bi- or polycyclic group or group G² is selected from the group consisting of bicyclo[1 .1 .1 ]pentyl, bicyclo[2.1 1 ]hexyl,

bicyclo[2.2.1 ]heptyl (norbornyl), bicyclo[3.2.1 ]octyl, bicyclo[2.2.2]octyl, bicyclo[3.2.2]nonyl, bicyclo[3.3.1]nonyl, bicyclo[3.3.2]decyl,

bicyclo[3.3.3]undecyl, tricyclo[3.3.3.1 ]decyl (adamantyl), all of which are optionally substituted by one or more groups L as defined in formula I. Most preferably the bi- or polycyclic group or group G² is selected from the group consisting of bicyclo[2.2.1 ]heptyl (norbornyl), bicyclo[2.2.2]octyl, tricyclo[3.3.3.1 ]decyl (adamantyl), all of which are optionally substituted by one or more groups L as defined above and below. Preferred compounds of formula IIA are selected from the following formulae

IIAA

NAB

MAC

wherein R on each occurrence identically or differently denotes P-Sp- or has one of the meanings given for R^q above, and one of the groups R in each of formulae IIAA-IIAC denotes P-Sp-. Further preferred compounds of formula IIA are selected from the following formulae

IIA1

IIA2

11 A3

IIA4

wherein P and Sp have the meanings given in formula IIA or one of the preferred meanings given above, W^{1 1} , W¹² and W¹³ are independently of each other H, F or Ci-Ci2-alkyl, preferably methyl, and the cycloalkyl groups are optionally substituted with one or more groups L as defined above.

Very preferred compounds of formula IIA are selected from the following formulae

wherein n is 0 or an integer from 1 to 8, W is H, CFb or C2H5 and W¹¹, W¹² and W¹³ are H, F or Ci-Ci2-alkyl, preferably methyl.

Further preferred compounds of formula IIA are selected from the following formulae

IIA1a2

IIA2a1

IIA2a2

IIA3a1

IIA3a2

IIA3a3

Preferably component A of the LC medium comprises one or more second polymerizable compounds selected of formula III P¹-Sp¹-G³-Sp²-P² III wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings p¹ and P² a polymerizable group,

Sp¹, Sp² a spacer group or a single bond,

G³ is a straight-chain, branched or cyclic alkyl group with 1 to 20 C atoms that is optionally mono-, poly- or perfluorinated and is optionally substituted by one or more groups P¹-Sp¹- or by one or more groups L as defined in formula II, and wherein one or more Chh-groups are optionally replaced by -0-, -CO-, -O-CO- or -CO- O- such that O-atoms are not directly adjacent to one another.

P¹ and P² are preferably selected from acrylate, methacrylate, ethacrylate, and vinyloxy groups.

Sp¹ and Sp² in formula III preferably denote a single bond.

If the hydrocarbon group or group G³ in the second polymerizable

compounds is a cyclic group, it is preferably a monocyclic cycloalkyl group, which preferably has from 5 to 7 ring atoms and is optionally substituted by one or more groups L as defined in formula II.

In another preferred embodiment of the present invention the hydrocarbon group or group G³ in the second polymerizable compounds is a bi-, tri- or tetracyclic group, and preferably has from 4 to 30 C atoms, which is optionally substituted by one or more groups L as defined above and below. Preferred bi-, tri- or tetracyclic groups or groups G³ in the second polymerizable compound are those having one of the meanings of group G^2A in formula IIA or its preferred meanings given above.

Preferred compounds of formula III are selected from the following formulae

P¹ -Sp¹ -(CH W^{1 1} )n2-(CH₂)n1 -(CH W¹²)_n3-Sp²-P² 1111

I M2

P¹-(CH₂)n2-(CF2)n1-(CH₂)n3-P² III3

(P¹-Sp¹-(CH₂)n4)n5CH_4-n5 III4 wherein P¹ , P², Sp¹ , Sp² are as defined in formula III,

W^{1 1} , W¹² are, on each occurrence identically or differently, H, F or Ci-Ci₂- alkyl, n1 is an integer from 2 to 15, n2, n3 are independently of each other 0 or an integer from 1 to 3, n4 is 0 or an integer from 1 to 15, n5 is 3 or 4 and the cyclohexylene ring in formula III2 is optionally substituted by one or more identical or different groups W^{1 1}.

In a preferred embodiment of the present invention the component A of the LC medium comprises one or more second polymerizable compounds wherein the two polymerizable groups are different from each other.

Preferably in this preferred embodiment the component A of the LC medium comprises one or more compounds of formula III or its subformulae wherein P¹ and P² are different from each other. Preferably in these compounds of formula III one of P¹ and P² is vinyloxy and the other is acrylate, methacrylate or ethacrylate, most preferably methacrylate. In another preferred embodiment of the present invention the component A of the LC medium comprises one or more compounds of formula III or its subformulae wherein P¹ and P² are identical groups.

In the third polymerizable compounds, the polymerizable groups are preferably selected from acrylate, methacrylate, ethacrylate and vinyloxy groups. Very preferably one of the polymerizable groups is vinyloxy and the other is acrylate or methacrylate, most preferably methacrylate.

Very preferred compounds of formula III are selected from the following formulae

CH₂=CW-C0-0-(CHW¹¹)n4-(CH₂)ni-0-CH=CH2 1111 a

CH₂=CH-0-(CHW¹¹)_n4-(CH₂)_ni-0-C0-CW=CH₂ 1111 b

CH₂=CW-C0-0-(CHW¹¹ )_n2-(CH₂)_ni-(CHW¹²)_n3-0-C0-CW=CH₂ 1111 c

CH₂=CW-C0-0-(CH2)n2-(CF2)n1-(CH₂)n3-0-CH=CH2 1113a

CH₂=CW-C0-0-(CH2)n2-(CF2)n1-(CH₂)n3-0-C0-CW=CH2 1113b

(CH₂=CW-C0-0-(CH₂)n₂)₃CH 1114a

(CH₂=CW-C0-0-(CH₂)n₂)₄C 1114b wherein W is FI, CFI3 or C2FI5 and W^{1 1} , W¹², n1 , n2 and n4 are as defined in formula III1 -III4, and the cyclohexylene ring in formula IM2a-c is optionally substituted by one or more identical or different groups W^{1 1}.

Further preferred compounds of formula III are selected from the following formulae

1114a2

IM4b1

IM5a1

IM5a2 In another preferred embodiment of the present invention component A of the LC medium additionally comprises one or more third polymerizable compounds comprising a cinnamate group of which the O atom is connected to an acrylate or methacrylate group via a hydrocarbon spacer group having from 2 to 20 C atoms.

Preferably the third polymeriziable compounds with a cinnamate group are selected of formula IV

P^x an acrylate or methacrylate group,

Sp^x straight chain, branched or cyclic alkylene having 2 to 20 C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -0-, -S-, -CO-, -C0-0-, -0-C0-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other,

R^x H, F, Cl, CN, P^x, P^x-Sp^x-, R^y, R^y-0-CO-CH=CH-,

P^x-Sp^x-0-CO-CH=CH-, R^y-CH=CH-CO-0-, P^x-Sp^x-CH=CH-CO-0-,

R^y straight chain, branched or cyclic alkyl having 1 to 25 C atoms,

wherein one or more non-adjacent CFh-groups are optionally replaced by -O-, -S-, -NR⁰-, -CO-, -C0-0-, -0-C0-, -O-CO-O- , -C(R°)=C(R⁰⁰)- or -CºC- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl, A^x an aromatic, heteroaromatic, alicyclic or heterocyclic group having 4 to 25 ring atoms, which may also contain fused rings, and which is unsubstituted, or mono- or polysubstituted by L,

-O-, -S-, -CO-, -C0-0-, -OCO-, -O-CO-O-, -OCH2-, -CH2O-, -SCH2-, - CH₂S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH₂)nii-, -CF2CH2-, - CH2CF2-, -(CF₂)nii-, -CH=CH-, -CF=CF-, -CºC-, -CH=CH-COO-, - OCO-CH=CH-, CR°R⁰⁰ or a single bond, L F, Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^q)₂,

-C(=0)Y^z, -C(=0)R^q, -N(R^q)2, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight- chain or branched alkyl having 1 to 25 C atoms in which, in addition, one or more non-adjacent CFI2 groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -O- , -S-, -CO-, -CO-O-, -O-CO-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more FI atoms may be replaced by F, Cl, -CN, R^q H, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -0-, -S-, -CO-, -C0-0-, -0-C0-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,

R°, R⁰⁰ FI or alkyl having 1 to 20 C atoms

Y^z halogen, preferably F or Cl, ml 0, 1 or 2, n1 1 1 , 2, 3 or 4. In a preferred embodiment of the present invention R^x is selected from P^x, P^x- Sp^x-, P^x-Sp^x-0-C0-CH=CH- and P^x-Sp^x-CH=CH-C0-0-, wherein P^x and Sp^x are as defined above and below. In another preferred embodiment of the present invention R^x is straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non- adjacent CFte-groups are optionally replaced by -0-, -S-, -NR⁰-, -CO-, -C0-0-, - 0-C0-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl.

Sp^x is preferably selected from -(CFteJpi-, -(CH₂)_PI-0-, -(CH₂)_PI-0-C0-,

-(CH₂)_PI-C0-0- or -(CH₂)_PI-0-C0-0-, wherein p1 is an integer from 2 to 12, and wherein Sp^x is linked to a group P^x or to a cinnamate group such that O atoms are not directly connected to each other.

In a preferred embodiment of the present invention ml is 0. In another preferred embodiment of the present invention ml is 1 or 2. A^x is preferably selected from,4-phenylene, 1 ,3-phenylene, naphthalene-1 ,4- diyl, naphthalene-2, 6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro-phenanthrene- 2,7-diyl, anthracene-2, 7-diyl, fluorene-2,7-diyl, coumarine, flavone, where, in addition, one or more CH groups in these groups may be replaced by N, cyclohexane-1 ,4-diyl, in which, in addition, one or more non-adjacent CFte groups may be replaced by O and/or S, 1 ,4-cyclohexenylene, bicyclo[1.1.1]- pentane-1 ,3-diyl, bicyclo[2.2.2]octane-1 ,4-diyl, spiro[3.3]heptane-2, 6-diyl, piperidine-1 ,4-diyl, decahydronaphthalene-2, 6-diyl, 1 , 2,3,4- tetrahydronaphthalene-2, 6-diyl, indane-2,5-diyl or octahydro-4,7- methanoindane-2,5-diyl, where all these groups may be unsubstituted or mono- or polysubstituted by L as defined above.

Very preferably A^x is selected from 1 ,4-phenylene, naphthalene-2, 6-diyl and cyclohexane-1 ,4-diyl, which are unsubstituted or mono- or polysubstituted by L as defined above. Z^x is preferably selected from -C0-0-, -OCO-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -CF₂S-, -(CH₂)nii-, -CH=CH-, -CF=CF-, -CºC-, -CH=CH-COO-, -OCO-CH=CH- or a single bond. Preferred compounds of formula IV are selected from the following formulae

wherein P^x, Sp^x, R^x and L have the meanings given in formula IV or one of the preferred meanings given above and below, and r is 0, 1 , 2, 3 or 4.

Very preferred are compounds of formula IV1 -IV4. In formula IV1 -IV12 R^x preferably denotes F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25, preferably 1 to 12, C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -0-, -S-, - CO-, -C0-0-, -0-C0-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl.

Very preferred compounds of formula IV are selected from the following formulae

IV4b

Further preferred are compounds of formula IV1 -IV4b wherein the acrylate groups are replaced by methacrylate groups.

In another preferred embodiment of the present invention component A of the LC medium additionally comprises one or more fourth polymerizable compounds comprising a maleimide group, which are preferably selected of formula V

R^d-sp^y-(A^y-z^y)_mi-sp^y-R^e v wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings

R^d, R^e H, F, Cl, CN, P^y or R^z, wherein at least one of R^d and R^e is P^y,

Spy straight chain, branched or cyclic alkylene having 1 to 20 C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -0-, -S-, -CO-, -CO-0-, -O-CO-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, or a single bond,

R^m, Rⁿ FI or alkyl having from 1 to 5 C atoms R^z straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent Chh-groups are optionally replaced by -0-, -S-, -NR⁰-, -CO-, -C0-0-, -0-C0-, -O-CO-O- , -C(R°)=C(R⁰⁰)-, -CºC- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more H atoms are each optionally replaced by F or Cl,

A^y an aromatic, heteroaromatic, alicyclic or heterocyclic group having 4 to 25 ring atoms, which may also contain fused rings, and which is unsubstituted, or mono- or polysubstituted by L,

Z^Y -O-, -S-, -CO-, -C0-0-, -OCO-, -O-CO-O-, -OCH₂-, -CH₂0-, -SCH₂-, - CH₂S-, -CF₂0-, -OCF₂-, -CF₂S-, -SCF₂-, -(CH₂)_{ni i}-, -CF₂CH₂-, - CH₂CF₂-, -(CF₂)_{ni i}-, -CH=CH-, -CF=CF-, -CºC-, -CH=CH-COO-, - OCO-CH=CH-, CR°R⁰⁰ or a single bond,

L F, Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^q)₂,

-C(=0)Y^z, -C(=0)R^q, -N(R^q)₂, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight- chain or branched alkyl having 1 to 25 C atoms in which, in addition, one or more non-adjacent CFI₂ groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -O- , -S-, -CO-, -CO-0-, -O-CO-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more FI atoms may be replaced by F, Cl, -CN,

R^q FI, F, Cl, CN, or straight chain, branched or cyclic alkyl having 1 to 25 C atoms, wherein one or more non-adjacent CFI₂-groups are optionally replaced by -0-, -S-, -CO-, -C0-0-, -O-CO-, -O-CO-O- in such a manner that O- and/or S-atoms are not directly connected with each other, and wherein one or more FI atoms are each optionally replaced by F or Cl,

R°, R⁰⁰ FI or alkyl having 1 to 20 C atoms,

Y^z halogen, preferably F or Cl ml 0, 1 or 2, n11 1 , 2, 3 or 4.

R^y is preferably primary alkyl having from 1 to 12, preferably 1 to 6 C atoms, secondary alkyl having from 3 to 15, preferably 3 to 10 C atoms, or tertiary alkyl having from 4 to 18, preferably 4 to 12 C atoms. Sp^y is preferably -(Chtejpi-, -(CH₂)_PI-0-, -(CH₂)_PI-0-CO- or -(CH₂)_PI-CO-0-, very preferably-(CH2)_Pi-, in which p1 is an integer from 1 to 12.

In a preferred embodiment of the present invention ml in formula I is 0. In another preferred embodiment of the present invention ml in formula I is 1 or 2.

A^y in formula V is preferably selected from,4-phenylene, 1 ,3-phenylene, naphthalene-1 , 4-diyl, naphthalene-2, 6-diyl, phenanthrene-2,7-diyl, 9,10-dihydro- phenanthrene-2,7-diyl, anthracene-2, 7-diyl, fluorene-2,7-diyl, coumarine, flavone, where, in addition, one or more CH groups in these groups may be replaced by N, cyclohexane-1 , 4-diyl, in which, in addition, one or more non-adjacent CFh groups may be replaced by O and/or S, 1 ,4-cyclohexenylene, bicyclo[1.1.1]- pentane-1 ,3-diyl, bicyclo[2.2.2]octane-1 , 4-diyl, spiro[3.3]heptane-2, 6-diyl, piperi- dine-1 , 4-diyl, decahydronaphthalene-2, 6-diyl, 1 ,2,3,4-tetrahydro-naphthal-ene-

2.6-diyl, indane-2,5-diyl or octahydro-4,7-methanoindane-2,5-diyl, where all these groups are unsubstituted or mono- or polysubstituted by L as defined above.

Very preferably A^y in formula V is selected from 1 ,4-phenylene, naphthalene-

2.6-diyl and cyclohexane-1 , 4-diyl, which are unsubstituted or mono- or

polysubstituted by L as defined above.

Z^y is preferably selected from -CO-0-, -OCO-, -OCH₂-, -CH₂O-, -CF₂O-, -OCF₂-, -CF2S-, -(CH₂)nii-, -CH=CH-, -CF=CF-, -CºC-, -CH=CH-COO-, -OCO-CH=CH- or a single bond. Preferred compounds of formula V are selected from the following formulae

wherein R^z, Sp^y, A^y, Z^y are as defined above and below. Very preferred compounds of formula v are selected from the following formulae

In another preferred embodiment of the present invention component A of the LC medium additionally comprises one or more fifth polymerizable

compounds comprising a ring system containing one or more aromatic or heteroaromatic rings or condensed aromatic or heteroaromatic rings, and attached thereto two polymerizable groups that are capable of radical polymerization.

These compounds are preferably selected from formula VI P¹-Sp¹-B¹-(Z^b-B²)_m-Sp²-P² VI in which P¹, P², Sp¹, Sp² are as defined in formula III, B¹ and B² are independently of each other, and on each occurrence identically or differently, an aromatic, heteroaromatic, alicyclic or heterocyclic group, preferably having 4 to 25 ring atoms, which may also contain fused rings, and which is unsubstituted, or mono- or polysubstituted by L as defined in formula I, wherein at least one of B¹ and B² denotes an aromatic or heteroaromatic group,

Z^b is, on each occurrence identically or differently, -0-, -S-, -CO-,

-CO-0-, -OCO-, -0-C0-0-, -OCH2-, -CH2O-, -SCH2-, -CH2S-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -(CH₂)nii-, -CF2CH2-, -CH2CF2- , -(CF₂)_ni-, -CH=CH-, -CF=CF-, -CºC-, -CH=CH-COO-,

-OCO-CH=CH-, CR°R⁰⁰ or a single bond, R° and R⁰⁰ each, independently of one another, denote H or alkyl having 1 to

20 C atoms, m denotes 0, 1 , 2, 3 or 4, n11 denotes 1 , 2, 3 or 4,

Particularly preferred compounds of formula VI are those in which B¹ and B² each, independently of one another, denote 1 ,4-phenylene, 1 ,3-phenylene, naphthalene-1 , 4-diyl, naphthalene-2, 6-diyl, phenanthrene-2,7-diyl, 9,10- dihydro-phenanthrene-2,7-diyl, anthracene-2, 7-diyl, fluorene-2,7-diyl, coumarine, flavone, where, in addition, one or more CFI groups in these groups may be replaced by N, cyclohexane-1 , 4-diyl, in which, in addition, one or more non-adjacent CFI2 groups may be replaced by O and/or S, 1 ,4- cyclohexenylene, bicyclo[1.1.1]pentane-1 ,3-diyl, bicyclo[2.2.2]octane-1 , 4-diyl, spiro[3.3]heptane-2, 6-diyl, piperidine-1 , 4-diyl, decahydronaphthalene-2,6- diyl, 1 ,2,3, 4-tetrahydronaphthalene-2, 6-diyl, indane-2,5-diyl or octahydro-4,7- methanoindane-2,5-diyl, where all these groups may be unsubstituted or mono- or polysubstituted by L as defined above. Very particularly preferred compounds of formula VI are those in which B¹ and B² each, independently of one another, denote 1 ,4-phenylene, 1 ,3- phenylene, naphthalene-1 ,4-diyl or naphthalene-2, 6-diyl, which are unsubstituted or mono- or polysubstituted by L as defined above.

Further preferred compounds of formula VI are selected from the group consisting of the following formulae:

L)r

VI1

P¹-Sp¹— <f "v Sp²-P²

in which P¹, P², Sp¹, Sp² and L are as defined in formula VI

Z¹ is -0-, -CO-, -C(R'R'J)- or -CF2CF2-,

R^f, R^g independently of one another, denote H, F, CH3 or CF3,

Z², Z are independently of each other -CO-O-, -O-CO-, -CFI₂O-, - OCFI2-, -CF2O-, -OCF2- or -(CFl2)ni i-, where n1 1 is 2, 3 or 4, r is 0, 1 , 2, 3 or 4 s is 0, 1 , 2 or 3, t is 0, 1 or 2.

Especially preferred are direactive compounds of formula VI2 and VI3. In the compounds of formulae VI1 to VI13 the group rably

wherein L on each occurrence, identically or differently, has one of the meanings given above or below, and is preferably F, Cl, CN, NO₂, CH3, C₂H₅, C(CH₃)₃, CH(CH₃)₂, CH₂CH(CH₃)C₂H5, OCHS, OC2H5, COCHs, COC2H5, COOCHs, COOC₂H₅, CFs, OCF₃, OCHF₂, OC₂F₅ or R-Sp-, very preferably F, Cl, CN, CFI₃, C₂FI₅, OCFI₃, COCFI₃, OCF_3J more preferably F, Cl, CFI₃, OCFI₃, COCFI₃, CF₃ Oder OCF₃, especially F or CFI₃.

In a preferred embodiment of the present invention the component A of the LC medium comprises one or more third polymerizable compounds wherein the two polymerizable groups are different from each other. Preferably in this preferred embodiment the component A of the LC medium comprises one or more compounds of formula VI or its subformulae V11 to V113 wherein P¹ and P² are different from each other. Preferably in these compounds of formula VI and V11 to V113 one of P¹ and P² is vinyloxy and the other is acrylate, methacrylate or ethacrylate, most preferably methacrylate.

Further preferred compounds of formulae V11 to V113 are those wherein Sp¹ and Sp² are a single bond. Further preferred compounds of formulae V11 to V113 are those wherein one of Sp¹ and Sp² is a single bond and the other is different from a single bond.

Further preferred compounds of formulae V11 to V113 are those wherein the group Sp¹ and Sp³ that is different from a single bond is -(CFl2)si-X"-, wherein s1 is an integer from 1 to 6, preferably 2, 3, 4 or 5, and X" is X" is the linkage to the benzene ring and is -0-, -0-C0-, -CO-O, -O-CO-O- or a single bond.

Very preferred compounds of formula VI are selected from the group consisting of the following formulae:

The concentration of the first polymerizable compounds, especially those of formula II or IIA, in the LC medium is preferably from 1 to 30%, very pref- erably from 1 to 25%, most preferably from 5 to 25%.

The concentration of the second polymerizable compounds, especially those of formula II or III, in the LC medium is preferably from 0.5 to 30%, very pref- erably from 1 to 20%, most preferably from 2 to 15%.

The concentration of the third polymerisable compounds, especially those of formula IV, in the LC medium is preferably from 1 to 30%, very preferably from 1 to 25%, most preferably from 5 to 25%.

The concentration of the fourth polymerisable compounds, especially those of formula V, in the LC medium is preferably from 1 to 30%, very preferably from 1 to 25%, most preferably from 5 to 25%.

The concentration of the fourth polymerisable compounds of formula V having one maleimide group in the LC medium is preferably from 1 to 30%, very preferably from 1 to 25%, most preferably from 5 to 25%. The

concentration of the fourth polymerisable compounds of formula V having two maleimide groups in the LC medium is preferably from 0.1 to 30%, very pref- erably from 0.1 to 10%, most preferably from 0.1 to 5%.

The concentration of the fifth polymerizable compounds, especially those of formula VI, in the LC medium is preferably from 0.05 to 5%, very preferably from 0.1 to 3%, most preferably from 0.2 to 2%.

The total concentration of the first, second, third, fourth and fifth polymerizable compounds, especially those of formula II, IIA, III, IV, V and VI, in the LC medium is preferably from 1 to 40% by weight, very preferably from 5 to 30% by weight.

In a first preferred embodiment of the present invention, the total concentration of the first, second, third, fourth and fifth polymerizable compounds, especially those of formula II, IIA, III, IV, V and VI, in the LC medium is from 10 to 40% by weight.

In a second preferred embodiment of the present invention, the total concentrat- ion of the first, second, third, fourth and fifth polymerizable compounds, especially those of formula II, IIA, III, IV, V and VI, in the LC medium is from 5 to 10% by weight.

In a third preferred embodiment of the present invention, the total concentration of the first, second, third, fourth and fifth polymerizable compounds, especially those of formula II, IIA, III, IV, V and VI, in the LC medium is from 1 to 5% by weight.

The total concentration of first, second and fourth polymerizable compounds, or compounds of formula II, IIA and V, with (exactly) one polymerizable group in the LC medium is preferably from 5 to 30% by weight.

The total concentration of the second, third, fourth and fifth polymerizable compounds, or compounds of formula III. IV, V and VI, with (exactly) two polymerizable groups in the LC medium is preferably from 0.1 to 15%, very preferably from 0.5 to 10% by weight.

Particular preference is given to LC media wherein the polymerizable

component A comprises one, two or three first polymerizable compounds, preferably of formula II or IIA, one, two or three second polymerizable

compounds, preferably of formula III, and optionally one, two or three third or fourth polymerizable compounds, preferably of formula IV or V.

Preferably the polymerisable component A contains one or more

polymerisation initiators that are capable of initiating free-radical

polymerization. Suitable types and amounts of initiators are known to the person skilled in the art and are described in the literature. Preferably the initiator is a photoinitiator. Suitable photoinitiators for free-radical

polymerisation are, for example, the commercially available Irgacure651®, Irgacure184®, Irgacure907®, Irgacure369® or Darocurel 173® (Ciba AG).

Preferably the concentration of the polymerisation initiator in the LC medium is from 0.001 to 10% by weight, very preferably 0.01 to 5% by weight, most preferably 0.01 to 2% by weight. Further preferably the polymerisable component A contains one or more photosensitizers. Example of suitable and preferred photosensitizers include isopropylthioxanthone (ITX) and thioxanthone.

Preferably the concentration of the photosensitizer in the LC medium is from 0.001 to 10% by weight, very preferably 0.001 to 5% by weight, most preferably 0.001 to 2% by weight.

Further preferably the LC medium comprises one or more stabilizers in order to prevent undesired spontaneous polymerization of the polymerizable monomers, for example during storage or transport. Suitable types and amounts of stabilizers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilizers from the Irganox® series (Ciba AG), such as, for example, Irganox® 1076.

Preferably the total concentration of the stabilizers in the LC medium is from 0.001 to 3% by weight, very preferably 0.01 to 1 % by weight, most preferably 0.05 to 0.5% by weight. Another preferred embodiment of the present invention relates to an LC medium comprising, in addition to components A and B as described above, one or more self-aligning (SA) additives. Such an LC medium is suitable for use in displays of the so-called“self-aligned” or“self-aligning” (SA) mode. Thus, it was observed that unfavourable interaction of the polyimide

alignment layer with certain compounds of the LC medium often leads to a reduction of the electrical resistance of the LC display. In such SA displays the alignment layers, which are usually present in LCDs to ensure specific initial alignment of the LC molecules, are omitted on one or both of the substrates. Instead, a self alignment agent is added to the LC medium that induces the desired alignment, for example homeotropic or planar alignment, in situ by a self assembling mechanism.

Suitable self-aligning additives are for example compounds having an organic core group and attached thereto one or more polar anchor groups, which are capable of interacting with the substrate surface, causing the additives on the substrate surface to align and induce the desired alignment also in the LC molecules.

Suitable self-aligning additives to induce homeotropic alignment are

disclosed for example in US 2013/0182202 A1 , US 2014/0838581 A1 , US 2015/0166890 A1 and US 2015/0252265 A1.

Preferred SA additives are selected from compounds comprising a mesogenic group and a straight-chain or branched alkyl side chain that is terminated with one or more polar anchor groups selected from hydroxy, carboxy, amino or thiol groups. Further preferred SA additives contain one or more polymerizable groups which are attached, optionally via spacer groups, to the mesogenic group. These polymerizable SA additives can be polymerized in the LC medium under similar conditions as applied for the RMs in the PSA process.

The LC medium preferably contains one or more SA additives in a

concentration of 0.1 to 2.5 %.

The SA mode can also be used in combination with the PSA mode. Thus, another preferred LC medium according to the present invention contains, in addition to components A and B as described above and below, a second polymerizable component C) comprising one or more polymerizable

compounds comprising one or more polymerizable groups that are capable of undergoing radical polymerization, and are preferably selected from formula R or its subformulae, and further contains one or more self-aligning additives as described above and below. Besides the polymerizable component A as described above, the LC medium according to the present invention comprises an LC component B, or LC host mixture, comprising one or more, preferably two or more LC compounds which are selected from low-molecular-weight compounds that are unpolymerizable. These LC compounds are selected such that they stable and/or unreactive to a polymerization reaction under the conditions applied to the polymerization of the polymerizable compounds.

Preference is given to LC media in which the LC component B, or the LC host mixture, has a nematic LC phase, and preferably has no chiral liquid crystal phase. The LC component B, or LC host mixture, is preferably a nematic LC mixture.

Preference is furthermore given to achiral polymerizable compounds, and to LC media in which the compounds of component A and/or B are selected exclusively from the group consisting of achiral compounds.

Preferably the proportion of the LC component B in the LC medium is from 70 to 95% by weight. The LC media and LC host mixtures of the present invention preferably have a nematic phase range > 80 K, very preferably > 100 K, and preferably a rotational viscosity < 250 mPa s, very preferably < 200 mPa s, at 20°C.

The birefringence Dh of LC media and LC host mixtures according to the invention is preferably preferably from 0.07 to 0.15, particularly preferably from 0.08 to 0.15.

In a first preferred embodiment of the present invention, the LC medium contains an component B or LC host mixture having a positive dielectric anisotropy De. Such LC media are especially suitable for use in TN, OCB-, Posi-VA-, IPS- or FFS-displays or related modes using LC-materials with De>0.

The LC media and LC host mixtures according to this first preferred embodiment preferably have a positive dielectric anisotropy De from +2 to +30, particularly preferably from +3 to +20, at 20°C and 1 kHz.

Particularly preferred is an LC medium of this first preferred embodiment, wherein the liquid-crystalline component B or LC host mixture comprises one or more compounds selected from formula A and B

in which the individual radicals have, independently of each other and on each occurrence identically or differently, the following meanings: each, independently

of one another, and on each occurrence, identically or differently

R²¹ , R³¹ each, independently of one another, alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated,

X° F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms,

Z³¹ -CH₂CH₂-, -CF₂CF₂-, -COO-, trans- CH=CH-, trans-

CF=CF-, -CFI₂0- or a single bond, preferably -CFI₂CFI₂-, - COO-, trans- CFI=CFI- or a single bond, particularly preferably -COO-, trans- CFI=CFI- or a single bond,

L²¹ , L ²², L³¹ , L ³² each, independently of one another, FI or F g 0, 1 , 2 or 3.

In the compounds of formula A and B, X° is preferably F, Cl, CF3, CFIF₂, OCFs, OCHF₂, OCFHCFs, OCFHCHF₂, OCFHCHF_2J OCF₂CH₃, OCF₂CHF_2J

OCF₂CHF₂, OCF₂CF₂CHF₂, OCF₂CF₂CHF₂, OCFHCF₂CF₃, OCFHCF₂CHF₂,

OCF₂CF₂CF₃, OCF₂CF₂CCIF_2J OCCIFCF₂CF₃ or CH=CF₂, very preferably F or OCF3, most preferably F.

In the compounds of formula A and B, R²¹ and R³¹ are preferably selected from straight-chain alkyl or alkoxy with 1 , 2, 3, 4, 5 or 6 C atoms, and straight-chain alkenyl with 2, 3, 4, 5, 6 or 7 C atoms.

In the compounds of formula A and B, g is preferably 1 or 2.

In the compounds of formula B, Z³¹ is preferably COO, trans-CFI=CFI or a single bond, very preferably COO or a single bond. Preferably component B of the LC medium comprises one or more

compounds of formula A selected from the group consisting of the following formulae:

in which A²¹, R²¹, X°, L²¹ and L²² have the meanings given in formula A, L²³ and L²⁴ each, independently of one another, are FI or F, and X° is preferably F. Particularly preferred are compounds of formulae A1 and A2.

Particularly preferred compounds of formula A1 are selected from the group consisting of the following subformulae:

in which R²¹, X°, L²¹ and L²² have the meaning given in formula A1 , L²³, L²⁴, L²⁵ and L²⁶ are each, independently of one another, FI or F, and X° is preferably F.

Very particularly preferred compounds of formula A1 are selected from the group consisting of the following subformulae:

in which R²¹ is as defined in formula A1 .

Particularly preferred compounds of formula A2 are selected from the group consisting of the following subformulae:

in which R²¹, X°, L²¹ and L²² have the meaning given in formula A2, L²³, L²⁴, L²⁵ and L²⁶ each, independently of one another, are FI or F, and X° is preferably F.

Very particularly preferred compounds of formula A2 are selected from the group consisting of the following subformulae:

in which R²¹ and X° are as defined in formula A2. Particularly preferred compounds of formula A3 are selected from the group consisting of the following subformulae:

in which R²¹, X°, L²¹ and L²² have the meaning given in formula A3, and X° is preferably F.

Particularly preferred compounds of formula A4 are selected from the group consisting of the following subformulae:

in which R²¹ is as defined in formula A4.

Preferably component B of the LC medium comprises one or more compounds of formula B selected from the group consisting of the following formulae:

in which g, A³¹, A³², R³¹, X°, L³¹ and L³² have the meanings given in formula B, and X° is preferably F. Particularly preferred are compounds of formulae B1 and B2.

Particularly preferred compounds of formula B1 are selected from the group consisting of the following subformulae:

in which R³¹, X°, L³¹ and L³² have the meaning given in formula B1 , and X° is preferably F.

Very particularly preferred compounds of formula B1 a are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B1 .

Very particularly preferred compounds of formula B1 b are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B1.

Particularly preferred compounds of formula B2 are selected from the group consisting of the following subformulae:

in which R³¹, X°, L³¹ and L³² have the meaning given in formula B2, L³³, L³⁴, L³⁵ and L³⁶ are each, independently of one another, H or F, and X° is preferably F.

Very particularly preferred compounds of formula B2 are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2. Very particularly preferred compounds of formula B2b are selected from the group consisting of the following subformulae

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2c are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2d and B2e are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2f are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2g are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2h are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2. Very particularly preferred compounds of formula B2i are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2k are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Very particularly preferred compounds of formula B2I are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B2.

Alternatively to, or in addition to, the compounds of formula B1 and/or B2 component B of the LC medium may also comprise one or more compounds of formula B3 as defined above. Particularly preferred compounds of formula B3 are selected from the group consisting of the following subformulae:

in which R³¹ is as defined in formula B3.

Preferably component B of the LC medium comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula C

in which the individual radicals have the following meanings: each, independently of one another, and

on each occurrence, identically or differently,

R⁴¹ , R⁴² each, independently of one another, alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or

alkenyloxy having 2 to 9 C atoms, all of which are

optionally fluorinated,

Z⁴¹ , Z⁴² each, independently of one another, -CH2CH2-, -COO-, trans- CH=CH-, frans-CF=CF-, -CFI2O-, -CF2O-, -CºC- or a single bond, preferably a single bond, h 0, 1 , 2 or 3.

In the compounds of formula C, R⁴¹ and R⁴² are preferably selected from straight-chain alkyl or alkoxy with 1 , 2, 3, 4, 5 or 6 C atoms, and straight- chain alkenyl with 2, 3, 4, 5, 6 or 7 C atoms.

In the compounds of formula C, h is preferably 0, 1 or 2. In the compounds of formula C, Z⁴¹ and Z⁴² are preferably selected from COO, trans-CH=CH and a single bond, very preferably from COO and a single bond. Preferred compounds of formula C are selected from the group consisting of the following subformulae:

wherein R⁴¹ and R⁴² have the meanings given in formula C, and preferably denote each, independently of one another, alkyl, alkoxy, fluorinated alkyl or fluorinated alkoxy with 1 to 7 C atoms, or alkenyl, alkenyloxy, alkoxyalkyl or fluorinated alkenyl with 2 to 7 C atoms. In another preferred embodiment of the present invention component B of the LC medium comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula D

D

in which A⁴¹, A⁴², Z⁴¹, Z⁴², R⁴¹, R⁴² and h have the meanings given in formula C or one of the preferred meanings given above.

Preferred compounds of formula D are selected from the group consisting of the following subformulae:

in which R⁴¹ and R⁴² have the meanings given in formula D and R⁴¹ preferably denotes alkyl bedeutet, and in formula D1 R⁴² preferably denotes alkenyl, particularly preferably -(CH₂)₂-CH=CH-CH3, and in formula D2 R⁴² preferably denotes alkyl, -(CH₂)2-CH=CH₂ or -(CH₂)₂-CH=CH-CH₃.

In another preferred embodiment of the present invention component B of the LC medium comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula E containing an alkenyl group

in which the individual radicals, on each occurrence identically or differently each, independently of one another, have the following meaning:

R^A1 alkenyl having 2 to 9 C atoms or, if at least one of the rings X, Y and Z denotes cyclohexenyl, also one of the meanings of R^A2,

R^A2 alkyl having 1 to 12 C atoms, in which, in addition, one or two non- adjacent Chte groups may be replaced by -0-, -CH=CH-, -CO- , -OCO- or -COO- in such a way that O atoms are not linked directly to one another, x 1 or 2.

R^A2 is preferably straight-chain alkyl or alkoxy having 1 to 8 C atoms or straight-chain alkenyl having 2 to 7 C atoms.

Preferred compounds of formula E are selected from the following sub- formulae:

alkyl— ( O )— o )— alkenyl E3

alkenyl— O )— ( o )— O-alkyl E4

in which alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl and alkenyl^* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms. Alkenyl and alkenyl^* preferably denote CH2=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Very preferred compounds of the formula E are selected from the following sub-formulae:

in which m denotes 1 , 2, 3, 4, 5 or 6, i denotes 0, 1 , 2 or 3, and R^b1 denotes H, CH₃ or C₂H₅.

Very particularly preferred compounds of the formula E are selected from the following sub-formulae:

Most preferred are compounds of formula E1 a2, E1 a5, E3a1 and E6a1 . In another preferred embodiment of the present invention component B of the LC medium comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula F

in which the individual radicals have, independently of each other and on each occurrence identically or differently, the following meanings:

Z²¹

-CH2CH2-, -CF2CF2-, -COO-, trans- CFI=CFI-, trans- CF=CF-, -CFI2O-, -CF2O-, -CºC- or a single bond, preferably -CF2O-,

L²¹ , L ²², L²³, L ²⁴ each, independently of one another, FI or F, g 0, 1 , 2 or 3.

Particularly preferred compounds of formula F are selected from the group consisting of the following formulae:

in which R²¹, X°, L²¹ and L²² have the meaning given in formula F, L²⁵ and L²⁶ are each, independently of one another, FI or F, and X° is preferably F.

Very particularly preferred compounds of formula F1 -F3 are selected from the group consisting of the following subformulae:

in which R²¹ is as defined in formula F1. In another preferred embodiment of the present invention component B of the LC medium comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula G containing a cyano group.

on each occurrence, identically or differently

R⁵¹ , R⁵² each, independently of one another, alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated, z⁵¹, z⁴² -CH2CH2-, -COO-, frans-CH=CH-, frans-CF=CF-, -CH₂0- , -CF2O-, -CºC- or a single bond, preferably a single bond,

L⁵¹ , L⁵² each, independently of one another, FI or F, i 0, 1 , 2 or 3.

Preferred compounds of formula G are selected from the following

subformulae

35

in which R⁵¹ is as defined in formula G and L¹ and L² are each, independently of one another, H or F. Very preferred are compounds of formula G1 , G2 and G5.

Preferred compounds of formula G1 -G9 are those wherein L⁵¹ and L⁵² are F.

Further preferred compounds of formula G1 -G7 are those wherein L⁵¹ is F and L⁵² is FI.

Very preferred compounds of formula G are selected from the group consisting of the following subformulae:

in which R⁵¹ is as defined in formula G.

In the compounds of formula G, G1-G7 and their subformulae, R⁵¹ is particularly preferably alkyl or alkoxy having 1 to 8 carbon atoms, or alkenyl having from 2 to 7 carbon atoms.

The concentration of the compounds of formula A and B in the LC host mixture is preferably from 2 to 60%, very preferably from 3 to 45%, most preferably from 4 to 35%. The concentration of the compounds of formula C and D in the LC host mixture is preferably from 2 to 70%, very preferably from 5 to 65%, most preferably from 10 to 60%. The concentration of the compounds of formula E in the LC host mixture is preferably from 5 to 50%, very preferably from 5 to 35%.

The concentration of the compounds of formula F in the LC host mixture is preferably from 2 to 30%, very preferably from 5 to 20%.

Further preferred embodiments of the present invention are listed below, including any combination thereof. a) The LC host mixture comprises one or more compounds of formula A and/or B with high positive dielectric anisotropy, preferably with De > 15. b) The LC host mixture comprises one or more compounds selected from the group consisting of formulae A1a2, A1 b1 , A1d1 , A1f1 , A2a1 , A2h1 , A2I1 , A2I2, A2k1 , B2h3, B2I1 , F1a. The proportion of these compounds in the LC host mixture is preferably from 4 to 40%, very preferably from 5 to 35%. c) The LC host mixture comprises one or more compounds selected from the group consisting of formulae C3, C4, C5, C9 and D2. The proportion of these compounds in the LC host mixture is preferably from 8 to 70%, very preferably from 10 to 60%. d) The LC host mixture comprises one or more compounds selected from the group consisting of formulae G1 , G2 and G5, preferably G1a, G2a and G5a. The proportion of these compounds in the LC host mixture is preferably from 4 to 40%, very preferably from 5 to 35%. e) The LC host mixture comprises one or more compounds selected from the group consisting of formulae E1 , E3 and E6, preferably E1 a, E3a and E6a, very preferably E1 a2, E1a5, E3a1 and E6a1. The proportion of these compounds in the LC host mixture is preferably from 5 to 60%, very preferably from 10 to 50%.

In a second preferred embodiment of the present invention, the LC medium contains an component B or LC host mixture having a negative dielectric anisotropy De.

Such LC media are especially suitable for use in VA, IPS and UB-FFS displays or related modes using LC-materials with De<0.

The LC media and LC host mixtures according to this second preferred embodiment preferably have a negative dielectric anisotropy De from -0.5 to - 10, very preferably from -2.5 to -7.5, at 20°C and 1 kHz. Particularly preferred embodiments of an LC medium according to this second preferred embodiment are those of sections a)-z2) below: a) LC medium wherein the component B or LC host mixture comprises one or more compounds selected from formulae CY and PY:

wherein a denotes 1 or 2, b denotes 0 or 1

R¹ and R² each, independently of one another, denote alkyl having 1 to

12 C atoms, where, in addition, one or two non-adjacent CFh groups may be replaced by -0-, -CFI=CFI-, -CO-, -OCO- or -COO- in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms,

Z^x and Z^y each, independently of one another, denote -CFI2CFI2-,

-CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C₂F₄-, -CF=CF-, -CFI=CFI-CFl₂0- or a single bond, preferably a single bond,

L^{1 4} each, independently of one another, denote F, Cl, OCF3,

CFs, CHs, CH₂F, CHF₂.

Preferably, both L¹ and L² denote F or one of L¹ and L² denotes F and the other denotes Cl, or both L³ and L⁴ denote F or one of L³ and L⁴ denotes F and the other denotes Cl.

The compounds of the formula CY are preferably selected from the group consisting of the following sub-formulae:

in which a denotes 1 or 2, alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-. Especially preferred are compounds selected from formulae CY2, CY8, CY10 and CY16.

The compounds of the formula PY are preferably selected from the group consisting of the following sub-formulae:

in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms, and (O) denotes an oxygen atom or a single bond. Alkenyl preferably denotes CFh=CFI-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂- CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Especially preferred are compounds selected from formulae PY2, PY8, PY10 and PY16.

Preferably the concentration of the compounds of formula CY and PY and their subformulae in the LC medium is from 10 to 70% by weight, very preferably from 15 to 50% by weight. Preferably the concentration of the compounds of formula CY and its subformulae in the LC medium is from 2 to 40% by weight, very preferably from 3 to 30% by weight. Preferably the concentration of the compounds of formula PY and its subformulae in the LC medium is from 2 to 50% by weight, very preferably from 3 to 40% by weight. b) LC medium wherein the component B or LC host mixture comprises one or more mesogenic or LC compounds comprising an alkenyl group

(hereinafter also referred to as "alkenyl compounds"), wherein said alkenyl group is stable to a polymerization reaction under the conditions used for polymerization of the polymerizable compounds contained in the LC medium.

Preferably the component B or LC host mixture comprises one or more alkenyl compounds selected from formulae AN and AY

in which the individual radicals, on each occurrence identically or differ- ently, and each, independently of one another, have the following meaning:

R^A2 alkyl having 1 to 12 C atoms, in which, in addition, one or two non- adjacent CFh groups may be replaced by -0-, -CH=CH-, -CO- , -OCO- or -COO- in such a way that O atoms are not linked directly to one another,

Z^x -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-,

-CO-O-, -O-CO-, -C₂F₄-, -CF=CF-, -CH=CH-CH₂0-, or a single bond, preferably a single bond, L¹-⁴ H, F, Cl, OCFs, CFs, CHs, CH₂F or CHF₂, preferably H, F or Cl, x 1 or 2, z 0 or 1.

Preferred compounds of formula AN and AY are those wherein R^A2 is selected from ethenyl, propenyl, butenyl, pentenyl, hexenyl and heptenyl.

In a preferred embodiment the component B or LC host mixture comprises one or more compounds of formula AN selected from the following sub-formulae:

alkyl— ( O )— o )— alkenyl AN3 alkenyl— O )— ( o )— O-alkyl AN4 alkenyl— O )— o )— alkenyl* AN5

in which alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl and alkenyl^* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms. Alkenyl and alkenyl^* preferably denote

CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-

(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Preferably the the component B or LC host mixture comprises one or more compounds selected from formulae AN1 , AN2, AN3 and AN6, very preferably one or more compounds of formula AN1 .

In another preferred embodiment the component B or LC host mixture comprises one or more compounds of formula AN selected from the following sub-formulae:

in which m denotes 1 , 2, 3, 4, 5 or 6, i denotes 0, 1 , 2 or 3, and R^b1 denotes H, CH₃ or C2H₅. In another preferred embodiment the component B or LC host mixture comprises one or more compounds selected from the following sub- formulae:

Most preferred are compounds of formula AN1 a2 and AN1 a5.

In another preferred embodiment the component B or LC host mixture comprises one or more compounds of formula AY selected from the following sub-formulae:

in which alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, "(O)" denotes an O- atom or a single bond, and alkenyl and alkenyl^* each, independently of one another, denote a straight-chain alkenyl radical having 2-7 C atoms. Alkenyl and alkenyl^* preferably denote CH2=CH-,

CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂- CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-. In another preferred embodiment the component B or LC host mixture comprises one or more compounds of formula AY selected from the following sub-formulae:

in which m and n each, independently of one another, denote 1 , 2, 3, 4, 5 or 6, and alkenyl denotes CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃- CH=CH-(CH₂)₂-. Preferably the proportion of compounds of formula AN and AY in the LC medium is from 2 to 70% by weight, very preferably from 5 to 60% by weight, most preferably from 10 to 50% by weight. Preferably the LC medium or LC host mixture contains 1 to 5, preferably

1 , 2 or 3 compounds selected from formulae AN and AY.

In another preferred embodiment of the present invention the LC medium comprises one or more compounds of formula AY14, very preferably of AY14a. The proportion of compounds of formula AY14 or

AY14a in the LC medium is preferably 3 to 20% by weight.

The addition of alkenyl compounds of formula AN and/or AY enables a reduction of the viscosity and response time of the LC medium. c) LC medium wherein the component B or LC host mixture comprises one or more compounds of the following formula:

in which the individual radicals have the following meanings:

R³ and R⁴ each, independently of one another, denote alkyl having 1 to

12 C atoms, in which, in addition, one or two non-adjacent Chte groups may be replaced by -0-, -CH=CH-, -CO-, -O-CO- or -CO-O- in such a way that O atoms are not linked directly to one another, z^y denotes -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-,

-OCH2-, -CO-O-, -O-CO-, -C₂F₄-, -CF=CF-, -CH=CH-CH₂O- or a single bond, preferably a single bond.

The compounds of the formula ZK are preferably selected from the group consisting of the following sub-formulae:

0

in which alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl preferably denotes CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Especially preferred are compounds of formula ZK1 .

Particularly preferred compounds of formula ZK are selected from the following sub-formulae:

wherein the propyl, butyl and pentyl groups are straight-chain groups.

Most preferred are compounds of formula ZK1 a. d) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds of the following formula:

in which the individual radicals on each occurrence, identically or differently, have the following meanings:

R⁵ and R⁶ each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent Chte groups may be replaced by -0-, -CH=CH-, -CO-, -OCO- or -COO- in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms,

e denotes 1 or 2.

The compounds of the formula DK are preferably selected from the group consisting of the following sub-formulae:

in which alkyl and alkyl^* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl denotes a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl preferably denotes CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-. e) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds of the following formula:

in which the individual radicals have the following meanings:

with at least one ring F being different from cyclohexylene f denotes 1 or 2,

R¹ and R² each, independently of one another, denote alkyl having 1 to

12 C atoms, where, in addition, one or two non-adjacent CH₂ groups may be replaced by -0-, -CH=CH-, -CO-, -OCO- or -COO- in such a way that O atoms are not linked directly to one another, Z^x denotes -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-,

-OCH2-, -C0-0-, -0-C0-, -C₂F₄-, -CF=CF-, -CH=CH-CH₂O- or a single bond, preferably a single bond, L¹ and L² each, independently of one another, denote F, Cl, OCF₃,

CFs, CHs, CH₂F, CHF₂.

Preferably, both radicals L¹ and L² denote F or one of the radicals L¹ and L² denotes F and the other denotes Cl.

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

in which R¹ has the meaning indicated above, alkyl denotes a straight- chain alkyl radical having 1 -6 C atoms, (O) denotes an oxygen atom or a single bond, and v denotes an integer from 1 to 6. R¹ preferably denotes straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, in particular CH3, C2H5, n-C₃Fl₇, n-C₄H9, n-CsHn, CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂- CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-

(CH₂)₂-. f) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds selected from the group consisting of the following formulae:

in which alkyl denotes Ci-₆-alkyl, L^x denotes H or F, and X denotes F, Cl, OCF3, OCFIF₂ or OCFI=CF₂. Particular preference is given to corn- pounds of the formula GG1 in which X denotes F. g) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds selected from the group consisting of the following formulae:

in which R⁵ has one of the meanings indicated above for R¹, alkyl denotes Ci-₆-alkyl, d denotes 0 or 1 , and z and m each, independently of one another, denote an integer from 1 to 6. R⁵ in these compounds is particularly preferably Ci-₆-alkyl or -alkoxy or C2-6-alkenyl, d is preferably 1 . The LC medium according to the invention preferably comprises one or more compounds of the above-mentioned formulae in amounts of > 5% by weight. h) LC medium wherein component B or the LC host mixture additionally comprises one or more biphenyl compounds selected from the group consisting of the following formulae:

BP3

in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl^* preferably denote

CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-

(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

The proportion of the biphenyls of the formulae BP1 to BP3 in the LC host mixture is preferably at least 3% by weight, in particular > 5% by weight.

The compounds of the formula BP2 are particularly preferred.

The compounds of the formulae BP1 to BP3 are preferably selected from the group consisting of the following sub-formulae:

in which alkyl^* denotes an alkyl radical having 1 -6 C atoms. The medium according to the invention particularly preferably comprises one or more compounds of the formulae BP1 a and/or BP2c. i) LC medium wherein component B or the LC host mixture additionally comprises one or more terphenyl compounds of the following formula:

in which R⁵ and R⁶ each, independently of one another, have one of the meanings indicated above, and

each, independently of one another, denote

in which L⁵ denotes F or Cl, preferably F, and L⁶ denotes F, Cl, OCF3, CF3, CFI3, CFI2F or CFIF2, preferably F.

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

F CF,

^R— ( ⁰ ) ( O ) ( O ) (0)C m_mH 2m+1 T13

F CHF,

^{R— 0} ) ( O ) ( O ) (0)C m_mH 2m+1 T14

in which R denotes a straight-chain alkyl or alkoxy radical having 1 -7 C atoms, R^* denotes a straight-chain alkenyl radical having 2-7 C atoms, (O) denotes an oxygen atom or a single bond, and m denotes an integer from 1 to 6. R^* preferably denotes CFh=CFI-, CFh=CFICFl2CFl2-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂-CH=CH-, CH₃-(CH₂)₃- CH=CH- or CH₃-CH=CH-(CH₂)₂-.

R preferably denotes methyl, ethyl, propyl, butyl, pentyl, hexyl, methoxy ethoxy, propoxy, butoxy or pentoxy. The LC host mixture according to the invention preferably comprises the terphenyls of the formula T and the preferred sub-formulae thereof in an amount of 0.5-30% by weight, in particular 1 -20% by weight.

Particular preference is given to compounds of the formulae T1 , T2, T3 and T21 . In these compounds, R preferably denotes alkyl, furthermore alkoxy, each having 1 -5 C atoms.

The terphenyls are preferably employed in LC media according to the invention if the Dh value of the mixture is to be > 0.1 . Preferred LC media comprise 2-20% by weight of one or more terphenyl compounds of the formula T, preferably selected from the group of compounds T 1 to T22. k) LC medium wherein component B or the LC host mixture additionally comprises one or more quaterphenyl compounds selected from the group consisting of the following formulae:

wherein

R^Q is alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated,

X^Q is F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms,

L^Q1 to L^Q6 independently of each other are H or F, with at least one of

L^Q1 to L^Q6 being F. Preferred compounds of formula Q are those wherein R^Q denotes straight-chain alkyl with 2 to 6 C-atoms, very preferably ethyl, n-propyl or n-butyl.

Preferred compounds of formula Q are those wherein L^Q3 and L^Q4 are F. Further preferred compounds of formula Q are those wherein L^Q3,

L^Q4 and one or two of L^Q1 and L^Q2 are F.

Preferred compounds of formula Q are those wherein X^Q denotes F or OCF3, very preferably F.

The compounds of formula Q are preferably selected from the following subformulae

wherein R^Q has one of the meanings of formula Q or one of its preferred meanings given above and below, and is preferably ethyl, n-propyl or n- butyl.

Especially preferred are compounds of formula Q1 , in particular those wherein R^Q is n-propyl.

Preferably the proportion of compounds of formula Q in the LC host mixture is from >0 to <5% by weight, very preferably from 0.1 to 2% by weight, most preferably from 0.2 to 1 .5% by weight. Preferably the LC host mixture contains 1 to 5, preferably 1 or 2 compounds of formula Q.

The addition of quaterphenyl compounds of formula Q to the LC host mixture enables to reduce ODF mura, whilst maintaining high UV absorption, enabling quick and complete polymerization, enabling strong and quick tilt angle generation, and increasing the UV stability of the LC medium.

Besides, the addition of compounds of formula Q, which have positive dielectric anisotropy, to the LC medium with negative dielectric anisotropy allows a better control of the values of the dielectric constants e and _±, and in particular enables to achieve a high value of the dielectric constant e while keeping the dielectric anisotropy De constant, thereby reducing the kick-back voltage and reducing image sticking.

I) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds of formula CC:

wherein

R^c denotes alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated,

X^c denotes F, Cl, halogenated alkyl or alkoxy having 1 to 6 C atoms or halogenated alkenyl or alkenyloxy having 2 to 6 C atoms, L^C1 , L^C2 independently of each other denote H or F, with at least one of L^C1 and L^C2 being F.

Preferred compounds of formula CC are those wherein R^c denotes straight-chain alkyl with 2 to 6 C-atoms, very preferably ethyl, n-propyl or n-butyl.

Preferred compounds of formula CC are those wherein L^C1 and L^C2 are F. Preferred compounds of formula CC are those wherein X^c denotes F or

OCF3, very preferably F.

Preferred compounds of formula CC are selected from the following formula

wherein R^c has one of the meanings of formula CC or one of its preferred meanings given above and below, and is preferably ethyl, n- propyl or n-butyl, very preferably n-propyl.

Preferably the proportion of compounds of formula CC in the LC host mixture is from >0 to < 10% by weight, very preferably from 0.1 to 8% by weight, most preferably from 0.2 to 5% by weight. Preferably the LC host mixture contains 1 to 5, preferably 1 , 2 or 3 compounds of formula CC.

The addition of compounds of formula CC, which have positive

dielectric anisotropy, to the LC medium with negative dielectric

anisotropy allows a better control of the values of the dielectric

constants e and _±, and in particular enables to achieve a high value of the dielectric constant e while keeping the dielectric anisotropy De constant, thereby reducing the kick-back voltage and reducing image sticking. Besides, the addition of compounds of formula CC enables to reduce the viscosity and the response time of the LC medium. m) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds selected from the group consisting of the following formulae:

in which R¹ and R² have the meanings indicated above and preferably each, independently of one another, denote straight-chain alkyl having 1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms.

Preferred media comprise one or more compounds selected from the formulae 01 , 03 and 04. n) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds of the following formula:

in which

R⁹ denotes H, CH3, C2H5 or n-CsFF, (F) denotes an optional fluorine substituent, and q denotes 1 , 2 or 3, and R⁷ has one of the meanings indicated for R¹, preferably in amounts of > 3% by weight, in particular > 5% by weight and very particularly preferably 5-30% by weight. Particularly preferred compounds of the formula FI are selected from the group consisting of the following sub-formulae:

in which R⁷ preferably denotes straight-chain alkyl, and R⁹ denotes CFI3, C2FI5 or n-C3Fl₇. Particular preference is given to the compounds of the formulae FI1 , FI2 and FI3. o) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds selected from the group consisting of the following formulae:

in which R⁸ has the meaning indicated for R¹, and alkyl denotes a straight-chain alkyl radical having 1 -6 C atoms. p) LC medium wherein component B or the LC host mixture additionally comprises one or more compounds which contain a tetrahydronaphthyl or naphthyl unit, such as, for example, the compounds selected from the group consisting of the following formulae:

in which

R¹⁰ and R¹¹ each, independently of one another, denote alkyl having 1 to 12 C atoms, where, in addition, one or two non-adjacent Chte groups may be replaced by -0-, -CH=CH-, -CO-,

-OCO- or -COO- in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms, and R¹⁰ and R¹¹ preferably denote straight-chain alkyl or alkoxy having

1 to 6 C atoms or straight-chain alkenyl having 2 to 6 C atoms, and

Z¹ and Z² each, independently of one another, denote -C2H₄-,

-CH=CH-, -(CH₂)4-, -(CH₂)₃0-, -0(CH₂)₃-, -CH=CH-CH₂CH₂-, -CH₂CH₂CH=CH-, -CH₂O-, -OCH₂-,

-CO-0-, -o-co-, -C₂F₄-, -CF=CF-, -CF=CH-, -CH=CF-, -CH₂- or a single bond. q) LC medium wherein component B or the LC host mixture additionally comprises one or more difluorodibenzochromans and/or chromans of the following formulae:

in which

R¹¹ and R¹² each, independently of one another, have one of the

meanings indicated above for R¹¹,

ring M is trans-1 ,4-cyclohexylene or 1 ,4-phenylene,

Z^m -C₂H₄-, -CH2O-, -OCH2-, -CO-O- or -O-CO-,

c is 0, 1 or 2,

preferably in amounts of 3 to 20% by weight, in particular in amounts of 3 to 15% by weight.

Particularly preferred compounds of the formulae BC, CR and RC are selected from the group consisting of the following sub-formulae:

in which alkyl and alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, (O) denotes an oxygen atom or a single bond, c is 1 or 2, and alkenyl and alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and alkenyl^* preferably denote CH2=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-(CH₂)₂- CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Very particular preference is given to LC host mixtures comprising one, two or three compounds of the formula BC-2. r) LC medium wherein component B or the LC host mixture additionally comprises one or more fluorinated phenanthrenes and/or dibenzofurans of the following formulae:

in which R¹¹ and R¹² each, independently of one another, have one of the meanings indicated above for R¹¹, b denotes 0 or 1 , L denotes F, and r denotes 1 , 2 or 3.

Particularly preferred compounds of the formulae PH and BF are selected from the group consisting of the following sub-formulae:

in which R and R' each, independently of one another, denote a straight-chain alkyl or alkoxy radical having 1 -7 C atoms. s) LC medium wherein component B or the LC host mixture additionally comprises one or more monocyclic compounds of the following formula

wherein

R¹ and R² each, independently of one another, denote alkyl having 1 to

12 C atoms, where, in addition, one or two non-adjacent CFh groups may be replaced by -0-, -CH=CH-, -CO-, -OCO- or -COO- in such a way that O atoms are not linked directly to one another, preferably alkyl or alkoxy having 1 to 6 C atoms,

L¹ and L² each, independently of one another, denote F, Cl, OCF3,

CFs, CHs, CH₂F, CHF₂.

Preferably, both L¹ and L² denote F or one of L¹ and L² denotes F and the other denotes Cl,

The compounds of the formula Y are preferably selected from the group consisting of the following sub-formulae:

0,

in which, Alkyl and Alkyl* each, independently of one another, denote a straight-chain alkyl radical having 1 -6 C atoms, Alkoxy denotes a straight-chain alkoxy radical having 1-6 C atoms, Alkenyl and Alkenyl* each, independently of one another, denote a straight-chain alkenyl radical having 2-6 C atoms. Alkenyl and Alkenyl^* preferably denote

CH₂=CH-, CH₂=CHCH₂CH₂-, CH₃-CH=CH-, CH₃-CH₂-CH=CH-, CH₃-

(CH₂)₂-CH=CH-, CH₃-(CH₂)₃-CH=CH- or CH₃-CH=CH-(CH₂)₂-.

Particularly preferred compounds of the formula Y are selected from the group consisting of the following sub-formulae:

Alkoxy Alkoxy Y6A

Alkoxy Alkoxy Y6B

wherein Alkoxy preferably denotes straight-chain alkoxy with 3, 4, or 5 C atoms. t) LC medium which, apart from the polymerizable compounds as

described above and below, does not contain a compound which con- tains a terminal vinyloxy group (-0-CH=CH2). u) LC medium wherein component B or the LC host mixture comprises 1

to 8, preferably 1 to 5, compounds of the formulae CY1 , CY2, PY1 and/or PY2. The proportion of these compounds in the LC host mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%.

The content of these individual compounds is preferably in each case 2 to 20%. v) LC medium wherein component B or the LC host mixture comprises 1

to 8, preferably 1 to 5, compounds of the formulae CY9, CY10, PY9 and/or PY10. The proportion of these compounds in the LC host

mixture as a whole is preferably 5 to 60%, particularly preferably 10 to 35%. The content of these individual compounds is preferably in each case 2 to 20%. w) LC medium wherein component B or the LC host mixture comprises 1 to 10, preferably 1 to 8, compounds of the formula ZK, in particular compounds of the formulae ZK1 , ZK2 and/or ZK6. The proportion of these compounds in the LC host mixture as a whole is preferably 3 to 25%, particularly

preferably 5 to 45%. The content of these individual compounds is preferably in each case 2 to 20%. x) LC medium in which the proportion of compounds of the formulae CY,

PY and ZK in the LC host mixture as a whole is greater than 70%, pref- erably greater than 80%. y) LC medium in which the LC host mixture contains one or more

compounds containing an alkenyl group, preferably selected from

formulae AN and AY, very preferably selected from formulae AN1 , AN3,

AN6 and AY14, most preferably from formulae AN 1a, AN3a, AN6a and AY14. The concentration of these compounds in the LC host mixture is preferably from 2 to 70%, very preferably from 3 to 55%. z) LC medium wherein component B or the LC host mixture contains one or more, preferably 1 to 5, compounds selected of formula PY1 -PY8, very preferably of formula PY2. The proportion of these compounds in the LC host mixture as a whole is preferably 1 to 30%, particularly preferably 2 to 20%. The content of these individual compounds is preferably in each case 1 to 20%. z1 ) LC medium wherein component B or the LC host mixture contains one or more, preferably 1 , 2 or 3, compounds selected from formulae T1 ,

T2, T3 and T21 , very preferably from formula T2. The content of these compounds in the LC host mixture as a whole is preferably 1 to 20%. z2) LC medium in which the LC host mixture contains one or more,

preferably 1 , 2 or 3, compounds of formula BF1 , and one or more, preferably 1 , 2 or 3, compounds selected from formulae AY14, AY15 and AY16, very preferably of formula AY14. The proportion of the compounds of formula AY14-AY16 in the LC host mixture is preferably from 2 to 35%, very preferably from 3 to 30%. The proportion of the compounds of formula BF1 in the LC host mixture is preferably from 0.5 to 20%, very preferably from 1 to 15%. Further preferably the LC host mixture according to this preferred embodiment contains one or more, preferably 1 , 2 or 3 compounds of formula T, preferably selected from formula T1 , T2 and T3, very preferably from formula T2. The proportion of the compounds of formula T in the LC host mixture medium is preferably from 0.5 to 15%, very preferably from 1 to 10%.

In the LC medium according to the present invention, the use of an LC host mixture together with the use of a polymerizable component comprising a combination of a first, second and third polymerizable compound as described above leads to advantageous properties in LC displays. In particular, one or more of the following advantages could be achieved: - easy and quick formation of polymer walls by polymerization-induced phase separation of the polymer formed by the first and second

polymerizable compounds,

- formation of polymer walls with highly defined shape and constant

thickness,

- constant cell gap,

- high flexibility of the display cell in case plastic substrates are used,

- high resistance of the display cell against mechanical pressure, and low variation of the cell gap under pressure,

- good adhesion of the polymer walls to the substrates,

- low number of defects,

- reduced formation of domains with different electrooptical properties like response time or contrast,

- high transparency,

- good contrast,

- fast response times.

The display manufacture process is known to the skilled person and is described in the literature, for example in US6130738 and EP2818534 A1.

The present invention also relates to a process for the production of an LC display as described above and below, comprising the steps of providing an LC medium as described above and below into the display, and polymerizing the polymerizable compounds in defined regions of the display by RAFT polymerization.

Preferably the polymerizable compounds are photopolymerized by exposure to UV irradiation.

Further preferably the polymerizable compounds are photopolymerized by exposure to UV irradiation through a photomask. The UV radiation can be generated by a variety of light sources which are known to the skilled person, including but not limited to arc lamps, led lights, laser light sources, or others. The photomask is preferably designed such that it comprises regions that are transparent to the UV radiation used for photopolymerization, and regions that are not transparent to the UV radiation used for photopolymerization, and wherein the transparent regions form a pattern or image that

corresponds to the desired shape of the polymer walls. As a result the polymerizable compounds are only polymerized in those parts of the display that are covered by the transparent regions of the photomask, thus forming polymer walls of the desired shape.

Alternatively to using a photomask, a light source can be used that emits light with an already shaped profile. Such profile can for example be generated by interference of two laser beams. In a preferred embodiment of the present invention, the display is subjected to a second UV irradiation step, preferably without a photomask applied, after the first UV irradiation step as described above. Thereby it is possible to complete polymerization of monomers that were not or only partially polymerized in the first step. The second UV step can have an emission spectrum and/or intensity which is the same as that of the first step, or which is different from the first step.

Alternatively two applying two separate irradiation steps, the intensity is changed during UV exposure. Preferably, the intensity is gradually increased during UV exposure.

For example, an LC display according to the present invention can be manufactured as follows. Polymerizable compounds as described above and below are combined with a suitable LC host mixture. This resulting LC medium can then be included into the display by using conventional manufacturing processes. The resulting LC medium can be filled for example using capillary forces into the cell gap formed by two substrates.

Alternatively, the LC medium can be deposited as a layer onto a substrate, and another substrate is placed on top of the LC layer under vacuum in order to prevent inclusion of air bubbles. The LC medium is in either case located in the cell gap formed by the two substrates, as exemplarily illustrated in Fig. 1a. These substrates usually are covered by an alignment layer which is in direct contact with the LC medium. The substrates itself can carry other functional components like TFTs, black matrix, colour filter, or similar.

Subsequently, polymerization induced phase separation is initiated by exposure of the LC medium, which is either in the nematic or the isotropic phase, to UV radiation with collimated light through a photomask, as exemplarily illustrated in Fig. 1b. This leads to the formation of polymer wall structures, restoration of the LC host, and alignment of the LC phase with the alignment layer, as exemplarily illustrated in Fig. 1c.

This process can advantageously utilize display manufacturing processes that are established in the industry. Thus, both the display filling process, for example by one-drop-filling (ODF), and the radiation initiated polymerization step after sealing the display, which is known for example from polymer stabilised or PS-type display modes like PS-VA, are established techniques in conventional LCD manufacturing. A preferred LC display of the present invention comprises:

a first substrate including a pixel electrode defining pixel areas, the pixel electrode being connected to a switching element disposed in each pixel area and optionally including a micro-slit pattern, and optionally a first alignment layer disposed on the pixel electrode,

a second substrate including a common electrode layer, which may be disposed on the entire portion of the second substrate facing the first substrate, and optionally a second alignment layer,

an LC layer disposed between the first and second substrates and including an LC medium comprising a polymerizable component A and a liquid-crystalline component B as described above and below, wherein the polymerizable component A is polymerized.

The LC display may comprise further elements, like a colour filter, a black matrix, a passivation layer, optical retardation layers, transistor elements for addressing the individual pixels, etc., all of which are well known to the person skilled in the art and can be employed without inventive skill.

The electrode structure can be designed by the skilled person depending on the individual display type. For example for VA displays a multi-domain orientation of the LC molecules can be induced by providing electrodes having slits and/or bumps or protrusions in order to create two, four or more different tilt alignment directions. The first and/or second alignment layer controls the alignment direction of the LC molecules of the LC layer. For example, in TN displays the alignment layer is selected such that it imparts to the LC molecules an orientation direction parallel to the surface, while in VA displays the alignment layer is selected such that it imparts to the LC molecules a homeotropic alignment, i.e. an orientation direction perpendicular to the surface. Such an alignment layer may for example comprise a polyimide, which may also be rubbed, or may be prepared by a photoalignment method.

The substrate can be a glass substrate, for example in case of a curved display. The use of an LC medium according to the present invention in an LC display with glass substrates can provide several advantages. For example, the formation of polymer wall structures in the LC medium helps to prevent the so-called“pooling effect” where pressure applied on the glass substrates causes unwanted optical defects. The stabilizing effect of the polymer wall structures also allows to further minimize the panel thickness. Moreover, in bent panels with glass substrates the polymer wall structures enable a smaller radius of curvature.

For flexible LC displays preferably plastic substrates are used. These plastic substrates preferably have a low birefringence. Examples are polycarbonate (PC), polyethersulfone (PES), polycyclic olefine (PCO), polyarylate (PAR), polyetheretherketone (PEEK), or colourless polyimide (CPI) substrates.

The LC layer with the LC medium can be deposited between the substrates of the display by methods that are conventionally used by display

manufacturers, for example the one-drop-filling (ODF) method. The polymerizable component of the LC medium is then polymerized for example by UV photopolymerization.

In case the polymerizable compounds are used as a replacement for spacer particles, the display manufacturing process preferably comprises the following steps:

In a first step, the LC medium containing the LC host and monomer precursor is applied to one of the two substrates, preferably by using one of the following deposition methods: one drop filling, ink jet printing, spin coating, slit coating, flexo printing, or a comparable method. The substrate in that instance may carry a colour filter, TFT devices, a black matrix, a polyimide coating, or other components typically found on a display substrate. The applied LC medium forms a thin, uniform film with the thickness of the targeted cell gap of the final device.

In a second step, the applied film is subjected to UV radiation having an intensity profile. This profile is generated for example by irradiating through a photomask, lithography, contact lithography, proximity lithography, projection lithography, using laser interference, direct laser writing, or a comparable method. Irradiation of the film can either occour from either side of the substrate. In case of using a photomask, the mask can either placed on the substrate and the LC film is cured by the light passing through the substrate, or the mask is directly brought in close proximity to the LC film and the LC medium is cured directly.

In this second step, polymer wall structures are created that function as spacer.

Subsequently, the second substrate, which may also carry colour filter, TFT devices, a black matrix, a polyimide coating, or other components typically found on a display substarte, is place ontop of the first substrate so that the LC film comes to rest in between the two substrates.

A further irradiation is now optionally possible to convert unreacted

monomers, generate adhesion between the two substartes, and/or seal the edges of the display. The polymerization of the polymerizable compounds can be carried out in one step or in two or more steps. It is also possible to carry out the polymerization in a sequence of several UV irradiation and/or heating or cooling steps. For example, a display manufacturing process may include a first UV irradiation step at room temperature to produce a pretilt angle, and subsequently, in a second polymerization step to polymerize or crosslink the compounds which have not reacted in the first step ("end curing"). Upon polymerization the polymerizable compounds react with each other to a polymer which undergoes macroscopical phase-separation from the LC host mixture and forms polymer walls in the LC medium.

Suitable and preferred polymerization methods are, for example, thermal or photopolymerization, preferably photopolymerization, in particular UV induced photopolymerization, which can be achieved by exposure of the polymerizable compounds to UV radiation.

Preferably the LC medium contains one or more polymerization initiators.

The polymerizable compounds according to the invention are also suitable for polymerization without an initiator, which is accompanied by considerable advantages, such, for example, lower material costs and in particular less contamination of the LC medium by possible residual amounts of the initiator or degradation products thereof. The polymerization can thus also be carried out without the addition of an initiator. In a preferred embodiment, the LC medium contains a polymerization initiator.

The LC medium may also comprise one or more stabilizers or inhibitors in order to prevent undesired spontaneous polymerization of the RMs, for example during storage or transport. Suitable types and amounts of stabilizers are known to the person skilled in the art and are described in the literature. Particularly suitable are, for example, the commercially available stabilizers from the Irganox® series (Ciba AG), such as, for example, Irganox® 1076. If stabilizers are employed, their proportion, based on the total amount of RMs or the polymerizable component (component A), is preferably 10-500,000 ppm, particularly preferably 50-50,000 ppm.

Preferably the LC medium according to the present invention does essentially consist of a polymerizable component A and an LC component B (or LC host mixture) as described above and below. However, the LC medium may additionally comprise one or more further components or additives.

The LC media according to the invention may also comprise further additives which are known to the person skilled in the art and are described in the literature, such as, for example, polymerization initiators, inhibitors, stabilizers, sensitizers, surface-active substances or chiral dopants. These may be polymerizable or non-polymerizable. Polymerizable additives, polymerization initiators and sensitizers are ascribed to the polymerizable component or component A. Other non-polymerizable additives are ascribed to the non-polymerizable component or component B.

Preferred additives are selected from the list including but not limited to co- monomers, chiral dopants, polymerization initiators, inhibitors, stabilizers, surfactants, wetting agents, lubricating agents, dispersing agents,

hydrophobing agents, adhesive agents, flow improvers, defoaming agents, deaerators, diluents, reactive diluents, auxiliaries, colourants, dyes, pigments and nanoparticles. In a preferred embodiment the LC media contain one or more chiral dopants, preferably in a concentration from 0.01 to 1 % by weight, very preferably from 0.05 to 0.5% by weight. The chiral dopants are preferably selected from the group consisting of compounds from Table B below, very preferably from the group consisting of R- or S-1011 , R- or S-2011 , R- or S-3011 , R- or S-4011 , and R- or S-5011.

In another preferred embodiment the LC media contain a racemate of one or more chiral dopants, which are preferably selected from the chiral dopants mentioned in the previous paragraph. Furthermore, it is possible to add to the LC media, for example, 0 to 15% by weight of pleochroic dyes, furthermore nanoparticles, conductive salts, preferably ethyldimethyldodecylammonium 4-hexoxybenzoate, tetrabutyl- ammonium tetraphenyl borate or complex salts of crown ethers (cf., for example, Haller et al., Mol. Cryst. Liq. Cryst. 24, 249-258 (1973)), for improving the conductivity, or substances for modifying the dielectric anisotropy, the viscosity and/or the alignment of the nematic phases. Sub- stances 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 LC media which can be used in accordance with the invention are prepared in a manner conventional per se, for example by mixing one or more of the above-mentioned compounds with one or more polymerizable compounds as defined above, and optionally with further liquid-crystalline compounds and/or additives. In general, the desired amount of the com- ponents used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing. The invention furthermore relates to the process for the preparation of the LC media according to the invention.

It goes without saying to the person skilled in the art that the LC media according to the invention may also comprise compounds in which, for example, H, N, O, Cl, F have been replaced by the corresponding isotopes like deuterium etc.

The following examples explain the present invention without restricting it. However, they show the person skilled in the art preferred mixture concepts with compounds preferably to be employed and the respective con- centrations thereof and combinations thereof with one another. In addition, the examples illustrate which properties and property combinations are accessible. Preferred mixture components are shown in Tables A1 and A2 below. The compounds shown in Table A1 are especially suitable for use in LC mixtures with positive dielectric anisotropy. The compounds shown in Table A2 are especially suitable for use in LC mixtures with negative dielectric anisotropy.

Table A1

In Table A1 , m and n are independently of each other an integer from 1 to 12, preferably 1 , 2, 3, 4, 5 or 6, k is 0, 1 , 2, 3, 4, 5 or 6, and (0)C_mH2 m+i means Cm H2m+1 or OC mH2m+1

189

ECCP-nm ECCP-nOCFs

Table A2

In Table A2, m and n are independently of each other an integer from 1 to 12 preferably 1 , 2, 3, 4, 5 or 6, k is 0, 1 , 2, 3, 4, 5 or 6, and (0)C_mH_{2 m+i} means Cm H2m+1 or OC mH2m₊₁

C-1V-V1

CCY-n-m

CCP-nV-m

CVY-V-n

CCY-n-kOm

COChrom-n-Om

CCNaph-n-Om

LYLI-n-m

YPY-n-m

Y-nO-OmV

YY-nO-Om In a first preferred embodiment of the present invention, the LC media according to the invention, especially those with positive dielectric anisotropy, comprise one or more compounds selected from the group consisting of compounds from Table A1.

In a second preferred embodiment of the present invention, the LC media according to the invention, especially those with negative dielectric

anisotropy, comprise one or more compounds selected from the group consisting of compounds from Table A2.

Table B

Table B shows possible chiral dopants which can be added to the LC media according to the invention.

CM 44 CM 45

R/S-1011 The LC media preferably comprise 0 to 10% by weight, in particular 0.01 to 5% by weight, particularly preferably 0.1 to 3% by weight, of dopants. The LC media preferably comprise one or more dopants selected from the group consisting of compounds from Table B. Table C

Table C shows possible stabilizers which can be added to the LC media according to the invention. Therein n denotes an integer from 1 to 12, preferably 1 , 2, 3, 4, 5, 6, 7 or 8, and terminal methyl groups are not shown.





The LC media preferably comprise 0 to 10% by weight, in particular 1 ppm to 5% by weight, particularly preferably 1 ppm to 1 % by weight, of stabilizers. The LC media preferably comprise one or more stabilizers selected from the group consisting of compounds from Table C.

In addition, the following abbreviations and symbols are used:

Vo threshold voltage, capacitive [V] at 20°C,

n_e extraordinary refractive index at 20°C and 589 nm,

n₀ ordinary refractive index at 20°C and 589 nm,

Dh optical anisotropy at 20°C and 589 nm,

i dielectric permittivity perpendicular to the director at 20°C and 1 kHz,

|| dielectric permittivity parallel to the director at 20°C and 1 kHz,

De dielectric anisotropy at 20°C and 1 kHz,

cl.p., T(N,I) clearing point [°C],

gi rotational viscosity at 20°C [mPa s],

Ki elastic constant, "splay" deformation at 20°C [pN],

K2 elastic constant, "twist" deformation at 20°C [pN], K3 elastic constant, "bend" deformation at 20°C [pN]

Unless explicitly noted otherwise, all concentrations and ratios in the present application are quoted in per cent by weight, and preferably relate to the corresponding mixture as a whole, comprising all solid or liquid-crystalline components, without solvents.

Unless explicitly noted otherwise, all temperature values indicated in the present application, such as, for example, for the melting point T(C,N), the transition from the smectic (S) to the nematic (N) phase T(S,N) and the clearing point T(N,I), are quoted in degrees Celsius (°C). M.p. denotes melting point, cl.p. = clearing point. Furthermore, C = crystalline state, N = nematic phase, S = smectic phase and I = isotropic phase. The data between these symbols represent the transition temperatures.

All physical properties are and have been determined in accordance with "Merck Liquid Crystals, Physical Properties of Liquid Crystals", Status Nov. 1997, Merck KGaA, Germany, and apply for a temperature of 20°C, and Dh is determined at 589 nm and De at 1 kHz, unless explicitly indicated otherwise in each case.

The term "threshold voltage" for the present invention relates to the capa- citive threshold (Vo), also known as the Freedericks threshold, unless explicitly indicated otherwise. In the examples, the optical threshold may also, as generally usual, be quoted for 10% relative contrast (V10).

Examples

A) Host Mixtures

The nematic LC host mixture N1 is formulated as follows.

CC-3-V 50.00 % cl.p. 79.4

CC-3-V1 4.50 % Dh 0.1094

CCP-V-1 13.50 % De 5.2

CPGU-3-OT 6.00 % e 8.1 PGP-2-2V 6.50 % yi 54 mPa s

PGU-2-F 10.00 %

PGUQU-3-F 7.00 %

PPGU-3-F 2.00 %

PUQU-2-F 1 .50 %

The nematic LC host mixture N2 is formulated as follows.

CC-3-V 40.00 % cl .p. 81 .5°C CC-3-V1 8.00 % Dh 0.0827 PUQU-2-F 3.00 % De 9.4 PUQU-3-F 8.00 % e 12.8 APUQU-2-F 7.00 % gi 75 mPa-s APUQU-3-F 7.00 %

CCP-3-1 7.00 %

CCOC-3-3 5.00 %

CCOC-4-3 5.00 %

CDUQU-3-F 10.00 % Monomers

Photoinitiators

Polymerizable Mixtures

Polymerizable mixture preparation: Polymerizable LC media for polymer wall formation are prepared by mixing LC host, monomers, photoinitiator and optionally the RAFT agent, and then homogenizing the resulting mixture by heating above its clearing point.

The polymerizable mixture compositions are shown in Table 1 below. The polymerizable mixtures C1 and C2 are comparison mixtures which do not contain a RAFT agent. The polymerizable mixtures M1 -M5 are mixtures according to the present invention which contain a RAFT agent.

5

Table 1

10

15

20

(Summe der Konz. fiir M1 ist 102%, bitte Oberpmfen)

Polymer Wall Formation

oc

Test Cells: The test cells comprise two 0.3mm thick glass substrates coated with ITO, which are kept apart by spacer particles or foils at a layer thickness of 3-4 microns and glued together by an adhesive (usually Norland, NEA

123). On top of the electrode layers polyimide alignment layers (Nissan SE-

6514 or SE2414) are applied which are rubbed parallel or antiparallel.

30

Wall formation:

The test cells are filled with the LC medium and placed on a black, non- reflecting surface. A photomask is placed on top of the test cells and the sample is subjected to UV radiation (Flg/Xe arch lamp, LOT QuantumDesign 35

Europe, LS0205). Radiation of the emission spectrum below 320nm is removed by a dichroic mirror. The UV intensity is measured at a wavelength of 365+/-10nm FWHM (for all steps).

Two UV radiation steps were used:

UV1 : 30min at 4mW/cm² followed by 30min at 10mW/cm²

UV2: 5min at 25mW/cm²

The photomask usually has a pattern of equidistant lines of the same thickness. The line thickness is 140 microns and the distance between the lines is 9 microns, unless stated otherwise.

Characterization: Samples are analyzed under a polarization microscope. The isotropic polymer walls can clearly be distinguished from areas containing birefringend LC. The width of the walls and inclusions of LC into the polymer walls, and defects in the pixel area caused by contamination of polymer, or misalignment of the LC caused by the wall formation process can be observed.

Device Examples

Polymerizable LC mixtures C1 , C2 and M1 -M5 are each filled into a test cell and subjected to UV irradiation under a photomask as described above.

Fig. 2-9 show polarization microscope images of test cells prepared from the polymerizable mixtures after polymerization. The formed polymer walls can be seen as dark lines, which means that the pattern of the mask has been reproduced in the reactive mixture.

Fig. 2 and 3 show polarization microscope images of test cells prepared from polymerizable mixtures C1 and C2, respectively.

As can be seen in Fig. 2, in case of mixture C1 there is still a certain amount of LC material trapped inside the polymer walls (visible by bright spots in the dark wall areas), which is attributed to lower degree of phase separation between the LC molecules and the formed polymer. As can be seen in Fig. 3, in case of mixture C2 the alignment of the LC molecules in the pixels is disturbed, which is attributed to the high amount of direactive monomer employed. Fig. 4-7 show polarization microscope images of test cells prepared from polymerizable mixtures M1 -M4, respectively.

As can be seen in Fig. 4-7, for all mixtures polymer walls were formed with a significantly lower amount of LC material trapped inside the walls due to better phase separation between the LC molecules and the formed polymer. Also the pixels show good alignment of the LC molecules.

It can also be seen in Fig. 7 (Mixture M4) that when using a RAFT agent even a high amount of direactive monomer (here 19%) can be employed without disturbing the LC alignment.

Fig. 8 and 9 show polarization microscope images of test cells prepared from polymerizable mixture M5 directly after polymerization (Fig. 8) and after 60 min thermal treatment at 70°C (Fig. 9). It can be seen that polymer walls are formed with good phase separation and good LC alignment in the pixels. It can also be seen that the polymer walls and the LC alignment are stable even after thermal treatment. The example was also in contrast to Fig. 1-7 prepared by using method UV2, which demsonstrates that thermally stable and well-formed polymer walls can be realized after a very short process time.

Claims

1. A liquid crystal (LC) medium comprising a polymerizable component A and a liquid-crystalline component B, wherein component B comprises one or more mesogenic or liquid-crystalline compounds, and

component A comprises one or more polymerizable compounds comprising a straight-chain or branched hydrocarbon group having from 1 to 30 C atoms, or a monocyclic hydrocarbon group having from 3 to 24 ring atoms, or a bi- or polycyclic hydrocarbon group having from 4 to 30 ring atoms, and attached thereto one or more polymerizable groups that are capable of radical polymerization, a RAFT agent, and optionally a polymerization initiator,

2. The LC medium of claim 1 , characterized in that the RAFT agent is

selected from formula I

X¹ -S-R^b, -0-R^b, -N(R^bR^c) or aryl or heteroaryl having 5 to 20 ring atoms that is optionally substituted by L,

R^a straight-chain or branched or cyclic alkyl with 1 to 60 C atoms that is optionally fluorinated, and wherein one or more CFh- groups are optionally replaced by -C(R°)=C(R⁰⁰)-, -CºC- , -N(R⁰)-, -0-, -S-, -CO-or -CS- or by a polyglycol chain - (CFhCFhOJ_n- in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms are optionally replaced by F, Cl, Br, I, CN or N3, or by a heterocyclic, aromatic or heteroaromatic group having 5 to 20 ring atoms that is optionally substituted by one or more groups L, or R^a is aryl or heteroaryl having 5 to 20 ring atoms, preferably phenyl, that is optionally substituted by one or more groups L,

R^b, R^c H or one of the meanings given for R^a, or R^b and R^c together with the N-atom to which they are attached may also form a heterocyclic or heteroaromatic group with 5 to 8 ring atoms that is optionally substituted by L.

L F, Cl, -CN, -NO2, -NCO, -NCS, -OCN, -SCN, -C(=0)N(R^q)₂, -

C(=0)Y^z, -C(=0)R^q, -N(R^q)2, optionally substituted silyl, optionally substituted aryl or heteroaryl having 5 to 20 ring atoms, or straight-chain or branched alkyl having 1 to 25 C atoms in which, in addition, one or more non-adjacent CFI2 groups may each be replaced, independently of one another, by -C(R°)=C(R⁰⁰)-, -CºC-, -N(R⁰)-, -0-, -S-, -CO-, -CS-, -CO-O- , -O-CO-, -O-CO-O- in such a way that O and/or S atoms are not linked directly to one another, and in which, in addition, one or more FI atoms may be replaced by F, Cl, -CN,

R^q FI, F, Cl, CN, or straight chain, branched or cyclic alkyl

having 1 to 25 C atoms, wherein one or more non-adjacent CFh-groups are optionally replaced by -O-, -S-, -CO-, -CO-O- , -O-CO-, -O-CO-O- in such a manner that O- and/or S- atoms are not directly connected with each other, and wherein one or more FI atoms are each optionally replaced by F or Cl,

R°, R⁰⁰ FI or alkyl having 1 to 20 C atoms,

Y^z halogen, preferably F or Cl, n an integer >1 , preferably from 1 to 300, or from 1 to 12.

3. The LC medium of claim 1 or 2, characterized in that the RAFT agent is selected from the following subformulae

R^a, R^b, R^c one of the meanings given in claim 2,

R^d straight-chain or branched alkylene with 2 to 30 C atoms, wherein one or more CFte groups are optionally replaced by - 0-, -CO- or -( CFteCFteOJ_n- and wherein one or more H atoms are optionally replaced by CN,

R^e straight-chain or branched or cyclic alkyl with 1 to 20 C atoms that is optionally fluorinated, and wherein one or more CFte- groups are optionally replaced by -C(R°)=C(R⁰⁰)-, -CºC- , -N(R⁰)-, -0-, -S-, -CO-,-CS- or -(CFhCFhOV in such a way that O and/or S atoms are not linked directly to one another, and in which one or more H atoms may be replaced by F, Cl, Br, I, CN or N3, or by a heterocyclic, aromatic or heteroaromatic group having 5 to 20 ring atoms that is optionally substituted by one or more groups L, or R^c1 is aryl or heteroaryl having 5 to 20 ring atoms, preferably phenyl, that is optionally substituted by one or more groups L,

Ar aryl or heteroaryl with 5 to 8 ring atoms, preferably phenyl, which is optionally substituted by one or more groups L

L one of the meanings given in claim 2, n an integer >1 , preferably from 1 to 300 or from 1 to 12.

4. The LC medium according to one or more of claims 1 to 3, character- ized in that the RAFT agent is selected from the following subformulae

wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings R^a1 phenyl, pentafluorophenyl or

R^a2 H, R^b1, phenyl or CN,

R^d1 alkylene with 2 to 20 C atoms or -(CH₂CH₂0)_n-,

Y³, Y⁴ H, CHs, CN or phenyl,

L one of the meanings given in claim 2, k 0 or 1 , n an integer >1 , preferably from 1 to 300 or from 1 to 12, r 0, 1 , 2, 3 or 4, s 0, 1 or 2.

5. The LC medium according to one or more of claims 1 to 4, character- ized in that component A comprises one or more polymerizable compounds selected of formula II

P a polymerizable group Sp a spacer group or a single bond,

G¹ a straight-chain or branched alkyl group with 1 to 20 C atoms, or a monocyclic alkyl group with 3 to 24 C atoms, that is optionally mono-, poly- or perfluorinated and is optionally substituted by one or more groups L, and wherein one or more Chh-groups are optionally replaced by -0-, -CO-, -O-CO- or -CO-O- such that O- atoms are not directly adjacent to one another,

L one of the meanings given in claim 2.

6. The LC medium according to any of claims 1 to 5, characterized in that component A comprises one or more polymerizable compounds selected from the group consisting of the following subformulae:

P-Sp-(CHW¹¹)n2-(CH₂)ni-(CHW¹²)n3-CH₃ 111

P-Sp-(CH₂)n2-(CF₂)n1-CFW¹³W¹⁴ M2

P, Sp one of the meanings given in claim 5,

W^{1 1} , W¹² H, F or straight-chain or branched Ci-Ci2-alkyl,

W¹³, W¹⁴ are H or F, n1 an integer from 2 to 15, n2, n3 0 or an integer from 1 to 3,

7. The LC medium according to any of claims 1 to 6, characterized in that component A comprises one or more polymerizable compounds of formula IIA

P-Sp-G² IIA wherein P and Sp have the meanings given in claim 5, and G² is a bi- or polycyclic hydrocarbon group, preferably a bridged or fused bi- or polycyclic alkyl group, having 4 to 30 ring atoms, preferably 6 to 25 ring atoms, which is optionally substituted by one or more groups L as defined in claim 2.

8. The LC medium according to any one of claims 1 to 7, characterized in that component A comprises one or more polymerizable compounds selected from the group consisting of the following subformulae

IIAA

NAB

MAC

wherein R on each occurrence identically or differently denotes P-Sp- or has one of the meanings given for R^q in claim 4, and one of the groups R in each of formulae IIAA-IIAC denotes P-Sp-.

9. The LC medium according to any one of claims 1 to 8, characterized in that component A comprises one or more polymerizable compounds selected from the group consisting of the following subformulae IIA1

IIA2

11 A3

IIA4

wherein P and Sp have the meanings given in claim 5, W^{1 1} , W¹² and W¹³ are independently of each other H, F or Ci-Ci2-alkyl, preferably methyl, and the cycloalkyl groups are optionally substituted with one or more groups L as defined in claim 2. 10. The LC medium according to any one of claims 1 to 9, characterized in that component A comprises one or more polymerizable compounds of formula III

P¹-Sp¹-G³-Sp²-P² III wherein the individual radicals, independently of each other, and on each occurrence identically or differently, have the following meanings

P¹ , P² a polymerizable group

Sp¹ , Sp² a spacer group or a single bond G³ a straight-chain, branched or cyclic alkyl group with 1 to 20 C atoms that is optionally mono-, poly- or perfluorinated and is optionally substituted by one or more groups P¹-Sp¹- or by one or more groups L as defined in claim 4, and wherein one or more Chh-groups are optionally replaced by -0-, -CO-, -O- CO- or -CO-O- such that O-atoms are not directly adjacent to one another. 0 1 1 . The LC medium according to any one of claims 1 to 10, characterized in that component A comprises one or more polymerizable compounds selected from the group consisting of the following subformulae

P¹ -Sp¹ -(CH W^{1 1} )n2-(CH₂)n1 -(CH W¹²)_n3-Sp²-P² 1111

5

0 P¹-(CH₂)n2-(CF2)n1-(CH₂)n3-P² IN3

(P¹-Sp¹-(CH₂)n4)n5CH_4-n5 IN4 wherein P¹ , P², Sp¹ , Sp² are as defined in formula III,

5

W^{1 1} , W¹² are, on each occurrence identically or differently, H, F or Ci- Ci₂-alkyl, n1 is an integer from 2 to 15,

0

n2, n3 are independently of each other 0 or an integer from 1 to 3, n4 is 0 or an integer from 1 to 15, c n5 is 3 or 4, and the cyclohexylene ring in formula 1112 is optionally substituted by one or more identical or different groups W^{1 1}.

12. The LC medium according to any one of claims 1 to 1 1 , characterized in that component A comprises one or more polymerizable compounds selected from the group consisting of the following subformulae

CH₂=CW-C0-0-(CH₂)_n2-(CF₂)_ni-(CH₂)_n3-0-CH=CH₂ 1113a

CH₂=CW-C0-0-(CH₂)_n2-(CF₂)_ni-(CH₂)_n3-0-C0-CW=CH₂ 1113b

(CH₂=CW-C0-0-(CH₂)_n2)₃CH 1114a

(CH₂=CW-C0-0-(CH₂)_n2)₄C 1114b wherein W is H, Chb or C₂H₅ and W¹¹, W¹², n1 , n2 and n4 are as defined in claim 10, and the cyclohexylene ring in formula IM2a-c is optionally substituted by one or more identical or different groups W¹¹.

13. The LC medium according to any one of claims 1 to 12, characterized in that.the concentration of the RAFT agent in the LC medium is from 0.001 to 5% by weight.

14. The LC medium according to any one of claims 1 to 13, characterized in component B comprises one or more compounds selected from formulae A and B

of one another, and on each occurrence, identically or differently

R²¹, R³¹ each, independently of one another, alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated,

Z³¹ -CH2CH2-, -CF2CF2-, -COO-, frans-CH=CH-, trans-

CF=CF-, -CFI2O- or a single bond,

L²¹, L ²², L³¹, L ³² each, independently of one another, FI or F, g 0, 1 , 2 or 3.

15. The LC medium according to claim 14, characterized in that component B comprises, in addition to the compounds of formula A and/or B, one or more compounds of formula C

on each occurrence, identically or differently

R⁴¹, R⁴² each, independently of one another, alkyl, alkoxy, oxaalkyl or alkoxyalkyl having 1 to 9 C atoms or alkenyl or alkenyloxy having 2 to 9 C atoms, all of which are optionally fluorinated,

Z⁴¹, Z⁴² each, independently of one another, -CH2CH2-, -COO-, trans- CH=CH-, frans-CF=CF-, -CFI2O-, -CF2O-, -CºC- or a single bond, h 0, 1 , 2 or 3.

16. The LC medium according to any one of claims 1 to 15, characterized in that component B comprises one or more compounds selected from formulae CY and PY:

wherein a denotes 1 or 2 b denotes 0 or 1

R¹ and R² each, independently of one another, denote alkyl having 1 to

12 C atoms, where, in addition, one or two non-adjacent CFh groups may be replaced by -0-, -CH=CH-, -CO-, -OCO- or -COO- in such a way that O atoms are not linked directly to one another,

Z^x and Z^y each, independently of one another, denote -CH2CH2-,

-CH=CH-, -CF2O-, -OCF2-, -CH2O-, -OCH2-, -CO-O-, -O-CO-, -C₂F₄-, -CF=CF-, -CFI=CFI-CFl₂0- or a single bond,

|_1-4 each, independently of one another, denote F, Cl, OCF3

CFs, CHs, CH₂F, CHF₂.

17. The LC medium according to claim 16, characterized in that component B comprises, in addition to the compounds of formula CY and/or PY one or more compounds of formula ZK

in which the individual radicals have the following meanings:

R³ and R⁴ each, independently of one another, denote alkyl having 1 to

12 C atoms, in which, in addition, one or two non-adjacent CFh groups may be replaced by -0-, -CH=CH-, -CO-, -O-CO- or -CO-O- in such a way that O atoms are not linked directly to one another,

Z^y denotes -CH2CH2-, -CH=CH-, -CF2O-, -OCF2-, -CH2O-,

-OCH2-, -CO-O-, -O-CO-, -C₂F₄-, -CF=CF-, -CH=CH-CH₂O- or a single bond.

18. The LC medium according to any one of claims 1 to 17 characterized in that the polymerizable compounds are polymerized by RAFT

polymerization.

19. An LC display comprising an LC medium according to any one of claims 1 to 18.

20. The LC display of claim 19, which is a flexible or curved display.

21. The LC display of claim 19 or 20, which is a TN, OCB, IPS, FFS, posi- VA, VA or UB-FFS display.

22. A process for the production of an LC display according to any one of claims 19 to 21 , comprising the steps of providing an LC medium as defined in any one of claims 1 to 17 into the display, and polymerizing the polymerizable compounds in defined regions of the display by RAFT polymerization.

23. The process of claim 22, wherein the polymerizable compounds are

photopolymerized by exposure to UV irradiation.

24. The process of claim 23, wherein the polymerizable compounds are photopolymerized by exposure to UV irradiation through a photomask.

25. A process of preparing an LC medium according to any one of claims 1 to 17, comprising the steps of mixing a liquid-crystalline component B as defined in any one of claims 1 and 14 to 17 with one or more polymerizable compounds, or with component A, as defined in any one of claims 1 to 13, and optionally with further LC compounds and/or additives.